EconomicGeology

Vol. 84, 1989, pp. 2139-2154

The Genetic Relationshipbetween Upper MississippiValley District

Lead-Zinc Mineralization and Minor Base Metal Mineralization
in Iowa, Wisconsin, and Illinois
KEITH B. KUTZ AND PAUL G. SPRY

Departmentof Geologicaland AtmosphericSciences,

253 ScienceI, Iowa StateUniversity,Ames,Iowa 50011

Abstract

Minor basemetal occurrencesare presentin Paleozoicdolomites,and to a lesserextent,

in slatesandsandstones in a broadzonesurrounding the mainUpper Mississippi Valley zinc-
leaddistrictin Iowa, Wisconsin, andIllinois.Theseoccurrences are of interestbecausethey
maybe remnantsof fluidpathwaysof UpperMississippi Valleyzinc-leadmineralization. Out-
lyingbasemetaloccurrences containmainlypyrite,marcasite, sphalerite,galena,andcalcite;
they occurin a variety of formsincludingverticalveins,gashveins,disseminated breccias,
vuglinings,andpaleokarstreplacementbodies.Two paragenetic typesof mineralizationare
evident:occurrences in whichsulfidesare generallyearlyandcalciteis late, andoccurrences
in whichcarbonate(eithercalciteor dolomitebut predominantly calcite)is earlyandsulfides
are generallylate.Similaritiesexistamongmineralogy, geologicsetting,andsomegeochemical
aspectsof the main Upper Mississippi Valley districtand outlyingoccurrences. However,
paragenetic,fluid inclusion,andstableisotopedataindicatemajordifferencesin the genetic
historyof the outlyingoccurrences.
Fluid inclusionhomogenization temperatures for outlyingsphaleriteandcalciterangefrom
37.8 ø to 115.8øC. These temperaturesare generallylower than thosereported previously
for thesemineralsfrom the mainUpper Mississippi Valley deposits(46ø-220øC). Although
measuredsalinitiesfor inclusions in sphaleritein outlyingoccurrences (15.6-23.8 equivwt
% NaC1)are similarto thosefor sphaleritefrom the mainUpper Mississippi Valley district
(19.6->23 equivwt % NaC1),salinitiesfor inclusions in calcitein outlyingoccurrences (5.1-
18.1 equiv wt % NaC1)are considerablyhigher than thosedeterminedfor calcite(4.8-5.1
equivwt %) from the mainUpperMississippi
Valleydistrict.The /•a4Svaluesfor outlying
sulfatesrangefrom21 to 31 per mil (CDT) andaresimilarto thoseof the mainUpperMississippi
Valleydistrict(22-36%0).Overallvaluesof/•a4Sfor sulfides
fromoutlyingoccurrences
range
from -22 to +36 per mil and contrastto that obtainedfrom "pitch and fiat" deposits(6-
30%0)and gashveins(approximately 1%0)from the mainUpper Mississippi Valley district.
Althoughsulfidesfromthisdistrictformedfromreducedconnatewatersulfate,the widerange
in sulfurisotopedatawascausedby the ore-formingfluid reacting,to varyingdegrees,with
isotopically
lightdiagenetic
pyrite.Valuesof/•aC and/•80 foroutlyingcalcites(-9 to +5%0
(PDB),and21-29%0(SMOW),respectively)tend to be heavierthancalcitesfrompitchand
fiatdeposits
in the mainUpperMississippi
Valleydistrict(/•laC= -13 to -2%0;/•180-- 17-
23%0).The/•l•Ovaluesforfluidinclusions
in outlyingmineralization(-8 to +6%0)aresimilar
to thoseobtainedfromthe mainUpperMississippi Valleydistrictmineralization(-5 to 6%0);
however,/•Dvalues(-95 to -20%0) arelighterthanvalues(-47 to +2%0)for the maindistrict.
Theseisotopicvaluessupporta connateseawatersourcefor the mineralizingfluidsfromboth
areas.Sulfur,carbon,andoxygenisotopedatasuggest that someoutlyingmineralization was
more stronglyinfluencedby local diageneticprocesses than by processes that formedthe
mainUpper Mississippi Valley deposits.

Introduction that formedlarge Mississippi Valley-typedepositsin

northernArkansas andthe Tri-Statedistrict.Similarly,
A NUMBER of investigationshavecenteredon the or- fluid inclusionstudieson trace occurrencesof sphal-
igin of minor basemetal occurrencesin the North erite in KansasandMissouriby CoveneyandGoebel
Americanmidcontinentareabecausethey maybe re- (1983), Coveney et al. (1987), and Goebel et al.
latedgeneticallyto largeMississippiValley-typede- (1988) suggested thatfluidsresponsible for their for-
posits.On thebasisof fluidinclusion
data,mineralogy, mationwere similarto fluidsthat formed large Mis-
and stratigraphic relationships,Leach (1979) sug- sissippi Valley-typedepositsin the Midwest(e.g.,Tri-
gestedthat minorbasemetaldepositsin centralMis- State,southeastern Missouri,northernArkansas). The
souri may have been derived from the samefluids most attention, however, has been directed toward

0361-0128/89/1014/2139-1653.00 2139

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by Society of Economic Geologists, Cesar Ricardo Vargas
 2140 K. B. KUTZ AND P. G. SPRY

understandingthe geneticrelationshipbetween Up- The presentcontributionusesstableisotope(S, C,

