In Magmas, Fluids, and Ore Deposits, Ed.: J.FM. Thompson, Mineralogical Association of Canada Short Course Vol.

23 (1995)

Chapter 19

Antonio Arribas Jr. Mineral Resources Department, Geological Survey ofJapan, 1-1-3 Higashi, Tsukuba 305, Japan


A consequence of the increased exploration for gold deposits during the late 1970s and early 1980s was the revision of the classification of epithermal deposits in order to account for the variations observed in styles of mineralization and inferred genetic environments. Among the numerous classifications that followed, one group of deposits clearly showed a common set of features; this deposit type is characterized by the presence of minerals diagnostic of highsulfidation states (e.g., enargite and luzonite) and acidic hydrothermal conditions (e.g., alunite, kaolinite, pyrophyllite). The terms enargite-gold (Ashley 1982), Goldfield-type (Bethke 1984, after Ransome 1909), high-sulfur (Bonham 1984, 1986), quartz-alunite Au (Berger 1986), acidsuifate (Heald et al. 1987), and alunite-kaolinite (Berger & Henley 1989) were applied to this group in reference to some of its mineralogical or inferred geochemical attributes. The term highsulfidation (HS) (Hedenquist 1987) is now widely used; the term was proposed originally to refer to a fundamental genetic aspect, the relatively oxidized state of sulfur contained in the hydrothermal system (i.e., initially S02-rich). This aspect is significant because it links HS deposits with one of the two main types of terrestrial magma-related hydrothermal systems (Henley & Ellis 1983), those associated with andesitic volcanoes whose surface manifestation includes high-temperature fumaroles and acid sulfatechloride hot springs and crater lakes. By contrast, low-sulfidation deposits form from neutral-pH, reduced (H2S-rich) hydrothermal fluids similar to those encountered in geothermal systems (Henley & Ellis 1983), with surface manifestation

including silica sinter-depositing hot springs and steam-heated acid-sulfate alteration. The main objective of this review is to summarize the characteristics of HS mineralization formed primarily within the epithermal environment, though recognizing the potential for HS conditions to occur at greater depths. Earlier studies have argued for a magmatic fluid component in HS deposits (e.g., Sillitoe 1983, 1989, 1991a; Hayba et al. 1985; Henley 1991; White 1991; Rye 1993; Hedenquist et al. 1994a), and the identification and characterization of HS deposits has contributed to a re-evaluation of the role of magmatic fluids in other types of hydrothermal systems (Hedenquist & Lowertstern 1994; Simmons this volume; de Ronde this volume). In this context, particular attention is given to the characteristics that are helpful in determining the nature of the magmatic contribution to the hydrothermal system through time and space. This review considers features of many of the deposits listed in Table 1, with locations shown in Figure 1, but is based on a selection of fourteen deposits for which the results of detailed geological and geochemical studies are available (Tables 2, and 3). For simplification, bibliographic references are not given in the text for general deposit features; these references may be fduh* in Table 1. For regional studies of HS deposits, particularly with respect to other types of magmatic-hydrothermai base- and precious-metal deposits, the reader is referred to reviews by Heald et al. (1987), Bonham (1989), Sillitoe (1989, 1991a), Berger & Bonham (1990), Camus (1990), White & Hedenquist (1990), Mitchell & Leach (1991), Mitchell (1992), and White et al. (1995).


A. Arribas, Jr. Table 1. Principal high-sulfldation deposits or documented prospects ordered geographically N°in Fig. 1 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 Deposit References

Asia & Australasia Dobroyde, Australia Whiter al. (1995) Rhyolite Creek, Australia Raetz & Partington (1988) Temora, Australia Thompson et al. (1986) Peak Hill, Australia Cordery (1986), Harbon (1988), Masterman (1994) ML Kasi, Fiji Turner (1986) Wafi River, Papua New Guinea Leach & Erceg (1990), Erceg et al. (1991) Nena, Papua New Guinea Asami & Britten (1980), Hall et al. (1990) Motomboto, Indonesia Perelld (1994) Nalesbitan, Philippines Sillitoe et al. (1990) Lepanto, Philippines Gonzalez (1959), Garcia (1991), Arribas et al. (1995b) Chinkuashih, Taiwan Huang (1955), Hwang & Meyer (1982), Tan et al. (1993) Zijinshan, China Zhang et al. (1994) Seongsan & Ogmaesan, South Korea Yoon (1994) Nansatsu (Iwato, Akeshi & Kasuga), Japan Izawa & Cunningham (1989), Hedenquist et al. (1994a) Yoji, Japan Yui&Matsueda(1994) Teine, Japan Ito (1969) Akaiwa, Japan Akamatsu & Yui (1992), Akamatsu (1993) Mitsumori-Nukeishi, Japan Aoki & Watanabe (1995) North & Central America Northwestern Vancouver Island, Canada Panteleyev & Koyanagi (1994) Goldfield, Nevada Ransome (1907,1909), Ashley (1974), Vikre (1989) Paradise Peak, Nevada John et al. (1991), Sillitoe & Lorson (1994) Summitville, Colorado Steven & Ratte" (1960), Stoffrcgen (1987), Rye (1993) Red Mtn-Lake City, Colorado Bove et al. (1990), Rye (1993) Red Mtn-Silverton, Colorado Burbank (1941), Fisher and Leedy (1973) Mulatos, Mexico Staude(1994) Pueblo Viejo, Dominican Republic Muntean et al. (1990), Russell & Kesler (1991) South America Julcani, Peru Petersen et al. (1977), Deen (1990), Rye (1993) Castrovirreyna, Peru Vidal & Cedillo (1988) Ccarhuarso, Peru Vidal ef a/. (1989) San Juan de Lucanas, Peru Vidal & Cedillo (1988) Cerro de Pasco, Peru Graton & Bowditch (1936), Einaudi (1977) Colquijirca, Peru Vidal etal. (1984) Sucuitambo, Peru Vidal & Cedillo (1988) Laurani, Bolivia Murillo et al. (1993) Choquelimpie, Chile GiOpper et al. (1991) Guanaco, Chile Puig et al. (1988), Cuitifio et al. (1988) El Hueso, Chile Sillitoe (1991a) Esperanza, Chile Vila (1991), Moscoso et al. (1993), Cuitifio et al. (1994) La Coipa, Chile Oviedo et al. (1991), Cecioni & Dick (1992) Nevada & Sancarron, Chile Siddeley & Araneda (1990) El Indio-Tambo, Chile Siddeley & Araneda (1986), Jannas et al. (1990) La Mejicana-Nevados del Famatina, Argentina Losada-Calderon & McPhail (1994) Europe Rodalquilar, Spain SSnger-von Oepen et al. (1989), Arribas et al. (1995a) Furtei-Serrenti, Sardinia Ruggieri (1993a,b) Spahievo, Bulgaria Velinovrtc/.(1990) Chelopech, Bulgaria Bogdanov (1982,1986) Western Srednogorie region, Bulgaria Bogdanov (1982), Velinov & Kanazirski (1990) Bor, Yugoslavia Jankovic et al. (1980), Jankovic (1982) Lahoca, Hungary Baksa (1975,1986), First (1993) Enasen, Sweden HaUberg(1994)

High-sulfidation Epithermal Deposits

C^IU-10 Western i f l P J5V-9 V *lcjk /S'fy g / Pacific


Figure 1. Worldwide distribution of high-<sulfidatfori deposits and principal documented prospects. The main highsulfidation metallogenic provinces are indicated. See Table 1 for deposit names and selected references.

Based on detailed research of the Summitville Au-Cu-Ag deposit, Stoffregen (1987) demonstrated that a nearly ubiquitous feature of HS deposits, fracture-controlled vuggy silica rock (intensely leached volcanic rock consisting dominantly of quartz; Fig. 2) is the product of very acidic conditions (pH <2 at T= ~250 °C) that occur within a sulfate-rich hydrothermal fluid formed by absorption of magmatic vapor. In addition to S0 2 disproportionate to H 2 S0 4 , significant concentration of HC1 from the magmatic vapor contributes to the acidic conditions necessary for alumina to be soluble, leading to vuggy silica alteration (Hedenquist et al 1994a,b). Neutralization of the acidic solution by reaction with the wallrock results in a sequence of alteration zones, outward from the hydrothermal conduit, which is indicative of decreasing acidity and is defined by the presence of alunite, kaolinite, illite, and montmorillonite ± chlorite (Steven & Rattd 1960; Fig. 2). This same alteration sequence, without the vuggy silica zone but with enargite-bearing ores, was documented in the Butte polymetallic deposit (Meyer et al. 1968) and in the roots of the

advanced argillic zones that commonly cap porphyry copper systems {e.g., Sillitoe 1973; Corn 1975; Gustafson & Hunt 1975; Koukharsky & Mirre 1976; Wallace 1979). Indeed, several of the deposits considered in this review are underlain by porphyry-type mineralization (Table 2). This advanced argillic assemblage is also typical Qf that associated with acidic crater lakes atop active volcanoes (Christenson & Wood 1993; Delmelle & Bernard 1994; Rowe 1994; Hedenquist this volume). The implications of a genetic relation between porphyry and epithermal mineralization, e.g., with respect to the origin of metals or the nature of the fluid inclusions in HS deposits, are discussed below. The observation made here is that an alunite-enargite assemblage records a similar geochemical environment, whether forming an epithermal deposit or as part of the alteration zoning of an orebody formed at greater depths. High-sulfidation deposits form in a position intermediate between intrusions and the surface; therefore, they may be located close to a porphyry copper deposit or in a near-surface environment, such as the roots of an acid crater lake. Comprehensive genetic models for HS deposits have been proposed only recently (e.g., Berger & Henley 1989; Sillitoe 1989; White 1991;


) Dis in stratabound VS/MS bodies. 183 t Ag. hbx + dis in MS Stratabound bodies commonly with hbx Mushroom-shaped bodies with stk + dis Veins Goldfield.y. hbx "Ledges" with veins. Au. qtz . Nevada Pueblo Viejo. del Famtina Veins. pyr = pyroclastics.5 my (Middle Voles) Qtz-monzonite porphyry <analyt.t.ons usea: CA disseminations. in earlier caldera -1. Cretaceous dac porpyhry+pyr Ands pyr. Japan Summitville.1 m. The change in genetic interpretation has more than anecdotal value because it illustrates the source of a not-uncommon misconception on the environment of mineralization of epithermal deposits. Colorado Age (Ma) 1.0-3. hbx.vuggy silica. Ag 60.y. Deposit form Hbx .0 -94 Dome along caldera margin? the distance and kind of rock traversed. 1994a). VS .) -130 9. dis in VS Hbx. location Motomboto. China Nansatsu. Pb. Argentina Rodalquilar. 4 i Au. preexisting ring 37. ands . hbx . complex Sillitoe. Table 2. 120. which can be generated by different mechanisms in three .5 Small volcanos Au 18 t Au (p) + 18 t in a caldera? Au reserves Au.(?) (poorly-dated) 5-3.7 m.y.) CA vol N/A 13-8 Veins + stk 4. error porphyry (±0. volx — volcaniclastics = . However.y.0 m.2 m.0 m. stk Dae dome.) Paradise Peak. pyr and volx Ands pyr + flows Ands/dac vol. 1201 Au(c) Au. Cu.2 N/A <analyt. error (±0. dis and stk surrounding veins Veins. rhy .100 t A g ( c ) Dome complex(?) Cu. as we understand them now. 1255 Ag to a central-vent 457 l Hg (p) volcano Au. rhy pyr. 1993) Ag. were formulated almost ninety years ago by Ransome (1907) following his classic study of the Goldfield Au-Ag-Cu deposit. sed . t 43 Ag. hbx + dis inVS "Ledges" with veins. Jr. 180tAg(c) Au 15 t Au (c) Cu. MS = massive silica.8 CAbimodal N/A (Rhy + basalt) volcanic suite Dac/rhyodacitic <analyt. Zn around a central diatreme Au. (c) » estimated total contained 1 Approximate number. Peru El Indio. Dome complex W.hydrothermal vein breccia or breccia pipes. veins.1 m.rhyol. collapse bxs + domes And/dacvd <analyt. dis in VS <analyt.3-1. Pliocene intrusive dacite Ands to rhy pyr flows. vol •» volcanic rock (unspecified).y. Hg Within or close 47 t Au.A. volx + ands flows Maar sed + basaltic vol (spilite) Dactorhyodacitic domes and tuffs Dac. Philippines Chinkuashih. Au. veins. Philippines Lepanto. error (±0. Ag Maar-diatreme >600 t Au (p. Taiwan Zijinshan. Chile La Mejicana & Nevados del Famatina. hbx.) Abbreviations used: w » calc-alkaline. Au >10 t Au (c) Local volcanic setting Central-vent volcano Small centralvent volcano Diatreme complex Dome complex Principal host rocks Genetically related rocks Time between host rock & deposit <1. error (±0. qtzdioritic stocks flows. error (±0. Cu. veins. Cu) Domes along 130 t Au. the quantity and character of admixed surface-derived waters. Indonesia Nalesbitan. Cu.000 tCu(p) Cu. Au.5 m.6 11-10 Dac/rhyodaoic porphyry stocks Ands flows + dykes <1. .000 Cu (p) fracture Au. the initially acid emanations would be neutralized and modified in their ascent through fissured rock . Ag 900. Arribas.) 1. error (±1. Ag. Ag >10-15tAu(c) Au 10 l Au (p) Caldera margin HorWende ands <0. the basic genetic controls. In his own words "the [ore depositing] solutions were essentially emanations from a solidifying body ofdacitic magma" and " .y. also hbx at N. Rye 1993. • IVIVUillVIWUVd ' (p) « produced. veinlets Vertical breccias. Ag Dome along 17lAu preexisting caldera margin Au (Ag.000 t Cu. Nevada 21 Miocene andesite Andesite <analyt. and the pressure and temperature gradients". dac + ands vol Paleozoic seds + granites.andesitic. ands/dac/rhy Dioritic. though it was quickly abandoned in favor of a "simultaneous solfatarism and oxidation" model (Ransome 1909).y.9 Metals. This concept formed the basis for Ransome's "direct volcanic hypothesis". hbx. Dominican Rep. quoted from paper or estimated from figures: 150 m for Paradise Peak is for individual orebodies Giggenbach 1992a.b r e c c t a ^ 5 n L 2 r f £ c k 'stk Abbrev. Au. flows + volx Qu-lalite porphyry None observed Qtz-diorite porphyry Dacite domes and flows Not reported Pliocene 1. stk « stockwork. Hedenquist et al. Miocene + older volx + metavol Dae vole Miocene sed Jurassic granite. Ag 92 t Au. Ag. stratabound replacements Veins or "ledges".5-1. Spain 19-18 Composite welded tuff.5 22. Veins. bre .segmentary rock. . The crucial aspect is identification of the origin of alunite or acid-sulfate alteration. Bi. (tonnes)1 Cu.000 i Cu.0 m. Main geological characteristics of 14 selected high-sulfidation epithermal deposits Deposit/district. Julcani. Cu Stratovo!cano(?) -140 t Au.

