Economic Geology

\:ol. 72, 1977, pp. 1321-1336

A Thermochemical
Studyof Alunite,Enargite,l,t,z{n,ite,
andTennantiteDeposits
JERRYE. KNIGHT

Abstract

Temperaturedependentphase relationshipsand irreversible reactionsbetweenfluids

and minerals in the systems K20-A12Oa-SiO2-SOa-H20 and FeO-Cu20-H2S-SO a-
As2Oa-H20 have been computedusing thermodynamicdata taken from the literature.
Pyrophyllite, rather than kaolinitc, forms at temperaturesbelow 200øC if the fluid phase
is supersaturatedwith respectto quartz. Pyrophyllite formed under these conditionsis
expected to occur with a roetastablesilica phase. Decreasing temperature at constant
ion activity favors precipitationof alunite over silicate minerals. Formation of alunite
requires acid conditionsand high sulfate activity. In volcanic rocks which are more
reducedthan the hematite-magnetiteoxygenbuffer, the presenceof alunite indicateshigh
H2S activity if the fluid containedgreater than 0.001 molal total sulfur when the tem-
perature of the fluid was 300øC. This fact greatly enhancesthe likelihood that alunite-
producingfluids alsoproducedhigh total sulfur mineralizationat depth. Decreasingtem-
peraturefavorsenargite (luzonite) and tennantiteover coppersulfidemineralsand favors
coppersulfideminerals over iron minerals. If the volcanic rocks above a porphyry pluton
are more oxidized than the pluton,the fluid will oxidize as it floxvsupward. This oxida-
tion favors formation of alunite, quartz, enargite (luzonite), and tennantiteover other
minerals in the systemsstudied. These facts suggestthat the vertical vein mineral zona-
tion in porphyry copperplutonsoverlain by more oxidized volcanic rocks is froin pyrite-
chalcopyrite-potassium feldsparin the pluton upward to enargite (luzonite)-tennantite-
alunite in the volcanic rocks.
Irreversible oxidationof a hydrothermalfluid in equilibriumwith potassiumfeldspar,
quartz,biotite,pyrite, and chalcopyritedecreases
the stabilityof all minerals•vith respect
to the solution,exceptquartz, alunite, and in someinstances,kaolinitc or pyrophyllite.
Irreversiblereactionbetweenan andesiteand a solutionin equilibriumwith alunite and
quartz producesthe following zonations,alunite: kaolinitc:montmorillonite:muscovite:
potassiumfeldspar if the solution maintains quartz equilibrium or alunite: kaolinire:
pyrophyllite:montmorillonite:potassium feldspar if the solution supersaturates with
respect to quartz.

Introduction This studyexamines the phaseequilibriumrela-

ALUNITE(mineralformulasare listedin Table2) tionships among some of the mineralswhichoccur
andcopper-arsenicsulfosalts with alunite and copper-arsenic sulfosaltsand the
occurin hydrothermally characteristics of irreversible and reversible solution-
alteredvolcanicand subvolcanicrocks,particularly
around porphyry copper depositsand prospects mineral reactions which produce these assemblages.
(Table 1). They occurin equilibrium relationshipsA morecomplete analysisof thesehydrothermal sys-
with one anotherand with a varietyof othermin- tems awaits the basic data necessary for computer
erals. The known chemistryof thesemineral as- simulations:permeabilities and geometriesof vol-
semblages pressure,and solu- canic
limitsthe temperature, rocks and heat sources,rock porosities,the
abundance and distribution of minerals.
tion chemistryunderwhichthe assemblage canform
andallowsoneto predictquantitatively
the reversible Previous Work
and irreversible chemical mass transfer between the
hydrothermal
solutions
andmineralphases(Helge- Alunite's mode of formation has long been a sub-
son et al., 1970). With the aid of numericalfluid ject of interest,and manyauthorshavediscussed the
flow analyses(Norton and Knight, 1977; Norton formationand physicalpropertiesof alunite and its
andCathles, in press;RibandoandTorrance,1975), occurrence. Fortunately, a series of review papers
one can also make reasonable estimations of subsur- has consolidatedmuch of this information, thus
facemineralassemblages in thehydrothermal system providingan entry into the alunite literature. Two
andbetterinterpretthe alterationmineralogy
above papersby B. S. Butler (1919, 1956) summarize the
buriedporphyrycopperdeposits. early chemical thought about formation of alunite
1321
1322 JEi?RY E. KNIGHT

TAULF, 1. Alunite Occurrences and Associated Minerals

Location t lost rock Associated minerals Reference

San Manuel, Arizona, monozonite, rhyolite quartz, kaolinite, sericite, Schwartz, 1953
Red Hill area pyrite, opal
Chino, New Mexico,
Niagra and Lee Hills
Ajo, Arizona, concentrator volcanics Gilluly, 1946
Concentrator Hill

Morenci, Arizona, shale-porphyry pyrite, kaolinite, quartz Lindgren, 1905

Ryerson mine contact

Ray, Arizona, schist Ransome, 1919

No. 1, 2, and 3 mines
Cananea, Mexico, tennantite, luzonite, Kelley, 1935
Coloradopipe and all mine kaolinite, quartz
Safford, Arizona,
shaft volcanics

Tyrone, New Mexico,

old town site

Butte, Montana, quartz, kaolinite, sericite,

Enargite vein, Steward mine enargite
E1 Salvadore, Chile, andesite to dacite pyrophyllite, diaspore, Gustafson and Hunt,
upper levels extrusives quartz, enargite 1975

Summitville, Colorado, quartz fatire volcanlcs quartz, pyrite, covellite, Mehnert, et al., 1973
South Mountain enargite
Patagonia, Arizona, volcanic rocks quartz, kaolinite, pyrite
high on Red Mr.
Silver Bell, Arizona, alaskite jarosite, opal, halloyslte, Kerr, 1951
oxide area kaolinire

Yirri, Papua, New Guinea andesite (subvolcanlc) quartz, zeolite, pyrite Jacquesand Webb,
1975
Cerro de Pasco, Peru porphyries enargite, pyrite, quartz, Graton and Bowditch,
close to ore kaolinite 1936

Lepanto, Philippines kaolinite, opal Gonzales, 1959

Chinkaushih, quartz, kaolinire, enargite, Huang, 1955
Taiwan luzonite

Morococha, Peru breccia pipe enargite S. R. Titley

(pets. cornretro.)

and other sulfateminerals. Early reportsof alunite many other minor variations, but these general
occurrenceswere summarizedby Ransome (1909), trends summarize the zoning in most alunite oc-
but since that time no comparablestudy has been currences.

published. The geometry of alunite depositsis varied, but

Alunite usually occurs in volcanic and subvol-
canic rocks and sulfide weathering systems(Ran-
some,1909; Hemley et al., 1969) with quartz, opal,
kaolinite,pyrophyllite,diaspore,or muscovite(Hem-
ley et al., 1969). The relationshipbetween these
minerals often suggeststhey were formed in equil-
ibrium with an aqueousphase. Spatial zoning along
and perpendicularto alunite-bearingveins includes:
(1) alunite: kaolinite: montmorillonite: muscovite
(Schoen et al., 1971; Takahima. 1972; Forgac,
1972); (2) alunite:kaolinite:chlorite-calcite(Kof-
man, 1971); (3) alunite:kaolinite:pyrophyllite-
kaolinite-muscovite(Kim et al., 1971): and (4)
alunite: dickite ---+pyrophyllite:
kaolinire:illite: mont-
morillonite:muscovite(Lodder, 1966). There are
most occurrencesare as massivepods, porcelaneous
veins, or replacementsof grains of alumina-silicate
minerals. The massive type is characteristic of
alunite depositsprospectedas a sourcefor alumina
(Thoenin, 1941) and may be in dose spatial rela-
tionship with the vein- or disseminated-typeoccur-
rences. Alunite and quartz and/or opal comprise
the bulk (>80•) of many of the massivedeposits;
kaolinite,pyrophyllite,and diasporeare also found.
Vein depositsconsistof millimeter- to meter-thick
veins of alunite and quartz and/or opal. The walls
of the veinsgenerallycontainkaolinire,pyrophyllite,
or diaspore. Gold-aluniteveins are examplesof
this type of deposit(Lodder, 1966). In the replace-
ment occurrences, alunite,quartz, and/or opal, and
 .4LUNITE, EN.4RGITE, LUZONITE AND TENNANTITE THERMOCHEMIXTRY 1323

