6 vis WF 2 Chapter 6 Characteristics and Genesis of Epithermal Gold Deposits Davi R. Coxe! Jor Ow Deposit Resenarh, University of Tasmania, GRO, Box 252-79, Hobart, Tasmania, TON, Austatin TUART F, SIMMONS Coathermal lativute anu Geology Drpeotment, University of Auckland, Priva Bag, 9201% Awrhland, New Zewlend Abstract his paper summarizes the characteristics of epithermal gold deposits and discvises potential ore de penition mechanisms. Epithermal deposits mostly form at shallow erusta levels (el ke) in sihacvial vole "canic settings. There are two clases of epitherival deposits which ean be icriminated in terms of thei xcologie environments, alteration mineralogy, and iluid chemistry: (1) low-sulfdation epithermal de: penits which ave spatial associated with magias, where ove deposivon generally occurs several Kime. tere abiose the site of iatrision, and quautzatduariasericite-carbonstealteration asseablages are cha ‘crise: and (2) high-sulfidation epithernsal deposits which have a closer spatial association with desing. Calealkaline magmas and ave characterized by residual quartz and hypogene advanced argillic alteration inscinhliges (quart ahinive-kaolinite psrophsite) The waters that precipitate lew-sulficiation epitherinal mineralvation have isotopic compositions that are consistent wih 4 predominantly meteoric source of water, and a magmatic valaile source for sll a fcushon. Alteration and vein mineral assemblages are consistent with near-neutral pH conditions. HS) is the predominant sulfur species in the mineralizing solutions. Temperatures of ore deposition are less than 400 € aud salinities are low (35 94 NaCl equi). High dissolved ges concentrations (CO, HS) feu increase the eepah of initial boiling ighssulfdision epitherml mineralization preeipitaes fiom waters that are predominantly maygmtic in origin, lise ov oxigen, hydrogen, and sulfur sowpe compositions, Oxidizing, sili waters form via the dispraportionation of magmatic SO... which generatesabundant sulfuric acid sue minor HLS. Ten peratites wary widely (HKP-UN°C), bit Slnities are generally Tow (<3 wh % NaCl equis). There i ve Mid inclusion evicence for magmatic brines in some deposits, These isubstantil mineralogical, aid inclusion, anc stable iotope evidence for boiling i low-sull lagi epithevaval satems and iran be a highly elfective process for electra deposition. Fhtid mining is less like co ne smspartant for ave formation. Mixing within the ore sone is generally resteicied te late= sage collapse of the hyerotheratal system, which allows descent of steamheated waters into the mineral. ive ensivonment and produces barren carbonate or sullate gangue, ‘Some high-wlfdation deposits contain vaequivocal isotopic and fel inclusion evidence for Hil mi ing. However it remains unclear whether mixing is responsible for ore deposition, gangue deposition. or conrielment of metas in gronnd waters For any given high-sulfidation deposit ifacid chloride hrines ary colts. ehiloice complex, then etution, cooling, and /or pH inerease can eanse gold w deposi, pow Sie ssing unising with ground waters, By contrast, gold is ransported asa hycrosilfide comple i i Tue aici yeters then gold may deposit in response to boiling oF to mixingrinduced oxidation. but not te enpprate, xilnity and pH changes. Introduction classification scheme for hyclrothermal ore deposits prom posed by Lindgren (1938). On the basis ofstratigraphic v6 Entirevtat gold deposits form in the shallow parts of — lationships in voleanie stratigraphy, but also by analogy with magmia-related hydrothermal ssstems, commonly in sub- mineral and metal occurences and mineral testes in aerial volcanic aves (Fig, 1). The deposits are host to both modern geothermal systents, he inferved that epithermal precious and axe metals but are aow mainly mined for deposits formed at <200°C and <100 bars their gold and silver contents, which ean be substantial in There was little advance in the understanding of ep- total production and can achieve spectacular bonanza _ithermal deposits until they became a major target of e: grades. The term “epithermal” derives from the genetic ploration as the price of gold rose in the 1970s andl 1980s. Fluid inclusion studies extended the temperature range of "aovvespanaing ston: en, eotaxin epithermal deposits to about 300°C, and stable isotopes 221 eCCOOKE AND StunoNs, ee oa oe sSiovmmtscee'binale Potrg sop lea oer | Mead : ) fe veto tes Seve 1 Mi | | FL, Selec diagram showing the postions of lar and high-ullidation «pithersal convents (sh Bye spectively) within hyerotbermnal stems ansorated with lowe sae seth atest yt (oie Hones and Eli, HS). A. The epitherinaf environment represented "> Meter ware ee reper at > La ougle convectin ate bs eat Foy a stein cea ag AL cep 102 hs fe tater table. wabin the npfiow 700}, mina temperanrespessire gradients ave came to Indiematic og Lele ToR3)- At hater level che dante racent cases rng Hd nose acral espe Ayton by ising with local growl waters 4 oem oti 0nex The thee elanentoey water t pe th om fuyrstEdation epiiernal enirowatert shor ave koma roo exphivotion dein, Buss ate ae ont Iclrostenl pune a a the moe nsporean For secon taper of prccee setas, These wel inenictions betwen deeply iris meteoric water ad magmatic somponeets (HAO, SO HL LICH neat the Ine ofthe eonveetion cel and sbaequene Mucpineral interactions (Giggenet, £7 peat. Thc ther too water pes are seat hese groin waters that gin Rest i aque ton ‘afta [enohaining sypot COs. HS) which separace ens deeply holier ‘eve comaining high eoncentexions of dissolved CO, (10 0 Ky tend Io acme sen Fese ‘he amore stagnant tagine dag 0 1,00 Beto the Water table thew dyion ees! Rae st Breland eden, 18}. Aci sia steaee att waters contin Tl eure ations slate 1 NN sR) Mt ve Irn oxidation of HS inthe wade zone, These weters dribble ous t he eer ewer Ue ks nits CO. bors. seambeated or eoride waters andl become rettalized within ew tensof meters (Seo etal. FITH Thee {stan af Hhege water aypes gels depen pin wprgraphicallscontesfed frie. fi lew elie cts sso ised with shyolgcwoleannn, the seanvheated water O€cut ove. ae on, she peter of the eles wey Dome. 6, The wsushapest hatched zane eepresent he epiteraia environment I Toco sea th sl Pax seanic cone nid above a desing saga i his set. acd de envi an ingle ai alates seid ehosidesulate waters. The outflow Zane fete om the hse edie wale able (aed lie wil tt flows the trace of topogtaphy)(CHARACTERISTICS AND GENESIS OF BPFTHERMAL, GOLD DEPOSITS proved the prevalence of mneteorie waters in the ore-form- ingenvironment (eg., Nash, 1972; O'Neil and Silberman, 1974; Kamilli and Ohmoto, 1977: Sawkins et al. 1979; Buchanan, 1981). Theoretical and experimental tech= niques were used 10 determine metal solubilities and min- eral stabilities under hydvothermal conditions (e.g., Bar on etal., 1977; Barnes, 1979), which led to numerical simulations of reaction paths and ore formation (Reed, 1982: Drummond and Ohmoto, 1985; Reed and Spyehe 1985; Spycher and Reed, 1989). Meanwhile, in New Zeakund, the United States, and other counties, the de- mand lor cheap clectricity involved geothermal explo- ration drilling and development, At depths of less than That, temperatures and pressures similar to those in the epithermal euvironnient were encountered (e.g., Henley andl Elis, 1083), Precious and hase metals were found to be wansported and deposited in wells and surface pipes (e.g, Weissherg, 1969, Hedenquist and Henley, 19854; Brown, 1986; Christenson, 1987: Krapp ane Seward, 1987), By the mid 1980s, genetic models hael been formukited to explain focenvences suid sonations of metals and minerals, to de- mareate the phisical-chemical conditions of ore deposition, in several epithermal deposits, and to speculate on the sources of fluids and metals (e.g., Sawkins et al., 1979; Buchanan, L081; Berger and Eimon, 1983; Hayba et al. 1985; Heald et al., 1987). In these models, hydrology was seen be an essential factor influencing ere deposition: howevex. only now can the terms “boiling” and “mixing” be applied as causative agents, Carlinaype deposits were included in the epithermall realm by several workers (6 Berger and Bethke, 1985; Berger and Henley, 1989), but they were later elefined asa distiner class of hydrothermal deposit (White and Hedengquist, 1990; see Hofstra and Cline, 2000). The modern use of the term “epithermal thus retains much of Linegren’s intent, although the ther- imal regime extends ~300°C wth formation depths no ipreater than 2 kin below the water cable, Lindgren (1933) showed that despite sharing common gangue mineral assemblages (c.g., quartz, carbonate, adit lariat, clays, Muorite, barite, pyrite), metal inventories of de posits were widlexanging, with varying proportions of gold, siler, and base metals, inetuding mercury, animony, tel lurium, ane! selenium, Nine