Indonesia Nalesbitan. 423 . (1994) porphyry Cu prospect Arribas etal. written commun. (2) by atmospheric oxidation of H2S in the vadose zone over the water table. permeable layers Steep normal faults + their intersections. H2S-rich fluid. Losada-Calderon et al. Zhang etal. but it may also appear in areas of advanced argillic alteration void of ore mineralization (e. Taiwan Zijinshan. Hall 1978). kaolinite. which are typical of hypogene (T = 200350 °C) acidic conditions (advanced argillic assemblage. (1994a) Steven & Ratti (1960). (1977). Spain Steep normal faults Porphyry Cu-Mo mineralization nearby Local faults Caldera ring faults + normal local faults <150 Losada-Calderon & McPhail HS ore at Nevado del Famatina is a part of a (1994).g. Deen(1990) Siddeley & Araneda (1986). and (3) by atmospheric oxidation of sulfides during weathering (supergene). 1995) John et al. (1993) Ren era/. Sillitoe & Lorson (1994) Russell &Kesler (1991). Ashley & Silberman (1976). associated with fumarolic discharge of vapor released by deeper boiling fluids (steam-heated). (1992). Arribasrta/. Magmatichydrothermal alunite occurs with minerals such as diaspore. Noble & Silberman (1984). bedding planes Steep strike-slip fault zones + contact of volcanic vent Steep fractures + permeable pyroclastic layers Steep radial fractures + dome contact Vertical extent of epith ore(m)2 Relation to porphyry system Porphyry Cu-Au prospects nearby. Rye et al. Julcani. Ashley (1974). 1992): (1) by the disproportionation of magmatic SOj to H2S04 and H2S following absorption by groundwater (magmatichydrothermal). Dominican Rep. China Nansatsu. Meyer & Hemley 1967). Stoffregen (1987). stk Au mineralization (East Zone) None known 600 >300 None known Pem El Indio. Tan etal. age within 1. Proposed. (1990) Petersen etal. Philippines Lepanio. Nevada Pueblo Viejo. steep fault Steep strike-slip fault Major steep + minor faults. Colorado Control on mineralization Contact between dome and volcanic rock. pyrophyllite.y. typical of geothermal systems that form low-sulfidation deposits. Mumeanero/. Rye (1993) Gray & Coolbaugh (1994) Ransome (1909). Jannas«ai(1990) 600(7) None known <150 None known 250 Intrusion-centered sericitic. diatreme contact. Philippines Chinkuashih. (1990) Garcia (1991). Alunite in steam-heated environments forms with kaolinite and interlayered illitesmectite at about 100 to 160 °C where fumarolic vapor condenses above the boiling zone of neutral-pH. and zunyite. Iwao 1962. (1995a) None known principal geologic environments (Bethke 1984. Menhert etal (1973). (1991). none known Above + adjacent same age porphyry Cu-Au deposit None known References Perell6(l°94) 250 ISO 500 800 Sillitoerta/. dickite. Japan Summitville.0 m. unconformity. Steep faults and permeable pyroclastic layers Diatreme ring fault + permeable layers Steep fractures <150 400(7) Sericitic. (1994) Izawa & Cunningham (1989). low grade stk mineralization None known Goldfield. Nevada Moderately + shallow dipping faults & fissures 400 Paradise Peak.High-sulfidation Epithermal Deposits Table 2 (continued) Deposit/district. Chile La Mejicana & Nevados del Famatina. (1995b) Huang (1955). location Motomboto. Hedenquist etal. Vikre (1989. This type of alunite is characteristic of HS deposits. Argentina Rodalquilar..

The six largest deposits or districts (Chinkuashih. Because of the relatively shallow and dynamic environment of mineralization.. as observed at the Summitville Au-Cu deposit. and the Julcani district has been a source of a remarkable polymetallic assemblage consisting of Ag. copper.. Gold.g. Pb. Arribas. Goldfield. shown at right (from Stoffregren 1987). Pueblo Viejo. Colorado. La Coipa. The concentration of deposits in young volcanic areas is mainly a reflection of the fact that older HS deposits are more likely to be eroded. and correct identification is important for exploration (Rye el al. VOLCANIC SETTING AND ASSOCIATED IGNEOUS ROCKS The high-sulfidation deposits considered in Table 2 occur within intermediate-composition volcanic rock sequences having ages broadly . or PreCambrian (the early Proterozoic Enasen Au deposit located in the Baltic shield of central Sweden. Goldfield. overprinting among the three types of acid-sulfate alteration (including supergene) is possible. the spatial relation of each type of alunite to ore is different. Fig.A. 1). Lepanto. Rodalquilar. and only a few deposits are Mesozoic (e. Some deposits (e. Au. This association is best observed in the Cenozoic deposits of the CircumPacific and-the Balkan belt of southeastern Europe (Fig.6 Ma) and occur in the central western Pacific (Kelly. deposits. Mercury is produced at Paradise Peak. No copper is produced at Paradise Peak and Pueblo Viejo. and variable amounts of silver are the main products of HS deposits (Table 2).g. Temora and others in southeastern Australia). Paleozoic (e. and Chinkuashih). Lepanto. Vuggy silica Quartz alunite PropylWc Chlorite-rich rock Montmorillonite-rich rock 100 m Figure 2. El Indio. Gold (Nalesbitan. occasionally with silica by-product (Nansatsu). 1992. HS deposits coincide worldwide with plutonic-volcanic arcs. Cu. Jr. and Zn (Table 2). White & Hedenquist 1995).y. Cross-section of alteration zones characteristic of high-sulfidation. porphyry copper deposits). however. W. These deposits occur in two main settings: in island arcs and at continental margins. Zijinshan). 1)..g. A G E AND ECONOMIC SIGNIFICANCE In common with other magmatichydrothermal deposits (e. Diagramat left (simplified from Steven & Ratte 1960) shows schematic outward zonation from a subvertical mineralized body. Summitville) formed in intracontinental regions during periods of extension that followed regional compression and subduction by several m. The tectonic regime during formation of the deposits seems to be dominantly extensional (Sillitoe 1993). The youngest deposits are Pleistocene (<1.. is the only economic metal in the smaller deposits. and Pueblo Viejo) each contains more than about 100 tonnes of gold.. Bi. The economic potential of this type of mineralization is clear in regions such as the Chilean Andes (Sillitoe 1991a).g. Tertiary HS deposits predominate. DISTRIBUTION. Rodalquilar).

1990). however. Some deposits are hosted entirely within a single dome (Summitville). Ju = Julcani. The data shown in Figure 3 suggest a relation exists between magma composition and 425 . 3). the age of the host rocks and the age of mineralization are within analytical precision. In = El Indio. even though these magmas can be genetically related to low-sulfidation and intrusion-related Au deposits (Sillitoe 1991b.0 m. Interestingly. See Appendix for references and information on data plotted. Ro = Rodalquilar. which contrasts sharply with the large field defined by volcanic rocks associated with lowsulfidation or intrusion-related Au deposits (>100 samples from 16 districts. no deposits have been discovered in association with alkaline or mafic magmas. Compositional fields after Keith et al. Where abundant radiometric ages are available. 1995a). Le = Lepanto. 3). In most cases the mineralization extends from the subvolcanic intrusion into country rocks. Some deposits. the three main volcanic settings for HS deposits (Table 2).g. it is typically less than ~1. The degree of alteration of the rock samples and precision of the analytical data are largely unknown. The ranges of wt. (Table 2). CM similar to that of mineralization. Muller & Groves 1993. K 2 0 versus Si02 variation diagram for rocks thought to be genetically related to high-sulfidation deposits. Richards this volume). with subordinate rhyolite (Fig. or within a dome complex (Julcani). Mo = Motomboto. (1991). Cq = Choquelimpie. The magmas thought to be genetically related to HS deposits have a remarkably limited compositional variation. the role of calderas in the formation of HS deposits seems to be limited to facilitating the emplacement of late intrusive magma along preexisting caldera ring-fractures (Rytuba et al. La = SCv. do not show any (known) spatial association with subvolcanic intrusions thought to be genetically related to mineralization (e. In the Rodalquilar Au deposit.. where a difference is indicated. however. Su = Summitville. A common spatial association exists between the deposits and shallow. 1993. Nalesbitan. Nansatsu). most of the samples are unaltered or very weakly altered.High-sulfidation Epithermal Deposits Figure 3. The main control on location of mineralization at Rodalquilar is the structural margin of two nested. These intrusions are interpreted to be the roots of volcanic domes or the feeders of central-vent volcanoes or maar-diatreme complexes. and intermediate-to-felsic alkali-calcic rocks are characteristic of the Summitville and Laurani districts (Fig. (wt%) Laurani. Na = Nansatsu. With the exception of Rodalquilar. Circles indicate average values for each highsulfidation deposit or district: Ch = Chinkuashih. such as the Main Vein Cu-Au-Ag deposit and associated breccia deposits in the Penshan area of the Chinkuashih district. PP = Paradise Peak. a larger intrusive body is thought to exist at depth (Arribas et al. resurgent calderas.% K 2 0 and SiC«2 for twelve deposits overlap greatly and show a dominance of calc-alkaline andesitic and dacitic compositions. Go = 50 70 80 60 Goldfield. Intermediate calcic volcanic rocks are limited to porphyritic intrusions in the Lepanto and Motomboto Cu-Au-Ag districts. 1993. dykes and small intrusions of hornblende andesite which are interpreted to be temporally related to the mineralization represent only a fraction of the altered and mineralized area exposed at the present depth of erosion. according to the individual data sources. Sillitoe O 1991b. typically porphyritic intrusions.y. Muller & Groves 1993). The samples from 12 deposits or districts (« = 140) define a small compositional field.

