ECONOMIC GEOLOGY

AND THE

BULLETIN OF THE SOCIETY OF ECONOMIC GEOLOGISTS

VOL. 87 JANUARY-FEBRUARY, 1992 NO. i

Hydrothermal Ore-Forming Processesin the Light of Studiesin Rock-

Buffered Systems:I. Iron-Copper-Zinc-LeadSulfideSolubilityRelations
J. J. HEMLEY, G. L. CYGAN,
U.S. GeologicalSurvey,Reston,Virginia 22092

j. B. FEIN,
Grant Instituteof Geology,Universityof Edinburgh,Edinburgh,ScotlandEH9 8JW

G. R. ROBINSON, AND W. M. D'ANGELO

U.S. GeologicalSurvey,Reston,Virginia 22092

Abstract

Experimentalstudies,usingcold-sealandextractionvesseltechniques,were conductedon
Fe, Pb, Zn, and Cu sulfide solubilitiesin chloride solutionsat temperaturesfrom 300 ø to
700øC and pressuresfrom 0.5 to 2 kbars.The solutionswere bufferedin pH by a quartz
monzoniteandthepurepotassium
feldspar-muscovite-quartz
assemblage
andinj•2-fo2largely
by the assemblage pyrite-pyrrhotite-magnetite.
Solubilitiesincreasewith increasingtemperatureand total chloride, and decreasewith
increasingpressure.The rise in solubilityis particularlysteepbetween 300 ø and 500øC and
between 1,000 and 500 bars.With increasingtemperatureat any given pressure,or with
decreasingpressureat any given temperature,metal solubilityeventuallypassesthrougha
maximumdue to increasingcompetitionfor chlorideby the alkali,hydrogen,andbasemetal
ionsandbecauseintersectionwith a two-fluidregioneventuallyoccurs.In that portionof the
two-fluidregionencounteredin the study,metalsolubilitiesin the brine were very high,but
solubilitiesin the gasphasealsowere significant.In a systemcontrolledby the potassium
feldspar-muscovite-quartz buffer, 1-m total CI-, and the assemblagepyrite-pyrrhotite-mag-
netite-sphalerite-galena-chalcopyrite,
solubilitiesin ppm at 1 kbarand300% 400ø, and500øC
were 237, 1,216, and 5,636, for Fe; 5l, 613, and 3,105 for Pb; 36, 423, and 2,649 for Zn;
and 11, 40, and 113 for Cu, respectively.At 400øC, 0.5 and 2 kbars,the valueswere 2,627
and500 for Fe; 1,262 and 194 for Pb; 983 and 120 for Zn; and60 and29 for Cu, respectively.
All of the abovewere in the single-fluidregion.Single-metalsolubilitiesalsowere investigated
to assessthe influenceof irononthe solubilityof the othermetalsandto corroboratepreliminary
dissociationconstantsfor the metal chloridecomplexesinvolved.
The effectof increasingchlorideconcentration on solubilityreflectsprimarilya shift to
lowerpH via the silicatebufferreactions.The effectof decreasing pressurereflectsprimarily
the relativechangein the dissociation constants of the chloridecomplexes involved.Increasing
sulfurfugacitylowerssolubility,but in systems controlledat relativelylow valuesby anrs2
buffer or wall-rocksulfidationreactions,solutionsof high metal contentrelativeto reduced
sulfurwill tend to developat high chlorideconcentrations.
Similarityin behaviorwith respectto the temperatureand pressureof Fe, Zn, and Pb
sulfidesolubilitiespointsto similarityin chloridespeciation,and the neutralspeciesappear
to be dominantin the high-temperature region.At 500øC and l kbar, the log KD valuesfor
FeCI•, PbCI•, ZnCI•, and CuC1ø are, respectively,-8.76, -9.14, -10.86, and -6.22.

Introduction a wide rangeof pressure,temperature,andfluidcom-

A BETTER knowledge,basedon experimentalstudies, positionis necessaryfor continuedimprovementin
of ore metalsolubilitiesin hydrothermalfluidsover our understanding of ore-formingprocesses andthe
9, HEMLEY ET AL.
geneticmodelswe attemptto deduce.Over the past
few decades,andparticularlyin the lastseveralyears,
a considerablebody of experimentaldata has been
developedin the subcriticalregionfor relativelysim-
ple systems.For example,the solubilitytrendsof a
number of individual metal sulfides over varied chlo-
ride or bisulfideconcentration
alongthe liquid-vapor
curve of water have been worked out. In a few in-
stancesthe experimentalsystemwas more complex
(e.g., the work of Wood et al., 1987) but againwas
limited to temperaturesof 350øC or less. Much of
this work has been summarized in extensive reviews
by BarnesandCzamanske(1967) andBarnes(1979).
More recent investigations, someof which involve
high-temperaturesolubilities(500ø or 600øC) of
metal oxidesin a sulfur-free system,are those of
Frantz et al. (1981), Seward (1981, 1984), Barrett
and Anderson (1982, 1988), Wilson and Eugster
(1984), Ruaya and Seward (1986), Bourcier and
Barnes(1987), Eugsteret al. (1987), andothers.From
the standpointof theoreticaltreatmentof high pres-
sure-temperature thermodynamic relations,a number
of investigators have contributed,but the mostex-
tensiveandusefulcontributionsfor solutionequilibria
have been those of H. C. Helgesonand coworkers
(e.g., 1976, 1978, 1981).
The purpose of the experimentalstudiesnoted
abovewasto definethe complexingor speciation be-
havior of the metal or metalsin questionto sucha
degree that dissociationconstantsand other ther-
modynamicinformationcan be deducedand calcu-
lationsandextrapolations then madeto morecomplex
systems andmoreextremeconditionsof temperature
and pressure.This approachhas been successfulto
only a limited degreebecausethe equationsof state
involved (i.e., the pressure,temperature,and com-
positionaldependenciesof activitiesfor the metal
complexesand other constituentsof the electrolyte
hostfluids)are simplytoopoorlyknownfor the prob-
lem at hand.Previouswork that relatesto the present
investigationwasdoneunder conditionsappreciably
different from ours and, for purposesof comparison
with ours, ones that generally require accurate
knowledgeof somekey variable,usuallypH, which
wasnotpossible withinthe contextof the givenstudy.
In other instances,importantderivedvariables,such
as dissociationconstants,cannotbe satisfactorilyap-
plied or extendedto the conditionsof our studybe-
cause of inadequate thermodynamicinformation.
Moreover,the differencesin characterof complexing
that develop under more extreme pressure-temper-
atureconditionsare sometimes not evenglimpsedin
lowertemperatureinvestigations. For theseandother
reasons,we still havea rather weakunderstanding of
somemajor geologicquestions,namely, (1) sources
of metalsand controlson the acquisitionprocess,(2)
controlsontransportanddeposition, especiallyunder
more extreme pressure-temperature
conditions,(3)
controlson zoningandparagenetic relations,and(4)
reasonsfor differencesin metalsuitesarisingin dif-
ferentgeochemical-geological environments.
To throwadditionallight on someof theseques-
tions,we have undertakenan investigationof solu-
bilitiesin a mixedmetal sulfidesystem(Fe, Zn, Pb,
and Cu) under bufferedconditions(i.e., controlled
pH, J•, andfo•) in chloridesolutions, overtemper-
aturesrangingfrom 300ø to 700øC and pressures
from0.5 to 2 kbars.Thisinvestigation is anextension
of earlier work on Fe in an aqueouschloride,sulfur-
free system(Whitneyet al., 1985) to a morecomplex
metalsulfidesystem.Asin the earlierwork,porphyry
copperand othermagmatically affiliatedhydrother-
mal depositsare emphasized,althoughthe applica-
tions are broaderthan for thoseparticularenviron-
ments. In other words, the result is a reconnaissance
mapofthe solubilitiesof fourmetalsovera fairlywide
range of geologicallyreasonablepressure-tempera-
ture-solutioncomposition(PTX) conditions.Because
this is a reconnaissance
study,highprecisionfor the
datawasnot the aim, althoughthe qualityappearsto
be comparableto much of that in the literature on
hydrothermalsolubilities.
TheoreticalBackground
To achievegeologicallymeaningfuland thermo-
dynamicallywell-constrainedresultsin sulfidesolu-
bility experimentsin an aqueouschloride,polymetal
system,the systemmust be controlledor buffered
with respectto thosevariablesthat determinemetal
solubility,namelypH andthe fugacitiesof sulfurand
oxygen.Granitic silicateassemblages are amongnu-
merousnaturalassemblages that act asbuffersto var-
iousionicratiosin a coexistingchloridesolution.Be-
causefeldsparsare the mostabundantphasesin the
assemblage, a primarycontrolonpH isthe hydrolysis
reaction of alkali feldsparto muscoviteor an alumi-
nosilicate (Hemley, 1959; Montoya and Hemley,
1975) throughreactionssuchas:
1.5KA1SiaOs+ H +
K feldspar
= 0.5Ktl2tlSiaOlo(OH)2 -t- 38iO2 -t-K+ (1)
muscovite quartz
and
KA1SiaOs -t- H +
K feldspar
= 0.5AlzSiO5+ 2.5SiOz+ K+ + 0.5HzO. (2)
andalusite quartz
The equilibriumconstants of thesereactions,com-
binedwith activitiesof the crystallinephases,fix the
 HYDROTHERMAL ORE-FORMING PROCESSES.
PT. I 3

activity ratio of aqueousK+/H+ and, combinedwith gram as indicated. The muscovitecompositionis

the dissociationconstantsof HC1 and KC1,controlthe movedslightlytowardparagonitcbut remainsclose
ratio of total KC1/HC1in the chloridesolutions.At a to end-membermaterial, as is to be expectedfrom
giventotal KC1,a•i* in the systemis then defined. the dataof Hewitt andWones(1984); alkalifeldspar
In thisinvestigation,
two slightlydifferentpH buff- compositions are thoseexpectedfrom the work of
erswere used,namely,the pure potassiumfeldspar- Orville (1963). For the potassium system,the buffer
muscovite-quartz assemblage andthe potassium feld- value is givenby the point on the K axisat the potas-
spar-andesine-muscovite-quartz assemblage for a rock siumfeldspar-muscovite boundary(1.95); the points
of quartz monzonitecomposition.For thisbuffer, the at 0.5 and 2 kbarsare alsoshown.Figure 1 is similar
compositionsof the alkali feldsparand plagioclase to the diagramgivenin Whitney et al. (1985), based
controlthe ratioof aqueous
Na+/K+ andCa+2/(Na+)
2 on relationsgiven in Montoyaand Hemley (1975),
in the solutionthroughthe exchangereactions: but it incorporatescorrectionson the positionsof the
potassiumfeldspar-muscovite and muscovite-anda-
lusite boundariesdevelopedas a part of this study.
NaA1Si3Os+ K- = KA1Si3Os+ Na- (3) The sodium-richsideof the diagramremainstentative.
albite K feldspar The presenceof Fe, Pb, Zn, and Cu chloridesin
and
the solutionintroducesadditionalmetal activityand
speciationrelations.Above 400øC all cations,both
CaA12Si2Os + 4SiO2 + 2Na+ alkaliandbasemetal,are presentlargelyaschloride
complexesrather than as free ions, and the relative
anorthite quartz concentrations of the elements then reflect a com-
=2NaA1SiaOs
+ Ca+2. (4) petition for the chlorideanion.This competition,in
albite turn, dependsuponthe strengthof the chloridecom-
plexesinvolved(i.e.,theirdissociation constants)and
The combined effect of alkali elements can be il- the equilibriumconstantsof the respectivesulfide
lustratedin log • KC1/• HC1versuslog • NaC1/• dissolutionreactions.Iron, in particular,becomesa
HC1relationsderivedexperimentally in thisstudyand majorcomponentof the solutionat hightemperature
shown in Figure 1. For the quartz monzonite, the and thereforea major competitorfor chloride.
solutionisessentially bufferedat the K feldspar-albite- Controlson sulfurand oxygenfugacitieswere ac-
muscovite-quartzquadruplepoint, except that the complished by internalbuffering(i.e., the bufferwas
activityof albite is reducedby solidsolutionwith Ca part of the charge)with the assemblage magnetite-
and K feldsparby Na. This solid solutionshiftsthe pyrite-pyrrhotite.The reactionsfixingO2 and S2fu-
point down and to the left on the K, Na-bearingdia- gacity at this triple point are:

2FeS2= 2FeS + S2(g• (5)

pyrite pyrrhotite
and

3FeS2+ FeaO4 = 6FeS + 202(g). (6)

pyrite magnetite pyrrhotite
Muscoviteß Fugacityrelationsare givenin Figure 2 for 500øC
and i kbar total pressurebasedon the SUPCRTpro-
• Albite gram (Johnsonet al., 1992). With decreasingtem-
perature, fugacity values decreaseand the triple
Andalusite pointsmoveawayfromoneanother,but the topologic
relationsremainthe same.Stabilityrelationsfor chal-
Pg
! ,11 , copyrite and someother copper sulfidesalsoare in-
1 2 3 dicated and it is apparent that chalcopyrite-pyrite-
log YNaC1/Y.HC1
pyrrhotite-magnetiteis a stable assemblage.Also
shown are fugacity contoursfor H2S and SO2 (SO3
FIG. 1. ExperimentalK feldspar-muscovite-quartz andK feld- valuesalsomight be indicatedbut are very much
pH buffer relationsat 1 m total smaller);the contoursindicate that the pyrrhotite-
spar-plagioclase-muscovite-quartz
chloride and 500øC. For the pure K system,ß = 0.5 kbars, pyrite-magnetitetriple point is well within the field
ß = 1 kbar, andß = 2 kbarspoints.The 1-kbarpoint within the
to the K feldspar-muscovite-andesine-where H2S is the dominantsulfurspecies.
muscovitefield corresponds
quartz equilibrium point projected to the K-Na plane. Sodium The dissolution reactions for the ore minerals result
sideof diagramis tentative.Pg = paragonitc. from the combinedeffect of the bufferingreactions
4 HEMLEY ET AL.

+2
Similarreactionscanbe written for galena,sphalerite,
and chalcopyrite:
2KCIø + muscovite+ 6 quartz + 0.25Fe304
+ ZnS(or PbS) = 3 K feldspar+ 0.25FeS•
S(v)
+ 0.5FeS + ZnCl•(or PbCI•) + H•O (11)
-2
and

KC1ø q- 0.5 muscoviteq- 3 quartz q- 0.125Fe•O4

+ CuFeS2: 1.5K feldsparq- 0.625FeS2
+ 0.75 FeS + CuCIø + 0.5HaO. (12)
-6 In thecomplexmixedsystemcontaining allbasemetal
sulfidesandall silicatephasesin excess,
the equilibria
expressed in equations(10-12) are concurrentlysat-
isfied.

Experiments
Startingmaterials
-24 The silicates,with the exceptionof quartz, were
syntheticto assure
rapidequilibration
rates(avggrain
Logfo2 size< 5 #m). The quartzmonzoniteassemblage cor-
FIG. 2. Buffer relationsfor Sz and O2 fugacitiesin the Fe-S- responds in composition
to Nockolds'(1954) average
O (solidlines) and Cu-Fe-S-O (dashedlines) systemsat 500øC hornblende-biotitequartz monzoniteand was syn-
and 1-kbar total pressure,basedon thermodynamicdata from thesized in bulk from a gel at 650øC and i kbar
SUPCRT. Dotted lines indicate SO2 and H2S fugacitiesand the
arrow indicatesthe sulfur condensationpoint; po -- pyrrhotite,
(Whitney,1972). The chemicalcomposition is given
cp -- chalcopyrite,bn -- bornite,cc = chalcocite,and cv = co- in Table 1. The material contained alkali feldspar
vellite. Only a portionof the bn/ccboundaryis shown. (Or70Ab30),
plagioclase,
quartz, minor biotite, and
minoramountsof magnetiteandclinopyroxene. Pla-
gioclase
discussedabove. As indicated, the control on H + is
composition couldnotbe determined by X-
ray or microprobe analysis
(all of the mineralswere
givenby reaction(1), anda dissolution
reactionfor a too fine grained for microprobework), but bulk
sulfidemay be illustratedas: chemicalanalysis,
coupledwithanestimateof mineral
2H+ + FeS= Fe+2+ H2S/m, (7) proportions,indicatesa composition of sodicande-
sine.The potassiumfeldspar-muscovite assemblage
Combining(1) and (7) yields: waspreparedasa gel of equalmoleproportions of
2K+ + muscoviteq- 6 quartz q- FeS the twomineralsandcrystallized at 550øCandi kbar
for oneweek. The resultingpotassium
feldspargave
= 3 K feldspar
+ Fe+• + H•S<g/. (8) an orthoclaseX-ray powder pattern; the muscovite
wasa mixtureof 1M and2M polytypes.The synthetic
Thus, the net or overall reaction consistsof the con-
sumptionof aqueousK+ plus muscoviteto produce feldsparcompositions
arecomparableto thoseof the
K feldsparandaqueous
Fe+•. Buttequartzmonzonite,whichalsowasusedasthe
Adding an appropriaterelationshipfor the buff- pH bufferin a numberof exploratory runs.The syn-
eringoffo2andfs•, theticandnatural materialsproduced the sameresults
withinthe experimental uncertaintyinvolvedin the
4H2S<•) + Fe304= FeS• + 2FeS+ 4H20, (9) study.
andexpressing the reactionmorerealisticallyin terms The magnetiteandsulfidemineralsusedwere nat-
of an aqueousassociated chloridespeciesinsteadof ural materials,characterizedby X-ray diffractionand
ions, we have: chemicalanalysis. Naturalmaterialwasusedto avoid
theanomalously highsolubilities
thatmayresultfrom
2KC1ø q- muscoviteq- 6 quartz q- 0.5FeS structuraldeficiencies,
andparticularlyfromthe fine
q- 0.25Fe304 = 3 K feldsparq-FeCI• grainsizeencountered, in syntheticsulfides.These
minerals,andtheir minorelementimpurities,alsoare
+ 0.25FeS• + H•O. (10) listed in Table 1.
 HYDROTHERMALORE-FORMINGPROCESSES.
PT. i 5

TABLE1. Compositionsof StartingMaterials

Quartz monzonite Natural minerals

Synthetic Butte I Minor elements

(%) (> 100 ppm)
SiO• 66.8 65.49 Pyrite, Park City, Utah: Zn = 1,900, Cu -- 880, Sn = 140
A12Os 15.28 14.49 Pyrrhotite, Stoneham,Maine: Cu -- 1,100, Mn = 490, Zn = 160,
FezOs 4.842 2.11 Pb -- 150
FeO 2.90 Magnetite, Cornwall, Pennsylvania:Cu = 700, Mn -- 670, Zn = 380,
MgO 1.40 2.45 Sn-- 140, Pb-- 130, Mo-- 130
CaO 3.41 4.29 Sphalerite, Balmat, New York: Fe -- 3%, Cd -- 2,800, Cu = 890,
Na20 3.57 2.80 Pb = 850, Mn = 630; Creede, Colorado: Fe = 0.17%,
K20 4.70 3.66 Cd -- 6,700, Pb = 270
TiO2 0.65 Galena, Park City, Utah: Sb -- 2,700, Cu -- 770, Ag = 380
P205 0.21 Chalcopyrite,Ellenville, New York: Zn = 1,900, Pb -- 910, Ag -- 450
CO2 0.05 Digenite, Butte, Montana
MnO 0.10 Chalcocite, Butte, Montana
SrO 0.04
BaO 0.05
S 0.01
H•O + 0.56
H20- 0.05
Total 100.00 99.91

Knopf (1957)
As synthesizedin gel; reducedto about 1:1 Fe+•:Fe+sbeforecrystallization

All solutions were madefromcommercialanalytical spikedto the apparentequilibriumvalue,for example,

standards; ferrouschloridewaspreparedwithin a few an element concentrationsometimespassedthrough
hoursbefore useto guardagainstoxidation. a maximumin the firstfew daysandthen taperedoff.
Rod bomb methods:Hydrothermalmethodsand
Experimentalprocedures precisionusingthe cold-sealrod bombswerebasically
Two experimentalmethodologies were employed thosedescribedin Hemley et al. (1980) andWhitney
in thisstudy:(1) a cold-seal,rodbombtechniqueusing et al. (1985). Gold capsules,rather than platinum,
a rapid ice-mushquench,modifiedto meet the diffi- were used to prevent lossof iron and sulfur to the
cultiesinherentin sulfidesolubilitywork;and (2) an tube from the iron mineral O•-S2 buffer. The runs in
extractionvesseltechnique using an internal, col- thesevesselswere of two types:preliminaryexperi-
lapsiblegoldbag. In methodology(2) the solutionis mentationto establishby successive equilibrationruns
extractedat P and T through an internal filter, and (i.e., the results of one run were the approximate
therefore,back-reaction with the solidson coolingis startingpoint for the next) the generalregionof sol-
avoided.Althoughmostof the work wasin coldseals, ubility equilibriumasshownby a constantsolubility
useof two methodologies gaveadditionalsupportfor vs.time plot; and a setof final equilibrationrunswith
the accuracyof the experimentalfindings.Moreover, initial compositions at andnear thissolubilityplateau
someinformation,suchasthe H2Scontentof the hy- in order to arrive at a final equilibriumvalue and its
drothermalfluid, couldbe obtainedonlythroughthe reproducibility.This equilibrationincludedreversals
extractionprocedure. in aqueousK, Na, and Ca in the quartz monzonite
The makeupof the solidreactantchargewasa sil- studies.A minimumof three final runsgenerallywas
icate buffer assemblage,either quartz monzonite made at each PT point and the resultsof theseruns
(QM) or potassium feldspar-muscovite-quartz(KMQ), are givenin Tables2 and3. The largenumberof runs
plus the iron mineral S2-O•buffer assemblage, plus leadingup to thesefinal equilibrationsare not pre-
sphalerite,galena,and chalcopyrite.Total chloride sented. Fresh solids were used in each of the succes-
for essentiallyall runswas1 molal.Aqueoussolution sive equilibrationruns, and in this way the solution
to silicateratio wasabout5:1 by weight,andsilicate wasforcedinto eventualequilibriumwith the solids
to total sulfide ratio about 1:1. Run times were 8 to listed in Table 1. The equilibrium reachedwasmeta-
12 weeks at 300øC, 3 to 4 weeks at 400øC, i to 2 stablein the sensethat slowadjustmentsin feldspar
weeksat 500øC, and about5 daysat 600øC. Fairly compositions are still required downtheir respective
longrun timesare needed,not onlyto bringmaterials solvi, but aqueoussolutionsand solid compositions
up to saturationbut alsoto bring them down. In runs are neverthelessappropriately matched. About 15
6 HEMLEY ET AL.
 HYDROTHERMALORE-FORMINGPROCESSES.
PT. I 7

TABLE 3. Mixed-Metal SolubilitiesUsing the SyntheticK Feldspar-Muscovite-QuartzBuffer and the Assemblage

Pyrite-Pyrrhotite~Magnetite-Sphalerite-Galena-Chalcopyrite(1-m total chloride)

0.5 kbars 1 kbar 2 kbars

Fe Pb Zn Cu Fe Pb Zn Cu Fe Pb Zn Cu

(ppm) (ppm) (ppm)

300øC

440 110 63 9 166 47 23 20

240 60 33 21 349 62 38 9
310 109 44 15 203 52 51 7
230 43 33 7

350øC

789 275 171 23 733 81 90 9

700 208 209 29 400 158 90 22
1,031 325 250 17

400øC

2,875 1,050 983 64 1,100 457 537 30 450 153 117 24

2,344 1,316 905 36 1,467 685 333 35 520 239 112 30
2,406 1,286 922 79 1,265 762 424 66 530 190 130 32
2,884 1,394 1,122 61 1,333 549 399 29

