$06 Reviews Vol. 18,2000, p. 221-244 Chapter 6 Characteristics and Genesis of Epithermal Gold Deposits Dav R. Cooxst Conte fe Oe Past Rene, Hosiery af Tasmamin, (PO, Raw 959-70, Habart. Tasmania. 7001. Australia AND Stuer F, SIMMONS, Geothermal Institute and Galogy Department, University of Aucland, Private Bag, 92019, Auckland, New Zealand Abstract ‘This paper summarizes the characteristics of epithermal gold deposits and discusses potential ore de- postion mechanisms. Epithermal deposits mostly form at shallow crustal levels (<1 kin) in subaerial vol fanie settings, There are two classes of epithermal deposits which can be discriminated in terms of their {geologic environments, alteration mineralogy, and uid chemistry: (1) lowsulfidation epithermal de- posts which are spatially sociated with magmas, where ore deposition generally occurs several kilome- {ers above the site of intrusion, and quartzadulariaseriite-carbonatealteration assemblages are charac teristic; and (2) high-slfidaion epithermal deposits which havea closer spatial association with degassing ‘Gaeubkatie nage at ae cagracierved by tense ust aud leypogene advanced angle alte assemblages (quartzalunitesaolinite-pyrophylite) “The waters that precipitate lowaullidation epithermal mineralization have isotopic composi consistent with a predominantly meteoric source of water, and a magmatic volatile source for sulfur and Carbon. sherstion and ral aemblages are consistent with near neutral pH conditions. HSiaq is the predominant sulfur species in the mineralzing solutions. Temperatures of ore deposidon are less than 800°C and salinities are low (<3.5 wt % NaCl equiv). High dissolved gas concentrations (CO, H,S) the depth of initial boiling dation epithermal mineralization precipitates from waters that are predominantly magmatic ‘based on oxygen, hydrogen, and sulfur isotope compositions. Oxidizing, acidic waters form via the disproportionation of magmatic 803, which generates abundant sulfuric acid and minor H,S. Ten peratures vary widely (>400°-100°C), but'salinities are generally low (<5 wt % NaCl equiv). There is rare uid inclusion evidence for maematic brines in some deposi ‘There is substantial mineralogical, uid inclusion, and stable isotope evidence for boiling in lowsulf- dation epithermal systems, and it can be a highly effective process for electrum deposition. Fluid mixing is ess likely to be important for ore formation. Mixing within the ore zone is generally restricted to late- stage collapse of the hydrothermal system, which allows descent of steam-heated waters into the mineral Jed environment and produces barren carbonate or sullate gangue ‘Some highsulfdation deposits contain unequivocal isotopic and fd inclusion evidence for uid mix- ing. However, it remains unelear whether mixing is responsible for ore deposition, gangue deposition, or ‘enrichment of metals in ground waters. For any given high sulfidation deposi, facid chloride brines trans port gola asa chionae complex, uien cuudont, cool, anu 01 PIT htereae ca cause yl ws Tepe por ‘bly during mising with ground waters. By contrat, if gol is transported as a hycrosulfide complex in di- lute acidic waters, then gold may deposit in response to boiling oF to mixing-induced oxidation, but not to temperature, sainiy, and pH changes. Introduction EPItHERMAL gold deposits form In we stiallow pants Ut rmagma-related hydrothermal sjstems, commonly in sub- acral voleanic arcs (Fig. 1). The deposits are host to both precious and base metals but are now mainly mined for Iieir gold and silver contents, which can be substantial mt total production and can achieve spectacular bonanza grades. The term “epithermal” derives from the genetic ‘Corresponding author: email, d.cooket@uras.eduau classification scheme for hydrothermal ore deposits pro- posed by Lindgren (1933). On the basis of stratigraphic re- Ealouslilps in voleanie suatigeapliy, but aloo by analogy wide mineral and metal occurrences and mincral textures in modern geothermal systems, he inferred that epithermal deposits formed at <200°C and <100 bars. There was little advance in the understanding of ep- ithermal deposits until they became a major target of ex: ploration as the price of gold rose in the 1970s and 1986s. Fluid inclusion studies extended the temperature range of epithermal deposits to about 300°C, and stable isotopes, 22292 (COOKE AND SIMMONS 'R,1, Schematic diagram showing the postions of low and high-ulfidaion epithermal environments (Aand B, re specivey) within hydrothermal pteis asocated nth Nowedome voleanic setngs of modest relief (medi from Henley and Elis, 1988), A. The epithermal envionment s represented by "y” Meteorie water circulates deeper than 5 Enuhang eamusvinn Anion hy hen fre an nding Feallring magma. At depth of 1102 km below the water ‘able within dhe upon zone, maximtom temperauurepressure gradients ave close to hydrostatic boing (Henley, 1965), At shallower eel, he icrane gradient cases rng Huds vo more laterally (us suppressing boling trough Gilution by mising with loal ground waters) to form outflow 2ones The dee endsemiber water types that form inthe foveslfdation epithermal environment shown sre known from exploration dling Buoyant chloride waters form the {pls ple snl the must spartan or aqueous transport of precious metal, Thre waters drive fom [eration between deeply circulated seteorle water and maginaie comporents (HO, CO, SO HS, HI) near the bhse ofthe convection cel and subsequent luxtmineral interactions (Ciggenbach, 1097); ther pH is close to neutral “The other wo water types ate seam-teated ground waters thar ain heat and aqueous consents rom condensation ‘ot team (containing vapor, COs, H,S) which separated from deeply bolling chloride water. Orch tea heated wa {Es contuning high concentradonsol diaslved CO, 10/000 mg/g) tend to accumulate 2 sav eves ana arape the more stagnant margins down to 1,000 below dhe water table; heir dstelbuon is best known at Broadland-Ohaaki (edenguist 1990), Acid sulfate steans-heated waters contain high concentrations of sulfate (1,000 mg/kg) thc de five ftom oxdation of HS in the vidoe sane, These waters clébBle down tothe water able where they mix with CO krishna orn strand hecome nevtetied within a few ens of meters (Sehoen ea 1974), The di ‘sibution ofthese water pes lange depends upon topographically conulledydrautic gradients In low relief settings tssocated with shyolide voleanism, the steanrheated waters occu? above, and on, the periphery ofthe chore water plume. B. The ovalshaped hatched 2one represents the epthesmal envionment Its fated beneath the summit of odes volesnic cone and above a degasng magma. In this sen, acid uids dominate and include aid sulfate and ‘Lu chturstezullae nasrn The uo tone ress fom the hydrlc gradient or water able (arhed line which a ‘ost follons the trace of eopography).(CHARACTERISTICS AND GENESIS OF BPITHERMAL GOLD DEPOSITS 223, proved the prevalence of meteoric waters in the oreorm- ing environment (e.g., Nash, 1973; O'Neil and Silberman, 1974; Kamilli and Ohmoto, 1977; Sawkins et al., 1979; Buchanan, 1081). Theoretical and experimental tech: niques were used to determine metal solubilities and min- cral stabilities under hydrothermal conditions (e.g., Bar- ton et al., 1977; Barnes, 1979), which led to numerical shuulaiots uf reacduu pails aud ure frunadivin (Roce, 1982; Drummond and Ohmoto, 1985; Reed and Spycher, 1985; Spycher and Reed, 1989). Meanwhile, in New Zealand, the United States, and other countries, the de- mand tor cheap electncity mvoived geothermal explo- ration drilling and development. At depths of less than 1 km, temperatures and pressures similar to those in the cepithermal environment were encountered (eg., Henley and Ellis, 1983). Precious and base metals were found to be transported and deposited in wells and surface pipes (e.g. Weissberg, 1969, Hedenquist and Henley, 1985a; Brown, 1986; Christenson, 1987: Krupp and Seward, 1987). By the mid 1980s, genetic models had been formulted to explain ‘occurrences and zonations of metals and minerals, 10 de- marcate the physical-chemical conditions of ore deposition In ceveral epithermal deporit, and to spectlate on tha sources of fluids and metals (e.g., Sawkins et al, 1979; Buchanan, 1981; Berger and Eimon, 1983; Hayba et al., 1985; Heald et al., 1987). In these models, hydrology was secu ty be at canutial factor influencing ore depositions however, only now can the terms “boiling” and “mixing” be applied as causative agents. Carlin-ype deposits were included in the epithermal realm by several workers (e.g. Berger and Bethke, 1985; Berger and Henley, 1989), but they were later defined as a distinct class of hydrothermal deposit (White and Hedenquist, 1990; see Hofstra and. line, 2000). The modern use of the term “epithermal” thus retains much of Lindgeen's intent, although the ther- imal regime extends to ~300°C with formation depths no greater than 2 km below the water table. Lindgren (1938) showed that despite sharing common gangue mineral assemblages (e., quartz, carbonate, adu- laria, clays, fluorite, barte, pyrite), metal inventories of de- posits were wide-ranging, with varying proportions of gold, Ever, and base matale, inebiding merrnry, antimony, tel- lurium, and selenium. Nine