per MississippiValley districtmineralizationand mi- O, and H) and fluid inclusiondata (1) to determine
nor base metal occurrencesin Iowa, Wisconsin, and the geochemicalconditionsunder which minor oc-
Illinois(Heyl et al., 1959; Heyl andWest, 1982; Gar- currencesin Iowa,Illinois,andWisconsin formed,(2)
vin, 1984, Coveney et al., 1987; Garvin et al., 1987; to identifypossible sources of ore-forming constitu-
Garvinand Ludvigson,1988; Ludvigsonand Millen, ents (i.e., fluids,carbon,sulfurand metals),and (3)
1988; Whelan et al., 1988). Heyl et al. (1959) and in conjunctionwith availablegeologic,mineralogic,
Heyl andWest (1982) proposedthat theseminoroc- andparageneticinformation,to evaluatewhetherthe
currencesmay be remnantsof fluid pathwaysfrom outlying occurrencesare cogeneticwith the main
main Upper MississippiValley mineralization.Simi- Upper MississippiValley district ores as has been
laritiesin form, mineralogy,paragenesis, sulfuriso- proposedpreviously.
tope compositions, andlead isotopesystematics have
been usedpreviouslyto suggestthat minoroutlying Geologic Setting
occurrenceswere cogeneticwith the main district The depositional andtectonichistoryof the Upper
mineralization.The significance of this suggestionis MississippiValley district has been describedby
that studiesof the minor sulfideoccurrencesmight Bunkeret al. (1985) in termsof Sloss's(1963) clas-
providevaluabledatawhich canbe usedto constrain sificationof the sedimentaryrecord of cratoniccon-
interpretationsof the size,geometry,hydrologic,and tinentalinteriors.Heyl et al. (1959) andHeyl (1968)
geochemicalnature of the fluid systemswhich pre- have provided details of the structuraland strati-
cipitatedboththe mainUpperMississippi Valleyore- graphicrelationsof mineralizationin the mainUpper
bodies and the outlying occurrences(Garvin et al., MississippiValley district.Figure i showsthe gen-
1987). eralizedstratigraphicnomenclaturefor the outlying

Pennsylvanian

Mississippian

Upper Devonian

Middle Devonian

Silurian

Ordovician

Cambrian

Precambrian

D fault or
u fault zone

0 50 km

FIG. 1. Generalizedbedrockgeologicmap of part of the Upper Mississippi Valley with the location
of outlyingUpper Mississippi Valley occurrences(compiledafter Bean, 1949; Willman et al., 1967;
Hershey, 1969; Heyl and West, 1982). The numbersrefer to the followingsulfideoccurrences:(1)
Lansinglead mines,(2) Mineral Creek mines,(3) Twin Springsquarry, (4) G. Huber farm, (5) Fairbank
quarry, (6) Pint's quarry, (7) Waterloo Southquarry, (8) Fergusonquarry, (9) Four County quarry,
(10) Martin-Marietta Cedar Rapidsquarry, (11) Conklin quarry, (12) CollinsonBrothersstonequarry,
(13) Midway quarry, (14) NortheastMoline quarry, (15) SouthRemry farm, (16) Buckwalterfarm,
(17) Morseville digs, (18) Stadermangold prospect,(19) Yellow Creek lead mine, (20) Warren lead
mines,(21) Exeterdigs,(22) HammersIcyConstructionquarry,(23) CamelHill quarry,(24) Speedway
roadcut(CountyRoadM) near Pine Bluff, (25) Demby-Weistmines,(26) Woodmanlead mine, (27)
Little KickapooIndian Cavernslead mines,(28) Plum Creek coppermine, (29) T. Rudd farm, (30)
StateHighway quarry.

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by Society of Economic Geologists, Cesar Ricardo Vargas
 Pb-Zn & BASE METAL MINERALIZATION, UMV•IA, W1, IL 2141

Upper Mississippi Valley regionin Iowa. The nomen- mostimportantoftheseare:thePlumRiverfaultzone

clature usedhere hasbeen adoptedfrom that used which extendsfrom the CedarRapidsvicinity in Iowa
by the Iowa Departmentof Natural ResourcesGeo- eastward to the Leaf River in northwestern Illinois
logicalSurveyBureau(Bunkeret al., 1985) anddoes (Figs.2 and 3); the Fayettestructuralzonein north-
not correspondexactly with nomenclatureused in easternIowa; and severalanticlinalbelts, the Meekers
neighboringstatesor with U.S. GeologicalSurvey Groveanticline,Synmagilanticlinalbelt, andthe Sa-
geologicnames. vanna-Sabulaanticline(Bunkeret al., 1985). Heyl and
Paleozoicstratawhich crop out in the studyarea West (1982), Ludvigsonet al. (1983), andLudvigson
includethe uppermostCambriansedimentaryrocks andMillen (1988) suggested that fluidswhichformed
(primarilythe JordanSandstone) throughthe Missis- mainUpper Mississippi Valley districtmineralization
sippianWarsawFormation.Theserocksarecomposed followed the Plum River fault zone and produced
of marinelimestonesand shales,primarily. Many of severaloutlyingminor Upper MississippiValley oc-
thelimestones haveundergone dolomitizationonboth currences.Mostof the structuralfeaturesin the Upper
local and regionalscales.SomePennsylvanian rocks MississippiValley resultedfrom Paleozoicdeposi-
are found at a few of the minor outlyingbasemetal tional and tectonic events.
localitiesin easternIowa andconsistmostlyof channel Nature of Mineralization
sands and karst fills within Middle Devonian strata
where the Mississippianand Upper Devonian rocks The form of the mineralizationin the outlyingoc-
havebeentruncateddueto erosion(GarvinandLud- currencesis controlledby the lithological,mineral-
vigson,1988). The larger of the outlyingoccurrences ogical,andstructural
characteristicsof the hostrocks.
are found in Late Cambrian rocks and dolomites of However,the degreeof fracturing,the jointing,and
the Prairie du Chien Group in northeasternIowa the faultingandporosityappearto be moreimportant
(Lansingand Mineral Creek mines; Garvin et al., controlson the morphologyof the mineral occur-
1987) andalongthe northernfringe of the mainUp- rences. Dolomitic carbonate rocks are more often
per Mississippi
Valley districtin Wisconsin.Although mineralized than shales or sandstones;unaltered
severalof these occurrenceswere exploitedduring limestones are rarelymineralized.Theserelationships
the 19th century, none are presentlyconsideredto appearto holdfor the mainUpperMississippi Valley
be of commercial value. To the south and west of the district and the outlying minor occurrences.Epige-
maindistrict,sulfidemineralizationisexposedin pro- netic mineralizationalsooccursin veinsandjointsin
gressivelyyounger rocks. Pyrite and marcasiteare coalbedsin the northernpartsof the ForestCity and
presentin nearlyeveryexposedunit of the Paleozoic Illinoiscoalbasins(Hatchet al., 1976; Whelanet al.,
section(Garvin et al., 1987); however, sphaleriteis 1988).
less widespread. Copper mineralization is more Heyl (1983) notedthateventhoughtherearemany
abundant in minor occurrencesin Wisconsin,whereas formsof epigeneticmineralization, pitch andfiatand
sphaleriteis more abundantin Iowa and northernIl- gashvein depositsare dominantin the main Upper
linois.Galenaappearsto be morecommonwith prox- MississippiValley district.The outlyingoccurrences
imity to the maindistrict.The majororebodiesin the havevariableformsalsoandinclude:(1) verticalvein
main districtoccurpredominantlyin limestonesand deposits(e.g., Lansinglead mine), (2) gashvein de-
dolomites of the Lower Ordovician Prairie du Chien posits(e.g.,DembyWeist mines;Mount Carrolllead
Group and the Middle Ordovician Platteville For- deposits),(3) disseminatedbreccia deposits(e.g.,
mationand GalenaGroup (Heyl, 1968). Rocksof Si- Mineral Creek mines), (4) vug linings (e.g., Pint's,
lurian ageare mineralizedonly in the extremesouth- Waterloo South,and CollinsonBrothersMilan quar-
west partsof the district,in Iowa. ries), and (5) paleokarstreplacementbodies (e.g.,
Severalimportantstructuralandtectonicfeatures Plum Creek coppermines).Typical formsof miner-
are presentin the Upper MississippiValley district alizationare shownin Figure 4.
andextendinto the outlyingregions(Fig. 2). The dis- The mineralogyof the outlyingminoroccurrences
trict is boundedto the north and northeastby the isrelativelysimplewhencomparedto the mainUpper
Wisconsindome and Wisconsinarch, respectively. Mississippi Valleydistrict(Table1). Principalsulfides
Three large intracratonicbasinsalsoflank the main in the outlying occurrencesare pyrite, marcasite,
Upper MississippiValley district and the outlying sphalerite,andgalena.The onlyprimaryphasefound
mineralizedzone:the Michiganbasinto the east,the in outlyingoccurrences whichhasnot been reported
Illinoisbasinto the south,andthe ForestCity basin in the maindistrictis fluorite.Strongcolorbanding,
to the southwest. A fourth basin, the East-Central like that presentin the mainUpper Mississippi Valley
Iowa basin(Bunker, 1981; Ludvigsonet al., 1983; district(McLimans,1977; McLimanset al. 1980), is
Bunker et al., 1985), coincidesgeographicallywith not recognizedin outlyingsphaleriteshostedin car-
the maindistrict.Severalmajorfaultandfoldsystems bonates but is present in coal-hostedsphalerite
are presentwithin andsurroundthe maindistrict.The (Whelan et al., 1988). The most commongangue