chal. bar. sph. qtz « quartz. cov « covellite. ena. die = = dickite. blank where not specified. bar. nat. ena-luz. PRO » Propylitic. bor. VS . sme . tell * tellurides. bor. cas. naLAu. bis. ele. nat. sele.Au. Bi. SER = sericitic. cpy.selenides. Hbx .Au. cpy. cin •» cinnabar. fam. wol . deeperC?) East Zone deposit) Early: Kao-py-qtz-* alu-py-qtz Late: MS-»pyo-dia Summitville ena-luz.luzonite. gal. gal . cpy. ten. bor. tell. arg. stb.vuggy silica. tell. col « colusite. bar. tou ™ tourmaline. chalc. ser • sericite. ele. sph.sulf Veins Silica core Silica core 10-20 VS/MS-*qtz-alu-lcao-» qtz-kao-ill-* ill-sme-chl <1 Abbreviations used: AA . bou = boumonite. mar.A. pyr. ena. dig •= digenite. mol. sph. nat. cpy. sph. mol = molybdenite. naLAu. bar.Ag. dig. nal. cov bar. sph. ten-let. gal. nat. naLAu.Te . nat. py. dig. cas. gal.calcite. e gol = goldfieldite. cal .illite. ena. ten-let. py « pyrite.Bi.Au = native gold. ceo = chalcocite. col Sn-Bi-Pb-Ag-sulf Py. luz. ceo. Jr.tetrahedrite.galena. cpy. can py. bis. ele. gal.sulf py. Nevadosdel Famatina Rodalquilar kao~*qtz-kao. bor. VS (MS) » vuggy silica dominant. arg. sta » stannite. bou VS/MS-* qtz-dic-«lu-» qtz. mar. cov. bar. tetl. sph. Main alteration and mineralization characteristics of 14 selected high-sulfidation epithermal deposits Lateral alteration zoning (outward from mineralized bodies) VS-»qtz-alu-*qtz-kao-» kao-sme-Mll-chl Silicified Hbx-*qtz-kaoalu-»ill-sme-chl-cal VS/MS-* tz-alu-kao-* kao-qtz-ill-*chl-ill VS/MS-*qtz-alu-kao-» ill-chl-kao VS/MS-*qtz-dic-alu-»qtzdic-ser-»qtz-scr Venical alteration zoning (shallow to deep) VS/MS-»qtz-alu-*qtzkao-*ill-kao-*cbl Silicified Hbx-*qtz-kaoalu-» ill-sme-chl-cal MSA'S-* AA-»SER-« (K-silicate in subjacent FSE porphyry copper) Ore mincratizaUon Princial ore minerals Py. ars.hydrotherma! breccia.advanced argillic. let-ten. sid = siderite. len-tet. sph. 2 Boiling (Hbx) -= boiling due to abrupt pressure reduction associated with hydrotherma! brecciation 426 . hue •= hubnerite. ten py. ill . kao kaolinite. bor •= bomite.Au. gal.Au. Pb.Pb. nat. naLS. sele. gal.S. sta. naLHg. hue. ars = arsenoyrite. stb. mol. emp.Au. can = canfieldite. gal. = rea « realgar. nat. geo. cpy. sid. got. Silica core <2 Silica core 2-20 Goldfield Silica core <1 Paradise Peak Silica core 10-30 Pueblo Viejo InAA + MS zones Veins 7 470 Julcani Pre-ore:VS/MS-»qrz-alu- Ellndio La Mejicana. are. ten-let. cpy = chalcopyrite. cpy. sph.famatinite (stibioluzonite). ena. cov. sph = sphalerite. ceo. ele. oro «• orpimcnt. ten. ena-luz. stb «• stibnite. nat. tell. bar = barite. ena-luz. sph. py. lentet. fam. cas » cassiterite. sph. MS •= massive silica. gal. Table 3. dig.alunite. ele « electrum. cov. cpy. sph. tell. fam py. bar. ten-let. mar •= marcasite. naLAu cpy. py. gal. ten ~ tennantite.native tellurium. tell Py. natS .Au. mar. mar. ele. ena. bor. ceo.native sulfur. bis = bismuthinite. alu . gal. sele . mar. Arribas. Bi.wolframite ' Based on fluid-inclusion (flinc) or geological (geol) evidence. nat. luz . py. col.Au. tel. cin. fam . tet . cov. ena. wol.sulfides or sulfosalts. Syn-ore: qtz-pyo-py-»qtz. py. cov. arg. sph dic-ser-»qtz-ser Silica core 4 Silica core 2 Silica core N/A Nansatsu VS/MS-* alu-dic-pyo-* ill-kao-sme-* PRO VS(MSh*qtz-alu--» qtz-kao-*kao-iU-* sme-chl MS{VS)-*qtz-alu-kao-* iII-sme-» PRO Vertical (due to deposit style): MS(VS)-* qtz-alu-kao-» sme-chl Complex + overprinted VS/MS-*alu-*dic-serpy-»ser-chl-»PRO VS(MS)-»qtz-kaoalu-*qtz-kao-*SER MS>VS-*qtz-alukao-*qtz-kao±pyo MS(VSHqtz-alu-kao (SER in faulted.Ag-bearing sulf Ena. emp « emplectite. chl • chlorite. = sulf. tell Deposit Motomboto in: Silica core Ag/Au 35-45 Nalesbitan Silica core Very low Ag Lepanto Chinkuashih Zijinshan Ena-luz. tell. pyo = pyrophyllite. geo » geocronite.kao-py-< qtz-scr-py •qtz-kao-sme Cu stage veins-* kao-aluser-qlz. cov. fam. gal. del Famatina porphyry copper) VS/MS-»qtz-alu-kao-* qtz-kao-ser-»qtz-ser-py tet. bar. fam.qtz. let.Au. cas.S.smectite. py. nal. Snbearing sulf py. gal. mol. sph.qtz = chalcedony or chalccdonic quartz. luz. cpy. Au stage veins-* ser-kao-pyo-qtz Alu-kao-*qtz-ser-» (K-silicate in N. nat.

and some of the veins at Julcani). Nevadosdel Famatina Rodalquilar 2 AA-»silica-py-Au 200-300 flinc + geol Boiling (Hbx)2 + Widespread to 80 mixing/cooling m.High-sulfidation Epithermal Deposits Table 3 (continued) N° and order of main mineral events 2 AA-> sulfide-Au 2 Py-qtz-»Cu-Au 3 AA-»Cu±Au -•Au 2 AA-»Cu-Au + late bar-Au SeveraK?). bar-Au may be partly by oxidation steam-heated Mixing/cooling. DEPOSIT FORM AffD CONTROL: CLASSIFICATIONS High-sulfidation deposits display a wide variety of styles of mineralization that includes veins. (1994). quartz-Austage veins at El Indio. (1990) Lepanto Chinkuashih Zijinshan Mixing/cooling Unknown Garcia (1991). lacusAlu-kao-py-Au-« trine sediments MS-pyo-dia-Au preserved Several 200-300 AA+VS-»tou breccias-* sulfide veins (main. Jannasrtai(1990) Losada-Calderon & McPbail. Claveria & Hedenquist(1994) Huang (1955). (1995a) La Mejicana. (1993) 500 Unknown Mixing/boiling Important in upper Ren el al. Widespread to 80 oxidation nv..and low-sulfidation mineralization (e. (1992). hydrothermal breccia bodies. (1994) 250 nv. with Widespread to 250 Hbx in early Au. Gray & Coolbaugh(1994) Ransome(1907. Sillitoe & Lorson (1994) Kesler«ai(1981) Russell AKesler (1991). mixing. 1909). Ashley (1974). late) 2 AA+Cu-» Au Widespread to 100 nv. Qtz-ser-dic-*qtzalu-dic-» sulfide 2 AA-*Cu-Au Inferred mineralization depth (m)1 Unknown 300-500 flinc Unknown Inferred oreforming mechanism Unknown Boiling (Hbx)2 Supergene oxidation/ secondary Au enrichment? Irregular to 100 m Deposit Motomboto Nalesbitan References Perello(1994) Complete to 130 m. some deposits present complex relations which may be composite. This variation in the structure of the orebodies is complemented with variations in other deposit features. supergene alunite(-lOMa) Boiling. stockworks. 3). Hedenquisl el al.m. paragenesis. supergene alunite (4-3 Ma) development of the oxidized and reactive magmatic vapor plume that is thought crucial to the formation of HS deposits. Munteane/a/.g. between high. 1995) John eial. Brodtkorb & Paar (1993) SSInger-von Oepen et al. (1990) Deen (1990). (1991).g. Vikre (1989. and disseminations or replacements. Zhang et al.) Stoffregen (1987). Rye (1993) Nansatsu Summitville 150-300 flinc Goldfield Paradise Peak Pueblo Viejo Julcani El Indio 3 400-500 AA-»Cu±Au-+ flinc + geol bar-base-metal-Au 5+ 100-300+ AA-»ena-»Augeol ten-py-Bi-Tc-» 3 Unknown AA-»Au-Ag-+ Hg 2 Shallow. including ore and alteration mineralogy. Definition of styles of HS mineralization 427 . written comm. supergene aluAg stage nite (10±0.5 Ma) Sulfidation + Widespread to boiling -100 m Mixing + boiling Mixing/cooling Mixing/cooling Siddeley & Araneda (1986). yes Izawa & Cunningham (1989).. (1994a) Steven & Ratte (I960. Tan el al. yes but may be steam-heated Cu-Au by Irregular to 100 m. (1989)Arribas«fl/.. yes Not important Sillitoe el al. and metal ratios (Tables 2. In addition. e.

veins. with chlorite. Nansatsu. kaolinite. A large group of deposits falls into White's (1991) Nansatsu-style. In Russian and eastern European terminology these rocks are commonly termed 'metasomatic quartzites'. and a lithologic unconformity (Pueblo Viejo. White (1991) distinguished three end-member styles of HS deposits. illite. and dickite quartzites (e. and low-grade vuggy silica and breccias. and Nansatsu. silicified ores dominate in the Temora-style. ALTERATION MINERALOGY AND ZONING As mentioned above. This advanced argillic assemblage grades into a second envelope of argillic alteration. stockworks of small veins. The width of each zone varies widely. In this context. the two types are broadly comparable with El Indio. which is characterized by wallrock-alteration zoning similar to that shown in Figure 2.g. Chinkuashih. Goldfield. Rodalquilar. Table 3). sericite.. respectively.A. In the majority of HS deposits. the dilational jog of a strike-slip fault (Nalesbitan). Jr. Local subvertical faults and fractures are the dominant control on HS mineralization and they are present in most deposits (Table 2). for example. however. /1">0 The deposit is 3 km long and consists of a main zone of breccia and replacement mineralization along the Lepanto Fault (Fig. Lepanto). and carbonate (Fig. Lithologic variations in the host rocks also played an important role in the formation of the deposit. 2 and 4). Cavity-filling veins with sericitic and clay-rich haloes are characteristic of El Indio-style Au deposits. diatreme ring-faults (Lepanto. and smectite. most of the ore is contained within the silica core.. the principal control is lithological (maar sediments at Pueblo Viejo. El Indio. kaolinite. smectite. illite. Table 2). The characteristic mushroom-shaped cross-section of many of the orebodies at Lepanto is related tc the intersection of the steeply dipping Lepanto fault and branch veins with the unconformity at the base of Imbanguila dacite (Fig. Other examples of structural controls observed in some districts among the fourteen selected include: moderately to shallow-dipping faults (Goldfield). the Missionary orebody at Summitville). and by the occurrence of enargite-bearing ores within a silica core consisting of vuggy or massive silica rock (Table 3). and interbedded pyroclastic layers at Paradise Peak and Nansatsu. cavityfilling planar veins at Julcani and El Indio may extend outside the zone of alunite-kaolinite. 1990). Pueblo Viejo). The innermost zone of vuggy or massive silica alteration commonly has sharp boundaries with a zone that may contain quartz. and an outermost halo of propylitic alteration. caldera ring and radial faults (Rodalquilar). inside the advanced argillic envelope (Table 3). Summitville).. Multiple veins associated with smaller diagonal faults branch from the main zone and extend into both the hanging wall and footwall (Garcia 1991). Velinov et al. as shown by lenses of stratiform enargite-luzonite ore which resulted from replacement of detrital layers within volcaniclastic and sedimentary basement units (Garcia 1991). alunite quartzites.g. the contact between a dome or volcanic conduit and country rock (Motomboto. and zunyite . alunite. A unique combination of the structural and lithological controls characteristic of HS deposits is exhibited by the Lepanto Cu-Au-Ag deposit. Ericksen & Cunningham (1993) distinguished two styles of HS deposits in the Andean province: Agand Au-rich polymetallic base-metal veins. These deposits contain breccia bodies. vuggy silica and advanced argillically altered rock form narrow (<70 cm) vein selvages at Julcani (Deen 1990).and Nansatsu-styles.g. 4B). named after deposits of the CircumPacific: Temora. and disseminated ores that replace or impregnate intensely altered country rock. dickite. 4A). Irregular bodies of disseminated. composed of minerals such as quartz. . Arribas. but form wide (>50 m) rock bodies at Summitville or Lepanto (Figs. Late-stage. In three of the fourteen deposits. diaspore. but useful for discussion of the differences among deposits and design of exploration strategies. diaspore quartzites. is difficult. with more specific names such as porous quartzites. 2. Mineralization in this style of deposit forms irregular stratabound bodies (e. Lepanto. Lepanto) or subvertical vein-like masses or "ledges" {e. pyrophyllite. the lateral alteration zoning that is characteristic of HS deposits reflects the reaction and neutralization of hightemperature acidic fluids with wallrock.