kaolinitc andfor l•y-rophylliteor diaspm'eoccur as laulite, Silumrile,and an t•l•l•alnedCOml)Om•d

have
1)seudomorphicreplacements of alnmina-silicate been identified. ()f these, enargite, luzonite, and
nfinerals,principally muscoviteand feldspar. An tennantiteare by far the most common,and for this
example of this type occurrenceis found at E1 reason only these three minerals are consideredin
Salvador,Chile (Gustarsonand Hunt, 1975). this study.
Thermodynamic parameters of alunite have been Experimental thermodynamicdata have not been
measured'by Kelley et al. (1946); their determina- measuredfor the copper-arsenicsulfosalts,and the
tionsare in satisfactoryagreementwith valuescal- phase relations determinedby Maske and Skinner
culated, in this study, from data on natural hot (1971) cannot be used to extract thermodynamic
springs,whichare depositing alunite(Raymahashay, data. However, Craig and Barton (1973) have
1968). However,phasediagramscalculatedfrom presenteda method,employedin this study,to esti-
these data conflict with the phase diagrams con- mate the free energiesof sulfosalts. BecauseCraig
structed from experimentalphase equilibria data and Barton's method cannot distinguish bet•veen
(see Hemley et al., 1969). luzonite and enargite,thesetwo minerals have been
The copper-arsenicsulfosaltscommonly occur treated as a single thermodynamicphase,arbitrarily
with other iron and coppersulfidesin hydrothermal called enargite.
ore deposits. Their occurrenceis not well sum- Luzoniteand enargiteare polymorphsof CuaAsS•;
marized in the literature but ,hasbeen reviewedby luzonite is the low-temperatureform. Maske and
Gustaison(1963). In general, accordingto Lind- Skinner (1971) have concludedthat the inversion
gren'sscheme(Laughlin and Behre, 1933), deposits from luzoniteto enargitetakes place between275ø
containing these sulfosalts are classifiedas meso- and 300øC.
thermal.
A tendencyfor copper-sulfide mineralsto develop Calculations and Thermodynamic Data
zonation from chalcopyriteor bornire at depth The hydrothermalchemistryot• alunite and cop-
upward into copper-arsenicsulfosaltsis observedat per-arsenic sulfosalts has been examined on the
Butte (Meyer et al., 1968) and the YugoslavJande- basis of equilibrium constants for dissociation
posits, Bor and Majnanpek (as reported in a series reactionsof aqueousspeciesand the hydrolysisre-
ot• lectures by M. Drovenik at the University ot• actionsot•mineral phases. These reactionsform a
Arizona, fall, 1973). This zoning is also impliedin linearly independentbasis for evaluating, by com-
the literature on other depositsbut is not specifically puter methods,all possiblereactionsin multiphase-
stated. At E1 Salvador the arsenic sult•osalt veinlets nmlticomponent systems. The equilibriumconstants
appearto ,haveformed late, and a trend t•romten- (Table 4) were comparedfrom the thermodynamic
nanrite at depth to enargiteat higher elevationsis data compiledin Tables 2 and 3. The tabulated
suggested (Gustarsonand Hunt, 1975). data, for the mostpart, was taken directlyfrom the
The phaserelationsamon.gthe copper-arsenic sul- cited literature after examination for internal con-
fosaltshave beendeterminedexperimentally(Maske sistency. However, the heat capacitiesfor arsenic
and Skinner, 1971). Enargite, luzonite,tennantite, aqueousspecieshave beencomputedby the met,hod

TABLE 2. Mineral Thermodynamic Data Used to Construct Phase Diagralns

Cp coefficients

Høf,,o•s(kcal/gfw) Sø_oes
(e.u.) a b X 10a c X 10-a

Alunite' KAla (SO•)2(OH)• - 1,235.58 78.4 153.45b 0.0 -54.95

Boehmite• A10 (OH) --234.93 11.58 14.43 4.2 0.0
Bornite d FeCu,S4 --84.82 91.0 44.4 40.0 0.6
Chalcopyritea FeCuS.• --44.55 31.2 15.6 21.6 0.6
Covellite d CuS - 11.61 15.93 10.6 2.64 0.0
Enargite• Cu,•AsS4 -- 42.78 85.17 0.0 0.0 0.0
Gibbsitca A1(OH)a - 308.10 16.75 &65 45.6 0.0
Hematite a Fe=Oa -- 197.30 20.89 23.49 18.6 -- 3.55
Kaolinitc d AI=Si=Os(OH) 4 - 980.02 48.53 67.93 19.22 -- 13.78
K-montmorillonite d KA17SinOa0(OH) s - 4,106.76 190.20 255.90 104.7 -- 59.1
Magnetitea FeaO4 -- 267.40 36.03 21.88 48.2 0.0
Microcline d KA1SiaOa - 946.00 52.47 63.83 12.9 -- 17.05
Pyrite d FeS2 -- 41.00 12.65 17.88 1.32 -- 3.05
Pyrophyllite• Al=Si4Ot0(OH)= - 1,343.17 56.6 81.37 35.62 - 19.18
Tennantite • Cu•.•As4S•a - 155.01 3l 1.28 0.0 0.0 0.0

Kelley et al. (1946). • Kelley (1960). e Beane (1972). a Helgeson(1969). ß Craig and Barton (1973).
1324 JERRY E. KNIGHT

T^m • 3. Aqueous SpeciesThermodynamic Data Used to Construct Phase Diagram•

/xHøf,.2os S%8
Species (Kcal/mole) (e.u.) (cal/deg mole) 100øC 150øC 200øC 250øC 300øC

As (OH) •-* -- 239.17 43.32 - 61.8 -- 70.4 - 67.8 -- 77.4 -- 83.0 -- 89.1
HAs (OH) •* - 245.73 63.52 17.5 20.5 11.9 11.6 11.4 18.5
HAs(OH)•-* --307.47 59.82 22.0 25.7 17.0 17.1 17.3 25.0
H•As(OH)6* -314.03 80.02 64.3 86.0 77.1 81.6 85.7 101.0
As(OH)8•-* -485.83 27.94 --101.8 --116.7 -107.8 -125.8 -138.2 --149.3
HAs(OH)• •-* -489.88 66.44 -17.0 --24.9 --33.1 -39.3 --44.8 --48.0
H._,As (OH)•-* -490.65 94.84 63.5 68.0 59.3 59.9 60.5 69.0
H•AS(OH)•* -488.96 110.84 101.4 111.7 102.8 106.6 110.0 124.0
HaSiO•- -- 348.06 45.84 49.0 49.0 46.0 46.0 46.0 45.0
Cu+'[' 16.93 9.4 33.0 44.0 43.0 47.0 50.0 53.0
Cu•+•' 15.39 --23.6 49.0 65.0 66.0 71.0 75.0 79.0
Fea+•' -- 21.0 -- 27.1 50.0 66.0 68.0 73.0 78.0 82.0
Fe•+•' -- 11.4 -- 70.1 70.0 93.0 96.0 105.0 109.0 115.0
AI•+•' - 127.0 -- 76.9 72.0 95.0 99.0 108.0 114.0 120.0
K+• -- 60.04 24.5 27.0 35.0 35.0 39.0 41.0 43.0
H+•- 0.0 0.0 23.0 31.0 33.0 35.0 37.0 39.0
S042:-t -217.32 4.8 --99.0 --108.0 --105.0 --114.0 --120.0 --126.0
S•-• 9.07 -- 4.0 -- 48.0 - 58.0 -- 61.0 -- 65.0 -- 69.0 -- 75.0
H•S•- - 9.03 30.9 46.0 39.0 35.0 32.0 33.0 35.5

* Wagman et al. (1968), heat capacitieswere computedafter Crissand Cobble (1964a,b).

