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In Magmas, Fluids, and Ore Deposits, Ed.: J.FH.

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 of Japan,
l-l-3 Higashi, Tsukuba 305, Japan

INTRODUCTION including silica sinter-depositing hot springs and


steam-heated acid-sulfate alteration.
A consequence of the increased exploration for The main objective of this review is to
gold deposits during the late 1970s and early summarize the characteristics of HS minerali-
1980s was the revision of the classification of zation formed primarily within the epithermal
epithermal deposits in order to account for the environment, though recognizing the potential for
variations observed in styles of mineralization and HS conditions to occur at greater depths. Earlier
inferred genetic environments. Among the studies have argued for a magmatic fluid
numerous classifications that followed, one group component in HS deposits (e.g., Sillitoe 1983,
of deposits clearly showed a common set of 1989, 1991a; Hayba et al. 1985; Henley 1991;
features; this deposit type is characterized by the White 1991; Rye 1993; Hedenquist et al. 1994a),
presence of minerals diagnostic of high- and the identification and characterization of HS
sulfidation states (e.g., enargite and luzonite) and deposits has contributed to a re-evaluation of the
acidic hydrothermal conditions (e.g., alunite, role of magmatic fluids in other types of
kaolinite, pyrophyllite). The terms enargite-gold hydrothermal systems (Hedenquist & Lowenstern
(Ashley 1982), Goldfield-type (Bethke 1984, after 1994; Simmons this volume; de Ronde this
Ransome 1909), high-sulfur (Bonham 1984, volume). In this context, particular attention is
1986), quartz-alunite Au (Berger 1986), acid- given to the characteristics that are helpful in
sulfate (Heald et al. 1987). and alunite-kaolinite determining the nature of the magmatic contri-
(Berger & Henley 1989) were applied to this bution to the hydrothermal system through time
group in reference to some of its mineralogical or and space. This review considers features of many
inferred geochemical attributes. The term high- of the deposits listed in Table 1, with locations
sulfidation (HS) (Hedenquist 1987) is now widely shown in Figure 1, but is based on a selection of
used; the term was proposed originally to refer to fourteen deposits for which the results of detailed
a fundamental genetic aspect, the relatively geological and geochemical studies are available
oxidized state of sulfur contained in the (Tables 2, and 3). For simplification, biblio-
hydrothermal system (i.e., initially SO*-rich). This graphic, references are not given in the text -for
aspect is significant because it links HS deposits general deposit features; these references may be
with one of the two main types of terrestrial found in Table 1. For regional studies of HS
magma-related hydrothermal systems (Henley & deposits, particularly with respect to other types of
Ellis 1983), those associated with andesitic magmatic-hydrothermal base- and precious-metal
volcanoes whose surface manifestation includes deposits, the reader is referred to reviews by
high-temperature fumaroles and acid sulfate- Heald et al. (1987), Bonham (1989), Sillitoe
chloride hot springs and crater lakes. By contrast, (1989, 1991a), Berger & Bonham (1990), Camus
low-sultidation deposits form from neutral-pH, (1990), White & Hedenquist (1990), Mitchell &.
reduced (&S-rich) hydrothermal fluids similar to Leach (1991), Mitchell (1992), and White et al.
those encountered in geothermal systems (Henley (1995).
& Ellis 1983), with surface manifestation

419
A. Arribas, Jr.
Table 1. Principal high-sulfidation deposits or documented prospects ordered geographically

win
Fig. 1 Deposit Reference
Asia & Australasia
1 Dobroyde, Australia White et al. (1995)
2 Rhyolite Creek, Australia Raetz & Parrington (1988)
3 Temora, Australia Thompson et al. (1986)
4 Peak Hill, Australia Cordery (1986), Harbon (1988), Masterman (1994)
Mt. Kasi, Fiji Turner (1986)
i Wafi River, Papua New Guinea Leach & Erceg (1990). Erceg et al. (1991)
Nena, Papua New Guinea Asami & Britte.n (1980), Hall et al. (1990)
ii Motomboto, Indonesia Perello (1994)
9 Nalesbitan, Philippines Sillitoe et at. (1990)
10 Lepanto, Philippines Gonzalez (1959). Garcia (1991). Arribas et al. (1995b)
11 Chinkuashih, Taiwan Huang (1955). Hwang & Meyer (1982). Tan et al. (1993)
12 Zijiihan, China zhang et al. (1994)
13 Seongsan & Ogmaesan, South Korea Yoon (1994)
14 Nansatsu (Iwato, Akeshi & Kasuga), Japan Izawa & Cunniigham (1989). Hedenquist et al. (1994a)
15 Yoji. Japan Yui&Matsueda(1994)
16 Teine, Japan Ito (1969)
Akaiwa, Japan Akamatsu & Yui (1992). Akamatsu (1993)
:; Mitsumori-Nukeishi, Japan Aoki & Watanabe(1995)
North & Central America
19 Panteleyev & Koyanagi (1994)
20 Goldfield,Nevada Ransome (1907.1903). Ashley (1974). Vikre (1989)
21 Paradise Peak, Nevada John et uL*(Wi), Sillitoe & Lorson (1994)
22 Summitville. Colorado Steven & Ratte (1960). Stoffregen (1987). Rye ( 1 9 9 3 )
Red Mtn-Lake City. Colorado Bove et al. (1990). Rye (1993)
E Red Mtn-Silverton, Colorado Burbank (1941). Fisher and Leedy (1973)
.25 Mulatos Mexico Staude(1994)
26 Pueblo Viejo, Dominican Republic Muntean et al. (1990) Russell & Kesler (1991)
south America
Julcani, Peru Petersen et al. (1977). Deen (1990). .Rye
. (1993)
Castlovirreyna,Peru Vidal & Cedillo (1988)
Ccarhuarso,Peru Vidal et al. (1989)
San Juan de Lucarras, Peru Vidal & Cedillo (1988)
Cerro de Pasco, Peru Graton & Bowditch (1936). Einaudi (1977)
Colquijirca, Peru Vidal et al. (1984)
Sucuitambo, Peru Vii & Cedillo (1988)
Laurani, Bolivia Murillo et al. (1993)
Choquelimpie, Chile Gtipper et al. (1991)
Guanaco, Chile Puig et al. (1988). Cuitino et al. (1988)
El Hueso, Chile Sillitoe (Wla)
-Chile Vii (1991). Moscoso et al. (1993). Cuitifio et al. (1994)
La Coipa, Chile Oviedo et al. (1991). Cecioni & Dick (1992)
Nevada & Sancarron, Chile sdd&y&Alaneda(1990)
El India-Tambo. Chile Siddeley & Araneda (1986), Jannas et al. (1990)
La Mejicana-Nevados de1 Famatina Argentina Losada-Calderon & McPhail(l994)

43 Rodalquilar,Spain S&gcx-von Oepen et cd. (1989). Arribas et al. (1995a)


Furtei-Serrenti, Sardinii Ruggieri (1993a.b)
zi Spahievo, Bulgaria Velinov et al. (1990)
46 Chelopech, Bulgaris Bogdanov (1982.1986)
Western Srednogorie region, Bulgaria Bogdanov (1982), Velinov & Kanazirski (1990)
dS Bor, Yugoslavia Jankovic et al. (1980). Jankovic (1982)
49 Baksa (1975, 1986). First (1993)
50 iiifEl?::Z
* Hallberg (1994)
Figure 1. Worldwide distribution of high-sulfidation deposits‘and principal documented prospects. The main high-
sulfidation metallogenic provinces are indicated. See Table 1 for deposit names and selected references.

OPENING REMARKS ON GENETIC advanced argiliic zones that commonly cap


ENVIRONMENT porphyry copper systems (e.g., Sillitoe 1973; Corn
1975; Gustafson & Hunt 1975; Koukharsky &
Based on detailed research of the Summitville Mirre 1976; Wallace 1979). Indeed, several of the
Au-Cu-Ag deposit, Stoffregen (1987) demon- deposits considered in this review are underlain by
strated that a nearly ubiquitous feature of HS porphyry-type mineralization (Table 2). This
deposits, fracture-controlled vuggy silica rock advanced argillic assemblage is also typical ‘of
(intensely leached volcanic rock consisting that associated with acidic crater lakes atop active
dominantly of quartz; Fig. 2) is the product of volcanoes (Christenson & Wood 1993; Delmelle
very acidic conditions (pH Q at T= -250 “C) that & Bernard 1994; Rowe 1994; Hedenquist this
occur within a sulfate-rich hydrothermal fluid volume).
formed by absorption of magmatic vapor. In The implications of a genetic relation between
addition to SOz disproportionation to H$O,, porphyry and epithermal mineralization, e.g., with
significant concentration of HCI from the respect to the origin of metals or the nature of the
magmatic vapor contributes to the acidic fluid inclusions in HS deposits, are discussed
conditions necessary for alumina to be soluble, below. The observation made here is that an
leading to vuggy silica alteration (Hedenquist et alunite-enargite assemblage records a similar
al. 1994a,b). Neutralization of the acidic solution geoehemical environment, whether forming an
by reaction with the wallrock results in a sequence epithermal deposit or as part of the alteration
of alteration zones, outward from the zoning of an orebody formed at greater depths.
hydrothermal conduit, which is indicative of High-suifidation deposits form in a position
decreasing acidity and is defined by the presence intermediate between intrusions and the surface;
of alunite, kaoiinite, iilite, and montmorillonite f therefore, they may be located close to a porphyry
chlorite (Steven & Ratte 1960; Fig. 2). copper deposit or in a near-surface environment,
This same alteration sequence, without the such as the roots of an acid crater lake.
vuggy silica zone but with enargite-bearing ores, Comprehensive genetic models for HS
was documented in the Butte poiymetallic deposit deposits have been proposed only recently (e.g.,
(Meyer ef al. 1968) and in the roots of the Berger & Henley 1989; Sillitoe 1989; White 1991;

421
A. Arribas,Jr.

Table 2. Main geological characteristics of 14 selected high-sulfidation epithermal deposits


