2the Coxco Deposit A Proterozoic Mississippi Valley-Type Deposit in The McArthur River District, Northern Territory, Australia

EconomicGeology
Vol. 78, 1983,pp 214-249
The CoxcoDeposit A ProterozoicMississippiValley-Type Depositin the

McArthur River District, Northern Territory, Australia
R. N. WALKER,
CarpentariaExplorationCompanyPry. Ltd., G.P.¸. Box 1042, Brisbane,Queensland,Australia
B. GULSON,
CSIRO Divisionof Mineralogy,Delhi Road,North Ryde,New SouthWales,Australia
ANDJ. SMITH
CSIRO Divisionof FossilFuels, Delhi Road, North Ryde, New South Wales, Australia
Abstract
The Coxcodepositis a Proterozoicstrata-bounddolomite-hosted lead-zincdepositwhich

showsmany similaritiesto Mississippi Valley-typedeposits.The depositis one of a groupof
lead-zincoccurrences in the McArthur River districtof the NorthernTerritory, Australia,the
largestof which is the stratiformH.Y.C. deposit.Thesedepositslie on or adjacentto the Emu
fault zone,a majorbasementlineamentwhichdefinedthe easternedgeof a Proterozoic fault
trough--the Battentrough.Alternatingsubsidence and uplift in the fault zoneduring the
depositionof the McArthur Group resultedin the preservationof thin sequences of the major
unitsand numerouspaleoerosional surfacesin this area.
The Coxco mineralization is contained within the Mara Dolomite Member, Reward Do-
lomite, and the Lynott Formation of the McArthur Group. The Mara Dolomite Member
consists of dololutitewith domal'stromatolites and istruncatedby a paleokarstsurface.Solution
cavitiesdevelopedbelow this surfaceare now filled in with finely laminatedspeleothems.
Stromatoliticdololutitesof the Reward Dolomitewere depositedabovethis unconformityin
an evaporiticshallow-water environment.Uplift followingthe deposition of thisunit resulted
in exposureof the sequencein a semiaridweatheringenvironment.The exposedsurfacewas
silicifiedand a karstcavernsystemwasdeveloped.Speleothems were depositedin the vadose
zoneof the cavernsystem;fine detrital phosphatic sediments, dolomitebreccias,and chemical
cementswere depositedin the phreaticzone.
An importantconstituent of the deepersections of the karstsystemare crustsof colloform
sphalerite,galena,pyrite, and marcasite(stageI mineralization)which were depositedon the
surfacesof the karst-produced solutioncavities.The remainingopenspacein thesecavities
is filled with detrital sedimentsand in many instances depositionof mineralizationalternated
with depositionof the detrital sediments.Textural evidencesuggests the rapid dumpingof
sulfideprobablyduringthemixingof metal-richandsulfur-richsolutions. The lowtemperature
of sulfidedeposition(lessthan 100øC),the ubiquitousassociation of the sulfideswith organic
matter,andthesulfurisotoperatiosof thesulfides suggest thatthe reducedsulfurwasproduced
by sulfate-reducing bacteriawithin the karstsystem.Followingtransgression of the paleokarst,
siltstones of the basalLynott Formationwere depositedin a quiet water environmentand
sedimentwas washeddown sinkholesand subsequently filled the remainingopen spacesin
the cavernsystem.
A secondstageof mineralization(stageII mineralization)consisting of coarselycrystalline
sphalerite,galena,pyrite,and marcasiteoccursin veinsand asthe matrixfor dolomitebreccias.
Matrix for the sulfideis sparrydolomiteand rare bitumen.The mineralizationcrosscuts the
RewardDolomite,the karstinfillingsin the RewardDolomite,and the basalLynott Formation
and therefore postdatesthe lithificationof the Lynott Formation. The mineralizedbreccias
vary from cracklebrecciasto open brecciasand suggestan origin of the brecciasby brittle
deformationfollowedby solutionwideningin someinstances.
There is a concentrationof the mineralization under the silicified zone at the top of the
Reward Dolomite and this impermeablebarrier is consideredto have acted as a cap rock to
the mineralizingsolutions.The temperatureof sulfidedepositionis estimatedto be in the
range100ø to 170øCbasedon the sulfurisotopefractionationbetweensphaleriteand galena
and homogenizationtemperaturesof fluid inclusionsin the sphalerite.The sulfur isotopic
0361-0128/83/130/214-3652.50 214
COXCO DEPOSIT, McAR THUR RIVER DISTRICT 215
ratiosof the sulfides,the presence

of bitumen,and thedolomitedissolutionsuggestthat reduced
sulfur,for precipitationof the sulfides,wassuppliedby inorganicreductionof sulfate..
The lead isotoperatiosof the sulfidesin both stagesof mineralizationare generallysimilar
to thoseof galenain the H.Y.C. deposit;however,a more radiogeniccomponentis present
in somesamples. The sourceof the nonradiogenic leadisconsidered to be deepbasinalbrines
which were introducedalongthe Emu fault zonewhereasthe radiogeniclead wasprobably
derived by brine leachingfrom within the MeArthur Group.
Introduction siblyAdelaidean(late Proterozoic)ageand is divided

THE Coxcodepositis a carbonate-hostedstrata-bound intothe Tawallah,McArthur,and RoperGroups(Fig.
lead-zinc depositlocatedin the MeArthur Biver dis- :3). Rb-Sr studiesof the sequencehave indicated an
trietof theNorthernTerritory,Australia
(Fig.1).This age for the McArthur Group of between 1,600 and
district is a major lead-zincprovinceand is best 1,400m.y. (Plumbet al., 1980);a U-Pb age of 1,680
knownfor the large stratiformH.Y.C. (Here'sYour m.y. hasbeen determinedon zirconsfrom tuff beds
Chance)deposit(Fig. 2) whichcontainsreserves of in the H.Y.C. deposit(Page,1981).
approximately 227 millionmetrictonsof 9.2 weight The basalpart of the Carpentariansequence,the
percentzinc,4.1 weightpercentlead, and 41 g/met- Tawallah Group, consistsof sandstones, basic to in-
ric ton silver. termediate volcanics, and minor dolostones. The
The Coxcodepositis locatedabout 10 km southeast overlyingMcArthurGroupischaracterized by evapo-
of the H.Y.C. deposit(Fig. 2). The nameof the de- rite-bearingshallow-waterdolostonescontainingstro-
posit is derived from a combinationof the namesof matolites and subordinate shales, siltstones, and
two smallareasof high-gradeoxidizedmineralization sandstones. The Roper Group is an alternating se-
(theCook'sand Cox'sprospects), whichwereworked quence of sandstone,micaceoussiltstone,and car-
by prospectors in the late nineteenthcentury.A re- bonaceousshale.The Proterozoicsequenceis uncon-
cent diamonddrilling programcoupledwith surface formablyoverlainby a thin sequenceof fiat-lying
mappinghasled to the currentgeologicknowledge
of the deposit.Indicatedreservesare on the orderof
severalmillionmetrictonsaveraging2.5 weightper-
cent zinc and 0.5 weight percentlead.
The Coxco mineralizationconsistsof sphalerite,
galena,pyrite, and marcasiteand occurswithin brec-
ciateddolostones of theProterozoic
McArthurGroup.
The deposithasmanysimilarities
to the groupof •NNH•M
carbonate-hosted
lead-zinc depositscommonlyre-
ferredto asMississippi
Valley-type
deposits.
Theage
of the mineralizationis, however, much older than OF'
is commonlyconsidered normalfor this type of de-
BASEMENT TO
posit(Stanton,1972, p. 54:3).The depositis unmeta- McARTHUR BASIN
morphosedand the originalfine-grainednature of

the hostcarbonates
hasbeenpreserved,
resultingin
the perfect preservationof the sulfide-dolostone
tex-
tures.Studiesof thesetexturesin conjunctionwith
sedimentologic, isotopic,and fluid inclusionstudies
haveallowedtheconstruction
of a depositional
model Mc ARTHUR RIVER
for the mineralization. DISTRICT
Regionalgeology
The McArthurbasin(Fig. 1) is a broadintracra-
tonicbasinwhichliesnearthe easternedgeof the
North Australiancraton (Plumb et al., 1980). The
basement rocks of the basin are felsic volcanics and KILOMETERS
graniticcomplexeswhichare late early Proterozoic

to early Carpentarian(middleProterozoic) in age Fie. 1. Geologicmap of northernAustraliashowingthe prin-
(Plumband Derrick, 1975). The sedimentary se- cipal tectonicelementsin the McArthur basin (after Plumb et al.,
quencewithinthe basinis of Carpentarianand pos- ]98o).
216 WALKER, GULSON, AND SMITH
LEGEND
•m] ALLUVIUM
BUKALARA
SANDSTONE
ROPER
GROUP
MC ARTHUR GROUP
overlying
BARNEY CREEK FORM.
MC
ARTHUR
GROUP
BARNEY
underlying
CREEK FORM.
TAWALLAH
GROUP
• MINERALIZATION
BARNEY
REFERENCE
in
CREEK FORM,
AREA
UNDERLAIN
BY
SHALES
OF BARNEY CREEK FORM.
FAULT
ANTICLINE
SYNCLINE
PROSPECT
RIVER
ORCREEK
ß MASTERTON ::'.-:'.'
øj•LABTOP
HILLo'L•Oøo\
' ',"
FIe;. 2. Geologicmap of the McArthurRiver districtshowingdistributionof the major deposits

(modified after Walker et al., 1977a).
" I I I
STOTT I
FM. I
LOOKING •
-z5oo, T STRETTON
GLASSFM. •; ;;/:;;;/ /; ;I:
•- SANDSTONE
Z::•
• YALCO
FM. DONNEGAN .........
LYNOTT / /
(n FM. '__ ._L_' ._Z•.'_
'' REWARD / /
DOLOMITE / / / • ZONE
RIDGE
ORE
• Z•Y•Z•y•Z•Y•Z•Y• • H.Y.C
ZONE ORE
tp --p --p
BARNEY HY.C p __p •__p __• o "CAULIflOWER"

CHERT
FM. _ p _ p• p/ COOLEY
'•' GYPSUM
/• /• /• / DOLOMITE PSEUDOMORPHS
-15OO /• P/• P_
//•/• SILTSTONE
SHALE T T
• SEDIMENTARY
• TEEN^ coxco•' I •' I •' i'• DOLOMITIC
o
/1,
MitCHELL
YARD
I I I SHALE
•OLOM•TE I I
• O / / DOLOMmC
O •mEMMERUGGA / //•' ! i! • SILTSTONE
TUffACEOUS
-,•oo
• u• DOLOMITE
MAR^ / I I I SIlTSTONE
• O
• DOLOMITe
I •'/ / I • MASSIVE
• O
o
.J
I
I
I
i
DOLOMITE
• o
m I I I THIN BEDDED
•; •:
•) MYRTLE ' • '•'--'•--'•--
,-- ß 7 ' 7' '•- • S STROMATOUTIC
DOLOMITE
SHALE.•/
I I
A IA AI A I
A
TOOGANINIE
FM. I I
/
I I
!
I A•'• GYPSUM
MASSIVE
PSEUDOMORPHS
-5OO IA i A I A I A I A
ß ß I I ß I* I. Iß • "RED
BED"
SILTSTONE
TATOO LA -•-
SANDSTONE ß' ß ß ß K- METASOMATISED
AMELIA
DOLOMITE ^^. A
A .•A /• A/.
•
v•'- 1AND SILTSTONE
BASIC EXTRUSIVES
MALLAPUNAH ^ ^ ^ ^ ^
.... FM "• '-•- ß'• ' '•- ' •-
-r' MASTERTON GOLDX ' '
o• SANDSTONE
•
-JO.
FM
WOLLOGORANG
VOLCANIC .v_.vLv.
-o• j• FM •/ •-.•--•
• SLY
CREEK
/ NO,
,X,OS,OSST
Mc DERMOTT
FM
FIG.$. Schematic
stratigraphic
columnof theTawallahandMcArthurGroups
in theMcArthurRiver
districtadjacentto the H.Y.C. deposit(modifiedafter Walker et al., 1977a).
217
feldspathicsandstone, the BukalaraSandstone, which Formationis only representedby dolomiticbreccias

is probablyCambrian in age (Plumb et al., 1976). of the upperbreccias,the youngestinformal division
The dominant tectonic element within the Mc- of Barney Creek Formation in the H.Y.C. basin
Arthur basinis the north-south-trending Battenfault (Murray, 1975).Southof the H.Y.C. area,the Barney
zone(Fig. 1). This fault zonedefinesthe locationof Creek Formation does not occur to the east of Cow-
the Battentroughor graben,whichwasactiveduring drey'sfault (Fig. 2).
depositionof the Carpentariansequences. A much The overlyingReward Dolomite is an extremely
thicker sequencewas depositedwithin the trough variable sequence.In the Emu Plainsbasin,the unit
than on the adjacent stable Arnhem, Caledon, Bau- consists of dolomitic shaleswhich reflect the persis-
hinia,and Wearyanshelves(Fig. 1). In the north,the tenceof the basinaldepressions in which the Barney
Battentroughwasboundedby the Parsons Rangeand Creek Formationwasdeposited.Elsewhereit consists
the Koolatongfaultsand wasactivefrom the startof of dolomitic siltstone and stromatolitic dololutite. The
Tawallah Group sedimentation(Plumb and Derrick, BattenSubgroup(Fig. 8) unconformably overliesthe
1975). In the south,the troughwasboundedby the Reward Dolomiteand consists of an alternatingse-
Four Archers-Tawallah and Emu faults. The Batten quenceof dolomiticsiltstone,dololutite,chert, and
trough ceasedto existas a separatestructurewithin sandstone.
the McArthur basinbefore the depositionof the Ro- Mineralization
per Group (Plumb et al., 1980).
Base metal mineralization in the McArthur River
Local geology districtcan be divided into fine-grainedstratiform
The major known lead-zinc mineralization in the (concordant)and coarse-graineddiscordant,strata-
McArthur River district lies within a 20-km semicircle bound occurrences.
centeredon the H.Y.C. deposit(Fig. 2). The oldest The stratiform mineralization consists of fine-
exposedrockswithin this area are a thin sequenceof grainedpyrite, sphalerite,and galenain thin laminae
the upper Tawallah Group which cropsout in the which are conformablewith the beddingin the host
core of the Masterton dome and also in two thin horst carbonaceous, dolomitic shale (Croxford and Jeph-
blocks which define the main fault branches of the cott, 1972). The mineralizationtype is restrictedto
Emu fault zone. the BarneyCreek Formationand the highestgrade
The basalunits of the McArthur Group up to the concentrations are the H.Y.C. and Ridge II deposits
Teena Dolomite (Fig. 8) compriseshallow-waterdo- in the H.Y.C. basin (Williams, 1978) and the W-Fold
lolutites with minor dolomitic siltstone, dolarenite, depositin the W-Fold basin.Controversyexistsas to
and sandstone. The dololutites are stromatolitic and whether the sulfideswere depositedsyngenetically
containevidenceof the former presenceof substantial (Croxfordand Jephcott,1972; Croxford et al., 1975;
sulfateevaporites(Walker et al., 1977b). The thick- Lambert, 1976) or postsedimentation (Williams, 1978,
nessof these units decreasesmarkedly toward the 1979).
Emu fault (Murray, 1975);within the fault zonesev- In addition to the Coxco deposit (Walker et al.,
eral of the dolostoneunits are truncatedby uncon- 1977a),significantdepositsof coarse-grained discor-
formity surfacesshowingevidenceof karsting. dant mineralizationoccurin the Cooley,Ridge, and
Followingdepositionof the Teena Dolomite,the Bulburraareas(Murray, 1975) (Table 1). The most
BarneyCreek Formationwasdepositedin a restricted detailedstudyof thisstyleof mineralizationhasbeen
area of the Battentrough,adjacentto the Emu fault on the Cooleyand Ridge deposits(Williams, 1978).
zone,referred to asthe Bulburradepression (Murray, The Cooleydeposits occurwithin the Emmerugga
1975). The formationconsists of red and green,do- Dolomite(Fig. 8), a sequence of massiveto laminated
lomitic, potassicshales(W-Fold ShaleMember), do- shallow-waterdololutites. The depositsare located
lomite breccia (CooleyDolomite), and interbedded adjacent to a branch of the Emu fault zone to the
carbonaceous, potassic,dolomitic,and pyritic shales, eastof the H.Y.C. deposit(Fig. 2) and they showa
dolomitictuffites,and sedimentarydolomitebreccias complexhistory of brecciationand mineralization
(H.Y.C. Pyritic ShaleMember) (Murray, 1975). The (Williams, 1978). The host rocks show evidence of
formation is now preservedin synclinal structures two major episodesof brecciationwhich postdatesed-
referred to locally as basins. Stratiform lead-zinc imentationand precedemineralization.
mineralizationhas been found in the Barney Creek The firstgenerationbrecciasconsistof angulardo-
Formation in the H.Y.C., Emu Plains, and W-Fold lolutite clasts in a dark-colored matrix of dolomite,
basins(Fig. 2). The H.Y.C. and Emu Plainsbasins pyrite, and carbonaceous
matter. The secondgener-
developedashalf grabensboundedto the eastby the ation breccias, which crosscutthe first, have a matrix
syndepositional Westernfault (Walker et al., 1977a). of basemetal sulfides(Table 1), dolomite,barite, and
To the east of the Western fault, the Barney Creek carbonaceous matter. Williams (1978) suggeststhat
COXCODEPOSIT,McARTHURRIVER DISTRICT 9.19
TABLE 1. Discordant Strata-Bound Mineral Occurrences throughthe Emmerugga and CooleyDolomites and
in the McArthur River District
may eventuallyhaveformedthe stratiformRidgeII
mineralization in the H.Y.C. basin.
Occurrence Sulfides Host formation
Barney Hill gn EmmeruggaDolomite Geology of the Coxco Deposit

