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

23 (1995)

Chapter 19

CHARACTERISTICS OF HIGH-SULFIDATION EPITHERMAL DEPOSITS, AND THEIR RELATION TO MAGMATIC FLUID


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

INTRODUCTION

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).

419

A. Arribas, Jr. Table 1. Principal high-sulfldation deposits or documented prospects ordered geographically Nin 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

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

WT

--TV?
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.
OPENING REMARKS ON GENETIC ENVIRONMENT

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;

421

A. Arribas, Jr. Table 2. Main geological characteristics of 14 selected high-sulfidation epithermal deposits
Deposit/district, location Motomboto, Indonesia Nalesbitan, Philippines Lepanto, Philippines Chinkuashih, Taiwan Zijinshan, China Nansatsu, Japan Summitville, Colorado Age (Ma) 1.9 Metals, (tonnes)1 Cu, Au, Ag 60,000 t Cu. 4 i Au, 180tAg(c) Au 15 t Au (c) Cu, Au, Ag 900,000 i Cu, 1201 Au(c) Au, Cu, Ag 92 t Au, 183 t Ag, 120,000 tCu(p) Cu, 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 <1.0 m.y. Deposit form Hbx , veins, dis in VS Hbx, veinlets Vertical breccias, veins, stratabound replacements Veins or "ledges", hbx, dis and stk surrounding veins Veins, hbx, stk

Dae dome, ands/dac/rhy Dioritic, qtzdioritic stocks flows, pyr and volx Ands pyr + flows Ands/dac vol, Miocene + older volx + metavol Dae vole Miocene sed Jurassic granite, Cretaceous dac porpyhry+pyr Ands pyr, flows + volx Qu-lalite porphyry None observed Qtz-diorite porphyry Dacite domes and flows Not reported

Pliocene 1.5-1.2

N/A <analyt. error (0.1 m.y.)

1.3-1.0

-94

Dome along caldera margin?

7.0 m.y.(?) (poorly-dated)

5-3.5

22.5

Small volcanos Au 18 t Au (p) + 18 t in a caldera? Au reserves Au, Cu, Ag Dome along 17lAu preexisting caldera margin Au (Ag, Cu) Domes along 130 t Au, t 43 Ag, preexisting ring 37,000 Cu (p) fracture Au, Ag, Hg Within or close 47 t Au, 1255 Ag to a central-vent 457 l Hg (p) volcano Au, Ag Maar-diatreme >600 t Au (p; complex Sillitoe. 1993) Ag, Cu, Pb, Au, Dome complex W, Bi, Zn around a central diatreme Au, Ag, Cu Stratovo!cano(?) -140 t Au, in earlier caldera -1,100 t A g ( c ) Dome complex(?) Cu, Au, Ag >10-15tAu(c) Au 10 l Au (p) Caldera margin

HorWende ands <0.5 my (Middle Voles) Qtz-monzonite porphyry <analyt. error (0.5 m.y.)

Dis in stratabound VS/MS bodies, veins, hbx "Ledges" with veins, hbx + dis inVS "Ledges" with veins, hbx + dis in MS Stratabound bodies commonly with hbx Mushroom-shaped bodies with stk + dis Veins

Goldfield, Nevada

21

Miocene andesite

Andesite

<analyt. error (0.4 m.y.)

Paradise Peak, Nevada Pueblo Viejo, Dominican Rep. Julcani, Peru El Indio, Chile La Mejicana & Nevados del Famatina, Argentina Rodalquilar, Spain

19-18

Composite welded tuff, volx + ands flows Maar sed + basaltic vol (spilite) Dactorhyodacitic domes and tuffs Dac, rhy pyr; dac + ands vol Paleozoic seds + granites. Pliocene intrusive dacite Ands to rhy pyr flows, collapse bxs + domes

And/dacvd

<analyt. error (1.0 m.y.)

-130

9.8

CAbimodal N/A (Rhy + basalt) volcanic suite Dac/rhyodacitic <analyt. error porphyry (0.1 m.y.) CA vol N/A

13-8

Veins + stk

4.0-3.6

11-10

Dac/rhyodaoic porphyry stocks Ands flows + dykes

<1.2 m.y.

Veins; also hbx at N. del Famtina Veins, hbx, dis in VS

<analyt. error (0.7 m.y.)

Abbreviations used: w calc-alkaline, MS = massive silica, VS - vuggy silica, ands - andesitic, bre - b r e c c t a ^ 5 n L 2 r f c k 'stk Abbrev.at.ons usea: CA disseminations, hbx - hydrothermal vein breccia or breccia pipes, pyr = pyroclastics, qtz - quartz, rhy - rhyol.t,c, sed - segmentary rock, stk stockwork, vol volcanic rock (unspecified), volx volcaniclastics = , IVIVUillVIWUVd ' (p) produced, (c) estimated total contained 1 Approximate number, quoted from paper or estimated from figures: 150 m for Paradise Peak is for individual orebodies

Giggenbach 1992a; Rye 1993; Hedenquist et al. 1994a). However, the basic genetic controls, as we understand them now, were formulated almost ninety years ago by Ransome (1907) following his classic study of the Goldfield Au-Ag-Cu deposit. In his own words "the [ore depositing] solutions were essentially emanations from a solidifying body ofdacitic magma" and " . . the initially acid emanations would be neutralized and modified in their ascent through fissured rock . .by the distance and kind of rock traversed, the quantity and character of admixed surface-derived waters,

and the pressure and temperature gradients". This concept formed the basis for Ransome's "direct volcanic hypothesis", though it was quickly abandoned in favor of a "simultaneous solfatarism and oxidation" model (Ransome 1909). 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. The crucial aspect is identification of the origin of alunite or acid-sulfate alteration, which can be generated by different mechanisms in three

High-sulfidation Epithermal Deposits Table 2 (continued)


Deposit/district, location Motomboto, Indonesia Nalesbitan, Philippines Lepanio, Philippines Chinkuashih, Taiwan Zijinshan, China Nansatsu, Japan Summitville, Colorado Control on mineralization Contact between dome and volcanic rock, steep fault Steep strike-slip fault Major steep + minor faults, diatreme contact, unconformity, permeable layers Steep normal faults + their intersections, 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, age within 1.0 m.y. Proposed, none known Above + adjacent same age porphyry Cu-Au deposit None known References Perell6(l94)

250 ISO 500 800

Sillitoerta/. (1990) Garcia (1991), Arribasrta/. (1995b) Huang (1955), Tan etal. (1993) Ren era/. (1992), Zhang etal. (1994) Izawa & Cunningham (1989), Hedenquist etal. (1994a) Steven & Ratti (1960), Menhert etal (1973), Stoffregen (1987), Rye (1993) Gray & Coolbaugh (1994) Ransome (1909). Ashley (1974), Ashley & Silberman (1976), Vikre (1989, written commun. 1995) John et al. (1991), Sillitoe & Lorson (1994) Russell &Kesler (1991), Mumeanero/. (1990) Petersen etal. (1977), Noble & Silberman (1984), Deen(1990) Siddeley & Araneda (1986), Jannasai(1990)

600(7)

None known

<150

None known

250

Intrusion-centered sericitic, low grade stk mineralization None known

Goldfield, Nevada

Moderately + shallow dipping faults & fissures

400

Paradise Peak, Nevada Pueblo Viejo, Dominican Rep. Julcani,

Steep faults and permeable pyroclastic layers Diatreme ring fault + permeable layers Steep fractures

<150

400(7)

Sericitic, stk Au mineralization (East Zone) None known

600
>300

None known

Pem
El Indio, Chile La Mejicana & Nevados del Famatina, Argentina Rodalquilar, 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), Losada-Calderon et al. (1994) porphyry Cu prospect Arribas etal. (1995a) None known

principal geologic environments (Bethke 1984; Rye et al. 1992): (1) by the disproportionation of magmatic SOj to H2S04 and H2S following absorption by groundwater (magmatichydrothermal), (2) by atmospheric oxidation of H2S in the vadose zone over the water table, associated with fumarolic discharge of vapor released by deeper boiling fluids (steam-heated), and (3) by atmospheric oxidation of sulfides during weathering (supergene). Magmatichydrothermal alunite occurs with minerals such as diaspore, pyrophyllite, kaolinite, dickite, and

zunyite, which are typical of hypogene (T = 200350 C) acidic conditions (advanced argillic assemblage; Meyer & Hemley 1967). This type of alunite is characteristic of HS deposits, but it may also appear in areas of advanced argillic alteration void of ore mineralization (e.g., Iwao 1962; Hall 1978). 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, H2S-rich fluid, typical of geothermal systems that form low-sulfidation deposits.

