EconomicGeology

Vol. 82, 1987, pp. 1575-1591

Genesisof Acid-SulfateAlterationandAu-Cu-Ag
Mineralization at Summitville, Colorado
ROGER STOFFREGEN*

Departmentof Geologyand Geophysics,

Universityof California,Berkeley,California94720

Abstract

The Summitville
Au-Cu-Agdepositoccurswithina porphyriticquartzlatite,primarilyin
a zoneof "vuggysilica"alterationcharacterized
by leachingof all majorelementsexcept
silicaandiron. Vuggysilicais bestdevelopedbetweenan elevationof 3,700 and 3,500 m
whereit occursin irregularpipesandlenticularpodsup to 70 m wideandisenclosed by up
to 30 m of intensequartz-alunitealteration.The vuggysilicazonesdiminishin sizewith
decreasing elevationandrarelyexceeda width of 2 m belowanelevationof 3,400 m. These
deepvuggysilicazonesare enclosedby quartz-kaolinitealterationwith little or no alunite.
Sulfidemineralization occursprimarilywithinthe vuggysilica.The sulfideassemblage
changes with decreasing elevationfromcovellite+ luzonite_ nativegoldto chalcopyrite
q-tennantite.Sulfides occurliningvoidsor in microveinlets andareaccompanied by minor
kaolinitcbut notby alunite.Goldalsooccursin a near-surface bariteq-goethiteq-jarosite
assemblage that crosscutsthe vuggysilica.
Consideration of alunite,kaolinitc,andpyritestabilityrelationsandof aluminumspecia-
tion at 250øCindicatesthat a pH of 2 or belowanda logfo2of -31 _ 1 (at 250øC)were
necessary to producevuggysilicaalteration.The chalcopyriteq-tennantitemineralization
occurringat depth in the vuggysilicazoneis indicativeof lessoxidizingandlessacidic
conditions. The covelliteq- luzonite_ goldassemblage requiresconditionsintermediate
betweenthosenecessary for vuggysilicaalterationand for deep sulfidemineralization.
Barite q- goldmineralizationis interpretedasa near-surface assemblage producedunder
highly acidic,oxidizingconditions.
Thesetexturalandgeochemical relationships indicatethatsulfideandgoldmineralization
postdate theformationof vuggysilicaalterationin thedepositandarenotdirectlyrelated
to thehighlyacidicsolutions
necessary for thisearlyacid-leachingevent.The changefrom
extremeacid-leaching to coppersulfideand preciousmetaldepositionmay representa
transitionfroma magmatic-vapor-dominated to a liquid-dominated
system,leadingto more
reducingandlessacidicconditions duringsulfidedeposition.

Introduction In contrastto these conditions,advancedargillic

THE SummitvilleAu-Cu-Ag depositis an outstand-
ing exampleof epithermalgold mineralizationasso-
ciated with the advancedargillic assemblageof
aluniteandkaolinitc.The depositoccursin the San
Juanvolcanicfield, a regionthat containsnumerous
epithermal precious metal veins. Several of these
havebeenstudiedin detailin recentyears,includ-
ing the Sunnysidemine (Casadevalland Ohmoto,
1977), the Lake City district(Slack,1980), andthe
Creede district,which hasbeen the subjectof ex-
haustiveresearchby the U.S. Geological
Survey,
includingStevenand Eaton (1975), Bethke et al.
(1976), Bartonet al. (1977), andBethkeandRye
(1979). Most vein mineralizationin these districts
contains sericite or chlorite in association with sul-
fides indicative of intermediate oxidation and sulfi-
dation states.
* Presentaddress: South- number of other characteristicsin common, includ-
Departmentof GeologicalSciences,
ern MethodistUniversity,Dallas,Texas,75275.
alteration requires high oxidation and sulfidation
states,as discussedby Meyer and Hemley (1967),
Hemley et al. (1969), and Brimhall and Ghiorso
(1983). This type of alteration is common in the
upper portion of porphyry copper deposits,suchas
Butte, Montana (Meyer and Hemley, 1967; Brim-
hall, 1980), El Salvador,Chile (GustafsonandHunt,
1975), andRed Mountain,Arizona (Corn, 1975). It
also occurs in epithermal environments where it
may be associatedwith high-gradegold mineraliza-
tion as at Summitville and Goldfield, Nevada (Ran-
some, 1909; Harvey and Vitaliano, 1964; Ashley,
1974), Rodalquilar,Spain(Lodder, 1966; Vivaldi et
al., 1971), and Chinkuashih,Taiwan (Huang, 1955;
Wang, 1972) or with silver mineralizationas at Jul-
cani, Peru (Noble and Silberman, 1984). These
epithermal deposits are all closely associatedin
spaceand time with volcanic activity and have a
ing high copper and relatively low lead and zinc

0361-0128/87/726/1575-1752.50 1575
1576 ROGER STOFFREGEN

contents,and large amountsof copper arsenicsul- over approximately 5 km2 (Fig. 2). It is intruded
fides(Heald et al., 1987). into the Summitville Andesitc, a series of massive
Although the conditionsrequired to produce homogeneous flowsinterpreted by Lipman (1975)
alunitic alteration from wall-rock silicate assem- as a caldera-fillingunit, and the rhyodaciteof Park
blagesof muscoviteand potassiumfeldsparhave Creek, a more heterogeneousunit localizedon the
beendiscussed in detailby Hemleyet al. (1969), northwest margin of the Platoro-Summitvillecom-
Knight (1977), and Brimhalland Ghiorso(1983), plex.Radiometricagesfor theseunitsfromMehnert
questionsremain concerningthe development of et al. (1973), Lipman (1975), and Perkinsand Nie-
the epithermalgold-aluniteassociation exemplified man (1982) are tabulatedin Figure 2. The rhyolite
by the Summitvilledeposit.In particular,the occur- of Cropsy Mountain, a coarselyporphyritic lava
rence of "vuggy silica" alteration at Summitville flow (Lipman, 1975) locally overliesthe quartz la-
suggests that pH valuessufficientlylow to prevent tite of South Mountain and postdatesit by 2 to 4
the formationof aluniteor kaolinitcexistedlocally m.y. (Perkinsand Nieman, 1982).
duringacidleaching.Thispaperconsiders the geo- The quartz latite of South Mountain is a distinc-
chemicalconditionsnecessaryfor this intenseacid tive unit characterizedby 2 to 8-cm phenocrystsof
leaching,and the relationshipbetween acid leach- pinkishsanidinethat standout againstan aphanitic
ing andthe depositionof sulfidesand goldat Sum- greenish groundmass.Partially resorbed quartz
mitville. eyesof 0.2 to 2 cm and euhedralbiotite booksof 1
Geology to 2 cm are alsovisible in hand specimens.Plagio-
clasephenocrystsare commonbut are not ascoarse
The Summitvilledepositis located in the south- grained as the sanidine. Apatite, magnetite, and
eastern San Juan Mountains of Colorado near the minor zircon occur as accessoryminerals.Though
northern edge of the Platoro-Summitvillecaldera mineralogicallysimilarthroughout,the quartzlatite
complex (Fig. 1). Lipman (1975) described the of South Mountain has been subdivided into several
evolutionof thiscomplex,whichisof earlyMiocene intrusive facies based on textural variations, as dis-
age,in detail.Mineralizationoccursprimarilyin the cussedby StevenandRatte (1960) andPerkinsand
quartz latite of SouthMountain,a porphyriticin- Nieman (1982).
trusioninterpretedby StevenandRatte (1960) asa The Summitville deposit occursadjacent to the
volcanicdome basedlargely on its morphological Pass Creek-Elwood Creek-Platoro fault zone, a
similarityto modern volcanicdomes. major northwest-trendingstructure recognizedby
The quartz latite of SouthMountain cropsout Lipman (1975) that cuts acrossthe center of the
Platoro-Summitville calderacomplex.In the areaof
the deposit this fault zone is called the South
Color•do Mountain fault and locally forms the contact be-
tween the quartz latite of SouthMountain and the
SummitvilleAndesitcasmappedby Lipman (1974).
108of •106 o A secondmajor structure,the Missionaryvein sys-
I
SAN JUAN tem, forms the contact with the Summitville Ande-
VOLCANIC
sitc on the northern border of the quartz latite of
FIELD• South Mountain.
The Summitvilledepositis comprisedof a num-
ber of discontinuousmineralized zones trending
-- .
38* north to north-northwest.Thesemay be localizedin
part on contactsbetween intrusive facies in the
quartz latite of SouthMountain (Perkinsand Nie-
man, 1982), and in some areas appear to occur
alongthe contactbetweenthe quartzlatite of South
Mountainand the rhyodaciteof Park Creek. Some
minormineralizedzonestrend nearly east-westand
DEPOSIT • / these tend to localize high-grade ore where they
co,o.
New Mex. intersect the northerly trending features (Enders
I
0
a I
40 KM
andCoolbaugh,1987). Stylesof alterationandmin-
eralizationare similarin all of thesezones,and they
FIG. 1. Locationof the Summitvilledeposit.Calderasare: B
-- Bachelor,C = Creede,LG -- La Garita, LC = Lake City, P
are discussedasa groupin the followingsections.In
-- Platoro, S -- Silverton, SJ = San Juan, SL -- San Luis, SM contrast,the Missionaryvein is mineralogicallydis-
= Summitville,andUN = Uncompahgre. ModifiedfromLipman tinct from the remainder of the depositand is not
discussedfurther in this report.
 SUMMITVILLEDEPOSIT,COLORADO:
ALTERATION& MINERALIZATION 1577