Time
CCpositIdistrict. A g e Meds, Local wlcanic Principal host GetlCtkally between host
location (Ma) w.xmes)~ se1ting E&s related roclcr rock & deposit Deposit form
Ma1ombo10, 1.9 cu. Au. Ag centi-vent Dac dams aruls/daf.%hy Mmitic, qlz- <1.0 m.y T; , veins, dis tn
lndarsia 50,ooo I cu. 4 t wkano flows, pyr and volx dioritic stocks
Au, 180 I Ap (c)
Nalesbitan, Pliocene Au Small central- Ands pyr + flows N o n e obserwd NIA Hhn. veinlets
Philippines 15 I Au(c) vent volcano
Lepanro, 1.5-1.2 Cu. Au. Ag lmreme Andsmac vol. Qudiaite canaly;. error venical breccias,
Philippines 9oo.ooo I cu. complex Miocene + older mm WI.1 m.y.1 veins, stmab0~nd
120tAu(c) volx + melavol XpplaCC!IWXS
Chinkuashih. 1.3-1.0 Au. Cu. Ag Dome complex Dac wlc Dade domes Veins or “tedgesw.
Taiwan 92 I Au. 183 I Ag, Miocene sed and flows hbx. dis and stk
12o.m I cu (PI sunwnding veins
Zijinshan. -W Cu. Au Dome along Jurassic granite, Na repted 7.0 my.(?) Veins. hbx. stk
China >lO I Au (c) c&erammargin? -sdac WY*&)
PwYhrl +pyr
Nansalsu. S-35 Au Small vokanos An& pyr. flows + HGltdeodeands <0.5 my Dis in stratabound
Japan 18iA~@)+)81 inacakkn? volx (Middle VOICS) VS/MS bodies.
Au resems veins. hbx
Summicville, 22.5 Au, Cu, Ag Dome along Qtz-latite porphyry f&z-mauocite canalp. error -tAQes- with
Cdo+ado 17tAu praxisring porpbw (ko.5 my.) veins, hbx + dis
crldcra~ in VS

21 Au (A& Cu) Domes along Miocene an&site Andeshe QilalyI. errw ‘Ledges’ with
130 f Au, t 43 Ag. preexisting ring (!Xl.4 m.y.1 veins. hbx + dis
37,W Cu (p) frxure in MS

Paradii Peak, 19-18 Au, Ag, Hp Within OT close Composite welded luff. Alldhkwi canalyt. error Sbalabeund bodies
Nevada 47 I Au, 12.55 Ag loa ceneal-wm vok + ads flows <*tl .o my.1 commonly with
457 i Hg (p) WIWIO hbx
Pueblo Viejo. -130 Au, Ag MaarW Maaf sed + basaltic CAbimodal N/A Mushroom-shaped
Dominican Rep. >600 t Ali (p; comptex vol (spilite) (Rhy 4 badI) bodies wi* stk +
Sillitoe. 1993) wlcanic suite dis
Julcani, 9.8 Ap, Cu. Pb, Au. Dome complex Dac to rilyodacitic Dac$ylydc canalyt. error Veins
PaU W. Bi, 2.n ammdaantral domts and tuffs (zJzO.1 m.y.1
diamlK
El India, 13-a Au, Ag. Cu stratowlcan&?) Dac. rhy wr CA vol N/A Veins + sfk
Chile -140 I Au. ineailexaldua dac+andsvoi
-1,1OOtAg(c)
La Mejiia & Ne- 4.0-3.6 Cu. Au. Ag Domecompk4?) pateaoic se& + Veins; also hbx ai
vados de1 Famadna
Argentina
Rodalquilar, II-10
>tO-lStAu(c)

AU caidera~n
granites. pliooerhe
intNsive d&c rtccks N. del Fan&a

Veins. hbx. dis in


&Ids m rhy pyr flows, Ands flows canalp. error
Spain 10 t Au (p) collapse bw + dcrmes +dyfucr (ti.7 m.y.1 vs

Abbreviations used: CA - c&-alkaline. MS - massive silica, VS = vuggy silica, ands = andcsitic, brc = bnwias. dac - dacitic. dis =
disseminations, hbx = hydrothermal vein bnccia or brcccia pipes, pyr = pyroclastics, qk - qunrtL, rby - rbyolitic, xd = sedimentary rock, stk
p: stockwork, vol -volcanic rock (unspecified). volx - volcaniclastics
’ (D) - moduccd, (c) * estimated total contained ’ Approximate number, quoted from paper or estimated from figures: 150 m for Paradise
P&c is for individual onhodicr

Giggenbach 1992a; Rye 1993; Hedenquist et al. and the pressure and temperature gradients”. This
1994a). However, the basic genetic controls, as we concept formed the basis for Ransome’s “direct
understand them now, were formulated almost volcanic hypothesis”, though it was quickly
ninety years ago by Ransome (I 907) following his abandoned in favor of a “simultaneous solfatarism
classic study of the Goldfield Au-Ag-Cu deposit. and oxidation” model (Ransome 1909). The
In his own words “the (ore depositing) solutions change in genetic interpretation has more than
were essentially emanations from a solidifying anecdotal value because it illustrates the source of
body of dacitic magma " and " . . the initially acid a not-uncommon misconception on the environ-
emanations would be neutralized and modified in ment of mineralization of epithermal deposits.
their ascent through fissured rock . .by the The crucial aspect is identification of the
distance and kind of rock traversed, the quantity origin of alunite or acid-sulfate alteration, which
and character of admixed surface-derived waters, can be generated by different mechanisms in three
High-Sulfidation EpithermalDeposits

Table 2 (continued)
verlical cxt-
Deposil/disuicc em or edlb. Relation lo
localion Cawol on mineralization

Maomboto, Contact Wween dome and 250 Porphyry Cu-Au Perello 61994)
Indcocsia volcanic rock. acep fault Pcspecur n-b-Y* ape
wilhin 1 .O m.y.
Nalesbitan, Steep coike-slip fault I50 RM Silliwe cr ol. (1990)
Philippines none know-i
Lepanto, Major steep + minor faulu. so0 Abuve + adjacent Garciaft991).
Philippines dianemc contac1. uncomfor- - age PWWY Anihas CI 01. ( I995b)
My. pameable layers Cu-Au deposit
Chinkuashih, Steep nwnal faults f 800 None known Huang (1955).
Taiwan their intefsectioos, -ran er al. ( 19933
bcddinlr Pla=
Zijinshaq Sleep aaike-slip fault mn None known Ren er al. (19921,
chii ?xaus+contactof zhangeral. (1994)
volcanic vent
NGUSi%Sll, Steep fi’icturcs + permeable <Is0 None known lzawa & Cunningham ( 1989),
Japan pyroclasic layers Hederquia cr uL (1994a)

Summiwille, Steep radial fractures + 250 InunsioMxnlcnd Steven & Rant f 1960). Menhen
Colorado dome c a l m cericitic, low pdc a 0L (1973). Stoffregen (1987).
cli mincraliion Rye ( 1993) Gray 8r Coolbaugh
WW
Moderately + cbi&3w 400 None known Rancome (WWf, AshIcy 11974).
dipping faults & fissures Ashley 8r Silberman (1976).
Vikre (1989. written commun.
1995)
sleep f&Is and permeable Cl50 Sericitic, nk Au Joho nul. (19911,
pyl‘oclas4c layers mhleraIizarion @act Sillitce & Loraon 11994)
Zanet
Pueblo Viejo, DiaUeme ring fault + a?) None known Russell & Kesler (1991).
Dominican Rep. pameablc layas Muntean n 41. ( 19901

J&Xii. svcp fraalues 600 None known Pc1crccn .?r ul. ( 1977,.
PaU Noble & Silbennao (1984).
Deen (1990)
El India, Steep namal fat&s >300 Papbyly cu-MO Siddeley
& Annala f lQ86~,
Chile miwralization Jannas cr aL ( 1990)

IA Mejicana & Ne- Lofal faults HS


- me a~ Nevado de1 Lxada-Calder6o & McPhail
vadoa dcl Famatina, l%unatinaisopanofa WQ4~,J~~&Wdec6ne~af.
- PPMY cu rxospect ww
RawquilW, Calh ring faults + <lx) None Iawwn hrribas et al. (lQ95a)
spin nonnaI Iocal faults

principal geologic environments (Bethke 1984; zunyite, which are typical of hypogene (T = 200-
Rye ef al. 1992): (1) by the disproportionation of 350 OG) acidic conditions (advanced argillic
magmatic SO2 to H2SO4 and H$ following assemblage; Meyer & Hemley 1367). This type of
absorption by groundwater (magmatic- alunite is characteristic of HS deposits, but it may
hydrothermal), (2) by atmospheric oxidation of also appear in areas of advanced argillic alteration
H$ in the vadose zone over the water table, void of ore mineralization (e.g., Iwao 1962; Hall
associated with fumarolic discharge of vapor 1978). Alunite in steam-heated environments
released by deeper boiling fluids (steam-heated), forms with kaolinite and interlayered illite-
and (3) by atmospheric oxidation of sulfides smectite at about 100 to 160 “C where fumarolic
during weathering (supergene). Magmatic- vapor condenses above the boiling zone of
hydrothermal alunite occurs with minerals such as neutral-pH, H$-rich fluid, typical of geothermal
diaspore, pyrophyllite, kaolinite, dickite, and systems that form low-sulfidation deposits.

423
A. Arribas Jr.

Mineralized vuggy
rock rock reck quartz rock

Figure 2. Cross-section of alteration zones characteristic of high-sulfidation “deposits,. as observed at the


Summitville Au-Cu deposit, Colorado. Diagranrat 1eA (simplified from Steven & Rat&4 1960) shows schematic
outward zonation from a subvertical mineralized body, shown at right (from Stoffregren 1987).