Bulburra py-sp-gn Teena Dolomite The Coxcodepositoccursin the McArthur Group
CooleyI py-sp-gn EmmeruggaDolomite sedimentssituatedadjacentto a horst of Tawallah
Cooley II py-mc-cpy-sp-gn EmmeruggaDolomite
bn-td Groupin the Emu fault zone (Fig. 2). The miner-
Cooley III py-sp-gn EmmeruggaDolomite(?) alizedsequenceis preservedin a north-plunging
an-
Coxco py-mc-sp-gn RewardDolomite ticline(Fig.4) andconsists
largelyof dololutites
with
RidgeI py-sp-gn CooleyDolomite variousstromatolitetypes.The sequenceoverliesa
RidgeII
(discordant) py-sp-gn CooleyDolomite
thin unit of red dolomiticsiltstones,
the Myrtle Shale
Squib py-cpy EmmeruggaDolomite Member (Fig. 5), which is an easily recognized
Turnbull's py-cpy-gn EmmeruggaDolomite marker horizonin the Battentrough.The dololutite
sequenceabovethe Myrtle Shalecan be divided,
Abbreviations: py, pyrite; mc, marcasite;cpy; chalcopyrite;bn, basedon comparisons with sequencesin the Batten
bornite;td, tetrahedrite;sp,sphalerite;
gn, galena
trough(Jacksonet al., 1978;Brownet al., 1978),into
the Mara DolomiteMember of the EmmeruggaDo-
the mechanism whichgaveriseto the firstgeneration lomite and the Reward Dolomite. The mineralized
brecciasmayhavebeeneithermovementonthe Emu sequenceis overlainby dolomiticsiltstones
of the
or Westernfaultsor collapsedue to solutionof evap- Lynott Formation.
orite minerals.The intimaterelationshipbetweenthe Dolomiteis the onlycarbonatepresentin the min-
secondgenerationbrecciasandthe mineralizationled eralizedsequence at Coxco.The finegrainsizeof the
Williams(1978)to suggest that thesebrecciasformed lutitesand the perfectlypreservedoriginaltextures
by solutioncollapseassociated with the introduction in mostof the lithologies
indicateeitherprimarypre-
of the mineralizingsolutions. cipitationof dolomiteor veryearlydolomitization of
The sulfidemineralsin the secondgenerationbrec- a calciumcarbonateprecursor(seealsoBrownet al.,
cias encrust the walls of veins and small dololutite 1978; Muir, 1979).
fragmentsin the veinsand generallydisplaytextures Mara Dolomite Member
indicatingopen-space growth.Two distinctperiods
of mineralizationare recognizedwithin the breccias. Thisunit consists
of approximately110 m of finely
The first occurson the edge of veinsand consists
of laminatedto massivedololutite,minor dolarenite,and
pyrite, marcasite,barite, and dolomite.Mineralsof flake breccia. The dololutite is characterized by
the secondstageovergrowthoseof the first in the domal and bulbosestromatoliteswhich commonly
parageneticsequencebornitc, chalcopyrite,galena, reachdiametersof up to 130cm. The environmentof
sphalerite,and dolomite.Pyrite from the earlier min- depositionwas probably shelteredintertidal or
eralizationperiodis frequentlyreplacedby the later ephemerallacustrine(Brownet al., 1978).The unit
base metal sulfides. differsin two respects from the Mara DolomiteMem-
The temperatureof formationof the Cooleymin- ber whichhasbeendescribed from the Battentrough
eralizationcould have ranged as high as 275ø to (Jackson et al., 1978;Brownet al., 1978).The first
290øC, basedon the sulfur isotopicfractionationbe- is the occurrence of irregularlyshapedlensesand
tween galena and sphalerite(Rye and Williams, dikes of brown weathered dololutite and dolomite
1981). However, thesetemperaturesseemmuch too brecciatowardthe top of the sequence.Theselenses
high giventhe geologyof the depositsand Rye and and their significance are discussedlater.
Williams (1981)notedthat a lowertemperaturerange Secondly,the unit containsfinely laminateddis-
of 120ø to 170øCis permittedby the carbon-oxygen cordantdolomite-quartzveinsin the top 50 m (Fig.
isotopicdata. 6A). Theseveinsreacha maximumwidth of 130cm
The coarse-grained Ridgedeposits(Table 1) occur but are morecommonly13to 4 cm wide. The wider
within the CooleyDolomite Member of the Barney veinsare planar whereasthe smallerveinsare anas-
Creek Formation and show a brecciation and min- tomosing,with their directionand width changing
eralization history similar to the Cooley deposits rapidly.The majorityof the veinsare approximately
(Williams, 1978). Based on metal zoning, mineral normalto bedding(Fig. 6A). Internal laminationsin
paragenesis, and sulfide textures,Williams (1978) the veinsare subparallelto the wallsand the contact
proposedthat the Cooley and Ridge depositswere with the host rocksis usuallysharp. The veins ter-
formed by a mineralizingsolutionwhich entered minate at the Mara Dolomite-Reward Dolomite con-
from the Emu fault zone and flowed westward tact and the width and intensityof the veinsdecrease
STRATIGRAPHIC COLUMN
BUKALARA
SANDSTONE
-T
LOOKING GLASS
FORMATION
STRETTON
SANDS TONE
YALCO
FORMATION
LYNOTT
FORMATION
REWARD
DOLOMITE
EMMERUGGA
DOLOMITE
TOOGANINIE
o
o FORMATION
TATOOLA SANDSTONE
AMELIA DOLOMITE
MALLAPUNYAH
FORMATION
MASTERTON
FORMATION
• o
LEGEND
SURFACE
PROJECTION
•OF
MINERALIZATION
Alluvium
k (•ossan
Geological
boundary
Creek
Fault
Antichnal
Axis
......•'•'Syn
clinal
Axis
Angled Diamond
Drill Hole
Vertical Diamand
Drill Hale
ß
-&'LEO
Strikeanddip
IO0 200 300

I
FIG. 4. Geologyof the Coxcodeposit.
220
COXCO DEPOSIT, McARTHUR RIVER DISTRICT 2œ1
progressively
downward from this contact.The do-
lomite(Fig. 6B) within the veinsis dominatedby a
columnarform (Walker, 1980) identical in habit to
the "palisade"calcitedescribed by Folkand Assereto .... _-_-_-_-_-_-_-_-_-_-_-_-_-_-_-_-_-_-_-_-_-_-_-_-_-_-_-_-_-_-_-_,,_,_,_,_,_,_,_,_-_-_-_-_-_-_-
-.
(1976)and Kendalland Broughton(1978).

Cluesto the originof the dolomite-quartz
veinsare
_- ! \
providedby the palisadetextureof the dolomite.It
is the habit adoptedby calcitein Recentand ancient
speleothems(Folk and Assereto,1976; Kendall and
Broughton,1978). The occurrenceof the palisade
dolomiteand the laminargrowthon the wallsof the J,',..2... % "', .,"
original cavities,which indicate extensivesolution,
are evidencethat the dolomite-quartzveinsare spe- ••.•-•,
............ _.½ -,.,, '• ••min.•o•-
Stage•••' /
leothemsor flowstones depositedin a vadosecavern e•al••'
J %• / '%•ccias
system.Sincethe majorityof the veinsare normal to
bedding,the originalcavitieswere probablydevel-
opedby solutionalongverticaljoints(Fig. 5). The
settingmay thuscorrespond to the verticalcavesys-
temswhichare developedin modernareasof deep
karstdevelopment(Sweeting, 1972).Suchsystems are
developed
withinthe vadose
zonein areasof strong
jointingandextremely
deepwatertables.Thephreatic
zoneof karstdevelopment hasnot beenrecognized
undertheinferredzoneat Coxco,possiblydueto the
pooroutcropof the lower partsof the Mara Dolomite.
The termination of the veins at the Mara Dolomite-
RewardDolomitecontactsuggests that the solution MARA OOLOMITE MEMBER
cavitieswere developedbelow this unconformity
prior to the depositionof the Reward Dolomite. The
erosion
ornondeposition
ofthetopof theEmmerugga MYRTLE %SHALE %• MEMBER
Dolomite,TeenaDolomite,and the BarneyCreek
Formationin the Coxcoarea indicatesthe majorna-
Fie. 5. Schematicunfoldedcrosssectionthrough the Coxco
ture of this unconformitysurface. deposit.
Reward Dolomite
The RewardDolomitecomprises light gray dolo- sociatedgypsumpseudomorphs wouldsuggest a shal-

lutitescontainingstromatolitetypesdifferentfrom low-waterevaporiticenvironmentof depositionfor
thosein the Mara Dolomite.The unit is approxi- this unit. The sandstone-siltstone lenses are similar to
mately 100 m thick, containslensesof sandstone-silt- lenses described in the Reward Dolomite to the south
stone,and is overlainby dolomiticsiltstones of the by Brown et al. (1978) and are interpreted as tidal
Lynott Formation (Fig. 5). The stromatoliticmacro- channels.
structure(Fig. 6C and D) variesfrom branchingco- Two features of the Reward Dolomite are in con-
lumnartoconical(Walker,1980).Theconicalvariety trast to the sectionsdescribedin the Battentrough
frequentlycontains acicularcrystalformswhichoc- (Jacksonet al., 1978; Brown et al., 1978). First, like
cur in radiatingclusterswithin the stromatolitetex- the Mara Dolomite, the Reward Dolomite contains
ture (Fig. 6D). The crystalshave pseudohexagonal crosscutting lensesand dikesof dolomitebreccia,do-
crosssections and are similarto crystalformsin the lolutite,and dolarenite,markedin outcropby a dis-
McArthurGroup previouslyidentifiedas gypsum tinctive brown weatheringsurface.Theselensesare
pseudomorphs (Walker et al., 1977b). Intervalsof described later.
sandstone
andfriableredandgraysiltstone
werein- Second,in outcropthe stromatoliticdololutiteand
tersected near the middle of the unit in drill holes in the overlyingLynott Formationare separatedby a
the vicinityof Cook'sworkings(Fig. 4). The sand- siliceouszoneof variablewidth (Figs.4 and 5). This
stoneconsists of well-sortedquartz grainswith an zone consistsof a variable amount of quartz, void-
averagegrain sizebetween200 and $00 #m, whereas filling chalcedony,and goethite. Relict textures
the siltstone
consists
of quartz,K-feldspar,apatite, includefinelaminationswhichappearto be stromato-
and minorpyrite.The stromatolitetypeand the as- litic structures,
breccias,and discoidalgypsumpseu-
FIG. 6. Host sequenceto the mineralizationin the Coxcodeposit.

A. Finely laminateddololutiteof the Mara DolomiteMember crosscut
by a finely laminatedvertical
dolomite-quartzvein (scalein centimeters).
B. Photomicrograph showinga palisadedolomitelaminawithin a dolomite-quartz vein in the Mara
Dolomite Member.
C. Plan view of conicalstromatolitesfrom the Reward Dolomite (scalein centimeters).
D. Plan view of conicalstromatolitesfrom the RewardDolomiteshowingthe radial arrangementof
aciculargypsumpseudomorphs (?).
domorphs.The goethitecommonly occursasaggre- quartzcomponentconsisting. of bothvoid-fillingand

gatesof polygonalcellssimilarto the gel goethite replacementquartz. Finely laminated chalcedony,
describedby Grovesand Whittle (1976).The contact microcrystalline quartz, chalcedonyspherulites,and
betweenthe dololutites andthe silicifiedzoneis only minor dolomiteinfill irregularcavities(Fig. 7A and
exposed in oneareawhereit is highlyirregular.To B).The originaledgesof thecavitiesareoftendefined
the westof Cox'sworkings(Fig. 4), an outcropof the by a thin discontinuous lamina, up to 80 lumthick,
BukalaraSandstone overliesthe zone,implyingthat of dark brown inclusionsin the void-filling chalce-
the silicificationdevelopedprior to the depositionof dony (Fig. 7A). X-ray diffractionstudiesof the ma-
this Cambrian unit. terial showedthat it containsgoethite.The original
In drill coreit is possible to distinguishtwo stages dolomiticsedimentis often replacedby irregularly
of silicification. The first is best seen in drill holes distributedareasof fine-grainedquartzrangingfrom
which intersected the. silicified zone below the zone 1 to 10 •umin diameter(Fig. 7B).The quartzin some
of Recentweathering.In theseholes,the top several instances displaysirregularfracture patternsand is
meters of the Reward Dolomite contain a variable bestdescribedascrazed.The grain boundaries of the
COXCODEPOSIT, McARTHUR RIVER DISTRICT 2213
quartz crosscut the fracturesand it is suggested that Shape:The breccialensesare extremelyvariable

the fracturesare syneresiscracksrelated to a pre- in shapeand the contactswith the enclosinglight
cursorgel phase. gray stromatoliticdololutitevary from crosscutting
The chalcedony cavityinfillings,and the fractures to conformable.In a typicaloccurrence,strata-bound
in the silicifiedrock,are truncatedby pyritic siltstones lenses up to severalmetersin lengthanda few meters
of the basalLynott Formation;thesesiltstones often wide are connectedby irregular crosscutting dikes
containfragmentsof the silicifiedrock. Theserela- (Fig. 5). The basesand topsof the lensesvary from
tionshipsimply that this first silicificationstagewas fiat to extremelyirregular (Fig. 7C).
followed by an erosionepisodethat precededthe Textureand sedimentarystructures:The dolomite
depositionof the Lynott Formation.This timing ev- breccias(Fig. 7C and D) consist of fragmentsof do-
idencecombinedwith the texturalevidencesuggests lolutiteand variousotherlithologieswith a maximum
that the first silicificationstagewas developedon a diameterof approximately1 m. The fragmentsare
paleoweatheringsurfaceas a resultof uplift of the poorlysortedandthebreccias rangefrom matrixsup-
Reward Dolomite. The silicificationis crosscutby ported to fragment supported.The fragmentsvary
sphalerite-dolomite veinsof the stageII mineraliza- from angularto well rounded.The fine-grained sed-
tion, indicatingthat the silicificationoccurredprior imentsin the lensesare usuallyfinely laminatedand
to the depositionof stageII mineralization. exhibita moderatedegreeof sorting.Poorlygraded
The secondsilicificationstageconsists of goethite- bedding,small-scale crossbedding, and scourstruc-
stainedmicrocrystalline quartz and void-fillingchal- tures occurrarely. Blind microfaultingand small-
cedony and metaquartz. Void-filling chalcedonyis scaleto relativelylarge-scale soft-sediment slumptex-
often found as the matrix to dolomite breccias,sec- tures indicate sedimentmovement prior to lithifica-
ondary lead minerals,and fragmentsof colloform tion within the lenses.
marcasiteand pyrite that are partly alteredto goe- Fine-grainedsediments:Fine-grainedsediments
thite. Void-filling quartz of this silicificationstage occur as the matrix to the dolomite breccias and in
crosscuts quartz of the first silicificationstage and lensesdevoidof fragments.The sedimentsare com-
predatesdepositionof the Bukalara Sandstone.It is posedof the following componentsin approximate
possiblethat the secondsilicificationepisodewas as- decreasingorder of abundance:dolomite, quartz,
sociatedwith a paleoweatheringcycle which imme- clay, organicmatter, feldspar,chert, iron sulfides,
diately precededdepositionof the Bukalara Sand- collophane, mica, and dolomitepseudomorphs after
stone. barite. A vertical zonationpattern is developedbe-
Silicificationon paleoweatheringsurfacesdevel- tween the breccialenseswith the percentageof or-
oped on carbonaterockshas long been recognized ganic matter, quartz, feldspar,and mica increasing
(Leith, 1925; Burdon and A1-Sharhan,1968; Chafetz, toward the top of the Reward Dolomite. This trend
1972; Maslyn, 1977). The silicifiedzone givessome isalsoreflectedin a progressive darkeningof the lith-
indicationof the climatic conditionsprevailingdur- ologiesupward.
ing its formation.The solubilityof amorphoussilica Detrital dolomitegrainsare the major component
is almostindependentof pH in the range1 to 9 and and rangefrom 10 to 40 ttm in diameter.Quartz is
increasesrapidly at pH greaterthan 9 (Alexanderet an extremelyvariablecomponentand comprises10
al., 1954). Thus the prerequisitesfor silicadeposition to 40 percentby volumeof the lithology.The grains
onerosional surfacesaresilica-charged groundwaters are 20 to 70 ttm in diameter, are angular to sub-
with a pH greaterthan 9, a mechanismto circulate rounded,and haveovergrowths in opticalcontinuity.
the groundwatersto the surface,and a precipitation Clay is a very variablecomponentand often forms
mechanism.Climatic regimeswheretheseconditions distinct thin laminae.
occurare semiaridenvironments receivingsufficient Organicmatterisubiquitous andusuallycomprises
spasmodicrainfall to causesubstantialfluctuationsin a few percentof thesediment.It occursasdarkbrown
the water table (Smale,1978). The sourceof the silica filamentouslaminae averaging8 ttm wide and as
presentsno problemsand is probablysuppliedby disseminations. Fine-grainedeuhedralpyrite with an
dissolution of detritalquartzgrains.The precipitation averagegrain sizeof 4 ttm is associated with the or-
mechanismmay be evaporationor a loweringof the ganic matter. Oval to irregular-shaped nodulesof
pH of the groundwatersby mixingwith freshwater collophane,which vary from 100 to 800 ttm in di-
or by reactionwith oxidizingdiageneticsulfides. ameter, occurwithin black organic-richareas.
Dolomite pseudomorphsafter a tabular mineral
Breccia lenses in the Mara and
with crosssectionsup to 50 by 450 ttm occur in rare
Reward Dolomites
clustersup to 2 mm in diameter(Fig. 7D). The crys-
Lenses and dikes of dolomite breccia and dololutite talshaveacuteterminationsand the interfacialangle
occurin the Reward Dolomite and the upper 20 m averages78ø. This is closeto the anglebetweenthe
of the Mara Dolomite (Fig. 5). (110)^(110)rhombicprismsof baritewhichis78o22.5'.
5 mm
I
224
COXCODEPOSIT,McARTHURRIVER DISTRICT 225
The pseudomorphs to be in diameter. In some breccias, the rims are thinner

