ECONOMIC GEOLOGY

AND THE

BULLETIN OF THE SOCIETY OF ECONOMIC GEOLOGISTS

VOL. 81 MAY, 1986 NO. 3

ThermodynamicPredictionsof the Hydrothermal Chemistryof Arsenic,

and Their Significancefor the ParageneticSequenceof Some
Cassiterite-Arsenopyrite-Base Metal SulfideDeposits
CHRISTOPHA. HEINRICH* AND PETERJ. EADINGTON
Divisionof MineralPhysicsand Mineralogy,CSIROInstituteof Energyand Earth Resources,
P.O. Box136, North Ryde,New SouthWales2113, Australia

Abstract

In the absence
of high-temperatureexperimental solubilitydata,thermodynamic
calculations
are usedto predictthe speciationof arsenicin hydrothermalsolutionsand the solubilityof
arsenicminerals.The calculationssuggestthat at neutral to acid pH the aqueousspecies
HaAsO•canaccountfor the transportof adequateconcentrations
of Asto explainthe asso-
ciationsof many hydrothermalAs minerals.Extrapolations of thermodynamicdata to high
temperatures madeusingconstant
heatcapacityof reactionfor equilibriainvolving"balanced
identicallike charges"were combinedwith experimentallydeterminedsolubilitydata for
pyrite.Thisisvalidprovidedthe calculations
are restrictedto the pH-fo2rangewhereH•Sø
is the dominantaqueoussulfurspecies.The As mineralassociations (1) orpiment+ realgar
+ native arsenic+ pyrite, (2) arsenopyrite+ pyrite, and (3) arsenopyrite_+pyrrhotite and
loellingite_+pyrrhotiteare predictedto reacharsenicsolubilitieshighenoughto accountfor
hydrothermaltransportat progressively highertemperatures in systemscontainingexcess
iron sulfide.The solubilityof arsenopyriteis morestronglydependenton oxygenfugacity
than most other ore minerals.
Calculatedarsenopyritesolubilityin relationto calculatedand experimentalsolubilitiesof
other ore mineralspredictsthe followingdepositionalsequences in aluminosilicate-hosted
cassiterite-sulfide
deposits.Cassiteriteis predictedto be followedby pyrite + arsenopyrite
+ basemetalsulfidesfor a hydrothermal solutionwhichremainsbufferedwith regardto pH
andoxygenfugacityby excessoxideandsilicatemineralsin the hostrocksthroughoutits
coolinghistory.Host-rockbuffersarelikelyto havedominated thechemical evolutionof fluids
in disseminated brecciaoresshowingpenetrativewall-rockalteration.
In contrast,the commonlyobserveddepositional sequencecassiterite + arsenopyrite pre-
cedingpyrrhotite+ basemetalsulfidesis favoredby very low oxygenfugacities.Thesemay
be attainedduringthe chemical evolutionandcoolingof fluidsof similarstartingcomposition
but with restrictedopportunityfor reactingwith host-rockredoxbuffers.This situationis
likely to occurwherefluidsare channeledinto narrowveinsandpipesin rocksof very low
permeability,where they depositedlocalizedconcentrations of hydrothermalmineralsin-
volvingonlylimitedwall-rockalteration.Here, precipitationof arsenopyrite by reductionof
As(III) complexes maycouplewith oxidation of Sn(II) complexes to precipitatecassiterite:
3SnCI• + 2H3AsO•+ 2FeCIø•+ 2H•Sø = 3SnO2+ 2FeAsS+ 10C1- + 10H+.
Coprecipitationof cassiteriteq- arsenopyriteby suchan oxygen-conserving redoxreaction
wouldprovideanefficientmechanism to extracttin fromsolutionovera shortcoolinginterval.
Thismayaccountfor the correlationof hightin ore gradeswith higharsenopyrite abundance
asobservedin somecassiteritedeposits.

* Presentaddress:Divisionof PetrologyandGeochemistry,Bureauof MineralResources,

G.P.O. Box378, Canberra,A.C.T. 2601,
Australia.

0361-0128/86/520/511-1952.50 511

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 512 C.A. HEINRICHANDP.]. EADINGTON

Introduction theticalstoichiometricarsenopyrite(Table2). Tem-

ARSENOPYRITE iS a particularly commonand often perature~independent heat capacitiesat 25øC for
abundantsulfidemineralin a wide varietyof tin de- loellingiteandarsenopyrite were takenfromNaumov
positshostedby aluminosilicate rockssuchasgranites, et al. (1974) andfor FeAsthe heatcapacitywases-
acidvolcanics, andpeliticto quartzofeldspathic sed- timatedby addingthe valuesfor the elements.Ther-
iments.It isrecordedfromlode-typeandsheetedvein modynamic datafor the Assulfidesrealgar(ASS)and
cassiteritedepositsin Bolivia (e.g., Kelly and Tur- orpiment(As2Sa) asmeasured by Johnson et al. (1980)
neaure,1970), Cornwall(Jackson et al., 1977, 1982; were used,but the smalltemperaturedependence of
Jackson,1979), Portugal (Kelly and Rye, 1979), the heatcapacitywasneglectedto be consistent with
southeastAsia(Hosking,1973), andeasternAustralia the extrapolationsusedfor the other solidsin the cal-
(Edwardsand Lyon, 1957; Goodeet al., 1982; Ead- culations.Thesedata are in agreementwith Barton
ington, 1983; Andrew and Heinrich, 1984) and it oc- (1969) but notwith the valuesquotedby Wagmanet
curs with cassiterite in disseminated breccia ores in al. (1968) whichare seriously
in error.Orpimentand
New Brunswick(Mulligan, 1975) and easternAus- realgarmelt at 312ø and 307øC, respectively,and
tralia (P. J. Eadingtonand D. J. Paterson,in prep.). liquidsof variableAs/Sratio are stableat somewhat
Detailsare givenin Table 1. In general,the typical lower temperature(Barton,1969). However,arsenic
parageneticsequencecommonto thesedepositshas sulfidemelthasbeenexcludedfromthe presentcal-
an early oxide stageof quartz q- cassiterite___ wol- culations, because the solid As sulfides themselves
framite,followedby a later basemetal sulfidestage becomesosolubleat temperatures above200øC (see
comprisingchalcopyrite q- sphalerite ___stannite below) that solidq- liquid arsenic sulfidecoexisting
___pyrrhotite___ pyrite. Arsenopyritemay be precipi- with a hydrothermalsolutionis unlikelyto occurun-
tated at the onsetof the sulfidestage,but in the ma- der geologicconditions.The iron arsenatescorodite
jority ofthe deposits largelyoverlaps (FeAsO4ß2H20), whichin natureoccursin supergene
itsprecipitation
with the earlierprecipitationof cassiterite(Hosking environmentsonly, is not consideredhere for lack of
and Trounson,1959; Hosking, 1973; Pitragooland thermodynamic dataat elevatedtemperatures.
Panupaisal,1979; andreferencesin Table 1). An un- Solidand aqueousFe-S-O-Hcompounds
derstandingof the factorscontributingto the asso-
Standardthermodynamicdata for the solid iron
ciationof cassiterite with arsenopyriteshouldhelp to
phases FeS• (pyrite), FeS (troilite-pyrrhotite; ne-
characterizehydrothermalsystems that producecas-
siteriteoresandto evaluatepossiblechemicalcontrols
glecting solidsolutionby assuming aves= 1 at all tem-
on the localizationandore gradeof tin deposits.. peratures), FeaO4 (magnetite), and Fe•Oa (hematite)
were taken from the data bank CPDMRLDATA of
The solidsolutionbehavior'ofarsenopyriteandits
Turnbull (1981). The samesourcewasusedfor HgO
stabilityrelativeto other solidphaseshavebeen es-
tablishedexperimentally(Barton,1969; Kretschmar (liquid water at vapor saturation)up to 300øC and
extrapolatedto 400øC by taking a constantheat ca-
and Scott, 1976; Scott, 1983), but so far no experi-
mental data on the hydrothermalsolubilityof arse-
pacity C• (573K)asanapproximation to describe the
subcritical,salinesolutionstypicallyinvolvedin tin
nopyriteor theoreticalinvestigations of the solution
mineralization.Data for the aqueoussulfur species
transportof arsenicand its precipitationas arseno-
were taken from CPDMRLDATA and CPDAQUD-
pyrite havebeen reported.In the absenceof exper-
ATA (Turnbull, 1981). Theseare basedon Wagman
imentaldatafor the speciation of arsenicin high-tem-
et al. (1968) with constantlow-temperatureheat ca-
perature aqueoussolutions,somehigh-temperature
pacitiesusedfor extrapolation.The resultinghigh-
solutionequilibriaare predictedby extrapolationof
temperature free energiesAG• (T = 298-573K) de-
the availablelow-temperaturethermodynamicdata.
viate by about I kcal from the resultsof the recent
This is a preliminary approachwhich may be su-
reevaluationof the S-O-H systemby Murray and
persededby future experiments,but the successful
applicationof the estimatedsolubilitiesin the second
Cubiciotti(1983) usingthe "principle of balanced
identicallike charges"(Cobbleet al., 1982, p. 4-12).
part of the paper, to explain the parageneticse-
quencestypicallyobservedin aluminosilicate-hostedArsine and aqueousspeciesin the As-O-H system
tin deposits,showsthat the thermodynamicextrap-
olations are realistic. Arsenichas a positive(q-3 or q-5) valencyin all
knownaqueous species, in contrastto itsreducedstate
ThermodynamicData and Uncertainties in arsenopyrite where it formsthe anionicpart of the
structuretogether with sulfur (Nickel, 1968). En-
SolidAs compounds thalpiesof formationandthird law entropiesat 25øC
Thermodynamicdata for phasesof the Fe-As-S for aqueousAs-O-H speciesfrom Wagman et al.
systemderived from experimentaldata by Barton (1968) formedthe basisfor estimatinghigher tem-
(1969) were used for FeAs, loellingite, and hypo- perature entropiesusingcorrespondingstatecorre-