Because of the relatively shallow and dynamic Proterozoic En&en Au deposit located in the
environment of mineralization, overprinting Baltic shield of central Sweden; Fig. 1). The
among the three types of acid-sulfate alteration youngest deposits are Pleistocene (4.6 Ma) and
(including supergene) is possible; however, the occur in the central western Pacific {Kelly,
spatial relation of each type of alunite to ore is Lepanto, and Chinkuashih). The concentration of
different, and correct identification is important deposits in young volcanic areas is mainly a
for exploration (Rye et al. 1992; White & reflection of the fact that older HS deposits are
Hedenquist 1995). more likely to be eroded.
Gold, copper, and variable amounts of silver
DISTRIBUTION, AGE AND ECONOMIC are the main products of HS deposits (Table 2).
SIGNIFICANCE Gold (Nalesbitan, Rodalquilar), occasionally with
silica by-product (Nansatsu), is the only economic
In common with other magmatic- metal in the smaller deposits. No copper is
hydrothermal deposits (e.g., porphyry copper produced at Paradise Peak and Pueblo Viejo.
deposits), HS deposits coincide worldwide with Mercury is produced at Paradise Peak, and the
plutonic-volcanic arcs. This association is best Julcani district has been a source of a remarkable
observed in the Cenozoic deposits of the Circum- polymetallic assemblage consisting of Ag, Cu, Pb,
Pacific and-the Balkan belt of southeastern Europe Au, W, Bi, and Zn (Table 2). The six largest
(Fig. 1). These deposits occur in two main deposits or .districts ..(Chinkuashih, El Indio,
settings: in island arcs and at continental margins. Goldfield, La Coipa, Lepanto, and Pueblo Viejo)
The tectonic regime during formation of the each contains more than about IO0 tonnes of gold.
deposits seems to be dominantly extensional The economic potential of this type of
(Sillitoe 1993). Some deposits (e.g., Goldfield, mineralization is clear in regions such as the
Rodalquilar, Summitville) formed in intra- Chilean Andes (Sillitoe 1991a).
continental regions during periods of extension
that followed regional compression and sub- VOLCANIC SETTING AND Associated
duction by several m.y. IGNEOUS Rocks
Tertiary I-IS deposits predominate, and only a
few deposits are Mesozoic (e.g., Pueblo Viejo, The high-sulfidation deposits considered in
Zijinshan), Paleozoic (e.g., Temora and others in Table 2 occur within intermediate-composition
southeastern Australia), or Precambrian (the early volcanic rock sequences having ages broadly
High-sulfidation Epithermal Deposits

Figure 3. K,O versus SiO, variation diagram


for rocks thought to be genetically related to
high-sulfidation deposits. The samples from
12 deposits or districts (n = 140) define a
small compositional field, which contrasts
sharply with the large field defined by
volcanic rocks associated with low-
sulfidation or intrusion-related Au deposits
(>I00 samples from 16 districts; Sillitoe
1991b, 1993; Mtiller & Groves 1993). The
Y
degree of alteration of the rock samples and
precision of the analytical data are largely
2 unknown; however, according to the
individual data sources, most of the samples
1 are unaltered or very weakly altered. Circles
indicate. average values for each high-
O-'I I ‘ I I I I'. 8 I sulfidation deposit or district: Ch =
40 * 60 60 70 60 Chinkuashih, Cq = Choquelimpie, Go =
SQ (WI%) Goldfield, In = El Indio, Ju I= Julcani, La =
Laurani, Le = Lepanto, MO = Motomboto,
Na = Nansatsu, PP = Paradise Peak, Ro = Rodalquilar, Su = Summitville. Compositional fields after Keith ef al.
(1991). See Appendix for references and information on data plotted.

similar to that of mineralization. Where abundant thought to exist at depth (Arribas et al. 1995a).
radiometric ages are available, the age of the host The main control on location of mineralization at
h-v, rocks and the age of mineralization are within Rodalquilar is the structural margin of two nested,
analytical precision; where a difference is resurgent calderas. With the exception of
indicated, it is typically less than -1.0 m.y. (Table Rodalquilar, the role of ealderas in the formation
2). A common spatial association exists between of HS deposits seems to be limited to facilitating
the deposits and shallow, typically porphyritic the emplacement of late intrusive magma along
-intrusions. These intrusions are interpreted to be preexisting caldera ring-fractures (Rytuba Ed al.
the roots of volcanic domes or the feeders of 1990).
central-vent volcanoes or maar-diatreme com- The magmas thought to be genetically related
plexes, .the three main volcanic settings for HS to HS deposits have a remarkably limited
deposits (Table 2). Some deposits are hosted compositional variation. The ranges of wt.% K20
entirely within a single dome (Summitville), or and SiOz for twelve deposits overlap greatly and
within a dome complex (Julcani). In most cases show a dominance of talc-alkaline andesitic and
the mineralization extends from the subvolcanic dacitic compositions, ..with subordinate rhyofite
intrusion into country rocks, such as the Main (Fig. 3). intermediate calcic volcanic rocks are
Vein Cu-Au-Ag deposit and associated breccia limited to porphyritic intrusions in the. Lepanto
deposits in the Penshan area of the Chinkuashih and Motomboto Cu-Au-Ag -districts, and
district. Some deposits, however, do not show any intermediate-to-felsic alkali-calcie rocks are
(known) spatial association with subvolcanic characteristic of the Summitville and Laurani
intrusions thought to be .geneticaIly related to districts (Fig. 3). Interestingly, no deposits have
mineralization (e.g., Nalesbitan, Nansatsu). In the been discovered in association with alkaline or
Rodalquilar Au deposit, dykes and small mafic magmas, even though these magmas can be
intrusions of hornblende andesite which are genetically r e l a t e d t o low-sulfidation a n d
interpreted to be temporally related to the intrusion-related Au deposits (Sillitoe 199 I b,
hMIn mineralization represent only a fraction of the 1993; Miiller & Groves 1993; Richards this
altered and mineralized area exposed at the volume). The data shown in Figure 3 suggest a
present depth of erosion; a larger intrusive body is relation exists between magma composition and

425
A. Arribm, Jr.

Table 3. Main alteration and mineralization characteristics of 14 selected high-sultidation


epithermal deposits

L.atcral aherak~~ zoning Vertical akralicul on!


(outward from minexa- zoning mmcrahzauon
Depose hzcd bodies) (shallow IO deep) Pnncial ore minerals tn: A&/Au

VS-tqu-alu+qtz-kaw WMs-rqtz-alu-rqcz- Fy, ma-luz, mar. sph. pal. ten- Silica core 35-4s
kao-sme-* ill- chi kao+ill-kao-tcbl b%, 813, cpy, arg, na~Au, tell

Nalesbitan Sihcified Hbx-+qrz-kao Sihcif-red Hbx-+qcz-kao- Py. chalcqtz. cco, bar, cov. S~ltca core VaY
alu-*ill-sme-chlcal aJu-+ili-smecblcal ena. tell low Ag

LepIllO VS/MS-+ u-alu-kaw MSNS-r AA+ SER-4 Ena-luz py. Len-tel. cpy. py, ele. Stlica core 4
kao-qo.-ill-rchl-ill (K-silicate in subjacenr sph, gal, mar, s&c. tell, Sn-
FSE porphyry copper) bearing sulf
Chinkuashih Vs!?vts-+qQ-ah&w+ py, ena-lur fam. ten-let. natAu, Silica core 2
ill-chl-kao cle, bar, nat.Hg, tell, spb, gal.
WY, two. bou
Zijinshan v!i/Ms-+qQdiC-&W$z- VSMS-r qQdk-alit-+ qe- py. dig. ew coy, mol, m&Au Silica core N/A
die-VqQ-ser dic-ser-rqrx-s4T cpy, bar. ml-ten, gal. sph

NiUlSalSU VStMS-tatudic-pyo-+ VSIMS-talu-tdic-scr- ma-luz, py, cle, nar.Au. arg. Siltca core <2
ill-kao-sme-r py-‘sa-chl-tPRO ;ci TV& bar. sph. gal, cas. sea
PRO
Summitvilie VS(MS)-rqu-ahi--, py. ena-lur cov, mar. nals. Silica core 2-20
qtz-kao-rkao-ill-r naLAu. s& gaJ, bar, cpy, ten
srne-chl
G3ldfikkl MSNShJrz-alu-m hisrvs-rqtx-alu- py. fam, an-bet, his. gol. Silica core Cl
ill-sme-r k-+qQ-WYo nat.Au. cna-lu& bar. dl. sph.
PRO cov
ParadisePeak Venical 6&e to deposit bar. stb, his, nat.Au, mar. py, Silica core 10-30
style): MSWW na1.S. ein. sph. gal. cpy, afs.
qtr.-aJu-kao-wne-chl tef arg, COY, bun
Puebla Viejo Complex * overprhwd py, sph, cna nal.Au, naLS. bar. In AA + 7
ten-ret, fam, gal, bar, stb. ele. MS zones
se.Je, teU, Bi- Pb- Ag- sulf
Julcani R-owVSiMS-rqtz-slu- py, wol, CBS. naLAu, ena. iuz, Veins 470
kao*qtx-kto; synore: I% ten, cpy. gal. sph bar. sid,
q@.-PYo-PY’qm- Lcao-PY-+ Pb- Bi- Ag-bearing sulf
qtx-ser-py-+qu-kaPsme
El lndio Cu stage veins-1 kao-ahr- Ena. py, tel. nat.Au, ten, cpy, Veins 8
srrqa; Au smge gal. spb. hue, bar, dig, emp,
veins-wr4mopyoqtz CM. -, bar.
La Mejicana, AJu-tmo-rqn-ser-r (K-s& py, ena. cpy. spb. ten-wt. COv, Silica core IO-20
NeMdosdef icateinN.deJFamatina CEO. fam, 1~ narAu. gal, mol.
FmllalhUl J=PbYcoppa) elc, tell, cot Sn-Bi-Pb-Ag-sulf
RodalqUiJar VSIMS-+qe-am-kao-1 VSIMS+qe-atu-kao+ f’y. naLAu, am tell, cas. col Silica core <1
qwkao-ill-t ill-sme-chJ CfUWVqo.aa-py cov. dig, bar, gal, spb, Bi- sulf

