Professional Documents
Culture Documents
Genesis of Acid-Sulfate Alteration and Au-Cu-Ag Mineralization at Summitville, Colorado
Genesis of Acid-Sulfate Alteration and Au-Cu-Ag Mineralization at Summitville, Colorado
Genesisof Acid-SulfateAlterationandAu-Cu-Ag
Mineralization at Summitville, Colorado
ROGER STOFFREGEN*
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.
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).
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
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 1579
s.
the upper assemblage. It occursin bladed crystals
up to several cm long that are intergrown with
Near-surfacealteration minor luzo.nite and kaolinitc.Somecovellite grains
Abovean elevationof 3,600 m vuggysilicaand are rimmed or veined by chalcopyrite (Fig. 7A)
quartz-aluniteare cut by severalstylesof late-stage whereasotherscontainirregularpatchesof chalco-
veins and fracture fillings. These include barite pyrite withinthem (Fig. 7B). Complexintergrowths
+ goethitefracturecoatingsanda barite+ jarosite of chalcopyrite, covellite, and luzonite with or
+ goethite+ goldassociation, whichislesscommon without pyrite and idaitc occur along boundaries
but occursin veinsup to 30 cmacross. Fine-grained betweencovelliteand chalcopyrite.
mixturesof aluniteandquartz,occuringasfracture Covelliteislocallyintergrownwith galena,native
coatingsand in 1- to 5-cm-wide veinlets, are abun- sulfur, marcasite,and sphalerite.Iron contentsin
dantin someportionsof the depositat thislevel. sphaleriterangefrom below 0.1 to 1.7 wt percent;
Cristobalite veinlets have also been observed but mostgrainscontaingreaterthan 0.2 wt percentFe
are rare. Cristobalite also occurs in mantos out- andshowevidenceof partialreplacementby covel-
croppingover severalhundredsquaremetersnear lite. Pyrite occursin relatively minor amountsin the
the summit of South Mountain. covellite mineralization,mainly as cubic grainsen-
closed by covellite or luzonite. Hinsdalite ((Pb,
Deep-levelalteration
Sr)AIa(SO•)(PO•)(OH)•)has been found in rotary
Vuggysilicaandquartz-alunitealterationare well drill cuttingsfrom the upper 100 m of the deposit,
developedabove an elevationof 3,500 m at Sum- but its parageneticrelationswith sulfidesare not
mitville, but each zone tends to decrease in thick- known.
1580 ROGERSTOFFREGEN
12
16
2O
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
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:
.................
'•'.;'•
•.,•
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
ibale of condenlatlon
eecendlng on fracturel
zone of mixing
- 500 rn
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
during this alteration is poorly constrainedbut is REFERENCES
believed to have been near 250øC.
Allen,E. T., andDay, A. L., 1935, The hot springsof the Yellow-
Sulfidemineralizationin the Summitvilledeposit stone National Park: Carnegie Inst. Washington Pub. 466,
can be subdividedinto a chalcopyriteq- tennantite 525 p.
SUMMITVILLEDEPOSIT,COLORADO:ALTERATION& MINERALIZATION 15 8 9
Ashley,R. P., 1974,Goldfieldminingdistrict:NevadaBur.Mines Harvey R. D., and Vitaliano, C. J., 1964, Wall rock alterationat
andGeology,Rept. 19, p. 49-66. Goldfield,Nevada:Jour.Geology,v. 72, p. 564-579.
Ball,J.W., Jenne,E. A., andNordstrom,
D. K., 1979,WATEQ2 Hayba,D. O., Bethke,P.M., Heald, P., andFoley, N. K., 1986,
--a computerized
modelfor traceandmajorelementspecia- Geologic,mineralogicand geochemical characteristics
of vol-
tion and mineral equilibriaof naturalwaters:Am. Chem. Soc. canic-hostedepithermalprecious-metaldeposits:Rev. Econ.
Symposium,Ser. 93, p. 815-836. Geology,v. 2, p. 129-162.
Barin, I., and Knacke,O., 1973, Thermochemicalpropertiesof Heald, P., Foley, N. K., and Hayba, D. O., 1987, Comparative
inorganicsubstances: Berlin, Springer-Verlag,921 p. anatomyof volcanic-hosted epithermaldeposits:Acid-sulfate
Barner, H. E., and Scheuerman, R. V., 1978, Handbook of ther- and adularia-sericitetypes:ECON.GEOL.,v. 82, p. 1-26.
mochemicaldata for compounds and aqueousspecies:New Helgeson,H. C., 1969, Thermodynamics of hydrothermalsys-
York, Wiley, 156 p. temsat elevatedtemperaturesandpressures:Am. Jour.Sci., v.