•- Helgeson (1969).

of Crissand Cobble(1964a, b) (see Knight, 1976, øandreactionspresentedare proba.blymuch as

for details). The standard state enthalpy for en- shown.
argite and tennantite(Craig and Barton, 1973) has The activitydiagramspresentedbelowwere calcu-
been changedto rhombicsulfur. lated either by hand or by computerprogram DIA-
Raymahashay(1968) has reporteda free energy GRAM (Brown, 1970). The irreversiblepath de-
of formationfor alunite obtainedby an extrapolation pendentreactionswere computedwith a local modi-
of hydrothermalsolubilitydata, assuminga constant fication of computerprogram PATHI (Helgeson,
entropy of reaction. When these data are extra- 1968; Helgesonet al., 1969; Helgesonet al., 1970),
polated using a temperature-dependententropy and the diagramsportraying the masstransfer calcu-
(Knight, 1976), agreement,within stated error, lations were prepared by computer program
with Kelley et al.'s (1946) calorimetricmeasure- PATPLT (Knight, 1976).
ments is obtained. The term activity ratio as used throughout this
Entropies for both diasporeand its polymorph, communication is defined as the ratio between t.he
boehmite,are subject to large errors (Ulbrich and activity of a given aqueousspeciesand the activity
Merino, 1974). The data for diasporehave been of the hydrogenion raised to a power equal to the
obtainedfrom experimentalequilibrium field mea- aqueousspecies'charge. The result for positively
surementsby Hass (1972) but are derivedfrom the charged speciesis a ratio, for neutral speciest.he
thermodynamic data of corundumwhich are known activity of the species,and for negativelycharged
(Apps,1970;Zen, 1972;UlbrichandMerino,1974) speciesa product.
to be inconsistent with the other data used in this
study. Beane's(1972) data for boehmitehavebeen Phase Relations
selectedin this studyfor calculationof the stability Pyrophyllite
relationsof the A10(OH) polymorphs.
The saturation surface of amorphous silica Phase relations in t.he system Ai2Oa-SiO2-H20-
(Kitahara,1960; Alexanderet al., 1954; Okamoto HC1 indicatethat pyrophyllitemay be formedbelow
et al., 1957) .has'beencalculatedfrom solubilitymea- 250øC by .hydrothermalsolutionswhich are super-
saturated with respect to quartz (Fig. 1). The
surements at one atmosphere at temperatures to
approximate temperaturesat .which pyrophyllite
100øC and at water-steam saturation pressuresfor formed can be determinedfrom the nfineralogyof
greater temperatures. the ,pyrop'hyllite-'bearing
rock. If diasporeor boeh-
Despite every effort to obtain consistentthermo- mite is presentin equilibriumwith pyro?hyllite,the
dynami.cdata, errors are no doubtpresent. These minerals formed between the uppermostkaolinite
errors may considerably affect the quantitativere- stabilitytemperatureand the lowermostandalusite
sultspresentedin this study; however,the trends stabilitytemperature, i.e.,270ø to 360øC. Pyrophyl-
 ,/ILUNITE, EAr,/IRGITE,LUZONITE ,•4XD TENN:tNTITE THER3fOCHEJIISTRY 1325

lite, in the absenceof diaspore and a metastable field extremes. The presenceof a roetastablesilica
silicaphase,can only form at pressureslarge enough plsasein equilibriumwith pyrophylliteimpliessuper-
to shift the quartz saturationsurfaceinto the pyro- saturation with respect to quartz and a formation
phyllite stability field (>300 bar) and at tempera- temperatureof lessthan 200øC becauseabovethis
tures betweenthe kaolinire and andalusitestability temperaturequartz equilibriumis maintainedin hy-
TABLE 4. Eqnilibrium Constants Used to Construct Phase Diagrams

log K at
Reaction 25øC 60øC 100øC 150øC 200øC 250øC 300øC

HAs(OH)4 = As(OH)4- + H + -9.22 -8.79 -8.56 -8.36 -8.53 -8.81 -9.52

HAs(OH)s- = As(OH)4- + H.20 0.06 -0.03 -0.34 --0.75 -1.48 -2.32 -3.58

H2As(OH)5 = As(OH)4- q- H20 q- H + -9.16 -8.77 -8.87 --8.87 -9.52 -10.38 --11.90

As(OH)8 a- + 0.25S•- q- 2H +
= As(OH)4- q- 0.25SO4•- q- 31-t20 25.70 24.60 23.64 22.69 22.08 21.67 21.39

HAs(OH)a 2- = As(OH)s •- q- H + --11.38 -11.15 -11.10 -11.00 -11.32 -11.73 -12.31

HeAS(OH)s- = As(OH)s•- q- 2H + -18.15 -17.93 -18.07 -18.32 --19.17 -20.23 -21.77

H•As(OH)• = As(OH)s a- q- 3H + --20.41 --20.43 -20.64 -21.07 -22.12 --23.38 -25.23

Ahmite
KAl.•(SO4)=(OH)• + 6H +
= K + q- 3AP+ q- 2SO4•- q- 6H20 -1.55 --5.50 --9.29 -13.23 --16.58 -19.61 --22.36
Boehmite
A10(OH) q- 3H + = AI a+ q- 2H20 9.00 6.82 4.89 3.03 1.69 0.64 --0.19
Bornite
FeCu•S4 q- 0.5H•O q- 6.75H +
= Fe •+ q- 5Cu + q- 3.875H2S q- 0.125SO4=- --79.36 -69.88 --60.86 --51.90 -44.42 -37.85 --31.82
Chalcopyrite
FeCuS2 q- 0.5H•O q- 2.75H +
= Fe=+ q- Cu + q- 1.875H•S q- 0.125SO4z- -22.07 -19.64 --17.31 -14.98 -13.06 -11.30 --9.63
Covellite
CuS q- 0.5H20 q- 0.75H +
= Cu + q- 0.875H•S q- 0.125SO4•- --17.46 -15.31 -13.29 -11.30 --9.69 --8.31 --7.05
Enargite
CuaAsS4 q- 5H=O q- 1.5H +
= 3Cu + q- As(OH)4- q- 3.75H2S q- 0.25SO4•- --74.65 -66.26 --58.54 -50.99 --45.19 -40.27 --34.95
Gibbsite
AI(OH)a q- 3H + = AI a+ q- 3H20 7.97 6.17 4.62 3.16 2.16 1.38 0.80
Hematite
Fe2Oa q- 3.5H + q- 0.25H•S
= 2Fe •+ q- 0.25SO4•- q- 2H•O 13.95 11.34 8.98 6.65 4.84 3.13 1.99
Kaolinite
A12Si•Os(OH)• q- 6H +
= 2AI a+ q- 2H4SIO4 q- H•O 7.63 4.75 2.27 --0.12 --1.72 -2.98 -4.00
K-Montmorillonite
KAbSinO.•0(OH)• + 22H + + 8H.,O
= K + q- 7AP+ q- 11H4SiO4 18.33 9.00 0.92 -7.11 --12.53 --16.92 --20.82
Magnetite
FeaO4 q- 5.5H + q- 0.25H2S
= 3Fe •'+ q- 0.25SO4•- q- 3H•O 22.45 18.41 14.74 11.10 8.30 6.08 4.18
Microcline
KA1SiaOs q- 4H20 q- 4H +
= K + q- A1•+ q- 3H4SiO4 1.29 0.42 -0.32 -1.11 -1.57 -1.99 -2.44
Pyrite
FeS= q- H=O q- 1.5H +
= Fe•'+ q- 1.75HzS q- 0.25SO4•-- -13.58 --12.13 -10.76 --9.41 --8.37 -7.39 -6.45
Pyrophyllite
AlzSi40•0(OH)= q- 4H20 q- 6H +
= 2A1•+ q- 4H4SIO4 1.33 --0.89 --2.78 --4.69 -5.95 --6.97 --7.94
Tennantite
Ct•t,.,As4S•,•q- 17H20 q- 7.5li v
= 12Cu+ q- 4As(Oit)4- q- 12.75112Sq- 0.25SO4•- -269.53 -238.94 -210.67 --183.03 --161.61 -152.81 -127.58
1326 ............... JERRY E. KNIGHT