----]
Quaternary
undif ferentiated

Age(my)

18.5-
.•
..•., Rhyolite
20.2 of Cropay Mountain

2t.4-
22.9 i• Quartz
latite
of
SouthMountain

26.6• Summitville
Andeaite

27.7 • Rhyodacite
of
ParkCreek

0 1
; , , KM

FIG.2. Simplified
geologic
mapoftheSummitvilleareamodified
fromPerkins
andNieman(1982)
and
Lipman (1974).
Therectangle
inthecenter
ofthefigure
corresponds
tothearea
shown
inFigure
4.
Ages
arefromradiometric
dating
byMehnert
etal.(1973),Lipman
(1975),andPerkins
andNieman
(1982).

Hydrothermal Alteration the vuggysilicabut lackslarge void spaces.It is

Wall-rock alteration at Summitville has been dis- irregularlydistributed'invuggysilicaandis grada-
cussedby StevenandRatte(1960)andPerkinsand tional with it. Locally, 1- to 10-cm-widediscontin-
Nieman(1982). Theseauthorsrecognizeda well-
definedalterationpatternconsisting
of an inner
zoneof nearlypure quartz("vuggysilica")en-
closedby quartz-alunite,illitc, and montmorillon-
ite-chlorite-alteration. This section describes the
mineralogyand distributionof these zones and of
otheralterationassemblages
developed
at Summit-
ville.

Vuggysilica alteration
The interior alteration zone at Summitville is
characterizedby the destructionof all primary
rock-formingmineralsexceptquartz.Stevenand
Ratte(1960)coinedtheterm"vuggysilica"for this
rocktype,whichisshownin Figure3.
Vuggy silica is composedof quartz, sulfides,
minoranatase,andtracezircon.The groundmass is
madeupof 10- to 100-#-diamintergrown anhedral
quartz grains.Quartz eyes identical to those in the
fresh!atitearealsopresentandhaveapparently
beenunaffected by thealteration.
Drusyquartz
commonly linesvoidspaces in therock,anddelicate
projectionsof quartzare locallypresentwithinthe
voids.Pyrite cubesof 0.1 to I mm are common
disseminated
inthegroundmass
andinfinergrained
aggregatesin biotite sites.These'clustersalsocon-
tain abundant fine anatase. FIG. 3. Typicalvuggysilicaalteration.Coarsevoidshavebeen
produced
bytheremoval
ofpotassium
feldspar
phenocrysts
from
A secondvarietyof nearlypure quartzrock, the quartz!atite of SouthMountain.Pocketknife at lower left is
knownasmassive
silica,
ismineralogically
similar
to approximately 8 cm long.
1578 ROGER STOFFREGEN

zone near its contactwith vuggysilicabut generally

appears in the interstices of intergrown alunite
blades as the contact with illitic alteration is ap-
proached.This quartz-alunite-kaoliniteassemblage
either gradesover a few centimetersinto illitic al-
terationor is separatedfrom the illitic alterationby
outcrop
or massiveofvuggy
silica
a quartz-kaolinitezone lessthan i m wide.
Pyrite is the only commonsulfidemineral asso-
undif ferentiatedciated with the quartz-alunitealteration. It occurs
quartz-alunite-
kaolinite
intimately intergrownwith alunite in feldsparsites
clay (Fig. 6A) and in the groundmass,aswell as in clus-
ters formed after biotite. Rare covellite and native
fresh sulfur alsooccur in the quartz-alunite zone.
Illitc and montmorillonite-chlorite alteration
The quartz-aluniteor quartz-kaolinitealteration
is bordered,generallyat a sharpcontact,by intense
o loo N
illitic alteration.In this zone primary feldsparsand
meters
i i
biotite are completely replaced by illitc and fine
quartz, locally accompaniedby minor amounts of
FIG. 4. Distributionof majoralterationzonesin the Summit- kaolinitc and montmorillonite. Pyrite is the only
ville depositin part after Perkinsand Nieman (1982). Note the common sulfide within the illitc zone and occurs
irregularoutcroppatternof vuggysilicaalterationandits occur- primarily in biotite sites. Chalcopyrite, galena,
rence almostexclusivelywithin larger areasof quartz-aluniteo
kaolinitc alteration. Clay includesboth illitc and montmorillo- sphalerite,and covellite occur on the marginsof
nite-chlorite alteration. Fresh rock includes both unaltered illitized potassiumfeldspar phenocrystsbut are
quartzlatite of SouthMountainand postmineraldikes.The con- F•tFC.
tour interval is 50 m.
111iticalteration grades into a distal alteration
zone characterized by montmorillonite, pyrite,
uousveinletsof massivesilicaappearto crosscutthe minor Mn-bearing chlorite, and carbonatesand by
vuggysilica.In mostareasof the depositmassive the absenceof magnetite,which is a commonacces-
silica is volumetrically insignificant relative to soryin the freshquartz latite. This distalalteration
vuggysilica(M. S. Enders,pers.commun.,1986). affectsmostof the quartz latite of SouthMountain.
Vuggy silica alteration occursin irregular pipe-
like bodies and also in more tabular units which
A
pinch and swell alongstrike. These rangefrom a
few cmto up to 70 m acrossandextendto a depthof 3700 -
100 to 200 m. In general they show more vertical
than lateral continuity(M. S. Enders,pers. com- I ./vuggy silica
mun., 1984). Their irregulargeometryis illustrated
by the outcroppatternin Figure 4 andin crosssec-
tion in Figure 5.
Quartz-alunitealteration ß 3500 -
Quartz-alunitealterationformsanenvelopeup to
30 m wide aroundvuggysilicaand alsooccursover
largeareaswithoutadjacentvuggysilica(Fig. 4). In
the quartz-alunite zone potassiumfeldsparsare
• 3400
-
completelyreplacedby bladedaluniteup to 250 •
long. The groundmass is similarto that observedin
vuggy silica alteration but also contains abundant 3300 - + qtz-kaolinite

