Hydrothermal Geochemistry and Ore Genesis of Sea-Floor: Volcanogenic Copper-Bearing Oxide Ores

Economic
Geology
Vol. 87, 1992, pp. 889-912
HydrothermalGeochemistry
andOre Genesisof Sea-Floor
Volcanogenic
Copper-Bearing
OxideOres
GARRY
J. DAVIDSON
Centre
for OreDepositandExploration
Studies,
University
of Tasmania,
Hobart,Tasmania
7005,Australia
Abstract
The term "volcanogenic copper-bearing oxide" mineralizationis proposedto describe

exhaledsea-floorchemical sediments, whicharedominated by magnetite, quartz,andhema-
tite, with subordinatechalcopyrite,pyrite, and in somecases,gold;they occurwithin or
closeto volcanicpiles.
ThreeAustralianexamples(the Starra,Osborne,andBigCadiadeposits)formthe basisfor
a moregeneralvolcanogenic copper-bearing oxidemodel.The shapes of the depositsvary
frommassive mounds andpods(Cadia)withnolaterallydeveloped sedimentary iron-forma-
tion,throughto extensive well-banded stratiformexamples (Osborne).The orebodystyleof
the depositscorrespondingly variesfromsmallhigh-grade Cu-AulensessuchasArea251 at
Starra(2.6 Mt at 6.7 g/t Au, 3.4% Cu), to largelowergradedepositssuchasOsborne(13.6
Mt at 1.9% Cu and 1.0 g/t Au, includinga highergradepod).In all casesintensefootwall
alterationispresent(ahallmarkof vent-proximal exhalative
sediments),varyingfromalbite-
ironoxide-chlorite,to massive quartz-ironoxide,to muscovite-epidote-chlorite,
depending
on the salinityandpH of the ore fluid,andthe presence or absenceof boilingsolutions.At
Osborne, threestratigraphic orepositions recordthreeepisodesofhydrothermal activityin a
stackedsystem,with evidenceof overprintingin the earlierexhalites.At StarraandCadia,
thereis evidencethatthe mostproximalexhalitesare dominated by magnetite,quartz,and
chalcopyrite,whereasthe distalportionsare hematitedominated andvariablypyritic.
Ore formation isattributedto precipitation fromtheoxidizedandH2S-deficient versionof
a volcanic-hostedmassivesulfide fluid, in an oxidized water column. Such fluids must be
bufferedby hematiteand/ormagnetite duringdeepfootwallfluid-rockreactionbelowvent
complexes, to providea sinkfor H2Sproducedby the reductionof seawatersulfate.Thusthe
oretypeisfavoredin intracontin•ntal basinswhicharecommon hostsfor therequisiteoxi-
dizedfluvialandshallow-marine sediments. A second possible sourceofoxidizedmetal-bear-
ingfluidsishighlyfractionated magnetiteseriesgranites; in theAustralian Proterozoicthese
areparticularlyprevalentin rift settings.To achieveCu-Ausolubilityaschloridecomplexes,
andto accountfor the ore mineralassemblages, the ore fluidsmusthavehada T = 260ø to
380øC,a logfo•-- -27.5 to -30, apH = 3.9 to 6, andan2;S'• 10-3M.Highsalinities arenot
an essentialconditionbut serveto greatlyenhancethe efficiency of metaltransportby in-
creasedchlorideion pair metalsolubility.Highersalinities favorthe transportof the ele-
mentsAu, W, Sn, Mo, and Co, whichconstitutea distinctsecondaryelementassociation.
Salinityisalsothestrongestcontrolonoredepositshapeby determining thebehaviorof the
fluidafterit exitsfromthe vent;for instance, modeling suggests thata high-salinityfluid
coolingat constant pH canexplainthe Si/Feratioandthickness of someStarraore lenses.
An importantgeochemical featureof volcaniccopper-bearing oxidemineralization is a
distinctdepletionof PbandZn (usually lessthan10 ppmof eachoccurs in orezones).Thisis
attributedto the verylow H2Scontentof the ore fluidandwatercolumn,whichpermits
precipitationofCu andFe aschalcopyrite andpyriteat temperatures greaterthan'• 280øC,
removingall H2Spriorto galenaandsphalerite saturation. A volcaniccopper-bearing oxide
brine,fromwhichCuwasremoved at thevent,couldmigrateacross a seafloorandprecipi-
tatePbandZndistallyin localized biogenic H•S-bearing deeps.Bythismeans, orbyslightly
increasingthe exhaledH•S concentration, Pb-Zn-richiron oxideoreswith greaterPb-Zn
contents couldbe produced, mineralogically transitional betweenvolcanic copper-bearing
oxideCu-Aubandediron-formation andBrokenHill-Pegmont-style Pb-Znbandediron-for-
mation ores.
Introduction termedthevolcanogenic copper-bearing

oxidestyle.
Passagealongstriketo unmineralized
bandedand/or
A NUMBERof areas in the world contain stratiform to massive iron-formation is a common feature. The
to strata-bound,
ironoxide-rich
copper_ goldminer- iron-formations
arecontainedvariouslywithinmafic,
alization,
withevidenceof sea-floor
deposition,
here intermediate,and felsic volcano-sedimentaryse-
0361-0128/92/1342/889-24$3.00 8 89
890 GARRYJ.DA•DSON
quences,are principally hostedby intracontinental Structuraleventsin the Starraregionconsistof (1)

basins,and have no clear time control to their occur-the Starrasheardevelopmentduring the D• exten-
rence. The literature dealingwith copper-bearing sion(Switzer,1987), (2) the peak metamorphicD2
ironformationisfraughtwith controversy andconfu- (mainphase)deformation,producingupright,north-
sionbecausethere is little agreementon genesis. trending, isoclinal folds--this deformationcorre-
Copper-bearingiron-formationsare also not com- sponds to the regionallyrecognizedD2 eventof Page
mon,whichhasled to the assignment of someexam- and Bell (1986), (3) the retrogressional left-lateral
plesto the skarnore classin lieu of a viablealterna- strike-slip on the Starra shear, producing local
tive. Many are strongly deformed and metamor- steeplyplungingandcommonlytransposed medium-
phosed. Exhalative volcanogeniccopper-bearing scalefolds (D•; late phase),(4) the D3 northwest-
iron-formationsarebestthoughtof asonememberof trendingfold and kink domains,and (5) the D 4 re-
a family of oxidized ores, with the other members verse movement on the Starra shear and nearby
being hydrothermal-replacementand magmatic MountDore faultzone,relatedto the regionalintru-
types. sion of the Williams batholith.
A specificproblemwith the assignment of anexha- An informalstratigraphicsubdivisionfor the base
lativeoriginto particularcopper-bearingiron-forma- of the StaveleyFormationin the Starraareais asfol-
tionsin the pastwasthe lack of a geneticframework lows.Lowermostis the Harley Member, a strongly
or modernanalogue.In this respect,this paperis a deformedchloriticunit with a tholeiitictuff compo-
predictivework,to supportthe notionthat oxidized
ore fluidswhichwere exhaledontothe seafloorpro-
duceda uniqueassociation of chemicalsediments.
Three important examplesof volcanic copper- +
bearingoxidemineralization occurin Australia.They

are Starra(Mount Isa inlier, Queensland),Osborne
(formerlyknownasTroughTank;Mount Isa inlier),
and Big Cadia (Lachlangeosyncline,New South
Wales).The geologyof the formertwo hasbeende-
scribedin greater detail in Davidsonet al. (1989).
The geologicdetailsof the Big Cadiamineralization
MN
+ +
+
MT ISA
Pb-z.•
',.
ß t
Gin Creek
are givenin Welsh (1975), Bajwah(1985), and Baj- Block
TROU6H
wah et al. (1987). This paper exploresthe special D2(LP) + Mt Dore Granite
physicaland chemicalconditionsnecessaryto form sinistral
syngeneticvolcanogeniccopper-bearingoxide ores,
;;;; Cu deposit
drawingprincipallyon theseAustralianexamples.
+
....... '
Geologyof the StarraGold-CopperDeposit ::::::::::::::::::::::::::::::
+
Starrais a strata-boundCu-Au deposit(5.3 Mt at + ß:::::::::::::::::::::::::::::

5.0 g/t Au and 1.98% Cu; Kary and Harley, 1990) + ßU nmineralise d .;.;.
hostedby stratiformmagnetite-hematite
iron-forma- 1;Eastern Hematites;;;
tion in the Mount Isa eastern succession,150 km Mineralised ;;;;(non-magnetic)
W•stern
southeast of Mount Isa. It occurs close to the base of
H•matites
the Staveley Formation, indirectly estimated at (magnetic) Kuridala
•1720 Ma by Page(1983). A roughPb modelageof Formation
1630 _ 120 Ma hasbeen reportedfor correlativesof ß :.:.:.:.:.:
the Starrahostsequence(Gulsonet al., 1990). The
StaveleyFormationis a member of the rift-related
middleProterozoicMary KathleenGroup and was
depositedin a shallowmarineto evaporiticsetting
prior to beingdeformedandmetamorphosed (Blake
et al., 1984). Peak metamorphicconditionscloseto
the ore are estimated at 500 ø to 550øC and 3.5 to 4.5
kbars.The locationof Starra (consistingof 4 geo-
graphicallyseparateorebodies;areas222, 244, 251,
and257), onthe marginof a majorgreenschist facies SouthernGrids • Known
economic
areas
of
shearzoneknownasthe Starrashear(Switzer,1987), Magnetic extension mineralisation
wasreflectedin a more complexstructuralhistory FIG.1. Regionalgeologyof the Starraarea;(inset)locationof

thanthat experiencedby surrounding rocks(Fig. 1). the Starradepositandthe Osborne-Trough
Tankprospect.
SEA-FLOOR VOLCANOGENIC COPPER-BEARING OXIDE ORES 891
nent,50 to 100 m thick.The HarleyMemberis con- eralized Starraironstonesare positivelycorrelated

