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Economic Geology

Vol. 64, 1969, pp. 112-115

DISCUSSIONS

HYDROTHERMAL TRANSPORT AND DEPOSITION OF GOLD

Sir: In the recentpaper on this topicby Helgeson plexesare importantin the transportof gold they
and Garrels (EcoN. Gv.ot.. Vol. 63, No. 6, pp. 622- seemto have left remarkablylittle evidenceof their
635) the followingstatementis madein the conclud- work in most gold-quartzdeposits. On the other
ing remarks--"Most theoriesof hydrothermalgold handthereis plentyof evidence to suggestthat sul-
depositionfail to accountfor the geologiccharacter- fur, antimony,arsenic,and telluriumcomplexes were
istics of gold ore deposits." I submit that the two intimatelyinvolvedin the transportof gold. Of
authorsof this paperhavethemselves fallen into this courseI am awarethat chloride,beingvery soluble
very pitfall. andmobile,maymigrateoutof a veinsystemleaving
I have little comment to make on the chemistry only tracesin liquid inclusionsand vugs.
sinceit has been known for many years that gold In the matter of liquid inclusionsin gold-quartz
is soluble as aurous and auric chloride complexes. veinsI am notfullyconvinced that theseare repre-
I am a little puzzled,however,to note in the dis- sentative of the solutions or media from which the
cussionof the equilibriumrelationsthat the sulfur bulk of the gold was deposited. In a study made
ligandsonly associate with the hydrogenion and someyearsago (Boyle, 1954) I observedthat some
the metalsonly complexwith the chlorideion. I gold in quartzveinsmay havebeendeposited from
suspectthat not all of the dissolvedspeciesthat one solutions represented by liquidinclusions that prob-
might find in the real systemsthat depositgold are ably containtracesof chloride. This gold was, how-
defined in the model, and that in natural solutions ever,late and was relatedmainlyto secondary liquid
one might have gold-sulfur,and especiallygold- inclusionsdevelopedin shearor fractureplanesin
arsenicand gold-antimonyspdciessince there is a the quartz. Both the gold and the solution in the
marked geochemical coherenceof gold with arsenic liquid inclusionsseemedto be quite unrelatedto the
and antimonyin many if not most types of gold- initial and major depositionof quartz, pyrite, and
quartz deposits. Part of the chemicalpictureas it arsenopyrite. Later work on gold ores with liquid
relates to the natural situation is, therefore, missing, inclusionshas tendedto confirm this opinion. If
an essentialpart it seemsto me if one is to explain gold is relatedto the liquid inclusionsin veins at all,
the origin of the many gold-arsenic-antimony quartz it is related to secondaryinclusions,the origin of
veins that occur throughoutthe world. whoseconstituentsI have not yet been able to dis-
However, I assumethat the authorswish to keep cover.
the modelsimpleand are most desirousof making The equilibrium or simultaneousdeposition of
the point that the critical dissolvedspeciesin the quartz, pyrite, and gold assumedby the authorsfor
media that depositedgold-quartzveins is an aurous gold-quartzveinsseemsto me to be in seriousdoubt.
chloridecomplexin acid sodiumchloridesolution. There are a host of references in the literature on
No amountof erudite thermodynamicmanipulation, the subiectof late depositionof gold in gold-quartz
I would mention,can indicatethat this in fact is the veins. Frank Ebbutt (1948) made a long study of
case in nature. One must look carefully at the this feature and has shown rather conclusivelythat
natural systemsto get the clues. gold is generallydepositedin late fractures,shears,
In high-temperature skarndeposits containinggold, etc.in the quartz. My investigations of varioustypes
quartz,and generallyabundantarsenicone might of gold-quartz ores confirm his observations. How
suspectthat if chloridecomplexes are importantin this feature is to be explainedI do not know. I
the transferof gold,that scapolite,chlorapatites, and once thought (Boyle, 1961) that the late gold was
.other minerals containingchloride would be abun- exsolved from early depositedauriferous pyrite,
.dant. In my experiencethis is generally not so. arsenopyrite,and sulfosalts,but I have sinceseena
Similarly,I havenotbeenableto discoveranyquan- host of examplesin gold-quartzveins where this is
tity of chloride-bearing mineralsin other types of obviouslynot so.
gold-quartzdeposits.Aboutall the chloridethat I Some natural hot springs that depositgold and
can find in gold depositsand their wall rocks is a silver in siliceoussinterhavebeendescribed. Many
sparsefew hundredpartsper millionthat wasprob- of these contain dissolvedchlorides. Some are acid,
by the hostrocks. If chloridecom- but those containing significantquantities of gold,
ablycontributed
112
DISCUSSIONS 113

