Economic Geology

Vol. 69, 1974, pp. 1328-1334

The FeS Contentof SphaleriteAlongthe Chalcopyrite-

Pyrite-BorniteSulfur FugacityBuffer
GERALD K. CZAMANSKE

Abstract

Concentrationsof 0.19 ñ 0.02 and 0.55 ñ 0.08 mole percent FeS have been measured
in sphalerite crystallized at 1 kbar in equilibrium with the chalcopyrite•pyrite-bornite
sulfur fugacity buffer at temperaturesof 271ø and 395øC, respectively. These data yield
a relationshipof log C----1353/T-I-1.77, where C is measuredin mole percent FeS,
T is in øK, and the pressureis 1 kb. The effect of pressureon C is evaluated. Hence-
forth, indications of equilibrium or disequilibrium crystallization and estimates of tem-
perature of formation may be made for the assemblagesphalerite-chalcopyrite-pyrite-
bornite at temperaturesin the range 150ø to 450øC.
The compositionof bornire in equilibrium with chalcopyriteand pyrite is found to be
Cus.24Fe0.s0S4.00at 271øC and Cus.02Fe0.0aS4.00 at 395øC. At thesetemperatureschalco-
pyrite and pyrite in the buffer assemblagedo not deviate measurablyfrom stoichiom-
etry. Bornite and chalcopyriteare found to incorporate0.03 to 0.18 and 0.00 to 0.43
atomicpercentZn in the range 197ø to 503øC.

Introduction relative variation of the FeS content of ZnS along

Mucr• experimental effort has been devoted to the cp•-py-bn,fs2buffermightbe greaterthan that
determiningthe FeS contentof sphaleritein equi- anticipatedfor variationin FeS contentalong the
librium with the assemblage pyrite-pyrrhotite,with pyrite-pyrrhotite,
fs2 buffer. On the basisof an
a view toward developingan ore geothermometer.
analysisof sphalerite
in a cpy-py-bnassemblage from
Papersrepresentativeof this effort includeScottand
the Iimori mine, Japan, and relationsset forth by
Barnes (1971), Boorman,Sutherland,and Cherny-
Bartonand Toulmin(1966), Yui and Czamanske
shev (1971), Chernyshevand Anfilogov (1968), (1971) estiinatedthat the Iimori ore formed at a
temperaturebelow300øC.
Boorman(1967), and Kullerud (1953), as well as
Becausethe pertinent relationshipspresentedby
the more general paper of Barton and Toulmin
(1966). Unfortunately,the resultsof thesestudies Barton and Toulmin (1966) are basedon extrapo-
indicatethat between550ø and 300øC,a temperature lated rather than direct experimentaldata, they are
range of much interest to studentsof ore formation, uncertain,particularlyin regardto the choiceof the
Henry's law constant,which relatesthe activity of
sphalerite compositionis constant at 20.7 +--0.6
FeS to the molefractionof FeS in sphalerite.There-
mole percentFeS (Scott and Barnes,1971) and is
thus not useful as a geothermometer. Concentra-
fore, the studiesreportedhere were carriedout in
orderto placetheserelationships on a firmerexperi-
tion of attention on sphaleritecompositionsalong
mentalfooting.
the pyrite-pyrrhotitesolvusreflectsthe tacit assump-
tion that sulfur fugacitiesduring ore formationfre- Experimental Procedures
quently correspondto those of pyrite-pyrrhotite
equilibrium. To promotereactionsinvolvingsphaleriteat the
Associations
of sphalerite
with the assemblage
relativelylow experimentaltemperaturesof interest
chalcopyrite-pyrite-bornite(hereafter referred to for this system,experimentationin hydrothermal
often as cpy-py-bn) are less common,principally solutionsis essential. Previousexperience(see, e.g.,
becausethat assemblage is stableonly at sulfurfugac- Czamanskeand Rye, 1974; or Scott and Barnes,
ities that are higher than thosetypical of most ore 1971) has demonstratedthat equilibrationwith ex-
environments(Holland, 1965; Barton, 1970). Bar- tensiverecrystallization can be obtainedin NH4C1
ton and Toulmin (1964, 1966) and Yui and Cza- and NH4I solutionsby applyinga thermalgradient
manske(1971) recognizedthat the FeS contentof of about50C over the 10 cm length of the platinum
sphalerite from the assemblagesphalerite-chalco-sampletubes.
pyrite-pyrite-borniteis a potentiallyuseful-geother- Sulfidephasesfor reactionwere preparedfrom
mometer. Barton and Toulmin (1966, fig. 17), in high-purityelementsby reactionat elevatedtem-
particular, presenteddata that suggestedthat the peratures in evacuated
silicatubes. Synthesized in
1328
 THE FeS CONTENT OF SPHALERITE 1329