subclasses of epithermnal de posits were thus grouped. Among these, gold alunite and gold telluvide remain distinguishable, whereas the remain- der are scen as part of a spectrum of deposit type termed low sulliciaion” (Hecenquist, 1987; White and Heden- guist, 1990, 1995; Hedeniquist et al., 1996; Hedenqutist and Arribas, 2000), “adithivia-sericite™ (Hayba et al, 1985; Heald ct a, 1987). or “low sulfue™ (Bonham, 1986). Low sulfidation refers 10 the predominance of reduced sulfiw species (HS", HS), whereas the adulariasericite classifica tion emphasises the neasneutral pH of the ore-forming fluids. Gold alunite deposits re now referred to as “high: stillidation” deposits (Hedlenquist, 1987; White and Heden- aquist, 190, 1995; Hedlenquist eval, 1996; Hedenguist and Arvihas, 20000), but these were also called “acid sulfate” and alunite-kaolinite” (Hayba et al,, 1985; Heald et al., 1987; 2s Berger and Henley, 1989) and “high sulfa” (Bonham 1986). High-sulfidation refers to the presence of i signif cant component of oxidized sulfur species (IISO;. SOF SO.) in the ore-forming fluids, whereas the gold alunite acid Sulfate and alunite-kaolinite nomenclature enaphasices their acid pH and hypogene sulfite mineralogy: Gold tel- luride deposits (e.g., Cripple Creek), which share several mineralogical similarities with low-sulfidation deposits, are considered separately. appearing tw be genetically Hinked 10 the emplacement of alkalic igneous rocks (Bonhan, 1986: Richards, 1995; Jensen and Barton, 2000) In this paper. we review the genesisol golé:besring, low sulfidation, and high-sulfidation epithermal deposits, and. wwe draw heavily upon several excellent summary papers of the last decade (White and Hedenquist. 14; Silliwc, 1993a, b; Arribas, 1995; White et al., 1995; Hedenquist etal, 1996). In doing so, we focus on 12 wellstutied rep: resentative deposits of the Pacific tim, the Caribbean, and southern Europe, where detailed mineralogical studlies in clude fluid inclusion and stable isotope dats. These resilts provide insights into the physical and chemical conditions Of ore deposition aswell as clues about the origins ol Ties and metals. In places, we refer to other deposits and stuck ies to highlight a specific relationship or 19 comment on genetic interpretations. The selection of lowsullidation de posits (Tables | and 2) reflects a range of deposit styles With a world class gold resource. By contrast, the selection of high-sulfidation deposits (Tables I and 2), which tend 10 contain a much smaller resource, is restricted 16 the sal ability of well-studied deposits. We also review the cond tions of gold transport and deposition sand view these in light of studies of modern epithermal cusironments, We discuss the most likely mineralizing water compositions in epithermal environments from the perspective of gold transport, and compare and conteast possible depositional processes, ‘Tectonic-Volcanic Settings, Space-Time Relationships, and Orebodies Epithermal-related hydrothermal systems are generally associated with subaerial volcanism and intrusion of cae kaalic magmas that range from basaltic andesite to andesite to dacite to rhyolite, Submarine examples ave also known (eg, Sillitoe et al., 1996), Inuusionsrelated hydrothermal activity results from plate subduction and niagenatismn in both island- andl continentakare settings, The apparent tb sence of epithermal deposits in hydrothermal systems as ciated with continental rifting or hot spot activity (e... East Africa, Iceland, Hawaii) suggests a strong cause snd elleet Tink between subduetion-related magnratism and ore for ‘mation (Sillitoe, 1993a). Although associated with a nts form fault structure, the emplacement of the Clear Like voleanie rocks and epithermal mineralization at Melatgh: lin, California, have been related to «un isolated subducted slab associated with the Farallon plate (Isherwood, 1942) and localized extension within the fold and thrust belt of the Coast Ranges (Tosdal et al., 1995). Although it appears that extensional tectonics are important, theve seems to be(COOKE AND SIMMONS 24"v2 3 =io generid enistalseale control on the localization of oe fornting environments (Sawkins, 1990; Sillitoe, 19934) Most epithermal deposits are Cretaceous or younger (ex Silltue, 1993). Older deposits are known, most no- ably the Paleozoic deposits of the Tasman fold beltin east. crm Australia (64, White et al, 1995). Since plate margins are regions of uplift and erosion, epithermat deposits gen conally have poor presesvazion potential, given their shallow dlepsh af formation. Furthermore, because high-sulfidation leposits can forny iat shallow levels in active volcanic edi fives (e.g., Fig. 1B), resurgent explosive voleanism can also desiroy these mineral deposits and/or their precursor ace live geothermal system, Although low- and high-sulfidation systems are largely products of subierial, magmaerelated hyelrothermal activity hoth mineralization sevies rarely occur in the same deposit. Bxceptions include Comstock Lode (Vikre, 1989), Em- peror (Eatou and Seuerfield, 1998), Masupa Ria (Thomp: son etal, 1994), and Lepanto (Hedenguist eval., 1998), al- thongh for each of these examples, the bulk of ore-grade mineralization isyestricted to either low-sulfidation or high- sulfidiation environments Epithermal districts cover areas hac range from a few km? to several res of km#. Orebodies are commonly usted by nearcoeval or older voleanie rocks, “basement” (metisediments anid metavoleanics), and/or rarely by sub- woleani¢ inwusions, The shapes of orebodies are variable, bnut they share the common feature of being zones of paleo permeability. Orehodlies extend laterally hundreds to thow sindls of meters (in maximum dimension), oceupying veins tdhat_ may be no move than a meter to several meters wide, Vertically. they ten! to be restricted to <600 m as exempl- fied by minevalizagion in the Pachuca-Real del Monte dis- ict (Big. 2). High dissolved gas contents in the fluids can extend the depth of first boiling (Hedenquist and Henl 1985), and this is helieved to have resulted in a vertical in. terval of ore mineralization that exceeds 900 m in the Baguio district (Cooke et al., 1996). Postore fauluing can, extend the vertical interval of mineralization, as isthe case at Conistock Lecle (Vikre, 1989; Hudson, 1993). Structure, lithology, and fluid composition influence the permeability of oreforming environments (Sillitoe, 1993p), Orebodies are found in steeply dipping veins (J=10'm wide} and vein swarms, stockworks, and less com monly, lowsngle veins (e-g., Comstock, El Indio, Hishikari, Lepanto, Mejicana, Round Mountain, Tayoltita}. These lo- cealized [uultsare the produces of extensional and transten- sional stress regimes that are regional in scale, but in many eases the fults have offsets of no more than a few meters, They require brittle failure as controlled by rock rheology. Mincral precipitation and dissolution by hydrothermal solutions also affects permeability. In low-sulfidation envi= ronments, permeability is reduced by quartz and calcite de- position, In contast, permeability is entianced in high-sul- fidation envivonmencs by acid solutions causing rock dissotution and formation of vuggy quartz. If fluids in et ther ensironment have high gas contents and are subject to sharp pressnre reduction, Mashing and hydrothermal erup: 5 CODK AND SIAIMIONS permeable hyeceia zones (¢ van Leeuwan etal, 1990; Lihit, Carman, 994) The aforementioned features are general aiwihntes of epithermal deposits. The charsezeristies thi distinguish lowsulfidation from high-sulfidation deposits ave empha sized below: tions ensue, forming 4. Relian, Low Sulfidation Mineralogical patterns in the vicinity of oxe-giadle snate rial provide the diagnostic evielenee that distinguishes low and high-sulfidation environmenis, ically portrayed in Figure 3. Ore in lowsnifidation deposits is generally associated with quartz and/or chaleedony, plus lesser, but variable, antounts These ave gr of adularia, calcite, thodochrosite, K mica (illite oF sevicite), chlorite and pyrite gangue. Lattice textures (pkuy caleite and its pseudemorphs) are conmyon wexieral ehaneteris: ties, as are crustiform and collofori bands, patienluly in shallowly formed veins (e.g. Hishikwi, Mel awghit7}, Collo- form bands were most likely deposited as aniorphons silica (eg. Fownies, (985), exystallizing to quarts with time. In deeper veins, coarse erysialline Comb quartz is common (egs Comstock, Tayoltita). Gold typically occurs as elee- trum or more rarely as telluridles (¢,,. Aeupaan) in asst Lion with acanthite, silversulfosalts, hase metal sulfides, ann pyrite (Table 2). From the vein selage innto the sudjacent counury Fock, aeularia gives way to illite, quire ieaendtance diminishes, and pyrite is comreion throughout. AILof these minerals