2the Origin of A Mississippi Valley-Type Deposit in The Viburnum Trend, Southeast Missouri

EconomicGeology
Vol. 76, 1981, pp. 1848-1872
The Origin of a MississippiValley-Type Deposit in the Viburnum Trend,

Southeast Missouri
DIMITRI
A.SVERJENSKY*
Departmentof Geologyand Geophysics,
Yale University,New Haven, CT 06520
Abstract
Petrologicand isotopicstudiesof the basemetal sulfidemineralizationin the Buickmine
haveestablished the followingparagenesis: an early stageof fine-grainedpyriteand marcasite
replacedthe dolostone hostrock;the iron disulfides and dolostone werereplacedby sphalerite
duringthe mainstageof sphaleriteprecipitation (•4SSP 16.5to 19.0%0).Followingthe sphal-
erite, two main stagesof galenawere precipitated--acuboctahedral stage($•4Sgn 21.8 to
10.0%0),during which galena replaceddolostoneand sphaleriteand grew in vugs in the
dolostone and in the sphalerite,and a cubicstage($•4Sgn 10.5 to 0.9%0).The two stagesof
galenaprecipitationwere separatedby a period during which the main stageof sphalerite
and the cuboctahedral galenawere partially dissolved and bladedmarcasite($a4smc 2.8 to
4.1%0)wasprecipitated,and followedby a periodof mild etchingof the cubicgalena.Minor
amountsof pale sphalerite($s4SSV 14.0 to 16.5%0)were then precipitated.White and colorless
rhombsof dolomitewere precipitatedat the sametime assomeof the main stageof sphalerite,
the cubicgalena,and the pale sphalerite.After the pale sphaleritewasprecipitated,chalco-
pyrite, quartz, and siegenitewere precipitated,followedby calciteand finally kaolinite.The
paragenetic andtexturaldatafor bothgalenaandsphaleritein the Buickminestronglysuggest
that thesemineralswere precipitatedand dissolvedrepetitivelyduringore formation.Similar
texturalevidencefor galenareportedby other workersfor different minesin the Viburnum
Trendimpliesthat repetitiveprecipitationanddissolution of galenawasprobablyan important
process during the formationof the entire Viburnum Trend.
Fluid inclusionsin late quartz crystalscoprecipitatedwith chalcopyritehave filling and
freezingtemperatureswithin the rangesreportedfor sphaleritefrom other partsof the Vi-
burnumTrend, demonstrating that the ore-formingsolutionsin the ViburnumTrend were
probablyat temperatures in the range105ø to 141øC(assuming a maximumpressure correction
of about 11øC) and were extremelysaline,containingabout4.0 to 5.0 molal chloride.Con-
siderationof typical chemicalanalyses of fluid inclusions from other MississippiValley-type
deposits suggests that the maximumlikely concentration of dissolvedCO2in the ore-forming
solutions wasabout0.05 molal.At theseconcentrations, the ore-formingsolutionsthat travelled
to the siteof depositioncouldhave had pH's abouttwo unitslessthan neutraland still have
been in equilibrium with dolomiteor calcite.
The rangesof sulfurand leadisotopiccompositions of galenafrom the Buickmine are very
similar to thoseestablishedby earlier studiesof the Old Lead Belt and adjacentsubdistricts.
However,the correlationof isotopicallylighter sulfur with more radiogeniclead is much
strongerfor the ViburnumTrend,suggesting thatgalenawasprecipitatedfrom manysolutions,
each of which carried lead and sulfur togetherand had different lead and overall sulfur
isotopiccompositions.
The textural,paragenetic,and isotopicdata for the Buick mine cannotbe easilyexplained
eitherby a sulfatereductionmodelin whichsulfatewasreducedby organicmatteror methane,
or mixingmodelsin whichbasemetalsand reducedsulfurwere transportedseparatelyto the
siteof deposition.Instead,the datastronglysupporta reducedsulfurmodelfor ore formation
accordingto which the basemetalswere transportedtogetherwith reducedsulfur(as H2S),
in the samesolutions, to the sitesof deposition.The reducedsulfurmodelis alsosupperted
by a theoreticalcalculationof the solubilities
of galenaand sphalerite,whichdemonstrate that
low, but economically significant,concentrations of lead oi' zinc couldhavebeentransported
aschloridecomplexes, togetherwith equivalentconcentrations of reducedsulfur,at temper-
aturesof 100ø to 150øC and pH's of one to two units lessthan neutral, and could have been
precipitatedby pH increases, cooling,or dilution at the sitesof deposition.
Introduction viewedby Bastin,1989;Heyl et al., 1974;Ohle, 1959,

1980; Roedder, 1967, 1976; Snyder, 1967, 1968;
NUME•tOtSS studiesof the geologicand geochemical White, 1968, 1974) have establishedthat the deposits
characteristics
of Mississippi
Valley-typedeposits(re- formed from hot, saline, aqueoussolutionsat some
time after the lithification of their host rocks. Yet, in
* PresentAddress:Department of Earth and Space Sciences,
State Universityof New York at Stony Brook, Stony Brook, NY spite of over 100 years of investigation,important
11794. aspectsof the origin of the depositsremain contro-
1848
ORIGIN OF A MISSISSIPPIVALLEY-TYPEDEPOSIT 1849
versial.MississippiValley-type depositscontain enor- TABLE1. Upper CambrianStratigraphicSuccession

in
Southeast Missouri and Subdivision of the Bonneterre
mous,highly localizedconcentrations of zinc, lead, Formationin the Vicinity of the Buick Mine
barium, fluorine, and sulfur, yet sourcesof these
elements,their concentrationsin the 'ore-formingso- Thickness
lutions,and the specificchemicalreactionsby which Unit (meters) Predominantlithology
they were depositedare not well established.The
Eminence dolomite 50-60 Dolostone
presentstudy is a contribution towards unravelling
theseproblemsfor one of the mostimportant Missis- Potosi dolomite 100-120 Dolostone
sippi Valley mineralizationdistricts--the southeast Derby-DoeRun Formation 40 Dolostone

Missouri lead district.
Davis Formation 50 Calcareous shale
This paper describesthe resultsand implications
Bonneterre Formation
of a detailedstudyof the mineralogy,mineralchem- Variable units 20 Dolostone
istry,textures,paragenesis,andthe isotopicgeochem- Calcarenite units :30 Oolitic dolostone
Reef unit :30 Dolostone
istryof sulfurandleadin the Buickmine,Viburnum
Variegated
unit :30 Dolostone
andlimestone
Trend, southeast Missouri(Fig. 1). A preliminaryre-
Lamotte sandstone 100 Quartz sandstone
port on the sulfurand lead isotopicgeochemistry of
the Buickminewasgivenby Sveriensky et al. (1979).
After Thackerand Anderson,1977;and Rogersand Davis, 1977
Other publishedmineralogicand paragenetic studies
of minesin the Viburnum Trend are thoseby Hagni
andTrancynger(1977)andStein(1980),whostudied
the Magmontmine,andClendenin(1977),whostud- (1956), Ault and Kulp (1960), Brown (1967), and Kulp
ied galena-bearing hand specimens from the Ozark (1956).Theseearly isotopicstudieshad pooranalyt-
mine (Fig. 1). The Old Lead Belt and neighboring ical precision;however,they do illustrateimportant
subdistricts(Fig. 1) were the subiectof mineralogic district-widecharacteristics. Modern high precision
and parageneticstudiesby Tarr (19•36)and Davis lead isotopicanalysesby Doe and Delevaux (1972)
(1960) and isotopicstudiesby Ault (1956), Ault et al. of galenaore and possiblesourcerocksfrom the vi-
cinity of the Viburnum Trend establishedthat the
genesisof this subdistrictwas closelyrelated to that
of the Old Lead Belt, and that the upper Cambrian
LamotteSandstone wasprobablyboth an aquifer for
the ore-formingsolutionsand an importantsourceof
the lead in the galena-bearingorebodies.
Geologic Setting of Mineralization in Southeast
Missouri
The MississippiValley-type depositsin southeast

Missouri(Fig. 1) occurin upper Cambrianand lower
Ordovician sedimentarystrata (Table 1), which un-
conformablyoverliea Precambrianigneousbasement
about1,500m.y. old (Bickfordand Mose,1975).The
area wasrepeatedlyuplifted and erodedduring the
Paleozoic era and a domal structure resulted. In the
center of the dome the Precambrianbasementcrops
out in the area of the St. Francois Mountains. The
sedimentsdip very gently outward from the center
of the dome, over buried Precambrianridges and
knobswhere, locally, the lowermostunits (the La-
motte Sandstoneand the Bonneterre Formation, Ta-
ble 1), pinch out. To the northeast,they are covered
by youngerPaleozoicsedimentaryunitsthat extend
Legend: into the Illinois Basin, and in the far northwest of the
::![[[[
Precambrion
outcrop
• Lead district
state,the lower Paleozoicstratabecomepart of the
• Borite-leoddistrict Forest City Basin. To the southeast,the Paleozoic
;.";.'Barite district unitsare coveredby sedimentsof the north-western-
most extension of the Gulf Coast Basin, and in the
FIG. 1. Major subdistrictsand mines within the southeastMis- southwest,they eventuallybecomepart of the com-
souridistrict (after Thacker and Anderson,1977). plexly deformedOuachita Mountainsin Arkansas.
1850 DIMITRI A. SVERJENSKY
Structural disturbance in southeast Missouri is mi- amountsof galenaoccurin veinsin the Potosiand
nor. The major faults (Fig. 1) trend predominantly EminenceFormations(Fig. I and Table 1). In the
northwest-southeast and are nearly vertical, normal far north of southeastMissouri,the Franklin County
faults,with displacements up to 200 m (McCracken, mines(Fig. 1) containmainly baritemineralization
1971). Some of the smaller faults have strike-slip in the lower Ordovician Gasconnade,Roubidoux,and
movement (McCracken, 1971;Gerdemann Jefferson
andMyers, City Formations(Snyderand Gerdemann,
1972).Breccias that resultedfrom explosive 1968).Clearly,thereis a district-wideprogression
Paleozoic in
activityoccurat FurnaceCreekand,together southeast
igneous Missouriby whichthe bariteto galenaratio
with basicintrusionsat Avon, are part of a line of increases to the north and reaches a maximum in the
similar features that extendsfrom Illinois through youngestformationspresent.
Kansas(Snyderand Gerdemann,1965).Thesestruc- The changefrom barite-freedeposits in the south
turesand major east-westtrending strike-slipfault to barite-richdepositsin the north is paralleledby
zoneswere named the $8th parallel zone by Heyl systematic changesof the isotopiccompositions of
(1972). galenain thedeposits (Ault,1956;Brown,1967;Kulp,
The major subdistricts of mineralizationin south- 1956).In the barite-freeleaddeposits, boththe sulfur
eastMissouri(Fig. 1) are IndianCreek,the Old Lead andleadisotopic compositions haveverylargeranges
Belt, Fredericktown,Annapolis,and the Viburnum of values,and in general,the lightestsulfuris asso-
Trend (Snyderand Gerdemann,1968).In all these ciatedwiththemostradiogenic lead(Fig. 15).Galena
areaslead-zinc-copper-cobalt-nickel sulfidedeposits from the barite-richdeposits hassulfurand leadiso-
occurmainly in brownor gray-browndolostone of topiccompositions that overlapwith the isotopically
the upperCambrianBonnetcftcFormationand to lightestsulfurand the mostradiogenic leadisotopic
a muchlesserextentin the underlyingLamotteSand- compositions of galenafrom the barite-freedeposits
stone.Away from the largestbasemetalsulfidede- (Fig. 15).In the past,the questionof the originof the
posits,the Bonneterre Formationis eitherbrownor barite-leadand barite depositsin the northernpart
gray-brown limestone or whiteor graydolostone. For of the southeastMissouridistricthasbeen regarded
example,morethan ten km to the westof the Vi- as a completelyseparateproblemfrom that of the
burnum Trend (Fig. 1), both the BonneterreFor- lead-zinc-copper-cobalt-nickel sulfidedeposits in the
mationandthe DavisShaleare about90 percentlime- centralandsouthern partsof the district(Snyderand
stone(Ericksonet al., 1978) and they still contain Gerdemann,1968). However, the mineralogicand
trace amounts of lead and zinc sulfides. However, no isotopictrendsdiscussed abovesuggest thatthe origin
orebodies have ever been found in limestone of the of the whole southeast Missouri district should be con-
Bonnetcftc Formation in southeastMissouri (Davis, sideredas a singleproblem.
pers.commun.),althoughorebodiesdo occurvery
near the limestone-dolostone interface in the Vi- Comparisonof the Viburnum Trend with the Old
Lead Belt
burnum No. 27 and No. 29 mines (Grundmann,
1977), in the Buick mine (Rogersand Davis, 1977), These two major subdistrictshave important geo-
and in the Old Lead Belt (Ohle and Brown, 1954). chemicalandgeologicfeaturesin common.Bothcon-
More than two km to the eastof the Viburnum Trend, tain lead-zinc-copper-cobalt-nickel sulfides,the lead
the Bonneterre Formation contains greater than and zinc sulfidesare by far the mostabundant,and
about10percentof grayandwhitelenses of dolostone, in marked contrastto other MississippiValley-type
locallytermed"whiterock"(Gerdemann andMyers, deposits,lead is far more abundantthan zinc. The
1972). Further east toward the St. Francoismoun- lead to zinc atomic ratio in the Old Lead Belt is about
tains,the whole upper Cambriansectionis white or 5 (Snyderand Gerdemann,1968) and in the Vi-
gray. Importantbasemetal sulfidedepositsin the burnurn Trend varies from as low as 1.$ for the Buick
white rock occurat Annapolis(Snyderand Gerde- mine (Rogersand Davis, 1977)to as much as 4 for
mann,1968)andthe ViburnumNo. 28 mine(Grund- the Viburnum No. 29 mine (Grundmann, 1977). In
mann, 1977).Trace amountsof galenaand chalco- addition,the isotopiccompositions
of the lead and
pyriteare commonin white rockto the eastof the sulfurin galenafrom the ViburnumTrend and the
Buickmine (Rogersand Davis, 1977). Old Lead Belt havevery similarranges(Brown,1967;
No significant
quantitiesof baritehaveeverbeen Doe and Delevaux, 1972; Sverjenskyet al., 1979).
found in the subdistrictsmentioned above (Snyder Althoughthe basemetal sulfideorebodiesin the
and Gerdemann,1968).However,in the Palmerand Viburnum Trend and the Old Lead Belt are strata-
Valle mine areas(Fig. 1), both galenaand barite bound within the BonneterreFormation, they occur
mineralization occur in veins in the lower Ordovician at a varietyof stratigraphiclevels.In the Viburnum
PotosiFormation (Table 1). Further north, in the Trend,manyof theorebodies occurin theupperthird
area, barite and much lesser of the Bonneterre Formation. In contrast,most of the
Richwoods-Palmer-Potosi
ORIGIN OF A MISSISSIPPI VALLEY-TYPE DEPOSIT 1851
orebodies in the Old Lead Belt and other subdistricts