423

A. Arribas, Jr. Vuggy silica Quartz alunite PropylWc

Chlorite-rich rock

Montmorillonite-rich rock

100 m

Figure 2. Cross-section of alteration zones characteristic of high-sulfidation. deposits,. as observed at the Summitville Au-Cu deposit, Colorado. Diagramat left (simplified from Steven & Ratte 1960) shows schematic outward zonation from a subvertical mineralized body, shown at right (from Stoffregren 1987). Because of the relatively shallow and dynamic environment of mineralization, overprinting among the three types of acid-sulfate alteration (including supergene) is possible; however, the spatial relation of each type of alunite to ore is different, and correct identification is important for exploration (Rye el al. 1992; White & Hedenquist 1995).
DISTRIBUTION, A G E AND ECONOMIC SIGNIFICANCE

In common with other magmatichydrothermal deposits (e.g., porphyry copper deposits), HS deposits coincide worldwide with plutonic-volcanic arcs. This association is best observed in the Cenozoic deposits of the CircumPacific and-the Balkan belt of southeastern Europe (Fig. 1). These deposits occur in two main settings: in island arcs and at continental margins. The tectonic regime during formation of the deposits seems to be dominantly extensional (Sillitoe 1993). Some deposits (e.g., Goldfield, Rodalquilar, Summitville) formed in intracontinental regions during periods of extension that followed regional compression and subduction by several m.y. Tertiary HS deposits predominate, and only a few deposits are Mesozoic (e.g., Pueblo Viejo, Zijinshan), Paleozoic (e.g., Temora and others in southeastern Australia), or PreCambrian (the early

Proterozoic Enasen Au deposit located in the Baltic shield of central Sweden; Fig. 1). The youngest deposits are Pleistocene (<1.6 Ma) and occur in the central western Pacific (Kelly, Lepanto, and Chinkuashih). 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. Gold, copper, and variable amounts of silver are the main products of HS deposits (Table 2). Gold (Nalesbitan, Rodalquilar), occasionally with silica by-product (Nansatsu), is the only economic metal in the smaller deposits. No copper is produced at Paradise Peak and Pueblo Viejo. Mercury is produced at Paradise Peak, and the Julcani district has been a source of a remarkable polymetallic assemblage consisting of Ag, Cu, Pb, Au, W, Bi, and Zn (Table 2). The six largest deposits or districts (Chinkuashih, El Indio, Goldfield, La Coipa, Lepanto, and Pueblo Viejo) each contains more than about 100 tonnes of gold. The economic potential of this type of mineralization is clear in regions such as the Chilean Andes (Sillitoe 1991a).
VOLCANIC SETTING AND ASSOCIATED IGNEOUS ROCKS

The high-sulfidation deposits considered in Table 2 occur within intermediate-composition volcanic rock sequences having ages broadly

High-sulfidation Epithermal Deposits Figure 3. K 2 0 versus Si02 variation diagram for rocks thought to be genetically related to high-sulfidation deposits. The samples from 12 deposits or districts ( = 140) define a small compositional field, which contrasts sharply with the large field defined by volcanic rocks associated with lowsulfidation or intrusion-related Au deposits (>100 samples from 16 districts; Sillitoe O 1991b, 1993; Muller & Groves 1993). The degree of alteration of the rock samples and precision of the analytical data are largely unknown; however, according to the individual data sources, most of the samples are unaltered or very weakly altered. Circles indicate average values for each highsulfidation deposit or district: Ch = Chinkuashih, Cq = Choquelimpie, Go = 50 70 80 60 Goldfield, In = El Indio, Ju = Julcani, La = SCv, (wt%) Laurani, Le = Lepanto, Mo = Motomboto, Na = Nansatsu, PP = Paradise Peak, Ro = Rodalquilar, Su = Summitville. Compositional fields after Keith et al. (1991). See Appendix for references and information on data plotted.
CM

similar to that of mineralization. Where abundant radiometric ages are available, the age of the host rocks and the age of mineralization are within analytical precision; where a difference is indicated, it is typically less than ~1.0 m.y. (Table 2). A common spatial association exists between the deposits and shallow, typically porphyritic intrusions. These intrusions are interpreted to be the roots of volcanic domes or the feeders of central-vent volcanoes or maar-diatreme complexes, the three main volcanic settings for HS deposits (Table 2). Some deposits are hosted entirely within a single dome (Summitville), or within a dome complex (Julcani). In most cases the mineralization extends from the subvolcanic intrusion into country rocks, such as the Main Vein Cu-Au-Ag deposit and associated breccia deposits in the Penshan area of the Chinkuashih district. Some deposits, however, do not show any (known) spatial association with subvolcanic intrusions thought to be genetically related to mineralization (e.g., Nalesbitan, Nansatsu). In the Rodalquilar Au deposit, 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; a larger intrusive body is

thought to exist at depth (Arribas et al. 1995a). The main control on location of mineralization at Rodalquilar is the structural margin of two nested, resurgent calderas. With the exception of Rodalquilar, 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. 1990). The magmas thought to be genetically related to HS deposits have a remarkably limited compositional variation. The ranges of wt.% K 2 0 and SiC2 for twelve deposits overlap greatly and show a dominance of calc-alkaline andesitic and dacitic compositions, with subordinate rhyolite (Fig. 3). Intermediate calcic volcanic rocks are limited to porphyritic intrusions in the Lepanto and Motomboto Cu-Au-Ag districts, and intermediate-to-felsic alkali-calcic rocks are characteristic of the Summitville and Laurani districts (Fig. 3). Interestingly, no deposits have been discovered in association with alkaline or mafic magmas, even though these magmas can be genetically related to low-sulfidation and intrusion-related Au deposits (Sillitoe 1991b, 1993; Muller & Groves 1993; Richards this volume). The data shown in Figure 3 suggest a relation exists between magma composition and
425

A. Arribas, Jr. Table 3. 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, ena-luz, mar, sph, gal, lentet, are, cpy, arg, nat.Au, tell Py, chalc.qtz, ceo, bor, cov, ena, tell

Deposit Motomboto

in:
Silica core

Ag/Au 35-45

Nalesbitan

Silica core

Very low Ag

Lepanto

Chinkuashih

Zijinshan

Ena-luz, py, ten-let, cpy, py, ele. sph, gal, mar, sele, tell, Snbearing sulf py, ena-luz, fam, ten-let, nat.Au, ele, bar, naLHg, tell, sph, gal, cpy, geo, bou VS/MS-* qtz-dic-lu- qtz- py, dig, ena, cov, mol, naLAu cpy, bor, let-ten, gal, sph dic-ser-qtz-ser

Silica core

Silica core

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-kaopyo MS(VSHqtz-alu-kao (SER in faulted, deeperC?) East Zone deposit) Early: Kao-py-qtz-* alu-py-qtz Late: MS-pyo-dia

Summitville

ena-luz. py, ele, nat.Au, arg, pyr, cpy, bor, sph, gal, cas, sta, mol, can py, ena-luz, cov, mar, naLS, nat.Au, sph, gal, bar, cpy, ten py, fam, ten-let, bis, got, naLAu, ena-luz, bar, tell, sph, cov bar, stb, bis, nal.Au, mar, py, nat.S, cin, sph, gal, cpy, ars, let, arg, cov, fam py, sph, ena, nal.Au, nat.S, bar, len-tet, fam, gal, bar, stb, ele, sele, tetl, Bi- Pb- Ag- sulf py, wol, cas, nat.Au, ena, luz,