reflect ove deposition in the presenec of a reduced and near-neutral pH lowsalinity water, Deeplevel andl re gionalscale alteration consists of a propslitic assenibkige containing quar chlorite, illite, pyrite, cileite, albite, ad. laria, and epidore (e.g.. Acupan, Comstock Lode, Romad Mountain, and Tayoltita). The intensity of alteration Largely depends on the existence of veuctive hist rk, cominonly volcanic, as well as porosity zee peruycabiliy Silica siier is deposited where boiling or boiled low-sul fidation fluicls discharge at the surface (Fig, 1A). Sinter nie tially precipitates as amorphous silica batt crystallizes ‘quartz within 50,000 years (Heedianjta et al, 2000). Siliea sinters demarcate the palcosurfaee jul the paleowater table and are commonly founid at he sume Tevel as the al. eration assemblage comprising ahunise, kaolinite, and opal, which form in the presence of acid sulfate steamy heated waters (Fig. 1A), Atdepths beaveen the paleowater table and mineralization (and sosneviies lateril 0 miner alization), rocks are variably altered yo clays (smectite, in terlayered illite smectite, illite, chlorite, kaolinite) and car bonates; veins are filled with earhonate (eg. Comstock Lode, Round Mountain, Hishikari). ‘These minerals ea form from COyrich steamheased hicarbonate waters (Fig. 1A; eg, Sbmnons et il, 2000) Fhuid inclusions Fiuid inclusion data are used! w deduce the emperanires and compositions of mineralizing fluids along with the formation depths of a deposit. They provide important constraints on the genesis of low-sullidation deposits,CHARACTERISTICS AND GENESIS OF EPITHERMAL GOLD pExOSITS 27 Pachuca - Real del Monte district - vertical extent of mineralized veins 00 EXPLANATION oa i= — ore neva Fc. 2 One ines tro loseaifiation epithermal veins in dhe Pachuca Real del Monte ditriet, Mesiew thea Gexne eta 18), Thereare over 100 veins irabia world chee AgAn district, The dseictvide upper snl lower its ‘hae winealize! hewn range 2.200 9 20m elev burn ideal veins, the elevations and vertical extents min hata ile eatCOOKE AND SIMMONS. Low Sulfidation crustiform | altered banded ore with host lattice textures rock High Sultidation disseminated | altered massive host Kaolinite (pyrophylite) ore rock _+/- sericite /illte mA smectite oes ‘smectite (| pyrite tite chlorite es calcite I oe epidote IH calcite nt pyrite \ Vi 3 epidote 2S quartz, chalcedony, | quartz adularia, pyrite, adularia base metal sulfides, | lite carbonates, Au-Ag| pyrite residual quartz (vuggy & massive), alunite, sulfides, sulfosalts, Au-Cu(-Ag) 110m T Quartz, lite / chlorite alunite a 2. Selemati diagram showing mine Foo Silt, 195) Most fluid inclusion daea fave been obtained from quart, which is volumetrically the most abundant min- ceral phase in ore material, Data have also been obtained for Auid inclusions hosted by calcite, adularia, and tvanslucent sphilevite. Bona fide primary fluid inclusions Uypieally ocewr in growth zones within medium: to coarse- grained euhedral quarts erystals (Bodnar etal, 1985). In epithermal deposits, sich material may be difficult to find and data may he obtained mainly from secondary incl sions (eg. Round Mountain; Sander and Einaudi, 1990), Sander and Black (1988) discuss the problems associated ‘wih studying Muid inchtsions hosted by crystallized and recrystallized silica niinerals, Furthermore, in many de- posits the best preserved fi inclusions occur in gangue minerals that gre mot intergrown with gold and may be separated from ore by several millimeters to meters of vein fil Most fui inclusions contain two phases (liquid + vapor) and ave liquichrich, with liquid dominating the volume by 368 percent. Vaporaich twoxphase inclusions are also com ‘han ln these, vapor comprises >98 percent of the volume, so that the inclusion cavity i lined wil a thin liquid film which is surely perceptible. Its usually impossible to mes sure either homogenization (T,) or ice-melting tempera tuves (T,,) from saporzich inchisions in epithermal env ronments (Roedder, 1984; Bocinar eta, 1985) logic zoning in low a Nigh dation epiahevna epost (eel Fluid inclusions range from irregular to smooth negative crystalshaped cavities; irregular shapes correkate wil peratures <280°C and smooth shapes correlate with tem: peratures 9250°C (Bodnar et al., 1985). Necking dl two- phase trapping of liquid and vapor are common and workers generally take care to avoid inclusions alfectedt by these processes. Even so, their effects are seen in the wide range of Th commonly measured in individual generations of fluid inclusions. Homogenization temperatures range from 150° 10 300°C: and icemelting temperatures range front 0" 10 -2°G, indi cating dilute Muids of generally less than 3.5 wt percent NaCl equiv (Table 2, Fig. 44) Hedenguist and Henley (1985b) showed that iccanelt ing temperatures between 0.0° 10 =1.5°C contd be solely attributed to the presence of aqueous carbon dioxide rather than dissolved salts (wt Se NaC equiv) as is com: monly interpreted. In some cases, crushing studies or gas analyses have demonstrated that the iccanelting tempers tures are at least partially due to aqueous carbon dioxide Sawkins et al., 1979: Vikre, 189: Sherlock et al 15). One other indicator of the gas contribution 10 ice melting temperature is the wend of the Ty-T, data shown in Figure 44. Curves IT and IIV show the cilvet of is loss due to boiling on the Ty-T,, data for a starting water that contains significant amounts (but less thant 1m) of dis(CHABACITIISTIES AND GENESIS OF BPITHERMAL GOLD DEBOSHIS: a 7 == Acupan be Comstock 200 2 Hishikan 2 [o> Motaughiin z 2 = Rouna mt 5 . == Tayoltta g 5 3 3 z zs ry = 2 S é so 2 ‘Temperature of homogenization (°C) 3 7 Lepanto 5 ” Nanwatsu on co Redelquiar be, : & *] = La Mejicana . < 3 —— El Indio ‘ 5 i 2 a 5 beens 3 | 77 ‘ : 5 é 5 5 Temperature of homogenization (°C) edenmyint and Henle, Ista: Sinnnane aid Christenson, 1984). The parent composition Ais similar to te ep Fide water (-0 75 Oy, 0.1 m NaCI, wheres B represents the compontion of the peripheral COsrich sesn-heset ver Cree I represents the effect of gas loss due to bailing fora water of the parent composition, curve I repre “ens the etc fis lose alter mining with seanrheated COteh water Cave represents che asin wend between Rhine sd core |sepresent the beng tend dae to Rayleigh evaporative tea lowe fd ps parent ‘i Simeone ane Simmons (1999) ad Snemons eta, (2000) sesertbe examples of Mil nelson data Er epithe thal depots where sch boiling trends ave interpreted.230) (COOKE SND SIMMONS Solved carbon dioxide. The gas loss trend is distinet from the boiling wend ofa dilute siline solution lacking any dis- solved gas (curve I, Fig. 4A). Mixing (curve Tl, Fig. 4A) can also allect fluid inclusion Ty and T,, data, For many data seis, the combined effects of mixing and boiling could ac. ‘count for the common clustering of data in the range 180° ty 270°Cand 0" 1 -2°C; ie, the data are bracketed by the boiling (IN) and mixing (2) erends (e.g, Hedenquist, 1990). Ina Jew eases, ieesinelting temperatures significantly layer than -2°C were measured (de Ronde and Blattner, 198s; Vikre, 1980 Cooke and Bloom, 1990; Conrad et al.. 1999; Sherlock et al., 1995; Scott and Watanabe, 1998), in- dicating the occurrence of waters with salinities exceeding. Lot percent NaCl. In deposits where obvious sources of brine, such as evaporites, are absent, these high salinities ‘ean be explained by variable amounts of evaporative con- centzatienr (steam loss) under open-system conditions (Sherlock ct al., 195; Simmons and Browne, 1997; Scott and Watanabe, 1998; Simeone and Simmons, 1999). The relatively saline parent solution of 4 to 6 wt percent NaCl interpreted by Vikre (1984) for Comstock is based on only five T,, measurements and may be revised with more data Using Hid inclusion data for geobaromecry and assum ing a hydrostatic boiling point for depth pressure gradi- em, estimates of the depth of mineralization range from. 100/10 5500 mi below the paleowater table. Figure 5 shows histograms of T, data from McLaughlin, where the post tion of the paleowater table is marked by the silica sinter thay hosts the top part of the sheeted ore-bearing veins, This fignre exemplifies the technique used by many work: ers to determine the depth of minezalization (e.g., Vikte, 1985; Cooke and Blowin, (990), Since hydrostatic pressure radients are common jn active geothermal systems (e.g, Henley, 1985), they are generally assumed in epithermal environments. As discussed by Sherlock et al, (1995), the partial pressure of gases (cletermined by gas chromato graphy) requives overpressuring of up to lithostatie values, . values in Figure 5. consistent with T Stabe isotopes Stable isotopes are measured in several of the commonly coccuyting mineral phases: oxygen in quartz, adularia, cal- cite, and clays; hydrogen