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by Society of Economic Geologists, Cesar Ricardo Vargas
 2142 K. B. KUTZ AND P. G. SPRY

..:...•.:•.•
Areaso1'Precambrian
outcrop
(major
Phanerozoic tectonically positive area)

.:• Areas ofPennsylvenien

Phenerozoic tectonicallyoutcrop(major
depressed area)

,•:::::,,
LimitO!Midcontinent
Anontally Geophsical
,,•Fault orfaultzone;
downthrown
side
indicated

.." Approximate location of East Central Iowa

"-" Basin

0 200 Miles
I I I I

FIG. 2. Generalizedmapof the majortectonicfeaturesof the north-central

midcontinentregion
(modifiedafterBunkeret al., 1985).Abbreviations:
AR = Ames-Rolandhorst,FSZ= Fayettestructural
zone, MG = Meekers Grove anticline, OA -- Oquawka anticline, PRFZ = Plum River fault zone,
SN = Synmagil anticlinal belt, SSA = Savanna-Sabulaanticline, TR = Thurman-Redfield structural
zone,UMV -- main Upper Mississippi Valley ore district.

mineral in the outlying occurrencesis calcite. Al- mineralization preceded deposition of galena and
thoughit commonlyformsasrhombohedraland sca- sphalerite.Recent studiesby Ludvigsonand Millen
lenohedralcrystals,it isnot clearwhethertheseforms (1988) suggestthat the third parageneticsequence,
canbe correlatedwith the distinctivesequenceof four whichis representedsolelyby the MountCarrolllead
forms (modified rhombohedrons,scalenohedrons, mines,shouldbe modifiedbecausedolomite(rather
truncated scalenohedrons, rhombohedrons),recog- than calcite)precedessulfidemineralization.In light
nized by Heyl et al. (1959) for calcitefrom the main of LudvigsonandMillen'sfindingsit is apparentthat
district. the third paragentictype is essentiallyidentical to
Garvinet al. (1987) classified the outlyingmineral the secondtype. Therefore, we recommendthat the
occurrencesinto three types basedon paragenetic three-foldclassification schemeof Garvinet al. (1987)
sequence:(1) occurrences in whichsulfidesare gen- for outlyingminor basemetal occurrencesbe aban-
erallyearlyandcalciteislate, (2) occurrences in which doned and replaced by a two-fold classification
calciteis early and sulfidesare generallylate, and (3) scheme.Parageneticsequences for outlyinglocalities
occurrences in which calcite is absent and, where are comparedin Figure 5 with that obtained by
more than one sulfideis present,iron sulfideis early McLimans(1977) for pitch andfiat depositsfromthe
and other sulfidesare late. As Garvin et al. (1987) main district.
suggested, occurrences of the firsttype are mostsim-
ilar to the main Upper MississippiValley deposits. Fluid Inclusion Study
Furthermore,they suggestedthat the third parage- Fluid inclusionscontainedin sphaleriteandcalcite
netic type is similarto the maindistrictdeposits(with in the outlying occurrencesare predominantlytwo-
the exceptionof the lackof calcite)in thatironsulfide phaseliquid-vaporinclusions.A number of single-

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 Pb-Zn & BASEMETAL MINERALIZATION, UMV--IA, WI, IL 2143

DOMINANT KNOWN STRATIGRAPHIC DISTRIBUTION OF

SYSTEM SERIES FORMATION LITHOLOGY SULFIDE MINERAL OCCURRENCES

Warsaw
Formation Sh. -•:•--Ft.Madison
area
< Keokuk Formation Ls.

