EconomicGeology

Vol. 87, 1992• pp. 23-43

Hydrothermal Ore-FormingProcessesin the Light of Studiesin Rock-

BufferedSystems:II. SomeGeneral GeologicApplications
J. J. HEMLEY
U.S. GeologicalSurvey,Reston,Virginia 22092

AND J. P. HUNT
8545 E1PaseoGrande, La Jolla, California 92037

Absiract
The experimental metalsolubilities for rock-bufferedhydrothermal systems, reportedby
Hemleyet al. (1992), provideimportantinsightsintothe acquisition, transport,anddeposition
of metalsin real hydrothermalsystemsthat producedbasemetal ore deposits.Water-rock
reactionsthat determinepH, togetherwith total chlorideand changesin temperatureand
fluid pressure,play significantrolesin controllingthe solubilityof metalsand determining
where metalsare fixed to form ore deposits.
Hydrothermalsystems circulatefluidsandheat,andthe transportpath of a hydrothermal
fluid is likely to lie somewherebetweenan adiabatic(no heat lossto adjacentrocks)and a
geothermal(completethermalequilibriumwith adjacentrock)path.The transportpath of
the hydrothermal fluidsemanating from,or circulatingnear,deep-seated crystallizing
plutons
canbe approximated by a quasi-adiabatic pressure-temperaturepath.In sucha quasi-adiabatic
setting,the pressureeffecton rock-buffered metalsolubilities
is significant
andallowsmetal
transportoverlongdistances because the trendof decreasingmetalsolubilitywith decreasing
temperatureis compensated by the trendof increasingmetalsolubilitywith decreasing pres-
sure.The high-temperature portionof a quasi-adiabatic hydrothermalsystemwill tend to
leachmetalsfrom the rock and fix K and Na in feldspars.The sourceof the extractedmetals
may be late-stagemagmaticmelt, trace metalsdistributedin the lattice of silicateminerals
destroyedduringrockmetasomatism, and/orsmallamountsof basemetalsulfidesdisseminated
throughouta givenrock.
Depositionof metalsin hydrothermalsystems occurswherechangessuchascooling,pH
increasedueto rockalteration,boiling,or fluidmixingcausethe aqueousmetalconcentration
to exceedsaturation.Relativemetal transportconcentrations, the availabilityof sulfur,the
disposition of the saturation surfaces relativeto eachother,andtheinterplayof thesevariables
throughtime are the major factorscontrollingthe patternof metal deposition(andnonde-
position).
Metal zoningresultsfromdepositionoccurringat successive saturationsurfaces.Zoningis
not a reflectionsimplyof relative solubilitybut of the mannerof intersectionof transport
concentrationpaths with those surfaces.The experimentalresultsare consistentwith the
typicaloutwardzonationof Cu-Zn-Pbobservedin porphyrycoppers,Butte-typebasemetal
veindeposits, skarns,andmassive sulfides. Implications
to mineralizationpatternsin Mississippi
Valley-type,sedimentaryCu, and other low-temperaturedepositsare alsoof interest,with
duerecognitionof the greateruncertaintyregardingspeciationandattainmentof equilibrium
in thoseenvironments. In suchdeposits, a probableoutwardzoningof Cu-Zn-Pb-Feissuggested
from the results.
Saturationsurfaceswill tend to migrate outwardand inward in progradeand retrograde
time, respectively,controlledby eithertemperatureor chemicalvariables.This,in turn, gives
riseto zonemigrationand,whereonezoneencroaches on another,the appropriateapparent
parageneticrelations.Suchtexturalimplicationsareincorrect,however,unlessviewedwithin
the contextof the overallmineralizationprocess.Additionalcontrolsbearingon metal pre-
cipitationsequence andcoprecipitation,thepresenceor absenceof zoning,reversals in zoning,
sulfidationstate,andtimingrelationsbetweenalterationandmetallizationare implicitin the
results and are discussed.

Introduction der conditionsthat are geologicallyreasonable,al-

THE work presentedin Part I of this report was an though by no meansall-encompassing, for hydro-
observational
study,at pressureandtemperature,of thermalore-formingprocesses. Geologicapplications
iron-copper-lead-zinc
sulfidesolubilityrelationsun- are therefore immediatelyevident and do not require

23
24 j. J. HEMLEYANDJ. P. HUNT

additionalcomputationsbased on thermodynamic tratedby the Buttesystem,discussed below,andmay

datathat are yet inadequatefor sucha purpose.Ac- be of moreimportance thanis generallyrecognized
cordingly,in this part of the paperwe proposeand in manyexamples of ore occurrence, particularlyfor
discussa number of applicationsto ore deposits rare metal and many high-gradebaseand precious
througha transport-deposition conceptualframework metal orebodies. Considerations such as these have
thatwe feel isimpliedby the resultsof the study.We been addressedby Skinner(1979).
wish to emphasizethe broad applicationsof the Third is the leachingof trace elementsfrom un-
chemistryto basemetal ore-formingprocesses, but mineralizedsourceor hostrocksin late magmaticand
we recognize,andattemptto address,the deficiencies postsolidificationtime by chloride solutionsdevel-
of ourgeneralizedmodelwith respectto the complex opedduringmagmaticdifferentiation,by convective
geologicproblemsinvolved.Additionalmodifying incorporationof seawateror salinegroundwater, or
considerations,aswell asapplications,are therefore by otherprocesses. Thesesolutions may,in addition,
respectfullyleft to the experienceand expertiseof increasein concentration by fluid-phaseimmiscibility
the reader. andboiling.The extractionprocess is conventionally
discussed
in termsof the Nernstdistributionconstant;
Metal Acquisition,Transport,and Deposition that is, the ratio of an elementor a pair of elements
Acquisition between fluid and mineral, fluid and melt, or mineral
and melt. Behind this formalism,however, one should
Let usbrieflyconsiderfirstmodesof acquisition of keepin mindthata replacement or exchange reaction
the ore-formingelementsby hydrothermalfluidsand is necessarilyinvolved.For example,for Pb in K feld-
the possiblerelevanceof this investigationto that sparwe mayassume a defectvacancyandthe reaction:
problem.The modesof acquisition fall intoessentially
threegeneralcategories.Firstisthe classicalprocess 2K+ + Pb(AlSiaOs)2 = 2KAlSiaOs + Pb+2, (1)
of acid volatile and exotic element enrichment in
magmaresulting from crystal fractionationand/or or for Zn in biotitewe maywrite:
otherdifferentiationprocesses, followedby separation
of an aqueousphaseandits partitionedconstituents 3Fe+2+ KZn3A1Si3010(OH)2
(e.g.,Whitney, 1975). Sucha processor combination = KFe3AlSi3010(OH)2 + 3Zn+2. (2)
of processes,althoughdebatablein detail,appearsto
be of fundamental importance, particularlyasregards Asshownin thisstudyandin Whitneyet al. (1985),
theacquisitionofvolatiles,thepegmatiteandoxyphile iron is a relatively abundantmetal componentin so-
suiteofmetals,andprobablycopperandmolybdenum lutionsequilibratedwith granitierocksandit, along
as well. For magmaticallyaffiliateddepositssuchas with hydrogenionsand the alkalies,is likely, there-
the porphyrycoppersand their skarns,this process fore, an importantagent in the extractionof other
alsoprobably appliesto Pb and Zn, but for various metals from trace element sources. Chloride is not
other deposit types, such as the sediment-hosted the only anion or ligand involved in the extraetion-
massivesulfides,the origin of the metals is more reerystallizationprocessesfor every metal and all
problematic. physical-chemicalenvironments,but its prevalence
Secondis the dissolution of minerals,accessoryor in geologicfluids and its generalcapacityto fulfill
major,composed largelyof the componentof interest. sucha functionindicatesa major, if not dominant,
This is illustratedby equations(10-12) (Hemleyet role.
al., 1992), whichinvolvedissolutionof metalsulfides Thesereactionsare basicallythe sameasthosedis-
andoxidesalreadypresentin the rock. Of these,iron cussedin the secondcategory,exceptthat thesedeal
isthe onlymetallikelyto be animportantaccessory, with minor componentsin a solidsolutionsubstrate
primarily asmagnetiteor ilmenite but sometimesas rather than with pure end-member phases.Also,
sulfide as well. Trace occurrences of other metals in leachingin theseinstances(i.e., where the phaseis
the iron phases,particularlyin magnetiteandpyr- not completelydestroyed)canneverbe completebe-
rhotite, are importantpotentialsourcesof thosemet- causethe activity of the leachedcomponentin the
als,but even with their partitioninto the aqueous solidphasemay fall to very low valuesbut never to
phasestronglyfavored,metalacquisition froma trace zero. The geoehemieal-hydrologie mechanismor
elementsourcewouldbe quantitatively insignificant modelby which extractedtrace elementsthen rise to
relativeto acquisition from an abundantmajorele- concentrationlevels required for precipitation (as
ment source,suchasFe from accessory magnetitein definedby the solubilitycurvesof fig. 3, Hemley et
an aqueouschloride environment. This secondcate- al., 1992, for example)in a postulatedenvironment
goryof extraction is the basis,of course,of the up- of deposition,is an additionalnecessary
consideration
gradingof weakly mineralizedvolumesof rock into sometimes overlooked in the assessment of source-
viable orebodies.This processappearsto be illus- rock and provenaneeproblems.
 HYDROTHERMAL ORE-FORMING PROCESSES:PT. II 25

Implicit in the extractionprocessis a control on

total acidityby rock-fluidequilibria.We havecalled
theseequilibria"buffer" reactions,but by thiswe do
not imply strictcontrolbut only a tendencythereto 600

in any real dynamic system."Mediative" reaction

mightbe a more appropriateterm. Thus,beginning
with the initial acid-volatilecomponentscontributed
by magmaticdifferentiationanddegassing (assuming
500
• K-felds
the magmais a sourceof chemicalcomponents

of at leastpartiallyeffectiverock-buffering
aswell
asheat in a giveninstanceof mineralization),a series
relation-
shipswill develop,culminatingin thosepresentat
the finalsiteof deposition.The pressure-temperature
400 Andalusi•e
""
"Ix
....
x•x\x
effectson solubilityat any point in the evolutionof
the fluid will be a function of the overall rock-buffer
relationship
involvedat thatpoint.Theywill be qual-
itativity similarto thosewe have seenfor the K feld-
3OO

