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    JHOEL_GEO
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    This document is a doctoral thesis submitted to Victoria University of Wellington that examines epithermal gold-silver and porphyry copper deposits in the Hauraki Province of New Zealand. The thesis includes experimental work analyzing the mineralogy, fluid inclusions, and stable isotopes of the deposits. It aims to determine the physicochemistry of mineralization at different areas and formulate a model of mineral genesis. The individual deposits are described in an appendix, incorporating the author's work and a literature review. The thesis focuses on a comparative study of the deposits to understand the processes and environments involved in their formation.

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    Thesis

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    This document is a doctoral thesis submitted to Victoria University of Wellington that examines epithermal gold-silver and porphyry copper deposits in the Hauraki Province of New Zealand. The thesis includes experimental work analyzing the mineralogy, fluid inclusions, and stable isotopes of the deposits. It aims to determine the physicochemistry of mineralization at different areas and formulate a model of mineral genesis. The individual deposits are described in an appendix, incorporating the author's work and a literature review. The thesis focuses on a comparative study of the deposits to understand the processes and environments involved in their formation.

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    © All Rights Reserved
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    420 просмотров863 страницы

    Thesis

    Загружено:

    JHOEL_GEO
    This document is a doctoral thesis submitted to Victoria University of Wellington that examines epithermal gold-silver and porphyry copper deposits in the Hauraki Province of New Zealand. The thesis includes experimental work analyzing the mineralogy, fluid inclusions, and stable isotopes of the deposits. It aims to determine the physicochemistry of mineralization at different areas and formulate a model of mineral genesis. The individual deposits are described in an appendix, incorporating the author's work and a literature review. The thesis focuses on a comparative study of the deposits to understand the processes and environments involved in their formation.

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    © All Rights Reserved
    Скачайте в формате PDF, TXT или читайте онлайн в Scribd
    Отметить как неприемлемый контент
    из 863

    Flontispiece: Battery buildt-ngs of the i{oodstock Goldmining Cunpanyt

    Karangahaker 189?. Watercolour by Christopher Aubrey (ftoruit


    LS76 - 1906). Alexander l\rnbul-l Llbrary.
    ATMHCNS BIRBT C-HRISII4

    ED0{D StCIItgI0ffi1 S{IABIE sqnQPE! AilD (Em[I$fi[fflRr


    OF P"OM.EINf, C. P.ER AIID @.ITTMNI{A,f, VETN .I}me6Tlg
    gP TIE EIIINAffI GAIO. SILIEN PINC'VIN@.,;

    MH ZBII.A}ilI

    v,ofiIt{E I

    &l.ttritted f,of Ghe degree of


    Doe,tsr of ptrllosqph.y
    in ,Ge.ologr. at the Vi,cDoda lNraiiversi.ty
    of lfell5.ngton

    .hgust 19{E
    (i)
    ABSTRACT

    Tertiary epithermal Au-Ag-Pb-Zn-cu vej-n, and porphyry copper


    deposlts oecur in the Hauraki Province.

    The epithernal deposits were extensi.vely mined for gold and


    silver in the rate i800t", and early 1900;s and produced. approx-
    inately 3oo nillion grans (to nilLion ounces) of gold and 1,000
    nillion grans (lo million ounces)of silver. They oecur in
    Jurassic greywaeke suite rocks, lower Miocene-Plioeene andesites
    and dacites, and upper Miocene-Pleistocene rhyolites although
    the deposits in the andesites and dacites produced most of the
    gold and silver nined

    Base netal assenblages of the epithermal deposits are


    dominated by pyrite, sphaleriter galena and chalcopyrlte, whereas
    acanthite and native gold (eleatrum) are the most eoiuruon precious
    metal minerals. Tellurides (e.g, hessite) and seleniferous
    selenide minerals are 1ocally important. Gangue minerals are
    nainly quartz and calci-te.

    Near neutral or slightly alkaline fluid pH is indicated for


    the epithermar fluid.s by the oecurrence of seiicite and./or
    adularia in wall roek alteration nj-neral assenblagso Aeidie
    fluids, forming kaolinite, are characteristic of l-ate stages or
    near surface envi.ronnents.

    Fluid inclusion filling tenperatures, and sulphur isotope


    temperatures fron sphalerite-galena pairs, indicate that base
    rnetal deposition occurred nainly between ]zo and. 280oc, precious
    netal assemblages predominantly in the,range of 290 - 200oc and
    late stage barite, in sone deposits, generally berow 200oc.
    There is fluid inclusion evj-dence for boiling during mineralisa-
    tion in sone deposits.

    Apparent salinities of the epithermal fluidsrdetlrmined fron


    fluid inelusion freezing tenperatures, range fron 0 - 5.1 eq. wt.
    fi NaCl. No consistent dlfference in average apparent salinity
    was recognised between the different types of epithernal deposits,
    although the highest recorded values were from the base r:etal
    dePosits' *-----
    Vicronl'r I JFIvE=.stry oF v/ELLINGToN
    (ii)
    The absence of liquid co2 i-n fluid inclusions linits the
    maxinum possible concentration of C0a to aoproximately 3 rnole %.
    Extraetion and measurement of C0, from some samples indi-cates
    an average concentratlon of appro.xi-nately 1 urole fi. Comections
    for dissolved COa required to transform apparent salinities to
    true salinities indicate that coe is the najor solute in row
    salinity inclusions and that its coneentration varied widely
    during nineral deposition in nost deposits.

    Thernodynamic models of the geochemical environments of


    mineral depositj.on indicate that the large gold-silver d.eposits
    were formed by solutions i.n which sulphur oceurred predoninantly
    in r6duced form, uhereas nany other d.eposits forned from
    solutions with approximately equal eoncentrations of oxidised
    and redueed aqueous sulphur species.

    ' Mineral deposition resulted fron several different proeesses


    i.ncluding: ehanges in fluid pH.accompanying reactions with the
    wal1 rocks, nixing with other types of fluids, boiring, and
    variations in the concentration of c0, i_n sorution. Thesb
    various processes acted separately in different parts of the
    hydrothermal system and general deposited characteristic mineral
    assemblages.

    . Deuterium/hydrogen ratios of water extracted from fluid


    incl-usions indicate that most hydrothernal fluids were originally
    neteorie water.

    Sulphur isotope ratios of sulphide and sulphaie minerals, in


    association r.rith the thernodynamic relations of the nineral
    assenblagesl-lndicate that the sulphur was derived. from at least
    two different sources; sedinentary sulphate and'magmatic S02,
    the relative inportance of each varyi-ng from one d.eposit to
    another.

    Two types of hydrothernal systen's are postulated. fot' the'


    fornation of the eplthermal-deposits. During andesitic volcanisn
    in the Mioeene-ear1y Pliocene, hydrothermal fluid eonvective
    cel1s were generated by heat from. near surface sna1l intrusive
    bodies of nagma, whereas during rhyolitic vol-canism in the late
    Miocen+Pleistocsrethe heat sources were J-arger plutons at greater
    depth.
    (iii)
    Porphyry eopper deposits are associated with quartz diorite
    stocks intruded i-nto Jurassic greywacke sui-te roeks and Miocene
    andesites. They are trd.ioriterr nodel hypabyssal and volcanic
    types. The najor ninerals are quartz, pyrite, chalcopyrite and
    sphalerite. Additional ninerals differ between the different
    deposits and d.efine two contrasting'geochemical environnents of
    d.eposition, one characterised by low fS2' fO, and.4S, i-ndicated
    by the presence of pyrrhotite, and the other of noderate to
    hlgh fS2, fOa and 4S, indicated. by the oceurrence of bornite,
    magnetite or henatite. Associated hydrothermal alteration is
    generally propylitic although linited phyllic and trpotassictr
    (defined by secondary biotite) types also occur i.n some deposits.

    Fluid inclusion and sulphur isotope stud.ies of the Miners


    Head. porphyry copper deposi-t'suggest that copper mineralisation
    occurred at a tenperature of approximately t*25o}'fron fluids
    with apparent salinities up to.15.5 ee. wt, f, NaCl and containing
    sulphur of nagmatic origlnr pred.ominantly as II2S.
    (iv)

    PREFACE

    The principal aim of this thesis i-s to deternine and


    conpare the physicochenistry of ninerali-sations fron several
    areas of Great Barrier Island and the Coronandel peninsula
    (Hauraki Gold - Silver Province). A secondary aj-m is to
    formulate a nodel of mineral genesis.

    The writers experi-nental work consisted of four najor


    proiects: 1. electron microprobe analyses of selected sulphid.e
    ninerals, 2. fluid inclusion heating and freezing studies,
    3. fluid i-ncrusion chenical and isotopic (trydrogen) analyses,
    and 4. sulphur isotope analyses of sulphide and sulphate
    ninerals. rn addition a brief study was nade of the ore
    petrography of some deposits.

    The geology and hyd.rothermal alteratj.on of the deposi.ts


    were not investigated by the writer because they have been
    studied. in detail within the last fifteen years by other
    workers. However much of this information is currently un-
    published. and is only available in rnineral expiLoration reports
    and theses. I{illians (1971), the nost reeent comprehensive
    review, incrudes naterial up to only 1971 and therefore it is
    appropriate to ineorporate an up-to-date review in this thesis.

    A description of the individual deposits, incorporating


    the writers work and a review of previous studies, is
    presented in volume 2. Beeause this thesis is prinarily a
    conparative study of the d.eposits, the forner section is
    presented as an appendi.x (Appendi.x r) rather than as a
    separate part within the rnain sestlon. However, it contains
    nost of the geologicar and physicochemical- data, and inter-
    pretationr on r.rhich the thesis is based and is therefore not
    a rrsubsidary additionrt i-n the strict sense of the word
    appendix (as defi-ned by the concise Oxford. Dlctionary; sykes,
    1976) .

    The choice of areas studied and the detail of inforrnation


    presented in thi-s thesis is i-nfluenced by the aecessibility
    of the individual ceposits. }linin3 in the pro.'rince was rainly
    (")

    confined. to the l-ate 1800ts and early 1900rs and most of the
    workings are nov partly or ful1y collapsed. Many of the nines,
    includ.ing the largest, Iilaihi, were nined from shafts and are
    now flood.ed. samples originatlng fron sone of these mines
    were obtained from nine dumps and museum, university and
    private collections. The precision with which their original
    locati.on within the mine ca! be deterni-ned. depends on the
    care taken in their original collection, eollation and storage.

    The deposits in the Thames Tapu, Kapowai- and Go]den


    Cross areas (Fig. 1-1) were not i-nvestigated. (although reviewed
    in Appendix r). Merchant (l9lg), concurrently with the early
    part of this thesis work, stud.ied. the mj-neralisation and
    fluid. inclusions of the Thanes - Tapu area and Dr. B.W.
    Rbbinson of the fnstitute of Nuclear Sciences has investigated
    the stabLe isotopes (unpubllshed). Although sone und.erground.
    workings are accessible at Kapowai, nineralisation is rare
    and the vein naterial generally unsuitable for fluid inclusi.on
    work (chalced.onie quartz and quartz pseudonorphs after calcite).
    The workings at Golden Cross are inaccessibl_e.
    ('i)

    coriTElrts 0F voluHs 1

    Page

    ABSTRACT (1)
    PRSFACE (rv)
    COHIEI{TS (vl)
    LIST O8 FIGUSES (xxl11 )
    LIST OF TASLES (xxxtv)
    ACKNOWLEDGEUEI{TS (xxxvl.tl)
    ABBREVIATIONS OT UII8RAL IIAMES (xl)
    CSAPfER 1 INT&ODUOTIO!I t
    LOCAIIOII OF STUDT 1

    ECONOMIC IIISTORY 1

    PEEVIOUS CEOT,OGICAT I{ORT ?

    c[APr8R 2 RECIONAL CEOLOGI 12


    IlrTR0DUClI0rl 12
    STRAIIORIPSI 12
    Hanala H111. Group 12
    te Kuttl Oroup 12
    Torehina Foroation 12
    Corouandel Group 15
    Introductloa 15
    Volcanic Rocks 15
    Intruslve Rockg 20
    lfeltevheta Dacltes 21
    Uhttlauga Group 21
    Great Barrler Islend 22
    Ubltlanga 26
    Paku Island 26
    Brokea Ellls 26
    Thanes 28
    tfeavesvllle 2E
    Ual-tekaurl. 2A
    l{altekaurl-Wathl 28
    Age of tbe l{hltlauga Oroup 28
    Pepauoa and Waltearlkt Igntnbrttes 28
    Eerlksrl Volcaalc Group 29
    Mercury Baeelte 29
    STRI'CTIIRE 29
    Iutroductlon 29
    Eauraki Depreaslon 29
    Coroqandel Dapreealon 30
    RELAIIOI{Of VOLCANISM TO PTATE TECTOIIICS 30
    Reglonal Settlag 30
    Magoa Geneals )L
    slt{0PsIs 71

    cuAPlER 3 EIDROIIIEBMAL ILTERATION 36


    II{TRODUCTIOII t6
    HYDROTHERMAL ALTEBATIO}I MINERAL CHECKLIST 36
    I{OHENCLATURE 36
    (vil)

    Paee
    Eaolln, Kaoll.nlte and Kaollnlte Croup 36
    Sarlclte 36
    tLOa Polyoorpha aad Leucoxene 41
    STILE OT EIDROTHERMAL ALTERATION III SPECIFIC ROCK TIPES Ll
    Greyrecke Sulte Rocke of the ilanala Hl1l Group 1l
    Andealtag and Daclteg of tbe Corooandel Group L)
    Intrusl.vs Bocks of the Coronandol Oroup 15
    thyolltes of the lfhltlauga Group 15
    ZOIIATION OF EIDROTEERMAL ALTERATION L6

    CHAPTER 4 HIXERALISATIO!I lr9


    IIiTRODUCTIOII
    't9
    CHECI(LIST OF PRIMART HINERALS l'9
    PORPHTRY COPPER DEPOSITS 19
    EPITHERHIL DEPOSITS 57
    Introductlon 5',t
    Gold./SlLvar Ratloe 67
    l{laerel Aeaenblagee 67
    1. Early [olybilenlte 67
    ' 2. Early Pyrlte 67
    ' 3. Pyrlte - thslcopyrlte AasenbJ-age 67
    1. Pyrlte - Sphalerlta - Galeaa - Chaleopyrlte
    . Aasenblage - 71

    5. Pyrlte - Sphalerlte - Gsleaa - Chelcopyrite -


    Electrun - Sllver lllnerals Aaaenblage 79
    6. Sb - Sulpbogal't Mlneral lsseobl'age 85
    7. Pyrlte - Acanthlto - Elocttuo Aaeenblage 88
    8. Pyrlte - Bonanza Electruu Aeeeoblage 88
    9. Au - Ag Sulphosalt lilneral Aasenblage 88
    10. Stlbntte 90
    1 1 . Barlte 90
    12. Glnaabar 90
    Oxldatlon and Socondary Enrlchnont 90
    Iutroductlon 90
    Eydrotberoal Leachlng 91
    Sulphtcle RePlacenent 93
    Solutlon and RedePosltlon 93
    . Poat Mlnlng Hloerallgatlon 95
    SecondarY Enrlchneot 95

    CHAPTER 5 ilIIIERAL CHEHISTRY 96


    IUtRoDUCtIOI{ 96
    ACANTHITE . ARGEI{TITE 96
    AROEilTIAH PEIITLANDITE 100

    BISMUTIT HINERALS 102


    CHALCOPIRIlE 102
    CILENA 102
    COLD AI{D ELECTRUI.I 102
    UESSIIE 104
    PIRITE 104
    PYRRHOTITE 106
    SPHALERITE 106
    TETRA}IEDRITE - TENNANTITE 110
    GEOTHERI'IOt{ETRT 112
    Tetrahedrlte - TeunanLlte/Enarglte - Faoatlnlte 112
    0eo tberloo at ar
    (,/'iii)

    Page

    l{lnor Eleneut Geotboruooetry 112

    CHAPTEB 6 FLUID INCLUSIOII IIORPHOLOGI, FILLItrC TSHPERITURE, FREEZIIG


    TEI.IPERATURE A}JD SALINITI 115
    IIITRODUCTION 115
    PRIHARI IICLUSIOIS 117
    Iatroductlon 117
    Vapour Rlcb and Vapour Fllled IueluslonE 117
    Zonea of Elongete faclugloaa 127
    Sollda . 12'l
    SECOI{DARY IIICLUSIOTIS 133
    I'ILLINC (HOI,IOCENISATIOI) TEMPERATUBE 133
    TEHPERATIIRE 0F EIITRAPI{EI{T : BoILIN0 ENVIRO}II{ENT 135
    TEMPERATURE 0F EI{TBAPMEilT: Nol{-BOILIlr0 E}MRONMEIIT 135
    DEPOSITIO}IIL TEMPERATIIBES OT SOME MIITERAL ISSEMBLAGES 136
    FREEZING TEHPERATURE 136
    IPPARENT SALINITX 1V8

    CSAPTER ? QUANTITATIVE AIIALYSIS OT IilCLUSION FLUIDS 139


    INTBODUCTIO!I 1)9
    TIIE CONCENTRATIOlI OF CELORIDE A}ID SOHE CATIONS II{ FLUID
    It{cLusI0Ns 139
    Procedure and Regultd 139
    ExporLoonts vlth Dlfferent Leachtng Solutlons 1lr)
    Developoeat of tbe Procedure 11)
    Leaching Patterne 115
    IilentlfLcation of Contanlnante 1lr5
    Quartz Anal.Yaea 115
    Sotial Incluslous ln Quartz 117
    Evtdence Froo Pravlous ltork oo traee Elenent
    Cooposltion of Quartz 151
    Dlgcueelon 153
    't 57
    Eatlnatl.on of Iocluslon Coopoeltlon
    Introductlon 157
    Cheulstry of Modero Geotberoal F1uids 157
    Cherge BaLauce 159
    Leachlng Petterne of Indlvtdual Ions 159
    Cooparlson of Ionlc Ratlos Betvoen Quartz and
    Leech AaalYsee 159
    Prsdlctlon of Na, K and Ca Contanlnatlon by
    Quartz Trace Eleraot Ratioa 161

    Conclusioas
    t[E coNCENTRATTOI{ otr co2 Ilr FLUrD'r]lclusroNs 16'r
    Heaaurenent 151

    Haxlouo Llnits of C0" Coucentratlon Deternlned Fron


    Phase Reletions ln t6e Systen H2O - CO2 163
    Introductlon 15)
    Abeence of Llquld COa 16)
    Abeeace of Clathratlon 16',1

    Dl e.cu e glon 167


    't67
    Aaalgnetl Values of C02 Concentratlon
    Flutd Inclugioo Sa11n1ty (8reez1ng Teoperature) 157
    Corroctlons
    Other Iopllcatloas of C0, Coacentratione 168
    (i")

    Page

    CHIPTER 8 SIDROGEII ISOTOPES 169


    ISTBODUCTIO!I 169
    HETSOD OP AIIALISIS 169
    TEST SAHPLE 169
    RESI'LTS 171
    ORICIII OF TTIE UATERS 173
    Introductlon 173
    Moteorlc and Geotheraal- Watera 1?3
    Haguatlc Water 175
    Prluary HeguatLc l{ater 175
    Modlfled Hegnatlc Wator 1't5
    Usters of l,lagaas Derlved by l{lxlag of Prlaary
    l,lagna ul-th Sedlneutary Rocke 176
    Foruetion (Connate) llater 176
    Mked Metooric - llagoatlc hlaterg 176
    c0lfcLusI0I{s 116

    CSAPTEE 9 SULPHUR ISOTOPES 177


    I.IEASUREMEil? 17?
    GEOTUERHOMETRI 177
    FTUID CSEMISTRI 18?
    Sulphur Specles ln SelutLon 18?
    . 631s ot Sulphur Specl.es Ln solutlon 187
    5 34s or the Total sulphur ln solutlon
    ' 188
    SOURCE OF SUIPEUR 192
    fntroductlon 192
    Sodluentary Sulphur 192
    . Magnatlc Sulphur 191
    Dla cuse lon 195
    .t95
    c0NcLusI0l{s

    CSAPTER 1.0 PHISICOCHEMISTRI IITD UODEL OF PORPHYRI COPPER !{IIERALISATIOII 196


    EYSICOCHEI.IISTRI 196
    Iatrocluctlon 1 96
    Oeochenlcal Envlronuent 195
    HODEL FOR PORP}ITRI COPPEB MII{ERALISATIOTI 198
    rntroiluction 198
    Genetlc Featurea of Porphyry Copper Depootta 198
    l.todels Proposed by Prevlous l{rlters 200
    Factors Dsterulnlng the Styl,e of Alteratlon and
    Mlnerallaatlon 200
    (1 ) Water Content of the Magna 200
    (2) Potasslun Content of the Magna 201
    (3) Depth of Enplacenent of the Intruelou 201
    (4) TeuglLe Strength of the Couatry Rocks 202
    l.lo<lel for the Eaurakl Gold - Sl1vsr Provlnce
    Porpbyry Copper DePoslts 202
    llagnatlc EnvLronneat 201
    Sydrothemal Envl.ronn ent 205

    CEAPTEB 11 PHISICOCEEHISTRT AIID MODEL OF EPITHER}'IAL VEIII XINERALISATIOI{ 207


    I}ITRODUCTION 207
    REVIEW OT MIilERAL TRANSPORT AIID DEPOSITIOIIII TEE
    HYDROTUERMAL ENVIROI{MENI 207
    Transport of Metels 1n Hydrothernal Solutloos 20'l
    Depoaltlou of Metals froo Hydrotheroal Solutlons 208
    (*)

    Paqe

    fntroductlon 208
    a c52- 208
    02 208
    pH 209
    Dl1utlon 209
    - a? 209
    - apt 209
    !letal Zoulag 209
    Traaeport aad Depositlon of !{oa-l,tetals 210
    Quartz 210
    Calclte 210
    Barite 210
    CEOCHEHICAL EI{VIROIIMENTS OF THE EPITHERilAL VEIU I{IT{ERAL
    ASSEHBLACES AND CAUSES OF MII{ERAI DEPOSIIION 210
    Introductlon 210
    Pyrite - Chal-copyrlto Aasenblage 2',t1
    0eochenlcal Envlronnent 211
    Mlneral- Dopoeltlon 211
    Pyrlte - $phalerlte - Galena - Chalcopyrlte t
    Electrun I Sl1ver Mlaerals, and Sb - Sulpboaalt
    Hlneral Assenblages 211
    Iutroductlon 211
    Geochetlcal Envlronnent 215
    Mlieral Depoaltlon 215
    Pyrlte - Acantblte - El'ectrun Aaaeublege 219
    Geocheulcal. Envl.ronoent 219
    lllnerel DePosltlon 219
    Pyrlte - Electruo Aaseoblage 220
    Introductioa 220
    Geocbenlcal Envlronneat 220
    l,llueraL DePoeltlon 220
    Pyrlte - Eoaauza Electruo Asaeoblage 220
    Geochenlcal Envlronuent 220
    l{1nerel DePoaltion 221
    Au - Ag Sulphosalt l'i1neral Envllouneat 221
    GeochenLcaL Eavlrono snt 221
    Mlneral DePoeitlon 221
    Stlbalte 222
    Geocheolcel Envlronuent 22?
    l{l.neral DePosltlon 222
    Barlte 222
    Geocbeolcal Envlronnent 222
    MLnaral DePoaltion 22t,
    !{ODEL OT EPITSERilAL VEIN HIIIERALISATIOI{ 221
    Introductlon 221
    Hydro)-ogy 221
    Eydrotherual Alteratlon and Solutlon Cheuletry 225
    Introductl'on 22'
    Quartz - Sericlte Zone 225
    Deep Argllllc Zone 226
    ProPYlltlc Zoae 226
    Hear Surfgce ArglJ'llc end Advanceil lrgllltc
    Zone s 227
    Mlserall setlon' 22?
    ('d)

    Paee

    CUAPTER 1 2 I{IIIERILISATIOX IHD VOLCAI{ISM 229


    I{If,ER.AIISATIOTI ASSOCIATED WITII A}IDESITE VOLCAIIISH 229
    The Belatlonahlp BetvEen Andealtlc Volcenlso aad
    Mlaerallaetlon 229
    Sequance of Eveuts Durlng AndealtLc Volcanlgl 1o the
    Eaurakl Provlnce 231
    HINER.ILISATIOI ASSOCIATED IJITU ETIIOLITE VOLCANISI,I 232
    Tha Relatlonahip Betyeen Rbyolltic Volcanign aad
    l,ll.neraLlgat1on 232
    Sequeqce of Evonta Durlng Rhyolt tlc Volcanlso ia the
    Eaurekl Provlace 236

    CHAPTER 13 COUPARISOX OF THE EPITHERMAL DEPOSITS OF THE EAURAKI PROVIUCE


    I{ITE SIHILAB DEPOSIIS Ir OltER PARTS 0F TBE I'TORLD 23?
    I}TTRODUCTIOT{ 237
    COLD PRODUCTIOII 237
    GEOCRAPHIC OCCI'RREUCE OF EPITIIERMAL DEPOSITS 237
    TIPES OF EPIIEES}IAL DEPOSITS 237
    CHABACTERISIIC FEATURES OI' EPITSERI{AL COLD IilD SILVER
    DEPOSITS 210
    IIIIIERALOCICAL ASPECTS OT EPITHERMAI. COLD A}ID SILVER
    DEPOSITS 212
    l'll.nerel- Zonlug aad Parageoogis 212
    Gold/Stlver Ratloa and Gold Flnenass 212
    Tellurlde Hlaerala 211
    Selenlferous and Selenlde l{lnerale 215
    PUISICOCHEI{ICAL ASPECTS 215
    Introductlon 2lr5
    Teuperature 215
    SallnIty 2ls
    pH 2l+8
    Agueous Sulphur Speclee, Oxldlsed/Beduced S Speclea
    RatLo 219
    SPECI!'IC HECS.INISMS 0F oRE DEPoSITIOU ztg
    Introduction 2lr9
    lllxlag 250
    8o11lug 250
    Fluctustlng Concentratlons of Volatlle Constituenta 251
    Suunary 251
    COI'IMON CENETIC I'EATURES 08 EPITHERMAL DEPOSITS 252

    OIAPIER 14 c0ucLusr0!Is 253

    RSFERENCES 256
    (rdi)

    COIITEI{TS OF VOLUHE 2

    APPENDIX I
    A R?VIEI{ OP IRE.I}TDIVIDUAL DEPOSITS
    OF THE HAI'RAKI GOLD - SILVER PBOVIIICE

    Pase

    IIITRODUCTIOII 271
    PSEAI.IBLE 271
    IlltRoDttcToRI ltotEs 2?1
    Ore Petrograpby 271
    lllneral eud Rock Chenletry 271
    Tberrocheulatry 271
    Scope of Blbllographlee 273
    Addttlonal Sourcea of Infornatlon 273

    I.A I{INERS ESII' .[UD THE ITEEDLES 2?5


    IIITSODUCTIOII zi5'
    GEOLOOI 275
    K-Ar AGE 2?g
    EIDROTHEBI{AI, ILTERATION 2'Ig
    I,IIlISRlLISATION 279
    Mlnere Head 279
    Eavlroasent 279
    Bypogene Miueralogy 279
    Supergeae lllneralogy 281
    . Tbe [eedlea 281
    tr.LUID IUCLUSIONS 281
    SULPHUR ISOTOPES 283
    OEPI$ 08 MINERALISAIIOIT 283
    TIIERI,IOCEEMISTRI 283
    GEIIESIS 285
    REFEREIICES AI{D SIBLIOORAPHI 287

    I-B TE AHUilATA 288


    IUTRODUCTIOI{ 288
    CEOLOOI 288
    EIDROIITERMAL ALTERITIO!I 290
    ilIIIERALISATION 290
    rLUID INCLUSIOIIS 292
    SULPEUR ISOIOPES 291
    DEPTB OF MII{ERALISATION 291
    THERI,IOCTIE}IISTRI 296
    Introductl.on 296
    Stage 1 296
    Stage 2a 46
    Stage 2b 300
    GEHESIS 303
    BEEEREIICES AND EIBLIOGRAPIII 30,
    I.C NOFTHERII COIVILLE PEI{IUSULA 30l+
    ITITRODUCTIOH 30l+
    CEOLOGI 3AL
    K-Ar AGE DATA )06
    (rd,li)

    Page
    HETAI.IORPSISM 306
    DEUIERIC ALTERATIOII 347
    EIDROTSERIAL ALIERATIOII 307
    I,III{ERALISATIOil 30?
    Dla getlaated Hlaerallgatlon 307
    Veln illnerallaatlon 308
    South Coagt 308
    Sorry llary Streen 308
    Ilope Streen 309
    309
    ;:H":';.H* 310
    Eva l{lne I 310
    Tangl,ero Streau 310
    xrneralogY 312
    Fr,urD rn.rorilisrsano 912
    SUIPIITR ISOTOPES 312
    LEAD ISOTOPES t11
    DEPTN OP HINERALISATIOII 3j4
    THERMOCHEI.IISTRI 311
    cEl{EsIs 319
    BETERENCES AIID EIELIOCRAPlrl J20

    I-D trI'AOTUNU 321


    IIITRODUCTION 121
    CEOLOCT 321
    EIDROTHERMAL ALTER.ATION 32)
    HI}IERALISATIOII 323
    FTUID IITCLUSIO}IS 325
    SULPEUB ISOTOPES 327
    THERHOCEEMISTRI 327
    GENESIS 329
    REFEREIICES AIID BIBLIOGRAPHT 730

    I-E TOKATEA, COROMANDEL 331


    INTRODUCTIOH v31
    cE0L0c! 3)1
    UIDROTHERI.IAL ALIERAIIOII 333
    I,IIilERALISATION 3t3
    Tokatea 81g Reef 333
    Tokatea l{lnes 333
    Success Hloe 135
    FLUID INCLUSIONS )3't
    SULPHUR ISOTOPES v?
    HYDROOEII ISOTOPES 339
    THERHOCIIEHISTRI 339
    CENESIS 313
    REI'EREIICES AIID BIELIOCRIPEI 143

    I-F TAURI BLOCK AND KAPAI{GA, COROMANDEL 31,1,

    INTRODUCTIOI{ 311
    CEOLOCI 311
    HIDROTHERUAL ALTEMTIOII 116
    }IINERALISATION )116
    Kaurl Block )16
    Kapanga 117
    (rd")

    Page

    TIIERMOCBEHISlRI 719
    0El{EsIs 351
    BEFERE}ICES AIID BI'BLIOGRAPIII 351

    I-G PETOIE STRSAU IREA 352


    Il{TRODUCtI0}f 152
    GEOLOGI 352
    BIDROTfl ERI.IIL ALTERAT IOII 352
    HIlTERALISATIOil 35lt
    trLIIID I}ICLUSIOIIS 358
    ITIDROCEII ISOTOPES 359
    SULPSUB ISOTOPES 159
    LEAD ISOTOPES 359
    TEERMOCHET{ISTf,I 359
    ' GET{ESIS 361
    RETEREUCES AND BIBLIOGRAPHY 361

    I-E I{HAUCIPOUA AI{D TIIE OPIIOIIUI }IIUE 36t,


    IiltR0DUCTr0il 364
    CEOLOGI 361
    IIIDROTHERUAL ALTERATIOII 361
    I.IITIERALISATIOI{ 365
    FLIIID IITCLUSIOilS 369
    SULPEUB ISOTOPES 371
    UIDROCETI ISOTOPES 371
    IEERI,IOCHEI.IISTRI 371
    Introductlon t71
    Stage 2 371
    Stage 3 373
    Stage {' 373
    GETIESIS 376
    RETEREICES AND BIBLIOGRAPEI 3'16

    r-r firulrl 37'l


    IT{TRODUCTIOI{ 37'l
    cE0t0cI ,7?
    fl YDROI[ERI.IAL ALIEBATIOTI txg
    I.IIITERALISATION 382
    CENESIS 382
    RSFERENCBS AI{D BIBLIOGRAPHT 381

    I-J KAPOI|AI )85


    III?BODUCTION 385
    CEOLOCI 385
    HIDROTUERI.TAL ALTERATIOII 385
    I,IIilSRATISATIOI{ 385
    cE!rl:sIs 387
    REFEREIICES AND BIBLIOGRAPEX 387

    I-K BROKETI EILLS 388


    II{TRODUClION ,88
    CEOLOOI 388
    HYDROTIIERHAL ALIERATION 388
    l,l I NERALI SATI0tl 392
    FLUID INCLUSIOIIS 391
    (or)

    Paqe
    DAPTH OP HIIIERALISATIOII t9L
    THERUOCEE}IISTRC 398
    csneslS 398
    Breccla Pl,pe 398
    Velna 401
    RStrSREICES A}ID BIBLIOORAPET 401

    I.L TAPU . TEAHES &o2


    II{TRODUCTIOII &02
    CEOLOOI 102
    K-Ar AGE DAtA 101
    HTDROTTIERHAL ALIER.ATIOT{ LOl
    HTilERALISATIO}T 405
    rLUID rlrcLuslof,s {10
    SULPIIUR ISOTOPES 112
    TUERUOCEEHTSTRY 111
    Porphyry !llaere11 eatlon 414
    VoLu Hl.neralleetl.ou d,r.{
    Cu - Bl l{l.nerallsatlon 116
    . Pb - Zn llluerallgatlon l|16
    OENESI9 418
    REFERENCES AI{D BIBLIOCRAPHI 122

    I-lt tEAl{ES 123


    Tf,AHES SPECIAL AREA t23
    II{TBODIICTION 123
    GEOLOCT 123
    EIDROTHERI{AL ALTERATION 128
    HI}IERALISATIOII 129
    rtulD I[cluslo]rs 130
    SUTPEUR ISOTOPES 132
    I'EPTR OP HIITERALISATTOI 13L
    THERI,IOCIIEMISTRI 111
    cEltEsIs 136
    REFERE}IC8S AIID BIBLIOGRIPIII 137

    I.il }IEAVESVILLE 138


    rltrR0Ducf r0lf 138
    GEOLOOY 138
    HIDROTHERMAL ALTERATIOlI 442
    HII{ERALISAIIOII 112
    lllnerallsetlon ln Andeelte 112
    l'llnorallsation la RbyolLte 113
    Graceg aad the trBluffgn 113
    Chanplon 115
    rLUID IIICLUSIOXS 115
    HTDROCEII ISOTOPES 117
    SULPEUR ISOTOPES +17
    DEITH OF I,IITIERALISAIIOII 117
    TEERMOCIIEHISTRX 119
    fntroductlon 119
    AJax Raef 119
    Grecea, Blrda and Oolden Arrov tlr9
    Dlscusglon 151
    CEI{ESIS 451
    (ori)
    Pase

    BEFEREXCES IIID BIBLIOC&APST 415

    I-0 t{ARlloro 156


    IIITRODUCTIOI{ 156
    OEOLOCI 456
    BIDROII{ERI.IAL ALTERATI OII 456
    I,III{ERALISATIOTI L58
    fatroiluctl.on 158
    Caooola Veln 162
    Sllver Quean Veln l,6l'
    FLUID IIICLUSIOTS lr1O
    SULPflUR ISOTOPSS 171
    crRBoll allD oIlcElI IsotoPEs 176
    UIDROoETI ISOTOPES 176
    DEPTI OF I{IIIERALISATIOII 176
    IHERMOCIIEHISTRI L?8
    CENESIS 182
    REFEREUCES ATID BIBLIOORAPHI lr85

    I-P GOLDEN CROSS lr86


    INTRODUCTION 486
    GEOLOCY lr86
    IITDROTITERHAL ALTER.ITIOII 486
    HIT{ERALISATIOII 186
    GENESIS 187
    RETEREITCES IND BIBLIOGRAPSI 187

    I-Q K0I,{ATA 488


    INTRODUCTION /.88
    0E0t0cr 488
    TTTDROTHERMAL ALTERAIIOII 488
    !'lIl,lERltISATI0lI 488
    FLUID I}ICLUSIONS 490
    liut puuR rsoroPEs lrg I
    DEPTH OF MIIISRILISATIO$ 19 t,
    GET{ESIS 191
    REI'EREITCES AIID BIBLIOORAPET 495

    I-R }TAITEKAURI 196


    IIITRODUCTIOII 196
    CEOLOCI 496
    ETDROTHERHAL ALTERATIOII 196
    I,tIIERALISATIOI{ 500
    FLUID IIICLUSIO$S 501
    SI'LPUUR ISOTOPES 501
    lIEBl{0cflEMISlRl 501
    CENESIS 50'I
    REFERE}TCES AIID BIBLIOCRAPEI 50'l

    I.S WAIIII 508


    II{TBODUCTIOII 5og
    cEot0cI 51t
    HYDROTHERMAL ALTERATIOII ,16
    HIIIERALISATIOI{ 5't9
    Hartha Veln SYsten ,19
    (xrii)

    Pepe

    Eoeeoont filll Velns 523


    FLUID ItrOLUSIOUS 525
    SULPITUR ISOIOPES 52',1

    UIDROGBI ISOIOPES 529


    DEPTE OT XIIERALTSATION 529
    THERI.IOCgEI,IISTRY 529
    Introductloa 529
    Deep Level utnerall'agtlon 531
    Interuedlete level nlnerallsatlon 531
    Sballov level olnerellgetlon 535
    GS!|ESIS 5t5
    RSTERST{CES AI{D BIBLIOGN.APRT 5LO

    I-I KIRIilOASAKE 5&1

    u{tBoDuctIoN 511
    CEOTOGI 512
    EYDROTUERI.TAL ALItsRAIIOU 512
    K-Ar AOE DATA ,[4
    I,{II{ERAI,ISATIOI{ 5L4
    Crosn Veln 5IL
    Uelcoue Veln 511
    l,larle Vela 516
    FLUID lllot Usrot{s 519
    SULPHUR ISOTOPES 551

    DEPIB 0P l'lIlfERALISATIOll 511

    T[ERI.IOCEEUISTRI 551

    cEllEsIs ,53
    REFERENCES AND BIBLIOGRAPII 551

    555
    I-U tur l.lrllE
    INTRODUCTIOU
    555

    GEOLOGI
    555
    ATTENATIOII 557
    "ETDROlHERMAL
    557
    K-Ar 408 DATA
    557
    I,IINSRALISAlIO}|
    FLUID IITCLUSIOIS 562
    561
    SULPUUR ISOTOPES
    568
    CARBOil AND OXYGEIT ISOTOPES OF CARBOIIATES
    oxrcEll ISOToPES 08 BARTTE' QUIRTZ' KAOLI}IITE AND FLUID
    IIYDROCEI{ AltD
    568
    INCLUSIONS
    570
    LEAD ISOTOPES
    570
    DEPTE OF UII{ERALISATIOS
    570
    THERI'tOC}IEIIISTRT
    577
    CENESIS
    577
    REFEREI{CES AIID BIBLIOGRAP}II

    579
    I.V TIAIORONCOHII
    579
    IllTRODUCtI0lr
    579'
    CEOLOGY
    579
    HYDBO T}TEBHAL ALIERATION
    5'.19
    I,IINERALISAIIOT{
    582
    NLUID II{CLUSIONS
    5E1
    HIDROOEN ISOTOPES
    586
    SULPHUR ISOTOPES
    586
    LEAD ISOTOPES
    (xvfir)

    4a+e
    uEPtf, oF [[sEnALrstTIoI, t06
    5El
    sEilESis 591
    SEF,BSTi-ilgW r,[D EtrBLI/9r8fi[PStr 59j
    tr-I UT SOSLT.A!.E{U S. DEPO 5I IS fr2
    trUTRODtrOTIOI
    HlIx.$tfir
    EA,t 'Ia
    ,92
    OOLIfLrc f,RA[, ,92
    ltalroRol|Itro vAu.Er 5E'
    olfE8f' ,96,
    EOAtr EARBO.UF m rrrEu,{ r96
    'ou!tf 196
    r{u|Gnt$cr r6[ee! 59r
    r.uG$ aT LASG t{r$tE, (r,filEEK,^ry,f, Y4&LSI} 5l9r8
    or{lEtr wtLtDE t98
    g'ElEl{OEqF - ilftrll[BA!{A A 6"EE$ ,.99
    yirur HotruilEilT wq
    OTHAEOI 600
    IrAOf,rITOUr 60e
    I,IUIRIS REDFS (TE PUIrS} 60?
    (*i*)

    CONTENTS Otr VOLUIIE 3

    Pase

    APPENDIX II' ELECIROIT MICROPBOBE AI{ALTSES: I{ETTIODS AUD RESULTS 604


    MEIgODS 604
    Instrurentetlou 504
    lleaaurlng Condltlona 60t,
    Stanclards 601
    Detectlon Llultg 60a
    Intarfsrences 604
    RESITLTS 606
    Acanthlte, AgaS 50?
    lrgentlan Psutlandlte' (treu1)t+I AEt-ISa 60?
    Blgnuthinltar BlaS, 508
    CbalcoPYrtter CuFeSt 50E
    Gold - Elactruul AuAg 609
    Ga1ena' PbS 610
    f,essite' AgaTe 612
    PYr!.te' PeSt 611
    Pyrrhotlte' FeS 61L
    SPhalerlte' ZnS 615
    letreilYulte, BlateaS 62t
    tetrahedrlter CuraSb4St: - tennantlte Cu12AE4S'3 62t

    IPPENDIX III PBOCEDURES AUD RESULTS Otr FLUID IIICLUSIOII TILLII{O TEI'IPERITURE
    FREE'IIG TE}TPERATURE AIID APPABENT SALIT{ITT I{EASOREI{ENTS 621
    PROCEDURES
    621
    Sanple preparatlon for optlcal exeol'natt'on 62L
    SelectLon of lncluelonE and thelr atorage 625
    Deterulnatlon of Fl1ltng lenperatures 627
    Deternlnatlon of Sallnltles 629
    Fraezlng Stage Constructloo 629
    ' Freezlng Stage 0peratlng Inetructlons 5t7
    RESULTS
    6tL
    ' tletbsil of Llatlng 6tti
    635
    UaIta
    l{iners Hesd 6t6
    636
    Ie Ahuuata
    636
    Northern Colvllte PenLaeula
    637
    Kuaotunu
    63?
    Tokatee' Coronanalel
    538
    Petota Streau, Coronaadel
    639
    Whangapoua
    639
    Broken Hllla
    619
    l{eavesvllle
    6LO
    Itlaratoto
    61.)
    Konata
    611
    l{altekaurl
    6L5
    Waihtr
    646
    Karangabake
    616
    Tul Hlus
    618
    l{alorongooal
    (o)
    Pase
    AfPEI{DIX IV FLUID IXCLUSIOT CRUSEI}IG AIID LEACHII{C EXPERIHET{TS 650
    SAI,IPLE P NEPARIIIO}I. 650
    CRUSSUIG PP.OCEDURE 650
    LEACEIflC 651
    RESULTS 658
    ASSESSHEIIT OF ETPERICENTAL COilTAHI}TATIO}I 661
    PRECISIOII: DUPLICAIES AND SAMPLB GR0IIPS 664
    IC9URACI: IESI SIMPLE 666
    ASSESSI,IEI{T OF AIIALISES OP IIIDIVIDUAL SAI.IPLES 667
    Quartz Saoplea 667
    Tokatea 667
    Petote Strean Area 669
    lfhaogapoua 671
    lleavosvl].le 61?
    l{aratoto 67)
    Konata 6't5
    I{altekaurl 676
    lfalhl 676
    Tul MLae 6?8
    lfaloroagoual 680 .

    Calcltes
    l{orthera Co1vllle Pen1trsu1a 682
    Tokatea 683

    APPENDII V THEE}IOCHEMICAL CALCIITATIONS 68{


    IIITRODUCTIOI{ 681
    I{OTATIO!I AND UNITS 68t
    EqIIILIBRIUM 685
    Introiluctlon 685
    (1) Eguillbrlua Betneon Aqueoua Specles 585

    . (2) Equlllbrtuo BetseEa the Fluld eacl Precipltatlag lllnerals 68'.l


    (3) Preeorvatlon or Mocllftcatlon of Assenblages 688

    . (1,) Mlneral-Fluld-Hlneral InteractLoa 588


    Dlscuss lon 589
    FLSID INCLUSIONS AND STABLE ISOTOPES
    EVIDET{CE FROt.t 590
    IONIC STREI|CTH (AT R00U TEMPER-{rURE) 692
    ASSOCIATION OF IO$S AT ELEVATED TEHPERATURE 692
    CALCULATIOI OF THE DECREE OF DISSOCIATION 693
    ACTIVITI AND ACTIVITI COEFIICIENTS 695
    pH 697
    CALCITE STABILITT AND 699
    PE
    T'UGACITT 701
    Introductlon 701

    FugacltY of C02 ?01


    FugacJ.ty of COa frou FluLd IncLuslon Data ?01

    Sugaclty of CO2 froo Eydrotberoal Altoratloa l{l'aera1


    A6 8eB OIAge 3 705
    FugacltY of St 706
    Introductlon ?05
    fS, Froo Sphalerlte CouPosltioo 706
    fSa Frou Pyrrbotlto CooPoeltlon 71)
    fS, Froo Electruo ConPoaltlon 713
    fS" Fron Mlneral Stablltty Relatlons on fSa Vergus
    720
    Tefiperature Dlagraos
    (r"d)

    Pugacity ot O2 720
    Introductloa 720
    fSa Vereue foa Dlagrans ?22
    Concentratlon of Total. SuJ,phur ln Solutlon 725
    f02 Versus pH Dlagrauo 729
    Fugaolty of Te2 7t4
    SPECIFIC HII{ERAL SISTEI{S 731
    Tungsten Mlnorals 'l)1
    Seleul.fsrous and SelealdE lllnerale 718
    Introductlon 738
    Tberuocbeolcsl Studlee 738
    Appllcatlon 710

    APPENDIX VI ORE PE1ROGRAPTIT OF SAI,IPLES PROH I.TAIHI ?12


    SAHPLE 13901 (whr6), HARISA Hr[E (UrrLoCArED) 7L2
    SAHPLE 13902 (t{b3?), ilABTHA }{ruE (It[tocATED) ?13
    SAMPLE 13903 (1{bi(,8) l{ARlgA l'lIlIE (UNLO0ATED) 7lrl
    (Wh2?),
    ' MARTHA MIITE (UNTOC.ATED)
    SAHPLE 13978 71r,
    SAMPLE 11032 (GJ3r, GRtilD JUHCtror{ }|INE (UNLoCATED) 7L5
    sAltPLE 11OJ9 (wh28),
    MARIHA |{INE (UlttoCATED) 71'
    SAMPLE 1 I,O l,O (rdb29), MARTEA Mrt{E (UIILoCITED) 716
    sAr.rPLs 1404,1 (ldh30), llARlHA HrXE (UNLoCAIED) 717
    SAHPLE 11013 (uh35), vrctoRrA vEill, ADrr LEVEL 7L7
    SAHPLE 1llOL6 (t{b13), HARTUA }|INE (UULOCAIED) 7 1,7

    sA!,lPLE 11,017 (wutr), MARTHA VE-[U, ? LEVEL . 718


    sAl,lPLE 1L018 (wu1,51, gilLocATED 719
    ,
    SAMPLE 11019 (t.th42) ttARtsA vErN nAT DEPlHfl 750
    .I
    sAl.tPtE 14050 (}{h4?), IIARTHA VEril, O LEVEL 750
    ,
    SAMPTE 1 4051 (r,rh4g) UNLoCATED 750
    SAUPLE 1t052 (wh50), I,{ARTHA VErN, 1O LEVEL 752

    APPENDII III ORE PETROORAPEI OF SAHPLES FROM KARANCAiIAKE 753


    sAr.rPLE 11023 (TL1?), TALISI.IA}I MINE (UNLOCATED) 753
    SAMPLE 14,O2IJ (TL21), TALTSHAII l{rlfE (ullLocATED) 751
    sAl,tPLE 1t+O25 (tL22r,
    TrLrsMAlt 14 LEVEL ?55
    sAtfPLE 11,026 (TL2t+1, TALTSMAN 13 LEVEL 756
    SAilPL8 1 LO27 (TL25), TALISMAII 13 LEVEf, 756

    APPE}TDIX VIII ACCESS AND ORE PETROCRAPIIT OT VEINS IU TBE WAIORONGOMAI AREA 757
    IIITRODUCTION 75',1

    PREMIER . COLONIST SECIION 757


    Iutrocluctlon 757
    Colonlet SolthY Level 761
    McLeane 1 'l 00 | Lavel 753
    Preller No.4' Vulcan and Vulcan Levela 761
    MAII{ VEIII 766
    Maln Vein, Dlaoond Creek Irlaterf all 766
    Nen FInd Sectloa of Haln Veln 766
    HAT QUEEI{ 768
    Hay Queen 1 Lavel 768
    Hay Queea 2 Level 768
    Hay Quoen ) Level 771
    NUI,IBER OUE REET 773
    !1o.1 Roaf Traovay 713
    ' llaterfall
    !lo.'t Roef t Dlaoond Craek 777
    ,(xd,5-)

    rFase
    B0uautt 779
    IIVERUBSg, LO,I.ILtrI AIID UErcOilE VEIIIS ?a1
    Looetios 7tI
    Irlvr.Aaas 7A'
    Loyelty ,IA3
    Uelcoue, Sostbarn Aillt (Eltlr or Fergutco.nls Dnire) ,18'
    UOA YEII 185
    -:
    APPEilDIT IiT LOCATIO{ INI' BnISF D.SSEAXFTXOU 9!: 8AIIPf,8S 756
    IUTROIIUCTORI I{OTES ?86
    letbsil of l.totl,ag 786
    Sauple,e aoC. Ltgted, 786
    Fl'eld [urnbsro 786
    Orljl, Eeferoueee 786
    DESC&IPTtrONS !18'I
    (:ociii)

    LIST Otr FIGURES Iil VOLUHB 1

    TTGURE Pase

    1-1 l{ap-of ulneral depoolte and paat olnlng centreg Ln the Haurakl
    Gol,d - SLlver Provlnce 2

    1-2 Bulllon productlon fron the uaia oLnlng centroe t


    1-3 Pbotograph of l{albi in the oarly 1900rs I
    1-1 Pbotograph of I'Ialbi Goltl Hlnlng Coupeayr.a battery and treatnent
    plant 5

    1-5 Photograph of Karaagabake ln 1914 5

    1-6 Photograph of the prorpectLng opencut 1n Hartha 8111' Walbt 6

    1-? l{.2. Geologlcal Survey bull.etlus and naps 8

    1-8 GooLoglcal tbeses aad associated publ.lcatl'ons 9

    1-9 Rsceat publlcatlono by DSIR staff 10

    1-10 Reporta by nl,uoral exploratlon coopauies 11

    2-1 Reglonal goologlcal naP 13

    2-2 Stratlgraphla coluon 11

    2-3 Fornatlons of Coronandel Group volcanl.c rocka 17

    2-t+ K - Ar agea of Corouandel Group voloanic rocks 18

    2-5 Phaaes of andeeltic volceolsn 19

    2-6 Hap of rhyollte rocks of tbe Eeurakl Gold - Sllver Province 23

    2-7 Stratlgraphlc colunn for the Table Mountaln area 21

    2-g Geologlcal nap of the area east of l{hltlanga 25

    2-9 FlssLon track ages of tlbltlanga Group rocke 27

    2-10 The Saurakl Rift and Corooaadel Depresslou 31-32


    ?-11 C.roee-aections of tbe Whltlanga Grabea )3
    7-1 Hydrotheroal alteratlon of Corouandel Group andesltes l+2

    3-2 Raglonal Zonatlon of hydrothernal alteratlon of Corooanilal Group


    rocks 1.7

    4-1 Map shovlug locatlon of porpbyry coppsr depoelta 55

    L-Z Map ohowing locatlou and gold/sllvor ratlos of epltheroal ileposlts 60

    lr-3 Photograph of brEccla nineral.isatlon ln a hand spacluen froo


    Petote Streao 61

    L-L photograph of, cruetlflsd ninerall.gatlon ln a band specl'nen froo Te


    Ahuuata 62

    lr-5 pbotogreph of crustLfled ore l-n a hand speclneu fron Harstoto 63

    lr-6 photograph of crustl-fled ore ln a hand speciuen frou Karangahako 6L

    1-7 Photograpb of cockade gtrucluro ln a hanil specLrea fron I'lalorongooal 65

    1-8 photograpb of vug quartz cry8tals ulth late carboaates aad pyrlte,
    froq Maratoto 65

    1-9 photograph of pLateo of berlte coatlng vug quartz crystala frou


    1{alorongonal 66

    4-10 Pbotoolcrogrpph of chal-copyrlte - pyrltE aod lator quariz -


    blgnuthlulte'-- natf ve gotii Stage i lut l{tna
    '
    ?0

    4-11 photoo!crograph of natlve gold, btanuthlnlte;.pfrl'te.l.tetradynlte


    ana quartz-lniluslone ln cf,alcipyrlte; Stago l;-Tul t'ltno 70

    tr-12 Photoulcrograph of heuatlte - chalcopyrlte - pyrlte - quartz; Stage


    i , Tul l.llne 72
    (:ociv)

    FICUltg Pase
    1-13 Photoolcrograph of honatLte - quertz - supergeDe goetbltei Stage 1,
    tul Mtse 72
    lt-II Photorl.crograph of replaceaent of pyrlte by galonai lokatea 7l
    1-15 Pbotoglcrograph of replecenent of pyrlto by quartz; aphalerlte and
    chalcopyrLte; Butt Greek 7t
    1-16 ?hotollcrograph of rfLah net! gelena - quartz lntergrovth; Stage
    - 2,
    Ualtekaurl 7j
    l.-17 Pbotoolcrograph of galena - beselte cooposlte grains and quartz;
    Stage 2b, Sllver Queen Veln, llerat,oto 75
    4-18 Photonlcrograpb of orlented lncluglone of cbalcopyrite in sphalerlt,e;
    Tokatea, Corooandel ?6

    1-19 Pbotooicrograph of orleoted lncluelons of cbalcopyrlto la aphalerlteS


    Martha Veln, Ual.ht ,,
    4-2O Photoqlcrograph of orlented lncluslons of abelcopyrlte 1n spbaLerlte;
    No.1 Reef, Waiorongonai 7?

    1-21 Photoolcrograph of galtra - pyrtte - quartz - chalcopyrlte aeaulag


    aphal,erlte; lokatea, Coronandel 'i,8

    1-22 Photoalcrograph of polkllltlc Lncluslons of galtra Ln ephalerlte


    and pyrlte; Wathl. 78

    1-2) Photonicrogreph of lanellar ophalerlte ln quartz; Martha Veln I'lalhi 80

    1-21 Photoolcrograph of dendrltic - berrlngbone galena ln quertzi No.l


    Veln Halorotrgonai 80

    1-25 Photonlcrograph of dendrltlc - tretreakyn galena + pyrlte +


    chaLcopyrLte ln apbaLerltei Mertha Velar lJalbt 81

    1-26 Photooicrograpb of polklLltlc lncluelons of galena' pyrrhotLte and


    pyrlte ln sphalerlte; Marthe Vein' Walht 81

    1-2'l .Photonicrograph of apbalorlte - galena lntergrovtb; Tallsnan 14,


    level, Karangabake 83

    4-28 Photoolcrogreph of aphalerlte - galena - chalcopyrlte - electruo -


    quartz lntergrovth; lal.lsnan 14 level; Karangahake 83

    1-2g Plotoulcrograph of polklltttc lacluslone of galeaa, cbalcopyrlte


    aud elactrun 1n sphalorltei Tallenan 14 level' f,arangahake 84

    1-30' Photonlcrograph of dendrltlc - Dstreakyn lncLusioae of galena,


    cbalcopyrlte and electruu ln sphalerlts; Tallsnan 14 leveL'
    Karangihake 84

    141 Photonlcrograph of chalcopyrltel aphalerlte aad galena luvadetl by


    later elecf,ruir * quartz; tillsnen 1,(, LevoL, Karaugahake 85

    L-32 Photoolcrograpb of sphalerl.te, chalcopyrite and galeua


    - scattered
    tn calclte-gaigue; Ciooola Veln, Maral6to 86

    L-33 Photoolcrograpb of lntergrouth betveen galena, chalcopyrlto'


    Bphelerite] alaathtte end calalte; Caooola Veln' Maratoto 8?

    lr-31, Pbotograph of barlte pletos coatlng a quartz cryatal fron tbe


    llolcooa Veln, llelorongooel 89

    lr-35 Photograpb of stalagtltes of llooulte ln Vulcan 4A level,


    Walor6ngboal 91
    j-l TetrahedrLto - tennantlte aad enarglte - fanatlnlte geotheruoueter 113
    5-1 Photonicrograph of prinary vapour fllled Lncluslous rlth aegatlve
    crystal shipe'frou itaratolo - 116

    6-2 Photoolcrograph of a prloary llquld-vapour lnclusl.ou vlth lrregular


    ahape fron-Tui Hlao 116

    6-3 Photoulcrograpb of prinary llquld-vapour lncluglong Ln nVtr gronth


    zon6s of quartz fron Tut l{lne 118

    6-1, Photonicrograph of prlnary ltquld-vapour lacLuslona in rVn grouth


    zoneB of quartz fron Tui Hlne 118
    (ro,t)

    FICURE pase
    6-i Photontcrograpb of a solitary vapour rlcb prluary lacluslon fron
    f,onata 121
    6-6 PhotooLcrograpb of a vapour rlch prinary lncluslon frou l{eavesvllLe 1ZL
    6-7 Photoolcrograph of vapour fllled prlnary !.nclugloag froo lfeavoevllla 125
    6-8 PhotouLcrograph of vapour ftlled prioary lncluslons froo Brokea
    8111s 12,
    6-9 Photoolcrograph of eloagate (-cyllndrlcal) prloary fluid lnclualona
    froq Maretoto 126
    6-10 Photonlcrograph of elongate (-cylLndrlea1) prlnary fluld tacLusLoae
    fron Maratoto 126
    6-11 Photoolcrogreph of orlented elongate prluary fluld iocluglona cut
    by a zono of socoadary fluld lscluslonsi Canoola Veln, llaratoto 128
    6-12 P!'otoulcrograph of a prlnary J-lguld-vapour lncLusl.on contalnlag a
    fibroue solLd pbeaei l{elcone VeLn, llaiorongoual 1ZB

    6-13 Photonlcrograph of prloary ltquld-vapour lnclusione contalntag


    flbrous soLidg; Jublloo Lov Lovel, Ualtekaurl 'l,29

    6-1L Photonicrograph of a llqutd-vepour inclueton contelni.ng a flbroua


    solLd; Eroadlaadg drIll bole 25 129
    6-1 5 Photonlcrograpb of flbrous Bollds ln flutd lucluglong and adJaceat
    quartz; Broacllarda rlr11l hole ? 130
    6-16 Photoulcrograph of a prluary ltquid-vapour lncluglon conta!.ulng a
    bexagonal go1ld pbeae; CoLoalet Soltby level, l{alorongoual 1)0
    6-17 Photooicrograph of eecoadery flutd lncluelons froo the Welcono
    Velu, llalororgoual 132
    5-r 8 Pbotorlcrograpb of s6condary flulcl incluelone fron tho Sllver
    Quoen Velu, Maratoto 132
    6- 19 Photoulcrograph of sscotrdary flulal hcluslons fron the Konete Mine 13tr
    7-1 Concentratlon trendg of lotrs leached fron crusbed sanplea of qurrtz 111
    7-2 P.botoolcrograph of calcite lncluslons in quartz frou Sorry Mary
    Strean, Northern Colvllle Penlnsula 1L9

    7-3 Photonlcrograph of calclt6 lncluelons 1o guartz fron Sorry Hary


    Strean, llorthern CoLvllle Penineula 119

    7-1 Photonlcrograph of nlneral lnclugions ln quartz frou Broken ElLlg 1 50

    7-5 Photoolcrograph of a flbrous nlneral in quartz fron l{altekaurl 1 50

    7-6 Welght ratlo plota of guartz trace eleoentg and sone ninerals 15L
    't-7 Grapbs of a1kall netalg versus A1 for quartz 155

    7-8 Graplr.of Eoaourd fluld lnclueloa COa ebncentratlon voraua uator


    rotlht ' 161
    7-9 Phase dlagran for the systso HzO - CO2 165

    8-1 Oraph of rlelgbt of flutd lnclugion vater analysed Yoraus 5 DSUoW 172
    1 0-1 fO, vereus tenperature dlagran for porphyry coPPar ulneralisatlona' 19'l
    1 0-2 !,fodale previously proposed for porphyry nl.ierallsatLon 199

    1 0-3 Model for porphyry coppor fornatloa tn thE llaurakl Gold-Sllver


    Provlnce 203

    11-1 fSo veraua fOo dlagran for the pyrtte-chelcopyrlte olneral


    ao6eoblages ' 212
    1 1-2 fO, veraus temperatura dlagrao for th pyrite-chalcopyrlte nlaeral
    as!eublage s 213

    11 -3 f0, vorauo pH dlagreo for the pyrlte-ephalerlte-galena-chalcopyrlte


    + Electruo ! ollver ulaorals, and the Sb-aulphoaalt alneral
    aasetr Drageg 216
    (roqrf )

    FICT'RE Pape

    11-1. !0a voreus {Te for the pyrlte-lPhetrerl'te-galena-chalcopyrlte


    Flsctruu * sllver ulaerale aoaetblages
    t-*u, 2't7
    71-5 f?z dtagran tor tbo pyrlte-sphalerlte-galena-
    ".t"r." t elestrun t gllvEr nlneiall aaaenblagea
    cbelcopyrlte 218

    11-6 Depth zonatlon lodlal. for epltherual deposLta 223

    12-1 Hap abovlag tbe locetlont of porphyry copPr depoelts ln the f,ortb
    Igl.ead 230

    12-2 ltodelg relatlng bydrotharnal ayaters to atyla of volcenlro 233

    12-3 tfegatlve lsostatl.c vertlcal gradieat gravlty aaonEll'os beneath


    Ubittange Group rocka 235

    13-1 Ideollged vertlcal zonatlon of eleuenta aad llaerala ln epigenet!.c


    golil ilepoelta 211

    13-2 Hlaeralo of tbe syeteu Au - Ag - Te 213

    13-3 Fluid lacluslon fllllag teuperatures fron eplthernal depoet'ta 216


    (rc<vii)

    LIST OF TIOI'F.ES Iil VOLU},IS 2

    FICII RE Pcse

    I-1 LocEtlon of areas descrlbeal lo goctlone I-A to I-V 272

    I-A-1 t{ap of the nlne and adJacent rocke, at t'llnEra Eead 276

    I-A-Z Photograph of tbe Lnslde of tbe uino at Mlaera Head 2'17

    I-A-3 Ceological llap of l{lners }teaal 278

    I-A-l, Grosg-sectlon of qlneralised breccta dike 280

    I-A-5 Mlners Head flulil lacluslon fllllng tenperature and apporent


    aallnlty hlstograne 282

    I-l-6 fSa versus fOa dlagran for Hlnera Haad and tbe lfegdlee
    nlneralieatlon 28L

    I-A-? fOa versuo tenPerature dlagran for Hlnerg Eead aud the Needlea
    ulnerallsatlona 286

    I-B-1 Geologlcal nap and cross-sctLon of Te Ahusata 289

    I-B-2 Paragenetlc aequence of, nlnerele at Te Abuoata 291

    I-B-3 Te Ahuoata ftuid Lucluslon flLllng tenperature and apparent aallnlty


    blatograus 293

    I.B- 4 Depth of nluorallgatloo at To Ahunata, 295

    I.B-5 fO, versus pH dlagran for Te Abuneta Stage 1 ulneralisation 298

    I.8.6 foa versua pH dlagrau for To Abuuata Stage 2a nlnerallsatioa 299

    I.B-7 fs2 versud foa dlagrao for To ahunata stage 2b nlnerellsatlon 301

    I.8.8 foa verous p8 dlagran for Te Ahuoeta stage 2b olnerall.satlon 342

    I-C-1 Ooological nap of Nortbera Colvllle Peainsula 305

    t-c-2 Iorthern coLv1lle Peninsula fluld lnclusl.on ft ll1ag teuperature


    and apperent sallnltY hlstograns 311

    l-C-i fS, vorsus f0, dlagrao for Parltu Coestel SectLon porphyry copper
    uinerallgetlon 315

    I-C-/, fSa versus f0a dlegrao for Northern Colville Peainsula voln
    oinersllsatlou 316

    I-C-5 fO2 versus pH dLagran for l{orthern Colville Penlnsula vein


    ninerallsatLon' )11

    I-P-1 Geological nap of the Kuaotuau area 322

    I-D-2 Paragenetic sequenco of veln nlnerale at Kuaotunu 321+

    l-D-3 Kuaotunu flulit lnclugton fllltag teuporatura and apperent oallnlty


    blstogran s 126

    I-D-4 fsa vorsus fOa dlegran for Kuaotunu veln nlneralLsa'"lons 328

    I-E-1 Coologlcal uap of the Corooaadel and Tokatea areas 332

    -E-Z Tokatea flulil lncluglon fl1llng taaperature aud apparent oallnlty 336
    ' blstograns
    I-E-3 fo, veraus pll dtagrao for Tokateg, bsge Eetal uinerallsatlon J10

    I-E-4 fs, vereus foa tllagrao for loketea gold-allver ulnerallsatloa 311

    l-E-5 f0, versus ptl dlagrao for Tokatea gold-ellver olasrallsatlon t12
    I-F-1 Hap of velng aod norklaga la tbe Kaurl Block anil Kapanga areaa 315

    I-F-2 fsa veraus fo, dtagreo for Kaurl Block and Kapange ulnereLlEatlons 118
    350
    I-r-3f0,versuspHdlagraoforKauriBlockandKaprogaolnerellsatlons
    (racriil)

    FICURE Pasa
    I-C-l Geologlcel nap of the Petoto Streeu aree 153
    I-C-2 Paragenetlc soqueace of uLaerala !n tbe velns of tbe Petote Strear
    a,re4 355
    I-C-3 Pbotograph of e nlnerallsed epeclnen fron tbe Eutt CreeL vela 356
    I-G-4 Petote Streau aroe fLuld lncl,uslon fllllng teoperature aud apparent
    eal.lnlty hletograra t57
    I-C-, fS2 veraus fOa dlagrau for Petoto Streao area Stage 1 olueral.lsatlon 360
    I-G-5 f0, versus pE diagrao for Petote Streau aree Stage 1 ulnarallaatlos 362
    I-[-1 Gaologlcal nap of tho Whaugepoua area 366
    I-H-2 Map of tbe hyilrothernal alteration zones ln the l{haagapoua aree 367
    I-H-3 Paragenetlc squanco of ulneralg ln veLna of the Wbangapoue area 368
    I.ll-I fSa versue tooperature dLagrao 172
    I-H-5 fOa veraus pll <llegran for Whangapoua Stago 2 olneraliaatlon 3?1

    I-E-6 fS2 versua f0, dlagraa for l,Ibangapoua Stage 4 ol.nerallaatlon 3',15

    I-I-1 Geologlcal nap and croas-a6ctl.on of the l{aneLe erea 379

    I-I-2 Hap and croas-action of the'hydrotheraal alteretlon zoneg la the


    Hanala area 380

    I-I-3 Paragenetlc seguenc of nlneralleitlou in the Manala area 381

    l-l-Ir Hodel for porphyry coPPor type ulnerallsatioo ln tbe l'lanala area 183

    I-J-1 Geological Dap of the Kapovai area 386

    I-K-1 Geological Eap of tho Broken llills erea 389

    I-K-2 Groes-sactlon of the Brokeo EllLe nine )90


    I-K-3 Plan of the vslna lu lon levels of the Broken Hllls Mtne )91

    I-K-4 Paragenetlc squenco of ninelalg fron the breccla plpe' Brokeo


    Hllls Mlne )93
    I-K-5 Plaa of 2 level Brokou f,llls Hlne 395

    I-K-6 Brokea 81Us fluld lnclusion fllllng teuperaturg and apparent


    aallnity hlatograoa 396

    I-K-? Doptb of olnerallsatlon et Broken HlUs 397

    I-K-8 fs, vorsue foa dlagran for the Brokan }ttlls olnarall-satloa 399

    I-K-9 fOa versus pll dJ-agran for tho Broken HllLg uinerallsatlon 400

    I-L-l Geologlcal oap of tho Tapu-Thanes area $3


    I-L-z Paragenetlc Eoquerce of nluerale 1n velns of tho Tapu-Thauea ara LO?

    I-L-3 Map ahovlng locatlon of porphyry copper style deposlte la the


    Tapu-Thanes area
    I-[-4 Paragonetlc sequenca of nlserala ta quartz-sorlclte zones of
    po.p[y"y syatede ln tbe lapu - Thaneg area 409

    1-L-j fS2 versue fOa dlegrao for Cu-Bl nlneralisatlon ln the Tapu-Tbanes
    velns 115

    I-L-6 fSa versus fOa iltagran for Pb-Za nlnerallgatlon ln the Tapu-Thauas
    velng |'t7
    I-L-? fO2 vereua ptl dlagrao for Pb-zn ulnerall-eatlon ltr the tepu-Thaoes
    vel ns {19
    I-L-8 fTea veroua fsa dtagrao for Pb-zn alaerallsatloaa ln the Tapu-
    Thanes vel-ns 120
    (r,ix)
    TICURES Pase
    I-t{-1 l,fap ehoulag tho locatlon of ntnes ln tbe Tbaueg area ' 121
    I-r{-2 Goologlcal nap of the Thanes area 125
    T.-11-3 Croes-geatlone of the Thanea area 126
    I.H.4 tog of tha f,uranul-Caledonla drlll bole 127
    I,r{ - 5 fS2 veraue f0, diagrau for tbe Thaoes gold-pyrargyrtto ulnerallaatLoal33
    I.M.5 fOa versuo pII dlagrao for ths Thanas gold-pyrargyrlte nlnerallga+,Lot 135
    I-il-1 CeoJ.oglcal rap of tbe lleavosvllLe area 1,39

    I-l{-2 Crosg-eectlon of the l{eavegville area UrO

    I-lr- 3 Claeslflcatlon of hydrothernally alterod rocks at lleaveavlLle 111


    I-ll-4 lleavesvllle fluld lncluslon flIllng tenparature and apparent
    oel1alty hlstograua |lrl
    I-l|-5 Depth of ulnoralLaatloa at lleaveevllle 116
    r-l|-6 fS, veraua fOa dlagreu for nlnerallea,tlon la tbe AJax vela,
    Heavosvill. ,tO
    I-l{-7 fO, vereua pE dlagran for ulneralleatlon lu the AJax vel.n,
    l{eaveevlll. tt,
    I-U-8 fS, vereue f0a dlegrao for nlnerelLsatLon ln tbe Bluffa sectlon,
    l{eevosv1ll" Ot,
    r-lr-9 foa veraua pll dlagran for ulnerellgatlon l-n thE Bluffe soctlon'
    l{oaveevll-le 15)
    I-0-1 Geologlcal uep of tbe ileretoto-Golden Cross-Kooata-UaltekaurL Area lt5'l
    I-0-2 lfap of velns ln thE Haratoto area 459

    r-0-3 Gauerall.sed plan anil longitudlnal sectlon of the Maratoto velrrll 161

    r-o-4 Paragenetlc 8qusncs of ulaerale in the Ceooola Veln, Maratoto 1163

    I-0- 5 Paragenetlc sequence of ulnerals ln tha SlLver Queen Veln, Maratoto 165
    r-0-6. Photoolcrograpb of Stage 2c SlLver Queen Veln ulneralisatlon lt6?

    I-O- 7 Photograph of Stage 2c Sllver Queen ninerallsatlon 1n baad specluea 458


    I-O-8 Photoslcrograph of Stage 2c Stlver Queen nlnerallsatl'on 159

    r-0-9 Haratoto fluld lnclusl-on filllng teuperature aud apparent sallnity


    biatogran 171-L72
    r-0- 1 0 513c 6130 dlagran for Maretoto carbonate nlnarals l+75
    ""ruuu
    I-O-1 1 Deptb of nlnerallsatlon et Maratoto Ir77

    I-0- 1 2 fSa vorsue fO, cllagrao for Stage 2 Maratot'o oinerallsatloa L?9

    I-0-1 3 fS, veraus f0, dlagran for Stage 2 Maratoto nlnerallsatlon 180

    I-O-1 4 fO, vereus pII dlegrau for Stage 2 llaratoto oineraligation L81

    I-0-1 5 fTe, verauo fS, illagraE for Stege 2 Maratoto olaerallsatlon L83

    I-0-1 5 f0, vereua pH iltagrau for Stage 2 l'taratoto nluerallsatlon 18L

    r-q-1 Longltudlnal sectlonE of tbo Konete Mlue 489

    r-q-2 Plan of Kooata 8 level 191

    r-q-3 Konata flutd lnc1ualon f1lltng teoperature aad apparent oallalty


    bl stograu a lr92

    r-q-1 Deptb of ulneralleatlon at thE Konata Mlne 1.93

    I.R-1 Geologlcal nap of the Valtekaurl area 197


    (o*)

    FIGURES Paee

    I-8.2 Cleasl.ficetlon of the hydrotberoal alteratlon olneralg tn tbs


    Waltekaurl araa L98

    I-R.3 Paragenetlc tquBce ol oiaerala la tha l{altelcauri Vein 199

    I.R.T Photonl.crograph of Ualtekaurl Stege 2 nlnerallgatlon 501

    I.R. lfaltekaurl flul<l luclugloa flll1ag teuperature aod apperont


    ' sallulty hlatograoe 503

    I.R-6 fSa veraua f0, diagrao for Stege 2 oinerallsatlon Ln the


    Waltekauri Vein 505

    I-R.7 f02 vrsus pll dtagrau for Stage 2 ulaerallsatlou ln the llaltekaurL
    Vsin 506

    I-S-1 Map of v61as la the Walhl area 509

    I-S-2 Deptb relatlons of alae levela 510

    r-s-3 Ceologlcal nap of l,lathl 511-512


    r,s-4 Croes-sectlone of the Martha Veln syotan 518

    r-s- 5 WaLht fluld tncluglon fllllng teopereture end apparent aallnlty


    hlatograoa 521

    r-s-6 Coupoolte f,luld lncLusion fllllug teuperature dlagran 525

    I-S-7 Depth of nl.nerallsatlou ln tbe Martha Veln aysten 528

    I-S-8 fs2 versus f0a di.agrao for deep level nlneralisatlon 1o the l{artha
    veJ.o eya ten 532

    r-s-9 foa versus pll dlagrau for deep levEl nlneralLsation ln the l,tarthe
    vein aysten 533

    r-s-1 0 f0, yersus pH rllagrao for lnteroedlate Level nineralieatlon in tbe


    Maltba veln sYsten 511

    I-S-1 1 fSo voraus f0, dlagran for shaLlov level ulaerallsatious Ln tbe
    Maftha veln sfsteo 536

    I-S-12 fO, versus p[ dlagran for ehallou lovsl ulnerallsatlon ln tbe


    Maitha veln sYatell 53'.t
    .

    I-S-13 Structural intarpretatLon of the Martha vota eysten 539

    I-t-1 l{ap of tbe veins and norklngs at f,arangahake 5l,J

    I-T-2 Croes-aectlon of tbe Karangahake velns 545

    I-T-3 Longltudlnal sectlon of thE tallsoln Mlne 51?

    I-1-4 Mlneraloglcal cbanges yltb deptb ln the Bonanza gectlon of tbe


    Marla Veln, Karangahake 518

    I-T-5 Karaagabake fluLd iucluslon fllllng tenperatura aad epperent ,50


    saltaltY hlatograns
    I-l-6 foa versus pll dlagraa for tbe tleep level nlneralisatioa ln the
    TalLsnan Mlne, Karangahake 552

    I-U-1 Geologlcal naP of Tul l{ine 556

    I-U-2 Cbanges ln uioeralogy vltb lncreaalng latensity of hytlrotheroal


    alteratlon at Tul Hl'ne 558

    I-U-3 Paragonetlc rgueooe of ulaerala 1o the valoo of Tul Hlne 560

    I-U-/, Photograph of Tut tllne hand specloeas contalnlng stage 1


    nlnErallsatton 561

    I-U-5 Pbotoolcrograpb of a vapour rlcb fluld Lncluel.on fron Tul Hlne 563

    I-U-6 Tul Hine fluld lucluslon fl111ng tenperature and apperent sal'lnlty
    h1 o tograas 565-566
    (rood)

    FIGURES Page
    t-u-7 513c dlagrau for luL Mlne carbonate olnorals '
    ""t"r,t 618o 56?
    r-u-8 Dep-tb of ulaerall.aatlon at lu1 li{lne 569
    I-rI-9 fO, versus pB dlagrat for Stagee 1 and 2 nlnerallsatLone lp vefae
    of the tul l{tae 521
    r-u- 1 0 forvereus pll dlegran for Stage 3 ulnerallsatlon 1n velns of the
    Tul Hlne 571
    i
    I-U-1 1 fSa vereua foa diagraa for Stage 1 oinerallgetLon iu velns of tbe
    TuL Miae 5?&
    I-U-1 2 f,Sa versus f0, dlcgrao for Stage 2 ulnerallsatt oa Ln velus of ths
    Tul Hine 57j
    I-U-l 3 fOa versus pH dlagrao for Stage 2 ulnerallsation ia velns of the
    Tul t{1ne j?6
    r-v-1 l,lap of, velns la the Uaiorongooal area jg0
    r-v-2 l{alorongoual. fluld Luclualon flJ.ltng teoperature aad apparoat
    -
    oallnlty hl.atograue ||j
    r-v-3 Depth of ulnerellsatlon at llaloroogoual flj
    r-v-4 fSa versus fOa for Stege 1 nlaerallsatl.ou ln tho l{alorongonaL volns fBI
    r-v- 5 f0a voreua pf, dlagrau'for Stage 1 .ulnerallgatlqn to the Wal.orongooal
    vel.ns 589
    r-v-6 fTe, versue fO, dlagrao for Stege 1 ulaerallsett.oa la the
    lleldrongonal velng 590
    I-lr-1 Locatloa oap for doposlta rvl.6ved ln Sectlon I-H 593
    I-W-2 Itap ehowlag depoelta Bot revlarreal ln lppendlx I 591
    r-t{-3 Crogs-sectlon of tbe l{ackaytorn ciunabar deposlt 601
    (roodi)

    LISI OF FIGURES II{ VOLUME 3

    Lr0nREs Pasa

    III-I Pbotograpb of ulcroscope beatlng stage 625

    III-2 Pbotograpb of olcroacope freezlng etage 628

    III.3 Croes-sectlon of freezlag stage fia


    III.4 Pbotograpb of parta of the freezlug etage 6tl
    TTI-' Dtcgrauatlc layout of freezlng stage aPparatug 632

    IV-1 Pbotograph of tbe electrolytlc cloanlng cel'le 651

    IV-2 Scheuatlc layout of tbe gleaa vacuuu line ueed to extrect nater
    fron fluld lnclueloas 65t
    rv-3 Photograph of tefloa eub-bol.Llug acld dlattl-latlon apparatus 655

    rv-4 Flov dlagrao of, crushlng antl loaching proceduro 651

    v-1 Effectg of dtsequlllbrluo betveen a hydrotheroal solutlos and tbe


    veln (nlnoral) eysten- 686

    v-2 Degroe of dlssoclation of l{a0l solutloas up to 300oC 691

    u-3 Ion product and neutral PH of neter at elevated teoporaturea 695

    u-1 Mlneral stabllity relatlons ln the systeo KZO - A1203 - 5102 -


    H2O - IlCl 598

    v-5 Orapb of fC02 versus teoPerature 701

    v-6 Conpoaltlon of sphslerlte ln equ111br5-uo nlth pyrlte and


    pyrihotlto as a iunctlon of tenporature aod fS, 709

    v-7 Effect of pressuro on ophalerlte coopositioo ln tha eseooblage


    sphalerite + pyrrbotlte 710

    v-8 Gonposltlon of-pyrrhotlte ln the Fe-S syeteu 8a a function of


    teuperature and fSa T2
    v-9 Suoothetl tarnlsb culvee for electrun coopoeltt'ona 715

    v- 10 Corractlon factorg for tbe rolatlonsbip- betneen electruo conposltion,--.


    isa-..a-t;nperaturo 716

    V-11 . l,llneral stabttlty


    - relatlone ln the systan As-S-O as a functl'on of
    is;-."a io; 72t,

    v-12 f0, versus pH dlagram ylth_contours of f8as la egulllbrlun ulth


    th6 prodonlnant aquaoue autphur specles 73O

    u-.13 f02 versus fs' dlagran lllustratlng tbe stabtllty of ferberLto 713

    V-14 f02 versus fSa dlagrao illustratlng the atab11lty of hueboerlte 735

    V-1j fOa versue fSa dlagran Lllustratlng the stabtllty of scheellte ?35

    V-16 Poa versus pH dlagrar lLLuetratlng the stabtllty fleLcla of tungaten


    and lron nlnerels 736

    u-1,1 f0a versus pH dlagran llluetrattng the eteblllty flelde of aqueoua


    seleai,uo and sulPbur aPecies 739

    VI-1 Photoulcrograph-.shovlng.raplaceuont of ophalerlte ead galena by


    quartz; Martha Ve1n, Ualhl 7.u1

    uT-z Photoulcrograph ebovlng replacenent of sphalerlte aud galena by


    quartz; r.raitni vetn, l,r;Ihl- 75'l

    VIII-1 l.lap of tba naJor vel,ae and vorkiage in the l'lalorongonal area ?58

    VIII-2 plaE of vorklngs ln the Colonlet and Preoler Sectlone, Walorougoual '159

    vIII-l Photograph of breccla nlnoraltsatlon ln a haud speclnen


    - frou
    760
    colonist Srilrti-i;";i' walorongooal
    (rodr1)

    TIOURE8 Fasc
    YtrfX=4 Pilan of, tbo 8ery FiEd Bo!&tagr, W&i.oEengoEd,. 165
    lf!lI-5 Fhotograpb o.f sor,LLngs iq the Neu Ftad See-tloa,r rfoiqroagonai 16!l
    VIIL'6 Plrotor.lqr0gtagh of alsndrltlc galeaa .la quartz; lfo.l Yeilr
    Hato*ongonat w1
    WII.? fhoto,gla.ph-9f talded rulpbldcr a&l gorb qlr"uta lua a hend lpec{nea
    frou lfo.1 Tel.nr lfaloroagoucl 7fl6
    VIfIr,8, Ptea of rorLlnga la tbe arra of the Fe[oocs anil fnvora,sgg Ve'{ae,
    Ualorongocat 18'2
    YIII.9 Plag sf tbe goutharq. adit iat,srpce'tlag the, [olcsu.a V,elu,
    S.eloroagonai. 78t
    (:oociv)
    LIS? OF TABLES III VOLUHE .'
    TABLE Pase
    2-1 Forratlons of volcaolo rockg tn ths Corooaadel Group 16
    3-1 Checkllst of hydrothoroal al-teratlou nLnerals t7
    3-2 BydrotberuaL altera,tlon ulaeral aeeeublagee ln groyracke suite rocta 40
    3-3 Hydrothernal alteratloa ulneral aeaooblagea 1n lutrueLve rocks 11
    4-1 Checkllst of prluary netallLferous rlneralg 50
    1-2 Cbeckl-tst of gangus nlaerale 51
    1-3 Porpbyry coppsr etyle ulnerallsatl.ona of the Eaurakl. Oold-slLver
    Provlnce 56
    1-1 8u1L1on ploaluctlon, boat rock, aeaoctated hydrotberoal elteratlon
    and ulneral content of sone epltbaroal veln deposLte 58

    1-5 Eplthernal veln nineral aaeeoblages 68


    1-6 0ccurreacs and ulnerel content of tbe pyrlte - chalcopyrlte ulneral
    aseeoblage 69

    1-7 Malu occuuencsa of the pyrlte - sphalerl,te - galona - chelcopyrlte


    nlneral assenbJ.age ?3

    1-8 l,taln occurreuces of the pyrLte - ephalerlte.- galena. - chalcopyrlte


    - electrun -, el,lver nlnerals aaoonblago 82

    1-9 Connoa 96condary nlneraLa and probable prl.nary ulneraLs fron nhlch
    they vere derl.ved 92
    5-1 Electroo nlcroprobe anelysea llgted ln prevloua sorks 9'.|

    5-2 Electron nicroprobe etralysos of, acanthlteg 98

    5-3 Eleotron Dlcroprobe analyeea of pyrrbotltes qnd argeotian pontlaadlte 99


    5-1 Electron Elcroprobe analyses of blsnuthinlte and tetlsilynlte 101

    5-5 ELectron olcroprobe analyses of gelena 103

    5-6 Electron oicroprobe analyaee of gold and electrun 103

    5-7 Electron nlcroprobe anal.yses of hossltes 105

    5-8 Electron ul.croprobe analyses of aphalerltes 107

    5-9 Cd/Un ratios of sphalerltos 109

    5-1 0 Electron olcroprobe analysos of tetrshedrl.tes 1't1

    6-1 Geograpbical varlation of prlnary fLuld iuclusl-on davelopuent 119

    6-2 FlUlng tenperaturo aud apparent sa1ln1ty rsults for prlnary


    f,luid lncluslons 124

    6-) Depoaltlonal teoperatures of epltheroal velo ninerel assonblages 13',1

    ?-1 Appareat fluld lncluelon conceatratlons of gone lons lndlcated by


    leach analyses 140

    ?-2 Quartz trace elenent analyses 116


    7-3 Elestron nlcroprobe analyaes of aluolniud in quartz 11,8

    7- l+ Celctuu carbonato coatent of quartz saupLes lndlcated by trace


    eleoent analyses 152
    7-5 Conpositlon of deep vators fron gooo aodern geotherual f1e1ds 156
    7-6 Selected partlal enalyeea of fluld inclusLona 160
    7-7 Concontratlon of C0a neaaured fron flutd Laclusl.oag 162
    7-8 Aoslgned concentratloaa of CO, end correctlons for flulat lncLuolon
    freeztng tooperaturea 165

    8-1 5 D valuee of seter extractod frou fluld lncluslosa 1?0


    (loow-)

    rA.B,E Paso

    8-a :8tf6,sge4 6lD uellla,a f'or ftr;uld ilsliu.si,on nqters ttI1


    9-1 6 34s vatuea of *utr!fi.lis snil rul,gbatu ullcr'alF aad, c*trett;Lste{
    tcnpetct{=ee 178

    9--z Tenporgturef and lsotoptc colgosttl,oa of eutrphur epealea la


    oolirttou lndlaated by bulphur leotope deta 185

    9*5 6j{S *.fuss 6f'totei ttrl hu! ln aol.u.tlsa du.r-lag .forre'tt t of gore
    of ltr dopoei,tc 'lad tbe trnobable soulre6 of, culphur r91

    5
    r+S valuea of plnlte !a grelmacte sulte rocls ef tbe f,-aroraq aret 1'9?.
    9-6
    1l -1 Geocbeulsal'paraueters for soEs reProeentatlveg of the Pyrlte--
    ophrlarlte -- gale.aa - chalcoP1rllte ! eloetruu + allver slnsrelr
    and Sb-gulphosalt ulaorgl'r aaEe[bl4g.rs 21:6

    1 3-1 preduetlos of tono f,aoouc epltbar'ra-L dlpoelf,l


    G.oJ.d 2ZA

    1!-2 Glrspl,ftaat!.ou sf eSltberral ui.rse-ra1 dopollia 2r9

    13,t' GeoEbent ec} palanetors !or so|[a o{i?seas eBi.thernel de-posttLa ?,47
    (romri)

    LISI OP TABLES Ilr VOLOME 2

    TAgLE Pase
    I.B-1 thgroochsnlccl paraoeters for nlnerallsatlons at Te Ahuuata 297
    I-C-1 Tberuochenlcal pareneters for oinerallgatloas ln lfortbern Colvllle
    Penlneula 31t
    I-E-1 Tbernocheol.cal paraoeters for ulnorallsetloas at Tokatea 338

    , I-H-1 Therrochoulcal. paranaterg for ulaerallsatlons at tfhangapoua 370


    I-L.1 Hlnerale of tbe lepu-?haoes area 105
    r.-L-2 5 34S valuea of nlnerals aad calculated teoperatures for the
    Tapu-fhaoes ara 111
    T.L.3 Theroochsolcal paraneters for tbe Tapu-Tb,anes epithsrnal
    nlnorallsatloae 11t
    r-u-1 5 34S ,r"lrr"s of nlnsraLg fron the Tbcnea area 131
    I-tr-1 Theruocheulcal paraoeters for the ulnarallsatlons at l{eavesvLlle 118
    I-0-1 CheckLiet of prluary natallla olneralg ln velna of the Maratoto
    arga 160
    I-O-2 Isotoplc coopoaltloa of eulphlde nl.aeral-s fron the Haratoto lllne 171
    I-S- 1 Stratigrapby of tbe rocka lu the lJal.hl eree 51 lI
    I-S-2 Theroocheulcal paraueterg for ulneralleatlone lD the tlartha VeIn
    Syeteo, Walhl 530
    I-U- 1 tbersochenl.cal paranet'ers for nlaerallsatlona at Tut t{Ine 573
    (rocrctrii)

    Lrsl oF TABLES ltl VOLUI.IE 1

    TIBLE Paqe

    II.1 Detectlon llnttg for Electron oLcroprobe analyaes 605


    IV-1 Electrolytlo cleanlag cell log 612
    IU-2 Aaalyaes of fluld lacluslon leachl,ng reagenta 656
    rv-3 Coacentrattong of lons leached froq erushod saaplea of quartz and
    calclte 659

    rY-1 Aaalyaee of blanlcg 66t


    w-5 Analyses of fluid lncl-usl.oas Ln calclts frou llgarha and nodern
    bore flul.cls 665
    v-1 Soue thernoahaulcal perauetera for aelected nlnerallsatlona 691

    v-2 Valuog of fCO^ celculated fron the concentretloa.of COa tn fluld


    lncLuslons ' ?00

    v-3 fGOo durlag depoaitloa of epltheroal depoelta at Suauyelde asd


    Bag0lo Dletrlct 702
    u-1 Log fS2 yalueg calculated fron tbe lron content Lo spbalerltea 'IO7

    v-5 Log fS2 veluos calculeted froq tha coopoaitlons of pyrrbotltea 711
    v-6 Log fSe values calculated fron tbe oole fraction of allver lu
    alectrfin and. golil ?18

    v-7 TheruodyneuLc deta uged to caLculate the fSa veraua tenpereture


    and fSa versua f,Oa illagrare 721

    Y-8 Concentratlons of total auLpbur ln solutLon aaalgned to gons


    eplthernal deposlte by otbei sorka 726

    v-9 Concentratlou of total eulphur Ln solutlon duriag forustlon of


    aooa deposits ln the llaurakl GoId - Sllver Provl.ace 727

    v-1 0 Therooilynaulc deta used to calculato the fOa versue pll illegraoe '128

    v-11 Therlodyneulc data uged to cal.culatE the fTea Yrsua fS2 illagraus 733
    ()oocniiJ')
    ACKNOWLEDGEMET,ITS

    This thesis waa suggested by Dr A. Wodzieki (fornerly of


    the N.Z.'Geological Survey) and supervised by Dr B.W. Robinson
    (Institute of Nuclear Sci-ences), Dr J,W. Cole and Prof . R.H.
    Clark (Victoria University of Wellington),

    The study was financed by research grants fron Mi.neral


    Resorrrces Counci.l and the Internal Research Conmittee at
    Vj-ctoria University of Wellington.

    Dr J.W. CoIe critically read all of the thesis while Dr


    B.l{. Robinson, Dr T.M. Seward (Chemistry Division), Dr R.L.
    Brathwaite (Geological Survey) and Dr M.K. Stewart (I.N.S.)
    have read and commented on substantial parts of it. Aspects of
    the tppic have also been di-scussed with graduate students and
    staff in the geology departments of Victoria University of
    Welrington and uni.versity of Auck1and, and staff of oeological
    Survey, Chernistry Division, fnstitute of Nuclear Scienees,
    Mines Division, B.P. N.Z. ttd and, AMOCO Minerals N.Z. ttd. In
    partj-cular, Dr T.M. Seward gave advice on aspects of thermo-
    dynamics.

    I glso wish to aeknowledge and express appreciation to


    the following people and institutions for assistance of various
    kinds. Research facilities were provided by Victoria University
    of l,Iellington and the Institute of Nuclear sciences. Mr B.P.
    Roser (V.U.W. ), Dr B.1rI. Robinson, Dr C.J.D. Adams. (I.N.S. ),
    Dr B.F. Houghton (Geological survey), Dr A. wodzicki and AM0c0
    Minerals Ltd assisted with field work- Dr B.l{. Robinson,
    Mr E, Coppard, Dr R.J. l,terchant, Dr S.D.C. Rabone, Dr H,W. Kobe,
    Mr W.R.H. Ransalr Mr J. Barbarich, Mr C.. Davi-s, l"lrs R. Handley,
    Dr P.R.L. Browne, the Geology Departnent of the University of
    Auckland' Auckland l,tuseuin, Geological Survey and Mines Division
    provided sanples for study. Mr E. Coppard. supplied information
    and plans of the locations of mines in the waiorongomai arsa.
    Dr R. Goguel, Mr J. Patterson and Mr W. Kitt of Chernistry
    Dlvision analysed the quartz samples and fluid inclusion leaches.
    Mr P. Taylor, Mr A. McOnie and Ms v. Bulr of Mines Division
    helped with research lnto m.inlng records and nineral exploration
    report s.
    (rood.x)

    . Mr B.P. Roser, l"lr K. Palner, the late I'lr l,l. Schafer (V-U.W.),
    Dr B.W, Robi.nson, l,lrs L Lowe, l,tr B. Shilton (I.N.S.), Mr N.
    0rr (Geological Survey) and Dr R.J. Merchant (fornerly at the
    University of Auckland) denonstrated preparation technlques
    . and the operation of analytical instrunents. Mr K. Calder and
    Mrs J. Brown nade thin sections and. sone pollshed nounts. -M""
    I. towet l,trs M. Coxr Mrs E. Duckworth and Mr B, Shilton helped
    rr with sulphur isotope and hydrogen isotope analyses at the
    Institute of Nuclear Sci-ences. Mr K. Whalon and Mr E. Millington
    of the University workshop (V.U.W, ) constructed the nicroscope
    freezing stage, Mr C.A. Snell of the Analytical I'acility (V.U.W. )
    . ttre sub-bolling aci.d d.istillation apparatus, and Mr I.C.
    Crighton and Mr C.D. Taylor (glass-blovers V.U,W.) the glassware
    apparatus.

    Mr M.D. King and Mr J.E. Casey of the Photographic Departnent


    (V,U.W. ) prepared sone of the photographs. The Alexander
    - Turnbull Library gave perni.ssion to reprod,uce sone of their
    phgtographs and the Aubrey watercoloure Mrs L. Booth and Mrs
    M.E. Coqper typed the thesis and Mrs J. Askwith drafted the
    dJ-agrans.

    I thank ny family for their patienee, help and encouragenent


    throughout the course of this study.
    (r,t)
    ABBREVIATTOTTS FOR },TIHERALS

    The abbrevj.ations used for nineral nanes in this thesis,


    foll-ow the scheme llsted below, unless stated otherwise,

    Metallic (r0reil) Mlnerals Gangue Minerals


    ac acanthite ad adularia
    agu aguilarite ak ankerite
    apy arsenopyrite .an anhydrite
    bi bismuthinite ba barite
    bo bornite ca calcite
    caI ealaverite carb carbonate
    cb cinnabar eI chlorite
    cc chalcocite do dolomite
    cv covellite f1 fLuorite
    e1 electrun q.tz quartz
    en enargite nu muscovite
    gn galena pyn pyronanganite
    hn henatite rho rhodochrosite
    nc marcasite sc seriei.te
    ng nagnetite sd siderite
    no nolybdenlte
    nul naunannite
    pb polybasite
    pg pyrargyrite
    po pyrrhotite
    ptz petzite
    sb stibnite
    sch scheelite
    sp sphalerite
    syl syLvanite
    thd, tetrahedrite
    wo wolfranite
    C}L\PTER, 1

    rlmRourclToN

    ISCATION OF SI'IIDT
    The area of study is
    termed here the Hauraki Co1.d - Silver Province
    and ccnprises Great Barrier IsLand and the Corqnandet Pelrinsula as far
    south as Te fuke (fig. 1-1).

    ECONCI'trC HISTCaf
    Epithennal vein ttrrpe deposits r*ere exbensively miled in the late 18@ts
    and early l900rsr establishing the area as a gold - sLlver prorince with
    gold production conparable witb the most successfirl gold mines in other parts
    of the world at that ti-ne. Between 1852 and tlJ? approx5rnately 3gg nirlion
    grans (1O mrttion ounces) of gold and I'OOO mj-llion grams (30 mitrion ounces)
    of silver we.re produced frqn the centres shobrn in Figs 1-1 and 1-2.
    Porp\yry cqpper mineralisation at Minerrs Head (trie. 1-1) yielded
    2J@ torures of copper ore between t857 and 186?.
    fnif,fa'l l yr primitive ore treatment and e>cbraction methods caused large
    quantities of gold and si-lver to be lost ln the tailings. This problem was
    mostly werccrne by the introductlon of cyanidation in the 18pOts.
    The.most successful mjnes were at t{aihi (the largest mine in l,lew Zealand,
    Figs 1-3 and 1-4) and Karangahake (nig. 1-5 and Frontispiece), where gold
    and silver values, although nct outstanding, were consistant throughout
    most of the production period of the mines (72 ana 6O years respectively).
    In contrastr mines at Cormandel and Ttranes had bocm and br.rst periods due
    to the occurrence of gold and silver in r.estricted bonanzas. Obher mining
    centres were generally onJ.y marginalty econsnic or were failures due to lqr
    gold values and, unsuitable treatrnent methods.
    Deposits at Te Aroha, Maratoto and Thames have been mined recently.
    Tui l.line (Te rtroha) was re-opened in the mid 1960rs by ltrorpac Mirring Cornpany
    and produced leadr zinc end copper concentrates for export. Declinlng
    concentrate pricesr mercurlr contanination and increasing orerheads caused
    itts closure in L974. Consilver re-opened the Maratoto mi.ne in 1!68 and
    produced s6e'l'l quantlties of silver and gold but thig venture also ceased
    lrl L973. Several small slmdieates are presently nining at Ttrarnes on a
    weekend basis (".g, Roberts famtly operating the Reuben Parr - Caladonian
    mine).
    ZE|'IAND

    6R,EAT
    BARRIgR
    t'|-ANIP

    b.q
    fuaohntr
    Minc
    Town
    City
    Wdftaita
    Flstkc

    ffr-.li
    COROMANDEL
    ,6cr*lc Mtlc PENINSULA

    \ts'tvtra
    THAI,{g' }'

    fantah t
    PAEROA T 'r

    Tui Minq
    o 50lt2025 .tE AROr.tA tr.
    Ywr url

    TAURAT{6A
    rTE RIKE
    tlAvrrrt ?cfrc

    Flgrrrc 1-11 Locatlon of olaeral ilcpoelte and part u!.n1ag centrcg tn tbe Eaurakl
    Golil-S1Ivcr Prorlnec.
    Soo
    Coroffid
    t2

    U4a-TVetr
    Uihcs 5'1
    t t.7

    a
    Naavesvillc
    0.?

    Flgure 1.2: Bullton (gold,plus allver) productlon fron tbe lala llal'ag ceatrca.
    Valueg are graaa 110o.
    .:rl

    't4 l
    r,d ()
    rd r-l Nd
    'HE{'9
    P FEI
    O+r
    ti d''.quo
    b! .q
    *4 +l r{
    Ct ,tl h
    $ld
    PE rr{
    +r.
    *r td Fr
    @.E8{
    i-{rO
    o+t
    {E 'H .l)
    .qU0S
    +t o Grl
    f{
    FlOc
    .F{ E{.O
    q.{
    Ro+t
    :r{ td (l
    E .|) 5i
    otru
    g O,l"
    3o
    o ?rd
    {t 'd, H
    Fld
    rr-l d &
    E
    .rd
    'ct
    (t+{tt )
    =Odh
    rd
    r-ldh
    .!o sl ,tr
    -lAsiF
    o5d
    ClboFlgt
    rJ.- k
    F O' hS 'r-{
    +r J4' ;-l
    >1 {: (I 3
    r{ cg d-O
    trFseg
    6h
    oFl@9
    o&Fr
    lD ,r{{9
    'ddE'{
    +!5 rD O
    ct 'd
    EiclE
    {Eid
    '.{ s: .ofi
    h'r{
    'qdFl
    r{gU
    dFl u
    F.Og()o.
    F{
    rr.t{OF 'lJ
    eq.q 5
    |.dtt O
    FdrStft
    B 6t '40
    o
    t{
    F
    a0
    k'd
    t

    llgure 1-4: Hathl GoId Htalag Corpaayrs 200'atenp battery and trcatlcnt plert
    at Ualklno. llexander TurtrbulL Llbrary.

    Flguro 1-51 Karengabrke 1911t rboyl.Dg the bulldlngo of lhc Tallslaa Goasolldrtcd
    Gonpaay: battery aad treatseut plant ln left forcground, and centrc nl.ddlc
    dletance, poucrbouee lu. ceutro and rlgbt foregrouad.. The nincl are ln
    ,. Karangaheke llouutelu ln tha background. Prlce Collectlonl llcraadcr
    - Turnbull Llbrary.
    6

    Ftgure 1-6: fhe prorpcatlug opcncut ltt Hartha f,lll' l{alhLt 1978. The vel'a
    'neteri.al (s'g. nhl'te roek ln bank bchtnil truck at rlght) rrea Processeil ln
    a nlll erected on tho sltc of ths old llafhl Conpcnyrs Unloa Battery (see
    lle. 1-?).
    Mineral exploratlon activity in the province rapidly increased lcith the
    rise j:r gold prices jn the rate 1970f s. rn tg76 fi'mco started a detailed
    eiploration program beginlng wi.th a 1or level aeromagnetj-c sunrey fo.Llored
    by slotematic geochemical sampling and geological mapping. They have since
    investigated and djannond drilled a nurnber of deposits, Cold l.{j.rres of 1tr.2.,
    Go1dfie1cls, l.lineral Resources Ltd - Obter llinerals, AllAX, CRA and BP have
    also been active in the area. Forloiii.ng l,ljnerar Besowces (li.z. ) lta -
    i'laih:i Minirrg and Developmentrs large ftprospecti:rgt'cut on the o1d liajii
    t"tine (fig. 1-5) al,lAX are presently drilling deeper Ievels.

    P.'rH/:roJis G.EoJ,lIllcAt Hoiu(


    Dtrring the majn period of nrining in the late 18o0rs and early 1t@ts
    a number of geological reports and bulletins were vrritten by nenbers of the
    Geological Sunrey and Mines Department, The most irnporbant works of thjs
    period tvere the serj-es of brrlletins describing the geology of the various
    subclivisions of the Corcrnandel Peninsula (fig. 1-7A): Fraser & Adans (190?),
    Ilaser (1910), BeI} & F?aser (tgtZ); Henderson & Bartrum (f9f3) and liorgan
    (L92h,) and a book by Dovrney (tglS) detailing the history and production of
    the individual mines.
    The geolog' from these early reports and hiLletins was conrpiJ-ed and
    updated in the [5]R 1:25O'0OO scale geological rnaps (Fig. 1-?B), Barrier
    (Thompson, .1950), Auckland (Scnofietd, 1;967) and Rotorua (Heaty g!_glr 19G4).
    The renewed miaing and *cploration activity jsr the late 195Ots spar,med
    a second phase of geological- literature,consisti:rg of theses at Auckland
    Un:iversity and publications resulting fron them (both referenced il Fig. 1-),
    publications by FIR staff (nig. f-9) and mileral' exploration ccrnpany repods
    (fig" 1-1O), A recent LSIR L:6313& scale geological map of the nort,hern
    part of the Cororandel Peninsula (SXinner, tg76i Fig. 1-?C) fras completely
    rev:ised the regional.stratigraphy fron that in earrier works.
    Most of the authors referenced above and in Figs 1-8, 1-9 and 1-10
    described the geologyt hydrothermal alteration and mineralisation of one or
    more of the indiv:idual mi.:ring centres, but recently there has been a trend to
    jnclude jnvestigations of the physicochemical conditions of mineralisation
    in their studles. Robinson (lg7l) studied stable isobopes of the
    mlnerarisation at Tui Mine, whereas Merchant (19?8), Torlcler (rgZs), Robson
    (1979 ) and bceg (fggf) included sqne flIuid, i.nc}rsion work in their studies
    of Thames - Tapu, i'ileavesvirle, Goronandel, t{ha:rgapoua and re Ahr.unata
    respectively. Robinson & Christie (1980) combined stable isotope and fIuid
    inclusion studies i-re their investigation of the l.Iaratoto lljne,
    B

    EARL' D'lR, ee#-osrcAL BuLLErlNe


    (\
    $T
    \\
    "r,/

    B
    DSIR GEOLOGrcAL MAP9
    c 12250,000 gCAt-E.

    Bdl aFrax4 fl.


    lgt2

    l/p/rqrr,Fl24
    Y
    $-lf, BrH,,*'u
    (@'vso)
    Naln,dat:gn t
    g,artflti,
    l917

    9l{E6T 3
    AUCKLAND
    c $rlofiasd,llOl)
    R,ECE!.IT D5IR,

    Rqfo uA
    -(lteaty ctal,li64)

    Plgure 1-7; Bullotl,aa and rape of tho geology of tba EaurakL area publtehed
    tbc f,.Z. Gcologlcal Survcy.
    Aaylor,954

    5kinner,1962
    tkack,967i Sklv'rcr,!967
    97O;1972.
    s,oParhrnson, t
    1male, ,1962 tjgo
    Edwardt ,lg7? Robson,1979

    5fate,ng, lg@ Harvey ,196'l


    @nwall ,l?67 Av6s,1976
    Ru$rp;rlord ,lg77
    Lawlon,lgft O'ladry,g7g
    Catpar, 1979

    lfiarchart,l97B V@rq1176;1979.
    tlorcQtcl
    ,lg78
    llair'r,lTTl;1979.
    Van elal lj72
    Rutsdl,tggo P,aborv l97lil975

    Cochrarte,196?\
    CarfutngW,lg82J

    Flgure 1-8r Oeologloal tbosea aod eaaoelated publlcatLoas relatlag to the


    rlnersl depoalia of the EeurrLl, Gol.d-Sllvsr Provlncc. .
    ..xo

    I
    Itbdzickrl,
    Yno
    b.o t
    ffiwn

    Pdln;rina @

    grodilrwdlfc 1KImw,g77b.
    tfrw

    Waiclbc4 t Wodtickl, tEft)


    i
    Wodzicfci $Ief*berq I Wle
    lfumc dd,wro
    RdErnrtolt; l9E
    lrnstTr . W75
    Kgr all/odzickt,hPYzn

    f1;B,u:rcl-ge Rac9qfi nubllgrtisae by DIIIR atrff rclatlag to th6 '$lncltl ile,poeltr


    of ttlc ftrrrrakil Esillil-'$llvar Pro' Jnc .
    11

    lbrom alMncq*,197,
    lbales t98o

    t+Yiyana,l?7ol
    Wodzfcb,l9To)
    b"o
    r*!iJ-
    O %Yva
    Wora,l979b |,loarc.
    t176'

    Coupcr, lg79
    ngl

    a Adavnson,
    ffil Marwcll,l9So

    Flgure 1-10: Eeportr by ulneral crploratlol oolpeatea'


    t2

    CHAPMR 2

    NESIOI{AL C.iEOIOGY

    -
    I}ITJTODUCTIOI'I
    follordng account of the geolot3r of the Corcnandel Peninsula and
    The
    Great Barrier Island is a s3':rthesis of previous work (theses and published
    material) ancl curuent thinking by exploration and academic geologists.

    STRATIGRAPHT

    Thestratigraphy presented in the follo,iing sections is illustrated in


    Eigs 2-1 and 2-2 and summarised in the synopsis at the end of the chapter.
    0n1y a brief account is g5,ven here ofselected formations as more deteiled
    descripti.ons are given by Skinner (tgl6) and other referenced works.

    Ilanaia JIjJ-I Group


    The oldest rocks of the Corsnandel Peninsula and Great Ba:ri.er fsLand
    are greyt/racke and argillitr" of the l,ianaia tfi|l Group. Rare fragmented
    fossils indicate an upper Jurassic (Ofrauan - Puaroan) (Stevens, 1970).
    "e"
    Skjnner (t972t t976) subdivided the group into l,toehau Fornration and
    Tokatea I'1i11 formatiorr.
    lloehau Fornation consists of slope-deposited turbidites characterised
    b;' a }-ithic volcanic gre)*Fracke and subgrey-v;acke suite (argiUite, siltstone,
    sandstone, chipvracke and conglomerate) derived frorn calc-al.ka1.irne volcanic
    and plutonic rocks and minor sedlmentary rocks.
    In contrast the Tokatea Hill- Formation consists of a feldspathic
    gre;macke suite (mudstone, siltstone and sandstone) ahost devoid. of
    volcanic detri.tus exeept near the base, derived frqn a more mature calc-
    alkaljne plutonic landrnass with minor sedimentary roclcs. The lorer mernbers
    of the formation are slope-deposited turbidites, rchereas the upper part
    resulted frqn stable deposition jl deeper water.

    Te Kuiti Group

    Torehina Formation
    The Torehina Forrnation consists of a series of linestones, caleareous
    siltstones (sone fossilijerous! Gigantostrea l*o.Llastoni), carbonaceous
    sandstones, conglanerates and thin coal seams (Kear, Lg55; $<irner, !976).
    Foraminifera indicate a Duntroonian (mid-Oligocene) age (Hornibrook,
    irr Kear L955).
    L3

    I
    CORAv$NOgL

    ,l . r
    6:.'.1
    ,w
    M{AI{GAMATA

    fiTl
    V;J
    Und.rFfcrcnf.ialzd
    dla <4)tal
    atlul//.al
    &P6at3.
    Plcirt66o11
    lD Rccctrr
    ,""tirt
    KER,IKERI VA-CAI'{IC GROUP
    E Marcury hxlltt Fcirtoctnc

    WAITEARIKI f. PAPAMOA |GNIMBRITES

    E Dacifa tgn..mttifai frcblotor

    WHITIANGA GROUP
    !in*,n &!'t ffi
    ?,ffiiax* ) r*n. viu't
    UliliL""
    rhvotllc
    t,u*,voue: and
    . |b Prnitto""'
    .evr&taslics ,I \t\
    Scdtfirant)'
    WAITAWHgTA DACITE9
    t-l gaate and ar:deiftc flowg. Pliocule
    t-ej pyralaslict a^d sadhfld$r
    COROMANDEL GROUP
    Fl lndcglfc.ond dactlc AWs, , ).
    I'v-f Wioclasfica hind sadivneirtls I Lowcr Mtoccnc ?a;ks d lnc Cerrlral Volunie Rcgion
    ?arrlu Plulovticr. auarlz diorile..| to Plfoccne
    = qa odiorilc ond' lonalilc -
    )
    TE KUITI GROUP
    E Inrffiz, Iaffi#:g,z&f1klfa+.,,,oot otisoccac
    MANAIA HILL GROTIP
    72 g:"r*^t!xq#.*z*' arsittitz

    FJ.gure 2-'ll Reglonal geologlcal nap.


    14

    Atfuvrurvt ?ecenf

    Mcrcury baEalls
    KER'iKERI
    -^..^)
    voLcANlc GRoUP( ?tdr*occnc
    \s
    s Witeainl<i and I
    IE} ?aPww'\nimbifict I
    J
    a-
    qf l=-E 5d"9'(ffif))*HrThN6A
    'os Mindavr W'rlotita
    l^',#[-" V
    i3
    c-orogtu Su\rodp1*.) GRoUP
    ts9
    t>
    I bot:{"r" ,
    -Y
    .gVr
    'tr lt
    -o
    E
    'e
    .9 Itt Wailavvhefa gactel Miid ?licr,eru
    ;
    7/

    Andestic and
    dacitic
    exlYusves Numcrou, foimalong d
    quarlz dbYlte vdcanic ard inlrusive Lowcr
    intrueivea roc*t (c.f. Fh 2'7 and COROMATIDEL
    Ilfoccne to
    VV v 1tzible 2-t) ' GROUP UVper
    ?liocqv'
    ?a:rtfu PlufonicE

    furdsloncs, ltme- Formafon TE KUITI ?ligoccne


    stancs r cml xon: Iorehrna . GROV?

    lokalea

    6rcywackc Fuvyurion
    Mochau

    Wz
    Flgure 2-2: StratlgraPblc coluun.
    t5

    Coromandel Gr-oup

    Introduction
    Thompson (1950) and Schofield ( L967) grouped the andesites (and sorn^*e
    dacites) of Great Barrj-er Is1and and the Corcmandel Penjlsula into the
    Beesons Islarrd Volcanics (synonymous with the First and Second Period
    Volcanics of the early writers), Subseguent geological stud.ies of these
    areas follcr',ied their example until Skinner (1976) formally restricted
    Beesons.fsJ-and Volcanics to a specific group of rocksl at present identified.
    only frcrn Tapu north to ColviIle. The Beesons fsland Volcanics of Tbonrpson
    and Schofield are nsr.r temed Corcmandel Group. This group includes Skj-nnerf s
    Beesons Island Volcanics Forrnation in addition to several other fonnations
    of volcanic and intrusive rocks formerly included in the Beesons Island
    Volcanics.
    Published det:'i'led mapping of the Corcmandel Group (i.e. Skinner, t976)
    cover on1-y the northern pa:t of the Corornandel Peninsula, north of the
    torm of Corsnandel, and therefore formal subdivision of the Corcrnandel Group
    is confined to this rr3r Hor.rever, several inforrnalJ-y defined formations
    descrlbed in Auclcland lhriversity M.Sc. and Ph.D. theses, and some presently
    bejJrg mapped by Skinner, are a).so included here.

    Volcanic Rocks
    Table 2-1 1ists sone of the forrnal.ly and inform.?'l]y defined formations
    of volcan-ic rocks included here in the Coromandel Group. Their distribution
    is sho,rn in Fig. 2-]. '
    Volcanic rocks of the Corqnandel Group range il age frsn lo'r-er l.liocene
    to late Pliocene. A compilation of K - Ar ages is shorsn ln Fig. 2-4.
    Skinner (pers. commo) eonsiders that these K - Ar agesr together rrith
    palynologicaL dates, inciicate that the Coranandel Group canprises three
    dj.stinct phases of andesitic volcanism as.iJlustrated in Fig. 2-5. These
    began in the norbh and centres were tlnn sited progressively further ssuth.
    The first two phases were separated by a period of volcanic quiescence,
    whereas the second and third phases l{ere separated by a period of rhyolite
    volcanjsm (Wtritianga Gnoql, see later section).
    16

    TABLE 2-1: Son6 fornation! of volcanlc rockr lncluated Ln tho Coronandol Group. OnIy the foruatlons llstcd
    uniler ilortharn Corourandel penlneular lncludlng the Beosons Island volcanLca (also Ileted undor
    Gentral Cororuanilel. penlngula), have been fornerly tlefined. The formatloha arc lleted r,lthln
    each qroup ln a generaL order 6f Lncreae!'ng age'
    .
    NcRIHERN C0ito{AltDEL PEllIllsul,it (sktnnerr 1976)
    Hahlnapua Andeslte:
    hornblende andegtte nlth hyperat,hane, and olnor euglte and blotlte; pyroclastica, flover aedluenbs
    and lntruslvos.
    Te Tutu Andeslte:
    2 pyrorene (hypcrathene domlnanL) baalc andaaltoi pyroclastlce'
    Parakete Fortr6tlonl
    hornblende dactte ulth hyperethenet pyroclastlcg, volcanlc (eplclastlc) aedluants and rere
    flova'
    Haterangl Andaslte:
    follatad coarsely porphyrltlc hornblende andsstte to quartz andeel'te rlth hyperethenc and augltet
    flovs, pyroclastlcs and lntruslves.
    l{hangapoua Andsslte:
    2 pyroxane (hyperathene doulnant) baalc andesl.te, flosr and pyroclastlca.
    Bceaons Islgnd VolcanLct!
    ' hornblenita-bearllg hyperathene an<leeltee (generally vlth etther augite or quartz plua blotlte);
    volcenl,c (eptclaatlc) eedirnente, pyroctaatlcs anil nLnor flous and P1ug8.
    Tuaieavs Andoalte:
    2 pyrorcnc (hyparalheae dornlnant) andeslte! flovr Pyloclartlcs enil tidloqnt.
    Te Karaka Andeslte:
    2pyroxene(hyperathenedonLnant')andesLtcifloeaandbrecclag'
    f,okunata Daclte:
    rsngs frou blotltg-hornblende daclter through blotl.te-hornblende-auglta andoslt to hornblonde
    pyroxono quartz andealle; fl,orar pyroclsstLcs and eedlnenta'
    Onoho Foraatlon:
    rhyodacltB and quarlz PorPhyryi tuffg antl sodlnontE'
    Port Charles Andoelte:
    hornblendo-plfrox6nal pyroxens-hornbLende-guartz and pyroxeno andeslteet flonar brcccLas and tuffr.
    GE}nRAL.CORoIjA}IPEL PEuIu.suLA (sklnner g!3l, 19?91 pcre.coarn.) I

    ffiaui.kau Andeslte at rable Hountaln), '

    dark etronqly porphyrltlc, feldapathlc, baalc andeslte (varletlca contalnlng auqltc, hornblendc'
    hyporsthone. ollvlne ancl quartz c.f. Schoflelilr 196?tllatn,1j71iRebone,19?1fltalresrd,l97{) 0rnahla
    AndesLte of the lfaltavheta erea uas K-Ar tlated at r,?8Dy by Sttpp (1968).
    Taurahuehue Andcalt:
    flne gralned glaaay Pytoxne andsslte.
    llauuaupakl VoLcanlcg:
    ' bornblonde bearlng felslc ondesLte to daclte.
    'l
    Beeaono Island Volcanlcg: (aoe prevlous sectlon).
    HoT ',IATEII BEAGHJ- TAIRUA (oYen6' 1976)
    Tapuaetahl Andealte:
    hyperltheno-auglte antlesltel flors, brecclas. tuffa encl dlkaa'
    THIHES (Frassr,1910)
    Preuler Andeslte:
    hyperaUhane auglte andeeltc f1ons.
    Taratu Anderlte: (nrlterra tcra)
    pyroxsn6, hornblendc-pfroxen6l hypersthene and hornblende endesltes and decl,teatflone'breeclaa i dlkcc;
    WIITE8AIIRI (Rabone, 19?!)
    Jublleo itndesltc:
    hyperathene antleglte fl'ovo and nlnor broeclaa.
    0hlnanurl Andaslte:
    quartz-hyperothene andsslte flows.
    Puketava Andealte:
    auglte-hyper!thon! andeslte flosE.
    TE ARollA (coctrrane, 1969)
    Suoolt Andeglts:
    auglt-hyporsthene rnd.slto f1oss.
    Ruakaka Quartt Andesl'ter
    quertt andeglte florrc. brecclae and tuffa"
    '".^*:;:I.-lyp","tt.",.canil.s,'tof1oge.K.Arrtr!cilat16.2n.y.byAilaneeta1(19?l).
    L?

    }ONHERN COROI./ANDEL PENIN5I,II.A

    N llohil'o.lc Nld,citc
    E Tc Tutu M&ltc
    B
    :
    garatrcle Fonratbn ( dacitc)
    llatcrryl An&ltc
    g Whorgapouo Andcirtc
    ts Sezsont l:tard Volcavrics
    % Tualcarra Andeitfe,
    ts \a Yor*a Ar:dcirtc
    I YoYudta Docib.
    N Omoho Fqrmaton
    E ?orf Charles Ardsitc

    i&'J'1 CENTRAL COROMAI.IOEL PENIN'UI-A,

    ffi Omahiq An&irtc (trrr;rrau lrrdetrlc ol Toblc I&)

    E latraLvchuc At:drcsrlc Fdl;g;y,y,


    ts Marmoupaki |,ndcritc

    m $ccsons lsland \rolcontr


    ?t<lrrrcr
    At:d,csilc tr lhld,ilferq*ialcd andaitc
    and dacitc-

    #
    otErStlt
    ttrr

    Flgure 2-3: FornallY cnd lnfornally dettued fornatloaa of volcallc rocket


    tncluded 1n the Cororaadel Group (aee Teblo 2-1 for doacrlptLons).
    18

    TI

    btr

    g.5a
    lto,l.rq
    il.j4.

    4.9,5-2d
    1'OOc

    162(t62-2

    2.54ce 0

    2gr"'"J

    Etgurc 2-4r Cuapllatlor of l(rAr ages for volcerd.c rocks of the Cormandel Group.

    a . Adano & othera (pcrs. ccrn.)


    b . Adaars gEL (19?rl)
    c - Sttpp (1968)
    COROM ANDEL GROUP
    Lalc ohosa
    N (Ptiocenc)
    lnlcrmodialc Chasq
    E (gai. upper Mibccnc)
    Fl Eorh Phosc.
    E3 iff] f,;**- to mfd llioccnc)

    ,$
    *

    Ftgurc 2-Jr Pbages of aadealtle volcenlan dletl,ugutsbcd by Dr D.X.8. Sklnr|er


    (pere. coon').
    Intrusive Roeks
    (a) Oroviffe Quartz Por?hyrite
    Ra.nsay (19?1) and Ramsay & Kobe (L971+) mapped a small intmsive body
    (approciruately 50o m in dianeter) in Coromandel Group andesites of
    the Te Ahumata area and narned the unit Oroville Qr.rartz Porplryrite.
    It consists of a trporph5ritic to panidiomorphic, granular quartz-
    tqrpersthene-augite rock with plagioclase phenocrystsn (naursay & Kobe,
    L97l+ pL45). Contacts with sunounding andesites ar not e:gosed.

    (b) Paritu Plutonics


    A composite pluton intnding both Moehau Formation (greyrvacke suite
    rocks) and Port Ctrarles Andesite at the northern end of the Corqnandel
    Penfuisula was named Paritu Plutonics by Black (L9?2). The predoninant
    rock tlpe is quartz diord.te (Sklrurer, L976)1 hotrever granodiorLte and
    tonalite are also maJor constituents. K - Ar ages renge frqn 16.0 to
    1f.1 m.y. (Rtchards g$!, 1966).

    (c) rai-iti Porphyrites


    Kai-iti Porptryrites are andesitlc and dacitic intrusive bodi-es in
    Manaia Hill Group and Coromandel Group rocks which are neither cJ.early
    the intrusive equlvalent of any volcanic enrptive formationr nor fall
    rvithin a mappable geographic - canpositional association (Skinner, 1976).
    Kai-iti Porphyr{.tes have been mapped in the northern part of the
    Coromandel Peninsula (north of the town of Goromandef) by Skirurer (t915,
    L976), in the Petote Strearn area (south-east of the tovrn of Coromandel) by
    Edwards (L9?9), and in the !,lanaia VaILey by Stevens (fg80). Ttre latter
    authors recommended abandoni-ng the terrn porptlyrite and renaming the
    fovrnati,on Kai-iti Intnrsives.
    A quartz diorite cernented breccia pipe at lllners Head and various quartz
    diorite porphyry dikes to the north of this local-ityr lntruding greyracke
    suite rocks on Great Barrier Is1and, have not been fomal]y narned. They
    are informelly included within the Kai-lti Porph3rrites in this Thesis.
    Similar1y; various intnrsives in greytacke or Ccromandel Group voLcanics
    noted by Fraser & Adans (190?) frorn the Tokatea and Opitonui Mines and by
    Brathwaite (f9AO) from the lfaiJri Mine are also here included Ln the Kat-iti
    Porphlrrites.
    ?he Miners Head i-rrtnrsive was K - Ar dated at 18.1" t 0.2 m.y. (n"
    C.J.D. Adanns & Prof. P.Iui. Blackl pgrsr comm.)'
    2L

    (d) Whangapoua Intnrsives


    Stocks of hornblende diorite porphyry and hornblende nlcrodiorAte
    porphyry emplaced in Coromandel Group andesites of the I'lhangapoua area
    r.rere named l-lhangapor.ra Intmsives by Robson (fg?g). The hornblende
    diorite porphyry stock is cut by several dikes of andesite porptqrry.

    (e) fainui Intrusives


    Merchant (19?8) recognised several high level intmsive stocks of
    quartz diorite porplryry and dacite porphpyr and deeper level
    leucocratic quartz diorite intnrding Coromandel Group andesites of the
    Tapu - Thames area. He collectively fntruslves.
    naned them Tainui
    K - Ar ages range from 9.3 to L2.6 (- t9.9 ?) m.y. (h C..I.D. Adans

    & Ilr R.J. Merchant prsr comm.).

    Waitawbeta Dacites
    t{aitawheta hcites, narned by Healy et aI (t96tr, c.f, Brtggs t9?3),
    occur predominantly south of Waikino although a f6r small tsolated
    occurrences were mapped in the area between CoromandeL and lfttitianga by
    Schofield (Lg67). Skinner (19?9) has suggested that the dacitl.c
    rocks of the Waitekauri arear mapped by Rabone (19?1 t t975) as
    r,.lhitianga Group (see ne:cl section)r m&y also be Waitawheta lbcites.
    Waitawheta Daci.tes cornprise daciti-c to andesitic lava flowst
    plrroclastics (ignimbrites and non-nelded tSpes) and sediments. In their
    type area they occur between Corornandel Group andesites and l{hitianga
    Group rtgrolites and igpimbrites but they have not been formally assigned
    to either of these groupsr
    Stipp (1968, p 2L5) detenrined a K - Ar age of 3.90 t O-O? r.[. for
    l,laitar.rheta Ibcites at the western end of the Kaimai Tunnelr

    Whitianea Group
    iitritianga Group (synonyrnor.rs with the Third Period Volcanics of
    The
    the early writers) consists of rhyolite pyroclastics and epiclastic
    sedlmentss igni.rnbrites and flow banded, spherulitic and llthoidal
    rtryolites. The stratigraphy and geology, wtth enphasis on the ptrrroclastic

    Thompson (1966) classified the Hhitianga Group into two


    ncontemporaneousn subgroups; Minden Rhyolite (flow bandedr spherulitic
    and and Coroglen Igninbrlte (ignimbritesr p;noclastlcs
    litholdal rhyolite)
    and sedirnents). Hayward (19?4) suggested that the latter should be
    22

    termed Coroglen Subgroup rather than Corogl,en Ignimbrlte becanse it


    is not entirely composed of igrrinbrite. The terms ltinden Rtryolite
    Subgroup and Coroglen Subgroup ar used in this thesis'
    Hanrey (L96?) 1 Bntherford (19?or 19?8)1 Havward (t97t, L9?7t tgzl+),
    Rabone (rgzr t L975) I Ramsay (rgzr), Ramsay & Kobe (L97D, Moore (L976t
    LgTg); Ovens (19tq, Merchant, (19?S), Torckler (rgZS)1 Barker et aI (1980)
    and Erceg (1981) irvestigated individual areas of l{hitianga Group rocks
    in detail and their results indicate a eonplex stratigraphic successi-on
    involving seguences of alteinating CorogJ-en Subgroup and l{inden R}tyo}lte
    Subgroup fornations. Skinner (in Sldnner ${r 1979) suggested that
    each dqne cmrplex and flow sheet rnust be treated as a separate. formatlon.
    Correlation frsn one area to another is therefore difficult.
    The most complete e4pooed seguence has been described frmr the
    Table ltosrtatn area (Fig.24) by Haywarrt (tgZtt t973t t97I+) and i's
    surnarised in Fig, 2-?. llayrard (L974) consldered that a volcanically
    - qraescent period of erosion took place between the Coromandel Group
    andesitic enrptions and the start of the Whitlanga Group rhyollte
    activity, forming a noderately dissected landscape and deposlting
    pockets of talus breccia.
    The first rhyolitic enrptions were a short errplosive pbase fol-lowed
    by a quiescent period of sedirnentatlon il snall lakes (Wainora Formation).
    Major tephra enrptions which burled the 1and beneath a thick blanket of
    ash and lapiJ-li shower deposits, hot pyrocrastic flov*sr ed lahars
    terrninated. the. l{ainora sedimentation, Although the lakes soon became
    infiiled, deposition of fLrnrial, subaerlaL, and ninor lacustrjne sedinents
    continued, in the valleys during the flrst half of ttds errrptive phasel
    after which aIL Coroglen sediments and tgnimbrites were subaerial.
    As the explosive tephra enrptions waned, tlinden Rhyollte dcmes rere
    intruded and extruded, possibly aLong sone of the pre-eldsting vents.
    Tr.ro phases of domes occur at Tab1e Mor:ntain and these are interbedded nith
    Coroglen Subgroup ptrnrocl-astics and epiclastlcs.
    The follow"ing descriptl-ons of other Whitlanga Group seguences are
    listed in geograpllcal order from north to south (c.f. Elg. 2-6).

    Great Barrier Island


    i.lhitianga Group rocks are e{posed on Great Barrier Is1and at }ft
    Hobson, Te Ahrmata (tlhitecliffs) and Okupu (fig. 24).
    The Hobson Rhyollte (tfrompsonr 1960) of Mt Hobson consists of
    23

    tr
    ffi #
    Hobton RhYolitc

    Ahuwrata 9iril'\ffiS
    Formalion '/ t"" Y)
    3ee Flq- I-B-l

    %oo
    T

    5on Fig 2-8

    ?aku .
    lSldtld
    0
    9rokar llill:
    5oe, FgI.K'l

    Nogva,svila
    toe Fig.I-N-l
    5ea F\g T'5'7
    Wattukauri.'
    1ca fiqs. /
    I-OJ r I-P-l '

    $wharo4, lanimbritE;
    Frn a d "Tridvmrfd
    Rhyolile . C

    WI{ITIANGA 6ROUP
    7V Vindqn Rtwoltta 5vbarot6-- Paparnoa
    V4 (ltott fu^ddd, rphcnrfrtra'
    alnvu'aat rhfolita) larivabrilc
    Coroalen guW?ou? dnd Ic Pt,;f;q
    lfl
    IEJ (lan*{brllc+. rVT lottlc' Brvanas
    p,lroclastiel t 4advwr*>

    Ftgure 2-6: f,hyol.ltle rockg. of thc llaurakl Gold-Sllver Provlnce.


    2l+

    ET WHITIAN6A 6ROU?
    GROU? COROMN.IDEL 6ROUP
    F
    \tuatumoo , Waiwawa, -+ +
    o
    =o-
    >-J ++
    Y,attaoranqq, and Voylcs r+ +
    ;LO rt Oftuhia
    rr Ol (otde,sf) rhyolifc J. \\\\
    tt
    t
    Ar.dcgille
    \9 dome,E.
    Zc0 ///
    ul=
    L)ln
    .1-

    = ,l
    5ubaerwl dcoealsz
    domirlarrtlv v,i ro cl o thi
    seryyal, lnin.'?9qlY I
    weldad $nimbrtlris I loova

    I
    6Om
    N
    .s
    o- s\)
    5
    o \
    0

    oz d
    LD
    co
    ts
    5
    rn
    =
    zUJ Watc.rlaid
    inlerlcnanie' tine - not
    J
    (D
    o
    coaftc aratned
    tcdimanb, wilh not
    ls
    OZ andzitfe,,- pumicc a
    o
    LJ rhyoltla ' Vloc,l;
    lfx|P.

    I
    - v UndilffcrzYtrtdted
    Ftng gralned highly vv
    cafDonaca,ou' vv vvv ar&itfe flows
    :
    cplcla;/'ic laKc vv
    SedimsYrts wilh lcaf vv
    YV arl cpiclaslic
    l!
    impresionS and vvv SedimanlE.
    yv vv
    s migsel fossils.
    o Prcccdcd by lre-laka
    .s pyroclaslict with
    5 and rhyotite
    etf::"

    Flgure 2-?: Stratl.graphlc colunn for the TebLc Hountaln aree conptled fron
    deecrlptloas by llayvard (1971et 1974b).
    25

    flgurc 2-g: Geology of the arce esat of Thitlauga" (Fron ovena, 1976 rtg 17.)
    26

    rhyolite lavas ninor breccia and tr.rff which may be part of an


    and
    eroded acrne (thonpson, 1950). A rhyolite dome also occurs at Olnryu
    (Erceg, 1981).
    The Ahumata Sl.nter Formation (narnsay & Kobe, L974) at Te Ahnmata
    is a lacr:strine sequence of siliceous sj.nterl rhyolite plrroclastics and
    carbonaceous shales (nansay & Kobe, t974).

    l{hitlanga
    The area east of Wtritianga (ftg. 2-8)
    was described by Hanrey (1967)
    and Oqrens (L976) and comprd.ses 1O domes, numerotxt smal] associated pumlce
    breccias and two ash florr (fgrfubrite) sheets of the Wtritianga Group.
    Harrrey (L96?) considered that dome fonmation began b5r exogenor grcrth
    5,rvolrrlng the effusion of flow rhyolites and pr.unlce breccias. Subsequent
    endogenous dme building produced the main dsne trith spherulitic outer
    and crystalline irurer phases. Sometime late in tttls sequence at ].east
    two domes errrpted fragmental materd.al fo:ming ash flovr sheets. Orens
    (L976) postulated that the Hhitianga Ash FIow was erupted frmt a vent
    slted in what is now Uhiti.anga Harbour, whereas the Ho't l{ater Beach
    Fomation (ignirnbrite) was considered to have or{.gi-nated frcrn a breach in
    the i{henuakite Dorne. The Hot 'rlater Beach Fonration occurs at the margin
    of the 'dhi.tianga Grorp and r.mconformably overlies Tapuaetahi Andesite
    Formation (Coranandel Group).
    Based on the geonorphologT, 0rrens concluded that the Whenuakite Done
    nas considerably younger than the other dores in the &rsar

    Palcu Island
    Rlryolite dcrae coaprising Paku Island (RLg, 2-6) was
    The l,ltnden
    deseribed by Butherfora (f9?O). It consists of a steep to vertica)- fllow
    Layered perlitic to glassy spherulitlc, obsidian rich outer zone swround-
    fuig a core or plug of inward dipping flLow banded lithoidal rlqrol.ite,
    Errptions of ignirnbrttes and purnice breccias occured prtor to endogenous
    dcns txri-ldlvtg.

    Broken HilIs
    The sequence at hoken !l{11s, descrd.bed by Moore (t976, t979)t
    consists of a lO0nr thick series of flow banded rtryolites (Uinaen
    BhyoLite) s uaconformably overl5rlng Cormandel Group volcanlcsr followed
    by Coroglen Subgroup pyroclastlcs.
    27

    (f{ayn;tn Rhyofrt-c,) gottwtown

    Flgurc 2-9: Flsalon treck agea of l{hltiaaga Oroup rockr: a = }ll'ndan Rhyoltta
    Subgroupr detertlned by Rutherford and b . Coroglen SubgrouPr ileteruined
    by f,ohn (1g7rl. Areeg of rhyoltte rockg (tfhltlanga Group and othcl unlts)
    arc abadcd,
    Thames
    ppoclastics and ignimbrites of the Corog]-en Subgroup are
    Otrly
    present in the Iookout Rocks of the Thames arear described by Merchant
    (fgZg). He conelated them with the I'lhitianga Group segtrence at ?able
    Mountain, XO kn to the norttr-east,

    !treavewille
    Minden Rhyoliteis also abent from the Neavesville area described
    by Torckler (1978) and Barker glg! (1980). At ttrts location the
    Coroglen Subgroup consists of ptrrroclastics followed by lacustrd.ne
    sediments and a further phase of subaerLal rhyolitic pyroclastics'

    Waitekauri
    In the !{aitekauri area (L97tt L975) napped rrnits of fine
    Rabone
    grained dacite breccias, maisive hornblende dacite flowsr ltthoidal
    rtryodacites and rhyolite, The dacitic rocks predominate.
    Skfuurer (in Stfnner g!{r L9?9) suggested t}6t a'l r the dacitic -
    r[yodacitic rocks of the Waitekaur:l area may be units of the lJaitawheta
    Ibcites.

    Waitekauri -
    Haihi
    In the soutlr-eastern section of the Haitekauri aree and over nuch
    of the Waihi Plains the l'lhJ.tianga Group consi*sts of sphenrllbl'c rhyollte
    overlaln by two ignirnbrites; the Oyharoa Ignimbrite Formatior (Rabonet
    L9?5), formerJ.y lmonn as Onharoite or Wllsoniter 8d the Trtdymite
    Rlryolite (c.f. EWarb & Healy, 1965 and srmmarlr by Figgs, L973).

    Age of the Whitianga Group


    Rutherford (19?S) dated l4inden Rlryolite obsidians frm flve locations
    (fie. 2-!) usrng the fisslon track method. His results (8.1 m.y. to 2.3
    m.y.) generally support the htrpothesls that rhyolite volcanism began in
    the north and progressed souttn*ards.
    Kohn (19fJ) aatea Owharoa lgnlnbrite Formation at 2.8p m.y. and
    Tnl{ymlte Rhyolite at 1.1 m.y. also r.rsing the fission track method.

    Pagamoa and Haiteariki Ierimbrltes


    The rhyolite pyroclastic units in the souLhern part of the
    re6ion were mapped by Hea1y {E],r (1964) as Papanoa Ignimbrlte
    and Wai.tearild. Ignimbrite. Although BrLggs (1973), in her revlew,
    29

    included then as part of the l{hitianga Group they have noL been
    formerly assigned to thls group and are therefore considered separately
    here.
    i.iaiteariki lgnimbnite is dacittc in cornpositionr whereas Papanoa
    Ignimbrite is dacitlc to andesiti.c. The units are similar i:c appearance
    and stratigraphic position and may be cotrelatives, Healy et-al (1954)
    assigned them a Miocene age, honever palecrnagnetic evidence suggests
    that the age of l'laiteariki lenj.lnbrite (and Papernoa lgrdmbrite?) may be
    miC-Pleistocene (c.f. Briggs, 19|13)'
    Papamoa Igrrimbrite is separated frcm oLder Corqnandel Group
    andesites by Te Pr:ke Breccias, a sedi.mentary unit consisting of pumice
    brecclas and trrffs, lrith interbedded freshwater siltstones and sandstor.leg
    (ueary g[j!, 1964).

    Kerikeri Volcanic Group

    Mercury Basalts
    MercurSr Basalts are a series of t'extrusives, intnrsivesr pyroclastites
    and epiclastites belongirg to a satrrrated high aluminar calc-alkaline
    basalt suite of tholeiitic parentaget' (Skinner, LJf6 p 15). They wer'e
    mapped by Skinner frqn the eastern tlp of the Kuaoturru Peninsulal Red
    Mercury Island and several nearby islands. He considered that they
    were younger than lower Pliocene (Skirurer, L976) and probably of mid
    or late Plejstocene age (Skinnerr in Skinner g[!r 1979).

    STRUCTURE

    Introduction
    The stmcture of the prorrince is dorinated by the Ntf - NNW trend
    of the Coromandel Peninsub and fold axes of the greyYacke basement
    (Uanaia Hill Group). Subsequent faulting was predonlnantl3r longitudinal
    (llt{ - NIfd) or transverse (}E - E![E) to thls trend, however Sdrrrer (19?6)
    considered that where there is ttrick Cenozoic rock cflrer the faults
    trend more Nlf and NE.

    Hauraki Depression
    The western margin of the Coromandel Peninsula is bounded by the
    Hsurald Depressi.on, deftned by the Hauraki P1afuts and the Firth of Tlnnes.
    Hochstein & Nixon (L979) suggested that the Hauraki Depression was part
    of a rift structure, the Hauralci Rift, which e:cbends for approxirnately
    30O kn from the Taupo Volcanic Zone, through the Hauralci Gulft to
    Whangarei (pig. 2-10). These authors considered that the rift was
    initiated in the upper Miocene and that recenL activity is indicated
    by active faulting, shallow earthquakes and the presence of numerous
    hot springs (e.g. Te Aroha).

    Coromandel Depression
    Otleary (fpZS) madea gravity sunrey of the easterar par! of the
    Corqnandel Peninstr-la and interpreted his results to lndicate the
    existence of a graben between tdhitia4ga and llhanganata (Figs 2-1O and
    2-11) fttred with Whitianga Group rocks. He named the structure the
    Wh:ltianga Graben. He proposed that the graben vtas offset at scrne
    IocatLons W tr1slf - ENE cross fauLts dirrid:ing i-t into a number of blocks.
    In cross-section (fig. z-LL) the western margln of this graben has a
    shallow dip, whereas the eastera margl.n dips steeply. The graben was
    considered to be approximat'ely 2.5 km deep.
    Hochstelr (1980) grouped the l,Ihitianga Graben r+ith sfuniLar grabens
    to the north and south (the tatter termed the l{aihi Graben) as parts of
    a strLrcture he naned the Goromand,el Depression (Fig' 2-10).

    nETATIgN OF_VoIC$NrSM T0 PIirE TECToNICS

    Reprional Setting
    Ballance (tgZ6) rrlated the upper Cenozoic volcanism in the northern
    pert of New Zealand to a series of six successive magrnatic arcs formed
    as a result of subduction of the PacifLc Ptate beneath the Indian Plate.
    The igneous rocks of the Corqnandel Peninsula and Great Barrler Island
    may be correlated with fotr of these arcs as fo.Llowsl
    Norttrland Arc (c.a. 18 m,y. to c.a. 15 m.y.): Early to mid lEocene
    Corqnandel Crroup ([Jartz diorite and granodiorite intnrsives (e.g. Miners
    Head and farltu) and andesite volcanicg.
    Corornandel Arc (c.a. 1! m.y. to 6 m.y.); Upper MLocene Corcrnandel
    Group andeslte volcanics and intrusives (e.g. fainul Intrusives).
    t{hitlanga Arc (c,a. 6 m.y. to J m.y.): Pliocene l{hitianga Group
    rtryolite volcanicsl I'laitawheta Dacltes and Corcmandel Group andesitic
    and dacitic volcanlcs and intmsives (e.g. Onahia Andestte).
    Tauranga Arc (c.a. J n.y. to o'?5 m-y.): Wtritjanga Group
    lgnfubrites (e.g. Orharoa lgnlnbrtte Formatisr and Tri$nnite Rhyolite)t
    papanoa lgni$brlte, Waiteariki lgninbrite and Mercurlr Basalts (ferilceri
    Volcanic Group).
    3t

    tt?

    ttthitianga
    6raban

    Warhr bYaban
    a
    !I
    -4

    Vletwrr^c
    ffi Alliuv,ftrvt.l

    EI Terttaryi Volearircg
    FA
    EI Tavitar,,1 1cdilymw,tls
    tw 6r'cyramcder- ba;wwvrfr

    E1g.qro ?-!Oa ntft ane Corsnanila1 Dolpea:dorr SIgr 2*1o{o rop (attir
    Fb:c ,Eaurald.
    Foohc.tcl.n t; Sixsrir r[9?9; tlo.o-blls$n l980l gtl'orry' 19?U] llrtd Flgr' &etl:EB:
    crossr I'c.s,ttso {rodlfled fror Eoehste!'n I ilixoar l9?9 3lE'10i}..
    33

    A lapu - gmr Harbour


    (ea
    //
    \\
    ?
    ),
    I

    5o- 2
    o\, ,
    Pauanul
    (lon
    E
    $
    et,
    o T b
    Kopu - 0poutare,
    e
    w8
    g' 7
    52 /,
    c
    83

    l0l(m

    E WhiYianga Sroup VoJa rncs

    E Cororrsrtde,l 6ror'tp Volcolrics


    n gasevneYt 6ralwacke

    Flgure 2-11: Gross rgctLoaa of the llhttlanga Oraben (Ftg.2-10). (Frou OtLearyr
    19?8 Ftgr 3' I antt 5.)
    3l+

    Theevolution of the nagnratic arcs in relation to the position and


    fonn of the Indian rlater/Pacific Plate boundary rcas discu,ssed by Cole &
    Ler+is ( rg8r) .

    Magna Genesis
    The genesis of the magmas which produced the intruslve and e:ctnrsive
    rocks of the Corornandel and lthiti.anga Groups is probably sirnjlar to that
    presentl-y forming andesitic and rhyolitic volcan:ism in the Taupo Volcanic
    Zone, the latter representlng a later stage il the etrolution of the New
    Zealand l"lags'ratic Arc (Ballance, tll6i c.f. CoIe & Iewisr1981).
    The models advanced by Cole (1981) for the genesis of the volcanic
    rocks of the Taupo Volcanic Zone are considered by the writer to be also
    applicable to the Coromandel and Whlti-anga Groups, He suggested that
    andesite magmas were formed by partial nrelti.ng of amph;ibolite in the
    subduction 'zetnet whereas hydratiur of the lower crust, causing parLial
    urelting of the greSn*acke suite rocks, produced the rhyolite rn3glta'sr

    SYI\IOPSIS

    The basement rocks of Jurassic gre;nracke and argillite (Manaia Hill


    Group) were intensively deforrned, uplifted and folded approximately along
    the axis ef the penirrsula during the Rangitata Orogeny (.Iurassic to
    Cretaceous). A long period of peneplanation follored, errlninating in a
    mid Tertiary marine transgression with the deposition of a succession of
    fresh water, estuarine and marine sed:irnents (Torehina Formation) around
    the periphery of the Coromandel Ranges.
    A volcanic arc (tttortnand Arc of Bal-lance, tJ'16) was inltlated in
    the lower Miocene by the formation of a westr*ard dipping subduction zone
    intersecting the surface east of the Coronandel Peninsula. Plutonic and
    hl4pa.byssa1 acid and intetmediate magmas intrrrded the greyracke (e.g.
    Paritu Plutonics and Kai-iti Porphyrites) and were associated with
    widespread andesitic volcanism (Iower Corqnandel Group) between 19 and
    16 m.y., Volcanic episodes began in the northern part of the regi.on and
    migrated southr+arrl with time,
    A perd.od of volcanic qulescence oecurred qrer most of the area
    between 16 and L2 m.y. to be followed by a seccrd period of intnrsion
    (e,g. Tainul Inlmstives) and andesitlc volcanlsm between 12 and 5 m.y.
    (Coromandel Arc of Fallance, L976). SsnetLne during this perd-od the
    site of subductlon began migrating souttpeastward to form successively
    the Tauranga Arc and the Taupo Arc. The changing tectonic patterre caused
    tensj.sral faulting and the developtent of the Corcrnandel Depression into
    rshich rtryolite volcanlcs (Wtritianga Group) were intnrded and errrpted
    between 9 and J m.y. (c.a. tftdt'knga Arc).
    Andesitic and dacitic volcanisn (e.g. Onahia Andesites and
    Waitawheta Dacj.tes) proceeded concnrrently rdth, ht in different
    areas to, the rltyolite volcanism.
    Volcanism culninated with the enrptLon of large pyroclastic fLon
    deposits (e.g, Olharoa Ignlnbrlte Fotmation and Trldynite Rhyolite)
    and basalts (Mercur'1y Basalts).
    . A zone of rlftlng curent\r occurs to the west of the Goronandel
    Penin$rlal in the Haurakt Depnessionr and is rlated to the presenL
    site of the nagmatic arc in the Taupo VolcanLc Zone.
    2.4
    Jv

    0HAPER 3
    I{YDROTHEnI..iAL *L1ETIr1.TIO}I

    IilTROppCTtoIr
    An urderstanding of the style of hydrotherrnal alteraLion of the
    country rocks is inportarrt to the study of mj:teralisation for the
    interp::etation of both the ph1'sicochemistry and genesis,
    This chapter reviews the ttrpes of hydrothermal alteration identified
    ln the prorrince $r prerious- r.riters.

    nrpRolHffilaAt A!TEna.TIOI,r MINERqJ,


    -CflEqKI,IST
    the hydrothemal alteratj.on ninerals identified froru the varlous
    areas studied by prevS-ous writers are listed in Table 3-1.

    N$FNCI.I1TUnE
    Some brief notes on a ferv hydrothermal alteration ninerals are
    tncluded here to rationalise the ncnenclattrre used in their identification
    by the different authors referenced in later seetions.

    Kaeljn' Kaolini-Le and I'+olirrii;e Grorq


    The tern kao]-in l'ras used by the early writers fe3 el'l hydrorbhernal
    clays and does not necessarily imply a kaolinite canposition. Therefore
    it is abandoned here and the term hydrotherrual cl.ay is used jnstead. the
    term kaoljnite is r:sed for the mineral-'species kaolfulte and is distinct
    frcrn the t'errn kaolinite group which includes g'l'l glays nith a kaoUnite
    2layer type stnrcture (".9. kaolinite, dickite, nacrite and halloSrsite).

    Serici!e
    Sericite is a term used to define fine grained uhite mica, either
    muscs\rite (r2ar,[si6ab]020[oH]l) or parasonite (l'larA14[si6a121oro[oH1').
    Only the pobassir.m form j-s ccnrsidered here.
    K-serj-cites tend to have higher SiO2r llgo and It O and l.stier K2O ttran
    muscovites and as such a1's i]lifes (r*rlt*[se+no_rJoro[ouJu), cla]ns
    of intermecriite ccnpositi,on and stnrcture between rnu.scorite and
    montmoril 1 onite (rrrosi*oro[oH]4) .
    X-ray diffraction studies of sericites of the ltrauraki Gold - Stlver
    Provilce have identified their csnposition as i]]ils, and irr scrne cases
    interlayered i]'lite - montmoril'lonite, the latter regarded by scme authors
    a].so as il'lifs (c.f. Krau.skopf , L979). The general term seri-cite is u.sed
    ,aE
    AA
    ';l \,
    '

    I
    Jt
    fF Eo*
    yiE
    NO

    d
    F
    d+ EI

    r
    C'
    :f.,
    ^J
    gsts
    ?rtv
    A^d
    4 E'
    to
    dL
    f{!,\ c

    ss d$r# oorird
    -o oa .i,
    0:t
    gcd.:a A!Eg
    ,J^ d gg g: 6or
    f i r;^
    clA
    f/tirst$A.+
    ,Fl.
    t43"
    {
    a,$8 z '1 I sE cd'
    eEm
    Fit { *d .
    'Ft(ll -:l lit il
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    -40

    !..AELts?-2st{s.d.rothqtlalatrteratlonnlneralaeoanh}cp'ggldeut'i'fto'tt.
    Lngnegraclseautrle'tock'softhetl'aurqk!'Gol'd'-S!'!"sor
    Frov,'lnee by prevloua'qtudil;o'g.

    H:"
    8L*asLft,eatl.cn
    PAtuts S,trecl lcea

    (Eiiwarits,'! 9791)
    }[,anate

    (8tgv,sns,1gEO)
    f,u,aoiunu

    (Fsrkilnop-n' l98Ot

    Fy,r!.tc, ep{ilote'r ehlqrl0e r alrlor:!fro, ptrrri.te I d,Plilote


    Dlop'yl |'c re.cond:rY qtraltz, calclte, asrlal,te ( lfff te . tY'Ps
    urd cJ.ay:t ctrays) Seoondary qil8F-ttr
    chl''srlts' calol,t&r
    ac,rlott.e (1111te aad
    ,8or1.e1t,1c Scrleito and quarte ia.tenlayored ttrlXle -
    uontoor:ltrtronl'to )l,,
    nontnorlllontta and
    gu*r?.a cndl .epr!,e'j[ti pyr lterbh1onit,e r scrl cite r reoll,treg
    (lntcrlayered llllts -
    QuartErsdrlcitt ,np,utqorltrlondfie &' tltlte'l
    interldyeirorl chlorlta -
    uot,tnor114on':l.te

    eu6Fta,r pfr,ltsr ufnor


    8!ll,etre aer lsl. t E',cha1 co gtnJ t
    antl .sovelli t'e

    Ii
    -,1
    -t-
    I
    I
    rl
    41

    here but is qualified by the more specific conpositional terms of i]lite


    and i.rrteriayered illite - montmorillonite where knsvm.

    TiO- Pobmor-ohs and Leucoxene


    Leucoxene and the polynorphs of TiOri anatase, brooki-te and rutilet
    have each been noied as hydrotherrnal aIleraiion produc'us (or vein minerals)
    j-r the roci<s of the i{aurs.ki Gold - Silver Prsvince. Ho',,rever, ihere js
    sqre confusion in the 1i'r,erature regarding the ccrnposition of leuco:sene
    and its relation to the TiO, folVmorphs, Deer, Howie & Zussr,ran (1966 pp
    l+12 - 413) considered that leucoxene ttj.s nornally finely crptalUrre
    rutile, but leucoxene composed of finely divided brookite is also lsrctwnilr
    vrhereas Kerr (1979) and Heinrich (t965) considered leucoxene to be an
    amorphous hydrated form of Ti02.
    Authors of early literature on the prorince appear to report all TiO2
    alteration minerals as leucoxene, therefore u.sing it as a general termt
    whereas scrne recent authors have differentiated the TiO, poltrmorphs nrtilet
    anatase and brookite frorn leucoxene (e.g. l4erchant, !978i &Iwards, tg79i
    Robson, tg79). Stevens (f98O) incorrectly considered leucoxene s1rronymous
    vdth anatase and nrbile (c.f. Stevensr 1980 p 45).
    .A,natase, broolcite, nrtile and leucoxene are considered as separate
    forrns of TiO, in this thesjs and are reported as such r'therever possible.

    STYLE OF HYDNOTHEil'iJi,LJILMqgIION
    I}; SFEJIF]C :tC3K TPES

    GrerSlacke Ste of tle I'Iaqp.ia HiJL Group


    Rocks
    The hydrothermal alteration of gre5noracke suite rocks in the Hauraki
    GoId - Silver Province has been described in detatl frorn only three areas
    (taUte 3-2): Kuaotunu (Parkinson, 198O)r Petote Stream area (Eclr.rards, L979)
    and I'lanaj.a (Stevens, 1980). Earlier authors (e.g. Fraser & Adanrs, t9?7i
    Snrale, tJ62i Sklnner, L975) used general terms such as ttpSz:itisedtf and
    t'si.licifiedft to describe the alteration of the greyvacke rocks.
    Edirards (tglg) and Stevens (f980) subd.ivided the altered rocks of the
    Petote Sbream and l"lanaia areas respectively irtto various ranks based on the
    hyclrothermal mjneral. assemblages (Tab.Le 34) . Parkinsont s ( 1980)
    description of the alteration at Kuaotr:nu suggests that it is very sirnilarl
    except that epidobe is absent and the clay minerals exhibit the depth'
    related d'istribution, irr order of increasing depth, of:kaoljniter sericite
    (i^Ltite) ! l<aofirrite, and sericite (illite)'
    p

    18
    ffi#trr
    l$fill,l
    liiii$:'
    ,eo?', ,o,,o.(on..
    eci6ot.,.atcit..
    .,N Ueolil:J J\fu
    *ngRo Aov^NEEo t tiilt'"uS* /
    ^Y'chyi{..cto,
    !r"'
    ^iHiilE*{ to'rin" \ /
    gvr.gl- it[:tl' u/nn'
    \ \ \ RAMsAy I K*BE tg74
    sERrCrTE,
    .
    \ )uo
    sr02- ""#i-
    /,. :Slfltn'o1r--.+ lllt',,-{,?lliil,it'^"t
    O Cf- n SE
    u, F/-
    ^nc,Lus --}--* -\pl(Ol ; i;-' \.,,,0," r*-u*i)!'
    chttrilc' I cotcitr'iliiotr

    ,.dt ."*n/'"' $ '*f"' ,rrhr**rrrlSuor,


    ups y!:;! =:ii: t,,.,*_i*n+,
    '-3;,9*-*fy'.-
    CDloJtlasr
    . efilotift
    oof !iii,llii!l'lf';,t. bto
    ,|',ilt. illtla

    - Ap6ltttg 3UAFTZ l0\l fiCED

    , 't"
    \91O ' i sEFlcllE ARGILLIC

    jcridr.. ,'..ior,,"
    ,oaun$ .o,oJn.., quorl:'Ptrir'
    rurrr .oider.-
    \49' *?ll'ri;r, **u""
    9ll'l1li6e
    AL*^L,s,uc^rE-fi ,,,.\:,)r,,,/;';i6*^)rrrrrK,BEtsT4
    pnop{LrTrc
    ::l* I rqnf lcs;* !tll,i. * I'JiD;1ff"?- qu.rr'..rorr
    I
    b,n,-1 -7 rierrlr \ 4e.

    nr^,.K. :5" Illi'\'%


    ,*,,:Xl:i3V
    .;f tor 11^,{u. *..i.?li1lil"' *""'b,*r:;o'r._"*
    *g,ut.,l''"' !ttu,,,i*ro
    quortfptritr. !
    qu'rlt'.l.tr
    gyttt
    Glotr
    lrDi'rrtnta..t

    ftgure 3-1: Sty1e of hydrotbcroal altcratlon of Gorooandel Group andeaLtee


    deteruinedt by prcvlbiir dtutllei. (8ror Ednardsr 19?9 Fl.ga. 3-1 and 3-2.)
    tg

    ,\ndesites and Dacites o ti-CoJomandel Groqtr


    Sone different types of hydrothennal alteration described frqn the
    Coromandel Group andesites and dacites are illustrated in Fig- 3-L. The
    alteration is fypically propylitic produci-ng a green rock containing a
    basic mineral assemblage of quartz, sericite, carbonate (mainly calcite
    but sideri-te and <tolsnite are often present), chlorite and pyrite. There
    are differences in add.itional alteration products bet-'*een the various &reos.
    For e>camp1e, the follolving plagioclase allerai;ion products have been
    identifiecl in sqne areas (c.f. Table 3-1): secondarlr albiter adulariat
    prehnite and the zeolites; heulandite, Iaumontite, stilbite and wairakite.
    Similarly, propylitic alteration of pJroxenes and hornblende has also
    produced epidobe, biobite and uralite at some locations (c.f. table 3-L).
    Progresslve prcpylitic alteration general.ly follows the sequence of:
    (1) alteration of the groundmass and phenocrystic h;persthene to chlorite
    (! epidote), (2) alteration 9f augite and hornblende to chlorite and
    calcite (! epioote), and (3) alteration of plagioclase to sericite and
    calcite (t adularia, t secondary albite and t zeolites).
    l,lith increasing intensity the alteration etranges frcr prqlylitic to
    inter:nediate argJJlic alteration (or a clay - sericite equivalent)
    developJng an assemblage of qr.larbz, clay and pyrite. Exanples were reported
    by Ramsay & Kobe (t971+) from Te Ahurnata (quartz, sericitel kaolinite and
    rar non-:pandilg chlorite and pyrite); Robson (L9?9) frorn i'lhangapoua
    (sericite, chlorite, quartzl pyrite and sphene); l,terchant (19?B) from Tapu -
    Thanes (sericite, pyritel quartz, kaoljrrite and chlorite); t'tain (197f) fro*
    Maratoto (quartzl kaolinite and pyrite) and Rabone (L975) from'r{aitekauri
    (qr:artz, kaolinite, sericite, ctr-lorite and p;nrite). The specifi-c cornposi-tion
    of the sericite jn scrne of these areas is listed j-n Table 3-1.
    The most advanced tpe of hydrothennal alteration in the andesites and
    dacites is quartz - sericita (equival.ent to phflfic). Examples vrere
    described by Robson (1979) and Mercharrt (fgZS) frorn the t{trangapoua and
    Tapu - Tha.ures areas respectively. This type of alteration produces an
    assemblage of quarta, sericite and plrite.
    Alteration of a different style to that Cescribed abwe occurs
    associated r.rith a nunber of small unnrineralised (except for pyrite) sinter
    deposits in the andesites north of Tairua (fapuaetahi Andesite). Dlost of
    the deposits probably represent former sites of hot springs and fimeroles
    although Ovens (tglt) suggested that some (e.g. Pqmkin Hillr also known as
    Pulcepaul<eua, about 1.5 lcn north of Tairrra) are in fact vein deposits formed
    at depth. The types of alteration that occur are silicificationt
    TABL9 3-]: llydrother:a1 alteration rnineral assenblages ldentifled
    fron intruclve rocl:s of the llaurakl GoId - iillver
    Province by prevlous studlee.

    Locat lon Parltu l,lanal.a lapu - Thanes

    (i.tadztckr,19?o;
    Classlflcatlon Sklnner, 1 9?5) (Stevens,1980) (tlerchant, 19?8)

    chlorlter epldote' chlorl.ter pyrtte, chlorite, calclte'ePldotet


    calclte' sericl.ter naqnotite' calclte' aeoondnry alblto, eecondarY
    Propylltlc aecondary quartzl seeondary quartz t qunrtz, serlcLt"cr PlrLteI
    adularla' pyrlte' leu- epidote and leucoxene. aeollte and rnontnorlllonlto.
    coxene, secondary albltet
    ephene, nKaolln tyPa
    clayn (skinner 19?5)

    S111 clfi catlon quartz and pyrlte

    Secondary quartzrpyrlto' Serlcite' pyrite' quartz'


    eerlelte (1111te and kaolinlte anil chlorlte.
    Clay-gerlelte I 111te-nontrnorlllonlte),
    ( arsllllc) chlorlte, lnterlaYered
    chLoilte, uontnorill-
    onlte aad kaoltnlte
    Secondary quartzr serlclte t Quartz, aerlclte and
    Quartz-sorlclte pyrlte I chlorl te , lnter- pyrtte
    ( phy111c) layered chlorlte -
    arontnorl.llonlte
    AIkaIt alllgate 0rthoclase Blotlte ' nagnetlte and
    ( Potasalc) secondary albLte
    45

    intermedjate argi].lic alteration and advanced argilllc alteration. The


    predon:irrant as.sernblage is qlrartz and kaolinite (Ovensr 1976) although
    Swind.a'le & Hughes (fg68) descri-bed the follosing ninbra]-s frsn
    Pukepaukeuar secondary quartz, kaoliniter pXrophyllite, di.ckite, di-aspore,
    montmorjl-lonite, sericite, epidote, p3rite and leueoxene.

    Intmsive Rocks of the Corqnandel Group


    The nature of the hydrothenral alteration of jltrusive Corqnandel
    Group .rocks has been described frcnr Paritu (liodzicki-, L97Oi Skirurer, Ig75) r
    Ilanaia (Stevens, 19&) and Tapu - Thanes (tierchant, t97S). The hydrothe:mal
    alteration milerals occurring at these locations and their associations
    are listed jn Table 3-3.
    The various jrrtrusive centres j.:n the Tapu - Thames area (Tainui
    Intrusives) extriUit a zonal distribution of hydrobherrral alteration in the
    order of quartz - sericite, argil-lic and propylitic frqn core to margin,
    whereas at l"lanaia the largest jntrusive body (a rnember of the Kai-iti
    Porphyrites) is zoned in a reverse direction with a central core of advanced
    propylitic alteration surrounded by successive zones of clay - sericite
    (argillic) atd qr:arLz - sericlte alteration. Zonal patterns of alteration
    have nob been recognised in the Paritu Plutonics with the various phases
    extribiting different degrees of alteration. For exarrple, Skinner (1g25)
    noted that hydrobhermal alteration varied frqn slight i:r the quartz diorite
    to intense in the granodiorite. The alteration is genera'lly propylitic
    althongh Skirner (tg6l) noted druses of oecondary orthoclase in the igneous
    rocks of the coastal sectlon whi-ch may constitute a Unrited develognent
    of potassic alteration.
    Some phases of the Paritu Plutonics and Kai-itl Porphyrites at Paritu
    have also been effected by pre-hydrothermal alteration stages of metamorphism
    (productlon of tourualine and epidote) and deuteric uralitisation (alteration
    of hornblende. and sqne p)roxene to r:ralite). SiraiJ-ar uralitisation uas
    reported frsn iltnrsive rocks (ttai-i.ti Porphyrites) of the PetoLe $bream
    area by Ednards (1979).

    Rhyolites of the I'lhitianga Group


    $drotherma-l alteration of the I'lhitianga Group rocks occurs spatia'l]y
    related to veins and sinter deposits. The major ty;2es of alteration are
    silicification and intermedirte argillis al-teration although advarrced
    argilJ-ic and alkali siJ-icate types also occur.
    SiJ-icification occurs il most areas of altered l.lhitintaGror4l rhyolites,
    partieularly the dqnes of l.ljlden RLryolite Subgrorp (c.f. Harvey, 1967i
    Hatrrvrard, t97b; and Orens,1976).
    l+6

    Interrnediate argillic alteration has been clescribed fran Te Ahunata


    (Erceg, 1981), the area south-east of i.Ih'itianga (Har:vey, Lg67i Crrens, t9?6),
    rtrolcen !li'l'ls (lioore, L976, Lg?g) and rhames (Merchant, tg?s). Q,trartz,
    kaoliniter sericlte and pyrite are the predominant minerals produced
    althottgh the assemblage in the Lookout Rocl<s of Tharnes is qr:arbz, dicirite
    and pyri.te. The accessory minerals at Te Ahuaata are metahalloysite,
    siderite and adrrlaria, whereas adulariar hal-J.oysite and morden:Lte occur at
    Broken l{i'l 'l s.
    Advanced argil]ic alteration occprs in the Lookoub Rocks. l.ierchant
    (1978) identified two d:lfferent assemblagess (a) natroalunite and qr.rartz
    ldth mi-nor hematite, barite and kaoliniter eC rare p;rite, and
    (b) pfoptryllite.and d:ickite, t diaspore, 1 qr:artz.
    In contrast to the style of alteration described above, ?or:clcler (fgZg)
    found that the rhyolite rocks at lleavesville nere al.tered to potassiwr
    silicate'assernblages. These predorninantly consisted of quarbz and adularia
    but also contained minor sericite and albite vrith rare carborate and
    chlorite. Torckler (fgZS) suggested that feldspar alteration proceeded
    in the order: plagioclase, albitel adularia and sericite.
    The occu:rence of adularia at Te Ahumata prompted F,rceg (1981) to
    suggest that internrediate argillic alteration at that locality orrerprjnted
    an irritial adularia - sericite alteration assemblage. The same seguence
    probably oecurued at Broken Hi'l'ls. The j:ritia] style of alteration at
    these loeations may have been sjmilar to the alka-li silicate alteratioql
    at Neavesvi'11e.

    zor.iATI-oN
    -oF
    A+,ryI?ATION''
    rrqpFOTr{EBl.nL
    $everal scales of zonation of hydroiherrnal alteration are present as
    fol].ows:
    (f) Oeptfr zonati.onr Parkinson (1980) noted that at Kuaotunu the clay
    minerals were zoned with increasing depth jn the order of kaol5:rite,
    sericite (iffite) t Uotinite, and sericite (illite).

    (2) Zonation aror:nd vejrrs: l.tost authors noted that the i:rtensity of
    tgrdrothermal alteration increased to'uards the epithermal veins with
    intensly altered rocks occurring adJacent to the vei-ns.
    (3) Zonation arowtd jatrusives: Patterns of concentric zures of hydrotherrnal.
    alteration have been recognised around intrusive centres in scrne areas
    (e,g. Petote Siream area, Edrards L97gi l.fanai-a., Stevens 1t8O;
    l'lhangapoua, Robson Lg79i Tapu - Thames, Merctrant tgTS). The zones
    exhibit a trend of decreasing intensity of alteration away trcni the
    I+7

    -tsYr.'r

    COROMANDEL 6RA)P
    El Wcak Wdrofne,rmal
    l::l altemtion.
    Mderafa, lo slroyu
    hy dro lne'ttul atlerhfi on

    Flgure 3-2: Hap of the Corolanilel Oroup Voleanlc roekr, llluetratlag ichofieldr o
    (1967, dtffcrentiatlon o! tareeg lorc exteaaively propylltlaed than'othersi.
    48

    i.ntru,sive centres (although the pattern at ltanaja is ccnplicated by


    reverse zonilg within the majl intn:^sive body).
    (4) neeional zonatl,oni The 1r25OrOOO scale geologlcal map of Auckland'
    (Schofiela, tg67), differenti-ated nareas more orbensively propylitised'
    within the andesite tenain (Goranandel Group rocks). Tilo; or
    possibly three (if Uaifri is ineluded)rpard-LeL N - S trending zones
    of regional alteration occur (Fig. l-2) separated by less altered
    rocks. fire trends may be a function of time (altered andesites are
    older and. the hydrothermal al-terati.on predates the J'ounger andesites)t
    erosion level (the hydrotherurally altered andesites represent deeper
    leve1s) or spatiqlly restricted intnrsive activity.
    h9

    CHAPIER l+

    MIIUERAIJST\TION

    -
    ITTIRODUCTION

    ?his chapter ccnpares the mj:reralised deposits of the Hauraki Gold -


    -
    Silver Prorince described individually in Appendix I.
    Porphpy cqpper and epithermal deposits occur j.:n the Province. The
    term epitherrnal is u.sed here in the sense of Schmit (fg:O) snd gi'llitoe
    (llg7?) to describe mineraljsations formed at shallcnr depth rrithout the
    inplication of J.on ternperature as originally suggested by Lindgren (c.f,
    Lindgren, 1933).

    crEcrrl,Iq1s 0F PRg"Aru qNsna4s_

    The prirnary rnetelll-c minerals identi^fied frqn the indivldual deposits


    are listed in Table 4-1, whereas the gangue minerals are listed in Table
    l+Q.

    POPf !ffBY-COPPER pF6I15


    Porphyry copper deposits occur at the northera end of Great Barrier
    fsland (the Needles and Miners Head)' Paritu, Manaia and between Tapu and
    Thames (fig. 4-1 and Table 4-3). They are of Hiocene age (nig. {-1) and
    are associated urith dikes, stocks and plutons of pred.cniraarrtly quartz
    dlorite to granodiorite cunposition (aria their volcanic equivalents),
    which intrude Jurassic grelnracke suite rocks and/or Miocene andesites.
    Jn tenns of Nielsents (t976) depth classification the Tapu - Tharnes deposits
    are vo.Lcarric, whereas the orbhers are h;pablissal.
    Fyrite and chalcopyrite are the major ngta]]is mi:rerals (taU-e 4-3)
    and occur dissemiratedr infilling shears or in qnartz veinlets. In sqne
    cases the veinlets form stoclcwork patterns cementing breccia,ted corntrXr
    rock. Spbalerite, rnolybdenite, pyrrhorbite and, magnetite are the main
    accessory minerals althotrgh the folLorsing rninerals have also been identified
    fron individual deposits: argentian pentlandite, arsenqlyrite, bornite,
    cassiteriter galena, gold, hematite, narcasite, rrrtil.e, tourmaline and
    wolfranite.
    AL1of the deposits described have been jnvestigated by mineral
    e:rploration cornpanies (includlng dr"i.Iting j.rn the case of Paritu and the
    Ohio Creek deposit in the Tapu -.Thames area) and their results to date
    suggest that the deposits s1.s srne'll, and presently ureconornic. However,
    firrther exploration work is being conducted.
    50

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    57
    EPITHm[r,\t pFP6It.S

    Introduction
    Sorne aspects of the epi.therrnal deposits ar sunmarised in Table 4=A
    and their locations are sho,rn in Fig. {-2. They occur in aIL bub the
    yor:ngest rocks of the province (Pteistocene ignirnbrites and basalts)
    and range in age from Miocene to Plejstocene,
    The mj-neralisation oceurs predoninantly in veins formed as fault
    fissure fillingsr although sone replacement mineraU.sation of uall rocks
    adjacent to the vejrts and in vein breccias of wal] sock also occurs,
    Dissemi.nated mineralisatiqe 5n cor:ntry rocks ar*ay frm the veins is miror.
    The faults are mostly tensional features, predcrninantly nonra-l and
    de:cbral with minera'lisation deposited in the resulting rlilatgnf, zones
    (c,f. Fiain, 1979). Bonanza rnineralisatj.on at Goromandel and Thanes and
    silver mineralisation at l{aratoto occurred at the intersection of a younger
    fault pattern, in scme instances sjnLstral- and/or reverse, with the pre-
    existing normal de:cbral. patterns,
    Practically all rnajor faults strike in the norLh quadtant (I\frf to I{E),
    a feature which can be equated to the arc - subductj.on tectonie system
    qlerating at the time. At sqne locations (e.g. i'Jaiorongcmai) a north-east
    trending fault pattern is superimposed on earlier north trending faults.
    The siae and tSrpe'of veins are dependant or the cornpetency of the host
    rocks, which can be ordered in decreasing cunpetency as! glleJn'racke, andesite,
    dacite and rhyolite. Large composite veins are mairrly fourd in greyuacke
    and andesite, whereas sma-ll vei.ns as v.ein slnstens are tpiea3- irt the
    dacites and jnterlacing networks of vej:rlets in the rhyolites.
    Brecciation and cnrstifi.cation are cqnmon vein te>cbures. In the former
    case the rnineralisation cemenis the breccia fragrnents (Fig. 4-3) which
    are either of waIL rock or early veLn material and rnay be up to a metre
    or so in size. Crustification usually takes the form of sSrmet3igr'l]y or
    assyrnmetricelly banded veins (nigr L+, l+-j and 4-6). Good examples of
    cockade structure (fig. 4-?) are rare. Comb structure and deposition in rmgs
    (nies 4- and l+-9) characterise the late stages of vein filling.
    The predorninant metallic minerals are pyrite, sphaleritel galena,
    chalcopyrite, acanthite and electrum (taUte 4-1) and these occur in a'gangue
    mineral assemblage of mainly gnarbz and calcite (table tb-?). Gold - silver
    selenide and tellr:ride rninerals occur in scme d,eposits and these are
    characteristic components of smle deposits, for example the niines between
    Tapu and Thames are notable for their telluride minerals.
    58

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    o-e (o.29 t o'431

    Flgurc L-2t' LocaLlons of the epltberual golil and gllver depoalta anil goldlellvcr
    ratlos for tbe naJor nlnlng centres. The nain aet of valuea sere derl,ved
    fron bulllon produetlon flgurea lleted in Donney (1935r, vheraas tha
    valuaa ln brackets are ratlog stated ln the llterature or calculited frou
    recent uetal productLon stetl,8tles, aa f,oIlors3 I = Raneay & Xobe (1j7ilt
    b = frager & ldeos (190?), o = rceBt productlon tecorda (llaratoto -
    Coasolldeted Sl1ver, Tul l{lne = tlorpac), d = BelI & Fraser (1912} and
    llorgan 1192!), and e . Ecrderson & Bartru! (1913).
    6t

    Flgure lr-3t Quartz, apbalerlter galena, cbalcopyri.te aad pyrlte celeatlng uaLl
    rock breccla, Cbelcopyrite Lode' Petote Streau (eaopJ.e 13988 reproduced
    llfs sl,ge) .
    6z

    Flgure l-l: Crustl-fl.eal veln texture ln a aaople frou thc J0lo adltr Iona Regloa'
    T6 Ahuuqta (Oreat Barrler Island). lbe vel'n contalnc aoettry chalcedonlc
    quartz but gllver ulnerallsatlou occurs ln bandls of the loeer part of the
    rpcelocB. The rpeel.ren Lg 13eu r 14cr.
    63

    tlggro 4-5: Crusttfled veLn terture l,n rilver ri.aerallntlon fro! the Caloola
    Veln, llaratoto. Late Stage 1 blocky calolta la the uppr thtrd of tbe
    opectnon ta folloved by Stage 2 bands of rbodoabroa!.te, ceLcltcl quartr,
    alderlts end sllver ulnsralleation. The opeclnea Ls approxtuately 20oo ,
    tn the longeat dloenslon.
    6h

    Figlrre ,{.6: Ban0e6 or.g f.r'98 tA lavol 'oif, thq 5aftlpoeil l{irno'r frn'eagaha&s (a,alp!e
    1d0'if,, aep.laatuEcd ltfe a!.re) - !h iler*, bcnilE ara tpladooilaentl-gt flne
    g,ral,pcil rpLel,lrite snd g+lpar ntv-h lsegogngtitg Largo.r gra!.uc of
    chaleoo3;rlgo (lttht gray trllagfrlarr grltue,l , lrbcreaq tho *hltq bands afir'
    qrrertg or eal.cltr. E[getrilt .lr *alatircLy ebnadeut la Sioliehcd rc;e'tlour.
    6f

    Plgure {-?: Hlnerallgatlon vlth eockade strueturer fron Hay Qusen, 2 level,
    l{aioroagonal (sanpJ-e 14,0?8). Breccla fragnents are aurlouniled by
    concentrlc banda' predouluantly contal,nlng quartz, aphalerite and galena.
    The spaces betyeen the oval structuree are filled ilth quartz, pyrlte and
    chalcopyrlte. The epecloen la 12cn slde by 11cn hlgh.

    1cm
    I

    flgurc 4-8: Vug quartz eryotala coated rltb late carbonates and pyrltc, Sl.lvcr
    Queeo vclnr Heratoto. Photo courtesy'of Mr E. Coppard.
    66

    flguro 4-9: Plates of barlte (up to 5or x 5un) coatlng vug quartz crystala (up
    to 20nn loag) fror the lloa lllne, l{alorongonal (eauple 11,0?O) .
    6Z

    Gold,/Silver Ratios
    Thegold/silver ratios shown in Fig. [-2 and Table [-{ were derived from
    two sources. One set of values was calculated by the writer fror br't]ion
    (8old plus sj.lver) production and lruIlion value figures listed i-n Dor,mey
    (1935), whereas sqne varues are arso presented that are averag,e assay
    values frcrn the literatr:re. The discrepancy between the tvro sets i.rndicates
    that the former set are maxi-uunr values only.

    l4i-nera1 Assemblages
    Folloring Mercharrtts (1978) scheme, several mineral assemblages are
    recognised (Table l-j). They occur as distinct episodes in the time or
    depth related pragenesis of the deposits and in the general ordei in which
    they are listed in Table 4-5 and deseribed in the fo]-lolling sectior.rs.
    Howeverr no single mineral assemblage llsted occure in at'r deposits and no
    single deposit contains al] of the mineral assemblages,

    1. Early l'lolyMenite
    Molybdenite was reporLed frorn three veins by the early nrj.ters: the
    syrvlar Tapu-Thames (Bossad, 1945)i Ajaxr Neavesrrirle (loarns, 1915); and
    an unidentified vein of the Marbha vein sSrstem, lfaihi (Morgan, LgzL).
    Their brief descriptions sqggest that it occr:red early in the vejn
    parageneses (c.f,. !4erchant, t9?8).
    Samples of molybdenite frqn lleavesville and',{ai}ri, jn the Geological
    survey corlection, consist of quartz + morybdenite (Barker gl-gt, 19so)
    and quarbz + molybdenite + pyrite + adularia + sericite + carbonate
    (hatlvaite, 1p8O) respectively.

    2. Early Pyrite ''


    Pyrite is an early congtituent in velns of rbost deposits and is
    scmetimes accompanied by marcasite (e.g. Te Ahr:matar'Manai-a and Thames),
    These mjnerals generally accompany quarbz gangue but calcite also occu1.;t
    j.:r some deposits (e.g. lularatoto, hlaitekaunl and iiaihi). This mineral
    assemblage is usuarry for.md cemeinting warl rock bneccjas,

    3. ?yrite - Chalcoplrite Assemblage


    Quartz wlth pyrite and chalcopyrite occurs as an early stage in veins
    betweelr ?apu and Thanes (e.g. Sylrria and, Monowai) and in the Chanpion and
    Ru.akakaveins of I\ri Mine. These mineralisations also generally have
    assocjated accessory Bi minerals (Tabte {-6) and goId.
    The te:cbure of the minerralisation is characterised by brecci.ation.
    :68

    i geer,E a-sr Epittreraral- vein mineral asserdsl-ages.

    Etris srudtr' .lhrehant (19781


    illraines -'Fapu A'rea
    l. Eerly moly,bdenite
    2. Early pyri-te
    3. Ffrfteehqleopyrlte assemblage gr - 3i
    4,, ryfJb-ssihalerci.te*ga.l,ena-chaleopltsite asser&lagp Fb - En
    ,5- plrr*e-spba1"':iffitffi;*i:H,*fffi:""r'NF pb - &u
    gb
    6. Sb - $f1EfttCIsa1t ndneral aeselDl-age Gr -
    7 . $rite.acanthite-eleatrrgl aseeliblagte

    8. 'ts1r,rd.te;b9na4&a electsrrln a-ssernblage Gold-pyrA"ngyrtte


    9. .Au-.Ag sulphosalt nineral asselblage ..r

    10. stibni-te 1
    ) stibnite-bacite
    ll. Barite J
    12. Cinnabar 3'

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    \at:'

    F1gurc,l,-10; Ghaleopyrtte (ysllov) auil pyrtte (crean) cut by a later veLn of


    quartz (dark grey) plua flae gralned blsnuthlntte (pale blue) anil natLve
    gold (brllllaut ye1lov); Pyrlte-Chsleopyrlte nineraL aaaenblage, Stage 1
    Tul lllner sanPle 13915. 50X.

    Flguro 4-11: IncLuslons of natlve golil (brllllant ycllor)r'blauuthlnttc (pals


    blue), pyrlte (crean), tetradynlte (creaor gcratched) and quarta (bl'ack)
    ln cbelcopyrlte (duIl yellov) ; Pyrtte-Chalcopyrlte nlneral aaecnblagel
    Stage 1 Tul l{lner salple 13909. 200X.
    7L

    The quartz and sulphides cement wal'l rock breccias and are themselves
    brecciated and cenented by'Iater mineral- assemblages. In unbrecciated
    partsr euhedral pyrite grains occur cemented by quartz and anhedral
    chalcopyrite. Iarge masses of chalcopyrite occur in specimens frso M Stope
    of the Chanpion Vein, Tui lutine. The chalcopyrite encloses rfhllsn of
    euhedral p;rrite grains believed to be replacements of marcasite (c.f.
    Cochrane, Lg69i llerchant, 1978),
    Bisrnuth minerals (selenlferous tetradynite, seleniferous tel.luro-
    bismutiter koberlite and ai.kinite at Tapu - Thanes; bismuthinite and
    tetradymi.te at ?ui Mine) and gord (rie" 4-10 and 4-11) generarly appear
    later than the mai-n chalcopyrite - pyrite phase and are follo*ed by more
    ptrnrite and sometinnes chalcopyrite.
    At lbi Miner hematite is also an important phase and occurs at first
    with pJrrite and chalcopSrrite (fig. l..L2) but later only with quartz (fig.
    4-13),

    ,+. Pyrite - Sphalerite - Galena -


    Chalcopyrite Assemblage
    Plrrite - sphalerlte - galena - chalcopJrrite is one of the nct csnmon
    fozms of minerali.sation presently exposed ln the prorrince. Table Ir-? lists
    the principal occurnences.
    The gangue is usually quarbz although calcite a].so occurs in scme
    examples' The mineralisation ttrpically occurs cernenting waIL rock breccia
    although it is sornetirnes also found in crustified veins.
    ?he paragenesis of individual veins shors that practr1'carry anf
    csnbination of the four sulphides can occur early or late althorgh at Tqi
    Mine an assemb.Lage of tetrahedrite pJ-us chalcopyrite occurs latel flIting
    fractures in earller mineralisatlon, and chalcopyrite plus pyrite occurs
    late in cqnbf and vuggy quartz in scrne veins of the petote Strean area,
    Waitekauri and l{aiorongonai, In lndividual bands there is a tendancy for
    spharerlte to be pal,red nith galena and chalcop5rrite wj.th p5n{te.
    Textures are generally slnple altbough brecciation and resorption of
    scme phases sqnetimes makes distinctiqr of boundary textures di.ffi.cult.
    Neverthelessr the various minerals Ln indirrtdual veirrs ssrra'tly have mutual
    boutdary relations indicating copreclpitation. Replacement textures mainly
    involve replacernent of ptrrrite by other sulphides (nig" 4-11+ and 4-1j).
    Pyrite is often euhedrall whereas the other minerals. are generally
    anhedral fiUing spaces between euhedral quartz grains, resulting in nfish-
    nettt textures (Figs 4-16 and 4-1?). Chalcopyrite is uhiquitor.rsly present
    as inclusions in sphalerite and may reach high proportions (Fig. &-19).
    the chalcopSrite hlebs are often aligned along cleavage planes and, growth
    zones (nrg" 4-19 and !+J:o) and were forned by exsorution, replacement or
    epitaxtaL grorth (c.f,. Craig & Vaughan, 1981 p 13;j).
    72

    Figura &-12: Blailed beretlte (pele blue) plug chalcopyrlte (yellos) and pyrlte
    (crean) i.u quartz (grey); pyrlte-cbalcopyrlte nlneral aeeonblage, Stage 1
    TuI l,llne, earple 13915. Supcrgene goethlta (alXghtly llghter grey than
    quartz) rsplaceo the hcratlte' 100X-

    Plgure 4-13r Bladeil heratlte (Ught grey) In quartz ald supergone eoethlts (both
    ilark grey) i pyrlte-cbalcopyrlte rlneraL aaaenblagat Stage 1 Tul }{lne,
    sarPh 13915. 50f.
    ,w

    ,o
    rio -
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    F1gurc 4-14:Replacenent of pyrlte (pale yetlon) by galeaa (pale bluteh grey)


    indlcated by eubaynents and potklllttc lncluslons of galene ln pyrlte;
    . salpLe 139i9 Tokatea, Coronandtai. The dark grey nlneral ls aphalerlte
    (contatnl.ng laeluelone of yellor chalcopyrite)rnhereas the black nlneral
    le quartz. 500X.

    Flgure 4-151 'Replacenent of pyrite (vhtte) Ladleeted by enbaynenta of'guartz


    (tlack) and aphalertte (ilark grey) antl Lncluslone of aphalerlte and
    chalcopyrltc (ttgfrt cr6y)t sauple 13986, Hutt Creek (Petote Strean araa)-
    200x.
    75

    Ftguro4-15: Oalena (nHte) lutergroun nith gubbedral quartz (derk grey - black)
    la a nflsh netn t,erture, Stage 2 Ualtskaurl Velnraanple 11,020. 2OOX.

    Flguro 4-1?: Galeaa-hegelte conposl.te grains (uhtte) fllllug apaco! betveen


    aubhedral gralna of quartzl Stage 2b Sllver Quean vela Haratoto, aanpl,e
    28513712. loox,
    76

    F1gure 4-18: Abunilant orlsnteil lncluaLons sxaoLved? chalcopyr!.6 (yeltow) tn


    of,
    ' aphaler!.te (grcy) i tokatca'r Coronqndslr aanple 13960. 200I.

    Ftglrc f-19: lbuudant laelucLonc of chalcopyrtte (uhlte) orlented In varloua


    patterns ta ephalerlte (grey) of eanple 13978, l{artha Velnrl{alhl. The
    aphalerlts gralno aro aurroundeit by quartz (dark grey) nhereae lncluslons
    of galeaa (rhltc-grcy, vstt gcratched-pltted' hlgh rellef) occur ln
    rphalerl.tc of thc left thtril of the photograph. 200f.
    77

    Flgure{-20r Inclucloqr of cbalcopyr!,te (yellou) arrangod aloug oleavege PIsDeg


    ln aPhelertrte (greY)' ot raoplc 140?2, llol ReelrUatorongoral. 100I.
    78

    Flgurc l-21: 'Scana of gal'caa (blu16h nhltc)' pyrltc (pale Yellor), quartz
    (Ulaek) and ulaor ebalcogyrits (ysllov) ln apholerl.te (grey) of aarPh
    13959 Tokatca Gorouandel. ' 100I'

    l.t f:?
    l'
    '* -t
    + r^

    flgurc l-22; Poltllltlc Loelrurlora of galeue (rMtc) ln cphalcrlte (srey)


    pyrltr (crcau) of aarple 14066 fron tfalht. 100X.
    79

    Ilore ccmplex te:cLures occur at Tokatea, lhames, l{aihi and i'laj-orcnrgcnai.


    rr' sample frcrn Tokatea ( L3959) contai-ns larse rlasses of sphalerite I uith
    abundant inclusions of chalcoptrrritel seamed by 1ater galenal chal,copyr4te,
    enlredra]. pyrite and quartz (Fig. t+-21). ;t,-rIeua replaces pyrite (fig. &-11).
    l'lerchant (1978) des,cribed complex Cencrriiic intergror+ths of gal-ena,
    quarLz anrl sphalerite frorn several veins in iire faipu - firiimes 6rrea (c.f.
    Photos 2-14 anO 2-1j on p 94 of llercharw, \97:";)" S-i:iihr tex$trres oceur
    in sa:irples frcrn the loner l-evels of .tailii (figr i-22 ;fi h-23) and jn a
    sanrple frorn :{aicrongonai (nig. L4.L). UnusuaL denciritic - poiJ<ilitic
    te;<tures of inclusions of chalcoplrlte, ppr"ite, galena and plrrhotite also
    occur i:r some ;Jaihi sa:nples (nigs l+-25 ard h-26).