formablyoverlainby the MariposaCreek Member with one another and with W, Sn, Si, Y, and Mn.
(beddedalbite-quartz rocks,consideredto havea fel- Both structural-metamorphic (Lainget al., 1988;
sic volcaniclasticprogenitor)45 to 180 m thick, Switzeret al., 1988) andsyngenetic (Davidsonet al.,
whichin turn is conformably overlainby the Starra 1989) genesismodelshave been proposedfor the
Iron-FormationMember(1-25 m thick),andthenby ores.A syngeneticoriginis favoredbecause(1) the
undifferentiated calcareous metasediments. To the orehorizoncoincides with a volcano-sedimentary in-
south and east, the Starra Iron-Formation Member terface;(2) alterationis highly deformedand con-
gradesfrom the mineralizedsegments into massive formswith otherexhalativehydrothermal systems in
hematiticironstones,conglomeratic ironstone,Ha- beingmainlyconfinedto the stratigraphic footwall;
mersley-stylebandediron-formations,and tourma- (3) mostsulfidesand iron-formationare folded and
linites, all intercalated with shallow-marine and flu- recrystallized by the earliestrecognizable deforma-
vio-deltaic sediments. The local ore environment is tion event; (4) the ore sulfidesare disseminated
interpretedasa deepersectionof the basinby com- throughoutthe iron-formationrather than concen-
parisonwith theselateral facies. tratedaroundcrosscutting structuralzones,asthey
A chemical-sedimentary originfor the StarraIron- are in acknowledgedepigenetic iron-formation-
FormationMemberis supportedby (1) its stratiform hostedgolddeposits; and(5) themineralization coin-
characterover610 km2;(2) a micro-andmeso-scalecideswith the locallythickestpart of the iron-forma-
bandingpreserved in someoutcrops; (3) a sedimen- tions,whichcannotreasonablybe accountedfor epi-
taryreworkingofiron-formation clasts intopolylithic geneticallybut is consistentwithin an exhalative
conglomerates at area222; (4) anintergrowth ofgyp- model. However, while the copper and gold ulti-
sumpseudomorphs with thinly beddediron-forma- matelyhavea syngenetic originandare in their ap-
tionconsistent with bothdiageneticandsynsedimen- proximate primary positions, deformationalpro-
tary evaporitegrowth;and (5) a lack of symmetric cesses havein someplacesfurther concentratedore
zoning,skarnmineralogies, or suddenterminations, zones into lineation-parallelshootsand in others
whicharetypicalof replacement iron ores. actedto dilute the ore duringreactionwith retro-
Starra mineralization consists of massive to banded gressionalfluids.The latter processmobilizedsome
quartz-magnetite-ehaleopyrite-gold _+scheeliteiron- copper (but not gold) into hanging-wallreaction
stone(ehaleopyrite variesbetween2 and20%by vol- skarns.
ume, andW variesbetween500 and 2,000 ppm),
gradinglaterallyto magnetite-quartz-hematite-ehal- Geologyof the OsborneCopper-GoldDeposit
eopyrite-pyrite,andthen to poorlymineralizedhe- Osborne,a resourcetotaling13.6 Mt of 1.9 per-
matite-pyrite _+magnetite ironstone, over '• 250 m at centCu and1 ppmAu (Laing,1991), liesunconform-
areas257 and251. Corresponding to thistransition, ably beneath30 m of Mesozoicsediment,40 km
wt percentSi/Fe ratioschangesystematically from southeast of Starra.It ispart of a projectareaknown
0.27 to 0.08 awayfrom the magnetite-ehaleopyriteas TroughTank (the depositname wasrecently al-
zone.The highestironstoneCu andAu gradesare tered to "Osborne" to honor its deceaseddiscoverer,
underlain by either massiveehlorite, or intense Robert Osborne).The knownmineralizedzone, re-
stringer-style magnetite-hematite-ehaleopyrite alter- ferred to as the "keel anomaly,"is •500 m long,
ation(Fe203totalavg= 43.6%;Fig. 2) pervasively occurring as the northern, most magnetic end
shearedand foldedmagnetite-albite-pyrite _+chlo- (16,000 nT abovereference)of a 7-kin-longnorth-
rite _+sericitenetworkalteration(avgFe•O3total = south aeromagnetictrend (Fig. 3). This trend
29.9%), includingdominantly hematiteandmagne- (termedthe "centralanomaly")repeats800 m west
tite-chalcopyrite vein types.Randomlyorientedsili- of Osborne.At presentthe centralanomalyis be-
cate inclusionsin sieve-texturedpyrite porphyro- lieved to correspondto a large D• synform,dislo-
blasts from the Starra footwall are considered evi- catedby northeast-and northwest-trending strike-
denceof theirpremetamorphic growthin anunlithi- slipfaults.Structuralterminology usedon thispros-
fledmedium,by analogy withpyritesknownto have pectfollowsthat of PageandBell (1986), beingthat
grownin suchmediaelsewhere(e.g.,Frater,1983). regionallyusedin the Mount Isa area.
The intensityof sulfideand oxide alterationde- Cu-Au-Comineralization is hostedmainlywithin
creases with depth.Chemically,lossof K, Ba,Sr,and three concordant,banded, magnetite-richunits
Ca and Na gainshaveresultedfrom regionallow- (bandediron-formations), in a sequenceof quartz-
gradealterationof the Starrafootwall,probablydur- ites, feldspathicquartzites,phlogopitic,and feld-
ing salinediagenesis. Mn, Zr, Nb, Pb, Zn, andLREE spathicschistsat least120 m thick.The bandediron-
wereremovedin moreintenselyalteredzoneswhere formations consistof alternating• 1-cm-widebands
Fe wasadded,leavingonlyTi, Na, andA1constant of magnetite_+apatite_+pyrite _+chalcopyrite,and
relativeto lowergradealteration.Cu andAu in min- quartzwith minormagnetite.In addition,someholes
892 GARRY
J. DAVIDSON
AREA 251 1275RL
[]
•
Pyritic
hematite
ironstone
Magnetite-hem-coy
2cChlorite
schist
ironstone
3aFeldspar-hem-mag-py
schist
•Transposition
brecc
ia -•-• - Reverse
1•50E• _•••=•:_• ,
•.• ---' [ GEOLOGY
• > 7.5 oom

• 5-7.5
[] 2.5-5
:.:[] 1-2.5
[] 0.5-1
[]<1
._
1550E
o 10m
i I
290.5*m
Au GEOCHEMISTRY
FIC.2. Geologyandgoldgeochemistry
oftheunderground developmentatarea251, 1275RL,Starra.
GoldvalueswereobtainedfromCyprusMinerals2-m rock-chipsampling
anddiamonddrilling.
containa discordantstyle of coarse-grained silica- permostbandediron-formationis hostedunsystema-

dominated mineralization. The conformable mineral- ticallyby either of theselithologies.Of these,the
izationstyleis extremelysimilarto thatat Starra,dif- middle banded iron-formationis most consistently
fering by being lessdeformedbut more metamor- mineralized,with an averageof 0.55 ppm Au and
phosed;upper amphiboliteconditionshaveresulted 0.53 percentCu (n -- 216), rangingto 52 ppmAu (an
in local anatexisin the feldspathicschists.The two indicationof nuggetingin the analyses causedby
lower and middle banded iron-formation horizons coarsegold).Covaluesrangebetween100 and2,000
(averaging15 m thick) are usuallyunderlainby a ppm. Bedsof biotite-anthophyllite-cordierite schist
massivepink feldspathicschistand are overlainby are not abundant but are most common near the base
feldspathicquartzite(coarsening upwardto isolated of the prospectandasbarrenequivalents of banded
pebble-bearing grits, arguingfor a shallowclastic- iron-formation.
hostedsedimentaryenvironment),whereasthe up- Pyrite,chalcopyrite,andrarebornitcarethe only
1210N
TT-42rc TT-43rc Tr 44rc TrHQ-9ddh Tr-45rc TrHQ-10ddh TT-46rc
123m
134m
141r
ProspectGeology
[• Coarse-grained
pegmatite 3•m
• Transgressive
qtz-mag+_py-cpy
i• Feldsparbin
quartzite
[• Variably
mineralised
magnetite
B1F
[•] Bedded
tomassive
albite
sclnsl
+phlog.
Keel
anomaly..••
/•'• Magnetite
and/or
pyrite-aReration
and
veining
m Oxide
BIF %'•,'-.•,•
i;;• Anthophyllite
+chrysotile,
cordierire
schist • Feldspathic
schist
• biotite
metres ,.'5'3
0 10 20 30 4050
FIG.3. A geologicsectionalongline 1210N (prospectgrid),Osborne;(inset)prospectgeologyde-

ducedfromdrillingandgeophysicalinformation
by Placergeologists
in 1988.
sulfidephases, occurringas disseminated grainsin coarseninggrain size (2-10 mm, annealledin thin
magnetite + hematitebands,withsimilargrainsizeto sections)and crosscutting folded mineralizedvein-
theotherrecrystallized components (magnetite aver- lets. The dominantfeature of this style is a clear
ages20 3tmin quartzlayers,and 0.4 mm in massive quartzmatrix,whichhostsfineeuhedraof magnetite,
magnetitebands).The conformable ore rarelycon- pyrite, chalcopyrite,and carbonateandis foldedby
tains more than 5 percent disseminatedsulfides. F•. Irregular blocksof feldspathicschist(1-5 cm
Quartzandsedimentbandsdo not normallycontain across)containedwithin the quartz matrix have
sulfide.Apatiteandsideriteare constantaccessorieschloritizedrims and are infiltratedby fine pyrite.
in magnetitebands,whereastourmalineis uncom- Theyarethoughtto representremnantsof thepreex-
mon.Pyriteandchalcopyrite are intergrownbut not istinglithology.The overallgeometryof varioussil-
replacive,indicativeof metamorphic equilibrium;in- icapipealterationzonesison averagebelievedto be
clusions of both occurin annealedmagnetite,and an upwardly facing funnel, characterizedby bed-
vice versa.Somemagnetitespreservelinesof quartz ding-parallelincursionsaway from the main discor-
and sulfideinclusions
parallelingthe larger scale dant zone and in which the top is so flared as to
compositional
layering,resultingfromthe metamor- be easily mistakenfor a stratigraphicunit. The
phic overgrowthof a bedding-parallelfoliationor surrounding feldspathic
gneisscontainsabundantpy-
relictbedding. rite-magnetite+ epidote+ carbonateassemblages as
Discretemassivesilicaandmagnetitezoneswhich veins,blebs,andstrings,somefolded,frequentlypar-
underlie concordant banded iron-formation mineral- allel to but alsocrosscutting
compositionallayering,
ization,andin placesoverprintit, arerecognized
by decreasing from a peak of 10 to 25 percentaway
894 GARRYJ.DAVIDSON
fromthe quartzzone,overabout10 m (thisalteration (1983) to have developedwithin an 800-km-long,

is mostsimilarto the pervasiveoxide alterationof northwest-oriented,mafic-intermediatemagmatic
Starra).Beyondthisa disseminated
cobalt-richpyrite arc, dimensionallycomparableto the present-day
zoneextends50 m or morealongstrike,withvariable Andaman-Nicobar arc. Massive submarine andesite
carbonate alteration. flows,agglomerates,
crystal,and lapilli tuff of the
A lack of outcroplendsuncertaintyto the strati- BlayneyAndesiteunderliethe orelens,but muchof
graphicpositionof Osborne.Minorprimarycarbon- the immediatehangingwall (alsosomeminorfoot-
ate in the sediments,acidvolcanism,andthe strong wall zonesand ore intercalations)is metalimestone,
similarityof the mineralization
styleto Starra,favors testifyingto a likely shallowmarineenvironmentof
a positioncloseto the baseof the StaveleyForma- oredeposition. Regionallythe association
of subma-
tion,within the Mary KathleenGroup.However,on rine volcanics and limestones indicates that volcanic
the basisof similar metamorphicgrade, Osborne edificesin the ancientenvironmentgrew to shallow-
banded iron-formationscould equally representa marine levels to form volcanic islands and atoll com-
continuanceof Pegmontbanded iron-formation plexes.Intercalatedvolcaniclastic
rocksand lime-
chemical sedimentswhich are exposed ---32 km stoneswithin the mineralization contain cobbles and
north-northeast
of the TroughTank project and are gravelsof massive magnetite-hematite, whichpro-
assignedto theupperKuridalaFormationby Stanton vide firm evidenceof the synsedimentary origin of
andVaughan(1979) andBlakeet al. (1984). Beards- thesecomponents (Bajwah,1985). Roundedfrag-
more et al. (1988) placedPegmontat least2,000 m mentsofbladedhematiteandmagnetitearealsopres-
belowthe StaveleyFormation,in the Mount Norma ent in the basalconglomerate of the overlyingPan-
Quartzite(a yet to be formallydefinedunit). uara Formation. A section of the mineralization is
thermallymetamorphosed by localMiddle Silurian
Geologyof the Big Cadia Copper-GoldDeposit monzoniticdikes of the Cadia Intrusive Complex
A summaryof the workof Welsh(1975), Bowman (Ambleret al., 1977); generally,however,the ores
et al. (1983),Bajwahet al. (1984, 1987), andBajwah haveonlyexperienced lowergreenschistfaciesmeta-
(1987) concerningthe Big Cadiamineralizationof morphism,which accompaniedbroad structural
New SouthWales (Australia)is presentedhere, to warping.TheCadiaIntrusiveComplexhasnotexperi-
documentthe featuresof a relativelyunmetamor- encedthismetamorphism. It containsseveralsmall
phosedmemberofthevolcaniccopper-bearing oxide porphyry-style Cu-Au-Moveinprospects.
mineralization
style.Therearesomesignificant
varia- Historically(1882-1945) 750,000t of oreaverag-
tionsbetweenBigCadiaandthe MountIsainlier ex- ing 50 percentFe, 6 percentCu, and6 g/t Au has
amples. been minedfrom Big Cadia(Bajwahet al., 1987).
Big Cadia, located22 km southof Orange,is a Althoughnowhole-rock dataareavailable,
Covalues
stratiformlensof well-beddedmagnetiteandhema- in pyriteaveraging 3,769ppm,andhighlyanomalous
tite, with sparsepyrite, chalcopyrite,andgold(Fig. concentrations in otherphases,areevidencethatthe
4). The hostrocksare andesites, rocks, mineralizationis Co enriched(Bajwah,1985). Prior
volcaniclastic
and sedimentsof the Upper OrdovicianAngullong to mining,the depositwas40 m thickx 600 m longx
tuff, a unit consideredby Caset al. (1980) andCas 250 m wide,althoughit ispartiallyeroded.A smaller
limestone main copperzone
siltstone
&sandstone
/
FIG.4. Theplansurface
geology
oftheBigCadiamagnetiteCu-Aumine,NewSouthWales(adapted
fromWelsh,1975,andBajwah,1985).The crossed
patternindicates
a monzonitic
intrusion.
similarlensoccurs2 km eastat Little Cadia (Mason, reticalestimateindicatesmoderatelyhottertempera-