in inclusion fluids and clays; sulfur in pyrite and related sulfides: carbon in carbonates. They hhave been used mainly to clecermine the source regions of aqueous and gascous constituents in mineralizing solueions and 1 help interpret paleohydrology (e.g., O'Neil and. Silberman, 1974; Kaaillianel Ohmoto, 1977; Sawkins et al., 1979; Matsuhist et al., 1985; Vikre, 1987; Conrad et al. , 1995; Matsubisa and Aoki, 1994; Sherlock et al, 1995), In general terms, the sulfur and carbon isotopes are consistent with magmatic origins for these components; however, scatter in data sets makes detailed interpretations difficult, Much more useful are the combined determina- tions of oxygen and hydrogen isocopes, which are used t0 interpret weer compositions, and hence, source regions, especially in young deposits where the composition of local meteoric waier at the time of mineralization can be confi- Eo Slee Ea 5 so 2 wo \ g \ os oa 7 100 14180 2208000 Homagenization temperatures (°C) Fic 5, Hid inclusion temperature of homoeization at plead hiagramsasa funetion of depth compare tion a esa ‘aporsaturate euives fom Meath Dire Shesockt a, 15). dently interpreted from modern compositions (egg. Aew pan, McLaughlin) ‘The interpretation of the water oxygen isotope composi: tions is calculated from the temperature-dlependent equi- librium between water and mineral phases (¢.g.. Matsubisa etal, 1985) and therefore variability exists in the 0/0 water values, on the order of ay 2 t0 + per mi, dite to Uncertainty iz he equilibration temperatures, D/H values tend to show a broad scatter of up 10a few tens of per wil, presumably because they are measured from inclusion lu ids that may comprise several generations of fluids, These variations in isotopic compositions are much wider than those measured in modern hydrothermal systems and so the scale of interpretation far ancient systeyps iy uot as fine as for modern systems, where, for example, the ellects of boiling and mixing are readily identilied (c4g.. Gigyenbach and Stewart, 1982; Giggenbach, 1992) Data for deposits shown in Figure ba are representative of the tends, The oxygen and hydrogen isotope compoxi tions of mineralizing waters ypically plot to the right of the global meteorie water line indicating ‘yiations in the 80/100 ratio. The data in Figure 6A indicate that local meteorie water is generally ke dominant constituent of the thermal solutions. Linear arrays connecting the local meteoric water composi- tion with the interpreted thermal water compositions that trend to the right (ie., horizontal) of the meteoric water line are thought to result solely from oxygen isotope ex change between country rocks and meteotie water (ex. i i !Craig, 1968), whereas a corresponding increase in D/H rae tips creates positive slope that suggests magmatic water in- puts (e. Giggenbach, 1992). Although the data eannot be taken asdiagnostie, they elo suggest that magmatic water may contribute up to 10 percent or more of the overall isotopic compesition of the mineralizing solutions in some lowstlf, dation cpithermal deposits ¢e.g., Sawkins et al., 1979; Sim- ‘mons, 1995). Any magmatic contribution to the McLaughlin ‘pithernal cnsironment is masked by extreme increase in oxygen ivtopes dite to water interacting with the rocks of the Great Valley Sequence, which have 0/160 values higher thin igncous rocks (Sherlock et al., 1995) High Sulfidation High-sulfidation gold + copper + silver ores are intimately associated with quartz, hypogene clay, mica, and sulfate gangue (Table 2). Hypogene covellite, alunite, and native sulfur are characteristic. Some minerals that are common, in lowsullidation deposits (.g., calcite, rhodochrosite, adu- luvia) ave absent [rom highsulfidation environments, and ‘openspaccil lextuves are comparatively uncommon, Many high-sulficlation deposits are characterized by a central residual or vuggy quuartz zone, which is interpreted tobe thesite of intense leaching and alteration by acid flu- ids (pl! <2: Stollregen, 1987). Characteristic gangue min- eral inelude quart ancl minor alunite, clays (pyrophyllite, F laolinite,clickite), diaspore, barite, zunyite, native sulfa alunino-phosphate sulfite (APS) minerals, rutile-anatase and pyrite. Ore minerals inelude gold, electrum, enargite- luzonite-fumatinite, tennantite-tetrahedrite, chalcocit bomie, chaleopsrite, covellite, and tellurides, Ore miner- alscan occur within secondary porosity (*vugs") generated byacid leaching of feldspars, other phenocryst phases, and breccia casts. The groundnyass is totally replaced by quartz, minor alunite, clavs, rutile (or anatase), and pyrite. Where the protolith isapluanitic, massive quartz may form, In ad- dition 1 vu alo occur in massive sulfide veins, quartzaluniteclay veins, and breccias, Zones ol alunite-quarty, kaolinite-pyrophyllite, smectite: ite, and propylitie alteration extend outward from the zone of residual quartz and mineralized veins over dis- tances of 1 10100 m (mostly 2-4 m: e.g, Lepanto, Nansitst, El Indio, Summitville; Fig. 3). Contacts between these mineral zones etn be knife-sharp. Sericite and pyro phyllite can extend! at depth below some high-sulfidation deposits (e.g., Lepanto, El Indio). Coeval and genetically related porphyry Carat deposits have been identified be- neath oi to the side of some high-sulfidation systems (e.g Lepanto, Lat Mejicamsa, Table 2; Paradise Peak, Sillitoe and Losson, 1994) There is a pronounced permeability contrast between, the vuggy quartz and clav alteration zones in many high-ul- fidation deposits. Deep weathering can strongly affect the residual quar zone, leaching sulfides and developing sec- ondary iro oxides aiel oxyhydroxides, and jarosite at sig- nificant depths in the mine environment, or even leach- ing them totally, In conuast, the impermeable advanced sid massive quartz, high-sulfidation ore can (CHARACTERISTICS AND GENBSIS OF BPITHERMAL GOLD DEPOSITS 231 argillic alteration zones are generally more resistant to ‘weathering and can contain fresh pyrite close to the pre= sent erosion surface (e.g., Summitville: Gray etal, 194) Rluid inclusions ‘The generally corrosive environment af ore formation linn its the material wailable for fuie inclusion studies. Most dat come from quartz crystals filling vgs, hough these ave con monly late, and from secondary inelisions in quartz phe= nocrysts, which are temporally unconstrained. Dats hase als deen obtained from enargite, alunite, barite, pyrite, sphae lerite, diaspore, siderite, and hiibnerite. Abunckant wails of secondary fluid inclusions ean make idemification of pris ‘mary fluid inchisions difficult (e.g., So et al.. 1998). fu rate cases, primary fluid inclusions have been documented to ‘occur within growth zones of euhedral quartz exystals (cg. Losada-Calderon, 1992; Ruggieri etal., 1997), though their relationship to ore genesis is unclear. Other workers have stated that primary uid inclusions are present, but they de not explain the criteria used to classify thean (e-g.. Mauneano and Campbell, 1995; Jannas et all, 199), High-sulfidation deposits mostly contain twexphase (liq uid + vapor) uid inclusions. Although both liquid-rich and vaporsich inclusions are recognized, most workers do not advocate boiling as an important depositional niechae nism (e.g.. Table 2). Rare multiphase brine inclusions that contain halite daughter crystals in aeition 10 liquid ane vapor + other daughter phases at room temperature hve been documented! from several eeposits (cag. Lar Mejieana Losada-Calderon and Bloom, 1990; Kastiga, Hedenquist ct al., 1994; Rodalquilar, Artibas et al. 1995); Furtei, Ruggient et al. 1997). Three-phase fluid inclusions th: ible CO, occur at Zijinshan (So et al., 1998) Microthermometric studies have revealed that some high-sulfidation deposits contain only dilate (cL to ~5 wt % NaCl equiv), moderate temperature (T), = 100'=850"C) wvo-phase fluid inclusions (e.g, Lepanco. El Indio, Pucblo Viejo; Table 2: Fig. 4B). Other deposits, such as Lat Meji- cana, Kasuga (Nansatst), Rodalquilar, Furtei, Summitville Paradise Peak, and Julcani, have fluid inclusions with sini- lay ranges in homogenization temperauures (some T,, val ues in excess of 400°C have been reported).but minch greater ranges in salinities (<1 to 46 wt S% NaCl equiv: Table % Fig. 4B; Arribas, 1995). Based! on fluid inclusion geobaromeity, estimates of paleodepths helow the water lable for high-sulfidation deposits range from 150 1 $00 m ¢Nansats), 60 to 680 m (Furtei), 300 to 700 mi (Lt Mejieana), and ~200 to 990 m (Rodalquilar). Stable isotopes Over the past decade, oxygen and deuterium: isotope studies have advanced our understanding of the forms. tion of high-sulfidation deposits significantly (c.x.. Rye et al, 1992). A variety of hydrous minerals that are suitable for analysis occur in different locations ane pargeietic