T•,BLE 1. FeS Contents of SphaleritesCrystallized in Associationwith Chalcopyrite-Pyrite-Bornite

Over the Temperature Range 197.ø to 400øC

Mole Percent Mole Percent

Experiment Crystallization Duration of Solution FeS in FeS in
Number Temperature, øC Run, Days Composition• Starting ZnS Product ZnS

176 197 4- 3 615 Sat. NH4C1 0.00 0.12 4- 0.03

145 272 4- 3 220 Sat. NH4CI 0.00 0.20 4- 0.03
202 272 4- 3 195 Sat. NHd 0.00 0.10 4- 0.04
237 271 4- 3 85 Sat. NH4CI 0.00 0.21 4- 0.04
238• 271 4- 3 85 Sat. NH•C1 1.00 0.18 4- 0.03
239 271 4- 3 85 Sat. NH•C1 2.00 0.19 4- 0.02
1083 400 4- 5 165 IN NH4C1 0.00 0.95 4- 0.12
179 396 4- 4 160 Sat. NH•CI 0.00 0.65 4- 0.05
180 396 4- 4 160 Sat. NH4CI 40.00 0.80 4- 0.07
227 395 4- 4 99 Sat. NH•C1 0.00 0.49 4- 0.06
228 395 4- 4 99 Sat. NH•C1 1.00 0.47 4- 0.04
229 395 + 4 99 Sat. NH•CI 5.00 0.49 4- 0.06
261 394 4- 4 193 1N NH•C1 0.00 0.64 4- 0.07
262 394 4- 4 193 1N NH•C1 1.00 0.52 4- 0.06
263 394 4- 4 193 Sat. NH4C1 0.00 0.62 4- 0.10
264 394 4- 4 193 Sat. NH•C1 1.00 0.64 4- 0.05
265 394 4- 4 193 NH•I 0.00 0.49 4- 0.05
266 394 4- 4 193 NHd 1.00 0.52 4- 0.05

Sat. indicatessolutionsaturatedat 25øC. Concentrationof NHd in runs 265 and 266 was 7.7 gm/10 mi.
Runs with consecutive numbers and identical run duration are from same reaction vessel.
Run carried out in cold-seal vessel and contained PbS.