are thereforeconsidered
after tabularcrystalsof barite. on the topsof fragmentsand are draped between
Fragmenttypes:Roundedto angularfragmentsof adjacentfragmentsproducinga geopetalfabric.
dololutiteare the mostfrequentfragmenttype. The Thesecond typeof rim materialisfinelylaminated
texturein thesefragmentsis identicalto the hostdo- andiscomposed of dolomiteandquartz.The laminae
lolutite and the fragmentsare consideredto be de- are variablyfiat, curved,or irregularin form. The
rived from thissource.Somefragmentscontainareas maximumthicknessobservedfor thistype of rim was
of microcrystalline and void-fillingquartz and chal- 6 cm with individuallaminaerangingfrom 0.2 to 2.0
cedonywhich are identicalin texture to silica vari- mm wide. Four major habits of dolomite occur in
eties observed in the silicified zone and the host se- random order in the rim and are described below in
quence.The diageneticquartz varietiesalsooccuras order of importance.The first consists
of columnar
discretefragments.Otherfragmenttypesare of local grainswith long dimensions between$00 and 600
importance.White siltstonefragmentsare comprised txmandrarelyup to 2 mm.The widthof the crystals
of poorlysortedangulargrainsof quartz and com- could not be determinedas the habit is alwayscom-
positegrainsof diageneticquartz habitsin a clay plicatedby a secondgenerationof dolomiteconsisting
matrix. The same siltstonelithology occursas rare of 10- to 50-txm-diameter,euhedral to subhedral
films on dololutitefragmentsin the brecciasand is grainsin randomorientation.The columnargrains
consideredto representa concentrationof insolubles show radial extinctionin clustersregularly spaced
from the hostsequence.Fragmentswith lithology alongthe laminae.The orientationof the grainsis
identical to the dolomite-quartz-collophane contact length-slow andtheyaresimilarto thepalisade habit
rims are of minor importance. of calcitedescribedby Folk and Assereto
(1976).The
In certainareasof the deposit,fragmentsof pyrite, secondis anhedralgrainswith diametersof 8 to 15
marcasite,sphalerite,and galenaare minor but im- txm and randomorientation.The third consists of
portant componentsof the breccias.These sulfides anhedralto subhedralgrainsaveraging150 #m in
alsooccurascolloformrims on fragmentsof various diameter. This habit usuallyhas random orientation
lithologies.This mineralization,which is referredto but whenadjacentto the firsthabit may displayover-
as stageI mineralization,is describedlater. all radial extinction. The fourth habit consists of mi-
Contact zone: The contact zone between the do- critic fragmentsup to 100#m in diameterin a sparry
lolutite host and the breccia lensesis commonly dolomitematrix. The quartz in the rims variesfrom
marked by a dolomite-richrim. The rims are of two fine-grainedreplacement quartzto void-fillingmega-
types.The firstis a light brownrim up to 5 mm wide quartzand chalcedony.In mostcases,the quartz is
composedof dolomite,collophane,iron sulfide,and stainedlight to dark brown,probablyby iron oxide
organicmatter. The dolomitewithin the zonescom- inclusions,and preferentiallyoccursin the coarser
prisesanhedralgrainsrangingfrom 5 to 100/xm in dolomite laminae.
diameter although layers up to 100 txm thick of A specialvarietyof the type 2 rim is composed
length-fastcolumnargrainsare not uncommon.The onlyof thecolumnardolomitecrystalsin spheroidal
yellowcollophaneis concentratedin zoneswhich are to ellipsoidalclusterswhich vary from 2 to 10 mm
in diameter(Fig. 7G). Eachclusterof columnarcrys-
parallel to the contactwith the dololutitehost (Fig.
7E and F) and is associatedwith reddish-brown or- tals exhibitsradial extinction.The clustersmay be
ganicmatter.Alsoassociated with the organicmatter isolatedor may havecoalesced to form veryirregular
are disseminatedskeletal marcasitegrains. These masses,and the overall texture is best describedas
grainshave a diameter of $ to 10/xm and a core of branchingnodular.
euhedralpyrite which is on the order of i to 2 txm Origin of the lenses:The featuresof the dolomite
Fie. 7. Hostsequenceto the mineralizationin the Coxcodeposit.

A. Bandedchalcedonycavity filling from the silicifiedzone of the Reward Dolomite.The original
edge(A) of the cavityisdefinedby ironoxideinclusions in the chalcedony.
Microcrystalline quartz(MQ)
replacesthe originaldolomiticsediment(D) hostingthe cavity.Thin section,planepolarizedlight.
B. Sameas A. Thin section,crossedpolars.
C. Karstcaverninfilling in the RewardDolomiteshowingthe dark colorof the karstsedimentand
the irregularfloor (highlighted)of the originalcave. Location:Cox'sworkings.
D. Negativeprintof a thinsection of a dolomitebrecciafroma caverninfillingin theRewardDolomite,
showingthe distributionof barite pseudomorphs (B).
E. Collophane-richdolomiterim on a karstcavity. Note the disseminated iron sulfide.Thin section,
planepolarizedlight.
F. Sameas E. Thin section,crossedpolars.
G. Negativeprint of a thin sectionof cave popcornfrom the edge of a karstcavernin the Reward
Dolomite. Chalcedony(black) fills the cavitiesbetweenthe dolomitenodules.
breccia and dololutite lensesin the Mara and Reward positionsimilar to siltstonesin the basalLynott For-
Dolomitessuggest that the lensesare fillingsof so- mation. Fragmentsof silicifieddololutite from the
lutioncavitiesdevelopedduringan episodeof kar- silicifiedzoneat the top of the Reward Dolomiteare
stiffcation.
Threemajorsources of fillingmaterialcan commonlyfoundin thissediment,asare many other
be recognized. fragmenttypes.This sedimentis consideredto have
Thefirstcomprisesdetritalfragments derivedfrom beenwashedintothe solutioncavitiesafter transgres-
mechanical and chemical erosion of the host dolo- sion of the karst surface.
lutitesequence.
Suchmaterialvariesfromlargefrag- The restriction of the dolomite breccia lenses to the
ments of the dololutite to concentrations of the in- sequenceunderlyingthe Lynott Formationand the
solublecomponents
of the dololutitesuchasquartz, occurrenceof lithologiessimilarto the basalLynott
clays,micas,andorganicmattertogether
withvari- Formationin the upper sectionsof the karstcaverns
able amounts of detrital dolomite. The sediments de-
indicatekarstificationpredatesthe depositionof the
rived from thissourcewere depositedin the cavities Lynott Formation. Karstificationwas therefore con-
in microenvironments which variedfrom oxidizing temporaneous with the silicificationof the paleo-
to highlyreducing.The oxidizingenvironments are weatheringsurfaceat the top of the Reward Dolo-
characterized by a lack of organicmatterand minor mite.
quantitiesof ironoxides.The reducingenvironments
are characterized with a highorganic Lynott Formation
by sediments
mattercontentanda highproportion
of fine-grained The baseof the Lynott Formation in the Coxco
diageneticiron sulfides.The commonassociation of area consistsof light to dark gray dolomiticsiltstone
ironsulfideswith organicmatterin thecavityfilling with minor light gray dololutite,black carbonaceous
wouldsuggest
that the sulfideprecipitatedby bac- siltstone,and rare dolarenite. Constituentsof the silt-
terial sulfatereduction(Berner,1970). stonesin order of abundanceare: quartz, dolomite,
The secondfilling materialco.•:•prises deposits of clay minerals,feldspar,organicmatter, iron sulfide,
dolomitewith variableamountsof quartz, collo- mica, and collophane.
phane,and organicmatter,deposited on the edges Quartz is the major constituentand consistsof
of the solutioncavities.The finely laminateddolo- poorlyrounded,subangulargrainsfrom 10 to 70 gm
mite-quartz depositsresemblestromatolitesin their in diameter. Feldsparsare of similar size but never
generalstructure.However, the lack of included or- comprisemore than a few percentof the rock. Do-
ganic matter, the predominance of chemicallyde- lomite is a highly variable componentand ranges
positedcarbonateover detrital carbonate,and the from a few percentup to approximately$0 percent.
presence of palisade dolomitelaminaesuggest that The clay mineralsoccurin thin laminaefrom 50 to
thedeposits are speleothems or flowstones ratherthan 200 gm wide, but with the exceptionof sericite,the
stromatolitestructures(Folk and Assereto,1976; individual minerals were not identified. Coarse seri-
Thraikill, 1978). The nodular dolomite rim has the cite grainsare alignedparallelto the laminationsand
internalstructureof cave popcorn(Thraikill, 1968, comprisea few volumepercentof the rock.
1971,1978).Thraikill(1978)describes cavepopcorn The colorof the rock is dependenton the amount
as clustersof carbonate noduleswith diameters from of organicmatter.This is commonlyon the orderof
2 to 100 mm. They are depositedsubaeriallyfrom a few volumepercentand occursasthin films,seams,
thin filmsof waterwhichare usuallysuppliedby and flakesof reddish-brownto black material. Pyrite
splash froman adjacent drip.It issuggested thatthe is ubiquitousand usuallyoccursas disseminated1-
nodulardolomiterim represents cavepopcorn within to 4-gm-diametereuhedralgrainsin association with
the vadosezoneof a karstsystem. the organicmatter.
The thin dolomite-collophane rims on the solution Collophaneconcretionsand collophane-richsilt-
cavitieshave a differentorigin. As well as the fine stone laminae are a common feature of the siltstones
detritaldolomite, therimscontaincolumnar length- althoughthey are not volumetricallyimportant.The
fast dolomite. This habit is that of normal carbonate collophane issubmicroscopic in grainsizeand varies
cavity-fillingcement(Bathurst,1964).The rim is in- from light yellowto reddishbrown in thin section,
terpretedasdetritaldololutiteandminorchemically dependingonthe amountof includedorganicmatter.
precipitated dolomite deposited on thefloorof cav- The concretions are diageneticin origin while the
ernsin the phreaticzone.The sediments havesup- siltstonelaminae are consideredto be phosphatized
portedanactiveassemblage of microorganisms which hardgrounds(Walker, 1980).
haveconcentrated phosphatic material(e.g.,Trudin- Where the silicifiedzoneis not presentat the top
ger, 1976). of the Reward Dolomite, a carbonate-rich detrital
The third sourceof filling materialis foundin the faciesoccursat the baseof the Lynott Formation.
uppersections of the cavernsystemand hasacom- This facies reaches a maximum thickness of 10 m and
COXCO DEPOSIT, McARTHUR RIVER DISTRICT 227
consistsof quartz dololutite,dolarenite,and doloru- from the hostrock by a dolomite-collophanerim. The

dite. The quartz-feldspar-mica componentof the lith- karst brecciasare consistentlypresentbelow the Re-
ologiesisidenticalto thatin thenormalsiltstone
facies ward-Lynott unconformitywithin the area covered
of the Lynott Formationand rangesfrom 10 to 40 by Figure 4, but stageI sulfidesare limited to the
percentby volume.Beddingvariesfrom finely lam- lower sections of the Reward Dolomite in the north-
inated to massiveand is commonly disrupted by ern end of the deposit(Fig. 4, drill holes 18, 19,
minor erosional breaks. Beds of rounded to oval- and 22).
shapedintraclasts up to 1 cm in diameterare a feature Form
of the faciesand clastsoften showreplacementof the
dolomiteby collophaneat the edges. The form of the mineralization is best described
The natureof the siltstones at the baseof the Lynott as vein (Fig. 8A) and cavity fill (Fig. 8B). Veins up
Formation suggests depositionin a quiet water ma- to • cm wide showparallel developmentof colloform
rine or lacustrine environment. The close association and coarselycrystallinesphaleriteand pyrite-mar-
of iron sulfidewith organicmatter suggests that the casitelaminae on each wall. The central portion of
sulfide precipitatedby bacterial sulfate reduction the veinsis filled with dolomitic siltstone,quartz do-
(Berner, 1970). The carbonate-rich sediment devel- lolutite, or a chaoticmineralizedbreccia,consisting
opedon the unconformitysurface,where the silici- of fragmentsof mineralizationsimilarto that on the
fled zoneis not present,appearsto representa tran- walls of the vein, in a lutite-sized matrix. The matrix
sitionalzone between the exposedsurfaceand the often transgresses the earlier deposited colloform
quiet water regime. crusts on the walls of the veins.
In the cavity fill mineralization, the colloform
Stage I Mineralization crustshavebeendepositedon the wallsof the cavities
Two distinctstagesof lead-zincmineralizationcan and on the edgesof fragments;the cavitieshavebeen
be recognizedwithin the depositand theseare des- filled with finely laminatedto massivedolomiticsilt-
ignatedstageI and stageII. The stagesare charac- stoneand quartz dololutite (Fig. 8B). In some in-
terized by different sulfidetextures,sulfidehost-rock stances,the mineralization can be shown to alternate
relationships,andtemporalrelationships with the host with brecciationand corrosionof previouslydepos-
rocks(Table 2). ited mineralization(Figs.8C and D).
StageI mineralizationconsists of sphalerite,pyrite,
marcasite,and galenain a matrix of lutite-sizedand Mineralogyof the sulfidecrusts
coarsergraineddolomiticsediment(Figs. 8 and 9). Sphalerite:Sphaleriteis the mostcommonsulfide
The sulfidesoccurascolloformand crystallinecrusts in the stageI mineralizationand is fine-grainedcol-
and as fragmentswithin the matrix. The matrix will loform or coarselycrystallinein texture. The collo-
be shownto be identicalin lithologyto the matrix form sphaleriteis usuallystraw yellow to red-brown
of the dolomite breccias which fill the karst caverns in color,displaysfine growthzoning,and variesfrom
developedbelowthe Reward-Lynottunconformity. flat laminatedto mamillaryin form (Fig. 8A). Several
The colloformsulfidecrustsarecommonlyseparated percent of quartz and dolomite inclusionsoccur
TABLE2. Comparisonof StageI and StageII Mineralization
StageI mineralization StageII mineralization
Sphalerite Straw yellow to red-brown colloformand Off-white to light red, coarselycrystalline

coarselycrystalline
Galena Coarse-grainedand often pseudomorphedby Coarse-grained
dolomite
Pyrite-marcasite Colloform crustsand coarselycrystalline Comb textureand coarselycrystalline