to the east of the St. Francois mountains occur in the
lower half of the BonneterreFormation, some just
aboveor actuallyin the Lamotte Sandstone(Snyder
andGerdemann,
1968).Theyfollowpinch-outs
of the 2
Lamotte Sandstone and the Bonneterre Formation
againstburiedPrecambrianridgesor knobs;they oc-
cur on the flanksor overthe crestsof ridge structures
in the BonneterreFormation (particularly where
blackshalesoccur);and they occurin algal "reefs"
of the middle BonneterreFormationalongthe con-
tact with coarse-grained clasticcarbonates(Snyder
and Gerdemann,1968).In the Viburnum Trend, ore-
bodiesare spatiallyrelated to buried Precambrian
ridgesor knobsin the Viburnum No. 27 mine (Grund-
mann, 1977), the Fletcher mine (Paarlberg and
Evans, 1977), and the Ozark Lead mine (Mouat and
Clendenin,1977).However,in the Magmont,Buick,
and BrushyCreek mines,the orebodiesoccuronly
in the upper third of the BonneterreFormationand
are not spatiallyrelatedto the kindsof primary de-
positionalstructuresthat seem to control ore distri-
bution in the Old Lead Belt.
Local geology
In the vicinity of the Buick mine, the Bonneterre
Formationhasbeensubdividedlithologicallyby mine
geologistsinto four approximatelyhorizontalunits
(Fig. 2 and Table 1), recognizablein drill corefor a
mile west and east of the mine. The Bonneterre For- I I
150
mationis similarlysubdividedby mine geologists in
the othermajorminesin the ViburnumTrend (Whar-
ton et al., 1975). Lyle (1977) and Larsen(1977) sug- 2Z
gestthat the variableand calcareniteunits (Table 1)

24
2!
915
DAVIS FORMATION
V552
SHELF FACIES f
".__-.-\ F•½;.$. Map of the Buickorebodies(after Rogersand Davis,

1977) showingsamplinglocalitiesof this study(seealsoFig. 8).
The section line 72 South crossesthe western, central, and eastern
• -- FACIES
--• •.•EEF •O
BACKREEF
orebodies.
belongto a shelf facies,the reef unit belongsto a

e• ß• e• e• e•FO•EF FACI•• barrierreef faciesthat intertongues
with a backreef
LAMOTTE
FORMATION 5• FEET facies(the sameas the planar stromatoliteand bur-
rowedcarbonatemud faciesof Howe, 1968), and the
variegatedunitsbelongto a forereef facies.Recent
work by Jordan(1978) suggests that the calcarenite
FIG. 2. Cross section of the Viburnum Trend in the north Buick
units form part of a large oolite bar, analogousto
area (after Lyle, 1977)showingthe faciesrelationships in the Bon-
neterre Formation. Also shown are the crosscuttinglimestone- thoseof the presentday in the Bahamas.
dolostone interface (-O-ß-) and the brown-white interface It is the highly ooliticbrowncalcarenites
that con-
(---). Brown dolostoneoccursbetween the two interfaces. tain the main orebodiesin the Magmont,Buick,and
I00 •m 1 •m
B
L_J
100 •m lO •m
100 •m 1
!
100 um I0 •m
1852
ORIGIN OF A MISSISSIPPI VALLEY-TYPE DEPOSIT 1851]
BrushyCreek mines.However,within the Bonneterre tation of cubic galena,and finally etching of all the
Formation,the orebodies
clearlycrosscut
the variable galena.
andcalcarenite
units(Rogers
andDavis,1977;Jordan, Clearly,galenawasprecipitatedand dissolved re-
1978). In the Buick mine, mineralization occurs in
petitivelyin the Buickmine.Repetitiveprecipitation
narrow elongateorebodieswhich define an ore zone and dissolutionof galenahasalsobeenestablishedfor
about200 m wideand30 m thick,extendingcontin- the Magmontmine (Hagni and Trancynger,1977;
uouslyfor about sevenkm north-southin the Buick and Stein, 1980) and for the Ozark mine (Clendenin,
property(Fig. 3). Within the orebodies,
galena,sphal- 1977). Other mines in the Viburnum Trend have not
erite, and chalcopyritemineralizationoccursas mas- yet beenstudiedin sufficientdetail.However,partial
sive, bandedreplacementsof the dolostone,as dis- to extensivedissolutionof cuboctahedralgalenahas
seminations and veinlets in the dolostone, and as been described for the Viburnum No. 27 mine
open-space
fillings.Individualmarkerunits(e.g.,the (Grundmann,1977), and the Fletcher mine (Paarl-
"Gray Beds"of Rogersand Davis, 1977) in the Bon- bergand Evans,1977),and partiallydissolved cubes
neterre Formation are fragmented, partially col- of galenahave beendescribedfrom the Ozark mine
lapsed,or brecciated withinthe orezone,and vugs (Clendenin,1977)and the Fletchermine (Paarlberg
up to twoft in sizeoccurin theorezone(Rogers and and Evans,1977),stronglysuggesting that repetitive
Davis, 1977; Jordan,1978). In addition, observations precipitationand dissolutionof galena was an im-
by Rogersand Davis(1977)stronglysuggest someof portantfeatureof mineralization throughout mostof
the brecciation was concomitant with the mineral- the Viburnum Trend.
ization.Alongwith the massivereplacementof the Disseminated galenacrystals
characteristically
have
dolostoneby the basemetal sulfides,thesefeatures a six-sided shapein crosssection(Fig. 5A). One or
clearlyindicatethat the ore-forming
fluidsdissolved two of the sixsidesis oftenmadeup of highlyirreg-
the dolostonehostrock while mineralizationpro- ular veinletsthat replaceddolostonebut which all
ceeded. end at about the same distance from the center of the
crystal(Fig.5A).Apparently,
thegalenacrystals
grew
Mineralogy,Textures,and Paragenesisof the dendriticallyas the dolomitedissolved.The charac-
Buick Mine
teristicsix-sided
shapeof the galenacrystalsis prob-
Galena ablya sectionthrougha cuboctahedron,because etch-
ingwit•dilutenitricacidreveals
growth
zonation
Galenacrystals in vugsareverycommonly coarse- attributableto two differentcrystalforms(Fig. 5A).
grainedcuboctahedra or cubesabout1 cm in length Accordingto Frondelet al. (1942)suchzonationre-
(Fig.4). Whenthetwoarein contact, thecubesperch vealsvariations of the silvercontentof the galena.It
ontopof or partiallyenclose thecuboctahedra, sug- is suggestedhere that the disseminatedcuboctahedra
gestingthat the cubeswere depositedlater than the of galenaarethesamegenerationasthecuboctahedra
cuboctahedra. The cubesalsocommonlyperchon or in vugs in the dolostone.Both are often rimmed or
partiallyencloseeuhedralrhombs ofdolomite in vugs. coatedby bladed marcasiteand have the same dis-
The cuboctahedra invariablyshowevidenceof hav- tinctiverangesof sulfurand lead isotopiccomposi-
ing beenetchedor partiallydissolved. An example tions(seebelow for discussion).
of mildetchingisshownin Figure4A andB in which
the octahedral faceson the cuboctahedraare dull and Sphalerite
pittedandthe cubefaceslustrous
andsmooth.Partial Three typesof sphaleriteoccurin the Buickmine:
dissolutionisshownin Figure4C, in whicha typical massive, extremelyfinegrainedyellowsphalerite that
extensively furrowedcuboctahedron of galenais ad- replaceddolostone; dark,almostopaquecrystalsdis-
jacentto a cubethat showsevidenceof mild etching seminatedin dolostone and lining vugsin the dolo-
only.Bothcrystals in Figure4C arecoveredby very stone;andclearpaleyellowto brown-colored crystals
similar,extremelyfine grainedlayersof galena,in occurringmainlyin vugs.The firsttwo are grouped
whichindividual tabletsof galenaalsoshowetchpits togetherhereasthe mainstageof sphaleriteprecip-
(Fig. 4D). In this sample,precipitationof cubocta- itation in the Buick mine. They were precipitated
hedralgalenawasfollowedby dissolution, precipi- beforethecuboctahedral stageof galena.Overall,the
FIG.4. Dissolution
featuresof galenaandsphalerite
crystals.
A. Partiallydissolved
cuboctahedron
of
galenafroma rug.B. Highlymagnified viewof partof thefrontoctahedral facein A. C. Partially
dissolved
cuboctahedronof galena
adjacenttoa cubeof galenain a rug.D. Layerof galenacrystals
that
grewonthesurface of thecuboctahedronin C. Individual
tabletsin thelayerarealsopitted.E. Early
darksphalerite
in a rug withrhombs of dolomite. F. Etchedsurface of thelargesphalerite
crystalin
E.G. Latepalesphalerite
crystalperched
ona partiallydissolved
cuboctahedron
of galena.H. Smooth
unetchedsurfaceof the sphaleritecrystalin G.
TABLE 2. TexturalRelationships
in Vug-Fillingand Disseminated
Oresfrom the BuickMine
Vug-
Filling CuboctGn Cubic Gn Dark Sp PaleSp Ms Qtz DI
CuboctGn Clusterslining vugs Cubeson oct Oct on sp Sp on gn Ms coatsgn Qtz coatsgn DI asragged
inclusions in
gn
Cubic Gn Clusterslining Gn on sp Sp beneathor Not observed Qtz coatsGn Euhedralrhombs

vugs included in or of dl as
perchedon gn included in or
grown on gn
Dark Sp Clusters Pale sp Ms coats Occurs on and DI occurs on and

lining vugs overgrowths
on dark sp adjacent to sp next to sp
dark sp rarely
PaleSp Clusters
liningvugs Not observed Qtz grewon and DI grewon and
adjacentto sp adjacentto sp
Clusters of Ms coated by qtz Ms coatsdl

bladed
crystals
Qtz Clustersof Qtz grew on and

doublyterm. adjacentto dl
crystals
Cp Not observed Cp on cubicgn Cp on sp Not observed Cp on ms Cp includedin Cp on dl

qtz or coats
qtz
Disseminated Gn Sp DI Ms
Gn Gn veinletscrosscut
growthzones Six-sided
crystalsof gn in Coarsems rims and veinsgn
in sp and surroundsp dolostone
Sp Raggedinclusions
of sp in Subhedralcrystalsof sp Coarsems rims and veinssp
gn or extremelyfine
grainedsp in dl
DI Raggedinclusions
of dl in gn Minuteeuhedralrhombsin sp Raggedinclusionsof dl in ms
Pv Not observed Fine-grainedinclusions

of py in sp Fine-grainedinclusions
of Coarse ms rims coarsepy
py in dl rhombsof ds
Ms luciusions of •ng and ms rims Veinletsand inclusions