this way were: a seriesof (Zn,Fe)S solidsolutions; tion texturesmay haveresultedfrom the relatively
FeS2; and an intimate, fine-grainedbuffer mixture slow quench. No reactionbetweenthe sulfidesand
containing roughly equal portions by weight of the platinumtubewasnoted.
CuFeS2, FeSa, and CusFeS4. Consumptionof the Crystallizationproductswere analyzed with an
FeSa componentof the buffer mixture was common ARL EMX-SM electronmicroprobeusing an ac-
in early experiments,so experimentsreported in celeratingvoltageof 15 KV and a specimen current
Table 1 typicallyused300 mg of the cpy-py-bnmix- of 2 x 104 ampereson brass. Lines analyzedand
ture, 75 mg of additionalFeSa, and 50 to 75 mg of crystals used for each element are as follows: Cu,
(Zn,Fe)S. Runs were startedwith compositions of Fe, and Zn, Ka, LiF; and S, Ka, ADP. Standards
(Zn,Fe)S that bracketed anticipated equilibrium used were: chemically analyzed, stoichiometric
compositions, so that equilibriumwas approached bornitefromButte,Montana,andchalcopyrite from
from both directions. O'okiep,Namaqualand, SouthAfrica; syntheticZnS
Reactantsand solutions (Table 1) were loaded containing0.00, 1.00, 2.00, and 5.00 mole percent
into 8 mm O.D. platinumtubes,which were flushed FeS; syntheticCuFeS•containing 0.50 weightper-
with hydrogen and flame-weldedwhile partly im- centZn; synethetic FeS containing2.00 weightper-
mersed in ice water. Groups of six sampletubes cent Cu; and a syntheticbornite of composition
were placedinto medium-sized(22.9 cm x 6.4 cm) Cus.44Fe0.82S4.oo. Reportedanalysesof sphalerites
pressurevesselswith modifiedBridgman-typeseals. represent 10-second countsat 30 to 60 discretepoints
Vesselswere loweredinto vertical,gradientfurnaces, on 5 to 10 homogeneous grains;for (Cu,Fe)-sulfide
such that nutrient and buffer phasessettledto the phases8 to 20 pointswere analyzed. All analyses
lower (hotter) end of the platinumtube and crystal- reportedare basedon directcomparison of counting
lization productsformedat the upper (cooler) end rates for unknowns and standards of similar com-
of the tube. All experimentswere conductedat 1 position, with appropriate correctionsfor background
kb pressureto promotesolutiontransportvia a rela- and instrument drift calculated
by hand. For anal-
tively dense medium. Temperature uncertainties ysesof sulfides,it is very importantto use either a
reportedin Table 1 includecalibrationof the thermo- rigorous, theoreticalcorrectionscheme,or a low
coupleand recorder,short- and long-term furnace acceleration voltage(Desborough et al., 1971), or
fluctuations,and an estimatedcorrectionfor separa- close standards. For example,at 15 KV using
tion of thermocoupleand sample (see Czamanske CusFeS4 as a standard,38.2 ratherthan34.9 weight
and Rye, 1974). Runs were quenchedby plunging percentS was obtainedfor CuFeS• by direct com-
the vesselsat pressureinto a bucketfilled with ice parison of count rates.
and water. Quenchesto room temperaturetook Many of the (Cu,Fe)-sulfide productsdisplayed
severalminutes,and some (Cu,Fe)-sulfide exsolu- exsolutiontextures,apparentlyrelatedto quenching
.1330 GERALD K. CZAMANSKE