1981).In detaila crudemineralogical zoningoccurs, turesthanthe observedfluid inclusiontemperatures
from well-beddedmagnetiteand hematite at and fromBigCadia(270ø-320øC),althoughthereiscon-
near the top (containingup to 2% sulfide),grading siderableoverlap.The presenceof scheeliteat Starra
downto massivemagnetite-hematite disseminated doesnotconstrain
+__ thetemperatureestimate,because
pyrite and chalcopyrite(averaging10% sulfide; it hasa largestabilityrange,120ø to >600øC (Wol-
Welsh, 1975). Initially hematitewas precipitated, lenberget al., 1977; Ivanova,1988).
but was subsequently reducedto magnetitein the The availablestudiesof the mobility of Au favor
lower parts of the body as hydrothermalactivity the dominanceof either thio or chlorocomplexesin
evolved.Chalcopyriteismainlyassociated with mag- hydrothermalfluids(Seward,1973; Cole andDrum-
netiteor pyrite.Smallatolltexturesin nodularpyrite mond,1986; HustonandLarge, 1989), with apossi-
are recognizedby Bajwah(1985) assimilarto open ble contributionfrom lessabundantspeciessuchas
growth structuresin ancientand modern sea-floor polysulfide,sulfite,bromide,ammide,telluride,and
massivesulfidedeposits. carbonyl-carbonate complexes,dependingon fluid
Andesitcbelow the ore lens displaysa distinctly composition (KerrichandFyfe, 1981;Seward,1984;
zonedalterationcontinuum. Anepidotite(70%)-chlo- Wilde and Bloome,1988).
rite-quartz-calciteassemblage (+ apatite,sphene,he- The predominantthio complexin hydrothermal
matite,andmagnetite)extends12 m beneaththe ore, systems is Au(HS)•, whichis mostsolublein the py-
whereit mergeswith a granular,chlorite-dominated rite field at <300øC, particularlybetween170ø and
(40-50%) zone (+ epidote,quartz, calcite,sphene, 250øC (HenleyandBrown,1985). However,Huston
apatite,magnetite,andhematite).Chloritealteration andLarge(1989) notedthe low solubilityof Au(HS)•
passesdown and laterally into a sericiterock which in the pyrrhotite, hematite, and magnetitefields.
has retained its volcanic textural character. Chemi- AuCI• is the onlyimportantgold-transporting com-
cally,Fe, Ca, andMg havebeenadded,andNa, K, Ti plexin the magnetiteandhematitefields,andthere-
and Si have been lost, in the zone of most intense fore is the only viable speciesfor gold transportin
epidote alteration.Bajwah (1985) concludedthat volcanic copper-bearingoxide systems.A high
epidotealterationhadresultedfromwater-rockreac- Au(HS)•solubilityisunlikelybecause of theverylow
tion by an unusuallyoxidized hot fluid (250ø- sulfurcontentof theAu-bearingores(2-5%). Huston
350øC)in whichFe+aionsgreatlydominatedFe+2 andLarge (1989) considerthat whereAu wastrans-
ions.Primaryfluid inclusions in quartzand calcite portedasa chloridecomplex,anassociation existsbe-
homogenizedfrom 200ø to 320øC, with a modeat
270øC;salinitieswere lessthan5 percentin the few
lOO
measured examples. The 6a4S valuesrangedbetween Osborne BIFs
+4.0 and-5.1 per mil, with distinctmodesfor both lO
pyriteandchalcopyrite at 0 and-3 per mil, approxi-
mately29 per millighterthanUpperOrdoviciansea- 1
water (•28%o; Claypoolet al., 1980). This valueis
substantiallygreaterthanthe fractionation expected .1
ß )
betweenanH2S-bearing fluidat 300øCanda crystal- ß
lizingsulfideat equilibrium.It isthereforelikelythat .Ol

ß
ß
the Big Cadia sulfidesprecipitatedover a very

narrowpH-fo2 rangefroma fluidwith a veryhigh 100
. -,, ....,i
Starra: Area 257

. ....,,.! ........ i ........ i ........
SO4/H•Sratio. ironstones
ß
Bajwah(1985)favoreda volcanic-exhalative
origin 10
ß
for the Big Cadiamineralization,althoughit is not

clear why the alterationof andesitcby seawaterat ß .. ßß
-• J,wl ß ß
>320øC shouldhave producedsuch an oxidized ! I
fluid.
,1 i$
'11
Physicochemical
Conditionsof Volcanogenic
Copper-bearingOxide Ore Fluids .01 ........ i ....... • ........ l ........ i ........
.•1 .01 .1 I 10
Temperature
The chalcopyrite-goldassociationobservedat
•m. 5. A log-logbinar• plot oECu •rsus Au, obtainedErom
StarraandOsborne,andconfirmedby a ubiquitous &ill •o1• intersections o• i•on-•o•mations.
Som•dispersion in t•
Cu-Aulinear relationship(Fig. 5), providesa useful a•a •57 datatowardlow• Cu at •ig• Au g•ad•sis attributedto
temperatureconstraintfor ore formation.This theo- de•ormational
leachingo• copperminerals.
896 GARRYJ. DAVIDSON
P:270 B, pH:5, T:350' C

tween Au-Cu _+Bi, Sn, and Mo. Gold is usuallyfree -2 i i , i • i , i i , i
milling,or hostedby chalcopyrite,anda strongposi- s,

Sv
Sulphidedominant Sulphatedominant
tive correlationbetweenCu andAu is evident (both
arechloridetransported, withnear-parallel
solubility
contoursin the pyritefield).Examplesareporphyry
Cu-Au systems,igneousskarns,relatively oxidized
high-temperature volcanogenic sulfideores,andre-
placementTennantCreek-styleores (Large, 1975;
Huston and Large, 1989; Wedekind et al., 1989).
-10-
The critical feature of AuCI• is its dominanceover
Au(HS)• above300øC (andin very oxidizedregions
-12-
of the hematitefield aslow as200øC). Au chloride
transportisfavoredby highsalinities
(ac•-= 10ø),oxi-
dizedfluids,andlow pH values(<4.5); golddeposi- -14'
tioncanbe achieved
by increasing
pH orfs•, or by
decreasing
a½•-,
fo2,ortemperature
(tobelow380oc; -16
-34 -32 -30 -28 -26 -24 -22 -20
HustonandLarge,1989). Chalcopyritedeposition is Log f02
favoredin salinesystemsabove250øC, becauseCu
chloro complexesexceedthe solubilityof Cu thio F!•.6. Alog fo•-logfs•diagram relevantatthe conditions
of
complexes at thistemperature(WalsheandSolomon, 350 C, pH = 5, P = 270bars. The intersection
(afterRaymahashay
of ES contours
andHolland,1969)withthemagnetite-hema-
1981). tite-pyritetriple-point
constrainsESto slightlygreaterthan10-a
Thus, the thermodynamics of joint ehaleopyrite- M, usingphaseequilibriaboundaries calculated
fromdatain Bar-
gold depositionindicateformationtemperaturesfor ton(1984)andHenleyet al.(1984).Theeffectofthechanging pH
the Starra-Osborne-Big Cadia ores in the range of is also shown for the ES = 10-a M contour.
250 ø to 380øC.
Sulfuractivity ablyafter sericite)occurson the marginsandin the

Sulfur activity hasbeen calculatedfor the Starra interiorsof the hematite-magnetite-pyrite_+chalco-
hydrothermal systemusingthemineralphaseequilib- pyriteveinsin contactwithalbite,butnotinthedomi-
ria in Bowerset al. (1984) andthe experimentaldata nantlyalbiticalterationmatrix.In theseveins,the pH
of Raymahashay and Holland (1969), plottedon an values must have been less than 3.9, at T = 350øC.
as•-ao2 diagram
' Intuitivelythe amountof sulfurin Muscoviteis absentfrom the magnetite-chalcopy-
the fluids,gaugedby the very highratio of oxidesto rite-pyriteveins,suggesting
that the peakore fluids
sulfides,wasprobablylow. The footwallvein assem- had a pH value> 3.9, or were undersaturated with
blage magnetite-hematite-pyrite suggestsZas -- respect to potassium.The hematite-pyrite-musco-
•--10-a M, givena pH valueof •--3.5 to 6, at 350øC vite-albite veins, thought to have formed below
(Fig. 6). Thisvaluemayincreaseto Zas-- 10-2'5M if 250øC, are calculatedto have had a maximumpH
the assemblage formedat higherpH values.Valuesas valueof 5.1, at an arbitraryT = 200øC.
low as•a s = 10-4'0M are unlikelybecauseat 350øC The solubilitiesof calciteand barite may alsobe
the pyrite field would shrinkto an unrealistically usefulguidesto pH values.The calculated stabilityof
smallarea.The value Zas -- 10-ø'øM hastherefore calciteis stronglydependent onthe assumed [Ca+2].
been adoptedto quantifyother fluid parameters. It is likely that subsurfacecarbonatedissolution
wouldhaveprovidedabundant Ca+2,asisthecasefor
Constraints onpH values the modernsalineSaltonSeageothermalfield fluids
Albite-muscoviteequilibria at Starra imposethe whichcontain•--0.9 M Ca+2(McKibbenandElders,
bestconstraints on pH values,but the lack of para- 1985).A [Ca+2]ofbetween0.01 and0.50 Mprovides
geneticcontroladdsuncertaintyto the acidityof the a minimumcalcitestabilitylimit ofpH value= 2.9 to
peaktemperaturephase.As a generalpoint, chloride 4.2 at 350øC. It is not surprising,giventheselow
metalcomplexingat temperatures> 200øC implies solubilities,that minor carbonateis commonlyasso-
acidpH values(PottorfandBarnes,1983). ciated with footwall alteration and auriferous iron-
At 350øC a minimumpH valueof 3.9 is calculated stone at Starra and Osborne.
for the muscovite-albite transition,usingthe condi- TheBigCadiasilicatealterationassemblage of epi-
tionsof 3.0 M NaC1and 0.5 M KC1,parameterscho- dote,gradingoutto chlorite,suggests thatpH condi-
sen to reflect the likely high ionic activity of the tionsmighthave differedin comparison to Starra.
Starrabrinesif rock evaporitewere leachedin the Carusoet al. (1988) andCharleset al. (1988) exam-
footwall. Albite and chlorite are the stable alteration inedthe stabilityof Fe+a-rich epidotein the oxidized
silicates.However,recrystallized muscovite (presum- SaltonSeahydrothermalsystemat 300øC.The domi-
10
nant controlson epidote stabilityand composition
arepH,fo2(controlling
theavailability
ofFe+a),
fco2,
andtheconcentrationofCa+e.Hydrothermalepidote
broadly characterizessystemsin which oxidized
300
øC,
86
bar/
fluidsaresaturatedin Ca+e, suchasmightbe gener-
atedby the leachingof carbonate-bearing
quences.
transition
(approximately
invariant
tofo•)occurs
clasticse-
In SaltonSeafluids,the K feldspar-epidote
ata
pH value •-, 5.2 (300øC), whereasthe muscovite-K
•,7 Albit•
feldsparreactionoccursat a pH value •, 4.9, and
chlorite(35 mole% ferriciron)is stableabovea pH
value •-' 5.8 (Fig. 7). Variation of these mineral
phaseswith pH canbe appliedto the Big Cadiasili-
• 4•__•
I K-spar
1 '• '•
cate zonation.In this instancethe lowestpH value
(epidotezone)in the Cadiaalterationsystemunder-
lay the ironstonebut wasnot sufficientlyacidicto
form massivemuscovite-silica,
as is commonlythe
case in more reduced sea-floor massive sulfide de- 0 3 6 9
posits.Big Cadia alterationcouldhaveoccurredat a log (a(K+)/a(H+))