subelasses of epithermal de- posits were thus grouped. Among these, gold alunite and gold telluride remain distinguishable, whereas the remain- Ser are scen aa part of « spectrum of deposit ype termed “low sulfidation” (Hedenquist, 1987; White and Heden- 4quist, 1990, 1995; Hedenquist et al., 1996; Hedenquist and Arvibas, 2000), “adularia-sericite” (Hayba et al., 198 Heald etal, 1967), OF Tow sulfur” (Bontiain, 1986), Tow sulfidation refers t0 the predominance of reduced sulfur species (HS", HS), whereas the adularia-sericite classitica- tion emphasises the nearneutral pHT of the oreforming Huias. Cold alunite deposis are now reterred to as “high sulfidation” deposits (Hedenquist, 1987; White and Heden- Quist, 1990, 1995; Hedenquist etal., 1996; Hedenquist and Arribas, 2000), but these were also called “acidsulfate” and “alunite-kaolinite” (Hayba et al., 1985; Heald et al, 1987; Berger and Henley, 1989) and *high sulfur" (Bonham, 1986). High-sulfidation refers to the presence of a signifi- cant component of oxidized sulfur species (HSO3, SOP, ‘SQ, in the orecarming Mids, whereas the gold alunite. acid Sulfate and alunite-kaolinite nomenclature emphasizes their acid pH and hypogene sulfate mineralogy. Gold tel luride deposits (e.g., Cripple Creek), which share several inincralogical similarities with love oulfidation deposit are considered separately, appearing to be genetically linked to the emplacement of alkalic igneous rocks (Bonham, 1988; Richards, 1995; Jensen and Barton, 2000), ‘in this paper, We review he yertess Of go-beat ig, Tove sulfidation, and high-sulfidation epithermal deposits, and ‘we draw heavily upon several excellent summary papers of the last decade (White and Hedenquist, 1990; Silitoe, 1993a, b; Arribas, 1995; White et al., 1995; Hedenquust etal, 1996). In doing so, we focus on 12 wellstudied rep- resentative deposits of the Pacific rim, the Caribbean, and southern Europe, where detailed mineralogical studies in- clude fluid inclusion and stable isotope data. These results provide insights into the physical and chemical conditions Cf ore deposition as well as clues about the origins of fluids Sand metals Tn places. we refer to other deposits and stide ies to highlight a specific relationship or to comment on genetic interpretations. The selection of low-sulfidation de- posits (Tables 1 and 2) reflects a range of deposit styles Mith nvorld clase gold resource, By contract, the eelection Of high-sulfidation deposits (Tables 1 and 2), which tend to contain a much smaller resource, is restricted to the avail ability of wellstudied deposits. We also review the condi- tions of gold uanspurt tal deposition and view these in light of studies of modern epithermal environments. We discuss the most likely mineralizing water compositions in cepithermal environments from the perspective of gold ‘anspor, and compare and contrast possible depositional processes. ‘Tectonie-Voleanie Settings, Space-Time ‘Reladoushiips, aud Orebodies Epithermal-xelated hydrothermal systems are generally associated with subaerial volcanism and intrusion of calc-al- {oti magmas that range from basaltie andesite to andesite to dacite to thyolite. Submarine examples are also know (cg, Sillitoe et al., 1996). Inrusionelated hydrothermal activity results from plate subduction and magmatism in both island-and continentalare settings. The apparent ab- sence of epithermal deposits in hycrothermal systems asso- ated with continental rifting or hot spot activity (e.g, Fast Africa, Iceland, Hawaii) suggests a strong cause and effect Tish Leimeen sulnlucdusrielated magination and ore for ‘mation (Sillitoe, 1998a). Although associated with a trans- form fault structure, the emplacement of the Clear Lake voleanic rocks and epithermal mineralization at McLaugh- iin, Caltornia, have been related to an Isolated subducted, slab associated with the Farallon plate (Isherwood, 1982) and localized extension within the fold and thrust belt of the Coast Ranges (Tosdal eta, 1995). Although it appears that extensional tectonies are important, there seems to befo ot one oe on ng onan a nen tren ot tie pectin tote atentennann ana crop oo women! w= nf pee oe A) ——voo ad wong fe ee ee es “ste crac amp HOR rat ene somes os swoon samt oom = calidad am et ce a NTN a . ce — ee ee cot women (como ang) 2 ‘armiposcionu omen 8 or ° 9 unde) ioensp astesteny i 5 a ee oe : g = 5 ee ™m Go om o moni Som swe as a ee os) ee ea one , as Wen on Pon on reco sm or asn'emthepn ma puns eps vest rot yess, er poe end po ted eae ee ce Se ee ernie Sa eee Tew =o Oran ea vam ios Goat Tapodog aaa Jo SHSLORIED 9BOpID TFL, 224295 (CHARACTERISTICS AND GENESIS OF BPITHERMAL GOLD DEPOSITS yume = ur somos = faqnosenn =n epi =o anon SaeU= a. “nreqES = 3 aso = de “masons = on ‘opurtt Supoa ures eunussiy UX weve st ono AST “emote Bajos (un) HIN, seis ssuyor el os, oon AT Senbepnt ude Buyoos (une) wasn Hoo gO eG OLIN OOM ACT ‘nasty Buyoo> (une) Fury ge on 0g s6FOZO SHES ACT me (ab) a4 oon Seno usogor O1G-06E TEA ‘ACT “Hogs, mole ae (pe ab) sasonmte> de Suyou ovens FOO See-Ost AT stony ‘went sot sa sa, Sen (0) > oem Tasting, ‘oye par sex ewer 2 £0: Sane os mabye ad aon sa Smog HOOD (ADVE L eS —GPTATY GB-OS "TeA‘AC] "oI “use, Bayoq (ab) gan (rz ro) ‘uopsn yaa Sw SRONETI™ (ab) Ge OL KE TIMED GORE TeA‘ACT OMEN “pesmi 02) 19 w amt souddras Souog (ab) z= orgs “eab) SEV — ALTO —OBEOOT TOA AST “uuoynsn "eg vunip oie OTRO] aE GED PD Te) Oa, Nompu sama EDU RESIS waa wntsodop OFFDae wim Sats ins wa, 20 7a PI Op aie,226 COOKE AND SIMMONS zo general crustalscale control on the localization of ore- forming environments (Sawkins, 1990; Sillitoe, 1993a) ‘Most epithermal deposits are Cretaceous or younger (cx, Silltoc, 1098). Older deposits are known, most no- tably the Paleozoic deposits of the Tasman fold belt in east ‘ern Australia (e.g., White et al., 1995). Since plate margins ‘are regions of uplift and erosion, epithermal deposits gen- Cratly have poor preset vaulon powenla, given Wie sualow depth of formation. Furthermore, because high-sulfidation deposits can form at shallow levels in active volcanic edi fices (e.g. Fig. 1B), resurgent explosive volcanism can also destroy these mineral depostts and/or their precursor ac- tive geothermal stem. Although low- and highsulfidation systems are largely products of subaerial, magyna-related hydrothermal activity, both mineralization styles rarely occur in the same deposit Exceptions include Comstock Lode (Vikre, 1989), Em- peror (Eaton and Setterfield, 1993), Masupa Ria (Thomp- son etal 1994), and Lepanto (Hedenquist et al., 1998), al- though for each of these examples, the bulk of ore-grade ‘mineralization is restricted to either lowssulidation or high- sulfation environments, Epithormal districts cover areas that range from a fow im! to several tens of him?. Orebodies are commonly hosted by near-coeval or older voleanic rocks, “basement” (metasediments and metavoleanies), and/or rarely by sub- wuleauic lnuusious, The shapes uf vicbudies are vasiable, but they share the common feature of being zones of paleo permeability. Orebodies extend laterally hundreds to thou sands of meters (in maximum dimension), occupying veins that may be no more than a meter to several meters wide, Vertically, they tend to be restricted to $600 m as exempli- fied by mineralization in the Pachuca-Real de! Monte dis- trict (Fig. 2), High dissolved gas contents in the fluids can extend the depth of frst boiling (Hedenquist and Henley, 1985b), and this is believed to have resulted in a vertical in- terval of ore mineralization that exceeds 900 m in the Baguio district (Cooke et al., 1996). Postore faulting can extend the vertical interval of mineralization, as is the case at Comstock Lode (Vikre, 1989; Hudson, 1993) Structure, lithology, and fluid composition influence the permeability af areforming environments. (Silitn 1993b). Orebodies are found in steeply dipping veins (1-10 m wide) and vein swarms, stockworks, and less com- ‘monly, lowangle veins (c.g., Comstock, El Indio, Hishikari, Lepanto, Mejicana, Round Mountain, Tayoltta). Theve lo calized faults are the products of extensional and transten- sional stress regimes that are regional in scale, butin many cases the faults have offsets of no more than a few meters. ‘hey require britue falure as controlled by rock sevlog). Mineral precipitation and dissolution by hydrothermal solutions aso affects permeability. In low-sulfidacion envi- ronments, permeability is reduced by quartz and calcite de- position, fn contrast, permeability is enhanced in hngsul- fidation environments by acid solutions causing rock dissolution and formation of vuggy quart. If fluids in ei- ther environment have high gas contents and are subject sharp pressure reduction, flashing and hydrothermal erup- tions ensue, forming permeable breccia zones (e.g., Kelian, van Leeuwan et al., 1990; Lihir, Garman, 1994) The aforementioned features are general attributes of epithermal deposits. The characteristics that distinguish owsulfidation from high-sulfidation deposits are empha- sized below. Low Sulfidation Mineralogical patterns in the vicinity of oregrade mate~ rial provide the diagnostic evidence that distinguishes low. and highulfidation environments. These are graphically portayea in Figure 3. (Ore