200
Pyophyte
cøve
Kaolinitc
spar-muscovite-quartz(KMQ) and K feldspar-mus-
covite-plagioclase-quartz (QM) buffers,but modified
in the manner discussedearlier in Hemley et al.
(1992). i i i I I
0 1 2 3 4
Asa frameworkfor the experimentalwork, we have
usedthe aboveassemblages. Thesewere chosennot log •KC1/•HC1
onlybecausetheir phaserelationsare fairly well un- FIG. 1. Stability relationsin the systemK20-AI203-SiO2-H20-
derstoodbut alsobecausethey correspond
to some HCI (quartzpresent)at i kbarand i m total chloride,asa function
commonmineralizingenvironments. Thisincludesnot of temperatureand (K+ + KClø)/(H+ + HCIø), experimentally
only the lower temperature sericite alteration so determined.Dashedcurvesare the corresponding boundariesfor
characteristic of base metal sulfide mineralization in K feldsparat 0.5 kbars (lower values)and 2 kbars. The arrow
denotesan initial compositionfor late magmatic-hydrothermal
generalbut alsosomehighertemperatureassociations fluid, as discussedin text.
characterizedusuallyby the presenceof K feldspar
andbiotite(potassic or K silicatealteration),andmore
closelyrelated to the late magmaticenvironmentin Expressingthe relationsin terms of an end-member
the porphyrycoppers(Gustafson andHunt, 1975; Tit- reaction, and choosingFe becauseit is much more
Icy and Bean, 1981) and porphyry molybdenums abundantthanMg in a hydrothermalfluidequilibrated
(Wallaceet al., 1978). An examplefromButte, inter- with graniticrocks,we have:
mediatebetweenpotassicandMain Stagesericitic,is 3Fe+2+ KAISiaOs + 4H20
the early dark micaceousalteration(Meyer et al.,
K feldspar
1968) consistingof K feldspar-biotite-muscovite-an-
hydrite _+andalusite. = KFeaA1SiaO•0(OH)•
+ 6H+. (3)
Althoughthe bulk compositionof the acid-volatile biotite
productsof magmaticdifferentiationand degassing
will fall in the acidregionof the KMQ stabilitydia- Reactionsrelatingplagioclase,
biotite, pyroboles,
gram (Fig. 1; seealsoBurnham,1979), the cooling chlorite, and epidote are likewiseimportant.To il-
fluidsmayor maynotbe sufficiently acidto intersect lustrate:
the K feldspar-andalusite boundary.The arrowindi- 6H + + 5CaFeSi•O6
catesone possiblestartingpoint and eventualinter-
pyroxene
sectionwith the K feldspar-muscoviteboundary,but
in thefeldspar-stable
regionothercation/H+exchange = CasFesSisOss(OH)s
equilibriawill mediateacidity.The downwardpath amphibole
will not be vertical, therefore, as it will be modified
by thosereactions.The characteristicstartingpoints + 2SiO• + 2HsO + 3Ca+s, (4)
in terms of Y.KC1/Y,HC1 (or cation/H+ ratio in the
general sense)for systemsof variouscompositions, 4Fe+• + Cae(FeA1)(SiaA1)O•e+ 4SiOe+ 4HeO
and the pathsof descent,are importantinformation pyroxene
yet to be obtained from much-neededadditional re-
searchinto late magmaticprocesses. = CaFesAleSi7Oe.2(OH)e
+ Ca+• + 6H +,
Amongrelationsof interestis K feldspar-biotite. amphibole
26 j. j. HEMLEYANDJ.P. HUNT

Fe+2+ 2K+ + CaFesA12Si70•,2(OH)•

+ 2H,20 The pH rangebufferedby reactionsinvolvingpla-
amphibole gioclaseand the maficmineralsis lessacid than that
of the muscovite-bearingassemblages, andmetalsol-
= 2KFe3A1Si30•0(OH)2 ubilitiesare appropriatelylower. Notice that the for-
biotite mationof hydrousmineralssuchas amphiboleand
chloritemayoccurvia cation-fixationreactions,aswell
+ SiO• + Ca+• + 2H+, (6) as by hydrolytic reactionsas conventionallyenvi-
sioned.Mostof the abovereactionsapplyto the mod-
4K+ + 17Fe+• + 2CaAl•Si2Os
+ 24H•O + 16SiO• erate(•-'350ø-500øC) temperatureregion,aswell as
plagioclase to higher temperatures.At low temperatures,of
course,maficmineraland plagioclasehydrolyticre-
= Ca•FesSisO•,2(OH)• actions,suchas amphiboleor biotite to chlorite, or
amphibole plagioclaseto smectite,are more characteristic,but
chloritization, like sericitization, covers a broad tem-
' + 4KFeaA1SiaO,0(OH)a
+ 38H+, (7)
perature range.
biotite
In summary,numerousintermineral reactionsare
4H+ + 2KFe3A1Si•O•o(OH)• inherentlypresentin the complex,water-rockequi-
biotite libria of an evolvingmagmatic-hydrothermal system
that will, dependingupon the assemblage and pres-
= FesAlaSi3Oi0(OH)s
+ 3SiO2+ Fe+a+2K+, (8) sure-temperature, havea regulatingor controllingef-
chlorite fectonpH andmetalsolubilityrelationships. The pH
conditionsfor the KMQ andQM buffersusedin our
5Fe+• + CaAlaSiaOs+ 8H20 + SiOa work, therefore, serve as only one illustration.The
plagioclase characteranddegreeof wall-rockalterationbuffering
at the site of ore depositionis not the only consid-
= FesAlaSi3Oi0(OH)s
+ Ca+• + 8H+, (9) erationof importance,but the natureof the pH con-
chlorite trol in the higher temperaturetransportand source
Ca+• + 3CaA12SiaOs
+ 2HaO environmentisimportantaswell. We haveattempted
to incorporatein the abovediscussion the essential
plagioclase aspects of boththe orthomagmatic andthe convective
= 2CaaAlsSi30•aOH+ 2H +, (10) ground-water-leaching viewpointsof metal source,
but the transportand depositionalaspectsare inde-
epidote pendentof considerations asto source.
H2SO4 + CaAI•Si,•Os
Transportand deposition
plagioclase
Two hypotheticalend-membertransporttrajec-
= AlaSiOs+ CaSO4 + SiOa+ H20, (11) toriescanbe postulatedaspathsof escapefor fluids
andalusite anhydrite emanatingfrom crystallizingplutonsor from crustal
and hot spotsnear plutons.Usingthe isobdricsolubility
curvesfrom Hemley et al. (1992) as a basisfor dis-
2K+ + Fe+• + CaFesAlaSi7Oaa(OH)2
+ HaSO4 cussion,thesearethe geothermalpath,with complete
amphibole thermalequilibrationof the fluid with adjacentrock,
and the adiabaticpath, with no heat exchangewith
+ 2HaO = 2KFe3A1Si30•0(OH)a
adjacentrock (Fig. 2). An isobaricpath, whichmight
biotite
be applicableovera portionofthe fluidtraverseunder
+ CaSO4+ SiOa+ 4H+. (12) specialconditions,is seen to be fairly closeto the
anhydrite geothermalpath.The pressure-temperature pointsof
origin in Figure 2 are at 500øC and i kbar and at
Equation (12) is a relation characteristicof the de-
600øC and 2 kbars(500øC and 2 kbarsfor copper).
velopmentof potassicalterationin early, porphyry Nearly adiabaticconditionsin naturalsettingscould
coppermineralization(Gustarson and Hunt, 1975). be expectedto occur in environmentswhere fluids
In the abovereactions,the fixationof Mg+2 rather arefreelymovingin anopenfracture(whichapprox-
thanFe+•, withproduction
of H+, wouldbe of major imatesan isentropicreversiblepath), andwherefluids
importancefor submarine
mineralizing
environments are rapidly movingin a tortuousfractureconstrained
involvingthe convectiveintroductionof seawater.For by a physicalthrottle (which approximates an isen-
additionalrelationsrelevantto ore genesisandalter- thalpic irreversiblepath). Thus, there are two end-
ationthe readeris referredto paperssuchasBeane member casesfor adiabatictransport.Under the
andTitley (1981) or Bowmanet al. (1987). physicalconditionsconsideredhere, the isentropic
 HYDROTHERMAL ORE-FORMING PROCESSES:PT. II
adiabaticand isenthalpicadiabaticpathsare similar,
althoughthe isenthalpicdecompression path shows
lesstemperaturedecreasethan the isentropicpath,
and under lower temperature conditions,can even
lead to heatingof the fluid (Wood and Spera, 1984).
The adiabaticpaths shown in Figures 2 and 3 ap-
proximatethe isenthalpicpath for pure water (Burn-
ham et al., 1969). This approximationis assumedfor
illustrative purposesfor the end-membertransport
path, recognizingthat it may be less accurate for
chloride-richsolutions,especiallynear their critical
point.
The geothermalpathsrepresentpurelyconductive
heat lossfrom the fluid alonga linear temperature-
pressuregradientfrom the PT point at depthto con-
ditionsat the surface.This assumption is unrealistic,
becauseit hasbeen shownby variousinvestigators
(e.g., Norton and Knight, 1977) that hydrothermal
fluidscarrytheir thermalregimewith themandbring
high temperaturesto relatively shallowlevels in a
nonlinearmanner.Nevertheless,as part of a frame-
work for settinglimits on the diagram,suchan end-
member trajectory seemsappropriate. On cooling
along the geothermalpaths, or any paths close to
them, there is continuousprecipitationof the metals
from saturatedsolutionsthat remain in equilibrium
with the appropriatesilicatebuffers.
Along the arching adiabaticpaths, on the other
hand, there is an initial increasein metal solubility,
and therefore, a capacityfor leachingof metal com-
ponents.The adiabaticpaths stipulateno heat loss
from fluid to the surroundings, with coolingexclu-
sivelythe resultof expansion.Conditionsfor suchex-
pansionare expectedin the hydrodynamicsof vein
systems. Asexpansion continues,the carryingcapacity
of the fluid decreases.Solubility eventuallypasses
througha maximumandprecipitationbegins.Upward
verticalpathson the diagramscorrespondto isother-
mal expansion.These will not apply to an outward
movingpathbecausetheyrequirecontinuous addition
of heat to the fluid, but they will temporarilyexistin
that environmentwhere an incrementof convecting
groundwaterisapproaching a heatsourceandinitially
moving upward (Norton and Knight, 1977). The
heating-upprocesson the incomingfluid also con-
tributesto leaching.Thus, a regionof relativelyin-
tensemetal leachingwithin, andwithin the environs
of, a crystallizingintrusionwill existbetweenthe iso-
thermal and adiabaticpaths.
Any real path outward from the intrusionis com-
plex and difficult to predict, but it will tend to fall
somewherebetween the adiabaticand geothermal,
as illustratedby the quasi-adiabatic dashedcurve A
(Fig. 2a). It shouldbe near-adiabaticin the proximal
region and trend toward a geothermalslopeas con-
ductiveheatlossincreases for the moredistalpart of
the path. Obviously,metaltransportcan occurover
longdistances providedthatincreasedsolubilitydue
27
to pressuredecreaseis not morethan offsetby de-
creasedsolubilitydue to temperaturedecrease.
Mineral depositionis governedby any of the tra-
ditionallydiscussedcontrols.Theseincludea decrease
in temperature,an increasein pH, dilutionfor those
constituents solubilizedby highercomplexesdue to
high chloride concentration,mixing of chemically
disparatefluids,acquisition of reducedsulfurby the
fluid, lossof volatiles (includingboiling) that may
controlpH orfo• or contribute
to specific
ligandfor-
mation(suchas CO.2or H2S), and possiblecombina-
tionsof theseseveralprocesses.Progressive dilution
outwardby meteoricgroundwater,for example,will
modifytemperature,acidity,andchlorideconcentra-
tion concurrentlyto favordeposition.If suchchanges
are gradual,they imply a gradualdissipation of min-
eral load and less likelihood of distinct orebodies. Ore-
grademineralizationis favored,of course,by a large
changeovera relativelyshortspatialinterval,aswell
asby a longtime spanof activity.For furtherdiscus-
sionof depositional
controlin termsof pH, fs•, and
other chemicalvariables,the reader is referred to pa-
perssuchasBartonet al. (1977).
The foregoingportrayalof any givenintermediate
path, suchaspath A (Fig. 2a) describesone possible,
essentiallysteadystate,conditionin the evolutionof
a hydrothermalsystem.All hydrothermalsystemsex-
perience prograde and retrograde temperature de-
velopment,however, and someadditionalconsider-
ationsare thereforeappropriate.At a later time in a
progradesystem,the host-rockenvironmentwill be
hotter and path A will extendfarther from its point
of originbeforeapproachinga geothermalend-mem-
ber path. In fact, if the intrusionis either sufficiently
shallowor sufficiently largerelativeto itscoolinghost-
rock environment,a near-adiabaticpath couldtheo-
reticallyextenditselfto the surfaceandbe manifested
there simply as a fumarolicvapor plume. Certainly
the more common manifestationof peak develop-
ment, however,is either quenchingor boiling in the
ground-waterzone or at the seafloor. The attendant
cooling and chemical shifts during these processes
appear to be commondepositionalcontrols.These
are probablybestdocumentedin the epithermalpre-
ciousmetal systems(Reedand Spychef,1985; Reed,
1989) and the modernsea-floorsulfideoccurrences
(Goldfarbet al., 1983).
Another representationof the transport-deposi-
tional frameworkis givenin Figure 3. Here iron and
coppersolubilitiesare contouredas a functionof P
and T, and the same end-membergeothermaland
adiabaticpathsfrom the hypothetical600øC and 2-
kbar hot spotsare shown.The gas-liquidboundaryis
that of 1 m NaC1. Depositionoccurscontinuously
alongthe linear geothermalpath, whereasleaching
occursalongthe isenthalpicor adiabaticpath. An in-
termediatecoolingpath suchasA in Figure 2a is also
illustrated.This path is initially near-adiabatic,goes
28 j. j. HEMLEYANDJ. P. HUNT