Abbreviations used: AA = advanced argillic, Hbx - hydrotbermai breecia, MS - massive silica. PRO = Propylitic, SER -
sericitie, VS = vuggy silica. VS (MS) - vuggy silica dominant, ahr = alunitc. ars - arsenoyrite, bar - barite, bis -
bismuthinite, bar - bornitc, bou - boumonite, Cal - calcite, coo - ob&oeite, obaJ.qtz - chalcedony or cb&edonic quartz,
ohl- chlorite, tin - cinnabar, oan - wnfmldite, oas - c.a&erite, cot - oolusite, eov - wvcltite, cpy - ehrdcopyritc, die =
dickitc, dig - digcnitc. cle - electrum, cmp - cmpicctim, fam - famatmite (stibiohmonitc), gal - galena, gee = gcocronitc,
got - gotdfielditc, hue - htibneritc, ill - illitc, kao = kaoiinim, hu - luzonitc, mar - mama&c, mol - molybdcnitc. nat.Au =
native gold, nat.S - native sulfur, nat.Te = native tellurium, on, = orpimcnt, py - pyrite, pyo - pyrophyllhe, qh - qua
rea - realgar, S&C - seicnides, SEC - sericite. sid - siderite, xme = smecthc. sph - sphalcritc, sta - stannitc, stb - stibnitc,
sulf - sulfides or suifosalts, tell - tc!lurides, ten - tcrmantitc, tct - tetrahedritc. mu - tourmaline, wol - wolframite
’ Based on fluid-inclusion (flint) or geological (geol) evidcncc; blank when not specified.
’ Boiling (Hbx) = boiling due to abrupt pressure reduction associated with hydrothermal brecciation
Table 3 (continued)

waMiorderor Infared Infelled OR- supergene oxidalid


main mineral mineraliwion faming
Dcposil events dcptb (rn)* mechanism References

Motomboto 2 unknown UUklWVB lmgularto IOOm


AA-+sulfidc-Au

Naksbitan 300-500 Boiling (Hbx12 Complete to 130 Sifliroe cl al. (1990)


Py&“-Au fiinc m; yes

3 unknown Mixing/cooling Not impowl Garcia ( 199 1 t. Clavena &


AA-t CL&AU Hedequisl(1994)
-rAu
Chiiuashih L
. 500 Hang ( 1955).
Unknown
AA-+ ‘&Au + Timer 01. WX43)
lau bar-Au
sevaal(?). URktKNll Mixing/boiling Importanl in upper Rcn CI of. ( 1992).
250 a; yes Zbang cl al. (1994)
rsg-$-$g
a-e
2 - 150-300 Mixingkooling WiiLoloO lzawa & Cunningham ( 1989).
M-r Cu- Au flint m: yeis but may Hedenquist Cf 01. wQ4a)
bcz3@aml-hatad
Summiwille 3 MO-so0 Cu-Au by ImguIar to IO0 m; suven & Rattc Ww,)
AA+CukAu+ flint + geol mixing, bar-Au -bf: Stmlvgcn (19871, Gray &
tsr-bwesrclal-Au by oxidation Coolbaugb 09941
Gddkld 9 IOO-3GOt Mixing/cooling; Widespread to SO Ransome ~1907.19091.
AA-rena-+Au- geol oxidation m; supergene Ashley (1974). Vikre (1989.
lut-py-Bi-Te-r &mite l-10 Ma) wfiuen comm.. IQ951
3 Boiling, witb Widesptead to 250 John CI al. WQI),
AA-+Au-Ag-+ Hbx in eariy Au- m; supergene alu- Sillita: & LoIson (1994)
Hg A8 stage nite mi 0.5 Ma)
2 stlaIlow; lanrs- .sulfidatim + I wit0 Keslerct al. (1981)
Alu-kao-py-Au-r tine sediments boiling -100 m Russell & Kesla (1991).
MS-p-a-Au prewud Munuan et al. f 1990)
Srvrral 200-300 Mixing + boiling Deen (1990). Rye (1993)
AA+VS-, 1ou
bnxeias-r sulfide
veins main, late)
El lndii L Mixingholing Siddeley & &ane& ( 1986).
AA+Cu-* Au Jsmas et of. ( 19901

LaMejicana
Nrvadasdcl
FS?JUtilul
Red&&k 2 200-.3&I Boiling (Hbx$ + Wkkqxead to 80
AA-rsilica-py-Au flint + geol mixingholing m: supeqene
alunite (4-3 Ma)

development of the oxidized and reactive and disseminations or replacements. This


magmatic vapor plume that is thought crucial to variation in the structure of the orebodies is
the formation of HS deposits. complemented with variations in other deposit
features, including ore and alteration mineralogy,
DEPOSIT FORM AND CONTROL: paragenesis, and metal ratios (Tables 2, 3). In
CLASSIFICATIONS addition, some deposits present complex relations
which may be composite, e.g., between high- and
High-sulfidation deposits display a wide low-sulfidation mineralization (e.g., quartz-Au-
variety of styles of mineralization that includes stage veins at El Indio, and some of the veins at
veins, hydrothermal breccia bodies, stockworks, Julcani). Definition of styles of HS mineralization

427
A. Arribas Jr.

is difficult, but useful for discussion of the The deposit is 3 km long and consists of a main
differences among deposits and design of zone of breccia and replacement mineralization
exploration strategies. In this context, White along the Lepanto Fault (Fig. 4A). Multiple veins
(1991) distinguished three end-member styles of associated with smaller diagonal faults branch
HS deposits, named after deposits of the Circum- from the main zone and extend into both the
Pacific: Temora, El Indio, and Nansatsu. irregular hanging wall and footwall (Garcia 1991). The
bodies of disseminated, silicified ores dominate in characteristic mushroom-shaped cross-section of
the Temora-style. Cavity-filling veins with many of the orebodies at Lepanto is related to the
sericitic and clay-rich haloes are characteristic of intersection of the steeply dipping Lepanto fault
Et India-style Au deposits. A large group of and branch veins with the unconformity at the
deposits falls into White’s (1991) Nansatsu-style, base of Imbanguila dacite (Fig. 4B). Lithologic
which is characterized by wallrock-alteration variations in the host rocks also played an
zoning similar to that shown in Figure 2, and by important role in the formation of the deposit, as
the occurrence of enargite-bearing ores within a shown by lenses of stratiform enargite-luzonite
silica core consisting of vuggy or massive silica ore which resulted from replacement of detrital
rock (Table 3). Mineralization in this style of layers ,within volcaniclastic and sedimentary
deposit forms irregular stratabound bodies (e.g., basement units (Garcia 199 I ).
Nansatsu, Lepanto) or subvertical vein-like
masses or “ledges” (e.g., Chinkuashih, Goldfield,
Lepanto, Rodalquilar, Summitville). These
deposits contain breccia bodies, veins, stockworks As mentioned above, the lateral alteration
of small veins, and disseminated ores that replace zoning that is characteristic of HS deposits
or impregnate intensely altered country rock. reflects the reaction and neutralization of high-
Ericksen & Cunningham (1993) distinguished two temperature acidic fluids with wallrock. The
styles of HS deposits in the Andean province: Ag- innermost zone of vuggy or massive silica
and Au-rich polymetallic base-metal veins, and alteration commonly has sharp boundaries with a
low-grade vuggy silica and breccias; the two types zone that may contain quartz, alunite, kaolinite,
are broadly comparable with El Indio- and dickite, pyrophyllite, diaspore, and zunyite’. This
Nansatsu-styles, respectively. advanced argillic assemblage grades into a second
Local subvertical faults and fractures are the envelope of argillic alteration, composed of
dominant control on HS mineralization and they minerals such as quartz, kaolinite, illite, sericite,
are present in most deposits (Table 2). Other and smectite, and an outermost halo of propylitic
examples of structural controls observed in some alteration, with chlorite, illite, smectite, and
districts among the fourteen selected include: carbonate (Fig. 2, Table 3). The width of each
moderately to shallow-dipping faults (Goldfield), zone varies widely; for example, vuggy silica and
caldera ring and radial faults (Rodalquilar), the advanced argillically altered rock form narrow
dilational jog of a strike-slip fault (Nalesbitan), (<70 cm) vein selvages -at Julcani (Deen 1990),
diatreme ring-faults (Lepanto, Pueblo Viejo), the but form wide (>50 m) rock bodies at Summitville
contact between a dome or volcanic conduit and or Lepanto (Figs. 2 and 4). Late-stage, cavity-
country rock (Motomboto, the Missionary filling planar veins at Julcani and El Indio may
orebody at Summitville), and a lithologic extend outside the zone of alunite-kaolinite. In the
unconformity (Pueblo Viejo, Lepanto). In three of majority of HS deposits, however, most of the ore
the fourteen deposits, the principal control is is contained within the silica core, inside the
lithological (maar sediments at Pueblo Viejo, and advanced argillic envelope (Table 3).
interbedded pyroclastics layers at Paradise Peak
and Nansatsu; Table 2).
A unique combination of the structural and ‘In Russian and eastern European terminology these rocks are
commonly termed ‘metasomatic quartzites' with more specific
lithological controls characteristic of HS deposits names such as porous quartzitcs, diaspore quartzitcs, alunitc
is exhibited by the Lepanto Cu-Au-Ag deposit. quartzites, and dickite quartzites (e.g., Velinov et al. 1990).
High-Sulfidation Epithermal Deposits

N Lepanto fault S

Figure 4. Longitudinal (A) and transverse (B) cross-sections of the Lepanto-FSE Cu-Au-Ag deposits (Philippines),
showing structural and iithologic controls on formation of the high-sulfidation and porphyry-type ores (simplified
from Garcia 199 1). Potassium-argon dating of country rocks and alteration minerals associated with the porphyry and
high-sulfidation deposits indicates that hydrothermal Gu-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 The lateral and vertical alteration zones
typically grade from a shallow silicie zone described above correspond to a generalized
through advanced argillic, argillic, argillic/ model. They are useful in exploration because
sericitic, into a sericitic or phyllic zone with they help in understanding the genetic environ-
quartz, sericite, and pyrite. This alteration ment of a deposit and provide spatial “markers”
sequence occurs over a vertical interval that within the extinct hydrothermal system.
ranges from a few hundred meters to more than Experimental data on the relative stability of
1000 m, and has been best documented by deep minerals such as alunite, kaolinite, pyrophyllite,
drillholes in the deposits of smaller size, in which and diaspore (Hemley et al. 1969, 1980), coupled
the vertical span of mineralization is less than with the temperature ranges noted for these and
about 300 m (e.g., Rodalquilar, Summitville; Fig. other related acid minerals in active systems
5B). At Lepanto, sericitic alteration at depths of (Reyes 1990; Reyes et al. 1993), also provide
400 to 500 m below the epithermal deposit gives information that contributes to definition of the
way, laterally towards the south, to K-silicate paleoconduits in extinct systems.
alteration of the FSE porphyry Cu-Au deposit. If studied in detailed, several superimposed
Porphyry-type stoekwork mineralization at and crosscutting stages of pervasive as well as
Paradise Peak is contained within the sericitic ores fracture (conduit)-related mineralization may be
of the East Zone deposit which, according to recognized in the majority of deposits. These are
Sillitoe & Lorson (1994), formed underneath the the expected result of variations, during the course
main HS orebodies in the area. A quartz-sericite- of mineralization, in temperature, pressure, and
pyrite zone with trace amounts of chalcopyrite and composition of the hydrothermal fluid and the
molybdenite surrounds an intrusion of monzonite degree of wallrock interaction. Detailed field and
porphyry s300 m below the HS deposit at petrographic studies at the Monte Negro orebody
Summitville (Gray & Coolbaugh 1994). in the Pueblo Viejo deposit have resulted in