of ms in sp Fine-grainedms or coarse
around gn bladed ms in dolostone
Cp Rimsof cp aroundgn Dendritic cp in sp Raresubhedralcrystalsin Cp inclnsionsin ms

dolostone
Sg Rimsof sgaroundgn Rimsof sgaroundsp Rare small disseminated Sg inclusions

in ms
grainsin dolostone
Qtz Euhedralqtz in gn Euhedralqtz in sp Euhedralqtz in spatry Euhedralqt7 in ms

dolomite
Abbreviatious
(;n = Galena,
Sp= Sphalerite,
DI = Dolomite,
Py = Pyrite,Ms = Marcasite,
Cp = Chalcopyrite,
Sg= Siegenite,
Qtz = Quartz
sphaleritesvary in chemicalcompositionfrom about face, they causepits with the sameradial distribution
0.4 to 10.0 mole percent FeS, and from about 0.4 to as the inclusions.Coarsergrained, clear, very pale
4 molepercentCdS.Typical chemicalanalysesof the sphaleritecrosscutsthe yellow sphaleriteas late vein-
two typesof main-stagesphaleriteare given in Ta- letsand occursin vugsin the yellow sphalerite,i•n-
ble $. plying at least two periodsof growth of sphalerite
The fine-grainedyellow sphaleriteoccursonly in separatedby a period of dissolutionof sphalerite.
the central orebodyof the Buick mine (Fig. $). In The dark sphaleriteoccurswest and east of the
thin sectionit hasa distinctiveappearance,containing fine-grainedyellowsphaleritein the centralorebody.
very pale yellow patchesand many minute, ragged, Thin sectionsrevealthat the dark colorin handspec-
opaqueinclusions (Fig. 5B), whichoftenhavea radial imen is causedby intenselycoloredzones(Fig. 5C),
distributionwithin a crystal. These inclusionsare aswell asa subtlecolorbanding,parallelto theoutline
probablyorganicmatter because,on a polishedsur- of the crystal,in which pale and darker yellow bands
overlap with zonesof minute (lessthan i #) fluid TABLE•3. ChemicalCompositions of the Two DifferentTypes
inclusions(Fig. 5D). The subtle color banding is of Main-StageSphaleritefrom the Buick Mine
causedby small variationsin the iron contentof the
ZnS FeS CdS
sphalerite,from 0.6 to about 2.0 mole percent FeS, (mole percent)
and is probablya growthbandingin response to fluc-
tuationsin the chemistryof the solutionsdepositing Dark sphaleritecrystal
the sphalerite.The intenselycolored zonesare su- with intense color
zoning:
perimposedon the much paler growth bands,but
occuronly in sectorsof the crystal(Fig. 5D, F, and Intensepurple-brown
H). Three different intenselycoloredzonesare com- zone,
mon:orangeor orange-brown,red-brownor purple- Centerof crystal 96.6 2.4 0.5

97.0 1.8 1.0
brown, and deep blue. A singlecrystalmay contain Edgeof crystal 97.2 1.4 1.2
only one type of coloredzone (Fig. 5G). However,
where a crystal containsall three types, then they Pale yellow part of crystal,
Centerof crystal 95.0 $.0 0.8
generallyoccur in the order given above from the 97.2 1.9 1.2
center of the crystalout to the edge (Fig. 5D). In 97.0 0.7 1.6
hand specimens, all the dark sphaleritecrystalshave 98.6 1.4 0.•
the samepredominantcolortype or sequenceof col- Edgeof crystal 97.2 1.6 1.0
ors.However, in the ore zone, there is no systematic Intensepurple zone 97.8 0.5 1.0
variation of color type either vertically or laterally. 97.0 1.6 1.0
The causeof the intenselycoloredzonesin the dark

sphaleriteisunknown.Because thesezonesare closely Yellowsphaleritecrystal
with inclusions of
associatedwith the subtle growth banding in the
organic matter:
sphalerite,it is suggested that they are alsoa growth
phenomenon.They are not causedby variationsin Pale yellow part of crystal,
Center of crystal 97.2 2.1 0.0
the majoror minor elementcontentof the sphalerites, 96.6 2.2 0.5
becauseelectronmicroprobeanalysesof the sphal- 98.0 0.9 0.4
eritesdo not showany correlationof chemical com- 97.6 0.9 0.3
positionwith theseintensecolors.The lower limit of 98.8 0.9 0.3
detectionusingthismethodwasabout0.2 wt percent Edge of crystal 99.2 1.2 0.3
for elements of the first transition series. The colors Yellow part of crystal 97.2 2.6 0.8
could be causedby variationsin the trace element 97.4 2.6 0.7
contentof the sphaleriteif chargetransferis taking

placebetweenelementswith multipleoxidationstates All analyses
carriedout by electronmicroprobeusingsynthetic
sphalerite-wurtzitestandards
suchas iron, cobalt,nickel, or copper,or they could
be causedby filmsof coloredorganiccompounds on
growth surfacesin the sphalerite.X-ray powderdif- nevercoatedby darksphalerite,but oftenhavegrown
fraction photographsdo not showany evidenceof on top of dark sphaleritecrystals.
crystallineimpurities or wurtzite sequencesin the The third type of sphalerite,called pale sphalerite
sphalerites. here, is minor in abundancecomparedwith the two
In vugs,the dark sphaleritecharacteristicallyhas typesdescribedabove.In hand specimenit occursas
very rough,dull pitted crystalfaces(Fig. 4E and F). pale yellow to brown-coloredcrystalsthat line vugs,
Clearly,thesecrystals,like the cuboctahedra of gal- or are perchedon partly dissolvedor etched cuboc-
ena, havebeenetchedand in someinstances partially tahedraof galena (Fig. 4G), or on rhombohedraof
dissolved. In thin section, the disseminated dark dolomite.It alsooccursasovergrowths on partly dis-
sphaleritecrystalsalsoshow evidenceof dissolution solveddark sphalerite(Fig. 5G and H) or on earlier
at interfaceswith thin overgrowths of very pale yel- fine-grainedyellow sphalerite.In thin section,it is
low sphalerite,which doesnot contain intensecolor remarkablyclear of solid or fluid inclusionsand of
banding(Fig. 5E). Suchinterfacesprovideevidence the intenselycoloredbandsdescribedearlier. How-
of two periodsof precipitationof sphaleriteseparated ever,somecrystalsdo containfaint patchesof orange
by a period of dissolution. or purple (Fig. 5G).
All the dark or fine-grainedyellow sphaleriteis Clearly,the texturalrelationshipsof the threetypes
crosscut or rimmed by galena,or occursassmallrag- of sphaleritein the Buick mine provide evidenceof
ged inclusions in galena(Fig. 5C and E). Individual periodsof repetitive precipitationof sphaleritesep-
growth zonesare crosscutby fine veinletsand net- arated by periodsof dissolution,just as was noted
worksof galena(Fig. 5C). In vugs,galenacrystalsare abovefor galena.Similarsphaleritetypesandtextural
I
A B
c D
I-I
1856
relationships
probablyexist in other mines in thestone.Lessfrequently,the bladedmarcasitereplaces
dark sphalerite.In onesample,bladedmarcasitehas
Viburnum Trend, but have not been reported simply
because
published
studiesdid not usedoublypolished grownaroundovoidpyrite grains.
thin sections(Barton, 1970) for microscopy.
Sulfidesof copper,cobalt,nickel,and iron
Iron disulfides
Chalcopyriteoccursassinglecrystalsdisseminated
Both pyrite and marcasiteare abundant in the with cuboctahedral galenain dolostone and as den-
Buick orebodies.Fine-grainediron disulfideswith a dritic growthsin the dark sphalerite.In addition,a
grain sizelessthan about20 # are typically rectan- very late generationof chalcopyritecrystalsoccurs
gular or squarein shapeand individualgrainsmay perchedon cubic galena,dark sphalerite,dolomite,
be either pyrite or marcasite,or partly pyrite and and quartz.
partly marcasite.In the orebodies,thesefine-grained Copper-cobalt-nickel-iron thiospinelsoccurrarely
irondisulfides
aremostabundantin fine-grainedparts as large (200 #) grainsin dolostoneand more com-
of a dolostone
(e.g.,clasts)that containverylittle base monlyassmallrimsaroundand inclusions in galena,
metal sulfide.In the coarsergrainedpartsof a do- or are closely associatedwith chalcopyriterims
lostone(e.g.,betweenclasts)where sphaleriteor gal- around galena. The thiospinelscontain predomi-
ena are abundant,the fine-grainediron disulfides nantly nickel and cobalt, with only a few percent
tend to occuronly in the dustybrowncoresof large iron, and are properlycalled siegenite(Craig and
dolomiterhombsthat are surroundedby rims of col- Carpenter, 1977).
orlessdolomite(Fig. 5E and F). Thesetextural re-
lationshipssuggestthat the fine-grainediron disul- Gangueminerals
fidesweredissolved duringthe formationof the clear
colorlessdolomiteand associated sphaleriteand gal- In decreasing order of abundancetheseare dolo-
ena.The fine-grainedirondisulfides are probablynot mite, quartz, calcite, and kaolinitc. Clear or white
diageneticbecauseelectronmicroprobeanalysesof dolomiterhombsare very abundantin vugsin the
them revealednickel and copper contentsof up to orezone.Unlikethedistinctivedolomitecrystals from
0.3 wt percent.It is likely that the fine-grainedpyrite the Tri-State district, the dolomite crystalsin the
or marcasite(possiblyboth) were precipitatedas the Buickmine are not saddleshaped,they are euhedral
earlieststageof sulfidemineralizationin the Buick rhombs.In vugs,the dolomiterhombsare frequently
mine. Becausesphaleritewasprecipitatednext,some coatedby small,clear,euhedral,doublyterminated
of the reducedsulfurand iron in the sphaleritemay quartz crystals.Euhedral quartz crystalsalso occur
bederivedfromtheearlyfine-grained irondisulfides. asinclusionsin disseminated cuboctahedra of galena.
Coarse-grained pyrite typically occursassubspher- Rare, coarse-grained quartz crystals(up to 2 cm in
icalor ovoidgrainsconsisting of aggregates of minute length)containinclusions of and are coatedby chal-
crystals.Thesegrainsare frequentlyassociated with copyrite.Largecalcitecrystals(up to 10 cm in length)
thin,shalyseams in thedo!ostone, andif intersected occurin vugswhere they encloseand surroundany
by a veinletof galenaor sphaleriteare partiallymar- of the other minerals,includingeuhedraldolomite
casite. Apparently marcasitereplaced pyrite, al- rhombs.The calcite is not, however,in oxygeniso-
thoughthis has never been achievedin laboratory topic equilibrium with the dolomite (Sverjensky,
experiments(Rising,1973). Coarse-grained marcasite 1980) becauseit is isotopicallyheavierthan the do-
is very common,typicallyasclustersof bladedcrys- lomite.It may havebeenprecipitatedat temperatures
tals,coatingcuboctahedral galenain vugsand rim- 30ø to 50øC lower than the dolomite.Fine-grained
ming cuboctahedraof galenadisseminatedin dolo- kaolinitcfills vugs,coatingall earliercrystals.
FIG. 5 Textural relationshipsof ore mineralsfrom the Buick mine. A. Six-sidedgalena crystal in
dolostone,etched with dilute nitric acid. 8.6 mm field width. B. Early yellow sphaleritewith radial
inclusionsof organicmatter (opaque).5.8 mm field width. C. Early dark sphaleritecrystal(center)with
intenselycoloredbands,crosscutby galena (black). 1.4 mm field width. D. Early dark sphaleritecrystal
(at left, in a vug) containingpale yellow growth bandsand intensebrown and blue bands.2.8 mm field
width. E. Veinlet of galena (black)crosscutting early yellow sphalerite(note organicmatter, lower left)
and a rhombof dolomite(upperright) that hasa browncore (with inclusions of FeS2)rimmed by clear,
colorlessdolomite.Note the curved plane of fluid inclusionsseparatingyellow and colorlesssphalerite
(a solutionunconformity).1.4 mm field width. F. Early dark sphaleritedisseminatedin dolostonethat
hasdolomiterhombswith dusty,browncores(andinclusions of FeS2)rimmed by clear,colorless dolomite.
2.8 mm field width. G. Early dark sphalerite(center)overgrownby late pale sphalerite.2.8 mm field
width. H. Early dark sphaleritein a vug overgrownby late pale sphalerite.1.4 mm field width.
GALENA becausethe temperaturefell, becausethe solubility