TABLU2. Compositions(in atomicpercent)of Bornite FeS contentof ZnS

Crystallizedat 197ø, 271ø,and 395øCin Association
with StoichiometricChalcopyriteand Pyrite
Sphaleritecompositions are the principalfocusof
Experiment this study. The single experimentat 197øC is
Number Cu Fe S not given weight in the derived equation;the mea-
197øC
suredFeS contentof 0.12 ñ 0.03 molepercentcom-
176T • 50.02 9.92 40.12 pares with the value 0.08 calculatedfrom 271ø and
271øC 395 ø data.
147T 3 50.2 8.3 41.5
202A• 58.7 4.7 36.6 Experiments237, 238, and 239 were plannedto
202A• 51.4 8.7 39.9 locatea pointat ,-•275øCandare in goodagreement.
237T 51.9 8.5 39.6 The average compositionfor these sphaleritesof
238A 52.1 8.3 39.6
238T 51.9 8.5 39.6 0.19 ñ 0.02 mole percentFeS also agreeswith the
239A 52.0 8.4 39.6 result of earlier experiment145, but differs from
239T 52.2 8.5 39.3
the result of experiment 202 (0.10 mole percent
Average composition
202A.,- 239T, Cu,.,.tFe.86St FeS), which used a solutionsaturatedin NH4I at
395øC
25øC as the transportingagent. AlthoughCzaman-
108T 49.9 9.5 40.6 ske and Rye (1974) have shownthat NH4I can
179T 49.2 9.9 40.9 have a different effect than NH•C1 on solution-min-
180T 49.1 10.0 40.9
228S 50.8 9.0 40.2 eral equilibria,experiments265 and 266 suggestthat
228T 50.7 9.3 40.0 this factor is not operativein the present system.
229A 50.6 9.6 39.9
229T 50.7 9.2 40.1
Failure of pyrite to be reactivein the systemis the
261T 50.3 9.4 40.3 preferred explanationfor the low FeS contentof
263T 50.6 9.2 40.2 the202 sphalerite.
264T 50.7 9.1 40.1
265T 50.1 9.4 40.4 Twelve experimentsin the temperaturerange394ø
266T 50.O 9.5 4O.5 to 400øCproducedsphaleritecrystalsup to 500ixin
Average composition 228S -- 266T, Cu6.0•Fe.93St •. sizethat werecompositionally homogeneous as deter-
minedby microprobeanalysis. On the basisof 10
• Lettersdesignatematerialas: T--transported; S•source; of theseexperiments, 0.55 ñ 0.08 mole percentFeS
A--annealed. is accepted for the compositionof sphaleritein equi-
2 Calculatedstandarddeviationsrepresentativefor all data
presented are Cu 4- 0.5, Fe 4- 0.2, andS 4- 0.6. librium with cpy-py-bnat 395øC, 1 kb. Resultsof
a Poor material for analysis. experiments108 and 180 can be explainedonly by
assumingthat equilibriumamongthe four mineral
(Brett,
19•),which
made
difficult
the
precise
deter- phasesdid not prevail,e.g.,supersaturation in FeS2
minationof bulk phasecompositions at the tempera- could be the reason. The homogeneityof crystals
turesof experimentation. To obtainmorehomogen- from these runs indicates that aberrant conditions
eousproducts, fromeachtemperaure were sustainedthroughoutthe runs.
severalsamples
were annealedat identical temperaturesin small- Data for the 500øC experimentsare presentedin
•,diametersilica tubes for which much superior only a fragmentaryway, as no consistentpicture
quenches wereobtained.Analyses of thesehomoge- emergesfrom them. Apparentlybecauseof tie-line
neousproducts are in goodagreement with "bulk" switchesand possiblemetastability in the Cu-Fe-S,
analysesfor the more coarselyexsolvedproducts buffering
system (Barton,1973; Cabri, 1973) sphale-
obtainedby using a defocussed beam and many rites with FeS 'contentsrangingfrom 1.07 to 3.77
pointsof analyses. molepercenthavebeenproducedat 500øC. Two
experiments produced two distinct,coexistingsphal-
Results
eritecompositions
, eachrepresented
by 4 to 7 homo-
Althoughexperimentswerecarriedoutat nominal geneousgrainsto 900t• in size. As a partial ex-
of 200ø, 275ø, 400ø, and 500øC,the planation
temperatures for the 500øCresults,P. B. Barton(writ-
most extensive and reliable results were obtained at tencommun.,
1973)suggests
thatZn mayenterthe
271ø and395øC. All resultsexceptthosefor 500øC intermediatesolidsolution(iss), and stabilizeit, so
are summarized in Tables 1 and 2. Certain results that the cpy+ iss+ py field persistsdown to, or
are consideredof greater significancethan others, below, 500øCratherthan disappearing below532øC
and the data will be consideredin detail. Experi- (seefig.6, Barton,
1973). Analyses of the (Cu,Fe)-
ment numbersreflectthe sequence of experiments. sulfideproductssupportthis interpretation by in-
Resultsare reportedin moleor atomicpercent,and dicatingcoexistence of iss (Cux.•oFeo.oS•.oo) and
uncertaintiesare given as one standarddeviation, stoichiometric chalcopyritein two runs, as well as
basedon microprobe
countingstatistics. the incorporation
of significant
Zn in chalcopyrite
at
 THE FeS CONTENT OF SPH,4LERITE 1331

503øC (Table 3). Considerableadditional study TAmE 3. Zinc Contents (in atomic percent)of Hydrothermal
Bornite and ChalcopyriteCrystallizedin Association
will be required to clarify relationshipsin the Cu- with Pyrite and Sphalerite
Fe-Zn-S systemin the temperaturerange 450ø to
535øC. T, øC Bornitc Chalcopyrite

( Cu,Fe)-sulfidecompositions 197 0.05 (1) 0.04 (1)

