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Chapter l9

CHARACTERTSTICS HIGH.SULFIDATION EPITHERMAL OF DEPOSITS, AND THEIR RELATTONTO MAGMATIC FLUID


Antonio Arribas Jr. Mineral ResourcesDepartment, Geological Survey of Japan, l-l-3 Higashi, Tsukuba305, Japan

includingsilica sinter-depositing springsand hot steam-heated acid-sulfate alteration. A consequence the increased of explorationfor The main objective of this review is to gold depositsduring the Iate 1970s and early summarize the characteristics HS mineraliof 1980s was tlre revision of the classificationof zation formed primarily within the epithermal epithermaldeposits in order to account for the environment, tlroughrecognizing the potentialfor variations observed stylesof mineralization in and HS conditionsto occur at greaterdepths.Earlier inferred genetic environments. Among the studies have argued for a magmatic fluid numerous classifications that 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 the by White 1991;Rye 1993;Hedenquist al. 1994a), et presence of minerals diagnostic of highand the identificationand characterization HS of sulfidationstates(e.g.,enargiteand luzonite)and depositshas contributed a re-evaluation the to of acidic hydrothermal conditions (e.g., alunite, role of magmatic fluids in other types of kaolinite, pyrophyllite). The terms enargite-gold hydrothermal (Hedenquist Lowenstern systems & (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-alunite Au (Berger 1986), acid- given to the characteristics that 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 reference someof its mineralogical to or and space. This review considers features many of inferred geoclremicalattributes.The term highof the depositslisted in Table l, with locations (HS) (Hedenquist sulfidation 1987)is now widely shown in Figure 1, but is basedon a selectionof used;the term was proposed originally to refer to fourteendeposits which the resultsof detailed for a fundamental genetic aspect, the relatively geologicaland geochemical studiesare available oxidized state of sulfur contained in the (Tables 2, and 3). For simplification,bibliohydrothermal system(i.e., initially SO2-rich). This graphic references are not given in the text for aspectis significantbecause links HS deposits generaldeposit features;these referencesmay be it with one of the two main types of terrestrial found in Table 1. For regional studies of HS magma-related hydrothermalsystems(Henley & deposits, particularly with respect othertypesof to 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)hydrothermal (1991), Mitchell (1992), and White et al. fluids similar to Leach thoseencountered geothermal (Henley ( I 99s). in systems & Ellis 1983), with surface manifestation

[NTRODUCTIoN

7-

A. Arribas../r. Table l. Principal high-sulfidation deposits or documcnted prospects ordered geographically N'in t;ig. I
I

Deposit

References

2 3 1 5 6 1
d

9 l0 ll

t2
l-)

l4 l-5 l6 t1 l8
la

20 2l 22
L-)

24 26 21 28 29 30 3l
.1.')

34 3-5 36 38 39 40 4l 42 43 44
A<

46 41 48 49 50

Asia & Australasia W h i t e e t a l .( 1 9 9 - 5 ) Dobroyde, Australia ( Raetz Panington1988) & RhyoliteCreek,Australia Thompsonet ul. (1986) Temora,Australia ( , ( , n 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( 1 9 9 4 ) P e a kH i l l , A u s t r a l i a Turner( 1986) M t . K a s i ,F i j i , I - e a c h E r c e g( 1 9 9 0 ) E r c e g t u l . ( 1 9 9 1 ) & e Wafi River,Papua New Guinea ( , A s a m i & B r i t t e n 1 9 8 0 )H a l l e r a l ( 1 9 9 0 ) Nena,Papua New Guinea ( Perell61994) Motomboto,Indonesia S i l l i t o ee t u l . ( 1 9 9 0 ) N a l e s b i t i u P,h i l i p p i n e s r ( , , e Lepanto,Philippines G o n z a l e zl 9 - 5 9 )C a r c i a( 1 9 9 1 )A r r i b a s r a / . ( 1 9 9 - 5 b ) , H u a n g( 1 9 5 . 5 ) , w a n g& M e y e r( 1 9 8 2 ) T r n e t u l . ( 1 9 9 3 ) H Taiwan Chinkuashih, Zhang er ul. (1991) Zi.jinshan, China Y o o n( 1 9 9 4 ) SouthKorea Seongsan Ogmaesan, & ( (lwato, Akeshi& Kasuga), Izawa& Cunningham 1989), Hedenquist ul. (l994tt) et Japan Nansatsu Yui&Matsueda(19921) Yoji, Japan -feine, Ito(1969) Japan ( A k a m a t s u Y u i ( 1 9 9 2 ) , k a m a r s u1 9 9 3 ) A & Akaiwa, Japan (1995) Aoki & Watanabe Japan Mitsumori-Nukeishi, North & CentralAmerica Panteleyev Koyanagi(1994) & Northwestem VancouverIsland,Canada , S t e v e n R a t t 6( 1 9 6 0 ) , t o f f r e g e ( 1 9 8 7 ) R y e ( 1 9 9 3 ) & S n Colorado Summitville, , B o v e e / c 1 .( 1 9 9 0 ) R y e ( 1 9 9 3 ) Red Mtn-LakeCity, Colorado FisherandLeedy(1973) Burbank(1941), Red Mtn-Sil verton,Coloradcr ( , R a n s o m e1 9 0 7 ,1 9 0 9 ) A s h l e y( 1 9 1 1 ) , i k r e ( 1 9 8 9 ) V Goldfield, Nevada S J o h ne r u l . ( 1 9 9 1 ) , i l l i t o e& L o r s o n( 1 9 9 4 ) Paradise Peak,Nevada Munteanet ul. (1990),Russell Kesler( l99l ) & PuebloViejo, DominicanRepublic Staude(1994) M Mulatos, exico SouthAmerica , , P e t e r s ee r u l . ( 1 9 1 1 ) D e e n( 1 9 9 0 ) R y e ( 1 9 9 3 ) n Julcani,Peru ( Vidal& Cedillo1988) Peru Castrovirreyna, Vidal er a1.( 1989) Peru Ccarhuarso, V i d a l & C e d i l l o( 1 9 8 8 ) SanJuande Lucanas,Peru ( , i 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 ( 1 9 1 1 ) & Cerro de Pasco, Vidal et ri1.( 1984) Peru Colquijirca, Peru V i d a l & C e d i l l o( 1 9 8 8 ) Sucuitambo, Murillo et al. (1993) Laurani,Bolivia et Chile Gri'ipper ul. (1991) Choquelimpie, P u i g e t a / . ( 1 9 8 8 ) , u i t i f l oe t a i . ( 1 9 8 8 ) C Chile Guanaco, ( Sillitoe1991a) El Hueso, hile C , , V i l a ( 1 9 9 1 )M o s c o s o t a l . ( 1 9 9 3 )C u i t i f r o t u l . ( 1 9 9 4 ) e e Esperanza, Chile Oviedoet ul. (1991),Cecioni& Dick (1992) La Coipa,Chile & Siddeley Araneda(1990) Nevada& Sancarr6n, Chile (1986),Jannas ul. (1990) er & Siddeley Araneda El Indio-Tambo, Chile & Famatina, Argentina Losada-Calderon McPhail ( 1994) del La Mejicana-Nevados Europe Oepenera1.(1989),Arribaset ul. (l995tr) Szinger-von Rodalquilar, Sparn Ruggieri( l993a,b) Furtei-Serrenti. Sardinia Velinov er al. (1990) Bulgaria Spahievo, ( B o g d a n o v1 9 8 2 ,1 9 8 6 ) Bulgaria Chelopech, ( (1982),Velinov & Kanazirski 1990) Bogdanov WestemSrednogorie region,Bulgaria Bor, Yugoslavia Jankovicet ul. (1980),Jankovic( 1982) ( B a k s a 1 9 7 5 , 9 8 6 )F i r s t( 1 9 9 3 ) 1 , Lah6ca,Hungary Hallberg (1994) Enisen. Sweden

420

H igh-sulfidation Epithermal Deposits

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

The main highprospects. and principaldocumented deposits of Figure l. Worldwide distribution high-sulfidation references. and selected names See are provinces indicated. Table I for deposit metallogenic suifidation

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

421

A. Arribas, Jr.

high-sulfidationepithermal deposits Table 2. Main geologicalcharacteristics l4 selected of


Deposit/disrict. location Motomboto. Indonesia Nalesbitin. P h i ii p p i n c s Lcpanto. P hi l i p p i n c s C h i nk u a s h i h . kiwu Ziiinshan. China Nansatsu, Japiur S u n r n r i nl l l c . Color:rdo Age {Ma) Metals. ( t o n n e sI ) Local volcanic setting Principal host roc Ks Genetically rclated rtxks Time betwecn host rock & deposit

Dcposit li)rm Hbx . vcins.dis in VS Hbx. vcinlcts Vcrtical brcccilrs, vcins. slralab0urd replacenrnls "letl{cs Vcins or . hhx,dis and stk sunounding veins Vcins. hbx. stk

1.9

C u .A u . A g Central-vcnt 6 0 , 0 0 0 t C u . 4 t volcanir Au. t80r Ag (c)


Small cenralvent volcano Diatreme complex

Dac donr, zrnds/dac/rhy Dioritic. qtzpyr and volx l-1ows. dioritic stocks Ands pyr + llows Ands/dac vol. Mioccnc + older volx + metavol Dac volc Mioccnc sed Jurassicgranite. Cretaceous dac porpyhry +pyr Ands pyr. llows + v o lx Qtz-latite porphyry None observed Qtz{iorite porphyry Dacite domes md llows Not reported

< 1 . 0n r . y .

Pliocene Au l5 t Au(c) I.5- .2 I C u .A u .A g 900.(100Cu. r 1 2 0r A u ( c )

N/A <analyl. error ( 1 0 . 1m . y . )

1 . . 1 - 1 . 0 A u . C u .A g Dome complex 9 2 t A u . 1 8 3r A g 120.000 Cu (p) r -94 Cu. Au Domc akrng >t0 r Au (c) caldcra m:trgin'l 5-J.-s
Snrall volcanos

7 . 0r n . y .l ( ) (Poorl rJatul) Y <0.5 nry

22..5

l t l r A u ( p ) + l 8 r in a c:rldrra'i Au reserves Au, Cu.Ag Dome along 1 7t A u preexrstlnS


c:ildera margin

Horblende :rrds (Middlc Volcs) Qtz-monzonite porphyry

<analyl.error (10.-5 m.y.)

Dis in stratatrountl VS/MS bodies. v c i n s .h b x ''hdgcs" with v c i n s .h b x + d i s in VS "[.cdges" with v e i n s .h h x + d i s in MS

Goldlicld. Ncvadir

2l

Au (Ag. Cu) Domes along l -10t Au. t 4.1 Ag. preexisting ring -17.000 Cu (p) fracrue Au, Ag. Hg 47 t Au, 12-55 Ag 457 r Hg (p) Au. Ag >600 I Au (p; Sillitoe. 199.1) Ag. Cu. Pb. Au. W, Bi. Zn Au. Ag. Cu -140 t Au. -1.100r Ag (c) Cu. Au, Ag >lll5 t Au (c) Au 10 t Au (p) Within or close to a central-vcnt volcano Mzurdiatreme complex Dome complcx around a cenual dlareme

Miocene andesitc

Andesitc

<analyl. crror (t0.,1 m.y.)