of dolomitein aqueoussolutions increaseswith a fall-
SPHALERITE
ing temperature.It is morelikely that an increaseof
the activityof CO•-2occurredin response to increases
of pH or bicarbonateconcentration.
DOLOMITE Figure6 alsoshowstwo periodsof precipitationof
iron disulfides.During the secondof these,bladed
marcasitewas precipitatedat the sametime as the
FINEGRAINED
FeS2 main period of dissolutionof cuboctahedralgalena.
It hasbeensuggested that precipitationof marcasite
BLADED MARCASITE often occursbecausepyrite fails to nucleateand so-
lutionsbecomesignificantlysupersaturated with re-
spectto pyrite (seeBartonand Skinner,1979).If this
CHALCOPYRITE
occurredduring the paragenesis shownin Figure 6,
it is likely that the precipitationof marcasitewould
SIEGENITE causea significant
decrease
of pH in the ore-forming
solution, which could account for the dissolutionof
the cuboctahedral galena.
QUARTZ m
The early fine-grainediron disulfidesare thought
to have been precipitatedduring hydrothermalre-
CALCITE placementof browndolomiteand then to havebeen
dissolved during precipitationof the clear, colorless
dolomiterims and the sphalerite.Becauseinclusions
KAOLINITE •
of the iron disulfidesoccasionallyoccurin the sphal-
FIG. 6. Paragenesisof ore and ganguemineralsin the Buick erite and in the clear dolomite, it is likely that, at
mine. Mineral growth is representedby solid blocksand lines; least locally, the solutionsprecipitating sphalerite
mineraldissolution
by dashedlines.
were saturatedwith respectto an iron disulfide,but
that in generalthe activityof FeS in sphaleritewas
Implications.of the paragenesis influencedby the iron-bearingdolomite. The iron
The mineralogical, textural,and parageneticrela- contentsof sphaleriteand dolomitein the assemblage
tionshipsdescribedaboveare summarizedin Table pyrite + sphalerite+ dolomite+ fluid can be de-
2 and Figure 6. Two featuresof Figure 6 have im- scribedaccordingto equilibriasuchas
portantimplications.First, the repetitiveprecipita-
tion and dissolution of sphaleriteand galenaimplies (FeS)sp+ CO2+ H20 = (FeCOs) dø+ H2S (1)
that the ore-formingsolutionsmovingthroughthe and
depositwere alternatelysupersaturated and under- (FeS)spq- 1/282
= (FeS2)py. (2)
saturatedwith respectto the basemetalsulfides.The The equilibrium constantfor reaction(1) cannot
simplestexplanationof this behavioris that the so- be calculatedaccurately,becausethere are no ex-
lutions carried both metals and reduced sulfur to-
perimentallydeterminedfree energydatafor FeCOs
getherand that their stateof saturation changedbe- or CaFe(COs)2indolomite.However,the free energy
cause of changesin theirtemperature,pH, oroxidation of FeCOsin sideriteis known (Helgesonet al., 1978).
state. Alternatively,many solutionswith markedly
By assumingthat the free energyof FeCOsin do-
differentchemicalcharacters, possiblyfrom different lomite is the sameasin siderite,the equilibriumfor
sources, might be responsiblefor the alternatingpe- reaction(1) can be calculatedfrom the equilibrium
riodsof precipitationanddissolutionof the sphalerite constants for the reactions
and the galena.
Second,precipitationof dolomiterhombssimul- (FeS2)
py+ 602(g)
+ 1/202(g)
= (FeCOs)
sid+ S2(g),
taneouslywith someof the sphaleriteand cubicgal-
ena impliesthat, at somestages,the ore-formingso- log Ks = 5.97; (8)
lutionswere saturatedwith respectto dolomiteand
basemetal sulfides.However,during the main stages (FeS)
spq-1/2S2(•)
= (FeS2)
py, logK4 = 12.93; (4)
of ore formation, while disseminated and massive
H2(• / + 1/22> = H2S(aq>
+ ¾zO2/,
sphaleriteand then galena were formed, the ore-
formingsolutionsweredissolvingdolostoneand must log Ks = -23.13; (5)
have been undersaturatedwith respectto dolomite.
The dolomiterhombscannothave been precipitated at 100øCand pressuresdefinedby the liquid vapor
equilibriumfor water. The valuesof the equilibrium rium betweensulfateandsulfidesuggested by Barton

constants shown above were chosen from the follow- (1967)for Mississippi Valley-typedeposits in general.
ing sources: logKswascalculatedusingthe computer Fluid Inclusions
programSUPCRT (Helgesonet al., 1978 and 1981);
log K4 is the averageof two valuesgivenby Barton Fluid inclusionsin sphaleritefrom southeastMis-
and Skinner(1979),which differ by only 0.49 log souriare generallyunsuitablefor study, as noted in
units;log Ks is from Helgeson(1969). an early reconnaissance studyof the Viburnum Trend
The resultfor equilibrium(1) is by Roedder(1977),whonevertheless did reportsome
_dol data for sphalerite.In the presentstudy,a sampleof
logK•= logI•CO2
aH2s + log"FeCO• coarse-grained quartz crystalscontaininginclusions
I•FeS of chalcopyritewasusedto determinethe nature of
the relativelylate-stageore-formingsolutions which
- loga,•o = -4.28. (6) had depositedthe chalcopyriteand quartz and to
comparethe resultswith thoseof Roedder (1977).
Assuming valuesof al•O = 1, ml•S= I X 10-6 molal, Fluid inclusionsthoughtto be primary (Roedder,
•l•S = 1.9 (thesameas•co2in 4 molalNaC1solutions, 1967)mostcommonlycontainedan aqueoussolution
extrapolatedfrom Helgeson,1969), and a vaporbubblethat disappeared on heatingin
ado•
FeCO$ = •¾do•
x FeCOa = 0.01, X½'es = 0.01, the temperature range 94ø to 150øC. The inclusions
provedvery difficultto freeze,suggesting
that the
•P•s = 2.4 (Bartonand Skinner,1967) fluid in them is free of particulateimpurities(Roed-
der, 1977).Completelyfrozeninclusions firststarted
results in a valueof 10-•'øbarsfor the fugacityof meltingat about-48 øto -65øC andwerecompletely
carbondioxidein equilibriumwith iron-bearingmeltedin thetemperature range-22 øto +14øC.The
sphalerite and dolomiteat 100øC(thisfugacityof largerangeof the firstmeltingtemperatures may be
carbondioxideis verysensitive to thevalueof ml•S causedby a rangeof fluid inclusionsalinities; how-
chosen; the relativelylow concentration of I •tm was ever,it mayalsobeattributedto the meltingof meta-
chosento be consistentwith the reduced sulfur model stablesuperheated ice, observedby Roedderfor the
discussed later).Therangeof ironcontents of sphal- fluid inclusionsin sphaleritefrom the Viburnum
erites from the Buick mine is about 0.001 to 0.1 mole Trend.In the lattercase,the lowesttemperature of
fractionFeS,whichcorresponds to a rangeof the finalmelting,-22øC, isthe mostusefulguideto the
fugacityof carbondioxidefrom 10-6 to 10-4 bars,if salinityof the solutions and it comparesvery well
theactivities of hydrogen sulfideandironcarbonate, with the rangeof -20.4 ø to -28.2øC reportedby
and temperatureare the sameas above.This calcu- Roedder.This range of temperaturesextendswell
latedrangeof fugacities of carbondioxideoverlapsbelowthe maximumdepression of the freezingpoint
with, but is significantlylower than, the minimum of water in the systemNaC1-H20, which is the eu-
of 10-4'2barscalculated by Barton(1967)andBarton tectic at -20.81øC and $.97 molal NaC1 (Potter et
andSkinner(1967),on the basisof the assemblageal., 1978),implyingthat the ore-formingsolutions
calcite and quartz without wollastonite.It must be musthave containedappreciablequantitiesof diva-
emphasized that the rangeof carbondioxidefugac- lent cations,such as calcium and/or magnesium
itiescalculatedaboveis that of the hydrothermalso- (Roedder,1977).
lutionsin equilibriumwith sphaleriteand dolomite Numerouschemicalanalysesof fluid inclusionsin
andisprobably differentfromthatoftheore-forming otherMississippi Valley-typedeposits (Roedder,1967;
solutions travelingto the siteof deposition. McLimans,1977)haveestablished that the majorele-
Equilibrium(2) impliesthat the rangeof ironcon- ment compositions of the ore-formingsolutionsare
tentsofthesphalerites, fromaF•S = 0.001to0.1,might well represented by the systemNaC1-CaCI2-H20with
correspond to a rangeof sulfurfugacitiesfrom 10-2•2 Na/Ca ratiosof about 1.7 to 5. Assumingthat the
to 10-2•'2at 100øC,or a rangeof temperatures from ore-formingsolutionsin the Viburnum Trend were
84øto 121øCat a sulfurfugacityof 10-2s(Bartonand alsoNa-Ca-Cl-richbrines,with similarNa/Ca ratios,
Skinner,1979).For the highestsulfurfugacityat the observedrangeof freezingtemperatures of the
100øC,the minimumoxygenfugacityfor which brinesin the fluid inclusions canbe comparedwith
magnetite isstableis 10© bars,whichiscompatible experimentallydetermined,low-temperaturephase
with significantquantitiesof sulfateaswell assulfide relationsin the systemNaC1-CaC12-H20 (Yanatieva,
in solution(e.g.,Anderson,1975).Therefore,the iron 1946;seealsoCrawfordet al., 1979)to determinethe
contentsof sphaleritesfrom the Buick mine and the approximate concentrationsof sodium and calcium
absence of magnetitedo not necessarily
implycom- chlorides.Using this method,the solutionwith a
pletelysulfate-free
solutions
or the redoxdisequilib- freezingpointdepression
of -22øC musthavea min-
-8
0 2 4 6 8 I0 12 14 16 18 20 22
Cp --
I I I I I I I I I I I It
oo ß Cp
• I
4 ,
6 '
8 •I I
12 I
14 I
ß I • •2l
.7.The
sulfur
isotopic
com•sitions
ofsulfide
minerals
in
the Buickmine:Cp = chalcopyrite; Ms = marcasite;
Sp = sphal- CUBOCTAHE•
erite;Gn = galena;O: crystals in vugs;ß -- disseminated
and CI•NTER ß MARGIN
massivemineralization.
All galenacrystalsfrom vugswith sulfur CUBE
isotopic
compositionsgreaterthan 11 per mil are cuboctahedra,
thoselessthan 11 per mil are cubes. FiG.9. Variationof sulfurisotopiccompositions
withina single
cuboctahedralcrystaland a singlecubiccrystalof galena.The
abscissa
scaleisarbitrary,butthetotaldistance
fromthecenterof
imum CaCI2contentof about0.64 molaland a max- eachcrystalto the marginis about7 mm for the cuboctahedron
and 18 mm for the cube.The cuboctahedral
crystalisfrom locality
imum NaCI contentof about2.8 molal (Na/Ca = 4.4;
26 (Fig. 3). The cubeis froman unknownlocationin the Buick
mcl-: 4.1 molal).The solutionwith a freezingpoint mine.
depressionof -28øC musthavea minimumCaCI2
content of about 1.6 molal and a maximum NaCI
contentof about1.8 molal(Na/Ca = 1.1;m½l_= 5.0). Tables4 and 5. Note from Figures7 and 8 that the
The rangeof chlorideion molalitiesfrom 4.1 to 5.0 sulfurisotopiccompositions of mostof the dissemi-
molalis very closeto the rangeof 4.6 to 5.6 molal nated six-sidedcrystalsof galenaand the cubocta-
determined by directextractionandanalysis for the hedra of galenafrom vugscover the sameranges,
UpperMississippiValleydeposits (McLimans,1977). implyingthatthesetypesof galenawereprecipitated
Bothranges aresignificantlyhigherthanmostvalues from solutions
with the samerangeof isotopiccom-
obtainedby directchemicalanalysis of chlorideion positions
at aboutthe sametime.Thereforetheyare
in fluid inclusionsfrom Mississippi Valley-typede- grouped togetherasthe cuboctahedral stageof the
posits.For example,Roedder(1967)reportsa typical paragenesis in Figures10and11.Figure7 alsoshows
fluid inclusionanalysisfrom the Tri-Statecontaining thatdisseminatedor massive
sphalerite
andsphalerite
3.5 molalchlorideion. The largervaluescalculated fromvugstendto havethesamesulfurisotopic com-
in thisstudyandthosereportedby McLimans(1977) positions.
The simplicityof the overallparagenesis
are significant
becausemorechloride-richore-form- deducedin this study(Figs.6 and 10, seebelow)is
ing solutions
cantransportgreaterquantities
of base a remarkablecontrastto that givenfor the Magmont
metalsas chloride complexes. mine by Hagni and Trancynger(1977),who chose
separategenerationsof disseminated, colloform,
and
Sulfur and Lead Isotopic Chemistry vug-filling
galena.However,theparagenesis of Fig-
Relationship betweendisseminated and vug-filling ures6 and 10 is very similarto that determinedby
mineralization Stein(1980),whoalsostudiedpart of the Magmont
mine.Hagniand Tracynger's disseminatedgenera-
The isotopic compositions
of sulfidemineralsfrom tion corresponds to part of the cuboctahedral gen-
the Buickmine are reportedin Figures7, 8, 9, and erationof this study.Their colloformgenerationis
based on the abundance of colloform iron disulfides
in the Magmontmineand probablycorresponds to
themaingeneration
of marcasite
precipitation
of this
N13 study.However,
theirvug-filling
generation
of galena
should have included both cuboctahedral and cubic
galenaandoverlapped
withtheearlierdisseminated
WESTERN OR galena.
I
i• ME'T•RS
i Spatialzonationof sulfur isotopiccompositions
FiG. 8. Variationof the sulfurisotopiccompositions
of dissem-
The two generations
of galenain the Buickore
inatedcuboctahedral crystalsof galenaacrossthe Buickmine at zonehavelargebut distinctrangesof sulfurisotopic
the section72 South (seeFig. 3). compositions.
The spatialvariationof oneof these,
TABLE4. Sulfur IsotopicData for the Buick Mine
Locality Analysis $s•S Locality Analysis $a4S