• Burlington
Formation Ls.
• Gilmore City Formation Ls.

• Hampton
Formation Dol. •:7[]--Ferguson
Quarry
• English River Formation Sh.

• MapleHill Formation Sb.

{!!iiiiii{
•j:•-Pints, Fairbank, Waterloo South,

• Wapsipinicon
Formation Ls. 11insonBrothers,Conklinquarries
• • otis
Formation Ls.
Bertram Formation Dol.
LUD-•

LOVIAN
• Gower
Formation
• Scotch
Grove Dol. '?•U
Dol.
Formation ?•/•-Midway
Quarry
--Martin-Marietta
'z!•--G.
Huber
farm
Quarry
(?)
• • Hopkinton
FormationDol.
• • BlandingFormation Dol.

• i Tete
des
Morts
Formation
Dol.
• Mosalem
Formation Dol.
Maquoketa
Formation Sh. :.D-Staderman
gold
prospect
• Dubuque
Formation Dol. iiiiiiiii-Mt.
C.... 11Mi.... Yellow
Creek
Wise
Lake ii iiiiiiii
Formation Dol. ili!iiii
i Mine,
f.... Mo
....illedigs,
farmS.Remry
Buckwalter
Dunleith
Formation Dol. iii__
main districtUMV oredeposits
• Decorah
Formation Ls. :: Camel
Hillquarry•
roadcut
(Co.
•o •• Platteville
Formation
Glenwood
Ls. ii i•.::•--
Rd. M)
, St.Highway
::•'•-Hammersly
Shale
Quarry
Const.
quarry
Sh.

St. Peter Sandstone Ss.

• Shakopee
Formation Dol. Mineral
Creek•
Woodman•
Plum
• Oneota
Formation Dol. i •Creek
Cavernsmines;
digs Little
Kickapoo
• Jordan
Sandstone Ss. iiii!i!i
ii•-T. Rudd
farm(Doylestown
Pbdigs)
• • St.Lawrence
Formation Dol. •-'-Demby-Weist,
Lansing
mines

FIG. 3. Generalizedstratigraphicnomenclatureand lithologiesfor Paleozoicrocksexposedin the

study area (modified after Garvin et al., 1987). Abbreviations:Dol -- dolomite, Ls -- limestone,
Sh = shale, Ss = sandstone.

phase liquid inclusionsare also present;however, ondaryinclusions wheretwo phasesare present)are

theseare generallysecondaryinclusions or are pri- extremelyconsistent onbothlocalandregionalscales.
maryinclusions whichshowevidenceof leaking.De- At room temperature,the vapor phaseusuallyoc-
terminationof the primaryandsecondary natureof cupies5 to 10 percent of the inclusionvolumefor
fluidinclusionswasmadeaccording to the criteriaof sphaleriteandapproximately 5 percentfor inclusions
Roedder (1984). Since most samplesdid not show in calcite.Althoughquartzandfluoriteare presentat
evidenceofthe directionof growthor werecomposed severallocalities,thesemineralsdid not yield inclu-
of intergrowncrystalmasses,any planar groupsof sionssuitablefor analysis.
inclusions were assumedto be of secondaryorigin. Heating and freezingmeasurements were deter-
Inclusionswhich were interpretedto be of primary minedusinga Chaixmeca heating-freezing
stage.This
origin were usuallyindividualinclusionsseparated stagehasbeenmodifiedto includeextraexternalin-
fromall otherinclusions
or werein nonplanar clusters. sulationand a smallersamplechamberusingthe de-
Liquid to vaporratiosof primaryinclusions (andsec- signof Cunningham andCarollo(1980).Two or three

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by Society of Economic Geologists, Cesar Ricardo Vargas
 2144 K. B. KUTZ AND P. G. SPRY

-lcm b

py

FIG. 4. Representativeforms of mineralizationfrom outlying base metal occurrences.(a). Early

pyrite (dark)lining cavitywall followedby late coarsecalcite(white) in limestonefrom the Fairbank
quarry (sampleFB-5). (b). Vug containinglate pyrite (py) coatingcoarsewhite scalenohedralcalcite
in limestonefromPint'squarry(samplePT-3). (c).White baritecrystalsandpyrite in vugin dolomitized
limestonefrom the Fergusonquarry. Pyrite cubesand cubo-octahedra are disseminated throughout
the hostrock and precededbarite mineralization(sampleFG-40). (d). Early pyrite and someminor
disseminated marcasitefollowedby white calciteand minorlate pyrite in solution-enlarged cavityin
limestonefrom the CollinsonBrothersquarry(sampleML-4).

heatingandfreezingexperiments
wereperformedon to 105øC and 75ø to 121øC, respectively.Note,
everymeasuredinclusion.The heatingandfreezing however,that the inclusionsmeasuredby Newhouse
dataareshownin Table2 andFigure6. Theprecision (1933) and Bailey and Cameron (1951) were in
of the homogenization
temperaturewas_0.2øC or
betterandreplicatemeasurementsshoweda repro- TABLE1. Primary Minerals from the Main Upper Mississippi
ducibilitywithin _0.5øC. Valley District and Outlying Minor BaseMetal Occurrences
Homogenization temperatures
(Th)for primaryin-
clusionsin samplesof sphaleriteobtainedfrom the Outlyingbasemetal
outlyingoccurrences rangefrom 57.4ø to 115.8øC occurrences Main district •
andoverlapwiththerangeobtained byCoveneyand Ankerite, barite, calcite,
Goebel(1983) and Coveneyet al. (1987) on the chalcopyrite,cobaltiteor
ConklinandMartin-MariettaCedarRapidsquarries safilorite, dolomite,
aspartof a regionalfluidinclusionanalysis
of minor Barite, calcite, chalcopyrite, enargite,galena,gold,
occurrences in the Midwest,predominantly in Mis- dolomite, fluorite, galena, marcasite, millerite,
souriandKansas. In general,thesetemperaturesare gypsum,
2 martasite, muscovite, pyrite,
cooler than those measured in fluid inclusions from millerite, pyrite, quartz, pyrrhotite, quartz,
sphalerite sphalerite,wurtzite
the main Upper Mississippi
Valley district(75ø-
220øC)by McLimans (1977).Newhouse (1933)and After Heyl et al. (1959); McLiman(1977)
BaileyandCameron(1951) reportedrangesof 80ø Possiblysecondary

