Chapter l9

CHARACTERTSTICSOF HIGH.SULFIDATION EPITHERMAL

DEPOSITS,AND THEIR RELATTONTO MAGMATIC FLUID

Antonio Arribas Jr.

Mineral ResourcesDepartment, Geological Survey of Japan,
l-l-3 Higashi, Tsukuba305, Japan

[NTRODUCTIoN includingsilica sinter-depositinghot springsand

steam-heated acid-sulfatealteration.
A consequenceof the increasedexplorationfor The main objective of this review is to
gold depositsduring the Iate 1970s and early summarize the characteristicsof HS minerali-
1980s was tlre revision of the classificationof zation formed primarily within the epithermal
epithermaldeposits in order to account for the environment,tlroughrecognizingthe potentialfor
variationsobservedin stylesof mineralizationand HS conditionsto occur at greaterdepths.Earlier
inferred genetic environments. Among the studies have argued for a magmatic fluid
numerousclassificationsthat followed, one group componentin HS deposits(e.g., Sillitoe 1983,
of deposits clearly showed a common set of 1989, 1991a;Hayba et al. 1985; Henley t99t
features,this deposittype is characterized by the White 1991;Rye 1993;Hedenquistet al. 1994a),
presence of minerals diagnostic of high- and the identificationand characterization of HS
sulfidationstates(e.g.,enargiteand luzonite)and depositshas contributedto a re-evaluationof the
acidic hydrothermal conditions (e.g., alunite, role of magmatic fluids in other types of
kaolinite, pyrophyllite). The terms enargite-gold hydrothermalsystems(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 aftention is
1986), quartz-aluniteAu (Berger 1986), acid- given to the characteristicsthat are helpful in
sulfate (Heald et crl. 1987), and alunite-kaolinite determiningthe nature of the magmatic contri-
(Berger & Henley 1989) were applied to this bution to the hydrothermalsystem through time
group in referenceto someof its mineralogicalor and space.This review considersfeaturesof many
inferred geoclremicalattributes.The term high- of the depositslisted in Table l, with locations
sulfidation(HS) (Hedenquist1987)is now widely shown in Figure 1, but is basedon a selectionof
used;the term was proposedoriginally to refer to fourteendepositsfor which the resultsof detailed
a fundamental genetic aspect, the relatively geologicaland geochemicalstudiesare available
oxidized state of sulfur contained in the (Tables 2, and 3). For simplification,biblio-
hydrothermalsystem(i.e., initially SO2-rich).This graphic referencesare not given in the text for
aspectis significantbecauseit links HS deposits generaldeposit features;these referencesmay be
with one of the two main types of terrestrial found in Table 1. For regional studies of HS
magma-relatedhydrothermalsystems(Henley & deposits,particularlywith respectto othertypesof
Ellis 1983), those associatedwith andesitic magmatic-hydrothermal base-and precious-metal
volcanoeswhose surface manifestationincludes deposits,the reader is referred to reviews by
high-temperaturefumaroles and acid sulfate- Heald et ul. (1987), Bonham (1989), Sillitoe
chloridehot springsand crater lakes.By contrast, (1989, l99la), Berger& Bonham(1990),Camus
Iow-sulfidation deposits form from neutral-pH, (1990),White & Hedenquisr(1990),Mitchell &
reduced(H2S-rich)hydrothermalfluids similar to Leach (1991), Mitchell (1992), and White et al.
thoseencounteredin geothermalsystems(Henley ( I 99s).
& Ellis 1983), with surface manifestation
 7-

A. Arribas../r.

Table l. Principal high-sulfidation deposits or documcnted prospects ordered geographically

N'in
t;ig. I Deposit References
Asia & Australasia
I Dobroyde,Australia W h i t e e t a l .( 1 9 9 - 5 )
2 RhyoliteCreek,Australia R a e t z& P a n i n g t o n( 1 9 8 8 )
3 Temora,Australia Thompsonet ul. (1986)
1 P e a kH i l l , A u s t r a l i a C o r d e r y( 1 9 8 6 ) H , a r b o n( 1 9 8 8 ) M , a s t e r m a (n1 9 9 4 )
5 M t . K a s i ,F i j i Turner( 1986)
6 Wafi River,PapuaNew Guinea I - e a c h& E r c e g( 1 9 9 0 ) E , r c e ge t u l . ( 1 9 9 1 )
1 Nena,PapuaNew Guinea A s a m i & B r i t t e n( 1 9 8 0 )H , a l le r a l ( 1 9 9 0 )
d Motomboto,Indonesia P e r e l l 6( 1 9 9 4 )
9 N a l e s b i t i uP
r ,h i l i p p i n e s S i l l i t o ee t u l . ( 1 9 9 0 )
l0 Lepanto,Philippines G o n z a l e z( l 9 - 5 9 )C , a r c i a( 1 9 9 1 )A , r r i b a se r a / . ( 1 9 9 - 5 b )
ll Chinkuashih,Taiwan H u a n g( 1 9 5 . 5 )H , w a n g & M e y e r ( 1 9 8 2 )T , rn etul. (1993)
t2 Zi.jinshan,China Zhang er ul. (1991)
l-) Seongsan & Ogmaesan, SouthKorea Y o o n( 1 9 9 4 )
l4 Nansatsu(lwato, Akeshi& Kasuga),Japan Izawa& Cunningham( 1989),Hedenquistet ul. (l994tt)
l-5 Yoji, Japan Yui&Matsueda(19921)
-feine,
l6 Japan Ito(1969)
t1 Akaiwa, Japan A k a m a t s u& Y u i ( 1 9 9 2 ) ,A k a m a r s u( 1 9 9 3 )
l8 Mitsumori-Nukeishi, Japan Aoki & Watanabe(1995)
North & CentralAmerica
la NorthwestemVancouverIsland,Canada Panteleyev& Koyanagi(1994)
20 Summitville, Colorado S t e v e n& R a t t 6( 1 9 6 0 ) ,S t o f f r e g e (n1 9 8 7 ) R , y e( 1 9 9 3 )
2l Red Mtn-LakeCity, Colorado B o v e e / c 1 .( 1 9 9 0 ) R , y e( 1 9 9 3 )
22 Red Mtn-Sil verton,Coloradcr Burbank(1941),FisherandLeedy(1973)
L-) Goldfield, Nevada R a n s o m e( 1 9 0 7 ,1 9 0 9 ) A , s h l e y( 1 9 1 1 ) ,V i k r e ( 1 9 8 9 )
24 ParadisePeak, Nevada J o h n e r u l . ( 1 9 9 1 ) ,
S i l l i t o e& L o r s o n( 1 9 9 4 )
PuebloViejo, DominicanRepublic Munteanet ul. (1990),Russell& Kesler( l99l )
26 M u l a t o s ,M e x i c o Staude(1994)
SouthAmerica
21 Julcani,Peru P e t e r s eenr u l . ( 1 9 1 1 ) D , e e n( 1 9 9 0 ) R , ye(1993)
28 Castrovirreyna,Peru V i d a l & C e d i l l o ( 1 9 8 8 )
29 Ccarhuarso,Peru Vidal er a1.( 1989)
30 SanJuande Lucanas,Peru V i d a l & C e d i l l o( 1 9 8 8 )
3l Cerro de Pasco,Peru G r a t o n& B o w d i t c h( 1 9 3 6 ) E , i n a u d (i 1 9 1 1 )
Colquijirca,Peru Vidal et ri1.( 1984)
.1.') Sucuitambo,Peru V i d a l & C e d i l l o( 1 9 8 8 )
34 Laurani,Bolivia Murillo et al. (1993)
3-5 Choquelimpie,Chile Gri'ipperet ul. (1991)
36 Guanaco,Chile P u i g e t a / . ( 1 9 8 8 ) ,C u i t i f l oe t a i . ( 1 9 8 8 )
E l H u e s o ,C h i l e S i l l i t o e( 1 9 9 1 a )
38 Esperanza,Chile V i l a ( 1 9 9 1 )M , o s c o s oe t a l . ( 1 9 9 3 )C , u i t i f r oe t u l . ( 1 9 9 4 )
39 La Coipa,Chile Oviedoet ul. (1991),Cecioni& Dick (1992)
40 Nevada& Sancarr6n,Chile Siddeley& Araneda(1990)
4l El Indio-Tambo,Chile Siddeley& Araneda(1986),Jannaser ul. (1990)
42 La Mejicana-Nevados del Famatina,
Argentina Losada-Calderon & McPhail ( 1994)
Europe
43 Rodalquilar,Sparn Szinger-von Oepenera1.(1989),Arribaset ul. (l995tr)
44 Furtei-Serrenti.Sardinia Ruggieri( l993a,b)
A< Spahievo,Bulgaria Velinov er al. (1990)
46 Chelopech,Bulgaria B o g d a n o v( 1 9 8 2 ,1 9 8 6 )
41 WestemSrednogorieregion,Bulgaria Bogdanov(1982),Velinov & Kanazirski( 1990)
48 Bor, Yugoslavia Jankovicet ul. (1980),Jankovic( 1982)
49 Lah6ca,Hungary B a k s a( 1 9 7 5 ,1 9 8 6 )F, i r s t( 1 9 9 3 )
50 Enisen. Sweden Hallberg (1994)

420
 H igh-sulfidation Epithermal Deposits

q9.:Balkans
\ ,--<+s-+s

prospects.The main high-

Figure l. Worldwide distributionof high-sulfidationdepositsand principaldocumented
and references.
selected
suifidationmetallogenicprovincesare indicated.SeeTable I for depositnames

REMARKSON GENETIC
OPSNTNC advanced argillic zones that commonly cap
ENVIRONMENT porphyrycoppersystems(e.g.,Sillitoe 1973;Corrt
1975; Gustafson& Hunt 1975; Koukharsky &
Basedon detailedresearchof the Summiwille Mirre 1976;Wallace1979).lndeed, severalof the
Au-Cu-Ag deposit, Stoffregen (1987) demon- depositsconsideredin this review are underlainby
strated that a nearly ubiquitous feature of HS porphyry-type mineralization (Table 2). Tliis
deposits, fracture-controlledvuggy silica rock advancedargillic assemblageis also typical of
(intensely leached volcanic rock consisting that associated with acidic crater lakesatop active
dominantly of quartz; Fig. 2) is the product of volcanoes (Christenson & Wood 1993;Delmelle
: -250 "C)
very acidic conditions(pH <2 at T that & Bernard 1994; Rowe 1994; Hedenquistthis
occur within a sulfate-rich hydrothermal fluid volume).
formed by absorption of magmatic vapor' In The implicationsof a geneticrelationbetween
addition to SOz disproportionation to H2SOa, porphyryand epithermalmineralization,e.g', with
significant concentration of HCI from the respectto the origin of metalsor the natureof the
magmatic vapor contributes to the acidic fluid inclusions in HS deposits, are discussed
conditions necessaryfor alumina to be soluble, below. The observationmade here is that an
leading to vuggy silica alteration(Hedenquist e/ alunite-enargiteassemblagerecords a similar
al. 1994a,b).Neutralizationof the acidic solution geochemicalenvironment,whether forming arl
by reactionwith the wallrock resultsin a sequence epithermal deposit or as part of the alteration
of alteration zones, oufward from the zoning of an orebody formed at greater depths.
hydrothermal conduit, which is indicative of High-sulfidation deposits forrn in a position
decreasingacidity and is defined by the presence intermediatebetween intrusions and the surface;
of alunite,kaolinite, illite, and montmorillonite + therefore,they may be locatedclose to a porphyry
chlorite(Steven& Ratte 19601'Fig.2). copperdepositor in a near-surfaceenvironment,
This same alteration sequence' without the suchas the rootsofan acid craterlake.
vuggy silica zone but with enargite-bearing ores, Comprehensive genetic models for HS
was documentedin the Butte polymetallicdeposit depositshave been proposedonly recently (e.8.'
(Meyer et al. 1968) and in the roots of the Berger& Henley1989;Sillitoe1989;White l99l;

421
A. Arribas, Jr.

Table 2. Main geologicalcharacteristicsof l4 selectedhigh-sulfidationepithermal deposits

Time
Deposit/disrict. Age Metals. Local volcanic Principal host Genetically betwecn host
location {Ma) ( t o n n e s I) setting roc Ks rclated rtxks rock & deposit Dcposit li)rm