429
A Arrrbas, .Jr.

Sericitic
Propylitic
intense supergene add-sulfate overprint

Figure 5. Generalized surface alteration map (A) and cross-section (B) of the Rodalquiiar
HS deposit in the Rodalquitar 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, particular features of the deposits listed in Table
interpreted to correspond to two distinct magmatic 3. Pyrite and enargite (and its low-temperature
pulses (Muntean et al. 1990). During the first dimorph lusonite) are the daminant sulfides in HS
stage (responsible for -60% of the Au in the deposits; pyrite is abundant but the amount of
deposit), shallow kaolinite-quartz-pyrite and deep enargite and luzonite is variable. Common ore
alunite-quartz-pyrite-quartz zones were de- minerals, listed by decreasing abundance from
veloped, with gold mineralization in association variable to very minor, include tennantite-
with disseminated pyrite in the wallrock; during tetrahedrite, covellite, native gold and argentian
the second stage (responsible for about 40% of the gold (electrum), marcasite, chaicopyrite, spha-
Au), an extensive zone of silicification with pyrite lerite, and galena. Famatinite is locally abundant
f sphalerite f enargite veins formed at shallow in some deposits (Goldfield, La Mejicana). Sparse
levels, above a zone of pyrophyllite-diaspore ore minerals include bornite, cassiterite, cinnabar,
alteration (Muntean et al. 1990). molybdenite, orpiment, realgar, stibnite, and
wolframite {the last locally important at Julcani).
ORE AND GANGUE MINERALOGY, AND Other minerals present in minor amounts in
TIMING OF MINERALIZATION several deposits include Pb-, Ag-Pb, Bi- and Sn-
bearing sulfosalts (Table 3).
White et al. (1995) and White & Hedenquist Fine-grained quartz is the dominant gangue in
(I 995) presented detailed discussions on various HS deposits. Other common but minor gangue
aspects of epithermal gold mineralization on the minerals include barite, kaolinite, alunite,
basis of observations from a large number of pyrophyllite, diaspore, and Ca-,Sr-, Pb- and REE-
deposits around the Pacific; their conclusions with bearing phosphate-sulfate mineral(s) such as
respect to ore and gangue mineralogy in HS svanbergite-woodhouseite or crandallite (Stoff-
deposits are included here, in addition to the regen & Alpers 1987). For example, high-grade
High-sulfidalion Epithermal Deposits

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

431
A. Arribas, Jr.

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

Host-mineral Temperature Salinity Associated


Deposit studied (“C) * (equiv wt.% NaCI) alteration
Moromboto. Indonesia Barite 150-180 <I AA/sil
Nalesbitan, Philippines Quartz 220-260 AA/sil
Lepanto, Philippines Enargite 170-290 0.2-4.5 AA/sil

Chinkuashih, Taiwan Quartz. bat-ice, 180-330 0.2-l 2


alunite
Zijinshan. China Quartz (no details 160-300 2-22 AA
=P=d) 220-380 3-19 Ser
100-160 Sil
(300-420) (EO)
Nansatsu. Japan Quartz 130-250 <I AA/sil
-270 up to 30 AA/sil
250-310 Ser
Akaiwa. Japan Diasnore 190-240 AA/sil
Mitsumori-Nukcishi. Japan Quartz barite 210-330 0.5-14 AA
quartz phcnoc
Summitville Colorado Quartz phenoc 180-280 2-18 AA/sil

(up to 9)
Barite “%Y
Coldfield, Nevada Quaazphenoc 230-480+ 5-18 AA/sil
Quartz barite 210-280 0.2-8 AA/sil
(370-410)
Paradise Peak, Nevada 180-210 <3 AA/sil
82 barite 300-380 30-35 Ser
(up to 450)
Julcani. Peru Quartz phenoc 160-280 5-24
Qu-phe= 360-450 38-46
Wol. ena. quartz 230-330 9-20
Siderite 220-250 6-9
Ccarhuaraso Peru 330-380 7-18 AAJsil
Colquijirca, Peru 230-260 4-11 AAlsil
Can-Can (La Coipa). 170-350 <l-4O AA/sil
Chile dominant
El Indio. Chile Sphalerite. quartz 190-280 0.1-4 AAlsa
hubnerite MO-180 0.1-2.7
Quartz phenoc (>300) (up to 27)
La Mejicana (LM) and N/A 2oo-460 l-37 AA + ser
Nevados Famatina (NF). 16O-340 0.3-12 AA
Argentina 230-480 3-47 ser

Rodalquilar. Spain Quartz, quartz 170-300 2-30 AA/sil


phenoc 220450 2-45 SW
Furtei-Serrenti. Italy 190-320 0.4-23 AAfsil
90-140. 0.4-1.6
(390-500) (32-45)
Abbreviations used: AA = advanced argillic, ena = cnargile, phenoc = phenocrysts. ser =
sericitic sil = silicic: wol = wolframitc; see Table 3 for paleodepth estimations
1 temperatures are rounded to the nearest lo”, brackets used to indicate high-temperature
inclusions typically interprctcd as having formed early or being anomaloUs

interpreted as “anomalous” or unrelated to ore and entrapment cannot account for all the high Th
are associated with early stages of alteration. values. The consistent presence of these fluids in
Two-phase entrapment may explain some of the several deposits indicates a high temperature
unusually high homogenization temperatures (T’), gradient, and implies the presence of a shallow-
particularly considering the shallow minerali- depth intrusion, and possibly lithostatic confining
zation depth inferred for many of the deposits pressures. On the basis of fluid-inclusion, as well
(Table 3). However, most workers agree that such a s isotopic (634S sulfate-sulfide) temperatures (see
High-suljdation Epithermal Deposits

Table 4. (continued)

Deposit Comments References


Motomboto, Indonesia RecoMaiSanCc study in late-stage barite Perelld ( 1994)
Nalesbitan, Philippines Reconnaissance study; liquid CO2 observed Sillitoe er RI. (1990)
Lepanto, Philippines Sampled interval 3 km long by 0.5 km high ; cooling fluids Mancano & Campbell ( 1995).
away from subjacent porphyry Cu-Au deposit, where Garcia (1991)
Th >45O”C & salinity up to 54 eq wt.% NaCl
Chinkuashih, Taiwan Poorly-documented samples along a 450-m vertical interval; Folinshee c/ crl. (1972). Yen
the higher ThS in samples at -750 m depth: CO1 observed (1976).Taneral. (IYY3)
Zijinshan, China Associated with main stage Cu Zhang er nl. (I 994)
Deep alteration zone (%OO m depth)
Associated with late, shallow silica-Au
Associated with early silica and quartzdickite
Nansatsu. Japan Late, vug-filling quattz Hedenquist er af. (1994a)
Qtz in breccia, saline liquid and low-salinity vapor coexist
Vein quattz 400 m below Kasuga deposit
Akaiwa, Japan coane-grained diasporc Akamatsu & Yui (1992)
Mitsumori-Nukcishi, Japan Not (known) Au or Cu mineralization. but high salinity Aoki & Watanabe (1995)
nuids
Summitville, Colorado Liquid-rich; salinity % eq wt.8 NaCl only in vuggy silica Bruha & Noble (1983). R.
associated with Cu mineralixat.ion; Ct& observed Stoffregen (written
Liquid- and vapor-rich inclusions; also polyphase inclusions commun., 1994)
Late barite-Au assemblage Cunningham (1985)
Goldfield, Nevada True Th is interpreted to be 2%290°C Bruha & Noble (1983)
Hydrostatic and near-lithostatic pressures suggested vikrc (1989)

Paradise Peak, Nevada Late, vug-tilling crystals in hydrothermal breccia; John eral. (1991)
From stockwork Au East Zone deposit; C& observed Sillitoe & Lorson (1994)

Julcani. Peru Quatix-aluniteipyrite Bruha & Noble (1983)


Pre-cre tourmaline breccia dykes, JithosmtJc pressures likely. Shelnutt & Noble (1985)
Main-stage ore fluids, also inner veins, liquid-rich inclusions Deen (1990)
Late-stage ore fluids, also in outer veins; P correction applied Deen (1990)
ccarhuaras0, Peru Quartz-alunitcbpyrite Bruha & Noble (1983)
Colquijirca. Peru Quartz-alunit&pyrite Bruha & Noble (1983)
Can-Can (La Coipa). Two generations identified: both may be very saline. Evidence Townley t I99 I )
Chile for P above hydrostatic and higher salinities at depth
El lndio, Chile Coppex and gold stages Jannas el at. ( 1990)
Late stage
lnterprcted as early, with vapor-rich inclusions, CO2 observd
La Mejicana (LM) and LM & NF: includes liquid-, vapor-rich and polyphase inclusions LosadaCaldcrbn & M&hail
Nevados Famatina (NFJ, NF: complete ttansition from porphyry-type fluids in K- (1994)
Argentina silicate stage (300-6OO*C, up to 67 eq wt% NaCI)
through se&tic to epithermal fluids in HS (AA) stage;
vapor-rich inclusions typically less saline
Rodalquilar, Spain Vertical tcmperaturc and salinity gradient: high-temperature Stigcr-von Ocpen er al. ( 1989).
brines coexist with low -alit&y vapor inclusions; Afribas er al. (199SaJ
hydrostatic and near-litbostatic pressures suggested
Furtci-Serrenti. Italy Includes high + low-salinity fluids (22-23, <6 eq wt% NaCI) Ruggieri (1993b)
Late stage

below), pressures above hydrostatic have been <l to -18 equiv. wt.% NaCl. With the possible
suggested for several deposits, including Julcani exception of deposits for which only the late-stage
(Shelnutt & Noble 1985) Goldfield (Vikre 1989), minerals have been studied, these typically liquid-
Summitville (Rye 1993), and Rodalquilar (Arribas rich inclusions are found in all deposits. Main-
et al. 1995a). stage ore fluids are contained within this group.
Group 2. Intermediate-temperature fluids The temperatures measured in fluid inclusions in
(e.g., 180-330 “C), with salinities variable from enargite at Lepanto (Mancano & Campbell 1955)