    5. Fyrite - Sphalerite - Galena - Chaleopyrite -


    Electrum - Silver l,finerals Assemblage
    Iijlerali-sation consisting of pyrite, sphaleritel galena and chalcoplrite
    either or both electruin and silver minerals occurs at the locations
    wi'i:h
    listed jn Table 4-8. The si-1ver minerals are either acanthite (lfaihi anC
    the Camoola Vein, I'laratoto), hessite (i3ax Vein, I,leavesvil]ei SiJ-ver eueen
    Veinr t'laratoto; and Hero and Colonist Veins of l.iaiorongomai) or hessite
    in association viith a variety of other silver and gold telh:rides (Tapu -
    Tharnes and Thames).
    t'ro predmrfutant types of base metal with silver mineral assennblag-es
    occur j-n the ?apu - Tharnes (l,ionolvai, Comstock and Syl.vi-a mines) and l'h.l'nes
    (',laitangi i.iine) areas which llerchant (fgZO) classified under his pb - ?r,
    and Pb -;\u assocj-ations. The rnineralogy of each assemblage is as foIlo',.rs:
    (a) Precious raeta-l mineralisation jn l,ierchantts Pb - Zn associati-on;' quartz,
    sphaleriter galenar chalcopyrite, pyrite, tetrahedrite, hessite, sylvanite,
    stutzite (.-empressite), petzite, coloradoite, altaite and go1d..
    (b) Pb - Au association: qr:artz, galena, electrurn and marcasite.
    llerchant (1978) described the textures of the mineralisations as
    ciuracterised by complex dendritic intergro'lths between galena - quartz -
    sphalerite (fU - Zn association) and galena - qval*,2 (fU -.iu association).
    The tellurides of his Pb - 7,n assocj-a,tj.on occur inter6rcnrn wiih or replacing
    galenar and electrum of his Pb - Au associatj.on occurs as i:rclusions jn
    8alena or cementing pre-existing cataclystic pyrite, sphaleriLe or quarta,
    Complex intergrowth texbnres between quartz, spha-lerite, galena and
    chalcopyrite also occur in a specimen of crustified ore from 14 level of the
    Talisrnan I'iiner Karangahake (f igs I+-27 ana 4-28i the hand specimen is shor*n
    in Fig. l*-6). Sphalerite sornetlnes contains j-nclusions of gal-ena,
    t chalcopyrite, t electrum arranged i3 poiJcilitic (Fag. 44g); dendritic -
    BO

    Ftgurc l-23: LarelLar aphaLerlte (11cht er{iy) ln guartz (dark grey); sanpl.e
    14052 frou 10 level of the Hartha Hlne' l{athl. 1 00X.

    Flgurc 4-2{: Dendrltlc-galena ivfrfto) 1n quartz (black) exhlbitlng a herrlngbone


    pattern. ?he d'ark grey nlnerat ia aphalerlte. Sanple 1t+O72 ttod llol veln
    l{alorongoual. 100I. See also Flg. VIII-6.
    81

    Plgure 4-25: Dandrltlc - ttatraatlt galena + pyrlte i chalcopyrtte (rblte) tu


    apbalerite (grey) of oanple 13978rMertba Vels' Uaihl. Ibe black ElEeraI
    La quartz. 100X.

    tlgure {-26: Potklllttc tacluplons of gal6na (ublte)' pyrrbottte (pale ptnk)


    aud pyrlte (pale yellou) la ephalerlte (greeal'gb grey) of eenple 11'01'0
    flon tbe llartba Miner Uelbl. lLay lnclugloae of ereolved? chalcopyrlte
    (yellow) also occur ta tbe ephalerlte. The dark grey-black nlneral
    surroundl4g spbalerlte ta guartz antl ths black aross ulthin tbe epbalerlte
    aro P1t8. 1200.
    82

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    83

    Itgure 4-2?; fJ.ne gratnecl sphalerlte (grey)-galeai (nblte) lotergroutb tbat


    .uekeg up noat of tbe dark balds of spaclnet 1LO25 (ffg. 4-6) fron taltsacn
    1ri, Isve1, Karangabake. Ia tbla vlev tbs galena aPPears'to flll sPacos
    betneeu ephalerlte grelna, hovever 1n eong other parts of the apeclnen,
    graphtc and nyruekltlc lntergroutbe occur. 100X.

    Ptgurs {,-281 Spbalerlte (grey) - galeaa (nblte) - cbalcopyrlte (dull yollov)


    . - electrun (brtlllant yellov) - quartz (bfack) lntergrovth lu oanple 14,025
    fron Tellsnan 14 level, Karaagabake (c.f. FIg. 1-27). The quartz and
    glectruo oay be later than the sulpbldee' ae ln sone other parts of tba
    apecloea (e.g. Flg. 1-31t. 100X.
    84

    Figurc 6-29: Polk1lttte lncluploas of galcua, chalcopyrlte anil eleetruu (all


    vhi.te)l.aaphalerlte(groy)ofeauple14025frogTa11euan14leveI,
    Karangahake. Tbis texture le consl.dered to repreeent a croas sectlon of
    tbe itenilrltlc - 'gtreakyi texture pborn !'u Plg. 4-30. 100x.

    Ptguro 4-30: Dendrltlc - iatreakyi lnclualona of gelenct ehaleopyritc, and


    olectrun (a11 shtte) ln sphalerlte (grey) of oanPle 14,025 frou fallsuan 1L
    levell Xarangahake. 1 00I.
    85

    t'sfreakyr (f ig. IFSO) and rnyrmekitic textures. Electnnn al-so occr:rs as


    i:rcrusions in chalcopyrite andr at a later stage, ',rith quartz invading
    the earlier sulphiries (Fig. 4-31), The base netal + electrunr fo-L1owed by
    rluartz + electrun sequence i.s repeated several times across the specimen
    (itiu. tr-6),
    liessite j-s believed to occur at Iiarangahake (Henderson & Bartrum,
    1913; l.:erchant, 197s) but rras not seen by the r,;riter. rt occurs r.rith
    breccia texLure base me'ua1 mineralisaiicrn at iieavesville (.ijerx .y'ein),
    ilaratoto (Silver Queen Vein) and iJaiorongomai (Hero and Colonist). An almost
    ubiquitous assocjation of galena and hessite nas noted at Fiaratoto.
    Rarc altaite was also identified in one sanpre frcn l{aiorongorai
    (sa;:rp1e 14100 frorn the 11OOr level, Colonist section) occurr!-ng r*ith hessite
    a-< inclusions in galena.
    Acani:hiie occurs in brecciated te:*ure base netal mineralisation at
    l'jaratoto (Camoola Vein) and l'.laj&i. In the former locality it ocer:rs in
    boi;h quartz and calciie gangue. Typical te>cLures are scattered grains of
    aeant,hite, rare electrurn and sulphides in the gangue mineral (Fig. 442).
    i{hen composite grains of sulphi-des and electrum occur the mineral-s usua1ly
    e,xhibit mutual boundary relations (nig. 443').

    5. Sb - Sr.rlphosa1t l.Iineral rl,ssemblage


    I'ierehant (19?8) differentiated a Cu - Sb nineralisation stage in the
    veins bet'seen Tapu and Thanes. He considered +-hat i-t postdated rnost pb - Zn
    mineralisation because it uas *frequently seen as vugh jnfill.ings in
    earU.er torer or as crosscutting veinlets tlpically rvittrln chalcop;mite -
    ppite assemblagestt (Merchant, t97S p L2O). The foalo.ring ].ist of minerals
    uas cenpiJ.ed frcm hj.s descriptions frqn variouE occurreneess tetrahedrite,
    argentian tetrahedrite, enargite, chalccptrrrite, chalcostibite, bournsnite
    and robinsonite.
    Robson (1979) also described Sb - sulphosalt mi.neralisation (hi.s stage
    2) frm a vein and float at l{hangapoua. f,he miaera}s present }rere as
    forlowsl p;rite r miarg3r:5-te, tetrahedrite, freibergite, fanatirrite,
    sphalerite, chalccpXrritel galena and native antirnony.
    Erce6 (1981) descrj.bed an assembrage of quai:bz, marcasitel pyrite,
    famatiniter miargimiter argentian tetrahedrite [- freibergite] and. misor
    clulco,pyrite cementing a farrlt breccia (wtr"ich he consiclered to be a <lcrnr-
    ward exbension of the lorra Vein) at Te Ahur"rata. Farnati.nite and mi*argyrite
    have not been identified frcm the qr:artz veins in the ar-ea which contain
    a pyrite - sphalerite - galena - chalcopyrite assemblage (al-so vrith marcasite
    and tetrahedrite).
    86

    Flgure 4-31: Eleatrur (brtlltant yellou) autl quartz (Ulaek) lnvadl.ng earller
    chalcopyrl.te (dull yellor) and sphalertte (gray) - galena (shfte)
    lntorgrortb la aauple 11,025 frou Tallsaan 14 level, Karangahakc. 100X.

    Flgure l-32: Oralns of aphalertto (erey), chalcopy:ltc (yellov) and galcna


    (nhtte) geattered In calclte gangu'(dark EreI), eauple l'{181S6 Canoola
    VeLn, l'laratoto' The lrregular narglns of the. aulphlile gralno Ln calcLte
    gangue (e.g. cbalcopyrlte ln thls f,lgure) glve the appearance ofa
    npepperadnor taplatteri textura. 100X.
    87

    llguro 4-33; Intergrovth betseea galena (nhlte), ohalcopyrlte (yelloy),


    apbalorlte (uedlul BroY), acaathlte (pal-e grey, ecratched) aad calclte
    (dark groy) in sanple 18186 fron ths Caooola Vela, Haratoto. tfbere
    contactlng eaah other, the sulpblde uinerals geoerally have Eutual boundary
    reletloao. 200X.
    88

    7. Pyrite - icanthite - Electrrxn Assennblage


    Plnriter acanthite (argentite) and electrun mineralisation is reported
    in the early literatr:re (e.g. BeIL & Fraser, tjI?i llenderson & Barbn-u'n,
    lgLii l.loraan, I92h) frorn many of the deposits ancl iiorrld appear to be the
    cianinarrt precious metal mineralisation at i(omata, ;Jolden Cross and in the
    upper leveIs of Karangahake and ,iaihi. The rrriter r-ias unable to obtain
    samples of this assemblage for study.

    E. Plnrite - Bonanza Electrru.n Assemblage


    Electnur mjleralisation concentrated in e:cbremely rich patches cal'led
    bonanzas occrured at Corcrnandel and Tharaes. The bonanzas were related to
    stnrcturar features, generally occuring at vei.n jntersections, and
    confined to near surface ho:rizons.
    The mineralogr of the tr'ro areas dj-ffers in that l"ierchant (fgZg)
    implied a ubiquitoust association of pyrargrrite with the electnrnr at Thanes,
    whereas silver mjnerals ltere apparently u'rcomnon jn the mineralisati on at
    Coromandel (c.f. descriptions by lbaser & Adams, LgO?). The minerals
    reported from each locality al as follours;
    Corsnandel (Fraser & Adams, 19O?)i qtnra,z, pSrrite, calcite, electrum,
    arsenqDncite, native arsenic, stibnite, pyrargFite and. aragonite.
    Thames (I.lerchant, 1g?B); quar+z, plrite, plrargrite, electrwn,
    barite I stibnite, arsencpyrite and chalcoprSrite.

    f. iu - Ag Sulphosalt l',ljneral Assemblage


    l'1j.:nerali.sations con'prising pyrite, electnrn and Au - Ag sulphosalts
    occur at Te Ahumata, Broken Hi]'ls and in the Tapu- Thames area.
    The erectrum and surphides are very fine grained and occur in
    chalcedonic qr:artz rrith a very 1o"r metalliferors minera/quarta ratio.
    The various minerals present at each rocality are as fo.Lrors:
    Te Ahunata (namsay & I(obe, Lg?l+h quartz, ppite, chal.cq>1rite,
    pyrargyrite, proustite, polybasite/pearceite, seleni.ferous agyrodite,
    a6uilariter naumarulite and electnm. A hand specimen is shor,vn in F5.g. 4-L.
    hoken Hi'lls (l,iooret t976i tg?g): quartz, barite, p;rrites cersrite,
    aguilarit e r naumannite/aguiltarit e, aguilarite/acanilrite, acanthite,
    trechmanniter eJ-ectrum, native silver and some conrplex.{u - Ag arsenic
    sulphoselenides.
    Norfo.Lk Reefr Tapu - 19?s)r quartz, pyrargrite,
    Thames (Merchant,
    polybasiter marcasite, charcopSrite, ptrrite, anatasel stephanite (?),
    miargyrite (t), galena and electnm.
    8g

    Ftgure 4,- 34: Platea of barlte (up t6 5nn acrosa) coatlng parta of a quartz
    eryatal (4oor long) frou tbe llelcone VeJ.n, lfalorongonral . Sauple 1t099.
    go .'
    10. Stibnite
    Sbibrite occurs j.rn late veil quarbz, particularly as needles on vug
    qlrarbzr at Te Ahumata, Wharqgapoua and Thames. Associated minerals are!
    pyrltel marcasiter chalcqrpite, sphalerite and arsenopyrite at Te Ahumata,
    pyrite at Wtrargapoua and barite at Thames.

    11. Barite
    In addition to the previowly mentioned occurrences of barite r.d-th
    gold - sjl-ver mineralisation at Broken fli'l'ls and Thamesl and sitibnite
    rnineralisation at Thames, barite also occr:rs as late stage coatings on
    vug quartz in vei-ns betr'leen Tapu and Thames and those at Thames, Tui }ljle
    and l'faiorongcnai. The barite occurs as large platy crXrstals (FiSs 4-9
    and 4-34)r W to 30nm long at Tui lline (Anstu, 19?5).

    t2. Cinnabar
    Cirrrabar occurs as thjn coatings on rmg quartz crystals and fracture
    snrfaces in veins at Tharnes (l.Ierchant, L978) 1 Olharoa (Morgan, tgzt+), I\ri
    Mine (Wodzicki & lieissbergr 1970) and l{aiorongornai (Henderson & Bartrrnr19l3).
    Cinnabar deposits occur associated with a number of sjJ-iceous silter
    formations around llackayLovrn (Karangahake Gorge) and in the Karraeranga
    Val1ey (east of Thanes).

    0xidation and Secondary En{ichment

    Introduction
    The geologists of the early 1909ts placed great importance on the
    presence of oxidation in the veins of the Hauraki GoId - Silver Provincer.
    many believing that the bonanza ores were products of secondary enri.chment.
    The bonanza ore zone at Thanes was perhaps the principal example, occumilg
    near the surface and havjng a fairly level lor.rer surface. Recently
    l,lerchant (rgZs) cornrincingry argued that this bonanza was forrTed by a
    boiling horizon in the hydrothermal s;rstem.
    A poor understanding of the processes of prirnary nrineralisation,
    oxidation and secondary enrichment and the typical rninerals for:ned by each
    process Ied to eonfusj-on in the early literature over the origins of the
    various forms of mineralisation, I.lorgan (tgU) in his study of the llaihi
    deposit considered scrne rich prirnary ore canpris5lg pSrite, sphalerite,
    galena ana cLlcopSrite as secondary naterial formed by the actioar of
    descending r+ater.
    91

    The early geologists identified t'oxidised oretr by the absence of


    primary sr,:lphides (".g. ppite, cha-lcoplrite, sphalerite and galena) and
    the presence of quartz pseudanorphs after calcite, supergene minerals
    such as covellite and chalcocite ancl oxides of iron and rnanganese. These
    occurred in sane deposits dotrn to very deep levels, for e:<ample oridised
    ore was recognised frcrn 13 level at i.Iaihi (n"u & ryaser, tgL2) and 11
    level at Karangahake (Henderson & Bartrum, tgt3). This orrldation r,ras
    attributed to the action of descen*ing water scrne considerable tjme after
    mineralisation and the depth of oxldation was believed to reflect the
    topography at the tjme of oxldation.
    The nrinerals and featr:res attributed to oxidation and seconda:1r
    enrj.chment by the early writers are divided here into for separate events
    as follovrs:
    (1) llydrothermal leaching Hypogene
    (2) Srrlphide replacement Combfuation h;rpogene-
    (3) Solution and reCepositi.on supergene
    (4) Post mining mineralisation Supergene

    HyCrothenaal Leaching
    Platy or lamel-lar quartz, temed trquartz pseudomorphs after celsitstt,
    was a najor gangue constituent jn many of the nines in the prorince
    (".g. lir:aotu:eur'Komata, GoLden Cross, l{aitekauri, [laratoto, iiaihi and
    Karangahake) and r,ras considered by the early geologists (e.g. BeIL & tr?aser,
    t)tzi Henderson & Barbn"rrn, LgLS) to be a replacement feature of quarbz
    after calci-te.
    Ilorgan (1921+) suggested that this interpretation was incorrect and
    that the feature was actrlally a qtrartz plus calcite j:rtergrorLh frorn which
    the calcite had been subsequently leached out by.oxidation.
    l.fairr (1971) demonstrated that Morganrs explanation was possible by
    dissokjng orLr rvith acid, the calcite from a block of Srntergrorn qr:artz
    and calcite taken from the I'laratoto Mi:ne. The resrrlting rock exhibited
    the sane platy qrrartz tercbrre typical of the quartz pseudcnorphs after
    ca]-ctte.
    The vriter basically agrees with l.lorgants interpretation but considers
    that in many (most ?) cases the leaching was not due to supergene oxidation
    hrt rather to hSpogene hydrothen:na1 leachilg caused by changes il pl{ or a
    decrease in temperatr:re of the hydrothermal fluid (tne tatter effect
    increases the solubility of calcite in the hydrothermal fluid at
    fCO2 < 1 molal; Holland, L979). This ls supported by several instances of
    vug qtrartz crXrstals occurring on the platy qr:artz, haviag been deposited
    ,98

    g!'t tjt'
    lt-tblfi il-9: gffitr6Er acoondary liast.fls ln t|rc dapostti,of.tlii ta-trrali! @la'tlsBrP'!6t1ns!
    tq{utF
    grobdbl: prl'ta* rdner'aJ,s tlo oli{rS clrbf rgttl dlG4]l|.d'

    P,tltnatY
    Sg9onArrl/ |{lnefal

    Urhafrs SliictEs $IFhi'!'r tre3rv' cicocnt


    drrarail
    Fr terly gold ('U
    eold..lcct'run ilair..ta Fld (al

    Ag qerlrrgflAta rire rllrrr'fn',


    lc.l|thlt- El; ecale rilvcrf"
    Bclittr EyPoffirlt

    Bt
    gViite llrcnl,-tc tiiirJce Joroa*ir
    (rEoctlil'tclL

    'Cu
    nalachi.,a' Araf.Caqtltttc dhqfisgoollq AatJvr' oqCnnr {Cl
    Ghalcogyrite cepritr
    azqlitr
    &i
    s,lrelettte 6d,th.oiiltc
    ?b
    Gatqt. otrotlta anglcbltc

    llE Dltr'gaF{t
    'l
    ihodoelrrrritc py.rrt'l|!..!tc
    llrrlgaFlt E6uE tEllonel.ll.
    catrciia sgd

    ocsusr.r'tdtar l1;, &Fer iaw& Itllttl .l-4!.", Trrtbl


    (,Al Gotdia a![qr' isEcmat Bfl1 ltinql o[ nanbf i'
    G5, t(*s.b9llilihq a6d rlthi
    tll d*rGt |lrd ru! U-!q.
    93
    there after remorral of the cal-cite (c.f. Fig. 2 of plate ff facing paEe 9
    of Morgan, L92l+i and epi.morphous quarLz after calcite of Ramsay, LITL).
    The hydrothermal, leaching stage, which seems to be cofinnon to moet veins
    contain:i-ng abundant ealciter msy in some cases be related to precious metaL
    deposition, Although leached caleite was conmon-ly associated with the ore
    in inany mines the appeara"nce of prirnary carcite in the veins often
    signified the end of econqnic mining (",g. Golden Crossr Komatal r,{aitekauri
    andl to a lesser extent, the Talisstan Mine at Karangahake).

    Sulphide Replacenent
    l,iost of the sulphide mjleralisatj-on in the provilce exhibiLs supergene
    replacenent to varyl-ng degrees, viz. replacement of chalcopyrite,
    sphaleri'"e and ga]ena by chalcociter covellite and bornite. Chalcocite
    and coyellite are the predorninant products, bornite onJ-y having been
    recordecl at a fevr locations (u,g. Petote Stream, Irlaraiot,o and liarangahake).
    A less frecluently obsenred replacement is that of stib,nite in the
    Te ihurrata, Coromandel and thanes areas by kenresite (Ransay, l97Li Flaser
    & Ariaq'rs, t)A7i and Flaser, 1!1O respectively).
    These replacements nray have occurred during the waning hydrothermal
    siages or by cold gror:nd uater.

    Solrttion and Redeposi'r,ion


    The prominent effects of oxidation are the solu'rion of priroary nnjnerals
    and subsequent <leposition of secondary oxides, earbonates, sulphates anri
    native elements. Table 4-9 lists the conmon secondari'ninerals reported
    from tire province by previous workers and the primary ninerals from rr'hich
    their metal]ic eonstituents r,rere derived. In addition the follcwing
    ninerals have also been cited and occur i:r rare quantibies in the areas
    U-stedc
    Arsenoli-te, orpinent and realgar: lokatea l,line, Corsnandel (Fbaser t-. Ada^rilsl
    i907) derived at this locality from native arsenic. Orpiment and realgar
    also occur at Te thunrata (Ransay, t97ti Erceg, 1931)

    l(erarg;rritel l{aikorsniko Valley, Corcrnandel- (fraser & ;dans, 19O?) and


    Talisman liine, Karangahake (Henderson & Bartrun, 1913).

    Cervantite, dioptase and melaconite: Tapu - Tharaes and lhanres (F?aser, 1910).

    Bromargyrite and iodargrite; Talisnran l{ine, I(arangahake (lienderson & Bartrwlr,


    Lgt3) r

    Stilpnonelane:'daihi (Morgan, L92h).


    9l+

    Flgurc 4-35: Stalaqtltes, of ltuontte grorn fron the roof of the nLua tuauel by
    grouarl satsr sepage glnee ulnlng operatlons oeaacd. Vulean 4[ (468u)
    levdr llalorongoaal.
    95
    Greenockite, hauleyite, tenorite, osarizawaite, linarite, beaverite,
    serpierites <ievilIi-ne and duiedasite: Tui lline (Ansi.n, tg75).
    I

    l.lost of the solution and redeposition featur"" ,nu* formed by


    weathering and circulating ground water, however a few may a-lso have
    occured duning late hydrothermal stages. The solution of mangan:iferous
    calcite and rhodochrosite with subsequent deposition of pyrolusite are
    parbly placed into this lasi catagory.

    Post l.lining llineraljsation


    Lfunonite (goethite), epsomite, mirabilite, chalcanthite, manganese
    oxides and various tqrdrous ah:nin:iun and iron sulphates (u.g. melanterite)
    vrere reported by tr"raser & Adams (1907), rYaser (1g1O), BeIL & rlaser (1912),
    Henderson & Barbrum (1913) I t,{organ (7921) and Ansjn (tg?5) to form coatings
    on walls of abandoned sections of the miness having precipitated froo the
    mine h'aters after mining had ceased in those sections. In'places limonite, _

    chalcanthite r and the hydrou^s aluminirrn and iron sulphates formed


    stalactites and stalagmites in the tunnels. Iag. h-35 i'llustrates
    stalactites of limonite encountered by the r,rriter jrr the Vulcan l-sw leve1
    (lA, 46Sr) of llaiorongcrnai.

    Secondary Enrichment
    Although marqr of the miles exlr:tbit a weathered and leached upper zone
    (".g. Maratoto, c.f. lfai:rr -L979) the degree of secondary enrichment i.rn
    preciou,s metals below this zone is probably much less than srrggested by
    the early writers.
    Leafy and mustard gold and lri-re and scale silver were probably formed
    by secondary enrichment but these are not ccrffnon jn the mines where they
    were recorded ('Oolden Cross; Waihi and Karangahake) and large scale secondary
    enrichment is negated by the fact that (as far as can be ascertained). rnost
    of the gold mined from the upper iloxid:isedtt zones nas electrum containjng
    quantities of silver indicative of prinary deposi-tion by hydrothermal
    solutions (c.f. Appendi:c V).
    SirniJarlyr the degree of leachjng implied by the early reports nay also
    be exaggerated. For example, the oxi-dised near surface or of the Marb,ha
    l'tine (Waj}ti) contained p;rrite and acanthite in addition to electnrm but vras
    considered to be very leached because other sulphides lrere absent. The
    absence of chal-coptrrite, sphalerite and gal-ena tras probably because ihey
    were not deposited there in the first place.
    ^t
    vo

    CHAPTER 5

    I.I]NERAL CH3T.TISI?Y

    Ii{.TRODUCTIC}J

    Analyses of minerals made vrith the electron probe micro analy-ser


    (feUl) during this study are listed with a description of the analybical
    conditions i-n,rppendix fI and discussed in the following sections in
    alphabeiical order. 'nlhere possible discussion is based on averages of between
    2 ancl 2j analyses of the speciJie minera]. in an individual sample.
    EPITIA analyses of minerals from the Hauraki Gold - Silver Prsui:rce

    determjned by previous workers are detaiJ.ed in Table 5-1 and a.l.so discussed
    in the fol-lowilg sections where apprqrriate.

    A.CA}ITHIE - ARGEITTITtr

    Acanthite and argentite are polynorphs of :iES, AerS is deposited in


    most hydrotlrenral deposits as argentite, but on cooling below L?7oC inverts
    to acanthite. Therefore Ae2S observed in sanples at roorn tenperature is
    acanthite and is termed so here although it is reported jt the early
    literattrre on the prwince (e.g. Geologicat Sr.rrrrey Bulletires) as argentite.
    The acanthites analysed here are selen:iferous (Tabte 54) 1 leading
    l,iain (1971) and l,tain et al- (tgZZ) to incorrectly suggest that aguilarite
    (AgrSeS) uas the predomirant silver mineral in the Camoola Vein of llaratoto
    (aguilarite was nob identified by the writer).
    Trvo analyses of the Se content of acanthite in sam5rle 285/3?/S (t't lZ)
    were quite different (o.t3 and 3.11 vft. {o Se), rvhi]-e in saqlle 14043 (i{h 35)
    two different populations of acanttrite occur, one with an average Se content
    of 1.OO wt,. /o (range of 3 analyss = 0.96 - 1,05 wu. 'fi) *d the other
    averaging 7.33 w1-. I se (range of 6 analyses = 6.50 - 9.73 w1-. fo).
    Keift & Oen (1973) reported that acanthite frcrn Sal.ida, Indonesia
    contains up to t*f" 5", uhereas Shikazono ( 19?S) reported acanthites trith up
    to 1C.O9 wt. ',t'Se from Japanese ore deposits.
    Petrr:k et a! (r97L) in a study of naurnannite (AESe), aguilarite and
    acanthite proposed that the solubility limit of Se in acanthite is approxirnately
    4.? wL. ;/o Se; higher concentrations, up to 11.1 wt $were considered to be
    caused by an acanthite - aguilarite 5.ntergrcx*th, They suggested that the
    single phase aguilarite should contajn at least !3.2 r,tt,. (o Se.
    *pplying thj.s classification to the sanples listed in Table J-2, t.he
    hielrly seleniferous population of acanthite in sample. t49l+3 (5.5O - 9.73
    wt. 1L Se) represents an aguilarite - acanthite intergrowbh, sample 1,4A32
    97
    IABLE 5-1: Electron rlcroprobc an&ly!cs of Dl'nsrals of the Haurakl
    Gold - Sllver Provlaco lletatl t'n prevlouo vorkg.

    SPHALERITE
    Whangapouet Robron (19?9 p121 )
    Corouandel: Edrarilr 11979 p127)-
    Tapu-ThaEo s: Hercbant (1978 P9'l and P11!)

    ELECTRUH
    Te Ahuuatc: Raueay & f,obe (197L p149), Erceg (tgsr p:t)
    Broken f,lllo: oor (1976 p'114)
    l,f

    Tbau es: Hercbsot (19?S pp117 ar'd 15)l


    leavcsvllle: Torckler (19?8 p99)

    TEIRArEDRITE
    lfbangapoual Robaon (19?9 pltt)
    lhalca: Herchrnt (19?S pl29)

    HrscELLlilEOUS
    Ifortbcrn Grcat Barrler Ialenil:
    Idlal,tc, covclll.tcr chaleopyrltcrboraltc aad
    gaonaLous bornttc (Wclgcl 1978 511,-5751
    lfhangapoua: Pyrlte, uarcaelte aad aracnopyrlte pp107-108
    llargyrltc p110
    frelbcrgltc p1 14
    Robson
    fauatlnlte pl 17 ( 1 9?9)
    stlbnlte pl 18
    galena p123 )
    Brokcn Elllg: Pyrttc ppl10-111
    natlve allvcr pl1 7
    ecauthlte-equllarl.tcr agullarlts t l{oors
    (1 9?6)
    a gullarltc'raurEa!1t 9't26
    couplex gold-alLvcr arccnlg
    \
    aulpboaclenldca pp128,1i211 t,
    a;rd 115

    Theoes: Alklalte ond aclealfcrous


    tetradyoltc 979
    aelenlf eroua tclluroblaoutltc 'P81
    galela and sLlver btalutb tcllurlilcp84
    kobcllltc P88
    hceeltc p98 l{erehant
    (1978)
    rtutzltc - cuprcar!.tc pl 02
    altalte p1 07
    petrltc and coloradoltc pl 11
    chalcoetlbltc p121
    bournoaltc 912L
    robl.nronltc p'l28
    cnargltc p132
    pyrargyrltc aail polybaalts p1 54

    urlilqntlf led uiuerala pp89,1 03,109 ,


    12? and 155
    g8

    TAEI*E 5-?; ElecDroit Elcr'oPfob aualy$ea of acc.sthttssr


    Eaeb alelyala reppe.sente aa aqerBge of tbe
    aunbo,ry t-irdlcatedl. :fhe Lnatlflilual anaLysea a
    +t
    are li.sted l.n SpposAlx: fI. ,s
    +4
    .c
    o
    lleratoto seoplee | ' | ,u..lbl gegp,l.ee
    ----i,a6ai' '- S.-
    E
    zs5lttt.l? 28,5;13:?l'8
    (tll'lr) (a:r?) u't818t ul8t86 || lroll r-fithr5)-------
    (cJ9) Popu!.atloa a PoFulsttoa B, t
    e
    lualyaoa 1273163
    Ag 80.?2 fa5.?18, '85.1? 8{.94 89:'rI .- 81.56 96.51 0"10
    s 1.4102 72.99 12.58 11,,7'5 itll .65 9,08 12:.*L 0,.05

    9e 1.g4 1.62 2.63 3.87 1.67 7.71


    ' i i'00 o.li'
    'Gu 7.9, 0,,.18 Eo,E. ti:.,a. B.',4. il.E. Dra. 0.06
    As 1.8O 0,..02 sr,E. h.,4. u.a. tlo'8r il.a-e ,, 0'.08

    lu 0.58 0.63 g,oar tlrSr R.E. oirSr 0"20


    1.8.
    rortiat 9i8,.9.9 100..66 100.38 100.56 99.b 99.9T 99'95

    Ee
    lit,n. 7.94 0.13 2.9ts ?"'l'rr 1.1+5 6,.50 0.9i6
    ,!lax.g'e 1.94 ?.11 ?,?h 4.OB 5.11 9.'13 i.05
    D.a. = not analyaetl
    99

    TABLE .5-3t El,ectron rnloroprobe analyses -of


    p:yrrhotites and argentl-an trlentLandite.
    ' The pyrrhstf.te analys.es are averages
    qf the analyses presentedl in Appendix
    II a9 lndl.cated below.

    FyrrhotLte Lngentian FentLandlte


    Hiners l.{iners
    Head lfai,ht Head
    1?965 140/i0 13965
    (Ms1) (I,Ihz9) (Uttt ) Detectlon r;init
    Analtrrses 13 7 1

    Fe 59.70 58.19 36.57 0. 04 Fe

    s 39.35 99.72 31.1+2 0.05 s


    7'n D. &. 1.3,1+ 0.07 0.,05 7rn

    Cu 0,.1 5 0. ol 0.70 0,05 0u

    si. 0.05 0.00 18. ?6 o.04 l{1


    As 0,02 a'31 0.00 0,.08 A.s

    0o 4,.3,2 0.00 0.01 o"04 0o

    Ag 0-01 ll .8'r 1.3.52 0.10 Ag

    od 0. 0,0 Ilr&o Iil . 8. 0.08 od

    ?otal '9.9.61 1oo"17 1oo',49

    rf"gFo 0,.9t 0,92


    .
    Dr&. = not ena1ys,ed
    100

    (1r.45 - 5.L1 ni.. /, se) straddles the acanthite/acanthite - aguflarrte


    bor:ndary (t*.? *t,,,3 Se), and the l.taratoto sarnples (255/37n(C5)t 2Sj/3?/Sl
    l'{18185 and }!18186) fn addition to the Iow Se populatlon in sanple LhOtB
    (uh 35) are acanthites.
    The occumence of an acanthite - aguilarite intergro'rth hes been reportecl
    previously from the province by lioore (L976). He noted exunples of the fg1l
    range of speci-es j,:r the acanthite - naunannite solid solution series
    (acanthite, acanthite - aguilari.te intergro,rth, aguiJarite, agul1ari.te -
    nallmannite i:rtergrowth and naumannitel Petnrk E!_.4, Jg74) from the hoken
    Ili l'l s l.jine.
    Shikazono (19?B) :related the Se content of acanth:ite to the a#/aS
    ratio and f0, of the ore fluid. These factors are d:iscussed jn Chapter 11
    and Appendix V.

    iI"RGENTHI,I PEI'ITTAIiDI TE
    Argentian pentlandite (faU1e 5-3) occurs as tiny (up to 50 micranetres)
    inclusicrs jn chalcoplrrite frcrn l'liners Head (appendj-x I-.t). 'fhe miner:trl
    j-s a variety of pentlandite which contains up to 14.8 wb si.Iver
    !6 and has
    the general fcrmr:la (re ni)g+* Ag1_* sg (scott & c,asparrini, ag?3).
    The Miners lleaci occunence has the fo:rnula, U"5., Nk.5 OgS?.g
    Argenti.an pentlandite was first described, by Shishicin gt aI (f971) from
    two nassj-ve copper - ni-ckeL sulphide deposits and a nickel - cobalt skarn
    deposit in the u.s.s,n. and subsequently by vuorela:inen et at (tgZz) tron
    ortolcumpu - type copper surphide deposits and magnratic nicker - copper
    deposits in lllnland and b;r Scott & Gaspdrrini (tgZl) from massive nickel -
    copper sulphide deposits of metamorphic origin in the Bird Fiver area,
    l'lanitobar Canada. In these deposits (11 in aII), argentian pentlandite is
    generally found as jnclusions jn chalcoplrite. I,Igr-rral. pentland.ite may or
    nay not be present. Obher closely associated sulphides j-nclude pSrri.te;
    pprrhotite, sphalerite, galena and cubani.te. Argentian perrtlendite is the
    chief carier of silver in many of the,deposits.
    Scott & Gaspar{.ruri (tgll) suggested that because silver replaces iroa
    and nickel only in octahedrzl- and not tetrahedral sites of argentian
    pentlandite the mineral is a distinct specj.es and not a member of an
    isomorphous series with normal pentland.ite (as is probably the
    'rargentian
    pentlanditen deseri.bed frsn Sudbery by l.{itchener ljrl llavr1ey, tg62J which
    contained 3.8 wb / silver).
    ?Ire l"liners Head argentian pentlandite occurrence i-s interesting in
    that it ls the only nickeli.ferous mi.neral noted at this locality: even
    coexistirg pSarhobite has less than O.1i6 Ni (faUe 5-j).
    108

    TABTI 5-lrt llectro,n mieroptobo anaJ.yses of


    bisauthi.nite and tetradynite fno;n
    Tui liine (oaaple 17 15j, The
    bX.Ernuthl.n.lte a'ralydr 1s an ar/eraje
    of the '9 lrrdittidual anal.;rsee listerl
    i.n App,endix trtr.

    Blsnuthinite Tetradynite D,eto,ctlon


    Lnalys,es 9 1 L!.ait
    B1 77.86 60.,91 0. /i0
    s 1V.?4 l*.77 0.05
    Fb 3.67 0,00 0.0?
    Cu 7 .15 0.07 o. c6
    Te 0,04 32.1+4 0,1 0
    Fe 0.08 0'00 0 .0/i
    Se 0.00 0.00 0'.13

    TotaL 140.54 98.13

    .:''u
    -;4e-
    L t,
    .
    .-- ''

    :,. ?

    -.--;Cd*uiC."".1ril-**. -.- .+--' i, Jx,


    toz

    HISMUTH MTNER{I,S
    Bisnuthinite and tetradymiie (fabte 5-4) were analysed frqn the early
    stage mineralisation at Tui l.1i:re. The bismuthinite eontai.:rs an average of
    3.67 wl. i{ Pb ana 1.15 r.t. ;3 Cu, r'rhereas these elements are present in ].ow
    concentratiqns jn the tetrad;mite.
    l{erchant (1978) analyse<i several bismuth minerals (aikinite, kobellite,
    tellurobismutite ancl tetradymite) fronr early mineralisation in the vei-ns
    of the Tapu - Thanres area. Kobellites from thjs area have Sb/Bi r.ueight
    ratios between O.32 and 1.O5 r 2.2 - 5.5 wb. fo A,g and, O,B - L,8 lrt. % Cu,
    whereas Se is a significant component j.n the tellurobjsmutite (7.A - 8.3
    vf /") and tetradymite.(t.3 - 1.8 wL. /o).

    CHAIiCSPYHTry
    Qily a few analyses were rirade of chalcopyr:ites and they are listed jl
    Appendix II. l{ith the exception of the major elements and small qr:antities
    of arsenj.c and gold in scroe specinrensl the csncentrations of most other
    elements analysed rrere belol their detection Urnits.

    GAI,E[!\
    Table 5-5 lists average anal-lrses of galenas frqn Lf sanples,
    I,laxi.rnum recorded concentrations of Ag, Sb and Fe are each O.OB r";t ;'/,.
    Considering the detection limits these measurements are probably nob
    significant. Ttte occurrence of argenti-an galena suggested by Fraser & Adams
    (1997) frsn several veins in the Coromand.el area was therefore not confirned.
    Bi uas a].so analSrsed in the galenas and althorgh absoluLe values of
    concentration are no0 lgrqrn becawe of interference problems rrith Pb during
    analysis (Appendix II), very lor concentrations are indicated and are
    probably of a sinilar order to Ag, Sb and Fe.:'

    GOrp ANp SLECI?rJM


    Thepunity of gold i-s expressed ln terrns of fineness, which is the
    proporbion of pure gold in the sample in parts per thqusand. Silver is
    generally the most contrnon impurity and a further paraneter, true fineness,
    considers only the ratio of Au to Au + Ag:
    Au
    Truefinerse= Au+Ag x10OO (r-r1
    Gold containing Zff' or more silver (true fineness of 80O or less) is
    tenned electn:rn (Boy1e, !g7g). -
    Average analyses of gold and el-ectrum are presented in Table 5J.
    l4ost of the concentrations of S, Cu, Fe, As and Te reported in Table 5-5
    103

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    104

    are near or belqr their detectj.on limits and are therefore not significant,
    preventing conparison betr.reen samples.
    The concentratiqr of siJver i-s related to physicochemical conditions
    during electrun or gold deposition and j.s di.scussed in Appendjx v,
    Zonixg of silver concentration was not obsenred in the golct and electn:m
    analysed here but has been reported frqrr Te Ahr.rnata (nansay & Kobe , tgTL),
    llroken Hi'l'ls (l"ioore, t976) and Thames (I{erchant, tgTg). E']-ectrurn frqn
    the Iona Qhnrry at Te Ahrmata is zoned r,rith silver csrtent decreasi:r,g fron
    core to ti-n (52.4 and 15.6 -wt. fo Ag respectively), whereas electnrm fror
    the breccia pipe in 2IeveI of the hoken gi]ls }fine ls zoned in a reverse
    direction wj.th silver increasing frcm core to rtn (Zl and &r wb. /o Ag
    respectively). Elecinuo frorn the Norf,olk Mine, Thames, 5s zoned frqn
    76.7 Lo iO.9 wb. /o Ag but lvlerctrant failed to mention in wtrich direction.
    ,(fgZS)
    Zonilg, particularly that resulting i:r silver rd.ch rims, is
    generarly attributed to changes in phlrsicochemical conditi.qrs (e.g.
    tenrperatr:re and fS2) during electrrrm depositicr althorrgh a silver depleated
    ri-nc jrr electrr:m or gold may also be caused by seLective leaching of Ag
    during supergene or weathering processes.

    HESSIlE
    The hessite anal.;rseslisted in Tahle 5-? contain variable qpantities
    of arsen-ic (0.o9 lo o.J6 vL. i!) although the concentrati.on of this element
    appears to be much higher at 'i'Iaiorongcnai than l,laratoto. In contrast
    the llaratoto hessites contai.n smal*l quantities of gold. (W to O.I& v{t. ,4.")

    whi.ch are not present in the iiaioronganai hessites.

    Pl?JNg
    The analyses of a few pgites are listed in eppendix rr. As with
    chalcopy:r"iter with the exception of the major elements, onJ.y smetl qrrarrtlties
    of arsenic and gold are present in sqne specirnens in concentrations of
    significance.
    Moore (t976) reported variable quantities of gold. and arsenlc (trith
    maxjrnums of 1.12 and 1.O wt.'/' respectivefy) fu pyrite from Foken Hitls
    and l?obson (L979) deseribed pyrite - marcasite i^ntergrorrbhs associated ryith
    arsenqpYrite in the nrineralisatisn at i'Ihangapoua in lrhich the arsenic content
    of the pyrite and marcasite averaged 1O.8 wt. $. The latter is probably
    a resrrlt of i-ntergrowths with arsenoptrrrite.
    16
    TAB&E 5-?'l S'llsCtroa nlcropnobe analyrsea of
    heesi.teg. Each 44aly,ala nep:e',esen,t,s
    an a$eragg of tbe nunbe,r lndi.eatad.
    The indl.vldual analyses afte, llsted
    l.n Appendix I'I.

    I t*etoto
    c!
    Toka.tea lilaiorongomal o
    .rl Ul
    1409?' 14100
    Ilzas/n/2'2e5/37/6
    1 7961 +) +)
    (TK?) (1'r12) (l'r13) (uia3) (r{i98 ) Erl
    OF
    +t.d
    AnaLyeeo 11 55 3' e Fl
    {D

    Ag 69.03 62.?1 62''51;' 61 .24 50.97 0" 10


    Te 3'.1.o5 35.98 37.1,5 37 .71+ 38.98 0. 10
    s lI .{!. 0.1 6 0.11 0.1 ? 0.05 0.05
    0u XLrSr 0.01 0,00 0,20 0.01 0.05
    Fe D.,f,. 0.01 0.01 0.01 0,'00 0.04
    Atl R.flr ],42 a.39 0,05 0
    "00 0"10
    Ae f,i.4r 0.09 0.,08 a.56 a.25 0.08
    Se II .8r 0.20 0.00 0.00 0.1 3
    13,
    'Total 1 00.0E 1 00.58 1AA .25 1OCI.35 1 00. 06

    BrE. = Dot analysed

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    106

    Prn4gorrrE
    Pyrrhotite occurs naturally in hexagonall nronoclinic and rrsllorne'l srrsr
    forns. Hexagonal pyrrhotite (re,_x s) is the only pyrrhotite structure
    stable abwe 3O6oc. Thi,s structure persists to lower temperatures .for all
    but the most st-tlphrrr - rich pyrrhotite compositions. l,lonocli-:tic pyrrhotite
    ("u?** sg) is stable on-ly up ta 25hoc but may be netastable up to 3o8oc,
    r'rhereas ancrnalow pprhotite (ner** Sg) r^ras described by Clark (f956) fron
    lotr temperatwe sedimentary ernrironments.
    The pyrrhotites analysed frcrn tliners Head and'.{ai}ri (faUte 5-3) are
    believed to have formed at around tC5oC and 325oC respectively (see
    Chapters 5 and 9) .ttd i;ere thercfore deposited as hexagonal p;rrrhotite
    although they have compositi,oars close to the Fe?Sg of nronoclinic pyrrhorbite.
    Plnrhotite con'positions are generarly expressed in terms of mole
    fraction FeS (XF.S). Average values of this parameter for the l,iiners Head
    and i{aihi pyrrhotites are 0.94 and O.t2 respectively. The raole fraction
    of FeS in hexagonal pyrrhorbite is a frrnction of ternperature and fS, (Toulmin
    & Barbon, L95l+). These factors are discussed in Append.ix V where j.t j-s
    concluded that the i,IaiJri pyrrhotite is iron defficient for he,xa5onal
    pJtrhotite. It may therefore have inverted to nssnoelinic pSmrhotite.
    The minor element chemistry of the l4iners Head anci l{aihi pyrrhotites
    differ jn that Cu and Co are present in small quantities in the l'liners Head
    sarapler whereas As occurs in the i'iaihi sample. An average value of 1.34 vrb.
    ',/" 7-n ocaers in the i'ta-ihi pyrrhotite, considerably higher than the solubili!;,
    lixdt of o.yfi 7r$ (c.o? wt. f" zn) suggested, by Barton & skjnner (tgzg).
    This high zinc concentration may be related to the occurrence of the
    pyrrhotite as ilclu'sions in sphalerite. Sinrilarly the copper content in
    the l"liners Head pyrrhotite may be caused by its occumence surround.ed by
    chalcoplrite.

    SFI{.\].ERITE
    The /p average sphalerite analyses presented in Table 5-8 have tbe
    fo.Llor,ving ranges in conposition: 0.22 to tL,h.T
    'rtL. /, Fe, o.o! to o.66 wL. $
    Gd and 0.O5 to 1.35 wb. /" pn. little variation r.ras obsenred across grains
    and therefore ccnpositionar zonation is considered to be rnjnor.
    The iron content of sphalerite is a firnction of depositional temperature
    and fS, and is discr:ssed in Appendix V.
    Both the concentration of Cd and l.ln are quite variable, the latter
    exhibiting the greatest range. The i.iaihi sphalerites have particularly 1o.r
    concentrations of Cd relative to the obher samples.
    l'iith the exception of sanpre 2sjh7/6 (l,t 13) the ratio of cd/,h is fai.rly
    107

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    109

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    s#
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    #ge S-.o$ooll S6?"r


    q+qqql S.oqo to
    i
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    *16

    fr$3 $r{}.eol R.{ !lHa

    g *IS d 8l .F.1 ..t (rlr


    -Ht-
    $e$ s-
    ddsttl :,:..l.
    s 3f. ot

    '$,
    FrA lo,fl88S <<R"
    '{Gftt
    sgEEfi
    $g
    ro9

    T&Bts 5:-gi tulro ratiors of.ephalerltqs' fron


    the analy,sea l-isted tn Fable J,-8.

    aTerage
    Nuuber .of cdt
    slrerage 'l'fn
    aualvse,s :iatio
    Ml.nEars Head 1 T..T
    Te Ahunata, 1 2.,5

    Doct.ors Creek 1t 0.6


    SorrSr ldary Strea,u 1 4.'tr
    To&atea 1 0.5
    Fetote Strean Area & 2 7

    l"laratoto (Z:$SInI6 ex,oludect) 5 0.5


    Waltekaull- 2 0.9
    KarangahakE (t+oPl eountecl 2 A,L
    as 1)
    Walh1 5 4.2
    Trtl l{ine 5 5.7
    Walorougonai 7 2.h
    110

    consi-stent for sphalerites from the sane area (taUte 5-8) althongh quite
    varj-a.b1e frcrn one area to anoLher (faUte 5-g).
    the concentration of l,ln variecl syrnpa'r,hetically
    Nash ( t975) note<l th;:.t
    to that of Fe irr sphalerites from the l.rayflcnuer l{ine (wah, u.s.A.),
    however cor'rparisor of the Fe eontents and fe/ln ratios shol,rs that such a
    eorrelation i.s absent, ]rere,

    TSTRAHEDRTIE - TE}nE\NTTTE
    llinerals in the isomorphous series tetrahedrite (currsb4s13) -
    terrnantite (c5r.l,sr*sr:) may be classified usilg Td." varues where

    Z=
    moles Sb + moles As x 10O (s-21

    In th:is classification TdtOO = tetrahedrite and TdO = tennantite


    Table 5-10 lists average analSnses of tetrahedrite frqn Tui l,Iine and.
    i{ai-orcnrgonai together r,rith analyses frqn l.jhangapoua and Tbames
    reporbed by Robson (].g7g) and l'lerchant (1g?g) respectively. Both
    tetrahedrite and tennantite occur in the tui l.line mineralisation, whereas
    only tetrahedrite has been identified f:orn the other locations (faUte 5-1O).
    The ful lline tetrahedrite (Td95) and tennantite (Td1) are different grains
    vrithin the sane sample. ltre tetrahedrites frso the otber 1ocalities extribit
    some variation in their canrposition particr:larly at l{hangapoua where a range
    of at least rd6* to Tdr-oo is indicated by Robsonrs analyses (raute 5-1o).
    Zn and Fe contents of Thames, firi Mine and llaiorongcrnai tetrahed,rite -
    tennantite are s5rnilar, whereas Fe is substantially higher in l{hangapoua
    tetrahedrite: Zn was not analysed in the latter b3r Robson. tlne 7n/Fe ratio
    ranges from approxirnately 2 Lo 4 and is iadependent of the Sb/As ratio.
    A si.njJ-ar relationship was obsenred by l,iu & piterson (L7TT) in tetrahedrites
    fran the Casapalca vein deposit (penr).
    lihere anal;rsedr Nir l,ln and Cd are belcn+ their detection ].i.rnits.
    Ag is lor in the 'daiorongcrnai tetrahedrite (0.13 t*t. f) and fui lvline
    tennantite (0.t1 wL. i4) but between O.!O arLd 3.gl+ ttl,. j in other samples.
    Wu & Peterson (L977) considered that the silver cortent of tetrahedrite is
    related to the SbA" ratio (because Sb rich tetrahedrites can acccrnodate
    more siJ-ver in their crystal structure than Sb poor tetrahedrites) irut for
    any given SbAu ratio the silver content j-s also a fwrction of the aAg+ACu+
    activity ratio jn the hydrothermal fluids. The former relationship is
    obserrred between the tetrahedrite and tennantite of llri Lline and Robsonts
    I,'Ihangapoua tetrahedrite analyses but not orer rt'l the samples
    listed j:r
    Table 5-10. Apparently low Ag concentrations irr the l.Iaiorongcnai and
    iL11

    o
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    Garbo I'line (Thames) tetrahedrites rnay be related to the fluid chemistry.


    True argentian tetrahedrite or freibergite occurs at fe .{,humata
    (lg ranged between 13.8 ancl ZO.J r'ti.. /" ut Z analyses reported by fceg,
    1981) and I'lhangapoua (eg ranged between 15.2 and 1f.O r.it. ,.:t in 5 arralyses
    by Robsont 1979).

    GEot't{aFEio}.Efxy

    Tetrahedrite - Tennantite /Erargite


    - Fal'natinite Geotherrncmeter
    Feiss (t971+) proposed a geobhermqneter based on phase relatisrs withi:r
    the tetrahedrite - tennantite/enargite - fanatinite s;rstem (rig. 5-1).
    The compositiqrs of tetrahedrite and enarglte frcra the Australasian mine
    reported by Merchant (19?8), equivalent to tn23 (average)x and e1 91
    (singte analysis) respecti.vely, are plotted in Fig. 5-1. Robsonrs (19?9)
    tetrahedrite and fanratjnite analyses frcrn the tdhangapoua mineralisation
    are not plotted becau.se the famatinite has a conpositLon of en O and is
    therefore not suitable for geothermcrnetry (c,f. Fig. 5-1).
    Althouglt experirnental cal-ibration of the sSrstem is presently absent
    below 39OoC (nig. 5-1), Feiss (Lg74) mentioned a tetrahedrite - enargite
    pair (tn 1p - en p6 respectively) from Jr:,1-cani (Peru) for which a sulphur
    isotope temperature of 325oC ivas tentatively suggested. Gmrparjson of the
    position of this pair and that of the Thames tetrahedrite - enargite in
    Fig. 5-1 suggests that the Thames lni^r was probably also deposited at a
    terperatr:re around 325oC or perhaps sltghtly higlrer (llO - 3lOoC Z).

    l.linor Element Geotherrnqnetnr


    Bethke & Barton (fgZf) suggested geothermoneters based on the
    parbitioning of Cdr ltn and Se between coexisting sphalerite and gaJ-ena.
    Elecause the concentrations of these elements are generally lovr in galena
    (e.g. galenas anallmed by Nash l]g75l and Urabe LtgZZf had less than
    XOO ppm Cdi 22O ppm t'.{n and 5O ppn Se) they nnrst be analysed by sorne method

    with a higher sensltivity than EFI.A (e.g. AAS).


    Although such anal1rses lrere not nrade here, several sphalerite and galena
    pairs frqn firi I'line were analysed using wet chemical method.s by ?Jeissberg
    and others (Dr. B.G. -{eissberg pers. comm.) Uut the results (r:narrallable)

    * Footnote: tn values are adopted in this section to describe the


    cmposition of tetrahedrites in order to conform rsith
    their usage by Feiss (tg|L) tny=1Oo-Tdz $-3)
    Lt3

    s
    iq 50
    g
    o

    tTlwrrct/
    25
    {'lrr.r/ \rz - fan-td - n^

    |lolc 'h en

    Plgurc 5-lr Tctrahcdrltc-tsnnantltc and eaargltc-faeatlnltc geothonrouctcr


    (after letar, 1g7lr. Thc 325oC polnt 1g baeed on a oulfhur laotopa
    tenparaturc of a tetrahcilrlta-cnarg!.tc palr (tn.19-cn 96 rcs.pectlvcly)
    fron Julcanl (Psml. Te.trabcilrttc and enarglte froa thc Auetralesl.an
    lllnc at Tbalgr, analyaed by lletebaat, plot al 23 nole f tn - 91 nole-f en
    and l.udlcatc a teopcraturc of approx{netaly 330oC.

    $ffibtll,'.
    11r+

    sonflicting terlperatu,lres, Merchant (1gZg) however, reponted a


    gal,re
    tenperatur- of 39O t 15tC,for nqqganese paltlt:iqnfng between sphalerit$
    and galena f,rqr hi.s rlad - Zirrclt associatioe (J-ocati.qr. of sanples and,.
    ettarytical method were nst stratedl, @&nirrn partitlonlng gave
    tesp-enatwes around MjoC wtrich l.Ierchant considered un:reallstic.
    tL5

    CHAPTER 5

    FLI-IID INCLUSION $O4PHOLOGT, fltLLII'lG TEIvFER.rfu4E

    FESEZ:TNG TM,{PEFAflAE AIID SAIJNIIY

    ilfTEopucTToJ

    origin of flLuid inclusions and the theories and assurnptions used


    The
    jx flLuid ilch:sion research are discussed j-n several review papers by
    Roedder (tg6z, :rg67t t972t ]976 and t979)' '

    @tieal examiaation of ftuid inclusions requires the preparation of


    thjn transparent plates of suitable rninerals. In this study mainly quarbz
    and, calcite were used although a few samples of barite and sphalerite
    rEerealso analysed. The preparation techrriques are detailed in Appendix III.
    The inch.rsions studied contained liquid, vapour and rarelyr solid phases.
    Three ttrpes were recognised on the basj.s of the pro'portion of their volume
    occupied by the vapour phase: normaL < I+U/" < vapour rich < 9q, < ygPg
    S99.
    Primary and secondary fluid inclu.sions were identi-fied by the criteria
    suggested by Roedder (fgZ6). They lrere present jr most samples analysed.
    pseudosecondary jnclusions r.rere not differentiated frqn secondary inclusions'
    r.juarbz was found be the most suitable mj:reral for fJ-uid inclusion
    to
    stuclies lrith most sanples containing prjfiary inclusions. Caleiter although
    easj.ly prepared for anallris 1 was generally found to contain a high
    proporbion of seecndary inclusions. Prinary inclusions l.rere rare jn samples
    of sphalerite stud.ied, although secondary inclusions viere abundantr hence
    few results are presented frorn sphalerite samplesp Barite sanpl-es r,rere
    slightly better than sphalerite and their ease of preparation meant that
    large numbers of plates cou.ld be checked for selection of the few prirna4y
    inclusions anal.ysed.
    Drring the cor:rse of thi.s thesis the vrriter also investigated fluid
    inclusions in samples of quartz and calcite frcrn sqre Nevr Zealand and
    overseas geothermal field.s, under contract to [StR (reported in Christier
    19S0), In terms of size, shape, general occlrrrencer filU.ng temperaturet
    freezing temperature and, ccrnposition, the ffuid inclu.si.ons in the geoibhernral
    sarnples were very simiJ-ar to those in nuch of the material studied frqn the
    Hauraki GoId - Sifver Province.
    116

    Flgure 6-lt A'zone of prlnery vaPour f,l1'led Lnclualoae, nith aegatlvc cryetal
    ehaper I'n Stagc J quertz (aauptr'e '13922, of the Sllver Queen Vcl,ar llaratoto._
    6Jl.

    Fl$rrc 6-2r A eolltary prhary llqutd-vapour tnclualonr rl.th lrregular lhapc'


    !.a Stagc 2 quarta (anplc 11064) froa thc Charplon Vcir, Tul' llinc. 160X.
    117

    PRII,IAro I}TCLUSIONS

    Introductipn
    The primary inclusions studied range in size fron sub-microscopic
    to 2 rrun. They occupy cavities varying fran perfect negative crystals
    (rrs. 5-1) to irregular shapes (Fig. 64). Sorne are solitary (F'ig. 6-2)r
    iihereas otirers are aligned in groups alorrg gro*lth zones (nigs 6-t, 61
    and L{).
    The quantity and average size of primary inclusions i.:a sarnples varies
    geographically (Table 6.1). tuiaterial frqn Corsoandel, 'c{aiJri and l(arangahake
    r'ras found to be partieularly difficult to use, as the preparation of large
    nunbers of plates was required to find only a fevr small primary incluslons.
    Some sal'rp1es were abandoned altogether. In contrast, practically al'l
    samples examined fror boken Hills and NeavesvilJ.e (rhyolite host rock
    section) contairred scme prirnary inclusions and. many contained ttte:rb bookt'
    specirnens up to 2mm lcng. This phenonenon l'ras no't related to cr;rstal.
    size and appears no! to be di.rectly related to depth of fomation. However,
    ftuid inclrrsisr fomation is probably favoured by variations jn the rate
    of crtrnstal grorth and the presence of suspend,ed particles in the fluid,
    factors shich are probably in turn related to the flol* rate of the
    hydrothermal fluid. Ssne of the largest fluld inelusions (in noken lli'l'ls
    and Neavesrille samples) were formed u:rder boiJ-iq conditions (discussed
    later) indicatS-rig that the influence of vapoul bubbles ancl possibly
    turbulence nay al'so induce fluid inclusion for:nation.

    Vapour Rich apd Vapour ltilled Inclusions


    The samples containlng vapourrrich and vapour filled inclusions are
    noted in Tab1e 6-2, Bamples of vapour rich j,nclu.si.ons are j]'l.ustrated
    in Figs &-5 ana 6-5, whereas vapour fil'led inclusions ar sho"m in figs 6-1,
    6-7 and &. These inclusions trapped quantities of vapour a-long w'ith
    liquid indicating that the hydrobherrnal ftuid in r.rhich the host nineral
    grew was boiling.
    Vapour rich and vapour filled inclusions range in shape frsn j.rregrrlar
    to negative crystal and sqne e:camples of elongate inclusions, simiJ-ar to
    ftcylindricalf inclwions noted W Kamilli A Ohmoto (L977), occllr.
    Samples containing vapour rich andr/or vapour fil'lgd jnclusions
    predoninantly contain normal and vapour fil3-ed jnclusion t;pes, vapour rich
    types are rare and absent altogether frqn samples L39l+3 (N 39) and 140?9
    (i{i 41). The distinction of sample ].39113 may not be justified because the
    118

    '_ c f'..
    ^f a

    ,.L t
    r{: 't -?itf
    lrl t i
    'tirrt r.+

    FIgure 5-J: PrluarY llquld-vaPour lncluslong Ln nVr grovth zonsa near the tlp
    of a euhedral quartz crYatal frosr the Chanplon Veln (Stags 2), lul Mlne'
    (Sanpre 14,056) . x63.

    t
    i

    Flgure 6-tr,: Prlnary llquld-vapour lncluslone ln nVr grovth zonea near the ilp
    of a euhedral quartz crYatal froo the ChanPlon Vein (Stage 2), ?ul l{lne.
    (sarple 1{056). 40I.
    1rg

    IIABI,E 6-X.: @ograSihical rmr.ia. ion of p:linary f[11'1d i.neJ.usion


    elev.e[oSmerrt-

    ?il f- (i) B:rokE-n lli.trIs and Neavesvi-trle (.r*rtolite host' rock)


    "g
    E''d ltilt
    ..{ A'otr | .Miners lleadr K(mata **!, lfaitekauri
    +, I
    5 lrl ltiii
    flE? ) NearrcsviLle (andesite host rock), llaratotor
    n$t Itri ltine ar,rd $ra;lorongouai
    tn-lt'..tr |I
    f; | (i'l Ire Alnuata and Faritu
    HS,FI
    g gi | (nt eorroffiBdel (uotsatea and Fetote Sltlrgan areafr
    -(, (t rt{
    wanbl and Karahgalteke
    diD
    HG

    I
    L20
    ro
    I T
    E
    5a
    z .n

    -s
    t

    - a'\ tr- an cd O\ a.\ O rO F\ \O q, 6|\


    xE<d >. H(\ oN(\ldolct od
    H
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    fron I level of the Xouata f{lae' 2'0X'

    tlgure 6-6r A vapour rlch prlnary lnclualon ln guartz of aanple 1J9L6


    Golden lrrov Opcoeutr llaavelvllle. 160I'
    a

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    Flgure 6-?: VaPour fllled prloarY laclusl'ons Ln quarti of oarPle 13942
    AJax 1 level, lleavesvllle. 631.

    t b{

    6-8: Vapour fllleat prlnery laclualono !,u guartz ol oalple 1i95O frol 2

    lavel Brolseu lll'Ilg lllae. 160I.


    L26

    a
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    a
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    e l7i -

    Plgure 6-9: Elongate (-cyltndrlcal) prlnary fluld lncluslons ln quartz of


    aaople 13922 frou the Sllver Queen Veln (Stags 3) Haratoto. 160tr.

    Nr"$,

    Lr

    -' T
    'r t\-:
    .^\'
    I ).1
    t)

    Ftgurc 5-10: Elongatc ( lcyltndrtcal) prluary fluld lnclualona ln a dlffercnt


    part of tha aara eaoplc (1J922) as ahovn Ln Flg. 6- 9 . fif .
    t27

    nunber of plates prepared and. the number of inclusions checked, were ssla'lr,
    AIL the vapour filled inclwions nobed in sample Ll+O79 occur along a single
    plane separate frqn the norrnal. type i:lc1.ttsions. Therefore these vapsur
    filled inclusions rnay record on].y a single short boiJ-ing episode durfu
    the qr:artz depositlon.

    Zones of Elonqate Inclusions


    Zones of regularly shaped inch.lsions, mostly elongater occur in
    large vr:o; quartz crptal-s frcrn Maratoto (samples t39L9 and 7JJ?2). The
    elongate j.nclusions are orientated parallel to each other (f:g" 6-9 ana
    6-fO) and a set of crystal faces. One group occurs in a plane paraale3. to
    a crystal face (Fig. 6-11), although the elongate inclusions themselves
    are orientated paral'lel to a different set of crtrrstal faces. Other gror4ps
    occur in non-planar masses (fttgs 5-p and 5-10).
    Ilost of the inclusions are normal types buL a fel vapour rich and
    vapour fi]lsd tppes also oceur. The normal tlpes have sirnjlar filling
    temperatrrres but contajl liquid vrith a dlfferent (very lol) apparent
    salinittr' to i:regular shaped primary inclusi.ons oecr:ming outside the
    groups.

    SoIids
    Itany i.nc}.r,sions contain minuie specks of a clear solid (generally
    spindle shaped) adhering to the vapour bubble, and ther"efore generally
    nob nobiced, at rom temperature. On heating, these particles begin
    bouncing off the bubble into the liquld, increasing il frequency lrith
    jncreasj-ng temperature. l{hen the bubble disappears at the fillirrg
    temperatr.rre the bouncing motion ceases and the parti.cles adhere to the
    jnclusion lvalls or float gently around jn the liquid. Because they do not
    dissolve during filling temperature experiments these par-Licles are probably
    not darrglrber minerals but may have been tratrrpedr along with the liqtrld,
    duri-ng jrrclr.tsion grorbh.
    Inclusions j.n a few samples (faUte 6-2) contajn a highly biref,ringent
    fibrous mineral (nigs 6-12 and 6-ti). There is a considerable variation
    in the particle/inclusion ftuid volune ratio frqn one inclusion to andher
    and in many (mostf) primary inclusions of these samples the mineral is
    absent altogether. The mineral- remains unchanged during firling temperature
    e:perJrnents.
    Durjng contract work on modern geothermal samples for DSIR the vriter
    noted sjrnilar occurrences in samples frqn koadlands flf i'11 holes (ftg"
    5-t4 ana 6-t5). In one sample frqn Broadlands an i.nc].usi.on of the mineral
    128

    Flgurr 6-1f: I zoac of elongatc lndlurlone orlcntctcd parellel to a cryctel


    facc.(both horlroutal) aud cut by a zone of recondaty Lnclual.ona (vcrtl.cal
    la photograph). Thc long arcr of ibe eloagatc lncluelona arc orleatated
    to a illffcrcnt cryatel face frou.that paralleled by the ovcrell zoneo
    Quarta of eerplc 13j19t Staga 3 Canoola Velu' Hanatoto. &0f.

    Itgurc 6-12r Flbroua colld (ecrtslte?) !,n a prilery llquld-vaPour lnclualoa ol


    aarple f4O8t (quartr) frol the lfelcolc Vcinr lfalorongoual. 63OX.
    r2g

    1n

    It8urc 6-13: Flbroug solld pbarc ltr prhary ltquld-vapour tncluslon'a of aalplc
    1LO1L (quartr) lror Jubllec Lou Levelr Ualtekcurl. 160X.

    ptgura6-1{: llbrous ao1ld ln a llquld-vaPour lnclurloa ltr quarta frol a dcptb


    . of 680r ln Broadl'anilc drlllbolc 25- 25ol'
    Figu.rr6-tiir Ftbrour rllcre!,r Ln quartl (arrorcd) end fltlil lnsllurloan (alrort
    fltrtrlrg lnslurl,on lcar Isft eilga of nhotograph) ln a eao;rlc frol a iliptb
    of 8961 ln Eroedlaaila .drlllholb ?. . 250*.

    ft4rr. 6-,:!6! lleragonal aolld pharc tn a prlnary llquld-vePour tnslualon ln


    quertl of aauplc 1r91{ fror Golonlrt Sulthy lovcll lfal,onongonal,. 250t.
    t3L

    occursin quartz between two fluid inclusions a]-so containing the mjneral
    (fig. 6-Lr). This occurrence sr:ggests that solid inclusions were trapped.
    frcm the hydrothermal fJ.ui-d dr:ring quartz grorrbh and jn most cases acted as
    nuclei for trapping fluid inclusions. An included origin for the particles
    is consistent r,rith the obsewed wide variation of parti.cte/inctusion flrrid
    volume ratio which r.iould be difficult to rationaHse j.f the particles lvere
    daughter mi.:rerals.
    The appearance of the fibrous mileral is very sirnjJ.ar to crystals of
    dawsonite ltlartfCOr[0H]z) described from ff-uid irrcIusions in a number of
    ore deposits by Coveney & KeILy (1971), who eonsidered them to be a
    daughter mjneral. They noted that the inclusions containing dawsonite
    were of lor* sal.inlty (3.5 eq, wt. /, NaCf) and CO2 rich, generally containing
    srna'Il quantities of liquJ-d COr. Althotrgh the inclusions of samples studied
    here are of sirnilay s:'linity (see later section), liquid GO, has
    not been identifled and water and gas e>cLraction erperirnenfs rgith some
    samples indicate 1or CO, contents of approximately 1 mole S (see nexb
    chapter). Present day geotherma-l waters in the Broadlands fie1.d have C0,
    concentrations of approximately O,9 mole f".
    Kanilli & Ohrnoto (1977) reported the occunence of a similar fibrous
    mineral in fl-uid jgrc]-wions frcrn the Einlandia Vein, Centra]- Pe:rr. firey
    visr,rally identified the rnineral as dawsonite but found no rnore than 0.5
    ,zCO,, !n inclusions of the dawsonite-bearing sanples. This occurrence
    no]:e jl,
    of dawsonite and the fibrow rnjsreral' described in ihis study are sjmil.ar.
    Kanilli & Ohnoto noLe that t'the dawsonite/i.:rclusiori ftuid volune ratio
    varies markedly in ssne samples, In apparently cogenetic groups of
    inclusions with virtually the same salinities and hcnogenisaticn
    temperaturesr dawsonite daughters can be totally absent or canpletely filr
    the irrcluslon cavityt.
    Because of the 1or* CO, concentration, varidble parbicle/inclusion fluid
    vohme ratio, and solid inclusion occurrence in quartz of the Foadlande
    sanple, the fibrow particles fu ftuid inclusi.ons frcm the llauraki GoId-
    Silver Frovence, hoadlands geothermal field and ftLrrlandia vein are almqst
    certainly nsb dalrsonite but are probably a clay mineral (e,g. seri-cite) I
    included during crystal. gro*thr-which has acted as a nucleus for fluid
    inclu,sion fomatim.
    A clear hexagmral crystal is present in a single jnclusion of sarnple
    14101 (lii 100) fron llaiorongorai (tte. 6-f6). The crystal r^ras obsenred to
    change pos5.tion bet"reen successive fi'l'l ing temperature neasurements
    a-I',,hough no charges i:n size or shalr occurred.
    t32

    Flgura 7: A zona of secondary fluld lnclusiona (noat vapour fllled)


    5-1 1n
    barlts of aanple 1 4099 frou the Welcone Veln' Walorongonal. 1 60X

    Ftgure 6-18: A zone of seeondary fluld Lncluslons (centre of photograph) ln


    quartz of aanple 13922, Sllver Queen Vein (Staga 3) ' Maratoto. 40X.
    r33

    sEcolrpalrY il{clusTol{q
    Inclusions occurring jl cunred planes, often cross-cutti.ng zones of
    prirnary jnclusions, are regarded as secondary (1tigs 6-f? ana 6-18). They
    are generally smal1 (Iess than 50 mj.crsnetres) but sone La.rge secondary
    inclusions rvith an t'outlinefl (writers terrn) appearance occur jn clear zones
    of scrne crXrstals (nig. 6-L9). The latter are tabular jn shape and occur
    together 5l planar zones.
    Sonae plates of, calcite rvere forrnd to contain thousands of small
    secondary jnclusiors with no apparent systematic orientation. Sj:rnjJ-ar1y,
    Iarge numbers of tiny secondary inclusions occumed near the base of vug
    quartz crtrretals gin:tng this end of the crXrstal-s a nJJJ<y appearence in
    hand specifien.

    EILI.Ii\ni .( HOl.f0cEsE&\Tr0N) TIl!trlrut ruRE


    It is generally that the most accurate method of obtaining
    accepted
    the temperature of of ftuid jnclusions is .by the visue-l
    entralment
    obsenration of their fillfng or liquid - vapour hanogenisation ternperature
    (c.f. Roedder, tg75;L979). Thi.s parameter is measured by heatJng the sample
    i^n a nicroscqpe heatj:rg stage and obsenring the expansion of the rnajor phase
    (liquid in nonml tlrpe inc}:sions and usr:ally vapour il vapour rich tlpes).
    The temperaUure at r*hich the major phase eventually fi.Lls the inclusion
    after disappearance of the mjnor phase (vapour in normal tlrpe ilclusions
    and usualJ.y liquid il vapor:r ri.ch ttrpes) is the fiJting or horaogenisation
    temperatr:re.
    Fi[ing temperatures of vapour rich inclusions are di-fficrrlt to neasure
    because of the uncertai:rty 5:r establishing the point at which the last fiJ.m
    of liquid on the inclwion walls di,sappears. Becarrse of ttris the r'rriter
    nas unable to detemine hcnogenisation temperatur^es in the vapour phase of
    any of the vapour rich fluid inclusions stud:ied, and ar 1 fiJ-ling temperatures
    quoted are thus of hanogenisations in the liquid phase.
    Results of fluld inclusion ffJJing temperature measuernents made durj4g
    this stu{r are presented as histograrns in Appendix I and sunmarj.sed in Table
    6-e (tfre individr.ral measurements are tatnilated in, Append.ix III, together
    niih a description of the equipnent u.sed).
    As a grotpl prirnar;r ftuid jlclr:.sions have higher fiJlirrg temperatr:res
    than secondary inclwions although j:rdividuaJ- secondary inclusions may
    have higher fi'lljng temperatures than individual primary inclusions. In
    scme samples, the secondary incl-usions have a rui-de range of fi]lirg
    temperatures, frun prlnary temperature range (generally 2OO - 3@oC) Oorvn
    to approxi.rnately 1OOoC, but other samples (including manSr of those franl
    t9.ri

    .{\

    :t
    Gto
    V
    Ftrgqric6-19;: Sreoadery llqutd-vepour lncLurlsn:c sith 'an ioUtXlnoi a !pc!?enc'a'
    .serplc 1!949 (quartt) ftrsr 8 t.ewl o.f the lbnate tttac. 160x.
    t35

    Liaratorto, c.f. Appendix have narrow secondary filring ternperature


    III)
    rurnges with nrodes onJ-y 1O or 2OoC lor,rer than the prirnary inclusj.ons.
    Iiany secondary inclusions t'rith filting temperatures in the prifiar:r range
    nay be pseudosecondary j.nch.r.sions.

    oF EIITEAP}EI{T: BO]IJNG ENIIII9}0GjI{.7


    TE[.lPEF,iTt{rE
    pj]]fng temperatures of inclu,si-ons t'rapped on the boiling currre need
    no correction for pressure, however the relationship between tenrperature
    of entraprnent and filting temperature depends on the conditions of trappi.ng,
    6gni]"li & Ohmoto (t977) suggested that roinerals growjrg jn a boiling
    hydrothermal fluld nay trap, in separate j-nclusions, either randcrn
    prqrorfions of liquid and vapour (situation A) or fOAl fiqrriA in sorne
    jnclusions and 10@ vapour in others (sitriation B). (f) resrrlts il a
    pqlulation of inclusions with a wide range of liquid to trapour ratios,
    rr'hereas (B) results in two d'istinct populations of inclusiors, one with a
    high proportion of vapour and the obher c0ntajnjng a high pnoportion of
    liquid,. pilling tenperature measurements on the first seL of inclr:sions
    vlil'l result in an anomolously high temperatr:re rangei the ]-g!vest temperatr:re
    bejng closest to the temperature of entrapnent. EiILing ternperatures of a).l
    inclr:.sions :i" (B) r.rill be tenperatures of entratrment (vaporrr rich inclusj.ons
    r.i'ill be hornogenised in the vapor.r phase).
    The occunence of apparently nornal type ilclusions, vapour fil]ed
    iaclusions and a felv j-:rclusions with intermediate liquid to vapour ratios
    (vapour rich types) in the samples eonsidered here, srrggests that the
    inclusions rr'ere forrned under sitr:ation (rt). 6sni]]i & 0hmoto suggest
    taking the lowest firling temperature as the temperature of entratrxnent of
    these samples, however the peak of the filtjrrg temperature tristogram
    (Appendix I) is u.sed here for'the folloving reasorss
    1. fi]]fug temperatures r{ere detemined only fron inclusions that
    looked }iJce the normal tJpe,
    2. inclusions with jnterrned.iate liquid/vapour ratj.os (vapor.rr rich
    types) are rare,
    3. jn a"l] samples except 13922 (M 5) and t39h7 quartz (fm f5q) tfre
    scatter of resrrlts about the mode of the histogran is nct significarrtly
    greater than in fitling ter4oerature histograms ccnpiled fran samples fo::rned
    frqn ncnr-bolting fluids,
    and lr. in sqne samples rrsiag the lorest filling temperature rvorJ-d
    produce inconsistent resr:Its with samples forrned under non-boililg
    conditions frqa the ssrn arEr
    The rride filling temperature range recorded fran sampLe 13?2 (U 5)
    is anomalorrs whlchever sj.tuation is chosen. The wide ra-nge of filling
    temperatures is dlfficult to rationalise as a normal type inclusion
    distribution and is sr:ggestive of case (l) but the lolest fi't l iJtg
    temperature is inconsistent with bracketing sarnples jn the paragenesis.
    The depositional temperatures assigned to sarnples forrned wrder
    bolJ-ing conditions are listed in Table 6-2.

    BAERqTU"nB OF SiTRjql4Sm: NOII-BOIIJM Ei\MIROgt'tEIiT


    In samples deposited under non-boiling conditions the temperattre
    of entra;xnent of the inclusions is considered to be the peak (* mode) of the
    filLirrg ternperatu,re histogram (rfppendix f) with the addition of corrections
    for pressr.re and salinity (see belcw). The spreacl of values about the
    peak is consj.dered representative of the sanrple and on-ly partiq'lry due to
    experirnental eruor (t fOoC). Although sqne thick plates were used, the
    thermal gradients jltroduced are not large enough to contribr.rte
    significantly to ssre of the ranges of fi]ling tanrperatures obsenredt sqne
    sanples with very sma'l'l filling temperature ranges were measr:red on tluick
    platesr whereas others with large ranges were rneasured on thin plates. The
    w5.de temperature ranges may represent periodic temperature fluetr.ntions in
    tbe hydrothermal fluid or reflect the proximi.ty of depositional conditions
    to the boiling cur:ve. Ternperature changes between di-fferent growth zones
    could not be di-fferenti.ated on the histograns,
    The nagnitude of the pressure comection depends on the depth of
    deposition and whether the load was hydrostatic or lithostatic. These
    aspecte are discussed in Appendix I and, the values estjmated were used,
    together with the apparent salinity results (see later secticm) and data
    frqn }Iaas (19?1) and Pottet (L97?), to derive the pressr:re-salinity
    corections listed in Tab1e 6-2. They have been added to the modes of the
    fi]llrrg ternperature histograms to give the tenperatures of deposition also
    listed in Tab1e 6-2.

    DEPCITIOIqL m{PERT.TURES oF Sq{E lltNERrrt, ASSE"IBLA$


    fhe tenperature ranges of sme of the epithermal mjreeral assemblages
    discussed i:l Chapter 4 are listed in Table 5-3. They were conpiled by
    combinj.ng the assigned temperatures of deposition (t fOoC) for the relevant
    saryrles lj.sted in Table 6-2.

    rEstszlNG_TEI,FInArUnE
    Ihe freezing temperatures of inclusion fluids are neasured in a
    rnicroscgr freezing stage. Because of problerns of metastability, the
    liquid in fl,uid inclu^sions must be supercooled by generally 3OoC belo,r
    r37

    SAEIE 6-3: Predorrinant te4E]erAtules arrd aPparelxt sal.inities


    during detriosLtion of gome etrlithermaL rrein nineral
    as.flt- l.ages a$ indidated by the f,Luld inclns,isr daLa.
    The v'alues a,re a c+lFi-llation of the assigned
    dtepositd.onaL tenperatwe anil average qfi,parent salinltl'
    va.Itres Preeented in Table 5-2.

    DaPositj.onaI APIterent
    ftritbermatr w-j-n tr[i.nes.af Eetmperatuae SallniW
    aesemblage (oC)
    (eq. wt- t, !$aCL)
    Range Average Range Atterage

    2,, Early PYrnle 240 - 2,0 250 0.6 - 2-2 1.2


    4, Py-sp-grl-eP .

    a.sser6lage 220 - 310 28'O 0.7. - 4.6 2.O

    5. qy-s.p-grr-cFFel-Ag
    minerratr ass,emb&age 23O - 2'9O 274 0,a - 1"..4 o.8,
    6. $ir'-acallt&i.te:el
    assenblage 190 - 280 24A O.5 - ,3-7 r-1
    9. Au-.Ag sulPhosalt
    n'Lnerail assmbtragg, 23o - 240 240
    10. Stiltri-te Lgo - 2:3o 2il.o

    lL. Barlte 110 - 240 150


    L38

    the ice melting temperature to achieve ice nucleation. The freezing


    temperature is recorded as a rrlast point of i-ce meltingrt temperaturet
    measured blr varmlng the stpercooled inclusion, melting the ice and recording
    the temperature at which the last particle of ice melts'
    The rnethods used here, results and details of a freezing stage
    consf,ructed by the Victoria University Workshcp are given in Appendix IIf.
    r\o evidence for the formation of liquid COzr COz hydrates or l[a01
    hydrates was noted durjing the freezing temperature experiments.

    AFPAFSNT SAIJIiIry
    The freezing temperature results were converled to salinity val-ues
    by r:sing the equation in Potter et a]- (1978). They are presented as
    histograrns i.n Appendix I and sunnarised in Table 6.Z (tUe individual values
    are tabulated in Appendix III).
    The salinity ranges of ssne of the epitherma-l mineral assernblages
    discussed in Chapter 4 are listed in Table 6-3.
    DissoLved CO, also depresses the freezing po5:tt of solutionsr and
    its effects are discussed jn Chapter 7. llo corrections for dissolved
    CO, have been made and therefore the salinity results presented here are
    apparent salinities only.
    The histograms of primary fluid inclr:sion salinities presented i.:a
    Appendix I give the i.nrpression of wide ranges of sal-j:rity in the orig'inal
    tqydrothermal fluid, Althorgh factors such as experirnental error, variable
    qr:antities of CO, and low maxirnurn salinity probably account for this spread
    in salinity values for rnost eamplesr and trapping of boiJ.ing ftuid in sqne
    crbhers, several samples have high maxinum sal5aity and the spread in their
    values might reflect changes in the origjnal mineralising fldd. Variation
    ln sme aspects of fluid canposition durSng individual crystal grorrbh are
    jndLcated at Broadlands W the ctranging orygen isotope composition deseribed
    by Blattner (L975). Salinities may also varSr
    Secondaqr inclusions were found to'generalty have very lcu salinities
    compared to primary inclusions, wlth no measurable depression of freezing
    point in most samples. This elirninates the possibility of correlatiag
    secondary inclusisrs in samples early jn the lnragenetie sequence wlth
    prirnary jnclusions later in the seguence'
    t39

    CHAPIER 7

    OUANTITATII'E AI,IAI,YSIS OF INCTIJSION FT,IIIDS

    INTgODUCTION
    This chapter describes anatyses of the dissolved salts and COt present
    in fluid inclusions in samples of quartz and calcite frcrn the eptthermal
    deposits. ?he deuteriunr/nyarogen analyses of the inclusion water are
    described in Chapter 8.
    ?he experinental procedure wed generally follor*s the technique
    developed by Roedder et al (L963). The sample was crushed under vacuun to
    extract the nater and CO, for quantitative and isobqlic analSrsis. The
    crushed saraple r.ras remfited frqn the vacuum l-ine and l-eached rrith a solvent(s)
    to dissolve the irrc3-uslon salts. The leach was then chernically analysed
    and the concentrations of ions present proportioned baek to an original
    fltrld i:rclusion corposition by using the rneasurement of the we:ght of fluid
    inclusion r"rater extracted.
    t'uo major sources of error occur j:r these tlpes of analyses:
    (a) contarnination by solution of ions frcm the broken surfaces of the
    host minera1 or frcrn e4posed minufe soU.d irlelusicnes in the host mineral,
    ana (b) inco,rnplete leaching due to adsorption of inclusi-on ions onto the
    large surface of the crushed sample.
    These factors nay be criti.cal in arnlyses of dalute solutions yet ti:ey
    have received little attention in previ-ous studies. They were investigateti
    dr:ring this study by e:<perir,renting with di-fferent leaching rnethods and
    solutions. This led to the d:iscovery of major contamjnation by solution
    of ions frmr apparently pure host mi:eerals, a feature whieh has prerior:-sly
    not been assessed.

    THE CoNCEI\IIEATTON OF CrILORip,E ANp. SSE


    C"iTl0Nq li,l FilED INctUSlOi,F

    Proqedure and Resrllts


    of precision and accuracy
    The methods used, leach analyses and esti.mates
    are given in ipoendix IV. The analyses, recalculated to apparent ftuid
    inclusion liquid ccnpositions, are listed in Table 7-1.
    140

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    tc it,{3,
    cc c 8R
    9.
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    sgs
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    N9.Y -+s,o
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    ol d i i qrq
    iC:tC CCC
    Yrq
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    ERI
    r.\ c
    d

    !-
    c Fl-t gRs ssR sBg dd8 883 SrS Fa -l \(,
    Ol.{ (r\ td aaa
    cc6 g.ig
    dgE ;;$ '{{'rr\ .a
    CEC
    a
    98tr N Ca.l
    .td
    d
    6
    7

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    ald
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    cd
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    gpn .O\O (t| 888
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    o
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    c'qtil . rO @OO ONCtI .O Ch
    a6c q,atct 888
    -.|; 8sE B$A
    RRd
    oto\ aco rr'\{, dd dto
    6 - ('\d ..CO
    ctd
    dd d aaaoaa
    cctS c4c {t a^ tt\
    (\ld?a
    o (fr-
    AA

    rt
    dr!
    oo
    Ct. r1
    +,
    <14(.:) <reo <gl(, <trlt <tr|t, <Jll(t <gl(t <Elct <4l(' <gl(t
    Ad
    to \-/ \-- \-J
    rVt \-J + -+
    r{ *o,- t- *.*^^ t*a I
    EI -E*rogiESflac'
    +. - + . in *,
    .a 3t
    F.
    g&

    t
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    d
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    ,6

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    a
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    $E6
    t.!
    rceo
    4?
    s s E3 $g rE gR e5 88
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    4* c!{n {!fl dlf{ .{4{{ .{1fl .f!f" I .r'
    e
    !{t
    a
    Ao {st'o s.

    $ go
    $p S* frts i,f g: Rg
    For *o i3 g$ qElto
    ss
    !ta
    sgt E6..t
    94ilrt'
    ifu-lo
    Dr!,
    do
    EF.
    g s EE
    !.ld|a*|
    a.t e
    F} <e <!| <*l .{G| <F <P 4'Fl {q {gl 55sFc
    Fl C
    t
    f,
    \r'..! V r-d *-j r-rr V b. \f !h.J
    dt.tt
    s
    tt

    H
    F 'g ry'"s?
    .+++ os I*g *e'd rl
    aa
    dit
    3i
    w
    Experi.ments, }I!t4 Different Leaching Solutions

    Previous iiork
    I,iost previous norkers who exLracted and analysecl the salts frorn fluid
    inclusions used only wafer to leach their sanrples (c.f. Roedderr L972;
    Drjojir L972i Casadevall & Ohmotot L977; Kami]li & Ohnroto, 7977; Rabonet
    1977; l.ierchant, t978t i{eigel, L978i and Eastoe, 19?8), hoi'rever Czamanske
    et a (L963) and Puchner & HoLland (L965) used rraier followed by acid
    leaches (fql, m,lO, and 6t{ HCt respectively) in their investigations of hear,6r
    rnetal contents of fluid inclusions. The results of Czananske ef gl (L963)
    i.:ndicate that the majority of Cu and Zn i-s dissolved by the acid leaches
    in contrast to the behavior.rr of Na rihich Puchner & Holland (t966) showed
    to be almost conpletely ( > 9@) dissolved by the initial water leaches.
    Both studies shovred that I,In is also mainly dissolved in the vrater leaches
    but to a lesser e:cLent (7Oi,) than Na. Puchner & HoILand (1966) nere unable
    to detect Cu and Aa in any of their leaches and were therefore unabiLe to
    verify the results of Czamanske et al G953) for these ions.
    These results demonstrate that large ions and those with a h-igh charge
    are strongty held by adsorption onto the surfaces of the cnrshed mineral
    and a strongly ionised. solution is required to dissolve them.

    Development of the Procedure


    * single water leach r,;as useci on sa;npIe 13941b (N 14b) to test the
    leaching rnethod and to establish the concentration levels of varj.ous ions
    in tlre leach for the seLection of analybical methods and the preparation
    of appropriate standards. The leach contaj:red measr:rable quantities of
    rnajor ions (Tab1e IV-3 of Appendi:c IV) and in approximately the proportions
    encountered in studies of other epithermal deposits (e.g. Drjoji. t972i
    Casadev:.ll & Ohmoto, I977i Flerchant, 1978).
    Successive water leaches of samples 13958b (nO Zf; , Ll+O34 (l.Jh 5) and
    llG 5 shov that the initial nater leach dissolves practical'ly al'l the ions
    dissolvable i:r water (the high Ca and I{g values in the second sater leach
    of sample NG 5 are due to progressive solution of the calcite host mineral).
    tS, r*ric acid solution lras used to leach samples L3939 (Ufe; , t394la
    (N 14A) 1 139571(Tk 21), 139s0a (m ra), 1398ob (m rt), 1Jp8oc (as rc),
    IUA5L.a (rui 5a), 14O54b (I\ii 6b) and 1l+0?1 (ui 16) to d:issolve the ions held
    by adsorption onto the surfaces of the crushed sanrple, in addition to those
    which ttould be normal]y dlssolved by leaching with r{ater. These }eaches
    contained unrealistically high concentrations of Ca, A1 and Mg (taUfe 7-f)
    u.l,

    s
    f

    B
    /\
    \
    \

    tt

    J
    Lcach Leach
    d,
    ts
    zs
    =u

    i
    i!
    \\

    Flgure ?-1: Gsneral concentratlon trendg of lona leached frorn erushed aanplea
    of, quartz by aucceeslve leaches of rrater, snnonlun nltrate solutlon and
    nltrlc acld aolutlon: A, lfa+ anit Ll+ at lo.!t concentratlonS 8r l(+ of 1ow
    ncentratloni Mg2+ at
    tL )+
    lon concentratlon but Ga'- at lon to hlgh concentratloni D' Zn-' at lon
    concentratlon but AI3+ at lor to hlgh concentretloa; E' CI at lou
    eoncentratl,on.
    t45

    to be attribubed to a fluid inclusion source and indicate sqne conLanination


    hes occnrred. Agreement of ion:ic ratj.os bettleen ftduplicatet' samples
    (e.g. 1&0541 and LIaAJ[r) attd tf clearrt blan]cs (*ppendix IV) indicate that
    the source of contamination is in the sample (so1id inclusions or the
    sanrpJ.e itse1-f) and not due to experimental procedural problems.
    If uas evident that the nitric acici solution r'ias too strong a solvent
    and that an alternative ';ras required. Therefore a furbher batch of samples:
    t3gt+Lc (i',r 14c)r 13941d (i'i r+a), 13962 (80 3) | Lt+a37t (:*r 10r) and 140372
    lllir fOr) lrere erushed and. leached r,^rith water followed by Ll',t ammonium rritrate
    solution (neutral pH), This seemed to be satisfactory for the major ions blrt
    not Cs and Rb which were below their detection limits. A].so these leaches
    di.d not ind'icate the amount of contamination presenf.
    For a conplete arnlysis a scheme of three successive leach solutions
    (water, ammoniurn nitrate and nitric acid) r.ras adopted for all subsequent
    samples.

    Leaching Patterns
    The results of the multiple leach anal;rse-s (Tables IV-3 and f-L) show
    that five different patterns of behaviotrr occur (frg. 7-L). tla+ and. Li+
    (smalI ions with lovr charge) were mostly dissolved by the lEater J-eachesl
    the ammonium nitrate and nitri.c acid leaches generally dissolved
    progressively smal.ler arnounts (Fig. ?-1A). K+ (sDghtly larger ion) was
    nainly ,li,ssolved jn the ammoniu;n nitrate leach (Fig. ?-1B), whereas
    praetically all the Cs* and Rb+ remained untj.l the nitric acid. leach (nig.
    )-, c.
    |-LC), Cao- and l{g'- also followed the pattern show'n in Fig. ?-1C but at
    high concentrations inciicatilg progressive solution' of a contanJ.nating
    source. *13+ and ZnZ+ foiloled another pattern, shol.rn in F5-g. |-tDt trhereas
    CI- follovied thaf, sho.rn in F5-g. 7-!8. AI3+ and aJ* i.rr the water and nitric
    acid leaches are mainly frcrn contanination.

    I.dentification of Contaminants

    Quartz Analyses
    In order to determine the source of contaninaticrn in the leaches of
    crushed quartz crystals several samples of qtrartz were analysed by wet
    chemical and EFI'IA methods.
    Uncnrshed chips r'rere selected froa the leached samplest pondered,
    acid digested and the resulting solutions analysed by atcrnic absorption
    and flame ernission methods at Chemistry Divisiont DSIR. The results are
    presented in table ?-2. Several trace elementsr principally Ca, .{I and Li,
    Ll+6

    TABLE 7-2: The concentrations of some trace elements in the samples


    of quartz used for fluid inclusion analyses. ltte
    analyses were made by staff at Chemistry Division, D-S.f.R.'
    using atortic absorption and flame emission methods on
    solutions formed by acid digestion of the sartples.
    Sample Nunlcer Concentration in mS/kS (PPm)
    V.U.W. No. Field No. Location NaKCaAlMgLi

    L3957 TK2 Tokatea Tokatea Big 53 91 55 L620 13.3 150


    Reef
    13958 BO2 " Buffalo l{ine L27 52 59 2610 6.7 395

    13907 Hutt 2 Petote Stream Area, 79 22 51 1713 5.3 254


    Hutt Creek
    13980 ASI rr rr Aitken Stream 343 11 1660 2.5 22r
    13998 PS15 , rr Fetote Stream 71 18 59 1-379 6.9 L77
    14006 PS26 'r rr Petote Stream 32 67 370 L440 a.2 136
    139r0 wg9 Whangapoua, Waingaro 99 32 29 1759 6.8 224
    Stream
    13912 N40 Neavesville Ajax 2 L L2 I L7 85 3.4 L2

    I3938 N44 " AjaxIL I5 8 I8 121 3.2 24

    1394r N14 " Alax2L 26 435 25 633 6.9 27

    r3919 ,rg. Maratoto Camoola 3 L L2 19 48 160 9.0 11

    L3926 Ml0 . rr Silver Queen 3 L84 I6 279 1430 2.9 15r


    13928 M19 t' Camoola 3 L 25 30 27 1_150 4.L t79
    13948 Kml8 Komata, I Level L2 I L7 t24 3.4 L7

    14013 wK4 Waitekauri, Maoriland 19 22 46 252 A.2 22


    Vein
    L4034 wh5 Waihi No 5 Shaft 72 69 58 r153 4.4 189
    Mullock heaP
    14035 wh4 tl rrnllIt 37 t9 35 38 2.8 6

    14037 whlo tt
    llartha 3 L 66 62 100 496 7.6 57

    14054 Tui 6 Tui l4ine ChamPion 5 L 2L 34 40 62L 3.9 49

    14056 Tui 13 tl tt ll 180 L28 120 2L60 L9-2 209

    14059 Tui 19 ,l Ill 238 r35 L67 3040 36.4 277

    14071 wi16 Waiorongomai Canadian 43 7,4 62 90r 11.1 95


    Ck float
    14090 wL67 tl Main Vein L2 T2 20 110 5.1 T2

    14091 V'Ii80 tl It ll
    29 16 25 523 6.5 89

    L4094 wi89 ll Welcome " 75 15 19 2372 3.3 396

    14098 wi94 ll Inverness tt 70 20 34 IB89 4 -O 384


    Ll+l

    are present in consj.derable quantities.


    sampre.s L395L (rR 6) | L3973 (SM ?), 13980 (rS r; and 14102 (N 40)
    were analysed by iiPl,h (Tab.Le 7-3), The 3 micrometre diameter spots
    analysed r'iere found to eontain wiriely varyilg o^r:antities of .ll (O to
    33OO pprn). The EPM,I is not able to analyse Li and bhe other trace elementst
    if present, were belw their d.etection lirnits. Sarnp1es L395I (fn elt
    73973 (St,j 7) and 1398D (.{S 1) contain A1 disiributed throughout the quartzt
    t'rhereas ir1 vras not detecteo in Pl,lA analyses of sarnple LI..IOZ (N 4O). The
    average concentration of aluminiun 5n sample 139S0 (eS f) cletermined W 23
    ilPl''L1, analyses is similar to the concentration determined by r'iet chemj.cal

    analysis (tgzO pprn and 1650 ppnr respectively).


    These results suggest that in sorne sanples (e.g. 13980) ;tI may be held
    i:r the lattice structure of quarbz or distrj-buted throughout the quartz in
    nricroj-nclusions, whereas in other samples (e.g. 1[102) it occurs in snall
    solid mineral inclusions.

    Solid Inclusions ln Quartz


    FoJ-lowing the dlscorrery of unexpectedly high J.eveJ.s of sorne ions jn
    the qr,nrtz, thi.n sections nere made of uncrushed c4rstals frcrn some of the
    samples alaltrrsed (or*Iy a few samples contained sr.rfficient material for
    sectionin*s). Sarnple 14102 (tl aO) vras for:nd to contain smal] inclusions
    of sericite (confi:rmed by EPl.lA analysis), whereas three smalJ. grains of
    feldspar ? r'rere present in a thin section of sarple 13980 (iS 1). Horgan
    (t921+) reporbed that sericite was a csnmon constituent of quartz in the
    l'iaihi mine and I'lerchant (1978) suggested that it may be a contami.:rating
    source of h:is fluid inclusion analyses of quartz samples fron the Tapu -
    Thames and Thames areas.
    Polished plates of qr:artz (prepared for fluld jnclusi.on filIihg
    temperatr:re and freezing temperature exper5ments) frocr the same sairnples
    as used in the crushing and leaching experirnents are visibly free of possihle
    contarni$ants, horever plates of scrne orbher samples; Li95L (Tr 6), t3973
    ($1 7) and 14012 (lfd 3), conLaia solid inclnsions, In sample L3973 (St'{ ?)
    inelr:^sions of calcite (confirmed by EPI'IA analysis) are ali-gned.along a ilIFf
    growth zone near the apex of the crtrmtal (nigs f-2 and 7-3), vrhereas
    si:ni.lar inclusions occur along a healed fracture in sarnple !395L (Fie. |-ln).
    Fibres of an rrnidentified mineral (probably sericite) ocsur ln sample LI+OL?
    (F.ig 7-5). In a'l'l 6xaffples, mineral inclusions were obsenred 5-n only one
    plate of the dozen or so prepared for each sanple.
    The occurrence of a fibrous rnineralr probably sericitel in primary fluid
    r1l8

    TABra 7-3: coticefiE:rabioa of alurninlum (mglltg or FPm) in


    Euartz deterrtined by eLerct-on mi.groproUe railalyses
    (3 mrl:erorreter diarne,ter beant) .

    Saqple Nurnber [39i12 13951 r.397.3 13980


    (NAo) (rrR6) (sM7) (Asl)

    IfnalysSs Nunbet
    I n.el. n,d" 880 IO70
    ,2 tt.d,, (140) I_040 l9E0
    3 O. d. !t, d. 1130 1110
    4 n-d. n.d. r,!.d. tr280
    5 ti. d. Brd. ro40 10ao
    n.d. 1050 'a3,90 lgE0
    6,

    7 n.d. (?o) 930 (?oo)


    I n.d. n.d. 23'7.4 500
    9 !r. d. ,3000- 560 (L6,0)
    ,42,6
    lo 30,3'0 870
    [1. 590 ?.970 Aieo

    t2 L780 2444 243A

    L3 2L2,A 430 (rlol:


    1.4 I[.d. 3200 930
    I5 n.d.. 33lO 970
    16 n.d. .1560 350

    L7 n.d- 31,60

    r.8 3.570

    19 24LA

    20 29'trO

    2L 2524
    22 268o
    33 1730

    !{ean 690 1920 930

    Star,dacd dev:l,atiron L094 l-o6a 691!

    I.argest Varlue 3o30

    n.d. i= not deteeted de.tection limit a, 350 PFm


    Ll+9

    f-

    llgura ?-2: Incluslons of calclle along a rvr gronth 206o nar th6 apex
    quartz crystal fron sorry l,lary strear, Horthera colvllLe Penlasuae
    (sanple 13973). 63X.

    Flgure ?-3: Inclualone of calclte along a trVi grorth zone ln gua:rtz of


    oatple 13973' Slnllar vtes to FLg,. 7-2 but at higher nagnl,flcatlon
    dlfferent plane of focus. 160X.
    15o

    Flgure ?-lt Iaclualons of an uuLdantlfled ntneral ln a planar zone (healeil


    fracture?) ln a quartz crYstal fron 2 leve1 of the Broken llll'Is lllne
    (eaople 1)951r. 6fi'.

    f -.*,
    r\,

    Ptgure 7-51 Incluslona of an unlitentlflod flbrous nlneral (gerlclte?) ln


    quartz fron the Jubllee Lov LeveL oullock heap, Ifaltekaurl (eauPle
    1t012). 63r.
    L5t

    inclusions of many samples vras noted in the previou-s chapter (c.f. Figs
    5-12 and 6-ti). Thj.s mineral vrasidentified within flLuid inclwions of
    four of the analysed quartz samples t L3926 (M 10) , 7n28 (Uf9;, 14006
    (rs ee; and Ll+056 (fui 13).
    In view of the abcnre docrmented occurrenees of solids in the quartz
    cri"rstals and flui.d i-nclusions it is probably not unreasonable to assume
    'bhai, small quantities of any mi-neral, stable under the physicochemical
    conditj-ons prevailing at ihe tirne, could be i:rcluded jl the groviing quartz
    crystal. Therefore one or perhaps several of the corilnon gangue and wall
    rock alteration minerals; albite, adulari-ar serS-citer ctr-lorite, calcite,
    epidote, l<aoli.nite and zeolite may be present as j-nclusions in the quartz.

    EVidence Fron Previous ;rtork on lbace


    D-ement Compositions of quarbz

    (a) introd.uction
    Previous studies on trace elernents in quarbz indicate that apar{
    frorn their occurrence as mj.neral inclusions, smal1 quantities of A1$ and
    scme a].kali cations substitute for Sih in the lattice structure and
    larse quantities of various trace elements may occur as microinclusions
    of polycrystalline precipitates.

    (u) sutstitution of .{3+ for si&+


    Deer, Howie & Zussman (7963) reported several studies i:rdicating ti:at
    ?4 L .! r'
    AlF, balanced rrith lia+ and Li+, substitutes for Sis in the quartz lattice.
    Frarrl<-Kamenetslgr & Kanentsev (f96S) considered that A13+ isornorphously
    substitutes for Sih but that the charge bal.ancing al-kali eations are
    inserted into the voids of tbe qr:artz strrrcture. Stavrov et e! (1978)
    coneluded frorn their analyses of quartz samples fron J.gneous and hydrotherrnal
    vein envirorunents that Li+ is the major al.kal.i metal charge ccnpensator for
    Ar3+ in si4+ substitution.
    A1l substitution tor Sih forms the basis of the alumjniurn ir: quartz
    geoLhermometer of Denen et al (fpZO). However, the aluninium geotherrnometer
    was ernpirically based on samples with very lcrw concentrations of aluminiurn,
    for example fronr 200 to 3OOoC, the range of temperatures of deposition of
    the quartz samples analysed here, the geothermcrneter predicts corresponding
    aluminiurn concentrations betr,reen 50 and 8O ppm. Several recent studies
    have questioned the validity of the alumirriurn in qr:artz geothermooeter
    because like this study many of the samples they analysed contained
    L'2

    table ?-4: .COrlceRtratioa of daCO. in guartz sarq[es essqnslitlgr


    r (and
    ttrat all ttae eel.ciu$ magnesirnn) detpctgd i.n
    't'lre quartz analJres {raibXe 7-2} is p'r"esents as
    inclusions of calqie.
    SanPle Ntrober Apparent wt- !B

    V.U.vr. No. FieIE No. eaCO3 il quarr.tz

    13957 EK: 0.CI14


    13958 BO? 0,0x5
    13907 Hllfr 2 0-0L3
    L39EO ASL 0roo3
    1399 PSr.5 0.0r.5
    14006 P26 o.093
    139LO l[gg o.00,?
    139L2 N40 o.o04
    L39.38 .N1[4 ' 1'@.o05

    13941 NI4 o,006


    139[.9 !fi2 o.ol2
    ct
    1,3926 lrlo 0.o70-
    13928 Ml9 ,o,'007-

    tr3948 IftrLB o.o04


    140n3 t[K4 o.0 ..1.

    r403'4 liltr5: o.015


    ,0i.009
    !4035 M[4'
    [4037 nllrLO 0"025
    140J11 'fili 5 0.010
    1,40s6 Eui 13" o.030
    ' 0"042
    .1.4059 Tui r.9

    L40?t $ri16 o.015


    Lxl@90 w1-67 O.,0S5

    14,091 w,i80 0.006


    L4094 'wl89 0,,005
    lrto98 wi94 O.i009
    relatively high concentrations of alurninium. For exanplet Bronne &
    ilodzj-cki (tgZl) fourd up t,o 17O ppn Al irt hydrothennal quartz fron
    BroadlanCs, and Schotford (L975) reported analyses up to 549 pput A1 jrl
    sarnples of ciuartz fronr pegmatite and hydrothermal veins, Stavrov et aI
    (19?S) consj-d,ered that the quantity ofl,'tJ.h substltution for Sih l-q-,r""t"
    was primarily a function of the avaiJ-abillty of Li,+ (i.e. the concentration
    of Li-+ in the hydrobhermal fluid) and not tei-rperature. The upper
    concentration liroi.t of A13+ that may substitute for Si4+ in quartz is
    therefore not defined by the a}.minium 5-:n quartz geothermoneter and is
    unkr@{n.

    (c) tCicroinch.rsions of Polycrinstalline Preci.pltates


    Cherrrsv & Khadzhi (1968) identi.fied O.O4 micrqnetre di.ameter inclusions
    in quartz fomed by the segregation of Na+, whereas Elicstein & Schieber
    (1971+) reporbed 2 lo 30 mi-crqnetre d:iameter inclusions, containing -{Ir l"lgt
    Fe and Na, fron both natr:ral. and synthetic qr.rartz, The qr:artz analysed by
    Elicstein & Schieber contained a tota] of 23I..Ju_ p,pn A1 and tr@ pFrn l{8r
    attributed to the microj.nelusj.ons which in the natural quarbz conta5ned up
    to L5,28 r.r| /o A]-,, Lh.lt2 wt. fr !4g and 9.?t+wt. ,4Fe.

    Diseussion
    The trace element compositions of the quartz samples listed i:r Table
    J-2 are attributed to mineral j.::clusions, substitution of Sih in tfre
    qrrarbz lattj-ce Uy:.r,13+ and alkali metals, and also possibly their occurrence
    i.rt polycr;rsta'l 1 ine microinclusions.
    Ca and Mg are considered to occur mainly as jrtclwions of calcite
    (taUte 7-\), r*hereas (some) Na, K and AL occur as inclusions of sericite
    and feldspar. The best example of the latter i.s sample L39hl (N 1le) which
    has hi-gh concentrations of K but low concentrations of AIr Li and Na
    relative to the other samples. the Al/iC atomic ratio i-s approximaleLy 21
    jrrdicative of the presence of inclusisns of sericite which were identified
    in thin section.
    l,iost of the obher sarnples contain relatively high concentrations of
    [1, Li and ]tra but lcnv values of K precluding a sirnple balance t'rith rninerals
    such as sericite or ferdspar (Fig' 74)' Fig' 7-7A demonstrates that there
    is a conelation between the concentrations of il and Li suggesting
    substltution by these elenents for Sih in the quartz lattice, hosrever the
    Al:Li atomic ratio is too high (X.99:1) for a correct charge balance
    (i.e. 1:1). Ad.*ition of Na (fte. 74F) or Na + K (rag. 7-?c) to the
    L5l+

    Na
    2

    uq

    Flgurc ?-6: Ifelght ratto pl.ota of quartz treec elenenta and gone po aalble
    contaulaatlng nlneralgr the latter calculated fron enalyaes ( eone
    averagetl) ln the ll.terature (uatnly Deer g!3!' 1966). 1 . aduleria,
    2 . albltar 3 = chlorlte' 4 = chlorlte alayr 5 = epldot6' 6 = inter-
    layereil tlllie - ronttrorlllonlte (eerlclte), ? = Iepldollte, 8and9=
    dlfferant nuseovltesr 10 = paragonlte, 11 = ralraklte, and 12
    zlnealdlta. Apart fron eanple 13911 (arroued) the quertz ltace elenent
    cotpositlong do not balance atuply betnaen posel.ble nlneral contamlnante.
    Tbe trace elensrts of sanple 13941 oay be accountetl for by the prosence
    of esrlalte and calclte.
    t55
    70

    ooo.//
    /
    / ./
    w
    44
    A o at'
    n
    ar' .Fo 0
    ?0
    .r.t 8
    t0
    o //o
    o
    o
    N 40 @ 80 100 t20
    AI

    70

    @ o
    o oa"
    w -r" o
    (s
    z40 o./ o
    +
    B
    3n OJ ,{
    ?rtoo-o
    u ,/
    o /'o
    l0
    v
    /O
    o
    0; 60 t00 tU
    AI

    70

    @
    o ou"
    50 ./ ,to
    \/ ' o-tt-/ o
    +drt ..o'
    s
    z7o o .//o
    94o o
    /o
    '3 zo /
    t0 /o
    gy"
    @ 80 t00

    Al'

    (14
    Flgure ?-?: Grapba lllustrcthg tbc corrcletton betneen the ooncentrrtlons
    unl.ta of ppo/atollc ve!.ght) of Al anil eole alkall nstals t'a the
    quartz
    trace oldrent oonpooltions. tbe plotted llnesr regreaaloa tllcs tadlaats
    retlos of A, Al, oo:LL, (oorrclatLoa cocfflol'eat'0.911)l Br Alt.t-tr
    [r,r+u"] 1 (""tt.iiiloa'coefflcleot ' o'93?)'
    and G1 Al1.?2tlLi+tla+KJtr
    (corroletlon socfllslent ' 0'949) t
    L56

    OCJilOS rl N N r{ C{ N CU Ol

    Vanr\t \ocr\3 F-\o\o


    I
    tff
    'E
    CF.-
    C0)qt
    b,
    (f\
    (r
    gp$s3s3g
    "ii
    A i i
    tdhE 6 o rn \o \o c- ol ,'\ qr
    ss,E
    t{ +)
    ft 6 'o r{ Fr ,{ .: *cr\
    ..-r d O Ol.
    ei& }+ -+ { R {r.\S R R
    'Y g
    H,ig rr{. A d' X e
    ,38
    (l)Fl 4l^ :|.
    G
    5S;*8
    'd \SpSSSgR
    g) lri tc\ -$ =t N \O rn
    or O-O. T{ -i
    3
    d
    F h,d
    ,gBg,- o o o o o, -o
    *o5ct
    .Aatl
    .-tr d +l
    |
    d EgRgsgg
    c'\
    - -
    rl F{ Fl rn - -
    O\ rr\ O\
    {.l - - - (.,

    S.:i3oorl 5 t{ $
    ;.ijd
    'otboh Eo o
    t{
    *8.3 P
    .Fl tr .t.l 0,
    P ,:
    dFlg rr '!r{
    E_iJ_ot s
    $
    bFB= A ro r(r\ \J'
    'E (l)=|t| r'E rr
    = d
    t-H
    or.Fl
    .P.

    6+: Frl
    H
    '8P:'{ q
    -
    c-
    rn
    5
    .\i
    d
    fieEE ts
    Efrfr:
    6 gS
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    r{ I I -$ o F{ rn
    .^ -t -i c^
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    'frF: iq P
    F35cs ?:;gjR3B
    * rrF rr q) ? ? q
    o)
    +
    () .rl rf
    tv
    CY Fl fd{|
    ^rd AN
    E?dr $aoaaeBS.,-.E
    cBrS)4 Sf SR.uS^* g.q o*g f,
    .5'fE
    ir.e ' F: -i E"i
    "FE* E o o c) o o o o ;
    ltsfl PSFgSgHS l:i,u'i
    H
    EE
    igfr'ol
    dlddr{ c^ -t -
    R I
    - - - F cl

    A AO fr
    E 5 &- F
    ,B 5
    ot cn \o t\ cr1 o o\ o\ [ [ hb--bf
    :oh:F6
    S{OO>
    a "i d d .i d,i,.i .'i F, s{
    not!
    .H
    oF{ ol
    8t'd.""
    J E.t F -e. S
    R R cer 3I
    U}

    N N cv' R N S
    it N il ctt et
    I
    .9 d'* d
    (ntn!4()
    +) blld
    'illt' tr-.o * B
    rl
    ****Ol Cn -+
    :t n I
    -a
    Eg:E
    SIBE r{.":'
    .u 01 B
    H
    u)

    rn 33 Ed o q
    eE.rrrhl.gf
    I
    g5g
    EE gSF e!,F
    l-
    r{
    FI
    tq
    gL
    O}.r{r{Oh+a
    g
    a
    fl fiAg.EE&dE
    L5?

    alkal.i metal fraction irirprorres the charge ratio brt insufficiently for
    a correct baLance (l.f8tl and L.T2z1 respectively).
    Dr R.L. Goguel (pers. comm.) analysed sample 13980 (fS f) by infrared
    spectroscopy and found. that the Li+ is acconpanied by II+ indicating that
    the lattice substituti.on is A13+ balanced with Li+ + H*. Goguel (pers.
    comiir.) coneiders that because of their sr:rall size the ti+ anci Il+ are able
    to fit into the qr:artz tattice structure '."ith .,r13+, vihereas l,la+ and K* are
    too large and are therefore probabJ-y not significantly jnvolved in the
    substitution. Instead tbese latter ions probably occur in inclusions of
    minerals or as ni-crojnclusions of polycrystallj-ree precipitates }lke those
    obserrred by Elicstei.r:r & Schieber (19714).

    Esti.nration_of , Inclusijrn Cornrposition

    Introduction
    Because of the contamination it is evident that each leach
    probleras
    analysis must be assessed jndividr:ally to see if contanination has
    occurred and to what degree. The factors d:Lseu.ssed. i-n the folloring
    sections were used in this assessment.

    Chernistry of I'lodern Geothermal Eluids


    A general cherirical cornposition for the inclusion fluids may be
    predi.cted by cornparison rrith modern geothermal r*aters. Table ?-5 lists
    some analyses of rnodern geothermal waters. The analysis of Broadlandts
    r.rater is parLi-cularly relevant to this study because these waters have
    passed through and eqrrilibrated with similar roek types to those of the
    Hauraki Gold - Sjl-ver Province and they are actively preci.pitati.:ng base
    metals at depth and precious metals near the sr.rrface (c.f. tJeissberg gL"I,
    LgTg). .

    Several geotherrncneters and thermodynamic relationships based on the


    chemistry of geothermal vraters have been proposed by rvorkers in this field
    and srne of these have been used il previous fluid jnclusion cnrshing and
    leaching stu<ii.es to assess tlrc validity of their anallrses.
    The Na/K geotherrnometer has been applied successfirlly to many modertr
    geothemal waters (nlti5 & l.iahon, L977) i.:ndieating that the exchange
    reactionl
    K+ + Na-feldspar = K-fel-dspar + Na+ (?-1)
    descri-bing the interaction of the water with wa'|] rock mj.neral-ory, is a
    controlling factor on the water chemistry.
    158

    Howeverr r.iaters in some overseas geothermal fields


    contaj.n much
    higher concentraticns of calcium than the l{eu Zealand waters and their
    esnnositions were consid.ered by Fournier & Trues<lelL (1973) to be controlle<l
    by anobher reaction:
    li? + Irla*cau-feldspar + Ayqua r*z = K-feldspa* * + Saz+ (7-2)
    "ttL+
    l-ournier & Truesdale (1923) proposecl an empirical Na-K-Ca geothernoneter
    to take account of this reaction. These r,nters ';ith higher calcium
    concentratj-ons generally have 1o.,r I,ia/K ratios (compared rith those expected
    frcrn the Na/K geothermoneter) and are tlpically of high werall salirrity.
    In extreme examples, such as the Sa1ton Sea, California, calcir:n may beeone
    a major component (taUte 7-5).
    Recently, 6iggenbach (1981) proposed that i;he dminant reaction
    determining the chenistry of waters in geothermal systems of the llew
    zealand tlpe was the conversion of primary plagioclase by co, to form
    ealcite and clays:
    plagioclase + C0, = clay+ calcite (74)
    Taking j-nto accsrmt the di"fferent hydrothermal alteration zones and
    the various ehenrical processes acting rsj-thin theur (c.f. &retrrer & Heur1ey,
    Lg67i Rose & Burbr L979) the d:ifferent views eited above may be reconciled
    by considering that the reaction described by equation (7-1) predominates
    in the poiassic zone and in scme propylitic al-teration zones in which
    adularia j"s present, whereas in other propyliti.c zones the reaction
    descrj-bed by equation (?-3) predominates. The invoLvenent of calcium in the
    plagioclase reactions fe.g. equation (l-21] is not consicler.ed important here
    because the plagi-oclase feldspars present in rocks of the Hauraki Gold -
    Silver Province are not very calcic.
    Therefore althsugh the I'la/K geothermoneter may provid.e a guide to the
    water chemj.stry expected in fluid inclusions of the sarnpJ-es analysed here,
    it is nob universally applicable and exceptional Na/K ratios may occur.
    In surnmaryr i.f the fluids in inclusi-onshave formed by the sanre
    proeesses as modern geothermal waters with 1o.r CO, content,lor salinity
    incru,sions should have l.lar/K ratios j-n aceordance with the l{aA
    geothermaneier and Ca should be only a ninor constituent. Hore saline
    inclusions may have Ca as a inajor consiituent rvith concmritant lor !ia/K
    ratios and faiJ-r.rre of the lla/ii geothermorneter. The concentrations of l,lal
    K and Ca however r.rou].d expected to give sensible temperatr:res using
    be
    the Itra-K-Ca geothetmcmeter. Inclusions forrned frqn waters r+ith high C0,
    content nray have lla/K ratios quite different frcrn those ex;rected by
    canparison with the Na/K geothermcrneter yet have J-ow concentrations of Ca.
    L59

    Other cationsr nanely Ll, ltg, Cs and Bb, occur in very J-or.r soncentrations il
    in a-l1 cases.

    Charge Balance
    Uncontanrinated analyses should have an approximate charge balance
    of the major ions:
    (7-b)
    An exact balance is unlil<eIy because of the inaccuraeies in the
    rnethod and also because an excess positive charge may be balanced by SO,2-
    At+
    and HCor-, whereas an excess negative charge may be balanced, by caz+ etl,
    These factors corrld accor:nt for an enor of up to t tOO/o in equation (?-[).

    Leaching Patterns of Individrial Ions


    General leaching trends for the tlifferent isns in the mrrltiple leach
    analyses have .been describecl earlier (c.f. Fig. ?-1). Anallnes free of
    contaminatiqr should shool a progressive deerease in concentration from
    one leach to the next, except in the case of large ions an4 those with
    large charge which might be e:qgected, to rrhang ont' until one of the stronger
    solvents is used.
    The 6enerar patterns of lia, K, Rb, cs and cl are thought to be the
    behaviour of these ions ire contanination free analyses, vhereas the patterns
    of Cal ,l1 and ]ig are Lhought to jnrli-cate cqrtamination. Oeviation of lla,
    K and cI frm the general trends to one of progressive i.ncreasing
    concentration thror:.gh the successive leaches is eonsid.ered to indi.cate
    contaninatica:.

    cornparisonof ronie Ratios Betneen errartz and. Leach Anarlrses


    Corparison of ratios such as t"t/*t and t-tg/Ca of the quartz and ff.ui.d
    inclu.sion leach analyses may be used. to indicate jJ contaminatisr has
    occtrred. This method was not rigorously applied in the case of Na and K
    because of the rrncerbaj-nty of their locatj-on in the quartz. For exanple,
    if they are held as a result of substitution jn the guarbz 1attice or as
    late segregations in polycrystalline microinclusions it is conceivable
    that they may have been incorporated in the sarne ratios as in the parent
    hydrobhermal fluid.
    150

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    161

    Prediction of NaI K and Ca Contamj::ation


    by i.)uartz Trace Blement Ratios
    By assurning that the concentrations of i\1, lE and Li of the leaches
    are frorn contami:ration, their ppm values may be multiplied by the
    appropriate ratios (".g. ua[I , Na/Li.'t xf* ana ca^.ig) of "r,he o.uartz
    ';.n111,'ses to predict level-s of acconrpan;,rilg ltra, I{ and Ca contamination.

    Parbicles of the fj-brous ririneral, nobed frcnr fluid jnclusions in


    poiis!:ed plates prepared for fillisrg temperature and freezing ternperatr:re
    ivork, rnay not contribute significantly to the trace elernent ccrqrositions
    of the quartz but could be strong contaninants in the leaches. assuning
    these particles are sericite, K contami-nation jn the leaches frqm thi.s
    source can 'pe predi-cted by substituting the A1 values of the leaches in
    an average analysis of sericit,e.

    Conclusions
    The indica'.,ions and degree of contamination of the various leaches
    are discussed in Appendix fV and the parbiat fluid jnclusion analyses which
    are considered essentially free of contarnination are listed in Table 7-6.
    This investigati-on has dernonstrated that contamination frcrn the host
    mineral is a major problem in crushing and leaching experiments of lovi
    sali.nity fluid jnclusions. Single or multiple r*ater leaches have
    relatively high Ca, I4g1 Li and Zn concentrations although charge balance
    r+ith chloride is possible in rnany cases. Leaching t'rith solutions of
    anrnonium nitrate and nitric acid protres tha'r, the bulk of these concentraiions
    are frqn contamj:'ration by the host mileral. A test for this cortamination
    j-n waier leaches rnay be the concentration of alurninium.

    THS COS3EI'IT&IIT0N 0F CO2 il'I. FLqfD E'ICLUSIOI'IS

    I'Ieasurement
    The concentration of C0, jrr fluid inclusions itas detennjned for 16
    sarnples by nleasuri-ng the pressure of CO, in fhe vacuun line during
    cnrshing and water exbraction exper5ments described in Appendix IV. The
    results are listed in Tab1e 7-7.
    An esti.rnate of the precision of the C0, concentration measurements
    may be gained frqn the duplicate anal;rses of saq>Ies t3Q28 (U fp) t t4O37
    (l'lh 10) and 14O51 (trrt f9). Analyses of sample sets split according to
    their clarity (1394!t L3g5S and 13980; Appen<ii:< IV) may not be used for
    this pr::pose because any differences between the jndividuals in each set
    may be caused by d:ifferent proporti.ons of prirnary artd secondary fluid
    inclusiqr"s if the concentrationr of CO2 in each generation is different.
    r62

    TABLE 7-7: Concentration of CO, (mole t) measured from fluid


    inclusions, with an'indication of precision error
    (+ mole I Co2) calculated from the duplicate analyses
    of samples 13928(M19) ' 14037(vfhl0) and 14061(rui 19).

    C\
    o
    U
    r{
    oodp Fl
    +)^
    dtn o co
    ! E E O-lO
    '.{
    aE
    d
    g5 fld 'd-
    "d
    t o tU O t{
    (t.A m tr
    Sample Number d >t ('dp qr{o
    ooH
    v.u.w.No. Field No. Locatiom E t +lo

    r3957 wz Tol<atea Tokatea Big Reef 9 o.4 0.6


    r3958 BO2 I' Buffalo t4ine 7 o.5 0.8
    a
    BO2b
    nlllt 12 1.1 o.4
    L3962 RO3 " Royal oak !{ine 7 L 13 r.9 o-4
    r3907 Hutt 2 Petote Stream area; Hutt ereek I L.4 o.7
    r3980 AS1 r il ,t Aitken stream 22 o.7 0.1
    a
    N1. tl tl ,30 1.1 o.r
    13998 PS15 ll tl
    'r Petote Strean 6 o.7 0.8
    r3910 wg9 Whangapoua, Waingaro Stream I 2-O o.7
    13931 Nl6 Neavesville Ajax 2 L 29 o.4 0.L
    r3941 N14b
    Itrn 55 o.2 0.1
    tl N14
    ll fl It 2A o.2 0.I
    c
    13919 M2 Maratoto Camoola 3L 7 o.2 0.8
    q
    L3926 MIO " Silver Queen 3t 11 o.8 0.5
    r3928 M191 " Carnoola 3t 27 o.2 0.1
    tl Ml-g2 ll !l ll 15 0.4 o.2
    14035 wh4 Waihi No.5 Shaft mullock heaP 6 2.O 0.8
    L4037 wh101 ||llttllll 4 1.8 1.O
    n !'1hrol lr ll ll ll ll 2 4.L 1.1
    I40s1 Tui 13 Tui Mine ChamPion 5 L 18 o.8 0.1
    14061 Tui 19, Illfln T2 1.4 0.4
    tl firi 192 tl ll ll tl 20 o.7 0.r
    L4094 wi89 hlaiorongomai, Welcorne Vein 9 1.0 o.6
    L63

    The duplicate analyses exhibit a trend of increasj.ng apparent CO,


    concentration trith decreasing nater field which becomes more marked. in
    sarnples with lor.r vrater yield (i.e. A CA2 concentration increases dcrrn the
    seriest 1392$, 14061 and 1403?). 'flnis relationship rras usecl to eonstruct
    the Sraoh of precision error (mole ii CO2) versus i.iater y:ield irlustrated
    in the inset of Fig. f-8. The precision errors for the individual. analyses,
    cierj-ved from this curvel 3r listed in Table "l-7 arfi shor.n as eror bars
    in the plot of co, concentration versus water trderci (Fi.:.?-g).

    l.{aximun timits of COo Concentraiion E:termined


    2o_: to2

    Introduetion
    Urnits of CO, eoncentration can be estjmated by consld,eri-ng
    l'{axirnum
    Lhe phase relations in the sy-stem
    %o - coa at lcr temperature (rie. ?-9)
    in terrns of (a) the absence of liquid co, and (b) the absence of
    clathration during freezing temperatr:re e:<periraents.

    Absence of Ligrrid CO,


    Liquid co, was not obserrred in any fruid inclusions stud.ied by the
    vrriter and on-Iy one instance of its oecr:nence in the llauraki Gold -
    Silver Province has been reported previously: I'Ierchani (:.gZq descri.ired
    inclusj.cnrs in quartz from the Garbo t'tine (Karaka Creek, Thanes) containin3,
    by volume t 50 - 6CI;!" vater vapour, liquid water [2o - 35f, ?J and 15 - zo4"
    liquid co, and hornogenlsine irl the vapour phase at arormd. 33ooc.
    A mjlirnum pressure of 65 bars j.s necessary for liquid COz formati-orr.

    tu ftuid jnclusions at 25oC (nig. 71). DcbrapoLation of the solubiJity


    data of iliebe & Gaddy (rplo)' !.talinirr & saveryeva (tg7z) and Mari.:ejn &
    Kr.rrorskaya (tgZS) indicates that approxirnately.2.J mole f, caz (1.4 mores
    CO, Per kg of solution) rnay be dissolved in an O,2 mol.al. l{ac[ solution
    (average lda0l equivalent concentration for the solutions csnsj-dered. here)
    wtder 55 Uars pressure. The Ostr.rald d.istnibution coefficient at Z5oC is
    about O.8 (c,f. Fig. 3 of rll't1s & Goldring, W63) indicating that
    approximately 89i of the CO2 in the fluid. inclusion is dissohred in the
    liquid phase, whereas 20f; occurs in the vapou.r phase. Therefore a total
    CO, concentratiqr in excess of approxinately 3 rnole ;/o is requircd. to fonir
    liquid C02 in a fluid inclusion.
    t64

    C
    8
    -c
    U
    o
    r r.a
    \o
    L
    \'
    u
    ! Et o.t
    .9 o
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    mq walcr ytcld
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    t9

    t0

    o.o 0.6 lo t.2 w zo '?.2 2.4 Q.o 2'a *o t'2 ,'4 ,$ ,a 40


    l:'6
    Apr4;r conccrll771niorl ol COz rh Ftuid rhdusiong (mole'h COz)

    Flgure ?-8: Plot of oeasurcd COa conccntration vcraus the yleld of nater
    obtalacd (proportloaal to volunc of incluetona aanpled) fror fluld
    incluslons ln aaupler of quartz anrl calcite crughed under YacuuE. The
    crror bars nere calculated fron the preelalon error curve (see orror graph,
    lnsot) estlnatetl enpirlcally,fron thc ilupltcate anal'ysea of eanple 13941' '
    1395g and 13980. IncLuelons nlth C0, conccntrat!.onc greater than 1.5 nole
    t ahoul<l exhlblt CO, clathratlon effecta durlng freezlng tenperature
    . cxpcrlucnts, vhcreat laaluelons rltb COt conceatratlono graater than 3
    uolo t ahould contal,u llqutit G0, (aee text). lleither of these propertlca
    ysre observed, suggeetlng that COa concentretl'on Daaurs[ants t'o the
    rtght of thc clathratlon llne (>1"5 uolc I C02) are probably ln srlor.
    L65

    6- Gorlgorf
    !-: itr0 lliEridl
    L3: CO2 lliquidl
    ll o COl hYdrotl
    f alcc

    ,
    I
    f.1

    Flgurc ?-9r Pbarc ill'rgral for tbr ryatcl 820 - O02. (Fror Oolltlr; t9?9r.
    $6

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    L67

    Absence of Clathration
    The clathrate compou:ndCOr' 5.75 l{ro was not obsenred to fotm in
    fluid i.nclusions during freezing temperature elqperiments made by the r.r'rj-ter
    ancl ruas not reporbed by i,lerchant (1978) or Erceg (1981), the orrly obher
    studies in which freezi.:ng temperatrres of fluid jrrclusions r'rere determjred
    in samples frorn the liauraki GoId - Silver Province. Hot'iever, because the
    fluid inclusions in some samples are snnall and poorly visible, it is
    possible that clathration may have occurred rdthout being obsewed.
    Therefore the apparent absence of clathration in sanples frcm the l{auraki
    Gold - Sj-lver Prsvincer al-thoth of signlficance jrt most samples, may not
    be applied as a universal furdicator of maximum CO, content in a'11 samplss
    for which ftuid inclusion freezi-ng temperatr:re information has been
    presented (Appendix III).
    The CO, - hydrate occurs j.rr ftuid inclu.siqrs at OoC r:nder pressures
    greater than 13 bars (Fig. 74). The Henr3rrs Iaw constant at OoC for
    rlilulg lla0l solutiors is ?90 (1.1r J.W, Hedenqui.st, pers. co$tm.; c.f. Fig. 2
    of trrlls & Goldringt 1963) and therefore by substitution of these values
    in the Henryts Iaw ecl:ation (".f. Appendix V) the indicated mole fraction
    of CO, under these conclitions i.s O.016. Rounding off this figure suggests
    that concentrations of CO, i.:n excess of 1.5 mole fo are required for
    clafirration.

    Diseussion
    The limits of CO, concentration calculated for clathration and liquid
    CO, are plotted in Fig. 7-8 and indi-cat'e that the measurements of ftuid
    j.nclusion CO, concentrati.on between 1.) and J mole 'i COZ G3962 at 1.!,
    13910 at 2.O, tl+O35 al 2.O and 14037, at 1.8) are sucpect and the sne
    abqve 3.0 (f4O3?Z * /4.1) is proiubly in error. Ttre first series of
    samples have preci.sion error bars extending into the clathrate free fiel.d
    of Fig. f-8 (belo,r 1.J mole fi, CO) and therefore may represerrb
    concentratisns of or slightly less than 1.5 mole y'" QQZ.

    Assigned Values of CO",

    Tab1e ?-8 lists the values of C0, concentration assigned to the


    samples after consideration of the various factors dlscussed absve.

    Fluid Inclusion Salinity (Freezing Temperature) Corrections


    the salinity values determjned frcrn freezing temperature measr:rements
    of fluid inclr.sions (c.f. Appendix lil) are apparent salinitles because,
    jn additiqr to the dissolved salts (e.g. NaCI and KCI)r dissolved CO,
    168

    depresses the freezing point of r.rater by 1.B6oc for every nore of co, per
    kg of so.Lution.
    The <iepression of freezilg point effect of the ,r2 concentrations
    determi:red in the previous section are listed in Table ? together vrlth
    the available fluid inch:.sion freezirtg ternperature inforrnation. The
    latter is listed i_n two forrns: one series of results (average and marinum
    freezing temperature) for the specific sample listed and another set
    including resul.ts for all samples frcrn the parent deposit. The latter
    are iJrcluded becau.se in sorne sarnples insr:ffieient freezing data are
    available to give a representative result.
    In rnany cases the corrections for dissolved co2 are equal to or
    exceed the measr:red freezS-ng temperatr:res, indicating that ej.ther (or bobh)
    the measured CO2 concentrations are werestimates or the measured, freezing
    temperatures underestimate the concentratiur of solutes.
    Given the inaccuracies of the CO, and freeziag temperature measurements
    and the few data avaiJ.able, roubine application of Co, concentration
    corrections to the apparent salinity data presented. in this thesis are
    impossible and therefore no corrections are rnade. Ho.lever, the Coa
    measurements are lmportant jn demonstrating that CO, is quantitatively an
    irnportant solute and nay be the major solute in ssne rtilute solutions
    (e,g. with apparent salinitj.es ( Z eq. wt. y'o NaCl).

    0ther. I$plicatio, ns of CO,


    -goncgl$lations
    The high concentration of co, relative to other sorrrtes in scnre
    samples may e:cplain the wi.dely variable freezing temperature resr:lts of
    individual sarnples. These may resr:rt frqn variations j:r co2 content
    frcrn one inclu.sion to another implying I'r5.dely varying CO, concentratlons
    (W order of magnitude) Ar,ring crystal growth.
    "t
    .$'pparent saUn:lties of most secondary jnch:sions measured (even those
    vtith fi]]ing temperatures sirnilar to those of primary fluid inch:sions)
    vrere too low to neasurer i.rndicating that the hydrorLhennal fluids were not
    only very dilute in terrns of salts but al'so contained only very mi;nor
    concentrations of COr.
    IE

    cll{P1m I
    TIYDP.CGE}I ISSTIPES

    IjjTBOpUCrr0lr
    The systematics of <ieuteriun/nyarogen (o/H) ratios u.nd thei.r use as
    i:ldicators of water ori-gin in the geological. environment were reviewed. by
    Taylor (tg7tr, L979). D/H ratios are reported as 6 D per rni-l va],ues which
    are parts per thous and (/or) deviation frqn Standard Mean Ocean 'rlater
    (SiCd). 6 D of Sl'I0.1 is O, Positive 6 D values indicate enrichnent in the
    heavy isotope (O) relative to the standard, vrhereas negative 5 D values
    indicate enrichment in the light isotope (H).
    Ocean, connate (formation water), metanotphic and magnatic waters are
    believed to be characterj-sed by certain values of 6D, whereas 5D of
    meteoric water varies widely and systematice'l'ly with lattitude and altitud.e.
    Howeverr at any parti.cular location the mean 5D value of the meteorlc
    rvater is constant in time prorS.ded latitude, altitude and cJ-irnate rernain
    constant.

    METHOD OF AIIj\.LY$S
    for the extraction of s.rater frqn the f1uid inclr.rsions is
    The method
    described in Appendir Iv. llydrogen was separated by passing the uater
    over hot zinc in a vacuuir line and isotopi.cally analyse{ in a mass
    spectrometer' llaximum experdmental error on the isorboplc measurement is
    considered to be t 1 per mil.

    IE.ST S.\MPLE
    The 5 D of fltrid inclusion water in a sample of calcite cuttings frmr
    approximately looom in drirt hole 5 of the Ng,ewha geothemal, fierdl
    Northland, was measured at -32 per rnil.
    The total discharge 6 D compositions of
    'rrater frcn Ngawha drill holes
    4 and 9 are -35 Wr mil and - 3l+ Wr mil respectively, however the deep
    ftuid composition is srrggested to be closer Lo -26 per rnil (Bror*ne gt al;
    1p81 p 119).
    Considering the difference il age between the inclusions and well
    water (not knovm), ttre rneasured variatj.ons in welt water 6 D values
    (c.f. Browne et all 19St) and the r:ncerbajsrty of the deep fLui.d ecnposition,
    the general agreanrent (a maximum d'ifference of 6 per miJ.) between the fluid
    inch:sion measurement and rnodern well water indicates that the method
    used here can be accurate.
    t70

    T^BLE8.1:5DvaluggofuaterxtractedfrorrrflulclincluslonElneanples
    are quartz except
    fron sone eplt'hernal deposlts' All sanples is calclte' the
    shich
    sanple 13g62 (P'oya1 Oak l'line' Tokatea)
    Iargenegatl.vava].ue(-75patdl)forearrplel,t'013(Ualtekaurl)
    lsattrlbuterltocontanlnatlonbyalradrnlttedthrou4hacrack
    formed ln the sanple tube iturlng crushlng'
    Depo- I1eld
    samPle l{unber Location sltlon- lletAht of 6Dsxow
    r.}i.s' Ito'
    V.U.H. llo, lto. -a54a6/- GeneraL
    91e1il
    Specific aI crushed nater
    (ns) si"e" (c)
    tokatea Blg 58 23 '31+
    13957 Tt 2 1 5 Tokatea Reef,
    nnnn ril/R 9 -28
    n lKzz 25

    il Buffalo Mlne 137 -32


    13958 B02a 21
    oullock heeP
    n Bo2b 2L l|||n L3 12 -36
    r noYal Oak t{lne 7L
    rN/R 11 -33
    11962 R03 27
    23J8 _ Ir9
    13907 ilutt 2 31 Petote Stn Area. llutt Creek
    n Altken Strean 26622 -39
    13980 ASI a 9
    263t0 -116
    nb 8 n

    nc 10 |l |ln 21158 -31

    139981 PS15 33
    ll Petote Streao 22)6 -37
    ChaIcoPYrite lode
    14,005 PS26 20 tl Petote Stn, Itnorthn 2296 -27

    13910 !de9 )2 tChangapoua l'lelngaro Streen L?1 8 -48

    u16 6 !leavesvl.lle AJ ax 2L L2 29 -36


    13939
    Itl4a 7
    lntl 52 20 _29
    1391,1
    n ll14c 1
    nn|l 1.5 ,5 -38
    n Ir14d 17 llln 1.9 28 -38
    n l{14e 16 rnn 1,2 31 '36
    1?919 fl2q 12 ilaratoto Canoola Veln 3L 3287 -11
    aouth etoPe
    o n Sllver Queen Vsln 3 29 11 - lr9
    13926 ltl 13
    3L
    13928 1.t191 15 n Canoola Vein 3L ,5527 _ lr1

    n l{192 1 t,
    || trnll 3 39 15 - Irlr

    r 4,013 vrri 11 llaltekaurl ltaorLl-ancl Vein 36 10 -75


    1 t035 l,lh4 29 lfalht l|o.5 shaft nullock Ll' 6 -15
    heaP
    tr Hartha Veln 192 +5
    1 L0)7 l,rhlo1 19
    '50 +5
    tlrtl 1
    tl 1{h1 02 18
    Tu16 a 7 TuI lll.ne ChanPlon Veln 35L12 -27
    1 4053
    nnt j *Nln 21 -35
    n Tu16 b L
    1 1056 Tu113 26 t ChanPlon Vein 5L 2 62 18 -31
    Ralse 17
    4061 Tu1191 22 n Chanplon Veln 5L 23612 -35
    1
    DD erose cut
    r Tu119, 23 ||nlllt 23920 -),
    1 t o71 !1115 2 lf alorongornal
    - Creek'Canaillan 25917 -37
    float
    14090 1{16? )o n Dlanond Gulley 2353 -23

    t 4094 1't189 28 tt ?lolco:le VoLnt 2539 -37


    northern adlt

    r tlot Recordett
    L7L
    RESTIIIS
    Table 8-1 lists the 6D analyses of water frorn fluid inclusions in
    samples of quartz and calcite frm a few of the epithermal depooits.
    Most values lie in a -23 to -50 per mil range. The very light (-25 p.r
    mi1) value for sample L$OL3 (,{K 4) is due to air contaminatisn a&nitted.
    'bhrough a crack in the sample tube, develcped during crushing.
    i\ 6raph of 6 D versus rrater lveight (pig. B-1) shov;s that very smarl
    sar,rpies have more positive 6 D values than larger ones and that d.uplicate
    analyses show a trend tovard positive values with decreasing sample size.
    These trends are probably caused by fractionation of the sanple i:: the
    vacuum line during vacuun disfil'lali.on stages or contamination by nfsrsignn
    water in the line or on surfaces of the sanple (e.g. atmospheric vapour
    producing light values). The fractionatlon and cqrtamination are
    insigrlificant with large samples but drastigally effect the 6D of sqne
    sanples belsw 1O mg. Similar problems were encountered. by Taylor et al
    ( 1979) .
    An absolute water weight limit for reliableanalyses is difficult to
    assign, For example, 5 mg of sample U+A35 (Wh 4b) seens to give a sensible
    6D value, whereas the same weight for sampre LSgLg (u eq) d.oes nob.
    Several quartz samples were spI1t into tr,ro or more sanrples, used for
    crushing runsr aceording to thejr clarity (Appendix rv). The 1399o
    series (3 samples) and !39L1 series (5 sanptes) do not shon any systematic
    change in 5D dovrn the seriesl )r,a, xb, xc and xd due to an increaslng
    prooortion of secondary inc'lusions. If the 6D of primary and secondary
    inclusion waters is di-fferent thls factor is completely overshad,ol^red by the
    sample weight problern discussed above.
    Representatj.ve analyses selected after appraisal of the samples, in
    terms of the factors mentioned abwe, are presented in Table g-2. The
    selected 6 D values range fror -33 lo -h9 per mil with an average around.
    -4O per mi1.
    These results differ frcn those determined frqn t\ri l{ine sarnples by
    Robinson (L974). He reported 6D values of -?O per rni]- and -24 per mil
    for Stage 2 galena and Stage 3 quartz prfunary fluid inch:sions respectlvely.
    The -7O per mil value may indicate the presence of nragmatic water as
    postulated by Bobinson (1974) or leakage during crnshirrg (c.f. sampre
    14o13r Table 8-1). The -24 per mil value, aborrt 1O per miJ. heavier than the
    general value for late Stage 2 - Stage 3 fui lline fluid measured herer may
    have suffered sirnilar problems of contamination as many of the samples
    analysed in this study.
    T?2

    60
    +

    ,o

    40
    Frocliondfion i ?robablo
    durina .tamPnl Fluid lnclu:ion Air Conlamrndlion
    oN
    -to
    C'\
    s.Pa(dfjov'l; l Sanqa I
    rl ++
    E a
    I
    n + l'o

    lo
    o f" ol
    \l '
    t0 z a
    o lqz,ked
    x
    a
    a
    .'l
    x a
    o +t0 o -lo -20 -n -40 -r0 -@ -70 -go

    6D *tovt

    Flgurc 8-1r Plot of 6D valucr neaguted frou fluld lnaluslon ratcrs, extracted
    by cruohlng saoplar of quarta and calelte under vecuun, versu! the relght
    of rater aaupled. Dota repreaent nsagurenentg of illff,erent eanplesr
    rhcrcas aaaplea ln rhlch nore than one loelrurenent vera nade ( either of
    dupllcate or guallty acrLeat aas text) aro ghown by epeclflc ayubole.
    Dlffercnt leaauroltrts of the aane eanple generally exblbtt a trend of
    ilecrcaslng 6O vtth decreaalng vater vclght, probably due to fractl.onatlon
    ilurlng rauple oeparatl.on (aa aoted ln the flgure) or contanlnatlon by
    leotoplc exchaagc vlth adleorbEil nater already preaent ln the vacuur liae.
    Therefore the htgh 5D valuee, and the very lon 6D value resultlng frod
    leakager are reJecteil leavlng a rang6 of -33 to -L9 per all rhlch le
    bellevcd to reprerant tho origlual raters.
    t73

    ORIGIN OF TI{E I,{..ITER^S

    Intro.dqction
    The nat',rally occurring types of i.raters that are considered to be
    j.nvolved in the ore forrning processes are; ocean, meteoric, geobhermal,
    formation (conrrate), magnratj.c and metamorphic (Taylor, !9?l+rt979; Sheppard,
    tg77).
    Because volcanism i.:n the Coromandel Peninsula and Great Barrier Island
    not considered to be an important component
    r'las subaerial, ocean water 1s
    of the mineral"isations. The absence of metarnorptr"ic rocks (greywacke is
    not considered a netanorphic rock for the pu?oses of thjs discr:ssion) in
    the area indicates that metamorphic water was also nsb irlvolved. $lost
    geothernraL r*aters have been shorrn to
    be cmrposed of heated recycled meteoric
    waters (mt is & Ilahon, t977i Taylor, 1979) and therefore these two classes
    are consj.dered together,
    The range of possible types of water imrolved irr the mjnera3.i.sations
    co:sidered here is therefore narrowed to meteoric - geothermal, formation
    and magmatic naters. These are considered separately belor.

    Meteoric and Geothermal Waters


    Robinson (tgZt) reported a 6D value of -3O.5 per miJ- for Te *roha
    thermal r*aters and an average ccmpositi-on of -30.1 ! 1.0 per miJ. (range:
    -28.9 to -31.3) for Te Aroha meteoric waters. Therr:oal spri-ng r'raters on
    Great Barrier Island, however have heavier values: -19.1 to -21.8 per nriJ-
    (r M.K. Stewart pers. cornm.),
    Asstuning that the fluid inclusisn waters neasr:red here were originally
    meteoric water, the trend of lighter values (up to a ma:d.mr.m of 20 per mil)
    than present meteoric water may be attributed to ehanges in climate,
    altitude laiitude.
    and
    A reduction in mean annual temperature of lo0 would cause meteoric
    lraters to be depleted in deuterium by approxinately 5.5 per miJ. (c.f.
    Stewart & Taylor, 1981) and therefore a maxjmr:m decrease in temperature
    of approximately 3.54C r.rould be required to explain the entire range of
    fluid inclusion values without j.nvolvement of any other process. A
    reduction of aror:nd 2oC is probably more realistic for periods of cooler
    climate dur5ng the late Terbiary,
    6 O of meteoric water varies by approximatel-y -1.8 per rail for every
    10orn increase il altitude (e.f. Stewart & Taylor, 1981) and therefore this
    effect may be secondary but additional to climatic changes for the very
    heavy 5 D fluid inclusion values, but could possibly be invoked as the
    1?4

    TABTE 8-2r Sel"ected 6 D, vaLueE fo:r fluid


    LnsluEion watrc$ fr:o,il the epi,thernatr
    deposits
    i

    .ri

    We,ter 6Il
    Oenenal ' l{uraber Uei.ght gl{OW Average dD
    Sanple
    Lse,atio'n V,II.W. Iio. Flex.d $o. mg per ni.1 per uriL
    T:okatea i3957 ,1,
    Tfi ?-'3 -34 I
    13958 Bo 3b 12 -76 I-34
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    175

    priaary process for the lighter va'lues.


    Variation of meteoric water d D values with changes in latitude are
    quite marked (u.g. Kaitaia: -1{ per mjl and Invercargil'l 3 -48 per mil;
    Stewart & Taylor, 1981). The effect of the change in latltude of the
    Ilorth Island with sea ff.oor spreading si-nce the tine of nineralisation
    (probably up to 1o m.y. B.p.) is difficult to assess but may have
    eon+"ributed slightly to the difference between the 6 D values of the fluid
    ilch:sion i.raters and those of present day meteoric rvater. There is no
    trend in the 5D values of Table 8-2 with changing latitude frcrn north
    (Tokatea, Petote Strearn and Hhangapona) to soubh (nri ltine and',,Iaiorongcrnai),
    probably becatse of the sma'l] dj.fference in latitude and also because of
    possible differences in age of mineralisation.

    l"la,q.rnatic i.Iater

    Prirnary llagnatic !,Iater


    The range of 6 D valued for prinrary magmatic water is considered to
    be -5o to -85 per rnil, vrith values t;4pica'r'ry around -fo per mil (Tayror,
    t979). The fluid inclusion vraters measrrred here are outside thj.s range
    and are therefore not prirnary magmatic traters.

    Ilod:ified llagnratic i'later


    sone heal,ry 6 D varues have been repor*r,ed for nagmatic water from
    fumeroric condensates, for example: r.Ihite rsland, -5.8 to -z7.j per mil
    (stewart & Hr:rston, !976h rceland t -l+L t,o 4L per mil (Aranson a
    Sigr:rgeisson, 1958) I Satsuma - Twojirna, Japan, -1? to -2T Wr miJ (ptatsuo
    .*-glr L97l+) and showashinaan, Japan, -j2 per mil (Hfur$ani, LgTg).
    Several explarations have been suggested to explain these @currences
    of apparently isobgpica'l'ly heavy magmati-c r.raters, mainly the mj:cing of the
    magmatic water w"ith sea water, surface l'rater or formationa-l water. For
    exampler the latter was u.sed by l,lizuLani (1978) to explain the Showashinzarr
    6 D val-ues. Hot'rever, Stewart & Hulston (916) seem to have abandoned the
    involvenent of prinary nagmatic sater altogethen at i.lhite Island by
    suggesting that the 6D values at this location resrrlted from vapour
    separationr near the srirface, from a boiling mi>dr:re of surface water and
    sea r.rater vrhi-ch had infiltrated the volcano. $orne obher occurences of
    heavy magmatie tqater remain unsoh'ed and indicate that magmatic water,
    probably due to sorne secondary process, may have 5 D values heavj.er than
    -5O per miJ..
    Waters of lhgmas Ilerived by I'li:d.ng of
    Pri:na:y with Sedjmentary Rocks
    l,iagma
    The hy-oothesj.s that the andesite and rhyolite maloas, responsible
    for the volcanic rocks of the Corqnandel Peninsula and Great Barrier
    Islandr lrere not primary but r'rere formed by mi-xing with, or anatexis of,
    i'iesozoic sedirnentary rocks suggests that the 6 D of such magma may be very
    different fran prirnary magma. Vary5ng proportions of pri.n,,ary magma and
    sedjmentary rock would produce internediate va'lues, the possihle range
    of 5D values for magmas derived by these processes is rmlorown.

    FoJmatj.on (Connate) liater


    The only non-volcanic rock type of any signi,ficance jl the Corsnandel
    Peninsula and on Great Barrier Island is the l,Iesozoic sedinentarlr rocks,
    These probably contajn water mainly held jn htraCrous minerals although a
    little jnterstitial water rnay be present. fire latter is probably ocean
    water (6O = O per mil). It is r:nlikely that these rocks csuld supply
    much water to the mineralising system without metamorphism and evolution
    of nater frcrn the hydro:s minerals.

    l{jxed Meteoric - l{agnatic i{aters


    The entlre range of values of fluid inclusicrr vlaters could
    measured
    be formed by a mixture, in vari.ous prqlorbions, of prirnary magmati.c nater,
    r.rith a 6 D lighter than -5O per rnil; and meteoric water, with a 5D value
    around -30 per nil (present day value).

    co$glusI$IS
    5 D values of fluj-d inclusion traters, representing intermed:iate and }ate
    stages in epithermal mineralisations of the Coromandel Peninsrrla, form a
    cornparatively tight cl:.ster (! 9 per mil) around -40 per mil and are
    concluded to represent waters of preda:ninantly meteoric origin with possibly
    a small magrnatic cqnponent in the earlier stage fluids.
    The average 1O per rnil depletion in deuterium compared H:ith present
    day meteoric ruater i.s considered to result frqn precipitation of the waters
    during a cooler cll-urate and at higher altitudes and latitudes (in order of
    imporbance) tilan present.
    177

    CHAPIE? 9

    SUI,PHUR ISOfOPES

    IiErSUP.S"lEiiT
    Sulphide minerals b,ere concentrated by heavy liquid (methylene
    iodide) separations of the 0.5 - O.tz5lrul size fraction of aggregates
    obtained by crushing the sample in a piston crusher or picked from the
    sample l'rith a vibratool. Individrra'l sulphide minerals vrere hand pi.cked
    (with a wet fine pai.nt brush) from these concentrates r:i,rder a stereo
    microscope and fibre optic light source (Sctrott cold light source KL 15OB),
    Barite, the only sulphate mineral arnlysed, occurred as plates
    growing on earlier quartz (I.igs 44 and 1.44) and was easily separated by
    breaking the plates off the quartz r^rith a trnir of pliers.
    The ratios of the sulphur isotopes 34S *a 32s of the sulphid.e and
    sulphate minerals r'rere analysed by the methods oublined in Robjrrcon (f974).
    The results, Iisted in ?able 9-!t are given as S34S per nil values which
    are parLs per thousand d.eviation of +,n 3LS/32S. ratio of the mj-neral relative
    to that of the Canon Diablo Troilite standard (Cm). The standard by
    definition is 0 per rni-I. Sarnples hatt:ing a higher proportion of the heavy
    isotope (3as) than the standard have positive s3LSvalues and are said to
    be heavier than the standard or enriched. ir, 34S. Conversely, samSrles which
    have a higher proportion of the light isotope (32S) cunpared vrith the
    standard have negative S34S values and are said to be lighter than the
    standard or depleted jrr 34S.

    GEOTIJSII!,IOMETNS

    The 5 34S of sr.rlphide and sulphate minerals precipitating fran


    solubion is dependant on a nurnber of variables including ternperaturer pH
    and S3hs of the total solulion (Ohmoto, tg72). For a given
    "qthTrir
    set of these conditionr, ''*S/t'S fractionation occurs between different
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    sulphate> pyrite> sphalerite) ehalcopyr"ite)galena (c.f, Fig. 1O.3 of
    Ohmoto & Rye I L979). Therefore the fractionation between a pal-r of these
    minerals can be used to calcrrlate their d.epositicral terrperature by
    ccrnpard"son with experimentally calibrated fractionatj.on cu:nres (c.f. Figs
    46 and t+? ot lYiedman & OtNiel, tg?]), provided the minerals in question
    grew under the same conditicnrs.
    The reli-ability of the various pairs as georthermometers is in part a
    178

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    function of the magnitude of their fractionation- Therefore the reliabiJ.ity


    should be in the orderr pJrite-galena ) sphalerit+galena > pSrr:ite-
    chalcopyrite ) pyrite-sphalerite ) sphalerite-chalcopyrite ( sr:lphate is
    qnitted as it is rarely found in an equiJ.ibriun assernblage ltith the ccnunon
    sulphides). Hovrever, previous studies have found'uhat pyriter although
    seemingly j-n textural equilibrium ttith other sulphides, nay not be j-n
    isoto'pic equiJ.ibrium, as shown by the failure to conply vrith the
    fractionation trenci p;rrite ) sphalerite ) chalcopyri.te ) galena. Therefore
    sphalerite-galena pairs eppear to be the most reliabIe.
    The a3as ( 5t'"*- e34sr) between cogenetic pairs ef sphalerite-gaLena,
    pyrite-chalcopyrite, pyrite-sphalerite and sphalerite-chalcoplrite and their
    derived temperatrrres, usi.:rg published fractionation cr:rrresr are given in
    ?,.
    Tab1e 9-1. A'*S and calcu-lated temperatures for aIL sphaleri.ts-galena
    and pyri-i;e-chalcopyrite pairs are presentedl trhereas this inforrnation is
    given for pyrite-galena, pyrite-sphalerite and sphalerite-chalcopyrite pairs
    only if sensible temperatures are obtai:red and sphalerite or galena is
    abseni frorn the sample, precluding the use of sphalerite-galena pairs.
    The fractionation curves of I(ajiurara & Krouse (f97f) are used for pyrite-
    galena, pSrrite-chalcopyrite, pyrite-sphalerite and sphalerite-chalcoplyrite
    pai.rs, whereas for sphaleri-te-galena pairs the cu:nre of Czamanske & Eye
    (t97ln) is used, because of its denonstrated agreement rvith fluid inclusion
    fiJling temperatures in a number of ore deposits (nyr I97l).
    The naximum experinental error of ! O.2 per nril on each mineral gives
    rj-se to an ocperimental error of ! 0.4 per mil on the a34s of a nrineral
    pair. The error on calculated temperatures is different for the different
    mineral pairs due to their different fractionations, for exarnple at 3@oC:
    +L0^ - +6s +1104^__.
    -i; for ptrmite-
    I j[ ro" pyrite-galena, !"Ui ro, sphalerits-galenas :
    cha1copyr5.t", : iffi for pyrite-sphalerite and ! ffo for sphalerite-
    chalcopyrite, and increases r,rith increasing tentperature. For simplicity
    the emor range on al.l cal-crrlated temperatures in this thesis are eonsidered
    to be ! 4ooc for pyrits-galenal t 6ooc for sphalerite-garena, 3 loooc
    for pyriie-chalcoplrite, ! t5OoC for pyrite-sphalerite and ! 2OOoC fo"
    sphalerS-te-chalc opyrite pairs.
    The sphalerite-galena pairs give interna3-ly consistant temperatures
    which are also generally cornparable to the fluid jnclusion firling
    temperatures frsn qr:arbz of the same depositional stage. Howeverr pyt"ite-
    chalcopyrite paj-rs genera'l]y give higher temperatures than seemingly
    cogenetic sphalerite-galena pairs in some deposits and unreasonably high
    temperatures in others (c.f. Table p-1) ralsing sorne doubt on the reliability
    18l}

    of the pyrite-ciralcopyrite pairs altogether. Because galena and sphalerite


    are absent from some mineralisation stagesr and jn some d.eposits absent
    altogether, a solubion io the p;rr:ite-chalcopyrite problem is Srnportant..
    The fractionation betrveen p;rrite and chalcopyri.i;e for the eicpecied.
    ternperature range 1 aogc 1.{ per mlJ at 30OoC, 5-s larger than the estirnated
    rnaximurn e:cperimental erors, r,;hich jr this case vlould reciuce the 1.4 per mil
    fractionation to 1.O per rnil. Therefore the ab.sence of significant
    fi'actj-onation ( > 0.6 per mlrl equivalent to < 6oooc) between a p}mite-
    chalcoptrlite pai-r is considered real and indj.cates that the mineral pair
    are not cogenetic. 1\*o explanations are possible. Either the chalcopyrite
    was deposited after the pyrite under different chernical or temperatgre
    conditions or the chalcoplmite is formed. partly by replacement of the pyrife
    r"rithout ccmplete isobopic re-equilibration of the sulphur.
    The determination of pyrite and chalcoptrrite paragenesjs by examination
    of their texLr:re in polished ore mounts is generally not possible because
    the use of their grain borxrdary relationshlps and the criteria of id.iornorphisrn
    has been shor.m to be r:nreliable (Stanton, tQlz), with pyrite tending to form
    euhedral boundaries against obher minerals even if preci-pitating later than
    the ad;acent minerars. rsotopic evidence is therefore imporLant.
    Averaging pyr:ite-chalcopytite values j-s no guarantee of achieving better
    accuracy because if the pyrite and chalcop3r'ite are out of equilibrium,
    due to either replacement of pfitg by chalcop;'rite or different periods of
    depositiot; a'l'l surnples should be eqrully effected.
    considerr for exanrple, the earry pyrite, chalcqlyrite and hemdtite
    mineralisation at rui l.{ine. Robinson (tglt) determj-ned five a34s py-cp
    values for samples from the Champion and Ruakaka Iodes, rangi.:ng frqn 0.6 to
    1.2 per mi1 and averaging 1.0 per rni.I, the latter i.:rd,icating a depositj-onal
    ternperature of 4@ t 80oc. lfith the addi.tion of sample 1&056 (a34s px-cp =
    O.8 per miJ-) frorn this study the average value of sj.x pyrite-chalcorppr-ite
    pairs is O.! per m5J indicating a temperature of 43OoC,
    rt could be argued that the occurrence of a range of A p,'-cp varues
    j.:ndicates that the sarnples are nob eqr:alIy effected by the problen.
    If
    equiJibrium was approached at sorne tfune, for example by a short period of
    ouerlappi-ng pyr:tte and chalccpyrite deposition, the most representative
    analysis of the series rrirl probably be the one rvith the largest A py-cp
    value (and therefore the lorsest depositional temperature). In the case of
    the early tui t'iine mineralisation this would be 1.1 per nil, indicating a
    temperatur"e of 3?OoC.
    Therefore it seems that there is no unambiguous solution to the pyrite-
    t85

    ?ABIE 9-2: A. Deposl,tional tenperatures calculated f,or sono deposltg from the isqtoPic
    fractlonation of sulphur betueen cogentic pairs of sulphide ninerals
    (rnalnlY sPhalerlt* and galena).
    B. Xsotopic coDposition of sulphur epecies in solution at the assigned
    tenperatures (based on a conlcination of sulphur isotoPe and fluid incluslon
    data), calculated from th. 534s values of the sulphide and sulphace minerals
    using fractlonation factors fron ohtnoto t Rye (1979).
    A B
    Fluld Composition
    Terq)eraEures essigned
    Stage from sulphur TemPRratur ,tnr"r" 634s"ooz- ,34sso2
    isotope (-c)
    data (per mil) (per rnil) (per nil)

    Miners Head 425 +I +lO

    Te Ahunata I 250 ( +26


    .2a 220 +rl +28

    2b 240 L +27

    Northe!n
    +3 +23
    Colville 350 325
    Peninsula
    (sorry tlary
    stn + Ibctors
    creek)
    Kuaotunu 2-3 250 -l +24
    +2 +25
    Tokatea Jcnu levels 280
    +2 +24
    Petols stEea& I 340 300

    Wtrangapoua 280 r +2O


    2
    4 200 ] -3 1 +27

    +2 tl +12
    Tapu ThaIBeg rCu-Biu 400
    350*r 280 +2tr +2s'2
    'Pb-Zn"
    Ttrane9 gold-pyrargYri te 230 +2.3 +29

    -7 +19t4
    barlte
    220 -2 +25
    Neavesville Bluffs section
    300 280 +2 +25
    l.taratoto 2

    340 280 +3 +26


    t{aitekauri 2
    +2 +23
    Halhi lor levels 340 325
    +3 +25
    xarangahake Iou levels 290 300

    I 400r5 400 +2.6 +12


    Tul l,tlne
    320 300 +3r6 +25
    2
    -L' +rBt7
    3 (barite) 200 .
    ttal,orongonai I 320 325 +I +22

    (barite) -16 +19r8


    3 150

    rl see Table r-Ir2, data fron Dr B.H. nobinson (pers' connr')


    )2 Agrees yith Robinson'E (see Table I-It2) +24.? Wt nil
    value neasured in barite
    fron l'lonoerai 3L
    13 see Table I-l+'1, data frotn Dr B'w' Bobinson (pers' corua')
    ra (see Table r-!!-l); used to calculate634! t"tt
    o":r* rEasurad by Roblnson
    ^r"t.*-lt;"
    .5 nobinson (1974)
    r6 Averaged f,rom data rePorted by Robinson (1974)
    1d
    values rePorled by Robinson (19?4! and sanPle 14067 listed
    a? Averagd fron 6- S barite
    in Table 9-I; used to calculate 6'"sn^s
    *1
    to calculate
    :. of, earnples l4o?o and 14099 (see Tabla 9-1!i
    used
    r8 Averaqe 63as.
    DarlEe
    .34:o"rt
    o
    186

    chalcopyrite problem. The accuracy of temperatures determined by pyrite-


    chalcopyrite fractionatists can only be established by cornparison rrith
    temperatures obtained by crbher rnethods or, if these are not available, by
    considerati.on of the paragenesi.s irr ccrnparison !'rith simllar mineral
    assemblages in sbher deposits where depositional temperature is lstown,
    In the case of the early Tuj. Mine nrineralisation an estimate of a
    realistic tenrperature can be made by considering the temperatr.rres of later
    galenar sphaleriter pyrite and chalcopyrite mi:reralisation. Robinsorr (tgZt)
    reported average A sl-gn values of 2.3 per mil for the Charrpion Lode and
    1.6 per mil for the Rr:akaka Ipde indicating terrperatr:res of 28OoC and. 38OoC
    respectively. The latter is probably too high because at least one Asl-gfi
    value (1.e per mjl for sanrpres 5&, ?able 5 of Robjnson, 1!f[) gives an
    unrealistic temperature estimate of approxi.rnatety t$OoC 5nd.icating that the
    galena and sphalerite are not cogenetic. Re-averaging the other sam5lles
    gives a A sl-gn value of 1.8 per mil and a teurperature of 35OoC for Rnkaka
    Stage 2 mjneralisation. Stage 1 mineralisation was probably deposi.ted at
    higher temperatures than Stage 2 mineralisation and therefore temperatures
    between 3?0 and 43Ooc would be possible. Robinsonrs or{-gina]. value of 4OOoc
    is used for thenrochernical caleulations jn Appendix V and rirodelling of the
    mineralisation il rlppendix I-U.
    I consi.der therefore that temperatures of n1neral. deposition derived
    from Apy-cp values are unreliable when unsupported, by other evid.ence and.
    at best may on-ly represent naxirnum temperature vat.ues.
    In conclusion, the temperatures assigned to the various deposits on
    the evidence of the fractionations of sulphur i.sotq>es between coexisti'g
    mineral pairs are listed in Table J-2. The temperatures presented, represent
    three of the epithemal minerar assenbrages (c.f. chapter ,|n) as forlq.rs;
    Pyrite - chalcopyrite assemblage3 Tui l"iine sarrples discussed
    previously. Average temperatr:re assumed to be AOOoC
    Pyrite - sphaleri,iie - galena - chalcopyrite assemblage; temperatures
    range between Z55oC and 4OOoC bub average around 30OoC

    Plrite - sphalerlte - galena - chalcopSrrite


    electrum - sAlver
    -
    minerals assemblage: Maratoto samples giving three tenrperaturesl
    2754c, zgooc and 33ooc.
    tsl

    FtlIID CHEMISTITT

    Sulphur Specigs in Folution


    Ihe. dominant sulphur species present in hydrothermal fluids at hilh
    ternperature ( ) 4moC; are HrS and SOr, whereas bel-ow 4oo - 35OoC ttre
    reduced spec5.es may be represented by
    ry- (itr arldition to HrS), and oxidised
    specj.es by sr-rlphate (e.g. I{Si and SO4t-). The exact temperature at which
    the concentration of SO, equals the concentration of tsbal sulphate is
    dependant on the f%O, {S, fO21 pH and salinity of the fluid (OtrmorUo a
    nye, 1979).
    hre (L979) classified the qqueoun sulphur species that corrld
    Ohmoto &
    becqne qtrar$itatively sigrificant in hydrortherrral fluids at temperatures
    below aboub 35OoC i.nto three groupss (r)
    .2- %S, (2) t6- and (3) sulphates
    (so4' , ffioi, oof, uasof and GaSO4). These authors considered that
    isobcpic fracti,onation betwe* %S and IIS- is much snq'llgr than estirnated
    by Sakai (1968) and that for practical purposes it can be assumed t,o be O.
    Isotopic fracti.onatlons between the variqus sulphate species are af-so small
    (Otrmoto, t972) and when cqnpared with the large sulphate - snlphide
    fractionation can sim5larly be ignorred. Therefore the isorbopic canpositions
    of the two sulphide species and the isobopic cortrlosition of the various
    srrlphate speci.es can be atrrproxirnated by consldering onJ.y a s5:rgle species
    frsn each class. HrS is chosen to represent the strlphide fraction, whereas
    S0A- is used to represent tlie sulphates, This is because in most previous
    sulphur 5-sobope studies of fossil and modern hydrothernal solutions these
    particuJ-ar species have been considered to be the dcminant refresentatives
    of their respective classes. Also, the isobqric fractionation between HrS
    /-
    and SOU has been the subject of greater study than any oLher sulphate -
    sulphide pair and is therefore probably the best lsnorn.
    .)t
    5'+S of Sqlphur Species in Solution
    are precipitated from a hydrorbhermal flu:ld, sulph:ide
    I'lhen minerals
    mineral su-lphur fractionates agailst the aqueous sttJ.phide species, whereas
    sulphate mineral sulphur fracti.onates against the aqueous sulphate strrecies.
    Therefore the gShS values of the varj-ous sulphr:r speci.es in solutj.on
    (trere represented by HrS and tOU'l can be calcr:l-ated using the relevant
    fractionation factors (e.f. F5.g. 10.3 of Ohmoto & Rye r L979) if the
    temperature is knorn and isotopic equilibrium conditiona are assuned.
    ttt* the temperature range of interest here 1>eoOoC) 634s",
    34S"n "rrA
    t ",. are close to t'U\, and therefore averaged analyees of either or
    188

    bsth of these minerals (depending on whettrer one or both are present)


    were used to approcimate moet of the S3LS, o values presented
    t2o
    in Table

    9-2. ,,lhere sphalerite and chalcoptrrrlte analyses were unavailable,


    --
    ' S34S---
    -PY
    values were used taking jrrto consideration the small fractionation between
    p;'rite and HrS. For sr.rlphate the isotcpic analyses of barite were used

    directly to approximate the parent SO,.2-


    4
    in solution, horiever most of the
    5
    rut, ,., 2- values of Tab1e 94 vlere derived u,sing the fractionation between
    vl
    +
    so4'?- and HrS at the assigned temperature.

    634s of the Totar Strlphur in Solution


    634s of the total sulphur in solution (5tur*g) iu the sum of
    34tr, dd 5 34sro, e- . This parameter i-s not onry dependant on the
    6 *
    4
    f 34t*, .r,u 534ssot:- but also
    '2D at tt
    indlv:idual- valuee of" on the relative
    concentrations of suJ.phide and sulphate (c.f. Fig. 5 of Rye & 0hrnoto, L97lr).
    ?t.
    6'nSlS in hydrothernral solubicnrs can be deduced by considering the

    63LS values of the sutphide and, sr:lphate mi.nerals and the mineral stability
    relati-ons on fA, versus pH rliagrarns. Some mineral assemb.lages limit the
    possible values of t34st, to a small range.
    Stage 1 mineralisation at Tui Mine consists of qr:artz, plmite,
    chalcopyrite and hematite i+ith minor gold, bisnruthilite and tetradymite.
    Flactionation of cglrecipitated pyrite and chalcopyrite
    S34S between

    was used by Bobinsm (1974) to jndicate a depositional temperature around

    lgOOoC. Robjnsonrs (19?f+) fO, versus pH diagram for this mineralisation i.s
    reproduced in Fig. I-U-g of Appendix I. The hydrothermal fIui.d in
    equllibrium with the obsenred mineral assemhlage must plob near the pyrite +

    chaleopyrite/hematite boundary and therefore probably had tbs , SOi:-


    "
    ratlo greater than 1 (t* z). The average 634s va-lue for Stage 1
    chalcopyrite analysed by Robinson is 2.5 per mrl indicating o 6345,, o of
    r12D

    approd.mately 2.5 per mil. At 4OOoc AgS-soUz- is approximately 15 per mAl


    and therefore O'Ut O,2- rvould be 18.5 per mil. If the ratio of ffrs;SOrz-
    LT
    189

    in the fluid is 1:2, 634tr.Sre 13 per mil. Given the inaccuracies of the
    temperature measurement, constnrction of the fO, versus pH di.agram (at
    35ooc as opposed, to isotopic data at 4OooC), the value of A *u
    %*rOU-
    the possibility that equilibrir:m may not have been completely achievedt
    orrly bor:ndary lirnits of say +10.5 per miJ. (gS , tar* = 1:1) and +16.O

    per mi1 (Hr$ : Sol- = Lz5) can be confidently assj.gRed. to tt'" ar.
    llowever, Robi-nson (tglt+) used the |SLS value of +16 per mil for ].ate stage

    barite to fix the va-Iue of 6345{5 by assuming that thi.s barite was

    depoeited by a fluid cortai-ning sr.rlphur alrnost exclusively as *U'- *


    which case 634s
    s \a 5'urro, z- + 15 per miJ-.
    4Dt
    $irnilarlyp late stage barite frcm Thames (Kuranui !{ine S34S = +L9.!
    ner mi]., I,toanataiari 3 levef 5 34S = +L7.2 per mi]., and !tralyconMine
    63hS = +!9.? per mil, Tab1e I4,I-1; data frqn Dr B.lI? Bobinson, pers. ccnnr.)

    and Waiorongcrnai ( S3AS = +18.8 per mil) indi.cates precipitation frcm a


    sr:].phate dcrninatedfluid with t345, S around, +16 per mil.
    An alternatS.ve explanati.on for these barites and those of Tui lline

    could be precipitation frcm a sulphide dcrninated fluid uith a 1or tal.ue of


    ?t.
    5-*SS. However, Oq*oU?- at the tenperatrrre of barite precipitation
    2OOoC or less)
    (probably 2OO-C less) is approximately +3O per mil (or greater with
    decreasi.ng temperature), necessitating a ,t*1", more negative than -1O per

    mi1 with a sj.lni-lar value for d3hSSr a situati-gn nol conpatj-b1.e with the
    63bS values for earlier sulphides (between -1 and +4 per mil). Therefore
    these barites could nob have been precipitated in i.sorbopic equilibriun
    with fltuids having a f 34S S around O per miJ. under arryr corbfuation of HrS
    a
    and SO,'-.
    4
    In contrast, barite from the Tapu - Thames area (l,{ononai 3 level;
    5 34s = +24.7 per miJ-, F B.w. Robinson, pers. corfuno) vias precipitated from
    ?r.
    a fIuid with 6--SU around O per mil and dissolved srrlphur predcrninantly
    in reduced for:m because l{erchant (fgZg p 239) recorded flluid inclusion
    fil:ring terrperatures for this occurence betlyeen 282 and 33ooc (o%*rour-
    lgo

    i.s approxinately 22 per mil at 3OOoC).

    Iate mi.rreral"isation was also to determiae 6345a, at the


    used

    l,taratoto Mine by Robinsor & Christie (rg80). They recorded S3LS values
    for main stage sulphldes (pyrite, chalcqlyrite, sphalerile and acanttrite)
    averaging 2.1 per mIL, whereas trvo ana-lyses of late stage p;rite gave d3LS
    values of +16.O and +16.9 per mil. Sulphate minerals have not been reponted
    jn any stage of the mj.neralisation. A s34s{s of +16 Per rnil was

    concluded b5r assuning that main stage minerallsation was formed from a
    fluid w:ith an %S , SO4'z- ratio of approxirnately 1:1 but that this ratio
    changed nith tine so that during late stage plpite precipitation the fluid
    srr'lFhuir species was alnost entirely Hrs and S3hs{S R^ S3A1s* t'\n
    The presence of pyrrhotite in assemblages of sulphide minerals, with
    d3LS values around, +t per miJ., at Miners Head (depositional temperatr:re
    atrryroxirnat eLy l25oC) and in the lor leve1s of the Waihi Mine (depositional
    terperatnre approximat e].:y 325oC) necessitates a simi].ar interpretation
    to that for the ]-ate Maratoto fluid. Precipitation of
    pyrrhctite (with pirite) at the temperatures considered here occurs frsn
    fluids in which sulphide predcninates otrer sulphate, or SO, in the case of
    l.liners llead (Figs I-A-? and I-S-9 of Appendlx I). Therefore 634sa, of the
    trydrothermal fluid is nob sslslsrtia]]y- dlfferent from t345,, o and hence
    ltzD
    ?r,
    6-nS of the sulph-i.des. AILo*ing fe the fact that pprrhotite is a minor
    phase relative to obher sulphides occurring at luiiners Head and is varSr rare

    ln the low levels of the Wai.hi Minel |SLSS at these localities was probably
    between +1 and +8 per mlL. A value of +5 is selected as being represenbative.

    llinerals that linit the pesible isobopic ccr;losition of the parent


    trtrrdrobhermal flLujds are absent froo most sbher deposits for wh-ich 6345

    values of the sulphides are lsrourn. Their mineral assemblages and sulphide
    sulphur isotope data ar.e compatibile with 6'Ut values between
    aU
    approxi.rnately O and +18 per mi1- by consideri:rg different mixes of sulphate

    to sulpblde concentrations in the tqrdrothermal fluid. Low value= or v63&s"s


    -e vr
    191

    TABI,E 9-3: 534s .rrlo"s of the total sulphur in solution 1 634srr)


    during formation of some of the deposits and ttre probabLe
    source of sulphur. 5tnra" values were derived from the
    dissolved sulphider/dissolved sulphate ratios of the
    hydrotherfial fhuids, estimated on the fO2 versus pH
    diagrans (eppendix l), and ttre indiviilual values of
    34s 2- (Tabre g-21 -
    5 -- - and 634s-^
    t2" DU4

    c.34-ois Source of SulPhur


    Miners Head +1 Magrnatic
    Te Atrumata +1 Magmatic
    Northern Colville Peninsula +3 Magrmatlc
    (Sorry Mary Stm + Doctors Creek)
    Kuaotunu o Magmatic

    ltokatea +2 Magnratic

    llhangapoua 0 Magimatic

    Tapu Itrames (Cu-Bi and Pb-Zn) + 2 &lagrnatic

    Thames (gold pyrargYrite) + 16 Sedimentary


    Neavesville + t6 sediulentary
    llaratoto + 16 Sedi:nentary
    Waitekauri + 4 lrlagmatic
    r{aihi + 5 llagmatic
    I(arangahake + 5 Magmatic

    Tui l4ine + 16 SedimentarY


    Vilaiorongcmai + I6 Sedimentary
    t92

    ("rg. +5 per miJ) are consi"stent nith h"igh sulphide to sulphate


    concentrations, whereas high values of 534Sgg (e.8. +16 per mil) are
    consistent w'ith sulphate equal to or in excess of sulph'ide.
    In conclusion, values of 634sa, which have been determined for sme
    of the mineralisati.ons of the Haurakl Gold - Silver Prsvincer by the
    methods outlined abwe, are listed in Table 9-3.

    souRGE oF sr,fiBgurn

    lntroduction
    Trro possible sor:rces of sulphur for the mineralisations of the Har:raki
    C'old - Silver Prouince have been d:iscwsed prerriorsly in the literaturet
    sed:imentary and magmatic.

    Sedimentary Sulohur
    Robinson (L971) and Robinson & Chrristie (1980) postu.lated that the
    srrlphur in sulphide and sulphate mj.nerals at tu:i lline and Maratoto
    origj+ated as Jurassic sea water sulphate deposited with settiments nol
    forming the grey*acke basement of the Corqnandel Peninsula and $reat Barrier
    Island. Sea vraier srrlphate during the Jurassi.c i.s believed to have had an
    average S34S value of +U per mil (Claypool $jL, L972) and therefore conld
    readily accorint for the 63LSaU value of +16 per miJ. postrrlated for the
    trydrothermal fluids.
    Simi-Larly, Kusakabe (tgll*) considered that hi.s assigned va-lue of +15,1
    per mil for 6 tU,,, of ','Iairakei geothermal waters indi.cated a Dtesozoic
    greywacke source for the sulphur.
    Robinson & Christie (1980) proposed that the mechanisms i:rvolved were
    the solution of sr.rlphate frqn the greyracke sulte rocks by the hydrothermal
    flLuid and gradual reduction to sr:lphider bM Fe2+ in the mafic minerals of
    the volcanic waIL rocks or by magrnatic hydrogen, durjrrg transport. The
    2t
    6t*S values of the sulphide and sulphate species in solution gradualJ.y
    becorne heavier as the pro'portion of sulphide to sulphate increasesr prorrided
    isotopic equllibrium conditions prevail (cornplete exchange between sulphide
    and sulphate).
    Roser (in pr"p.) suggested that sulphrrr i's present in greSncacke
    as sulphate; in connate water, and sulphide of both voleanlc and sedirnentary
    2,
    orj-gin. 6t*S values between -1.6 and -4.O per mil were determined frsn
    six sarnpJ-es of pyrtte in Weltington argillites by Roser (in prep.), whereas
    Mr. F. Reid (pers. Connl.) Oeterrniled values of +t3.5 and +13.9 for pyrites
    tgF

    EflEiE 9+{l 63h ral*so of py-r!.t'c in gre;ruracke eul'te rocks of tbr


    f,asatau atel. Date eourtcay of l{r tr' Reld

    A. Fgr,.lte xn f,Ft'sh grtytlaEe flol aurfeo! c{pltsErjt,l l'n the f,avcsau a;let
    g34
    gEnpL lhrinbEr opt Fynlic
    Eleifi!-gs' -.{npr nll}
    V.$--Si", F6,.
    +1r3, -
    1tt60 nqa
    160a4 062 +17.:9

    8,. Py..Ltr l3 [yd$qt-hrfnally' e].tased grey!*ccke fror drlltr


    Sanplle l{uubcr Dsi,Iin hs[q sptl! filscur svrlto'
    Xi&r&-lt!l. IrEgEe &'t ,- ,,uo, -.,: ---4- . .(g?r ni.ll. .
    KAZS 116& +5.9,
    i 59to. n5816:5[g1
    '15,,98-1 R58"6510t, f,L?5 119t *.6.0'

    15p;8& R5865lU? ar25 {1998-1399 *5.5


    Iigqj G5865/.0{ RA3' ro35, *6r5
    x5996 e5/s:6!l0l8 KLz' ta7 +t.o
    r5ggs, n:5a69Na2 KAz9 995 +t.9
    n5s65lo5 Eil22 '11:56-1157 *6,.1
    nGnrof i

    [i8651016 K[2{ t2t0 *6.1


    B,rg65109 ,hAe4 12r& *5-'6
    19b

    in unaltered greyracke (Reidts samples HQ 2 and 0S 2 respectivelyr Table


    p-{) frm Kawerau. In contrastr Reid determined that hydrothermally altered
    grelnrracke of the Kawerau geotherual area contained. pprite rdth tiLS values
    between +3.9 and +6.2 per miI (Table 9-4)-
    Giggenbac'n (1977) analysed the isotopes of sulphur in wraltered
    grey*acke from areas bordering the Taupo Volcanic Zone. He separated
    suJ-phide and sulphate fraetions chemj.ca'lIy and concluded that average g34S
    val-ues of bobh fractions viere bstween +6 and +? per mil, with ranges of
    -7.3 Lo +1-5.'l per mi3- for sulpkt-ide and -7.8 to +17.8per rnil for sulphate.
    Giggenbachrs (1977) maxirnum value for sulphate is similar to the +L7
    per mil vaLue suggested by Robinson (1974) for sea water sr:lphate
    incorporated into the sedi.rnerrts, however the range of values measured b;r
    Giggenbaeh (dom to -7.8 per mil) suggests that sqne seconrt"ry process has
    rrariably depleted the sedimentary sulphate of 34S, This may be due to onel
    or a ccmbi-rnatiur, of the folloringe diagenesis, rnetamorphisnr hydro0hemal
    alteraticn, ground water leaching, surface weathering or surface bacterial
    actisr. If some of these latter processes have been active in depleating
    3&s, ciggenbachrs light 5345 sulphate values may norb be representative of
    greynacke at depth (e.g. 1-3 km). The average value jn these deep rocks
    is probably heavier than the +? per miJ. value suggested by Giggenbach and
    may be as much as the +1J per mjl value suggested by Robinson (1974)r
    Knsakabe (i971+) and Robinson & Christie (1980), horever exact defj.nition
    is not possible with the information avai1able at present.
    The 534S of total sulphur in greywacke depends on the individr:al SSbs
    values of sr-rlphate, sulphide and other su-Lptrur sources and their prqrortions.
    Therefore values from about +1f per nrjl to scrne lighter value are possible.

    I'{a..rnatic Sulphur
    l.leasured d34S values of i-gneors rocks average close to the meteoritie
    value of O per mjl and therefore prirnary (mantle) magna is considered to
    have a S34s value of 0 per mil (orrmoto & Sre , t979).
    Although no measurenents have been made on the volcanic and jrrtnrsive
    rocks of the Coromandel and 'rlhitianga Groups they are considered to have
    SSLS values heavier than the meteoritic value due to the c<rntrLbublsn of
    crustal material in their formation. Based on measurenents of the sulphur
    isotopes in greywacke, and the values reported in the literatr:re for
    geotherrnal waters at I'lairakej. and Ketetatri, and fimerolic discharges frcm
    ilhite Island, Giggenbach (1977) derived the following series of 6345 rr"1,r""
    for the rocks of the Taupo Volcardc Zone: basaltr O per mil; andesite;
    L95

    +2 to +{ per mil (in accord r*Lth the l{hite fslAnd measrunents of +3 lo +3.5
    per mil); rhyoliter +l+to +5 per mil and gre;nracke, +6 to +f per miI.
    Simjlar values of +? to +4 per rniJ for andesites are postulated here
    for the Corqnandel Group andesites and dacites but the rhyolites of the
    rdhitianga Group are probab\r heavier than Giggenbacht s range for Tar4ro
    rhyolitesl especie'lly if the value for Manaia HiIL Group gretrn*acke js around
    +1? per mi-l (see previous section),

    Discussion
    5,t+S,,qS of andesitic magma is believed to be around, +4 per mil,
    whereas 6'*5{5 of gre;n*acke suite rocks could be as high as +1J per miJ..
    6tasrs of rhyolitic rnagra is probably intermediate, Therefore if a
    -sulphur source
    with a 63bS value of around +[,per mil is indicated for a
    specific deposit, a magmatic origin is concluded. In contrast, if a rralue
    of arowtd +16 per miJ. is indicated the srrlphur probably orlginated frm the
    sedirnentary rocks. Values between +l* ed +16 per mil may indicate either a
    rhyolite magrna or sed:irnentary source of sr.r-lphur
    Suggested sources of sulphur for scrne of the deposits of the Hauraki
    GoId - Silver Prsrjnce are listed in table 94.

    CON.CLUSIONS

    Both magmatic and sedimentary suJ-phur ar^e considered to


    have contributed
    to the mineralisations of the liauraki GoId - SiLver Province although their
    respective roles differ betreen individr:a1 deposits.
    196

    9HAPIm, 10

    PrngrcocHEMIslBY Allp MODEI, OF

    PORPHTRY CC'PPER MINENALISATTON

    PHYSTCOCHEI"IISTRY

    fntroduction
    The geochemical environments of'mjneralisati.on for the individual
    porphy:ry cqpper depooits of the llauralci Gold - Si}1rer Province are
    estimated in Appendix I using data calculated in Appendix V. This section
    co.Llates and sr:rnnarjses that information into a canparative descriptS.on of
    all 9f the deposits.