Motomboto. 1.9 C u .A u . A g Central-vcnt Dac donr, zrnds/dac/rhy Dioritic. qtz- < 1 . 0n r . y . Hbx . vcins.dis in
Indonesia 6 0 , 0 0 0 t C u . 4 t volcanir l-1ows.pyr and volx dioritic stocks VS
Au. t80r Ag (c)
Nalesbitin. Pliocene Au Small cenral- Ands pyr + llows None observed N/A Hbx. vcinlcts
P h i ii p p i n c s l5 t Au(c) vent volcano
Lcpanto. I . 5 -I . 2 C u .A u .A g Diatreme Ands/dac vol. Qtz{iorite <analyl.error Vcrtical brcccilrs,
P hi l i p p i n c s 900.(100 r Cu. complex Mioccnc + older porphyry ( 1 0 . 1m . y . ) vcins. slralab0urd
1 2 0r A u ( c ) volx + metavol replacenrnls
C h i nk u a s h i h . 1 . . 1 - 1 . 0 A u . C u .A g Dome complex Dac volc "letl{cs
Dacite domes Vcins or .
kiwu 9 2 t A u . 1 8 3r A g Mioccnc sed md llows hhx,dis and stk
120.000r Cu (p) sunounding veins
Ziiinshan. -94 Cu. Au Domc akrng Jurassicgranite. Not reported 7 . 0r n . y .l () Vcins. hbx. stk
China >t0 r Au (c) caldcra m:trgin'l Cretaceous dac (PoorlYrJatul)
porpyhry +pyr
Nansatsu, 5-J.-s Snrall volcanos Ands pyr. llows + Horblende :rrds <0.5 nry Dis in stratatrountl
Japiur l t l r A u ( p ) + l 8 r in a c:rldrra'i v o lx (Middlc Volcs) VS/MS bodies.
Au reserves v c i n s .h b x
S u n r n r i nl l l c . 22..5 Au, Cu.Ag Dome along ''hdgcs"
Qtz-latite porphyry Qtz-monzonite <analyl.error with
Color:rdo 1 7t A u preexrstlnS porphyry (10.-5 m.y.) v c i n s .h b x + d i s
c:ildera margin in VS

Goldlicld. 2l Au (Ag. Cu) Domes along Miocene andesitc "[.cdges"

Andesitc <analyl. crror with
Ncvadir l -10t Au. t 4.1 Ag. preexisting ring (t0.,1 m.y.) v e i n s .h h x + d i s
-17.000 Cu (p) fracrue in MS

ParatliscPcak. lg-lti Au, Ag. Hg Within or close Compositc welded tulf. And/dac vol <analyt. crror Stratabourrrl
btxlics
Nevai:r 47 t Au, 12-55Ag to a central-vcnt volx + ands f'lows (+1.0n).y.) commonly with
457 r Hg (p) volcano hbx
P u eb l o V i e j o . -l-l(.) Au. Ag Mzurdiatreme Mau sed + basaltic CA bimodal N/A Mushrtxrnrshapcd
D o n r i n i c a nR c p . >600 I Au (p; complex vol (spilitc ) (Rhy + basalr) bodics with stk +
Sillitoe. 199.1) volcanic suite dls
Julcani, g.lt Ag. Cu. Pb. Au. Dome complcx Dac to rhyodacitic Dac/rhyulacitic <analyr.crror Vcins
Peru W, Bi. Zn around a cenual domes and tuft.s porphyry (+0. I m.y.)
dlareme
El Indio, ll-tt Au. Ag. Cu Stratovolcano('?) Dac. rhy pyr; CA vol N/A Veins + stk
Chile -140 t Au. in cirlier caldera dac + ands vol
-1.100r Ag (c)
La Mejicana & Ne- 4.0 -1.6 Cu. Au, Ag Dome complex( l) Paleozoic seds + Dac/rhyrxlactic <1.2 nr.y. Veins;alsohbx at
v a d o sd e l F a n i a t i n a . >lll5 t Au (c) granitcs. Pliocene porphyry N. dcl Famtina
Argcntlna illtrusivc dacite stocks
RrxJ:rJtluilu. I l-10 Au Caldera margin Ands to rhy pyr flows. Ands flows <analyt. error Vcins.hbx. dis in
Spain 10 t Au (p) collapse bxs + domes + dykes (+0.7 m.y.) VS

Abbrcviations used: CA : calc-alkaline, MS - massive silica, VS : vuggy silica, ands : andesitic, bre : breccias, dac - dacitic, dis =
disseminations,hbx = hydrothermalvein breccia or brecciapipes, pyr - pyroclastics,qtz = quartz,rhy : rhyolitic, sed: sedimentaryrock, stk
- stockwork, vol : volcanic rock (unspecifled),volx : volcaniclastics
I 2
1p; : produced, (c) : estimaled total contained Approximate number, quoted from paper or estimatedfiom ligures: 150 nr lbr Paradisc
P e a ki s f b r i n d i v i d u a lo r e b o d i e s

Giggenbach1992a;Rye 1993; Hedenquistet al. and the pressure and temperature gradients". This
"direct
1994a).However,the basicgeneticcontrols,as we concept formed the basis for Ransome's
understandthem now, were formulated almost volcanic hypothesis", though it was quickly
"simultaneous
ninety yearsago by Ransome(1907)following his abandonedin favor of a solfatarism
classicstudy of the Goldfield Au-Ag-Cu deposit. and oxidation" model (Ransome 1909). The
"the change in genetic interpretationhas more than
In his own words [ore depositingJsolutions
were essentially emanations from ct solidifuing anecdotalvalue becauseit illustratesthe sourceof
" "
body rf dacitic magma and . . the initially acid a not-uncommonmisconceptionon the environ-
emonqtionswould be neutralizedand modified in ment of mineralizationof epithermaldeposits.
their ctscent through fissured rock. .by the The crucial aspect is identification of the
distance emd kind o.f rock traversed, the quantiQ origin of alunite or acid-sulfatealteration,which
and characler of admixed surface-derived waters, can be generatedby differentmechanismsin three

422
 H igh-sulfidalion Epithermal Deposits

Table 2 (continued)

Vertical ext-
Dcposit/district ent of epiri. Relation to
locatlon Control on mineralization ore (m)2 porphyry systen) Relerences

Motomhoto. Contact bctwcen dome and 250 Porphyry Cu-Au Pcrcll6 ( I 994)
lndurcsia volcmic Krk. steep lault prospectsnearby. age
within 1.0 m.y.
Nalcshitan. Stecp strike-slip lault 150 hoposcd, Sillitoe ?r a/. ( I 990)
Phi lippi nes none lo)owr)
Lcpanto. Major steep + minor faults. 500 Above + adjaccnt Garcia ( l99l ),
Phi li ppi ncs diatrcn)econtact.unc0mlor samc age porynyry Anihas et a/. ( I 995b)
mrty, permeable layers Cu-Au dcposit
C h i n l u a s hi h , Stecp normal laults + 800 Nonc k-nown H u a n g( 1 9 5 5 ) ,
Taiw;rrr thcir intcrscctions, Tan et al. (1993)
bedding plancs
Ziiinshan. Steep srike-slip fault 60()(') None known Rcn er a/. ( 1992),
China zones + contact 0f Zhang et ul. (1994)
volcztntcvent
Nansatsu. Stecp lractures+ permeable <150 None known Izawa & Cunningham ( I 9fl9).
Japiut pyroclastic layers Hedentluist et al. \1991a)

Sunrmrtville. Steep rldial fracturcs+ 250 Inrusion-ccncred S t e v e n& R a t t i ( 1 9 6 0 ) .M e n h c r l

Colorado dtxnc contact scricitic, low grade et al. (19'73). Stoffregen ( I 987 ).
stk mineralization Rye (199,j)Gray& Coolbaugh
( 1994)
Goldlrcld. Modcratcly + shallow 400 Nonc lnown R a n s o m c( 1 9 0 9 ) ,A s h l e y ( 1 9 7 4 ) .
Nevalir dipping faults & fissures A s h l c y & S i l b e r m a n( 1 9 7 6 ) .
V i k c ( 1 9 8 9 .w r i t t e nc o n r m u n .
I 995)
ParadiscPcak. Stccp Iaults antl permeable < 150 Sericitic. stk Au J o h n ? / a / . ( 1 9 9 1) .
Nev:da pyroclastic layers minerahzation (East Sillitoe& Lorson (1994)
Zone)
P u c h l oV i e . j o . Diatreme rinq fault + 4UXt) Ntne l*rown R u s s e l l& K e s l e r ( 1 9 9 1) .
D o n ) i n i c a nR c p . permcablelayers Muntean et a1.( I990)

Julcani. Steep liactures 600 None klown PeterseneI al. (19'11\.

Pcru N o h l e & S i l b e r m a n( 1 9 8 , + ) .
Dccn ( I 990)
El lndio. Stccp normal faults >l(x) Porphyry Cu-Mo Siddcley & Araneda( 1986).
Chile mineralization Jannasel a1. ( 1990)
nearby
La Me.jic:na & Ne- LOcal I aults HS ore il Nevado del Losurda-Calder(xr & McPhail
vadosdcl Fantatina Famatina is a pirt of a ( I 994). Losada-Caldcr6nel a/.
AJScntlna porphyry Cu prospect { I 994)
Rrxllrit1uiIar. Caldera ring faults + <150 Nrne Lrown Anibas e/ d/. ( I 995a)
Spaitr nornral local faults

principal geologic environments(Bethke 1984; zunyite,which are typical of hypogene(T : 200-

Rye el al. 1992):(l ) by the disproportionation
magmatic SOz to H2SO4 and HzS
absorption by groundwater (magmatic-
hydrothermal),(2) by atmosphericoxidation of
H2S in the vadose zone over the water table,
associatedwith fumarolic discharge of vapor
releasedby deeperboiling fluids (steam-heated),
and (3) by atmospheric oxidation of sulfides
during weathering (supergene). Magmatic-
hydrothermalaluniteoccurswith mir-rerals
diaspore, p y r o p h y l l i t e ,k a o l i n i t e ,d i c k i t e ,a n d
of 350 "C) acidic conditions (advanced argillic
following assemblage; Meyer & Hemley 1961).This type of
aluniteis characteristic of HS deposits,but it may
also appearin areasof advancedargillic alteration
void of ore mineralization(e.g., Iwao 1962; Flall
1978). Alunite in steam-heatedenvironments
forms with kaolinite and interlayered illite-
smectiteat about 100 to 160 'C where fumarolic
vapor condensesabove the boiling zone of
suchas neutral-pH,H2S-richfluid, typical of geothermal
s y s t e m st h a t f o r m l o w - s u l f i d a t i o nd e p o s i t s .

423
A. Arribcts,,Ir.

Quartz alunite
Leached
Propylitic Argillic + Adv. argillic silicic

, I
'100
m
Kaolinitic Mineralizedvuggy
rock rock rock rock quartz rocl(
1
Figure 2. Cross-sectionof alteration zones characteristicof high-sulfidationdeposits,as observed at the
Summitville Au-Cu deposit,Colorado.Diagram at left (simplifiedfrom Steven& Ratte 1960) shows schematic
outwardzonationfrom a subverticalmineralizedbody, shownat right (from Stoffregren1987).