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, Nevadosdel Famatina Rodalquilar

kao~*qtz-kao; Syn-ore: qtz-pyo-py-qtz- kao-py-< qtz-scr-py qtz-kao-sme Cu stage veins-* kao-aluser-qlz; Au stage veins-* ser-kao-pyo-qtz Alu-kao-*qtz-ser- (K-silicate in N. del Famatina porphyry copper) VS/MS-qtz-alu-kao-* qtz-kao-ser-qtz-ser-py

tet, ten, cpy, gal, sph, bar, sid, Pb- Bi- Ag-bearing sulf Ena, py, tel, nat.Au, ten, cpy, gal, sph, hue, bor, dig, emp, ceo, mar, bar, py, ena, cpy, sph, ten-let, cov, ceo, fam, luz, naLAu, gal, mol, ele, tell, col Sn-Bi-Pb-Ag-sulf Py, naLAu, ena, tell, cas, col. cov, dig, bor, gal, sph, Bi- sulf Veins Silica core Silica core 10-20

VS/MS-*qtz-alu-lcao- qtz-kao-ill-* ill-sme-chl

<1

Abbreviations used: AA - advanced argillic, Hbx - hydrotherma! breccia, MS = massive silica, PRO Propylitic, SER = sericitic, VS - vuggy silica, VS (MS) vuggy silica dominant, alu - alunite, ars = arsenoyrite, bar = barite, bis = bismuthinite, bor = bomite, bou = boumonite, cal - calcite, ceo = chalcocite, chal.qtz = chalcedony or chalccdonic quartz, chl chlorite, cin cinnabar, can = canfieldite, cas cassiterite, col colusite, cov covellite, cpy = chalcopyrite, die = = dickite, dig = digenite, ele electrum, emp emplectite, fam - famatinite (stibioluzonite), gal - galena, geo geocronite, e gol = goldfieldite, hue = hubnerite, ill - illite, kao kaolinite, luz - luzonite, mar = marcasite, mol = molybdenite, nat.Au = native gold, natS - native sulfur, nat.Te - native tellurium, oro orpimcnt, py pyrite, pyo = pyrophyllite, qtz quartz, = rea realgar, sele - selenides, ser sericite, sid = siderite, sme - smectite, sph = sphalerite, sta stannite, stb stibnite, = sulf- sulfides or sulfosalts, tell * tellurides, ten ~ tennantite, tet - tetrahedrite, tou tourmaline, wol - wolframite ' Based on fluid-inclusion (flinc) or geological (geol) evidence; blank where not specified. 2 Boiling (Hbx) -= boiling due to abrupt pressure reduction associated with hydrotherma! brecciation

426

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-CuAu -Au 2 AA-Cu-Au + late bar-Au SeveraK?), 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; yes Not important

Sillitoe el al. (1990)

Lepanto Chinkuashih Zijinshan

Mixing/cooling Unknown

Garcia (1991), Claveria & Hedenquist(1994) Huang (1955), Tan el al. (1993)

500 Unknown

Mixing/boiling

Important in upper Ren el al. (1992), Zhang et al. (1994) 250 nv, yes Izawa & Cunningham (1989), Hedenquisl el al. (1994a) Steven & Ratte (I960,) Stoffregen (1987), Gray & Coolbaugh(1994) Ransome(1907, 1909). Ashley (1974), Vikre (1989, written comm., 1995) John eial. (1991), Sillitoe & Lorson (1994) Keslerai(1981) Russell AKesler (1991). Munteane/a/. (1990) Deen (1990), Rye (1993)

Nansatsu Summitville

150-300 flinc

Goldfield

Paradise Peak

Pueblo Viejo Julcani

El Indio

3 400-500 AA-CuAu-+ flinc + geol bar-base-metal-Au 5+ 100-300+ AA-ena-Augeol ten-py-Bi-Tc- 3 Unknown AA-Au-Ag-+ Hg 2 Shallow; lacusAlu-kao-py-Au- trine sediments MS-pyo-dia-Au preserved Several 200-300 AA+VS-tou breccias-* sulfide veins (main, late) 2 AA+Cu- Au

Widespread to 100 nv, yes but may be steam-heated Cu-Au by Irregular to 100 m; mixing, bar-Au may be partly by oxidation steam-heated Mixing/cooling; Widespread to 80 oxidation nv, supergene alunite(-lOMa) Boiling, with Widespread to 250 Hbx in early Au- m; supergene aluAg stage nite (100.5 Ma) Sulfidation + Widespread to boiling -100 m Mixing + boiling

Mixing/cooling

Mixing/cooling

Siddeley & Araneda (1986), Jannasrtai(1990) Losada-Calderon & McPbail. (1994), Brodtkorb & Paar (1993) SSInger-von Oepen et al. (1989)Arribasfl/. (1995a)

La Mejicana, Nevadosdel Famatina Rodalquilar

2 AA-silica-py-Au

200-300 flinc + geol

Boiling (Hbx)2 + Widespread to 80 mixing/cooling m; supergene alunite (4-3 Ma)

development of the oxidized and reactive magmatic vapor plume that is thought crucial to the formation of HS deposits.
DEPOSIT FORM AffD CONTROL: CLASSIFICATIONS

High-sulfidation deposits display a wide variety of styles of mineralization that includes veins, hydrothermal breccia bodies, stockworks,

and disseminations or replacements. This variation in the structure of the orebodies is complemented with variations in other deposit features, including ore and alteration mineralogy, paragenesis, and metal ratios (Tables 2, 3). In addition, some deposits present complex relations which may be composite, e.g., between high- and low-sulfidation mineralization (e.g., quartz-Austage veins at El Indio, and some of the veins at Julcani). Definition of styles of HS mineralization

427

A. Arribas, Jr. is difficult, but useful for discussion of the differences among deposits and design of exploration strategies. In this context, White (1991) distinguished three end-member styles of HS deposits, named after deposits of the CircumPacific: Temora, El Indio, and Nansatsu. Irregular bodies of disseminated, silicified ores dominate in the Temora-style. Cavity-filling veins with sericitic and clay-rich haloes are characteristic of El Indio-style Au deposits. A large group of deposits falls into White's (1991) Nansatsu-style, which is characterized by wallrock-alteration zoning similar to that shown in Figure 2, and by the occurrence of enargite-bearing ores within a silica core consisting of vuggy or massive silica rock (Table 3). Mineralization in this style of deposit forms irregular stratabound bodies (e.g., Nansatsu, Lepanto) or subvertical vein-like masses or "ledges" {e.g., Chinkuashih, Goldfield, Lepanto, Rodalquilar, Summitville). These deposits contain breccia bodies, veins, stockworks of small veins, and disseminated ores that replace or impregnate intensely altered country rock. Ericksen & Cunningham (1993) distinguished two styles of HS deposits in the Andean province: Agand Au-rich polymetallic base-metal veins, and low-grade vuggy silica and breccias; the two types are broadly comparable with El Indio- and Nansatsu-styles, respectively. Local subvertical faults and fractures are the dominant control on HS mineralization and they are present in most deposits (Table 2). Other examples of structural controls observed in some districts among the fourteen selected include: moderately to shallow-dipping faults (Goldfield), caldera ring and radial faults (Rodalquilar), the dilational jog of a strike-slip fault (Nalesbitan), diatreme ring-faults (Lepanto, Pueblo Viejo), the contact between a dome or volcanic conduit and country rock (Motomboto, the Missionary orebody at Summitville), and a lithologic unconformity (Pueblo Viejo, Lepanto). In three of the fourteen deposits, the principal control is lithological (maar sediments at Pueblo Viejo, and interbedded pyroclastic layers at Paradise Peak and Nansatsu; Table 2). A unique combination of the structural and lithological controls characteristic of HS deposits is exhibited by the Lepanto Cu-Au-Ag deposit.
/1">0

The deposit is 3 km long and consists of a main zone of breccia and replacement mineralization along the Lepanto Fault (Fig. 4A). Multiple veins associated with smaller diagonal faults branch from the main zone and extend into both the hanging wall and footwall (Garcia 1991). 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. 4B). Lithologic variations in the host rocks also played an important role in the formation of the deposit, as shown by lenses of stratiform enargite-luzonite ore which resulted from replacement of detrital layers within volcaniclastic and sedimentary basement units (Garcia 1991).
ALTERATION MINERALOGY AND ZONING

As mentioned above, the lateral alteration zoning that is characteristic of HS deposits reflects the reaction and neutralization of hightemperature acidic fluids with wallrock. The innermost zone of vuggy or massive silica alteration commonly has sharp boundaries with a zone that may contain quartz, alunite, kaolinite, dickite, pyrophyllite, diaspore, and zunyite . This advanced argillic assemblage grades into a second envelope of argillic alteration, composed of minerals such as quartz, kaolinite, illite, sericite, and smectite, and an outermost halo of propylitic alteration, with chlorite, illite, smectite, and carbonate (Fig. 2, Table 3). The width of each zone varies widely; for example, vuggy silica and advanced argillically altered rock form narrow (<70 cm) vein selvages at Julcani (Deen 1990), but form wide (>50 m) rock bodies at Summitville or Lepanto (Figs. 2 and 4). Late-stage, cavityfilling planar veins at Julcani and El Indio may extend outside the zone of alunite-kaolinite. In the majority of HS deposits, however, most of the ore is contained within the silica core, inside the advanced argillic envelope (Table 3).