Matrix Dolomitic siltstoneand minor collophane Sparry dolomite, clay, and bitumen
Vein edges Commonly a brown collophane-dolomiterim Irregular edgeswith disseminatedpyrite-
marcasiteand minor sphaleritein the host
Form Colloform crusts, vein fill, and breccia Vein fill, matrix of solutioncollapsebreccias,
fragments and minor replacement
Temporal relationship Crosscuts Reward Dolomite and occurs within Crosscuts Reward Dolomite, cavern infills in
the karst cavernbrecciadevelopedbelow the the Reward Dolomite and the basalLynott
Reward-Lynott unconformity Formation
DOLOLUTITE
KARST INFILL B
KARST
INFILL A
\
\ ß.. DETRITAL
'- ..SPHALERITE
ß
SPHAL-
i
SPHALERITE
RIMS AND •\ SPHALERITE
FRAGMENTS \
RIM
DOLOLUTITE
I cm
,GROWTH
(DIRECTI(•N
c
COXCO DEPOSIT, McARTHUR RIVER DISTRICT 9.9.9
within the sphalerite.The quartz grainsare com- is a massiveto finely laminateddolomiticsiltstone

monly euhedraland rangefrom 25 to 80 ttm in di- andquartzdololutite(Fig. 8B, C, and D). The lutites
ameter. In one instance,a 400-ttm-wide lamina in the vary from light gray to blackin colordependingon
colloformsphaleritecontainsup to 20 percent by the amountof disseminated organicmatter.The con-
volume of disseminatedirregular areasof reddish stituents of the matrix can be divided into nonsulfide
brown to opaque organic matter (Fig. 8A). These and sulfidecomponents. The nonsulfide components
concentrations of organicmatter are roughly elon- consistpredominantlyof quartz and dolomitewith
gated in the growth directionof the sphaleriteand minor mica, K-feldspar, collophane,organic matter,
presumablyare intergranularinclusions. and chert,and are identicalto the components of the
Coarselycrystallinesphaleriteislessabundantthan fine-grainedsediments in the karst cavitiesin the
the colloformsphaleriteand showseuhedralto sub- Reward Dolomite.
hedraloutlines.The coloris usuallystrawyellowand The sulfidecomponentof the matrix is extremely
the crystalscontainonly rare inclusions of dolomite. variable.The moststrikingcomponents arefragments
It occursin laminae up to 5 mm wide within the of colloformsphalerite,pyrite, and marcasite(Fig.
colloformsphalerite(Fig. 8A) andasinclusions in the 8B and C), which rangefrom lessthan a millimeter
colloformpyrite and marcasite. up to a few centimetersin diameter.Thesesulfide
The iron contentof the sphaleritein one sample fragmentsare usuallyangularand are identicalin
was investigatedby electron microprobeanalysis texture to the sulfide crustspreviouslydescribed.
(Brunckhorst,1979). Three spot analyseson straw Fine-grained sphaleriteis commonlyconcentrated in
yelloweuhedralsphaleriteindicatea rangein iron laminae, from 0.5 to 1.0 mm wide, parallel to the
contentfrom 0.5 to 1.1 mole percentFeS, whereas laminationsin the matrix (Figs.8C and D, and 9C).
four analyses on light to dark yellowcolloformsphal- The laminae consistpredominantlyof irregularly
erite indicatea rangein iron contentfrom 0.13to 13.5 shapedred-brown-colored sphaleritegrains which
mole percent FeS. rangefrom 20 to 50 #m in diameter.Accompanying
Galena: Galena is a minor constituent of the min- the sphaleriteare euhedralto subhedralquartzgrains
eralization and occurs as isolated euhedral to subhe- which average50 ttm in diameterand minor pyrite,
dral grainswithinthecolloformsphaleriteandpyrite- marcasite,and dolomitegrains. The color of the
marcasite.Compositegrainsof galenaand dolomite sphaleriteis identical to the colloformsphalerite
are very commonand displaytexturesindicativeof whereasthe euhedralquartz grains are similar to
dolomitereplacementof galena(Fig. 9A). Evidence quartz inclusionsin the colloformsphalerite.The
for thisinterpretation is the perfectcrystalboundary sphaleritelaminaedrape over mamillarycolloform
whichis definedby bothgalenaanddolomitegrains sphaleriteand show prelithificationslumpingand
and the similarcrystallographic orientationof seem- erosionalfeaturesindicatingthe facing of the se-
ingly disconnected galenagrainsasshownby the at- quence (Fig. 9C). Thesesedimentarystructuresin-
titude of cleavagepits. dicatedetrital accumulationof the sphaleritegrains;
Iron sulfide:Iron sulfideoccursin the sulfidecrusts the similarityto the sphaleritein the colloformcrusts
as interlayeredpyrite and marcasite(Fig. 8C). The would indicatethat the sphaleritegrainsare disag-
grainsizeof the sulfideisextremelyvariableasis the gregatedcolloformsphalerite.
colorof the pyrite whichvariesfrom yellowto brown- Sphaleritealsooccursin regularto irregularthin
ish yellow. The pyrite-marcasitelaminae often con- strata-bound lenseswithin blackorganic-richsiltstone
tain upwardof 130to 40 percentsphaleriteandgalena laminae.The individualsphaleritegrainsaverage200
inclusions aswell asdistinctcolloformsphaleritelam- ttm in diameterand are separatedby concentrations
inae. Colloformpyrite-marcasiteis rarely replaced of organicmatterand minordetritalquartzand do-
by sphalerite(Fig. 9B). lomite grains.
Matrix: The matrix of the stageI mineralization Euhedralto subhedralpyrite and marcasitegrains
FIe;.8. Photomicrographs showingtexturalrelationships betweenstageI sulfidesand the karstinfillings

in the Coxeodeposit.All photosare negativeprintsof thin sections.
A. Dololutite of the Reward Dolomite (black) crosscutby a breccia vein of stageI mineralization
consisting of eolloform(e) and coarselycrystalline(co) sphaleritein a matrix of dolomiticsiltstone.A
strata-boundzoneof organicmatter inclusions(om) occursin the colloformsphalerite.
B. StageI mineralizedkarstbrecciawithinthe RewardDolomite.Colloformsphaleriteand pyritecoat
theedgesof the originalkarstcavityandfragmentsof dololutite(black).The matrixisa dark carbonaceous
dolomitiesiltstonesimilarto siltstones
of the Lynott Formationand containsfragmentsof disaggregated
crust material.
C, D. StageI mineralizedkarstbreceia.Dolomiticsiltstone
of karst-fillingA predatesdeposition of the
eolloformmarcasite-pyrite-sphalerite
crustand depositionof dolomiticsiltstoneof karst-fillingB.
•ii00 •um
I E
G ! 50jim I
COXCODEPOSIT, McARTHUR RIVER DISTRICT 251
occurdisseminatedthroughthe matrix. Thesegrains able but with smallirregularembaymentsoccupied

vary in sizefrom a few micronsup to a few hundred by the overgrowingsulfide,usuallysphalerite.The
microns.Compositegrainsof pyrite and marcasite presence of inclusions
of collophanewithin the sphal-
often with a euhedralpyrite core and with a radial erite in theseembaymentssuggests replacementof
textureare common(similarto Fig. 9E but up to 200 the collophaneby the sphalerite.
ttm in diameter).
Paragenetic sequence
Fragments
Pyrite,marcasite,and sphaleriteappearto alter-
The matrix for the mineralizationcommonlycon- nate in the colloform crusts in a random manner,
tainsangularto roundedfragmentsof dolomiticsed- suggesting thereis nota clearlydefined,simplesul-
iments with a maximum diameter of several centi- fideparageneticsequence.Insufficient
workwascar-
meters.Thesefragmentsare commonlyrimmed by ried out to definewhethergroupsof bandscouldbe
colloformsulfidecrusts.The dominantfragmentli- correlatedbetweensamplesto definea "sulfidestra-
thologyis dololutite;however,collophane-rich lutites tigraphy"(Pinckneyand Rafter, 1972; McLimans,
and dolomiticsiltstonefragmentsare also present. 1979).
The lithologiesare identicalto fragmentlithologies
in the brecciafills in the karstcavernsdevelopedbe- Aspectsof the origin of stageI mineralization
low the Reward-Lynottunconformity. StageI mineralizationwas depositedas sulfide
crustsontheedgesof opencavitiesandonfragments.
Dolomite-collophanerim The mineralization both predatesand postdatesdo-
StageI mineralizationfrequentlyhasa dolomite- 1omite-collophane rims whichhavebeeninterpreted
collophanerim separatingthe sulfidesfrom the do- as detrital and chemicallyprecipitatedmaterialde-
1olutitehost,althoughcolloformsulfideshave been positedon the floorof cavernsin the phreaticzone
found between the dololutite host and the dolomiteof a karst systembelow the Reward-Lynottuncon-
collophanerim (Fig. 9D). This rim is similarin tex- formity. The fine-grainedsedimentsand breccias
ture to that on the edge of the karstcavitiesin the which were depositedwithin this karst systemare
Reward Dolomite but containsa higher proportion identicalto the matrix of the stageI mineralization.
of disseminated sulfidesand red-brownorganicmat- The mineralizationwasthereforedepositedwithin
ter. The rim containsskeletalpyrite-marcasite grains the karstsystem.The brecciationand disaggregation
(Fig. 9E) andelongategrainsof galenaand lesscom- associated with the mineralization indicates that some
monly sphalerite.The sulfidegrainsare commonly mineralizationwas depositedduring the active ero-
15 to $0 ttm wide and are either elongatedparallel sionalstageof the system.The association of the
to the laminationsin the rim or are markedlycross- mineralization with the dolomite-collophanerims
cutting.Thesegrainsare associated with void fillings which are confinedto the phreaticzoneof the karst
of red-brownorganicmatter(Fig. 9F). Thereis ob- system,the absence of mineralization
associated with
viouslya closespatialrelationshipbetweenthe sulfide the speleothem deposits,the association
of the sulfides
and the organicmatter. In someinstances, the sulfide with organicmatter reflectingreducingconditions,
occursasa thin edgeonorganicmatterconcentrations and the confinement of the mineralization to the
(Fig. 9G). deepersections of the RewardDolomitesuggestcon-
The contactbetweenthe dolomite-collophane rim finement of the mineralization to the phreatic zone
and the colloformsulfidecrustsis broadly conform- of the cavernsystem.
Fie. 9 Photomicrographs showingsulfidetexturesin stageI mineralization.

A. Galena (G) crystalovergrownby pyrite (P) and sphalerite(s) and partially replacedby dolomite
(D). Polishedsection,plane polarizedlight.
B. Colloformmarcasiteand pyrite (white) partially replacedby sphalerite.Polishedsection,plane
polarizedlight.
C. Negativeprint of a thin sectionof karstbreccia.The dolomiticsiltstonefilling containsfragments
of dololutite(black)with colloformsphalerite-pyrite
crustsand thin laminae(L) of grainsof disaggregated
colloformsphalerite.
D. Colloformgrowthsof sphalerite(s)and pyrite (P) on dololutiteof the RewardDolomite(D) on the
edgeof a karstcavity. StageI sulfidesare overlainby the collophane-dolomite rim (R). Thin section,
plane polarizedlight.
E. Skeletalmarcasitegrains disseminatedin a dolomite-collophane rim. Note the central euhedral
pyrite grains.Polishedsection,plane polarizedlight.
F. Strata-boundconcentrationof organicmatter from a dolomite-collophane rim. Thin section,plane
polarizedlight.
G. Concentrationof organicmatter (ore),almostcompletelysurroundedby a galenarim (R), from a
doiomite-collophane rim. Polishedsection,plane polarizedlight.
S•
o il
282
Althoughthe absolutetime of mineralizationcan- the hostrock in a matrix of stageII mineralization.

not be defined,its relative timing with respectto the Fragmentsvary from angularto rounded(Fig. 10C
enclosingsedimentsis well defined. Mineralization throughF) and includeboth dololutitefrom the Re-
was later than the uplift which exposedthe Reward ward Dolomite and the dolomitic siltstone and do-
Dolomiteto erosion,andearlierthanthe transgressionlomitebrecciawhich fill the karstcavities(Fig. 10G).
which precededdepositionof the Lynott Formation Fragmentsreach a maximum dimensionof several
and filling of the remainingopenspacein the cavern centimeters.In somebreccias,progressive deposition
system. of sulfideson the sidesof the fragmentshasgivenrise
to cockadetextures(Fig. 10G) whereasin other in-
Stage II Mineralization stancessulfidegrainsare disseminated in the matrix
StageII mineralizationis volumetricallymore im- and their growth is unrelated to the edgesof the frag-
portantthan stageI and is concentratedin the 40 to ments (Fig. 10C).
60 m of the Reward Dolomite below the silicified The brecciasvary in texture between two end
zone.Within thisinterval,zonesof high-grademin- members.At one extreme, the fragments are sub-
eralizationseveralmetersacrossaveraging10 to 20 rounded,the sedimentarystructuressuchasbedding
weight percent lead plus zinc are concentratedim- in the fragments are randomly oriented, and the
mediately below the silicifiedzone. Similar zonesof mineralizedmatrix may make up 130percentof the
high-grademineralizationare randomlydistributed rock by volume (Fig. 10G). At the other extreme,
throughthe restof the interval.Minor mineralization fragmentsare angular,sedimentarystructuresin ad-
also occurs in the silicified zone, in the basal few jacentfragmentsare onlyslightlydisoriented,andthe
metersof theLynottFormationandin theunderlying mineralizedmatrix may make up only a few percent
Mara Dolomite. Mineralization occurs over a strike of the rock (Fig. 10E). This type of brecciacouldbe
lengthof approximately 8 km andistruncatedalong classedas crackle breccia and commonly contains
strikeby the Emu andCoxcofaults(Fig. 4). bitumen as the last infilling material. Brecciasbe-
tween theseend memberscontain angular to sub-
Form roundedfragmentsand the fragmentsshowsomero-
tation althoughthey can usuallybe fitted back to-
The mineralization in drill core occurs in veins gether (Fig. 10F).
(Fig. 10A and B) and asthe matrix to dolomitebrec-
cias(Fig. 10C throughG). The veinsvary in width Mineralogy
from hairline fractures where the base metal sulfides The stage II mineralizationhas a simple sulfide
occuras discretegrainsup to zonedveinsa few mil- mineralogyconsistingin order of decreasingabun-
limeterswide.The wallsof theveinsvaryfromknife dance of sphalerite,pyrite, marcasite,and galena.
edgeto transitional.
In the transitional
edgespyrite, The gangueis usuallya ferroandolomitewhich may
marcasite,and lesscommonsphaleritecan be seen containglobulesof bitumen.
to replacethe dololutitehostover distancesup to Sphalerite:The sphaleriteis off-white, straw yel-
severalmillimeters (Fig. 10A). The veins contain low, or light red in colorand occursin combtexture
smallroundedfragmentsof the hostdololutite. on the edgesof veinsor as isolatedeuhedralto sub-
The mineralizedbrecciasconsistof fragmentsof hedral grains(Fig. 10A, B, and G). Grainsreach a
FIG. 10. Photomicrographs of sulfide-host-rocktexturesof stageII mineralization.

A. Edge of a mineralizedvein with spongypyrite (P), marcasite(M), and sphalerite(S). Polished
section,plane polarizedlight.
B. Vein with pyrite (P), sphalerite(S),galena(G), and dolomitegangue(D) crosscutting dololutiteof
the RewardDolomite.Thin section,planepolarizedlight.
C. Two generationsof stageII mineralized solutionbreccia (DB1 and DB2). The matrix of DB1
contains60 percentdisseminated pyritewhereasDB2 contains coarsesphalerite(S).Note the fragments
of DB1 matrixin DB2. Thin section,planepolarizedlight.
D. Solutionbrecciawith angularfragmentsof dololutitein a mineralizedsparrydolomitematrix.Note
thefragments of pyriteandtherimsof sphalerite (S)andpyriteon brecciafragments. Thin section,plane
polarizedlight.
E. Polishedslabof stageII mineralizedcracklebreccia.Fragments of RewardDololutitein a matrix
of dolomite(white),sphalerite(gray),and bitumen(black).
F. Polishedslabof mineralizedsolutioncollapsebreccia.Fragmentsof a dark dololutitebed show
slightrotation.Matrix is fine-grainedsphalerite.
G. Negativeprint of a thin sectionof mineralizedbreccia.Fragmentsof dololutite(D) from the Reward
Dolomiteandquartzdolorudite (QD) fromkarstinfillings
in theRewardDolomite,in a matrixof pyrite
(white),sphalerite
(lightgray),andspatrydolomite(black).Notethefragment(MC) of collophane and
marcasite in the karst sediment.
2134 WALKER,GULSON,AND SMITH
maximumdiameterof 2 mm and containirregular ever,the textureis morecomplicated.For instance,