pressure. Summitville. in which the vertical span of mineralization is less than about 300 m (e.g. If studied in detailed.High-sulfidation Epithermal Deposits ® h>B ® Lepanto fault Age (Ma) 1. 1980).2-0. 1969.45-1. 1993). Experimental data on the relative stability of minerals such as alunite.8 Cre. Fig.e. 5B). Detailed field and petrographic studies at the Monte Negro orebody in the Pueblo Viejo deposit have resulted in 429 . sericitic alteration at depths of 400 to 500 m below the epithermal deposit gives way. and diaspore (Hemley et al. sericite. Porphyry-type stockwork mineralization at Paradise Peak is contained within the sericitic ores of the East Zone deposit which. The zones of alteration with increasing depth typically grade from a shallow silicic zone through advanced argillic. and composition of the hydrothermal fluid and the degree of wallrock interaction.9 (ill 22-1. according to Sillitoe & Lorson (1994). The lateral and vertical alteration zones described above correspond to a generalized model. laterally towards the south.. volcanic vents of Pliocene dacite. coupled with the temperature ranges noted for these and other related acid minerals in active systems (Reyes 1990. showing structural and Uthologic controls on formation of the high-sulfidation and porphyry-type ores (simplified from Garcia 1991). in temperature.-Mto..56-1. and has been best documented by deep drillholes in the deposits of smaller size. and pyrite. argiHic/ sericitic. pyrophyllite. several superimposed and crosscutting stages of pervasive as well as fracture (conduit)-related mineralization may be recognized in the majority of deposits. quartz diorite intrusions. into a sericitic or phyllic zone with quartz. 1995b). also provide information that contributes to definition of the paleoconduits in extinct systems. Note the overall spatial overlap of the magmatic and hydrothermal "plumbing" systems (i. These are the expected result of variations. A quartz-sericitepyrite zone with trace amounts of chalcopyrite and molybdenite surrounds an intrusion of monzonite porphyry £300 m below the HS deposit at Summitville (Gray & Coolbaugh 1994). during the course of mineralization. At Lepanto. m raaftHi -700m Jea level pgg BSa RS|9 ^ ^ f=g Vuggy silica/ massive silica Advanced argiHic ArgiHic JSWfl® 1 Propyiitic Figure 4. kaolinite. Longitudinal (A) and transverse (B) cross-sections of the Lepanto-FSE Cu-Au-Ag deposits (Philippines). formed underneath the main HS orebodies in the area. Reyes et al. This alteration sequence occurs over a vertical interval that ranges from a few hundred meters to more than 1000 m. to K-silicate alteration of the FSE porphyry Cu-Au deposit. They are useful in exploration because they help in understanding the genetic environment of a deposit and provide spatial "markers" within the extinct hydrothermal system. t»3 rIM B Ore deposits and lithology High suttkJation Cu-Au ore Porphyry Cu-Au ore Post-mineralization cover Ouartz-oloiUe porphyry Dacte porphyry & pyroclastics Basement rocks " )n/mineralizatJon m Stratabound f ^ . Rodalquilar. argillic. and deeper parts of epithermal mineralization). Potassium-argon dating of country rocks and alteration minerals associated with the porphyry and high-sulfidation deposits indicates that hydrothermal Cu-Au mineralization took place in the middle of a Pliocene to Pleistocene event of dacitic-andesitic magmatism (Arribas et al.17 I [ 1.22 E%3 1. porphyry deposit.

listed by decreasing abundance from variable to very minor. alunite. include tennantitetetrahedrite. 1995a).A.and REEbearing phosphate-sulfate mineral(s) such as svanbergite-woodhouseite or crandallite (Stoffregen & Alpers 1987). and Ca-. chalcopyrite. molybdenite. margin N Mm§^7 rffflsRSm ^^V^ \ jHodafottf/ar • i Vuggy silica "^ (||l . above a zone of pyrophyllite-diaspore alteration (Muntean et al. cassiterite. A A A / [A A A * :i££j|HrA I vf* % A A A /X A A Pb-Zn-{Cu-/ quartz veins Figure 5. southeastern Spain (from Arribas et al. Other minerals present in minor amounts in several deposits include Pb-. 1990).and Snbearing sulfosalts (Table 3). Bi. shallow kaolinite-quartz-pyrite and deep alunite-quartz-pyrite-quartz zones were developed. during the second stage (responsible for about 40% of the Au). pyrophyllite. The boundaries shown between alteration zones are irregular and gradational. Other common but minor gangue minerals include barite. During the first stage (responsible for ~60% of the Au in the deposit). high-grade White et al. orpiment. _ ip^lttjr • TO3 Argillic ^^^5i2Sii5S>liS*i^^^^^\.||flp-::f LA»*I Serkatic p l l Propylitic G O Intense supergene actd-sulfate overprint OD ® Au-{Cu-TeSn) Nghsutfidation deposits r 400 . La Mejicana). their conclusions with respect to ore and gangue mineralogy in HS deposits are included here._ f. an extensive zone of siliciflcation with pyrite ± sphalerite ± enargite veins formed at shallow levels. Jr. Famatinite is locally abundant in some deposits (Goldfield. Common ore minerals. A A A * A A A J . A A X. stibnite. A A A * A 4* * . diaspore. covellite. in addition to the 430 . pyrite is abundant but the amount of enargite and luzonite is variable. For example. with gold mineralization in association with disseminated pyrite in the wallrock. Fine-grained quartz is the dominant gangue in HS deposits. and galena. native gold and argentian gold (electrum). Ag-Pb. 1990). Generalized surface alteration map (A) and cross-section (B) of the Rodalquilar HS deposit in the Rodalquilar and Lomilla calderas. Sparse ore minerals include bornite. identification of two stages of mineralization. ® Rodalqultar caldg£»--r? margin ^<^^•"•'•' ^KmSmm§ iominacakieraV ftt^ls)/ ^Un s. Arribas. r = j Advanced argilltc **V. cinnabar..Sr-. AND TIMING O F MINERALIZATION particular features of the deposits listed in Table 3. and wolframite (the last locally important at Julcani). marcasite. 0 . kaolinite. realgar. Pyrite and enargite (and its low-temperature dimorph luzonite) are the dominant sulfides in HS deposits. interpreted to correspond to two distinct magmatic pulses (Muntean et al. lilHi A JCSJSSw -400 Elevation Lower limit of sulfide oxidation A A ft. Pb. (1995) and White & Hedenquist (1995) presented detailed discussions on various aspects of epithermal gold mineralization on the basis of observations from a large number of deposits around the Pacific. O R E AND GANGUE MINERALOGY. sphalerite.

High-sulfidation Epithermal Deposits vein specimens from Chinkuashih..or base-metal-rich deposits.% NaCl. in contrast to that noted for lowsulfidation Au versus Ag deposits (Hedenquist & Henley 1985). The most reliable data on the ore-forming fluids are obtained through infrared microscopy directly on ore minerals. each group. >300 °C) fluids of variable salinity. Combination . the last typically without sulfate (alunite) but with quartz-sericite gangue and wallrock alteration. and are followed by Cu ± Au ± Ag deposition. Large variations in both temperature and salinity also occur within a single deposit. and La Mejicana have spectacular intergrowths of ore minerals with kaolinite. a late stage of baritegold has been documented. alunite. Hedenquist this volume). provides relevant information on various genetic aspects. temperature and sources of hydrothermal fluids in HS deposits. such as enargite (Deen 1990. The most common evolution is from an early leaching and alteration stage to a later ore-forming stage. from 90° to 480 °C and <1 to 45 equiv. The framework for the interpretation has benefited from information on the composition and fluxes of volcanic discharges and active magmatic-hydrothermal systems (Hedenquist & Lowenstern 1994. El Indio. Group 1. Fluid-inclusion Evidence Suitable hosts for fluid-inclusion studies are scarce in HS deposits. or pyrophyllite. Detailed studies in some districts (e. have resulted in identification of two metal stages. wt. as significant variations exist among and within deposits. The transition from quartz-alunitepyrite alteration to enargite-pyrite and finally to tennantite-tetrahedrite. Vuggy silica rock and the advanced argillic assemblage with disseminated pyrite form typically early-stage acidic alteration. as the gangue minerals are typically fine-grained and even millimeter-size hydrothermal quartz crystals are usually late stage and vug-filling. The temperature boundaries chosen for each group are only indicative. Higher temperature (e. Satisfactory results are obtained on secondary fluid-inclusions in igneous quartz phenocrysts from altered wallrocks. however. the other possibility being AuCl2~(e. The temperatures and salinities estimated for HS deposits define a wide range. with high. A minimum of two stages of alteration/mineralization has been recognized in most deposits on the basis of crosscutting relations (Table 3). This observation implies that ore formation occurred under moderately acidic to acidic conditions. Mancano & Campbell 1995). Giggenbach this volume. respectively (Table 4). an early Cu-rich. however. and tellurides.and low-salinity fluids interacting during the course of mineralization. which are inconsistent with transport of Au as Au(HS)2" (Seward 1973).g.and low-temperature and high. Lepanto). associated with intermediate-sulfidation-state sulfides such as tennantite-tetrahedrite and chalcopyrite.. although lacking temporal information. The number and order of mineralizing events provide critical information for reconstruction of the hydrothermal system that results in HS mineralization. indicates a fluid progressively more reduced and less acid. Cu-poor stage. There is no systematic difference in salinity among Au-. these inclusions seem to provide a representative cross-section of the fluids involved. and a late Au-rich. Recent studies of Au solubility in high-temperature acid sulfide solutions have resulted in identification of AuHS° as one of the principal gold complexes in HS mineralization (Bening & Seward 1994). these reflect the dynamic environment. which have been documented in several deposits and are generally 431 Results of recent detailed fluid-inclusion and stable-isotopic studies reveal much about the composition. Goldfield. CHARACTERISTICS AND SOURCES OF HYDROTHERMAL FLUIDS of these data with geological and mineralogical observations mentioned above allows the nature of the altering and ore-forming fluids to be determined. dominated by enargite-luzonite. Table 1).g. and Ag. Four broad groups of hydrothermal fluids are recognized here on the basis of the estimated temperatures and interpretations given by most workers. Au-poor stage. 1994a).g. Hedenquist et al. At Summitville and Chinkuashih (also Tambo and Furtei-Serrenti..