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by Society of Economic Geologists, Cesar Ricardo Vargas
 Pb-Zn & BASEMETAL MINERALIZATION, UMV--IA, WI, IL 2145

MAIN UMV DISTRICT PINT'S QUARRY

studyoverlapthe dataobtainedby McLimans(1977)
MC • MC
py •-- py ......... ,
andCoveneyet al. (1987), no pressurecorrectionhas
CP ...... GN -?- been added.
SP SP -?-
GN •- • BA
Freezingexperimentsperformedon primaryand
• --- •
BA ....... FL ,.--,secondaryinclusionsin sphaleriteand calcite from
•
ML CC •
EN •
the outlyingsulfideoccurrences showedinitial melt-
CC
E
, ,
L
ing temperatures(Te) lower than -38øC. Sincethe
a hE L majority of the Te measurements lie between -60 ø
COLLINSON QUARRY MO.•U
N_T C.
ARROL
.L and-49øC, it is suggested that appreciablequantities
MC -4
of CaCb.,and possiblyMgCI•., in additionto NaC1
PY , • • IDO •
PY m ,
MC • • are presentin the fluid inclusions.
Final meltingtemperature(Tin)determinationsof
•P
CC

E -"--'•L • •

Ii] I= i.
ice for primaryinclusions in sphaleritefromthe out-
lying occurrences(-11.6 ø to -21.6øC) indicatethat
MC,
FERGUSON QUARRY
i
FAIR
N.•____.•K
BAQUARRY fluid salinityrangesfrom 15.6 to 23.8 equivwt per-
PY , • Py , ,
cent NaC1.This rangeoverlapswith that reportedby

MC
-•
SP • -._ CC • •
CC , , McLimans(1977) for sphaleritefromthe mainUpper
BA -,- •'
MississippiValley district (19.6->23 equiv wt %
i• E L f E L
NaC1)usingthe calibrationof Potter et al. (1978). In
FIC. 5. Parageneticsequences of primarymineralsfor (a) the contrast to the maindistrict,nodaughtercrystals have
mainUpperMississippi Valleydistrict(McLimans, 1977), (b)Pint's been recognizedin outlyingsphalerites.Secondary
quarry--type 2 mineralization(Garvinet al., 1987), (c) Collinson inclusionsin outlying sphaleritestended to yield
Brothersquarry--type1 mineralization, (d)MountCarroll--type higher final melting temperaturesthan primary in-
2 mineralization(Ludvigsonand Millen, 1988), (e) Ferguson
quarry--type 1 mineralization,(f) Fairbankquarry--type 1 min- clusions,althoughin severalexamplesprimary and
eralization.Abbreviations:BA = barite, CC = calcite,CP -- chal- secondary inclusionsin the samesamplesyieldedin-
copyrite,DO = dolomite,E -- early,EN = enargite,FL = fluorite, distinguishable valuesof Wm(Fig. 6).
GN = galena, L = late, MC = marcasite, ML -- millerite, PY Final meltingtemperaturesof inclusionsin calcite
-- pyrite, SP = sphalerite.
yieldedvalues(-20.7 ø to -8.0øC) whichare signif-
icantly different from those reported by Hall and
sphaleritefromlater stagesof sulfidemineralization. Friedman (1963) for calcite from the main district
Homogenization temperatures obtainedonsecondary (-3.1 oto -2.9øC). Corresponding salinityvaluesare
inclusions fromsphalerite in outlyingoccurrences are 11.7 to 23.2 and 4.8 to 5.1 equiv wt percent NaC1,
48.8 ø to 75.1øC and tend to be lower than those for respectively(Fig. 6).
primaryinclusions fromcorresponding samples(Fig.
6). Someoverlapof homogenization temperatures Stable Isotope Study
doesoccurand,in somecases,secondary inclusions
yielded higher homogenizationtemperaturesthan Sulfur, carbon, oxygen, and hydrogen isotope
primaryinclusionsfrom the samesamples. compositions were determinedonsamples of outlying
Homogenizationtemperaturesfor primary inclu- sulfides,sulfates,carbonates(calcite and host dolo-
sionsin calcite associatedwith outlying sulfideoc- mite), carbonaceousshales,and fluidsextractedfrom
currences rangefrom37.8øto 75.4øC(Fig.6). These inclusionsin sphalerite,calcite,andfluorite.The data
temperaturesare similarto the 50ø to 78øC range in thisstudyare comparedwith resultsobtainedfrom
reportedby BaileyandCameron(1951) for inclusions other stableisotopestudiesundertakenon the main
from middlecalcite-stage mineralizationin the main Upper MississippiValley depositsand outlying oc-
Upper MississippiValley district and to the 46 ø to currences (McLimans, 1977; Garvin et al., 1987;
74øC rangereportedby Erickson(1965) for calcites Garvin andLudvigson,1988; Ludvigson,1988; Lud-
of variousagesfrom the main district.The number vigsonandMillen, 1988; Whelan et al., 1988).
of datafor homogenization temperatures for second- Stable isotope values were obtained at Indiana
aryinclusions in calciteislimited;however,therange Universityusinga FinniganDelta-E massspectrom-
of homogenization temperaturesoverlapswith that eter for 6•3C, 6•80, and •D determinationsand a 6"
recordedfrom primaryinclusions. 60ø sectorNuclidemassspectrometer for •34Sdeter-
McLimans(1977) and Coveneyet al. (1987) have minations. Analyticalprecision forvaluesof •aC and
suggested thata pressurecorrectionof approximately •80 aregenerallybetterthan_+0.05permil,for
10 ø to 12øC shouldbe added to Th data for the main between 0.05 and 0.10 per mil, and for •D, _+1per
UpperMississippi Valleyorebodiesandto minorUp- mil. Details of the analyticalmethodsare given in
per MississippiValley-type occurrencesin the Mid- Kutz (1987) and individualanalysesare givenin Ta-
west,respectively.Sincethe Th dataobtainedin this bles 3, 4, and 5.