inclusions
of fine-grainedpyrite and galena.Subhe-
fragmentsof dololutitewith a mineralizedrim on one
dralto anhedralgrainsof sphalerite
infrequentlyoc-
edgewill occurin a solutionbreccia(Fig. 10D) or
cur disseminated in the hostdololutiteadjacentto
fragmentsof the matrix of one solutionbrecciawill
thinsphalerite-bearing
veins.Thesegrainscontainup occurin a later crosscutting solutionbreccia(Fig.
to 130percent irregular inclusionsof dolomite. The 10C). These textures indicate that solution and col-
proportion
of sphalerite
in thehostrockfallsoff rap- lapsehavealternatedwith deposition
of the miner-
idly over a few millimetersfrom the veins.In some alization.
veins,the sphaleritegrainshavebeenfracturedand
are healedby sparrydolomite. Aspectsof the origin of the
P•trite:Pyrite occursin coarselycrystallinecomb stageII mineralization
textures andasisolatedeuhedralto subhedral grains Timing: The stageII mineralizationcrosscuts the
(Fig. 10A).Marcasiteusuallyoccursassubhedral laths Reward Dolomite including the silicifiedzone, the
in thecombpyriteor in euhedral to subhedral crystal caverninfillingsin the Reward Dolomite,the stage
aggregates with pyrite. Aggregates of pyrite and I mineralization,and the basal Lynott Formation.
marcasitegrainscommonlyoccurdisseminated in the The mineralizationwasthereforedepositedafter lith-
host dololutiteadjacentto the veins and contain a ificationof the basalLynott Formation.A lower age
high proportion
of dolomiteinclusions
(Fig. 10A). limit for the mineralization cannot be determined on
Irregularfracturingof the combpyrite is a common the evidence available.
feature and the fractures are healed with dolomite.
Origin of the mineralizedbreccias:
The following
Galena:Galenagrainsvary from subhedralto an- characteristics of the mineralized breccias must be
hedral and reach a maximum diameter of several consideredin any geneticmodel.
millimeters(Fig. 10B). It occurspredominantly
as
discretegrainswithinthe sparrydolomite. 1. The breccias
arealwaysfragmentsupported and
Gangue:Coarsesparrydolomiteis usuallythe last thereforecontrast
sharplyto the breccias
within the
mineral depositedand fills the center of the veins karst-produced caverns.
(Fig. 10B).It istypicallya highironvarietyasshown 2. There are no exoticfragmentsin the breccias.
by stainingwith potassium ferricyanide. 13. The fragments vary from roundedto extremely
Bitumenakcumulations up to a few millimetersin angular.
sizearea commonfeatureof the veinsalthoughthey 4. The breccias vary from crackle breccias in
are notvolumetricallyimportant.The bitumenoccurs which there is no relative movement between adja-
eitheras roundedglobuleswhichare enclosed by cent fragments to brecciasin whichthereiscomplete
dolomitegrainsor asirregularmasses which fill the rotationand displacement of adjacentfragments.
remaining open spacein the veins. The bitumen is 5. The breccias average 10 to 20 m in dimension
composed of high molecularweight aromatic-rich and are preferentiallydeveloped in the Reward Do-
hydrocarbons andis considered to representthe res- lomite immediately below the silicifiedzone.
iduefrom a degradedcrudeoil (Saxby,1978). The characteristics of the cracklebrecciassuggest
an origin by brittle deformation,for instance,hy-
Paragenetic sequence
draulicfracturing(HubbertandWillis,1957;Phillips,
StageII intergranulartexturesare usuallysimple 1972).The high porewaterpressure may havebeen
andsuggest bothsimultaneousandsequential growth. providedby a mechanismsuchas seismicpumping
Pyrite and marcasiteare usuallythe first sulfidesde- (Sibsonet al., 1975) in the Emu fault zone.Suchfrac-
positedon the wallsof the veins,on the edgesof turing may have provided accessfor solutions,in-
fragments,and within the hostrock. The next sulfide cludingthe mineralizingsolutions, whichcauseddis-
is usuallysphalerite.However,the deposition of the solutionof the dolomiteto producethe openbreccias.
ironsulfideandthesphalerite is usuallyseparated in The open brecciasshow a closeresemblanceto the
time by a brecciationepisode.This is indicatedby solutioncollapse
brecciaswhichhavebeendescribed
elongatefragmentsof pyrite which have poeledoff from the SilesianMississippiValley-type deposits
thewallsof theveinsandaretotallyenclosed in sphal- (Sass-Gustkiewicz, 1974) and from the Central Ten-
erite. Depositionof galenaoverlappedthe sphalerite nesseezinc district (Kyle, 1976).
and continuedafter depositionof the sphalerite.Mi- Cap rock: There is a noticeableconcentrationof
nor pyrite accompanied both sphaleriteand galena the mineralizationin the sequenceimmediatelyun-
deposition. derlyingthe silicifiedzoneat the top of the Reward
The remainingopen cavity is usuallyfilled by Dolomite.This is considered to reflectthe imperme-
coarse-grained
sparrydolomitewhich may contain able nature of the silicified zone and the confinement
finely disseminatedsulfide.In someinstances,how- of the mineralizingsolutions,
that is,the silicifiedzone
hasactedasa caprockto the mineralizationsolutions. igin.However,somegroupsshowevidenceof necking

In the areaswhere the silicifiedzoneis not present, down and the fiat nature of the inclusionssuggests
the basalLynott Formationcontainsthin vein min- a secondary origin.Planesof irregularfiat inclusions
eralization over a few meters. in the sphaleriteare obviouslysecondaryinclusions
Fluid Inclusions
andprobablyrepresent healedcleavagefractures.All
the inclusionsfoundin the sphaleriteconsisted of liq-
Severalsamplesof stageI and II mineralization uid and vapor. No daughtercrystalswere seen.
wereexaminedfor fluid inclusions in doublypolished Dolomite: Fluid inclusions are more common in
plates.No usableinclusions for temperaturestudy the coarsesparrydolomitethan in the sphalerite.
were found in stageI sphaleriteand the studywas However, it was impossibleto distinguishprimary
concentratedon sphaleriteand dolomitefrom stage andsecondary inclusions.
The largestinclusions range
II mineralization. from 20 to 50 gm in sizeand occursinglyor in small
Details of sample preparation are describedin groupsand vary from roundedto very irregularly
Walker (1980). After microscopicinspectionof the tabular in shape.Severalwere found to containa
plates,inclusionswere selectedfor temperaturede- smallorange-colored daughtermineralaswell asthe
terminations. Selected inclusions were examined first normalliquid and vaporbubble.The daughtermin-
in a freezingstagein which a samplechamberfilled eral has two commonshapes.The first is prismatic
with propanolwascooledby a flow of nitrogengas with doubleterminationsand crystalson the order
from a liquid nitrogenheat exchanger.Becauseof of 5 by 1 •tm. The second is pseudohexagonal tabular
the smallinclusionsize,the precisionof measurement with diameterson the order of 4 •tm. The shapeand
was not high and severalfreezing runs were per- the intensecolorin sucha smallcrystalwouldsuggest
formed on each inclusion.In generalthe spreadof the mineral is hematite. Numerousplanesof small
valueswaslessthanIøC. The accuracyof thefreezing elongateinclusions probablyrepresenthealedcleav-
temperaturesobtainedwason the order of _1 øC. In age planes.
all runs,the freezingpoint wasapproachedfrom be-
Results obtained
low to avoiderroneousresultsfrom metastabilitydue
to failure to nucleateice. In someinstances, freezing Freezing temperatures: Freezing temperatures
of the inclusionfluid wasextremelydifficultandsome were determinedon nine primary and possiblypri-
inclusion fluids in dolomite would not freeze at mary inclusions in sphalerite(Table 13).The temper-
-150øC. Freezingtemperaturesare only reportedif aturesrangedfrom -22.2 ø to -27.8øC. Theseinclu-
the vaporbubblewaspresentat the pointof disap- sionsincluded the subsphericalprimary inclusions
pearanceof the lastice crystal.Homogenization tem- and the larger isolatedpossiblyprimary inclusions.
peratureswere then measuredon a calibrated Leitz Thesefreezing temperaturescorrespondto very sa-
heatingstage.Heatingrunswereattemptedonall the line fluidsalthoughthe salinitycannotbe expressed
inclusions for which freezingtemperatureshad been asunitsof percentNaCI equivalents,becausethe low-
obtained. However, becauseof the poorer optical est freezing temperaturein the pure NaC1-H20 sys-
quality in the heatingstage,worthwhiledata could tem is -21.1øC at 213.13 equivalent weight percent
only be obtainedon a few inclusions. The accuracy NaCI (Roedder,1962).The low temperatureindicates
of thedatareportedisprobablyontheorderof +$øC. the presenceof saltsother than NaCI, for instance,
CaCI2. Freezing runson the two obvioussecondary
Nature of the inclusions inclusionsin sphaleritegave freezing temperatures
Sphalerite:Recognizableprimary fluid inclusions of -8.7 ø and -19.8øC, indicatingthe containedfluids
in the sphaleriteare confinedto small (6-12 •tm in are lesssalinethan thosein the primary inclusions.
diameter)subspherical inclusions. The criteria(Roed- Becauseof the metastabilityproblem, freezing
der,1976)uponwhichtheinterpretation of a primary temperatureson inclusionsin the dolomitegangue
originhasbeenbasedare occurrencein a smallthree- were only obtainedon onegroupof inclusions (Table
dimensional groupremovedfrom otherobvioussec- 13).This groupof three inclusionsgave temperatures
ondaryinclusions,equantshapeof theinclusions, and between -25.5 ø and -27øC, which indicate that the
occurrenceof severalinclusions in a growth zone. dolomiteprobablywasdepositedfrom a brine of ap-
Theseinclusions wereextremelydifficultto studyin proximatelythe samesalinityas the sphalerite.
the heatingandfreezingstages because of their small Homogenizationtemperatures:Limited homoge-
sizecoupledwith opticalproblems causedby internal nization temperatureswere determined becauseof
reflectionsalongthe wallsof the inclusions.Several the opticalproblemsencountered.Resultsare given
isolatedor groupsof largerinclusions up to 40 in Table 4. A subsphericalprimary inclusionin the
in diameterwerefoundin the sphalerite.The isolated sphaleritehomogenizedat 169øC as did a large pos-
natureof the inclusions
wouldsuggest a primary or- sibly primary inclusion.Homogenizationtempera-
256 WALKER, GULSON,AND SMITH
TABLE13. FreezingPointDeterminations on Fluid Inclusions

in Temperatureof depositionof the
StageII Dolomiteand Sphaleritein the CoxcoDeposit stageII mineralization
Drill Depth The actual sediment cover at the time of miner-
hole (meters) Mineral Last ice alizationis not known,but a maximum possiblevalue
of 1,065 m has been estimated (Walker, 1980). As-
Coxco 18 128.2 Dolomite (1) -25.5 ø
-25.5 ø sumingthis figureand usingthe data of Lemmlein
and Klevtsov(1961) for 20 percentNaC1, the maxi-
Dolomite (2) -25.8 ø
mum hydrostaticpressurecorrectionto be added to
-25.9 ø
-25.9 ø the homogenization temperatureis probablylessthan
10øC. The temperaturerange indicatedfor deposi-
Dolomite ($) -27.0 ø
tion of the sphaleriteis 100ø to 170øC and for the
-25.9 ø
dolomite 120 ø to 150øC.
-27.8 ø
-25.$ ø
Comparisonwith other Mississippi
Coxco18 128.2 Sphalerite(1)
-22.2 ø Valley-typedeposits
Sphalerite(2) -22.8 ø The freezing and homogenizationtemperatures
-21.8 ø obtainedin stageII mineralizationare consistentwith
-28.5 ø the resultsobtainedfrom Mississippi Valley-typede-
posits(Roedder,1976). The homogenization temper-
Coxco18 128.2 Sphalerite(1) -24.6 ø
aturesfor the main-stagesulfidesin thesedepositsare
-24.4 ø
-24.4 ø
generallyin the range 100ø to 150øC and rarely as
high as 220øC (McLimans,1979) or as low as 60øC
Sphalerite(2) -25.8 ø
(Roedder,1968).The freezingtemperaturesof Mis-
-25.2 ø
-25.5 ø
sissippiValley-typeinclusionfluidsare commonlyin
-25.4 ø the range -10 ø to -$0øC and indicate the presence
of appreciableamountsof ionsother than Na+ and
-25.0 ø
C1- (Roedder,1976).
-25.$ ø
Sulfur Isotopes
Coxco 18 128.2 Sphalerite -24.7 ø Previous studies
-24.5 ø
-24.7 ø This study presentsthe first sulfur isotopemea-
-24.7 ø surementson the Coxcomineralization.Sulfurisotope
studieshave, however, been carried out on the H.Y.C.
Coxco18 128.2 Sphalerite(1) -25.$ ø deposit(Smith and Croxford, 1978), on the lateral
-22.2 ø stratigraphic
equivalentsof thismineralization(Smith
Sphalerite(2) -22.8 ø and Croxford, 1975), on the Ridge and Cooley de-
-21.8 ø posits(Rye and Williams, 1981), and on the barite
-23.5 ø in the McArthur Group (J. W. Smith and R. N.
Walker, unpub. data).
Coxco16 84.0 Sphalerite -27.8 ø
The sphaleritefrom the H.Y.C. depositanalyzed
-27.7 ø
by Smithand Croxford(1978)had a •a4Srangefrom
-8.4 ø
8.8 to 8.9 per mil, the galenasa rangefrom -1.2 to
Coxco 16 84.0 Sphalerite(1)
-9.0 ø +5.7 per mil, and the pyrite a range from -8.9 to
+15.9 per mil (Fig. 11). The relativeconsistency of
-18.6 ø
the isotope fractionation between sphaleriteand ga-
-18.8 ø lena indicatesthat thesesulfidesmay have precipi-
tated in isotopicequilibrium at a temperature be-
tween 100ø and 260øC (Smith and Croxford, 1978;
Williams and Rye, 1974). The isotopicratiosof the
turesof a groupof inclusions
whichshowedevidence pyrite indicatethat it did not precipitatein isotopic
of neckingdowngavevaluesof 119ø and 99øC.Two equilibriumwith the coexisting sphaleriteandgalena.
secondaryinclusionsgave temperaturesof 100øC. Smith and Croxford (1978) interpretedtheir sulfur
Three homogenizationtemperatures were deter- isotoperesultsasimplying a dual sulfursource.They
mined in the ganguedolomiteand gave valuesbe- consideredthat the pyrite precipitatedby bacterial
tween 120 ø and 127øC. reductionof seawatersulfate,and the sphaleriteand
T^Bt•: 4. HomogenizationTemperaturesof Fluid Inclusionsin Dolomite and Sphalerite

from the StageII Mineralizationin the CoxcoDeposit
Drill Depth Temperature

hole (meters) Mineral (øC) Remarks
Coxco 18 128.2 Sphalerite 169 Possiblya primary inclusion

Coxco 18 128.2 Sphalerite1 119 Possiblya primary inclusion
Sphalerite2 99 Possiblya primary inclusion
Coxco 16 84.0 Sphalerite1 100 Secondaryinclusion
Sphalerite2 100 Secondaryinclusion
Coxco 16 84.0 Sphalerite1 169 Primary inclusion;temperaturevery approximateonly
becauseof poor visibility
Coxco 18 128.2 Dolomite 120
galenawereintroducedassuchwith the mineralizing containeda mixtureof pyrite and marcasite.The sul-