433
A. Arribas, Jr.

and Julcani (Deen 1990) are broadly similar, but Temperature (“C)
their salinities are distinctly different (0.2-4.5 200 300 400 1

equiv. wt.% NaCl versus 8-18 equiv. wt.% NaCI,


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-l 80 \I 200
\\ 2 (hydrostatic)
“C), dilute (typically <5 equiv. wt.% NaCI)
liquids; these have been documented in a few
4 3
\ \ -I (lithostatic)
t
deposits associated with late-stage (e.g., Au- \
I .g
.-
barite) mineralization. The late-stage ore fluids at 2 PQ
A
t >’
Julcani are hotter (220-250 OC; Deen 1990) and ,
I
‘ %
slightly more saline (6-9 equiv. wt.% NaCI), than I
these averages, but no correlation among the late -z 1
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
300
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 tem- Figure 6. Elevation versus temperature diagram
showing the range (horizontal line) and average
perature and salinity along a >600-m vertical (vertical line) of fluid-inclusion homogenization
interval (extending 500 m below the ore zone; Fig. temperatures measured in the Rodalquilar Au deposit,
6) shows a gradient which correlates with the Spain. Also shown are the temperatures calculated, on
change in dominant alteration, from silicic and the basis of I?S sulfide-sulfate for four coexisting alunite-
advanced argillic (T = 170-300 OC, salinity = 2-15 pyrite samples (large filled circles), reference boiling-
equiv. wt.% NaCl at the elevation of the orebody) point curves, and vertical spans of the alteration zones
to sericitic (T= 220-450 OC, salinity = 2-45 equiv. mentioned in the text. Estimated salinities of fluid
wt.% NaCI) assemblages. inclusions in the shallow advanced argillic/silicic zone
The transition from advanced argillic alteration, and deep sericitic zone range between 2 to 30 equiv.
through .quartz-sericite-pyrite, to K-silicate wt.% NaCl and 2 to 45 equiv. wt.% NaCI, respectively
alteration and typical porphyry-type high- ..(modified from Arribas et al. 1995a).
temperature (600+ “C) and high-salinity (up to 67
equiv. wt.% NaCl) fluids of magmatic origin is
displayed, among the examples reviewed, at the rich hypersaline inclusions (i.e., with Groups 1
Lepanto-FSE and La Mejicana-Nevados de1 and 4, above). These fluids may be the result of
Famatina epithermal-porphyry copper systems. boiling of a high-temperature liquid, or they may
The cooler and less saline inclusion fluids reflect immiscible vapor and hypersaline liquid
documented in the ore zone of the HS deposits are derived directly.. from shallow-emplaced .magma
interpreted to reflect mixing of magmatic and (Rye 1993; Hedenquist & Lowenstern 1994;
meteoric fluids. in an environment shallower than Shinohara 1994; Hedenquist this volume).
that of porphyry mineralization. Furthermore, in
common with porphyry-type deposits, high- Surfur-isotope Evidence
temperature, vapor-rich, low-salinity fluid The abundance of coexisting hydrothermal
inclusions coexist with high-temperature, liquid- sulfides and sulfates, in addition to the possibility

434
High-sulfidation Epithermal Deposits

1 -Sulfides - I Sulfates - va v- 634Szs A%+s-so,


Temp. (“c)’ H2S’ so4

Lepanto 220 - 420 2-6


Chinkuashih 220 -270 -
Nansatsu 200 -240 3

Summitville 200 -390 4


Goldfield 200-350 -
Pueblo viejo 180-260 -
Julcani 210-270 5
El Indio
Rodalquilar 220-330 5
*(mineral pairs)

Figure 7. Range of 834S (per mil) values for sulfides and sulfates from nine high-
sulfidation deposits. Also shown are the values calculated for 634S 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 634Szs 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 34S/32S in host rock and genetically 634S values of pyrite and enargite from the same
related igneous rock (Sasaki et al. I979), allows vein, these values indicate drastic changes in
sulfur-isotope studies to provide information on H2WSO4 during the course of mineralization
the composition, temperature, and sulfur sources (similar to those for the Red Mountain alunite
of the hydrothermal fluids. The results of detailed deposit; Bove et a/. 1990; Rye 1993).
studies in nine HS districts show a remarkable The main conclusions of the sulfur-isotope
consistency (Fig. 7). In agreement with the studies in HS deposits are: (1) sulfur in the
observations in active volcanic-hydrothermal deposits is magmatic, but the magmatic sulfur is
systems (e.g., Kiyosu & Kurahashi 1983), sulfide overall heavier than mantle values (from 634S = 2
and sulfate minerals are mainly in isoto ic -f 2’100 at Summitville, to 9 f 2 “/OO at Rodalquilar;
5:
equilibrium, and, therefore, their overall 34S/ S Fig. 7). This is not surprising given the most
depends on the temperature of mineralization and common geological setting of the deposits;
the “St2S of total sulfur in the hydrothermal isotopically heavy igneous sulfur is common in
system. Only the data for alunite from the volcanic arc environments (e.g., Ueda & Sakai
Campana vein in El Indio (Fig. 7) are different. If 1984). (2) A simple mass-balance calculation
the measured El Indio alunites are not steam- done in several deposits using the 34S/32S values
heated or supergene (unlikely as they contain fine- of the igneous rocks and the average 34s/32s
grained pyrite; Jannas ef al. 1990), the most likely values of sulfides and sulfates indicates that
explanation is a “magmatic-steam” (Rye ef al. H$S/SO4 in the hydrothermal fluids was generally
1992) origin, in which the 634S of alunite is close about 4 f 2 (Fig. 7; Rye er al. 1992; Hedenquist el
to the composition of total sulfur in the system al. 1994a; Arribas ef al. 1995a). This is a
(e.g., Alunite Ridge in Marysvale; Cunningham el minimum value for ore-forming fluids because it
al. 1984; Rye ef al. 1992) . Combined with the applies mainly to the early stage of hydrothermal

435
A. Arribas, Jr.

alteration, which is characterized by a sulfate-rich lack of post-depositional effects that disturb the
alunite-pyrite assemblage. (3) Isotopic equilib- stable-isotope systematics, and (4) the availability
rium between sulfide and sulfate in the of detailed information on the isotopic
hydrothermal solutions results, in a majority of the composition of fluids in active geothermal and
deposits, in reliable temperatures calculated on the volcanic-hydrothermal systems, which allows
basis on A34SH2~-~~4 (Fig. 7). Pyrite-alunite fluids estimated in HS deposits to be compared
mineral pairs were used most commonly, and with those in their active equivalents.
where sampling with depth is available, they show Some limitations still exist. These may be
a thermal gradient: e.g., 220 to 330 “C over 200-m independent of obvious factors such as sampling
elevation at Rodalquilar (Arribas et al. 1995a), or mineral-preparation procedures (fundamental
200 to 390 “C over -900 m at Summitville (Rye for achieving representative and reliable results),
1993); 220 to 420 “C over 500 m at Lepanto analytical imprecision, and natural variations, as
(Hedenquist and Garcia 1990; J.W. Hedenquist, observed in active systems (e.g., Aoki 199 1, 1992;
,unpub. data). Other mineral pairs used with Rowe 1994). Important limitations that must be
consistent results include pyrite-barite (Vikre taken into account for optimum use of the stable-
1989; Deen 1990), sphalerite-barite (Vennemann isotope. data are related ..to (I) the choice of
et al. 1993), and pyrite-gypsum (Vikre 1989). The temperature of mineral formation for calculation
range of isotopic temperatures is consistent with of the fluid isotopic composition, (2) the lack of
temperatures estimated from fluid inclusions and mineral-water fractionation factors for some
alteration mineralogy (e.g., Hemley et al. 1980; minerals (e.g., pyrophyllite), and (3) the
Reyes 1990; Reyes et al. 1993). The range is also disagreement a m o n g fractionation constants
consistent w i t h f o r m a t i o n o f alunite a t proposed for even common minerals such as illite
temperatures below 400 OC, when SO2 gas starts (see Dilles et al. 1992, for a discussion) and
to disproportionate in the hydrothermal solution kaolinite. For example, at 200 OC there is a
(Sakai & Matsubaya 1977; Bethke 1984). difference of -20’/00 between the D/H frac-
tionation constants for kaolinite - water as given
Oxygen- and Hydrogen-isotope Evidence by Marumo et al. (1980) on the basis of samples
In terms of oxygen and hydrogen isotopic of minerals and water from active systems, and by
composition, the fluids that form HS deposits are Liu & Epstein (I 984) on the basis of experimental
arguably some of the better documented and results. For these reasons, discussion of the
understood in ore-deposit studies. This situation sources of water during acidic alteration in the
contrasts sharply with that of a decade ago, at deposits considered here is based on the average
which time no data were available to corroborate of the data collected for alunite, for which
the affinitysuggested between fluids in active fractionation factors are well-known (Stoffregen
volcanic-hydrothermal systems and HS deposits ef al. 1994). .The .magmatic-hydrothermal alunite
(e.g., Heald et al. 1987; Hedenquist 1987). Stable- typical -of-HS deposits :gives goodresults because
isotope studies of HS deposits are particularly it is relatively coarse-grained (post-mineral D-H
illuminating because of: (1) the abundance and exchange is not a problem; Stoffregen et al. 1994)
variety of oxygen- and hydrogen-bearing minerals and commonly is closely associated with ore, thus
(e.g., alunite,illite, kaolinite), (2) the development recording equilibrium conditions of a fluid closer
of analytical procedures for complete stable- in composition to the ascending mineralizing
isotope analysis of alunite, including 6’*0,,, and solution than the kaolinite or illite from outer
6’*0,, that help to distinguish the various types alteration zones.
of alunite and associated acid-sulfate alteration Oxygen and hydrogen isotopic compositions
(Rye et al. 1992; Wasserman et al. 1992), (3) of water in HS deposits are clearly consistent with
fewer limitations on the interpretation of the mixing between a high-temperature magmatic
isotopic data because of the relatively young age fluid of 6’*0 = 9 f lo/m and 6D = -30 f 20’/00 and
of mineralization of most HS deposits and general meteoric groundwaters (Fig. 8). In part because of
High-suljidation Epithermal Deposits