Barton,P. B., Jr., andSkinner,B. J., 1979, Sulfidemineralstabil- 267, p. 729-804.
ities, in Barnes,H. L., ed., Geochemistryof hydrothermalore Helgeson,H. C., Delany, J. M., Nesbitt,H. W., andBird, D. K.,
deposits:New York, Wiley Intersci.,p. 278-403. 1978, Summaryandcritiqueof the thermodynamic properties
Barton,P. B., Jr., Bethke, P.M., andRoedder,E., 1977, Environ- of rock-formingminerals:Am. Jour.Sci.,v. 278-A, p. 1-229.
mentof ore depositionin the Creedeminingdistrict,SanJuan Hemley, J. J., Hostetler,P. B., Gude, A. J., and Mountjoy,W. T.,
Mountains,Colorado:Part III. Progresstowardinterpretation 1969, Somestability relationsof alunite: ECON. GEOL.,v. 64,
of the chemistryof the ore-formingfluid for the OH vein: p. 599-612.
ECON. GEOL., v. 72, p. 1-24. Holier, H., 1967, Experimentelle Bildung von Alunit-Jarosit
Berger, B. R., and Eimon, P. I., 1983, Conceptual models of durch die Einwirkung von Schwefelsaureauf Mineralien and
epithermalpreciousmetal deposits,in Shanks,W. C. III, ed., Gestein:Contr. MineralogyPetrology,v. 15, p. 309-329.
Cameronvolumeon unconventionalmineral deposits:New Huang, C. K., 1955, Gold copper depositsof the Chinkuashih
York, Soc. Mining EngineersAm. Inst. Mining Metall. Petro- mine, Taiwan,with specialreferenceto the mineralogy:Acta
leum Engineers,p. 191-205. Geol.Taiwanica,no. 7, p. 1-20.
Bethke,P.M., andRye,R. O., 1979, Environmentof ore deposi- Knight,J. E., 1977, A thermochemical
studyof alunite,enargite,
tion in the Creede mining district, SanJuanMountains,Colo- luzonite, and tennantite deposits:ECON. GEOL., v. 72, p.
rado: Part IV. Sourceof fluids from oxygen,hydrogen,and 1321-1336.
carbonisotopestudies:ECON.GEOL.,v. 74, p. 1832-1851. Kyusu,K., and Kurahashi,M., 1984, Isotopicgeochemistryof
Bethke,P.M., Barton,P. B., Jr., Lanphere,M. A., and Steven, acid thermal waters and volcanicgasesfrom Zao volcanoin
T. A., 1976, Environmentof ore depositionin the Creedemin- Japan: Jour. Volcanology Geotherm. Research, v. 21, p.
ing district,SanJuanMountains,Colorado:II. Ageofminerali- 313-331.
zation: ECON. GEOL., v. 71, p. 1006-1011. Langmuir,D., 1971, Particle size effect on the reactiongoethite
Brimhall, G. H., Jr., 1979, Lithologicdeterminationof mass -- hematite + water: Am. Jour. Sci., v. 271, p. 147-156.
transfermechanisms of multiple-stage
porphyrycopperminer- Lipman,P. W., 1974, Geologicmap of the Platorocalderaarea,
alizationat Butte, Montana:Vein formationby hypogene southeasternSan Juan Mountains, southwesternColorado:
leachingandenrichment of potassium-silicate
protore:ECON. U.S. Geol. SurveyInv. Ser. Map 1-828.