In Russian and eastern European terminology these rocks are commonly termed 'metasomatic quartzites', with more specific names such as porous quartzites, diaspore quartzites, alunite quartzites, and dickite quartzites (e.g., Velinov et al. 1990).

High-sulfidation Epithermal Deposits

h>B

Lepanto fault

Age (Ma) 1.56-1.17 I [ 1.45-1.22 E%3 1.2-0.9 (ill 22-1.8 Cre.-Mto. t3 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 ^ ,

m raaftHi

-700m

Jea level

pgg BSa RS|9 ^ ^ f=g

Vuggy silica/ massive silica Advanced argiHic ArgiHic

JSWfl

1 Propyiitic

Figure 4. Longitudinal (A) and transverse (B) cross-sections of the Lepanto-FSE Cu-Au-Ag deposits (Philippines), showing structural and Uthologic controls on formation of the high-sulfidation and porphyry-type ores (simplified from Garcia 1991). 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. 1995b). Note the overall spatial overlap of the magmatic and hydrothermal "plumbing" systems (i,e., volcanic vents of Pliocene dacite, quartz diorite intrusions, porphyry deposit, and deeper parts of epithermal mineralization). The zones of alteration with increasing depth typically grade from a shallow silicic zone through advanced argillic, argillic, argiHic/ sericitic, into a sericitic or phyllic zone with quartz, sericite, and pyrite. This alteration sequence occurs over a vertical interval that ranges from a few hundred meters to more than 1000 m, and has been best documented by deep drillholes in the deposits of smaller size, in which the vertical span of mineralization is less than about 300 m (e.g., Rodalquilar, Summitville; Fig. 5B). At Lepanto, sericitic alteration at depths of 400 to 500 m below the epithermal deposit gives way, laterally towards the south, to K-silicate alteration of the FSE porphyry Cu-Au deposit. Porphyry-type stockwork mineralization at Paradise Peak is contained within the sericitic ores of the East Zone deposit which, according to Sillitoe & Lorson (1994), formed underneath the main HS orebodies in the area. 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). The lateral and vertical alteration zones described above correspond to a generalized model. 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. Experimental data on the relative stability of minerals such as alunite, kaolinite, pyrophyllite, and diaspore (Hemley et al. 1969, 1980), coupled with the temperature ranges noted for these and other related acid minerals in active systems (Reyes 1990; Reyes et al. 1993), also provide information that contributes to definition of the paleoconduits in extinct systems. If studied in detailed, several superimposed and crosscutting stages of pervasive as well as fracture (conduit)-related mineralization may be recognized in the majority of deposits. These are the expected result of variations, during the course of mineralization, in temperature, pressure, and composition of the hydrothermal fluid and the degree of wallrock interaction. Detailed field and petrographic studies at the Monte Negro orebody in the Pueblo Viejo deposit have resulted in

429

A. Arribas, Jr.

Rodalqultar caldg--r?
margin ^<^^"''

^KmSmm
iominacakieraV ftt^ls)/ ^Un s, margin N Mm^7 rffflsRSm ^^V^ \ jHodafottf/ar i Vuggy silica "^ (||l , r = j Advanced argilltc **V. _ ip^lttjr TO3 Argillic ^^^5i2Sii5S>liS*i^^^^^\.._ f;||flp-::f LA*I Serkatic p l l Propylitic G O Intense supergene actd-sulfate overprint OD

Au-{Cu-TeSn) Nghsutfidation deposits

400 .

0 ,

lilHi
A JCSJSSw

-400 Elevation

Lower limit of sulfide oxidation

A A

ft. A A X. A A A * A A A J , A A A * A 4* * , A A A / [A A A *

:ij|HrA I vf* % A A A /X A A

Pb-Zn-{Cu-/ quartz veins

Figure 5. Generalized surface alteration map (A) and cross-section (B) of the Rodalquilar HS deposit in the Rodalquilar and Lomilla calderas, southeastern Spain (from Arribas et al. 1995a). The boundaries shown between alteration zones are irregular and gradational. identification of two stages of mineralization, interpreted to correspond to two distinct magmatic pulses (Muntean et al. 1990). During the first stage (responsible for ~60% of the Au in the deposit), shallow kaolinite-quartz-pyrite and deep alunite-quartz-pyrite-quartz zones were developed, with gold mineralization in association with disseminated pyrite in the wallrock; during the second stage (responsible for about 40% of the Au), an extensive zone of siliciflcation with pyrite sphalerite enargite veins formed at shallow levels, above a zone of pyrophyllite-diaspore alteration (Muntean et al. 1990).
O R E AND GANGUE MINERALOGY, AND TIMING O F MINERALIZATION

particular features of the deposits listed in Table 3. Pyrite and enargite (and its low-temperature dimorph luzonite) are the dominant sulfides in HS deposits; pyrite is abundant but the amount of enargite and luzonite is variable. Common ore minerals, listed by decreasing abundance from variable to very minor, include tennantitetetrahedrite, covellite, native gold and argentian gold (electrum), marcasite, chalcopyrite, sphalerite, and galena. Famatinite is locally abundant in some deposits (Goldfield, La Mejicana). Sparse ore minerals include bornite, cassiterite, cinnabar, molybdenite, orpiment, realgar, stibnite, and wolframite (the last locally important at Julcani). Other minerals present in minor amounts in several deposits include Pb-, Ag-Pb, Bi- and Snbearing sulfosalts (Table 3). Fine-grained quartz is the dominant gangue in HS deposits. Other common but minor gangue minerals include barite, kaolinite, alunite, pyrophyllite, diaspore, and Ca-,Sr-, Pb- and REEbearing phosphate-sulfate mineral(s) such as svanbergite-woodhouseite or crandallite (Stoffregen & Alpers 1987). For example, high-grade

White et al. (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; their conclusions with respect to ore and gangue mineralogy in HS deposits are included here, in addition to the

430

High-sulfidation Epithermal Deposits

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

A. Arribas, Jr.

Table 4. Summary of fluid-inclusion microthermometric data for high-sulfidation deposits


Host-mineral studied Barite Quartz Enargite Quartz, barite, al unite Quartz (no details reported) Quartz Diaspore Quartz, barite, quartz phenoe Quartz phenoe Barite Quartz phenoe Quartz, barite Quartz, barite Quartz Quartz phenoe Quartz phenoe Wol, ena, quartz Siderite Quartz phenoe Quartz phenoe Sphalerite, 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.9E- NaCI) alteration <1 0.2^.5 0.2-12 2-22 3-19 0-5 (3-20) <1 up to 30 0.5-14 2-18 (up to 9) 5-18 0.2-8 <3 30-35 5-24 38-46 9-20 6-9 7-18 4-11 <l-40 0.1-4 0.1-2.7 (up to 27) 1-37 0.3-12 ^47 2-30 2-45 0.4-23 0.4-1.6 (32-45)
AA/sil AA/sil AA/sil A A/si 1 AA/sil AA/sil

Deposit Motomboto, Indonesia Nalesbitan, Philippines Lepanto, Philippines Chinkuashih, Taiwan Zijinshan, China