Taiwan Zijinshan. Philippines Lepanto. ser = sericitic. Summary of fluid-inclusion microthermometric data for high-sulfidation deposits Host-mineral studied Barite Quartz Enargite Quartz. and implies the presence of a shallowdepth intrusion. However.NaCI) alteration <1 0. Chile El Indio. Nevada Paradise Peak.9E. Peru Can-Can (La Coipa). quartz phenoe Ser AA/sil Abbreviations used: AA = advanced argillic.5-14 2-18 (up to 9) 5-18 0. ena = enargite. Two-phase entrapment may explain some of the unusually high homogenization temperatures (7*). brackets used to indicate high-iemperature inclusions typically interpreted as having formed early or being anomalous interpreted as "anomalous" or unrelated to ore and are associated with early stages of alteration. al unite Quartz (no details reported) Quartz Diaspore Quartz.2^. Japan AA AA/sil Summitville.^ Ser AA/sil Akaiwa.6 (32-45) AA/sil AA/sil AA/sil A A/si 1 AA/sil AA/sil Deposit Motomboto. Spain AA + ser AA Ser AA/sil . Italy Quartz. particularly considering the shallow mineralization depth inferred for many of the deposits (Table 3). Colorado Goldfield. Nevada Ser AA/sil Julcani.2-12 2-22 3-19 0-5 (3-20) <1 up to 30 0. Table 4. barite. Peru Ccarhuaraso. Japan . barite. as well -34 as isotopic (8 Ssuifate-suifide) temperatures (see . ena. barite Quartz Quartz phenoe Quartz phenoe Wol.A. quartz Siderite Quartz phenoe Quartz phenoe Sphalerite. Argentina Rodalquilar. On the basis of fluid-inclusion.1-2. barite Quartz.4-1.7 (up to 27) 1-37 0.2-8 <3 30-35 5-24 38-46 9-20 6-9 7-18 4-11 <l-40 0. quartz phenoe Quartz phenoe Barite Quartz phenoe Quartz. quartz hubnerite Quartz phenoe N/A Temperature (°C)' 150-180 220-260 170-290 180-330 160-300 220-380 100-160 (300-420) 130-250 -270 250-310 190-240 210-330 180-280 (300-390) -100 230-480+ 210-280 (370-410) 180-210 300-380 (up to 450) 160-280 360-450 230-330 220-250 330-380 230-260 170-350 190-280 140-180 (>300) 200-460 160-340 230-480 170-300 220-450 190-320 90-140 (390-500) Associated Salinity (equiv wt.4-23 0. Japan Mitsumori-Nukcishi. barite. sil = silicic: wol = wolframite: see Table 3 for paleodeplh estimations 1 temperatures are rounded to the nearest 10°.5 0. The consistent presence of these fluids in several deposits indicates a high temperature gradient. most workers agree that such All entrapment cannot account for all the high Th values. Philippines Chinkuashih. Funei-Serrenti.3-12 ^47 2-30 2-45 0.1-4 0. China AA Ser Sil AA/sil AA/sil Nansatsu. . Arribas. Chile AA/sil AA/sil AA/sil dominant AA/Ser La Mejicana (LM) and Nevados Famatina (NF). Jr. phenoe = phenocrysts. and possibly lithostatic confining pressures. Peru Colquijirca. quartz phenoe Quartz. Indonesia Nalesbitan.

cooling fluids away from subjacent porphyry Cu-Au deposit. Japan Mitsumori-Nukcishi. (1994a) Akamatsu & Yui (1992) Aoki&Watanabe(1995) Bruha & Noble (1983). Japan Akaiwa. these typically liquidrich inclusions are found in all deposits. saline liquid and low-salinity vapor coexist Vein quartz -400 m below Kasuga deposit Coarse-grained diasporc Not (known) Au or Cu mineralization. and Rodalquilar (Arribas etal. shallow silica-Au Associated with early silica and quartz-dickite Late. also in outer veins. Peru Ccarhuaraso. vug-filling quartz Qtz in breccia. Indonesia Nalesbitan. 1994) Cunningham (1985) Bruha & Noble (1983) Vikrc(1989) John et al.and vapor-rich inclusions. Stoffregen (written commun.. CO2 observed LM & NF: includes liquid-. (1990) Losada-Caldcr6n & McPhail (1994) Goldfield..5 km high . Spain Furtci-Serrenti. liquid CO2 observed Sampled interval 3 km long by 0. where Th >450°C & salinity up to 54 eq wt. also inner veins. Philippines Chinkuashih. CO2 observed Quartz-alunite±pyrite Pre-ore tourmaline breccia dykes. Mainstage ore fluids are contained within this group. Evidence for P above hydrostatic and higher salinities at depth Copper and gold stages Late stage Interpreted as early. Summitville (Rye 1993). Yen (1976). Peru Colquijirca. Argentina Rodalquilar. vapor-rich inclusions typically less saline Vertical temperature and salinity gradient: high-temperature brines coexist with low -aiinity vapor inclusions. 180-330 °C).. but high salinity fluids Liquid-rich. up to 67 eq wt% NaCl) through sercitic to epithermal fluids in HS (AA) stage.High-sulfidation Epithermal Deposits Table 4. pressures above hydrostatic have been suggested for several deposits. Colorado - Hedenquist et al. Main-stage ore fluids. R. including Julcani (Shelnutt & Noble 1985). (1993) Zhang et al. CO2 observed Associated with main stage Cu Deep alteration zone (>600 m depth) Associated with late. vug-filling crystals in hydrotherma! breccia. Garcia (1991) Folinshce el al. lithostatic pressures likely.% NaCl Poorly-documented samples along a 450-m vertical interval. liquid-rich inclusions Late-stage ore fluids. Philippines Lepanto. (1995a) Ruggieri (1993b) below). <6 eq wt% NaCl) Late stage References Perell6(1994) Sillitoe et al. Tan el al.1o NaCl only in vuggy silica associated with Cu mineralization. the higher T|. (1972). 1995a). Italy Sanger-von Ocpen et al. Intermediate-temperature fluids (e. salinity >6 eq w. Peru Can-Can (La Coipa). CO2 observed Liquid. hydrostatic and near-lithostatic pressures suggested Includes high + low-salinity fluids (22-23. with vapor-rich inclusions. Nevada Paradise Peak. Taiwan Zijinshan. with salinities variable from <1 to ~18 equiv.s in samples at -750 m depth. vapor-rich and polyphase inclusions NF: complete transition from porphyry-type fluids in Ksilicate stage (SOO-oW^C. Chile La Mejicana (LM) and Nevados Famatina (NF). (1994) Nansatsu. The temperatures measured in fluid inclusions in enargite at Lepanto (Mancano & Campbell 1955) 433 . Arribas <•<«/. (continued) Deposit Motomboto. P correction applied Quartz-alunite±pyrite Quartz-alunite±pyrite Two generations identified. Goldfield (Vikre 1989). Chile El Indio. Japan Summitville.% NaCl. wt. Group 2. China Comments Reconnaisance study in late-stage barite Reconnaissance study. From stockwork Au East Zone deposit. Nevada Julcani. (1991) Sillitoe &Lorson (1994) Bruha & Noble (1983) Shelnutt& Noble (1985) Deen(1990) Deen(1990) Bruha & Noble (1983) Bruha & Noble (1983) Townley(1991) Jannase/tz/. With the possible exception of deposits for which only the late-stage minerals have been studied. both may be very saline. also polyphase inclusions Late barite-Au assemblage True Th is interpreted to be 250-290°C Hydrostatic and near-lithostatic pressures suggested Late.g. (1989). (1990) Mancano & Campbell (1995).

Group 3. Furthermore. Hedenquist & Lowenstern 1994. or they may reflect immiscible vapor and hypersaline liquid derived directly from shallow-emplaced magma (Rye 1993. among the examples reviewed.5 equiv.dMuifatt for four coexisting alunitepyrite samples (large filled circles). respectively (modified from Arribas et al.600 1 o -200 I Q. low-salinity fluid inclusions coexist with high-temperature. reference boilingpoint curves.% NaCl. above). The late-stage ore fluids at Julcani are hotter (220-250 °C. "Sericitic" fluids. 6) shows a gradient which correlates with the change in dominant alteration. These fluids may be the result of boiling of a high-temperature liquid. Elevation versus temperature diagram showing the range (horizontal line) and average (vertical line) of fluid-inclusion homogenization temperatures measured in the Rodalquilar Au deposit. vapor-rich. these have been documented in a few deposits associated with late-stage (e. Jr. Although detailed documentation is lacking for many deposits. salinity = 2-15 equiv. Hedenquist this volume). The transition from advanced argillic alteration. respectively). in common with porphyry-type deposits. salinity = 2-45 equiv. at Rodalquilar (Arribas et al.% NaCl. with Groups 1 and 4. documentation of temperature and salinity along a >600-m vertical interval (extending 500 m below the ore zone. wt. Sulfur-isotope Evidence The abundance of coexisting hydrothermal sulfides and sulfates.% NaCl) liquids.% NaCl). and Julcani (Deen 1990) are broadly similar. wt.. rich hypersaline inclusions (i. at the Lepanto-FSE and La Mejicana-Nevados del Famatina epithermal-porphyry copper systems. but no correlation among the late stages in different deposits is attempted here.% NaCl at the elevation of the orebody) to sericitic (7"= 220-450 °C. Spain.% NaCl and 2 to 45 equiv. wt. sericitic (quartz-sericite-pyrite) is the most common alteration assemblage observed below the ore zone in some HS deposits.g. wt. to K-silicate alteration and typical porphyry-type hightemperature (600+ °C) and high-salinity (up to 67 equiv. Arribas. Aubarite) mineralization. wt. dilute (typically <5 equiv. Lower temperature (e.2-4. For example. wt. than these averages. Shinohara 1994. 800 -400 I Figure 6. 90-180 °C). 1995a). but their salinities are distinctly different (0. Group 4.. hightemperature.% NaCl) assemblages. Estimated salinities of fluid inclusions in the shallow advanced argillic/silicic zone and deep sericitic zone range between 2 to 30 equiv. through quartz-sericite-pyrite. and vertical spans of the alteration zones mentioned in the text. Also shown are the temperatures calculated. liquid434 Temperature (°C) 200 300 400 500 400 Elevation of Onto deposits HjO + 5 wt% NaCl (hydrostatic) 200 (hydrostatic) (lithostatic) B1 « -|400 s 200 3 1 I I > ! 3 . Fig.% NaCl) fluids of magmatic origin is displayed. wt. on the basis of 834S suir. 1995a)..g. wt. in addition to the possibility .e. The cooler and less saline inclusion fluids documented in the ore zone of the HS deposits are interpreted to reflect mixing of magmatic and meteoric fluids in an environment shallower than that of porphyry mineralization.% NaCl versus 8-18 equiv. wt. providing constraints on the role of a saline magmatic liquid (versus low-salinity vapor) in the generation of HS deposits. from silicic and advanced argillic (T = 170-300 °C.A. As mentioned above. Deen 1990) and slightly more saline (6-9 equiv. higher temperatures and higher salinity fluid-inclusions seem to characterize the sericitic zone with respect to the shallower zones of alteration (Table 4).

Arribas et al. (2) A simple mass-balance calculation done in several deposits using the S/ S values of the igneous rocks and the average 34S/32S values of sulfides and sulfates indicates that H 2 S/S0 4 in the hydrothermal fluids was generally about 4 ± 2 (Fig.420 220 . (°C)* H 2 S/S0 4 220 . Cunningham et al.. but the magmatic sulfur is overall heavier than mantle values (from 534S = 2 0/ 0/ ± 2 'oo at Summitville. The main conclusions of the sulfur-isotope studies in HS deposits are: (1) sulfur in the deposits is magmatic. isotopically heavy igneous sulfur is common in volcanic arc environments (e. Rye et al. 1994a.270 2-6 + Lepanto Chinkuashlh Nansatsu Summltville Goldfield Pueblo Viejo Julcani El Indto Rodalqullar —T— I I i +• + 3 4 200 . This is not surprising given the most common geological setting of the deposits. Kiyosu & Kurahashi 1983). Hedenquist et al. Bove et al. 7) are different.. H2S/S04. in which the 834S of alunite is close to the composition of total sulfur in the system (e.g. 1992) . of measuring 34 S/ S in host rock and genetically related igneous rock (Sasaki et al. 1984. The results of detailed studies in nine HS districts show a remarkable consistency (Fig. the most likely explanation is a "magmatic-steam" (Rye et al. Fig. 1990).240 200-390 200 . Rye 1993). Alunite Ridge in Marysvale. 1979). Also shown are the values calculated for 834S for total sulfur in the hydrothermal system (triangles). 7. 1995a). sulfide and sulfate minerals are mainly in isotopic equilibrium. See Appendix for references and information on data plotted. these values indicate drastic changes in H 2 S/S0 4 during the course of mineralization (similar to those for the Red Mountain alunite deposit. In agreement with the observations in active volcanic-hydrothermal systems (e. 7).High-sulfidation Epithermal Deposits —. temperature. CDT) 1 h20 '(mineral pairs) 5 30 Figure 7.. their overall S/ S depends on the temperature of mineralization and the 34S/32S of total sulfur in the hydrothermal system.Sulfides — — Sulfates — T &V . therefore. 1990. Range of 834S (per mil) values for sulfides and sulfates from nine highsulfidation deposits.350 180-260 210-270 5 220-330 -H -10 1 1 0 1 1 10 &*S (%. Combined with the 8 S values of pyrite and enargite from the same vein.534SJS A 3 4 SH 2 S-SO4 Temp. to 9 ± 2 'oo at Rodalquilar. This is a minimum value for ore-forming fluids because it applies mainly to the early stage of hydrothermal 435 . Ueda & Sakai 1984). and sulfur sources of the hydrothermal fluids. 1992. Jannas et al. and. If the measured El Indio alunites are not steamheated or supergene (unlikely as they contain finegrained pyrite. Solid triangles indicate deposits in which 834S£S was calculated on the basis of isotopic analyses of samples of unaltered whole rock genetically related to mineralization. 7).g. and the range of temperatures determined from sulfide-sulfate mineral pairs.. Rye et al. allows sulfur-isotope studies to provide information on the composition. 1992) origin.g. Only the data for alunite from the Campana vein in El Indio (Fig.