    Geochepi.cgl Dvironment
    porptryry copper deposits of the Hauralci GoId - Sl-lver Pror5nce (the
    Needles, Mjners Head, Paritu, Mapaia and Tapu - Ttranes) are believed to
    have formed at terperatures aborre AOOoC frcnr sohrtions in equ5librium
    with biotite or serLcite (propylitic or guartz - sericite alteration).
    Secondary orthoclase has been identified on3.y at Paritu where it occurs
    rarely, posslbly associated with the formation of tour:araline veinlets.
    The mineral assemblages at, the various locations are: (1) Nee&les:
    bornlte and chalcopyrite; (2) Miners Head; chalcoppriter pyrite, sphaleritet
    pyrrhotitep argentian pentlandite and galena; (:) pa"itu Coastal Section:
    pSrrite, chal-copyrdte, nolybdenl,te, pSrrrhotiter arsenopyrite and wolfrarite;
    (l) paritu DriIL Holes (biotite qrrartz diorite phase): pyriter chalcoptrrrite
    and nagnetite; (5) Manaias pyrlte, chalcopSn{te, nagnetitei and (6) fapu -
    ?hanas: pgite, chalcopyrite and a sequonce of plrrrhotiter nagnetite
    an4 hematite, In addition tourrnaline occurs at Paritu (Coastal Section)
    and Manaia.
    Etuid ibclrrsion evidence is cnly for the Miners llead deposit
    avaiJ-abiLe
    which forrned at approxirnat eLy l&SoC from non-boiting fluids rcith a salinity
    of approxlmately 1O eq. wt'. fo NaCI.
    The mineralisations are modelled on an fO, versus tenperature diagram
    (fig. 1O-1) at a temperature of l&ro1. S*lphur was present in the ftuid
    predcminantly as HrS. The absence of bor:rite frm most deposits and
    prsence of plrrrhotite (a mineral rarely recorded'fron porphlrry cqpper
    deposits) in some, suggests lovr sulphur fugacities. The lcnrr oxJrgen .

    ftrgacities jndicated by the absence of magnetite fron assemblages of the


    Paritu Coastal Section and ssne stages of other deposits (B in Fig. 1O-1)
    t9?

    oN
    -2A
    (r
    o

    -70 (,f,

    -t5
    7@ 400 500 6N 1nw
    Tevvperafurz, ('C)

    Flgure "10-1: Oxygen fugaclty veraus tenpcrature dla6ran (based on flg.4 of


    Eurnhau & Ohooto, 1980) relating the fOr-t flelds of tha Haurakl Gold-
    SLlver Frovlnce porphyry nlnerallsatlon (aLI nodelled al LZ5oCl to the
    otabtllty fleLds of pertlnant lron-bearlng nlneral aeseoblages (at
    approxinately 1 kbar), aqueous sul.phur epecies (at ptl=4) and overleas
    porphyry copper deposlta (stlppled area). ?he lfeedles bornlte I
    chalcopyrlter end the Parltu and Manais uagnetlie + pyrlte +
    chalcopyflte olneiallgatlons are rrprsaented by fleld 1 r uhereas fleld
    2 ls tha Hlners Head and Parltu Coastal Sectlon pyrrhotlte * pyrlte +
    chalcogyrltc nlnerallgatloas, The arrov represents the changlng
    pbyslcoeheoical eondltlons lndlceted by the lron-baaring nlneral oquence!
    pyrrhotlte folloved by uagnetlte folloued by henatlte' ldentlfled fron
    the Talnul (Tapu-Thanea) porphyry depoalte by ilerchant (1978). Flutde
    contslnlng sulphur predonlnantly tn reduced foro are lndlcatetl for the
    Haurakl Provinee nl.nerallsetlonar honever flutdg vith predonlnantly
    oxldlsad aul,phur spectea (nore typlcal of, econonlc porphyry coppr
    depoolts c.f. Burnhan & ohaoto, 1980) nay have been present at tho
    Needles, ParLtu (OonEohl Streao), ilanala and Ta1nul tf the depoe!.ta rere
    forncd at nueh hlgher tenpcraturca (e.g. 6O0oC).
    198

    itrplies lcn* torbal stlIphtir for these mineraU-sations (c,f. Brrn]ram &
    Ohmoto, 1980).
    These features nay account for the indj.cated. poor developnent of
    corpper and rnolybdenum mineralisation in the deposits.

    UqLEI, FOR POFItrIIY CCPPER I,trTI-ERAII9ATION

    Introduction
    severar genetic features of q/erseas porplqny cqpper deposits and
    models for their formation are briefly descr:Lbed belor before a model is
    presented for the deposits in the ltar:raki GoId - Si]-ver provjrce. For
    discussiqls of the geolory, mineral.isatisr and classification of porphyrly
    cqpper deposits the reader is referred to the ord-gi-nal references cited
    berow and the reviews by r,ceerl &Guirbert (rgZo)1 Rose (19?o)rcuilbert &
    LoweIL (19711)1 Hollister (f97S) and 1"ittEr& Beane (19S1).

    Geneli.c Featuresof Porphyrlr.Cwper Deposlts


    Althorgh individual porplqry cqpper deposits differ in specific details
    such as alteration and ore rnjneral assemblages, Gustafson & I{unt (1g?5)
    considered that these differences are cnly rrygr'iations on a themer a36
    that sinilar processes and evohzblonary trends are ccmmq.t to al't porphyry
    cqpper deposi.ts,
    Several features ccrrnonly found in syerseas porp$r3r copper deposits,
    that are important to the csnsideration of their genesis, are:
    1. their association w'ith porphyxitic calc-alkaline or atkatine
    rocks,
    2. thejr relative shallow eroplacement (generally i-n the subvolcanic
    ernr"ircnrment) ,
    3. the general occurrence of concentric'patterns of hydrothermal
    alteration njleralisation;
    and
    and lr. the usual presence of bneccia features such as rrspssl<]grr breccias,
    breccia dlkes and breccia pipes.

    In addition, stable isorbope erridence suggests that waters associated.


    with pobassic zone alteration and nLneralisation were magnatic, whereas
    those associ.ated with alteration and mineralisati.on in the phyllic zone
    (and therefore probably also the argit]ic and. propylitic zones) were
    meteoric or formattonal waters (c.f, Taylor, LgTt* lg79i shepprd, !g77).
    Fluld incl-usions also record the e>d.stence of two separate fluids,
    one a hiehly sarine fluid at high temperature (?oo - 5oooc), boirtng in
    199

    Flgure 10-2: Hodels prevlouoly proposed (see text) for porphyry ulnerallsatlon:
    A. Hlnsrallsattoa and hydrotheroaL altatstl.oa are forned by a Eagnetl.e
    fluld uovlng out fron a cryetallirlng pl'uton.
    B" Prorlual hJ.gh teupereturc nlneralLsatlon ancl hlgh gratle hydrothernaL
    alteratloa are foraed by a nagoatio agueous vapour phase vlolently
    released fron a pluton durlng crackle breccta fornatlon. Relatl'vely
    diatalr lorer tenpereture nlnerallsatl,on and lorrar grade hydrotherrrral
    alteratlon are forned by lncurslon ofr and nlxlng of the naguatic
    flulal nlthl ground vcter convcctlon cc1ls.
    c. l{l.narallsatlon antl hydrothernal altcratlon are form.ed by ground
    nater convectlon through a gubaollduc pluton. A vapour donlnated
    at6ar phase lg generate locally abovo thc pluton.
    2W

    sqne d.eposits, and the other a cooler (lOO - 2OOoC) non-boiling fluid of
    moderate salinity (Nash, t976).

    Ilodels Prmosed by Previous rrlriters


    ttg. 10-2 i'llustrates three models that have been proposed to ercplain
    the formation of po{ph}rry copper deposits;
    (a) fhe first model is a simple orthonragmatic model (e.g. Rose, 19?0)
    in which a magnatie fluid msves out frm the intrtrsion forming the dlfferent
    alteration and mineraU.sation zones in response to falling temperature.
    (U) The evidence frorn stable isoibopes and fauid jnclusions or.rtlined.
    in the prevlous sectior has prcmpted severa-l authors (e,g. Burnharnl t967t
    Lg79t HolJ.andr Lg72i l{hitney, L975i Henley & l.lcNabb, t978i and Burnham &
    Ohmobo, 1980) to prqrose the involvernent of a magmatic aqueous vapour phase
    generated by retrograde boJJ.5ng (c.f. hrrnham, L979) dunhg the early stages
    of hydrcrtherrnal and mineralisation. In some models (".g. Henley
    alteration
    & ttcllabbr Lg78i Buuharn, 1979i Burnhan & Ohmoto, 1980) circulating gror.rnd
    water (meteoric or formation water) becones the predminant alteratim and
    mjneralising agent dr.rri.:ag the j-:ntermediate and late stages.
    (c) Catnfes (fg??) proposed a model in which nineralisatisn and
    hydrothermal alteration is formed by grorrnd water cornrection through a
    subsoU.dus pluf,on. that a vapour dcninated steam zone
    He considered
    worrld be generated abwe sune plutons and would account for the boi-ling
    recorded by fluid jnclusions. ?he magmatic water irnput jrr this sSrstem is
    presrnrably snrall eunpared to nrodels (a) and (b).

    Factors Deterrnining the Style of


    Alteration and !,lineraltsation

    The predomjrantfactors which determine the style of alteration and


    mineralisation in porphyry cqpper deposits, and which of the three models
    described prerlorsly qlerates, are!
    (1) water content of the magma,
    (2) portassiun content of the magma,
    (3) deptfr of emplacement of the intnrsion,
    and (4) tensife strength of the country rocks.

    (1) !'later Content of the Dlagrra


    A mirrjnum content of water is requi.red in the magma to
    generate a
    magmatic aqueors phase for mineralisation, ho*ever too nruch water wiJ-l
    causte the magma to crXrstallise in Lhe pluturic envircnrment (Burnharn, t979i
    Burnham & Ohrnoto, 198O; Gwtafson, L979). Between these two e:ctremes the
    201

    relative nater conient of mineralising fluid


    deterrni:res the quantity
    avaliable and, together with sorne oiher factors (e.g. the depth of
    nineralisation and tensiJ-e strength of the corrrtry rocks), the degree of
    retrograde bolling and brecciation of the country rock (general.J.y the
    qDper solidified parfs of the pluton), Some irrtrusives rnay eontajn sufflcient
    water to generate several cycles of retrograde boiling, brecciation and
    mi.:r'reralisation.

    (2) Fotassj.r.m Content of the t"lagma


    The potassium content of the magma ilfluences the conpositions of
    both the crystallising rock (increasing potassiun content dcnrn the seriesi
    quartz dioriter granodiorite and quartz monzonite) and the partitioning
    magnratie aqueous phase (e.g, Na/K and KCVHfl ratios), These factors are
    irnporbant j.rr determjnjrrg the pattern of hydrotherual alteration produced,
    (i.e. whether abr:ndant K-feldspar alteratioar occurs in the pof,assic zone).
    High potassi.um and lou potassium t;rpe deposits are represented by the tLor*eII
    &Guilbert mode1.r and the tdiorite nodelr respectivel-y (ttre reader is referred
    to HoIljster, L)18, for a review of these models).
    ?he porphyry copper deposits of the }lawakj- GoId - Sjlver Province
    may be classified as diorite type deposits. because they are associated
    tlrith quartz d'iorite and granodiorite intrusives and secondary orthoclase
    is either absent or not well developed in their ltpotassic zonesl (c.f.
    the alkali silicate alteration of Tapu - Thamesi l,lerehant, 19?8). The
    predominant tlpe of alteration associated r'rith copper mi:reralisation in
    these deposits is quarbz-- sericite (phyatic).

    (3) Depttr of Bnplacement of the Intrusion


    Theeffects on poryhlmy cqpper deposit'morphology resulting frcrn
    d:ifferent depths of magma ernplacement vrere discussed by Sutherland. -
    Brcrrrn (L976) and l{ielsen (f976). Deposi.ts formed in the plutonic
    envirsnment cmtain nineralisation generally confined to veins and have
    poorly defined hydrothermal aLteration zorsr fn contrast, hypabyssal and
    volcan:ic poryhyry copper deposi.ts cmtain both disseminated and vein
    mineralisatj.on and the trydrothe:rnal alteration zones are generally weLL
    develcped.
    These properties probahly
    resrrlt frcr,r differences jn roek perneabali.ty
    and the ability of retrograde boiling to produce extensive fractrre systems
    in shaals,u environments, allowing for more exbensive circu1ation of
    hydrothernral fluid (both magnratic and meteoric - formation waters) and
    202

    hydrothe:mal alteration.
    In the depth related classification scheme of Nielsen (fgZ5) tfre
    deposits at the Needles; luliners Headr Paritu and Manaia are hpabyssal
    types, '.rhereas the Tapu - Thames deposits are volcanic. keccia di-kes
    (h)'drottrenral and igneous) occur associated vrith nost of the deposits and
    the deposits at the lrleedles and l.ljrters Head are themselves mineralised
    breccia dikes. Quartz vein stocki.Iorks, although i-dentiJied fron the Paritut
    l.ianaia and Tapu - Tharnes deposits; a'r not e>ct,ensive, indicating that
    eliher crackle breccias were not lteIl developed for one of several reasons
    (".5. loti rsater content of the nagrna) or that the main vein stocki,rork zones
    are below the leveIs of e:cposure or depths drilled.

    (4.) fensife Strength of the Corntry Rocks


    Errr:]ram & Ohmoto (1980) and Sillitoe (f98O) d,iscussed the effects of
    fracture and failure of the werlying country rocks during retrograde
    boiling of subrvol-eanic jntrusives. Th:is parameter is interdependent r.rith
    depth.
    Liinited fracturing may produce the creckl.e breccias believed to be
    assocjated uxith stoclarorlc vei-n formation, whereas large fractures may
    a'l]ow the formation of hydrothermal brecciar igneous brecci-a or porphyry
    dj-lces and pipes. In the exbreme case, complete failure of the rock may
    result in caldera forrnation and ercplosive volcanism with dispersion of the
    metal s.
    l.ierchant (fgZg) identified several circular geomorphi.c features in
    the andesites of the Tapu - Thames area and suggested that they were
    eroded calcleras. $orne are coincident with the centres of porphJTy
    mileraU^sation (".g. a 2 lsn d:lameter feature surrounds the Ohio Creek
    deposit) and offer another possible explanation for the presently indicated
    poor developnent of subuolcanic porphyry copper mineralisation (c.f.
    $illitoe r 1980) .

    l'lodel for the lla-urak_i Gold - Sjlver


    Provi:nce Ponch]rrTr Copper Deposits

    The model illustrated jn Fig. 10-3


    and described belor is based msin'ly
    clrl si-rlitoe (tg73i 19S0)1 Burnham (Lg7g) and Errnham & Ohmoto (f9AO) ana
    emphasises the development of the patterns of hydrothermal alteration and
    mineralisation in the porphyry copper deposits of the llauraki GoId - Silver
    Province. It is divided into two major environments: magmatic and
    hydrothermal.
    203

    l++

    A B c
    Emolacemenl Formalion ol Vol canitwt
    of 'plufon. atVola.

    bvv,cc\a

    lqne,ow dike
    .t- +
    +++
    D E
    Rctroqrade, brifing Por1hyry mineralvahbn

    Ftgure 10-3: ltodel for porpbyry copper foruetlon la the Eaurakl.Gold-Sll-ver


    Prorlace. Follor1ng eoplaoeuent of a plutou (l), tUs concentratlon of
    volatlles neer the roof cauaes the developoent of a cupola zons lntruded
    lqto ths bypabyeaal envlronueut (B). Ground vater eonvectlon cel1e forn
    (C), causlng uldeapread hydrothernal- alteration ln the country rocka.
    Ventlng of thc cupola to th6 surfaoe produceo subaerLal volcanlsu.
    Cessatl,on of volcanlsn and retrogracle bo11lng' acconpanylng.crystallleatlon
    of the lagoa, forns a uaguatlc aquoous vapour phaee vhlch sccunulates near
    tcupola (D). Eventuelly the lluld prsgsuro excseds the
    the top of the
    ' eonflnlug pieasure and hydraullc fracturLng of thb conflnlng rocka occurs
    (E). lhe aagratlc flutd Ls vlolently orpelled througb the neuly orsated
    channelo to forn atockrorks, yeLn6, breccla dikes or lgneoue illkes.
    lll.neral deposltlon uay reault fron the effects of nlxln.g of the ragnatlc
    fluld rlth ground nater.
    204

    l4agmatic Ervironment

    (a) ttagma Generation


    for porphyry copper mineralisation were
    The magrnas responsible
    fornred by parbial melting of amphibolite jn the slab of t4rdrated crwt
    descending dor.rn the subduction zsne.

    (U) Crystallisation of the Hagma and Formation


    of the Magrnatic Aqueous Phase
    The magma ascended through the crust and r.ras emplaced jn the plutonic
    environr:nent. Pu1ses of nagma rose from a zone(s) in the roof of the pluton
    to form multiple jntrusions in a trypabyssal cupola zone(s). Ventir4g of the
    cupola(s) to the surface produced an and.esite stratavolcanoe(s). A
    convective s;rstem of deeply ci-rculating meteoric water was generated in the
    suroundi-ng country rocks.
    Once volcanism had ceasedr a magmatic aqueous vapour phase, generated
    by crystallisation and retrograde boiJ,ing (c,f. Burnhan, L979), accumulated
    in the upper part of the sutvolcanic magrna chamber. The internal pressure
    increased, because of the tendancy for the crystalti-sing nagma to e4pand,
    until the fluid pressure exceeded the confining pressure (lithostatic
    pressure plus the tensiJ-e strength of the werltrring crystallised igneous
    rocks and the country rocks) and the overlying rocks fractureC to accommodate
    the e;pansj-on of ihe nagma, Crackle brecciatj-on (Paritu, }{anaia and Tapu -
    Thames), breccia pipes and dil<es (the Needles and l{jners Head) and igneous
    dikes vlere formed jn the overlying rocks and the nagmatic aqueous phase
    was expelled as a vapour plunre through the varior:.s conduits to rnix ricith
    the eirculating meteoric water convective cells.
    The quartz d.iorite stocks of the Tapu - t'hames deposits represent a
    second. magmatic cycle 5rrtruding a pre--eristi-r:g volcanlc environment and
    may possibly be associ.ated wit,h the resurgent phase of calderas.

    (c) Composi.tion of the l,tagmatic Aqueous phase


    The magmatic aqueous phase predorninantly consists of HrO, NaCl-, XCl,
    HClr H2Sr SO2r CO2r Fe0lrr FeCl, and IIF but also contains most of the
    nretals such as Cu, Pb, Zn, Au and .A,g that were originally irr the melt.
    The relative concentration of the variorr^s constituents depends <rn the
    original composition of the magma, the previling physicochemi.cal conditions
    and the stage of cr;rstallisation (c.f, Ernharn, 1979), ltrevertheless, by the
    time the systern reaches the magmatic/hydrothennal bowrdary
    205

    (equivalent to the HrO - saturated solidus of the magna i.e. the temperaturet
    for a given totaL pressurel below which hydrous silicate melt is not
    thermodlmamically stable) I,la0l and KCL make up approximately )(' of tlne
    total chlorides and theNac/fCt ana HrS/SO, rati.os typieallyra1'

    Hydroiherme* Srvironment
    After leaving the crystallisiag nagma the magmatic hydrothernal vapour
    pirase reacted with the solidified parls of the intrusion and the country
    rocks causi-ng hydrothermal alteration and mineral. depositiono
    In sorne deposits the NaCVKCI ratio of the 1f-uid llas sufficiently low
    to cause poLassium rnetasornatism (rrpotassict' al.ieration) "td the formation
    of seconciary qirartz and biorbite (Miners Head and Tapu - Thames) or orthoclase
    (Paritu Coastal Section), whereas jn others rvith relatively high NaC/KGL
    and low KCL/HCL ratios, hydrogen metasornatisrn was the major forra of high
    ter,iperature alteration, forrning secondary quartz and sericj-te (equivalent
    to phyllic alteration).
    In the former deposits, potassirm metasmratj.sm caused depletion of
    potassiun in the ftuid, and, together with the release of Na+ by the waIl
    rocks, resulted in an inerease jn the NaCVKCI ratio or the f3-uid. Therefore
    a stage of hydrogen metasornatism'was also initiated jn these deposits.
    Dissoci.e.tion of HCI and other acids with decreasing ternperature was probably
    also an irnportant factor in causing hydrogen metasomatism.
    At some stage in these seguences the nagmatic hydrothe:mal fluiti
    encountered and mixed with deeply eircrrlating meteoric water. In most
    porphyry copper deposits this is considered to occur ln the phyllic
    al-teration zone and is an important mechanism of mineral deposition.
    The meteorlc water caused hydrol-i7sis of the magmatS-c SO, to HrS and

    %SOin
    via the reaction:
    4SO2+4Hro=H2S+3 H,SOU (10-1)
    hrrnham & Ohnoto (1980) suggested that SO2 may also react w5-th ferrous
    iron bearing minerals in the walI rocks via:
    So, + $ ttPgott * %o = IlS + 3 nFe2o3x (lH)
    The resultant increase in HrS activity caused metal sulphide
    (particularly pyrite) deposition and production of HC1- as follows:
    4 (tte)cl, + ? H2s + HrsoL = le (Me)s, + /+ Hro + I HCI (10-3)
    The magmatic fl"uids of the }tauraki Gold - SiLver Province had rblatively
    high H2S/SO, ratios (c.f. Fig. 1O-1), especially in the case of the Pari,tu
    Goastal Secti-on, and therefore the SO, hydrolysis effect would be l5rnited
    and probably accounted for only minor metal sulphide deposition. DilLutj,on
    206

    and a decrease in temperature during mi:dng of the magmatic fluid l'rith


    meteorj-c vlaber nere probably the main deposition mechanisms.
    In the deposits r.rith the lowest IIZS/SOZ ratios in their magrnatS.c ftuids
    (t;anaia and Tapu - Thames), the S0, hydro)-yses and subseguent acid produeing
    reactions were sufficient to shi-ft the fluid/mineral equiJ-ibria frqn
    sericite to kaolilite (or pyrophyllite) and produce an argillic alteration
    zone consis""5lg of kaoliniter sericite, quartz and pyrite. This argillic
    aiteration tendeci to neufralise the pH of the f1uid, increasing the KCVHCI
    ratio.
    With the increasing KCVHC1 rati.o, caused by quartz - sericite (phy1lic)
    or argillic alteration, together with decreasing temperature, reactions
    involving CO, and calcium metasmatism became important and ninerals such
    as chloriie, calcite and epido,be vrere produced, forming propylitic alteratisr
    zones. However, some of these zones probably existed before porphfy cqlper
    mineralisation, due to the pre-existing hot meteoric water convective
    sSmtem formed at an eariy stage of jntrusive activity. fn these cases the
    quarbz - sericite and argillic alteration zones probably werprinted large
    volumes of propyliticalry al'vered rock.
    4A,.'
    ..v I

    CHiPTBR 11

    PH:TSICOCMPNSTRY AIID I,ICDS, OF

    FI THER].'r,I,L Vlffi lI Nf t[dililJS.rTf 0!;

    INTPOIUCMCN
    This chapter investigates the physicoehernistry of the depositicnral
    enrrironrnents of the vanous ttrpes of epitherrna]. rnineralisation found in
    the liauraki Gold - SiJ-ver Province ln order to identify the characteristic
    processes that form the indirridual mjneral assemblages. A rnodel for the
    cteposition of a hypothetical deposit, containing the various mineral
    assemblages, is presented.
    Hor.;ever, before cornmencing this discussion it is necessary to bri-efly
    review the current knowledge on the transport of metals and non<tetals in
    hy-drothermal solutions and the processes that cause mineral deposltion.

    Rqiirlgtl oF MIlFsiL ri?Ai{q)ORJ' Ai\D DL"OSITION


    IN TI{E ffDnorHFn},HL EUnRo}ll'tHgT

    Transport of Hetals in Hydrothennal Solutio.ns


    The e>perj:nental and therrnodynannic evidence on the solubiJ-ity of
    rnetals in hydrothernral solutions, reviewed by tsarnes (fg]g), indicates
    lhat meii:rls are transported in lrydrothermal solutions as chloride and
    sul-phJ-de complexese although other ligands (e.g. hydroxide) nray be
    important r:nder cerbain chenical conditions.
    Present evidence suggests that cadr,riumr copper, iron, leadr sj-lver
    and zinc'are transported predominantly as chloride cornplexes, whereas
    antimony and mercury are transported predcmlnantly as sulphide cornplexes
    (c,f. Bames, !979).
    Gold is transported as borbh ctflori-de and sulphide cqnplexes r their
    rel.ati.ve j-mportance being dependant on the tennperature and oxidation
    state of the f1uid. Gold chloride ccrnplexes appear to be dmrinant in
    high temperature and relatively oxidising solutionsr r.;hereas gold thio
    conplexes are dorninant at ternperatures belo* approxi.ruately 3OOoC and
    under relatively reducing conditions.
    Thermodynamic and mineral structural erridence, together with the
    evidence indicated by the natural occurrence of silver mi:rerals in ore
    deposits and geothermal areas, suggests that jn addition to chloride
    conplexes, sulphide cunplexes are also inportant transporters of silver.
    Barnes (t979) suggested that at lower temperatures sulphide ccrnplexes
    208

    are more importani, as for gold, but that aborre 3moC ch-Ioritie complexes
    becone domjrant. The separation bett^ieen regions of domilance of chloride
    and sulphide coriplexes is co,rrplex and depends on conditions of Sr 01r
    pl{; T anci fOr.

    Jeoosi'"io.n of lietals frgn Hydrothermal Solttrons

    InLroduc'bion
    of metals frorn hydrothermal solutions occurs at a
    The deposition
    point where ihe transporting ccrnplexes becorne r:nstable. Barnes (tg|g)
    dlscussed representative reaetions for netal sulphicle deposition froill
    ehloride and sttlphide complexesr llls reactions and lhe most important
    faci-ors that make thern proceed (listed i:r order of effectiveness) were as
    folLovrs:
    (a) Chloricie complexed metals
    Reacti on: l'IeCI, ("q) *
    %S ("q) = MeS + zt{ + 2Cf (11-1)
    Proceeds r,triih +Amr2-, - 02, +apH, dilution, -ATr -opt
    (A) Srfphide complexed metals
    Reaction: lte(XS)"- (.q) = IuIe + ItS- * %t (.q) ( 1-L-2)

    Proceecis l.rith -.omr2-, + O2t --ApHr dilution, -6.Tr -APt

    A m*2-
    A change jl the concentratioql of sulphide fe.g. I{rS for equati.on
    (11-1) and HS- * %S for equation (tt-2)] fras the opposite effect on the
    solubi'lity of the tvro t;rpes of complexes.
    The concentration of HrS in solution may increase (causing deposition
    of metals frcm chlorS-de cm,plexes) by srrlphate reductionl reactj-on from
    organic cornpounds or mixing vrith sulphide solutions, whereas it nay
    decrease (causing deposition of metals frcrn sulphide ccrnplexes) because
    of bollilg and conseguent separation into the vapour phase.

    o2

    O,ridising conditions may cause deposition of nretals fran sulphide


    contrrlexesr whereas reducing conditions favour deposition frsn chloride
    conplexes.
    Barnes (ryZg) considered that oxidation uas the most effective
    chemical process to cause instability of the sulphiti.e complexes because it
    decreases both total sulphide concentration and pH. Hor^rever, the linriting
    209

    factor is the quantity of oxidant locally available.


    oxidation may occur because of interactions of the solution with
    wa'l'l rock ninerals r for example the conversion of magnetite to pyrite in
    ihe ualJ. rocks, or by mixing with o,xtrrgenated traters.
    F.educLion j.:: terr:ts of the concentraLion of sulphide has been dealt
    uit,h uniier the A nr^2-i>
    headins above.

    pH
    Changes in pH have opposite effects on the stability of chloride
    and sulphide ccnplexes. rnereased pH, cawed by either reaction with
    carbonates or feldspars, or boiling off acidic gases, eauses deposition of
    metals frsn chlori-de canplexes, whereas a decrease in pH may change the
    sulphide aciivity product ("HS- . r%S) by the reaction:
    IE- + n* = %t ("n) (11-3)
    causing deposition of metals fron sulphide conplexes.
    Earnes (1979) also noted that because the conplex l{e(}F)r- reaches
    maxirnum concentration where pH = PKH^S arry pH beloo this value causes
    depositlon. '

    Dilution
    DiJ.utio'r (".g. by mi:ctng with circulating meteoric rrater) causes
    deposition of metals from both chloride and sulphide conplexes because
    of the decreased chloride and sulphide concentrati-on.

    -AT
    A decrease in
    temperature causes decreasing solubiJity of both types
    of conrplez bdt a large change i.n temperature is required to precipitate a
    significant quantity of sulphicie.

    -APt
    .! decrease in pressure l.lithout initiation of boiljng is considered to
    have only a minor effect in promoting sulphide deposition frqn solution.
    l'he effecNs of boiJing have already been discussed.

    Ftetal Zoning
    Barnes (L975; 1979) considered that the generalised zoni-ng sequence3
    molybdenit-arsnopyrite-pyrrhotite-pentlandite-stamite-chalcoplr'rite-
    sphalerite-tetrahedrite-galena-acanthite-go1d telluride s-stibnite-c innabar r
    tlpical of rnost hydrothermal deposits and sj.rnil-ar to that obsenred here,
    210

    correlates with increasing solubiJity of the metal cunplexes. Sl*itching


    betrreen adjacent minerals in the sequence (".g. chalcq>yrite-sphalerite)
    happens uhere the relative concentrations of the metals in the deposit
    are locally reversed.

    Tralrllort and Peoositio+ of ltron-rqglals

    tuertz
    liiiica is in hydrothermal solutions generally as species r,rith
    present
    the fornrula SiOr. n%0, The solubility of the silica polynrorphs is
    dependent on tenpera'r,ure and pressure but, virtr:a11y i-ndependant of ionic
    strength and pH in the acj-cl to slightly al.kaljne range (Hottand, 7979).
    The pri.mary mechanisrn for quarbz deposition i-n ore deposits is considered
    to be a decrease in temperatr:re (HoUana, t979).

    Calcite
    The solubility of calcite in hydroLhermal solutions can be erqpressed
    as follows:
    .t,
    CaC0, + CO, *
    ibO = Ca* + 2HCO3- (11-4)
    Cal-cite solubility Sncreases with decreasing ternperature and
    i-ncreasing COZ pressure (but decreases with increasing CO, pressure at
    constant total pressure when mCO, > 1 molefkg). Deereasing temperature
    alone i.rilI therefore not precipitate calcite fror solution. HoILand
    (f979) considered that calcite was deposited in most ore deposits as a
    result of boiting [causing a decrease jn mCO, and a shift of the equilibria
    to the left in equation (11J+)] and changes in plt due to rva'l'l rock
    reactions.

    Barite
    The solubiJ-ity of barite increases with increasing temperature,
    pressure and ionic strength (c.f, HoILand, tg|g). The simplest depositional
    mechanj-sm is one of decreasing temperature.

    G{lnlqgcji,t- EilwtRcS,'mNTS 0F Tlry nplTnnrutt ErN


    I'IIFE&iL .\SSq:.1BI4C'.ES AND CAUS 0F ltillq&Il' Drpos.ITIO{

    IntroductSon
    The geochemicaL envirorunents of mineralisation in some indirridual
    epithermal deposits are investigated in Appendix I usi-ng the data
    calculated irr Appendix V. The conclusions derived fronr these different
    2tL

    deposits prouide sufficient information to collectively discuss the


    ph)'sicocheririsiry of the depositional environrnents and mechanisns for
    seve:'al- of i;he vej.:n mineral assemblages discussed in Ghapter 4.

    Pyriie :- Chalcopyrj-te 4ssemblage

    Ge ochemi-cal llnvirorunent
    Early vein miaeralisations of Tapu - Thames and Tui liine rrere deposi-ted
    at high temperature (aror:nd AOOoC) by fluids of near neutral pH (in
    equ-ilibriunr vrith sericj-te in the waIL rocks),
    Boiling occured during the Tapu - Thames mineralisation but no
    evi-dence for or against boili.ng of the early fui l"line fluid is avaiJ-able,
    Althcugh l,lerchant (1978) cited an indivj.dual occumence of pyrrhotite
    in minerallsation of his Cu-Bi mineral association j-n the Tapu - ?hames
    area, pyrite - chalcopyrite assemblages seen to have genera'l'ly been
    cleposited in the vei-ns of Tapu - Tharnes anrt Tui l.{ine at high fS, and f0,
    (figs 11-1 and 11-2). These parameters were hi-gher at Tui. l,line than jn
    the Tapu - Thames veins as indicated by the occurrence of hematite (higir
    for) and possibly bornite (trigh fS2) j.rr the former.
    $ulphur was present predomiaantly as HrS in the Tapu - Thanes fl.uids
    but S0oz4or 50,2- were also impcrLant constituents in the Tui l,tine fluid
    (fig. tL-z). The concentration of total sulphur in solution'rrras around
    O.05rn,

    l'iineral Ileposition
    l{ineral deposition frorn chloride cornplexed metaLs jn solution probably
    occurred because of an increase in pH of ihe fluid due to reactions rvith
    the lralJ. rocks (u.g. sericitisation of the feldspars) and in the ease of
    the Tapu - Thames deposi.ts because of boil-ing and loss of the aci.di.c gases
    such as COr. Dilution and reduetj.on are also suggested as possible
    rnechafiisrls in later sections.

    Pygite - Sphalprite - .Galena - Chalcopyrite


    t Electrurn
    t Silver Minera]., and Sb - Sulphosalt l4ine-ra1 .Asgmblages

    Introducti.on
    pyrite - sphalerj.te - galena - chalcopyrite, pyrite - sphalerite
    The
    - galena - chalcopyrite - electrum - silver mineralr and Sb - sulphosalt,
    raineral assenblages are considered together in this section, The mineral--
    2L2

    -2 5 h'ouid
    5-vaPotl
    -4 BoexffErPYRfT ,)
    (c504
    -c
    -8
    PYRITE H: u'\
    C{
    rn
    -lo
    PYRRHOTITE
    \
    (s
    s -12
    EMATTTE
    -w
    MAGNE'tITE
    -t8
    IRON
    :10 -16 -* -x -t2 -?o -N -26 -AL -22 -tg

    Log foz

    Plgure 11-1r fS, verrue'fO, dlagran (4OOoC) for the pyrlte-chalcopyrlte nl.neral
    aeseoblage ln vel.us et
    lapu-Thaoeo and Tul lllue. The detalls of
    conatructlon of the dlagran ere glven Ln Appencllx V.
    Thc fleld lor the early Tapu-Thanee nineralLsatlon 1o deflned by
    rare pyrrhotlte (early) and lors couron pyrite-chalcopyrlte- sphalerlta.
    The lron conteat of ephaleriteg f,rqn the. latter aaeeublage lnclJ.eeteo log
    fSa valueo betveen -4.4 ana -4.6 at 4OOoC.
    The fleld for the early luL lllne nlneralisatton ls deflned by
    coaron pyrlte-chalcopyrJ,te2 lese counoa pyrltc-hsnatlta anil henatlte, tho
    aole fractlon of, gllver ln natlve gold'(lndlcat!.ng log fSa valuea' betueen
    -3.9 anil -4.6) and alao poealble rery rare bornlte.
    Ihege flelde lnallcate that the pyrlte-chalcopyrlte ulneral
    aaaeublage le generally iteposlted at reletlvely btgh eulphur and orygen
    fugacltlcr.
    2L?

    I
    -t
    oc{
    ,
    I
    fuf Mln"
    so iry
    -J

    Temwature("C)

    Flgure l1-2: foa vereue terperature diegrau (bageil on Flg.{ of Burnbau & Ohuotor
    1980) relatlng the f0a-t ftelds of tbe fapu-Tbanot and Tul l{Lne pyrlte-
    ebalcopyrl.te nLneral esseublages to tbe stablllty flelde of pertlaent
    iron-bearlng u!.aeral aseeublagee (at approxluately 1 kber) and aqueous
    sulphur opecleo (at pH=4). the early Tapu-Tbanos nlnerellsatlon uaa
    deposlteil frop a flutd contalalag ilLasolved aulpbur predonlnaatl'y la
    reduced forur nhereas the coscentretlon of aqueous oricllgeil sulphur epecleo
    tay have been equal to, or exceeded, tba conceutrat'ton of aqueoue reduced
    aulghur apeclee durlng dopoa!,tlon of tbe early Tul Hlae nlaeraligatloa.
    2L4

    TABLE 11 - 1r Oeochealoal paraueters for aoIle reprogentatLves of


    the pyrlte - Bphelerlte - galena - chelcopyrite +
    electnun ! stlver olneral, aad 5b - sulphosalt
    nlneral aosenblagee' derlved fron the data presented
    ln Appenill,x I.

    pH dlagnostlc
    aLteratlon-veln Predonlnant S
    toc ptl nLnerals specles ln solutlon
    Te Ahunate Stage 1 ?1O 5 gerlclte -. adularta auLphlda

    Parltu 325 5"6 aerlclte - adularia sulphlde


    Tokatee Bese netal 280 1.5 - 6.5 ssrlcl te (ailu3.arla? ) oulphlde
    Petote Strean Stage 1 300 ,.6 serlclte sulpbtde
    llhangapoua Stege 2 28O 1.5 - 5.5 serlclte sulphltle
    Tapu - Theues Pb-Zn 280 1.9 serlcite eulphide
    Neavoevlllo AJax 25O 6.2 serlcl.te - adularia. aulpbtde - oulPhate

    lfaratoto Stage 2 284 5.5 - 6.5 eerLcLte - ailuleria aulphlde - sulphate

    l{Eltekauri Stage 2 28O 5.6 - 6.2 serlcl.te - adularla sulphlde


    tlatht lov levelp 325 5.0 - 5.7 geric!,te * adulerla sulphl<le

    WalhL lnternedlate levele 280 1..5 - 6.6 sarislte and sulphide


    sertrclte - aduLarla
    Karangahake lov levele 30o 5.1 - 5.6 eerlclte - adularla sulphlde
    Tul lllnE Stego 2 30o 6.0 - 6.3 sericlte - adularLa eulphlde - sulphate
    tleiorongonal Stago 1 725 5.3 - 5.6 eerlclte eulphlde - eulphate
    2L5

    isations consist predorninantly of pyr:ite, sphalerite, galena and


    chalcopyrite i.n quartz and calcite gangue but acanthite, hessite, electnm
    and various Sb - As stdphosalts occur in some deposits.

    Ce ochemica] Srvironrnent
    Table 11-1- lists srJrne of the aspects of the nrineralisations consiciered
    i:r th:is section.
    Temperatures of mj.neral deposition are considered. to 'r:e generally in
    the region of 27O to 34OoC but mineralisations at lower temperaiures
    occui'red, ai l,ieavesvil-Ie (250oc) and fe Abumata (ztooc). -ltro conclusive
    evidence of bojLing blas noted frcn any of the deposi.ts although widely
    spread fluict inclusion filling temperature h5-stograms (e.g. l.{aratoto) ma3r
    indicate proximity to the boiti:eg cu.n e.
    The hydrothermal fluids were i-:rr equilibriunr with sericite and in
    rnany cases adularia jn the l'raII rocks and veinsri.:ndicating near neutral
    _ pH conditions.
    Sulphur fugaciti-es during mjneralisations of thj.s stage for the
    different areas are very sj.rnilar (alloidng for the difference in temperature)
    with bornj.'i;e absent from aIL deposits and pyrrhotite present only irr two
    sar,rpies frorn l{aihi.
    The concentra'bion of total sulphur in solutj-on varies lri.th iemperature
    of mj-neralisation but is sj.rniJ'ar for deposits forned at simllar temperatlrres.
    In rnost deposifs sulphi:r rras present in solution predonrinantly in
    reduced fonn although in others the ratio of dlssolved sulphate to dj.ssolved
    srilphid.e is quite varj-ab1e (trig. 11-3) and, in the case of the Carnoola Vein
    of l.iaratoto, may have exceeded 1. The occurrence of sel-enium in sorne
    sulphicies (".g. acanthite) is consiclered to indicate oxidising conditions
    in scne veins at Maratoto and ilai}ti.
    The occurrence of telluride minerals i-n some deposits is related to
    the concentration of total telluriun jn solution (nig. 11-4) and fTe,
    (itig. 11-)) which were particu1arly high in the vei-ns of Tapu - Tharnes
    and Thenes (hessite, stutzite, sylvanitej altaite, tell:robismutite, petzite,
    coloradoite and nagyagite) lfaiorongomai. (hessite and altaite).
    "rrd

    Hireral Deposition
    Although the causes of mineral deposition vary between deposi.ts of
    this group, two meehanisns are considered prevalant: changes in fluid pH
    (due to reactions of the fluid with the waIL rocks) and trr. SoU2-ff%S *
    IS-] ratio (oxidation - reduction generally caused b1r mixing with aifferent
    fluids).
    2L6

    Kaolirtrte, lgeric\fe

    ---\
    -?o :
    6' I uRsuatrrg
    S-rz
    U
    7'

    PH

    Flgure 11-l: f0, vereus pH tllagran for the pyrlte-aphaLerlte-galena-


    ehalcopyri.te i elect"ut i sllver n!.nerale, and the Sb-aulphosalt.rnlneral
    aaaenblagee. The dlagran nas construeted for a touperature of 300oC and
    a conctrtratloa of total sulphur ln eolutlo-n of 0.01n, by tha E6thod6
    outllnoal ln lppendlx V. The poaltlon of the kaollntte/serlclte boundary,
    aerl.elta/K-feldapar boundary and gtablllty flelde for the rarl.oua deposita
    have been extrapolated fron aevsral dlagraue at dlfferent tenperatures
    (Appendlx 1 ).
    Fleld 1 ' lfsavesvllle (AJax), [sratoto (Stage 2), Iul ltlne (Stage
    2) and ifaloroagoaal (Stage 1).
    Flel,d 2 . Te Ahunata (Stage 1 ), lforthern Colvltle Peni.neula (Sorry
    llary Strean and Doctors Creek), tlaltekaurl (Stage 2) and Walhl (lnter-
    oedlate levels)
    Fleld 3 = Tokatee (base netal)r Petote Streao area (Stage 1) and
    Tapu-Tharnes (ru-Zn).
    Fteld 4 = llhangapoua (stage 2).
    Fleldj=Walhl(Lon levela).
    lloet reprisentatlvee of thesa asseublages are forned frou
    aolutlonr at near neutral pH and -containlng dl.esolved aulphur predonlnantly
    Lu reducsd forr.
    2t7

    (\
    o
    -36
    so

    Log m *,Te

    In solutloa dlagrau
    flgure 11-12
    . fOa veraur coscontratlon, of total tellurlun
    (baaod'oo Ftg.10-/o of Abnad, 19?9) il.fuotratlng the stablLity'-flelde of
    eone tsllurldo bearlng pytlto-epbal.erlto-galena-chalcopyrite I electruo
    1 allver uineral aeeenbJ.agee at t . 25oocr n 45 ' 0.014, pll r J.! and
    I = 1. Increaslng concentratloag of totel tellurlun ln solutlon are
    . tndlcated dosn the fol,loving eorless
    (a) hegalte (etlppled): Tokatea, Tapu-lbaoeg, Thaoeg, Noavegvllle
    (AJax), Maratoto (ualnly the Sllver Queen veln), Ualhl (Roseuont Hlll
    velna only) Karangahake aud llalorongouel.
    (b) coloradolte (croaaee): thanea'
    (c) altalte (dlagonal l'lneE): rapu-lbeueg, Thaqes, andl llal'orongoual
    (ono occurrence),
    (d) calavorlte anil natlve tellurlun (uot deslgneted): Tapu-fhaoee
    (one occurrsnce roported by Raudohrr 1980).
    Sone error la appareat ln tbe phaae relatlons shouu becauae the
    occurronco of altalte ylth electruu, but not celraverlte; ln the Hrurakl
    Gold-SlLver Provl.uce 1e belleved to occsr at hlgher oxygB fugaclty than
    ghosn on the dlagrao (even taklng lato account tbs extrapolutlon,betneen
    the depoeltlonaL tenperature and Eodelled tenperature) ' Tberefore tbe
    electrun/calverlte boundary nay ba at hlgher values of 1og u Te than
    tbose for the goLit/calaverlto boundary, at aay glven value of 1og f02.
    21.8

    -c I I

    Ic sdid
    'te va?aur
    /
    7

    Calavertle(Au
    I Gda
    Y
    P
    (\, - I

    (F-
    o
    I
    E
    *- .g
    c 'I'
    /
    +
    l a i:i1ri,t;
    CAnrnAoila &. :,. .1 .I
    .E
    rl :...':" Zr-\
    Mcrcury J"' ( (f' 'iC 6-
    -
    )- +
    o .g
    12

    -''-tT
    _l3r |
    -12 -rl
    { r
    s
    s
    .s
    (,
    ' '
    -to
    # r'=
    -9 ' ' r
    -g '
    - -
    -7
    ! 'io
    c I
    -s
    (/ cO

    - !

    -b

    4fiz

    Flgure 11-5: fTe, vereus f$a dlagrao for sone tellurtde nlneral-bearlng pyrlte-
    sphal.erlte-galena-chalcopyrlte ! electruu t gllver nlnerals aeeenblagee.
    The cllagra! vao conatructecl for e tenperature of 30OoC by the nethocts
    outllnail ln Appendlx V. Increaelng f?e, 1a lndlcated for the prograsslon
    of ulneraL aaoeoblages: hesslte (atlppleit)r coloradolte (croegea), altalte
    (illagonal llaag), calaverlta and natlvE-tellurlun' Prasnt ln soEq of the
    ttaurakt rlnerallsatlons (see llgt ln captlon of Flg. 11-4). Blgher valueg
    of fS, are ladlcatcd for the altaitB occurrenees (aee Flg.11-4) than
    shoyn ln the dlagrao, a-s lndlcateil by the a,rron antl therefore the elect,run/
    calaverlte boundary la coneldered to be at a hlgher value of fTe, than tha
    golil/calaverlte boundary shovn (e.g. 1og tTer ' -71.
    z1g

    The varj-ab1e concentration of dissolved CO2r indicated by fluid


    inclusion studles, probably had a marked effect on fluid - wall rock
    erluili-bria, calcite depositionr calcite solution and pHr however
    insufficient data are avaifable to investigate these effects in detail.

    Pyrite - .{canthite - negtr-un Assemblg.qe

    Geochemical Ervironment
    Although pyrite - acanth:ite - electrum mineralisation i-s reported in
    the early literature frorn many of the deposits and vlould appear to be the
    donrinant precious metal mineralisation at Komatal Golden Cross and in the
    upper levels of ';Iaihi and Karangahake, the writer was unable to obtain
    samples of this assenblage. Quarbz veins ercposed jn the upper levels of
    lJaihi and I and 12 levels of the Telisman Mine (Iiarangahake) 1 and qr:artz
    plus calcite vejns exposed j-n I level Kornata, contain no vj-sible
    mineralisation (except for pyrite) even though assaJrs irrdicate the presence
    of golcl and silver (generaI3-y 1o* grade).
    Eluid inclusi-ons in quartz and calcite of these veins indicate
    depositi-ona1 temperatures around 2OO - 23OoC and these temperatures are
    considered to approximate those of pyrite - acanthite p electnrm
    rrrineralisation.
    The fluid rvas in ecluilibrir:ia vrith sericite and possibly also adularia
    in the wal-I roclcs indlcating a near neutral pH. Kaolinite ls reported fron
    the veins and vral1 rocks of sone deposits but it is considered to represent
    ar later stage of alteration.
    The occurrence of boiUrrg was noted in sorne material froir Konata and
    daitri but its relationship to the mineralisation is unlsrcrrrn,

    l{jneral Deposition
    Pyrite - acanthite - electrum rnj-neralisation probably occurred due
    t,o a nurnber of different factors qlerating at <iifferenf locations. Boitine
    may have been irnportant at Komata and possibly for some of the i{aihi
    mjneralisation. Decreases jrr fluid pH were probably al.so irnporbant at
    :,,taihi. l,lixing of the hydrothermal fluid vlith near surface neteoric rvater
    is another possible rnechanisrn and may have been inrporLant at Karangahake.
    One deposition appears to have been often assocjated with zones of
    leached calcite (goId tenor was reported to fal.l on j:rrtersection of prirnary
    calcite) suggesting that, if the two are associated, conditions causing
    hydrothermal leachjrrg (decreasing pHl decreasing temperature, and S.ncreasing
    fCO2) were conducive to the deposition of electruro and acanthite.
    220

    Fvnlte - Electrum .\ssemblage

    lntroduclion
    Pyrite - electrum mineralisation at the Bluffs section of lleavesville
    vias not differentiated frorn the pyrite - acanthite - electrun assemblage
    j.n Chapter /ar because of its very lirnited occunence. Flowever, a separate
    rlescription is included here because of the good geochernical control
    on the environment of deposifion.

    Geochernical Brvironment
    fltuid inclusions indicate thaf the pp:ite - electrwn assemblage was
    deposited at approximately 22OoC from boiling fluj.ds with log fCO, around
    1.2. A near neutral to slightly al.kaline pH is indicated by the presence
    of adularia in the waIL rocks. fS, values, calcrrlated frsn the ccnposition
    of electrum analysed by Torckler (1975), help define the dissolved sulphate/
    dissolved sulphide ratio to a value of approximately 1 for a concentration
    of total sulphur in solution of O.O1m (c.f. Eig I-lI-9 of ippendix I).

    I'lineral Deposition
    The principal mechanism of electrum deposition appears to be boiJ.ing
    in a relatively oacldising envjronnent.

    P.','rj-te - Bonirnza Electrrun isseroblaEe

    Geochemical Srvironment
    Pyrite - bonanza eleetrun mi.neralisation occured in quartz veins at
    Corsoandel (Kauri tslock and I',apanga l,lines) and Thames.
    Merchant (19?8) concluded that the Thames bonanzas were formed at
    approximately 23OoC frcrn boiting f,Luids. Kaolinite and sericite nere
    present in the veins and waIL rocks indicating that the flulds tgere acidic.
    a si.railar enrrironnent is envisageC for +.he Ooromandel bonanzas

    a-lthough no f1ui.d inclusion evidence is avaiJ,able to substeunfiate thi.s


    h3pothesis.
    UineralogicaL evidence indicates a predoninantly reduci.ng emrirqment
    during both Corcrnamdel and Tharaes mjneralisations, wi.th sulphur present in
    solution predcrninantly as HrS. However, the presence of barite and enargite
    in some of the Thanes mineralisatlon may indicate the local occunence of
    ocidising condLtions, possibly a dcnrnward incursion of the acid sulphate
    water environment present ln the werlying alunitised rhyolite rocks.
    22L

    The concentrati.on of total sulphur in solution is considered to have


    been about 0.0O1m.
    Values of 1og fCO, as high as 1.5 or possibly 2 are possible wifhout
    the fornration of graphite in the Thames bonanzas but this parameter must
    have been lower than O.5 aL Coromandel.

    l{ineral Deposi.tion
    If ihe boiJ-ing ernrironment hXpothesis is eorrecf , boiling r+ould have
    been the predaninant nechanism cau.sing mineral deposition. BojJ.ing off
    of HrS frorn the fluj-d would cause instability of gold and silver stflphide
    cornplexes in solutj.on and the acidic ervironrnent indicated for the Thames
    mineralisation would also help prcrnote deposition.

    Au - *.e Sulphosalt l.Iinera1 Assemblage

    Geochemi.cal Sovironrnent
    Epithermal pyrite, Au - At sulphosalt ald electn:m mineralisation
    occurs in qu,artz veins at Te Ahunata, hoken l{i]]s and Thames,
    Fttling temperatrrres of fluid inclusions in quarfz from this assemblage
    indicate water temperatures around 22OoC at Te Ahumata (Erceg, 1p81) and
    23AoC af Broken 11i'l]s (this study). The Broken IIiILs fluid ruas boiling.
    Sericite and kaolilite occur in the naIL rocks, although adularia has
    also identifLed at Te Ahumata and Bnoken Hills, The kaol,lnite is
    been
    interpr'eted as a late stage overprint on earlier sericite plus l(-feldspar
    assemblages and therefore the pH of the early fhrids was probably near neutral,
    The occr:mence of seleniferous and selerrj.de minerals in this assemblage
    suggests a relatively high d'issolved sulphate/dissolved sulphide ratio il
    the hydrolhenral fluid (c.f. Appendix V). Some assemblages at Broken Hil1s
    also contain barite, indicating that this ratio may have exceeded 1.
    fhe concentration of total sr:lphur in solution was approxirnately O,OO1m.

    Eineral. Deposition
    Mineralisation occurred as a result of instability of the metal sulphide
    complexes in so).ution caused by mj-xing of the hydrodhermal fltuid w'5-th dilute
    cool near surface uaters (causing dilutiwr, a decrease in temperaturel and
    oxidation of the hydrothernral fluid) and, in the case of Bnoken HiILs,
    boiJ.iag.
    222

    Stibnite

    Geochemical Environment
    The stibnite mineralj.sation at dhang,apoua ("taingaro Stream) was
    deposiieei at temperatures of approxi.rnately 2OOoC or les.s from boS.ling
    fluids, r,+hereas sjnil-ar iaineral.isation ocsured ai Te 4hunata frorn non-
    boiling fluids at temperatures aror.md 24OoC. Information on conditions
    of stikri.te mineralisation at Tharnes j-s not avaiJable.
    Fluids depositing stibnite were acidic (in equilibrium lvith kaolin:ite
    and sericite in the veins and ','raIL rocks) and characterised by relatively
    lotr o>rygen and carbon dioxide fugacitiesr and high concentrations of total
    sulphur. Sulphur in solubion was present predaninantly in reduced fornr
    (gS Hf,), although SO4'?- may have hreen loca]ly iruporbant irr scme of
    "tta
    the Thames mineralisation where barite was also deposited. The presence of
    arsenoplrite in scrne of the Te Ahumata stibnite nineralisation jlctlcates
    conditions of relatively Iou fSr.

    l,lineral Deposition
    The instability of anti-nony sulphide canplexes in solution and
    subsequent deposition of stibnlte appears to have occr:rred at Te Ahumata,
    i'ftrangapoua and Thames because of decreasing pH, coupled lrith boilfug at
    '!.ihangapoua and oxidati.on at Thames.

    tsarite

    Geochemical Sovironment
    The temperatureof barite deposition appears to have been quite
    variable and spans a considerable range. Iierehant (fqZA) noted fluid
    inclusion fi[in; temperatures ranging frcn ?3O - tO5oC (but mainly betr.ieen
    Z6OoC and 23OoC) for samples frqr the l,tonorai Vein and Stokes Reefs north
    of Thames and a range of 2BB - it32o} was recorded here for plates of barite
    coati.ng Stage 3 vug quartz crystals frcrn Tui Mine. In contrast, r^r"ith the
    exception of one inclusion at 196oC, filling temperatures for sjmiJ.ar
    barite from l.laiorongcrnal" were between 98oc and 128oc.
    Robj:rson (L971), using olqfgen isotope fractionations, calculated
    tentperatures of 21O ! 30oC for barite grown r*ith Stage 3 vug clrrartz and
    15O t 3OoC for barite coating Stage 3 qr:artz of fui liine.
    Fluid irrclusions in hoksn Hil'ls barite have not been investigated,
    ho*ever temperatures of deposition are probably between 2OOoC and 25OoC
    (c.f. Eroken Hills qrrartz).
    I

    ?23

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    tr,

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    P
    E- s.9 u
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    9.O tJ= {- 's d
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    +." H'F. .9 =
    .r.r.9
    T5 E
    u
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    b):5
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    221+

    Kaolinite and sericite occr:r in the wall rocks of the barite


    rninera'l'isation i.ndicati:eg that the hydrobhermal fluids were acidic,
    particularly at 1ow temperatures. Orrygen fugacities rirere relatively high
    rvi-th the fluiCs containjlg approximately eqr:al proportions of sulphate
    and sul-phj-de, or sulphate predorninating wer su!:hide.

    lli:rerei ilepositlon
    Late stage barite dsposition at Tapu - lhames, Td luiine and
    .Jai.orongonai appears to have occumed as a result of falling temperature
    and generally oxidj-sing conditions.
    Deposi.tion of barite du:cing gold - silver rnj-neralisation at Broken
    Hi]]s and Tharnes (gold - pyrarglrrite association of l,Ierchant, lpf8) was
    probably related to boiling, oxidati.on and a decreasing pH.

    Mormr. 0I' EPITHEPMAI" IIEIN MINERTUJSATIOII

    Introduction
    The hydrothermal fluj.ds responsible for the epithermal vein deposits
    originated as deeply circulating meteoric water, wh5.ch in some instances
    penetrated to sufficient depth to rnix lv'ith magmatic fluj-d. Components such
    as sulphurr carbon and the metals rvere derived frso the ruagi'natic fluid anC
    by walI roek }eachiogt the relative importance of these two sources
    var;rin6 according to depth of fluid circulation and proxinity to the igneous
    heat source.
    The forn,ation of the various vein mjneral assemblages is modelled
    on a hypothetical depth zonation scheme 'i'llustrated in Fig. 11-5. Deposition
    of the variot:.s vein mineral assemblages oceurs in response to the changi.:n-q
    physicochenrical enyircrnment, resulting frtrr the inter-reactions of the
    hydrothermal ftuid with the waIL rocks as the fluid aseends
    through the vei.ns to the surface. The occurence of specific urj.neral
    assemblages depends on the presence of favourable structural envirorunents
    in ad&ition to suitable physicochenical conditions, Therefore, the presence
    of a particular mjneral assemblage in a deposit does nob necessarily iunply
    that lrith changing elevation there shorfld be a transition into the adjacent
    mineral assemblages shovrn in the model.
    Three aspects of the model are elaborated j.n the fo1low5ng sections.

    Hydrology
    Three major hydrological zones are shorvn in Fig. 11-51 (a) a deep
    mixing zone where magrratic fluid mixes with deeply circulating meteoric
    2,5
    water, (U) r" intermed.iate zone in which the changirrg composition of the
    hydrothermal fluid is predominantly related to i-nter-reactions rdth the
    rval-l rocks (Uut not mixing), and (.) near surface rai:ci:rg zone t*here the
    ^
    hydrothermal fluid rnj:,xes r,rith cooler and oxygenated near surface water.
    If the magnatie fluid has a vapour conponent (c.f. Chapter 10) the
    first zone rnalr represent a boiling horizon (e.f. 3u - 5i;ssociation of
    .lapu - Tharnes; I:erchant, f973). Boilind may occur at other horiaons if
    the ouiflols of the hydrothermal s;nstem exceeds the reclnr6e (c.f. vapour
    clcrninated systems of l,ltr-ite g!4r t97I) or as a resu-lt of pressure release
    following dislodgement of vein obstructi-ons (e.9. explosive clearing of
    veins necked due to crSnstdlisation) and hydraulic brecciation of porous
    waIl rocks (e.g. breccia pLpes at Broken HIILs and Neavesrrilte). The most
    frequent locaticn of boti-ng appeers to be near or abone the Junctiqr of
    zonss (b) and (c).

    Hydrothermal Alteralion and Solgtion Chemirstry

    Introduction
    The sequence of hydrotherrnal alteration assemblages, in order of
    decreasj.ng depth, is: quarbz - sericite, argi'l'lic (c1ay - sericite),
    propylitic, argi.llie and advanced argi3-lic.
    The hi-ghest grade of alteration encountered in some deposits is
    propylitic, suggesting that sqne water circulation cells did not penetrate
    to sufficient depth to1cquire fhe physicochenical characterj-stics necessar]'
    for quartz - sericite and deep argillic alteration capability. Therefore,
    at least tr'ro starting poi.nts occur in the rnodel, one in the quartz -
    sericite environment (high degree of magnnatic input) and the sther in the
    propylific environment (Ior,i degree of magrirati,c input) .

    Quarbz - Serici.te Zone


    Etuid - vrall rock reactions in the quartz - sericite zone produce
    secondary quartz, sericite anC pyr:ite in the -itnlI rocks by h;r}:egs:'r
    (Oominant) potassiunr (subordinate) metasomatism acccrpanied by release
    "nd
    of lrla+, c.2* .rrd t-lg2+ to the 1Luid. Consequent\r the rl.iaf( antt KCI/HCI
    ratios of the fl-uid increase througlr the zone.
    i\t high temperatures (i.,e. above 4OOoC) oxi.dised sulphur is present
    in the fluid as SOr. Uith decreasing temperature the SO, hydrollnses to
    HrS and %SOf, (eqr:ation 1O-1, Chaptei 10) and the resulting ilcrease in
    HaS activity may be a major nechanjsrn for sulphide deposition.
    The quartz - serieite environsrent i.s depicted in IAg. 11-6 as the zone
    where magmatic fluid mi:ces vrith meteoric water. Sulphide deposition may
    therefore also result frqn the effects of dilution and a decrease in
    226

    temperature.

    Deep ;irgillic Zone


    The prociuction of HCI during sulphide deposition in the qtiarbz -
    sericite zone (c.f.e.iuation 1O-3, Chapter 1O)s coupled with increasing
    dissociati-on of acids such as H01 and %SOio wj.th decreasin6 temperature,
    results i:r a decrease i'n ttre KCI/HCI ratio in the h]'clrothermal fruid and
    possibly a shift of the fluid - mileral equilibria froro sericite to
    kaolinite or p;rrophyllite. The resulti-ng increase i:r hyclrogen metasqnatisnt
    of the waIl rocks (argillic alteration) tends to neutrali.se the fluidt
    ilereasing tbe KCI,/HCI ratio. Therefore this zone rnay be equivalent to
    Giggenbacht s (X981) ttPrinary Neutralisation Zoner.
    flr R.L. Brathwaite (pers. conm.) considers that deep argillic
    alteration in the sense used here is not weIL dweloped jn the ftrauraki
    GoId - Silver Prorince but that quartz - sericite alteration generally
    Ixrsses into propylitic alteration zones without an argiLlic intermediarJr.
    He considers that the interrnediate argill:lc aI',,eration zones adjacent to
    medi-rln temperatr.rre (1.e. 25O - 32Ooc) vein deposits (e.g. Maratoto) may
    be retrograde assemblages'formed by late stage orerprinting on origjJtal
    propylltic alteration assesrblages. Therefore in these cases the decrease
    in KCL/HCI ratio of the fluid, frcn sulphi.de deposition in the quartz -
    sericite zone and dissociation of acids, did not reduce the pH sufficiently
    for kaolirdte deposition. The absence of appreciable acid dissociation
    (e,g. qsoa) i.mpLies a l-ow sulphate/sulphide ratio in the fluid.

    Propylific Zdne
    !{ith <lecreasing temperature and acidity (increasing KCl/Hgl ratio)
    the alteration changes to propylitic and minerp,ls such as chloriter epidotet
    calcite and adularia-becone stable in addition to p;rite, qr.lartz and
    sericite. The specific alteration mineral assemblage depends ct fCO,
    (u.g. epidote, wai.rakite and/or calcite; eppentlix V)r pH {t<aolinite,
    sericite or adularial c.f. Fig, V-[1 .ippendix V] and temperature (e.g.
    heuLandite or wairakite)
    The hydrothermal fLuid passi-ng through the propylitic zone i.s of the
    alkaLi chlorj.de tirpe (c.f,. EL[j.s & I,'lahon; t977). The nain fl-uid - roall rock
    reactions i.nvolve COrr h:rdrogen, calcium^and potassium rnetasqiratism irith
    concsri'Lant release of lla+, Mgt*, and ,i1)+ to the fluid, Giggenbach (19S1)
    stressed the imporbance of the plagioclase + CO, = calcite + clay reaction
    in modern geothermal fields as a controlling reaction of water chemistry.
    ?27

    The pred.mTinance of sericite and calcite in most propylitic zones of the


    Har:raki Gold - Silver Prorince suggests that this reaction vas si.milarly
    i.rirportant there.
    Propylitic alteration is the most widely recognised tfrpe of hydrothermal
    alteraiion in the prorrince and j.s generally acco.apanied by deposition of
    lretal sulphide 1 electrwr mineral assemblages in veins. jiome veins contajn
    abundant calcite and a few also contaj-n adularia, suggesii-:rg that near
    neutral pH is favoured for this t;pe of mineralisation.

    liear $.rrface Argillic and Adrranced Argillic Zones


    l4ixing of the hydrothermal fltuid r,rith near surface oxygenated water
    2-
    causes progressive oxidation of the remainj-ng fbs irr solution to SOu--
    and a decrease jn pH. This may be cornpounded in sorne cases by condensation
    of CO, and HrS (with subsequent oxidation. to tOU'-)1 enarratins frqn lower
    boiling zones, forrni-ng acid sulphate waters (e.f. Ell.is & Mahon, L97?).
    ,r second cycle of hydrogen metasomatism occurs producing argillic
    and advanced argillic alteration. Kaollnite dominates the clay mineralogv
    of these zones although montmorjJ-lonite sornetimes occurs. In areas r,ihere
    the concentration of sr:lphate is iLigh i.rr the fluid, alr:nite may be
    produced.

    Mineralisation
    The various vein mineral assemblages are shown in a depth zonation
    sequence i-:n Fig. 11-6 ancl are groupe<l into four netal zones: Ito zone,
    Cu zone, Cu-Pb-Zn zone and Au-Ag zone.
    The generalised verfical metal zonation; ;{r}.'1o, Cu, Bi, Pbs Zns ;ru,
    .tg, Sb, and llg, is believed to reflect increasing solubility of the metal
    carrying canplexes (Ieast soluble deposited first, most soluble deposited
    last) coupled 'rrith the changing role of chloride and sulphide conplexes as
    transporters of the metals and the different responses of these complexes
    to the .rertieally changing physicochemical environment (upiward cleereasing
    temperaLure, d,eereasing pH and increasing ox5-di.sing conditi.ons) -
    Deposition of metallic minerals in the !lo, Cu and Cu-Pb-Zn vein zones
    is believed to occur from rnetals transporbed in solution as clrloride
    cornplexes. In contrastl deposition of metal-lie nninerals at lower
    temperatures in the *u-;.g zone occurs frorn rnetals transported in solution
    as sr.r-lphide complexes. Because these dj.fferent t;pes of cornplexes respond
    differently to specific changes j.n sqne of the principal physicochernical
    parameLers (viz. *S2-, fO, and pH) tnis property 5-s a major contri-buti.:ng
    factor to the zonation. For example, deposj-ti-on in the Mo, Gu and Cu-Pb-Zn
    228

    ueaes J.s csrsidsred to have predmi:nantllr ocs-u--Tfad duo to- an fuie,rcaec in


    plt {beearrse of, reactisrs wlth the r*atL r:oc}rs e boi}ing) anrl raducfil-urn
    where,as decr,easir,lg pH, oxidation end decrcasing
    %f- (due to boiti^ng off
    or !ir$) carsed rnfieral depotltion io the Au-Ag zom*
    . Oecreasing tomperature, altholqih nc# c,clsiderod Lhs prine5.pal cauEe
    of rnetal depooitS.mr determlnes the ovcral"l netaL eanat'-iqr tpcause it
    coubrsl.s.the oolub tlity tre,nd and also the rolative frporta-rre of chlordde
    end sr,rlphide coqilexes of 6o.I'd and si1rtr,
    . Sprne guarlap bstween the Etrloride oeimplexed, Eetal. ad su.lBihide
    eonplexod metal s'onos occurs, par.ti[c:nLe:si[5i'if rnlseral depooii],on results
    frqr fector whlch caueca instabi}ity of chl.@=4dc and euXpbida
    eone
    ctmplexcs eqnaXly (a.g, dtl,rrtd.sl utthout sngpitricsrfi oddatier).
    229

    CHAPTER 12

    r-1Ir!ERj\IJpA?.101I Ar{p VoLCsr{IS.r

    l IIllEILiIJS.rTIOl'l ASSOCIATED ;'!"lTI{


    df ilisi ?Ic voIgAl'IISg,

    The Relationship Between rlnCesitic.


    Volcanism and llineralisation
    of the epithermal vein deposits are
    The porph;my copper and sqne
    consldered to have been deposited as a resu-lt of hydrothermal activity
    associated with the emplacement and cooling of intrusive magna bodies
    now represented by the intrusive rocks of the Corsnandel Group.
    The nrineralising envirsnnent envisaged is an andesitic volcanic
    terrain similar to the present Tongariro Centne of the Taupo Volcanic Zone
    (c.f. Cole, 7979). i4agna bodies occur at various leveLs beneath the cones
    of the modern ccrnposite andesi-te volcanoes. The occurrence of parasite
    cones and flank eruptions of lava indicate-the presence of various au:ci-Llary
    neeksl plugs and dikes of nagrna within the cone, in addition to the nain
    neck supplying the central vent (c.f. i'Iill.iams & ltcBirney, L979)- The rnain
    nagrna reseruoir occurs at deeper lerrel.s and recent work has demorrstrated
    that a conplex series of hypabyssal and plutonic magma bodies rnay underlie
    the voleanoes, in contrast to the classic simplistic picture of a single
    large magna chamber. For example, on consideration of geryhysical eridencet
    Iatter (1981) postulated the exlstence of magnra bodies at various depths
    below the volcanoes of the Tongariro Volcanic Centre.
    Btrapolating thi-s envj.ronrnent to the Corsnandel Group rocks reatiily
    accounts for the multiplicity of intrusive bodies corprising the Kai-iti
    Poryhyrites, Intnrsives and Tainui Intrusives in the volcanj-c
    'r'lhangapoua
    enrrironnent and Paritu Plutonics and scrne Kai-iti Porphyrites in the
    hypabyssal environnent.
    The epithermal vein deposits were probably forrned il shal.low (<2 !*)
    geothermal s;nstems generated by the general intrusive activity in a
    volcanic centre (i.,e. a sulte of hlpabyssal and volcanic intrusives),
    r+hereas the porphyf,y copper deposits r{ere associated urith speei.fic
    hypabyssal jrrtrusions ernplaced at depths greater than 1.5 km.
    The &ifferent mechanisms and depths of formation give rise to the
    contrasting spaci.ng relationships between porphyry cq)per and epithemal
    vei.n deposits suggested by Sawki.ns ( 1980). Porphyry copper deposits are
    spaced in the order of tens of ki.lcrnetres (Sawkins suggested an average
    23o

    CW lo1!},/,
    KIttUC{LEi POD.TT 17'Gmy.

    KAURI MOL/NTAN
    .COW6?.MINE lglAND l9-16'7rr.Y.
    HaAo la'lm'Y'
    o Stn"te
    I Cuvicr lsla(nd t6.) - t9.6m'y.
    $
    A
    rerryur (o.l) a.bs.tt't\.

    Flgure12-lt PorplryrT coppci Btylc dcpoat'.a (at aXt locatlma ahonr crecpt for M.cr
    Icland rhcrc ihs lntrnrlves arc urlrllncrallscd) of th. Nofth falsnd occur ln a
    chaln frcn Kinrckle Polnt, aouth to Tatnut (fagu - Tbanca). f,-{r agcs (ahom)
    of thc acaocl,alcd lntnrsiw rocka auggcat tro pcrl,odr of lonnatlorr zo - 16
    n'y. (ftnucldc Polnt, f,aur{, Ir{outalrr?1 Coppcr ltlnc laland, }llnera Hcgdr parliu
    Hanafs?) and 13 - ! n.|e (falnui).

    Sourc of l(-l,r agccr Parltu &nd Curt'cr lrland. arc fror glcharda g!-g! (1966),
    rhcrcac thc raldndcr arra fron llr C.at.D. Adlm and otbcru (pera. cam.).
    23t

    of 50 km) probably representing sites of rnajor r.rprise of magmas r whereas


    ,
    eplthermal vein deposits are spaced onJ-y a few kjJ-ometres apart (Sawt*ls
    cited examples averagi:tg approximately 5 trcn) represenLing the dinensions
    of the conrective ce1ls. The specific location of the vein deposits also
    d.epen4s on the presence of suitable structural envirorunents. Upi*ard
    rnovernent of the hydrothermal fluid rria far:lt fissures produces the mushroom
    cross-scctional shape that is typical of most nodern geothermal s;rstems
    (".f. Elcter, Ig65i t966). The largest conveetive cells penetrated deep
    leve1s (to tfre quartz - sericite Bc,ne of Fig, tl4) and probably interacted
    with magmatic f1ui.d,s, whereas the magmati-c component of the shallou
    convective celLs (penetrating to fhe propylitic zone of Fig. L1-6) vras
    probably minor.

    Seouence of Events lluring Mdesitic


    Volcanism in,the l?uraki Provincg
    ilnring the early Miocene (c.a. 2C - L6 m.y.), volcanism probably
    i:r-itial1y comprised several r,ridely spaced andesite strato-volcanoes fed
    frcrn chambers of granod.iorite and qr:artz diorite magna in the underlying
    greyracke. The latter are represented by a chain of nineralised irrtrusi.res
    (pig. t2-L) consistilg of the poryhyry copper style deposits at Cape
    Karekares Kauri llountain, Gopper Mjne Island., Miners Head, Paritu and
    Manaia, in addition to the r:nrnineralised intnl,sives of Cuvier Island.
    The first extrusive rocks of th-is series are represented in the
    Hauraki Gold - Silver Prorrince by the group of vo.Icanics at the norlh-
    eastern end of the Colvi.Lle Peni:rsu1a conTprising Port Charles Andesitet
    Onoho Forrnationl Kokr:mata Dacite and Te Karaka Andesite (fig. 2'4).
    The fuoho Formatiqn consi.sts of large pyfoclastie ff-*r deposits and
    probably originated by caldera eollapse of one of the volcanoes.
    The early l,fi.ocene volcan:ic episode ended Vrith the enrption of the
    Beesons Is1and VoLcanics and Tuateawa Andesite i-n the Coromandel -
    i{hangapoua area and the Tui And,esite (dated at 16'1 m.f,. bf, Adans g!g!t
    LgT4) at Te Aroha. Early andesitic volcanism in the Tiumes (Fremier
    rindesite) and Waihi areas may also have occurred around this time (c.a.
    15 m.y. ),
    These various volcanic formations (parbicularly the Ileesons Island
    Volcanics) contain rutnerous intmsive stocks, plugsr neclcs and dikes r'+hich
    lvere probably contemporaneous with exbrr,rive volcanism and are believed
    to have caused the hydrothermal alteraticnr and epitherrnal mi.neralisation
    in the Colvi}le and Corqnandel areasr and possib.Ly at lrlail1i.
    Dr:ring the mid M:Locene the volcanic sequence jgr the northern ara
    232

    conti-rnred r.rith the Andesitel lulaterangi Andesi-te; Parakete


    l{hangapoua
    Formation; Te Tutu Andesitel Ruaporoa Basaltie Andesite and l{ahinapua
    .tndesite, the latter dated at' 13.8 and 11.[ m.y. (Dr C.J.D. --idamsl pers.
    comm.). Some of these formations have been intruded by various sme'll
    stocks and di-kes of the llhangapor:a Intrusives whleh orobably generated
    the epiLhermal vei:rs in ihe l,'Jhangapoua and Kuaoturu er3sr
    In the southern region, the Tararu .indesite of Tapu - Thanes tras
    enrpted betl*een approxinately 13 and 9 m.y. and was intruded by high
    level quartz <iiorite stocks of the Tainui Intrr.r,sives (t2.9 - 9.3 fl.f,ri
    Dtr C.J.D. Adar:rss pers. cohtno), possibly related to caldera resurgence.
    Porphlry eqpper and epithermal vein mi^neral"isatiurs of the fapu - Thanes
    area occurred at thls time.
    In the late Miocene volcanoes began erupting in the vicinity of
    l4aratoto, I(crnata and Paeroa (f - fr ages of 9"1, 7.O and ?-O n.y.
    respcctively; Stipp, 1968). The I'launaupaki Andesite and andesites in the
    viciruity of Karangahakep Golden Cross and }Iaihi (second phase) may also
    have forrned dr:ring this period. The phase ended betl.reen 5 and { m.y.
    (c.f. le m.y. K - Ar age date for Corornandel Group andesites frqn the
    western end of the Kai;nai 1\urre1 by Stipp, 1968). Taurahehue Andesi-te
    probably formed at the end of this periodr around J m.y..
    The relatiotship betleen andesite volcanism and mineralisation in tlds
    southern region is compli.caied by the overlap with 'tfhitianga Oroup rhyo.Lite
    volcanism which riay a1-so have contributed to the mi:terali.sations (e.6.
    Thames, I(arangahake and. Tui liine). Nevertheless, whether these southern
    mineralisations are due to andesite or rtryolite volcanism they appear to
    have occumed less than 9 fi.5r. sgor
    The Coromandel Group sequence ended igr the Iate Pliocene with the
    intrusion and extrusion.of basic andesites of the Onah-i-a Andesite-(3.8 m.yo;
    Stipp, 1968)r

    I'IINEFAIJSTTTIPE ASSOCIATED','IITH
    ETIYoIJTIC VpL9ANISM

    The Relationship Betr,Ieen Rh.'roliti.c


    Volcani-sm and Mineralisation
    The deposits at Te Ahumata, Kapovrai, Bnoken HiILsl Phoenix Hill t
    NeavesvjJ.le, Luck at Ie.st and l.faihi Beach can be related to hydrothermal
    activity associ.ated with Pliocene rhyolitic volcanism because they occur
    partly or conpletely within ldh-itianga Group rocks. Several deposits that
    occur only in andesites are al-so considered to be related to rhyolite
    233

    :3fig
    lumcrole

    lal,tiarY
    valcavic, avd

    4
    7 GrcywacYc
    2

    Fig. 12-2A
    Vrlon:c.treg

    94 r 2 |

    Fig. 12-28 Yilort'etrcs

    (fig.
    Flguro 12-2: HocleLs for bydrothernal oyateus duriug antleEltlc volcan!'an
    . 12-2A) anit rhyolltlc volcanlgu (Ftg. 12-2F1. Durlng andeal?lc volcanlsn
    hydrotherual aystens, centered approxloately 5kn apartl ar8 goDerated by
    nany lntruslve bodLee. The close proxlnlty of the tragEa to the ground
    vater (neteorlc) .eonvectl'vE cellc al],ove a hlgh degree of nagnatlc lnput.
    ThehotteeteystensnaybeagaoclatodvlthporphyrycopPertypegystelrB
    beneath st,rato volcanoes or calileras. In contraet, durlng rhyolltlc
    volcanLsn the ragua chanbera are probably decp plutons (-bathouths)
    rhlch generate vtdely apaced (approxlnately 1Okn) hyclrothernal eystens.
    The nagnatlc lnput, apert froo heat and C0r, lnto the grountl ratet con-
    veetlve cells 1a ProbablY sna1l'
    ?3t+

    volcanism on the evidence of stratigraphy, stai:le isotopesr K - "rr age


    data, or hydrothermal alteration of the orerlying rhyolite rocks. In th:is
    group are 'uhe deposits at' Thames, Karangahake and Tui lline.
    The deposits associ-ated vrith rhy.olj.te volcanism are considered io
    represenN cen:ures of fossiJ. geothermal areas analogous to present day
    6eothermat activ5-ty in rhyolite roeks of the Taupo Yolcanic Zorre. fhe
    validity of this comparison is supporbed by the si,nil-ar tectonic setting
    and geologJ. of the ti.io rhyolite terrains and the presence of precious and
    base metal mineralisation in some of the modern geothernal fielcis (c.f.
    l{eissberg gEI, L979). Also they have sjrnilar spaci-ng relationsirips: the
    deposits that occur jn contj-nuous rhyolite terain of the Coranandel
    Peninsula (viz. Kapowai, Phoenix, boken llilJ.sr }Ieavesville and Luck at
    Iast) have an average spacing of approximately 11 lcn (range: I - 12 l<rn)
    compared with the modern Taupo Volcanj,c Zone geothermal field spacing
    of 12 15 tsn (Iatter, 198C).
    -
    The cornrective cell systems generated by rhyolite volcanism are
    considered to differ from those formed during andesite volcanism in their
    dirnensions and type of interaction with the i-ntrusive nragmas (Fig. L2-2).
    In the previous seetion lt r.ras suggested that dr:rjlg andesitic volcaaismt
    Iarge intrusive bod:Les of magma penetrated very shallow leveIs (within 1.f
    lsn of the surface) and in mamy instances directly interacted with
    circulating ground water (both porphyry copper and epithermal deposit.s).
    1n contrast, avai-lable evidence for the genesis of the Taupo Volcanic Zone
    rhyolites suggests that the rhyolite magna resenroirs are probably granite
    batholiths at, a ciepth of greater than 5 km (c.f. B'rarL 9L3I, L975).
    Plmoclastic flow and rtryolite lava (aome building) eruptions appear to
    directly tap these deep resenroi-rs nithout intermecliate sha1lo,r charnbers.
    p'il]lng in nodern geotherrnal fields of the Taupo Volcanic Zane, to depths
    greater than 2 lcr, has penetrated rhyolite pyrgclasti.cs, lavas and sediments,
    scne andesites, and greyrracke basement, but apparently no irrirusive sub-
    vollcanic rhyolite nagma rsersoLrs. AIso the geothennal (freat) gradients
    in these systeras arb too low for the rnagmas to be in close proximify.
    Therefore the hydrothermal coacvective ce1ls operati.ltg during rhyolite
    volcanism are csrsidered to be large but relatively Cecoupled from the
    nragmatic heat source (Fig. t2-2). Apart frcrn heat the magmatic contribution
    to the hydrobhermal s;rstem is probably smalL rtith most of the fluid
    eonponents being derived by leaching fron the sedi$entary and volcanic
    country rocks.
    235

    o25
    lllllr

    Kilorne.fres

    Whangamata

    T > -20

    N -to to -20

    ffi o lo -t0

    Elgnre I24z Negatlve isostatic verticaL gradient gravity anonalies


    (after Uoodwardl 19?1)I beneath the tlhitianga Grorpr which nay
    represent centres of rhyolitLc volcarrlsm (Dn D.l{.B. S}cirmerr pers.
    com.). Anmalies associated wC.th nqr-rtryolitic rocks j-n other
    parts of the Prorince are not shctryn, Anomal3r values in E6t vds
    .. -4 -2,
    units(1O's-).
    Sequence o.f ,Evgp,ts D.rring Rhyol*tic
    Volcanisrn i:r the Har:raki Prouince
    Durirg the late }liocene an extensional tectonic re;;ime vras initiated
    in the region followi:r6 the migration of the subduction zone to the soutlt-
    east. A series of grabens (ccrnprising the Corsnand.el Depression) forrned
    j:r t,he eastern pari of the region r.rith concomj-tant rhyolite volcanism.
    Ski-nner (pers. conmo) considers that several volcanic centres (ltg.
    L2-3) may be represented by negative gravity anornalies in the Isostatic
    Vertical Gradient Anonaly Map (Woodward, 19?1). These nay be anilogons'to
    the rhyolite volcanic centres of the Taupo Volcanic Zone, the latter
    representing firuJ-tipie caldera collapse stnrctr:res with each major'
    p;roclastic flow enr.ption havjng been fo.Llowed by coJ-lapse of the vent
    area and err:ption of Lava (dornes) and tephra (Cofer 1981). A similar
    eruptive seguence is recognised i-n some sections of the l,lhitianga Group
    (c.f. Table l.lor:ntail; ilay*ard, L974) but cyclic volcanic events have
    left a more ccrnplicated sequence i.n others
    Although rhyotite volcanism may have begr:n in the norbhern parb of
    the prorrince and proceeded southward (c.f. fug. 2-9)1 the ages of the
    assocjgted mineralisations may not necessarily fol-loo this trend. If the
    hydrothermal slretems vrere generated by heat fron deep batholithsr as
    suggested previousl-y, then geothermal activity may have becn contemporaneolls
    throughout most of the reg5.on, analogous to the w'idespread geotherrnal
    acfivity in the Taupo Volcanic Zone today'
    237

    CHAPIER, 1'

    COI{PARISON OF TTIE EPITHERI.IAT DFGITS OF TIE

    $AURAKI
    pROrryr{.CE HITH SIMIIAR pEPOSITS IN

    OTHSR PARIS OF THE WORI.D

    I}ITRODT'CTION
    The geologf and geochemistry of some tSpes of epithermal depoeits
    have recently been revlewed by Sillitoe (tglZ) and Boy1e (L979), whIle
    Hhite (19S1) and Henley & ELti.s (in press) have related the formation of
    epithermal deposits to modern georbhermal processes.
    this chapter glves a brief introduction to the occurencer character-
    isation and classification of epithermal deposits and cffipares the deposits
    of the Haural<i Protdnce r*ith sone sverseas examples in terns of sizet
    specific mineralogical and physicochemical featuresr and genetic models.

    COLD PRODUGAION
    Elithernal deposits have accounted. for approxirnately 5f'of the worlds
    totaL gold production, rar*ing thJ'd after placer deposits (approximately
    65f") ana deposits in Archean greenstone belts (approx5rnately LSfi] .
    production frsn the rnajor deposits in the }lauraki Pronince and sste other
    farnous epitherma1 deposltsr i.s listed irt Tabl-e lTL.

    ffiocApHrc occgRRENcE 0F wImIEnMAL DEPoSITS.


    The largest group of eplthermal gold and silver deposits occurs around
    the circum-Pacific volcanic belt and lncludes New Zealandl IlLJir the
    Philippines, Irulonesia, Japan, Colorado - Nevadal MexJ-cor Ecuador, Columbd.a
    and pernr. Howwer, depoeits also occur in U.S,S'R., Rolnania (Transylvanfa)
    and Spain.

    trPEs oF EFITHERMAL DEPGITq


    A mineralogicelly based classificatj-on of epithermal depositsl partly
    after LLndgren (tgZl) and Boyle (1979) is glven in ?able Lyz. The overseas
    exarnples cited are historically large gold and silver producers (faUte 13-1)
    and therefore in classifying the Hauraki deposlts orfly Waihil Karangahake
    and Thanes are of simjJ.ar econqnic slgniflcanceo These latter deposits
    E"fl.ELE '17-11 8s-1d p,rod,uetilon of, EoEe fauoue epithernaL depo si't.e.

    l'ti.ne or distrlct Ke oq S,q14


    HE,!{ BEAtAilO !{ai'bl,r t 2,Or0 r 0t0O

    Shanes 40,0o-o
    Eareagahaks !tn0oo

    ryXJ.I Enpeler Slae 111


    "7O0-

    IFD,0SSSIA Be.g&oetrefri 34,1'00

    F$EITFPTN,SS Accupan ,and fiatonok Hj.nes e05f 00|0

    ${sxIg0 Guanajuato '124" 4,010

    P3Rg tr'i.al,eadie n600.

    U, S. A ![eva*a Consto:ek ' 2A,6170,0


    'trdfic1ll 13d, OoO
    9oaopah ' 58'0Oo
    Silver Glty 2E,,000
    Rortind Mo-uata:Ln 12,000
    Jarbrtclga . ?,000
    GoLorado GrippLe 0reek 622r oo,o
    Su'nnyo,i.de 13'r,000

    Washington ftepubL:le 15,2A0,

    4u produeti.on fi.ggreo frou Dovneyl s. (.t ?35l Au * Ag bul3.ton


    totalg oorrest,ed by' the estiaeted AulAg ra.tlo,
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    2ho

    belong to the gold - silver catagorltr as suggested, by I;indgren (L933),


    If smaller deposits of the Hauraki Prq/ince are consideredl some of the
    other classes of epithermal deposits are also represented, B.gr3 silver -
    go1d, l4aratoto; gold - telluride, l,lonorai and Sylvia (Tapu - Thames);
    lead - zinc - copperr Tui t"iine; and mercuryp Mackaylown and Kauaeranga
    Va11ey.

    cHAqaclERISrIc rH{rqnEs oF ryrF}qq4At col.p ANp sIL_riER pEPITS


    Sillitoe (L977) noted that epithermal deposits are characterised by the
    foalorring features:
    1. They are ccnmonly emplaced in volcarric sequences ranging from andesite
    to rtryolite which are mid- to late Cenozoic i:r age.
    2. Veins occupy pre-.existing tension fractures, including faultsr and
    occur in branching patterns whlch are conmonly jncreasingly complex upwards.
    3. The host rocks are altered to propylitic assemblages on a regional scalet
    whereas the more restricted alteration haloes bounding the vejns consist
    of elther sericitisation and silicification (cormonly with adularia) or
    argillic and advanced argillic a-lteration (rrith clays, alunitel pyrophyJ.litet
    diaspore, etc.) acccrnpanied by vridespread silicification.
    l+. The deposits contain principally precior-r,s metaLs i.rr various proportionst
    but also base metals. Silver occurs as acanthite and arsenic- or antimony-
    bearing sulphosalts; gold as native goId, electrurn or as tellurides; Iead
    as galena, and zi.nc as sphalerite. Copper is plentifulr but comnonly occurs
    as enargite where advanced argillic alteration is developed. Stibnitet
    cinnabar and selenides can also occur. The main gangue is quartzr commonly
    as aphanitic chalcedonyr accompanied W varying quantities of pyriter calci.tet
    dolornite, bari.te; adularia, rhodochrosj-te and fluorite.
    5. Ipw confjni:ng prssure i.s jndlcated by veln featr:res such as drusy
    cavlties, filting, conb, colloform and cmstiforrn texbures and inter-rnineral
    breccias. Ore and gangue ninerals are ccrnmonly fine - grained.
    6. The shallow depths of emplacement, perhaps from 1OO to 10OOn beneath the
    surface, are emphasized by the abnrpt dslvnward termination or t bottqtLngr of
    mlneralisation or the donnward increase of base metal sulphides at the
    eryense of gold and silver, Ore shoots in veins have rarely been worked for
    more than 60Jrn verbj.call3r.

    * Footnote: Afthough the velns at Thamescontain gold and silver


    telluride rai.rnerals they are not gold - telluride deposits
    because the predonhant gol-d ninaral- Ls electrwt rather
    thart a gold or gold - silver telluride.
    zl+L

    Au/Ag pEisrgrrt INDET I'IOET MINNALS BEMARKS


    IOHE SURFACE PEnSr3l6Nt MlilEnAL9
    n^no ELEHEilTS ELEMH'!

    slgt, FaCa
    Ou.rtr lchrlc.dontl. Thlr a@.lr.rcli rutl dn
    I 9r9.F !rydtaFrult.. Brdl.. lludll.. (cl^otb.4 Ornatrllt brran ol gold .t l tlhf,
    M!. |rr, E
    cartonat
    Or.rU lclr.lodott. qmlbt, rc.lgt, dPl6a.i. tnaddr 6lnt thlt rer 6.tbr
    3102. F.,Cr H9. Sb. Ar.
    Dtdt .6rcDlla,
    a
    lrt. Mo g 8.. S', F dlbdllr, lrll.. tlso.ll. rurltfu.nd t!f,illf|@.
    ilbon116
    Ac..thlt., told. ltlbnllG
    Ld plphogltt.'l.llutldr
    A9!Au.Ar, Ou&l! (chrlc.dortl, FlrnldG birdutttltilr
    Ca sb.c0, lo, Dtrllr, crtbo^rlG, rpllhrntl gold-tihtt d.porila
    310a. Fr.
    t t grlila, tphallrllr.
    U9. n.3 Pb,8t. T., rdrlrlr. aluntlt rllvd Into 66. a- O.nd.llt
    S. rbrda ln d..gel.d d.9dltl
    lllctruc).lmlt$mll{ nuo.llq D..llt ltardm.l,
    lFlltr6lt.'
    Coh@dt ldr d l.rt6 ln
    ir
    Ou.rlr. 9'.llr. ott( c'ul@"trli!,9ttlta lold
    Slot, F1 Ca iv. Zn grlanl lptrrlTit!,
    a Mt.M4s
    ?D rghrlctll., 9.1ila brdlt 6ray .tdhdFtl ,lF,to rlnl
    Ou!d. Pttttt, Calqnllgh.Ldla.
    Av.l!. Cu, Sthrlsllr Effiltltils
    C..
    t 3102. Fa-
    tln.S
    Pb, Zn,A. g.rldr. rphtlcrllc, lr;.rrhlitl. tulqt6rltt, rllh d.pril
    M9. 3b.la ch.lcogt?t|., gold, l!6hdlilcL (rclitrf, Il.L
    lFoltbd.nlt.l lalluridd. told
    Cli!lcopyritr. l!lrah.d.ll+
    Olrdt, tt lla, lr^rritilq n,ollt:
    3iOr.F1C+ Au.Ae,qA tunottrlla. lrslnllr lpilchbl6d.li lfu.g6horilt
    I Mt ur.s Ar. SD orbo^rto. oold, Ftr.llfa. ElltFiil.,
    lmlrbdsitft tlllu,ldd, 9old,
    flOutm.lio.l
    Os.rt. t 'rtla. ADlngqrll.. ch.l@ptrll.,
    Slot.raC|. Au, Ag. At- r|!@Btrila. lla,go l.lo I
    , M9.vqS Tt. C{.w rbgn.lcr,ltldtgr,
    Ehnlila Flrtadila.
    tou.drllnr, l.llu.ldct. gold
    aon.
    gold,lrulttd.nilrt
    lllgh Ou.rtt, ttrl?a, tttttodla, rylr. ptrholilrl
    510t, F.. Cr. au, Ae. Cu. lcldrgaa, crrbontlitt ch.lcoptrlt'. nFoPidla.
    i Me.Uag w loumalln.. egld. tchGliI.. sllrrml|!. told.
    lrcltbddiLl losflttllna
    Ftrll] pt"6otlir. blt6ulh,
    t{,3t Os.rt, l.ldr9.t oolybdrnilr. r6crcttrlh.
    t SlOt.tr I Mo.
    lrtrlt .ttdholltr. blroulhlnila. rcllt..dla. Orntdt bttF ot tptd .ttd tllw
    A.A, F, Ar
    mly!d.dt. shrrlila, ltrilarllr,
    tomdlnrr lo9u

    Elgure 13-1r fdeallaed vcrtlcal zsutlqr of clenrcntg and nlncrala ln cplganctic


    gold.dcpoolta, after Eoylc (19?9), AXthough rany apcclllc nlnarala and
    rolc zon?s of ths lllurtrated rctruoG arc abscnt lra the cplthernal dcpocl,tu
    of thc ltaurakl Cold - Sllwr Prwlnccr tha goneral Glcnrn?al' and ndncra.l
    trenda arc alrnllar.
    2p.

    The deposits of the Hauraki Gold - Silver Prsrince have generally


    simil-ar features to those described aborrer but differ j-n scrne points of
    deta-i1. For example, fluorite is absent and enargite has been noted from
    onl-y the deposits at Thanres.

    !fiI'IEFi\J,0GICAL AEPECIS 0F EF. TI{sRI',lAl GOLD ANDj:ILITER DS,CIT$

    Fljnegal _Zgning and Paragenesis


    The generalised depth zonation scheme proposed here for the Hauraki
    Gold - Silver Province r.esembles Boylets (1979) idealised vertical mineral
    zonation for gold deposits (nie, L3-L) I particularly zones 1 to [.
    Sinilarly, the mineral parageneiic trends recognised in the irtdiltdual
    deposits of the tlauraki GoId - Silver Province generally conform. to Boylets
    (t979, pp 415 - l+17) suggested paragenesis for gold deposits:
    1. pyrite and arsenopyrite, 2. wolframlte and scheellter 3. molybdenite,
    !r. native bismuth and bismuthiniter 5. sphalerite, 6. uraninite andr/or
    bran:rrerltet 7. chalcopSrriter tennantitel tetrahedrS.ter enargiter cubanlte
    and borrrite, 8. galena, 9. acanthlte, 1O. stibnite and various sulphosa-lts
    (e.g. pyrargtrrrite), 11. native bisnuth and bismuthinite, 12. precior:s
    metal and base metal telluridesr 13. native gold and electn:mr 14. auro-
    stibiter and 15. cjlnabar, orpiment and realgar. Stages 6, tt and 14 have
    nob been recognised in the llauraki Prorrince and Stages 1O, 12 and 13 are
    reversed.

    GolVSilver Ratios_and Gold FinenesE


    The golCr/silver ratio of gold deposits generally decreases with
    decreasi:rg depth (noyle, L979) because of the increasing prqrortion of
    silver minerals near the surface (c.f. Karangahake and Waiorongcnai).
    Similarly the fl.neness of gold (-Lectn:n) decreases with decreasing depth
    but this trend i.s direct\r related to phtrrsicochemj.cal factors (fS, and
    temperature, Bee Appendix V).
    Although native gold fu rare in gold - teJ-luride depositss vrhen
    found it usual-Ly has a high fineness (noyle, L979) indicating that the
    equillbr{.um reaction ;
    (in electrun) + Te, = 2 LgrBe (hessite)
    4 Ae (13-1)

    trends more strongly to the right than the analogous sttlphide reaction
    [equation (v-to)].
    g'.ti3

    ftlo*lve Tellurium

    I,
    I Colsverlio
    .Aife2 Enrprgsstts
    i AgTe
    Montbroy,ite
    ;
    AugTe3 SlueElte
    &rTer
    i Hessile
    I
    Ag,Se
    I,
    I
    I
    I
    I
    't-
    I

    ia,
    i WEI6f.tT FERCEilT
    Ag

    Slellae LT-?r }lrcrale o.f the strtrten Au - Ag -- f,s. (.Frffi KEItxr &
    (bddard* Lg6F")
    244

    Telluride Minerals
    The phase relati.ons fu the s;nstem Au - Ag - Te were investj.gated
    experimentally by lrtarkham (fg5O) and Cabri (tg55) and empirical.ry W
    Kelty & Goddard (L969). The stoictrlometric ccnpositions of the naturally
    occurring minerals in the systern are shovsn in Fig. !3-2,
    Aparb fronr hessiter gold and silver telh:rides generally occur i:r
    or-ly sma]l guanfities in epithermal gold - silver, silver - gold and silver
    deposits. However gold - telluride deposits are characterised by the
    dcrninance of eu and Au - Ag teJ-luride minerals (calaverite, krennerite,
    sylvanite and petzite) over electrrrn.
    Hessite has been noted frcrn several mj.ra:ing centres i:r the Hauraki
    Province (tatle 4-L) but representatives of the Au and Au - Ag telluride
    mineraLs (and native Te) have been identified only irr the ?apu - Thames and
    Thames areas (by lterchant, 19?B and Rarndohr, 1980). The quantity of
    sylvanite and petziter relative to electnln - go1d, in scrne depo.sits of the
    Tapu - Tharnes area (e,g. Monowai and Sylviai c.f. Merchant, 1!f8) may
    Justify their classi-fication as gold - tel-lurlde deposits (rnineralogical'ly
    but without any econcrnic conotation).
    In his classifj.cation of tel}:ride deposits, Markham (1960) suggested
    that tel-luride rnineralisation in Terbiary volcanic settings (equival-ent to
    gold - telluride epithermal deposits) are characterised by an abundance of
    native tellurium, rarity of native gold (electrum), predorninance of
    kreruterite over calaveriter and a paucity of tellr.rrides, other tha^n those
    of gold and silver. Howevere KeILy & Goddard (fg6g) noted that these
    features were not consistent for all epithermal gold - te]-luride deposS.ts.
    In the Acupan vein (PhiJ-ippines) for exampJ-el electnrm is ccrnmon, native
    tellr.rrirxr absent and caLaverite predcminates orrer krennerite. These authors
    considered that rfAt present, there does not appear to be any consi.stent
    scheme of classification of teJ-luride deposits fuherent in the tellurium
    mineralory Egg' (feffy & coddard t L969 p 185).
    In Chapter 11 and Appendix V the occunence of gold, and silver telluride
    minerals is related to the concentration of total Te j-n solutionl gold -
    telluride deposits probably result frcrn fluids relatively r5.ch in tellurium,
    Physicochemical facbors (e.g. temperature) *.y deterrrine whether gold and
    silver or other tellunides (e,g. Bd. - tellurides) are deposited. (e.g.
    tetradyni,te at high temperature and hesslte at moderate temperature ).
    Detailed therrnodynamic investigati.ons of these aspects is not possible at
    present, uith the current state of lsilowledge of aqueous teJ-lr.rrC.nm species anc
    teJ-lurd.de metal complexes.
    u5

    Seliniferoujr and Selenide Mi.nerals


    It may be demonstrated empirically, with son,e therrnodynamic basist
    that at meditun and bigh temperatures selenium isomorphously substitutee
    for sulphur in sulphide minerals, wher.eas selenide minerals are precipitated
    at l-ow tenperatures and under relatively oxidi.sing conditj-ong, Therefore
    gold - selenide deposits would be expected to forrn at low temperatures and
    frqn solutions with oxidisedr/reduced aqueous sulphur species ratios greater
    than 1.
    Nar.snannite is the only selenide mineral that has been identifj.ed frqn
    the Hauraki Prorinee and it occrrrs at Te Ahumata and boken Hills in
    associ-ation with various seleniJerous sulphide minera-ls, The relative
    abwrdance of naunannite in these deposlts hsbrever is insufficient to
    classify them in the gold - selenide catagory. Both deposits were formed
    at relatively loir temperatures but only the rnineralisation at Broken Hi'lls
    appears to have been deposited under relatively oxidising cond:itions. The
    5.Se/ {S ratio of the hydrofhermal flLuid may have been the controlling
    parameter at ?e Ahumata.
    In epithermal deposlts, isomorphous substitubion of selenium for
    sulphur is most nobable in acanlhlte (e.g. Kieft & Oen, L973i Petruk
    r L97t+i shikazono, L978i this study) arthorrgh it also commonty
    occurs, but generally to a lesser extent, in o,ther sulphides such as galenat
    and sphalerS.te, and in the Hauraki. Prcnrincer tetradlmite and telluro-
    bismutite (l'terchant, 1978).

    PHvgI cgsrEl'qcAJ, aSPECTS

    Introd,uct*on
    Although recent fluid inclusion and stable isotope studies have
    prorided temperature and apparent salinity data for a large number of
    epibhernal depmits (c.f. Sillitoe, t977i Boyle, L979) orrLy a few studies
    have incLuded a detailed ther:nodynamic interpretation of the chemistry of
    the depositional environment. Most of the latter are sumrnarised j.n Table
    tj-3.

    TeJnperaturg
    The iemperature of formatj-on of overseas epithermal depositsr deter"mined
    by ftuid lnclusion and stable isotope studiesr are generally in the 2OO -
    3moc range (pie, 13-3) although tenperatures up to 385oc (Slack, 1t8o;
    Iake Clty, Colorado; no'b shown in Fig. t34) have been recorded, The
    lhrl lu rt.lrrl.l,
    Silvffton di3ttiat
    vaini. Colo?ado
    Rrd |.lountoin
    Pipc5. Cotorodo
    Sunnysida minc.
    SitEiton district.
    Colorodo
    Cr"!d! districi.
    Colqodo
    Prrcio:-nclol
    d.por{r,l,l.Edo
    Chinluochih,
    loiwon
    Guonoiuoio,
    llc:ico
    Pochuco,
    llcrico
    Finlondio minr.
    ccntrol F.ru
    Coudoloto.
    canlrol Pcru
    Eosa-
    ,no!ot
    Jopon
    loyoho,
    Jopqn

    Co3qpolco.
    Pcru

    t34t Fluid Lnclusion fil].ing


    Figure temperatures frcrn epithermal-
    deposits. (P** Sil].itoe t L977.)
    247

    T BtE 13-3r Ceochenical' Parsnetera tor Bqle orterseac eptthemal dep'olta caLculated by previous workers roe l,ot
    foz *7 Hechanlso
    tl .6 -^r\ fsz COo Agueoua
    Class -2 -2 PreaeureJ ^ *4r5 Sallrdty
    t"C-
    14
    aD of ore
    Locatl"on Hino/vela Beference (lVlg) ore nineralg' Gangue ntnerala- (depth) pH (bars) (bars) (d") s aPeciea deposltion

    (1)aprgn,pyrthd, (l)gtzrplmrrho t1)uo-?2o (1)2tr32o (1)0 to 3.6 0.o3"o.0? 4.6 ( 1)-91.1 decrearlrg
    o.5 Eurcka
    Colorado Eureka
    (San Jr,ran Dlstrlct
    Surugrslde
    ltine
    CasadevatrL At-Au
    & Ohnoto (0.o4) '-'iiiiti,,'.ir,ui, (2)qtz'flrcalrho (rt(z)ro-zooo1
    ll
    (rm1
    (2)1?c2r+5, (2) 1
    l+.r-5.9 (o.ot) t'o
    -.o
    to
    1g.g to o>r tenperature dstd.ct,
    'Hormtalns) (19??) edtlnrie,hi (4oo) 8t 2lP b and Increas-
    (2)sp;,cp' B lns Cl
    (l)ptt"prgltr"?t l)qtz rrhorca racl (1)260-185 (1)0'1 to botIhg Leke Clty
    - Slack At-{u ( 2
    Iake City
    Dtgtrict
    Ute
    llldden (1980) thdrapyrtnlcl f,t I+
    5,\ 0.01 -11.2 -31+.4 to o l r and Dlatri.ct
    treasure (2)pylthdlgnrsPrcPr (2)barqtz trhorac; (2)20'385 (2)1.3 to ,+0 t hrottllng
    vein apyreulpboaalt;t claya B at 250 li!.\
    ayateo hnrngrpltchbbndc (25o)
    Au-{g telluraderrcl
    gnrsprcPrPyrtntthd, qtzlcl-1ad1ba1rbo1 t&to 19o-c@ 4.9 to 0.018 to -9 -91+
    to
    Creede
    D[strlct
    Creode Earton
    et af
    At-tru
    (o.01) ---elrlb f,Lrrd (5ms) B
    4-L2 5.9
    (t.4)
    o.3o to
    _r3
    o> r r8
    Iirtrd.ct' 0H veln (250) (0.o2) -tt
    1F7?)
    (l)thd,Ag aulptrocaltg (1)gtz,nurod 74 (1)25o-29O (r)o.z- l+.7 to 0.0, to 4.6 -3t.2 L5 Colgul
    Psru Golqu5, Elnlandla Kanllll & Ag-Au
    elrsprgnrPt
    - B 8.2 5.5
    (5.1)
    O.0m3 to to
    :t5.o to O!af boffLtg Distrlct
    Dtatrlct Ye1.n Ohnoto
    (2)"p'gt-- (2)qtz'18tt ba (>1m) (27a) P)u.r (o.o0r) -10.8 4
    lrrzz) Q)260-710 8
    qtzrclrnurad -)7
    Japan (1) I8t^anl f EptgnrcPrPort!
    acrel Hn-stllcate 200 urt,l o.01 to o<<r
    Xstard
    Pb-Zn I l{rr+arb. to 0.? to to -lt0 oxldatlon
    Iatant veln B,attorr. Ag+u'l
    qtzlad
    zfi 1.3 o.001
    (o.01) +l+
    Uins
    (11)f,anlaara
    l- aprgnrcprelracrPl
    (25o)
    Hl.ae
    Au-lg veln
    (19?r) {* to or r
    -t9
    150 o.01 -r3.5 48 (1)o< r ToYoha
    ! (I)Soya vetn Ag-Au PY'sPtgn'cPlbllPo
    gtz rcarblcl to o.2 to ? to to to > 0.1 reductlon H111e
    Toyoha
    Ulne (11)TaJrna
    Shl.kazono
    (1e?5)
    alabendltc
    2ro 3.7 0.001 -16.5 -t \.5 (2) o >- r
    veln (o.01)
    Eagulo
    Au pylelrcprgplcp qtzrca ratr 7t 25G30o
    - Dtstrlct
    PhtliPplnes Ec919 Antaook and Sai&tns
    t el'
    -
    tellurlde (em) B 0to5
    D[at,rl'cl Actpan
    velnc (treJ (1)

    pyreprthdrcP! gtzrad!,. 2V32 L70-3L7 [.6 to


    ^'-i-' 1
    to-6 ^ M.
    o.ool -1O.t -15 o,25 Vatukoula
    Vatukoula &Peror Aload Au - 5.
    (5'5) ro to
    raJr
    Eilr (19?9) telLurtde Au-Ag tellurldesl ttoecoe.Llte (2@-350) eiol 7.1 -t2 4'l to
    2.5
    O:^ f bo{1{ng
    (1 to 0.4) nat'lve Telelroc, anrdorca
    apy
    ls glven ll brscksta t7 o -oddlsodr I - re&rced
    irr Valuc used lor therarodpanlc oodel
    r1 Table 13-1.
    Seo
    t5 B - Bo1l1rrg
    .8 Not atated lpeclficrrly ibut Probably lrvolve decreaslng
    .2 Sce llgt of abbrevlatlons. t;;;;;a*" ina "rarng ps" (Eirton cL aL t97? 9 n)'
    rt Presture irr bars, dePtb tn tlet'ra' *6 Sallr|tty tn oqulvalent re18ht f naCtt fro fluld lncluslon
    treczlng teoPeraturc data.
    2l+8

    Hauraki minerali.sations were deposi-ted over a sjmilar temperature range


    although the temperature of deposition for the early pyr:tte - chalcopyri.te
    mineral assernblage at Tapu - Thames and Tui Mine may have been slighLly
    higher (approxirnately IOOoC).
    Fluid inclusiqn studies have al-so indieated that preeious metal
    deposition in a nurnber of epithermal deposits was acccrnpanied by boiling
    and th:is is thought to be a characteristic feature of the bonanza type
    deposlts (c.f. Kamilli & Olunoto, t97?).

    q+j"'rity
    The apparent salinlty of fluids durlng deposition of precious metal
    stages in epithermal deposits are general.ly lor*, predoninantly in the range
    of O to lr eq. wL. fo }IaCl (c.f. Table L34i Sillitoe, t977t Boy1el I9?9),
    although much higher values have been recorded for rnixed precious metal -
    base metal assernblagest f .1 eq. wtr. f" ItraCI fran Vatulcoula (Rmaar L9?9)
    and 12,d eq. wt. y'o NaCI frcrn Iake City District (Slack, 1t8O), However,
    sqne of these high values may result frqn the increase in concentration of
    the ccrnponents renaini-ng after steam separation during boiling (c.f. Slaek,
    1g8o).
    In individr:al deposits apparent salinities of fluids present during
    deposltion of bse metal stages are generally higher ttnn during precious
    metal stages although as a group they overlap and have simiJ-ar maxirnum
    values (e,g. 1l eq, w1". fi lla0J. durlng sphalerite - galena deposition in
    the lllnlandia vein; Kanilti & Otrnoto, L97?).
    The difference 5n ranges of true sa'linity betrseen the precious and
    base metal stages may be greater ttnrt jrdicated by the apparent salinities
    because of the larger relative effect of dj-ssolves CO, on the low salinity
    results (because liquid CO, is generally nob present in fluid inclusions of
    epithemal deposits, the conectisrs required for the concentration of
    dissolved C0, are less sign:ificant wlth increasing apparent salinity),
    Precious rnetal stages of the deposits in the Hauraki. Prorince have
    simiLar apparent sa1irrlties to those of overseas deposits (i.e. O to 4 eg.
    w1.. fo NaCl), horever salinities recorded frcrn the base metal stages (e.g.
    Northern GoIvj.ILe Peninsrrlal Petote Stream, Tapu - Thames and Tui Mine)
    are generally lon cornpared wi-th their overseas counterparts, the maxi-num
    recorded value being 5.1 eq. tt+,. % NaCl frm 1\rl Mine.

    PE
    The w'idespread occurrence of adularia as a vejn mineral and waIL rock
    alteration product srrggests that most epithermal gold and silver deposits
    249

    foxmed under condj-tions of near neutral (i.e. pH = 5.5 to 5.7 at the


    tenperatures of deposition) or slightly alkaline pH. Goldfield (fevada)
    is a notable exception, where acidic conditions are indicated by the
    occurrence of abundant alunite.
    Shikazono (19?S) noted that in Japan adularia is ccrnmonly found in
    Au - Ag vein type deposits wh:ile serj-cite is cornrnon in Pb - Zn vein type
    deposits indicating di-fferent pH ranges for the formati-on of the tlso
    different tlpes of deposits. However, such a consistent relationstr-i.p is
    not fou:ad in all epi.thermal districts of the world with exceptions to the
    Japanese trend occurring fu both Au - Ag (exemplified by Goldfield) a.nd
    Pb - Ax ttrpe deposits.

    Aqueous Su].phur Species, Oxidised/heduced SiFpecies RaLio


    Thermodynamic studi-es of
    s\terseas epithermal deposits by previous
    workers (faUte LT}) ind:icate that in the majority of cases mi:reraJ-
    deposition appears to have occurred from solutions containing approxirnately
    equal proportions of aqueous sulphate and sulphide species, and in two
    (Swrnyside ltiae and Creede) the concentration of oxldised species is
    believed to have exceeded that of the sulphide species. Eluids containirrg
    predominantly reduced sulphur species have been identified frqn only two
    deposits of the group listed in ?able L34t both Japanese pb - Zn t5pe
    deposits.
    In contrast many of the deposits in the llauraki Province are believed
    to have forrned from fluids containing sr.rlphur predoninantly in redueed form
    and this appears to be the case with the largest econcmic deposits: Waihi,
    Tlunes and possibly also Karangahake. Relatively oxidised fluids were
    present nainly in the deposits believed to have been formed in relatively
    shallow enviionrnents and the deeper, predcminantly base metal, deposits at
    Tui Mine and l{aiorongcrnai.

    spEclglc r-lEcHaNlsl4s oF oRE DEPoSITIoI

    Introduction
    Various mechanlsms of ore deposition have been prglosed by prerrious
    studies to explain the localisations of ore in epitherrnal deposits (c.f.
    Table LTTi Boy1e, L979). They include:
    (i) decrease in temperature
    (ii.) rnixing w"ith other fldds
    (iii) changes in fluid chemistry as a result of fluid - wa}l rock reactions
    250

    (iv) boiling
    (") flluctuating concentrations of volatile consiituents
    Some of these processes may be modelled thermodlmamically and by
    canparison rrith modern geothermal s;Etems.

    Mixins
    Mixing of the hydrothermal fluid with ground water is an attractive
    mechanism for ore deposition in the epithermal environment because it causes
    instability of both chlorj-de and sulphide canplexed metals in solution
    (see Chapter 11). Drurunond (1981) modelled the process thermodynamically
    and concluded that the nost funportant effect on the hydrothermal fluidt
    wiLh regard to mineral deposition, is the resulting decrease in temperature.
    Hen}ey & Seward (in prep, cited in Hen1ey & El]is, in press) consider
    that the relatively high oxygen fugacity of the ore deposition errvironment
    (where IISO,> f!S) of many epithermal ore deposits is most J.ikely the result
    '4t-
    of mixing ri'"h steam-heated acld sulphate waters generated abcnre the boiling
    zone of the hydrothermal systems. This is analogous to errrrironments in
    modern geothernal systems where deep alkali chloride ttr4pe waters rnix with
    shallow acid sulphate type waters. Henley & It'l'lis (in press) cite examples
    i.:n nodern geotherrnal fields where acid srflphate waters occur at deep J.eve]s
    (deeper than 500rn at l,latsuo and ?OQn at Matsulcaua).

    BojLins
    fummond (1981) thermodlmamicall-y modeJ*led the effects of boiling in
    hydrothermal solufions and concluded that o,pen boiling under isoenthalpic
    condltions (i.e, boiling accompanied by coolilg) tends to oxid:ise solutions
    by remsrrlng reduced ccnponentu (%S, CH4r H2, etc.) from solution more
    rapidly than their less volatile cor.rnterparts (SO4--, SO2r Co21 etc.).
    Closed boiling has tittle effect on the oxidation state of the soluiion
    since al't sf the redox conponents are confined within the tiquid - vapour
    s;rstem. Boilirrg also tends to increase pH by renoring acid volatile species
    (i.e. H2CO.. tlsOy'frcrn solution. The relatlvs importance of the resulting
    oxidation versus lncreasing pH effects on the deposition of metals frqn
    ctr,loride and sulphide cmrplexes in solution probably depends on the originaf
    composition of the solution and the quantity of gas separation. The
    decrease in temperatrrre accompanying boiling may also be imporbant in
    cawing mjneral deposition jn some instances, however a large fraetion of
    the water must be boiled off to produce a significant drcp in the
    temperature (c.f. Dnrmnond, 1981).
    25t

    Kamilli & Ohrnoto (L977) suggested that the advent of boiling at a


    particular elevation may be caused in at least three different ways: by
    an increase in volati.le constituents, a drop in total pressurer or an
    increase in temperature, In the case of the Finland:ia Vein they considered
    Nhat boiJ-i:rg was caused by a process of gas effenrescDor
    A drop ln tqtal pressure may be caused by tectonic effects (e.g. sudden
    open'ing of the vein by far:.lt, movement) or by sudden explosive clearing of
    blocked channels. In the latter case, gas pressures may build up ln sealed
    systerns leading to hydrauli.c fracturing and hydrobhennal exploslons wj-th
    subsequent boiling, gas loss (with associated increase in fluid pit) and
    ienperaLure dropr causing minera1 deposition, resealing of the system and
    the begjnnirlg of anorther cycle (Hedenquist, 1!81). Sjrnilar effects may
    al.so occur in porous rocks in the near surface errvironment, foming
    hydroihermal breccia pipes (e,g, breccia pipes in rhyolite tuffs at Kapowail
    hoken Hills and NeavewiJle).
    Temperattre data for epitherriral deposits are generally not sufficiently
    detailed to eva}.rate whether temperature increases are an important
    mechanism for the tinitiationr. of boillng.

    Eluctuatins Concentrations of Volatile Constituents


    Carbon di.oxide is generally the dominant gas ccrnponent in nodern
    tryrdrothermal slnstems (c.f.
    SLLis & Mahon, Lg77i Elljs t L979) and its
    concentration is important i-n regulating the fluid pH [equation (11-tr)]
    and the maximum depth (pressure) of boiting (i.e. position of the boiljng
    point of water versus depth cunre). Wide ranges of apparent salirnity il
    fluid inclusions in epi-thermal deposits (tabtes G2 and L3-3) and geothermal
    s3rstems (e.g. bovrne g!-g}, L97bi Christier 1t80; Hedenquistr in prep.) ray
    indicate that large fluctuations in gas content ocellrr These may be
    important nechanisms, via their influence on pH or the initiation of boiling,
    of mineral deposition,

    Surnmary
    No single deposition mechanism cited aborre accowtts for ttre fonratLon
    of all types of epitherrnal deposits and in r-eality probably alJ. of the
    mechanisms operated indiv:idually in dj.fferent deposits. The depth zonatj.on
    model proposed by the writer (Cfrapter 11) uses inost of the prcviously
    described mechanisms, separately in different parts of the hlpothetical
    s;rstem, and suggests that the different environments in whj-ch the different
    mechanisms operate deposit generelly characteristic nineral assemblages.
    CCilT4ON GBSBTIC EEATTNES OF FITI{EM{AL DBPffiITS

    In Sillitoe's (1!f?) review of epithermal depositsl he concluded


    that jn individual depositsr
    (") A suitable structural environment for veln deposition is created by
    volcanism.
    (b) Orr deposi.tion ccnnronly foU,ows the deposition of the host volcanic
    rock by 1 to J m.y. (aftfrough it may be rrp lo t5 m.y.).
    (") The cornposition of the host volcanic rock is not a crucial feature.
    (d) Intrusions are scmetimes spatial'ly related to mineralisation.
    (u) The ore ftuid general-ly had a Low salinity and was at a moderate to
    1ow temperature. The water r*as predoninantly meteoric in origin.
    (f) The metals, carbon and sulphur $rere derived frqn either a magma or by
    leaching frqn basement roeks.
    These statements are generally eqr:ally applicable to the epitherrnal
    deposits of the Hauraki Go.Ld - Silver Fovince except that with regard to
    poirrt (c) andesites have provided better ore forming environments than
    rt4yolites both in terms of stmcture and, as suggested herer proximity to
    heat souree. AJ.so, regarding poin'" (a): many o\rerseas depositsr parb5.cular1y
    those in coloradol are stnrctural-Iyr arthouglr genera]-ly not temporallyt
    related to caldera formationl hcwever caldera land fornrs have been recogn:ised
    in on3-y two or three locations in the Hauraki Prorince and their genetic
    relationshi-p to nearby gold - silver deposits has not been definitely
    established.
    253

    ctraPllrR 14

    CO}ICLUSIONS

    The rnetaliferous ririneral deposits of the Hauraki Gold - Silver


    Province may be grouped into porph3rry copper and epithemal. - vein
    associations.
    The porphyry copper deposits are associated with quartz diorj,te
    stocks of lorer and mid Miocene age, intruded into Jurassic gre;nuacke
    suite rocks and Mioeene andesites. They are rdioriter .modeI, hlpabyssal
    and volcanic t;4pes. Surface geological mapping, stream sediment and rock
    chip geochemistryr together with li&ited subsurface dri1l hole analysis
    by mineral exploration ccrnpanies, has indicated that the deposits are sma1l
    and presently uneconqric.
    fiLuid inclusion and sulphur isotope studies of one of the porphyry
    depositss ltlners Head, suggest that copper mineralisation occurred at a
    temperature of approximately lrZSoC from fluids with apparent salinities
    up to t5.5 eq. wt. /" NaCl and containing sr:lphur of magnatic origin. Ttre
    Iow values of :.S, fS2 and fO, indicated for the depositional environments
    of some of the deposits may explain the absence of atrundant copper
    mineralisation.
    The epitherrnal deposits range in age frbm Miocene to Pleistocene and
    occur as fault fissure fillings in greywacke, andesite, dacite and rhyolite
    rockg. Some small deposits in rhyolite tuff host rocks occur cementi:rg
    hydrotherrnal breccias.
    The historically profitahle epithermal deposits are gold - silver tlpes
    although sllver - gold, silverr gold - tellurider Cu - Pb - Zn and nercurli'
    type deposits are also found in the prorince. Acanthite and electrum
    dominate the precious metal assemblages although tellurides (mainly hessite),
    seliniferous sulphide and selenide minerals are losally irnporfant. The base
    metals; sphalerite, galena, pyrite and chalcopyrite, oecur in most deposits.
    Gangue ninerals are mairrly quartz and caleite,
    'daIL rock alteration assemblages are generaJ.ly propylitic and
    characterised by sericj.te and/or adrrlaria i,ndicating that the pH of the
    hydrotherrnal fluids was near neutral or sliglrtly alkaline. Argillig
    assenblagese danlnated by kaolinitel are considered to have formed by
    reactions with late acidic fluids as retrograde stages or, if prirnary, in
    the near surface ernrironment.
    flu:id jnclusion and stable isotorpe studies
    Temperatr:res derived from
    indj-cate that base metal deposition occumed predominantly in the range of
    32O - metal deposition occurred between 28O and
    28OoC, whereas preciou.s
    ZgOoC. I-ate barite precipitation in some deposits occured generally belo'*
    26pog. Boi.ling during mineralisation is indicated in some deposits b5r the
    occurrence of vaporir rich and vapour filled fluid inclusions.
    Se'tinities of epithermal fluid,s were predcrnirrantly in the range of
    O to 4 eq. wt, i.to NaCI. No consisLent difference in apparent sallnity
    between the different t3pes of epithernral deposits was recognisedr although
    the highest maxinum values (up to 6.1 eq. vtt,,. {o }IaCl) were recorded from the
    base metal deposit at Tui Mine-
    The concentration of CO, averages 1 mole y'" in line deposits in which this
    aspect was stud:ied and it is believed to be belor* 3 mole / (possibly below
    1.5 mole f") in alr deposits except the Garbo Mine (Thames) where Merchant
    (Lg|S) reported the occurrence of liquid CO, in fluid inclusions.
    Moderate values of fS, and fO, are indj"cated for base netal and nixed
    base metal - precious metal assemblages of most deposits by the predaninance
    of ptrrrite + chalcopyrite sver other iron-beari::g phases; primary bornite is
    absen!, whereas pyrrhotitel hematite and magnetite rarely occur in the veins.
    Ttre largest gold - silver deposlts fo:cned frcm solutions in which the
    sulphgr species in solution were preduninantly reduced. Near surface
    environments and scme d.eep, predornirnntly base metal, deposits rvere forrned
    frorn solutions with approximately equal concentrations of oxidised and
    reduced sulphur species.
    A variety of mechanlsms of d,eposition are recognised, viz: (a) fluid -
    wat l rock reactio,ns r'clth their assocj.ated effects on fluid pHl (b) mixtng
    with sther tlpes of flui.ds, (") boiling, anA (d) vary5ng concentrations of
    CO, in solution, These mechanj-sms are belj.eved to operate at specific
    horizons within the hydrotherrnal strmtem and deposi.t generally characteristic
    mineral assemblages.
    The cornbination of specific depositional mechanism with favourable
    structural environment, in the andesites has formed two different types. of,
    large gold - silrrer deposit,s. The bonanza gold deposits of Thanes and
    Coranandel are considered to resqlt from near sufface boiling of hydrothermal
    fluids in a ccrnplexly faulted terrain. In contrast, the large ccrnparatively
    low grade, gold - silver deposits of Wai}.i and Karangahake formed over a
    rridc verbical range Ln a small number of maJor fault fissures with sinjlar
    strike. Several dLfferent depositional rnechanisms operated loca1lyr ht
    probably the most Jmportant orrerall uere changes in pH resulting frcm
    255

    reactisns of the fluid with walI rocks and varyilg concentrations of COr.
    Telluride rnj.nerals were forrned in sqne deposits from solutions with
    relatively high concentrations of tobal tellurium, whereas selenide and
    seleniferors sulph:ide mineral.s r{ere generally preeipitated because of
    favourable physicochemical conditions: oxittising Ion temperature
    envirgnr,rents.
    neuterir.m/hydrogen ratios of water extracted frsn fluid jnclu"sions
    indicate that the lgrdrotherma-I fluids mostly originated as meteoric water.
    Sulphur isotope ratim of sulphide and sulphate nrineralsr fu association
    vvl-th the thermodyna.oric rel-ations of the mineral assemblages, indicate that
    the sulphur was derived frsn at least two different sources; sedimentary
    sulpbate and magrnatic S0rr the relatlve Smportance of each varying frsn one
    deposit to another.
    T,vo tSpes of lgrdrothermal s3rstens are postr.rlated for the formation of
    the epithermal deposits of the Har:rrakl Prorince, Iluring andesitic
    volcanisrn in the Mioceae - early Pliocene hlntrothermal fluid csrvective
    cells $lere generated by heat frqn near surface small intntsive bodj.es of
    magna, whereas during rhyolitic volcanism in the late Miocer - Pleistocene
    . the heat sources were larger pl-utons at greater deptb.
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    257

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    19E1t Slze pattarne of gold-rtlvcr depoalta tu tbc Hrura}.l Goldflcld.


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    BnofxE, p.R.L. I UODZICf,I. A. 1977t Tb. rlur1!lrrr-lE-qurrtr tGotb.t:o!.trrr r flrld trrt.


    lleu Zcafand Deoartrent ol Sclentlftc rnil IPouatrlel Rcgearch BuIlctl! 21Et )5 ' )6.
    BUntL. c.u. 1g672 llydrolboroal flulda at tbs rrglr1lc etlge: ln rc.ocborlriry of Eydrotb.rrsl
    Ore Depoeltlt cd. 8.L. Barncr. Uolt, Rlachrrt, rnd tJh.to!' Iov IorL. tL ' 75.
    .19?9. Haguao sDal bydrotbrrlsl rl,u1d8l La rGeocberl.try- of hydrothoilal Oro
    Doposlt.r cd. Il.L. Beraer. Yt'toy, Xrv iorL. 2ad rd. 71 ' 136'
    BURltlAX. C.ll.1 oHHOlo, H. 1980: Lrte-rtage procoss.r of fe]alc raglrtlrlr. Soclcty of xlnlp!
    Gaoloplcta of JaDan Soeclal Issuo 83 1 - 11.

    CABRI, L.J. 1965r Phaae relatlona la the ryatea lu-Ag-Te and thelr rinoraloglcal !lg!McaEca
    Econonlc Geolo''v 60: 1569-1606.

    ClBTIRtcHlr t,.J. 1982r Geology o! thc l{aloroagorrl Vellcy. Tc lrohr. (unpubllahcd X.Sc. thrrlr
    lodged la the Llbtary, Unlvenlty of luckhud.)
    CISADEVILL. T. I OHHO!0, H. 19'17t Sulayalde Xlae, Eurokr Hlalrg Dlatrlct. Sra Juaa Couatyr
    Colorador geoohenlatry of gold rnd baee retal ors deporltlon 1a r volcarilc cuvttoarlat.
    Econoulc Ooologv 721r1t 1285 - 1320.
    CA?HIJS. L.H. '19'I?t Aa analyata of tlrs coollng of lDtrullvce by grould-v.tcr coDv.ctlon vbloh
    lncludeo bolltng. Econoulc Geolo!'v 72(ila8Ol - 826.
    CllAtLISf O.A. 19?1: Chenlcgf analyaea of llov Zealaud rocLs aDd llaerela vl.tb C.I.P.l{r Dortt
    eud petrographlc deBcrlptlono '1911-5?. Part 1: Igneoua aud pyroclratlc !ock!. lles
    Zealand Goolopl,cal Survey Bulletln 84.

    CHIPt{lrl, S. !.d,r rcororandel 1a tbe Golden Dryrr ?lrer CorrcrelrL Prlntcrrr lerlltol.
    CltERl{OV, t.A.f KHADZHI, V.8. 1968: Trapplng of colloldal lnclutlonr ln thc grovth of qurrtr
    cryatala. Journal of Crvatal orosth Sllt 611 - 616.
    CHRISTIE, A.B. 1980: Fluld Incluglon rtudlea fron geothereal flclda. (Bnpubllebcd rGPolt oE
    DSIR rssoarcb contrAct SIR2 VVl6129 todgect la tbo Llbruy. Oeologlcal Surv.y, Lover f,utt.)
    CLIRI. 1.8. 1966r Stabtllty fleld of ronocllnlo pyrrhotlte. fpttttutloD of HlnlaR rnd
    Xetallurev lraneactlonq Leillqo B 75, 8232 ' 82t5.
    cl.tlpool, G.E.l HOLSER,.I.?.r trAPLlt{. J.R.t S^!(AI, [.t Zltr, I. '1972t Sulpbur rad o:ygeu
    laotope gochsElatry of ovaporlt aulphatee. Geoloqlcal Socletv of Alerlca Aaaual
    Heetlnns, Abatracte ulth Prosraua lt 173.
    COCgRLltE, lt.A. 196j2 Geology of Tul, lllne Ht. Te lroba. (Unpubllahcd l{.Sc. theala lodgcd t'a
    th Llbrary, 0ntvoralty o! lucklaacl.)
    COLEr J.U. 1979: Structuro, petrology, aud goaeala of Cenozolc vo)'caalal. ?eupo YolcaaLc Zour.
    lley Zsalaad - e r6v1u. Ngv Zealand Journal of, Geoloqv and Geoohvelcr 6t1-657.
    "rrtrr
    1981: Geneair of lavaa of the ?rupo VolcanLc Zon6, lforth Ialand, Nev Zealaad.
    Journal of Yolcanoloqv and Gootharual Research 102 317 - 337.
    coLE, J.ll.t LEWIS, X.B. 1981: Eyolutlor of tbs Taupo - Hlkurangl.ubaluctloa !y!tor.
    ?ectonqobvalca 722 1' 21.
    COLLII|S, p.L.F. 1g7g. Ce! byahate6 la CO2 - beerlag flulil laclurloar aad tbc uac of fr..tlD8
    data for .rtllatto! of ealinlty. Econonle Geoloev 'llt 1L)5 ' 1414.
    CONSILVEB 1g7)z Beport on IoDa aad BaFlsr rcefa ayatcn aud Suabou f,ecf - Grcat Barrlcr
    Irland. Couaolldated Sllvsr Hlalng Corpeoy of ll.y Zerlaad. I oopy 1r bsld o! oPc!
    fllr. (refercace 12116/11?0) et Hlner Dlvlalon' Ucllla8toa'
    coopER. J.A.t RICtt RDs, J.R. 1959: Lcad lootopo toaauro!ntl oa volcanlcr rad raaoclatcd
    galonao fror tho Coronandol - Tc lroha r.g1on. llov Zoaltnd. Oeochellcal Journal
    321-1L.
    CORIYEIJ., lt.L. 19672 ?hc geology of tbe Tapu - Hauala dlatrlct, Gororaadel Peahruh.
    (Unpublbhed l{.Sc, thealg lodged 1u the Ltbrary, Unlverrlty o! Aucllead.)
    COUPER, p.G. 1g,lrz Geocberlcal laveatlgatlons 1u thc Teraru Yrllry' tbeaea. (IIrPubIlrhcd
    X.Sc. thosla lodgod ln the Llbraly, Unlverrlty of lucllaocl')
    1g792 Flnal Report. Proapecttng Llceace 31{80 - llrballrru. Cororaadcl Pcnlarulr'
    Ucy ?ca1aad. AHOCO lllnerelr (X.2.) tt.t. I copy la hcld on oPcD flfr (rcfcrcscr
    121161'135d & xllo! Dlvl.1oo. Icllla3ton.
    COVEIE!, R.X.t trELLt, U.C. 19?1r Devronlto rr r drughtrr rlnrrrl-1tt bydrotbrrrel tluid
    1acluEloo!.ContJlbutlona to l{lneraloqv and Pctrologv 32t 971 - t12.
    CRIIG, J.R. I SCOTT. S.D. 1971:. SuLpblcle phaoe equl11brla: ta tHlneralotlcal Soclety of lrerlcr
    Short Courgs Not6a, VoLuoe 1: Sulphlde Hheralogyr ad. P.B. Ribble CSI - CS110.
    CRIIC. J.R.r VIUCHAN, D.J. 1981: r0ro Hlcroecopy and Ore Petrograpbyt. Ul1oy, lleu torL. 406P.
    CZAHAilSI(E, c.X. 19'l1r ?he FeS conteat of apbalerltc along tbe chelcopyrftc - pyrltc ' boialtr
    aulphur fugaclty buffer. Econorlc Geolosv 692 1)28 ' 1t31'
    CZAIfINSI(B, 0.X.t RoEDDER, E.r BURIS, f,C. 196J2 lleutror actlYatlou rorlyatr of flulil
    lncluslona for copper, laaaooso qntl zlnc. Sclenca 1'(,0: 401 ' 1O3'
    CZAHMStrE. G.l(.1 RIE, R.O. '19'lI.r Experluentally deterrlned aulphur lsotopo fractlorltloD.
    betvaea epbalerlte and galeaa 1n the tenperetute range 6000 to 2't5oC. @
    Coolosv 69r.r: 17 - 25.
    DTIUVERoNE. p. 19,tIc: Oeologlcal agasgeoeDt of the llhttecllffa rad HLaerc Beed areaa, of Grolt
    Barller Islaad. Aqultsr. A copy lf bel.d oD opoD ftle (referoDca 12/16/1170 rnil
    121t6/1216) at Hluea Dlvlelon, tJe1llugton.
    19?4br Gold go11 goocheoiatry la tbe ltbltecllffr rro. of Great Barrlcr Ialead.
    lqu1trD6. I copy 1g hcld oE opoD fllc (rcfrrs\c.12116111?0) rt Xlaca Dlvlrloa.
    DEER. Y.I.1 BOYIE, R.l.l ZUSSHlll, J. 1966r tAa Introductl.oa to thc Rocl-Forrlug Xlncrrlrr
    Lougoan, Londou. 528p
    DEltt{E}t. y.H.l BLIoKBURN. U.H.r QUESIDA, A. 19?0: llunlnl.ua t! qu3rtl ra a gcotbcrlolotor.
    Contrl.butlona to HlncraloFv and Pctroloev 27t 312 ' )12.
    DOUIIEI, J.F. 1g35r rcold HtDc! of the Hsurrkt Dlrtrlc!, tfov Zcaludr. Govcranont Prlatrrr
    l{c111agtoo.
    DRUr,tHOllD. S.E. Jr. tg81t Botllag end ulxlng of hydroth.rlsl flutd.t ohgllorl .ft.ctr oo
    nlaeral preclpltatloo. (uopubrlabed Ph'D' therir lodgcd la thc Llbrrry' Pcnurylvratr
    Stato Ualveralty. )
    DUCKI,JORT!|, E. I BOBIXSOU. B.Y. 19',19. CallbratLon of the cbelrloca llcrotbernorotry .PPrlrtur.
    Interoal publlcatloa IttS - Lll - 50, Iuatttut of llucleer Scloncel. DSIR. Lorer f,uti.
    DrIICUK0VI, I.B. I IHoDAXOVSKII, I.L. 1968r Thernodyaarto .qutllbrh ln tbc !y!t.!s 5-9201
    Se-H20 anit le-Ha0 tn tho 25 - IOOoC terperature raagc eod tbrlr geocherlcal
    latorpretatlona. Geocheolstrv Internattonal 5: 110E ' 1125'
    EASTOE, C.J. 1g'lgt l flulat lncluaton atudy of the Penguna porpbyry coPPor deporlt'
    Bougainvtllc. PaPue tleY Gulnca. Econouic Geolosv 73(r, 721 ' 718'
    EDUIRDS, p.E. 1g7g. Altorailon and llaerellsatlon of greyuackca aad raroclltad rocla aclr
    Coronandel, llev Zealand. (UapubUebcd X.Sc. tbealr lodgcd ta tbe tlbraryr u[lY.!!ttt
    of luckland. )
    EIlflUDI, tt.T. 1977. Envlroueat o! ors depoaltlon rt Col'ro Do Paaco' Peru' Econoulc Geoloev
    't261t Egt ' 92L.
    ELDER, J.y. 1965t Pbyaloel procoaaor ln geotherlal ereag. loerlcan Geophvslcrl Unloa,
    Geophvalcal l'lonoeraoh Serlcs 8: 2'11 ' 2t9'
    1966: Iloat and lcas traosfer la tbc carth: bydrotherlal eyatorr. Departlont of
    Sclent,lflc and fndustrlal Rosearch Bulletln 169'
    ELLIS, l.J. 19?gr Explored Gsotberrrl Syateorr lu tGcochclletry o! Hydrothrnel Orr Dcpolltr'
    6d. lt.L. Brrnog. t{tleyl ltev IorL. 2ld od' 6'2 ' 683'
    ELLIS, l.J.t CICCEIBACR, y. 19?1r f,ydrogen aulphlile lontrattoa tail rulphur bydrolyall ta
    hlgh tenporaturs eolutloa. Gcochenlca et Cosnochorlca lcta )5t 2lr7 - 260.
    ELLIS, l.J.t ooLDRIllG, R.H. 19612 ?hs aolublllty of carbon dloxldc ebova 100oc lu uat.r
    rad
    ln roallu! ohlorlde solutlour. Anerlcan Journal of Sclanco 26'lz L1 - 60.

    ELLIST A.J.l l{lltoN, rr.A.J. '19771. rcbenl;try aod cootbcrral sylterar lcaderlc Prclr, fcY IorL'192P'

    EilJOJI, H. 1972t gtudlos on fluld laclualonr rr thc rctllr of tbG or' fornrtloa' Elgg'S
    Rport3 or th Tot(vo KvolLu DalPaku. sctlon c costaDhvrGoloFY and HlnGraloPv
    2(roe)s 79 - 127'
    2&

    EuARt. l.l Hu LI, J. 1g65t Ignlrbrltcr of tbc yrlht Dlrtrlct, In Tholpaon, B.ll.. f,crtodr,
    L.O. and Evart, I 1965r llev Zoaland volcauology, Ccntral yolcanlc Rcgloo. I.Z.
    Geological Survey HanCbook. Departoent of Sctentlflc and fndugtrlaL Regearch
    fnforaetlon Serleg 50.
    EflR?, t.t HILDnETu, Y.l cfRfiIiflfEL, g.E, 1975, Qurtcrnery rcld [gnr la lcv Zcelrgit.
    Contrlbutlona to Xlneralosv and Patrolosv 51r 1 - 27.
    rEISS, P.G. 19'1L.. Reconaalsgaace of thc tetrahadrltc - taEDaDtlt6/aarglic - felatln!.te phaao
    relatl,ona aa a poaalblo geotheruosotor. Econoolc Geolosv 69t 383 - 390.
    5'IltLtISON, l.f{. 1909t ProbLena ln the geology of thc Hrurakl Gold Plcldr, llev ?otland.
    lSgnorlS_c"eleCl 1t 632 - 6tt.
    FISgER, J.R.t BARilES, H.t.. 19722 Tbc lou-product oonrtert of vrtcr to JJ}o.Journal ol Phvrtcel
    Chsnlatrv ?5(r)r 90 - 99.
    FLICSTEII. J.t SCIIIEBER. X. 197L:. Hlcrosegrogatlon ot hpurltlea ln bydrotberoally-grova quartt
    crystale. Journal of Cryatal Grovtb 21/252 603-609.
    FOIIRIIIER, R.0.1 TRUESDELL! A.H. 1973r An eoplrlcal lla-f,-Cr gcotboiloroter fot natural. nator!.
    Ceocheulca et Coanoehlolca lcta )7r 1255 - 1275.
    rR^NI-rIXENETSK!, V.4., NTHENTSEV, I.E. 1968: Subriltuttoael ard lateratitlrl lrpurltlcr !a
    quartz and thalr nlaereloglcal rlgulflcanoat lB rfntsraatloael lllacreloglcel
    laaoclatlon. Papers and Proseeilllgr of thc Flftb Gsneral Heotlngr Cubrldgcl EngLatil
    lugurt J0 - Septenb.r 3' 1966r Tbe Xlncnloglcal Societyr Loadoa. 131 - fr9.
    FRISER, C. 1910r ?hc geology of tbc Tharcr Subdivlrloa, Eeuretll luotlud. llcv ZeiFuS
    Gcoloalcel Survev Buflatln 10.
    PRASER, C.t IDAHS, J.H. 1907: Tbc geology ol thc Corolaadcl Subdlvlllo!' Brurell. Auctlaad.
    !!eu Zealand Geoloslcal Survev Bulletln 4.
    FREIDXIII, J.l 0tilEIL, J.R. 19772 Couplletlon o! atablc laotopc frectlonatloa lectorr of
    goochElcal- lnteregt. Chapter K.f,. lu rData of Geochorlatryr 6th 6d. X. Flotecbcr cd.
    U.S. Coolopical Survev Profeaelonal Paoer 440 - X[.
    FRElfCg, B.H. 19?1t Stablllty rcletloar of cldcrlte (FeC03) ln tbr ryltcr Fc-C-o. lrcrlcan
    Journal of Sclance 2'I1t 17.- 78.
    ClLVIll, P. 1906; rTho Ney Zealand t{lulng Haadbookr. Govotarent Prloter, Ialllagton. 589p.
    GIRRELS, R.H.t CHRIST, C.L. 1965: rsolutloDs, l{laeralc ead Equl).lbrler. Eerpcr & Rov. Iev
    Iort. 1509.
    GICGEXBICU, Y.f. fi77t The laotoplc eolporltloD of !ulpbu! la roillreutary rocl.r bordorlag
    tbe Taupo Yolcculc Zouc. Nov Zealand Dcpartrcnt o! Sclentlflc and Induatrlal Rerearch
    Bulletln 218t 57 - 61.
    'l9E1 r Geotherual llnorrl .qulllb!1,r, @ 45t
    39t - 110.
    CRECC, R.C.l PETRIE, J.tl.l ClRLSOlt, J.R.3 OtCo[ll0R. l.P. 197Ot Grologlcel report oa thr aortb
    cad of Groat Barrler IsLand prepared for CoDaolldated Sl,lror Hlalng Coupray ol lloY
    Zealand Llalted. Layt,oa & lssoclater. A copy 1o beld on opsu flIc (refarcncc
    12/1611216) at HlDo! Dlvlrlon, uelllagton.
    GUILBEnT, J.H. I LOIIELL, J.D. 19712 Varlatlonr ln roalag patterur in porphyry orc doporltr.
    ganadlan llinlnE and Xetallurplcal Bulletln 67eLZl, 99 - 109.
    costlFsolt, L.E. 19792 Porpbyry coppcr dposltr rad crLc-alkallus volourtrrr ln rTbo Errth
    Its 0r1gln, Structuro and Evolutloor cd. X.I. XcElhlaay. lcaderlc Prcrr, LoDdon.
    127 - 1,68.
    CUSTAtrSOI, L.B. I HUilT, J.P. 19752 Tbo PorPhyry coPPrr doporlt et El Srlvrdor, Cblk.
    Econoolc GaoIoPY ?O(il, E57 - 912.
    GYILLIAI{. C.E.J. 1968: fgltekauri }llnor rad battoricr. Ohlaerurl Rerlonal Hlrtorv Journel
    5p1t 38 - to.
    26r

    llls, J.L. Jr. 19?tr fbr rlfrst of rrJ.lalty oa tbr lrrlrul tbonrl grrdlrnt of r hydrotbcnrl
    ryrter rt hydrort.tlc pr.trur!. Econoulc 0colorv 661 940 - 9a6.
    IAXCOCI(, P.ll. 19?0r Gaologleal !oport os thc ]tbltccllffa and ccatrrl rcgtoa Orcrt Brrrl.r
    Irlrait. Laytoa I lasoclatea fo! Coulolldatetl SLlvcr ttlalng Cotprny of Xev Zcllaad.
    I copy ts held on opeD fllo (reforor.cc 12l16ltl?0) at Xiaca Divlrloar fclllugtoa.
    1979:. Iav66tlgatlo!B on tho t{artha 8111 gold proapect. Paper preacat.d rt th!
    luatralae|an Ioatltute of Hlnlag aud Hetallurgy Aunual Confsraacorl9?9 3! Groylouib.
    BlBYEt, C.O. 196?t Rock alteratlou ln tbe South-Eaat lrlbltlanga aror. (Uupubllabod X.Sc.
    thesla loilged lo tbe Llbraryr Ualvoralty o! Aucklcnd.)
    UITTORI, f,. 1975t 0eochenlatry of ore dcpoaltlon at thc lrtanl lcad-zlnc aad gold-rllvor
    depoalt, Japeu. Econoolc Geolocv 70(4)t 677 - 691.
    Bll{LEt'J.E.1962:TheSudburyo!9c:th1rr!'nera1ogyrudor!'g1n.@?t
    50 - 55,
    f,AIlER, I.B. 1951. Tbe geology of the routbera aud pert of tho coatral Portloa ot Grort
    Barrlcr falaad. (Uapubl.labeit t{.Sc. tboala lodged la thc !1br8ry, Uolvcrrlty o! luckhad.)
    gltfARD. B.t. 19712 ceo]'ogy and aruptlve hlotory ot tbo Teble l{ountall Rcgloa, Cororaadcl
    Penlnsul. (Unpubllahed B.Sc. 8oaa. thesls lodged Lo tbe Ltbluy. Ualveraity of
    luckland. )
    19732 Upper ?erLlary freahuater ougsel fosalla fror thr Corortadel Volorslc
    toqucac.. Journal of the Roval Soclctv of Xcv Zcaland 3111 6t - 69.

    1g7/rtt Co]ogy aa<l oruptlve btrtory of. TrbLe tlouatrlB trct' Cororaldrl Pralalulr.
    Nev Zaaland Journal of Geoloqv and Geophvalce 17p1t 10) ' 122.
    19?4br i{hltlanga Croup redfuenta of tbc Trbh xoultrlD et|ca. Cororrudcl
    Peallaula. Journal of the Rovgl Socletv of Nev Zaelasd 412;t 16f - 176'
    BElLi. J.r SCHoFIEID, J.C.r THOHPSON,B.f,. 19641 Sbeot 5 Rotorur (1.t Ed). rGeologlorl Xrp
    of Nec Zcaland 1:250.000r Dcpartlent of Sclcnttflc rnil Iaductrlrl Relo.rcbr Iolllagton'
    llcc Zcalrld.
    HEDEilqUIgT,J.I. 1981r Geologlcrl aril gaocherlcal ovldence for oycllc vrrlatloar ta
    toEp.raiuro and gar chonlrtry at l,lalotapu geotberlal ryrten. ll.Z.t. lnpllcatloar for
    epltheroal.typelu.Agulnerallaatlon.rnlbatracteo'paPcr.prcaoatcdltl9El
    ooochcnlctl Group Conferencc, ll.z. 0eOChel!.caI Crouo ltavalctter 64t1.

    lD pr.p: Gcoebenlrlry aad rtneralltrtlon of ra rotlvr bydrothrilel ry.t.r.


    yalotapu, llev Zeeland. Pb.D. tbcalr la Geology; Ilnlvcrelty of AucLhnd.
    HEIIfRICH, E.ll. 1g65t lHlcroacoplc Iclentlflcgtlon of Hlleralor NcCr.Y - 8111' Icv forl 11{P'
    IELCESOU, H.C. '1967t Solutlon chenletry anil retarorphlar: 1n cd. P.f,. Abelaoa. rRclerrcb'!
    ln caocberlstryt v.2 ttlloy. lleu lort )62 - LQl.
    1969r lbernodyaanlco of byilrotbernal ayatera rt clcvrtetl terperrturct eail
    preaaurea. Aoorican Journal of Sclence 2672 72i - 804'
    HEI{DEBSOI, J, 19311 Great Barrler Copper l{loc. 2Jth laaual Roport (tter Scrlor) of tbc
    Departrent of Sclettlflc and IDdustrlal Rcsearch, 19r0-r1 ooologlcrl Survry Braach
    pi:rO - rZ'
    1gt9r rho coppsr rlourcoa of ttev Zecleud. Hev zealand Journal of Sctencc and
    technoloPv 20 (1B)3 1?? - 180'
    HEIfDERSON, J.l BAR?RUI{, J.A. 19132 Tbo geology of thc lrobr Subdlvlrlo!' Erurrkl' lucklend'
    llay Zealand Geoloslcal Survqv Bullotlu 16.
    R.Y.I ELLIS. l.J.
    tsEf,l^El, ,.! prssrr Geothorul ryrtcra raclout ratl rodorst r geocbctlctl
    rlYlu. .
    HENLEf, n.U.t HcilABB, t. 19?8r Hrgnatlo v.pour pluree and ground-vatrr latcractloD lD porpbyry
    copper elplaeenant. Econoulc Caoloqv l3(lr 1 - 20.
    HoCUSTEIII, tl.P. 1980: Ilaurakl Rlft! lD ll.P. Hochatela aad l.H. Bunt otla rGuidc to C.oPbyslc!
    of tbe Volcanlc and Oeothernal Arcac of tbe ll-orth Ialand, tlev Zealaudr. Roval Socletv
    of Hev Zealand, Hlacellaneoua Serlga 3t 28 - 31.
    HOCHSTEI!, H.P. I llIIOI, I.il. 19'l9z Geopbyalcal atudy of tbellrunkl Depreaalou, llortb Ialaad'
    tles Zoa1and. l{ev Zealand Journal of Geoloev rnd Geophvalca 22(ort 1 - 19.
    HOLLltlD, H.D. 1959. Sooe appllcrtlolr of therlocbcllcrl detr to problcar of or. doPotlt!.
    I. St,ablllty relatlona along thc orl,deo, rulphiclea, aulpbater rad carboaatea ol orc
    aad gangue tlnerala. Econonlc Oeoloev 51! 181' - 23t.
    1965.. Sooe appllcatlo!a of thersocheulcal dsta to problers of ora depoatta
    II. Hlnaral aaaeob).agee and tbe cooposltlon of ore fonlng lluldc. Econoole Coolorv
    6015,;: 1101 - 1166.
    19?2tGren1tag,go]utlonra!dbaaoretaIdepor1ta.!s,.@.g'6?l
    281 - 301.
    HOLL XD, H.D.t HALINIX. S.D. 19?9s The eo1ublllty ead occurtouc. of son-ore rloerglrr la
    ,Cocbo.lrtry of Hydrotbernrl Ore Depoaltri cd. H.L. Baracr. Ylloy' Iev forl. 2nd ed.
    161 - 508.
    [oLLISIER, V.F. 19782 rGoology of tbe Porphyry Coppor Depoalte of tbc Io!taD Bcrlrpbcrcr.
    llerlcaa lDEtltuto of l{lningr Xetrllurglcal, anil Pctrolcut Eaglaccrrr Xcv IorL. 219p.
    H0IIE.^.s.1899'ReportoaGreatBirrr1erIr1rad.@2|Et3o9.311.
    USU, L.C. 19'l6t The steblllty of tho rolfrarltc E.rl.!. lporlcap Nlnoraloetlt 6lt 9t{ - 955.
    197,1t Effccta of orygn eail aulphur fu8scltlo! og tbc rbrclltr-tungrtcaltc lud
    pouell!.tc - rolybdealte atrbtllty relrttonr. Econoolc Gcolory 72(il 66L - 570.
    198'lr Phere relttlons of rooe tungrtete rlaerala undor hydrothcrnal coldltloBr.
    lncrlcan Xlnsralorlat 66t 298 - ,08.

    HSU. L.C.l G^LLI, p.E. 1973t 0rlgla of.tbo aeheslr.lc - povcllltr..rt.r ot rlacrrlr.
    @ :-eotoCX 68: 681 - 696.
    UUTTOI, C.O. 19llr Ineal,tc froo Urlbt lllacr ]lorth ltlrad, ]tcn Zcehnd. Tranractlona of thc
    RovaL socletv ot' Nav Ztaaland ?1(f)t 99 ' 1O2.
    HU?Iof,, tr.l{. 1869r Repori on the geology of Great E.rrlcr Ialead. Reporta of Gcoloslcal
    Erploratlona, llev Zealand Geoloalcal Survev. 1868-1859, llo.5t I - ?.
    IltAIf [. ,19?8: rGeologlcal Studlcr o! tbc rlncral dcpoalta la Jrprn end Errt Aeier Uulvcrlety
    of tokyo Proao, TokYo. )929.
    IgDlLE, l.X. 1967t rHlltory of rthe Rivcr tharclr I.Z.r Xauuravl Couuty Chronlclc Prcrr.
    I(AJIIARA, l.l f,RousE, f,.R. l9?1r gulphur l.otop. putltloalDt la rotalllc rulphldc !y!t.r!.
    canadlan Journal of Earth sclencca 8z 1297 - 1408'
    f,.lNILLI, R.J.t oHltOTO, H. 19'17t Parrgener!.r. zoalog, fluld tuclueloa rad lcotoplc rtudlcr
    of the Flnlaadle Veln Colqul Dlrtrlct, CoEtrrl Peru. Econonlc Gcolosv 726yt 950'9E2.
    trEtBr D. 1g55t Hcrozolc snd Iover tcrtlary .tntlgr.pby rnd llroltoao dcpolltr' torrhl'ue,
    Corouasdel. Nev Zealand Journal of Sclcncc rnd lochnolorv Sccttoa B 3?121t 107 - ffa.
    .19572 f,8u8orang8 oulphtdc d6Porlt, tbuel, fey zealaacl. llcv zealand Journal of
    Sclcncc and Technoloqv 382 Aei - a95.
    1958. !lotor on four llnor rulphldl proapectr aser cororladll. tfcY zarlrad Journal
    of Geolopv and Geophvclca tt 514 - ,1E.
    f,ELLl. Y.C.t C0DDARD, !.X. 1969r ?rllurldc orcr of Boul'dor Couatyr Colorrdo. 9.@S.t-c..f
    @t09.
    KEtttEDI, Y.C. 1961,t Yaltavhata recoll,ectloug: (aad) old Uettolrurl. g.$no!u4-!g!9gf
    Hlgtorv Journal 1111: 2{ - 28.
    xER. D.S.1 I/oDZICKI, A. 1n pr6as: Report on uudorground dlaaond drllllag rnd furtbor
    geologlcal rapplng, Tul l{lac. Ts lrohr. @ E, Sclcaoc
    Inforoatlon Dlvlaloa D.S.I.R..
    f,ERR, P.F. 19772 roptlcal Xlneralogyr. xccrrY-8111, llev lort 4th cd. 492p.
    XIEF!, C.t oEN, I.3. 19732 Ora rlaerrlr lu the tollurlde-beerlag gold-lllvcr orcr of Salidr,
    Iadoaeala, ultb epeclal refereneo to tbe dlstrlbutloa of aelealuo. l{lnerallul
    Deposlta 8z 312 - 32O.
    KIT1, Y. 19?8: Gold, gllvor aad plat!'nuD asreys 1922 ' 1976. Chenlatrv Dlvlslon (DSIR, x'z'l
    fug! 2272.
    trggtt. E.P. 1g'13r Sore atudlea of llev Zealand Quaterncry pyroclertlc rocLa. (Uapubllabrd
    Ph.D. thalr lodged ln the Llbrary, Vtctorla Unlvoralty of Uelllugton.)
    I(OID8, tt.l BIiATTACHAItJI. S. 1975t Fornetloa of fracturE atouad lagratlc latrua!.oor rad
    thslr role 18 oro locallgatloa. Econonle Goolopv ?0(4), ?61 - ?99.
    I(OLOXIU. G.R.l SIIInOI|OSOVA, G.P.l LIPTEV, Y.Y. '1975, Exporl!6atrl cbccklag of tberrodyaulc
    diagronr of the ateblllty of lf. Xo. rud 81 elncrrlr uadcr bydrotbcrtel condttloor.
    Fortschrltio der XlneraloEle tzr 161 - 16?.
    XRAUST(OPr, X.B. 1969r theroodynarlcl urccl la gcochallrtryt ln rBruclbook of Goocbcllrtryr
    Volulc 1 od. I.H. tladepohl Sprlnger-Vcrlag, Bcrlla. 37 ' ??.
    19'lgt rlntroductloD to GcocboDlrtryi. Xccrav-8111, Xcv lork 2ad cd. 61?p.
    ruBlscHEl{sxlr 0.1 ALCoCK, C.B. 1979t rl{etallurglcaL lbernocbcrlatryr. Psrguoa, orford.
    5th od. ,l'{lP.
    KUSAf,ABE' H. 19712 Sulphur l,rotoPlc rarlatloaa la nature. Ites Zsaland Jouraal of Sclenco 1?t
    18r - 191
    LITTER, J.U. 1980r Volcanooa la tey Zealand. A&!E 6 (DSIR Erteaaton laforlrtl'oa Scrlcr).
    1981r Locatlon of ronea of rDoroloully hlgb S-vavc rttenuatloa la tbr uppcr crurt
    near Ruapohu and Ngauruhoo Volcanoea, tlev 2eeland. JournaL of Volcraolosv rnd
    Ceothsroal Regsarch 10r 125 ' 156.

    LtflOI, D.C. 1971t Dollnoetloa ol th6 lloDovrl rccf, ?barcc by gcophyalcal retbodr.
    (Unpubtlahrd B.Sc. Hong tbealr lodged la thc Ltbrary' Unlveralty of lucllaail.)
    IIXDCREI|, I. 1933t rHlaeral Deposlter. HcGras-f,lll, toY IorL. 4tb od. 910p.
    LIU, C.t LIXDSII. H.1. Jr. 1972t Therrodyaaricr of rodlur chlorldc rolutloar et blgb
    teoperaturor. Journal of Solutlon Choolatrv 11t1t 45 - 69.
    LOI{EIL, J.D.l GUILBERT, J.N. 19?01 Lrtcral rad vortlca1 rlteiltloa-rlacralleetloa roulog
    ln porphyry oro deposlts. Econortc Ocoloev 65(f)t t7t ' l0E.
    !{AIX, J.V, 19?'lr Gcology of the Xaratoto - Irlprbcle arct Cororaodef Ptalnrulr.
    (Unpubllehetl ll.Sc. tbealr lodgod la the Llbrary, Ualrcrrlty o! Aucklud,)
    19792 Preclour netal bearlag vetaa of thc Xrrrtoto-Yoltvorth er.r, Erurrll
    Goldflcldr liey Zcrhnd. tlev Zcaland Journrl of Ccoloev rnd Gcoohvaler. 221t1t
    41 - 51.
    J.y.t RODCERS. X.A.s f,oBE. !.Y.1 IOODST C.P. 19?22 lgulhrttc fro. thr c$oole
    Bcof,
    HI III ,
    xgratoio vBlley, Nev zealand. l{lneraloslcaf Haeazlns 3E: 961 - 96L.
    rt rlcvrtctl
    HAIIIIII, S.D.l XURoVSKIIA. N.A. 1915t .Solubll!,ty of G0, la cblorlda tolutlonr
    rnd co, proa!u!or. Geochenlrtrv rntcrnatlongl 't212)r 199 - 201'
    tclperrtuler
    XALIUIf,, 3.D.1 STVEIIEVA, ll.I. 19't2z Tbc aolublllty of CO2 !'n BeCl rad Crclt aolutloar rt
    25, jO end ?5o uadcr cJovetcd C02 prtrurorr Gcocherlrtrv futcrnatlonel 9131r
    . 410 - 41s.

    HTRKHAI{, lt.L. 1960: synthetlc aud aatural phaaee ln the systo! lu-Ag-te. Pat.tt 1 and 2'
    Econonlc Ceoloqv 55! 111,8-11?8, 1160-117r.

    x^lsuo,S.lSUZUOf,I't.lNusAtrrBE.l{.IIADA,E.ISUZUXI.}|.19?4tllotoploudcborlor]'
    coDPosltloDs of voleanlc gaaea fror sataura-rvoJlaa' Japan' @E4'$!-J3g4!
    8s

    't65 - 173.
    ot tbc
    HtTtlllsoll. J.x. 1971t Preparatloa of ultrapurc BI|, lCI and Htl03. aaaual Report
    Dtrector. Gcophyolcal Laboratory' Crracglc tDltltutloD 19?O - 19'11t 266 - 268'
    lttIIEL!, l{. 1g80r Bcport on thc grology rnd rlacrrl!'r.t1on of tlbu3rrrtr E.L' tt062'
    CoId
    Hl.uea of tl.z. Ltd. I copy 1s hs].d oE oPoD fllc (refcrenc. 9l2t?) lt HlEs! Dlvlrloqr
    llrlllugtou.
    1981t Report on thc geology end rlDcral rrPlolatlott of tbc Ybltlrugr - lrlrur
    r.g!'on, E.L. 3308' Coroaandel Pealnlula. Goltl Xlgcg of tr.Z. Lt.t. ^ ooPy
    tr bcld
    oroPGD!11o(rcfereu'cegl2S2latlllnscDlvlrlon'Yclllugton'
    XcA84,J.8.19782|col.lHlDlDgatl{alhl,1E?8-1952lldelbl'SlrtorlcelSoclotylletbi34EP.
    HcLrHlNS, f,.t(.r BARNES, ll.L.r oENOro. H. 1980r Sphalsrltc atrrtlgtephy of tbr upprr
    }|1!st!s1PP1VrlleyZlnc.LeadD|atrlct.SoutbvogtUlacourta.EconollcGeolonv?51,1t
    351 ' 161.
    IIcNEIL. l.g. 1967t rllsnorlcr of Early coronaatlcl Lrldlav Prlatlag, l{rnursYt.
    lrloru
    HERCHAIT, n.J. 1g7tr Aapecta of thc geology geocherlatry rnd rlnerellrrtloa of thc
    thetl! lotlged la tbc Ltbr'r|y' 0alvcralty
    vrlleyr Tharss. (uopubllahod B.sc. [onr.
    of Auctlanil.)
    of Aucklend')
    Zealaail. (Uapubllobed Ph.D. thcclr loitgcd ls thc Llbraryr Ualveralty
    HEIERTc.IHEHLEITJ.J,'196'lttJallrookrltcntioa:lnrGsocbenl'tryoff,ydrothcrrrlOrc
    Deporltr cat. H.L. Balnea. Holt. Rlncbrrt arit l{i'uaton. 166 ' 2t5'
    l{IZUtlttI, I. r9?Er llotoplo cooporltlona of volcratc rteal lror sbovlrhtazen Yolceuo'
    Bollaldor Japen. Goocheulcal Journal '2' 57 ' 67'
    HODRIllIlx, tt.t HARSDEN, E. 19r8s Expertrentl I'u gcophyalcal
    aurvcy lo llen zcalrnd' r
    1. 92p.

    xou.!ol^.J.lJ.rHEHLEI.J.J.19?5ztctlvltyrelattoaganiletabllltlsl!grlLellloldrper
    and llca altoratton r6acttolr' Ecoaoulc Ocoloqv ?0(3)t 577 ' 583'
    265

    H0OnEr C.R. 19762 0o1d - allvcr !1D6rall,ratlon of ths Brolca H1III ar.r, Ulkual.
    ' (Unpubllahcd H.Sc. thealr lodged la tbo Llbrery. Unlvcralty of lucthnd.)
    1978t Flaal report on l{bargapoua fI, Proepectlag Llceace 71710. l}l0CO Hloerel.r
    (lt.Z.) Ltd. 'A copy la hcld on opcn flle (refersuco 121161110?) rt xlaoa Dlvlaloa;
    lJelllngtoa.
    19?9a: F!.ral report or l{hangapoua I Proapectllg Ltceaca 31462 Cororaadcl
    FenlnouJ.a, llev Zealand. IHOCO Hloerels ([.2.) lta. A copy 1g beld oD opou flIe
    (iofereace 12/ 16/1221) at |llnea D1vla!.oa, l{eL11ogtoa.
    19?9b: 0eology and olnerall,aatlon of t,he foraar Eeotes 8111s gold rlne, Hllsurlr
    0oronaudel, l{ey Zeal.aad. Nev Zealand Journal of C6olglg1!-..!392[p!g 22Or,
    3t9 - 351.
    XORCAI|, P.0. 1921, The geology and Ilaes of the Yslbt D1atr1et. laurekl Goldflel,d. llsu
    Zealand. lfev Zealand Ceologlqal Survey Bulletla 26.
    1925, The so-calIod rprudolorpbouar quartr of Tcrtlsy gold - rllvsr vclar.
    Econoolc Geologv 20C, 2O3 - 2O7.
    lflsH. J.f. 1915, Geochsulcal atudlcs La tbe Park Clty Dlstrct: II aulpbldc rtucralogy rud
    rlnor-eleoent cheoJ.atry, Xayflover l{lne. Econoulc Geolopv ?0(g)t 1038 - 1019.
    19762 fluld-luclualon potrol.ogy-data fron porphyry copp6r depoalta aud
    appllcatlona to exploratloD. U.S. Ggoloelcal. Survev Profearlonal Paper 90?-D. 16p.
    NEILsEllr f,.I. 1968: lSARco DovelopEe.t ([.2.) Lhltod. ErploratLou Xortb Islcad, llov
    Zealaad. Jauuary 1967 - Juty 1968. I copy lr bcld o! opGE fllc (rcfercacc 912321
    at NlDos Dlvl,aloo. lrlelllogton.
    IfIELSEU, R.L. 1976t Roeeut developoonta lu the rtudy ot porpbyry coppor depoaltr - r r.ylar.
    Lanadlqn !rrc!1,Lttl6 of l,llnlnu and Hot 15t lE? - !00.
    llOI,Alt. ?. 19772 iHlatorlc Gold ?ralla of the Coronandelr llt t lU Rceil' Yclllagtol.
    OH'{OTO, B. '19?22 Syatenatlca of rulphur end carbon laotopsr ia hydrothentl orc dcporltr.
    Econoolc Gooloev 61 (ilt 551 - 5'18.
    OHHOIO. H.t RYE, R.O. 1979a Iaotopoa of aulpbur aril earboa: ls rGeocbeelttry of Hydrotherrrl
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    OTLEIRI, C,P. 19?8r A geophyalcal atudy ot the Uhltlanga 0raben. (Uapubllabcd B.Sc f,oar.
    theals lodgotl tn the Ltbrary' Ualvcratty of luctlaad.)
    OVElfS, S.A. 19762 Oeology of tho falrut - llot Yrtcr Bocoh erce. (Urpubllrbcd X.Sc. tbcalr
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    PlRf,IllSOtl, P.C. 19801 ccology of thc lletozoto, Tertlery rnd lu - lg riaerallscd rocll of
    t(uaotuuu, Goronanilel Penlnsule. (Unpubllabod ll.Sc. thsalr loilgad h tbo Llbr.ry,
    Unlveralty of luckland.)
    pETRUf,, I.t oYEllS, D.R.r STEUART, J.lt.t XURRAI, E.J. '19712 obrcrvrtloaa on rcarthltc,
    agullarlto aud nouoalalte. Canadian Hlneraloplat 12rc1r J65 - ?69.
    PBILLIPS, Y.J. 197)z Hechanlcal tfoct! of 16trogrrdo bolllng aad lts probrbl. hportracr
    !n tho fornatloa of aono porphyry oro dpo!1tr. Inetltutlon of X1ulnp rad
    l,letallurpv Ttanaactlons Sectlon E 81t 890 - 898.
    POTIER. R.l{. II 1977t Pregaure corrtctlon! for fluld-lnclualon bologealaatloa tcrpcrrtur.l
    baaod on thc voluoetrlc propcrtlc! of th. lyrte! t{aCI - H20. U.S. Geolorlcel
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    sodlur chlorldo aolutloar. @!g@!gf 'l3pyt 281 - 2E5.
    PUCUXER. l.F.l XOLLIHD, 8.D, 1956r Studtea 1r thc Provldeaclr arca' Xcrlcol fII acutroa
    act1va|1oaaao1yaoroff1utdlDc1u!loD.frol||ocboBu.nr.E@gr61r
    1390 - 1198.
    RABOIiE' S.D.c. 19?let lgaaoua gcology of tbc yortorD ldrl,telourl Vrlby, Obluuur!.
    (Uapubllrhcd lt.Sc. tbsl! lodgcd la thc Llbr.ry, UDiv.r.lty of Aucllud.)
    1971b: Seport ou folloy-up plotrtr, aortb oarl. Great Brrrlcr frhnd.
    Coarolldatcd S!lvcr illulDg ColpaDy ol X.rr Zealend Llrttcd. I copy 1r bcld oD op.n
    fllc (roforcaco 1211611216) et Hlaer Dlvtaloa. ttolllagtoa.
    19?5t Potrogrephy rad hydrotheroel rltorrtloD of tcrttrry radraltr-rbyolttr
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    of Ceoloev and Geophvslcg 18p1t 239 - 258.
    1977t Holybdeauo-baae-retel-blasutb llnorallcrtloa rt Eltot Croel, f,rreror
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    RlxsAt' V.R.H. 1j71t Oeology of South csntral. Oraat Barrler Icl,aad. (Uopubllabed
    tb6816 lodgecl lu the Llbraryp Ualveralty of Auckland.)
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    R0BI ilSolt, B.lr. 19'llz The orl.gla of llacrellzltloa it tbc lul Hlne, lc lrohr. Icv Zrrhnd.
    ln the llgbt of atable laotope rtudlca. EconouLc Geoloay 6915;l 910 - 92r.
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    ROEDDER. E. 19622 Anclcnt flutdg 1n cryotab.Sclcntiflc Aoortcan 2A7t 3E - 17.
    196?: F1uld locluel.ona ro aenpler of orc flulda: ln rGsochellatry o! Bydrothcrrrl
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    19122 Corpoaltlon of fluld Locluslona. Chepter JJ. lu rDrtr of GeocherLrtryr
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    19'l6z FLuld-lnclualon ovldaocc o[ th6 gencala of orei ln acdlueutery and volcrnlc
    rocks: ln rHendbook of Strrta-bound rnd Stratltolr Orc Dcporltcr cd. X.H. Uolf.
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    1979. Fluld iacLurlonr aa aerplcr of or. fluldal la rGcochoolrtry of Sydrothcrrrl
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    ROEDDER. E.l INGRAM, 8.1 ltAlt, Y.E. 196Jt Studter of !1uld laclurioa. III: grtractloo rnd
    quantlt.,tlro rnelyala of lnclugi,onr ln tbe rllllgrel r.ag.. Econoalc Gcoloqv
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    ROSE, l.U. 19'lO; Zonal relatlona of vallrocl elteretlon rad aul.pbiile distrlbutlos rt porphyrt
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    ?orlerre, Yalpapa and Haart Schlat tcnrucl. Pb.D. tboair lD CooLogyr Ylctorla
    tlnlvoralty of Uellllgton.
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    19'tlz Ftssloa-tracl rge rud trrce rlersnt geocherlrtry of torc l{l'adeu
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    SCHIEEBERC, E.P. 1973t SuJ.phur fugaelty lerrulcnsatr vlth tho olastrocheotc.l sell ,glMI,l
    lg2*rS,fSr. Ecoaoulc Ceology 68: 507 - 51?.
    SCHSFIELD. J.C. 19672 Sbeot 3 tuckleod (trt fa.) rGcologlcrl ltrp of lcv Zee1aail 1r2501000r
    Departrent o! Sclcotlflc lnd Industrlal Reacarcbl Ielllugton, t{cu Zealend.
    SCOTFORD, D.N. 19752 I tsst of aluotalun La qurrtr rr e geotheuorote!. laerlcan Xlneraloslat
    601 139 - 112.
    SCOTI, S.D.l BlRltES, H.L. t9?1: Sphelerlte gootb.rroDrtry antl t.obrrotctry. Esonortc C.olo,EX
    66t 653 - 669.
    SCoTT, g.D.3 GASpARRI!{I1 E. 19?)z lrgentlrn pcntlrndltc, (Fc,lll)tfg6t. fror Blrd Rlvrrr
    llanltoba. Canadlan Hlneraloslot 'lzt 165 - 168.
    SEIiARD. t.H.
    ,1976t the atablllty of chloride conploxee of rlfvcr ln bydrothcrnel rolutlone
    up t,o 350oC. 0eocblolca'et Coaooehlolca lcte l,Oz 1329 ' 1111'
    191jt Bydrothopal traBaport and depoaltton of golds ln r0old Hlusralllatlolr
    cdr J.E. Glovar and D.t. Crovcr. PubLlcatlons of thc Ocolosv Dboartroat and
    Ertenslon Servlcc. Unlvergltv of l{crtern AuatraXla' 3t 15 - 55'
    19811 lletal. cooplcr fornattoq la aqucoua rolutlonr rt clcvrted tclparrturot rad
    prorruro!. ltobel Syrportul on Ch!lrtry end Geochcrlttry of .olutloD. rt Blgb
    prergurss aad Terporetureat 1a lbyalca eail Cbeutgtry of th. Bartbe Yol 1l ' 1l
    F. lflcklan I D. Rlckard cill. Pcrgauoa Prcra.
    SUEPPIRD, S.t{. . '1977t ldeutlflcatlo! of tbc orlgia of orc forrlng rolutloaa by thc urr of
    rtable 1aolopea. Ia !Volcanlc Procolgel la 0ro Geaoal.at. Spcclal Publlcatlon lo.?
    of the Oeoloslcal Socletv of Londont 25 - 11.
    sglxtzoxo. l{. 1j75t Hlnerallgatlon rnil cballcal snvlroalcnt o! tb. toyoba lcail-rluc YclD-tJrP.
    dcpoalta, f,olkaldo. Jrpan. -Econoolc Geolopv ?0(t)t 69L - 7O5'
    19?8: Selenlur coateat of, rcantblte rDd tbo cbcllcll cavlronreutr of Jlplacrr
    vcln-tyP. dePo!1t!. gconoolc Goolosv 13(tl, 521 ' 5t3'
    sBISf,trIX. I.lt.l HITEIKOV, C.t.r XIKHAILOYI, V.l.' RlDlsf,Svs[II, X.S.l STDOEOY. l.F'l
    IARPE]IIOY, l.H.l f,oHDRAT'EV, A.V., B0Df,O. I.A. 19?l: Bogat'abya lercbron razaovlduortl
    PntIand1tr(^l11vcrrlchpcntIaad1tcrrrlcty).@100t
    l8l - 191.
    sILLIlo!'R.u.1972trhctoprradbottorro!porpbyrycoPP.rd.Po.1t..E@gr68t
    799 - 81r.
    SILLITOE, R.H. 1977t Xotr1llc alncrellrrtlos rffllhted to aubrcrlll volorallr: e rovi'sv.
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    1980r Ceuldron aubrldcncc ae e pooclblc lnblbltor of porphyry coppcr fonatloD.
    Socletv of lllnLnp 0aoloelrta o! Japan Speclal Isaue 8t 85 - 93,
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    19672 Geology of tbe CoroDaadel regloa vlth erpbta!,a oD 80!6 ecoiorlc aapectl.
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    ltsxrnol, x. 19?11 Tbo lroa-tungatea-rulpbur ryrteu .!d lts gcologlcrl raaoclrtloa'
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    S!EVE||S, C.R. 19?0r Upper Jurrrrlo Belor altca fror f,urotunu (Cororandcl Pcnlarulr)
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    19792 Orygea aad bydrogcn laotopc rclat!'oaabtpr !'a bydrothcrrd rlnrrll
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    IHOXPSOI, B.N. 1960r Sbeot 28 Barrl.cr (trt fa.; rGeologlcal Xrp o! Ncy Zerlead 1t2501000r
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    or1d.iloa potentlal aud plt. Ceochsrlatrv taternatlonal 7t 1205 - 1225.
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    TORCf,LXR. L. 19?82 the geology o! tbe l{eayoavllle erer. (Unpubllahcd H.Sc. tbsrll loilgcd ln
    ths Llbrary' Unlveralty of tucLl'aad.)
    ?O0LXII, p. IIIr BARTOII, P.B. Jr 196tr I thcrnodya$lc rtudy of pyrltc aail pyrrhotlto.
    Geocherlca ct Cogoochiulca Acta 28t 611 ' 5'11.
    URIEE. t. l9,l'lt partltloD of cailllul and raagaueac bstysca coorlrtl[8 aphelcrltc rnd grlonl
    fron role Jtptaeae epltbernal depoalta. Hlnerallus Depoglta 12t 319 ' tt0.
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    penlurula, lley Zealand. tcrulnal report oD Jolnt Yottturo vlth Conallvcr (J.Y.
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    VIf,RE, p.C. 1981: Sllv6r alaerallsatlon ln the Rochertcr Dtatrlct, Perahlng Couatyr lcvade.
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    vuoRtlllxEf,. I.t ui[LI. ?.A.t PlPUltgXr !. 1972t lrgeullen peatlrndltr lror lorc tlaalrb
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    UEICEL, D.A. 19782 IdeLte rcur.jfrs6.rt .od rolrted phaaca: thclr pbyalco-chollcrl fceturor,
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    UELLXIX, g.Y. 195{r Streas patt6rD controlllng lodc lonrtloa rud trultlDg rt Urlbl 11!c atld
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    eorparetl sltb bot-vater ryrtote. Econoulc Gaolozv 662 75 ' j7.
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    rppllcatlon to porphyry oopp.r d.potltt. Econoulc Gcoloqv ?0121r 316 ' 358;
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    frot 12 to 40o and at prsaulGs to 5OO etaoapberea. Crl,tlca1 Pbenorear. J.@.g
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    Sclentlflc aud fnduatrlal Rcoearcb Internal Report. I copy la beld ou open tllc
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    Hlacr of ll.z. Ltd. I oopy 1r held oD opcE flIe (rsfrrcacc 913231 rt ilta.. Dlvlrtoo.
    tfolllngton.
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    Reaerrchr IelIlngton. tlcY Zcc1aad.
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    aulphldc llncrala. Hlnoraltup Dcoo'tltq 11r f9? - 2O9'
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    Journal of Pctroloev 7z 151 - {88.
    A$TI($tr EINBI CEISIIE

    EIIID llwtrffioD$tr g,raEin lwr(Fgi AilD eiEoct-'Eltr$rru

    oF FOEP,ftlE OeP8fi AID EPITIEIUAI; UEffi IiECtms

    0r @' HIII8AE Gi4O - SILVEfi, F[OUf,ilGEl

    MEI ZEAIAIID

    vourlrB 2

    AIFEIIDII 1

    a nsnrnr 0F !-E r![DtVlu[,['I, usp@ffi


    CF TTIE SAURAI(I GOLI' - SILVER TNCiVNUCN

    lwus l9e
    (i)

    collTElr1s oF voLuME 2

    . APPENDIX I
    A REVTEV OF TITE IilDIYIDUAL DEPOSITS
    OF THE HAURAKI COLD - SILVER PROVII{CE

    Paeo

    INTRODUCTIOII 271
    PREAHBLE 271

    IlttBoDttcToRl lfoT8s 271


    Orc Petrography 271
    !llneral and Rock Chenlrtry 271
    lheruocherlotry 271
    Scope of Blbllogrsphj.ca 27?
    Adalltlonal. Sourcea of Inforoatlon 273

    I-f, IIINERS UEAD AT{D TIE NEEDLES 275


    INTRODUClIOII 275
    CEOLOCI 275
    K-Ar AGE 279
    IITDROTHERMAL ALTERATION 279
    I.II NSRALISATIOil 279
    l,llnera llead 279
    Envlroaooat 279
    Bypogene lllneralogy 2'Ig
    Supergeaa l{lneralogY 281
    Tho l{eedles 281
    FLT'ID IIICLUSIOilS 281
    SULPf,UR ISOTOPES 28t
    DEPTH OF I.IINERALISAIIOII 2e,
    THERHOCTISMISTRT 281
    GENESIS 285
    NSTNNBHCNS AND BIBLIOCRAPITI 287

    I-B IE AIIU}.IATA 288


    INTRODUCT]ON 288
    cEoL0cx 288
    HTDROTHERMAL ALTERATIO}I 290
    HINERALISATIOII 290
    FLUID INCLUSIOIIS 292
    SULPSIIR ISOTOPES 291
    DEPTH OI' MIIIERALISATIOII 291
    TIIERI{OCHEUISTRI 296
    Introductlon 296
    Stage 1 296
    Stage 2a 296
    Stage 2b 300
    GEI{ESIS 30t
    EEFERENCES AND BIELIOGRAPU tot
    I-C IIORTNERI COLVILLE PE}IIXSULA tot,
    I[TRODUCTION 301
    cEoLOcl ,04
    K-Ar AOE DATA 305

    VEronl.e, rJhlvERstry oF wELLti.lcTC.N


    (il)
    Paqc

    HETAI{ORPBISH t06
    I'EUItsRIC ALTERAIIOX 30?
    EIDROISERXAL ILTERITION toT
    I{IIIERALTSATIOII to7
    DLsgaolaated l{lnerallsatisa 70?
    Velu Hlnerallsatlon 308
    Soutb Coest 308
    Sony l,lary Strean 308
    Eope Streal 309
    Stony Bey Creek to9
    Doctorg Creek 310
    Eva l{lne 310
    Taugiaro Strear 310
    Supergene l{laeralogy 312
    rLUID II{CLUSIONS 312
    SI'LPEI'R ISOTOPES 312
    LEID ISOTOPES 311
    DEPIH OT ITilERALISAIIOTI 31L
    THBRHOCIIEI{ISlRI t11
    GENESIS 319
    REFERENCES AND BIBLIOGRAPHI t20

    I-D IUAOtUNU 321


    IIITRODIICTIOil 121
    CEOI,OCI 321
    HIDROTITERI.IAT ALTERATIOII 32t
    I{IilERTLISATIOII ?2'
    FLUID IIICLUSIONS 125
    SULPSUR ISOTOPE$ 127
    TEER}.IOCEEI{ISTRI 327
    GEIIESIS )29
    REFERENCES AI{D BIELIOGRAPHI J30

    I.E IOKATEA, COROMANDEL 3tl


    Il{tR0DucTIotf 311
    CEOLOCY 3tl
    HYDROTIIERHAL TLTERATIOU t?,
    I.IINERALISAIION 333
    tokatea B1g Reef t)t
    lokatea l{lnea 133
    Succegs l{lne tt5
    FLUID IIICLUSIONS 117
    SULPIUR ISOfOPES ,37
    HYDROGEII ISOTOPES )39
    THERMOCHEHISTRI tt9
    CENESIS 3It
    REFERET{CES AIID BIBLIOGRAPEI tLt
    I-F trAURI BLOCK AT{D KAPATIGA' COROTA!{DEL 1U
    INTRODUCTIOH ,11
    OEOLOGI 7tl
    HYDROTIIERI{AL ALTEMIIOII t16
    I{INERILISAlIO!I t16
    Kaurl Block )16
    Kapanga 3l'1
    (iij.)

    Paco

    l$EnlrocHEHrslRl 719
    CENESIS 351
    BEFESETICES. AIID BIBLIOGRAPIII )51

    I.O PETOTE STREAH TREA 352


    I!tTRODUClI0lf 352
    , CEOLOGI t12
    EYDROTEERI,ITL ALTERATION t52
    HIIIERALISATIOII 351
    FLUID IIICLOSIOIIS 358
    UIDROGEII ISOTOPES t59
    SULPEUR ISOTOPES )59
    LETD ISOTOPES 359
    IHEBI{OCHE}IISTf,I 359
    ' GEUESIS 361
    REFEREICES AIID BIBLIOORAPET 35)

    I.E I{HAIIGAPOUA AND TflE OPIIOTIUI HIIS 361


    I!|lRODOCII0!l 36t
    GEOLOCI 361
    TIIDROTTTERMALILTERAITOlI t6t
    UITIERALISATIO!I t55
    rLUID IIICLUSIOI{S 369
    SULPHUR ISOTOPES t?1
    TTDNOOEN ISOTOPES )71
    lHERI,IOCIIEI,I ISTRI 371
    fntroductlon t11
    Stage 2 371
    Stage 3 ,7)
    Stage { 373
    CEf,ESIS 3'16
    REI'SREICES II{D BIELIOCRAPf,I )76

    I-r filurtr ?77


    IiltR0D0c?Ioll )77
    CEOLOGI 377
    IIIDROTTIERI.IAL ALTERAIION l?8
    HII{ERALISATION 382
    CEHESIS 182
    REFEREUSES AITD BIBLIOGRAPEI 381

    I.J KAPOUAI 785


    IUIR0DUCtI0!l 185
    CEOLOCI 385
    HIDROTUERI,IAL ILTERATIOf, 385
    H IXENALISAIIOII )85
    CElIESIS t87
    REFERSNCES AT{D BIBLIOCRTPEI t87

    I.T BROKEII f,ILLS 388


    IilIBODUCTIOII t8E
    cEoLo0l 38E

    IIIDROTUERI.IAL ILTERATIOlI 388


    HIIIERALISATIOil t92
    FLUID INCLUSIOlIS 39t,
    (iv)

    Pase
    DSPTH OF HIilERALISATION 391
    THER}IOCIIEIIISIRT 398
    csNssrb 398
    Ereccla Plpa 398
    Vetns 401
    REFEREIICES ATID BIBI,IOCBAPflI 401
    , I-L trPU - lEAlES l.o2
    II{TRODUCIIOII l.o2
    GEOLOGI 102
    K-AT AGE DATA lOlj
    HYDROTIIERI,TIL TLTERA TI OII LOl
    }IIT{gRALISATION 106
    FLIIID IIICLUSIOIS 410
    SUTPIIUR ISOTOPES 't12
    ISERI{OCHEilISTRI 111
    Porphyry lllaerall eatlon 111
    Vsls lllnereltaatloa 11L
    Cu - Bt l{tnerall.satloa 116
    Pb - Zn lllnorellgatLon 4r6
    OEilESIS 418
    REFERENCES AI{D BIBLIOCRAP}IY L2?