higherpH value (between4.9 and 5.2) and lower FI(•. 8. Equilibriumactivitydiagramin the systemHC1-H•O-
Na/K ratiothanthat inferredfor Starra(•'3.9-6). (Al•O3)-K•O-Na•O-SiO•,300øC,0.086 kbar,datafromBowerset
al. (1984).
Salinityvalues
Salinityvaluesgreaterthan26.2 wt percentNaC1
equivhavebeendocumented for primarypremeta- Na+/H+;Fig. 8) are all considered
to be indirectevi-
morphicfluidinclusionsat area222 of Starra(David- denceof high salinitiesat Starraduringsedimenta-
son,1990a),whichareintimatelyassociated withhe- tion, ore formation,diagenesis,andmetamorphism.
matite-quartzalteration.Unfortunatelythese have On theaboveevidence,a salinityvalueof 3.0 M NaCI
proven too small for thermometricmeasurement. hasbeen assumedfor Starra and Osbornefluids,be-
Evaporitepseudomorphs in adjacentshallow-water causeit is the highestsalinityvaluefor whichthere
sediments,chlorine-bearing metamorphicminerals, areabundantrelevantthermodynamic dataavailable.
andabundant hydrothermal albite(promotedby high The actualfluidvaluemayhavebeenevenhigher.
In contrast, the direct fluid inclusion evidence
from Bajwah(1985) indicatessalinityvaluesof less
T=300 ø C, Stot= 0.005 M, P = 250 bar, Chl = Ch135
than5 wt percentNaCIequivfortheBigCadiaminer-
alization,i.e., closeto that of seawater.It is therefore
apparentthat the oxidemineralogyand the Cu-Au
geochemistry of the volcaniccopper-bearing oxide
oretypeisnot dependenton salinity;salinitycontrols
the efficiencyof transportof elementscomplexeddi-
rectly with CI-, suchasAu, Cu, Fe, andW (Crerar
and Barnes, 1976; Kwak et al., 1986; Huston and
Large, 1989; Wood andVlassopoulos, 1989), sothat
volcaniccopper-bearing oxide ores probablyaccu-
mulatemorerapidlyfrom moresalinefluids.Differ-
encesin salinityandthe ratiosof the ioniccompo-
nentsNa/K/Caarealsothelikelycontrols onthedom-
inantmineralogyin the alteredfootwall.
Oxidation state
I 2 3 4 5 6 7 8 9 I0 The dominanceof magnetiteand hematiteindi-
pH catesthat the StarraandBig Cadiaironstones
were
deposited
athighfo2.Hematitemayhavebeenpres-
F•G.7. The stabilityof epidote(Ca•Al•Fe+aSiaO•o(OH))
in an ent at Osborne, but evidence of this has been re-
oxidizedhydrothermal system,conditionsasindicated(modified
after Charleset M., 1988). The diagramwaspreparedto model moved by amphibolitefacies metamorphism, and
phasebehavior in theSaltonSeageothermal system(SS-21Awell; therefore,thepresentmineralogy isnota reliablein-
Na, 5.73%; Ca, 2.99%; K, 1.89%; CI, 15.76%). dicatorof theoriginaloxygenfugacity.Theoxidation
898 GARRY
J.DAVIDSON
statehasbeendetermined
onanfo2-pHdiagram
in A DetailedSyngenetic
Ore GenesisModel
theFe-Cu-S-Osystem at 350øC,usingphasestabili-
tiescalculatedfromBowerset al. (1984)andothers, Theformationof oxidizedprecipitates
ontheseafloor
specifiedin Figure9. A numberof mechanisms havebeen proposedto
Hematite-magnetite-pyrite-muscovite_+ chalco- formoxideprecipitatesontheseafloorduringhydro-
pyrite_+bornitcveins(Starraorestage)formedat T thermal activity. These include low-temperature
> 300øC,pH < 4, andfo_• -24 to -28 (Fig.9). The (•150øC), exhalation-producinghematite-quartz
assemblage
magnetite-chalcopyrite-albite
_ pyrite, "tetsusekiei"mantlesin kuroko-stylemassivesul-
whichcharacterizes the mostgold-richStarrairon- fides(Kalogeropoulous andScott,1983),oxidationof
stone,and the underlyingintensealteration,must sulfidesin the watercolumnduringplumefalloutin
haveformedbelowthestabilityfieldofhematiteatT oxic waters(Lydon,1988), oxidationof sulfidesat
> 300øC,pH -- • 4, andfo2-- -27.5 to -30; the the seaflooror duringdiagenesis (asobserved in the
absence of bariteconforms to thisrange.Hematite- Red Seadeeps;PottorfandBarnes,1983), bacterial
pyrite-muscovite veins,and pyrite porphyroblastsfixationof oxides-around low-temperature vents(Ju-
which commonlycontainhematitebladesdissemi- niper and Fouquet,1988; Duhig et al., 1992), and
natedin the footwall,areinterpretedaslowertem- exhalationof oxidizedfluids(Large, 1977; Frater,
peratureproducts withT < 250øC,•;as• 10-a'ø,and 1983).Thesemechanisms representaninterplaybe-
fo2 • -38 to -36. Similarlow-temperature con- tweenthe oxidationstateof the hydrothermalfluid
straintsare suggested for proximalanddistalbarren and the oxidation state of the water column. Above-
hematite-pyrite ironstones. Thepresence of onlyal- sea-flooroxidationmechanisms wereunlikelyto have
biteandchloritegangue in ore-stage veinsandiron- producedthe Starraor Osborneoxideblankets,be-
stoneisevidence thattheprecipitation ofAuwasac- causeveinoxidesoccurupto 100 mbelowthe proba-
companied bydecreasing fo2andpHvalues. ble palcosea floor.Asdiscussed previously, theseas-
The presenceof epidotein an alterationsystem semblages requiredeposition fromoxidizedfluids.
(e.g.,BigCadia,Osborne, andtheSaltonSeageother- The featureswhich the ore-formingfluid must
malsystem) imposes alowerlimittofo2,asillustratedprincipallyexplainare the transitionlaterallywithin
in Figure 7. Starraironstonefrom magnetite-chalcopyrite (Si/Fe
• 0.27), to magnetite-hematite-chalcopyrite-pyrite,
to hematite_ pyrite(Si/Fe• 0.08) assemblages and
Bornitc
• :•S= 10-3'0 m 10-2'5 the distal presence of massive hematite lenses which
-151 • il r I ' ! ' 35o,i
gradeto cherty iron-formationand tourmalinitein
I
[ I I: ! Hematite
shallowto subaerialsedimentary settings.
At BigCa-
dia it is necessaryto explainthe gradationfrommag-
netite-hematite at the top of the body,to magnetite-
hematite-pyrite-chalcopyrite at the base.A further
featureof the ore is rapid deposition,which is re-
quiredto explainthe verylow concentrations of clas-
tically concentratedelementssuchasZr, TiO•, and
ß AI•O3in ironstone(Davidson,1989). To accountfor
. :: thesefeatures,the solubilitiesof iron and silicawere
-35.......
•........
-- •
•............................
• • Magnetite
i,,
examined.
A reviewof ironsolubility
-402 4 6 8 10 12 Theoreticalandexperimentalstudiesof iron have
pH
shown it to be readilysolubleaschloridecomplexes
in manygeologicfluids.Fe+• dominates in the range
FIc.9. A Iogfo•-pHdiagram forvolcanic copper-bearingoxide 50øto 200øC,FeCI+ from200øto 300øC,andFeCI•
assemblages formned between •;S= 10-2'5and10-3'ø.Accessory> 300øC (Barnes,1979; HemIcy et al., 1986), al-
bornitcoccurs in somefootwall alterationassemblagesandsome thoughin the raresituationof Cl--barrenwaters,hy-
Au-rich ironstonesatStarra
(forsimplicityonlytheoxidized region
of thebornitcfieldisshown here;seeFig.7 forthecomplete droxyandorganiccomplexes gainimportance(Sew-
field).Otherrelevantparameters areNaCI-- 3 M,K+= 0.5M,Ca+2 ard, 1977;Creraret al., 1985; Hennetet al., 1988);
= 0.5 M, azc= 10-]'ø(which[H2CO3] approximatesin solution), Fe+3ionsare onlypresentin veryoxidizedsolutions
azB•= 10-4'ø(asBaCI+). Thefieldofbaritemaybe morelimited (Barnes,1979).Iron solubilityis distinctlyincreased
thanis shown in thisdiagrambecause of thegreaterstability
of at lower pH values,at highertemperatures, and at
sulfate-alkali
ionpairsin brines(Henleyet al., 1984).(Fe-S-O
phaseboundaries: which greaterchloridecontents,with lesserinfluencesof
namesapplyto •;S-- 10-2'5M conditions,
are drawn as continuouslines; •;S = 10-3'øM boundariesare fo• andfs•(Creraret al., 1985;Whitneyet al.,1985;
dashed). Hemley
•t al.,1986).In addition,
a significant
in-
i i i
creasein thesolubilityofFeClø•with decreasing pres-
sureledHemleyet al. (1986) to concludethatascend-
ing hydrothermalfluidswere capableof scavenging Quartz
solubility
solutions inNaC1
(500 bars) /
/
Fe at near-adiabaticcooling.Theoreticallyandexper- 2000 /
imentallyFe is very solublein hydrothermalfluids; /
/
Creraret al. (1984) foundthatFe solubilityasa chlo-
ride complexincreases dramaticallybeyond250øC, • •./
transporting tensto thousands of ppmFe. Very high
Fe valuesin somemodernsalinehydrothermalsys-
temssupportthis data.For instance,McKibbenand
•
- '51
ß
Elders(1985) document93 to 4,200 ppm Fe in the 1000- Z//