Becauseof the relatively shallow and dynamic Proterozoic EnAsenAu deposit located in the
environment of mineralization, overprinting Baltic shield of central Sweden; Fig. I ). The
among the three types of acid-sulfatealteration youngestdepositsare Pleistocene (<1.6 Ma) and
(including sLrpergene) 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 concentrationof
different, and correct identificationis important depositsin young volcanic areas is mainly a
for exploration (Rye et al. 1992:. White &. reflectionof the fact that older HS depositsare
H e d e n q u i s1t9 9 5 ) . more likely to be eroded.
Gold. copper,and variablearnountsof silver
DISTRIBUTION, AGE ANDECONOI\{IC are the main productsof HS deposits(Table 2).
StcNInrcaNcB Gold (Nalesbitan, Rodalquilar), occasionallywith
silica by-product(Nansatsu),is the only economic
In common with other magmatic- metal in the smaller deposits.No copper is
lrydrothermal deposits (e.g., porphyry copper produced at Paradise Peak and Pueblo Viejo.
deposits),HS depositscoincideworldwide with Mercury is producedat ParadisePeak, and the
plutonic-volcanicarcs. This associationis best Julcanidistrict has beena sourceof a remarkable
observedin the Cenozoicdepositsof the Circurn- polymetallicassemblage consistirrg of Ag, Cu, Pb,
Pacificand the Balkanbelt of southeastern Europe Au, W, Bi, and Zn (Table 2). The six largest
(F-ig I ). These deposits occur in two main deposits or districts (Chinkuashih,El Indio,
settings:in islandarcs and at continentalmargins. Goldfield, La Coipa, Lepanto,arrd Pueblo Viejo)
The tectonic regime during formation of the eachcontainsmore than about 100tonnesof gold.
deposits seems to be dominantly extensional The economic potential of this type of
(Sillitoe 1993). Some deposits(e.g., Goldfield, mineralizationis clear in regions such as the
Rodalquilar, Summitville) formed in intra- C h i l e a nA n d e s( S i l l i t o e1 9 9 1 a ) .
continentalregionsduring periodsof extensiotl
that followed regional compression and sub- VoLCANIcSITTTnCANDASSOCIATED
ductiorrby several m.y. IGNEOUS ROCKS
Tertiary HS depositspredominate,and only a
few deposits are Mesozoic (e.g., Pueblo Viejo, The high-sulfidationdeposits consideredin
Zijinshan),Paleozoic(e.g., Temora and othersin Table 2 occur within intennediate-composition
southeastern Australia),or PreCambrian(the early volcanic rock sequenceshaving ages broadly

\
/t '
*t"'""
50 60 70
SiO2 (wt"/")
Na - Nansatsu,PP : ParadisePeak,Ro : Rodalquilar,Su - Summitville.Compositionalfields afrerKeith et al.
( 199l). SeeAppendixfbr references
and informationon dataplotted.
similarto that of mineralization. Whereabundant
radiometricagesare available,the age of the host
rocks and the age of mineralizationare within
analytical precision: where a difference is
indicated,it is typicallylessthan-1.0 m.y. (Table
2). A comrnon spatial associationexists between
the depositsand shallow. typically porphyritic
intrusions.Theseintrusionsare interpreted to be
the roots of volcanic domes or the feeders of
central-ventvolcanoes or maar-diatrernecom-
plexes,the three rnain volcanic settingsfor HS
deposits(1'able 2). Some depositsare hosted
entirelywithin a single dome (Summitville),or
within a dornecomplex (Julcani).In most cases
tfre mineralizationextendsfrorn the subvolcanic
intrusion into country rocks, such as the Main
Vein Cu-ALr-Agdeposit and associatedbreccia
depositsin the Penshanarea of the Chinkuashih
district.Somedeposits,however,do not showany
(known) spatial associationwith subvolcanic
intrusionsthought to be geneticallyrelatedto
mineralization (e.g.,Nalesbitan.
Nansatsu). In the
Rodalquilar Au deposit, dykes and small
intrusions of hornblende andesite which are
interpreted to be temporally related to the
mineralizationreprcsentonly a fraction of the
altered and mineralized area exposed at the
presentdepthof erosion;a largerintrusivebody is
H ig h-sulfi dat ion Ep i t her ma I Deposi ts
Figure 3. K2O versusSiO, variationdiagram
for rocks thoughtto be geneticallyrelatedto
high-sulfidationdeposits.The samplesfrom
12 depositsor districts (r : 140) define a
small compositionalfield, which contrasts
sharply with the large field defined by
volcanic rocks associated rvith low-
sulfidationor intrusion-related Au deposits
ca\c.,^ ( > 1 0 0 s a m p l e sf r o m l 6 d i s t r i c t s ;S i l l i t o e
3\Katt" 1 9 9 1 b ,1 9 9 3 ;M r i l l e r & G r o v e s 1 9 9 3 ) .T h e
degreeof alterationof the rock samplesand
precisionof the analyticaldata are Iargely
unknown; however, according to the
individualdata sources,most of the samples
are unalteredor very weakly altered.Circles
indicate average values for each high-
sulfidation deposit or district: Ch
C h i n k u a s h i h ,C q = C h o q u e l i m p i e ,G o -
G o l d f i e l d ,I n : E l I n d i o .J u : J u l c a n i .L a
L a u r a n i ,L e : L e p a n t o ,M o - M o t o m b o t o ,
tlroughtto exist at depth (Arrrbas et al. 1995a).
The main controlon locationof mineralization at
Rodalquilaris the structuralrnarginof two nested,
resurgent calderas. With the exception of
Rodalquilar,the role of calderasin the formation
of HS depositsseemsto be lirnitedto facilitating
the emplacementof late intrusive magrna along
preexistingcaldera ring-fractures(Rytuba cl rzl.
1990).
The magmasthoughtto be geneticallyrelated
to HS deposits have a remarkably limited
compositionalvariation.The rangesof wt.% K2O
and SiO2 for twelve depositsoverlap greatly and
show a dominanceof calc-alkalineandesiticand
dacitic compositions,with subordinaterhyolite
(Fig. 3). Intermediatecalcic volcanic rocks are
limited to porphyritic intrusionsin the Lepanto
and Motomboto Cu-Au-Ag districts, and
intermediate-to-felsicalkali-calcic rocks are
characteristicof the Summitville and Laurani
districts(Fig. 3). Interestingly,
no depositshave
been discoveredin associationwith alkaline or
mafic magmas,eventhoughthesemagmascan be
genetically related to low-sulfidation and
intrusion-related Au deposits (Sillitoe 1991b,
1993; Miiller &. Groves 1993; Richards this
volume). The data shown in Figure 3 suggesta
relation exists betweenInagma cornpositionand
A Arribas, Jr.

Table 3. Main alteration and mineralizationcharacteristicsof 14 selectedhigh-sutfidation

epithermal deposits

Lateralalterationzoning Vertical altcration ( )re

(outwardfrom nrinem- zonin-9 mineralization
Dcposit lizcd txxlies) (shallow t() dccp) Pnncialore nrinerals rn: Ag/Au

Motonlboto VS ,qr-alu |qt7-kao ) VS,MS rqtz-alurqtz- Py. ena-luz,mzu.sph.gal. tcn- Silicacorc 35--15
k a o - s m cr i l l - c h l kao rill-kao lchl lct. ars.cpy. arg. nat.Au.tcll

Nalcsbitan SilicificdHbx rqtz-kao- SilicificdHbx )qL.-kx> Py. chalc.qtz, cco. hor. cov. Silicacorc Vcry
alu rill-sme-chl-cal alu rill-sme-cbl-cal ena. tell Io* As

Lcpanto VS/MS , tz-alu-kaor MS/VS rAA ISER r Ena-luz, py. ten-tet. cpy. p_v-..e lc. Silic:r corc
kao-qtz-illrchl-ill ( K-silicatein subiacent sph. gal. nrar. sele. tell. Sn-
FSEporphyrycopper) bearing sull'
Chinkuashih VS,MS rtltz-alu-kaor py. ena-luz. f :rm. tcn-tet. nal.Au. Silica corc
ill-chl-kao elc. hu. nat.Hg. tcll. splr.grl.
cpv. geo. hou
Zijrnshar VSA4S tqtz-dic-alut9?- VSA4S rqu-dic-alu r90- py. dig. ena.cov. nrol. nat.Au Silicacorc N/A
dic-\er rqtz-Scr dic_Sor)qU_ser cpy. hor. tet-ten. gal. sph

N:ursaLsu VSA4S ralu-dic-pyo' VS/h4Sralu 'dic-ser- e n a - l u z .p 1 ' .c l c . n a t . A u . a r g . S i l i c uc o r e <2

ill-kao-smct p Y ) s e r - c h lt P R o plr. cpy. bor. sph. gal. cas. stir
PRO n)()1. can
Sunrnritville V S ( M S ) t q t z - a i u -t vs(MS) ,qrz_kao_ py. cna-luz. c()v. mar. nat.S. Silicaeorc 2-10
qu-kao 'kao-ill I x l u r q t z - k a or S E R nat.Au. sph. gal. bar. cpy. ten
snrc-chl
Goltllicld M S ( V S ) r q r z - : r l u - k aro MS>VS .qr1__alu- py. lam. ten-tet. bls. gol, Siliclrcore <|
ill-smc I kao |q?-klolpyo nat.Au. cna-luz. bru. tell. sph.
PRO cov
Pu'irdiscPeak Vertical(dueto deF)sit M S ( V S )) q l z - a l u - k ( ) bar. stb. his. nat.Au. nrnr. pl. S i l i c uc u r e 10-30
: S ( V S )|
s t y l c )M (SERin laulted.deeper('l) nat.S. cin, sph. gal, cpy. ars.
q?-alu-kaorsme-chl EastZonedeposit) tet. arg, cov. f:ul
P u e h l oV r e j o Conrplex+ overprinted Early:Kao-py-qu r py. sph. cna. nal.Au. nal.S. b2rr. InAA+ 7
du-py<ltz tcn-tet. fan. gal. bar. stb. cle. MS zoncs
L a r e :M S r p y o _ d i a selc, tcll, Bi- Pb- Ag- sull'
Julcuri pre<rrc:VS/MS)qtz_alu- py. wol. c:rs. nat.Au. ena. lur. Vcins .170
kart rqtz-kao:Syn<rre: tel tcn. cpy. gal. sph. biu. sid.
qtz-pyo-pyrqu- kao-py+ Pb- Bi- Ag-bearing sull'
q?-siir-py lq(Z-kao-smc
El Indrr Cu stageveins rkao-alu- Ena. py. tel, nat.Au. ten. cp-y. Vcins
scr-qU:Au stagc gal. sph. hue. hor. dig. cnrp.
vcins rser-kao-pyrt-q? cco. nlar. Dar.
La Mcjicaua. Alu-kto rqu-scr )(K-sil pV. cna. cpy. Splr, ten-lct. cov. S i l i c uc o r e 10-10
Nevrdrx drl icatc in N. del Farnatina cco. lam, luz. nat.Au. gal. nlol
Fiunatina porphyrycopper) ele. tell, col. Sn-Bi-Ph-Ag-sull
Rulalquilar VS,MS rqtz-aiu-kaor VSMS rqtz-alu-kaor Py, nat.Au. cna. tell. cas. col. Silicacore <I
qtz-kao-ill r ill-sme-chl qtz-kao-sel qt !-ser-py cov, dig. bor, gal. sph. Bi- sult

A b b r e v i a t i o n su s c d :A A : a d v a n c e da r g i l l i c ,H b x - h y d r o t h e r m abl r c c c i a ,M S : m a s s i v es i l i c a , P R O - P r o p y l i t i c .S I J I { :
s e r i c i t i c ,V S - v u g g y s i l i c a , V S ( M S ) = v u g g y s i l i c a d o m i n a n t ,a l u - a l u n i t e , a r s : a r s e n o y r i t eb, a r - b a r i t c . b i s :
b i s m u t h i n i t eb , o r = b o r n i t e ,b o u - b o u r n o n i t ec, a l : c a l c i t e .c c o = c h a l c o c i t ec, h a l . q t z: c h a l c e d o n yo r c h a l c e d o n i cq u a r t z ,
c h l : c h l o r i t e ,c i n = c i n n a b a r ,c a n : c a n f i e l d i t ec, a s : c a s s i t e r i t ec,o l - c o l u s i t e ,c o v : c o v e l l i t e ,c p y - c h a l c o p y r i t ed, i c :
d i c k i t e ,d i g : d i g e n i t e ,e l e : e l e c t r u m ,e m p : e m p l e c t i t e f, a m - f a m a t i n i t e( s t i b i o l u z o n i t e )g,a l : g a l c n a ,g c o - g e o c r o n i t r ,
gol : goldfielditeh , o l : m o l y b d c n i t c ,n a t . A u:
, u e - h i i b n e r i t ,e i l l : i l l i t e , k a o : k a o l i n i t e ,l u z : l u z o n i t e ,m a r : m a r c a s i t cm
n a t i v e g o l d , n a t . S: n a t i v e s u l f u r ,n a t . T e: n a t i v et e l l u r i u m ,o r o = o r p i m e n t ,p y - p y r i t e .p y o : p y r o p h y l l i t c ,q t z : q u a r t z ,
rea=realgar,sele:selenides,ser=sericite,sid-siderite,sme:smectite,sph:sphalerite,sta=stannite.stb:stibnitc,
s u l f - s u l f i d e so r s u l f b s a l t st,e l l : t e l l u r i d e st,e n : t e n n a n t i t et,e t : t e t r a h e d r i t et o , ol : wolfiamite
, u : t o u r m a l i n ew
I
B a s e do n f l u i d - i n c l u s i o n( f l i n c ) o r g e o l o g i c a (l g e o l )e v i d e n c e b; l a n k r v h e r en o t s p e c i f l e d .
'Boiling
( H b x ) - b o i l i n g d u e t o a b r u p tp r e s s u r cr e d u c t i o na - s s o c i a t ewdi t h h y d r o t h e r m abl r e c c i a t i o n
A. Arribus,Jr.