IRON
COPPER

I I I i
300 400 500 600

T•

ZINC LEAD

I I I I I I I I
300 400 500 600 300 400 500 600
TøC T•
FIG. 2. Saturatedmetaltransportpathsfromhypothetical
intrusions
or crustalhotspots.Pathsare
plottedwithreference to theisobaric saturation
curvesof Figure3 (Hemleyet al., 1992).Asshown
in(a)foriron,end-member pathsareadiabatic andgeothermal.
Precipitation
occurs downthegeothermal
pathswhereas leaching
occursinitiallyalongtheadiabatic
paths.Dashed pathA illustrates
a geologically
morerealisticintermediatepath.Diagrams(b), (c), and (d) are analogous
relationsfor copper,zinc,
and lead.
 HYDROTHERMAL ORE-FORMING
through an interval of nondepositionparallel to the
contours,andthen beginsto crosscontoursin a man-
ner depictingprecipitationanda moreintensecooling
environment.As projected, the path correspondsto
a hypotheticaltransitionfrom a lithostatic,late-mag-
matic regimenear the sourceto a hydrostaticregime
in the more distal region. A lithostaticregime, al-
thoughapplicableto the porphyrycoppersand mo-
lybdenumsin their earlystagesof mineralization,does
not characterizethe bulk of their hydrothermalhis-
tory (Gustafsonand Hunt, 1975).
SimilarPT solubilityrelationscouldbe shownfor
the other metals, and because the contours would not
be parallelfrom metal to metal, it is apparentthat a
quasi-adiabaticpath correspondingto nonprecipita-
tion or leachingfor one metal could involve precip-
itation for another. In this way, a differentiationin
the precipitation processcould occur. For example,
alonga portionof the quasi-adiabatic path in Figure
3, iron will be leachedwhile copperisdeposited.Fig-
ures 2 and 3 are inadequatefor proper illustrationof
zoning,however,becausethey portraysaturationfor
all metalsat the momentof departurefrom the high-
PT hot spot.A different representationis therefore
givenin the followingparagraphs, whichisthen used
asa basisfor a generalizeddiscussion of mineralzon-
ing and parageneticrelationsin ore deposits.
Metal Zoning
Figure 4 is a compositeof the 1-kbar saturation rium with those oxide or sulfide accessories. Sulfur
curves(fromfig. 3, Hemleyet al., 1992) onthe KMQ
buffer for all of the metals. The dotted curves will be
2.0
1.0
0.5
FIG. 3. Saturatedtransportpathsandsolubilities
relationsin Figure2a. G = gas,L -- liquid,S = solid,assumingrelations
1 m NaCI. The intermediatepath A is analogous
to path A in Figure 2a.
PROCESSES: PT. II 29
discussedbelow. For the presentdiscussion, the rel-
ativepositionsof the curvesare importantbut notthe
absolute values on the ordinate. For example, the
curvesrefer to 1 m total chloride;for a higherchloride
concentrationthey will be raisedappropriately,pro-
vided the same metal chloride speciesdistribution
applies.Similarly,a higher pH buffer controland a
higherj• environment
will lowerthe curves,andvice
versa,but their mutualrelationswill remainbasically
the same. Because mutual relations will tend to remain
the samedespitechangesin bufferingconditions,the
1-m total chloridecompositediagramcanbe usedfor
general illustration,bearing in mind that for some
changes
in pH-j•-fo• bufferassemblage
andchloride
concentration,the relativepositionsof the saturation
curvescouldbe significantlydifferent. Certain char-
acteristicsof the curvesexistdue to the fact that they
are plotted on a log basis.The Pb and Zn curves,for
example,divergeslightlyat low temperatures,but in
fact, the difference in solubility is much greater at
500 ø than at 300øC (450 vs. 17 ppm). On a more
realistic arithmetic plot, therefore, the curves are
convergingat low temperature,not diverging.
As indicated earlier in the discussion, the metals
will possessdiffering degreesof saturationin their
evolvinghydrothermalfluid. Iron concentrationwill
be high at high pressure-temperature,reflectingei-
ther near-saturation with the common accessories or
partitioninginto the aqueousphaseof a melt-aqueous
fluid end-stagedifferentiatewhichis itselfin equilib-
concentration is difficult to assess,but observations
suchasthe evolutionof sulfurgasesin activesystems
Fe (ppm)
Cu (ppm)
/
/ L
6000
6OO
for ironandcopperon a PT grid, analogous
to
for theH•O-NaC1system at
30 J.J.HEMLEY
ANDJ.P.HUNT

The horizontalarrowsrepresenthypothetical,un-
dersaturated,transportpathsfor the respectivemet-
als.These concentrationvaluesmustvary with time,
and thereforethe valuesshownmight representthe
maximumvalue over a selectedtimespanof interest
for a givenmineralizationprocess.For the porphyry
coppersthis spanmight extendfrom late magmatic
to the beginningof pyrite-sericitealteration.Because
we yet lack a workabletheoreticalor experimental
basefrom which to deducetransportconcentration
valuesin the evolutionof hydrothermalsystems, we
mustreasonsomewhatafter-the-factanduseappro-
priate geologicconsiderations, notablyrelativemin-
eral abundancesand fluid inclusions, to aid in this
• 2 effort.For example,for copperin the earlieststages
of mineralization,the relationsin Figure 4 are some-
what unrealistic.Under pH-fs•-fo•bufferingcondi-
tionsmore appropriateto the high-temperaturepor-
tion of the porphyry copper environment,iron and
copper apparently exhibit comparablesolubilities,
thereby givingrise to a depositionalpattern of com-
parable abundance of Cu and Fe. A limitation of
Figure 4 is that it impliesthat K feldspar-muscovite-
quartz and K feldspar-andalusite-quartz are the me-
diatorsfor acidityin the highertemperatureenviron-
ments. As discussedearlier, however, this would not
be the casein manysystems.
200 300 400 500 600
The prominenceof K feldspar-biotitein porphyry
TEMPERATURE 'C coppermineralizationhasalreadybeen noted.Also,
the earliestcopper-ironsulfidemineralizationisbor-
FIG.4. Composite 1-kbar,l-m totalchloridesolubilitydiagram
usingthe K feldspar-muscovite-quartz buffer in the mixedsulfide nite or bornite-chalcopyrite,
oftenin association
with
system,showingimplied transport,deposition,and zoningrela- magnetite.Bornite-chalcocite-magnetite,thoughless
tionsfor the metalsasa functionof temperature.Other controls common,alsooccurs.Exploratory experimentswere
are discussed in the text. Dashed extensions of the saturation
therefore run with K feldspar-biotite-magnetite-
curvesare visualextrapolations.Horizontal arrowsare undersat-
uratedtransportpathsfor the metalsin anincrementof migrating, quartz-chalcopyrite-bornite
as the fs•-fo2-pHbuffer
coolingsolution.Precipitationoccursdownthe saturationcurves assemblage at 500øC and 1 kbar (seefig. 2, Hemley
when the curvesare intersected.With pressureasthe third axis, et al., 1992, for the sulfidephaserelationsandHewitt
the saturation curves become PT saturation surfaces. The dotted
andWones,1984, andCyganet al., 1991, for refer-
curves are hypothetical saturationcurves for Fe and Cu under
differentbufferingconditions,asdiscussed in the text.
encesonfoa). The biotite wasnaturalmaterialwith
an FeO/MgO ratio of approximately2. A high KC1
concentration(6 m or 31%) was used inasmuchas
fluid inclusionsindicatehigh chloride (35-40 wt %
andthe occurrence of pyrrhotitein the BishopTuff NaC1equiv) in the early fluids (Gustafsonand Hunt,
(Hildreth, 1977) have obviousimplicationsto the 1975) and the occurrenceof chalcopyritedaughter
compositionof late magmaticmeltsandassociated as- mineralpointsto high Cu concentrations (Sawkins,
semblages. Copperconcentration maybe closeto sat- 1981). The averageof three runswasapproximately
urationsimplyby virtueof the lowsolubilityof chal- 2,000 ppm Fe and 600 ppm Cu, with the aqueous
copyrite,whetherthesource beaqueous partitioning Fe/Cu ratiorangingbetween3 and4. The bulkacidity
froma melt,extraction froma sparse chalcopyrite ac- of the fluid (H+ + HCI'), as estimatedfrom quench
cessory, or extraction as a trace element from other pH, wasnearly an order of magnitudelessthan that
phases.Lead and zinc, whatever their absolutecon- on KMQ in i m KC1, hence the lower total metal
centrations, are derived as trace element extractions solubilitydespitegreater opportunityfor chloride
frommineralsor froma late magmatic melt.Zincin complexing.Note that equation(3) isnotKC1depen-
Figure4 is shownhigherthanlead,sincezincis gen- dent, andtherefore,the highbulk aciditiesgenerated
erallymuchhigherin itsnaturaloccurrences in rocks by KMQ at hightotalchloridedo not exist.Leadand
(Wedepohl,1972, 1974a),but bothwill be far from zinc solubilities are also lowered, of course, under
thesaturation
valuesofsphalerite
andgalena inahigh- thesedifferent bufferingconditions.
PT environment. The new concentration values for Fe and Cu at
 HYDROTHERMAL ORE-FORMING PROCESSES:PT. II 31