eraIs,althoughthe relativelyhigh concentrations of

potassium in 'some hydrothermal solutions can
easily provide all the potassiumnecessaryto form
alunite. Aluminum, becauseof its relatively low
solubility,is often conservedin the solidphasedur-
ing hydrothermalreactions. The observationthat
in disseminateddepositsalunite is found replacing
= 200-
feldsparsand muscovitesupportsa local sourcefor
aluminum.
Dissolution of aluminum from silicate minerals
I00 requiresthe consumptionof hydrogenions. Analy-
GIBBSITE //:•/ / sis of the processof obtainingaqueousaluminum
//?,'•/ / AMORPHOUS[ ions from minerals has shown that the amounts of
O•
-6 -4 -2
LICA
] 0
hydrogenion consumedor liberatedvaries among
minerals and mineral groups. If aluminum is con-
LogG(H4SiO
4) sidered to be conservedin the solid phases,the
amountsof hydrogenionsconsumed
or liberatedby
FIG. 1. Temperature-log a(H4SiO•) diagram for the
system Al•Oa-SiO•-H20-HC1. The following conventions replacementreactionsmay be qualitativelycon-
were used in this and subsequentactivity diagrams. There sidered. T.he first column of Table 5 contains the
is an aqueousphase present over the entire diagram. The ratio of hydrogenionsto aluminumionsin the hy-
activity of water and mineral phasesis assumedunity. The
solid lines representthe phaseboundary between two mineral drolysisreactionsfor severalclassesof aluminum-
phases and the dashed lines represent mineral saturation bearingalterationminerals. Replacementof feld-
surfaces (note that points at activity ratios greater than
the saturation surfacesare supersaturatedwith that mineral). spar by alunite requiresthe consumption of two
The pressure is one bar for temperatures less than 100øC. moles (column 3, Table 5) of hydrogenions per
_At higher temperatures the thermodynamic data for the moleof aluminumor six moles(column2, Table 5)
aqueousphaseis for the vapor-liquid equilibrium pressurein
the H20 system at that temperature, while mineral thermo- of •hydrogenionsper moleof alunite. .Asshownin
dynamic data are for one bar pressure. Table 5, this is greaterthanthe amountsof hydro-
genion consumed
by any othermineral. Thus,in
drothermal systems(see, for example,Arn6sson, aluminumconservative
systems,formationof alunite
1975). by replacement
of feldsparis more dependent on
Alunite largehydrogen
ionactivities
thanis theformation
of
any othermineral.
Precipitation of alunite from a solution may be
viewedas a two-stepprocess. The first ,stepis the
The phaserelationshipsamongalunite,kaolinite,
destructionof an aluminum-bearingmineral or min- pyrophyllite,
silicaminerals,
and aqueous solution
erals in the ,hostrock; the secondis the combination maybeexamined withtheaidofactivity-activity
dia-
of this aluminum with sulfate and possiblypotas-
siumfrom the solutionto precipitatealunite. Potas- •'ALUNITEI I
sium may also be derivedfrom the host rock rain- \too_X
N-o&x
L•--AMORPHOUS
FSILICA

TABLE 5. Hydrogen Ion Consmnption during FI• MICROCLINE

Replacement of Feldspar
QUARTZ
Moles H + ion Moles H + ion i i I
ALUNITE
consumed by consumed per
t
H+: A1•+ producing mole of
ratio in 1 mole of feldspar
hydrolysis mineral from aluminum m • PYROPHYLLITE PYROPHYLLITE

reaction feldspar replaced

Grossularite
Feldspars
Muscovite
Montmorillonites
Kaolinire
6: 1
4: 1
10:
22:
3:
3
7
l
--4
0
2
2
2
--2.0
0.0
0.67
0.87
1.0
t' ' -4
I I
-2 0
i
Log O(H4SiO
4)
ii
-4
ii I
B

Gibbsire 3: t 1 1.0
Boelunite 3: 1 1 1.0 Fxc,.2. Log a(K+)/a(H+)-log a(H•SiO0 diagramsof
Corundum 3: t 2 1.0
Andalusite 3: l 2 1.0
thesystemK•O-AI•Oa-SOa-H•O-HC1 at 25øC. Loga"(H+)ß
a(SO?-) is equalto --16 in FigureA and--10 in FigureB.
Pyrol)hyllite 3: l 2 1.0 The increasingsulfate activity ratio stabilizesalunite at
.\lunite 2: I 6 2.0
smallerpotassium
activityratiosandlarger silicaactivities.
Note that in B muscoviteis no longer a stable phase.
 .4Lt?NI7'E, EN,41•GITE, LUZONITE
MICROCLINE
8 lnuscovite-alunite
?¾ROI•WLLITE
!
-16.00
I
-14.00
I
-12.00 -I0,00
LO0
Fro. 3. Log a(K+)/a(H+)-log a2(H+) .a(SO•2-) diagram
of the system K20-Al,O:•-SiO2-SOa-H,-HC1
silica activity set at amorphoussilica saturation.Phyro-
phyllite is stableat this temperatureonly if the solutionis
supersaturated in silicawith respectto quartz (compareto
Fig. 4A, which is at the sametemperaturebut at quartz
saturation).
grams of the system KuO-AIuOa-SiO2-SO.•-H20-
HCL (Figs. 2--4). Kaolinite is stablebelow 275øC
in 'solutions
at equilibriumwith quartz;at somewhat
highersilicaactivitiespyrophylliteis stable. Intro-
ductonof potassum andsulfatein sufficient
quantities • 6
allows alunite, K-montmorillonite,muscovite.and
microcline to form,in additionto pyrophyllite and
kaolinite(see,for example,Fig. 2).
_Atquartzsaturation the lnUSCOvitestabilityfield
is locatedat largerlog a(K+)/a(H +) valuesthan is
the kaolinitestabilityfield (Fig. 4). At evenlarger
values of log a(K+)/a(H *) microcline is stable.
The alunitestabilityfield is locatedat greatervalues
of log a(K+)/a(H +) and log a2(H*).a(SO42-)
than the kaolinitestabilityfield and at greaterlog
a2(H+)'a(SO42-) values than the muscovitesta-
bil.ityfield.
At amorphous silicasaturation,pyrophyllitewill
be the equilibriumlow potassium-low sulfatephase
(Fig. 3). At this silicaactivityan increasingvalue
of log a(K+)/a(H +) will causethe solutionto equi-
librate with microcline. Muscovite does not form
at intermediatepotassiumratios, for the increasein
silica activity required to stabilize pyrophyllite
causesthe muscovitestability field to pinch out
(Fig. 2a). The increasedsilica activity also re-
.4.VI) TENN.4NTITE THERMOCHEMISTI•Y 1327
quires larger values
stabilize ahmite.
Temperatureincreasecausesthe kaolinite-alunite
equilibriumboundaryto shift to larger valuesof log
a2(H+).a(S04, 2-) (Fig. 4). Simultaneously,the
andkaolinite-muscovite equilibrium
boundaries 1hove to larger values of log aø-(H+)ß
a(SO• -ø-)and lower valuesof log a(K+)/a(H+), re-
spectively. Thus, decreasingtemperature favors
alunite, relative to the silicate minerals consideredin
RLUNITE
this system,at all temperaturesless than 270"C.
Equilibration of a solutionand alunite may be pro-
duced by increasing the value of log a2(H+) ß
a(SO•-ø-), by increasingthe value of log a(K+)/
a(H +) if the sulfateproductis sufficientlylarge, by
decreasingtemperature,or by any combinationof
theseprocesses.
Equilibrationof alunitein a solutionsaturatedor
supersaturated with respectto quartz requiresrela-
tively large values of log a•(H +) -a(SO•"-), regard-
-8.00 -6.00
lessof temperature. Replacementof rock by alunite
consumes both hydrogenionsand sulfateions.Main-
tenance of the product log a2(H+)'a(SO4 -•-) at
at 25øC and values greater than about -13, which is necessary
to stabilize alunite, requires that both ions in the
product be extremely abundant (pH < 4, SO•
100 ppm) or that they be continuallyreplenishedas
they are consumedby reaction. In lnodern hot-
springsystemsthere is evidencethat the valueof this
ion productis increasedto, and maintainedat, alunite
saturationlevelsby oxidationof sulfidesulfur, pos-
MUSCOVITE
[ •
-16 -12 -16 -12
c
MICROCLINE
• MUSCOVITE
• KAOLINITE
-ll6 -12
Log
Q(H+)
2.Q(SO•-)
Fro. 4. Log a (K +)/a (H +) -log a•(H +) -a (SO• •-) diagrams
of the systemK_oO-AI•O,,-SiO.o-SO•-H.oO-HC1. Silica activity
has beenset at quartz saturationin each diagram. Diagram
A is for 25øC, B is for 100øC, and C is for 200øC. As tem-
perature increases, larger sulfate ratios are required to sta-
bilize alunite at a given potassiumratio and smallerpotassium
ratios are required to stabilize muscovite and microcline at
a given sulfate ratio.
1328 JERRY E. KNIGHT