271 0.13-0.18, 0.16 (2)x 0.00-0.05, 0.02 (4)
Determinationof compositions of product(Cu,Fe)'- 395 0.03-0.12, 0.09 (5) 0.05-0.13, 0.09 (7)
503 0.11 (1) 0.33-0.43, 0.38 (4)
sulfide phaseshas been an integral aspect of the
present study. At 197ø, 271ø, and 395øC chalco- •Sequenceof values: range of concentrations
measured,
pyrite is homogeneous and stoichiometricwithin the averageconcentration,
numberof samplesanalyzed.
uncertaintyof microprobeanalysis,with the qualifi-
cationthat Fe contentsare typically 0.1 to 0.2 mole tion field and the Cu2S-rich limit of intermediate
percent low becauseof Zn substitution(Table 3). solid solutionfield, as definedfor 500øC by Yund
On the other hand, bornitc producedat 271ø and and Kullerud (1966). Grainswith bulk composi-
395øC is not stoichiometric(Table 2) but has a tions at the limit of the bornitc solid solution field
compositionalong the bornite-digenitejoin. Born- showincipientdevelopment of a chalcopyrite
exsolu-
ite crystals to 250t• producedat 197øC are com- tion texture similar to that shownby Brett (1964,
positionallynear stoichiometric bornitc. Inasmuchfig. 8) Grainsof former,intermediate solidsolution
asYund andKullerud (1966) presentonlyschematic showdramaticexsolutionof chalcopyrite in bornitc,
relationships below 500øC,theseanalysespresently quite like the "basket-weave" texture shown by
constitutethe only publisheddata for compositionsBrett (fig. 3). Average, bulk compositions are
of bornitcin equilibriumwith chalcopyrite
and py- Cu4.7oFex.o9S4.oo and Cu•.•oFeo.94S•.oo. Two runs
rite at low temperature. producedstoichiometric chalcopyritein association
The nonstoichiometricbornitesdisplayexsolution with intermediatesolidsolution,suggesting,
as noted
textures developedduring quenching. Textures of earlier,that Zn altersthe phaserelationshipsof Cu-
the 271øC bornites strongly resemblethe "basket Fe-S. One run produced stoichiometric
chalcopyrite
weave"
texture
offigure
5 inBrett(196•/),whereasin association
with a phaseintermediate
in composi-
thoseof the 395øC bornitesappearas a fine, regular tion to bornitc and idaitc, i.e., Cu46.6Fes.•S•5.•
cell-work
withborni•e
cellstwoor threetimesaslong (atomicproportions).S. Yui (oralcommun.,
1973)
as they are wide arranged in parallel chains and has producedphasesof similar composition,ap-
separatedby thin filmsof digenite. (Brett mentions parentlymetastably,in the courseof a detailedstudy
developmentof a dominantorientationin one of his of idaite.
experimentson this join). This texture was ex- Representativeproductphaseswere checkedfor
cellentlydevelopedduringan otherwiseunsatisfactory extraneouselementsat the 0.01 mole percent level:
polishing attempt employing Fe2Oa suspendedin sphaleriteand pyrite for Cu; pyrite, chalcopyrite,
chromicacid (Cameronand Van Rensburg,1965). and bornite for Zn. No Cu or Zn were detected in
Phase relationsalong the diagenite-bornitejoin, pyrite and no Cu was found in sphalerite. Deter-
as presentedby Yund and Kullerud (1960, fig. 47), minationsof Zn in chalcopyrite(no data for isscom-
are apparentlyrelated to two results of (Cu,Fe)- positionsare reported) and bornitc are summarized
sulfideanalysis:(1) experiment202 at 272øC pro- in Table 3. The data show a distinct increase in the
ducedtwo phasescompositionally near the limits of Zn contentof chalcopyriteas a functionof tempera-
the digenite-bornitesolvus shown by Yund and ture but suggestthat the Zn contentof bornitc is
Kullerud; (2) the compositionof bornite produced relativelyconstantat 0.08 to 0.16 molepercentunder
at 197øC in experiment 176 is stoichiometric,or the conditionsof experimentation.
nearly so, in contrastto the distinctlynonstoichio- Discussion
metric bornitesproducedat 271ø and 395øC. The
phaserelationsshownby Yund and Kullerud sug- Critical analysis of the sphaleritecompositional
gest this result to be reasonable. Differencesin com- data is complicatedby the fact that minor discrepan-
positionbetweenthesephasesproducedat 197ø and cies exist amongthermodynamicdata for the Fe-S
272øCandthosepredictedfromYund and Kullerud, and Cu-Fe-S systems. As a frame of referencefor
figure 47, may relate to equilibrationwith chalco- discussion,Figure 1 has beenconstructedas follows:
pyrite andpyrite in the presentstudy. (1) The three equilibriumunivariant curves other
"Bulk" compositions(averagesof repetitivemea- than chalcopyrite• bornitc -t- pyrite, as well as the
surementswith a defocussed beam) of (Cu,Fe)-sul- contouringof the pyrrhotite field, have been taken
fide grains from the 500øC experimentstypically from Scott and Barnes (1971, fig. 2) with modest
plot at the FeSz-rich limit of the bornitc solid solu- extensionof the isoplethsfor sphaleritecompositions
1332 GERALD K. CZAMANSKE