in low-sufidation deposits is generally associated with quartz and/or chalcedony, plus lesser, but variable, amounts Of adularia,calite, thodochrosite, K mica (ilite oF sericite), chlorite and pyrite gangue. Lattice textures (platy calcite land its pseudomorphs) are common textural characteris: tics, as are crustiform and colloform bands, particularly in shallowly formed veins (e.g, Hishikari, McLaughlin). Collo- form bands were most likely deposited as amorphous silica (eg Fournier, 1985), crystallizing to quartz with time. In deeper veins, coarse erystalline comb quartz is common (ea, Comeinel, Taynltie) Gold typically aceurs a8 elec: trum or more rarely as tellurides (eg., Acupan) in ssocia- tion with acanthite,silersulfosalts, base metal sulfides, and pytite (Table 2). From the vein selvage into the adjacent Petiney rock, 2dularia vce way to iit, quarts abundance diminishes, and pyrite & common throughout. All of these inerals reflect ore deposition in the presence of reduced and nearneutral pH lowsalinity water. Deeprlevel and re- glonalscale alterations wounists of a propyitic assemblage Containing quartz, chlorite, illite, pyrite, calcite, abite, adu- laria, and epidote (e.g., Acupan, Comstock Lode, Round ‘Mountain, and Tayolita). The intensity ofalteation largely depends on the existence of a reactive host rock, commoniy volcanic, as well as porosity and permeability. Silica sinter is deposited where boiling or boiled lowsul- fidation fluids discharge atthe surface (Fig, 1A). Sinter ink tially precipitates as amorphous siliea but crystallizes «o «quartz within 50,000 years (Herdianita etal, 2000). Silica sinters demarcate the paleosurface and the paleowater fable andl are commonly fosind at the same level asthe al teration assemblage comprising alunite, kaolinite, and ‘opal, which form in the presence of acid sulfate steam hreated waters (Fig. 1A). At depths between the paleowater table and mineralization (and sometimes lateral to miner alization), rocks are variably altered to clays (smectite, in- terlayered illite smectite, illite, chlorite, kaotinite) and car bonates veins are filled with carbonate (e.g., Comstock Lode, Ruuind Mousa, Tishikori). ‘These minerals can form from COzrich steam-heated bicarbonate waters (Fig. 1A; e.g., Simmons et al. 2000), Fluid inclusions Fluid inclusion data are used to deduce the temperatures and compositions of mineralizing fluids along with the formation depths of a deposit. They provide important constraints on the genesis of lowsullidation deposits. i | | i | |(CHARACTERISTICS AND GENESIS OF EPITHERMAL. GOLD DEPOSITS 297 Pachuca - Real del Monte district - vertical extent of mineralized veins EXPLANAIION wo [ae — orem 2400 Baas one working Fic, 2. Ore intervals from lowsulidation epithermal veins inthe Pachucs Real del Monte district, Mexico (from Gere et al. 1968), Theve are over 100 veins itis word clas Ags dtc. The dstectede upper and lower limits tf the iterated horzon range 20 0 2800 ele, but india vein, dhe elevations and eral extents Of te eraliztion difer great228 (COOKE AND Low Sulfidation crustiform | altered banded ore with | host lattice textures | rock SIMON High Sulfidation disseminated | altered massive | host Kaolinite (pyrophylite) core | rock _+/sericite z |_smeetite i ite oF pyiite ite Ie] chlorite \ P27 calcite pyrite epidote TPP EF PETIT EP IFA DYG, ee smectite a ee ‘6, ees ai at Fn ag se $e Sa ef te oS iS quartz, chalcedony, adularia, pyrite, adularia base metal sulfides, | ilite alunite, sulfides, Sulfosalt carbonates, AU-AG | pyrite residual quartz (vugay & massive), ts, AU-CUl-Ag) 7 40m io 8, Schematic diagram showing mineraloge zoning in low and highaulidation epithermal deposts (modified {rom Slitoe, 1930). Most fluid inclusion data have been obtained from quart, which is volumetrically the most abundant min- ral phase in ore material, Data have also Deen obiained for fluid inclusions hosted by calcite, adularia, and translucent sphalerite. Bona fide primary fuid inclusions typically occur in groweh zones within medium to coarse- grained euhedral quartz crystals (Bodnar etal, 1986). In epithermal deposit, such material may be difficult find and data may be obtained mainly from secondary incla- sions (e.. Round Mountain: Sander and Einaudi. 1990), Sander and Black (1988) discuss the problems associated with studying fluid inclusions hosted by crystallized and recrystallized siica minerals. Furthermore, in many de- posits che hest preserved finid incisions aeeurin gangue ‘minerals that are not intergrown with gold and may be separated from ore by several millimeters to meters of vein fill Mos fluid inclusions contain two phasco (liquid 1 vapor) and are liquid-rich, with liquid dominating the volume by >65 percent. Vaportich two-phase inclusions are also com ‘mon. In these, vapor comprises >98 percent of the volume, so dias Wie luclasion cavity Is Bae wha alu Ugalde ‘which i rarely perceptible. tis usually impossible to mea- sure either homogenization (Ty) oF icemelting tempera- tures (T,) from vaporrich inclusions in epithermal envi- ronments (Roedder, 198%; Bodnar etal. 1989) Fluid inclusions range from irregular to smooth negative cxystalshaped cavities; irregular shapes correlate: peratures <290°C and smooth shapes corretace wit peratures >250°G (Bodnar etal, 1985). Necking and two- phase trapping of liquid and vapor are common and workers generally take care to avoid inclusions affected by these processes. Even so, their effects are seen in the wide range of Th commonly measured in individual generations of fluid inclusions. Homovenization temperatures range from 150° to 300°C, and ice-melting temperatures range from 0° to -8°C, ind cating dilute fluids of generally less than 8.5 wt percent NaCl equiv (Table 2, Fig. 44). Hedienquist and Henley (1985b) showed that iee-melt- ing temperatures between 020° to -1.5°C could be solely attributed to the presence of aqueous carbon dioxide rather than dissolved salts (wt % NaCl equiv) as is com- monly interpreted. In some casos, erushing otudiee or gas analyses have demonstrated that the icemelting tempera- tures are at least partially due to aqueous carbon dioxide {e.g., Sawkins et al., 1979; Vikre, 1989; Sherlock et al., 1999}. Oue uilies indieawn UF die yes wymubution wy ieee melting temperature is the trend of the Ty-T,, data shown in Figure 4A. Curves III and I’ show the effect of gas loss duc to boiling on the TyTq, data for a starting water that contains significant amounts (but less than I'm) of dis(CHARACTERISTICS AND GENESIS OP EPITHERMAL GOLD DEPOSTTS Es a _ es ae e oo 1 = Comstock oS) os A = Hishikar g act S-2 MLaughin = : : = Teyotta g E ° 3 . : 2 2 00 38 2 & 5 5 & ‘Temperature of homogenization (°C) = Lepante 7 Nansatsu aa 2+* Rodalquilar +" La Mejicana 2 ctingio We % NaCl equivalent ‘Temperature of fal ice melting (°C) ‘Temperature of homogenization (°C) Fo. 4, Temperature of homogenization verws temperature of ce meling (apparent sali) for uid incusions| from lowsullidstion (A) and high-ulidation deposits (Un Table 2. The shaded area between 00 and 15°C repre: sents the ellect of aqueous carbon dioxide on the iemeldag temperate of water wth np to 08 m0, (HHedenguist fn Henley, 1965b) Tn B,halitesatarated Sid inclusions from La Mejicana, Rodalgula, and Nansatsu ate not shown Deca nae amsoitit tempera rater at eemelng cenperatnes were sel a dere re elie. ‘The ive in A shows the trajectories of boing and mixing for fide nthe Broadlands Ohall geothermal system (rom -edenquis and Henley, 185; Simmons and Christenson, 194). The parent eompaston As simis othe deep cho- fide water (-0.75 m OO,, 0.1 m NaC, whereas B represents the composition of dhe peripheral COrch team heated tater Cure Ill epresents the elect of gas oes due to boing Fora water ofthe parent composition: curve I’ repre Sh the elect of slater ising wih teaneated COrrich water Curve represents the mixing wend betrees !Nand hand cums [represents the boing tend dew Rayleigh etaporative stam oso iute,guypoor parent I ‘uid Simeone and Simmons (1899) and Simmons etal. (2000) describe examples offi inclusion data from epither ‘nal depose where sch bailing trends are interpreted 229230 (COOKE AND SIMMONS solved carbon dioxide. The gas loss trend is distinct from the boiling trend of a dilute saline solution lacking any dis- solved gas (curve I Fig. 4A). Mixing (curve Il, Fig. 48) can also affect fluid inclusion Ty and Ty data, For many data Sets, the combined effects of mixing and boiling could ac- count for the common clustering of data in the range 180° to 270°C and 0° to -2°C; ie, the data are bracketed by the Dolly (ON) aust unig (1) wena (ex Fedennuiat, 1990), Tin a few cases, ice-melting temperatures significantly lower than -2°C were measured (de Ronde and Blatiner, 1988; Vikre, 1989; Cooke and Bloom, 1990; Conrad et al. 1992; Sherlock et al, 199; Scott and Watanabe, 1996), 10 icating the occurrence of waters with salinities exceeding 10 we percent NaCl. In deposits where obvious sources of brine, such as evaporites, are absent, these high salinities can be explained by variable amounts of evaporative con- centration (steam loss) under open-system conditions {Sherlock et al., 1995; 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 (1989) for Comstock is based