ParatliscPcak. Nevai:r P u eb l o V i e j o . D o n r i n i c a nR c p . Julcani, Peru El Indio, Chile

lg-lti

Compositc welded tulf. volx + ands f'lows Mau sed + basaltic vol (spilitc ) Dac to rhyodacitic domes and tuft.s

And/dac vol

<analyt. crror (+1.0n).y.)

Stratabourrrl btxlics commonly with hbx Mushrtxrnrshapcd bodics with stk + dls Vcins

-l-l(.)

CA bimodal N/A (Rhy + basalr) volcanic suite Dac/rhyulacitic porphyry CA vol <analyr.crror (+0. I m.y.)

g.lt

ll-tt

Stratovolcano('?) Dac. rhy pyr; in cirlier caldera dac + ands vol Dome complex( l) Paleozoic seds + granitcs. Pliocene illtrusivc dacite Ands to rhy pyr flows. collapse bxs + domes

N/A

Veins + stk

La Mejicana & Ne4.0 -1.6 v a d o sd e l F a n i a t i n a . Argcntlna RrxJ:rJtluilu. Spain I l-10

Dac/rhyrxlactic porphyry stocks Ands flows + dykes

<1.2 nr.y.

Veins;alsohbx at N. dcl Famtina Vcins.hbx. dis in VS

Caldera margin

<analyt. error (+0.7 m.y.)

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

et Giggenbach1992a;Rye 1993; Hedenquist al. as the basicgeneticcontrols, we 1994a). However, understandthem now, were formulated almost (1907)following his ninety yearsago by Ransome study of the Goldfield Au-Ag-Cu deposit. classic "the In his own words [ore depositingJsolutions were essentially emanations from ct solidifuing " " body rf dacitic magma and . . the initially acid emonqtionswould be neutralizedand modified in .by the their ctscent through fissured rock. distance emd kind o.f rock traversed, the quantiQ and characler of admixed surface-derived waters,

and the pressure and temperature gradients". This "direct concept formed the basis for Ransome's volcanic hypothesis", though it was quickly "simultaneous in solfatarism abandoned favor of a and oxidation" model (Ransome 1909). The change in genetic interpretationhas more than it value because illustrates sourceof the anecdotal on a not-uncommonmisconception the environdeposits. of ment of mineralization epithermal The crucial aspect is identification of the alteration,which origin of alunite or acid-sulfate in by can be generated differentmechanisms three

422

H igh-sulfidalion Epithermal Deposits

Table 2 (continued)
Dcposit/district locatlon Motomhoto. lndurcsia Nalcshitan. Phi lippi nes Lcpanto. Phi li ppi ncs C h i n l u a s hi h , Taiw;rrr Ziiinshan. China Nansatsu. Japiut Sunrmrtville. Colorado Vertical extent of epiri. ore (m)2 Relation to porphyry systen) Porphyry Cu-Au prospectsnearby. age within 1.0 m.y. hoposcd, none lo)owr) Above + adjaccnt samc age porynyry Cu-Au dcposit Nonc k-nown

Control on mineralization Contact bctwcen dome and volcmic Krk. steep lault Stecp strike-slip lault Major steep + minor faults. diatrcn)econtact.unc0mlor mrty, permeable layers Stecp normal laults + thcir intcrscctions, bedding plancs Steep srike-slip fault zones + contact 0f volcztntcvent Stecp lractures+ permeable pyroclastic layers Steep rldial fracturcs+ dtxnc contact

Relerences Pcrcll6 ( I 994)

250

150 500

Sillitoe ?r a/. ( I 990) Garcia ( l99l ), Anihas et a/. ( I 995b) H u a n g( 1 9 5 5 ) , Tan et al. (1993) Rcn er a/. ( 1992), Zhang et ul. (1994) Izawa & Cunningham ( I 9fl9). Hedentluist et al. \1991a) S t e v e n& R a t t i ( 1 9 6 0 ) .M e n h c r l et al. (19'7 Stoffregen ( I 987 ). 3). Rye (199,j)Gray& Coolbaugh ( 1994) R a n s o m c( 1 9 0 9 ) ,A s h l e y ( 1 9 7 4 ) . 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) J o h n ? / a / . ( 1 9 9 1) . Sillitoe& Lorson (1994) R u s s e l l& K e s l e r ( 1 9 9 1) . Muntean et a1.( I990) PeterseneI al. (19'11\. N o h l e & S i l b e r m a n( 1 9 8 , + ) . Dccn ( I 990) Siddcley & Araneda( 1986). Jannasel a1. ( 1990) Losurda-Calder(xr McPhail & ( I 994). Losada-Caldcr6n a/. el { I 994) Anibas e/ d/. ( I 995a)

800

60()(')

None known

<150

None known

250

Inrusion-ccncred scricitic, low grade stk mineralization Nonc lnown

Goldlrcld. Nevalir

Modcratcly + shallow dipping faults & fissures

400

Paradisc Pcak. Nev:da P u c h l oV i e . j o . D o n ) i n i c a nR c p . Julcani. Pcru El lndio. Chile La Me.jic:na & Nevadosdcl Fantatina AJScntlna Rrxllrit1uiIar. Spaitr

Stccp Iaults antl permeable pyroclastic layers Diatreme rinq fault + permcablelayers Steep liactures

< 150

Sericitic. stk Au minerahzation (East Zone) Ntne l*rown

4UXt)

600

None klown

Stccp normal faults

>l(x)

Porphyry Cu-Mo mineralization nearby HS ore il Nevado del Famatina is a pirt of a porphyry Cu prospect

LOcal I aults

Caldera ring faults + nornral local faults

<150

Nrne Lrown

(Bethke 1984; principal geologic environments of Rye el al. 1992):(l ) by the disproportionation following magmatic SOz to H2SO4 and HzS groundwater (magmaticabsorption by hydrothermal),(2) by atmosphericoxidation of H2S in the vadose zone over the water table, associatedwith fumarolic discharge of vapor by released deeperboiling fluids (steam-heated), (3) by atmospheric oxidation of sulfides and during weathering (supergene). Magmaticsuchas aluniteoccurswith mir-rerals hydrothermal 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 diaspore,

zunyite,which are typical of hypogene(T : 200350 "C) acidic conditions (advanced argillic Meyer & Hemley 1961).This type of assemblage; but it may of aluniteis characteristic HS deposits, argillic alteration also appearin areasof advanced (e.g., Iwao 1962; Flall void of ore mineralization environments 1978). Alunite in steam-heated forms with kaolinite and interlayered illitesmectiteat about 100 to 160 'C where fumarolic vapor condensesabove the boiling zone of neutral-pH,H2S-richfluid, typical of geothermal t s y s t e m s 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.

Propylitic

Argillic + Adv. argillic

Leached silicic

Quartz alunite

, I
rock rock rock Kaolinitic rock vuggy Mineralized quartz rocl( '100 m

of of Figure 2. Cross-section alteration zones characteristic high-sulfidationdeposits,as observed at the Summitville Au-Cu deposit,Colorado.Diagram at left (simplifiedfrom Steven& Ratte 1960) shows schematic 1987). mineralized body, shownat right (from Stoffregren outwardzonationfrom a subvertical

Becauseof the relatively shallow and dynamic Proterozoic EnAsenAu deposit located in the environment of mineralization, overprinting Baltic shield of central Sweden; Fig. I ). The (<1.6 Ma) and deposits are Pleistocene among the three types of acid-sulfatealteration youngest is occur in the central western Pacific (Kelly, (including sLrpergene) possible;however,the The concentration of Lepanto,and Chinkuashih). spatial relation of each type of alunite to ore is different, and correct identificationis important depositsin young volcanic areas is mainly a reflectionof the fact that older HS depositsare for exploration (Rye et al. 1992:. White &. more likely to be eroded. 1 H e d e n q u i s t9 9 5 ) . Gold. copper,and variablearnountsof silver AGE ANDECONOI\{IC are the main productsof HS deposits(Table 2). DISTRIBUTION, Rodalquilar), occasionally with Gold (Nalesbitan, StcNInrcaNcB (Nansatsu), the only economic is silica by-product other magmatic- metal in the smaller deposits.No copper is In common with lrydrothermal deposits (e.g., porphyry copper produced at Paradise Peak and Pueblo Viejo. Mercury is producedat ParadisePeak, and the HS depositscoincideworldwide with deposits), is arcs. This association best Julcanidistrict has beena sourceof a remarkable plutonic-volcanic consistirrg Ag, Cu, Pb, of of assemblage observedin the Cenozoicdeposits the Circurn- polymetallic Europe Au, W, Bi, and Zn (Table 2). The six largest Pacificand the Balkanbelt of southeastern deposits or districts (Chinkuashih,El Indio, (F-ig I ). These deposits occur in two main margins. Goldfield, La Coipa, Lepanto,arrd Pueblo Viejo) settings:in islandarcs and at continental more than about 100tonnesof gold. eachcontains The tectonic regime during formation of the 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 ( 1 A Chilean ndes Sillitoe 991a). Rodalquilar, Summitville) formed in intracontinentalregionsduring periodsof extensiotl ANDASSOCIATED VoLCANIcSITTTnC that followed regional compression and subROCKS IGNEOUS m.y. by ductiorr several and only a Tertiary HS depositspredominate, The high-sulfidationdeposits consideredin few deposits are Mesozoic (e.g., Pueblo Viejo, Table 2 occur within intennediate-composition Zijinshan),Paleozoic(e.g., Temora and othersin (the early volcanic rock sequenceshaving ages broadly Australia),or PreCambrian southeastern