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 As HYDROTHERMAL CHEMISTRY: THERMODYNAMIC PREDICTIONS 513

lations.For the ioniccomplexesthe methodof Criss arsenopyrite(lessthan_+2at. % Asin the temperature

andCobble(1964aandb) wasappliedto obtainen- rangeof interest;seeScott,1983), althoughsignifi-
tropics up to 250øC, which were then fitted to the cant,makea relativelysmallcontributionto the un-
relationshipSø(T)- Sø (298K) vs. In (T/298K) as- certaintiesin the estimatespresentedhere. The prin-
suminga constantaverageheat capacity.The method cipal sourcefor potentialerrorsis believed to be in-
of Helgeson(1967; asprogrammed
by Barherand volvedin estimating
free energiesof aqueousspecies
Scheuerman,1978) was used for the neutral com- at high temperatures.
plexesHaAsOs
øandHsAsOø4.
Estimated
low-temper- In caseslike the thioarsenitecomplexes,where
atureheatcapacities(Table2) werepreferredto heat bothSOandC• haveto be estimated,
errorsmaybe
capacitiesaveragedoverthewholetemperature range large and are difficult to assess.It is therefore safer
25 ø to 200øC allowedby this method(whichwould to regard the resultsbased on these data as semi-
be 10-20 cal mole-1 K-1 higher),for reasonsdis- quantitativetrends.The assumptionof constantav-
cussed later in the text. erageheat capacityestimatedfromexperimentalen-
Data for the gasarsine,AsHs(g),were takenfrom tropicsfor the As-O-H speciesmight involveerrors
CPDNPLDATAofTurnbull(1981).Thesesupersede up to _+50cal mole-• K-1, but errorsin AC• of re-
the earlierfree energyquotedby Latimer(1952), actionsare probablysmaller.A heatcapacityerror of
according to whicharsinewouldbe extremelyunsta- 50 cal mole-1 K-1, when extrapolated to 250øC,
ble. Arsineis very weaklysolublein water, with a wouldresultin a free energyerror of 3.5 kcal.This
Henryconstant of 10-5 atroomtemperature
decreas- wouldshift,for example,the equilibriumboundary
ingevenfurtherastemperatureincreases (Sergeyeva HsAsOsø-arsenopyrite (+ pyrite)(Fig.ld, eq.1 inTa-
andKhodakovskiy, 1969). ble 3) by 1.2 logfo• units.At highertemperatures
Thioarsenitecomplexes heatcapacities of chargedspeciestypicallybecome
stronglynegative and the Criss-Cobbleestimatesin
At low temperatures arsenic forms thioarsenite Table2 shouldthereforenotbe extrapolated beyond
complexes of the type (HAsS•ø)n
and (AsS•)n.Ther- 250øC without particularprecautions.The heat ca-
modynamically
controlledexperiments coveringthe pacitiesof neutralcomplexesgenerallyvaryfar less,
wholepH rangeof geologic
interestby Mironovaand but errorsof 50 cal mole-• K-1 probablycannotbe
Zotov (1980) showthat at 90øC, the binuclear com- excludedin extrapolations to 400øC, where suchan
plexesH2As2Sø4 and HAs2S• are more stablethan errorwouldshiftequilibrium(1) by 3.5 logfo• units.
H3AsOs øin neutralto acidsolutionswithexcess H•Sø. Theseerrorsappearto be high,but it shouldbe con-
At 20øC,titrationexperiments were interpretedby sideredthatthe dataevenfor experimentally studied
AngeliandSouchay (1960)to indicatethe presence equilibriasuchaschalcopyrite solubilitymaylikewise
of trinuclearspeciessuchas H3AssS6 ø. Indeed, dis- involveuncertainties of 2 log K units(J. L. Walshe,
sociation to lowerpolymerization numbers andfinally unpub.data;seealsoCrerar et al., 1978, p. 1433).
to the mononuclear complexes HAsS•øandAsS•would It is concludedthat the presentlyavailabledata
be expectedto occurwith increasing temperature, onlyalloworder-of-magnitude predictionsof thehy-
but because of the changein stoichiometry it is not drothermalgeochemistry of arsenicat hightemper-
possible to calculate partialmolarentropiesfromthe ature but that the errorsare acceptablein this first
temperaturedependence of publishedequilibrium approachto understanding arsenopyrite-forming re-
constants. An estimationof the maximumlikely sta- actionsin tin deposits.However, the data are not suf-
bility of the speciesHAsSø• andAsS•at elevatedtem- ficiently accurateto constrainquantitativemass
perature has therefore been based on the measure- transfercalculations. A dangercommonto all ther-
mentsof MironovaandZotov(1980)andthe conser- modynamic extrapolations
of aqueous equilibriaisthe
vativeassumption that the mononuclear complexes possibility thatanasyetunknownspecies maybecome
mightcontributeup to 10 percentof the total dis- stableat hightemperature. This uncertaintyis the
solvedarsenic at 90øC(cf.MironovaandZotov,1980, mostseriousrestrictionof this kind of study.
fig. 3). Heatcapacityvalueswereestimated withthe
samemethodsasusedfor the As-O-Hcomplexes but PredictedSpeciationin the As-S-O-HSystem
hadto bebasedonentropies whichwerethemselves NinetydegreesC isthe onlytemperatureat which
estimatedvalues,followingthe methodof Cobble the As-S-O-Hsystemcan be calculatedover a wide
(1953, eq. 8). rangeof pH andredoxconditions. Figurel a shows,
Magnitudeof possibleerrors asa functionof pH andoxygenfugacity, the stability
fieldsof arseniccompounds coexisting
with a sulfur-
Uncertaintiesin the free energiesof formationof bearingaqueous solution.In the predominancefield
all solids
canbe conservatively estimated at _+2kcal/ of reducedaqueoussulfur,the stabilityfieldsof the
moleat all temperatures. This uncertaintyand the solidarsenicsulfides orpimentandrealgararedelin-
neglectedeffectsof solidsolutionin pyrrhotiteand eatedby theirdissolution to thioarsenite
complexes.

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 514 C. A. HEINRICH AND P. J. EADINGTON

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 As HYDROTHERMAL CHEMISTRY: THERMODYNAMIC PREDICTIONS 515

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 516 C. A. HEINRICH AND P. J. EADINGTON

TABLE 2. StandardThermodynamicData for ArsenicSpeciesin the SystemAs-Fe-S-O-H

•xi•?(298•) so(298•) %o(298•)

(cal/mole) (cal-moledegree)

As (s;arsenicnative) 0 8.5 5.9 Turnbull(1981)

As•Oa (s;arsenolite) -157,000 25.6 23.8 Turnbull(1981)
AsS (s;realgar) -8,252 14.8 11.2 Johnsonet al. (1980)
As2Sa (s;orpiment) -21,893 39.1 27.6 Johnsonet al. (1980)
FeAsS (s;arsenopyrite) -25,200 25.9 17.6 Barton(1969), Naumovet al. (1974)
FeAs2 (s;loellingite) -10,400 30.4 17.8 Barton(1969), Naumovet al. (1974)
FeAs (s) -4,200 23.3 11.9 Barton(1969),Cp
øsumof elements
AsHa (g; arsine) 15,900 53.2 9.2 Turnbull(1981)
HaAsO•(aq;arsenious
acid) -177,400 46.6 39.0 Wagman
et al. (1968),Cp
øestimated
H2AsO•(aq) -170,840 26.4 19.6 Wagman
et al. (1968),Cv
øestimated
HAsO•• (aq) -163,200 -3.4 -57.6 Wagman
et al. (1968),Cp
øestimated
AsO•• (aq) -157,100 -44.4 -113.1 Wagman
et al. (1968),Cp
øestimated
HaAsO](aq;arsenic
acid) -215,700 44.0 72.4 Wagman
et al. (1968),Cp
øestimated
HaAsO•(aq) -217,390 28.0 27.2 Wagman
et al. (1968),Cp
øestimated
HAsO•• (aq) -216,620 -0.4 -43.5 Wagman
et al. (1968),Cp
øestimated
AsO•a (aq) -212,270 -38.9 -99.7 Wagman
et al. (1968),Cp
øestimated
HAsS0 (aq) >•-5,310 40.0 18.4 Maximumstabilityallowedby
Mironova and Zotov (1980),
AsS• (aq) >•-6,410 20.0 -57.4 SoandCp
øestimated
H•As•S4
ø (aq) AG•(363K)-- -22,290 Mironova
andZotov(1980)
HAs2S•(aq) AG•(363K)= -14,780 Mironova
andZotov(1980)
As•S•
• (ag) AG•(363K)= -3,410 Mironova
andZotov(1980)

AH• = standardmolarenthalpyof formation

fromelements;AG• = Gibbsfreeenergyof formation
fromelements;
SO= standard
molarthirdlawentropy;%o= standardmolarheatcapacity;
s = solid;g = gas;aq -- aqueous
Referencestatesare pure solids,ideal gasesat 1 bar, pure liquid water at vaporsaturation,andhypotheticalideal aqueoussolutes
at 1 mole/kgH•O