is difficult, but useful for discussion of the The depositis 3 km long and consistsof a tnain
differences among deposits and design of zone of breccia and replacementmineralization
exploration strategies.In this context, White alongthe LepantoFault(Fig. 4A). Multiple veins
(1991) distinguished three end-memberstylesof associatedwith smaller diagonal faults branch
HS deposits,namedafter deposits of the Circum- from the rnain zone and extend into both the
Pacific:Temora,El Indio, and Nansatsu.Irregular hanging wall and foot'ivall (Garcia l99l). The
bodiesof disseminated, silicifiedoresdominatein characteristicmushroom-shaped cross-sectionof
the Temora-style. Cavity-filling veins with many of the orebodiesat Lepantois relatedto the
sericiticand clay-rich haloesare characteristic of intersectionof the steeplydipping Lepanto fault
El Indio-style ALr deposits. A large group of and branch veins with the unconfonnity at the
depositsfalls into White's(1991)Nansatsu-style, base of Imbanguiladacite (Fig. aB). Lithologic
which is characterizedby wallrock-alteratiort variations in the host rocks also played an
zoning similar to that shown in Figure2, and by importantrole in the fonnation of the deposit.as
the occurrenceof enargite-bearing ores within a shown by lenses of stratiform enargite-luzotrite
silica core consistingof vuggy or massive silica ore which resultedfrom replacernentof detrital
rock (Table 3). Mineralization in this style of layers within volcaniclastic and sedirne ntary
deposit forms irregular strataboundbodies (e.g., basement units(Garcial99l ).
Nansatsu, Lepanto) or subvertical vein-like
"ledges"(e.g.,Chinkuashih, Goldfield, AITEN.ITIONMINERALOGYANDZONING
massesor
Lepanto, Rodalquilar, Summitville). These
depositscontainbrecciabodies,veins,stockworks As mentioned above, the lateral alteration
of small veins.and disseminated oresthat replace zoning that is characteristicof HS deposits
or irnpregnate intensely altered country rock' reflects the reaction and neutralizationof high-
Ericksen& Cunningham(1993)distinguished two temperature acidic fluids with wallrock. The
stylesof HS depositsin the Andeanprovince: Ag- innermost zone of vuggy or tnassive silica
and Au-rich polymetallic base-metalveins' and alterationcommonly has sharpboundarieswith a
low-gradevuggy silica and breccias;the two types zone that may contaitrquartz, alurrite,kaolinite,
are broadly comparable with El Indio- and dickite,pyrophyllite,diaspore,and zunvite'.l'his
Nansatsu-styles, resPectivelY. advancedargillic assemblage gradesinto a second
l,ocal subverticalfaults and fracturesare the envelope of argillic alteration, composed of
dominant control on HS mineralizationand they mineralssuch as quartz,kaolinite,illite, sericite,
are present in rnost deposits (Table 2). Other and smectite,and an outermosthalo of propylitic
examplesof structuralcontrolsobservedin some alteration,with chlorite. illite, smectite. and
districts arnong the foufteen selected include: carbonate(Fig. 2, Table 3). The width o1' eacl.t
rnoderatelyto shallow-dippingfaults (Goldfield)' zonevarieswidely; for example,vuggy silicaand
caldera ring and radial faults (Rodalquilar),the advancedargillically altered rock fonn narrow
dilationaljog of a strike-slipfault (Nalesbitan), (<70 cm) vein selvagesat Julcatri(Deen 1990)'
diatremering-faults(Lepanto,Pueblo Viejo), the but form wide (>50 m) rock bodiesat Sumrnitville
contactbetweena dome or volcanic conduit and or Lepanto (Figs. 2 and 4). Late-stage',cavity-
country rock (Motomboto, the Missionary filling planarveins at Julcaniand E,l Indio may
orebody at Summitville), and a lithologic extendoutsidethe zoneof alunite-kaolinite' ln the
unconfbrmity(PuebloViejo, Lepanto).In threeof majority of HS however,
deposits, most of the ore
the fburteen deposits, the principal control is is containedwithin the silica core, inside the
lithological(maarsediments at PuebloViejo, and advanced argillicenvelope('Iable3).
interbeddedpyroclastic layers at ParadisePeak
and Nansatsu;Table 2).
lln
A unique cornbinationof the structuraland Russian and eastern IJuropcan tcrrninology lhcse rtlcks are
'metasomatic quartzites" with nrorc specilic
conrmonly termcd
lithologicalcontrolscharacteristicof HS deposits names such as porous quartzites, diasporc quartzitcs' alunite
is exhibitedby the LepantoCu-Au-Ag deposit. q u a r t z i t e sa, n d d i c k i t eq u a r t z i t e s( e . g . .V c l i n o v e t u l . 1 9 9 0 ) r '
 High-sulfidation Epithermal Deposits

@
NW

Figure 4. Longitudinal(A) and transverse(B) cross-sections

of the Lepanto-FSECu-Au-Ag deposits(phitippines),
showingstructuraland lithologic controlson formationof the high-sulfidationand porphyry-typeores (simplified
from Garcia l99l ). Potassium-argon
datingof countryrocksand alterationmineralsassociatedwith the porphyryand
depositsindicatesthat hydrothermalCu-Au mineralizationtook placein the middle of a plioceneto
high-sulfidation
Pleistoceneevent of dacitic-andesiticmagmatism(Arribas et al. 1995b).Note the overall spatial overlap of the
magmaticand hydrothermal"plumbing" systems(i.e., volcanic vents of Pliocenedacite,quartz diorite intrusions.
porphyrydeposit,and deeperpartsof epithermalmineralization).

The zonesof alterationwith increasingdepth
typically grade from a shallow silicic zone
through advanced argillic, argillic, argillic/
sericitic, into a sericitic or phyllic zone with
quartz, sericite, and pyrite. This alteration
sequenceoccurs over a vertical interval that
rangesfrom a few hundredmetersto more than
1000 m, and has been best documentedby deep
drillholesin the depositsof smallersize,in which
the vertical span of rnineralizationis less than
about300 m (e.9.,Rodalquilar,Summitville;Fig.
5B). At Lepanto,sericitic alterationat depthsof
400 to 500 m below the epithermaldepositgives
way, laterally towards the south, to K-silicate
alteration of the FSE porphyry Cu-Au deposit.
Porphyry-type stockwork mineralization at
ParadisePeakis containedwithin the sericiticores
of the East Zone deposit which, according to
Sillitoe & Lorson (1994), formed underneaththe
main HS orebodiesirr the area.A quartz-sericite-
pyrite zonewith traceamountsof chalcopyriteand
molybdenitesurroundsan intrusionof monzonite
porphyry >300 m below the HS deposit at
Summitville(Grav& Coolbaush1994\.
The lateral and vertical alteration zones
described above correspond to a generalized
model. They are useful in exploration because
they help in understandingthe genetic environ-
ment of a depositand provide spatial "markers"
within the extinct hydrothermal system.
Experimental data on the relative stability of
rnineralssuch as alunite, kaolinite, pyropliyllite,
and diaspore(Hemley et al. 1969, 1980),coupled
with the temperaturerangesnoted for these and
other related acid minerals in active systems
(Reyes 1990; Reyes et al. 1993), also provide
informationthat contributesto definition of the
paleoconduitsin extinctsystems.
If studied in detailed, several superimposed
and crosscuttingstagesof pervasiveas well as
fracture (conduit)-relatedmineralizationmay be
recognizedin the majority of deposits.Theseare
the expectedresultofvariations,during the course
of mineralization,in temperature,pressure,and
compositionof the hydrothermalfluid and the
degreeof wallrock interaction.Detailedfield and
petrographicstudiesat the Monte Negro orebody
in the Pueblo Vieio deposit have resulted in
A. Arribas, .Jr.

IKM

I Vuggysilica
Advancedargillic
ffi
l ^ ^ a
Argillic
f-'-^l Sricitic
tl Propylitic
m Inlensesupergeneacij-sulfateovsrprint
Au-(Cu-Te-Sn) htgh-
@ sulfidation deposits

-100
500m I
Elsvation(m) |

Figure 5. Generalizedsurfacealterationmap (A) and cross-section (B) of the Rodalquilar

HS depositin the Rodalquilarand Lomilla calderas, southeastern Spain (fiom Arribas e/
at. 1995a).The boundariesshown between alterationzones are irregular and gradational.

identification of two stages of mineralization, particularfeaturesof the depositslisted in Table

interpretedto correspondto two distinctmagmatic 3. Pyrite and enargite (and its low-temperature
pulses (Muntean et al. 1990). During the first dimorph luzonite)are the dominantsulfidesin HS
stage (responsiblefor -600/o of the Au in the deposits;pyrite is abundantbut the amount of
and deep
deposit),shallow kaolinite-quartz-pyrite enargite and luzonite is variable. Common ore
alunite-quartz-pyrite-quartz zones were de-minerals, listed by decreasingabundancefrom
veloped,with gold mineralization in variable to very minor, include tennantite-
association
with disseminatedpyrite in the wallrock; during tetrahedrite,covellite, native gold and argentian
the secondstage(responsiblefor about40% ofthe gold (electrum), marcasite,chalcopyrite, spha-
lerite, and galena.Famatiniteis locally abundant
Au), an extensivezoneof silicificationwith pyrite
+ sphalerite+ errargiteveins formed at shallow in somedeposits(Goldfield,La Mejicana).Sparse
levels. above a zone of pyrophyllite-diaspore ore mineralsincludebornite,cassiterite,ctnnabar,
alteration(Munteanet al. 1990). molybdenite, orpiment, realgar, stibnite, and
wolframite (the last locally importantat Julcani).
Ono aNu GANGUEMINERAL0GY'AND Other minerals present in minor amounts in
TIMINGOFMINERALIZATION severaldepositsinclude Pb-, Ag-Pb, Bi- and Sn-
bearingsulfbsalts(Table3).
White et ul. (1995)and White & Hedenquist Fine-grainedquartzis the dominantganguein
(1995) presenteddetaileddiscussionson various HS deposits.Other comrnon but minor gangue
aspectsof epithermalgold mineralizationon the minerals include barite, kaolinite, alunite,
basis of observationsfrom a large number of pyrophyllite,diaspore,and Ca-,Sr-,Pb- and REE-
depositsaroundthe Pacific;theirconclusions with bearing phosphate-sulfatemineral(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-suffidationEpithermalDeposits

vein specimensfrom Chinkuashih,Goldfield,and of these data with geologicaland mineralogical