stages within high-sulfidation deposits (e.g. alumite, kuoli- nite, illite). Oxygen and deuterium isotope analysis of thehydrous phases ane quartz has allowed Auiel evolution and. water saeteces in individual deposits to be characterized in detail In general, alunite has oxygen and deuterium isotope Compositions consistent with deposition from water pre- dominantly of magmatic origin (Fig. 63), Hedenquist et al. (2098) calculated that alunite at Lepanto precipitated fiom water which formed by condensation of up to nine parts mmaginatic vapor into one part meteoric water. Based fon oxygen and deuterium isocope compositions, the wae ters that precipitate hypogene clays, silica, and ore miner lization have a greater component of meteoric water rela- tive to those that precipitate alunite (e.g., Nansatst, Rodialquias, Lat Mejicana; Fig. 6B) Sulfur isotope data have been obtained from sulfide, sud fosalt, and sulfate minerals (e.g, pyrite, enargite, galena, sphaigrite, alunite, barite) and native sulfur, The data have deen aved to trace snlfr sources, estimate fluid composi= tions, aad for geothermometry (Arribas, 1995; Fig. 7). The source of sulfur is generally interpreted to be maginatic, though the sulfur isorope composition of the source is typ icaily calculated to be greater than zero in most deposits, up © a maximus of 9 = 2 per mil at Rodaiquilar (Fig. 7) Using pyrite-alunite isotope pairs, calculated equilibration temperatures range from 180° to 420°Cand are consisteste with temperatures ef SO, disproportionation in hy- drothermal fluids (Atribas, 1995) Sulfide minerals have distinctly negative BMS values in many deposits (Fig, 7), The negative sulfur isotope com- positions of sulfides and sulfosalts are consistept with sede Fide precipitation under osidizing conditions, with redox controlled isotopic fractionation driving enrichment of 8S, in the sulfides and sulfosalts (e.g. Heithersay and Walshe, 1995). Coprecipitating sulfates become progressively en- Hiched in, resulting in_the trend toward 55 valaes in excess of 30 per mit (Fig. 7) Epithermal Mineralization im Modern Environments Modern geothermal systems provide a context in which the mineral products of hydrothermal activity can be compared directly with coexisting fluids at known tem peratures, pressures, mass flows, and chemical compos tions. The lowsulfidation epithermal environment has heen explored by drilling a number of systems in vol- canie ares (e.g, Japan, Philippines, ladonesia, United Suites, Mexico), bat the best suidied are those in New Zealand, sich as Broadlands Obaaki where precious and dase mctals are depositing (Browne, 1969: Weissberg, 1969; Wensberg et al, 1979; Brown, 1986; Simmons and Trowue, 2000). By contrast, she higivsulfidation envi rome itis known only through surface study of thermal features of active voleanoes and the hydrothermally ak teed material ejected during their eruption, such as at White Ishind (Giggenbach, 1987; Hedenquist et al, 193). Both examples are Joeated ia the Taupo Voleanie owe (Fig. 8), providing a unique opportunity to exam inc the two subelasses of epithermal environments within dhe sime modem geologie context. COOKE AND SIMMONS Broadlands Ohaaki BroadlandsOhaaki shares many of the features of Jove sulfidation environments shower in Figure 1A, Over 50 wells have deen drilled at Broadlands Ohaaki over an area of about 8 km?, Most of these are vertical, ranging from 400 to 2,600 m depth. The deep (production) water is diltte (1,000 mg/kg Cl) with high concentrations af dissolsed gas (-26,400 mg/kg CO,, 100 mg/ky H.S). Iris nearneue ‘al pH, reduced and responsible for widespread alteration of felsic volcanic host rocks to quartz, calcite, Mite, adie latia, albite, pyrite, and chlorite a iemperaures t Figure 9A shows that precious and base metal sinevad ization occurs in three spacally distinct cusironments: in geothermal well scales and precipitates. at the Ohiaki Pool, and in vugs and veins in hydrothermally altered rocks (Sim- mons and Browne, 2000). The scales andl precipitates in geothermal wells contain the highest concentrations of gold and silver and are important for understandinng ore forming processes in lowsillidation environments. The drilling of production wells provides fyee low paths. for chloride waters to ascend to the surface. Here, steep, pressure gradients promote high nis flux, Hashing, aur mineral deposition. For example, platy calcite precipitates, ar the level where phase separation begins near the well feed point, due (0 exsolution of CO,. Such deposits ex: tend for only 100 t 300 m up the well (Tulloch, 1982). Ln surface pipes, electram and chiileapyrite deposit on back pressure plates, attaining spectacular concentrations of up fo 5 wt percent gold and 17 wt percent silver (Brown, 1986); downstream of these and the separator, ancorphous, silica deposits occur, commonly in collofoynr erustiform bands. In some cases, precipitates and rock detrites ave carried in the flow seream (0 the surface; theve seule out in the weir box where the chloride water discharges to the ate mosphere. These unconsolidated materials comprise amorphous silica, sulfides, and rock chasis nd contain up, to 100 ppm Auand 1,000 ppm Ag (Simmons snd Brswne 2000). Brown (1986) showed that the deep, preboiled chloride water at Broadlands.Ohaaki contains about 1.5 pg/kg Au and 8 j1g/kg Ag, consistent with subsequient analyses of Wa ters collected with a ceramiclined doniriote sumpler (Brown et at, 1997}, From thisand the average upflow rate for the whole system (~100 kg/s), Brown (1986) calculated that I Moz. of gold flows through the system in approxi= mately 6,400 yr By contrast to the wells, the soleiicie cocky tint are hy: drothermally altered by the chloride waters contain low amounts of gold and silver, with pnaxinian values of about L ppm Aw and <5 ppm Ag, despite sporadic occurrences of disseminated and vein sphialerite, galena, auc chalcopyrite (Simmons and Browne, 2000). ‘Mineralization at the surface is restricted to the Obaatki Pool (800 m2), which before exploitation discharged a mixed chioride-bicarbonate water (Hedenquist, 1990). In 1957, a red-orange focenlent was observed. and over the next few years, it became ineorpored into the siliea sinterCHARACTERISTICS AND GENESIS OF EPFTHERMAL COLD DEPOSITS oss aa 20 -| oft = 4 atone 3 ose Fe ~ ‘ret va % detrei secon a”) © antenctacssan QB -100 4 | 6 erosatanss-chaakt 120) D Metaughlin 4 tata 140 + st o 4 0 6 o 6 ® 8 2» "0 (%o, SMOW) od 3 20 =o” = 8 a a “ io ne a dei de gh e Selena | © Lawojcna-cuane 8 4 Q -100 © taMajena sre Lf ( anene otro some 120-4 © ore mnaasion sage / ° " 140 wo 4 4 5 0 5 30 (%,SMOW) a6 840: BD fn ineralrng watersineprete fr epthermal dept. A Daa fom quar andi Au ncn ran towadation depot B. Dats rm aac fom Rgholidaton dep (ee oA ‘ih 18 wis ana data ron Loma Calder, 18). The compan ofthe deep is ho Bro ‘Ohl anit Int ares soem A The ae of capstone of eater shaped tom ges Hates sides voles mtines te hx abe oleae spore (igen: HAE} the vo in felie melts onttinedt hy the ho labeled "Fence" (Tale, HME). Aves int T= hwate (Sanaa. Ka = Ranga (Naa, PV = Pueblo Viejo Ro = Rovtalia: Tining the pool, Analyses indicate that the precipitate com- prised amorphous antimony sulfide (metastibnite), with high concentiations of gold (85 ppm), silver (900 ppm), mercury (2,000 ppm). thallium (630 ppm), arsenie (400 ppm), aud artiniony (10,000 pny; Weissberg, 1969). This mineralization is similar to thatat the Champagne Poo! at Waiotapu and acid sulkite-chloride springs at Rotokawa (Weissherg, 1969; Hedenquist and Henley, 1985a; Krupp and Seward, 1987). All of these most likely share a com- inion formation enechanism involving effective scavenging of aqueous gold and silver from solutions undersaturated in precious metals onto amorphous arsenicamimony-sul- fur colloidal compounds in acid solutions (Renders and Seward, 1989). Although this syle of mineralization is not known in lowsulfidation orebodies, the process of gold scavenging may be relevant in Catlinaype deposits whese gold and arsenic show strong correlation (Hofstra sud Cline, 2000) In its natural state, oregrade precions metal mineraizt tion did not form in the BroadlandyOhaaki sem, een though the deep fluid was transporting substantial aqueous gold (Simmons and Browne, 2000). Insteud the requisite permeable channels for ore deposition, in which boiling and high mass flows are sustained, were formed by he cll of wells, reinforcing the concept that epithermal ore ebeposits ace mainly sites where metal deposition is ellcient234 COOKE AND SIMMONS = Sulides == Suiaes Wa 85m] TO sso, 7 7 T T = Lepanto te 220-420 26 Nonsatsu 1 FF 1 mmemiamme! 