500øC fall on the two dotted saturation curves shown

Porphyrycoppersand othermagmatic
in Figure4. The valuesrequiremorerigorousquan- hydrothermaldeposits
tiffcationasequilibriumpointsbut are adequate for
thisillustration.The dottedhypothetical saturation Usingthe KMQ curvesfor illustrationof zoning
curvesare drawnto mergewith the KMQ curvesat but keepingtheforegoingdiscussion in mind,thatfor
lower temperature,whereKMQ moreoftenconsti- typicalporphyrysystems the transportarrowswould
tutesthe characteristic buffer.With decreasing tem- intersect the dotted curves,at the onset of mineral-
perature from 500øC, the curvestraversetransitional izationthe iron and coppertransportpathswill in-
alterationtypes,suchasbiotite-chloriteandchlorite- tersecttheirrespective saturationcurvesat a fairly
sericite, but accurate delineation of suchrelations in- hightemperature.Movingdownthe iron curve,de-
volvingnewbuffers,assemblages, andvariedconcen- pendingon62 andtemperature,oneor moreof the
trationsmustawaitfurtherstudy. iron mineralsinvolvedin the studywill be precipi-
The aqueous Fe/Cu ratiogivenby the pointsis in tated.At anygivenconcentrationof total sulfurin the
satisfactoryagreementwith abundanceratiosfor Fe fluid,relativestabilities will favora trendfrommag-
andCu in the earlyassemblages of the porphyries, in netite to pyrrhotiteto pyrite at successivelylower
contrast to theveryhighratioimpliedby thetransport temperatures.Magnetite is commonas a late mag-
arrowsshownfor Fe andCu on the KMQ curvesand maticor earlyhydrothermal phasein the porphyries,
controlledby the pyrite-pyrrhotite-magnetite-chal- andpyriteistheabundant lowertemperature mineral.
copyrite(or pyrite-hematite-magnetite-chalcopyrite) The rarity of pyrrhotitepresumably resultsbecause
assemblage.Strict agreement, however, between fo2doesnottypicallyfallto lowenoughvaluesin the
transportconcentrationvaluesand mineral abundance porphyry copper environment.
ratiosshouldnot be expected.Abundanceratiosre- Associated with magnetite,and outsideof a rela-
flect the integrationof metal flux (concentrationtivelybarrencorezone,chalcopyrite or bornitewill
X flowrate)overtime (sometransportconcentrations be deposited. The typical early,high-temperature as-
maychangemorerapidlythanothers)aswell ascom- semblage in the porphyries isbornite ___
chalcopyrite
pleteness ofprecipitation, beyondthe _ magnetite,followedby chalcopyrite,and then
considerations
scopeof this generalizedpresentation,and of our chalcopyrite-pyrite outward in thepattern.Pyriteand
currentunderstanding oflatemagmatic-hydrothermal borniteare antithetic(Gustafson andHunt, 1975).
evolution.Anotherfactoraffectingmineralabundance For Main Stage vein mineralization at Butte, later
ratiosis the possibilityof somemagmaticcrystalli- stagesof porphyrycoppermineralization,and most
zation of a copper-ironsulfidemineral or minerals. Cordilleranor Andean-typebasemetal mineraliza-
This point is further discussed
below. tion, the iron transporttrajectoryintersects its satu-
The transportpathsare horizontalon a concentra- ration curve at a lower temperature, in the pyrite
tion-temperatureplot, but in reference to pressure rather than magnetite field of precipitation, and the
as the third dimension,they will follow curvedtra- pyrite is an earlier productfrom an incrementof fluid
jectories. With pressureconsidered,the saturation than is a copper-ironsulfide.
curvesbecomesaturationsurfaces andthe piercement Lead and zinc, becausethey are well below the
pointsarepointswhereprecipitationbegins.Geologic saturationvaluesfor galenaandsphalerite,musttravel
precipitationpaths,whateverthe metalinvolved,will to muchlowertemperatures beforeintersectingtheir
plot on suchsurfaces.Horizontaltransportpathsfor saturationcurves. This high degree of undersaturation
the metals,asthey emergefromthe hypotheticallate is obviously the reason that porphyry leadsandpor-
phyryzincsshouldnotbe expectedin naturalsystems.
magmaticor high-PThydrothermalenvironmentthat
Tracing the path of a given incrementof solution
producedthem, are shownonly for simplestillustra-
acrossthe diagramfromright to left, anddescribing
tion.The pathscannottrenddownwardbecausethey the idealizedsequence of precipitationfor the system
are not yet precipitatingmetal, but they may trend
we have postulated,iron will precipitate first, then
upwardalonga quasi-adiabatic path and continueto be joinedby copper,then iron pluscopperby zinc,
gathermetalasthey movethroughthe rocks(but as andsoforth.Asiron,however,becomes progressively
notedearlier,copperismuchlessaffectedby a pres- depleted(moreexactly,asthemassof ironbeingpre-
suredropthantheothermetals).Theimportantpoint cipitateddecreases logarithmicallydownthe curve),
is that the pathsare undersaturateduntil they inter- lessiron will be coprecipitatedwith zinc than with
secttheir respectivesaturationsurfaces.Precipitation copper,andevenlesswill be coprecipitated withlead.
thenoccursdownthe successive surfaces astheyare Sucha controlon coprecipitationwill apply to any
intersectedby the outward-migrating incrementof metal relative to its successors throughoutthe se-
solution.The readermaypreferrepresentation of the quence.The patternof sequentialprecipitationsim-
saturationcurvesandtransportpathsona molalrather ulatesthat seenin the Cordilleranor Butte-typeore-
thanpartsper millionscale,but mutualrelationships bodiesthemselves,asdiscussed, for example,by Pe-
would remain the same. tersen (1965b) in his review of the applicationof
32 j. j. HEMLEYANDJ.P.HUNT

conventionaltriangular saturationdiagramsto ore- phyries, althoughpart of the sameoverall thermal