AA Ser Sil
AA/sil AA/sil

Nansatsu. Japan

.^

Ser
AA/sil

Akaiwa, Japan Mitsumori-Nukcishi, Japan

AA
AA/sil

Summitville, Colorado

Goldfield, Nevada

Paradise Peak, Nevada

Ser
AA/sil

Julcani, Peru

Ccarhuaraso, Peru Colquijirca, Peru Can-Can (La Coipa), Chile El Indio, Chile

AA/sil AA/sil AA/sil dominant AA/Ser

La Mejicana (LM) and Nevados Famatina (NF), Argentina Rodalquilar, Spain

AA + ser

AA Ser
AA/sil

. .
Funei-Serrenti, Italy

Quartz, quartz phenoe Quartz, barite, quartz phenoe

Ser
AA/sil

Abbreviations used: AA = advanced argillic, ena = enargite, phenoe = phenocrysts, ser = sericitic, sil = silicic: wol = wolframite: see Table 3 for paleodeplh estimations 1 temperatures are rounded to the nearest 10; 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. Two-phase entrapment may explain some of the unusually high homogenization temperatures (7*), particularly considering the shallow mineralization depth inferred for many of the deposits (Table 3). However, most workers agree that such
All

entrapment cannot account for all the high Th values. The consistent presence of these fluids in several deposits indicates a high temperature gradient, and implies the presence of a shallowdepth intrusion, and possibly lithostatic confining pressures. On the basis of fluid-inclusion, as well -34 as isotopic (8 Ssuifate-suifide) temperatures (see

High-sulfidation Epithermal Deposits Table 4. (continued)


Deposit Motomboto, Indonesia Nalesbitan, Philippines Lepanto, Philippines Chinkuashih, Taiwan Zijinshan, China Comments Reconnaisance study in late-stage barite Reconnaissance study; liquid CO2 observed Sampled interval 3 km long by 0.5 km high ; cooling fluids away from subjacent porphyry Cu-Au deposit, where Th >450C & salinity up to 54 eq wt.% NaCl Poorly-documented samples along a 450-m vertical interval; the higher T|,s in samples at -750 m depth; CO2 observed Associated with main stage Cu Deep alteration zone (>600 m depth) Associated with late, shallow silica-Au Associated with early silica and quartz-dickite Late, vug-filling quartz Qtz in breccia, saline liquid and low-salinity vapor coexist Vein quartz -400 m below Kasuga deposit Coarse-grained diasporc Not (known) Au or Cu mineralization, but high salinity fluids Liquid-rich; salinity >6 eq w..1o NaCl only in vuggy silica associated with Cu mineralization; CO2 observed Liquid- and vapor-rich inclusions; also polyphase inclusions Late barite-Au assemblage True Th is interpreted to be 250-290C Hydrostatic and near-lithostatic pressures suggested Late, vug-filling crystals in hydrotherma! breccia; From stockwork Au East Zone deposit; CO2 observed Quartz-alunitepyrite Pre-ore tourmaline breccia dykes, lithostatic pressures likely. Main-stage ore fluids, also inner veins, liquid-rich inclusions Late-stage ore fluids, also in outer veins; P correction applied Quartz-alunitepyrite Quartz-alunitepyrite Two generations identified; both may be very saline. Evidence for P above hydrostatic and higher salinities at depth Copper and gold stages Late stage Interpreted as early, with vapor-rich inclusions, CO2 observed LM & NF: includes liquid-, vapor-rich and polyphase inclusions NF: complete transition from porphyry-type fluids in Ksilicate stage (SOO-oW^C, up to 67 eq wt% NaCl) through sercitic to epithermal fluids in HS (AA) stage; vapor-rich inclusions typically less saline Vertical temperature and salinity gradient: high-temperature brines coexist with low -aiinity vapor inclusions; hydrostatic and near-lithostatic pressures suggested Includes high + low-salinity fluids (22-23, <6 eq wt% NaCl) Late stage References Perell6(1994) Sillitoe et al. (1990) Mancano & Campbell (1995), Garcia (1991) Folinshce el al. (1972), Yen (1976), Tan el al. (1993) Zhang et al. (1994)

Nansatsu, Japan Akaiwa, Japan Mitsumori-Nukcishi, Japan Summitville. Colorado -

Hedenquist et al. (1994a) Akamatsu & Yui (1992) Aoki&Watanabe(1995) Bruha & Noble (1983), R. Stoffregen (written commun., 1994) Cunningham (1985) Bruha & Noble (1983) Vikrc(1989) John et al. (1991) Sillitoe &Lorson (1994) Bruha & Noble (1983) Shelnutt& Noble (1985) Deen(1990) Deen(1990) Bruha & Noble (1983) Bruha & Noble (1983) Townley(1991) Jannase/tz/. (1990) Losada-Caldcr6n & McPhail (1994)

Goldfield, Nevada Paradise Peak, Nevada Julcani, Peru

Ccarhuaraso, Peru Colquijirca, Peru Can-Can (La Coipa), Chile El Indio, Chile La Mejicana (LM) and Nevados Famatina (NF). Argentina Rodalquilar, Spain Furtci-Serrenti, Italy

Sanger-von Ocpen et al. (1989), Arribas <</. (1995a) Ruggieri (1993b)

below), pressures above hydrostatic have been suggested for several deposits, including Julcani (Shelnutt & Noble 1985), Goldfield (Vikre 1989), Summitville (Rye 1993), and Rodalquilar (Arribas etal. 1995a). Group 2. Intermediate-temperature fluids (e.g., 180-330 C), with salinities variable from

<1 to ~18 equiv. wt.% NaCl. With the possible exception of deposits for which only the late-stage minerals have been studied, these typically liquidrich inclusions are found in all deposits. Mainstage ore fluids are contained within this group. The temperatures measured in fluid inclusions in enargite at Lepanto (Mancano & Campbell 1955)

433

A. Arribas, Jr. and Julcani (Deen 1990) are broadly similar, but their salinities are distinctly different (0.2-4.5 equiv. wt.% NaCl versus 8-18 equiv. wt.% NaCl, respectively), providing constraints on the role of a saline magmatic liquid (versus low-salinity vapor) in the generation of HS deposits. Group 3. Lower temperature (e.g., 90-180 C), dilute (typically <5 equiv. wt.% NaCl) liquids; these have been documented in a few deposits associated with late-stage (e.g., Aubarite) mineralization. The late-stage ore fluids at Julcani are hotter (220-250 C; Deen 1990) and slightly more saline (6-9 equiv. wt.% NaCl), than these averages, but no correlation among the late stages in different deposits is attempted here. Group 4. "Sericitic" fluids. As mentioned above, sericitic (quartz-sericite-pyrite) is the most common alteration assemblage observed below the ore zone in some HS deposits. Although detailed documentation is lacking for many deposits, higher temperatures and higher salinity fluid-inclusions seem to characterize the sericitic zone with respect to the shallower zones of alteration (Table 4). For example, at Rodalquilar (Arribas et al. 1995a), documentation of temperature and salinity along a >600-m vertical interval (extending 500 m below the ore zone; Fig. 6) shows a gradient which correlates with the change in dominant alteration, from silicic and advanced argillic (T = 170-300 C, salinity = 2-15 equiv. wt.% NaCl at the elevation of the orebody) to sericitic (7"= 220-450 C, salinity = 2-45 equiv. wt.% NaCl) assemblages. The transition from advanced argillic alteration, through quartz-sericite-pyrite, to K-silicate alteration and typical porphyry-type hightemperature (600+ C) and high-salinity (up to 67 equiv. wt.% NaCl) fluids of magmatic origin is displayed, among the examples reviewed, at the Lepanto-FSE and La Mejicana-Nevados del Famatina epithermal-porphyry copper systems. 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. Furthermore, in common with porphyry-type deposits, hightemperature, vapor-rich, low-salinity fluid inclusions coexist with high-temperature, liquid434
Temperature (C)
200 300 400 500

400 Elevation of Onto deposits

HjO + 5 wt% NaCl (hydrostatic) 200 (hydrostatic) (lithostatic) B1 -|400 s

200

1 I

>

3
- 600

1
o

-200

Q.