200-240 9 1 1 1 Puede Velo] — 1 om t | te0-260 Juleani ee fence: 210-270 5 Rodalquilar — { mmmmene | 220-330 5 to" 0 1 2 a0 35%, COT) 27 ute afr ie eminem highland hg et mvapntionton st ta: The emul ope Macon kompeannge eked sarees siesee fpitsane sha as Wiangles the eaeubaied 348/80, ration ae len shone. Mexified Irn Attias U8) ERAN Bay of Plenty wn)/ | f => 08, ie Lake a te OF hom | . ont GEOTHERMAL AREAS. | | | | enon © Delineated by driling © Delineated by geoptysics © Other thermal area | sa A voucano Aes anne OQ 2 075m | Fi. & Map ofthe Taupo Voleanie Zone inthe Nosh sand, New Zealand sowing the locations ofthe fella ‘OFsaki gecrial sem and White Ind wleano (mid fom Hedenggi, 1986). The Taupo Vane Zo es tains aout 0 equiapaced geotherinal ters ssociated with eaeafkaline magnatism. Abu hal af Ce sens ane hen cleat ws depts of 500 to 2.800 m. Hose ocks comprise a sequence of Qtateraay vane dpi of pedo inal sve composition that unconfoemabt overie low rink Metamonphned grasickeCHARACTERISTICS AND GENESIS OF KPTTHERMAL GOLD bEvOstTS 235, production well (Onaaks Pool 8 ‘Mineral deposition Mineral deposition '" Pe” spaces in ope spaces, su 7 woo FOE LS secre a | ig - 5, cow [E é lea \ ; a é ie € 000. j i 5 2 wane ence 7 sore: : 2 vate > ; / lao 2 ’ are tevaul pri we aber actrees es al the Ok Pol Benen eatin {aeRO ps quats and amoyphocs ea hep toi computed sag S79 si CHILLER pene anes oid depute dyatteam a the pint off tg eg othe ann trea C2, tome lig sien nee’ lsh Uvenghsiaton an pH nce tig Co de pes enna oir wenperstarecen te eedon OFFS bree dun he gu bie anpeses Yon Sear 19) Wit stan White Island is currently the most active volcano in the Taupo Voleatic Zone of New Zealand (Fig. 8) and is the site of a modern high-sulfidation epithermal system {Hedenquist et sl. 1993). The compesite cone is com suracted of andesiticlacitic lavas and rises 700-m from the shallow sea tloor. The anain erater floor, which is close 0 sea level contains highvtemperature fumaroles and acid Springs awociated! with the degassing andesite magma, Se Mrter aveurson is locked by the deposition of anhyrite, ‘hich Torys seal and isolates the ‘magmatic hydrother inal system, Thus fumavolie discharges come directly from asubjaceat degassing magina (Giggenbach, 1987), An- deste ejecta trom the volcanic vent coatain pervasive and fractarecontrolled eristobalitealiniteanhyerte-pyrite al teration assemblages snd veins filled with alunite, anhy- dite, Avieh chlorite, snd trace pyrite, The 84S analyses of cinexisting slate pairs indicate SO, disproportionation hd equilibration temperatures of 30°C = 50°C “The magmatic yasesdiselarging from White Island have oxidation potentias near the SO,/ 11 gas buffer, consistent with the oxidized conditions inferred for high-slfidation epithertmal deponits (Giggenbach, 1987), Taking the ther- mal ouput (850) Moe) and SOy fla, along with results of aeronol sampling, the daily flux of copper and gold in the snaggmatie gas plume is 280 kg Cu/d and 0.1 kg Au/d (Hediegiist etal, 1995). At this rate, 1 Moz of gold dis changes in “8500 Hovsever there is tle evidence that sig- nificant amounts of copper oF gold are currently depositing, in the hydrothermal sistem (Giggenbach. 1987; Hedenquist, etal, 1993). So, like BroadianlsOhaiaki. White Iskinel also appears to lack a favorable environment for metal deposi- tion, but the results show that cale-alkaline magutas niay be sources of metal-transporting ligands. atid of the anetals themselves, he ical Environments of Ore Deposition In this section, we review the current understanding of gold and sulfur speciation in hydrothermal fluids aie discuss the potential implications for epithermal ore formation, Gold speciation jold occurs in the +1 valence state in aqueous species under hydrothermal conditions, due 16 the low-oxidation potential of most hydrothermal waters (Seward, 1991) Here, gota has low sohubility as a bare ion (Ans). Signiti- cantly higher gold selubilities can be achieved when gold forms aqueous complexes vith various ligands (e.g., CP, HS-, CN*, etc.}. These are necessary (© generate the rel tively high aqueous gold concentrations (24 ppb) in ore forming hydrothermal solutions (¢.g., Brown, 1985; Seward and Barnes, 1997; Cooke et al., 2000). Processes of metal deposition are dependent on gold speciation in epithermal environments. Ligand availability and the prevailing physical and chemical conditions con- trol the abundance and composition of individual goldspecies. This in turn dezermmines the total amount of gold athact att be dissolved in mineralizing solutions, ie, ZAw = m(Au(HS)3) + m(AUHS a3) + m(HAN(HS)y qi) + mn(AuCl sete. wo A depositional processe may be effective at precipitating gold from one golé-bearing aqueous complex but may have no effet on the stability of another, For example, boil ing will cause HLS to degas from a mineralizing solution, can destabilize complexes such ay AudHS precipitate, However, HyS loss does not ak and boiling of solutions in which old occurs predominantly as a chloride complex may not Cause gold depasition Seward (1991) provides a detailed discussion of gold chemistryin hydrothermal environments, Au readily forms aqueous complexes with halagen- or sulfur-bearing ligands al solutions, Based on experimental studies, erature thermedynamie properties for several gold complexes have been derived: 6. S)3, Seward, 1973; Shenberger and Barnes, 1989; Ganumons and William-ones, 1995; Benning and Seward, 1996). HAU(HS)ajaq; (ivashi ane Ohmoto, 1991), ancl AufiSi.q, (Benning and Seward, 1996). Based on their ex- pevimental data, Benning and Seward (1996) concluded that AWHS,,,, was the donsinant gold-transporting species in low pH solitions over a wide range of total sulfar concen- ‘wations and temperatures, Consequently, we restrict further discussion of hydrowefide gold transport to AUMS,,9) and Au(AS)5. Other aqueous gold hydrosulfide and sulfide coniplexey may exist; however, their high-temperature thermodynamic properties have not been derived. Hydlrosulfide complexes are important for gold transport when watery are reduced (Em. > Em), sulfur concentra ave Ligh (58.00 mi), and temperatures are less than to 330°C (Figs. 10 and 11), Sich conditions are typi- ca of low-sniidation epithermal environments (Fig. 11) AUHS 4 dominates under moderately Em, concentrations, whereas Au(HS)3 neutral pH and elevated Ems concentrations (Fig. U1; reaction 2). The sofubility maximum for gold as a hydro- sulfide complex occurs in the concentrations (Fig. 11; ve- action 2). The solubility maximum for gold as a hydrosul- fide coniplex occurs in the Au(HS)3 field, at nearneutral pH conditions, straddling the sulfate-sulfide boundary (Figg. 1 amd 11) AMES gy + HS gy € AUCHS)3 + @ The relative stabilities of ate halide complexes are as Follows: Ai a (Seward, 1991), However, beeaise chloride concentrations are much greater dean oxfier halides in hydrothermal ystems, AuCl; fs likely be the most important gold halide complex. Chloride complexes have strongly temperature-dependent stabilities, such that gold chloride is unlikely co be impor- 36 (COok AND SIMMONS tant as a transporting agent at emperataes below 300°C, unless waters are highly oxidized, sicidic, and/on saline (Figs. 10 and 11). Such conditions may oecur in highs dation epithermal environments. fe thearetcill’ poss ble that an itcrease in pH oF HaSjaq) concentrations, ora decrease in salinity or temperanire may catise switchover from chloride to hydrosulfide complexing, without result ing in gold deposition (Fig, 10) AUCH + HySj.q) © AUHS,,., + HE #20, o phase sold and Although stil not well weerstond ay 102; Ssmonds and Reed, copper transport (Heinrich et al, 1993; Mountain, 1999; Ulrich et important for the genesis of some highs ihheranal gold copper deposits. It could also be imparsant for entiehing reservoir Sinids wich gold in low-sullidacion systems, Sulfur speciation Hedenquist (1987) proposed that lly chemistry should be the basis for classifying epithermual deposits, beans oF| fundamental differences in the inlened oxidation pote tial and pH of the minevalizing solutions. tnterving the pH ‘of a mineralizing solution is Early simple, because the st bilities of many common hydrothermal sheration miverals (clays, muscosite, adularia, earbonates, ev.) ave pH depen dent The oxidation potential ofa hydrothermal solutions more difficult to determine. I) yest fe fnterted from hye pogene mineral assemblages and/or silfixr or easbon joe ope compositions. The situation is camplicuted because minerals used to infer the oxidation potential of hydro- thermal solutions (e.g. sulfides, sulfosis sulltes. oxides, tc.) can precipitate tinder both oxidizing sand reducing conditions (e.g, Cooke eta, 2000) From a hydrothermal perspective, itis logical 10 deline the redox state of waters in cerms of sulin speciation. be cause of aqueous sulfiu’s strong controls on base aid pre: cious metal solubilities and ove deposition 2000). Hecenquist (1987) defined low-sulfidation ste as those where sulfur generally occursats reduced aquenus species (-2 valence state) in prineval the epithermal environment, High sul in reference wo systems where volcanic sass co dominantly as SO, yg, (+4 valence state), the predominant sulfa species in oxidined magmatic systems, Whe) the Sy is absorbed by ground waver. disproponionsation can pre duce an acidic water (Rye, 1993) in whieh sulfur occurs predominantly as sulfate species (+6 valence state), e953 4804 ¢) + 4H,0 9) BHSOF+ HS ag) + SH “ Note that the terms low ant igh sulfation do not re dave to the abundance of sulfur, which is highly yaviable and generally unquantifiable in cach deposit type In the following discussions, we define oxidized waters as those in which sulfur occurs predominamily as dissolved sulfate species (HSO}. SO¥-, etc.: Figs 19 auct 11). Re- duced waters are defined as those where aqueous sulfide iA a aidenCHARACTERISTICS AND GENESIS OF EPITHERAIAL. GOLD DEPOSITS 2a7 2 2 . Faas | | a BES eae ros 4 [Bcterime of ag 4 ae © i | Hematite | Hematite 12 1 ! AuClg ' \ cit ocased | % | % Hematite | = of satamtastions | Leica . tes e eo e ' Au(HS)5 ' 7 af it eto q Pyrite Pyrrhotite low salty water 2 2 2 ‘so 100 150 200 250° 300 aso 6010050 00 250. 