La Mejicanahave spectacularintergrowthsof ore observationsmentionedabove allows the nature
mineralswith 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 inconsistentwith transport sition and fluxes of volcanicdischargesand active
of Au as a bisulfide complex (Seward 1973). magmatic-hydrothermal systems (Hedenquist&
Recent studies of Au solubility in high- Lowenstern 1994; Giggenbach this volume;
temperature acid sulfide solutionshaveresultedin Hedenquistthis volume).
identificationof AuHS" as one of the principal
gold complexesin HS mineralization (Bening& F I uid-in cI usion Ev idence
Seward 1994), the other possibility being AuCl2 Suitablehosts for fluid-inclusion studiesare
(e.g.,Hedenquiste/ al. 1994a). scarcein HS deposits,as the ganguemineralsare
The number and order of mineralizingevents typically fine-grainedand even millimeter-size
providecritical informationfor reconstructionof hydrothermalquartzcrystalsare usually late stage
the hydrothermal system that results in HS and vug-filling. Satisfactoryresults are obtained
mineralization.A minimum of two stagesof on secondaryfluid-inclusionsin igneous quartz
alteration/mineralization has been recognizedin phenocrysts from altered wallrocks; although
most deposits on the basis of crosscutting lacking temporal information, these inclusions
relations(Table 3). The most common evolution seemto provide a representative cross-sectionof
is from an early leachingand alterationstageto a the fluids involved.The most reliabledata on the
laterore-formingstage.Vuggy silica rock and the ore-formingfluids are obtainedthrough infrared
advancedargillic assemblagewith disseminated microscopy directly on ore minerals, such as
pyrite form typically early-stageacidic alteration, enargite (Deen 1990; Mancano & Campbell
and are followed by Cu + Au + Ag deposition. 1ee5).
Detailedstudiesin some districts(e.g.,El Indio, The temperaturesand salinitiesestimatedfor
HS depositsdefinea wide range,from 90o to 480
Lepanto),however,have resultedin identification
oC and <l to 45 equiv.wt.% NaCl, respectively
of two metal stages,an early Cu-rich, Au-poor
stage,dominatedby enargite-luzonite, (Table 4). There is no systematicdifference in
and a late
Au-rich, Cu-poor stage, associated with salinity among Au-, and Ag- or base-metal-rich
intermediate-sulfidation-state deposits, in contrast to that noted for low-
sulfides such as
tennantite-tetrahedriteand chalcopyrite, and sulfidationAu versusAg deposits(Hedenquist&
Henley 1985). Large variations in both
tellurides. The transition from quartz-alunite-
I
I temperatureand salinityalso occur within a single
pyrite alterationto enargite-pyriteand finally to
!
tennantite-tetrahedrite, deposit; these reflect the dynamic environment,
the last typically without
with high- and low-temperatureand high- and
sulfate (alunite) but with quartz-sericitegangue
and wallrock alteration, indicates a fluid low-salinityfluids interactingduring the courseof
progressivelymore reduced and less acid. At mineralization. Four broad groups of hydro-
Summitvilleand Chinkuashih(also Tambo and thermalfluids are recognizedhere on the basisof
the estimated temperaturesand interpretations
Furtei-Serrenti;Table l), a late stage of barite-
gold hasbeendocumented. given by most workers. The temperature
boundaries chosen for each group are only
CsaRactnRISTICS ANDSoURCESoF indicative,as significant variations exist among
HvuRorsnRMAL FI-utos and within deposits; each group, however,
providesrelevantinformationon various genetic
Resultsof recentdetailedfluid-inclusionand aspects.
"C)
stable-isotopicstudies reveal much about the Group 1. Higher temperature(e.g., >300
composition, temperature and sources of fluids of variable salinity, which have been
hydrothermalfluids in HS deposits"Combination documentedin severaldepositsand are generally

431
A. Arribas, Jr.

Table 4. Summary of fluid-inclusionmicrothermometricdata for high-sulfidationdeposits

Host-mineral Tcmpcrature Salinity Asstriatcd

Deposit studicd ("C)t (cquivwt.%NaCl) altcration

Mrxoniboto, Indoncsia Barite 150-180 <l Atusil

N a l c s b i t a n ,P h i l i p p i n e s Quartz 22(J-260 AA/sil
L c p a n t o ,P h i l i p p i n e s Enargitc t](\-290 0.24.5 AA/sil

C h i n k u a s h i h ,T a i w a n Quartz, baritc. I8{).330 o.2-t2

alunite
a 1 a
Z i . l i n s h a n .C h i n a Qu:rtz (no dctails I 6(f-3(X)
rcfx)rtcd) 220 380 3 ,t 9 Scr
l 0(I- 160 0-5 sir
(300-+20) (3-2( ))
N a n s a t s uJ, a p a n Quartz 13(l250 <l AA/sil
-210 up to 30 AA/sil
25F310 Scr
Akaiwa, Japan DiasJnre I 9(I-240 AAisil
Mitsumori-Nukeishi, Japan Quartz. ba-ritc, 2I(I 330 0.5-1.1
quanz pnen(x
S u n i m i t v i l l e ,C o l o r a d o Quartz phcnoc l8(}_280 2-18 AA/sil

(300-390) (upto 9)
Baritc - t(x)
Coldlielcl,Nevada Quartz-phenoc 230-480+ 5 1 8 AAisil
Quartz, baritc 2I (),280 0.2-8 AAisil
(37(H10)
Pradise Peak, Nevada Quartz, barite r80-2I0 <3 AA/sil
Quartz 300,380 3[r35 Ser
(upto 4-50)
Julclni, Peru Quartz phenrr I 60-280 \ ) 4 AAisil
Quartz phenoc 36045t) 38,46
Wol, ena, quartz 230-330 920
Sidcritc 220,250 6-9
Ccarhuaraso, Peru Quartz phenoc 330-380 7 18 AA/sil
Colqui.jirca,Peru Qufiz phcnoc 23(f,260 .+-ll AA-/sil
Can-Can (La Coipa), l7(I 350 < l-40 AA/sil
Chilc donrinant
El Indio, Chile Sphalcritc. quartz I 90-280 0 .l 4 AA"/Ser
hiibnerite i4(}-l80 0.t-2.1
Quartz phenoc (>3(n) (upto 27)
La Mejicana (LM) and N/A 2(XI'+60 t 3 l AA + scr
Ncvados Famatina(NF), l6(i-340 0 . 3 , 12
Argentina 230-480 341 Scr

Rrxlalquilar,Spain Quartz, quartz 17F300 230 AA/sil

phcnm 22(}.450 245 Ser

Furtei-Serrenti,ltaly Quartz,barite, I 9(),320 0.4-23 AA/sil

quartzphentr 9(I 140 0.4-I .6
(390-5m) (32 45)
Ahbreviations used: AA = advanccdargillic, ena = enargite,phenoc = phenocrysts,ser =
sericitic, sil = silicicl wol = wolfiamite: see Tablc J for rraleoderrthestimations
I r e m ; ^ * r a t u r c , a r c r ( ) u n d e d l ( ) t i c n c i r c s tl t ) " : h r a e k c i s u s c d t o i n d r c a t c t u g h - t c n r p c r a t u r r .
inclusions typically interpretedis having formcd early or being anomalous

"anomalous"or unrelatedto ore and entrapment cannot account for all the high 17,
interpretedas
are associated with early stages of alteration. values.The consistentpresenceof thesefluids in
Two-phase entrapment may explain some of the several deposits indicates a high temperature
unusuallyhigh homogenizationtemperatures (4), gradient,and implies the presenceof a shallow-
particularly considering the shallow minerali- depth intrusion,and possibly lithostaticconfining
zation depth inferred for many of the deposits pressures.On the basisof fluid-inclusion,as well
(Table 3). However,most workersagreethat such as isotopic (634Srrrrut.-rurna")
temperatures(see

432
 H igh-sulfdation Epithermal Deposits

Table 4. (continued)

Dcposit Commcnls Rcl'crcnccs

M ( ) t o r n b o t o I, n d o n c s i a Rcconnaisanccsrudy in latc-stagcbarite Percll6( I 99:l)

n * a l c s b i l a nP. h i l i p p i n c s Reconnaissancc studyi liquid CO2 observcd Sillitm el rr1.(1990)
L c p a n t o ,P h i l i p p r n c s Samplcd intcrval 3 knl long by 0.5 kn hieh t ctnling tluitls Mancano & Campbell (1995),
awav fionr subjaccntporphyry Cu-Au degrsit, whcrc Garcia(1991)
Th >.150'C & salinity up to 5.1eq wt.rl NaCl
C h i n k u a s h i h .T a i w a n P r x r r l y - d o c u m e n t esda m p l e sa l o n g a ' 1 5 ( l n r v e r t i c a li n t c r v a l : Folinsbeeet trl.(.1912).Ycn
the highcr Ths in sanples lt -7,50 m dcpth: CO2 ohserved ( 1976),Tanet uL.(.1991)
Z i . j i n s h a nC
, hina Asstrciatcdwith main stagc Cu Zhanger al. (1991)
Dorrpaltcration zonc (>6(X) nr depth)
Associatcd with late. shallow silica-Au
Assrriated with carly silica and quartz-dickite
N a n s a t s uJ, l p a n Late, vug-lilling quirtz et ul. (1991.t)
Hcdcnquist
Qtz in brcccia. salrneliquid and krw-salimty vapor cmxist
Vein quartz -4(X) m helow Kasuga deposit
A k a i w a ,J a p a n Coarsc-grainedclilsgrre Akamatsu& Yui (1992)
M i t s u m o r i- N u k e : i s h iJ, a p a n Not (known) Au or Cu mincralization, but high salinity Aoki & Watanabc(199-5)
lluids
S ur n m i t v il l c . C o l o r a t i o L i c l u i t l - r i c h :s a l i n i t y > 6 e q w l . 7 N a C l o n l y i n v u g g y s i l i c a Bruha& Noblc( 1983),R.
associatedwith Cu mineralization: CO2 obscrvcd Stoflicgcn(written
Lrquid- and vapor-rich inclusions: also polyphaseinclusions c o m m u n .1, 9 9 4 )
Latc barite-Au assemblagc Cunningham (1985)
ColtlliekI, Ncvatla Truc T5 is interpretedto be 25(1290"C Bruha& Noble(1983)
Hydrostatic and ncar-lithostaticprcssuressuggested Vikre( 1989)

PiiraclisePcrk, Ncvatla Latc, vug-lilling crystals in hydrothermal brcccia: J o h ne t a 1 (. 1 9 9 1 )

Frorn stockwork Au East Zonc dcoosit: COr observed Sillitoe& Lorson(l99tl)

J u l c a n i ,P c r u Quaru-alunitetpyrite Bruha&Noble(198.1)
Pro-oretourmalinc brcccia dykes, lithostatic pressureslikely. Shclnutt& Noble(1985)
Main-stagc orc fluicls, also inner veins, liquid-rich inclusions Dccn ( 1990)
Latc-stageore fluids, also in outcr vcinsl P correction applied Deen( 1990)
Ccrrhuaraso, Pcru Quartz-alunitctpyrite Bruha&Noble(l9ti3)
C o l c l u i l i r c aP
, cru Quartz-al u ni tetpyrite Bruha& Nohlc(198.1)
C a n - C a n( L a C o i p a ) . Two generationsidcntillcdl both may be very salinc. Evidcncc Townley( 1991)
Chile firr P abovc hydrostatic and higher salinities at dcplh
El Indiu, Chilc Coppcr and gold stages Jannaser a/. ( I 99(l)
Late stage
Interprctcd as carly, with vapor-rich inclusions,CO2 observetl
La Mc.jicana(LM) and LM & NF. includes liquid-, vapxrr-richand potyphasc inclusions Losada-Calder6n
& McPhail
Ncvacirs Famatina(NF), NF: complctc transiLionliom porphyry-type fluids in K- ( l 994)
Argcntina silicatc stage (30(),6(X)+"C, up to 67 eq wtq, NaCl)
through sercitic to epithcrmal f'luids in HS (AA) stage;
vapor-rich inclusions typically less saline
Rrxlalquilu, Spain Vcrtical temperature and salinity gradient: high-lcmperature Sdnger-von Oepenat a/. ( I 989),
brines coexist with low -;Llinity vapor inclusions: Arribis et al. (1995a)
hydrostatic and near-lithostatic pressuressuggested
Furtci-Scrrcnti, Italy Includes hi-eh+ low-salinity fluids (22-23, <6 eq wt% NaCl) Ruggieri( I 993b)
Latc stagc

below), pressuresabove hydrostatichave been <1 to -18 equiv. wt.% NaCl. With the possible
suggestedfor severaldeposits,including Julcani exceptionof depositsfor which only the late-stage
(Shelnutt& Noble 1985),Goldfield(Vikre 1989), mineralshavebeenstudied,thesetypically liquid-
Summitville(Rye 1993),and Rodalquilar (Arribas rich inclusionsare found in all deposits.Main-
et al. 1995a). stageore fluids are containedwithin this group.
Group 2. Intermediate-temperature fluids The temperatures measuredin fluid inclusionsin
(e.g.. 180-330"C), with salinitiesvariablefrom enargiteat Lepanto(Mancano& Campbell 1955)