GEOL.,v. 74, p. 556-589. -- 1975, Evolutionof the Platorocalderacomplexandrelated
-- 1980, Deep hypogeneoxidationof porphyrycopperpotas- volcanicrocks, southeasternSan Juan Mountains, Colorado:
sium-silicateprotore at Butte, Montana:A theoreticalevalua- U.S. Geol.SurveyProf.Paper852, 128 p.
tion of the copperremobilization
hypothesis:
ECONGEOL.,v. Lodder,W., 1966, Gold-alunitedepositsand zonalwallrockal-
75, p. 384-409. teration near Rodalquilar,southeastSpain:Univ. Amsterdam,
Brimhall,G. H., Jr., and Ghiorso,M. S., 1983, Origin and ore- Geol. Inst. Mededeel.,no. 318, 95 p.
formingconsequences
of theadvanced
argillicalteration
pro- Mehnert,H. H., Lipman,P. W., and Steven,T. A., 1973, Age of
cessin hypogeneenvironments
by magmaticgascontamination mineralizationat Summitville,Colorado,asindicatedby K-Ar
of meteoricfluids:ECON.GEOL.,v. 78, p. 73-90. datingof alunite:ECON.GEOL.,v. 68, p. 399-401.
Buchanan,L. J., 1981, Preciousmetal depositsassociated
with Meyer, C., and Hemley, J. J., 1967, Wall rock alteration, in
volcanic environments in the southwest: Arizona Geol. Soc. Barnes,H. L., ed., Geochemistryof hydrothermalore deposits:
Digest, v. 14, p. 237-262. New York, Holt, Rinehart,andWinston,p. 166-235.
Casadevall, T. J., andOhmoto,H., 1977, Sunnyside mine,Eureka Noble, D.C., and Silberman, M. L., 1984, Evolucion volcanica e
miningdistrict,SanJuanCounty, Colorado:Geochemistryof hidrotermaly cronologiade K-Ar del distritominero de Jul-
goldandbasemetalore deposition in a volcanicenvironment: cani,Peru:Soc.Geol. del Peru, Vol. Jubilar,p. 1-35.
ECON. GEOL.,v. 72, p. 1285-1320. Nordstrom,D. K., 1977, Hydrogeochemical andmicrobiological
Corn,R. M., 1975, Alteration-mineralization zoning,Red Moun- factorsaffectingthe heavy metal chemistryof an acid mine
tain, Arizona: ECON. GEOL., v. 70, p. 1437-1447. drainagesystem:Unpub.Ph.D. thesis,StanfordUniv., 210 p.
Cunningham,C. G., 1985, Characteristics of boilingwater table Perkins,M., andNieman,G. W., 1982, Epithermalgoldmineral-
and carbondioxidemodelsfor epithermalgold deposition: ization in the SouthMountain volcanicdome, Summitville, Col-
U.S. Geol.SurveyBull. 1646, p. 43-46. orado:Denver RegionExplorationGeologistsSymposiumon
Day, A. L., andAllen, E. T., 1925, The volcanicactivityandhot the genesis of RockyMountainoredeposits: Changeswith time
springsof LassenPeak:CarnegieInst. Washington Pub. 360, and tectonics,Denver, Colorado,Nov. 4-5, 1982, Proc., p.
190 p. 165-171.
Enders,M. S., andCoolbaugh,M. F., 1987, A geologicmodelof Ransome,F. L., 1909, Geologyand ore depositsof Goldfield,
goldmineralization for exploration,
development andproduc- Nevada:U.S. Geol. SurveyProf. Paper66, 258 p.
tionat Summitville, Colorado[abs.]:Geol.Soc.America19, p. Reed, M., andSpycher,N., 1984, Calculationof pH andmineral
245. Abstracts with Programs,v. 19, p. 245. equilibriain hydrothermalwaterswith applicationto geother-
Fournier,R. O., 1986, The behaviorof silicain hydrothermal mometryand studiesof boiling and dilution:Geochim.et Cos-
solutions:Rev. Econ. Geology,v. 2, p. 45-60. mochim.Acta, v. 48, p. 1479-1492.
Ghiorso,M. S., 1980, Mineralsolutionequilibriain volcanichot -- 1986, Boiling,cooling,and oxidationin hydrothermalsys-
springs:Unpub. Ph.D. thesis,Univ. of California,Berkeley, tems:Calculations of gas,aqueous,and solidphasechemistry
381 p. appliedto epithermaloregenesis: Rev.Econ.Geology,v. 2, p.
Gustafson,
L. B., andHunt, J.P., 1975, The porphyrycopper 249-270.
depositat E1Salvador,
Chile:Ecoa. GEOL.,v. 70, p. 857-912. Schoen,R., White,D. E., andHemley,J.J., 1974, Argillizationby
1590 ROGER STOFFREGEN
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
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
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
Figure 13
Covellite field
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