lathsof alunite.Summitville
alunitecontains
up to
75 molepercentsodiumbut generallyrangesfrom
10 to 25 mole percent sodium(Stoffregen,1985).
Svanbergite,a strontium-and phosphate-bearing
3200 -
/• 1-2
m.
vugg
silic
analogue of alunite, is also common in trace FIG. 5. Crosssectionalongline A to A' (Fig. 4) showingthe
distributionof vuggysilicaandquartz-a]unitealterationandtheir
amountsin the quartz-alunitezone (Stoffregenand relationshipto the narrowvuggysilicaandqu•tz-kao]inite alter-
Alpers, 1987). ation presentat greater depth. Vertical and horizontal scalesare
Kaolinitc does not occur in the quartz-alunite identical
 SUMMITVILLEDEPOSIT,COLORADO:ALTERATION& MINERALIZATION
FIO. 6. A. Photomicrograph of typicalqu•tz-alunite alter-
ation.C!e• anhe•al qu•tz is intergrown•th bladedalunite mineralsand the chalcopyrite+ tennantiteassem-
andwith pydte (py).B. Photomicrograph of kaolinitcreplacing' blageis rare. A third sulfideassemblageof digenite
alunite at an elevation of 3,390 m. The bladed habit of alunite is + chalcociteappearsto be the result of supergene
stille•dent, althoughkaolinitch• completelyreplacedalunite copper deposition(Stoffregen, 1986) and is not
in thissample.Scaleb• in bothA andB in,oates 0.1 min.
s.
Near-surfacealteration
Abovean elevationof 3,600 m vuggysilicaand
quartz-aluniteare cut by severalstylesof late-stage
veins and fracture fillings. These include barite
+ goethitefracturecoatingsanda barite+ jarosite
+ goethite+ goldassociation, whichislesscommon
but occursin veinsup to 30 cmacross. Fine-grained
mixturesof aluniteandquartz,occuringasfracture
coatingsand in 1- to 5-cm-wide veinlets, are abun-
dantin someportionsof the depositat thislevel.
Cristobalite veinlets have also been observed but
are rare. Cristobalite also occurs in mantos out-
croppingover severalhundredsquaremetersnear
the summit of South Mountain.
Deep-levelalteration
Vuggysilicaandquartz-alunitealterationare well
developedabove an elevationof 3,500 m at Sum-
mitville, but each zone tends to decrease in thick-
1579
nesswith decreasing elevation.Below3,400 m, the
vuggysilicararely exceeds2 m in width and is en-
closedby quartz-kaolinitealteration with little or
no alunite (Fig. 5). Within this zone phenocryst
sites are filled with fine kaolinitc mattes that form
slenderblades20 to 100 # in length (Fig. 6B). This
morphology-suggests that kaolinitc formed by re-
placement of alunite, an interpretation also sup-
ported by the presence of minor alunite within
someof thesebladedareas.Fine disseminated pyr-
itc is alsopresentin this quartz-kaolinitezone.
Mineralization
Sulfidesand gold mineralizationin the Summit-
ville deposit occur primarily in the vuggy silica.
Sulfidesare mostabundantin the rectangularvoids
producedby feldsparleaching,but they alsooccur
in microveinlets, as matrix material in microbrec-
cias,or asfine disseminatedgrains.In addition,rare
bonanzagoldmineralizationoccursin brecciapipes
up to 20 m long and 10 m in diameter that are
characterizedby vuggysilicafragmentsin a matrix
of kaolinitc(Stoffregen,1985).
Sulfides
Two distinct sulfide assemblages occur at Sum-
mitville. The narrow vuggy silicazonesthat occur
below3,400 m are characterized
by an assemblage
of chalcopyrite+ tennantite.Above 3,400 m, co-
vellite and luzonite are the predominant sulfide
consideredfurther in this report.
Covellite is the most abundant sulfide mineral in
the upper assemblage. It occursin bladed crystals
up to several cm long that are intergrown with
minor luzo.nite and kaolinitc.Somecovellite grains
are rimmed or veined by chalcopyrite (Fig. 7A)
whereasotherscontainirregularpatchesof chalco-
pyrite withinthem (Fig. 7B). Complexintergrowths
of chalcopyrite, covellite, and luzonite with or
without pyrite and idaitc occur along boundaries
betweencovelliteand chalcopyrite.
Covelliteislocallyintergrownwith galena,native
sulfur, marcasite,and sphalerite.Iron contentsin
sphaleriterangefrom below 0.1 to 1.7 wt percent;
mostgrainscontaingreaterthan 0.2 wt percentFe
andshowevidenceof partialreplacementby covel-
lite. Pyrite occursin relatively minor amountsin the
covellite mineralization,mainly as cubic grainsen-
closed by covellite or luzonite. Hinsdalite ((Pb,
Sr)AIa(SO•)(PO•)(OH)•)has been found in rotary
drill cuttingsfrom the upper 100 m of the deposit,
but its parageneticrelationswith sulfidesare not
known.
1580 ROGERSTOFFREGEN

up to severalmillimeterslong and tracesof covel-

lite, chalcopyrite,and kaolinitc.
In the assemblagethat predominatesbelow 3,400
m chalcopyriteand tennantite are intimately inter-
grown with pyrite and with sphaleritecontaining
between 0.5 and 2.0 wt percent Fe (Fig. 7C). Co-
veilitc is absentfrom this assemblage,
but luzonite
and enargite are both locally abundant. Minor
amountsof kaolinitc and drusy quartz occur with
the chalcopyrite.+ tennantite mineralization,and
veinlets of kaolinitc -I- quartz -I- marcasiteare also
present.

Gold and silvermineralogy

This sectionsummarizesthe work of Stoffregen
(1'986) on the gold and silver mineralogyof the
Summitvilledeposit.This studywas conductedon
heavymineral separatespreparedfrom rotary drill
cuttings.
In unoxidizedore, gold occursin grainsof up to
50 t• that locallyenclosesmallpyrite grainsor, more
rarely,are themselves rimmedby supergenedigen-
itc. Covellite, pyrite, marcasite,and minor luzonite
and sphaleriteare commonin the samplesthat con-
tainvisiblegold,but the disaggregated natureof the
samplesprecludesobservationof textural relations
betweengold and theseminerals.In oxidizedore,
gold occursas irregularly shaped5- to 10-#-diam

12

16

2O

FIG. 7. A. Photomicrograph of chalcopyrite(cp) growingon

the marginof coarsecove!lite(cv). B. Photomicrogr.
aphof covel-
lite enclosingirregularpatchesof chalcopyrite.C. Photomicro-
graph of chalcopyrite+ tennantite (tn) + sphalerite(sl) inter-
growthtypicalof the deepSummitvillesulfideassemblage. Pyrite
(py) is alsopresent.Scalebar = 0.1 mm on eachphotograph.
-log
al.•+
aso
•
FIG. 8. Stability fields of alunite, muscovite,kaolinite, and
potassium
feldspar
at 250øC,plottedin loga2•.aso;S-log
ah+aso;
•
space.Dashedlines representalunite and kaolinitc saturation
Althoughcovellite is the main sulfidemineral in boundariesat the specified
valuesof logaA]+saso4
2 a -•ßFor a given
the upper assemblage,nearly pure luzonite-enar- valueofloga2•]+3asao;
s,thesolution
isundersaturatedwithalunite
andkaolinitcto the left of the appropriatecontourandisin equi-
gite mineralizationis alsocommon.This is charac- librium with quartz only. This is equivalentto the Summitville
terized by 10- to 100-#-diam anhedral luzonite vuggysilicaassemblage. Thermodynamic datausedto compute
grainsintergrownwith prismaticenargitecrystals thisandother diagramsare tabulatedin the Appendix.
 SUMMITVILLE DEPOSIT,COLORADO:ALTERATION & MINERALIZATION 15 81

grainsdisseminated in goethitefracturecoatings,a teration. Though mineralogically similar to the