433
A. Arribas,Jr.

and Julcani (Deen 1990) are broadly similar, but Temperature("C)

their salinitiesare distinctly different (0.2-4.5 200 300 400
equiv.wt.% NaCl versus8-18 equiv.wt.% NaCl,
respectively),providing constraintson the role of H2O+5wf/.NaCl

a saline magmatic liquid (versus Iow-salinity

vapor) in the generationof HS deposits.
Group 3. Lower temperature(e.g., 90-180
"C), dilute (typically <5 equiv. wt.yo NaCl)
liquids; these have been documentedin a few o
0)
deposits associatedwith late-stage(e.9., Au-
q)
barite)mineralization.The late-stageore fluids at dno 6-'
(g

Julcani are hotter (220-250 oC; Deen 1990) and o

(s
slightlymore saline(6-9 equiv.wt.% NaCl), than 3
theseaverages,but no correlationamong the late q)

stagesin differentdepositsis attemptedhere. A

"Sericitic" fluids. As mentioned
Group ./.
above,sericitic(quartz-sericite-pyrite)
is the most
common alteration assemblageobserved below
the ore zone in some HS deposits.Although
detailed documentation is lacking for many
deposits,higher temperaturesand higher salinity
fluid-inclusionsseemto characterizethe sericitic
zone with respect to the shallower zones of
alteration(Table 4). For example,at Rodalquilar
(Arribas et al. 1995a), documentation of tem-
perature and salinity along a >600-m vertical
interval(extending500 m below the ore zone;Fig.
6) shows a gradient which correlateswith the
change in dominant alteration,from silicic and
advancedargillicQ : 170-300oC,salinity:2-15
equiv. wt.% NaCl at the elevationof the orebody) point curves,and vertical spansof the alterationzones
to sericitic(T: 220-450oC,salinity:2-45 equiv.
wt.% NaCl) assemblages.
The transition from advancedargillic alteration,
through quartz-sericite-pyrite, to K-silicate
alteration and typical porphyry-type high-
temperature(600+ "C) and high-salinity(up to 67
equiv. wt.% NaCl) fluids of magmaticorigin is
displayed,among the examplesreviewed,at the
Lepanto-FSE and La Mejicana-Nevados del and 4, above).Thesefluids may be the result of
Famatina epithermal-porphyrycopper systems. boiling of a high-temperature
The cooler and less saline inclusion fluids
documentedin the ore zoneof the HS depositsare
interpretedto reflect mixing of magmatic and
meteoricfluids in an environmentshallowerthan
that of porphyry mineralization.Furthermore,in
common with porphyry-type deposits, high-
temperature, vapor-rich. low-salinity fluid
inclusionscoexist with high-temperature, liquid- sulfidesand sulfates,in additionto the possibility
- -n' n o;
a,
E
q)
o
Figure 6. Elevation versus temperature diagram
showing the range (horizontal line) and average
(vertical line) of fluid-inclusion homogenization
temperatures measuredin the RodalquilarAu deposit,
Spain.Also shown are the temperatures calculated,on
the basis of 63aSsurfide-surrare
for four coexisting alunite-
pyrite samples(large filled circles),referenceboiling-
mentioned in the text. Estimated salinities of fluid
inclusionsin the shallowadvancedargillic/siliciczone
and deep sericiticzone range between2 to 30 equiv.
wt.% NaCl and 2 to 45 equiv.wt.% NaCl, respectively
(modified from Arribas et al. 1995a).
rich hypersalineinclusions(i.e., with Groups 1
liquid, or they may
reflect immiscible vapor and hypersalineliquid
derived directly from shallow-emplacedmagma
(Rye 1993; Hedenquist & Lowenstern 1994
Shinohara1994;Hedenquist this volume).
Sulfur-is otope Ev iden ce
The abundanceof coexisting hydrothermal

434
rt H igh-sulfidation Epithermal Depos its

I -Sultides - * Sulfates^ V& V= 634515

aSSHzs-sor

l Temp.("C)' H2S/SO4

t Lepanto

Chinkuashih
--F

'1-
r
I
V p0 - 420

20 -270
2-6

It Nansatsu

Summitville - l i
- t vI
! v @
l r f f i
t
I
l
200 - 240
200- 390 4

F
I
Goldfield --.--* r s z I
200- 350
r J I
PuebloViejo
Y ry 180- 260
I Julcani - l v 210- 270
I

i El Indio -; o
I

:.
a Rodalquilar r
t - ' l
Y l
@"f"
I 220- 330 5
t l I
'(minerat
pairs)
10 20
6345(%",CDT)

!-igure 7. Range of 63o5(per mil) values for sulfidesand sulfatesfrom nine high-
sulfidationdeposits.Also shown are the valuescalculatedfor 5'oS for total sulfur in the
hydrothermal system (triangles), H2S/SO4.and the range of temperaturesdetermined
from sulfide-sulfate mineral pairs. Solid triangles indicatedepositsin which 6toS* was
calculated on the basis of isotopic analysesof samples of unaltered whole rock
genetically related to mineralization. See Appendix for referencesand information on
dataplotted.

'oS/"S
of measuring in host rock and genetically 63aSvaluesof pyrite and enargitefrom the same
related igneousrock (Sasaki et al. 1919),allows vein, these values indicate drastic changes in
sulfur-isotopestudiesto provide information on H2S/SO4during the course of mineralization
the composition,temperature,and sulfur sources (similar to those for the Red Mountain alunite
of the hydrothermalfluids. The resultsof detailed deposit;Bove et al. 1990;Rye 1993).
studies in nine HS districts show a remarkable The main conclusionsof the sulfur-isotope
consistency (Fig. 7). In agreement with the studies in HS deposits are: ( I ) sulfur in the
observations in active volcanic-hydrothermal depositsis magmatic,but the magmatic sulfur is
systems(e.g.,Kiyosu & Kurahashi1983),sulfide overall heavierthan mantlevalues(from 63aS: 2
and sulfate minerals are mainly in isotopic + 2 o l o o aS
t u m m i f v i l l et o
, 9 + 2 o / n o a tR o d a l q u i l a r ;
'oS/1'S
equilibrium, and, therefore,their overall Fig. 7). This is not surprising given the most
depends.onthe temperatureof mineralizationand common geological setting of the deposits;
'"S/"S
the of total sulfur in the hydrothermal isotopicallyheavy igneoussulfur is common in
system. Only the data for alunite from the volcanic arc environments(e.g., Ueda & Sakai
Campanavein in El Indio (Fig. 7) are different.If 1984). (2) A simple mass-balance calculation
the measuredEl Indio alunites are not steam- 3oS/"S
done in severaldepositsusing the values
heatedor supergene(unlikely as they containfine- 'oS/"S
of the igneous rocks and the average
grainedpyrite; Jannaset al. 1990),the most likely values of sulfides and sulfates indicates that
"magmatic-steam"(Rye et al.
explanation is a H2S/SO4in the hydrothermalfluids was generally
1992)origin, in which the 63aSof aluniteis close about4 * 2 (Fig. 7; Rye et al. 1992;Hedenquistel
to the compositionof total sulfur in the system ctl. 1994a; Arribas et al. 1995a). This is a
(e.g.,Alunite Ridge in Marysvale;Cunninghamel minimum value for ore-formingfluids becauseit
al. 1984: Rve el al. 1992\ . Combined with the appliesmainly to the early stageof hydrothermal

43s
 ./r.
.4..4rrihns.

alteration.which is characterized bv a sulfate-rich lack of post-depositional effectsthat disturbthe

alunite-pyrite assemblage (3) lsotopic equilib- stable-isotope systematics. and (4) the availability
rium between sulfide and sr-rlfate in the of detailed information on the isotopic
hydrothermal solutionsresults,in a nrajorityof the compositionof fluids in active geothermaland
deposits.in reliabletemperatures calculated on the volcanic-hvdrothermal systems. which allows
basis on A3aSrr:s-so+ (Fig 7). Pyrite-alunite fluids estimatedin HS depositsto be compared
rnineral pairs were used most commonly, and with thosein theiractiveequivalents.
'fhese
rvheresamplingrvith depth is available,thev shorv Some limitationsstill exist. rnay be
oC over200-m rndependent of obviousfactorssuch as sampling
a thermalgradient:e.g.,220to 330
clevationat Rodalquilar(Arribas et al. 1995a). or mineral-preparation procedures(fundamental
200 to 390 "C over .--900m at S'.tmmitville(R1'e for achievingrepresentativc and reliableresults).
1993)1220 to 420 'C over 500 m at l-epanto analyticalimprecision.and naturalvariations,as
(Hedenquistand Carcia 1990: J \\r. Hedenquist. observedin activesystems(c.g.,Aoki 1991,1992,
unpr-rb.data). Other mineral prirs used with Rowe 1994).Importantlimitationsthat rnust be
consistent results include p1'rite-barite(Vikre taken into accourrtfor optimum use of the stable-
1989: Deen 1990),sphalerite-barite (Venncmann isotope data are related to ( l ) the choice of
et al. 1993),and plrite-g1'psurn (Vikre 1989).The temperatureof mineral formatiott fbr calculation
rangeof isotopictemperalures is consistentlvith of the lluid isotopiccomposition.(2) thc lack of
temperaturesestimatedfrom fluid inerlusions and mineral-water lractionation factors for some
alterationmineralogy (e.g., Flemley' et ul. 1980; minerals (e.g, pyrophyllite), and (3) the
Reyes 1990;Rey'eset ul. 1993).l-he rangeis also disagreement among fractionation constants
consistent with formation of altrnite at proposedlbr evencommonmineralssuchas illite
temperatures belorv-400 "C, rvhenSO2gas starts (see Dilles er a/. 1992, for a discussion)and
to dispropottionatein the h1'drothermalsolution kaolinite. For examole.at 200 oC there is a
(Sakai& Matsubaya1911;, Bethke1984). difference of -20" lno between tlte D/lI fiac-
tionationconstantsfor kaolinite - water as given
Oxygen- and Hydrogen-isotope Evidence by Marumo et al. (1980) on the basisof samples
In terms of oxygett and hydrogen isotopic of mineralsand rvaterfrom activesystems,and by
composition,the fluids that form HS depositsare t,iu & Epstein(1984)on the basisof experimental
arguably some of the better documentedand results. For these reasons.discussionof the
understoodin ore-depositstudies.This situation sourcesof water during acidic alteratiorrin the
contrastssharply witli that of a decadeago, at depositsconsideredhere is basedon the average
which time no data were availableto corroborate of the data collected for alunite, for which
the affinity suggestedbetween fluids in active fractionationfactors are well-known (Stoffregen
volcanic-hydrothermalsystemsand HS deposits et al. 1994).The magmatic-hydrothermal alunite
(e.g.,Healdet al. 1987;Hedenquist1987).Stable- typical of HS depositsgives good resultsbecause
isotope studies of HS deposits are particularly it is relatively coarse-grained (post-mineralD-H
illuminatingbecauseof: (l) the abundanceand exchange is not a problem; Stoffregen et al. 1994)
variety of oxygen-and hydrogen-bearing minerals and commonlyis closely associated with ore, thus
(e.g.,alunite,illite, kaolinite),(2) the development recordingequilibriurnconditionsof a f-luidcloser
of analytical procedures for complete stable- in compositionto the ascendingmirreralizing
isotopeanalysisof alunite,including6l8orooand solution than the kaolinite or illite from outer
alterationzones.
6'tOu' that help to distinguishthe varioustypes
Oxygen and hydrogen isotopic compositions
of alunite and associatedacid-sulfatealteration
of water in HS depositsare clearlyconsistentwith
(Rye et al. 1992; Wassermanet ctl. 1992), (3)
mixing between a high-temperaturemagmatic
fewer limitations on the interpretationof the
isotopic data becauseof the relativelyyoung age f l u i d o f 6 1 8 0 : 9 + 1 o / naon d6 D : - 3 0 + 2 0 " / o a
ond
groundwaters (Fig. 8). In part because of
of mineralizationof most HS depositsand general meteoric
F

H igh-su(idation Epithermal Depos its

n Alunite
alteration
stg. Subduction-related
Ore mineralization
stg. volcanrcvapor
Q
Alteration/
O . ^?y,
-40

3
-ou
>
a
d
t9 -eo
o
ta

-100

-tzv

-140

6180(%",sMow)

Figure 8. Summary diagram showing variation in oxygen- and hydrogen-isotope compositionof hydrothermal
fluids in high-sulfidationdeposits.The averageisotopic compositionfor the main stagesof acidic alteration
(squares)and ore-mineralization (circles)fluids are shown. Where possible,only alunite data were used for the
alterationstage(6D and 6r8O5eo); 6'tOo, is not usedbecausehydroxyl oxygenrequilibrateswith the hydrothermal
fluid during cooling (Rye et al. 1992),Tie-lines befweendata points connectsamplesfrom the same deposit.Inset
shows the isotopic composition of fields defined by waters from active geothermalsystemsand high-temperature
fumarolecondensates in subduction-related andesiticvolcanoes(from Giggenbach1992b).Go: Goldfield, Ju:
Julcani,Le- Lepanto,Nansatsudistrict: Ka - Kasuga,Iw : Iwato, NF : Nevadosdel Famatina,PV : Pueblo
Veijo, Ro : Rodalquilar,RM : Red Mountain, Lake City, Colorado, Su : Summitville. The approximate
compositionsof groundwaterssuggestedfor severaldepositsare indicatedby the intials parallel to the meteoric
water line. SeeAppendix for referencesand information on dataplotted.