silver, sulfur, antimony,arsenic,and the other ele- silicasincequartzcomprises well over95 percentof
ments commonlyfound in gold-quartzdepositsare most deposits. Many years ago Knopf (1929),
neutral or alkaline, mainly the latter. Those at studying the Mother Lode System of California,
Whakarewarewadescribedby Grange (1937) are proposedthe hypothesisthat the silica in the veins
particularlypertinentto the questionof the transport was derivedby alterationof the countryrocks. I
of gold in chloridesolutionsin the presenceof abun- took up this hypothesisat Yellowknifeand was able
dant silica. Thesewatersare alkalineas emphasized to show by analysesthat this is preciselyhow the
by Grange,not acid as proposedby the theoryunder silica in the quartz veins is derived (Boyle 1955,
discussion.A similarsituationprevailsat Steamboat 1961). Later chemicalwork, not yet published, has
Springs as describedby Brannock et al. (1948). amply confirmedmy findings not only for green-
Other similar occurrencescould be mentioned, but stonerocksbut for variousporphyries,granites,and
these are sufficientto show that in natural systems other types of rocks. It is evident that as water,
gold and silver are transportedmainly in alkaline carbon dioxide, and other volatiles attack the coun-
chloride solutions,regardlessof what the thermo- try rocks large amountsof silica are liberated,and
dynamicequationsmay predict. The state of the this silica is transferred to local dilatant zones where
gold in thesenatural chloride-bearingsolutionshas it crystallizesas quartz. There is, therefore, no
not beendetermined. It may be presentas chloride needto transportsilicaany distancein hydrothermal
complexes. On the other hand thesesolutionsgen- solutionsas proposedby the authors.
erally containmuch sulfur, antimony,or arsenic,a The authorsseemto assumethat gold-quartzveins
feature that again suggeststransport of gold as a are predominantlyreplacements of pre-existingrock.
complex of these elements. I doubt that this is the case. Most quartz veins and
That gold- and silver-bearingsolutionsare highly lensesoccur in structural dilatant features, and there
acid (pH 2-4) is not supportedby the natural data is actually little removal or transfer of rock com-
that I have collected. More generallythey are neu- ponents except in the wall rocks adjacent to the
tral or alkaline. The argumentin the paper under dilatant features such as fractures, faults, or open-
discussion that only acid solutionswill leachalumina ings on the anticlinesof foldedrocks (saddlereefs).
is not entirely valid. Aluminum is an amphoteric The wholesaleremoval of rock componentsto make
element whose oxide has two marked solubilities,one way for quartz veins and lensesis not generallya
at approximatelya pH of 4 and anotherat a pH of chemicalfeatureof mostgold-quartzdeposits.There-
10, the latter indicatingthat alkalinesolutionswould fore, large amountsof acid hydrothermalsolutions
certainlytend to leachsomealumina. The transfer seem unnecessary.
percentages for aluminain many of the wall rock The authorsdo not seemto appreciatethe complex
alterationzonesof gold-quartzdepositsare not high chemicalsysteminvolvedin the precipitationof gold-
(Boyle 1961,p. 124) indicatingan environmentnear quartz veinsand lensesfor they make the statement
the neutral point, in someveinsprobablyslightly on If the fluids moved aggressivelythrough the rock, there
the acid side and in othersprobablyon the alkaline would be little chance for development of alteration
side.
mineral assemblagesproduced by differential attack
In a simple systemone probablyneedsan acid through ionic diffusion on the silicates adjoining the
solutionto transportiron, if in fact, iron is trans- veins. Furthermore, there would be little change in the
portedin the solutionsthat depositgold-quartzveins. compositionof the vein solutionas a result of dissolving
The data availableto me do not supportany wide- the wall rock. Under these conditions, the mechanism
scaletransportof iron. On the contrarythey support responsiblefor the precipitationof quartz and accom-
panying gold is independentof the chemical and min-
the late ProfessorMcKinstry's (1957) contention eralogic environmentof the gold-quartzvein.
that much if not all of the iron in wall rock alter-
ation zonesand gold-quartzveinsis derivedlocally Such a situation probably never prevailed. Most
from the rocks on which the depositingmedia have gold-quartzveins in volcanicrocks,porphyries,and
acted. One alsowondersabouthighly acid solutions granites are marked by intensivezonesof wall rock
depositingcarbonates in gold-quartzveinsas pointed alterationin placestens of feet in width. Only in
out by Hemley in the note appendedto the paper. certain sediments are the alteration zones absent or
I feel that the authorsgreatly underestimatethe very
only developedon a minor scale. Certainly the
common occurrence of carbonates in gold-quartz precipitationof most gold-quartzveins has involved
veins, evenin someof thosethat have a gold-quartz- reactionsbetweenthe depositingmedia and the host
alunite association. rocks.
Any theory purportingto explain the origin of The authorsplacegreat emphasison temperature
gold-quartz veins must as a primary consideration as being the controllingfactor for the depositionof
take into accountthe derivation and chemistry of gold-quartzveins. This is a debatablepoint. The
114 DISC USSIONS