texture interpretedby Stoffregen(1986) to reflect goethite + gold assemblageformed by surficial
localremobilizationof goldduringweathering. weatheringin the upper 100 m of the deposit,this
The silver-bearingphasesobservedat Summit- barite + gold assemblage is believedto be contem-
ville are covellite, an Ag2Sphase,matildite, stro- poraneouswith hypogenecovellite mineralization,
meyerite,andelectrum.Enargite,luzonite,tennan- asdiscussed below. Quartz-alunitefracturecoatings
tite, and sphaleritecontain negligible amountsof and minor cristobaliteveining observedlocally in
silver. Covellite, which containsup to 5 wt percent the top of the depositalsopostdatevuggysilicaal-
Ag, is the main host for silver. Most gold contains terationandmayhaveformedin part duringweath-
lessthan 2 wt percentAg, but goldwith up to 18 wt ering.
percent Ag occursin a relatively silver-rich area on
GeochemicalConditionsduring
the southeastmarginof the deposit. Wall-Rock Alteration
Late barite-jarosite-goethite-gold
association In the following sections,argumentsbasedon
A distinctive assemblageof barite, jarosite, equilibrium thermodynamic considerations are
goethite, and native gold occursin veins and on usedto estimatechemicalconditionsduring alter-
somefracture surfacesin the upper portion of the ation and mineralization at Summitville. The devel-
Summitvilledeposit.This assemblage containsup to opment of the ore mineral assemblageswill be
1.0 oz/ton Au but constitutesonly a minor portion treated separatelyfrom vuggy silica and related
of the goldore in the deposit.It doesnot appearto wall-rock alteration, because these two associations
extend more than 60 m below the current surface. appearto representdifferentstagesin the evolution
Bariteis the mostabundantphasein thisassociation of the deposit.
and occursin 1- to 5-mm-longeuhedralto subhe- A temperature of 250øC has been used in esti-
dral crystals.Interlayered goethiteand mamillary mating the chemical parameters at Summitville.
jarosite partially fill the intersticesof these barite Temperatureis not well constrained,reflecting in
grains. part the absenceof ganguemineralssuitablefor
fluid inclusion studies. The 250øC value is selected
Paragenesis
basedon existingstudiesof secondaryinclusionsin
The texturalinformationpresentedabovesug- quartz phenocrysts(Stoffregen,unpub. data). This
geststhe followingparagenesis for the Summitville temperature estimate is consistentwith observed
deposit.The vuggysilicaand quartz-alunitealter- pyrite-alunite sulfur isotope fractionation (R. O.
ationappearto haveformedprior to significantore Rye, pers.commun.,1986) andwith the occurrence
depositionat Summitville,asindicatedby the oc- of kaolinite and not pyrophyllitein the wall-rock
currenceof sulfidesin open spacesin the vuggy and gangueassemblages. Phaserelationsdiscussed
silicarock and in veinletscuttingvuggysilica.In below are relatively insensitive to pressure, and
addition,the replacementof aluniteby kaolinitein vapor saturation pressure (40 bars) has been as-
thedeeperexploredportionof thedepositsuggestssumed. Stratigraphic argumentsmade by Steven
that the ore stage,whichis characterized by the and Ratte (1960) suggestthat lithostatic pressure
presenceof minor kaoliniteas a ganguemineral, did not exceed 300 bars during formation of the
postdates aluniticalterationandis accompanied at deposit.
thislevelby replacement
of "wall-rock"aluniteby Origin of vuggysilicaalteration
kaolinite.
Paragenetic relations among the ore minerals Vuggysilicaalterationwasformedby the dissolu-
themselves are not well defined.The intergrowths tionof feldsparsandbiotitefromthe quartzlatiteof
of covellite,luzonite,and enargitecommonabove SouthMountain,producinganassemblage of quartz
3,400 m suggestcontemporaneousdeposition of + pyrite. The occurrenceof this assemblage within
thesephases. In contrast,chalcopyrite occurring the alunite zone at Summitville indicatesthat pH
above3,400 m commonlyveinsor replacescovel- valueswere locally too low for the formation of
lite or is itselfreplacedby covellite.This suggests alunite or kaolinite. Where these minerals could not
conditions which fluctuated between covellite and form, aluminum released by feldspar dissolution
chalcopyritestabilityin this part of the deposit. wasremovedfrom the rock, producingvuggysilica
Below3,400 m, chalcopyriteappearsto be depos- alteration. In order to interpret the conditionsre-
itedtogetherwithtennantite andsphalerite, assug- quiredfor this aluminummobilization,it is there-
gestedby the intimateintergrowths of thesephases fore necessaryto evaluatethe stabilityof alunite
in the deepassemblage. andkaoliniteasa functionof pH at œ50øC.
The barite + jarosite+ goethite+ gold assem- As originally noted by Hemley et al. (1969),
blagecrosscuts and thuspostdatesvuggysilicaal- alunite and kaolinite stabilityrelationscan be con-
1582 ROGER STOFFREGEN

300
venientlyrepresentedona loga•+aso•-loga•i+aso•
•
activitydiagram.The aluniteandkaolinitcdissolu-
tion reactions:
AI(OH)
2+
KA13(SO4)•(OH)6
+ 6H + ß 200
= K+ + 3Al+3 + gSO•-• + 6H•O (1) := -1.0

"- 150
and
E
Al•Si•Os(OH)•+ 6H+ = 2A1+3 ß lOO

+ 2SiO2, + 5H20, (2)

(quartz] 50
!

can alsobe plotted on this type of diagramif it is I 2 3 4 5 6 7

contoured
fortheloga•+aa•o•• (Fig.8). Thedashed
lines in Figure 8 representsaturationwith alunite pH
andkaolinitcfor a givenlog,Al+•,so4
-• A_a_•: to the left of FIG. 9. Predominantaqueousaluminumspeciesasa function
these lines the solution is undersaturated with re- of pH, temperature,andtotal dissolvedsulfatecontent.Lineson
spectto these phasesand is saturatedwith quartz the figurerepresentequalactivitiesof the aqueous
species in the
only. This is equivalentto the vuggy silica alter- adjacentfields.Thedashed
boundary
aroundtheAl(SO4)
+ fieldis
ation. indicatedfor differentlogsulfatemolalities.
Thisfigureillustrates
that AI(OH)+• is the predominantaqueousaluminumspeciesat
Figure 8 was constructedassumingequilibrium low pH above 200øC.
between solution and quartz. This assumptionis
basedon the abundanceof quartz and the absence
of other SiO• polymorphsin the vuggy silica and
quartz-alunitezonesat Summitville.It is not clear The maximumpH, 4.12, usedin the calculation
how theseobservations relate to experimentalstud- wascomputedfor the assemblage
quartzq- alunite
ies (e.g., Holier, 1967; Fournier, 1986) which indi- q- kaolinitc q- muscovite(cf. Hemley et al., 1969).
catethat quartzprecipitationis inhibitedat low pH. At thisvaluethe computedamountof dissolvedalu-
Reactions(1) and (2) can be usedto calculateex- minumis near 1 ppm, suggesting that negligible
plicitly the amountof dissolvedaluminumin equi- transportof aluminumshouldbe expectedin associ-
librium with an assemblage of alunite, kaolinitc,and ationwith advancedargillicalterationasdefinedby
quartz as a function of pH, provided that the spe- Brimhall(1980), comprising the gangueassemblage
ciation of aluminumis known. The pH required for quartz q- alunite q- kaolinitc q- muscovite.Com-
vuggy silica alteration, that is, the pH at which putedtotal dissolved
aluminumincreases with de-
large-scalealuminumtransportmay occur,canthen creasingpH, reaching1,000 ppm A1 at a pH near
be estimated. 2.0. The value of dissolved A1 should continue to
The predominantaluminumspeciesasa function increaseat stilllower pH, but uncertaintyaboutac-
of pH, temperature,and total aqueoussulfatecon- tivity coefficientsin these increasinglyconcen-
centration are illustrated in Figure 9. Above tratedsolutions precludesextendingthe calculation
200øC,AI(OH)+• is the predominantdissolved alu- below a pH of 2.
minumspeciesunder acidicconditions,whereasthe Thiscalculationindicatesthat significantleaching
Al(SO4)+ complexis not significanteven at high of aluminumfrom an alunite q-kaolinitc assemblage
total sulfateconcentrations.Other ligandssuchas is unlikelyto occurmuchabovea pH of 2. More-
F- andB(OH)j can form complexeswith aluminum over, the curve shownin Figure 10 is shifted to
(e.g., Ghiorso,1980); however,there is no mineral- lower pH valuesif the solutionis assumed to be in
ogical evidenceto suggestthat either fluorine or equilibriumwith an assemblage of aluniteq-quartz
boronwasimportantin the Summitvilledeposit. without kaolinitc. This is a consequenceof the in-
Dissociationconstantsfor the aluminum species creasein log a•+aso• • required to move off the
consideredin Figure 9, when combinedwith the alunite-kaoliniteboundaryat a givenpH, whichdi-
massactionequationsfor reactions(1) and (2), dis- minishes the amount of dissolved aluminum needed
sociationconstantsfor HSO• and other pertinent to saturate with alunite. It is therefore concluded
species,anda chargebalanceconstraintcanbe used thatthe leachingof aluminumresponsible for vuggy
to solvefor activitiesand molalitiesof aqueousspe- silicaalterationat Summitvillerequired a pH of 2 or
cies in equilibrium with the assemblagealunite below.
q-kaolinitc q- quartz. The resultsof these calcula- The valueof oxygenfugacityduringvuggysilica
tions are presentedin Figure 10, which illustrates and quartz-alunitealterationcan be estimatedby
the relationshipbetweenpH andtotal dissolvedalu- considering the stabilityof pyrite andnativesulfur
minum at 250øC. (liquid)at 250øC. The dissolution
of pyrite under
 SUMMITVILLE DEPOSIT, COLORADO: ALTERATION & MINERALIZATION 1583

1.0
The boundaries established in Figure 11 for
1,000
vuggy silica alteration are somewhatarbitrary, be-
causethey are basedon solubilitycontoursand not
2.0 on equilibrium between coexistingminerals.How-
100 ever, in spite of the inherent limitationsof this ap-
3.0
proach, the diagram demonstratesthat there is a
region of pH-fo2 spacein which the vuggy silica
10
alteration,characterizedby (1) intenseleachingof
4.0 aluminum, (2) generally low or negligible pyrite
cb solubility,and(3) absenceof nativesulfur,wouldbe
expectedto developunder equilibrium conditions.
5.0
I I I• The field of quartz-alunite alteration, labeled Ib,
2.0 3,0 4,0 is alsoillustrated in Figure 11 for a log total potas-
pH
siummolalityof-4. This field occursin the region
where the stabilityfieldsof pyrite andaluniteover-
FIG. 10. Computedvalueof totaldissolved aluminumin equi- lap. Higher potassiummolalitiesincreasethe alu-
libriumwith the assemblage aluniteq- kaolinitcq- quartzas a nite and muscovitefieldsat the expenseof kaolinitc
functionof pH at 250øC.Negligibledissolved aluminumoccurs
at a pH of 4.12 (smallarrow),the calculatedvaluefor coexistence (Fig. 11). The kaolinitc field disappearsfrom the
of the aluniteq-kaolinitcq- quartzassemblage with muscovite, sulfate-dominantportion of the diagram at a log
buttheamountof dissolved aluminum increases with total potassiummolality of -2.8.
significantly
decreasingpH. Vuggysilicaalterationis inferredto havedevel-
opedat a pH below 2, asdiscussed
in the text.
T - 250 ø
acidic,oxidizingconditionscan be representedby
the reaction:

4FeS2+ 4H20 + 7H+ = 4Fe+2+ HSOj + 7H•S(aq).