500øC

6,632 4,301 4,081 185 5,625 3,154 2,512 127 2,316 1,284 928 66
7,500 3,750 3,047 108 5,000 3,054 2,290 104 2,500 1,700 975 79
6,875 6,027 3,287 117 5,357 3,841 2,964 79 2,313 945 1,475 105
.............................. 6,110 2,372 2,388 141
6,090 3,104 3,092 114

Italicized valuesfrom extractionvessel;dotted lines outlinebulk valuesfor two-fluid phases

percentmuscovitewasaddedto the quartzmonzonite ceduresin whichsphalerite,chalcopyrite,andgalena

to assureequilibriumalongthe potassiumfeldspar- reactantmaterialcouldbe separatedfrom the rest of
hydrolysiscurve. At the chargeafter openingthe capsulebut beforeacid-
plagioclase-muscovite-quartz
600øC and above, andalusite rather than muscovite ification.Perforatedtubeor "tea bag"runswerefirst
is stableand was usedin the buffer assemblages. tried in whichcoarsesulfideswere placedin a small,
The studyof metal sulfidesolubilityat elevatedP finelyperforatedgoldtubeenclosed in a largerthick-
andT by a cold-seal,rod bombprocedureis not fea- walled capsule containingthe remainder of the
sible unless a method can be found to evaluate'the charge.Precisionwasimprovedby abandoning the
amountof metal sulfidethat might precipitatewhen perforatedtube techniquein favor of a few large,
the vesselisquenched.Exploratorywork alongthese partiallyroundedgrains(roundedin an X-ray crys-
lineswasundertakenand the problemwasfoundto tallographer'sspheregrinder)of sphalerite,galena,
be tractable.First,ironandzincsulfidesgavenovisual andchalcopyrite(2-3 mmdiam)in the chargeitself.
evidenceof precipitationfrom the moderatelyacid Thisproceduregavereasonable results,providedthat
chloridesolutions involved.Moreover,roomtemper- spallingof fine materialfrom the sulfidegrainsdid
ature experimentsshowedthat 0.1 N HNO3 would not occurduring the run, as the particleswould be
immediatelydissolvefineprecipitatesof thesemetals attackedin the acid treatment. Apparentlyspalling
if theydid precipitate,and0.1 N HNO3 wastherefore did occuroccasionally with galenaand the simple
used as the initial rinse. The acid had no effect on the coppersulfides,asevidencedby very highPb or Cu
coarsesolids.Lead and copper proved to be more values in the boiled acid treatment in some runs. The
difficult, but the use of a more concentratedHNOa, results of such runs were excluded for all metals.
stepwisewith boiling,wassuccessful
with theseele- A typicalrun in a rod bomb capsuleconsistedof
ments, as described in more detail below. 200 mgof silicatecharge;150 mgof 1:1:1pyrrhotite-
Theseacidifyingtechniqueswere usedin run pro- pyrite-magnetite(80-150 mesh);two roundedfrag-
8 HEMLEY ET AL.

mentseach of galena,sphalerite,and chalcopyrite; analyzedfor alkalies,basemetals,and SiO2. Fe and

and1 ml of 1-mchloridesolutionof appropriatecom- Zn were at their full values,but Pb andCu were gen-
position.The typical size of the rod bomb capsules erally below detection.Analysiswasdone usingin-
was38 mm long X 9.5 mm diam.Two typesof sphal- ductivelycoupledplasma(ICP) andatomicabsorption
erite were used, a material from Balmat, New York, techniques, with matrixmatchedstandards. Analytical
containingabout3 percentFe for runsat 400 ø, 500 ø, precision was ___2 percent.
and 600øC, and a nearly Fe-free material from The solids were examined under a binocular mi-
Creede, Colorado, for runs at 300 ø and 400øC. No croscopefor problems(e.g., spallingor breakingof
consistent differences were foundin the solubilityre- the sulfideballsor oxidationas hinted by a trace of
suitsfor the two typesin parallel400øC runs. hematite).All sulfideswere usuallysparkling,andthe
Extractionvesselmethods:The rockingextraction chalcopyritewas multifacetedand gemlike. Occa-
vesseldesignwas similar to that of Dickson et al. sionalinteractionsamongsulfideswere noted.No re-
(1963). The internalcollapsiblegoldbagwasa tube, placementrelationswere seenamongpyrite,pyrrho-
127 mm long X 19 mm in diam, with a total volume tite, and magnetite, but galena was sometimes
of about35 ml, andweldedat both ends.Extending perched on chalcopyriteand there was sometimes
fromoneend,with a smallsinteredgoldfilterattached partial replacementof sphaleriteby galenaor chal-
internally,wasa platinumdeliverytube 300 mmlong copyrite. Sphaleritewas never observedto replace
X 0.4 mm in internal diam. This tube, enclosed in other phases.Theseoccurrences were probablythe
conventionalpressuretubing, extendedoutsidethe resultof competingratesof solutionandprecipitation
bomb and furnace to a stainless steel valve. The valve duringthe run. For example,it wasapparentthat ga-
remainedcooland wasopenedto the appropriatere- lena dissolvedand wastransportedmostreadily and
ceivingvesselon sampling. that chalcopyritewasprobablythe nextmostmobile.
In a typical run at 500øC and i kbar, 15 ml of Galena,therefore,apparentlydissolvedandreached
solutionwas equilibratedwith 3 g of silicatebuffer an initial supersaturated statefor the mixedsystem
plus about 2 g of pyrite-pyrrhotite-magnetiteand 3 quiterapidly.Sphalerite,however,wasmoresluggish,
g of galena,sphalerite,and chalcopyrite.The size and to reach its saturation value at the fixed total
range of the sulfidesand magnetitewas 80 to 150 chlorideandfs• valueof the run, galenahad to re-
mesh.Initial compositionof the solutionwasbased precipitate.Thereforegalenamayhavereplacedsome
upon the successive equilibrationruns in cold seals sphaleriteassphaleritewent into solution.Smalltem-
to determine approximateequilibrium composition. perature gradientsof about iøC acrossthe capsule
As in the cold-sealruns, solutionswere purgedwith alsomayhavebeena factorin producingsuchresults.
argonbefore loadingand weldingto insureabsence New minerals, such as cubanite, were not detected
of oxygen.The solutionsgenerallywere spikedwith in the products.
the basemetalsat slightlyabovethe expectedequi- After the 0.1 N HNOa rinse, removal of the
librium value in order to demonstrate reversals. roundedsulfidefragments,andfiltering,the remain-
Difficultywasencounteredin runsat 500øC with ing solidswere treatedwith 4 N HNOa for 4 min,
regardto Pb andCu becauseof the tendencyof their filtered, and washed.The resultingsolutionwas an-
sulfidesto precipitate in the delivery tube on sam- alyzedfor Pb, Zn, and Cu. Pb would likely be high,
pling. The first few samplesfrom a run appearedto but Cu wasusuallyvery low, indicatingthat Cu was
be satisfactory becausethe finely crystallineprecip- not yet dissolved.Zn wasfully dissolvedby the 0.1
itate wassimplycarriedthroughto the receivingves- N HNOa. The solidswere then treated againwith 4
sel, but once sulfidesaccretedto the walls, a substrate N HNOa and taken to a gentle boil for 30 seconds.
for crystallizationwaspresentandsubsequent samples The solutionwas cooled, filtered, and analyzedfor
were alwayslow. With continuedsamplingovera long Pb andCu. Thisproducedthe mainCu number,with
period of time the tube becamecloggedwith sulfide. the Pb usuallyno more than 15 percent of the cold
solutionvalue.Only runswith coldtreatmentPb val-
Sampling,observations, and chemicalanalysis ueshavinglowboiledtreatmentvaluesassociated with
Rod bomb experiments:At the end of an experi- them (but not added to them) are given in Tables '2
ment usinga rod bomb,the vesselwasimmediately and 3. After the final filtration, the solidswere boiled
quenchedin anicebathandthe capsuleremovedand in aquaregia to assurethat all copperhad been ex-
openedinto a beaker. The pH of the solutionwas tracted.
measured,all productswere washedinto the beaker A few samplesnot subjectedto the strongacid
with 0.1 N HNO3, and the capsulerinsedwith 0.1 N treatmentwere givena moredetailedopticalandX-
HNO3. The roundedgrainsof chalcopyrite,galena, ray examination. Hydrolyticalterationproductswere
andsphaleritewere carefullyremoved,the remaining suppressed in the finalassemblagebecause the chem-
productswere passedthrougha 0.45-tamfilter, and ical drive for their appearancewaseliminatedin the
the solutionwasdilutedfor analysis. Thissolutionwas successive equilibrationproceduresused.Thus,feld-
 HYDROTHERMAL
ORE-FORMING
PROCESSES.
PT.I 9

spar compositionsin the final equilibration assem- quenchingwere expectedto be smallto negligible,
blageswere essentiallyunchangedrelative to the but pH, in fact, drifted a few tenths of a unit lower
startingmaterial. Muscovitewas presentin all runs in someruns.This wasdue to precipitationof sulfides
asan initial componentof the charge.The alteration on quenching,with consequentformationof HC1.The
productsdiscussed in Whitneyet al. (1985), however, extent of precipitationof metal sulfidewasvariable,
were thosefoundin the preliminaryrunsin thisstudy however,and in runsinvolvingonly iron or zinc, no
initiated at low pH and carried througha long run sulfideappearedto precipitate.Nevertheless,in the
period.Theseproductsconsistedof feldsparaltered Zn runs the quenchpH was still slightlylower than
to muscoviteat 500øC, muscovite,mixedlayer mus- expected.This shift may have been due to colloidal
covite-smectite,and a smallamountof chlorite (non- sulfide that was difficult to detect in the clear solu-
expanding
14•t phase)at 400øC.Annitewasnot a tions,but somemeasureof complexingof molecular
product,which is not surprisinginasmuchasthe sta- HC1 with the ZnC1+ or ZnCI• speciesis alsoa possi-
bility of anniteis suppressed
by the presenceof pyr- bility. This remainsa topic for future research.How-
rhotite-pyrite(Hammerbackand Lundqvist,1972). ever, it would be surprisingif associationsof thistype
Smectitewasdominantat 300øC in quartzmonzonite did not occur to someextent and contributesignifi-
runs.In the 1985 work, distinctchangealsooccurred cantlyto the aciditybalancein high-temperaturesys-
towardmore potassicK feldsparandmore sodicpla- tems. Ruaya and Seward (1987), for example,have
gioclase,particularly at 400øC, becausesuccessive suggested the occurrenceof HAgCI• in their solutions.
equilibrationwasnot used.Sucha changewouldbe Such considerations illustrate the uncertainties in at-
expectedin assemblages that had undergonestrong tempting to reconstruct,through calculation,ther-
acidattack,with selectiveremovalof Na, andpartic- modynamicparameterssuchaspH or activityof dis-
ularly Ca, followedby equilibrationand recrystalli- solvedspeciesin complexmixedsystemsat elevated
zation. pressuresandtemperatureson the basisof dissociation
Extraction vessel experiments:Samplingproce- constantsderived from studiesin simple systems.
duresfor the extractionvesselwere relativelysimple. The pH buffers:The quartz monzonitepH buffer
For determinationof the metals,0.5-ml samplesgen- wasusedin this investigationto provide greater geo-
erallyweretakendirectlyintoanopencentrifugetube logic relevance,as well as continuitywith the 1985
or other receiver. This material was reacted with 6 N work in the sulfur-freesystem.However, we alsode-
HC1to removesulfideasH2Sandthenevaporatedto siredto extend experimentationto 300øC to expand
near drynesstwice with perchloricacidto solubilize the studytoward a wider rangeof ore-formingenvi-
all metals. The residue was diluted to 5 ml, acidified ronments.At that temperature we anticipatedthat
with HNO3, and analyzedby ICP. A second,smaller the bufferwouldno longerfunctionwell inasmuchas
samplewastakenfor analysisof the alkalies,SiO2and the fine grainsizeandhighreactivityof the synthetic
C1-. The precipitatedsulfideswere centrifugedand materialwould promotethe tendencytowardmeta-
a smallaliquotof supernatant liquidtakenanddiluted stableproducts,excessive leachingof alkalies,and a
for the analysis.For sulfur determinations,2-ml sam- run pH that would be excessively high. The marked
plesgenerallywere takenin deoxygenated i N KOH drop in metal solubilityin the 400øC QM data may
solutionsto sequesterall H2S.Becausemetalsexceed reflect the effect of an excessively
high run pH. At
sulfurin theserunsby a factorof morethan two, this 300øC, the problem would be worse.Use of the pure
procedureimmediatelyprecipitated all H•S, pre- potassium feldspar-muscovite-quartz buffer was
dominantlyas iron sulfide.This material was centri- therefore initiated at 300 ø, 400 ø, and 500øC to over-
fuged, separated,andoxidizedto sulfate.The sulfate lap the quartz monzonitestudiesand to examinethe
wasanalyzedeither gravimetricallyasbariumsulfate, effect of two differentpH bufferson the sulfidesol-
or when H•S was low, as soluble sulfate on the ion ubility pattern.
chromatograph. The supernatantfluid from the cen- Single-metalexperiments:A number of runswere
trifuge tube containedthe oxidizedsulfurcontentof madeto determinesingle-metalsolubilities;only the
the run, whichprovedto be negligibleon the pyrite- pH buffersandthe individualsulfideswere employed
pyrrhotite-magnetite bufferbut of somesignificance (Table4). For Fe, the assemblage pyrite-pyrrhotite-
on more oxidized buffers. magnetite and each of the individual mineralswere
Significanceof quenchpH: The quenchpH readings investigated.Althoughnot controlledrelative to one
for the sulfide runs in both the rod bombs and ex- anotherbecauseS• fugacitywasnot fixedat a definite
traction vesselwere typically a few tenths of a pH commonvalue, these experimentswere of value in
unit lower than the KMQ buffer curve aloneideally assessing the solubilitybehaviorof the metalsin their
predicts, that is, a value of 1.95. Becauseliquid to pure systemscontrolledby a givenpH buffer. Equi-
solid ratios were much higher in this study than in librium was assessed usinglong runs and solubility
the 1985 investigation(5:1 vs. 1:1), back-reactionin vs.timeplots.The experiments wererunin goldtubes
the rod bombs and pH drift to higher values on purgedof oxygen;f• thereforewasat somevalue
10 HEMLEY ET AL.