    I.H fEAHES lr23


    THAHES SPECIAT AREA 123
    IIITRODUCTIOI{ &2t
    GSOLOGI 123
    EYDROTHERHAL ALIERASIOIT L28
    HIITSRALISATIOT 129
    FLUID IIICLI'SIOIIS 130
    SULPHUR ISOTOPES 132
    DEPTE OF HIIIERALISATIOI t3t
    lEERI,IOCEEH ISIRI 131
    0ElrEsIs 136
    REFEREIICES AIID BIELIOGRAPET 137

    I.N TEAVESVILLE 138


    INTRODUCTIO!I 138
    CSOLOGI n8
    HTDROTHERHAL ALTERATIOII t,12
    HITIBRALISATIOI t42
    HlnEraltgatloo la Andestte lr12
    Mluerallsetl.on ln Bbyoltte lrl+3
    Gracel aail the nBluffgr lr13
    Chanploo *15
    FLUID IIICTUSIONS u5
    HIDROCEII ISOTOPES Ll7
    SULPIUR ISO1OPES 117
    DEPTH OF }IIUERALISA?TOf, 111
    Tf,EBHOCUEI.{ISIRT 119
    Introduotloo 149
    lJax Reef LL9
    Gracee. Blrda and Oolilen Arrou 419
    Dlscuaglon 451
    OENESIS L5t,
    (")

    Paee

    RESERETICES ATID BIBLIOCNAPUT 115

    r-o xrnrroio 156


    IIITRODITCTIOII 156
    OEOLOGI 156
    IIIDROTIIERI{AL ALTERITI OU 156
    !,rIl{ERAI,ISATI0I{ lr58
    ,r:
    fntroductlon 158
    Caroola VeLn L62
    SlIvEr Queen Vela 1,61
    FturD rlrcluslo$s 1?o
    SULPBI'R ISOTOPES 171
    CARBOH rlD oXTCSU ISOIoPES 176
    ITDROOEII ISO1OPES 176
    DEPTH OF I{INERALISATION 176
    tcERl,l0cIEllIsTRY L78
    GEIIESIS 182
    REFERE}ICES AND BIBLIOCRAPHX 155

    I.P COLDEII CROSS {86


    I[IRODUCTION 186
    GEOLOGI 486
    RIDROTTTERT,TAL ALTERAT IOII 186
    IINSRALISATIOI {86
    cs{EsIs 187
    REFERENCES AIID BIBLIOGRAPII 187

    I-Q f,ol,l^TA 488


    IIIIBODUCTION 488
    oE0Locr 488
    ITIDROIHERI.TAL ALTERATTON 488
    }II!IENALISATIOII 488
    FLUID II{CLUSIONS 490
    'sureuun IsoToPEs 191
    DEPTU OF HIIIERALISATIOT{ 19 t,

    GE}TESIS 191
    REFERENCES AUD BIELIOCRAPEY 195

    I.R WAITEKAIIRI 496


    It{lRoDuclI0ll 196
    GEOLOCI 496
    EIDROIEER}IAL AI,TERATIOII 196
    HIIIERALISATION 5oo
    FLUID IITCLUSIOITS 501
    SULPUUR ISOTOPES 501
    lBERI.IOCHE}IISTRI 50L
    CE[ESIS 50?
    REFEBEIICES AT{D BIBLIOGRAPEI 50?

    I.S I'AIITI 508


    mTRODUCII0t{ 508
    CEOLOGI 51t
    HYDRO1IIERMAL TLTERAIIOX ,16
    . 519
    HIITERALISATION
    Hartha Veln SYetcc 519
    ("r)

    PaEc

    Boaeaont 8111 Velns 52'


    TLITID IXCLIISIOIS 525
    SULPEOB ISOIOPES 527
    BTDROCEU ISOTOPES 5?9
    DEPTS OP IIIIIERALISATIOU 529
    IBERMOCBEHISTRI 529
    Introductlon 529
    Deep level alaerallaatiou 5Jl
    IaternedLcte level atnaraltsatloa 531
    Shallon level nlneral!satlon 535
    cElf EsIs 57'
    REFEREIICES AIID BIBLIOCRAPEI 510

    I.1 TAEATICA.HAKE 511


    rulR0DuclI0il 5L7
    OEOLOCI 512
    [IDROTEERI,IIL AI.IERATI O[ 512
    E-Ar AOE DAIA 511
    }III{ERALISATIOT{ 511
    Crovt Vela 511
    lfelcoue Veln ,It
    llarlo VeIn 516
    TI,BID ITICLUSIONS 519
    SULPIUR ISOTOPES 557
    DEPTE OP MIT{ERALISATIOII 551
    THERMOCEEMISTRI 551

    cEllEsrs ,53
    REFSRENCES AND BIBTIOORAPET 554

    I-U TUI I.IIUE 555


    INTBODUCTION 555
    CEOLOCI 555
    .ETDROTHEBHAL ALTERATION 557
    f,-Ar A0E DATA 557
    I{IilERALISATIOII 557
    FLUID IXCLUSIOIIS 562
    SULPHUR ISOTOPES
    561
    CARBOII AND OITGEN ISOTOPES OF CARBOIIATES 568
    UIDROGEI{ AND OXIOETI ISOTOPES OF BIBIIE' QUARTZ' TAOLITIITS AND TLUID
    rNcLusI0lls 568
    LETD ISOTOPES 570
    DEPTU OP I,II}IERALISATIOII 570
    TIERI{OCTIEHISTRY
    510
    CENESIS
    577
    5?7
    REFERENCES AIID BIBLIOCRIPf,I

    579
    I.V WAIOROIIGOMAI
    INlBODUCTIOII ,79
    GSOLOGI
    579
    579
    f, IDROIU ERI.IAL ALTERAIIOII
    5?9
    }IITTERALISATIOil
    582
    FLUID INCLUSIOI{S
    HIDROCEN ISOTOPES
    581
    586
    SULPIIUR ISOTOPES
    586
    LEAD ISOTOPES
    (vrx)

    tre,
    DEPTE OT IIf,ER^LISIIIOI 586
    568
    cErEs.rS ,9,r
    EBflEruilc8 TilD DE.IEIbCETFST ,91

    [tI8qSr,LrNEoius DoPosfliB 592


    ,IIITROTDUCXIOtT ,92
    , rfif,TuItr B*I 592
    goLYTLtE tREr 5r2
    tirlt(oRorrtro v'tEuEr J95
    ol{sRA 596
    tnol' 616rr0;u-B t9 laxau* 596
    oEur 596
    f,NU,TE8AIGA V,ffif,Ef, 59r
    I"UOI( lf LA$T UrtrE (Wfl,tREfifilll VATLLEE) t98
    ot'taEu yu&Er 598
    TE.!|I-rfl}R[$ r HAlf,GlfflTA AREI 599
    il^rfll Icfu]rEilf 5eE
    or{t{ Rotl 600
    ilAgKAIIOIIT 60P
    ITX'IRIg REEF8 (T8 FffiT) 602
    (vlii)

    LIST OF FICURES III VOLU!{E 2


    FICI'R8 Paac

    I-1 tocatlon of areae tlaacrl.becl ln aectlons I-A to I-V 272

    I-A-1 Xap of tbe slne antl adJaceut rocks, at Mlners Sead 276

    lr-A-2 Photograpb of tbe lnelda of tbo nlne at Hlnera Head 277

    I-A-3 Geologlcal l,lap of Hlners Eeed 2't8


    { I-A-4 Croas-sectloa of nlnerallsed breccla dlke 280

    I-A-5 Hlaers Head fluld lncluglon fllJ.lng tenperature and appareat'


    aallnlty hlatograua 282

    I-A-6 fSt veraua fO, dlagral for lllners Eead and the l{eedlag
    nlnsrallsatlon 28t,

    l-I-7 f0, veraus teoperature dlagran for l,llnera Eead and the l{eedles
    nluerallsetloaa 286

    I-B-1 Geologlcal oap and crors-Eectlon of Te Ahuneta 289

    I-B-2 ParagenetJ.c aquoace of nlaerale at Te Abuoata 291

    I-B-3 te Abuueta fluld luclusloa fllllng telpereture and apparent aallnlty 293
    hl.atograoe
    I-B-4 Depth of nlnerallgatlou at Te Ahunata 295

    I-8-5 fO, vereua pH dlagrau for Te lhunate stage I nlneralleatlon 298

    I-8-6 fOa voroua pH dlagrao for Te Abuuata Stage 2a olnerellgatlon 299

    I-B-? fs2 vorous fOa dlagrau for Te Ahuoata stage 2b nlnsrallgatlou 301

    I-B-8 foa versus pH dlagrao for Te Abuuata Stage 2b nlnerallsatlon 302

    I-C-1 Gaologlcal D8P of Nortbern Cofvtlle Penlneula 305

    I-C-Z llortbern Colvllle Penlnsula fluld lncluslon fllllug teuperature


    and apparont gallultY bistograns 311

    l-C-l fSa versua fOa dlagrao for Parltu Coastal Sectlon porphyry copper
    nlnerallsatlon 315

    I-c-4' fSa versus f0, dlagras for Northern Col-vllle Penlnsula vElu
    olnerallsatloa 316

    I-C-5 fot verous pll dlagral for l{orthera ColvtlJ-e Penlasula veln
    ol.oerallsatlon 317

    I-l-1 Geologlcal oap of tbe Kuaotunu alea 322

    I-D-2 Paragenetlc soqueuc of velo ulaarals at Kuaotuuu 32t,

    I-D-3 Kuaotuau fLul,d laclucton fllllng teoperature asd appareni aallalty


    hlstograus J26

    I-D-4 fsa vereus f0, dlagraq for Kuaotunu vslu olneralisattons )28

    I-E.l0eologlcaloapoftheCorooandelaqdtokateaarag 132

    I-E-2 tokatea flutd lnclusloa fllllag tetperature aud apparent sallnlty 336
    hJ,etograoa
    I-E-3 fOa versua pll dlagrao for Toketes base uetal nlaerallsatlon 310

    I-E-4 fs2 veraua f0, dlagreo f,or Tokatea gold-allver nlaeralleatlol 3L1

    I-E-5 f02 veraua plt dlagrao for Tokatee gold-rllver oluerallratlon 112

    I-F-l Map of velae aad rorklnge tn tbe Kaurt Bioak end Kapange sroat 3t5
    I-l'-2 fsa versua fo2 dlagrao for Kaurl Block aud Kapanga rlaerall'srtlong 318
    350
    I.r.3f0.versuepHdlagrauforKaurlBlockandKapraganloorall'satlons
    (i')

    FIGURE Pase

    I-G-l Oeologlcel rap of thc Petote Streao area 35)


    I-O-2 Parageaetlc aequ6nc6 of ulnerale ln the relns ol the Pctote Stroal
    atea t55
    I-C-3 Pbotograph of a ulnaralleed apeclnea frou tbe Hutt Creek vel.n 356
    I-C-4 Petotc Strean arcc flulil lnclualon fllllng teuperature aud apparent
    aallnlty htatograoo 357
    I-C-5 fS, veraua fO, dlegran for Petote Streal area Stage 1 nlaerallsatlon 360
    I-C-6 fOa versua pII dlagran for Petote Streer area Stage 1 olnerallaatlon 362
    I-B-1 0eo1og1.ca1 rap of the Whangapoua ar6a 355
    I-U-2 l{ap of tbe bydrotbernal alteretlon zones ln the l{baagapoua area 367

    I-H-3 Paragenetlc sequenco of ulaeralc lE velns of tbe Uhengopoue area t68


    I-H-4 fSa veraua taoperature diagreo )72
    I.e-5 fO, veraua pH dlagrau for l{bangapoua Stage 2 olaerallsatlon 37 t,

    I-H-6 fS, vareua f0, dlagreo for llhergepoua Stage 4 nluerallsetlon 3?5

    I-f-l Oeologlcal aap and cross-sectloa of tho Hatrala ara 379

    I-l-2 Map and cross-sectlon of tbe bydrotherusl alteratton zoneg La the


    Hanaia area 380

    I-I-3 Paragonetlc aequence of olnerellgAtl'on l-n the Mauala grsa 381

    I-I-4 l{odel for porphyry coPpor type uj'aerallsat'lon ln tbe l'lanaia area 383

    I-J-1 Oeologlcal uap of tha Kapoval ares 386

    I-K-1 Geologlcal oap of tbe Broken lllLLs aree ,89


    I-K-2 Croea-eeotlon of tbe Broken 8111s qlne 390

    I-K-3 Plan of the velaa 1o 1on levela of the Broken l|llls Hlne t91
    I-f-4 Paragenetlc sequotrce of nlaerels frou tbe breccla plpe' Broken
    H.iLlg }|lue )93
    I-K-5 Plan of 2 level Eroken 8111e Mlne 395

    I-K-6 Erokau ElUs fluld lacluslou fllllng tenporature end apparent


    salLaiby hlatograne 396

    I-K-? Depth of oinsralleetlon at Broken lltlls 397

    I-K-8 fSa versus f0, dlagran for the Broken Bille ulnarallsatl-oo )99
    I-K-9 f0a vorsua gH dlagrao for the Broken tltllg nlneralLeatlou 400

    I-L-1 Geologlcal uap of the Tapu-Thanea area Lo3

    I-L-z Paragenetlc EequencE of olnerals ln vel,ne of tha fapu-Tbaues ara 107

    I-L-} Hap shovtug locatlon of porpbyry coPPr etyle daposlta ln the


    Tapu-Thaoer area 408

    I-L-4 Paragenetlc s6queDc6 Of qluerele- 1o guartz-serlclte zoaes of


    porphyry eyeteoa ln tbe lapu - Thaoes area 109

    I-L-5 fs, vereus foa dtagrao for cu-Bl ol.neralleatloa ln tho Tapu-?benes
    velns 115

    I-L.6 fsa verous fo, illagrao for Pb-zn nlaerallsetloB ln the Tapu-Thalcs
    velag 117

    T-L.7 f02 veraue p9 illagral for Pb-zn nlnerallaatloa lq the tapu-Tbareo


    vel'na 9
    '1
    I.L.8 ftea versus fS, dlegrao for Pb-Zn olneralleatlone ln tho ?apu-
    thanos valns 12O
    (*)

    9IOURgS Paeo

    r-!t-1 llap ehovlng tbe locatloq of ulnee ln tbe Thaues area ' 121
    I.H-2 Geologlcal rap of tbe Thaoeg area 125
    r-!,t-, Croae-aectl,ong o! ths Tbaoea area 125
    I.M.4 Log of tha Kuranut-Celedonla drll} bole 127

    I-H- 5 fS2 veraua f0a dlagrao for the Thares gol.d-pyrargyrtte ulneralleatLool33
    t I-H-6 fO, verauo pB dlagran for the Thaoea gold-pyrargyrtte llaerallsatlos 435
    I -lt- 1 GeologJ.cal oag of the lleavegvllle area 139

    I.N-2 Cross-sectlon of tbe lleavesvllLe area 1,10

    I-t{- 3 Cl.agslficatlon of hydrotheroally altered rocks at feaveavllle l,L1

    I-|l-t l{eavesviLle fluld Lncluglon fllllng tanperature and apparent


    saltnlty hlatograue l,1l
    I -lr- 5 Deptb of ulnerallsatloa at l{eaveevllle 116
    I-tf-5 fSa veraua fOa dlagrao f,or ainerelisatlon'ln the lJar vela,
    llesvesvllle l'5O

    I-!l- ? foa versua pll dlagral for olaeralleatlon ln tbe AJar vela,
    lleavegvLlle 151

    I-n-8 fS, veraus f0a dlagrao for olnerallaatlon ln the Bluffs aectlon,
    !leavesvl1le 152
    I-lf -9 fO, versue pH tllagrau for ul.nerallsatlon ln tbe Bluffs aectloa,
    lf eave sv111e 1,53

    I-0-1 Oeologlcal nap of tbe Hargtoto-Goliloa Cross-Kouata-tlaltekeurl Arsa 157

    I-0-2 Map of velng ln tbe llaratoto araa 159

    I-0-3 Generallesil plan entl loagltudlnal sectlon of the l'laratoto veing 161

    I-O-4 Paregenotlc soquoncs of uluerala ln the Caooola Velnr Maratoto 116)

    I-0-5 Paragenetlc segunco of nl.nerrla ln the Silver Queea Velu, Haratoto t65
    I-O-6. Photoolcrograpb of Stage 2c Sllver Quaen Veln ol.aerall.setloo 16',l

    I-0-? Pbotograpb of Stage 2c Sllver Queen nluerellaatLon ln hand specluen 45e

    I-O-8 Photollcrograph of Staga 2c Sllvsr Quoea uiasrallaatloo 169

    I-0-9 f{aratoto fluld lncluslon fllIing teoperature and apparent eellnlty


    hlstograo lr71 - Ir72

    I-o-10 5 13c ,"t"uu 5 130 dlagrao for l{aratoto carbonate olneralg 175

    I-0-11 Deptb of nlnerallsatlon at Haratoto L77

    I-O-12 fSa veraua f0, ellagrao for Stege 2 l'faratoto olueralleetion 179

    I-O-1' fSa verauc foa illagran for stage 2 lleratoto tl,uerallsatlon 480

    I-0-14 fOa varaue pE dlagran f,or Stege 2 llaretoto nlaercllaatlon 481

    I-O-15 fte2 veraua fSt dlagral tor Staga 2 l'laratoto nlneralleatlon L8t
    I-O-16 foa veraua pE dlagrao for Stagc 2 f{aratoto uluerallsatlou 1,81,

    I-q-1 Lougltudloal sectloag of the Koaata Mlne 489

    I-q-2 Plan of Kooata 8 level 491

    I-Q-3 Koaata fluld luclualoo fllllag teoperature and appareat eallnlty


    blatograua 492

    I-Q-1 Depth of olaeraltoatlon at the Koneta l'llne 19)


    I-R-1 Geologlcal nap of tbe Wal'tokaurl area 197
    (rd)

    FICI'RES Pase

    I.R-2 Claoglflcatloa of the hydrotberoel alteratloa olneralg ln the


    I{altokaurl aree lr98

    I.B-3 Parageoetlc soquEco of olaeralg ln the Waltelcaurl Veln 199

    I.R-4 Photoulcrograpb of !{altekaurl. 9tage 2 ninerallaatlon ' 501

    I.R. l{eltekaurl fluld lnclualoa f1l1lag teuperature and apparent


    ' aellalty hlatograoa 50)
    { I.R.6 fSa veraua f,Oa dlagreu for Stage 2 ulneralleatlon ln the
    $altekaurl Voin 505
    I-R-7 fO2 versue pH dlagraa for Stage 2 uinerallsatlon lu the l{altelcaurl
    Veln 506

    I-S-1 Map of vslns ,.n the l{alhi area 509

    I-S-2 Depth relatlons of rlne levela 510

    r-s-3 Geologlcel uap of l{aihl 511- 5',t 2

    r-s-4 Croea-sectlong of tbe Hartba Veln syeten 518

    r-s-5 l{elhl flutd lnclualon fllllng tenperature and apparent aallnlty


    hLatograoa 521

    r-s-6 Coupoalte fluld hclueloo f1ll1ng teoperaturc dlagran ,26


    I-S- 7 Depth of olnerallsetloa ln the Hertha Veln eyeten 528

    I-S- 8 fs, versus f0a dlagren f,or deep level olaerallgatlou la thE llartha
    vein systen 532

    r-s-9 f0a versus pH dlagran for deep 1evel ulneralleatlon in the l,lartha
    veln eysteu fi3
    I-S-1 0 f0" versua pH dlagrao for lotErnectlate level olaerallsatl-on ln tbe
    Haitha veln aysten 53t,

    I-S-1 1 fS, versua f0o diegraq for ghallon leve1 !1!6rall8atLous ln thc
    Mafthe voln sfsteo 536

    r-s-1 2 f0, versus pH dlagran for ahall-ov level ulnorallsatlon ln thE


    Haitha veln syateo 53',1

    I-S- 1 3 Structural lnterpretatloa of tbe Martba veln aysteu 519

    I.T.1 Map of the vel.ns and norklngs at f,arangahake 5|t


    I-T.2 Croes-soctlon of tbe Karaogabake veins 5lr5

    I.T.] Longltudlnal sectlou of tbe Tallsuin Hlne 51,7

    I-T-4 ilineraloglcal changes vlth deptb ln tbe Boaasza sectton of the


    Harla Vein. Kgrangahake 518

    I.T-5 Karaagahoke fluld lnclusloo filllng teoperature and apparent


    sallnlty hlstograos 550

    r-r-6 f02 versua pil dlagraa for tbe deep level olnerallsatlon 1n the
    TaIleoan }line, Karangahake 552

    I-U-1 Geologlcel uap of TuL l'llqe 556

    I-s-2 cbaages tn ulneralogy vlth lncreaalng lntenelty of bydrotheroal


    alteratlon at Tut lllue 558

    I-U- 3 Paragenetic aoquenco of olnerals lu the relna of TuL l'llne 560

    r-u- 4 Photograph of Tu1 Mlne hand apecinons contalnlag Stage 1


    elnerall setLoa 551

    r-u- 5 Photouicrograph of a vaPour rlcb fluld tnclualon frol tul l{lne 563

    r-u-6 Tul Hlne fLuld lncluslon fll1lng teaparature and apparent aallalty
    hlotogreos 565-566
    ('dr)

    trIGURE9 Pape
    I-u-? 613c 618o rlLagrau tor tul HLne carboaato nlaeralc 56?
    ""t",rt
    I-U-8 Depth of rlacrallratloa at Tul Hlne 569
    '3
    I-U-g foa veroua pf, dlagral for Stagee 1 and 2 llaerallsatl.onr tn velns '?
    ol the Tul l{lne 571
    ._'!t
    I-U-10 fOrversua pE dlagral for Stege 3 nluerallsatl.oa 1a vstns of the
    r Tul l{l-ne 5?1

    I-U-11 fS, veraua foa dtagrau for Stage 1 qlneralLartlou ln velaa of the
    lul Ulne 571
    I-U-f2 fSa vereus fO, dlagrao for Stege 2 olaerallaet'lon Lo velng of tbe
    Tui lllne 5',15

    I-U-13 f02 veraur pE dlegreo for Stege 2 lLnerallgatlon la velns of the


    tu1 l{lne 576
    I-V-l l{ap of veing ln the l{alorongoual area t80
    I-V-z Walorougooel fluld lncluelon fllllng tenpereture and, appcrent
    sallalty hlotograoe 5E

    I-V-3 Deptb of rinoralLgatloq et tlaLoroagooai 585


    I-V-4 fS, versue f0, for Stege 1 nlneiellaatlon ln tbe lfaloroagoual velns 587
    I-V-5 fOa versus pll dtagran for Stage l.olnerallaatl.on ln the llalorongonal
    veLna 589
    I-V-6 fTeo versus f0, dlagren
    - for Stage 1 ulnerallsatlou ln the
    t{al6roagooal v6tns 590
    I-lf-1 Locatlon uap for deposlte revl,evsd ln Sectloa I-ll 593
    I-W-z llap ehovlng depoalts aot revleued ln Appeadlx I 591
    I-U-3 Crosa-gectloa of the Mackeytovo clnnabar tlepostt 501

    - -.*$
    (rdir)
    LIST OT TTBLES Itr YOLUIIE 2
    .
    fABLE Paec

    I.8.1 Tberloehacl.cal paranetcrs tor rlncrallsatlona at ts lhuEata 29'l


    I-C-1 tberlocheotcal paraueterg for qlneraLleatlons ln Xorthcra Colvills
    Panlsoula ,1'
    I.E-1 fhorqocheulcal parauoterg for alnsrallsatloas at Tokatea 338 .:,E

    I.H.1 Therlocheni,cal paraueterr for slaeralleatl'ons at lfbaagapoua 370


    a
    I.L-1 tllaerale of tbe lapu-Theooa aloa 405

    I.L-2 5 34s values of oluerala aad calculat,ed teoperaturea for tbe


    Tapu-Thaoeg at6a 111

    T.L.3 Thernocheqlcal paraueters for tbe lapu-Tbaoes epl'tharual


    riaerellsatlons 11'
    I-lr-1 5 3{s varuos of ElBarals troq the thaueg area 131

    I-t{-1 Thernochaltcal paraoeterg for the rl'nerall'eatlons at Xeavesvllle 118

    r-o- 1 Cbeckllgt of prloaly qetallLc llueralE la velns of, the llaratoto


    ara 460

    r-0- 2 Ieotoplc coopoeltlon of eulphlde llserala fron tbe Haratoto lll.ne 173

    I-S-r Stratlgraphy of tba rockg la tbe lJel'b1 aree ,11


    I-S-2 Theroocheolcal parauetera for nlnerallsatLoaa ln the llart'ha Veln
    Syatea, l{aihl 530

    I.U-1 Tharoocheqlcal paraoeters for olneralleatloas at Tul l{lne 573


    271

    APPENDIX I
    A REVIEW OF TIIE INDIVIDUAL DEPOSITS
    0F THE HAURAKI coLD -_SLLVER PROVTNCE

    II'ITRODUCTION

    PREAMBLE

    This appendix reviews the d.eposits of the Hauraki Gold


    SiLver Provi-nce individually in a geographical order fron
    north to soutb (Fig. I-1 ). It conbines both the writers
    work and infornation from previous studi,es.

    INTRODUCTORY NOTES

    Ore Petrography
    Where d.etailed. descriptions of the ore petrography of
    ind,ivldual deposi.ts are available in prevlous works this
    appect is only briefly rnentioned. here. Hovrever, sone areas
    have not been investigated recently and where sanples were
    avallable for stud.y detailed descriptions are given. Because
    of the large nunber of speci-nens investigated fron Waihi,
    Karangahake and Waiorongonai, samples fron these areas are
    described separately in Appendices VI, VII and VIII respec-
    tively.

    Mineral and Rock Chenistrv


    Aspects of nj-nera1 and rock chenistry (e.g. EPMA, XRD
    and XRF analyses) are generally not revieued here unless
    pertinent to sone partlcular discussion.

    EPMA analyses of netallic ninerals nad.e d,uring this


    study are listed in Appendix II and sunnarised in Chapter j.
    Those mad,e by previous studies are referenced in Table 5-1.

    Thermoehenistry
    The infornation and methods used to calculate the therno-
    chenlcal paraneters discussed in this appendix are described.
    in Appendix V.
    272

    I-A
    Mlhcrr H

    I-C
    Northcvn
    Cdvilla
    Pcainsila
    b.o
    I:E lokalca t-o
    I.F K^ti glocl Yw,ohnttt
    rdryga I-n Wh'dty|a,q.ouq
    ^
    I-G 9elotc
    fuaa
    aljk; o
    r-r-L-':E-Lrar-a
    25k,rr

    I.L %vt
    Tqt- ta?ovtit 0
    '@t- Br*cn HiUs
    t-M
    @ux
    'olo

    .*,i^Jx,::
    *1filq,Psrs1-fr @V
    E
    I-U Tui M'*
    14.
    l-v v,laiuorrynait

    -l

    .Flgurc I-t r Locatlon of arcar dqacribcd ln grctloar I-A to I-V.


    2?3

    Scole of Bibliosraphies.
    at the end of each deposit seeti.on
    The bibliographies
    refer to the relevant Geological Survey Bulletin of the early
    19001s and subsequent works. References to earlier works are
    not included because they are listed in the bulletins as
    follous (see Fig. 1-? for locations):
    Coronandel Subdivision; Fraser & Adans (190?)
    pages 9 to 11
    Thane s Subdivi. sion ; Fraser ( 1 91 0 ) pages lr to 7
    tr{aihi - Tai.rua Subd.ivision; Bell & Fraser (1912)
    pages 4 to 6
    Aroha Subdivisioni Henderson & Bartrun (1913)
    pages 5 Xo 9
    Waihi District; Morgan ('lgZ+) pages 11 to 13

    Addi.tional Sourees of Infornatlon


    Kitt ('lgl1) listed al1 assays of nineral sanples for
    gold, silver and platinun carried out at Chenistry Division,
    DSIR between 1922 and 1 976. Chemical .aualyses of rocks nade
    between 1 91 7 and 1957 are listed in Challis (1971) .

    In addition to the geological sourees referenced in this


    appendix, nine p1ans, photographs and. historj-eal aecounts of
    tbe mining can be inportant to the geological interpretation
    of the nineraLisations.

    Detailed nine plans for rnany of the o1d workings are


    held ai the Huntly braneh of the Mines Divislon (ttinistry of
    Energy).

    Historlcal photographs of the mines and nining subjects


    are he1d. by the Alexander Turnbull Llbrary, Auckland l,tuseun,
    Coronandel School of l,lines Museum and the llaihi Art Centre
    and Museum.

    Historical accounts of the nines and niniug in the


    province include Bale (1971), Chapnan (z), Gwil1ian (1968),
    Isd.ale (1967), Kennedy (196t), McAra (lgla), Mcltreil (1967),
    , 'f
    271 ,-

    NoLan (1977), Read (196il, Siopson .(1971r, SonnervllLe (19 9)


    and Sparke & 0aueron (1965).

    Details of rnine developuent and production for the


    naJor nineg are gi.ven in a seriEs (geaerally annual) of MineE
    statEuentE (ParrLauentary Fapers; eop{.es are herd in the
    Llbrary of tbe Mines Dlvisioa, Seltringtoa) and, Galviu (1906).

    A detaiLed bibliography of publtshed and unpublish_ed


    $orks r,elatl,ng to the ninos iq gtate Forest eras ls given by
    Slaue & l{hLte (19S0).
    2?5

    I-A
    MINERS HEAD AND THE NEEDLES.

    INTRODUCTIgN

    Between 1857 and 1867 approximately 50r000 tonnes of


    rock uere nined fron i4iners Head, frorn whieh zj00 tonnes of
    copper ore were coacentrated, and exported,.

    Brief descriptions of the Miners Head area were given


    by Hutton (1859), Park (1897), Bartrun (1g?1r) and Henderson
    (1931, 1939), whereas a detailed report on the geology uas
    given by Gregg e! aI (1970). The geology of the area north
    of Miners Head was napped by Rabone (1971) and drAuvergne
    (197t+ar. Heigel (19?8) briefly described. the sutphide
    nineralogy of the deposits at Mj.ners Head and the lleedles.

    The mine at Miners Head. consists of a chanber lr5a x 1Zm,


    accessible by adit from the south, with a 22n deep shaft in
    one corner (Figs I-A-1 and I-A-2).

    GEOLOGY

    I'liners is a composlte breceia body intruding grey-


    Head.
    wacke suite rocks (nostly argilllte) of the Manaia H111 Group.
    It consists of an argillite (-greywacke) breccla .stocktr
    cenented by quartz and quartz diorite*porphyry (Fig. r-A-3)
    separated fron the uainland by a pair of d,lkes; a
    western mineralised breccia dike ('1.5 - i 5n wide) and an
    eastern quartz dlorite porphyry d,lke.

    Quartz diorlte and andeslte-d.aeite porphyry d.ikes oceur


    in the argillite and, greywacke to the north of l"liners Head
    (Rabone, 1971; drAuvergne, 197t+a) and at the Need.Ies ninera-
    lised breecia and pebble dikes s.lso oceur (Heigel, 19?8). The
    latter contain fragnents and pebbles of greywacke-argilrite
    and andesite porphyry.
    276

    lz t L't
    E a" mncmli*cd Wcer'ia dike,
    a-a-
    f,l 0t,a'r" drl,lte povPhyry d;/r;c
    9il'cifid and mdl.eraltscd
    wrjmttu.
    't
    M rnc sitictfrie/ arirllrtc
    ff
    Chanbar +

    flArgitlitz
    p-- Fault
    f enaFt,

    O lOfi
    Samplet
    t7965
    bqG6

    }-
    +
    +
    l
    ?ortal

    Plgurc I-l-1: Mepof ihc nlac ead adJeccnt roclsr, et Hlncrt Faad. (ilodtfted
    fror Grcgg 9L4, 1970,)
    277

    Flgure I-A-2: InsldE the olne at Mlners Head looklng south along the strlke
    of the nlneralised breccla dlke. The roof oS the olne above the caoera
    posltlon has collapsed forolng the h111 of rubbl.e ln the foreground. The
    log {once eurrounds a 22o deep shaft, nou fllled irlth uater. the valLs
    of the olne are stalned ul+.h oxldatlon products (nalnly nalachite and
    azurlte) of the olnerallsatlon.
    2',18

    w=
    rTfi
    l'..-..''J fulldw 6aach

    Etr Cu ftirlrzrdlisol Wonc\a dgc


    )
    Qrrartz dior\tc,prp\ry dikc |COROMA
    N
    = lnlrutivc etocv (auartz d;oAtc I CROI/P
    W,,H\"qW*;.P&UWlv)
    E---l Argtllitiz qrd grzyvacha- MNAIA t{lLL
    Far"rlt

    F1gure I-l-31 ocol,ogtcal uap of l,llners flead. (uoatftea froo Gregg .9t4,, 19?0-)
    279

    K AT AGE
    Biotite fron the quartz diorite at l,tiners Head was
    dated. at 18.1 t 0.2 m.y. by the K - Ar nethod. (Dr. C.J.D.
    Adans aud, Prof . P.M. Black pers. conx[.).

    HYDROTHERI'IAL ALTERATION

    The hydrothernal alteration of the igneous and greyracke


    cuite rocks is generally propylitic (secondary quartz,
    chlorite, serieite, pyrite, epidote, calcite, prehnite and
    zeorites i Gregg 94.L' 1970) , however tr{eigel (lgrc) con-
    sidered that phylllc alteratlon also occurs and, Prof. P.H.
    Black (pers. cotrln.) identlfied second.ary biotite (npotassicn
    style alterati.on) at Miners Head.

    MINERATISATION

    Miners Head

    Environnent
    Chalcopyrite with ninor pyrite and sphalerite nineralisa-
    tlon is exposed on the wal1s of the nine chanber, around the
    shaft, and on the southern eoast of the head.land in and around
    three sma1l adlts (Flg. I-A-3). It oecurs in a quartz
    cenented.argillite breccla dike ieparating the breccla nstockn
    fron a quartz diorite porphyry dike and the nainland.
    Tbe breccla dike is divisible ioio four parts based on
    the degree of sllieification and nineralisation (Fig. I-A-4).
    The nineralised zones (zones 3 and l) consist of brecclated
    argillite and greyuacke fragnents (5Onn dla.) cenented by
    quartz veinlets ranging fron 2 to 20nu thiek. Vugs contain-
    iug quartz crystals up to ?nu long oecur frequently.

    Henderson (lgll) reported eeveral analyses of the copper


    orer ranglng up to 23fr Cu. One sanple, ulth ?.71rfi Cu, also
    contained 3oz.9d,wt.7gr. (106 ppn) Ag.

    Eypogene Mineralogy
    Weigel (1978) d,escribed the sulphide niaeralogy as
    280

    /ode
    -:';: zone zor2e -dgke,
    zone
    ,-i"-,:_, { _\ t:
    Igneous ,"
    Sfoc,R

    ]1lil.Hl
    Llf +tl
    l-l l+ ''
    -#
    {
    torf?nSrr1rcopgrrfe

    Flgurc r-t-tr Dlagraratle c'oas-lcctLon of thc routhcrn coastal "*po"orl of t.


    (Frol Grc'tie 3!-l4,, tgZO')'
    . thc ulncrallced brcccl,a dikc at lllacru 8cail. :

    zonc 1: brccclated argllllta, osgaalonelly llacrallrcd and vcry ll,llccour'


    .-|
    I

    Zonc 2: brcccletcd argLlllter lerr rl'llcQou!, oscallolally nlncraltscd" I

    I.oac 3; brcocleted arglllltc and dlkc roct. ltot vcry rlllccourr tnrt ebunilent 'a
    llncraltratlon. ;

    Zoac 'l: Pockcte of ahalcopyrltc ulncrallratlon'

    ,II

    *
    281

    chalcopyrite containing inclusions of ffskeletal flagellate


    (exsolution?) sphaleri.tei zoned pyrite; nackinawlte
    (cubanite?) oecurs as fine skeletal lncluslons, tiny pri-sns,
    f lanes and thread.srr . , . . .. . .l rrpyrrhotite occurs as coarser
    anhedral inclusionstf (t'iiegel , 1978 p565). ltrolframite was
    rrtentativelyrr identified in altered greywacke contal.ning fine
    chal.copyrite d.i sseninations .

    Samples examined by the writer consisted predominantly


    of chalcopyrite with ninor pyrite (av. 0.5nn, max. 0.?nm),
    sphalerite (nax. 0.3nn) and pyrrh,otite (nax. 0.5nn). Small
    (nax. 50 nicronetres) inclusions of argentian pentlandite
    (i'Ieigelrs mackinawlte cubanj.te?) and rare galena occur in
    tha chalcopyrlte. Sphalerite, pyrite and pyrrhotite were not
    in conplete equilibriuu as denonstrated by the iron content
    of sphalerite (Appendix V).

    Supergene Mineralogy
    The walls of the chamber (Fig. I-A-2) and the cliffs of
    the headland at the outerop of nineralisation are stained
    with malachite, azurite and lirnonlte (goethite). In polished
    section, eovellite replaces chalcopyrite, whereas goethite
    replaces pyrlte.

    The Needles
    Weigel (lgl9) srentioned several sulphide assenblages
    occurrlng in the Needles area either ilsseninated. in the wall
    rocks adjacent to altered pebble and brecej.a dikes or sithin
    the dikes cementing the pebbles or breceia fragrnents. He
    suggested, a paragenetlc sequence of: bornite * chaleopyrite
    + rutile followed by bornite + ehalcopyrite * sphalerlte +
    galena + Ag-Ge-Se sulphosalts + rutile. The gangue nineral
    is quartz.
    FLUID INCLUSIO}IS
    Merchant (in lleigel, 19?8 p515) deternined filling temp-
    eratures betr.reen 260 and llaoC and salinities of tr.5 - 9.5
    Be. wt. I ltaCl for two phase prinary and secondary incluslons
    282

    Secpndary lnclusions

    filling TernVaralurd 'C 5abnity cq.wf /, l,laCl

    9inglo valucg: tr

    Efgure I-A-5;Ilistogranrs of frlling tenperatures and aplnrent saL:lnLtLes


    for prd-mary and secordary inc}.rsions in quartz (sanple 13965) l}on
    the nlneralised breccla dike. ftre indirirldrral neasurenerrts are
    Iisted in rrppendfur III.
    283

    il quartz fron Miners Head. In contrastr vu3 quartz crystals


    colrected by the srj.ter from the nineralisation beside the
    shaft 1n the chamber, have filling tenperatures of prinary
    inclusions between 365 and Lazoc (Fig. r-A-5), with a peak in
    the 3gO to /+0OoC range. Freezing tenperature results group
    1n two narrohr rangesi -2.7 to -2.8oC and -10.4 to -10.?oC
    indieating salj.nities of around lr.5 and 11r.5 g. ut. $ Iia0l
    respectively.

    Assuning a depth of mi,neratrisati.ou of approxinately 1.J


    - 2 kn, and a lithostatic to partly hydrostatic pressure regine,
    a total pressure of 400 bars is indicated. At thls pressure
    the pressure salinity correction which nust be add.ed to
    filling tenperatrres of 395oC is approxlnately 3OoC for a 101
    NaCl solution or 25oe for a 15l NaCl solutlon. Therefore a
    tenperature of trZSoC is assigned to the Miners Head. nineralisa-
    tion.

    SIILPHUR ISOTOPES

    6345 values of chaleopyrite and pyrite are presented. in


    Tabre 9-1. Two cp - py pairs were analysed. Their fraction-
    ations of 0.1 per mil and 0.4 per ni1 suggest disequilibriun
    because of the unrealistically high tenperatuTes indicated.

    DEPTH OF MINERALISATION

    There is no positive evldence to.indicate the depth at


    which nj.neralisati.on oecuned at Mluers Head and the Needles,
    however conparison wlth other d.eposits of a sfuilar type
    suggests that nj.neralisation oecurred, at clepths greater thaa
    1 kur possibly greater than 2 kn. A depth between 1.j and 2 km
    is used here.
    THERMOCHEMISTRY

    The geochernical environnent of the quartz, chalcopyrite,


    pyrlte, sphalerite and pyrrhotite mlnerallsation at Miners
    Head is illustrated in Fig. I-A-6.
    The envj.ronnent is linited by the preseace of pyrite,
    28t,

    -2
    -4
    -o
    N
    rtl -a
    r.h ,\
    -p
    s
    J -t2
    PYRRT{oTITE
    ,v

    -|+ I{EMAIllE

    -E

    Log f}z

    Flgurc I-l-6: fS, vcrrur f02 illagrar rt 1,25oC rborr!.ag thc gcgahclleel cnvlron-
    ncntr for (l)s ltlacrr Bcad quartz-.chalcopyrltr-pyrttc-pynhotltc-aphalarl,tc-
    argcotl.an pcntlandttc rtncrsllgatlonr and (B) thc lfecdlra cha1'copyrlte l
    bornltc llncrallgrtloa. 49r.0.511 pH.J.5t Log.fS2 frol tphalcrl.tc colpo-
    ,rlttoar (lttacru Ecad only) .. -6?2t anit log f52 frol pyrrhotltc corporltlonr
    (Hlncre f,ceil only) . -6.6. Dctallr of eonrtruatl,oa arr glvcn la Appcndk V.
    285

    chalcopyrite and pymhotite but absence of bornj.te, nagnetlte


    and henatlte. fS2 is defined by the pyrlte/pyrrhotlte
    boundary (1og fSe = 6.t) and. the FeS content of sphalerlte
    (fog f$e = -6.2).

    Contours of log n lS in the HrS region, eonstructed for


    a pH of 5.5, indicate that 1og z 4S lras greatar than -2, or
    nagnetite would be the stable iron phase rather than pyrlte
    and pyrrhotite. Becaugs 1og n{S values greater than -1 are
    generally cousidered uulikely for hydrothernal deposi.ts (Barnes
    & Czananske, 1967; Ohnoto, 1972) a value of -1.3 (0.05n) ts
    chogen.

    At log fS2 = -6.3 and log z {S = -1.3, 1og fOa is flxed


    at approxinately -28,0. Fig. I-A-7 indlcates that uader
    these condltlons HaS predoninates over SOa in solution, the
    eoncentratlon of the latter probably being neglLgible.

    The probable environnent of quartz, chalcopyrite and


    bornite rnineralisati.on of the Need.les 1s also shown in
    Figs I-A-6 and I-A-7. The presence of bornlte requires a
    much higher sulphur fugacity than present during the Miaers
    Eead ninerallsation and also indleates a bigher eoncentration
    of SOa ln the hyd.rothernal fluid,. (Fle. I-A-7) althougig EaS
    stlll predoninates over S02.
    CENESIS I
    The igneous and hydrothernal breccfui d,ikes. and rf stockn
    at the northern end, of Great Barrier Island are sinilar to
    features typically found above hypabyssal plutons and, they
    xoay therefore indicate the presence of larger igneous bodies
    at depth. The quartz diorlte porphyry cenEnted argtllite
    brecela nstockn at Miners Head tray represent the apex of such
    an iatrusive.

    The sequence at l,liners Head. began


    with the i-ntrugLon of
    a pluton and stoping of the roof rocksto forrn the breccla
    pipel Intrusion of porphyry dikes into the surroundlng
    285

    -t5

    oc\l -20

    _E-
    4'

    -r0

    -r5
    4N 5m 6N 700900
    Tevnpa.rafure, ('C)

    Flgure I-A-?l foa vereue teoperature dlagren showlng the proposed geochenlcal'
    envlronnents of (A); lllaerg llead guertz-chalcopyrlte-pyrtte-pyrrhotlte-
    ephalerlte-argentlan pentlaudlte nlnerallgatlon and (B) the Nesillea
    cbalcopyrlt,e * bornlte nlnerallsatton. The base dlagrau' fron Flg. 4 of
    Burahau & Ohooto (1980)r shovs the stablltty ftelile of pertlnent iron
    bearing ulneral asaenblages at 1 kbar, ancl th SO2/ltSOj and HSoj/HaS
    boundarLes for unlt actlvlty ratLos at pB = 4.
    287

    argillite occurred d,uring this phase or later, acconpanying


    soridificatlon of the pluton. Lastly, the nagnatic aqueous
    phase, forned by retrograde boiling (c.f. Phillips, 1973i
    Burnhan, 1979), was expelled explosively fron the solidifying
    pluton to forn the hydrothernal breccia dlkes, The copper
    nineralisation was probably forned in the zone of nj-xing of
    the nagnatic hydrothernal fLuid with neteoric water (ttre
    noderate salinity of the fluid inclusions suggests that the
    hyd.rothernal fluid was not purely nagnatic).

    REFERENCES A}ID BIBTIOGRAPHY

    BARTBUM, J.A. 1921


    dTAUVERCI{E, P} 197lra
    GREGG, R.C.; PETRfE, J.l.l. ! CARLSOI{; J.R. t 0rCONNOR, A.P. 1970
    HENDERSON, J. 1931
    1939
    IIUTToN, F.W. 1 859
    PARK, J. 1897
    RABoNE, S.D.C. 197lb
    TIIOMPSON, B.N. 1 960
    I{IEGEL, D.A. 19783 see pp 530 537, 559 568 and. 571-577
    WILLIAMS, G.J. 1971r: see p176
    288

    I-B
    TE AHUI,IATA

    IIITRODUCTION

    The epi.thernal Ag - Au veins of the Te Ahuuata region


    of Great Barrier Island (Fig. I-B-1) l,rere mined predominan.tly
    between '|'892 and 1908, producing 1.3 nillion grans (lr1 ,61*0
    ounces) of bullion fron 17330 tonnes of quartz (Downey, 1935).
    I'lost of the prod.uction was fron Lees Reef .

    Consoli.dated Silver I'tining Co. prospected. the area in


    the late 1960ts to the early 1970rs (Hancock, 1970i Consilver,
    1973; drAuvergne, 197t+a, 197lrb, exeavated. an unknown quantity
    of mineralised quartz fron one of the deposits (Iona Quarry)
    and transported it to their treatnent plant at l,laratoto.
    Because of the short period of this operation it is assuned -
    that the ninerallsatlon proved to .be of too 1ow grade for
    profitable nining. During this tine the geology and nj-nera-
    llsation of the deposlts were described by Ransay ('lgll) and
    Rarnsay & Kobe (1971).

    The area was reinvestigated by AM0C0 and Ereeg (19S1)


    and in 1980 Ai,l0CO drilled three d.ianond dril1 holes fron the
    top of the plateau at Te Ahunata. The holes passed. through
    nainly l,lhitianga Group rocks but. tvo penetrated. the under-
    lying Coronandel Group and.esites.
    GEOLOGI

    Three rock types outcrop in the area (Fig. I-B-1 ). A


    poorly bedded sequence of Coronandel Group andesite lava flows
    and pyroclastics (in a ratio of 2:1) is intruded by a quartz
    diorite porphyry terned the 0rv111e Quartz Porphyrite by
    Ransay & Kobe (19'llr). These authors considered that the
    latter formatj.on was a correlative of the Kai-iti Porplryrites
    at the northern end of the Coromandel Peninsula. The
    andesites and quartz diorite porphyry are unconfornably over-
    lain by the Ahunata Sinter Fornati.on (Ramsay & Kobe, 1971r);
    a 100 23On thick (Ransay & Kobe, 1971r; and Erceg, 1981
    respectively) rnassively bedcled sequence of sillceous sinter,
    289

    7 #iwrkt Rccfs .
    ' ,r-t
    /f t
    \ \ t t-i\-rari -'/ '
    ATe. P&vvnata lrig
    \ Vain
    FauJl
    --
    wJ Ofryu
    I 97695 Scdon
    T ooJl Dianr'a'rdrDr\tl O lO Urtr
    4
    ;, GR,EAT BARRISR

    TE AHUMATA AREA

    tr Alluviw,n

    E Unditletwiiatcd rhyolilc rocVs


    E )rocta*ic llow dcpoAts WHITIANGA GROUP
    E Ucinnly volcanogeric Scdincrlrs ] o**n o srNrER
    FoRMAlloN
    m Ltndilfarcvtiatcd J
    m OROI/ILLE OUARTZ PORPI{YRIIE
    COROMANDEL GROUP
    K Andeite

    m Gralwa&e su\tc ror;Ug MANAIA HILL 6ROUP

    OF TE AHUMATA AR,EA I
    U

    ;
    s

    Iit
    E
    U
    E

    Flgure I-B-1: Geologlcal uap (top left) and crosa-aectlon (bottou) of the Te
    lhunate area, Great Berrler Ieland (top rlght). Detalled nlne plans and
    locattona nere glven by Rausay (19?1). (ttape conplled fron fhorpson, 1960;
    Rauaay I Xobe, 19?l; Erccg, 1981, Cross-sectlon frou Erceq, 1981.)
    __
    290

    rhyolite pyroclastics and carbonaceous shales. Ransay &


    Kobe consi.dered that the Ahunata Sinter Forma.tion was d.e-
    posited in a lake during the Pliocene Pleistocerre.

    HYDROTHERMAL ATTERATION

    Dreeg ( 1 981 ) described the hydrothernal alteration


    nj.neraL assenblage of the Ahunata Sinter Formation as:
    quartz, kaolinite, sericite (itt:.te and interlayered illite
    nontnorillonite) metahalloysj.te, siderite and a single
    occurrence of adularia. The alteration may therefore be
    classifled as lnternediate argilIic. He considered that
    there was originally a zonal patteru of alteratlon around
    fluid channelways consi.sting of an inner adularia/ittlte
    zon, a central interlayered illite nontnorj.Ilonite zo\e
    and an outer Ca-nontnorillonlte zone. However, this was later
    overprinted by nacid oxidati-ve leachingn producing quartz and
    kaolinite,

    Ransay & Kobe (1971r) studied the hydrothernal alteration


    of the underlying andesites and quartz diorite porphyry. They
    recognised a zonal pattern of hydrothernal alteration around
    the areas of ninerallsation. Propylitic alteration (chlorite,
    sericite, carbonate, and pyrite) is present as initlal or
    fringe alterati.on, interuedlate argillic alteratLon (quartz,
    interlayered illite nontmorillonlte, kaolinite and rare
    non-expanding chlorite and pyrite) occurs closer to the veins
    and in the nore porous rocks, whereas advaneed. argillic aliera-
    tion (kaolinite) and silicification are characteristic of
    fissures and vei-ning.

    MINERALISATION
    Eplthernal nineralisation occurs in three areas; Barrier
    Reefs, fona and Sunbean (Fig. I-B-1 ), Ransay (lqZl ) and
    Ransay & Kobe (1971r) studtied Ag - Au and base rnetal. nlnera-
    lisation in quartz veins of all three areas, whereas Erceg
    (tg8t ) d,escribed Ag - Au nineralisation fron a quartz veln
    exposed at the surface in the lona area and a base net6,1
    ninerallsed fault breccia intersected, ia one of the Al'10C0
    drlll holes ('lZg - ltrt*a in DDH 2).

    The veins and nj.neralised breccia stud.ied by these authors


    291

    Quartz

    lAarcasile
    ?yrrhdlilc
    Pyritc
    CMcopYritc
    SgFnlorilc
    Galq,na
    let"raihcdritc
    Falvrifiv'itc
    Mtararqyr\fc

    5ilvcv
    Sulpho:r.lts

    Acqirlile
    5tibnilc

    Kaolinitc
    tiva 9ilwr

    Kcrmcslfd
    Rcalqar
    Orpimont

    Flgurc f-B-2t Paragcncttc rcqucncc of ulncralo at Te Ahuneta. (Conplled


    Rarrryr 19?'tt Raraay I f,obcl 19?ll Erecg, 19811 thla atudy.)
    292

    occur in andesite but Ramsay & Kobe (1971.) noted that some
    extend. up into the overlying Ahunata Sinter Fornation.

    The paragenesis (Fig. I-B-2) was conpiled frou Ransay


    (lgll), Ransay & Kobe (19-7lr), Erceg (tgst) and the writers
    or'rn field observations. A base netal stage (Stage 1), pre-
    doninantly consisting of pyrite and nareasite, is foLlowed
    by a silver sulphosalt (Stage 2a) or a stibnite (Stage 2b)
    stage. The exact tine relati,oaship of the stases 2a and 2b
    is not clear because they are not found together, but they
    are arbitarily placed. in this order. The silver sulphosalts
    of Staga 2a are doninated by pyrargyrite although proustite,
    polybasite (-pearceite), seleniferous argyrodite, aguilarite
    and. naunannlte also occur. The stibnite stage (Stage 2b) is
    best developed. in the Barrier Reefs region where stibnite
    occurs in quartz and kaolinite gangue, either solitary in
    veins and vugs or with other sulphides in veins.

    Quartz is nalnly chalced.onic in the Iona region (Fig. lr-lr)


    but cornonly finely crystalline in the Sunbeam and Barrier
    Reefs reqions. Al.so found in the latter regions are
    epimorphous quartz on calcite and. quartz pseudouorphs after
    caLcite. Rarasay (lgl't) suggested that these features in-
    d.icated an early stage of calcit.e d.eposition followed by
    quartz, dissolution of calcj.te (hydrothernal leaching) and
    fi.nally, d.eposition of the base and precj.ous netal nineralisa-
    tlon with quartz. '.

    FLUID II{CIUSIOI{S
    Both the writer and Ereeg (tggt) studied fluid inclusions
    in sanples of quartz fron ?e Ahumata. Erceg (1981) studied
    indlvidual sanples fron Barrier Reefs, Iona and Sunbean
    areas, whereas the wrlter studied one sample from the Barrier
    Reefsarea, and two from the Sunbean (Fig. I-B-1 ). The
    paragenetic positions of the uriters saurples are shown in
    Fig. I-B-2.
    The fluid incluslons are two phase' liquid. plus vapour,
    293

    lco 2& 220 240 2@ 2AO 0t2


    r-'-'r"--l

    17152

    t??r7

    t7954

    tEttrl

    tq 8@ 220 ?& 2@ 2gO ot2


    oC
    Fiffrhg \urry<rature 5alinifV
    cq.wl il NaCl
    5'hqle valves: Er Et.

    Flggrc I-B-Xr Eietogreur of ftlllng terpcraturca and apparcnt sellaltlor for


    prlnary fluld lnclualonr Ln quartz aarpleel 13952 cnd 13953, Stage 'l
    Sunbear Roglon; 1395L, Stage 2b Barrler Reefa Reglon. The lndlvldual
    lcasurelcntc arr ltatcal ln lppcadlr III.
    29lt

    nornal types with no evidence of boiling. Ereeg (1981)


    d.eternined filling tenperatures pred.oninantly i-n the range
    of 200 - 23OoC, whereas the writers results (Fig. I-B-3)
    indicate tenperatures generally 1O to 20oC higher, partly
    due to dlfferent paragenetic posi-tj.ons of sone sanples.

    The uriters sarnples fron the Sunbean area have apparent


    salinities between aporoxinately 0.5 and 2 eq. Irt. 6 $aC1,
    whereas Ereeg neasured anoualously high apparent salinities
    (one result of approxinately 8 Be. wt. f ltacl, uhereas the
    rest were between 2.5 and l+.1 Bg. wt. fi tlaCt) in sanples
    fron the Barri.er Reefs and rona areas. Ercegl s results are
    consid.ered to be in error.

    The filling tenperatures require the atlditlon of a


    pressure salinity correction whlch, consi.derlng the shall-ow
    leve1 of nineralisation (see later), is probably less than
    5oC. Therefore, based on ny filling tenperature results,
    the average depositional teoperature for Stage 1 is conSidered
    to be 24OoC, whereas Stage 2b fornned around. Z3OoC. Two of
    Ercegf s samples i-ndicate that Stage 2a nineralisation occurred
    at 22ooc.
    SULPHUR ISOTOPES

    t34S values of pyrite, chaleopyrite and. stibnite


    sanples are listed in Table 9-1. They range fron -0.2 per
    rnil (stibnite) to +1 .3 per ni1 (pyrite).
    DEPTH 0F MII'IERA.LISATION

    The Ahuilata Sinter Fornation was considered by Ransay &


    I(obe (1971r) to be a lake deposlt and the top of the fornation
    tras regarded by then as being equal to the forner land
    surface at the tine of mineralisation. The depth reconstroc-
    tion illustrated in Fig. I-B-/r u6es a surface datun 150n above
    Te Ahumata Trig and assunes a value of 230n for the ori.ginal
    thickness of the Ahumata Sinter Fornation (c.f. Fig. I-B-1
    and Erceg, 1 981 ).
    :295

    Dhr.llnota lrrq
    -lq (Wn &6,n sd lcvc\

    g3m dt
    g -
    F
    ||r mn .actit
    - l;Nr;A

    z gd/rt

    -sfim
    -1;976
    611ft
    I'T, '**,
    =19;; 41ft
    r1iia adtt Bgrrria;r Rccfg
    - A.8n adtl
    -

    Ftgure f-8qlllltrgrqla?le fcpirs.s'olt0etlon ot tba ilcBth rclati,oanr at ths ttrc


    of lLncrel!,saftol,r for tha To Ahuuata deporlt. fhe porttLou of tbc turfaes
    detoo 1r baccrl on r! rsrondd thlslcasrs of 230n for t.lra Ahuuata Strn!-er

    1:":t:":-(:"'
    u'T:::-Y:" "Y,t:::ll: ...-+F
    296

    of evidence for boillng of the hydrothermal


    The absence
    flulds in the fluid i.nclusions investigated by the wrlter
    and Erceg (tget) is consistent with the reconstructlon
    (hydrostatic pressure would. a1low boiling to naxinun depths
    of 25Qn at 22OoC and 37en at Z4,OoCi Haas , 1gT1).

    TIIER,}{ OC iiE i,I I S TRY

    Introduction
    Three nineralisations are nodelled: stage 1 base netal,
    stage 2a silver gold and stage 2b stibnite. Table r-B-1
    Llsts several paraneters of these uinerarisati.ons.

    The descriptions of hydrothernar alteration by Ransay


    (1971)' Ransay & Kobe (197t) and Erceg (tgat) tnoieate that
    the early fluids (Stage 1 ) r.rere in equilibriun with r.rall rock
    assenbrages containing serieite and possibly adularia, but
    that late fluids (Stage 2b) were in equilibrium with kaolinite.
    Staee 1

    log fsa versus pil diagran for stage 1 base netal


    The
    mineralisati-on (r:.g. r-B-5) was constructed for a total
    surphur in solution eoneentration of 0.005,n (log n {s = -2.3).
    The nJ.neralogy (Fig. I-B-2) limits the geochemieal environment
    to the pyrite plus chalcopyrite stability field. Log fsz
    values around. -12.4 are indicated by the iron content of
    sphalerites and therefore contours of rog fs, for values of
    -12 and -13 are shown in Fig. I-B-5. A pH near that of the
    sericite/K-teldspar bound,ary (6.1 ) llnits 1og fOe between
    approxiuately -39 and -40 as shown by the shaded area in
    Fig. r-B-5- The general value of +1 .j for 1og fcoz i.s pre-
    cluded. and a value around 0 seens nore appropriate. sulphur
    was present in sorutlon predourinantly 1n reduced forn.

    Staqe 2a

    stage 2a silver - gold niueralisatlon plots in the pyrite


    plus chalcopyrite field of the f0, versus pH diagran (Fig.
    I-8-6) constructed for a total sulphur in solution concentra-
    297

    TABLE _I-B-Ir Gsnera]' thernschcnlcel pEfaqeters


    for the dapoaltlonal onvlronnent.s
    of the epltberual veLn ulnetal,Lsa-
    tl,oag at !e Ahuuata.

    :Stagc I Stagc 2a 9tage 2b Bqfercaca


    (baso u:stal) (eu-lg) (stibutte)
    Tenpercturu oc 2,1,o 220 23A Table Y-l
    Tnue lontG atraugth 0.1 5 0.r t 0,15 I l!

    Sel1nl.ty (rlaOtr aq.) 0.1? 0.1,7 r it


    '0.1?
    r[+ (rsoq toup.) 0t02t 0,020 0.0t2 r t!
    PtrI 6.0 6.o 4.9 ree te*t
    pH of kaollalte/
    s;srlclte b:ouadaty &.7 &.8 *r9 Tatle T-l
    pH of, aerlcltc/f,-
    6.1 6.2 6.2 t l!
    foldspar botradary
    !ota1 S (Log ll{8} .2.3 '3.0 -3.0 ree text
    Lsg f8a (afhalrl+e
    -12.1r Teble'V-41
    oonp. )
    Log /$2 (ulac{rur -'t2.9 ts
    coipr ) -79r5 leUlc 1i-68
    Log fga -lQto-{O -t0to-{1 . ! -t8to-&1 flguner c.tteil
    (Frcl-ts-51 (rugr-r-6; (3!.eI-E-8)
    nog Jcoz +1.5 +1 .5 +tf t Table V-l
    298

    -70

    -31 i u-raaspr
    I
    '72
    Ituunrne
    -tt
    -x
    -t
    N\i- I
    T

    I
    I

    -)L
    o -n
    -?s
    J Lmfcoz !
    -r9
    -&
    .41

    -42
    _4t NRRHOTffE ;

    -&i ,
    Pll'

    Flgure I-g-5, f02 verrur pH dlagreu at 24OoC ahovlng the gcochenlcal envlrou-
    lent (shaded) of Stage 1 quarts + pyrltc i norcaslte i chalcopyrltc !
    ephalerlte ! galena ! tetrahedrlte ulnerall,aatlon ln vetna of the To thuuata
    arsa. (see Table I-B-1 for relevant tbornocheolcal peraneters cud Appendlx
    V for rethoda of constructlon.)
    299

    -tl
    -?2

    -,,
    -*
    -19

    -ro
    c{
    o -n
    .+.

    r
    J
    -rs
    -m
    CHAITOP{RITE

    PYR,ITE
    -&
    -41
    :,r'-9#S- |
    -42

    -4,
    -4 PYRR,HOTITE

    PH

    Flgurc I-Bi6r fO, veraua plt illegrao at 220oC rhovlng thc geocheolcal cnvlron-
    lcnt (shadctt) of Stagc 2a guartz + pyrlte + chalaopyrLte + allvor eulphooalta
    I elcctrun ul.ncrallratl.on ln velng of the Te Ahuuata area. (Sae Table I-B-l
    for relcvant thernoehealcal perauetere and Appendlx V for nethode of con-
    gtruetlon. )
    300

    tion of nAS = -3). Values of log fS, between


    0.00112 (1og
    -12.9 and -13.5 are lndicated by the nole fraction of sj.lver
    in electrun analyseri by Ransay (1971) and Erceg (t9At),
    confining the nineralisatlon to the redueed sulphur species
    field of Fig. I-8-6 in the absence of magnetite and henatite,
    Like the other stages of nineralisation at Te Ahunata, low
    C0, fugacities are indicated, probably around log fC02 =
    0. Sulphur was present in solution predomlnantly i.n reduced
    forn.

    Stase 2b
    fS, versus f0, diagran used to mod,el the stibnite
    The
    nineralisation (Fig. I-B-7) is sinilar to Fig. 55 of Ransay
    (1971) but much lower values of fS, and fO, are consld,ered
    here for the mineraliaation.

    The ni.neralj.sati.on occupies the area to the left of the


    stibnite/Sbzs2o boundary in the pyrlte plus chalcopyrite
    field of Fig. I-B-7. The presence of ninor arsenopyrite,
    reported by Ransayr linits fS, to values below the
    arsenopyrite/pyrite + arsenic boundary at 1og fSe = -13.3
    when arsenopyrite 1s present.

    0n the fOa versus pH diagras (Fig. I-B-8) stibnite +


    Pyrite + arsenopyrite rniueralisation occupies the lower end
    of the shaded area and. indicates that HrS was the predoninant
    sulphur species in solution. Wid.er rdnges of fluld conpositlon
    in terns of fS, and f0, (up to the oxldised./reduced S species
    boundary ln Fig. I-B-8) are possible for stlbnite + pyrLte,
    without arsenopyrite, nlneralisati.on but a fluid containlng
    sulphate ) sulphide is preclud.ed by the Sb2S20 field and
    posslbly also by the absence of barite (Fig. I-B-8).

    The general log fCOa value of *1.5 is preeluded. and a


    value of around 0 is required to shift the graphite/CO,
    boundary below the shad.ed area and. 1og fC02 valueg possi.bly
    as low as -2 nay be required for arsenopyrite + COZ stability
    (c.f. Fig. I-B-?).
    301

    GI
    r.l.i
    rYRffE I

    (r
    o
    --+
    }IEMATITE

    Log f oz

    Plgure I-B-?s fS, versua fO, dlagrau at 230oC chorlng the geochcolcal envtron-
    nent (ltne of crosses) oi st"ge 2b quartz + etlbnlte ! kaollnltg ! pyrtte
    ! uarcaait" 3 .t""nopyrlte nlnerallsatlon ln vetna of the Te Ahuorata area.
    (See Table I-B-1 for relevant thernocheulcal paranetera and Appendlr V for
    rcthods of constructlon. )
    302

    -n
    -tl iK-feld
    I
    I
    -?2 i
    II
    -,, IHEMAT
    I
    -* :
    -r5
    i:s I
    I
    :

    (\f
    o
    ({^ -n

    J
    s -r8
    I

    -19

    -41

    -42
    -4'
    -4

    PH'

    Flgure I-B-8; foa vcraur pH dlagran at 23OoC rhoulng the geocheo!.ccl cavlron-
    rent (ahaded) of Stage 2b nlaerall,rattol. r8a2t.0.0001. (See Tablc I-8-1
    for other relevant thsrnochcllcal paraoetors aad Appendtr V for lethoda of
    oone truc tt on. )
    3a3

    GE}IESIS

    The epi.thernal vein deposits of Te Ahunata were forned


    in a geothernal systeu generated by rhyolitic volcanisn i.n
    the Pliocene - Pleistocene.
    '1. t
    5'*Sr,S of the hydrothernal fluid was probably near 0
    per nil because sulphur was present in solution predoninantly
    in red.uced form (fres. I-B-5, I-8-6 and I-B-8) and S3Lt r"
    uay therefore be represented by S3LS of the sulphide ninerals
    (e.g. t34scp = +0.'7 per ni1). The sulphur was probably of
    nagnatic origin.

    The nineral paragenesis (Fig. I-B-2) resul.ted fron general


    deereases in fluid tenperature and pH, Early stage nineral
    deposition probably oecurred as a result of fluid - walI rock
    reactlons and their effects on the fluld chemistry (e.g. fCO2
    and pH), ho',rever nixing ftith near surface water, and later
    acidie conditions, are thought to be responsible for the
    subsequent stages, All stages are charaeterised by
    antlmoniferous rni.nerals (Stage 1: niargyrite and tetrahedrite-
    freibergite; Stage Zaz pyrargyrite and polybasite; Stage Zez
    stibnite) and may lnd.icate a relatively high concentration of
    antj.nony in soluti-on. Sinilarly, seleniferous and selenide
    ninerals of Stage 2a (aguilarite, seleniferous argyroilite and
    naumannite) suggest a relatively. high * Se/ {S ratio because
    of the low dissolved sulphate/dissolved sulphide ratlo (see
    Appendlx V).
    REFERENCES ANq BIBTIOGRAPryY

    BARTRUI,I, J.A. 1921 THoMPSoU, B.lI. 1950


    CONSILVER 1973 I,IILLIAI.{S, G.J . 1971+: see pp125,
    df AuvnRGItrE, P. 197lra l*22 lr2l+ and, t 28 lr29
    197 |rb

    Doi,iNEY, J.F. '1935: see pp 262 - 25[ and, 289


    ERCEG, M.M, 1 981
    HANCoCK, P.M. 1970
    HAITER, I.B. 1951r
    H0WIE, A.S. 1 899

    RAMSAI, W.R.H. 1 971


    RAMSAI, W.R.H. t KoBE, H.W. 197 lr
    30t,

    r-c

    }IORTHERN COLVILTE PENITISULA

    II{TRODUCTIOI,I

    Skinner (1967) drew attention to the posslbility of a


    porphyry copper orebody bei-ng associated with the Paritu
    Pluton at the northern enC of the Coronand,el Peninsula.
    subsequently, i.{itsui !'lining and sneltiug co. Ltd carrj.tid out
    a geochenical exploratlon survey and in ljlO dianond. drilled
    three holes (hole 'l = 150n, hole 2 = 5?n and hole 3 = 150m;
    Aklyana, 1970) in a zone of Cu anonalous soils (ZSO - 1 ?00
    ppn Cu compared to background values of 20 - lro pptr) in the
    0ngohi Stream area (Fig. I-C-1). The reeovered. core con-
    tained disseninated pyrlte and chalcopyrite nineralisatlon,
    averaring 0.16/" Cu (naxinun analysis of O.)3?fr Cu) in hole
    llo. 1 .

    In joint venture by Southern Cross i'{inerals


    1973 a
    Exploration Ltd and Fleteher l,{ining and Exploration Co Ltd
    (Erown & Hancockrl973) discovered. another zone of cu anonalous
    soils, in Stony Bay Creek, however this area has not been
    d.rilled.

    In adCition to porphyry style nineralisation, several


    base metaL quartz veius oceur associ.ated with the intrusive
    rocks. Also, snaI1 silver - gold veins in Hope Strean,
    Okatutahi streau (nva l,line) and rangiaro strean were nined
    in the late 1800rs but prodused only a few thousand grans of
    gold and silver.

    GEOLOGY

    The geology of the Colville Penlnsula uas d.eseribed by


    Fraser & Adans (1907) and Sklnner (1962, 1967, 1976), whereas
    the Paritu Pluton was specifically studied. by Blaek (1967)
    and Skinner (1975a). A geological map conpiled fron these
    sources is presented ln Fig. I-C-1.
    305

    L
    o
    E
    E
    .!l
    u,
    t E
    tt o
    l.
    C{
    nt
    a,
    .-{
    o
    E
    o
    o
    >t
    d
    A
    t
    o
    tr
    g
    o
    A.
    o
    A
    >.n
    r{r
    oo\
    c)F
    g.
    !. J'l
    ot)
    EO
    +tO
    lrd
    ort
    2E
    q{.l
    o
    c
    ir
    l't
    h!.
    hoo
    Ol.gl
    11
    o
    o
    L'
    \o
    .. ro\
    I
    <J
    F{ t:
    \o
    os
    LF
    bo

    dnoa? l3oNvnoaol JJ
    d
    f:.

    r^
    tJ
    '-2
    dP
    oa=
    t 4.Jo.
    cL
    a
    lu
    10
    a og
    ?'t 9-<
    =H
    +
    io E=
    i+
    a
    E?T
    E;+ an
    8.'s
    tt'
    5 +
    '^q
    - s s
    vt -' = .TE
    i" 6 P=
    6g.Eu
    G'-
    =
    <o.
    S5 h.9
    3g +\
    EF
    tes
    PE I-
    .olt.9
    E
    t
    F
    H8='6
    o=1"*
    P
    G

    ge
    +s
    E"' 'E
    5
    b
    's
    I s-s
    H

    9
    E H [.t
    -6h s E 5
    -l E-9
    &: & EIF ESprg * u$ * $ -U

    =p
    FI:
    z r
    3E
    5
    E
    8
    :l &3
    ftE* i$gFrHr; tr 1s<
    i,P3=d,5ddx F S 9'P
    'LJ
    =H
    FE D mEElllzs= r\ trns \
    306

    The Paritu Pluton is a composite body of quartz di.orite'


    granodiorite and aplite intruding a Jurassic greywacka suite
    of the l,loehau Fornation (l.lanaia Hill Group) and, I'iiocene Port
    Charles Andesi.te (Coronandel Group). Plugs and dikes of
    andesite and dacite porphyry (f<a:.-iti Porphyrites) are also
    found intruding these forrnations and although aany are con-
    tenporaneous with' soile are considered to predate and others'
    postdate the intrusi-on of the pluton. Brown & Hancock (1973)
    nentiou the oeeurrenee of diorite breccia dikes in quartz
    diorite at several locaLities.

    Contacts between the pluton and country rock are


    generally discordant. I.lear contacts with the l'loehau
    Fornation the pluton contains recrystallised xenoliths of
    greywaeke oroducing a narginal tonolite zone. -

    Skinner (1916) descrlbed the Port Cbarles Andesite as


    andesite pyroelastlc and flow rocks wlth rare carbonaceous
    layers but locally abundant petrified. 1ogs. The pyroclastics
    lrere deposited subaerially and subaqueously and consist
    nainLy of iuff to 1apil1i tuff although breccias with a tuff
    to lapilli tuff natrix are also found.

    K - Ar AGE DATA .,
    K - Ar ages of 16 to 17.1 tr.3r. were deternined fron
    biotite and hornblende concentrates of the plutonic rocks
    by Richards et aI (1966).

    I"IETAI{ORPTIISI'I

    Black (lglZ) described Ern isoehenical netanorphlc aureole


    in l4oehau Fornation, deflned up to 900n fron the contaet with
    the pluton by porphyroblastie quartz' orthoclase' albite'
    epidote, biotite, hypersthsne' hornblende' acti.nollte'
    nagnetiter alnandi.ne and tournaline.

    Skinner (1975a) considered that the connon occurrence of


    yellow porphyroblastic epidote in granodiorite fron Sorry
    I'lary Strean resulted fron netanorphisn ind,uced. by lntruslon
    of later quartz diorite.
    307

    DEUTERIC ALTERATIOI{

    i.Iodzicki (lgZO) and Skinner (19?5a) described the


    alteration of hornblende in the plutonic rocks to a
    secondary green fibrous amphibole, uralite. Both authors
    ascrlbe this al-teration to a deuteric phase.

    IIIDROTHERI'IAL ALTERATIOiI

    Propylitic alteration is ubiquitous and has resulted in


    partial and occasionally complete replacenent of hornblend.e
    and uraLite by chlorlte, epidote and. calcite, ninor replace-
    nent of plagioclase by sericite, epidote and eccasionally
    adulari-a, and replacenent of oxi.des by pyrite, leucoxene
    and ninor chalcopyrlte (Wod.zicki, 1970). Skinner (lglSa)
    also recognised secondary albite and sphene as alteration
    produets. Skinner considered that hydrothernal alteration
    r,ras nnly slight ln the quartz diorite but intense in the
    granodiorite.

    Potassic alteration nay be represented by the occurrence


    of second.ary orthoelase replacing plagioclase in sone igneous
    phases of the pluton (c.f . Sklnner, 1g77p3{1) and in druses
    with quartz and later epidote and calcite. Sklnner (1975a)
    attrlbuted the lattep to a pegnatitic phase of the pluton.
    The formation of thin veinlets of tourmali.ne, sone contai-n-
    lng sulphides (c.f. Skinner, 1967), was correlated with the
    plagioclase alteratlon by Skinner (1975a).

    MI}TERALISATIO}I

    Dls senlnated l,!ineralisation


    Sklnner (1967) descri.bed disseninated. chaleopyrj.te,
    pyrlte, volframiter plrrhotite and narcasite in the igneous
    and hornfels rocks of the coastal seetion south of Paritu
    (Fig. I-C-1 ). He consldered that pyrrhotite replaced
    wolfranite and. was itself replaced. by narcasite.
    ' Wodzicki (lglO) d.escribed disseninated pyrite,
    chalcopyrite and nagnetite rnineralisation in drill eores
    308

    fron 0ngohi Strean, I4ost of the nineralisation oceurred in


    a biotite quartz diorite phase of the pluton, found only in
    core of hole i'Io.1. The biotite quartz diorite ls the least
    altered of a suite of rocks in the drilL holes and nearby
    surface exposure, being uneffected by uralitisation and onJ-y
    slightly propylitised.

    Brown & Hancock (1973) note that the natrix of diorite


    breccia dikes in the quartz dLorite contain disseninated.
    pyrite and ehalcopyri.te.

    Vein Mineraliglrtion
    Veinlets connonly oceur infilling joints and shears in
    the i.gneous roeks and surrounding greywacke and contain
    quartz, pyrite and occasionally epidote, chlorite and calcite.
    Veinlets and veins containing sulphides other than pyrite
    occur ll,ess frequently. Known exanples are described. be1ow,
    west to east.

    South Coast.
    !'linor molybdenite, pyrrhotite, narcasi-te, sphalerite,
    chalcopyrite and arsenopyrite nineralisati-on occurs in quartz
    veinlets filling thears and joints in the igneous and hornfels
    rocks along the coast south of Paritu (Fig. I-C-1 ). fn sone
    instances this ni-neralisation 1s assoeiated, with the
    disseninated nineralisati-on described fron the sane area
    (Skinner,1967). ' I

    Sorry l,lary Strean


    Skinner (1967) noted quartz boulders with sulphide
    ninerali.sation in Sorry Mary Strean. The veln outcrop
    (flg. I-C-1 ) was later discovered by Brown & Haneoek (1973)
    and its location noted on their l,lap 1 (S).

    The vein conslsts of a 0,4rn wide zooe of quartz cenented


    wall roek breccia, The host rock and brecci.a fragnents are
    quartz d.iorite of the Paritu PLutonics. Concentratlons of
    quartz veinlets occur near the hanging walI and footwall.
    309

    The latter zone, approxinately 80nn r+id.e, contains nost of


    the sulphid.es. The quartz veinlets, up to 30mn thick,
    surround. brecci.a fragments up to 5Omn in dianeter.

    Pyrite occurs disseminated in the wall rocks and breccia


    fragnent s.

    of quartz, pyrite, sphalerite, chalcopyrite


    T',ro stages
    and galena oceur; the first, fine grained and the second,
    nediun to coarse grained. The latter stage has also grown
    into vugs with quartz crystals up to 1 Onn long with rare
    coatings of sulphides near tbeir bases.

    Textures of the sulphide nineralisation are simple as a


    result of the brecclated nature of the vein. Indivldual
    grains of sulphides occur surrounded by quartz; contacts
    between di.fferent sulphides are rare. Quartz is generally
    euhedral to the sulphides and. sphalerite eharacteristically
    contaj"ns abundant j.nelusions of chalcopyrite, sometimes
    arranged along grain bound.aries or zones.

    Hope Strean
    Fraser & Adans (190?) noted that an east-west striking
    quartz vein in Hope Strean was pgospected. by aditlng in the
    late 1800rs. Although they were unable to view the vein due
    to eollapse of the ad.i.tsr they noted. that blocks of quartz on
    the d.urap ranged i-n size up to 0.6m and. eontaj-ned pyrite,
    galena and sphalerite. A single sarnple assayed. 1dwt. 6 gr.
    Au and g ounees 1/*dwt. 8 gr. Ag per ton (1.9ppn Au and29?ppn
    Ag) '
    Stony Bay Creek
    Skinner (1967) described nineralisation occurrinq ln a
    nurnber of quartz strS-ngers (generally less than 1Onrn but up
    to 1 00nm thick) crosslng a plunge pool in Stony Bay Creek
    (Flg. I-c-1 ). Epidote oceurs as an early phase folLowed by
    galenar chalcopyrite, sphalerj-te and pyrite. The texture of
    the nineralisatiou is sinilar to the Sorry l,tary Stream vein.

    The country rock is greywacke of the Moehau Fornation.


    310

    Doctors Creek
    Brown & Hancock (1973) noted on their l,lap l, the occurrence
    of a quartz vein, containing sulphides, in the western branch
    of Doctors Creek. The vein was relocated by the writer and
    found to be & 1n wide zone of quartz eernented wall rock
    breccia.

    The country rock is a porphyry d.1ke which intrudes


    greywacke of the Moehau tr'ornatlon,

    Sphalerlte, galena, chalcopyrlte aud pyrite (in order of


    abundance) oecur in quartz veinlets up to ?mn thick cementing
    the breccia fragnents (up to 120nn in dianeter). Later
    brecclation of the first stage was followed by further quartz
    deposition with rare sulphides. Vugs lined with quartz
    crystals up to 7nn are conuon in this late stage.

    The texture of the sulphid,e rnineralisatj.on is si.nilar to


    the Sorry Mary Stream veln (e.g. Fig. lr-19),

    Eva Mine
    Downey (1935) noted that the only record.ed production
    fron the Eva l.line in 0katutahl Strean was 15,000 qrans (trll
    ounces) of bullion duriug 188? and 1888. The ninerali.sation
    has not been described.. Skinner (1976) shows the location of
    the nine in Port Charles Andesi,te.

    Tanglaro Strean
    The nineralisation in Tangiaro Streanr also in Port
    Charles Andesite, occurs ln a 1n wide quartz and kaolinite
    cenented, breccia vein strlklng 3250 and dlpping 7Lo to the
    uest (Sklnner 1967). Marcasite, pyri.te and arsenopyrlte
    occur in the central part of the veinr fhereas later pyrite,
    arsenopyrite' tetrahedrite' chalcopyrite' sphalerite and rare
    galena and electrum oeeut in quartz stri.ngers and comby quartz
    between the hanglng waIl and central zone.

    Al-though Fraser & Adans (1907) suggested that acanthite


    uas prbsent it was not ldentified by Ski.nner. fnstead Skinner
    sonsidered that the si.lver occurred in tetrahedrite. Analyses
    ';i ' 't'r'
    311

    24A zbA 280 1ffi ,2A t^A 9W


    i
    0t-T.-]-t-r
    | 2

    l79il
    EI

    lvt97z + 1317?,

    E---- -Jar-
    1 ,,+ r--r-J-l-t
    l l n r r
    24OWWr$ar2oW7@ olz
    Fi I I rnq 1,emp eralure,'C 5alin\tv
    J cq. wt },'NaCt
    ''o
    valueet: r:

    Flggac I-0-2r Blctogreur of fllllng teuBeratur-er sad apptgcat rallrlltlos fsll


    .pr.xoaryflultl!.no[w:Lonrtuqu*rtzfirolthabeeclata1.etrlgh.lii'arej'salr
    Docturo graek (rar.gla f,3-9?1) and So1 f Hory Streer tsarpjtat 1X812 a'qil 13-9?3).
    f.hc tqiivldual reaairflEeata ern llstid tt lypaadt* IfI.
    )12

    of vein naterial were reported by lleKay (1897) as 105 ounces


    to 110 ounces Ag and a trace to 1? dwt. Au per ton (3214 fo
    3367 ppn Ag and ? to 26 ppn Au), whereas a sanple taken by
    Fraser & Adarns assayed onJ-y 19 ounces 1 dwt. 5 gr. Ag and
    22 gr. Au per ton (Sel ppm Ag and, 1.4 ppn Au).

    Supergene Mineralogy
    Covelllte limonite are the predoninant supergene.'
    and
    ninerars found replacing the sulphides in the veins although
    chalcoeite, in additlon to covellite and, llnonite, occurs in
    specinens fron Sory Mary Strean and Sklnner (1967) noted,
    henatite in naterial fron Tangiaro Strean.

    FLIiID II CTUSIONS

    The results of fllIiag and freezing tenperature Eeasur-


    rnents on fluid i.nclusions in vug quartz crystals fron the
    veins in Sorry l{ary Strean and Doetors Creek are presented
    in f ig. I-C-2 and Append.ix III.
    Thefi1l1ng ternperatures, with a 15oC pressure-sallnity
    correction (assuuing a depth of 1 kn and llthostatic partly
    hyd.rostatic pressure), indicate depositlonal tenperatures of
    approxinately ZgOoC for second stage sulphid,es in the Sorry
    Mary strean vein and 31Ooc for post - surphide nineralisation
    quartz in the Doctors Creek veinl Salinitles are 1.2 - 1.7
    and 1.9 g. !rt. fi NaCl respectivellr.
    I

    SULPHUR ISOTOPES

    6345 values of sulphide ninerals fron the veins in


    Sorry i'lary Strean, Doctors Creek and Tangiaro Strean are
    presented in Table 9-1. They range fron +0.4 j (galena) to
    +3.9 (pyrite) per niI.

    Three deposltlonal temperatures for the Sorry Mary


    Strean nineralisation are d.erived fron sp - gn pairs ()ZO,
    3lr} and 3?OoC), *rereas tenperatures fron a py - cp pair
    (32OoC) and a py - gn pair (ZAOoC) are caleulated. for the
    Doctors Creek nj.neralisation in additlon to tro sp gn pairs
    of 350oC aad /r6OoC. The 460oC tenperature seens in error
    319

    TABIIE I-Cr1l Geuerel. theroch.enical paranc.trate for tbedepostrtlonel


    nvjlFonnontr of tha Fari'tu Lco3ttal ag'stl-on porphyryr
    GoPpar rlnsral:ltatLoa and the basc retal quartz vcln
    otnctallratlong Ln Sorrry llary Str,eal' Stony Bay Croo-k
    and Dostors Grcak.

    Porphyry Gopper Pb-En-Gu Bsference


    Ooaatrl Seatlon Vg,Lns

    Tgnlrcraturc oC &5 ?25 taDle V-l


    o.l 2 lf
    Tn'ue toatc. ,rtlength 0,1 9
    'Sa1trn'lty (r$a0t eq'l 1.2 o.tl I

    o..75 on0rl t
    rX*
    pU 5.5 Se te*t
    pX oi kaollntts/acrlclte bE rqdcf,y 1.9 'ti I
    ',''A Tablo V-1
    t
    pttof sarlolte./f,-fclilstrlar boundiry 5.6 5.6
    lotal $ (log n(S) . _1 .3 -2.0 Scc text
    Log fst (aphaX.arita cotp.) .7.9to.9.0 Tablo V-4t
    (eqtraul'atea) -5,.rto!6t.5
    (FLg.f-O-!!
    f,og f,9,e -25.5to-26.5 -1A,7io-92. f,lgure,a
    (Ftg.I-G-l) (rls.I-o-5) elterl
    Log IGo, +t.t +1.5 fable $-1
    ' 311*

    and is rejected on the grounds of possible non-equilibri-un.

    LEAD ISOTOPES
    Gooper & Richards ('lg5g) neasured lead isotope ratios
    in sanples of galena frorn the base netal veins'in Sorry Mary
    Strearn and Stony Bay Creek. Comparison of these values uith
    lead isotope ratios i-n sanples of greyr.racke (Armstrong &
    Cooper, 19?1) and and.esite and rhyolite (Cooper & Ri-chard.s,
    1969) fron other locations in the Coromandel Peninsula
    suggests that the lead. in the galena is affiliated with lead.
    in the greywacke and rhyolite rocks but has a different
    parqntage fron lead in the andesites (c.f. Fig. 5 of
    Roblnson , 197 t*). Cooper & Richards ( 1969) conclude{ that
    lead. in the veins and rhyolite rocks was derlved fron the
    Mesozoic greywacke suite rocks.

    DEPTH OF MINERALTSATION

    Skinner (lgAZ, 1975a:1976) considered that the v6leanic


    rocks intruded by the Paritu Pluton (Port Charles And.esite)
    nay have been only about 1 kn thiek. Black ('tglZ) and
    Skinner (1975, 1976) therefore postulated. that the total
    thickness of rock cover above the pluton at the tlne of
    intrusj-on was slightly less than 1 kn (i.e. approxinately
    900n). Presunably porphyry copper and base metal vein
    nineralisations occurred at sinilar depths although preci-ous
    netal vein mineralisations in Okatutahi Stream (Eva Mine) and
    Tangiaro Stream probably occurred at shallouer levels.

    THER}'IOCHEMISTRT

    Table I-0-1 lists sone paraneters of thg geochenical


    environnents responsible for the'tuo high temperature rsineral
    assenblages nodelJ-ed here (a) the quartzr pyrite, chalcopyrite,
    pyrrhotite, rnarcasite, sphalerite, arsenopyrite, nolybd.enite
    and lrolfranite disseninated. and vein mineralisatlon of the
    Paritu coastal section and (b) the quartzr pyrite, sphalerite,
    galena and chalcopyrite vein rnineralisations-i-n Sorry Mary
    Strean, Stony Bay Creek and Doctors Creek. fS2.versus fOZ
    diagrans for these nineralisations are presented in Figs
    I-C-3 and I-C- /, respectively.
    315

    (\r
    (n NRRHmne:A
    ct-
    a

    ., 4 1+ -t2 -30 -28 -20 -22 -20

    Lq loz

    Flgure I-C-3: fS, versus f0, dlagraa aL t,25o} shorlng the geochenlcal
    env!.ronnent (star) for the dlsseolnated and veln porphyry etyle alnerallsa-
    tlon of the Parltu coastal sectlon. The arros lndlcatee the paragenotte
    sequonce of quartz + pyr!-ta * chalcopyrtte t uolfranlte folloved by
    quartz + pyrrhottte t chaleopyrlte ! uolybttenite ! argenopyrlte !
    sphalerlte. (See Table I-C-1 f6r relEvant tharnocheoical paranetere and
    Appencllx V for detalls of conEtructlon.)
    3'15

    PARITU 725'C

    (\f
    rrt

    (t
    o

    MAGN TtTE

    ^el

    -4? -40 -n -x -% -32 -ro -n -26 -zt -22

    Log f 0z

    F!.gure1-C-lz fS2 vereus fo2 dlagrar at 325oC ohov!.ag the general field of
    atablllty (shaaled) for tbe quarta + pyrtte +. opbalerlte t galena *
    chalcopyrtte ve1n olnersllsatlons ln Sorry Hary Strean, Stoay Bay Creek and
    Doctore Creek, (gee Table f-C-l for relevant tbcrnocheslcal parauetere and
    Appendlr V for nethocls of coustructl'on.)
    317

    -t2
    -7' Kaolf
    -24
    .E
    I{EMATITE
    -20
    -27

    -n
    oN -n .MAGNETITE
    (t -r0
    o
    J
    -rl
    -n
    trft;5-;
    -9
    -t4
    F/RRHcrrftE
    -t,
    -*

    Fl,gure fOa varaua plt itlagrau at 325oC and tS.0.01r a[oulng tbe geo-
    I-C-r,
    eheuloal cnvlronocnt (ahadaat) for the quartz + pyrlte * sphalerlte + galena
    + chalcopyrlte reln nlnerallaatlons ln Sorry Hary Stream, Stony Bay 0reek
    and Dbetors Creek. (Sec Table I-C-l for roloyent thernoeheolcal paranetere
    and lppendlx V for lcthocls of construetton.)
    318

    The sulphur fugacity of the coastal seetion vein


    nineralisation j.s defined by the pyrite - pyrrhotite and
    arsenopyrite - arsenic plus pyrite boundaries 1n Fig. I-q-3.
    A 1og fSZ velue of -6.3, equi.valent to the pyrite
    pyrrhotite boundary, is chosen to represent this mineralisa-
    tion.

    The stability relations of wolframite are discussed. in


    Appendlx V, vrhere it 1s concluded that the Paritu wolfranite
    should plot in the pyrite field near the pyrite pyrrhotite
    nagnetite triple point of Si.g. I-C-3. The diseeninated
    pyrrhotite is later than the rolfraoite and records the
    changing conditions of fS, with a nove i-nto the pyrrhotite
    stabiJ.ity field (represented by the arrow in Fig. I-C-3).

    Assuning a 1og rzr S vaLue of -1.J (c,f. Seetion I-A


    l,liners Head) the sulphur and oxygen fugacitles of the eoastaL
    section nineralisation can be defined as follor,rs:
    Log fS, Log f0,
    Early dissersinated. naineralisation
    wolframite)
    ( -5.5 -25.5
    Late disseminated nineralisation
    pyrrhotite)
    ( -7.0 -27.0
    Vein nineralisation -6.3 -25.0

    The occurrence of sericite and ninor K-feldspar in the


    hydrothernal alteration accoillpanying the base netal vei.n
    deposits in Sorry Mary Strean, Stony Bay Creek and Doctors
    Creak suggests a pH of around. 5.6 (pH of the serleit,e/K-
    feldspar boundary, Table I-C-1 ). Conparison of the log n S
    dontours, constructed at this pH in Fig. I-C-4, with the
    1og fS, values defined by the FeS eontent of sphalerites
    indicates that 1og n {S r,ras approxirnately -2.0. An fOe
    versus pH d.iagrarn for this value of n 1S is presented. in
    Fig. f-C-5. The region of urineral deposition is Ehown by
    the shaded area and suggests that the fluid contained
    dissolved sulphur predonlnantly in red.uced forn.
    319

    GEI{ESIS

    The porphyry nnineralisations of the paritu coastal


    section and in the On3ohi drill holes nay each represent
    different reineralising epJ-sodes.

    The coastal section minerarisation nainly occurs in the


    hornfeLsed rocks of the contact between the unnetanorphosed
    greywacke suite country rocks and the quartz diorite phase
    of the pluton. rt was deposited. fron a hyd.rothernal fluid
    with rel.ati.vely 1ow fS2, f0, and n2Sr possibly in a con-
    veetive qround water systen generated, during the intrusion
    of the maema (c.f. Cathles, 1977).

    rn contrastr the style of nineralisation in the biotite


    quartz diorite phase of the Ongohi dril1 holes is nore typical
    of porphyr;.r copper deposits. rt was probably d.eposited after
    hydraul ic brec ciati.on ( c. f . Phillips , 1973 i Burnhan , 1979 ;
    Burnhan & 0hmoto, 1980) of the biotite quartz d.iorite by a
    nagnatic hydrothermal fluid generated by retroErade boiling
    (c.f . Burnham, 1979) in an und.erlying nagma chanber. The
    chalcopyrite-pyrite-nagnetite mj.neralisation nay have been
    deposited at the site where the nagnatic hydrothernal fluid
    encountered ground water or due to changes in the chenistry
    of the naqnatlc hydrothermal fluid accorilpanying fruid. - wa1l
    rock reacti-ons.

    The vein mi-nerali-sations (e.g. Sgrry l,fary Strean,


    Stony Bay Creek, Doctors CreeE, Okatutaki Strean and
    Tanglaro strean) nay represent concurrent d.epo$its peripheral
    to the porphyry copper mlneralisatj.on or deposits forned at
    a nuch later stage during a different intrusi.ve (-volcanic)
    episod.e. rn either case they were probably deposited from
    fluids consisting predoninantly of rneteorie water. The lead.
    isotope results of cooper & Richards (lg0g) suggest that the
    lead in galena of these veins was derived. fron the greywacke
    sui.te rocks.
    120

    REFERENCES AID BIBLIOCRAPIT

    AKISAMA, S. 19V0
    BATSS, T.E. 1980
    BLAOK, P.!'t. 1967
    197A
    197?
    ER0$IN1 I.R. t IIASOOCK, P,M. '1973
    COOPER, J.A. i RICHARDS, J.R. 1969
    DO-IIIIIEI, J.F. 1935t sge p5l)
    FRASER, G., ADAMS, J,fi. 19O72 see pp 108 aad 109
    RICIIARDS, J.n.t COOPER, J.A.t BLACK, P.M. 1966
    scHoFIELD, J.C. 1967
    $Klxg6p, D.lf.B., 1962
    1E67

    19754
    1976
    THol,tPs0N, B.N. 1966
    IIILLIAI'|S, G.J. 197/': see pp 99, 391 and 392
    uoDzIcKI, A. 1 970
    321

    I-D

    KUAOTUNU

    II,ITRODUCTIOiI

    Two large quartzvelns, the Bald Spur Locle.(also known


    as the Try Fluke) and. the ifaitaia Vei.n' l,rere mined between
    1889 and the 19301 s. l{ines on the Bald Spur Lode
    (principally the 0reat i{ercury' I{apai Vernont and Try Fluke
    liines) produced. 2.2 miI11on grans (Zt ,98J ounces) of bullion
    fron 88r039 tonnes of quartz, whereas the trlaitaia and Mountain
    King t4ines on the ilaitaia Vein prod.uced. only 620,000 grams
    (19,949 ounces) of bull-ion fron 10,789 tonnes,of quartz.
    Production fron other workings in the Kuaotunu area accounted
    for only 109,000 grans (3,50A ounces) of bullion.

    The veins r{ere nined from adits which uith the exeepti-on
    of an upper level of the t'Iaitaia l'line have collapsed or been
    filIed in.

    Parki-nson (tgAO) studied the geology and nineralisation


    of the area i.n association with a geochenical exploration
    progran by Gold l{ines of ilew Zealand Ltd.

    GEOLOGY

    The geology of the Kuaotunu'"t.. has been recently


    napped by Skinner (lg16) and Parkinson (t9eO). A geological
    nap conpiled fron these sources is presented in Fig. I-D-1.

    A large block of Jurassic greywacke suite rocks (l.lanaia


    Hill Group) outcrops in the Kuaotunu area, flanked by ilpper
    lliocene Coronandel Group anclesites: Te Tutu Andesites to the
    west and l4ahiapua Andesite to the south and ea3t. Contenpo-
    raneous Upper I'liocene - Lower Pliocene lacustrine and
    hydrothermal deposits (Black Jack Fornation and i{aitaia
    Sinter respectively) occur oveflying the greywacke east of
    Kuaotunu. Parkinson (tgS0) recommended tbat fiaitaia Siuter
    should be renaned tr'laitaia Silica Deposit because the fornation
    includes silicified voleanic breccia and sed.inents in ad.dition
    to chenical preeipitates.
    322

    T ItahinaVua fu,1

    \\
    I

    7/ ,/

    7!;k;1
    t//

    wffi lrrtrui,r'.t
    Ltlartr.cfrzl

    KERIKERI VOLCANIC GRA)?


    $J rrrencunv ot)Av-,e
    Fl glrcr .tec< FoRMATfoN, WAITEMATA GROUP
    E7 (CFfuiucu^l, Xdivnent>)
    ffiwxrxtx aNrER

    l3l urn,Nrrua ANDE:TrE GROUP

    El tt ruru N.rgE5rrE
    MANAIA I{ILL 6ROUP
    Il-l I (Orcywackc
    MoeL{N.{ FoeMATtoN
    tuite rocks)
    --- Fauli
    ,t Mme,

    Flgure I-D-1: 0eoloqy of the (uaotunu area (after Skinnerr 19761.


    . 323

    HYDR,O Ti{ERi.lAL ALTERA TIOI{


    Parkinson (tgao) identified the following hydrothermal''
    alterati-bn ninerals assoeiated rsith the gold silver
    rnineralisatj-on in the Kuaotunu arear secondary quartz, elays
    (kaolinite','illite, montnorlllonite and interlayered illite..-
    nontnorillonite)', chlorite (ninor abundance), zeolite (rare
    abundanee) and calcite.

    Alteration is nost i.ntense close to the najor quartz


    veins.

    ' The clay nineralogy has a depth related zonal distribution


    with. a progression of the assenblages kaolinite, sericite
    (irrite) t kaorinite, and seri-cite (ittite ) correspo-nding
    to increasing depth.

    other ty$es of alteration have 1oca1J.y restricted


    Two
    occurrenees. A red elay deposit occurs in volcanic breccia
    of re Tutu Andesite in the northern part of l{aitaia Ridge.
    rt is gradati-onal to surrounding quartz, kaolinite i chlorite
    alteration. Parkinson attributed its fornation to localised.
    sulphate alterati-on. Skinner (1968, 1976) noted alunite and
    kaoli-nite associated with plugs df l{aitaia Sinter.

    MINERALISATION

    Gol.d - silver rnineralisation occurs in two widely


    separated, seni parallel., easterly dipping veins, the Bald
    Spur Lode and the l,Iaitaia Vein (ffg. I-D-1). Both veins are
    predoninantly in greyuacke of the Moehau Fornation although
    they extend southward.s into adjacent Mahinapua Andesite
    ( Coronand.el Group) . They each range up to lrn uide sith
    average thicknesses of 0.3m (liaitaia) and greater than 0.8n
    (nafa Spur Lode), and dip steeply.

    Quartz is the only recorded gangue nineral although in


    the Bald. Spur Lod.er erartz pseudonorphs after calcite pre-
    doninate , indicating that calcite r.ras ori-ginally a najor
    rcineral.

    Fraser & Adarns (19O7) noted only nanganese oxides,


    )21+

    ;hT-'roqa1 I 2 7 4 5
    Quarlz
    Cnlc\lc,

    fritc o
    llarcasilc
    sU
    Arcar:opyrio,
    Elcctrvrrl
    gVllalerte o
    Galena v
    Hcsitc (,
    z
    forrhotilc E
    litanonqncttc ?
    t!
    lcncilc
    kaolinilc

    Flgurc r-D-Z: Parageaetlc sequoucc of veln olaerele in the Kuaotunu area


    (bascd oa descrlptlons by Fraecr & ldana, 190?, and parkl.naon, l98O).
    325

    henatite (forning pseudonorphs after calcite) and electrun


    ninerarisation in the Bald spur Lode but pyrite, arsenopyrite,
    galena, sphalerite and eLectrun (average Au:Ag ratio = 1:0.4)
    are recorded fron the l'Iaitaia vein. Electrun in both veins
    ( tut especiaLly the Bald spur) was very f i.ne grained. and,
    widely dispersed in the quartz causing considerable probrens
    with the early treatment nethods.

    Parkinsonts (tggo) vein paragenesis for the region is


    as follows: (1 ) calcite and quartz (now represented by quartz
    pseudonorphs after calcite) followed by brecciation, (Z)
    nicrocrystalline quartz, (3) grey quartz often aeconpanied,
    by brecciation, and lastly (/-) quartz and clay. The rast
    stage. is repxesented. by large euhed,ral quartz cry3tals, in
    the central part of the veins, set in a quartz clay (kaolinlte
    near surface, illite belor,r 100rn) pug.

    Parkinson identified pyrite, arsenopyriter pyrrhotite,


    sphalerite, galena and titanonagnetite in a single polished
    nount of the grey quartz naterial (phase 3 df above). An
    unidentified Ag - Te nineral, probably hessite, occurs with
    galena inclusions in pyrite of this specimen.

    rn an earli-er section of his thesis (p97) parkinson


    nentions the occurrence of quartz, pyrite, narcasite,
    arsenopyrite veins erosscutting the veins of quartz
    pseudonorphs after calcite. Their relation to the other
    stages is not stated although on p1 28 they are listed after
    the veins of quartz pseudomorphs after calcite and before the
    grey quartz nineralised vei.ns. Fig. r-D-2 sunnarises this
    information with consi.derable inference by the rrriter.

    FLUID INCLUSIOTTIS

    Fluid inclusions were exanined in three sanples of quartz


    (unnineralised. except for pyrite) fron the Kuaotunu aretl:
    1l+007 (K3) , 14008 (XA) fron the llaitala Ridge t{ine (ttaitaia
    Vein) and 1/+009 (Cl,t) frorn the Gold.en Link Mine. Fluid.
    lnclusions in all three sanples are two phaser liquid. plus
    vapour, nornal types.
    326

    tg' 2N 220 240 260 - 290 ,00

    EI EI 14007

    l-l t4009

    | | | J; 'r t | | | , I ,r I
    'r
    too 200 ?'20 240 260 2go 300

    Fif lrhg Tavngeralarc "C

    Sringla value: El

    Flgure I-D-3r Flatograoa of prhery flutd Lncluglon fllllng teuperaturoa for


    raoplea of quartz frou tho l{aliata Rldge l{lnc (1400? and 14008) and Gol.den
    Llnk l.tlnc (11,009), ?he lndtvldual lossurcronta arc ltsted ln Appandk fII.
    32i.

    Prinary fluid inclusi'ons are ra.re and of snarl size


    ln the I'laitaia vein sanplesr. hence only a few filrtng
    tenperatures could be deternined. frou these saroples. The
    results are presented in Fig. I-D-3. pre'ssure salinity
    corrections of between 5 aad 10oc nust be added. to the
    filling teuperatures. vhich indicate i. probable tenperature
    iange of nineralisation betlreen Z5O and Z?OoC.

    SULPHUR ISOTOPES

    Three sanples of pyrite fron the Waitaia Mine have


    534s' values between *0.5 and +1 .0 per ni_I (Table 9-1).

    THERMOCUEI''f ISTRY

    Parkinson (tgao) related the dtepth zoned distribution


    of alteration ninerals at Kuaotunu (kaolinite and
    nontroorillonite at the surfaee giving way to sericite at
    depth) to the pH of the hydrothernal fluids, suggesting that
    the near'surface vaters were aeid.ic, whereas the deeper.
    vaters uere neutral or slightly arkaline. A pH value of 5.j
    (neutral pH at 250oc) was used to construct the contours of
    Iog z S shown in Fig. f-D-4.

    Stage 2 nineralisation is defined by the presenee of


    pyrite and arsenopyrite but absenee of borniter plrrhotite,
    tregnetite and henatite. fsz of this nineralisation is there-
    fore linited between the pyrite/pyrrhotite and arsenopyrite/
    pyrite plus arsenic boundaries.

    Pyrrhotite titanonagnetite are present in Stage 3


    and.
    nlnerali-sation suggestiug close proxinlty to the pyrite-
    pyrrhotite-nagnetite triple point in F.ig. I-D-4. Because
    graphlte is absent fron this nineralisation a log fcoz varue
    of +1.5 (the general value used where ncO, has not been
    neasured) i" precluded. A value close to 0 for this paraneter
    seens rore reasonable and ls also plotted in Fig. I-D-4.

    The concentratlon of total sulphur ia sorutj.on during


    Stage 3 uineralisation was aporoxinately O.OOzm (fog z S =
    -2.7) and by using the sane value for sbage z mineralisatlon
    328

    ll
    Dlt*t.vld
    1t^fhlcr.

    C.rt

    w,
    \ii
    8-
    J {Ad.
    d,,ti"i7
    '{$i
    / H?l: ?
    *'o
    MAGNETITE wifq
    'r...ta

    Log f 0z

    Plgurc I-D-{c fSZ vcrsus fOa dlagrao at 250oC ahoulng the geochenleal envlron-
    uent for Stage I quartz + pyrtte * electruo depoeltlon (atar) and the
    tranrltlon froa Stage 2 quartz + pyrlte t tarcaslte + pyrrhotlte to Stage J
    quertt + pyrltc l araenopyrlto + sphaler!.te + galsna * pyrrhotlte {
    tltaaouagnetl tc (arros). {S*0.002nrp8-5.5r1og fSa fron electruu conpoeltlon
    (Stagc t only' aee text) r -10.1. Detallg of conatructlon are glven ln
    Appendtx V.
    the progression fron stage.2 to stage 3 cen be represented
    by the arrow in Fig. I-D-4.
    j
    Therefore if temperature remained constant , foz and. fs,
    decreased frou Stage 2 to Stage 3. Alternatively a sinilar
    changeinninera1ogycanbecausedbyas1ightincreasein
    tenperature (eooc) at constant fo2 and fs, . A decreasing
    temperature, fOZ and fS, regine seeEs trore likeIy.

    Fraser & Adams (t9oz) recorded au average gold:silver


    ratio of 1:0..4 for the l'Iaitaia ore. Silver ninerals other
    than electrun were not reported by then. Equating the
    gold.:silver ratio to 'r,he average conposition of electrun, a
    1og fsa value of -10.1 at 250oc rnay be calculated. rf a
    silver nineral uere present (for exanple hessite as
    tentatively identified by Parkinson) the proportion of silver
    in electrun would be l-ess and indicate a higher value of fSa.
    Nevertheless, whether a silver nineral is present or not the
    sulphur fugacity derived for electrun deposition is rnuch
    hi-gher than indicateil for stage 2 and stage 3 and by the
    possible presence of arsenopyrite with the electrun as
    suggested. by Fraser & Adansr description of the nineralisation.
    Either, conditions were very di.fferent duri-ng electrun
    deposition with nuch hlgher sulphur fugacities or the gold
    - to si-lver ratio reported. by Fraser & Adans is not representative
    of the electrun conposition. In the forner case a
    hydrothernal lluid containing approxinately equal coneentrations
    of sulphate and sulphide is indicated (Fig. f-D.4).

    In conclusionr the base netal nineralisation at Kuaotunu


    is characterised by a relat5-ve1y low concentration of total
    sulphur j-n eolution and 1ow fugacities of 02i s2 and cOr.
    Electrun depositi-on nay have occurred. at higher fugaeities
    of 02, SZ and COr.

    GE}IESIS

    Parkinson (rgao) postulated that the epithernar Au - Ag.


    veins j-n the Kuaotunu area were near surfaee deposits of a
    fossil geotherreal systeu. They were considered to occur at
    33a

    the boundary betueen ouart.z - illite and quart,z l:aolinite


    ua1l rock alteration vhich Parkinson interpreted as rnarking
    the change of fluid pH fron alkaline to acidic and netal
    carrying cornplexing ions in solution fron doninantly chloride
    to doninantly b5-sulphide.

    Developi-ng Parkinsonrs latter hypothesis, Stage j


    nineralisation was probably deposi-"r,ed as a result of reduction
    of the fluid (.s represented by the decrease in f0, and fse
    fron stage 2 to stage 3) or lncreases in pH due to wal1 rock
    reactions. Conversly electrun d.eposition (Stage l) was
    initiatecl by decreasing pH and possibly oxidation (suggested
    by tbe high fS, and fO, values indicated by electrun
    conposi-tions) .

    REFERENGES AND BIBLIOGRAPHY

    D0WNEY, J.F. 1935: see pp 39-5lr and 267


    FRASER, C.lADAMS' J.H. 19O7 t see pp 133 - 137
    PARKINSOI{, P. C. 1980
    scHotr'IELD, J.C. 1967
    SKINI{ER, D.N.B. 1 968
    1972
    19?6
    STEVENS, G.R. 19?O
    IIILLIAI'IS, G.J. 197 t+. see p1 00
    331

    I-E
    T0KATEA,_ C0R0MANDEL

    INTRODUCTI0ITI

    SeveraL veins oecur in the Tokatea-Suceess ranqe


    innediately to the east of Coronandel to'.+nshi-p. The largest
    is the Toliatea Big Reef, a generally unnineralised quartz
    vei.n, approxinately {kn long and up to 45n wide. Veins
    containing Au - Ag and base metal nineralisation occur on the
    footwall (eastern) side of the Tokatea Big Reef and. were
    nined. in the Tokatea - Royal Oak and Success nines.

    (1935) recorded a total produetion of 3.9 nillion


    Dovrney
    grans (125,688 ounces) of which 1 nill-ion grails (j't,ZZ5 ounces)
    were produced from 7,788 tonnes of quartz.

    Skinner (1967) briefly described the Tokatea Big Reef


    but apart fron a geochenical exploration progran carried
    out by ASARC0 ( Neilsen, 1968) no geologleal work has been
    reported on the nineralisations since Fraser & Adans ( t 9oz) .

    GEOLOGY

    The section of the Tokatea Suceess range of interest


    here (Fig. I-E-1 ) conprises greywacke of the Tokatea Hill
    Fornation (Moehau Group) and andesites of the Beesons rsland
    Volcanics ( Coromand.el Group) .

    The Tokatea Big Reef occurs in both rock types, whereas


    veins of the Tokatea - Royar Oak rnines occur only in ?okataa
    Hill Fornation and veins of the success l{ine occur onry in
    Beesons rsland volcanics. Fraser & Ad.ans (1902) thought that
    the latter was tuffaceous in the vlcinity of the Success lline.
    These authors also considered that the nost productive portions
    of vei-ns in the Tokatea l'lines occurred. where tuffaceous
    sed.lments (of the Tokatea H111 Fornation) were found i-nter-
    stratlfied with the ord.inary sandstone and argillites of the
    Tokatea Hill Fornation.

    llorkings on the Tribute vein 1n the Rgyal Oak Mine


    332

    m
    n GROUP

    =
    m Crcyurcke, ToKATEA HILL FoRMATtoN ,MANAIA !{lLL GROUP

    \ I*afca gig Pezf


    Fauft
    *= R.md
    x Mine

    Flgure I-E-ls Geology of, the Coronandel and Tokatoa aroas (after Sklnner,1976l.
    't-,i

    encountored a hornb'lende porphy'ry dille approxinately 7.5R


    rFide and dipping eastward.s (normal to the strike of the vein).
    The dike occurs in Tokatea Hill Fornation. The Tribute vein
    crossed. the dike but at a reduced uidth or by breaking into a
    few snall stringers.

    HYDROTHERI.IAL ALTERATTOl{

    Fraser & Adans (1907) noted that the sedinentr,ary rocks


    i-n the Tokatea l.{ines were silicified, pyritised and bLeached.
    They described the alteration of the Beesons fsland Volcanics
    in the Success l'line as propylitie with no further qualificatj-on.
    .Nei1sen(1968)consideredthattheanclesiteSsurIoueding
    the Success Mine were only moderately altered.

    MINERALISATION

    Tokatea Bis Reef


    The Tokatea Big Reef extend.s southwards fron the l'laverly
    Fault along the we3t flanks of the Tokatea Range, branches
    into two veins in the vi-cinity of the Buffalo Mine and ends
    on the Cadnan Fault (rig. I-E-1 ) . sk:i.nner (1967, 1976) con-
    siclered that the veins'outcropi-ng in Cad.nan Strearn' Aitken
    Stream, Hutt Creek and Petote Strean (described in Section
    I-G; Petote Strean Area, Coronandel) are continuations of
    the Tokatea Big Reef on the southern side of the Cailnan FauLt.

    The Tokatea Big Reef varies in uidth between 10 and l*5n


    ancl dips to the west 40 to 75o (Skinnerr119T6). Outcrops
    eontain cross cutting veins of eonby and vuggy arnethystiue
    quattz with crystals connonly 100rnn 1ong. Very ninor base
    netal sulptriae mineralisation oecurs at a few localities (e.g.
    Buffalo Mine) tut go1d. and silver are absent.

    Tokatea l{i-nes
    Veins containing gold and sil-ver occur .-on the f ootwall
    sj-cle of the Tokatea Big Reef near Tokatea Saddle. The largest
    rnine was the Royal Oak I'hich consi-sted of seven adit leveJ-s
    and two l-ouer levels i;ori:eC fron e sliaft. llost of tire ore
    taken fron this nlne cane frou the Tokatea and Tribute veins
    which strike east-north-east and east respectively. The
    followi-ng description of these veinp is sunnarised fron Fraser
    & Aclans (190?) .

    The major vej-n constituents are quaitz, calcite (far


    nore abundant than in the liauri Bl-oclr and }iapanga ni-nes, see
    Section I-F), pyrite and electrun. lianganese oxides (e.g.
    pyrolusite), native arsenic, arsenolite, orpinent and realgar
    were al-so noted. The latter three oecurred as coatings on the
    wal1 of the veins and are probably of supergene origin as rl'as
    also. the uanganese oxides. Tn the I{est To}:atea and other
    nines siiuated south of Tokatea Saddle the arsenic was usually
    in the forn of renj.forn nodules. Geodes exceeding 1 50mn in
    dianeter were not uneonson and often enclosed fiiarnents of
    electrun. ''

    Electrum oecurred in bonanza shoots related to supposedly


    nore perneable layers in the greywacke termed rnineral headstr
    or nbarstr. In the lower levels the bonanzas generally
    oceurred. at the intersection of trflintlesn ("o calIed because
    of thbir fine grained siliceous nature) vith the veins, or
    oecasionally in corul""tion uith faults of slight displacenent.

    Vugs lined with crystals of quartz and cal-cite were


    eonaon, sone exceeding 3n long by 0.3n wide, and lrere often
    assoeiated-with bonanza ores. Electrun was usually assoei.ated
    vith quartz and pyrite but sone visible grains and threads
    . a occurred in cleavages of calcj-te crystals. The quartz and
    caleite i-n the veins were rroften irregularly associatedn but
    Fraser & Adans describeci a crustified speciur6n consisting of
    1) pyri-tised waI1 rock, 2) white crystalline quartz containing
    fine disperseil electrun, 3) coaby crystall5-ne quartz, and l-)
    large rhornbohedral calcite crystale.

    Fraser & Aclans (1907 p122) state that n_!he goltl occurs
    with sil-ver in the average proportion of 100 to 50 by ueightn.
    It is not clear whether this refers to the overall Au:Ag
    rati-o in the ore or the electruir cotrposition as quoteil by theu
    for sone other deposlts.
    335

    Three samples ori-ginating fron the Tokatea ni.nes uere


    obtained frorn institutional collections- A saurple of boaanza
    gold ore (sanple 1j961) contains fine grained hessite,
    electrun and ninor chalcopyrite scattered in quartz euhedral
    to the netallic ninerals. The following banded sequence
    occurs: quartz plus hessite
    qnartz plus hessite, eleetrun and ninor chalcopyrite
    quartz plus electrun
    vug quartz ( crystals up to 2nn long)

    The other two samples contain quartz, sphaleriter galeoa,


    pyrite and chalcopyrite. Sanple 13960 (TK6) coatalns nediuu
    to coarse grained sulphid.es iu the ord,er (textural interpre-
    ta.tion):
    quartz plus pyrite
    quartz plus sphalerite and galena
    quartz plus chalcopyrite and pyrite
    quartz

    The sphalerite is charaeterised. by abund.ant incluslons


    of (int,erstitial and exsolved?) chalcopyrite (Fig. 4-17).

    Sanple 13959 (TK1) exbibits an unusual texture, consisting


    predorni nantl;r of large uasses of sphalerite, with abund.ant
    chalcopyribe i-nclusions, seaned .(Fig. t*-21) Uy fine grained
    galena, chalcopyriter plrite aud, quartz (subhedral to the
    sulphi-des). Replacement of pyrite by galena is i.ndicated by
    poiirilitic texture (Fie. 4-14).

    Success l'line
    The principal veins in the Success Mine were the Jubilee
    i'ios 1 and 2, Success Nos 1 and 2 and Janes nEast and West
    Reef rr. Little is knorrn of the nineralisatLon other than that
    the eLectrun occumed in bonanzas and that in the upper levels
    ttsheets of rgoldt (electrun) without any adnixture of gangue-
    minerals were found enclosed in open cavities in the vein
    f*ssure. These irere descrlbed to the wilters ras hanglng
    fron the top of the cavity like leaves of a bookr n (Fraser &
    Adams, 1907 p12l).

    r,I
    336

    oJJll

    t7965
    EI
    11956
    --tF
    --

    tffl fte57
    E,J-l

    h Bqss

    |ffi
    SalinilV
    .q. wt'& NaCl
    a

    e.l--l- t-) . El
    ?fngE .'r-1.
    valueq: El

    Fi.gureI-E-2r [lrtogtarr of, ftl,llag tenp*oturer sail epguren:t ral{nl,tl,oa for


    prlnary f1uJd inelnrslone !,a ,seopl..es of, qrtartz i 139rr, 7 Lsvrl Royrl Oet Ffl,net
    13956 Roycl Ork l{lae (unlscatad)t 17957 fskatse B!.g Reefl Tokatca sad.Ust
    1tgr8l Buffalo illnc. fhc biltvtdual talturrnsntr arc llctcd la ippendlr IfI.
    337

    FTUID I}ICLUSIOUS
    I'luid inclusions in sanples fron ? level of the Royal
    Oak l,line ( sanples 13955 quartz and, 1 3956 calcite) , Tokatea
    Big Reef near ?okatea Saddle (lZgSl) and the Buffalo l,line
    tip head (13958) are nornal two phase, liquid plus vapour
    types- These locations are shown in Fig. I-E-1. Hlstograils
    of filling tenperatures and salinj-ties for the samples are
    presented in Fig. f-E-2.

    Sinilar depositional tenperatures for the two saroples


    fron the Royal Oak l,line and the sanple fron the Tokatea Big
    Reef are indicated by the sinilar ranges of their fi1.llng
    tenperaturas. Pressure - salinity corrections are probably
    less than 5oC and therefore a d,eposi.tional tenperature of
    22OaQ is assigned to these sanples,

    The sanple fron the Buffalo Miue has generally higher


    filJ.ing tenperatures and a pressure - salinity correction of
    up +,,o 1OoC rnay be requiredr giving a depositional tenperature
    of aporoximately Z65oC. Thls higher tenperature is to be
    exDected because the Buffalo l{ine is at a louer level in the
    Tol:atea Big Reef than the Tokaiea Sad.dle (approxinately 300n).

    Apparent salini-ties of the Tokatea Big Reef sanple nay


    be higher than those of the Royal Oak sanple although this
    difference nay not be si$nificant eonsid,ering there is only
    one result for ihe latter.

    Partial chenical analyses of fluid.'inclusions in sanples


    13957 (rre) , 13958 (eoz) and 13962 (no3), d,eterni.ned, by
    crushing and leaching experinents, are presented in Table 7-7.
    All three sanples have Na/K ratios around, 2, considerably
    lower than theoietical values, between 5 and. 'I .5, pred,ieted.
    by the I'ia/K geothernoneter for ihe d,epositional tenperatures
    consldered.

    SULPHUR ISOTOPES

    Sulphides in a sanple of ore fron the Tokatea l.lineE ha.ve


    63LS values of *2.6 per ni1 (pyrite) +2.3 per ni1 (chalcopyrite)
    338

    TABLE I-E-l.r Oeacral tharrochetl,eal peraret'sng f,o'r the rilepoeitl'onal


    cnvl,ronilsnta of ths cpLtharual baae us 'aI anit gold -
    sllvcr tlncraltgatlonr in the lohetoe lllnelr oorone:rdgl'

    Staga
    Baac ustal '0o1d - 9tlver BcfcErncc

    Torpeleture oG 280 224 Eable,Y.l


    true tronlc Strergth 0'.21 0'1,7 t
    t
    Saltrnlty (r'!taOl cq.) 0.26 0.23
    .C a.oL5 0.0e5 r
    pH ,,, ,.9 Sae t'ert
    pH of kasl-lnltey'rsrl.clte Y-l
    bouadary
    1'? f.8 ?ebXe

    pd of esrlc!.te/f,-feldsplr t
    boundary
    5rg 6.!
    (log ers)
    T-o,tal S -2.0 -2rQ Sas tcxt
    Log f8p (ephalerl.te coup.) -1 0.9 TrbLs V-lA
    ('etrectruo; oonP.) -12. r. Teblc V-6A
    -11.? Tablc S-6C
    Log Id2 -35.Oto-!7.0 -t8.lto-10.,O Flgurel clted
    lrtg t-n-l) (fle. I-E-5)
    f,og fo0a fl rI +11 .7 TabLr Y-l
    339

    and +2.0 per nil (sphalerite). ninerals are.not in


    The
    isotopie equilibri-un as indicated by their failure to obserye
    7
    the nornal fractionation trend py> sp2 cp and therefore '
    d.epositional tenperatures calculated fron their fractionations
    are not realistic;

    HYDROGEN ISOTOPES

    i'Iater fron fluid inclusions in sanples 13957 (tXZ),


    13958 (802) and 1 3962 (R03) was extracted under vacuun and
    the hydrogen separated. anil analysed by nass spectroneter.
    5D values were rneasured as -33.2 (13962), -31r.1 (lZgSZ) and
    -36.3 0395A). These values are consistent with a neteorie
    water origin (possibly during a cooler clinate than present)
    although other types of water could be involved by invoking
    various nod.ification processes.

    THERMOCHEMTSTRY

    Tr+o rnj.neralisations are nodelled for the Tokatea ltines,


    an earry relatively high tenperature (zsooc) base netal stage
    and a ]iter lower temperature (22OoC) gold - silver stage.

    Table I-E-1 lists so&e of the parameters characterising


    the geochenical environnents of these nineralisations. An
    fOa versus pH diagrarn for the high tenperature nj-neralisatlon
    is presented, ln Fig. I-E-3, whereas fS, versus f0, and f0,
    versus pH d.iagrans for the l-ou tenperature nineralisation
    are presented in Figs I-E-,[ and, f-E-5 respectively.

    Fraser & Adans ('tgOl) described, the hydrothernal


    alteration of the greyr.racke wal.l rocks as siliclfication.
    The presence of the pE diagnostic potassiun ri-nerals Has not
    noted. Therefore regioas of rnineral deposition over a range
    of approxinately 1 pH unit either sicle of neutral (p[ of 5.j)
    are shown in Figs I-E-3 and I-E-5.

    Because of the absence of henatite and nagnetite, the


    hytlrothernal fluids plot in the reduced. sulphur species region
    of the high tenperature f0, versus pE diagran (Fig. f-E-3),
    whereas fluids with dissolved. sulphur in solution predoninantly
    3t&

    -Lto

    -n 5ericie {- felds7ar
    -n
    -n
    HEMATITE
    -n
    -rl *$*..-
    otrl AOR,NTTEI F/RITE
    - MAGNETITE

    (F -A c$Atl;ovtRt're i
    o
    -t PYRITE I

    -% brafritz = t l'
    -.LoqJSz:==1),
    -n
    -t8
    -19

    PH

    Flgure I-E-3: foa veraus pll dlagran Et 28OoC and 4.S=0.01a ehonlng the broad
    geocheul.eaL envlronuant (ehatted) for quartz + pyrLte + chelcoPyrlte +
    ophalerlte + galsna (l electrun?) olneralleatlon ln the Tokatea tJl.nes. (See
    Table I-E-1 for relevant tberoochenlcal paranetera and Appeadlx V for
    uethods of corstructloa.)
    3lt1

    -2
    -4
    .6
    -8

    (\. -to
    rt.|
    -a
    $ -t4
    -tG

    -tg
    -20

    -n
    -24
    10 -49 -46 4 -A -10 -79 -76 -34 -t2 -n
    lntfoz '

    F!.gurc I-E-4: fSa vcrrus fO, dl,agrarat 220oC ohonlng tbc probable cboolcal
    cavtronnont (shaeea) for quartz +pyrlte f clectrul ! hasstts ! argentltc
    (aoanthlte) ! aatfve arrculc deposltloa ln the velng of thc Tokatea illnec,
    (Scc teble I-E-1 for rclevant thcrlocheulcal paraletera and Appendlr V for
    dotallr of sonatructlon.)
    3 l|?

    BORNTTE + PVRITE

    I
    I

    t
    I

    !
    I
    PYRRHoTTTE !

    Fi.gure I-E-5r f0, versus pH dlagrau at 22OoC and I$.g.pgla ah.ovlng two poaalble
    geocheulcal cnvlronoents (A anit B, ehaded) for quartz + pyrlte * electrun
    al
    I hegalte f argentlte (acanthlte) t."11ve areenlc depoaitlon ln tbe velne
    of tha Tokatsa MLnee. Envlronoeat B, coaeletent rlth the higher teuperature
    baee oetal oLncrallsstlon, le preferred hera. The pH of the cal.clte
    aol.ub1e,/insolubla boundary o 4.9. (See Table I-E-l for othar relevant
    therllocheltcel paraoetera and Appendlx V for detatlr of constructlon.)
    3l+3

    as sulphate (rieta ttAtt of Fig. r-E-5) or sulphide (rieta rBl


    of Fi-g. I-E-5) are possible at 220oC. To be consi.stent with
    the high tenperature fluid and because sulohate ninerals (e.g.
    barite) are absent, field B in the reduced sulphur species
    region is preferred. At both tenperatures 1og fCOA nay be
    less than initially suggested, (i.e. the general log fC02 value
    of *1.5 for the high tenperature rnineralisationr and the
    neasured vtlue of *1.? for the ].ow temperature nineraLisation),
    possibly as low as log fCO, = 0 at 280oC.

    GENESIS

    The occurence of sulPhur,in solution predoninantly.in


    reduced forn indicates tbat 6'4t t, is equivalent to 5 SLru t2oq
    which ln turn is approxinately equal to i3+, of the
    sulphide Einerals such as chalcopyrite and sphalerlte.
    Therefore a value of *2 per nil is assigned to 534S a S and is
    lndicative of a nagnatic source for the sulphur. In contrast,
    a rneteoric origin for the uater is suggested. by 5D values of
    the fluid Lnclusions.

    There is insufficient i.nfornation to define the specific


    eauaes of mineral d,eposition in the Tokatea area or uhy
    precious and. base netal rninerelisatlon is essentially absent
    from the Tokatea Big Reef.

    REFEREIICES AND BIBLIOGRAPHY

    DOWNEI, J.F. 19352 u"" ni g-1g and 265-256


    FRASER' C.; ADAMS' J.H. 1907: see pp 119-121,
    KEAR, D. 1958
    NEITSEN, K.I. 1968
    scHoFIEtD, J.C. 1967
    SKINNER, D.N.B. 1967

    1g'12

    1976
    I{ILLIAMS, G.J. 19742 see p103
    3lrl,
    t-F

    [4r]Rl BL0CK Arip KAPAIJGA, CoRol.rAr'rpEL

    INTRODUCTION

    The nintlralisations consi-dereil here are those nined in


    the iuroediate vicinity of Coronandel townshipi the Haurakj-
    and Bunkers Hill nines of the Kauri Block to the west of the
    town and the Kapanga l,iine to the nor'r,h (Fig. f-F-1).

    Like the deposits at Thanbs, the Coronandel deposits


    differed fron other nj-neralisations in the provi-nce by having
    bonanza style ni.neralisation with -very high Au:.Ag ratios. The
    Coromandel d.eposits vere also unutual- in the nurober and diverse
    strike of tbeir veins and the general absence of silver
    ninerals other than electruo.

    The three mines prod.uced, a total of ?.4 nillion grans


    (2fi,4o? ounces) of bullion fron 66,81,5 tonnes of quartz
    (Downey,1935).

    The nines lrere uorkedfron shafts and are now inaccessible.


    The only geological investigation of the nineralisation was
    nade by Fraser & Ad.aus. (190?) although the descriptions of
    the nines by Downey (1935) give sone insight, to the style of
    rnineralisation.

    GEOTOGY

    The nineralisations occur in hypersthene andesite and


    hornblende dacites of the Beesons Islanil Volcanics of the
    Coronaudel Group (fig, I-F-1).

    Fraser & Adans (190?) noted. that the rocks encountered in


    the upper levels of the Kapanga and Scottys (groupecl here uith
    the Kapanga) nines were fine gralued tuffs interstratified
    rrith solid, flows of andesite and daeite, whereas fron
    approxinately 220n to 37On below surface (tlO to 300n below
    eea level) the country roek consisted, enti.rely of tuff beds
    (dipping at low angles to the uest and. south-west) and, an 0.6n
    thick carbonaceous layer (dipping southwards), encountered at
    3lr5

    d t\

    I KaVanqa

    t
    mc,lvcg

    E thaft
    blagroveu o
    \- Vcrn *

    Yalnlean
    ,
    ryt
    Crovt4

    Kauri Block
    *iiu

    Coromarlde,l
    Harbour

    Flgura I-F-'l t Loeatlon of veLng and rorklngo ln the Kaurl Block and Kapanga
    Er6B8o Detalled plane of sone of tho nlnee are held at the lluntly Branch
    of Hlaee Dl.vlslon.
    31,6

    approxinately ?8'7n (213n below sea level).

    The rocks of the Kauri Block are predoninantly andesite


    flows although fragnental rocks also occur. A hornblend,e
    porphyry dike forned a hard bar in worklngs of the Golden Pah
    l.line and Fraser & Adans (tgoz) consid.ered. that it probably
    extended into the union Beach section of the iiauraki l,fine.

    HYDROTHER}IAL ALTERATION

    Fraser & Adams (tgOZ) described a depth zoned pattern of


    alteratlon ln the country rocks of the Kapanga and Hauraki.
    l,{ines. In the top 120m of the Kapanga Mine (fron surface to
    50n below sea level) ttre and,esitic rocks were alterednto a
    bluihh r+hite pyritised kaolinitic-like nasstr ia which
    rrsilicification is not an unconnon featuren (Fraser & Adans,
    19A7, p100). Between 120n and 270n (5On and 200n below sea
    level) ttthe andesites penetrated rlere harder, and of a dark-
    greenish colouri alteration in this zone apparently resulting
    nainly in the developnent of chlorlte aad., in a lesser degree,
    of carbonatestr (Fraser & Adarns , 1907, p100). Fron 2'l0n to
    370n (ZOO to 300n below sea level) another zone of intense
    alteration was encountered.

    Similarly the rocks in the upper levels of the Hauraki-


    Mine uere intensely altered but passed into less altered nhard
    dark-greenishrr rocks with d.epth. Intensely altered rocks
    were qgain encountered at approxinate{v 1 20n below sea level
    (beIow the {00 foot level).

    MINERALISATION

    Kan*l Block
    A large nunber of velns of dLverse strike were rorked in
    tbe Eauraki hnd Bunkers Hill niaes. The veins averaged. 150nn
    in width but varj.ed fron trnere stringers to strong ore-bodj.esn
    1.5n uide. The nost productive vein was Legges Reef (also
    knorsn as No. 2 Haurakl) ln uhLch the ore shoot neasurdd, 45n ln
    length nnd extend6d frou the surfaee -dorn to a depth of 80n.

    The najor vein constituents rrere quartz ( Uf ui sh-white


    colour), pyrlte, sparse calcite, arsenopyrite and. nanganese
    J4'r
    ta
    '

    oxides, I'lative arsenic (generally nassive), stibnite


    (Hauraki and Blagrovets l,tines), pyrargyrite (Golden Pah l,line)
    ancl kernesite (Hauraki Mine) were also found. Vugs Lined. with
    drusy quartz were nabundantrr and. wa1I rock brecci-as occurred
    troccasionallyn. The vein raaterial was sharply separated fron
    the snooth sliekensided surfaces of the lrall rocks by a narrow
    npugn (fault breccia) zone. Electrun (averaging 7lrfr go1d. and
    26fi silver) occurred in bonanza shoots generally related to
    vein intersecti-ons. Ore containing nthree ounces to the
    poundtt (200C/kS) was rtnot unconroonn, and nany tonnes of ore
    lrere mined averagj-ng over nan ounce to the poundn (lOg1yt1 .
    Although uorki.ngs were runk to 120n and the lowest bonanza
    was -nined at 90n, nost of the gold vas von frorn within 65la
    of the surface. The bonanza sections of the nines occurred.
    in intensely altered country rock.

    Kapanga
    Two. north stri-king, but very sinuous, velns known as
    Kapanga and Scottyts were mined to belor.r 180rn fron the surface
    in the Kapanga Mine. Their westerly dip of 25 to 35o in the
    upper levels increased with depth at a point where the country
    rock becane hard.er and nless alteredn. In the deeper leveIs
    this palr of veins were not id.entified., with nining on the
    940 foot (ZAZn) and t O6O foot (305n) leve1s being on two
    lresterly striking vein3 knovn as llartrid.gers aud Anniversary.
    The latter veins uere not located above the 940 foot level
    and therefore the relationship between the two pairs of veins
    is not known.

    AJ-l four veins were very Darrolr wlth naxinun widths J-ess
    than 0.5n. Quartz and pyrite predoninate over calcite.
    Electrun (averaging T!fi golcl snd, 3Afi silver), often.visible,
    occurred in bonanza shoots at bends and. elbows in the veins
    or at the i-ntersections vith cross veins. ltrati-ve arsenic
    (reniforn nodules and rnassive forms) and arsenopyrite uere
    cornnon in the rich orer Aragonite was found, ln Scottyts Reef,
    Strong pyrite nineralisation and hyd,rothernal alteration of
    the waIl roeks acconpanied, t,he bonanza nineralisati-on. The
    richest bonanza ln Hartridge;s vein occurred. in the gl.'0 foot
    leveI (28?u) nea!!:.Larnaeh Shaft where the vein contacted the
    3l+8

    -2
    -4
    -c
    -8
    -to
    C\f
    (.r\
    -t2
    (F -t4
    o
    -tG
    -tg qi
    Sl
    trj
    l--
    Eii -qit
    -a .ul zloid
    sl
    -72
    5|u =
    -A
    4 -14 -44 -44 -42 -4 -?g -16 -% -?2 -n
    Log f0z

    Flgure I-9-2t fS, versue f0, dlagran at 220oG ehoulng the geochenl.cal envlron-
    nent (llne of croagee) of quartz + pyrlte * electrun I er"tnopyrtte !
    natlvc areenlc depoeltlon ln the velns of the Kaurl Block anil Kapanga lltnes
    Coronandel. Log fS2 fron eLectrua coupoeltlons . -10,7 to -11.3' andl 1og
    f C02 ( csthateil) . l1 . 5. (Sea Appendix V for uothodo of conatructlon.)
    3lr9

    0.6m carbonaceous layer nenti.oned earLj.er, The latter uas


    strongly pyrltised.
    r;

    THER},IOCHE},IISTRY

    The Kauri Block and Kapanga nineralisations are


    nodelled at a tenperaiure of 220oC in the fS, versus tOZ
    (Fig. I-F-2) and. f0, versus pH (Ffg. I-F-3) d.iagrans.

    Average electrun conpositions given by Fraser & Ad.ams


    (1907) indicate log fS, values around -11 (-10.7 for the Kauri
    Block and^ -11.3 for Kapanga) at 220oC, but the presence of
    natlve arsenic and arsenopyrite in sone parts of the ore
    requlre 1og fS, to be below -12.3 and -13.8 respectively.
    The presence of pyrite but absenee of pyrrhotlte fixes the
    lowest possible log fS, value at -'45. Therefore a range
    between -1O.5 and -14 is consi.dered. here.

    Linits of f0, nay be asslgned by consi-dering the presence


    of caLcite but absence of graphite and anhydrite if fC02 is
    known. Unfortunately this pananeter can only be estinated.
    and graphite/CO, and calcite/anhyd.rite boundarj-es are shown
    in Fig. I-F-2 for a log f00a = +1.5.

    less than 5.7 are iad,icated by the range in


    pE values
    1og fS, values and the probable 'b.bsenee of K-feld.spar in the
    veins and wall rocks (tUe presence of K-feldspar was not
    mentioned by Fraser & Adans, 1907). Neutral pII at this
    tenperature is about 5.5.

    The exact conposltion of l'raser & Adans nkaolinitic-Like


    nasstr associated. wlth the ore ls not known and although it
    could be kaolinite it nay also have been another clay nineral
    such as serlcite or nontnorillonite which have been noted.
    fron other Ceposits in the province. The presence of clay
    without knovledge of its conpositlon ls therefore not very
    halpful in defining pH. In conclusion the pH of the fluid
    uas probably sorner,rhere in the range of 4.5 to 5.'7.

    The probable area of fluid eonpositLon, consi.stent with


    the above d.ata, is shornr as a shaded area in Fi.g. I-F-3.
    ..{
    t i"
    350

    HEMATITE

    oORNITE + N
    P{RITE

    PYRITE
    k.g-'Llu.-E--

    PYRRHOTITE

    Flgurc I-F-3; fO, veraua plt tllagrau at 220oC and{S'0.0014 ahovlng the geo-
    chsulcal snvlronnent ( ahaded) of quartz + pyrtte * electruro * areenopyrlte
    I natlve arscnle ilepoeltlon ln the volag of the Kaurl Block and Kapanga
    Hlnesr Coronandel. i=0.1J, .raf,+=0.02rVH=5.1!A.6, 1og fSa fron electruu
    cooposl.tlon. -10.? to -11.3, 1og fS2 for natlve areenls itepoeltlon =1-12.3,
    Iog fS2 for areenopyrlte ilepoaitlon '<-13.8. (See Appendlx V for uethoda
    of constructlon.)
    351

    Electruu deposition pred,oninantly occurred at log fS, values


    around -11 but values as lov as approxinately -'14 occurred.
    Log fOa was approxinately between -38 and -42. A fluid
    contalning sulphur in solutj.on in reduced foru j-s indicated.,
    probably wlth HaS predoni.nating over iIS-.

    GEUESIS

    The bonanza nineralisationsof the Kaurj- Block and Kapanga


    nines are related to structural features in a near surface
    environnent and 1n this respect resenble the gold deposlts of
    Thanes- Electrun deposition probably resulted fron boiling
    of the bydrothermal fluid aud loss of HrS, eausing
    instability of the gold tranpporting sulphide conplexes.
    variations in the conceutration of Hrs nay also aecount for
    the vide range of fS, and f0, indicated by the nineral
    assenblages,

    BIBLIOORAPHI A}.TD REFERE}ICES

    DOI.INET, J.tr" 1935: see pp 2-9' 19-31 and 265-266


    FRASER' C., ADAMS, J.H. 1907: see pp 111-118
    NEILSEN, K.I. 1 968
    SCHOFTELD, J.C. 1967 {
    SKINNER, D.N.B. 1967
    1976 r

    WILLIAMS, G.J. l97l+z see pp 100-103


    352

    I-G

    PETOTE STREAM AREA

    II'{TRODUCT IO},I

    Quartz veins containing base metals outcrop in Cadman


    Streao, Altken Strean, iiutt Creek and Petote Strean (Ffg.I-G-1)
    and were considered by Skinner (1967, 1976) to 'be extensions
    of the Tokatea B1g Reef. They were descrj.bed by Fraser & Adans
    (1907) and Sklnner (196?) and reeently re-e*anined by Edward.s
    (tgz9) .

    Although minor prospecting by tbe excavation of small


    trenches and short adi.ts was carried. out in the late 1800rs
    and early 1900rs, the deposlts were found to be small and no
    nines uere established in the area.

    GEOLOGY

    A geologi-cal nap of the area is presented in tr'lg. I-G-1

    in greywacke of the Tokatea Hill


    The veins occur
    Formation. Intrusives (Coromandel Group Kal-iti Porphyrites),
    ranging fron dikes one netre across to stocks 1 50n across,
    also occur in the area aad, were c.-lassified, by Ed.uards (1979)
    as follows:
    (i) Intruslves predatlng reglonal hydrothernal
    alteration, Lower to Mid Miocene; soaL1 dlorite plutons and
    quartz dlorite and apllte d.ikes.
    (ff) Intrusives eontenporaneous with regional
    hydrothernal alteratlon, Mid to Upper Mloeene; quartz diorite,
    and to a lesser extent diorlter porphyries, formi.ng dikes and
    snall stocks.
    (ffi) Intrusives postdating regional hydrothernal
    alteration, Upper I'liocene; predourinantly and.esi.te and daclte
    porphyries and intrusive andesites.

    HYDROTIIERI'{AL -At TERAT I ON

    Edwards ('|.979) described the hydrothernal alteration of


    the greyuacke country rocks, in ord.er of L!,creasing grader &s
    fo]-]-owsl
    353

    v V V lV V v-/ v v
    v v ,rl,r Y

    ?-.r<?
    W ///
    /\\\
    / -/ /

    m
    maaritc, BrEtoNe |tLl]le r/otr,ANrc
    [! J conoum.,roeu
    K4 rurrerue ANoE rrE I G?OU"

    fJ OroV,*ck,roKArEA utLL FM I UnUetl HILL .


    ffi e*yr*rka, MoEHAu FM I ocoue
    '/.at Faull
    Yeiv'r
    c 1arade Locafbrl

    Flgurc I-G-l: Geology of thc Petote Strean area (aftsr Sklnner, 1967t 19?6).
    35lj

    1. Propylitic; pyrite, epidote, chlorite, seeondary


    quartz, ealcite and clays.
    2. Sericitj.c; sericite, quartz and pyrite.
    3. Quartz-sericiti.e; quartz, sericite and pyrite.
    L. Silicie; quartz, pyrite, ninor seri-cite )
    chalcopyrite and covellite.

    MI}IERALISATIO}I

    Several nineralised quartz veins up to 2m wide oceur


    in the area (Fig. I-G-1) and consist of quartz and sulphid.e
    cenented wa1l rock breccias (Fig. lr-3). The sulphides are
    generally med.iun grained. comb and vug quartz are connon in
    some of the veins. The ratj.o of sulphi.de to quartz varies
    bu', is high in the Hutt creek vein, Galena Lod.e and chalcopyrite
    Lode, Sphalerite is generally the nost connon sulphide,
    followed by galena but chalcopyrite is particularly abund,ant
    in the Chalcopyrite Lode.

    A geueralised paragenesis (n:.g. I-G-z) consists of


    the following:
    1. Repetativesequences of brecciation sith subsequent
    quartz and sulphide deposition.:.(J-n some veins the resultin5i
    texture eonsists of individual grains of sulphides separated
    by quartz ).
    2. Comb and vug quartz with pyrite and soneti.nes
    chalcopyrite.
    3. Late calcite followed by kaolinite deposition on
    quartz crystals in vugs (only present in the chalcopyrite torle).

    The detailed paragenesis within Stase 1 of the Hutt


    creek, Galena tode and charcopyrite toce is conplex ulth some
    speclmens exhiblting banded textures (rig. r-G-3 , and also
    Plates 105 and 110 of Skinnerr 1967). The absenee of unneathered
    vein secti-ons at liutt Creek and the Ga1ena Lode nakes
    elucidation of the eomplete Stage 1 sequence at these loeations
    imposslble but skinner (1967) deseribed the banded aequence
    in half of a symnetrical crustified veinlet (originally 30nn
    witle) from the Chalcopyrlte Lode as follows:
    country roek t pyrite
    quartz f pyrlte
    pyrlte * ninor sphalerite
    355

    !fh#?* I 2 7 4
    Qanwtz
    Pyr.ita
    Chatcopynte
    ---
    Sphalentc
    ,dena
    ---
    C.alc:rlc

    Yaaliqtfe,
    Chalcocif.e
    eodiita
    Goethil'.a

    Fl,gure I-G-21 Paragoaet*c BsqUBBsB of ulnsrelt {tr ths *sinc of tho Ftto,to
    Stroai!. trn:at.

    I
    356

    -r''

    Ftgurc I-G-3: Sauiled, brecala, nedluu to coarge grrlaeili rulphLde olnerrllsatloa


    frol the llutt creetr veln (Sanple 13989, 5'5cn vlds x 5cr hlgh).
    I
    357

    I
    Artken i Pelolc Sfre,am
    gtrcarnl Galeno ctralcopyrrtc Lodc
    North Vcrn
    Lodo
    ouortz calcitc t40
    ,40
    .Tt
    |l :
    IL '@,6
    J
    o-
    rno 3
    l_/ tf '\T
    F- t $ F iF s
    t8
    o
    o
    6f
    o
    o
    l.tl Ffc o s
    \D
    :9
    22e{
    F
    tgo
    vr !G
    -\D 1961 (1
    a

    .D
    4 w a
    F \.n
    --ss
    I ri:
    1

    ? F 0 =*?
    I trI
    'Q
    o o

    Shgle value,sl 1 Fillmg Tcmp. 0 9alhity

    Flgurc f-G-{l lllstograle of prlnary flulil laclualon fllllng tenperatures end


    apparent sallnltles for aaoples of Stage 2 quertz (139801 1L006) 14005 and
    Chalcopyrlie Locle quartz: '13992 + 13993C + 1)995 + 13996 + 13997) and Stage
    3 calcltc (13991 + 11993c1 fron the Pstote Strear area. The lndlvtdual
    loasursilcntr are llstcd ln Appcndtx III.
    358

    chalcopyrite * ninor sphalerite + galena (irreguLar)


    sphalerlte * ninor galena (iiregulbr)
    chalcopyrite
    galena cubes
    quartz
    calcite
    sequenee repeated in reverse order

    The latter quartz and calcite (centre cif vein) equate


    with Stage 2 and Stage 3 respectively of Fig. I-G-z-

    Covellite replaces ehalcopyrite along fractures and


    rins in sone speclnens fron tbe veins ln Aitkea Strean tnd
    Petote Breek exauined by the writer. Supargene ninerals were
    not identified ln samples fron the Hutt Creek vein. Skinner
    0967) noted. Li.nonite, in addition to covell-ite, in sone of
    his samples and Edward.s (1979) also reported. replacenent of
    chalcopyrite by chalcocite ln the Aitken Strean vein.

    FTUID IiICLUSIONS
    F1uid inclusions in Stage 2 ouartz and caleite fron
    Aitken Strean and Petote Strean are nornal two phase li.quid
    plus vapour types except for a few inclusions in sanples
    13996 (pstO) and 14,006 (PS25) shich also contain a fibrous
    soLid phase (see Ghapter 5).

    Histograns of filling tenperatures and apparent


    saLlnLties are presented in Fig. I-G-4i A pressure - salinity
    correctlon of approxinately 1OoC nust be ad,ded to the filling
    tenperatures. Sone of the histograins are broad, and. lack well
    defined, nodes, however d.epositional ternperaturds are assigned.
    as follows:
    Aitken Strean Stage 2 quartz 3 29Oo
    Petote Strean north Stage 2 quartz 3 3109
    Galena Lode, Petote Strean, Stage 2 quartz z 2'IOo
    Chalcopyrlte Lod,e, Petote Strean, Stage 2 quartzs 290oC
    Chalcopyrite Lode, Petote Strean, Stage 3 calcite:250oC

    Partial chenical analyses of fluid inclusions in sanples


    359 -

    13907 (Hutt 2),139s0 (AS1) and 13gg8 (PS15), deternined, by


    crushing and leaching experinents are presented. in Table 7-7. .
    The Na/K ratios of alL these sarnples ('lZgol = 2lr, 13980 =
    15.3 and 13998 = 10) are roucb higher than the theoretj.cal
    values, between l+ and 6, predicted by the Na/K geothernoneter.

    HIDiIOGEI'I ISOTOPES

    FluiC inclusions in sarnples of quartz contain waters


    uith 5 D values of - 36.7 per ni1 (sanple 13998) ' -tr5.7 per
    nil (sanple 13g8O) and -4,8.9 peir ni1 (sarople 13gO?). These
    values probably result from a neteoric water origin (during
    a cooler clinatel however the latter two values are close to
    the'-50 to -8J per ni1 range considered charaeteristic of
    prinary noagnatic waters (Taylor, 1979) ancl nay indicate the
    presenee of a rnagnatic uater eonponent.

    SULPHUR ISOTOPES

    The 6lLS values of sanples fron the Petote Strean area


    are listed in Tabl-e 9-1 witb depositional tenperatures d,erived
    -from sp - gn pairs. Two of the sanples fron l{utt Creek
    (samples 13986 and 13989 ) give unrealistic tenperature
    estinates and a third (sanple 13987) also appears to be too
    high in conparison vitb the rernaining 6 tenperature estinates.
    Therefore it is eoncluded that Stage 1 sulphid'e deposition
    oecurred. at tenperatures around. 290 to 32OoC.

    LEAD ISOTOPES
    Cooper & Richard.s (1969) neasured the lead isotope ratios
    j.n a sanple of galena fron the Chalcopyri.te Lode in Petote
    Strean. Conparison with lead isotope ratj.os in sanples of
    vein galena, andesite, rhyoli.te (Cooper & RiChards, 1969) and
    greyvacke (lrnstrong & Cooper, 1971) fron other arsas of the
    Coronand,el Penineula (c.f , FLg. 5 of Roblnson' 19.71r) suggests
    that the lead. in the Petote Strean veins lras derived fron the
    greyvacke suite rocks.

    THERI'IOCHEMISTRY

    The geochenical environnent of the Petote Strean


    nineralisation is liniteil .on the fS, versus f0a diagran
    360

    Plnivad r, Ot*vcl
    Jratphide i Sulpfratz

    f.
    rn
    '7^,',
    s
    $!e ,i$'
    q; q#.
    !)$
    tTEsl HEMATTTE

    + -4? 4 -38 -rL -A -r2 'b -B


    Log f 0z

    Flgura I-G-5: fSa versue fO, dlagran at SOOoC chorlng the geocheolcal envlron-
    oent (ahadeil) of Stage 1 quartz + sphalerJ.te i galena + pyrlte +
    chalcopyrlte olnerallgatlon ln velns of the Petote Strean area. l8o0.01ar
    pH=1,6r 1og fS2 frou apbalerlta couposltlons . -9.0 lo -9.1+r and log fCOt
    froa fluld lncluslon tra6ulorontr o .11.6. (Sae Appendlx V for datalls of
    constrrrctlon. )
    361

    (Fig. r-G-5) by the presence of pyrite and chalcopyrlte but


    absenee of pyrrhotite, nagnetite, henatite and. bornite. tog
    fS, values between -9.0 and -g.tr are indicated. by the
    sphalerite courpositions and at these sulphur fugacitLes rog
    fOn is linited between -31*.4 and -31 .0 by the absence of
    graphite and magnetite respeetively.

    Sericite occurs in the wall rocks, whereas K-feldspar


    and kaolinite are absent (although kaolinite oecurs as a late
    stage vein nineral). Therefore. a pH of around 5.6 (near
    neutral) l* ind.icated..

    . An toz versus pH diagran, eonstructed. for a total sulphur


    in solution concentration of 0.01m (1og n4.s = -zr, is presented
    in Fig. r-G-6. The shaded area of the diagrau ("..d also in
    Fig. r-c-5) represent the region of nineralisation. A fluid
    with HS- as the predorninant sulphur speeies in'solution is
    indicated. Values of log fO, are between -33.0 and -33.5 at
    a pE of 5.6

    GE}IESIS

    Edwards hypothesized that the nai-n. period, of regional


    hyd.rothermal alteration- in the Petote Strean area vas related
    to deep porphyry copper nineralisation during the nid to upper
    Miocene and that vein ninerarisations now exposed. at the
    qurface rdere reLated to a l_ater second period, of porphyry
    nineralisation in the late Miocene to early Pliocene.

    Theforner ninerarisation is conjecture, however the


    vein nineralisations are undoubtedly associated with a period
    of intrusion of Kai-iti Porphyrites and their_ deeper equivalents.
    The vrlter envisages a g'eotherroal- systen initiated by the
    intrusives. The nineral-ising fluid was deeply ci,rculating
    neteoric water whioh leaabed nost of the nineralising conponents
    fron the greywacke basenent rocks. Sulphide deposition uas.probably
    a result of decreases ln fluid pH due to reactions with the
    wall rocks.

    The uncertainty of the dissolved. sulphate,/dissolved,


    362

    Kaoltnito, iSarrcte
    il!
    I

    I{EMATITE I
    -n
    -?s

    -t,
    o -n
    G|

    (F -31 EORNITE T PYRITE \I- UNENETITE


    J
    o CHALCOPYR,ITE
    '12
    !
    .,, PYRITE I

    -v I

    -19 Itbq iao?-,


    -%
    -t7 P{R,RHOTffE
    -t6

    Flgure I-G-61 f0, versue pH illagran at 300oC and (S.O.O1ar ehovtng the geo-
    eherolcal envlronnent (shaded) of Stage 1 quartz * sphalerlte * galena *
    pyrlte + chalcopyrlte ulnaraltsatlon ln velns of tho Petote Strean area.
    i - 0.11, ,gj '0.006. pH 5.6, Loq fSa fron sphalerlte conposltlons =
    -9.0 to -9.{,, log fGO, froo fluid lncluslon measureoents = *1.6, and the
    pH of the ealclte eoluble/lnsoLuble boundary . 5.(). (See Appendlx V for
    nsthodr of constructlon.)
    363

    su1phiile ratio of the hydrothernal flutd (c.f. tr'Lg.. I-C-6)


    prevents definltlon of 6'Ota, and the orlgin of the sulphur.

    Do,l{Ngr, J.F. 1935


    EDI{ARDS, P.E. . 1979
    FRASER' C. i ADAl.fS, J,U. 1987:. see pp 126 - 128
    scgoFIELD, J.L. 1967
    sKIlIl.{ER, D.l{. B. 1967
    1972
    1976
    IIIII,IAMS, G,J. 1971+z see pp 99 - 101
    .: .-.4

    iIHAIIGAPOUA Ai]D T}iE OPITO]{UI ].iI1IE

    INTRODUCTIO!{
    ' The 0pitonui Mine produced. 1 nillion grans (3O,9lZ
    ounces) of bullion (5l,l3l tonnes of quartz nined), pre-
    doninantly betlreen 1895 and 1901+, fron three eas',-1.'est
    strlking veins known as I'iaiden, Carvill and Hilda. Several
    northerly striking veins such as the Opitonui' although
    auriferous, proved unprofitable. The veins lJere nined on two
    adit 1eve1s anil lr shaft 1evels, all no1{ ineccessible.

    Robson (1979) recently investigated the geology,


    hydrothernal al'r,eration and nineralisation of the,. i'lhangapoua
    area concurrently with a strearn sedinent and. rock chip
    geocheuical exploration progran by Al't0CO (reported in l'loore,
    1979a).

    GEOLOGY

    The geology of the llhangapoua area (fig. I-H-1 ) con-


    sists of andesites of the Tuateawa Andesite, Beesons fsland
    Volcanics and l{hangapoua Andesite fornationsr intrudeil by
    stocks of hornblende diorite porphyry and. hornblende
    nicrodiorite porphyry. terned llhangapoua Intrusives by Robson
    ' (19?9). Several.dikes of andesite porphyry cut the diorite
    porphyry stocks and andesites. A11 fornations beiong to the
    Coronand,el Group.

    Fraser & Adams (tgOZ) described the rocks in the


    Opitonui Hine area as andesites although they noted that the
    presence of hornblende porphyry ltas indicated by a specinen
    found on the tip head.

    HYDROTHERI.IAL ALTERATTON

    Robson (1979) classifiecl the hydrotherpally altered


    rocks of the llhangapoua area into five groups as follolre (iu
    order of increasing intenslty of alteration):
    365

    1. lleak propylitic: chlorite, calcite and nagnetite


    2. Advanced propylitic: chlorite, epi-dote' launontite'
    pyrite, sericite (interlayered. illite : rnontrnorillonitei'
    ninor calcite, minor sphene, nagnetite and, rare adularia.
    3. l4agnetite-chlorite-calci-te: nagnetite, chlorite, calci-te'
    sericite (interlayered illite nontnorillonite), pyrite
    and chalcopyrite.
    l+. Clay-sericite (equivalent to argillic alteration):
    sericite (il-tite and interlayered iIlite nontnorillonite),
    chl-orite, pyri-ter euartz, and accessory sphene.
    5. Quartz-sericite (equivalent to phyllic alteration): quartz;
    pyrite, seri-cite (itfite and interlayered. illite -
    .nontnorillonite), ninor chlorite and accessory sphene.
    Kaolinite is restri-cted to shear zones ancl veins where
    it occurs with sericite. For exarnple, it is associated with
    vein stibnlte nineralisation.

    A boneentric zonal pattern of the di-fferent alteration


    types is not well d.eveloped because of the pronounced
    structural control which offseis the alteration qones and,
    induces llraited superposition or telescoping of assenblages
    (Robson, 1979). However, tuo centres of intense alteration
    Irere d.efined (Fig. I-H-2).

    M,INERALTSATION

    The nost producti.ve voin of the Opitonui Mine' the


    Maiden vej-n ranged fron 0.6n to lr.3m j.n width with an average
    of about 1.8n (Fraser & Adans, 190?). In the lotrest nj.ne
    level (/* levet at 113n below surface) thq width of jthe Maid.en
    vei.n contracted to 0.3n on intersecting a nhard barn which
    Fraser & Adans postulated to be a dike of hoinbl'6nde porphyry.

    Downey (1935, considered that the econonic ninerallsation


    of the Opionui Mine uas concentrated in conparatively
    restricted shoots near the surface' vith poor grades in the
    lower levelso

    Fraser & Adans described the ninerallsation as consisting


    of electrun, with approxinately equal proporti-ons of gold and
    365

    /) * /*
    ''\\ffx x 6 x,{-v

    F,'g(r,ry'ffi \t.

    |C*:'jffi
    \ /-t
    ,t, / \.1 r'*(* \jxx
    xx
    ,a\
    A Vr
    t^
    t\ t /, n i

    r"ir
    \ \ t iX
    I
    )* in
    IX }7
    ol
    \i* a
    K^, v
    iopiioiui^
    /-4 r x * ,[l
    Yilovnelra;" 1
    a \^
    \ Frl;;-
    )t
    CORO}'/AN?5L gR)U?
    Extruirve, RocVg lnfrug\ve, ?ocks
    WHANGAPOUA ANDE9ITE FORMATION WHANGAPOUA INTRU9IVES FOR}.iATION
    porghyrfic ande,Afe diKe, (lnformal unit )
    N
    d il:nr,g?' fiN!!" xo'lc PYro @ Q6,te, porphyry (6mr Rock)
    BEEIzNS ISLAND voLcANlct F0nx,tnttoN s nndcsiia porphiry drke
    EI no-ulcnde- pyroxs'r1q mrda,E\fe, flows ffi Honnut ande,- rficrdionla gorphyry
    TUATEAWA ANDE9ITE FORMNTION ffi oiorifc porpv'.l^t
    ffi a+t$te.- inr1ry;sN'v,ne ar:dredffe. fbws
    t)ndiftaranfthte.d
    ffi vot* ritclaglicE
    / Ye.in .'-'Faull / ?,oad
    f l"lw;rstfnenc atgite. andcslfie dike,

    Flgure I-H-1: GeologY of tlre Whangapoua area (after Robson, 1979).


    5it.
    \.\ \ \
    (\ \\\
    Y.
    \
    \-hL? \ \'
    /z\ \ \ \,\\ \
    \-/ \ ' \ \'r

    tl{i
    r\\\
    \ \ \ \:1\\
    A\
    2A'.,
    \txr
    /\\
    - \ \.
    \ \ \\\
    \ \1.-\
    \ \ \ \.;+---l
    \ -
    [r r
    Lr

    !t I

    .,1Yxr\
    '-.'lX-/\\ \r
    \
    Y N \
    .\5
    {rli*,,S. \

    N
    Ir.\
    Rrt \>
    l.'Wi
    R
    _r. Y

    N 'r\\\\ \
    t..$+
    ".tit
    .\r t

    7 Vnallered rocXt n cby - 5aricte alleration

    etopylilrt N Quartz- Scric\tc alteration


    $ altorafrov't

    8lgura I-H-2: Generallged digtrlbutlon of hydrotheraal alteratlon zonaa Ln


    tho llhangapoua area (after Robson, 19191 .
    36s

    illnt"rlg I u' tll TT


    Fc Ph;?n,Ag.lb-rSb-Cu(Fel As (Fal sb

    nytlt! =---
    m rearltg
    nilrrgyrltr
    tatrahcdrJ'tc
    frslbrrgttc
    'fatnrtfnlta
    sphrlcrltc
    chrlcopyrltc
    galttu
    .ntlilny [nattvc)
    artflrlrnatasa,
    rrceaopJrlte
    rtgenle '(nrtfue)
    .stlbaltr -

    ftgu e I-S-31 Poragcnetl.c sequetce of qlu-orals La vcdnr ofl the lfhqngepour


    alorr (Frou Flg. j.2 st Roboon.l 19?9!)
    369

    silver, fairly evenly disseminated throughout the quartz vein


    although some concentrations oceurred nin eertain thin partj.ngs
    in the veintr (Fraser & Adans, '|907 p130).

    Robson (1979) studied. saroples fron a 0.2n wide quartz


    vein and float in llaingaro strean-, apprixinately z.5km wedt-
    of the Opitonui l'Iine. The noineralisation consisted of various
    assenblages of pyrite, trareasite, stibni-te, arsenopyrite,
    niargyrite (agSUSr), tetrahed.rite, freiberglte (argentian
    tetrahed.rite), fanatinite (CurSbSO), sphalerite, chalcopyrite,
    galena, native antinony, rutile/anatase and native arsenic.
    R.obsonrs proposed paragenesis is shown in Fig. f-E-3. Sti-bnite
    associated with banced and vug quartz and occasionally also
    pyrii,e is the only assenblage found conrnonly in float of
    lfaingaro Strearn.

    Rare isolated occurrences of chalcocite,' nolybdenite


    and pyrrhotite lrere record.ed, fron a few localities by Al't0c0
    (Moore, 1979a).

    FLUID INCLUSIONS
    Robson (1979) deternined fluitl inelusion filling
    temperature ranges of ?70 37OoC and 220 - 360oC for an un-
    mineralised 1rn wid.e quartz veln and unnineralised quartz float
    respectively in upper.hlaingaro Strean. Eistograns of the
    filLing tenperatures (rigs 5.5 and 5.6 of Robson) have nodes
    at approxinately J00oC. Robson correlated his Stage z
    nineralisatlon with 2?0 33OoC group5-ngs in the filling
    temperature histograms.

    A float sanple fron Waiugaro Strean, studied by the


    writer, contained needles of stibnite intergrown with vug
    quartz crystals on earlier vein quartz and pyrite. The sanple
    is correlated with Robsonr s Stage 4. nineralisation. The
    quartz crystals contain iany vapour filled primary inclusions
    indicating that the hydrothernal fluid uas boiling at the
    tine of crystal growth. Tvo nornal type prirnary inclusions
    gave filling tenperatures of 1 90oC. This sanple was also
    crushed and leached (Chapter 7) to deternine the chenical
    couposi.tion of the incLusi-on fluids. The results ind.icate the
    fia

    TABITE f-H-1 : Genera,L thern,oehenleal parenete'rg for Stbge 2 aud


    Stage I quartz vela utrnqral'lsatl'on ia tbe trfaLag-aro
    Strsar alea t{hangcPoue.

    Stoge 2 Stage 4 Befolence

    Telpelattrre o0 280 (crura bolltng) Tabile lt-l


    0.2'l 0.11 !l
    Tlue Lonic strengtb
    l|
    Saltnlty (rc lta01 eq.) 0.26 0.11
    o,01 2 I
    rK* 0.045
    pI 5.1 5'2 See tert
    pft of kaolln1te/ aertei.te
    boundary 1.' labne V-1

    plt of rorLcltr/fi-f eldcPar


    ''2
    tounilary 5.8 6.t i

    tstal S (log a(S) -2.Q -3'0 Sae taxt


    Log lS2 (sphalcrlto ooDpo) -9-Tto-9,9 [abX.a V-lD
    I'oe lOe -93.5+,o45.A -39tP-[1.,5 .f-lgures ei.tad
    (Fle. I-il-5) (Ple.I-,il''6)
    ros N00a +1.5 #2. O
    371
    -

    presence of 23OA ppn lla*, t 5o ppu K*, 3?00 ppn C'l- and 0.8
    noles/kg of COZ.
    .

    SIITPHUR ISOTOPES

    .' j... .. Stage L stibtite nnd. pyrite fron-float_in Haingaro Strean


    have 634s values of +1.5 and. -2.1 per nil respectively.

    HYDROGEN ISOTO-PES

    Fluid inclusions in quartz (sanple 13910) from the Stage


    ,(, quartz plus Stibnite nineralisation contain water with a
    5 D value of -117.6 per nil. This value is close to the upper
    linit of the 5 D range considered. characterisiic of prinary
    nagnatie water (-SO to -85 per nil) although eonsidering the
    paragenetic position of the sarnple a predoninantly neteoric
    water origin is considered. nore l-ikely. '

    THERI'IOCHE}'IISTRY

    Introduetion
    Table I-H-1 lists the paraneters of the vari.ous geo-
    cheni.cal environnents nodelled. lhn the following seetion.

    . of the hydrothernal alteration


    nbUsonts d.escrS-ption
    indieates that with the exception of the low tenperature
    (approxinately 200oC) Stage 4, fluid which deposited. kaolinite
    the fluids were in equilibrium with sericite in the wall rocks.

    Staee 2

    An fSa versus tenperature diagran (Fig. I-H-4) denon-


    strates that not all of the various ninerals _grouped in Stage
    2 by Robson (Fig. I-H-3) were in equilibriun at the satre'time.
    At least two mineral assenblgges can be interpreted. fron
    Robsonis text descriptions: (a) tetrahedrite, fauatinite,
    freibergite, uiargyri-te and native antirnony (Robson, 1979 p1?7)
    and (b) pyrite, sphalerite, tetrahedrite, chalcopyrite and
    galena (Robson, 19?9 pp121 123). The forner is not an
    equilibriun assenblage because native antinony and fanatinite
    are deposited under very di-fferent fSZ conditions (fig. I-H-4).
    372

    jry

    ...X -"
    |.h, ;$9
    ;.\9
    -9_,,
    ,c
    Fr

    2n'c
    _rli

    1.9
    looo
    To Kclvivr

    Flgure I-H-4: fSa versus tenperature dlagrao for varLoue sulphldablon reacitons
    relavant to the Whangapoua (l{alngaro Strean) nlnerelLsatlons. The diagran
    deuonstrateg that natlve antlraony and faoatlnlte of Robsonrs (19?9)
    Stagc 2 ulnerallsatlon rere deposlted under very dlfferent fSa condltlons.
    (Hothods of constructlon are glvan ln Appendlx V. )
    t't3

    For exanple, at 280oC (corresponding to 1.8 on the 1000/T:1


    scale in Fig. r-H-4) the famatinite/tetrahedrite boundary ,
    occurs at a 1og fs, value of approximately' -7.7, uhereas
    native anti-rnony is stable only at 1og fs, values less than
    (nore negative) -13.0.

    The FeS eontent of Stage 2 sphalerites analysed by


    Robson j-ndicate 1og fS, values betlreen -9.'l anii -9.9 at 280oC.
    Therefore log fSa values between -7.7 and -1 0 are considered
    here for stage 2 nineralisatioq in the fOa versus pE diagran
    (Fig. I-H-5). The native antimony is regarded as a later
    phase possibly occurring with arsenopyrite, native arsenic
    and.rutile/anatase of Stage 3.

    Tworegions of Stage 2 nineralisatlon are shor.rn in


    Fig. I-H-5, area A representing the tetrahed.rite,' fanatinite,
    freiberglte and roiargyrite nineralisation and area B the
    pyrite, sphalerite, tetrahed.rite, chalcopyrite and galena
    nineralisation. The transition fron one to the other con be
    characterised by chauges in fOa and fS2, probably a reduction
    i.n values of both paraneters so that nineralisation nAn
    preceedecl nineralisation rrBrr.

    Staee 3

    The appearance of Stage 3 nineralisation represents a


    red.uetion tn fS, (with or without a drop in tenperature) fron
    Stage 2 particularly if native antinony was d.eposited in the
    latter stage (c.f. Fig r-H-4).

    Stase 4

    The possible range of conditions for stibnite


    ninerali,sation at 200oc are shorrn by the shaded, area in
    Fig. I-H-6.

    for a total sulphur in


    The pH contours'are constructed.
    solutlon eoncentration of 0.001n (Iog rz{S = -3). At values
    below 0.0005n (1og nls = -3.3) sb2s20 is stabre rather than
    eti.bnite.

    Except uud.er cond.itions of high sulphur fugacity (J-oe


    37 t,

    G|
    o IMAGNETITE

    s -7q13;;=8----1
    -t+{Lzt'-*---l-----

    PYRITE

    FfRRHOT h

    PH

    Flgure r-H-5c fo, vereuo pH dlagranr at 28ooc aui!{s-0.01n ehorlng the geo-
    cbenlcaL euvlronoents of (l) Staqo 2 quartz * tetrahedrite * faraattnlte +
    frelberglte * nlargyrlte ninerallsatl.on and (B) sta4e 2 quartz + pyrlte +
    sphalerlte * tetrahedrlte + chalcopyrl!6 * galena nlnerallaatlon ln velne
    of the welngaro streao area, whanqapoua. (seo Tabla r-H-'l for relevant
    theroochenlcal paranaters and Appendtx V for nethods of constructlon.)
    375

    I
    I r'#
    (\|
    (n
    r.|a
    et\
    o
    J
    ,ifl \
    uEMArrrl

    ,l'.Fr:1
    ilLirt
    h;,
    -rz -n -4t -{ 44 -42 q -?$ -* 4
    Lqfoz

    Slguro l-H-61 fS2 vemUl fOO dlagran at Z00og rhortng the geocbeltaaX,
    enylronrent (Irre of croises) for Stago { quertr + stlbnlte + pyrttc !
    , laoll.rlte depositloo Ln rsins of tbc Ualagaro'Stresr arc,a, Ibon8apoual

    (see Table tr-[-l fsr raLovant tberloobenlcal paraoetcre and tppendlr V for
    dotal,ls of songtruetlon. )
    376

    fSZ ) -t0.4) stibnite is deposited fron fluids in uhish


    dissolved sulphid.e predoninates over sulphate. At log fSa
    values greater than -10.8 concentrations of dissolved, sulphate
    may be equal to or slightly exceed dissolved sulphide, houever
    because gb2s20 is absent highly oxidised fluids are precruded.

    GENESIS

    (tglga) consid.ered that tha


    Robson (1979) and l,loore
    pattern of hydrothernal alteration zones and, stream sedinent
    and rock chip geochenistry in the i,,ihangapoua area was
    charaeteristic of a..high leve1 exposure of a porphyry copper
    deposit. Robson (1979) suggested that the postulated, porphyry
    copper nineralisation was related to intrusives enplaced below
    a developi.ng stratovolcano in the upper Miocene. Regional
    faulting during the Plioeene provided zones into nhich the
    l-ate nineralising solutions nigratecl and deposited. the
    nlaeralised quartz veins.

    The writer considers that the hydrotherraal fluid


    responsible for the vein nineralisatlons uas deeply cireulating
    neteoric water. The change in fluid chemistry fron Stage ?A
    through Stage 28 (Fig. I-H-5) to gtage 3 is one of progressive
    reduction of the hydrothernal fluid (increasing proportion
    of reduced aqueous sulphur species in the fluid) and, was
    probably the priucipal nechanisn''of sulphide d.eposi.tion fron
    chloride conplexed uetals i-n soluti.on. Durlng Stage 4 boiling
    of the hydrothernal fluld with conconltant loss of H^S caused.
    d,epositioa of stibnite fron sulphide cirplexed antirnfny in
    solution. Changes in pH resultlng fron reactions of the fluid
    wlth waI1 rocks nay also have pronoted. nineraLisatioa,
    particularly the acidic pH during Stage 4. indicated. by the
    presence of kaolinite associated. with the stibnite rnineralisation.

    REFEREIICES AND BIBTIOGRAPHY

    DOIIINEYl J.F. ',9353 see pp 5lr-59


    FRASER, C.i ADAi'lS, J.H. 1907: see pp 1?g-1j0
    Mo0RE, C.R. 1979a
    RoBSOll, R.N. 1979
    SCHOFIELD, J.C. 1967
    SKTNNER, D.N.B. 1976
    IfIILTAMS, G.J. 19712 see p104
    377

    I-I
    )'IAIIAIA

    IiITRODUCTION

    Quartz vei.ns lrere worked between 1885 and 1901 in two


    areas of the l"lanaia Valley, the Golden Hills (or Victoria)
    Clain and the Jubilee Cl-ain, but yielded a total of only
    9,000 grans (296 ounces) of buLlion (Dor.rney 1935).

    Reeently AM0C0 Minerals Ltd identifled porphyry style


    nlneralisatlon r.rhich was subsequently described by Stevens
    (1980).

    CEOLOGY

    The geology of the Manaia area was described by Fraser


    & Adans (1907), Cornwe]_l (1967) and Stevens (1980). A
    geologlcal nap and cross sedi.on based on the l-atter description
    are shown in Fi3. f-I-1. The najor uni.ts are as follows:

    l,lanaia Hill Group (Jurassic): sreywacke sandstone, arg5.1lite,


    chi.pwacke and eonglornerate.
    Coromandel Group (i{iocene) : Beesons Island Volcaniesi
    a4desite flows and volcaniclastics
    Kai-lti Porphyrites: stoeks
    and di.kes of hornblende
    andesite porphyry, hornblende
    quartz diorite porphyry,
    hornblende microdlorite porphyry
    and. hornblende. olcroquatt,z
    d.iorite porphyry.

    Stevens (1980) inferred age relatlonships betueen the


    intrusives by the presence or absence of hydrothermal altera-
    tion and mlneralisati.on and considered that two or three
    separate periods of intrusi.ve activity occurred.

    Stevens also noted. the oecurrence of an 0.2m wlde breccia


    d.ike and several pebble dikes (ni1led breccias) generally less
    378

    than 1min width. They all occur in l'{anaia Hill Group rocks.
    He suggested that the dikes r.ter.e a result of hydrotherroal ,-

    activity; the breccia dike probably being associ-ated with the


    intrusion and. related hydrothernal activity of a hornbl-end'e
    quartz d.iorite stock. blt the pebble dikes post dating this
    period.

    HYDROTHER}.{AL ALTERAT I ON

    Stevens classified the hydrothernally altered rocks of


    the l,lanaia area into the f ollowing four groups, in order of
    increasing intensity of alteration:
    propvlitic: (") pvrite'
    'neak ;il:H':":::'":i:il:"'
    (b) greywacke suite roeks:
    chlorite and pylite.
    2. Advanced. propylitj.e: (") igneous rocks: secondary quartz'
    epidote, clinozoisite, chlorite'
    calcite, pyrite, nagnetite'
    leucoxene (rutile and
    anatase), seri-cj-te (inter-
    layered il1ite-nontnorillonite)
    and very rare tournaline.
    (b) greywacke suite rocks:
    pyrite, chlorite, ePidote and
    sericite (ittite type claYs).
    3. CIay sericite: igneous rocks only; secondarY
    quartz, pyrite and clay (i[ite'
    interlayered i1lite-rnontnorillonite r
    chloriter'interlayered chlorite-
    rnontnorill"onite ancl some kaolinite)
    lr. Quartz sericite: ( a) igneous rocks: seconclarY

    quartz, serieite' (ittite


    and Lnterlayered illite-
    nontnorillonite), PYrite,
    chlorite and interlaYered
    ri 11 onite.
    chl ori te- nontmo
    (b) greyuacke suite rocks: PYrite'
    chlorite, sericite (ittite
    and interlayered. illite-
    nontnorillonite) and inter-
    3.ayered, chlori te-nontnorillonite.
    t'tv

    d-.
    \ \f

    6..L
    F

    ')* + Er +!

    v /vr
    \v/ v
    w
    v "\.v v\.

    E Horrtblende,
    Andadfa,, 9EE5ON, I9LAND
    avartz microdior\lc
    VOLCANIC9

    K mlciodtorl'tc.
    C- PrPhyY. rai- iti COROMANDEL
    GROUP
    E llornblct:de, quarlz dior\tc crrPtryy Porphyrilas

    f er^yarke,, undsfone,, argilllfe, a conglomcrafe, MANAIA I.IILL 6ROUP


    w,Hydrofnarrnal bruccia dke'

    --'FAull -..--r..WAlkrhg'lrack

    Al
    CToEE
    f\ A ,oo p
    U
    +I s
    v 2oo'E
    .s wo I tlt ,O .E

    .5o v
    Y
    lir +{+
    I oE
    E
    I -rob
    v ti,
    I
    I
    ++.1..1
    +++ -'-
    U 7-- l+ + + +
    .:
    -E
    -2Ao u)
    6 -20c

    Plgure I-I-1: Geologlcal uap and croae-aectlon of the Hanata area (after
    Stavens. 1980).
    P roVylil ic alferatior'r
    chlorita, caldte, mhgnelite ton. Advarrccd propyl;trt
    I allcraliott
    Egidore zor'rc I
    Clay -
    sericilc alterafon
    Quar|z - qeriirle allcralwn
    Alturafcr'r attoaotd w\h latc
    etage hydrolnervnal acfivity
    Walkrha 'fracY

    Flgurc I-I-2r Hap aod crosa-sectlon of the hydrotheraal alteratlon roner ln


    the Narala area (aftor Steveng, 19S0)'
    3,81

    - PERAL DORPETF.I I BoPBEIBY tl EDIlEESlllt g,pFE CENE

    '
    Dygldc -, -'t ---'i a

    Al-slcliler
    Ghalo.!ryrl,te
    lblybdcnttt '''' ' ;'l ' '
    GoLd ' , , ',t-
    adrclsdtc +=
    ' - '-'
    Gelena
    - t{agrctlte
    Ourtta rf

    . tiarctsitc

    . Gslrrulll.tr
    rdnpnttn/
    Jarodts r :'

    llrlaelrits

    Elgrrrc l-N-Ar Paragcncttc toquoDca of ,utncrrll,satl,oa la hc tl'aqal.a qrsa' (fror


    I!6. {.1{ of Eteronsr 198Or)
    382

    A zonal pattern of hydrothernal alteration occurs around


    a mineralised (porphyry style) quartz d.iorite porphyry (Fig.
    I-I-2) as follows: 1. a central core of advaneed, propylitie
    alteration, 2. clay sericite, 3. quartz sericite , 4. advanced
    propylitic' 5. propylltic, 6. alteration restricted to veins
    and sbears (epitherrnal aLteration), and 7. propylitically
    altered dikes and snall stocks, away from the main area of
    alteration and post-dating the porphyry niaeralisation and
    alteratlon.

    MII{.ERALISATION

    Stevenst paragenesis for the niaeralisatlon in the Manaia


    area 1s shorrn in Fig, I-I-3.

    Porphyry style nineralisation consisting predominantly


    of quartz-pyrite I chalcopyrite vein stock,rorks and nagnetite-
    chalcopyrite t pyrite veins occurs in the pervasively
    hyd.rothermally altered rocks. Two stages of porphyry
    mineralisation and hydrothernal alteration were recognised
    (Flg. I-I-3) - altered to advaneed. propylitlc assenblages
    Rocks
    (Stevenst chlorite-cal-cite-magnetite zone) contain pyrlte,
    uagneti.te, chalcopyrite, sphalerj-ter galena and nolybdenite
    (ln order of abundanee) mlueralisatlon in quartz veins and
    infilllng joints and shears and are grouped, as Porphyry I in
    Fig. f-f-3. Porphyry II ioineralisatioo occurs in the quartz-
    sericite anC clay-sericite altered rocks and consists of
    pyrite and rare pyrrhotite anil chalcopyrite in intrusive host
    rocks and pyrite and rare chalcopyrite in greywaeke suite rocks.

    Epithermal nineralisation (Fig. I-f-3) consists of


    quartz veins with pyrite, mareasite, sometines kaolinite and
    presunably rare electrun (e.g. in worked veins of the Oo1den
    Hi1ls and Jubilee Claims). Pyrite nlneralisation in the
    brecci.a dike in l.lanala Gorge was also attributed. to the
    epithernal stage.

    GENESIS

    Stevensf nodel for the Manaia porphyry nineralisatLon ls


    j.Ilustrated. in Fig. r-r-4. Ee consldered that a hyd.rothernal
    383

    o- 5'':-
    "lot.3.niordi
    : 1.,
    ,o - - '
    - -e ,
    c
    E -9
    oo
    Ati o
    L
    >r f{ o
    I
    o
    t'ok
    QO
    A>
    Ovl
    T'E
    >rd
    k-l
    hi'
    i/--t'?
    >ql
    .cE qt t\ .Fi
    "i
    9.
    AE
    o
    AO
    E
    ,
    O+t Lt
    t
    +t 'ttg E.s
    |.st e9
    o
    q{E
    qt
    J
    t .f
    ^O
    oh
    co +t
    o\ cr)

    nEoce
    vOS

    slctL
    6
    E
    e
    o
    L
    ii3i -k I

    95
    o+)
    dcto
    s
    E
    INJd
    !lx
    >r lZ
    e_ q b
    .rtoo;i
    oco:
    o)tlo\l
    OoFI
    rL-{ I
    ofr - |
    ,.(rol
    o.c50 tr I
    I
    r{n}I
    oo;
    {to+t
    o-qra
    .f:
    - q{
    nd
    {)o
    t+t
    Hdh
    lg,
    Ho. qiD f->r*
    OO+l
    kde
    a E g-"---
    h0
    ;l ;;
    3q a'
    E8 3.E
    6 ::1 =-
    >o
    s_E_
    \s
    CL .C' lLL
    Oa
    r
    , >
    t\ 9= r t'-E
    r o
    \t 9=
    teL

    systeu eonsisting of neteori,o water end. Late oagnatj.c ftrultls


    was in:ltiated by the intrusion of a quartz dionito porplyry
    and produoed, a central zono of ad,vaqced propylitic abratLou
    (.ehJ-,orite-.eatreite-nagnetlt sone) and .Porphyry f aineralisation.
    Tbi.s wes largely overpfiated !y con,tinued bydrothernal activlty
    uhich produeed the eoncentric clay-sericlte and quarluz-
    serieite and uarginal p-rop5plitic zon'es aad porphyry rr
    nineraltr.sa:tLon.

    Cessetl'sn of pervasive atrteratlon and ninerallsatiqn was


    fo1lowed by a resurgenee of nagnatic acti.vlty nith the
    intruslon of dikes. An eptrthero.al uinerall.satLoa event
    followecl thls, givlng rise to quanta neefs and pebble d,ikes.

    BET'EfrElrCES A$p pTnLI0GRAPHI

    trf,L.
    coRlluEtl,i 195'l
    D0WUEI, J.F. 1g3ir ses pp 66-6V aad 26g
    FBASER, C,; ADAHS, .f ,8. 1g07t see pl29
    S0g0FIELD, J,C. 1967
    STEVENS, M.R t . 1gg0 r'
    WILLIAM$' G.f . 1971+s see p10{,
    385

    I-J
    KAPOI.IAI

    II'ITRODUCTIO}I

    Three srall- ui-nes in the Kapowai area (Kapovai, l'Ielcone


    Jack and Big Beetle) produced. 192,000 grans (6,15a ounces) of
    bullion fron 5,'186 tonnes of quartz between 1899 and 1933.

    In tbe late 1960r s (reported in Nellson, 1968)


    ASARCO
    investi.gated the area for posslble 1ow grade bulk tonnage
    prospects but were unable to flnd any favourable areas. AH0C0
    are presently investigating the area but results fron their
    work are not availabLe.

    GEOLOOT

    The rocks of the Kapowai area consist of i'Ihitianga Group


    rhyolite f1ows, tuffs and aeglonerates (Eig. I-J-1 ).

    HYDROTHERI'{AL ALTERATI ON

    Neilson (1 968) noted that various zones of silicification


    (Fie. r-J-1 ) occur in tbe rhyolite tuffs, whereas the flow
    rocks are generally unaltered,

    MINERALISATION

    According to Bell & Fraser (1912I gold ni-nerallsation in


    the Kapowai Mine vas confined to snal1 pipes and segregated
    veins in an east-west trendlng, southr,rard dipping, zone of
    siliclfled. rhyolite tuff. The footwall of the zone ls fairly
    well defined and dlps at angles less than /r5o tut the hanging
    wall portion nerges gradual-ly into unsilicified. altered.
    rhyolite tuff. The width of the zone is d,escribed, onl.y as
    trwiilen. The largest pipe, 0rConnersr had naxlnum horizontal
    dlrirensions of 15m x 9n and was followed vertically for 21n to
    near surface where lt spl1t into a nunber of branches.

    Bell a surall easterly dipping pipo


    & Fraser also describe
    with a naxinun d,ianeter of 3.7n which nas stoped. vertlcally
    for 1?nrand a 75cn wide ncross-refrf uhj-ch was stoped,
    vertLcally for 115n. These authors noted, that the lensoid,al
    386

    Flgure f-J-1: Geology of the Kapovai area and plan of the Kapoval Hlne (after
    Ne1leen, 1958).
    387

    pipes were erratj-c and there was no feature in the surrounding


    rock to indicate where they night occur.

    In the Welcone Jack l{ine, gold nineralisation oceurred in


    a 20cn wlde quartz vein striking 0g2o and d,ipping steeply. to
    the south. The vein is in rhyolite flow rocks and was nined
    fron two levels. The ore shoot i.ras approxiaately 50n long j-n
    the upper 1e're1 but wedged out with depth and becane non-payable
    approxinately nidway betveen the two levels.

    GEI{ESIS

    The oecumence of gold nineralisation Ln pipes at the


    Kapouai Mine suggests that, like soue other deposits in
    rhyolite pyroelastic rocks (e.g. Broken Hills and the B1uffs
    section of lleavesville), electrus deposition nay have been
    linked with proeesses of boiling and hyd.raulic breceiation.

    REFERE}ICES AND BIBLIOGRAPHY

    BELL, J.M. ; FRASER, C. 19123 see pp 72 - 71,


    Dol,*iltEy, J.F. 1935: see pp 192, 193 and 289
    NEILSEN, K.I. 1968 ra
    scHoFrELD, J.C. 1957
    I'JILLIAMS, G.J. 1971+: see pp 122- 123
    388

    I-K
    BROKEN HILLS

    II.iTRODUCTION

    A nunber of snal1 gold deposi-ts occur in 'rtrhitianga Group


    rhyolite roeks of the Broken HiJ-ls area. Tbe bulk of the
    nining activity was confined to the perioct 1895 - 1913.
    Downey (1935) recorded that up to 1935, 1.? million grans
    (551199 ounces) of bullj.on uere recovered from 40,015 tonnes
    of quartz. The Broken Hills Mine accounted for nearly a1-J.
    of this production: 1.6 nillLon grans (5'l,012 ounces) conpared
    with 114.,000 grans (3,611 ounces) fron Golden Hills and 15,000
    grans (5lA ounces) fron various other nines in the area.