(3)
Contoursof logaFe+2
in equilibriumwith pyrite (and
hematite)are shownin Figure11, a PH-fo2diagram
constructedat a log sulfurmolalityof -1.5. The -2
contourfor log aFe+2 represents,neglectingactivity
coefficients,a value of roughly 500 ppm iron in
solutionin equilibriumwith pyrite. At or abovethis
amountof dissolved ironit islikely that somepyrite
dissolution,
or possiblyevenlarge-scale
leachingof
iron from the rock, would occur. The abundanceof
pyrite in the vuggy silica, particularly in biotite
sites,indicatesthat iron wasnot significantly mobi-
lized duringacid leaching,and impliesthat pyrite
wasrelatively insolublein this acidicenvironment.
Alsoshownin Figure 11 is the field of sulfursatu-
ration. Althoughnative sulfur doesoccur locally 0 2 4 6 8
within the vuggysilicazone,it is invariablylocated pH
in void spacesand appearsparageneticallylate.
Vuggy silica alteration is thus inferred to have de-
FIG. 11. A pH-fo• diagramconstructedat 250øC and vapor
veloped outsidethe field of sulfur saturation. saturationpressure,showinginferredfieldofvuggysilica(Ia) and
The lightly shadedarea labeledIa in Figure 11 quartz-alunite(Ib) alteration for a log total sulfur molality of
representsthe inferred field of vuggysilicaalter- -1.5. Alsoshownare dashedlines indicatingthe log aFe*•in equi-
ationat Summitville.The maximumpH boundaryof librium with pyrite and hematite in the vicinity of thesefields.
2.0 is from the above discussion on aluminum mo- The upperpH limit for vuggysilicaalterationis setat 2, andthe
other boundariesare set by the native sulfur field and the -2
bility. The upperfo2boundaryis providedby the contour for log aFe*•(see text). An increasein the total sulfur
-2 solubilitycontour of log aFe+2in equilibrium molalityto -1.0 shiftsthis regionto highervaluesof logfo•, as
with pyrite, andthe lower pH andfo• limitsby the shownby the field labeled with an asterisk.The quartz-alunite
field is boundedby the stabilitylimits of alunite and pyrite at an
sulfursaturationboundary.Increasingthe assumed assumedlog total potassiummolality of-4. Alunite, kaolinitc,
logtotalsulfurmolalityto -1.0 shiftsthisregionto andmuscoviteboundariesare alsoshownfor a log total potassium
a slightlyhigherfo2 value (Fig. 11). molalityof-3.
1584 ROGER STOFFREGEN

GeochemicalConditionsduring Ore Deposition T= 250 ø

The most useful subdivision of ore minerals in the , ' TI•' I i
•1 •1•1
28
Summitvilledepositis into a highJ•2 and a low rs2 I II

assemblage, corresponding to the shallowcovellite-

luzonite and the deep chalcopyrite-tennantiteas- 3O
semblages.The theoreticalbasisfor this distinction :,?so4"•1•',,,.
is discussedby Meyer and Hemley (1967) and by 32 _
Brimhall and Ghiorso(1983).
Assuminga temperature of 250øC, as for the - CV '• -
vuggy silica alteration, it is possibleto assignspe-
cific limits to the sulfidation states of the two sulfide
-
assemblages. This is illustratedin Figure 12, anfoa- 0
j•a plot. Figure 12 showsstabilityfields of chalco- !

pyrite, covellite, tennantite, and other pertinent _e• •

//
phasesat 250øC. The upperfsalimit for chalcopy- 38

.................
'•'.;'•
•.,•
Y'•?
•".•'•
.........
.'"",••
rite, defined by the bornite q- pyrite field, is not
directly relevant to the Summitvilledeposit,which -•IZ•99F•Oli
S
contains essentially no bornite. This reflects the
high arseniccontent of the system,which has fa-
vored the formationof copper arsenicsulfidesin 42 po
log • S = -1.5
place of bornite. Pertinent phaserelationsare dis- I
0
I I
2
I I
4
I
6
I I
8
cussedby Knight (1977) andBrimhall(1979).
The Summitvilleore assemblages conformwell to pH
the stabilityrelationsevident in Figure 12. In par- FIC. 13. A pH-fo2diagramat 250øC and vapor saturation
ticular, the apparentdisequilibrium,basedon tex- pressureshowingthe fieldsof vuggysilica(Ia), quartz-alunite
tural criteria, between associatedchalcopyriteand (Ib), chalcopyrite-tennantite(IIa), and covellite-luzonite(IIb)
mineralization
for a logtotalsulfurmolalityof-1.5 andalogtotal
covellite and the almostcomplete absenceof ten- potassium molalityK of-4.0, as in Figure 11. The kaolinite-
nantite from covellite-bearing areas is consistent alunite and kaolinite-muscovite boundaries are also shown for a
with calculatedphaserelations.It shouldbe noted, log •K of -3. The upperpH limit for IIa mineralization is pro-
vided by the kaolinite-muscovite boundary,and the upperfoa
limit for IIb mineralizationby the kaolinite-aluniteboundary.
T=250 o The lowerpH limit on boththeseassemblages is uncertain.This
figureindicatesthatthe ore assemblages (IIa andIIb) couldnot
form underthe highlyoxidizingand acidicconditions required
4 S•L• for the vuggysilicaandquartz-alunitealteration(seetext).
' Slv,.I • 1Tb _•.
6-cvcc
f /
I • '•'
pyrlte / \FeSO
4 {/ 0

however, that some of the chalcopyrite-covellite

1• 'tn IZn99FemlS -'[Ea • / •• intergrowthsobservedin the deposit may have
............................................
...............
/,' / formed due to pyrite supersaturation(cf. Barton
12' IZn9Fe, IS .../,? and Skinner, 1979).
............. •. •,' / '"' '
•............................ • /
In Figure 13, a pH-foadiagram,inferredstability
fieldsof the low (IIa) andhigh (IIb)rs2 assemblages