vertical range of precipitationof many gold-quartz pal mechanisms


in the formationof mostgold-quartz
veinsis very greatin someplaces,frequentlyseveral deposits(Boyle 1959, 1961, 1963).
thousandsof feet without a marked changein the The problemof the transportof gold in nature is
tenor of the ore. This suggeststo me that temper- not a simple one, and it is certain that no single
ature may be only of limited importance. Of more complexis the responsibleagent. To emphasizethe
significance
is the dilatancyof the structurein whichcomplexityof the problem,I have for instancefound
the gold veins and lensesare present. If there is gold to be migratingin the permafrostzoneand con-
no dilatancythere is no deposit. Dilatant zonesare centratingin ice veins (Boyle, 1951). In mostgold-
sitesof lowpressure andhencelowchemical potential quartzveinsarsenicand antimonycomplexesappear
within a structure. I suggest,therefore,that pres- to be the principalagentsof transport. This is sug-
surechanges are far moresignificant
thanare changes gested by the nearly constant associationof gold
in the temperatureof the systemdepositinggold- with arsenicor antimonyin most gold-quartzde-
quartzdeposits. posits and the common occurrenceof aurostibite
acid sulfate- (AuSb.o) in many veins. Sulfur complexesappear
The origin of gold-and silica-bearing
chloride waters in "red bed" sediments does not to be responsiblein other settingsand tellurium com-
appealto me. Suchsediments maygiveriseto solu- plexes in still others. Chloride complexesmay be
tionsthat precipitateothertypesof mineraldeposits, importantfor a few veins, but we still require much
but I doubt if they accountfor gold-quartzveins more proof than a few thermodynamiccalculations
and lenses. I can find no referencesto an association to confirm that this is true.
of gold-quartz
depositswith "redbeds,"andin my Finally, I wouldlike to say that the authors'view
experienceI haveneverseengold-quartz depositsthat thosewho haveinvestigatedgold-quartzdeposits
anywhere near "red beds." My colleagues and I havenot paid attentionto the geological,and I might
haverecentlyinvestigated
a barite-sulfide
depositin also say the chemicalcharacteristics, seemsto be
red bedsthatmayhavederivedits constituents
from basedon an inadequateknowledgeof the literature.
brinescirculatingthroughthesebeds (Boyle and As a chemistI admire efforts to quantify the geo-
Jambor,1966). It contains
abundant silverbutonly chemistryof ore deposits. As a geologistwho has
infinitesimalamountsof gold. My statisticson the spentmuchtime examiningore depositsin the field
occurrence of gold-quartz
veinsshowthemto be in I realizehow complexthe chemicalsystemsare. I
or nearvolcanicrocks(greenstonesand propylites), am not impressedby the moderntrend of warping
porphyries of varioustypes,and shale,quartzite, thermodynamicand synthetic investigationsinto
slate and schistsequences of marine origin: The theories that fail to take the field facts into account.
goldmayhavecomefromtheserocks. Gold-quartz R. W. BOYLE
deposits
are remarkably
rare in or nearcontinental
sediments. GEOLOGICALSURVEYOF CANADA,
OTTAWA,
The enormousvolumeof water (2.3 X 108 tons) November 26,1968
required
by theauthors to precipitate
a quartzvein
1,000feet high,1,000feet longand onefootwide REFERENCES
doesnot seemto me to be geologically
feasiblecon-
sideringthegeneralgeological natureof gold-quartzBoyle, R. W., 1951,An occurrence of native gold in an ice
lens, Giant-Yellowknife Gold mines, Yellowknife, North-
veins.To provide for flowsof 10,000cubicfeetper west Territories: ECON.GEo,..v. 46, No. 2, pp. 223-227.
dayas the authorssuggest wouldrequirean open --., 1954, A decrepitationstudy of quartz from the Camp-
fractureor fault extendingfrom the sourceof the bell and Negus-Rycon shear zone systems,Yellowknife
Northwest Territories; Geol. Surv. Canada Bull. 30.
solutionto the surfaceor to an open reservoirin , 1955, The geochemistryand origin of the gold-bearing
therocks.A fewgold-quartz
deposits quartz veins and lensesof the Yellowknife greenstonebelt:
maybeformed ECON. G•.o,.. v. 50, p. 51-66.
in sucha plumbing
system,
buttheyarerarein my --., 1959,The geochemistry,origin, and role of carbondi-
experience.
Moregenerally
gold-quartz
veinsand oxide, water sulfur, and boron in the Yellowknife gold
lensesare blind,especiallythoseformedin great deposits,Northwest Territories, Canada: ECON.GEon.v.
54. p. 1506-1524.
schistor shearzonesand thosedepositedin saddle , 1961,The geology, geochemistry,and origin of the
reefsand other structuresin sediments(Bendigo gold depositsof the Yellowknife district: Geol. Surv.
type). Theyare completely in most --.,Canada
surrounded Memoir 310.
1963,Diffusionin vein genesis;Symposium--Problems
cases
by schist,
faultgouge
andbreccia,
or country of PostmagmaticOre deposition,Vol. 1: Prague 1963,
rock and showno evidenceof everhavingbeencon- p. 377-383.
nectedwith openconduits alongwhichmassive , and Jambor,J. L., 1966,Mineralogy,geochemistry and
origin of the Magnet Cove barite-sulfidedeposit,Walton,
volumesof solutionhavecirculated.Facedwith N.S.: Trans. C.I.M.1V[. wok LXIX, 394-413.
thisgeological
factI havebeenforced
to concludeBrannock,W. W., Fix, P. F., Gianella,V. P., and White,
thatdilatancy
anddiffusion
processes
aretheprinci- D. E., 1948,Preliminarygeochemicalresultsat Steamboat
DISCUSSIONS 115