300 380 $0100 150200 50 300 a0 T (eC) TEC) TEC) Fi “Rye eagram showing she sabi fet of Fe oxides, e slides, kaolinite (kal) nite (lun. calkte (ce), ul antnite Canhy), gold sls contours and predominance elds for agen sling and go Testing species Ry dened sy log. iyi, sl fet eature of oxy poe, with ger ealen i erespunalng io morc osdiring conto. Ry elated 0 Tog Sng the eqn lg Foy = Beh = 29.5 Ivhere'T hin degrees Rein (Ciggeatach, 1997). 28 = 0 ° 2.04 mpl ~ 6 sliny = 0.5 st rte NaCl equi EC tho = O1N038 m2. 168 10M. K feldspar ithe sable KA sieate for dhe conditions pores. B.S 1101 m, pil 2 Coats = 5 percent NaCl eqs EC =O my ge = DOSE: ey = 244 # 10 Mencete a chesable KA iit for dhe crn perv C, E8001 pH «3, sini’ =25 0 percent NaCl equi, B= 026 way = OR $0511 Bom persue, Theemoriymaic data Yeo jsin etal (1802), Bening and Seve (19816) ave Gams sl kanoones (1995), Disebnion of specie cle Tit spreaeie species are predominant (H:S jag). HS", etc; Figs. 10 and 11). These definitions are independent of the sctual total amount of sullu dissolved in the water Deposition Processes Although hydrology is important for water and gas mk: gration into and shwongh epithermal environments, gold deposition results from the chemical reattions that take place within the fluids and adjacent wall rocks. In this sec- tion, we diseuss posible depositional mechanisms for ep- ithermmal snineraliration, within the framework of gold spe- ciation behavior Lono-sulfdation epithermat deposits In Jowsullidacion deposits, gold is transported primarily as Au(HS)3 in dilute, reduced, near-neutral pH waters (Fig. 11}, Chemically effective reactions for gold deposi- tion inehide FS jnq) fos sia boiling (reaction 5), wall-rock ations mace by Neat Ragheon eral ang np sulfidation (reaction 6), or destabilization of reduced sulfie bearing species via mixing with sulfate-bearing ground water (reaction 7) AW(HS)5 + 11° +0.5Hy iq) € At + 2HS,e 6) Au(HS)3 + [FeO] +H* © Aug + eS +H,0q) +0.5Hypa9- w and Au(HS)3 + BHO, © Any # 280} 49H 75H o Whereas these are all viable mechanisms for gold depo238 A COOKE AND siMONS. High Sutidahon Deposits 5 suon sunaoion Deposte | Low Sutsaton epost °° Focteee £0) wo, [2 ae : ~ euwrm |S 28 5 s Pyrite ; i i reswcoa | 3 az —— a4 i Magnetite | 2 2s id 7 Pyrhotite | | 7 1 a “ham 4g | 3 ag re | Hh = 2 “0 0 A " o1 23 4 8 6 7 6 9 0 “oO 1 2 3 4 5 6 7 8 8 0 pH Fe. pH Log fy pH agra at 300" snd 0.5 wt percent NaCl equ. A. The abil Fld wf Fe asides an Fides. teepa (RD - muscovite (ms) kaolinite ho), alunite an) ele (Ca) dayton) sa the pe ominace fields 0 HIS. WS ‘nied after Cowke et ay 1996). sition, each process should produce distinctive gangue a senibiages and Sct compositions that could be readily dis cvimtcated Numievical simalations have demonstrated the effec- tienes of boiling for gold and silver deposition in epi+ thermal exvisonments (Drummond and Ohmoro, 1985: Reed and Spyeher, 1985: Seward, 1989; Cooke and MePhuil, 2001, Simmons and Browne, 2000). Boiling of ‘rewtal chloride waters can also reste in the deposition of abundan carbonate and adalatia, die to the pH increase associated with COgg, loss (Browne and Fis, £970; Reed and Spyehe, I985)- In modern systems, proof of the chemical effectivesiess of boilinginduced HyS loss is pro- sided! dy clectram deposits on back pressure plates in geo thermal wells (Brown, 1986). The distinctive gangue min- eval assemblages and textures produced by boiling of lowsalinity nearncuteal pH waters (e.g., bladed carbon- ate, lasice textured qua, acuta) are present or abun- ant in most lowsulfidation epithermal deposits (Sim mons and Browne, 2000). Finally, the relatively narrow xevtical intervals of ore deposition in low-sulfdation reins and thei ftuettation in space (e.g, Big. 2) 1s also attrib tutable to the boiling enviroment (Simmons and Browne, 199, 2000) Despite widespreacl evidence for boiling, some workers advocate mixing as the principal mechanism of ore depo- Scion in lowsullidation epithermal deposits (e.g., Vikre, Raphon iteration using an umpablshed sprendsect. BS = AH ae EC= 0-41 weous sufarearing species. B. Gold solubility contoars and the presanassnee elds ye AUCT;- nd aqueot silfunbenring spectes, Shaded seas in B mark comely ligt lol Bilis, eae te shown on the right vestiea axes for comparative pu nes. Disbion i apevies earn 1989; Corbett and Leach, 1998). Apart from excellent fluid | inclusion data at Creede (e.g., Hayba, 1997), which is am AgPb-Zn epithermal deposit, there is ustally scant eve dence in support of mixing models for lowsullidation ¢} ithermal deposits, and chemical andl mass bakuiee couse: erations are usually not discussed, The physirt problems associated with mixing two watery eat have diferent den- sities and temperanies in porous andl fractured rocks are also generaity ignored ; Itis difficult to spectlate on the chemical clfeets of mis ing without knowing the compositions of both waters in volved in the mixing process. If mixing eauses a reeluces nearneutral pH water to be oxidized to suliaie-table con ditions, then gold may precipitate (Reed and Spyeier 1985; Spycher and Reed, 1989 Figs. 10) and U1: reaction 8). This would require mixing with steanelieated aeil st fate water, which is largely restricted to Ue ster table (Hedenguist, 1991). Furthermore, depending on the ini- tial oxidation potentiat of the chloride water, gold deposi tion may be suppressed initially hy mixingindlucedd oxida tion hecause, as for boiling, this can increase golel solubility while HyS i,q) Femains the dominant aqucons sullur species (Figs. 10 and 11; Cooke and McPhail, 2000). With contin- ued mixing, dilution could then lower gold concentrations so that saturation is never achieved. Mixing of chloride water and peripheral bicarbonate water iso ineffective at depositing gold (Simmons and Browne. 2000)(CHSRACTERISTICN AND GENDMIS OF EPITHERMAL CoLD DkpOStIS 230 From a chemical perspective, walhrock sulfation reac- matic gases into a heated ground-water convection ect tions can result in ore deposition in lowsulfidation ep- which produces an acidic. lowesahinity mineral ithermal deposits (Senetion 7). However, because most of and (2) mineralizing magmatic brines which ascenel te the gui isvein or breccia hosted, sulfidation reactions are region of advanced argillc alteration, where thes probably not important for ore deposition. Ifwallock sul shallow ground waters and precipitate high-slfiation ore, fiat key depositional mechanisin at an individe "Although the models summartzed by Arvibss (198%) are ual Toe ion deposit, then gold would occur primar~ consistent with observed paragenetic anid yeoe ily as nelusions or substituted within the crystal littice of Tationships in many deposits, tis doubttul whe seconclaty pyvite in the altered wall rocks. of the stage two waters are oxidized (or high sul Conductive cooling may occur in low-sulfidation enwie from a chemical point of view (eg. fanas et al. 19) ronments if watenrock ratios are low and repose times are Based on our current understanding of gold speciation: fong (Drummond and Ohmoto, 1985), but such condi- there are dhree viable scenarios for gold anspor in his tions do not favor axe formation, Figure 10 illisuates that _sulfidation environments temperature change has Title effect on the solubility of gold asia hydvosulfide complex from 300° 10 150°C, and so 1, Gold (and copper?) are transported as hydzosultide cooling alone is not an important mechanism for ore dee complexes (g.. At ISjaq)) in lowsalinity seid waters that Position in lowsulfidation environments (cf, Sander and contain high concentrations of reduced sulfur (Stal Eins, 1980) 1983; Giggenbach, 1997; Hedenquist ct al. 199%: Jamas eral, 1999); .