slbly with someaid fr,,m bacterialcatalysts(Brock i•ms, oxidation of bibulfide ions to sulfate ions is
and Mosser,1975; Brock et al., 1976). still a likely mechanism. A ten weight percent
If oxidationis the agent which producesthe acid alunite rock contains0.24 moles of alunite (0.48
necessary for the formationof aluniticrocks,reduced molesof sulfateions) per thousandgramsof rock.
sulfur speciesin the source solutionsare required. Thus, 0.048 moles(1,500 ppm) of sulfidesulfur is
The amount of reduced sulfur required to replace requiredfor a water: rock ratio of 10: 1. An original
value of log a(HuS)> -2 is indicated.
feldsparwith alunite can be calculatedif the identity
of the reducedsulfur speciesis known. A rock con- The hydrogenions and sulfateions necessaryfor
taining ten weight percent alunite is equivalentto alunite formation may be derived from a solution
0.24 moles of alunite per thousandgrams of rock. with high initial sulfateactivities. A possiblesource
:Eachmole of alunite producedby replacingfeldspar is the oxidation-reduction of sulfite(SOa•-) sulfurto
requiresthe consumption of six molesof hydrogen sulfideand sulfate sulfur as the temperaturein the
ions, as shownin Table 5; thus, 1.4 molesof hydro- hydrothermalfluid decreases(Holland, 1965). But
genionshavebeenconsumed per thousandgramsof sincethe oxygenfugacitiesof hydrothermalsystems
rock. A water:rock weight ratio of 10:1 requires generallydo not greatly exceedthe oxygenfugacity
the solutionto provide 0.14 molesof hydrogenions of the hematite-magnetite buffer, solutionscontaining
per kilogramof water. If the oxidationof bisulfide high total sulfate ion concentrationsmust also con-
ions to sulfateions is the hypotheticalsourceof the tain high total sulfide concentrations. For example,
hydrogenions, a solution with log a•(H+)'a(SO42-) = -12 at
300øChasa log a(HuS) of approximately-3 if the
2H2S + 402 = 3H + + HSO4- + SO4-ø, rockhasan oxidationpotentialnearthat of the hema-
then 0.09 molesof bisulfideper thousandgrams of tite-magnetitebuffer. More reducingenvironments
water (3,000 ppm) must be oxidized. An initial require larger HuS activities. Again, the presence
loga(HaS) valueof -2 or greateris required.Such of alunite implieshigh HuS activity in solutionand
a large value almostcertainlyinsuresthat sulfide enhances the possibilitythat sulfidemineralswere in
mineralswere in equilibriumwith the solutionprior equilibrium with the solutionsprior to formationof
to oxidation. alunite.

If thelimitingfactorfor theformationof aluniteis

Cu-Fe sulfidesand Cu-•Is sulfosalts
the production of sulfateionsratherthan hydrogen
The portionof the systemsFeO-CuuO-HsS-SOa-
As2Oa-H20-HCI representedby the aqueousphase
MAGNETITE
•//' and the mineralphasesmagnetite,hematite,pyrite,
pyrrhotite,chalcopyrite,
bornite,chalcocite,
covellite,
• 2o• enargite,and tennantite
hasbeenconsidered in this
study. Shiftsin thepositions
of mineralequilibrium
fieldsin this systemare dominatedby the tendency
iz IO• of copper-bearing
mineralsto becomestableat in-
/•CHALCOClTE creasinglylower values of log a(Cu+)/a(H +) as
ß I I I I I
temperaturedecreases(Fig. 5). Precipitationof
300 copper-sulfur
minerals,rather than pyrite or mag-
netite,is favoredin any fluid flow regimewherethe
telnperaturedecreasesalong the flow path. Of
course,formationof coppermineralsis limited to
200

PYRITE
//EORNITE solutionstransportingsufficientcopperto stabilize
them regardlessof temperature.
IOO ////TENNANTITE Geometryof isothermalequilibriumfieldsof cop-
,,•///,•-•CHALCOCITE per-iron-sulfur
mineralsmay be represented on log
/ C a(Fe2+)/a2(H+) -- log a(Cu+)/a(H +) diagrams..At
-14 -I0 -6 -2 -14 -I0 -6 -2 low arsenicand iron activity ratios the zoning from
Lo(]O(Cu+)/O(H
+) low to high copperactivityis pyrite-covellite-bornite
LogO(Cu+)
/ O(H
+)
(Fig. 6). At intermediateiron activityratiosthe
Fro. 5. Temperature-log a(Cu+)/a(I-I *) diagrams of the
system FeO-CmO-H.oS-SO•-As.,Oa-H•O-HC1.The fixed covelliteequilibriumfield shrinksaway, resultingin
activity ratios are: the copperactivity zoningof pyrite-bornite. If the
Log a(Fe•+)/a•(H +) = 4(A), 2(B), 0(C), --4(D) activityof HuS is sufficiently
large, chalcopyrite
will
Loga(H.zS)= --2(A), --2(B), -2(C), --3(D) have an equilibriumfield at large, > 1.0, valuesof
Log a(H +) -a(As(OH)4-) = - 12(A),- 12(B),- 12(C), - 12(D) log a(Fe2+)/a•(H +) (Fig. 6). Also. at large iron
 ALUNITE, ENARGITE, LUZONITE ,4ND TENNANTITE THERMOCHEMISTRY 1329

higher arsenic concentrations the tennantitefield

expandsto lower copperactivitiesand may be in
I I i contact with covellite, enargite, pyrite, and chal-
copyritefields(see,for example,Fig. 8), in addition
to bornite.
A solutionat equilibrium•vith K-feldspar,biotite,
pyrite, and chalcopyrite
in a porphyrycopperpluton
will be subjectedto decreasingtemperaturesas it
flowsupwardinto the overlyingvolcanicrocks. The
½H•L½O½ITE
volcanicrocks, having been exposedto the atmos-
Ig phereduring their deposition,are likely to be more
/•.•PYR
RHOTI
Tœ
oxidizedthan the plutonand, therefore,oxidizethe
solution. Knowing this, one can qualitativelyex-
I aminethe verticalzoningof sulfideand sulfosaltmin-
[•"IflU•I]PYR1
\ eralogyaboveporphyrycopperplutonswhich have
beeneraplacedinto a volcanicpile.
Comparison of the temperaturedependenceof the
equilibriumconstantsfor reactionsbetweenthe re-
ducedand oxidizedaqueousspeciesof iron, copper,
sulfur,and arsenic(Table 6) indicatesthat decreas-
•. PYRI1'E ing temperaturefavors the reducedforms of iron
and arsenicand the oxidized forms of copper. Be-
tween 300ø and 200øC cooling favors sulfate, but
g / COW:LL]TE
• between 200 ø and 100øC sulfide is favored.
these trends, that for arsenic is strongest.
Of

i i i
I I I
•LO.00 -e.00 -6.00 -q.00 -e.00 0.00
Leo A(CU+J/R(H+ )

Fro. 6. Log a(Fe•)/a-ø(H+)-log a(Cu +)/a(H*) diagram

of the system FeO-Cu•O-HgS-SOa-HC1. The temperature
is 300øC,and tog a(H•S) is set at •3. This diagram sho•vs
the relative positions of common hydrothermal copper and
iron sulfide and oxide minerals in activity space.

activity ratios pyrite will give way to magnetiteif

H._,Sactivity is moderate to large (i.e., under re-
ducing conditions) or to hematite if I•I2S activity is
TEl,•cm•T I TE
small (i.e., under oxidizing conditions). Whenever
a hematiteequilibrimnfield appears,it will have a
boundarywith magnetitewhichis independentof the
activitiesof bisulfideor arsenic,and the chalcopyrite ,•CHALCOCITE

field will be very smallor absent.