800

-400

Figure 6. Elevation versus temperature diagram showing the range (horizontal line) and average (vertical line) of fluid-inclusion homogenization temperatures measured in the Rodalquilar Au deposit, Spain. Also shown are the temperatures calculated, on the basis of 834S suir,dMuifatt for four coexisting alunitepyrite samples (large filled circles), reference boilingpoint curves, and vertical spans of the alteration zones mentioned in the text. Estimated salinities of fluid inclusions in the shallow advanced argillic/silicic zone and deep sericitic zone range between 2 to 30 equiv. wt.% NaCl and 2 to 45 equiv. wt.% NaCl, respectively (modified from Arribas et al. 1995a).

rich hypersaline inclusions (i.e., with Groups 1 and 4, above). These fluids may be the result of boiling of a high-temperature liquid, or they may reflect immiscible vapor and hypersaline liquid derived directly from shallow-emplaced magma (Rye 1993; Hedenquist & Lowenstern 1994; Shinohara 1994; Hedenquist this volume). Sulfur-isotope Evidence The abundance of coexisting hydrothermal sulfides and sulfates, in addition to the possibility

High-sulfidation Epithermal Deposits


.Sulfides Sulfates T &V - 534SJS
A 3 4 SH 2 S-SO4

Temp. (C)* H 2 S/S0 4 220 - 420 220 - 270 2-6

+
Lepanto Chinkuashlh Nansatsu Summltville Goldfield Pueblo Viejo Julcani El Indto Rodalqullar
T I I i

3 4

200 - 240 200-390 200 - 350 180-260 210-270

220-330 -H -10 1 1 0 1 1 10 &*S (%., CDT) 1 h20


'(mineral pairs)

30

Figure 7. Range of 834S (per mil) values for sulfides and sulfates from nine highsulfidation deposits. Also shown are the values calculated for 834S for total sulfur in the hydrothermal system (triangles), H2S/S04, and the range of temperatures determined from sulfide-sulfate mineral pairs. Solid triangles indicate deposits in which 834SS was calculated on the basis of isotopic analyses of samples of unaltered whole rock genetically related to mineralization. See Appendix for references and information on data plotted. of measuring 34 S/ S in host rock and genetically related igneous rock (Sasaki et al. 1979), allows sulfur-isotope studies to provide information on the composition, temperature, and sulfur sources of the hydrothermal fluids. The results of detailed studies in nine HS districts show a remarkable consistency (Fig. 7). In agreement with the observations in active volcanic-hydrothermal systems (e.g., Kiyosu & Kurahashi 1983), sulfide and sulfate minerals are mainly in isotopic equilibrium, and, therefore, their overall S/ S depends on the temperature of mineralization and the 34S/32S of total sulfur in the hydrothermal system. Only the data for alunite from the Campana vein in El Indio (Fig. 7) are different. If the measured El Indio alunites are not steamheated or supergene (unlikely as they contain finegrained pyrite; Jannas et al. 1990), the most likely explanation is a "magmatic-steam" (Rye et al. 1992) origin, in which the 834S of alunite is close to the composition of total sulfur in the system (e.g., Alunite Ridge in Marysvale; Cunningham et al. 1984; Rye et al. 1992) . Combined with the 8 S values of pyrite and enargite from the same vein, 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; Bove et al. 1990; Rye 1993). The main conclusions of the sulfur-isotope studies in HS deposits are: (1) sulfur in the deposits is magmatic, but the magmatic sulfur is overall heavier than mantle values (from 534S = 2
0/ 0/

2 'oo at Summitville, to 9 2 'oo at Rodalquilar; Fig. 7). This is not surprising given the most common geological setting of the deposits; isotopically heavy igneous sulfur is common in volcanic arc environments (e.g., Ueda & Sakai 1984). (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. 7; Rye et al. 1992; Hedenquist et al. 1994a; Arribas et al. 1995a). This is a minimum value for ore-forming fluids because it applies mainly to the early stage of hydrothermal

435

A. Arribas, Jr.

alteration, which is characterized by a sulfate-rich alunite-pyrite assemblage. (3) Isotopic equilibrium between sulfide and sulfate in the hydrothermal solutions results, in a majority of the deposits, in reliable temperatures calculated on the basis on A SH2s-so4 (Fig- 7). Pyrite-alunite mineral pairs were used most commonly, and where sampling with depth is available, they show a thermal gradient: e.g., 220 to 330 C over 200-m elevation at Rodalquilar (Arribas et al. 1995a), 200 to 390 C over -900 m at Summitville (Rye 1993); 220 to 420 C over 500 m at Lepanto (Hedenquist and Garcia 1990; J.W. Hedenquist, unpub. data). Other mineral pairs used with consistent results include pyrite-barite (Vikre 1989; Deen 1990), sphalerite-barite (Vennemann et al. 1993), and pyrite-gypsum (Vikre 1989). The range of isotopic temperatures is consistent with temperatures estimated from fluid inclusions and alteration mineralogy (e.g., Hemley et al. 1980; Reyes 1990; Reyes et al. 1993). The range is also consistent with formation of alunite at temperatures below ~400 C, when S0 2 gas starts to disproportionate in the hydrothermal solution (Sakai & Matsubaya 1977; Bethke 1984). Oxygen- and Hydrogen-isotope Evidence In terms of oxygen and hydrogen isotopic composition, the fluids that form HS deposits are arguably some of the better documented and understood in ore-deposit studies. This situation contrasts sharply with that of a decade ago, at which time no data were available to corroborate the affinity-suggested between fluids in active volcanic-hydrothermal systems and HS deposits (e.g., Heald et al. 1987; Hedenquist 1987). Stableisotope studies of HS deposits are particularly illuminating because of: (1) the abundance and variety of oxygen- and hydrogen-bearing minerals (e.g., alunite, illite, kaolinite), (2) the development of analytical procedures for complete stableisotope analysis of alunite, 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. 1992; Wasserman et al. 1992), (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, and (4) the availability of detailed information on the isotopic composition of fluids in active geothermal and volcanic-hydrothermal systems, which allows fluids estimated in HS deposits to be compared with those in their active equivalents. Some limitations still exist. These may be independent of obvious factors such as sampling or mineral-preparation procedures (fundamental for achieving representative and reliable results), analytical imprecision, and natural variations, as observed in active systems (e.g., Aoki 1991, 1992; Rowe 1994). 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 lack of mineral-water fractionation factors for some minerals (e.g., pyrophyllite), and (3) the disagreement among fractionation constants proposed for even common minerals such as illite (see Dilles et al. 1992, for a discussion) and kaolinite. For example, at 200 C there is a difference of 20 A between the D/H fracw tionation constants for kaolinite - water as given by Marumo et al. (1980) on the basis of samples of minerals and water from active systems, and by Liu & Epstein (1984) on the basis of experimental results. For these reasons, 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, for which fractionation factors are well-known (Stoffregen et al. 1994). 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; Stoffregen et al. 1994) and commonly is closely associated with ore, thus recording equilibrium conditions of a fluid closer in composition to the ascending mineralizing solution than the kaolinite or illite from outer alteration zones. 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. 8). In part because of

4 -> r

High-sulfidation Epithermal Deposits

0G -20-40O Q Alunite alteration stg. Ore mineralization stg. Alteration/ mineralization Subduction-related volcanic vapor Arc + crustal felsic magmas

Acidic fluids In high] sulfldation deposits .20 W W o

Active systems
(Giggenbach, 1992b)

so 6D(%.)
-100

Volcanic Geothermal 10 15 20

-20

i -15

1 -10

1 -5
6
18

1 0

'r 5

0 (%o, SMOW)

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

437

A. Arribas, Jr.

Hedenquist et al. 1994a; Arribas et al. 1995a). The O and D enrichment of the volcanic vapors with respect to their parent magmas (Fig. 8) is a consequence of fractionation during degassing from the melt (Taylor 1986, 1992; Matsuhisa 1992). In an alternative interpretation proposed by Deen (1990) and Rye (1993), 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), beneath the ore zone. This interpretation requires that there have been chemical and isotopic equilibrium between the magmatic fluid and country rock; however, this would likely result in neutralization of the magmatic fluid, a condition that would not favor the extreme acidity required for formation of vuggy silica at shallow depths (Giggenbach 1992a).
SOURCES OF METALS