salinegeothermalwatersof the SaltonSea.
At low temperatures(<50øC), iron is solubleas
Fe+•2,or asFe(OH)+ at alkalinepH. However,in the
presentday,fo2is toohighandPco2is toolow to
permitsignificantFe+2transportin the frameworkof
the equilibria(Garrels,1987)
, I I I
FeCO3+ H20 + COa = Fe+• + 2HCO•, (1) 0 200 3• 4• 500
with the result that the modern oceans do not contain Tempe•mre o C
appreciable Fe in solution.However,Whitneyet al. F•o. •0. A graphic•resentationo[ the e•eet o[ saltson silica
(1985) observedthat in high-temperatureaqueous solubility.Salinit•is an important[actorabove300øC(mo•ige•
experiments, Fe+•remainedin solutionafterquench- •rom Fournier, •983).
ing. They suggested this metastablebehaviorwould
alsooccurin natureand couldexplainthe consider-
able distancesseparatingsourcevents from some of suchsalinesolutionswouldlead to rapid silicade-
stratiformferruginous cherts. position,becausealthoughboilingincreases the fluid
salinity,this is insufficientto accommodate the tan-
A reviewof silicasolubility dem increaseof SiO2partitioninginto the fluid dur-
Under marineand mosthydrothermalconditions, ing the rapidexsolution of vapor(Fournier,1983).
SiO•is solubleasmonosilicic acid,Si(OH)4(Holland Whereassilicaconcentrations are predictabledur-
andMalinin,1979). The solubilityof quartzat 25øC ingrapidhydrothermal destabilizing events,suchas
(1 bar) in seawateris4.4 ppm,amorphous silicais 56 boiling,RimstidtandBarnes(1980) haveshownthe
ppm,andsilicagelis 114 ppm(Kastner,1979).In the importanceof kinetic effectsduringsimplecooling.
modernseas,biogenicactivitymaintainsgeneralsil- SiO•precipitation increases in proportiontotheavail-
ica undersaturation, whereas Precambrian marine ablenucleation surfacearea,expressed astheratioof
waterslikely hadsilicacontentswhichwere closeto surfacearea to the massof SiOn-bearingwater.
saturation,with the resultthat evenslightevapora- Where pluminghot fluidsmix abovethe sea floor
tionwouldhaveledto amorphous silicaprecipitation with cold seawater, the available surface area of
if feed water valueswere closeto the presentday otherprecipitatingmineralsislow, anddilutionwith
(60-70 ppm;Garrels,1987). undersaturated seawateris rapid, resultingin mini-
Hydrothermal solutionswhich have interacted malsilicaprecipitation.Ohmotoet al. (1983) suggest
with typicalcontinentalcrustin the range 150ø to that low silica/sulfide ratiosare goodevidencethat
350øC are closeto quartzsaturation,carrying100 to many massivesulfide ores formed from sulfides
1,500 ppm silica(Rimstidtand Barnes,1980). Ideal whichprecipitatedabovethe seafloor duringfluid
silica solubilityis dependenton temperatureand mixing,aswell asconstitutinggoodevidenceagainst
pressure, but virtuallyindependent of pH (belowpH boiling.In contrast,largeamountsof silicaaredepos-
= 8; Fournier,1983). Silicasolubilityis slightlyen- ited in systemswhich are characterizedby slow
hancedby increases in ionicstrength(Fournieret al., coolingand large availablesurfaceareas,such as
1982). These featureshave permitted the formula- the fractured stockworks below some VMS ores.
tion of silicageothermometers basedon the silica Kalogeropoulos and Scott (1983) recognizedthat
contentof geothermalfluids(Truesdell,1976), also low-temperaturehematite-quartz"exhalites"must
allowingthe approximationof silicaconcentrations have formedby precipitationof silicaon the many
withoutconsideration of otheraqueous species. The mineral surfaces within unconsolidated sediment and
effectof addedsaltis to increaseslightlythe peak volcaniclastic debris.It followsthat hydrothermal
temperature of retrograde solubility, promoting fluids dense enough to follow sea-floorcontours,
moredissolved silica(linesA andB; Fig. 10). Boiling suchasthe type I andII salinefluidsof Sato(1972)
900 GARRY
J.DAVIDSON
(Fig.11) andthedistalexhalites
ofLarge(1977),are layer-parallelsulfidegrowthistypicalof the modern
very likely to depositmoresilicathanturbulently SaltonSeahydrothermalfieldin unconsolidated sedi-
mixingfluids,suchasblacksmokerores. ments (McKibben and Elders, 1985) and strata-
A Model for the Concentration of Silica and Iron bound sulfidedeposits,suchas Meggen,Rammels-
berg, McArthur River, and Mount Isa (Lambert,
Starra:Wasfluid discharge focusedor dispersed? 1976). In contrast, the presence of some con-
Stringer-styleoxideveinletsare pervasivein the solidated rockduringalterationisevidenced by brec-
Starrafootwall,increasing in abundance towardthe ciation(in this instanceunrelatedto deformation)in
iron-formation; themajorcopper-gold-bearing lodes the intense oxide alteration zones below area 251;
are also associated with local intense chloritic alter- theserocksmayhaveoriginatedaslavaswithin the
ation(areas'257and 244) or severelocaliron oxide felsicpyroclastic-epiclastic sequence.Thechloriteal-
alteration(area251;Fig. 2). Thepervasive alteration teration is attributed to elevated seawater-rock inter-
is evidenceof dispersed exhalationat manypoints, actionin the stockwork,permittedby hydrothermal
accompanied by focuseddischargebeneathmajor brecciationand seawaterentrainment(Riverinand
orebodies. Texturalevidencewaspresentedin Da- Hodgson,1980; Lydonand Galley, 1986). Severely
vidsonet al. (1989)for thegrowthofpyritein uncon- iron oxide-alteredzoneswere similarlyfocuseddis-
solidatedsediment.A porousstate of the altered chargepoints,but were presumablysealedfrom the
mediumcouldalsoaccount forthecommon bedding- water columnat an early stageby the depositionof
parallelnatureof stringerveinletsandthe dissemi- hydrothermalprecipitates.
natedpervasivenatureof oxidealteration.Pervasive, Fluid behavior
The formof exhaledorebodies iscontrolledprinci-
pallyby fluidbehaviorandmodeof discharge during
exhalation,as arguedby Sato(1972), Solomonand
Walshe (1979), and Turner and Campbell(1987).
Thisis mainlya functionof fluiddensity;Sato(1972)
suggested that very salinefluids(type I; Fig. 11)
would remain more dense than seawater and form
densitycurrentsandbrinepools,whichresultin thin,
well-layered,tabularbasemetalores,suchasthoseof
the Red Sea deeps.These could alsoform by dis-
persed hydrothermaldischargefrom many small
vents,asissuggested for theRoseberydepositof Tas-
mania(Huston,1989). Turner andGustafson(1978)
emphasized theoreticalnonlineardensitymixingfor
exhaledsalinefluidsand thermohalineeffects,which
_"
/ype II
' /12,0/
I//// /
7/ / have since been demonstrated for Red Sea exhalation
by Pottorf and Barnes (1983) and Ramboz et al.
(1988). TurnerandCampbell(1987) havecalculated
thatall fluidshotterthan300øCwill be initiallymore
buoyantthanseawater,but if salinityis greaterthan
• 7 wt percentNaC1,will showa buoyancyreversal
onmixingwith seawater,formingthe typeII fluidsof
Sato(1972). Modern hydrothermalsystemsat mid-
Type I ///'?'7-//'
oceanridgesdischargein buoyantplumesconform-
ing to the type III fluidsof Sato (1972). Approxi-
•Hydrolhermal
(•Hydrothermal
vent plume mately97 percentof the mineralload precipitates
highin the plumeduringturbulentmixingandis dis-
•.•,.e a floor • Brine
pool
persedover a wide area.The remainderis incorpo-
ratedinto the sulfidemound,whichowesits growth
Sulphide nucleationzone
to the formationof anhydritechimneysduringthe
solubilitydecreasethat anhydriteexperiences when
FIG. 11. A schematic representation of threefluidtypes,modi- heated to 130øC (Haymon and Kastner, 1981). A
fiedfromSato(1972).TypeI solutions aretopography hugging smallproportion of dischargingfluidistrappedin the
because of theirhighsalinities,
typeII reversing plumeshavein-
termediate salinities,
andtypeIII solutions aremorebouyantthan pores of the anhydrite wall,depositingsulfides
across
seawater. TheverysalineStarrafluidislikelyto havebeena typeI a steeptemperature-pHgradient.
or II solution. High silica ironstoneat Starra,which correlates
positivelywith Au (Davidsonet al., 1989), precipi- Seyfried,1984), as occursin typicaltype III fluid
tated closestto the ventsat Starra.Followingthe plumedispersal(Sato,1972), asa testof the conclu-
logicof Ohmotoet al. (1983), the highlysiliceous sionsof the previousdiscussion. Thiswouldresultin
characterof somecopper-bearing iron-formations is a continuous increase
in pH andfo2duringcooling to
evidencethat they did not form from a type III moveintothehematitefield(A; Fig. 12). Evendisre-
buoyantlydispersing plume.At •350øC and high gardingthe aforementioned kinetic effectson silica
salinity,a type II reversingplumecollapsing into a precipitation,thispathresultsin an accumulation of
typeI densitycurrentis mostlikely.A secondpossi- iron closeto the vent, rather than silica.
bility is the depositionof proximalsilicaby advec- The secondpath(B;Fig. 12) assumes thatthe fluid
tive-conductive coolingin the outerpart of a semi- mixedwith seawaterin the 300ø to 350øC range
matureoxide mound,sealingit, and thereforein- prior to collapsingon the vent, as envisagedby
creasing intramound fluidmixing.So-called seafloor TurnerandCampbell(1987). It thencooledby con-
"whitesmokers," precipitating barite,silica,andpy- ductionandslowmixingasa densitycurrentmoving
rite, are thoughtto evolvein thisway (Rona,1984; downslope from the vent, maintaininga near-con-
Herziget al., 1989).Suchsubsurface goldsilicadepo- stantpH. Thisvariationproducesan initial decrease
sitionmay have occurredat Starra,but where well- in silicasolubilityrelative to iron, which could ex-
definedbandsof quartzarepresentin theironstone, plain a ventwardconcentrationof SiO2.Silicawould
an origin by precipitationon the seafloor is most depositwhenthecollapsing plumecontacted thesed-
likely. imentsurface,with the kineticcontrolon silicapre-
cipitationproducingadditionalsilica,althoughthis
Iron-silicasolubilitypaths wasnot modeled.PathB furtherpredictsan areaof
On the basisof the previousdiscussion, two fluid retrogradeFe+2solubilitybetween150ø and100øC,
pathswere modeledto assess their effectson Fe and whichwouldencourage the distaltransportof iron.
Si deposition. Giventhe swarmof assumptions, this A pathof coolingwithoutchangein pH valuesbest
exercisewasintendedto be approximate, ratherthan explainsthe featuresof Starraores.It is envisaged
reproducethe exactSi/Fe ratiosof the Starrairon- that asthe chemicalsedimentcomplexgrew,rising
stone.Bothfluidpathswereassumed to commence in fluidsenteredandreactedwith it, for instance, by
the magnetite-chalcopyrite field, from singledis- alteringearlierhematiteto magnetiteandpyrite to
chargepoints(Fig. 12) at 350øC,pH -- 4.5. chalcopyrite.This couldexplainthe commoncom-
Thefirstpathinvolves continuous linearmixingof pleteabsenceof pyritein the magnetite-chalcopyrite
seawater (assumed atpH -- 7,fo2-- -64; Janecky and zoneandthe notedconcentration of goldtowardthe
fO2 -47 -40 -35 -32 -30 -25

1 oooo
HEMATITE
1 ooo
1 oo
lO
.1
pH=5.6
• SiO2
(200B)-- Fe ßpH varies
.Ol
6 =5.9 . FeßpH=4.5
.OOl
0
!
1 O0
!
200 300 400
Temperature øC
FIG.12. Saturationpathsforsilicaandironunderthe specificconditions

ofNaC1= 3 M, 2;S= 0.001 M,
andpressure= 200 bars.The diagramassumes Fe to be transported
fromthe magnetitefieldinto the
hematitefieldasFeCIø•,
FeC1 +,andFe+•.Silicatransportisindependent ofpH in thediagram,
whereas it
isanimportantcontrolonironsolubility.PathA models anidealFe-richsolution
mixinglinearlywithcold
seawater,henceregularlychanging the pH (bouyantlydispersing
plumedischarge). PathB modelsan
idealFe-richsolution
whichcoolswithnochange inpH, suchasa densebottom-hugging brine.Equilibria
wereobtainedfromBarnes(1979) andBowerset al. (1984).
902 GARRY
J.DAVIDSON
topof someironstones (KaryandHarley,1990)dur- evolved meteoric or marine water, with a connate