on only five T,, measurements and may be revised with more data "Using flvid inclusion data for geobarometry and seem ing a hydrostatic boiling point for depth pressure gradi- ent, estimates of the depth of mineralization range from <100 to >500 m below the palcowater table. Figure 5 shows Mstugiains uf Ty, data fivns MLoughlin, where the post tion of the paleowater table is marked by the silica sinter that hosts the top part of the sheeted ore-bearing veins. ‘This figure exemplifies the technique used by many work: crs to determine the depth of mineralization (¢,, Vikre, 1985; Cooke and Bloom, 1990). Since hydrostatic pressure gradients are common in active geothermal systems (e.g. Fienley, 1985), they are generally assumed in epithermal ee partial pressure of gases (determined by gas chromato- ‘graphy) requires overpressuring of up to lithostatic values, Consistent with Tf, values in Figure 5. Stable isotopes Stable isotopes are measured in several of the commonly occurring mineral phases: avygan in quartz, advlaria, eal. ite, and clays; hydrogen in inclusion fluids and clays; sulfur in pyrite and related sulfides; carbon in carbonates. They have been used mainly to determine the source regions of, aqueous and gascous constituents in mineralizing solutions ‘and to help interpret paleohydrology (e.g:, O'Neil and, Silberman, 1974; Kamilli and Ohmoto, 197; Sawkins et al., 1979; Matsuhisa et al., 1985; Vikre, 1987; Conrad et al., 1992, 1999; Matsultist 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 dithicult, Much more uselul are the combined determina: tions of oxygen and hydrogen isotopes, which are used to interpret water compositions, and hence, source regions, especially in young deposits where the composition of local meteoric water at the time of mineralization can be confi t — i : i a 100 140180 Homogenization temperatures (°C) Fi. 5, Hi incon temperature of homogentaton dita pote in ‘sporsaturated curves from McLaughlin (rom Sherlock et a, 1905). dently interpreted from modern compositions (e.g, Acu- pans, MeLaugllin ‘The intexpretation of the water oxygen isotope composi tions is calculated from the temperaturedependent equi- librium between water and mineral phases (€-g., Matsuhisa etal, 1986) and therelore vartabilly exists n tie !90/!°U ‘water values, on the order of up to 2 to 4 per mil, due to "uncertainty in the equilibration temperatures. D/H values tend to show a broad scatter of up to a few tens of per mi presumably because they are measured from inclusion fl fds that may comprise several generations of fluids. These ‘atations in isotopie compositions are much wider than Ihave measired in marier hydrothermal stems ands the scale of interpretation for ancient systems isnot as fine as for moder systems, where, for example, the effects of boiling and mixing are readily identified (eg, Giggenbach and Stewart, 1982; Giggenbach, 1092). ata for deposits shown in Figure 6 are representative of the wends. The oxygen and hydrogen isotope composi- tions of mineralizing waters typically plot to the right of the global weturie mates le tudicag varatvus fu Use 80/10 rato. ‘The datain Figure GA indicate that local meteoric waters generally the dominant constituent ofthe thermal solutions. {Einear arrays connecting ine local meteorie water compost tion with the interpreted thermal water compositions that uwend to the right (.e., horizontal) of the meteoric water Tine are thought to result solely from oxygen isotope ex- change between country rocks and meteoric water (€(CHARACTERISTICS AND GENESIS OF EPITHERMAL GOLD DEPOSTTS Craig, 1963), whereas a corresponding increase in D/H ra- tios creates a positive slope that suggests magmatic water in- puts (eg., Giggenbach, 1992). Although the data cannot be taken as diagnostic, they do suggest that magmatic water may contribute up to 10 pereent or more of the overall isotopic ‘composition of the mineralizing solutions in some lowstulf- dation epithermal deposits (e.g, Sawkins etal, 1979; Sim tmone, 1005). Any magevatie nitration to the Mcfanighlin epithermal environment is masked by extreme increase in ‘oxygen isotopes due to water interacting with the rocks of the Great Valley Sequence, which have 90/160 values higher than igneous rocko (Gherlock ct al, 1995). High Sulfidation High-sulfidation gold ¢ copper = silver ores are intimately associated with quart, hypogene clay, mica, aud sulfate gangue (Table 2). Hypogene covellite, alunite, and native sulfur are characteristic. Some minerals that are common in low-sulfidation deposits (cg. calcite, rhodochrosite, adu- laria) are absent from high-suifidation environments, and ‘openspace-fll extures are comparatively uncommon. ‘Many high-sulfidation deposits are characterized by a central residual or vugey quartz zone, which is interpreted tobe the site of intense leaching and alteration by acid flu ids (pH <2; Stoffregen, 1987). Characteristic gangue min- erals include quartz and minor alunite, clays (pyrophyllite, Vantinite, dickite), dinepore, harite, sinyite, native sulfie alumino-phosphate sulfate (APS) minerals, rutile-anatase, and pyrite. Ore minerals include gold, electrum, enargite- luzonite-famatinite, tennantite-tetrahedrite, chalcocite, bornite, chalcopyrite, covellite, and tellurides, Ore miner. als can occur within secondary porosity ("vugs") generated by acid leaching of feldspars, other phenocryst phases, and breccia clasts, The groundmassis totaly replaced by quartz, immor alunite, cays, ruule (or ttatase), and pyrite, Where the procolith is aphanitic, massive quartz may form. In ad- dition to vuggy and massive quart high-sulfidation ore can also occur in massive sulfide veins, quartzalunite-clay veins, and breccias. ‘Zones of alunite-quartz, kaolinite-pyrophyllite, smectite- illite, and propylitic alteration extend outward from the zone of residual quartz and mineralized veins over dis- tances of 1 to 100 m (mostly 2-4 m; eg, Lepanto, Nansatsu, El Indio, Summitville; Fig. 3). Contacts between, these mineral zones can 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 CusAu deposits have been identified be- neath or to the side of some high-sulfidation systems (e.g., Lepanto, La Mejicans, Table 2; Paradice Peak, Silitne and Lorson, 1994) There is a pronounced permeability contrast between che vuggy quartz and clay alteration zones in many higit-sul- uadivn deprnie, Deep wealesing van strongly affect the residual quartz zone, leaching sulfides and developing sc ondary iron oxides and oxyhydroxides, and jarosite at si nificant depths in the mine environment, or even leach- ing them totally. In contrast, the impermeable advanced 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 et al., 1994) ‘Fluid inclusions ‘The generally corrosive environment of ore formation lim its the material available for fluid inclusion studies. Most data ‘come from quarts crystal filling wgx. rhowigh these are com- ‘monly late, and from secondary inclusions in quartz phe- ‘nocrysts, which are temporally unconstrained. Data have also been obiained from enargite, alunite, barte, pyrite, spha- lovite, disopore, cderite, and hbmerite. Abundant tale of secondary fluid inclusions can make identification of pr- mary fluid inclusions difficult (e.g, So et al., 1998), In rare cases, primary fluid inclusions have been documented to ‘occu wilt yrowth zones of euhedral quartz expstals (¢. Losada-Calderon, 1992; Ruggieri etal, 1997), though their relationship to ore genesis is unclear. Other workers have stated that primary fluid inclusions are present, but they do not explain the enteria used to classify them (e,g., Mancano and Campbell, 1995; Jannas eta, 1999). High-sulfidation deposits mostly contain two-phase (liq uid + vapor) fluid inclusions. Although both liquid-ich and vaporich inchisions are recognized, most workers do not advocate boiling as an important depositional mecha- nism (e.g,, Table 2). Rare multiphase brine inclusions that contain halite daugbter crystals in addition to liquid and vapor + other daughter phases at room temperature have been documented from several deposits (e.g. La Mejicana, Losada-Calderon and Bloom, 1990; Kasuga, Hedenquist et al, 1994; Rodalquilar,Arribas etal, 100%; Furtei, Rigger ‘etal, 1997). Three-phase fluid inclusions that contain vis ible CO, occur at Zijinshan (So etal, 1998). Microthermometric studies have revealed that some jou dcposits contain only dilute (<1 to--5 wt © ‘aCl equiv), moderate temperature (Ty, = 100"-350°C) two-phase fluid inclusions (e.g., Lepanto, El Indio, Pueblo Viejo; Table 2; Fig. 4B). Other deposits, such as La Meji- cana, Kasuga (Nansatsu), Rodalquilar, Furcet, Summievl Paradise Peak, and Julcani, have fluid inclusions with simi- lar ranges in homogenization temperatures (some T), val tues in excess of 400°C have been reported). but much greater ranges in salinities (<1 to 46 "wt % NaCl equiv; Table 2; Fig. 4B; Arvibas, 1995). Based on fluid inclusion geobarometry, estimates of palcodepths below the water {able for high-sulfidation deposits range from 150 to 300 m (Nansats), 60 to 680 m (Furte), 300 to 700 m (La Mejicana), and ~200 to 900 m (Rodalquilar), Stable sctepoe Over the past decade, oxygen and deuterium isotope studies have advanced our understanding of the forma- Hon of high sulfidation