Enargite and tennantitehave stability fieldswhich
appearon this diagramif log a(H +) .a(As(OH)4-)
is greater than -14. The enargite field plots be-
/I
E)•C!•'OI TE

tween that of covelliteand bornire. If log a(H+) ß

a(As(OH)•-) is greaterthan -11, the enargitefield
completelyoverrides the covellite field (Fig. 7).
Enargite may coexist with chalcopyriteat large
arsenite and sulfide activities. At all arsenic activities
- 4.0o
,/ -]o.oo -e.oo
LO0 R(CU+)/R(H+)
•.o0

the tennantite field is located at lower iron and

Fro. 7. Log a(Fe•)/ae(H+)-log a(Cu*)/a(H •) diagram
greatercopperactivitiesthan the bornitefield. How- of the systemFeO-CmO-H•S-SOa-As•O.•-H•O-HC1at 100øC.
ever, unlessmore than 0.01 ppm arsenic is present, Log a(HeS) is set at --3 and log a(H +) .a(As(OH)•-) at
--12. This diagram shows the relative positions in activity
the tennantitefield is locatedat uurealisticallylarge spaceof enargiteand tennantitewith respectto copperand
activities of copper at all temperatures. VVith iron sulfide minerals.
1330 JERRY E. KNIGHT

I I I fastest,followedby Cu+, HeS, and As(OH)c, in that

order. Furthermore,the activity ratio of As(OH)i-
will vary nmch more slowly than that of the other
species. The exact relativevariationsdependupon
H•As(OH)
5 the ratesof temperaturedecreaseand oxidation,and
their ordermay changeundersomeconditions.

HAs
(OH)•
The relativeactivityratio changesprojectedabove
producethe zoningof copperminerals:chalcopyrite-
tennantite-enargite(circles in Fig. 5) or chalco-
HAs(OH)
4 pyrite-enargitevolcanicrocksif more than 50 ppm
I I I
•As(OH)•4 arsenicis presentin the solution. If the solution
i I i i containslessthan 50 ppm arsenic,tennantiteand/or
, ,. enargite may not form. Vertical copper mineral
zoningin low arsenicsolutionsconsistsof chalcopy-
rite, chalcopyrite-covellite,
and chalcopyrite-bornite-
covellite.
H•As(OH)•
•lrsenic aqueousspecies

•s(0•)•- The distribution of arsenic aqueousspecieshas

been calculatedas a functionof oxygen fugacity,
temperature,
andpH (Figs.8 and9). Thesecalcu-
lationsindicatethat, at all temperaturesbetween0 ø
IO Ii 12
4 5 6
pH
7 8 9
and 300øC with a pH less than 9, and at oxygen
fugacities
of hydrothermal
solutions
(nearthe hema-
Fig. 8. Temperature-pH distributionof arsenic aqueous tite-magnetite buffer), the arsenitespeciesare more
species. The distribution fields are boundedby lines of
equal activitiesof two speciesand representthe conditions stablethan the arsenatespecies. This conclusionis
wherea given specieshas the largestactivity of all arsenic notlikelyto bealteredby the discovery of additional
species.Under hydrothermalconditionsthe arseniteaqueous arseniccomplexes.
species (A) are more abundant than the arsenate aqueous
species (B). In general, oxidation favors the arsenate Calculations of Irreversible Reactions
speciesand reductionthe arsenite(see Fig. 9 also).
Changesin the chemistryof sulfur-richhydro-
Oxidation of the solution will tend to decrease the
thermal solutionsflowing upward from plutonsinto
activitiesof all reducedaqueousspeciesand increase volcanicrock environmentsare controlled by three
thoseof all oxidizedspecies.Oxidationalsoproduces interrelatedprocesses: (1) a decreasingtempera-
hydrogenions,xvhichaffectsthe activityratiosof ture alongfluid pathlines,(2) the tendencyof solu-
the variousspecies.Reductionof pH by one unit
changes the log activityratioof Fe2+by -2 units,of
Cu+ by -1, of S2-by +2, andof As(OH)i- by +1. 0[ I I I I
\Yhen the combinedeffectsof temperaturedecrease
and oxidation are considered,one predictsthat the
activityratiosof Fe2+,Cu+,I-I2S,andAs(OH)c will
I H2As(OH)
• __
I00
øC
all decrease.Onealsopredictsthatthe activityratios
of thesefour specieswill vary at differingrates: Fe2
-40 -

TABLE6. Equilibrium betweenSolutionSpeciesat _

Hematite-Magnetite Equilibrium Reaction

H2As(OH)5
log K -60 -

Reaction 100øC 200øC 300øC -70 -

Fe 2+ q- H + q- 3/2Fe2Oa
-BO I I I I I
= Fea+ q- FeaO4q- 1/2H,,O --8.85 --8.33 --8.02 3 4 5 6 7 8 9 1o [i 12

Cu + q- H + q- 3/2FeeOs pH
= Cu-*+q- FeaO4q- 1/2H2 --0.15 --1.13 --1.85
H2S q- 12Fe•Oa Fro. 9. Oxygenfugacity (/o,_,)-pHdistributiondiagramof
= SO•2- q- 2H + q- 8FeaO• --9.77 --8.67 --8.85 arsenicaqueousspeciesat 100øC. The arsenatespeciesare
As(OH)•- q- 3H20 q- 3Fe.oOa favored by oxidizing conditions,the arsenite speciesby
= As(OH)•a- q- 2H + q- 2FeaO• --30.56 --17.80 --9.02 reducingconditions. Distribution diagramsfor other tem-
peraturesshowthe samegeneralrelationships.
 ./tLUNITE, E.,V./tRGITE,LUZONITE ./tXD TE.VN.4NTITE THER.•IIOCHE3[IS'TRY 1331