Alunite alteration stg. Subduction-related


Ore mineralization stg.
Alteration!
mineralization

-20 -15 -10 -5 0 5 10 15 20


s’so (%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 6’80s04); 6’n00H 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 de1 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 relations are identical to those of volcanic-
meteoric water, this meteoric-magmatic water- hydrothermal and geothermal systems associated
mixing trend is displayed particularly well by the with subduction-related volcanism (Giggenbach
three stages of alter&ion/mineralization at Julcani 1992b; Fig. 8, inset). The similarity is even closer
(Deen 1990; Rye 1993): from a magmatic-water- between the composition of acidic alteration fluids
dominated early stage of (alunite) acid-sulfate (large shaded field, Fig. 8) and the vapor
alteration (Ju; Fig. 8). through main ore-stage condensates from high-temperature fumaroles of
fluid-inclusion waters (Jut and Juz), to meteoric- andesitie volcanoes (dark shaded field, Fig. 8,
water-dominated Iate ore-stage fluid-inclusion inset), such as Nevado de1 Ruiz, Satsuma
waters (Jus), In addition to Julcani, the ore fluids Iwojima, or White Island, the last documented to
at Summitville (Rye ef al. 1990; Rye 1993) and have a geochemical environment similar to that of
Rodalquilar (Arribas et al. 1995a) also have lower HS mineralization (Hedenquist ef al. 1993).
6’*0 values than those of acidic alteration fluids, The origin of the D-enriched magmatic (end-
indicating greater dilution by groundwater (Fig. member) fluid of HS deposits has been interpreted
8). The extent of an O-shift in the groundwater in two ways. Most workers conclude that the
component due to water-rock interaction, as acidic fluid in HS deposits is derived from
typically seen in some neutral-pH geothermal absorption of magmatic vapors outgassing from
systems, is not known, but such a shift is not arc volcanoes or felsic magmas in crustal settings
indicated by the Julcani data. (e.g., Hedenquist & Aoki 199 1 ; Matsuhisa 1992;
The overall oxygen-- and hydrogen-isotope Giggenbach 1992a; Vennemann et al. 1993;

437
A. Arribas, Jr.

Hedenquist et al. 1994a; Arribas ef al. 1995a). 1994). Detailed and comprehensive radiogenic
The 180 and D enrichment of the volcanic vapors isotope studies are needed, particularly in districts
with respect to their parent magmas (Fig. 8) is a where a majority of the host or country rocks are
consequence of fractionation during degassing expected to have isotopically distinct signatures
from the melt (Taylor 1986, 1992; Matsuhisa from those of the genetically related igneous
1992). In an alternative interpretation proposed by rocks.
Deen (1990) and Rye (1993), the enrichment in If magmatic fluid is accepted as the dominant
deuterium is the result of reaction in a low metal source in porphyry copper deposits, then the
water/rock environment between magmatic fluid best evidence for a magmatic fluid source in HS
of 6D -SO”/,,,, (calculated on the basis of the D/H deposits comes, perhaps, from consideration of
of igneous biotite) and wallrock at magmatic the common genetic connection between the two
temperatures down to T = -400 "C (Rye 1993), deposit types (Sillitoe 1988, 1989, 1991a, this
beneath the ore zone. This interpretation requires volume; Henley 1991; Mitchell 1992). In this
that there have been chemical and isotopic context, Arribas ef al. (I 995b) have argued for a
equilibrium between the magmatic fluid and common magmatic metal source for the FSE-
country rock; however, this would likely result in Lepanto porphyry-epithermal HS copper-gold
neutralization of the magmatic fluid, a condition system on the basis of the intimate spatial and
that would not favor the extreme acidity required temporal relations (Fig. 4) and similar metal
for formation of-vuggy silica at shallow depths associations (i.e., Au/Ag values and high Te, Sn,
(Giggenbach 1992a). and Bi).

SOURCES OF METALS POST-DEPOSITIONAL EFFECTS

The origin of metals in HS deposits is more In deposits that have not suffered deformation
speculative. There is consensus among most and metamorphism (those in Table 1, aside from
workers (e.g., Sillitoe 1989, 199la; Henley 1991; the Paleozoic deposits in southeastern Australia
White 1991; Rye 1993; Hedenquist er al. 1994a) and. the Proterozoic En&en deposit in Sweden),
that the bulk of the ore-forming components is the principal post-depositional processes affecting
contributed by magmatic fluid, either directly by a HS deposits are mineral deposition from near-
magmatic vapor or hypersaline liquid that is surface steam-heated or supergene waters. Both
incorporated into the hydrothermal system, or can result in acid-sulfate alteration which may
indirectly by remobilization of metals from a mask hypogene alteration zones and ore. On the
porphyry-type protore. The study of radiogenic basis of geological and mineralogical criteria, K-
isotopes so far has not provided conclusive Ar dating, and stable-isotope analyses of alunite,
evidence. The reason for this is a consequence of identification of the origin of acid-sulfate minerals
the common intimate association between the overprinting should be straightforward (e.g.,
deposits and host rocks; all are indistinguishable, Hayba et al. 1985; Rye et al. 1992; White &
e.g., for Pb-isotope systematics. Lead-isotope Hedenquist 1995). At Paradise Peak, a drop of the
studies at Summitville (Doe ef al. 1979) and paleowater table during a late stage led to
Rodalquilar (Arribas ef al. 1995a) have shown overprinting of steam-heated acid leaching with
that the Pb in the deposits is igneous, but these Hg mineralization and abundant cristobalite
studies provide no information about the (Sillitoe & Lorson 1994). Atmospheric oxidation
processes by which the hydrothermal system of sulfides during weathering in at least three HS
acquired the metal (i.e., leaching of the host rocks deposits (Goldfield, Rodalquilar, and Summit-
or derivation from a crystallizing magma). By ville; Table 3) led to development of surficial
contrast, in low-sulfidation gold deposits it is not supergene acid-sulfate blankets. Supergene alunite
uncommon to detect a component of basement- at Rodalquilar forms white to yellow,
rock Pb (e.g., Doe ef al. 1979; Arribas & Tosdal porcelaneous veins consisting of tine-grained
High-sulfidation Epithermal Deposits

(commonly <50 pm) pseudocubic alunite with (Jannas ef al. 1990).


subordinate jarosite, kaolinite, and hydrated A feature of HS deposits which has been
amorphous silica (Arribas ef al. 1995a). In the noted commonly is a change in the hydrothermal
western United States, formation of supergene system with time towards a fluid that is less
alunite at -10 Ma at Goldfield and Paradise Peak reactive and less oxidized. To explain this
(Table 3) seems to be related to regional tectonic observation, Berger & Henley (1989) suggested
episodes (e.g., Arehart ef al. 1992). For an account that precious-metal mineralization in HS deposits
of supergene effects in deposits of the Chilean is introduced by later incursion of low-sulfidation
Andes, see Sillitoe (199Ia). 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), G i g g e n b a c h ( 1992a), R y e (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-sulfrdation 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 ore- The 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 talc-alkaline magma to within a few
metallic deposits formed within magmatic- kilometers of the paleosurface. Rather than a
hydrothermal systems (i.e., including low- spatially and temporally isolated magmatic event,
sulfidation deposits, porphyry-type deposits, the subvolcanic intrusions seems .to represent an
replacement skam deposits, and even submarine “aborted” late-stage feeder . of a comagmatic
volcanogenic massive sulfide deposits). This central-vent volcano or a maar - diatreme or flow-
aspect is important from a genetic perspective; as dome complex. Within the ascending, crys-
it 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
Lowenstem 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 (Lowenstem 1994;
‘1990). In contra&crosscutting relations at Julcani Shinohara & Kazahaya t h i s v o l u m e ) . A t t h e
are unambiguous; the early stage of acid-sulfate confining pressure of a few kilometers depth ( 5 0 0
alteration 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 (Foumier 1987; Hedenquist & Lowenstem
early enargite veins and later gold-quartz veins 1994; Shinohara 1994), with chloride-complexed

439
A. Arribas Jr.

ALTERATION ORE DEPOSITION

0
(km

meteoric water

Maamatic vapors Q
Vuggy silica
Alunite
Kaolinite
Sericite
K-Silicate

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 8,: 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 low-
salinity, mixed magmatic-meteoric ore fluid (Hedenquisl 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 reaches shallow depths of less than a kilometer, it
l i q u i d (Hemley e t a l . 1 9 9 2 ; H e d e n q u i s t t h i s may be absorbed by groundwater if it does not
volume). discharge as a fumarole. The acidity of this
At this early intrusive stage, several modes of groundwater-absorbed vapor condensate increases
magma degassing may occur which will lead to as the liquid cools, first at temperatures below
different styles of magmatic-hydrothermal -400 OC by disproportionation of SO2 to form
systems with or without associated mineralization H2S04 and H$ (Day & Allen 1925; Sakai &
(Giggenbach 1992a). To form the styles of Matsubaya 1977), then by progressive disso-
alteration and the spatial distribution of alteration ciation of H2S04 and HCI at lower temperatures
zones characteristic of HS deposits, degassing (a00 “C). Reaction of the increasingly acidic
must be very efficient, with oxidized high- liquid with wallrock results in the upward
temperature magmatic vapor reaching shallow alteration sequence o f sericite-+kaolinite+
depths with little reaction with rock or dilution by alunite-tvuggy silica (Fig. 9A); the residual
groundwaters at greater depths (Fig. 9A). Dilution vuggy silica rock results from complete leaching
with groundwaters is unlikely because the high of the rock components, except silica, by a
temperatures surrounding the cooling magma hydrothermal solution with a pH <2 and
cause meteoric water cells to be displaced From temperatures probably <250 OC (Stoffregen 1987).
the magma core (Fig. 9A). In addition to the The extremely acidic conditions may even lead to
relatively law pressure at the depth of intrusion, formation of dissolution cavities in which the only
effective degassing will be favored by the remnant of the host rock is a basal sedimentary
structural factors characteristic of HS deposits, layer of quartz phenocrysts (e.g., Rodalquilar;
such as fractured volcanic domes or roots of Arribas et al. 1995a).
domes, caldera or diatreme faults, volcanic vent For the quartz-alunite-pyrite assemblage of
contacts, and active faults with a dilational the advanced argillic zone, the stable-isotope
component. evidence is consistent with magmatic vapor being
As the high-temperature magmatic vapor absorbed by meteoric waters, with the latter
High-sulfidation Epithermal Deposits