H ig h-sulfi dat ion Ep i t her ma I Deposi ts

Figure 3. K2O versusSiO, variationdiagram for rocks thoughtto be genetically relatedto high-sulfidation deposits. The samplesfrom 12 depositsor districts (r : 140) define a small compositionalfield, which contrasts sharply with the large field defined by volcanic rocks associated rvith lowsulfidationor intrusion-related deposits Au \ ( > 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 /t ' ca\c.,^ 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 alteration the rock samples of and precisionof the analyticaldata are Iargely unknown; however, according to the individualdata sources, most of the samples are unaltered very weakly altered.Circles or indicate average values for each high*t"'"" sulfidation deposit or district: Ch 50 60 70 Chinkuashih, q = Choquelimpie, o C G SiO2 (wt"/") 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 . a L 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 , Na - Nansatsu, : Paradise PP Peak,Ro : Rodalquilar, - Summitville. Su Compositional fields afrerKeith et al. ( 199l). SeeAppendixfbr references information dataplotted. and on

similarto that of mineralization. Whereabundant radiometric agesare available, age of the host the rocks and the age of mineralization are within precision: where a difference is analytical indicated, is typicallylessthan-1.0 m.y. (Table it 2). A comrnon spatial association exists between depositsand shallow. typically porphyritic the intrusions. Theseintrusions are interpreted be to the roots of volcanic domes or the feeders of central-ventvolcanoes or maar-diatrernecomplexes,the three rnain volcanic settingsfor HS deposits(1'able 2). Some depositsare hosted entirelywithin a single dome (Summitville), or within a dornecomplex (Julcani). most cases In tfre mineralizationextendsfrorn the subvolcanic intrusion into country rocks, such as the Main Vein Cu-ALr-Agdeposit and associated breccia deposits the Penshan in area of the Chinkuashih district. however, not showany Somedeposits, do (known) spatial associationwith subvolcanic intrusionsthought to be geneticallyrelatedto (e.g.,Nalesbitan. mineralization Nansatsu). the In Rodalquilar Au deposit, dykes and small intrusions of hornblende andesite which are interpreted to be temporally related to the mineralization reprcsent only a fraction of the altered and mineralized area exposed at the present depthof erosion;a largerintrusivebody is

tlroughtto exist at depth (Arrrbas et al. 1995a). The main controlon location mineralization of at Rodalquilar the structural is rnarginof two nested, resurgent calderas. With the exception of Rodalquilar, role of calderasin the formation the of HS deposits seems be lirnitedto facilitating to the emplacement late intrusive magrna along of preexistingcaldera ring-fractures(Rytuba cl rzl. 1990). The magmasthoughtto be geneticallyrelated to HS deposits have a remarkably limited compositional variation.The rangesof wt.% K2O and SiO2 for twelve depositsoverlap greatly and show a dominance calc-alkaline of andesitic and dacitic compositions, with subordinate rhyolite (Fig. 3). Intermediate calcic volcanic rocks are limited to porphyritic intrusionsin the Lepanto and Motomboto Cu-Au-Ag districts, and intermediate-to-felsicalkali-calcic rocks are characteristic the Summitville and Laurani of districts(Fig. 3). Interestingly, depositshave no been discovered association in with 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 mineralizationcharacteristics 14 selected of high-sutfidation epithermal deposits


Lateralalterationzoning (outwardfrom nrinemlizcd txxlies) VS ,qr-alu |qt7-kao ) k a o - s m cr i l l - c h l SilicificdHbx rqtz-kaoalu rill-sme-chl-cal r VS/MS , tz-alu-kao kao-qtz-illrchl-ill VS,MS rtltz-alu-kaor ill-chl-kao VSA4S tqtz-dic-alut9?dic-\er rqtz-Scr VSA4S rqu-dic-alu r90)qU_ser dic_Sor Vertical altcration zonin-9 (shallow t() dccp) VS,MS rqtz-alurqtzkao rill-kao lchl SilicificdHbx )qL.-kx> alu rill-sme-cbl-cal MS/VS rAA ISER r ( K-silicate subiacent in FSEporphyrycopper) ( )re mineralization rn: Ag/Au Silicacorc 35--15

Dcposit

Pnncialore nrinerals Py. ena-luz, mzu.sph.gal. tcnlct. ars.cpy. arg. nat.Au.tcll


Py. chalc.qtz, cco. hor. cov. ena. tell Ena-luz, py. ten-tet. cpy. p_v-.. e lc. sph. gal. nrar. sele. tell. Snbearing sull' py. ena-luz. f :rm. tcn-tet. nal.Au. elc. hu. nat.Hg. tcll. splr.grl. cpv. geo. hou py. dig. ena.cov. nrol. nat.Au cpy. hor. tet-ten. gal. sph

Motonlboto

Nalcsbitan

Silicacorc

Vcry Io* As

Lcpanto

Silic:r corc

Chinkuashih

Silica corc

Zijrnshar

Silicacorc

N/A

N:ursaLsu

Sunrnritville

Goltllicld

Pu'irdisc Peak

VSA4S ralu-dic-pyo' ill-kao-smct PRO V S ( M S ) t q t z - a i u -t qu-kao 'kao-ill I snrc-chl M S ( V S ) r q r z - : r l u - k aro ill-smc I PRO Vertical(dueto deF)sit s t y l c ) M S ( V S )| : q?-alu-kaorsme-chl + Conrplex overprinted

VS/h4Sralu 'dic-serp Y ) s e r - c h lt P R o vs(MS) ,qrz_kao_ x l u r q t z - k a or S E R MS>VS .qr1__alukao |q?-klolpyo M S ( V S )) q l z - a l u - k ( ) (SERin laulted. deeper('l) EastZonedeposit) Early:Kao-py-qu r du-py<ltz Lare: S rpyo_dia M

e n a - l u z .p 1 ' .c l c . n a t . A u . a r g . plr. cpy. bor. sph. gal. cas. stir n)()1. can py. cna-luz. c()v. mar. nat.S. nat.Au. sph. gal. bar. cpy. ten py. lam. ten-tet. bls. gol, nat.Au. cna-luz. bru. tell. sph. cov bar. stb. his. nat.Au. nrnr. pl. nat.S. cin, sph. gal, cpy. ars. tet. arg, cov. f:ul py. sph. cna. nal.Au. nal.S. b2rr. tcn-tet. fan. gal. bar. stb. cle. selc, tcll, Bi- Pb- Ag- sull' py. wol. c:rs. nat.Au. ena. lur. tel tcn. cpy. gal. sph. biu. sid. Pb- Bi- Ag-bearing sull' Ena. py. tel, nat.Au. ten. cp-y. gal. sph. hue. hor. dig. cnrp. cco. nlar. Dar.

Silicu ore c

<2

Silicaeorc

2-10

Siliclrcore

<|

Silicu ure c

10-30

V Puehlo rejo

InAA+ MS zoncs Vcins

Julcuri

pre<rrc:VS/MS )qtz_alukart rqtz-kao: Syn<rre: qtz-pyo-pyrqu- kao-py+ q?-siir-py lq(Z-kao-smc veins rkao-aluCu stage scr-qU: stagc Au vcins rser-kao-pyrt-q? Alu-kto rqu-scr )(K-sil icatc in N. del Farnatina porphyrycopper) VSMS rqtz-alu-kaor qtz-kao-sel qt !-ser-py

.170

El Indrr

Vcins

La Mcjicaua. Nevrdrx drl Fiunatina Rulalquilar VS,MS rqtz-aiu-kaor qtz-kao-ill r ill-sme-chl

pV. cna. cpy. Splr, ten-lct. cov. cco. lam, luz. nat.Au. gal. nlol ele. tell, col. Sn-Bi-Ph-Ag-sull Py, nat.Au. cna. tell. cas. col. cov, dig. bor, gal. sph. Bi- sult

S i l i c uc o r e

10-10

Silicacore

<I

a l s A b b r e v i a t i o n s s c d :A A : a d v a n c e d r g i l l i c ,H b x - h y d r o t h e r m ab r c c c i a ,M S : m a s s i v e i l i c a , P R O - P r o p y l i t i c .S I J I { : u , 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 : q , o , b i s m u t h i n i t e b 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 y r c h a l c e d o n i c u a r t z , , c c , c , c h l : c h l o r i t e ,c i n = c i n n a b a r , 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 e ,o l - c o l u s i t e , 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 : ( g , e e d i c k i t e ,d i g : d i g e n i t e , l e : e l e c t r u m , 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 ) ,a l : g a l c n a ,g c o - g e o c r o n i t r , , g o l : g o l d f i e l d i t e h u e - h i i b n e r i t , i l l : i l l i t e , k a o : k a o l i n i t e , u z : l u z o n i t e , a r : m a r c a s i t cm o l : m o l y b d c n i t c , a t . A u: , l m n e 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, t, , s u l f - s u l f i d e s 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 e o u : t o u r m a l i n ew o l : w o l f i a m i t e o I ( l n ; 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 ( g e o l )e v i d e n c e b l a n k r v h e r e 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 ce d u c t i o n - s s o c i a t e dt h h y d r o t h e r m ab r e c c i a t i o n wi l r a

Jr. A. Arribus, of The depositis 3 km long and consists a tnain is difficult, but useful for discussion of the zone of breccia and replacementmineralization design of differences among deposits and alongthe LepantoFault(Fig. 4A). Multiple veins exploration strategies.In this context, White with smaller diagonal faults branch associated stylesof three end-member (1991) distinguished from the rnain zone and extend into both the of deposits the Circumnamedafter HS deposits, Irregular hanging wall and foot'ivall (Garcia l99l). The Pacific:Temora,El Indio, and Nansatsu. of cross-section mushroom-shaped characteristic in silicifiedoresdominate of bodies disseminated, at many of the orebodies Lepantois relatedto the the Temora-style. Cavity-filling veins with of intersection the steeplydipping Lepanto fault of sericiticand clay-rich haloesare characteristic and branch veins with the unconfonnity at the El Indio-style ALr deposits. A large group of dacite (Fig. aB). Lithologic falls into White's(1991)Nansatsu-style, base of Imbanguila deposits variations in the host rocks also played an which is characterizedby wallrock-alteratiort importantrole in the fonnation of the deposit.as zoning similar to that shown in Figure2, and by shown by lenses of stratiform enargite-luzotrite ores within a the occurrenceof enargite-bearing of massivesilica ore which resultedfrom replacernent detrital of silica core consisting vuggy or ntary within volcaniclastic and sedirne layers rock (Table 3). Mineralization in this style of units(Garcial99l ). bodies (e.g., basement deposit forms irregular stratabound vein-like Nansatsu, Lepanto) or subvertical "ledges"(e.g.,Chinkuashih, ANDZONING MINERALOGY AITEN.ITION Goldfield, or masses Lepanto, Rodalquilar, Summitville). These As mentioned above, the lateral alteration containbrecciabodies,veins,stockworks deposits oresthat replace zoning that is characteristicof HS deposits of small veins.and disseminated reflects the reaction and neutralizationof highor irnpregnate intensely altered country rock' temperature acidic fluids with wallrock. The two (1993)distinguished & Ericksen Cunningham innermost zone of vuggy or tnassive silica Agstylesof HS depositsin the Andeanprovince: with a commonly has sharpboundaries alteration veins' and and Au-rich polymetallic base-metal the vuggy silica and breccias; two types zone that may contaitrquartz, alurrite,kaolinite, low-grade and zunvite'.l'his diaspore, dickite,pyrophyllite, are broadly comparable with El Indio- and gradesinto a second assemblage argillic advanced resPectivelY. Nansatsu-styles, envelope of argillic alteration, composed of subverticalfaults and fracturesare the l,ocal kaolinite,illite, sericite, mineralssuch as quartz, and they dominant control on HS mineralization and an outermosthalo of propylitic and smectite, are present in rnost deposits (Table 2). Other of structuralcontrolsobservedin some alteration,with chlorite. illite, smectite. and examples districts arnong the foufteen selected include: carbonate(Fig. 2, Table 3). The width o1' eacl.t vuggy silicaand faults (Goldfield)' zonevarieswidely; for example, to rnoderately shallow-dipping rock fonn narrow advancedargillically altered caldera ring and radial faults (Rodalquilar),the at jog of a strike-slipfault (Nalesbitan), (<70 cm) vein selvages Julcatri(Deen 1990)' dilational at but form wide (>50 m) rock bodies Sumrnitville the diatremering-faults(Lepanto,Pueblo Viejo), cavity(Figs. 2 and 4). Late-stage', or Lepanto contactbetweena dome or volcanic conduit and country rock (Motomboto, the Missionary filling planarveins at Julcaniand E,l Indio may ln the outside zoneof alunite-kaolinite' the orebody at Summitville), and a lithologic extend however,most of the ore deposits, majority of HS In unconfbrmity(PuebloViejo, Lepanto). threeof is containedwithin the silica core, inside the deposits, the principal control is the fburteen ('Iable3). argillicenvelope advanced at (maarsediments PuebloViejo, and lithological interbeddedpyroclastic layers at ParadisePeak Table 2). and Nansatsu; A unique cornbinationof the structuraland of lithologicalcontrolscharacteristic HS deposits is exhibitedby the LepantoCu-Au-Ag deposit.