brine and precipitatedon the seafloor.Williams and fideswereconverted
tosulfurdioxideby heatingwith
Rye (1974) reinterpretedthe resultsas implying ini- cuprousoxide at 900øC in a sealedevacuatedtube
tial pyrite precipitatedby bacterialreductionof sea- (Kaplanet al., 1970). Isotopicmeasurements
on the
watersulfateandlater pyritetogetherwith sphalerite sulfur dioxide were made on a Micromass 602 ratio
and galenadepositedfrom an epigeneticallyintro- massspectrometer.The resultsare reported in per
duced brine by replacementof initial pyrite. Wil- mil variation relative to the Cation Diablo troilite
liams'(1978)epigeneticmineralizationmodelfor the standard. Analytical precisionof the data is 0.1
stratiformmineralizationinvolvingabiological sulfate per mil.
reductionis alsocompatiblewith the sulfur isotope Results and discussion
results.
Rye and Williams (1981) analyzedthe sulfur iso- Sulfur isotopicmeasurementswere made on 49
topiccomposition of 19 samples of pyrite,galena,and samplesof iron sulfide(pyrite and marcasite),sphal-
sphaleritefrom the coarse-grained mineralizationin erite, and galenafrom diamonddrill core from the
the CooleyI, CooleyII, and Ridge II deposits(Fig. Coxcodeposit.Thesesampleswereselectedasbeing
11).The •34Svaluesvaryfrom 5.8 to 10.1per mil for representative of the varioussulfidetypesin the de-
pyrite, from 0.4 to $.8 per mil for galena,and from posit.
4.8 to 6.2 per mil for sphalerite.The isotopicfrac- The sulfurisotoperesultsare listedin Table 5. The
tionationbetweensphaleriteandgalenais2.2 per mil sulfurisotopicfractionations
betweensphaleriteand
for the CooleyI deposit,2.8 per mil for the Cooley galena (Aa4Ssphalerite-galena) are only reported
II deposit,and variesfrom $.4 to 4.5 per mil for the wherethe individualsulfideswere sampledfrom ad-
RidgeII deposit.Thesefractionations indicatemax- jacent grains.
imum isotopictemperaturesof 290øC for Cooley I, Disseminatediron sulfides:The majority of the
275øC for Cooley II, and 120ø to 180øC for sedimentsin the RewardDolomiteand the Lynott
RidgeII. Formation contain minor finely disseminatediron
Thirteen samplesof barite from the McArthur sulfidesassociated
with organicmatter.It hasalready
Groupshowedbs4S values(Fig. 11) from 19.9to $1.5 beensuggested that thissulfideformedby anaerobic
per mil (J.W. Smithand R. N. Walker,unpub.data). bacterialreductionof sulfateduringdiagenesis.
The
The samples werecollectedfrom environments which rangesof sulfur isotoperatiosof theseiron sulfides
varied from diageneticnodulesin supratidaldolo- are -0.6 per mil (RewardDolomite), 10.7 to 20.2 per
stonesto materialfrom fault zones(Walker, 1980). mil (Lynott Formation), and 15.9 to 16.6 per mil
(cavefillingsin the Reward Dolomite).
Experimental method Few measurements have been made on the sulfur
The coarsegrain sizeof the sphaleriteand galena isotopiccompositionof disseminatediron sulfide in
allowedsufficientlylarge samplefor analysesto be Proterozoic sediments. Disseminated iron sulfide in
excavatedusinga vibratingtungstenneedle.Thiswas the Barney Creek Formationaway from the strati-
not alwayspossiblein the caseof the iron sulfidesand form lead-zincmineralizationgivesvaluesbetween
the concentrate
wasusuallycleanedby boilingin 10 -5.4 and +27.0 per mil (Fig. 11), and the samples
percent hydrochloricacid to remove other sulfides from Coxcofall withinthisrange.In youngersedi-
(Smithand Croxford,1978).The iron sulfidesamples ments,Schwarczand Burnie(1978)showedthat there
• 34 $ o/•
be expected.The oppositeextreme is a shallowma-
i I
rine or brackishenvironmentwhere the supplyof
-5 0 5 I0 15 sulfate is limited. The ba4Sdistribution of the sulfides
DISSEMINATED in thisinstance
wouldshowa fiatdistribution ranging
PYRITE IN COXCO HOST
SEQUENCE in valuefrom seawatersulfateto a depletionof about
25 per mil (Schwarczand Burnie, 1975).
PYRITE
Assuminga seawater sulfate value in the same
STAGE I
SPHALERITE
range as the barite in the McArthur Group, that is
COXCO
I ß DEPOSIT
20 to 32 per mil, the •s4Scomposition
of the diage-
GALENA (a)
neticironsulfides at Coxcowouldsuggest deposition
II of the sequencein shallow marine to brackishde-
PYRITE
positionalenvironmentswhere the available sulfate
I1 ß l! supply is limited. Such environmentsare consistent
STAGE TT with the generallithologyandsedimentary
structures
SPHALERITE COXCO of the sedimentscomprisingthe Reward Dolomite
DEPOSIT andthe cavefillingsin the RewardDolomiteand the
GALENA (a) Lynott Formation.
StageI sulfides:
Nine samples
of colloformpyrite-
i ß ß PYRITE marcasite,sevensamplesof sphalerite,and three sam-
plesof galenafrom stageI mineralizationwere an-
HYC alyzedand gaverangesof 8.6 to 21.7 per mil, 6.5 to
DEPOSIT 15.4 per mil, and 1.$ to 11.5 per mil, respectively.
(b) The •s4Svaluesof the colloformpyrite-marc•asite
GALENA
showa spreadof approximately15 percentand show
a range and mean similar to the diageneticpyrite
I ß
(10.7-20.2%0)in the karstfillingsin the RewardDo-
PYRITE
1COOLEY
! AND lomiteand the Lynott Formation.The •$4Svaluesof
SPHALERITE ! RIDGE the sphaleriteshowa rangeof 9 per mil and apart
|DEPOSITS from the lightesttwo valuesare outsidethe rangeof
GALENA J (C) the sphaleritein the stageII mineralizationat Coxco,
PYRITE
BARNEY CK. FM
HYC BASIN BELOW
theH.Y.C. deposit,andtheCooleyandRidgedeposits
ß ß I ß ORE BEDS (d) (Fig. 11).The valueshavea similarbut lighterrange
BARNEY CK. FM than the associated iron sulfides.The galenavalues
PYRITE HYCBASINABOVE
ß ß ß ORE BEDS (d) alsoshowa relativelywide (10%0)rangeand havea
PYRITE BARNEYCK.FM lower mean than the sphalerite.
ß ß Ii BMR 2DD(d) StageH sulfides:Twenty-foursulfidesamples from
Mc ARTHUR
BARITE GROUP
the stage II mineralization were analyzed. The •s4S
== "11= (e) values vary from $.6 to 16.1 per mil for iron sulfide,
from 2.9 to 7.$ per mil for sphalerite,and from 0.9
I I I
- 5 0 5 I0 15 20 25 30 to $.4 per mil for galena.
The sulfur isotopicfractionationbetweenclosely
FIG. ll. Summarydiagram of all sulfur isotopicresultsfrom
associated sphaleriteand galenapairsvariesfrom $.8
the McArthurRiver district.(a. thisstudy;b. Smithand Croxford, to 5.1 per mil. The valuesindicate an isotopictem-
1975;c. Rye and Williams,1981;d. Smithand Croxford,1975;e. peraturerangeof 128ø to 191øCusingthe fraction-
J. Smith and R. Walker, unpub. data). ation factor of Smith et al. (1977) or 105ø to 165øC
usingthe fractionationfactor of Ohmoto and Rye
is a systematicrelationshipbetweenthe •j$4Sdistri- (1979).Theserangesare consistent with the homog-
butionof sulfidesin clastic,marinesedimentary rocks enizationtemperaturesof the fluid inclusionsin stage
and the depositionalenvironment.The differencesin II sphalerites.At the depositionaltemperaturesin-
isotopeeffectsare controlledby the kinetic isotope dicated by the sphalerite-galenafractionation, the
effectwhich is dependenton the amountof nutrient iron sulfideis not in isotopicequilibriumwith these
availablefor thesulfate-reducing bacteria,andby the sulfides.
open or closednature of the systemrelative to the This feature is consistent with textural evidence
sulfateand hydrogensulfide.In deep euxinicbasins, whichindicatesthat, althoughthe sphaleriteand ga-
a narrow bs4Sdistributionshowinga fractionation lena were precipitatedadjacentto the iron sulfide,
with respectto seawatersulfateof -50 per mil can the iron sulfidewas depositedearlier than the other
TABLE5. SulfurIsotopeData for Sulfidesfrom the CoxcoDeposit
Drill Depth Pyrite/marcasite Sphalerite Galena

hole (meters) bas (%0) •IS (%0) •lS (%0) A•lSsph.gal
(%0)
StageI mineralization
Coxco 7 71.0 8.6
Coxco 8 27.7 18.4
Coxco 8 52.7 16.0
Coxco 8 54.4 13.4
Coxco 15 39.6 17.1
Coxco 15 39.6 17.6
Coxco 18 161.0 9.1 1.3
Coxco 19 214.3 10.1 6.5 3.1
Coxco 19 234.6 13.0
Coxco 19 234.6 15.4
Coxco 22 173.7 21.0 14.5
Coxco 22 174.0 21.7 14.2
Coxco 22 177.0 14.5 11.5
StageII mineralization
Coxco 7 84.5 15.4 5.2
Coxco 7 84.5 18.8 5.8 2.0 8.8
Coxco 18 155.2 7.0 8.4 8.6
Coxco 14 78.0 16.1 5.8 1.7 4.1
Coxco 14 78.7 10.8 2.9 8.0
Coxco 15 45.4 5.2 6.5 1.4 5.1
Coxco 15 68.8 8.6 5.6 0.9 4.7
Coxco 18 101.6 8.6 5.2 1.0 4.2
Coxco 19 211,8 7.8 2.2 5.1
Disseminated iron sulfide in Reward Dolomite
Coxco 9 112.7 -0.6
Disseminated
iron sulfidein karstinfilling
Coxco 9 58.7 15.9
Coxco 15 208.5 16.6
Disseminated
iron sulfidein Lynott Formation
Coxco 18 81.0 10.7
Coxco 19 152.0 20.2
Coxco 19 160.9 19.2
sulfidesand its depositionwas separatedin time by exchangebetweenthe hostcarbonateand the min-

a brecciationepisode. eralizingfluids.Carbonisotopicratioswere alsode-
It is importantto note the similarityin the distri- terminedon two samplesof bitumenassociated with
butionof the sulfurisotopevaluesof the basemetal stageII mineralization.
sulfidesin the Coxco stage II mineralization,the Previous studies
H.Y.C. deposit,and the Cooleyand Ridge deposits
(Fig. 11). This similaritypermitsthe suggestion that Studiesof the carbonand oxygenisotopiccom-
the sulfidesin eachof thesedepositswere deposited positionsof carbonatesfrom the McArthur River dis-
from sulfur sourcesof approximatelythe same iso- trict have been carried out by Smith and Croxford
topic composition,by the same sulfur reduction (1975) and Rye and Williams (1981). No previous
mechanism,and under similarphysicochemical con- isotopicdeterminationshavebeencarriedout on car-
ditions. bonatesfrom the Coxcodeposit.
Smith and Croxford(1975) carried out analysesof
Carbon-OxygenIsotopes dolomite from mineralized samplesfrom the H.Y.C.
Carbonand oxygenisotopicmeasurements were depositand unmineralizedsamplesfrom stratigraph-
determinedon a suite of 18 samplesof carbonates ically above,below,and adjacentto the deposit.They
from the Coxcodepositto investigatepossible isotopic interpretedtheir resultsasindicatingthe marinena-
ture of the sedimentsand suggested that the isotopic The alternative model is based on the addition of
variationin the resultswas not significant. isotopicallylight carbonto the mineralizingfluid and
Rye and Williams (1981) analyzeddolomitefrom suggestsa lowertemperaturerangeof 100ø to 200øC.
the H.Y.C. and Ridge stratiform depositsand the Smith(1981)disputesthisinterpretationand con-
Ridge and Cooley coarse-grained deposits.Isotopic tends that an exotic mineralizingfluid is not de-
analysesof the dolomitesin the mineralized shales mandedby the isotopicdata. He suggests that sea-
from the H.Y.C. and Ridge stratiformdepositson a water and atmosphericcarbondioxidein equilibrium
b]sCvs.b]sodiagramfall on a lineartrend (Fig. 12). with dissolvedoxygenatedcarbonspeciesin seawater
The isotopicanalysesof the dolomitegangueasso- are the majorsources
of oxygenand carbon(Fig. 12).
ciatedwith the CooleyI and CooleyII mineralization Dolomiteequilibrationtemperaturesmore consistent
are lighter than for the dolomitein the mineralized with mineral textures are obtained if Smith's model
shalesand fall on the continuationof this trend. Bye is applied.
and Williams(1981)suggest that isotopicratiosof the
mineralized samplesare isotopicallydistinct from Experimental methods
unmineralized sampleswhich fit into a box defined All samplesanalyzedwere selectedfrom freshun-
by a •180 rangefrom 17.2to 25.6 per mil and a bl$C weathered diamond drill core. The carbonates were
rangefrom -2.0 to 0 per mil. Dolostoneclastsfrom reactedwith 100 percent phosphoricacid usingthe
the interore brecciasin the H.Y.C. depositexhibit method of McCrea (1950) and the carbon dioxide
variableisotopicvalues.The interiorof the clastshave liberatedwasmeasuredmanometrically.Where acid-
isotopicratiossimilarto the unmineralizeddolomites solublesulfidesoccurredin the sample,hydrogensul-
whereasthe edgesof the clastshave isotopicratios fide wasremovedby holdingthe gasesover coarsely
intermediatebetweenthe unmineralizedsamplesand powderedsilverphosphate. The samplesof bitumen
the mineralizedsamples. were scrapedfrom the hostrock and combusteddi-
Rye and Williams (1981) proposetwo modelsto rectlyto carbondioxidein an oxygenatedatmosphere
explainthe linear isotopictrend of the mineralized at 1,100øC (Kaplan et al., 1970).
samples.The first model is basedon carbonatepre- The isotopicmeasurements were made on a Mi-
cipitationfrom, or equilibrationwith, a mineralizing cromass602 ratio massspectrometer.Carbonisotopic
solutionof constantbl$c and b180composition. This ratiosare reportedrelative to the Peedeebelemnite
modelsuggests a temperaturerangeof 825ø to 175øC (PDB) standard.The oxygenisotoperatioswere mea-
for the carbonate in the discordant mineralization. sured with respectto PDB and were convertedto
0/
I A SMITH(1980 ,4./ []
COXCO DEPOSIT
LYNOTT FORMATION
// ß THEORETICAL CURVE FOR CARBONATE
DEPOSITION FROM EQUILIBRIUM SYSTEM:I SILTSTONE
! SEAWATER$•80=0%ø; ATMOSPHERIC
•-•J 175øC
ß DOLOLUTITE IN KARST
/ co28'3C
=-7.0'/** J• • I CAVITY INFILL
(• DOLOLUTITE REWARD
DOLOMITE
+ PARTLY SILICIFIED
67'c 2o*c DOLOLUTITE
./ / • /I RYE S WILLIAMS
'o• / • / ( 198l ) • SPARRY DOLOMITE
0 PHOSPHATE FRAGMENT
m / / 275 c •WITH-99% H20• H2CO
3 APPARENT IN KARST BRECClA
/ .•_ •1 • IDOMINANT
CARBON
SPECIES,
•1127•C
• • 300•C L•mo
- 12-5%.
AND613C
ß-2.75%e
I I I
18 19 20 21 22 23 24 25
Sis0%o, 5MOW
12. A b]aOvs.b]SCdiagramfor carbonates

from the Coxcodeposit.
SMOW using the following relation (Friedman Host carbonates: The carbonates from the Reward
and O'Neil, 1977; Rye and Williams, 1981): Dolomite,Lynott Formation,and karst fills showa
/5•SO•s•aow•
= 1.08086/5•sO•pr•B• for spreadin/5•SO•sMow•
+ 80.86.Theresults valuesfrom 19.8to 24.7permil
/5•sCare reproducibleto _0.1 per mil and for /5•so and/5•sCvaluesfrom -$.0 to -0.1 per mil (Table 6,
to ___0.2
per mil. Fig. 12). Except for two samplesfrom the Lynott
Results and discussion
Formation,the valuesare within the range of un-
mineralizedregionalsamplesof Rye and Williams
Bitumens:The samplesof bitumen from stageII (1981) and of typical marine carbonatesof Protero-
mineralizationgave/5•sCvaluesof -81.7 and -82.5 zoicage (Veizerand Hoers,1976).Althoughresults
per mil whichcomparewith the rangeof/5•C values from individuallithologies appearto clusterandthere
of the organicmatter in the BarneyCreekFormation isa fairly widespreadin/5•so,no reasons for thiscan
of -27.5 to -$1.0 per mil (Smithand Croxford,1975). be advanced.
The valuesare within the rangeof the ratiosof pe- Dolomite gangue-stageII mineralization: Two
troleum and other biogeniccarbonaceous material samplesof sparry dolomite gangue from stage II
foundin sediments(Degens,1969) and thusare con- mineralization gave/5•SO•sMow•values of 18.2and20.4
sideredto be of biogenicorigin (Hoering,1967). per mil and/5•C valuesof -0.8 and -1.$ per mil.
TABLE6. 5•aCand 5•sOValuesof Carbonates
and Bitumensfrom the CoxcoDeposit
Carbonate
Drill Depth contentas •aC, %0 •SO, %0
hole (meters) Stratigraphicunit Sampledescription %C PDB SMOW
Coxco 7 62.5 Reward Dolomite Partially silicifieddololutitefrom 5.8 -0.4 22.8

unconformitysurface
Coxco 7 84.5 Reward Dolomite Dololutite 11.0 -0.8 22.0
Coxco 7 84.5 RewardDolomite Sparrydolomitegangueto 7.0 -0.8 20.9

mineralization
Coxco 8 $9.0 Reward Dolomite Black bitumen -gl.7
Coxco 16 84.0 Reward Dolomite Dololutite 8.$ -0.9 20.2
Coxco16 48.$ Lynott Formation Dolomiticsiltstone 0.6 -$.0 20.6

-2.5 20.7
Coxco18 81.0 Lynott Formation Dolomitic siltstone 0.g -1.0 25.$

Coxco18 100.9 Lynott Formation Dololutite 9.$ -0.5 24.4
Coxco18 101.6 Lynott Formation Dololutite 11.8 -0.6 24.2
Coxco18 115.5 Lynott Formation Fragmentcomposed of dolomite 4.7 -0.1 24.1
and collophanefrom a cave
infilling
Coxco 18 128.0 Reward Dolomite Sparrydolomitegangueto 9.8 -1.g 18.7
mineralization
Coxco 18 128.0 Reward Dolomite Black bitumen -82.5
Coxco 18 128.2 Reward Dolomite Dololutiteinfilling from a cave 9.5 -0.2 24.6
Coxco 18 154.6 Reward Dolomite Dololutiteinfilling from a cave 7.2 -0.2 25.2
Coxco 19 141.0 Lynott Formation Dolomitic siltstone 0.2 - 1.$ 24.1
Coxco 19 176.9 Reward Dolomite Partially silicifieddololutitefrom 5.9 -0.4 24.6

unconformitysurface
Coxco 19 197.4 Reward Dolomite Dololutite breccia with a 9.9 - 1.2 28.7
collophanedolomite matrix
One of theseanalysesfalls within the rangeof the Lead Isotopes

dololutites from the Reward Dolomite while the sec-
ondhasa lower•so/•60 ratio (Fig. 12). Thirteensamplesof sulfidesfrom the Coxcodeposit
This similarity in isotopic compositionof the were analyzedfor their lead isotopiccomposition.
gangueand hostdolomiteis to be expectedas long The samples were selectedas representativeof the
as the mineralizingfluidsdid not introducean over- varioussulfidetypeswithin the deposit.
whelmingabundance of carbonand oxygenof mark- Samplingand analyticaltechniques
edlydifferentisotopiccomposition. Texturalevidence
indicates that extensive dissolution of the host car- The sulfideswere excavatedfrom polishedslabs
bonatetookplacebeforeand during the influxof the usinga vibratingtungstenneedleexceptfor the alia-
mineralizingfluids.Thus the original isotopiccom- geneticpyrite from the Lynott Formationwhichwas
positionof the mineralizingfluidsmightbe expected separatedby heavy liquidsand magneticmethods.
to be modifiedby the dissolvedcarbonate.Dolomite The sulfideswere dissolvedby techniquesdescribed
subsequentlyprecipitatedfrom these fluids would elsewhere(Gulson,1979)andleadseparatedby anion
havean isotopiccomposition approaching that of the exchangechromatography followedby anodicelec-
host dolomite. trodeposition.
Most sampleswere analyzedfor lead
The isotopiccomposition of stageII ganguedolo- and uranium concentrationsby isotopic dilution.
mite is dissimilarto ore-stagedolomitein the Cooley Lead isotopicratioswere measuredusingsilicagel-
and Ridge deposits,and suggests that the deposits phosphoricacid on an AVCO series900A, $5-cm-ra-
were formed by mineralizingfluidsof different iso- diussingle-sector massspectrometerundercomputer
topic compositionor that the fluid compositionwas controlfor peak searchand alignment,ion beam
controlledby differenteffectivewater/rock ratios. switching,electrometer rangeselection, and data ac-
T^mE 7. Lead IsotopicData for Samplesfrom the CoxcoDeposit
Drill Depth U Pb
hole (meters) Mineral •Pb/2ø7pb 2ø7pb/aø•Pbaø•Pb/aø4pbaø7pb/aø4pb
aø•Pb/aø4pbaø4pb/2ø•Pb(ppm) (ppm)
A. Diageneticiron sulfidesin karstfillingsin the RewardDolomite