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 2146 K. B. KUTZAND P. G. SPRY

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 Pb-Zn& BASEMETALMINERALIZATION,UMV---IA, WI, IL 2147

UMV Calcite 1ø inclusions UMV Sphalerite 1ø inclusions

30- (Hall and Friedman, 1963} (McLimans,1977) to +16.4%0 and -8.8 to -4.0%o, respectively).The
I 1
large variationin sulfurisotopecompositions of iron
sulfidesoccurswithin individualdepositsat the Col-
25-
linsonBrothersquarry (-21.0 to +28.5%0), the Fer-
gusonquarry (2.8-33.1%0), and the Fairbankquarry
20- SPHALERITE
(-19.6 to -0.3%0) and was reported previouslyby
[] 1ø inclusions Garvin et al. (1987) for the Martin-Marietta Cedar
[] 2 ø inclusions Rapidsquarry (1.0-35.1%0) and the Mount Carroll
CALCITE
[] 1ø inclusions
mines(-20.0 to +1.5%0).The lightestisotopevalue
•[]
ß 2Oinclusions
(-22.3%0) from this studywas obtainedfrom pyrite
hostedby carbonaceous materialin a karstfill at the
Four County quarry.
One/i•4Svalue(30.1%0)of baritewasdetermined
andisconsistentwith valuesobtainedfor barite(22.4
and30.7%0)fromthe ConklinandPint'squarries,re-
o
o lb 45 2o 2'5
spectively,
by Garvinet al. (1987)andthe mainUpper
Salinity (equiv. wt. % NaCI)
MississippiValley occurrences(22.3-35.9%0) by
McLimans(1977).

20- UMV Calcite 1ø inclusions

UMV Sphaler•te 1ø •nclusions Carbonand oxygenisotopes
(McLimans,1977}
(McLimans,
1977)
I I
SPHALERITE
Carbonandoxygenisotopecompositions
wereob-
tained on late and early calciteassociated
with min-
15-
i!• [] 1øinclusions eralizationfrom nine outlyingoccurrences (Fig. 8).
[] 2øinclusions
CALCITE Valuesof/i•sOrangefrom21.3 to 28.5 per mil and
[] 1øinclusions are isotopicallyheavier than values(16.8-22.8%0)
obtainedfromcalciteassociated withthemainUpper
t .'.• • :•2ø
inclusions
....
Th,
e Mississippi
two samples
Valley district(McLimans,1977). Only
analyzedin thisstudyoverlapwith those
determinedfor the maindistrict(Fig. 8). In contrast
to the oxygenisotopedata,carbonisotopecomposi-
tions(-8.8 to +3.3%0)fromthe outlyingoccurrences
o
2o 4o 6o 6o
I
partially overlap with those (-12.6 to -2.1%0) ob-
Th (øC) tainedby McLimans(1977) from the main district.
There doesnot appearto be anydistinctionbetween
FIG. 6. Histogramsfor datafromfluidinclusionheating(top) /i•sOand/i•aCvaluesfromearlyandlatecalcitefrom
andfreezing(bottom)experiments.DatafromHall andFriedman's
(1963) and McLimans'(1977) studyare givenfor comparative
the outlyingoccurrences.
McLimans(1977) suggested
purposes. that the morenegativevaluesof/ilaC fromthe main
district may have been influencedby an influx of
ground water or by oxidationof methane or other
organic compounds.Although organic matter and
Sulfur isotopes methane have not been detected in fluid inclusions
Seventysulfurisotopeanalyseswere obtainedon from any outlyingoccurrences in Iowa, Illinois,and
sulfidesandsulfatesfrom 19 outlyingmineraloccur- Wisconsin(cf. with the Jumbomine, Kansas,where
rences.Thesedataarepresentedin Figure7 together petroleum was recognized;Blasch and Coveney,
with dataof McLimans(1977), Garvinet al. (1987), 1988), carbonaceous and organic-richlaminaeare
Garvin and Ludvigson(1988), and Ludvigsonand presentin mineralizedhorizonsat many of the out-
Millen (1988). Data obtainedin the presentstudy lying occurrences(e.g., Pint's,Waterloo South,Col-
showa rangeof/i34Svaluesfor sulfides(-22.3 to linsonBrothers,FourCounty,Ferguson,andConklin
+33.1%0)thatis almostidenticalto the range(-18.9 quarries).Two carbonisotopeanalysesof organic
to +35.1%0)reportedby Garvinet al. (1987). This shalesamplesfrom the Fergusonand Four County
range contraststo that (5.4-29.9%0) obtainedby quarriesyieldedvery light/ilaC valuesof -25.1 and
McLimans(1977) for sulfidesfrompitchandflat de- -26.0 per mil, respectively.
positsin the mainUpperMississippi Valleydistrict. In order to determine whether the host rocks in-
Althoughsamples of pyritefromthisstudyyielded fluencedthe isotopiccompositions of calcite asso-
compositions whichspanthe entirerangeof/i34Sval- ciatedwith the outlyingoccurrences,carbonand ox-
ues(-22.3 to +33.1%0),sulfurisotopecompositionsygen isotopecompositionsof somecoexistinghost
of sphaleriteandgalenaare morerestricted(-14.2 rockswere alsodetermined(Fig. 8). Calciteandco-

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 2148 K. B. KUTZ AND P. G. SPRY

TABLE3. Sulfur Isotope Data of Sulfidesand Barite from Outlying BaseMetal Occurrences

•a•s• (%0)