1995a). Other mineral pairs used with consistent results include pyrite-barite (Vikre 1989. including 8 l 8 O s o 4 and 61 0 O H that help to distinguish the various types of alunite and associated acid-sulfate alteration (Rye et al. they show a thermal gradient: e.7). at 200 °C there is a difference of —20 A between the D/H fracw tionation constants for kaolinite . 1994).g. and natural variations.. unpub. Wasserman et al. 1987.A. in reliable temperatures calculated on the basis on A SH2s-so4 (Fig.g.g.g. 1992. Oxygen.and hydrogen-bearing minerals (e. sphalerite-barite (Vennemann et al. Hedenquist. analytical imprecision. (3) fewer limitations on the interpretation of the isotopic data because of the relatively young age of mineralization of most HS deposits and general lack of post-depositional effects that disturb the stable-isotope systematics. Reyes et al. In part because of 4 -> r . These may be independent of obvious factors such as sampling or mineral-preparation procedures (fundamental for achieving representative and reliable results). 1992). The range is also consistent with formation of alunite at temperatures below ~400 °C. (2) the lack of mineral-water fractionation factors for some minerals (e. Reyes 1990. 200 to 390 °C over -900 m at Summitville (Rye 1993). Stoffregen et al. 8). 220 to 420 °C over 500 m at Lepanto (Hedenquist and Garcia 1990. in a majority of the deposits. The range of isotopic temperatures is consistent with temperatures estimated from fluid inclusions and alteration mineralogy (e. 1993). Some limitations still exist. Deen 1990). which allows fluids estimated in HS deposits to be compared with those in their active equivalents. The magmatic-hydrothermal alunite typical of-HS deposits gives good results because it is relatively coarse-grained (post-mineral D-H exchange is not a problem. when S0 2 gas starts to disproportionate in the hydrothermal solution (Sakai & Matsubaya 1977. which is characterized by a sulfate-rich alunite-pyrite assemblage. Bethke 1984). and pyrite-gypsum (Vikre 1989). 220 to 330 °C over 200-m elevation at Rodalquilar (Arribas et al.. J. alteration.g. (3) Isotopic equilibrium between sulfide and sulfate in the hydrothermal solutions results.. For example. (1980) on the basis of samples of minerals and water from active systems. Jr. pyrophyllite).W. 1992. data). illite. alunite. the fluids that form HS deposits are arguably some of the better documented and understood in ore-deposit studies. and by Liu & Epstein (1984) on the basis of experimental results.. For these reasons. Important limitations that must be taken into account for optimum use of the stableisotope data are related to (1) the choice of temperature of mineral formation for calculation of the fluid isotopic composition. (2) the development of analytical procedures for complete stableisotope analysis of alunite. 1993). Pyrite-alunite mineral pairs were used most commonly. as observed in active systems (e. thus recording equilibrium conditions of a fluid closer in composition to the ascending mineralizing solution than the kaolinite or illite from outer alteration zones. and (3) the disagreement among fractionation constants proposed for even common minerals such as illite (see Dilles et al. Oxygen and hydrogen isotopic compositions of water in HS deposits are clearly consistent with mixing between a high-temperature magmatic fluid of 8 18 0 = 9 ± l°/oo and 8D = -30 ± 20^oo and meteoric groundwaters (Fig. at which time no data were available to corroborate the affinity-suggested between fluids in active volcanic-hydrothermal systems and HS deposits (e. Hedenquist 1987). This situation contrasts sharply with that of a decade ago. 1980. Aoki 1991. for a discussion) and kaolinite. 1994) and commonly is closely associated with ore. Heald et al. discussion of the sources of water during acidic alteration in the deposits considered here is based on the average of the data collected for alunite.g. kaolinite). for which fractionation factors are well-known (Stoffregen et al.. and (4) the availability of detailed information on the isotopic composition of fluids in active geothermal and volcanic-hydrothermal systems. Arribas.water as given by Marumo et al. 1992. Rowe 1994).and Hydrogen-isotope Evidence In terms of oxygen and hydrogen isotopic composition. Stableisotope studies of HS deposits are particularly illuminating because of: (1) the abundance and variety of oxygen. Hemley et al.. and where sampling with depth is available.

1993. the very light isotopic composition of local meteoric water. inset). or White Island. Alteration/ mineralization Subduction-related volcanic vapor Arc + crustal felsic magmas Acidic fluids In high] sulfldation deposits .. Go = Goldfield. RM = Red Mountain. indicating greater dilution by groundwater (Fig. Giggenbach 1992a. Rye 1993) and Rodalquilar (Arribas et al. PV = Pueblo Veijo. the last documented to have a geochemical environment similar to that of HS mineralization (Hedenquist et al. The average isotopic composition for the main stages of acidic alteration (squares) and ore-mineralization (circles) fluids are shown. Vennemann et al. such as Nevado del Ruiz. Su = Summitville.High-sulfidation Epithermal Deposits 0G -20-40O Q Alunite alteration stg. The origin of the D-enriched magmatic (endmember) fluid of HS deposits has been interpreted in two ways.and hydrogen-isotope relations are identical to those of volcanichydrothermal and geothermal systems associated with subduction-related volcanism (Giggenbach 1992b. NF = Nevados del Famatina. to meteoricwater-dominated late ore-stage fluid-inclusion waters (Ju3). Fig. See Appendix for references and information on data plotted. Satsuma Iwojima.and hydrogen-isotope composition of hydrothermal fluids in high-sulfidation deposits. Nansatsu district: Ka = Kasuga. Rye 1993): from a magmatic-waterdominated early stage of (alunite) acid-sulfate alteration (Ju.20 W W o Active systems (Giggenbach. 1995a) also have lower 5 1 8 0 values than those of acidic alteration fluids. Summary diagram showing variation in oxygen. Ju = Julcani. 8) and the vapor condensates from high-temperature fiimaroles of andesitic volcanoes (dark shaded field. Ore mineralization stg. Ro = Rodalquilar. 1992). The similarity is even closer between the composition of acidic alteration fluids (large shaded field. the ore fluids at Summitville (Rye et al 1990. inset). In addition to Julcani. Most workers conclude that the acidic fluid in HS deposits is derived from absorption of magmatic vapors outgassing from arc volcanoes or felsic magmas in crustal settings {e. &I800H is not used because hydroxyl oxygen requilibrates with the hydrothermal fluid during cooling (Rye et al. but such a shift is not indicated by the Julcani data. Tie-lines between data points connect samples from the same deposit. 8). 1993). SMOW) Figure 8. Fig. through main ore-stage fluid-inclusion waters (Jut and JU2). 437 . 1992b) so 6D(%. 8). Lake City. Le= Lepanto. 8. The overall oxygen. Hedenquist & Aoki 1991. this meteoric-magmatic watermixing trend is displayed particularly well by the three stages of alteration/mineralization at Julcani (Deen 1990. as typically seen in some neutral-pH geothermal systems. only alunite data were used for the alteration stage (SD and 8l8OSOi. is not known. Where possible. Inset shows the isotopic composition of fields defined by waters from active geothermal systems and high-temperature fumarole condensates in subduction-related andesitic volcanoes (from Giggenbach 1992b). The approximate compositions of groundwaters suggested for several deposits are indicated by the intials parallel to the meteoric water line. The extent of an O-shift in the groundwater component due to water-rock interaction.) -100 Volcanic Geothermal 10 15 20 -20 i -15 1 -10 1 -5 6 18 1 0 '—r 5 0 (%o. Fig. Colorado. Matsuhisa 1992.). 8. Iw = Iwato.g. Fig.

all are indistinguishable. Rye 1993. Hedenquist et al. By contrast. the enrichment in deuterium is the result of reaction in a low water/rock environment between magmatic fluid of 8D ~-80°/Oo (calculated on the basis of the D/H of igneous biotite) and wallrock at magmatic temperatures down to T = -400 °C (Rye 1993). a drop of the paleowater table during a late stage led to overprinting of steam-heated acid leaching with Hg mineralization and abundant cristobalite (Sillitoe & Lorson 1994)..A. Atmospheric oxidation of sulfides during weathering in at least three HS deposits (Goldfield. aside from the Paleozoic deposits in southeastern Australia and the Proterozoic Enasen deposit in Sweden). 1989. If magmatic fluid is accepted as the dominant metal source in porphyry copper deposits. On the basis of geological and mineralogical criteria. this volume. 1994a.g. Arribas & Tosdal In deposits that have not suffered deformation and metamorphism (those in Table 1. Rye et al. and stable-isotope analyses of alunite. Table 3) led to development of surficial supergene acid-sulfate blankets. particularly in districts where a majority of the host or country rocks are expected to have isotopically distinct signatures from those of the genetically related igneous rocks. Au/Ag values and high Te.. 1985.g. At Paradise Peak. 1979. 1995a).. 8) is a consequence of fractionation during degassing from the melt (Taylor 1986. Sn. Arribas. beneath the ore zone. The study of radiogenic isotopes so far has not provided conclusive evidence. Doe et al. 1992. but these studies provide no information about the processes by which the hydrothermal system acquired the metal {i. The reason for this is a consequence of the common intimate association between the deposits and host rocks. White 1991. porcelaneous veins consisting of fine-grained A1<2 . the principal post-depositional processes affecting HS deposits are mineral deposition from nearsurface steam-heated or supergene waters. 1991a. Mitchell 1992). Hedenquist et al. Sillitoe 1989. Arribas et al.. Hayba et al. There is consensus among most workers (e. 1995a) have shown that the Pb in the deposits is igneous. White & Hedenquist 1995). KAr dating. SOURCES OF METALS 1994). and Summitville. then the best evidence for a magmatic fluid source in HS deposits comes. a condition that would not favor the extreme acidity required for formation of vuggy silica at shallow depths (Giggenbach 1992a).. POST-DEPOSITIONAL EFFECTS The origin of metals in HS deposits is more speculative. The O and D enrichment of the volcanic vapors with respect to their parent magmas (Fig. 4) and similar metal associations (i. for Pb-isotope systematics. Both can result in acid-sulfate alteration which may mask hypogene alteration zones and ore. either directly by a magmatic vapor or hypersaline liquid that is incorporated into the hydrothermal system. 1994a) that the bulk of the ore-forming components is contributed by magmatic fluid. this would likely result in neutralization of the magmatic fluid. Jr. however. Arribas et al (1995b) have argued for a common magmatic metal source for the FSELepanto porphyry-epithermal HS copper-gold system on the basis of the intimate spatial and temporal relations (Fig. identification of the origin of acid-sulfate minerals overprinting should be straightforward (e. in low-sulfidation gold deposits it is not uncommon to detect a component of basementrock Pb (e. 1991a. perhaps. Rodalquilar. 1979) and Rodalquilar (Arribas et al. Matsuhisa 1992).e. or indirectly by remobilization of metals from a porphyry-type protore. Detailed and comprehensive radiogenic isotope studies are needed. leaching of the host rocks or derivation from a crystallizing magma).g. In an alternative interpretation proposed by Deen (1990) and Rye (1993). and Bi).. This interpretation requires that there have been chemical and isotopic equilibrium between the magmatic fluid and country rock. Lead-isotope studies at Summitville (Doe et al. In this context. Supergene alunite at Rodalquilar forms white to yellow.g.e. Henley 1991. from consideration of the common genetic connection between the two deposit types (Sillitoe 1988. Henley 1991. e. 1992.