Springs, Nevada: Trans. Amer. Geophys.Union, vol. 29, division, Rotorua and Kaimanawa Divisions: New Zealand
No. 2, pp. 211-226. Geol. Surv. Bull. No. 37 (New Series).
Ebbutt, F., 1948, Relationshipsof minor structures to gold Knopf, A., 1929,The mother lode systemof California; U.S.
deposition in Canada in Structural Geology of Canadian Geol. Surv. Prof. Paper 157.
Ore Deposits: vol. 1, pp. 64-77. McKinstry, H. E., 1957, Source of iron in pyritized wall
Grange, L. I., 1937, The geology of the Rotorua-Taupo Sub- rocks: EcoN. GEOL.v. 52, p. 739-754.

EVOLUTION OF THE FORE-SUDETI•N COPPER DEPOSIT

Sir: In our paper (EcoN. GEOL.,v. 63, 1968, pp. TABLE 2. The Pressureand TemperatureChangesduring
the Evolution of Fore-SudetianCopperDeposit
372-379) we omittedto attachTable 1, Table 2, and
the list of references. These are now given below. Thick- Pres-
hess of sure
TABLE 1. Division of Zechsteinin the Top-Soil (kg/ Temp.
Fore-Sudetian Monocline Period (m) ccm) (øK)