TABLE 4. Single-MetalSolubilities(in ppm, 1-m total chloride)

K feldspar-muscovite-quartz
buffer• Quartz monzonite buffer

300øC 400øC 500øC 600øC 400øC 500øC 600øC 700øC

Fe Fe
1 kbar 1 kbar

270 1,783 9,444 17,500 657 5,800 12,300 15,000

230 1,667 8,258 20,348 821 7,143 13,200 16,204
9,705 • 18,295 • 740 7,762
8,260 (po) 6,858
8,200 (mt) •788 •
7,031 (py) 7,587 •

Pb (ga) 0.5 kbars

217 1,384 8,559 2,760 13,500

322 1,535 8,488 2,470 14,500
2,389 14,500

Zn (sl) 2 kbars

141 1,046 5,166 198 1,852 6,250 11,560

209 1,082 4,983 172 2,054 6,100 11,250

Cu (dg) Cu (dg)
0.5 kbars I kbar 2 kbars 0.5 kbars I kbar 2 kbars

500øC 500øC

1,077 822 2,164 1,180 400

920 835 1,259 823 640
1,414 960
1,774(½c)

400øC

253 145 89
119 110 56
102

300øC

21 24
33 18
41 43

Unlessotherwisestated,Fe is from pyrrhotite-pyrite-magnetite,Cu from digenite

Italicized values from extraction vessel;dotted lines outline bulk values for two fluids
• K feldspar-andalusite-quartz
at 600øCandabove
• Hematite-pyrite-magnetite
a 700oc

within the H2Sstabilityfield. Nickel-nickeloxidealso Coppersolubilitywasnotinvestigated usingchal-

wasplacedin the vesselasan externalbuffer because
gold is permeableto H2 to a limited but significant
extent.The effectiveness of this methodis question-
able,however,belowabout500øC (ChouandCygan,
1990).
copyritein single-metalrunssincechalcopyrite
would
havebeensubjectto incongruentdissolution andthe
formationof a surfacephasethat mighthavebeen
difficultto characterize.
Therefore,thebinarysulfide
digenite (Cu9S5)was used. Chalcocite,the data for
 HYDROTHERMAL ORE-FORMING PROCESSES.PT. i 11

which are used in SUPCRT, was investigatedin a in Tables2 and 3 andsummarizedin Figure 3. Some
numberof runs,but it behavedpoorly.Roundedfrag- resultsdiffer slightlyfrom those of earlier reports
mentsoften exhibitedmuchspallingandgavea wide (Hemley et al., 1986, 1987). Increasingtemperature
scatteringof results.The chalcocitevalue given in and decreasingpressurefavor increasedconcentra-
Table 4 for 500øC is probablysatisfactory,but lower tions of the metals. Table 2 summarizes results for
temperaturevalueswere excessively high. the quartzmonzonitebuffer andTable 3 for the po-
Coppersolubilityproblems:The solubilityrelations tassiumfeldspar-muscovite-quartz buffer. Somere-
of copperwere difficultto evaluatein this investiga- lations in the more restricted two-fluid region are
tion for two reasons.First, the observed solubilities given in Table 5 and the sulfurdata in Table 6, and
were very low andthereforemoresusceptibleto con- are discussed in later sectionsof the paper.Note that
taminationandanalyticaldifficulties.Second,copper in Table2, although the principalfs•bufferusedwas
tendsto alloy with the gold container,especiallyat pyrite-pyrrhotite-magnetite, roughlysimilarsolubility
highertemperatures.Thisbehaviorwasdemonstrated relationsfor the metalswere obtainedusingpyrite-
by runningcupricandcuprouschloridesolutions (100 hematite-magnetite. The geologicapplications of the
ppm) in gold capsulesat 500øC and i kbar for the dataare thereforefairly broad.Goldvaluesfromthe
averagerun time. Concentrations decreasedby a fac- goldbag usedin the experimentswere all lessthan
tor of two or more (diffusionof H2 into the capsule 0.1 ppm.
to reducethe Cu ionsis required in the process).Sil- The solidandbrokencurvesin Figure 3 represent
ver whosesolubilitybehaviorin this mixed system the QM and KMQ runs, respectively.The slightly
would be extremelyinterestinggeologically,shows higher solubilitiesin the pure K systemcorrespond
an evengreatertendencyto alloyandthereforewas to slightlyhigher aI•+at the KMQ equilibriumpoint
not systematicallyconsidered.Molybdenum(using compared to the muscovite-plagioclase-potassium
molybdenite)wasaddedto somerunsand exhibited feldspar-quartzequilibriumpoint. The uncertainty
consistentlylower solubilitythan copper. barsin the figuresrepresentthe spreadin resultsfor
Althoughresultson the QM buffer were erratic, the final set of equilibrationruns (i.e., the experi-
work on the slightlymore acid KMQ buffer using mentaluncertainty)at eachPT pointasgiveninTables
chalcopyrite gavefairlyconsistent,andevenreversed, 2 and 3. The symbolshownon eachbar represents
solubilitydata.For thisreason,chalcopyritesolubility the averagevalue for the numberof runs involved
is shownonly in runsusingthe KMQ bufferin Table andthe sizeof the symbolreflectsthe uncertaintyin
3. Thisdifferencein behaviorsuggested thatthe plat- analysisand pressure-temperaturecontrol.
ing-outreactionwasbeingoverriddenby morerapid Althoughthe effectof temperaturein the experi-
dissolutionof the coppermineral.To test this point mentsis asanticipated,the effectof pressure,at first
further, three consecutive runsusingthe samegold examination,might seem surprising.The greater
capsulewere made,without vigorouscleaningafter densityof the solventat higher pressureshouldin-
each run. The results of these runs are the i kbar and crease,not decrease,its solventability, viewedasa
500øC digenitevaluesin the QM bufferindicatedin functionof hydrationonly. The pressureeffectcan
Table 4; the highestvalueisfor the initialrun. If plat- be understoodin termsof the KMQ equilibrium(here
ingout onthe innersurfaceof the goldwere a serious eq. 1 in reverse),a dissolutionreaction(eq. 7), and
problem,as the thicknessof Cu-rich gold increases their sum(eq.8), writtenin termsof aqueous chloride
with eachrun, we would expectthe observedsolu- complexes,where the superscript,,o,, denotesthe
bilitiesto be higherin later runs.Higher solubilities, associatedneutral species:
however, did not occur. These results indicate that 2KCI ø + muscovite+ 6 quartz
the rate of dissolutionof copperwasgreaterthanthe
rate of alloying,andthe constancy of the resultsfur- = 3Kfeldspar+2HC1 ø, (la)
ther impliesthat the solutionwassaturatedwith cop- 2HC1ø + pyrrhotite= FeCI• + H2S•g•, (7a)
per sulfide.Moreover, runs in the extractionvessel,
and
whichwerespikedwith initialhighvaluesof Cu, pro-
duced the same results as the cold seals. The solubil- 2KC1ø + muscovite+ 6 quartz + pyrrhotite
ities at other pressuresalso showedconsistent,re-
produciblevalues.The copperresultsgivenin Tables -- 3 K feldspar+ FeCI•S•g• + H•S(g). (8a)
3 and 4, therefore, are interpreted as equilibrium The KMQ equilibrium(eq. 1a)isshiftedto theright
data. by a decreasein pressure(Hemley, 1959) and the
Experimental Results increasein total acidity is then availableto operate
on the metalsulfide.If the metalchloridecomplexis
Pressure-temperature effects more stronglyassociated than HC1ø, aswould be ex-
The homogeneous fluid region:The resultsof the pectedby analogywith other divalentcationssuchas
experimentson mixedsulfideassemblages are given Ca+•, equation(7a) alsowill tendto proceedto the
19. HEMLEY ET AL.

.1 1041
_
COPPER

.03 .O3

103-
.01
.01

.003
.003

102_ 102
-

.001

.0003

10• '
' .0001

I I I I I I I i I i
300 400 500 600 700 300 400 500 600 700

T• TøC

104- - .05
ZINC

.02

.01
.O3

103ß .005
103' ß
.