formingprocesses. event,isnot the outerexpression of the earlyprotore
As typified by Butte Main Stageveins, lead and mineralization,or if so, it occursto a very minor ex-
zinc are observed in the outer reaches of mineraliza- tent. Rather, the sericite-pyritealterationincreases
tion asa sphaleritezone followedby a galenazone, in intensitywith time and appearsto be associated
(althoughmanganesemineralization is much more with continuingtectonicdevelopment,morethrough-
abundantthangalenain the peripheralveinsat Butte). goingfracturing,and a greater contributionby me-
Unlesscarbonatehostrock is presentin the environ- teoric water. It is clearlysuperimposedon the earlier
ment,however,leadandzincappearto be essentially hydrothermaleffects.In fact, the alterationdestroys
lostfrommostporphyrycoppersystems, perhapsdis- and remobilizessomeof the early mineralization.
sipatedin a near-surfaceground-waterzone and hot In termsof the systematics of Figure4, the pyrite-
springenvironment.This suggestionis basedon the sericite-quartz mineralizationat thislater, coolertime
relative paucityof porphyry copperlead-zincmin- is representedby a horizontaltransportpaththat has
eralization in silicate host-rock environments, but it movedto lower concentrations in the figure,thereby
shouldnot be overgeneralized.The concentrations of intersectingthe iron saturationcurvefartherout and
lead and zinc may simplyhave been exceptionally producingthe characteristic pyrite cap andhalo.At
low in some systems.At Potrerillos, Chile, for ex- thistime,the pathfor copperhasfallento insignificant
ample,no lead-zincmineralizationoccurs,but a car- low values as far as mineralization is concerned. The
bonate-bearingsectionis present. transportpathsfor lead andzinc alsowill havefallen
The closeproximityof the lead and zinc curvesin to low values,but not necessarilyat the samerate as
Figure 4 is in agreementwith the generallycloseas- that of copper.In fact, the peak concentrations for
sociation of lead and zinc mineralization in the field. the lead and zinc pathsappearto occurat a slightly
The width of the sphaleritezone producedbefore later time than that of copper,assuggestedby field
beginningof galenaprecipitationdependsuponrel- relations (Atkinsonand Einaudi, 1978). Transport
ative concentrations,but during much of the miner- concentrations for differentmetalsappearto rise to
alization(i.e., afterthe Pb curveis reached)they will their highestlevels,andfall to low levels,at somewhat
coprecipitatedown their respectivecurvesand give differenttimesin the overallmineralizationprocess,
rise to the mixed sulfidetexture typical of lead-zinc with magmaticdegassingand meteoric water con-
ores. vective activity decliningover a still greaterspanof
Anotherinfluenceon zoningin the porphyrycop- time. These observations illustrate that we must con-
persis evidentin the pressurecurvesof figure3 in sidernot onlythe effectsof earlysolutionson precip-
Hemley et al. (1999,).Copper solubilityis muchless itation sequencesand the resulting mineralization
enhancedby pressuredecreasethanthoseof the other patternbut alsothe effectsof changingsolutioncom-
metals.This differenceimpliesthat the explosivehy- positionwith time. Thesepointsare discussed more
drofracturing event and pressurerelease ("second fully in the next section.
boiling") that is possiblein late magmatiecrystalli- The alkali-fixationchemistryof the innerporphyry
zationasa resultof PH2O build up (Burnham,1979), zone (Creasey,1959) is in agreementwith the quasi-
andwhichpresumablygivesriseto the pervasive,fine- adiabaticpathin Figures2 and3, asillustratedby the
texturedstockworkcharacteristic of the porphyries, shift of equations(10-12) (Hemley et al., 1992), to-
will stronglyinducelead, zinc, andiron to moveout- ward K feldsparwith decreasein pressure.This path
ward in the system,whereascopperwill have a ten- also implies metal leachingand there maybe some
deneyto remainwithin the plutonandits immediate leachingof ironin thiszoneat E1Salvadorasindicated
environs.It shouldbe pointedout, however,that the by the disappearanceof a portion of the accessory
outwarddecreasein Cu/Fe ratio anddisplacement of iron oxides(Gustarsonand Hunt, 1975). In fact, the
lead andzinc, with copperbeingdeposited,are con- potassically alteredbarrencorezoneof the porphyries
sistentwith the effectsof a high-temperaturequasi- is itself permissiveevidenceof sucha leachingpro-
adiabatictransportpath, such as that illustratedin cess.In otherwords,the simplecoolinganddeposition
Figures9,and 3, regardlessof the accentuatingeffect depictedin Figure 4 may havesuperimposeduponit
of the late magmatiehydrofracturingevent. at the highesttemperaturessomemeasureof the adi-
Alteration is an intrinsic part of the metallization abatic effect which limits or reverses the metallization
processes just discussed. The alterationpattern as- process.To the extentthat the adiabaticpath devel-
sociatedwith earlyandhighertemperatureporphyry ops,it is analternativemechanism offeldspathization
metallizationis KNa feldsparandbiotite in the inner to that describedin Hemley et al. (1980), whichpro-
bornite-ehaleopyritezone and ehlorite in the outer poseda pluton-drivenconvectivesystemwherebyal-
ehaleopyrite-pyrite zone(Gustarson andHunt, 1975). bitization (and possibledesilication)occursat the
The heavy quartz-serieite-pyritealterationso char- bottom of the body where incomingwatersare heat-
acteristicof the upper andmarginalzonesof the por- ing up andK feldspathization (andsilicadeposition)
 HYDROTHERMAL ORE-FORMING PROCESSES:
occursoutwardfrom the top where they are cooling.
For plagioclase,Na enrichment occurs at the top.
These effectsare due to the direction of changeof
the equilibrium constantsof the feldspar exchange
reactionswith temperature. Such a pattern, for ex-
ample, is observedat Yerington, Nevada (Carten,
1986). The feldspathization that resultsfrom pressure
decrease,however, as comparedto convectivecool-
ing, apparentlywill not causepreferentialfixationof
K in the alkali feldsparsproduced.If any changeoc-
curs it should be minor fixation of Na. The K-Na-Ca
data in table 2, in Hemley et al. (1992) are fairly
coarse,but they indicate little or no changein the
aqueousNa/K ratio from high to low pressure.On
the other hand, the aqueousNaZ/Caratio doesde-
crease.This decreaseimplies that, as pressurede-
creases,Na will be fixed at the expenseof Ca in pla-
gioclase.This relation is in agreementwith a major
feldspathizationeffect observedat E1Salvador(i.e.,
oligoclasereplacementof a more calcicplagioclase)
(Gustarsonand Hunt, 1975). Both the temperature-
and pressure-controlled processesof alkali fixation
will occur to varying degrees,of course,in natural
systems.
Another plausibleapplicationof the alkali-fixation
reaction that occurswith decreasein pressureis the
origin of the sericite-islandtexture characteristicof
the early dark micaceousalteration at Butte (Meyer
and Hemley, 1967). In this pattern, muscoviteis al-
ways separatedfrom quartz by a rim of K feldspar.
As pointed out by M. H. Reed (pers. commun.),the
K feldsparrimmingmaywell havebeen the resultof
a pressuredecrease(e.g., from lithostaticto hydro-
static)that probablyoccurredwith the changefrom
Early to Main Stagemineralizationrather than the
result of a later increasein K activity or temperature
(Brimhall, 1977).
Hydrolytic alterationoccursalongthe remainder
of the mineralization-alteration path in the porphyries
outwardfrom the zoneof potassicalterationandhigh
Cu/Fe mineralization.The alteration sequencepro-
ducedis typicallybiotite-chlorite,chlorite,and chlo-
rite-sericite.This changeresultsfrom HC1 released
on sulfideprecipitationaswell asfrom the increased
dissociationof entrainedacidicconstituents(i.e., HC1
plusthe H2SO4derivedfrom SO2disproportionation;
Meyer and Hemley, 1967). At shallowlevels, an ad-
ditional increment of acidity is likely to be derived
from oxidation of HgS.
The foregoingdiscussion of porphyrycoppermin-
eralizationhasbeen oversimplifiedin the sensethat
theseorebodieshave a complex,multi-intrusiveevo-
lutionaryhistory.Despitesuchcomplications, the ex-
pectedpatternof metal zoningin the porphyriesand
in vein depositssuchasButte, Montana,and Magma,
Arizona (Hammer and Peterson,1968), is consistent
with geologicobservation. This patternalsoholdstrue
PT. II 33
for other complexmagma-relatedorebodiessuchas
skarns(Einaudi, 1982), Cordilleran-basemetal de-
posits (Petersen, 1965a), volcanogenicmassivesul-
fides (Franklin et al., 1981; Ohmoto and Skinner,
1983), and carbonate-hosted,skarn-related,sulfide
depositssuchas the chimneyand mantodepositsof
Mexico (Megaw et al., 1988). Iron nearestthe source
is sometimespresentedas pyrrhotiteand/or magne-
tite, but pyrite is usuallythe characteristiciron min-
eral. The zoning outward in the sulfideassemblages
is again Cu-Zn-Pb. The intensity and locationof Fe
mineralizationcan be quite variable.At Jerome,Ar-
izona,for example,the pyrite zoneoccursoutsidethe
chalcopyriteand sphaleritezones(P. Lindberg,pers.
commun.),which in terms of Figure 4 corresponds
to a lower concentrationvalue for the Fe transport
path, and therefore, intersectionwith the Fe satura-
tion curvebeyondthe corresponding intersections for
Cu andZn. The geologicenvironmentof volcanogenic
massivesulfide mineralizationis quite distinctfrom
that of the porphyrycoppers,but the chemicalcon-
trols on mineralization, as broadly outlined in this
study, would neverthelessapply. In the porphyry
copper skarns,iron metasomatismis as frequently
manifestedassilicateandoxideasit is sulfide.Astyp-
ified by the Bingham,Utah, district, iron in silicate
tends to showan interestingand distinctivepattern
correlativewith sulfidedistribution:andraditegarnet
(with crosscuttingchalcopyritemineralization)near-
estthe intrusion,and iron-rich pyroxene(with cross-
cuttinglead-zincsulfides)farther out (Atkinsonand
Einaudi, 1978). The Cu-Zn-Pb pattern at Bingham
(Hunt, 1924; RubrightandHart, 1968), with the most
distal lead mineralization occurring in unaltered
limestone,is one of the classicexamplesof district-
wide, basemetal zoningin ore deposits.
Referring to Figure 4, someadditional considera-
tionsshouldbe noted.The zoningsequencediscussed
is based on the saturationcurves (or surfaces)pre-
sentedin Figure 4, asfoundin our experimentalstudy.
However,a changein chloridespeciationof onemetal
relative to another, as a function of temperature,
pressure,or chloride concentration,will changethe
slopesof the respectivesaturationsurfaces.In terms
of chloride, this canbe visualizedby assumingchlo-
ride concentrationas a third axisin Figure 4. Inas-
much as the diverging-converging surfacesare then
more likely to intersect, differencesin speciationin
differentenvironmentscantheoreticallyresultin dif-
ferencesor reversalsin metal zoning.
Anothercontrolon zoningsequenceis the position
of the transportpaths.The Zn path on the diagramis
arbitrarily drawn higher than that of Pb becauseZn
is typicallymoreabundantin igneousandclasticrocks
and therefore is expectedto be more abundantas a
leachedor late magmaticderivative. For that reason,
even if lead solubilitywere slightlylower than that
34 j. j. HEMLEYANDJ. P.HUNT

of zinc,whichispossible withinthe experimental un- real system,copper mineralizationmay occur but it

certainty, zoningrelationswould tend to remain the will be relativelyweak and not of the true porphyry
same.However, if the Pb and Zn arrow pathswere type. Fournier (1967) has discussedsome of these
interchangedit is apparentthat their zoningwould problemsin relationto coppermineralization at Ely,
be reversed because the Pb curve would be reached Nevada.Saturation on the liquidusmaytypicallyoc-
before the Zn curve. This control is an illustration of curat thetimeofhydrofracturing anddecompression
the "massactioneffect"discussed by Taylor (1963). duringlate-stage magmatic crystallization.
In anycase,
We preferthe phrase"transportconcentration effect" liquidussaturation
isa possibilitythatintriguedMeyer
becauseit conveysthe role of a movingfluid aswell on the basisof purely geologicobservation,and it
aschemistry,but in either caseit is obviouslyan ex- remainsaninterestingtopicfor muchneededresearch
tremely importantfactor in determiningthe course intolatemagmaticcrystallization-differentiation pro-
of anymineralizationprocess.Continuedresearchon cesses.The calculationsof Cline and Bodnar(1991)
extractionchemistry,suchas equations(1) and (2) are a step in that direction,but more experimental
and manyanalogous relationships, will help resolve work is needed.
questions asto the originandcontrolson theseearly In usingFigure 4 as an illustrationof zoning,we
concentration relations. In this connection numerous haveimplicitlyassumed a temperaturecontrolon de-
workersmerit recognition,suchasGraybeal(1973), position.While temperatureis no doubtof majorim-
Sverjensky(1985), Hendry et al. (1985), and Ilton portance,particularlyon a broador districtwidescale,
andVeblen(1988) on mineralogical problems;Can- other controlscan be assumedalongthe horizontal
dela andHolland (1984) and Urabe (1985) on melt- axiswith equivalentresults.IncreasingpH in the di-
fluidpartitioning;Smith(1979) andHildreth (1981) rectionof transportat constanttemperaturequalita-
on magmazoning;SeyfriedandMottl (1982) on sea- tively hasthe sameeffectasdecreasing temperature
water-rockinteractions,and many others.Progress in the directionof transportat constantpH. Zoning
will be slow,however,becauseof the complexand relationswill remainthe same.Similarly,if precipi-
generallyobscurenature of the sourceand prove- tation is the result of entering an environmentof
nanceproblem. higher H2S or sulfideion activity, the metalsmost
The same considerations on the control of initial sensitiveto sulfidewill precipitatefirst (i.e., the sol-
or early transportconcentration valuesapplyalsoto ubility sequence givenby the curvesin Fig. 4), but
copper.Coppertendsto be fairly abundantasa trace zoningrelationsagainwill remainthe same.
constituentin intermediateand mafic igneousrock The availabilityof reducedsulfuris of majorim-
(Wedepohl,1974b) and perhapsgenerallyexperi- portanceto the problemof depositionor nondepo-
ences increased enrichment in the differentiation sitionof the metals.We haveassumed amplesulfide
process leadingto the formationof porphyrycoppers, in our discussionthus far, but it will be recalled that
aswell. But,if aqueous Cu isappreciablyhigherthan we are dealingexperimentallywith sulfide-deficient
asillustratedon the curvein Figure 4, it impliesCu solutions,which may, in fact, be commonin ore-
supersaturation at the end stagesof igneouscrystal- formingprocesses (e.g.,fluidinclusionevidencecited
lization. In other words,a copper-ironsulfidewill by Roedder,1979, andthe prominenceof sulfatein
precipitateon the liquidusin a melt-solid-aqueoussomedepositsasmentionedin Hemleyet al., 1992).
fluid systemif saturationis achievedthat early.This This deficiencycanexistwhether we conceiveof the
isa pointthathasnotbeensettledin porphyrycopper sulfurasentrained in thefluidor ofthefluidaspassing
genesis.In classicdisseminatedmineralization,bor- througha moresulfur-rich environmentat somepoint
nitc and chalcopyriteblebsare sometimesobserved alongits path, asinto seawatercontainingbiogenic
in K feldsparandquartzcrystalsbut neverin plagio- H2S.Referringto Figure 4, for example,if limited
clase.That they aretruly lockedin quartzisevidenced sulfuris available,it canbe substantially
consumed
by their survivalof the rigorsof acid supergeneal- in precipitating Cu and Fe down their curvesbefore
teration (Gustafsonand Hunt, 1975). Most of these galenaandsphaleritesaturationis ever attained.Sim-
blebsexistat crystalboundariesand alongminute, ilarly,limitedsulfurduringdeposition of sphalerite
almostinvisible,hairlinecracks,whichis wherethey canresultin muchof the sulfurbeingconsumed be-
would be expectedto be, coexistingwith the asso- fore galenaprecipitation
is reached,thuscausinga
ciated aqueouschloridefluid that rejected them. In relativelylimited measureof lead mineralization.This
CharlesMeyer's view, porphyrycoppergenesismay situationmay have occurredat Butte, as suggested
well be an expression
of evolutionanddifferentiation by the very smallamountof lead mineralizationcom-
of the late magmaticmelt to the extentthat suchliq- pared to zinc.
uidus saturation does occur. If differentiation is in-
Sulfurdepletionhasthe effectof raisingthe satu-
terrupted before this point by intrusion,a distinct ration curvesof the remainingmetalsand thereby
tectonicbreak,andthe development of a hydrother- increasingthe degree of undersaturationof the re-
 HYDROTHERMALORE-FORMINGPROCESSES:
PT. iI 35