    The Broken Hi1ls nineralisation was i.nvesti.gated by a


    Newmont - Itinzinp (fCf) jotnt venture reported by Uttlng &
    Ad.anson (1971r) and nore recently by a Mlnzinp - I'latties joint
    venture who drilled a 300n hole to test the conti-nuation of
    the nineralisation into the andesi-te underlylng the rhyolites.
    Infornation on the latter vrork is not available.

    The geology and ninerallsatlon of the Broken Hills area


    were recently descrlbed by Moore (1976, 1979b).

    GEOLOGY

    The geologyof the Broken Eills drea is illustrated in


    Fig. I-K-1. In the vlcinity of the Broken HiJ.ls Mine flow
    bauded rhyollte (t{lnden Rhyolite Subgroup) is overlain by
    rhyolite pyroclastics (Corog1en Subgroup), capped. by several
    slnters. Three breccia plpes occur, two are intersected in
    the nlne and the third is se6n in surface exposure only (Moore,
    1976). The largest breecla pipe (ton in dianeter in 2 levet)
    is rapresented by ucavert stopes in 2, J and 4 levels (Fig.
    I-K-2) and is believed to eomnence in the flow banded rhyolite
    of l+ Ievel (Uoore, 1976). A snaller pipe is found in 2 and
    3 levels near their eastern portals.

    HI:DROTHERMAL ALTqRATION

    The
    .
    hydrothernal
    ,i;
    alteration of the pyroclastics is
    389

    W
    ffi'.
    -. !,i
    ),':i:
    ,)\3il,Lili'r$iilj
    JJ i
    1'.!', iai
    V'$:i:i\;i-S:lij
    'I1l,iil;.
    .xr,',t',' ) -l : i l-l.!t

    '::;'i.i;;,;"1L; ;/" x x

    ;,i11,L1t-; i'l:
    iftii.r:';;I^:W"x
    J,'i1_'.]o':, xx
    i.l'-S.,'l.':
    lil'rffi#':iy'^o.^ * T
    fiiH YTi,if^Hlffr,
    i^'ffifilW
    iflr
    l;lif,i
    j'r',7:,

    u oDse,'vedfoults I I1THOLOOY utlffs 0F wHlTtailGr 6&wF


    I a-,.tt- I yoLcA H,CS W rfv tHFoRtilL
    -:^a^-J

    )::';l;'#0,!T::"^o,,,", ottitucie
    lrrrr* E oruvium NAttES I'ID UNCEPT''V
    stn At t 6P t PH, c P asrTror
    l{l - I rLE'r uLc*
    ,, ;; i J, ii
    tlow bonding ptESrOCEpe
    - -- r
    rl:n: ,,
    "ii',
    uJ,
    I Mff :, ffiDocJte
    @ntonituns
    centre
    P.. dditz';i:;ve l r,orr*
    -'--- -- N#xli;'lii::
    lo" banded Rhyolitc ^
    {:+}Broken Hilt
    Pyroc!oslics
    | f

    -(A Trisnometricotstotionluncexe E,e";;I;1tr,.

    Figure I-K-l; Ceology of the Broken IiiILs area- (fran F1g. 1


    of Moorer 19?9b.)
    390

    !.r*rra aw*

    r..( --*
    -

    ptgurc tr-[-2r Dlagrsnetts dtosl-gocttron Ef r-ho Bloks El'tle t{!ng. Dctel,ld


    dnc plrna rarg: g{vcn by utttag I f,ieoson (19$l rnd }loora 119?16r.
    391

    ! a}/-@Ift.
    Mrne Tunnsl
    t, Vsin

    llgrrrr f-f,;lr PIas ot thc votue ln lov level,.s of tlr-q Brohoi f,ll].r illne (cfter
    8;U-r Fraer!, 1912).
    392

    generally in the forn of sillcification although arg1l1ie


    alteration occurs ln various pug vei.ns, punice clasts, and
    snall breccia pipes in and, above 2 leve1 (Moore, 1976). fn
    contrast, the predominant alteration type in the flow band.ed
    rhyolite is argiI1ic. Moore (1976) described. the clay
    nineralogy of the argillic alteration as sericite (illite ana
    i1lite-nontnorlllonite courplexes) lrith ninor kaolinite and
    amorphous c1ays.

    Adularia occurts in the wall rocks adjacent to the veins


    and nay record an early quartz serlcite - adularj.a stage of
    alteration whlch was later overpriuted by argillle alteration.
    r.,TTNERAI.I SATI0I
    A cross section of the Broken Hil1s nlne ls illustrated,
    in Fig. I-K-2 and a plan of the vej.ns encountered during
    nining in the lover levels (e.g. Battery Level) ls shown in
    Fi,g. I-K-3.

    Minerali.sation occurred. in breccia pipes (d,escribed. in


    the geology section), siliceous zones and quartz veins. 0,n1y
    the latter proved econonically lnportant and. of the various
    veins nined ilo. 1, ltlight, Blueher and t:Jestern uere the nain
    producers of gold.
    .r

    strike approxinately north-south and dip at


    The veins
    high angles to the west. BeIL & Fraser (1912) noted that they
    characteristlcally contained, chalcedonic quartz antl wall rock
    breccia and seldon exceeded a thickness.of 2.lrm. Slickensided
    selvages uith puggy naterial and quartzose crusts along the
    vein-walls were connon. The veiu ore uas nainly confined to
    shoots oceurring in the zone shown ln Fig. I-K-3. Within
    the shoots the rlchest or occurred at the intersection of
    the nain reefs with flinty stringers (particularly the one
    known as Slwerrs Leader), at narked. bends i.n the reefs them-
    selvesr or at the localities ftere the reefs joined.

    Battery Level has collapsed not far fron the portal and
    therefore Mooret s stud.y of nineralisation in the und,erground
    dorklngs was confined to the upper 1evels where only the
    393

    5110e 5rqf" t'T"


    lv??<,
    euartz 'trrl
    Pvrffe.. --
    (lu,Ad,, A;5e5o
    Czraronff\fc.
    (nunC,e A:3c79e
    Aqullarile
    N6umanwte/
    aqullartc
    Elcdtruva
    AuAq3 (5e5)z
    NafiVc 5llvcr F

    Trcehrcrrrfrhz .?
    Acanthrfe
    barte ?-
    Arnorphottt claY

    .flgure I-K-4; Paregenatlc Equeneo of ulnerale deterolnetl by Hoore (t920,


    Ftg.19) fron the large breccla plpel Eroken HllLs l'llne'
    391+

    breccla pipes and parts of.Bluchers Reef and Sieverl s Leader


    are accessible. t

    VisibLe nineralj-satlon is rare as the grain size is


    generally finer than.50 microneters anil often subni-croscopic.
    The paragenetic diagrarc shown in Fig. i-f-4 is'?fter Fig. .|9
    of Hoore (1976) and represents the rnineralisation found in
    thin quartz and pug veins in and surround.iug the large breccia
    pipe. Pyrite, electrun and a nunber of gold-silver sulphosalts
    are present. Bluchert s Reef contains electrurn and an
    acanthite-aguilarite intergrowth. The gangue ninerals are
    quartz, barite and clays. The quartz is nostly chalcedonic,
    however finely crystalline quartz occurs in veins around the
    breccia pipe and crystals up to 1 Onn long were collected by
    the vriter frorn vugs in 2 level (Fig. I-K-5).

    FTUID INCLUSTO}IS
    The locations of two sanples of vug quartz collecteil by
    the sriter fron 2 leve]- of the Broken Hills Mine are shown in
    Fig. I-K-5 and their position ln Moorer s paragenetic schene
    is shown in Fig. I-K-4,.

    Large prinary inclusions are common in both sanples.


    Nornal, vapour .rich and vapour filled (fig. 6-8) types are
    present, the latter types indicating that the hydrothernal
    fluid. uas boiling at the tine of nineral deposition.

    Filling temperatures and salinity histograns .for


    apparently normal type inclusions are presented in Fig. I-K-6.
    Because of a boiling fluid regirne no pressure correction is
    required for the filling teraperatures. Allowing for the
    possibility that sone of the higher filling teroperatures nay
    result fron inclusions uhich trapped soall quanti-ties'of
    vapour, a tenperature of 24OoC is selected as representative
    of the depositional tenperature.

    DEPTH OF MII{ERALISATTON

    The presence of sinter or siliceous sed,inent deposits


    and the evid.ence of boiling of the hydrothernal f1.uid at 2
    3,95

    BqSl
    Brt,citm
    PtW

    vnbdd
    6g'talcc

    o&4O
    . ...il

    tnatv?g

    n $wolitP lufr *il Dreccia


    I | (uimwst GRoUP)

    ,/ Qluulrtz vern

    Fi,gurc E-[-!r Plaq of ! lerdl Srshon 8tr].ls X,lnori ohorlng, .loeatlone of quar.t.r
    rarptrce rtui!,lcile
    396

    200 ?2a 240 260 280 ?@ 0t27


    |-T_|-|

    nqsl

    l-f l't_-
    llllrrtr.rlr l-l-.r-r
    zoo zzo 240 260 nO - ?@ o1.27
    Filfing lemVeralure cC
    ?{'lfl3*.,,

    Singlc valucE' El EI

    Flgure I-K-6: H!.rtogrona of ftlltag terperetures and apparent salinlttce for


    prlnary fluld lnclualong tn senplee of quartz fron the locstlona ahonn in
    Flg. I-K-5 (the lndtvldual reasureqeats are llated lu Appendk III)' In
    addltlon to noroal llquld-vapour laclugloaa, botb oanplea coDtaltr vaPour
    rlcb ead vapour fll,led lnclualonc (Flg. 6-8) lndlc8tlns that tho bydro-
    tbertal fluld vae bolllng at the tloe of guertz dcposltlon.
    397

    2lwl
    3 la&l
    4 lcval

    Edtwy lcrlrl

    FXgure I-Er?t Dlrgnarrtl 1.eoonctruet,|oa of tho doptb relelloes ri ths ErCIeo


    B,{11a. Hl,ss at tbr tfu,e sf lln,srellEritlon. The poel[i,on of thd t.u$rrce
    rlat.un ls baaad on thc p1rts.11c,. of boil{ng at ? Xevelr Undor hydroatattc '
    lrrrstut. a,oniltte'nr.'
    398

    level give sone control in the reconstructlou of the d,epth of


    ninerali.sati-on. rn the schene ilLustrated in Fig. r-K-2,
    boiling 1n 2 level is assuned to have been under hydrostatlc
    pressure cond.iti.ons.

    TiIERI,!OCHEI"{ISTRY

    The geochenical environnentof the Broken Hills


    nineralisation is shown in the fs2-fo2 diagrarn (Fig. r-K-g).
    The environnent is limited by the presence of pyrite but
    absence of pyrrhotite, nagnetite, henatite and bornite;. The
    latter nay not be slgnificant because chalcopyrite is also
    not present.

    Logfsa values of -11 anil -11.{ were carculated fron the


    nole fraction of :si.lver in electrun fron S.ieverts Leader and
    the Breccia pipe in 2 level, respectivery (tue electrun
    analyses were reported by Moore , 1976) . A val_ue of -1 1 is
    chosen to represent the nineralj-sation.

    The occurrence of sericite with ninor adularia in tb.e


    wall roeks indicates that the fluid pH was about 6.1 (equivalent
    to the pH of the seri.cite/K-feldspar boundary).

    contours of 1og nts (Fig. kK-s) at pH = 6.1 ind.icate


    that the concentration of total sulphur in solution uas around.
    0.001n (1og rz{ s = -3), 'liniting log f0, between approxinately
    -36 and -38.

    An fOa versus pH d.iagran, constructed for a lz d S of


    0.001n,1s shown in Fig. I-K-9. The log fS2 = -11 contour
    and stabllity field of barite are also included on the diagran.
    The ninerallEation plots on the oxidised sulphur species,/
    reduced sulphur specles boundary as shown by the shaded are&
    in Fig. I-K-9.

    GENESIS

    Breecia Plpe
    Moore (19?9b) consid.ered'that tre large breecla pipe lras
    -399

    (\l
    rn
    !#
    llEM,pfl'nE
    g'
    I ,!. I

    $ls
    *l+ ,
    ti!

    8r0

    MA6NET|TE
    tl 'qg
    i ra-*
    b.

    4 ,& 4 '42 4 -8 46 -W $2'n


    LoE f oz '.4

    Flgu,tat-f,-g; f92 verrur !02 dtagrao rt 240oG sholrl,ng thg geoehauical gnvtrsn-
    sent (sb*iied) of geld-ellver (I barlio) Etaerrligltton 'lu, guartz votBs of
    tbs Erokea lllllg ltlne.. {8'O.001rr!fl.6.1 ' 1og f82 f,rol alsctrur ol!,t}s'litLong
    r -iIr0 to -11 r4.. (t{ethoda of oonstruotlon arr dessrlbed l,a lpPeniltx. !t']
    400

    ?t)t,nito tileriarc
    lr- rotateo,
    ilrl
    t
    il
    t,
    :!r|I
    \-!3
    '
    i iItEMATtTE

    o({
    8- --!egl!:-'-:ll--
    Co" Loq f(
    draphite '-+

    PYRRHOTffE

    PH

    plgurc I-K-9: !02 verlur rt 24OoC .o6 4srp.001r rboulng t}e


    pH dlagran
    gcochcutcal eavl,ronocat (shedeit) of gold-sllver (! Urlte) alnerall'aatlon
    ln quarta v61n8 of thc Broken f,l1la lllno. i ' 0.1J, r(+'9.0?3, pH:a6,
    log fS, froo eleclru! colposltloua r -11.0 to -11.ar.Be2t (erttnatcd)
    .0.0001 and log fC02 (eetlqatgd) - t1.5. (See lppenitlx V for nethoda of
    oonatructlon. )
    iL t

    forned so:ret,ine efrr,er the t'ein systen, by either a process of


    hydrauli.c brecciat,ion or by a h;'droihernal explosion a-ent. ,H"
    suggested that the gold and silver lrere transported. in the '
    hydrothernal fluid as sulphide conplexes. Gold ancl silver
    deposition occurred where the conplexes becaue unstable as a
    result of boiling (witb concomitant loss of ErS) and oxidation
    (c.f. Fig. I-K-9).

    Vei-ns

    The presence of barite in .sone of the aecessible veins


    suggests that precious netal deposition in these locations
    nay have also been a result of oxidatj-on of hydrotherroal fluids
    carrying the netals as sulphide conplexes. Saraples suitable
    for fl-uid inclusion stpdy were unobtaineble and therefore it
    is not knovrn whether the hydrothermal fluid in tl." veins uas
    bolling, although the occuTrence of nineralisation at vein
    intersections is suggestive of pressure releas'e situations
    possibly . with associated boiling. Moore ( 19?9b) considered i-r

    that part of the vein sySten (tfre ore zone) represents a fault
    bounded breccia zone vhich acted as an aquifer for surface
    waters. Mixing of surfaee waters with the hydrothernal
    solutj.on nay have pronoted oxidation of the netal carrying
    sulphide conplexes (lloore, 1976i 1 9?9b).

    REFERXNCES Al'lD BIBLIOGRAPHI

    BELL, J .l,l. ; FRASER, C. 1912t see pp 77 81


    Dol{NER, J. F. 1935t see pp 171+ 177 end 285
    l{00RE, c.R. 19?5
    't979b
    SCHOFIELD, J.C. 1967
    UTTIIIG, B. S. ; ADAMSOI{' R. G. 1971+
    I{ILLIAMS, G.J. 197lrz see p12)
    102

    I-L
    TAPU - THAMES

    INTRODUCTION

    Although the nines between Tapu and rhanes prod.uced only


    snall quantltles of precious metals they are notable for their
    unique (relative to the other nineralisatlons in Great Bamier
    rsrand and the coronaadel Peninsula) type of ni.nerarisatlon,
    characterised by a variety of gold and si.lver telJ.urlde ninerals.

    The najor ninEs rers the Sylvia (3.4 nilLion grans or 1 2j r75}
    ounces of buLlton) and Monorai, (1.2 uillion gratrs or 38,637 ounces
    of bulltoa), togetber accouatlng for ?71 of the areas bullion
    production.

    The perlod of iatense niu{ng ceased about 1911, arthough


    detalled prospecting of the syrvia Reef including drllling and
    sbafting was carried out between 193j and 1945 (reported in
    Wil-lians, 1971'). In 1960 South Seas Minlng drilled a 23on d.i.anond
    drillhole on the Sylvia Reef and in the early 19?0ts Central
    PacLflc Minerals (N.2.) ltd drilled several holes on the Monowai
    Reef . Recsntly' AM0C0 Minerals lil.Z. Ltd have identl-fied centres
    of porphyry nineralisation in the area (Merchant, 1978') and
    drilled the largest centre in Ohio Cresk.

    GEOLOGY

    The geology of the Tapu - Thanes area is shorn ln F1g. I-t-1.


    Jurasslc greywacke baseneut rocks (uanala Etll Group) have
    linited outcrop on the coast at Rocky poLnt (uorth of rararu)
    and i.n Tapu River less than 1kn fron the coagt. They are ur-
    confornably overlaln by MLocene - tower Pliocene volcanle roeks
    of the Coronand.el Oroup.

    The oldest rocks of the Coronandel Group ia the Tapu - Thanes


    area are a sequenee of rhyolLte flows and pyroclastice. These
    are followed by nore typical Coronandel Group andesite aad dacite
    flows and pyrocLastics.

    Hypabyssal quartz d.iorlte and daclte porphyry stocks (Talnul


    Intruslves) lntrud.e the andesites and d.acltes and uere considered
    by Merchant to occur assocl,ated with circuLar geouorphic featurs
    lr03

    TAPt.I

    )i, .fl"
    v zr.-V,\ v - V

    wAloMu

    TE PUR,U

    :.r',"xt:)/;1
    FIRTH OF
    THAME'
    ';",J,', Couefi v
    srt
    Vv

    U;ti;
    il
    .ei-e

    RockV
    Polnl'

    {+*i
    ': N''L\ /.v
    \..'..'.\

    E Allwrum

    6 R\plrtc Vyrochalice of thc l.rnnlw RlcY,


    etmrtz dionlc and docrlc oorphvips )
    WHTTIANGA GROUP

    ts ol lnc TAINUI PLI'JTONICs I COROMANDEL GROUP


    E Ar&6te and doirta. lloras
    brcywacke and or$rll,ife
    .and Vyrxlasfw )
    MANAIA I{ILL 6ROUP
    %
    Quartz veir't
    Pcbt/,e, dikc
    - Fautt
    1C Lfrnc

    rlgure I-L-l: Geology of tbe Tapu-thanes aroe (aftsr Herchant' 19?8)'


    10t,

    interpreted as caldera collapse structures.

    of the area are the Lookout Rocks, a


    The youngest rocks
    series of rhyolite pyroclastics, which Merchant (fgZg) correlated
    with the whitianga Group. He also noted. the occurrenee of
    rhyolite tuffs 1n Tararu Strean.
    K - AT AGE DATA
    Dr C.J.D. Adans, Dr R.J. Merchant and Ms J.E. Gabites (pers.
    corDrr.) deternined K Ar ages between 9.5 and 11.9 rnolo for
    Coromandel Group andesites of tbe Tapu - Thanes area, whereas the
    K Ar ages they neasured ln nenbers of the Tainui Intruslves, vith
    the exception of one age of 19.9 n.y., ranged fron 9.3 to 12.6 Dolo
    The 1t.t rn.y. age nas deterrnlned iu a sanple of quartz diorite
    porphyry fron Tararu va11ey and appears spurious la relatlon to
    the otber agcs bacause it seerls to indicate that the porphyry is
    nuch older than the other Corouandel Group rocks that it lntrud.es.
    Iloweverr &D. alternative explanation, is that, the ages represent
    trro perlods of volcanic-lntrusive activlty, one at cr8o 20 m.y.
    and the other at 12-9 E.fr The older volcanic rocks have either
    not been sanpled or have been inprinted with a younger K Ar age
    due to hyd.rotbernal alteration.

    EYDRO TIIERMAL ALTERATION

    Merchant (lgli) classified the hydrothernal alteration ia


    rocks of the Tapu - Thanes Coronandel Group and TaiuuL lntrusives
    lnto the followiug five groups, i; ord.er of increaslng lntensLty
    of alteration:
    1. Weak propylltic; chlorlte, cal'cite, epidote, secondary
    al.blte, seeondary quartz, serLcite, pyrlte, zeolite and
    nontnorlllonite .
    2. propylltic; pyrlte, calclte, chlorite, epl.dote,
    Advanced
    eecondary albite, secondary quartz and sericite.
    3. Arglllici gertclte, pyrite, quartz, kaolinlte and
    chlorlte.
    4,. Quartz serLcite; quartz, sericlte and pyrite.
    5. Alkali sllicate; bi.otLte, nagnetlte and secondary albite.
    fn contrast, hydrothernaL alteration of the rhyollte
    pyroclastics, sedlnents and breccla plpes of the Lookout Rocks
    vas described as lnternediate argilllc (dtckite, quartz and
    TABLE I-L;1: HlneraLe lilentlf,led by l'terchant (19?8) froo veins tn the
    Tapu-Thanelt arear The table was conpiled by the wrlter
    fros lterchantrs text descrlptlon and follous hls
    paragenetlc schone.

    Stage SyLvla Veln HouoyaL Vel.n Other Velns

    Mo nolybdenlte
    anhydrlte
    ( tungsten? )

    galena, natlve goLd, selenLferous tetradynlte chalcopyrlte' pyrlte


    chalcopyrlte, pyrite alklnite, tetrahealrlte sphalerite, argentlan
    0u-Bi rutlle' 6elanlferous pyrlte, cbalcopyrlte tetrahedrlte, rutlle'
    tellurobl sDuttte' pyrrhotit6' kobellite,
    sphalerlte. arsenopyrlta,

    galene - ephalerlte galena - ephalerlte, galena - sphalerlte,


    pyrlte, ohalcopy!1te telluriiles: heeslte, tellurldes as !'lonoYaL
    Pb-Zn tallurldea: hessl.te' etutzlte' sylvanltet except for petzlte
    sylvanlte, altalto, altalte petzlte
    oagyrlte, tellurobis
    nutite gold

    galenar electrun' Itsuspectedrr but not galena' eJ-ectruo.


    Pb-Au oarcaslto encountered narcs site

    tetrahedrlte,
    Cu-Sb chalcopyrlte
    chaLcogilblte

    eloctruu Norfolk illne: eLectruo.


    ( pyrargyrlte? pyrargyrlte, polybaslte'
    Ool-d- pyrlte? ) Earcaslte' chalcoPyrlts,
    Pyrergyrlte pyrits, anatase,
    stephanite, uiargyrlto'
    galeoa

    c arboBst6 g barlte baflte or calbonates


    (r angenoandolonlto, (occur soparately)
    black calclte) c arbonates : l'Jatchnan H lne
    Stl.balte -
    Barlte ealcic rhodochrosita,
    Peroquet = black calcltc
    Dunedln = rhodonite and
    l,ln carbonate
    lr!6

    Pyrite) and advanced argillic (natroalunite - quartz assenblage


    with specular heuatlte, barite, kaolinite and rare pyrite, pr
    a pyrophyllite dickite assenblage).

    Sone rnenbersof the Tainui Intrusives have also been


    altered to an ad.vanced. argillic assenblage (pirophyllite, *-
    dickite, d.iaspore and quartz).

    MII'IERALISATIOIi

    Several quartz veins containing precious and base netal


    inineralisation occur in the Coronandel Group and.esites between
    Tapu and Thanes. These include the Zeehan, Paroquet, l.lonorvai,
    CoLorado (Constock), Vulcan, Sylvia, llorfolk and i,.Iatchnan
    (Fig. I-t-1). Base netals predoninaterwith pyrite,
    chalcopyrite, sphalerite and. galena being the nost connon
    netallic ninerals although the area is characterised by the
    occurrenee of gold, silver and bisnuth tellurj-des. In contrast
    to the gqld mines at Tharnes and Corornandel their Au:Ag ratios
    are generally low (typically 1 l4).

    Table I-L-1 lists the minerals described fron the Tapu -


    Thanes area by Merchant (t9ZS), grouping then j-nto the various
    paragenetic stages dedu.ceil by hin. Merchantrs (tgZA)
    parageneti-c diagran is reprodueed in Fig. I-L-z.

    ., Recently, attention has. been given to nolybdenite


    nineralisation, ori-gina11y noted. by Allen 1te99), and its
    significance to porphyry style rnineralisation. In recent
    geocheni.cal exploration work, Al"iOCO Minerals Ltd identifi-ed
    five centres of nolybclenite nineralisation; in the I'iaionu,
    Puru, Pohue and Ohio Creek areas (Fig. I-L-3).

    The Ohio Creek and Puru urineralisations were described


    by llerchant (lgZA). Molybdenite occurs in the quartz diorite
    porphyry country rocks in the following four settings: (a)
    as paint on joint faces, (b) uith pyrite, uagnetite, rutile,
    henatitb, chalcopyri.te sphalerite and. tetrahedrite in quartz
    veins up to 30nu thick, ( ln thin quartz veinlets in
    ")
    stoekuork'patterns and (d) d.isseninated. in the quartz sericite
    altered rock. The pyrite contains inclusions of rutile,
    hernatite and pyrrhotite. l.!erchantts paragenesis for this
    lr0?

    L
    o
    Cr

    ol
    I
    .\,

    AD
    ll rl
    u
    2 h
    t!
    :' qt
    o
    g f.
    cl or rt
    ro
    t d
    F +t
    g^
    U
    zg -l dtt
    o
    C,
    E
    A
    ll C'E
    tsl
    {rt
    -C-
    >l !t

    rl pc
    o
    ,.o
    ho
    OE
    q.
    c

    ct
    CA
    dts
    I
    o,
    OA
    cl 6
    {, F.
    a
    do
    OE
    6it
    trtr
    +)
    rD tt
    AO
    od
    u!+)
    c6
    ho-
    a?t
    AFI
    d
    h
    aO
    Nt!
    l'|
    .lE
    I
    .{ll
    oe
    h>
    tbD
    ll.t A.
    ll I
    f,r
    2 .!! * i- tE -.3. '
    :iia
    a

    iuui
    o= siiii;E;5 :9!oa F3 i '
    C'.,
    2

    E ii i I Esiliii;;;ii: i i$!
    408

    . fuphy1y co?Wr Uincralisalion CQnIrc

    m Rlnyolifc Vlrxlasfics- t oKour ?occt^- WHITIANGA GR0UP

    cRouP
    E ;;;;,;"and dactcc ,
    WTV| Gr"ywac*c a argitite MANAIA HltI GROUP

    Flgure I-L-it Locstlon ol porphyry coPPor proapecta, la the lapu-tbale6 ar.eat


    at preeoat belng lnveetlgated by tH0c0 Mtnerals (!I.2.) Ltd. (couplled i

    lror text and flgures of Horchant' 19?8.)


    ,&49

    rQorftrs

    sEnactI|lB
    ,f
    Itr'IDElltllt
    F3'Eisotttl
    'inrrr -
    F$|rat{B,
    rurlt.B. -
    calrooFllsls
    TBlnl|tl TTIG

    $rcilE I1!'
    sPf,llEnr8t

    ftrErrc I+B-l.r Finego-nrtde {nferrcil by lfcrchaat (19?S. Fi,g. 2-l 1) for


    rcqu.gncc
    qualtr-lc l,cttr ro!c! of pociihyry ayttan'l ln'tbr fapu--16n*rt .!ts.a-
    l+'lo

    ninera].i-satlon is shown in Fig. T-L- lr.

    Drilling by A!,10C0 at 0hio Creek revealed the nineralisatlon


    at depth to be pyrite and chalcopyrite with ninor gold, but
    only trace nolybd,enum, in the geochenical analyses of dril1
    core.

    FLTIID IIICLUSIO$S
    tlerehant (1978) studied f1ui.d inclusions in sanples of
    quartz, sphalerite, barite and ankerite fron the Tapu Thanes
    area. The inclusions are general.ly nornal two phase llquid
    plus vapour types, but vapour rieh and vapour fil1.ed tlrpes
    also oeeur in many sanples of the hlgh teuperature
    nineralisatlon (Cu - 81 stage only?) indlcatlng that the
    inclusions were trapped, fron boillag fluld.

    fluid i.nclusion filling tenperatures


    Merchant deterni.ned
    ranging fron 95oC (barite, Zeehan Reef) to t35oc (quartz,
    Kaiser Reef)x. He grouped his analyses on several histograros
    and correlated. their various peaks with individual stages in
    hls assigned paragenesis as follows:
    Cu Bi; 360 41OoC (periods of boiling)
    Pb Znt 23O 32OoC
    Pb Au; 282 3l5oc '

    plrargyrite nlaerallsa-
    The inininun temperature of gold r.
    tion was consi.d.ered to ba ind.icated by
    a sanple of quartz from
    the llorfolk Reef (Tararu) containiag fluld lnclusions uith
    filJ.lng tenperatures between 190 and. 200oC. Tenperature
    ranges for predoninant gold-pyrargyrite and stj.bnite - barite
    ninerali,satj.on $ere defined as 215 - 23AoC and 200 Z6OoC
    respeetlvely by filling temperatures of inelu3ions in barlte
    fron the Thanes area, discussed in a later sectj-on (t-t-t).

    Merchant invsstigated. the freezing tenperatures of sone


    flutd inelusions and, presented, his results graphi.cally. It

    FOOTT{OTE3 *Merchant record,s tenpeiatures as 1O5 LtSoC in


    his Tables 4-1 and 4-3 but these have an additioaal 10oe
    pressur correction.
    l+11

    TAETE I-L-2: 634S vatueo of Elnerale Eld tenperaturea calsulated


    f,ron tbe fraettonattqo of sphalorlta - galeaa pa.lra
    ln sanples frou the Tapu - Theues alee. Al.1 valnes
    aro ef unpubllshed aaalynes by Dr' B.!f. &oblnson.

    tr.11. s. ttLnaral SP-gn


    Sanple CbalCo- A tenpErature
    nunber Locatlon Barlta PyrLte 9'phelorite pyElts Galena Sp-gn 'c

    5549:l1a^-d. SylvLa
    l{l.ne 3L +1.7 +1 i4 +0,8 -0,.6 2.0 j15
    5513110 Sylvia
    rr'-b lll'ne 3L +Z.A -1.3 3.3 190
    55t;91Za-d' $ylvlr
    lllae 4L +,1 .6 +0.8 +1 .1 -1 .? 2.1 3O5
    551+9f'VA slokes
    1 L dunp +2.9 +2.0 +1,9
    551i9/18 'l
    +l.j +1.?
    ,r49l3e ' 4 t1,.9 *1.4 .0.8 2.2 290
    t51r/g?-e n +1.9 +1.4 +0.3 1.5 410
    55L9lrl Stokeg2I" .9 *1,5 +1.?
    Beef +1

    55,19118 '|'
    +i.g +1.7 +1 .?

    55tgl10A n 3I; +2.1 +1 . L +l .7 -0.5 tr9 t1,95

    ,51315Vd. o +1 .1 +1.2 +0.3 0.8 > 500


    5rt I l,A rB Kalser
    9 .

    illno
    ToP
    L iluop +1.6 ft.0
    ' 55t 91',11 rl +2. I
    i
    ,5t9l2a +'t .0
    J519t12s-b Kalssr
    Beef +3.0 +2.3
    ,rtgl6L Zeehan
    Hlne 5L +1.9 +2.6' -0.1 g'0 )15
    5549/68 rl +1.6 +0.3 1.6 ,9A
    trLqlTA rl
    f3r1 .8
    +1 +2.0 +0.3 1'5 0
    Pshue
    55L9l8 i +2.5 +2.7 '*1

    55L9{9A,B rl
    *0.8 +1.4 +2,1 +0.2 1.1 430
    duEp
    5519112 l,tsnoset 3L +2.3 11" g

    ,.51312 tt +24.q1
    t51 3111 ab n +2.0 +0.9 1.1 > 500
    412

    1s apparent fron his Fig. 4-5 that ineruslons in sanples fron


    the Sylvia' Moaovai and Kaiser veins had'freezing tenperatures
    in the range -0.9oc to -2.2oc correspond.ing to salinities of
    1-6 lo 3.7 g. rut. $ itacl (for consistancy with this thesis
    eonversi.on data of Potter et, aL [rfza] were used,), whereas
    naterial fron the biotite alteration zone in Ohio Creek range
    fron -2.7 to -3.40C correspond.ing to salinities of t+.5 to 5.5
    ee. wt. fr IIaCl.

    I'lerchant analysed the flluid incl,usions in sanples of


    quartz and barite by crushing the sanples, leaching then wlth
    nater a"d analysing the leachates by AAS and colorl-netric
    nethods. He combined the conpositional data of sone of the
    leaches with apparent salinity data fron fluid incluslon
    freezing tenperature stud,les to derive the chemical- conposition
    of the fluid inclusion waters.

    The resulting analyses are d.ominated by ila*, C^2*, CI-


    and oceasionally Li+. The concentration of c"2* exceeds that
    I
    of Kr i.n many analyses and. is also higher than }ia+ in a few
    analyses. Li+ concentrations are very high and in sone
    analyses predoninate over all other ions. i'iost I'Ia/K rati.os
    are around 2 although they average 3.0, uith a range of 0.8
    to 11 (ll sanples).
    The problens of contanin*t1; encountered, in fluid
    j.nclusion analyses during this study (j"" chapter 7) ind.icate
    that }lerchantrs analyses are probably also contaninated to
    varying d.egrees. His high c^21 and tl* concentrations are
    believed to be caused. by contanination as are sone of his
    +
    high K? concentrations relatlve to Na*.

    SULPHUR ISOTOPES

    unpublished sulphur isotope anaryses by Dr B.r,I. Roblnson


    of sulphides and barite fron the Tapu - Thanes area are
    listed in Table r-L-2. 634s values of the sulphid.es range
    fron -3.1 per niI (pyrite) to +3.6 per niI (pyrtte aad
    sphalerlte), uhereas barite fron !,lonowai 3 level has a 5 3lrS
    value of +21t.7 per ni1,
    I+13

    TABL-E I-[-31 Ocneral tlaroobheoleal Bar.auetsra fqr the ,ilepoaltloaol


    nr:l,roaurnts of t{ar'ebautrr (197) Cu'Bl, and Pb-Zn
    ascoclatl.onr ln tho quartz rstns betvetn fapu qnd
    Thancs (ralaly tb-c Sylvt'rt end ltonoset velna).

    $tagc
    Gu-Bl Pb-Zn Rsference

    oo fabls Y-l
    Taupatat'ur9 i00 280
    (ftula b,oll.ltg)
    AJE t
    T.rustoate s-trongtb 0.0?
    Srtlatty (r [a0l cq.] 0.34 o,.r5 I
    ri+ 0, og6 o.og5 rn

    Fs 5'0 ,,.0 Sce tert


    pll of kaotlnttt/ssrlcltp
    L.e {.1 Tabla T-t
    beuhdaiy
    pf, o.f ge,rtcita/fi-fE1d It
    horutiiary 5.6 5.6
    Total S (Iog rt8) -1.3to-2.0 -2.0 9oe text
    Log fS2 (ephaled,tp eoa.pr -4..4to-4,.6 -7.3to-9,.8 Table 1l-40
    Lo6 loa -24lio-28 -37.9b-15'5 Flguree altod
    (Flg.r-r,-51 (rtg.r-tr-?)
    Los fco2 +1.5 +1 .t . Tablc Y-l
    lr'l l*

    Tenperatures calculated by fraetionation between


    cogenetic pairs of sphalerite and galena range from 170 to
    (sanple R5513/5c-d, with A
    5O0oC rp_g, = 0.8 per nil dis-
    garded). The average fractionation of 1.8 per nll is
    equivalent to a depositional tenperature of 3|OoC.

    THER}{OCiiEI4ISTRI

    Porohvrv I'lineralisati.on
    l,terchant observed a zonation (tirne, tenperature or both)
    of pyrrhotite - pyrite (earliest or highest temperature),
    nagnetlte - pyrite and henatite - pyrite in the porphyry
    nineraLisation. He consid.ered that the ehanging nineralogy
    could be explaineC sinply by depositlon at d.eereasing
    temperatures fron a fluid with constant fOa and fSZ.
    Alternatively fOa and fS, nay have changed naking the sj-tuation
    nore conplex.

    Eis suggesteil parameters for the porphyry nineralisation,


    at a temperature of 35OoC, were log izts = -'l to -2, pH =
    3.2 to 5.2, 1og foz = -25.4 and log fS, = -J.8.

    Vein l,llneraLi sations


    fS, versus f0, and f0, versus pil diagranns were not
    calculated by llerchant (1978) for' ttre vej-n type ninerali.satioas
    and therefore two of his raineral assocatiors, Cu - Bt and
    Pb - Zn, are nodelled here. Additionq,Uy the gold - pyrargyrite
    associ.ation is nodelled in the Thanes section (t-U;. These
    particular associations were chosen because both temperatures
    (fron fluid lnclusions and sulpbur istotopes) and sulphur
    fugaci.ties (fron sphalerite and electrun eonposi.tions) are
    known, whereas one or both are unknown for the other nineral
    as s.ociattong.

    Table I-L-3 lists vari.ous parameters for the geochemieal


    environnents of the Cu - Bi and Pb - Zn ni.neralisatlons. fSZ
    values, derived fron wt /" le i.n sphaleri.tes, presented in
    Table I-L-3 differ fron those given by l{erchant because of
    the dlfferent nethod of calculation and also beeause only
    speciflc tenperatures are considered here, whereas Merchant
    listed values for ranges of temperatures.
    lrl 5

    (\
    (n PYRRH0TITE ,/1 ,,t
    Dr' ,Y7,
    s /f,
    ,, /,r
    !+
    rl

    -4 48 -y '* -t2 -N -25 -20 '24 -22 '20 -to

    Log f Oz

    Flgura I-L-5: f,Sa veraus fO, dlagrau at 400oC ehorel.ng the geocheuical
    anvlronnent (ahaded) progoaed here for Cu-81 Dluorallsatlon deecrlbad by
    tlerchant (fgZS) fror the velne 1n the Tapu-Thaueg (and Thares) area. t{oet
    aseeoblages of tbls etaga contatrn pyrlte' chalcopyrlto and sphalerlte and
    plot rear tbe upper end (trtgh fSa) of the ehaded area, horever pyrrhotlte
    and arsenopyrlte arc prsent ln aone asaenblagea lnillcctlng that the latter
    uere depositrd In an envtronuent representeil by the louer end (lorr fSr) of
    the ahaded area. (See Table I-L-3 for relevant thernochenlcal parauetera
    and lppendlx V for detalla of conetructlon.)
    lr16

    Cu - Bi l,lineralisati.on
    An fs, versus f0, diagrarn, constructed for a tenperature
    A''
    of 400"c to represent cu - Bi- ni.ne'ralisation, is presented
    in Fig. I-L-5.

    A conparison vith other high temperature nineralisations


    suggests tbat the concentration of total sulphur in solution
    duri.ng nineralisation was probably around. 0.01n but nay have
    been as high as 0.05n (1og nls values of -2 to -1 .3
    respectively) . Contours of log n HrS, approxinately equj.valent
    to log z { S in the pyrrhotite and pyrite pJ.us chalcopyrite
    fields, are plotted in Fig. I-L-5.
    On the basis of the textures observed in a saurple fron
    the Dunedin Reef, Tararu valley, !4erehant (lgls) considered
    that the earliest ntrreralisation of the cu - Bi association
    uas pyrrhotite followed by arsenopyri-te anc then later pyrite
    + chaleopyrite * tetrahedrite * various other ninerals of
    the association. sphalerites in the latter indi.cate 1og fse
    values of -tr.t+ Lo -4,.6, at 4O0oC, whereas 1og fS, nust be
    lower than -6.5 for arsenopyrlte stability and rower than -7.2
    for pyrrhotite to be stable. Therefore, as l.terchant suggested,
    the d,eposi.tional sequence pyrrhotite, arsenopyrite, pyrite
    plus chalcopyrite at constaut or.sli.ghtly decreasing
    tenperature ind.icates increasing fSr. The resulting range
    of Cu Bi ni.nerallsation in Fi-g. I-L-5 is sbown by the
    shaded area. rf the increase in fsa fs achieved witbin the
    ranges of 1og n 2S values suggested previously, a range in
    1og f0 2 of approximately -28 to -2l, is indlcated.

    In conelusion it is suggested that beeause the early


    pyrrhotite and subsequent arsenopyrite nineralisations are
    rare the nore typical cond.itions of deposition of Cu - Bi
    mineralisation are eharacterised by log fS, values around
    -1r.5 and 1og f0, values around -21r.

    Pb - Zn Mineralisation.
    The stabllity of the Pb - Zn ni.neraLi.sation of the Thanes
    Tapu d.eposits is linited on the fS, versus f0, di-agran (Fig.
    t+17

    -4
    -b
    -g
    comP.
    -to
    (\a
    rn tr/R.ITE
    -a
    s -t4
    TYRR,HOTTTE
    HEMATITE
    -16

    -B
    MAGNETITE
    -20

    -zt
    -24 e
    4 -44 -42 q4o -78 46 'U -tZ -U -2C '26 -24

    Lq foz

    Flgure l-t-sr fS, veraua f0, illagran at 280oC ehovtng broatl llslta of
    stablllty (baf,ore conelderatlon of the concentratlon of total eulphur ln
    aolutlon) propoeeil here for Pb-Zn nlnerallgatlon ldentlfled by Herehant
    (19?g) fron vel.ns ln the Tapu-Thanes (and Thanes) area. (See Table I-L-3
    for relevant theruocheulcal paranaters and Appendlx V for uethotls of
    conatructlon. )
    418

    r-t-5) by the presence of pyrite and chalcopyrite but absence


    of pymhotite, nagnetite, henatite and bornite. l,lerchantr s
    sphalerlte analyses indicate 1og fsa values rangiag fron -7.3
    to -9.8.

    A log f0, versus pH diagrarn constructed for a total


    sulphur in solution concentration of 0.01n (1og n S = -2)
    is presented in Fig. I-L-?.

    that seri.cite eomuonly acconpanies


    !,lerchant considered
    Pb zn rniaerallsation, whereas kaolinite and K-feldspar are
    abgent. Therefore a pH.of 4.9 ls consid,ered representatlve.
    The field of probable mineral deposltlon is shown by
    the shaded area i.n Flg. I-L-?. Deposition was fron a fluid
    containing sulphur pred.oninantly or almost excl.usively as^HrS.
    Deposition fron a fLuid. with sulphur predoni.nantly as S04t-,
    at a pH of around. [.9, i-s preclud.ed by the sphalerite
    conposlti-ons.

    Log f0, values ranging fron approxinately -35.5 to -33.3


    are indicated and COa coneentrations up to 1og tC1Z = *1.5
    aTe possible with the absence of graphite,

    The Tapu - - Zn ni.neralisation is defined on


    Thanes Pb
    the fTe, versus fSe (Fig. I-t-8) and f02 versus rzlte
    (Flg, 11-4) d.iagrans by the presence of hessite and altaite.
    Relatively high values of fTe, and niTe are ind.icated.

    GEITESIS

    Merchant (fgZe) consid.erecl that the porphyry styleand


    base netal veln type ninerallsations between Tapu aad Thanes
    were nnanifestations of a high 1evel porphyry nolybdenun
    deposit which forned at a depth of approxiuately 2 km in a
    greyuacke dacite and.esite pilert (Merchant, 1978 p2). He
    suggested the following sequence of events:
    1. Greyvacke basenent rocks lntruded by ')
    quartz diorite pluton(s?) with associated Lower to Mid
    I,
    subaerial, andesite volcani.sn J Miocene
    u9

    LMAGNETITE
    oN
    (t
    o r-Fs?:--B--lI -
    V$t-st::2-l
    '-lc.-^- -a

    PYRITE

    I
    I
    :
    ryR,RHOTITE

    Flgure I-L-?t f02 vcraur plt dlagrat at 280oC and {S.0.01n shovlng the gco-
    chenlcal environnent (ehaited) of Pb-Zn nlnerellaatlon ln the lapu-thares
    (and Thaoes) rclne. (Ses Table I-L-3 for relevant theruocheulcal para-
    neterg aad lppenili.x V for uethoda of constructlon.)
    lr2o

    lfro^ 5prnaleito
    Te, sol;d
    @

    Calavcrte (ht
    Ig
    -2 rc
    |\I l+
    r.U
    r{-
    rg
    IE
    -lo
    s iq
    -ff
    Coloradoitd
    -12
    Marcury
    \
    s
    _t1 -s
    F(
    r
    .s
    U
    -14
    -ll
    lo9. f 5z

    Flgure I-L-8: ftea vereua f9, dtagrar et 28OoC eho*lng the geocbeulcal
    eavlronoeat (shaded) of lepu-Tbaoes Pb-Zn acseublages-contalnJ.ng hssslte.
    Sooe eapooblagea aleo couteln altalte (+ electruu?) and sere forned elther
    at loyer valuos of fSa tban lndlcated by the sphalerlte conposltlona or at
    hlgb vaLues of fler. Becauss calaverlto la apparently absont froo thege
    aaaooblagoe (although reported lu float by Raodobr' 1980) the sloctruq/
    calaverlte boundary Dugt occur at hlgher fte, thaa tbe gold/oalaverlt,c
    bouadary ahovn, to allov altalte preclpltatl.on ulthout calavsrlte at log
    lSavaluee arouod -9.5.
    )
    I
    lr21

    2. Ernplacenent of nolybdenun ore she1ls


    at shallow depths (2krn)
    3. Formation of distal pyrite
    Eaqnetite and pyrite - henatite haloes Ftid to Upper
    l+. Deposltlon of base netals and quartz 14iocene
    in fissures above the ore shell in the order
    of Cu - Bi nineralisation followed by Pb - Zn
    tellurides ninerali.sation at depths of 1.5km
    and 1.5kn or less respeetively.

    The existence of l"terchantrs porphyry nolybdenum deposits


    is dlsputed here. Recent drilllng by AM0C0 failed to locate
    trore than trace Mo at depth although Cu and Au occur in cores.
    Also the tectonic environment is not favourable for the
    occurrence of a porphyry molybdenun d,eposit of the Colorado
    type (c.f. Westra & Keith, 1981). Instead the porphyry
    ninerali-sation 1s consid.ered to be of the porphyry copper t,ype.

    l,terchant recognised several circular features in the


    andesites of the Tapu - Thames area which were interpreted as
    caldera structures. Such structures nay be unweleone features
    for porphyry copper exploration 1f Sillitoets (1980)
    hypothesis, that cauldron subsidence nay pronote veln
    nineralisation but inhibit porphyry coppsr fornation, is
    correct. However, this theory would be consistent with the
    apparent absence of eeononic copper mlneralLsation at depth
    in the Tapu - Thanes porphyry deposits.
    The 63LSvalue of barite fron ltonorai 3 Ievel indieates
    that 5345 a, in solutlon was approxinately 0 per mi1 (Chapter
    9) and therefore the sulphur in the veln deposits nay have
    orlglnated from a nagnatic souree.

    Merchant (1978) suggested that sone of the vein d.eposits


    nay represent peripheral nineralisations to tire porphyry
    copper deposits. His view is supported by the very high
    iemperatures of the early Cu - Bi nineralisation. This stage
    nay have been deposited by a hydrothernaL fluid, partly
    nagnaticr euanating fron the porphyry environnent. DiLution
    by deeply clrculating neteoric water probably reduced. the
    nagnatlc water conponent to an inslgnlficant quantity by the
    tine of Pb - Zn d.eposition.
    122

    I'ron i,'lerchantr s descrj.ption the Cu - Bi staqe appears to


    have been characteri.sed by boiling fluids and this factor nay
    have been an inportant rhechanisn for nineral deposj.tion.
    ilerchan',, found no evid.ence for boiling during Pb - Zn
    nineralisation, however, a wide range in fS, is indi-cated by
    the conpositions of sphalerites and nay be a cl-ue to the
    reasons for nineralisation. One possible nechani-sn night be
    fluetuati.ons in IirS concentrations caused by periodic influxes
    and condensations of HrS vapour evolved from lower (Cu - Bi)
    boiling horizons. If such a nechanisn operated, d.eposition
    of sulphides would occur fron chloride conplexed netals in
    solution d^uring influxes of HaS. Altarnativelyr or during
    other periods, fluid - wa1l rock reactions nay have been the
    nai n causes of urineral deposition.

    REF IRIT;CjIS AiIp BIBLToGRAPHY

    BossARD, L. 19116
    DOl.Iii:I, J . F. 19352 see pp 1l'5 - 167 and 27O 281,
    COUPEA, P.G. 197 5
    Fi,ASER, C . 191 0
    tA''dTOii, D. c. 1973
    l,{ERCHAi'lT, R.J. 1973
    1978
    S0HoFIELD, J.C. 1967
    I{IILIAMS, G.J. 1971+z see pp 117 . 119
    lr23

    I-M
    TIIAMES

    THAI,IES SPECIAL AREA

    Fraserts (tgtO) rThanes Speclal Arean roughly consists


    of a triangular shaped area of land with the Lookout Rocks as
    the apex, tbe Thanes foreshore the base anil Tararu Creek and,
    part of Hape Creek, the northern and southern sides respectively
    (fig. I-M-1 ). However, because the Sylvia, Day Dawn, Norfolk
    and lrJatchnan Mines have nineralisations different to other
    nines of the Thanes Special Area but sinilar to nines north
    of this area they are excluded fron this section and discussed
    in the Tapu - Thaues sectLon. Therefore the northern boundary
    of the Thanes area considered here is placed innediately north
    of the },Iaitangi Mlne and Shellback Creek, rather than Tararu
    creek (Fie. I-M-1).

    INTRODUCTTON

    The Thanes area, although only the third largest gold


    prod.ucing centre in the Coronandel Peninsula (69 nillion grans
    or 2.2 nillion ounces of Au and Ag bullion) is fanous for its
    rich near surface bonanza deposits. Most of the gold and
    silver eane fron within 1 50n of the surface in a 80 heetare
    bloek.

    Pockets of extrenely goltl rieh oDe' cal.Ied bonanzas,


    lrere eneountered in five localitles:
    Shotover (3.2 nlllion grans or 102,000 ounces of bullLon),
    Moaaataiari (4,6 nilli.on grans or 148'000 ounces of bullion),
    Galedonlan (8.5 nillion gralls or 2771000 ounces of bullion),
    Cambria (1.8 nilllon graus or 591000 ounces of bulllon) and
    Waiotahl (2.2 nllllon grans or 70,000 ounces of bullion)
    One 2 tonne stope block fron the Caledonian assayed,
    approxiroately 56fi gold, 16fr silver and 28F quartz.

    GEOTOGY

    The geology of the Thaues area is lllustrated in Figs.


    I-M-2, I-M-3 and I-M-4. Tbe rocks are predoninantly and.esites
    lr2l,

    fliv\a

    )ax
    -<- ^..o...,.-""'-'.{['a..^ ti
    +o **"wawt ......""' \ t
    $q f
    / ."t""'o'-
    /-..*.1.*iiiiyy2ll{
    :1..=q"\
    Y Y"|[d,
    ,{
    '\ \Hfi

    I
    I
    fl t.
    -hrtt ri
    H
    T
    b
    It
    Jlrqtkl"'t
    VJalold'tl t
    5cronl
    erchanSr, j
    ",'59{\

    I SwFr
    Mif
    o Kurarvi -C.abfufian dril hole iite
    o Vdloria Companct drill holc cte
    Itt Itloa Aovndary ol -lhamce Are.a

    Ftgure I-M-l: tacatlon of soua ulneg yorked ln the Thaoes area durlng ihe
    lete 1E00rs. Seo Flg. f-L-l for the relatlon botveen the Thanae and lapu-
    Tbales arsas aa deacrlbed here. (t'lap coupiled frou Fraser, 1910i llerchant'
    19?s.,
    lr25

    ft
    Ir) K +++l++t'r
    + ? *l *. - :.,i
    l') l"-\ lri .tl*..-f+
    )i I I//'-/-
    t
    tr
    rrk5=/) \s) ]p.r+)'',o
    f,u+st{ i ;r( .Ti" " n/
    D'. o,,

    +
    r(.*
    !
    ./ .
    o,/s .r

    d t*^*
    1)1
    \\+ LI'
    v)
    /
    :: Vl{-\ )tJ ,,;J+

    / r4N
    vt
    I
    i'A.';= Ii
    :.7i:.\v
    a;J-?;l.r
    i't)'lr v
    ' r7r' X-= '6
    *.-'"'
    v _(J ,v
    Iv
    \:.:1..'\
    7Fi
    .ft \ !---,
    t't /:7':,K i)
    v, ),f:7/.^,
    lt
    qD! it
    A
    ?
    ^A
    FIRTH OF
    A
    A
    THA!'/'E A
    yl\r\\
    t)(.

    7( r r rt
    /7 ////

    f , //,/
    r\r\
    / / / //
    \\\\

    m Alluvir,rrvr

    @ Rnyolttc V,yxbtftcsollnc LookarT KxcK, WHITIANGA 6R0UP

    B and daCia,
    Ya/na ardeiia,
    (loxs'*td p[oclaslice. \
    I
    tr 3ffi^iYll'*#n*1,''k
    ilwrs hc
    r^,., I
    exoesnef
    ol
    conouANDEL
    GROUP
    m Andedrc PPEMTER

    E It*ittc , dactc aad fiiver r}ryolitc;


    llovtt1 d^d
    Grz,,!wacka,,
    fywCtasl\ce ' )
    onA anjilltfe ol lha MANAIA l.{lLL 6R0UP
    %
    r--,' QVAftZ veilt

    --- Favll
    Ag Ln,e ot
    '9 CrcrrE.gechon shown t;n F\.I-M-?A
    g Lwo ot C,ro*;-Seclton shovtn in F\. I -M - 38
    .l
    Plgure I-H-2: Ceology of the Thaneg arsa. (Conplled fronr Fraaerr 1910t I

    Merehantr 1978.)
    trz6

    a5
    S -C-r
    \f,Tt
    .l
    9 ;$
    rr
    tqsc
    ts rs-S.E I
    S E

    ,i#* Tttlll g HS s
    o
    o
    5
    lf|
    I
    E!
    ill l lrlt ilt
    i t

    A B
    VWr Ul
    zo^ta

    Lower Orc
    AAA zofilc
    AAA

    o Kitl

    E Alluviurra
    FIowI OT INC PREMIER, N.IDESITE
    m
    lvdcstfc. daqfe, and rnrcr..
    I .,*'"ANDEL
    ts rrtyollte'flowt ad pyrodatftcs GRoUP

    E lnfrus\vc rocks
    J
    braywacVc and arqrlltc
    = Qsartz vcir'rs
    ,/ $qvra otc
    N Orc Zu* .

    \'.5.1 A^A^A.A^A

    v VVr,Vr,
    UPLAND slocK
    YvYvvv
    vvYVvv
    I Krn

    Flgure I-ll-3: NI{-SE gnd SU-NE crogg sectlone of tbe thanes area (see Flg. I-tl-2
    for locatlone), tlote that dlfforent acalea have been used. (Xodlfled fros
    Fraaor' 1910; Mercbaat, 19?8.)
    lr27

    dorrfob dgtrncc ellrrelon


    In _ lccl
    tnrner:logt
    v
    v C-Sf. c
    v c-ca:s-P-c
    v
    c-o.+-Q
    o C-CL-P;c
    o c-P{
    C -CL-P-c
    V
    c
    jo--P<
    o- I
    l
    o CCLSPO c
    6 v
    C-CL-S-P-c
    lrl
    cl
    v C'cL'S'FQ.c
    I v C CLPc
    &
    o C CL S Pc
    L'
    0 C S P0 c
    +
    + C-9Q-P-c
    'o CSPQc
    v . c-cr--s.Fq

    v C tlj-c
    o C -CL-S-P-c
    + c 'cL-s-P
    t c-s- C cJcrlc
    P CL d{arl:'
    +
    I C -Q -Pc. S rercrle
    O qrertr

    I
    C.- P-c P pyntr
    C .cht
    /,/ *m
    C'Fc'
    *
    JE
    G.P.c
    v ."?f,l:
    c- cL.s.q d-rlettor",
    o
    <J
    aB
    G.

    t, c-P
    c- p:e -
    r.
    j
    hornbhl*
    rhycllb
    'c.cl-s-p lrUieltnrlec
    :E
    '&
    'r;
    i

    :-- C. CL.P-e --- fnudstond


    or Ps2.
    I

    F!.gure l-ll-4: Drlllhole log of the 1904 Kuranul.*Caledonla drlllhole (see Flg.
    I-l{-1 for loeatlon). (Fron Flg. 1-2 of, Hrchtnt' 19?8.)
    lr28

    of the Coronnndel Group. Fraser (1910) aist:.nguished two


    lithostratigraphi,c units; (a) a conplex series of alternating
    andesite aud dacite flows and breccias and associated dikes,
    hereafter terned. the Tararu Andesite, and (b) a relatively
    unifoun non-brecciated pyroxene andesite flow unit, whieh
    because it was. ho*,to approxinately 90fr of the gold and silver
    miaeralisation, was naned the Premier Andesite.

    The 1901+ Kuranul - Caledoni.an drillhole (located near the


    entrance to the l'{oanataiari Tunnel) provides the only detailed
    stratigraphic section througb the field). Fraser (1910)
    described the down hole sequeace as follows (botton of hole
    depth 448u scaled off Ftg. 1-2 of Merchant, 1978)z
    .Oo : lr6n ('ztrn
    (-Ztrn below n.s.l.)
    n.s.1.) Prenier Andesite I] (coronandel Group)
    116 - 378n (21- - 355n b.n.s.l-.) Tararu Andesite J
    ?78 t+70a (lSt l+t+8?a b.tr. s.1. ) greywacke (l'lanaia l{i1l
    0rouP )

    l'{erchant (t9Zg) investigated the dri1l core and conpiled.


    the column reproduced ln Fig. I-M-/*.

    Two najor north-west strlking faults, the 14oanatalari


    Fault and the Beaeh Slide, divide the Thanes area into three
    bLocks; the Back B1ock, i{iddle Bloek and, Seaward Block
    (FiS. I-M-3). The l,loanataiari Fdult has a proninant surface
    expression for a considerable d.istancer nnd uas located in
    several unclerground workings. ft dips. tr5o to the west and
    has a vertical displacenent progressively increaslng southward,s,
    estlnated at 1 83n j.n Moanataiari Strean and 305n at Una Hill
    (Fraser, 1910).

    The Victoria Conpanies drillhole, located 262n west of


    the n01d Big Punp Shaftnr wae drilled 7lr1a into alluvium of
    the seaward block but fa1led to intersect hard rock, lndicating
    a considerable throw on the Beach Slide.

    HYDROTHE RI,IAL AITERATI ON

    The and,esites are hydrothernally altered to propylitic


    (chlorite, carbonate, sericite, epidote and pyrite) and
    arglllic (sericita, pyrlte, quartz, kaolinlte and ehlorite)
    assenblages. : .
    lr29

    The miners teraed the weakly ehloritieally altered rock


    rrhard barstt, beeause of their greater resistanee relative to
    i

    the clay pyrite areas. '

    ).1I IiNRALI SATIOIi

    i,iineralisation of the bonanza type r{eneral-ly occurred in


    stringers and s'r,ockworks associated l.rith north-west trending
    eross reefs terned ftfllntiesrt (so called beeause of their
    fine grained siliceous nature) and at the interseetion of
    these veins with older north-east trending crystalline quartz
    and cbglcedoni.c reefs. The Eague- Srnith and l'foanataiari
    Cross Lode were notable exceptions to the lll{ and }IE trends.

    Dips on the vei-ns uere a nininum 45o and generally to


    the north, but a*, Una Hill dip direction is variable, and
    south of the Saxon Shaft in the I'tiddle Block' dips to the
    south are connon.

    The quartz veins pinch and swell, varying in wid.th fron


    a few centj.netres tottbLowsrt of 9m, although the average width
    was aoproxiuately 1ut.

    ilassive white chalcedonic quartz characterised the veins,


    but tranded, crustiforn, conby and vuggy textures also occurred.
    Velns l,rere usually weII defined and bounded by npuggytt clay.
    In sone areas, generally in proxinity to the major faults'
    hard bars and pr"esent land surface, the najor velns bifurcated.
    ox branched consid,erably.

    t"li-neraLisation uas predoninantly pyriter plrargyrS-te and


    electrum although sphalerite, stibnlte' arsenopyrite'
    chalcopyrite, marcasite, enargi.te and cinnabar Itere also noted
    by Fraser (t9tO). In addition to this listrllerchant (1978,
    identified. galena, several telluride minerals (hessite,
    sylvanite, stutzite, altalte, petzite and coloradoite),
    kobelllte, tetrahedrite and bournonite fron some of the nines.
    The najor gangue minerals were quartz and barite although rare
    carbonates (identified as ankerite and d,olonite by Herehant)
    uere noted. The paragenesi-s is sinilar to the northern ni.nes
    (Tapu - Thanes c.f. Fig. I-L-z), however the relative abundance
    Verbru,r rJlll'.'i.".1;T'( c=,,.,,511:)i:;c;'.i
    na

    of the stages is different r,rith the gold - pyrargyrite and.


    barite - stibnlte stages being almost overwheLmingll' doninant
    in the Thanes area.

    FLUID IIICLUSIONS
    l,lerchant (tgZg) studied f1ui11 inclusions in quartz,
    sphalerite and bari-te fron several of tbe mineralisations in
    the Thames area. They are generally two phase liquld -o1us
    vapour nornal types, but vapour rich and vapour filled types
    aLso oecur in nany sanples from the high tenperature
    nlneralisatj.ons, indieating that the inclusions were trapped
    fron a boiling f1uid. Liquid GOa was identified in a few
    vapour rich inclusions in quartz frou the Garbo Mine, Karaka
    Creek and individual sanoples of quartz from the tucky IIit and
    l4agnet i{ines eaeh eontai.ned a single inclusi.on wlth a spindle
    shaped daughter mlneral (tbese dissolved at the filling
    tenperature and therefore differ from ineluded ninerals
    described in this thesis frorn other areas, see Chapter 5).

    i4erchantrs (1978) visual esti.mate of the relative voluioes


    of water, liquid C0, and vapour in the fluid inclusions from
    'r,he Garbo i'line, trhen corrected for relative denslty, are used
    here to indicate a COa concentratj.on of around 20 nole %.

    Merchant deternined fluid irr"fu"fon filling tenperatures


    ranging fron 120oC (quartz, Haleyon low level) to 4oooc
    (quartz, ilalcyon 1or.r level and Atlanti'c 2 1eve1) *. Filling
    tenperatures of incluslons in barite from the l{oanataj-ari
    Gross Lode ranged from 2'15 238oC and, were coasid.ered, to
    represent gold - pyrargyrite stage nineralisation, whereas
    inclusions in barite coexisting with stibnite in the i"lagnet
    Mine, representing stibnite - barite nineralisatj-onr ranged
    fron 200 - 260oC. Various samples fron Thanes, together with
    samples fron the nines in the Tapu - Thanes area, indlcated.
    tenperature ranges of 360 - 4,10oC and 230 - 3eooc for Cu - Bi
    and. Pb Zn stages respectively.

    FOOTNOTE: * Merchant reeord.s tenperatures of 130-41OoC in hls


    Table L-1 but these have an additlonal 1OoC correction for
    presEure.
    lr91

    TIBLD l-ll-ls 634S vatuca of ultnalg fto! tbo fhruea crea. AlI' vrLuca
    arc o:t unpubllabed an-rlyrar by llr B.lf,. Robi.ngon.

    I.ll.S. 9urple . ltineral


    llurbsr Loeatloa Barlte Pyrttel Splrrlerl Ghalaopyrlte Stlbnlts
    i513tl fo'b f,urtnul llinc +19.1 +2.6
    ,513/'7b Rsubca FaFr +2,8
    JSlil8atb liloanataLartr +17.2 +2.1
    ,51il3 e 1' llalcyon t{'trne +19.7 -2.6
    i519175a,v Log Drive +2.9 +0.1

    591311?+arb 0ltca* Great +2.8 +1.7

    ,51)11 1.2 Cllnar Greek


    551X/16a-e Sood 0rsstt +2.2
    ,51V|7 l{agnet ltlae +1.0 +?.6
    lr32

    Freezing temperatures of fluid inclusions in sanples


    representing Pb - Zn uineralisation of the Shellback' Atlantic'
    l'iaiotahl - Canbrla and, Lucky Hit veins range fron approxina'r,ely i

    -1.1 to -1.8oC (read off l,lerchants Fig. l.-6) correspond.ing to


    a sallnity range of 1.9 to 3.0 Be. wt. I UaCt (using the
    conversion data of Potter et a1 , 1978').

    Merchant (lgl!) analysed the fluid inclusions in sanples


    of quartz, barite anC calcite by crushing the samples' leachi.ng
    them with water and analysing the leaches by AAS and.
    colorinetric nethods. He conbined. the conpositional d.ata of
    some of the leaches with apparent salini,ty data fron the fluld
    inclusion free zir,g temperature studies to clerive the cbenical
    conposltion of the fluid inclusion waters.

    Like the analyses of naterial fron the Tapu Thanes


    area the resulting analyses lrere doninated by N"*, C^2+, Cl-
    and Li+. l.lost I{a/K ratios were around 2 although they
    averaged /+.4 and range fron 1.3 to 37 (?3 ataLyses). The
    concentration of sulphate in some analyses was equal to
    chloride but l,lerchant aeknowledges that some contaninatlon
    nay have occurred from sulphide mi-nerals.

    The wrlter considers that the high concentrations of


    several elements in l,lerchantts aralyses, particularly C^2*,
    and Li* are also due to contanination (c.f. Chapter 7). This
    may account for the generally low Na/K ratios exhibited by
    Merchantl s analyss.

    SULPHUR ISOTOPES

    Unpublished sulphur lsotope analyses by B.l'I. Robinson


    of sulphid.es aud barite fron the Thanes area are lj-sted. in
    Table I-M-1.

    63LS values of the sulphides range fron -2.6 per nil


    (pyrtte) to +2,8 per nil (pyrite and stibaite), whereas the
    barltes range from +17.2 per nil to +21.3 per ni1.

    Although the absence of galena analyses linits the


    applLcation of sulphur isotope, geothernouetry, fractlonatioa
    betreen a pyrite - chalcopyrite pair fron Clinax Creek ( sanple
    133

    s vaea.v g1
    s g
    q 3t

    (\l
    (n

    (r
    o
    K"9 $,E
    MA6NETITE i$F
    HEIVIATITE

    Ei,;-i'd
    .-E
    -r0 -46 4g 4 -42 -& -t8 -rc -A 42 -n -a
    Log f oz

    Flgure I-M-5r fS, vereus f0, dLagran at 230oC ahowlng the gtabl1lty rolatlona
    of sons riaerale depoalleil durlng t{erehantre (lgZs) gold-pyrargyrlta etage
    of the Thanes veln deposl'"o. The predonlnant sssenblage appears to be
    pyrlte * electruo + pyrargyrlte' ropreaanted by the gtar, honevelp son
    aosenblages also contaln etlbnite and nere deposlted at loser valuee of
    fO2 (and hlgber valuea of aS), to the left of thE ettbnlte/ksrneslte
    boundary, lrhereae othera contaln arsenopyrLte and vere deposlted at lower
    values of fS2r belov the araenopyrtte/pyrlte i araenlc boundary. S160.001n1
    ' plt=t.{ anil 1og fSa fron electruo conpoeltlons=.-11.0. (Sea Appendlx V
    for oethode of constructloa.)
    l+31

    R5513/1ta,b) indicates a depositional tenperature of 3?0oC.


    Because of problens experienced with py - cp pair tenperatures
    fron other areas (c.f. Chapter 9) this figure probably
    represents only a naxj.nun teraperature.

    DEP,TH OF },III.iERALISATIOiI

    Boiling of tbe early high tenperature fluid and the


    presence of liquid C0 Z in lnclusj-ons i-n a sarnple fron the Garbo
    l.tine lndlcate a pressure of around 300 bars (c.f . l,lerchant,
    1978) corresponding to clepths between approxinately 1kn
    (lltUostatic pressure) andl 3kn (nydrostatlc pressure). Bonanza
    gold (gold - pyrargrite) nineralisation oecurred, at nuch
    shallower depths, i.e. 300 - 500m, if boiling occurred at
    tenperatures between 200 and 2lr}oC (Merchant, 1978 p2?8).

    THERMOCIIEMISTRY

    The geochenical environnent of gold - pyrargyrite


    nineralisation i-s linited on the fS, versus f0, diagram (Fig.
    I-14-5) by the absence of nagnetite, hemati.te, pyrrhotite
    and bornite and presence.of pyrite and i.n sone instances
    barite, chalcopyrite, arsenopyrite and stibnite, Log fSe
    values around -11 are ind.icated. by Merchantrs electrurd
    analyses but values loser than -13.3 are required for the
    stability of arsenopyrlte. The presence of pyrite but absence
    of hematite indieates that log fOa was lower than -)3.0.
    The general valueof +1.5 for log' fCOa does not seen
    applicable herei lower C0, fugacities ere indicated for the
    stability of sone sulphides in tbe absence of graphite (viz.
    log fCOz < +1.0 for electruu t stibnite and 1og fCO2 < -1.5
    for stibnite + arsenopyrite; Fig. I-M-5).
    l{erchant ('1978) noted that although kaolinite ls the
    conloon clay nineral associated with the gold - pyrargyrite
    ore, sericite was also present. Therefore a pI{ of L.l+ (pH
    of the kaolinite/serlcite bound.ary) is indlcated.
    Contours of total sulphur j.n solutlon at a pH of l+.lr
    indleate that log zS nust be greater thaa -,{ for arsenopyrite
    stablJ.ity snd possibly as nuch ast -2 for deposition of stibnlte.
    :.
    435

    I{EMATITE

    N
    o
    N..,
    s | ---l
    J -LEle-_-rL__itE__-
    Le'Ft.z = -tz !
    ---?--:- -TF/ffiET'-'-.
    ----1'-----

    -I6dT'4a-:- ZJif 8:-


    5=-::1 ---
    - = =--

    PYRRHoTffE

    flgure I-t{-6r f0, veraus pll dlagran at 230oC anil {S=0.001n chorlng the
    geocheolcal envlronuentE of varloua Thaueo gold-pyrargyrlte aseenblagea:
    (A), elsctrutr + pyrargyrite + pyritet (B), electrun i pyrargyrlte t
    pyrlte + arsenopyrttel (C) aud (D) Elternatlvee for electrur + pyrargyrite
    + pyrlte + barlte. i - O.)5, p|el.tr, log fS, frou electrun
    "K* ' 0.056,
    couposltlons rt-11,0, and log fCOa (estloated) = +1.5. (M6thods of
    constructloa are descrlbgd lu Appendlx V.)
    l-36

    of -3 (n{S = 0.001n)' sinilar


    An interrned.iate 1og rzrS value
    to other mineralisatlons around. this'tenperature, is used to
    construct the f0, versus pH diagran (Fig. I-11-5)

    contours of log fs, llotted in Fig. I-!i-5 ind,icate that


    low sulphur fuqacities (below 1og fSa = -11), without the
    presence of hennatite, are only possible in the EtS pred'oroinant
    f i.eld,.

    The depositi.onof the various nj.ueral associations,


    electrun + pyrargyri-te + pyrite I arsenopyri,te i stibn1te
    l barite, can be nodelled by variations of f0a, fS2 and a{S
    at eonstant temperature and pii (although in reality the latter
    paraneters nust have also varied). For exanplet assune that
    electrun * pyrargyrit,e + pyrite mineralisation was forned'
    predominantly at 1og fSa = -11 and 1og nlS = '3 (Fleld A of
    Fig. f-1.{-5). An assemblage of electrun * Pyrargyrite * pyrite *
    arsenopyrite nay be formed by a deerease in log fs, to -13.5,
    accompanied by either a decrease in f0, (fieta n of Fig. I-M-6)
    or rz4. S (c.f . Fig' I-l{-l) ; electrun } pyrargyrite + pyrite
    * stlbnite is forned. by an increase in 1og ;z{S, acconpanj-ed
    by a decrease in fOZ (c.f . Fig. I-14-5), whereas eleetrun +
    pyrargyrite + p;;rite + barite nay be preeipitated by an
    increase in fOa (fieta C of Fig. .I-M-6). Alternatively the
    latter assexrblage uay be forned by a decrease in pH (tieta O
    of Eig. I-l{-6).
    !,terehantrs proposed boiling ffoia envi.ronnent for the
    deposition of the Thanes bonanzas offers a nechanisn for varying
    the concentration of dissolved sulphur, f02 and pH by loss of
    HZS (and other acidic gases in the case of pii) during period,s
    of boi1i.ng.

    GTIiESIS
    (lglA) consider:ed that the electrun pyrargyrite
    l.lerchant
    nineralisation at Thanes was deposited above a boiling zone 1n
    a fossil geothernal systen durlng the l'iid to Upper Pliocene'
    Merchantr s evidence for boiling 1s nainly inferential but
    convlnclng. Bonanza mineralisations are related to structural
    features where pressure release and ulxinS of uaters probably
    occurred,. .
    l-3?

    Bolling off of H2S fron the fluid wouJC cause instability


    of gold and silver sulphide conplexes in solution and the
    acldic environnent indicated by the alteration mineral
    assenblage in the wall rocks r.rou1d. also help promote deposition.

    Bel-owthe boiling zorre, nineralisation characterised by


    tetrahedrite and sevaral sulphosalts was deposited presunably
    fron chloride eomplexed netals in solution.

    of barite indicate a sedinentary source


    634S values
    (greywacke suite rocks) for the sulphur and sulphate ninerals.
    The hydrothermal fluid was probably reeirculated neteoric
    water.

    The alunltised rhyolite rocks of the Lookout Rocks area,


    described. in the previous section (f-f,, Tapu - Thames),
    probably represent the near surfaea acid sulphate water
    environment of the Thanes hydrothernal system. If sor then
    the Thanes mineralisation must have oceurred during the period
    of regional rhyolite volcanisu (i.e. during deposltion of the
    tlhitianga ilroup) itt the Pliocene as suggested. by i,lerchant (t9Za).

    REFERE}ICES AI{D BIBLIOGRAPHY

    DOl'llIEY, J.F. 1935: see pp 68 - 11'lr, 157 - 162 and 270 - 283
    FRASER, C. 1 91 0 r
    l,lERcHANT, R.J. 1978
    scHoFrELD, J.C. 1967
    l'[LLf AMS , G.J . 1 97 l+t see pp 1 04 - 107
    47e
    I-N
    }IEAVESVITLE

    I}ITRODUCTION

    Although the deposits of the I'ieavesville area produced.


    only snall quantities of gold and silver the area is par-
    ticularly interesting because it is on the boundary betr.reen
    Miocene Coromandel Group andesites and Pliocene t''Ihitianga
    Group rhyolites, with nineralisation occurriag in both rock
    types.

    The nain workings occur in two groups geographically;


    a northern group consi.sting of the Golden Belt (Aiax Reef),
    Birdsr Golden Arroru and Graces and a southern gr.oup consisting
    of the Chanpioa llorkings. Mining began ln 1875 and continued
    internittently until 1938 produeing 910,000 grs.ns (Z9,ZgZ
    ounces) of bul-lion fron 21 ,?56 tonnes of quartz. The Ajax
    Reef was the major producer accounting for approxinately 80tr
    of the fields production (lZOr000 grans or 23,160 ounces).
    ASARCO ( Nellsen, 1968) investigated. the area i.n the late
    1 950r s with a program of geological napping and geochemical
    sampling. Torckler ( t gZA ) studied the geology and rainerali sat5. on,
    and further geological inforrnati-on gained from recent diamond.
    drilling by Al,lOC0 was reported by Barker et al (1980).
    GEOLOGY

    The geology of the lleavesville area is sunnarised. in


    Figs I-N-1 and I-N-2. Coromandel Group and.esites, consisting
    predonlnantly of lavas with ninor breccias and lapiIIi tuffs
    are overlain by l'Ihitianga Group pyroclastic rocks. The
    latter conslst of a sequence of tuffs and breeeias' initially
    andesj.tlc to dacitic' but later rhyolltlc in colnposition'
    interrupted by a carbonaceous shale and interlayered rhyolitle
    tuff unlt. The carbonaceous shale unj.t contains coal fragnents
    and a beech pollen mieroflora and is considered. by Torckler
    to have been deposited ln a J.ake, 2 to 3kn in dianeterr
    containing a nunber of thernal springs. The indivldual shale
    units vary in thickness from 10n to a feu centineters, being
    conposed, of alternating quartz and carbonaceous laninae and
    lr39

    WS,--4
    i t,. tt tt.,
    .llri{
    .Nol-rri-- ii:rl.
    rl I tllll
    rl n il [-tl
    I
    4-=-7: =TS
    if::r'i:
    =__,4-i:i 11:;,'#
    'a'rt i !F
    >e-ca..7---
    t <h-

    ffi a
    Section

    ffi$
    It,lr tllF^

    [i;i::?il
    {r
    ffi
    ,f
    I dl-
    ,r ! ,l-
    L
    tl tl t\
    ll,.ll
    i;,i#\
    lt
    I tll
    iil

    rt
    t {{
    Wsn
    .u,7,$.il

    ;i:,:i*
    .=>\\
    i!ft i$;;v
    Geologicol contact
    Fauhobserved
    Rhyolitic pumlce lapilli tuff -/
    _.-/ Fauttinlorred
    Accretionary lapilli tutf Quartz reef
    -r/X Mine workirrgs
    Rhyolitic lithic lapilli tuff
    Black Shale & rhyolitic tuff
    Dacitic & Andesitic tuff & breccia Road
    ="
    ffiu Andasitic lava & breccia

    l'1gure I-N-1: Geology of the Neavegvllle area (after Ftg.l of Barkor g!3].,
    1980). Detalled plana aud locatlona of ths ulnes rrere glven by Nellsen
    (tfaa1 and Torckler (19?8).
    lrlr0

    E B
    rt
    t- E
    Es? -
    'o-? 6r
    E(t I o6
    di
    *-t: ij:i#
    o r l ltr r r x lF_-:-=13art'.lr a.: r
    I u I r r r ts--.5--5-\f.<?r^-r-
    || s--r _ lJ.q l-
    i I t t, :tt'l'.<6----.5ffi
    lf,tD
    rtt t-
    S'Ei",Ei
    r..r.-"liSGl...:_lF
    ' arart r,l trrtr.arl lrllrll

    Dsbris florv dcpoit


    Rhyolitic lithic lapilli h.rff H - High rank altration
    Black Shalc $ rhyolitic hrff M-Medium rar*aharilion
    Dacitic E andeitic tuft & breccir

    !ffiif^""tt Fa Andasnic hva & brccde

    F1gure I-N-2: Crosg-soctlon A-B located ln Flgure.I-l{-1. (8rou Ptg.2 of Earker


    9!-31' 1980.)
    lrlrl

    '[*n*"r' ANT

    FJ rt"-*-" Arr'
    .El
    * ausitc A
    |
    ABT
    Iute*,it"
    Amirsln
    RT
    Io'ro'it"
    . catcirc A
    I
    .
    edootc A
    I
    l(llartr A.RIT
    I nrr,rn" RTA

    El"ou" 8TA

    1'0" RTA
    il*n,,no,n,o. RT,A

    xaolinitc RT
    I
    A
    lfaumntitc
    A
    lWrinkitc
    la*ra,rt A
    I Sphcnc A
    Lcucorrnc ANT
    I
    A.RTi
    Intt"
    0urrtr-
    | trr. cs,A
    l.rrinlctr
    A. endosita 61. 3tr;'orlitic tuff, CS - cltbonecon rhalc

    Flgure I-!l-lt Claastflcatlon of hydrotherually altcratcd rockg at lleaveevl]'lc.


    (Fron Ftg.3 of Barker, et alr 1980.)
    l+l&

    containiag 5 - syngenetic pyrite and marcasite


    30%
    roinerallsatlon. The other tr{hitianga Group pyroclasti.c units
    were considered by Barker et aI (1 980) to have been deposited
    subaeri.ally as non-welded pyroclasti-c flows and air-faIl tuffs.

    HYDROTHERi'{AL ALTERATI ON

    Torckler (1978) noted ihat hydrother,ral alteratl-on of


    the andesites at lleavesville is propylitic (calcite, chlori.te,
    zeolites, epidote and quartz) increasing in i-ntensity towards
    quartz veins, r,rhereas potassiun silicate assemblagesr consist-
    j-ng nainly of quartz and ad.ularia with niuor serici'te and
    plagioclase' occur ln the rhyolites.

    Barker et a1 (1980) classified the altered rocks into


    three alteration rank classes; low, rediun and high (Fig.
    I-N-3) which they considered to approximately correspond to
    propylltic, argillic and phyllic alteration types. The
    alteration assemblages are very similar to those of modern
    geothernal fields at Broadland.s and Wairakei.

    MIIIERALISAT IOiI

    Iollneralisatlon in Andeeite
    l,lineralisation i.n andesi.tic,host rocks 1s mainllr confined
    to a lenticular quartz vein known ag the Ajax Reef. Torckler
    (19?8), working with sanples fron mine dunps, found rare fine
    gralned chalcopyriter galena, sphalerlte, hessite and pyrite
    ln a gangue assenblage df quartz, adularia' sericite and
    brookite. The quartz is eonmonly coarsely crystalline;
    large vug crystals up to :/r0nn are abund.antly present on dunps
    of 1 and 2 levels. Torckler considered that the occurrence
    of the sulphide nninerallsation in breceiated. quartz zones
    ind,lcated that it was deposited late in the vein sequence. -

    tsarker et a1 (t 9AO) noted that rnaterial fron 1 Level


    dunp contalned grains of electrun, 0-03 0.05nm ia length'
    included ln large (0.4nn) pyrlte grains ln wa1l rocks adjacent
    to vein quartz.
    lrlrS

    Adans (1915) reported the mining of approxinately 20Okg


    of nassive molybdenite fron footwall and hanging wall zones
    of the Ajax Reef (iio. 1 level?) in 1915- Barker et al (tgao)
    descri-bed an unlocated sanple from the Golden 3elt workings'
    i.n the Geoloqical Survey Collection, containing fine grained
    nolybdenite as a thin crust on vein quartz.

    l,lineralisation in Rh'rolite
    Graces and the rrBluffsil
    Several zones of post depositional brecciation occur ln
    the rhyolitic tuff and these are coasidered by Barker g[3!
    (1980) to have been forned by hydraulic fracturing. The
    breccias have been silicifled and infilled with interconnecting
    netrrorks of quartz veinlets containing minor pyrite and
    electrun minerali-sation.

    The strongest nineralisation (assay values up to 175


    g/t Au and 88g/t Ag for quartz vein sanples) oeeurs in Graces
    r.rorkings (Fig. I-N-1) where silicified tuffs contact the
    pyritised. carbonaceous shales. Quartz vei-ns 0.5 to 300nm
    in width, containing vu{s up to 30nn in dianeter' occur ln
    the contact zone. Two phases of electrun deposition oecurred;
    the first forning coneentrati.ons at the quartz vein - shale
    interface wlth partial replacement of syngenetic marcasite
    and pyrite contained in the shale, whereas the second is
    eoncentrated near the centrd of the quartz veinlets, often
    on vug quartz crystals (torckler, 19?e). The electrun occurs
    as anhedral nasses varylng in size fron less than 0.00Jnn up
    to 2nn long.
    Birds and Gold.en Arrow open cuts have been excavated in
    locallsed areas of brecciation anil lntense quartz veining
    in a NNi{ trendi.ng zone of intense slliciflcation along the
    nBluffsrt. Netvorks of quartz veinlets and vugs (with quartz
    erystals up to 20nn long) cenent the breccia and in Bird.s
    Qpen Cut electrun occurs as scattered. gralns 0.03 0.08nm
    in size, i' the late stage vei-n quartz (Barker 44' 1980).

    NeLlsen (1968) record,ed typical Au assay values of


    lrlrlr

    120 t6o 200 240 260 0 I 2


    l'-1

    t7940
    =,J
    r-l
    {J Bq+l

    rfl
    Et -F ,l- 17942 tl
    trl t7947
    n
    tl t7944

    h_,
    Fl-l-
    ll-Er tr,45
    EI
    -l

    n
    C]=
    tve46 .t
    no 160 z@ 240 2gO O .a ?

    Fitf ing Temperalurz oC Salinilv


    eq,wf '7. NaCl
    5tringlo valuesz Er

    Flgure I-t{-l: lllato.graus of prloary fluid lnclual.on fllllng teuperaturee end


    apparent scllnltles deternlnod ln aanplea of quartz frou the lleavesvllle
    area (thc lnrtlvldual arauronsnta ara 1latad ln Appcndtt III). Sanplee
    13912 through to 139116 contaln vapour rlch (Ftg. 6-6) antl vapou! fllled
    (Ftg. 6-?) fluld lncluslousr ln addltlon to nornal llquld-vapour typee'
    lntlcatlng that the hydrotherual flul.d frou nhlch they grer naa bolllng.
    lrlrS

    4.8ppm in Graces open cutr' 2ppn'in Birds and 5ppt in Golden


    Arrou with an overall Tange of 0.5 to 15.1pps. - |

    Chanpion
    Nine adits have been excavated. in rhyolitic tuff of th-e
    Champion area to intercept a 15n wide zone of intense
    silicification. Downey (1935) recordeil that the venture
    generally proved unprofitable and ASARCO I s assays showed that
    the zone was generally unnineralj-sed except for a few patches
    containing up to 4ppn Au (Neil'sen, 1968).

    FLUID IIICLUSIONS
    Torckler deterrnined filling teraperatures of fluid
    j.nclusions in vug quartz sanples frorn Graces and Birds open
    cuts. Histograns of his results (fig. 5.2 of Torckler, 19?8)
    have vell defined nod.es of approxinately 21OoC and 230oC
    respectively.

    Seven sanples were investigated by the writer' one of


    vhich (139ltlr) uas Torcklerls sanple frors Graces oPen cut.
    The location of tbe various samples is shown in Fig. I-N-1.

    All sarnples contal-n 2 phase liquid plus vapour nornal


    type fluid inclusions but sanples 1391r2, .139tr3, 139lrl', 1391r5
    and 1 39t6 also contai-n nany vapour rich (ffg 6-5) and vapour
    fl1Ied (Ffg. 6-7) inclusions indicating that the hyclrothernal
    fluld was boillng at the tine of their entrapment.
    Fil11ng teuperature and salinity histograns are presented
    in Fig. I-N-,4. Filling tenperatures for Torcklerrs sarnple
    (sanple 139lrlr) presented here Here deternined by the rrriter
    and the results differ slightly from those given by Torekler
    (Fig. 5.2 of Torckler, 19?8). partly because Eore neasurenents
    are presented here and also because in sone cases dlfferent
    inclusions nay have been neasured..

    Pressure salinity corrections are not required, for the


    filling tenperatures of the sanples forned in a boiling
    environnent and are less than soC for the two other sanples
    t+l*6

    Pad$w*i
    -

    z
    -'
    E
    It
    o' 'Avds
    gddqt Frrayr'
    -

    .- fijq I lctpl

    Aiar 2 Vvd
    -
    Ajar t lwel
    -

    flgurc- !.[-!l DiogFrElt{c rap!$;ssutctlon of tho ricpGh rqleilonr, a,t tha tinc
    of ll.acrellr*ilona for tto Goldcn Bol,t e:ctr Xeewrvlllao thc "6ael aEswla!
    ifrat totttng of tho hydrotheraal, flutC oscurra:d la tJar 1 leno.l (enit abov,c)
    lndor fydlortullo oouil t'l!on's.
    lll+7

    (llg+O and 1391r1). Therefore the filling tenperatures are


    believed to indicate d.epositional tenperatures of 260 23OoC
    for base netal nineralisati-on of the Ajax Beef, 23O - 190oC
    for gold-silver nineralisation of the Bluffs seetion (Birds
    and GoLden Arrow) and Graces r.rorkings and.220 - 210oC for
    gold-si-lver nineralisation of the Chanpion area.

    Salinities are l-ow, being l-ess than 1 eq. wt- S llaOl,


    possibly reflectlug a low concentration of COt due to boillng
    off.

    A partial ehenical analysis of fluid inclusions in quartz


    from Ajax 2leve] (sanple 1?9t1), d.eternined. by crushing and
    leachi,ng experinents (Chapter 7) indicates the presenee of
    7/r0pptr N"*, 630ppn K+, 31ppn Li*, 1220ppn C1.- and approxinately
    0.14, moles/Kg of COr. Quartz from Ajax 1 leve1 (sanple 13938)
    was also analysed but because the water content is not known
    only tfre Na/K ratio of 2.6 can be reported.

    HTDROGEN ISOTOPES

    Fluid inclusions in quartz fron Ajax 2 level (sample


    1391+1) contain llatuer with a 5 D value of -38.3, iadicating
    a probable origin fron meteoric waters.

    SUTPHUR ISOTOPES

    Samples of pyrite collected by the sriter fron Graces


    adit have 63LS values of -0.3 per nnil'(sanple 13g}t+) and -0./.
    per nll ( sanple 13905) .

    pEPTA oF I,ITNERALTSATIoN
    A reconstruction of the depth regine at the tine of
    nineralisatlon is illustrated in Fig. I-N-l using a paleo-
    surface datuur 200ur above the highest peak in the araa'
    Pakirarahi (ZAZn B.s.l.). This nodel assunes that boiling
    occurred. in Ajax 1 1eve1 (and above) under condi-tions of
    hyd.rostatic pressure .
    4lr9

    ll,Bl8 trrll-1 I Ganeral thgraooharleel paratotaft fo'r aPltharlal


    !ia.r81$atl,oa'i ln tho AJax,ve!.a and Eluf,fe
    aectlos of llgavsarl,Lle.

    l!ax Eluffa Rc-fercnccr


    Sectlon

    Bogt roel.s aailollte rbyoJ.Lte


    terpdrature oG 220 lebla v-l
    .250 (ttuu.toluug)
    It
    lruo lonlc tttaugth 0.04 0,.10
    i
    $allnt?Y (n lfaCl egr) 0,11 o.10.
    t
    .f,* 0.016 0.01 2
    Pfi 611 6.5 ;
    Ssa taxt
    pH of haoltalte/gerlel.tc fsblc V-l
    bouailary
    1.7 t.0
    pB of eerlct tc/Krfeldtpar g.'7 6.i, I
    touadary
    foral g (1eg r.{$) -2.0 -2.O Soa toxf
    Log fSa (elsctrur coop') -1'1.1 tabb V-68
    estrfuatsd -10:lo-12.L
    (Ersrr-r-6) i

    Lsg ioz -95.51,o-38.O -J8.Oto-d0.0 Flguraa elteil


    (llg.I-[-,7) (fts.I-!l-9)
    Lsg laa" +1.1 +1.2 Tablo V-l
    lrl+9

    THERMOCiiEMISTRT

    Introduction
    Two nineralisations are uodelled for the Neavesville area:
    (a) quartz, ad.ularia, sericite, brooki.te, chalcopyriter galena,
    sphaleri-te' hessite' pyrite and electrun nineralisation of the
    Ajax Reef in andesite host rocks and. (u) tne lower tenperature
    quartz, pyrlte and electrun nineralisati-on in the overlyi.ng
    rhyolites (Graces, Blrds and Golden Arrow uorkings). Table
    I-I[-1 lists sone parameters of the geochenical environnents
    of these mineralisations.

    A.i ax Reef
    The geochenical environment of the Ajax Reef is Limited
    on Ln fS, versus f0, dlagram (Fig. I-i{-6) by the presence of
    pyrite, chalcopyrite and galena but absence of pyrrhotite,
    bornite, nagnetite, henatite and graphlte. A pH of 5.1,
    calculated for the K-feldspar - sericite bound.ary uslng the
    concentratiou of K+ neasured frou fluitl inclusion analyses,
    ls assigned to the hydrothernal fluids because both K-feldspar
    and seri.cite are vein constituents.

    Contours ofn2S plotted at pH 6.1 in Fig. I-II-6


    1og
    indicate that concentrations of total sulphur i-n solution
    between 0.1 and 0.001 m are possible (1oS nlS = -1 to -3).
    Conparisons with other nineralisations suggest that a value
    around 0.0112 night be approoriate (sUiaea in Fig. I-l{-5) and
    therefore this value was used to calculata the f0, versus pH
    diagran shown in Fig. I-i'tr-?. The shaded area in Fig. I-N-7
    represents the Ajax Reef fluid.s.

    Graces, Birds and Golden Arrow


    The quartzr pyrite and eleetrun nineralisation in the
    rhyollte host rocks (Graees, Birds and Golden Arrow uorkings)
    is uodelled in Figs I-lI-8 and l-i"l-9 at 22OoC. Analyses of
    electrun fron Graces open cut reported by Torckler (tgZg) are
    used here to define a 1og fSa value of -11.3.

    Torckler described secondary quartz and. K-feldspar


    lrSO

    fr;l*lrtedt oir*hmd
    tqP*|*l.t$atz

    c{
    (n
    q-
    so PYRRHcrTFE
    /'l I
    t*uor,)
    gl=
    g; \,t:
    d,*2^ qr
    erlr E
    l- ir
    -49 -& 4 42 -4 -?g -rc -9 -t2 -* -n -?s

    Log f 0z

    Flgure l-lt-6r fS2 vereue f0, dlagran at 250oC shor!.ng the {eochenlcal
    envlronncnt (ltne of croaaes) of quertz * adularls + chalcopyrlte + ga1na
    + ephalerlte t hoasl.te + pyrlte * electrun ulnerallsatlon ln the AJax Velnl
    lfeavcsvllle. (Scc table f-il-l for relevant theroochanleal paraoeters and
    Appondlx V for netboda of conetructloa,)
    451

    -71 K- {e,ldepar
    I
    -n I{EMATITE
    .?,
    :
    -v
    -7'
    (\' -*
    o
    -n
    (t i
    o -16
    s r*l.lI
    -n -L..slagtl.
    -&
    -4t
    -42
    PYRRHOT
    -4' '+I

    Flgure l-tl-?: fO2 veraur pH itlagral at 250oC cud {,S.0.01r ehoulng tbc
    geoaheulcal onvlronocnt (cheilsd) of quartz I adulerle * chalaopyrtte +
    galena * sphalerlte t hessltc t pyrtte * sloetrun ll.rarallsatlon lo tha
    AJar Vela, Neaveavllle. (Sse labls I-lf-l f,or relevaat thernocheolcal
    paraoctcra aad Appendlx V for ucthods of conrtructlon. )
    lr52

    $r
    glii
    DlilillVal Dfs:d,vad
    -1 t"rrye
    Strrphirlc

    Sr
    trr

    s f',
    #, \\e
    "J'b
    MAGNETITE HEMATITE

    -r2 -9
    Log f 0z

    Flgure l-lt-8: fSa versus fO, dlagran at 22OoC for eleatruo olneralleatlon
    ln the Bluffs gectlon, Neavesvllle. The cooposltlon of electriru (reporte<l
    by Torckler, 1978) Lndllcates a log fS2 valuc of -11.3. lhe absence of
    graphite and heratlte l1nlt log fOa betveen -40.6 and -35.8 respectlvely.
    Flnally the lntergectlons of, 1og n lS contours rrlth the log fSa = -11.3
    llne auggest that log n{S was approxlnately -2.0 and therefore that the
    chaoical onvilonosnt of deposltlon rras near the lntereactlong of the log
    n {S = -2 contour, and dLssolvecl aulphlde = dl.esolved aulphate boundaryl
    rtth the log fSa = -11.3 llne. (See Appendtx V for uethods of construetlon.)
    l*53

    Scrtctle I f-fuldspr
    :
    I
    I
    I

    iurunrne
    I

    oN
    rtl.Z I

    a -=ii.-t-
    -tZ
    :
    I
    I

    PYRR,HOTTTE !

    PH

    F!,gure l-ll-9r fr02 verrue pH diagrar at 220oC aud {S.0.0k aboulng tbe
    gooclronlcal snvlronrent (ahrdcd) of electrul l!.neralLgatl.on tn the Bluffr
    Sectloa, lleaveavllle. (See leble I-N-l for rclsvant therqochellcal
    paraoetcra aud Appenrllx V for lethodg o! constructton.)
    l-5L

    alteration ln the warl rocks and, therefore the pH of the


    fluid is considered to be around 6.4. (equivalent to the
    sericite/K-feldspar boundary). Contours of 1og * I S,
    plotted in Fig. f-II-8, indicate that the coneentration of
    total sulphur in soLutj.on was around 0.01m (loc za{s = 2.0).
    Therefore this value was used to construct the f0, versus pH
    diagran (Fig. I-1tr-9). The probable region of nineral
    deposition in this figure is shown by the shaded. area. A
    flutd with approxlnately equal eoncentrations of sulphate and
    sulphide is indi.cated.

    Discugsioa
    conparison of the two sets of diagrans for the d.ifferent
    nineralisatlon tenperatures (Figs. r-H-5 and r-i{-? at z:-ooc
    and, Figs. I-lI-8 and I-N-9 at 22OoC) shows that tbe two fluids
    occupy sj.milar flerds of stability. Tbe dlfferences in fOr,
    fs, and ,z I s values are rnainly a function of the diff erent
    tenperatures. Therefore it is probable that tire different
    mineralisati.ons were concurrent and thei.r plunbin3 systens
    interconneeted. The nrineralisation in the rhyollte host rocks
    was forned at a high level, slightly lower tenperature anc
    from nore evolved fluids than that of the Ajax Reef. The
    slightly higher pH ind-icated for the lower tenperature
    nineralisation was probably caused by boiling (as evideneed
    by vapour rich fluid incluslons) and loss of COa.

    The Bluffs section and Ajax vei.:0, are considered to


    represent different levels of a single fossll geothermal
    systen. The hydrothernal solution was'hot recirculated
    neteolic water.

    Mineralisati.on in the Ajax vein was probably in response


    to an increase in pE of the hydrothernal fLuid caused by
    reactions wLth the wall rocks and resulting in deposition of
    netals fron ehlorid.e eonDlexes.

    At a higher leve1 ln the hyd.rothernal systen, boiling


    oceurred. and, gold (electrun) was deposited, at various sites
    L.i

    I
    l'55

    along the Bluffs EeetLoa fron suJ.phidJ oorpluxes as a result


    of the loss of Hrs frou t'he fluld, 0xiclatioa ( by eixlng with
    n-ear surface waters) is lndicated b,y the gtabilLty relatioas
    in Fig* r,-I{-9 (ar,rd pos,sd.bly ar,so n'lg. r-g-?) and nay have arso
    beere an Lnportant faotoar.

    ngrnneNces .e,ND nlsrrocnEpnr

    ADAI{S, A.fl, 191'


    BABKER, R,G. i BRATETfAItE, R,L.; T0ROKLER, I,. 1990
    BIESL, J.lol.; FRASER, 6. 1912a see pp 8l g7
    D0HI[EI, .].F. 1935: see 1?O - 173 arld Z8i
    NEIISEDI, E,r . 196g
    S0HOFIELD, J,C. 7967
    TOROIffiER , L, 1978
    $IIU{-IS!{SI C.,J. 1971+:. see pp 123 - 121,

    t,

    r_ -'
    lr56

    I-0
    }lARATOTO

    Ii.ITRODUGTION

    Bell & Fraser (lglZ) noted that the history of nining in


    the i'laratoto area had been one of repeated. fai-Iuras because
    of the difficulty in treatS-ng the low grade argentiferous ore
    and. the d.ecreasing ore grad.e with depth. Recent attenpts at
    nining sone of the deposits by Consolidated, Silver l.lining
    Conpany proved no excepti.on and in 1973 they abandoneil their
    operations on the Canoola and Silver Queen Reefs

    680r000 grams (21 ,gia ounces) of fullion trere prod.uced


    fron 12,830 tonnes of quartz up until 1935 (Do'..mey, 1935),
    vhereas Consolid,ated, Silver Mining Gonpauy prod.uced. 3 nillion
    grans (951000 ounces) of sj.lver and, 23,000 grans (lZo ounces)
    of golC between 1958 and 1973 (i.lines Division record,s).

    The geology and aj.neralisation of the deposits uere


    described by Ball & Fraser (1912) anC I'lain (lgll ,1979), while
    Robinson & C;hristie (tgeO) investi.gateC the stable isotopes
    anC f1uid. incluslons of the Canoola and Silver Queen veins.
    t

    During the writers study onJ-y 3 Ievel was read.ily


    accessible, the levels belorv being flood.ed.. Rapid deterioration
    in the state of the workings was noted between visits, the
    Last i.u early 1978.

    GEOLOGT

    A geologi.cal nap of the area is presentetl in Fig. f -0-1 .


    The veins occur in Coronand.el Group and.esites and d,acite flows,
    breccias, tuffs and intercalated. sed.inents (conglonerat6g,
    sand,s and silts).

    EYDROTEERI'IAI, ALTERATIO}I

    Main (lgll) noted that the hydrothernal alteration of


    the and.esite and d.acite flow and breccia rocks in the lfaratoto
    area occurred. in a concentrle zonal pattern around the quartz
    ]'
    I+57

    i'?a!* ^'fi

    ffi a*Axrl AlrEESrrE COROvIANDEL


    c*ouP
    \
    FoRv^rror{
    OU,}IAROA IGNII|SRTTE

    a
    I..-J
    0acrtc
    Rr'drtr,
    florsrbtzcirarl
    an4.
    Rrr.iodacrta floua
    " "'
    -J6RoUP
    lwurrtrNgl

    Efiftrr,rcn& ondcdrte
    lC*O#
    An&rrte and do<rte lGRO!.lP
    tlwr, Vw,crrorl t xdiacr{BJ
    Vah4

    ,t29
    Klbvtrctras '----IN \-

    Fl6ure I-0-1 c Geology of the Haratoto-Golden Croae-Kouata-llaltekaurl area.


    (Cooptled fron Bell & fraaer' 1912; Rabona, 19752 Haln, 19?9.)
    458

    veins. The sequence was describeclr.in order of increasing


    intensity of alierationr ELS follows3
    Zone 1 unaltered rocks :

    Zone 2 nild1y altered rocks: alteration of pyroxene


    to chlorite and carbonates.
    Zote 3 noderately aliered rocks: pjrroxene eonpletely
    replaced, whereas feldspars and opaques show
    varying de3rees of replaceaent. The alteration
    produces chlorj.te, epid,ote, carbonate, sericite,
    secondary quartz, adularia, zeolite (heulandite),
    pyrite and. minor c1ay.
    Zooe. l+ hi.ghly altered rocks: an assenblage of quartz,
    clay (kaolinite and nixed layer chlorlte
    uontnorillonite identified in one specinea fron
    the Canoola vein) and pyrite is prod,uced,.

    !"I T I.IEP.AI I S A T I O1.I

    ction
    Ini;roclu
    17 veins lrere mined in the l,laratoto area, the nost
    inportani; beinq the Payrock, Haratoto, Silver lueen aad
    Canoola (l'lg. f -0-2) . The Payrock and i'iaratoto are the
    largest veins, traceable for 3 and 2.8kn respectively. l{ost
    of the veins average less than 3qr thick but the Canoola
    averages 6.1,1 and attains a naxinun thickness of 2lr.b (Uain
    1g7g).

    nineralisation is fine grained and occurs ia quartz,


    The
    quartz pseudonorphs after calcite and calcltd gangue.
    Table I-0-1 lists the netallic ninerals reported, fron sone
    of the 'relns by Bell & Fraser ('lglZ) and llain (lgll ) aad
    additional ninerals id.entified here. Au:Ag ratios are
    qenerally less than 1:100. Sllver oeeurs as acanthite
    (argentite), hessite and nati.ve silver: eJ.ectrun l.s extreueLy
    rare. !,lain (lgl't) and l,lain et a1 (1972) also recorded,
    aguilarite (AgaSeS) Uut this could not be confirned by the
    writer even after exanination of l'laint s specinens i'118185 and.
    1,118186. The latter contained si-lver anC selenlun as
    seleniferous acanthite, Chalcopyrite' sphalerite and. galena,
    although absent (oxid.ised.?) from the upper levels, are the
    lr59

    o roo zoo3oo (oo5oor'----\ /i


    ll
    ---- / /:-c

    ( /F=d"#

    d.';tXH

    /F
    Cro

    99V",* rith dip ongle. Foults I proboblet === Rosd to mine


    -t--l

    FtgureI-O-2: The velns of the llaratoto area (after Roblnson & Ghrtatle. 1980
    1l1e.2). Detallecl plana of thc fiaratoto Hl.ne rere glven by ilatn (19?1)-
    &6a

    SABI;E I.O-1 r dhoelllttt of ptr.Ecny lotalllc d,uera].a ln aole ot the


    vo,!,ls of tbc llmetoto arsar fdeatlftoatl,.eua by:
    I r Epltr I Sraser (1912), 2.,!t.rta, (19?1f r ,! . lllln (tlzgl,
    4 r tblo rtudy' (? '- uneertetn trdcatlflettlgn)

    oHO
    {thOff
    Il.noral crt3 rt>rE{l.tf
    tr*aOrlh
    .5 dottt{roo3 .rt
    ct Fl. r, +r
    'rt.{(,Oglarfflt l| i{ r, .{
    It ,ilOr{ILhE
    o tllA?lCoalrq

    3t, f,lppo 2 2

    OrqooLa L 2 , 2 4 2 2
    $llvcr Quesn 1 2 L 2 1?1 2 ?
    Ju1lc 1 1 'l 2
    0srbetts 1 7:

    BoyaX, 2
    Gord.ens
    (llolcpre Jaok)
    Goldsa Spur , tn t 2t2 I

    l(aretsto 1 32 I 22
    Pr roct 1 2 1
    l'61

    Flgure I-O-3: Gaaerallaed plan and longltudlnal gectlon of tbe Maretoto vel.nal
    after Hsia (19?9 ffg.?). llatu (1979, concluiled that allver nlneralleatlon
    at ltaratoto occured ln lan ahapetl zonee (Iongltudlnal sectlon) wlilenlng
    upvards. thege !oa6 uers asEocLatedl vlth the wlilest parte of tho velua
    and e varlaace of veln ctrlke dlractlon.
    L52

    predoninant nineralisation in the lower levels of the veinp


    in vhich they were recorded (".g. Canoola and Sj-lver Queen).

    Follovring a d.etailed. appraisal of the structure and


    prod.uction reeords of four veins (Silver Queen, Canool-a,
    I'iaratoto and Golden Spur) ilain (1979) conelud,ed that the silver
    ininerali.sation occurred j.n fan shaped zones r,ridening upwards
    (FiC. I-0-3). These zones nere associated, lrith the widest
    parts of the veins and a variance of vein strike d.ireetion.

    Canoola Vein
    The paragenesis of the Canoola vein is illustrated in
    !'ig. f -0- 4..

    Stage 1. The Canoola vein is d.oninated by breccias.


    coniai.ning blocks (up to 1.5n) of country rock, calclte or
    both, cenented by calcite, quartz and. pyrite. These are
    followeC by calcite deposition in an open vein prod.ucing a
    band of blocky ealcite.

    Stage 2. A series of alternating quartz and calcite


    band.s (Sta3e 2a) preceeC the sulphicle mlneralisation (Stage 2b).
    Bands of rhod,ochrosite (l,tn carbonate) are also deposited at
    this stage and later d.uring initial sulphid,e nineral.isatj.on,
    whereas siderite occurs at various tines throughout
    nineralisation and after it.
    d

    In hand speeinen the nineraU.satioa (Stage 2b) occurs


    as a singl,e or paired narrow (up to 40nm' e.f,. sanple 285/37/3)
    black band, of fine grained sulphides i.n quartz and caleite
    (Fig . l,-5).

    In porished sections (13937, 13967, 285/37/7 and 285/37/8)


    sphalerite, galenar pyri.ter' chalcopyrite' acanthite, electrun
    and hessite (in order of abunCance) occur as ind.ividual
    grains or aggregates scattered in quartz and calcite gangue
    (figs. l+-32 and, lr-33). The vari.ous netallic ninerals generally
    nake up only 5 t,o 2O9 of the band but j.n sone parts they are
    up to 5Tfi (ZA5/31/l). The nlneralisation is .generally fine
    graiaed averaging 0.3nn (".g. 285/37/? ana, 285/37/8) Uut
    t+63

    4
    "ffi 2 3
    a I b I c

    Qrrrlz

    Calcite
    O >od+l
    oo
    tl ?lol
    ?yirtc
    fu'todocMoirtc
    --l-rl i

    Sidq.rltc
    ll
    5rttalr;rife
    Galcv'ta
    tl
    Qtalcopltite l-l
    Acarthifs
    Elaclrvm
    Hesste,
    C}rblcocile
    Corqlhla
    MavtqaneSa
    OxidaS l\

    Flgurc f-O-t: Peragcnctlc roqucnc. of ulnorals la thc Ceooola Velnr Haratoto.


    t 6l,

    consid.erably finer grained nineralisation' averd.gi.ng 0.05nn


    occurs 1n sone speci-nens (13937 and. 1396',1).

    The sulphides oecur as regular grains in quartz, the


    latter generally exerting euhedral grain bound,aries on the
    sulphi.d,es, especi-ally galena, whereas in calcj.te gangue the
    sulphid,es are irregular, generally finer grained (especially
    in 13937 and 13967) and often scattered in a ttpepperedrt texture
    (Fig. 4-32). In the latter, grains of sulphide nay be
    surrounded by large nurnbers of ninute blebs of sulphid,e often
    oriented in Itstreakytr textures. Acanthite also occurs as
    thin ribbons aloug tbe nargins of euhedral quartz grains in
    all specineas. In calcite it cornnonly occurs as atollS.
    Generally, when contacting, the sulphid'es have nutual
    bouudaries (Flg. lr-3)) .

    Stage 2 end.s with a periocl of barren quartz deposition


    (stage 2c).

    Stage 3. Stage 3 consists of vug quartz eoated with


    later carbonate and pyrite. Quartz crystals up to 40nrn occur.
    In ons sanple collected by the writer the euhedral quartz
    crystals are assynetrically coated. by later sinerals.
    However, because this feature was not observed, in situ 1n
    the nine and the ori.ginal orientation of the specinen is not
    known, the flov direction of the hydrothernal fluid' cannot be
    deternined.

    A1-though supergene rainerals were absent fron Canoola


    Veiu roaterial studied by llain (l9lg), chalcocite and rare
    covellite occur in saaples 13937 and' 285137/7 replacing
    chalcopyrite and a few grains of galena.

    Silver O,ueen Vein


    The paragenesis of the Silver Queen vein is illusirated
    !n I'ig. I-0-5. Three depositj-ona1 stages are recognised. fron
    observations in the nine and of hancl specinens and' polished
    sectionsr '

    Stage 1. Brecciation of the country rock with subsequent


    465

    Xeot 2 3 4
    \
    Mrncrals a b C d

    Quartz
    t^ c
    Calirfe, o
    Pyritc
    Sphalcrrle
    Galena
    t- L
    t-

    F
    ChalcoVyitc
    t_
    I

    Hasslfe,
    Acarnthrfc
    Eledrt'trr'r
    Chalcoite
    rf-
    -

    Covallife
    bovifie,
    Wrcane.sc
    Oxidds

    Stgure I-O-5r Parageaetlc lrsquence of nlaerals ln the SIlnEr Queen Velnr


    Haratoto.
    166

    deposltlon of quartz and calclte has produced a number of bands


    of quartzr quartz cemented wall rock breccia and quartz
    pseudonorphs after calcite which nake uo the bulk of the vein.
    Pyrlte was deposlted at various times durine this stase.

    stage 2. An inltial period of barren quartz deposition


    (staqe 2a) 1s followed b;r quartz with scattered fine qrained
    conposite grains of calena and hessite (ear1y stage 2b). Fine
    grained sphalerite and pyrite appear later (late Stage Zb)
    acconrpanied by quartz and qalena - hessite. These early
    periods of nineralisation were recoqnised ln only a single
    specinen (285/)7/6). The sulphides oeeur as ind.lvldual gralns
    (galena - hessite conposite) scattered. in quartz, the latter
    naking up 60 to 70fr of this naterial. The galena - hessite
    grains oecur as T, x, and Y shapes f111ing spaces between
    euhedral quartz crystals (Fig. l.-1'l).

    Staqe 2e contains an assemblage of fine grained sphalerite


    qalena - hessite (composite gralns), ehalcopyrlte and pyrite
    ( in order of abundance) and is the predominant forn of
    nlneralisa'uion with 'rarious eonbi-nations of these ninerals
    occurrin- in all oolished sections (llgZO, 1jgT5, 13931.-
    13932, 139/*5, 139t6, 285/37/2 and ZB5/37/5.

    Sta-:e 2e ninerals ,'enerall.y occur as individual grains


    or a-rqre;ates of tr+o or three qrains seattered in quartz, the
    proportion of nineralj-sation to varyinq fron one sanple
    "angue
    to another (quartz averages 801). The sulphides generally
    fill spaces between euhedral ouartz grains, a texture nost
    narked in the case of galena - hessite (fig. I-0-6) and
    chalcopyrite. When contactin3, the different sulphlde nineraLs
    appear to hav'e nutual boundary relations arthough sone pyrite
    may be replaeed by J.ater ninerals.

    Stage 2c sllver nlncrallsatlon 1s lnterrupted by a 2 to 5nn


    band of flne to nedluu grained chalcopyrltE, sphalerlte and
    quartz (13931 and 285/31/6). fn one hand speclnen the
    ehaleopyrltc and sphalerltc occur lnterJ.ayered ylth the silver
    nlncrallsatloa (fig. I-0-?). In contraot to eerller quartz
    douhant alnerallsatlon, quartz nakeg up only 10 to LOI of the
    ohalcopyrLte and aphalerlte nlaerarlsatlon. chaleopyrlte
    1167

    Flgure f-O-6: Galena-hcsette eoupoalte grelae (uhlte) eurrpunded by subhedrd.


    ouhodral quartz (grey), Stage 2c, Sllver Qucen VeIn. Sanple 13936. 1100.
    lr68

    Ftgure I-0-?r 6ut rurfacc of, r hand apocluen fror tte 9tlver qusoo voln thoulng
    alternatlng baaih ol Stago 2c rllver (blaelt) aad ohalcopyrLtc - rPhalsrLte
    (yellorl nl,nerallortlon. Photo courtcay of l{r E. Coppard.
    1169

    flgure I-O-8: lledluu gralned Stage 2c aphalertte (grey) r cbalcopyrlte (rhlte)


    and quarta (dark grey-blaek) frou tbe Sllver QuEen Vginr tfaratoto (eaople
    285t3716r. the sphalerttc exhlblta a graphlc-polkl.llttc latergrorth vlth
    quartz. Thc pal'e grey clrcular spota ln chalcopyrlte arc tarnLsh, wbereaa
    the black crcss are pltr. 1100.
    L7o

    pre d.orei nete s and has nutua.l bounCary relations uith adjoining
    sphalerite. The J-atter displays a graphic to poikilitic i
    intergrowth with quartz (Fie. I-0-8).

    . Stage 2 end,s vith barren quartz deposition (stage turi.


    Stage 3. Late quartz occurs in vugs and is coated with
    laier carbonates and pyrite (Fig. 4-8). Quartz crystals up
    'r,o ?Onn J-ong occur (..g. sarnple 13922).

    covel-lite and chaloocite occur ri-nning and.


    Supeggene
    veining the sulphides in sone specinens. Hain noted. rare
    oecuruences of bornite and although he initial1y considered
    then to be !,ypogene (c.f. Fig. 52, p121, of l.lain 19?1 ,) he
    later assigned then to the supergene assenblage (Ilain, 1979
    Plrlr) o

    FLUID II.ICLUS]ONS
    Fluid inclusions in quartz, calci-te and sphalerite are
    generally truo phase, liquid plus vapour, nornal types although
    sone inclusions contain a fibrous solid. phase (sarnples 13916,
    13926, '13927, 13928 and 139115; see Chapter
    13921
    ' 13922, 13923,
    6) and sanples '13919, 13922, 13925 and. 139115 have vapour rich
    and vapour filled (Fig. 6-1 ) inclusi-ons in addition to nornal
    types.

    Large vug quartz crystals (sanples 13919 anil 13922)


    contain zones. of orientated. regularly shaped, (generally
    elongate cyelind.rical) inclusi-ons (f igs . 6-9 and 6-10). ltost
    of the inclusions are nornal types but a feu vapour rich and
    vapour filled types also occur ( see Chapter 6) .

    Filling tenperature and salinity neasurements are Listed


    in Appendix III and, presented as histograns in Figs. I-0-9A
    (Canoola) and I-o-98 (Silver Queen). Fllling tenperatures of
    sanples 13918, 13922, 13925 and 1391.5 require no pressure -
    salialty correction but approxiuately l OoC rnust be adcled to
    fi1-ling temperatures of other sanples to obtain depositional
    tenperatures.
    l'71

    oC 5allniV
    Fiflrhg lempordrurd
    o4.vtf '/"Xacl
    RRRRRSR
    ffi
    $sto

    r= E--5r.rl- tlet}

    dr
    n
    l--,
    ut
    o
    4 -J-
    = tfl
    F
    $ ln2s
    ===

    {} 17970

    ztt)
    =JlfL Bq27 4
    3
    A
    a
    J b0
    rl
    o
    o -r 17916 h

    (,
    N r.r-r..r= l?g74 0l
    tt,
    o
    F
    (ns !.fl-,_ t7g2l

    11924 tq Et

    17?24 e)

    ;(9 E13 tlgt8


    tr trg2g

    RR$RRRR c{r $.- O


    l$72

    Filling lemperalure,'C Salnily


    o aq.wt'7. NaCl
    !i
    nn
    R8
    (fr 83
    c{N $RRB
    a{r
    o
    r.9
    Sc.\NO

    rrLJr-1-
    ilr rvgzz I
    rt

    J
    L l-l-r EI EI
    lt+tE
    tlgFE$r
    C o trrl sl t O
    u) LO=
    |3oro.q00
    (D
    oe.5 o C.l AE
    k rr drJ 'i c, r{
    F
    rr\
    t-lOL>+t
    rrLTal
    dtarFl&lo
    lrt>5+{E
    OOr{OOtP
    zttl t?926 At< r{ tr A d
    alnctstr{+t
    o}.(>rla
    +tFao(!
    !+rOr{bc
    dl ttlx+,g>6g
    tr{O{lE'{
    .r{d<tEl 5I<t1
    zIrl r{trEood
    r{Orthrt\CO
    g. A^
    'lAt-tD o O\ O
    trl l3gt7 utcte <<qt.+){'
    F6{r-t
    :5 00lFt
    g +lOOO
    o O l -t C r{'E
    tvt-l!tc+tvt
    Aar{2
    O 0l . tt rn 'tt Fl
    o/ C +r !O't Ol g{
    |r)
    -rrl 179t7 Quarlz ra4aa>Cq,
    Crhvlc
    rdrtv'EtetrC r{
    J -s - radF:t{E
    tlr?t-|<

    L
    ACNOO
    6 t{-{oAtc4
    r]OIC'rO.,
    >ral>Fr(Y\Y{O
    lrFoh
    qt fo d ,E
    E+r-1..r{>
    17927 '|lrOoO\o
    kco+rFr:
    AtEoC'lO
    dd+)mE
    i{L)6ea1r
    Or{&e
    oosrott+r
    |E g{. - o\o rt
    N El+tFlE
    stog.+t
    h O E^ E b0
    rd boi{ O Q at 'l io
    o o+rko\t/rhg
    +tilertvrl

    6u E t--l-
    rl h- B92A
    trt
    oCO+,
    rt?t
    i4-IOHHOOt
    lO | .t
    rlFlHeld+t
    6A.HFtrtt
    ..E|b!.rlllo
    lt .

    O\+tat+{Xt{rltr
    1619,9.+l!t
    O o vct h
    tL^C:tl|lt{
    Hd4Cooqr'{
    AovlAAqoqrt
    O q'{ O >r!
    ,{a+r><>.)+t

    t}
    t
    bo

    h
    S :---l !- t?1?5

    rtltttttl

    $R$RR RRREs q..|sla

    rrl
    O.
    6I
    H
    a
    o0
    E
    l*71

    TABLB tr-Otz,t Isotopic coEpotltlo! of, rU:Phtalc !l.nrsL! ,fror the ilaratoto
    lllaor aftor Roblaron & chrlgtl.a (1980)' Sore oeuple Duqbotrs
    bavo bqan ehangeit to elnforr vith thoee utaal tn thls fhea{s
    aa.l thc atrlv.er nlng-f,al trlstsd as agulltd'tc by E.bblngon &
    Chrlatte (1980) raa lilentlflsd bsro al rclsnlferoul acantbtt6,.
    q3i!ss'
    179:29 Oeuoerle I Level 1 ElochY calaltc rltb ultror Fyrtte +t.0
    ltg?g South Stope 2b g5e-gralnod al,l*st lc.antblta +1.6
    btncrals antl gulfldeg
    1rgz9 'il
    zblllit PSrIte +3.6,
    tnill Chalcopyrl,Ec *2.2
    13976 Caoos]a 3 Lgvel 2b S:tluer nlnerall.zatlon and Aeo'thlt, +0.,1
    North Stopc gulfXdss
    13916 n ir|'t C,baleopyrltc +1.6
    285lt\l2 silrsr Su qn 3 ?b-giin Py.ritr +r.1
    trevct
    figle I ll tifr Chril.cogyrlte *2',6
    11920 .: 5 2c Flne-gr4ined sllvcr Ghalcopyrlte t1.6
    nlnerell.latlsa
    11920 '|| n t Coargc rul.fide banit Sphelerlte +2.,6
    1r9e0 t rl ,rl.t G,baleopyrltt f2r.1
    2s5lrxl6 ' , ri i.rt|' Sghaleflto +1.0
    285ltrl6 . i I tllt ChBlqopyrlte *1.&
    11922 's , , Po,st ],atc cel,cl,to Pyrlta +1,,6.9

    1Vg:2? i t trrtl Pynltc +1 6,0


    i
    l+7 l+

    13920is the onl-y sanple stud.ied. representing sulphide


    nineralisation: al1 other sanples occun either earlier or
    later in the vein paragenesis. iilevertheless fairly constant
    tenperaturesr &s inCicated by the slodes of the fi]-]-in,g
    tenperature histograns (fig. I-0-9), occurred. throughout the
    various stages of the Silver Queen and Canoola veins.
    Sulohide nineralisation probably occurred in a tenperature
    range of 2?O-300oC. A telperature oi 280oc is consld.ered
    reDresentatlve.

    Salinities were also fairly sinilar throughout the various


    vein stages although considerable variabllity is displayed. by
    individual sanples-
    Table 7-7 lists pari;ial chenical analyses of f1uid
    inclusions in quartz sanples 13919 and 13926, deterained, by
    crushing and leaching experinents. The i{a* and, C1- values
    o.f tbe two analyses are very sinilar, whereas 13919 has a
    higher proportion of K+ aad nuch less COz (tatte 7-gll than
    13926. The IIa/K ratio deri-ved from 129"6 is approxinately
    the sane as that predicied by the Iia/K seothernoneter at a
    tenperature of d.eposition around. 280oC, whereas the nalK ratio
    of 13919 is nuch lower than pred,icted. theoretieally, 3.L
    instead of around 7 at 23OoC.

    SUTPHUR ISOTOPES

    Robinson &Christie (t9eO)" lnvestigated. the sulphur


    isotopes of sulphide mineral-s fron the Canoola and. Silver
    Queen vej-ns. Their results are reprod.ueed in Table I-O-2.

    63LS values of *0.7 per


    S.tage 2 sulphid,es range fron
    nil to *1.5 per ni1., 3 pyrite
    whereas two sanples of Stage
    have unusually high 63LS values of i16.0 and, +16.9 per nil.
    Because of difficulties experienced, in separating the very
    fine grained, sulphides only two cogenetic sineral pairs coulC
    be measured, their fractionations ind,icating tenperatures of
    zgo! 6ooc (1zgzg, py-cp) and, 275! 100oc Ozgza, sp-cp) in
    agreenent with the fluid inclusion filting tenperatures.

    FOOTI'IOTE: The wrlter vas involveC in on-ly a few of these


    analyses.
    t, ,
    l+7 5

    518 0 suow l%ol


    U
    ^02r,6810 12
    -
    1t, 16 18

    ,/' ,t //'
    -2 -/' // z/ -/'
    ,"ttt-"-.r"
    l/ ^./ -/' //
    E tt'-//stoge 3'
    s)
    (D
    -4 -,2\"6\t'tt
    fr\- /- -/
    o /
    -tt-Y I '\/
    a\-
    o-
    L)?
    avr -o
    // -.:,itoqY
    -ao

    -8 dt#:#>.iir'
    _?-:+y+/Stgse 2.
    -10
    3s0 300 2s0 200 1s0 100 60
    Temperoture ("Cl for 518 Oore fruid =-to/oo

    Flgurc I-o-10: A plot of 513c r"t"rr" 5180 for vel.n carbonateE fron the I

    Caooola anit Sllver qusen velns' Haratoto, (after Robtnson & Chrlstle, 1980
    r1g.4). Tho telperature Beale, def,Ined for a value of 5180 flutd = -4
    per u11, lndlcatea a decreaelng tenperature regl.ua donn to 60oC for late
    overgrorthe of calclts on Stage 3 quartz. . The poaltlon of the aenples
    reletlve to the 61Jc urco, contours (ilashed ltnes) suggeate a value of
    -? per ull for thls pariueier (elso rA 613c,.ol.
    l'76

    cAF.BoiI Ailp oxYcgil ISoTOPES

    Robinson & Christie (t9ao;o analysec the carbon and oxygen


    j.sotopes of several vein carbonates. 6180 values ranged fron
    +0.7 per ni-} to + 17.5 per nil, r.rherea= 513C .r"Iues ranged-froic
    -A.7 to -9.2 per nil; When plotteC on a 613C versu, 6180
    d|agrao (Fig. I-O-10) these analyses can be used, to indicate
    depositionatr tenperatures for a specific value of 51BO in
    the hydrothernal fluj,d. A value of -4 per mil was used and
    defined a decreasing tenperature regiae d,own to 5OoC for late
    overgrowths of calcj-te on Stage 3 vug quartz. A few dissrep-
    ancies r,rith fluid inclusion filling tenperature evidence ttere
    8O value of
    reconciled. by considering variations of the 51
    the hydrotherrnal fluid. The carbon isotopes were believed to
    relate to a E13C value of -? per nil for iIrCO, in solution
    (tfre carbon fluid species fractionating against the precipitating
    carbonates).

    HYDRoqEI,IIS0T03ES :

    Fluid lncLusions in sanples 13926'and 13928 contai.n uater


    rith 5D values of -48.5 and -112.4 per ni.I respectively. If the
    water uas originally neteoric it nust have been forned in a
    cooler clinate than present. Alternatively, if the neteoric
    water had a sinilar 6D to present day waters the neasured
    6 D values of the fluid inclusj-on waters could be forned by
    a nixture of meteoric and nagnatic uaters.

    DEPII{- 0F !,III{ERALIS.ATIoN
    The depth of nineralisation ls constrai-ned by the
    occurrence of boilingr at a nini.mun tenperature of approxiroatellr
    260oc, in 5 lever during Stage 3. Depending on the concentra-
    tions of dissolved, salts and C02 in tha fluiil' boiling could
    oceur at Z6OoC under hydrostatic pressure conditious at
    naxlnu.to clepths between 5LAn and slightly greater than 1kn
    (e.f. Haas, 1971; Merchant, 1978). A depth of 800n uas used'
    for this factor in the construction of the depth nodel
    illustrated. iu Fig. I-0-1 1.

    $,1Q!!@: * A11 carbon and oxygen istopic analyses and'


    intarpretation by 8.tr'I. Robinson and staff of I.II.S.
    -. t.
    L77

    Flgurr }O-1 lt D!,agrelat1e. roconrttxotlon of thc drpth of r'lnatal,tsaiioll at thc


    tlaretoto lfinsr tlhc poslu,on of ths aqrfioe ilatun i'g llnLtcil by the
    osoualrrco of boi,llaf aD 5 lsvel ilurlng Staga 3.
    47a

    TIIERl'IOCHEI"IISTRY

    The geocheurical environnent of nineral deposition for


    both the Carnoola and Silver Queen veins is lioited on the fSZ
    versus fOa diagram (Fig. I-0-12) by the presence of pyrite
    and chaleopyrite but absence of pyrrhotite, magnetite, henatite
    and bornite.

    Valuescf 1og fSa between -8.8 and -11 are indicated by


    the sphalerite and electrun conpositions, whereas log fOe 1s
    Limited betweea -36.1 and -32.5 by the absence of .graphite
    and the presence of ealci.te but not anhydrite, respectively.
    A further linitation on fOa in the Camoola vei.n is provided
    by the presenee of rhodochroslte but absence of alabandite (UnS)

    Intermittent periods of siderite d.eposition occurred


    duning Stage 2 nineralisation in the Carnoola Vein. The
    approxinate (see AppenCix V) position of the siderite stability
    fietd at 1og fCOa = *1.2 is shown in Fig. I-0-13 toqether with \

    the probbble field of sulphide mineralisation (the shaded area


    transferred fron Fig, I-0-12) anC indicates that the transition
    fron pyrite to siCerite Ceposition was probably caused by a
    decrease in fSZ or an increase in fOZ (or both).

    An f0, versus pH diaeran, c.onstructed for a total sulphur


    in soluti-on concentration of 0.01n (1og m S -- -2), is presented
    in Fig. f-0-1/+. The shaded area ltArr represents the posslble
    range of nineralj-sation for the Canoo'la vein and^ indi-eates
    deposition fron a fIuld contai-ning approxi.nately equal
    concentrati.ons of dissolved sulphate and sulphide aid at a
    pH around 6.2, in equilibrlun with K-feldspar and sericite in
    the wal1 roelis. The absence of rhodochrosite and alaband,ite
    in the Silver Queen vein allows a greater possible range of
    fluid composltions (fielas I + B in Fi3. I-0-1/,) extendins
    well into the reduced sulphur species predoninant fieldr &s
    far as the caLcite soluble/insoluble boundary at pll 5.5.

    The stability field of siderite sho',rn in Fig. I-0-13


    demonstrates that the nagnetlte field of Fig. I-0-1 4. noay in
    fact be occupied by si.deulte. Therefore periods of siderite
    deposltion in the Canoola Veln (e.g. at 1og fOa =.!2.O to
    -33.0 in the rrmagnetiten field of Fig. I-0-1/+) probably re-
    "i)
    l*79

    N
    (/r
    ?YR HortlE
    IF
    o /

    unonLrns
    I

    Lq foz

    Flgure I-0-12c fS2 verrus fO2 illagrau at 280oC ahovlng thc chenlcal envlrontent
    (shaaled) of Stage 2 quartz + calclte * sphalerlte * galena + pyrlte +
    ehalcopyrlte t acanthtk t heaslte ! electruu nlnerall.satlon Ln the llaratoto
    vel,ng. Log fs, frou apSalerlte coopqeltlona o -8.8 to -9.7, Iog fS, fron
    electruc. conposltlooe (Ganoola veln only) '-10.7 to -11'0r and log f0ot
    froo f,t-uld lncluslou aaalyees - 11.2. (Constructlon rethods are degcrlbed
    lu. Appendlx V. )
    1.80

    (r|
    rt\
    tf-
    gr
    o
    -l

    4b 4* '4z '4 -n -rr3 -g-n#q


    Lo9 lat

    8!,gulo I.O-13r f82 varlua 80, dlagral rt 28got" lnslrdlng the t,trdortte
    rlobrtl,ty llcl6 aL 1og f062 g r1'2r for g.tage'.' rjltcs.raltsstlon tn thc
    ceroole llel,n. Interrnlt ant pertoilc of sidcrlte' ilcpos4llo8 uQFc p:,o.ba'b1y
    cruaed by a. ilocrasre le fs, artt/:o.r an lacraqgr 1l foa relrtl,ve to tha
    rore eoDtloa pyrl.to t olalcopyrlte (+cphslerlts f galeua * acantbl-te I
    elcgtrurl depol!.tlonal envtroureat.
    481

    c{
    o
    r+
    BOR'{ITE f, F/RffE
    ct
    s
    wlz;i;--q---1
    !eqL2z---'Lo----i---
    'l
    J4-Llz::!L---J :
    e
    !s
    PYR,R,I{OTITE ! Is

    Flgure I-0-'14,: f0, versus pH dlagran at 280oC anil 4,S= 0.01a shoulng posslblo
    chenlcal onvlronnents for Stage 2 quartz + calclte + sphelerlte * galena
    + pyrlte + chaleopyrlte t a,canthl.te I electrun * rhodochroelte nl.neraltsa-
    tl.on ln the Caooola Veln (ohadod area A) and Stage 2 quartz + calclte +
    sphalerlta * gaS.eoa + pyrlte * chalcopyrlte t heaalte nlneralleatlon ln
    the Sllvor Queea Vatn (ebaatsd area B+upp6r part of A), f ' 0.09r aK* .
    0.019, pHra6,1oq fS, fror ephalorlte coupooltlons. -8.8 to -9.?r log
    fS, frou electrur conPosltlons (Caooola Veln only) ' -10.7 to -11.0, and
    1og fCO, f,roo fluld lnclualon analyaea o t1.2. (Hethods of constructlon
    ate dcscrlbed ln Appendtx V.)
    ' lr82
    sulted fron increases in f0, and the dissol-ved'sulphate/
    dissolved sulphide rati-o.

    Kaolinite in the wall rocks and veins was not in


    equilibrium with Stage 2 fluids and. uas probably deposited
    at a later stage at lower temperatures. The..Stage 2 ffui{l
    are however considered to be in equilibriun with Mainr s Zoue
    3 noderately altered rocks containing sericite end [-felilspar.

    The fTea versus fS, diagran (Fig. I-0-15) denonstr&s


    'Lhat fTea was higher in the Silver Queen Vein, where silver
    was d.eposited as hessite, than in the Canoola Vein, where
    silver occurs as aeanthlte. This nay be a refleetion of the
    contentration of total Te in solution (c.f. Fig. 11-4).

    GENESIS

    Robinson & Christie (tgaO) consid.ered that 5 34t a, of


    the I'laratoto fluid uas represented by the SSlrS value of Stage
    3 pyrite (+16.0 and +16.9 per nil) and assigned a value of
    +1 6 per nil for this pararaeter. They suggested that the
    probable source of sulphur with this S34S value was Jurassj-c
    sea water sulphate leached fron the greywacke basernent rocks,

    The source of cerbon, however, was postulated as naxrnatle


    i0, because of the -7 per ui1 613C value derj.ved. for the
    HZCO3 in solutj.on.

    to be neteoric water precipitated


    The water was consj-dered
    during a cooler clinate or onto a higher altitude location
    than at present. The water was deeply circulated through the
    volcanic and basenent rocks in an area of high geotherraal
    gradient. It exchanged oxygen isotopes with the wall rocks
    and. becane enriched in various elenents.

    Deposition of Stage 2 sulphide ninerals with t34S values


    be.tween +0.7 and +).6 per uj.l sust have occurred fron a fluid
    containi-ng approxiroately equal proportions of dissolved
    sulphate and dissolved sulphide (Fie. I-o-16) if 634s es Lras
    around +1 6 per nil. Therefore both the Canoola and Sj.lver
    Queen Stage 2 environnents nust plot in field A of Fig. I-0-1 4,.
    lr83

    s3 e
    ;e l.
    -Q'
    s
    j$
    .S
    G-
    (n
    srL
    -6
    I
    et
    !:o i
    ls5
    -7
    \e, solid
    I
    I H

    i/
    Ia vapour I
    I
    I
    I
    -a I
    Calaverife, (Au la,a\ I ./
    -9
    Gotd I e
    L

    ffi
    I

    #
    L
    N I o
    o
    e
    (+. -t0
    I (,
    s ail
    g i,#
    -s
    u
    -tl
    !'
    i2F
    s
    t'
    I
    I
    -12
    lvlerr,ury I
    \ I

    M
    s I 60""-
    -s
    -t, s I
    s I
    .S
    I
    I
    -t4
    -t4 -t7 -t2 -[ -]0 -q -g -1
    log f5z

    Plgura I-0-15: fTe, veraue fSa dlagrao at28OoC shorrlng the dlfforent atablIlty
    regions relatlve io fTerr of the heealte-bqerlng nlnerallsatlon of the
    Sllvor Queen Veln (sttppleil area) and the acanthLte (argentlte) - bearlng
    olnerallsetlon of tha Canoola Veln (dlagonally ruled pattern). (ilethods
    of congtructlon ara descrlbed tn Appendlx V.)
    lr8 l,

    -n
    -4
    HEMATITE
    -n
    -p
    N -31
    a
    *, -72 MAGNETITE
    sa -71 EORNTTE T FIQ,ITE
    J
    -4
    -7'
    -%
    -n
    -%
    -7? PYRRHOTITE

    PH

    Flgure I-0-16: f0r',vereue pll dtagral at 28OoC anil S-0.01r elth cootoure of
    -6^3.Lt
    534S**, fo" rS- +16 per ol1. Preclpltation of Staga 2 eulphlde
    olnerala urtn 631s betveen +0'? anil +3'6 Per nil nuet heve occurred
    ".iut" (1.e'
    Dcar or on the oxldiaed = reduced aquour sulpbur apeclea boundery
    tho sOA2-/HS- boundary tu tbe rllagrau). Thla luforoatlon, together nltb
    that piceeoted ln Fig. I-O-1{, auggeots that Stage 2 olaerallsatlon ln
    both the Canoola and Sllver Queen velng uaa foraeil Ia an envlroouent
    repreaented by tbe ahqded area lu tbe dlagrau above'
    Rot,i:-1son E' ct-rj qur) considered the,.t tl.e ratio of
    stie tt
    oxidiseC:reauced. sp'tphur i;:ec*es i_n ti:e fluid decreased pro-
    gressively in time so that during late Stage 3 the fluid ,,
    contained sulphur alnost exclusively in redueed, forn. Sulphate
    reduction uas considered to have resulted fron react,ioni with
    wa1l roek ninerals {e.g. pyrite) or by reaction vith hydrogen
    in the fluid. Stage 2 uineral deposition was considered to
    result froa changes in fluid pH, also due to reactions with
    vall rocks.

    The nixing noclel suggested by Henley & Seward (:-n prep)


    for epithernal deposits offers an alternative nechani.sn for
    nineralj-sation. In their nodeJ- a hydrother;al fluid
    Srr,age'2
    containing sulphur preConinantly i-n reduced forn rixes with
    near surface waters causi-ng dilution, oxidation a decrease in
    tenperature and therefore mineralisation. However, this
    nodel is difficult to reconcile with the apparent regression
    to a reduced fluid during Stage 3.

    Boiling occurred during Stage I ancl was possibly the


    predominant mechanisro of nineral depositi-on during this stage.

    REFERENCES AND BIBLTOGRAPHY

    BELL, J. 11. ; FRASER , C. 19122 see pp100-105


    DO'vIlfEY, J. F. 19352 see pp227-231r ancl 287
    HAIN, J.V. 1971
    1979

    MAIN, J.V. , R0DGERS, K.A; KOBE, H.t'I .; I.IOODS, C.P. 19?2


    R0BII{SOII, B.I,{. ; CHRISTIE, A.B. 1980
    ScH0FIELD, J.C. 1967
    !IILLrAl.lS, G. J. 197lrz see pp109-110, lr2lr-1,26
    and lr29
    485
    I-P
    G0Lt):ii ci03s
    :

    II TRODUCTION .

    Discovered in 1892, the 9olden Cross l41ne uas r*'orked


    fron 1895 to 1917 produci-ng 12 nillion grars (386'331 ounces)
    of bullion fron 157,667 tonnes of quartz nined (Doi^'ney, 1935)
    The veins uele nined fro:i sl:afis vhich have since collapsed
    naking the nine inaccessible.

    lto geological investigations have been nade on the


    deposit since Bel-l & Fraser ( t 9t Z1 .

    GEOLOGI

    Bel1 & Fraser (tgtz) rnapped the area around the Golden
    Cross nine as pyroxene dacite (c.f. Fig. I-0-1).

    HYDROTHERMAL ALTERATION

    Be11 & Fraser ('lg'tZ) describecl the hydrothermal alteration


    as propylj-tic.

    MII{ERALISATION
    ' Three seni--paralle1 veins; Enpire, Realm and Golden Cross'
    occur in the nine, however the Golden Cross proved to be the
    only one with sufficj-ent gold for profitable uining. '

    In the Golden Cross vein gold anC silver oceurred in a


    single ore shoot as very fine grained electrun in a gangue of
    quartz and quartz pseudonorphs after calelte. Acanthitet
    pyrite and other sulphides occurred j-n the lower levels.

    The ore shoot uas.bounded. at both ends by barren prinary


    calcite. It was longest near tbe surface and.rras gradually
    pinched out by the calcite uith clepth. At the lowest'1evel
    of raining, llo. ? level (approxiruately 210n below surface),
    the vein consisted of ttnunerous para11e1 jointsr narrou
    fj-ssures.and pug-fi-Iled shatt,ered zones, in which little or
    no calcite or quartz has been Cepositedtr (8e11 & Fraser, 1912
    p111). Three dlanond drill holes uelre Put dow:r frcn 7 1eve1,
    187' .

    the longest go!"ag dors:r a further 247n, but no ore was inter-
    sected..
    ;
    BeLL & t'raser (lgta) noted. that large caverns (up to 60n
    Long) uere f,ound ln the or-e sboot during alnilng and. were
    s.tt3.iblrted,tothedissb]-ut5.onoforJ.giua1ca1aite.

    0EltE.srs

    Tbe assoc,iation of ore r.'itb zones of l-eaebed ealcite


    suggests that the physioeocheni.cal condit-ious eauslng
    hyd:lotbernal leaehing llalo have been conduejtve to pre,eious
    uetal clepos$tion. The solubility of ealclte in hydrothernal
    solut,ions ge,nerally i.ncreases wi.th deereasi4g tenperature and
    pu (firoa neut,ral.) aud- i.ncre,a'si.ng fcoz. The.se factors Eay have
    be6l1 responsi.ble for ore dep,osition at Go1den Oross.

    BEFEBE,NCES i.I{D BIBTIOGRAPNI

    BELLr .T.!1. t FRASERT O. 1912: see pp' i10,8 - 112


    D0?J!{EI, iI.F. 7935= 's,e pp 212-215 and 2.8?
    $CEOFIEI;D' J. C. 1967
    l'IIttIAl{sn G.J. 1'9'7 f+t aee p 108

    t
    :?
    488

    I-Q

    i(01.{ATA

    I}TTP,ODUCTIOII

    The Eonata Reefs


    'rere
    nined. fron 1891 until the 1930ts
    producing 16.6 aillion grans (Sltr,852 ounees) of bullion fron
    206,0/+0 tonnes of quartz (Downey, 1935). The nine ranks fourth
    in gold prod.uciion conpared uith other nining centres of the
    Fiauraki Gold - Si.lver Province. It consisted of eight ad.it
    levels. The ore was passed d.own a shaft to 8l.evel fron
    higher levels and taken to the baitery by tranway.

    Recently 8 Ieve1 lras reopened, by Handley & And.erson for


    extraction of andesite to be crushed. aud used. on roof ti1es.

    i{o geologieaL investigations of the nine have been


    reported since BeLl & Fraser (t9tz).

    GEOLOGY

    The Konata Reefs occur in d.acite flows ancl, less eonnonl'r,


    breccias (8e11 & Fraser, 1912) of the Coronand.el Group (c.f .
    Fig. I-C-1 ).

    HYDSOTiiER}IAL ALTERATIOTI

    Bel1 & Fraser (191?) described the hydrotherraL


    alteration as propylitic.
    i,III.IERALISATIO}I

    iiost of the ore fron the Konata Mine eane fron a pair of
    parallel veins known as I{o. 1 and No. 2, showa in longitudinal
    section in Fig. I-Q-1. These veins tend to converge nith
    depthr'bei-ng approximately .lrOm apart at the surfaee but only
    10n apart in the lowest uorhlngs (gett & Fraser, 1912). Both
    veins are lenticular in longitudinal and vertieal- section and
    spllt into stringers at their northern extensi.ons. The widths
    of the veins and ore grade varied i.rith the hardness of the
    country rock, with naxinun uldth of 3n (although lio. 2 Reef
    had Local bulges up to 6n wide) and good, ore grad.e occurring
    in hard rock.
    I(OMA,TA REEF!} MINE

    KOMATA REEFS MINE


    !t'* 2 nEEP

    Flgurc I-Q-1c Loagltudlnal eectlons of vorklngs on llo.'l anil llo.2 Reefs of tbe
    f,ooata lllne. (Fron Ftga. 25 and' 26 of Dovney, 1935.)
    lr9O

    Three ore shoots were found., Tvo occurred ttback to backr,


    one in ilo. 1 and the other in ilo. 2r in the northern part of
    the nine, vhereas the third occurred only in llo. 1 Reef. The
    truo for:ler shoots attained maxiroun length at L level and nere
    found, to be patchy and generally not profitable belou I level.
    The ihird ore shoot apoarently became unprofj-tab1e at 7 level.
    The richest ore found in the third shoot occurred r'rhere a
    generally barren vej.n, Lavingtons, joined llo. 1. Both I{o.1
    and Lavingtons were strongly nineralised in the vicinity of
    their junction.

    The veins consisted of a wall r:ock breceia (fragnents up


    to 1n) cenented. by quartz and calci'r,e (netf & Fraser, 1912).
    Quartz pseudonorphs after calcite vere coninon in the leached.
    parts of tbe veins. The nineralisation, consisting of pyrite,
    electrun and acanthite, occurred, nainly i.n band.ed quartz but
    also in the breccia fragnents.

    Several veins are exposed in the rsorkings presently


    accessible on 8 Ievel (fia. I-Q-z). They contain quartz and
    calcite, but no vislble nineralisati.on, although the ra1-l rocks
    are pyritised. Vugs are co:naon and contain euhudral quartz
    crystals up to 25nn 1ong, The stoped veins are very leached
    and contain abund.ant plaiy quartz, tlpical. of quartz pseudoaorphs
    after calcite

    rl,ulp INCryrSIolig
    Fluid inclusi.ons were investigated in sanples of quartz
    and calcite fron the locations shown in'Fig. I-Q-2, The fluiC
    lncJ.uslons are two phase llquid plus vapour nornal tSrpest
    with the excepti.on of sanple 1391+7 quartz in shi.ch vapour rich
    (fig. 6-5) and vapour filled inelusions also oceur, ind.i.catinq
    that this Later sanple was forned. ln a boiling enviroanert-
    Filling tenperature and salinity neasuretrents are presented.
    as histograns in Fig. I-Q-3. Pressure - salinity correctLons
    of approxiaately 5oC nust be add.ed. to tbe filling tenperatures,
    except those of sampe 1391-7 quartz. The corrected fiLling
    tenperatures indlcate d.epositional tenperatures pred.oninantly
    in the range 27O - LLOoC. The filling tenperature histogran
    191

    I t3141
    t794g.
    2m calcrle (mirpr a$m.?rlldfe,l
    quartz, wl?'t. qnrtz
    qudtz Wvl.
    var',l-)
    lm calclfa, vdnT - /
    o,25tm cahittawrh
    ?oorn

    n wisa

    txguro t-0:-2c ?len ef tlla oecaeslble ael60lsas of 8 lerclr fioEsta lt!"nsr shotrl,tlg
    tho locatlor of aenplea gtuilied.
    lr9Z

    t40t50ttu?@220?frz@UoW O | 2 t
    ;_i_'._
    4

    13941 quarfz

    E=- Jl\- E:- Er Et Er

    ns4t catito,
    ,& [=
    n
    F_FLJ l_
    Bq48 quarfz

    /l Be4B catitc
    J\
    [ht7e4e EEI
    l--l-l---f-l
    @z@rcroo|214
    Filling Tcmporalurz 'C r Salirify
    Qq. wr.f,-Nacl
    5in9lc wlues: Er

    Slgure I-Q-31 f,lrtoglana of prluary flulil laclualoa llllLng tenpcrlturor and


    rpparcnt nllnt,tleo f,or raoplee of guartz ard calcitc ftol 8 lovel of the
    f,ooata tllno (f1g. I-O-2). Tbc lniltvlducL lsrauroDlatg are llotcd la
    tppeudlx III' Satplo 1391? coatalna vapour rlch (818. 6-5) and Yapour
    ftlled lncluslon, la aililltlon to loroat llqutd-vapour types lndlcatlng
    that the hydrothernal fluld uas bo1llng durlng lto grouth. Sanple 13949
    I,a quartr.
    h93

    ur
    lrl
    ric
    F
    IT
    E

    lloppcr

    eritry
    2 lctr;l

    I lsya!
    - 4 lcvcl
    -
    S lqvcl
    a laval
    -
    - 7 lewl
    - 6ley.el
    -
    '!r

    Sigura I-Q-l: Dl,ag.ranatlc raoonrtnlatlor of, the depth of nlneraltsrti.or at


    tbe f,orata tllne a,soqqlAg that bol.l!.ng of the hyilrotherual flulil et 8 lsvcl
    ooqurrad undcr hyilrortattrc pjrorrurr oondltlonr.
    L9L

    of sarDle 13/1 c-uartz na:,' i::dicate a 'l o'..'er tc;.reia.uure of


    ,a

    around 21Ooc but because of its co;plicated shape such an ,..


    interpretation is not nade uith nuch corrfidenc. The '

    initiation of boiling indicated by this sanple probably re-


    sulted fron a reduction in pressure (e.g. further opening of
    tbe fissure). Boiling nay have in turn caused a drop iu
    tenperature.

    The anparen't salinities are ouiie high cor.sicering ,r,he


    type of nineralisaiion and nay. resul-t fron high concentrations
    of C0^.
    z

    SUi,PHUR ISOTOPES

    Pyrite in a sarple of vein material (13905) taken off


    the nullock heap outsi-de I level has a s34s value of *2.g
    per nl1.

    DEPTH OF }.III{ERALISATIOT{

    The fluid inclusions in sanple 1391+7 quartz indicate that


    the hydrotheru,ar fluid was boiling at a depth nou represented
    by 8 1eve1 of the Koroata iiine. Boiling probably occurred at
    a -tenperature around 22OoC under hydrostatic pressure conili-tions,
    indicating deptbs betweeu 250 aud B00m (depending on the
    concentration of dis'solved C0, in the fl-uidl c.f . cata of
    Haas C1gltf and Fig. 5.-6 of i{erchant [tf ZA] ). A depth of
    6O0n ltas assigned to 8 1eve1 to construct the nodel illustrated
    in Fig. I-q-|.

    GEIIESIS

    The Kouata Reefs are characterised by the apparent absence


    of base netal mineralisatj-on. This factor, together urith the
    fluid incl-usion evidence for boiling at 8 leveI, suggest a
    near surface environment of nineralisati-on. l.lixture of the
    hydrothernar fluld uith near surfaee oxygeaated waters,
    resulting in dilution, cooling and oxidation, togeiher uith
    boiling are therefore suggesteil as oossibl-e neehanisns for 'ore
    deposiiion.
    195

    BELL, J.H.; FRASER, C. 191": see pp 105 - 108


    DO1'[{EY, J.F. 1935: see pp 22? - 227 and 287
    scHoFrELD, J.C. 1967
    i{ILLIAl.lS, G.J. 1971r: see p 110
    l'96

    I-R
    i,iAITEKAURI

    Iii?.D.ODUCTIO}I

    The l{aii;ekauri area supported several suall gold nines


    uhich collestively proCuced 1./* nillS.on grans (|tt1038 ounces)
    of bullion fron 35r9ltL toones of quartz betr,reen 1875 and. the
    1930ts (Do',rneyr 1935l . One of these nines, the Jubilee, lras
    re-investigatecl by Consolidated Silver llining Co. in the early
    1970rs. They reopened the Jubilee Low Level but discovered,
    that on this level tbe l{aitekauri vein containecl niaor base
    netal sulphide nineralisation but practlcally no precious
    rnetals. In.conjunction irith this work Rabone (1971 , 1975,
    studied the geology of the llaitekauri area and the accessible
    ninerali sations.

    cE0rj0GY

    The geology of the l{aitekauri &rea (Fig. I-R.-1) consists


    of Coromandel Group andeslte flor,rs (Puketawa Anilesite and
    Jubilee Andesite) and sedlnents, i'lhitianga Group dacite flous
    and pyroclastics capped by igninbrite (Owharoa Igninbrite
    Fornation).

    HYDRoTTiEnIIAL ALTERATTgU

    Rabone (lgll) classified the hydrotherually altered. rocks


    of the l'Iaitekaurj. area into four zones as sumnarised in Fig.
    I-R-2. Zones I to III are regarded, here as propylitic
    alteration, whereas zone Ms lnternediate argillie alteration
    (andeeites) and potassiun sillcate aLteration (dacj.tes).

    lwo types of ''.Zone'IIf alteratLon occur: where carbonate


    activity was relativetry" high, carbonates' clay roinerals'
    ninor sericite, rare epidote and rare secondary biotlte occur'
    whereasin non-carbonate alteration, assenblages of pistacitic
    epidote, secondary pl.agioclase (albite oligoclase)' prehnite
    and apatite occur.

    Intense aLteration (Zone IV) developed. assenblages of


    l+97

    I
    t

    A
    -

    v#
    ,o
    x
    rA
    A

    A
    \ AI
    A
    A

    '+,

    cul to Portal

    $lqifaY-auri Van
    -

    Jublloe Low Level


    t
    Flguro I-R-1: Gaology of tbe l{altekaurl araa and locatlon of the Jubllee Los
    F
    |.
    i
    Level (after Rabone, 1975). I
    49e

    ZONE, I ll ill IV
    fvzsh rxh wcalc to moacraltz lY'tcnsa
    ALTERATION: to wak mode,ralc lo Slrm

    Chlorifc
    C-arborvle
    Clay Mrhamls
    Sericito,
    Epldote'
    e--^.-)^.-.,
    )v*rJrwf f ^r--:
    Ytq,1,v\
    Suor&ry biotifc
    Scconhry quarlz
    Prehntc
    Pyrrlc
    Y-feldepr
    Aematife,

    Ftgurr I-B-2: Sydrotberorl altoratloa ntnerals Ln andesl,tes 8$d dacltca of the


    l{altekauri area and tbelr rslatlou to alteratlon l,ntenslty. K-feldgPer
    and benatlte oecur only ln the dacttee. (Corplled fron descrlptlonc la
    Rrboue 1971t 1975.)
    l*99

    4
    uNu a
    2
    o c
    3

    Quarlz
    5t Ei Fi
    I

    !o c
    Calcita !l .sl
    l.lr
    \rl
    EI
    $t
    UI
    L,
    Sphaleita Ei -al -bl
    I
    ChalcoVyilc .'ol !r
    I

    151
    Galam s
    El s EI
    Pvirfe,
    Abulana
    I
    s.l 7 s l-4- PI;
    .51 E
    Kaolfntta t 5l
    5l f,
    Cnalcocie, Ni E
    'Et
    Cowllitc I

    Flgure I-R-3r Paragenetl.c sequanco of rlnsrals ln the lfalttkaurt Velnr Jubllee


    Lor Lavel.
    500

    quartz, clay (chlorite, with ni-nor kaolinite and illite) and


    ,cyrite alihough in the dacites this zone is represented by
    assenblages of quartz, K-feldspar (adularia) and. heaatite.

    :iri;lsALISATIori
    Quar'u2veins occur in both the and.esites anC d.aeites of
    the i{aite}<auri area although in the latter their ten<l to be
    snaIl and grouped as vein systens, due to their }ess coapetent
    hcst rocks.

    The nain veins are Durbarr Grace Darling, Huanui,


    l'laitekauri (Jubilee), Scotia and l,iaoriland. (Fig. I-0-1 ). The
    i{aitekauri vein is the largest of the groupr being approxinately
    1kn long and connonly up to 2.5a uide although a naxinun wid.tb
    of 1 0n was recorded.

    The ninerali.sation in the various veins consisted. of very


    fine grained, electruro widely dispersed in quartz and quartz
    pseudonorphs after calcite gangue. Priuary caleite r.ras rare
    or absent 1n ihe veins. In the lol.r levels of the Jubilee rline
    the ';iaitekauri vein contains pyri'ue, chalcop;rrite, sphalerite
    and galena, but el-ectrun is generally absent. lhe Scoii-a vein
    al-so contained. sulphi-Ces, including acanthj.te, but only in
    sna1l patches and very fine grained. (8e11 & Fraser, 1912).

    Rabone ('1971a, 1975) investigated. the ni.neralisation of


    the llaiteliauri vein in the Jubilee Low level (Fig. I-R-1)
    after it was reopened, by Consilver in the ear|y lg?0rs. The
    vein varies in uidth fron 0.5 to 3n. Quartz and, calclte are
    the rnain constituents but ad,ularia' kaolinite' pyrite'
    sphalerite, galena and chalcopyrite also oscur.
    The paragenesis, illustrated. in Fig. I-R-3' was conpiled
    froa R.aboner s d,escriptions and the writers observatlqns of
    sanples donated by Rabone.

    SeveraL periods of fauli; Eovement and. brecciation occurred.


    durlng Stage 1 r.rhich ls represented. by band.s of quartz and
    caleite and waI1 rock breccia cenented by quartz and calcite.
    A large proporti.on of the calcite has been subse.quently leached
    501

    Flgure I-R-4: Stage 2b geleua (pale grcy-uhlte) replaolng Stage 2e aphalerlta


    (grey, upper rlght) arouad the rlue of gralns. Tbe galena la ln turn
    replaceit by eupergene covel11te. Stege 2b eubhedral pyrlte. (rhlter csntor-
    left and bottou left ) coatalna abunilant lncluglons of galcna (pgle grey'
    blgh rcltef) and a fev iucluslong of cbelcopyrlte (pa1e grey, no rallaf,)
    probably replaclng tha pyrlte. The ilark grey-b1ack background Ls guartz
    aad tha black spott art pLts. Sanple 14020. I2OO.
    502

    out leaving quartz pseud.onorphs after caleite. Stage 1


    naterial ualres up aost of the vein. ..

    Stage 2 nrineralisationr conslsting of fine to coarse


    ;rained quartz, sphaleriter gaIena, ehaleopyri.te and p;rrite'
    occurs in a 20nm to 0.3m r'ride (averaging 0.1n) band near the
    hangin3 wa1l. Early nineralisation (Stage 2a) consisting of
    nediun to coarse grained sphaleri-te' chalcopyri.te, galena and
    p;rrite ( in ord.er of abundance) oecurs ia quartz veinlets and
    also as replacement mineralisation in saIl rock breccia. The
    ratio of sulphlde to gangue is high in coarse grained
    ni-neralisatlon but 1ow i-n fine grained. nineralisatlon. Mutual
    boundary relations betvean sphalerite' chalcopyri.te and galena
    and rare subgrgphic intergrowths of galena and sphalerite
    noteil by Rabone (1971a, 1975) indicate that these ninerals
    precipitated together. Pyrite is a ninor phase and generally
    euhedral.

    A period of ninor brecciation is folloued by Stage 2b


    nineralisation eonslsting of fine to nedium grained quartz,
    galena and pyrite, Galena occurs as replacenent rins on
    earlier sphalerite (fiS. I-R-lr) and intergror'In with quartz in
    a ff fishnettt texture (Fig. lr-16), whereas pyrite occurs as
    solitary subhedra] grains in quartz. The pyrite contains
    abundant inclusions of galena possibly forned by replacenent,
    (Fig. I-R-4).

    Further brecclation is followed by quartz with nj-nor


    pyrite and chalcopyrite deposition (Stage 2c). Snall quartz
    crystals (up to 5nn long) are developed i.n vugs. Pyrite and,
    ehalcopyrite f111 cracks in Stage 2a sphalerite and also oeeur
    as solitary sulphide grains on vug quartz crystals D

    Sta,ge 3 is narked by vug quartz crystal depositlon and


    later filling of vugs and shears by kaolinite.
    Supergene covellite and chaleocite replaee Stage 2
    chalcopyrite, sphalerite and galena along cracks and around. rins.
    503

    JUBILEE MAORILp'l\ID
    5tago, I Stage 3
    I
    loo'c
    t I
    f
    F= z@'c \.s

    II FhF zzo'c
    tr
    u l-aFl
    a
    F
    o
    F
    r$$
    oao
    O - r\) t00'c
    fE rrr
    N
    e
    ; F

    4 ur
    s
    0 ) 3
    +
    2

    uEh I

    o
    l-1 +
    |a


    lFe

    3iryle, valueE, I FillingTeriiparafutu n Safinily z.


    s
    C)

    Flgure I-R-51 Btetograua of prlaary flutil lncluelons fllllag teupereturea and


    apparent ealtrnitles lor eanplee of quarta froo the Waltekaurl area. Tha
    tnillylitual leasurEenta are ltrtett ln Appcuttlx III .
    '50t,

    F'LUID II{CLUSIOI.IS

    Fluid inclusions in quartz.sanples fr.on the Jubilee aqil


    I'laoriland vorkings are generally two phase, liquid plus vapourt
    norrnal types, although a fibrous solid phase a1-so occurs.
    'in.sone fluid inclusions of samples 14,010 and 1LO1l+
    - -- -i
    (Fig. 6-13).

    Filling ternperature and salinity neasurenents are


    presented as histograns in Fig. I-R-5. A Dressure salinity
    correction of approxinately 1OoC nust be ad.ded to the filling
    tenperatures. Corrected filling ternperatures indicate
    depositional tenperatures between 260 and. 280oC for quartz
    sanples braeketing the sulphide nineralisation i-n the
    l.Iaitekauri vein and quartz deposi-tion i-n the Maoriland vein.

    SUTPHUR ISOTOPES

    of sulphid.e ninerals fron the Jubilee Hine


    S3l'S values
    are listed in Table 9-1. They range fron +0.3 per nil (galena)
    to +J.8 per mil (sphalerite). Because galena is'not connon in
    the sulphide nineralisation and is generally fine grained,
    sufficient galena for isotopic analysis coul-d be separated.
    fron only tuo sanples: 1/+010 (Ut< 1b) and 14020 (Ut< 13)-
    Fractionation betueen galena and. sphalerite ind.icates
    depositional tenperatures of 355 - 39OoC (two d.ifferent sp-gn
    pairs of sarnple 1/+010) and 280oi respectively. Other nineral
    pairs are general1.y not in isotopie equilibrj"un.

    TIIERI.IOCHEI.IISTRY

    . The geochenlcal environnent of Stage 2 nineralisation is


    linited on the fS, versus f0, diagran (fig. f-R-6) by the
    presence of pyrite and chaleopyrite but absenee of pyrrhotite,
    nagnetlte, henatite anil bornite. The iroa content of
    sphalerites indicate log fS, values betueen -9.7 and -1O.1',
    whereas 1og fOa is linited betueen -32.0 and -36.O by the
    presence of calcite but absence of graphite' anhyilrite and
    naguetite.

    A value of 0.01n was used for the concentration of total


    sulphur in solution (log z S = -2) in the construction of
    the fO, versus pH diagrau shown in Fig. I-R-?.
    505

    tffitfrrcicritt
    (\|
    (n
    PVRRHOTNE
    cn
    o si
    q
    ET

    -46 -4 42 4 48 -re -U -r2 -r0 -28 -26

    Lo9 lOz

    Flgure I-R-6: fS2 reraua fO, dtigraar at 280oC ehovlng the geocheulcal environ-
    nent (shaded) of Stage 2 quattrz + pyrlte t chalcopyrlte t ophalerlte +
    galena nlaersllsatloa ln the l{altskaurl Velu. Log fS, fror cphalerl,te
    conposltlol,a - -9.7 to -10.4, and 1og fG02 ' +1.5 (eatluated). (Methode of
    constructl.on ars deaorlbed tn Appandf V.)
    5a6

    Sericife.i K- fal

    :HEMATITE
    I
    :

    oal BOR,NTTE t

    s"
    Lm f 52. -to I

    CNOTaC
    rlNllt, I
    I
    :

    F'RRHOTNEi

    Flgure I-R-?: fO, vereue pll dlagrau at 280oC and S- 0.01c ahonlng the
    oheptcql snvlronoent (shaded) of Stage 2 quartz t pyrite t chalcopyrlte *
    cphalerlte + galoaa nlnerallsatlon ln the ltqlteksurl Veln. i - 0.15, rKl.
    0.040' PHlA 5.8r log fS2 fron aphelerlte conpoaltl,ons o'9.? to -10.{" aad
    log fCO, (egtlnated) - t1,5. (Hethode of congtructlon are cleacrlbed ln
    lppeudlx Y.)
    5s?

    K-feldspar occurs as a vein aineral, ',rhereas the ua]-l


    roek alteration is characterised by the occurrence of sericj.te
    (secondary henatite and kaoliniie in sone intensely altered
    rocks oi the l,'Iaiiekauri area are considered. to result fron
    post Stage 2 f luids). The hydrotherraal iluid is therefore
    consid,ered to have had a pl{ near that of the seri cite/K-feldspar
    boundary (S.A) and is represented by ihe shaded, area in
    Fi-g. I-R-7. Sulpbur ruas present in solutioa predorninantly
    in reduced. forn.

    cEliasrs
    Deposi.tion of Stage 2 reineralisatioa at t{aitekauri
    probably occurred bscause of changes in fluid chenlstry (e.g.
    pH) as a result of fluid - wa1l rock reactions.

    5"t *, of the hydrothernaL fluid was probably around


    t{, per niL' sinilar to the S34S values of the sulphide
    ainerals, because sulphur was present in solution predoninantly
    in reduced forn. Therefore the sulphur was probably of
    nagnatie origin.

    RE?EREI.iCES A}ID BIBLIOGRAPHY

    BELL, J.II.; FRASER, C. 1912: see pp 113 - 117


    DorillEr, J.F. 19353 see pp211-213, 215-222 and 2A?
    RABoNE, S.D-C. 1971 a

    1975
    scIioFrELD, J.C. 1967
    itILLIAMS, G.J. 197t+! aee pp 107 - 109
    508

    I-S
    IfAIIII

    INTRODUCTION

    The mines at liaihi compri.sed the largest and most


    successful long term gold mining venture in New Zealand.
    Between 18?8 and 1952 1.1 billion grams (35,523,768 ounces)
    of bullion lrere produced fron 1 2 nillion tonnes of quartz
    (Willians, 197D. The ore was taken from 1/r levels and an
    opencut representing a total vertical range of J00n.

    The veins in the Waihi area occur j.n two geographically


    separate groups (Fig. I-S-1 ) , one und.er Martha Ei1l and the
    town of Waihi (tlartha, Enpire, Royal and associated veins)
    termed. here the Martha vein systenr &nd the other under
    Rosenont 8111 (Union, Mascotte,Anarantb, Silverton and.
    Gladstone veins), termed here the Rosenont Hill vej.ns.

    vein systen produeed approxinately 200


    The l,lartha
    nillion grans (6.5 rnillj.on ounces) of gold, whereas the
    Rosenont Hill veins produced less than one million grams
    (3orooo ounces).
    't

    Several companies operated in the area in the late 1800rs


    but by the turn of the century uere nostly analganated, into
    threei the llaihi Gold 'Mining Co. (W.O.M.Co.), Grand. Junction
    Co. (G.J.Co.) and the tr{aihi Extended. Co. (W.E.Co.). The
    areas of operation of these conpani.es are shown in Fig. I-S-1.
    The literature describing their operations j-s confusing
    because although the.nines nere adjacent and generally
    operating on the sane najor veinsr they uere worked. fron
    different levelsr so that levels with the sane nunber occurred.
    at narkedly different depths in the d.ifferent nines (Fig.I-S-2)
    The Irl.E.Co. was taken over by the G.J.Co. around. 1918
    and the latter conpanies operations were taken over by the
    W.G.M.Co. in 1925. During its eontinued procluetion until 1952
    the operati-on was generally known as the Vlaihi or Martha Mine,
    The latter tern is used here.
    509

    WAIHI EX ENDED , WAIHI REEFS


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    systen (l.larthe Enplre, Royal and aegoel.ated velua) and the Roaeuont H1.11
    velnr (Ualon, Hascotte, Aoaranth, SLlverton ancl Gladatone ve!.na)-
    510

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    Fitt s
    O\
    tt 6-
    s E q{
    .l\ 5b
    s-s xt g
    s ts
    N o- F
    FrO
    g h!c
    5
    ETTE ir
    o9
    o, T St*b .{h
    Icl

    ; FiF tr $ I
    E
    \
    t
    u)
    st4 lr- 5S$; F s;! ?:E
    (J
    a
    .r Al
    |Yra

    trlli g,l?agt

    E t.iT r{I e|
    ,9 O
    'l.-
    a
    tt
    ,*
    ,!'

    vl
    h
    513

    At present the A}lfu\ !,lj.neral Resources - Green &


    l'lccahiIl consortiun are evaluating the possibility of reopen-
    ing the l,tartha l"line. l4ineral Resources - Green & l.teCahill
    tested the upper levels with a large open cut prospec.,,ing
    operation (r'is, 1-6) reported. bv Hancock (1g7g), whereas AliAll
    are presently carrying out an extensive diarnond drilLing
    progratr. They had, Crilled 28 holes (averaglng 200n) u:c to
    i{ovenber 1981 and pranned, to drj.ll a further 2/, up to the
    encl of '|-982.

    . The geology of the tlaihi ni.nes was d,escribed by 3el1 &,

    Fraser (lglz) and l{organ (lgz+). Brathwaite (tgeo) described.


    the thin sections of trIaihi rocks in the Geological surveyt s
    collection and is presently studying AilAXt s drill core. The
    ninlng history uas described by Dor,rney (lglS) and McAra (lglg).

    l'lodriniak & l,larsden (19fi) carried. out a conprehensive


    geophysical survey on the surfaee, using seismic refraction,
    nagnetic and electrical resistivity nethods. Fron their
    results they interpreted rock type (andesite or rhyolite) and,
    zones of hydrothernal alteration at d,epth, in addition to
    napping several nelt faul-ts and deternining extensl-ons of so:ie
    previously knor.rn faults ani, veins.

    At the tine of the rsriters investigation sone of the upper


    levels were opened, by l,lineral Resources Ltd and. liuited access
    was gai.ned to the I'lartha Vein and a parallel vei,n teraed liartha
    Branch.

    GEOLOGY

    The geology of the rlaihi area is illustrated. in Fig. r-s-3,

    Be11 & Fraser ('lglz) and l,torgan (1gzt) distinguished, two


    units of andesites and dacites (Table I-S-1): (t) an early
    series of pred,oninantly flor.r rocks identifiec as dacites by
    tseLl & Fraser but terned quartz and.esites by l.lorqan, and (2)
    a rater series of flovs and uinor pyroclastics (ttre latter
    nainLy in the G.J.Co section) of pyroxene and.esites and lesser
    dacites.

    Brathwaite (t9ao) confirned Morganrs d.escription of the


    -l
    '| '
    51lr

    TABLE I-S-1 r Stratlgraphy of the rocka lu the l{alht aroa sboving


    tbe dtvlclong of EeIl t Fraaer (1912), tlotgan (1924']t
    aait the aohene atloPted hcic.

    'Cooplletlon (schsue adopteil here)


    Bell & fracer (1912) llorgaa 1924
    Trlilyrlte Boartng RhYolltc Trldynite Rhyollte Trldyulte nhyoff te lgoroglen
    Tl.laonlte Rbyolltlc tulfa orharoe rgnlnbrltc isubgrouP
    Foruatlon . iJ
    F
    Spherulltlc rhyollte Spherulltlc Rhyollte Unrllfferentlated )!tl.ntlen
    (rpherulltlc )Rhyollte F.
    l{
    rhyollte) )SubgrouP F
    t

    Andealteg Becsone Iglatd Onahla AnilesLte


    A
    (lato pyroxene aaileal'tss) F
    o
    (Second Per!.od Volcaales) Serl.ee &

    lf
    (lnteruetlLatc
    -andccLte, pyroxene FT
    o
    Daeltca Roeliout Htll) 2
    (Flrat Par!.od Voleanles) Kapanga Serles (aarly quartz pltroxona
    -andeilf,e, -
    o
    Hartha H111) d
    C'
    C'
    515

    lorrer unit as predoni.nantly quartz anclesite rather than dacite


    but consid.ered that the rocks of Rosenont llirl were pyroxene
    and.esites rather than the dacites and quartz andesites of Bell
    & Fraser (lglZ) and l.torgan (lgZD respectively.

    rn addi-''ion to cotrpositional differences (presence or


    absence of phenocrystic quartz) trre distinetion between the
    two units described by Be11 & Fraser and ltorgan rjras also
    narked. by the oecurrenee of the quartz veins and noderate to
    stronq hydrothermar alteration in the quartz andesite unit,
    whereas the upper pyroxene andesite unit was not penetrated by
    the veins and was only weakly altered. Bell & Fraser (lg'tZ)
    considered that the boundary between the two unj.ts was
    irregular and postulated that a period of erosLon and weathering
    oecurred between their.respective depositlon, producing a very
    disected landscape on the lor,rer unit.

    Bell- & Fraser (1912) postulated that the rnajor portlon


    of the producing field was contained vithin a large intrusive
    dacite boss. This hypothesis was not substantiated in later
    work by liorgan (1921+) and Brathwaite (1980) who considered
    that nost roeks from this section were voleanic quartz and.esites.
    Howeve.r, the latter author did identify two roeks (from the
    iI.G.l{.Co. sction) in thin sectj-on as dacite porphyry intrusi-ves
    indlcating 'Lhat snall intruslve boilies clo oecur in the volcanic
    s equenc eI

    Thin beds of pyroclastics interstratified with the


    andesj-te flous were identified by Brathwaite (tggo) as dacite
    and. rhyolitic crystal and lithic tuff and fine grained
    siliceous tuff . l.{organ ('lgZL) considered that sone
    pyroclastic beds i{ere i-n fact sedinents (volcanic epielastites)
    and he also noted the occurrence of various carbonaceous bands.

    The andesites of Black llirl (Fig. r-s-3) were consj.d.ered


    by Bel1 & .praser and by !'torgan to be intrusive and were mapped
    by Schofield (1967) as Onahia Andesj-te as sbown in Fig. I-S-3.

    A series of eon3lonerate beds were iCentified between the


    andesites and overlying rhyolites by Be11 & Fraser and were
    consldeieri. by these artthors to be fluviatile anrl ind.icate a -l;
    516

    period of erosion bef,veen the andesite and rhyolite volcanissl.

    In- suianary the Coronandel Group sequence at Waihi consists


    of at least f our and.esiies as follows ( in order of decrefiiog
    age): (1) quartz pyroxene andesite (conprising l'{artha HiI} -"-
    and host 'i;o the llartha vein system), (2) pyroxene and.esite
    (conprising Rosemont Hill and host to the Rosenont Hill veins),
    (3)'pyroxene andesite (barren of nj-neralisation) and (a) an
    lntrusive hornblende andesj-te (Omahia Andesite) conprising
    Black llilL.

    The lJhitianga Group sequence consists of spherulitic


    rhyolite (tlinAen Rhyolite Subgroup) overlain by a serie" oi
    welded and non-welded pyroclastics of the Coroglen Subgroup
    (classified as 'uhe 0r+haroa fgnirobrite Foruation and the
    Tridynite Rhyolite).

    IIYDROTHERI{AL ALTERATTOII

    Be]1 & Fraser (1912) and l.{organ (1921+) deserlbed the


    \ydrotherrnal alteration of the andesites and dacj-tes in the
    i.lartha Mine in a general sequence as chloritic, propylitic
    and silicic with increasi.ng proximity to the veins: These
    authors noted the following trends:
    (1), feldspars r.rere altered to sericite, carbonates, adularia
    (valencianite in the early literature), secondary quartz and
    apatite
    (2) ferromagnesians were altered to ehlorite, seirpenti.nous
    naterial, secondary quartz, leucoxene, pyrite and carbonate.
    (2) nagnetite and. ih'renite were altered to leucoxene and
    pyrite.

    The carbonate lras nainly calcite althou,gh l.lorgan suqgested


    that doloni-te also oceurred and BeII & Fraser considered that
    nruch of the leucoxene uas siderite but this was refuted by
    I'lorgan.

    Thezeolites stilbite and launontite were noted. in sone


    altered andesites of the !I.E.Co. section by l.lor3an (lgZt, p89).
    517

    The intensity of hydrothernal alteration was considered


    to be prinarily a function of the proxinity to veins although
    sone exceptions uere noted by BeI1 & Fraser.

    Brathvaite (1980) classified the hydrotherral alteration


    of the andesites in his thin seetion stud.y as follovs:
    'l,Ieakly altered andesites: these contai.n hydrothernal
    assenblages of carbonate, chlorite and. traces of sericite
    (iffite). is conpletely replaced, blr chlorite,
    Hypersthene
    augite is fresh or partly altered to chLorite and carbonate,
    r.rhereas plagioclase is unalteted.
    l{od.erately altered andesites: these contain hydrothersal
    a.ssenblages of carbonate, chlorite, sericite (ittite),
    adularia, sphene, pyrite and one rare oecurrence of epi.dote
    (as a plagioclase alteration product). Augite is repl.aced by
    carbonate 'and chlorite, plagloclase is variably altered to
    earbonate plus sericite (ittite), or adularia, or ad.ularia
    plus albiie, whereas prinary nagnetite is d,estroyed and is
    indirecily repl assd by sphene and pyrite.
    S'imngly altered and.esites: these contain hydrotirernal
    assenblages of secondary quartz (in grounCnass and veins),
    sericiie (iltite), adulariar chlorite'(1ess thaa in noC.erately
    altereC rocks), carbonatesr pfri-^ue (l 25fi of rock), sphene
    (ubiquiious) and apatite. Plagioclase is conpletely replaeed
    by adularia, sericite (iffite) and earbonate, and. sericite
    (iftite) in turn replaces ad.ularia.

    Braihuaite (tggO) noted that there were Do obvious trends


    in increasing or deereasing alteration along strilce or with
    Cepih (totfr strongly altered and weakly altered roclcs oecurred.
    around the 1000 foot level).

    The unnineralised pyroxene and.esites (Second Period


    Volcanics of Be1l & Fraser and Beesons Island. Series of i.iorgan)
    lrere generally on1y weakly altered and the nineralised pyro:iene
    anrlesites of the Rosemont iiiIl area were unusual in'r,hat they
    contained no carbonate (Brathwaite, 1980). Brathwaite
    considered that the latter rnay be related to the intense
    silicification of the samples.

    In the hydrothernal alteration of walJ. rocks in


    sutraLrlr
    ',,he l"lartha Mine is eharacterised by the developuent of adul-aria
    518

    I
    I
    I
    I
    ,
    I
    I
    I
    ri
    I

    U:I rt
    ro\
    z,

    fl
    P
    E
    o
    E
    !t
    A
    FI

    -
    E
    o
    lr
    f{

    g
    I o
    it 4J
    v,

    -lf: |a

    I 5
    o
    c,
    .tt
    k
    rt
    =o
    !!
    [ii ;il c{
    o

    j
    o
    g
    irlN o
    +t
    o.
    o-C

    "q
    I ol
    .l F
    8E
    no\
    3:t F

    Ii
    o
    t{.
    (tAt
    dl
    3
    c,
    ..'.:.
    -{t
    b0:
    O
    !-
    5i

    i
    vt
    aL
    I
    l-/
    l-l
    +t
    ot{
    Arl
    J
    bo

    L
    /
    519

    and serieite (iIli'"e) and the intensity of alteration is


    related to the proxinity to quartz veins.

    I.II}IERALISATIO}I

    I'{artha Vein Svsten


    {
    Econoni-c nineraLisation occurred i-n a nunber of veins ln
    the !.!artha vein system, the nost inportant being the tbree
    se:uj--parallel veins known as the I'lartha, Empi-re and Royal
    (fig. I-S-1 ). These veins lrere found to converge with depth
    (fig. I-S-/r). 0n1y the i.lartha outcrops at the surface.

    Gold oceurred in the llartha l,line as very fine grained


    electrun (not visibl-e to the naked eye) although visible
    tleafyt gold was reported fron Snithy Level (l.lorgan, 1921,, p93)
    aad occurrinq tton j oint - surfaces not far below the outcroprr
    of the llartha Reef (ilorgan, 1'924, p105 and 1tB). The electrum
    had an average fineness of about 550 (Be1l & Fraser, 1912 p58;
    l,{organ , 1921, p93) .

    Silver, in addition to that in electrun, occurred pre-


    doninantly as acanthite although native silver, in the forn
    of scales and wire nas found on various levels in the Hartha
    vein and 11 level of the Enpire Lod.e (p 93 of I'lorgan) and
    pyrbrgyrite (AErSbSr) and proustlte (Ag3AsS3) occurred in
    cleavages and vugs at several locations between 2 level
    G.J.Co. (1193,) and 11 level'['I.G-]l.Co. (1301 t). .Hessite r+as
    not recorded and no trace of Te r.ras detected, in the assays cf
    ore although these contained small quantities of Se which
    Bel1 & Fraser (1912) suggested. was held in acanthite. Analyses
    of acanrhite by the writer confirm this hypothesis.

    The overall Au:Ag ratio of the ore was quite variable


    with the following figures quoted:
    (1 ) 1t6 to 1z7i average f or the '!f .G.l.l.Co. seeti-on (tfre }tartha
    l,line at this ti.me consisted of the i'I.G.l.l.Co. and the G.J.Co.
    sections), estimated from production figures up to 1922(?) by
    Horgan (1921r p153) .
    (2) 1z lri for the t..f ,Co. section, estinated. froa
    aver3.ge
    production fiqures up to 19?2 by )iorgan (lgZt, p16)).
    52o

    3) 123 to ltlr; oxidised. ore (8e11 & Fraser, 1912 p139).


    ( lr) 1 z l+. 5 i l.lariha open cut.
    (5) 1 z3A in sulphide ore at its upper limit on 2 level (nett
    & Fraser p1/r1 quoting earlier work by l,lorgan) . =-

    (5) 1:9; averaEe for all ore minecl by the 'l^l.G.I.Co. durins='
    ,- 1910. (eeft & Fraser, 1912 p137).
    (Z) 1:0.5 to 1:5i 5 1eve1 of Jelicoe Lode (Morgan, 1g2t+ p15Z).
    (S) 1z?i ilo. 2 Lod.e 1'I.E.Co. (l'lcrgan, 192t+ p168).

    Assays of Ai.lAXts dri1l core averaEe approxiurately 129


    (),lr :1. Baker, A:lAX, pbrs. conn. 1980) .

    The bullion producti.on (35,523r?68 ounces) up to 1952


    and its value (2A,496,01 1 pounds sterling) quoted by t'Iilliams
    (1971r) indicates an average Au:Ag ratio of approxinately 1:5
    for the entire ni-ne.

    Pyrite occurred throughout the mine and was often host to


    the electrun.

    Sphaleriter galena and chalcopyrite were found in the


    internediate and lover levels. Sphalerite was the most abundant
    of these sulphides. Galena occurred on 3 level (iI.G.l,{.Co.
    section) and deeoer levels. Chalcopyrite, frora its initial
    appbarance in the upper level-s, increased in quantity to a
    maxinum in the lnternediate levels but decreased towards the
    lower Ievels. -

    llolybdenite was reported by l.lorgan (lgZ+ p171) fron the


    l'I.E.Co. l.{ine. It occurred. as spots and. i-rregular streaks in
    a quartz vein j-nterseeted (in a shaft?) 23r- above 7 level and
    sinllarl;r 1n a snalI vein on 7 leveI. The foruer vein assayed
    0.13 - 0.115/, i{o but contai.ned only traees of Au and Ag.
    Brathwaite (tgeO p"5) described a sanple (f 7915) of a quartz
    veln frou 7 level of the III.E. Co. section containi4g fine
    gralned (0.3un) nolybdeni-ter pXriter adularia, sericite and
    carbonate. l.lolybdenite was not recorded. fron any other
    locations in the Har.tha i,fine.

    The ganglle ninerals i-n approxinate orrLer of abundance


    t.,Ierequartz,ca1ci+,e,adu1eria,!:ao1inite,sericite(rrrite)
    521

    and ehlorite.

    Quartz was general1y chalcedonic but fine grained quartz


    with'coub structure uas found i-n r'nteruediate and deep levels:
    coarse grained. quartz and vug quartz were rare. AnethyBtlne
    quartz was quite connon in the lt{artha l.line, frequently lining
    !. cavities (:torgan lg?tr). AI,{AX have founcl concentrati-ons of
    anethystine quartz on the footwall sid.e of the ;.{artha vein and
    consider ii to be a late stage vein nineral (:,tr it. Baker pers.
    conm.). l,torgan (1924, p95) attributed its colour to l,fn.

    Quartz pseudomorphs after calcj-te were quite conmon in


    so cal-led rroxidised orerr froin 2 level clovrn, however in the'
    l.iartha Vein prinary calcite did not appear until 5leve1, was
    nost abundant at 8 level, and was absent below 9 leve1 (although
    quartz pseuclonorphs after calcite occurred in the lower levels).
    lluch of the calcite lras maneahiferous and rhod.ochrosite
    occurred in several parts of the uine (l.lorgan, 1921+ c.f . p95).

    Adularia (valencianite in the early literature) also


    first occurred at 5 level and persisted into the deeper levels.
    It was a eomnon constituent of the sanples studied by
    Brathwaite (t9eO).

    . Kaol-inite was found mainly i-n the upper levels. Be1l &
    Fraser (lglZ p57) report an analyses of kaolinite fron 6 1evel
    'lrl.G.l'l.Co. secti-on uhieh I'lorgan consid.ered a nixture of
    kaolinite and sericite.

    Sericite (iffite) was a fairly persi.stant although ninor


    consti-tuent in sanples originating fron 5, 6, 7 and 9 levels
    of the iI.G.!.l.Co. section studied, by Brathwaite (1980). ilorgan
    (lgZt- p89) noted that it occurred as fine white or pale -
    brorsn fibres lncluded ln vein quartz.

    Chlorlte occurred as soft greenish scales and masses in


    several veins and was partieularly abundant in the Roya1 Lod,e.
    Morgan (1921, p89) noted that in the upper and.niddle levels
    of the l,{artha i,line chlorite was an indicator of ore but this
    relationship did not always hold in the loi.ier levels.
    Brathwaite ( t ggO ) i,jentif ied chlorite in onl1r one veln speclcen
    522
    (P18 5l+3 liartha Lode 5 l,evel !1.G..',l.Co- section) durin.3 his
    study. '

    Bell & Fraser (lglz) divided the paragenesis into three


    sta,3es: (1) calcite .rein fi1ling, ( 2) breceiation '..rith subse-
    cluent ore deposition and (3) later gold - silver bearinq
    suJ-phide stage, cross-cutting Stage 2. llorgan (1921r), however
    clained that BeIl & Fraserrs earl;y calcite stage did not ecist.

    ft is apparent from the earl1r d.escriptions of tlie nain


    ore stage t"hat ii uas characterised by ual1 rock breccia with
    replace:nent nineraLisation occurring in the breceia fragnents
    and fissure fi1l1ng band.ed nineral-isation betr'reen the fragnents.
    The banded inineralisation j-s nost conaonly alternating veinlets
    of 'quartz and quartz r,rith pyrite, acanthite and electrun in
    +"he upper leve1s but galena, sphalerite and chalcooyrite also
    occurred in the internediaie and lower levels.

    Several adits in l,{artha Hill are accessible to r.rorkings


    on bhe ilartha Vein anC a vein knolrn as l'lartha Branch- In
    these, tlr.e veins consi st of banded chalced.onic cuariz. A fer.r
    vu.gs are found and contain quartz crystals up to 6nrn lon.3.
    Tlie vej-ns contain gold anrl silverr 3s inclicated- by assays,
    but it is u"t'"uoely fine qrained (in tne order of 5 nicronetres,
    ilr E. Coppard. pers. conin.) and was not observed by the ruriter.