ing zonerefining(Eldridgeet al., 1983). contribution(Davidson,1990b). Abundantfinely
Hematite lenses in the ore environment are envis- bedded hematite and an absence of carbonaceous
agedto haveformedat lower temperatures (50ø- matter provide evidence that the water column
150øC),whenbrineswere pondedby topography, above the accumulatingStaveleyFormationsedi-
precipitatingiron oxidesduringfurther coolingand ments(Starraenvironment)waswell oxidized,aswas
slowmixingwith the ambientoxidizedwaters.This the diageneticenvironment.NegativeCe anomalies
processproducedvery thick but barren hematite in somesouthernStarrabandediron-formations,and
lenses,suchasthoseof areas232,244, and 276. The thoseat Osborne,are evidenceof marine waterswith
elevatedW, Sn, and Cu valuesin theselenses,com- a similaroxidationstateto that of the presentday
paredto moredistalbarrenlenseswith similarminer- (Davidson,1989).
alogyandmajorelementchemistry,is attributedto A circulationhistory,whichbufferedthe fluidoxi-
their evolution from hotter fluids. dationstateto highfo•, issuggested
by theoxidized
Distal hematite lenses,suchas those of area 186, natureof lowertemperatureveinsat StarraandOs-
andthe easternhematites,canalsobe explainedin borne.The oxidationstateof hydrothermalfluidsis
termsof path B (Fig. 12). Massivebarrenhematitic normallycontrolledby aquifermineralreactions,for
ironstoneswere depositedproximally around hot instance,oxidizedseawaterbecomeshighlyreduced
springventsin shallowsubbasins, at temperatures at midoceanridgesduringbasaltinteractionby the
belowthoseconducive to highgoldandcoppersolu- reactionbetweenquartz,fayalite,magnetite,andthe
bilities. fluid(QFMbuffer,fo• -- -39.5 at 275øC;Bischoff
Modernsea-floor studiesrecognize a groupoflow- and Seyfried, 1978; Mottl, 1983). The Tennant
temperatureiron oxidedepositswhichform by the Creek epigeneticoresof centralAustraliaare an ex-
bacterialoxidation
ofhydrothermal ferrousiron(Alt, ampleof a fluidbufferedto a hematite-magnetiteoxi-
1986; Juniper and Fouquet, 1988; Duhig et al., dationstateby reactionwith an oxidizedfootwall
1992). The hydrothermal fluidstransportverylittle (hematite-and magnetite-bearing turbidites;Large,
H2S,thereforedepositing onlycrystalline andamor- 1975; Wedekind et al., 1989). In a similarfashion,
phousiron oxidesand opalinesilica--not sulfides the oxidized sedimentswhich typify the shallow-
(Hekinianand Fouquet,1985). The chemistryof water evaporiticMary KathleenGroup and upper
someofthesedeposits issimilarto thatof Starradistal Kuridala Formation could have constituted effi-
hematitelenses,asshownin Table1, raisingthespec- cient oxidationbuffers.The presenceof significant
ulationthat depositionof someStarrahematitelenses amountsof reducedbasalt,ilmenite-bearing felsic
mightalsohavebeenbiologically facilitated. volcanics,or carbonaceousshale in the Starra foot-
wall is discounted,becausefluid reactionswith these
Fluid and metal sources
materialswouldhaveproducedreducedrather than
Two typesof fluid are postulatedat volcaniccop- oxidizedassemblages, andthe presenceof abundant
per-bearingoxidemineralization sites.The firstwas carbonaceous rocksisnotsupported by sulfurisotope
the free-standing
water columnand the secondwas evidence.The natureof the deep footwallat Starra
the hot, metal-bearing,hydrothermal fluid. Hydro- can only be inferredin this way, becauseit wasre-
thermalsolutions which are formingmodernmid- movedduringpostoretectonism.
oceanridgeCu-Znoresoriginateasseawater,chemi- A secondimportantpotential sourceof oxidized
cally modified during fracture-controlleddescent fluidsis highlyfractionated,
K-rich,magnetiteseries
and subsequentfluid circulationclose to a heat (I-type)granites,whichareparticularlyprevalentin
source.Oxygenisotopes fromironstonecalcites,and Australianearthhistorybetween1600 and1500 Ma
thehighsalinities
of area222 inclusions, suggestthat and are present in the Mount Isa area, although
the circulating
StarraandOsbornefluidoriginated as mainly aged youngerthan the ore sequencesdis-
T• 1. AverageVolatile-FreeIron andFe/SiRatiosfor SomeModernSea-FloorOxidePrecipitates,

Comparedto the AverageStarraDistalHematiteLensComposition
F%Oatot•(wt %) Fe/Si Reference

Starra distal hematites 81.6 12.8 Davidson(1989)
Oxide muds at 21ø30 t S on the East Pacific Rise 65.8 11.5 JuniperandFouquet(1988)
Red Volcano seamount 71.5 8.3 Alt (1986)
Core B, Santorini, Greece 47.9• 8.6 Bostrom andWidenfalk(1984)
Not calculated on a volatile-free basis

Temperature
øC
I I I I I•/
mag-cl:)Y,•l:)Y••g_cl:)y
HEMATITE
- ;,•.,•' / MAGNETITE
-40 -
'/. •' • PYRRHOTITE
-50-
FIc. 13. A 1ogfo2-temperature

diagram
illustrating
thelikelycooling
pathof theStarrafluids.This
pathhasbeenusedto calculatethe metalsolubilityalternatives
presented
in Figure12.
cussed here(Wybornet al., 1988).Lyons(1988)pos- sionof eventsoutlinedabove(Fig. 14). An upwelling,

tulatesthat at extremedegreesof fractionation,an more reduced,saline,metal-richbrine diapir mixes
Fe-F-C1-CO2-H20-dominated immiscibleliquidmay with an overlying,oxidized,metal-poorfluid at an
exsolvefrom a graniticparent,andeither ascendto ascending interface.In the volcaniccopper-bearing
the surfaceto form oxide-dominatedlava flows, or oxide modificationof the model, the lower fluid in
more commonly,crystallizeat depth evolvingeven equilibriumwith magnetitebreachesthe sediment-
moreoxidized,acid,volatile-richfluids.The culpa- water interfaceand depositsAu-rich ironstone.In
bility of sucha sourceis uncertainfor the three Aus- thewaningphasethe systemcoolsandthe fluidinter-
tralianexamples discussed,
but seemsmostlikely for face subsides,
drawingin cooleroxygenatedwaters
Big Cadia, where the immediatefootwall is domi- andforminglate-stagehematiticveinsat depth.The
natedby reducedandesites. hematiteveinsare mostlikely postpeakhydrother-
A hypothetical fluidcoolingpathforStarraisrepre-
sentedin Figure13. Heating(accompanied by leach-
ing of iron and silica)followeda constantoxidized ] IMag
netitc
I - ".....
ing [I Hematite
I
•SO4/H2Scontourfrom 25ø to 200øC in the hema-
tite stabilityfield.The •;SO•2/H2Sratioof the fluid •.tera• ••e _. I alter• __
then alteredby (1) an increasein rate of reactionof
the equation
SO•2 + 2H+ = H2S+ 202,
in heatingfrom200øto 350øC;(2) anhydritedeposi-
tion duringheatingfrom T >_150øC (Bischoffand
Seyfried,1978);and(3) entrainmentofdeeper,more
reducedwaters,evidencedby a componentof oxi- FIc. 14. A brinediapirmodelfor oreformation,modifiedfrom
dizedorganiccarbonin ironstone calcite(Davidson, the uniformitarian approach
of McKibbenet al. (1988).A. A brine
1990b). diapirof hot salinefluid (H), drivenby a risingpluton,ascends
McKibbenet al. (1988) haveproposed a modelfor through a layerof intermediatesalinityfluid(M) to exhalemagne-
tite-Cu-Auore at the seafloor.B. Uponcooling,the brinediapir
theSaltonSeageothermal fieldwhichcanbe applied descends, drawingin cooleroxidizedwaters(L) whichformsub-
in a modified form at Starra and relies on the succes- surface hematite veins.
904 GARRY
J.DAVIDSON
mal,becausethe prepeakhematiteveinswouldhave assume that Cu and Au were leached from the same
beendestroyed
by the ascending
brinediapir. sediment volume.
The anomalous W and Sn in the Starra ores could
be explainedby entrainmentof magmatic fluidsfrom Thefate of lead and zinc:Potentiallinkswith
theunderlying heatsource,orby alterationofW-rich Pegmont-Broken Hill-stylePb-Znbandediron-
detritusin the footwall(Ririe, 1989); the relative formationores
easeof transportingW asan ion pair (NaHWO4 ø) in Lead andzincoccurat extremelylow abundances
salinefluidshasbeen demonstrated by Wood and in volcaniccopper-bearing oxidemineralization(for
Vlassopoulous (1989). Cu enrichmentat Starra is instance,the averagein area257 ironstoneat Starra
readily explainedby leachingof typical oxidized is 1.0 ppmPb and2.9 ppmZn). Thisposesa paradox,
shallow-waterMary Kathleen Group sediments, becausethe stronglychloride-enriched Starrafluids
whicharelikely to containelevatedbasemetalback- musthavebeenPb-Znrich,asillustratedby the high
groundconcentrations (e.g.,RedBeds,Renfro,1974; Zn andPb abundances of the analogous salineSalton
Muir, 1979). Cu enrichmentthroughoutthe region Seafluids(•,350øC, 3 M NaC1;average506 ppmZn
alsomay owe its originto sucha preconcentration. and95 ppmPbfor the deepaquifer;McKibbenet al.,
However, even modest assumptionsconcerning 1988). Evenat theseconditions,SaltonSeafluidsare
averagesedimentCu contentsanddegreesof leach- markedlyundersaturated in PbandZn (Fig. 15); satu-
ing indicatethat the StarraCu tonnagecan be ac- rationof 506 ppmZn is onlyapproached at •240øC
countedfor by geologicallyreasonabledepthsof (2•as-- 10-3 M), whereasthe averageSaltonSeaCu
fluidcirculation.The 8.8 X 10]øg of Cu in area251 value of 6 ppm is saturatedat •330øC, usingthe
canbe produced by 10 percentleachingof 11.7 km3 solubilitydataof WalsheandSolomon(1981). These
of sandstone and shalecontainingaverageCu con- valuesprovidereasonablecluesasto the fate of Pb
tents(28 ppm, assumed densityof 2.7 g/cc;Brown- andZn in volcaniccopper-bearing oxidefluids.It is
low, 1979).Thisequatesto a leachingconewith the suggested that precipitationof chalcopyriteandpy-
formulaH -- 11.2/R2, where H is the heightof the rite in the Starramagnetiteironstoneoverthe range
cone in kilometers,and R is its basalradius.A leach- 330øto 260øCdeposited90 percentof the Cu, over-
ing coneof 2-km-radiuswill extendto a depthof 2.8 lappingwith pyrite deposition,and in doing so re-
km.A volumeof •' 18 km3 isrequiredto providethe movedall H2Sfromthe fluidprior to Pb andZn satu-
1.7 x 10v g of Au in area251, againassuming 10 ration.The highlyoxidizedwater columncouldnot
percent leachingof averageterrigenoussediment supplyreducedsulfuron the sea floor. Pb and Zn
(3.5 ppb; Boyle 1979). Given that salinesediments which did deposit within the ironstonewas sca-
havehigherAubackgrounds thanaveragesediments, vengedby expandingisothermswithin the accumu-
(haliteevaporiteshavean averageof between20.8 latingexhalitesanddispersedinto the watercolumn
and 23.8 ppb Au; Boyle, 1979), and that these (zonerefiningof Eldridgeet al., 1983).
formedat leastpart of the footwallsequenceto ac- Essentiallythen, the lack of Pb and Zn is not re-
countfor the highsalinities,an evensmallervolume lated to sourcedeficiencies, but to the very low H•S
would suffice.Thus for Starra ores, it is feasible to contents of the ore fluid and the host surface waters.
Conditions:
pH = 4.5, NaC1= 3M, [SO4]/[H2S]= 0.01, Y•S--0.001M
10.0
• Cu
ß T_,Au(el)
-- Pb
ß Zn
Cu -- T_.,Au(H
S)2
0.0
Au(C1)
Au(HS)2 -
-10.0 , ,
100 200 300 400
Temperature 0 C
FIG. 15. Metal saturation
curvesfor chloride-complexed
Cu, Pb, Zn, andAu andfor Au(HS)2.
Circumstantial verification of this mechanism ex- fur isotopesignature. Limiteddataaveraging •ia4S=0