14 ///,/ are comparedwith thosefor vuggysilica(Ia) and

quartz-alunite(Ib) fromFigure 11. Asin Figure 11,
a log total sulfurmolalityof-1.5 wasusedto con-
, , •'zf ./, /, ........... structFigure 13. Constraints on the ore stages(IIa
44 40 36 32 28
andIIb) are providedin part by the tennantite,co-
vellite, and sphaleritereactionsfrom Figure 12.
-logf02 The upperfoa boundfor the IIb assemblage is pro-
FIG. 12. Logfo2-1ogJ% diagramat 250øCandvaporsaturation videdby the boundarybetweenkaoliniteandalun-
pressure.Arrowsrepresentthe rangeof sulfurfugacityfor the ite, basedon the commonoccurrenceof kaolinite
deepchalcopyrite+ tennantiteassemblage (IIa), providedby the with covellite in the deposit and the absenceof
enargite-tennantite reaction and the maximum iron content alunitein this assemblage. Kaolinitestabilityis also
(roughly1.0 mole % Fe) observedfor Summitvillesphalerite,as
well as for the covellite+ luzonite assemblage (IIb). Note these usedto providea maximumpH for the IIa assem-
assemblages provideconstraintson sulfurfugacitybut not on blage.The lowerpH limit is not definedfor either
oxygenfugacityduringore deposition. sulfideassemblage, althoughthe occurrenceof the
 SUMMITVILLE
DEPOSIT,
COLORADO:
ALTERATION
& MINERALIZATION
native sulfur with covellite mineralizationsuggests
relativelylow pH conditions,at leastlocally,for the
IIb assemblage.
As illustrated in Figure 13, both the IIa and IIb
fields occur outside those of vuggy silica and
quartz-alunite alteration. This relationshipis main-
tainedregardlessof the sulfurmolalityusedto con-
struct the diagram; it is consistentwith the textural
evidence that sulfide depositionwas not contem-
poraneouswith vuggysilicaalteration.
Figure 13 alsoillustratesthat the IIb field occurs
at higher fo2 valuesthan the IIa field, suggesting
that the changefrom ehaleopyrite+ tennantiteto
eovellite + luzonite mineralization observed with
increasing elevation at Summitville reflects an in-
creasein oxygenlugdeity. However, this transition
from the IIa to IIb assemblage may alsoreflect an
increasein total sulfur molality at constantfo2, as
discussedin Hayba et al. (1986). Sulfur isotope
studiesare currentlyin progresson the depositand
shouldprovide better constraintson fo• valuesin
both ore stages.
Barite + gold mineralization
The barite q- jarosite q- goethite q- gold assem-
blage observedlocally in the upper 60 m of the
Summitville deposit is indicative of a restricted
highly oxidizing environment.Fluid inclusionsin
barite from this assemblagehomogenize near
100øC (Cunningham, 1985), suggesting that it
was not produced by sulfide oxidation during
weathering.
The conditionsnecessaryto produce a goethite-
jarosite assemblageat 100øC can be estimatedby
consideringthe reaction
6FeO(OH) + 2K+ + 2H + + 4HSO•
(goethite)
= 2KFea(SO4)2(OH)6. (4)
The positionof the goethite-jarositeboundary in
pH-total sulfatespace,contouredfor potassiumac-
tivity, is shownin Figure 14 for a temperature of
100øC. Note that a relatively high sulfur molality
and low pH are required to produce the goethite
+ jarosite assemblageat this temperature. These
values are even more extreme than those required
for jarosite formation at 25øC (ef. van Breeman,
1972; Nordstrom, 1977). They indicate that the
barite + jarosite + goethite+ gold assemblage de-
veloped at Summitville was associatedwith acidic,
sulfate-rieh solutions.
These conditions are similar to those inferred for
the vuggysilicaalteration.However, the absenceof
pyrite in the barite-gold mineralization requires
that this assemblagedevelopedunder more oxidiz-
ing conditionsthan thoseresponsiblefor the vuggy
silica.
1585
1
o,O
-2
-3 • i i i
0 I 2 3 4
pH
FIG. 14. Boundarybetweengoethiteandjarositestabilityat
100øCandvaporsaturation pressure,
contouredfor logtotalmo-
lalityofpotassium.Thisdiagram indicatesthatbothlowpH anda
highaqueous sulfurmolalityare requiredto producea jarosite
+ goethiteassemblage at thistemperature. The Summitvilleas-
semblage of barite+ jarosite+ goethite+ goldis thereforein-
terpretedto haveformedfromacidic,sulfur-richsolutions. The
complete absence of sulfidemineralsalsoindicateshighlyoxidiz-
ingconditionsduringformationof thisassemblage.
Interpretation
This section considersthe processesthat may
havecausedvuggysilicaalterationin the Summit-
ville deposit.Theseincludethe formationof sul-
furicacidby near-surface oxidationof H2Sandthe
introductionof anSO2-bearing magmaticgasphase,
yieldingsulfuricacidand H2Sby SO2dispropor-
tionation.In addition,a geologicmodelis presented
to explainthe transition fromthe earlyacid-leach-
ing stageto sulfideandgoldmineralization in the
deposit,and to accountfor the observedvertical
variationin ore mineral assemblages.
The vuggysilicarockismineralogically
similarto
acid-leachedzones formed in many modern hot
springs. Theseareascontainquartzandanataseor
other titanium oxidesof presumedresidualorigin
(e.g.,Schoenet al., 1974), alongwith opal,cristo-
balite, and minor amountsof pyrite and/or iron
oxides.
Theyareformedbythesurficial
oxidation
of
H2Sevolvedat a boilingwatertable,producingthe
H2SO4necessary for intenseleaching,asoriginally
documented by Day andAllen (1925) in the Mount
Lassenareaandby AllenandDay (1935) at Yellow-
stone. This processhas been incorporated into
modelsof epithermalore depositionby Buchanan
(1981) andBergerandEimon(1983).
Acid-sulfatealterationcan alsodevelop at depth,
in the absence of near-surface oxidation. Assem-
blagesof quartz,alunite,and/orpyrophyllitenot
related to surficial oxidation have been observed in
a numberof geothermalfields,suchasMatsukawa,
Japan(Sumi,1969), and other examplescited in
Fournier (1986).
1586 ROGER STOFFREGEN
Moreover, advancedargillic alteration is present
in the upper portionsof someporphyry copper de-
posits, most notably Butte, Montana (Meyer and
Hemley, 1967; Brimhall, 1979, 1980). This type of
alterationin a hypogenesettinghasbeen attributed
to the effects of magmaticallyderived sulfur gas
species(e.g., Meyer and Hemley, 1967). Brimhall
and Ghiorso (1983) demonstratedthe theoretical
basisfor this interpretationby modelingthe inter-
actionof quartz monzoniteprotore,water, and sul-
fur gasspeciesin the Butte deposit.
The extreme acidities required for vuggy silica
alteration can thus be produced in two fundamen-
tally different ways: by near-surfaceH2S oxidation
abovea boiling water table or by hypogeneintro-
duction of oxidizing magmatie gases.These two
mechanisms are not necessarilymutually exclusive.
The vuggy silicaand adjacentalunite zone at Sum-
mitville are believed to result primarily from the
effectsof magmatiegasascendinginto a relatively
near-surface environment, and not from oxidation
of H2S abovea boilingwater table. This interpreta-
tion is basedon the followingarguments.
First, alunitie alteration in the depositis contem-
poraneouswith the crystallizationof the quartz la-
tite of SouthMountain,basedon radiometricdating
by Mehnert et al. (1973) and Perkinsand Nieman
(1982). This intrusive unit provides an obvious
source of the magmatie SO2 needed to produce
aeid-sulfatealterationin a hypogenesetting.The
large vertical extent of acid leachingat Summitville
alsosuggests a hypogenesourcefor thesesolutions.
The occurrenceof vuggy silica and alunitie alter-
ation over a vertical range of 300 m is in contrastto
the geometryof mostaeid-sulfatecappingsin geo-
thermal areas.These generallyextend to depthsof
no more than 50 m, as at SteamboatSprings,Ne-
vada (Sehoenet al., 1974).
Anotherpotentiallyusefultest for discriminating
between hypogeneH•SO4 formation and surfieial
acidproductiondue to H•S oxidationisprovidedby
sulfur isotopes.As noted by Hayba et al. (1986),
hypogene acid formation resulting from the SO•
disproportionationreaction:
4SO• + 4H20 = 3H•SO4 + H2S, (5)
producesisotopicallylight sulfide and heavy sul-
fate. In contrast, oxidation of H•S in the near-sur-
face settingshouldnot result in isotopicfraetiona-
tion of sulfate and sulfide. Kyusu and Kurahashi
(1984) demonstrated that these theoretical rela-
tionships have practical value in distinguishing
mechanismsof sulfurie acid formation in Japanese
geothermal areas. Preliminary results from the
Summitville deposit (R. O. Rye, pers. eommun.,
1986) showthat sulfatein alunite is 20 to 25 per mil
heavier than sulfide in coexistingpyrite, againsug-
gestingthat SO• disproportionationand not H=S ox-
idationwasthe mostimportant mechanismfor acid
generationin the deposit.
Basedon thesearguments,it is believed that the
vuggysilicaalterationat Summitvilleresultedfrom
the introductionof magmaticgasin a near-surface
environment, contemporaneouswith the crystalli-
zation of the quartz latite of South Mountain. The
base of the vuggy silica alteration is interpreted to
mark the depth at which the magmaticvapor phase
beganto condense,or to encounterdownwardper-
colatingsurfacewaters,producingthe acidic,sul-
fate-rich solutionsrequired for this type of alter-
ation.
Figure 15A providesa schematicillustrationof
the depositduringacidleaching.Vuggysilicaalter-
ation probably extended upward to the palcosur-
faceduringthis time, where it may havebeen asso-
ciated with fumarolic activity. This early, magma-
tic-vapor-dominated alterationstagecausedintense
cation leachingbut did not contribute significant
goldor other metals.
The depositionof sulfidesand gold in the vuggy
silicazone is believed to result from the collapseof
the magmatic-vapor-dominated systemand its re-
placementby a liquid-dominatedphasewith a sig-
nificant meteroric water component. A similar
model involving a transitionfrom vapor to liquid
dominationwas presentedin Perkins and Nieman
(1982). This influxof relativelydilute waterswould
end acid leachingby causingdilution of acidiccon-
densatesin the vuggysilica.Its effecton redoxcon-
ditionswould dependon the sourceof the waters.
Ground water buffered by the surroundingfresh
quartz latite assemblageof potassiumfeldspar
+ magnetite+ biotite would decreasefo2, whereas
oxygenatedsurfacewaterscouldincreaseit.
The occurrenceof the chalcopyrite 4- tennantite
assemblage in the base of the vuggy silica and co-
vellite + luzonite at higher elevationssuggestsan
increase in oxidation state and dissolved sulfur con-
tent with elevation during ore deposition. This
changemaybe in part relatedto the replacementof
alunite by kaolinitc observedin the base of the
vuggysilica.Thiscanbe illustratedby the replace-
ment reaction:
2KAla(SO4)•(OH)6+ 6SiO2 + 3H•O
= 3AI•Si•Os(OH)4+ 2K+ + 4HSO• + 2H +. (6)
This reaction causes an increase in the total sulfur
contentand oxidationstateof the fluid by the addi-
tion of bisulfate. Note also that although the reac-
tion introducespotassiuminto solution,it produces
an equalamountof hydrogenion, thustendingto
maintainsufficientlyhighacidityto stabilizekaolin-
ite instead of muscovite. This is in accord with the
absence of sericite in vein mineralization in the
Summitvilledeposit.
 SUMMITVILLE DEPOSIT, COLORADO: ALTERATION & MINERALIZATION 15 8 7