depocies significantly (eg, Bye etal, 1993}. A variety of hydrous minerals that are suitable for analysis occur in different locations and paragenetic stages within high-sulfidation deposits (e.g., alunite, kaoli- nite, illite), Oxygen anil deuterium isotope analysis of the232 (COOKE AND SIBIMONS hhyerous phases and quartz has allowed fluid evolution and water sotrces in individual deposits to be characterized in dewal. Tn general, alunite has oxygen and deuterium isotope ‘compositions consistent with deposition from water pre- dominantly of magmatic origin (Fig. 6B). Hedenquist et al, (1998) caleulated that alunite at Lepanto precipitated fine watts wich formed by wonndeanative of up to mine parts magmatic vapor into one part meteoric water. Based ‘on oxygen and deuterium isotope compositions, the war ters that precipitate hypogene clays, silica, and ore miner- zation have a greater component of meteoric water Tela- tive to those that precipitate alunite (e.g., Nansatsu, Rodalquilar, La Mejicana; Fig. 6B) Sulfur isotope data have been obtained from sulfide, sul- fosalt, and salface minerals (e., pyrite, enargite, galena, sphalerite, alunite, barite) and native sulfur. The data have heen used to trace sulfar sources, estimate fluid comps tions, and for geothermometry (Arribas, 1995; Fig. 7). The source of sulfur is generally interpreted to be maginatic, al though the sulfur isotope composition of the source is typ- ically calculated to be greater than zero in most deposits, up te a maximum of 0 2 por mil at Redtalqitar (Fig-7) Using pyritealunite isotope pairs, calculated equilibration temperatures range from 180° to 420°C and are consistent with temperatures of SO disproportionation in hy- Urothermal vids (Asvibes, 1905). Sulfide minerals have distinctly negative 64S values in ‘many deposits (Fig. 7). The negative sulfur isotope com- positions of sulfides and sulfosalts are consistent with sul- fide precipitation under oxidizing conditions, widh redux controlled isotopic fractionation driving enrichment of 5, in the sulfides and sulfosalts (e.., Heithersay and Walshe, 1995). Coprecipitating sulfates become progressively en- Hehe in BS eaulung ite tend toward 9 values th ‘excess of 30 per mil (Fig. 7). Epithermal Mineralization in Modern Environments Modlern geothermal systems provide a context in which the mineral produets of hydrothermal activity can be compared directly with coexisting fluids at known tem- TReratires, preeentre, maee flaws, and chemical composi tions. The low-sulfidation epithermal environment has been explored by drilling a number of systems in vole canic arcs (e.. Japan, Philippines, Indonesia, United States, Mexico), but the best studied are those in New Zealand, such as Broadlands-Ohaaki where precious and base metals are depositing (Browne, 1969; Weissberg, 1960; Weisberg etal, 197; Brown, 1986; Simmons and Browne, 2000); By constant, dhe Iighesulfalativns coi ronments known only through surface suidy of thermal features of active volcanoes and the hydrothermally ak tered material ejected during their eruption, such as at, White island (biggenbach, 198/; Hedenquist et al. 1993). Both examples are located in the Taupo Volcanic Zone (Fig. 8), providing a unique opportunity to exam- ine the to subclasses of epithermal environments within the same modern geologic context. Broadlands Ohaaki Broadlands-Ohaaki shares many of the features of low- sulfation envieonments shown in Figure 1A. Over 50 wells have been drilled at Broadlands Ohaaki over an area of about 8 km®. Most of these are vertical, ranging from 400 to 600 m depth. The deep (production) water is dilute (C1, 000 mg/g C1) with high concentrations of dissolved ss (-26,400 mg/kg COs, -100 mg/kg H,S).Itis nearnew tral pH, reduced and responsible for widespread alteration of felsic volcanic host rocks to quart calcite, illite, adu- Tart albhe, pyrite, aud ehdurive at wemperatures £250" C. Figure 9A shows that precious and base metal mineral ization occurs in three spatially distinct environments: in ‘geothermal well scales and precipitates, atthe Ohaaki Pool, 4nd in vugs andl veins in hydrothermally altered rocks (Sim- mons and Browne, 2000). The scales and precipitates in geothermal wells contain the highest concentrations of gold and silver and are important for understanding ore- forming processes in low-sulfidation environments. ‘The drilling of production wells provides free flow paths for chloride waters to ascend to the surface. Here, steep pressure gradients pramate high mass finx. Mashing. and mineral deposition. For example, platy calcite precipitates at the level where phase separation begins near the well feed point, due to exsolution of COs. Such deposits ex: tend for only 100 40 800 m wp the well (Tulloch, 1082). Im surface pipes, electrum and chalcopyrite deposit on back pressure plates, attaining spectacular concentrations of up to 5 wt percent gold and 17 wt percent silver (Brown, 1996), downstream of these and the separator, amorphous silica deposits occur, commonly in colioform crustiform bands. In some cases, precipitates and rock detritus are carried in the flow stream to the surface; these settle out in the weir box where the chloride water discharges to the at- mosphere. These unconsolidated materials comprise amorphous silica, sulfides, and rock clasts and contain up ‘o 100 ppm Amand 1,000 ppm Ag (Simmons and Browne, 2000). Brown (1986) showed that the deep, preboiled chloride water at Broadlands Ohaaki contains about 1.5 g/kg Au and 8 1g/kg Ag. consistent with subsequent analyses of war ters collected with ceramiclined downhole sampler (Brown ct al, 1997), From this and the average upflow rate for the whole system (-100 kg/s), Brown (1986) calculated that 1 Moz of gold flows through the system in approxi- mately 6,400 yr. By contrast to the wells, the volcanic rocks that are hy- drothermally altered by the chloride waters contain low amounts of gold and silves, with maaimum valuco of about ppm Au and <5 ppm Ag, despite sporadic occurrences of disseminated and vein sphalerite, galena, and chalcopyrite (Simmons and Browne, 2000). “Mineralization at Mie surface ts resutexed w dhe Obaahi Pool (800 m?), which before exploitation discharged a mixed chloride-bicarbonate water (Hedenquist, 1990). In 1957, a red-orange flocculent was observed, and over the next few years, itbecame incorporated into the sia sinter(CHARACTERISTICS AND GENESIS OF EPITHERMAL GOLD DEPOSITS 233, °4 A 277 8 Z a rs : z Ga ? © amarok Acipan aaa jM.. © eadriOnal ) © Comstock Toy EE 140 A Teyohtta os 0 5 0 6 0 & ® 5O(%o, SMOW) “| ‘Volcanic vapors | | . 404 , = ebiemagres é “ a fe al ‘Acidic fluids in high | WB Lepanto- alunite. é. siege, | Tmt Bm Y © La Mejicans -sevicite gL 1 Atte ateaton stage ~~ (© or mineralization 398 os 1D Ateration | mineralisation 50 (%-,SMOW) io. 6. 80, 5D for minerlcing ater iterpretc for cpithermal depose, A Data ftom quarts and quarthosted ‘uid inclusions from lowsuldation deposits. B, Data fom alunie from highsulfidation deposts (mode from Ar "has, 1995, with addional daa from LasadaCalderon, 1992). The compositions ofthe deep Mids from Broadlands- ‘Oakland White Island are ako shonm in A. The range of compositions of water discharged from hightemperstre fury on andes oleanoes aid bythe bx ele Voie pore (Gignac, 19) the age of ‘ompontions of ater dasolved sn fle melt sound by the box sbeied else magna (Layton KE). Able ations v= leat (Nass), Ka = Kasuga (Nansaes), PV = Pueblo Vio, Ro = Rodale lining the pool. Analyses indicate tha the precipitate com prised amorphous antimony sulfide (metastibnite, with high concentrations of gold (85 ppm), silver (500 ppm), sercury (2,000 ppm), thallium (680 ppm), arsenie (100 pm), and antntony (10,000 ppm; Welberg 1909). hls Iineralzation is similar to that atthe Champagne Pool at Waiotapu and acid sulfatechloride springs at Rotokawa (Weisberg, 1968: Hedenguist and Henley, 1985a; Kru ind Seva, eB). All of these mom lkCh share «coe mon formation mechanism involving effective scavenging of aqueous gold and siker from solutions understurated in precious metals onto amorphous arsenicantimony st fur colloidal compounds in acid solutions (Renders and Seward, 1989). Although this style of mineralization is not known in lowsulfidation orebodies, the process of gold scavenging may be relevant in Carlin-type deposits where gold and arsenic show strong correlation (Hofstra and Eine, 2000). In its natural state, ore-grade precious metal mineraliza- tion did not form in the Broadlands-Ohaaki system, even though the deep fluid was transporting substantial aqueous gold (Simmons and Browne, 2000). fnstead the requisite permeable channels for ore deposition, in which boiling and high mass flows are sustained, were formed by the drilling of wells, reinforcing the concept chat epithermal ore deposits are mainly sites where metal deposition is efficient.234 (COOKE AND SIMMONS = Sulicos = Sufates Wav Mos ] OMS. nss0. i T T T 7 T { Lepanto ‘ee 9 | ete 220-820 26 | Nansatsu a Vo | tem] 200-2409 1 \ Puctio Viejo! —— ‘Y ee ee i Jule i a : a! 210-270 | Rodalquiler | | — | mms | 220-330 { 400 OO 5¥S(%, COT) Fo. 7, Sullar isotope data for sue and slate ner from highsuldain depos, showing the eet of ie proportonation a 910°C The equilibrium Hotope