istsat the MobsLeaseandBlockbuster prospects20 per mil from the Pegmontdeposit(Vaughanand
kmnorthof Starra,in anequivalentstratigraphic
po- Stanton,1986), similarto the averageof Starraand
sition.Theseare magnetite-quartzexhaliteswhich Osbornesulfide(Davidsonet al., 1989), favorsthe
sharethe Au-Cu-Wassociation of Starra(henceim- latter option,but a migratingbrine model may be
plyingtemperatures> 260øC),but alsocontain75 to applicableto otherexamples.
1,490ppmPband115to 1,480ppmZn (unpub.Cy- In summary,it is likely that a chemicaltransition
prusMineralsgeochemical data).The hangingwall exists between Cu-Au +_W +_Co banded iron-forma-
containssomegraphiticshale,which suggests that tionsof the volcaniccopper-bearing oxidestyleand
more reduced sulfur was available on the sea floor Pb-Zn-richbandediron-formation oressuchasPeg-
than at Starra,permittingprecipitationof somePb mont,and that the latter couldtheoreticallybe de-
and Zn. rivedfromthe formerduringthe lateralmigrationof
Pegmont-stylePb-Zn-Agbandediron-formations a denseand coolingbrine. Chemicaland physical
in the Cloncurrydistrict(in the vicinityof Starraand transitions wouldbe dependentonthe initialtemper-
Osborne)are an ore stylewith manyfeaturesof the atureof the fluid, its H•S content,andthe H•S con-
AustralianBrokenHill ores(StantonandVaughan, tent of the surrounding waters.
1979)andmaybe viewedwithinthesametheoretical
framework.To explaintheir features(Pb-Zn-Ferich, Therelationship betweendepth,salinity,
Cu-Au-Wdeficient),it is suggested here that they and fluid boiling
developedfrom relativelylow temperaturefluids Starra:The acceptedproof of boilingwithin a hy-
(<260øC)incapableof dissolving Au andCu aschlo- drothermalsystemis the presenceof heterogeneous
ridecomplexes. Sucha fluidmayhaveoriginated asa liquid-vaporfluidinclusions withsimilarhomogeniza-
migratingbrinewhichwasinitiallyveryhot andhad tion temperatures; thisproofis unavailableat Starra,
alreadydeposited a proximal Au-Cudeposit(seeFig. Osborne,or Big Cadia. Secondaryevidenceis the
16),or it mayhaveoriginated asa lowertemperature generation of footwallbrecciazonesaccompanied by
fluidwith a higherintrinsicsulfurcontent,closeto metalandsilicadeposition; silicain particularattains
the centerof a ventsystem. In the distalcasesulfides saturationrapidlyby boiling,asattestedin numerous
wouldbe deposited whenthefluidsscavenged H•Sin epithermalsystems. At Starra,evidenceof footwall
anaerobicsea-floordepressions and would very hydrothermal brecciationor silicadeposition isscant,
likely exhibita biogenicsulfurisotopecharacter, althoughthe formermayhavebeenlargelyobscured
whereas proximal low-temperaturePb-Zn ores by subsequent deformation. In addition,the majority
wouldexhibita magmatic or seawater-dominated sul- of metals and silica are confined to the ironstone
beds,whichsuggests that any boiling-related metal
precipitationoccurredon the seafloor,notbelowit.
Usingthe boilingcurvesof Haas(1971), depthsof
The formation of Pegmont-style Pb-Zn in BIF, from a between670 and1,030 m wouldhavebeenrequired
laterally migrating saline VCO brine.
to preventthe boilingof 300ø to 350øC, 25 wt per-
centNaC1equivsolutions envisaged for Starra.
- deeps
Osborne: With respect to the probable initialtem-
S exhausted by cpy
before Pb-Zn saturation perature,sulfurfugacity,salinity,andmetalcontent,
the OsborneandStarrafluidswereprobablyverysim-
e ilar, on the basisof their similarchemistryandalter-
ationmineralogies. The scaleof Osbornealterationis
yet to be demonstrated to be aslargeasthatofStarra.
o Its focused,brecciated,andsilicifiednatureare a fur-
ther contrast,as are the associatedmore continuous
Pegmont-style Pb-Zn and well-banded iron-formations. On the basis of the
deposition, 100-250 ø C
Oxidised saline previousdiscussion, the silica alteration zonesare
Iow-H2S fluid,
T= 280-400 øC bestinterpretedasproductsof fluidboiling,resulting
in coolingof the solutionthroughquartz,magnetite,
FIc. 16. The diagrammatic formationof Pegmont-style
Pb-Zn- and metal precipitation.The result wasthe deposi-
rich bandediron-formations froma laterallymigratinghot brine tion of a largerproportionof subsea-floorAu andCu
whichoriginated at a volcanic copper-bearing oxidevent.Local thanis evidentat Starra.The salinityanddensityof
HaS-bearing marinedeeps(A) area criticalpartof the model.Pb-
Zn-richbandediron-formation couldalsoformfrommoderately
the remainingfluid wasenhancedby vaporsepara-
oxidized200ø to 250øCfluidsat a ventsite(B),a modelwhichis tion,emerging ontotheseafloorasa typeI or II fluid
advocated for Pegmont itselfby the sulfurisotopeevidence(Da- of Sato(1972)to forma brinepool.Cu andAuvaried
vidson,1989;Davidson andDixon,1992). systematically awayfromtheventin thewell-banded
iron-formations, due to conductivecoolingandfluid andpH _<6 (to promoteCu solubility).

While high
mixingon the brine-waterinterface.With time, in- salinitieswouldpromotethis ore depositstyleand
of the hydrothermalsystemoverprinted potentially
tensification increase
orebodysizeby increasingchlo-
and redissolvedsomestratiform exhalites;three ma- ride ion-pairmetalsolubilities,
theyare notmanda-
jor hydrothermalpulsesare requiredto explainthe tory.High salinities
inducelow pH andstabilizeal-
three main iron-formation levels. The distinctive Co bite relative to muscovitein the alteration.High-
and P enrichment, like the W enrichment at Starra, is fluid calciumcontentsand highfo2 can stabilize
bestexplainedin termsof footwallpreconcentration. epidotein the alteration.Salinity,waterdepth,and
ElevatedCo hints at a large maficbody within the modeof discharge are interrelatedcontrolson the
footwall, or Co-rich shales. extentof individualdepositsandtheir silicacontents.
A fastchemicalsedimentaccumulation rate is sug- This distinctassociationof physicaland chemical
gestedfor Osborneby the lackofa clasticcomponent features,not previouslyaddressed by existingore
withinthe orebands,despitetheir intercalation with genesis models,warrantsthe definitionof a newmin-
coarse-graded,and crossbeddedquartz- and feld- eralizationclass,the "volcanogenic copper-bearing
spar-richmetasediments. Alternatingmagnetiteand oxide"deposits. Their deposition is favoredin (but
quartzmesobands are interpretedasproductsof sin- notconfinedto) shallowcontinental rift settings,
be-
gle hydrothermalpulses,separated by the kineticef- causethesecan containthe requisiteoxidizedsedi-
fectswhichhinderSiO2precipitationduringcooling mentsor evolvedmagmas capableof producingoxi-
(Rimstidtand Barnes,1980). dizedhydrothermalfluids.
The strongbeddingplanepreferencefor Osborne In thispaper,thisclassis regardedastransitional
alteration,resultingin extremelyflattenedfunnel between barren, low-temperature, volcanogenic
shapesof the silicazonesandlayer-parallelveins,is massiveoxidedeposits(e.g., the ancientLahn-Dill
attributed to the unconsolidated state of sediments andTeliuc-Ghelarsubtypes; Quade,1976; Krautner,
duringmineralization. Presumably expansion of the 1977; and modernexamples;Bostromand Widen-
boilingfluidswasfocusedalongbedding,whichcon- falk, 1984; JuniperandFouquet,1988; Kimberley,
stitutedtheweakestsubsurface parting.True veinsof 1989) and volcanic-hosted massivesulfide(VHMS)
magnetiteand pyrite were probablyonly possible orescontaining significantmagnetiteCu zones,such
once areasof intensesilicaor feldsparcementation as Golden Grove, Corbet, Orchan, AndersonLake,
had lithified the sediment. Balcooma,andBoksputs (Large,1977; Knuckeyand
BigCadia:At BigCadiaa subcircular (plan)mound Watkins, 1982; Walford and Franklin, 1982; Frater,
of magnetite-hematite givesway with depth to a 1983; Huston,1989; Geringeret al., 1987). The
magnetite-hematite-pyrite-chalcopyrite assemblage. Caledonianvolcano-sedimentary rocks of Norway
There is no distaldevelopmentof stratiformiron ox- containores which cover this complete spectrum
ide beds,andthe oresclearlyoverliea distinctzone withina singlebelt (Waltham,1968; Nilsen,1978).
of focused alteration. These features are best ex- This transitional character is considered in terms of
plainedby the ascentof an oxidizedlow-salinityore temperature,H•S•uia,andH•S..... terin Figure 17.
fluid into oxidizedseawaterto form a hydrothermal It isnottheintentionofthispaperto gliblylumpall
plume(typeIII fluidof Sato,1972). The presenceof stratiform-strata-boundmagnetite-copper-bearing
the sulfidephasesonly at depthin the bodyis evi- rocksintothe volcaniccopper-bearing oxideclassifi-
dencethattheyformedby replacement of earlierpre- cation,but there are manydepositsdistributedfrom
cipitatesfrom below, rather than aspure exhalites. the Archean to the Phanerozoic of sufficient resem-
There is no physicalevidencedocumented to date blance to warrant consideration,which have to date
that the fluidsboiled during their ascent,but it is resistedclassification
andunderstanding.
The genesis
likely that they did, giventhe sedimentaryevidence of eachneedsto be carefullyconsideredin the light
of a shallowdepositionalenvironment. of anynewdata.Globallydistributed examples ofpo-
tentialvolcaniccopper-bearing oxidemineralization
A Comparisonwith Other Ores: include Fosdalen(Norway); Pahtohavore,Viscaria,
The Definition of a New Classof Volcanogenie Saxberget,Ljusnarsberg (Sweden); Atikokan,Snake-
Copper-bearingOxide Deposits weedLake, Granduc,Pacand,Bousquet4 lens(Can-
The detailedcomparison of three Australiancop- ada);Salobo3A (Brazil);andthe Athensmine(Zim-
per-bearing,sea-flooroxide depositssuggeststhat babwe,Africa)(Frietschet al., 1979;Kirkham,1979;
the primary controlon their mineralogyand geo- Carlson, 1991; Filho et al., 1988; Foster, 1988).
chemistryisthe low H2Scontentof the ore fluid and Their featuresare summarizedin Table 2. The very
ambientwatercolumn,coupledwithhighhydrother- largetonnageofSaloboisanindication oftheconceiv-
mal temperatures.In detail the controllingparame- able importanceof the style among ore genesis
tersareT >_260øC,highfo2,H•Sauid
< •10 -•'5M, models.
SEA-FLOORVOLCANOGENIC COPPER-BEARINGOXIDE ORES 907
inWaterco/utah zones
H2S of barren oxide faciesiron-formation; the simi-
larity of the elementassociation to (a) alsosuggests
350 bisulfidegold complexing(MacDonald,1983; Phil-
lips et al., 1984; Groveset al., 1987).
300 _•
Conclusions
2•0•E' A syngeneticmodelwith no knownmodernana-
OOo• o
Iogueis advancedto explainAu-Cu mineralizationat
c)
StarraandOsborne,supportedby evidencefromthe
BigCadiadeposit.The heatsourceandplumbingsys-
tem for the Mount Isa exampleswere providedby
extensionalfaulting and acid basicmagmatismin a
secondaryrift or pull-apart basin; hydrothermal
fluids equilibrated with oxidized halite-rich sedi-
ments,ascending throughandpervasively alteringan
Possible coolingpath to unconsolidated rhyodacitic pyroclastic-epiclastic
Pb-Zn BIFfroma VCO fluidby pile. These salineexhaledfluids initially produced
entryintoan H2S-rich
environment low-temperaturehematite strata, possiblyprecipi-
tatedwith the aid of bacteria.A magnetite-dominant
systemevolvedby the deepeningof fluid circulation
to includemoremagnetite-buffered waters,or specu-
latively,by the ascentof a reducedhigh-temperature
brine diapir to the seafloor, modeledon the Salton
Seaaquifersystem(McKibbenet al., 1988). In sev-
FIG.17. A schematic representation
ofthevariationoftempera- eral areas, poddy breccia-bearinghematitic iron-
ture,theamountof H2Sin ahydrothermal fluid,andtheamountof
H2Sin thewatercolumn,fordifferentoretypes.Blacksmokerand stoneswere developedby fluid invasionof subsur-
kuroko-style volcanic-hosted
massivesulfideoresformfromH2S- face,porous,sedimentary conglomerates; at area222
richfluidsenteringH•S-poorseawaterat 250ø to 350øC.In con- thesefluidscarriedAu and Cu, which mayhavede-
trast, Starraand other volcanogenic
copper-bearing oxideores positedby decompressional boilingin the porousma-
formedfromfluidslowin H2S,enteringa lowH•Senvironment, at trix of the conglomerate.Synmineralization fluid in-
VHMS temperatures. Increasingwater columnH•S whichis avail- clusions in these breccias are the best evidence in the
able to a densemigratingvolcaniccopper-bearing oxidefluid
couldproducePb- andZn-enrichedbandediron-formationof the Starraareafor the high salinitiesof the ore fluids.
Pegmontstyle. At areas257 and 251, Starra, an ironstonezonation
of magnetite-chalcopyrite-gold, to magnetite-hema-
tite-chalcopyrite-pyrite_+gold,to hematite_+pyrite,
A dominanceof iron oxides,and the disseminated accompanied by a steadydecreasein silicacontent,is
natureof the copperandiron sulfides,separatethis interpreted as the product of physicochemical
ore type from: (a) silicate-carbonate-sulfide facies changes in a fluidasit movedawayfroma vent,over-
iron-formationgold deposits,such as Homestake lying chloriticandoxidealteration.Subsurface alter-
(Sawkins andRye, 1974), MorroVelho(Bernasconi, ationof the earlyhematiticassemblage to magnetite-
1988), The Granites(Ireland and Mayer, 1984), chalcopyrite aroundthe ventisenvisaged. Fluidcon-
GoldenDike dome(Nicholson, 1980),Jardine(Hal- ditionsof golddepositionwere T -- 260 ø to 380øC,
lager, 1982), and the Salisgnes depositof France pH -- 3.9 - 6, Iogfo•-- -27.5 to -30, salinity >_3 M
(Bonnemaison et al., 1986), whichhavein common NaCI;Au andCu were transportedaschloridecom-
reduced sulfide assemblages, low iron oxide con- plexes,whereasW was most likely transportedas
tents, and an As-Sb-Au-W _+Pb, Zn, and Cu associa- NaHWO4 ø (WoodandVlassopoulos, 1989). The dis-
tion; the features of such ores could be accommo- tributionof silicaandgoldalsois evidencethat any
datedby metalbisulfidetransportin a reducedset- fluidboilingdid notcausesubsurface SiO2saturation
ting,at lowertemperatures thanthoseenvisaged for at Starra,whereasthiswasverylikelyat Osborne.Big
volcaniccopper-bearing oxideores;and(b) replace- Cadiaformedfrom similarlyhot oxidizedfluids,but
ment Au-bandediron-formationdeposits,such as salinitywascloseto that of seawater.Thisresultedin
Hill 50, Australia(Phillipset al., 1984),Lennox,Zim- a dominance ofK-richphases andepidotein thealter-
babwe(GilliganandFoster,1987),andLupinmine, ation pipe and probableplume behaviorof the as-
Canada(LhotkaandNesbitt,1988),in whichmassive cendinghydrothermalfluid as it entered the water
sulfides (pyrrhotite,pyrite,arsenopyrite) areepige- column(a far lessefl]cientmeansof metal deposi-
neticallyconcentrated withinstructurally permeable tion).
908 GARRY]. DAVIDSON
TABLE
2. A Compilation
of Ore DepositswithFeaturesof VolcanogenicCopper-Bearing
OxideOres
(excludingthosediscussedin thispaper)
Name Location Age Size Ores Setting