A poiilble zone of lurflclal oxidetlon

zone of hypogene acid-leaching

- 500 m redox condltlonl controlled

by H2S-SO2 content of vapor

ibale of condenlatlon

SO2 -H2S-(HCI) bearing vepor

eecendlng on fracturel

B bolling and oxidation with

barite and Au deposition

zone of mixing

cv and Au deposited due to

Influx of acld-sulfate condensate

- 500 rn

cp-tn deposEIon and

alunlte replacementby kaollnlte

FIG. 15. A. Schematicillustrationof formationof the vuggy silicaand enclosingquartz-alunite

alteration (stippled pattern) at Summitville.Acid-sulfatealteration in the depositis interpreted to
reflect an influxof magmaticgasinto the baseof the system.Condensationof this gas,representedby
black dotsindicatingliquid water, generatesan acidic solutionrich in H2S and HSO• and initiatesacid
leachingover a vertical range of severalhundred meters.This stagemay have been accompaniedby
fumarolicactivityat the paleosurface.B. Schematicillustrationof sulfidemineralizationat Summitville,
illustratingthe developmentof three differentore assemblages at differentlevelsof the deposit.The
blackarrowsrepresentliquid water, whichhasoccupiedthe vuggysilicaareadominatedin the previous
stageby magmaticgas.This water is not in equilibriumwith wall-rockaluniticalterationin the baseof
the systemm•d replacesit with kaolinite. The deep level chalcopyrite+ tennantiteassemblage is
depositedin thisportionof the deposit.The circlesnear the surfacerepresenta vapordevelopedabove
a boilingwater table, accompanied by depositionof the shallowbarite + jarosite+ goethite+ gold
assemblage. The intermediatecovellite + gold zone is producedby the influx of surficialcondensates
backinto the vuggysilicazone,where they mix with, and oxidize,ascendinghypogenesolutions(see
text).
1588 ROGER STOFFREGEN

Other factors may also have acted to favor the assemblage that predominatesbelow an elevationof
formationof the covellite-dominatedassemblage in 3,400 m, and a covellite q-luzonite assemblage that
the upper portion of the Summitvilledeposit.De- predominatesabove it. A considerationof the sta-
creasingtemperature in the higher portionsof the bility fields of these assemblages
indicatesthat sul-
depositwould favor covelliteover chalcopyrite,as fide mineralizationoccurredunder more reducing
discussedby Knight (1977). However, an absence andlessacidicconditionsthan thoseresponsiblefor
of geothermometricdata precludesevaluatingthe vuggy silica alteration. This observation,taken in
importanceof temperaturegradientsin the deposit. conjunction with textural relationshipsbetween
Localization of the covellite assemblageat rela- sulfideq- kaolinite mineralizationand vuggy silica
tively high elevationsmay also reflect draining of alteration, demonstratesthat ore depositionpost-
surface-derived acid-sulfate condensates back into datesthe formationof the vuggysilicaand alunitic
the vuggysilicazoneduringsulfidedeposition.This alteration.
processhas been studied by Reed and Spychef Gold mineralization occurs in association with the
(1986), who used a computer simulationto model covellite-bearingassemblage at Summitvillebut not
the mixing of acidic, sulfate-bearingwaterswith a with the deeperchalcopyriteassemblage. Gold also
more reduced "hypogene" fluid. Their study indi- occursin a near-surfacebarite + jarosite q-goethite
catesthat a kaolinitc q-covellite q-gold assemblage, assemblage.This associationof gold with assem-
similarto the SummitvilleIIb stage,could be pro- blagesindicativeof relatively oxidizingand acidic
duced within this zone of mixing. Gold precipita- conditionssuggests that golddepositionoccurredin
tion occurs in this model due to decreases in solu- response to destruction of gold-bisulfide com-
tion pH, which destabilizegold bisulfidesby con- plexes, due to an increase in acidity and oxygen
verting HS- to H2S. fugacitywith increasingelevationin the system.
The potentialimportanceof surficialoxidationin The transitionfrom acidleachingto sulfidedepo-
the Summitvillesystemduringore depositionis also sitionobservedat Summitvilleis interpretedasthe
suggested by the barite-gold assemblage. This result of a change from a magmatic-vapor-domi-
highly oxidized assemblagestrongly suggestsfor- nated to more reducing liquid-dominated system
mation by interaction with atmosphericoxygen, as (cf. Perkins and Nieman, 1982). In this model,
discussedby Cunningham (1985). Its positionjust chemicalconditionsduring acid leachingprimarily
abovethe covellitezone makesit a plausiblesource reflect the disproportionationof magmaticallyde-
of acidic, oxidizingsolutionsthat could drain back rived SO• to yield sulfuricacid and HgS.Ore deposi-
into the vuggy silica zone, leading to the mixing tion occursin a subsequentliquid-dominated sys-
effects discussed above. tem, with more oxidized assemblagesforming at
The proposedpattern of sulfidemineralizationis higherelevations.This trend mayreflectan input of
illustratedin Figure 15B. The complextextural re- surface-derivedacid-sulfatewaters into the top of
lations in the intermediate portion of the deposit the system(cf. Reed and Spychef, 1986), and also
suggestfluctuation between covellite-stable and an increase in bisulfate concentrationscaused by
chalcopyrite-stableconditions,possiblycausedby alunite-destructive reactions occurring at lower
variationin the depth of penetration of these sur- elevations.
face derived waters. The barite-gold assemblage Acknowledgments
forms at or abovethe water table and is produced
by surficialoxidation. This work wassupportedby a grant from the An-
acondaCompany. I would like to thank George
Summary and Conclusions Brimhallfor his supportand encouragementduring
Hydrothermalactivity in the Summitvilledeposit the courseof this study. I also thank Bill Nieman
and Mike Perkins of Anaconda and Steve Enders
can be divided into two stages:an early period of
acid leachingthat was responsiblefor vuggy silica and Mark Coolbaughof GalacticMinerals for shar-
and quartz-alunite alteration, and a later period ing their observations with me. Helpful reviewsof
when copper, gold, silver, and arsenicwere intro- this manuscript or the thesison which it wasbased
duced. Geochemicalargumentspresented in this were provided by the individualsmentionedabove
report basedon the stability of alunite, kaolinite, and alsoby Phil Bethke, J. K. Bolhke, Dan Hayba,
pyrite, and native sulfurindicatethat the vuggysil- H. C. Helgeson,T. N. Narisimham,and two Eco-
ica alterationformed at a pH of 2.0 or below, and at nomic Geologyreferees.The U.S. GeologicalSur-
an oxygenfugacityslightlyabovethe boundarybe- vey assistedin preparationof figures.
tween the H2S and bisulfate fields. Temperature July 30, 1986; March 2, 1987
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APPENDIX

Thermodynamic
Data Usedto ConstructDiagrams
Log K
(250øC, vapor saturation
Reaction pressure) Source