Litostratigraphical Thickness Cyclothem Quaternary 50 162.5


Level (m) Middle Polish Ice Strata =
Ice Age 312.5 1500 m
Upper Red Mudstone 10.0- 32.0 Cyclothem 5 (bottom) Rocks Strata =
650 m
Light-Gray Anhydrite End of the
or Gypsum 0.2- 0.5 Cyclothem 4• Neogene 600 150.0 293.2
Lower Red Mudstone 3.5- 12.0
Light-Gray Anhydrite 0.0- 4•2.0 Cyclothem 3 Beginning of
Gray Mudstone 2.0- 14•.0 the Neogene 250 62.5 281.5
Light-Gray Anhydrite 16.0- 35.0 Cyclothem 2 End of the
Gray Dolomite 0.0- 16.0 Trias 1,250 312.5 315.0
Upper Gray Anhydrite 20.0- 50.0 Cyclothem1 End of the
Rock Salt (Sieroszowice) 0.0- 76.0 Perm 250 62.5 281.5
Gypsum Mudstone 0.0- 6.0
Lower Light-Gray
Anhydrite 30.0- 70.0
Limestone and Dolomite 7.0-110.0 J. OBERCANDJ. SERKIES
Copper-Bearing Shales
(Kupferschiefers) 0.0- 1.1 DEPARTMENTOFPHYSICALGEOLOGY,
Dolomite in the Bottom
UNIVERSITY•WROC[AW,POLAND,
INSTITUTE OF INORGANIC CI-IEMISTRY AND M•rAL-
Shales 0.0- 0.2 Cyclothem 0 (local)
White Zechstein Sand- LURGYOF•RAREELEMENTS,TECI-INICALUNIVERSITY,
stone WROC[AW•POLAND,
December 5, 1968

REFERENCES

Garrels, R. M., 1960, Mineral Equilibria at Low Temperature the Fore-Sudetian copper ore: Bull. Acad. Polon. Sci.,
and Pressure: New York, Harper Brothers. Ser. sci. geol. et geogr., v. 13, p. 1-7.
K•apcinski, J., 1959, The Triassic north-east of the Fore- Serkies,J., 1965b, Some physico-chemicalaspectsof cementa-
Sudetian Block: Rocz. Pol. Tow. Geol., v. 28, p. 361-408. tion processes:Bull. Acad. Polon. Sci., Ser. sci. geol. et
Konstantynowicz,E., 1967, Copper-bearingrocks of Sudety geogr.,v. 13, p. 85-89.
and Fore-Sudetian Block: manuscript. Serkies, J., 1965c,Effect of physico-chemicalfactors on the
Krumbein, W. C., and Garrels, R. M., 1952. Origin and structure of ore-bearing veins in the Fore-Sudetian copper
classificationof chemical sediments in terms of pH and deposit: Bull. Acad. Polon. Sci., Ser. sci. geol. et geogr.,
oxidation-reduction potentials: J. Geol., v. 60, p. 1-33. v. 13, p. 249-255.
Lgtowski, F., Serkies, J., and Niemiec, J., 1966, Application Serkies, J., Krason, J., and Idzikowski A., 1965, On some
of potential-pH diagrams for determination of the occur- differences between formation processes in the North-
rence forms of trace elements in some economic mineral Sudetian and Fore-Sudetian copper deposits: Bull. Acad.
deposits:EcoN. GEOL.,V. 61, p. 1272--1279. Polon. Sci., Ser. sci. geol. et geogr., v. 13, p. 195-200.
Serkies, J., L•towski, F., and Niemiec, J., 1966, Application
Oberc, J., 1962, Wroclaw Monocline and vicinity formations: of potential-pH diagrams to characteristics of some Zech-
Przegl. Geol.,v. 11, p. 573-575. stein copperdeposits:EcoN. GEOL.,V. 61, p. 1266--1271.
Oberc, J., 1966, In collective work: Problems of Legnica- Tomaszewski, J., 1963, Geological structure of area between
Glogow copper region: Wroclaw, Ossolineum, p. 79-82. Lubin-Sieroszowice: manuscript.
Oberc, J., and Salski, W., 1967, Folds and fissures of the Wojciechowska, J., and Serkies, J., 1966, The geochemistry
Lower Zechsteinrocks in the region of East Shaft Lubin of rhenium in the Fore-Sudetian copper deposit: Bull.
Mine: manuscript. Acad. Polon. Sci., Ser. sci. geol. et geogr., v. 14, p. 1--6.
Pourbaix, M., 1963, Atlas d'Equilibres •;lectrochimiquesfi Wojciechowska, J., and Serkies, J., 1967, Traces of gold in
25ø C: Paris, Gauthier-Villars. the Fore-Sudetian copper deposit, region of Lubin: Bull.
Serkies, J., 1965a, The possibility of supergenicchangesin Acad. Polon. Sci., Ser. sci. geol. et geogr., v. 15, p. 107-112.

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