8 105.6 py-mc 2.207• 0.9498 16.279 15.454 85.929 0.06148 0.17 565
B. Diageneticiron sulfidesin the Lynott Formation

19 160.9 py-mc 2.1618 0.9180 16.948 15.554 36.619 0.05902 0.65 0.27
19 168.0 py-mc 2.1729 0.9249 16.690 15.437 36.266 0.05992 0.81 835
C. StageI mineralization
8 27.7 mc 2.1958 0.9488 16.368 15.440 86.026 0.06110 8.0 745
8 54.4 mc 2.2155 0.9550 16.149 15.426 85.748 0.06192 0.06 655
8 54.4 carb. res. 2.2172 0.9569 16.121 15.426 85.748 0.06203 0.58
18 161.0 gn 2.2210 0.9568 16.175 15.474 85.920 0.06188 3.6 •74%
19 214.2 gn 2.2195 0.9564 16.181 15.476 35.914 0.06180 0.92 •20%
2.2189 0.9560 16.172 15.460 85.884 0.06184
19 214.3 gn 2.2132 0.9519 16.292 15.508 36.057 0.06150 2.28 •38%
D. StageIlmineralization
7 84.5 py-mc 2.2120 0.9545 16.186 15.450 85.808 0.06178 0.44 1,520
2.2115 0.9587 16.174 15.425 85.769 0.06188
10 128.9 gn 2.2015 0.9481 16.361 15.469 $5.920 0.06129 0.095 •79%
2.2028 0.9466 16.876 15.502 86.078 0.06106
14 78.2 sph 2.2187 0.9571 16.!88 15.441 85.794 0.06198 0.04 •28%
18 115.$ gn 2.2221 0.9574 16.160 15.472 85.909 0.06188 0.19
2.2209 0.9571 16.154 15.460 85.876 0.06190
2.2176 0.9568 16.182 15.484 85.772 0.06199
18 128.2 py-mc 2.2168 0.9567 16.188 15.489 85.774 0.06197 0.87 785
E. AverageH.Y.C. ore (12 samples,Isomass

54E)
2.2183 ñ 15 0.9570 ñ 4 16.150 ñ 9 15.456 85.826 0.06192
Abbreviations:
gn, galena;carb.res.,carbonaceous
matterresidue;
mc, marcasite;
py, pyrite;sph,sphalerite
quisition.Errorsfor the 2ø7pb/2øaPb and 2øSpb/aø•Pb 37.0

ratiosare +0.05 percentand for the aø•Pb/aø4pb
+0.1
percent. Replicate analyses,that is, separatedissolu-
tions,given in Table 7, are consistent with this esti-
mate. The data have been normalized to NB5 SRM
36'5
981 usinga correctionof +0.07 percentp.m.u.
Previous
work g
Richards(1975) analyzedtwo surfacesamplesfrom o•
Coxco (samplesCox'sand Cook'sin his table 1) and 36'0
concludedthat the lead isotopicratios were radio-
genicwith respectto lead from the stratiformH.Y.C.
deposit.A studyof lead isotopicratiosin the H.Y.C. ß COXCO-Stoge II Sulfides
deposit(Gulson,1975) showedthat the galenaand ß HYC Mossive Ore
sphaleritehave uniform lead isotopicratios (•ø•Pb/ 3s.s i i I I I
2ø4pb,
16.07-16.15;•ø7pb/•ø4pb,
15.137-15.47;
•øSpb/ lS.60
aø4pb,
135.137-135.89)
whereasthe pyrite hasvariable
and quite radiogenicisotopicratios.Gulson(1975)
proposedthat the tracelead in the pyrite wasderived
from at leasttwo sources, one being an exhalative lS.Ss
sourceand havingidenticalratiosto the galenaand
sphalerite,
andthesecond beingradiogenicandde- g
rivedfrom leachingof the countryrocks.A more • is.s0
systematicexaminationof the lead isotopevariations o•
throughthe H.Y.C. orebodieshasrecentlybeencom-
pleted usingthe fully automatedIsomass54E mass
_ xß C••50
Mo
spectrometer (Gulson,unpub.data).The higherpre- lS.•s
cision data obtained on this instrument demonstrate
that the lead isotopicratiosin the H.Y.C. depositare
homogeneous
theaverages
to better than +0.1 percent(1 a) with
andstandard
deviations
(1a)for12dif-
ferent samples as follows: 2øspb/zø½Pb, 2.21813
lS.•0
16.0
155o
Mo
i i t i
16'2 16% 16'6 16'8 17-0
+ 0.0015; aø7pb/aø•Pb,
0.9570+ 0.0004; aø•Pb/aø4pb, 206/20•
16.150 + 0.009.
FIG.18A. ZøsPb?ø4pb vs.a(•Pb/Zø4pb diagramfor sulfidesfrom
the Coxcodeposit.The growthcurveof Cummingand Richards
Results (1975) is indicated.The error barsgiven in the upper left hand
cornersof the figureare at the 2 a level.B. •øVPb/•ø4Pb
vs.aø•Pb/
The leadisotopic
results
uncorrected
for radiogenic aø4Pbdiagramfor the sulfides fromthe Coxcodeposit.
lead addition for uranium are listed in Table 7 and
plottedin Figure 113.
Uranium concentrationsand organic material: lead consideringthe affinityof uraniumand carbo-
The amountsof uraniumin mostof the samplesare naceousmatter. However,as part of an ongoingre-
high and are at leastpartly due to the presence
of searchprogram,we have routinelyanalyzedthe or-
collophane associated
with stageI sulfides.
However, ganic residuesfor uranium and lead concentrations
asthe majorityof samples are galenaor containga- and lead isotopicratiosand, in all casesto date, the
lenainclusions asshownby their highlead concen- isotopicratiosin the organicsand host sulfidesare
trations,radiogenic leadderivedfromuraniumdecay similar.The isotopicdata for the carbonaceous matter
is an insignificantcomponentof the lead exceptfor from sample8/54.4 m givenin Table 7 illustratethis
the diagenetic ironsulfides andmarcasite (sample8/ point.
27.7 m) from stageI mineralization.We have found StageI sulfides:The isotopicratiosin two samples
that corrections for radiogenicleadaddedfrom ura- of galenafrom the stageI mineralizationare similar
nium decayare fraughtwith inconsistencies because to thosein the H.Y.C. deposit,but the third (sample
of possible recentmigrationof uraniumand/orlead, 19/214.13m), only 10 cm awayfrom oneof the other
a problemalsoalludedto by Staceyet al. (1980).We samples, hasradiogenicisotopicratios.All threega-
havefound--particularlyin shale-hosted deposits-- lenasamples haverelativelyhighamounts of uranium
that after dissolutionof the sulfides,
an organicresi- rangingfrom 0.9 to 13.6ppm, but this could not ac-
dueispresent. Thisisa possible sourceof radiogenic countfor the radiogeniclead in sample19/214.13m.
Two samplesof colloformpyrite-marcasitefrom the Comparisonwith othercarbonate-hosted deposits:

stageI mineralizationwere analyzed.Thesesamples Coxco, located in a mid-Proterozoic carbonate se-
were selectedfor the absenceof associatedgalena quence,is the oldestMississippi Valley-typedeposit
althougheachcontainedseveralhundredppm lead. known to us as all othersare hostedby Phanerozoic
One of the samples(8/27.7 m) washighlyradiogenic rocks.The main lead isotopicsignatureof Coxco
whereasthe other(8/54.4 m) wasnonradiogenic and mineralizationis a nonradiogenic valuesimilarto the
wassimilarto the isotopicratiosin the H.Y.C. deposit. H.Y.C. depositwith a minor radiogeniccomponent.
The radiogenicsamplecontainedthe highesturanium With its smallradiogeniccomponent,Coxcoresem-
contentof all the samplesanalyzedat 8 ppm, and at blesthe Mississippi Valley-typedeposits in the United
leastpart of the radiogeniclead componentof this States;on the otherhand, the extremevariabilityin
sampleis derived from uranium decay. Pb isotopes,so long considereda characteristicof
StageH sulfides:Two samples of pyrite-marcasite Mississippi Valley deposits,appearsrestrictedto the
from the stageII mineralizationwere analyzed.Both type locality.All other depositsin Australia(Vaasjoki
have high concentrations of lead at 785 and 1,520 and Gulson,1981),Silesia(Zartmanet al., 1979),Pine
ppm and similar amountsof uranium at approxi- Point (Cumming and Robertson,1969; Gulson,un-
mately 0.4 ppm. The samplewith the highesttrace pub. data),and the Irish deposits(Greiget al., 1971)
lead (7/84.5 m) hasslightlyradiogenicisotopicratios have homogeneous isotoperatios.
whereasthe other samplehasratioswhich are iden- The major nonradiogenic isotopecomponentin
tical with the majorityof galenasfrom the deposit Coxcoand the other depositsabovemay be partly a
and alsothe averagevaluefor H.Y.C. lead.One sam- functionof the age of the mineralizationrelativeto
ple of sphaleritewasanalyzedwhichcontainedhigh the country rocksand, thus, to the sourcematerial
lead and its isotopicratioswere similar to the H.Y.C. (Vaasjoki and Gulson, 1981). In the southeastern
lead. The two samplesof galenaanalyzedfrom the United Statesthe metalsare probablyderivedorig-
stageII mineralizationhavedifferentisotopicratios. inally from Precambrianbasementand thusthere are
One galenahas nonradiogenic ratiossimilarto the hundredsof millionsof yearsseparatingthe age of
averageH.Y.C. leadwhereasthe otheris radiogenic. sourcerocksand the deposits.This time spanpermits
the build-upof significantradiogenicPb from U and
Discussion
Th and probablyaccountsfor the radiogenicnature
Sourceof metals:The high amountsof common of thesedeposits.In contrast,in Ireland, France, Po-
lead in somesphalerites and iron sulfidesas well as land, avd the NorthernTerritory,the agedifference
galenaindicatethatthe variationin leadisotopes ob- betweenthe suggested sourcerocksand the deposits
servedin thesesamplesis primary and not due to is fairly small and there was little time for build-up
radiogenicadditionfrom uranium.However,in some of radiogenicPb and so the depositsare relatively
of the iron sulfideswith only tracelead, a smallcom- nonradiogenic.
ponentof the radiogeniclead is due to uranium
A Metallogenic Model
decay.
The spreadin isotopicratiosfor the highleadsam- The Coxcodeposithasmany of the characteristics
plesfrom both stageI and stageII mineralization of MississippiValley-type deposits(Table 8). Al-
suggests that the leadwasderivedfrom at leasttwo thoughdeposits of thistype havemanycharacteristics
andpossibly moresources. Many of the samples have in common,in detailthey are foundto exhibita wide
ratiossimilar to thoseof the averageH.Y.C. lead rangeof sulfide-host rocktextures,leadisotoperatios,
whichsuggests that a majorsourceof the leadin the sulfurisotoperatios,and trace elementcompositions.
mineralizationstagesat Coxcowasthe sameasthat These differences reflect variable metal sources,sul-
supplying the H.Y.C. The sourceof the metalsin the fur sources,sulfide precipitation mechanisms,and
H.Y.C. depositisconsidered to be deepbasinalbrines timing of the mineralizationwith respectto the age
with solutions beingintroducedalongthe Emu and of the hostrocks.A metallogenicmodelfor suchde-
Westernfaults(Walker et al., 1977b;Williams, 1978). positsmustthereforeaddress itselfto delimitingthese
A lead sourcewith a more radiogeniccomponent variables.
is alsoindicatedalthoughinsufficientsamplingwas
undertakento suggestthe composition of the lead StageI mineralization
from sucha source.Richards(1975) analyzed vein It hasalreadybeenshownthat stageI mineraliza-
galena,fromthe RewardandEmmeruggaDolomites, tion was depositedin open cavitiesin the phreatic
whichalsocontainedradiogenicisotoperatiossimilar zoneof an active karstcavernsystemdevelopedbe-
to thosefoundin Coxco.It may be that the radiogenic low the Reward-Lynottunconformity.Depositionof
leadin Coxcowasderivedby brineleachingpossibly the mineralizationas crustson the surfaceof frag-
from within the McArthur Group itself. mentsand cavitiesalternatedwith the depositionof
TABI,E8. Similaritiesof the Coxco Deposit to Mississippi (seeBernard,1972). Alternatively,it couldbe intro-
Valley-Type Deposits
ducedby pulsesof brinesderived from a different
1. The depositis hostedby a shallow-waterdolomitesequence. deep aquifer with a high uranium content.
2. The hostsequenceis generallyshallowlydippingand Severalpossiblemechanisms of sulfidedeposition
unmetamorphosed; igneousintrusionsare absent. in MississippiValley-type depositshave been pro-
$. The depositis locatedon a basinmargin in an intracratonic
area. posed(seeSummaryin Anderson,1978) and can be
4. The predominantore mineralsare sphaleriteand galenaand evaluatedfor the depositionof stageI sulfides.The
are accompaniedby variableamountsof iron sulfides. mechanisms canbe subdividedinto precipitationdue
5. The sulfidesvary from colloformcruststo coarsely to rapid changein the physicochemical natureof the
crystallineand were depositedpredominantlyin open
cavities. mineralizingsolutionsat the site of sulfideprecipi-
6. The sphaleriteis a light-coloredvariety indicatinga low iron tation, and precipitationdue to the mixing of intro-
content. duced metal-rich solutions with sulfide-rich solutions
7. The ore containsa very low level of preciousmetals. at the siteof deposition.The depositionof the sulfides
8. The gangueis predominantlyspatrydolomite. in an activekarstcavernsystemindicatesdeposition
9. Bitumen is a minor but common associate of the
mineralization. at atmosphericpressureand possiblytemperaturesof
10. The mineralization is strata-bound. depositionbelow 100øC,althoughintermittentinjec-
11. Inclusionsin the ore mineralscontainvery high salinity tion of fluidsat temperaturesabove100øCcannotbe
fluids. discounted.
1•.. The temperatureof depositionvariesfrom 100ø to •.00øC.
The sphaleritein the stageI mineralizationis in-
timately associated with organicmatter. The sphal-
chemical and detrital sediments in the cavities and erite lensesin the caverninfills are alwaysassociated
the brecciationof previouslydepositedmineraliza- with the laminae richestin organicmatter, and or-
tion. ganic matter occurswithin the colloformsphalerite.
The following characteristics
of stage I sulfides This intimate relationshipsuggests that the organic
mustbe explainedby or be consistent
with any pro- matterwasinvolvedin the sulfideprecipitationmech-
posedmodel for the metal source: anism. As the temperatureof depositionof the sul-
fideswasprobablylessthan 100øCand at suchtem-
1. StageI sulfidesare limited to a smallarea of the peraturesbiologicalreductionof sulfateis the only
deposit. knowneffectiveprocess of sulfatereduction(Ohmoto
2. The col|oform texturesof thesulfides
wouldsug- and Rye, 1979), the involvementwas probablybio-
gesttheir rapid deposition(Bartonet al., 1977). logicalrather than abiological.
13.The replacementof the collophane-rich dolo- Although many micro-organisms are capable of
lutite by sphaleriteindicatesdisequilibriumbetween reducingsulfateto sulfide,major productionof hy-
the mineralizingsolutionsand the chemicalsediments drogensulfideis only carriedout by a groupof spe-
in the karst cavities.
cializedanaerobicbacteriabelongingto the genera
4. Deposition of mineralization alternated with
detrital sediments in the karst caverns.
Desulfovibrioand Desulfotomaculum(Trudinger,
1976).The bacteriaappearableto survivein extreme
5. The lead isotopicratiossuggestthat the major environmentsand it has been suggested(Berner,
sourceof the lead in stageI galenawasthe sameas 1970;Trudinger,1976)that the majorcontrolon the
that for the H.Y.C. deposit,alongwith a minor,more extentof bacterialsulfatereductionmay be the avail-
radiogenicsource. ability of organicmatter.
These characteristics of the mineralization are not It hasalreadybeensuggested that the fine-grained
consistentwith the majorityof the basemetalsbeing euhedralpyrite in the sediments filling the karstcav-
a naturalcomponentof the karsticgroundwater. It ernswasdeposited duringdiagenesis by bacterialsul-
is suggested that the mineralizingsolutionswere in- fate reduction.The physicochemical factorswithin
troducedin pulsesinto a restrictedarea of the karst a karstdrainagesystem(Bernard,1972)are certainly
systemandthatthe sulfides wererapidlyprecipitated. within the environmental limits of the sulfate-reduc-
A mechanismsuchasseismicpumping(Sibsonet al., ing bacteria (Zobell, 1958). Thus the associationof
1975)couldaccountfor the mineralizingpulses,with stageI sulfideswith organicmatter,the largequan-
the conduitbeing the Emu fault zone.Basedon the tities of organicmatter in the cavern sediments,the
leadandsulfurisotopicratios,the majorsourceof the low temperatureof sulfidedeposition,
and the phys-
basemetalsis seenasdeepbasinalbrinesof the type icochemicalconditionsof the karstsystemare all con-
suggested asthe sourceof the H.Y.C. stratiformmin- sistentwith, and would suggestthat, the sulfidespre-
eralization.The minor, more i'adiogeniclead source cipitatedfrom reducedsulfurproducedby bacterial
couldrepresenta basemetalcomponentin the karstic sulfatereduction.A plentiful supplyof sulfatein the
groundwaterderivedby weatheringof the hostrocks groundwaterscanbe assumed consideringthe evapo-
ritic nature of the McArthur Group (Walker et al., An important considerationis why the solutions
1977a). The sulfur isotoperatiosof stageI sulfides causeddissolutionwhere they did and not during
(6.5-21.7%0)and the diageneticiron sulfidesin the their passagethroughthe underlyingcarbonates. The
karstsediments(10.7-20%0)havesimilarrangesand localizationof brecciationwould suggestthat the so-
are consistentwith a bacteriologicalorigin for the lutionswere unreactiveto the underlyingdolomites
reduced sulfur. The colloform nature of the sulfides and a drop in pH occurredat the site of major dis-
isalsoconsistentwith their rapid precipitationduring solutionto form the breccias.The abiologicalreduc-
the mixing of metal-richsolutionswith reducedsul- tion of sulfateat the siteof metal deposition(Barton,
fur-bearingkarsticgroundwaters. 1967;Dunsmoreand Shearman,1977) wouldexplain
Probablythe closest modernanalogueto the mech- the followingcharacteristics of the brecciasand min-
anismproposed, althoughnot a naturalphenomenon, eralization:
occursin the Cheleken Peninsula(Lebedev, 1975).
1. Acid is producedin the reactionand could ac-
In thisarea,brinesare pumpedfrom depthsbetween count for the dissolution of the dolomite and the ul-
1300and 1,450 m as a source of iodine and bromine.
timate formation of the breccias.
Someof the brinescontain up to 77 mg/1 lead and
5.4 mg/1 zinc whereasotherscontain appreciable 2. The solidbitumenscouldrepresentthe remains
quantitiesof hydrocarbonsand hydrogen sulfide. of petroleumin whichthe lightermolecularweight
Where thesetwo typesof brinesare mixedin surface hydrocarbons
moved.
being more reactive have been re-
installations,
densecrustsof colloformsphaleritecon-
tainingdisseminated 13.The basemetalsmay be precipitatedby the re-
galenaand pyrite are forming. duced sulfur formed in the reaction.
Lebedev (1967, p. 199) concludesthat: "Sphalerite
is thus formed when metalliferous thermal solutions Such a mechanism is not inconsistent with the sul-
mix with hydrogensulfide-bearing
waters,and it is fur isotoperesults.
similarin its textureand trace elementsto the sphal-
erite of telethermaldeposits." Relationshipbetweenthe Coxcomineralization
An alternative mechanism could involve the mix- and the Cooley-Ridge-H.Y.C.
mineralization
ing of a salinemetal- and sulfur-richsolution(Sver- It is now generallyacceptedthat the H.Y.C. strat~
jensky,1981) with relativelylow-temperaturekarstic iform mineralization was depositedsyngenetically
groundwater. Suchmixing would result in an in- (Croxford and Jephcott,1972) or within severaltens
creasein the pH and a decreasein the salinity and of meters of the sediment-waterinterface (Williams,
temperature of mineralizing solutions.All these 1979). Thus within the H.Y.C. basinthere are at least
changesmight be expectedto result in the precipi- two distinctperiodsof basemetal mineralization,the
tation of the metals as sulfides. This mechanism would last of which may also have formed the coarse-
not, however,explainthe spatialrelationshipof the grainedCooley-Ridge mineralization(Williams,1978).
sulfideswith organicmatter. These two periodsof mineralizationwere synchro-
nouswith depositionof the Barney Creek Formation
StageH mineralization and thereforeprecededthe depositionof the stage
Depositionof stageII sulfidesoccurredafter lith- I mineralizing period at Coxco.Thus there are now
ificationof the basalLynott Formationand the cave at leastfour mineralizingperiodswhich can be rec-
infillingsin the underlying Reward Dolomite. The ognizedin the Emu fault zonein the McArthur River
mineralized breccias are considered to have formed districtand they suggestthe periodictappingby the
by brittle deformationfollowed by solutionalong Emu fault zone of a deep circulatingbrine system.
cracksto givea rangeof texturesrangingfrom crackle The Cooleyand Ridgemineralizationhasbeenlik-
brecciasto openbreccias. ened to the MississippiValley type by Williams
The closespatialrelationshipbetweenthe breccias (1978), althoughit differsfrom mostdepositsof this
and the mineralization,especiallythe alternationof type in containinghigh copperand silverand being
mineralization and brecciation, would indicate that formed at higher temperatures.The Coxcodeposit
the solutionsdissolvingthe dolomitewere the min- is similar to the other end of the spectrumof Missis-
eralizingbrinesor a precursorphaseof thesebrines. sippi Valley-type deposits,i.e., relatively low tem-
Presumablythe temperatureof thesesolutionswas perature,karst-related,and rapidly dumped sulfide.
on the sameorder as the depositionaltemperatureof Thuswithin the oldestknownMississippi Valley-type
stageII mineralization,that is, 100ø to 170øC. The districtthere is a wide range of type characteristics.
solutionswere therefore not normal ground waters
Conclusions
and had obviouslyevolvedat greaterdepths.This is
consistentwith the lead isotoperesultswhich suggest The characteristicsof the host sequenceand the
a deepbasinalsourcefor the brinesand the majority mineralizing events and the relationshipbetween
of the contained base metals. them are summarizedbelowand in Figure 5.
COXCODEPOSIT,McARTHURRIVERDISTRICT 247
1. Followingdeposition of the Myrtle ShaleMem- 9. At somelater period subsequent to the lithifi-