Figure 8
Alunite-kaolinite-muscovite-feldspar
equilibria
1. KAla(SO4)•(OH)6
+ 6H+ = K+ + 3A1+a + 2SO•• + 6H•O -19.58
2. AI•Si•Os(OH)4
+ 6H+ = 2A1+a+ 2SiOg(quartz)
+ 5HgO 1.22
3. KAlaSiaO•0(OH)•
+ 4H+ + 2SO•• = KAla(SO4)•(OH)6
+ 3SiOn(quartz) 23.43
4. 3KA1SiaO8+ 6H+ + 2SO•e = KAla(SO4)•(OH)6
+ 9SlOg(quartz)
+ 2K+ 31.37
5. 2KAlaSiaO•0(OH)e
+ 2H+ + 3H•O = 3AleSilOs(OH)4+ 2K+ 4.01
6. 3AI•Si•O•(OH)4
+ 6H+ + 2K+ + 4SO•• = 2KAla(SO4)•(OH)•
+ 3H•O+ 6SiO•(q,•a•tz) 42.84
7. 3KA1SiaO8
+ 2H+ = KAlaSiaO•0(OH)•
+ 6SiOg(quartz)
q-2K+ 7.95

Figure 9
Aluminumspecies
8. A1+a+ H•O = AI(OH)+2+ H + 1.31
9. A1+a+ 2H•O = AI(OH)• + 2H+ -1.00
10. A1+a+ 4H•O = AI(OH)• + 4H+ -12.20
11. A1+a+ SO•2 = Al(SO4)
+ 5.53

Figure 11
Aqueoussulfurspecies
12. H•S(•,)+ 202 = 2H+ + SO•• 56.36 1,4
13. H.zS(•,)+ 20• = H + + HSO• 61.77 1,4
14. H•S(•,)= H + + HS- -7.35 4
15. HS- + 20• = H + + SO•• 63.71 1,4
16. HSO• = H + + SO•2 -5.41 4

Sulfur saturation

17. 2H•S(•q)+ O• = 2S(t)+ 2H•O 35.50 1,5

18. 2H+ + 2HSO• = 30• + 2S(t)+ 2H•O -88.02 1,5

Muscovite, alunite, and kaolinite

19. 2KAla(SO4)•(OH),
+ 6SiO2(quartz)
q-3H•O = 3A12Si20,(OH)4+ 2H+ + 2K+ + 4HSO• -21.24 1,4
20. 2KAla(SO4)•(OH),+ 6SlOg(quartz)
q- 3H•O + 2H+ = 3AI•Si•O,(OH)4+ 2K+
+ 4H•S(•q)+ 80• -268.28 1,4
21. 2KAlaSiaO•0(OH)•+ 3H•O + 2H + = 3AI•Si•O,(OH)4 + 2K+ 4.01 1

Hematite-pyrite
22. 2FeS• + 7.50• + 4H•O = Fe•Oa + 8H + + 4SO•• 193.43 1
23. 2FeS• + 7.50• + 4H20 = Fe•Oa + 4H + + 4HSOj 215.03 1,4
24. 4FeS• + 4H•O + 140• = 4Fe+• + 8HSOj 410.56 1,4
 APPENDIX (Cont.)
Figure 11
Hematite-pyrite
25. 4FeSz+ 4HzO+ 8H+ = 4Fe+a+ 8H2S(aq)
q-2Oz -83.60 1,4
26. 2FezO3+ 8H + = 4Fe+z + 4HzO + Oz -19.50 1

Figure 12
Iron oxide and sulfide minerals

27. FeaOa + 2Sa = 2FeSa + 1.50a -29.55 1

28. 3FeSa + 2Oz = FeaO4 + 3Sa 35.50 1
29. FeS + 0.5Sa = FeSz 7.01 1
30. 2Fe304 + 0.5Oz = 3FeaO3 17.65 1
31. 3FeS + 2Oa = Fe304 + 1.5Sz 56.54 1
32. 2FeSz + 60• = Fe2(SO4)3+ 0.5S2 169.46 1,6
33. FeaOa+ 1.5Sz+ 4.50z = Fe2(SO4)3 139.91 1,6

Coppersulfideminerals
34. 2CuS = CuaS + 0.5Sa -3.39 1
35. 4FeSa + CusFeS4 = 5CuFeSa + Sa -8.60 1
36. 2FezOs + CusFeS4 q- 3S• = 5CuFeSz + 3Oa -67.70 1
37. 2FesO4 + 1.5CusFeS4 + 4.5S• = 7.5CuFeSz + 4Oz -83.90 I

Miscellaneous

38. 2S(l)= Sz(g) -4.73 5

39. 8CuaAsS4= 2CulzAs4S13q- 3Sa -29.22 5
40. FeS(sphalerite)
+ 0.5Sz = FeSa logv•eS
Asphalerite
= -7.38 - 0.5 1ogfsa7
Sulfide-sulfate
equilibria
41. PbS + 2Oz: PbSO4 63.38 8
42. CuS + 2Oa = CuSO4 52.52 8
43. CuzS + 4Oz + 0.5Sz = 2CUSO4 108.64 8

Figure 13
Covellite field

44. 2CuS + 1.5Oz + HzO = CuzS + 2H + + SO•z 37.59 1

45. 2CuS + HaO = CuaS+ HaSlaq)+ 0.5Oa -18.77 1,4
46. 2CuS q- 1.5Oz q- HzO = CuzS q- H + + HSO• 42.99 1,4
Iron oxide and sulfide minerals

47. 2FesO4 + 0.5Oz -- 3FeaOs 17.65 1

48. 3FeSz + 6HzO = FesO4 + O2 + 6HS- + 6H + -100.92 1,4
49. FeS + 0.5Oa + HzSlaq)-- FeSz + HzO 22.40 1, 4
50. FeS + 0.5Oz + HS- + H + = FeSz + HzO 29.75 1, 4

Chalcopyritefield
51. 5CuFeSz+ 4H + + 2SO;a = 4FeSa+ CusFeS4q- 3Oz + 2HaO -73.36 1
52. 5CuFeSz+ 2H + + 2HSO• = 4FeSz + Cu5FeS4+ 3Oz + 2HzO -84.18 1,4
53. 5CuFeSa+ Oz + 2HzSlaq)
= 4FeSz+ CusFeS4+ 2HzO 39.37 1, 4
54. 5CuFeSz + 2HS- + 2H + + Oa = 4FeSa + CusFeS4+ 2HaO 54.07 1, 4
55. 2.5CuFeSz+ 6Oz + 3HaO = 0.5CusFeS4q- FeaOs+ 6H+ + 3SO•z 156.79 1
56. 2.5CuFeSa + 6Oa + 3HaO = 0.5Cu5FeS4 q- FezOs q- 3H + q- 3HSO; 172.99 1, 4
57. 1.5CuFeSzq- 3.5Oz q- 1.8HzO -- 3.6H+ q- 1.8SO•z q- 0.3Cu5FeS4q- 0.4FesO4 90.54 i

Tennantite-enargiteboundary
58. 8CusAsS4q- 9Oz + 6HzO = 2CulzAs4Sl3q- 12H+ + 6SO;z 216.63 1, 4,5
59. 8Cu3AsS4 q- 902 q- 6H20 = 2Cu12As4S•s+ 6H- + 6HSO• 249.09 1,4,5
60. 8Cu3AsS4
+ 6HzO = 2CuI2AsiSI3q- 3Oz + 6HzS(aq) -121.53 1, 4,5
61. 8Cu3AsS4q- 6HzO = 2Cu12As4S13
q- 3Oz + 6H + + 6HS- -165.63 1, 4,5

Iron in sphalerite
l
62. FeS(sphalerite)
+ HzSt•q)+ 0.5Oz = HaO + FeSz 20.77 1, 4, 7
63. FeS(sphalerite)
q- HS- q- H+ q- 0.5Oz = HaO q-FeSz 28.12 1, 4, 7
64. FeS(sphalerite)
q-SO•2 q-2H+ = 1.5Oa+ HzO+ FeSa -35.59 1, 4, 7
65. FeS(sphalerite)
q-2.25Oz+ HaO = 0.5FezOs+ 2H+ + SO•z 61.13 1, 4, 7

Figure 14
66. 6FeO(OH)(goeth,
te)+ 2K+ + 2H+ + 4HSO; = 2KFes(SOa)z(OH)6 9.43a 1, 9, 10

References:1, Helgesonet al. (1978); 2, ReedandSpychef(1984); 3, Wolery(1983); 4, Helgeson(1969); 5, BartonandSkinner

(1979);6, BarinandKnacke(1973);7, ScottandBarnes(1971);8, BarnerandScheuerman (1978);9, Ballet al. (1979); 10, Langmuir
(1971)
i LogK valuesforthesereactions
arecomputed
for 1 molepercentFeSin sphalerite
z LogK at 100øC,vaporsaturation
pressure
1591