tions to oxidize as they fioxv through near-surface complexesincreasesthe hydrognion activity by re-
environments,and (3) a reaction with host rocks movingfree sulfateionsfrom the solutionand, thus,
that are generally more oxidized than the pluton. requiring bisulfate ions to dissociateto sulfate and
Each of thesehas beenconsideredseparately. hydrogenions.
Activities of all aqueousspecies,other than those
Temperature variations
containingsulfide,sulfate,ferric iron, and aluminum,
The qualitativeeffectof variabletemperaturehas remainedvirtually constantthroughoutthe oxidation
been deducedfrom temperature-activitydiagrams process.An observedincreasein aluminumactivities
and activity-activitydiagramsat multiple tempera- is the result of a decreasingsolution pH and a
tures. Theseeffectshave beenpresentedin previous sinmltaneousdissociationof aluminum hydroxide
sections. At present,the rigorouscomputationof COlnplexes.The changesin the activities of other
mass transfer as a function of temperature is not speciesare a result of the oxidationand coupledpH
possible. change.
The activity ratios of all simple ions, other than
Oxidation of solutions
alulninumand sulfate,decreasethroughoutthe reac-
Irreversible reactions between a sulfur-bearing tion. The activity ratio for aluminumalso decreases
solution(stoichiometricionicstrengthapproximately for muchof the reaction(Fig. 10), but at a rate less
0.1) and pure oxygengashave beenrun at 25 ø, 100ø, than the one predictedby pH changealone. This
and 300øC in order to observe the oxidation effects. behaviorimpliesthat the oxidationof hydrothermal
Oxygen gas was chosenas the reactant so that the sulfide-richsolutionsmovesthe solutioncomposition
effectsof changingoxygenfugacity couldbe isolated; away from the stability fields of most silicatemin-
similar results would be obtained for other oxidation erals and toward the activity-spacefield representing
methods. Aluminmn, potassiumsodium, calcium, undersaturated solution. In the absence of a host-
magnesium,iron, silicon, sulfur, and chlorine have rock reaction, only sulfate- and, to a lesser degree,
been set at relative abundancesobservedin hydro- aluminum-bearingminerals will be precipitated by
thermal fieldscontainingahmitedepositsat ¾ello•v- isothermal,oxidizing, sulfur-rich solutions.
stone Xational Park, \Vyoming (Raymahashay, The activityof aqueous silicadoesnot dependupon
1968). Initial pH - 6 and equalinitial total toolall- the oxidationstate or pH of the solutionin acid to
ties of sulfate and sulfide sulfur have been used in slightlyalkaline solutions(Helgeson, 1969). Also,
each run. Runs stoppedwhen the oxygen fugacity quartz,opal,andaluminumsilicates, suchaskaolinire,
of the solution increasedto approximately ten log pyrophyllite,and andalusite, becomeincreasinglyin-
units greater than hematite-magnetite equilibrium. solublewith a decreasingtemperature. When these
The general trend observedat every temperature factsare coupledwith the tendencyof oxidizingsul-
is, of course, the oxidation of multivalence elements fur-rich solutions to stabilize only sulfate- and
to their higher oxidationstates. In addition,the pH alumimun-bearing minerals, the ubiquitous equi-
is decreased. The exact reaction of oxidation de- librium association of hydrothermalalunitewith only
pendssomewhaton temperaturebut is similar at all alumimunsilicates,silicaphases,and aluminumoxide
temperaturesat equivalentpH's. In the following mineralsis predicted.
discussionthe 100øC reactionswill be presented,but
the conclusionsare applicableto other temperatures Reaction with host rocks
as •vell.
An initial solutionin equilibriumwith eitheralunite
At 100øC the reaction, integrated from the pH of or the assemblagealunite-pyrite-kaolinite has been
6to3, is usedin eachof the followingmodels. Silica activity
02 + 0.05 Na + + 0.10 HS- + 0.40 HsS + 0.0l Ca -o+ has either been held at quartz saturation or allowed
= 0.20 SO42- + 0.24 HSO4- to supersaturate with respectto quartz.Thesemodels
+ 0.01 CaSO4 + 0.05 NaSO4 + 0.66 H +. are designed to simulate the reaction between an
acid solutionand rock. Therefore, the'models simu-
On the average,1.3 molesof hydrogenions are pro- late mineral zoning in ahmite-quartz,alunite-quartz-
duced for each mole of sulfide sulfur oxidized to sul- kaolinite, and alunite-amorphoussilica-kaolinite oc-
fate sulfur. It must be emphasizedthat the coeffici- currences.

entsfor the overall reactionor for any instantaneous
reactionat a given pH dependon the bulk composi-
tion of the solution (Helgeson et al., 1969). In
particular, the activities of the alkali and alkali-earth
lnetalshavea largeinfluenceon the an•ountof hydro-
gert ions produced. Forlnation of alkali-snlfate
Compuations which are constrained by quartz
saturationpredict changesin activity ratios typified
bv thoseplotted in Figure 11. The projectedsolu-
tion composition shiœtsaway from the alunite sta-
bility field toward the kaolinite stability field. At
this point the additionof iron from the countryrock
1332 JERRY E. KNIGHT

•2 •L+++ -1
I=) K+
(:D N•+ -3
' CA++

FE++

•
•
•
• FE+++
-7
s04--
PH -10

• I

•
•I . I I
8

-6.00 -5.00 -4.00 -3.00

LOG (REACTION PROGRESS)
Fro. ]0. Activity ratio-log react{on progress plot for the oxidation of a solution at ]00øC.
The oxidation consumes sul6de su]fur and produces hydrogen and su]f•te •ons. The
creash• pH causesthe cation acdv•ty ratios to decrease.

causespyrite to equilibrate with the solution before Solution-host rock reactions which have been al-
kaolinite. When kaolinireequilibrateswith the solu- lowed to supersaturatewith respectto quartz differ
tion, the rate of hydrogenion consmnptiondecreases, from thoserun at quartz saturation,primarily in that
allowing the solutioneventuallyto leave the pyrite nmscovite does not occur in the predicted zoning
and alunite stabilityfields. Once the solutioncom- while pyrophyllitedoes. Absolutemassesof mont-
positionhas shiftedaway from the alunite-kaolinite orillonitespredictedare larger in the supersaturated
boundary,the reactionsequentially equilibrateswith runs, and the mass of alunite is smaller.
montmorillonite, muscovite,and microcline. When The absolute mass of each mineral encountered in
biotiteequilibrates,
thepotassium-hydrogen ion activ- a typical isothermalrun at quartz supersaturationis
ity ratio becomesconstant,while the sulfate-hydro- shownin Figure 12. Figure 12 may also be viewed
genion activityratio continuesto decreaseuntil final as a paragenesisdiagram; the sequenceof minerals
equilibriumis attained. encounteredis a functionof time (representedby the
In summary,the predictedisothermalzoning pat- reactionprogress). The reactioninitially produces
tern adjacent to and along alunite veins (quartz is kaolinite; it then equilibrateshematite and pyrite
present in each case) is: alunite, alunite-pyrite, before equilibratingwith pyrophyllite. Upon equil-
alunite-kaolinite-pyrite, alunite-kaolinite, kaolinire, ibrating with pyrophyllite,equilibrationwith respect
mortmorillonite,muscovite,microcline,and, eventu- to kaolinite is lost. Alunite equilibration follows,
ally, unalteredhost rocks. but the mass producedis not large becausethe in-
All the observedzonings in quartz-alunite occur- creasingsilica activity forces the solution to equil-
rences•verereproducedby changingthe composition ibrate with pyrophyllite and undersaturate with
of the initial solution. For example, reducing the alunite. The reactionthen seqnentiallyequilibrates
initial sodium,potassium,and calciumeliminatesthe with magnesiummontmorillonite,amorphoussilica,
montmorillonitezone. Alternatively, increasingthe sodium montmorillonite, microcline, annite, and,
initial concentrationsof these elements can produce eventually,the entire volcanicrock (Fig'. 13).
the predictedzoning, alunite:montmorillonite,with Predicted zoning'alnong silicateminerals for silica
no il•terlnediate kaolinite zone, supersaturated
runsis: kaolinire,pyrophyllite,
pyro-
 .4LUNITE, EN.4RGITE, LUZONITE .4.VD TENN.4NTITE THERMOCHEM'ISTRY 1333

causesa changein tile rate of enargite and quartz

MICROCLINE l,recipitation(Fig. 14). The reactiontheH1)n•cet'ds
_ / _ tmtil equilibrimnwith microclineand chalcopyriteis
established. At this point the solutionundersatur-
musco- \\ I
4 VITE \\ I ates with respectto enargiteand pyrite.
• - N•.MNT - Prior to muscoviteequilibration,enargite is pro-
-t- '=-•'.+MNT
duced at a molecular rate approximately 15 times
larger than the rate at which pyrite is produced.
• QTZ
+ Veinlets produced under these conditionsand then
'• 0- ALUNITE- isolatedfrom the solution would have copper:iron
massratiosof 22: I. After muscoviteequilibration,
o
enargiteand pyrite continueto be produced,but the
differencein their molecularrates of productionde-