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 alterationlmineralization 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 (Ju1 and Ju2), to meteoric- andesitic volcanoes (dark shaded field, Fig. 8,
water-dominated late ore-stage fluid-inclusion inset), such as Nevado del Ruiz, Satsuma
waters(Ju3).In addition to Julcani,the ore fluids Iwojima, or White Island,the last documentedto
at Summitville (Rye et al. 1990:'Rye 1993) and havea geochemicalenvironmentsimilar to that of
Rodalquilar(Arribaset al. 1995a)also have lower HS mineralization(Hedenquistet al. 1993).
6180 valuesthan those of acidic alterationfluids, The origin of the D-enrichedmagmatic(end-
indicating greater dilution by groundwater (Fig. member) fluid of HS depositshasbeeninterpreted
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 absorptionof magmatic vapors outgassingfrom
systems,is not known, but such a shift is not arc volcanoesor felsic magmasin crustalsettings
indicatedby the Julcanidata. (e.g.,Hedenquist& Aoki 1991;Matsuhisa1992;
The overall oxygen- and hydrogen-isotope Giggenbach 1992q' Vennemann et al. 1993;

437
A. Arribas, Jr.
ALTERATION
Absorptionof
high P vapor
J
uagmatic-'j
brine ll
Figure 9. Model showing the two main stagesof evolutionof HS deposits.A: Early stageof advancedargillic
alterationdominatedby magmatic vapor. B, and Bt: Two genetic hypothesesproposedfor the stage of ore
formation.B, - absorptionof high-pressure vapor by entrainmentin meteoricwater cell at depth to explain low-
salinity, mixed magmatic-meteoricore fluid (Hedenquistthis volume). B, - ascendingmetal-bearingmagmatic
brine with shallow cooler meteoricwatersto explain high-salinity,mixed magmatic-meteoricore fluid (White
I 99 I ; Rye I 993; Hedenquistet al. 1994a).
metals strongly partitionedinto the high-density
liquid (Hemley et al. 1992; Hedenquistthis
volume).
At this early intrusivestage,severalmodesof
magmadegassingmay occur which will lead to
different styles of magmatic-hydrothermal
systemswith or without associated mineralization
(Giggenbach 1992a). To form the styles of
alterationand the spatialdistributionof alteration
zones characteristicof HS deposits, degassing
must be very efficient, with oxidized high-
temperature magmatic vapor reaching shallow
depthswith little reactionwith rock or dilution by
groundwatersat greaterdepths(Fig. 9A). Dilution
with groundwatersis unlikely becausethe high
temperatures surrounding the cooling magma
cause meteoric water cells to be displacedfrom
the magma core (Fig. 9A). In addition to the
relativelylow pressureat the depth of intrusion,
effective degassing will be favored by the
structural factors characteristicof HS deposits,
such as fractured volcanic domes or roots of
domes,calderaor diatremefaults,volcanicvent
contacts. and active faults with a dilational
comporrent.
As thc high-temperatureInagmatic vapor
440
Mixing with
shallow
meteoric water
Heated \ 1
oroundwater I I
\ Ionvective
cell I
Heated
Metal-bearing
-
hypersaline /
liquid l-
groundwatet
reachesshallowdepthsof lessthan a kilometer,it
may be absorbedby groundwaterif it does not
discliarge as a fumarole. The acidity of this
groundwater-absorbed vapor condensateincreases
as the liquid cools, first at temperaturesbelow
-400 "C by disproportionationof SO2 to form
H2SO4and H2S (Day & Allen 1925; Sakai &
Matsubaya 1971), then by progressive disso-
ciation of H2SOaand HCI at lower temperatures
(<300 oC). Reactionof the increasinglyacidic
liquid with wallrock results in the upward
alteration sequence of sericite-+kaolinite*+
alunite+vuggy silica (Fig. 9,A'), the residual
vuggy silica rock resultsfrorn completeleaching
of the rock components,except silica, by a
hydrothermal solution with a pH <2 and
temperatures probably<250'C (Stoffregen1987).
The extremelyacidic conditionsmay even leadto
forrnationof dissolutioncavitiesin which the only
remnantof the host rock is a basal sedimentary
layer of quartz phenocrysts(e.g., Rodalquilar;
Arribas et ctl. 1995a).
For the quartz-alunite-pyriteassemblageof
the advanced argillic zone, the stable-isotope
evidenceis consistentwith magmaticvapor being
absorbed by meteoric waters, with tlre latter
r
$
i
l { igh-.su I/idat ion Epit hermctl Depos its

constituting a relativelvsmall part of the rnixturc- discrimination.hou'ever.can be made betweena

-l'he
(gcnerally <113, ltig. 8). fluid-inclusiorr
evidence,by contrast.is inconclusivebecauseof
the lack of ternporal infonr-ration. Nevertheless,
high-temperature, high-salinity inclusion fluids
have been interpretedto form early in most I{S
deposits(e.g., Bruha & Noble 1983: Ruggieri
l993bl Arribaset ul. 1995a).TheseflLridsrnal'be
restrictedto greater depths. as demonstratedat
Rodalquilarand in other depositswlrere high-
salinityinclr-rsion fluid is associated rviththe deep
sericiticalteration (Table 4). This latter obser-
vationsuggests an episodicasccntof high-salinity
magmaticliquid fiom the greaterdepthsof the
hydrothermal system,rvherethe hypersaline liquid
tendsto staybecause of its high density(Fig. 9A).
These nragmaticbrines rnay be rnore closely
relatedto the K-silicatealteration(and,in places.
porphyry m ineralization) that envelopes the
intrusion ( F i g .9 A ; S i l l i t o c1 9 8 9 ) .
The conditionsduring the rnain stageof ore
fbrmationare not yet as lvell-understood,and this
reflects the much rrore variable geochemical
environmentin cornparisonwith that associated
with acidic alteration.During the ore stage,the
hydrothennalliquid may bc lessdominatedby a
"sulfur-
magnraticvapor phasearrd its associated
'fhe
gas bufibr" (Giggenbach1987). presenceol-
this SO2-H2Sbufltr is the reasorrthat the early
stageof alterationis so oxidized,as reflectedby
the alunite-pyriteassernblage(Whitney 1988;
Giggenbach1992a).Instead,conditionsduringthe
ore stage f'luctuate within a range of redox
potential that is reflectcd by enargite-pyrite+
aluniteand enargite-tennantite-chalcopyrite asso-
ciations,which are relativclyhigh to intermediate
sulfidation-stateassemblages,respectively (see
Fig. 3 in Hedenquist, this volurne).tn the Lepanto
(Claveria & l'ledenquist1994) and El Indio
(Jannas et al. 1990) deposits, these two
assemblages are relatedto CLr-richand Au-rich
mineralization, respectively, with the latterbeing
of later stage in both cases.The more reduced
corrditionsare a likely consequeltce of increased
water-rock interaction, and, to some extent,
increased dilution of the oxidizedrnagrnatic fluid
by meteoricwater; this trcnd is also consistent
with the isotopic compositionof waters in tlre
main ore stageof variousdeposits(Fig. 8). No
meteoric-rvater componeutthat is incorporatedat
deep or shallorvlevels rvithin the hydrothermal
system.lmportantly.salinitiesduringthe main ore
stagecan be low (c.g.,Lepantoand El lndio. <4
equiv.rvt.oZNaCl: T'able4; or moderateto high
( J u l c a n ru,p t o l B e q u i v .w t . % N a C l ;Z i j i n s h a nu. p
'lable
t o 2 2 e q L r i vw. t . % N a C l : 4).
Assessmento.f a |lfodel
No single model adequatelyexplainsall oi
tltesevariousobservations. and severalhypotheses
have beenpropcsed.eachrellectingan emphasis
on individualdepositsor dil-ferentinterpretations
of the 1'luid-inclusion and stable-isotope data. A
basic urrderstandirrg o{' this ore-forming eur,,iron-
rnentmay be gainedby consideringthe principal
end-rnembertluid componentsand ore-forming
processes. The spectrum of characteristics
displayedby HS depositsmay be then analyzedin
the contextof sucha geneticframer,vork.
Four lluid regimeshave been iderrtifiedin the
[{S environrnent; evidencefor all is presentin the
early stageof IIS alteration,and threeof them are
critical to fbnnation of porphyry systerns(c.g.,
'Ihese
Henley & IvlcNabb1978; Sillitoe 1989).
end-membersare: (l) a metal-rich hypersalinc
rnagmaticliquid which tends to remain in the
vicinity of the intrusion,but mav ascend(or be
driven) to shallorve r depths if the ambient
ternperatureis low enough (<400 "Cl) for the
mechanical strength of the rock to increase
sLrfficientlyto resultin brittle fiacturing(F'ournier
1992),(2) a lou'-salinity'magmatic vapor whose
metal-transporting capacitydecreases sharplywith
decreasing pressure (lJedenquist this volume),(3)
heated meteoric or connate water in deep
conveclion cells that collapse inward and
downward as the intrusive stock progressively
solidifiesand cools, and (4) shallow and cool
meteoricgroundwater.
Two nrain end-member ore-forming
"volatile
hypothesesare considered.In the
transport"hypothesis(Fig. 981), the magmatic
hypersaline liquidmay remainat depththroughout
the evolutionof the hydrotherrnalsystem,and the
low-salinityvaporsare responsible for minerali-
zation (Sillitoe 1989; Vennemannet al. 1993);
deepmeteoricwater entrainmentof high-pressure