Note the two fo•-independentboundariesbetween complexes,which intuitively might be expectedas

the orpiment, HAs•S•, and As•S•• fields. These As-transportingspeciesin hydrothermalsulfide-de-
boundariesrepresentthe equilibriameasuredby Mi- positingsystems.Figure 2a showsthat at a given pH
ronovaand Zotov (1980) on whichthe free energy the complex AsS• tends to become replaced by
derivations
for thethioarsenite
complexes
werebased. HAsSø•
with increasing
temperature,in accordwith
As-O-H complexesare only stablein the sulfatefield the generaltendencyfor neutral speciesto be stabi-
and at very high pH at these conditions.Arsenolite lized relative to ionic speciesat elevatedtempera-
or claudetite,As•Oa,hasno stabilityfield at the de- tures.The diagramsuggests that, if any thioarsenite
pictedconditionsbut would replacethe arsenicsul- speciesis presentat the pH-T conditionsassociated
fidesat higher arsenicand/or lower sulfuractivities with cassiteritemineralization(stippledarea), it is
(see, for example, Sergeyevaand Khodakovskiy, more likely to be HAsSø• than AsS•. Under alkaline
1969). conditions,however,AsS• or its polymerscouldbe
Figure lb showsthe predicted stabilityrelations importanteven at high temperatures,and this is in-
for the samesystemat 250øC. The calculationin- deed suggestedby the high solubilitiesof orpiment
cluded the minimum estimatedfree energy of the in stronglyalkalineNa•S solutionsat •<200øCasmea-
mononuclearthioarsenitecomplexesHAsS• ø and sured(unfortunatelywithout pH control)by Weiss-
As•S•, asgivenin Table 2 anddiscussed above.There berg et al. (1966). Someof the field boundariesshown
is no stabilityfield for thioarsenitecomplexesat the with heavy broken lines in Figure lb and d may
specified
activities
of aqueous sulfurandarsenic
(10-2 therefore be metastable.
and10-a, respectively).
Also,thesolidarsenicsulfides Figure 2b showsthe likely maximum extent of
are too soluble to be stable under these conditions. HAsSø•
relativeto HaAsO•.It suggests
that at the for-
Instead,HaAsO•coversa wide stabilityrange ex- mation temperaturesof cassiterite-sulfidedeposits
tendingfromthe predominancefieldsof oxidizedsul- unrealisticallyhigh sulfideactivities(>10-•) would
fur far into the H2Sø field andcoveringthe geologi- be required to make HAsSø•predominantover
callyimportantpH rangefromacidto weaklyalkaline. HaAsO•.Considering the uncertaintyin the datathis
The curvespresentedin Figure 2 were calculated argumenthas to be taken with caution,but even if
to explorefurther the likely stabilityof the arsenious HAsSø•
were presentin comparableconcentration
to
acid complexHaAsO• relative to the thioarsenite that predictedfor HaAsOa ø, thiswouldprobablynot

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 As HYDROTHERMAL CHEMISTRY: THERMODYNAMIC PREDICTIONS 517

TABLE 3. SomeExperimentaland CalculatedEquilibrium Constantsat High Temperatures,as Used

in the Constructionof Figures 3 to 5

Equilibrium constantlog K

Reaction 200øC 250øC 300øC 350øC 400øC

(1) 4FeAsS
+ 4H2S
ø+ 502g+ 2H•O = 4FeS•+ 4HaAsOa
ø 218.2 191.3 169.0 150.2 134.1
(calculatedfrom Table 2 and CPDMRLDATA data bank by
Turnbull, 1981)
(2a) FeS•+ C1-+ 2H+ + H20 = FeC1+ + 2H•Sø+ 0.502g -22.9 -18.5 -15.5
(2b) FeS2+ 2C1-+ 2H+ + H•O -- FeCI•+ 2H•Sø+ 0.50• -15.2 -8.7
(combinationof equilibriumconstantsin Walshe and
Solomon,1981, appendix2; recalculatedfrom Crerar et
al., 1978)
(4a) 4FeAsS+30•+4Cl-+8H ++6H•O= 4FeC1
++4H2Sø
+ 4HaAsOa
ø 126.6 117.3 107.0
(4b) FeAsS+ 30• + 8C1- + 8H + + 6HaO -- 4FeClg + 4HaSø
+ 4HaAsO•a 108.2 115.4
(combinationof reactions2a andb with 1)
(6) SnOa+ 2C1-+ 2H+ = SnC12
ø+ HaO+ 0.502, -22.7 -18.8 -15.4 -12.4 -9.6
(EadingtonandGiblin, 1979; Eadington,1982; calculated)
(9) KAlaSiaO•o(OH)a
+ 3SiOa+ 8FeAsS
+ 24HaO+ 6Oa•
= KFeaA1SiaO•o(OH)a
+ FeaA12SiaO•o(OH)s
+ 8HaAsOa
ø
+ 8HaSø 197.5 176.3 158.9 144.1 131.6
(calculatedincludingsilicatedata from Helgesonet al.,
1978, andWalshe, 1984; seetext)
(10) 4KAlaSiaO•o(OH)•
+ 12SiO•+ 20FeAsS
+ 62H•O + 150•g
= 4KA1SiaOs + 4FeaA12SiaO•o(OH)s
+ 20HaAsOg
+ 2OHaSø 493.5 441.1 398.0 361.7 330.7
(as reaction 9)
(11) 2FeS+ 2HaS
ø+ O• -- 2FeSa+ 2HaO 52.4 45.4 39.5 34.6 30.4
(calculatedfrom CPDMRLDATA data bank; Turnbull,
1981)
(12a) 4CuFeSa+ 12H + + 2HaO + 8C1- = 4FeC1+ + 4CuCIø
+ 8H2S
ø+ O2• -57.2 -42.4 -32.8
(12b) 4CuFeSa+ 12H+ + 2HaO + 12C1- -- 4FeClø•+ 4CuC1ø
+ 8HaS
ø+ Oa• -31.6 -2.4
(combinationof equilibriumconstants
in Walsheand
Solomon,1981, appendix2; recalculatedfrom Crerar and
Barnes, 1976)

Log K valuesrefer to activityproductsaccordingto the standardstatesspecifiedin Table 2, bottom

alterthequalitative
conclusions
regardingparagenesisthereforebeen calculated.Figure lc andd showthe
andredoxmechanisms intindeposits
(below),because stabilityfieldsfor As(-Fe)compounds,under other-
arsenichasthe same+3 valencyin bothcomplexes. wise identicalconditionsasin Figure la and b. The
However, it would affect the massbalance in a sulfide- stabilityboundariesof the coexistingFe phaseare
depositing
system because
arsenopyrite
precipitation markedby finebrokenlines,but the boundaries for
fromHaAsOaøwill consume
H2Søwhereasitsformation the sulfurspecies(seeFig. la andb) in the aqueous
from HAsSz
ø would liberate sulfur. solution that occur throughout the diagramsare
Arsine,AsHa(g)canclearlybe excludedasa pos- omittedfor clarity.At 90øC,the additionof Fe causes
sibleAs-transporting speciesundernaturalhydro- arsenopyrite,loellingite,andFeAsto replacepart of
thermalconditions, becauseit is stableonly at un- the stability field of native arsenic,but the Fe-As
realisticallylow oxygenfugacity.For example,at the phaseshaveboundarieswith aqueousAsspeciesonly
oxygenfugacitycalculated fortheAsHa-As boundary at very high pH. Arsenopyriteand loellingite have
at 250øC, a hydrogenfugacityfH=of severalkilobars solubilitiesthat are toolow for significant
hydrother-
would be attained. mal transportunder rock-bufferedpH conditionsat
such low temperatures. At 250øC, however, arse-
PredictedHigh-TemperatureEquilibriumPhase
nopyrite(+ pyrite)reaches a solubility
of 10-a to 10-2
Relationsin the As-Fe-S-O-HSystem
asHaAsOa ø, accordingto the incongruent dissolution
Stabilityrelationswith excess
Fe phaseto 250øC reaction:

In nature, arsenopyriteis often associatedwith 4FeAsS+ 4H2Sø + 502 + 2H20

pyrrhotiteor pyrite. Hydrothermalphasecompati-
bilitieswith excessFeS,FeS2,Fe304, or Fe2Oahave = 4 FeS2+ 4HaAsOøa.(1)

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 (a) (c)
90 øC As-S-O-H 90øC Fe-As-S-O-H with excess Fe
i

H2AsO•,
o

H•AsO• HAsO]-
-5O '-.... As02•
-_

orp

" -60 HAs2S•,,

As

-70
asp

toe

-8O

I I I

0 2 • 6 8 10 12 1• 0 6 8 lO 12 1/,

pH pH
(b) (d)
250oc As-S-O-H 250 øC Fe-As-S-O-H with excess Fe
-2O
s0•.

=,• • I HAsO•-
-3O
H3AsO•
" AsC•
• I

-•_o•
' ,_H•
•;• ..... --- ,
-L So?-

,
•----•
• '
I
m ,
'2

.....
PY
H3AsO•

".•-T•'-.
._ .-' •1 "'•.,,m
I ! -J
m l
', • m '-• ---
asp / /, • •1
HAsO
3 .j J
AS m m

• ...... •--•
toe /

-5O - I
'
i I
,
i
As0 •--• _p_o
.................
F.
.'
FeAs
AsH)(g) •,, '•'A
, i i i I i I i I
0 2 • 6 8 •0 12 1• 0 2 • 6 8 10 12 1/,
pH pH
FIG. 1. pHvs. logfo• diagramsshowingcalculatedpredominance
fieldsfor arsenicspeciesin
equilibrium
with a sulfur-bearing
aqueous fluid.Stabilityfieldsfor the solidphasesorpiment(orp,
As•S3),
realgar(rea,ASS),nativearsenic(As),arsenopyrite (asp,FeAsS), 1oellingite
(loe,FeAst),and
FeAsaregivenforconstant activityOfall aqueous sulfurspecies at 10-• (predominancefieldsshown
by finelinesin theleftdiagram
only)andof all aqueous
mononuclear
Ascomplexes
at 10-3. The
binuclear
complexes
H•As•S4
øandHAs•S•areatanactivityof5.10-4.Arsine(ASH3)fugacitywaschosen
as100bars.Thiscorresponds
to anapproximate
activityof aqueous arsineof 10-3 sincetheHenry
constant is about10-5 molekg-] bar-]. Thioarsenitecomplexes suchas(AsS•),couldbe stableat pH
> 6.5 at 250øC (seetext).Therefore,someof the fieldboundaries shownby brokenlinesin diagrams
b andd maybe metastable(cf. Fig. 2). Abbreviations are explainedin Table 1.