number number Sample (permil) number number Sample (permil)
3 16-4 Pale sphaleritein vugs 12.3 u 34-5 Cubeof galenain vug 5.5
14 16-5 Pale sphaleritein vugsin 19-1 14.6 $ 34-6 Cubeof galenain vug 4.4
25 16-6 Dark sphaleritein vugs 16.4 $ 34-7 Cuboctahedron of galenain vug 14.7
20 17-1 Dark sphaleritein vugs 18.5 25 34-8 Cuboctahedron of galenain vug 21.1
$ 18-2 Dark sphaleritein veinlets 18.3 25 35-1 Cubeof galenain vug 3.5
23 18-5 Dark sphaleritein vugs 18.8 14 •.5-2 Cubeof galenain vug 9.5
26 18-6 Palesphaleritein vugs 12.2 14 $5-3 Cuboctahedron of galenain vug 13.0
14 19-1 Fine-grainedyellowsphalerite 16.2 27 $5-7 Cuboctahedron of galenain vug 14.9
16 19-2 Dark sphaleritein vugs 17.6 26 35-8 Cubeof galenain vug 6.5
20 29-5 Dark sphaleritein vugs 18.1 27 36-1 Cuboctahedron of galenain vug 14.4
2 40-1 Pale sphaleritein vt,gs 12.8 u 37-5 Outermostlayerof cubefrom vug 0.9
14 40-8 Palesphalerite on galena35-3 14.4 u 37-6 Innermostportionof 37-5 cube 6.6
14 41-1 Palesphalerite on galena35-2 14.1 2 40-2 Cuboctahedron of galenain vug 19.2
27 41-3 Palesphaleriteon galena41-4 13.6 14 40-3 Veinletof galenain yellowsphalerite 13.3
H5 44-1 Pale sphaleritein vug 12 8 14 40-6 Cuboctahedronof galenain vug 15.0
KI3 44-2 Dark sp with disseminated gn 42-4 16.8 14 40-7 Cubeof galenain 40-6 9.9
NI3 44-3 Dark sp with disseminated gn 42-5 18.0 14 41-2 Cubeof galenain vug 9.7
Lll 44-4 Dark spin veinwith gn 44-5 17.4 27 41-4 Cubeof galenain vug 0.2
915-1124 44-6 Pale sphaleritein vug 9.0 B13 41-7 Disseminated
galenain dolostone 13.9
1986-4 44-7 Dark sphaleritein vugs 16.8 D5 41-8 Disseminated in dolostone 14.3
u 35-4 Chalcopyritecoatinggalena34-5 10 1 F2 42-1 Disseminated in dolostone 17.8
7 35-5 Chalcopyritecoatinggalena31-4 9.8 V-28 42-1A Cubeof galenafrom vug 1.4
25 $9-6 Marcasitecoatinggalena34-8 2.3 H5 42-3 Disseminated
20 39-7 Martasitecoatinggalena34-3 4.1 K13 42-4 Disseminated
910-1094 45-8 Chalcopyrite disseminated with gn 45-7 15.8 N13 42-5 Disseminated
3 18-4 Cubeof galenain vug 7.7 T5 42-6 Disseminated
25 29-6 Cubeof galenain vug 4.3 V-28 42-7 Octahedronfrom samevug as42-1A 15.4
20 •0-1 Cuboctahedron of galenain vug 19.4 L11 44-5 Galena from veinlet 16.0
14 •0-2 Vein of galenain sp 19-1 11.6 910-1067 45-3 Cubeof galenafrom vug 5.2
25 •0-4 Disseminated galena 20.6 1986-4 45-4 Cubeof galenafrom vug 1.5
19 •0-6 Vein of galenain dolostone 7.9 1986-4 45-5 Cubeof galenafrom vug 4.5
6 •0-8 Vein of galenain dolostone 3.6 910-1054 45-6 Disseminated
26 31-8 Cuboctahedron of galenain vug 15.4 910-1094 45-7 Disseminated
7 31-4 Cubeof galenain vug 7.7 910-1107 46-1 Disseminated
8 31-6 Disseminated galena 16.5 Q17 46-2 Disseminated
3 31-7 Disseminated galena 18.1 R3 46-3 Disseminated
$ 31-8 Galena from veinlet 18.1 S8 46-4 Disseminated
20 34-2 Cubeof galenafrom vug 6.0 1981-80 46-6 Disseminated
20 34-$ Cuboctahedronof galenain vug 18.8 1081-60 46-7 Disseminated
u 34-4 Cuboctahedronof galenain vug 17.0
the cuboctahedral galena,wasstudiedin an east-west are beingdifferentiatedby a moredetailedstudyof

crosssectionof the orezone(Fig. 8). Throughoutmost variationsof the lead and sulfur isotopiccompositions
of the width of the ore zone,the sulfurisotopiccom- of galenaverticallyand acrossthe ore zone.
positionsof cuboctahedral galenaare approximately
constant.On the westernmargin of the ore zone, TABLE5. Lead IsotopicAnalysesof Galenafrom the Buickand
however,they becomesignificantlyheavier,and on Viburnum No. 28 (*) Mines, SoutheastMissouri
the easternmargin they becomesignificantlylighter
than in the central zone. Such a pattern could be Analysis Locality aø•Pb/ aø7pb/ aøsPb/
No. No. gø4pb gø4pb gø4pb
explainedby severaldifferent modelsthat depend
mainly on assuminga predominantdirectionof flow 42-1A* * 22.576 15.992 41.694
of the solutionsdepositinggalena. If the solutions 29-6 25 21.749 15.919 40.733
31-4 7 21.657 15.916 40.640
flowed in a north-southdirection,then it is possible 18-4 3 21.495 15.919 40.562
that theychangedisotopically asthey approachedthe 37-6 u 21.510 15.914 40.529
marginsof the ore zone (e.g., during reactionwith 37-5 u 21.509 15.910 40.405
the host rocks).If the predominantdirection of so- 31-6 8 21.225 15.889 40.095
42-7* * 21.182 15.883 39.874
lution flow was east-west,the solutionsmay have
30~2 14 21.097 15.872 39.825
evolvedisotopicallyas they crossedthe ore zonede- 31-3 26 21.019 15.865 89.781
positingcuboctahedral galena.Alternatively,the cu- 30-1 20 20.480 15.825 89.326
boctahedralgalenain the marginalzoneswasdepos- 30-4 25 20.435 15.817 39.288
ited at a different time, by isotopicallydifferent
solutions,to that in the centralorebody.Thesemodels Analyses
by M. H. Delevauxand A. Hassan
22
mine each sulfidewas precipitatedin isotopicdis-
equilibriumwith the immediatelyprecedingone.
One cannotevenassumesurficialequilibrium(Barton
et al., 1968) for this deposit.Therefore, the sulfur
isotopiccompositions of pairs of sulfidescannot be
usedas geothermometers, in remarkablecontrastto
the Upper Mississippi Valley-typedepositsfor which
McLimans (1977) demonstrateda closeagreement
betweenthe homogenizationtemperaturesof fluid
inclusionsin sphaleriteand temperaturescalculated
from the sulfur isotopiccompositionsof sphalerite
and galena.
In the Viburnum Trend, the maximum tempera-
Dark Cuboct Mc Cubic Pale Cp ture at whichsphaleritewasdepositedisabout150øC.
Sp Gn Gn Sp In Figure 11, the sulfur isotopiccompositions of HaS
PARAGENESIS (in solution)that would be in isotopicequilibrium
FIG. 10. Variation of the sulfur isotopiccompositionsof the with the individualsulfidesof Figure 10 are plotted,
sulfidesasa functionof paragenesis.Each line connectsthe com- assuming a constanttemperatureof 150øC.Obviously
positionsof crystalsfrom a single hand specimen.Abbreviations this assumptionregarding temperature cannot be
as in Figure 7.
checkedfor galena,but the rangesof/•34Sof galena
are so large that they cannotbe attributed to fluc-
Sulfur isotopiczonationwithin singlecrystals tuationsof temperaturealone.The valueof •4Sn2s
in equilibriumwith the sulfidesshowsvery largefluc-
Some of the galena crystalscollectedfrom the tuationsin Figure 11. It increasedafter precipitation
Buick mine were large enoughthat intracrystalline of the early sphalerite,and duringthe precipitation
zonationof sulfurisotopes couldbe investigated.
The of cuboctahedralgalenait becameasheavyas26 per
resultsfor two suchcrystalsare shownin Figure 9. mil. Note that at 100øC this value would be even
The individual analyseswere made on extremely larger, about 28 per mil. Thesemaximum valuesof
small samples,about0.1 to 0.5 mg, dug out with a •4Sn2s areimportantbecause the totalsulfurisotopic
steel needle from polishedsectionsthat had been composition of the solutions(/5•4Szs)
mustbe at least
stainedwith dilutenitric acidto revealgrowthbands. as largeasthe maximumvalueof •4S•2s(Ohmoto,
Boththe crystalsin Figure 9 displaylargevariations 1972),and it is the •34Szs
of the solutionthat reflects
in their sulfur isotopiccompositions,suggesting
rel- the sulfurisotopiccompositionof the sourceof sulfur
atively large changesof the sulfurisotopiccomposi- in the hydrothermalsolutions.Therefore, the isoto-
tions of the ore-forming solutionsduring crystal
growth.
26
Variation of •348in the paragenesis
Figure 10 showsthe sulfur isotopiccompositions 22
of the sulfidesas a function of the paragenesis.
Clearly, the different generationsof sphaleriteand
galenaestablishedearlier from the textural observa-
tionsalsohavedifferentrangesof sulfurisotopiccom-
position.Early dark sphaleriteis isotopicallyheavier
than later pale sphalerite,and cuboctahedral galena
is isotopicallyheavier than later cubic galena. The
bladed marcasitedepositedbetween periodsof de-
positionof cuboctahedraland cubic galenais isoto-
pically lighter than any of the galena associated
with it.
The sulfurisotopicdata in Figure 10 alsoshowthat
different sulfide mineralsare in sulfur isotopicdis- Dark Cuboct.Mc Cubic Pale Cp
equilibrium. In many other base metal sulfide de- Sp Gn Gn Sp
positsthe •34Svaluesof the sulfidesdecreasein the PARAGENESIS
order pyrite, sphalerite,chalcopyrite,galena (Rye FIG. 11. The sulfur isotopiccompositionsof HaS in solutions
and Ohmoto, 1974), consistentwith sulfur isotopic that would be in isotopicequilibrium at 150øC with the sulfides
equilibrium between the sulfides.Yet in the Buick of Figure 10.
pieallyheavycuboctahedral galenain the Buickmine

requiresan isotopicallyheavy sourceof sulfur with 280
SOUTHEAST MISSOURI
LEAD DEPOSITS ß
a •s4Svalue of at least26 per mil. BARITE-LE,M:I OEPOSITS '1"