facionaton temperature (bred On coextng sulidesulate Bain) ae shown as anges he clculted HeS/S0, ato are to shown, Modified from Arne (908). i GEOTHERMAL AREAS 4 Delineated by ding Delineated by geoptysies ; Other thermal area VOLCANO i O50 7K Fig 8. Map ofthe Taupo Volenic Zone in the North sland, Ne Zealand, showing the locations ofthe Broadland Ca! geothermal te and White sand wlcan (if rom Heder, 198) The Taupo Vleane one com : taints about 0 equbapaced geothermal systems atocited with cle alkaline magiratim. About hal ofthe systems have 4 ‘een dled vo dept of 00 te 3.800 mr Hove roche comprite sequene of ntenaryvlranie dept a rodn ‘andy yolte composition that nconformably omer low rank metamorphosed grayeacke(CHARACTERISTICS AND GENESIS OF EPITHERMAL GOLD DEPOSITS 295, B Mineral deposition in open spaces ‘Mineral deposition ‘in open spaces pie aie z = 2 TAs \ ee kom gm ye $ 2 tanto Resor 7 sore An del Fig 9. Hydrothermal mineralization inthe Broudlands Ohaaki geothermal ssem (mode from Simmons and Dome, 2000). da dana ic dhuw sista entnonmene of precious met deporion ime ges hema! production wel subvert fsctres in voianic host oc, and dhe Ohaaki Pool. B Vertical distbution af el ‘ek eldepar (adslaria, gold, quar, and'amorphous sila that deposit due to baling, computed using the SOLYEQ. find CHILLER prograans, Note that god deposi downsrcam of the point of fst oiling due to the inital emoval of Hand CO, from the liquid, which increases gold solubility through oxidation and pH inerease in the liquid, Gold de [rhidon enfues tt coole tmperstes when the exsolaton ot Hye breaks Con tne got sui complexes (STOW, 1956; Seward, 1980) White Island White Island is currently the most active volcano in the Taupo Voleanic Zone of New Zealand (Fig. 8) and is the site of 2 modern highsulfidation epichermal system (Hedenquist et al., 1993). Lhe composite cone 15 con- structed of andesitiedacitic lavas and rises 700 m from the shallow sea floor. The main erater floor, which is close to sea level, contains high-temperature fumaroles and acid Springs associated with the degassing andesiic magma. Sea- water incursion is blocked by the deposition of anhydrite, which forms a seal and isolates the magmatic hydrother- ‘mal gxtem. Thns famarolie discharges come directly from a subjacent degassing magma (Giggenbach, 1987). An- ddesitic ejecta from the volcanic vent contain pervasive and fracture-controlled cristobalite-alunite-anhydrite-pyrite al- teration asvemblages and veins filled with alunite, anhy- drite, Avich chlonit, and trace pyrite. The 88 analyses of ‘coexisting sulfate pairs indicate SO, disproportionation and equilibration temperatures of 380°C = 50°C. "The iayva. gana discharging froma White Land eve oxidation potentials near the SOg/H,S gas buffer, consistent with the oxidized conditions inferred for high-sulfidation epithermal deposits (Giggenbach, 1987). Taking the ther ral output (-390 MW) and 309 fax, along with resulss of aerosol sampling, the daily flux of copper and gold in the magmatic gas plume is 280 kg Cu/d and 0.1 kg Au/d (Hedenguist et al., 1993). At this rate, 1 Moz of gold dis charges in ~850 ye: However, there is litle evidence that sig- nificant amounts of copper or gold are currently depositing in the hydrothermal system (Giggenbach, 1987; Hedenquist et al., 1993), So, like Broadlands-Ohaaki, White Island also appears to lack a favorable environment for metal deposi doh, UE the rests show that calcalkaline tags way De sources of metaltransporting ligands, and of the metals themselves. Chemical Environments of Ore Deposition In this section, we review the current understanding of gold and sulfur speciation in hydrothermal fluids and discuss the potential implications for epithermal ore formation. Gold speciation Gold occurs in the +1 valence state in aqueous species under hydrothermal conditions, due to the low-oxidation potential of most hydrothermal waters (Seward, 1991) Here, gold has low solubility as a bare ion (Aut). Signifi- ‘cantly higher gold solubilities can be achieved when gold Forms aqueous complonce with various ligands (og Cr, HS-, CN’, etc.). These are necessary to generate the rela- tively high aqueous gold concentrations (21 ppb) in ore forming hydrothermal solutions (e-g., Brown, 1986; Seward atid Bates, 1997, CuURE etal, 2000). Processes of metal deposition are dependent on gold speciation in epithermal environments. Ligand availability and the prevailing physical and chemical conditions con- {tol the abundance and composition of individual gold236 (COOKE AND SIMMONS species. This in turn determines the total amount of gold. that can be dissolved in mineralizing solutions, i, ZAM = m(AU(HS)2) + M(AUHS yg) + m(FAU(HS) gg) # m(AUCH) +. ete a) ‘A depositional procease may be effective at precipitating gold from one gold-bearing aqueous complex but may Ihave no effect on the stability of another. For example, boil ing will cause H,S to degas from a mineralizing solution. ‘Ths tn turn cat destabilize complexes such & AUC) causing gold to precipitate. However, H,S loss does not a fect the stabiliy of AUCH, and boiling of solutions in which gold occurs predominantly as a chloride complex may not Cause gold deposition, Seward (1991) provides a detailed discussion of gold chemistry in hydrothermal environments, Au* readily forms aqueous complexes with halogen- or sulfurbearing ligands in hydrothermal solutions, Based on experimental studies, high-temperature thermodynamic properties for several hydrosulfide gold complexes have been derived: e.g., AN(HS)z, Seward, 107%: Shenherger and Rarnes. L0K4: Gammons and William-Jones, 1993; Benning and Seward, 1996), HAU(HS)9i,q) (Hiyashi and Ohmoto, 1991), and AUHIS),.) (Benning and Seward, 1996). Based on their ex- porimotital dats, Bonning and Seward (1006) conchided that AUHS,,,) was the dominant gold-ransporting species in low pH solutions over a wide range of total sulfur coneen- trations and temperatures. Consequently, we restrict further discussion of hydiosulfide guld Wauspurt w AULISiag, aud Au(HS)3, Other aqueous gold hydrosulfide and sulfide complexes may exist; however, their high-temperature thermodynamic properties have not been derived. ‘yctrosuitide complexes are important for gold transport when waters are reduced (Em. > Em), sulfur concentra- tions are high (20,001 m), and temperatures are less than 300°C to 350°C (Figs. 10 and 11). Such conditions are typi- ‘al of low-sulfidation epithermai environments (Fig. 11). AUHS,,g) dominates under moderately acidic and/or lower Ems. concentrations, whereas Au(HS)3,, dominates under near-neutral pH and elevated Emp. concentrations (Fig. 11 reaction 2). The solubility maximum for gold as a hydro- sulfide complex occurs in the concentrations (Fig. 11; re- action 2). The solubility maximum for gold as a hydrosul- fide complex occurs in the Au(HS); field, at nearneutral pH conditions, straddling the sulfate-sulfide boundary (Figs. 10 and 11): Aull iag) | M8 yq) “+ Aw (TIO)3 11 @ The relative stabilities of gold halide complexes are as follows: Auly > AuBrg > AuCly >> AUF (Seward, 1991) However, because chioride Concentrations are much greater than other halides in hytirothermal systems, AuCls is likely to be the most important gold halide complex. Chloride complexes have strongly temperature dependent stabilities, such that gold chloride is unlikely to be impor tant as a transporting agent at temperatures below 300°C, unless waters are highly oxidized, acidic, and/or sal (Figs. 10 and 11). Such conditions may occur in high-sulf- dation epithermal environments It is theoretically possi ble that an increase in pH or HyS,a,) Concentrations, of a decrease in salinity or temperature may cause a switchover from chloride to hydrosulfide complexing, without result ing in gold deposition (Fig. 10). AuCl; + H,Sjgg) © AUHS 9) +H +2CP. 8) Aluiough sui noc well understood, vapor phase gold ana copper transport (Heinrich etal, 1992; Symonds and Reed, 1993; Mountain, 1999; Ulrich etal, 1999) may be important for the genesis of some high-sulfidation epithermal gold- copper deposits. It could also be important for enriching reservoir fluids with gold in lowsulfidation systems. Sulfr speciation Hedenquist (1987) proposed that fluid chemistry should bbe the basis for classifying epithermal deposits, because of fundamental differences in the inferred oxidation poten- fal and pH af the mineratizing eabatione Inferring the pit ‘of a mineralizing solution is fairly simple, because the sta- bilities of many common hydrothermal alteration minerals (clays, muscovite, adularia, carbonates, ec.) are pH depen- dont. The oxiddtion potential ofa hydrothermal solution i ‘more difficult to determine. It must be inferred from hy- ;pogene mineral assemblages and/or sulfur or carbon iso- ope compositions. The situation is complicated because ivetals used w infer de vaidation potential of hyde ermal solutions (c.g. sulfides, sulfosalts, sulfates, oxides, etc.) can precipitate under both oxidizing and reducing conditions (e.g, Cooke et al., 2000). ‘From a hydrothermal perspective, itis logical to detine the redox state of waters in terms of sulfur speciation, be- ‘ause of aqueous sulfur’ strong controls on base and pre- cious metal solubilities and ore deposition (Cooke