518

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 As HYDROTHERMAL CHEMISTRY: THERMODYNAMIC PREDICTIONS 519

b) 1478). Cobble et al. (1982) have shownmore gen-

\1 • ,/[ I I I [ ]
erallythattheheatcapacitychangeAC•,of equilibria
involvingonly neutral speciesand the samenumber
possibly // of equallychargedionson both sidesof the reaction
6
do not vary by more than the experimentaluncer-
dominant/ tainty over the whole temperaturerangefrom 20 ø to
, •:..."•';'.-(/•i:?•:
/// H3AsO at least 300øC. This principle of balancedidentical
like chargesis consideredby Murray and Cubiciotti
•x•
100
I I
200
log
OK+=-1
x
I
300
I
gO0
xxxx
x dominant
I
100
I
200
I
300
I
t, 00
(1983) to be more accuratethan the extrapolationof
the corresponding statecorrelationsbeyond200øC.
Thisiswhy estimatedlow-temperatureheatcapacities
T of H2Sø andHaAsO•canbe usedin determiningthe
FIG. 2. Activity-temperaturediagramsshowingthe estimated
heat capacityof reactionwhich is then extrapolated
maximumhigh-temperaturestabilityof the thioarsenitecomplexes to high temperatures.
HAsSø• andAsS•.(a).The estimated pH (or pK) of the deproton- The followingextrapolations
to temperatures above
ation reaction HAsSø2= AsS• + H + in relation to the H•Sø-HS- 250øC (Figs.3, 4, and 5) have been strictlyconfined
boundary,the line of neutralpH, aon- -- an+,and contoursof log to thestabilityfieldofH2Sø.Thisallowstheprediction
aK+referring to the pH buffered by K-feldspar q- muscovite
q- quartz, after Montoya and Hemley (1975). At pH and T con- of solutionequilibriainvolvingonly neutralspecies
ditions associated with the formation of aluminasilicate-hosted and their combinationwith publishedequilibrium
tin deposits(stippledarea),AsS•is unlikelyto be the predominant constantssupportedby direct high-temperaturesol-
As-transportingcomplex. (b). The maximumexpected extent of ubility experiments.As a consequenceof this pro-
the stabilityfieldof HAsS•
ørelativeto H•AsO•asa functionof H•S cedure the calculatedequilibriumconstantsgivenin
activity.The calculatedcurve suggests
that at temperaturesabove
200øC unrea!isticallyhigh H•S activitieswould be required to Table 3 shouldnot be extrapolatedto higher pH or
stabilizeHAsSø•
relativeto H•AsO•
ø.

I ] [ [ 0/ [/
togOFeœ12n-n
_Z
t/?/ /
This reactiondescribesthe equilibriumbetween an
HzSø-bearing
fluidandcoexisting
arsenopyrite
+ py- ,,\, / -
rite throughoutthe acid to neutral pH range of in- -8.•///,"
terestfor manygeologicsystems.
Predictionsfor theH•Søpredominance
field to 400øC i i

The principleof balancedidentical like charges:

All arsenicspeciationboundaries occurringasheavy
linesin Figure 1a to d within the field of H•Sø asthe
predominantsulfur speciesare horizontal,because
the corresponding reactionsdo not involveH +. More
-50
generally,they involveonly neutral aqueousspecies
and solidphases.An exampleis reaction(1) given
aboveandin Table3, whichdescribes the equilibrium • I I I I I
boundaryarsenopyrite-HaAsOa ø in Figureld. 150 200 250 300 350
The result of the calculationsdiscussedsofar, that Temperature (øC)
two neutralaqueousspecies,HaAsO• øandHzSø,con-
FI•. 3. Oxygen fugacity log fo• vs. temperature (scaledto
trol mineral-fluidequilibriain the Fe-As-S-O-Hsys- inverseabsolutetemperature)diagramshowingcalculatedstability
tem (and arsenopyrite solub'ilityin particular) fieldsof thearsenicspecieswithinthepredominance fieldof H•Sø.
throughouta wide pH-fo=rangeof geologicimpor- AqueousH•AsO• øis at activitiesof 10-4 and10-s (full anddashed
tance is favorablefor the extrapolationof the ther- field boundaries,respectively).The Fe-As-S-O-Hsystemis shown
modynamicdata to high temperatures.The partial in equilibrium
withanaqueous
solution
atgivenactivities
of H•$ø
and CI-, togetherwith an excessof Fe sulfidemineral (pyrite or
molarheat capacityof unchargedaqueousspeciesis pyrrhotite,respectively,aboveandbelow the indicatedboundary).
expectedto vary far lessin responseto changingdi- All reactionsdefiningfield boundariesshownassolidlinesare pH
electric propertiesof the aqueoussolventat high independentand involve only solid and neutral aqueousspecies
temperaturethanthat of ions.In additionthe activity (Fig. I andTable 3), exceptfor the upperlimit of aqueous
H•Sø
stability and the fine dashedcontoursfor total iron activity (as
coefficientsof the neutral specieswill not deviate FeCI•-") in the H•AsO• solutionfield. Theseare calculatedfor
markedlyfromunity sothat activitiescanbe approx- pyrite saturationat ac•- -- I and a pH fixedby aK+= 0.1 with the
imatedby concentrations (Helgesonet al., 1981, p. presence
of excess
muscovite
q-potassic
feldsparq-quartz.

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 520 C.A.HEINRICH
ANDP.J.EADINGTON
i i i i
effectonthe boundariesof the H3AsO3 øfieldbut shifts
the boundaries betweenall solidsdownby œlogfro
-25,,...•-•
=%•S
o=1m '•....
-.....
_',,,•_,•
units. At all geologicallyrealisticconcentrations,ar-
senopyriteprecipitation is restricted to low redox
conditions where reduced sulfur is dominant in so-
lution. As discussedaboveand seenby comparison
with Figure2b, the boundaries
of the H3AsO•field
with the As-Sphasesat temperaturesbelow 150øC
could be metastable relative to thioarsenite com-
plexes,whichwouldalsobe stabilizedby higherH2Sø
activity.
The concentration of iron in solution asFeCI + and
FeCI•isbuffered--atgivenpH, CI-, andH2Søactiv-
I I I • I I ities-by thepresenceof anFe sulfide,pyriteor pyr-
150 200 250 300 350 •00 rhotite:
Temperalure (•C)
FeS2 + nC1- + 2H + + H20
•. •. Co•tou•s{o• the eo•me•t so]ubilit•o{ •se•op•ite
•eeo•i• to e•ui]ib•[• (• • b) (seetext •d T•ble 3), •t e•u•] = FeCln
z-n+ 2H2Sø + 0.502 (2)
and
•t •eut•] to •eid p• buffe•edb• the p•ese•ee
t•ssie{eldsp• + •u•t•. The ]•bels ]6 to ]6•000 ppm •die•te FeS+ nC1-+ 2H+ = FeCln
z-n+ H2Sø. (3)
•pp•oxim•teeo•espo•di• concentrations • mfi][•ms o{ •e•sS
i• ]-k• •ueous solution,t•ki• •et•vit• eoe•eie•ts •s ]. U•li•e Thecontours ofFe(total)in theH3AsO3ø+ pyritefield
those{o• mostothe• om mi•e•]s (e{. •i•. •), the slopeso{ the (fine broken lines) were calculatedfrom combined
solubil•t•eo•tou•s[o• •se•op•ite •e •tte• th•n the solid-solid log K valuesgiven by Walshe and Solomon(1981,
•ie•el-•ieke] oxide (•O), • /•]ite-m•etite + •u•tz Appendix2, recalculated fromexperiments by Crerar
(FMQ), andbecomenegativeat T > 300øC, where FeCI• rather et al., 1978). They change their slope because
than FeCI* is the predominantaqueousiron speciesin solution. FeCI• displaces FeC1+ asthe predominant ironcom-
The intersectingdmhedcontoursegmentsm•k the pyrite-pyr- plex at temperaturesaboveabout 300øC.
rhotitebound•y for the corresponding H•Søactivitiesa•so = 10o
to 10 -4. Arsenopyrite solubility:The reactiondescribingthe
congruentsolubilityof arsenopyrite:
4FeAsS + 302 + 4nC1- + 8H + + 6H20
more oxidizingconditions.Relativelyhigh pH con-
ditionscompatiblewith HS- rather than H2Sø could = 4FeCI•-n + 4H2Sø + 4H3AsO3
ø, (4)
occurin carbonate-hostedtin deposits,whichwill not
be includedin theapplication presented in thesecond doesnot satisfythe criterionof balancedidenticallike
part of the papermainlyfor thisreason. chargesas definedby Cobble et al. (1982). Equilib-
Equilibriumrelationswith excesspyrite or pyr- rium constants for reaction(4) have thereforebeen
rhotite:Figure 3 showsthe predictedstabilityfields calculated by combining theexperimental equilibrium
for arseniccompounds coexisting with aniron sulfide constantsfor pyrite solubility(reaction2) with the
(pyriteor pyrrhotiteasmarked)and an aqueousso- calculatedlogK valuesfor reaction(1) describingthe
lutioncontaining10-2 m H2Sø, similarto Figurelc incongruentsolubilityof arsenopyriteto pyrite.
and d but now asa functionof temperatureand log Figure 4 showscontoursfor the solubilityof ar-
fro. Exceptfor the upperboundaryof the H2Søpre- senopyriteaccordingto equilibrium(reaction4), in
dominancefield (full fine line) and the fine broken a chloride solutionwith ac•- = 1 and aic+= 0.1 buff-
contours in the H3AsO3
øfield,all equilibriumbound- ered with regardto pH by potassicfeldspar+ mus-
ariesare pH independentin the neutral to acid pH covite+ quartz(MontoyaandHemley,1975). Similar
region. to the fine brokencontoursin Figure 3, the contours
As the oxygenfugacityis loweredor the temper- of arsenopyritesolubilitychangeslopenear 300øC
atureisincreased,orpimentisreducedto realgarand whereFeCløz replacesFeC1+ asthe predominant iron
nativearsenic(in the pyrite field) and eventuallyto complex(reactions4a and 4b, Table 3). The contours
arsenopyriteandloellingite(in the pyrrhotitefield). in Figure 4 are given at the equal activities of
The lower limit of the field in which arsenic can be a•I3aso•= a•i•s0= aFeCl•-".Sincethe three aqueous
effectivelytransportedasH3AsO3 øisgivenforconstant specieshave the same stoichiometriccoefficientin
activitiesofa•i3aso•
= 10-4 (corresponding to 7.5 ppm reaction (4), contoursfor any other combinationof
As;full line)and10-s (0.75 ppmAs;brokenline).A activitiescanbe readily obtainedfrom Figure 4: for
tenfoldincreasein H2Sø activityhasrelativelylittle example,the 10-2 contouralsorepresents
the solu-