24O ,a•LYTIC•L
•Cl,,• I
The earlysphaleritewasclearlynotdeposited from ß
ß
ß
solutions containingH2Sasisotopically heavyasthat 20O
discussed above.However, the textural relationships ße

e• ß
stronglysuggest that at leastsomeof the sulfur(and '•. ..
iron) in the early sphaleriteis derivedfrom the dis- 12.0 e e• :.ß ß ß
ß ß
solution of fine-grained FeS2.The sulfurisotopiccom- 8.0
e• ß ß
positions
of theearlyfine-grained
irondisulfides
have ee : eee
not yet been measured.Whether or not the iron di- 4.O
ß
ß eee
ee
sulfidesare isotopically light, it is likely that while 0.0 ß
theydissolved, metastable sulfur-bearing species such ß
as thiosulfateformed. During disproportionation of -4D

i I I I + I
thiosulfate,kinetically-controlled sulfurisotopicfrae- 205 21.0 21.5 22.0 22,5
tionationsoccur(Agarwalaet al., 1965),which could 2ø•pb/
resultin a decrease
of •a4S,sand a correspondingly
low •s4Sfor the sphaleritecomparedwith later cu- FIG. 13. The lead and sulfur isotopiccompositions
of galena
from the majorleadand barite-leaddepositsof southeast
Missouri
boctahedralgalena not affected by dissolutionof exclusiveof the Viburnum Trend (takenfrom Ault, 1956;Brown,
FeS•. 1967;and Kulp, 1956).
The enormous variationsin •s4S,sthat occurred
during precipitationof galena(Fig. 11) couldbe
attributed to fluctuations of the oxidation state or the Table5. For eachsample,approximately
i to 20 mg
pH of the solutionsduring precipitation,provided of a singlecrystalor grainwassampledwith a needle.
that completeredoxequilibriumexistedin the solu- Partof eachsamplewasusedfor sulfurisotopic anal-
tions (see Ohmoto, 1972, for discussion).However, ysis(Table 4) and the remainderfor lead isotopic
fieldandlaboratory evidence summarized by Ohmoto analysis.
and Rye (1979) suggestthat redoxequilibriumbe- Despitethe very largerangesin the measuredlead
tweenreducedand oxidizedsulfur-bearing species is and sulfur isotopiccompositions, cuboctahedralor
very unlikelyat temperatures lessthanabout200øC. cubicgalenacontainingleadwith any particulariso-
Consequently, it is far morelikely that the enormous topic compositioninvariably containssulfur with a
variationsof •S4SH•s duringprecipitation of galenain predictableisotopiccomposition(Fig. 12). The cor-
the Buick mine reflect variation of the overall sulfur relationbetweenthe lead and sulfur isotopiccom-
isotopiccompositions of the solutions. positions
of galenawaspreviouslyreportedto be lin-
ear (Sverjenskyet al., 1979).However,morerecently
Correlationbetweenthe lead and sulfur isotopiccollecteddata, and comparison with the early data
compositionsof galena for southeast
Missouri reportedby Ault (1956),Brown
of ten samplesof (1967)and Kulp (1956) (Fig. 15), suggestthat the
The lead isotopiccompositions
galenafrom the ViburnumTrend are reportedin correlationhasa nonlinear,possiblyS-shapedchar-
acter. Unfortunately,withoutarbitraryassumptions,
the datain Figures12 and 15 cannotbe plottedto-
getheron a singlediagram becausethe early lead
isotopicanalyses are notconsistent
with the newhigh
precisionanalyses. Nevertheless,
there is a very sim-
ilar correlationapparentin bothfigures.
The correlationin Figure12 consistsof a progres-
sivechangefrom the unradiogeniclead and isoto-
picallyheavysulfurof cuboctahedral galenato the
more radiogeniclead and isotopicallylighter sulfur
of cubic galena.This impliesan overall change
throughtime towardisotopically
lighter sulfurand
more radiogeniclead. However,it doesnot neces-
21.0 2L5 220 22,5 2
sarilyimply monotonicchangesof that kind. Indeed,
aø•pb?ø4pb the intracrystalline
zonationpatternof sulfurisotopic
FIc. 12. The correlationbetweenthe lead and sulfur isotopic compositions in the cuboctahedronof Figure 9 is not
compositions
of galenafrom theBuickand ViburnumNo. 28 mines, monotonic.Further studiesare in progressto unravel
Viburnum Trend, southeastMissouri. the nature of the intracrystallineisotopiczonation
patternsin galenaand their spatialdistributionin the at least two different sources.In the Buick mine, the
Buick mine. isotopicallyheaviestgalenais about21 per mil, sug-
Althoughthe detailed variation with time of the gestingthat •$4SH2 S valueswere as high as 26 to 28
isotopiccompositions of solutionsprecipitatinggalena per mil (assuming that the temperatures of deposition
in the Buick mine are not yet established,the cor- were 150ø and 100øC, respectively).Brown (1967)
relationof the lead and sulfur isotopiccompositions reportedgalenafrom the Old Lead Belt with sulfur
of the galenais believedto have two importantim- isotopiccompositions as heavy as 28 per mil, sug-
plications.First, the correlationand the wide ranges gesting •34SH2
svaluesashighas$$ to $5 permil. The
of lead and sulfur isotopiccompositions cannotbe only likely sourceof sulfur as heavy as 28 to $5 per
attributed to physicochemical processes in a single mil isthe sulfurin evaporites(Ohmotoand Rye, 1979,
solution(e.g., variationsof oxidationstate, pH, or fig. 10.1). The sulfurisotopiccompositions of ancient
temperature, even under conditionsthat only ap- evaporitesvary as a functionof geologicage (Holser
proach redox equilibrium). Such processes could re- and Kaplan,1966),and only evaporitesof Ordovician
suit in a wide range of sulfur isotopiccompositions, or Cambrianage have very heavy•34Svalues,sug-
but they could not causesimultaneousfractionation gestingthat the isotopicallyheavy sulfur in the Lead
of lead isotopes.Therefore, precipitationmust have Belt galenasmay be derivedfrom dissolution of early
taken placefrom many solutionseach of which had Paleozoicevaporites.In the nearby Illinois Basin,
different lead and overall sulfur isotopiccomposi- Ordovicianage evaporiteshave sulfur isotopiccom-
tions. Second,the correlation cannot be explained positionsof 25.6 per mil for the Knox Formation and
simply in terms of a model in which separatelead- 25.5 per mil for the JoachimFormation (Thode and
bearingand sulfur-bearingsolutionsmet by chance Monster,1965). If the suggestion of an evaporitic
at the site of deposition.Separatetransportrequires sourceof sulfur is correct,the ore-formingsolutions
that separate,distant,lead-bearingandsulfur-bearing that transportedlead and isotopicallyheavysulfurto
sourceschangedtheir isotopiccompositions system- the Lead Beltsmay have been sulfate-dominantbe-
atically and independentlyas a function of time. It causedissolution of gypsumfrom an evaporiticsource
is conceivablethat suchchangescould be (indepen- should have released sulfate to the solutions. Alter-
dent) monotonicfunctionsof time. However, in the natively, reductionof sulfatederived from an evap-
caseof sulfur, mostsuchchanges(e.g., sulfatere- orite sourcemay have taken place in the sourcere-
duction in closedor partially open systems)should gion, for example, within a sedimentarybasin,or en
yield progressivelyheavier sulfur isotopiccomposi- route to the final site of deposition.In this casethe
tionsasa functionof time, whereasthe overallchange ore-forming solutionsarrivingat thesiteof deposition
through the paragenesisappearsto be toward pro- might have containedsulfide(asH2Sor HS-) rather
gressivelylighter sulfur. In addition, as discussed than sulfate.
above,the changeswithin the cuboctahedral stageof The lowestvaluesof fia4S of galenafrom the Buick
the paragenesis are notmonotonic.In the caseof lead, mine are about+0.9 per mil, suggesting that the sul-
it might be expectedthat a singlesourcewould pro- fur isotopiccomposition of H2S in the ore-forming
duce progressivelymore radiogeniclead with time solutionwas as low as +5 per mil at 150øC. This is
by radioactivedecayof uraniumand thorium.How- significantlylower than the sulfur isotopiccomposi-
ever, recent ion microprobemeasurementsof the in- tions of most evaporites(Ohmoto and Rye, 1979),
tracrystallinelead isotopiczonationof a cuboctahe- implying that the sourceof this sulfur was not eva-
dronof galenafromtheBuickmineshowa progressive poritic. It was more likely reduced sulfur from dia-
changetoward lessradiogeniclead with time (Hart genetic pyrite, petroliferousmaterials,or crystalline
et al., 1981). Consequently,it seemsmuch simpler igneousbasementrocks. The associatedextremely
to accountfor the correlationand the wide rangesof radiogeniclead could also have been derived from
lead and sulfurisotopiccompositions by transportof any of thesesources.
the lead and sulfurtogetherin many different solu- The lead isotopicanalysesreportedin Table 5 and
tions with different isotopiccompositions, some of Figures12 and 15 confirm the similarity betweenthe
whichmay havebeenmodifiedby interactionswith Viburnum Trend, the Old Lead Belt, and the Central
the aquifer(s) and/or the host rocks at the site of Missouribarite-leaddistrict noted by Doe and De-
deposition. levaux (1972). The latter concludedfrom a lead iso-
topic study of ore and possiblesourcerocks in the
Sourcesof sulfur and lead southeastMissouridistrict that the upper Cambrian
The solutionsthat depositedgalena in the Buick Lamotte Sandstone, which underlies the Bonneterre
mine had sucha wide rangeof isotopiccompositions Formation, could have been the source of the lead
thattheyprobablyacquiredbothsulfurandleadfrom in the orebodies. However,asnotedby Sverjensky et
al. (1979), the correlationbetweenthe lead and sulfur TABLE6. Modelsfor the Transportationand Precipitationof
BaseMetalsand Sulfur in Mississippi
Valley-Type Deposits
isotopiccompositions of galenasuggests that the La-
motte Sandstone is not the sole source of the lead in
Transportation
of ore-forming Mechanismof precipitation
the ores.Trace amountsof galena in the Lamotte constituents of ore
Sandstonehave the samerange of isotopiccomposi-
tions as the ores (Doe et al., unpub. data), which I. Basemetals transported a. Mixingwith solutions
stronglysuggests that the LamotteSandstone wasan by solutionswithout containing H2S
any significantsulfur b. Replacementof diagenetic
aquifer for the ore-formingsolutionsand that at least content iron disulfides
some of these solutions achieved their final lead iso- c. Thermaldegradationof
topic compositions
before entering the Bonneterre organiccompounds
Formation. If the Lamotte Sandstone was the most releasingreducedsulfur
importantaquifer for the ore-formingsolutions,it is II. Basemetals transported a. Reductionof sulfateby
highly probablethat the first solutions
to travel sig- togetherwith sulfatein reactionwith organic
nificant distances in the Lamotte Sandstone derived the same solutions matter or methane
at least some lead from the sandstone. This lead would b. Reductionof sulfateby
reaction with iron-
have been relatively unradiogenicbecause,in the bearingminerals
paragenesis,the mostunradiogeniclead was precip-
III. Basemetalstransported a. Increaseof pH
itated in cuboctahedralgalena (Sverjenskyet al., togetherwith reduced b. Dilution
1979). The sourceof the lead in the cubicgalenasis sulfur in the same c. Decreaseof temperature
notknown.However,thestudyby Doe andDelevaux solutions
(1972) and more recentwork by B. R. Doe (unpub.)

imply that it was not derived from the Bonneterre
Formation,or from any of the youngerupper Cam- lutionat lowandapproximatelyequalconcentrations.
brianunitsor the localPrecambrian crystallinebase- The causeof precipitationin thiscasecouldbe neu-
ment. tralization(Helgeson,1970),cooling,or dilution(An-
derson, 1978).
Transportation and Precipitation of the Base In the case of the Buick mine, the textural and
Metals and Sulfur
isotopicdata reportedaboveare consistent
only with
Over the last100 yearsmany different mechanisms the third model in Table 6--the reduced sulfur
havebeenproposedto accountfor the transportation model. In particular, the textural evidence for re-
and precipitationof basemetalsand sulfur in Mis- petitive precipitationand dissolutionof galena and
sissippiValley-typedeposits(seereferencesin the in- sphaleriteis very simplyexplainedaccordingto the
troduction).Table 6 containsa summaryof thesein reduced sulfur model because the state of saturation
termsof threesimplealternativemodels.According of the ore-formingsolutions(with respectto sulfide
to the first model, which can be called a mixing minerals)couldhave changedwith changesin their
model, it is suggestedthat basemetalswere trans- temperature,pH, or oxidationstate. By contrast,re-
portedin one solution,that sulfidewas transported petitive precipitation and dissolutionof the base
separatelyin anothersolutionor assourgas,and that metalsulfides is notsimplyexplainedif precipitation
precipitation took place where the two solutions occurredbecause separatemetal-bearingand sulfide-
mixed (Anderson1975, 1977;Beales,1975;Bealesand bearingsolutionshappenedto mix at the site of de-
Jackson,1966;Davis, 1960, 1977). Other theoriesin- position.If, as seemslikely, the concentrationsof
cludedin this modelsuggestthat basemetalswere metal in the metal-bearingsolutions and sulfurin the
transportedto the site of depositionwhere they en- sulfur-bearingsolutionswere rather different, then
countereda sourceof reducedsulfur suchas diage- mixingthe two solutions wouldresultin precipitation
neticironsulfides,or sulfurreleasedby thermaldeg- of metal sulfide until the scarcer of the metal or the
radation of petroliferousmaterials(Skinner, 1967). reducedsulfur were exhausted.At this stage,the
Accordingto the secondmodel, a sulfate reduction mixture shouldstill containa significantconcentra-
model, it is suggested that basemetalswere trans- tion of metal or sulfur, in equilibrium with metal
portedin solutionstogetherwith sulfate(ratherthan sulfide,dependingonwhichonewaspresentin excess
sulfide)and that precipitationtookplacebecause of beforemixing.Undertheseconditions, because metal
a reactionduring which sulfate was reduced to sul- sulfidesare soinsoluble(Fig. 14), large decreases of
fide,possiblyby oxidationof organicmatteror meth- pH or increasesof temperaturewould be required
ane (Barton,1967).Accordingto the third model,a to causesignificantdissolutionof the metal sulfide.
reduced sulfur model, base metals and reduced sulfur Consequently, a mixing model is unableto explain
(as H2S) were transportedtogetherin the sameso- the texturalevidenceof repetitiveprecipitationand
about 0.52 to 10.61 wt percentorganiccarbon.By