spectivetransportpaths.As a consequence,precipi- of the curvesin Figure 4 to lower temperatureen-

tationof the remainingmetalsis shiftedto lower tem- vironments,suchthe Mississippi Valley-typedeposits,
peraturesandmightevenbe lostfromthe system.As are worth considering,if only for instructionalpur-
mentionedearlier with respectto leadandzinc, such poses.Simple visual extrapolationsuggestsPb-Zn
a lossmaybe substantially true for porphyrysystems valueson the order of 10 ppm at 100øC for thissys-
in silicate host-rockenvironments.A questionthat tem, but with the total chloride significantlyhigher
remainsis whether the metalsare permanentlydis- (e.g.,the • 5 m valueof manyMississippi Valley-type
sipatedand lost in an attenuatedhot spring-ground brines),suchnumberswouldbe raisedconsiderably.
watersystem,widelyanddiffuselydepositedin a pro- There is considerableuncertainityasto the character
pylitic zone in somedepositsor typicallydeposited andrangeof buffering,of course,but aspointedout
in an epithermalenvironmentat higher levels. in the abovediscussion of high-temperatureenviron-
In a more reactive carbonate environment, char- ments,the mutual relationsof the curvesmight well
acterizedby a shift in solutionpH to higher values remainmuchthe same.The controlon the suggested
and therefore a downwarddrop in the solubility inflection in the experimentalcurvesin the 300øC
curvesof Figure4, thereappearsto be adequatesulfur regionisweak,but aninflectionmusteventuallyoccur
for precipitationof the lead and zinc, or at leastan (as can be seenmore clearly on an arithmeticplot)
appreciableportion thereof, in most instances.The becausethe curvesmustpassthroughessentially zero
absence of lead-zinc mineralization in districts such concentrationat earth-surfacetemperatures.
asPotrerillos,Chile, discussedaboveis likely not the For the MississippiValley-type deposits,acquisi-
resultof sulfurdeficiencybecausesignificantevidence tionof metalsiscommonlyviewedashavingoccurred
for hypogeneleadandzinccarbonatemineralization in basinalbrinesat moderatelyelevatedtemperatures,
would be expected.Thus, the more solubleiron ap- with depositionoccurringin rocksupdip in a shelf
pearsto be the major excessmetal. Correlativeevi- carbonateor a reef-typeenvironment.If represented
dence for this assumptionis the iron metasomatism in Figure4, therefore,they wouldbe shownasorig-
that often occurs,assiderite,magnetite,andcalc-sil- inatingat no morethanabout250øC andproceedto
icate mineralsin carbonate-hosteddepositsassociated the left to cut the saturation curves in the 100 ø to
with magmatic
activity. 150øC region.The controlon precipitationmaybe
In summary,dependingupon the availabilityof acquisitionof reduced sulfur or someother mecha-
sulfur,aswell astransportconcentrationrelationsof nism. For low-temperatureenvironments,the very
the metals,Fe-Cu depositswithoutPb-Zn, or Fe-Cu- highironconcentrations characteristicof chlorideso-
Zn depositswithout Pb, asare socommonin the por- lutionsequilibratedwith granticrocksat high tem-
phyriesand massivesulfides,are to be expected.On perature will not exist. All transportpathswill plot
a fine scale,thesecontrolsevenapplyto the chimney at lower concentrationson the diagram.Anotherim-
walls(HaymanandKastner,1981) of the modernsea- portant feature in Figure 4 is the greater separation
floor sulfide occurrences. The temperature and that occursat low temperaturesbetween the iron
chemicalgradientsin the walls are steep,but they curve and the lead and zinc curves than occurs at
are qualitativelythe samegradientsasthoseillustrated high temperatures.In other words,iron tendsto re-
in Figure 4. Changingtransportconcentrationvalues mainin solutionmoreat low temperaturethanat high,
with changein sourcerock may, in turn, generally relative to the other metals. These considerations
reflect changingrock-fluidand melt-fluid element suggestthe likelihoodof a differentzoningposition
partitioningrelationsin an evolvingpetrogeneticse- for Fe, namely,on the outsideonly. Distinct zoning
quencefrom basaltto felsic igneousrock (Sawkins, in the Mississippi
Valley-typedepositsis oftendifficult
1990). Ore districtsthat are very high in lead are to define, probablybecausemultiple stagesof min-
more difficultto explain,and in the contextof Figure eralization (Hagni and Trancynger, 1977) obscure
4, require higher transportlead concentrations rela- relations.A tendencytoward outward and upward
tive to other metals than occur in the usual case. The zoning in the sequencechalcopyrite-sphalerite-ga-
mostappropriateand reasonablesourceis often dif- lena-pyrite(marcasite) is suggested
in somedeposits,
ficultto define.Isotopeshavegreatutility in assessing however,asillustratedby relationsin the Buickmine
source,andthe considerable researchactivityexisting of the ViburnumTrend (RogersandDavis, 1977).
in this areais well justified. Low-temperaturecopper replacementdeposits,
suchasWhite Pine, Michigan(White, 1971), andthe
Lower temperaturedeposits red-bedcoppers(which,of course,are not red where
Let usnow turn our attentionto lowertemperature the copperoccurs),alsoexhibitthe patternexpected.
and apparentlynonmagmatically affiliatedorebodies. In thesedeposits,the sourceof sulfurappearsto be
Althoughourtemperatures of experimentation extend generallyindigenouspyrite. With copper-bearingso-
onlyto 300øC,the implicationsof the generaltrends lutionsenteringthe system,andwith the pyritecurve
36 J.J. HEMLEYANDJ. P. HUNT

well aboveanycoppermineralcurvein Figure4, iron tain. Becauseof theseambiguities,the term paragen-

isprogressively solubilizedandflushedout ascopper esiscurrentlyseemsto imply, for manyauthors,sim-
is fixed.The resultis a zonationof decreasing Cu/Fe ply the mode of origin of a phase relative to its
ratioandincreasing J•2,awayfromthe source,man- neighbors,includingall processes that might be in-
ifestedas copper,chalcocite,bornitc, chalcopyrite, volvedin the texturaldevelopmentof a suite (e.g.,
and pyrite, althoughall membersof the seriesmay by exsolution,recrystallization,
fracturefilling,or re-
not appear.If pyrite is not the sourceof sulfuror the placement).The moredefinitivephrase"paragenetic
reductant,the sequenceof mineralogyandchangein sequence"is then usedto describethe chronologic
fs2wouldstill be the same.Somelead andzinc are orderof formation,andit isthisaspectof the problem
likely presentin the solutionsaswell, but they tend that we address in this section.
to be lost from the systembecauseof deficiencyin Parageneticconsiderationsare important in the
reduced sulfur. contextof this studywhenwe considerthe implica-
Further discussion of low-temperaturedepositsis tions of zonal growth. Depositionalzoningreflects
not appropriatebecauseof the possibilityof domi- changein assemblage over an interval of spaceat a
nanceof othertypesof complexing (bisulfide,organic, given time, whereasparageneticsequencereflects
etc.) that may occur,and controlsolubilities,aswell changein assemblage at a givenpointoveraninterval
asthe greaterlikelihoodof nonequilibrium processes. of time. The term zoningsequence(asopposedto
Ore depositsare amenable,however,to the type of zoningpattern)can thereforebe confusingunlessit
analysis we havegiven,makinguseof whateverfield, is clear we are referringto sequentialreactionsin a
experimental,or theoreticalinformationis available. migratingincrementof solutionat a specifictime. A
For example,the PbandZn solubilitycurvesof Figure thoroughparageneticstudyis then an attemptto in-
4 may very well crossat lower temperatures,and in tegrate many points of observationinto a coherent
fact,erossingisindicatedby the low-temperaturesol- history,but overinterpretation andovergeneralization
ubility dataof BarrettandAnderson(1989.).In terms becomehard to resist.Large-scalefeaturesand frac-
of nonlogarithmicconcentrationthe curvesare al- ture-controlledcrosscuttingrelationsare the most
ready converging,asnoted earlier. Even with no rel- reliablecriteria. Parageneticdiagramsare usefulbut
ativechangein the Ki• valuesof the complexes of the shouldbe usedconservatively. They canbe counter-
two metalswith decreasingtemperature,erossingis productivebecausethey tend to obfuscateand con-
more likely becauseeomplexingbecomesweaker at fuseage and spatialdistributions. What is occurring
low temperature and solubility productsbegin to in one part of a depositcontemporaneously with an-
controlsolubilitiesto an increasingdegree,the value other part is not adequatelycovered by these dia-
of the solubilityproductfor PbSbeingsmallerthan grams.Objective,factualrepresentation is oftenbest
that of ZnS. Sucherossingof the curvesillustratesa servedby time-slicemapsandcrosssectionsof a com-
third possibilityfor producing,or contributingto, a plexorebodyor district.Thesealsominimizesemantic
reversalin metal zonation.The processmay apply, problemsthat sometimesdevelop in discussions of
for example,to the commonlyreversedpositionof paragenesisand zoning. Fine time lines are usually
galenaand sphalerite(i.e., ehaleopyriteto galenato difficultto establish,but roughtime lines,suchasused
sphalerite)in low-temperature,sediment-hosted de- by Gustafsonand Hunt (1975) at E1 Salvador,are
positssuchasthe Kupfersehieferof Europeandpos- generallyevident.
sibly Mount Isa and MeArthur River in Australia Zonalgrowthcanbe controlledby eithera thermal
(Gustarsonand Williams, 1981). or chemicalprocess.Let us considerit first from a
thermal,or prograde-retrograde,standpoint. We refer
to Figure5, whichshowsthe samerelationsasFigure
Paragenesis 4 except that the horizontal axis now representsa
The term "paragenesis"implies a characteristic partialcrosssectionof a hypotheticalporphyrycopper
mineral associationin ore depositsconnotingcon- or Butte-type orebody.We will assumeiron miner-
temporaneous formation(BatesandJackson,1987). alizationoccursthroughoutasin the Butte system.In
An examplefromthe contextof thisstudymightbe the contextof this diagram,the numbersdesignating
the pyrite-covellite-dickite-alunite
paragenesisof the temperature and concentrationare no longer fixed
deep central zone at Butte. Equilibriumis not nec- but changeas the spatialinterval either heatsup or
essarilyimpliedby the term. With the development coolsoff. The solubilitycurvesthereforerepresent
oftheterminology ofmodernmetamorphic petrology, solubilityfrontsat any giventime in the evolutionof
however,it hasbecomeevidentthat where equilib- the system.With the passageof time, in a prograde
rium is impliedthe more generaland well-accepted system,curves will rise to higher values. Conse-
term "assemblage" is probably preferrable, and quently, copper, zinc, and lead mineralizationwill
where not implied, the term "association"is ade- continuallymove upward and outward, and if juxta-
quate. Contemporaneity,moreover, is often uncer- posedaszones,eachzonewill replacethe nextouter
 HYDROTHERMAL ORE-FORMING PROCESSES:
PT. II 37