-J- KAOLINITE
• -
-4

-18
-

-14 -I0
-

-6
LogQ(H+)
•, O(SO•-)
Fro. 11. Reaction path for a reaction between a volcanic
rock and a high total sulfur-bearing aqueous solution at
quartz saturation and 100øC. Solid parallel lines indicate
that the mineral in the stability field is in equilibrium with
the solution; dashed lines indicate the solution is under-
saturated with respect to the mineral. Circles indicate a
phase boundary. A plus sign indicates the mineral has
equilibrated with the solution; a minus sign indicates the
mineral's equilibration has been lost. Abbreviations used are:
quartz (QTZ), pyrite (PY), montmorillonite(MNT),
annite (AN). This reactionpath producesa mineral zoning
commonlyobservedaround and along alunite-bearingveins.
creasesfrom 15:1 to 5:1. Just before pyrite and
enargitedisequilibrium(Fig. 14), the copper:iron
mass ratio is 7: 1.
The predictedzoningand paragenesis in and near
enargite veins in volcanicrocks is: quartz, quartz-
enargite-pyrite (very high Cu:Fe), quartz-musco-
vite-enargite-pyrite(increasinglylower Cu: re), K-
feldspar-chalcopyrite, and eventual host-rock equi-
librium.
When the identical solution in equilibriumwith
enargiteis reactedat 200øC with a rock composed
of
PYRITE
HEMATITE
-1

LOU ALBITE -3
KAOLINITE -4
phyllite-montmorillonite,montmorillonite-opal,K- PYROPHYLLITE
MA-MOMTMORILLOMITE -6
feldspar-montmorillonite-opal,
and, eventually,host- CA-•OMT•ORILLOMITE
MG-MOMTMORILLOMITE
-7
-B
rock equilibrium. Pyrite, hematite,and magnetite ALUMITE -9

may be present over much of the reaction path, a

silica speciesmay form over the entire path, and
alunite equilibriumcan only be maintainedin the
presenceof kaolinireor pyrophylliteor by itself.
Mineral zoning with respect to copper-arsenic
sulfosalt veins at 200øC has been studied in two
ways. First, a solutionin equilibriumwith enargite
has been reactedwith a rock of andesirecomposition
to simulate zoning along copper-arsenic sulfosalt
veins in volcanicrocks. Second,a solutionin equi-
librium with enargite has been reactedwith a rock
containingonly quartz,kaolinire,and aluniteto simu-
late zoningbetweensulfosaltveins and alunitic rocks.
The initial solutioncompositionfor the andesite-
reactant model is a high total sulfur solution which
would be in equilibrimnwith pyrite-chalcopyrite-
biotite-K-feldspar at 300øC. The total arsenic con-
centrationis set at log a(H +) .a(As(OH)•-) = -12, -8.00 -6.00 -4.00 -2.00
and the total iron concentration is setat log a (re "+)/ LOG (REACTION PROGRESS)
a?(H+) -ø-- -4.
FIG. 12. Log grams of minerals produced per kg of I-I.20--
The irreversiblereactionstarts at quartz satura- log reaction progress plot for a reaction between an andesite
tion and equilibrateswith enargiteand pyrite after a and a high total sulfur solution at 100øC. The solution •vas
small amountof reactionprogress(Fig. 14). This allowed to supersaturatewith respectto quartz. The mineral
zoning producedby the reaction path is commonly observed
is followedby equilibrationwith muscovite,which in alunite-bearing veins.
1334 JERRY E. KNIGHT

stableassemblage,and no zfmingis predictedl)etween

enargiteveins and quartz-kaolinite-ahmiterocks.
Discussion
• I,•,•-AMOR
PHOUS
• I SILICA
An analysisof fluid flow around pluton heat
8- • SATURATION
sourceshasshownthat aqueousfluidsmovefrom the
topsof plutonsinto overlyingrocksand coolas they

•'__
',•
ALUNITE
• !MICROCLINE K-MONT'•No MNT
flow upward (Norton and Knight, 1977; :Ribando
and Torrance, 1975). In volcanic-subvolcanic en-
vironmentsthe tops of plutons are often in contact
with volcanic rocks of similar composition. The
predominantdriving force for hydrothermalfluid-
• (KAOL // rock reactionsalong fluid pathlinesis the decreasing
temperature, not changesin the reactant rock com-
O- / +ALU - position. Alteration mineralswhich are favored by
decreasingtemperatureconditionswill form in this

-4
-6
GIBBSITE
I t •PYROPHYLLITE
I I
-4
I I II
-2
I
0
regime.
Alteration mineralogy above plutons which are
anomalouslyrich in sulfur will reflect both cooling
Log Q(H4Si04) alongfluid pathlinesand the anomalouslylarge sul-
fur activitiesin the pluton environment. The chemi~
Fro. 13. •eaction path •or a reaction between a vol- cal relations presentedin this communicationpre-
canic rock and a high total suffur-bearing solution at
quartz supersaturation.Abbreviationsare: alunite (AL•), dict the formation of copper-arsenicsulfosaltsand
magnesium montmorillonite (Mg•NT), pyrophyllite alunite under theseconditions,particularly •vhen the
(PYRO), amorphoussilica (A. SIL), sodiummontmoril- solutionsare subjectedto oxidation. The predicted
lonite (NaMNT), and microcline(MI). The alunite equi-
librium field is drawn as it was when amorphous silica spatial zoning in and above sulfur-rich plutons is
saturation occurred. (See Fig. 12 caption (or •urther ex- from chalcopyrite-magnetite below to copper-arsenic
planation.)
sulfosaltsabove and from anhydrite-K-feldspar-bio-
alunite,quartz, and kaolinite,only enargiteand the tite below to alunite above (Fig. 15). Pyrophyllite
three rock minerals are encountered in the reaction plus opal (amorphoussilica) may also occurabove
path. Thus, enargite-quartz-kaolinite-alunite
is a these plutons. It should be interpreted as a low

O CH•LC0PYR
I TE
O OU•RTZ -3
I"IICROCLIHE -4 4

• C•i- .USCOUITE
EHRG[TE

• 6I I
ß

• I
•-8.00 -'7.00 -6.00 -5.00 -4.00 -3.00
LOG (REACTION PROGRESS)

Fro. 14. Log grams of minerals produced per kg of water--log reaction progress for a reac-
tion betweenan andesiteand a hydrothermal solution containing high concentrationsof copper,
sulfur, and arsenic. The reaction predicts the zoning quartz: quartz, enargite, pyrite:quartz,
muscovite, pyrite, enargite: quartz, chalcopyrite, microcline, and variable copper to total sulfide
ratios.
 •ILUNITE, EN•IRGITE, LUZONITE
AMORPttOUS- .gl[ICA
PYNOPHYLI. I I i::
•]1
I CO.,-NaCI-HCI:
; Univ., Evanston, Ill.
!..=.I.(•..O..
....... .' ' PYRITE
- ENARGITE
PYRITE -TENNANTITE
'500
',
'[PYRITE
-MAGNETITE-
;
=300
.'T= CHALCOPYRITE
...T.:.•OO - T
Time = 50,000yrs.
Fro. 15. Possible mineral zoning patterns with respectto
a pluton intruded into volcanic host rocks. The dotted lines
are isotherms. This figure is drawn for a 50-thousand-year-
old hydrothermalsystem (Norton and Knight, 1977).
temperature(<200øC) assemblageand used as an
indicatorof upflowinghydrothermalfluids.
Acknowledgments
I wish to thank D. L. Norton for his guidanceand
many useful discussions throughoutthis study. I
thank T. Gerlach,R. Knapp,and R. N. Villas for
their discussionsand useful criticismsand John
Anthony and Spencer Titley for supervisingthe
thesisfrom whichthe paperwasderived. I wishto
thank Cheri Wachterand Lynn McLeanfor many
improvements in the manuscript.This studywas
fundedin part by NSF Grant GA41136. All com-
putingwas doneat the Universityof Arizona Com-
puter Center. The ComputerCenter'sdonationof
matchingfundsis gratefullyacknowledged.
DEPARTMENT OF GEOSCIENCES
UNIVERSITY OF ARIZONA
TucsoN, AmZ0NA 85719
]•tly 21, 1976; February 10, 1977
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