I • I ' I • I contrast,
the organiccarboncontentof unmineralized
t50 -- 't ,NEUTRAL
pH/ -- BonneterreFormation is only 0.04 to 0.137wt percent
(Sverjensky,1980).It is, therefore,very unlikelythat
significantamountsof the basemetal sulfidesin the
Buick mine were precipitatedas a resultof sulfate
reductioncoupledwith oxidationof organiccarbon
from the host rocks.
Sulfatereductionby methaneis alsoan inadequate
mechanism,but for a different reason.The equilib-
rium for the reaction
CH4(a
) q-SO•• q-Pb+• = PbS+ CO•(g)
+ 2H•O(t)
I I I I I I I
lies so far to the right-handside that no significant
4 5 6 7
amountof reversalcouldbe expectedundergeolog-
icallyrealisticconditions. For example,at 100øC,100
barstotalpressure, fcm = fco2,anda,2o= 1, the mass
t•01 •EUTRAL
pH._ actionexpression for the aboveequilibriumis
al,b•X aso4-•
= 10-•'a
(calculatedusingSUPCRT of Helgesonet al., 1978,
1981), which impliesthat no significantamountof
lead and sulfatecould coexistin a solutionin equi-
librium with galena (cf. the very similar resultcal-
culatedby Barton,1967),evenif a largeincreaseof
the fugacityof CO• relativeto methaneoccurred.
Therefore,no significantamount of dissolutionof
galenais likely to occurby reversalof the reduction
• I ISATU•ATIO
•TE • !
N• •Zd•.O5
•1
m?lal)
• I/
/ reaction.Consequently,the textural evidenceof re-
4 5 6 7 petitiveprecipitationanddissolution of galenacannot
be accountedfor by a sulfate reduction model in-
pH
volvingmethane.
Fro. ]4. The stoichiometric
solubilities
of galenaand sphalerite In the BonneterreFormation,the only othergeo-
solutioncontaining2.8 molalNaCI and 0.64 molalCaCI• at chemically abundant element which has multiple
pre•urescotresendingto the liquid-vast equilibriumfor water, oxidationstatesis iron. A possiblereactionbetween
calculat• usingHelgesonet al. (]98]). iron and sulfate is
8Fe+• + SO;-• + Pb+• + 8H•O --•

dissolutionreportedin this paper.It is alsounableto
explainsimplythe sulfurand lead isotopicdata. The 4Fe•Oa + PbS + 16H +.
latter imply that sulfur and lead were transporte d
togetherin the samesolutions to the siteof deposition Sulfatereductionby oxidationof ferrousiron hasnot
(Sverjenskyet al. 1979), which supportseither the previously beensuggested asa causeof precipitation
reduced sulfur model or the sulfate reduction model. of MississippiValley-typesulfidedeposits,probably
The sulfate reduction model is discussed next. becauseore-stagemagnetiteor hematiteare never
Accordingto the sulfate reductionmodel, base found in thesedeposits.In the BonneterreFormation,
metalsand sulfatewere transportedtogetherin the extremelyfine grained iron oxidesare an important
samesolutions.Precipitationoccurredwhen the sul- cause of the brown color of the Bonneterre Formation
fate was reducedto sulfide,by a reactionin which (Sverjensky, 1980). However,the formationof these
someothercompoundwasoxidized.Sulfatereduction ironoxidesprecededthe earlieststageof sulfidemin-
by oxidationof organiccarbonin the hostrockswas eralization,and therefore sulfate reductionby oxi-
an importantmechanismof basemetal sulfidepre- dationof ferrousiron cannotbe responsible for pre-
cipitation for the stratiform lead-zinc depositsat cipitationof the basemetalsulfides. In addition,the
McArthur River, NorthernTerritory, Australia(Wil- acid soluble iron content of unmineralized Bonne-
liams, 1978). These depositsoccur in organic-rich terre Formation is far too low to causeprecipitation
blackshalesthat priorto the mineralizationcontained of any significant amountof metalsulfideaccording
of the abovereaction(Sveriensky, TABLE7. ActivityCoefficientsof AqueousSpeciesin a Solution

to the stoichiometry
Containing2.8 molalNaCl and 0.64 molalCaC12
1980)whichrequireseightmolesof Fe+2for precip-
itation of one mole of lead as galena. log 3q
In summary,the data reportedin thispaperon the
southeast Missouri lead district are all consistent with Temperature(øC)
and indeedrequire explanationby a reducedsulfur Species 50 100 150

model,accordingto which the basemetalsand re- Pb +2 -0.87 -1.27 -1.75
ducedsulfurwere transportedtogetherto the siteof PbCI + -0.11 -0.078 -0.11
depositionin the samesolutions.This conclusionwas PbC1-3 -0.49 -0.36 -0.30
also reachedby McLimans (1977) and McLimans, Zn +2 -0.65 - 1.12 - 1.67
Barnes,and Ohmoto (1980) for the Upper Mississippi ZnCI + -0.004 -0.012 -0.079
Valley district,basedon studiesof the sphaleritestra- ZnCI-3 -0.$8 -0.$0 -0.27
tigraphyandthesulfurisotopiccompositions of sphal- CI- -0.054 -0.095 -0.19
erite and galena.Becauseof all the aboveresults,it
is essential to know how much lead and reduced sul- CalculatedusingHelgesonet al. (in press)
fur or zinc and reduced sulfur hot saline solutions can
carry, and whetherthesequantitiesare sufficientto
form large basemetal sulfideore deposits.Because from Mississippi Valley-typeoredeposits
demonstrate
mineralssuchas galenaand sphaleriteare so insol- that chloride is so abundant comparedto any other
uble, experimentalstudiesof their solubilityhavenot anion in the ore-formingsolutions(e.g., Roedder,
yet yielded unequivocalanswersto thesequestions. 1967) that chloridecomplexingof the basemetals
Consequently, the remainderof thispaperis devoted should be considered the dominant mechanism of
to theoreticalcalculationof the solubilitiesof galena metal transport.
and sphaleriteand evaluationof the reducedsulfur Solubilities
of galenaandsphaleritewerecalculated
model. in thisstudy(Figs.14A and B) asa functionof tem-
perature and pH at pressurescorrespondingto the
Theoretical Calculation of the Solubilities of
liquid-vaporequilibriumof water for a solutioncon-
Galena and Sphalerite and Evaluation of the taining 2.8 molal NaC1and 0.64 molal CaC12(stoi-
Reduced Sulfur Model
ohiometricchlorideion molalitymc•- = 4.1 and ionic
It has long been recognizedthat ore-formingso- strengthI = 4.72). As discussed above,even higher
lutionscouldonly have carried significantquantities salinities(mc•- up to 5.0 molal) are implied by the
of lead, zinc, copper,and iron as complexes,yet the lowestfluid inclusionfreezingtemperatures recorded
type of metalcomplexhasbeencontroversial (Skinner for the southeast Missouri district. In these solutions,
and Barton,1978). The importanceof metal chloride basemetal sulfidesolubilitieswould be greaterthan
complexinghas been establishedby the work of reportedin Figure 14A and B. The methodof cal-
Helgeson(1964, 1969, 1970), Roedder(1967, 1976, culationof the galenaand sphaleritesolubilities was
1979), and Anderson(1978), but until recently metal basedon that of Anderson(1977) but was extended
bisulfidecomplexinghasbeenemphasizedby Barnes to high pH valuesby providingfor HeS/HS- equi-
(1967, 1979) and Barnesand Czamanske(1967). In librium. Sulfatecouldbe presentin suchan ore-form-
the caseof lead, the metal bisulfidecomplexingthe- ing solutionbut it wouldvery likely be in redoxdis-
ory wasdemonstratedto be inadequateby Hamann equilibriumwith the reducedsulfurspeciesover the
and Anderson (1978) and Giordano and Barnes temperaturerange of interest (Ohmoto and Rye,
(1979), who concludedfrom experimentalstudiesthat 1979) and, therefore, was not consideredin Figure
ore-formingsolutions at temperatures lessthan200øC 14A and B. Both NaC1 and CaCle were assumedto
with total dissolved sulfur contents of less than about be completelydissociated(at 150øC the true ionic
1 molal (82,000 ppm) do not transportsignificant strengthI = 4.58 shiftsthe calculatedsolubilities by
quantitiesof lead aslead bisulfidecomplexes.Similar only0.1 of a pH unit according to the dataof Helge-
conclusions may be drawn for zinc bisulfidecom- son,1969,for the formationof the complexNaClø).
plexing(e.g., McLimans,1977) and for copperand Equilibrium constantsfor the formation of metal
iron bisulfidecomplexing(at least for solutionsin chloridecomplexes weretakenfrom Helgeson(1969),
equilibriumwith the assemblage chalcopyrite-pyrite- andsolubilityproductconstants for galenaandsphal-
bornRe,Crerar and Barnes,1976). Therefore, it seems erite werecalculatedusingSUPCRT(Helgeson et al.,
reasonableto concludethat metal bisulfidecomplex- 1978 and in press).The activity coefficientsof the
ing need no longerbe consideredsignificantfor the aqueousspecieswere calculatedusingthe equations
genesisof MississippiValley-type ore deposits.In- and data summarizedby Helgesonet al. (in press)
deed, the chemical compositionsof fluid inclusions and are listedin Table 7. The activity coefficients of
all singlychargedmetalchloridecomplexes werecal- thesoutheast