0.44 +
-

0.15+.02

-Io

-12

-15
MONOCLINIC
PYRRHOTITE
/,,,/
/ / <q"ø•x
-
2O0 250 275 300 400 500 600 700 800
TEMPERATURE, øC

Fro. 1. Relationshipsbetweenthe compositionof sphalerite in mole percent FeS (light, solid lines) and pertinent uni-
variant equilibria, as a function of fugacity of sulfur and temperature at 1 bar. Several isoplethsfor avesin the area of
interest are shown as dotted lines. Measured values for mole percent FeS in sphalerite at 271ø and 395øC have been cor-
rected for the pressurechangefrom 1 kbar to 1 bar and are indicated. Methods of compilationdiscussedin text.

in the pyrrhotitefield, basedon their equation(2). (3) Isoplethsfor aveswithin the pyrite field have
The Scott-Barnesunivariant curve for pyrite • been locatedas follows: a) at 475øC, the approxi-
pyrrhotitehas beenchosenover that of Toulmin and mate crossoverpoint of the Toulmin-Barton and
Barton (1964) for threereasons:a) with the study Scott-Barnespyrite-pyrrhotite univarlant curves,
of Toulmin and Barton in hand, Scott and Barnes aveshas been calculated from the relation 2FeS -I- S•.
locateda univariant curve which is consistent,within •-2FeS•., using the expression•xG*=-70,740-I-
statederror limits, with both setsof data; b) inde- 69.04T (Barton and Skinner, 1967, table 7.2).
pendentstudiesby Giletti et al. (1968) and Schnee- Based on the calculatedspacings,isoplethswere
berg (1973) have eachsupportedthe slightlyflatter constructedparallel to the Scott-Barnesunivariant
curve (in log fs2-1/T space) of Scott and Barnes; curve. This procedureis not entirely arbitrary be-
and c) data from the presentstudyrelate better to causethe constancyof the iron content of sphal-
the Scott-Barnesunivariant curve. (2) The 'uni- erite in equilibriumwith pyrite and pyrrhotite,from
variant curve for the reactionchalcopyrite + S•.• 250ø to 550øC,stronglysuggests that the isopleths
bornite+ pyrite has beenlocatedon the basisof the of FeS activityin the pyrite field mustparallelthe
electrochemicalmeasurements of Schneeberg(1973), pyrite-pyrrhotite'univariant curve. (Minor inac-
which fit the equationlog fs•- 12.560- 1.1067x curaciesthat may exist-becausea free energy ex-
10b(i/T). Schneeberg's univariantcurve was se- pressionhas not been derived for the Scott-Barnes
lected because it is based on more extensive and univariant curve are considered to be well within
inherently more precise data than the univariant the overall uncertaintiesof this treatment.) (4) A
curve of Barton and Toulmin (1964); the two uni- Henry's law constantof 2.5 for sphaleriteof low
variant curvesare parallel and that of Barton and FeS content is obtained from Barton and Toulmin
Toulmin lies at valuesof rs2only 0.2 log unit lower. (1966) by drawinga straightline throughthe origin
 THE FeS CONTENT OF SPHALERITE 1333