¢,, reduced (low sullidation) waters (Fig. 10) Aneslaton epithet deposits 2 Gold and copper ave tanyported Inthe apr ple Debate aout the genesis of high-sulfidation deposits as sulfide and/or chlorite species sic 2s A Wo. OF aves from uncertainties concerning the chemical compe- CuCl, (Losad-Calderon, 1992; Arsibas, 199 Mountain, sions of their minevalizing waters, Arribas (1995) 1999). reduced (low sulfidation) gases. Sized i tworstaye genetic model for 3. Gold and copper are transported as chloride con posits (Fig, 12), haseet on a previous model by White plexes (e.g., AuCI5, CuCl5) in acidic brines of maginatic (1991), In the first stage, magmatic gases cause intense acid derivation (eg., White, 1991; Hedenquist et al, 199}. Gold leaching snd development of advanced argillic alteration transport may occur under oxidized or vednced condition asscinbhages. Stage two waters exploit the secondary poros- provided that the mineralizing by ity and permeability created by the acideaching event and acidic, hot, and saline (Fig. 10), precipitate gold andl copper minerals, Arribas (1995) pro- For high-sulfidation epithermal deposits where gold is pesed two posible origins for the mineralizing stage to wansported as AUES;. 1 lowsalinity acid waters (e.g, FL raters (Fig. 12); (1) condensation oF dissolution of mag: Indio; Jannas etal, 1990), the chernical wea tions Hite con t : t | i : res are sulliciently ALTERATION ‘ORE DEPOSITION A yor By By on om xf Aeration Maing wih ‘eveope ? snatow neteoie Absotonatnane ne opmatc vapors tial 5D» Hct Alunte Magratic ) aicte acer come Frc. 12, Twrsage onde! for highstilfidation ore formation proposed by Arias (1905), moditied uw highlight ike ou involved in each sage of ore genesis. Sle | (A) i the ground preparation stage where irate ses encrate a acid sulfate highslfdation water that responsible forte ial hare seo ese sandaanced alc alieration, The second sage involves gold eepostion fram acid elieride esulicain novde brines (Bs) sears (B,) 2240 twol gold deposition will be similar to those outlined above for lowsulfidation epithermal deposits, e.g. AUHS 4) + 0.5Hyi4y) $9 At) + HS 5, «s) AUHS,) + 0.5[FCO] © Auyy + 0.5FeS,, + 0.5HLO pm, (9) and ANEES ay # AHO © Attys + SOR agp Hy 2s (uo) As for AuHS3, removing H,S from the mineralizing water sa highly effecrise method for depositing gold (reaction 8). Boiling of lowsalinity acid waters (e.., from 300° to will cause pH to decrease due to the dissociation of ion pais suc as Hho, and HySQgj,q) and may lead to gold deposition in association with quar, kaolinite, and cavellite (Reed, 1992), Unlike lowsullidation environ- ments, however there are no mineralogical indicators to prove that boiling occurs other than the presence of coex- dsting liquiderich and vaporrich fluid inclusions. By in- creasing the acidity ofthe residual liquid, boiling may cause augillic ane advanced argillic mineral assemblages to de- posit, whereas the solubihity of base metals may increase, Wailhrock sulfidation reactions (e.g, reaction 9) are prob- ably not important for the precipitation of gold in the residual silica zones of high-sulfidation deposits. The initial stage of ne formation iavolves acid leaching and the de- velopment of residual quartz and advanced argillic alter aon assemblages (Fig. 12). Because iron is leached from the protolith, the residual siliceous rock is not a favorable site for later wallrock sulfidation reactions. Gold, sulfides, and salloxales generally aecupy secondary pore spaces, i ‘cating that the metals and sulfur were probably precipi- tated directly from stage owo fluids rather than via water. rock interaetions, Most workers on high-sulfidation deposits advocate fluid nixing as their preferred ore deposition mechanism (€-. Table 2). Oxygen and denterium isotopes have been used to demonsttate effectively that the waters which precipitate silica ancl advanced! argillie alteration assemblages are mix lures of nuagmatie and meteoric sources (Fig. 6). However, Avid inchision evidence for mixing is lacking at the site of fre deposition in some systems that have been the subject oF detailed investigation (e., El Indio}. The stabilities of saqucons gold species discussed herein further suggest that fluid mixing could increase, rather than decrease, gold sok bility. IC mixing iy important for gold deposition from AUHS,,,) it lowsalinity acid waters, then the same chemi- cal arguments for and against mixing apply, as outlined above for Au(HS) Evidence for mixing is well documented from Lepanto. Hedenguist eval. (1998) have used oxygen and dewterium isotope data obtained from gangue minerals to caleulate a COOKE AND siswons, change in the ratio of maguatie aod neni wacom ponents from Ur to lil over a distance oft ban aera Mancano and Campbell (1998) prosied fsid intion evidence from enargite for mixing of saline hot wate wt % NaCl equiv; 260°C) with steam-heated gronnd water Both data sets support Mui Le (0 wt % NaCl equi 150°C tnining inthe oreforming ensronone thes, the presence of viponvich hid eh at Lepanto (Mancano snd Campbell, 1 Slusion evidence for a steamheated phase separation was occurring ato below the simple Stes Thos boiling may have aso contited to wollte Postion at Lxpanto, Some highsulfidation deposit contain thd inchion evidence for highsalinity ines (able 2), hn hesesyene Ach brines could anspor god aw AUCs nner oxide Sr ff he temperature is have “HN%) rete! Cade tions (Figs 10€ and 12). For these ines, go can pe Gipitate i Fesponte to cooling, pH increase. tei and/orsalinity decrease mo. Hove AuCly + 0.5Hyjaq) € Aly + HP + 2CP, ay H,S toss via boiling, oxidation, or walkyock su 0 will have no effect on gold solubilities, in conmtiast to its effects on hydyosulfide complexed gold in dilite warers, Mixing could favor gold deposition from acid brines if any orall of the following events occur: salinity decrease, cool ing, pH increase, or reduction. However, these processes will compete with dilution of aqueous gold, and pot tially with a switchover to hydrosulfide gold complexing (reaction 4), which can both inhibit or prevent gold de- position. Condnetive cooling could result in gold deposi tion but is unlikely to produce ore, hecause itis slow and requires low flow rates, which will result in insufficient metal fx. Suonmary Substantial mineralogical, fluid inclusion, and stable jso- tope evidence shows that boiling is the principal cause of electruim precipitation in many low-sulfiation epithermal deposits. High dissolved gas concentrations favor precious metal transport and increase the depth of initial boiling, Buoyant ascent of boiling chloride waters yenerally restiets mixing to the top and sides of upllow zones, Oy h and acid sulfate steamheated waters accur (Fig, 1). Mixing of the waters within the ore sone may ocewr cuving, collapse of the hydrothermal systen (e-g., Reed and Phi lee, 1992), producing barren clay, carbonate, or silliate ‘gangue as steam-heated waters descend into the mineral ized environment (e.g., Simmons et al. 2000) Some highsulfidation deposits contain unequivocal iso- topic and fluid inclusion evidence for fluid mixing. For many deposits though, it remains unclear whether this, process is respansible for (1) increasing the solubility of gold by entrainment of ligands and/or meus fiom mag- matic brines or vapors, (2) ore deposition, (5) gangue decngeonee moma eremnenaeram ets mae CHARACTERISTICS AND GENESIS OF EPFTHERMAL. GOLD DEPOSITS. a position, (4) rock dissolution, or (5) a combination of the four preceding scenarios. For any given high-sulfidation deposit, if acid brines transport gold as a chloride com- plex, then dilution, cooling, reduction, and/or pH in- crease ean cause cleposition of gold, possibly during mixing with ground waters. In contrast, if gold is wansported in highsultidation environments as AWHS),4) within acidic, reduced, lowsalinity waters, then mixing'induced oxida. tion or boiling may promote gold deposition, but cooling, diution, and changes in pH are unlikely to be effective de- positional mechanisms, Acknowledgments We ate indebted to Mark Simpson for assistance with as: sembling the datahase on epithermal deposits and for prepa ation of nany of the figures, We thank Noel White and Patrick Browne for their timely and thought-provoking re- ‘ews, ane 10 Andrew Davies for constructive comments on an earlier draft of this manuscript. Thanks also to Alex Losada- Calderon for wselul discussions, S.FS. received financial sup- port for this paper from the Foundation for Science and ‘Technology (New Zealand), which is gratefully acknowl edged. D.R. thanks the Australian Research Council for their support through the Special Research Centre program. 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