et al. 2000). Hedenquist (1987) defined low-sulfidation systems as those where sulfur generally occursas reduced aqueous species (-2 valence state) in mineralizing waters entering the epithermal environment. High snlfidarion was defined in reference to systems where volcanic gases contain sulfur dominantly as $0. i») (+4 valence state), the predominant sulfur species in oxidized magmatic systems. When the SOag is absorbed by ground waters, disproportionation can pro- duce an acidic water (Rye, 1993) in which sulfur oceurs predominantly as sulfate species (+6 valence state), e.g. 4509 g) + ATMO, + 9TTBOG + M95yuq) + DHL “ Note that the terms low and high sulfidation do not re- Jate to the abundance of sulfur, which is highly variable and generally unguantiapie in each depost ype In the following discussions, we define oxidized waters as those in which sulfur occurs predominantly as dissolved sulfate species (HSO;, SO}, etc; Figs. 10 and 11). Re- duced waters are defined a8 those where aqueous sulfide(CHARACTERISTICS AND GENESIS OF EPITHERMAL GOLD DEPOSITS 237 2 a seve sac. sham ae oa teouced Jon Say at “Pyrite : 2 t60 200 250 a0 5080 Tro 100 100 150 AUlHS)3 100 wee To) ‘AuClz nn 7 2) 280-900 350 © 50 100 150200 280 TO) Fo. 10. Ry digrans showlog the sab feds of Fe oxides, Fe ules, acini (hol), lite (lun, calee (ca ard anhydite (any), goa solubily cootoure and predominance els for aque slfurbeaing a gold bearing species “Ry is defined log info). a ina measure of oxidation responding to Nove ondsng contigo et eated tog shee isin degrees Ketan (Ciggenbach, 1087-AES- 0004 mpl = toys =DDTE = 2188 1 feldspar ite stable rossi, ‘ptt. Thermodynamic dt rom fohnaon etal (1993), Benningand Seward (1906) venti, with higher values of “Ry Iythe equation tog joy » 5.825 332/1=2 Ra, 6 saliniy=0.5 we percent NaCl equi, 3G» 0.41 -KeAlsileate forthe conditions poruajed. B25 0.01 m, pH 00886; ans. ~ 2:44 109, Moscovite the stable KAl cate nd Willamefones (1095). Distibuton of species cleuations made by Nevor-Raphson iteration wing an unpab- lished spreadthect species are predominant (H,Siaq), HS", ete; Figs. 10 and 11). These definitions are independent of the actual total amount of sulfr dissolved in the water Deposition Processes Although hydrology is important for water and gas mi- gration into and through epithermal environments, gold deposition results from the chemical reactions that take place within the fluids and adjacent wall rocks. In this sec- tion, we discuss possible depositional mechanisms for ep- ctinal minesalieativn, within the framework of gold spe Ciation behavior, Lowsulfidation epithermal deposits In lowsulfidation deposits, gold is transported primarily as Au(HS)z in dilute, reduced, near-neutral pH waters (Fig. 11). Chemically effective reactions for gold deposi- tion include HS.) loss via boiling (reaction 5), wall-rock sulfidation (reaction 6), or destabilization of reduced sulfur bearing species via mixing with sulfate-bearing ground water (reaction 7): Au(HS)§ + H+ 0.5Hyjaq) © Atty + 2H2Sip © Au(HS)3+ [FeO] + H* € Aug, + FeSgi +Hg0¢) + 0.5Hajq) @ and Au(H8)z + 8HjOp, © Aug) + 280F uo 4 BHP + 75H o Whereas these are all viable mechanisms for gold depo-238 COOKE AND SIMMONS B sugn suniatonoopsts Low uttton Dope Di Los fy crams 0" m0 8 pret Nga The sly feof ole and a fides, Rela ( iuscovite (ns), kaolinite (kao) alunite alun), calcite (Ca) and akyéte (ak), and the pre- dominance Hels of aqueous wufurbearing specie. B. Gold solubility coors andthe predominance elds of nan bility Ry values Ste shown on the right vertical axes for comparative purposes. Distribution of species ealealaions made by Newton-Raphson iteration using an unpublished spreadsheet, BS = 0004 me 2C = Ol me 351 LO (modied alter Cooke eel 1996) sition, each process should produce distinctive gangue as semblages and fluid compositions that could be readily dis: criminated. Numerical stmutations have demonstrated the ettec- tiveness of boiling for gold and silver deposition in epi- thermal environments (Drummond and Ohmoto, 1985; Reed and Spycher, 1985; Seward, 1989; Cooke and McPhail, 2000; Simmons and Browne, 2000). Boiling of neutral chloride waters can also result in the deposition of abundant carbonate and adularia, due to the pH increase associated with CO loss (Browne and Fils, 1970; Reed and Spycher, 1985): In modern systems, proof of the chemical effectiveness of boiling-induced HS loss is pro- vided by clectrum deposits on back pressure plates in geo- thermal wells (Brown, 1986). The distinetive gangue min- eral assemblages and textures produced by boiling of low-salinity nearncutral pH waters (e.g., bladed carbon- ate, lattice textured quartz, adularia) are present or abun- Matit fu aise Towoulfidaivu epidicssuel depusics (Si mons and Browne, 2000). Finally, the relatively narrow vertical intervals of ore deposition in lowsulfidation veins and their fluctuation in space (e.g., Fig. 2) is also attrib- table to the boiling environment {Simmons and Browne, 1998, 2000) Despite widespread evidence for boiling, some workers advocate mixing as the principal mechanism of ore dey Sion in lowsufidation epithermal deposits (eg, Vile, 000487; as 1989; Corbett and Leach, 1998). Apart from excellent fluid inclusion data at Creede (e.g., Hayba, 1997), which is an AgPbZn epithermal deposit there is usualy scant ei dence in support of mixing models tor low-sullidation ep ithermal deposits, and chemical and mass balance consid- erations are usually not discussed. The physical problems associated with mixing two waters that have different den- sities and temperatures in porous and fractured rocks are also generally ignored. Itis difficult to speculate on the chemical effects of mix- ing withont knowing the compositions af hath waters in volved in the mixing process. If mixing causes a reduced, nearneutral pH water to be oxidized (0 sulfatestable con ditions, then gold may precipitate (Reed and Spycher, 1085; Spycher and Reed, 1980; Figs. 10 and 11; reaction 8). This would require mixing with steam-heated acid sul- fate water, which is largely restricted to the water table (Hedenquist, 1991). Furthermore, depending on the ini- Gal vaidadiun potendal uf dhe clluvide water, guid deposi tion may be suppressed initially by mixing-induced oxida- tion because, as for boiling, this can increase gold solubility while H,S,,9) remains the dominant aqueous sulfur species (rigs. 10 an 11; Cooke and Merhaii, 2000). With conbn~ ‘ued mixing, dilution could then lower gold concentrations so that saturation is never achieved. Mixing of chloride water and peripheral bicarbonate water is also ineffective at depositing gold (Simmons and Browne, 2000) ani(CHARACTERISTICS AND GENESIS OF EPITHERMAL GOLD DEPOSITS From a chemical perspective, wall-rock sulfidation reac- tions can result in ore deposition in lowssulfidation ep- ithermal deposits (reaction 7), However, because most of the gold is vein or breccia hosted, sulfidation reactions are probably not important for ore deposition, If wallrock sul Fidation was the key depositional mechanism at an individ- ual low sulfidation deposit, then gold would occur primar- I #s hnlusiuus vt subadcaied wide de yell lattice of secondary pyrite in the altered wall rocks. Conductive cooling may occur in lowsulfidation envi- ronments if waterrock ratios are low and repose times are tong (Drummond and Unmoto, 1985), but such cond- tions do not favor ore formation. Figure 10 illustrates that temperature change has litte effect on the solubility of told a a hydrosulfide complex from 300° to 150°C, and so Cooling alone is not an important mechanism for ore de- position in low-sulfidation environments (cf. Sander and Binaudi, 1990) High-sujudation eputhermal deposits Debate about the genesis of high-sulfidation deposits arises from uncertainties concerning the chemical compo- Hitions of their mineralizing watere, Arrihae (1005) eynthe: sized a two-stage genetic model for high-sulfidation de- posits (Fig. 12), based on a previous model by White (1991). In the first stage, magmatic gases cause intense acid Teaukiug aud derstopmicat of advanced argillic alteration assemblages. Stage two waters exploit the secondary poros- ity and permeability created by the acid-leaching event and precipitate gold and copper minerals. Arribas (1995) pro- ‘posed two possible origins for the mineralizing stage wo ‘waters (Fig. 12): (1) condensation or dissolution of mag- 239 matic gases into a heated ground-water convection cell, which produces an acidic, lowsalinity mineralizing water; and (2) mineralizing magmatic brines which ascend to the region af advanced argille alteration, where they mix with shallow ground waters and precipitate high-sulfidation ore. ‘Although the models summarized by Arribas (1995) are consistent with observed paragenetic and geochemical re lationships in many deposits, ie io doubeFal whothor sithor, of the stage two waters are oxidized (or high sulfidation) from a chemical point of view (eg. Jannas et al., 1999). Based on our current understanding of gold speciation, ‘here are three viable scetatios fon gold waste iat gh sulfidation environments; 1. Gold (and copper?) are transported as hydrosulide complexes (6 ANHS,yp)) 1 lowsalinity acd waters that contain high concentrations of reduced sulfur (Stoffregen, 1985; Gigenbach, 1997; Hedenquist et aly 1998; Jannas etal, 1999); Le, reduced (low sulfidation) waters (Fig. 10). 