and given the amount of water in the precious-metal veins by emplacement of type of magmas associated with HS deposits. formation of supergene alunite at ~10 Ma at Goldfield and Paradise Peak (Table 3) seems to be related to regional tectonic episodes (e.High-sulfidation Epithermal Deposits (Jannase/a/. see Sillitoe (1991a). 1993) and Masupa Ria.diatreme or flowaspect is important from a genetic perspective. the total most cases. These unusual conditions seem to have presented recently by various workers. Similarly. Deen 1990). In contrast.g. 1990. Arehart et al. For example. reaches the shallow depth (Lowenstern 1994. kaolinite. in fluid phase in the roof of the intrusion. a low-salinity vapor and a hypersaline also shows clear crosscutting relations between liquid (Fournier 1987. which incorporates were identified. Aoki et al. the subvolcanic intrusions seems to represent an replacement skarn deposits. sulfidation deposits. crysit is unwise to place strict limits between these tallizing. Berger & Henley (1989) suggested that precious-metal mineralization in HS deposits is introduced by later incursion of low-sulfidation geothermal-type fluids into previously formed HS alteration zones of magmatic origin. and cooling magma. the early stage of acid-sulfate confining pressure of a few kilometers depth (500alteration is separated from the base. A selection occurred at the Kelly mine. with chloride-complexed (commonly <50 \ixn) pseudocubic alunite with subordinate jarosite. crosscutting relations at Julcani = Shinohara & Kazahaya this volume). typically origin of HS deposits in the broad context of intermediate calc-alkaline magma to within a few metallic deposits formed within magmatickilometers of the paleosurface. Most of these models consider the deposit is emplacement of an oxidized. 3 in Hedenquist this volume). At the are unambiguous.. 1990). and even submarine "aborted" late-stage feeder of a comagmatic volcanogenic massive sulfide deposits). Philippines (Comsti et that emphasizes the variations in conceptual al. models includes Sillitoe (1989). (1994a. To explain this observation. Rather than a hydrothermal systems {i. However. For an account of supergene effects in deposits of the Chilean Andes. Within the ascending. 1995a). Giggenbach (1992a). Shinohara 1994). porphyry-type deposits. 1990). and hydrated amorphous silica (Arribas et al. minor and lie primarily in the details of the oreThe initial requirement for formation of a HS forming stage. mineralization in a main stage of acidic wallrock alteration (early) HS deposits does not occur under the reduced to a main ore-forming stage (late). overlapping hydrothermal assemblages Hedenquist et al. as dome complex. Rye (1993). a hydrothermal ore-forming environments (Hedenquist & fluid phase exsolves and concentrates ore-forming Lowenstern 1994).and 1000 bars). Berger & Henley Indonesia (Thompson et al. the tourmaline-pyrite-quartz-altered breccia dykes magmatic fluid will separate into two aqueous (Shelnutt & Noble 1985. A feature of HS deposits which has been noted commonly is a change in the hydrothermal system with time towards a fluid that is less reactive and less oxidized. 439 . This central-vent volcano or a maar . In precious-metal mineralization occurred during the common among these models is an evolution from low-sulfidation stage. Because of magma described here should be considered as successive convection and concentration of the magmatic phases of an evolving hydrothermal system..e. and Sillitoe (this volume). much of the precious-metal potential suprajacent hydrothermal system far mineralization at Pueblo Viejo was directly exceeds that of the comparatively small stock that associated with acidic alteration (Muntean et al. In these two deposits the known White 1991). El Indio phases. The differences conditions of low-sulfidation-type geothermal among the models mentioned above are relatively fluids (see Fig. the two stages metals and volatiles. Hedenquist & Lowenstern early enargite veins and later gold-quartz veins 1994. without sharp boundaries between amount of water and metals available for a them. In the western United States. distinct. where two (1989). including lowspatially and temporally isolated magmatic event. This model GENETIC MODELS requires coincidence of two distinctively different hydrothermal fluids along the same plumbing Genetic models for HS deposits have been system. 1994). 1992).

volcanic vent contacts. For the quartz-alunite-pyrite assemblage of the advanced argillic zone.. B2 = ascending metal-bearing magmatic brine with shallow cooler meteoric waters to explain high-salinity. Rye 1993.. Arribas et al 1995a). mixed magmatic-meteoric ore fluid (White 1991. The acidity of this groundwater-absorbed vapor condensate increases as the liquid cools. it may be absorbed by groundwater if it does not discharge as a fumarole. effective degassing will be favored by the structural factors characteristic of HS deposits. and B2: Two genetic hypotheses proposed for the stage of ore formation. the stable-isotope evidence is consistent with magmatic vapor being absorbed by meteoric waters. Sakai & Matsubaya 1977). Reaction of the increasingly acidic liquid with wallrock results in the upward alteration sequence of sericite-»kaolinite-» alunite-^vuggy silica (Fig.g. except silica.. Dilution with groundwaters is unlikely because the high temperatures surrounding the cooling magma cause meteoric water cells to be displaced from the magma core (Fig. 9A). Jr. ALTERATION ORE DEPOSITION B2 Heated ground. To form the styles of alteration and the spatial distribution of alteration zones characteristic of HS deposits. 9A). then by progressive dissociation of H 2 S0 4 and HCl at lower temperatures (<300 °C). first at temperatures below ~400 °C by disproportionate of S0 2 to form H 2 S0 4 and H2S (Day & Allen 1925. mixed magmatic-meteoric ore fluid (Hedenquist this volume). A: Early stage of advanced argillic alteration dominated by magmatic vapor. several modes of magma degassing may occur which will lead to different styles of magmatic-hydrothermal systems with or without associated mineralization (Giggenbach 1992a). B. Arribas..• waters Magmatic vapors (incl. = absorption of high-pressure vapor by entrainment in meteoric water cell at depth to explain lowsalinity. 9A). metals strongly partitioned into the high-density liquid (Hemley et al 1992.A. S 0 2 . Hedenquist this volume). As the high-temperature magmatic vapor reaches shallow depths of less than a kilometer. degassing must be very efficient. Rodalquilar. with oxidized hightemperature magmatic vapor reaching shallow depths with little reaction with rock or dilution by groundwaters at greater depths (Fig. The extremely acidic conditions may even lead to formation of dissolution cavities in which the only remnant of the host rock is a basal sedimentary layer of quartz phenocrysts (e. such as fractured volcanic domes or roots of domes. Model showing the two main stages of evolution of HS deposits. In addition to the relatively low pressure at the depth of intrusion. the residual vuggy silica rock results from complete leaching of the rock components. 1994a). and active faults with a dilational component. by a hydrothermai solution with a pH <2 and temperatures probably <250 °C (Stoffregen 1987). H a ) * f Vuggy silica Alunite Kaolinite Sericite K-silicate Absorption of high-P vapor 7* j Heated groundwater Magmatic brine Magmatic brine Possible Cu{Au) Figure 9. B. with the latter 440 . Hedenquist et al. caldera or diatreme faults. At this early intrusive stage.

<4 equiv.% NaCl. the hydrothermal liquid may be less dominated by a magmatic vapor phase and its associated "sulfurgas buffer" (Giggenbach 1987). as reflected by the alunite-pyrite assemblage (Whitney 1988. as demonstrated at Rodalquilar and in other deposits where highsalinity inclusion fluid is associated with the deep sericitic alteration (Table 4). Instead. and this reflects the much more variable geochemical environment in comparison with that associated with acidic alteration. In the Lepanto (Claveria & Hedenquist 1994) and El Indio (Jannas et al. these two assemblages are related to Cu-rich and Au-rich mineralization. 8). with the latter being of later stage in both cases. Henley & McNabb 1978. 1990) deposits.g. wt. Sillitoe 1989). however. Assessment of a Model No single model adequately explains all of these various observations. The presence of this S02-H2S buffer is the reason that the early stage of alteration is so oxidized. (2) a low-salinity magmatic vapor whose metal-transporting capacity decreases sharply with decreasing pressure (Hedenquist this volume). Vennemann et al.). Bruha & Noble 1983. (3) heated meteoric or connate water in deep convection cells that collapse inward and downward as the intrusive stock progressively solidifies and cools. porphyry mineralization) that envelopes the intrusion (Fig. high-temperature. Sillitoe 1989).g. the magmatic hypersaline liquid may remain at depth throughout the evolution of the hydrothermal system.High-sulfidation Epithermal Deposits constituting a relatively small part of the mixture (generally <l/3. This latter observation suggests an episodic ascent of high-salinity magmatic liquid from the greater depths of the hydrothermal system. salinities during the main ore stage can be low (e. Zijinshan. Importantly. Table 4). in places. During the ore stage. up to 18 equiv. Nevertheless. Ruggieri 1993b. is inconclusive because of the lack of temporal information. In the "volatile transport" hypothesis (Fig. Lepanto and El Indio. 8). wt. which are relatively high to intermediate sulfidation-state assemblages. respectively. increased dilution of the oxidized magmatic fluid by meteoric water.g.. each reflecting an emphasis on individual deposits or different interpretations of the fluid-inclusion and stable-isotope data. but may ascend (or be driven) to shallower depths if the ambient temperature is low enough (<400 °C) for the mechanical strength of the rock to increase sufficiently to result in brittle fracturing (Foumier 1992).. No discrimination. 3 in Hedenquist. The fluid-inclusion evidence. 9A. Four fluid regimes have been identified in the HS environment. evidence for all is present in the early stage of HS alteration. A basic understanding of this ore-forming environment may be gained by considering the principal end-member fluid components and ore-forming processes.% NaCl. wt. high-salinity inclusion fluids have been interpreted to form early in most HS deposits (e. this trend is also consistent with the isotopic composition of waters in the main ore stage of various deposits (Fig. by contrast. Fig. respectively (see Fig. The spectrum of characteristics displayed by HS deposits may be then analyzed in the context of such a genetic framework. 9A). Table 4) or moderate to high (Julcani. deep meteoric water entrainment of high-pressure 441 . and three of them are critical to formation of porphyry systems (e. These fluids may be restricted to greater depths. and. Giggenbach 1992a). where the hypersaline liquid tends to stay because of its high density (Fig.% NaCl.. The conditions during the main stage of ore formation are not yet as well-understood. Arribas et al. Two main end-member ore-forming hypotheses are considered. These magmatic brines may be more closely related to the K-silicate alteration (and. and (4) shallow and cool meteoric groundwater. 1995a). and the low-salinity vapors are responsible for mineralization (Sillitoe 1989. can be made between a meteoric-water component that is incorporated at deep or shallow levels within the hydrothermal system. and several hypotheses have been proposed. up to 22 equiv. 9B. this volume). 1993). These end-members are: (1) a metal-rich hypersaline magmatic liquid which tends to remain in the vicinity of the intrusion. conditions during the ore stage fluctuate within a range of redox potential that is reflected by enargite-pyrite ± alunite and enargite-tennantite-chalcopyrite associations. to some extent. The more reduced conditions are a likely consequence of increased water-rock interaction.

Most known HS deposits are young in age.g. and oxidized magmatic fluid derived from a degassing intrusion is supported by the following observations: (1) the volcanic rocks hosting HS deposits were erupted immediately prior to mineralization. Highsulfidation deposits form dominantly in subduction-related plutonic-volcanic arcs. Similarly. volcanic host rocks. but both hypotheses agree on a dominantly magmatic source for metals. Rye 1993. As a source of Au. such as that which may have formed close to the intrusion (e.. high salinities should not be as common as they are — unless they are explained by local boiling of dilute to moderately saline meteoric or seawaterdominated fluids. For example. Julcani). and because their mode of occurrence and the potential to overlie porphyry-type mineralization have been widely recognized only within the past 10 to 15 years.. by equilibrium fractionation between H2S and SO4 in solution at T -200-400 °C. Such seems not to be the case. and in the site of meteoric water dilution. HS deposits represent a valuable exploration target that has been overlooked in some regions. mineralization spatially associated with domes or volcanic conduits). possibly resulting from the abrupt pressure reduction associated with hydrothermal brecciation. they may occur in the same HS deposit as the magmatichydrothermal system evolves. A part of the ore-forming components may originate from leaching of wallrock. has not been suggested as the main ore-forming process in any of the deposits reviewed in this study..A. Hedenquist et al. if metals were supplied only by a dense. variations in depth of emplacement. and Ag (and in a few exceptional cases also Hg. These conditions are consistent with the low salinity of the Lepanto and El Indio fluid-inclusion data. None of the three models satisfies the overall evidence. In the "hypersaline liquid transport" hypothesis (Fig. metal associations. Cu.g. SYNTHESIS Gold. (3) the isotopic composition of hypogene sulfides (e. The principal difference between the two hypotheses is in the nature of the magmatic phase responsible for transporting the metals into the epithermal environment. alunite and barite) commonly can be modelled from the 34S/32S of sulfur in igneous rocks thought to be genetically related. W..g. assimilated here from the literature. not at depth in the meteoric water convection cell. This hypothesis has been proposed to explain the high salinities recorded by inclusion fluids in several deposits (e. The intimate relationship among HS deposits. following waning of the magmatic vapor plume responsible for early alteration.e. The three models for formation of HS ores. are not mutually exclusive. however. if alteration and mineralization were solely the result of interaction between groundwater and low. Sillitoe this volume). and changes in the local 447 tectonic and hydrodynamic environment. vapor is required for transport of sufficient amounts of metals (Hedenquist this volume. Tertiary and even Quaternary.and high-pressure vapor. and ore grade or metal abundances of the various deposits. A potential contributor to ore formation in HS deposits involves remobilization of the metals by a meteoric-water-dominated hydrothermal system from a subjacent K-silicate assemblage and porphyry-type protore. Bi. Jr. The deposits form at a depth intermediate between the surface and shallow (few kilometers depth) intermediatecomposition intrusions. Arribas. with an increase in the meteoric water component with time. commonly during crustal extension. and (4) on the basis of . Pb. The dominant ore-forming mechanism in this case is mixing of the metal-bearing hypersaline liquid with cooler groundwaters at the site of deposition. This mechanism. White 1991. a relation would be expected among estimated salinities. respectively. 1994a). and Zn) are produced from HS deposits. (2) the ore-forming hydrothermal system commonly follows the same plumbing as that of the magmatic system (i.g.. with complexities arising from multiple intrusions. Brimhall 1980). Mineral deposition in this case may be caused by mixing with cooler groundwater or by boiling. 9B2). on the contrary. the lithostatic-pressured system fractures and the metal-bearing hypersaline liquid ascends into the porous leached zone (Deen 1990. enargite and pyrite) and sulfates (e. high-salinity liquid.