Location Sampleno. Sphalerite Pyrite Galena Barite

Camel Hill quarry CH-SP-1 1.5

CH-SP-2 1.7
CollinsonBrothersquarry ML-1 -1.9
ML-S-1 -10.2
ML-SP-5 -7.5
ML-SP-6 -10.5
ML-SP-7 - 12.9
ML-SP-8 -7.4
ML-SP-9 - 11.6
ML-4 -21.0
ML-5 -1.7
ML-7 20.1
ML-13 10.9
ML-15 -7.8
ML-30 28.5
ML-46 22.5
ML-47 17.0
ML-50 -10.3
ML-PY-NOD 10.7
Exeter digs EXE-G-1 2.0
Fairbankquarry FB-2 -15.3
FB-3 -15.0
FB-5 -19.6
FB-6 -0.3
FB-7 -15.2
FB-10 -18.1
FB-11 -18.2
FB-12 -13.5
FB~NOD-1 17.9
FB-MC -15.1
Ferguson quarry FB-SP-1 - 12.1
FG-PY-2 2.8
FG-PY-5 7.4
FG-PY-6 27.7
FG-PY-7 12.3
FG-PY- 10 33.1
FG-11 15.6
FG-13 20.1
FG-BA 30.1
Four County quarry 4C-26-P 3.2
4C-27 -22.3
4C-29 18.2
FS-1 15.8
FS -3 -10.5
G. Huber farm GH-SP-1 16.4
GH-SP-2 16.1
Speedwayroadcut SWAY-G-1 -4.0
SWAY-SP-1 -0.3
State Highway quarry STHY-SP-1 3.7
Twin Springsquarry TS-SP-1 -6.2
TS-SP-2 -11.9
TS-SP-3 -6.7
T. Rudd farm TR-G-1 4.3
Waterloo South quarry WS-1 -18.1
WS-3 -16.5
WS-2 -7.1
Woodman lead mine WOOD-G-1 8.1
WOOD-G-2 8.8
Hammersly constructionquarry VER-SP-1 -0.8
Little KickapooIndian Caverns KICK-G-1 7.4
lead mines KICK-G-2 6.5
Lansinglead mines LAN-G-1 -4.3
LAN-G-2 -0.8

Midway quarry MDWY-SP- 1 14.2

MDWY-SP- 2 14.8
Northeast Moline quarry FJ-SP-1 14.0
FJ-SP-2 13.6
Moline 75-1 15.4
Conklin quarry CN 1-20 9.6
CN-KST-SP -6.3

Data are presentedrelativeto the CDT meteoricstandard;the standarderror of eachanalyses

is _+0.05per mil

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 Pb-Zn & BASEMETAL MINERALIZATION, UMV--IA, WI, IL 2149

TABLE4. Carbonand OxygenIsotopeData from Outlying BaseMetal Occurrences

A•SO4
Location Sampleno. MineralI b•SO2 b13C3 (eeof water) TøC5
Collinson Brothers ML-18 cc (late) 21.31 -5.40
quarry ML-236 cc (late) 23.19 - 1.62 25.35 41
ML-4H 6 ls 23.04 - 1.14
ML-30H ls 25.12 -0.29
Fairbank quarry FB-3• cc (late) 28.50 -2.27
FB-CC-10 cc (late) 28.15 -1.74
FB-4H • ls 28.52 - 1.15
Ferguson quarry FG-CCo6 cc (late) 26.33 -3.57 27.61 29
FGoCC-8 cc (late) 25.97 3.26
25.84 3.19
FGo5H ls 29.00 5.36
FG-SH sh -25.14
Four County quarry 4C-27 sh -26.01
Martin-Marietta Cedar CR-11 cc (late) 26.01 -3.73
Rapidsquarry
Mineral Creek mine MC-lu-FE cc (late) 27.01 -7.47
Pint's quarry PT- 1 cc (early) 27.84 - 1.72 29.09 22
PT-3 cc (early) 27.84 -0.62 23.59 51
Conklin quarry RPS-3 cc (late) 24.82 -0.61
C-1 cc (late) 23.11 -2.01
Twin-Springs quarry TS-1 cc (late) 22.81 -8.77
Waterloo South WS-1 cc (late) 24.53 -6.85
quarry WS cc (late) 26.90 1.19

cc = calcite, ls = limestone,sh = shale

Valuesgivenarein per mil relativeto standard meanoceanwater(SMOW)
Valuesgivenare in per rail relativeto Peedeebelemnite(PDB)
Values determined from/5•80 of fluid inclusions in Table 4 and bxso of calcite in this table
Temperaturedeterminedutilizingthe calcitewater-oxygen
isotopefractionation
of O'Neil et al. (1969)
Mineralandhostrockpairsarebracketed

existingdolomitefromtheselocalitiesdisplayalmost at the Martin-Marietta depositand the Four County

identicalvaluesof blac, whereasvaluesof •j180 for and Conklinquarriesthat are almostthe sameasiso-
calciteare slightlylighterthanthosein coexistingdo- topicvaluesobtainedonhostlimestones anddatare-
lomite.Thisrelationshipisconsistentwith the findings
of GarvinandLudvigson(1988) who reportedcarbon OUTLYING OCCURRENCES [Mt Carroll area)
5•
andoxygenisotopedatafor vein andfracturefillings
n=11r
] i gash
veins-
Ludvlgson
and
Millen
[1988)
MAIN UMV DISTRICT [Fessler mine)

TABLE5. HydrogenandOxygenIsotopeData • gash

veins
Ludv•gson
and
Millen
(19881
from Outlying BaseMetal Occurrences
1001
ßSPHALERITE
[] BARITE • MAIN
UMV
DISTRICT
{-
b1802 bD •
• 751• PYRITE[] ß pitch
and-flat
deposits

[]CHALCOPy
j•-MoL
.....
(1977
Location Sampleno. MineraP (%o) (%o) MARCASITE
• 50
t [•GALENA
LU 5
CollinsonBrothers ML-S-1 sp 5.19 -63.7 I•L n=31B
quarry ML-SP sp 4.97 - 28.5 , , , , P , , ,• F-- 'T'--- 7' , ,
ML-1 cc 1.56 -22 OUTLYINGOCCURRENCES-Garwnand Ludv,gson
•1988)

ML-23 cc -2.16 -18 5:1.=34

Fairbankquarry FB-5-CC cc -2.04 -64.8 i i i I i i i i i i i i

OUTLYING OCCURRENCES-Garvln et al (19871

FB-CC-10 cc 0.28 -52.3
Fergusonquarry FG-CC-1 cc -1.92 -50.2
FG-CC-6 cc -1.28 -83.2 .... •, ß •,• ? .......