lln Russian and eastern IJuropcan tcrrninology lhcse rtlcks are 'metasomatic quartzites" with nrorc spe cilic conrmonly termcd names such as porous quartzites, diasporc quartzitcs' alunite ( 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 se . 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 cross-sections the Lepanto-FSECu-Au-Ag deposits (B) of (phitippines), showingstructuraland lithologic controlson formationof the high-sulfidation and porphyry-typeores (simplified from Garcia l99l ). Potassium-argon datingof countryrocksand alteration minerals associated with the porphyryand high-sulfidation deposits indicates that hydrothermal Cu-Au mineralization took placein the middle of a plioceneto Pleistocene event of dacitic-andesitic magmatism(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 deeper partsof epithermal mineralization).

The zonesof alterationwith increasing depth 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 documented deep by drillholes the deposits smallersize,in which in of 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 epithermal gives deposit way, laterally towards the south, to K-silicate alteration of the FSE porphyry Cu-Au deposit. Porphyry-type stockwork mineralization at Paradise Peakis contained within the sericiticores of the East Zone deposit which, according to Sillitoe & Lorson (1994), formed underneath the main HS orebodiesirr the area.A quartz-sericitepyrite zonewith traceamounts chalcopyrite of and molybdenite surrounds intrusion monzonite an of porphyry >300 m below the HS deposit at (Grav& Coolbaush Summitville 1994\.

The lateral and vertical alteration zones described above correspond to a generalized model. They are useful in exploration because they help in understanding the genetic environment of a depositand provide spatial "markers" within the extinct hydrothermal system. Experimental data on the relative stability of rnineralssuch as alunite, kaolinite, pyropliyllite, (Hemley et al. 1969, 1980),coupled and diaspore with the temperature rangesnoted for these and other related acid minerals in active systems (Reyes 1990; Reyes et al. 1993), also provide informationthat contributesto definition of the paleoconduits extinctsystems. in If studied in detailed, several superimposed and crosscutting stagesof pervasiveas well as (conduit)-related fracture mineralizationmay be recognized the majority of deposits. in Theseare the expected resultofvariations,during the course of mineralization,in temperature, pressure,and compositionof the hydrothermalfluid and the degreeof wallrock interaction. Detailedfield and petrographic studiesat the Monte Negro orebody in the Pueblo Vieio deposit have resulted in

A. Arribas, .Jr.

IKM

I ffi
l ^ ^ a f-'-^l

tl

m @

Vuggysilica argillic Advanced Argillic Sricitic Propylitic acij-sulfateovsrprint Inlensesupergene


Au-(Cu-Te-Sn) htghsulfidation deposits

-100 (m) Elsvation


| 500m I

(B) map (A) and cross-section of the Rodalquilar alteration surface Figure 5. Generalized Spain(fiom Arribas e/ southeastern and Lomilla calderas, Rodalquilar HS depositin the shown betweenalterationzonesare irregularand gradational. The boundaries at. 1995a).

identification of two stages of mineralization, to to interpreted correspond two distinctmagmatic (Muntean et al. 1990). During the first pulses stage (responsiblefor -600/o of the Au in the and deposit),shallow kaolinite-quartz-pyrite deep zones were dealunite-quartz-pyrite-quartz in veloped,with gold mineralization association pyrite in the wallrock; during with disseminated for stage(responsible about40% ofthe the second zoneof silicificationwith pyrite Au), an extensive + sphalerite+ errargiteveins formed at shallow levels. above a zone of pyrophyllite-diaspore (Munteanet al. 1990). alteration

particularfeaturesof the depositslisted in Table 3. Pyrite and enargite (and its low-temperature dimorph luzonite)are the dominantsulfidesin HS deposits;pyrite is abundantbut the amount of enargite and luzonite is variable. Common ore minerals, listed by decreasingabundancefrom variable to very minor, include tennantitecovellite, native gold and argentian tetrahedrite, gold (electrum), marcasite,chalcopyrite, sphalerite, and galena.Famatiniteis locally abundant (Goldfield,La Mejicana).Sparse in somedeposits ctnnabar, ore mineralsincludebornite,cassiterite, molybdenite, orpiment, realgar, stibnite, and wolframite (the last locally importantat Julcani). AND Other minerals present in minor amounts in MINERAL0GY' Ono aNu GANGUE severaldepositsinclude Pb-, Ag-Pb, Bi- and SnTIMINGOFMINERALIZATION (Table3). bearingsulfbsalts quartzis the dominantganguein Fine-grained White et ul. (1995)and White & Hedenquist on detaileddiscussions various HS deposits.Other comrnon but minor gangue (1995) presented on minerals include barite, kaolinite, alunite, aspectsof epithermalgold mineralization the and Ca-,Sr-,Pb- and REEpyrophyllite,diaspore, basis of observationsfrom a large number of mineral(s) such as with bearing phosphate-sulfate theirconclusions the Pacific; around deposits or svanbergite-woodhouseite crandallite (Stoffrespect to ore and gangue mineralogy in HS to the & Alpers 1987).For example,high-grade regen deposits are included here, in addition

High-suffidation hermalDepos Epit its

I I

Goldfield,and from Chinkuashih, vein specimens of intergrowths ore La Mejicanahave spectacular pyrophyllite. mineralswith kaolinite, alunite, or This observation implies that ore formation occurred under moderately acidic to acidic with transport which are inconsistent conditions, of Au as a bisulfide complex (Seward 1973). Recent studies of Au solubility in highhaveresultedin acid sulfide solutions temperature of identification AuHS" as one of the principal (Bening& in gold complexes HS mineralization 1994),the other possibilitybeing AuCl2 Seward e/ (e.g., Hedenquist al. 1994a). The number and order of mineralizingevents of providecritical informationfor reconstruction results in HS the hydrothermal system that A mineralization. minimum of two stagesof has alteration/mineralization been recognizedin most deposits on the basis of crosscutting relations(Table 3). The most common evolution is from an early leachingand alterationstageto a laterore-formingstage.Vuggy silica rock and the with disseminated advancedargillic assemblage acidic alteration, pyrite form typically early-stage by Cu + Au + Ag deposition. and are followed studiesin some districts(e.g.,El Indio, Detailed however,have resultedin identification Lepanto), metal stages,an early Cu-rich, Au-poor of two and stage,dominatedby enargite-luzonite, a late Au-rich, Cu-poor stage, associated with sulfides such as intermediate-sulfidation-state and chalcopyrite, and tennantite-tetrahedrite tellurides. The transition from quartz-aluniteand finally to pyrite alterationto enargite-pyrite the last typically without tennantite-tetrahedrite, gangue sulfate (alunite) but with quartz-sericite and wallrock alteration, indicates a fluid progressivelymore reduced and less acid. At (also Tambo and Summitvilleand Chinkuashih Table l), a late stage of bariteFurtei-Serrenti; gold hasbeendocumented.

of these data with geologicaland mineralogical mentionedabove allows the nature observations of the altering and ore-forming fluids to be determined.The framework for the interpretation has benefited from information on the compoand sition and fluxes of volcanicdischarges active (Hedenquist& systems magmatic-hydrothermal Lowenstern 1994; Giggenbach this volume; this Hedenquist volume). F I uid-in cI usion Ev idence Suitablehosts for fluid-inclusion studiesare as scarcein HS deposits, the ganguemineralsare typically fine-grainedand even millimeter-size quartzcrystalsare usually late stage hydrothermal results are obtained and vug-filling. Satisfactory on secondaryfluid-inclusionsin igneous quartz phenocrysts from altered wallrocks; although lacking temporal information, these inclusions of cross-section seemto provide a representative the fluids involved.The most reliabledata on the ore-formingfluids are obtainedthrough infrared microscopy directly on ore minerals, such as enargite (Deen 1990; Mancano & Campbell

1ee5).

and salinitiesestimatedfor The temperatures HS deposits definea wide range,from 90o to 480 oC and <l to 45 equiv.wt.% NaCl, respectively (Table 4). There is no systematicdifference in salinity among Au-, and Ag- or base-metal-rich deposits, in contrast to that noted for low& sulfidationAu versusAg deposits(Hedenquist Large variations in both Henley 1985). and temperature salinityalso occur within a single deposit; these reflect the dynamic environment, and high- and with high- and low-temperature during the courseof low-salinityfluids interacting mineralization. Four broad groups of hydrohere on the basisof thermalfluids are recognized the estimated temperaturesand interpretations given by most workers. The temperature boundaries chosen for each group are only indicative,as significant variations exist among oF CsaRactnRISTICS ANDSoURCES and within deposits; each group, however, HvuRorsnRMAL FI-utos providesrelevantinformationon various genetic aspects. and Resultsof recentdetailedfluid-inclusion (e.g., >300 "C) Group 1. Higher temperature studies reveal much about the stable-isotopic fluids of variable salinity, which have been composition, temperature and sources of in Combination documented severaldepositsand are generally fluids in HS deposits" hydrothermal 431

A. Arribas, Jr.

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


Host-mineral studicd Barite Quartz Enargitc Tcmpcrature ("C)t Asstriatcd Salinity (cquivwt.%NaCl) altcration

Deposit Mrxoniboto, Indoncsia N a l c s b i t a n ,P h i l i p p i n e s L c p a n t o ,P h i l i p p i n e s

150-180 22(J-260 t](\-290

<l 0.24.5

Atusil AA/sil AA/sil

Chinkuashih, aiwan T Zi.linshan. hina C

Quartz, baritc. alunite Qu:rtz (no dctails rcfx)rtcd)