43. E. O. R. G. in which the same HS geochemical environment has been documented. J. COMSTI. near Otaru. (1995): Gold mineralization in an evolving magmatic hydrothermal system at Mitsumori-Nukeishi area. REFERENCES AKAMATSU. 155-164. who also provided abundant documentation on HS deposits worldwide. (1993): Acid Hydrothermal Alteration at Otaru City. Yui. Most HS deposits evolve from an early period of acidic wallrock alteration to a late period of precious. the waters involved in formation of HS deposits are identical to waters in active volcanic-hydrothermal systems. On the other hand. eds. In Hydrothermal Ore Deposits and Wall Rock Alteration in Southwestern Hokkaido (H. Cunningham. Surv. ACKNOWLEDGMENTS Valuable insight on various aspects related to this exciting ore-forming environment was gained through discussions and field work with M. & WATANABE. Geol. Rye. respectively.. Factors such as multiple intrusions and opening or closing of fractures (conduits) result in variations in the temperature. Bening & Seward 1994. and veins) that usually occupy a limited vertical span of <300 to 500 m (except for >800 m at the giant Chinkuashih deposit). M. J.. A.C. M. LAZO. 1994 fiscal year. northern Honshu. Resource Geol. & MATSUHISA. Anne Thompson. Hedenquist. General Evaluation of Geological Structure. and Jeff Hedenquist. S.and base-metal mineralization.and T. pressure.. Geol. Acidic alteration is characterized by advanced argillic assemblages and porous (leached) rock. and the hydrothermal fluid responsible for this alteration is dominated by high-temperature magmatic vapor containing S0 2 . (1992): Acid sulfate alteration at Akaiwa. Philippines. Geol. (1993): Advanced argillic alteration and geochemistry of alunite in an evolving hydrothermal system at Baguio. Peter Vikre. Ministry of 443 . Congress Field Trip Guide Book d. Y. A. C. Arribas Sr. southern Hokkaido. M. Andrew Campbell. Y. M. Japan Report 279. J. AOKI. that a magmatic fluid interacts extensive ly with country rock and groundwaters on its relatively short path to the earth's surface. Rytuba. & K. Sapporo. Japan.High-sulfidation Epithermal Deposits oxygen and hydrogen isotopic ratios. John Thompson. Surv. AOKI. Aoki. Ore formation in some HS deposits may accompany acidic alteration.C. Steven. 35-37 AOKI. these conditions lead to a variety of deposit styles (mainly replacements.). Kurosawa.B. 17-23. Soc. and HC1. Tokyo. breccias. Minamikayabe. H2S. Seward 1973). & YUI. Hokkaido Univ. M. Less reactive and oxidized fluids are typically responsible for ore mineralization. the presence of moderate to high salinities in many HS deposits. Matsueda. (1992): Magmatic fluid discharging to the surface from the Osorezan geothermal system. the intimate association with porphyry coppertype deposits. and geochemical evidence. and recent studies of the hydrothermal geochemistry of Au provide preliminary evidence that this element may be transported in HS and low-sulfidation systems as different hydrosulfide complexes (AuHS0 and Au(HS) 2 . mineralogical. Japan Report 277. Noel White. K. S. Kelly. and composition of the ascending solutions. (1991): Mineralogical features and genesis of alunite solid solution in high temperature magmatic-hydrothermal systems. Japan (in Japanese) AKAMATSU. and the assumptions of the most recent genetic models (transport of Au and Cu by either hypersaline liquid or high-pressure vapor) indicate that chloride complexes must also be considered for metal transport. illustrates the basic genetic condition of HS deposits. particularly the association between the orebodies and the lateral and vertical zones of alteration. thesis. Resource Geology. 16-21 AOKI. Earlier versions of this manuscript benefited from constructive reviews by Phil Bethke. In Report of Regional Geological Survey. 29th Intemat. Hokkaido. K. southwestern Hokkaido. F. The geological. northern Luzon. Combined with the shallow environment of mineralization. W.S.

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1971. LI. 1984. n = 4 (A. unpub. 1993). analyses in Sillitoe 1993). «H2s = 19. n . Korea. & MATSUEDA. C. (1991): High sulfidation epithermal gold deposits: Characteristics.C. 9-20. Nansatsu. Geol. 1990). 86-92. 1991. n = 31 (John et al. Geochem. n S o 4 = 9 (Hedenquist et al.N. unpub. 1995a). N. Econ. 1995). dacite and rhyodacite. D. Geol. 93-99.1 (Arribas et al. hornblende andesite. China [Taiwan] Proceedings 19. & HEDENQUIST. 83. Geol. Open-file Report 92-9. 127-133. Surv. YOON. Soc. Upper Formation and hornblende andesite in Middle Volcanic rock. and 8. 7. number of samples (w).445-474. and rhyolite domes. Goldfield. n = 10 (Petersen et al. (1976): Trapping temperature and pressure of the fluid inclsuions in the gangue minerals of gold-silver-copper deposits at Chinkuashih. Econ. sulfates («so4)» sulfide-sulfate mineral pairs («A34S)> and references: Lepanto. «A34S = 7 (Jensen et al. rhyodacite n = 6 (Ransome 1909. M. & HEDENQUIST. 1995). 305.A.C. McCAUGHEY.C. Explor. «H2S = l g3 » 453 . Chinkuashih.W. 1977). « s 0 4 = 38 (Hedenquist & Garcia 1990. Izawa. Ashley. Resource Geol. LI. 44. Surv. Summitville. YEN. (1995): Epithermal gold deposits: styles. Japan Report 227. Given below are the number of measurements for sulfides ("H2S). J. Pueblo Viejo. 277. n = 2 (E. Geol. LEAKE. n S 0 4 = 17. Rodalquilar. & ZHANG. 44. Choquelimpie volcanic complex (5 units). unpub. 1972). n = 15 (Maksaev et al. Goldfield. YUI. J. Hedenquist & M.C. Summitville. Laurani volcanic and intrusive rocks. n S04 = 16. Choquelimpie. CHEN. Nansatsu. Paradise Peak. C. 36. ZHAO. 1993). Soc. (1988): Composition and activity of sulfurous species in quenched magmatic gases associated with pyrrhotite-bearing silicic systems. WHITE. (accepted). Geol.. & PARRIS. and guidelines for exploration. characteristics and exploration. J. average of Younger andesites. (1994): The Zijinshan deposit: the first example of quartz-alunite type epithermal deposit in the continent of China. and a model for their origin.S.J. WHITE. Vikre 1989).18 (Chen & Huh 1982). Julcani.. Newsletter 21. Explor. N. Z. 1991).High-sulfidation Epithermal Deposits separation and total stable isotope analysis of alunite. data).W. n = 10 (Jimenez et al. Resource Geol. J. « H2S = >11. J.. Julcani. S. Cerro de las Tortolas Formation. Taiwan. «H2s = 16. Fisher quartz latite. porphyritic intrusions. D. El Indio. 1994a). "A34S = 7 (Rye et al. and written comm. K. (1994): Gold content variations in the acid-sulfate alteration zone of the Seongsan and Ogmaesan clay deposits in Naenam area. S. Nagano prefecture. n = 20 (Gropper et al. n = 10 (Perello 1994. N. The name of lithologic units analyzed. J. B. in Sillitoe 1993). N. Geochem. (1995): Epithermal deposits of the southwest Pacific. WHITE. n^s = 4 (Vennemann et al.H. written comm. dacite n . J. Imbanguila dacite and least altered quartz diorite porphyry. (1994): Several mineral deposits in Saku-Machi. «H 2 S = 6. Motomboto. n = 7 (Steven & Ratte 1960). n S04 = 7. ZHANG. and data sources are given: Chinkuashih. (1990): Epithermal environments and styles of mineralization: variations and their causes. WHITE. APPENDIX 1 Summary of data and references used to compile Figures 3. Lepanto. WHITNEY. Figure 3 K 2 0 versus Si0 2 variation diagram. «A34S = 2 (Folinsbee et al. chemical data for the feldspar porphyries genetically related to mineralization are not available). «H2S = 52. Figure 7 Range of 534S (°/oo) values. data). H. Y.W. Laurani. Aoki..C. 44. U. Arribas. (accepted). Resource Geol. wH2S = 4> n S04 = 2. dacite tuff.

data). n = 6 (Arribas et al. El Indio. Ju3 = late-stage ore fluids in barite. Hedenquist. 1992). Matsuhisa & J. NF = suggest that mixing of enriched magmatic fluid waters may result in hydrothermal acid-sulfate 1989). K-silicate and quartz-sericite at Nevados del Famatina have 8 O between 4 and 10°/oo. Lake City. Jr. stage V alunite-kaolinite. Su = Summitville. Rye 1993).A. siderite. «H2S = 44. 1995a).4 (Arribas et al. nS04 = 1 1 . 1990) and Lepanto (7" = 420 °C at the 700-m level. reflecting a larger magmatic component (Losada-Calderon & McPhail 1994). Figure 8 8D versus 8 O variation diagram. Rodalquilar. 1995a). Sulfide-sulfate mineral temperatures higher than 350 °C were documented only at depth at Summitville (T = 390 °C. On the basis of phase equilibria. kaolinite. nH?s = U> "SO4 = 3 (Jannas et al. alunite. 9 in Vennemann et al. Ju = Julcani. Iw = Iwato. alunite n 1 ft Nevados del Famatina. (1990) to be about 3 and 35. chalcedonic ore. PV2 = stage 2 pyrophyllite (Fig. 1995a). 8D are not available for this stage but present-day groundwaters. RM = Red Mountain. The main ore stage. and botroidal pyrite (Deen 1990). 6 O values of residual vuggy silica associated with ore in both depositsfall between Ka and Iw (Hedenquist et al. 1994a). alunite. and galena fluid inclusions. alunite (/? = 6). average of n = 10 (8D) and n = 16 (8 18 0) (Rye et ah 1992). Le = Lepanto.and 8 Owith isotopically light D. tetrahedrite. a the 8D. the sulfide/sulfate values for the Pueblo Viejo stage 1 and stage 2 mineralization were estimated by Muntean et al. respectively. n = 2 (Y. 1992) i o = 2. 1990). and illite fluids in the deposits have a limited range of 8D values. (1972) and more recent fractionation equations. ore fluids from Rye (1993). The data for stage 2 at Rodalquilar and Pueblo Viejo should be viewed as approximate. alunite. PV = Pueblo Viejo: PV] = stage 1 alunite and kaolinite. 1990. 1993). Stage 2 (pyrophyllite) fluids for Pueblo Viejo involve several assumptions with respect to the choice of fractionation factors for oxygen and hydrogen. Nansatsu district: Ka = Kasuga. Temperatures for Chinkuashih were calculated using the 4 S/ S data from Folinsbee et al. the average 8D and 8 . unpub. -900 m below the present surface. immediately above the FSE porphyry copper Rodalquilar (stage 2) is based on 8 1 8 0 of chalcedonic quartz. enargite. Ro = Rodalquilar. Hedenquist & Garcia 1990). n = 12 (Bove et al. n = 10. « A 3 4 S . Colorado. Jut = average of main-stage ore fluids in wolframite. hypogene alunite. Rye et al. Arribas. alunite. alunite n = 1. «A34S = 7 (Deen 1990). n = 1 (Rye et al. "so 4 = 55. 8 0 values for La Mejicana {n = 9) are similar to NF. alunite. Explanation: Go = Goldfield. Data for a single alunite for Goldfield (Rye et al. Ju2 = average of main-stage ore fluids in sphalerite and chalcopyrite.and O-depleted fluids (see also Vikre 454 . suggesting significant variations are unlikely (Arribas et al. n = 1 (Losada-Calderon & McPhail 1994).

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