tern the Cu front collapsesinward, as shownby the

inner dottedsaturationcurve,but if the transportpath
alsois falling, the effectis to counterthat collapse.In
thisway, we canbetter understandthe manyramifi-
cationspossiblein a complexore-formingsituation;
for example,why onezonemigratesandanotherdoes
not, or why no clear zoningpattern at all might de-
velop.The geologicexpression, overan extendedpe-
riod of time, is basicallya reflectionof the interplay
between the changingpositionof the saturationsur-
facesand the changingvaluesof the transportcon-
centrations.
A final considerationof this interrelationshipis the
length of time a given transportconcentrationvalue
or range of valuesoperatesgeologically.If the ces-
sationof mineralizationis rapid (i.e., the rapid fall of
a horizontaltransportpath to low valuesin Fig. 5),
there will be relatively little manifestationof this
changein the rocks.The late fracture-controlled py-
rite depositionin porphyries,on the other hand,is a
majorgeologicfeatureandappearsto pointto a long,
cooling,iron mineralizationhistory (Gustafsonand
Hunt, 1975).
In the retrogradepart of the cycle of mineraliza-
deposit deposit tion, the outer zonesencroachinward and downward
fringe center
in the reversesequenceof the progradeseries.How-
ever, the two partsof the cyclediffer in that, during
DISTANCE
the progradestage,the oldersulfidemineralsbecome
more solubleand are replacedby the younger;as a
FIG. 5. Samerelations as Figure 4 plotted as a crosssection resultthe evidencefor the prior existenceof the older
of a hypotheticalporphyry copper or Butte-type orebody at a
givenpointin time. Curvesthen representsolubilityfronts,which
is oftendestroyed.Duringthe retrogradepart of the
rise in a progradesystem,fall in a retrogradesystem.Dotted re- cycle,on the other hand,the older mineralsremain
lations are discussed in text. stableandthe youngermerelyovergrowor fill frac-
tures in them. This can be seen more clearly by re-
ferringto Figure5. Aboveanygivensulfidesolubility
one. In terms of a textural study, this replacement curve (front) in the figure, the aqueousphaseis su-
implies that chalcopyriteis later than sphaleriteand persaturatedwith respect to the mineral, but the
that sphaleriteis later than galena.Theseagerelations mineralis stablein that aqueoussolution.Downward
are indeedcorrect,but only at the point of observa- migrationof the fronts,therefore,simplyextendssta-
tion. It is easy,therefore,to seehow, in a mineralog- bility fieldsdownward,withoutanytendencyfor dis-
ically and structurallycomplexdistrict, overall con- solutionor replacement.Somedistrictsrecordmostly
temporaneityin mineralizationcanbe confusedand the firstpart of the cycle,andcollapseoccurswithout
misinterpreted.This wasthe situationfacedby Sales leavingmuch of a record.More typically,the retro-
and Meyer (1949) in their effort to systematizethe gradepart of the cycleis the bestrecorded,thereby
mineralization of the Butte district. providingthe basisfor the commonobservationthat
Continuingthe illustrationof zonemigration,con- the parageneticovergrowthsequencematchesthe
sideranygivensaturationcurvein Figure 5, saycop- zoningpattern.Chemicalandthermalperturbations,
per, and its assignedtransportpath. As the Cu curve however,aswell asmultiple cyclesof mineralization,
risesin the contextof risingcurvesor frontsin a pro- sometimescomplicatethe record.
grade system,the point of intersectionwith the Cu The foregoingstatementsare not meantto imply
transportpath continuouslymovesoutward or to the that dissolutionand replacementdo not occurin ret-
left. In other words,the copperzone movesoutward rogradeprocesses.When they do occur, however,
as illustratedby the outer dotted saturationcurve. they are the result of the impositionof a new and
However, if the concentrationvalue of the transport contrastingchemical environment,and not simply
path alsois rising,asillustratedby the upper copper lowertemperatures(e.g.,a descending acidfrontfrom
dotted arrow, the effect will be to reduce the outward a high-levelboilingzone,or the replacementeffects
migrationof the zone. Similarly,in a retrogradesys- associatedwith a descendingsupergenezone).
38 j. j. HEMLEYANDJ.P. HUNT

At Butte, the principal evidence of outward ex- Stage copper mineralizationand the inner limit of
pansionof metal zoning is the growth of the inner commercial zinc mineralization are shown by the
high copperzone (pyrite-chalcocite-bornite-enargite)stippledarea.Within this area,sphaleritemineraliza-
againstthe chalcopyritezone and the displacement tion is progressivelymore intenselyreplacedas one
of the sphaleritezone by the copper sulfides.The approachesthe inner boundary.Theseboundaries,in
spatialextentof displacement or migration,however, the parlance of Butte, are known as the "Copper
is difficultto establishand may havebeen smallcom- Front" andthe "Zinc Behind." Contraryto suggestion
pared to the size of the zonesthemselves.Evidence by Bartos(1989), zincappearsto be neitherearlynor
of inwardmigrationat Butteismeagerbut apparently late in termsof the overallprocess(SalesandMeyer,
is manifested in a few localities where breeeiated 1949). Somequartz-serieite-pyriteveinsdeep in the
sphalerite is cemented by rhodoehrositefrom the central zonethat do not carry coppermightbe early,
outer manganesezone. One of the moststrikingex- but this cannotbe demonstratedby crosscutting re-
amplesof the inward migrationof the curvesis in the lationsand may only representa temperaturediffer-
porphyries,where the retrogradecollapseof the iron enee in the intersectionsof the transportpaths of
curve in Figure 5 givesrise to the typical crosscutting copper and iron along their respective saturation
pyrite-serieiteveinletsin background(early) ehal- curvesin Figure 4 (i.e., the deeperdepositionofpy-
eopyrite-bornitemineralization. rite without copperis at a higher temperature).
Figure6 is anillustrationof zoningrelationsin the In the Buttesystem,developmentof a thermalpeak
Butte veinstaken from Meyer et al. (1968). Bound- duringMain Stagemineralizationmayhaveoccurred,
aries marking the outer limit of commercialMain superimposedon the overall Butte cooling record.

.BADGER

I t
! I
t I
t t
I t

;? MT. CON.

! I
I i
HIGH ORE SF

KELLEY SH.

:::!:•:-
ST EWARO • H..!:i.?i:
ANACONDA SH.
LEONANO
SH.
ANSELMO SX.
;/'ORIGINAL

ß
:.:BELMONT I)ITT9MONT 9#.

EMMA

•) ß , , t• DO ,
SCALE •
4.o00 , •
e.ooo , , FEET
e,ooo
FIG. 6. Zoning in the Butte district. Compositeplan of the 2800 and 3800 levels showingthe zone
within which there is no sphaleritemineralization,the zone beyond which there is no copper ore, and
the outer edge of the zone of quartz-molybdeniteveinlets,all in relation to the principal shafts(SH)
of the district. The Intermediate zone of overlap of copper and zinc is stippledfor the 2800 level but
delimited only by lines for the 3800 level (from Meyer et al., 1968). [] -- zone of overlap of copper
oresand sphalerite,2800 level; [] = zone of numerousquartz-molybdeniteveinlets,2800 level.
 HYDROTHERMAL ORE-FORMING PROCESSES:PT. II 39