1994). Detailed and comprehensive radiogenic isotope studies are needed, 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. If magmatic fluid is accepted as the dominant metal source in porphyry copper deposits, then the best evidence for a magmatic fluid source in HS deposits comes, perhaps, from consideration of the common genetic connection between the two deposit types (Sillitoe 1988, 1989, 1991a, this volume; Henley 1991; Mitchell 1992). In this context, 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. 4) and similar metal associations (i.e., Au/Ag values and high Te, Sn, and Bi).
POST-DEPOSITIONAL EFFECTS

The origin of metals in HS deposits is more speculative. There is consensus among most workers (e.g., Sillitoe 1989, 1991a; Henley 1991; White 1991; Rye 1993; Hedenquist et al. 1994a) that the bulk of the ore-forming components is contributed by magmatic fluid, either directly by a magmatic vapor or hypersaline liquid that is incorporated into the hydrothermal system, or indirectly by remobilization of metals from a porphyry-type protore. The study of radiogenic isotopes so far has not provided conclusive evidence. The reason for this is a consequence of the common intimate association between the deposits and host rocks; all are indistinguishable, e.g., for Pb-isotope systematics. Lead-isotope studies at Summitville (Doe et al. 1979) and Rodalquilar (Arribas et al. 1995a) have shown that the Pb in the deposits is igneous, but these studies provide no information about the processes by which the hydrothermal system acquired the metal {i.e., leaching of the host rocks or derivation from a crystallizing magma). By contrast, in low-sulfidation gold deposits it is not uncommon to detect a component of basementrock Pb (e.g., Doe et al. 1979; Arribas & Tosdal

In deposits that have not suffered deformation and metamorphism (those in Table 1, aside from the Paleozoic deposits in southeastern Australia and the Proterozoic Enasen deposit in Sweden), the principal post-depositional processes affecting HS deposits are mineral deposition from nearsurface steam-heated or supergene waters. Both can result in acid-sulfate alteration which may mask hypogene alteration zones and ore. On the basis of geological and mineralogical criteria, KAr dating, and stable-isotope analyses of alunite, identification of the origin of acid-sulfate minerals overprinting should be straightforward (e.g., Hayba et al. 1985; Rye et al. 1992; White & Hedenquist 1995). At Paradise Peak, 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). Atmospheric oxidation of sulfides during weathering in at least three HS deposits (Goldfield, Rodalquilar, and Summitville; Table 3) led to development of surficial supergene acid-sulfate blankets. Supergene alunite at Rodalquilar forms white to yellow, porcelaneous veins consisting of fine-grained

A1<2

High-sulfidation Epithermal Deposits

(Jannase/a/. 1990). 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. To explain this observation, 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. This model GENETIC MODELS requires coincidence of two distinctively different hydrothermal fluids along the same plumbing Genetic models for HS deposits have been system. These unusual conditions seem to have presented recently by various workers. A selection occurred at the Kelly mine, Philippines (Comsti et that emphasizes the variations in conceptual al. 1990; Aoki et al. 1993) and Masupa Ria, models includes Sillitoe (1989), Berger & Henley Indonesia (Thompson et al. 1994), where two (1989), Giggenbach (1992a), Rye (1993), distinct, overlapping hydrothermal assemblages Hedenquist et al. (1994a, which incorporates were identified. In these two deposits the known White 1991), and Sillitoe (this volume). In precious-metal mineralization occurred during the common among these models is an evolution from low-sulfidation stage. However, 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). The differences conditions of low-sulfidation-type geothermal among the models mentioned above are relatively fluids (see Fig. 3 in Hedenquist this volume). minor and lie primarily in the details of the oreThe initial requirement for formation of a HS forming stage. Most of these models consider the deposit is emplacement of an oxidized, 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. Rather than a hydrothermal systems {i.e., including lowspatially and temporally isolated magmatic event, sulfidation deposits, porphyry-type deposits, the subvolcanic intrusions seems to represent an replacement skarn deposits, and even submarine "aborted" late-stage feeder of a comagmatic volcanogenic massive sulfide deposits). This central-vent volcano or a maar - diatreme or flowaspect is important from a genetic perspective, as dome complex. Within the ascending, crysit is unwise to place strict limits between these tallizing, and cooling magma, a hydrothermal ore-forming environments (Hedenquist & fluid phase exsolves and concentrates ore-forming Lowenstern 1994). Similarly, the two stages metals and volatiles. Because of magma described here should be considered as successive convection and concentration of the magmatic phases of an evolving hydrothermal system, in fluid phase in the roof of the intrusion, the total most cases, without sharp boundaries between amount of water and metals available for a them. For example, 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. reaches the shallow depth (Lowenstern 1994; 1990). In contrast, crosscutting relations at Julcani = Shinohara & Kazahaya this volume). At the are unambiguous; the early stage of acid-sulfate confining pressure of a few kilometers depth (500alteration is separated from the base- and 1000 bars), and given the amount of water in the precious-metal veins by emplacement of type of magmas associated with HS deposits, the tourmaline-pyrite-quartz-altered breccia dykes magmatic fluid will separate into two aqueous (Shelnutt & Noble 1985; Deen 1990). El Indio phases, a low-salinity vapor and a hypersaline also shows clear crosscutting relations between liquid (Fournier 1987; Hedenquist & Lowenstern early enargite veins and later gold-quartz veins 1994; Shinohara 1994), with chloride-complexed (commonly <50 \ixn) pseudocubic alunite with subordinate jarosite, kaolinite, and hydrated amorphous silica (Arribas et al. 1995a). In the western United States, formation of supergene alunite at ~10 Ma at Goldfield and Paradise Peak (Table 3) seems to be related to regional tectonic episodes (e.g., Arehart et al. 1992). For an account of supergene effects in deposits of the Chilean Andes, see Sillitoe (1991a). 439

A. Arribas, Jr. ALTERATION ORE DEPOSITION B2

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

440

High-sulfidation Epithermal Deposits

constituting a relatively small part of the mixture (generally <l/3; Fig. 8). The fluid-inclusion evidence, by contrast, is inconclusive because of the lack of temporal information. Nevertheless, high-temperature, high-salinity inclusion fluids have been interpreted to form early in most HS deposits (e.g., Bruha & Noble 1983; Ruggieri 1993b; Arribas et al. 1995a). These fluids may be restricted to greater depths, as demonstrated at Rodalquilar and in other deposits where highsalinity inclusion fluid is associated with the deep sericitic alteration (Table 4). This latter observation suggests an episodic ascent of high-salinity magmatic liquid from the greater depths of the hydrothermal system, where the hypersaline liquid tends to stay because of its high density (Fig. 9A). These magmatic brines may be more closely related to the K-silicate alteration (and, in places, porphyry mineralization) that envelopes the intrusion (Fig. 9A; Sillitoe 1989). The conditions during the main stage of ore formation are not yet as well-understood, and this reflects the much more variable geochemical environment in comparison with that associated with acidic alteration. During the ore stage, the hydrothermal liquid may be less dominated by a magmatic vapor phase and its associated "sulfurgas buffer" (Giggenbach 1987). The presence of this S02-H2S buffer is the reason that the early stage of alteration is so oxidized, as reflected by the alunite-pyrite assemblage (Whitney 1988; Giggenbach 1992a). Instead, conditions during the ore stage fluctuate within a range of redox potential that is reflected by enargite-pyrite alunite and enargite-tennantite-chalcopyrite associations, which are relatively high to intermediate sulfidation-state assemblages, respectively (see Fig. 3 in Hedenquist, this volume). In the Lepanto (Claveria & Hedenquist 1994) and El Indio (Jannas et al. 1990) deposits, these two assemblages are related to Cu-rich and Au-rich mineralization, respectively, with the latter being of later stage in both cases. The more reduced conditions are a likely consequence of increased water-rock interaction, and, to some extent, increased dilution of the oxidized magmatic fluid by meteoric water; this trend is also consistent with the isotopic composition of waters in the main ore stage of various deposits (Fig. 8). No