I8{).330 I 6(f-3(X) 220 380 l 0(I- 160 (300-+20) 13(l250 -210 25F310 I 9(I-240 2I(I 330 l8(}_280 (300-390)

o.2-t2
a 1 a

3 ,t 9 0-5 (3-2( ))
<l up to 30 0.5-1.1 2-18 (upto 9) 5 1 8 0.2-8 <3

Scr

sir
AA/sil AA/sil Scr AAisil

N a n s a t s uJ a p a n ,

Quartz

Akaiwa, Japan Mitsumori-Nukeishi, Japan S u n i m i t v i l l e ,C o l o r a d o

DiasJnre Quartz. ba-ritc, quanz pnen(x Quartz phcnoc

AA/sil

Baritc Coldlielcl,Nevada Quartz-phenoc Quartz, baritc Quartz, barite Quartz Quartz phenrr Quartz phenoc Wol, ena, quartz Sidcritc Quartz phenoc Qufiz phcnoc

- t(x)

Pradise Peak, Nevada

Julclni, Peru

Ccarhuaraso, Peru Colqui.jirca,Peru Can-Can (La Coipa), Chilc El Indio, Chile

230-480+ 2I (),280 (37(H10) r80-2I0 300,380 (upto 4-50) I 60-280 36045t) 230-330 220,250 330-380 23(f,260 l7(I 350 I 90-280 i4(}-l80 (>3(n) 2(XI'+60 l6(i-340 230-480 17F300 22(}.450 I 9(),320 9(I 140 (390-5m)

AAisil AAisil AA/sil Ser AAisil

3[r35
\ ) 4 38,46

920 6-9 7 18 .+-ll < l-40 l 0.4 0.t-2.1 (upto 27) t 3 l 0.3,1 2 341 230 245 0.4-23 0.4-I .6 (32 45)

La Mejicana (LM) and Ncvados Famatina(NF), Argentina

Sphalcritc. quartz hiibnerite Quartz phenoc N/A

AA/sil AA-/sil AA/sil donrinant AA"/Ser

AA + scr Scr

Rrxlalquilar,Spain

Quartz, quartz phcnm barite, Quartz, phentr quartz

AA/sil Ser

Furtei-Serrenti,ltaly

AA/sil

Ahbreviations used: AA = advanccdargillic, ena = enargite,phenoc = phenocrysts, = ser sericitic, sil = silicicl wol = wolfiamite: see Tablc J for rraleoderrth estimations Irem;^*raturc,arcr()undedl()ticncircstt)": hraekcisuscdtoindrcatctugh-tcnrpcraturr. l inclusions typically interpretedis having formcd early or being anomalous

"anomalous" unrelated ore and to or as interpreted are associated with early stages of alteration. Two-phase entrapment may explain some of the (4), temperatures unusuallyhigh homogenization particularly considering the shallow mineralization depth inferred for many of the deposits (Table 3). However,most workersagreethat such

entrapment cannot account for all the high 17, presence thesefluids in of values.The consistent deposits indicates a high temperature several gradient,and implies the presence a shallowof depth intrusion,and possibly lithostaticconfining pressures. the basisof fluid-inclusion,as well On as isotopic (634Srrrrut.-rurna") temperatures(see

432

H igh-sulfdation Epithermal Deposits

Table 4. (continued)

Dcposit M ( ) t o r n b o t oI n d o n c s i a , n * a l c s b i l a nP h i l i p p i n c s . L c p a n t o ,P h i l i p p r n c s

Commcnls Rcconnaisancc srudy in latc-stagcbarite Reconnaissancc studyi liquid CO2 observcd Samplcd intcrval 3 knl long by 0.5 kn hieh t ctnling tluitls awav fionr subjaccntporphyry Cu-Au degrsit, whcrc Th >.150'C & salinity up to 5.1eq wt.rl NaCl P r x r r l y - d o c u m e n t e d 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 : sa the highcr Ths in sanples lt -7,50 m dcpth: CO2 ohserved Asstrciatcdwith main stagc Cu Dorrpaltcration zonc (>6(X) nr depth) Associatcd with late. shallow silica-Au Assrriated with carly silica and quartz-dickite Late, vug-lilling quirtz Qtz in brcccia. salrneliquid and krw-salimty vapor cmxist Vein quartz -4(X) m helow Kasuga deposit Coarsc-grainedclilsgrre Not (known) Au or Cu mincralization, but high salinity lluids Licluitl-rich: alinity>6 eq wl.7 NaCl only in vuggy silica s associated with Cu mineralization: CO2 obscrvcd Lrquid- and vapor-rich inclusions: also polyphaseinclusions Latc barite-Au assemblagc Truc T5 is interpretedto be 25(1290"C Hydrostatic and ncar-lithostatic prcssures suggested Latc, vug-lilling crystals in hydrothermal brcccia: Frorn stockwork Au East Zonc dcoosit: COr observed Quaru-alunitetpyrite Pro-oretourmalinc brcccia dykes, lithostatic pressures likely. Main-stagc orc fluicls, also inner veins, liquid-rich inclusions Latc-stageore fluids, also in outcr vcinsl P correction applied Quartz-alunitctpyrite Quartz-al u ni tetpyrite Two generationsidcntillcdl both may be very salinc. Evidcncc firr P abovc hydrostatic and higher salinities at dcplh Coppcr and gold stages Late stage Interprctcd as carly, with vapor-rich inclusions,CO2 observetl LM & NF. includes liquid-, vapxrr-richand potyphasc inclusions NF: complctc transiLionliom porphyry-type fluids in Ksilicatc 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 Vcrtical temperature and salinity gradient: high-lcmperature brines coexist with low -;Llinity vapor inclusions: hydrostatic and near-lithostatic pressuressuggested Includes hi-eh+ low-salinity fluids (22-23, <6 eq wt% NaCl) Latc stagc

Rcl'crcnccs

( Percll6 I 99:l) (1990) Sillitm el rr1. (1995), Mancano Campbell & Garcia(1991) Folinsbee trl.(.1912).Ycn et (.1991) ( 1976), et uL. Tan Zhanger al. (1991)

T Chinkuashih. aiwan Z i . j i n s h a nC h i n a ,

N a n s a t s uJ l p a n ,

Hcdcnquist ul. (1991.t) et Akamatsu Yui (1992) & (199-5) Aoki & Watanabc Bruha Noblc( 1983), R. & (written Stoflicgcn c o m m u n .1 9 9 4 ) , (1985) Cunningham Bruha Noble(1983) & Vikre( 1989) J o h n ta 1 ( 1 9 9 1 ) e . (l99tl) Sillitoe Lorson & Bruha&Noble(198.1) Shclnutt Noble(1985) & Dccn ( 1990) Deen( 1990) Bruha&Noble(l9ti3) Bruha Nohlc(198.1) & ( Townley 199 1) Jannas a/. ( I 99(l) er Losada-Calder6nMcPhail & ( l 994)

A k a i w a ,J a p a n , M i t s u m o r i- N u k e : i s h iJ a p a n S ur n m i t v il l c . C o l o r a t i o

ColtlliekI, Ncvatla

PiiraclisePcrk, Ncvatla

J u l c a n i ,P c r u

Ccrrhuaraso, Pcru C o l c l u i l i r c aP c r u , C a n - C a n( L a C o i p a ) . Chile El Indiu, Chilc

La Mc.jicana(LM) and Ncvacirs Famatina(NF), Argcntina

Rrxlalquilu, Spain

Sdnger-von Oepen a/. ( I 989), at Arribis et al. (1995a) ( RuggieriI 993b)

Furtci-Scrrcnti, Italy

below), pressuresabove hydrostatichave been for severaldeposits,including Julcani suggested (Shelnutt Noble 1985), & Goldfield(Vikre 1989), (Arribas (Rye 1993), and Rodalquilar Summitville et al. 1995a). fluids Group 2. Intermediate-temperature (e.g.. 180-330"C), with salinities variablefrom

<1 to -18 equiv. wt.% NaCl. With the possible exception deposits which only the late-stage of for mineralshavebeenstudied, thesetypically liquidrich inclusionsare found in all deposits.Mainstageore fluids are containedwithin this group. The temperatures measured fluid inclusionsin in at enargite Lepanto(Mancano& Campbell 1955)

433

A. Arribas, Jr.

Temperature ("C) and Julcani (Deen 1990) are broadly similar, but their salinitiesare distinctly different (0.2-4.5 200 400 300 equiv.wt.% NaCl versus8-18 equiv.wt.% NaCl, H2O+5wf/.NaCl providing constraints the role of respectively), on a saline magmatic liquid (versus Iow-salinity vapor) in the generation HS deposits. of Group 3. Lower temperature(e.g., 90-180 "C), dilute (typically <5 equiv. wt.yo NaCl) o liquids; these have been documentedin a few 0) deposits associatedwith late-stage(e.9., AuThe late-stage fluids at ore dno 6 barite)mineralization. oC; Deen 1990) and Julcani are hotter (220-250 o (s slightlymore saline(6-9 equiv.wt.% NaCl), than 3 theseaverages, no correlationamong the late but stages differentdeposits attempted in is here. A-n n ; - ' o "Sericitic" fluids. As mentioned Group ./. a, E above,sericitic(quartz-sericite-pyrite) the most is q) common alteration assemblage observed below o the ore zone in some HS deposits.Although detailed documentation is lacking for many deposits,higher temperatures and higher salinity fluid-inclusionsseemto characterize sericitic the zone with respect to the shallower zones of alteration(Table 4). For example,at Rodalquilar Figure 6. Elevation versus temperature diagram (Arribas et al. 1995a), documentation of temshowing 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 the RodalquilarAu deposit, in 6) shows a gradient which correlateswith the Spain.Also shown are the temperatures calculated, on change in dominant alteration,from silicic and the basis of 63aS for four surfide-surrare coexisting aluniteoC, advanced argillicQ : 170-300 salinity:2-15 (large filled circles),reference pyrite samples boilingequiv. wt.% NaCl at the elevationof the orebody) point curves,and vertical spansof the alterationzones oC,salinity:2-45 equiv. mentioned in the text. Estimated salinities of fluid (T: 220-450 to sericitic inclusions the shallowadvanced in argillic/siliciczone wt.% NaCl) assemblages. and deep sericiticzone range between2 to 30 equiv. The transition from advancedargillic alteration, through quartz-sericite-pyrite, to K-silicate wt.% NaCl and 2 to 45 equiv.wt.% NaCl, respectively (modified from Arribas et al. 1995a). alteration and typical porphyry-type high(600+ "C) and high-salinity(up to 67 temperature equiv. wt.% NaCl) fluids of magmaticorigin is rich hypersaline inclusions(i.e., with Groups 1 displayed,among the examplesreviewed,at the del and 4, above).Thesefluids may be the result of Lepanto-FSE and La Mejicana-Nevados liquid, or they may Famatina epithermal-porphyrycopper systems. boiling of a high-temperature reflect immiscible vapor and hypersalineliquid The cooler and less saline inclusion fluids are derived directly from shallow-emplaced magma in documented the ore zoneof the HS deposits (Rye 1993; Hedenquist & Lowenstern 1994 interpretedto reflect mixing of magmatic and 1994;Hedenquist volume). this Shinohara meteoricfluids in an environmentshallowerthan Furthermore, in that of porphyry mineralization. Sulfur-is otope Ev iden ce common with porphyry-type deposits, highThe abundanceof coexisting hydrothermal temperature, vapor-rich. low-salinity fluid in liquidsulfidesand sulfates, additionto the possibility inclusionscoexist with high-temperature,
q) -' (g q)