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 As HYDROTHERMAL CHEMISTRY: THERMODYNAMIC PREDICTIONS 521

bility for ai•sAso•

= 10-ø, aFec•-n = 10-I, and ai•2so thesesulfidesoccurredtogether,commonlyindicate
= 10-2. The labelsin ppmindicatethe approximate a temperature of formationin the range of 220 ø to
concentrationof total FeAsSin solution,takingactiv- 320øC (e.g., Bertman,1976; Henley et al., 1976; Cox
ity coefficientsasone (in reality,3•isAsO•
_• 3•i•2so
• 1 et al., 1983; Roedder, 1984, table 1). The frequent
> 3•Fec•+ is more likely). associationof pyrite and arsenopyritein theseveins
These calculationsindicate that arsenopyritesol- could reflect direct couplingof the precipitationof
ubility is morestronglya functionof oxygenfugacity pyrite and arsenopyrite(reactions2 and 4) to an ox-
thanof temperature.Thisbehaviorcontrasts with that ygen-conserving coprecipitation reaction:
of most other common ore minerals for which the
solubilitycontoursare eitherfo• independent(pyr- 2H3AsOo ø + 5FeC1+ + 8H•.Sø
rhotite, sphalerite,galena)or have a steep positive
sloped(logfo•)/d(1/T) (pyrite, chalcopyrite,cassit- = 2FeAsS+ 3FeS•.+ 5C1- + 6H•.O + 10H+. (5)
erite) within the H2Sø field. In addition to the general associationof gold + ar-
Comparisonwith SomeNatural Occurrencesof senopyrite+ pyrite in quartz vein deposits,high Au
Arsenic Minerals gradesoftencorrelatemorecloselywith arsenopyrite
than with pyrite enrichment(Boyle, 1979, p. 188).
Orpiment, realgat, and native arsenic This andthe commonobservationthat high goldval-
Figure 3 indicatesthat, dependingon H•.Sø con- ues occur where the veins transect carbonaceous
centrations,realgar, orpiment, and native arsenic metasediments(e.g., Wilton, 1984, p. 510; Hutch-
reach solubilitiesas HaAsOa ø which are sufficientfor insonand Burlington,1984, with earlier references)
hydrothermaltransportat temperaturesof lessthan could be related to the experimentalobservation
200øC, even if the possiblepresenceof thioarsenite (Seward,1984) that gold precipitationalsorequires
complexesat these conditions is neglected. This a reductionfrom oxidizedcomplexesto nativemetal.
agreeswith the commonparagenesis of the As-Smin- In manyvein depositscontainingarsenopyrite,gold
erals, which form at low temperaturestransitional precipitationoccurredlater and at lower tempera-
between late hydrothermalactivity (includinghot tures (220ø-320øC) than the formation of arseno-
springs)andthe onsetof weathering. pyrite + pyrite, which formedat temperaturesin ex-
Althoughpyrite can stablycoexistwith a solution cessof 340øC (Coveney,1981; Green et al., 1982).
depositing orpiment+ realgar,the iron concentration Gold depositionon grainboundariesandin cracksof
of lessthan10-s istoolowforeffectivetransportationpreexistingarsenopyritecan be explainedby minor
in the samesolution.This is in agreementwith the redissolution of arsenopyrite accordingto reaction(4),
observation that the As-Smineralsare rarely found a processwhich would act as a local redox-trap for
to have coprecipitatedwith an Fe sulfidebut rather gold precipitation.
are depositedtogether with other low-temperature
sulfidessuchas antimonite,proustitc,pyrargyrite, Loellingiteand arsenopyrite+ pyrrhotite
and variousAs sulfosalts(Ramdohr,1980, p. 369 Thecalculated boundaries oftheH3AsOa øfield(Fig.
and 890). 3) indicatethat at a givenfluidcomposition increasing
At the Lengenbachdeposit (SwissAlps) pyrite temperaturefavorspyrrhotiteinsteadof pyrite asthe
+ realgar+ orpimentdo occurtogetherin vugsof a iron sulfide phasecoexistingwith an As mineral.
low-grademetadolomite, but Graeser(1975) hassug- However, pyrrhotite itself is so solubleat tempera-
gestedon different groundsthat arsenic(and other turesabove350øC, that undermostore-formingcon-
elementssuchasCu, Sb, andT1)were mobilizedby ditions the loellingite + HoAsOa ø (+ pyrrhotite)
late metamorphic solutionsfrompeliticandquartzo- boundaryin Figure 3 will be metastable.This iscom-
feldspathicgneissesand precipitatedin the more patiblewith the observationthat loellingiteoccursin
reducing,primarilypyritic metadolomite.The sug- pegmatitic rocks without any coeval sulfides(Ram-
gestionof two different sourcesfor the chemicalcom- dohr, 1980, p. 858). However,no attempthasbeen
ponentsthatformedthe largenumberof rare sulfosalt madein the presentstudyto estimateloellingite sol-
mineralsat Lengenbachis in agreementwith the ubility in the possiblysupercriticalsolutionsof this
present calculations. environment.
Similarly,the boundaryin Figure 3, alongwhich
Arsenopyrite+ pyrite in gold-bearingquartz veins arsenopyrite + pyrrhotite+ H3AsOaøarepredictedto
The lowest realistic concentrationsat which As, S, coexist,is likely to be stableonly if either H•.Sø in
and Fe can be transportedoverlapin the 200ø to solution is much in excess over iron and arsenic or if
300øC temperaturerangewhere arsenopyrite+ py- oxygenfugacitiesare below the fayalite-magnetite-
rite coexistat the boundaryof the H3AsOa ø field in quartz (FMQ) buffer. Arsenopyrite + pyrrhotite
Figure 3. Fluid inclusions
from gold-bearingquartz- (_ pyrite) does occur in some gold-bearingquartz
arsenopyrite-pyriteveins, in which precipitation of veins,where it indicatesvery low oxygenfugacities

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 522 C.A. HEINRICHANDP.J. EADINGTON