    In contrast sanples of nineralisation ob'r,ained from


    institutj-onal- coll-ections contain abuidant sulphid.e
    mineralisa'ui-on and a few also eontain nicroscopically visible
    gold. 0f the dozen sulphide sanples originating fron the
    l.iartha vein only three are located to specific Levels; 1LAL7
    (1.ih44) fron 7 level and 1t050 (iih4?) and 14a52 (ltrr5o) fron 10
    level. Presunably the reiaainder are also fron deep levels.
    Because the tine and spatial relationshlps betr.reen the speciroens
    is unknorvn and they differ widely in content a detailed aceount
    of the petrography of indivldual specirnens is not given here
    but nray be found in Aopendix VI. The follor'rinr1 description
    sunnnnarises the most iraportant characteristics of the suite
    of sannles.

    i,iost saroples eontain sphaleriter galena, chalcopyrite


    and pyrite, sone eontain'acanthite and/or electruro (lt*O32,
    5"3
    1101+3, 1lr1lr5, 1l+01+7, 1l*Ol*8 and 1l+052), two contain pyrrhoti.te
    (13978 and 14,0,4,0) and one contai.ns tetrahedrite (ltOSZ). Host
    are band,ed with individual bands contai-ning sphaleriter g4lena,
    pyrite and. chalcopyrite in various quantities, or associations
    of sphalerite and galena, or pyrite and chalcopyrite. A period
    of chalcopyrite enclosing euhedral pyrite oceurs in 1r*orr7 (vrnLl;
    7level) and 1l+O5O (l'Ih4.?; 10 leve1). Sphalerite and. galena
    bands generally have sphalerite predonrinating and, sone (l3gza,
    1lr0l+0 and 1l+o/+6) contain complex orientated intergrowths. In
    1 t ol$ (l.lh43) 't streaksil of galena oeeur in
    sphaleri-te and in 13978 (1,{h27) and 1t+Ol+O ('l.Ih29) rstreaksrt of
    Ealena j-n various conbinations with one or nore of pyrite,
    chalcopyrite and pyrrhoti.te oecur ln sphalerite (Flg. 4-25).
    Also in these speclmens sone sphalerite gralns eontain
    i.ncl-usions of these ninerals in a poikilitic texture (Fig. I+-26)
    whieh is interpreted as being cross-sections of the ttstreakyn
    texture. Sanples 1tot9 (Wh42) aad 1 40i.Z (Wh50r 10 level)
    exhibit a lamellar texture of sphalerite ln quartz.
    Electrun occurs as blebs (S nicronetres) in galena,
    sol-itary in quartz or as grains i.ntergrown uith galena (av.
    0.01 , max. 0.02nm) in 1t0tr7 (Hh4/*i ? level) but generaily in
    pyrite in 1t+01+6 (WnL3).

    RosernontHill Veins
    The nineralisation in the Rosenont Hi].l area occurred Ln
    four north-west trendlng (para11el to the naJor t{artha vein
    systen) veins known as the Union, Mascotte, Anaranth and
    Oladstone, and the llNI/ trending silverton vein (Fig. r-s-1).
    l'{ost of the fierds production eane fron the union vein.
    Several unnineralised tfquartz blowstr (nassive lenticular bodi.es
    of ehalcedonic quartz) also occurred outcropping in the area
    (rig. r-s-3) and were interpreted as sinters by Bell & Fraser
    (tgtz) .

    Only scant infornation is available concerning the


    mineralisation of the veins because the early writers were
    unable to enter the mines and. observed only surfaee exposures,
    d.unp naterial, nnine plans and nine reeords. However, the
    following description is gleaned. fron BeI]. & Fraser (1912) and.
    l'lorgan (1921r) .
    52lr

    q114
    Quartz SamPlQ5

    : wol1
    1407t
    -
    trl t40?5

    nlr
    -J'l- l- r-
    t=:r 14045
    s.."c=- l4o4z EI
    r,--t__ _zaftiw t] r-l
    Calcif'a gavnples
    #b 14044 Frt
    -,'-rtfl 14071
    EI
    r Er 14072
    --fL woso u
    l&t60 tw2n2u242@2u7@ o 2 4 6
    Flll'hg Temperollvrz "C 5alinity eq.wt /. NaCl.

    Srhglc value.s'. r EI

    Flgure I-S-5: filetogreue of prluary flulal Lncluslon ftlltng ,"tp"t"aut"" ""U i


    apparent sallnltles for eanplee of quartz autl oalelte frou l{alht. Ths
    lnillvliluel leasuroronta are Ilated 1n Appeadlr III. SaapLes 1LOL5, 1l+051
    and 7t+l7llo aontaln vapour rlch ancl vapouF f,lUed lnclul.ona' ln addltlon
    to J.lqutd-vapour aornal typeer Lnillcatlng that perlotle of bolllng oceurredI

    durlng ltucrol depoaltlon


    525

    The eeononic mineralisation oceurred near the surface


    below poorly nineralised outcrop. fine grained elctrun (up
    to 30 nicronetres, l,lr E. Coppard pers. eona.) and acanthite
    occurred in quartz and quartz pseudomorphs a.fter calci.te ganque.
    Primary calcite was apparently absent. The ore was considered
    to be oxj-dised, bein3 stained ulth i.ron and nanqanese oxides
    and contalning trreranantsrr of pl/rite and chalcopyrj-te (:alena
    anC sphalerite lrere suspeeted to have occurreC in the original
    vein rnaterial). i.lustard gold was found in sore speeinens and
    was attributed to secondary enri-chnent.

    Te, Se and Sb r.rere detested in analyses of ore (8e11 &


    Fraser, 1912; l,lorgan, 1g2t). The forner vras attributed to
    hessite, identified in sone naterial, whereas the latter vas
    believed by i"lorgan to indieate the presence of pyrargyrite.

    l,lorgan listed several assays of ore from the d.ifferent


    veins in which the Au:Ag ratio is typieally around. 1:6 with a
    ranrje of 1:1 to 1:100.t In another section (l'lorgan, 1921+ p132)
    he sugqested that the Au:Ag ratio was approxinately 1 z1 but
    quotes a value of 1 z?.f suggested by Griffiths for the
    Silverton Lode.

    :LUID IIJCLUSIOIIS

    Prinary fluid inclusions in sanples of quartz and calcite


    frorn the i{artha !'line are rare anC of srirall size. They are
    eenerally two phase, liquid plus vapour nornal types but
    sarnple s 1 11045 (i'1h41 ; Enpire Vein 12 level) and possibly also
    sanples 1l+051 and 7l'/7/10 (1'Ih49 and l'Ih45 respectively; both
    unlocated) contain vapour rlch and vapour fillerl inclusions
    indicating that the hydrotherinal fluid, was boiling at the tine
    of thelr entrapinent.

    Results of filling temperature anC sallnity (calculated


    fron freezing temperatures) deterninations are presented. as
    histoqrams in Fig. I-S-5. Because of their snall size only a
    fer,r i.nclusions were suitable for freezing tenperature measure-
    nents and hence the sna1l nunber of salinity results.

    Pressure - salinity corrections required for filling


    temperatures of sauples other than 1lr0l-5 (wir4t), 1l+051 (t'tfr4g)
    526

    160 tgo 200 z,20 240 260 29o

    t@ tw 200 220 uo zCO ztu


    Filling Temperafuru, oC

    Sinqlc value

    Flgure I-S-6c 0onposlte prlnary flutd Lncluslon fllllng tenperature hlotograr


    for salples of quartz frou the upper levela of ths Hartha l{lne (eenplea
    1)913,14O35t 14036 an(l 'lIO37). the aode of, the hletogran le between 190
    and 20OoC, al,ullcr to thc avorage value of approrlnataly 2O0oC.
    527

    ana 7l+/7/1o (wna6) are less than 15oc. A value of 10oC is


    suggested for all unloca$ed saaples, whereas the corrections
    for ILaLL (1fh40; 5 Ie'rel) is less than 5oC and those for
    sanples 1t036 (llrra), 1tO37 (l'lutO ) anil 14038 (1'Ilr1 5) are
    ne:11igib1e (probabl-y only 2 or 3oc).

    sanples 13913 (1.1h2l'), 1t035 (ilh4), 1LA35 (vha) and 1t+o37


    (ltntO), consisting of snall quartz crystals collecteC fron rare
    vugs in otheruise bande<i chalcedoni.c or finely crystalline
    quartz in the upper levels, have filling tenperatures rangi.ng
    fron 150 to ZgOoc. i'Ihen grouped together (Fie. I-S-6) they
    occur pred,oniaaatly betveen 190 and 230oC. The nod,e of the
    bistogran (Flg. I-S-6) i.s around 190 200oc and the rue&sur-
    inents average approximately 200oC. Although visible nineralisa-
    tion is not present assays of the band,ed quartz by I'lineral
    Resources Ltd indieate that gold. and si.lver are present.
    Therefore an average tenperature of 200oC is d,educed, for
    shallow level gold - silver nineralisation.

    Vug quartz crystals srowlag or earlier quartz plus sulphide


    bande..l .'rein minerallsation (sanple 14051) indicate tenperatures
    of 260 to 2g}oC folLowins sulphid.e Ceposition in interreCiate
    or deep leve1s (ttre sanple is unlocated.).

    Airethystine quartz fron Enpire 12 level (sanple llrDlt5)


    was deposited. betr.reen approxi.aately 260 and 290oC, whereas
    unlocated. anethystine quartz of sanples 1,('0/r2 antl 77/7/1O
    ind.icate d.epositional teaperatures iu the 210 to 25OoC range,

    The ihree sanples of calcite appear to have been deposited.


    during different phases at d.ifferent tenrperatgres: sample
    jLa3o (c,rt) around 25ooc, 'l!+031 (c.re) 23o - 190oc and. l Lot'L
    (',{h4o; 5 lever) 210 18ooc.

    SIILPHUR ISOTOP5S

    631'S values of sulphid'e ninerals fros sanples 14A3g


    (1{h28),11$41 (ilh30) and, 1t,.05'l $l}llt+g) are listed in table 9-1 .
    Flne banding an{ complbx intergrowth textures (e.g. Figs.
    l+-25 and. 1r-26) precluded. separation of cogenetle sulphld,e
    ninerals fron otber llaihi sauples.
    The ueasured S3l'S values range froo -1 .0 per nil
    528

    Otound Surface

    Mar.tho
    - Trt1. I
    I I
    tn4ittvt I
    - c\ I I
    -Mt I I

    lr
    _,
    -? :l
    i $i
    -4 I
    -5 .E
    t
    -b -g
    E
    -7 I

    -8
    _,
    E
    J
    *\,
    u
    ul
    rg
    rE
    -p s cs.
    !.
    N s5 l
    \
    5 '(t 9l
    g:t 9

    Flgura I-S-?r Deptb of nlneralloatlon ln the llartha Veln eyaten, based on


    evldence of boillng at 12 level and Brathraltete (1980) couparleon of the
    hydtotheroal alteretLon ul.neral aasenblagea vlth thoae of nodern geothernal
    BystenE. The depth ranges ehonn for gone aLnerala are based on thelr
    occurronce tu the ui.ned ors' as aoted by BelI & Fraeer 119121 and llorgan
    (1924).
    t
    t', -l
    5?e

    (galeua) to +?.1 per ni1 (pyrite). Fraetionation between


    sphalerite galena pairs ind.icate deposi.tional tenperatures
    of 3150 (sanple lLOt1), 335oC (sanple llOlg) and, 37OoC
    (sanple 14051). All sanples cone frou institutional collectlons'
    and vere described as origiaatJ-ng frou the |ti'lartha l,fi.nen.
    Presunably they lrere collected, fros one of the d.eep levels on
    'uhe l,{artha Veie where sulphide ore was comton.

    rffpRoGErI .lsoTcPES

    Fluid. inclusions in sanple 1l+075 (1,fh4) eontaia water with


    a 5D value of -l*lr-5 per nil. Several d.ifferent origins ars
    possible.: neteorie water precipitated d.uring a cooler cliaate
    than at prdsentr nod,ifLed rnaguatic water, aixEd, nagnatic .-
    neteoric waters and lastly fornation (connate) water. An
    origin fron neteoric uater is favoured, h,era.
    pEPT:I_QF l,l+ NERATISATIgN

    A scale of depth belorr the surface at the tirne of


    nineralisatlon is shor,rn in Fig. I.-S-7 for the l{artha vein
    systen. The surfaee datun is considered to be now representeC
    by a leveL 200rn above Martha Trig. The evj.d,ence for choosing
    this partieular datun j-s the near surface style nineralisa',io:l
    in the upper levels and the pressure - depth constrai.nts of
    the hydrothernal fluid boiling on 12 1evel.

    is consistant with the depth of


    The reconstructi.on
    ninerallsation indicated by the hydrothernal alteration
    assenblages i l'25 600o ( Braihwaite 1 980) .

    THERl,t0CiiEr{IqTRY

    Introduciion
    Three mineralisatlons of the I'Iaihi I'line are nodeLled, as
    folLotts 3
    (a) deep 1eve1 quartz, calcite, K-feldspar' sericite' pyrite,
    ebalcopyrite , sphalerlt,e, galena, .acanthite, electruu, t
    pymhotite at 325oC .
    (b) lnteraed,iate 1eveI quartz, calcite, sericite, K-feldspar'
    pyri,te, acanthite, electrun, t ehalcopyrite, t sphalerite'
    1 galena at 280oC.
    lA
    530

    lfBtiE I-$-2: Oeaarel theruoebsulell pererstcrc for threc illfferent


    tbT|ro!tronir of, Elnsrrl ileporftlon !n thc l{artha lfcln
    llyrtel r ltstlt,

    Enylrongeat
    fuietuedl'a c Sppsr
    Los levele Lovels lrcvel,g iefrrrnre.e:
    og ,25 280 ?20 TabLe V-1
    tgrponature
    0.t0 |l
    trug lou,Lo atrcngtt 0020 o.23
    '0.t9 n
    Selinlty (lr llaCl, aq.) 0_33 0.?;3
    I
    rtrt 0.0?Q 0.05? o.otg
    pS 5.'5 5.5 5.6 See tart
    pfi of taoUnits/serlstte
    &.:1 L.2 {.5 Table V-l
    bouadery
    pE of e rl61telE-fs1dsPat tt' t
    5.5 5;7 O.
    boundery
    Tota'l B (log rS) .2.0 -2.O -3' 0 Sao tett
    Log fS2 (cn-ha!.crlta eolP.) -8"Oto-1 0.1 lab1a,V-44
    (elcctrls corp.) -9. ?ta-l 0. -ll.rl fable V-6A
    Lss f@Z -3O.5to-32,2 ;r)*",2to-t6. -?9.Oto
    Lg. IiS-9) Elg. f-S-lO) -19,.5 flgurca ettail

    teg fCo. +1'. ? fl.g labla V-l


    531

    (c) shallo"r 1evel quartz, sericite, K-feld.spar' pyri.te'


    acanthite, elactrun at 220oC.

    Table I-S-2 lists soae of -r,he paraneters for these


    dif feren'b ninerali sations.

    Deeo level nineralisation


    The geochenical environnent of the d.eep J-evel urineralisation
    j.s licited on the fSa versus fOa diagran (Fig. I-S-8) by the
    presence of pyrite and chalcopyrite but absence of henatite,
    nagnetite aad, borniter Pyrrhotlte i.s present with plri'ue.
    aad, chalcopyrlte as inclusions in sphalerite in onJ-y two
    sanples studied.

    The FeS contentof sphalerr tes ind.icate a range in log


    fSa values frorn -8.0 to -12.1, whereas the graphite/Coa and
    calcite/anhydrite boundaries, defined by the log fCO2 value
    of +1.7 (extrapolated, fron the fluid inelusion analyses of
    late stage quartz sanples) ltnit fOa between -32.7.and. -29.2.

    nineralisation plots in the red,uced. sulpirur speci-es


    The
    region of t,he f02 versus pll diagraa (shaded area of Fig- I-S-9)
    and indicates a fluid containing sulphur in solution
    predoninantly as IIS-.

    Int erse4iat e 1e'rel .jnlnerali sation


    Internediate Level quartz, calclte' sericite, K-feldspar,
    pyrlte, acanthlte, electruu t chalcopyrite, t sphalerite and,
    :t galena nlneralisatlon is represented by the shaded area in
    the fOoI
    versus pH dlagran (fig. I-S-10). The nole fraction
    of silver in electrun lndicates log fSt values betueen -9.7
    and -1A,3 at 280oC. The absenee of nagnetite and heuatlte
    restricts the nlnerallsation to the reduced sulphur spe.bies
    field.

    fS, values stated., are posslble at 1o3 fCO, = +1


    The 1og o

    only when the graphite free nlneralisation is in eguilibrlua


    uith K-fe1d,spar. Asseoblages containing sericite nust have
    been deposLted at lower C0, fugacities.
    532

    ryRrrE
    N
    (n lro.m

    J
    s HEMATNE

    PYRRI{OTTE

    -42 4 _t8 _16 14 _r2 p _its -2C _*

    Lq foz

    Flgure I-S-8: fS, versue fOa dlagrao et 325oC ahowlng the geochenlcal
    envlroBoent (shaded) of quartz (I calclte) + pyrl-te + chalcopyrlte +
    aphalerlte + galena ! acanthlte t elsctru, t t"ttrbedrltc t pyrrhotlte
    veln uluerallsatlon ln tho 1or levels of the l.lartha vcln aysteur Ualhl.
    (See leblc I-S-2 f,or relevant thornochenlcal pereuetcra and AppendLl V
    for rethoda of constructlon.)
    533

    Kaolin Scricifc, I K- fcldspar


    l
    !}IEMATITE

    i$fr Ir
    :

    I lrl

    e Stt- lMnsNErtrr
    J

    -LE-Lstz=9.-+---
    I

    -Lstfu-,--9--!---
    flf52.-to i
    FY RRHOTI]E
    I u"t

    Elgure I-S-9: t02 verauo pB dlagrar tt t25o} and S . O.O1r ehoulng the
    geocheulcal envlroanent (sbaded) of quartz (t cclctte) + pyrtte t
    ohalaopyrlte + rpbalorlte t galena ! acanthltc I clectru. t t"t".hedrlte
    ! pyrrhotlte vcta ulaerallsatton la tbe lou levels of tbe l{artba Vcln
    rystD, tlalhl. pH of the ealclte aolubla/lsao1uble bounilary - 5.9. (See
    fable I-S-2 for other rclevant thernocbell,oal peraaetera and Appaudtr V
    for rethoda of consttuctlos.)
    531-

    oN MA6NETITE

    s I

    I
    f
    I

    FTRRHOTTI+

    Flgurc I-S-10: f0, rcrsua ptl dtagrao ai 280oC anil {S'0.01nr ahoulng thc
    geocberlcal envlronoent (shaateit) of quartz (! calclte) + pyrlte i acanthl'tc
    i elcctrun t chalcopyrlta t aphalerltc t. galena veln ui.nerallsatton ln
    the lntcrueillata levela of the l{artha Vel,n syster, Ualhl. (See Table
    I-S-2 for relevant theroochealcal paranetarg end Appendlx V for uethoda
    of coastructi.on. )
    ''l I

    535 |I
    I
    I

    ff.2 and, Te in solution uere probably higher ll1 tho


    rz
    Rosenont HiIl veins than in the t.lartha Vein Systen as indicated' I

    by the occurrence of hessite i.n the fornEr but acantirite in


    t,he latter (c-f . Fi3s. 11-/t and 11-5) '

    Snellgw ]--gvel ainarali sa-ui9+


    ?he 3eocheaical environaent oi the shaIl levq1 nLneraliss-
    iioa is shosn as shad,ed areas in Fi3s. I-S-11 auC I-S-12.

    Saaples strictly of the nineral:Lsatlon nod,elled. here trere


    aot available for stud,y bui the nole fractlon of silver in
    electruo in sanple 1 l$32 (GJ3) (lou tenperature P:frtte'
    acanthita, spbalerlte, galena and elEstruu nlneraltsatloa) ls
    used here to calculate an apProxluate value for sulphur
    fugacity of tha 1o'r tenperature oineralisatlon. A Log fSt
    valua of -11.1 is inCi.cated.

    Log f02 is linited betneea -39.8 (graphitelCO;- boundary)


    anil -36.10 (ealcite/anhydrlte boundary) at log fS" =-11.1 by
    the presence of ealcite but abseace of graphite and' aohyd'rita
    (Fig. I-.s-11).

    A totaL sulphur in solution eoncen^r,ration of 0.00112 T as


    used for the eonstruction of the fOr. versus plt diagraa
    (nig. I-S-12). The nlneralisation plois on or near the
    oxidised sulphur specles/reduced, sulphur speeies bouud'ary in
    Fi.g. I-S-12.

    GEIIESIS
    A value of^15 per nil is asslgned to S34SS ln solutLon
    based, on the SSLS values of tbe sulphlde sinerals and' the
    appareni presence of sulphur J.n solutlon ia red'uced' fora-
    Therefore the suLphur probably origLnated, as na'geatlc sulphur-

    The 5 D value of -45 per nil neasured, ln late stage fluids


    ( c.f . Chapter 8) is beu.eved, io indicate that thE sater ttas
    predonlnantly neteorj.c. A sinllar origin ls postulated, for
    uater of the oaln stage fluids. The d'eeply eirculailag
    neteorlc water nlxed witb nagnatlc fLuiC and, acguLred' sulphur
    (SOZ), carbon (COZ), netaL chloridE and' aatal sulpbJ'tle
    536

    Astolvad
    t)lilrarE,
    t'
    G|
    rfr
    (t\ TYRITE -{.f-'
    _3

    bJ&"
    -4 -& 4 -ql # 40 -|6 'X -?2 -70
    Loj f0z

    Flgurc I-S-11! fSZ eorau! f,Oa dlcgran at 220oC rhoning the gcocheo!,cal
    envlronoent (linc of croes-ea) of guartz (t calcttc) + pyrtte I acanthltc
    I clectruu vel.n ulncrall,gatlon ln the uppr levels of tbe llartha Veln
    ryateo. (See Table I-S-2 for relevant tbernochen!,cal paranctcra aad
    tgpenillx V for ucthodg of conetructLon.)
    53?

    I 3

    I
    t.. I
    I
    IJ
    l\) iHEMATITE
    F
    I

    o({ SORNIIE } PYR]TE

    ct-
    o L4,ILz=lr---1-!--
    coz
    C0z '
    rm'fcoz I-r-
    Giafiila-t*'T'l-

    PYRru{Orffd

    PH

    Flgurc I-S-121 fO2 veroua p[ illcgrar at 220oC and { S - 0.001r ahovlng tbo
    geocheolcal eailronnent (sbaaletl) of quartz (t calclte) + pyrlte + acantblte
    + electrun veln ni.nerallgatlon la tbe upp6r levela ol the llertha Vetn
    !yBt6E' llatht. the pf, of the qelclts golubls/lnaoLuble boundary . 4.9.
    (See lable I-S-2 for otber relavant theruocbelJ,cal paraoeters aad Appcadlx
    V for Dothoilr of constructlon.)
    538

    coniplexes pred.otrinantly froa this source. The fluid ascend.ed


    via the various fault fissures d.epositing sore of ii;s con-
    stituents along 'uhe r.lay.

    The ver',,ical neial zonation in the veins at l.Iaihi is


    attricuted. to changing pht'sicochesical eonditions with depth
    resu]ting fron fluicl - r'rall roek reactions, boiling horizons
    and :;rixing of the hyd.rothernal fLuid rvith oxygenated uaters
    near the sufface. Variations in f0Oa are consiCered to ha.re
    e.lso hacl a narked effect on nineral d.eposition (and r*a1l rock
    alteration) and nay have been inoortant in causing hydrothernal
    leacning of calcite. Extrapolation of the fC02 values suggested,
    for the internediate and sha1lor.r revel late stage fluid.
    (iluia inclusi.on analyses) to the deep revel environnent
    indicates i,ha'," calcite was stable at onry high values of pH.
    Therefore, although large quantities of ealcite were deposi.ied,
    especiall-y during the early stages of veln fillin.gr period,s
    of d,eposition nay have alternated, uith episod.es of hydrotheraal
    leaching. Thj-s alternaiing d.eposition - solution process lras
    prcbabiy caused by fluctuati_ons in tenperature, pH and, fC02r
    possibly as a result of boiling, reactions with lrall rocks or
    varj.atlons in the tenperature and. conposition of the fluid.
    supplierj to the systei.r ( source variations) .

    The large size of the llaihi deposits suggest that the


    hyclrothernal systea and. the rrarious nechanisn of deposition
    lrere active over a long period of ti.ne. Suitable structural
    environaents for vein fornation nust have been continually
    produced d.uring this peri.od,. rn fact the structuraL aspects
    nay be the nost i.nportant factors that d,eternj-ned the size
    of the l{aihi deposit and nay give a clue to its genesis.

    The l'lartha vein systea conprises a group of veins uith


    three prcd.oninant trend.s: lFiI (i.iartha, llel.cone and north-
    eastern sections of tb,e Enpire and Royal Loces) , i'IiIrJ (Edruard
    and Albert Lodes) and l{}j'rl (south-l,iestern sections of the
    inpire aiid, ito;'aL Lo,ies) forning an overall loop vein pattern.
    The north-eastern extension is cut by a d.etral transcurrent
    fault strilcing o05o (i.Iellnan, lgslo],. The v.eins converge with
    depih (Fig. I-S-/r)r gnrally onto the }lartha Lod.e, and the
    d.isplacenents of country rock fornr a series of collapsed.
    539

    ,'
    Flgurc I-S-13t Block dLagran ahov!,ng tha veln pattern and relatl.vc tlleplaee-
    uants of couatry rock Ln tbs Hartha yoln Eylten (Flg. I-S-13A). The
    ryateu appsars to cooprise a gerler of collapaed luverteil elllptlcal GoDeEl
    onc lnsl,ds the othsr and rasenbles the Etructutes that f,oide & BhattaaharJl
    (19?5'l and Kolde (la part VII-Z of Ina!.r 19?6) congtdsr occur above goare
    nagnatlo latruslons (f18. I-S-1]B).
    5ta

    j.nverted eLlpticaL eones, one ,inside tbe othe:r, produced by


    tens,Lon tn $tl - SB direations.. l{ortrc by 8ol,:rle & BhattaeharJi
    (1975, bnet Koj.de (in Part VII-2 of l,nal, 19?8) Lnd.lcates thet
    . 6ush a pattarn eouLd be p-roduoed, above a nagrrattre lutrusifon
    (Fi"g, I-S-13). I{or*ever, thi.o interpretation requires that
    *a the upper pyroxeae andesl.t,e be p:rasent prior to vein fornatl,on
    (nagrnatlc intrusign) wbieh uay not be eoapatlbl.e rcltlr tho
    apparent abser'*ce of, signi.f,lcaht hydrottreraaL alteration in
    this unlt (e..f,. Be1L & Frasero 19'12; ldqrgan, 1924.1 .

    BpFE4S!I Cqg A$n. DXBtIoGRAPItx

    BELL, J.M. i FRASDR, G. 1912! see pp123-172


    BRAIHI.IAITE, R.L. 1 980
    DO['iiIEg, J.F, 1935! s'e:e pp?35-Zltg and 288
    HAI{C00Kr P.:.1. 1979
    HUTTo,$, C.0. 19 t+l
    [lODRtrI{trAK, N. i IIARSDEN, E. 1935: see pp67-7'2
    HOBGA}T" P.O, 19.21+
    1925
    scEoFIstD, J.G. 19,6in
    rEf,LlIAlI, II.lf . 195t*
    t{ItLIA}tS 19'l I+z see pp1 1 0-1 1 4
    ' '0.I.
    5lr1

    I-T
    KARAITGAHAKE

    Ii'ITR0DUCTI0N

    The mines in the Karangahake area produced 125 nilllon


    grams (41011 ,7t+1 ounces) from 1.11+ nilli.on tonnes of quartz
    between 1875 and the 1930rs. Although a large nunber of
    small conpanies lrere active i-n the early years of the fields
    development, the high cost of nining and ore treatraent due to
    the steep and rugged terrainq and low reeovery of gold fron
    the ore, allowed two conpanies, Talisnan and Crown, to
    eventually take over the rest.

    The Talisnan was the seeond largest nine ln the provlnce,


    after rdaihl, and the third largest in llew Zealand.
    The Karangahakenining area is aLso notable for the
    first application of the cyanide treatnent process for extrac-
    tion of gold from the crushed ore, introduced by the Crown
    Mines in 1899.

    Ih" investigation by Henderson & Bartrum (1913) is the


    most recent published orlginal geological descri"pti-on of the
    deposits. They have since been reviewed by Downey (1935) and
    William s (1965, 1971,) .

    In the early 1970r s Southern Cross Mlnerals reopened 7


    and 8 levels for Au and Ag mining but after spending most of
    their money on plant and machinery found insufficient gold in
    the veins for continued work. Around '|.972 they dianond drilled
    from just above river 1eve1 ( corresponding to 1 1 level in the
    nine) d,own several hundred, feet to i.ntersect the najor quartz
    veins. The results of this activlty are held on closed file
    at the Mines Departnent. Recently Southern Cross have renewed
    activity i.n association with an overseas conpany.

    Dr. R.L. Brathwaite of the Geological Survey ls presently


    investigating the geology, hydrothernral alteration and
    nineralisation of the Karangahake aree
    '..:
    5lr2

    GEOIOGY

    The country rocks in the Karaugahake area are nostly


    Corornandel Group and,e.site flous and pyroclastics, however
    Whitianga Group spherulitlc rhyolite caps l'{t. Karangahake -

    Henderson & Bartrum (1913) d,escribed the succession of


    rocks in the Talisntur Hine, in asceadi.ng orderr &s follows:
    (") andesita, (U) breccia with argillite fragments, (c)
    andesitic tuff, (a) breccia with andesitic fragments on1y,
    ( e) augite hypersthene andesite and ( t) spherulitic dacj.te
    (regarded here as sphertrlitic rhyolite). They noted (Eenderson
    & Bartrun, 1913 p59 tfrat basenent argillite (llanaia lliLl Group)
    was reported to have been reached, at the botton (335n below
    sea l-evel) of a drlll hole sunk by the Woodstock Conpany.
    The louest level of worki.ngs in the nine, 16 Ievel, was
    approxirnately (sca1ed, off Fig. 23 of Downey, 1935) 160m below
    sea leveI.

    FIp.R0THE4MAT ALTERAT IoN

    The bydrothernal alteration of the anclesites was described,


    by Henderson & Bartrun (1913) as propylitic. They observed
    the following sequences
    1. The first stages of alteration are narked. by the
    conversion of hlrpersthene and feldspars to chlorite, sone
    sericite and tuo unid,entified, ninerals, one descrlbed as
    nserpentinous naterialt and the other as nresenbling uralitert.
    2. Further alteration lnvolves the breakdovn of auglte
    to chlorite, epld,ote, calcite and secondary quartz and the
    eonversion of the nserpentinous rnateriaLn to chlorite.
    3. Feld,spars are altered to sericite' calclte and quartz.
    Epldote is eonverted to chlorlte, caLcite and guartz. Siderite
    and eonetines Leucoxene are prod,uced fron the breakdown of
    lron oxldes.
    4,. Intense alteratiou adjacent to the veins produces a
    rock cnnsistlng of a fine shitish mixture of quartz, serLcite,
    calcLte and pyrlte.

    In another section of thelr bulletin, Henderson & Bar''


    neation that ad,ularia lras present in sone rocks. Dr. R.L
    Brathuaite (pers. cotrDc) consid,ers tbat ad,ularia is uore
    - i :i}r,.:^i:'i-; :-:ii,''.'Tr','i:-.: r: ';r -:"' :
    ':.:.-;j!!f.;.',:a '

    . i. ' .r,,-- "*i'iii*:;ir -:-l , , ""


    5lr3

    scAr.E
    tq, o tooofr

    v'l
    rt- 5= t--
    iu*l

    Flgure I-T-1: Hlne rorklnge and velns of the Karangahako arsa (fron Wl1llara,
    1971,i atlar Hsnderson & Bartrunr'l 913.)
    5 l,lr

    cotrnon thaninplied by Henderson & Bartrunrs description and


    is a najor alteration prod.uct in the uall rocks a{.jacent to
    the veins.

    The I'Ihitianga Grouprhyolile rocks capping Mt. Karangahake


    are also hydrotherraally altered (Brathwaite, pers. conn-),
    however the speci-fic types of alteration have not been
    described..

    K AT AGE DATA

    Eydrotheraally altered and.esites fron Karangahake have


    been K-Ar d.ated at 4.8 E.y. (2 sanples), sbereas sanples of
    unaltered and.esite gave ages of 4.9 and J.2 m.y. (nr C.J.D.
    Adang and, Dr'A. Wodzicki pers. connm.).

    MI}IERALTSATION

    Hineralisation occurs in three najor veins (fig. I-T-1 );


    the Crown, lfelcone (Uotfr Crornr i,lio"") and Maria (Ta1isnan and.
    I{oodstock Mines), All Karangahake sanples studied, here are
    fron the Maria Vein-
    Crown Vein
    The Croun vein was the smallest producer of gold of the
    three.najor veins. It strikes north-north-east and. dips west-
    vard at a high angle. From the Gross-section (Fig. I-T-2) the
    croun vein appears to be a |tfootwall droppertt from the lfelcone,
    although no Junction was ever found.. Little geological
    infornation is record,ed, although Henderson & Bartrun (1913)
    noted, that the l-od,e vas best d,eveloped on 3 Level.
    Welcons Vein
    The Welcoue vein uas traced, for 1.2kn and found, to etrike
    north-north-east aud dip 5Oo to the west. It is displaced by
    a nunber of faults clividing it into blocks but no definite
    ore ehoots lrere recognised. n0xi,disedrr ore occurred. in al-l
    leve1s with the exception of a snall quantlty of sulphide ore
    in the d,eepest level. ?he gold to sllver ratio in oxid,ised,
    ore lras 1:1. The vein was nined fron 12 levels (six adit and
    six shaft) aud, Hend,erson & Bartruu (1913) noted that levels
    1 to 3 contained little goJ.d.
    5lr5

    N-2. CRorVil Mlt{ES

    Flgure I-T-2: Grosa seetlon of the velas lu Karangahake llountaln (frou


    Ecndcrson & Bartruu, 1913.)
    5l*6

    Maria Vein
    The Maria vein was traced for 2.0kn and, ln contrast to
    the general north east sttike of nost of the other vej.nsr ltas
    found to have a conposite strike being, from north to south:
    north-east, north-west, north-east and north (Fig. I-T-1).
    In the lower levels of the north strikiug section nunerous
    snall stringers, striking north-east, join the hanging wall
    but do not leave the footwall.

    The Marla proved to be the nost profitable vein at


    Karangahake prod,ucing approxinately ten tines as nuch gold and
    sllver as the l,lelcone and Crown Telns together. South of the
    Waitawheta Rlver lt contained four ore shirots known as the
    Wood,stock, Talisnan, Bonanza and Dubbo (Flg. I-T-3).
    Practically all the rich ore cane fron the Talisnan and
    Bonanza shoots whlch uere worked fron 1 4 levels and several
    lnternediate levels, eleven of whieh were adit levels' the
    rernbining belng fron an underground shaft.

    The Bonanza section of the Marj.a Reef is the only vein


    secti.on ln the Karangahake area where the geology was recorded
    in any detail. Henderson & Bartrun (1913) noted changes in
    vei,n content with depth and these are sunnarised. ln Fig. f-T-/r.
    In the upper and internediate..levelsr the veln consists of
    quartz and quartz pseudonorphs after ealcite and contains
    narcasite, electrun and acanthite, whereas in the lower levels
    quartz and caLcite contai.n pyrite, sphalerite, chalcopyrite'
    galena, acanthite and electrun. In addition the presence of
    hessite was suspected by Hend.erson & Bartrum (Te vas detected
    la sone ore assays) and' Mercbant (19?8) noted its occurrence
    in a sanple fron an unstated locatLon in the Marla Lode. The
    gold to silver ratlo varies systenattcally towards the lowest
    value in 11 level (1:15) ancl reaehes the highest record.ed,
    value in the internedLate'Ievel betueen 1/+ and 15 levels'
    where gold predoninates over sllver. In the J.ow leveLs'
    barren portions of the vein are narked by the presence of
    abundant calcite.

    Southera Gross Minerals Exploration Ltd^ reopened 7 and 8


    levels in the late 195Or s - early 197Of s but foqnd' insufflcient
    5lr7

    TALTSMAN MINE
    KARANGAHAKE

    Scrb:? , Y F 4aota

    Slgure I-T-3: Longltutllaal gectlon of the Tallauan l{lne (uoetly the l{arla
    Veln), Karangahake ahorlng the etoped blocks (shaded) end ore ehoots
    (lfoodstoek, Tall.anan, Bonanza aad Dubbo). (Fron Flg. 23 o? Dorneyr 19t5.,
    5lr8

    Kararqahake lrig, (Sunuirt d Vt lrrruryhrrkc\


    _ Rlnyolite WVifiargra Gratp

    Andcitc Corutrqrdel Gratp

    fu: Aq
    tul'?io"rr,-,
    I lcv?l fincncst
    I Lsually balwsan
    '8W.)
    2 lcwl --
    .uu
    7 lcvcl i.E
    5f CI
    4 lcva.l
    !B
    6 lcwl tT I

    ".tl
    nFE
    6 lcvcl
    T;
    .nS
    -$!-L
    OFr
    :l
    z lcval gql
    e !3t'
    .E &r
    FI
    *P
    G:t !'6
    x.Ntr
    '6 o= s) 1
    I lcvcl 96
    EE
    9 lcrlql
    r=p
    o\
    :t >\ I
    o levcl cro-

    It lorcl l: 15

    Lrzwl t \Alaifawhcta .t
    '5 pT
    Riwr.
    12levcl
    , -!'E t l: l0 Corcllilc tn
    tua Vwl t rich orc.
    .o
    s
    ls*t*+-
    lz7
    t}lovul I l"-Etp! Wirc Sitwr.

    t4lcwl
    lnlcrmediatc
    tffi lrl
    Au >19

    Flgure I-t-4: Sote ll.ncraloglcaL changes vtth depth tn the Eouaazc sectlon
    of ths llerla Vein (colpllcd fron descrlptlone by Benderaon & Bartruu,
    r913). The hypothetlcsl depth of nlnerallsatlon acale glven'dovn tbc
    left hand elale of the dlagraD us6s a surfase datus 200n above llt.
    f,arangahake.
    5l+9

    gold values for profitable extraction, The present caretakers


    have opened 8 leve1 to beyond the Talisman shaft. The Maria
    vein is exposed, in a cross eut and here consists of mainly
    chalcedonic quartz but many vugs containing snall euhedral
    quartz crystals occur. I'lo visibLe nineralisation is present.

    No.11 1eve1 is also presently aecessible but only to the


    beginning of the l{ood.stock section. A few quartz veins and a
    stope were found but no vislble nineralisation other than
    pyrite.

    A few samples of sulphide ni-nerali.sation were obtained.


    from ilrstituti.onal collectiorrs. The petrography of the
    individual specinens is described in Appendix VII aad therdre
    only a brief account is given here.

    A sanple of a crustifieil vein fron 14 level consists of


    banded quartz and calcite with sphalerite, galena, chalcopyrite,
    pyrite and electrun (Fig. lr-6). Sphalerite and galena oecur
    in conplex intergrowths (e.g. Figs. l+-27 and. t+-28) and in a
    few bands sphalerite contains inclusions of galena t
    chalcopyrite t electrun in poikilitic (fig . lr-2g), dendritic
    rf streakyu (Fig. lr-30) and nyrmekitic textures. Electrun

    also occurs as inclusions in ehalcopyrite and, at a later


    stage, with quartz invading the earlier sulphides (Fig. lr-31\.

    0ther sanples contain bands of fine grained sulphides,


    and in one case rare electrun, in vhich the netallic ninerals
    generally occur as individual grains scattered in quartz. The
    ratio of sulphld,es to gangue is approxinately 1:3 in the
    sulphide bands but nuch less when the whole specinen is
    considered. Silver ninerals apart fron electrun were not
    ldentified in the specinens and their absence nay account for
    tbe high Au:Ag ratios reported frou the lowest levels by
    Henderson & Bartrun (lgl3).

    FLUID INCLUSTO}IS
    Pri.nary fluid inclusions in quartz from 11 level ( sanple
    1l+022) and 8 level (sample 1l+021) of the Talisuan nine and
    outcrop of the Marmion Extended Lode ( sample 1l+029) are rare
    550

    200 220 240 2@ 280 0t2?


    t-r-t-l

    t4029

    Etr EI

    t+o22

    t4021

    t--J--J-l
    200 220 240 260 2@ o | 27
    Fiffing -femperafurc 'C
    ZT!'*{vnNacl
    9inale.
    --'-2 - valucs z EI

    Ftgure I-T-5: El.etograua of prluary flull tncluslon fllltng tcnperat'urca and


    apparcnt rall,uLtt.es f,or gsuPlee of quart'z frou the TalLrnan Hincp
    Karaugahaksc 14021, 11 1evelt 11O22r 8 levell 1L029t l{arnloa Extenileil Lode.
    lhe Lniltvldual ueasureuenta ars llateil la lppendlx III.
    551

    and of snall size, They are two phase, liquid plus vapour'
    norrnal types.

    Filling tenperatures and salinities are shown as histograns


    in Fig. I-T-5. Pressure-salinity corrections i-n the ord.er of
    5 - 1OoC nust be add.ed to the filling temperatures. Corrected.
    filling temperatures indicate deposi-tional tenperatures around
    Z3OoC for the 8 level sample and 260oC for the others.

    0n1y a few inelusions i-n the Talisman saraples were


    suitable for freezing ternperature neasurements and these
    indicate fluid cornpositions of relatively high sa1lnity,
    around 2.5 ee. !rt. I ltaCl.

    SUTPHUR ISOTOPES

    Complicated. intergrowths of sulphide ninerals (e.g. tr'igs.


    l*-2? to l+-30) precluded separation of cogenetic sulphide
    ninerals in tt all sanples from Karangahake except sanple 11,,023
    (Tt 17). 6)45 values of this saurple are; chalcopyrite +3.0
    per nilr sphalerite +2.9 per niI and galena *0.7 per nil. The
    fractionati-on betrleen sphalerite and galena indicates a
    depositi.onal temperature of 290oC.

    location of sanple 1l+023 (Tt 17) within


    The original
    the Talisaan l{ine is not known but because it contalns
    abundant nedium grained sulphid.es, and sulphides were reported
    by Henderson & Bartrun (1913) to be connon only below 11 level,
    it presunably cane from this lower region.
    DEPTH OF MINERATISATIOI{

    A scale of depth below the surface at the tine of


    nineralisation is shown i.n Fig. I*T-4. Assuning that
    ninerallsation occurred around the tine of rhyolite volcanisn
    and allowing for some rhyolite cover, the ori.ginal surface ls
    consldereil to have been approximately 200m above the trig on
    top of l,lt Karangahake.

    TiIERI,I O CI{ EI,{ I ST RY

    The geochenical- environment of the quartz, calcite, pyri.te,


    552

    -A
    -E
    -26

    -n
    -n
    -4
    (\I
    o -10
    i- MAGNETTTE
    s -r1
    -t2

    -t -t
    !sz-2--+---
    -x ryRITE I A
    -t5
    -*

    PH

    Flgure I-T-6: fOa veraus pH dlagran at 300oC and {S = 0.01rr ehowlng the
    geoehenlcel envlronoent of (A) quartz (1 calcite) + pyrlte + chefcopyrite
    + ephalcrlte + galena and (B) quartz t electruu nlnerall.aatlona of the
    Marla Veln 1n the lor levels of the Talleoan lllne, Karangahake. i =
    0.2?, nKl . O.o?5t pH = 5 - ,.5,1og fS, fron aphal.erlte conpogltlons =
    -9.i to -9.9 (A), Iog fSa frour electrun coaposltlons = -8.6 to -8.7 (B),
    and log fC02 (estlnated) = ]1.5. (MEthodo of conetructlon are deecrlbcd
    tn Appendtx V. )
    553

    sphaleritel galena, ehalcopyrite and. eleetrun minerali.sation


    in the low levels is modelled in the fOa versus pH diagran
    (Ffg. I-T-6) at a tenperature of 3OOoC and a total sulphur
    in solution ooneentration of 0.01a.

    Fraser & Adans (1907) deseription of the hydrothermal


    aLteration and unpublished work by Brathwaite (pers. conm.)
    indicate that the flulds were in equilibriuu with sericite
    and adulari-a in the wa1l rocksr rstricting pH to values near
    the sericite/K-feLdspar bound.ary (S to 5.5).

    Log fS, values between -9./* and. -9.9 are ind.icated by


    the iron content of sphalerites, whereas values between -8.6
    and -8.7 are indicated by the rnole fraction of silver in
    slightly later electrun. Therefore two fields of nineralisation'
    A; base netal and Bi electrun, are shown in Fig. I-T-6. Both
    nineralisations plot in the redueed sulphur species pred.oninant
    field of the diagr&ltr Values of log fC02 up to the general
    value of +1.5 are possible in the absence of graphite.

    GE}IESIS

    Based on the values of 534S for the sulphide minerals


    and the apparent presence of sulphur in solution pred.oninantly
    in reduced form, a value of *5-per nl1 il assigned to S34SaS
    '
    (i'e. ? -t<S). The nost
    )Ls,, ^:.3L^
    .^ o
    6-*S"ulphide ninerals-
    "2o"r-
    likely source of sulphur with this 6'*S value is nagmatic
    sulphur.

    The short intervalbetween the d.epositi.on of the and,esite


    rocks at Karangahake and their subsequent hyd.rothermal
    alteration, as indicated by the K-Ar ages' suggests that the
    early stages of vein formatj-on and nineralisation nay have
    been associated with the waning of and.esitic volcanisn.
    Hydrothernal aetivity continued. during rhyolite volcanisn as
    evidenced by the presence of hydrothernal alteration in the
    rhyolite rocks capping I'lt. Karangahake.
    Favourable structure allowed the developnent of a large
    geothernal systen in the Karangahake area with upward nigration
    55t,

    of the hyd.rothernal fluid (predominantly meteoric water?) via


    the various fault fissures. A vertically zoned nj-neral
    sequence was deposited in the vei-ns as a result of the changing
    physicochenical cond.itions with decreasing depth. Base netal
    with ninor precious netal roineralisation was deposited at
    depth with quartz calcite and. adularia, as a response to f1uid. -
    wall rock reacti.ons and varying f00r. l'{ixing of the hydro-
    thermaL fluid with oxygenated near surface vaters and decreasing
    tenpernature and pH were the probable causes of precious metar
    deposition i-n the shallow Levels.

    The large sizeof the Karangahake deposits inplles that


    a large quantity of hydrothernal fluid circulated through the
    systen and that it was active for a long time,

    BEFEREITCES AIID BIBLIOGRAPHY

    DOi'INEY, J.F. 19352 see pp 199-211 and ZB7


    HEIIDERSOII, J. i BARTRUI'!, J.A. 1913t see pp 81,,-8?, 89-101 and
    110 to 116
    scHoFrELD, J.C. 1967
    lIfLLIAi,lS, G.J. 197trt see pp 11 L-117
    555

    I-U
    TUI i,iT}iE

    Ii'iTRODUCTION

    Tui. l{iqer under nanagenent of Norpae i'fining Co.,


    produceC copper, lead and zinc concentrates for export to
    Japau between 1967 and 19'llr. Total prod,uction for this
    period, vas 71291 tonnes Zn, l+rlrZl* tonnes Pbr 4,0,(, tonnes Cut
    2.119 roillion grans (90,000 ounces) Ag and 60,000 grans
    (t *95e ounces) Au. (Alf f igures for pure netals, ltines
    Divisi.oa records).

    During this period, of operation the d,eposit was studied.


    by Auckland University students (Cochrane, 1969; i{eigeI, 1978)
    aud^ several nenbers of the DSIR (l'Ieissberg & I'Iodzi.cki, 197Oi
    Wod.zicki & lleissbergr 19lO; Adarns et al, 19?t+; Bobinson, 1971r;
    Ansia, 1975).

    Before closure of the nine the ttines Departnent funded


    the drilling of two holes to test the nineralisaiion belos
    Charnpion 5 leve1 (pig. I-U-1). Both holes sere clriLled fron
    the sane location in 5 level but at dlfferent angles. 45o
    aud,.?0o. The results are ibported, by Ker & I{odzLckl, (fn
    press) . .: '1 :: i
    . i-..

    GEOLOGY

    lui Mine is located on }lt Te Aroha, a 952rl high peak


    conposed of andesites of tbe Coronanclel Group. Goehrane (1969)
    coLlectlvely naned, then Te Aroha AndesLtes and, subclivided
    thoa as follows:
    1, Tui AnCesite j a nassLver euartz free tuo pyroxene
    andesite, occurring on the surface belotr an elevation of i(,88n.
    2. Ruakaka Quartz Andesite; a quartz and.esitE vlth
    nasslve'breccia and tuffaceous phases, occurring on the
    surface between elevations of {,88n and, 914.o.
    3. Sunait And.esite j a nassive andesite' identical with
    the Tul And,esite, forning a hard, c,ap on the sunnit of l.It Te

    t r;,
    ,1. I
    556

    . LEGEND
    rocr rtrt3
    notllrt oll wrofH
    Q rveoxtrt : r{ctott
    Erurr : Oft00_0!rrtrrl3
    @roxvntrl @, ortolt-o!.ntrr:t
    f:Tl l!!|l 0t!o !a- | 0Ftrrrt
    r o^cfraNotrrl
    s Ouarrr I or>to
    liAil Qualrz
    s e oactraaNorgtt
    tllccra
    ,vitotS
    -ii. Sttrrt o'or aaoDtr{G
    ri! ttrltr ^io
    .ia Dtr C (O'tt
    /-- ./rl_\_ -\\
    -r irrrradorr dnNl|a!r[uoroffr!
    .r; (-1__lrz-\>Jr/
    \\\\/ \J
    Itlrxrddtdt|{r^rt \ .
    s/ tlut{Gtd!.|clexr|Dtt \'\ \)\
    r.r. tr'racaroocourcro' \_-..--\ \'\
    iF soercrour.owoulct \)a. .t\
    ?--= ruttacC roaon \ -r
    r\ ,eis. ))
    t\:tt=====t\ {t'-V'y^
    II
    ii

    .i/it $iii';'-

    /-
    N
    fifr') i'::I'-.'
    z'./-
    1i'
    II
    ,l
    \l
    / {
    \

    IUAXAXA

    0 lO tF Fd.
    C l(. l(r| Etr.r

    Fieure I-U-lr Ceologl and worldngs ln the 1\rL Mine. (ft*


    WodziclC. & t{eissbergt Lg?O.)
    55?

    The geology within the nine is sho'.rn in Fig. f-U-1


    reproduced froio llodzieki & l'Ieissberg (tgZO). The predorni.nant
    rock type, pyroxene and.esite, is equivalent to Cochrauets
    Tui Andesite, whereas all the other units noted belong to
    Cochranel s Ruakaka Quartz And.esite. The sequence of roeks
    in 5 level cross cut in Fig. I-U-1,is sirailar to Cochraners
    cross section (Fig. "ll, of Cochrane, 196,o).

    itIDR,0TIlER!:lAt ALTERATT o$
    Hydrothernal alteratj.on in tbe Tui l.fine area is
    propylitic r,rith various assem-blages of chlorite, pyrlte,
    epidote, adularia, serieite, calcite, quartz, nontnorillonite
    and kao-linite. tr'Ieissberg & I.Iodzicki (19?0) classified these
    assenblages into four groups (Fig. I-II-2) with the progression
    fron Groups f to IV representing increaslng intensity of
    alteratioa. The nost altered rocks (Group IV) oceur ln
    narro'f, zones adjaceat to and. in between the two najor veins,
    the Chanpion aad Ruakaka Lod,es.

    l,Iod.zieki & lleissberg ('tglO) constd.ered. that at a given


    Location, adularia forned before sericite and that
    nontnorilloai.te, interlayereil illite-nontnorillonite ( sericite)
    and. kaolinl'r,e were fornecl by late stage low tenperature 'fluid.s.

    K - AT AGE DATA
    Ad,ans et a1 ('lg7lr) deternined wbole-rock K-Ar ages on
    nine sacples of andesite, displaying various d.egrees of
    hydrothernal alteration, fron Tui Mi.:oe. The rocks yielded a
    spread of ages fron 16.2 my to 2.6 ny. Adans et al (19?4)
    coneLuded that the naxinun age of 16,2 .ny (tfre least altered
    anCesite) lras a close approxi.rcation to the eruptive age of
    the andesitesr tuhereas hydrothernal alterati-on occurred, at
    least 2.6 my, but Less than 7 ny ago.

    I{II{ERALISA?IO}I
    ZLnc,- lead, - copper nineralisation occurs ia two quartz
    veinsr the Chanpion and Ruakaka todesr forned in fissures of
    nor:ral faults dlpping between 50o-80o-north:lrostr and 50o-85o
    sgut] respectlvely. Several stages of fault novement,

    ,': ' ' ' iiil ;$ i ',ir1.1,iil!*fi,,i'ftrt.,' ,iii .;*i "', .


    'ii,
    558

    AlTnR|Ttoir GRoUPS
    MINERAIS tr tr nt
    VTt r>-
    llognclilr

    Hypc6utffi ab.
    $l &dlr ,,DA

    P'lcgiodort
    ,rr>_

    Oiloritr

    furito -a2,
    E*tola
    DTrtt>

    Folo$ ftHspor -tta77z. b>_


    ztTVVt
    Scricilc
    FI Cqlcitc
    ,-ttZD
    0uatr
    llontrnorillonilr

    Xoolhrtc

    Flgurc I-U-2; Changes ln tlnaraloly ulth lncrcaelng lntenelty of hyitrotherral


    alteratlon (oroup I veakly qltereil ihrough to 0roup IV atrongty eltereil). '

    (Frou lfodzlckl t tfeLasberg, 1970.)


    i
    I
    I
    !

    559 I

    earlier vein naterial, and. rnineral d,eposition occumed


    ultinately forning quartz veins up to 2a (Chanpion) and 8n :

    (R,uakaka) tfrict. The paragenetic d,iagrarn (Fig. I-U-3) and. i

    folloving descr5-ption are conpi.led fron several conpllnentary


    publisheC deseriptions of the nineralisation (Cochrane, 1969;
    Itod.zicki & lleissbergr 1979; Robinson, 1971,; Ansi.n, 1975; Ker
    & l'Iod.zicki, in press) and the wriiers observations of Stage 1
    uaterial.

    The najor vein constituents are quartz, sphalerite,


    galena, pyrite, kaolinite and chalcopyrite. I'linor anounts of
    carbonate, ad.ularia, epidote, wairakiter tetrah,ed,rite,
    narcasite, cinnabar, barite, henatite, gold aad prehnite are
    also found. Recently bornite, lrolfranite aud bisnuth
    tellurides were reported (llerchant, 1978i lleigel, 1979).
    .Bisnuthinite and, tetrad.ynite Trere id.entified during this stuCy.
    1. The first stage of ninerali.sation is characterised.
    Stage
    by a nilky quartz cenented waIL rock brecci.a 1 to 5n in width.
    Pyrlte occurs d.isseininated in th,e waII rocks and. in the nilky
    quartz. 0n Chanpi-on 4 and. 5 leveLs, between t*25 and, ?00a i.'.E.
    of the 5 leve1 access cross cut, significant quantities of
    chalcopyrite, sphalerite and,.galena in ad.dition to quartz,
    pyrite and ninor henatite occur (Ker & -r'Iodzicki. in press).
    Chalcopyrite preceeds galena and sphaleriie. . The sulphides
    are generally rned.iun grained. (less than 2nu) and. the Iod.e,
    connonly uider than 1n, has poorly defined, walls.

    Sanples of Stage 1 natenial fron il. Stope, 5 level


    Chaupion, contain chalcopyrite, pyrite' henati.te, bisnuthinlte,
    gold and. tetradynita. The fo3-lowing sequence, d,ed.uced. fron
    the specinens shown in Fig. I-U-4,, is tentatively assigned:
    1. nasslve chalcopyrite with rare narcasj.te balls (nou
    represented by pyrlte) infllling waIl rock anC quartz breccia
    (fragments up to 10nn).
    2. quartz plus blsnuthiaite, gold and tetradynite (Figs.
    /r-10 and 4-11).
    3. quartz plus pyrlte.
    4,- pyrite plus hematlte plus chalcopyrite (FiS . Ir-12) .
    5. henatite plus quartz (Fig. t -1il.
    :9; eoa.tz, fil.-allV devellping.into vugs
    ':..1{i:i.-;.i.'l.,....,.'.i.'.,.''..,:,'{i;iL
    ' 'l; ').'i11.,.-'' , ".",i1: l l.: .,, ,j.e -.. " :,i.#"rt . :.
    ' '
    560

    ufr;;55Qflf: I 2a 2b 3 4
    Qtwlz
    h/rib +
    (rl ,--- .io_l _
    l'lhrcc,sile
    Chalcoryrfia
    lalvu,d/ivl-if? zo =l
    Pl
    !---r
    lt
    Hcmafila
    GoV E
    3! i| i?-
    -?- Hi
    t
    Br'snlulhinilc u
    ut |
    Bowillc
    Wolfruvnifa
    d
    o
    -?- 'i ^ | I
    Cnlena
    Solvlerllc
    tirmwdrtc
    o
    z el%i.1
    Cinrnabar
    6arllo,
    Calcllo
    o
    z
    ei I a.-
    '51 |I I
    r---
    t-
    5
    Dolomile,
    Stdaite,
    5
    f; ol
    =t Il;- _ I

    ll(aolinitc
    lCerusite
    l9n*hsultc til l
    F
    l-

    F!.gureI-U-3: Paragenetlc aquanca of alnerala ln the Chauplon and Ruakaka


    volnul lul lllne. (UoAtftea fron Yotlzlckl & l{eiseberg, 19?0i Roblason' 19?lJ,
    t
    i
    561

    FLgure I-U-4: Cut surfaces of haad specloeno coatalulug Stage 1 cbalcopyrlte


    (brleht yollos) pyrlte (du).I yellos) and heoatlte (dark reil), trhlch ls
    brecclated, velned and coated (e.g. rlght bentl elile of specJ'oen at top
    rtght) by stege 2 sphelerlte (brown), galoua (grey) and quartz (rrbtte -
    translucent). lhe Stage 1 oaterLal also contalns natlve gold' blenut,hlnltc
    and tetradyolte. not vlslblo ln baad spec!.oen. Saoplea f,ron ll stopo
    Chaoplon Velu, courteay of Dr ll.ll. Kobe. The longest dluenolon of tbe
    largeat aanple ls 1?co.
    I

    562

    Stage 2. Reneued fault novenent resulted in the fornation


    of a narroi.r zone (usually less than 0.5n uid.er rrith r.re]-l
    d.efined walls) aad ihe deposition of Stage 2 ninerals. These
    i-ncLuCe coarse grained (greater than 10an) galena and
    sphalerite folloved. by nj.nor chalcopyrite' tetrahedrite,
    p;rrite, narcasite and. interaitteni quartz d.eposition and
    breceiati-on. .

    Stage 2 chalcocyrite is found enclosing anC partly replac-


    ing younger Stage 2 pyrite and together these ninerals forn
    veinlets in galena and sphalerite. I'4arcasite forns rirns
    around chalcopyrj.te and a further generation of chalcopyrite
    in turn rias the narcasite. This third generation chalcopyrS.te
    oecurs together uith tetrahed.rite.

    In the Chanpi.on lode Stage 2 nineralisation usually occurs


    within the early part of the 1od.e systen (Stage 1) but in
    parts of 4 level it is in the footwall- and in parts of 5 level
    it is j-n the hangi.ng wal1 (tter & llod.zicki). Stage 2
    nineralisation in the Ruakasa toCe occurs in one horizontal
    ore shooi uhich has a variable Po/Zn ratio,.rith depth (]-orl in
    5'Ieve1 and hi3h in 3 and, lr levels). The ore in tire lower
    part of the ore shoot is 1ow graile ttbreccia typett cenented by
    Si:age 2 quartz and sulphides (Ker & i'iod.zicki).

    Stage 3. Stage 3 nineralisation is represented. by quartz'


    kaoli.nite, bariter plrite, henatj-ter cinnabar, and, several
    carbonate ninerals partially filling the reaaining carri.ties
    and. late foraed joints.

    Supergene sugary calcite, snithsonite coatings and,


    eerussite infilllngs are sho'.rn as Stage 4 in the paragqnetic
    diagran. Ansin (197il record.ed a nunber of other supergene
    and secondary ninerals including covellite.

    FLUID IiiCtUSIO:{S
    Fluid inclusions in saeples of Stage 2 quartz and,
    sphaleiite aed. Stags 3 barite are generally tvo phase liquid
    plus vapour norqal types alihough a fibrous solid is also
    present in sone inclusions of sarnples 1tr}56 (Iui 131 , 1LO6l+
    569

    rlg!|rs l-Iti'a llhe ,iitnglr r.apour l}tE[ plthrry fluld lnslu,iiotl Ldcn'tifie.al ftou
    lul tll,rc (rarple 1406&' Stage 2 qnirtr)i 16l.
    561,

    (tu:. 22), and 14063 (tui 28), and a vapour rich inclusiou gtas
    identified, j.n sanple 1LO6t+ (Tqi 22i Flg. f-U-5). The latter
    indicates that vapour llas gr,rapped along with liquid at the
    iinne of fornation and therefore the parent hyd.rotheraal fLuid
    nay have been boillng.

    Filling tenpera',,ure and salinity neasurenent results are


    presented. as histograns in Figs. I-U-6A (Chanpion) end I-U-69
    (ituakaka).

    - salini'uy corrections that nust be ad.ded, to the


    Pressure
    fitling tenperatures to equate then vith d.epositional tenperature
    are approxinately 1OoC. Corrected filling tenperatures
    indlcate d.epositional tenperatures betr'reen 280 and 31OoC for
    stage 2 quartz and sphalerite- Filling tenperatures of
    prinary and, secondary inclusions (their generation could not
    be deternined) in S+,age 3 barite record, a uid.e teuperature
    range fron approxinately egOoC dor'rn to 120oC with no rsell
    defined peak.

    Salinities of priaary fluid inclusj-ons in Sta3e 2 quartz


    are higher than those of other vein d,eposits in the province
    with a rnaximutr treasurenent of 6.1 oe. wt. I i{a0l and an avera?e
    around 3 ee. wt. $ i'laCl.

    partial chernical analysi.s of fluid. inclusions in


    A Stage
    3 quartz frol the charnpion Lod.e (11+o5lr), deterained by
    crushing and leaching experinents, indicates the presence of
    52oo ppr t{a+, 1000 ppn K+, 11o,ppn Li+ ,antl 8000 ppn c1-. The
    leasured lIa/K ratlo is in agreenent vj.th that pred'icted,
    theorotically by the $a/li 3eothernoneter at a tenperatur.e
    arounC 2?0oc.

    SULPHUR, ISOTOP,IS

    Robinson (1g7t) deternj.ned.. 63Ls values for sulphid.es


    betr'reen -2.1, per rail (ralena) anC t4,.9 per nil (sphalerite)
    and indivld,ual values for barite of *15.0 per rnil and +19.5
    per ni1 fron sanples of Tui llj.ne naterial. Fractionation
    between cogenetlc Stage 1 pyrite-chalcopyrite pairs lndicated
    a d.epositional tenperature of around' 4,00oC, whereas a
    tenperature around, 320oC rvas indicated, for Stage 2 nineralisa-.
    ' ' i:.;^ '-<,-.q
    :j ;.-tz,'-:])
    565

    Stago 2 gllastwiFfian Wn
    ,i,60 7@ -n
    5- -o

    5'
    I I 110 *.
    ?2a
    l'L
    Fi t
    ilTI ll- .i$
    r- rlJh hh'
    tltt
    2W
    ||
    t-----_|
    tt
    tl b tN E i

    It-
    tf-
    sT
    -+
    Si
    g f qH
    tl
    2& F F lytoti
    a $r
    o
    6\ $
    $$ E$ $
    [*
    rs
    EFI
    ^J n l: e$ i
    lL-
    tr F bt 1',:,
    ro g
    i

    ginqla vduaEz I FilllngTernPauf;ure, I Eati nity

    ELg. I-tr!-6A
    566

    RuakaV.a Vatn
    5tog.u 2 Stqe ?
    720 ?20

    w wI!
    <.
    M
    2@
    b 2ffi .5 ul
    2@
    I -
    O' ac
    2@
    0
    2&l -9
    720 2u) ss
    2@ 2@ sfi
    \
    t@ ss
    OQ)
    Bo 6I

    t@
    wo
    8S t@ ril
    ,40
    t?o tu
    g

    E l: i*
    $
    6
    !
    4
    2
    l.;3
    lz 5'
    o Joe

    Fig. 1-g:53

    ?lgurc I-U-6t lllttogranr of pylnary llulil lnclualon fllllng tclpcraturea and


    apparant salbltlea for oauplea of quartz, gphalcrltc (14063) cnd barltc
    (11,06?) fron thc Charplon Veln (Flg. I-U-6A) a.ad Ruakaka Vela (F1t. r-U-68),
    Tul l{lne. The Lncllvldual noacurouoatt aro llatcd ta lppeldlr III.
    567

    . .a/ t Delomil.
    t ,Z*r . sirr.rirt
    zfoo9".- ? gmnrh$ilr
    t- 9>' f crrurstfr
    -

    'o
    :jl
    ..t6tn
    I
    go
    l- rnrorcrrcet
    "Erjf,iii-' srFCicrrrE
    6 -. Culrl ClRlOilAlCs

    ft.Cl tc. et|Cir.

    glgu:c tr-U-?l A plot or'61tc ve!!r$us 618o f"rl, hyBogene and aupergsns veLn
    earlrcnltea fror Tul, l{lre (froa F!.g. 10 of Roblngo\, 191L1. fhe teuperetrric
    rcalo for gaLclterileflard for e value of 6180 rtna c -1 pc:r l11r
    LnilLcates e decreas. tl teupertture ftou 250:C aloun to approxtratcly 60oC
    alurtng Sttga ,r Tbs catbonatal,ndt,eatc a 513C t*lo" of -6.f par ul,l .for
    thc f,aco, tn thc fr.util ( rA 6r3c *r).
    568

    tion by sphalerite galena pairs.


    An ad,ditional Stage 1 pyrite chalcopyrite Pair fronr the
    Chanpion Lode and a Stage 3 barite fron the Ruakaka Lode were
    analysed, during this study. The E)Ls values deterni.ned,
    +2.5, .*1.7 anil +18.8 respecti.vely; conforn sith Robinsonr s
    data.

    cAP.BOir AJIq oXI,G9ll ISoToPIS 0F CAF-tso}IATES

    51
    8o 613c values of stage 3 carbonates ranging
    "rrd
    fron +5.6 to *28.3 per rcil and -1 5.5 to +0.1 per ni1
    respectively, uere deterninecl by Robinson (1971r). I'Jhen plotted
    on a 613c versus 518o diirgrarn (Fig. I-u-Z) these analyses
    d,eflne a trend of d.ecreasing tenperature batrveen ZSOoC and'
    /rOoc for a solution havi.ng a 6180 value oi -1 per niL' A
    tna
    6')C iC value of -5.{ per nil was also ealculatecl by
    nobinsoi (1g7t).

    HIDRoGEU At{D ofrcEll rS0ToPES 0F BARITE,


    OUARTZ. KAOLI}ITTE AND FLUID I}ICLUSIO}IS

    618o values for Stage 2 quartz (+6.0 per nil)' Stage 3


    quartz (+9.2 per nil) and Sr,age 3 barite (+7.4 and' +11.2 per
    n11) and 6 D values for Stage 3 kaolinite (-51r.6 and' - 59.3
    per nil) were deterrnined by Robinson (19?4). He also analysed
    fluicl lnclusion waters by decrepitating large (2501.) saraples
    of Stage 2 galena ( 5 O of prinary inclusions = -?0.0 per niL),
    Stage 2 quartz ( 5 O of second,ary incl-usions = -35.1 per nil) ,
    Stage 2 sphalerite ( 6 U of secondary inelusj.ons = -17.2 per
    ni1) and by crushing a 3009 sanple of Stage 3 quartz 1 f, 180
    and f,O of prinary lnclusions lrere -1 .0 aail -2{.0 per nil
    re spectively).

    The 5 D value of -?0 per ni.I for StaEe 2 galena inclusion


    water was concluded to indicate the presence of priuary
    aagrnatic trater, rlhereas other 6 D values were interpreted' to
    represent uater of neteori.c origln. 6180 values of Late
    stage sarnples uere considered. to result by uoxygen isotope
    shiftr fron rneteoric water d.ue to reactLon with wall rocks.

    ''j.', :',:i'. '


    569

    p 4oo Summit of MTTc Aroha


    b -

    t lsyEl
    - 4 lcwl
    - E lwcl
    -

    Ftgrro Fhsbeblc eopth of ai,nenall,aatton at tsul, l{inc itur!,ng Staga 2


    I-U-8r
    (4no rurfres ilttu,rq ec oro.d .for the Setonongoa'at ilbgtb s'oconttructloa).
    Strgc {: dnoralllttlon rey bew oesurtlsii et gl.''oatcf ocptb - P-r?!!urcr
    570

    The hydrogen isotopes of fluid inelusion waters fron


    three sanples of quartz were analysed .d,uring this stud.y.
    !{aters fron late Stage 2 quartz sanples 1L056 (Tui 13, and
    1/+051 (fui 19) have 5 D values of -il+.3 and -3tr.8 per ui]-
    respectively, vhereas a value of -35.0 per nil uas d,eterniaed
    for rsater froa inclusions in Stage I quartz (sanple 14A5L).
    These 5 D values are consistent uith a neteori.c water origln.

    Problernsof corta;elnation encountered. d.uring crushing


    and, water separation phases of analyses for thi.s stud.y raise
    sone doubt over Robi-nsonrs beavy (-21, per nil) and light (-ZO
    per nil) 5 O values. The foraer nay d.iffer frou the values
    d.eternined iu this study because of water contaninatLon or
    fract,ionation within the vacuua llne, whereas the latter
    value nay result fron leakage of vater intor or saaple out
    of, the vacuun line

    LNAD ISOTOPES
    Coopar & Richards (1969) neasured. the ratios of 1ead.
    isotopes in sanples of galena and andestte fror:r the Tui I'iine
    (Chanpion /r and Chanpion 5 and 6 levels respectively), in
    adCition to saaples of galena, andesite and rhyolite fron
    other locations in the Corourandel Penin'sula. Tbeir d.ata,
    together with neasureaents of lead isotope ratios in llanaia
    HiJ-J. Group greyuackeby Arnstrong & Cooper (tgZt), ind.icate
    that the lead. in the hydrothernal- veins rras def ived froa the
    greywacke basenent roeks (c.f . Fig. 5 of Robinson, 1971r).

    DEPTR OF I,IINERALISATIO}I

    A reconstruction of the tleptb regine d,uring Stage 2


    nlneralisation is ilLustrateC in Fig. I-U-8. The surfaee
    daturn is taken at /r00m above the sunnlt of l{t Te Aroha, the
    sane as used for the iiaiorongonai reconstruction. Stage 1
    nineraLisation nay have occurred at greater d,epths (e.5.
    1I:n), the difference in depth.betr.reen Sta3e 1 and, Stare 2
    beln3 due to uplift and erosion between nineralising episodes-

    THERI,IOCHEI.ITSTRY

    Robinson (197t-) node].led the Tui i,line nineralisations on

    ,r,': t
    ,'ii:,
    i,..
    571

    -22
    \z -\\ rr5
    .--3---g
    Pvrite
    -24

    -26

    -28
    o
    tn
    o -30

    -32

    -34

    -36

    Fl.gureI-U-9: The geocbealcal envlronoant of Stages 1 auil 2a oiueralleatloua


    (star) calculateil on an f,O2 versus pB dlagrau at 35ooc and *S = 0.01a
    by Roblnaon (19?1,, flg. 7).

    -: -l-r tt
    t..,.,,.

    MAGNETITE
    \
    \\ BARITE

    \]----.

    xAoLrNrrE
    l--");
    pH

    Ftgura I-U-l0c The geocheolcal euvlronoent of Stage 3 alneralisetton (star)


    calculateil oD arr f0a veraus pf, dlagrau at 1 50oC autl t,S . 0.001a by
    Roblneoa 11971' Flg. 8).
    572

    fOa versus pH diagrans: Stages 1 and, 2 aL 35OoC (fig. I-U-9)


    S3"gu 3 eL 150oC (Fig. I-u-10). By conbinin4 nineralogical
    "ttd
    and stable isotope evidenee he conclud.ed that the chenical
    conditions during nineral deposition were representeC by the
    reSions narked stars in Figs. I-U-9 anC I-U-10.
    .with
    Additioual infornat'ion on i;he tenperatttre of Stage 2
    (ftuia inclusion si;udies), nineralogy of Stage 1 (borniie?
    r.rolftarnite?) and fS, conditions of Stage 1 (gold conposi.tions)
    and. Stage 2 (sphalerite conposi.tions) nineralisations r.rarrants
    a reappraisal of the geochernical environnent of these systens.

    Table I-U-1 lists sone of the paraneters used. here to


    rlod.el Sta3e 1 and, Stage 2 nineralisations.

    Stage 1 nineralisation is represented. by the shad,ed. area


    in Fig. I-U-11. It is defiaecl by the fSa values indicated by
    the gold analyses and the presence of pyri.te' ehalcopyrite'
    hernatite and possibly rare bornite.

    An fS, versus fOa diagran for Stage 2 nineralisation is


    presented in Fig. I-U-12. The iron content of sphalerites
    suggest 1og fS, values between -9.3 and -9.5, r+hereas Lo9
    f0, ls linited betneen -3lr.l, and -31 .0 by the abseaee of
    graphite and, nagnetite respeetively.

    Kaolinite, sericite and. ad,ularia occur in the wall. rocks


    and veins, however only sericite and, ad.ularia rrere in
    equllibriun uith the Stage 2 hydrothernal fluid.: kaolinite
    forned. at a later stage. Therefore a pH of around' 6.0
    (equlvalent to the serlcite/tr-fetaspar bouadary) is indicated,
    for the Stage 2 fluid.
    Contoursof concentration of totaL sulphur in solution
    shown ln Fig. f-U-12 were constructed for a pII of 5.O. A
    value of 0.01;z (1og ra S = -2) uas used for t'his paraneter
    to construct the f0, versus pH diagrara presented. in Fig.I-U-13.
    The region of nineral deposition is represented. by the shaded.
    atea in Fig- I-U-13, lnd.icating that sulphur rvas present in
    solution in approxlnatoly equal coneentrati.ons of sulphate anil
    sulphlcle
    Ij
    '57'3

    IABL0 I-U-ll c Gsnsra!, ttgruo'eherlsal p.areottre for thr ilapoeltioaal


    onvlrolrentrs sf $!r.ga 1 and Stagc 2 ulnsrelloatlona'
    tul lllae.

    $trge I Siagc :8 Eefc!clco

    tcup.craturc
    oo &o0 too labla T-1
    tnre l,patc rlt-rcngth 0.10 0.1,9
    Sctiatty (r [aOl rq) 0" t1 0.38 ,'.
    -f,i 0.14 . 0.0e6 I

    5.5 6.. Ssr t',a$t


    Pf,
    (Ftg.I-U-ll)
    ptr of kaolllltcy'aqrleltc fablc f,-l
    boundaty
    *.1 1.'
    nE of s6riclta/,[-f-6ld:gPar j.5' 6-0 ,
    tiounitqry
    [s?el s (,tog rtg) -1rt -2.0 S,cc tqlt
    goe fsz (ephelsri.tc oolP.) -9.3to.J9.6 lab1c V'-{,4
    (Eote c6rpol -9.91o..1e7 lablc V-64
    Log f'0O -ll ,9ls-:Q);.j -?l .r:+o-12., flgurer citad
    ,
    (Flg.r-u-11 ) (Flg.I'lt-'l1l
    r,og fgo2 +1.t +1 .6 la6lo S-1
    5? tr

    .4,
    PYRITE
    N
    ur
    qt\ PYRRHOTITE
    o

    MAGNETTTE
    I

    -75 -* -?4 -12 4 -n 4b -U 42 -?O


    Lag f oz

    Flgure I-U-l1: f9, yereua fOa dtagran at 400oC shorlag tbe geochorlcal
    envtroapent (shaaled) of Siage 1 quartz + pyrlte + chat.copyrlte ! heuatite
    t golat I blsouthlnito ! tetradyolte t volfraolte? t bornlte? in ths
    Cbanplon and Ruakaka velrs of Tul l{tne. (Ses Ieble f-U-1 for relevant
    thernocheolcel pareueterg and Appendlx V for rethods of coactructlon.)
    575

    I Oissotved
    i r.no}tr,le'

    GI
    rn
    (F
    o

    tli
    "/'4'"'
    p
    eer.Elirr J

    s|n
    -A
    4 -42 -6 -A -79 -* 42 4p-28 -26 -24
    trg f oz

    Flgure I-U-tZ: fS, veraus fO, ttla6rao at 300oC shorlng the geocheulcal
    .elvironnent (shaded) of Stage 2 quertz + apba1erLte * galena + pyrlte +
    chalcopyrlte ! tetrahedrlte Elnsrslisatloa ln the Ghaoplon aad Ruekaka
    velus of Tul l,llne. (See Table I-lI-1 for relevaat theraoihenlcal para-
    ueters and lppcnrtlx V for oetbods o! construotlon.)
    576

    os| @EHTTE + P{RffE

    s Ft'RlTEi
    2t:2,--i---

    TVRRHCTTITE

    PH

    rlgurc I-U-13: fOa varauo pH dlagrar at 300oc anil t9 r 0.01r abonlag tbe
    geocbeulcal euvi.rotnost (shaaled) of Stage 2 quartzt apbalerlte * galeua
    + pyrtte + chalcopyrtte ! tetrahedrlto ulnerallsatlon ln tbe Cbarploa
    aad Bua&aka velns, Tul X1ne. rhe envlronoent prOposad here tc
    characterleed by a btgher pH and loner relatlvc orygon fugaclty tban tbet
    propoac6 for Stage 2 nl,norallastton by Roblnros (197lt c.f. Flg. I-lI-9).
    lbc pH ol the cal,alte aoluble/lnsoluble boundary La 5.6. (Sse Tablc
    I-U-1 tor other relevant theroocherlcal paraueters aail Appenilk V for
    retboda of conetruotloo')
    577
    GEITESIS

    Robinson (1971+) concluded fron the isotopic eonpositions


    of veln ninerals and ore fluid that the sulphur ',ras originally
    Jurassic sea water sulphate, leached fron underlying :reywacke
    rocks, uhereas the carbon (in carbonates) ?ras <ierived fron
    aagnatic C02. ile postulated that the initial ore fluid was
    possibly of na3natic origin, whereas the later ore fluids were
    deeply cj-rculaii.ng seteoric water. R,obinsonrs evidence for
    na3natic uater is consid,ered suspeet by the vrlter alihou;3h
    no addl tional evidence has been presented to ei',,her support
    or refute the hypothesis of the presence of a 3a.J:atic water
    component in the early nineralisation.

    The changes j.n nineralogy and physieochenical paraneters


    fron Stage 1 to Stage 2 lndicate a general trend of increasing
    pH, caused by reactions with the wa1l rocks and deereasing
    tenperatursr These factors are considered by the writer to
    have caused nineral deposition fron chlori ,e conplexed. netals
    in solution during Stages 1 and 2. Dilution nay have also been
    inportant. Processes of oxi-datlon, decreasing pH and d.eelininq
    terroerature occurred during Stage 3 and were the cause of late
    stage nineral- deposition.

    The K - Ar age d.ata su5ges''"s that hyCrotheraal alteration


    ancL ni-neralisation occurred sone 9 to 12 ny after the fornation
    of the host volcanic rocks and together wiih Pb isotope data
    reported by Cooper & Rj.chards OgAg) and Arnstrong & Cooper
    (1971) indicate that the nj.neralisation iray have been
    affiliated to rhyolite volcanisn d.urlng the Plioeene.

    REFEREiiCES A}ID BIBLIOGRAPHY

    ADA:iS, C.J.D. ; IlODZIC.'(I,A. ; IIEISSBfRG, 3-G. 197 tr


    Allsrti, R.L. 197 5
    c0cilRAi{E, R.H.A. 1969
    Dol{iiEY, J.F, 1935: see pp250-251 and 284
    HiALY, J. i SCiiOFISLD, J.C.; T}i0:iPsoit, P,.:i.'lg6t.
    HEIIDERSOII, J.; BARTRU}'I, J.A. 1913: see o1 1 8
    KER , D.S.; \,{ODZICKf T A. in prees
    578

    RoBINSoN, B.!I. 1971,


    WEIGEL, D.A. 1978
    WEISSBERG, 8.G., \|ODZICKI, A. 1970
    I,IILLIAI'IS, G.J . 1971+z see pp120-122, lr25-l*27 and
    l-29
    woDZIcKI , A.i wEIssBERG, B.G. 1g7o
    579

    I-V
    tiAI0R0liG0itAI

    I:ITP.ODUCTIO}I

    The spectacular surface exposure of quartz veins and


    sulphide nineralisation in the l''iaiorongonai area. tenpted
    consideratrle investcrent and nining activity in the l-ate 180Ots'
    The Piako County Council built several kilornetres of tranway,
    j-nclud.inq three self acting inclines, linking the nining area
    uith the i;reatnent plants. Unfortunately' due to a Buccession
    of treatrent problems and lou grade ore' the various ventures'
    with the exception of that by E.F. Ilardy (between 1899 and,
    1905), lrsre conplete financi.al failures. Dormey (1935)
    recorded that the total produetion for the .area sas 2.1
    urlllion grans (6g195f ounces) of bul$.on from 51 ,661* tonnes
    of quartz-.

    The geology and inineralisation of the rrlaioroggonai area


    lrere descrlbed by llenderson & Bartruu (19131 and Cartrright
    (1982) although the latter lrork r,ras not availabJ-e at the ti-ne
    of conpletion of this thesis.

    CgOLOGY

    The rocks . of the l..'Iaiorongomai area are and.esites of the


    Coronandel Group.

    IIT DR,gTHERI'I AL ALTERA TI ON

    of the llaiorongonai area are hydrothernally


    The and,esj.tes
    altered to propylitic assenblages. The naior ninerals are
    quartz, sericiter chlorite, calcite and pyrite: ad'ule'ria
    was not apparent ln specinens collected by the writer (although
    a detailed stucly of the hyd.rothernal alteralion of the area
    vas not uade).

    I.III{ERALISATIO}I

    A large quartz vein knotm as the nBig Buck Reeftt strikes


    north-south and forns a proninant feature along the western
    sid,e of the .fiaiorongonai Valley (Fig. I-V-l). The reef is &
    580

    1\
    oz

    SCAI,E
    500 frcr
    r 0 IOOO

    Flgure f-V-l: Velns of the WalorongonaS, area (fron l'lllllaurs 19?4; after
    Henderaon & Bartrun, 1913). See also Flg. VIII-1.
    581

    nearly vertical, 10 to /,0n wid.e, zone of interconnecting


    lonqituriinal and transverse ouartz veins and country rock,
    with pug zones anC breccias present at several J.oealiti.es.

    liorth-east striking branch veins intersect the Bi6 Buck


    i.eef and penetrate withou'u crossing it- Some of the branch
    vei-ns on reaching the Big Buck Reef cirange their course and
    follow iis walIs for a iistance before ultinately penetrating
    anC ner3ing with it (iieni.erson & Bartrun, 1913).

    Although ninor quanf,itles of gold and silver were nined


    fron the north-east striking veins the najor production was
    fron the l'len Find, Colonist aud Prenier secti.ons of the Big
    Buck Reef (known as the Hain Reef at these locations) where
    it was intersected by the north-east striking veins, 1'Io.2,
    l'Jarrior and Vulean respectively. In all other locations the
    Big Buck Reef was essentially barren of nineralisation.

    A conrnon feature of the nain and. branching veins i.s tbe


    coarsely crystalline and vuggy nature of the quartz. Base
    netal nineralisation occurs in nost of the branch veins and
    in the iiev Find, Colonist and Prenier sections of the nail
    vein. l{enderson & Bartruil recorded the najor minerals as
    being quartz, pyrite, sphaleriter galena, chalcopyrite and.
    electrum. They also noted the occurrence of abundant calcite
    in the lorsest adit leve1 of the Prersier Lode' hessite from
    the Prenier, cj-nnabar fron an unstated. locality and suggested
    that antinony found in ore analyses nay have been present in
    the forn of tetrahedrite or pyrargyrite. The writer has con-
    flrnecl the presence of tetrahedrite but not pyrargyrite, and,
    also identifiecl barite and very rare a1tai.te.

    Although a narked, depth zonatLon of nineralisatlon' such


    as present at Karangahake and Li;ai.hi, uas not observed, a.t
    l.'Iaiorongonai by Iienderson & Bartrun (19'13) these authors did
    note that ncopper-pyrites fchaleopyrite] of the upper 1.eve1.s
    showed. a tendancy to give place to sphalerite in d.epth. ft
    rnay also be nentioned that herer &s at Karangahake' copper-
    pyrites is a good, iadicator for gold..rt Also rrln the Prenier
    the gold sj.Iver ratio wasr in the upper levels, 1 to tri in
    the lowest leve1 in which stoping has been done the ratio nas
    582

    1 to 2i. tt (Both quo'i;es are from p96 of ilenclerson & Bartrun


    1913).

    Secause of the lar3e nuaber of vei.ns investigated.' d.etails


    of tireir aceess and ore petrography are given j.n Append'ix VIII
    and. only a brief suntrary follows.

    The veins generaLJ-y consist of '1a11 roch breccia' ceuented


    by quartz witb nediun grained sulphid.es (Stage 1 ) foLlowed by
    eonblr and vuqgy quartz (Stage 2) and, in sone veinsr plates
    of barite coating the vug quartz crystals (Stage i).

    the sulphides are generally banded, with successive band^s


    of quartz and sulphides differing in the proportion of the
    various ninerals and tbeir grain size. Pyrite i-s often early
    folloued by sphalerite then galena and. chalcopyrite. As uith
    the nineralisations at Waitekauri and Petote Strean area'
    Late quartz often contains pyrite and' chalcopyrite.

    The band.ed sulphides ioay be arranSed. concentrically


    'be subsequently
    arouncl the breccia f ragnents (FiS . lr-7) or
    brecciated, thenselves and infilled with later quartz' wiih or
    without acconpanying sulPhides.

    Textures are generally sinp1e.. A eoamon texture resultin;;


    frou brecclation and later quartz cenentation is the oecurrence
    of lndivid,ual erains of sulphides seattereC in quartz. The
    only unusUaL texture seen was i.n a specinen fron lio.1 R'eef
    Ln rhlcb dendritlc-hergingbone galena occurs ln quartz (Ftg. It-zlr)

    FLUIp lllgl,usloifs
    Fluld inclusions in Stage 2 quartz and. Stage 3 barite
    are generally nornal two phase, liquid plus vapour' types.
    Sone inclusions in sa:np1es 13979 (i'litoo), 14081 (i'ii/'5) , lLogl*
    (:,If56) ana 1'408? (Wi64) also contain a fibrous solitl phase
    (r-i;,6-12), one inclusion of saaple 11979 (:Ii10O) contains a
    hexagonal solid phase (fig. 6-16), and vaPour rich and. vapour
    fllled inclusions occur, in addition to nornal t34pes' in
    sanple 1l+093 (1.118?) . The later inilicate boiling of the
    hydrothernal fluid at the tine of fluid lnclusion fornation.
    583

    oC
    Fiffing Temprolrurz 9alrnity
    aq.w+ %'NaCl

    (fi.a gltto
    |,4070 dh -rltll!
    O l-l +l r{ rl
    $ oFrqttk
    AH{Jd'
    trlatld
    .|:@XoFl
    #d t4099 IT-I
    E .(-l
    !..tEAA
    o
    QEloo\EF{
    Ea\.1
    E O AO k +l
    t, hO

    f,i
    O t A-{t O O
    +tC.<rCF

    t_
    bDo El o o o
    3t+r'lF{.|r{
    dilO.t
    F{ ll{ E t
    Fl at o st O'tt
    t4084 -1
    q{o+t,I a, t/, +{ r{
    .<t rf rl ?1
    r,aA.dq
    O qt
    dO!'{CF{ ^qo
    o r| LH at
    :'.rtltCE
    140e+ dF|XrlBr
    a, d o*t ...1
    o
    c t+td
    r{ttcttlD+t
    ooclo
    dq{ 6 qo k
    ia O o qd
    tk<?t7r
    A'|'',A
    t?l
    L-.-Il-r l-l- 14097 +.ootFl
    =[J >rAo
    F{dtttQ gE
    t{EEldd'r:
    .tdO
    grtr{+td{J
    '1!too6
    k'{a'|Aa
    fodFlFl{r
    qdtl

    *!- ,_-rq, 14087 E


    r{
    O ltrl
    oilct*rtt
    > oq
    E+trlOOqtO
    dr{vOAOrl
    t{
    o'ElrlLrl.
    n0
    tr

    tC-{d+{+t tt !t
    t|o+l d Q >
    g fl--- t4074 [= d
    O|{ O E
    +tdhqtrlf{
    .lrEdolco
    lrt {t r{ }l
    GtdOFoo
    d
    TI F
    .C{
    o
    oAoqO
    .. k O 0' d hr{
    6t!ttollL.)F.
    I o.c o E
    >Aor{kk.t
    fdk4'A:'r'
    r'-t_ r. l40gl
    r-roqtoo
    ,ct'ltrCLAO
    odcodarF
    AC=FlF>+)
    a
    U
    il
    h

    --,a-L, t79t4
    '11 J[ l-r-l-r-l-..E

    RR R R R R RB g 3 8 B 8
    \9G(\|O
    58r,

    Histograns of filling tenperature and. salini.ty Eeasure-


    nents are presented in Fig. I-V-z.

    ';lith the exception of sanple 1l+O93 (rJi8?) the filling


    tenperatures reouire the aCd.ition of a correction -for pressure
    anC salinity. Reconstruction of the d.epth relations duri.ng
    nineralisation (see Depth of l'lineralisation section) inaicate
    that corrections ranging fron 5 to 10oC are required. The
    exaet figure depend.s on the vertical location of the individ.ual
    sanple in the urining area.

    Corrected filling tenperatures ind.icate that Stage 2


    quartz deposltion occurred. at tenperatures betseen approxinately
    2lr0 ancl 290oC but predoninantly around, 265oe. Stage 3 barite
    appears to have been deposited at tenperatures near 120oG
    aLtbough a single fluid lnclusion in sanple 1t'O99 (Wi9?) has
    a filling tenperature of 'tg6oC ind.ieating that d.eposition nay
    have also occurred at higher tenperatures.

    A feu lnclusions in sanple 13979 (ttitOO) appear to have


    unusually high saLinities (up to 5.5 eq wt. g llaCl)in
    comparison to oiher samples vhlch average 1 .6 eq. lrt. S ltraC1.

    The results of crushing and leaching erperinents on four


    sanples of quartz are listed. in Table 'I-7. Partial chenical
    analyses of the fluid. incluslons were deternined for sauples
    1l+o?1 (lri16) and 14090 (lli67) but on].y \IalK ratios are
    reported for sanples 1l+o9'l (tfieO) and 14098 (I{i94) because
    the quantity of their inclusion fluid ana-lysed was not
    neasured. Using the theoretical Na/K geotbernoneter, the
    average naeasured tla/K ratio of lr.l* (range fron 3.2 to 5.'l')
    indlcates a fluid tenperature around. zg}o1 conpared, with a
    range of approxinately 250 - 290oC ind.icatecl by the fluld.
    incLusion fi11in3 tenperatures.

    :{IDR0GEII ISOT0PIS
    6 D values of -36.8 and -3'1.3 uere neasured, in fluid
    inclusion waters of late stage quartz sanples 1lr071 (git e )
    and 1 l+091- (1'Iis9) respectively (Chapter 8). These values are
    consisteat with a neteoric water origin (possibly d,uring a
    periocl of .cooler clinatic conditions) altbough thei.r origin
    585

    gurrlwfil of W'7c hrdlv.


    -

    Nsrii find at
    pmsanl sfiCaea
    -
    5lc$cl .- t s
    ffiicr tg

    -*E!
    -8S =f
    f;'.[*yfl*ti?*
    fullhadif
    Welcons
    - -
    I
    I
    ptgUna !-V-3iD6p-th o! nlnc,ral.isetlon aahsuo f;or. the Wetoroagonf,l 6cpod,tc
    i
    souotruete6 b11 aaaud11g 'l1ot borll'lag oeeurre-d, .!tt the ilsw fluil acsttpa
    Srcilodnratll hylrsstettre Pfat8drd conill,tiorta.
    I
    .
    u.ndsr I
    586

    from other types of uaters with sone moCification is also


    po ssi-ble.

    SULPIIUR ISOTOPES
    6345 values of neasured sulphid,es and barites are listed.
    in Table 9-1 . The sulphid,es have S 34S values ranging fron
    -2.0 per ni1 (galena) to +2.5 per nil (chalcopyrite), r"rhereas
    the two sanples of barite analysed, have values of +18.8 and
    +18.9 per nil.

    Tenperatures calculated fron fractionations between


    eogenetic palrs of sphalerite and galena range fros 255 to
    39OoC with the average fractionation value (z.l per nil)
    indLcating a tenperature of 31OoC. As vould be expected.
    average tenperatures of the veins d.eerease with increasing
    elevation: Hero 1100t 1evel (sanple.14100) 35OoC, llay Queen
    3 level (sanple 14080) 35OoC, Colonist 3 level (sanples
    1lr0?6a, 1&076b, 1l$77, 1lr}92a and 1t+Ogzb) 3z5oc, l{o. 1 Vein
    l,Iaterfall ( samples 1t$73 and 1tr}7il 285oC and l,iain Vein
    l,laterfall ( 14089) 2550 c .

    LEAD ISOTOPES
    Cooper & Rlchards (1959) neasured the ratios of lead
    isotopes in galena and anCesite (oae sanple of each) from
    the Waiorongouai area. llhen vieued. '*ith 1ead, isotope
    neasurem.ents of galena, andeslte, rhyolite and greywacke fron
    other locations i.n tbe Coronandel Peninsula (Cooper & Rlchard,s,
    1969 'i Arnstrong & Cooper, 1971; c.f , F.r3.5 of Robinson, 197t),
    a greywacke basenent source is ind,icated, for the lead j.n the
    hydrothernal velns. .

    DEPTH OF. I,IINERALISATIO}I

    Fig. I-V-3 illustrates a reconstruction of the depth


    regime at the tine of nineralisation. The surface d,atun i-s
    taicen a',, /r00n above the sunni.t of i'lt Te Aroha. The nodel j-s
    consistent with bolling at a tenperature greater than 24OoC
    in the ltrev Find, Section provid,ed that the pressure regine was
    predoninaatly hydrostatic (at the tine of boiling) and the
    concentration of COa in the f1uid was greater than 0.6 nole
    587

    GI
    coftP.' -tfi-
    rt\ PYRITE ./
    -to g
    (t
    o -n
    4
    ,i,i
    -t6 ['r,
    -.t8

    -m
    -nt-
    &r
    -q2 4 1C -X -v 12 -U -26 46 -U -?;2

    4 tn^
    { "'t

    Flgure I-V-4r fS2 verauo fOa itlagral at' 325oC sbowlng the geocheolcal
    enT!.roEllont (ehadeil) of Stage 1 quartz * aphalerl.te * gaLena + pyrlte {
    cbalcopyrlte t hesalte t tetrahedrlte t olectruo llnerallsatlon ln volDe
    of tbe llalorongonal aroa. iS c 0'01n, Pll o 5.1* Log fSa fror aphalarlte
    coEposltloas = -7o3 to -8.3t log fS2 fron electrun coEpoaltlone ' -7.2
    aail log f00a fron flultl lncluslon DsasurDorte = *1.5. (See ApPenillr V
    for uetbods of constructlon.)
    588

    (data fron I'lerchant, 1978 Fig. 5-6). The sane d.atun is


    .1'
    used in the Tul lline reconstruction.

    !:i :i ? i ! 0 C :{ El'i I S T,?-Y

    Sta';e 1 nineralisaiion plots in the pyrite + chalcopyrite


    field of the fSa versus f0, diagran illustrated in Fi4. I-V-4.
    ?he lron content of s:rhalerites indicate sulphur fu3aeiti.es
    of log fS, = -7 .3 to -8.3, whereas the rnole fraction of
    silver in electrun suAgests a 1o3 fS, value of -7.?. f0a is
    ltni'ued by the absence of 3raphite, na.3netite and heaatite,
    and in the case of the lou levefs of the Prenier, by the
    presence of calcite but absence of anhyd.rite.

    of 5.1, ( in equilibriun with sericite in the irall


    A pH
    rocks) was used to construct the contours of concen',,ration of
    total suLphur in solution in Fig. T4-lr. A value of 0.01m
    (1oS ;z S = -2) for this paraneter is eonsistent ',rith the
    other d.ata and was used to construct the fOa versus pH d.iagraa
    shoirn in Fig, I-V-5.

    6345 values of late stage barite (+18.8 and. +18.9 per


    nil) may be used, to Ceternin 63" * , by assuring t::at barite
    "
    was d.eoosited fron a fluid in which dissolved. sulphur occurred.
    pred,ominantly as sulphate (c.f. Chapter 9). Therefore
    34to"rite s r 34sso
    E
    ,z- ot34t a , . A value of *16 per ni1- is
    assigned to s 34s,
    ,:
    Contours of 5 34S;1^s are shovn in Fig. I-V-5 for t 34s 6 s
    = *16 per nil and indieate that Stage 1 sulphid,es
    1 $31'S values ranging fron -0.2 to +2.5 per niI) nust have
    been dei:osited from a fluii uhicir plots near or or the
    oxidlsed sulphur species/reduced sulphur specles boundary.
    The nost like1y region of nj-neral deposition is sho',rn by the
    shaded area in !'ig. I-V-5.

    fTe, versus fS, diagran (fig. I-V-6) i.ndieates that


    Tbe
    fTe, relatively hlgh during sone stages of the .'Ialorongonai
    was
    nineralisation as evid.enced by the presence of hessite and
    rare altaite.
    589

    jtul K-te,ldsVar

    !r
    lr

    ii

    oN
    so : -z-- !--:
    -J

    COz loqf(O
    C*Q?it< ']l't

    PYRRHgrffE!

    PH

    Flgure f-V-51 f0, veraua ptl dlagrau at 325oC and {S = 0.01n ehoulng the
    gaochenlcal envl.ronoent (ghaaleat) of Stage 1 quartz + sphalerlte t galena
    + pyrlte + chalcopyrita i hesel.te i tetrahedrlte i electruo alnerallaatlon
    ln tha velns of the Walorongooal area. i = 0.08, nK+ = 0.021, pH = 5.4',
    log fS, fron sphalerlte conpoeMons = -7.J to -8.3r log f9a fron electrun
    cotpoaltlons = -?.2r log fC0, froo fluld lncluslon Esaourenente = tl.5'
    and the pH of, the calclte soluble/lnoo1ublo boundary = 5.g. 6'krr, -a
    eontours ar constructed for 534s *r= +16 per uil. (l.tethods of
    constructlon arc degcrlbed tn Appendlx V.)
    590

    'is,
    -u
    s
    d-
    tn
    eO-
    ts
    Pd
    l''* e-I
    ll

    -8
    sr
    .\t
    *-?
    s
    s
    -t0

    tqf5z

    Flgura I-Y-6: fToa vereuo fSa dlagra! at J25oC aho"log tbe posetble atabtllty
    rpng6s of stage 1 aesenblagos contalnlng hosslte * electrun (vIdaly
    apaced dlagonal.ly ruled pattern), heealte (vldeIy apaced dlegonally
    ruled pattern pluo otlppleil area), enal heesl'te * altalte (elosely epaced
    dlagonally ruled pattern). (Methods of conetructlon are descrlbeil ln
    lppendtx V.)
    591
    dE:,IESIS

    ?he value of *16 per nil for 6345o, indicates that the
    source of sulphur in the :{aiorongonai sulphide anC sulphate
    rlnerals :uas probably sectinentary sulphur leached fror the
    ';reywacke basenent rocks. In this and. several other aspects
    (e.g. nineralogy and physicocheroical cond.itions of nir:.eral
    deposltion) the ninerah-sation at !traioronqonai is genetically
    s'inilar to.that at Tui l.line and because of 'their close proxinity
    ihey nay have been rela',,ed to the sane naguati c geotherural
    epi.sode. ilowever, tr\e srineralisations differ in that the
    early high tenperature copper-bisnuth-goIri. (-tungsten?) stage
    of Tui l4ine appears to be absent fron the I'Iaiorongonai area
    and the coneentration of Te Ln solution appears to have been
    higher at ?Iaiorongonai than Tui I'line.

    Stage 1 nineral deposition at l{aiorongonai probably


    occurred due to changes in pE associated with reactions of
    i;he fluicl vith the r"iall rocks although the high dissolved
    sulphate/d,issolved sulphide ratio indicated. for tbe fluid
    suggests ui.neral deposition in a rnixlng zone where the
    hydrothernal fluid encountered oxygenated saters (c.f- noCe1
    of Henley,& Sevard, in prep).

    REFEREITCES Ai{p BIBLIoGRAPT{Y

    CAR,TI{RIGHT, A.J. 1982


    DOl'nlEI, J.F. 1 9352 see pp2J5-261 anC 288-289
    HEALY, J.i SCHOFIELD, J.C,; TEOl.lPS0it, B.l{. 1961.
    HnllDFlRS0ll, J.; BARTRUX, J.A. 19132 see pp88-92, 95-98 & 116-11e
    i.,IrLtIAt{s, G.J. 197t+: see ppl19-12'l

    rl
    592

    I -i'{
    I,IISCELLA}IEOUS DEPOSITS

    I:ITRODUC?IO}I

    The Locations of the deposits revier.red in this seetion


    are shorrn in Fig. I-i{- 1 . They are described i.n geograohical
    orCer fron north to south.

    Se'reral deposlts are not reviewed here because of their


    sna]]- size (eu - Ag production less than ,0'000 grans or 1'000
    ounces) and because they have not been studied sj.nce thelr
    d,escription ln the early Geologica1- Survey Bulletins. These
    incJ.ude the f ollowlng (locations shoun in Fig. I-fi-2):
    Preeces Point (9rt5O grans ot 3Ol, ounces), Ocean View (5,51O
    grans or 179 ounees), l,[oewai (Z,5AO grans or 83 ounces),
    Mahakirau (lS,Z56 grans or 587 ounces), Te I'lata (5,530 qrans
    or 210 ounces), tiaihi Beach (less than 91000 grans or 280
    ounces) and Eliza (160 grams or J ounces). The read.er is
    referred. to the early Geological Survey Bulleiins for
    infornati.on on these' deposits.

    I'IAIKAI{AU BAY

    . Several- snrall quartz veins oceur in Port Charles Andesite,


    Kokunata Dacite and Tuateawa Andesite (CoromandeJ. Oroup
    forsations) of the l.Iaika:vau Bay area (c.f. Skinner, 1976).
    Skinner (1967) considered that they are characterised by the
    oecurrence of arsenopyrite and marcasite in addition to pyrite.
    Fraser & Adans (tgOZ) noted that veins in Cousin Jack Creek
    (Cousin Jaek ttine), Gisborne Creek and l,'laikanae Streau
    (liaianataharalceke area: i.ti11t s l?.eward and llarcaroni lli::es)
    are auriferous but total productlon fron the.area was
    apparently l.ess than 2000 grans of gold, and sj-lver (c.f.
    Do'"meyr 1935, .

    COTVILLE AREA

    nineralisation and several quartz


    Disseninated. arsenical
    veins occur in rhyodacitic pyroelastic rocks of the Onoho
    Fornation (Coronandel Group) in the ColvilLe area. The quartz
    593

    brs

    l-,.J-r-.-1,.&a
    O zJftrl

    TAIRUA

    t la,fi tnoocttr r 6rcat tkrican)


    $wry
    t citnauar
    'uilc

    (ARAI{oAHAXE

    s'tcPvW
    r tlrit Rcaft

    Flgura f-I-1s Locatlon of depoelta revle$sd 1n Sectloa I-!f.


    594

    Soo

    r-r-r+l
    o. ?I5Ala

    vtij'r btfrtr

    F13ural-lf-Zr Logatlona ol deporlta not re'vlsHed bere. fheLr ploduotlon of


    goll and allvsr usc goall (1esr thea 30!OOO 8raE5 or 1,000 ounass) lnal
    lhay have aot becn ilescrlbod ip tbe lltoraturc oinc,a tbe Goologlcrl Surrrcy
    Bqllettno of th'e ,eerly l900rr.
    I
    "" I

    5g5 I

    veins contain pyrite, arsenopyrite and narcasite and one in


    I

    I'lgakul:u Strean also contains pyrrhotite and cbalcopyrite


    (Skinner, 1967 '1976). Approxioataly 20,000 grans (6OO ounces)
    of qold and siLver l,tere nined fron quartz veins in tha Jerseyr
    ,ihite Star and. 3ay i/lew llines (c.f . Fraser & Adass, 19A1i
    Dor.mey , 1935). .

    :rAl:ioag){Mo .VALLEg
    The quartz veins of the fiaikoroniko Valley area and' tbe
    llhangapoua or tillis i.line (.tu - Ag proCuctlon o! l'7,AAQ -fraEts
    or 1 r5O2 ounces) nostly occur in Beesons Island Volcanics
    (Coronandel Group), however Skinner (nli) napped, the host
    rocks of the Four In Hand l,tine ( Ru - Ag production of 332'000
    grans or 1C,?13 ounces) as Tuateawa Andesite (Coroaandel Group).
    Iiunerous dlkes d Kai-iti Porphyrites intrud,e the Beesons Island
    Volcanics.

    The'area was successively investiSated by Fraser & Adans


    (1go?), Kear (1958), Skinner (1967) and ASAR.CO (lleilsen, 1958).
    Fraser & Ad.ans (190?) noted that in the 10 to 120cn thick
    Four In lland vein, electrun occurred isith pyrite di-r,her in
    shoots or disseninated in the quartz. Bonanza style ore
    occurred in a hanging wall branch vein, particularly where it
    contacted, the main vein -

    The nain vein of the llhangapoua i,line varieC in thicl<ness


    fron 5 to ?5en and in the upper levels the ore occurred in
    rich ttpocketstt, The gold (electrun ?) sonetines ttresenbleC
    a Loosely conpressed Bass of thread-like netal turningsn
    (Fraser & Adarns, 1907 p'125).

    Skinner (1957) differentiated tuo iypes of quartz veins


    in surface exposures of the area: (a) veins with suSqary
    quarta, pyrite, rare narcaslte and arsenopl'rite, and late
    calcite and vuSgy quartz, and (b) rhoneyco;brr irpre'3nati.ons
    oi quartr in shear zons, contaiirin3 cisse:inate'l or collofor:i-
    like bands of pyrite.

    Ilellsen (1958) noted that the uall rocks ad.jacent to the


    veins lrsrg onlr nod.erately effected. by hyd,rothernal alteration'
    596

    although ueatherlni obscures this feature in the vicinity of


    the Four In Hand l.iine

    0:inRA

    . The O.:rera rinini area (incluCing i'lurphyts liill) produced


    ?1 ,000 Lirars (2 .ZAD ounces) of ;old and silver (Doi'rney, 1935)
    iron quart,z velns in '.iaterangi -b,:lesite (Corouandel Group).
    ?racticallir all of tne production r.tas fron the Owera Veln
    '*hich averages 60c;r wi.le, dips steeply and strikes NilS (Fraser
    i .,lda:rs, 190?).

    3OAT HAP,BCI]R TO TA.IAUA

    BelL & Fraser (1912) and 0vens (tgZ6) d,escribed quartz


    veins at tsoat Harbour (Heai;her Bell Reef ), Iieaves Bay and Te
    Itaro Bay, and si.nter d.eposits between Te Karo Bay aaC, Tairua
    (e.g. Punlcin ililL). i'iear these deposits the host rocks,
    Tapuaetahi Andesites of the Coronandel Croup (0vens, 1976);
    are altered to prop;rf1tri" assenblages (chlorite, seri-cite'
    pyriie, calcite and quartz) but strong hyd.rothernal ali;eraiion
    ad.jacent to sors veins and siniers has prod.uced intersediaie
    argillic and advanced argillic alteraiion with l:aoliniie pre-
    doninatin3 (S'.rlndale & IIu3hes, 1 968; Ovens, 1976) .

    Pyrite occurs in the quartz veins and associated with


    some sinter deposits but gold and silver are practieaLly absent
    (tire recorded Au - Ag prod.ucti.on for the area'is only 280
    ?rans or 9 ou[ces, Downey, '1935).

    OHUI

    ?uartz veins and sinter deoosits oecur la I'Ihitianga


    Oroup ri:;,'olites and Corourandel .jroup and,esites bf the Ohui
    area. Dovney (1935) recorded, a total Au - Ag prod,uctioa of
    ?r3OO grans (23t, ounces), practically alL of r,rhich care fron
    the Creat ilexican and Phoenix llines,

    In the Great i,lexlean' electrun and pyrite occurred in a


    quartz vein lcnown as the iiaori Dreara Reef. This vein had. an
    average uidth of /r0cn (aaxi.nun vridth'of 1.2n) anil. 'sas
    char-eterised by a low anqle of Cip: the northern part was flat
    lying (geft & Fraser, 1912r. The host rocks are.andesites of
    597

    the Coronandel Group.

    Ti'ro thin quartz veins (averaging 18 aad JOen wide, with


    a ..;a::inu;r r'ridth of 5Cen ) i.rere 'ororlied in the Phoenix liine and
    't:ese-occurred '"r:-thin a na:roir zoiLe of brecciateC anrl
    silicified spherulitic biotiie rhyoliie (itinden Rhyoliie
    Sub;roup of the l{hitian3a Oroup). The veins eontained. nilhy
    ''ilrie quartz $ith a proncunced ribbon structure, elecirun,
    acanthite, aad evidense of pyrite snd calcite uljch had. been
    o:ridiseC and leached. cut respactivelir.

    A nunber of siater deposits occur capping Phoenlx 8i11,


    in ',fhitianga Group rhyollte. A chenical analysis of tho
    sinterous ,lateri.al r,ras gi.ven by BelI & Fraser (1912, p61 ) and
    denonstrates that gold and silver are preseat in oal.y extremely
    low concentnations.

    KAI]A3RA]ICA VALLSY

    Gold, cinnabar and dissenrinated pyrite nineralisations


    occur in the Coronandel Grottp anCesites of the Kauaeranga
    Val1ey,

    Fraser (1910) briefly described. aurlferous quartz veins


    of the Otanui i'tine in Otanui Streaa (l,langakirikiri Valley) ,
    hor.rever according to proCuction figures given by Dorrney (1935)
    they appeal to have been uniaportant eeononically' haviag
    prod.uced. less than 11000 grans (tOO ounces) of bulIion.

    iiear the junction of }langalciriklri Stree,n and, the


    Kauaeraaga River, cinnabar nineralisation oceurs in bands of
    sillceous slnter, and occasionally in the intensely silieifieC
    ani brecciated. zones of the propylitised and.esL^r,es uhich
    enclose these bands (Fraser, 1910). Less tban one tonne of
    cinnabar ore rtas rnined.

    Iiear (1957) d.escribeC disseninateC pyrite a-C =arcssl'r,e


    nLneralisati-on (up to 32iI sulphur, equi.valent to 60 ert. I
    sulphide) ia propylitised andesite lavas, pyroclastics
    (breecias and tuffs), d.ikes (up to 2.5s wide) and sedi-aents
    (siltstone, sandstone and conglonerates) in the i{aikato Strean
    598

    8.r&. Surfaca napping and core from 7 drill holes (naxinun


    depth: 13lra in hole G) j.nd,icated that the niuerali-sation r,ras
    ieainly by replaceaent,. confornable to bed.ding anr,I lithoJ.ogicalllr
    con.trolled, being stronlest ln carboaaceous seciinents.

    LUCE AT L-{ST :,lli.iE (i.iHART:iAlI-{ VALLEY)


    ?he host rocks of the Luck Ai; Last ),11ne trere riapoed. as
    Piioceng ttrhird, Perioctr vorcanics by Bell & Fraser (lglz) anc
    iiinclen R,hyolite by Scaofield (1967), although BelI & Ifraser
    (1912, p93) descrlbed then as pyroxene iiacites r..ri.th nfaintly
    observabletr flou structure. The propylitic alteratioa in
    these rocks, adjacent to the veins, ttd.iffers itt D,o respect
    fron ihat afford,ed by a nornal andesiten (8e11 & Frasar, 1912,
    p93). Biotite rhyolite was encountered ln ths northern workings
    of ihe rine.

    A single quartz vein (with ninor brauches and loops) was


    workea in 't,hree adit levels and prod.uced, 4081000 grans
    (l3,tl6 ounees) of gold and silver betreen 1S99 anC 1901 (geft
    & ^Fraser, 1912; Dorvney, 193il. It strikes at 0200, dips
    steepl;'to the east and varies in vid,th fron Q.3 to 5a, (averale
    r'rid,th of 1 .5n) . The fj.ne] y crystalline ailky uhite quartz
    contained, go].d and silver but rt]-ittle or no F:.rrite or other
    sulphi-desrr.

    O!{AI{U VALLEY

    Gol-d, silver lrere prod,uced fror three nlnes in the


    and
    Onahu Valley: Sheet Ancholr(45,OOO gralcs or '! ,480 ounces),
    IIe Three (t?,000 Arans or 539 ounces) and. f,londyke (t,OOO
    grans or 35 ounees). The following d.eserLptions are sunnariseC
    fron tsell & Fraser (t9tZ).

    In the Sheei Anchour I'llae a 1 to 1.5n thicl: nver;r flat


    lyingtr ."rei:r contains fine nilky quartz, electrun a::d, acanthite.
    The vein occurs in rbyoll;" tuffs (Coro.qlen SubSroup of the
    ,ihitian:a Group) at or near 'uheir irregular conrr,act uith
    and,esltes of the Coronand,el Group.

    The quartz vein ia the 'l'Ie Three lliue strikes at 0200,


    has a narinua ufulth of approxinatelX 30cn and, occurs in
    Coronand.el Group andeslte. Oold, aud silver were nined frou
    599

    ihe oxidi-sed near surface section.


    iilondyke }.{ine is situeted in rhyolite tuffs of the
    Tt:.e
    Coroglen Subgroup ('ihitiange Group) r.rhich contaln intruslons
    of rirS'olite anC Caci'"e. The vein consists of rrsnall erra"tc
    seaEsll .

    IdEIITUORTII - I.IHAI{GA}:ATA AP"EA

    Several quartz veins r*ere nined in the llentwort'h Val1e;r


    but only tvo produced significant gold anC s1lver: the
    l'trentwortb or Auckland l,tine (&g grars or 15,086 ounces)
    '00e
    and. the Goldwater Vein of the Glaeorgan Clain (45,000 gretrs
    or lrtr'l} ounces). The country rocks are ancl.esites and dacj.tes
    (geft & Fraser , 1J12i l,iain , 1971, 1979) . The f ollor,rlng
    descrlption is sunirarised fron BeII & Fraser ('lglZ).

    An un-naned quartz vein, toaether rlith tire ,Raunui Loop


    Vein riere gorked. on lr adit levels in ihe i{enir;orth liine. The
    nain vein had an averae wiCth of 50cn, wi',h a strihe of 0200
    ancl dip, ?0o, to the east. It contained quartzl pyrite and,
    visible elec'vrun. The oXe oecurred in the upper levels, nainly
    between 1 leve1 and the surface.

    The Goldwater Vein had an averate vridth of 2.5n or less


    and coniaj.ned. ouartz, quartz pseudoaorphs after calcite' soae
    carbonate, pyrlte anC acanthite, '"he latter apparently being
    the on.]-y econocie nineral. Bel]- & Fraser (191?, p97) Lisi an
    assay of the ore in vhich the Au:Ag ratio is apororinatel-y
    1 :1 00.

    i.IAIfiI ir0m]l.{Ei{?

    The p1'ritiseC slnter deposits of i;he iieihi Honunent sere


    descri.bed by Be1l & Fraser (t9tZ), lior;an (192L) and Skinner
    (t9Z5t). They consist of t'.'ro sinter nound,s of sliEhtly
    pyr5.tic, silicifieC, partl;y breccia'"ed'r opalisei Coronaniel
    Group andesi'r,esr 60n apart a:rd each aoproxiraiely 10r ::i:h
    (Slrinaer, 1975b). They ere surround'ed by a 3 to 5n thick 1-e;;er
    of puniceous and quartzose sand and silt (interpreted by
    Skinner as being the distal part of I'ihitianga Group tuffs and
    sedinents of the liaihi Plai.ns) covering Coroaand.el Croup
    and.esites.
    600

    Prospecting in the late 1800ts' in the forn of aCiis and


    a shaft, revealed strong pyrite nine:'alisation but ver;,' 1o"r
    'ralues of gold and silver. DriLllng in the lgroOrs (a sin.ile
    hole to a depih of 192n at 55o dijr, equival-ent to a vertical
    C.epth of aopro:rlnaiely 160n, follol:ed -o;,'20 holes eaci: i'o a
    de1;th oi apnroxinateiy 13n) intersee',ed a stronll;l lta.oiinitisei
    an'-i pyriiise'.l, intrusi'.re rhyslilg pipe or plug approxinatel'. 6Cn
    in cilaneter. Skinner (1975b) su-.;gested that the pine ne.)r iisv.
    been a feeder to an overlyin.g liinlien i'ryolite dc:e'uira',, !:as
    been stripped by erosi.on.

    0ifiiAR0A
    The geology anC nineraLisation of lhe Cuharoa area vere
    Cescribed, by Bel-l & Fraser ('tglZ), ilorgan (lgZlr) anc P'abone
    (tglt, 1975) .

    Beti.reen 1975 anc] 1933, 2.3 nillion grans (2e,580 ounces)


    of ;o1d and sil'rer (Douney , 1935)'uere prod.uced f ron c-uartz
    veins r.rhich oceur in 'i'.'hitianga Group (1":inden Rhyoliie Sul:;roup)
    rhyodacite flor.rs.

    The rh1'6daci'r,es have been intensely hydrothernally


    aitered to asseablales of cluartz, sericite, ai.ularia ancl
    her:atite (Rabone, 1971 i 1975).

    In the Largest nlne, the Rising Sun, three quartz veins


    lrere worked on three leveJ.s producing 2 nillion graias of golc
    and silver. They sirj-ke at 0200, dip steeply to the lrest or
    ver'ricaIly, and, have average widths of less than 50cn rvith a
    nar:inur: recorCed wiCth of 1.5i:r in l;o.1 Lode. The veins are
    uainl;r finel;' crystalline nilky quartz but the;r also contain
    Euggarj/ quartz, vug quartz, seai-p1ati.' o.uartz (quartz
    pseudonorphs after calciie), ;;.'rite, acantbite, eleetru:l
    (ttoccasional-l-v vislble in association ui'rh the'sulihi d.estr i
    lell i: lreser' 1912) and ci:rrai:ar' the latter for:rin:
    encrustations on cuartz.

    The Au:Ag ratios j.n tuentl.' assa:r's of ore fron t,he 'l oti
    level were reported by liorgan (1921* p127) to vary betveen
    1:1.23 and 120.'l'lt except in one case, where the ratio ttas
    1:3.8. The assays averaged l ounce 10 d,wt. I grans of 'goJ-d.
    601

    /g*fac1 debris

    Upor sidterbcd

    ?
    Ercnmfiong /I
    ffi thin cnatWWry,ry

    I Lowcr strdrerbsd

    0l'finivl'ruri Andcgifc

    tiguro I.-U*}r Dtcgr,auatle dsorgr aastlsn of the qinnebar drapoglt at the


    lreot lftdsr l{ackay0ora (arter Bl1l t fraaerr 1912r Rusoall, 1989)'
    602

    anC 1 ounce 10 dwt. 15 grans of silver per ton (approxiaately


    42 ppn each).

    The ore uas coniined 'uo I vertical ran3e of approxinately


    1COa. l'lith increasin; depth the quartz veies uere founC io
    split uc i-nto stri.naers.

    The nineralisatj-on ia other workilgs of the Owharoa area


    (e.g. Snile of Fortune, 220'000 grains Au - Ag; Rad.ical , 5l|'000
    -gra;s Au - i,E) oecurred in a nunber of itiE trending cuartz
    vei-ns confined to a 'l50n vide zone. The veins nresenbled the
    stock-work iype of deposits, each including nunerous para1le1
    stringers and erratically disposed, streaks and bunehes of
    quartz and such soft ninerali.sed, country rock, tha whole of the
    raaterial being Eore or lesE auriferousrr (Belf & Fraser, 1912,
    p118), Ore occurred near ihe surfaee but values d.ecreased.
    with increasing d.epth.

    I'IACKAYTO1NI

    Bell Fraser (1912) and, Russell (1980) d.escribed ci.nnabar


    &
    depositsr principally the Ascot Cinnabar l'line, near }lackairtorln.
    The deposits occur in ridges and knobs of intensely silicifieC
    I'lhitianga Group rhyolite ',rhieh fores thin (approxinately 30q)
    cappings on propylitised, 0hinenuri And.esite (CoronanCel Group).
    fn other locali.ties the rhyolite is overlain by Onahia Andesite
    (Coronandel Group).

    the Ascot i,line the niaeralisation oceurs predoninantly


    A'u
    in a 1.5n thick kaolinitisecl, horizon sand,wiched betrveen two
    nsinter (Fig. I-u-3). The cinnabar occurs in red. pug3y
    bedsrr
    seansr FuBB filled cavities (often lined. r,rith d.rusy quartz),
    whltish flinty quartz veinlets and in a fairly persistant
    thin (ioaxlnun width of 30cn) quartz vein located. near the base
    of the 1.5n kaolinitised horizon. Tbe nines uere unprofitable.

    iille t s R5EFS ( TE PUIlrr )


    lluirr s Reef s ( also knorno as Te Puke R,eef s and. Fleniagt s
    H111) occur approxirnately 6kn south-west of Te Puke in
    hypsrsthene augi.te and,eslte flows (Bartrun , 1913) of the
    Coronandel Group." l{ear the v6ins the rocks are hydrothernally
    .:.
    603

    altered, to propylitic assesblages of cb.lorite, second,ary


    ouartz, carboaate and pyrite (Bartrun, 1913).

    Beti.reen 1895 and 1928t 1.? sillion Srass (5trr'tlZ ounces)


    of .golC and silver ?rere proCuced, fron tvo :{ile trenCing ouartz
    vei-ns, l{uirs Reef anC l{assey Reef, nined. on l levels to a
    depth of 150n below the surface (Dovney, 1935). iiost of the
    ore cale froro iiuirs Beef in worlings near the surface. The
    average r.riCih of this vein varied fron 1 .5n in the upper
    leve1s io lr.6a, in tbe louer levels, with a naxiaun r.rldth of
    18a (Do:aey, 1935)

    Bartrus (1913) noted that oIr 1 level the accessible parts


    of the vej.n (Curing his vislt) contained nareyistr falrly
    friable quartzrt although siaterous banded. quartz vas pleutiful
    intheuu11ock.heaps.Quartzpseud.onorphsafterca1c1te
    occurrsd. on 2 Level and Bartrun considerecl ihat the vein
    naterial resenbled that in the upper levels at !'Iai hi. Below
    2 leveL the veia rpincheC considerably and uas very puggytt. '
    AITTHCIIT BANRT CHRISTTE

    rutnD INCUFIo[f;ir StAnr.n ISqr@Et AND @ogHEt'{ISmr


    OF PONFHTBI C@PEN illD EFITHEA!{AI. VEIN IEPGIIS
    oF TUE HAI'nAKI GOID - SILVER PnOrINCE,

    NE{ 2EAL$TD

    voililE 3

    APPENDIGES II TO l[r
    T,NCIBO{ MICNOPROBE AIID ETTIID INCLT'SION

    MEIHOE AI{D REilTLTS, THmMoCHEMICAI.


    c,aIsuIATIOlS, AND SAI,|PLE DESCRIPTIOIF

    August t9g2
    (i)

    CON?ENTS OF VOLUHE "


    Pass
    604
    tPPEItDIxII.ELEoTR0THIcRoPRoBBANALISES;HElgoDsArDREsuLTs
    504- .'
    HE?EODS
    60L
    Inatrunentstloo
    601
    l{eaeurlng Condltloag
    604
    Staadards
    601
    Detectlou LluItg
    604
    Ioterfereneea
    606
    BESI'LTS
    607
    Acanthlter AgaS
    Argeatlan Pentlanitite' (8etti)t+X ABt-ISg 607
    608
    Blauuthlnlter BlaS,
    60E
    CbalcoPYrlta, CuFeSa
    509
    Gold - Electrun' AuAg
    510
    Galena, PbS
    612
    Besslte, Agate
    613
    PYrlter PoSa
    611
    PYrrbotlto, FeS
    615
    SPheIerl.te' ZnS
    62)
    TotradYolter BlaTeaS
    6")
    Tetrahedrlter CuraSbtsfl - Tennantlte Cut2A"4St3
    APPENDIX III PROCEDURES AND RESULTS. OF FLUID INCLUSIOII FILLING IEI{PERATURE
    621
    rREE;ii;-iriiiENIiUNE AID APPARENT SALIIITT I{EASOREMENTS
    62t,
    PROCEDURES
    62L
    Sanple proparetlon for opttcal exaoinatlon
    625
    SelectLos of lnclualons end tbelr atorage
    627
    Deterutnatlon of FtLltng Teoperaturea
    629
    Detornllatlon of Saltnltleg
    629
    Freezlng Stage Constructlon
    ' 6t3
    Freezlag Stago 0perattng Inatructl'one
    6)1
    RESULTS
    ' 6)1
    Usthod of Lletlag
    635
    Unltg
    676
    Mlnerg Eead
    6)6
    Te Ahuoata
    636
    l{orthern Colvllle Penlneula
    617
    Kuaotuau
    637
    Tolatea, Corooandel 638
    Petote Strean, Corooandel 6)9
    UhaagaPoua
    639
    Broken H1lIa
    639
    !{ esvo avll-Ie
    640
    Haratoto
    613
    Kouata
    611
    llaltekaurl 6lr5
    I{alhl 616
    Karangahake
    6t6
    Tui Hlne 618
    tJaioroogooal

    Vterog,r, t il{l','E:.::TY cr',,''rl'.illaroN


    I

    (ri)
    Paso

    IV FLUID IUCLUSIOS CRUSEIilG AI{D LEACTTIT{G EXPERII{EIITS 650


    TPPEXDII
    SAUPLE PREPARAIIO!I 650
    CRUSSITIG PROCEDI'BE
    650
    LEACf,I}IC
    65L:
    RESITLTS
    658
    ISSESSHEHT OT EIPERIUEIITAL COIIIAHIXATIOTI 661
    PRECISION: DUPLICATES AllD SAIIPLE CR0IIPS 661
    ACCURACY: TEST SAMPLE
    666
    ASSESSHSNT OF AIIALISES OI' I}IDIVIDUAL SAMPLES 667
    667
    . Quartz SanPler
    Tokatea 667
    Petote Stroao Area 669
    l{haagapoua 671
    lleavesvllle 672
    l{aratoto 67)
    Kouata 675
    l{altekaurl 6?6
    l{alhl 676
    Tul l{lne 6?8
    680
    Uaiorongonal
    CalclteE
    Northeru ColYllle Penlueule 682
    Tdkatea 68t
    68A
    IPPEIIDIX V TITERHOCHE}IICAL CILCSLATIONS
    681
    I}ITRODUCTIOII
    684
    }TOTATIOIT AND UNITS
    685
    EQUILIBRIUM
    6E5
    Iatroducttoa
    685
    (1) Equflfbrlun Betneen Aqueoue Specles
    (2) Equlltbrluo Betsoen tbe Flutd and Preclpltatlng lll'nerals 687

    (3) Preoervatlon or Modlftcatlo! of Asseublagee 688


    688
    ( 4.) l'llneral-Fluttl-l'llnoral Interactlon
    589
    Discuealon
    690
    EVIDENCE FROI,I FLUID INCLUSIOIIS AND STABLE ISOTOPES
    692
    IONIC S?REIIGTIT (AT ROOM TEMPER.ITURE)
    692
    ASSOCIATION OF IONS AT ELEVATED TEHPERITURE
    693
    CALCULATIOII OF THE DEGREE OF DISSOCIATIOII
    695
    ACTIVITI AND ACTIVITI COESSICIEIITS
    697
    pH
    699
    CALCIIE STABILIII AND PH
    ?01
    FUGACITI
    ?01
    Iutroductlon
    ?01
    FugacitY of COa
    ?01
    Fugaclty of CO2 fron Fluld IncLuglon Date
    Fugacltyofco2fronEydrothoroalAlteratl.onHlneral 'lo5
    Aesenblagea
    706
    FugacltY of Sa
    706
    Introductlon
    706
    fSa Fron SPhalerlte CouPosltlon
    713
    fSa Froo PYrrhotlte CooPoeltloa
    713
    f,Sa Fron Electrun CooPoaltlon
    fS^ Froo Mlaeral Stablllty Relattose oa fS2 Versus 120
    TefiPerature Dlagraos
    (iii)
    Page

    FugacltY ot O, 720
    Introductloa 720
    fSa Versua fOa Dlagrane ?22
    Conceotratlon of Totol Sulphur ln Solutloa 725-
    f02 Varous PE Diagrana 729
    FugacltY ot te, 73t,
    SPECII'IC MIIIERAL SISTEMS r31
    ?
    Tungstea l'llnerels 731
    Selsaiferoug and SelealdE Mlnerals 7t8
    Introductlon 738
    Thersochenlcal St'uilles 738
    AppJ.lcatLon 740

    APPEI{DII VI ORE PETROCRAPHT OF SAI{PLES FROM WAIHI 712


    SAI{PLE 1'901 (Wh36), HARTEA MIXE (UNLOCATED) 7L2
    SAHPLE 13992 (Uh3?)' HARTHA UrUts (ulILocATED) 713
    SAHPLE 13993 $h1,8), HARTHA HINE (UIILOCAIED) 711
    SAMPLE 1)978 (Wh2?), !'|ARTHA MrlE (ul{LocATED) 711
    715
    sAl{PLE ',]1032 (GJ3), CRAND Junctrou l{rNE (uxLocAfED)
    715
    sAlfPLE 1trl3g QIh28), MARTEA MrIE (UiltocATED)
    716
    stMPLE 1tOlO (ttb29), I,IARTHA UIilE (UILOCATED)
    SAHPLE 11,01,1(l{bro), MARTEA MINE (UNLOCATED) 7 l+7

    VICTORIA VEII{' ADIT LEVEL 7 lt'l


    SAI{?LE 11943 OIbl5),
    l'7
    sAl,lPLE 1t'0t,6 (l'Ib43), llARtgA l'lrxE (u[LocATED)
    7

    718
    sAl,tPLE 110/'? (l.rh41,), I'tARtlIA VErX' 7 LEVEL
    719
    sAl.tPLE 14048 (Wh45)' UI{LoCATED
    750
    sallPLE 11919 (Wh42) , MARTUA VErl{ 'rAT DEPTHn

    sAl.{PLE 1495q (ub4?)' I'IARTEA VEr}l' 10 LEVEL '150


    750
    SAMPLE t4q51 (Wh49)' UNLoCATSD
    10 LEVEL ?52
    SAHPLE 11,052 1UU:O), MARTEA VEII| '
    753
    APPENDIX VII ORE PETROORAPII OT' SAMPLES FROIII KARANGAIIAKE
    t
    TALISI'|AN I'TINE (UNLOCATED) 753
    SAI,IPLE 11023 $L1?),
    TALTSHAII MINE (UllLocATED) ?5tt
    SAMPLE 1to2l, (TL21)'
    14 755
    SAMPLE 1t+025 $L22), TALTSHAII LBVEL
    756
    sA}lPLE 14026 (rt24)' tALTSHAI 13 LEVEL
    (TL25), IALISMAN 13 LEVEL 756
    SAHPLE 1t+027

    OF VEINS IN THE WAIORONGOHAI ARFA 757


    APPENDIX VIII ACCESS AIID OBE PEIROGRAPHI 757
    IlltRoDucrroN 751
    PREI.IIER . COLONIST SECIIOf,
    757
    Introductlon
    coloolst snlthY Level
    l{cleang 1100t tevel
    12i
    76L
    Preoler llo.1,, Vulcan No'4i and Vulcan No'2 Levele ,166
    MAITT VEIN
    766
    Maln Veln, Dlaoond Creek Waterfall
    766
    Neu Flnd Sectiou of Haln VeIn
    768
    l{AI QUEEN
    ?68
    MaY Queeo 1 Level
    768
    MaY Quoea 2 Leval
    - HaY Quen .3 Level 771
    77)
    tfut{BER ouE REEF
    T',t3
    l{o.1 Reef, TratuaY
    7'17
    No.1 Reef, Dlanond Creek llaterfall
    Eoulxza rn
    If,VESllEsSr Ib0llLll ltrD lD.LgOil8 rBIfis 7n
    Locrtles 7U
    Itrvori[cs! 78'
    Lo,y*lty T87
    talsonoe Soilthru Adft ([1I1t or Ferguaronre Dr{,ve) 78,
    t l{01 vElll 78t

    *PPETD:IT II LOO4TIOI AID FBIET DS8CEIPIIOII OF STUPI,ES ?a6


    IITBODUGfOBI trOf88 ?85
    l{,ethod of Li.s:tllg ?85
    Senplec not Llstad ?86
    Fl'rfal [unbcrr ?86
    Grtd Referenoea 'l,g:6
    DESCRIPITOIS lt8?
    FICURES Pase

    III-I Pbotograph of nlcroscope beatlng atege 626

    III-2 Photograpb of nlcroecope freezlng stage 628'-'


    III-3 Cross-soctlon of freezlng etage 630

    III.4 Photograpb of Parte of thc freezlng atage 631


    *
    III- 5 Dlagranatlc layout of freezl'ag stege epparatua 632

    IV-1 Pbotograph of tbe eloctroLytlc cleanlng cella 651

    IV-2 scheuatlc layout of tbe glaes vacuuo llne used to ertract vater
    frou fluld lncluslous 65)
    IV-3 Photograpb of teflon eub-bolllng acl'd distlll'atlon spParstus 655

    rv-4 Flor dlagrao of cruahing and leachlag procedure 657

    v-1 Effectg of dlsequlllbrlun betveen a hydrotbernal golutloa and the


    valn (ulneral) sYateo 686

    v-2 Dogroe of dj-eaoclatlon of l{aCl aolutloae up to 300oC 591

    v-3 Ion product and neutral pE of sater at elovsted tenperaturea 696

    v-4 Hlneral stablltty rel-atlons 1n the syeteo K20 - Alz0i - S1O2 - 698
    H2O - UCI
    v-5 Oraph of tCO, Yorsua tenPerature 70L

    v-6 Conposltlon of aphalerite ln equlllbrlun vl'th pyrlte and


    pyribotlt" as a iuactlou of tenpereturo and fSa 709

    Y-7 Effect of preerure on ephalerite coupoeltlou in the aaeenblage ?10


    ephalerlte I PYrrhotlte
    v-8 coopoeltlon of pyrrbotite ln tbe Fe-S eyoteo as a fuuction of 712
    tenperature ancl fSt
    v-9 Snootbed tarnlgh curves for electrun conpoeltloag 715

    v- 10 Gorrectlon fectore for the relationshl,p botueen electruu conposltionr,', a


    fSa aail tenPerature
    V-11 . !,llueral stabiftty re1-atlong in the oysten As-S-O as a functlon of 721
    fS, and fOt
    u-12 foo versus pH dlagran nltb-contours of fEaS in equllibrluo rltb
    lUd p""aotinant aqueoue aul'phur spacles 730

    v-13 fO2 versus fs, dl'agran lllustratlng the stebllity of ferberite D3


    v-l4 foa versuo fsa dlagran l-llustretlng the etablllty of huebnertte 'It'
    V-15 f0a versus fSa dlegran lllugtratlng tbe stablllty of achoellto 735

    v-16 Poa veraus pH dlagrau lllugtratlng the stablllty flelde of tungeten


    ?35
    aud lron olneralg
    v-1? fOa veraue p[ dlegran lllustratlng the stablll'ty fielde of aqueoue
    soleol.un aod sul.phur epecles '139

    vr-1 of sphalerlte aacr galeaa bv


    751
    ll::i:1"il:FiinouSliitfiSrilint""euent
    ur-z ll::??l"rTFiilrr:liltfi5r;in.'"eneat
    of spharerlte and s'1ens bv
    751

    VIII-1 Map of the uaJor velna aad norklngs ln tho llaioroagonai area 758

    VIII-2 plao of vorklage 1a the coloo!.st and Preoler sectlonel waloroagonal 't59

    VIII-3- Pbotograph of breccla rolnerallsailon ln a band speclnen froo 760


    Colonie t Solthy leve1, l'Ialorongooal
    _ a''b
    . a,rtl*

    l+ p8,e.u.{EF' ' P'qgs

    v::t-4 Ft1a o.f tb* [,slr FdnC ror.&l-ag,sr Fia:t roag.otal n6,;E

    YIIE-' P-betegr.cpb of uo-rtJggp fu'tbe, tr.u Sl+d S*.et'log, fl,llor.pngsnr{ '!161

    VX.II.6 Pt'ylorlersgprph ef dggdrl.tl's grX,e4p [a qgeltat' fe'c,l' fs{s,r


    tctftr6a oslri T?.*
    yrtrI-t Pbotogrepb of beodcil aulpilder and oonb quartc la a haad, rpeollea
    fro.u lfo.l Yelar llctroroagonrl 7'15

    UIIJ.E Plaa of rorktraga la tbc tlcr of thc lfelcole rnd l4veracst Valaae
    Tato*oagoneL 782
    v,r,trtr-r9 E!.rn of tbe rog'thrr4 ad:td {1aterssot{l.B tbe fc!.ao,r-s'Sei.Br
    Eetrotongoeei, f,8{
    (lrrr)
    LISI OF TABLES Tfl VOLUHE q

    TIBLE !,sce,
    II.1 Detectlon llolta for electron olcroprobe aaalyeeo 605

    IV-1 El.ectrol.ytlc cleanlng ceL1 log 65?.:='


    rv-2 Analyeea of flutd lncluglos leachlng raageota 656

    rv-3 Concentratlooe of long leashed fron crughed saopleo of ouartz


    . and
    calclte 659

    rv-4 Analyaea of blanlE 667

    IV-5 Analyeea of fluld lnclua!.ona ln salolte frou lfgauhe and oodero


    bore flulds 665

    v-1 Sooe thernochenlcal parauetera for selectad nlnerallsatlona 691

    v-2 Values-of fCO" cslculated frou the conceatlatlos of COa ln fluld


    lnclualons 700

    v-3 fCO, durlng depoeltlon of epltberual depoelta at Suanyslde anil


    Bagfilo Dlstrlct 702
    v-4 Log t8, velueg caloulated fron the iron conteat ln ephalerltea ?o?

    v-5 Log fS2 valuee celcul.atsil frot tbe conpoaltlonc of pyrrhotltee 714
    v-6 Log fS2 vslues calculotetl fron tbe uole fractl.on of sllver l'u
    electrGn and gold ?18

    v-7 Tberoodyaaulc data used to calcul-ate tbe fSa versua teuperature


    and fSt Yareua foa dlagraoe 721

    v-8 Coacentretlone of toteL eulphur lq aolutlon aaalgned to eono


    epltherual deposlte by other rorks 726

    v-9 ConceatratLou of total sulphur I'u eolutlou durlng foruatlon of


    aone deposlta ln the Haurekl Gold - Sllver ProvLnee 727

    v-l 0 to calsulete the fOt voraua p[ dlagrala


    Theruoilynallc date usecl 728

    v- 11 lbernodynaule drta uaed to aaloulste thc flea Yeraua fS2 diagraus 733
    604

    APPEi{DIX II
    ELECTROII I.IICROPIi,OBE ANALYSHS :

    UNTHODS AI,ID R.ESULTS

    I'!ETHODS

    Instrumentation
    EPI{A analyses were nade on the Jeol 733 Superprobe in
    the Analytical Facility, victoria universi-ty of trJel-lington,
    using the ZAF (atornlc nunber, absorption and. fluorescence)
    correction progran.

    i"l easurine Conditlons


    i"leasuring conditions were eenerally; z5kv accelerating
    potential, 2.0 x 10-8 anps specinen eurrent and 3 mieroaetre
    bearndlameter, vith the following counting tiues: peak, Z at
    20 seconds; background, 2 at 10 seconds. some analyses of
    acanthiter electrum and hessit,e lrere nade at lor,rer aecelerating
    potential and specinen current and/or wid.er beam dianeter.

    Standards
    Pyrite and galena (Broken Hill, l{.S.!J.) lrere used as
    standard.s for sulphur and, lead. respeetively, r,rhereas pure
    erements lrere used as standards for all other elenents.

    Detection timits
    Detection linits are l-isted. in Table rr-1 and were car-
    culated using the following fornrula:

    Detection limit = 2,r


    nVTb (rr-t )

    where Rb= background count rate


    Tb= background countinq time
    m = counts per seeond per I

    The values listed are those calculated for analyses of


    the elenents when present in loru concentration, Concentrations
    below the detection llnits are eonsidered not slgnificant.
    @5

    TABTE II ' 1: Detect'i.on linits for electron


    nicroprobe analyses.

    Eleaentl

    Ag 0.10
    Au 0.20
    Ae 0,08
    Bi 0.40
    Ccl 0.08
    Go 0.04
    Cu 0,05
    Fe 0.04
    Ma 0.03
    Ni 0,0/i
    Pb o.03
    s 0.05
    sb 0.08
    Se 0.13
    Te 0.10
    Ztt 0.05
    66
    Interferences
    Interferences of Bi anil Pb prevented routj-ne analyses
    of these elenents together. The peaks used for counting Bi
    and Pb were ad.jacent and the background count of Bi occurred '

    on the tail of tbe Pb peak, causing negative corrected counts


    for Bi in analyses of galena.

    RESULTS

    The mj-nerals are listed. in alphabetical order. The


    ind.ividual sanples are listed. within each rnineral category
    in ord.er of lncreasing V.U.W. (or other) sanple nunber.
    Sanple nurnber sdbscripts (a), (b) and (c) indlcate different
    polished nounts of the same sanple- The locations and
    descriptions of these samples are given in Appendix IX.

    11.&. = not analysed


    Acanthltr A%S

    1tp32(cJ3) 14Or+3(Wh35)
    1 12 3 L23\ 6

    Ag $.55 st.L9 83.96 g3.n 84.41 83.24 84.80 84.21 g).1+9

    s \2.33 11.28 LL.)3 8.89 7,q 9'1.o 9.61. g.Lt 9.50


    So l+.b5 5.LL /,4I$ 7.62 9.73 6.92 6.10 6.12 6.70
    Cu n.a. Rrar l|rar t|r8r n.A. E.A. B.a. Br8o ll.8 r
    A! n.8. llo8r nra. D.ao n.A. D.A. Dr& n.A. Drar
    Au llr ar lbSo Ro8r lLSr llo8r DrA. n.a. !r8. lI.8 o

    fotA]. 100.33 99.58 99.75 gg.1t 1@.03 99.56 1m.94 99.S6 n.69

    zt5/37h$u) zesfiilapsz) H18185

    789 1 L2 I
    ag 86.5I+ 85198 87.s @.72 8L.t3 85.14 e5.g
    s 12.94 12.2t, tz.L, t2.o2 LT.3T t2.l+9 72.1+5

    S 0.96 0.98 L.O' 1.94 o.13 3.LL 2.58


    Cu BoAr E.l. DrAo L.93 o.27 O.O9 Drao

    Aa B.8r BrAr tfoar 1.80 o.ol o.6 q,t


    AU hr8r RoEo lrar 0.58 t.26 0,m Doar

    Totr.l 10O.t4 99.20 1m-20 98.n n.Lg 101.83 1@.20

    1r18185
    I
    Ag 8r.28 55.18 Sl..6S 85.70 84.58 85.t1 s3.?o 85.04 66.09
    5 12,8' 72,17 12.75 72.6 W.6L 72.78 11.85 12.23 11.16
    sc 2.56 2.I+ 2'6L 2.?r 2.5t+ 2.67 L,og 3.?8 ?.74
    Cu n.a. D'Eo RoEo ll.8o tlo8r [.Eo llr8r B.lr tloSo

    As RoEr ar8r irar llo8o n.a. Br8r D.ao Eo8. n.t.


    lu n.A. ltrSr Brar lloSr
    tLSo fl.8r E.ao BoEo ll.8r

    ?otal 100.6? 1m.?9 100.0? 100.l}? n,79 t@.n n.67 101.05 1m.99

    Argentlan PantJrndltc, ( fc t[1)er*Agf-*Se

    1396t (r4{1)
    1

    Fc t6.5L
    ul L8.26
    18 L3.r2
    3 1L.rC
    Gr O.?O
    Z^ O.g?
    Ar O.0o
    Co 0.01
    Total 100.49
    6oe

    Bl,rnuthtrdtc, E S.

    13915 (l\tr 27)


    1 23 b5 6 ? 89
    Bt 78.30 78.t& 76.3r 79.8 763e 78.18 76.5t+ n.32 79.W
    s L?.q 18.00 1?.85 L?,78 17.98 r7,66 L7.6 1?.50 U.6r
    Pb 1.?3 3.L6 b.36 2.18 4.91 3.75 L.4g 3.gg 2.$
    Cu 1.14 o.n r''.g o.g2 1.41 L.13 r.38 1.21 0.81
    ?s 0.02 0.06 0.16 o.otl o.o3 o.@ o.ol o.03 0.02
    rotal 10O.gt 1@.64 99.93 1m,?5 1OO.?1 L@.7, 16.01 10o.o5 10O.3O

    Chalcopyrttcr Cu Fc Sz

    139?9(stud raoaS(a) r4o58(r'lr 15)

    1 L(M2' I 2tb
    Or 34.23 ?l+.12 3l+.3O 3t+.t5 33.* 3L.26
    Fc t..o2 30.45 n.vl 31.06 tO.?O 30.56
    s tt.9o lt.8, tL.19 35.L7 35.Ot+ 3[.88
    A! o.q) o.36 o.41 o.L? o.@ o.o5
    Au Drar 0.11
    - llrSo n.Er ILar DoSr
    7.8 0.01 DoEo o.10 o.o2 o.vl o.o5
    ill o.06 tloS o 0.03 o.o1 0,01 0.00
    l8r 0.@ DrBr 0.@ 0.00 0.q, o.01
    cd 0.6 Br8r 0.@ 0.03 0.@ 0.@
    sb o.02 DeE. o.01 o.s ' o.o3 0.og

    rotel 99.25 99.29 n.fl 1s.6r n.69 99.?t

    ar 3L.26 3\.r3
    Fc 29.9L n.n
    s gh.8 tb,26
    ls o.og o.55
    Au lloSo n.a.
    7n 0.58 0.09
    l|t 0.o o.@
    Hn 0.00 O.01
    cd o,@ o.o2
    sb
    L
    0.05 o.08

    lotc.l 99.72 100.33

    -
    609

    Gold - Electn:a AuAc

    139o9(Tr! 30)
    L2
    Au 89.05 89.69 91.03 9t.35 91.@ W2 89.?8 89.08
    Ag 8.82 8.& 7.o5 7.18 1.LL 8.11 8.55 8.9t+
    s o.17 O.12 o.2J 0.1r O.1g O.12 0.19 0.13
    cu 0,06 o.o? o.r4 o.og o.og o.vl o.u o.23
    Fa o.O2 O.O3 O.Og o.ol O.O4 O.O2 o.t4 0.14
    As O.@ 0.0O O.oo O.01 O.m O.0O O.00 0.02
    le O.m O.0O O.O2 O.0O O.O? O.O3 O.0O O.m

    rota.l 98.12 ge33 98.13 98.?8 98.\' 98.67 98.88 98.5t,

    13915(nrt 2?) L3937$A3) 13961(n7)


    t2 t2 L23L
    Au 87.n 90.22 53.79 55.E) 6L.i\ i8.3r 6.24 h.r3
    Ag 11.? 7,75 l+3.84 U.1.2 36.15 39.32 38.3L 39.L9
    s o.o? o,0l o.51 0.3' o.o8 0.10 0,16 0.03
    Al o.@ o.o2 o.o o.03 0.00 0.@ o.@ o.(xl
    Fo 0.00 0.01 o.rj 0,62 o.s o.00 0.0o o.or
    Ag o.@ o.oo o.@ 0.00 0.26 0.18 O.27 O.t2
    Te 0.o9 0.06 o.o2 0.01 0.04 0.r2 o.0o o.@
    lotaL 99.72 98.10 98.70 101.25 98.Ct 98.04 98.88 99.n

    t/1@l561(M 2l
    l2
    Au 61.34 60.61 6A30 73.6 ?5.27 T,.t$ ?b.96 n.29
    As 39.8 3e.t1 39.ot+ 2?.5? 25.35 26.02 26.L9 26.W
    s o.o5 o,o8 o.fl o.m o.q7 0,01 o.or o.o5
    Cu 0.00 0.05 0.01 0.00 0.o 0.00 0.00 0.m
    f 0.00 O.0O 0.@ 0.02 0.@ 0.@ 0.00 0.00
    Ac 0.11 0.31 O.m o.r7 o.m 0.@ 0.@ o.o5
    Tc O.OO ' O.OO O.O9 o.@ o.@ o.05 0.00 0.@

    Totgl 101.18 99.21+ n.5l 101.96 100.69 99.52 101.16 99.89

    r&251u) $1226) uo32(or3) lrlo&,3(rfb35)


    112t L2'L
    Au 7L'3t+ 5L.76 52.69 ,2.t L 65.95 6\.2s 65.08 6gae
    Ag 26,67 116.Az L6.85 t 6.Zt t2.5' tb.tp 3\.t5 T,t+O
    s 0.06 o.o9 0.05 o.@ 0.u 0.10 0.08 0.o4
    Ol o.0o 0.@ 0.03 0.00 o.@ 0.@ 0.m 0.03
    Fo o.o0 o.o9 0.00 0.01 o.o3 O.@ 0.00 0.02
    Ae O.OO O.0O O.rr1 0.95 o.m 0.00 0.00 0.00
    Tc 0.05 o.03 0.18 O.O9 0.13 0.16 0.00 0.03

    ?otal 98.12 98.81 1@.22 n.e, 96.81 98.9t+ 99.5L 101.90


    6ro
    CoId - ELectno (Contlnued\

    ugl(rUr5) (contlnucd) 1,tptl6(Htrl.3)


    t67e 1

    Au 6t.5L 6?.10 6n.n 69.26 68.15


    Ae ' 37.or 32.n 32.L5 35.6 3L.?6
    ,s o.gt 0,13 0.06 o.13 O.1O

    Cu O.@ O,tl 0.Ol 0.0O O.0o


    Fc O.@ O.otl O.O2 O.O3 0.13
    Ag 0.26 0.19 O.O5 O.zL O.0O

    Te O.OO O.1O 0.00 0.05 O.0o

    rotal 100.85 9.89 99.70 99.46 n.1b

    qorp(nbl}t) 1J+82(xLct)
    L23br67 1

    Au 6L.93 63trL 62.35 8.8 6t.S 6L.t8 $.e @'27


    Ag 36.03 36,49 36.25 37.12 96.57 3?.bt t6.n 19.64

    S O.15 g.L3 O'13 0.09 O.10 O'0r/ O':4 BrBr


    Cu O.11O.gl O.2O O.O5 O.2L 0.06 O.17 Drsq

    Fc O.O5O.O3 O.@ 0.08 O.14 0.07 O'm BeEr

    As O.2gO.37 O.15 O.m O.2 O'm O'02 D'eo

    te O.@ O.O1 O.@ 0.01 O.O9 O'01 0'O{ loao

    totsL 98.56 100.62 99.ro L6.?7 101.9 99.05 100'69 99'91

    285/7il8 (W,
    123b5
    Au tg.gt+ 58.50 55.7L 58.t+9 60.4
    Ag t&.56 N.65 tz.n LL.52 38.18
    g 0.17 O.n o.24 O.33 0.18
    tu o.or o-08 o.@ o.o3 o'oo
    fs o.ol o'01 o'o[ o'71 o'zt
    Aa o.@ 0.18 0.26 0.00 0.00
    To O.O O.O2 0.18 O.0O O.11
    rotat 100.68 n.IL 98.92 101.q7 99-57

    C'alena' Pb S

    139?1(Dcu)
    $959(1n)
    t2tt56L2t
    pb 86.72 86.2t S6.S0 36.19 86.18 e6-la 86'92 86'tf. e6'65

    s13.0212.g||9.2L'2.9t+L3.|21'.L619.t61,.1113.10
    Ag O.O2 O.O1 O.Ol O.O4 O.O5 O'04 0'06 O'02 o'q)
    Sb O.O1 o.ot O.gq 0.69 0.06 O.OO O.08 O.O3 O.O5

    Fo O.OO O.m O.S O.@ 0.16 O'11 O'O2 0'0o O'OO

    Tor8l n.78 n.8 1OO.O' n.LI n.6 99.'12 1m'45 99'60 99'80
    6Lt

    Galena. Pb S (Contlnued)

    :.397r(Dc12) (contLnuca) 13971*(SM11)


    \56 1 2 3 t+.
    Pb 86.s) 86.02 56.99 86.63 85.15 85.06 86,75
    s r3.4 rl.n 13.30 13.00 L3.2L t3.Or+ t2.94
    Ae o.O3 O.O3 O.O9 o.o5 0.01 0.00 0.o2
    sb 0.00 0,05 0.@ o.00 0.03 a.a o.o9
    Fc O.OO 0.0O 0,0O 0.@ o.ol 0.00 0.03
    ror8]. 10o,m 99.31 100.39 99.6e 99.hL 99.4 99.s)

    13985(Bc3) 13e89(Hs4
    J
    123b I 2t b5
    Pb 86.A. 86.95 85.93 st.?z 85.82 86.?1 86.7? e6,28 86,t+L
    s 73.W L3.4 L3.22 L3.54 L3.22 $.q L3.1L u.o3 L2.96
    Ag o.@ 0.02 0.o1 0.o1 0.00 o.o2 o.04 o.a3 o.o4
    sb 0.06 0.oo o.o2 0.02 0,00 0.05 o.o5 o,o3 0.04
    F6 o.ol o.oo o.00 0.00 0.02 o.m 0.00 0.or o.o1
    Total 10O.0O 1@.24 100,18 .100.?9 99,06 99,88 1m.1? 9.99 99.46

    lrpl5(l,rK6) t@25 $1226) r4o4o(i,h29)


    L2 1"2to) 3Ir t2
    Pb 86.02 86.4 86.03 e6.?6 86.2, 86.76 85.02 86.54
    s t3.r3 13.29 L3"2L 12.93 L3.L7 t?.24 L3.9 13.32
    Ag o.o1 0.o1 o.o8 0.06 0.@
    0.00 0.00 0.03
    sb o.o7 o.05 o.o3 o.t5 0.06
    0.03 o.ol} 0.06
    Fe o.o1 0.@ 0.03 0.05 o.0o
    0.01 o.o1 0.@
    Total n.23 99.6t+ 99.t+L 99.?3 n.65 100.08 99.19 99.9t+

    uor|6(r{r43) t4ol(l{bl}')
    t4 56 L2 L2
    Pb 86.23 66.46 85.89 86.U 85.6r+ 86.16 86,2t+ e6.22
    s 13.28 L).L1 LJ.32 t3.3O 13.t6 13,10 L3.27 Lr.3?
    Ag o.o5 o.oo 0.04 o,o? o.o4 o.sl o.o5 0.11
    sb 0.08 0.05 o.o5 0.0t 0.10 0.04 0.05 0.02
    Fe 0.0o o.o5 o.L3 0.q7 0.08 0.07 o.o1 0,m
    Total n.6L n.73 n.l+2 9e.6 n.u n.& n.62 99.72

    ge59(nd r?)
    3lt 1 2?l+56
    Pb 86.0[ 86.2t s7.L9 ,6.rr+ s6.62 86.79 86,66 6?.18
    s 9.95 12.83 13.00 L3.@ t9.J9 L3,L6 t3.99 13.30
    Ag o.o7 0.o7 0.03 0.0, o.tt 0.o8 o.o9 o.@
    sb o.o2 0.12 0.03 o.oo o.o3 o:08 0.05 0.10
    Fs 0.00 0.00 0.00 o.0o o.o1 0.@ o.o3 0.oo

    Total 99.o7 n.23 L@.25 gg.6s 1@.12 100.10 7@.22 1@.51


    6t2

    Oalenar Pb S (Contlnued)

    1406o(tu1 18) 1r.061(1111 19)

    L2 t2
    Pb t1.59 86.57 87.30 e6.65 et.r5 e6.?2 86.52
    s t3.25 L2.93 L3.12 r3.o3 rr.36 12.7b
    o.o1 'A.6U
    Ag O.02 O.0O O.Olr 0.00 0.11 0.08
    sb 0.04 0.00 o.o5 0.03 o.0o o.o9 o.o7
    Fc 0.O1 0.01 O.@ o.o3 0.02 o.00 0.00

    Total 1@.91 99.52 l@.72 99.75 100.63 99.05 99.Jr

    r4&o(wr96)
    1 23l+
    Pb 86.26 s6.7t a6.j7 e6$o
    s u.8e 72.'18 r3.L5 Lr.L6
    Ag 0.06 o.o3 o.m o.o5
    sb o.00 o.0o .0.01 o.dl
    Ec O.0o o.@ o.00 0.00

    totsl 99.2A n.rr+ w.?3 9.59

    Heaaltc, l,erTc

    g95r(x?)
    L2 34 ,6'1 8910
    As 63,t7 6?.26 62.29 63.30 62.1? 63.t+g 63.40 63.36 62.tF 62.n
    tc ?7,8 J7.2J 36.9? 37.re 97.70 37.26 37,L5 35.71 37.u1 36.5L
    S n.a. n.a. |l.a. [rao De!. lrar lloSe tlolr n'4. A'g'
    Cu DoSo n.a' Ro8. lLSr tlo8e n.At n.A. n.e. Br8o n'A'
    Fc Drar n.a. B.ar Drao n.a. r|ra. n.A. Doa. n.e. D.ar
    lu nrsr n.er ll.ar n.a. R.ae n.A. n.A. lt.8r n.a. Brao

    Aa nra. n.a. n.a. n.a. tlrar [rA. iloa. rlra. . n.A. n.A'
    Sr Dra. trrar tLar lloSe nr&r [ra. n.a. [.a. n.e. Dear

    Tot-l 1e.58 1@.49 n.26 1m.48 99.27 100.?5 100.t8 rm.o? n.55 w.50

    u$2(YLt}l 1r'o94(lfl.98)
    11 L2 t 1 234
    tg 6t.t+2 6e.6t 60.06 61..05 . 62.16 58.2L &.5t 61.r/)
    Tc 36.9b 37.& 38.t+7 g?.1!. F.Al l+1.11 lO.O8 3?.1+5
    S a.e. o.o7 0.22 o.22 0.0l} o.o3
    0.02 0.o9
    Cu !.a. 0.1? 0.28 0.14 o.@ o.o1
    0.o1 0.10
    Fr D.a. o.@ o.@ o.02 ' 0.00 o.o1
    0.@ o.o0
    Au n.a. o.G) o.19 o.m
    '
    0.00 o.@
    o.22 0.@
    ls ttolo o.3rt 0.5& o.75 Q.j2 o.@
    o.x2 0.50
    36 Drro o.72 0.36 0.00 o.00 0.00
    o.00 0.@
    Iotal 1m.36 101.55 100.1& 99.32 100.79 99.37 100.9 99.5e
    6tz

    Itclgtt.r A% Te. (Contlnt:d)

    upgr(n9s) 285/37/2 (t4r2)


    5123h5
    Ae 62.02 6L.7O 62.tC 69.12 63.19 62.7tt
    Te 3?.7L 37.LL 36'36 36.81 37.L5 n.Ls
    g O.Og O.Ul O.3t+ 0.11 O.1O 0.12
    Cu 0.13 O.@ 0.Ol O.O[ 0.00 0.0o
    Fa o.O0 O.0o O.0O O.0O 0.Ol 0.0o
    Au O.@ O.@ 0.08 0.0o O.57 l.t&
    la O.11 O.Vl O.1! O.@ 0.26 0.00
    sc o.oo o'18 o'lr1 o'27 o'12 0'@
    lotal 1m.05 99.18 99.75 100.35 101.83 r01.7t

    2s5/ril6 (Artl
    123,+'
    Ag 61.2e 62.7? 6t.Zl 62't;t 62.80
    Tc t?.t+, 36.99 37.L5 36.78 37.39
    3 0.10 O.U 0.Og O.1O 0.O9
    G'l o.@ o.o1 0.@ o.@ o.@
    !c 0.00 0.05 O.@ O.m O.o0
    Au O.@ 0.86 0.82 O"25 0.@
    As O.OO O'13 O.@ O.0o O.2,
    Se O.@ O.m 0'00 O.00 0.0O
    . Totsl lm.83 '1qr.98 99.35 n.56 1@,53

    Ptr{tcr Fc %

    30)
    r,9o9(rt4 r3915(ftr 2?) tt+r'l561(rfj-gl w32(6rt,
    112tL2
    Fa 45.81 t6.9t+ t+6.4 !6.90 hr.35 b5.92
    S ,3.5t+ 53.L, 53.t+J 53.3t 52.90 52.36
    Gtl 0.39 O.m 0.gf O.O3 0.00 0.06
    Au O.O2 0.18 O.0O O.25 0.26 O.31
    As 0.00 O.O o.o4 0.03 O.o5 o.@
    As O.0o 0.@ O.0O O.23 l.5O t.l+6
    Tc O.O3 0.@ O,0O 0.00 O.OO 0,6
    sc o.o2 0.06 0.68 0.16 0.16 0.@
    lot I 1@.81 1@.33 100.52 1@.91 100.61 10o.1lr
    6Lt+

    P1rrltor Fo S, (Contbud)

    ilo,{5(uw) ugp(ruo') lro58(1ul 15)


    L2 11
    Fa t+6.t& ,6.6t 46.9? EI.l$
    s 52.L3 9.9J 57.55 53-t5
    ol O.ol o.o0 0.15 o,@
    lu 0.00 0.0o O.m lLEr
    Ag O.ol O.@ O.0O O.o1
    Aa 1.06 O'r4 0.01 O.@
    tc O.S O.m O.oo n'a'
    sc o.@ o.oo o.g3 .- n,a.

    Tot&r 99.66 1@.21 1@.91 1m.66

    2s5hil7 (nu,, 285/3il8 $A2)-


    11L2
    Fc l+1,tb 46.71+ lt6.2L
    s 5?,.t* 59.36 52.98
    Crr O.O3 O.OA O'1O
    Au O.OO O.OO 0.76
    Ag O.OO O.@ O.O5
    As 0.56 o.Vt 0.0o
    Tc O.O5 O.@ O.0O
    So O.oo O'00 O.00
    totar LCF.53 99.5h 1oo'10

    @e!1!er-Ee-E-

    $e551.1(rar) Ln55151(ma)
    - 1 2 9 1.- 2 1 4 5 6

    !c ,g.75 5g.g3 5g.2t 59.6 5g-'$ 5?-n 59.92 59.4 59'n


    s io.q7 Vg.55 39.t+8 3g'7t+ 19't 5 }g'o} tg'r2 39'3t 39'26
    Zi n.a. !r8o tloSo n.f. Br8o BoSo tlo8. EoE' tlo8r

    Cu O.2O 0.13 O.3S O.15 O.O5 O'02 O'U O'10 O'08

    It 0.06 o.o3 o.o5 0.06 o.o5 0.O8 0'06 0'06 o'oL


    Aa O.O3 O'Ol O'OB O.@ O.@ O'@ 9'02 O'00 O'00

    CoO.2O.25O,2rO.[3O'tzO'33O'280'38O'tj
    AB O.Oo O.9O O'O3 O.OO O'@ O'@ o'@ 0'03 O'OO

    cdo.ooo.@0.@o.o0o.ooo.@o.0oo.0oo.oo
    tot r. L(/c..33 99'90 n.ro 9.9s 99'L5 n'25 n'52 99'19 n'lo
    6t5

    P:rrrhotlte' Fe S (Contfuiuad)

    r39651p1(run) (contlnuea) 13965(c)(Ifi1)


    ?8 L2
    Fe 59.93 59.e 59.79 59,86
    s 39.2t, 39.00' 19.29 )8.9e
    7.\ ttoa. n.a. n.ar tr.a.
    Cu 0.18 O.O9 o.2a 0.21
    r{1 o.s? 0.05 o.o5 o.o8
    Aa 0.02 O.gl 0.00 0.o1
    co O.4 O.33 o.3t o.32
    Ag O.0O O.Ol 0.01 0.o2
    cd o.@ o.00 0.00 0.@
    Total 99.68 99.37 n.67 n.48

    14Or.O(Hir2g)
    \23br67'
    Fo 58.77 ,9.38 59.otr ,g.LL 58.e 58.53 57.85
    s t9.37 $.q 39.t0 38.81 t&.tt w.L1 39.?8
    ?.^ 1.05 1,101 L.45 L.t+6 1.58 L.38 1,O8
    Cu O.0O O.0r 0.01 O.O2 O.@ O.0O O.O1
    Nt o.00 0,00 0.@ 0.00 0.@ 0.m 0.@
    As O,3'l 0.08 0.11 O.1O 0.14 O.3? 0.99
    Co 0.00 O.0O O.0O O.0O 0.0O 0.00 O.0O
    Ag DoSo DoBr n'4. tro8. D.8o n.a. D.a.
    Cd tloao tloar llear Ro8. n.a. n.a. D.8.

    rots"L n.r6 1m.97 100.01 gg,5o 100.95 100.45 n.1r

    Srhalerate. Zn S

    13908(cB 5)
    L2tt+5678
    za 65.9t, 65.8 65,86 65.65 65.n 6,.t2 $.Al 66.01
    Fe 0.91 1.0o o.9? 1.13 1.02 2.,& l.m 0.81
    s 32.05 32.& 32.7t 32.28 y.Vl 32.e 32.28 32.tO
    cd 0.13 o.x' 0.13 0.16 0.13 0.17 0.U 0.16
    t{n 0.0? 0.08 o.o7 0.o9 0.06 0.02 0.0r. O.ot
    cu o.o1 o.0o o.o2 0,06 0.@ o.35 O.@ O.O2
    rotel 99.11 99.9L 99.76 n.37 n.2? 99.92 99.tb n.L5

    L39J7(u33) 13959(xtl)
    1231+ L2'L5
    bt 66.55 66.52 66.9t, 55.6t+ 65.L? 63.t& 6t+.23 &.lZ 65,t8
    Fc o.28 0.26 0.26 O.t+3 2.L6 3.65 2.29 2.3L L.52
    s 32.9 32.n 33.LL 32.3L 32.03 33.07 32.69 33.rL 32.65
    cd o.3o o.19 O.23 O.28 0.26 0.25 0.18 0.15 0,2
    l{n O.27 O,33 O'18 O.9O 0.15 0.r.,5 O.P O.3O O.3O
    Cu Drar DoBr n.a. i.a. B.a. Drllr n.a. D.a. [.ar

    Total 100.39 n.77 L6.72 99.16 99.',19 100.85 n.$ 1OO.19 100.1?
    6t6

    Sphalertto, zn S .(Co+tnusd)

    13956(a) (ilHl)
    t2 t4 56 ?8
    ?sl 5't.u 57.64 57.52 56.6? 56.r't 56.7)
    8.72 9.2t, '5.9t 9.62 9.5t
    Fc 9.29 S.86 '6.88
    9.36 9.79
    s 32.29 33.h5 32.8 33.1+6 32.59 33.t+9 32,n 1),U+
    cd o.52 O.53 o,5t o.5j o.r+9 o.r? o.52 0.56
    Un 0.11 0.11 0.11 0.11 0.11 0.05 0.10 0.11
    Cu 0.09 0'04 O.ori 0.15 o.15 0.14 0.31 0.2,

    TOtsI ggS/+ 100.63 99.35 100.51 99.25 n.96 n.39 100.30

    1396101(wr)
    L23 l+5 67 89
    7a ,6.r? 56.b5 56.37 56.L5 56.10 ,5.00 57.03 56.26 55.m
    fc 9.60 9.79 9.75 9.t* 9.50 g.jj B.9tr g.n 10.41

    s 33.5X 32.5e n.r5 ,2,7o 3J.96 32.7L 33.34 32.97 33.6'


    cd o.r4 o,r2 o.53 o.52 O.53 0.r8 0.56 o.52 0.55
    l,tn .0.08 o.o9 o.o9 o.10 0.10 0.09 o.1o 0.09 0.06

    Cu o.27 O.p o.l* O.t3 O.25 0.36 0.20 0.15 0.58

    Tot&l 1@.59 99.e5 L6.?3 99.@ 100.1* 99.19 100.17 99.46 1@.25

    13966(c)(14t1) 13966(d) (rot1)


    1 23 3 L2t lt,

    Z^ ,6.33 56.7e 56.t+7 ,6.78 . 57.LO 5?.59 57.30 57.33


    Fe 9.31+ 9.35 9.6'+ 9.29 8.95 8.91 8.S9 8.96
    s )2.92 33.\l 33.p ,2.W 33.32 33-25 32.3A 33.05

    cd 0.51 O.55 o.19 0.16 o.82, 0.59 o.52 0.62

    Hn 0.10 0.10 o.11 0.1o 0.09 o.o9 0.10 0.10


    R.ao n.a.
    Gu o.22 0.20 0,30 lloSo [oA. llrS'

    99.t3 100.08 lm.IA gg.2\ 100.06


    tota]. n.h2 100.45 L@.23

    139?1(DCU)
    t23 t+56 ?8910
    Ar 6t-e5 64.s6 64.85 6b.49 6t.7s 6t+.t3 62.88 62.32 64.05 63.91
    Fa 2.&, 3.01 2.91 2.66 3.0f 2.94 3.66 \.27 ?.32 3.q
    s 32.OJ 3t.69 32.t* 12.65 32,59 32,te n.:tr+ 12,92 ?z.Ot 33.08
    cd o.J5 O.n o.38 o.2o o.1? o.24 o.33 O.32 O.32 O,32
    Hn o.25 O.22 O.25 o.?4 . 0.31 0.25 0.56 o.3? 0.30 o.5o
    c\r Erao n.a. D.Ar Rrar n.A. n'a' tr.ar n.a. n.a. n.a.
    fotal 99.29 100.2' 1OO.9O 100.2& 100.10 99.gs 1@.u 100.19 100.02 1oo.9l
    6tT

    SphalerLte. Zn S (Contlnued)

    t397r(rfJ2) - 139?4(sH11)
    11 L2345 678
    Zn 63.80 66.2g 65.?8 66.24 6r.?t+ 66.30 66.9L 65.99 66.15

    Fe 2.56 0.?1 0.81 O.?e 1.05 0.89 0.60 0.98 O.9t*

    s 32.15 32,& 32.6) 12.59 32.?J+ 92.50 31.77 32.63


    cd o.25 O.t& O.53 O.5O O.A4 o.Ip o.37 0.31 '2.58
    0.37
    Hn o.34 O.O5 O.O8 0.06 O.O5 O.12 o.o9 0.16 o.13
    Cu n.e. ltrar Do8. Drao llo8o n.a. n.a. n.a. n.a.

    TotaI 99.Ip 1OO.09 99.8J 100.17 99.52 100.21 99.94 100.07 1OO.1?

    13979(Hu1o) 139e2(As5)
    1 27 b5 L2
    Zn 66.38 66.10 67.12 66.9) 67.r+5 55.79 6L.67 66.r.8 6r"97
    Fc o.9J 0.62 0.48 o.55 0.54 L.7L L.72 L.'.12 t.75
    s 3L.62 32,2L 31.90 31.90 32.12 J2.2 32.85 92.L9 32"05
    cd 0.1? 0.2r. O.2l+ o.28 0.72 o.33 o.29 O.31 O.3)
    l{n o.23 0.15 O.11 o.o9 0.26 0.08 0.10 0.11 0.08
    Cu DrSr D.a. nia. n.A. D.a. ll.Ar [.Ao n.a. n.A.

    Total 99.33 99.J2 99,85 99.66 100.48 100.14 99.63 100.81 100.18

    13985(Hs3)
    5 L2 3b5678
    7rr 65.38 65.72 57.0t 6L,7e 66.51 66.92 66.u 66.+s 66.52
    Fe r.7L 0.65 0.73 t.2t+ o.gg a.r+g 0.96 0.86 0.90
    s t2.ltL )3.2L 32,05 32.76 32.& 32.?8 9.@ 39.t3 32.58
    cd o.36 0.19 O.zL o.2+ o.25 O.4 0.32 A.25 O.3)
    lln 0.11 o.10 0.16 o.14 O.19 O.15 O.2O O.19 O.1?
    Cu n.8. 0.08 0.10 O.84 n.&. D.ar n.a. DoE. $oar

    TotaI 99.98 1m.01 L@.29 99.99 1OO.Z' 100.64 100.68 100.92 100.52

    13989(Hc4)
    9r0 t2 3l+
    Z^ 56.to 66.66 6.,+2 65.86 6j.92 66.05 66.q ' 66.r,1
    Fs o.79 O.81 o.8a 0.85 0.80 0.77 0.67 0.86
    s 32.rL 12.8' 32.2L 33.29 32,01 32.1+9 32.u+ 32.55
    cd o.L? o.22 o.4 o.28 o.31 0.2' o'29 0.1?
    Mn o.L5 O,14 o.2t o.2 a.?2 0.23 o.1g o.19
    Cu D.A. A.a. n.a. a.a. n.a. n.a. n.a. D.tr
    lotaI n.gz 100.69 99,95 lm.rO 99,26 99.80 99.69 1@.18
    618

    Sphalerlte. Zn S (Contlnued)

    13991(P64) 14000(Ps21c)
    r23 4 5 6 r23
    zz 67.45 (A.lt, 66.53 6r.7L 67.u| 66.o9 66.r,9 6j.jz 65.rL
    Fe o.13 t.3) 1.16 r.8 L,O7 L.L2 L.l3 l't+5 1-41
    s 32.rL 32.28 32.W 72.59 31.61 32.t&. 32.75 3J.58 3L.85
    cd o.27 O.?2 O.18 o.26 0,31 O.)l+ o.24 O.23 0.30
    l4n 0.06 0.05 0.10 o.07 0.05 o.11 0.05 o.ot 0.0?
    Cu n.a. n.a. n.a. Br a. n.a. n.a. [.ar n.a. n.a.
    ?oral 100.63 100.21 100.86 99.93 100.11 100.11 100.66 100.8a n.L7

    ulm2(Ps21h)
    b56 L23tl- 56
    Zn 65.67 6\.91 66,v1 66.69 66.s\ 66.15 67.oj 67.s7 6j.96
    Fc 1.0o L.66 1.10 0.82 o.rt 0.s6 0.49 o.'t+ t.75
    s 32.rO ?2.27 32.5\ 3t.et 32.26 32.6 32.r+9 31.16
    cd o.33 0,16 0.27 0.4 o.2g '2.7L
    o.22 0.21 o.28 0.28
    Hn 0.06 0.06 0.o5 o.2, 0.20 0.1? o.t8 0.06 0.16
    Cu n.a; n.e. Dra. n.a. n.e. n.a. n.a. D.A. Drao

    Total 99.t7 99.q 1oO.O4 99.93 100.45 100.30 L@.r3 1@.45 99.30

    1&015(rfi5) 14020(l{K13)
    7 r23b 5 L2
    ?A 66.23 67.33 67.U 66.87 65.3r 66.\t 65.& 66.00
    Fc 0.92 o.27 0,31 0,31 1.52 o.54 o.7't 0.98
    s 32.50 t2.28 32.t+6 3r.15 33,5' 72.t7 31.9J 32.28
    cd o.t2 a.?2 o.27 0.26 0,23 0,23 o,25 O.J'
    t{n o.@ 0. 18 o.3o o.3o 0.28 o.3L 0.16 0.16
    Cu llr 8. n.a. n.a. n.a. n.&. n.a. n.A. n.A.
    Tqtal 100.06 100.28 10o.r8 100.89 100.8 99.66 99.36 1@.21

    10 11

    ZrL 65.8 64.?2 6t+.27 6t+.27 64.61 6\.92 65,tt+ 65.01 65.09
    Fc r.34 1.85 1.go 1.85 L.58 1.dl 0.81 . L.26 O.9I+
    s 32.12 3L.96 32.2L 32.@ 32.5L 32.LO 12.26 32.LJ J2.5'
    cd 0,30 0,37 0.36 o.29 o.3l o.3b o.29 O.35 0.r+0
    Hn 0.r5 0.59 0.58 0.61 0.63 0.60 0.16 O.53 O.5t+
    Cu n,a. n.e. lLAo n.t. n.a, n.a. Ro8. n.a. noar
    Tolal 99.73 99.m 99.30 99.04 99.6r, n.o3 W.36 99.28 99.52

    u+@3(Ttt7) 14025(a)(rU2'
    L2 345 1 23
    7.rr 63.27 64.15 62.r,8 63.72 63, ]7 63.8t+ 63.68 63.72
    Fc 2.22 2.O4 2.72 2.28 2.7L L.t16 t.35 r.zL
    s 32.92 39.q t2.99 3J.37 33.@ t3.03 93,2e y.24
    cd o.t1 0.38 o.ro 0.36 0.38 o.16 o.18 0.21
    l,lo o.53 o.ts o.5, o.sb o.55 o.96 o.9? o'88
    Ar irar Drilr n.e. .n.9, n.a. !.a. n.a. n.a.
    lobal 99.3L 100.14 99.U L@.29 100.01 n.45 n.tra 99.26
    6tg
    Sphalerlte' Zn S (Contlnued)

    14025(b)(11226 ) 14c/z5g1$e2
    s)
    L2 3l+ L2t\
    Ur 6t,.?6 65.04 64,65 6t.lo 62.55 53.67 6r+.O1 62,37
    Fe L.53 1.r+5 L,57 L.57 1.8O L.3\ 1.10 1.l}3
    s 32.65 32.LL 32.n 32.32 3t+.o8 33.28 33,57 3r.r1
    cd o.1g o.12 o.15 0.15 o.27 0.25 0.24 0.23
    Hn o.gl o.dl 0.91 0.85 l.r| r.22 0.79 L.53
    Cu n,8. nr80 n.a. n.ar n.a. n.a. n.a. n.a.
    Total 99.9 99.6a 99.t+B gg.lg 16.5? 99.76 99.7L 99.09

    14040(Ht9) &045(H'43) .

    1 234 56 L2'3
    ?rt 53.78 ,t.3L 54.q 51.86 5t+.L3 60.61+61.89 ,g.79
    Fa 11.76 12.11 U.83 10.80
    't+.tC LL.12 11.21 5.69 L.o3 6.5L
    s 33.62 3t.31 33.81 33.59 33.37 33.28 32.OL 33.LO n.8
    cd o.10 o.o? o.otl 0.10 o.o8 0.10 0.o5 o.o9 o.o5
    lln o.g2 1.O3 O.S9 O.72 o.79 0.70 0.69 o.77 o.?L
    Cu n.a. n.a. n.a. n.a. n.8. Iloa. D.ao n.a. n.a.
    Totd 100.18 99.8j r@.?O 99.63 T),4 n.Q 99.06 gg.8 lm,ro

    rrc47(l{r44)
    I L2t
    Zn 59.t5 59.n 59.29 59.8 58.1J+ 59.3t+ 66.13. 6j.n 6b.25
    Fe 1.rt 6.80 6.e, 6.39 7.b9 6.11 L.43 2,O8 1.92
    s 33.2L 33.38 32.29 93.53 33.26 33.2t 33.Ot V2.46 32.3r+
    cd o.o9 0,og 0.04 0.08 0.08 0.10 0.11 0.18 0.13
    Mn o.?4 0.72 0.66 o.T2 o.7, o.Tl o.27 O.52 O.rlO
    Gu n.a. n.a. i.a. n.a. n.a. n. a. n.a. [.ar n.8,.
    Tstal L@.32 100.76 99.10 10O.15 1@.02 99.53 1m.95 100.34 99.0I|

    u.o,+8(r{h45)
    l+5 67 I L2
    Ar 63.93 63.9? 65.99 66,!+6 65.or 65.63 66.36 66.39 6r.26
    Fc z;64 2.t$ 1.10 t.oz L.p 1.00 o.70 0,6 1.20
    s 32.26 32.90 3t.94 32.12 32.73 32.8 31.81 . 32.7L 32.9J
    'cd o.r8 0.1: o.o8 o.og o'09 o.14 0.15 0.15 O.1g
    Hn o.53 0.53 o.t+2 0.39 o.l}6 o.56 o.t$ 0.t8 0.72
    Cu lloSo Drar n.a. n.a. n.e. n.e. n.a. D.a. n.a,
    Tot81 99.5\ 99.96 n.L4 1@.o8 n.1L L@.U n.5L L6.J3 100.30

    14052(wh5o)
    789 10 11 L2
    Z^ 65.3t 65,Ja 6*3o 66.t7 66.17 65.ot4 6j.t+I 60.51 60.63
    Fc 1.28 L.23 L.36 O.rg 0.96 L.33 L.22 6.02 j.n
    s 32.L1 33.03 32.q 72.1r+ 32.66 32.75 32.97 32.2J, .3L.89
    cd o.t2 0.16 o.r4 oJ2 o.r7 o.19 0.17 o.o8 0.07
    Xn 0.60 0.67 0,69 0.lo 0.46 0.65 0.49 o.27 0.93
    Cu n.a. n.a. Doa. n.a. n.a. n.a. n.a. n.e. n.a.
    ?otal 99.t& 100.39 n.78 99.5L 1m,4rf n.96 L@.32 99.13 99.10
    620

    Sphaterlte. zn S (Contlnued)

    14052(Hh5o)(Cont'd) 14O5?(1\d 14)


    3 1 23 456
    Ut 6.sl 6s.96 6r.36 66.0f 65.rn 66.6g 65.65
    Fe 5.67 1.20 r.29 1.3O L.3t+ L.Vl 1.1O
    s 32.tL 32.25 3t.9I 3t.sl 32,2b 3r.rz 32,t8
    cd o.l2 0.50 O.3rl O.3t+ o.2g o.l& o.1o
    lln o.30 o.0L 0.15 o.1O o.o8 O.O5 O.l31
    Cu n.a. D.ar n.a. n.a. n.a. n.a. n.a'
    Tot:l 99.N 99.9' 99.01+ 99.65 99.06 99.37 99.80

    14058(nd lt) uo59(ft1 17)


    L23 ,+56 7 t2
    Ztr 6j.7i 65.7e 66.01 6r-.gj 6i.32 66./,16 6r.2 6j,6? 65.32
    fe r.16 L.67 2.r2 2.q 1.41 L.J6 r.28 l,tz 1.lo
    s )2.O3 32.59 3L.78 3t.w 32.05 32.05 12.25 32.2t n.O?
    cd o.28 0.38 O.38 o.37 0.62 o.rt o.37 o.t+1 O.l8
    l{n, o.og 0,11 0.11 0,08. o.o9 o.o7 0.11 0.08 0.11
    Cu D.ae [.e. l|.8o n.Ar n.A. n.a. lle8o 0.01 0.ol
    fotsl 99,4 1m.52 10O.rO 99.36 n.50 100.48 99.n n.T+ 10o.l0

    1r.06o(ftr 18)
    3b 7e t2'
    Zn 6rr,j3 6l.00 6[.31 65.97 6r+.69 64.03 6j.6 66.o1 66.2,
    Fc 2.O7 L.gt 1.8[ L.39 r.68 2.92 L.zg 1.34 1.16
    s 33.05 32.s1 32.53 12.79 32.3L t3.Ot t2.6\ 32.90 33.2r
    cd 1.O9 0.91 o.@ o.ro3 o.78 0.95 0.36 0.24 0.21
    l{n o.t2 0.11 0.10 0.o7 o.11 0.1& 0.06 0.04 0.06
    Cu 0.00 0.0o o.m o.o2 0.o2 0.og n.a. n.e. D.ao

    Tqt8r. 1OO.c7 99.s1 99.t+7 1m.66 99.78 100.21 99.95 100.54 1m.9o

    U061(nrr 19)
    L'6 7 L23tr
    Zn a+,79 6r.50 65.33 65.6h 6t+,6j 65.6s 65.t+5 6s.a
    Fc L.'A LJ6 O.g3 L.O2 1.50 l.tF L.t+3 1.3ltl
    s v3.o5 32,89 32.54 32.?L 93,05 y.o6 33.rL ?2.63
    cd o.51 0.37 0.32 o.n o.5L 0.67 O.5O 0.6&
    Mn 0,08 0.o7 0.u o.05 o.o& o.o? 0.06 0.06
    Cu n.a. Dra. n,a. n.a. . 0.00 0.00 0.@ o.o2
    Tots]. 99.85 10O.2O 99.29 n.63 n.7\ 100.93 L@.r' 100.29

    rr+O/2([Ir21)
    L23 l+5 6?8
    7a 65.?0 66.9t 66.6 66.:1 66.59 66.n 6.Lq 66.8L
    Fe o.58 O.b9 O.6t 0.66 0.66 0.60 r.6t 0.83
    s 32.e6 32.6 32.t9 3L.t+3 3L.gI 31.98 32.27 32.L3
    cd 0.31 O.t+) 0.48 o.r9 0.57 0.51 O.t& O.41
    Itr o.q7 o.r2 o.10 0.16 0,15 o.15 O.O9 0.06
    Cu R.a r n.s. n.a. n.a. n.a. n.a. tl'ao n.a.
    Total 99.52 100.56 1@.o2 99.17 99.95 99.36 1oO.A/ 100.27
    62t

    Slhaler:tte, Zn S (Contl.nued)

    tAal5(vt27) ' 14o82(Hr53)


    t2 3l+ 56? L2
    7,i 66.22 66.27 66.0, 55.29 6r.92 65.95 66,e 66.04 6s.zA
    Fe 1.03 O.95 1.03 r.75 o.gl L.?l+ 1.4 o.55 0'41
    s 32.13 32,22 3t.63 32.96 32.t3 t2.6e 32.?g 32.5r+ 32.5J
    cd 0.16 0.20 0.24 0.06 0,26 0.16 0.11 0.36 0.23
    ttn 0.05 0.11 o.09 0,03 o.o5 0.06 0.06 o.1o o.15
    Cu n.a, n.B. n.a. n.a. n.a. n.a. n.a. n,a. n.a.
    Total 99.60 99.?6 n.oJ 100.09 99.63 100.60 100.45 99.& 99.08

    1r+086(1t158)
    31. 567 89 l2
    Zn 66.u+ 66.17 64.60 65.7e 65.97 66.24 65.12 65.80 . 65.t*B
    Fe 0.51 0.58 r.57 1.60 1,03 0.76 0.?o 1.15 1.13
    s 33.2L 32.27 32.84 32.78 72.tt )2.r+8 32.49 J2.59 32.U+
    cd o.2g o.2? 0.1.o 0,38 0.23 0.31 0.38 0.18 0.28
    lln o.o7 0.16 0.07 0.o,r 0.06 o.o9 o.o7 o.o9 o.o8
    Cu ira. n"a. D.A. n.a. n.a. n.g. n.a. a.s. n.a.
    Total 100.53 99.84 99.80 99.98 99,8 99.8e 99.{l 99.C2 99.41

    L/|@,2(xt83)
    3l+ ,6 t2 3 b5
    7.rr 66.05 65.47 6b.n 6b.22 6j.90 66.3t+ 66.1r 66.19 66.u
    Fe 1.16 L.3g 2.O3 L.73 0.l|8 0.34 O'l+7 o.tl6 o.5o
    s 32,30 32.67 32.t+9 32.70 32.iD 32.t2 32.O5 32.25 t2.L4
    cd o.21 o.og o.?2 0.30 0.30 0.26 o.2g o.27 0.2t+
    lln o.og o.o9 o.07 0.q7 o.35 0.t3 o.33 o.32 O.3r+
    Gu Drae l|rl. n.a. n.a. n.a. n.a. n.a. 'n.4. n,a.
    Total 99.81 99.71 yt.5L 99.03 99.26 99.69 99.45 n.r+8 n,?:

    14100(!f198)
    6? 8910 1 234
    Zn 6s.6b 67.39 66.32 66,6 66.67 65.56 6t,zs 66.20 66.tp
    FG o.52 0,48 o.37 o.t}o o.39 0.73 o.72 0.67 0.6rr
    s 32.1L 3L,68 32.23 32.L? J2.t3 33.t2 32.68 n.q 32.r,1+
    cd o.30 0.30 o.13 0.23 0.3) o.4 o.24 0.2L O.27
    Hn 0.36 o.?,b o.)7 0.33 0.36 0.14 0.14 O.Og O.15
    Cu nrao a.a. n,a. n.e. n.8, n. a. [.ar n.a, n,a.
    Tot8l n.3t 100.20 99.41 n.89 t@.22 99.79 n.8 100.26 gg.90

    285/3?/6(t413)
    t 56 12 1tri67
    l,rt 6.08 66.07 65.t+6 6l+"13 6\.?7 6h.ob 6j.j2 6r+.9s 65.t+g
    Fe 0.69 0.5& 0.47 1.08 0.60 o.rc o.4r o.53 0.rg
    s 32.78 32.09 31.6L n.rg 93.2? 3t+.tz .33.7L 14.L6 33.97
    cd o.27 0.23 0.76 0.72 o.73 1.14 1.15 O.8O O.75
    ltr o.1o o.1g o.o4 o.05 o.o4 0,06 0.06 o.oro o.o5
    Cu n.a. n.a. nra. n.a. n.a. n.a. n.a. n.a. [ra.
    TotJ,L 99.92 99.r2 t6.37 99.57 n.\L 99.76 100.65 16.51 100.85
    6zz
    Sphaler{.fe. zn S (Conttnued)

    285/3?n(v1t+) zsi/3?/s(tiiz)
    L2 L2
    Z^ $.gs 67.oL 66.6L 66.9s 66.9t 66.89 66.9+ 66.65 66.t+3
    Fe o.?2 4.30 o.3? o.28 o.3o o.t3 o.31 0.36 0.36
    S 3L.3t, 7r.t* 3L.)7 33.V1 ,1.s3 )2.72 32.95 3t.29 32.9t
    cd o.27 0,24 o.32 O.23 o.4 o.33 O.zL o.23 0.26
    l,tn o.36 0.38 o.4o o.27 o.33 0.29 0.46 o,5o o.45
    Cu llo&o n.a. n.a. n.a. n.tr D.a. n.a. n.a. n.a.
    Total 99.24 99.37 g9.or 100.83 99.72 100.55 1oO.8? 99.03 100.1.?

    u18185
    89 10 11 12 L23 L
    ZrL 66.33 65.67 6j.96 66.86 65,13 65.3? 55.52 65.52 65.L8
    Fe o.29 O.\9 0.28 0.21 o.35 o.3L O.32 O.32 o.30
    s 32.83 32.38 32.?7 31.11 32.9L 3\.r9 n.et 34.11 33.67
    cd o.z? o.?2 0.28 0.2' 0.28 0.2o o.22 o.1g 0.19
    lln o.t$ 0.65 o,48 A.27 o.5? o.3o o.t+, o.5o o.t&
    Cu Boar n.a. a.a. nra. lleSr n.a. n.a. n.a. nra.
    lotal 100.15 99.41 99.7? 99.00 n.59 L@.7? 1oO.38 100.64 n.n
    H18185
    56? 89 r23 3L
    Z^ 6t+.93 65.54 65.89 6r.gt 65.8t+ 66.20 65.12 65.10 55.tC
    Fe 0.26 0.25 A.23 0.28 0.23 0.1? 0.20 0.r1 0.r1
    s 33.92 3t+.o? J3.7O T.t+6 73.9t 3t.79 .fi.t$ 73.19 13.77
    cd o.u o.22 o.1? o.2t o.18 0.20 0.20 o.2o 0.19
    !{a L.62 0,6? O.59 0.49 O.5tt o.bt o.39 o,4o 0.58
    Cu tr.8. n.8. n.a. n.a. n.A. n.a. a.a. n.&. nra.

    total 1@.90 100.?5 L@.52 99.7' 100.52 100.?9 99.',19 99.80 t@.Tl

    56 78
    7.\
    'f"
    66.o2 6r.96 &.96 &.a
    o.2g 0.26 o.o2 0,01
    s 3tJ' 32.2tr 33.30 33.12
    cd 0.18 0,23 0.18 O.19
    tln o.5? 0.51 L.21 L.39
    Cu n.a. n.a. llrar n.A.
    Tota1 loo.lrl n.zo 99.@ 99.53
    623

    Totradyulter Bl, Tc, S

    ?Il,
    ';8L5(n$.
    I
    Bl. 6o.9L
    Te 32.t&
    S [.71
    Cu 0.q7
    Pb 0,00
    Se O.0O
    Fo O.0O

    Tota,l 9e.9

    Tatrghdrater Cr\, Sbt St, - Tennsntltcr Cu:2 laa Saa


    ,

    TotFhedr{.tc
    139?9(il111o) ilp56(1tl 15) letrabedrdte
    L234L214'
    c! }g.tL ,p.10 39.55 ' 35.t8 36.L2 36.10 36.51 35'85
    s 25.t+5 26.@ 2r.6 24.8 23.e' 2t+-62 ';6-38
    2L.W 24'75 n'yl
    sb 2o.w L?.17 ?2.6? 23.gg ' 29.4L 25.7L 29,t& zl''5t 29'98
    As 6.81 - g.Y 4.s? 5.vl 0'62 o'8lr o'91 2'3o O'85
    zn ,.96 6.,$ 5.79 6.6, b.gt t+.?9 5'5t &'81
    2-6t z.ta 'l't|3
    2'59 r'96 2't#
    Fe 1.69 L.5? L.72 1.05
    'Ag0.100.090.110.202.362.622.6p 2.322.5b
    ltt o.o1 o.ol} o.o1 O.O1 o-@ o.oo o'05 o'oo o'o4
    'ltnO.SO.@0.OO.mO'OOO'mO'0OO'0OO'@
    cd o.oo o.@ 0.11 0.13 o.o5 o'05 o'oo o'@ 0'06
    rotsl 99.60 1m.96 99.90 !N,37 99.57 1@.15 1m.5f 100.98 16.56

    ?ennantl'te

    612
    cu ,6.t& l&.52 t$.O5
    S 2ro.O? 27.83 27.16
    sb 29.8 0.38 0.15
    Ar O.r2 t8,95 L9.39
    ?,^ 4.81 6.?, 6'7e
    FG 2.n 2.56 2.n
    Ag 1.72 o.U o-o4
    ltt 0.@ o.@ o.m
    ltn o.@ o.@ 0.00
    cd 0.oo 0.0? 0.0?
    lotal t@.27 n.4 n.z'l
    f st
    o.4

    APPENDTX IIT

    PROCEDURES AND RESULTJS OF FLUID INOLUSION


    FILLING TEMPERATURE' FREEZING TE

    AND APPARENT SATIINITY MEAgUREI{ENTS

    PROCEDURES

    reDaration for ootical exanination


    Plates of barite were separated, fron quartz crystals with
    a pai-r of pliers and used. without further preparation.