Missouri
district,isotopic
studies
suggest
culatedusingeffectiveelectrostatic radii generated thatthe LamotteSandstone
wasa far moreimportant
from entropyradiuscorrelationplots(Helgesonand aquiferfor the ore-formingsolutions than limestones
Kirkham, 1976) and standardpartial molal entropies or dolostones. In addition,any estimateof the max-
of the complexes.The latter were calculatedfrom imum likely partial pressureof CO2 of the ore-form-
entropies of dissociation
estimatedusingthe method ing solutionsis highly uncertain.In this study, a
of Helgeson (1969).Activitycoefficients
of theneutral maximum concentration of dissolved CO• (as
metal chloridecomplexes were assumedto be equal H•CO•/•pp•) of 0.05 molalwasusedto plot the curve
to one, and thoseof the doublychargedcomplexes for saturationwith respectto dolomiteshownin Fig-
were assumedto be equal to the activity coefficients ure 14A and B, becausechemicalanalysesof fluid
of the respectivemetal ions. inclusionsfrom Mississippi Valley-typedeposits sug-
It is evidentfrom Figure 14A and B that low, but gest maximum likely bicarbonateconcentrationsof
by no meansinsignificant,concentrations of base about$,000 ppm (Hall and Friedman, 1965;seealso
metalsandreducedsulfurcanbe transported together McLimans, 1977, who found 0.02 to 0.14 molal car-
at temperaturesbetweenabout 100ø and 150øC and bon dioxidein fluid inclusions from the Upper Mis-
at pHslessthan neutral.For example,at only onepH sissippiValley district).Clearly,evenif the ore-form-
unit below neutral at 100øC, concentrationsof 6 •m ing solutionsin the southeastMissouridistrict had
Pb (1.2 ppm) or 40 #m Zn (2.6 ppm) couldbe trans- been in equilibrium with dolomite, at 100øC their
ported with equivalent amountsof reduced sulfur. pH couldhavebeenaslow as4.4 yet still within two
At 150øC and at one pH unit below neutral 90 •m unitsof neutrality.
Pb (18 ppm) or 760 #m Zn (50 ppm) with equivalent The pH of the ore-formingsolutionsthat traveled
amountsof reducedsulfur could be transported.At to Mississippi
Valley-typedepositshas alsobeen es-
pH's more than one unit belowneutralevenhigher timatedby assuming equilibriumwiththeassemblage
concentrations of lead or zinc and reduced sulfur can K-feldspar-sericite-quartz(Barnes, 1979; Giordano,
be transportedtogether.The galenasolubilitiesre- 1978; McLimans,1977). However,the only descrip-
portedin Figure 14 are aboutthreetimeslargerthan tionof the association K-feldspar,sericite,and quartz
thosecalculatedby Anderson(1975), and about five in a Mississippi Valley-typedeposit(Heyl et al., 1964)
times larger than those of Giordano and Barnes merely has implicationsfor the pH of the solutions
(1979), becauseof the higher NaCI concentration in the wall rock,not for the pH of the solutions that
usedin this studyand different methodsof calculat- precipitatedsphaleriteand galenain the adjacent
ing activitycoefficients.However,for the purposeof veins,or for the ore-formingsolutionsthat traveled
evaluatinga reducedsulfur model thesedifferences to the siteof deposition.
are not important. Far greater uncertainties are as- The chemistryof potentialore-formingsolutions
sociatedwith estimationof the actualpH of the ore- buried in sedimentarybasinssuchas the Gulf Coast
forming solutionsand the concentrations of metals Basin(Carpenter,et al., 1974; Hanor, 1979; Kharaka
and sulfurthat mustbe transportedto form geolog- et al., 1980) is alsoa usefulindicationof the pH of
icallyand economically significantbasemetalsulfide MississippiValley-type ore-forming solutions.Al-
ore deposits.It is the contentionof this paper that thoughthe pHs of thesebrinesand of oil field brines
pHs of one to two units lessthan neutral and metal in generalare not yet well established, they can be
and sulfurconcentrations of the orderof 10 •m (about estimatedwherethe mineralogyof the hostrocksand
1 ppm) are realistic estimatesconsistentwith the the chemicalcompositions of the brinesare known.
chemistryof fluid inclusionsand oil field brines,the For example, lead and zinc-rich oil field brines in
mineral assemblages of MississippiValley-type de- CentralMississippi at 155øCand $90 barsin equilib-
posits,and the sizesof the deposits,possible flow rates rium with the assemblage kaolinite-muscovite-quartz
of the ore-formingsolutions, and the amountof time (Carpenteret al., 1974) shouldhave a pH of about
required to form a typicaldeposit. 4.$ (D. A. Sverjensky,in prep.). Geopressured brines
Attemptsto estimatethe pH of the ore-forming in the Upper TexasGulf Coastat 150øC and about
solutions that traveledto the siteof deposition have 800 barshave pH's of about5.4 (D. A. Sverjensky,
beenmade usingseverallinesof evidence.Anderson in prep.) and possiblyas low as 4.1 (Kharaka et al.,
(197•3,1975,1977)assumed that the ore-formingso- 1980).Theseexamplesdemonstratethat at leastsome
lutions must have traveled significantdistances deeplyburiedbrinesin sedimentarybasinshavepH's
throughlimestones and/or dolostones, that theywere significantly lessthan neutral.Therefore,the pH's
in equilibriumwith calciteand/or dolomite,and that requiredby the reducedsulfurmodelare not geo-
themaximumlikelypartialpressure of CO2wasabout logicallyunreasonable. They are consistent with all
I bar, from whichhe inferredthat the minimumpH availablefluid inclusion and mineralogical datafrom
of the solutionswasabout 5.7 at 100øC. However, in Mississippi Valley-typedeposits,aswell asthe chem-
ical compositions
of oil field brines buried in sedi- amountsof reducedsulfur) couldbe transportedby
mentary basins. ore-formingsolutions in the southeast MissouriLead
Even greater uncertaintysurroundsattemptsto district.Assumingthat the total amountof lead de-
estimate the actual concentrations of base metals and positedin southeast Missouriis about$2 X 100kg
sulfur in the solutionsfrom which Mississippi Valley- (Davis,1977),this rangeof concentrations impliesa
type depositswere precipitated,despitestatements total volumeof ore-formingsolutionsof about2,100
to the contrary in the literature. Barnesand Cza- to $2,000kms.Althoughsuchvolumesare enormous,
manske(1967)and Barnes(1979)statedthat the min- they couldhavebeencontainedin sedimentarybasins
imum concentrationof lead or zinc necessary to form the size of the Gulf Coast or Illinois Basins. In ad-
a majorore depositis about10 ppm. Anderson(1975, dition,assuming a flow rate of 1 t•/s alongthe length
1975, 1977) suggested a minimum of 2 ppm lead. of the Viburnum Trend across an area of about 100
One of the most useful estimates is that of Roedder m by 10 km (similar to that of the Lamotte Sand-
(1960, seealso1976), who inferred from the absence stone),the wholesoutheast Missourileaddistrictcould
of sulfidedaughtercrystalsin fluid inclusions that the haveformedin a periodof 67,000to 1,000,000years.
maximum likely concentrationsof base metals are Therefore, even concentrations of lead as low as 1
between about i and 1,000 ppm. Direct chemical ppm in the ore-formingsolutions are sufficientlylarge
analysisof the metal and sulfurcontentsof fluid in- to form giant galena-richore districts.
clusionshasnot yet resolvedthe problembecauseof In summary,the reducedsulfur model suggested
difficultiesassociatedwith analysisof suchextremely earlier to accountfor the textural and isotopicdata
smallquantitiesof material (e.g., seethe discussion reportedin this paper on the Buick mine is strongly
in Czamanskeet al., 1965). Nevertheless,such anal- supportedby theoreticalcalculationsof the solubili-
ysesdo place useful maxima on the concentrations ties of galena and sphaleriteand is consistentwith
involved. For example, McLimans (1977) reported geologicallyreasonableestimatesof the pH and ac-
about250 ppm zincin fluidinclusions in galenafrom tivity of carbondioxidein the ore-formingsolutions,
the Upper Mississippi Valley district,and Czamanske possibleflow ratesof the solutions,and the amount
et al. (1965)andPinckneyand Hafty (1970)reported of time required to form the southeastMissourilead
10 to 1,040 ppm zinc in fluid inclusionsin fluorite district.
from the Illinois-Kentuckydistrict.That thesevalues Conclusions
are maximais demonstratedby the work of Tsui and
Holland (1979), who used a laser microprobetech- 1. The texturaland parageneticdata for bothgal-
nique to establishthat the upper limit of the copper ena and sphaleritein the Buick mine, southeastMis-
contentof a fluidinclusionin a sampleof quartzfrom souri,stronglysuggest that thesemineralswere pre-
Creede, Colorado,was about i to 20 ppm, much cipitated and dissolvedrepetitively during ore
lowerthan 60 ppm, whichwasthe lowestvaluemea- formation. Similar textural evidence has been de-
suredby Czamanskeet al. (1965) usingcrushingand scribedfor galenafrom otherminesin the Viburnum
leachingtechniques.Chemicalanalysesof the total Trend, suggesting that repetitive precipitationand
dissolved sulfurcontentsof fluid inclusions give max- dissolution of galenawasprobablyan importantpro-
imum valuesof about 1,000 ppm (Roedder,1976) to cessduring the formation of the entire Viburnum
4,000 ppm (McLimans, 1977). Trend. In the Buick mine, the main period of dis-
Clearly,our presentknowledgeof the actualcon- solutionof galenaappearsto coincidewith precipi-
centrationsof base metals and sulfur in Mississippi tationof marcasiteand may have beencausedby a
Valley-typeore-formingsolutionsis limited to mea- pH decreaseassociated with precipitationof the mar-
surementsof maximumlikely concentrations. Mini- casitefrom solutionsthat were supersaturatedwith
mum likely concentrations are not yet measureable. respect to pyrite.
However,they can be inferred from estimatesof the 2. The ore-formingsolutionsin the Buick mine
total volumeof solutionsrequired to form any par- wereundersaturated with respectto dolomiteduring
ticulardeposit,likelyflowrates,andgeologically rea- mostof the ore-formingprocess, but locallythey be-
sonableestimatesof the length of time over which camesaturatedand evensupersaturated with respect
the depositformed (seeRoedder, 1960, 1976, for a to dolomitewhile minor amountsof late pale sphal-
summary of the relationshipsbetween these vari- erite and someof the cubicgalenawere precipitated.
ables).It shouldbe emphasizedthat becausethese The stateof saturation(with respectto dolomite)of
estimatesare highly uncertainand geologicallyrea- the ore-formingsolutions travelingto the siteof de-
sonablerangesmustbe suggested, thereis no unique positionis not known; they may have becomeun-
minimum metal and sulfur concentration. For ex- dersaturatedat the site of depositionsimply by
ample, it wasestimatedabovethat concentrations of cooling.
about i to 18 ppm lead (togetherwith equivalent $. Fluid inclusionsin late quartzcrystalscoprecip-
itatedwith chalcopyritein the northBuickareahave helpedand encouraged my effortsto understandthe

homogenization and freezingtemperatures in essen- formationof the Buickorebodies. Clif Jordan(for-
tially the samerangesreportedby otherworkersfor merlywith AMAX) verygenerously sharedhisstudy
sphalerite.The fluid inclusiondata suggest that the of theBuickorebodies
andhelpedmy studyin every
ore-formingsolutionsin the Viburnum Trend were possible
way.Mostof thispaperistakendirectlyfrom
probablyat temperatures in the range105ø to 141øC my doctoraldissertation
supervisedat Yaleby D. M.
(assuminga maximum likely pressureof about 125 Rye and B. J. Skinner,whosesupportand advice I
bars)and wereextremelysaline,containingabout4 greatlyappreciate.The research wasfundedmainly
to 5 molal chlorideion. Considerationof typical by NSFGrantEAR-18715(D. M. Rye).I alsogreatly
chemicalanalysesof fluid inclusions
from other Mis- value discussions
with and help from R. A. Berner,
sissippiValley-typedepositssuggestthat the maxi- P. M. Orville, JohnRodgers,and K. K. Turekian of
mum likely concentrationof dissolvedCO2in the ore- Yale,JohnWaltherof Northwestern University,and
forming solutionswasabout0.05 molal. For concen- H. C. Helgesonof the Universityof California at
trationsashighasthis,theore-formingsolutionscould Berkeley.
have had pH's about two units lessthan neutral and
stillhavebeenin equilibriumwith dolomiteor calcite. October31, 1980;April 4, 1981
4. The sulfur isotopiccompositions of sphalerite
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2the Origin of A Mississippi Valley-Type Deposit in The Viburnum Trend, Southeast Missouri

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2the Origin of A Mississippi Valley-Type Deposit in The Viburnum Trend, Southeast Missouri

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EconomicGeology

Vol. 76, 1981, pp. 1848-1872

The Origin of a MississippiValley-Type Deposit in the Viburnum Trend,

Introduction viewedby Bastin,1989;Heyl et al., 1974;Ohle, 1959,

versial.MississippiValley-type depositscontain enor- TABLE1. Upper CambrianStratigraphicSuccession

sippi Valley mineralizationdistricts--the southeast Derby-DoeRun Formation 40 Dolostone

The MississippiValley-type depositsin southeast

orebodies in the Old Lead Belt and other subdistricts

gestthat the variableand calcareniteunits (Table 1)

".__-.-\ F•½;.$. Map of the Buickorebodies(after Rogersand Davis,

belongto a shelf facies,the reef unit belongsto a

Cubic Gn Clusterslining Gn on sp Sp beneathor Not observed Qtz coatsGn Euhedralrhombs

Dark Sp Clusters Pale sp Ms coats Occurs on and DI occurs on and

Clusters of Ms coated by qtz Ms coatsdl

Qtz Clustersof Qtz grew on and

Cp Not observed Cp on cubicgn Cp on sp Not observed Cp on ms Cp includedin Cp on dl

Pv Not observed Fine-grainedinclusions

Ms luciusions of •ng and ms rims Veinletsand inclusions

Cp Rimsof cp aroundgn Dendritic cp in sp Raresubhedralcrystalsin Cp inclnsionsin ms

Sg Rimsof sgaroundgn Rimsof sgaroundsp Rare small disseminated Sg inclusions

Qtz Euhedralqtz in gn Euhedralqtz in sp Euhedralqtz in spatry Euhedralqt7 in ms

mon:orangeor orange-brown,red-brownor purple- Centerof crystal 96.6 2.4 0.5

the samepredominantcolortype or sequenceof col- Edgeof crystal 97.2 1.6 1.0

The causeof the intenselycoloredzonesin the dark

detectionusingthismethodwasabout0.2 wt percent Edge of crystal 99.2 1.2 0.3

contentof the sphaleriteif chargetransferis taking

GALENA becausethe temperaturefell, becausethe solubility

equilibriumfor water. The valuesof the equilibrium rium betweensulfateandsulfidesuggested by Barton

TABLE4. Sulfur IsotopicData for the Buick Mine

Locality Analysis $s•S Locality Analysis $a4S

the cuboctahedral galena,wasstudiedin an east-west are beingdifferentiatedby a moredetailedstudyof

pieallyheavycuboctahedral galenain the Buickmine

a •s4Svalue of at least26 per mil. BARITE-LE,M:I OEPOSITS '1"

solutions containingH2Sasisotopically heavyasthat 20O

discussed above.However, the textural relationships ße

theydissolved, metastable sulfur-bearing species such ß

as thiosulfateformed. During disproportionation of -4D

(1972) and more recentwork by B. R. Doe (unpub.)

about 0.52 to 10.61 wt percentorganiccarbon.By

8Fe+• + SO;-• + Pb+• + 8H•O --•

of the abovereaction(Sveriensky, TABLE7. ActivityCoefficientsof AqueousSpeciesin a Solution

and indeedrequire explanationby a reducedsulfur Species 50 100 150

all singlychargedmetalchloridecomplexes werecal- thesoutheast

itatedwith chalcopyritein the northBuickareahave helpedand encouraged my effortsto understandthe

Bickford,M.D., and Mose,D. G., 1975, Geochronology

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