-.01
- .002

.001
.003

102- 102-
ß

.001

.0003

10l-

I I I I I I I I I I
700
300 400 500 600 700 300 400 500 600
TøC TøC

FIG. 3. Metal solubilitycurvesin the mixedsulfidesystemsat 1-m total chloride;A = 0.5 kbars,¸
-- 1 kbar, [] = 2 kbars.Solid curvesand symbolscorrespondto the quartz monzonitebuffer and the
assemblage pyrrhotite-pyrite-magnetite-sphalerite-galena.
Dashedcurvesandopensymbolscorrespond
to the K feldspar-muscovite-quartz buffer and the assemblage pyrrhotite-pyrite-magnetite-sphalerite-
galena-chalcopyrite. Plotb isdistinctin that the uppercurvecorresponds to single-mineral
solubilities,
open symbolsto digeniteand chalcocite(cc)with KMQ buffer, and solidsymbolsto digenitewith QM
buffer. The 0.5- and 2-kbar curvesare omitted from the upper set of curvesin b.
 HYDROTHERMAL ORE-FORMING PROCESSES. PT. I 13

TABLE
5. Liquid-Vapor
Compositions
UsingtheQuartzMonzonite
Buffer(1-mtotalchloride,500øC,and0.5 kbars)
HC1 K Na Ca Fe Zn Pb C1

Vapor
• 0.079m 0.017m 0.036m 0.006m 1,423ppm 711 ppm 1,275ppm 0.238m
Liquiff
2 0.038m 0.24m 0.42m 0.073m 14,300ppm 7,900ppm 11,930ppm 1.6m
Measured
Calculated

right.The pH changewith a decrease in pressuredoes changein free energyof dissociation

of a givenspecies
not favorincreasedmetalsolubilitybecausea}•+be- is givenby:
comessmallernot larger. It is the increasein HC1ø
in equation(7a), togetherwith the relativechangein A(AGdissoc.)
= fA•dP = -RTA In Kr•, (13)
the dissociation of the metal complexand HC1ø, or
of the metal complexand KC1ø in the net reaction where R is the gasconstant,T is the absolutetem-
(eq. 8a), that producessuchan effect. perature, andKr) is the dissociationconstant.In equa-
For a more detailedanalysis,let us considerthe tion (1), Kr),c•-is decreasedmore stronglywith de-
fundamentalthermodynamic relationfor the effectof creasein pressurethanisKr)m-,asshownin Table7,
pressure.This is given by AG = fVdP for the free in agreementwith the volume changefor equation
energychangeof a givenconstituentor phase,where (la) notedabove.In equations
(7a)and(8a),Vpyrrhotite
G isGibbsfree energy,V isvolume,andP ispressure. is 18 and•;H2sa•
is43 ccat 400øCand1 kbar,but
The corresponding pressureeffectonthe free energy thepartial
mof•l
volumes
oftheappropriate
Fe-C1
of a reaction,AGr, is givenby A(AGr) = fAV•dP, complexesare not yet available.However,the weaker
where/XV•is the total volumechangeof reaction,at dissociation of the metal chloridecomplexesrelative
any given temperature. Volume is expressedas a to HC1ø andKC1ø, at a givenpressure,isseenin Table
functionofpressure forexactevaluation. Forequation 8 vs.Table 7. Also,subsequent work onFe speciation
(la), AV solidsis 49 cc, consistentwith a shift of the (J.B. Fein et al., in prep.)hasshownthat ironchloride
equilibriumto the right with a decreasein pressure. dissociation decreases morestronglywith decreasein
The observedshift,however,islargerthancalculated, pressurethanthat ofHC1ø andKC1ø.This is consistent
especially_athighertemperatures, whichindicates a with the net positivevolumechangeimplied by the
positive AV, the changein partial molal volume,for observedincreasein solubilitywith decreasein pres-
the aqueous constituentsas well. Such a volume surefor equation(8a). The sameanalysisappliesto
changeis in agreementwith availabledata,valuesfor equations(10-12).
the partial molal volumesof HC1 and KC1 at 400øC A significantfeatureof reactionssuchas (8a) and
and 1 kbar,for example,being65 and42 cc, respec- (10-12) is that they are volatilizationreactionsfor
tively (D. Sverjensky,pers.commun.).An important H2S and H20, respectively,and the positiveAV as-
point, however, is that in the absenceof reliable vol- sociatedwith releaseof volatileswill have an appre-
ume informationon aqueousspecies,as is the case ciable, but not necessarilydominant,effect on the
for manyhigh-temperature electrolytespeciesand dissolutionprocess.At 400øC and 0.5, 1.0, and 2.0
especially metal-bearingcomplexes,the relative kbars,for example,the valuesof V•-i2o are 31.2, 26,
changein dissociation-association constants provides and22.7 cc,respectively,but largerchanges areseen
a guide to the direction of reaction.This followsfrom in •r}zc•owhichare 57.7, 42.3, and 37.6 cc. Not all
the free energy relations given above, where the reactionsinvolvingthe releaseof metalsfromminerals

TABLE6. SulfurData (1,000 barstotal pressure)

Calculated Observed

øC logK1 f,•o fH•s q•,•s

2 P,•s mH2S mH2S

5OO -1.932 459 5.36 6.38 8.4 X 10 -• O.O47 0.05 + O.Ol

4OO -2.264 262 1.42 31.04 4.6 X 10 -2 0.003 0.007 + 0.002
3OO -2.697 105 0.209 321.1 6.5 X 10 -4 O.OOOO36 0.0008 __+0.0002

SUPCRT
for0.5pyrrhotite
+ 0.25pyrite+ H20(g)
= 0.25magnetite
+ HaS(g),
K = f}•s/fu•o
Flowers(1979)
14 HEMLEY ET AL.

TABLE 7. Log DissociationConstantsUsedin CalculatingSpeciesDistribution

øC kbars KCIø NaC1

ø HCIø CaCI• KOHø NaOHø H20 KMQ•
300 0.5 -0.18 -0.68 -0.84 -2.44 -1.13 -1.42 -10.92 3.60
I -0.02 -0.44 -0.65 -1.93 -1.00 -1.17 -10.63 3.69
400 0.5 -1.31 -1.74 -2.70 -4.92 -1.96 -2.45 -11.36 3.45
1 -0.77 -1.15 -1.81 -3.76 -1.58 -1.86 -10.84 3.55
2 -0.40 -0.67 -1.30 -2.75 -1.30 -1.36 -10.18 3.67
500 0.5 -5.39 -5.66 -10.00 -12.17 -4.47 -5.99 -14.04 3.25
1 - 1.79 -2.14 -3.63 -6.07 -2.30 - 2.78 - 11.35 3.43
2 -1.00 -1.27 -2.32 -4.38 -1.76 -1.92 -10.46 3.56
600 1 -3.23 -3.53 -6.37 -8.94 -3.18 -4.00 - 12.40 3.47
2 -1.61 -1.89 -3.46 -6.05 -2.20 -2.48 -10.85 3.85

Other values

400 1 -0.992 -0.893 -2.082 -4.094 -1.42

-1.885
500 1 -2.272 -2.103 -3.582 -8.084 -2.42
-2.596 -4.265
600 I -3.672 -3.323 -4.932 -12.644 -3.62
-2.976 -6.905

Other data used at 500øC and I kbar log K

2H+ + 0.5Po + 0.25Mt = Fe+2+ 0.25Py + H20 1.672
2H+ + Ga = Pb+2+ H2S(g) 1.156
2H+ + St = Zn+2+ H2S(g) -0.061
2H + + Cc = 2Cu+ + H2S(g) -4.O77
2H+ + Ga + 0.25Mt -- Pb+2+ 0.25Py + 0.5Po + H20 0.421
2H+ + St + 0.25Mt = Zn+2+ 0.25Py + 0.5Po + H•O -0.796
2H + + 2Cp + 0.25Mt = 2Cu+ + 1.25Py + 1.5Po + H20 -6.848

Abbreviations:
Cc -- chalcocite,
Cp = chalcopyrite,
Ga -- galena,Mt = magnetite,Po = pyrrhotite,Py -- pyrite,SI -- sphalerite
I LogK foreq. (1);Sverjensky
et al. (1991) 4FrantzandMarshall(1982)
• Franck(1956) 5FrantzandMarshall(1984)
3QuistandMarshall
(1968) 6RitzertandFranck(1968)

TABLE8. Thermodynamic
Propertiesof Metal Complexes(500øC and 1 kbar)

Experiment FeCI• PbCI• ZnCI• CuCIø

Log dissociationconstants
Mixed system -8.25 _ 0.13 -8.68 _+ 0.13 -10.33 _+ 0.13 -6.14 _+ 0.2
-8.66 -9.09 -10.73 -6.34
Pyrite-pyrrhotite-magnetite -8.45 _+ 0.13
-8.86
Galena only -8.78 _+ 0.13
-9.18
Sphaleriteonly -10.60 ñ 0.13
-11.00
Chalcociteonly -5.90ñ0.2
-6.09

Other properties
Gfcal/mole• -98,209 -580 -95,813 _ 487 -118,899 -+663 -46,645 _+ 834
Hf cal/mole -69,184 -+ 783 -66,551 _+1,007 -92,609 _+972 -27,847 _+1,447
g_
cal/K/mole 65.96_+ 0.68 68.47_+ 1.14 63.20_+ 0.92 40.26_+ 1.53
V cc/mole 96.7 _+ 1.1 113.5 _+ 6.1 102.8 _+ 1.0 55.5 _+ 4.3

Italicized-- activitycoefficients
calculated(Helgesonet at., 1981);nonitalicized-- all activitycoefficients
unity;uncertainties
are
1 sigma
• Basedon avglogKDfor italicizedvalues
 HYDROTHERMAL ORE-FORMING PROCESSES. PT. i 15

are, of course,volatilizationprocesses.
In the release at constanttemperature also cannot continue indefi-
of Pb from K feldsparby aqueousKC1(Hemley and nitely. At the point of intersectionwith a two-fluid
Hunt, 1992), for example,equation(1), the volume field, a salt-richliquid phaseseparatesfrom a salt-
changeof the solidis negligibleand the measureof poor gaseousphase, with base metal concentration
reactionwithchange inpressure isexclusively a func- favoringthe liquid or brine phase.Solubilityin the
tion of the AV of the electrolytespecies,or of the brine phase may continue to increaseas the brine
correspondingchangein their dissociation constants. itself increasesin C1concentration.At the sametime,
In Tables7 and8, KI•pbc• isseentobemuchsmaller however,the totalmassof brine is decreasing because
thanKi•Kc• o, thusfavoringthe leachingof lead,andif an increasingmassof gasis being producedfrom it.
lowerpressure furtherdecreases Ki•pbc• relativeto This decreasemusteventuallylead to a decreasein
Ki•Kc•o, as is indicatedin the experiments, leaching bulk or overallmetalsolubility.The ultimatestateof
will be enhanced. suchan expandingsystemwould be solidmetal sul-
In summary,if a givendissolutionreactionis char- fidesandsaltscoexistingwith a tenuousgasphase.
acterizedby exchangebetweentwo electrolytes,de- The gas-liquidregion:Figure 4 showsthe phase
creasingpressurewill dictatereactionin the direction relationsfor the systemNaC1-H20,accordingto Sou-
of the speciesshowinggreatestdecreasein dissocia- rirajan and Kennedy (1962). More recent work (Bis-
tion (e.g., the decreasefor the metal complexesvs. ehoffandPitzer, 1989) givescorrectedrelationsover
KC1ø in eq. 10-12). The volumechangeassociated a portion of the PT range, but the Sourirajanand
with other constituents(solids,H20, etc.), however, Kennedy diagram is most appropriate for broader
will modifythat effect.Volumechangefor the solids representation.Becauseof the strongchemicalsim-
will be of relatively little significancein the higher ilarity of KC1andNaC1,our mixedsystemis unlikely
PT regions. to showmarkeddeviationfrom this diagramand the
Parallelwith the effect of pressure,the effect of diagramshould,therefore,be applicableas an ap-
temperatureon the free energyof reactionis a func- proximateworking model. Obviously,phasesepara-
tion of entropyof reaction,asexpressed in the relation tion boundariesin the KC1-HeOsystem,and in geo-
/X(/XGr) -- -f/XSrdT.In reactions suchas those logicallyrelevantmixedsystemswith significantmetal
we have considered,the positiveentropychangeof present, would constitute valuable information.
volatilization will promote dissolutionwith increase Aboveeachloopin Figure4, a gas-liquid regionexists
in temperature. The entropy changefor the solids at the givenpressure.At 1 m NaC1(5.5%) and 1 kbar,
will tend to remain more or lessconstantwith change the two-phaseregion is not intersecteduntil a tem-
in temperature,but the changefor the aqueousex- peratureof about670øC is attained.At a lowerpres-
changespeciesof a reactionwill be lesspredictable. sure,the two-phaseregionis encounteredat a lower
Trends in association-dissociation constants with temperature and in Figure 4 at 0.5 kbars the tem-
temperature,however, will againserveas a guide. perature is about 475 øC. The recorded solubilitiesin
The increase in total metal concentration with in- Tables 2 and 3 at 500 ø and 600øC and 0.5 kbars, and
creasing temperature at constant pressure, as illus- at 700øC and 1 kbar, therefore, representthe total
trated by the isobaricsolubilitycurvesof Figure 3, valuesfor the two fluids combined.In the quartz
eventuallyfiattensand apparentlypasses througha monzonitesystem,total metal concentrations are still
maximum. The trend toward a maximum is indicated increasingat 500øC and 0.5 kbarsalongthe smooth
in the 0.5-kbar data for the four metals(Tables2 and isobarictrends shown,even thoughtwo fluids are
3 andFig. 3), andin the 1-kbardatafor the Fe-only present,but in the KMQ systemsolubilitiesare be-
ginningto drop at this point, as indicatedin Figure
system(Table4). The 700øCironvaluesareprobably 3. This differencesuggests that phaseseparationin
too high, moreover,becauseappreciablepyrrhotite
theK systemoccursat a somewhat lowertemperature.
appearsto havedissolvedon quenchingasa resultof Inasmuchasa pressuredecreasealonein thischlo-
theveryhightotalacidityproducedin veryhightem- ride-dominant, rock-bufferedsystemtendsto produce
perature runs.The plateauand maximumare the re- an increase,ratherthandecrease,in metalsolubility,
suitof intersection
with a two-phase(gas-liquid)field, metaldepositionasa resultof pressuredecreasere-
mineralogic changes in the rock-bufferreaction(eq. quiresthe moreextremeprocessof phaseseparation
2), andthe effectof increasingcompetitionfor chlo- and the accompanyingtemperature or chemical
ride. As metal concentrationrisesand its complexes change.Boiling,strictlydefined,is a steadystateease
becomea supplieraswell asa consumerof chloride, of phaseseparationat moreor lessconstantpressure
chloridebecomesmore stronglydistributedtoward andtemperature,the heatbeingsupplied,in the geo-
H +. At 700øC, for example,HC1ø becomesa major logic context,by upwelling,eonveetingwaters.The
constituentof the aqueousphase. consequences of boiling,notablylossof volatilesand
The observed increase in total or overall metal sol- resultant potential shift in pH, oxidationstate, etc.,
ubility(gas+ liquidphase)with decreasing
pressure have becomewell appreciatedwith regard to ore-
16 HEMLEY ET AL.