discrimination, however, can be made between a meteoric-water component that is incorporated at deep or shallow levels within the hydrothermal system. Importantly, salinities during the main ore stage can be low (e.g., Lepanto and El Indio, <4 equiv. wt.% NaCl; Table 4) or moderate to high (Julcani, up to 18 equiv. wt.% NaCl; Zijinshan, up to 22 equiv. wt.% NaCl; Table 4). Assessment of a Model No single model adequately explains all of these various observations, and several hypotheses have been proposed, each reflecting an emphasis on individual deposits or different interpretations of the fluid-inclusion and stable-isotope data. A basic understanding of this ore-forming environment may be gained by considering the principal end-member fluid components and ore-forming processes. The spectrum of characteristics displayed by HS deposits may be then analyzed in the context of such a genetic framework. Four fluid regimes have been identified in the HS environment; evidence for all is present in the early stage of HS alteration, and three of them are critical to formation of porphyry systems (e.g., Henley & McNabb 1978; Sillitoe 1989). These end-members are: (1) a metal-rich hypersaline magmatic liquid which tends to remain in the vicinity of the intrusion, 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), (2) a low-salinity magmatic vapor whose metal-transporting capacity decreases sharply with decreasing pressure (Hedenquist this volume), (3) heated meteoric or connate water in deep convection cells that collapse inward and downward as the intrusive stock progressively solidifies and cools, and (4) shallow and cool meteoric groundwater. Two main end-member ore-forming hypotheses are considered. In the "volatile transport" hypothesis (Fig. 9B,), the magmatic hypersaline liquid may remain at depth throughout the evolution of the hydrothermal system, and the low-salinity vapors are responsible for mineralization (Sillitoe 1989; Vennemann et al. 1993); deep meteoric water entrainment of high-pressure 441

A. Arribas, Jr. vapor is required for transport of sufficient amounts of metals (Hedenquist this volume; Sillitoe this volume). These conditions are consistent with the low salinity of the Lepanto and El Indio fluid-inclusion data. Mineral deposition in this case may be caused by mixing with cooler groundwater or by boiling, possibly resulting from the abrupt pressure reduction associated with hydrothermal brecciation. In the "hypersaline liquid transport" hypothesis (Fig. 9B2), following waning of the magmatic vapor plume responsible for early alteration, the lithostatic-pressured system fractures and the metal-bearing hypersaline liquid ascends into the porous leached zone (Deen 1990; White 1991; Rye 1993; Hedenquist et al. 1994a). The dominant ore-forming mechanism in this case is mixing of the metal-bearing hypersaline liquid with cooler groundwaters at the site of deposition, 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.g., Julcani). A part of the ore-forming components may originate from leaching of wallrock, but both hypotheses agree on a dominantly magmatic source for metals, with an increase in the meteoric water component with time. The principal difference between the two hypotheses is in the nature of the magmatic phase responsible for transporting the metals into the epithermal environment, and in the site of meteoric water dilution. 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, such as that which may have formed close to the intrusion (e.g., Brimhall 1980). This mechanism, however, has not been suggested as the main ore-forming process in any of the deposits reviewed in this study. The three models for formation of HS ores, assimilated here from the literature, are not mutually exclusive; on the contrary, they may occur in the same HS deposit as the magmatichydrothermal system evolves, with complexities arising from multiple intrusions, variations in depth of emplacement, and changes in the local
447

tectonic and hydrodynamic environment. None of the three models satisfies the overall evidence. For example, if metals were supplied only by a dense, high-salinity liquid, a relation would be expected among estimated salinities, metal associations, and ore grade or metal abundances of the various deposits. Such seems not to be the case. Similarly, if alteration and mineralization were solely the result of interaction between groundwater and low- and high-pressure vapor, respectively, 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.
SYNTHESIS

Gold, Cu, and Ag (and in a few exceptional cases also Hg, W, Bi, Pb, and Zn) are produced from HS deposits. As a source of Au, 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, HS deposits represent a valuable exploration target that has been overlooked in some regions. Most known HS deposits are young in age, Tertiary and even Quaternary. Highsulfidation deposits form dominantly in subduction-related plutonic-volcanic arcs, commonly during crustal extension. The deposits form at a depth intermediate between the surface and shallow (few kilometers depth) intermediatecomposition intrusions. The intimate relationship among HS deposits, volcanic host rocks, 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, (2) the ore-forming hydrothermal system commonly follows the same plumbing as that of the magmatic system (i.e., mineralization spatially associated with domes or volcanic conduits), (3) the isotopic composition of hypogene sulfides (e.g., enargite and pyrite) and sulfates (e.g., alunite and barite) commonly can be modelled from the 34S/32S of sulfur in igneous rocks thought to be genetically related, by equilibrium fractionation between H2S and SO4 in solution at T -200-400 C, and (4) on the basis of

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

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453

A. Arribas, Jr. "so 4 = 55, A34S = 7 (Deen 1990); El Indio, nH?s = U> "SO4 = 3 (Jannas et al. 1990), Rodalquilar, H2S = 44, nS04 = 1 1 , A 3 4 S - 4 (Arribas et al. 1995a). Temperatures for Chinkuashih were calculated using the 4 S/ S data from Folinsbee et al. (1972) and more recent fractionation equations. Sulfide-sulfate mineral temperatures higher than 350 C were documented only at depth at Summitville (T = 390 C, -900 m below the present surface; Rye et al. 1990) and Lepanto (7" = 420 C at the 700-m level, immediately above the FSE porphyry copper deposit; Hedenquist & Garcia 1990). On the basis of phase equilibria, the sulfide/sulfate values for the Pueblo Viejo stage 1 and stage 2 mineralization were estimated by Muntean et al. (1990) to be about 3 and 35, respectively. Figure 8 8D versus 8 O variation diagram. Explanation: Go = Goldfield, hypogene alunite, n = 1 (Rye et al. 1992); Ju = Julcani, alunite (/? = 6), Jut = average of main-stage ore fluids in wolframite, enargite, tetrahedrite, and galena fluid inclusions, Ju2 = average of main-stage ore fluids in sphalerite and chalcopyrite, Ju3 = late-stage ore fluids in barite, siderite, and botroidal pyrite (Deen 1990); Le = Lepanto, alunite, n = 2 (Y. Matsuhisa & J. Hedenquist, unpub. data); Nansatsu district: Ka = Kasuga, alunite n = 1, Iw = Iwato, alunite n
1 ft

Nevados del Famatina, stage V alunite-kaolinite, n = 1 (Losada-Calderon & McPhail 1994); the average 8D and 8 , 8 0 values for La Mejicana {n = 9) are similar to NF; K-silicate and quartz-sericite at Nevados del Famatina have 8 O between 4 and 10/oo, reflecting a larger magmatic component (Losada-Calderon & McPhail 1994); PV = Pueblo Viejo: PV] = stage 1 alunite and kaolinite, PV2 = stage 2 pyrophyllite (Fig. 9 in Vennemann et al. 1993); Ro = Rodalquilar, alunite, n = 10, chalcedonic ore, n = 6 (Arribas et al. 1995a); RM = Red Mountain, Lake City, Colorado, alunite, n = 12 (Bove et al. 1990; Rye 1993); Su = Summitville, alunite, average of n = 10 (8D) and n = 16 (8 18 0) (Rye et ah 1992), ore fluids from Rye (1993). The main ore stage.at Rodalquilar (stage 2) is based on 8 1 8 0 of chalcedonic quartz; 8D are not available for this stage but present-day groundwaters, alunite, kaolinite, and illite fluids in the deposits have a limited range of 8D values, suggesting significant variations are unlikely (Arribas et al. 1995a). Stage 2 (pyrophyllite) fluids for Pueblo Viejo involve several assumptions with respect to the choice of fractionation factors for oxygen and hydrogen. The data for stage 2 at Rodalquilar and Pueblo Viejo should be viewed as approximate. Data for a single alunite for Goldfield (Rye et al. 1992)
i o

= 2, 6 O values of residual vuggy silica associated with ore in both depositsfall between Ka and Iw (Hedenquist et al. 1994a); NF =

suggest that mixing of enriched magmatic fluid waters may result in hydrothermal acid-sulfate 1989).

a the 8D- and 8 Owith isotopically light D- and O-depleted fluids (see also Vikre

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