ber, a majortransgression occurredwith deposition cationof the basalLynott Formationand the sedi-
of the intertidal stromatolitic dololutites of the Mara mentsin the karst infilling, the Reward Dolomite
Dolomite Member. underwentbrittle fracture.The fracturingwascon-
2. After depositionof the Mara DolomiteMember fined to the upper sectionof the Reward Dolomite,
and precedingdepositionof the RewardDolomite, possiblyreflectingthe build-upof fluid pressurebe-
major uplift occurred in the Emu fault zone with low the impermeablesilicifiedzoneat the top of the
exposureof the sequenceto subaerialweathering. RewardDolomite.The mechanism of fracturingwas
This uplift may have beensynchronous with major possiblyhydraulicfracture,and the solutions respon-
uplift in the Emu fault zone adjacentto the H.Y.C. sible may have been the mineralizing brines.
basinduring depositionof the Barney Creek For- 10. Initial fracturing was followed by solution
mation. alongthe fracturesand the depositionof sphalerite,
8. Solutionoccurredalong vertical jointsin the pyrite,marcasite,andgalenain theopenspaces. Brec-
Mara DolomiteMemberin the vadosezoneof a deep ciationalternatedwith depositionof mineralization.
karstsystem.Thesesolutioncavitiesare now largely 11. The mineralizingsolutionswere very saline
filled in with finely laminated speleothems. The fluids containingsaltsother than NaC1, probably
deeper sectionsof the karst systemhave not been mainlyCaC12,andat temperatures between100ø and
identified. In the Coxcoarea, approximately100 m 170øC.
of the Mara DolomiteMember are preserved. 12. Reducedsulfurwasprobablyproducedat the
4. Followinga major transgression, the stromato- siteof sulfidedepositionby the abiologicalreduction
litic dololutitesof the Reward Dolomite were depos- of sulfateby hydrocarbons. The bitumenspresent
ited i.nan evaporiticshallow-waterenvironment.Sul- in the mineralizedveinsprobablyreflect the heavy
fate evaporitemineralswhichwere depositedwithin hydrocarbons remainingafter thisreaction.The re-
the carbonatesedimentswere replacedby dolomite action also resultsin a decreasein the pH, which
presumablyduring early diagenesis. couldexplainthe widespreadsolutionof dolomite.
5. A secondperiodof major uplift occurredwith Acknowledgments
exposureof the Reward Dolomite in a semiarid
weatheringenvironment.The exposedsurfacewas The majority of this studywas undertakenas an
silicifiedand a karstcavernsystemwasdeveloped. M.Sc.projectat the JamesCookUniversityof North
Speleothems weredeposited in the vadosezoneof the Queensland by R. N. Walker;he wouldlike to thank
cavernsystem.Within the phreaticzoneand espe- his supervisors W. C. Lacy and R. Taylor. R. N.
cially in quiet anoxicenvironments fine dololutites Walker alsowishesto thank the managementof Car-
were depositedwhich were partiallyreplacedby or- pentariaExplorationCompanyPty. Ltd., in partic-
ganicallyconcentrated phosphate. Fine to coarsedo- ular E. M. Bennett,W. J. Murray, and W. D. Smith,
lomitic sedimentswere depositedin higher energy for permissionto undertakethe studyand to publish
subsurface environments. theresults.
Mostof thelaboratorystudies werecarried
6. Metalliferousbrines were introducedperiodi- out at the CSIRO Divisionof Mineralogyand the
cally into the phreaticzoneof the karstsystempos- Divisionof FossilFuelsat North Ryde, Sydney.We
sibly througha branch of the Emu fault zone. The wish to thank R. Wilkins, fluid inclusionstudy;J.
brinesmixed with reducedsulfur-bearingground Saxby,hydrocarbonstudy;K. J. Mizon, Pb separa-
waters,andcolloformcrustsof sphalerite, pyrite,and tions;and L. Brunckhorst,probe work, for their as-
marcasitecontainingminorgalenaweredepositedon sistance. The followingpeoplehavealsocontributed
theedgesof cavitiesandfragments. The reducedsul- to the studyand their valuableassistance is acknowl-
fur was probablysuppliedby sulfate-reducing bac- edged:G. Wood, P. Cheyne,G. Lowcock,W. Van
teria. Oosterom, J. Shewan,L. Leben,S. Fleming,and M.
7. Coarse dolomitic sediments alternated with de- Meikle. N. Williams, D. Paterson,and R. Logan
positionof mineralizationduring the infilling of the kindlyreviewedthe manuscript andsuggested valu-
karst-produced caverns.The coarsedolomiticsedi- able improvements.
ments contain a high proportion of fragmentsof
mineralizationwhichresultedfrom the physicaldis- June 9, October28, 1982
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2the Coxco Deposit A Proterozoic Mississippi Valley-Type Deposit in The McArthur River District, Northern Territory, Australia

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2the Coxco Deposit A Proterozoic Mississippi Valley-Type Deposit in The McArthur River District, Northern Territory, Australia

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EconomicGeology

Vol. 78, 1983,pp 214-249

The CoxcoDeposit A ProterozoicMississippiValley-Type Depositin the

The Coxcodepositis a Proterozoicstrata-bounddolomite-hosted lead-zincdepositwhich

ratiosof the sulfides,the presence

Introduction siblyAdelaidean(late Proterozoic)ageand is divided

morphosedand the originalfine-grainednature of

graniticcomplexeswhichare late early Proterozoic

FIe;. 2. Geologicmap of the McArthurRiver districtshowingdistributionof the major deposits

BARNEY HY.C p __p •__p __• o "CAULIflOWER"

feldspathicsandstone, the BukalaraSandstone, which Formationis only representedby dolomiticbreccias

Barney Hill gn EmmeruggaDolomite Geology of the Coxco Deposit

IO0 200 300

FIG. 4. Geologyof the Coxcodeposit.

(1976)and Kendalland Broughton(1978).

The RewardDolomitecomprises light gray dolo- sociatedgypsumpseudomorphs wouldsuggest a shal-

FIG. 6. Host sequenceto the mineralizationin the Coxcodeposit.

domorphs.The goethitecommonly occursasaggre- quartzcomponentconsisting. of bothvoid-fillingand

quartz crosscut the fracturesand it is suggested that Shape:The breccialensesare extremelyvariable

The pseudomorphs to be in diameter. In some breccias, the rims are thinner

Fie. 7. Hostsequenceto the mineralizationin the Coxcodeposit.

consistsof quartz dololutite,dolarenite,and doloru- from the hostrock by a dolomite-collophanerim. The

TABLE2. Comparisonof StageI and StageII Mineralization

StageI mineralization StageII mineralization

Sphalerite Straw yellow to red-brown colloformand Off-white to light red, coarselycrystalline

Pyrite-marcasite Colloform crustsand coarselycrystalline Comb textureand coarselycrystalline

within the sphalerite.The quartz grainsare com- is a massiveto finely laminateddolomiticsiltstone

FIe;.8. Photomicrographs showingtexturalrelationships betweenstageI sulfidesand the karstinfillings

occurdisseminatedthroughthe matrix. Thesegrains able but with smallirregularembaymentsoccupied

Fie. 9 Photomicrographs showingsulfidetexturesin stageI mineralization.

Althoughthe absolutetime of mineralizationcan- the hostrock in a matrix of stageII mineralization.

FIG. 10. Photomicrographs of sulfide-host-rocktexturesof stageII mineralization.

maximumdiameterof 2 mm and containirregular ever,the textureis morecomplicated.For instance,

hasactedasa caprockto the mineralizationsolutions. igin.However,somegroupsshowevidenceof necking

TABLE13. FreezingPointDeterminations on Fluid Inclusions

T^Bt•: 4. HomogenizationTemperaturesof Fluid Inclusionsin Dolomite and Sphalerite

Drill Depth Temperature

Coxco 18 128.2 Sphalerite 169 Possiblya primary inclusion

galenawereintroducedassuchwith the mineralizing containeda mixtureof pyrite and marcasite.The sul-

TABLE5. SulfurIsotopeData for Sulfidesfrom the CoxcoDeposit

Drill Depth Pyrite/marcasite Sphalerite Galena

Disseminated iron sulfide in Reward Dolomite

Coxco 9 112.7 -0.6

sulfidesand its depositionwas separatedin time by exchangebetweenthe hostcarbonateand the min-

12. A b]aOvs.b]SCdiagramfor carbonates

Coxco 7 62.5 Reward Dolomite Partially silicifieddololutitefrom 5.8 -0.4 22.8

Coxco 7 84.5 RewardDolomite Sparrydolomitegangueto 7.0 -0.8 20.9

Coxco 14 75.7 Reward Dolomite Dololutite 10.1 -1.1 21.6

Coxco 15 45.4 Reward Dolomite Dololutite 11.5 -1.0 21.6

Coxco 16 84.0 Reward Dolomite Dololutite 8.$ -0.9 20.2

Coxco16 48.$ Lynott Formation Dolomiticsiltstone 0.6 -$.0 20.6

Coxco18 81.0 Lynott Formation Dolomitic siltstone 0.g -1.0 25.$

Coxco 18 128.0 Reward Dolomite Black bitumen -82.5

Coxco 19 176.9 Reward Dolomite Partially silicifieddololutitefrom 5.9 -0.4 24.6

One of theseanalysesfalls within the rangeof the Lead Isotopes

T^mE 7. Lead IsotopicData for Samplesfrom the CoxcoDeposit

A. Diageneticiron sulfidesin karstfillingsin the RewardDolomite

B. Diageneticiron sulfidesin the Lynott Formation

E. AverageH.Y.C. ore (12 samples,Isomass

quisition.Errorsfor the 2ø7pb/2øaPb and 2øSpb/aø•Pb 37.0

Two samplesof colloformpyrite-marcasitefrom the Comparisonwith othercarbonate-hosted deposits:

1. Followingdeposition of the Myrtle ShaleMem- 9. At somelater period subsequent to the lithifi-

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BARNEY HY.C p p •p __• o "CAULIflOWER"