8OO

775

750
Gas compositions
725 Liquidcompositions _
7O0 Criticol
points •:i•i•3QQO.
O•t•O I .-- ,
II
675

650

? 6•5
• 600

<•575 I

Lu
n 550
• 525
500

475

450

425

400

375

350

I moial

3OO I I I I I I I• I I
001 .005 .01 .05 .i .5 1.0 5.0 io 50 ioo

NaCI (wt. %)

FIG. 4. Isobariccurvesin the gas-liquidregionin the systemH20-NaCl, fromSourirajanandKennedy

(1962).

formingprocesses(e.g., Drummondand Ohmoto, leverrule andFigure4, usingthe gasconcentrations

1985). Even with boiling, however,the occurrence from the extraction vessel and the overall or total
of precipitationwill dependuponthe degreeof un- concentrations. The total concentrations of the metals
dersaturation of the metalat the onsetof boilingand andalkaliesare givenby the corresponding cold-seal
the extent of the chemicalchangesinvolved.Note experimentsat 500øC and 0.5 kbars.The log total
alsothat a diagramsuchasFigure4 showsthatphase acidity(HC1ø + H +) is -1.25 m on the QM bufferat
separationinvolvinga relatively dilute solutionwill 0.5 kbars.Asexpected,thevaporphasecontainsmuch
producea liquidphasemuchmoreconcentratedwith lessof every constituentexceptHC1, yet the vapor
respectto the alkaliesthan its precursor,and there- also containssignificantmetal. If the fluid had not
fore,metasomatic effectsmightbe fairlyextreme(e.g., beenequilibratedwith lead andzinc sulfides,the iron
the depositionof adularia).A concentratedsolution, contentof the liquid and gasphasewouldhavebeen
on the other hand,will producea liquid phaseclose evenhigher.The implications to vaportransport(e.g.,
to the originalcomposition,and metasomaticeffects the vapor transportof magnetite)are not inconse-
inducedby phaseseparation likelywill notbe asgreat. quential.Two-fluidmetal solubilityrelationsare ob-
An attempt to samplethe compositions of the two viouslyof greatrelevanceto ore-formingprocesses,
fluidsin thisstudyat 500øC and0.5 kbarsusingthe but a thoroughstudyof this region was beyondthe
extractionvesseltilted upward andthen inverted was scopeof thispreliminaryinvestigation.
only partly successful. Samplingthe gasapparently
The role of chloride
presentedno problems,but cloggingof the delivery
tube occurredquicklywith the liquid becauseof the We also investigated,althoughonly for general
veryhighmetalconcentrations. Table5 contains liq- comparativepurposes,the effectof chlorideconcen-
uid- andgas-phase dataobtainedwith the helpof the tration on solubility.In the pure Fe system(pyrrho-
 HYDROTHERMAL
ORE-FORMINGPROCESSES.
PT.i 17

tite-pyrite-magnetite without other base metals) on absolutetemperatures, againin disagreement

with the
the QM buffer at 500øC and 1 kbar, iron concentra- behavior of the individual metals as discussed earlier
tionsare approximately200, 6,900, and 21,000 ppm (Robinsonet al., 1988). The concentrationratiosare
at 0.1-, 1.0-, and 2.0-m total chloride,respectively. an approximation of the equilibriumconstants
of the
This increase is the result of both the effect on chloride exchangereactions,for example,
complexingand the increasein total acidity (via the
silicatebufferequilibrium)engendered by higherto- ZnCI• + FeS = Fe CI• + ZnS, (14)
tal chloride,the latter effect being much more sig- where K = a•ec•daz,•ci•. Suchreactionsshow,inci-
nificant.Comparablechanges likelywill occurfor the dentally,that if the two metalswere presentascom-
other metals. These differences show that the role of
plexesof equalstability(i.e., the sameKr• values),
total chlorideisclearlyvery important,but it isa con- their ratioswouldbe simplythe ratiosof the solubility
trol already well appreciatedin the literature and productsof the two sulfides.The slopeof log K vs.
thereforeis not a point of emphasisin this investi- 1/T øKcorresponds to the enthalpyof reactionin the
gation. Van't Hoff equation
An averageligandnumbercloseto 2 is suggested
for the iron chloride complexat 500øC, 1 kbar, and
1-m total chloride,basedon thermodynamicextrap- In K - + C, (15)
RT
olation from lower temperatures(200ø-300øC) of
provisionalstabilitiesfor FeC1+ and FeCI• (D. A. where C is a constantof integration.The constant
Sverjensky,pers. commun.).Dominanceof the spe- slope(withinexperimental uncertainty) indicates a
ciesFeCI• is thereforetentativelyassumedand will zeroACpof reaction for equation(14), whichis ex-
serveasa basisfor calculations givenbelow.At lower pectedfor twosimilar basemetalchlorides suchas
temperaturesor higher pressures,increasedioniza- iron and zinc. The dissolutionreactionsfor the indi-
tion would occurand the speciesFeCI+ shouldbe- vidualmetals,on the otherhand,equations (10-12),
comeincreasinglyimportant.Similarly,at very high involve the base metals vs. H + or K+, and for these
chloride concentrations,speciessuch as FeCI• and reactions a divergence fromlinearityisexpected and
FeCI•2 couldbe expectedto increasein importance, observed.
andconversely, at lowerconcentrations, FeC1+ should The role of sulfur
againbe favoredoverFeCI•. If higherchloridecom-
plexesbecome dominant,a large enhancementof Total dissolvedsulfurvalueson the pyrrhotite-py-
metal solubilityresults,proportionalto the chloride rite-magnetite bufferwere0.05, 0.007, and0.0008
concentrationraisedto the power of the chlorideli- m at 500 ø, 400 ø, and 300øC, respectively,as given
gandnumber.Statedbriefly, becausethe dielectric in Table6. Thesevaluesrepresentaverages of two or
constantof water decreaseswith increasingtemper- threesamplings fromoneruneachin theKMQ system
ature, unchargedspeciestend to be more strongly at 1 kbar and run timesof up to 3 monthsduration.
favored with increasingtemperature,but pressure Thisrs2bufferiswellwithinthereduced sulfurfield
(higherpressureincreases the dielectricconstant)and at all temperatures, and therefore,the sulfuris es-
concentration haveappropriatemodifyingeffectson sentiallyall H2S.Alsoshownin Table6 arethe cal-
speciesdistribution. culatedmolalitiesand fugacitycoefficients for H•S.
Amongthe four metals,the similarityin behavior The valuesarecalculatedusingthe modifiedRedlich-
of iron, lead, and zinc with respectto changein tem- Kwongequation(Holloway,1977), ascorrectedby
perature and pressuresuggestssimilarity in the Flowers(1979). Agreementis goodat 500øC, and
aqueouschloridecomplexingof thosethree metals. the pooragreement at thelowertemperatures isdue
With increasein temperature,the solubilitycurves either to experimentalerror or inaccuracies in the
are roughlyparallel,and with increasein pressure, equation in solutionsof extremelylow molefraction
approximatelyequal concentrationchangesare dis- H•S and low temperature.
playedbetweenthe 0.5-, 1.0-, and 2.0-kbar curves An importantpointis that H•S concentrationis in-
for each metal. Dominance of the neutral dichloride dependent of pH. Thebuffercontrolsfs2
andfo=,and
speciesisthereforeassumed
for leadandzinc,aswell therefore,alsocontrolsf•i•s
throughaqueousequilib-
asfor iron, at 500øC and 1 kbar, whereasfor copper ria. This controlis alsoexpressed
in equation(9). In-
the monochloride CuC1 ø is assumed. creasingacidityby increasingtotal chloride,there-
Reflectingthe similarityin the pressureshiftof sol- fore, simplyincreasesthe dissolutionof magnetite,
ubility for the metals,the ratiosof Fe/Zn, Fe/Pb, and not the concentrationof H=S. The result of the dis-
Pb/Zn are relativelyinsensitiveto pressure.This in- solutionof magnetiteis a sulfide-deficient
solution
sensitivity isin markedcontrastto thebehaviorof the (i.e.,themolalmetalcontentexceeds thatof thetotal
individualmetals,asshownby the curvesin Figure reducedsulfur).At 500øC, 1 kbar, and 1-m total
3. Moreover,the logarithmsof the concentration ra- chloride,the aqueoussulfidevalueis0.05 m, andthe
tios displaya linear trend with the reciprocalof the ironvalueis0.125 m in theFe-only,QM system;
these
18 HEMLEYETAL.