of their figure 14 tangent to their array of data. rite-pyrrhotitesolvusdid not agreewith measure-
Basedon this value, sphaleritecompositional points mentunlessvolumechangesin the coexistingphases
were located at 475 øC from the calculated ares values. as a functionof temperatureand pressurewere con-
Compositional isoplethswere constructed parallelto sidered. Sphaleritecompositions measured in this
the ares isopleths(and to the pyrite-pyrrhotiteuni~ studyagreereasonably with existingdata whenun-
variant curve) as requiredfor a Henry's law con- correctedfor pressure,and well when pressurecor-
stant insensitiveto compositionand temperature. rected;however,it seemsadvisableto apply correc-
(5) A field for monoclinicpyrrhotite has been tionsto high pressurewith caution.
shown schematically below its apparent upper It is appropriateto discussthe implications
of the
stabilitylimit at 248øC (Kissin and Scott, 1972). presentstudy for the sphaleritefrom the Iimori
(6) The two data points representingthe results mine,Japan,studied by Yui andCzamanske (1971),
of this study (see Table 1) have beenpressurecor- as this is at presentthe only knownapp!ication of
rected to 1 bar (see below) and have been placed data from the Cu-Fe-Zn-S systemto geothermome-
on the chalcopyrite•-bornite + pyrite univariant try. Reanalysis of the Iimori sphalerite
duringthe
curveof Schneeberg
(1973) at 271ø and 395øC. courseof the presentstudysuggests
that.0.053-
The effectof pressureuponsphaleritecomposition 0.009 molepercentFeS is probablya bettermeasure
has received attention from Barton and Toulmin of its FeS content than the value 0.044- 0.009
(1964), ScottandBarnes(1971), andScott(1973). given by Yui and Czamanske(1971). According
Along the pyrite-pyrrhotiteunivariant curve, in- to the presentstudy,0.0.53mole percentFeS in
creasedpressuremarkedlydecreases N•-•} at con- ZnS shouldcQrrespond to a formationtemperature
stant temperature. In contrast,along the chalco- of ,•170øC, if the sphaleriteis in equilibriumwith
pyrite• bornite+ pyrite univariantcurve,increased cpy-py-bnat 1 kb. Although this temperatureap-
pressureincreasesN•-V&slightly at constanttem- pearslow in comparison with publishedestimatesof
perature. Using the molar volume data of Robie conditionsduring ore formation(see Yui and Cza-
et al. (1966) for bornite and pyrite, Hall and manske, 1971), some studentsof Sanbagawameta-
Stewart (1973) for chalcopyrite,and Barton and morphismwill find it quite realistic(Yui, oral com-
Toulmin(1966) for •rvessph, AV• is calculated
to mun., 1973). The possibleeffectbf pressureon the
be----•-0.5 calfbar for the reaction5CuFeS2•- calculatedtemperatureis marked for the Iimori
CusFeS4+ 2FeS2+ [FeS](•n ,pha•erite). It can be sphaleritebecausepressuresof 5-7 kb have been
shown that postulatedduringformationof the Iimori ore. This
pressurecorrectionwould call for even lower tem-
-- AVrdP -- 2 RT d In peraturesof equilibration.
Assumingthat AVr is constant,partial integration
Acknowledgments
givesthe desiredequation,
Critical reviews by G. M. Anderson,P. B. Bar-
-/xVr (P2- P1) = 2.303 RT [log(aees)r.o ton, Jr., L. J. Cabri, J. T. Nash, and S. D. Scott
- log(a•,es)r, ]
have materiallyimprovedthe clarity and contentof
At 1 bar (the pressurefor whichthe frameworkof this manuscript,and I haveprofitedfrom numerous
Figure 1 is constructed),ares will be •80 percent stimulatingdiscussions with C. L. Christ.
of its valueat 1 kb, the pressureof experimentation. [J. S. GEOI•OGICAL SURVEY
Values for the mole fraction of FeS in sphaleriteat 345 M•DDLEFIEL•) ROAD
1 bar are.thereforeestimatedat 0.15 -- 0.02 (271øC) M•/•o PAR•C,C^t.tFOR•tA94025
and 0.44-0.07 (395øC); these values fit quite February 28, May 7, 1974
well into the framework of existing data (Fig. 1).
REFERENCES
Becauseares= (y•-•}) (N•"•), where y•.o• rep-
resentsthe Henry'slaw constantand 'NTsph
the mole
ß x FeS Barton, P. B., Jr., 1970, Sulfide petrology: Mineralog. Soc.
America Spec. Paper 3, 187-198.
fraction of FeS in ZnS, another way of considering 1973, Solid solutionsin the system Cu-Fe-S: Part 1:
the new data is to derive the Henry's law constant The Cu-S and CuFe-S joins: Eco•v. Gzor..,v. 68, p. 455-
which relates the measured ß, res values to the con- 465.
and Skinner, B. J., 1967, Sulfide mineral stabilities,
toured a•os values. The calculatedvalues of 2.5 ----- in Barnes, H. L., ed., Geochemistry and hydrothermal
0.3 and 2.6-+ 0.4 for 271ø and 395øC, respectively, or• deposits: New York, Holt, Rinehart and Winston, p.
236-333.
are in goodagreementwith the data of Barton and Barton, P. B., Jr., and Toulmin, P., III, 1964, Experimental
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59, p. 747-752.
Scott (1973) found that calculationof the pres- 1966, Phase relations involving sphalerite in the Fe-
sure effecton sphaleritecompositionalong the py- Zn-S system: Ecoa. GzoI.., v. 61, p. 815-849.
1334 GERALD K. CZztMANSKE

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