434

r t
I

H igh-sulfidation Epithermal Depos its


aSSHzs-sor Temp.("C)' H2S/SO4

-Sultides -

Sulfates^

V& V= 634515

t
I t
i :.
a

Lepanto Chinkuashih Nansatsu Summitville Goldfield PuebloViejo Julcani El Indio Rodalquilar


r

--F

r
I

p0 - 420 20 -270
l r f f i t
I @ I I I

2-6

'1-

- t v I
l i

200 - 240
l

! v

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

F I

--.--* -;

r
J

z ry v

Y
l
I o

r t - ' l t

l l

@"f"

I
I

220- 330
'(minerat pairs)

10 20 6345(%", CDT) !-igure 7. Range of 63o5(per mil) values for sulfidesand sulfatesfrom nine highfor Also shown are the valuescalculated 5'oS for total sulfur in the sulfidationdeposits. and the range of temperaturesdetermined hydrothermal system (triangles), H2S/SO4. 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 in host rock and genetically of measuring (Sasakiet al. 1919),allows related igneousrock sulfur-isotopestudiesto provide information on and sulfur sources the composition,temperature, the hydrothermal fluids. The resultsof detailed of studies in nine HS districts show a remarkable consistency (Fig. 7). In agreement with the observations in active volcanic-hydrothermal (e.g.,Kiyosu & Kurahashi 1983),sulfide systems and sulfate minerals are mainly in isotopic 'oS/1'S equilibrium, and, therefore,their overall and of the depends.on temperature mineralization '"S/"S of total sulfur in the hydrothermal the system. Only the data for alunite from the vein in El Indio (Fig. 7) are different.If Campana the measuredEl Indio alunites are not steam(unlikely as they containfineor heated supergene pyrite; Jannas al. 1990),the most likely grained et "magmatic-steam" (Rye et al. explanation is a in which the 63aS aluniteis close of 1992)origin, to the compositionof total sulfur in the system (e.g.,Alunite Ridge in Marysvale;Cunningham el al. 1984: Rve el al. 1992\ . Combined with the

valuesof pyrite and enargitefrom the same 63aS vein, these values indicate drastic changes in H2S/SO4during the course of mineralization (similar to those for the Red Mountain alunite deposit;Bove et al. 1990;Rye 1993). The main conclusionsof the sulfur-isotope studies in HS deposits are: ( I ) sulfur in the depositsis magmatic,but the magmatic sulfur is : overall heavierthan mantlevalues(from 63aS 2 + 2 o l o o a S u m m i f v i l l e o 9 + 2 o / n o a tR o d a l q u i l a r ; t t, Fig. 7). This is not surprising given the most common geological setting of the deposits; isotopicallyheavy igneoussulfur is common in volcanic arc environments(e.g., Ueda & Sakai 1984). (2) A simple mass-balance calculation 3oS/"S done in severaldepositsusing the values 'oS/"S of the igneous rocks and the average values of sulfides and sulfates indicates that H2S/SO4 the hydrothermal in fluids was generally about4 * 2 (Fig. 7; Rye et al. 1992;Hedenquist el ctl. 1994a; Arribas et al. 1995a). This is a minimum value for ore-formingfluids because it appliesmainly to the early stageof hydrothermal

43s

./r. .4..4rrihns.

which is characterized a sulfate-rich bv alteration. assemblage(3) lsotopic equilibalunite-pyrite rium between sulfide and sr-rlfate in the results, a nrajority the in of hydrothermal solutions calculated the on in temperatures deposits. reliable (Fig 7). Pyrite-alunite basis on A3aSrr:s-so+ rnineral pairs were used most commonly, and thev shorv rvhere samplingrvith depth is available, e.g.,220to 330 oC over200-m a thermalgradient: clevationat Rodalquilar(Arribas et al. 1995a). (R1'e m 200 to 390 "C over .--900 at S'.tmmitville 'C over 500 m at l-epanto 1993)1220 to 420 (Hedenquist and Carcia 1990: J \\r. Hedenquist. unpr-rb. data). Other mineral prirs used with consistent results include p1'rite-barite(Vikre (Venncmann 1989: Deen 1990),sphalerite-barite (Vikre 1989). The plrite-g1'psurn and et al. 1993), lvith is rangeof isotopictemperalures consistent and estimatedfrom fluid inerlusions temperatures (e.g., Flemley' ul. 1980; et alterationmineralogy et Reyes 1990;Rey'es ul. 1993).l-he rangeis also consistent with formation of altrnite at belorv-400 "C, rvhenSO2gas starts temperatures solution in to dispropottionate the h1'drothermal (Sakai& Matsubaya Bethke1984). 1911;,

lack of post-depositional effectsthat disturbthe and stable-isotope systematics. (4) the availability of detailed information on the isotopic composition fluids in active geothermal of and systems. which allows volcanic-hvdrothermal fluids estimatedin HS depositsto be compared with thosein theiractiveequivalents. 'fhese rnay be Some limitationsstill exist. rndependent obviousfactorssuch as sampling of (fundamental procedures or mineral-preparation for achieving representativc reliableresults). and as analyticalimprecision. and naturalvariations, (c.g.,Aoki 1991,1992, in observed activesystems Rowe 1994).Importantlimitationsthat rnust be for taken into accourrt optimum use of the stableisotope data are related to ( l ) the choice of temperature mineral formatiott fbr calculation of (2) of the lluid isotopiccomposition. thc lack of lractionation factors for some mineral-water minerals (e.g, pyrophyllite), and (3) the disagreement among fractionation constants proposed evencommonminerals suchas illite lbr (see Dilles er a/. 1992, for a discussion) and kaolinite. For examole.at 200 oC there is a difference of -20" lno between tlte D/lI fiacfor tionationconstants kaolinite - water as given by Marumo et al. (1980) on the basisof samples Evidence Oxygen- and Hydrogen-isotope and by In terms of oxygett and hydrogen isotopic of mineralsand rvaterfrom activesystems, (1984)on the basisof experimental t,iu & Epstein the fluids that form HS depositsare composition, results. For these reasons.discussionof the documentedand arguably some of the better This situation sourcesof water during acidic alteratiorrin the studies. in understood ore-deposit here is basedon the average depositsconsidered contrastssharply witli that of a decadeago, at 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 alunite systemsand HS deposits et al. 1994).The magmatic-hydrothermal volcanic-hydrothermal 1987). Stable- typical of HS depositsgives good resultsbecause (e.g.,Healdet al. 1987; Hedenquist (post-mineralD-H particularly it is relatively coarse-grained isotope studies of HS deposits are et is exchange not a problem;Stoffregen al. 1994) and of: (l) the abundance illuminatingbecause with ore, thus associated minerals and commonlyis closely variety of oxygen-and hydrogen-bearing of conditions a f-luidcloser equilibriurn (2) the development recording (e.g., illite, kaolinite), alunite, in compositionto the ascendingmirreralizing of analytical procedures for complete stablesolution than the kaolinite or illite from outer 6l8orooand of analysis alunite,including isotope zones. alteration the 6'tOu' that help to distinguish varioustypes Oxygen and hydrogen isotopic compositions acid-sulfatealteration of alunite and associated with are of water in HS deposits clearlyconsistent (Rye et al. 1992; Wassermanet ctl. 1992), (3) magmatic mixing between a high-temperature fewer limitations on the interpretationof the o o f l u i d o f 6 1 8 0 : 9 + 1 o / na n d6 D : - 3 0 + 2 0 " / o a n d of isotopic data because the relativelyyoung age (Fig. 8). In part because of and general meteoricgroundwaters of of mineralization most HS deposits

F
H igh-su(idation Epithermal Depos its

Alunite alteration stg. Oremineralization stg. Q Alteration/ O . ^?y, n


-40

Subduction-related volcanrc vapor

3
> a
d

-ou

t9 -eo
o ta -100
-tzv

-140

(%", 6180 sMow)


compositionof hydrothermal Figure 8. Summary diagram showing variation in oxygen- and hydrogen-isotope fluids in high-sulfidationdeposits.The averageisotopic compositionfor the main stagesof acidic alteration (circles)fluids are shown. Where possible, (squares) only alunite data were used for the and ore-mineralization hydroxyl oxygenrequilibrates with the hydrothermal stage(6D and 6r8O5eo); alteration 6'tOo, is not usedbecause 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 (from Giggenbach volcanoes 1992b).Go: Goldfield, Ju: in andesitic fumarolecondensates subduction-related district: Ka - Kasuga,Iw : Iwato, NF : Nevadosdel Famatina,PV : Pueblo Julcani,Le- Lepanto,Nansatsu Veijo, Ro : Rodalquilar,RM : Red Mountain, Lake City, Colorado, Su : Summitville. The approximate for compositionsof groundwaterssuggested severaldepositsare indicatedby the intials parallel to the meteoric and information on dataplotted. water line. SeeAppendix for references the very light isotopic composition of local meteoric water, this meteoric-magmatic watermixing trend is displayed particularly well by the three stages of alterationlmineralization at Julcani (Deen 1990; Rye 1993): from a magmatic-waterdominated early stage of (alunite) acid-sulfate alteration (Ju, Fig. 8), through main ore-stage fluid-inclusion waters (Ju1 and Ju2), to meteoricwater-dominated late ore-stage fluid-inclusion relations are identical to those of volcanichydrothermal and geothermal systems associated with subduction-related volcanism (Giggenbach 1992b; Fig. 8, inset). The similarity is even closer between the composition of acidic alteration fluids (large shaded field, Fig. 8) and the vapor condensates from high-temperature fumaroles of andesitic volcanoes (dark shaded field, Fig. 8, inset), such as Nevado del Ruiz, Satsuma

Iwojima, or White Island,the last documented to havea geochemical environment similar to that of HS mineralization(Hedenquistet al. 1993). The origin of the D-enrichedmagmatic(end6180 valuesthan those of acidic alterationfluids, member)fluid of HS deposits hasbeeninterpreted greater dilution by groundwater(Fig. indicating 8). The extent of an O-shift in the groundwater in two ways. Most workers conclude that the acidic fluid in HS deposits is derived from component due to water-rock interaction, as typically seen in some neutral-pH geothermal absorptionof magmatic vapors outgassingfrom arc volcanoes felsic magmasin crustalsettings or systems,is not known, but such a shift is not (e.g.,Hedenquist Aoki 1991;Matsuhisa1992; & indicated the Julcanidata. by The overall oxygen- and hydrogen-isotope Giggenbach 1992q' Vennemann et al. 1993; waters(Ju3).In addition to Julcani,the ore fluids at Summitville (Rye et al. 1990:'Rye 1993) and Rodalquilar(Arribaset al. 1995a)also have lower