2, "Gold and copper are transported in the vapor phase as sulfide andor chloride species such as AUS, CaS, oF Gul, (Losada-Calderon, 1982; Arrbas, 1995; Mountain, 10008» rednced (low slfidation) gases 3. Gold and copper are transported as chloride com- plexes (e., AuCls, CuCl) in acidic brines of magmatic Gerivation (eg, White, 1991; Hedenquist etal, 1994). Gold tranoport may cecur wider oxidiaed or reduced conditions, provided that the mineralizing brines are sufciently Acide, hot, and saline (Fig, 10) For high-ulfdation epithermal deposits where gold is teamported a6 Aul15 gq in lowsalinigyacid waters (64. El Indio; fannas etal, 1989), the chemical reactions that con- ALTERATION ‘ORE DEPOSITION: Be tn Fo, 12, Twostage model for highsulfidation ore formation proposed by Aribas (1886), modified to highlight likely water compostions invohed in each stage of ore genesis, Sage 1 (A) is dhe ground preparation sage, whereby tmaghtic gases generate an aed slate high-slfidation water that esponsible fr the nial barren stage of ese tal slic and advanced apie alteration. The second stage involves gold deposition from aid chloride Yowsulfidaton ‘waters (B) of acid chloride Drines(B)240 COOKE AND SIMMONS twol gold deposition will be similar to those outlined above for low-sulfidation epithermal deposits, e.g.: AHS) + 0.5Fguy € At) HS, cy AUHS jg) +0.5(FCO] © Au +05FeSyiy + 0.5105, (9) and AUNS fay) + AHO) Ally + SOF (a) + 2H" + 8. 5H jag) (19) ‘As for AuHIS3, removing H,S from the mineralizing water isa highly effective method for depositing gold (reaction 8). Boiling of low-salinity acid waters (e.g. from 300° to 100°C) will canse pH to decrease due to the dissociation of ion pairs such as HCl,,q) and H,SO4i,) and may lead to gold deposition in association with quartz, kaolinite, and covellite (Reed, 1992). Unlike lowsulfidation environ- ments, howeven there are no mineralogical indicators to prove that boiling occurs other than the presence of coex- isting liquid-rich and vaporsich fluid inclusions. By in- creasing the acidity of the residual liquid, boiling may cause ‘ail uid aulyauived argilic unuefal asseublages eo de> posit, whereas the solubility of base metals may increase. Walkrock sulfidation reactions (eg, reaction 9) are prob- ably not important for the precipitation of gold in the residual silica zones of higitsulidation deposits. The mitt stage of ore formation involves acid leaching and the de- yelopment of residual quartz and advanced argilic alter- ation assemblages (Fig. 12), Because iron is leached from the protolith, the residual siliceous rock is nota favorable site for later wallock sufidation reactions. Gold, sulfides, and sulfosalts generally occupy secondary pore spaces, in- ddicating that the metals and sulfar were probably precipi tated directly from stage two fluids rather than via water rock interactions. ‘Most workers on highsulfidation deposits advocate fluid mixing as their proforred ore deposition mechanim (e.g ‘Table 2). Oxygen and deuterium isotopes have been used to demonstrate effectively thatthe waters which precipitate silica and advanced argillc alteration assemblages are mis- tures of magmatic and meteoric sources (Fig. 6). However, fluid inclusion evidence for mixing is lacking at the site of, ‘ore deposition in some systems that have been the subject of detailed investigation (e.., El Indio). The stabilities of aqueous gold species susie rein rte sgest nat ‘mixing could increase, rather than decrease, gold sol- If mixing is important for gold deposition from AWHS,,,) in low-salinity acid waters, then the same chemi- ‘al arguments for and against mixing apply, as outlined above for Au(HS)5 Evidence for mixing is well documented from Lepanto. Hedenquist etal. (1998) have used oxygen and deuterium isotope data obtained from gangue minerals to caleulate a ‘change in the ratio of magmatic and meteoric water com- ponents from 9:1 to I:1 over a distance of 4 km laterally. Mancano and Campbell (1995) provided fluid inclusion cevidence from enargite for mixing of saline hot water (1.5, ‘wt % NaCl equiv; 260°C) with steam-heated ground water (0 we % NaCl equiv; 150°C). Both data sets support fluid mixing in the oreforming environment at Lepanto. Flow- fever, ue preserice of vaportich luld inclusions in enarglee at Lepanto (Mancano and Campbell, 1995) and fluid clusion evidence for a steamrheated water indicate that phase separation was occurring at or below the sample Sites. hus boiling may have also contributed to gold de- position at Lepanto. ‘Some high-sulfidation deposits contain fluid inclusion ty brines (Table 2). In these systems, les could transport gold as AuCly under oxidized the temperature is above ~300°C) reduced condi- tions (Figs. 10C and 12). For these brines, gold can pre- cipitate in response to cooling, pH increase, reduction, and/or salinity decrease: evidence for high-salinit acid be AuCly + 0.5Hyiaq) € Aug +H +200 ay H,S loss via boiling, oxidation, or wallzock sulfidation will have no effect on gold solubilities, in contrast to is feffecis un hydicdulfie woinplened gold in Wiluce waters 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 poten- tially with a switchover to hydrosulfide gold complexing (reaction 4), which can both inhibit or prevent gold de- position. Conductive cooling could result in gold depos tion but is unlikely to produce ore, because itis sow and requires low flow rates, which will result in insufficient metal ux. Summary Substantial mineralogical, fluid inclusion, and stable iso- tope evidence shows that boiling isthe principal cause of sltcirum precipication in many low-eulBlation epithermal Geposis. High dissolved gas concentrations favor precious metal transport and increase the depth of initial boiling, Buoyant ascent of boiling chloride waters generally restricts mixing to the top and sides of upflow zones, where COr rich and acid sulfate steam-heated waters occur (Fig. 1) Mixing of the waters within the ore zone may occur during collapse of the hydrothermal system (e.g. Reed and Plum tee, 1¥¥2), producing barren clay, carbonate, or sulfate sgangue as steam-heated waters descend into the mineral- ized environment (eg, Simmons et al., 2000). Some high-sulfidation deposits contain unequivocal iso- topic and fluid inclusion evidence for Auld mixing. For many deposits though, it remains unclear whether this, process is responsible for (1) increasing the solubility of gold by entrainment of ligands and/or metals from mag- matic brines or vapors, (2) ore deposition, (3) gangue de- Mii(CHARACTERISTICS AND GENESIS OF FPITHERMAL GOLD DEPOSITS 241 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- ‘ease can cause deposition of gold, possibly during mixing with ground waters. In contrast, if gold is transported in high-sulfidation environments as AUHS 4a) within acidic, reduced, low salinity waters, then mixinginduced oxida tion or boiling may promote gold deposition, but cooling, dilution, and changes in pH are unlikely to be effeetive de- positional mechanisms. Acknowledgments, We are indebted to Mark Simpson for assistance with as- sembling the database on epithermal deposits and for prepa- ration of many of the figures. We thank Noel White and Patrick Brovine for their timely and thought-provoking re- views, and to Andrew Davies for constructive comments on an earlier draft ofthis manuscript. Thanks aso to Alex Losada- Calderon for usefl discussions. SFS. received financial sup- port for this paper from the Foundation for Science and ‘Technology (New Zealand), which is gratefully acknowl edged. D.RC. thanks the Australian Research Council for ‘their support through the Special Research Centre program, REFERENCES Arthas A. Je. 1005, Charartrtiee of high-eidasion epthorral de ‘posits and thei relation to magaatic id: Mineralogical Assocation oF Eznada Short Conrse Notes, 25, p. 419-454. 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Diamond ‘Cuxsactenistics axp Mopas ro CamnTre Gown Deposirs Albert H, Hofetra & Joan S. Cline (Giasactenistics AND GeNess oF Eptrnemat Gown Derosirs David R. Cooke & Stuart F Simmons EXPLORATION FOR EPITHERMAL GoLD Devostts ——_Jiffiny W. Hedenquist, Antonio Arras R., & Eliseo Gonzale-Urien Got Devosmrs RELATED TO ALKALINE MaGMATIsM ric P. Jensen & Mark D. Barton ‘Gout-Rics Porreyay Devosrrs: Descairnive axp Generic MopELs AND THRIK ROLE IN EXPLOKADON aNb) DISCOVER? Richard 1, Silttoe ‘GOLD IN SkARKS RELATED TO EPIZONAL INTRUSIONS Lawrence D. Meinert GOLD DEFOSHIS RELATED 10 REDLLAD GHANEIIG INEKUSIONS Jon F.F4. Thompson & Rainer. Newberry Gop in VoueaicHostep Masave SuLAe DEPostrs: [DisTRIBUTION, GENES, AND EXPLORATION David L. Huston Gop iw Sepex Derostis Poul Emsbo ‘Wrrwateesaanp GoLp Fists: GeoLocy, GENESIS, AND EXPLORATION ‘Tue Geonvnaaics oF WortD-Ciass Gon Devostts: (CraRAcTERsTiCs, Sesce-TiMe DISTRIBUTION, AND ORIGINS Robert Kervich, Richard Goldfarb, David Groves, & Seven Garvin il Phillips @ Jonathan D. M, Law ‘Tate CURRENT STATUS AND FUTURE OF THE INTERFACE BETWEEN THE "EXPLORATION INDUSTRY AND ECONOMIC GEOLOGY RESEARCH, TC. McCuaig & I. M. A. lronshy SOCIETY OF ECONOMIC GEOLOGISTS, INC.