valuesindicatesulfidedeficiencyby a factorof 2.5. The reader shouldnote that the solubilityof mag-
At 0.1-m chloride, on the other hand, sulfide remains netite alone is essentiallythe sameas that of the as-
at 0.05, but iron is only 0.004 m, indicatingsulfide semblagepyrrhotite-pyrite-magnetite, indicatingthat
in excessby a factorof morethan 12. Thus,the sulfide sulfur-metalcomplexesare not significantcontribu-
contentmayrangefromstronglydeficientto strongly tors to iron solubility.This similarityin solubilityis
excessive,dependingupon total chloride contentof to be expectedbecause fs•-fo•conditions are within
the solution.The geologicimplicationsof suchrela- the H2S field and H2S is itself a rather minor com-
tions are important. Whether one is dealing with a ponentof the aqueousphase.Similarly,chloridebal-
tightly bufferedconditionsuchasthe pyrrhotite-py- ancecalculations indicatethatFe+3isaninsignificant
rite-magnetitetriple point, or a slidingrelation such contributorin the dissolutionof magnetiteand the
as pyrrhotite-magnetite or pyrite-magnetite, the assemblage pyrite-hematite-magnetite.
presenceof magnetiteor other iron-richphasesis a Calculations
critical consideration,as their presencewill tend to
suppress fs• andallowstronglysulfide-deficient con- As additionalbackgroundfor discussion of metal
ditionsto developin stronglysalinefluids.At Butte, sulfide solubility relationsin geologicsystems,the
moresulfurwasfixedaspyrite fromiron in wall-rock concentrations of majoraqueousspeciesin the metal-
oxideand silicatesthan was depositedin the pyrite- free solutionsfor the quartzmonzonitebufferandfor
rich orebodiesthemselves(Salesand Meyer, 1949). the K feldspar-muscovite-quartz buffer are given in
When part of the aqueoussulfideis presentassul- Table9. In addition,speciesin the mixedmetalsystem
fateor SO2,sulfide-deficient conditionsare,of course, in the KMQ buffer are given for 500øC and i kbar.
evenmoreprobable.Assemblages containinganhy- The calculationswere madeusingthe SUPCRT-92
drite (e.g.,earlyButteandmanyporphyrycoppers), database(Johnsonet al., 1992) for the ionsandmin-
therefore,may very well representsulfide-deficient erals, and with the choice of dissociationconstants
conditionsduringtheir formation. for HC1ø and the alkali complexesgiven in Table 7.
Someexperiments wererunonfs2-fo• bufferpoints The constantsare from Sverjenskyet al. (1991) and
otherthanpyrrhotite-pyrite-magnetite. Althoughthe are basedon Shockand Helgeson(1988). At 500øC
dataareincomplete, ironsolubilities forhematite-py- and0.5 kbarsthere is considerableuncertaintyin the
rite-magnetite appearcloseto, butapparently slightly thermodynamicdatabase.The calculationprocedure
higherthan, thosefor pyrrhotite-pyrite-magnetite solvesfor the speciationgiven the appropriatesi-
(Table 4). This is in agreementwith earlier work multaneousequationsand constraintson the system.
(Whitneyet al., 1985),inwhiehfo•wasfoundtohave Activity coefficients,7's, for the ions are assigned
a relatively smalleffect on iron concentration.There unity in one set of calculationsand calculatedby the
are some differences at other more extreme values of methodof Helgesonet al. (1981) in the other.The 7
fs•-fo2on other Cu-Fe-S-Obuffer points,but these unity valuesare of greaterinterestin the highertem-
arebeyondthe scopeof thisreport.Exploratory runs peraturerealmwhere the theoreticalbasisof activity
coefficient
onthepH-fs•-fo•bufferK feldspar-biotite-magnetite- correction becomes more uncertain. The
quartz-ehaleopyrite-bornite,however, are discussed simultaneousequationsubroutineis ZSPOW in the
in Hemley and Hunt (1992). Full evaluationof the International Mathematics and Science Library
response andaccuracy of thevariouspH andfo•and (IMSL) series.The standardstateschosenfor H20
fs• buffersmustawaitfuturework. andfor the solidphasesare the pure fluidsandmin-
In additionto the experiments sys- erals, respectively,at the P and T of interest. For
infs•-buffered
tems, some were done in an unbuffered environment aqueousspecies,the standardstateis the hypothetical
(seediscussion
of the single-metal
sulfidesolubility 1-m solution at the P and T of interest whose behavior
experimentsand Table 4). In theseexperimentsH2S is that at infinite dilution.
was fixed by its stoiehiometrieequivalenceto dis- To illustratethe calculations,
the followingequi-
solvedmetal,asillustratedby equation(7a).Thepur- libriaareappliedin the solutionof speciesdistribution
poseof the experimentswas to assess relative solu- usingthe KMQ buffer andiron mineralsonly:
bilitiesof the individualsulfidesin systemsnot dom- 2H + + 0.5FeS + 0.25Fe304
inated by iron and to cross-cheekthe calculated
dissociation
constants
of the chloridecomplexes.
The
resultsare given in Table 8 and discussed
below. =aFe+•'
=Fe+2+H20+0.25FES2,
K•6 a•+' (16)
The solubilityvaluesfor digeniteand ehaleoeite
are of particularinterestas they are significantly KC1ø =K ++CI-,
aK+aCi-
K•7 =--' (17)
higher than thoseof ehaleopyrite,particularlyat aKCI*
higher temperatures(see Fig. 3b). This difference
showstheimportantroleof ironin suppressingcopper KOH ø =K ++OH-, KlS= aI•+ao.•; (18)
solubilityby forcingthe formationof ehaleopyrite. GKOH*
 HYDROTHERMAL ORE-FORMING PROCESSES.PT. i 19

T^BLE9. SpeciesDistribution(-log activities)

Quartz monzonitebuffer, no metals

log
øC KCI ø NaCIø HC1ø CaCI• K+ H+ Na+ Ca+9' OH- C1- K•o •'+'- •,+9.

1 kbar
600 0.55 0.41 1.20 0.90 2.01 5.79 2.19 6.27 6.61 1.78 6.20
O.59 0.43 1.20 0.90 2.03 5.77 2.19 6.26 6.63 1.80 -0.57 -2.30

5OO 0.60 0.25 2.21 1.33 1.34 4.79 1.35 5.31 6.56 1.04 5.68
0.81 0.37 2.20 1.35 1.48 4.71 1.39 5.18 6.64 1.13 -0.64 -2.56

K feldspar-muscovite-quartz
buffer, no metals

log
øC KC1ø HCIø K+ H+ OH- KOHø C1- Kx•2o 3,+'-

1 kbar
5OO 0.066 1.656 0.928 4.358 6.992 5.620 0.928 5.68
0.261 1.851 1.027 4.457 6.895 5.620 1.026 -0.67

2 kbars
5OO 0.139 2.379 0.570 4.130 6.331 5.140 0.569 5.23
0.392 2.632 O. 696 4.256 6.204 5.140 O. 696 -0.47

0.5 kbars
4OO 0.090 2.159 0.705 4.155 7.205 5.950 0.705 5.68
0.390 2.450 0.850 4.300 7.060 5.950 0.850 -0.62

i kbar
400 0.179 2.669 0.475 4.005 6.776 5.670 0.474 5.42
0.497 2.987 0.634 4.164 6.617 5.670 0.633 -0.47

2 kbars
4OO 0.270 3.040 0.335 4.005 6.175 5.210 0.335 5.09
0.612 3.382 0.506 4.176 6.005 5.210 0.506 -0.38

0.5 kbars
300 0.344 3.284 0.262 3.862 7.058 6.190 0.262 5.46
0.770 3.710 0.476 4.076 6.845 6.190 0.476 -0.40

i kbar
300 0.409 3.459 0.215 3.895 6.735 5.950 0.215 5.32
0.834 3.884 0.427 4.107 6.523 5.950 0.427 -0.36

K feldspar-muscovite-quartz
buffer, with metals

øC KCI ø HCI ø K+ H+ OH- KOH ø FeCI• PbCI• CI-

1 kbar
500 0.241 1.831 1.016 4.446 6.904 5.620 0.996 1.824 1.015
O.445 2.035 1.119 4.549 6.803 5.620 O.996 1.824 1.118

log
øC ZnCI• CuCI
o Fe+a Pb+a Zn+a Cu+ HaS Kx•
2o 3'+'- 3'+a

i kbar
1.393 2.750 7.281 8.470 9.687 7.870 1.33 5.68
1.393 2.750 7.426 8.678 9.895 7.973 1.33 -0.62 -2.50

Non-italicized= activity coefficientsunity; italicized -- activity coefficientscalculated(Helgesonet al., 1981)

20 HEMLEY ET AL.

aH+ac1 - an approximatesolution to the speciationproblem

HC1ø = H + + CI-, K19= --; (19) and are presentedonly for the purposeof mutual
aHCIø
comparison.This approximatecharacter,however,
aFe+ahl doesnot reflect upon the rigor of the calculations.
FeCI• = Fe+2 + 2C1-, K2o =--; (20)
aFeCl• More detailedwork on the speciationof Fe and Zn
and
over a rangeof pressuresandtemperatures is being
completedby J. B. Fein (in prep.) and G. L. Cygan
(in prep.).
H20= H++ OH-, K2•- ai-i+aoH•(21)
aH20 Conclusions
For the pH constraintwe may use either the ex- The experimentalmetal solubilitiesfor rock-buf-
perimentallyobservedEKC1/EHC1= (K+ + KCIø)/ fered hydrothermalsystemsreportedhere provide
(H+ = HC1ø)equilibrium
quotientfortheKMQbuffer importantinsightsinto the acquisition,transport,and
or the equilibriumconstantfor equation (1), K1 depositionof metalsin porphyrycopperand other
= a•c+/aI-i+.
We alsohave the electricalbalancerela- magmaticallyaffiliated hydrothermalsystems.The
tion, rock buffer reactionsdescribingsilicatemineralhy-
K+ + H+ + 2Fe+2= C1- + OH-, (22) drolysisand base metal sulfide dissolutioncan be
combinedinto a setof generalizedreactionsrelating
and massbalancerelationssuchastotal Fe and CI-, primarily alkali (Na and K) and base metal contents
of the hydrothermalfluid;otherimportantvariables,
• Fe = Fe+e+ FeCI• (23) suchasfo•,fs•, andtotalchloride,are definedby the
• CI-=CI-+KC1 ø +HC1 ø+2FeCl•. (24) system.The solubilitycurvesare sigmoidal,with flat-
ter slopesat low andhightemperatures.Solubilityis
We now have 10 equationsand 10 unknowns.Ionic increased by higherchlorideandby lowerfs•, with
activitycoefficients
are firstapproximatedfromionic relativelylittle changewith changeinfo2, provided
strengthsderivedassuming3' = 1 andthen iterated reducedsulfurremainsthe dominantsulfurspecies.
to constantvaluesof 3'. At high chlorideconcentrations in fs•-bufferedsys-
Important aspectsof speciesdistributionare the tems, high dissolvedmetal to reduced sulfur ratios
strongdiminutionof free ion concentrationwith in- may develop.
creasein temperatureand decreasein pressure,and Increasingtemperature and decreasingpressure
the increase in HC1 concentration relative to the cor- drive the base metal sulfide-saturated fluid toward
responding alkalispeciesunderthosesameconditions. highermetal relativeto alkaliconcentrations until the
Thisbehaviormeansthat coolingthesehigh-temper- fluid entersthe two-phase(liquid-gas)field. In the
aturefluidsresultsin a stronglyacidpH, eventhough two-phasefield, total solubilitymusteventuallyde-
pH at P andT is only1 to 2 logunitsbelowneutrality creasewith decreasingpressureat constanttemper-
(Ki•«H20).The hydroxyspecies are relativelyinsig- ature, or with increasingtemperature at constant
nificantcontributors to the equilibria.For CaCI• the pressure.Gas-phaseseparation(i.e., "boiling") can
overalldissociation constantis used,asthe refinement therefore result in base metal precipitation, even
usingbothconstants hasan insignificant effectonthe thoughpressuredecreasein the homogeneous fluid
relations.The salientfeatureof the tableisthe strong regionresultsin higher metal solubility.
contrast between the concentrations of the metal ions Similarityin behaviorofFe, Zn, andPb sulfidesol-
andtheir metal chloridecomplexes. ubilitiespointsto similarityin chloridespeciation,
and
The dissociation constants of the metal chloride the neutralspeciesappearto be dominantin the high-
complexes calculatedfor the mixedsystem,andby a temperature region. Copper solubilitiesare much
differentprocedure,for the singlemetal solubility lower (usingchalcopyritein the mixed system)and
runs, are given in Table 8. The latter procedurere- followa shallowerslopewith temperature,but CuC1ø
quiresa valuefor the fugacitycoefficientof H2S.Also, is alsoassumedto be the dominantcomplex.Calcu-
for copperdifferentmineralswere involved,chalco- lationsof the Ki• valuesfor FeCI•, PbCI•, ZnCI•, and
pyrite vs. chalcocite.The uncertaintiesare basedon CuC1øby two differentmethods,usingdatafromthe
the errorbarsin Figure3. The Ki• valuesrefer to total single metal and polymetal experiments,yield re-
dissociationand involve the assumptionthat com- markably consistentresults for each metal, which
plexingisexclusively represented by the neutralspe- tendsto substantiatethe accuracyof both the ther-
cies at the given P, T, and chloride concentration. modynamicdatabaseand the experimentalfindings.
However, our limited data on iron at 500øC and 1 The framework of total solubilitiesoutlined herein,
kbar indicate an appreciable contribution of the inasmuchasthey are well controlledin termsof pH
monochloride,andthisis probablytrue for lead and andthe fugacitiesof S2and02, shouldserveasa valu-
zinc aswell. TheseKi• values,therefore,represent able guide to our evolvingcapabilitiesat high PT
 HYDROTHERMALORE-FORMINGPROCESSES.
PT. 1 9,1