Granduc BritishColumbia, Lower Jurassic 13 Mt @ 1.27% Cu, 0.6 Mag-py-po-ccp, Stronglydeformed,underlain
Canada g/t Ag, 0.1 g/t Au gradingto by maficvolcanics,
(Thompson
and (extracted; oxide-silicate overlainby graphitic
Kirkham, preproduction BIF siltstones,gypsum-
1979; reservesof 39.3 mt limestones,tuff, and
Thompsonand @ 1.73% Cu conglomerate
Panteleyev,
1976)
Fosdalen Norway Paleozoic 25 Mt @ 60.2%mag, Well-banded Stratiform lens on the contact
(Waltham, 3% py, and0.2% ccp mag-qtz_+ between acid and basic
1968; Freitsch ccp, py volcanics,devoid of
et al., 1979) alteration
Tverrfjellet Norway Lower 19 Mt @ 1% Cu, 1.2% Mag-py-ccpore Agglomeraticacid volcanic
(Waltham, Ordovician Zn, and0.2%Pb formsa lens host devoid of alteration
1968; Nilsen, within a
1978) sphal-py-ccp
body
Viscaria Sweden 1930_+5 Ma 30 Mt @ 1.5%Cu;avg 3 X 0.7 kmthin Ore in tuffitic intervals of a
(Martinsson, gradeis •2.5% _ Zn, sheetofpo- basiclavasequence (Kiruna
1991) Co, As, Sn,Bi mag-ccp- greenstones),with
calcite with a associatedpotassic
distinct Cu- alteration
rich zone
Pahtohavore Sweden(Carlson, 1930_ 5 Ma 2 Mt @ 4.3% Cu and Chert-hosted Basic lavas, sediment, and
1991) 3.7 g/t Au ccp-mag-Au pyroclastics,
overlainby
(one of graphiticschist
several
styles)
CopperBlow NewSouth ---1600Ma 0.94Mt @ 1.0%Cuand 2 m X 1.5 km Host rocks: biotite-albite
Wales, 1.9 g/t Au mag-qtz-py- schiststratigraphically
Australia, po-eeplens below the main Pb-Zn ore
Willyamablock
(Barnes,1980)
Atikokan Northwest Arehean 21.8 Mt @ 0.4% Cu _ 10-80 m thick Intense deformation, hosted
Ontario, Ni, Go X 20 km; withina greenstone
belt
Canada mag-po-py- toward the base of a mafic
(Kirkham, ccp sequence
1979)
Salobo3A Carajasdistrict, Archcan- 455 Mt @ 1.3% Cu, 0.4 Mag-grunerite- Oxide-silicate facies iron-
Brazil(Filho Lower g/t Au albite-ccp- formationin amphibolite-
et al., 1988; Proterozoic bornitc lens gradetonaliticgneiss
Lindenmayer, (2,758 _+ 3 km long (metavolcanic)and
1990) 2 Ma) magnetiteschist
Athens mine Zimbabwe Archcan Unknown Ore is zoned Volcano-sedimentary
(Fabiana, from po-ccp packageof basalts,
1987; Foster, to py-ccp to komatiites, and sediments
1988) py-mag
Abbreviations:
BIF= banded
iron-formation,
ccp= chalcopyrite,
mag= magnetite,
po= pyrrhotite,
py= pyrite,qtz= quartz,sphal=
sphalerite
A new strata-boundmineralizationstyle is sug- uted from the early Archeanto the Upper Ordovi-
gested,termedvolcanogenic copper-bearing oxide cian, someof considerablesize. Commondenomina-
deposits,a debutanteto the familyof exhalativeores. torsarehighSoxiazedSreducedbothin thehydrothermal
The style is transitionalbetween low-temperature fluid and in the overlyingwater column,tempera-
volcanogenic oxidedeposits,suchas the Lahn-Dill tures> 280øC, and pH < 6. Very low Pb and Zn
type(Quade,1976),andvolcanic-hosted massive sul- abundances are attributedto scavenging
of the avail-
fide oreswhich containintegralstringerand basal ableH2Sby chalcopyrite andpyrite,priorto Pb-Zn
magnetite-chalcopyrite zones.Thedescription could saturation,ratherthanto an originaldepletionof Pb
encompass a significant
numberof deposits, distrib- andZn in the fluid.This featuremaybe the key to
chemical transitions within exhalative banded iron- of seawaterfrom 25 ø to 350øC: Am. Jour. Sci., v. 278, p. 838-
86O.
formationsof the easternsuccession (for instance,
Blake,D. H., Bultitude,R. J., Donchak,P. J.T., Wyborn,L. A. I.,
Pegmont)and otherProterozoicsequences (for in- andHone,I., 1984, Geologyof the Duchess-Urandangi region,
stance,BushmanlandPb-Zn-rich iron-formations); MountIsainlier,Queensland, Australia:AustralianBureauMin-
Au-Cu bandediron-formations at Starrarepresent eral Resources Bull. 219.
the hot H2S-poorend member,whereascoolingand Bonnemaison, M., Crouzet,J.,Thiercelin,F., andTollon,F., 1986,
Controlsonexhalative golddeposits hostedbyvolcaniclastic sed-
migrationof thisbrine to an H2S-richsettingcould iments in the 'SchistesX', Salsignegold district, Montagne
evolvea Pb-Zn-richbandediron-formation.Justas Noire, southernFrance,in Macdonald,A. J., ed., Gold'86: Wil-
feasibly,Pegmont-Broken Hill-stylebandediron4for- lowdale,Ontario,KonsultInternat.Inc., p. 457-468.
mation-hosted Pb-Zn depositscould developproxi- Bostrom,K., andWidenfalk,L., 1984, The originof iron-richmuds
malto a vent systemin whichtemperatures were too at the KameniIslands,Santorini,Greece:ChemicalGeology,v.
42, p. 203-218.
low to dissolveAu andCu (•260øC), but dissolved Bowers,T. S., Jackson, K. J., andHelgeson,H. C., 1984, Equilib-
H•S wasgreaterthan in a typicalvolcaniccopper- riumactivitydiagramsfor coexistingmineralsandaqueousspe-
bearingoxidefluid. Thesetwo modelsfor Pb-Zn de- ciesat pressures andtemperatures to 5 kb and 600øC:Berlin,
positionshouldproducedistinctlydifferentsulfur Springer-Verlag,397 p.
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monwealthpostgraduate scholarship. of the Lachlan fold belt southeastern Australia: Geol. Soc. Aus-
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Hydrothermal Geochemistry and Ore Genesis of Sea-Floor: Volcanogenic Copper-Bearing Oxide Ores

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Hydrothermal Geochemistry and Ore Genesis of Sea-Floor: Volcanogenic Copper-Bearing Oxide Ores

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Economic

The term "volcanogenic copper-bearing oxide" mineralizationis proposedto describe

Introduction termedthevolcanogenic copper-bearing

quences,are principally hostedby intracontinental Structuraleventsin the Starraregionconsistof (1)

bearingoxidemineralization occurin Australia.They

Starrais a strata-boundCu-Au deposit(5.3 Mt at + ß:::::::::::::::::::::::::::::

wasreflectedin a more complexstructuralhistory FIG.1. Regionalgeologyof the Starraarea;(inset)locationof

nent,50 to 100 m thick.The HarleyMemberis con- eralized Starraironstonesare positivelycorrelated

AREA 251 1275RL

•.• ---' [ GEOLOGY

• > 7.5 oom

containa discordantstyle of coarse-grained silica- permostbandediron-formationis hostedunsystema-

FIG.3. A geologicsectionalongline 1210N (prospectgrid),Osborne;(inset)prospectgeologyde-

fromthe quartzzone,overabout10 m (thisalteration (1983) to have developedwithin an 800-km-long,

limestone main copperzone

similarlensoccurs2 km eastat Little Cadia (Mason, reticalestimateindicatesmoderatelyhottertempera-

lizingsulfideat equilibrium.It isthereforelikelythat .Ol

the Big Cadia sulfidesprecipitatedover a very

Starra: Area 257

for the Big Cadiamineralization,althoughit is not

P:270 B, pH:5, T:350' C

milling,or hostedby chalcopyrite,anda strongposi- s,

Sulfuractivity ablyafter sericite)occurson the marginsandin the

posits.Big Cadia alterationcouldhaveoccurredat a log (a(K+)/a(H+))

Elders(1985) document93 to 4,200 ppm Fe in the 1000- Z//

fO2 -47 -40 -35 -32 -30 -25

FIG.12. Saturationpathsforsilicaandironunderthe specificconditions

topof someironstones (KaryandHarley,1990)dur- evolved meteoric or marine water, with a connate

T• 1. AverageVolatile-FreeIron andFe/SiRatiosfor SomeModernSea-FloorOxidePrecipitates,

F%Oatot•(wt %) Fe/Si Reference

Not calculated on a volatile-free basis

'/. •' • PYRRHOTITE

FIc. 13. A 1ogfo2-temperature

cussed here(Wybornet al., 1988).Lyons(1988)pos- sionof eventsoutlinedabove(Fig. 14). An upwelling,

Circumstantial verification of this mechanism ex- fur isotopesignature. Limiteddataaveraging •ia4S=0

iron-formations, due to conductivecoolingandfluid andpH _<6 (to promoteCu solubility).

Name Location Age Size Ores Setting

carbonatic equivalentof the Lahn-Dilltype,in Klemm,D. D., Nilsen,O., 1978, Caledoniansulphidedepositsandminoriron-

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