437

A. Arribas, Jr.

ALTERATION

Mixing with shallow meteoric water Absorptionof high P vapor Heated oroundwater cell \ Ionvective

j uagmatic-'
brine ll

Metal-bearing hypersaline / liquid l-

Heated groundwatet

A: argillic of Figure 9. Model showing the two main stages evolutionof HS deposits. Early stageof advanced proposedfor the stage of ore alterationdominatedby magmatic vapor. B, and Bt: Two genetic hypotheses in vapor by entrainment meteoricwater cell at depth to explain lowof formation.B, - absorption high-pressure metal-bearing this volume). B, - ascending magmatic ore salinity, mixed magmatic-meteoric fluid (Hedenquist mixed magmatic-meteoric ore fluid (White brine with shallow cooler meteoricwatersto explain high-salinity, 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 may occur which will lead to magmadegassing magmatic-hydrothermal different styles of mineralization with or without associated systems (Giggenbach 1992a). To form the styles of alterationand the spatialdistributionof alteration zones characteristicof HS deposits, degassing must be very efficient, with oxidized hightemperature magmatic vapor reaching shallow depthswith little reactionwith rock or dilution by groundwaters greaterdepths(Fig. 9A). Dilution at the high groundwatersis unlikely because with temperatures surrounding the cooling magma cause meteoric water cells to be displacedfrom the magma core (Fig. 9A). In addition to the at relativelylow pressure the depth of intrusion, effective degassing will be favored by the of structural factors characteristic HS deposits, such as fractured volcanic domes or roots of domes,calderaor diatremefaults,volcanicvent contacts. and active faults with a dilational comporrent. Inagmatic vapor As thc high-temperature

reaches shallowdepthsof lessthan a kilometer,it may be absorbedby groundwaterif it does not discliarge as a fumarole. The acidity of this groundwater-absorbed increases vapor condensate below as the liquid cools, first at temperatures -400 "C by disproportionation SO2 to form of H2SO4and H2S (Day & Allen 1925; Sakai & Matsubaya 1971), then by progressive dissoand HCI at lower temperatures ciation of H2SOa oC). Reactionof the increasingly (<300 acidic 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 probably<250'C (Stoffregen1987). temperatures The extremelyacidic conditionsmay even leadto cavitiesin which the only of forrnation dissolution remnantof the host rock is a basal sedimentary layer of quartz phenocrysts(e.g., Rodalquilar; Arribas et ctl. 1995a). assemblage of For the quartz-alunite-pyrite the advanced argillic zone, the stable-isotope with magmaticvapor being is evidence consistent meteoric waters, with tlre latter absorbed by

440

r
$
i

l { igh-.su I/idat ion Epit hermctl Depos its

constituting relativelvsmall part of the rnixturca -l'he (gcnerally <113, ltig. 8). fluid-inclusiorr is because evidence, contrast. inconclusive by of Nevertheless, the lack of ternporal infonr-ration. high-salinity inclusion fluids high-temperature, have been interpreted form early in most I{S to deposits(e.g., Bruha & Noble 1983: Ruggieri TheseflLrids rnal'be l993bl Arribaset ul. 1995a). greater depths. as demonstrated restrictedto at Rodalquilarand in other depositswlrere highrviththe deep fluid is associated salinityinclr-rsion (Table 4). This latter obsersericiticalteration vationsuggests episodic an asccnt high-salinity of magmaticliquid fiom the greaterdepthsof the system, rvhere hypersaline the liquid hydrothermal (Fig. 9A). to of tends staybecause its high density These nragmaticbrines rnay be rnore closely (and,in places. to alteration related the K-silicate porphyry m ineralization) that envelopes the ( i n t r u s i o nF i g .9 A ; S i l l i t o c1 9 8 9 ) . The conditions during the rnain stageof ore yet as lvell-understood, this and fbrmationare not reflects the much rrore variable geochemical in with that associated environment cornparison During the ore stage,the with acidic alteration. by hydrothennal liquid may bc lessdominated a "sulfurmagnraticvapor phasearrd its associated 'fhe presence gas bufibr" (Giggenbach 1987). olthat the early this SO2-H2S bufltr is the reasorr stageof alterationis so oxidized,as reflectedby (Whitney 1988; the alunite-pyriteassernblage 1992a). Instead, conditions duringthe Giggenbach ore stage f'luctuate within a range of redox potential that is reflectcd by enargite-pyrite+ assoaluniteand enargite-tennantite-chalcopyrite which are relativclyhigh to intermediate ciations, respectively (see sulfidation-stateassemblages, tn this Fig. 3 in Hedenquist, volurne). the Lepanto (Claveria & l'ledenquist1994) and El Indio (Jannas et al. 1990) deposits, these two and Au-rich are assemblages relatedto CLr-rich with the latterbeing respectively, mineralization, of later stage in both cases.The more reduced of are corrditions a likely consequeltce increased water-rock interaction, and, to some extent, fluid dilution of the oxidizedrnagrnatic increased by meteoricwater; this trcnd is also consistent with the isotopic compositionof waters in tlre (Fig. 8). No main ore stageof variousdeposits

discrimination. hou'ever.can be made betweena meteoric-rvater componeut that is incorporated at deep or shallorvlevels rvithin the hydrothermal system. lmportantly. salinities duringthe main ore stagecan be low (c.g.,Lepantoand El lndio. <4 equiv.rvt.oZ NaCl: T'able or moderate high 4; to ( J u l c a n r ,p t o l B e q u i v . t . % N a C l ;Z i j i n s h a nu p u w . 'lable t o 2 2 e q L r i v . t . %N a C l : w 4). Assessmento.f a |lfodel No single model adequately explainsall oi tltesevariousobservations. severalhypotheses and have beenpropcsed. eachrellectingan emphasis on individualdeposits dil-ferent or interpretations of the 1'luid-inclusion stable-isotope and data. A basic urrderstandirrg this ore-forming eur,,irono{' rnentmay be gainedby considering principal the end-rnember tluid components and ore-forming processes. The spectrum of characteristics displayed HS deposits by may be then analyzedin the contextof sucha geneticframer,vork. Four lluid regimeshave been iderrtifiedin the [{S environrnent; evidence all is present the for in early stageof IIS alteration, and threeof them are critical to fbnnation of porphyry systerns(c.g., 'Ihese Henley & IvlcNabb1978; Sillitoe 1989). end-members are: (l) a metal-rich hypersalinc rnagmaticliquid which tends to remain in the vicinity of the intrusion, but mav ascend(or be driven) to shallorve depths if the ambient r ternperature low enough (<400 "Cl) for the is mechanical strength of the rock to increase to sLrfficiently resultin brittle fiacturing(F'ournier 1992),(2) a lou'-salinity' magmatic vapor whose metal-transporting capacitydecreases sharplywith (lJedenquist volume),(3) pressure decreasing this 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 (Fig. 981), the magmatic transport"hypothesis may remainat depththroughout hypersaline liquid the evolutionof the hydrotherrnal system,and the vaporsare responsible mineralifor low-salinity zation (Sillitoe 1989; Vennemann al. 1993); et of deepmeteoricwater entrainment high-pressure

441

A. Arrihas, Jr.

vapor is required for transport of sufficient amounts of metals (Hedenquistthis volume; Sillitoe this volume). These conditions are consistent with the low salinityof the Lepantoand El Indio fluid-inclusion data.Mineral deposition in this casemay be caused mixing with cooler by groundwater by boiling, possiblyresultingfrom or the abrupt pressure reduction associatedwith hydrothermal brecciation. In the "hypersaline liquid transporl" (Fig. 9B2), following waning of the hypothesis rnagmatic vapor plume responsible for early alteration,the lithostatic-pressured system fractures and the metal-bearinghypersalineliquid ascends into the porousleached zone (Deen 1990; White l99l; Rye 1993;Hedenquist al. 1994a). e/ The dominantore-formingmechanism this case in is rnixing of the metal-bearing hypersaline liquid with cooler groundwaters the site of deposition, at not at depthin the meteoric waterconvection cell. This hypothesis has been proposed explain the to high salinitiesrecordedby inclusion fluids in (e.g., several deposits 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 increase the meteoric in water component with time. The principal differencebetweenthe two hypotheses in the is 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 remobilization the of metals by a meteoric-water-dominated hydrothermal system fiom a subjacent K-silicate assemblage and porphyry-typeprotore, such as that which may have formed closeto the intrusion (e.g.,Brimhall 1980).This mechanism, however, has not been suggested the main ore-fbrming as 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 magmatichydrothermalsystem evolves, with complexities arising from multiple intrusions, variations in depth of emplacement, and changesin the local

tectonicand hydrodynamic environment. None of the threernodels satisfies overall evidence. the For example,if metalswere suppliedonly by a dense, high-salinityliquid, a relationwould be expected among estimated salinities, metal associations, and ore gradeor metal abundances the various of deposits. Suchseems to be the case.Similarly, rrot if alterationand mineralizationwere solely the result of interaction between groundwater and low- and high-pressure vapor, respectively. high salinitiesshouldnot be as comtnonas they unless they areexplained localboilingof dilute by to moderately saline meteoric or seawaterdominated fluids. SYNTHESIS Gold, Cu, and Ag (and in a few exceptional casesalso Hg, W, Bi, Pb, and Zn) are produced from HS deposits. a sourceof Au, and because As their mode of occurrenceand the potential to overlie porphyry-typernineralizationhave been widely recognized only within the past 10 to l5 years, HS deposits represent a valuable exploration target that has been overlooked in someregions.Most known HS deposits young are in age, Tertiary and even Quaternary. Highsulfldation deposits fbrm dominantly in subduction-related plutonic-volcanic arcs, 'fhe commonlyduring crustalextension. deposits form at a depth intermediate betweenthe surface and shallow (few kilometersdepth) intermediatecomposition intrusions. The intimate relationship amongHS deposits, volcanic host rocks, and oxidized magrnaticfluid derived from a degassing intrusion supported is by (l) the followingobservations: the volcanicrocks hosting HS deposits were erupted immediately prior to mineralization, (2) the ore-fbrming hydrothermal systemcommonly follows the same plumbing as that of the magmaticsystem(i.e., rnineralization spatiallyassociated with domesor (3) volcanic conduits), the isotopic composition of hypogenesulfides(e.g., enargiteand pyrite) and (e.g., sulfates alunite commonlycan be gnd.barite) 'oS/"S modelledfrom the of sull'ur in rgneous rocks thought to be genetically related, by equilibriumfractionation betweenH2Sand SOain T -200-400 oC, and (4) on the basisof solutionat