thermodynamiccalculationsin aqueoussystems.In Frantz, J. D., and Marshall,W. L., 1982, Electrical conductances
and ionization constantsof calcium chloride and magnesium
thisway, experimentalandtheoreticalstudiesshould chloride in aqueous solutionsat temperatures to 600øC and
complementoneanotherandmutuallystimulatepro- pressuresto 4,000 bars:Am. Jour. Sci., v. 282, p. 1666-1693.
gressovera wide rangeof ore-formingenvironments. -- 1984, Electrical conductances of and ionization constants
of salts,acids,and basesin supercriticalaqueousfluids;pt. I,
Acknowledgments Hydrochloricacidfrom 100ø to 200øC andat pressures to 4,000
bars:Am. Jour.Sci., v. 284, p. 611-667.
We wishto thank M. H. Reed, D. A. Sverjensky, Frantz, J. D., Popp, R. K., and Boctor, N. Z., 1981, Mineral-so-
J. K. Boltke, B. R. Doe, P. B. Hostetler, andtwo Eco- lution equilibria, V Solubilitiesof rock-forming mineralsin su-
nomicGeologyreviewersfor helpfuldiscussions and percriticalfluids:Geochim.et Cosmochim. Acta, v. 45, p. 69-
77.
criticismsof the manuscript.We are indebted to Hammerb•ick,S., and Lindqvist,B., 1972, The hydrothermalsta-
H. C. Helgeson and his coworkersfor the SUPCRT bility of annitcin the presenceof sulfur:Geol.F/3ren.Stockholm
databaseandto D. A. Sverjenskyfor someadditional F/3rh.,v. 94, p. 549-564.
current estimateson thermodynamicproperties of Helgeson,H. C., andKirkham,D. H., 1976, Theoreticalprediction
of the thermodynamic propertiesof aqueouselectrolytesat high
aqueouselectrolytes.Analyticalsupport,in addition pressures andtemperatures, pt. III, Equationof statefor aqueous
to that givenby W. M. d'Angelo,draftingsupportby speciesat infinite dilution: Am. Jour. Sci., v. 276, p. 97-240.
Pam Conrad, and especially the support of the Helgeson,H. C., Delany, J. M., Nesbitt, H. W., and Bird, O. K.,
U.S.G.S. machine-shopstaff are also gratefully ac- 1978, Summaryand critique of the thermodynamicproperties
knowledged. of minerals:Am. Jour. Sci., v. 278A, p. 1-229.
Helgeson, H. C., Kirkham, D. H., and Flowers, G. C., 1981,
Theoretical prediction of the thermodynamicbehavior of
August 1, 1990; August 20, 1991 aqueouselectrolytesat high pressuresand temperatures.IV
Calculationof activity coefficientsosmoticcoefficients,and ap-
REFERENCES
parentmolaland standardandrelativeparticalmolalproperties
Barnes, H. L., 1979, Solubilities of ore minerals, in Barnes, H. L.,
to 600øC and 5Kb: Am. Jour. Sci., v. 281, p. 1249-1516.
Hemley, J. J., 1959, Someminera|ogicalequilibriain the system
ed., Geochemistryof hydrothermalore deposits:New York,
K•O-AI•Oa-SiO•-H•O: Am. Jour. Sci., v. 257, p. 241-270.
Wiley Intersci., p. 404-460.
Barnes,H. L., and Czamanske,G. K., 1967, Solubilities and trans- Hemley,J. J., and Hunt, J.P., 1992, Hydrothermalore-forming
port of ore minerals, in Barnes, H. L., ed., Geochemistryof processes in the light of studiesin rock-bufferedsystems:
II.
Some general geologic applications:ECON. GEOL., v. 87, p.
hydrothermalore deposits:New York, Holt, Rinehart andWin- 23-43.
ston, p. 334-381.
Barrett,T. J., andAnderson,G. M., 1982, The solubilityof sphal-
HemIcy, J. J., Montoya, J. W., Marinenko, J. W., and Luce,
R. W., 1980, Equilibriain the systemAI2Oa-SiO•-H•Oandsome
erite and galenain NaC1brines:ECON.GEOL.,v. 77, p. 1923-
1933. general implicationsfor alteration/mineralizationprocesses:
ECON. GEOL., v. 75, p. 210-228.
-- 1988, The solubilityof sphaleriteand galenain 1-5 m NaC1
solutionsto 300øC: Geochim. et Cosmochim.Acta., v. 52, p.
Hemley, J. J., Cygan,G. L., and d'Angelo,W. M., 1986, Effect
813-820. of pressureon ore mineral solubilitiesunder hydrothermal
conditions: Geology, v. 14, p. 377-379.
Bischoff,J. L., and Pitzer, K. S., 1989, Liquid vapor relationsfor
the systemNaC1-H20: Summaryof the PTX surfacefrom 300 Hemley, J. J., Cygan,G. L., Woo, C. C., and d'Angelo,W. M.,
to 500øC: Am. Jour. Sci., v. 289, p. 217-248.
1987, Exploratorystudieson metal sulfidesolubilitiesin buf-
Bourcier, W. L., and Barnes,H. L., 1987, Ore-solution chemistry feredsystems: Implicationsto zoningin ore deposits[abs.]:Geol.
Soc. America Abstractswith Program, v. 19, p. 699.
VII, Stabilitiesof chloride and bisulfidecomplexesof zinc to
Hewitt, D. A., and Wones,D. R., 1984, Experimentalphasere-
350øC: ECON. GEOL.,v. 82, p. 1839-1863.
lations of the micas:Rev. Mineralogy, v. 13, p. 201-247.
Chou, I-M., and Cygan, G. L., 1990, Quantitative redox control
Holloway,J. R., 1977, Fugacityandactivityof molecularspecies
andmeasurement in hydrothermalexperiments: Geochem.Soc.
Spec. Pub. 2, p. 3-15.
in supercriticalfluids,in Frasier,D. G., ed., Thermodynamics
in geology:Dordrecht, Holland, Reidel, p. 166-181.
Dickson, F. W., Blount, C. W., and Tunell, G., 1963, Use of hy-
Johnson,J. W., Oelkers, E. H., and Helgeson, H. C., 1992,
drothermalsolutionequipmentto determine the solubilityof
SUPCRT 92: A softwarepackagefor calculatingthe standard
anhydrite in water from 100øC to 275øC and from 1 bar to
molal thermodynamicpropertiesof minerals,gases,aqueous
1000 bars pressure:Am. Jour. Sci., v. 261, p. 61-78.
Drummond, S. E., and Ohmoto, H., 1985, Chemical evolution species,and reactionsfrom 1 to 5000 barsand 0 ø to 1000øC:
andmineral depositionin boiling hydrothermalsystems:ECON. ComputersGeosci.,(in press).
GEOL., v. 80, p. 126-147. Knopf, A., 1957, The Boulderbatholith of Montana:Am. Jour.
Eugster, H. P., Chou, I-M., and Wilson, G. A., 1987, Mineral Sci., v. 255, p. 81-103.
Montoya, J. W., and HemIcy, J. J., 1975, Activity relationsand
solubilityand speciationin supercriticalchloride fluids, in U1-
mer, G. C., andBarnes,H. L., eds.,Hydrothermalexperimental stabilitiesin alkalifeldsparandmicaalterationreactions:ECON.
techniques:New York, JohnWiley and Sons,p. 1-19. GEOL., v. 70, p. 577-594.
Flowers,G. C., 1979, Correctionof Holloway's(1977) adaptations Nockolds,S. R., 1954, Average chemicalcompositionof some
of the modifiedRedlich-Kwongequationof statefor calculation igenousrocks:Geol. Soc.America Bull., v. 65, p. 1007-1032.
of the fugacitiesof molecularspeciesin supercriticalfluidsof Orville, P.M., 1963, Alkali ionexchangebetweenvaporandfeld-
geologicinterest:Contr. MineralogyPetrology,v. 69, p. 315- spar phases:Am. Jour. Sci., v. 261, p. 201-237.
318. Quist, A. S., and Marshall,W. L., 1968, Electricalconductances
Franck,E. U., 1956, HochverdichteterwasserdampfIIionen-dis- of aqueoussodiumchloride solutionsfrom 0 to 800øC and at
soziation von HCI in H20 bis 750øC, III ionen dissoziationvon pressuresto 4000 bars:Jour. Phys.Chemistry,v. 72, p. 684-
HCI, KOH and H•O in uberkiritschemwasser:Zeitschr. Phys. 703.
Chemic, v. 8, p. 107-206. Ritzert, G., and Franck, E. U., 1968, Electrische Leitfahigkeit
22 HEMLEY ET AL.

wasserigerLosengenbei hohenTemperaturenund Drucken. pressures

and temperatures:Correlationalgorithmsfor ionic
I. KC1,BaC12,Ba(OH)• und MgSO4bis750øC und 6 kbar:Bun- species
andequationof statepredictions
to 5 kb and1,000øC:
sengesell.Phys.ChemieBer., v. 72, p. 798-808. Geochim. et Cosmochim.Acta, v. 52, p. 2009-2036.
Robinson,G. R., Jr., Hemley, J. J., and Cygan, G. L., 1988, Fe, Sourirajan,S.,andKennedy,G. C., 1962, The systemH20-NaC1
Pb, and Zn ratiosin sulfide-saturatedchloride-dominatedhy- at elevated temperaturesand pressures:Am. Jour. Sci., v. 260,
drothermal[abs.]:V. M. GoldschmidtConf. Programsand Ab- p. 115-141.
stracts, v.1, p. 69. Sverjensky,D. A., Hemley, J. J., and d'Angelo, W. M., 1991,
Ruaya,J. R., and Seward,T. M., 1986, The stabilityof chloro- Thermodynamicassessment of hydrothermal alkali feldspar-
zinc(II) complexesin hydrothermalsolutionsup to 350øC: mica-aluminosilicateequilibria:Geochim.et Cosmochim.Acta.,
Geochim. et Cosmochim.Acta, v. 50, p. 651-661. v. 55, p. 989-1004.
-- 1987, The ion-pair constantand other thermodynamic Whitney,J. A., 1972, Historyofa granodioriticandrelatedmagma
propertiesof HCl upto 350øC:Geochim.et Cosmochim.
Acta, systems:
An experimentalstudy:Unpub.Ph.D. thesis,Stanford
v. 51, p. 121-130. Univ., 192 p.
Sales,R. H., andMeyer, C., 1949, Resultsfrompreliminarystudies Whitney, J. A., Hemley, J. J., and Simon,F. O., 1985, The con-
of vein formation at Butte, Montana: ECON. GEOL., v. 44, p. centration of iron in chloride solutionsequilibrated with syn-
465-484. thetic granitic compositions:The sulfur-free system:ECON.
Seward,T. M., 1981, Metal complexformationin aqueoussolu- GEOL., v. 80, p. 444-460.
tionsat elevatedtemperaturesandpressures, in Wickman,F., Wilson,G. A., andEugster,H. P., 1985, Cassiteritesolubilityand
and Rickard,D., eds.,Physicsand chemistryof the earth: Ox- tin-chloridespeciationin supercriticalsolutionslabs.l:Geol.
ford, Pergamon,p. 113-129. Soc.America Abstractswith Programs,v. 16, p. 696.
-- 1984, The formation of lead(II) chloride complexesto Wood, S. A., Crerar, D. A., and Borcsik,M.P., 1987, Solubility
300øC:A spectrophotometric
study:Geochim.et Cosmochim. of the assemblagepyrite-pyrrhotite-magnetite-sphalerite-ga-
Acta., v. 48, p. 121-134. lena-gold-stibnite-bismuthinite
argentite-molybdenitein H•O-
Shock,E. L., andHelgeson,H. C., 1988, Calculationof the ther- NaCI-CO• solutions from 200 ø to 350øC: ECON. GEOL., v. 82,
modynamic andtransportpropertiesof aqueousspeciesat high p. 1864-1887.