possiblyrelated to carbonaceous matter. The associ- important in the depositionof ore mineralsas rela-
ationis alsocommonin vein-typecassiteriteores,but tively narrow shellsor orebodiesof economicmetal
in thesedepositsarsenopyrite isinvariablydescribed grade (seebelow). Althoughboiling is probablyan
asthe earlierhigh-temperature phasewhichwaslater importantadditionalprocessin porphyrycopperde-
followedby lower temperaturepyrrhotiteprecipi- posits(e.g., Cathies, 1977, p. 823; Cunningham,
tation(Table1), asdiscussedin the followingsections. 1978), isotopicdataand fluid inclusionevidencefor
a decreaseof salinitywith time suggestthat mixing
Applicationto the ParageneticSequenceof of igneousfluidswith meteoricwatersmay be more
CassiteriteSulfideDeposits importantin the formationof somevein-typetin de-
Somebasicparameters posits(Eadington,1983;SunandEadington,in press;
see alsoBarton and Toulmin, 1961, p. 349). Since
Beforediscussing
the parageneticrelationof ar- meteoric fluids will be generally much cooler, the
senopyrite in aluminosilicate-hostedcassiteritede- thermal effect on mineral solubilities is believed to
posits,it isnecessary
to considertwo of the parameters be far more importantthan the chemicaleffectsof
thatareconsidered to be of particularimportancefor mixing,'suchas ligand dilution which is sometimes
the chemicalevolutionof fluidsformingthis broad invokedto explainmineralprecipitationby decom-
groupof deposits. plexingof dissolvedmetal species.
Cooling:Severallinesof evidenceshowthat a fall Redoxconditions: The precipitationof mostof the
in temperatureisanimportant,perhapsthe mostim- majoroxideandsulfidemineralsfoundin tin deposits
portant, singleparameter that controlsthe chemical involvesa changein valencyof the metalliccompo-
evolutionof manycassiteritedepositsandtheir ore- nent.The chemicalevolutionof a metal-bearingfluid
formingfluids. during coolingwill therefore dependon the redox
Direct observational evidence from fluid inclusion conditions(measured,for example,by oxygenfugac-
studies invariablyshows a dropin temperature during ity) which, asborne out by the followingdiscussion,
the evolutionof thosedeposits,for which the fluid is considereda key chemicalfactorin the develop-
inclusionchronologycouldbe relatedto the textural ment of the parageneticsequences observedin cas-
evidencefor the relativetimingof mineralprecipi- siterite-sulfide deposits.
tation (Table 1). In particular,the precipitationof the economic
The importanteffectof temperatureonoremineral mineral cassiterite involves an oxidation. Thermo-
solubilityisborneoutby experimental dataandther- dynamiccalculations by EadingtonandGiblin (1979),
modynamic predictionsfor manychemicalsystems. Pattersonet al. (1981), Eadington(1982), andJackson
Solubilityis an exponential functionof temperature. and Helgeson(1985) and preliminaryexperimental
For example,for 90 percentof anySnClø• presentin data (R. Pabalanand H. L. Barnes,pers. commun.;
a hydrothermal solutionto be precipitatedascassit- WilsonandEugster,quotedby Eugster,1984) indi-
erite(atconstant oxygenfugacity,pH, andC1-activ- catethat in graniticrockstin is transportedin hydro-
ity; seeeq. 6, Table 3), a temperaturedrop of less thermalsolutions mostlyasreducedSn(II) complexes,
than20øisrequired(or 40øfor 99% of the tin). Fur- for example,SnClø•,
ratherthanasSn(IV)thio or hy-
ther examples shownin Figure5 anddiscussed below droxy-chloro complexes (Eadington and Giblin,
indicatethat for mostore mineralsthe temperature 1979). Precipitationof cassiteriteinvolvesan oxida-
intervalsneededto precipitatethe bulkof anymetal tion to Sn(IV):
presentin solutionis smallcomparedwith the total
temperatureintervalindicatedby fluid inclusiondata SnCIø•
+ H20 + 0.502 -- SnO2+ 2H+ + 2C1- (6)
fortheformation
ofa tin deposit
orevena singlevein. andthereforedependscriticallyon oxygenfugacity.
Forthe mechanisms of cooling,severalsuggestions
havebeendiscussed by BartonandToulmin(1961). Redoxprocesses and the chemicalevolutionof
Quantitativemodelingof the coolingof shallowin-
granite-derivedhydrothermalfluids
trusionsby fluidconvection(Cathies,1977) suggests
that a fastrise in temperatureshortlyafter the em- Under the reducingconditionsdepictedin all fig-
placement of a plutonisfollowedby anextendedpe- uresof this paper, rocksandhydrothermalfluidsdo
riod of fluid circulation,duringwhichisothermsfall not containsufficientfree, elementaloxygento sup-
backtowardthe plutonandtemperatures at anyone port oxidationreactionswith 02. If oxygenfugacity
point in the upperpart of the intrusionandthe over- is chosenas a measureof redox state (Barnesand
lying hostrock decreaseslowly.This is considered Kullerud, 1961), the speciesO2 necessarilyappears
the mostlikelystagewherea paragenetic
sequence in reactions,but net chemical redox processesmust
recordinga fall in temperatureisformedin a mineral always involve balanced O2-conservingreactions.
deposit,althoughBartonandToulmin(1961,p. 349) Precipitationreactionsfor many ore mineralscom-
aswell asCathies(1977, p. 822) concludethat ad- monly found in hydrothermaltin depositsinclude
ditional,possiblynonthermal,parametersmustbe changesin oxidationstate,which mustbe balanced

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 As HYDROTHERMAL CHEMISTRY: THERMODYNAMIC PREDICTIONS 523

eitherby reactionsin the wall rocksor by concomitant andothermodifyingfactors,the relativeimportance

reactionsinvolvingother speciesin the fluid. of which will vary between different deposits,and
At high temperaturewhere metal-richfluidssep- factorsmayact concurrentlyduringthe evolutionof
arateasa late magmaticphaseor where fluidsof any a hydrothermalsystem.However, despitethis sim-
originpenetrativelyleachmobileelementsfromlarge plification,someof the broad similaritiesand differ-
masses of graniticrock, redoxequlibriaamongsolid encesbetweenthe structural,paragenetic,and fluid
host-rockmineralsincludingFe silicatesand Fe-Ti inclusionpropertiesof cassiterite-arsenopyrite-base
oxidesarelikely to controlthe oxygenfugacityin the metal sulfidedepositscanbe explainedprimarilyby
fluid-rocksystem.In ilmenite seriesgranitoidsthat different levels of oxygenfugacity associatedwith
are typically associatedwith tin mineralization,the thesemodelprocesses.
oxygenfugacityis at leastinitially bufferednear the
Ni/NiO buffer by equilibria involving ilmenite, Theoreticalcoolingpathsfor Sn-As-base
sphene,andFe+a-bearing silicatessuchaspyroxenes, metal sulfidedeposits
amphiboles,and micas(Ishiharaet al., 1979; Shima- Figure 5a andb showexperimentalandcalculated
zaki, 1980; Wones,1981). Rock-dominated evolution solubilitycontoursfor someore mineralscommonly
of a hydrothermalfluidoccurswhenthe fluidremains found in cassiterite-arsenopyrite-base metal sulfide
in contact with a sufficient mass of host rock to buffer deposits.They providea frameworkfor discussion of
its chemicalcomposition throughoutits coolinghis- the chemicalevolutionof a hypotheticalSn, As, Fe,
tory. Alternatively,a fluid may becomephysically S, Cu, Zn...-rich high-temperaturesolutionduring
separatedat somestageand follow a chemicalevo- coolingand a comparisonof the effectsof rock-buff-
lution that is controlledby redoxequilibriaamong ered (path B-E, Fig. 5a) and dominantlyfluid-con-
solutionspeciesandprecipitatingmineralsonly.This trolled redox processes(path B-H, Fig. 5b) on the
canbe termeda fluid-dominated hydrothermalevo- parageneticsequence.Most contoursrefer to con-
lution.Fluid-dominated controlisexpectedto be im- gruentmineralsolubilitiesandeachof thesecontours
portantin thosetin depositswhere the localizedoc- is calculatedfor equalactivitiesof the aqueouscom-
currenceof ore mineralsin veinsandpipesindicates ponents,i.e., H•.Søandthe dominantmetalcomplexes.
channelingof fluidsandlocalhighratiosfor the total However, no fixed startingcompositions will be as-
amountof solutesintroducedby the fluidto the total sumedandmassbalanceconstraints oncompetingre-
amountof hostrockaccessible to alteration.Physical actionswill not be consideredquantitatively.The
separationof the fluid is favoredby hostrocksof re- predictedcoolingpathswill thereforebe qualitative
strictedpermeability,leadingto relativelynarrowal- only.For both pathspH is assumedto be bufferedby
terationhalos,andby the growthof selvages of hy- the presenceof excessmuscovite+ potassicfeldspar
drothermal minerals on the vein walls. + quartz and a solutionwith constantaK+= 0.1 and
The presenceof muscovitein localalterationzones ac•-= 1.0.
andasa veinmineralin almostall cassiterite deposits Rock-bufferedchemicalevolution:If oxygen fu-
andthehighabundance of feldsparstypicallypresent gacityis maintainedat or near the Ni-NiO buffer by
in the aluminosilicate hostrocks(andsometimesalso host-rocksolids(Shimazaki,1980; Eadington,1982),
in the veins,e.g.,Cornwall;Table1) indicatethatpH the coolingfluid will first reachcassiteritesaturation
is morelikelyto be rockbufferedby hydrolysis-type at a point, say,B (Fig. 5a). The oxygenrequiredto
alterationreactionsthan by any other mechanism. precipitate99 percentof an original10-•' mole/kg
Evenif the pH is not entirelyrockbuffered,it is at Sn(II) ascassiteritebetween B and C is then balanced
least generallyconstrainedto the stabilityfield of by reactionsin the host rock, suchas reductionof
muscovitethroughoutthe mainstagesof mineraliza- Fe+a-Tisilicatecomponents to ilmenite.With contin-
tion. In contrast,oxygenfugacityis morelikely to be ued rock-buffering,arsenopyritewill alwaysreach
fluidcontrolledbecauseof the low availabilityof ox- saturationat a distinctlylower temperaturethan the
idized Fe in typical hostrockssuchas the ilmenite rangeof cassiteriteprecipitation.For an assumedini-
seriesgranitoidsand their associatedvolcanicsor in tial ai-i•A,o• -• al%cl•• ai-i=so-• 10-•, this will occur
reducedsediments suchasthe metasiltstones hosting near point D. If the solutioncontainssimilarconcen-
manyvein depositsin easternAustralia(e.g., Sun- trationsof As, Fe, andS, pyrite will reachsaturation
down;Andrew and Heinrich, 1984). Processes in- at approximatelythe samepoint asarsenopyrite,ac-
volvingmorethanonefluidphase,notablyboilingor companiedor shortlyfollowedby basemetalsulfides
mixingof a granite-derivedfluid with chemicallydif- suchas ehaleopyriteand sphalerite.If Fe and S sig-
ferent and/or coolerfluids,providethe third main nificantlyexceedAs in solutionor if oxygenfugaeity
type of controlon the evolutionof an ore-depositing is even higher than shownby the path B-E, precipi-
fluid. tationof pyrite asthe earliestsulfideis favored,which
In reality,formationof a particulartin depositwill may causerapid depletionof Fe and S in the fluid
notconform to anyoneoftheseindividualmodelpro- and suppressdepositionof large quantitiesof arse-
cesses. Rather it will involve a combination of these nopyrite (e.g., Bolivianporphyry-styledeposits,see

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 524 C. A. HEINRICH AND P. J. EADINGTON

b)
[ I i I i I I 1

Rock
- buffered Fluid- buffered
/ /
?
•'t •/ B [
/ cooling
-•0 -.