    Most of the plates of calcite and sphalerite studied ltere


    obtained by cleaving then off sanples with a pocket knj-fe or
    fine cold chisel. other sanples of calcite and. sphalerite and'
    all sanples of quartz uere cut into thin pl.ates and ground' and
    polished on both sides.

    consi.d.erable problens were experienced in polishing


    sanples of quartz (and ore mounts) 4uring the course of this
    thesis. Ilouever, by experinenting with d'ifferent poLishing
    materials, the following technique was finally adopted.

    Saroples nere glued to glass slides wlth1akesj-de cernent.


    The glass slides were attached r^rith candle wax to special
    aluniniun holders to facilitate hand holding during the follow-
    ing procedures.

    Grinding: (1) diaroond lapr water lubrieant


    (2) carborundun powders on glass plates or
    rotating zinc lapst 280, 400 and 600 grades,
    water lubricant (approxinately 3 ninutes on
    each grad.e on rotating zinc laPs)
    (3) Aluniniun oxid.e powders on glass plates;
    12.5yn and, 5[rt gradesl water lubricant (2-3
    ninutes each grade)

    Polishing: Sanples l,rere hand heJ.d' on a Struers DP1O


    nachi-ne using Bueler cloths and, d'iarnond
    pastes.
    (1) 6pn on nylon cloth, water lubricant (arip
    fed), 2O ninutes.
    625

    (2) 1pt on nicrocloth, polishing oil lubricant'


    10-15 d,rops appliecl to dry cloth or less to
    danp cloth before connencenent of run' then
    one or tvo drops ad'd'ed' periodically' 10
    ni-nutes Polishing tine.

    After final polishing cleaning the slides were renoved


    and.
    fron the aluniniun holders, heated., the quartz plates turned'
    over, and the slide reattaehed to the alunj-niun holder. The
    exposedroughsldewasgroundandpolished'asabove.

    Polishingclifficultiesencrrunted'before the ad,optlon of


    the technique d'escribed' above are attributed to:
    (1) use of coarse d.ianond paste ( 15pn) for initial polish-
    ing (folloued by 6pn and 1Pt grad'es)
    (2) incorreet eloths for dianond' grade
    (3) use of oi1 lubricant for initlal polishing stages
    causing difficulties in cleaning. snall quantities
    of contanination lod.ged in open inclusions and probably
    contanlnated' finer grades'
    (/-) insufficient polishing tine on initial stages.

    Plates were generally nade to a thickness of approxlnately


    1nm and naxinurn dianeter of 25nn' selected' areas
    of the large
    plates lrere trinned to fit into the heating and freezing stages
    bygrind.ingonad'ianond.laporatrternativelycutfromthe
    plates,r.lhj.lecenented'onglasssli.de,witha20nndianeter
    dianond d.isc nounted. j.n a d.entists ttrill (KaVo vorksbop hand-
    oi.ece 277 and notor 5?O) .

    Sel,eetion o incluslons their to


    Plates were scanned under the nicroscope at room tenpera-
    ture for selectj.on of inclusions suitable for filling tenpera-
    ture and free zlng point deterninations. suitable fields of
    view were drawn, noting the nagnification (for later na&sur-
    nent of inclusion size from the drawings) and the plate trans-
    ferred to the heating stage on another nieroscope.

    Plates used for filling tenperature neasurements trhere


    nsellotaPrr,
    subsequentlY nounted on a glass slide with
    626

    Flgura IfI-l g Leltz 1350 heattng etage oounted on e LeLtz Sll Lux Pol nlcro-
    soopc rLth vertlcal illuuinator attachuent. Tbe tenpelrture l,s adJuated
    by regulatlng tbo curront supplleil to tlro etage fron the transforuer 1n
    the rlght backgrouarl, andl Ls read dlrectiy off the oater tn the foreground.
    the outer perte of ihe stage an ttatsr cooled.
    627

    retaining the sane orientation as in the d'rawing. Depending


    on the uidth of the sellotape usedr gP to lr plates can be
    nounted on a single 25x76nn glass slide with room for the label.
    in this way allowed for quick location of lnclusions
    l.{ounting
    for freezlng point deternrinations or later reference'
    Dut"rtitttiot of Fifritts J"tpg"ttttt""
    AI1 filling temperatures are liquid - vapour honogenisation
    in the liquid phase. They were determined usi-ng a Leitz 1350
    heating stage. Initially this was nounted on a Lei-tz DIALUX-Po1
    nicroscope fitted rvith binocular head', X10 eyepieces and- X3.5
    and X10 objectives. Special long focus H20 and' H32 objectives
    were later used. for higher nagnifieation but required an
    infinity tube length, not obtainable on the standard. DIALUX-PoI
    nicroscope. This was achieved using a SM-LUX-PoI nicroscope'
    Fig III-1, fitted with the vertical illuninator attachnent and
    binocular head., but still used i.n transnitted light node. The
    NPL (incident light) 5x/0.09P and 1 Ox/0.20P objectives, fitted
    with 6mn and 15mn extension rings respectively, provided a
    parafocal objecti-ve set with the H20 and H32 (ttre nornal
    transmitted light 4 and, 10x objectives give a poor inage with
    the vertlcal j-lluminator in place). 18x eyepieces were experi-
    nented with but gave no better resolution with the H32 than
    the norrnal 10x. Therefore the latter were used throughout.

    The si;age was periodically calibrated usj-ng organlc nelting


    point standards fron a Thomas 66OA-Ut 0 Test Reagent Set
    (obtained fron Arthur H. Thonas Co., Philadelphia, Pa, U"S"A)
    for the tenperature range lrSoc - 328oC and Kr0ra0, for 398oC.
    Precision of filling tenperatures and standards uas found'
    to be vithin t 3oC at approxinately 30ooc. Once the stage is
    calibrated. the aecuracy of a filling temperature neasurernent
    is dependant on the thickness of the sanple used and the height
    of the fluid i-nclusion within the sanple (because of thernal
    graclients set up within the systen). Sone rthickn plates (up
    to 2nn) were used in this study. The accuraey of ind'ividuaL
    measurenents is therefore probably no bbtter than t 1OoC.
    Therefore an overall experinental error of t 1 OoC is assigned
    to the filling tenperature neasurenents reported. in this thesis
    although in nost sanples it will be considerably less but in a
    few perhaps slightlY greater.
    62g

    fl.gure III-21 Freezlag etage oountEil on a LeLtz Dlalu* nlcroscope (aae alao
    Flg. III-5). The tcnperature ia read illrectl.y off the nreter ln the fore-
    ground.
    629

    D erninat ion oJ--gef-initi.e s


    et
    Freezing point depressj.ons (last point of ice nelting
    tenperatures) of i-nclusion fluid.s uere neasured in two instru-
    ments ? a rrhonemadett freezing stage (Fig III-2), described
    below, and a chaix-Meca combined heating-freezing stage
    installed at the Institute of Nuclear Seiences. The operation
    and calibration of the latter is deseribed by Duckwsrth and'
    Robinson (1979). The freeziag point depression results were
    converted. to sal-inities using the equation in Potter et al
    (t9ze).

    Experinental errors in freezing point neasurenents'


    translated into errors in salinity values are considered to
    be within I 0.5 wt.S ltaCl over the range of measurenents quoted.
    These large errors for equipnent r^rith apparently very accurate
    temperat,uTe Ineasuri.ng d.evices are due to therrnal grailients in
    the Ghaix-Meca stage with thick plates and changing gas flow
    conditions between neasurenent of sarnple and standard in the
    llhonemad.ert stage.

    Freeziqg $taee Construction


    The free zing stage, constructed by the Victoria University
    Workshop, is based on the design suggested by Smith (1973) but
    differs in roaterials used and. tenperature measuring i-nstrumenta-
    tion. Figs III-3 and III-4 illustrate the general details of
    construction.

    The bod.y was nad.e by rnilling out a bloek of 62rnn d'ianeter


    PTFE teflon rod. and ad.ding a teflon base plate ineorporating
    a perspex wiridow. A perforated copper gas delivery tube and'
    three copper gauzes, for nixing the cooling Easr are held' in
    pilace r,rithin the chamber by circular perspex spaeers. The
    sarnple sj.ts on a cl6ar clrcular plate sanple holder fron the
    LeLlz heating stage (l,eitz catalogue No.515052) resting ln a
    lip on the top copper gauze. The top wind'ow is also a' spare
    part fron the heating stage (tfre lower rvind,ow, part No' 5150lr3)
    and. sits in a recess milled. into the top of the stage.

    Misting of the top window, encountereil in trial runsr was


    later preventect bY the incorporation of a glass collar surround'-
    ing the microscope objeeti:ve and fed with dry nitrogen gas'
    dertrtter

    o ro 20
    I

    Flgure III-3: Crosg aectloa of the freezlng atage coaetructed by the Unl.veralty
    Uorkshop (see Flg. III-4 for parts deacrtptlon).
    63L

    r/\
    j

    'o
    +(

    'o
    .m
    'o-\ ,3 ft

    ti'-
    \{

    Ft{ure III,-4: Fartg of tbe fre,ezlng etage (see Flg. III'3 for
    illueaglons)l
    f r'top ulnilowl 2rL'6 anil 8 - por'spor spaclag collars' 3'5 andbodyl ! - aoPP"r
    o
    gauueat 9 r donlgtlng colleri 10 sauple holder; 11'stags 12 =
    lorer plate of stage rr|.th bottou rrlndogt 13 = screua, 1{ = Beg dellvery
    with ltcraesi 16 = louatlng screvsi 17 n
    tubsl 15'nounting, trans:Latt'on
    . subale.ge utth blue fltrter'
    Gauqa
    Flow mcfa.rc l(uoltta prwsure)
    Drv rilruan qa,
    frim bhftie'
    P,e,gulalor

    Necdle y6lvct

    rubbe,r
    de,l\very hoset

    Ccitlcd copqer tube


    gewar fillad wrth
    fiquid filroqcn

    glgure III-5: Dtagranatlc layout of freezlng etage apparatue' Dry nltrogea'


    oupplled fron a bottle, le cool.ed by passlng lt through a copper coil
    lnnorsed 1n llqutd nltrogen and than feil to the atage vte c rubber
    dellvery hooe. Tbe latter 1s lnsuLated uith polystyrene collars to
    prevent frostlng and tclng. The tenperature of the stage'ts adjustecl by
    varylng the fl.on of, cold gas wlth the neectle valve. Dry nitrogen (at
    roon teoporature) ls elso supplled to a glass col.lar around the nlcro-
    scope obJectlve, to prevent olatlng. Mlstlng of the bottoo wlndow did
    Dot occur, probably because of, the doublb ulndou arrangouent const'sting
    of tbo botton ninclou of the freezlng stage and the blue filter ln the
    eubatage.
    6lt
    The col-lar rests on the top window' preventing it from lifting
    and allowing exit of the Basr as in the original design. There-
    fore a serles of hol-es were drilled i.nto the body of the stage
    around the edge of the top window.

    The stage is inounted via a set of translational screws


    (off an old Suift mj-croscope) to a perspex substage r,rhich is
    screwed onto the nicroscope stage.

    Dry nitrogen fron a cylinder is supplied separately' via


    needle valves and flow netres, to the denister and' a copper
    coil inrnersed. in liquid nitrogen. The cold ni-trogen gas fron
    the cooling coil- i-s fed to the stage via a rubber tube insulated
    with polystyrene collars.

    Tenperature neasurenent is by copper-constantan thernocouple


    (urade fron 0.005nn teflon coated natched thernocouple wire
    obtained. fron OI'IEGA Engineering Inc. P.0. Box l*Ol+7 Stanfordt
    Conn. 06907, U-S.A.) eonnected to a Comark 1621+ electronic
    thernoneter giving a readible range down to -60oC.

    Freezlsg St,aee 0pergting Instructions


    The systen is assenbled. as shown in Figs, III-2 and III-5.
    Dry nitrogen gas is run through the cooling systen for several
    rninutes to renove all traces of water vapour whj-eh night other-
    wise cond.ense as ice in the next 'step.

    trIhile stil1 naiataining a slow flow Of dry nitrogen gas


    through the systen, liquid nitrogen is poured into the cooling
    coil d,ewar, I'trhen the liquid nitrogen ha$ ceased' boiling
    vigorouely the flow of gas ean be redueed to a level just
    suffi-cient to prevent air backing into the systern.

    The Cornark electronj-c thermoneter can be turned on, its


    batteries checked and the eontrol set to the anbj.ent tenperature
    range.

    . The sanple is plaeed on the sanple hold'er, &e top wind'ov


    seated in its recess and the objective with demister co1lar
    suung into position (tne denister eollars are nad.e to fit a
    Leitz x1A/0.25P objeetive found on the DIALUX-Po1 nicroseopes).
    A slow flow of d.ry nitrogen is supplied to the deni-ster.
    63t+

    When a suitable inclusion j.s located in the sanple the


    gas supply to the cooling systen is opened and the temperature
    r.rithin tbe stage reduced while adjusting the range on the
    eLectronic thermoueter, l,lost inclusions freeze between -30
    and -/r0o0, shown by a sudden reduction in bubble size and loss
    of spherical shape. The tenperature can be raised to near the
    last point of nelting by reduci-ng the gas flow. Great care is
    needed near the end poi-nt, especially if reversi-bility is to
    be tested. In the latter technique, the ice crystals are
    allowed to nrelt until- only a very small fraction of ise re-
    uains, at which point the system is cooled. slightly to allow
    the crystals to regrow and then warned to conplete nelting.
    fdeally this can all be acconplished. r.rj.thin a 0.2 to 0.3oC
    tenperature range.

    Although the scale of the electronic thernoneter can be


    read to 0.1oC and estinated to 0.01oC, its accuracy and the
    precislon of neasurenents are linited by its internal referenee
    +
    junction to f0.5oC. . To obtain greater accuracy a sealed.
    capil.lary tube containing a very snall quantity of double-
    distil-led water is placed. in the stage alongsid.e or on the
    sanple and its freezing point deternined. lnnediately after
    that of the sanple, during the sane warn up run. Thus the
    last point of nelting neasurement of the sarople will be a
    freezing point deviation fron the pure water standard. and not
    a reading fron the electronj-c thernoneter cali-brated. at solile
    other tirne. However, if this procedure is used. care nust be
    taken to ensure that the sane nunber of gas exj-t holes surround-
    ing the top uind.olr renain uncovered. throughout the nanoeuvre
    of shifting position and focus from the sanple to the caplllary
    tube, otherr,riee the gas flow conilitions nay change within the
    chanber resulting in a different teurperature balanee between
    the thermocouple, sanple and cap5-l1ary.

    RESULTS

    of Listine
    l'lethod
    The filling temperatuTe, freezS.ng tenperature and. apparent
    salinity result for eaeh sanple are listed together. The
    sanples are grouped. geographically north to south into the
    various nining centres d.i-scussed. in Append.ix I. They are
    arranged within these groups in order of increasing V.U.ltr.
    $5 \,-

    s,anp.le nri@beri. Fi.eld it'ueborg aad niaEreL id,eutifl.gst:iolt are


    e-Leo given; Thre loE-,at1on anil a br5.ef desori.ptttin of easb
    sar pJ.e is gLven Ln ilX.
    .AppenAix
    Uplts
    Ft]L!qg, aa:dt fve'eztag tenpera-tures arit givea |n d,egrees
    centf.g,radg, !qhe?-g&F a.ppar'ent EaLini,.tles are I'n unlts of
    . equive,I n,t wej.g'h:t perceat eqd.i,uu ehloridE (c,wt-,,$ SeOL).
    636

    ilINBRS NETD

    11966 (ltH2) Qurrtt


    TILLIIIG TEI{PERATURE Prlnary lucluslona (aZ): 365, 371, 181(l) ' 382, J87, 39O.
    191 , 792
    rc1, )93 ()l r 3941 1 s1 '
    395, 396121, 197 (Lr, 798(L), t99.
    400 and L02G).
    Secondary lnclualons (21): 3223'1' 129. 336' 1?7. 1)9131t
    tlli;i, tA2, tt6, 37o(t, and
    )71$r.
    TRTEZ,ING TEHPERATI'R8 Prlnary lncluslonl (26)z -2.7(,to), -2.8, -10.L, -10.5(rr)
    anil -10.?
    Sacondary lnciluclolc (11) : r. -o.7err -0.9'
    -0.t., -0.{(
    -1.0 and -1.1(l).
    APPIRE}II SALIIIIII Prlnary lnclual'ona (261 c 1.5110), A.6, 11.5, rt'6113; and
    1 a.8
    Secondary Inctuslotr! ( 11) : o.:, O.?(3), 1.t(21. 1.6, 1.? and
    1'e(r)'

    rE llol{ATA

    13952 (c810) Quarta


    PILLIIIC TEIPERATURE Prluary Lnblueloag (3712 197. 2o1. 215, 221e), 222,
    2"3(3r' 22l(il' 226' 227 121, 224'
    229 (3, . 211 ,
    e) 272 ( rl ' 2Lt,121 ,
    21rr 2L9. 25t, 25|19;, 255,
    258(ll and 262.
    TNEEZIilG TE}IPERATURE Prluary lnclualonr ('tzlz -0.3e1 r -0.1191 and -0.J.
    TPPARENT SALIIIr! Prlnary lnclualoaa (12)r 0.5(2), 0.?(g) entl 0.9.

    139r, (cB9) Querta


    . Prluary lnclueloas l2llt 21L, 222, 225. Z26elt 227137t
    trILLIilC IEHPERATURE
    229, 2tt' 21t,' 236121, 239gy,
    21t, 253p1. 25!., 261' 263 antl
    265.
    REEZINC TEI.IPERATURE Prl,oary lnclualons ( 6):-0.61,1. -A.1 antl -1.0
    APPAREIIl SAI.IIIIT: PrLuary lnoluelona ( 6): 1.1(l). 1., and 1.7

    11951 (c812) Quarta


    IILLINC IE}.IPERATUBE Prloary l,lclutlonr (le) 18o. 2oL. 206, 210(3rt 217131t
    215py, 21?G), 218121, 219, 221 t
    222G), 223. 221127, 225121, 227t
    232, ztr. 21O(r, 21,J, 2L6, 2L7.
    2L8, 252 end 254.
    Secondary iocluelone ( 6): r?6121. 2oo. 215. 218 and 27L.

    trORTfigRT COLVILIE PEIIISULA

    139?1 (DCl2) Quarta


    rILLITIC TEIIPERITURE Prluary lncluslona (5il2 ZGZ, 263(z). 267, 2711 2?r' 271.
    . 27r. 276, 281. 282(Zl, 281171t
    2g1, 286t 287, 289, 29O, 291, 292,
    293,'), 291ey 29511;,, 296, 297 127,
    )Ao, ?O212l, ?O)pl, 3O9. 31r)
    31 L(L,t, ,17, 326' t29, t3o'
    331 (Z) aad 3rr5.
    Secondary lnclutlons (t1)z 225p1. 21,6. 252, 2',1), 27L.
    275121, 2?8 and 2X9Q,
    FREEZ II{O f 8I'IPERATI'Rts Prlaary lncluclons ( 1): -1 .1
    APPAREIIT SILIITITI PrlEAry lnclugtona ( 1)r 1.9
    87

    1t9'12 (sx11 Qusrtz


    FILLIIIO IEI.IPERATURS Prluary lrclueloac (16). 2r1, 261, 265. 212(zr, 273121'
    Z7l, 275, 282. 2Bj. ZAE121, 292,
    293 a,ail 3O2.

    11973 (sH7) Quartz


    TILLINC TEIIPERATI'NE Secondary lnclualons (1or| 2i5, z5opl, zi9, 260,
    "rr,aad 253121.
    262(z)
    PREEZIilC TBMPERATUNE Prl.Dary lnclusloar ( 2): -0.? and -1.0
    APPAREUT SALIIIITT Frluery laelusloaa ( 2): r.3 and 1.?

    TUAOTI'NU

    1400? (f, ,) Quartz


    FILLIUC TEI{FB8AII'RE Prloery lncluri,oar | 2lz 192 end 25O.

    14008 (K /.) Quarta


    TEI,IPERATURE PrtEBry or Secoaclary ( 5): 184' 187, 195, 196 aad 249.
    'ILLTNC Lnclusions

    14009 (CLl ) Quarta


    TILLIIIC 1E}IPERATIIBE Pr!.nery tnclueloaa (t5rs 221, 229121, 213, 21a, 24r. 251t
    252(r), 253, 255(2,). 256..260'
    261(zr. 262 ;,r, 253(3). 26L,
    265(lr. 268. 2721 273, 271, 282
    cnd 291.
    Secondary LuolusLous (25)t 156, 161, 197. 202. 2a1,, 215. 2f7.
    21912r, 25o, 252171, 25Lo 2550
    256, 258121. ?.61r 263. 265. 27O,
    271, 2?3 ard 291.

    !@r94r4989!A@
    13955 (R01 ) Quartz
    FILLIIC TEMPERATURE Prlrary hc1ual.ona ()7)t, 18)t 18?' 190(3), 19i, 2O5, 2O7,
    2OSt 217131t 2rL. 215171' 216'
    219Gr, 22OO), 221 s 2221 22)1
    224e), 229. 23O, 2tt. 231. 217
    aud 239.
    FRSEZITIC TETPERATI'B8 Prllary lacluai.oas ( 1): -0.5
    APPABEI{T SIIIIIITT Prlnary lnclustoaa ( 1)r 0.9
    11956 (Ro?) Quartz
    SILLIIIC TEI,TPERAIURE Prloary lnsl,ugloug (12)r 'ls?' 195p1, 2o3, 206, 270' 226.
    229, 236, 2t9, 2L1 and 27?.

    13957 (TKz) Quartz


    FILLIIIC TEMPERATUNE PrlEEry lnclualonr (la): 1?6(6),185(3)' 187, l90' 19714;'
    218, 219(Zl. 222, 221. 225. ?2?,
    229,a1. 232, 2311i1, 237, 241(4)'
    212. 213 anal 245.
    FREEZII{C IEI'.IPERATUBB Prlnary loc1u6lolr ( 7): -0.6. -1.1, -1.3, -1.{ and -1.7(f).
    APPAITENT SALINIlY Pr!.uary lncl,uglons ( ?): 1.1, 1.9r 2.2t 2.1 and ?.8(3).

    f1958 (802) Quartz


    FILLIIIG TEI.IPERATURE Prlnary hcl,uoloaa (11): 2t,1, 215, 215121t 219' 25?r
    25191, 262 aad 26!.
    Secoadary Lacluslona ( 8): 77O. 1'12. 1711g,r, 1?5' 185' 200
    .nd 234.
    638

    PETOTE STREAil' COROI'IAIIDEI,,

    1 t98o (Asl ) Quartz


    FILLIlto TE}IPERATURE Prfuary lnclugtone (31 ): 2O7, 226, , 232. 2t431 2l'L111'
    231
    21,5 '21. 2rr, 257 |
    "r8287127, 2a8'
    (r, , 26',|. ,
    271; 281, 28L, 285,
    2g9, 291, 297e) anil 3ol .
    Secondary lacluelons (11 )l 180, 186(2). 187, 188. rPl ' 193121t
    19?, 201 and 275.

    11951 (AS2) Quartz


    Secondary locluglols (16): 166, 177, 186(2), 190, 19), 195'
    trILLIBG TEHPERATURE
    197, 198, ZOO, 207121' 201,. 2O8.
    213 and 215.

    1J984 (flct) Quartz


    rILLilfc TEIIPERATURE Sacondary lacluglona ( l) I 206, 21o, 211 aad 219.

    1t991 (Ps{} carcrte


    18)t 213, 2tO, 2t+1 , Zr,L, 245p1,
    TILLIf,C TEHPERATURE Prtuery Lnelualoaa (1 4) t
    2L9, 252. 258 and 261'
    SeeontlarYlncluclong ( 1): "16lll,
    168
    REEZIdC TEHPERATSRE Prtoary Lncluglona ( 2): -0.9 andl -1.4
    APPTREIT SALINI?T Prtnary luclusloar | 2)2 1.6 anil 2.4

    13992 (Ps5) Quartz


    FILLINO TEilPEBAII'RE gecondary lncluslona ( 2): zra(2)

    1399' (PS?) Calclte


    FILLI}IG TEI.IPERATI'RE Prloary lnclugloaa ( Z) I 180, 2oa. 2Or, 2O8, 211t 213 and
    2't5.
    Sccondary tnclu6lolr! ( 1)t 1?1

    13991 (Ps7) Quartz


    FII,LINC IEUPERATSRE Seconclary iaclus!'ona ( {,): 1971 2OO. 2OZ and 249'

    11995 (Psto) Quartz


    FILLII'IG TEMPERATI'RE Prluary laclueLons (t6)t 257, 258. 261, 263171, 265141,
    "5A,
    266. 268(21, Z691zl, 271. 27)31t
    275. 2??, 283(1.l' 288(() , 292t 29-1o
    306. 308' t1O. 312, 311, 311', 316,
    J17, 3'lE, ,2t. ?27 and 331121.
    IREEZ IIIO TEI'IPERATI'RE Prhary hclutr.on! (11): -0.?1a;r -o.9131, -1.0(3) end -1'3
    IPPAREIIT SALIIIITT Prlnary lncl'ualonr (rl): r .1(lr' 1.6(r), 1.71t1 and 2.2

    11996 (PS1{a) Quertr


    IILLIIIG IEHPERATI'RE Prluary hcLual.ons (25)z zt6, 222, 221161, 228(z), 214111t
    25O . 26? , 27). 27 4. 275 , 281 ,
    28). 285. 288(Z), 2JO and' 29J.

    13991 (Pslf) Quarta


    TILLIIIG TEMPERATI'RE Prluary lnclusLong ll1)2 25L, 256j 258. 2r9. 260. 261. 262'
    26J' 268.27O' 2?1,272c 27)131o
    27l,;,r, 275, 276' 278, 285,
    288(2), 291(2r' 297lzl' 299,7o2
    enil 303.

    14005 (Ps2f) Quartz


    TILLIIIC TEHPERATUIG Prioary lnel.ugl,onr 111)t 2l,l'. 2r3, 25L, 25819,1, 261
    151t
    26i iad 271 (z).
    639

    Secoadary lsolurlo!! (21): 11?. 1?1' 180, '184, 185(a), 186'


    1s8(Z), 195, 2oo(17, 2o1121, 2O1,
    2o5; 426, 229, 2t'2 arit 261 -
    FRE$ZI,IIG TEHPERAIURE PrlDary lncluslona 2): -0.9 and -1.8.
    Secondary lrclualous 2rz -1.5(2,
    APPAREI{T SAI.IIIIT! Prlu&ry lnclusLona 2): 1.6 aad 3.0
    Secondary laclualons zlz 2.6(zl

    11,006 (Ps26) Quertz


    FILLIIIO TEHPERAfURE Prl.nory loclualoar lstlt 215$r. 221. 23o' 251171,, ?1?trt_,--
    265:-268(21, 27,pl, 271t 2802
    -283t
    2sE(r), 2901a). 291t 29212t, l9llzl,
    zetiti, 2e6. 2e7(r, 3oo(l)'_?12'
    )or; 3o4. 308(l), 31O' 31t,, t1',l
    4A t22-
    PREEZIIIC TEI.|PERTTUAE PrLnary Laelualoar (13): -0.?1r1, -1.?,'1.5(lr, -1.?r
    -1.9(f) aud -2.1121. - _
    IPPAREIIT SALIIIIII Prlnary llcl'ualoBs ItSle tJ1)y-, z.z' 2.6(ll' 2.8r 1.2(zl
    aud 1.512).

    T,HAIICAPOUA

    1r91o (lte9) qualtz


    FILLIttG IEt.IPERATURE Prfuary lnclual'olg ( 2): 190( 2)

    BROKEN HILLS

    13950 (TR9) Quartz


    TILLIIIC 1EHPEBATURE Prloary tacluslons (15)z 2OO' 21Or 2l5er, 216, 222. 223,
    221121, 225, 232121. 213, 235121.
    236i2r' 2?9t 213131o ,"al\Zl' ?!rtn,
    21',t"-2l9, 255(j). 256, Z6Z, Z1J
    etd 271.
    (12): 210(2) , 215(31. 211. r'l.d 222'
    Secondary 1ag1u61qaa
    (11): -0.i,'-0.+tzj "tz(Sl.
    -o-e121 and_-0.?
    FREEZIIIO TEI{PERATURE Prluary lncluslonc '
    APPARENT SALIIIIIY PrlB.ry lnclusl'one (ff)l o.f, o,?(zj, r.1(z) anrl 1.3

    11911 (TR6) Quertz


    FILLIIIO IEUPtsBATURE Prrnlry lscluoloaa l25lt 203. 2oLi)1, 2o5127' to5:-tt?1-
    216G1, 21',t, 221 , 222. 223, 232'
    233, z)5, 277, 2t+2t 21), 215t 255o
    268' 283 antl 293.
    Seconclary lnclucloaa (25) 221. 222' z3|1zl' 275711'
    236' 2V7'2)s"?9'
    13y,2)9 12y,21L.215 | 1l'
    246rzr' 251 arod 289'
    I}REEZIIC TEHPEBATURES PTIDTIY lucluslola ( 6): -0"i1'-o'5p1' -o'5' -l'1 aril -1'3
    APPAREIIt SALINITI PrLnarY lnclugl.oag ( 6): 0.?, O.gtZi'-1'1' 1'9 aad 2'2

    ilEAVESVILLE

    11940 (!t26) Quariz


    PrlDarY lncluelone (10)3 '188. 206' 209' 212, 2ltl/), 21 I aacl
    FILLII{G TEI.TPERATURE
    2t1.
    6to

    1t9L1 ltttl) Quartr


    ?IL[I!TG TEIIPERATI'RE Prlnary lnclualoaa (2ol| 232, zJ9el, 2t't o 2A3121, 2t l,
    21r(Zr. 2L9. 252. 25)p, ond 25115,;
    FREEZING IElIPERATI'RE Prluary LneLueLonr | 7lz -o.lpr, -o.L1;;,, -0.512) and -0.6
    APPARENT SALINITT Prlnary lncl.ueioac ( 7)! 0.5(2), o.7(z)' 0.912) and 1.1

    1t9L2 (!Ii2) Quarta


    FILLI}IC ItsI{PSRATURE Prloery Lnclusl.otr (2O), 193, 2O7j 215. 229, 2)1,(Z), 239.
    2Lt, 21.6n 21,8, 2t912y, 25J, 251,
    255e), 258(21,265 a',.d 27t .
    TRESZI}IO TEilPERATURE Prluary taclusLona ( l): -0.1. and -0.5121
    IPPAREITT SILIIIII Prlnary lncluslona ( 3lz 0.7 aad 0.912)

    1t9lt (X39) Quartz


    FILLilC IEHPERA?I'RE Prlaary lncluelona ( zrt 221 and 22L

    1t911 (!147) Quartz


    PILLIIIC IEI|PERAIURE Prluary lnclual.ons (30)t 190, 191(2,1, 19L(jl, 195121,
    196(S), '197, 2O1, 20t, 2OL. 205r
    206. 212. 215. 231 anat 219.
    FREBZIIIC TEHPERATITRE Prlnary lnclual.onr ( 6): -0.1, -O.2(2r, -0.1 an<t -0.112;.
    IPPARE!|I SALINIII PrLrary inclualorr ( 6): 0.2r 0.3py, O.5 aarl 0.712),

    119i,.5 (!128) Quartz


    FILLING TEUPERATIIRE Prlrary Lncluatoaa (141. 126, 2r5(lr, 217, 2151.31, 22212y,
    225. 2)1,, 211 alld 281.
    Secondary lnclualonr ( tlr 215b,
    FREEZII{C TEHPERATURE Prluary lncluolong ( 2): -0.1 and -0.5
    APPAREIIT sALItlITl Prl.aary tucluslona ( zlt O.7 and 0.9

    139L6 (ua6) Quarta


    FILLITC TEMPERATURE Prlnary lrclurloas (11)! 206, 2o8, 21o) 2tL(lr, 215(ll a!'d 222.
    NEEZII{C ?BI{PERAII'RE Priuary hclurlone ( 6)3 -0.,1,(11 and -0.5
    IPPAREIIT SAf,IIIITT Prluary Laclualong ( 6): o.?15y and 0.9

    I,IARATOTO

    13916 (cN')
    (17rr 22o, 2501';,
    TILLIIIG ?EMPERA?I'RE PrLoary LncJ'ugl,ora 251
    1zl, 252. 251,,
    256121, 257, 258, 260(f.r. 263'
    265 and 299.
    Secondary lncLualona 1 91t 21Op)' 25O. 256, 260, 273. 275'
    276 ard.277.
    FREEZII{G TE}IPERATURE Prlraly lnclueloar ( 3)! -o.j(3)
    APPAREIIT SALIIITI PrLuary Lncluglonr ( l)r 0.9
    tr917 (tll) Quartr Cora
    SILLIIfC IEHPERA?URE Prtnary lnolualora (14)r 222. 23o, 256, 259,262t26)131t
    267. 268, 272, 273,278 ind 282.
    Sccondary lncturlona (13)r Z6op), 261, 26212r' 261, 26r'
    267t 26812yt 27o1p't and 298.
    ?REEZMG IEHPERATURE Prloary Laclqal.ons ( 2): -0.1 and -0.6
    IPPAREIIT SALINITY Prlnary lnclugloar ( 2): 0.2 and 1.1
    Quart: grorth roac around cort
    FILLI$GTEHPERATURE Prlnary lnclusLou ( 6): 255, 258. 259(Zl, 26O anlt 276.
    Calclte zone
    FILLIIIC IEHPEBATIIRE Prloary lacluslonr fttlz t95, 2O81"1o21O127o212t222t235t
    239, 21,O. 247 (2, .ZLi ZLA,z51
    , fi53 t
    6l+r

    2rB, 26O(Jl, 261, 26212y, 26a,


    271. 277,278.281'288'29O ead 306.
    FREEZIlIC TEIPERATUIIE Prl,Eary lacluelona ( 2): -0.1 ard -0.2
    APPAREIII SALIIIITY PrlEary lnolusl,ons ( 2): 0.2 and O.,

    1391s (x2 calcit6) Calclte


    FITLIIIC TEI{PERATURE PrlBary i,nolueloaa (40): 230, 23a. 239, 21o, 212. 215p1,
    2t'1 , 218(zr, 25o(r), 251 251,t
    12y,
    256, 258or, 260ol. 262(Lr, 261,
    266 ,r, 267, 268, 270121' 275,
    27812yt 29O add 292.
    TREEZIUG IEITPERATURE Prloary luolusloaa ( a): -t.1 12;, -1.2 and -1.7
    IPPAREIIT SALINITT Prtoary hclualoas ( 1): 1.9121, 2.1 snd 2.8

    13919 (r{2 quertz) Quartz


    FILLII|C TEI.IPERATURE Prluery laclullosa 129)? 2O2. 2O9. 2lO. 211. 211. 218, 220(2)
    22112yt 222.221) 225.228| 229Q,
    ,3o(tl,
    232, 2)712;r 238, 210.215
    219, 261 and 259.
    Secouilcry laclusloug (22r. 21o, z18t 220121' 222, 226. 22812'1'
    2)o(lr, z1o(3), 21812y, 25o12,1,
    252 and 255e,
    FEEEZIIIC TEHPERI1URE Prloary lqclualoll ( 5): -0.1, -0.r(2)' -0.1 aoil -0'!
    Secoadary Lnclualous (27)s O to- 0.11151 and -0.3
    APPAREII? SALINITI Prloary LnalusloBs ( 5)z o.z, 0;5(2), 0.? gad 0.9
    Seoondery lnclugloar (27)z 0 to 0.2126) aad 0.5

    13920 (t{l) Quartz


    TEMPERATURE Prluery lnolugl'oae? (Silz 2Xoer.zLO. 2t3, 2ll4 21812,1o :

    'ILLIUC 250 ,r,251 e),252 ( 1r,253 121,


    255(Zr. 258. 260(;.1,262157, 265t
    26814)r 2'10. 2?2t 27537.27'l' 2?8. .
    280(6),285,299.3oo 121')O5,22o rad 123'
    FREEZIIIC TEI.IPERATUSE Prinary tucluglons? ( l): -o.t,r; aucl -0.?(z)
    APPARENT SALITI?Y Prlnary lnclueloas? ( l): O.z,r, anrl 1.312)
    13921 ( r,r4)

    PILLryC TEHPERATURE Priuary ltrcluslols ()7r. 215, 222e1. 226, 233. 2)512yt
    2l2(ll, 213, 215(31, 2L7t 218121t
    250
    121
    ,251 ,r, ,252 e) .253171,255 t
    25siZ62 ,26L ,267 .268 ,269 ,27O ,
    el
    2?8 aatl 290.
    FREEZIIIG TEHPERATURE Prlnary lucl'uaLoas ( 5): -o.t' -0.4(z) 8ed -0.?(Z).
    APPAREII1 SALINITI Prlnary llclurlora ( 5)r 0.2r o.Tpl aad 1.t12).
    11922 (!.t5) Quartz
    srllnfc TEMPERAIURE prtuary lactualoag ,rrr..
    :\:0,,1r^f,,,r"ro1,.1rrlr"1to\r,rI;olt",
    2L, ,;.r,2L7, 2t B 121,25o 121,25]
    '
    252 12r' 2JJ,25L 121'255 137 t257 121,
    25Ei21,259 ,26o 61 ,262lzl
    '26),261'
    265 i 21, 266, 257,268'269 1 21,272'2'l 1,
    27 r;27 6,28o,285 ( 286' 288 ( o
    31, a),29o 131
    293, 295177 and 300'
    Secondery lucluslons (21 ) . 2o8, 21 6, 27 b,22o,225 111'2L1.215'2 17 .
    2 4a ,252 ,260 .261 26',1 ,?58 ,269 .
    121 '
    272e1 and 2?5.
    t'RgEZINC TEt{PEIiATUnES Prluary lscluslosg 5): -0.'i r -0.2.r -0.5, -'1 .1' aad -2.0
    Sacondary lncLuolol r all aear 0.
    APPARENT SALIIIITI Prinary lacluelooa ( 513 o.2t 0.3, 0.9, 2.1' aad 1.4
    Secoudary lBclullonr r all aesr O.
    13923 (H6)
    rILLIIC IE}IPERATORE Prlrary lnelualona (92): 230121, 2L1, 2L2(31, zt5e)r 25014yr
    251 , 25212,1t 258,260, ?61,266,
    270(5)' 271 277, 278 Q), 28O, 282.
    '
    290 and 292.
    FREEZINC TEHPERAIITRE Prluary lnclualona (6) : -0.1t -O.2t -O.L, -1.01t1 and 1.'l
    APPARENT SALIIIII Prluary lnclucloae (6) ! 0.2' 9.7, O.'lt .7 121 and 1.9 '1

    11921 (HBb) Quartz Quartt bantl closcto culphlde band


    FILLIIIO TEIIPERITURE Prlrary lncluelona (1$lr 225e1, 228(2). 231, 235. 239er,
    242, 2Lr, 25l(lr, 253, 255, 26O,
    264 and-267,
    IltcruailLatc Quartz bend
    IILII,MC TE|{PERATURE Prlnary laclual.oae (341 ? 228. 2)'l' 2)8' 279, 2tO, 2L2,
    243e), 2L5 (r,2L9, 251 121. 252.
    257
    e), 251, 255 171,256.25a,
    259 (
    l,l.26t' 266, 267,27O,27 3,27 5,285 (21
    FREEZIIIC TEHPERATITRE Prlncry lnclual.ona (tl)t -0.1161, -O.21t1 and -1.2
    APPARES? SALIIITI Prlnery laclusr.oaa (11)t 0.2(6). 0.3(4) and 2.1
    Quartr band furthcr avey frou eulphldc band
    fILLilC TEIIPERAIURE Prllarylnclualoaa 6).. 275,278,280,29O,292 aad 295.
    ?REEZfilc TEHPERAIURE Prlrary lnclus!,onr 1): -0.2
    . APPAREII! SALII{I?r Prhary lacluelone 1):0.3
    1192' (t{9)
    FILLINC TEI{PERATIIRE Prloarylnc}ualonr (16lz 258,260,270,27',t .275,27I (4; ,280121
    '
    281 ,282,28r,28 I ,285,2861 2; 288 ,
    121 '
    290 ,2r,291 (
    3r,292 ( r,29 3,29 5 t299 .
    3O1
    ' t09, 110 and 320pl.
    Sccontlary lacluetoae ('l!) r 190 .235 1237 .219 ,25O (2, .26t r
    '260
    267,269,275,278 and 286.
    IREEZI}IC ?EIIPE8ATURE Prl.uary lnclugloar ( 1)l -0.3
    APPAREIIT SALIIIITX Prhary !.ncluatona ( f)r 0.,

    13926 (Hlo)
    FILLIIIC ?EUPERITURE Prloary laclualoar (60): 172.178 ,180 ,'tj2,255,260 (Zy ,261 121 ,
    262 (1, ,26L121,265 (tt) t266,267 111 t
    269
    1
    g t270 (2,t,2?1 ( 1.1.272,27J ( Jl.
    2?J (il, 276 | 28O (5).281'282'285 (rl
    ead 2901r1.
    FREEZIIIC TEITPERATORE Prlnary lnclualone ( 2): -o'5( z)
    IPPARENI SALIIITI Prlnary lnclurl.ola ( 2)z o.9 (2,

    11921 (H11) Baniletl quartl Quartz baud closa to culphlile band


    FILLMG ?EHPERATURE prluary laclualonc (3,}rz ZtO,Z\","45,Z5O1Zlo2i214,2|j.2|6.
    25.7, 260 (
    i.261 .262.2611 26{1
    41
    .
    3;'
    265 (Z),268,270 (tl and 275.
    ?AEEZI$C TE}IPERTTURE Prl,nary laelurtonc ( 1): -0.1
    IPPAREN? SALINIIY Prhary lacluetona ( f ): o.2
    Interocilletc quart! band
    FTLLIIIC TEMPERATURE Prllary lnoluaLona (tt ): 259 el, z60
    21,261,262 ( 2r,26r,266 |
    1
    261 and 275.
    Quart'a bandfurthcr avay froo aulphlde band
    rILLIUC TEI{PERAII'RE Priaary lnclusloar | 9lr 246,25O) 251.255,260,262,26),
    268 and 272.

    13928 (Mr9) Quarta


    FILf,IIIC TEHPERATUNE Prl.rary hcluel.oac (1J), 239, z11t 218p1, 260(4). 261,262,
    263, 265, 267. 268(ilo 269, 27O111t
    272(
    t,), 27) 131' 277. 278 (5r,279'
    280p1.281 ,283,289.292,295,)10 aaal 11 5.
    FREEZIITC TSHPERATURE hloary lnclualona ( t r t -1 .5 and -1 .6e).
    el
    6t$

    IPPAREUI SALIUITI Prlnary lnclueioae I lrt 2.6(2, rnd 2.?12).

    73929 (M28)

    TILLilC TS|.IPERITURE Prluary lhcluslo[8 ('t 8) t 225'23o t232 c217 131'218 t219 l3r.
    250(Zr, 251' 255, 268' 27O' 2'17
    auil 2El .
    Secondary lucluslona Dt 199. 2OO. 2OZ alrd 205.
    I'REEZINC TEHPERATUIIE Prlnary lncluelosE ,rt -o.3(2, and -0.4
    APFARENl SALINITI Prlnary lneluslong 3)t 0.5121 and 0.7

    13930 (H8r)
    PILLIIIC TEI'IPERATURB Prloary lncluslon 0)) t 210 ,215
    12)
    ,248 1zl
    '25o
    ,252 12y t
    251 J5 1 ,255 t z5 6 r 257 o
    121
    .
    260(4) 261.263.265, 268 1g1t
    269 t27 2 1, z7 5 27 8, 287 .
    121,2, 1Zl.
    FREEZ I I{C TE.{PERAIURE Prlnary ltrc1uglols ( l): -O.3e, aad -0.5
    APPARE}TT SILIHITI Priuary lnclusloaa ( :): o.5e) aad 0.9

    11915 |Hz?l
    FILLING 1E}TPEBAIUBE Prlnary lnclurloas (tZ)t 22 4 r22'.1, 211,233, 239 . 21O. 2 11 .
    212 (21,213
    Gl .zLt, (j, .215 '
    216
    er,zLT ,2L8121 t219 121t,250 o
    252, 253 12r,z5 L o 25 5
    121,256 121,
    261,27O'213.288(Z) end 291.

    trOHATA

    ltgL'l (f,rl5) Quartz


    rILLI}IC TEI,IPERNTURE Prluary lncluElo!t (3tr t 1 11.1 19.1 52.1 6?'1 86. 1 88' 1 90'
    . 191Gr,19116;)195,201.206.
    21O .21
    1 g1,21
    1 ,.21o.4?1 .
    121,213
    t
    221, 221 2) 1, 211 .215' 272.27 3'
    282 er.d 297.
    FRESZIUC TEI.IPERATUBE Prlaery iBclusloBg ( l): -0.4, -1.0 and -1.8
    APPARE}IT SALIIIIlI PrJ.oary lneluglons ( !): 0.?' 1.? and 3.0
    Calclte
    FILLINC IEHPEBATSRE PrlEary LncI.uelons 11Sl z 215 p1 . 21 8 .23O ,23t ,223 'i11121 .
    ,35 ,239 ,21'O,2lr1 ,212 ,21) ,
    e) 127
    2t Lg1,2L, (il,250,251 rtr,252lZl,
    25 1;258,261,26i,26 1,,266,272 tzd 277.

    TREEZII{G I8}TPERATURE Prluary incluslols ( 9): -0.9, -1.0(l), -1.1(4) snil -1.?
    IPPARBIIT SALI}IITI Prlnary loclualong ( g): 1.6'1.?(l), 1.9(4) and 2.E

    13918 (x818) Quartz


    FILLI}tC 3EI{PERATURE PrlEsrlr Lnclurl,olr 112t. 219, 221er, 239. 211, 243,
    211tet, 2L9, 252 and 261.
    trREEZIITO TEUPERATURE Prluary Lnslusloug I tlz -0.i7' -0.6, -0.?(41 auil -1-?
    TPPARENT SALIIIIlI Prlrary LnclusLono ( ?): 0.9. 1.1, 1.3(4) ard 2.8
    Calclte
    FILLIIIC TEHPERATU8E PrLnaly t aclusloaa (38r. 212,235,21,L,215 1g'l.2l,9 121,251'
    259
    25 1
    61,25 5 er, e),26Q .261. 171'
    262,263,265 (r1. 266,261 121,269 (t),
    .t 275' 278(r1,28) aud 284.

    ltglq (Ko10) Quartz


    FILLI}|G TE}TPERATUBE Prluary lnelurtons (28rr 231,231,2J1,236p1,2)91g1'211'
    211.217 .252 (5y.255,258 c 2S'J,26 It
    268,269, 2?1 ead Z'l5gy.
    Secondary laclusl'oad lZll t 2"7 p1,22s lzr,229 ( 0,27o,231 127'
    2fi ( 23 1 2)6 L2,
    sr, 121,235 er, 121,2
    .- 215, 2161 217 asd 258.
    6ll+

    TREEZING TEIIPERATURE Prlnary lacluslonl I -0.5 and -1.8


    APPABEIIT SALI}IIfI Prlnary lnclualons : 0.9 and J.0

    YAITEXAI'RI

    t {010 (Ifil ) Quartz


    rILLI}IG TEIIPERATIIRE Prhary lucLugLoos (te): 216. 21,1 . 2L5, 251 1r1' 252p1,
    253(lr, 25t,151,255' 216' 26Q'
    261. 262(t),265, 26815y, 269,
    27O.272(jr, 273(Zl. 271, 276'279,
    280,281 (21. 282, 28i. 285 and 290.
    Secoodery lnelualons (4&): 229' 212G1, 2)9. 242121,21,)p1,
    2Lt,, ZLt, 2L9, ZjZ, Z5)13y, Z5L,
    255, 2r7(D, 258(ilo 259' 261 16t
    Z62pl, 26t(2r' 2?1, 272, 27L;
    275(lr, 276,. 279. 282 aail 2891r;.
    FREEZ IIIC TEMPERAflIN.E Prioary lBcluLoa, ( 1): -0.4
    IPPIRETT SAI,IIIIIT Prluary Lnclusloaa ( 1): 0.7

    1t011 (Hr2) Quartr


    PTLLIIIC TEI{PERATI'RE Prluary lncluslonr ( 38) 2 2t 4,216.2 11,.2L6 ( 5r'2t 7 t2'!8 127
    t
    2[9 ,252,25)
    121,25Lt25?
    ,219 p7 ,
    261 26t 26 L
    Gl, Q)' | 11,26r'267,271 )
    272e,1, Z71p) and 281 .
    FfiEEZING TEIIPERAII'RE Prluary lacluslonr ( 2): -0.3 anil -0.4
    IPPTREIl SIL$Ilfr Prloary Lacluglonc ( 2l: 0.5 and 0.7
    14012 (urr) Quartr
    rU,EI}IC ?EHPERATI'RE Prluary ilclutlons ( 47) ? 227.zLo.212.211 o2L5 .2L6
    12,1
    t
    ZLT
    121,218,25o 1z'1.
    252, 25711yt
    251( t 255,256.258,260'261,
    ),
    262Qr, 26)141' 26l(rl, 26J(zl'
    266,272,27),276,292121.'296 anil 3t\4.
    TREEZIIIC TEI{PERATURE Prlnary iaclueLona (10)r -0.5131' -0.6' -0.9r -1.o(a)'
    -1 .re) and -1.9
    IPPARETT SALilITI Prluary tacluslour (10): 0.9111, 1.1"r.5,'t.7121, 2.2(Zl
    ' and J.2

    11011 (ltI 4) Quartr


    TILLISG IEMPERATURS Prl.uary laclusloaa (tZl: 1 7 1, 1 90, 21 0,21 1, 227, 229 ( 2)'2t2,
    2)5.217,218 (rr, 2L2t2L) 12y,
    244p1 t 2L5(Zl,2L9 12y.251 ,252.
    25A(zr, 256, 258, 261 2l, 262,263.
    264,.267,268,271 (
    0.27 L.27 5,279 rad 286.
    FREEZI}IC TEHPERAIURE Prtoary Loclualona ( 8): -0..1(t), -0.5(3) and -0.9
    IPPAREIIT SALIIIIII Prl,rary Lnclugloac ( 8): 0.?(n)' 0.9(l) and 1.6

    tlolt (tfi 5) Quarir


    TILLII{O TEI{ PERATI'RE Prloary lnclugionr 159rl. 206.224,,22' (rr,226 (31,27i.131 '
    2)9 (
    I't,2 L2 1 Zl'2L1,2L1 121 t2 48,
    219 (, t25o ,251 ,25L131 ,255 ,
    258 (Z),261
    nr 1262,26) (51,264121,
    2651'1' 268(t) , 269p,yt271 anld, 272.
    Secoudary laclueloar (2J): 22o. 222(2r, 226. 216(i1. 238t212,
    24,t121, 25L(d, 255121. 2J7. 262'
    267 atd 265.
    FREEzIttc ISHPERAIURE Prluary Lnclualonc (12): -o.t1zl, -0.6, -0.7(z)r -0.9131r
    -r.012) aail -1.1121.
    TPPAREIT SALI]|III Prluery lncluatona (12)r 0.?(r). 1.tr 1.J(Z), t.6lt)'
    1.7(2, end 1.91.1.
    gAIg!

    13911 (!,hz1) Quartz


    FILLIilC TEHPERATORE Prlnary laeluoloss ( 14): 1 58r161 , 166, 167, 't68 o 1',l1
    127
    185. 189 and 190121, 191, 19,
    abd 200.
    1 4oro (oJ1 ) calclte
    FILLIIIC IEHPERA?URE Prlnary lacluaLouc (20): 212, 216, 219, 2210 228t 23112yo
    212, 2L7(3r' 21t,151, 217, 252,
    253 o,nd 251.
    FREEZIIIC TEHPERATURE Prluery luclueloar ( t) r -0.?, -0,9r -1.0 aud -1il
    APPAREIIT SALI}IITI Pr!.oary lnclugloas ( 4) l 1.),1.6,1.? end 1.9

    14Ot1 (cJ2) CalcLte


    FILLIUC TEHPERATURE Prlnary lnslualons (f4): 7 69'176,1 79 .1 e5 (2r.19O. 79?,'197.
    2O3o213p1,215, 216 and 219.
    Seeondary luclualola ( 3): 187, 2o3 aad 205.
    FREEZIIIC TEHPERIIURS Prluary laolusloac ( t): -o.9
    APPANEUT SALIIIIlI Prluery lnclualona ( 1): 1.5

    1l+o32 (oJt) quartz


    FILLIIIC TEHPERATURE Prluary lncluolona ( a), 229, zLt s:ld 21,1,(2).

    14035 (l,tblb) Quartz


    rILLI}IC TEI.IPERATURE Pr!,rary laclueloua ( 3): 229 (2,
    Secoudary furclusloaa (18) : 18712;r 2o5, 210(3rr 21515;,
    21912r,221,229. 272 l;td' 293.

    11016 (llh8) Quarbz


    TILLITIC TEMPERATURE Prlnary lnclugloaE ( 1): 271
    Seconilcry lnolualons (11) : 189 ,221 (2, '225 121,229,2301 21 .
    23?. 21t au.d,23L.

    11ot7 (Wh10) Quartz


    . TILLIIIC IEMPERATURE Prluary lnolualoaa ( ?lt 199 and 20i1,
    Secoadary Luclugloas ( l,lz 116, l'l?e, aad 193.

    14019 (Whl 5) Quartz


    FILLIIIC TE}IPBRATURE Seconclary laclugl,ons (27)z 156, 183' l9l' 192, 219121,222,
    223, 22512y0 226er,228, 229'23o,
    2)1, 23J, 216. 211, 213, 211(zl,
    257, 2r8, 267. 26j snal 28?.

    11,012 (Uh32) Quartz


    FII"LIIIC TEI.IPERAIURE Prloary incluslcas (ta): 185(a), 2o9. 213. 226e1,229121,
    2t1a 235, 2360.239t 212. 216.249,
    251' 265 end 2?6.
    Secondary lncl-ugloas (1512 z15g'1, 216, 217, 21 8(l), 219,
    220e1' 222 and 2219.1.
    NREEZINO TE}IPERATIIBE PrS,nary lncluslolc ( 6): -1.3(zr, -1.J' -1.912; an<l -2.!
    APPARE}II SALIIIITI Prlnary lnclualonc ( 5). 2.212r, 2.6, l.2 . ,l aad 3.9
    14041 (llb10) celclte
    FILLIdO TEHPERATUNE Prlnary lnclusl'oas ( 6): 159'161,17?.181.186 and 199.
    SREEZII{O TEI{PENA?URE Prloary lue1uetonr ( l): -0.4r -0.5 aad -l.l
    TPPARENT SALIIIIIY Pr!.uary lncluslonr ( 3)z O.7, 0.9 aud 2.2

    11015 (l'h1l).
    FILLIIIG TEI,IPERATURE Prllrry lnol.uelosr | 5)t 251, 259' 261, 26lr ratl 271.
    6t6

    Secondary lnclurlonc 7lt 228, 231, 231, 235(, end 237'


    FREE?INO TEI{PERATURE Prlnary Lncluslona 7): -2.2151 ancl -2.3
    APPAREIII SALINI?I Prlaary Lncluslonr 7rl. 1.1 $, and J.9

    r40il lmlr)
    TII.LINC TEI{PERAIURE Prluary lncluslour (t6). 177,207,21 1,21 l. 131.217'221'2J8.
    25O,251, Z5), 25 L 121 o 261, 26) 1 37 t
    268,?7 1,27 2 (zl, 27 3 27 I', 27 5
    91 t 1 17,
    278)282,283,28'1.288 aild 296'
    TREEZIIIG TEYPERATURE Prlnary Lnclual.ons ( 5): -0.61t; antl -0.7
    APPARE!I1 SALIIIITI Prlnary LncLuslona ( 5): 1.11a; and 1.3

    7117l10 (r{h16)

    FILLIIG TEilPERATI'RE Prluary Lnclurlonr (21rt 213, 215(r, 216t 222121, 22L121,
    226, 228. 2rO. 232, 21L171, 2)5,
    2J9. 2l'O, 2t5, 251, a'nd 273.
    TRBEZTNO TETPERIII'RE Prllary inclugloal (10)r -0.5131' -0.6, -o.7. '2.7. -3.o,
    -1.1 and -j.ze).
    IPPARENT SALIIIr! Prfuery lnolurions (10): 0.91r1' 1.1' 1.1' 4.5, 1.9. 5.1
    ana 5.2(2).

    trARIIIGARA[ts

    1{021 (Ttz) Quarta


    TILLITIG TEIIPERATIIRE PrLuary lncluglone. (21): 2I'/',21. 2L6, 24,8, 250' 252, 25L.
    257121, 261, 265, 262121, 268,
    273, 27L121, 279, 28112; and 283.
    Seconilary lnclueloaa 5lt 219, 217, 219, 285 and 290.
    REBZIIIC TEHPERATURB Prluary LncLualoas 3)r -1.3 and -1.1(Z).
    APPAREIIT SALITIITT Prl,uary lnclualoug 3)t 2.2 and 2.&(Zt.

    11022 (lL8) quartt


    TILLIRC TEMPERATI'RE Prluary lnclug!.ons (ZSlz 22l(ll, 22r. 226(1.1, 229111;,
    232(zr, 23l1zl. 237. 219. 240121'
    2L2, 2L3141t 25L and 257.
    FREEZITIC TE}IPERATURE Prloary lnclugLone ( Z)z '1 '5 (t,
    IPPAREIII SILIIIITI PrIEary luclualoar ( 7) I z'6,z)

    1a029 (t{l{2) Quartz


    . ?ILLIIIC TEUPERATURB Prl,lery lnelucloor (251t 195(Z), 210(e) ' 215. 219' 222plt
    227' 210. 21,2, 2L5, 2L7 121, 252t
    253, 2rl(2r, 255,.257r 258, 261,
    267, 269 and 289.
    Sccoadary tncluelonr (19): 190' 191 r 191,161 195plr 2OO.2O2.
    297, 21 5 (2r,21 6.21 9,236,25 L'265 aill
    291.

    TI'I HIilE

    1torl (tur3) Quarte


    rILLI}IO IBI.IPERITURE Prloary LnclusloD! ( l)r 2'11 .2'I) and 285.
    Sccondary lncluetonr ( 9)r t74p1, z6o, 269121o 27o aad 27)111.

    11Or5 (lur12) Quartr


    rILLII|C TEilPERATI'RE Prlaary lnclusloal (2rrt 27o, 272(2r, 27te), 2711g1, 2756yt
    27? c286 t
    '278,28O,293 '281t285 (21
    288(") ) 289. 29O and 293.
    FREEZIIIC TEIIPERAT0RE Prluary 1nclur!.oac ( 6)l -z.tr'. -2.5. -2.7, -1.9, -t.1 . -t.t.
    IPPAREf,I SfLIllItI Prlnary lncluslong ( 6): 1r.0r4.2'L.5rl'.9, 5.0 and 5.{
    14056 (Tul13l Quartz
    rILLIIIO TbHPERATUNE Prluary lncLuslona (le):
    1r.r^,"rr.11t:?la trt,265 p1,266 (2, ,
    ;;;;;:;;;:;;;:t1t";;;111,;;;t,
    2_!ae1,275
    | ty t2761278,280( 3) .282.
    28).281(2r.
    28).28
    --t (2r, .e
    c--+1 (2). 28 )5 ((3,
    3r'286,289 ;290.
    '.oe
    TREEZIIC ?EHPEBATUNE Prlocry Lnclualoss
    292 (g),293
    6il, 29 1,296,300, r, ard 301.
    (re): -0.1. -0.212),-0.4( Eld -0.6.
    APPARENT SALINITY Prlnary lncluslong (t21, 0.2' 0.3(2)'0.1(il, ,,-o.5(,
    0.9(3) end 1.1.
    14060 (Tuf18) Quartz
    rILI.IIIO TEHPERATURE Pr!.oary tnclusloua (13) t 28361,288121,290, 293,291p1 ud
    2r5.

    1 {061 (tuft 9) Quertr


    rILLIIC IEIIPEBATI'RE Prbary hclurloar (271t 2191', 252()r, 251l1.r. 256p1o
    254 o 251(a), 26213r, 263, 265.
    15)
    rnd 2?1.
    11062 (Tu12O) Quartz
    FILLINC TEI'IPERITURts PrlDary lacluElonc (zglz zrz, ztL, 239. 2jL, z7o. 2,t2,
    273er, 271121, 275(i.l, 276'
    277121o 278t 28112y, 28212,1,
    28)p1t 28.1,. 28'1 . 292 aud
    FREEZIIIC TEUPEBA1ORE PrJ,nary Lnoluglona ( ?): -1.4r -1.6, -2.2. -2.1. -2.8."91(Sr.
    -3.6 and -3.8
    IPPARENI SALIIIITI Prlaary Laclual.onr | ?lz 2.1.2.7,1.'1,I.o,1.?,5.6 ard

    1106) (rut21) Sphalerlte


    FILLITIC IEHPENIruNSJ Prluary laclurl.onr | 6)t 27302?5.276$, aad 284.

    14064 (1ur22) Quartz


    . FILLITIO TEHPERATURE Prlnary !.nclugiona (87r. 255e), 261 (rr, 26r, 261,, 265(r,
    266131. 268(4), 261' 271121o
    271 (3r, 1( tt, 275 151,
    "7'(tl,
    276121. 271 "7
    278111, 2'19,
    12l,
    2811y1t 282. 283(2r, 281131,
    2gi(t. Za6. 2BB. 289121, 290,
    291141r 292, 293121, 2911gy,295,
    296, 297, 298(Z), 299. 30O.

    FREEZIIIO IEI.IPERASURE prruary hcrugrosr t.or, lll!?t:r:ili?l T:.il: -0.?111,


    -''4' -1'e121.
    :ll,g; :1.3'
    APPAREHT SALI[ITI Pr!.uery lncl.ugtoar (20): 0.5' 0.9(f), 1.1(3), 1.3141.
    1.513y, 1.7,2.1' 1.2121,3.? an'd
    5.1.
    11055 (ruf23) Quartz
    FILLISC TEHPERATURE Prloary laclualoar (41): 273121, 275, zEt, 28r, 290, 291(3)'
    ,9"(rl, 293121' 299, r00(4)'!01131,
    7o2(tr, 303(n) ' 3o'l1Zl, 309,310131'
    121' Z't2pl, 322, 137
    311 and 315.
    FREEZIIIC IEITIPERATURE Plhsry lacluglonr ( 8): ''1 .L, '2.1 (21 . '2.5, -2.7' -2.8.
    -2.9 aual -3.0
    APPARENT SALINITT Pl1rary laelualoag ( e): 2.1' 3.5e1, 1.2, 1.5, 1,.6.1'.8 rlal
    1.9.
    1106? (tur26) Barlte
    FILLINC TE}IPERATURE Priuery or Secondary (21,): 1r2, 111. 116,',t56, 16r, 166, 169,
    lnolugloaa 1'17, 181, 2O5, 216, 219. 226, 212,
    2)L(lrt 217o ZL{t 26E. 271. 275.
    2E6 end 288.
    1a068 (tufZe) Quarta
    FILLINC TEHPERAIIIRE Prlnaty lrcluslons 172). 256,265,2?0,271.2?2( il,273 (r),21 L.
    .275 t278 111),279 1 41,
    1 41,276121,277
    280(rr' 281(9), 282(6rc 2831tr1t
    28L' 285 ic'\,286,288 (ir,289 121,29o,
    2Q2o 29Ap1, 3O1, i}z. 3o4, 307,aad 327'
    FREEZII|G TEI{PERffltRlS Prlcary laclusLona ( 8): -1.0, -1.r(r), -1.1(zl and -1.5p1.
    APPABEII SALI$IT! Prlnery lneluglonr ( 8): 1.7, 2.2O), z.t1zl and 2.6121 .

    glgRol|g0Hlr

    1t91L (flll00) Quartr


    fILLrl{C lEl{?ERtT0RE Prlnary incluslonr ( I,l"l z 25J,25 L,262,26) ( 1.r, 26 L p1,265
    1 31,
    266,267 .269.269,271 (il,272 (Zl.
    27 J ( ll, 27 L ( 3r', 27 6 ( rj, zt t, 261;282 1 2,1,
    ( 41,28L'285,287,29O,292 anil f03.
    28J
    PREEZ II{C TEHPERATI'RE Prluary Lncluglone (11r): -0.21r1, -0.61r1, -0.9r -2.3(il ura
    APPIBEI{T SALI}IITI Prluary Lncluslour (14): 0.3(?), 1.1(3), 1.6. 3.9(21 anil
    5.5.
    140?o (wrr) Quartr
    PILLIUO TEMPERTTURE Prloary lncluslona (171t 213. 215, 221, 234, 216, 24,6, 2L9.
    258,;'r, 262, 26)' 26r,2)r 27A, 273)
    271 61;1 101.
    Secondary lncluclonc ( flz 232t 234, 252 and 265.
    Barltc
    TILLIIIC TEHPERATURE Prlaary laclucl.ons ( 6) r 98' 195, 1O7 121, '117 anil 128.

    1l,o?a (T125) Quarta


    FILLIIIG TEI{PERATURE Prluary lnclualona (39rr 232,2tL121,2)5,236i237.241121.251t
    252 025 L (2r, 262 (3r,263 1 g1,
    1 31.261
    26 I ( Lr.265. 267, 27 o, 271 p1, 27 2
    1 11'
    273121 and 2711.i1.
    Sccoodary laclualoae 11 31 z 1j3
    e).221,.225.2)O.232.23L.235,
    236.23?.261, 26! anil lOt.
    TREEZI}IC TEIIPERA?ORE Prlnery lnclurl.ona ( 6): -0.4, -0.6 and -t.?(f).
    APPAREIIT gAIIIgITT Prlnary lncluololr ( 6)r 0.?,1.1 and 2.8(*).
    1408r (wt4') Quartr
    FILLU{O TEI.IPERATURE PrLllry lnclualone (lo) c 1 8, | 227, 229. 231'232. 2t L (
    Zl, 275,
    236 ( 2)A t ZLl, 31, 2L5
    il, ( Z), 2 1,2
    1 1 2y,
    2t 6.2L?
    Or,2I'9 (11,250 e),25'l 121,
    252.257,25L (11.25?,261 antl 271.
    FREEZIIIO TOI,IPERI,TURE Prloary laclustonr ( 2): -o. j(z)
    IPPIRETIT SALIIIITI Prlrery incluslone ( a)r 0.9( z)

    14084 (rr56) Quarta


    TILLIIIC TEI{PERA?UBg Prloary !'nclu6Lo!! (ltlz 21 t,2)2, 233
    1{, ( 5r,235 ( s},
    23 L

    236 ( 2La, 2L2. 213 o zLL,


    Sr, 131
    215
    er,Z16 p),2L7,275 and 288.
    6tg

    r*os? {116.&} gr!$tE


    F,I.E&IIIC DSl,t?,SRlfARg Frtluly luslu*loar Itl ),t eZa rZl2, 3rl3r 2*{1 21, Zt's*rr',e42,
    251 r 252e
    3501
    21 r rl2, l 6 o255 13yr
    256.2rc ( rr t259 t261 1 21, 261 1 4;'
    255 &66 26E 269 6
    12y, " 121,27 131,
    282 ard 2811o1,
    FEtDid!il0 tEltF,Etrt4.8U:EE Prturl.ll tBotrt,rtoBr ( 7)r -0.712;i -1.01a1 rnil -l.l
    TFFABB'TI g LlilI''-! Prd,!u!y llocilutloltt ( ?lt 1.31r;r i.?141 rnd 2'2
    !509t furs?') :Qurfig
    tr t&I$6 r4lrP,Efla8u'BE PrfuGl., tEctrrrttrooa lzSlt 2341 2Ji, 278121r e41(l), 244'
    ?.15, ?d'.6, zigr 252. 260. 261.
    ' e6!' 266gU' 36?1s1. e?032tr.
    Zeflt ?f-3127 rail 2?1.

    'raEBurue tB[@ER'tr0nB Ftl"Erlt *Eclutio'l'r ( llz -O.5t -0.6131r -0.?r -l .l uil -l-5.
    tfnUfdg sALI{l A F4lart laclnaLoan ( f)r o.9r 1.1(rt;-1.1, 2.1 rnd 2.6
    n*99{ 0tl.s9.} Qu*rta'
    llgfifr0 Tf,]F&fltTBnE 'P'li!rt l,nclus'4err (Jl)a 2161 2?7' 239o 2{1o' 242t ?Llt
    ?lQ, 252, ?s,1..265 rod 865.

    It09t (1J19?) barlts


    . f[L&I{lll f&tF[,Rf!t!RA Pri,uary l*-e,Lrlg:Lo&c ( 6ll Eti tO?r 1r13r,31 lrd 196.
    65o
    APPENDIX IV

    FLUID INCLUSION CRUSHING AND


    LEACHING EXPERIME}ITS

    SAMPLE PREPARATION

    Cl-ear chips were sel-ected from the samples in order to


    obtain a high percentage of primary inclusions. In the case
    of vug quartz this was achieved by cutting off and collecting
    the clear tips of the crYstals-

    Quartz samples were boiled suceessively in concentrated


    aclds (Uf followed by HCl, Hll03 and finally H2S04) ' tap water,
    distilled water and deionised water, whereas a short immersion
    in dilute HCl was substituted for the boiling acid stages in
    the case of calcite samples. Fina11y, all samples were electro-
    lytica11y cleaned in an apparatus similar to that deseribed by
    Roedder (1g54): a bank of four cel1s (pig.IV-1) was constructed
    and wired in para1le1 and the total current drawn at 90 volts
    was monj-tered by an ammeter, The sanples are cleaned by draw-
    ing off surface absorbed ions causing an increase in the con-
    ductivity of the water and a corresponding rise in the current
    drawn by the ci.rcuit (rnonitered on the amrneter) . The water
    (initiatly deionised but later double deionised) was chaoged
    period.ically until tbe rise in current over a peri-od of a few
    days was only snalli r This process required between 10 days
    and four weeks, the cal-cite sauples being the rnost difficult
    to clean, Table IV-1 is a typical 1og of a batch of four
    sanples. The values given are only applieable to the systen
    d.escribed as different values would be obtained with changes in
    cell dinensions and surface area of the'electrodes.

    CRUSH]NG PROCEDURE

    Stainless steel tubes ( 17mm inside diameter, 19rnrn outside


    dianeter, approxinately 300nm 1ong, welded at one end and open
    at the other) were cleaned with a solution of HNOrr detergent
    and water (it the proportions 1t122) foLlowed by rinsing in tap
    water, distill-ed water, deionised water and double deionised.
    water.

    A tube, loaded with up to 60g of sample, was attached. to a


    vaeuum line (fiS.IV-2), heated to a temperature of approxi-n"ately
    65t

    Ftgure IV-ly Bank of four.eleetrolytlc cleaalng eslla. The tndlvldual 'Ur tubc
    cells arc each fllleit nlth a aauple and trater. Posltlvq pletlnuu elee-
    trodee are lsoerscil Ln oua al.de ald aegdtlve platlnuo electrodes in ths
    ' othsr. The eells are rrlrcd ln serlee, end tho currcut drann at 90 volte
    . Ls nonttorsd on tbc anoeter.. A cover lr plaeeil orer tbe callo durt'ng
    opcratlon to prcvent tluat gettllng lnto thc tubcr.
    652

    TAEITB: XV-!l; 01oani.ng 0411, Log forq$arrta sarprtras 1991 $'16)t


    199t9 (tll&), 1398p ({Sl) and 11A,54 Fur6}

    DATg TI!{E I'U&nE:uT= fuJil


    ?4 lug.ust, 197? Loailod s'aup-le,s'i.$to es[le abai fltld s3th iilelonlaed trag"
    o J,.l0r p,.u", 0r1Q9
    t 5.30 p.r. 0.,1 li!
    2! August, 2.00 p.n" 0.'r r 9
    26 lugueti' $.,1j, arn. 0.1?O
    I 2.00 p,a. g'.1t,:4

    0banged r,srt,qrr r.aftli.ed slth daJoalscd ttbilslt


    I 2.Of, P.u'- &ofq
    t! 1.21 g.so 9,o19
    T f.r00 .p.,!t,t . 0.ogtl
    Sg August l$:,1;t a.n,., O.1 21,
    Ghengoil n'atar1 r,eftlled wlrtb: daleiaised uitr
    r.. 8.4,0,t.pr, 0.11 4.
    t 9.1! 'a.-t'. 0,.'l I t
    '1 l.'tr0,8.D;' o.1 1?
    I {.!O p.ue 0.1'14
    ll lugust '- 8.30 d.n. 0,,125
    uharngcat satorr pefl}llorl rttilatoi.onlesd B*ter
    tl $-{! a..D,r o.08?
    I 9.1 5 Piql O.098
    i Saptelber r8..110 a..lit'. ^o"099
    Glranged lratGn, ref,ll,l*d satgl
    r,1th iletronija''ed
    T 8.?0 .d.r,r 0.1,04 (fflletl r,ctY hlgh)
    lg.lf arDr
    .
    0.1 08
    5 Sspt-eiuber "9..90.4.n. 0.119
    Cha4ged rrata!' rgfXtleit *tth double' 'aalonised satat
    t !!r,lro .arOL. 0qo82
    |l 1.1O Pin. 0.o99
    o 3.3O P.s,. 0',0,98
    ri {,.1ji p'n,. 0l'101'
    Chengsii ltdteir, refl ,'treat s!,th doubl[e deaooise-il gater
    t {..20 Bcn. o.05,6
    ? Sapt:enbel 8-00 a..u. 9r lOO
    'qbargsd $ctBh re,ftrl,Iied rllth double deionlsred ratG..r'
    t ' 9.O5 o,.r[.. 0.090
    t 9.69 Itn. 0.092
    tl 12-00 aoon . 0,094
    .t 12.{,0 p.n. o.09.5
    ! 2'30 g.tr'. 0.096
    F.euoveii taDPllts
    6rt

    s
    s.
    tI s c So-
    .9
    ul E
    5
    5 o- =g
    .E*
    o
    p 9E
    Sl
    r,E
    .cJ \
    vrs r0i
    'o
    t{oLOYlOtl .r, rl g
    O Ft iD .E! Fl {,
    -'q-r E C @ o -- o
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    120oC by means of a heating tape wound. around it and. pumped


    down by diffusion pump for approxinately lr8 hours to remove
    water absorbed onto the surfaces. The condition of the sample
    was rnonitered. by closing the Line off from the vacuum punp and
    observing the rise in pressure in the line over a peri-od of 10

    ninutes. this was negligible (O,OOt torr) the tube was


    When
    removed from the l1ne and, with the sample stil] under vacuum'
    crushed three times, Between crushings the tube uas turned
    through 90o to restore its shaPe

    The tube was reattached to the line and agai-n heated'' The
    vapour released on opening the tube to the line was separated
    j-nto H20, CO, and non-cond.ensable fraetions by vacuum distilla-
    tion, The non-condensable and CO, fractions were always small
    (c.f. Table ?-8); the latter being too small for oxygen isotope
    analysis. HZO was condensed into a sanple bottle and trans-
    ferred to another vacuum line for hydrogen separation (by passing
    over hot zinc) and subsequent D/H analysis in the mass spectro-
    neter. The D/H ratios for the sanples are given in Table 8-1 '

    LEACHING

    Three different leaching solutions were used': double de-


    ionised water, ammoni-um nj-trate solution and nitric acid
    solution. To obtaln a 1or,r level of contami-nation in the
    reagents, analytical grade nitric acid was distilled in a sub-
    boiling dlstillation apparatus (Fig. IV-3) constructed from the
    design ilescribed by Mattinson (1971). The rtpurett nitric acid
    was mixed with double deionised water to nake the nitric acid
    solution and withtrMERCK Pro analysi aromonia solution GR (0-91 )r
    (supplied in 5 l-itre plastic eontaj-ners) and double deionised
    water to neutral pH for the anmonium nitrate solution- Table
    IU-? lists analysos of these reagents.

    Initially only a single water or nitric acid solution was


    used to leach samples, but later a nultlple leaching scheme
    lras adopted (Fig.IV-4). The crushed samples were transferred'
    fron the stainless steel tubes to pre-cleaned. 25OnL polyethylene
    bottles (obtained frorn Industrial Moldings Ltd, Seaview, Petone).
    Approximately 3Ag of leaching solution was added, agitated
    period.ically for 10 minutes, centrifuged at 2'000 1'.p.1n. for
    one hour, and siphoned off into a pre-cleaned 100n1- polyethylene
    bottle ( slmil-ar to those made by Nalgene) . Only two-thirds
    655

    ftgurr IV-tr Teflon aub-botJ,lng aEld dlstlllatlon apparatuc coagtrlrateil fror


    the ilesLgn dessrlbeil by llattlnsoa (19?1). Analyttoel grade altrl.c acld
    rea heatail in onc bottl,e by tha lanp and the rapour condenoed, ln the
    othar. Dullag operatlon altutatuu foll ras usoal to screotr the eontleastng
    bottle flon'the 1ao'p anil a plaog vae alao uaed over the top of the othar
    . bo'ttlq to reflect b.set back Lnto thc bdttlc. The ayater gavs ai ou&put
    of epprorhetely 100 rt1llLitrer pcn rceL.
    656

    TABTE trV-2: Conaentratlons, in parts per billion,


    of N.*, K*, Mg2*, . and a,l?+ . in the
    fluid inclusion leaching reagents.
    Analyses by Mr J.E. Paterson' Chenistry
    Dlvision D.S.I.R.

    20% 20%
    arnnoalun nitrlc
    nitrate acld.

    Na*
    +
    K'272
    ry
    "'2+
    Mg'' 1 5 1
    ?l
    a l,- 1r0 10 10
    65:l

    lI'GiIV-4: F,tov dtograc of ib6 ciFurklnt! aad lea.ohlng


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    I
    I
    Quart r orushttraasf errcil
    ton ,totD-td.

    lrt Laaohl,ag aolutton!


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    Znd Lcrch (aOg 1 ,ad.g[,ead
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    I
    o
    Qurr'Ez Glusb gaEd
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    lltrete eelutlon
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    ?ril lerdllag toLntlor! I
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    ,r{ a3!ch (soB rtp}oacd


    sft rnd. Enaltre.ra!
    '
    65s
    of the leach could be siphoned off the top of the crushed
    sample without contaminati-on from the sludge, Therefore, for
    the second. leach , 2Og of 20f' ammonium nj-trate solution was
    ad.ded to the crushed sample giving a 30g leaching solution of
    approxinately 13f, amnonium nitrate. Simil-ar1y, after this was
    centrifuged. and siphoned off 10g of 13f, ammonium nitrate solu-
    tion renained in with the crushed sanple. The third leach of
    131g nj-t-rie aeid solution was obtained by adding 20g of 20f,
    nitric acid solution to the crushed sample. The residues
    left after each l-each have been corrected for in the analysgs
    presented in Tabl-es IV-3 and 7-1 so that the individual fi.gures
    in these tables represent the weights dissolved by only the
    si-ngle leach and do not include traces of prevj-ous leaches.

    The water and ammoni-um nitrate leaehes were acidified


    with distilled nitric acid to make 2/" solutions and. aL1 leaches
    were analysed. for Na, K, Mg and A1 by atomlc absorbtion, Ca
    an6 Li by flame enission and CI by the colourinetric teehnique
    described by Swain (1956). Zn, Rb and Cs were also analysed'
    for j-n sone samples: Zn and Rb by atonic absorbtion and' Cs by
    flame enission, The cation analyses were by Dr. R.L. Goguel
    and Mr J, Paterson at Chenistry Division, DSIR, usi-ng Perkin-
    Elner equiprnent, whereas the ehloride analyses were by the
    writer using a Beckman Model B spectrophotoneter, housed in
    the Geology Department, Victoria Unj-versity of Wellington. The
    standards used were a set of multi-el-ement solutions (to
    minimise errors due to interference) containing conc.entrations
    of the eations and chloride bracketing and equal to those en-
    countered in the analyses. '

    RESULTS

    Table IV-3 lists the leach analyses and these have been
    correeted. by the dilution factor ( calculated frour the fluid
    incLusion water yield measurements) to give the apparent fluid
    inclusion eomposj-tions presented in Table 7-1 .
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    663

    f,AB!,B 'I-V - .{1r Anr[fsos ef t.].glrkst Fg of lons gatdqa..+ tr:eaohjedfroa tro sanplles'
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    661+

    ASSESSME{T OF EXPERIMETTITAL CO}TTAMINATION

    Three blanks were prepaied by cutting lengths of silica


    glass tubing (Spectrosil) into smal1 pieces, They were eJ-eaned,
    crushed and l-eached at different times by the same techniques
    used with the samples. Analyses of the leaches (Table IV-/r)
    show that the ions of interest were not detectable, or present
    i-n only trace quantities, indicating that contamination duri-ng
    the experlmental procedure is mj-nina1,

    PRECISION; DUPLICATES AND SAMPLE GROUPS

    Sufficient rnaterial for several crushing and leachlng


    experinents was avaj-lable for some sanples. Chips of the
    sample were sorted according to their quality (=cLarity) to
    give a series of samples identified by the subscripts a,bre,
    etc. in deereasing order of quality.

    In cases where the rnaterial could not be separated, due


    honogeneity of the sauple, the separates are regarded as
    duplicates and are glven the subscrlpts 1 'and ?.

    Four pairs of duplicates were crushed but only three;


    1292s (M19) , 1t+037 (wirro) and 1t+061 (Tui19) , were leached. with
    the identical solvents.

    The two samples of 12925 (M19) show very good agreement


    except for lla* whi-eh is lower in 129281 than 129282 (Tables
    IV-3 and 7-1), The two analyses of 1l+037 (Wh10) have simj-Iar
    ionic ratios and the eoncentration values, uncorreeted for
    inclusion water yield, are also sinilar. l'Ihen the analyses are
    comected for the incluslon water weight (table 7-1) the agree-
    nent is diminished suggesting that one of the water yield
    neasurements is incorrect. Corrected and uncorrected analyses
    of 1t+061 (Tui19) are in good. agreenent except for K* whlch, 1n
    the corrected analyses, is higher in 1l+0612. The use of a
    successi-on of different solvents on 139572 ftKz) compared with
    the single solvent used on 139571 $f.za) and possibly inaccurate
    uater yield results may contribute to the poor agreenent in
    absolute eoneentrations of soue ions between the two sanples,
    +
    although Na', Li- and Cl are not very different.
    .665

    T.&BIE IV-5; !{ajor Lon asa-Ly,ses of f-l'uid i,aelu'sioas in


    ealeii.te from the lri[gawha geothernal s;rste,n,,
    . eqd uo.dern bore fluids,. 0oncentratlone
    a re given ia mg/-kg (ppm) .

    FX,uid inel-usion Average anal-yses of


    wa,tcr anal.ysis 'nodern'wate,r in ue:l-l-s.
    ($ample NG5) 1 ,2,rA and 9.

    +
    l{a' 652 1,028 1,086
    K+ 126 89 92
    ga2+ 2l {'00 13 $,

    A:t 3 Tltr a 0.5


    l,tsE* 2n1ltO 1 0.,.,

    Li+ lii$ 13 14
    01* . 1 ,90O 1,&7'6 1,610
    NalK 5.2 :iltf.6 11.8

    * +t. average of alL enalSrse's of wofl water and steaa lieted


    l.n TEihIe 6-4 of, Brorrne Et ,a-1 (tgat).
    2
    r+F' averags of well water analtrroee only (,Fane sourse as
    above)
    666

    The samples separated into quality series generally also


    show good. agreement. Three analyses of the 13980 (ASt 1 series
    are in reasonabfe agreement but a fourth' 1 3980b, although having
    a sim|lar lila/K ratio to the others in the series has nueh
    greater relative concentration of the other i-ons.

    Considering that the five samples of the 13939 + 1391+1


    (i,tt6 + N1/r) series were leached with different solvents four
    sanples are in good agreement, whereas the fifth,13939 (Nl6)'
    contains much hlgher rel-ative concentrations of K* and l'lg2+.

    The two (Tui5) samples are the best palr, having


    1l..051+
    very si-milar ionic ratios but slightly different absolute con-
    centrations, the latter presumably d.ue to incorrect water yield
    measurenents.

    In conclusion, the duplicate and group samples generally


    show good agreement, but indicate that the water yield neasure-
    ments are not very accurate.

    ACCURACY:. TEST SAMPLE

    A sample of calcite cuttings from approxinately 1 000m in


    d,rillhole 5 of the Ngawha geotherrnal field' ltrorthl-and, was
    processed along with the other samples. Unfortunately no other
    modern geothermal sanples could be obtained whieh had sufficient
    rnaterial for the proeedure.

    The sample was crushed and leached with r,rater twice-


    Table IV-5 presents the analyses of the combined water leaches
    (they are shown separately 1n Table IV-3) along vith an
    analyses of the nodern bore water. -Agreenent of Na*, K*, Li*
    and Cl- is good.. High values of Mg2+, cu?r and A13+ in the
    leaches (Table IV-5) are due to contamination from the calcite
    host. Di-fferences in Na* and K* concentrati-ons between the
    fluid inclusj-on analyses and the nodern waters are opposite
    (Na+ in the incluslon analysis is about 35% lower than in the
    nod.ern water, whereas K* is about trT% higher than in the modern
    water) and lead to a large difference in Na/K ratio z 5.2 in
    the fluid. inclusion waters and approxinately 11.5 in the mod.ern
    bore water.

    These results are very encouraging if the chemistry of the


    667

    Ioodern geothernal- water is assuned. to be similar to the


    waters present when the inclusions forrned.

    ASSESS},IENT OF A}IALYSES OF INDIVIDUAL SAMPTES

    Introduction
    The results of the crushing and leaching experinents on
    each sanple (Tables 7-1 and IY-3) are discussed. individually
    in the following sections to deterni-ne the presence and d'egree
    of contanination in the fluid incLusion analyses. The criteria
    used. for assessi-ng the degree of contamination are discussed.
    in Chapter 7.

    Quartz and calcite are grouped. separately and the saurpleS


    of each nineral are listed in the geographical order-of their
    location (north to south).

    Quartz Sanples
    Tokatea
    Sample 13957 (TK2)
    sanple 1395'l consj.sts of quartz crystals fron a comby
    quartz vein within the Tolcatea Big Reef near Tokatea Saddle.
    The sanple was split into two dupticates 139571 and 1 39572.

    139571 gave a good yield of riater (23ng). The erushed'


    sample was leached with nitric aeid only. Aluninj-un contanination
    is low and conparisons with I'la/Al, Na/Li and K/A1 ratios in
    the quartz analysj.s suggest that contamination of Na and K in
    the leach, if present, is negligible. The Ca/t'lg ratio of the
    quartz analysis indicates that most of the Ca present in the
    Ieach is from contamination. Na and K are only slightly out
    of balance with CI,

    139572 gave a water yield less than half that of 139571


    (9rg). The crushed sanple was leaehed with the three different
    leaching solutions. A1 contamination is very high but
    comparisons with the IIa/A] and K/Al rati-os in the quartz
    analysis i-ndicate that I'la and K contamination from this source
    would'be insignificant. In contrast if the A1 is eonsidered to
    pred.oninantly come from parti-cles of serj-cite in the fluid
    66s

    lnclusions, half of the K wou1d. al-so be from this source.


    Cornpensation for this, changes the lIa/K ratio of the leaches
    to a value similar to 139571. Practically all of the Ca in
    the leaches is fron contamination. There is insufficient Cl
    to balance wlth the }ia and remaining K even after adjustment
    for possible seri-eite contanination.

    In appraisal the Na, K and Cl concentrations of the fluid


    inclusions is considered to be best represented. by 13957,r2
    3/r00ppn Na, 1500ppn K and /e600ppn CI.
    Sample 13958 (802)
    Sample 13958 consists of large quartz erystel s fron a conby
    quartz vein within the Tokatea Big Reef at the Buffalo I'lj.ne.
    The sanple was split into tr.ro of different quality, 13958" and
    't395sa.

    13958a gave a poor water yield (lng from t3S of quartz).


    The crushed quartz vas Leashed with the three different
    solutj-ons. IIa and K display good, leaching patterns. Al
    contanination is very high, however lila/A.l, Na/Li and K/Al
    ratios of the quartz analysis and leaches indicate that
    contaninati.on of Na and K would be insignificant from this
    source. Ca contamination is also high and is matched with the
    quantity of l"lg expected by eomparison with the 'l{S/Ca ratlo of
    the quartz analysis. The leaching pattern of CI follows the
    general trend. but the total eoncentration of Cl is slightly
    defficient for a good charge balanee with Na and K,

    13958b gave a l-ow yield of water (12ng frou l+3e of quartz).


    The crushed sanple was leached three times with water, The
    second and third leaches contained extrenely low eoncentrations
    of ions except for snal1 quantities of CI and IIa. A1, Ca and
    Mg contamination are uuch greater in 13958a than 13958a as
    indicated by their higher concentrations in the water leaches
    of 13955b compared with the single initial water leach of 13958a.
    Nevertheless the Na/K ratios are sinilar r"ihen calculated from
    the three different leaches of 1 ltJ8" and the three water
    leaches of 13958a.
    669

    In appraisal the ltra and K concentrations of 'the fluid


    inclusions are eonsidered to be best represented by 13958a.
    7500ppn Na and 2700ppm K although a }tra/l( ratio close to j nay
    be nore appropriate. 8300ppm Cl is present.

    Petote Stream Area


    Sample 13,aA| (Uutt 2)
    sanple 13907 consists of large vug crystals fron the Hutt
    creek area. The sample gave a low to noderate yield of water
    (8ng fron 33g of quartz). The crushed sanple was leached, once
    with water.

    Ca contanination is evident but Li, Mg and A1 concentrations


    are very Iow1 although this is to be expected with a water
    l-each and therefore does not discount the possibility of these
    values being from eontanination. The eoncentration of cI
    balances very well with the Na and K.

    The indicated, partial conposition of the inclusions is:


    JJ00ppm I{a, 140ppn K and {000ppra cl. These are probably niniuum
    values, whereas the Na/K ratio of 2t, is a naxinun (f is
    proportionately higher) .
    Sanple 1 3980 (As1 )
    Sample 13980 consists of large vug quartz crystals fron
    Aitken Strean. The sample was split into four of varying
    quality. I'Iater yields of 13980a, and 1 SgSAc uere good (22
    and 30 ng respectively). The glass tap attaehnent to the
    evacuated. stainless steel tube broke after the first crushing
    of 13980d allowing ai-r into the tube. After repairs the sanple
    was puuped down and crushed again yielding 8ng of water
    indicating that the origS-na1 i.nclusion r^reight (fron which the
    leached salts are d.erived) was probabry between 20 and J0ng.
    139800 was not crushed. und.er vacuuur because of the snall quantity
    of sanple.

    13980a, 13980c and 13980d were leached only once each with
    aitric acid solution, uhereas 13980U was leached with all three
    leaehing sorutions includ.ing several ad.ditionar nitric acid
    leaches.

    The Leaches of 13980a, 1 3980c and 139S0d have very similar


    67o

    concentrations of the various ionS. Ca and l"1g contamination


    is very low conpared with other sanples' whereas A1 and Li
    contanination is about average. Comparj-son with the Na/Al'
    t'Ia/Li and K/Al- ratios of the quartz analysis indicate that
    significant lila and K contatrination has not occurred' although
    sinilarl-y high Na/l< ratios occur in the leaches and quattz
    analysi.s. CI was only analysed fronr 13980d and although not
    balancing perfectly with Na and K its concentrati-on is of the
    right order.

    In eontrast to the above sanples the concentrations of


    various i.ons leached fron t3980U are very low indicating a 1ow
    content of leaehed fluid inclusions. Ca, Mg, Al and ti (tfre
    latter nearly as much as Na) concentrations, in proportion to
    l,la and K, are nuch higher than in previous samples. The t'ta/K
    ratio is consj-derably Lower indicating that the analysis nay
    have been contaninated with K in addition to Ca, Mg' AI and Li.

    The successive aeid. leaches experimented with on 1 3980b


    failed to yield any nore Na and K but the last leach contained
    considerable quantities of Ca and C1 indicating possible
    contamination of the leaeh during handli.ng.

    In appraisal an average of 1 1980" and 1'3980" is considered'


    representative of the fluid inclusion conposition: /r900ppn lla
    and 320ppn K with considerati-on that the Na/K ratio is sinilar
    to that of the quartz. Cl nust be extrapolated. fron 13980d'
    indicating 3900ppn C1.
    sanple 13998 (Ps1 5)
    Sanple 13998 consists of snall vug quartz erystals,
    intergrown with Stage 2 chalcopyrite and pyri.te' fron the
    Chalcopyrite lode of Petote Strearn. The water yield was 1or.r
    (6nS), however only a snal1 quantity of quartz was crushed
    (23d. The crushed. sarnple was leached with all three different
    solutions.

    Ca and Mg contanination is very lov with no Ca d,eteeted in


    the nitric acid. leach. Al and Li contanination also appears to
    be low compared with other sanples. The leaching patterns of
    Na and K are very good and follow the expected behaviour for
    67t

    these ions. The pattern of Cl is not so good but the total


    quantity balances very well- with the Na and K.

    A few fluid lnclusions in pdlished plates of another sanple


    of quartz (13gg5) fron this stage contain a fibrous solid
    rnineral (sericite?), however the high N"/f ratio and. good. Cl
    balanee suggest that contamination fron this roineral is
    insignificant.

    In appraisal- the leaehes of 13998 appear to be sone of the


    better analyses although the suggested fluid inclusion partial
    analysis of 1800ppn Na' 180ppm K and 2000ppn CI gives a high
    trla/K ratio of 10.
    Sample 1 Loo6 (esee;
    Sanple 1l+005 consists of sma1l vug quartz erystals from a
    vein crossing the Petote Strean track. The sanple gave a Jow
    yield of water (6mg fron 29g of quartz). The crushed sanple
    was leached with the three different solutions.

    Ca and A1 coneentrations are extrenely high particularly


    in the nitric acid leach, whereas Flg and Li are comparatively
    low (with ref,erence to their ratios in the quartz analysis of
    this sample). Connparison with the Na/Al, I{a/ti and K/Al ratios
    of the quartz analysis suggests that contamination of Na and K
    could account for only lr and, 15fr respecti-vely of that recorded
    in the leaches. However, Na contamlnation has oecurred as
    evidenced by the increasing quantities of lla in successive
    leaches. Cl is far too low for a reasonable balance wlth the
    total- Na and K.

    Particles of a fibrous nineral were observed in soue of the


    fluid inclusions of plates prepared for heating and freezLng
    study.

    In conclusion the leaches of this sample are considered to


    be generally contaminated.

    lJhangapoua
    Sample 13910 (Wg9)
    Sample 13910 eonsists of surall vug quartz crystals inter
    6lz

    grown with stibnite f ron tdaingaro Strean - A moderate to good


    yield of water (8mg from 219 of quartz) was obtained. The
    crushed sample was Ieached with the three di_fferent solutions.

    Na and K exhibit good leachi-ng patterns and cl balances


    r,rel1 with these ions. Contanination of Ca, Al, Mt and Li is
    about average conpared with other samples. The lla/K ratio of
    5.4. indicates a teroperature of approxinately 250oC (lia/f
    geotherrnometer) compared with the fluid i-nclusion filling
    tenperatures of 19OoC (Ua/fra9).

    In appraisal the nartial- analysis of 23o1ppm lia, {J0ppn K


    and 3?00ppm C1 is considered. to be representative of the fluid
    lnclusion water.

    Neavesvilie
    Samp1e 13938 (N44)
    Sample 13938 consists of large vug quartz crystaLs picked
    off the Ajax 1 Jevel nulLock heap. Because of the small sanple
    size (8S) the sanple was not crushed. und.er vacuum and therefore
    the ueight of inclusion water is not known.

    The crushed sample was leached with the three different


    solutions. ca, Mg, Al and Li contaminati-on are present. The
    leaching patterns of t{a and K indicates that signiflcant
    contanination of these ions has not oesurred. Inclusions of
    seri.cj.te present in the quartz of Ajax 2 level nay also occur
    1n quartz of 1 level, irnplying that K bontamination of the.
    inclusions is possibre. The high concentrati on of cl i_n the
    water leach indieates that contanination of this ion occurred
    during handling.

    In appraisal a N*/n ratio of 2.6 is indieated for the


    inclusion waterr provided K contanination has not oceurred.
    sanples 13939 (lr 1 5) and 139 t+1 ( Nl 4)
    Sanples 13939 and 1391r1 are large vug quartz erystals fron
    Ajax 2 level. Because of experimentati-on with the d.ifferent
    leaching solutions, the large quantity of naterlal colrected
    uas eventually portioned. into five samples of d.ifferent grad.e
    (13939, 139t+1a, 13gtr1b, 139/*1c and 13gt+1d) crushed individually
    or in pairs at different times with batches of other samples.
    A.ra

    /
    All five samples gave good water yields, 139t1O being
    exceptionally good at 55ng.

    139lr1b lrasthe first sample crushed in this study and was


    leached once with water. to test the viability of the technique.
    139lr1a and 13939 uere each leached. once wlth nitric acid
    soluti.on, whereas 13941 and l39lr1a were successively leached
    with water and amnonium"nitrate solution.

    The quartz analysis indicates the presence of sericite


    j-nclusions and therefore K contamination nay have oecurred
    during leaching. This appears to be the case in the nitric
    acid leach of 1 3939 where the concentration of K is three
    ti-nes that of iTa. Ca, Mg and Al- contanination is also high in
    13g3g relative to the '13g41 sanples.

    In eontrast the renaining sanples have Ua/K ratios close


    to 1 uith lla predominating in 1391*14 1391+1O and 139111" but K
    predoninating in l39lr1a. Ca, A1 and Mg contamination is
    noderate in leaches of these sanples and l,lg is very 1ow in
    139t1a. I,i values are near nodern geothernal water levels anC
    may be representative of the inclusion waters. Because the
    quartz contai-ns little Li (quartz analysis, Table 7-2),
    contanination frorn this source wouId be ninor. The CI
    concentration is fairly consistant in all samples, having an
    average indicated coneentration of 1200ppm. Except for 13939
    and 139lr1a the Cl balances with the Na and K.

    In appraisal, a partial analysis of 74.0ppm Na, 530ppn K,


    31ppn Li and 1220pprn Cl is obtained. by average total values of
    these ions from the various leaches of 139111 a, l39lr1A, 13941 e
    and 1391r1a. However, the K value nay be too high because of
    contanination from sericite as indicated in 13939.

    Maratoto
    Sampte 13919 (Mzq1
    Sarnple 13919 consistsof large vug quartz crystals fron
    the CamooLa vein, The 289 sample gave a low water yield (?mg)
    The crushed sanple was leached with the three different
    solutions.
    674

    Ca and Mg contaminati.on are very high and in a similar


    Ca/ilg ratio to that in the host quart z as indicated by the
    quartz analysis. Al- and Li contamination are extremely lotr
    and the coneentration of Li in the leaches may be representative
    of the incLusion waters. The leachi-ng patterns of Na and K
    differ fron the general patterns with possible K contaninatlon
    in the nj.tric acid leach. However, conparison of Na/AL, Na/Li
    and K/Al ratios with the quartz analysis suggest contamination
    is not from this source. The total Cl concentration is very
    high compared with IIa and K as in other samples from I'faratoto
    (see following).

    In appraisal the partial analysis of J000ppn Na, 88,0ppn K'


    dOpprn ti and 12000ppn Cl suggests either Cl contamination or
    the presence of Ca rich fluj-ds.
    sanple 13926 (uto)
    Sample 13926 consists of small vug quartz crystals fron the
    SiLver Queen vein. The sample gave a moderate yield of water
    (ttmg) considering the quantity of quartz crushed (zgg). The
    crushed sample was Leached with the three different solutions.

    Minor Ca, A1, l,lg and Li contami-nation is present in the


    leaches.

    The leaching patterns of lla and K follow the general Na


    pattern. Although the Na/K ratio of the leaehes and the quartz
    are sinilar (5.3 and 5.2 respectively), conparison of the lia,/Al,
    Wa/i,i ana K/Al rati.os sugeests that contanination of Na and K
    is insignificant. Particles of a fibrous rnlneral occur in fluid
    inclusions of plates prepared for heating and freezing work and
    provide a possible contamlnation souree if present in large
    numbers. If these particles are sericite a balance with the
    A1 contamination can account for all of the K present in the
    leaches. The total concentration of CI is high conpared with
    Na and K as in other l,laratoto samples.

    'fn appraisal the partial analysi-s of 2700ppm Na' JlOppn K


    and 11000ppm CI suggests C1 contanination or the presence of Ca
    rich f1uid.
    6ts

    Sample 139?S (M19)


    Sample 13928 eonsists of small vug quartz crystals from
    the Camoola vein. The sanple was split into two duplieates
    13928,,and, 139282 of equal quality. These sanples gave sinilar
    water yields; 13928r, 27ng from 55g of quartz and 139282, 15ng
    from 39g of quartz. The crushed saroples vere each leaehed uith
    the three different solutions.

    The concentratlons of various ions in the leaches of the


    two samples show good agreement (when corrected for water
    yields) except that ltra and Mg are slightly l-ower in 139281
    than 139282. Ca, Mg, AL and Li contamination has occurred.
    Compari-sonswith the quartz analysis shows that the l4g/Ca
    ratios of the leaches are alnost identical to that of the host
    quartz. Similarly the Na/K ratj-os are very close. However the
    leaching patterns of l{a and K follow the general trends for
    these ions and conpafison with the Na/Al, wa/i,i and K/LL ratios
    of the quartz analysis suggest that both Na and K, proporti-onal
    to A1, contanination is insignificant. Particles of a fibrous
    mineral were present in the inclusions of plates prepared for
    heating and freezLng work. Approximately half of the K present
    in the leaches can be balanced with Al if contani-nation from
    seri-cite oceurred. The low lIa,/K ratios of the 13928 sanples
    relative to the other l,taratoto analyses (13919 and 13926) and
    the ratio pred.i-cted by the IIa/K geothermoraeter (5 at 270oC)
    suggests K contanj-nation. The total concentration of Cl- is
    high'conpared with lria and K as in other I'laratoto samples and
    requires balancing ruith Ca.

    In conclusion, although the water yield and the leaching


    patterns of tla and K appear to be satisfactory the low l{a/K
    ratios of the analyses are believed to indicate that contamination
    of K, in addition to Ca, I,lg, Al and Li nay have occurred.

    Konata
    Sanple 1391r8 (Km18)
    Sample 1391+8 consists of vug quartz crystals from 8 level.
    Because of the snal1 quantity of sample (1trd it was not crushed.
    under vacuum. The crushed sample was leached with the three
    different solutions. Although the quartz analysis indi-cates
    that the sample contalns very little Ca, Ca contarnination i-n
    676

    the leaches appears to be at a high IeveI. A1, Mg and' Li


    contamination appear to be low. The leaching patterns of Na
    and K and the tla/K ratj-o of /,.8 suggest that no significant'
    contaminatj-on of these ions has oecurred. The total quantity
    of Cl present is very high conpared with ltra and K and requires
    balancing with sone Ca.

    tr'Iaitekauri
    sample 1t*013 (tlK4)
    sample 1 LO13 consists of large vug quartz crystals fron
    the l,laorlLand vei-n, The sanple was crushed under vacuum but
    the stainless steel tube cracked. admitting a small quantity of
    air into the system. The water yield of 10ng is therefore
    consldered to be a maxlnum value,

    The crushed. sarnple was leached with the three different


    solutions. AI and Li contamination is l-ow and rnay be present
    only in the nitric acid leach, whereas Ca and l'1g contamination
    is more general and. present in larger quantities. The l'lg/Ca,
    Li/Al and also N"/tC ratios of the conblned leaches are sirnilar
    to those of the quartz analysi.s- Na and K contanination may
    also be indicated by the increase in Na in the nitric acid
    leaeh, the progressive increase in K through the three leaches
    and. the overall 1ow Na/K ratio ( 1.4)'. If Na and K contanination
    has occurred j.t is in a nueh greater proportiOn than A1 and Li
    as indicated by the Na/Al, ita/l,i and K/Al ratios of the quartz
    analysis. The total concentration of C} is high conpared
    with Na and K and requires sone Ca for an ad'equate charge
    balance.

    In conclusion the sanple is considered to be generally


    eontaninated and not representative of the original i-nclusion
    waters.

    Idaihi
    Sanple 1lr03l, (tUtrl)
    Sample 11103/, consists of srnall- vug quartz erystals frout
    the mulloek heap of No.5 Shaft. Because of the srnall quantity
    of quartz 1t was not crushed under vacuun. The erushed. sample
    lras leached. with water three tines. Little ad.ditional naterial
    _6?7

    lras dissol-ved by the second and third water leaches' Ca and


    Ilg contaminatj-on nay be present but the degree of contani'nation
    is difficult to assess without annonium nitrate and nitric aeid
    Ieaches. However, Li contanj.nation i-s evident. The concentra-
    tion of K nust be considered a ninirnum value in relation to Na
    because of the absenee of anmoniun nitrate leach values. The
    total concentration of CI indicates that if a full analysis
    were available a good eharge balance with Na and K ntght be
    achieved.

    fn conclusion if Na and K contanination is ninor a naximun


    Na/K ratio of 1/, is indicated fo.r the inclusion fluids-

    Sanple 1t+035 (l{h4)


    sanple 1l+O35 consists of smalL vug quartz crystals picked
    off the mullock heap of No.5 Shaft. The sample gave a lou
    water yield ( 6ng from t*t+g of quartz) . The erushed' sanple vas
    leached. with the three different solutions.

    Al and Mg contauoination is low. Except for a snall increase


    in Na concentration fron the water to the annoni-um nitrate
    leach the leaching patterns of Na and K look satisfactory' Li
    nay be uncontaminated.. The total concentrati-on of C1 is
    slightly high relatj.ve to lla and K and nay requj-re balancing
    with a snall quantity of Ca but not to the concentration present.
    Therefore most of the ca is fron contanination.

    In appraisal a tta/K ratio of 3.6 is indicated for the


    inclusion fluiits and a srnall quantity of Ca is required' to
    balance Cl. The partial analysls is 2800ppn l,lar ?80ppn K'
    4?pprn Li and 5300pPn cl.

    sanpLe 1t*037 (wuto1


    sanple 1LA37 eonsists of snall vug quartz crystals from
    3level. The sample was split into two d'uplicatesr 130371
    and 13Q372. Both samples gave very Poor water yield's: 2 and
    {rng respectively fron about 50g of quartz.

    The crushecl sarnples were eaeh leached with water and


    annoniun nitrate solutlons. The leaches of the two samples
    are very consi.stent,
    678

    Although nitric acid leaches were not used, strong


    eontamination of Ca, A1, Mg and Li is indj-cated by the annoniun
    nitrate leaches. Cl is present in greater quantities than can
    be balaneed r*ith lrla and K and some Ca is required. to complete
    the balance. Both samples gave Na/K ratios of 0.6 suggesting
    K contamination.

    The absolute values of the various ions in the two sets of


    leaches are very close but when corrected for fluid j.nclusion
    water yield.s they are considerably different. This can be
    taken to indicate that the original water yields were identi-eal
    and the measurements in error or that because the water yields
    are so Iow the leach analyses only reflect equal leve1s of
    contarninatlon.

    fn conclusion lf the leach analyses of Na, K and' Cl are


    believed to be correctr &Il average of the two analyses gives
    an indicated partial composition for the fluid inclusion
    water as; 2900ppm Na, /r600ppn K and 13000ppn Cl. Ga nust be
    considered as a naior component to balance Cl.

    Tui Mine
    Sanple 1lr05l+ (Tui 6)
    Sample 1lr}5t, consists of large vug quartz crystals from 5
    level of the Champion vein. The sanple was split into two of
    different quality, 1/*0J{" and 1l+054b. The crushed sanp}es
    were ]eached only once r,rith nitric acid. Although the sanples
    gave different water yields (1405L,. 12mg and 1t054b 21urg) ttre
    uncorrected leach ana}yses are remarkably consistent. After
    correction for water yields the agreenent i.s not so good'. A
    possible explanation is that 1lrl|l+b contained more secondary
    inclusions resulting in a nore dilute solution. Alternatively
    one of the water yleld neasurements nay be incorrect.

    Ca contanination is high, whereas contarninati-on of A1 and


    Mg is noderate. The Li/Al, lIa/K, Na/Al and Na/Li ratios of
    the leaches and quartz analyses are very different indicating
    that Na, K and Li contanination may be minor.

    Particles of a fibrous mineral were identified in fluid


    679

    inclusions of plates prepared for heatinq and freezir^q work


    and all the K present in the leaches can be balanced with the
    AI lf these r.eSu1t from contaninati-on by sericj-te. However'
    the Na/K ratio of f .2 glves a temperature (t'la/t< geothermorneter)
    in reasonable aqreenent with fluid inclusion filling temperatures'
    suggesting that K contamination has not oecurred.

    c1, analysed only in the leach of 1l*o5l+a, balances well


    with the I{a and K.

    In concl-usion 1 t+054,. is considered to be the most represen-


    tative analysis and indicates a partial fluid inclusion
    conposition of 5200ppn Na,1000ppm K,1?0ppn Li and 8000ppn cl.
    Sanrple 14056 (tui 13)
    Sample 1t+056 (vein quartz fron Raise 17, Champion 5 leve1)
    gave a moderate yield of uater (18rcg fron 62g of quartz). The
    crushed sample was leached uith the three different leaching
    soluti-ons,

    The leaches contain strong A1 and moderate Ca, Mg and Li


    contamination. The leaching patterns of IIa and K suggest that
    contamination has also occurred with these ions. Both have
    rnininun concentrations in the water leach and naxi.nun
    concentrations j.n the annoniun ni.trate leach. The Na/K and'
    Mg/Ca.,.ratios of the combined leaches and quartz analyses are
    simi-lar although the ti/Al, ua/aL and K'lAl are different'

    particles of a fibrous nineral occur in fluid inclusions


    of plates prepared for heating and freezing work, and balancing
    K and Al i.n the leaches as sericite can aceount for nost of
    the K as contanination fron this source.

    The total concentration of CI is insuffi-cient to balance


    even Na.

    fn conclusion the leaches of 1 l+056 have been generally


    contaninated.
    Samp1e 1t+061 (Tui 19)
    Sample 1t+061 conslsts of vein quartz from DD.'cross-cutr5 level
    Champion vein. The sanple was split into two duplieates'
    6so

    1t+0611and 1l+0612. The two sanples gave different water yields'


    12ng and 20ng respectivelyr frorn sinilar quantities of quartZ'
    Both crushed sanples were leached with the three different
    solutions.

    The leaches contain similar concentrations of the various


    ions before eorrection for the different water yields' but
    when the latter correction is nade the agreenent, although
    reasonable, is not as good. If the sanples are duplicates as
    originally considered., one of tbe water weight neasurenents nay
    be in error or alternatively the Leaches nay reflect equal
    anounts of eontanination rather than fluid inclusion corlposition.

    A1, Ca, Mg and Lt contamination are strong' The leaching


    patterns of Na and K suggest contamination of these ions also.
    The conbined leaches and quartz analyses have sinilar Na/K
    rati-os but different tta/At, Kf A!, l|g/Ca and Li/A1 ratios.
    Snal1 particles of a fibrous nindral occur in fluid i.nclusj-ons
    of plates prepared. for heating and freezing work' Balancing
    K and A1 of the leaches as seri-cite can account for al'l of the
    K, but only half of the A1, as contanination fron this sourcr
    The quantity of cl, is insufficient to balance Na * K.

    In conelusion the leaches of 1 4061 are considered' to have


    been generally contaminated'

    Waiorongonai
    Samp1e 1t$71 (Wi15)
    sanple 1t$71 consists of large vug quartz crystals
    coLlected fron a boulder in 0anadian Creek' Wairongonai'

    The sample gave a large yield of water ' l+7ng froro 599 of
    quartz. The crushed sanple was leached only once with nitri.c
    acid solution.

    Ca and A1 concentrations are moderate but when corrected for


    the dilution factor are very low. Mg and. Li may be representa-
    tive of the inclusion fluids. The various ionic ratios for
    681

    the leach analysis are d.ifferent from those of the quartz


    analysi-s. Cl was not analYsed.

    In conclusion, the high water yield and relatively 1ow Ca


    and A1 contanj-nation indicate that the leach is generally
    representative of the inclusion fluids, with a partial analysis
    of 3500ppur Na, 1100ppm K, 89ppn Mg, 89pprn Ll, 4.5ppn Rb and'
    /r. 3ppn C s.
    sanple 1 4090 (Wi 67)
    Sample 1/+090 conslsts of vug quartz crystails from the t'lain
    veln. The sanple gave a very low water yield, lng fron 35g of
    quartz.

    The crushed sanple was leached with the three different


    solutions. Ca and I'tg contanination is very high, whereas A1
    and Li contanination is low. The leaching pattern of lla
    fo11or.rs the general trend but K rises slightly in the nitric
    aci-d leach. A charge balance of Na, K and CI is aceeptable.

    In concluslon a partial analysi.s of 2300pprn lla, 500ppn K


    and, 2?00ppn CI is considered representatj-ve of the fluid
    inclusion waters.
    Sanple 1t+091 (bli 80)
    Sanple 1 4091 consists of large vug quartz crystals fron
    the l,laln Reef (bfg slip) between the Premi-er and New Find
    sectj.ons. Because of the sna1l amount of naterial ( gg) the
    sanple was not crushed under vacuun. The crushed sample was
    Leached with the three different solutions.

    Ca and A1 contanination are low, whereas Mg and Li


    contamination are moderate. The extremely high total
    concentration of Cl, relati.ve to Na, K and Ca, indieates Cl
    contami.nation has occurred.

    The leaching patterns of Na and K follow the general


    patterns and nay indicate that the eoncentrb.tions of these
    ions are representative of the inclusion fluid. If so the
    inclusion fluid.s have a Na/K ratio of L.
    Sanple 1t+091, (Wi89)
    Sanple 1lr09l+ consists of l-arge vug quartz erystals fron
    682

    the trlelcome vein. The sample gave a low water yield, 9rng of
    water from 53g of quartz. The crushed, sarople was leached' with
    the three different leaching soluti-ons'

    A1, l.lg and Li contaminati-on are high, whereas ca contanina-


    tj-on is low (reflecting ''he trace elenent composition of the
    quartz). The leaching patterns of both Na and K deviate from
    the general patterns, with Na being highest in the ammonium
    nitrate leach and. K highest in the nitric acj.d leach.

    The total concentration of Cl is insuffici-ent for a correct


    charge balance with Na and K'

    The total salinity of Na+K+Li is of a similar ord'er 'to


    other sanples but the possibility of Na contanination nay be
    indicated by: the low water yie1d, high concentration' of Al
    and Li, the unusual leaching pattern of Nar &r overall abundance
    of Na*K over Cl, and the high Na/K ratio of 14 (tne water
    leach and the eombined leached have the same ratio).
    sample 14098 ('gi 9lr)
    sanrple 14.098 consi-sts of large vug quartz crystals frorn
    the Inverness Vein. Because of the small quantity of sample
    it uas not crushed uuder vacuum. The crushed' sanple was
    leached with the three different solutions'

    High Levels of Ca, A1, , an<i Li eontarsination have


    oceurred. The total concentration of Cl is high relati've to
    Na+K and. contamination nay have occurred. in the water leach.
    The leaching pattern of Na follows the.general trend' but K is
    very high in the nltric acid leach relative to the water and
    annoniun nitrate leaches.

    Using only the coneentrations of Na and K fron the water


    and ammonium nitrate leaches gives a tia/K ratio of 5.7 which
    mayberepresentativeoftheinclusionfluids.
    Caleltes llorthern Colville,Peninsula
    Sanple 13970 (oc lr)
    saurple 13970 consists of calcite fron a vein erossing a
    tributary of Doetors creek, Paritu area. The sanple was not
    683

    crushed under vaeuum. The crushed. sample was leached once


    with water.

    As expected Ca and l"lg contanination is high. The


    concentration of Li nay be representative of the inclusion
    fluid. Cl is high j-n relation to lrla+K and requires balancing
    with Ca if no CI contamination has -occurred. K nay be a
    ninimun value due to the absence of amnoni,um nitrate leach
    values.

    In conclusion, if the sample is representative of the


    inclusion waters they have a Na/K ratio of J-ess than 3.t+ and.
    a Na/Li ratio of 120.

    Tokatea
    Sanple 13962 (no 3)
    Sanple 13962 consists of calcite fron the Royal Oak nine
    (? leve1). The sanple gave a moderate yield of water (13mg).
    The crushed sanple was Leached. suecessj-vel.y with water and.
    amnonium nitrate

    Ca was not analysed but l,lg contamination is high, Li nay


    be representative of the lnclusion uaters- The leaching
    patterns of Na and K deviate fron the general patterns but
    the total coneentration is insufficient to balance the
    coneentration of Cl ind.icating that only sllght contaninatlon
    could have occurred. The presence of a snall anount of Ca
    nay be neeessary to balance the Cl.

    In concLuSion, the partial analysis is 720ppn Na, 380ppm


    K, 15ppr ti and 1700pprn C1.
    684

    APPENDIX V

    THERMoCHEMI CAr C+LCIIIATI0NS

    INTRopUCTI0N
    Thermodynanics may be used in the study of ore d.eposits
    to calculate various physical and chemical parameter:s that
    nay characterise the conditions of rnineralisation. Ttre
    ultinate ain of this application j-s to establish tbe reasons
    for the presence of particular assernblages of ninerals and
    the absence of others in any individual deposit.
    NOTATION AND UNITS

    ai Activily of ion i
    aio Effective radius of ion i
    (ag) Aqueous ioni-c or noLecular speeies
    nr1 Constants of Debye - Hiickel equation
    BJ
    I
    eq.wt.$ NaCl Apparent salinity fron fluid inclusion
    freezing tenperature data (equivalent weight
    percent sodiun chloride)
    tj Fugacity of species i (Uars)
    fjo Fugacity of species i j.n its standard. state
    G Gibbs free energy (J. ro1-1 )
    (g) Ionlc or nolecular species in the gaseous state
    H Euthalpy (J, nol-')
    I Ionic strength
    I True ionic strength
    i lonic speeles
    j Ionic or nolecular species
    J Joule
    K Kelvin tenperature
    K Equilibriun coastant
    Kg Henryr s Law coefficient
    (1) Liquid nolecular species
    log Logarithn to the base 1 0
    ni [Iolality of species j (concentration in noles/Ue)
    M; Molarity of species i (concentration i.n noles/titre)
    no1 MoIe
    P Pressure (bars)
    685

    PJ Partial oressure of species j (bars)


    pil liegative logarJ-thn of the hydroqen ion acti.vity
    ue Entropy (J. l(-1. mol -1 )
    ( s) Solid nolecular speci-es
    ms Concentration of total sulphur in solution
    T Tenperature in degrees l{elvin, K = t, + 273.15
    t Tenperature in celsius (oC)
    d.egrees
    ,\J iiole frae',,ion of species j
    Zi Char3e of ion i
    F De;iree of d.issociati.on
    Vst Stoichionetric nean ionic actlvity coeffi.cient
    trj Activiiy coeffj.ci.ent of ion i
    5 Deviation, in per ni1, of an isotopic ratio
    fron the standard
    I Sumnation

    EOUITIBRIUI.,t
    #

    f ntrod.uctio4
    Barton et al (1963) stressed. the iirportance of evaluatins
    the degree of attainnent o.f equilibriun before applieatlon of
    mineral assen]:lage and nineral composition data to the i.nter-
    pretation of the physicochemical environnent of nineralisation.

    Barton et aI (lgll) considered the following four aspects:


    u ) the degree of attainnent of equilibrlun between aqueous
    (1
    species:' (2) tne degree of attainaent of equilibriun between
    the ore fluid and the ninerals being deposited. from it; (3)
    the degree to r+hich the original state (equilibriun or other-
    wise) has been preserved, or to which it has been nodified by
    post,C.epositional changesi and (a) the ,leTree to r*hieh mineral
    phases can be considered to be in connunication vith the ore
    fluid (and through it r.rith each other) at an;' gi.ven time.tt
    (1) gqui_libriun Between Aqueous Specigs
    Barton et a1 (1963) and Barton et al (1977) stated that
    ilost reactions between aqueous species are rapid even at roon
    tenperature and equi-libriun is qulckly attained. I'Iith the
    exeepti,on of reactions between oxidised and red"uced sulphur
    species these reactions can be eonsid.ered, alnost instantaneous.
    666

    'Gel' precipitoter
    rFibrsus cryslolc
    Very fine cryrlolr
    Skcletol cryslok
    4t Saslor-zoned eryslols
    e
    lSelectiva rcplocemcnl, I
    ll,
    o-
    :)
    at tilJ,"J,th bo nd ine'
    i "Jl"." I

    SATURATION = EQUITIBRIUM
    z Selectivo etehing
    o Mild ctching
    6 Dcep etching
    an
    fotol removol

    t.,','

    1llgnrc y-lr "Etfeeta of dl.tcgullibrtul ,bubrecn a hyilrotheraal rolut!.on anil tbo"


    '.--j;i.:
    vof,n (rtnernl) lyltca. (rroi Bartor 9,94' 1g77r. 1.
    (2) Eq-uili-briun Between the Fluid
    Precipitatine i'linerals
    and
    Reactions between crystal-s and aqueous solution are rapid
    relative to the tine involved for ore - fornring proeesses but
    inuch slor.rer than reactions between aqueous species.

    Fi.g. V-1 lllustrates the effects of disequilibrlum betueen


    ciystals and the hydrothernal fluid. Although sone super-
    saturation 1s required for nucleation, once thj-s has been
    achieved Barton g!.3! (1963) considered that it is possible
    for crystals to grow fron almost inperceptibly supersaturated
    solutions (i.e. 8t equilibriun in Fig. V-1). The rate of
    crysta3. growth irill probably be proporti.oual to the degree of
    supersatur&tion.

    Variations ln erystal supersaturated fluid disequllibriun


    are denonstrated. by growtn zoni.ng i.n cr;'rsta1s. Soue exanples
    e:rcountered. j.n thls study arei (a) grovrth zoning in quartz,
    generally defined by zones of fluid inclusious (Figs. 6-3 and
    6-/.) but in one exanple by inclusions of another ai-neral
    (fia.7-2), (b) grorvth zoni-ng 1n sphalerite d.efineC by colour
    banCs (probably due to varying iron coneentrations) or by
    chalcopyrite inclusions (Fig. 1r-19) (c) grovrth zonlng in
    pTrite defined by zones of inclusionsrand (d) alternating
    zones of quartz anil calcite in so:ire crystals fron l'{aratoto and
    Konata.

    0ccurrenees of erystalun.i.ersiturated fluid dis-


    equilibrium causes hyd.rothernal leaehingp. the partial or"'
    conplete re-solution of hydrothernal minerals by later hyd,ro-
    thernal- solutions und.ersaturated r.rith respeet to those rninerals.
    Hydrothernal leaci:ing of ealcite oecured in r:any of the veins
    within the study area as evidenced by the presence of quartz
    pseudonorphs after calcite. The quartz pseudonorphs originally
    eonsi.sted of an intergrowth of quartz and, calcite, hor,rever at
    sone tine af,ter deposition 'uhe calcite was leaehed oui, leavlng
    the quartz with a platy or lanell-ar texture. Re-soluiion of
    quartz also occurrecl in sone d,eposits, for exanple sotre vug
    quartz crystals at Maratoto are etched and corroded..
    588

    (3) Preservatign or l{odi-Lication of AssenbLaqes


    The cleposlts studied have presumably been subject to
    con-,inuouS uplifi since +,heir fornation and thelefore uere not
    subjectecl to reqional netanorphis:n, deep burial or crushing.
    j.io,,rer/er, sone earl;1 siages of nineralisati-on iaay be overprinted
    b;i laier stages (e.;i. Thanes c.f . i{erchant, 1978) and supergene
    processes :tay have renoved nany of the vein constitUents and
    oossibly redistributed sone others (e.,i. the occurrence of
    native sil-.rer anC nustard gold'is attributed' to processes of
    secondary enriciiment), ln addition to forning the readily
    id.entified second.ary replacements of prinary sulphid'es and'
    oxides (e.g. supergene covellite' chalcocite, azurite and
    linoni-te ) .

    Si.ni1ar1y, there appears to have been considerable over-


    printing of early propylitic i'rall rock alteration assenbla'qes
    by late ttoxyacidicrt solu'r,ions which formed. internediate
    argillic assemblages i-n the wall rocks and d.eposited i:aolinlte
    in the veins (e.f' Te Ahunat,a anC. Broken Hi11s).

    ilevertheless the sulphide and oxiCe assenblagas ideniified'


    fron uno:<idi-sed sanples by petrographic stud,ies are consi-dered
    here to be representative of the assenblages prevailing at
    the end of nineralisation and provided that the parigenesis
    has been adequately d.efined the assenblages will represent
    assenrbla3es of minerals conpatible with each other and the
    hyd.rothernal fluid at the tlue of d'eposition.

    Ilinera1 - Fluid - l"linera1 Interactidn


    ( /-)

    Barton et 4 (1977) consid.ered that there is i.nsuffieient


    lniornation known about any deposit to adequately fu1fil their
    fourth eriterion because it requires the Cefinition of all
    phases, ecnponents and variables d the speeifi-c equilibrium
    assenblaqe in question. frHow can ue eonpletely d'efine the
    chenical renvironnentt in a chenically d;rnanic systen?n
    (Barton et al, 1977 p7) .

    The closest approach to this last criterion has been


    achieved. by a few sphalerite stratigraphic studies (e.g.
    689

    ilclinans et al, 1980) in rvhich indi-vidual- zones in sphalerites


    have been defined anC correlated in different parts of a deposit.

    D i_s cu s si- on

    The sulphur isoiope data reported i-n Chalrter I contains


    rnany e:<ailples ',rhich depart from isotopic eciuil-ibriu:n between
    seei;ringI-v cogenetic sulphirle species. This evidence to.qether
    with observed crystal zoning and crustified vein textures
    (u.g. Fig. lr-6) prove that the various assi-.gned parar'lenetic
    stages are only groupings of broadly sinil-ar ind.ividual events
    in the evolution of the veln systems.

    Barton et aI (1953) aitferentiated between equilibriun


    in the sense of conpatibility oi phases and. equilibriun in the
    sense of compatibility of nineral conpositi-on. The latter is
    required for the application of sulphur isotope data to geo-
    thernometry but provided the ranges in conposition of the
    individual ninerals are sma1l, averaged conpositions (e.g.
    moLe /, geS in sphalerite) of indiviiual ninerals together ruj.th
    the generalisecl nineral assenblage data nay be used to infer
    broad liniis on the physieochemistry of nineral deposition.

    This thesj-s, like most previous sinilar studies takes tire


    broad. generalised approaeh, assuming tha'u the ra.nge of
    conpositions in zoned crystals is snall and that individual
    stages in the recognisetl paraqeneses represent equilibriun
    assernblages. fn this uay averaqe values for ter:rperature and.
    selected chemical pararceters can be defined for individual-
    mineralisations.

    Consideri4.T the linita',ions of the thernoeirenical d.ata


    used to calculate the varioUs parameters, irrther refinenent
    of the analytical data anC uineral phase i-nfornation, with the
    exception of a detailed sphalerite siratigraphy study, would
    probably add l-iti1e to the folloi.ring interpretation.

    An investigation of sphalerite stratiqraphy of an


    individ.ual deposi-.t is not possible in the stud.v area at preseni
    because of the absence of a sui'r,able suite of adequately
    located sanples of sphalerlte fron any of the deposits' hor+-
    ever, if the present mineral- exploratj-on activity produces a
    69o

    working nine in the future such a stud.y nay be feasible.

    EVIDE}ICE FROi'i FLIi :TCLUSfOI{S AI:TD STABTE ISOT0PES

    values of tenperature (from flr-riil inclusj.on and'


    l,leasured,
    stable isotope Cata), avera{e apparent salinity (fron fluid'
    inclusion-freezlng tempe:'atttre d.ata) and concentrations of lla+'
    i{*, Cl- and, C0, (fron fluiC inciusion chenieal anal3rses) for
    soge of the deposits are listed underlined in TabLe V-1.

    Although the few values for coneentration of indivi.dual


    species relate to late stage fluids they are used here to
    approxinate the fluids d,uri.n3 nineralisation. The validity
    of this approxiuation is supported by the fact that the total
    apparent salinity (fron fluid inclusion-freezing tenperatures)
    of fluiCs in fl-uid inclusions d.oes not differ significantly
    between main and late stage aaterial.

    Values of ilaCl nolality underli.ned in Table V-1 have been


    averaged fro;r the fluid j.nclusion apparent salinity and, ehenical
    analysis data to red.uce the erors inherent in the differen'"
    types oi neasurenent- Apoareni; salinities calculated. fron
    freezln: teaperatures are orobably naxinun vaLues of equivaleni
    i.TaCl concentraiion because they have not been corrected' for
    the presence of dissolved C02+ rshereas ec.uivalent lla0tr concen-
    tratlons caleuLaied fron the i'ia*, K* a1rd Cl- concentratlone
    of fluld inclusion leach analyses are probably nini.mun values
    because other ions (e.g. C^2*, lO4
    2- etc) nay be present in
    si gnif icant quantitie s.

    Values for tenpera'i;ure' ealinity, r,rolality of ltra0lr i{a+


    anC Cl- not und.erlined in Table I/-1 have been interpolated'.
    For exanple, l{a+, i(* and CJ'- coneentrations lfere calculated'
    fron neasured, or assigned salinity and teuperature values by
    using lla+/K+ ratios calcula'ued fron tne lta/K geothernometer
    of Ellis & l"tahon (1977) and finally balaneing ltra+ and, K*
    concentrations rvith CI- to natch the total salinity values'
    i{a0l raolality values uere deriveC fron the apparent salinity
    data.
    6ga

    Factag page.

    TANIE V-1: Sme thnmoehwricel panameters for ealected. milneralI.satiqls.


    Vellree tuderff-bed r{er esl,culsted froq f,tuJd iaedlsefq and stable
    tsofropg datal r*reroas. aI,I, Ether v.alues rero est'i.tsated (oc trxt),

    Notec' tft - teqryena,burre asdgrrcd to the tlf,,nerslfsa,f,1En,(%)"


    pll ot pn ot
    tnoc #ti"nv Na/K
    eq.wt ) arNaCl xl.ralic ra lla+
    $hal
    mYr m Cll mC02 I * NaC i Lodrtl(
    e5'c)
    Loq
    (il'c)
    K LooIK Wok bod(.
    nXl LDql
    ifor I) $oi 1) (zg'c) ftL'c)
    Kaolintt ,<ircfie1
    6an<ln <-fzldl,f
    lCazt fi\c}{ lcoz f C}z -9rq
    (bars't
    lxro-z;
    IINER5 I{EAD 42r_ p t.1 2.4 1.2 o.5 1.1 .1 o-l o.t-7 -0., -1.7 -1.-74 -l.ol -2.04 -2.71 4.' t-5

    19tan. I 240 l- o.l7 6.4 o447 o.a2, o-t1 ot7 0.9 o.t5 -1.@ -1.60 -o.27 -o.2, - t.9l -11, 4.-7 6'l r.5
    TE Al{UMA-t Al5laqe 2a 2?O I o'11 1.' o't o o.q20 o.t7 o.t7 o9 o'19 -t.70 -1.74 -o.25 -o.24 -t.q5 -l98 4'g 6.2 t5
    l5taa, tu 270 o-17 6.9 o.146 o-o'fz o.n o.t7 o9 o.t5 - t.66 -tno -o.26 -o.2, -t.92 -l-q, 49 G-2 t-5

    PAR,|TU I Cooshl *db( 42' 7 1.2 2.4 o.e, o.7' 1.2 1.2 o.l o.t2 -o40 -l4b -lSfa -t,t? -2.12 -2.5? 4.9 8,6 t'5
    lcu-fla-zn Vrnl 125 1.6 o'n 7.7 o-21, o.or-l o.n o'z-l o.-7 o.1g -t.24 -1.40 -oq -o45 -t.17 -t-85 4'l ,.G 1.5

    AURI - KAPANGA 220 I o.t7 7.' o't o o.o20 o.t7 o4-f o.9 o.t5 -t.7 -t.-74 -o.2' -o.24 -t.q5 -1.?o 4.1 6-2 t.5

    TOKATEAI Baq, lffials 2go .t o.2b 4.8 o-2tu o.e9 o.20 o.26 o.6 o.2l - t-7, - t.4+ -o'77 -o.A -1.-tz -t-76 +.t 5.4 t.$
    Au- Aa 220 2-l A:24 2.O o.qo o02, o og7 o., o.t\ o.q7 o.t1 -t'@ -1.G2 -o.7, -o.25 -1.9, -).gl 4.8 6.1 -o.L -u:[t 49 o.9 56 t-7

    PE1OIE STREAh/ ?oo 2.1 O.Zl 16., aJ* O'OO{. o.o% o'b o.lz o.a6 o-tl -2.26 -2.28 -o.t2 -o.7, -2.11 -2.E' 5- L9 -o9G -o.29 6.6 l.o 4l r4
    WHANGAPOVAI5Taa 2 280 t.> o."G 4-g o.2t9 oo49 o'2b o.2Q o.8 o-21 -t-75 -1,& -o.r-7 -o.v4 -ln2 -t.79 4.7 ,.4 1.5
    'l9r&,4 200 I o-l v- o-to O:Ol2 o.laq o.3 o.tl o.g7 o-l -t q4 -1.% -o.20 -o.% -2-t4 -2.t4 5.2 G.' -o'67 -o.1. 4. )? 2.O

    luAoTuNu 250 o.n G o.t4c o.o24 o-n o47 o.9 o.,5 -t-62 -t-bl -o-28 -o.27 -l go -194 +.6 6.1 1.,

    N HILL9 240 l- a.n 6.4 o.141 o.oz, o.t1 o.l7 o.g o.t5 -t.64 -1.62 -o.21 -o.2, -t'ql -tqt 4.'7 6,1 t'5

    TAPU. I Cu-Bi 4Ae 2 o.74 2.6 o.24b o.@4 o.7+ o.z4 o.2 o.o7 -t.o, - l'-7' -o.9, -o.r7 -1.99 -2.70
    o.9 -t.o? - t.tg -o.46 -o.41 -t'40 -t-r?
    4.2 ,'b 1.5
    Ttf AMEt I Pb -ZY1 4.2 o.r9 a.6 o'$fr o.n, o.55 o.5, o.-7 4.1 t.6 t-5
    "80
    THAMES uld-anrarai(ft 7vo z.b o.44 69 o.7U o.orc o.44 o'4+ o.8 o.7, -t.E -l-78 -o.75 -o'v2 -1.60 -1.o7 4.4 59 1.5

    {EAVE9VILLE) AIoX 250 o.7 o.ll o.o72 o.olb o.or4 o.2 o'o4 o.cr' o.o+ -t.79 -1.'79 -o.lG -o.tb -,.rt, -t'9u 4.7 6-l -o.r+ -o.t E. o'zL l.
    I Bluft: 220 o.6 o.lo -t', o.ooe o.o,2 o.to o.lo >o9 o'10 -t.92 -l'72 -o.20 -o.20 2't2 -2')z 5.o 6.4 o.2C IG 1.2

    MARATOTO 2go I o-11 +.1 o'l?4 o.otg o.ov+ cr. t o.o? o'?7 o.o9 -t-71 -t.14 -o.25 -o'E -t-9, -t 99 +.6 6.1 _ o.6l -o.2, 5.> o't8 l(' 1.2

    JAI1EKALIRI 200 o't9 4.9 o't U.U+( o-t9 o.tc) a'6 o-t, - t.+a - l.qt) -o.B -o.71 -t.1t -t- a 4.+ 5.9 1.5

    \ low lcvcl5 725 ItL o.v, 7.7 o.264 o.o7a o.n o.7' o.b o.20 - t.t5 -1.78 -o-r2 -o4, -t.67 -a.6, 4.1 ,., -1.72 o.40 5.9 t-5 5A t.7
    iJAlHl I thterncdialc tor. 260 t-9 o.7, 4.s 0.27 o.or7 o.7V o.vv o-7 o.z7 - 1.2, -t.40 -o.29 -o.E -1.6V -1.-t> 4.' 5.7 t'5 72 t.9
    ) upoor Wvels 220 4.9 o.1q 7.' o.2?l o o79 o.7t o.8 o.V7 o.g o.vo -1.41 -t.45 -o.11 -o.ro -1.72 -1.7, 4.G 6-O -o-gl -o.n +9 1., g1 2.o
    KARAN6AHAKE (lary lcrclr loo 2'7 o.7? +-2 o.7tt o.t7, o.r9 o.79 o.7 o-n -l-12 -t.29 -o'49 -o.*z -t.26 -r.7 4., ,-,
    fUl MINE l9laae I 4aA 7 o-rl 2.9 o.77 o.l1 o-r, o.rl o.2 o.to -o.85 -1.>, -t.06 -o'G't -1.91 -2.21 4.1 ,.5 o.97 t? t-V
    | 5taae 2 too , o.18 6.2 o.2' o.gza o.nG o.9 o.24 o.80 o.g -t.99 -t.68 -o-40 -o-77 -).99 -2-O' 45 6-O -t-rg -o.74 5.Q o77 42 l'("

    WAIORON6OMAI ,2' 1.6 o'ta 44 o-t, o.o2l ooTc o.G o .to o.7g o.o8 -1.(4) -1.7e -o.7b -o.qa -".09 -2.11 4.' , '', -1.q. -o.7, E.? t.o v2 1.9
    692

    to,'ilc stn;ltctii (at aooit ln:.teeRatuRe)


    Ioni-c strength, I, rtis a quantitative neasure of the
    interatonj-c effects of ions on the basis of the concentra!-ions
    of , and the charges orle the i.onstt (p316 Vaughan & Crai-g, 1978).
    It i-s defined. as follous:

    +
    -LL
    ,, .2.2 (v-1)

    ilhere r:..
    L
    is the nola1ity and Zi is the charge of the i th ion
    in the solution, the sunnation being talien over all ions,
    positive and negative.

    The ionic strengths of analysed inclusion fLuids at


    "oot
    tenperat[rgr assuning complete dissociatlon of ion paj.rs' are
    listed underlined in Table V-1. Ionic strength values not
    underlined ln Table V-1 were caleulated fron the apparent
    salinity values (freezing tenperature neasureaents) assuning a
    sinple ltraCI fluid conposition.

    ASSOCIATIOI{ OF IOItr,S AT ELEVATED TEIIPEF.ATURE

    At elevated. tenperatures ions in solution forn ion pairs


    and conplexes, reducing the ionic strength of the solution and
    the activity (see follor.ring section for discussion on activity)
    of ',he various ions. Therefore the true ionic strength (T) at a
    speci-fic elevated ienperature nay be related to the ioni-c
    stren3th at room ienperature (f) by a correction for association.
    The ezpression used here is;

    T- =I< ( rr-z)
    lihere o< is the degree of d.issociation of the conplex or i-on
    Dair.

    Evaluation of oc requires knowledge of the dissociation


    constant (Kd) and the stoi-chionetri-c nean ioni-c activity co-
    efficient ( y st) for the various ion paj-rs and conplexes.
    Experinentally derived data for these parameters is sparse for
    the various species assuned to be present in the hyd.::otherrnal

    :
    i00T,iC i-f & i s sonetiires expressed as the degree of
    F'<

    associa+,ion (e.f. 5e'*arcl , 1981 ) l" r,rhich ca-se associatj.on


    = I - & d.issoc'ietion.
    6gt

    fluid,s. fn fact for the teaperatures and, conceatrations con-


    sidered here, d,ata are available for only iIaCI. Therefore
    for the evaluation of high ternperature association ihe systen
    is coasidered, to be represented. by the reactioni
    NaCIo = Ha* + cl-
    This approxS.nation is probably not far fros the real
    situation because ltra* and CI- are
    +
    the d.oninant ions found i.n
    fluid j-ncluslon analyses and K', tl" aext.nost connot! lon'
    exhibits siailar bghaviour with CI- to lia- (c.f, Fig- 2 of
    ilelgesoa, 1969) at these tenperatures and. coacentrations.

    0ALCUT.ATTO$ ,0F THE pEGREE OF DISSoCIATTqI{

    Tbe und,erlined values of oa lla0l, the degree of d.issociation


    of tbe NaCI ion pairr presrted in TabLe V-l were calculated,
    by the nethod, described by Seward (tgZg) - Three equation,s
    are required, for the calculati.on:

    (v-/-)

    (nodified forn of equatlon 23 of Seuard, 1976I


    Yst of Seward.,
    Ycr- = oC
    ( equation 2l+ 1976)
    (v_ 5)
    2"t
    Y [c r-]
    d-=1-
    ttd..tu
    (equation 25 of Serard.' 1976) (v-6)

    where [cr-] = concent,ration of free G1- (unknosn)


    lU= d,issociation constant of ilaC]. (values fron
    Fig. 6.? of Seward., 1981)
    -a
    Inr-
    L"* J in
    I - concentration of total Cf = neasured conGoil-
    tration of Cl- in fluid, inelusion leaeh
    experinents
    Y"t = stoicbionetric Gea4 di.vity coefficieat of
    l{aOl (values fron Table /* of Lui & Lind.say'l972)
    Y,, = aetivity coeffi.cient of the i{aCI ion pair
    (taken as unity)

    Equation (V-4) uas solved iteratively for [tf-] , initially


    -,:..,. ..t, :
    69!+

    (,
    6
    z,

    nliuf.i l'-2r' '!Dc ilcgr.ic.o! dl.oroolatien 1oa I of tteGl rolstisne up to too9c.


    '(ffo.dUtrd f"r.or;ftg:' 6.'9 of serrr{l. ltSt',)
    @r

    by naking YC1- = Y and then by using neu values of / ,rt


    derived fros equations"t(V-5) and (V-5)rusing each ner+ valu.e of
    f Cf-J fron equation (V-4) until essenti.ally constant values
    of [cf-l nere obtained, Betveen two and four cycles through
    '"he se'r, of three equatlons r,tere required to obtaia each
    unCerlined, value of o( }la0l presented. in Table V-1 .

    Values of oc IIaGI not underlined in Table V-1 were inter-


    pol.ated. from Fig. V-2 for the assigned values of tenperature
    and l{aCl equi.valent concentration.

    It i-s apparent frorn the calculated. aad interpoLated values


    o! & llaGl that for nost of the nineralisations consid.ered here
    ion association j-s not a very inportant factor and when the
    possi.ble errors on the vari-ous paraneters (e.g- tenperature,
    salinity, etc) are consid,ered,, the association eorrectj-on for
    aineralisations forned. belolr 325oC could probably be ignored.
    However, to avoid problens in selection of a cut-off point,
    corrections for assoeiation are nad.e here for af.]- nineralisations
    considered..

    ACTIVITY AiLp ACTIVTTY COEI'FICIE!'ITS


    Activity is a neasure of the effective concentration of
    a reactant or product in a chenicaL reactioa.

    The activity (") of a specific ion i is reLated, to its


    concentration (expressed in nolality units; oi) by the activity
    eoefficient ( X i) as d.efi-ned by;
    oi = ti''i (v-?)

    Activity coefficients nay be derived, experinentally or


    calculated by one of various equations based on the Debye"-
    Hiicirel theory. Experinental derivation of activi-ty eoefficients
    at high tenperatures and in dilute soLutions is dj-fficult and
    consequently few d.ata are available for these situations.

    listed in Table
    Debye - Huckel
    q6

    TilfPffiAfljRE

    Ff,gudp Vr.,|ri oll 5bo;6ruta* aad nautral. Bf, of retn':r at olsyetiii! ioupcratule'rr
    (Ff.ottrd frpa iletr la flpbor & Fsresp,r 1rgqI'l
    6gz

    A. z12,,G
    1og Ui = (v-e)
    1+ . g{l
    "jo

    Where Z,L"Lis the charge of the i th ion and al is its


    effective radi.us (values fron Table 2.'l of Garrels & Christ'
    1965), I 1s the ionic strength of the solution and A and B
    are constants characteristic of the solvent (considered here
    to be water) at the specified temperatures. Values for A and
    B, for temperatures up to and including 325ocr were taken fron
    Table 1 of Helgeson (1967)' hotrever values for 400oC and' t25o}
    uere extrapolated graphically fron Helgesont s d.ata because the
    highest tenperature listed for these constants is 35OoC.
    Extrapolated. values for A and B used. here are as follows:
    A; 400oc = 3.0, l+25oc = 4..0 and B; 4.00oc = o.t+75 and lrz5oc =
    0.510.

    E
    pH is defi.ned as the negative of the logarithn of the
    hydrogen ion activity;
    pH = -1og a H* (v-9)
    Neutral pH is 7 aL ZSoC but changes with increasing
    tenperaturer Fisher & Barnes (lglZ) investigated. the ion
    product of water, and hence neutral pH' at elevated, tenperatures
    (100 to 350oC). Their results are shown in Fig. V-3. Between
    200oC and 350oC, a range bracketing nost of the nineralisation
    tenperatures of the d.eposits studied here, neutral pE is
    betrreen 5.5 and. 5.7.

    of the hydrothernal fluid can be estinated using


    The pH
    the activity of potassiun in solution and, the wall rock
    alteration nineral assemblage. The stability relations betneen
    the diagnostic alteration ninerals are illustrated in Fig. V-l+
    and defined by the following hydrolysis reactions:
    1.5 K-feldspar * E+ = 0.5 nuscovite + 3 quarl,z + K+ (v-10)
    nuscovite + E+ + 1. j E20 = 1.5 kaolinite + K+ (at <3oooc) (v-tr
    nuscovite + H+ + 3 quartz = 1 .5 pypophyll-ite + K+ ^ (V-t e)
    (between approxinately 300 and 400-C)
    nuseovite + H+ = 1.5 quartz + 1.5 andalusite + '1.5 HZ} + K+
    (at> 4oooc) (v-13)
    ,',w

    lilFflir|'r*

    llgsro 9*.4t H.trncrrl, ateblllt, i'all,i'ti,oar ia thc ayrtcr K:29-A12Ograi62-f,i0-SC1.


    (Fron ftlg.lr of lioatoXc l. fic,illsy/' 7975.1
    6gg

    The pE of the reactions can be expressed as follows:

    pH =J.ogK- logaK+ (v-14)

    Where 1og ,( is the equilibrium ratio oH* read off Fi-g.


    oK* f
    Y-lr, for speci.fic tenperatures, and log aK+ is the activity of
    potassiurn in solution without correction for conplexi-ng and
    ion pairlng effects at the elevated tenperature beeause these
    are aecounted for in the stability diagran (Montoya & Hen1ey,
    197 5) .

    of the relevant hydrolysis reactions for the


    pE values
    various deposits studied irre presented, in Table V-1.

    CALCfTE STABITITI AND pH_

    calcite is stable can be calculated


    The pil above which
    fron the C0, content of the fluid using the following
    relationship:
    (K,r)z (Kz) Vc^2t . nlrcl, ("p.)
    (ow+)? = ( v-1 5)
    2 l(ce vs
    ' gco3

    Where /(r r lt,are the equilibriun constants for


    and' Kce
    the following reactions respectively:
    *p.
    H2co3 = H* + Hco3- (v-15)
    Eco3- = H* ,o .,'- (v-1?)
    -+
    caco, = c^2+ + co32' (v-18)

    YC"2+ is the activity coefficient for Ca2*, YttCO, ls


    the activity coefficient for HC03-, and nHTCOU (ap.) ts equated
    to nCQ, analysed fron the fluid incluslons.

    The ni.ninun pH values for calcite stability calculated


    fron measured concentrations of COa are presented. in Table V-1.
    A value for high temperature nineralisation at tiaihi (rWaihi
    7oo

    c\,1
    o
    L)
    (i{ \+\O O cO \C rr\ C) N r \O C{ O O tr\ C\ tr"
    aaaaaaaaa.aaaaaa
    bn rCVrrCJrrrrOlCVrr-
    o
    r{

    cvm oC \+ O O.\ \ CV C\t


    Ot{ O t-- cr\ \t cr. tr- O.l c^
    cc\ \t
    q{P N \+ Cf. \O -+ cf\ O. r- r O. O\ (\ tr\ l(\

    (-)^
    dcv OOOOOOOOOOOOOOOO
    O O O O C)-O O O O O O O O O O O
    Gr'i o F rf\ o cc oo oJ \O rn O co oo o \o \* cv ol
    .D Y-) tt \n tr\ \C \+ \+ \t \C \n \O -+ \t \C \O \+ rr\ lr\
    d'
    t{
    +)
    H
    oooooooooooooooo
    rr\ cr\ co co cc o rr\ a\
    -+ e{ oc| co cf\ Q| o. \o \o
    o {JO O,l nj N c\2 ol C{ N C! CV e{ CV Oi C! c{ C{
    o.
    5o.
    ol *x(**** t- Ot F
    c-.
    c) *+ cC va \t O. tr* rr\ cr\ Ol OO cn u\ r @ O C)
    -c
    -lJ
    c)
    rl o
    e{ OOTOOTOOOOTO
    OOOOOOOOOOOOOOOC)
    p aaataaaaaaaaaaaa
    frd
    oF{ X oooooooooooooooo
    F{v
    m
    .rJ g
    oo .-l
    {J
    cdt'
    r-l A o
    :Jr{ nd
    oc) o
    r{g Flr, gFl
    dEl e
    o cdodo
    't, o{ro
    c{ .rl .!.i f-l .rl E ,g O
    OJ qr O-P[rc0r.'lg
    r) rJ O. 01
    c+-.t
    a+{ osrFr.fucf\ofuo
    qrg oogo{roo
    doocnHr{A
    O o
    O 'rl
    bi i Fl
    {J J4 r{ (!) FI r{t, AFtr.c\ Fl O
    C- +r {r cd O Ff Fl t(\ E
    (a ol }{ rt'rt J.r{ .q tJ ol c\ A cr\ E O
    oo o caE}1i{ ov)
    5c) .rl tdh0xdailP.r{Oor{ oo
    'd
    .J
    q-{
    p d O O - . r g d r{ fu rl q{ O r{ .Ft 0)
    d o-1 cddcd'-{.-?OOOcd rl r{
    c) J)d-{OOOcd
    c#{ . dcd
    o d cd tt F F{ e -l F @ d d d
    d :1 qr =
    O7O...-O()r4()rn+()C)rJ c{ c^
    O,l EiPCd FSEd-lrtuE qr q{
    1',
    i
    +J{J=Jr{t.rQd...O
    a r . Cq A A O .rl O O O Z t
    dddp.
    O O b..l oo
    O O O O O O cJ v, O O O - .. .r{ .r{ O oo
    F: Jr -P {J {r .+J {r hf, O {r +J +r .rl .rl E Fl
    dddooog =, dd
    A{ J4 Jd {r + P cd d F. ! ${ .-t .rt .rl .r{ 'rl HH
    oc)
    E{ oOOoooslosdrdoddd==d
    tr E-r H P{ Pr g{ F Z E E E ts t E-{ F F dd
    s ol
    o
    N
    .rd ot+c\o\
    rl vt416.\Org1
    c) C\t C{ (\ \O Ct c) O\ -* e .-t .rl cJ
    pc) .rl ld O O = A A b.0 r Ol r .q. 5 J .r{
    F.r F{icdi{

    -+
    O.
    (\
    r.F
    o
    E\ co N C- O co c' O\ or\ \O CO \t C- C- r -+
    a rnrf\\OOCOoF\rCf\
    F O\ O\ O\ O\ C) O O O O
    Cf. O. cl\ O\ O\ O\ O. (q
    c cf\ cr\ f\ 01 r cl c\ c\ cr\ \t \+ -t -+ -+
    t-t-l.-,r-rrli-rrr
    701

    low levelstt) is also listed and was calculated for 3?50C


    using the neasured COe concentration frorn the low tenperature
    fluid,s.

    FUGAGITY

    Irtroduction
    The fugacity (f) of a gas is the reffectiver partial
    '
    pressure of the gas and. nay be regard.ed. as being the ioeasured
    partial pressure corrected for deviation from perfect - gas
    behavi.our. At s1all pressures (<1bar)fugacity
    approxinates partial pressure.

    Fugacity is related. to activity by the follosing expression:


    f
    a= where fo is the fugacity of the gas in (v-19)
    Jo its standard, state,

    Krauskopf (1972) pointed out that in nost geological


    applications a = f for gases.

    Fuzacitv of C0^

    Fugacity of COZ fron Fl-uid Inclusion Data

    The fugacj-ty of C0, can be ealculaied' fron the raeasured,


    fluid i-nelusion concentratioa of C0, using Eeuryt s Law,
    expressed. as foll.owst ;i.

    , K-g=:% (v-20)
    ^ao,
    llhere Kn Ls the Henryts Law coefficient, fCO2 the fugacity
    of GOa and XiO^ the nole fraction of CO, in the fluiel- Values
    of Ko for specffic tenperatures llere read off Fig. 2 of ELlis
    & Goidring (1967).

    fCO2 vaLues calculated. frorn selected fluid inclusion


    analyses--(c.f. Chapter 7) are listed. in Table V-2. The fluiCs
    that these represent were gen'erally later in t?re vein para-
    genesis than'tbose responsible for tfre nain ni-neralising events.
    ?02

    TABLB V-3: f,COa durtng ileposltlon of eplthernal deposJ.ta at Sunnyelde' Colorado


    (Ta;ls V-3A) aad Bagulo Dtstrlct,r Phllipptnea (Table V-iB)' based on
    flulit lnclusion analyeea by Casadevall & 0hnoto (19??) aird Savktns .49l
    (19?9) respectlvely.
    Although Casadevall & Ohooto ('19771 calculated valuso of log fC0,
    batvean -0.3 and +0.6, thelr data are recalculoted here bacause of
    geveral nlatakes in thelr paper shlch appar to have been lncorporated
    tnto thelr calcul.atlong. For exauple they lncorrectly atated (oa pl302)
    that Ellls & Ooldrlngte (1953) data ladlcate that X.s a+' 2OOoC 1g 4,?00
    nheroas tbls value ahould be 5r?00. AIeo the range of XCO^ glven ln thelr
    t llsted ln
    textr 0.001 to 0.0001, does. not agree vlth the valuea
    thclr tables (approxl'lately 0.01 to 0'0002) '

    TABLE V-3Al Sunn;.'side (Sanple nunbersrC0, analysee and


    . tenperatures fron CasadevalL and Ohrnoto, 1977)

    Sanplo llol Stage


    ttoa *1
    t oc l(e fC02 1og fCOt

    9-20-9 2 0.0029 1 300 1300 13 +1.'l


    tc-1 5-73 3 o.oo35 *2 290 4L00 16 +1 .2

    20LO t 0.00025 30o L300 1.1 +0.0


    g-1e-5 5 0.00360 300 t|300 15 +1,2
    2090- 1
    ( 0.00350 300 /r300 15 +1.2
    9-11-1 6 0.00071 230 6000 lr.3 +0 .6
    21 50 6 0.00017 230 6000 1.0 0.0

    i1 Values fron X condensables column ln Table 6 of Casatlevall &


    Ohnoto (1')771 usad to approxlnet" Xco- (co, nakes up ) 95{ of
    the condenslble gas fraction)
    *2 llsted as 0.00036 by Casadevell & Ohnoto but nuet be 0.0035 to
    agree wlth their statect aCO, value of 0..20 (also thelr Table 6)

    TABLE V-38: Bagulo DLstrlct (oample nunbersrCO, analysea and


    . terperatures fron Sarklns et al, 19?9)

    Sanple lto: t*l oc l*2 rs fco2 log fco,


    "o,
    75-B-21 0.001 3 280 L700 6.2 +0.8
    75-B-1 0.0029 280 4700 11 +1.0
    75-B-22 0.0030 260 53oo 16 +1 .2
    76-B-1 6 o.oo22 280 1,700 11 +1 .0
    76-D-22 0.0006 310 4000 2.5 +0. a
    76-8-2 0.00?4 280 l+7OO 35 +1.5
    76-F.20 0.0052 t?00 2L +1 .L

    t*1 approxlnate teaperature Lndicatetl by fluld lncluelon f111ing


    tenperatures for the speclflc eanple.
    |,12 tenperature aasigned to sanple here (no teroperatures Il steil
    by Sawklne et aI)
    703

    fC0,I values for nain stage fluid,sr presented underlined in


    Table V-1 were e:'.trapolated. by averaging the C0, coneentrations
    of individ.ual analyses for each Ceposi.t and'using values of
    Iienryrs Law coefficiebt for the higher tenperatuf,es.

    The rrnaj-n stagetr fC02 values together r.rith fC02 values


    for si-nilar Ceposits, reported, in the literature (listea in
    Table V-3), are plotted. on a 1og fCOZ versus teuperature
    graph (Fig- V-5) in an attenpt to define sone relationship
    that nay be used. to predi-ct fCAZ values for nineralisations
    where no analyses are available.

    A naxLuun value of fC02 can be predicted for nost d,eposits


    because:liquid COa is not found in the fluid inclusj.ons and
    C0, clathration was not observed during fluid inclusion
    freezing temperaiure experinents. These factors are d.iscusseC
    in Chapter ? where it was eoncluded that they represent naxinua
    COZ concentrati.ons of 3 and 1.5 nole f, respectively.. The
    value of 3 nole I GoZ, defined by the absence of liquid COt
    is used here because freezing teieperatr,ure experiinents were
    not perforned on all inc1usi.ons stud.ied and therefore '"he
    absence of claihration nay not be a uni.versally applicable
    criteria.

    Using a value of 3 rnole fi for the C0, concentration and


    the Henryr s Law equation, values of naxinun fGO, for flqid
    inelusions free of liquid. C02 ltere deternined. for different
    tenperatures and. plotted, as a line in Fig' V-5.

    Giggenbach (1 981) considered that j.n llen Zealand geotherual


    systens (e.g. t'Iairakei, Kawerau and Broadlands) C0, pressure
    is related, to teraperature by the follo'nring seni enpirical
    fornuLa:
    1og PrO 15.26 - ry (where T = of) (v-21 )
    Z=
    This reLaiionship is illustrated in Fig. V-5.

    Although the neasured, fCO^


    .4
    values fron fluid inclusions
    plot in a r.qndon pattern there is some agreenent ulth
    . .:.1 :

    _r". .i " .;,o,q. .

    r ; ,i " ,1, i;tidi'lri. 1,,, ,


    7Ol+

    ) |{auraki Gold -9\lver Prwrnca


    (*e'arVo Minc,Tnamcs liqurd COz
    n tVtd intlu:lonr)
    o lunrryAdo,, Colovado.
    * Baqho Dirtrrct, Philliprhel.

    -l

    o
    oNo
    r-,
    o
    rs\ rl
    o

    +2

    fosnperdrurc 'C

    Ftgurc Vr5r Plot of fCO, veraus ienparature. The fCOa valuee nere ealculated
    us!.ng equatlon (i-ZO) frou COa concentratlons reagured ta fluid
    lnalluslona (Tablea V-2 ancl V-3). AIao plotted a'ire a graphleal forn of
    GlggeubachrB (1981) expresston P00r. 15'26 - ?850, corr6cted to fugacltyl
    and a llue belov yhlch fLuLd lnclual.ona eould be expected to contaln
    ltqutil G02 (obaervedl tu only one aanple frou the Baurakl Provl.nce, by
    l{erchant 19?8). A log fG02 value of i1.5 1g gelected for all ilepoalts
    (at all teaparaturea eonslderod) ln rhlch Do [eaaurerents rere lade.
    705

    Giggenbaehrs curve bei,..reen 2BAoC and 30OoC, appra).iuately the


    upper telperature ranEe of nost ller,r ZeaLand geothernal systeas.
    Beloru 2B0oC Giggenbachr s equation underestinates the fCO, in
    tb.e fossil hycirotheraal fluids. Conversily above 32OoC his-
    curve crosses the li-ne delineatin3 the naxi-uun fCAZ limit for'
    fl-uid inclusions free of liquid COa (fig. '[-5) and therefore,
    with the exception of the single sample from the Garbo l'{ine
    .reported by llerchant, olrerestinates fC0a for the lni-'-ln
    tenperature fluid inclusions stud.ied here and by i,ierehant.

    Fluid incluslons frora at least two hi3h tenperature


    ninerali.sations (Sta4e 1 nineralisation of Tui lline and
    porphyry copper nineralisation at Paritu) have not been stuti-eC
    because of the absence of suitable rnaterial and therefore'the
    hydrotherrnal fLuids responsible for these d.eposits may have
    contai-ned high concentrations of COZ. Gig3enbacht s formula
    predicts C0, partial pressurei of approxirnately 3,000 and
    10,000 bars respectively for these deposits, however considering
    that their naxi-nun confining pressures are thought to be i.n
    the order of 400 (fui i''tj-ne) and ?00 bars (i{iners Head) tfre
    values of fC02 r.ril-l be of a sinilar nagni.tude or less.

    Based on the available data presented in Fig. Y-5 a


    value of *1 .5 f or 1og fCO2 ,.+ould appear to be a reasonable
    ap:roxi-iation for the deposits rrrhere measured CC, ccncentratj-ons
    are unavailable, vith the provision that higher concentrations
    may ha're been present during early nineralisation at Tui l{ine
    and in the porpi:yry cop?er ninerali-sa'r,ion at Paritu.

    Fugaeity of C0a Froa Hydrotherroal Alterai;ion l.{ineral Assemblages


    Bro,,rne & ;llis ( 1 9?0 ) ,JenonstrateC that the siabilitlr of
    caleiun ::inerals such as trairal:iie and epidote are related to
    the fugacity of COZ in solution. At high concentraiions of
    CO2t calcite tends io be d.eposi-ted at the expense of epldote
    or uai-rakiie. Therefore the sequence of aineral assenblages:
    epidote + r'rairakite + calcite, wairakite + calcite and calcite
    represent increasing fC02 (c.f. Figs 3.8 and 3.9 of El-Iis &
    ilahon, 1977). The presenee of walrakite and epidote in an
    alterati-on assenbla-3e nay'therefore be used to Ei're 4 general
    indicaiion of the CO eonceniratiotr in the hydrotirernal f luid.
    "
    fn'r,he case of epid,ote this nay be fur'uher refined to give
    a value of fCO* if the epidote conposition (itt terns of rnole
    fraction pistacite) and tenperature are l:nor'm, by usinE the
    Cata of 3ird. & Helgeson (1981). Robson (19'79) caleulated COa
    fugaciiies beiueen 5.5 and 25 atnospheres (1og f.COe = 0.7 to
    1./r bars) :-n ttre tenperature range of 250 io 3?:OoC fron his
    analyses of epldot,e ln propylitic a1i;eraiion of the '-ihan3apoua
    ZLTe?. Propyli'r,ic assercblages, forned. bet',reea 25A an'i 32OoC,
    in rahich epi-i.oie is absent were probably ia equilibriua r'rith
    a iluiC containing higher fugacities of C0a.

    Fugacity of St

    Introduction
    The fugacity of S, can be estinateC froin the iron (l'eS)
    content of sphalerites in equilibriun with pyrite or pyrrhotite'
    fron the iron (feS) content of pyrrhoti-te' fron the nole fraction
    of silyer in electrun or by considering the mineral stabilit:r
    relations on fSa versus tenperature d.iagra;:rs. These di-fferent
    nethods are diseussed separately below.

    fS, Fron Sphalerite ConPositl.on


    For the estinataiion of fSa in the hyd'rothernal fluids'
    the iron eontent of sphalerite is conventionally expressed'
    in aole f Fes;
    uoleq EeSsP x 1oo (v-22)
    l,ioLe I FeSsP =
    moles FeSsP + noles ZnSsP

    Values o.fthis parameter for the sphalerites analysed'


    in this stuily are presented in Table V-4'
    Fig. V-6 illust,rates the effect of fSa and tenperature
    on sphalerite colrpositions. Scott & Barnes (lgll) noted that
    at any specific pressure sphalerite in equilibriua '.'rith
    pyrite and pyrrhotite (on the pyrite * pyrrhotite bound'ary of
    Fig. V-5) has a consistent conpositj.on at tenperatures below
    55aoC (i.e. 20.7 ! 0.6 rnole $ FeSsP at 1 bar pressure). The
    effect of pressure on sphalerite conposition in the assenblaee
    sphalerite * pyri.te * pyrrhotlte is shorrn in Fig- v-?.
    707

    TABTE'/.iA

    Sanple ilurber Veln ':iI. 7 loefS,


    V.U.';1. llo. F ield llo. Location Star;e f e F:3".fi "3
    1 3965 lirl 1 l'llners i{ead l.iine 9.00 15. L6 L25 -
    6.2
    13908 cB5 To Ahurata Barrler Reefs 1.',t6 2.O2 2lr|-'t2.L
    13971 DC1 2 ilorthern Colvllle Doctors Creek 3.15 5.1.7 325 - 9.0
    Pen.
    1397L s:r11 r Sorry llary Strean 0.87 1.52 12' - ?.9
    11959 lri 1 Tokatea Tokatea lllne 2.39 1,.15 280 -10.9
    13982 AS5 Petote Stu.area lltkcn Strean 1 1.72 2.99 300 - 9.6
    13985 l|c3 tl llutt Creek 1 0.84 1 ..4,6 n - 9.0
    1 3989 l{C {a T Ilutt Creek 1 0.80 1.39 n - 9.0
    PSI tr Chalcopyrlte Loile 1 1 .11 1 .9L n -9.2
    1 3991
    1 4000 PS21 c n Galena Lode 1 1.29 2,25 n _ 9.t,
    1 4002 Ps21 h r Galena Lode 1 0.89 1.55 n - 9.0
    1 3937 lr,3) llaratoto Canoola Veln 2b o.31 0.55 280 - 9.1
    285/37/6 il1) ll Sl1vor Queen Veln 2c 0.58 1 .01 n _ 9.7
    ?s5/37/7 il14 n SlLver Quson Vein 2c o.31 O.5ll n - 9'1
    285137/e tqz tl Sllver Queen V,:ln 2c o.3i 0.57 d -9.2
    (r.u. H181 85)) n Canoola tJoln 2b 0.28 0.L9 r - 9.0
    (1.0. !.t18186) r tl Canoola Veln 2b 0.22 O.38 r - 9.8
    1 1,015 r'rk5 l'leltel:aurl Jubllee Lov level 2a 0.59 1.03 n ' 9.7
    1 4020 ifk13 n JublLee Loe level 2a 1.30 2.26 n -1 0.4
    1 4040 t:!h29 lfalhi i.lartha lllne 11 . t+7 19.63 325 -10.1
    1LOl,,6 l,rh43 n llartha illne 6,33 10.92 n -. 9.6
    1A01,7 l.ih44 n I'iartha ?L 1 .75 t.Ol' n - 8.5
    1ltoL8 irh4 5 llartha lilne 1.o3 1.79 n - 8.0
    'l
    1 LO52 i,rh50 t] , liartha 10L 5.98 10.33 u ' 9.6
    1t+023 tL17 Karanlahako Tallsnan iilno 2.39 l+.15 300 - 9.9
    11,025 rr.22Ql tl TaLlsnan iilne 14L 1.31r 2.?3 n -9.4
    11,025 rL22rc) t Tallsiran lllne 1l.L 1.5L 2.68 n - 9.5
    1 4025 tL22G) t Tall.snan ilne f 14,L 1.1,2 2.L7 n -9.5
    1 LO57 Tul li Tui lline Charplon 5L 2 1 .23 2.1 t, 300 - 9.3
    1t058 Tul 15 t Ruakaka 3L 2 1 .58 2.?5 n - 9.5
    14,059 ?ul 1? n Chanplon JL ? 1.67 2.90 n - 9.6
    1 4060 Tul 18 |l Ruakaka 3L 2 1.21 2.11 i - 9.3
    't 4061 Tul 19 tl Chanplon 5L 2 1.8 2.1,9 n -9.5
    13979 ul 110 l'lal.oron3oral llay ?ueen 3L 1 O.(r2 1 .08 325 - 7,6
    11,072 . r.n 21 It llo,1 Reef tlrerraynl 0.76 1.32 n - ?.8
    1to75 ';II 27 n IIo.1 Reef 1 .23 2,1t, r -9.2
    nllaterfalln
    1 40e2 r'r1 53 It Eonanza 1 0.85 1.48 n - 7.9
    1 4086 lrl 58 r 'rloleono Valn 1 1.8 2.1+9 1 _ 9.3
    1l,,Og2 1'r1 83 t Golonlst' Snlthy 1 o.t L o.77 n _ ?.3
    level
    1,{,1 00 lft 98 n Coloni st-llero 0.67 1.17 n _ 7.?
    1 1 00r 1ovol

    r Aueklanil Un lveratty sanple nunbers


    ?,08

    TABTE V-4: toS fS, values, for th.e asstgned


    teuperattrres, calculated frou the
    trron c,ontent i,n sBhalerites. Log
    fSa values derived. fron sphalerite
    anal;rs'ee me,d.e during this strtdlr are
    .Lisbed i.n Table V-4.4, whereas Table
    V-48 llsts log fS, values tlerived.
    ' fron sphalerite analyses report.ed Ln
    Ft'evloU$ work'e!

    TABLE trI./,B

    tocatloa 8anp1e Refe:isne,e I,Itfi ltolef t 1og


    Nunber Fe FeS oC fSe

    Iharoes 0u-Bi Stage


    $'tronswqi Reef Arr28g56 l,lerchant 01.43 A.V j 400 -L.40
    Kaiser Reef LTE251A2 (t qza p91 ) o.ii o,92 400 -4.5,8

    Tba,nes Pb-En Stage l,nerehant


    llsnotrui au?s956 ( 1978 p1 1 5) O.35 O.61 280 -9.2
    $ylvia AU?530'8 n 0.16 0.28 tt -9.5
    0arbo. Ml,ne AU289.40 tt 0.1? Q.29 fl -8.6
    Iioanataiari LT1,2,8955 ir 0.60 1 .04 ti .9.1
    Austra-lae i-en i,u2Eg63, tt 0.1/+ 0.2& n _9.L
    ?latchnan AU28933 tt 0.0/+ 0.07 rt _7..7
    l{onoraai ( 3t ) n 0.22 0.18 ff -8.E
    ' n n -9.2
    It A. jL O.5g
    Zeehan " 0,35 0'61 rr' -Q.2
    SyLvla n 0..72 1 .26 tl :9.8
    l,Iatehrsan Couper 0.46 0.80 rfi -9.5
    (ri 97 j)

    trdhangapoua Stage 2 P53,11,,27 &obson 0.61t 1.12 -9.'l


    (19119 p121 )
    PS3t &28? 0,78 1.29 -9.9,
    '7q9

    Flgurc V-6r Gonpoatrtiod of' rphal'e!'t'tc tno1o f'FrStPl fu cquttitriun r!ib, pyrtrte
    ' and ptslhotlls ag. a fuaotlon' of tcapoFrturqc aa4 f8,n. (Fron 9zesa!'ab-o.,
    7g7lol
    ?10

    C'
    a
    lri
    a
    EI
    o
    C!
    F
    e

    ll/lole Prcrosnt FeS. in Sphs,lerite

    Flgurc V-?: Effcct of prerrurc (barl) oa rpbalerlte colporltloa ln the


    grlerbl,aga sDhalortt]c I gyrrbot{tr. tlt|or Stott & Baracr, tg?Jt.}
    i

    ' ?11

    sanples containing an assenblaSe of sphalerite * pyrite


    * pyrrhotite were encountered, fron only two areas d'uring this
    stud.y and they are represenied' by sample 13965
    (15'5 Eolo fr
    ,r.Ssi) fron !:.liners Head. and. sanple 14.040 (t9.6 ,oole I FeSsPl
    fron lJaihi. The sphalerlte of sanple 1404'0 ('.*1.29) is in
    reasonable agreenent nith Scott e. Barnes ('lgll) ezperiuentally
    deterdrined value of 20.7 ! 0.6 nole $ FeSsP for the sphalerite
    + pyrite + pyrrhotite assenblaga' howe'rer even wittr a eorrection
    for a naxirnuro pressure regime (2.5kn cover and lithostatic
    pressure, equlvalent to approxinately ?00 bars) sphalerite
    of sanple 13965 1:,riit) shoulci cqntain 19 nole s res (Fig. v-7,
    consi.derably higher than the observed' 15.5 mole I feS' This
    d.iserepancy may reflect eiisequilibriun bet'reen the sphaleri+'e
    + pyrite + PYrrhotlte assenblage'

    The conpositions of sphalerites coexistilg '-tith pyrite


    but not p'rrhotite or boraite (i.e. plotting in ihe pyrite
    field, of Fig, V-6) are related to the aetivity of St b]' the
    follorsing relationship fron Barton & Skinner (1979):

    1og x"essp = 7.16 - ry - log2 asa (v-23)

    nole I'
    --[1T- (;I-2L)
    B ecau se FeSsP =

    Then 1og l(r"rsp = log rnole $ FeSsP - 3-o'rj 100


    = 1og nole.f FessP - 2 (v-25)

    Therefore 1og nole t" FessP - / = 7'16 - ry


    - log oSz (v-26)

    or log cS2 = 9.16 - ry - log mole I FeSsP (tt-zt)


    2

    Final1y, because aS, = f'S, at low pressures:


    (v-28)
    1og fsz= 18.)2 - w - 2 Log nole F Fessp
    values of 1og fs2' calculated. fron the sphalerite coif,-
    positions using equatlon (V-ZS), are presented in Table V-4.
    ?.12

    ,l

    I
    il'
    '-+4'

    Ffgnri 't[-8r goryrosdttou of pSrtrhqu.ta (Eo.ls Jniottoa'f,e$po] to the Fe-8 ageten


    *a e funotio,n of tclBcratura tE'-d f,Sa. (Fren To,r*lrtia I Dtrton* 19:64,J

    i'.:
    r!.

    7t3

    fS, Frol PYrrhotite ConPosition


    Toulnin & Barton (196lr) experinentally deterrnined the
    relationship bet'..reen fS, and pyrrhotite comoosition as shown
    in Fig. V-8, deri'.red fron the follovin'1 equation:
    1o3 fs2 = (zo.o3 - Bi.s3 xrespo) ('3oo - 1) +

    3g.?o - 1 1.91 ( v-2e )

    irhere XF"Spo is the nole fraction of FeS (in trris case nole
    fraction = tuice the aton fractiotr of PeS) ia PYrrhotite.

    Pyrrhotites fron two locatioas were analYsed here' the


    results and calculated log fSa values for the assigneC
    d.epositional temPeratures are presented j.n Table Y-5.

    The 1og fs, value of -6.6 ealculated fron pyrrhotite in


    sample iilil is j.n reasonabLe agreement r,tith other data, however'
    the value of -7.9 derj-ved f ron pyrrhotite of sanple i'1h29 is
    nueh too high and inCicates that the pyrrhotite is iron
    defficie4t. At i;he assiqned Cepositional tenperature (32-SoC)
    r,he pyri-r,e - p;;rrrhotite boundar;r oecurs at log fSz = -'lC'0'
    Under these eond,iti-ons the nole fractio:r of feS in pyrrhoti'r,e
    shoulcl be apilroxina'',e1;1 0.95 ( c. f . Fi3' v-8) '

    fS, From Eleetrun ConPosition


    Barton & Toulnin (196t ) exper!.nentally deterrnj-neC the
    relations between tenperatuler fS, and. electrun conposition
    with the in+,,ention of providing an fS, indicator for laboratory
    experinents on stlphur systens. They found' that abovs a certain
    fs, electrun tarni.shes, due to the fornation of argentite
    (acanthite) fron the alloyed si.lver, via the reactioni

    4 A'g (in electrum) + s2 2 LtrS (arieniite) (V-30)

    For a speeific tenPerature' Icr*sr fuqaeities of S 2 a?e


    requlred to forrn a tarnish trlth increasin4 nole fractions of
    s j-lver (Fig. V-9).

    Their data have subsequently been used by a nunber of


    autbors (particularly Japanese rg. Hattori. 1971 and' Shikazono
    ?Lh

    TAtsLE 'V-5i I"og f,S, vaLues, for the .aE,sLgrie+


    teuprerat lres" g,e1e.uleted, f:ron t'he
    ' coapoeitionE of trlymhotXt,ea,

    V.U.I,l,.iYg, 13965 146*o


    Flald ilo. (iElir ) (xfh29)
    LqaatioA bli.aers Scad ?fartha lr[lner Flaihl
    trlt. f ne 59,70 58;T9
    Ut. t" S 3:9.35: 39.72
    Atou f,raetion Pe A.LI o.L5
    uole fraetLon FeS
    o.g+ a.g2
    (x*"rsn)
    Taapereture o:f
    . Depos:i.t5.on 425o9 3250C

    log fSe- -6.6 -T.g


    7L5

    ia

    ternlgb suryot for elca,lrul oolpoelttela (lole fraetlor


    I

    ir' Ftgure V-9r Snoothail


    . agcr). (lron Barton & Toulollr 1964')
    -:
    TL6

    -**-rl*ET
    ..---_],-_Nr..r

    t.
    . f'1. .. .
    .. ,"
    -----)J ' ',';-I

    tlgpoc Y-10c gsfr,6a+isn Jact'ora (atog fBrl ttrat eguets Barton it.Tsuluiaf r
    (1g54J 6quitlo! fism squlttoa (v-!r]J r rotratlag olelrttun eorBo,rlt,too to .:
    t8a ead tclp.ercturar to expcr!.nerte1. data. Tbe dacled trlnar aii after -' -'
    3't'.'
    'Dc,rtgt t foqhnF (19.64-), iborgtr tta lo1-{d 'l:Laaa (nsad ia tb:tp ptudy) ara r
    !f,'tcr Sartor (tSSOr. i , .:- ' .
    ?L7

    1g7S) to deternine fS, in ore deposits fro:n the conposition


    of electrun. The assunpti-on nad.e is that the electrun is1
    d^e::osi-ted. in equilibriun r+ith the hyd'rotherrsal solui'ion
    ar.Tentite, as dcscribed by the equatj'on above.

    Sarton & Toulni.nrs theoretical equatlon relatin3 f,St to


    el and tenPerature i-s as follows:

    o3 fs2 = **rffi{-rttto + 15.52 r- 18 .296 T log xo.el

    + lt (r -xooer )2 L565a 1 600 (t -xo*er) -


    1.375 r] ] (v-31

    Corrections required to equate solutions of the above


    equation to Barton & Toulaints (1961-) experimental results
    are shor,'n graphieally in Fig. V-10.

    Values of fS-'I calculate,C, fron go1c1- anC electrun analyses


    deternj-ned duri-ng ihis study are presented in Table
    \!-6A.

    (lgll), !{oore (1916) , l.lercharrt (t 9ze) ' Torckler


    Ransa;r
    ( l gZg) and Ercel ( t gAf ) also reported electru:a anallrses f ron
    the province but did not use then to calculate sulphur -'[-6P,
    fugaciiies. Tjrerefore their analyses are lisied in Table
    together uith fS, values ealculated' here'

    All of the electrUs analyses reierred to above r.{ere


    d,eternined by the electron probe nicro-analyser, hovever
    Fraser & Ad,ans (lgal) reported average electrum analyses anrl
    gold: silver ratios fron several mj-nes, d'eternj-ned- b.v fire
    assay nethod.s. These are listed in Table V-5C togetirer nith
    cal eulaied values of fS2.