441
A. Arrihas,Jr.
vapor is required for transport of sufficient
amounts of metals (Hedenquistthis volume;
Sillitoe this volume). These conditions are
consistentwith the low salinityof the Lepantoand
El Indio fluid-inclusiondata.Mineral deposition
in this casemay be causedby mixing with cooler
groundwateror by boiling, possiblyresultingfrom
the abrupt pressure reduction associatedwith
hydrothermalbrecciation.
In the "hypersaline liquid transporl"
hypothesis(Fig. 9B2), following waning of the
rnagmatic vapor plume responsible for early
alteration,the lithostatic-pressured system frac-
tures and the metal-bearinghypersalineliquid
ascendsinto the porousleachedzone (Deen 1990;
White l99l; Rye 1993;Hedenquiste/ al. 1994a).
The dominantore-formingmechanismin this case
is rnixing of the metal-bearinghypersalineliquid
with cooler groundwatersat the site of deposition,
not at depthin the meteoricwaterconvectioncell.
This hypothesishas been proposedto explain the
high salinitiesrecordedby inclusion fluids in
severaldeposits(e.g.,Julcani).
A part of the ore-fbrming componentsmay
originate frorn leaching of wallrock, but both
hypotheses agree on a dominantly magmatic
sourcefbr metals,with an increasein the meteoric
water component with time. The principal
differencebetweenthe two hypothesesis in the
nature of the magmatic phase responsiblefor
transporting the metals into the epithermal
environment.and in the site of meteoric water
dilution. A potentialcontributorto ore fbrmation
in HS deposits involves remobilizationof the
metals by a meteoric-water-dominated hydro-
thermal system fiom a subjacent K-silicate
assemblageand porphyry-typeprotore, such as
that which may have formed closeto the intrusion
(e.g.,Brimhall 1980).This mechanism,however,
has not been suggestedas the main ore-fbrming
processin any of the depositsreviewed in this
study.
The three models for formation of HS ores.
assimilated here from the literature, are not
mutually exclusive; on the contrary, they may
occur in the same HS deposit as the magmatic-
hydrothermalsystem evolves, with complexities
arising from multiple intrusions, variations in
depth of emplacement,and changesin the local
442
tectonicand hydrodynamicenvironment.None of
the threernodelssatisfiesthe overall evidence.For
example,if metalswere suppliedonly by a dense,
high-salinityliquid, a relationwould be expected
among estimated salinities, metal associations,
and ore gradeor metal abundances of the various
deposits.Suchseemsrrotto be the case.Similarly,
if alterationand mineralizationwere solely the
result of interaction between groundwater and
low- and high-pressurevapor, respectively.high
salinitiesshouldnot be as comtnonas they
unlessthey areexplainedby localboilingof dilute
to moderately saline meteoric or seawater-
dominatedfluids.
SYNTHESIS
Gold, Cu, and Ag (and in a few exceptional
casesalso Hg, W, Bi, Pb, and Zn) are produced
from HS deposits.As a sourceof Au, and because
their mode of occurrenceand the potential to
overlie porphyry-typernineralizationhave been
widely recognizedonly within the past 10 to l5
years, HS deposits represent a valuable
exploration target that has been overlooked in
someregions.Most known HS depositsare young
in age, Tertiary and even Quaternary. High-
sulfldation deposits fbrm dominantly in
subduction-related plutonic-volcanic arcs,
'fhe
commonlyduring crustalextension. deposits
form at a depth intermediatebetweenthe surface
and shallow (few kilometersdepth) intermediate-
composition intrusions.
The intimaterelationship amongHS deposits,
volcanic host rocks, and oxidized magrnaticfluid
derivedfrom a degassing intrusionis supported by
the followingobservations: (l) the volcanicrocks
hosting HS deposits were erupted immediately
prior to mineralization, (2) the ore-fbrming
hydrothermalsystemcommonly follows the same
plumbing as that of the magmaticsystem(i.e.,
rnineralizationspatiallyassociatedwith domesor
volcanicconduits),(3) the isotopiccompositionof
hypogenesulfides(e.g., enargiteand pyrite) and
sulfates(e.g.,alunitegnd.barite) commonlycan be
'oS/"S
modelledfrom the of sull'ur in rgneous
rocks thought to be genetically related, by
equilibriumfractionationbetweenH2Sand SOain
solutionat T -200-400 oC, and (4) on the basisof

oxygen and hydrogen isotopic ratios, the waters
involvedin formationof HS depositsare identical
to waters in active volcanic-hydrothermalsys-
tems, in which the same HS geochemical
environmenthas beendocumented.
Ore formation in some HS deposits may
accompanyacidic alteration,and recentstudiesof
the hydrothermal geochemistryof Au provide
preliminary evidence that this element may be
transportedin HS and low-sulfidationsystemsas
different hydrosulfide complexes (AuHS" and
Au(HS)2, respectively;Bening & Seward 1994;
Seward1913).On the other hand,the presenceof
moderateto high salinitiesin many HS deposits.
the intimate associationwith porphyry copper-
type deposits,and the assumptionsof the most
recentgeneticmodels(transportof Au and Cu by
either hypersalineliquid or high-pressurevapor)
indicate that chloride complexes must also be
consideredfor metaltransport.
Most HS depositsevolve from an early period
of acidic wallrock alterationto a late period of
precious- and base-metalrnineralization.Acidic
alteration is characterizedby advancedargillic
assemblages and porous (leached)rock, and the
hydrothermalfluid responsiblefor this alteration
is dominatedby high-temperature magmaticvapor
I containingSO2,H2S, and HCl. Less reactiveand
oxidized fluids are typically responsiblefor ore
mineralization.Factorssuchas multiple intrusions
and opening or closing of fractures (conduits)
result in variations in the temperature,pressure,
and composition of the ascendingsolutions.
Combined with the shallow environment of
mineralization,theseconditionslead to a variety
of deposit styles (mainly replacements, breccias,
and veins) that usually occupy a limited vertical
spanof <300 to 500 m (exceptfor >800 m at the
giant Chinkuashih deposit). The geological,
mineralogical, and geochemical evidence,
particularlythe associationbetweenthe orebodies
and the lateral and vertical zones of alteration,
illustrates the basic genetic condition of HS
deposits,that a magmaticfluid interactsextensive
ly with country rock and groundwaterson its
relativelyshortpathto the earth'ssurface.
High-sulfidationEpithermalDeposits
ACKNOWLEDGMENTS
Valuableinsight on variousaspectsrelatedto
this excitingore-formingenvironmentwas gained
throughdiscussions and field work with M. Aoki,
A. ArribasSr.,C. G. Cunningham, J. Hedenquist.
W.C. Kelly, R. O. Rye, J. J. Rytuba,andT. A.
Steven. Earlier versions of this manuscript
benefited from constructive reviews by Phil
Bethke,Andrew Campbell,Anne Thompson,John
Thompson, Peter Vikre, Noel White, and Jeff
Hedenquist, who also provided abundant
documentation on HS depositsworldwide.
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Summary of data and references used to compile
Figures 3, 7, and 8.
Figure 3
K2O versusSiO2variationdiagram.The name
of lithologic units analyzed,number of sarnples
(n), and data sources are given: Chinkuashih,
daciten : 18 (Chen & Huh 1982);Choquelimpie,
Choquelimpie volcaniccomplex(5 units).n - 20
(Gropper et al. 1991: chemical data fbr the
feldspar porphyries genetically related to
mineralization are not available); Goldfield.
rhyodaciten : 6 (Ransome1909;Ashley, unpub.
analysesin Sillitoe 1993);El Indio, Cerro de las
TortolasFormation,n: 15 (Maksaevet al. 1984
in Sillitoe 1993);Julcani,daciteand rhyodacite,
n
: 10 (Petersenet al. 1917); Laurani, Laurani
vofcanicand intrusiverocks, n : 10 (Jimenezet
al. 1993); Lepanto, Imbanguila dacite and least
alteredquartzdiorite porphyry,n : 4 (A. Arribas.
unpub. data); Motomboto, porphyritic intnrsions,
n: 10 (Perell61994, and written comm. 1995):
Nansatsu, Upper Formation and hornblende
andesitein Middle Volcanicrock, n :2 (E lzawa,
written comm. 1995); ParadisePeak, averageof
Younger andesites, n : 3l (John et al. l99l);
Rodalquilar,hornblendeandesite,dacitetuff, and
rhyolite domes, n : 7 (Arribas et al. 1995a);
Summitville,Fisher quartzlatite,n: 7 (Steven&
Rattd i 960).

Y U I , S . & M A T S U E D A , H . ( 1 9 9 4 ) :S e v e r a m
l ineral Figure 7
deposits in Saku-Machi, Nagano prefecture. Rangeof 63aS1o/oo) values.Giverr below are
ResourceGeol. 44,305. the number of measurements for sulfides (nrirs),
sulfates (nso+), sulfide-sulfate mineral pairs
ZHANG, D. LI, D., ZHAO, Y., CHEN, J., LT,Z. &
(rA'oS), and references:Lepanto,flr2s: 52, n.no
ZHANC, K. (199a): The Zijinshan deposit: the
:38 (Hedenquist & Garcia1990;J. Hedenquist &
first example of quartz-alunite type epithermal
depositin the continentof China. ResourceGeol. M. Aoki, unpub. data); Chinkuashih,nvzs : 4,
^ 3 4
44.93-99. trsoo : 2, ,L"S : 2 (Folinsbee et al. 1972);
Nansatsu,nszs: 6, n soq: 9 (Hedenquistet al.
1994a);Summitville,flLts : >11, n ssa : 17,
, A t o s : 7 ( R y ee t a l . l e e b ; :c o t a n e l d .n l 1 r s : 1 6 ,
n so+:16, n63ag: 7 (Jensenet al. 1911;Vikre
1989);PuebloViejo, ngzs: 19,n s174:7,ny3aS:
4 (Vennemannet al. 1993); Julcani,n11rs: 183,

453

A. Arribas,Jr.
r?so+:55, n6345:7 (Deen 1990);El lndio, ns2s_
11, n5sa: 3 (Jannaset ol. 1990), Rodalquilar,
r , g z s : 4 4 , n s s a : l l , , A 3 a S: 4 ( A r r i b a se t a l .
1995a). Temperatures for Chinkuashih were
'oS/"S
calculatedusingthe datafrom Folinsbeee/
al. (1912)and more recentfractionationequations.
Sulfide-sulfatemineral temperatureshigher than
350 oC were documented only at depth at
Summitville (T : 390 oc, -900 m below the
presentsurface;Rye e/ al.1990) and Lepanto(I:
420 "C at the 700-m level, immediatelyabovethe
FSE porphyry copper deposit; Hedenquist &
Garcia 1990).On the basisof phaseequilibria,the
sulfide/sulfatevaluesfor the PuebloViejo stageI
and stage 2 mineralization were estimated by
Muntean et al. (1990) to be about 3 and 35,
respectively.
Figure 8
6D versus 6'80 variation diagram.
:
Explanation:Go Goldfield, hypogenealunite,n
: I (Rye et al. 1992);Ju: Julcani,alunite(n:6),
Jui average of main-stage ore fluids in
wolframite,enargite,tetrahedrite,and galenafluid
inclusions,Ju2: averageof main-stageore fluids
in sphaleriteand chalcopyrite,Ju3: late-stage ore
fluids in barite,siderite,and botroidal pyrite (Deen
1990);Le : Lepanto,alunite,n : 2 (Y. Matsuhisa
& J. Hedenquist,unpub. data);Nansatsudistrict:
Ka : Kasuga,aluniteft: 7,lw : Iwato,aluniter
2, 6r80 values of residual vuggy silica
associatedwith ore in both depositsfallbefween
K a a n d 1 w ( H e d e n q u i s te / a l . 1 9 9 4 a ) ;N F :
F
Nevadosdel Famatina,stageV alunite-kaolinite, n
I (Losada-Calderon& McPhail 1994); the
average5D and 5l80 valuesfor La Mejicana(n :
9) are similar to NF; K-silicateand quartz-sericite
at Nevadosdel Famatinahave6180between4 and
10o/oo,reflecting a larger magmatic component
(Losada-Calderon & McPhail 1994);PV : Pueblo
Viejo: PVI stageI aluniteand kaolinite,PV2 :
:
stage 2 pyrophyllite (Fig. 9 in Vennemann et al.
1993); Ro Rodalquilar, alunite, 10,
chalcedonicore,n:6 (Arribas et al. 1995a);RM
: Red Mountain,Lake City, Colorado,alunite,n :
12 (Bove et al. 1990; Rye 1993); Su
Summitville,alunite,averageof n - l0 (6D) and n
: 16 (6'80) (Rye er at. 1992),ore fluids from Rye
(1993). The main ore stageat Rodalquilar(stage
2) is basedon SltO of chalcedonicquartz;6D are
not available for this stage but present-day
groundwaters, alunite,kaolinite,and illite fluids in
the depositshave a limited range of 6D values,
suggesting significant variations are unlikely
(Arrlbas et al. 1995a). Stage 2 (pyrophyllite)
fluids for Pueblo Viejo involve several
assumptions with respect to the choice of
fractionation factors for oxygen and hydrogen.
The data for stage 2 at Rodalquilar and Pueblo
Viejo shouldbe viewed as approximate.Data for a
single alunite for Goldfield (Rye et al. 1992)
suggest that mixing of a the 6D- and 6180-
enriched magmatic fluid with isotop^icallylight
'oO-depleted
waters may result in D- and
hydrothermalacid-sulfatefluids (see also Vikre
1989).