75/ / • • •/ :.;::..'
,,'

/ /-• - i -3 -• i i i i
200 250 300 350 •00 •50 500 200 250 300 350 goo g50 500
Temperefure (%)

FIG.5. Solubility
contours
forsome
commonoreminerals
incassiterite-arsenopyrite-base
metal
sulfide
deposits,
andtwopossible
paths,
indicated
byarrows,
forthechemical
evolution
ofa metal-
andsulfur-bearing
hydrothermal
solutionduringcooling.
(a).If redox
equilibria
arebuffered
throughout
cooling
byanexcess
ofhost-rock
ironsilicates
and
oxides
along
pathA-E,theparagenetic
sequence
ofearlycassiterite
followed
bypyrite+ arsenopyrite
+ basemetalsulfides
islikelyto be formedby mostgranite-derived
fluids.
(b).Channeling
ofa similar
fluidintoveins
whichallowonlyrestricted
wall-rock
interaction
may
leadtoa 1owerfo2
path,B-H,favoringthedepositional
sequencecassiterite
+ arsenopyrite
(stippled
area)followed
by pyrrhotite+ basemetalsulfides.
Thesolubility
contours
fortheequilibria
corresponding
tothenumbersincircles
werecalculated
forequalactivities
ofaqueous
components(labeledinlogunits),
asfollows:
equilibria
(2)and(3):
aFecl•-"
-- ams0;equilibrium
(4):aH•,o•
ø= aFecl,
•-"= ams0;equilibrium
(6):as,cid;
equilibrium
(12):
ac,cl0= aF•cl,
•-" = ams0;andequilibrium(13): az,cl? = ams0.
LogKvalues
forequilibria
(2),(4),(6),and(12)aregiveninTable3.Pyrrhotitesolubility
contours
according
toreaction
(3)(text)
wereconstructed tobeconsistent
with(2)and(11);sphalerite
solubility
contours
(13)arefromBarrettandAnderson (1982,table6).TheshadedbandfH2 = 100barsrefers
tothedecomposition
ofwateraccording toH•O-- H• + 0.5O2•andrepresents thelowerlimitof
redoxconditions
whichcanbeattained
ina shallow
hydrothermal
system.
TheNi-NiObufferlinealong
path
A-EisfromWones (1981,
table
2).Allsulfide
equilibria
refertoH•S
øasthepredominant
aqueous
sulfur
species.
Theircontours
become metastable
athigh
oxygenfugacities
inthesulfate
field,
butthis
is omittedfor clarity(seeFigs.3 and4).

below). The parageneticsequencecassiterite--• ar- at oxygenfugacities

closeto the pathB-E (Fig. 5).
senopyrite + pyrite+ basemetalsulfides predicted ThepathB-Eisthusnotin accordwiththe textural
bytherelatively highfo•pathB-Ecorresponds qual- observation frommanydeposits, thatthesetwo min-
itativelywith observations from the CanadianMt. erals
largely coprecipitatedprior
tothedeposition of
Pleasantdeposit,where arsenopyrite precipitated thebasemetalsulfides.
The differentsignofthe slopes
later than the oxide ore minerals cassiterite+ wol- ofthearsenopyrite andcassiterite
solubilitycontours
framitcbutaccompanied otherlatesulfidesincluding (Fig. 5) indicates
that thisparageneticsequence is
pyrite(Mulligan,1975;seeTable1). Mt. Pleasant is favored by loweroxygen fugacities.
Oxygen fugacities
to be an exampleof a W-Sn porphyry- muchbelowthe Ni-NiO buffer canbe attained,for
considered
typedeposit by Sillitoeet al. (1975,p. 925)andthe example, byequilibration
ofthesolution
withreduced
associationof disseminated mineralization in breccia carbon,
e.g.,graphitic
rocks.Butevenwithoutany
withextensive
andpervasive
alteration that externalreduction
indicates by thehostrock,a decrease
in ox-
indeedhost-rockbuffersexertedthe dominantcontrol ygenfugacitywilloccur
during
fluid-buffered
cooling
on oxygenfugacity. ofa single
fluidthatbecomes
separated
fromanyre-
Fluid-controlled redox evolution:The calculated ducible host-rockmineralsafter reachingcassiterite
solubility
contoursforcassiterite
andarsenopyrite in- saturation.
In thiscaseoxygenfugacitycanbecome
dicatethat simultaneousprecipitationof thesetwo effectively controlled
by equilibrium (6) between
mineralsfrom a solutioncontainingrealistic trans- cassiterite
anda solutionof constant
SnCI•content
porting ofSn,As,S,andFeisunlikely (pathsegment
concentrations B-F).Despite
furthercooling,
cassit-

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 As HYDROTHERMAL CHEMISTRY: THERMODYNAMIC PREDICTIONS 525

eriteprecipitation
willbeinhibiteduntiloxidized
fluid iscompatible
withthegradienttowardtherockbuffer
speciesstartto becomereducedin sufficientquantity alongpathB-E. The neglectedsolidsolutionin chlo-
to balancecontinuingoxidation-precipitationof tin. rite andbiotite hasan effectof lessthan onelog unit
A lowerlimittothisdropin oxygen fugacity
iseffected andis partlycounteracted by phengitesolidsolution
where H•.O becomesreduced to H•. in amountscom- in muscovite.

parableto the Sn(II) presentin solution,and cassit- The subsequent chemicalevolutionalonga fluid-
erite deposition canoccuraccording to the reaction: bufferedcoolingpathwill dependstronglyonthe ini-
tial fluidcomposition andon massbalanceconstraints.
SnCI• + 2H•.O -- SnO•.+ Ha + 2H + + 2C1-. (7) In generalthe lower oxygenfugacityalonga path
suchas F-H favorspyrrhotite rather than pyrite as
Alternatively,a processmaytake placenearthe stip- the Fe sulfide.In contrastto the highfo2 path pre-
pled areaF (Fig. 5b), in whichprecipitationof arse- dicting the sequence cassiterite --• arsenopyrite
nopyritemayprovidethe reductionrequiredto bal- q-pyrite + basemetalsulfides,the lowerfoa path
ance continuingprecipitationof cassiteriteby oxi- favors the sequencecassiteriteq- arsenopyrite-•
dationof SnCI•, accordingto an oxygen-conservingpyrrhotiteq-basemetalsulfides.
redox reaction:
Saturationwith anyof the later Fe-bearingsulfides
3SnCI• + 2HaAsOøa + 2FeCI• + 2H•.Sø suchas pyrrhotite or chalcopyriterequiresthat Fe
and S were at least slightly in excessover As at
= 3SnO•.+ 2FeAsS+ 10C1- + 10H +. (8) the stageof initial saturationwith arsenopyrite near
The predictedsulfurandmetalconcentrations of point F.
0.01 to 0.1 m, where this processcould occur,are The low foa path, which may result from domi-
realisticfor granite-derivedfluids (see Eadington, nantly fluid-controlledoxygenfugacity,can explain
1983, table 3), and the temperaturerange340ø to why pyrrhotite occursexclusivelyasa late sulfidein
400øC indicatedby the stippledarealargelyoverlaps vein-typecassiterite depositsshowingconfinedalter-
with fluidinclusion datafor cassiterite q-arsenopyrite ation halos in their aluminosilicate hostrocks(Table
precipitationin mostdepositsshownin Table 1. 1). The occurrence of chalcopyrite asanequallylate-
Instead of congruent precipitation, arsenopyrite stage mineral in most tin deposits indicates
relatively
formation could also include sulfidation of Fe +•' com- low Cu concentrations in the initialmineralizingfluid
ponentsof host-rocksilicatesaccordingto reactions comparedto Fe, S, and As concentrations(Fig. 5).
such as: This is expectedfor fluids derived from a granitic
(ratherthan a more mafic)igneoussource.
biotite q- chloriteq- HaAsOaø q- H•.Sø The Boliviandepositsprovidea particularlygood
exampleof the two contrasting coolingpathsB-E and
= muscovite q- quartz q- arsenopyrite q- H•.O q- O•. B-H, becausetwo differentstructuralstylesof min-
(9) eralization have formed in the same host rocks at sev-
eral mineralizedcenters(Table1) andprobablyfrom
and
the sametype of fluids(Kelly andTurneaure, 1970;
Sillitoe et al., 1975, p. 925; Grant et al., 1980).
K-feldspar
+ chlorite+ HaAsOa
ø + H•.Sø Abundantpyritebut no pyrrhotitehasformedin the
= muscovite+ quartz + arsenopyrite+ H•.O + O•. low-gradedisseminated and stockwork-veinlet(por-
(10) phyry-type)cassiteritemineralization.The extensive
and pervasivealterationassociatedwith this style of
mineralizationsuggeststhat host-rockbufferswere
(seeTable 3 for stoichiometry). A combinationof the mostimportantcontrolonmetaldeposition along
thesewith feldsparhydrolysis reactionsrequiredto a coolingpathBE. In contrast,injectionof fluidsinto
neutralizethe H + productionby reaction(6) or (7) the "lode" veinswhichshowonlyrestrictedalteration
canexplainthe ubiquitousreplacementof feldspars hasled to high-gradecassiteriteq- arsenopyritemin-
q-ferroussheetsilicates by muscovite q-quartznext eralizationfollowedlaterby pyrrhotiteq-basemetal
to nearlyall cassiterite-sulfide
veins.LogK for equi- sulfides,aspredictedby the fluid-dominated cooling
libria (9) and(10) havebeencalculated usingther- path B-H.
modynamicdata from Walshe(1984) for the cham- During the stageof basemetal sulfidedeposition
ositecomponentin chloriteandfromHelgesonet al. represented by the pathsegmentG-H, oxygenfugac-
(1978)fortheothersilicates (Table3). For equivalent ity is likely to be controlledby equilibriabetween
concentrations of SandAs,bothreactions reachequi- sulfides liningthe veinwallsandaqueous species,for
libriumat anoxygenfugacityof about5 logfo2units example,by equilibrium(1) or other reactionscom-
abovethe stippledareaF. Thisreflectsan expected patiblewith the commonlyobservedlocaldissolution
gradientin oxygenfugacityfromthe vein to the un- andreplacement of earlyarsenopyrite
with Fe sulfides
alteredcountryrock(indicatedby the arrow),which andbasemetalsulfides.Alternatively,influxof (gen-