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

441
A. Arribas, Jr.

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

oxygen and hydrogen isotopic ratios, the waters ACKNOWLEDGMENTS


involved in formation of HS deposits -are identical
to waters in active volcanic-hydrothermal sys- Valuable insight on various aspects related to
tems, in which the same HS geochemical this exciting ore-forming environment was gained
environment has been documented. through discussions and field work with M. Aoki,
Ore formation in some HS deposits may A. Arribas Sr., C. G. Cunningham, J. Hedenquist,
accompany acidic alteration, and recent studies of W.C. Kelly, R. 0. Rye, J. J. Rytuba,and T. A.
the hydrothermal geochemistry of Au provide Steven. Earlier versions of this manuscript
preliminary evidence that this element may be benefited from constructive reviews by Phil
transported in HS and low-sulfidation systems as Bethke, Andrew Campbell, Anne Thompson, John
different hydrosulfide complexes (AuHSO and Thompson, Peter Vikre, Noel White, and Jeff
Au(HS)2-, respectively; Bening & Seward 1994; Hedenquist, who also provided abundant
Seward 1973). On the other hand, the presence of documentation on HS deposits worldwide.
moderate to high salinities in many HS deposits,
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High-sulfdation Epithermal Deposits

separation and total stable isotope analysis of APPENDIX 1


alunite. U.S. Geol. Surv. Open-file Report 92-9.
Summary of data and references used to compile
WHITE, N.C. (1991): High sulfidation epithermal gold Figures 3, 7, and 8.
deposits: Characteristics, and a model for their
origin. Geol. Surv. Japan Report 227,9-20.
Figure 3
WHITE, N.C. & HEDENQUIST, J.W. (1990): K20 versus SiOl variation diagram. The name
Epithetmal environments and styles of minerali- of lithologic units analyzed, number of samples
zation: variations and their causes, and guidelines (n), and data sources are given: Chinkuashih,
for exploration. J. Geochem. Explor. 36,445-474. dacite n = 18 (Chen & Huh 1982); Choquelimpie,
Choquelimpie volcanic complex (5 units), n = 20
WHITE, N.C. & HEDENQUIST, J. W. (1995): Epi- (Gtipper et al. 199 I ; chemical data for the
thermal gold deposits: styles, characteristics and feldspar porphyries genetically related to
exploration. Soc. Econ. Geol. Newsletter 21, mineralization are not available); Goldfield,
(accepted).
rhyodacite n = 6 (Ransome 1909; Ashley, unpub.
WHITE, N.C., LEAKE, M.J., McCAUGHEY, S.N. & analyses in Sillitoe 1993); El Indio, Cerro de las
PARRIS, B.W. (1995): Epithetmal deposits of the Tortolas Formation, n = 15 (Maksaev et al. 1984;
southwest Pacific. J. Geochem. Explor. (accepted). in Sillitoe 1993); Julcani, dacite and rhyodacite, n
= 10‘ (Petersen et al. 1977); Laurani, Laurani
WHITNEY, J.A. (1988): Composition and activity of volcanic and intrusive rocks, n = 10 (Jimenez et
sulfurous species in quenched magmatic gases al. 1993); Lepanto, Imbanguila dacite and least
associated with pyrrhotite-bearing silicic systems. altered quartz diorite porphyry, n = 4 (A. Arribas,
Econ. Geol. 83,86-92. unpub. data); Motomboto, porphyritic intrusions,
YEN, C.C. (1976): Trapping temperature and pressure n = 10 (PerelIo 1994, and written comm. 1995);
of the fluid inclsuions in the gangue minerals of Nansatsu, Upper Formation and hornblende
gold-silver-copper deposits at Chinkuashih, andesite in Middle Volcanic rock, n = 2 (E. Izawa,
Taiwan. Geol. Soc. China [Taiwan] Proceedings written comm. 1995); Paradise Peak, average of
19, 127-133. Younger andesites, n = 31 (John et al. 1991);
Roclalquilar, hornblende andesite, dacite tuff, and
YOON, C.H. (1994): Gold content variations in the rhyolite domes, n = 7 (Arribas et al. 1995a);
acid-sulfate alteration zone of the Seongsan and Summitville, Fisher quartz latite, n = 7 (Steven &
Ogmaesan clay deposits in Naenam area, Korea. Ratte 1960).
Resource Geol. 44,277.

WI, S. & MATSUEDA, H. (1994): Several mineral Figure 7


deposits in Saku-Machi, Nagano prefecture. Range of 634S (o/oo) values. Given below are
Resource Geol. 44.305. the number of measurements for sulfides (n,,,),
sulfates (n&I, sulfide-sulfate mineral pairs
ZHANG, D. LI, D., ZHAO, Y., CHEN, J., LI, Z. &
ZHANG, K. (1994): The Zijinshan deposit: the (na”S), and references: Lepanto, nHZS = 52, ?rso,,
first example of quartz-alunite type epithermal = 38 (Hedenquist & Garcia 1990; J. Hedenquist &
deposit in the continent of China. Resource Geol. M. Aoki, unpub. data); Chinkuashih, nHZs = 4,
44,93-99. %04 = 2, nA34S = 2 (Folinsbee et al. 1972);
Nansatsu, nH*s = 6, n so4 = 9 (Hedenquist et al.
1994a); Summitville, nHZS = >l 1, n so4 = 17,
rz~~‘S = 7 (Rye ef al. 1990); Goldfteld, nn~s = 16,
nsm = 16, nb34S = 7 (Jensen ef al. 197 1; Vikre
1989); Pueblo Viejo, nnzs = 19, n so4 = 7, nA34S =
4 (Vennemann ef al. 1993); Julcani, +s = 183,

453
A. Arribas, Jr.

nso4 = 55, ?zA~~S = 7 (Deen 1990); El Indio, nn2s = Nevados del Famatina, stage V alunite-kaolinite, n
11, nso4 = 3 (Jannas et al. 1990), Rodalquilar, = 1 (Losada-Calderon & McPhail 1994); the
nH2S = 44, nS04 = 1 1, nA34s = 4 (Arribas ef al. average 6D and 6’*0 values for La Mejicana (n =
1995a). Temperatures for Chinkuashih were 9) are similar to NF; K-silicate and quartz-sericite
calculated using the 34S/32S data from Folinsbee et at Nevados del Famatina have 6’*0 between 4 and
al. (1972) and more recent fractionation equations. IO”/,, reflecting a larger magmatic component
Sulfide-sulfate mineral temperatures higher than (Losada-Calderon & McPhail 1994); PV = Pueblo
350 “C were documented only at depth at Viejo: PV, = stage 1 alunite and kaolinite, PV2 =
Summitville (T = 390 “C, -900 m below the stage 2 pyrophyllite (Fig. 9 in Vennemann et al.
present surface; Rye ef al. 1990) and Lepanto (T = 1993); Ro = Rodalquilar, alunite, n = 10,
420 OC at the 700-m level, immediately above the chalcedonic ore, n = 6 (Arribas et al. 1995a); RM
FSE porphyry copper deposit; Hedenquist & = Red Mountain, Lake City, Colorado, alunite, n =
Garcia 1990). On the basis of phase equilibria, the 12 (Bove et al. 1990; Rye 1993); Su =
sulfide/sulfate values for the Pueblo Viejo stage 1 Summitville, alunite, average of n = 10 (SD) and n
and stage 2 mineralization were estimated by = 16,(S!*O) (Rye et al. 1.992); ore-fluids .from Rye
Muntean et al. (1990) to be about 3 and 35, (1993). The main ore .stage I-at .Rodalquilar (stage
respectively. 2) is based on 6’*0 of chalcedonic quartz; SD are
not available for this stage but present-day
Figure 8 groundwaters, alunite, kaolinite, and illite fluids in
6D versus ai80 variation diagram. the deposits have a limited range of 6D values,
Explanation: Go = Goldfield, hypogene alunite, n suggesting significant variations are unlikely
= 1 (Rye et al. 1992); Ju = Julcani, alunite (n = 6), (Arribas et al. 1995a). Stage 2 (pyrophyllite)
JUI = average of main-stage ore fluids in f l u i d s f o r P u e b l o Viejo i n v o l v e s e v e r a l
wolframite, enargite, tetrahedrite, and galena fluid assumptions with respect to the choice of
inclusions, Ju2 = average of main-stage ore fluids fractionation factors for oxygen and hydrogen,
in sphalerite and chalcopytite, Jus = late-stage ore The data for stage 2 at Rodalquilar and Pueblo
fluids in barite, siderite, and botroidal pyrite (Deen Viejo should be viewed as approximate. Data for a
1990); Le = Lepanto, alunite, n = 2 (Y. Matsuhisa single alunite for Goldfield (Rye et al. 1992)
& J. Hedenquist, unpub. data); Nansatsu district: suggest that mixing of a the SD- and 6’*0-
Ka = Kasuga, alunite. n = 1, Iw = Iwato, alunite n enriched magmatic fluid with isoto ically light
?8
= 2, a’*0 values of residual vuggy silica waters may result in D- and O-depleted
associated with ore in both depositsfall between hydrothermal acid-sulfate fluids (see also Vikre
Ka and Iw (Hedenquist ef al. 1994a); NF = 1989).

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