This temperatureincreasecould have controlled,or andhighsulfidationassemblages deepin the Central

contributedto, zonemigration,asoutlinedabove.Al- zone.Thesecontinuouslygeneratedacidconditions,
though relatively subdued(no more than 300ø- together with the effect describedin the next para-
350øC; Brimhall, 1980) in the main mininglevelsof graph,couldhave producedthe outwardmigration
the district, the thermal rise would have been caused of the copperzones.The attendanthighfI•2Swould
by intrusive bodies affiliated with, but somewhat have producedthe high sulfidation,namely,pyrite-
younger than, the Butte quartz porphyry complex bornitefrom chalcopyriteat higherlevelsin the cop-
(Brimhall and Ghiorso, 1983). These are postulated per zoneandpyrite-digenite-covellite at depth(Sales
by BrimhallandGhiorsoto havemobilizedMain Stage and Meyer, 1949).
mineralizationfromthe deep,low-grade,widespread, At this point we must alsonote the possiblerole
disseminatedchalcopyritemineralizationwhich was of wall-rockalterationzoning.Contemporaneous with
their host.Unfortunately,the temperaturerecordat Main Stagemineralization,this is the other type of
Butte is not asclearaswe wouldlike (C. Meyer, pers. simultaneouszonal growth processdocumentedat
commun.),and this uncertaintytendsto be true of Butte (Salesand Meyer, 1948). The growthprocess
hydrothermaldepositsin general,becausefluid in- is controlledby lateral diffusionalexchangewithin
clusionevidenceonthe progradepathisprogressively the wall rock.A sequentialdevelopmentof alteration
destroyedby recrystallizationand lostfrom the rec- at Butte from early argillic-propyliticto sericiticto
ord. Much clearerat Butte is the chemicalimprint. late advancedargillic,asillustratedby Bartos(1989),
We have presentedthe terms progradeand ret- is therefore inappropriateto Butte evolution.As the
rogradein a temperaturecontext, and maintaining compositesericitic-argillic-propyliticalteration en-
thisclassical metamorphicdefinitionin relationto ore velopeswiden with time, there isincreasingchemical
deposits,althoughperhapsnot essential,is desirable. insulationof vein fluid from fresh rock, and therefore,
Potential chemical controls,which may not always a steadyrise in acidity of the adjacentvein fluid at
act in concert with temperature, therefore need to anygivenlevel in the vein.The effectisto moveacid-
be differentiated.A decreasein pH, which in turn ity upward and thereby contribute to outward mi-
impliesdecreasingactivityof sulfideionsat constant grationof metal zones.It is thesechemicalprocesses
temperatureandfs2,will causethe curvesof Figure that probablyshouldbe consideredthe basicmech-
5 to rise, andconversely,an increasein pH will cause anismof sulfidezonemigrationat Butte, inasmuchas
themto fall. Similarconsiderations applyto a decrease Main Stage mineralizationand alteration may have
or increase,respectively, in•2 at constant pH. There been largely or entirely retrogradein termsof the
appearto be three basicscenariosthat governpro- temperature profile. In that sense,Butte would be
grade-retrogradephenomenain ore deposition:(1) analogous to other porphyrydistrictsfeaturinga ma-
temperatureincreasewith increasedchemicalactivity jor, later hydrothermalmineralizing event, suchas
andoutwardexpansion of the system,(2) temperature seenat Chuquicamataand Collahuasi,Chile.
decreaseand concordantchemicalcollapse,and (3) At Butte, contemporaneityin alteration and min-
temperaturedecreasebut continuedchemicalexpan- eralizationis demonstratedby detailed mappingof
sion (sometimesmanifestedas stronghydrolytic al- progressivestructural changesand associatedmin-
teration)over part of the coolinghistory. eralization-alterationin the district through Main
A riseandfall in sulfurfugacitywill tendto follow, Stagetime. Each successive veinlet carriesthe same
in a generalway, the temperatureprofile inasmuch compositealteration envelope and the sulfidemin-
asthe sulfurfugacities for sulfideassemblages, such eralizationappropriateto the sulfidezone in which
as thoseof fig. 2 in Hemley et al. (1992), shift to it occurs.Contemporaneityis the norm for hydro-
highervalueswith increasingtemperature.The sul- thermalore depositionin the sensethat somedegree
fidationstate,however,will notbe reflectedin any of interactionwith the wall rockby the fluidsinvolved
particularmanner.For example,if the retrogradede- in metalsulfidedepositionis expectedandgenerally
creasein •, controlledby magmatic degassing,oc- observed.Alteration, however, is a broader chemical
cursmorerapidlythanthedecrease in theequilibrium processthanthe depositionof anygivenmetalor suite
constantof a givendesulfidation
reaction(e.g., en- of metalsand thereforepartially sequentialrelation-
argiteto tennantite),the lower sulfidationmineralwill shipsare also to be expected.This is supportedby
result,but the alternativeprocessalsooccurs.Simi- the observations of numerousinvestigators(e.g., Sims
larly,the progradepathwill notnecessarily
produce and Barton 1962; Tooker, 1963; Einaudi, 1977; Mor-
increased sulfidation. ris andLovering, 1979; Bartos,1987). The summary
As discussedin detail by Brimhall and Ghiorso presentedby Bartos(1989) is pertinentandusefulin
(1983), the intrusiveevent at Butte discussed above that respect.In an earlier paragraphwe statedthat
apparently contributed a new influx of volatilesand the retrograderecordof mineralizationis frequently
low pH conditions,the most obviousevidence of the best expressed,and sometimesthe only record
whichwasthelocaldevelopment ofadvanced argillic expressed,in the rocksof a givendistrict.Associated
40 J.J.HEMLEY
ANDJ.P.HUNT

alteration,however,may have been partially pro- the aim of soundparageneticstudies,however,to re-

grade, givingrise to the observationthat somealter- late as many featuresaspossibleto the overallpres-
ation preceded ore deposition.The control on the sure-temperature evolution of a district without
evolutionof thesecontrasting patternsof formation "turningonandoffthe spigotsat the source,"asReno
of ore andalterationis not yet clearandmustawait Salesexpressedit. The curvesof Figure 4 further il-
furtherresearchintothesystematics oflatemagmatic-lustratethis point. In the MississippiValley ores,for
hydrothermal evolution. Fluidphaseseparation may example,chalcopyrite ischaracteristically
veryminor,
be importantin manyinstances.In the contextof the but onecommonoccurrenceisaslate crystalscoating
discussion in Hemleyet al. (1992),for example,es- vugs and fractures.Keeping in mind that absolute
capeof the acid-rich,metal-poorvaporphasecould concentrationson the diagramare largely a function
produceextremehydrolyticalterationon condensa- of chlorideconcentrationandare unimportantto the
tion, followedby later ascentof the metal-richbrines argument,reasonablelead-zinctransportpathscould
andore deposition, but documenting sucha process intersecttheir respectivecurvesat, say,150øC. The
isdifficult.Anotherrelationshipofcriticalimportancecopper path, however, may be present at a much
will be differences in the rate of increase of metal lower concentration such that it cuts its curve at
transportconcentrations
(in the contextof Fig. 4) rel- 100øC or lower. As the orebody then cools past
ative to acidity.Thesedifferenceswill determinethe 100øC,leadandzincwill alreadyhavebeendeposited
abilityof the system to continuously purgeandsup- and copperwill be depositedas chalcopyritein the
pressthe deposition of metalin the earlystageof its remainingpore space,namely,vugsand open frac-
development (oratanystageofdevelopment). In the tures. Thus, the coppermay well have alwaysbeen
high-temperaturevein depositswe have discussed, presentin the fluid, and its depositionnot be due to
for example,only iron mighttypicallyexceedsatu- a late minor surgein coppersupplyat the source.
rationin the earlystageandbe depositedaspyrite.
The othermetalsare sweptupwardto be deposited Conclusions
at higherlevels,and with collapseof the system, We haveendeavoredto setforth a broadsynthesis
wouldtendtomigrate downward andbefoundcutting of geochemicalcontrolsandrelationsfor basemetal
earlier alteration and metallization. sulfideore formation(specificallyFe, Cu, Pb, andZn)
The course of alteration versus metallization in the light of experimental studieson buffer-con-
throughretrogradetime is alsoof interest.The two trolled, mixed sulfidesolubilityrelations.Aspectsof
might ceaseessentiallytogether, as was the caseat metal acquisition,whether by leachingor orthom-
Butte(exceptfor minorlatecalciteandclay).Alter- agmaticgeneration,of transport,and of deposition
natively,the advanceof wall-rockalterationmight have been briefly reviewed. Becauseof the notable
cease,but acidityrelativeto K+ mightremainin the effect of pressureon solubility,transportis perhaps
sericite field, with metal concentration of sufficient best representedas a quasi-adiabaticpath interme-
magnitude that deposition
continues for a periodof diate between two hypotheticalend-memberpaths,
time,perhaps evencuttingearlieralterationthrough the geothermaland the adiabatic.Depositionneces-
refracturing
andcontinued collapseof the system.On sarily occursalong geothermalpaths, whereasin-
the otherhand,lowertemperature produces greater creasedsolubilityoccurs,where the volumechanges
ionizationof acidicconstituents,and therefore,with sodictate,alongthe majorportionof adiabaticpaths
continued abundant supplyof theseconstituents,hy- in the high-temperature or near-source region.
drolyticalterationwill continueto occurandperhaps Transportfor long distancesis possiblebecausede-
even intensify to produce advancedargillic and creasingsolubilitywith decreasingtemperaturemay
stronglyleachedassemblages. High sulfidationand be compensated for by increasingsolubilitywith de-
advanced argillicassemblages are evidentin many creasing pressure.
examplesof shallow,low-temperatureconditions, as Depositionis the result of the piercementof the
in the highlevelsof porphyrycoppermineralization saturationsurfacesof the metalsby their respective
wherepreserved.High productionof acidityover- transportpaths, and either a chemicalchangeor a
whelmedthe feldspar-muscovite-quartz buffer,and temperature decreasemay be responsiblefor that
decreasingtemperature,but continuedaccession
of piercement.Metal zoningresultsfrom depositionoc-
H2S, induced fixation of S and the formation of min-
curringat successive saturationsurfaces.These sur-
eralssuchaseovelliteandenargite. facescan migrate outwardand inward in prograde
The foregoing considerationsontimingandpara- andretrogradetime, controlledby eithertemperature
genesisin magmatie-hydrothermal depositsapplyas or chemicalvariables.This migration of one zone
well to lowertemperatureorebodies. Refraeturing againstanothergivesriseto the appropriateapparent
andentirelydifferentmineralization
does,of course, parageneticrelationships,asdefinedby the texture,
occurin the evolutionof manyorebodies,andwe do eventhoughsuccessive stagesof depositionwere not
not meanto underemphasize thatpoint.It shouldbe involved.Thus, the interpretationof parageneticse-
 HYDROTHERMAL ORE-FORMING PROCESSES:PT. II 41

quencecanbe misleading andincorrectif notviewed is attributed in terms of major contribution,but all

in the contextof a total mineralizationprocess.Metal authorsmadesignificant contributions to bothaspects
transportconcentrations, the availabilityof sulfur,the of the investigation. Finally,we wishto thankBecky
dispositionof the saturationsurfacesrelative to one Bagcantand Dot Manley for their assistance in the
another (i.e., their spacingand slopes),and the in- typingof PartsI andII of the manuscript.
terplayof thesecontrolsthroughtime are the major
August 1, 1990; August 20, 1991
factorscontrollingthe final pattern of deposition.
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temsin general.From suchstudieswe will be better
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We may have reachedthe point in the maturationof formingconsequences of the advancedargillicalterationprocess
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Variousaspectsof CharlesMeyer's contributions Burnham,C. W., Holloway, J. R., and Davis, N. F., 1969, Ther-
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Detailed criticismby EconomicGeologyreviewersis experimentaltechniqueslabs.I: Am. Geophys.Union Program
alsogreatlyappreciated.Authorshipof PartsI andII and Abstracts,v. 72, p. 312.
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