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oxygen and hydrogen isotopic ratios, the waters are involvedin formationof HS deposits identical systo waters in active volcanic-hydrothermal in which the same HS geochemical tems, has environment beendocumented. Ore formation in some HS deposits may of and recentstudies acidic alteration, accompany Au provide the hydrothermal geochemistryof preliminary evidence that this element may be as in transported HS and low-sulfidationsystems (AuHS" and different hydrosulfide complexes Bening & Seward 1994; Au(HS)2, respectively; of Seward1913).On the other hand,the presence in many HS deposits. to moderate high salinities the intimate associationwith porphyry copperof type deposits,and the assumptions the most of geneticmodels(transport Au and Cu by recent vapor) either hypersalineliquid or high-pressure indicate that chloride complexes must also be for considered metaltransport. evolve from an early period Most HS deposits of acidic wallrock alterationto a late period of Acidic precious- and base-metalrnineralization. advancedargillic by alteration is characterized and porous (leached)rock, and the assemblages for hydrothermalfluid responsible this alteration vapor magmatic by is dominated high-temperature containingSO2,H2S, and HCl. Less reactiveand for ore oxidized fluids are typically responsible as multiple intrusions Factorssuch mineralization. and opening or closing of fractures (conduits) pressure, result in variations in the temperature, of the ascendingsolutions. and composition Combined with the shallow environment of theseconditionslead to a variety mineralization, breccias, styles (mainly replacements, of deposit 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, the orebodies between particularlythe association and the lateral and vertical zones of alteration, illustrates the basic genetic condition of HS extensive that a magmaticfluid interacts deposits, on its ly with country rock and groundwaters surface. shortpathto the earth's relatively

ACKNOWLEDGMENTS relatedto Valuableinsight on variousaspects was gained this excitingore-formingenvironment and throughdiscussions field work with M. Aoki, J. A. ArribasSr.,C. G. Cunningham, Hedenquist. W.C. Kelly, R. O. Rye, J. J. Rytuba,andT. A. Steven. Earlier versions of this manuscript benefited from constructive reviews by Phil John Bethke,Andrew Campbell,Anne Thompson, Peter Vikre, Noel White, and Jeff Thompson, Hedenquist, who also provided abundant worldwide. on documentation HS deposits REFERENCES AKAMATSU, K. ( 1993): Acid Hydrothermal Alterationat Otaru City, Hokkaido.M.S. thesis, (in Japan Japanese) Hokkaido Univ.,Sapporo,
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TAYLOR, B.B. (1992): Degassing of H,O fiom rhyolite magma during eruption and shallow intrusion, and the isotopic composition of magmatic water in h;rdrothernal systems.Geol. Surv..lapctnReport 219, 190-194. T H O M P S O N ,J . F . H . ,A B I D I N , H . Z , B O T H , R . A . . MARTOSUROYO, S., RAFFERTY, W.J. &. THOMPSON, A.J.B. (1994): Alteration and epithermal mineralization in the Masupa Ria J. volcanic center,Central Kalimantan,Indonesia. he Geoc m. Explor. 5A, 429-4 56. T H O M P S O N .J . F . H . ,L E S S M A N , J . & T H O M P S O N , r : A . J . B . ( 1 9 8 6 ) :T h e T e m o r ag o l d - s i l v e d e p o s i t A high sulfur newly recognized style of of in mineralization the Lower Paleozoic Australia. 38. Econ. Geol. 81, 732-'7 TOWNLEY, B. (1991). Evoluciony Zonacidn de la Mineralizacidn de Au y Ag, en el Sistema Epitermal de Can Can, Ill Region. B'S. thesis, Univ.deChile.

and ore alteration TURNER, S. (1936):Fluid inclusion, m l studies of an epithermal vein system: V I L A , T . ( 1 9 9l ) : E p i t h e r m as i l v e r - g o l d i n e r a l i z a t i o n mineral area,Maricungabelt, high Andes at the Esperanza Mount Kasi, Vanua Leva, Fiji. 1r Proceedirlgs Chile.RevlslaGeol. Chile 8,31 -54. of northern Symposium5, Internat.VolcanologicalCongress, Hamilton, New Zealand 1986. Univ. Auckland, s s W A L L A C E , A . B . ( 1 9 7 9 ) :P o s s i b l e i g n a t u r eo f b u r i e d Centre Continuing Education, Auckland, New in deposits middle to lateTertiary porphyry-copper ST-94. Zealand, volcanicrocks of westernNevada.1n Proceedings s Internat.Assoc. on the Cenesisof Ore Deposits, A . & S A K A I , H . ( 1 9 8 a ) :S u l f u r i s o t o p e t u d y UEDA, 5th Symposium.Nevada Bur. Mines Geol. Report volcanic rock from the Japanese of Quaternary 33,69-76. Acta 48, 1837IslandArc. Geochim.Cosmochim. I 848. W A S S E R M A N ,M . D . , R Y E , R . O . , B E T H K E , P . M . & ARRIBAS, A., JR. (1992): Methods for VELINOV. I. & KANAZIRSKI, M. (1990): For-

452

High-sulJidation Epithermal Deposits

separationand total stable isotope analysis of alunite. U.S.Geol. Surv. Open-fileReport92-9. g e W H I T E , N . C . ( 1 9 9 1 ) :H i g h s u l f i d a t i o n p i t h e r m a l o l d and a model for their deposits:Characteristics, origin. Geol.Swv. Japan Report227,9-20. wHrrE, N.c. & HEDENQUIST, J.W. (1990): Epithermal environmentsand styles of mineralization'.variations and their causes,and guidelines Explor.36,445-474. for exploration. Geochem. ,J. W H I T E , N . C . & H E D E N Q U I S T ,J . w . ( 1 9 9 5 ) : E p i and thermal gold deposits:styles. characteristics exploration. Soc. Econ. Geol. Ne*-sletter 21, (accepted). W H I T E , N . C . , L E A K E , M . J , , M C C A U G H E Y ,S . N . & o l P A R R I S ,B . W . ( 1 9 9 5 ) :E p i t h e r m ad e p o s i t s f t h e southwestPacific..J.Geochem.Explor. (accepted). a W H I T N E Y , J . A . ( 1 9 8 8 ) :C o m p o s i t i o n n d a c t i v i t yo f sulfurous species in quenched magmatic gases with pyrrhotite-bearing silicic systems. associated Econ.Geol.83, 86-92. and pressure YEN, C.C. (1976): Trappingtemperature of the fluid inclsuionsin the ganguemineralsof gold-silver-copper deposits at Chinkuashih, Taiwan. Geol. Soc. China fTaiwan] Proceedings

APPENDIX I 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. n rhyodacite : 6 (Ransome1909;Ashley, unpub. in analyses 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 andesite Middle Volcanicrock, n :2 (E lzawa, in written comm. 1995); ParadisePeak, averageof Younger andesites, : 3l (John et al. l99l); n hornblende andesite, dacitetuff, and Rodalquilar, rhyolite domes, n : 7 (Arribas et al. 1995a); Summitville,Fisher quartzlatite,n: 7 (Steven& Rattd i 960). Figure 7 values.Giverr below are Rangeof 63aS1o/oo) for the number of measurements sulfides (nrirs), sulfates (nso+), sulfide-sulfate mineral pairs (rA'oS), and references: Lepanto,flr2s: 52, n.no :38 (Hedenquist Garcia1990;J. Hedenquist & & M. Aoki, unpub. data); Chinkuashih,nvzs : 4, ^ 3 4 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 (Jensen al. 1911;Vikre et Pueblo 1989); Viejo, ngzs: 19,n s174:7,ny3aS: : 4 (Vennemann al. 1993); Julcani,n11rs 183, et

r9,127-133.
YOON, C.H. (1994): Gold content variationsin the acid-sulfate alteration zone of the Seongsanand Ogmaesanclay depositsin Naenam area, Korea. Resource Geol. 44,277. l Y U I , S . & M A T S U E D A , H . ( 1 9 9 4 ) :S e v e r a m i n e r a l deposits in Saku-Machi, Nagano prefecture. Resource Geol. 44,305. ZHANG, D. LI, D., ZHAO, Y., CHEN, J., LT,Z. & ZHANC, K. (199a): The Zijinshan deposit: the first example of quartz-alunite type epithermal Geol. depositin the continentof China. Resource 44.93-99.

453

Jr. A. Arribas,

El r?so+:55, n6345:7 (Deen 1990); lndio, ns2s_ : 3 (Jannas ol. 1990), Rodalquilar, et 11, n5sa 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 e/ datafrom Folinsbee usingthe calculated equations. al. (1912)and more recentfractionation higher than Sulfide-sulfatemineral temperatures oC were documented only at depth at 350 Summitville (T : 390 oc, -900 m below the present surface;Rye e/ al.1990) and Lepanto(I: "C at the 700-m level, immediatelyabovethe 420 FSE porphyry copper deposit; Hedenquist & the equilibria, On Garcia 1990). the basisof phase valuesfor the PuebloViejo stageI sulfide/sulfate and stage 2 mineralization were estimated by Muntean et al. (1990) to be about 3 and 35, respectively. Figure 8 variation diagram. versus 6'80 6D : Goldfield, hypogene alunite,n Go Explanation: : I (Rye et al. 1992);Ju: Julcani, (n:6), alunite average of main-stage ore fluids in Jui and tetrahedrite, galenafluid wolframite,enargite, ore of Ju2: average main-stage fluids inclusions, ore Ju3 and chalcopyrite, : late-stage in sphalerite pyrite (Deen and botroidal fluids in barite,siderite, 1990);Le : Lepanto,alunite,n : 2 (Y. Matsuhisa unpub. data);Nansatsudistrict: & J. Hedenquist, : Kasuga, aluniteft: 7,lw : Iwato,aluniter Ka 2, 6r80 values of residual vuggy silica with ore in both depositsfallbefween associated 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 :

Nevadosdel Famatina, stageV alunite-kaolinite, n I (Losada-Calderon& McPhail 1994); the average and 5l80 valuesfor La Mejicana(n : 5D 9) are similar to NF; K-silicateand quartz-sericite have6180between and at Nevados Famatina del 4 10o/oo, reflecting a larger magmatic component (Losada-Calderon McPhail 1994);PV : Pueblo & : stageI aluniteand kaolinite,PV2 : Viejo: PVI stage 2 pyrophyllite (Fig. 9 in Vennemann et al. Rodalquilar, alunite, 10, 1993); Ro (Arribas et al. 1995a);RM chalcedonic ore,n:6 : Red Mountain,Lake City, Colorado,alunite,n : 12 (Bove et al. 1990; Rye 1993); Su of Summitville,alunite,average n - l0 (6D) and n : 16 (6'80) (Rye er at. 1992),ore fluids from Rye (1993). The main ore stageat Rodalquilar(stage quartz;6D are 2) is basedon SltO of chalcedonic 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 Data for a Viejo shouldbe viewed as approximate. for Goldfield (Rye et al. 1992) single alunite suggest that mixing of a the 6D- and 6180light enriched magmatic fluid with isotop^ically 'oO-depleted waters may result in D- and hydrothermalacid-sulfatefluids (see also Vikre 1989).