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by Lulea University of Technology user
 526 ½.A. HEINRICHAND P.J. EADINGTON

erally more oxidized)meteoric water may become O'001m

SnCI•
Redox- mechanism
increasingly importanttowardthe late stagesof hy-
drothermalactivity, as indicatedby progressivede- controtting
creasein fluid inclusionsalinityandby stableisotope deposition of 0-011
rnSnCI•
10-2 mote Sn02.'
data(e.g., Kelly andTurneaure, 1970; Charoy, 1979;
Eadington, 1983; Sun and Eadington, in press). A
mineralogicalexpressionof such oxidationby low- Sn-oxidotion
temperaturemeteoricsolutionscouldbe the common boloncedby
replacementof pyrrhotiteandothersulfidesby late- As-reduction
stagepyrite,marcasite,
carbonates,
andFe+aoxides to orsenopyrite
andhydroxides(Table1). Thispossibility
isindicated
schematically
by the pathsegmentH-I in Figure5b. Excess /
hostrock •'
PrecipitationMechanismsand Ore Grade
The calculations suggestthat simultaneous precip-
buffer • 0-093
0'100
m H,AsO•
øø
rnH3AsO•
$n-oxidolion
itationof arsenopyrite+ cassiteriteisfavoredby very boi•nced•,• AT(As)i
reducingconditions.These may occurin aluminosil- by HzO logfo•
icate-hosted deposits whenphysicalisolationof fluids, reduction &.T(rock)
!
which are channeled into veins and pipes, prevent toHz AT
(•) •T
completeredoxbufferingby host-rockalterationre-
actions.In this situation,equilibriabetween precip-
itatingmineralsandaqueousSnandAs couldactively FIG. 6. Relativeefficiencyof three redoxprocesses to deposit
controlthe redoxstateof a coolingore solutionduring cassiterite.
In thisexamplemassbalanceisobeyedfor precipitation
of 0.01 mole cassiterite(1.51 g)from i kg of a coolingsolution.
cassiteritedeposition.The possibilityof this mecha- Path segmentshave curve spacingand slopescalculatedin the
nismcouldbe of considerablepracticalinterest,be- samerelativescaleasin Figure5, butthepositions
arearbffrary.
causeof itsinfluenceonthe ore gradeof anyresultant The coolinginterval AT(As)requiredto precipitatethe given
tin deposit.The type and availabilityof reducible amountof cassiterite isrelativelysmallif tin oxidation-precipitation
coupleswith arsenicreduction-precipitation accordingto reaction
speciesin the fluid-rocksystemwill in part determine (8) in the text. The shortcoolingintervalAT(As)indicatesthat
how efficientlytin is extractedfroma givenfluid over redoxcoprecipitation of cassiterite
with arsenopyrite wouldbe a
a given temperature gradient. This is shown sche- particularlyefficientmechanism to extracttin fromhydrothermal
maticallyin Figure 6 whichillustratesthree possible solutions,favoringrelativelyhigh tin ore grades.
mass-balanced processes to deposit0.01 mole (about
1.5 g) of cassiterite
from1 kg of solution.
The curve
spacingand slopesin Figure 6 are calculatedas in precipitatedover the smallercoolinginterval.The
Figure 5, but their absoluteposition,which is more favorablecouplingof Sn oxidation-precipitation
of
uncertain,is placedarbitrarily.If the precipitationof cassiteritewith the reductioninvolvedin precipitation
cassiteriteis entirelybalancedby host-rockbuffers, of arsenopyrite could,for example,explainthe ob-
then a coolingintervalAT(rock)isrequiredto deposit servationat the Ardlethan tin mine (I. Keyes, pers.
10-2 molesof tin. In contrast,if the solutioncontains commun.)
that cassiterite
ore gradesshowa marked
oxidizedarsenicin tenfold excessover tin (whichis correlationwith the abundanceof arsenopyrite(but
not unrealisticconsideringthat arsenopyriteis much not with any other sulfide)in the ore.
moreabundantthancassiteritein manydeposits),then
coprecipitationof arsenopyriteand cassiteriteac- PresentApproachShortcomings
and
cording to reaction (8) may causea rise in oxygen Future Work
fugacity.In thisprocess
the sameamountof cassiterite
is depositedover a considerablysmallercoolingin- It shouldbe stressed
againthat manyof the solu-
terval AT(As).Conversely,if cassiteriteprecipitation bility equilibriausedin the foregoinginterpretation
were inhibited until H20 reduction to H•. becomes of mineralparagenesis are basedon thermodynamic
the dominant mechanism to balance Sn oxidation, extrapolations which have not been tested experi-
cassiteriteprecipitationwould be dispersedover a mentally.This is not only the casefor the arsenic
larger temperatureinterval AT(H2). Cassiteritepre- equilibriabut alsofor the solubilityof cassiterite,
for
cipitation over a small temperature gradient favors which a new extrapolationof the low-temperature
its accumulationas a relatively high-gradeore. This datawaspublishedby Jackson andHelgeson(1985)
effectisfurtherenhancedbecauselessquartz--which while thispaperwasin review.The new predictions
is the mostimportantganguemineraldiluting cassit- corroboratetheresultsofEadingtonandGiblin(1979;
erite in most aluminosilicate-hosted ores--will be asusedin Fig. 5) with regardto tin speciation
but

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by Lulea University of Technology user
 AsHYDROTHERMAL
CHEMISTRY:
THERMODYNAMIC
PREDICTIONS 527

would shift the contoursof equilibrium (6) to lower restrictedto the H•Sø predominancefield indicate
temperatureiby 30ø to 40øC. If the K valuesgiven that, in contrastto most other ore minerals, arseno-
by Jacksonand Helgeson(1985) were the more cor- pyrite solubilitydependsmore stronglyon oxygen
rect, then coprecipitationof arsenopyrite+ cassiterite fugaeitythanon temperature.The calculations
are in
would require somewhatlessstronglyreducingcon- agreementwith textural observationson the para-
ditions.AqueousAs(III) would then becomean even geneticsequences in aluminosilieate-hosted
eassit-
more likely reduciblefluid speciesto balanceand erite-sulfidedeposits.They explainthe early eopre-
controlcassiteriteprecipitationactivelyunderfluid- eipitationof eassiterite andarsenopyrite observedin
buffered conditionsrather than alternativepossibili- manyvein-typetin deposits at geologically
reasonable
ties such as the reduction of H20 to H2. However, metal concentrationsand at temperatures in agree-
the clearseparationof the two parageneticstagesob- ment with fluid inclusiondata. Coupled redox pre-
servedin tin depositsis more easilyexplainedby the cipitationof eassiteritetogether with arsenopyrite
datafromEadingtonandGiblin (1979) adoptedhere. couldbe a very efficientmechanism for extractingtin
These differencesin the extrapolateddata again froma coolingsolution,a mechanism thatwouldfavor
show that we are far from a quantitative model to relativelyhigh-gradeaccumulations of eassiterite.
explain mineral paragenesis,and from determining
which of the competingmechanisms controlimpor- Acknowledgments
tant processessuchasprecipitationof economiccas- We would like to thank A. G. Turnbull and M. W.
siterite grades.The present approachusessimple Wadsley(CSIRODivisionof MineralChemistry)for
congruentsolubilityas a measureto interpret the providingthermodynamic
dataandassisting
with the
parageneticrelationof differentore minerals,but it use of computer programs of their CSIRO-NPL
does not take into account the mass transfer con- THERMODATAsystem. Theworkhasbenefitedfrom
straintson the chemicalevolutionof a coolingfluid. interesting
discussions
withA. H. Ewald,A.M. Giblin,
When more quantitativeand reliable solubilitydata R. G. Robins, and R. W. T. Wilkins. Earlier versions
becomeavailable,the next step will be to combine of this manuscriptwere read by A. H. Ewald, R. R.
thermodynamic with mass transfer constraintsto Large,andA. R. Ramsdenwho contributedvaluable
model quantitativelychemicalevolutionpathssuch suggestionsfor improvement.Very stimulatingEco-
asthe onessketchedin Figure5. Our broadtreatment nomicGeologyreviewsaregratefullyacknowledged.
of aluminosilicate-hosted cassiteritedepositsas one This researchwas supportedby a postdoctoralre-
group may then need revision.In particular, copre- searchfellowshipof the Schweizerischer National-
cipitationof cassiterite+ arsenopyriteclearly cannot fonds zur FiSrderungder Wissenschaftlichen For-
be the onlymechanism to producehigh-gradetin ores, schungto C.A.H.
asexemplifiedby the rich but nearlysulfide-freeSan
Rafaeldepositin Peru (A. H. Clark, pers. commun.). December3, 1984; September19, 1985
Masstransfermodelsfor specificdepositswill have
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