    Lo fsz corrections indicated fron 3i;. v-10 are


    significant for the qold analirses (tatrle Y-5A) a'.d have been
    a-cp1ied, hor.rever correct j.ons inCicated for the electrun
    analyses are less than -0.1 andrconsidering the possible
    errors in the data are Probably not significant and were
    not applj.ed.
    718

    TA3LIV.6:Lolfs,valueslfortheassiqne(ltenperaturos,
    calculated fron the nrole fraction of silver 1n
    elcctrun and golC'
    Table V-6A, EPI'IA analyses rnade durln[ thls study'
    Tablev.68'sP:'jtanalysesreporteclnprevlousstudles.
    Tablc T-6Cr flre assay end ;old - silver ratlos
    reported by Sraser & Adanrs (190?).

    TABLE v-6t\: (1) Electrua


    t
    Saaple llunber
    V.U.'l{. ilo. Fiald IIo. Locat,lon Au
    ,,{t 7
    Ae
    r;l oc loqfsa

    Tii Tokatea, Tokatea !!lne 60, L 18.6 o.5L 220 -'t2.3


    13961 7

    2851 37 / I u32 liaratoto Sllver queen 58.7 L0.7 0.56 280 -10.7
    il33 l,laratoto Canoola 51,.8 Ll*.1 0.60 280 -11 .0
    1)937
    14025(a) rL22(2) Karangahake Tallsoan 1 lrl 71r.2 26.3 0.39 300 .-8.6
    o (b) rL22(6) It It ll 70.5 25.6 0.40 300 - 8.7
    n (c) rr22( 9) r 71.2 25.1 0.39 30o - 8.6
    1L032 cr3 I'ialhi, Grand Junctlon 52.3 1,6.1 0,62 270 -1 1 .1

    'l I,ol,J 1,rh35 l'lal.hlr llartha iilne 65.8 33.e 0. t8 ?80 -10.0
    1LOL6 lrh43 nn 68.2 31.1 0.46 280 - 9.7
    I,IhL5 nt 62,9 36.6 o.52 280 -1 0.3
    1/.0,1,8

    (rr) cota Cor-


    reC- Correc-
    vtl t tlon ted
    V.U.tl, l{o. Fteld llo. Locatlon
    ilu Ag
    x;; oc
    log
    fsz (Fie
    v-1 0) logfS,
    ui a Chanpion 5L
    It Tul 27( b) tl 88.8 9.6' 0.15 400 -3.57 -0.50 - lt.1
    13909 Tui 30b It 90.2 8.0 0.14 400 -3.38 '0.5[t -3.9
    'l 1,092 rft 83 I'laloronqonal 80.27 19.61, 0 .31 325 -7.09 - 0.1 -7.2
    TABTB V-68: (i) Electrusr 7t9

    Iteference tnt !0,, x ;c


    nu il tros fsa

    Sunbean i(obe ( 1 9?,4.)

    Iona Quarry
    zoneg
    . coro n 17 53 0.67 220 -13.5
    r'1u tl 84, 16 0.26 7-2C - 9.0
    Iona :irco.l ( 1981 ) 51 t+I o.63 224 -13.1
    BROKEII HILLS lloore (1 976) 67 33 o . lr'l 22A -11.7
    Slevors Leader tl ll tl 2l,o -11 .0
    Brsccla Pige 2 61" 36 0.51 ?-2C -12.0
    level fi tr tl 2t0 -11.t+
    TIIAI,IES l!erchant
    GoJ-d-pyrargyrite Uwa) 70 30 o. lrl 230 -11.0

    IIEAVIJSVILLE TorckLer
    Gracos.Open Cut ( 1 9?8) ?o 3O o.4t, 22A -11.3

    ( il ) Golci

    \!r5 . t 1o.f Correction Corrected


    Au 4,3
    Y
    it, oc tsz (Fi: Y- 10) 1o1 fS,

    lrrTu-rillrtns
    Pb-rlu stage of,
    Sylvla-1{atchaan fse 1B o.zg 280 -?;7 < -0.'t -7.8
    area (iierchant,
    rantc]t, 6 0.11 290 - t".7 -0.1 -5.1
    1 97s)

    TA9LE V-6C;

    rr+ t
    ';l
    a,
    a 6 -aV ,a

    Loeatlon *f *4 Au All oF 1o; fSa

    Kaurl Bloch illnos 113 A 7lt 26 o.39 ?20 -10.7


    Coronandol
    Kapanga lltno 117 A ?o 3O O .l+l+ 22C -11.3
    CoronandoL
    Royol Oak illne 122 3 67 3) o.lr7 220 -11.7
    Tokatec, Coronandel
    0pltonul l{lne 130 ,l 50 5O 0.55 220 -13.3
    l,lhcn;;apoua
    l'laitaia !.llne 135 n 72 28 0.4,2 25O -1 0.1
    i(uaotunu It n It n ll ?2e -11.0
    * Page nuuber ln lraser & Adans (190?)
    rz otated os eloctruu eotrpositl,on
    ,lI,
    Bt ratlo of rloLd to slLvor 1tr ore, but no silver ::irsral
    noted.
    72U^

    fSa f'ro;r Hineral Stability Relations on fSa Versus


    Tenperature Diagratrs

    If',,he depositional tenperature of anineraL assenbla;e


    is by conparisoa of the
    lino-,+n, linits of fSZ can ba dei,erilined
    sulphid.at,ion reaetions of the various uinerals plotte<i on an
    fS, versus tenperature dlagran (c.f . Fig I-Ii-/*). liost of the
    cori:or sulphida'ulon reactions are illustrated i-n Figs - 7-21,
    7-22o.-tc 7-23 of tsarton & Slrinner (19?9). A linear 1G3. o-1
    tenperature scale is used so that the reactions plot as
    straigh'" Ii.nes.

    of the nineralisations stud.ied here contaLn pyrite


    l.'lost
    ancl chalcopyrite and therefore plot between the pyrLte/
    pyrrhotite and chalcopyrite/boraite plus pyrite reaetions
    (c.f . Fig. I-U-/r). 0ther diagnostic reactions used, to C.eternine
    1og E2 are antinony/stibnite, silver/argentite, arsenopyrlte/
    pyrite plus arseni e, arseni-c/reaLgar and. tetrahedrLtel
    fanatinite (Fig. f-H-,{, and .figures cited, fron Barton. & Sklnner
    1g79) o

    Tre occurrence of the silver,/argentite reaction (c.f -


    Fi,3. 7.23 of Barton & Sllj.nner 1979) at very 1o'* sulphur
    fugaciti-es, lor+er than the pyrri:o'bite/pyrite reaction'
    Cenonstra*.es that native silver in nineral assenblages contairt-
    in,.; pyrite, is not prirnary but r'ras deposlted. at sone later
    stage, probably during supergene processes. Siuilarly, uative
    antlnony oecurring r'rith pyrite and other sulphiCes at
    I'trhangapoua (Ff S. I-H-4) is considered to have originated
    durln3 a later stage of nineralisation than the ad,jaeent
    nlnerals.

    Fugacity of 0a

    Introduction
    OxyEen fu;;acity estinated fron nineral siability
    roay ba
    relations on fS, versus foa ancl f0, versus pH d.iagracs. lhe
    construction of the latter requires knowledge of the concentra-
    tion of total sulphur in solution (n S) and therefore this
    paraioeter will be considered. beiween d,iscussion of the fS,
    versus fOa a:nd f0, versus pH d,i.agrans ..
    72t

    TiDL0 V-?: Thernodynanlc data usod to calcul-ate the fS, versus


    ta:Petaturo 4nd fSt versus f0. d!-a;rams. Thc free
    ener;:r chan;e is liven ln the'forn Go =All-TAJo

    liquatlon ilunber lleac'ulon Iree encrgy chanqo Source


    (ln joulco ior T In I()

    (v-32) 2IcfSt=2FeS -300,500 + 105.10f (1)

    (Y-n) Slrtu*02=lrero, -551,O3O + 15t,.527 (1)

    (v- 34) LFerA^* Q2= SFerOt -t88,620 + 278.191 (1)

    (v -35) 3 FeS + 2Q, = lerll +


    )/ZSZ -651,315 + 151.387 (1)

    ( v-:5 ) 2 FeS + 3a = 2leSt -280.t66 + 279.781 (1)

    + 202 = Fer0O a 3SZ -207,35.1 - 281 .927 (1)


    (v- 3? ) 3 FeSa
    (1)
    (v-3s ) 2 PcS, r 3/z o" = Fero, + 2s2 -219,658 - 14,1 .59t
    ,869 + (1)
    (v-3e) 5 CufeS, * SZ = CutfeSn + 4'1"eS2 -211 ?1,,0. 1,,57

    Fero, + s2 + t/ro:- = 2 Fes04 -1,151,ooo + 615.57 (2)


    (v- 40)
    + 21,,1 .8r (2)
    (v-,4,1) FeSa + 20a = 3'sgg Ir + LSz - 680 , 300

    -115,1,8) + 130.297 (1)


    (v-42) Sa(v) = Sa(s)
    Fe+Goa+l(02)=pec03 -351,,4AO + 251.0r (2)
    (v- t,3)
    -193,93O + 177.07 (z)
    (v- 4/,) FeS + co2+ Lo2 = FeC03 r LsZ
    (v- i5 ) FeS, + coz+ Loz = FeCo, + 52 - lr7 ,lrBE + l+9 .oT (2)

    (v-16) le'}r+ 3CXZ = 3FeCO, 1)zOZ - 31 ,3BO + /rla.oT o)


    -36),10O -1379 (t+31
    (v-4?) feC0, + 3O2 = 6Fet0, + ISCOZ T

    (v-48) c+02-coZ '3i1,,133 - 0.841 (a)

    (v- 49) Caco, + ts, + 3/, o, = caso, + co2 -681+1837 + 189.8?T It )

    (v-50) ltnS + C0, 1 l0Z = :lnG03 a lSe -222,798 + 195.987 (a)

    (v-51 ) llnS+20r=;'lnS04 -851 ,86Q + 1?2.ltT (4)

    (v-52) HnGo, I lsz r 3/r oa = iinSo, + co2 -628,981 + 181.597 (4)

    (v- 53 ) 2Ls+Sa=2AsS -203,828 + 177.L1,7 (1)

    (v- 54) Ll sa r sz = 21, sarsu -231,919 + 167.78I (1)


    u
    (v- 55) lAg+Sr=2AgS -175,(rLL + 69.127 (1)
    (v-56) 2 I'eAsS* 52 = ZFeSa + 2Aa -257,731++ 258.157 (1)
    (v-57) 21, cu.resb4sr + sz - t/ cursbs, -173,958 + 165.737 (1)
    ) u

    (1) Ilarton & Skl,nner 11979)


    (2) ilolland (1959)
    (3) rtotlana (lj65)
    (,4,) :'-ubaschewskl & AlcoeL (19791
    ?22

    fS, versus f0t Diagrams

    Thd fS2 versus tOZ di-agrarns presented in Appendix I y.ere


    - constructed at various teaperatures by the nethods outlined.
    in Vaughan & Craig (lglA pp255 and 257) using the data listed
    rr" in Table V-7. The follor,ring explanatory notes detail specific
    . aspects of their construction and di-scuss aspects of sone
    specific nineral systens.

    (i) Consi.stency of Data on Stability Relati-ons of fron


    i{inerals

    The thernodynanic d.ata used. in the construction of the


    fSa versus f0Z diagrarns were found. to give generally conslstent
    results with the exceptions of the pyrite pyrrhotite
    na3netite and pyrite henatite - FeSO, triple points. In
    both cases the boundari-es which neet to define the triple
    points dld not intersect. The error uas snall in the former
    case but relatively large in the latter case.

    To forn an intersection for the pyrite.- pyrrhotite


    nagnetite triple point the pyrite-pyrrhotite line ruas plotted.
    as cal.culated but,the pyrrhotite - nagnetite and pyrite
    nagneii-te lines were adjusted.

    In the case of the pyrite henatite - FeSO, triple point


    the data involving FeS04 vas considered to be the least
    reliable and 't,herefore only the henatite/f eSO, and pyrite/FeS0,
    bound.aries lrere adjusted.

    Intersect,ion at the irorr pyrrhotite - magnetite and


    nagnetite - henatite - pyrite triple points uere satisfactory
    and no adjustnents were required.

    (ii1 Chalcopyrite/Bornite Plus Pyrite Bound.ary

    The data used for the eonstruetion of the chalcopyrit,e/


    borni-te plus pyrite bounrlary (tisted in Table 7.2 of Barton &
    51;inner 1979 but cri-;ineily fron liehneeberg 1973) is applicable
    only to tr,rperatures oi 23o - 532oC. Iunrl & iiellerucl (1966) ."

    bonsidere..l that asse;rbla'es of bcrniie arll -D'rri.te are unsta'rIa ::


    _t

    723

    below 228oC (Barton & Skinne r 1979 sutqested that this lower
    l-init should be 2?OoC).
    Therefore ihe chalcop;rrite/bornite olus plrrite reactior
    :.':e..., not be appliceble at tenoaratures belou ?TAoC- Tl:e
    reLevant reaction nalr ins'ueed be ehal copyrite/Cigeniie plus
    ;:;',ri
    "e
    '
    Iio'rrsver, assenb'lages of Fi'rite plus borni'be rrare quite
    co:non in aany ore bod.ies, inclucling i'ta,qaa llj-ne, Arizona'
    the elevated rock tenperatures (at least as high as 50oC)
    r.rhere
    have provid.ed us with extraordinary long tern experinentsrt
    (Craig & Scott, 19?l+ p CS-69)

    In rrieis of this conflj.ctin3 evi.dence the chalcopyrite/


    boraite plus pyrlie bounCary is plotted on aJ.J. fSa versps
    f.0, diagrars presented in Append,ix L Because ro other
    relevant d.ata could be founil-, Schneebergts 230 532oC data.
    ruas also used for tenperatures between 23AaC and 20OoC (tfre
    lo',lest tenperature consi-dered) .

    ( iii) ico,

    fugacity of C0, is knor,rn it can be used. t'o-


    i'ihere the
    caleulate stability field of siderj.te (equations IJ-/r"3 to
    "he
    V-trl, Table v-7); graphite/C},- (equaiion V-/*9, Table V-7)
    anC calcite/anhydrite (equatioa Y-\9, Table V-7) bound.aries.

    (lgll) experinentally stud,ied sone aspects


    Ali;hough French
    of sideriie s-uabillty1 his resulis uere not conclusiver and
    therefore the nost recent co;aprehensive d.ata remai-ns that
    iisted by iiol1and, (1g59, 1965). i{or*ever soine aut}rors consider
    that this clata is j.naccurate (c.f . Solla'd' 1965; Srench, 1971 i
    Einaucli , 1977') end its application here .3ave inconsistent
    results: sotle l:ineral boundaries required. consirlerable adjust-
    nent, fron th.eir calculateci positions on the fS, versus fOZ
    dia3rans, to forn intersections

    siderite field, although probably only approxinate,


    The
    is shornn in Fig.I-0-13for the l.laatoto d.eposit because of the
    i
    vCrbnrA tj't'iivEr'5lTy oF viELLil'lcTc'
    Tel+

    t
    I
    g\
    g
    {tr
    q5 Rqrtlaar
    u
    L (As 5I
    u
    5
    (rl hkafive
    vt
    (.l- hrgonic
    (As)

    fo,'ivteroasrg -+
    r

    B'trgsrE Dl,egrauatl,c rqFDs6ataitoa of the.streblLtty relatLole of ocle


    V.ll't
    ph&ifr ia the ayeter ls-S-O os a fuo:gtloa of fg. ald f02 et eorstatt
    teapor*tgrc- f,rtl'vc argran e tsd posri.bly regl,gEr *nc loaatdored fio"ta '.'i:
    .tti enJy phasoa tailrcraat to bypogeuia llneraJ--lrctfloas la'the Eauakd ' .
    'Frsrlnso Dc.aailgc of tlt blg.b valuea of f$a aati. fO, requfi,retl; to'r tbe ;

    stcb1ltty of or-1p:tpqnt, .arsit arneuolrlte roagloetlrretrf (aotc tbet both of l'

    there i,beacc b*ve tet rtporteit,firot ttrB provtnea as suFargelie,rlnQratral .


    725

    occurrence of siderite adjacent to the sulphide :nineralisati.oa,


    horqever it is not ploited in other di.a'lrarcs beeause of the
    ineonsistencies in the thernodynani.c d.ata and tbe apparent
    absenea of sideriie fron nost, prinary nineralisations. ilever-
    theless, it should be note.{.. that ths s!rleri-,.e iield r,ra;r replace
    a large partr or all, . of ihe aagnetite fiel d j-n the 1o'* to
    nod.erate tenperature (up to 28$oC) sysi.ens :ritil values of
    fC0Z betr'reen 10 and 30 bars (1o'g fCO2 = 1to 1-5).

    (i+) l.ianqanese lli.nerals

    Rhodochrosite occurs with sulphid,e uineralisatioa at


    i,laratoto and theref ore the stabil ity of the various nanganese
    ninerals (rbodoehrosite lln00r, alaband,lte l.!nS, and i'inSoa)
    are plotted in Fig. I-O-1 2 usi-ng equations V-5C' V-51 anC
    V-52 of TabLe V-7.

    (v) Arsenic Systen

    ilative arseni-e occurs in ihe nineralisation around


    Corosairclel (Kauri Bloclc and. Kapanga i'iines) and. :{han.?a.pou&'
    an,f therefore t:.re stabilitl,' oi native ersenic is of interes-,,.
    The ni.neral stabiliiy relations in the si'sten As - S - 0 are
    shoyn in irig. V-11 - Data f or the arseni-e/realgar reactj.on
    at elevated temperatures are lisf.ed ia Tab1e V-'7, (equation
    V-5il, however conpatible d.ata . could. not be found. for the
    reactions involvlng arsenolite. The lattsr are considered to
    be i.rrelevant to the minerallsations studied. due to iheir
    alnost cerbaia occurrence ',rithin the nagaetite and.hena'r,ite
    siability fields. Therefore only the arsenic./realgar reaetion
    is considered inportant here.

    Concentration of Total Sulphur in Solution


    The concentration of tota'l. sulphur in sol-u'r,ion (t, a S)
    cl.uring ore deposition is considered, by nost r'iorkers to be in
    tl-e ran,,Ie of C.1 to 0.00114 (Barnes & Czananske 19()7, Ohmoto
    1972). Table V-8 lists values of n S calculatei. for epithernal
    ore deposits by previous studj.es. Based on ihis rtork a general
    schene o! m S values for the different d.eposits of Grea',,
    Barrler Islaad, and the Coroaaad,el Peninsula is presented. in
    Table V-9.
    :'7'26
    TAELE V-8: Gonoenlr.a.ttong of totel au.trptulr n.n ' /
    aoluti,on eoeLgfiod, to sou6 epi,tharual
    depoaLts by other. Horks.

    DeposLt nS lo,gnS Reforene.e


    '-.--: .---n!!r
    -'-"-

    nl. lline - 0.001 -2 to -g


    0.01 -.i-a--
    Robi,naon(lgz4)
    trIetukouLar FaJl 0.00'1 - -3 Abuad (lg?g)
    .Oreede' Golora.do 0,0e -1"'l ts-a1toa et q& ng|7l- i
    '-1
    sunnysldEr colo,rado 0.CIt .3 Gaaedgvarl. & 0:fosst,6
    ( 1g??)

    Lska Cl.ty" Colerade 0.Ol -l $Lack (l9BO)


    t-
    :

    Fialendia' Feru 0ro03 -2,.5 Kaol,lLl & Ohoto


    (r e?fi
    Eatetpl., tapaa 0.01i - O.001 -,2 ts -3 *attort (1gB5l
    To3ro:har .faF'an 0.01" - 0.,001 -2 la -9 Shlkazqno (lgrtS,
    ?27

    TAELE V-9: Conceatratlon of total suJ-phur ln solutlon durlng


    fornatlon of eoue doposits la the tlaurakl 0o1d -
    Silver Provlnce. the estlneted values represeat a
    general schone baseal on values cal-culatecl by other
    studiae for glnllar deposits (e.g. Tab1e V-8)' shereas
    the calculated values uere derived by coaparlson of
    ulneral atabllity relatlons vlth contours of 1og I S
    plotteil on fS, vsraus fOa diagraas.

    Total sulPhur ln solution


    Locatlon Stage t Estiaated - CalcuLated
    oc n { S log arts ar {S log a {,S Reference

    f,f lners lleaal L25 0'05 -1 '3


    Ta Ahumata 1 (base netal) 2i(,0 0'005 -2'3
    2a (As-Au) 22o 0'001 '3'O
    2b (sttbntte) 23o 0.001 '3'O
    llorthsrn ColvlLlo Par:Ltu coastal sectlon 425 0'05 -1'3
    PenlnsuLa Cu-pb-Zn velng 325 0.01 -2.0 0.01 -2.O r-c-4
    Z5O 0'005 '2'3 0.005 -2.3 I-D-4
    Kuaotunu 3
    Tokatea Dege netal 280 0'0'l '2'0
    Gold - eLlver 220 0.001 -3.0
    Kaurt-Kepanga 220 0'001 -3'0
    1 3oo o'01 -2'0 0,01 -2.0 r-c-5
    Potote stroaa
    llhangapoua 2 280 0'01 -2'O
    4 (stibnlte) 200 0.001 -l'0
    1 and 2 zLO 0.005 -2.3 0.00't -3.0 I.K.8
    Brollen 11tUs
    Tapu Thanea Cu - Bl 400 0'05 -1 '3
    Pb - Za 280 0.01 -2'O
    Thanes Goltl - pyrargyrlta 230 0'001 -)'A 0.001 -3.0 I-:{- 5
    (to (to
    0.01?) -2.0?)
    lloavesvllls AJex 250 0.005 -2.3 ,a0.005 * -2.3 r-il-6
    Bluffs sectlon 220 0.001 -3.0 0.01 -2.O I-lr-8
    Maratoto 2 280 0.01 -2.0
    llaltekaurl 2 280 0.01 -2.0
    llathl Lotr lovels. 325 0.01 -2.0
    Intornedlate Levels 280 0.0'l -2.0
    Upper levels 220 0.001 -3.O )o.oor > -3,.0 I-S-11
    Karengebake Lou levels 3oo 0.01 -2.0
    Tul .lllue 1 400 o.o5 -1.3
    300 0.01 -2.4 0.01 -2.0 I-U-1 2
    2
    325 0.01 -2.0 0.01 -?.0 r-v- {
    llatorongomal 1
    728
    TABLE V-10: Theroodynantc data usad to calcul-ate the f0, vlsus
    pH dlagrane. Ths froe nsrgy chaage ls glven Ln the
    forn AGo = aH-l.aso

    Free energy change


    Equatton (ln Joules for ?
    lluober Reactlon ln K) Souree*

    (v-58) 2Hzs("q) * 0z(e) = sz(s) + 2ua0(r) '367,'t3o + 95.8T (1)


    (v-59) lse(g) + 3/2 oz(e) + Ezo(r) = to?ire)* ztl+(aq) -687,6LO +t+72.LT (1)
    (v-eo) tti.*)*nt"n)-Eas("q) -20,083 - 66.5T (1)
    ( v-61 ) flzs(oq) + zoz\d = ttori.n) * 8t.q) -855,377 +427,6r (1)
    ( v-62) Hsoi(.q) = sof-1"r) * Ht.q) -16,108 + 92.0T (1)
    (v-53) Bsi"e) + 2oz(e) - soa2i"q) * Ht*q) -891,569 +t53.51 (1)
    ( v- 51) res("c) + zoz(d = 4i"q) soafiq) -871.485 +519.7T (1)
    "
    (v-65) zresle) * 2ns[ae) * oz(g) * 8t"ql . 2resa1"1 + 2Hz06r) -688,36tr, +242.',11 (t+21

    ( v-56) s.s(") * Ees("q) * 0e(g) = 2Fosr1") + Hzo(r) -618,198 +375.7T (1+2)

    ( v- 6?) 6ros16) * 0z(r) + 6E2o(t) = 2Fer0o1")*6Esi"q)*6[t"el -78,935 +1,11,.6T (1+2)

    (v-68) F"304(")*6ssi"q)+anf"n;+oa(e) = 3F"se( -1,016,3U, +1?0.3t (1+2)


    ")+6Hzo(r)
    ( v-6e) 3Fesr1")+6uzo(r)+r 102(s) = F.304(")*6sor?iql*trtt.nl -4,,333,068 +2.5L8T (1+2)

    ( v-?0 ) 2Fes.1 0z(g) - F"203(")* soiiuq)*8Hl"e) -2,97A,116 +',|,715.6T (t+Z)


    il+I,x2o 0,t+1512
    ( v-71 ) 2ros.1r)+4Hzo(r) +t512 0z(e) - reaOrlu;+4ltf.qy+aHsoi1"ql -2,905,?17 +1,17?.1, (1+2)

    (v-72) 5cureSal = CurFeSrla)+4Fest,")+2F20(r) - 579 ,601 + 336 .l,t ( r+ Z;


    ")*2H2S("q;+02(e)
    (v-73) 5cuFesal r) +2HSi.q) +021 g) +2Hf o +4F"se1 +2Hzo ( rlr.,r,ra,
    .o; curFes4( s ) u1
    +zo7.3T ( 1+2)

    ( v-?1) ,urr"ur(, *rrurr( t) * 3oe( g) = rcuF"s2( sl


    *.tooilnl *ant
    )
    { "n)
    "r+aneo
    -1,163,370 +702.91 (t+Z;
    ( v-?r) 3lz 0z(c)*Ez0(r)+lsz(e) - st"e) * Hsoti*q1 -671-,532 +3',|9.9T ( 1)
    ( v-?6) 2usi"e) * o.(r) * eHt.q.) = se(e) + azo(r) -407,898 - 3?.2r (1)

    ( v-??) cac0rlr) * Hzs("ny+2oz(e) = casoa1")+coz(c)*Ezo(r) -868,-?03 +238.1T (113)

    ( v-?8) casoa1 s;+co2191+ffao(r) - saco3( r)*sor?ie)**i"n, -2,782 +281.7t (t+l)


    (v-?9) l'tns1";+c02(c)+Bzo(r)' nsi"q) + Mncorlu) *^El"q) -18,81,9 +21t,.5I ( t+31
    (v-so) -91o.397 +557.3T (t+31
    r;+Hao{r) =
    Mnsl }loc0r1
    u)*sol?le)*ttt"nl
    (v-81 )
    "y+co2(g)+2oz(
    Hos( r)+coz(c)+fl20(r)*202(g1 = Mucorlq)*Ht"c)*nsoi(rq) -8gt,,rog +575.fi (1+3)

    ( v- 82) t"?ln; * t.ii.uy + 20a(e) 'Basoo1.) *.2Et"e) -89?,175 +t?O.1T (1)


    (v-83) r"?l;; + Esi.q; + oe(e) = Baso.1,) * Et"e) -917,258 +35t,.0r (1)

    ( v- 8i,) t"tlnl 1 nsoiaq) = Beso4(e) * Ht.s) -41,798 - 7.5T (1)

    * (1) Eetgeooa (1969)


    (2) Barton & Sklnner (tglS)
    (3) Kubaschssskl & ALcock (1979)
    729

    The estinated values of raS nay be cheeked by coraparison


    of the nineral stability relatj-ons uith contours of m S
    plotted on fS2 versus fOZ diagraros. Contours of n' S ltere
    calculated, for specific values of tenperature and pl{, by the
    method outllned by Raynahashay & Ilolland (1969). The method
    consj-sts of the followin* four stepst .
    (r) Contours of HaS (independ.ent of pll) and tor*t- (pii
    dependent) were plotted on the fS, versus f0, diaerana usin51
    equatLons V-58 and V-59 of Table V-10 respectively.
    (b) Concentrations of ilrS, HS-, to4t- and IIS0.- Here
    calculated at the pyrlte-pyrrhotite-magnetlte and pyrite-
    nagnetlte-henatj.te trlple polnts by subetltuting the fSa and
    fOe coordinates of these points in equatJ.onp V-58, V-59, V-60
    and V-61 of Table V-10 fespectively.
    (c) The individual concentrations of HrS' HS-, tor*t and
    l{SO,
    4
    were sumned to give the ra {S at each triple point.
    (d) Contours of rn ( S were drawn para11eI to the HZS and
    t04'- contours usin;1 the trlple point la { S values as reference
    for contour value and spacing.

    a S contours were calculated for only a few represen-


    tative fSa versus f0a diagrama at different teuperatures (e.g.
    Flgs I-C-lfi I-D-/*, f-G-5, I-ii-8, I-l.t-5, I-li-6, I-N-8, I-S-11,
    I-U-12, and I-V-4) because of the i-nvolved nature of the
    calculatLons and the fact that ihose calculated wBre SleneralIy
    consj.stent with the estimated values of n ( S (Table V-9).

    fO,z versus pH D5-agraras


    The f0, versus pH <iia ;rams presented in Appendix I were
    constructed Ly the i,:ethods outlined in Vaughan & Craiq (lllA
    pp 927 - 33O) frorn the data listed 1n Table V-10. The
    stability of the aqueous sulphur speci-es (tisOr-, to4t-, iiZil
    and ils-) lrere calcul-ated i'irst, fol-Iolred by the boundaries of
    the various iron phases ( p;'rrhotite, pyrite, na,qnetite,
    ]renatite an,C r'e.SOr). These t1,pes of Ciarrans are only relc,vant
    up to teri:eratures betueen 350 and 400oC. At hiqher tenperatures
    SO, anct il.,q are the <ioruinant sulphur species ( c.f . Fi6s 10-1
    ancl I-A-6).

    The aqueous sulphur species and lnineral stabilit;y f ielris


    'w

    c
    LG

    i
    '.-
    sg
    -i,

    r'!gFr6 il,-:lll: iQ$itouar of fRrg ln aguf,tr;lbcLuo rlt'b the ,prodooiaaa't :cgu,coira


    rrllpbur rgolt at:lS I O.trn rnt e-59g' (n,e4fflod :trsr f;!g*!' :e Brlapr *
    f,rtlSlred,r 1961. t
    73t

    of tire fO, versus pil diagrans represent fields of predorninance


    and are not necessarily exelusive of species in adjacent fields'
    particularly near the bouadaries. 0n aley speeific boundary
    the concentration of the species ropresented. on either siEe
    of the boundary is 121 and vrith progression into one'fiel<i
    the eoncentraticn of the predoninant s;iecies increases at the
    e:<pense of the o'ther species (Fig. V-12).

    Thp follovring explanatory notes detail specific aspects


    in the construction of the d.lagrans:

    (i) Effect of tJariation in the Concentration of Total


    Sulphur in Sol-ution

    ,iii;h the exception of the boundaries involving liquid


    sulphur (licruid sulphur/HsO4-.and liquid sulphur/HZS),
    posi-tions of the boun.,laries between the various aqueous sulphur
    species are independant. of variaticns in the coneentration of
    total sulphur in solution. In contrast the positi-ons df the
    bound.aries betveen the iron ninerals are dependant on the
    concentration of total sulphur in solu-uion. .l'Iith 5-nereasing
    concentrations of total sulphur the chalcopyrite/bornite
    plus pyrii;e and. pyrite/pyrri:oiite boundaries expand outr.rard"
    increasing the stabj-lity range of the pyri+.e and pyrrhotite
    fieids ai ihe expense of magnetite and henatlte.

    (ii) C}:alcop';1r:-'vefgorni't,e clus Pyrite Boundary

    The connents cliscussed unCer this heading in the fSe


    versus fA, dlagran section applir equally here.

    ( iii )r,o; fSz Contours

    '.ihere required, contours oi log fS, r.rere eonstrueted by


    the nethod outlined by Vaughan & Craig (tgta pp 329 - 33o)
    usln3 equations V-58, V-59, V-75 and V-?6 (Tab1e V-10).

    (rv) rco2

    .ihere iC0, i-s kno'.ri1 several potentiall;r liniiing bound_ariu.:=;


    T)2
    :

    can be defined. The COr/graphite boundery is dependant only


    on fOa and tlierefore its position is defined as for the tSZ
    versus fOZ diagrans. The anhydrlte/calcLte boundary, bouever,
    is rlependant on both tOZ and. fSr. Its posl-tion was calculated
    usin,3 equations V-7? and V-?8 (Table V-10). The pH of the
    calcite so1ub1e,/1nsolub1e boundary is dealt with in the earlier
    section of this Appendix tltled rrcalclte stability and pilr'.

    (v) llanrlanese ilinerals

    The rhodochrosite/alabandite bouniiary was calculated


    usini; erluatlons V-7g, V-80 and V-81 (f aUle V-10).

    (vi) Barite Soluble/fnsol-ub1e tsoundary

    The barlte soluble/insoluble boundary was calculated


    usins etluatlons V-82, V-83 and V-84 (taU1e V-10). I value of.
    0.0001n for the concerrtration of 8"2* in solution is inrticateC
    by other sturlies ( e. ii. Ilobinson , '197 t ) and theref ore this
    value uas used here.

    (vii) 534sttrs contours

    Contours of 634s,r^, (and IIS-) can be plotted. on fOa versus


    pll diagrans for . gitr;fr"va1ue of t34s .
    s
    for sone diagrams in this
    The contours.were constructed
    theej.s by proportioning out e34s- to t34tr^r, 534srr-,
    83&sro-,2-, g34s'so,- u"irrgfFactj.onatilfr'rr"to"" fron
    "r,o
    (4lglZ) and
    Ohmoto assignaing the valuesto contours of xf
    sulphide - r*fr sulphate calculated from equations V-61 , V-63
    and V-61+ ot Table V-10.

    This approach is not as rlgorous as that suggested by


    0lrmoto (lglZ) and Ohmoto & Itye (1 ,a79), in vhich the concentra-
    tion of a larxe nunber of sulphur species ls evaluated (usint
    activlty coefficients) at various points ln the f0, versus
    pH diagrau, hovrever considering the errors involved 1n the
    construction of the f0, versus pll diagram and the cal-culation
    of the paraneters of the j-ndividual mineralisations (teroperaiure
    fS2, pll etc) the method described here is considered adequate.
    733

    TABTE V-'11: Thernoilynanlc data used to caLculate the


    fTe, versus fllt dlaqrars. ?he fres encrr:y
    chan4e is 4ivon ln lhe forn a|,o = AII-T AJo.
    All ilata are ftoo fable ?-2 of Barton & Sklnner
    (ie?9).

    Iquatlon ileactLon -['reeener;;r chanlo


    iiunbor (ln joulos-ior T in K)

    ('/- 85 ) T"z(") - 2?e(s) -156,620 + 1t9.667


    (v- 86) Au+Tet=AuTe, -1?5,920 + 155.t,tT
    (v-s?) ,(,A';+Ter=2AgaTe -209,564. + 67.367
    (v-88) 2llg+Tet=Zllgle -2LOt7?,1 + 173.267
    (v-8e) 2Pb+?e=2PbIe -29(r,085 + 16L.26't
    (v-eo) 2ltg+S=2llqS -299,071+ + 215.57
    (v-e1 ) Zil:To+52=ZilfiS+Te - 19,213 + 39.37

    STABIL]TY OF FERBgRITE
    377'C IOOO borr

    FlgureV-l3: The stablllty of ferberite (feWOa) aa a functlon of fO, aarl fSa


    at, 577oc and 1 kbar: t{E - Feror/tero3, frNo = lll/l|10, rMQ = Fe2s10a/Fe30a
    + S1O2 antl lfM 't Fc0,/Fer01. (Fron Heu, 1976.)
    ii
    ti
    nb l'i

    Fuqgcit:" of T.q2
    it

    S", $as estinated for a few nineralisations by plotting


    rl

    'ihe aineral stability relations on ff"z versus fSt diagrass


    ;

    (ligs 11-5, I-L-8, I*0-15 ancl I-V-6). Tlre d.iagrans vere coll- i

    structed. usin.3 the equations listed in Table \r-11 f ollotling a


    sinilar procedure to that enployed' in the construction of the
    fSa versus fOa diagransr

    sPSCrJ'rC urll,ERAi/ SlSTEl',lS,


    ':'
    Tunqsten i.{inerals
    Skinner (1g6il iCentified disseninateC wolfranite in the
    igaeous and, hornfels rocks of the coastal sectioa south of
    Paritu, and. I'Ieigel (tgZA) noted. its occurrence in the early
    nineral.1sationatTuil,[ine.lieitheroccurrence!'aSconfirned'
    Curing this study and the conposition of these ni.nerals in
    relation to the wolfranite solid soluiion series ferberite
    (FeIJ0
    - ,) huebnerite
    u^'v:*vv (t,tnt+0,
    \"""-4' ) is unknor,rn. Scheeli'r,e (Cat'iO 4r.) '
    the othu"
    '+
    najor naturally occurring tun3sten nineral has not
    been founC in the Province.

    The stability relations of a nunber of tungsten ninerals


    have recen-r,ly been i-nvestigated. py stenproek (1971) ,. ilsu &
    Galti (1g7i) and. Esu (1976, 1977, 1981). Figs V-13' V-1/' and
    V-1j illustrate the stability relations of ferberite, buebnerite'
    scheelite ancl tungstenite (ifs2) at SlfC and 1000 bars pressure.
    Altbough the tungsten nineralisation at .Paritu and Tui itine
    is believed to have occurred, at tenperatures around IrZ5oC,
    it-surs high tenperature and pressure diagrans are used here
    because thernoCynanic data, without consid.erable extrapolationt
    are not available for tenperatures between 25oC ar:d' 577oG'

    Thestabiliiy relations of ferberite at 300oC shown i-n


    FiE. U-1,o calculated by Kolonin et aI (lglS) by extrapolation
    of Z5oC d.ata, are ineonpatible with the experinental d'ata of
    Hsu (1976). For exarnple Kolonin et alts diagrarn preclud,es
    assenblages of ferberlte with magneti.te or henatite whieh
    have been produced, under experinental condi.tions (Stenprock,
    19'11 ;' llsu, 1976). This case dernonstrates the
    d'angers of extra-
    .'
    ''. ..
    ; '1, :
    w5

    I{UEEiIE.RITE
    IOOO |borr

    /
    ot/
    "7e

    ifiaS rWSe

    Flggm,'9r-,1jn ?ts atobLtrlty,sf buebqarlto I lro{}ee a fuaetlon ef f0j.rna f9,,


    x3 5??9C anil 1 &barr, Syubog ll trot Flt.'V-13. fryror f,pu,r 9?6'.1

    5?7'C' lOOOib

    Grwor +ShrS; .
    SSi,.OcElO' fle'or

    FtrAurc $.15t tiho rte,brld.ty s! sGlecll.l,tc (oattoa) er e fune,t{c'lr


    -
    ai to, sil,al l8e
    st 5'fla} and 1 tbar. (Frou Eru, 19?7.)
    n6

    .ltgurc V-l6: thc rtabl'llty flcldr of tuagrtca and lron rlnctdt rr r fuaotloa
    o! log POa (ra tOa) and Ptl at ,OooC. (Fror f,oloala 1[3!, 1975.1
    73?

    polating thermodynanic data over large temperature ranges.

    Tungstenite is rare ln nature, requi.ring cond.itions of


    very loru f0, and hig'h fSe (Stemprock, 1971; I{su, 1977) to be
    stable (rlg. V-13, 'l-1lu and V-15). Scheelite is stable over
    a wid,e range of fOa and fSa conri.itions (Fig. V-15), whereas
    ferberite and hubnerite have a tnore restricted. occurrence,
    havlng linited fields of stability with pyrite and very
    linited stability fields with pyrrhotlte i.n conparison r,rith
    scheelite (c.f . Figs V-13 and V-1lr). Both seheellte and
    wolfranite are stable under a wide range of cond,itj.ons with
    rnagnetite and henatite. The assenblage ferberite plus hematite
    is repLaced. by ferric tungstate (Feri"IO5) and tr'iO, at high
    oxygen fugacities above 5l,ooc (i{su, 1976).

    The wolfrarnite at Paritu occurs uith pyrite but is


    replaced. by pyrrhotite (Ski-nner, 1967). Therefore rvolfranlte
    d.epositi-oa occumed r'rithin the pyrite stability field probably
    no'u far from the pyrite/eyrrhotite bouni.ary so that only a
    sna'l I change 1n fSa is required to nake pyrrhotite stable at
    a l-ater stage. The wolfra,rit,e/t;S, boundary i-n the pyrite
    fielC of Figs V-13 and V-1lr restri.ets r+olfranite stabi.lity
    in the pyrite field close to the pyrite/nagnetite boundary
    and iherefore the Paritu tungsten mineralisation must plot
    near the pyrrhotite pyrite - rnlgnetite triple polnt in
    Fig. I-C-3.
    n
    The occurrence of wolfranite at Tui .l{i-ne has not been
    described be.rrond l,.Ieigelts (tgZg) mention of its presence as
    an early phase, therefore its relation to other ninerals is
    not l<nown.

    Tui I'iine Stage 1 minerali-sation consists of p;.'rite'


    chalcopyrite, hematite, ninor bisnuthinite, electrun, rare
    tetradynite and possibly bornite althou,;h not all coexistlng
    together. Pyrrhotite has not been record'ed. The Staqe 1

    assenblage plots on or near the henatite/pyrite boundary in


    Figs V-13 and V-14. Sinilar cond'itions for wolfrarnite
    deposltion are conpatible wlth the ferberite anL huebnerite
    stability diagrams.
    738

    The absence of scheelite from the tungsten nineralisation


    at Paritu and Tui l,line may be attrlbuted to a low activity of
    calciun in 'r,he hyd.rotheraal solutj-ons.

    SeIeni-_ferous and Sel-enide iline,r'als

    Iniroduction
    Because seleni.um has sinilar cheni-ca1 and physical
    properti-es to sulphur it may isornorphously substitute for
    sulphur in sulphide nineraLs. Such substltution is the nai-n
    forn of occurrenee of selenium in nedi.un and high teuperature
    ore deposits: selenlde ninerals generall-y occur only in
    d.eposi'us formed ai low temperature and under relatively
    oxidislng cond.itions (Tischendorf & Un4ethfi.n, 195t*; Dryachkova
    & i(hodakovskiy, 1968).

    The prooortlon of Se/S in sulphid.e ninerals j-s considered


    to be relateC to the ratio of dissolveC reduced seleniun
    species/dissolved redueed sulphur species in 'r,he parent hydro-
    i:herrnal fluid. Recent s+'udles have sugqested that this ratio
    is no'., only- dependent on the ratio of total Cissolved.
    seleriiur to totel dissol'red. sulphur (Se/S) in solu+'ion but
    nay also be infl-uenced by the oxidation stater PI{ and.
    tenperature of the solution. Therefore ihe oeeurrence of
    seleniferous of selenide minerali in a nineral assenblage nay
    be used to inCicate the o:cidation state of the hydrothernal
    F'l ,,; 't
    i-LU!U. a

    Thernoshemieal Stud ie s
    Tischendorf & Ungethfir,i (1961) suggested. that for a si-ven
    tenperatue and rati.o of {Se/ { S in solution, the ratlo of
    -t.)
    Se'-/S'- in solution increases rrith increasing oxidation
    potenti-al and decreasing pil. Dtyaehakova & iihod.akovskiy Oge,g)
    supported. their hypothesis and. added 'r,irat the SuZ-/o2- ratio
    also increased with d.ecreasini tenirerature.

    Shikazono (1978) applied. these relaiionships to several


    iapanese ore deposits using the Se content of acanthj.tes to
    help deternj-ne the fOZ and pH conditions of nineralisation.
    Yananoto (1976) took the raethod a step further by eonparin3
    739

    sl
    o
    (r
    o

    PH

    Flgure V-l?l Predonlaaat aquaous aeleirlun and aulphur apecJ.es as a function


    of fO2 and plt, st 3O0oC, 1og a L3 - -2 aird 1og a(Se = -?. The gelealun
    specleo boundarleg vere redrarn fron PLg. 1c of lauaraalo (1976). The
    o:Cldleeat/reduced aqueous selenl.un specleo boundary occure at a hlgher'.
    fo, than the oxldlgeil/redueeil aqueous aulphur apecles boundary and
    tbereforc the ratlo of reduoed gcleulun apeelea,/redueed aul,phur apecl,ee
    ln solutlon lacreasee vlth lncreaalng fO, abova the oxtdlsed/reiluced
    Bulphur speclea bouadary. The effect Ls belleved to lndlcate tbet the
    praclpltation of gelealferoug end selealde nlnarals ls oost llkely to
    oocur ln oxldlsLag envJ.ronoeate.
    T+O

    Se/S ratios cf rli-fferent sulphid.e ninarals (pyrit,e, pyrrhotite'


    sphalerite, chalcopyrite and bornite) vith the ratios of their
    sulphur -isotopes.
    - 1|"

    Iiowever, these studles assunecl that 52- is the iruportant


    ailphur speeies in solution, whereas E1lis & Giqgenbach (1971)
    demonstrated that und.er nost natural condi*"ions the concentra-
    tion of s2- 1n hycro',,herraa1 soluti-ons is insignificant,
    invalidating much of the thernochem1cal daia presented by the
    authors cited previouslY.

    i{everthe}ess, their qeneral conclusionsr that l,he


    d.eposition of seleniferous or selenide ninerals j-s favoured. by
    oxidising condi-tions and l-ow tenperature, is probably correct
    beeause the oxidised/reduced aqueous seleniun speeies
    bouncLary occurs at a higher f0, than the oxid'ised/reduced' ,

    aqueous sulphur species bounCary (3ig. V-17). Therefore the


    ratlo of red.ucecL seleniun species/reduced sulphur species in
    solution increases ruith increasing fO, above the oxidised/
    reduced sulphur species bounclary. The separation of the two
    boundaries is believed. to increase with decreasi-ng temperature'
    therefore increasing the effect. .

    A'rigorous appraisal of this effect is not posslble


    becAuse of the probable inaccuracy of the available therno-
    d.ynanic d.ata for aqueous seleniun species (tfre d'ata has not
    been si-gnifj-cantly revised since Dryachkova & Khodakovskiy'
    1 968).

    Application
    The relationship of Se to tenperature in d'eposits of the
    i{auralii- Gold - Sil.rer Province seers to follo'.v that su-ggestecl
    by Drirachkova ?r I{hod.akovsltiy (tg5e): i-n noderate to high
    tenperature environnents Se isonorphously substiiutes for S
    in tetradynite (l,lonovrai, Tapu Thames; ,''[erc]rant, 1978),
    tellurobismutite (Sytvia, Tapu - Thames, i'lerchan',,, 1078) and
    acanthite (i,laratoto and. I'Iaihi; c.f . Table 5*2) , r'rhereas
    seLenid.e (plus Seleniferous) ninerals occur in the l-Ow
    !r,erprort,UIe rLeposits at Te Aiiu:aia (a,3uilarite, naunanni't'e,
    seleniierous aiyrocli+,e and selenif erous qalena; Ramsay , 1971)
    a.nti lrol:en iij.11s ( aguilarite, narlnanni'ue I a';uilarlte
    7l+L

    nauma.nnite 5-ntergror.ri:,hs,acanthite aguilarite intergrowths


    and sone eonplex gold silver arsenic sulphoselenide ninerals;
    l.{oore , 1976).

    Fig, V-17 illustrates that the presence of seleniferoub'


    and seleni-de nlnerals in an assenblage nay refleet a relatively
    high sulphate/sulphide ratio in the parent hyd.rothermal fluid.
    This appears to be the case al, Broken Ilills-(f ig. I-K-9) and
    l.taratoto (rig. I-o-13) but not Te Ahunata (fie. I-8-6) Tapu
    Thanes (f -l-Z) and tr{aihi (f-s-10). The lSe/ S ratio of the
    hydrothernal fluid nay have been the controlling paraneter
    in the Latter systems.
    7t&

    APPEI{DIX VI

    ORE PETROGRAPHY OF SAI4PLES TROM WAIHI

    SAMPTE 13901 (hlh35), MARTHA MINE (UNLOCATED)

    Sample 13901 is finely banded as follows "(in order of


    deposition):
    1. 1nm band of quartz.
    2. 0.3mn band of quartz with subordinate galena (av. 0.08nn,
    trBXr 0.3mn) ttre latter filling spaces between subhedral
    quartz. A singile aggregate (0.3mn dia.) of a sphalerite
    (av. 0.02nn, nax. 0.05rnrn), pyrlte (0.05nn) and galena (av.
    0.01mn, max. 0.05nm) intergrowth occurs surrounded by quartz.
    Very rare gralns of electrum (less than 0.01mm) occur in
    quartz.
    3. 1nn band of quartz qnd a discontinuous string of subhedral
    pyrite grains ( a'u. 0 .2mn , n&x. 0. 5nm ) . The pyrite contains
    inclusions of galena and sone gralns that occur adjacent to
    galena of the prevlous band are embayed by galena.
    lr. Q.3 - 0.5nm band of quartz.
    5. 1nm wide quartz band containlng a subordinate pyr'ite
    galena intergrowth. Pyrite and galena (both av. 0.1mro max.
    0.3mm) have nutual boundary relatlons and fill spaces
    betr.leen subhedral quartz.
    6. 0.3mn band of quartz.
    7. 1 urn band of nalnly quartz but with isolated grains of pyrlte,

    sphalerite and galena - acanthite conposi.te grains all


    averaging approximately 0.1mm.
    8. Q.2 - 0.8mn wide ribbon-like band of aLmost continuous
    pyrite grains. The quartz on both sides is subhedral to-
    wards the pyrite. Galena and acanthite occur as inclusions
    in pyrite and rarely as grai.ns (up to 0.1mn) scattered along
    both sides of the pyrite band.
    9. 0.5mn band of quartz.
    10. 3nn band of a complex lntergrowth betueen pyrite (av. 0.1mn,
    mcrXo 0.3mm) and equigranular (av.0.05nm) quartz, sphalerite
    galena - acanthj-te composite grains and very rare electrum
    (max. 0.03mm). Pyrite contains abundant inclusions of
    galena - acanthite and el-ectrum. The quantity of pyrite
    varies in different parts of the band.
    11. 0.03nn ribbon-Like band of chalcopyrite.
    12, 3x7nn lens of quartz with subhedral to anhedral- pyrite (av.
    0.2mm, max. 0./rmn) and le.sser galena (av. 0.1mn, max. 0.3mm),
    sphalerite (av.0.05mm, max.0.3mn) and chalcopyrite (av.
    0.05mn, max. 0.1mm). Ga1ena, sphalerite and chalcopyrite
    occur mainly at the marglns of and enbay the pyrite grains.
    Pyrlte contalns inclusions of galena.
    13. The remalnS-ng part of the secti.on (up to 1Onm)contains galena
    acanthlte composite grains (av. 0.1mn, max. 0.3mn), pyrite
    (av. 0.1nm, max. 0./*mm), sphalerite (av. 0.1mn, nax. 0.6nm)
    and chalcopyrite (av.0.1mm, nax.0.3mn) generally as
    isolated grains or agsregates of two or three gralns filling
    spaces between subhedral to euhedral guartz. There 1s a
    general coarsen5.ng of graJ-n size auay from band 12. The
    sulphides make up less than 50% of the band and their pro-
    portions vary; galena - acanthite being dominant near band
    12 but pyrlte becoming dominant several niLlimetres avray
    from band 12. Sphalerite and chalcopyrite are locally
    abundant at the outside edge of band 13 (ttre edqe of the
    specinen). Boundaries between adjacent sulphides in
    conposite grains appear mutual. Sphalerite contains
    abundant tiny blebsrand a few larger areasrof chalcopyrj.te.
    Pyrite contains abundant inclusions of galena - acanthite
    (generally 10fl but up to 30% of the pyrite grain). Some
    pyrite grai-ns adjacent to and embayed by sphalerlte also
    contain abundant inclusions of sphalerite.

    SAMPLE 13902 (I,Jh37), I4ARTTIA }'IIIIE (UNLOCATED)


    Individual grains of anhedral to subhedral pyrite (av. 0.1
    rnrnr max. 0./+mm; approximately 20fl of section), anhedral
    chalcopyrite (av. 0.1mn, max. 0. /rmrn; approximately 2% of section)
    anhedral galena (av. 0.1nm, max. 0.2mmi approxirnately 1% of
    section) and groups of smal-L scattered rounded grains of
    sphalerite (av. 0.03nn, max. 0.1mm; approiimately 5% of section)
    occur filling spaces between subhedral to anhedral grains of
    quartz (av. 0.1mm, max. 0./+mm; approximately 72fr of section).
    The sphalerite nay represent rennants left after replacement
    (resorption) by quartz.
    7144

    SAMPLE 13903 (Wh/-8), I4ARTHA MINE (UNLOCAJqED)

    Bands (approxinately wide) of quartz with scattered


    3mm
    grains of subhedral pyrite (av. 0.2mn n&xr 0.5mm) alternate
    with bands (t - 4nm wide) of quartz with scattered subhedral
    pyrite (av.0.1mm, max.0.5mm) and aggregates (up to 1nn ln
    dlameter) of sphalerite, galena, pyrite, chalcopyrite and very
    rare electrun. The sphalerite is subhedraL to anhedral to
    surrounding quartz and contains abundant but extremely sua1l
    (approximately 1 micrometre or Iess) blebs of chalcopyrite.
    Larger i.nclusions (0.O1mn), veinlets and grains (less than 0.1mm)
    of ehalcopyrite occur rarely in sphalerite. Chalcopyrite aLso
    occurs as rare solitary ovoid, grains (av. 0.04, nar.0.1mn) in
    quartz. Galena (av.0.03mm1 rnsXr 0./+mm) generally occurs inter-
    grown with sphalerite or as ovoi-d i.ncLusions and cores j-n
    pyrite, but rarely as solitary grains ln quartz. Sphaleri-te
    has nutual enbaynent relations with adjaeent grains of pyrite
    although rare veins of pyrite penetrate sphalerite. Ilare
    electrun generally occurs as isolated grains (0.02mm or less)
    in quartz although one inclusion was noted in galena. The
    sulphides make up less than half of the sulphide bands.

    SAMPLE 139?8 (I,ihz?), MARTIIA t"lrNE (UI{LoCATED)


    Subhedral to euhedral grai-ns of sphalerite (av. 2mm, il&Xo
    5mm) are separated anci replaced by lnterstitial apeas of quartz,
    galena (av.0.2nm, max.0.5mm) and nj-nor pyrite (av. 0.1mm,
    nax. 0.2mm). The sphalerite grains contain abundant tiny blebs
    of chalcopyrite (Fig. 4-19) and larger inelusions of galena,
    pyrite, chalcopyrite and pyrrhotite arranged in dendrltlc
    rr streakytt (
    Fig . lr-25) and poikilitic ( f ig . tr-26) textures .The poikititic

    textures are interpreted &s cross-sections of the streaky


    textures. The pyrite, chalcopyrite and pyrrhotite are generally
    ovoid shaped inclusions (0.01 - 0.02mm in diameter) in both
    the streaky and poikilitic textures, whereas the galena occurs
    as long rlbbons up to 0.05mm wide and 0.5mm long in the streaky
    textures. The two types of textures consist of either galena
    or a combination of galena with chalcopyriter pyrrhotite or
    pyrrhotite plus pyrite. In some gralns contalning polkilitic
    galena plus chalcopyrite it is difficul-t to distinguish the
    chalcopyiite of the poikilitic texture from that of the usual'
    chalcopyrite in sphalerite exsolution, expitaxial growth or
    7t+5

    replacement. Chatcopyrite nay nake up substantiat proportions


    of the sphalerite grains in these cases.

    The sphalerite, plus contained inclusi-ons, generally nakes


    up approxinately 90f of the sectioni however in one nount this
    material is eross-cut by a 2 - 4mn wide vein of anhedral galena
    (=the matrix, grain size approximately 1mn?), subhedral pyrite
    (av. 0.3mn, max. 0.5mm) and subhedral to anhedral quartz. The
    pyrite is commonly embayed by galena.

    In sunmary, the textures are interpreted as representing


    a sequence of sphalerite invaded and replaced by various com-
    binations of galena + quartz 1 pyrite. 1 chalcopyrite t pyrrhotite,
    in turn followed by galena + pyrite * quartz.

    JUNCTION

    A 2 - 3nm band, in otherwise barren quartz, contains scattered


    grains of pyrite (av. 0.2mm, max. O.4mm) fitting spa.ces between
    subhedral grains of quartz. Sphalerite (av. 0.06mm' max. O.1mm),
    galena - acanthite composite grains (av. 0.03mm' max. 0.1mm) and
    electrum (av. 0.01mm) occur as solitary grains filling spaces
    between subhedral quartz (av. 0.1nrn) or intergrown with each
    other in small aggregates (up to 0.2mm in dianeter) or intergrown
    wlth the larger pyrite qrains ( exhibitinq mutual boundary rela-
    tions with each other and pyrite). The pyrite gralns, both when
    solitary in quartz or intergrown with aggregates of other
    sulphides, contain abundant ( typically 107,, of the pyrite grain)
    inclusions of galena (-acanthite?) and eleetrum (Uottr typically
    0.01mm) and l,ess common inclusions of sphaleri-te. Except for
    minute blebs in sphalerite' chalcopyrlte is very rare. ELectrum
    oeeurs solitary in quartz or associated with any of the sulphides
    but most eommonly with galena as inclusions in pyrite. The
    content of the mineraLised band is approxinately 60ft quartz, 23il
    pyrite, 8% sphalerite, 8% galena (including subordinate acanthite)
    and l-ess than 1% chalcopyrite and eLeetrum.

    SAMPLE 1tr039 (1,Ih28), MARTHA l"lrNE (UNLoCATED)

    In polished section, speeimen 14439 consists of large masses


    of sphalerite with occasional smal1 intergranular areas (0.2
    0.5mm) of interstitial chalcopyrite, quartz and galena. Thin
    ?l+6

    (typically 0.01nm, but up to 1na in the case of quartz) vein-


    Lets of chalcopyrite and. quartz r*ith sparse ind.ividual grains
    of subhedral pyrite (av, 0.08mm, nax..0.2mn) and anhedral galena
    (av. 0.1mn' nax. 0.3nm) penetrate and' fill craclcd in the
    sphalerite nasses. ?he sphalerite contains abund.ant tiny
    inclusions of chalcopyrite which d.elineate grain b'oundaries,
    indicating aq average grain size of 0.2mrn for the sphalerite.

    At one ed.ge of the polished roount a 2 x 1nn nass of galena


    containing subhedral pyrite'(av. 0.03nnr nax. 0"08nn) ancl
    anhed.ral ehalcopyrite (av. 0.03mrne r&xr 0.06nn) interfingers
    with the sphalerite.

    SAMPTE 14040 (i.Ih29) , I{ARTHA I,IINE (U}iLOCATED)

    The two polished nounts exanined, of sanple 7l+Ol& are very


    sirnj_lar to sanple 13978. In one, subhedral to euhedral grains
    of sphalerite (av. 1.5nn, nax. {mn) occur separated by quartz'
    the latter naking up only about 20$ of the nount. Snall (av.
    0.1nm, nax. 0.2nn) subhedral to euheilral grains of pyrite
    comnonly occur at the nargins of the sphalerite grai.ns. Galena
    also oceurs as narginal grains (av. 0,1mn, max. 0.3nn) to
    sphalerite bui nore comnonly as poikilitic and dendritic
    streaky inelusj-ons within sphalerite, in assoeiation with
    pyrrhotite, pyrite or chalcopyritg (ttre latter grains generally
    0.01 to 0.02mn in diameter). However, this poli.shed. nount of
    1 40/10 differs fron 13978 in that there appears to be a eonplete

    transition fron the dendritic - streakf *td poikilitic galena


    to large (0.1 O.5rnn) grains of galena in the sphalerite and,
    in adjoining quartz gangue. The quartz also contains isolated
    subhedral grains of pyrite (av. 0.08nn' nax. 0.2nm). Finally
    a lnrn r.rid.e band of quartz cross-cuts and incl.udes sone fraguents
    of the earlier naterial.

    fn the second, poltshed mount of sanple 1I$l+O the grains of


    galena (av- 0.15nm, nax. 0.6un) and pyrite (av. 0.O5nn1 1n4X.
    0.2nn) are nuch nore abundant, the poikilitic and dend,ritic
    streaky galena t pyrite t pymhotite (chalcopyrite d'oes not
    appear to be associated. with these textures in this nount)'.Iess
    conmonr and the nount is characterised, by a greater degree of
    brecciation and, infilling by later barren quartz. The pyrite
    711?

    graj-ns are subhedral, contain abundant inclusions of, and are


    very eorr6ded (e.g. embayed) byr fialena. The quantity of
    chalcopyrite bl-ebs in sphalerite is quite variable, ranging
    from abundant in some grains to almost absent in others. Like
    the other mount of this sample, &t one edge the sphalerite
    predominant material is j-nvaded by a large area (6 x 3mm) of
    galena containing anhedral sphalerite (av. 0.15mm, max. 0.3nm),
    anhedral quartz (av. 0.08mm, max. 0.20mm), subhedral embayed
    pyrite (av. 0.0/rmm, max. 0.1mm) and smaLr bLebs of chaLeopyrlte
    (max. 0.03mn), j-soLated in the qalena.

    sAt4pLE 14,0/-1 (i,Ih30), MAITTIIA l.rINE (UI[LoCATED)

    Sample 11r041 contains predominantly galena (approximately 55i")


    and chalcopyrite (approximately 20f,) with mi-nor sphalerite (5%)
    and pyrite (5/,) cross-cut by a 0.2 - 1.5rnm wide band of cluartz
    (5%) and euhedral pyrite (av.0.0Jmur, max. 0.2rnni approximately
    5ft of the secti-on). In the forner naterial, large masses of
    chalcopyrite (approxinately 2-3nn) contain clusters of anhedral
    to euhedral pyrite pseudomorphing mareasi-te balrs originally
    averagi-ng 0.5mm in diameter. The chalcopyrite masses are
    surrounded by areas eontaining predomj.nantly anhedral roundecl
    grains of galena (av.0./+mm, max. 1mn) with interstitial
    chalcopyrite (matrix), sphalerite (av. 0.1mm, nax. 0.2mm), quartz
    (av. 0.06mm, max. 0.2mm) and pyrite (av. 0.1mm, max. 0. /rmm) tir"
    latter euhedral to chalcopyrite but embayed by and eontainlng
    inclusions of galena and sphalerite.

    Supergene eovell-ite replaces margi-ns of chaleopyri-te.

    SAMPLE 1/*O/*3 (l/Ih35), VICTORIA VEIN. ADIT LEVEL


    (0.5 - 5mm) of virtually barren
    Sample 1lr0lr3 contains bands
    quartz alternating with bands (0.5 - 2mm) contalning scattered
    individual grains of acanthite (av. 0.05mm, ma.x. 1.Omm) ano
    electrum (av. 0.1mn, max. 0.2mm). The mineralised bands
    contain up to 30% acanthlte but less than 1% electrum.

    SAMPIE 1/+046 (llh/-3)1 MAITTHA I,tINE (Ut'itOCAIUO)

    Sample 1 lr0116 is banded as follows ( in order of deposition):


    1. 2mm band of quartz containing rare isolated grains (0.05mm)
    of subhedral pyrite and sphalerite.
    2. Zmm band of quartz with scattered subhedral pyrite (av.
    7l+8

    0.1mm, max. 0.3mmi 25-30% of band) and blebs (av. 0.02mm,


    m&Xr 0.05mm) of sphalerite (5fi) and galena (2%). pyrite
    contaj-ns abundant lnclusions of sphalerite and galena (arr.
    0.01nm each) and a fevr inelusions of electrum (0.005mm).
    ? 2mm band of sphalerite (av. 1nm, raX. 2mm) containing
    abundant inclusions of galena in poikilitic (FiE. L-ZZ)
    and dendritic - rrstreakytt textures.
    In. 0 - 0./+mm band of pyrite (av. 0.2mn, nax. o.3mm) subhedral
    to folIowin,3 quartz but interfingers with sphalerite of
    band 3 (Fig. lr-22). The p.yrite contaj-ns abundant inclusions
    of'galena.
    E
    3mm band (remainder of mount) of quartz with scattered
    grains of subhedral - euhedral pyrite (av. 0.3mmp rndxo 0.8rnrn)
    which, in contrast to pyrite of band lr, contain very few
    lnclusions of galena. The pyrite grains are generally
    fractured.

    sAi'{pLE 11,04,7 (tIhl,l,), I.IARTHA VEIN, 7 LEVEL

    Three phases of mineralisati-on, represented by different


    bands, occur in specimen 1t0l+7. Two are observed in polished
    section, uhereas the third was noted in hand speeimen.

    An early phase of euhedral pyrite grains (av. 0.2mm, max.


    0.5mm) in clusters surrounded by chalcopyrite is brecciated ancl
    the ? - 3mm fragments are surrounded by quartz.

    The second phase consists of sphalerite (av. lmmrmasses up


    to 2.5nm) ancl quartz with Lesser qalena (av. 0./rmm, max. 0.8mm),
    ehalcopyrite (av. 0.2nm, max. 0.Bmm), pyrite (av. 0.1mm, max.
    0.2mm) and eLectrum. The sphalerite is subhedral and eontains
    variable quantities of tiny chalcopyrite j-nclusions and larger
    inclusions of chalcopyrite and galena. Oalena occurs as 6lrains
    adjacent and i-nterqrown with sphalerite and also separately
    in quartz. chalcooyrite oceurs as thin rims and blebs at the
    junction of sphalerite and ;lalena and also as larqer masses
    intergrown with qal-ena, sphalerite and quartz, subhedral pyrite
    occurs solitary in quartz or with sphalerite, galena anc
    chal-eopyrite, often embayed b./ these sulphides. It contains
    abundant j-nelusions of i1alena. El-ectrum occurs as small blebs
    ( 0.005rnm ) in ,lalena, 1ar,jer areas (av. 0.01mm, ,nElX e 0. 03mm )
    749

    intergrown with galena, solitary ln quartz, and ln one instance


    as two 0.02mn inclusions in sphaleri.te.

    The third phaser rcognised in hand specinen, consists of


    nediun grained quartz (2nn) with interstitial fine grained (0.5mn)
    pyrlte and chalcopyrite.

    SAMPLE 140/+8 (l'Ih45), UNL0CATED

    Sample 1l*01+8 is banded as foll-ows (in order of deposition):


    1 . 5 - Srnm band of quartz, subhedral pyrite (av. 0.3mm1 rnsxr
    0.?nnt 25fi of band) and chalcopyrite (av. O.2nmr fiBX. 0.5mm;
    5fr of band), the latter filling spaces between subhedral
    euhedral quartz.
    2. 1 - 2mn band of sphalerite (av. 0.1mm, nax. 0.5mm i lr0*) ,
    chalcopyrite (av. 0.1mm, nax. 0.3mm; 15fr), acanthite
    galena composite grains (av. 0.05nn, nax. 1.Omnl 3fi) and
    electrum (av. 0.02nn, nax. 0.2mml 1fr) interqrown with each
    6ther and quartz. Quartz is subhedral - euhedral towards
    the sulphides, particularly chalcopyrite.
    3. 2mn band of subhedral - anhedral rounded pyrite grains (av.
    0.3mn, max. 0.6mm; varyj-ng fron 50{" to a continuous chain).
    Pyrite is intergrown with, and contains abundant inclusions
    of , electrum (av. 0.05nm, max. 0.12nra); some pyrite grains
    contaj.ning up to 20% electrun. Pyrite also contains less
    conmon and snaller (0.01nm) inclusions of qalena. Bancl 3
    i-s not praI1e1 with the other bands and appears to partly
    cross-cut band lr.
    lr. 2 - 6nm band of near equi-granular quartz ( av. 0. 1 mn e rBX .
    0.3nm t lrofr), sphalerite (av. O.1mm, max. O./nmm i 30%), qalena
    - acanthite composi-te grai-ns (av. 0.05mm, max. 0.3mn ; 15fr) ,
    pyrite (av. 0.1nm, max. 0.5mni 1}fr), chaleopyrite (av. 0,1nm,
    nax. 0.3mn | 5fi) and electrum (av. 0.02mms rnsxo 0.15nn; less
    than 1fr). The quantity of pyrite and chalcopyrite relative
    to sphalerite and galena - acanthite varies fron one part
    of the band to another and areaa 1ocal1y doninated by pyrlte
    or chalcopyrLte occur. Boundary relationg betseeu the
    different sulphides are nutual but quartz ig genrally
    subhedral to the sulphides. Electrun occurs iatergrovn rlth
    all other phases.
    5. ?nn band of quartz slth scattered gralns of pyrite (av. 0.1nu,
    750

    nax. 0.5nmi 1A%), sphalerite (av. 0.05mn' nax. 0.2mm; 1ft)


    and ehalcopyrite (av. 0.05nnp IIIELX. 0.3nn; less than 1%).
    Pyrite is subhedral but sphalerite and ehalcopyrite fi1-l-
    spaces between subhedralquartz. '

    6. Quartz crystals projecting up to 0.5nn into vugs.

    SAMPLE 14049 (I'Ih42) MARTHA VEIN I'AT DEPTHN

    Sample llr}t+g consists nostly of quartz with approxinately


    30fi pyrit,e (av. 0.1nn' nax. g./rmm), 8 - 10{o sphalerite (av.
    0.2nn, max. 0.8mn) and 1 - 2% galena (av. 0.05mm' max. 0.2nn).
    Pyrite occurs as individual grains or clusters of a few grains
    scattered in the quartz gangue. The smal-1er grains of sphalerite
    occur as cores within large pyrite grains.or pyrite clusters'
    r.rhereas the larger grains occur in quartz but have grains of
    'Pyrite
    pyrite distributed discontinuously around their rims.
    is euhed.ral in quartz but sphalerite i-s subhedral within or
    when adjoining pyrite. Galena al-so occurs as cores and
    incluslons in pyrite, intergrown with sphalerite or separately.
    It very rarely occurs as isolated. grains in quartz, Chalcopyrite
    occurs only in sphalerite as tiny blebs which are extremely
    snaIl and generally uncommon.

    SA},IPIE 14050 (I,Ih/+?) I.IARTHA VEIN, 1O LEVEL


    'Sanple 1l+050 exhibits cockade structure, consisting of
    breccia fragnents eoated by a 1 to 2ron band of seni-continuous
    chalcopyrite enclo sing subhedral to anhedral quar.tz ( av . 0 .1 nm ,
    nax. 0.2nm) and euhedral pyrite (av. 0.05rcu' max. 0.15mrn).

    SAMPIE 14051 (Wh/+9), UNLoCATED

    Large nasses of sphalerite (up to 5mm i-n di.ameter) have'''


    narginal grai-ns of subhedral pyrite (av. 0.1mm' uiax. 0.8rnrn),
    anhedral galena (av. 0.2mm, nax. 1.Onm) and anhedral chalcopyrite
    (av. 0.08mn, nax. 0.4mm). . Tiny blebs of chaleopyrite are un-
    comnonly present in the sphaleri-te, however chalcopyrite and,
    to a lesser eixtent, pyrite penetrate sphalerite along thin
    veinlets (typieally 0.01nm and generally less than 0.06mm wide).
    This nateri-al is brecciated and followed by subhedral quartz
    (av. 0.1nn, nax. 0.3mn) subhedral pyrite (av. 0.1mnr max. 0.4mm).
    and anhed.ral chalcopyrite (av.0.1nm' max.0.dnm) and, later,
    by nore abundant fi-l1ine of subhedral to euhedral second
    75L

    Flgure Vr-1: Replacenent of sphalerlte (11ght grey) and galena (vhlte) by


    quartz (dark grey) ln sample 14052 fron the Hartha Veln, 10 LeveL, i,lalhi.
    sooe sphalerl-te gralna exhlblt a lanellar texture vi"th quartz. The
    gnall black areas are plte. jOX.

    Flgure VI-2: Replacenent of galena (Hhtte) ephalerlte (Crey) by quartz ( dark


    ' grey) ln eaople 14052 frou the Hartha Veln 10 level, l{alhl. Ths ga1 ana
    exhlbl t s a dendrltlc texture 1n quartz. 5OX.
    752

    generation quart z (av. 0. {.mm r nax. 1 .0mm ).

    The proportion of the various minerals (regardless of


    stage) is approximately lr5% sphaleri-te, 35fr quartz, 1Qfr pyrite,
    8fr galena and ?fi chalcopyrite.

    SAMPLE

    A 2nm wide band containing grains of subhedral pyrite (av.


    0.3nm1 rn&xr 0.5mm) scattered in quartz (approxiurately 70fr gangue'
    30fi pyrite) oceurs adjaeent to a 12mrn band contai.ning approx-
    inately 50ft quartz, 30fr sphalerite, 16fi galena, 2% pyrite , 1fr
    ehalcopyrite and colleetively 1fr tetrahedrite, acanthite and
    eleetrum. In the Latter band the sulphides appear to be
    replaced by quartzr Ee denonstrated by 1ame1lar texture of
    sphalerite (Figs. 4 - 23 and VI-1) and dendritic - vernicular
    texture of galena (fig. VI-2) in quartz. Sphalerite masses and
    laths occur up to 2mm long and contain abund,ant tlny incluslons
    of ehalcopyrj.te, sometines in preferential orj-entations' and
    inelusj-ons of tetrahedrite (av. 0.01mn, inoxo 0.03nm). Galena
    occurs as interconnecting ato115, ribbons etc. 0ecupying areas
    up to 2mn in whieh isolated grains of galena are typlcally 0.1
    to 0.2nn long.

    In addition to the abundant bl-ebs ln sphalerite, chalcopyrite


    aiso occurs as grains (av. 0.05nmr max. 0.12mn) generally
    tntergrown with galena. Similarly acanthite ( av. 0.02nu 1 IIlsx o

    0.05mn) and electrum (av.0.02mrn' max.0.0/*nm) also generally


    occur lntergrown with galena although acanthite also occurs as
    solitary grai-ns in quartz. Subhedral- to euhedral pyrite (av.
    0.1mn, nax. O.5mm) is embayed by and contains inclusions of
    galena (and rarely sphalerite) indicating replacenent of pyrite
    by the other sulphides. Galena may also replace sphalerite in
    some parts of the band.

    In sumnary a sequenee of; pyritel sphalerite * tetrahedrite'


    galena * chalcopyrlte * acanthj-te + electrumr and quartz, is
    lndlcated.
    753

    APPENDIX VII

    ORE
    - -; PETROGRAPHY OF SAMPLES
    FROM KARANGAHAKE

    AMPLE 1LO2 TL1 ? TALISMAN MINE (UNT,OCRTSO)

    In sanple 1t+023 (TL1?) nediun graiued (but nainly as


    nasses up to 5mn) galena, sphalerite and hhalcopyrite occur
    approxirnately ln equal proportions r,rith lesser quantities
    of quartz and pyrite, Galena is generally subhedral to
    sphalerite and sone sphalerite grains penetrate adjacent
    galeua as rare veias. chalcopyrlte fron the large nasses
    fill fractures in adjacent sphalerite grai-ns and also pene-
    trate and include galena. This is particularly narked in a
    later phase .bf chalcopyrlte introd.nced by late quartz.
    Anhed.ral pyrite fron this stage also penetrates galena fron
    the nargins of the quartz vein, the galena being subhed.ral
    to the pyrite. snall inclusions of galena occur in
    ehaLcopyrite and vice vTSor Tiny incLusions of chalcopyrite
    occur in sphalerite (exsolution, replacenent or epitaxial
    growth). Rare pyrite (one grain 0.4nr0) occurs in sphaleri-te
    with sphalerite being subhed'ral to the pyrite'
    spherules (av. 0.8nn; ,o.xr 2.0un dia) of pyrite (after
    narcasite?) and quartz occur in chalcopyrite. In the largest
    example the quartz has penetrated the chalcopyri-te along a
    narrow vein. The pyrite consi-sts of sua1l grains (av' 0'05nn,
    rrsxe 0.1nn), subhedral near the nargins of the spherules and
    fi.brous teward the eentres. Euhedral grains (av, 0.2nn1 I1&Xo
    0.4nn) of pyrite also occur in chalcopyrite'

    These relationships are interpreted. as indicating near


    sinultaneous deposition of galena and. sphalerite (perhaps
    with some galena before sphalerite) followed by chaleopyrite
    and pyrite, the latter pair probably in tuo stages.
    7slr

    SAMPTE ), TALISMAN MINE (IINL.OCATED)


    1402/* (TL21
    Sanple 1t+Ozt+ (flZl) eontains a sequence of thin quartz
    and sulphide bands, ending j.n vug quartz crystals (up to 2nrn
    long) overgrown by laqge crystals of gypsun.

    The sequenceis continuous (uninterrupted by breceiation


    etc) beginning with a 1mn band. of quartz containi-ng scattered
    gnains of euhedral fine grained pyrite (av. 0.1mnr tnax. 0.3nn)
    lining very altered country rock.
    An 0.5nm band follows containing ind.ividual grains of
    galena (av. 0.2nn, nax. 0.5nn) surround.ed by eirhedral quartz.
    A further 0.5mn band of quartz contains sphalerite (av. 0.3nn,
    In&Xo 0.5nm), galena (av. 0.1nnr nax. 0.3nm) and ninor pyrite
    and chalcopyrite (both av. 0.1nn, nax, 0.3trn) generally as
    aggregates of a few grains seattered in quartz. The sphalerite
    is anhedral, margined and penetrated. by adjacent galena and
    contains a few large inclusj-ons of galena and abundant tiny
    inclusions of chalcopyrite. The galena.contains a fetr snall
    graj.ns of chalcopyrlte (nax. 0.05nn), enbays pyrite aad occurs
    as inclusi-ons i-n pyrite (replacenent of py by gn). Both 0.5nn
    bands eontain approxirnately lr0% sulphides and are reeognisable
    in hand specirnen as a conposite black band contrasting with
    the adjacent clear and nilky quartz.

    A further 0.5n0!0 of quartz contains .a fetr individual


    band
    euhed.ral grains of pyrite (av. 0.2mm trLXo 0.5nn). These bands
    are separated. fron another sulphide band. by three 1nn band,s of
    barren quartz. The last sulphide band. (2-3nn) is nostly
    quartz rith subhedral pyrite (av. 0.3nm1 rlsxr 1.0nn). The
    pyrlte contains inclusions of sphalerj.te and galena and is
    enbayed by these ninerals when they oceur as adjacent grains
    (replacenent of py). Sphalerite (av. 0,2nn1 ELXo O,gnn) and
    galena (av. 0.1nn1 rrBX. 0,4rnn) also oecur as individual grains
    or as aggregates of two or three grains in euhedral or sub-
    hedral quartz. Chalcopyri.te (av. 0.05nn) occurs as rare
    ind.ividual grains in quartz. Vug quartz with crystals up to
    2mrn Long follows and is coated by large (3Onn long) crystals
    of gypsum.
    755

    SAMPTE 14025 (TL22) TALISI'IAN 14F tEVEt


    '
    Sanple 1L025 $L22) frou 1/+ level ls crustj-fied.' consist-
    ing of sulphide bands separated by bands of nilky quartz and
    carbonate. (Fig. t-6). In polished seetion sphalerite and
    galena predoni.nate although chalcopyrite is 1ocaI1y abundant.
    Pyrite and electrum are present in lesser quantities.

    Several different textures occurr the particular texture


    developed depend.ing on the proportion of the various sulphides.
    Sphalerite and galena generally occur in conplex intergrowths
    (Figs. t+-T'l and, lr-28) which surround and penetrate larger
    nasses of chalcopyrite (nax. 3nm) and sphalerite (rnasses up
    to frun). In a few exanples quartz aeconpanies sphalerite and
    galena j-n the complex textures but generally it oecurs as
    distinct grains surrounded by the sphalerite-galena inter-
    - growth, acconpanying the larger grains of chalcopyrite and
    sphalerite or invading theu'

    Large nasses of chalcopyrite (iax, 5mn) occur in sone


    bands. They contai-n euhedral gralns of pyrite and inelusions
    of galena , electrun and pyrite. chalcopyrite generally
    penetrates fractures in adjacent sphalerite nasses.

    sphaLeri.te contains abunclant tlny inclusions 6f


    chalcopyrite (exsolution or epitaxial growth) and in a few
    bands large nasses of sphalerite contain inelusions of galena'
    galena and chalcopyrite or galena, chalcopyrite and electrun
    arranged in poikilitie (fig. 1,-29), dend,rltie nstreakyrt
    (fig. t-30) and nyrnekitic textures.

    Pyrite oecurs as sna1l grains in chalcopyrite or galena


    and. larger grains (nax. 1nn) in quartz. One pyrite after
    narcasite ball occurs in a large. nass of chalcopyrite of p.s.
    llrOZiT $L22i. When contacting galena' pyrite is enbayed.
    and contalns abund,ant inclusions of galena.

    Electrun oceurs as abundant tiny grai.ns in nany bands of


    the speclnen. It raainJ.y occurs witb quartz invading earLier
    sulphides (Fig. l--31) but also as intergrovths uith galena
    ln the conplex galena-sphaleri-te intergrouths. Ineluslons of
    electrum in chalcopyrite and sphalerite are eomnon in sone bands.
    756

    Carbonate occurs as sinall aggregates in soue quartz bands


    but also as a 5nn thick band which replaces the sulphides
    (particularly rnarked r.rith galena and chalcopyrite along its
    margins. )

    SAMPLE 14026 (TL2l,), TAITSMAN 13 LEVEL

    Sanple 1L026 (Tt2{F) eontains two bands of scattered


    subhed.ral pyrite grains (av. 0.5nn1 rn4xo 2nn) in quartz with
    rare chalcopyri.te (av. 0.05nn)' separated by 2 /tnrn of barren
    quartz fron a central 2nn band. of fine grained pyrite (av.
    0.1nn' rlaxo 0.8nn) with very ninor sphalerite (av. 0.1nn1 tr8Xo
    O. Q.?nn), galena (av. 0.05nns D4xo 0./+nn) and chalcopyrite
    (av. 0,05nn). Pyrite is subhedral to anhedral and together
    with chalcopyrite, sphalerite and galena oeeurs as individual
    grains or aggregates of a few grains interstj-tial to quartz.
    Exanples of mutual intergrowth occur between all four sulphides
    indicating coprecipitation. The sulphides nake up approxinately
    30fi of the central band which is easily d.istinguished in
    hand. speeinen because of its black quartz (chalcedony) in
    contrast to adjacent nilky quartz.

    SAMPLE 1402? (TL25'I , TALISMAN 13 LEVET


    Sanp1e 14p27 (1L25) contains three sulphide bandsr each
    2 to 3nn thick, separated by barren quartz. An early band,
    containing scattered individ.ual grains of sphalerite (av.
    0.05nrn1 osXr 0.1nrn) in quartzrcoats the country rock. Rare
    electrun (one grain 0.01nn seen in p.i. TL25) occurs in guartz
    of this stage. This is follouect by a band of pyrite (av.
    0.2nn1 IItsXo 0.5nm), sphalerite (av. 0.05mmr nax. 0.1nn) and
    rare gal-ena (av. 0.03nnr nax. 0.1nn) and a band of sphalerite
    (av. 0.05nnr nax. 0.?nn), chalcopyrite (av. 0 0.05nu1 Esxr
    0.1nn), pyrite (av. 0.2nn1 1gsxr 0.5nn) and galena (av. 0.03nn,
    D&xr 0.1nn). In the Latter bands pyrite is anhedral to
    euhedral and contalns a few inelusions of sphalerite and
    abundant inclusj.ons of galena. Galena grains usually occur
    with sphalerite. The sulphides occur scattered in quartz and
    general.ly rnake up only 20fr of the band.s but in plaeesr the
    sphalerS.te and quartz band contains up to lrl% sphalerite.

    Supergene chalcocite and covellite rin chalcopyrite aud


    chalcocite rins sphalerite.
    757

    APPENDIX VIII

    ACCESS AND ORE PETROGRA.PITT OF


    VEINS IN THE I'IAIORONG0I'IAI AREA

    INTRODUCTION

    The Locations of the najor veins and workings in the


    Waiorongomai area are shown in Fig. VIII-1.

    PREMIER - COTONIST SECTION

    Introduction
    The workings on the llero, Colonist, Prernier and Vulcan
    veins, at the northern end of the Waiorongonai Val1ey' are
    the l-argest underground workings in the area (figs. VIII-1
    and VIII-2). The mine plans (fie. VIII-2) show the extent
    of workings and the location of referenced samples.
    0f the workings west of the tranway only Colonist Snithy
    level was found to be accessible' The extrance to Mcleans
    1100r level has been covered by a slip and therefore naterial
    fron this level was collected. fron the nnullock heap. Both
    the entrance and nullock heap of' the 1l*04r level are buried
    und.er another slip. The other levels were not located.

    North of the tranu&yr 1 480r levei is covered by a slip


    but Prenier No.4, Vulean No.4A, Vulcan No.2 (eastern drive)
    and, Mcleods 1786r leve1 are accessi.ble vi.a their portals,
    The portal to Vulcan No.2 uestern drive is collapsed but the
    drive is accessible (although very wet) behind the portal,
    where the roof has eollapsed, and via a cross cut fron No.2
    eastern d.rive. Sinilarly the portal of Vulcan No.3 (1630t )
    level j.s collapsed but further around the hill part of the
    level has been opened because of roof collapse. The levels
    nentioned as aceessible via their portals are generally open
    over their entire length although VuLean No.2 (eastern drive)
    is inpassible beyond the crosscut to the western dri.ve due
    to stoping from below.
    758

    Fl6. Vill:2

    ATc Aroha Colonllf


    1rr9 - Aaro

    canadrirt

    Ft6.vtil-4

    ?'di
    ,I

    ,,..:l'l;'#
    q^4
    T
    \+ Oallcry
    :"\.-'7
    lXm t
    I

    $
    fl
    dl
    \-/ Ve'iv'r

    Tramwa\ $I
    lrack I
    : v (otd itu of
    Road Aardy's Datlcry)

    plgure VIII-1: Locatlons of the uaJor velns and rorklngs 1n the tdaloron8onal.
    area'(based on olct olne plans and the dlagrana ln llenderson & Bertrun,
    191 3).

    - Hclcans 11@r l.eval (sanpfe f410O)


    I - l{ay Quecn 2 lenel' (sanplo 140?8)
    C - t{al Queen 3 level (sanplcs 14O?9r 1lO8O and 1I+O81)
    tl . llo. I Rcef Dtariond Creelc uaterfall (ranrples U+0?2 througlr lo Ll$15)
    E - Haln Vclnl adlt abwe pack track (sanple 1l09o)
    F - l.laln Veln Dl.anond Creek vatcrfalJ. (aamplca 1l0i'tt 14088 and 1lp6!)
    759

    llcw*wns
    6Gim I
    rz
    lrt

    ac
    r_u

    rr)>

    re
    &

    7
    $fln

    w vrcck
    Ne5
    49bvl

    E3\

    "s!*-J

    1404'
    Wvcl

    s3
    -ao ta
    rru t 0
    .s
    |n-
    # |lcLcans
    t?ot Lcvd
    oEu'odefo@40Ps9ry oAIOO

    ' F!,gure VfII-2r Plaa of, the Golonlrt (Eero aail Col.onlst Velns) and Preuler
    ;.' ,'(preuler anil Vulcau Velna) Seatlona, also knonn as Eardyrl illnee, redrann
    .' f,rol old ni'no plauo. See Flg. VIII-I for locatLou'
    flguro VIII-3! Brccclated ncrtliu to coetse gralncd rulphi.dc llaerallaatlon
    (pre6oulnantly aphaletlto and galsna)'frou Colontet Sulthy Level. Thc
    . eeuplc (14077) le 15cu ulilc.
    76L

    Colonist Srnithy Lev,el


    The location of Colonist Snithy leve1 is shown i-n Fig'
    VIII-2. A falI prevents aecess beyond a big stope open to
    the surface. A nunber of quartz veins (up to 120nn wide) are
    exposed in the southern wall of a side tfroonn. They contain
    several stages of brecciation and quartz d'eposition. Thin
    band.s (up to 5nn) containing rare fine to nediun grained'
    sulphides, generally a combination of sphalerite and galena
    or pyrite and chalcopyrite' occur in the sequence of quartz
    bands, coating breccia fragnents of country rock and along
    the vein nargins. The centres of the veins are generally
    vuggy with quartz crystals up to 12nm long.

    In contrast sanples found. on the floor of the stope


    contain abundant nediun to eoarse grained sulphides (Fig.
    VIII-3). A 100nn wide speci.nen (1t+077) rich in sulphides
    is coated with fine vug quartz erystals on one side indicating
    that the original vein was at l-east 200n vide if synnetrical-
    The sanple reeords a history of several phases of brecciation
    and nineral deposition. The nai-n sulphide gtage contains
    fragments of wall rock and an early fine grained' sulphiile
    and quartz stage.

    In polished section (140?6b) the early nateri-al contains


    euhedral pyrite (av. 0.1nn' Esxo 0'3mn) ninor chalcopyrite
    (av. 0.2nnt nax. 0.5nm) and. rare sphalerite (av. 0.2nm, o&Xo
    O.5mn) individual graj-ns scattered, in quartz. The nain
    "s
    sulphide stage is itself breeciated. (fragnents 6O x 40nn)
    ancl filled with later quartz veinlets (av. 5nn, but up to
    30rnn in 1t+09?a) that crisscross the specinens. Sone of
    these quartz vej.nlets developed vugs with quartz crystals up
    to 5nn l-ong. In hand speeinens of the rich sulphide naterial
    sphalerite predoninants and occurs in nasses up to 10mn in
    dianeter. chalcopyrite and gal-ena are locally abundant and
    also occur in large nasses, up to 20nro and 8nm resPectively'
    pyrite is not seen ia hand. specimen. In polished section most
    of the 1arger sulphide ninerals are fractured and fl1led with
    quartz (p.s. 1t+076a, 1l+O?6b, 1l+O77a and 1l+077b), however two
    sanples (p.s. 14092a and 1t+092b) show only ninor fracturing'
    Sphalerite appears to have crystalised. early in the sequence
    762

    and is penetrated by later chalcopyrite and galena (p.s.


    1t+077a and 1/+092b). Pyrite is rare in the ned'iurn to coarse
    grained, rnineralisation but occurs as euhedral grains (av' 0.2nn,
    oaxo 0.3mn) in chalcopyrite of p.s, 1LO76b. Hessite and
    electrun oceur as smal1 inelusions of various shapes i-n galena
    (p.s. 1l+077, 1/+092a and 1L092b).

    Sample 1t+092a shows that in sone parts of the vein the


    sequence of deposition of the nain sulphide stage is more
    conplicated. Tbe sanple i.s cut by a 10nn thiek base netal
    veia which is zoned' as fo].lowsl

    Zone1. Chalcopyrite (av. 0.3mn1 E&xr 2.0nn) anil


    sphalerite (av. 0.5nm1 rn4x. 1.Omm) are developed. interstitially
    to an early ehuedral quartz phase along the vein nargins. The
    larger nasses of chalcopyrlte contain sone euhed'ral grains
    of pyrite (av. 0'2nn1 D&xr 0.1mn) with quartz. Chalcopyrite
    contains a few inclusions of sphalerite, sphalerite contains
    very snall blebs of chalcopyrite, whereas pyrite contains
    sna1l inclusions of chalcopyrite and galena arranged zonally.
    The sulphides occur scatterett in euhedral quartz (lOfr
    sul-phid.es).

    3nn j,nto the vein, galena (av. 0.3nn1 0.5nn) and


    rn?.Xo

    chalcopyrlte (av. 0.3nnp rn&xr 0.'5nm) occur scattered betueen


    subhedral quartz in a band approxinately 1nn vide. They
    interfingrr contain i.nclusions of each other and appear to
    have precipatated. together. The galena enbays earli-er pyrite
    and occurs as inclusions in the pyrite (indicating replacenent
    of py by gn). Earlier sphalerite is subhedral to galena and
    chalcopyrite, its fractures filled by chaleopyrite. Galena
    contains inclusions (O.Olrnrn) of hessite.

    Zone 2. Galena (av. 2.0nn1 EELXo 4nu) l-ines the above


    zone and, interfingeTs wlth later Bassive sphalerite. Sone
    chalcopyrite (av. 0.2nn, nax. 0.4nrn) occurs in galena especially
    at narrow points in the string of grains' defining grain
    bound.aries.Veryrare(linp.s.1t+092)inclusions(0'02nm)
    of electrun and a few elliptical iuelusions (0.02mn) of
    hessite occur i.n galena. Grains of galena (av. 0'5nnn1 r&xo
    763

    1.0mn) continue into the massive sphalerite at the end of the


    trfingersrr but for at least 2nn sphalerite is practically the
    only phase (tiny i-nelusions of chalcopyrite and thin veinlets
    of quartz being the only exceptions).

    At approxinately Bnnin fron the beginning of zone 2,


    chalcopyrite (av.1nm but masses up to 4nn), pyrite (av.0.3mn,
    od.xr O.?nn) and galena (av. 0.5x08' nax. 1mn) reappear-
    Chalcopyrite and galena interfinger and appear to have
    coprecipitated,. Although boundaries with sphalerite appear
    nutual, chalcopyrite filLs fractures in the sphalerite.
    Galena contains rare inclusions of hessite. In this naterial
    sphalerite stil1 predoninants, followed in order of abundance
    by chalcopyrite, galena and lastly pyrite. Pyrite oceurs as
    subhedral grain.s in quartz and contains snall inclusions of
    chaLcopyrite and a few inclusions of galena. It has
    subhedral to euhedral boundaries with galena and. chalcopyrite'
    but is enbayed by quartz.

    Mcleans 1100r Level.


    Sanples (1 00mn dia. ) of nineralj-sation fron the mulloek
    heap of the 1100t leve1 are conposed. of nassive ned.iun grained
    sphalerlte and galena eross cut by veins of barren coarsely
    crysta,lline quartz. In polished section (14100a and 14'100b)
    the nlneralisation contains appr'oximately t 5# pphalerite,
    ',0% galena, 3f, pyrite, zfi chalcopyrite and t+0fi quartz.

    Sphalerite (av. 1nn but nasses up to.4nu) is brecciated


    and veined by later quartz. Replacenent by chalcopyrite is
    indicated by the occurrence of snall inclusions of chalcopyrite'
    rare in the centre but abundant near the nargins of the
    grains, and areas (av. 0.3nn1 IIt&Xo 0.5nn) of chalcopyrite
    within the grains. Sphalerite embays earlier pyrite (av. 0.3ron,
    o&xr 0.5nn) which is also replaced. by galena and quartz.

    Galeaa occurs in areas adjacent to sphalerite and as


    networks in quartz. Grain size appears to be approxinately
    1nn but nay have been nuch larger before replacenent by later
    quartz. Galena contains inclusions of sphaleritet
    chalcopyrite, hessite and rare altaite. It is enbayed. by
    euheilral quartz and. appears to replace sphaleiite and pyrite.
    ?64

    It enbays (replaces?) and occurs as inclusions i-n pyri-te, but


    has nutual boundary relati-ons with chalcopyrite.

    Pyrite occurs nostly in galena, Iess in sphalerite and


    rarely in quartz (euhedral in this case).

    At least two generati-ons of quartz ocour in p.s. 14100a'


    Qne acconpanles the sulphides, euhed'ral to their margins and
    filling their fractures. A second' occurs as a 1nn vej'n cross-
    cuttiqg the specinen.

    Supergene covellite and' a translucent nineral (cerussite


    or anglesite?) rePlaee galena to the extent of 20 to 30fr.

    emier N Vu an No./.'A and Vulcan Nor?--l-evel


    0f the accessible levels north of the tranway only
    Vulcan No.2 (eastern d.rive) has been extensively stoped
    (although Vulcan No.3 level is stoped up to No'2 level) ' In
    1532t No./r leve1 a 2m wide quartz vein is exposed in the
    cross cut to a winze (Fig. VIII-?). The vein contains frag-
    nents of r.rall roek eenented by sulphides and several stages
    of quartz. The sulphides, ned.iun to fine grained (av. 1nn)
    galena, sphalerite, chalcopyrite and pyrite are present in
    snal.l- quantities.

    Apart from the single exposure described, above' pyrite


    was the only sulphide found in the nassive quartz veins of
    Prenj.er No.4, Vulcan No.4A and Vulcan No'2 (eastern and
    western d.rives). Calcite nay have been present in Vulcan
    No.2 leve1 as blocks of ptaty quartz (quartz pseudonorphs
    after calcite) are abundant on the nullock heap and slip
    below the portal of .the eastern d.rive. Henderson & Bartrun
    (1911) noted. that calcite was present in the lowest adit of
    the Prenier (5 level?) but absent above this ]eve]. They
    also stated that the go1d, to silver ratio in the upper levels
    of the prenier was 1:4 but rose to 1t2.5 in the lowest stoped
    1evel.
    765

    Tlwal

    CAtlADlAtl o# mdw,g too

    s- Vrin
    il
    i{
    \
    'N:- Aivona ,'/-='t?.
    lovel

    NNM FND NP 2
    974m
    I o \'-\c.
    *
    '
    tu '{
    ii
    \\ 'r

    \ ,tl
    J\ i \
    NE\,V FIND Ne I
    \"A_ri

    (\,
    *l

    Plgurc VIII-4: Plan of the Iter Ftnd vorki.age, rgdravn fror oltl nlno plane.
    , For lotatlon aee Flg. ErI-l .
    766

    I"IAIN VEIN

    l,lain Vein, Diarnond Creek WaterfaIl


    The pack track erosses Dianond. Creek at the head, of a
    high waterfall. At this 1oca1Lty two sets of veinlets con-
    sidered to be part of the Main Vein cross the strean and
    eoalesce on the southern side. The eastern veinlet dips 42o
    at 0900 ( strike due north) , whereas the western veinlet
    strikes aL 33oo (dip not discernable).

    The veinlets are up to 30nn thlck (14,089). A thin band.


    (av. 1nn, up to 2rnm) of fine grained sphalerite and galena
    llnes the vei-n nargins (14'OAZ and 14089) and oceurs as
    stringers in the adjacent wall rocks. Medium grained conby
    quartz fil1s the vej.nlets and crystals up to 7nn are devel-oped
    ln central vugs, Fine to nediun grained (up to 2nn in 141088)
    pyrite and chalcopyrite occur as a thin band part way into
    the vein (l4OAl and14088) or as aggregates of grains in the
    central quartz zone (111087 and 1,4'089) .

    New Find Section of Mair.r Vein


    To the south of the Prenier and Vulcan sections' the
    Main Vein and its adjoining branch veins have been worked in
    the New Find Sectj-on (figs. VIII-1 and VIII-l). The worki.ngs
    are exposed at the surface as a 2n wide cleft in the rocks
    (Fig. VIII-5) which is several tens of netres deep (probabLy
    up to 60n) iu places. Ore fron the dleft was probably stoped.
    fron below and taken out via the New Fi.nd Low Level ('l503t ) ,
    Arizona No.2 Level and an unnaned adit at the southern end
    of the section (Fie. VIfI -4) .

    A shaft (at least 30n deep) fron Arizona No,2 Level opens
    to the surface by a track below the brow of the eastern side
    of the cleft. A short tunnel connects this area to the
    cl-eft and continues into the rock on the other sid,e for about
    3m.

    Downon the hillsitte a trarnway eonnects Arizona No.2


    tevel (entrance collapsed) to an iron shoot (for passing ore
    down to a bopper on the tramway below) and. two ad.its at the
    767

    llgure VIXI-5: 01sft etcavatcd ln tbe ttgs llnd sectlon. ?hc cleft la greatcr
    tbah 60r doap (the old lrlans auggcet 9fu) ta frout of, .the rock bridge
    on ubich tbo flgurc 1,r atauillng.
    ?68

    southern end of the New Finil workings. Both southern adits


    are accessible but a stope in the northern one has collapsed
    opening the roof to the surface, but naking further passage
    irnpossible. The southern adit eontains a thin quartz vein
    but no visible nineralisation.
    }[AT QUEEN

    Mav Oueen 1 level


    The May Queen worki-ngs are located in Dianond' Gu1ly
    south of the May Queen Incline (Fig. VIII-1 ) ' Fron the top
    of the May eueen i.ncline the tranway branehes north and' south.
    the southern bnanch fo110vs on a level contour of the hill
    and after 35n passes an adit (considered here as I'tay Queen
    No.1 Level) driven 3n into the sid.e of the hill. An 0.8n
    quartz vein j.s exposed along the northern side of the adit'
    on the roof of the portal and on the ground outside, crossing
    under the tranway. The vein strikes 3?5o and consists of a
    number of cross cutting conby, coarsely crystalline quart'z
    veins with sone vugs. A track up by the northern side of the
    aclit leads to a 5n open cut situated. a litt1e above the ad'it.
    The expo6ure is very weathered and litt1e can be seen of the
    vill .

    Mav Oueen 2 level


    A snall hole in the ground. (approxinately 1.5n by 0.8n)
    outside the southern side of the 1 1eveI adi-t opens out to a
    lower level situated at sone eonsiderable d'epth. The
    entrance to the l-ower leve1 (considered. here as May Queen 2
    Ievel) is covered by a slip but sone samples of vein naterial
    were collected fron the nullock heap.

    naterial generally consists of quartz cenented


    The vein
    r.rall rock breccias with nedium grained sphalerite and' galena
    lining the fragnents and coarse conby, sonetines vuggy' quartz
    (crystals typically 20nn long) filling the renainder of the
    vei-n. However sone blocks exhibit COCkad,e structurer eo[-
    sisting of breccia fragnents surrounded by concentric rings
    of sulphicles and. quartz (Fig. l*-7).
    The breccia fragnents contain dissdninated. fine grained
    769

    pyrite. Large nasses of sphalerite (up to 15 x 25nn) occur


    developed from the banded sulphides in cavities and eontain
    galena (av. 0.5mn, nax 1.0nm), chalcopyri-te (av. 0.2nn1 ELXo
    1.0mn) and pyrite (av. 0.05nn). Galena appears to be inter-
    stitial to sphalerite. Chalcopyrite oecurs as grains in
    sphalerite or as snall grains or inclusions at the ed'ge of
    galena. Smal1 i-nclusions of chalcopyrite occur in sphalerite
    and tend to be more eoncentrated near fractures and grai-n
    edges possibly resulting fron a replacement rather than
    exsolution origin. A few euhedral pyrite crystals oeeur in
    or ad.jacent to pyrite. Quartz occurs in fractures or as snall
    areas, however the sphalerite nasses are approximateLy 98f
    sulphide.

    The band.ed ninerali,sation in sarnple 1/*078b is in the


    following order:
    1. The inneruost concentric ring surrounding the breccia
    fragrnents is a band., approxi.nately 3 to 4nrn thick, pred.oni.nantly
    conposed. of sphalerite (av. 2nn, max. 4mn) but also containing
    chalcopyrite (av. 1nn but nasses up to 4nn), galena (av.
    1rnrn, rn4xo 3nn) and pyr5-te (av. 0.2nmr nax. 0.?mn) occasionally
    separated by quartz (the band contains approxinate1y 70%
    sulphides). Sphalerite contains only a few tiny inclusions
    of chalcopyrite (exsolution, replacenent or epitaxial growth).
    Pyrite is subhedral to euhedral and oecurs in or adjacent to
    chalcopyrite. Grains of chaleopyrite, sphalerite and galena
    have nutual boundarY relations. !

    Two generations of pyrite occur and differ in size. The


    larger grains are euhedral and contaj,n snall inclusions of
    chalcopyrite, sphalerite and quartz and Larger inclusions of
    galena. The snaller pyrite grai-ns occur with quartz as
    naggregatestt (av. 0.1nn) in chalcopyrite. Pyrite llay be re-
    pLaced, by quartz t,o give this aggregate texture'

    2. 2nn bandof quartz containj.ng qpproxirnately 10fi


    chalcopyrite (av. 0.2nn), and lr\fr galena. Grain bound'aries
    indicate that the galena, chalcopyrite and quartz precipitated
    together.
    770

    3. Chalcopyrj-te (av. 0.5mm1 IlLXr 1.Onn) and subhedral


    pyrite (av. 0.2rnn, max. 0./*nm) occur preeeding, with and
    postdating a 0.5nn to lron white band of quartz proninant in
    hand. specinen. The white band merges j-nto galena of band' 2
    but d.oes not itself contaj.n any galena. Quartz is the najor
    constituent of the zone. Chalcopyrite contains a few pyrite
    balls (av. 0.1rnn dj-a.) and snall- elliptical inclusions of
    galena. Pyrite has abundant inelusions of chalcopyrite and
    galena,

    After lmur of this zone, sphalerite (av. 0.5nm' nax.2nm)


    appears. The sphalerite is enbayed by quartz and eontains
    abundant tiny inclusions of chalcopyrite. Galena (av' 0'5nn,
    nax. 1nn) also gccurs associated with' but in lesser
    quantiti.es than sphalerite. Galena and sphalerite are enbayed
    by euhedral quartz. Band 3 is generally 2mm wide but up to
    3mm loca}ly and contains approximately 50fi
    sulphides.

    l+. 0,5x0n band of unuineralised quartz.

    5. 5nn band containing predoninantly masses of chalcopyrite


    (up to 4um long) surround.ing subhedral to euhed'ral pyri-te.
    Large nasses of galena also .oceur (up to 2nn long) surrounding
    euhedral crystals of quartz. They have nutual boundary
    relations with ehalcopyrj.te and.sphalerite. Sphalerite (av.
    0.5nu, nax. 1.Ornn) is a ninor constituent of this band' It
    occurs as grai.ns surrounding and embayed by euhedral quartz
    and contains abundant snall inclusions of chalcopyrite. It
    also occurs as snall grains in chalcopyrite. Chalcopyrite
    also contains sma1l elliptical inclusions of galena (av. 0.01nn)
    The band contains 50-60% sulphides'

    6. A j-5nn band of chalcopyrj-te (av. 0.5mmr nax. 1.0mn)


    lesser pyrite (av. 0.1nme In&Xr 0.3nn) and quartz averages
    approxirnately 30fr sulphldes. Chalcopyrite contains rare
    pyrite? baI1s and tiny elliptical inclusions of galena.
    Chaleopyrite is enbayed by euhedral quartz. Chalcopyrite and
    pyrite generally occur as ind.ivid.ual grai.ns separated by quartz.
    The nargins of chalcopyrite grains are serrated' due to
    alteration to goethite and covellite.
    7?t

    Band. 6 is invaded by a thick quartz plus pyrite


    1mm
    (av. 0.1mn, max. 0.3mm) vein. The pyrite is subhedral to
    euhed.ral and occurs in quartz naking up approximately 50fi of
    the nateri-aI. It eontains abundant tiny inclusions of
    chalcopyrite.

    In hand speci.nen the areas between the banded nineralisa-


    tion are filled with quartz, ned,iun to coarse grained.
    chalcopyrite and fine grained. pyriter possi-bly a developnent
    of baud 5 described above. Vugs containing quartz crystals
    up to 1 Onm long are developed.

    Galena is variably altered to a translucent nineral


    (cerussite or anglesite?) and covel-lite.

    May Queen 3 Level


    Further down the hill the oecurrence of No. 3 Level is
    narked by another nullock heap. The adit was located. but
    found to be eollapsed a short d.istance i.n fron the portal.
    The tunnel follows a 50mn wide quartz vein (exposed. along the
    roof for a short distance before reachi.ng the fall). Another
    adit on the sane Level, 8m to t'he south-east, is also
    collapsed just insj-de the portal. Blocks fron the nul-lock
    heap indicate that the vei.n is a quartz cenented uall rock
    breccia. Several stages of bredciation and d.eposition can be
    identified.
    Sanples 1l+07g, 1/+080 and 1 3g7g coot.in early unbrecci.ated
    nineralisaiion. A seri-es of bands of quartz and sulphides
    coat the wal1 rock which contains disseninated pyrite, In
    polished section 13979 these bands are:
    1. 2 to 3mm band of pyrite (av. 0.2mn' nax, 0.8nn) with
    ninor chaLcopyrite (av. 0.3nn, max. 0,8nn), and rare sphalerite
    (av. 0.3nn' nax. 0.5nn) and galena (one grain 0.5nn), broken
    up with white clay (sericite?) in plaees expanding the band
    to 15nn locaIly. Pyrite rnakes up approxi.mately 5Afi of the
    band and occurs as aggregates of a few grains or strings of
    interlocking grains. The pyrite contains abundant tiny
    inclusions of chalcopyrite and larger inclusions of galena
    orientated along growth zones, A few grains contain large
    '172

    inclusions of sphalerite and others quartz. Quartz surround-


    ing chalcopyiite is euhed.ral to the chalcopyrite. Sphalerite
    contai-ns tiny inclusions of exsolved? chalcopyrite.

    Z. 5 to 8nur band of predominately sphalerite (massive),


    with quartz, galena (av. 0.5mn1 oElXr 1.Omm) and chalcopyrite
    (av. 0.5ton, max. 1.5nn) oeeurrj-ng along the inner nargin of
    the band. (most enbaying the sphalerite nass) or as inclusions
    in the sphalerite. Inclusions of galena are subhedral to
    sphalerite. Rare tetrahedrite occurs in chalcopyrite ailjacent
    to sphalerite and with chalcopyrite filling fractures and
    voi.ds in sphalerite. The sphalerite nass is fractured (in-
    filled with quartz) into approxinately 1nm fragnents.

    3. Along the outer rnargin of the sphalerite bandr galena


    (av. 0.8mn, masses up to 2.5mn), chalcopyrite (av. 0.4mm,
    nasses up to 1mn), pyrite (av.0.1nn' nax' 0.2nm) and quartz
    oecur j-n a 1 to 3nm band. in the approxinate proportions ? lrjfi
    quartz , 35{f galena, 23fi chalcopyrite and. 2% pyrite. Quartz
    is euhedral to the galena and. chalcopyrite, but pyrite is
    subhedral to quartz' Chalcopyrite contains inclusions of
    sphalerlte, pyrite and tiny blebs of galena. Rare tetrahedrite
    (nax. 0.2nn) occurs as inclusions in chalcopyriter at the
    nargi-ns of chalcopyrite and sphaleri-te and with chalcopyrite
    filling fractures in sphalerite.'
    !+. A 5 to 10urn band of quartz (65%), contains scattered
    aggregates of pyrite (av. 0.3nn' nax 0.8nn) aud chalcopyrite
    (av. 0.5nn1 DLXr 1.Onn but nasses up to 2nrn) in approxinately
    equal proportio4so Pyrite is subhedrbl and contains tiny
    inclusions of chalcopyrite and galena arranged zonally and
    rare larger inclusions of sphalerite (nax. 0.02mm). Quartz
    is euhedral to sphalerite. chaleopyrite contains inclusions
    (av, 0.03nn1 r1&xo 0.2nn) of galena and sphalerite. Pyrite
    and chalcopyrite generally occur separately but when together
    pyrite is euhedral tor.rards chalcopyrite. Some cbalcopyri.te
    contaj.ns abundant srnall grains of euhedral pyrite (av. 0.03mn).

    In hand specinens 1LA79 and,14080 band 4 is followed by


    a 5nn band of ned.iun grained sphalerite and gailena and' sub-
    sequently by nore quartz, pyrite and' chalcopyrite.
    773

    several periods of breccj-ation and. quartz deposition


    followed. the banded mi-neralisation resulting in a vein breecj-a
    of sulphide fragnents (typically 20nrn but up to 60nn across)
    bounded by eomby quartz veinLets (up to 35nn wide, 13900) '
    ,l/ugs with quartz erystals up to Jmm long are developed. This
    breccia appears to be the doninant vein naterial'

    sone sulphide deposition followed an initial stage of


    brecciation, as evideneed by a large grain of chalcopyrite
    (8nn) surrounded., penetrated by, and containing inelusions
    of, euhedral pyrite (av. 0.4mn, nax. 1.5nn) and. galena (av.
    1.gnn, nax. 2.0mm) itr p.So 1/r080a. Galena ad.jacent to the
    chalcopyrite is graphically intergrown with quartz j-n a coarse
    texture. However, nost of the later quar:tz is unnineralised'
    NUMBER 1 REEF

    No. 1 Reef, Tramway


    235a along the tramway south of May Queen No.1 (and 12rs
    south of the rtNew Findtr hopper) a 1m wide vein is exposed' in
    the western bank. It consists of approximately seven quartz
    stri-ngers (nax. width 12nn) d.ipping 65 - 9Oo al 235 (strike
    3250) transeeti-ng an earller quartz and. sulphide cenented'
    vall rock breccia vein of undeternined width (Uut less than
    1rn), dip and striker

    The latter vein contains breccia of silicified' wa1I roeks


    (fragrnents av, 30nn but are up to ?onn) eenented. with
    sulphides and quartz (veinlets up to 12nn). The fragnents
    contain approxinately 1Ofi disseninated sul-phides (p.s. 14072),
    nainly pyrite (av. 0.02nnne Intxr 0.1mn) but ninor sphalerite
    (av. 0.05nnr mgx 0.2mn) and very rare galena (same size as
    sphalerite) also oecur' Pyri.te grains are euhedral and' eontain
    inclusions of galena arranged zonally'

    The sulphide veinlets contain a uoned, nediun grained


    sphalerite, galena and quartz stage (approxinately 60 80%
    sulphides) followed by barren vug quartz and cross cut by
    latter vei.nlets of barren quartz (tire quartz stringers noted'
    initially).
    774

    ftgure VIII-6: Dendrltlc galena (shlte) ln quartz (dark graY-b1aek). The grey
    ol.neral la ephalerl'te. Sanple 14072 fron !1o.1 vela. 50X. See al.eo
    tLg. L-2L. t
    775

    Individ.ual grains or snal1 aggregates of subhedral pyrite


    (av, 0.2nm, nax. 0.3mn) occur at approxinately lrnn intervals
    separated by quartz along the nargins of the braccia fragments.
    Sphalerite occurs veinward of the pyrite and embays its
    nargins. An intergrowth of galena and sphalerlte ranges fron
    nargi-ning and interfingering to snall veinlets of galena along
    fractures in the sphalerite suggesting replacement of
    sphalerite by galena. The proportion of galena to sphalerite
    varies. fn one part of p.s. 1t+072 galena nakes up 10 to 20fi
    of the cross-section as opposed to 50 t,o 609l sphalerite,
    whereas over nuch of the sanple a zonatj.on is developed' away
    fron a breccia fragnent. For the first 2mn galena is a ninor
    phase (t O - z}fi), however fron 2 - {nn away fron the fragnent
    it equals sphalerite in quantity and fron 4nn onwards it
    predoninates, the total width of the sulphide stage being pnrn.
    Sone areas of the sulphide veinlet contaj.n only galena and
    quartz. The latter occur in a herringbone dend.ritic-skeletal
    texture (f:.Ss. VII-6 and t-2lr).

    Euhed.ralpyrite (av. 0,05rnn) occurs very rarely and


    generally in quartz. Chalcopyri-te occurs as small elliptical
    inclusions in galena and sphalerite anil as snall blebs (av.
    0.03mn, nax 0.1mn) with galena along the nargins or veining.
    In the areas where sphalerite renaj.ns the doninant mi.neral
    throughout the vein cross section, chalcopyrite inclusions
    are largest, rnost abundant and arranged in various patterns
    indicating replacenent or epitaxial growth (fig. L-20). In
    sone grains chalcopyrj-te nakes up 20fr of the sphaleri-te grain.

    The sulphides are succeeded by vuggy quartz at the vein


    centre. Some snall grains of euhed.ral pyrite (av. 0.05nn)
    and anhed,ral chalcopyrite (av'. 0.05nn, E&xo 0.3mn) oecur at
    the nargin of the sulPhide band.

    In sunnary pyrite appears to be the first sulphlde


    precipitated, followed and replaced by sphaleri-te. Ga}ena'
    chaleopyrite and quartz follow, replacing the sphalerite' and'
    the quartz continues j.nto vugs.
    Ftgurc VtrII-?: Gut alde of rpccltea 1197? fror lfo.l vcla c*hlbltlag bended
    aufpb.liter fotrtrored by quertr (at fl.rst vlth uinor tulphld-ea) r!,th aoab
    structui.ri Tte ratptre (9cu s.i.de I 8ai htrgh) rapraaentg pert (app.rorlnetetrt
    ?Of ot tbc rtithl of an arlruuetrlal Yelrr (the sulPh'tdeg sele- pood-y
    drvclopcd aloag thc othcr vcla larBln).'
    777

    No. 1 Reef , Diamond. -Creek tr'Iaterfall


    A 2n wld.e vein (strike 3500, dip t+o - 50o west) crosses
    Dianond Creek at the head 6f a waterfall. The vein is con-
    sid.ered to be a continuation of No. 1 Reef and is designated
    No. 1 Reef Waterfall- in Fig. VIIf-1. It contains two paralle1
    unnineralised 30-50mm vuggy quartz veins' one defining the
    footwall and separated fron the other by 0.3n of eountry rock,
    followed by 0.15n of country roek and a 2.5m zone of 50 to 150nn
    l.rs.Vfr cross cutting, eomby quartz vej-ns. The latter contain
    eoarsely crystalli-ne quartz (crystals up to 30nn long) and
    veins on the footuall si-de of this zor:re are nineralisedr Br$r
    sample 1l+073 shown in Fig. VIII-?. The rninerau.sed veins are
    band.ed, not always synmetrically, with band's of sulphides and
    quartz lining the wa1ls and coarse conby, rarely vuggyr Qrlertz
    filling the cavities. Fragnents of wall rock are rare.
    Although slightly variable between veins a general sequence
    after 1t+073 (Fie. VIII-?) is as follows!
    1. Fine grained pyrite disseminated. in the wa1I rocks.

    2. 3nn band of fine grained sphalerite and. pyrite occurring


    as individual grains oi: aggregates of several grains scattered
    in quartz, Polished section (11$75) contains sphalerite
    (av.0./+nm, nax. 1mm) and pyrite (av. 0.2nme r&xe 0.3nn) in
    equal quantities and rare chalcopyrite (av' 0'1nn) ' sphalerite
    contains inclusions of chalcopyrite probably fron replacenent
    or epitaxial growth. Pyrite is euhedral aud contains a few
    inclusions of galena, chalcopyrite, sphalerite and quartz.
    In a few exarnples where it occurs with sphalerite it enbays
    the latter possibly replacing it. Clusters of ascicular
    crystals (individuals 0.15nn long by 0.01nn wide) of pyrite
    occur i.n quartz. Galena oceurs only as inelusions in other
    ninerals.

    3. 5nn band (Uut up to in other sanples srgr 14A75) of


    30nrn
    white fi-ne grained to microcrystalline quartz with snall
    vugs sonetines developed. Fine grained pyrite oecurs seattered'
    sparsely in the white quartz.

    L. 1mn band. of fine grained pyrite and sphalerite in quartz.


    polished, section (1t+O752) cont'ains sphalerite (av. 0.Znn1 il&x.
    ?78

    0.4nr0) and pyrite (av. 0.1rnm2 1nBXr 0.3mm) with ninor galena
    (av, 0.1mn, nax. 0.3mrn) and chalcopyrj-te (av. 0.05mn1 otXo
    0.1nn) as single grai-ns or aggregates of tr'ro or three grains
    scattered. in quartz. Sphalerite contains inclusions of galena
    arranged. along cleavage planes, Boundaries between sphalerite,
    galena and chalcopyrite appear to be mutual. Pyrite ls sub-
    hed.ral to euhedral and contains inclusions of the other
    sulphid.es but it nay also be contenporaneous. One grain of
    electrun (O.03nm dla,) oceurs solitary in quartz of this stage.

    5. 1un band of white very fine grained or -nlcrocrystalline


    quartz.

    6. 5 to ?nn band. of ned.iun grained galena (av. 1.5nn1 IIIlx.


    3mm) and sphalerite (av. 2.0nmr Eax. 3rnm but nasses up to 10nn
    long) uith ninor chalcopyrite and pyrite. 'The proportion of
    galena and sphalerite vary between di-fferent sanples so that
    the band nay alnost entirely consist of galena or sphaleri'te'
    The band i-s segregated into two in p's' 1.1$752 ' The band'
    nearest the wall of the vein is 2nn wide and contains sphalerite
    (av. 0.5nn1 Eoxr 2nn) and. pyrite (av. 0.3nnt nax 0'5nn) with
    lesser chalcopyrite (av. 0'2nn1 ELX. 0.3nm) and galena (av'
    0.3nm, max. 1.Qnn). The sulphid,es occur as aggregates of five
    or six grains separated by quartz. Sphalerite contains in-
    clusions of chalcopyrite generally arranged regularly along
    zones d.ue to replacenent or epltaxial growth. Pyrite is
    subhed.ral to quartz and chalcopyrite but anhed.ral to sphalerite'
    exhibiting an intergrowth texture probably forned by
    coprecipitation. Pyrite contains inelusions of sphalerite'
    galena, and chalcopyrite. sphalerite is subhedral in eontacts
    with chalcopyrite. Galena has rnutual bound.ary relations with
    chalcopyrite.

    2nn of nediun grained quartz crystals separates the


    first sulphid.e sub-band. frorn the second which consists of
    grains of galena and, sphalerite (both av. 1.5rnn1 IIIsxr 3nsl)
    separated by smal-l quantities of quartz. Ga1ena predoninates
    over sphalerite but the two ninerals have nutual boundary
    relations. Chalcopyrite occurs as inclusions in sphalerite and
    rarely as grains (av. 0.3mn1 rn4x. lnrn) in aggregates vith
    77e

    sphalerite and galena (adjacent grains fill fractures in


    sphalerite) but more eomnonly as ind.ividual grains (av. 0.05nn,
    nax. 0.1mn) or with pyrite and sphalerite (both av. 0.05rnm,
    Bax. 0.1nn) in quartz interstitial to the uediun grained
    galena and sphalerite.

    7. 1 of coarse grained quartz (crystals up to 7nn


    5nn band
    long) with grains of pyrite, chalcopyrite, sphalerite and
    galena occurring between the crystals.

    8. Coarse barren conby quartz fills the eentre of the vein


    with vugs sometines developed.

    BONANZA

    At a bend in the paek track the location of the Bonanza


    l,tine is narked by the sound of water falliag d.own a holer otl
    the uphill sid.e of the track, into a stope below (l'ig. VfII-1).
    0n the dounhill side and approxj.nately 10n below the track the
    adit entrance is covered by a slip but samples of veia naterial
    were colleeted fron the mullock heap, This naterial was
    probably taken fron the Bonanza vein although i-t nay have cone
    fron the Three Fools vein (FiS. VIIf-1 ) because, on the nine
    plans, both veins appear to have been intersected..

    The vein is a quartz anil eenented wall rock


    "rrtnnrd"
    breccia(1t,083). Breccia fragnents (up to 40 x 30nn) contain
    disseninated. subhedral to euhedral py"it" (av. 0,1nmr Inax.
    0.4mn). They are coated by banded sulphides which are described.
    below from two polished sections (bands 1 to 3 fron 1l+O83a
    and, bands 4 to 9 fron 1 4083b) and. in order of deposition around,
    the fragnents.

    1. Breecia fragneats are coated by a 0.8 to 2nn quartz


    band containing subhed.ral to euhed.ral pyrite ("v. 0.2nn, E&xr
    0./rnrn), sphalerite (av. 0.3nx0r nax. 0.5nn), ninor chalcopyrite
    (av.0.1nn, nax. 0.3nn) and rare galena (av.0.05nrn1 llaxo 0.1nn).
    Quartz enbays all other phases and an interstitial relationship
    to quartz is particularly noted. in the ca6e of chalcopyrite.
    Pyrite contaj.ns inclusions of quartzr chalcopyrite' gal,ena
    and occasionally sphalerite anil develops subhedral to anhedral
    ?Bo

    boundaries to grains of these ninerals. The sulphid-es appear


    to have precipitated together and occur as individual grai-ns
    or aggregates of a few grains in qr'1s31t' The sulphides nake
    up approxirnatelY 304" of the band'

    2. 0.8nm band of barren quartz'

    3. A barid up to 5nm (in trand speeinen) contains a strj'ng of


    sphalerite (av. 1.5mm1 ItlLX. /*mrn) grains separated by later
    galena (av. 0.3nn, nax. 1nn), subheclral pyrite (av. 0.1mn,
    tr&X. 0.5mrn), chalcopyrj-te (av. 0.3nn1 o&X. 1.gmm) and quartz'
    These ninerals aLso occur as inclusions (galena; av. 0.2nn,
    nax. 0.6mn and pyrite; 8V. o.1nrur nax. 0.3nn) in ttre sphalerite
    masses. cb,alcopyrite blebs are arranged zonally in sphalerite
    ind'icatingreplacenentofsphaleritebychalcopyriteor
    epi-taxial growth. Larger inclusi-ons of chalcopyrite (av' 0'1ron)
    also occur. The band contains approxirnately 60{* sphaleri-te'
    20fr quartz, 8f" chalcopyrite, 8% pyrite and' l'% galena'

    4. 2 t,o /rrnn band of interlocking anheilral pyrite (av. 0.3mn,


    max. 0,8rnn) with subhed.ral quartz, ninor sphalerite and very
    ninor ehaleopyrite and galena. The chalcopyrite (av. 0'2nn,
    t1&Xr 0.6nm) and galena (av. 0.2nrn1 IIIBXo 0'3nrd) occur intersti-tial
    to euhedral quartz. Sphalerite (av. 0.3nm' nax. 0.6mn)
    generally occurs in the pyrite nasses at grain bound.aries or
    on the pyrite margins with quartz, probably replacing the pyrite'
    The pyrite contains tiny j-nclusions of sphalerite and larger
    inclusions of galena (av. 0.05nm). The band' is approximately
    701f, pyrite , 20fr quartz , 1fi sphalerite,
    1% galena and' 1fi
    chalcopyri-te.

    5. 3rnn band of chalcopyrite ("v. nasses up to /tnn)'


    1mrn,
    galena (av. 1mn, r14xr 3nn), sphalerite (av. lnno) and' quar:?tz'
    Chalcopyrite surrounds nost of the sphalerite and may replaee
    it. chalcopyrite oceurs &s abundant tiny inclusions in
    sphalerite.Italsorraybelaterthangalenawhichhas
    subhedral boundaries to chalcopyrite and occurs as inclusions
    in chalcopyrite. In sunnary galena and sphalerite precipitated
    together followed by chalcopyrite. The bancl contains
    approxinately 30ft chalcopyri-te, 20fr galena, 10fr sphalerite and'

    [Of, quartz.
    781

    6. Subhedral pyrite (av. 0.5mm, nax. 0.8mm) occurs in


    clusters separated by subhed.ral quartz with interstitial
    ehalcopyri.te (av. 0.4mm, masses up to 2nm). Sone pyrite grains
    are partially coated by rims of chalcopyrite. Sphalerite
    occurs as rare inelusions (av. 0.03nm) in chalcopyrite, and
    pyrite contains sma1l inclusions of chalcopyrite (av. 0.005mm)
    and rarely galena (av. 0.01nn). The band is approximately
    50% pyrite, to% quartz and 10fr chalcopyrite. In hand specimen
    the band can be seen to develop lobe struetures into the vei-n
    so that it varies fron 5 to 10mn thick.

    1nn band of barren quartz.

    8. l, to 10nn band (variable because one margi-n is straight


    and the other follows the lobate structure of band 5) of
    nassive sphalerite. A few inclusions of galena (av. 0.1mn,
    t'BXr 0.3mn) occur and, are arranged. along grai-n boundaries.
    Thin fractures (0,05nm approx) j.n sphalerite are filled uith
    later galena, chalcopyrite and quartz. Chalcopyrlte (av. 0.5nm,
    nasses up to 1 .5nrn) , euheitral pyrite (av. 0.2nn' nax; 0.4.mn)
    and galena (av. 0.1nn, nax. o.Jnn) also filL enbayments
    (Iargest Jmm long by 1.5nn wide) in sphalerite fron band 7.
    Galena and chalcopyrite have nutual bound.ary relati.ons. Pyrite
    contaj.ns snal] inelusj-ons of chalcopyrite and galena.
    Chalcopyrj.te contains snall j-nclusions of galena.

    9. A quartz band witb ninor pyrite d'evelops into vugs.

    In sone parts of the vein the earlier banded. sulphides


    have been brecciated and infill-ed with quartz containing in-
    dividual grains or aggregates of pyrite (av. 0.2nn' nax. 0.8nn),
    ninor chalcopyrite (av. 0.2nn1 III&x' 1.0mm) and rare sphalerS-te
    (av.0.1mn1 III&X.0.5nn) and galena (av.0.1nnr nax.0.5mn) as
    shown in sample 1t+O82. This is in turn cut by quartz plus
    abundant ind.ividual grains of eubedral pyrite (av. 0.04nn,
    lt&Xr 0.1mm) and later barren quartz developing vugs. These
    episode" correlate with band 9 of 1l+083.
    :"t
    INVERNESS, LOYALTI AND WETCOME VEINS

    Location
    The locationsof the Invernessr Loyalty and Welcorce veins
    782

    i$
    I
    I
    o. 9a
    lo vaetrci

    ,rLS

    Ft6. Vilt-9

    Flgure VIIf-8:' Plan of rorkLnga ln the area of the lleleone and fnverncss Valnsr
    redrarra fros old ll'nc Planl. Sec Flg. VIII-1 for locatlon.
    783

    are shown in Figs' VIII-I and VIII-8' They are described


    separately below.

    Inverness
    A 50mn quartz vein striking 1800 i.s exposed on the walls
    approximately 8n in fron the portal of the vermont Drive
    (Fig. VIII-8), Several snall open cut trenches were found
    betueen the Vernont and the northern adit (unnarned') which is
    collapsed approxinately 22n in fron the portal. A traroway
    (tracks stil1 preserved outside the northern adit) originally
    connected the two adits but parts have been covered by a roek
    slide and others, slipped away' Quartz boul-ders lying outside
    (1/t098)'
    the northern adit contain large vuggy quartz crystals

    toyalty
    The workings on the Loyalty vein are shown in Fig' vrII-8'
    The Phoenix Drive and Loyalty Low Level Drive uere not located'
    The toyalty upper Level has collapsed just inside the
    portal
    but the vein is exposed at this point. It strikes at 2000'
    is at least 1n wid.e and. consists of conby and vuggy quartz
    (ltr}gt+, 11a095, 1t$96 and 1lr}97) o

    Although some Plans differentiate the LoYaltY and


    Welcone as seParate veins (e.g. nap 10 of Henderson & Bartrum
    191.3) sone of the larger scale nine location naps conbine tben
    as the Welcone vein.

    l{elcome, Sout[e Adit (nitts or Fer sont s Drive)


    Near its southern end., the upper pack track passes the
    portal of an adit (itillrs or Fergusonts Drive) drj'ven into the
    hill beside the track. The adlt 1s approximately [r5n long and
    intersects two veins as shown in Fig' VIII:9' These veins
    are eonsidered to be part of the welcone vein.

    The vej.n nearest the en6 of the tunnel dips 660 at 1150
    (stiike O25o) and j.s approxinately 50nn wide. It consists of
    conbquartzd'evelopingcentralvugswithquartzcrystalsup
    to 1/+nn long. In places it breaks into thin stringers. Pyrite
    is the only sulphide present and occurs d'isseminated' in the
    wall rocks.
    ?8h

    6q qnrtz
    YaV't.

    I.f'

    ftgurc Yt[X.-9r Fla.q of tlrc lcrut&cra adtt (gtltro or tlo,r"gtluroat]o Dr{voll lnter.
    ooo-tltg, tho lletrcoas Vqlo, ae son by thc rrLter. For lo:oatilo,n aac tgr.,j ,
    ' f,trll-l and 9fltr-8'
    _
    . .t'
    :
    ?85

    The vein nearest the portal dips 22o at 13Ao (strike


    0/*0o) and is approxlmately 0.3n wide. This vein contains
    nainly nediun to eoarse grained quartz surroundi-ng small breccia
    fragments of uall rock. Vugs are developed with quartz crystal
    up to 10mn long. Rare grains of sulphide (galena, sphalerite'
    chalcopyrite and pyrite, up to 1nm) occur with the coarse
    quartz but a band (up to 10mm thick) of sulphid'es is present
    along the footwall of the vein. The sulphid'e band is composed'
    nainly of sphalerite but chalcopyriter $elena and pyrite are
    also present.

    Material richer in sulphides is found on the ground' just


    outside the portal, WaIl rock fragnents generally 5 to 1onn
    diameter are cenented by quartz and' sulphides. This rnaterial
    is further brecci-ated into fragments aPproxinately 20nn square
    and separated by criss-csossing veinlets of quartz 5 to 15nm
    thick.

    In polished' section 1 /1085, the early breceia fragnents


    contain abundant disseninated. fine grained subhedral pyrite
    (av. 0.05mn, max. 0,1nn). These are eoated, by a thin band
    (0.3 to 2mm) of quartz containing subhedrb.l pyrite (av' 0'2nn,
    nax. 0.4r[n) and very minor chalcopyrite (av' 0'05mm' nax'
    0.1nn). A band up to /rrnn thick of raassive sphalerite follows
    but at intervals j-s separated fron the earlier naterial by
    individual grains of galena (av. 0.3nmr Eax. 1.Onm). Tiny
    inclusions of chalcopyrj-te in sphalerite are arranged zonally
    and along grain boundaries indicating'replacenent of sphalerite
    by chalcopyrite or epitaxial growth. The sphatr-erite is
    followed by quartz uith chaleopyrite (av. 1.0nm' nax 3'0nn)
    and euhed.ral pyrite (av. 0.5nn, max. 0.8nn). The chalcopyrite
    replaees the sPhalerite.

    MOA VEIN

    A branch of the Moa vein is intersected by an ad'it


    located below the tranway (fig. VIII-1 ). ft consists of a 3n
    wid.e zone of quartz veins with no visible nineralisation. A
    sample (fig . lr-g) reputed.Iy fron the Moa vein, and therefore
    probably from this nine, was donated by Mr R. Ansin and consists
    of quartz crystals (t5nrn long) covered by plates (up to 6nn
    across) of later barite.
    786

    APPSNDIX IX

    LOCATiON AIID BRIEF DESCRIPTIOII OF SAI,IPLES

    INTRODUCTORY }TOTES

    l{ethod of Listine
    Referenced samples lodged in the rock collection of the
    Geology Departnent, Victori-a University of Wellington' are
    listed here in truo groups; the first with nunbers beginni-ng
    ?55/37/- and the second containing nunbers 13900 to 14100.
    Sanples within each group are listed in ord.er of increasing
    sample number.

    SaTrples not Listed


    I\418185 and I"118186 are Geology Departnent, University of
    Auckland, nunbers and are not listed in the followi-ng sections.
    The samples were collected fron the Camoola Vein of the
    l,laratoto Mine by I'1r J'V. Main and the reader i-s referred to
    Main (lgll) for their specific l-ocations.

    Field_Hunbers
    Alpha-numeric numbers tisted.'within brackets after V.U.l'f.
    nunbers are the writers f,ield nunbers.

    Grid. Referencss
    Grid references are fron the 1t50'000 netric topographic
    naps N.Z.M.S. 25g and N.Z.M.S. 260 (StO, T10' T11, T12 and T13)'
    Grid references for sheets 510' T10 and T11 (unpublished at
    the tirne of conpletion of this thesis) were converted. fron
    grict references for N.Z.l'1.S. 1 sheets using the Geological
    Surveyl s computer progran.

    Samples located trnearn specific grid references orj-ginate


    fron uithin ikm of the stated grid reference.
    787

    s{luer,Es

    Zg5l37l2 (H12), Bosr Tlr/560 280, tteretoto, Sllvor Queen VeIn: Stege 2a qtz aad Stagc 2o
    flao gralaed qta, ap1 8n. ba, cp aad py.
    2grt37l6 (Xlr), !.ea]. T131160 280, llaratoto, Sll,ver Queen Veiu: Stage 2a qtrp Stage 2b flne
    gralaed qtz, gu; ba, ap anit py, aad Stage 2e q|"z nltb flno gra!.n opl gu' ho' cp anil py'
    Zg5h?t7 (U14), aeer T13/560 280. !{aratoto, Canoola Vela: Stage 2b flne grainetl qtz' apr
    BBr pyr op. ao aud hs. Supergele oc.
    zg'.l)7tg (X32), ae"r l13l560 280, Haratoto, Cauoole Vol!r Stago 2b flue gralned qtr, !p'
    g!, cp' pyr 8c aad el.

    ij90o (If43), tli,|53'l 034, l{alorongouel; Hay Queen 3 lcvel (Flg. VIII-1), rullock heap:
    ' Staga I lecllut gralacd qtrx1 ep, gnr cp and py, anil Stoge 2 qtr vlth colb structurc.
    ,, 1r9ot (Cb36). aeet t17.162O 200. llalhlr l'lariha vell: qtz sral ft'B. gralaeil PYr 8r' lPr cpr cc
    gad
    ij,cL. $arplo courteoy of llr J. Earbcrl'cb.
    . 13gO2 (yb77r, trsar tlr/620 200, Walhi, tt{artba lotle at noilerate deptbrl qtz vltb lLac
    ' gralned plr gurvey acrple llo:?941.
    .!pr cp 8tral Br' Geologtcal
    13glr' (fb48), llalbl, ullocated! qt! vltb llne gralaed PYr lPr thr cP ead el.
    Hlner Dlvlalol ',l)1620.2OO.
    dlaplay apocloeo.
    13g}l $13'l), T121495 439, llecveavllle, Gracea Adltr alLlalfled blaet sbalo YIth fllc
    grel[oit Py.
    lJg'j $36r, T12l 195 L39, tleavaavllle, Gracee ltllt: stllclftoil bl.ack sbals vltb fh.
    gralncd py.
    13906 (f,r31), T131535 24?, f,onata Xlne, uu].lock beap outotda 8 lovsli qtz, calclte enil
    flae gralned PY.
    1390? (flutt 2) . 1101361 903, Petots Streaq !rer, Sutt Craek, floatr vug qtz rlth cryatalo
    up to 10nn lolg.
    ftgOS lAB5lr zjgl672 723, te Ahuuata, Barrler Reefa 8oglon, aullock heap outalde 12Jr
    .alltt tl!. gralled {tz, py, !!cr aP, 8Br cPr PBr .1r PblaPY aqd kaolhltc. Sanple court6rt
    of Hr ll.R.E. RalsaY.
    11909 (tut3g), leEr l1rl521 Ofi (5 levol portrl), Tul Hhe, Cbanplor Veln J level, H
    llopor Stage 1 qtz, op. py, bonstlt, blauuthtntts. g,oltl and tetradyllte and Stage 2 qtrl
    lpr BDr op and py. Supergene goetbJ'tc. Sauple courtty of Dr E'lJ' lobe'
    13910 (Ig9), near T11/4Oo 892, llhangapoua, lrlalagaro Stroa!, floet: Stago 4 qtz. py aad rb.
    1tg1l (ygl0), near fl1/400 8!2, Ubangepoua, galngaro Stroan, float: stago 4 qtr, py aad
    lb.
    13912 (xAO), tt2/4gg 1Lj, l{eevcgvlller tJa:2 levef, lullock beapr corb autl vug qtrl
    cryrtrl.r up to il,0m long.
    .13913 (fb24), I1:.l51,l 201. tlalhl, 2 lsvelr arall quartr otrl!8ors betvaer 30 aad 50cr
    rya:/ fror laln vala (Hartha?): vug qtrr crystrl! up to {lr loag'
    lSgtl (UffOO). tlll575 038. Uetorongora!., CoLonlat Srltby lgvel (?l8.VIII-2)' vclD crporcal
    lD loutbyolt.ra corlor of tiopc: gtagc 1 lcdlul gralnctl qtt, lpr 8nr eP ud Py, and Stagc
    2 qtr vlth vug cryotrle up to 8nl J'ong.
    ljg1j (Iut,2?), r,oarllt/iz1 o5J $ Ievel portal), tut Xtre, Chanpl'or Yelnr 5 Levelr ll
    at,oprr Etrgo 1 qtr, cp, py, boratltc, blalutblatte, gold auil totrailyultc. suporgcnl
    goetblto. Sarplc oourtoay of Dr E.I. Kobe'
    13916 (Cils), sosF 1i1tt560 280, Haratoto Xlue, Csloole Veta' 3 levelr north atope: Stage
    2o llac gillaed qta, aP' !41 8G1 cp rnd PIr alil gtago 2d qtr. Salple courteey o! Dr B'I'
    Roblnronr
    13917 ([1), aear T111560 280r l{aratoto t{lBo' Sl].ver Que.l Vc!n, 5 level: Stage 2c qtz
    ald calcltc. 9alplo courteay Dr 8.11. Roblnaon.

    'L-
    rt
    13918 (x2 calolto)r D6! T131560 280. llaratoto Hl.Bo, Ceooola Vel.l, aouth: Stago 1 calclto.
    Saaplc courtaey Dr B.l{. Robl.aaoa.
    1)919 (HZ quartz). ror!'11)1560 280, tlaratoto !{lno, Caroola Voln, 3 lsrol, sxteneloa of
    aouth drlve: Stgge 3 vug qtz rl.th cryetala up to 40rr lotrg. Sauple courteay Dr B.I{. Robl!!o[.
    13920 (H3). uear l1r/560 280, Haratoto Mlno' Sllvcr quo.B VolD, i levoL: Stagc 2a qtr and
    Stage 2o llnc gralneil qtz, ap, g!, h6 end cp. Seople courbeay ol l{r E. Coppard.
    13921 (l{4), aear T131560 280, Moratoto Nl[o' Ceooola Velnr 3 ]'evel, soutb stope, artrcre
    old of vorkluga: Stago 2a qtu 8ad calcito. SalpJ,e courtoay of Dr. B.H. Roblneoa.
    13922 (H5), aear t13/560 280r Haretoto HLro' Sllvor Quoea Velo: Stagc J yug gtr' cry8tala
    " up to ?0ul Loagr ard py. Sauple courteay of Dr B.l{. ioblnson.
    I: 13923 (116), n.rr l1tl560 280, |laratoto lllno, CarooLa Veir, 3 Isvcl, routhsrr rorklugs:
    Stage 3 qts ald calclte v!.tb vug qtz cryoiala up to Jnl long. Sarplc courtery of Dr B.Y.
    . Roblneol.
    '"i.,. 71921 (t{8b), r.earllS/560 280, }lerctoto l{lner Cauoolc Vela, oouthcra vorklagr: Stagc 2e
    :
    .j'traaca qtr ard ca.lclte.. Salp)'c courteey of Dr E.W. Boblleou.
    11925 ([9), aear t13/560 280, tlaratoto lll,te, Sil.var Queea Velur Stagc ?a qtz aud Siagc,2c
    ftne grailed qta, rp' Bar hsr cp aad py.
    t 13926 (HlO), ucor T131560 280. ltaratoto Hlnc, StlvcrQseea Veln, 3 lerel: St8t., qta rltb
    vug oryaiala up to 10nr 1ong.
    ,
    11927 (fll), near T111560 280, llaratoto }{lne, Silvcr Queon Veln. 3 levelr Stegc 2o l!.ac
    gralicd qtes apr gn, bal cp aail Py' rod Stagc 2o qtz.
    11928 (Hl9), asar T1)1560 280, llerrtoto H!'ro, Caroole Voln, 3 level: Stage 3 qtz vlth vug
    .. cryrtrla uP to 10nl long.

    .- i Salplc oourteey of Dt t.U. Roblnaol.


    ' 13g3O (X8r); !re&r T13/560 280. ltaratoto H1re, Caroola Velnr Stagc ! qta aad calclte Yltb
    , vug qtr oryatrlr up to $r loog.
    : 1j9J1 (A2ilt aeat t13l 560 280, Haratoto Nr.ro, SiiLvcr Quesn Yalar Stagc 2a qtr and Strge
    2e flne grataeil qlz, agt ga, ha, cp end py. Saople oourteoy of l{r C. Davla.
    -l 11912 (H24), near T111560 280, !{aratoto }llac, SLlver Quoen Veln, 3 level: Stage 2a qtr
    -' ' aad Strge 2c flne gretueil qtz, !p, grrr har cp rnd py. Salp1e courtesy of l{r C. Davlr.
    , 1lgt, (Xr5), aear T131560 280, Haratoto lllnt, Caooola Veln, routhor! uorklngot calot'te.
    : SarpLe oourtcay oi Dr B.lf. Bobllron.
    13911 (l{?), ucar lltl160 280, Haratoto Hlne, Cauoola Vcla, aouthcrn uorkings: calclto.
    Saoplc eourt.fy of Dr B.Y. Bobinsoa.
    13gr|' (x22), aear f13/!60 280, llaratoto Hlae, Canoolr Vela,'3 lcvel: Stagc 3 quarta ard
    t caloltc vltb vug.qt. orystalc up to 20rr loag.
    .
    - 13'9,6 (H2?), !'cet 713156O 280, t{aratoto HiDo, Sllvcr Quccn Velar rhaf! ruuk to 5 lcvcl:
    ' St.g" 2l qtr and Stage 2c flne gralued qtz, apr gn, bop cP arral Py. Sanple courtesy of
    .'. Dr S.D.C. f,abouc.
    13937 lll33), uear T1?/560 280, t{aratoto }llnc; Canoola Vcin: Stege 2b linc grelacd qtr,.
    caloltcr lpr llr eo, cp, py and o).. Supergonc ov aad cc. 9anple court.sy of Nr E. Gopprrd.
    ll9r8 (Xl4), T12l1g9 4,33. lleevoav!.11o; AJax 1 levclr rulloek beap: wg qtzl cryatair up
    to l0lr lol8.
    1lgtg ([16), l12lt99 41,5, Nervervillcl AJar 2 lovelr Eul}ock heap: Yug and corb qtr rltb
    ' oryrtrll uP to {0uu loag.
    13940 (126), t12l496 429, treavseille. Chanplo! Ntrar' Adtt 4 (ace rcp 3 of lorcllor'
    19?8)' .hatt at cnd ol aallt: qt..
    13911 (X14), Tl2ltgg {4,5, f,eavesvlllor Uar 2 1eve1r vug alil coub qtr. cryrtrlr up to
    . 35u long.

    j
    789

    1lgiz ([42), T12l1gg /r43, ]leaveavlllel AJar 1 levelr 85n ln fror portal' northern rall:
    qtz ultb vug cryltaLa up to {Ono long'
    fi919 (f39), T12l$a 440, Neaveavlller Blrds 0peucutr Vug qtzr cryatalo up to 20nn long'
    ljglL $17r, T121 195 L39, !lsaveavlller Gracol opencutr vug qta cryatak' Sarpl'e court'8y
    of Xr L. lorokler.
    11915 (f28), t12lL95 439, lleavervi'Ile, Gracer Adlt: vug qtz' crvstcla up to 15sn lont'
    'Eg16(x46),t12lLgl438,xoavarvl1le,ool'IeuArror0poacut:vugqtz'crystalaupto
    15nl loug.
    13gL7 (Erl5)r 8 leYol. (r1g. I-Q-2)t qtr Brd cclclte'
    T13l 51,0 2/.6r Kooata !l1no'

    13948 (rrte), T17lr1o 246' Eoreta lllno' 8 level (ffg. I-Q-2): qta and calclto'
    t1)1515 2rl'5. f,onata HLne' I level (Plg. I-q-2)s qtt ultb vug
    cryetrla up to
    1tgl9 (1r10)r
    18ol lolg.
    (Flg. I-f-5)r vug qtzl crystals uP
    13950 (';rlgr, T121512 517' Brolea Hllls Hlne, 2 levsl
    to 10or loag.
    1)951 $A6r) t121542 517. Broken f,l'rls lllna, 2 1cve1 (Ftg. I-f,-5)! vug qtzr cryatala up

    to 10nr 1ong.
    gunboan Reglon, uullock baap bealclo rhaft of the
    13952 (G810), 25g|6D 7o,|. To Ahunatar
    hlgb lavel vorklnga: Stago 1 qtz alil py'
    heap outaltle gouthcrn adit
    1)g5? rcsgr,25gl6,70 707, Te Ahuqetar surboaE Reglol' nullock
    of 1or lovsl vorklnge: Stage 1 qtz, py alil ap'
    13g5t'(G812)r2rgl6'I?T2l,Talhunate,EsrrlerReefaBeglonrlullocLheapoutsldeadLt
    up to 10na loag'
    Uclov,blgb leveL track: Stego 2b qtz aad eb' Vug qtz cryatale
    13915(Rol)rt10/r5295).Tokatea(Corouandel)'RoyaloakHlne'?leval:qtzandcalclto'
    13956(80?),110/r52953,fokateo(corooaudel)'RoyalOakHLue:qtzn!'tbvugcryrtela
    up to 15ou loug. AucLles'l t{uosur oalple No' HCl3989'
    Blg Reef' outcrop nerr lokatea
    13957 (tf2), 310/rt9 916,3okatea (Corooea'Iel)' lokatea
    gaildlel qta (aoelbyrtlne) sltb conb atructure' crystqls up to J0ru loag'
    nullock beap: qtr (aa;thyctlns)
    1)grg (802), TtO./352 g27, tokat,oa (Gorouandel), Buffalo l{Lne,
    vttb oolb atruoture, orystalc up to !0oo long'
    1Jg5g(ttrl)rnsarl.:,glij';gg46,totcatee(corooaadel')'ualocatcd:oedtuntollaogralued
    qta'Fp.ElloPaldpy.onlveraityofAucklauil(0eol.DeptJaanpleNo:HC416.
    11960(1X5),!ea!T1Ol919946.Tokatea(Corola^adel)'unlocatetl:reclluntocoarsogralueil
    qtrl opr tPr 8E anil py. Geologlcal Suwey earple No:?934'
    rloketla Reeft: llno gral'netl qtt' bt'
    1)961 (1tr?), near 71Ol)L9 946, tokatee (coronanclel)r
    ap aail cl. Geol-oglcal gurvey aalple No' 79?0'
    oak l{luel ? level: qtz eod celoltc.
    1'962 (Ro,), 11o/,52953' Tokatea (Corooandol), Royal
    13961rcBil,259167072,,teAbuuata,BarrlerBeefa8eg!'onr89.hatl!t';Stage2bqtrrab
    to Unlverel'ty o! Auok]'ald (Geol'
    .!d py. Salple courtesy of !b U.nJt. Rsosay. tsqulvelent
    Dapt.) aeoPlc No.19863'
    rlurflce olpoauro of 0.251 rldc rccf
    1396{ (oB),,2591658 ?o?, Te Ahunatr, Sunbgal Reg!'oa,
    21 9tt, py, Pg dt't argyrodlte'
    rtrlklng E/l{ and dtpFlBg lteop].y to tbe nortbn: stage
    supergcue tatlvc Ag roal ae. saople courtosy
    oflhl|lni'Rauaey' Equtvatoat to unlvcralty
    of luckland (Gool. DcPt.) Sauple llo' 19854'
    13965(HE1),259160090.(,}llueraf,erd,r'egtrallofatopeoppoat'tcsbaft(rrg.I.A.1):
    qtzr cp' PIr sPr Por 8D anit argentlan petrtlandlts-
    13966(il82),2,gt60o904',!{tnerrHead,ucetyallofstop.oppoglteeheft(Fr8.I.A.1)rqtr.
    .13967(N34),ncerT1)|,60280,}|aratotoXl.ne.CanoolcVo!.alStage2bflaegralncilqtr'
    .c8lot't.'lpr$!trPIroPlacagd6.I.suPorgonoGc.SanplccourtoayofDrB.T.Robiuaou.
    '1t968(fcl),T10/r12llLtUortbcraCoLvll]'ePenlnaula'lang!'aroStrean'heaglngvallof
    cltereil coutrtry rock vlih l'lno
    lveta l! tog actl! eaatorn e!.de of alroaor bydrotberaally
    . gratood. PY.
    790

    1396g GBI), 2jg/67) 7O7. Te Ahuoata, Sunbean Rogton, rsuobeao adltt: Stage 2a gtr' cP'
    rp. pgr PIr Dcr ergyrodlte, el and pb. Sanple courtssy of ltr I'R'f,' Reosay' Equlvalent
    t,o Urtverslty of Auckland (Geol. Dept. S.anple llo. 19852).
    13g,lg (Dg1,), SIO/2,11 '168, llortbsra Colvl11e Penl.nau1,a, Doctort Creelc. float; crlclte,
    coarre grclned (nex. 12!!n)
    .1tg7l (nCtZ), S1Ol271 i68, ttorthorn Colvll1o Pel!.naula. Doctora Crockt nsdlur to coarde
    'gralned qtel gn, tp' cp and py, vug qtz cryetala up to 6ra long'
    1rg72 (Silt), SIO/Ajg 121, l{orthsro Co1vllle Penlaaula, Sorry ilary Stroaut nedlur to
    ooarto gratncd qtsrEp. BBr cP ald py, vug qtz crystalr uP to 5uo 1oa8'
    13971 (SH?), Slo/23g 12t,, llortharu Golvllle Pealaeula, sorry Hary strear: eodlur to
    corlro gralaed gtr; opr gnr cP end py.
    ' .1Jg71 (Sll11), S1Ol2)9 121,, North.rn colvllle PonlnbulE, Sorry ltary gtrcan: uctllur to
    .i"o"tr" grelncd qtB' tpr gur cP and py, vug qlz cryetalo up to 6oo long'
    Paolnaular Sorry Hery Stroalr ledlur to
    . 11915 (St{12), S1Ol239 124, ltortbern colvlltc
    . coarre gralled qtzl rpr 8D, cP aad pyr vug. qtt cryatelo up to Jro long'
    .1'976(sxl4)'s1ol2'g124,NortheraCo1vll].ePeal'naula,SorryHsryStreao:nedlulto
    . '. corlEc gratned qtr' tP. 8!, cP and py, vug qtl cryatelr up to lll long'
    13977 (l{t4), T1O/55A g15, f,ueotunu, ualtela Hlaer 4 leve1' couutry rock 1u fror'velnt
    byclrotbcrrelly altered greyvacko nLth tine gralacd py'
    l3gT ([h2?), DLaar 113/620 200, Waihlr r]{arthe Lodgt: aetllun to ftne gral'ned qtz, apr
    gtr, cp, py aad po. Aucklend l'luaeus aaaple nurben |1C681''
    .l3g7j (111110), T1t/rJ1 014, l{atorongoral., }tay Queen, 3 level (Flg.vIII-1)r rullocl heaPr
    gtagr 1 redluu gratneil gtt, EP' 8!' cPr py antt tb\and Stage 2 qta'
    139g0 (ts.t), T1Ol360 908, Potote Strean araa (CoronandeL). tltkeu Streau: Stage 2 qtrp
    vug cryrtall uP to 20ro long.
    13981 (AS2), m1l360 908, Petote Streau (CoronaaileJ.)r Altken Stroar: Stege 1 redlur to
    coarEo gratled gtzp gar rp, pI end cpr end Stage 2 qtz ancl py nl'tb vug
    qte cryatala irp
    to 8ul Loug.
    13982 (AS5), TlO/350 908, Patote streau aree (coroueutlel)' Altken streau:
    stege 1
    , lcdlur to coarEa gralneil qtz; ga1 apr PY anil cp, alal st886 2 qtz aad py r,lth vug qts
    -,l ,eryatala up to 6un loug.
    ',,,tnaZ
    (HCZ), l1ol361 go3, petote Strsan area (Cororrnilcl)' flutt Creolc: Stagc 2 vug qtzl
    oryotala up to JOon lou!.
    13g1l 1g63),110/36t 9Ol, Petotc Strear area (corongndcl)' Eutt crcek: stagc 2 vug gtrl
    . cryatalc up to 10nn lorg.
    ' 13985 (SC3a), l1'l;!36'1 903, Petote Strean area (CorocBrilsl), Sutt,Crccki St'age I rcillur
    ' to coerae gralnod qtz; apr gur cP end py.
    .lt39g6 (EC3b), ?11li61 903r Pelote Straan araa (Cororandal), Sutt greel: Stage 1 rcilt'ur
    ' to ooarac grahed qtz' tP, 8nr cP ancl py.
    : 1398? (SC3c), tllli,61 903, Petote Strean rree (Corooaadal), f,uti Creek: Staga 1 retll'ur
    i to eoarao gralled gtl, sPr EDr cP aad py'
    . 13g8g (Ectd), l1ol361 90lr Petote strean arer (coronesdeL)r f,utt creek: stage 1 radLur
    to ootrss graiued qtz, apr 8!, cP end py.
    13989(gcl,|,110|16lgoS,PetotcStrccnarea(Coronandel),EutiCree}rStaScllcdl.ul
    to oosrt. Srrtlod qlzt spo 8!, oP and py'
    13990(HC42).t'lll)6'lg03,PetotoStreaoaro!(CoroDaadel),Hutt0reek:Stagelrcdlur
    to coarae gralnetl qtz, rpr 8[r cP antl py'
    11991(Ps1),T11/36lsgg,Pototsstrcarlrsi(corolardel)'Pctotesttear'chaLcopyrl'topy
    Lodor Stagc I qtr, cp, py, ap aad go (necllul to ooart Sralscil). Stagc 2 qlzo cp and
    (ledlultogoargeSralaeil,vugqtzcryetalauptolOnulong)andStege3cclelte(nax'4nl).
    79L

    .13gg2 (rs:), t11lt6t E99, Petote gtrcro arss (cororauctel), Petot. Stroan; cbalcopyrllo
    Lodcr Stago 1 qtr, opr pyr ap aad gn (uectlur.to ooargc gralaed), Stage 2 glz, cp aad py
    (coaroe gralned, vug qtz oryetala up to 10nn long) aad Stage 3 calclte'
    13993 (Ps?)l T11l)6' 899, Petote Strean area (corEga,ndo]'), Pototo Strear,Chalcopyrlto
    Lode: Stage 2 qtz (vug crystsl9 up to 12nn long) coaree gralaed py aud cPr aEd stago 3
    calolte (rax. Ju).
    ltggL (ps9), I11176) 899, petote strar area (0oronaailel), Petots StroarrChalcopyrlto
    , Lodol Stage 1 lsclLul to coarre graluod qtz, cp, PYr oP eacl gn, aad Stege 2 qtr.
    . ltgg1' (pglo), T11l36i 899, petots Streer aroa (corouaailel)r Psiote StrearrChalcopyrlto
    Loder gtrge I neillus to coarao gralne<l qtrr. sP, 8!, PI and cpraBd stags 2 vug
    qtz vltb
    , . crystals uP
    ' to 1 Onl long.

    '.. ttgg6 (ps1ls) ,t11136) 899r Petoto Strean arer (Corooandel), Potote str6sEtcbalcoPyrttc
    ,. .Loder stage 1 aeilluc to oorrse gralned qtB' ap. 8lr PI auil car stagc 2 qtz;Pl eud cp
    -,' (ooaric'gralnod vug quartl cryrtala up to 7on tong)'
    139g?(psl4)tllli6S8ggrPetoteStreararaa(Coronandel)rPetoteStreao.Cbaloopvritc
    . PY aad cpread stage 2 qtt' elth
    Loilcr stcge 1 !edl,u! to coarse gralaetl qtz' tP, gnr
    .. co4lac grelned PY and cP'
    '.
    139g8 (psl5, , t11/361 899, Petotc gtresn area (Coronandel)' Pelotc Streaa'
    Chslcopyrltc
    ' Lodc: Stagc 1 goarBe gralned ql,z, apt 8ar PI aoil cp, gtage 2 qtz, Py aad cp (ooerac
    graloed, vug gtz cryeta!'e uP to 10 nn long) aad Stage 3 ealclts'
    Vulcan 2 level (flg.Vfff-a)r Stage 2 qta and pyr
    . 1)ggg (Itt?O), T1tl5t5 040, Ualorongorell
    .vug qtz orYatala uP to l{nr loug'
    , 14OOO (PS21c), 7,11l36t 899, Potote Streeu area (Coronantlel), Petote Stroar' Oaleae Lotle:
    stage I nsdlul to coarge gralaecl qtz, gn, rpr pr anil cpraril stage 2 qtr rltb vug
    cryetala
    '. up to 6rr loag.
    14001 (ps21g). T11/36) 899, petote strean area (Gorooauilsl), Petotc
    strean, Galcna Lode:
    slege I ooarao gralned qtz, rp, gtrr cP and pyrand stege 2 qtz vlth vug cryatala up to ?ol
    long.
    11,OOZ (P921h), 11llt6t 899, Pctote Stroeq Arca (Gororaudel), Potot' Strsarr Galeaa Lodc:
    Stagc 1 nodlun gralned qtl. ap. 8rr cP ard Py'
    14003 (PS21f). T11136? 899, Pot'ote Stroan Arer (Cororandel)' Poio! Strean'
    Galsna Lode:

    Stage 1 lediul graLneit qtz' sP' gnr cP and py'


    I

    hcag: qte and flao


    14004 (ut15), T1Ol5r8 915. Kuaotunu. llaltala Hlaer { level aul'Iock
    grillail PY aad uc-
    Streal, Galenr Loder
    11oo, (Ps24), T11|'63 899, Petote Streal erea (corolcntte].), Petote
    Stago 2 vug qtz crYstela.
    11,006 (ps26), TlOl)rg 901, Petote streal area (oorooaadol).
    vsln'crosshS accoBa track ot
    cryetala up to 15nr loaS'
    blll,r aouthera atile of letoto streao: stage 2 qtz vlth vug
    qtz.
    1{oo? |K3,1 . T1o|,58 9,|', Kuaotunu. Uaj'talat{lner 4. leve1 nul].ock baap:
    qtl.
    .11i008 (Kil, T,|ol 558 91'. Euaotunu, t|altala l|14c, 4 leval nullock heep:
    1l,oo9(cL1).[car:l.a||,n940,Euaotuuu,coldenLlnkl{lne:qt!yltbvugcrlrltAl!uptolllo
    jloog. luoklald !'luaeun aauplo No' 368'
    berp: stago 2 nedlul
    l4OlO (Ir1), T13l55t 215r ljaltekaurl' Jubl'lee lov level' nulloclc
    gralaedqtrlgn,sp,oPandPy,andStagesqtzyltbvugcryotalrupto{B[1olg'Sarplo
    courleaY of Dr B.J. Herchant'
    11,011 (Ufz), T171551 2151 l{el,tekaurlr Jubtlee lov level,
    rullock beap: Stago 2 recll'ur to
    cryatelr up to Jrl lorg'
    flno graluail qlz' ap' PIr cP and garaad Stago 3 gtz vltb
    vug
    Sarplo courtosy o! Dr B.J' }lerchant'
    lullock hcap: stagc 2 nediur to
    11012 $t)1, T1tl15) 215. ualtekaurtr JublLec lov level,
    flncgralnedqtu'.!P.oplPlaodSnraldStrgcsqtzultbcryotaleup!olOonlong.Salplc
    ' oourtorY of Dr R.J. l{crshanb'
    792

    14,013 (1{84), tlr/450 2O5. Wa!.tekaurl. Heorllan<l Velu (c.f. Babouo, 1971r 986, bottoE thtee
    llnca)r vug qt! cryctala up to J0ln loag. Sarple courteay of Dr S.D.C. Eabone.
    1401{, lVK'l, T1)lrhg 215. }Jaltokeurl, Jublleo lov level Bt ,ulctl,on of crosscut and drlve:
    vug qtr cry3t41t up to 25nn long. Seopla courtcsy of Dt S.D.C. Raboae.
    11,01, (ltK6), T13l5lr7 212, tlaltet<aurl, Ju611eo lov levsl: gtage 2 qtz anil flne gralaod cpl
    apr FY aacl gn. Seople courtosy of Dr S.D.C. Raboae.
    14016 (nf?), ll3lrt).215r Ualt,ekeurl, Jubllec 1ov level Bulloclc beap: Staga 2 redlur
    gralneit qil, apr cp, py aud gn, aad Siago I qtr rltb vug cryetala uP to 4Dr long. Saople
    couriooy of Dr R.J. l{erchaat.
    1101? (Uf,9), necrrl13l211 545, l{altekeurl, Jubllee HLne 2 levol: Stago 2 nodlur gralueil
    qtr, cp a6d py. Ualvoraity of lucklaoit (Geol. Dept) aanple Nc. llC1,60ftueae1l Gollectloal2?2).
    14olg (Uf11), T13l5L7 212, lJattekaurl, Jublloc lov levolr ?90r ln fror portal.: Stagc 2
    ltlc gralnecl qt., py, cp, sp au<l g3r ald Stags 3 qtz, PY arrd cP vltb vug gts cryatall uP
    to gu loug. Salple courtecy of Dr S.D.C. Rabone. Equlval,eat to llllverclty ol Aucklaad
    (Gcol. Dept) sanPle No.18519.
    1&Ot9 (t{Xl2), 113/553 215, l{atlekaurt. .IubLler lov level lu]-lock heapr Stage 2 tLn. gralucd
    qtr, !p, cpr ga and py. Sauple court.y of Dr S.D.C. Rabola. Equlvalcnt to Unlversl'ty of
    Auoklend (Gool,. Dept) sanple 1Io.18606.
    ll,O2O (lff1r), Ti3l5fi 215, Waltekaurl, Jubllec lon levol Dullock beapr $tago 2 redluu
    gralaed qt!, ep, cp, gu and py, and Stage 3 qtz sltb vug crystals ult to 4!}I. Supergenc ov.
    Sanple courtry of Dr S.D.C. Rabons. Equivalent to llnlverglty of luclrlend (C6ol, Dept) aanple
    11o.18600.
    1{OA1 (lL2), l13lr11 156. EsrragahaLe, TeJ.larar tllns, 11 lovelr approrlratcly 601 ln fror
    ' portalr cbelceclontc, conb asd fllg qts. Vug qil ctyttelE up to 5na loag'
    . 1LO2z (TLgr. ?"j1)1j13 155, Karangahakep ?allguaa Hlner I levol, HtriB YolDs chalcedoric
    qtr vltb raro Yugs coutalatng qta cryateh up to 5nl long.
    1LO23 (lL1?), \68j. T11/5'l) 1J1, Eerangabake, Talleoca Xlaer uulocated: {tz' gn. tPr cP
    Erd py. Unlveralty of tuckl'antl (Ceol. Dept) aauple l{o. llC:853'
    , l40Z{ (lLZl), !'ear 11315'17 1Jl, f,arangahakc, ?allaral Xlac' Harle Veh: qtr' Syfrtu!' tp'
    trr cP ucl py. Oeologtcal sutry aanple No:843?.
    . 1LO25 l11Lzzr, o,eat 1131513 151, f,arcagabcke, Tallenaa Xlne, 14 levclr HarLa Tein: qtr'
    calcLter rP' gn' cPr PY ancl el. oeologlcal.furvey illoplay aaople'
    14026 (1L24), naat T131513 151, f,arangabalcer taLlgnau H!.ne, '13 level. Sonauzl ccciioa of
    Harla 1etn lt lee levclt IZO oz. 6ilrt 169r. lu aral l8 oz. {dvt. 22gr. Ag pcr ton) qtrl pyr
    cpr .!p and gn. Auckl'and Xugeun apeclnen, uo aUuber.
    11027 $LZ|.l, o,ear 113!5i3 151, (arangahalcr tal,l.gnrn Ninc"l3 levs1, Eolarzr aactlou of
    ||rrl'a Yela 3u be]'oy saa 1evel: (9 oz. 17dut. 1581, Au and j2 oz. |dvt. 8gr. lg pcr ton)'
    qte, tp, plr cpr gn and el. AucLlald llueeun rPoctrsa' no lulbcr'
    l{,028 (Utta), T1Ol558 915, f,ueotuuu, }leltala t{luer 5 level nul}ock beap: qtr ard rcillun
    to flla grrlned PY antl narcaolte.
    11029 (U}lz), !;eat 151, f,arangehaLe, tellgnan MLner l{arnlon Exteadcd Lode: qtr
    vlth vug cryatala 'r1)1513
    up to {lr long. Aucklancl t{ugcun aalple lio' 52?'
    l4OrO (Gf1)r ;,urr 7111625 205, !{alb!r Grqnil Juaclto! Nllo' uulocated: qtr aad ca}cl'te.
    tucklead l{useun raoplo no. }lC:6813.
    1LOj1 (CJ2), o.r" 21J1625 205, Ualhlr crancl Juactl,oa Hl,nc, ualocatcdl selclto. lucklanil
    lluaoul ttrplo ao. HC:5913.
    1LOr2 (CJ3), nerr T131625 205, t{elh1r Graail Juacttoa }{lae, ualoceted: ftne gralaad qtr'
    PJrrPrSlroPracandetyltbletervuggtz(cryatalruptoSutJ'oag).!dpg"|ucklaad
    lfuscur tarPlo no.' l4Ct679).
    1401, (CJ4), nszr 7131625 20!, lfa!.bt; Grald Juactlon Hlns, ualocaiotl: fluc gralnecl gtr,
    Bnr 9Pr py anil cp. l'tlnea Dlvlelon dloplay ap'clnoa'
    793

    11,031 (Ubi), 3/622 19g. l{alhtr llo.5 abaft, DuLl,ock heap: cbal'cedonl'crconb alal Yu8 qtz.
    T1

    Vug qtl cryatalo uP to Jno long.


    1L03, (lrb4), T13/622 1gg, Ua1hl. !1o.5 ahaftr nullock boap: cbalcodonlcrcorb anil vug qtz.
    ILO)6 (l{b8). necr 113/618 202, Ualbtr at botton of vlnze .f,ron opeucut to a drlvc on the
    llarthc veln, qtz atrlngor parallel to llartha: chalcedouLc snd vug qtz. vug qtz cryatalc
    up to 10ru long.
    11037 (Uhl0), Tltl618 201, l{atb1, 3 level (Hartha lllll), Btope lD Hartba Velnr chelcedonl'c
    anil vug qtz. Vug cryotals up to 10ur loag.
    1t038 (Ublj), nesr T'13/6tg 202, ljalbl.r at bottoo of, thzo frou opencut to a drlve on the
    xartha velu, qtz atrl[gors parellel to ]lerthB vein: vug qtz, cryetsl,r uP to 5rn loag.
    14039 (ilb2g), aott T13l62A 2OO, Ua1bl, llcrtha Velu, unlocated: aedlun to llns gralnod qirl
    opr gllp cP Eld Py. lucklaad llueeur aanple ilo' HC:6855'
    fiq4o (gb29). \eatTli/6zl 200, tJalhl, HartheHlue, ualocated: redlur to flne grahedqtr,
    apr gar pl/. cp aad po. letsr eonb (cryatalo up to 10nu) and vug (cryetalr uP to 3ul) qtr.
    luclclalil lluaour oarpla [o. l'l0:69?9.
    11,01,1 (Ih3O), t1)162O 200, llalhl, l'lartha !{lnc, unlocated: reillur to f,Iae gralned qttt
    ^6^r llusesu aanple tlo' HC:6855'
    !!r Gpi py anil ep' lucklend
    ILaLZ (Ubr2). f13l620 200r Talbl, Hartba lllaer ualocatcd: qtr (arethyrttle) vl'th
    ''oat
    co[b ltructuro, cryEtals uP to 3OD! long. Auclland llugeuu eanple Xo' ]10t6949'
    IL}IJ 1uu35), Eesr T13l520 200, Walbl, Vlctorle Vetn, adlt level: flne gralned qtz. aP'
    B[r pyr cP, ao atrd I. Auckland Huseun saEP]'o llo. 294'
    14014 (Ib4O), s6a7 ll)/62a 200r t{alht, tlartha vsln eagt, ! level: calcl'te. Geologloal
    sulvoy aanple fro. 2?76.
    1lo[, (Uh41). Drr 1.lr/620 200, l{alht, Euptre veln' 12 lsvel: gtz (arotbyatlne) rlth corb
    atruoturo, cryatele up to 1Onn loag. Geologlcel- Survey aalple Xo' 8060'
    14046 (UlhIl), rleaE t13l62l 200, tta1hl, Hartba xlne, unlocated: flne grainad qt.t sp,
    gnt
    py, cp and el. Geologlcal Survey oanple l{o' 7810'
    l{0{? (Wb44), r,Oat t1316?O 200r l{albl, t'lartha Velnr ? level; flao graheil qtrl a9'
    gu;
    py' cP end el. Geologlcal' Survey aauple l{o' 7988'
    ac rucl
    110{S (yb4r). noet 173/620 200, IsLbl. unlocateil: fl,ae gre!'red qt8' tp' gn' eP' py'
    cl. Auckland Hugeul Speclneu. no aunber.
    rat tlaptht: flae gralnod q!e' opr glr
    11049 (Uh{2), uear.T13/620 200, }Jalhl, Hartbe Veiu,
    py auil cp. Geologtcal gurvcy !lo. 7935.
    qtz' cp ard
    140j0 (f/b{?), \oat 1131620 200, Ualhlr llartha Veln,'10 levell reillur gralned
    pt. SalpJ'o oourtcBy of Mr J. Barbarleb.
    '14051 (llh49), tear T13/620 200, uelhtr udoeateal: gtz' ap' P!r' cP aud gn' tll[c! D','tlst'o!
    dtaplay aPec!.lel. 1.

    1to52 (Uh'O), noar tl11620 200, llalblr lle:tha veln, l0 Levsl: reiltur to fluo grahed qtal
    lpr !tr1 o9r PY, acr thd asd el' Hlaes Dlvlalon illaplay spsclEo!''
    11O5t (fut3). rest :I13 521 O51 l5 level portal), tut M!'ae, Chanplon
    Veln' 5 level: Stage
    2 radlul t'o coarso grelaed qtz, ape 8D, oP and py'
    1Lo51(tur6),D,e^'-2131521ofi(,J'evolportel),1u1'l|!.ne,GbalplocVe!.n,5leve].:Sta8c
    ! qtr. Saople courteey of llra R. Baldley'
    levclr
    f10t, (1u112)1 Dra! Tl1l521 Ofi (5 lcvel portrl), Tul l{lno, CbarPloa Vetn' 5
    genple of Dr B'lf' Boblnron'
    Stagc 2 oouia grallrd qtz, rpr 8Br PY and cp' courteoy
    ltor6 (Turl3)1 !oE! 1131521 051 G level portal), Tul t{lnc, Cbanploo Vela' 5 levolt
    gnr py aril cprand corb qtz (cryotclo up to 10un loaS)'
    Stagc 2 uetllun grrlneil tPe
    VoLn' ! laYol' StoPe
    1LOrl (1u111), noer 113/521 Olt lr level' portal), Tul lllne, Cbanplon
    of Dr B'T'
    L1r stago 2 nedlur to ooarse gralaed qiz, ep, lar cp and py. sanple
    oourtaay
    Robl!ao[.
    levclr 20r
    1&058 (tur15), lorr t131521 OlJ 15 revor portal)r tul lltne, Ruatgka vela' 3
    2 gratneil sFr Rlr PIr cP aacl thd. sauple courtaay of Dr
    aortb of rtopo 18s stege coBrso
    B.ll. Bobtuooo.
    ,
    1lorg (Tull?), noar t1t/521 05J 15 levol porta),), Tu1 t{lno, Charploa ve1a, 5 Levcl, oad
    o! nortlngs ('l.973)t Stage 2 ugdlun gralaed gtz, op, grr py and cpraad gtago j conb qtz
    (oryatala up to 12on loag)'and taollntte. Saople courteay of Dr B.lf. Roblnsol.
    11'060 (ru118), a6ir !1t1521 o53 (5 level portal,), Tul Hlae, Ruakala Veln,3 levol,20u
    rorth o! Stops 18: Stago 2 coars gralned apr gnr pI, cp aad qtz vlth vug crystalB up to
    1Our long.
    11051 (Tut19), Borr T1t/521 Orj (5 lovel portal), tul Nl!c. Chauplon Ve1u, 5 level, DD
    croslcuti Stagc 2 ooaraB grained apr Bor p)l' cp and qtarancl Stage J conb qtr vlth cryotala
    up to lJon long. Scop1e eourteay of Dr B.U. Roblnson.
    14062 (tut20). aoE! T13/521 O51 (5 levcl portal),lul l{lne, Buakaka Vola,2 level.: Stage
    2 oodlur to coaroe gralned apr gar pyr cpr coob qtz (cryatals up to ?lu) aud vug qtz.
    Saeplo courteoy of Dr. E.l{. Roblnson.
    11061 (fuf21), !6ar T1tl521 o53 (5 levc1 portal), lul lll,ae, Oharplon Velu, 5 leveL,
    approxl,natcl! 175s XE lror acceE. cross-cut! Stege 2 coa!r6 gralaed, vug qta, ap aoil gn.
    Saeple courteoy of Dr A. lloilzlckl.
    1{064 (fufez)' hoa! T111521 053 (5 Lovel portal), ?ut l{lne, Gharplon Ve1a, 5 level,
    approxhatcll L75n llE fron accsa! sror!-outs eerly Stage 2 qtr. Sarple courteay of Dr A,
    Ioilrlckl.
    11065 (Tu123), D6a! T1tl521 O5t (5 1evel, portel), Tul lllnel cbauplon vo1n, 5 lovel.,
    approrS.ratell 175n tlE fron accosa crora-cut! Stage 2 corale gralaeil qtr, sp, gn, py aatl
    cp. 9anplc courteoy of Dr A. llodzlclsl.
    11066 (Tut 25), near l1t/521 o53 (5 Level portal), tul H1uo, Gharploa Votu, 5 level: stagc
    1 redlun to flao grelaetl qlz, py' cp and bouatltc. Supergele goetblte. Sanple courteay
    of Hr E. Coppard.
    1106? (1u126)r loar T131521 O53 (5 leval portal), lul Xlnsr Ruakaka Vela; Stage 2 necllur
    gralaeil ap anil gn covered vltb Stago 3 qtz antl ba. Platea of ba up to 8nn acroae. Salple
    oourtely of llr E. Goppard.
    11068 (tu128)1 Dor! l1)1521 053 (5 lavel portal), Tul Hluo; Gbarplon Voln, 5 levcl, rl
    ltepct Slag! 1 redlun gralaed qtz cp ald py' and Stage 2 qtl rlth rug cryatala up to 6nl
    loag. Saoplc courteoy of Dr [.1J. Kobc.
    l{'069 (1u129) , T131521 051, lul Htne, rulloclc bcapr qtr.
    1.f0?0 (Vt3l,7131028 538, llaloroagonel, lloe Vela (ffg. vUI-1): Stage 2 qta (vug crystals
    up to lOu long) coatad rlth platea (up to 5ur aeroga) of Stage t ba. Saaple courtcey of
    llr R. Aaaln.
    11071 (U116), t13/535 0l!, tfalorongonal, Caaaillan Creok (rlg. VIII-I) floats Stage 2 vug
    qtr, GryElalr up to 1Ouu Long. t.
    11072 (1121)' T13lr96.0JJ, Yatororgoral, Dlarontl cully' Xo.1 Reelr !,rrr a hoppar oD tbo
    tralray (ffg. Vttf-f); Stage 1 ledlur grahed qtl, apr gtrr cp ald py, atd StEgc 2 qtr,
    lto?E (v122). Tl)t515 0J3, llalorongooal, tlo.1 Veta expoaed 8t tbo head of a vaterfalL la
    Dlalond Graok (Fig. VIII-I)s Stago 1 rediun to coarao grallod qtr, rp, 8a, DIr cp and el1
    and lltrgr 2 qtt ylth colb cryrtal up to 1 Jrr loag.
    140?l (Yf25), ll1l535 033, Ualoroagoral,l llo.l Vetn oxporoal at tbc bcarl of a vaterfall la
    Dluond Orcek (Flg. YIII-I)r Stagel aodluo gralaed qb,sp, Enr pI aEA cprand Stage 2 gtz
    rltb vug oryltela up to 10rr loag.
    11075 (Ir2?), Yt/535 033, l{al,oroagoual. f,o,1 Veln expoaed et the bcail of r vaterfrll la
    Dlrnord Crccl (flg. VIII-1); Stago 1 nsdtuo to coarro gralBed qt.r.p. Bar py aril cprard
    Stagc 2 qtr.
    11016 (If3l), tltlfi5 038, llaloroagorat, col.onlst Snlthy tevel (Flg. vIIf-2). looae
    Eatcrlsl oa floor of rtopo: Stage 1 ledl.un to coarac gralnod gtzr 8P' Bnr cp aail py, and
    Stcgo 2 qtz.
    11017 (1135), t131535 038. ualorongooal.. colorlrt sultby tevol (Plg. vlrr-2), Ioorc
    latcrlel on floor of atopct Stage I redLun g!.lBod qtz' .pr gn, oP, PIr ba cad el' and
    Etago 2 qtz vlth vu8 oryrtalt up to {nu loag.
    ?95

    -1,{,O?8 (U139), t1?1531 034, }Ial.orongoncl,, Xay Queeo 2 I'cvsl (81g. VIII-1), nullock borpr
    Stage 1 Dodlu! to coerB grouad qtz, tP, 8rtr cP and pyranil Stage 2 qtz rl'th vug
    cryrtals
    up to lnn loog. Supergeno cv altd goethlto'
    1tplg (t{141), T13/53? 034, ljalorongonel., }lay Queea 3 Isve1 (F19. VIII-I) nullock heap,
    Stege 1 aallur to ooalto gralned qtz, sp, gnr cP aod Py. aud Stage 2 glz vlth conb/vug
    crystrl! uP to 12on long.
    1t080 (f142), T131537 031,, llalorongonel; Hey Queea 3 level' (flg. YIII-1)' rullock beaP:
    Stago 1 redlul to ooarge grelaed qtz' sP, 8Br cP and Py' cail Stago 2 gtz'
    14081 (t{1t5), t1lt537 031,, tlalorongooal, Hay Qusea ! lsvol (P18. VIII-I)' Eullock heap:
    Stagc 2 qta.
    (91s. VIII-I)' rullock
    1{082 (l{151). r13/o3o 5l5r ltalorougoro!.' Bonanre (-l Foola?) Veln
    adlt: stage 1 oedlur gralled qt3r sP, 8trr cP aad Pyr ald ste88 2
    bcap out,alde collapr6d
    qta and py.
    (Fl'8. VIII-1), uullock
    14083 (Ifi4)r tlilOSO 536, tfalorongo4al' Bonrnza (-3 FooLs?) Vlu
    hoap outrltle collspted adlts Stage 1 uedlul to cogrsc gralaoil qtt. sP' tnr cP Bad Pyr 8Bd
    Stago 2 qtr aad PY.
    gouther! edlt (Flgr YIII-I' and
    11,084 (Wf56), l1)/g2g 53?r llaloroagorelr lfelcona VaLn
    vIII-g), J0cn qtz vctn 8n li frol portal: stage 1 letltul to coerae grelaed qtzr sP.,8['
    op aoal pyratld Stege 2 qtz vlth vug cryetale up to 4r! loBg'
    (F1gt VIII-I' ald
    1L085 (U15?), T13lO2g 5J?, l{elorongonal. tlelcoqe VsLn soutbera a'lli
    vIII-g)1 loooe oatcrlal, outglde edltr strge 1 DoilluD to colt|es Sralneil qtgr aPr tnr cP
    aad pyread Stage 2 qtz.
    (Flg! YIII-1 aBd
    140g6 (lli58), g13lo2g 53?, ltatorongontt!t Uelcooo Veia gouthern atltt
    aud py1 end
    vIII-g), loose uaterlaL outaide adltr stage 1 nedlun gr.l[ad qtt, !p, 8nr cP
    Stsg. 2 qtz.
    1{,Og? (U164), t13t5?1 oJJ, lJaloroasoral, llalq veln axPosod at tbe hoad
    of e vatorfall La
    (flg. vrrr-l)r stagc 1 nedluu gratnoal qtz, gal rp, Pr allal cPraBd stage 2 qtr
    Drrnond croek
    ullb Yug cryrtala uP to ?uo long.
    of a Uctorfall
    1{,088 (l{165). 113|fi4 033, l{elororgolell Hala Veh expoeod at th heeil
    qtze ga1 gPr cPrard staE
    1n Dlarood crorL (glg. vrrr-1): stage 1 nodlul Errlloal Pr aDal

    2 qtr. .r
    11,Ogg (u166). t1315?L 033r llaloroagoDrlr Malr:rveln erporotl ai the beail of I vatorfEll 1!
    Dlarond cr6cL (Fig. vrrr-l): stage 1 4edlun grelned qtz' gn' aPr Pr aud
    cp, ard stage 2 qtr'
    11090 (Uf6?), T13l5tL 033, lJalorongonall 1,0cn tblok qtz Y61D erpoaetl 50q ln fror
    portaL
    pert ot }laln VaIn: Stagc.2 vug glz
    tn au adt! above tba pack track (f1g. VIII-I) Probably
    rltb orYatala uP to 80oo 1ong.
    olrp. (Frs'
    11091 (il180), t17t53L 039r lJalorongonal, ll& vo!-r crpoacd at headol a largo
    VIII-1)1 Stage 2 qtal rug cryatale up to 15rr loag'
    (Flc' vIII-2)' looro
    1&Og2 (Ursl), l1Jl535 038. Ial.orongonal, Coloalat sultby leYol
    lstorlrl on floor of 6loPot Stago I Ildlu! to cotrle gra!'ncil qtr' tP' tl' cP' PIr ha
    and elrrnd Stagc 2 gtz.
    140g1 (Itg?). T13t51lr 0l5, l{slorongona!, lfel. Plnd, bouldor
    of qtul et uorthsrn end of
    to 20![ long'
    op.rout (Ft8r. vul-l anil vIII-4)r Stage 2 vug gtz, cryotale up
    a'ltt (r18t VIII-1 anit
    1lOgI (Ir8g), 113llro 5l?, l{alorongoual; l{slcore velur aorihera
    qtr' cryetala up to lJnl long'
    VIII-8), Yettl expoaed ls ln frou Pottal: Stage 2 Yug
    eillt (F1gs YIII-1 anit
    14095 (XfgO), 1111rrjf| 5l?, lJalorongoual', Velcose Vetn, nortbern
    la froq Portsl! Stegc 2 qtz' vug cryetela up to 201 long'
    VIII-8)r YeIn erpooed 1u
    a'Ut' (Flgt VIII-I and
    11096 (1191), T13IO3O 53?, Ualorongonal. llolcore Ve1n, northcrs
    qtzr cryatala up t'o 2Jnn loag'
    vIII-g), veln expooett ln lu frou portall stagc 2 Yug
    etltt (Fl8s VIII-1 aad
    1Logl (w192)' T13|o)o 53?r l{elorongonal, tlelconc Vela; northern
    fron portal: Stago 2 qtz' vug cryatall up to 20un loug'
    VIII-S), Veln elpoaed lu Lq
    14f9g . tlgl.ggb l3?r tlel:arrrngosalr rnroraaaa,
    11g,1..*)
    Iloln nsr-thers a!t!'t (F{'es tllTrrl .od
    gtage a uqg qtrl' qyyota'Ir u'p t'e ?lut !ong'''
    o11X-g)n 16oae bl.ou,b ef qtrr emts$itrg Portell
    sr'-lsgX$ 408E loaq c'ry'e-bal of qte
    ltogg (tf,lg?'r tl,3l0-:99: 53S, flrhicr,o$gooalr. t{eJ.core Tail,a':
    (Pl'g' A-3&)' SEcpl'a ,.'o$nts!r' '}l* Br
    soated ul,tb ptltet i."; ;; ;.- "..i"aol;otr Stage 3'ba
    Goppard.
    14|o.olililgs''Tti,15:,'.0J6'tfai.ono]tlgo6li'}|c.freaotdl.looi!xpvgl(f,{,esgllx,-lanilVE,[I-Z)"
    orr" hi' sEil' a"ltllteT Slbogs A g&z eld
    nultre,et heap;, Eta,gg 1' dod$.uE 16rcired 'qi'9r1 aPr $rBr P:Ir
    SUPOI!'8Gn cv.

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