Pint's quarry
FG-CC-7c
PT-1
cc
cc
2.90
-2.25
-54.8
-44 5•n•IOm OUTr•YING
i
OCCURRENCES-
i
Th•s
study • i i i i • i i i i

PT-3 cc 4.25 -59

-20 -10
-30 0 10 20 30 4'0
•34S%o
PT-SP-1 sp 5.93 -31.4
PT-FL fi -8.53 -94.4 FIG.Compositesulfurisotopehistograms
7. for the mainUp-
per Mississippi
Valley (UMV) district(McLimans,1977; Garvin
cc = calcite,fi = fluorite,sp= sphalerite and Ludvigson,1988) and outlyingoccurrences(Garvinet al.,
Valuesgivenarein per mil relativeto SMOW 1987; Garvin and Ludvigson,1988; this study).

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by Society of Economic Geologists, Cesar Ricardo Vargas
 2150 K. B. KUTZ AND P. G. SPRY

onlyrecentlybecomeavailableongashveindeposits
o calcite-this study-type1
(Ludvigson,1988; Ludvigsonand Millen, 1988).

1Ocalcite--this
study-type2
ß
ß host rock-this study o
r• calcite--Garvin et al.(1987)-type1 Geochemical data have not been obtained from
ß host rock--Garvin et a1.(1987) o
stockwork,bedded replacement,solution-collapse
McLimans
(1977) oß breccias,fissureveinsand lodes,and ore-lined giant
• -2-•13C /•calcite-main
=-26.01
to UMV
district
-25.14
organicshales ' 00'
vugsor smallsulfideencrusted
cavesthatarepresent
in the main district. In view of these limitations, a
discussion
of the geneticrelationshipbetweenthe
0
0
outlyingminorbasemetaloccurrences andthemain
_

district will be restrictedto the pitch and fiat and

gashvein deposits.
Fluid inclusiondataindicatethat there are signif-
-12
t
i
16
i i
18
i
2[0
i
2[2
i
2•4 2•6 2s8 30
icantdifferencesbetweenfluidsthat formedoutlying
occurrences and orebodies in the main district. The
6180
mean homogenization temperaturesof fluids in
FIG. 8. Plot of •]aC vs. /5]80 values for calcite and host rocks sphaleritefrom the outlyingoccurrences is approxi-
fromtype I and2 outlyingsulfideoccurrences. Carbonandoxygen mately80øCandissignificantly lowerthanthemean
isotopecompositions of calcitefromthe maindistrictareplotted
in the enclosedarea.Alsoshownare$]aCvaluesfor organicshales homogenization temperature of 120øCforsphalerite
fromtwooutlyingoccurrences (seetextfor details);
modifiedafter fromthe maindistrict.The highesttemperaturefrom
Ludvigson(1988). an outlyingoccurrence is only 116øC.Homogeniza-
tion temperatures for calcitesfromthe outlyingoc-
currencesand the main districtoverlap,but salinity
portedhere. Carbonand oxygenisotopedatafrom determinationson fluidsin calcitefrom the outlying
the present study suggestthat calcite may have districtindicatethattheywereconsiderably moresa-
formedby dissolutionof the hostcarbonates during line.The absence of organicmatter,CO•, anddaugh-
late diagenesis
andthatisotopically
light carbonmay ter crystalsin inclusionsin the outlyingoccurrences
havebeenderivedlocallyfromorganic-richstrata. andtheir presence in someinclusions fromthe main
district indicate further differencesin fluid compo-
Oxygenand hydrogenisotopes from fluid inclusions sition.
Oxygenandhydrogenisotopeanalyses were per- Garvinet al. (1987) classified
the outlyingminor
formedon fluidsextractedfrom 13 samplesof calcite, sulfideoccurrences asthree groupsbasedon sulfur
sphalerite,and fluorite from the CollinsonBrothers, isotopecomposition:(1) thosewithweaklyto strongly
Fairbank, Ferguson, and Pint's quarries (Fig. 9). positivevaluesof 5348(1-30%0),(2) thosewith
Fluids extractedfrom outlyingcalcitesdisplaycon- strongly
negativevalues
of•a4S(-20 to -10%0),and
siderablescatterin valuesof •180 and •D (-2.3 to
+4.3%0 and -83.2 and -18%0, respectively)and
overlapwith the one sampleanalyzedby McLimans
(1977) from the main Upper Mississippi Valley dis-
trict. Note that fluidsextractedfrom two samplesof ß sphalerite

sphaleriteyielded•D valueswhichare slightlylighter ßcalcite

than thoseobtainedfrom sphaleritein the main dis- ßfluorite I/ MOW/ IUMV
main
• • l auIfid'
trict (Fig. 9). The singleanalysis
of fluoritefromthe / I ß • stage

Pint'squarryyieldedthe mostisotopically light ox- •D•.- / I' f ß ß leMcLimans(1977}

ygenandhydrogen
values(•180 -- -8.5%0,and•D
= -94.4%0).
• UMV calcite staga ß
Discussion

Prior to the studyby Garvinet al. (1987), minimal

-80
• ß•cLimans(1977}
'
ß

geochemical datawere availableto supportwhether

the outlying occurrenceswere cogeneticwith the $180•.(SMOW)
mainUpper Mississippi Valleydistrictdeposits.Pre-
viousinvestigations (e.g., Heyl andWest, 1982; Gar- F•C. 9. Plot of$]80 vs. $D for fluids extracted from inclusions
vin, 1984; Garvinet al., 1987) havemadecomparisons in calcite,sphalerite,and fluoritefrom outlyingmineraloccur-
with geochemical datain McLimans'(1977) detailed rences. Shaded boxesrepresent
from the mainUpper Mississippi
therangeof $D and$•80values
Valley districtsphaleriteand
studyof the main district.It shouldbe noted,how- calcite. Abbreviations:IL -- Illinois basin,MI = Michiganbasin,
ever,thatMcLimans(1977) concentrated onthe large MW = meteoric water line, SMOW = Standard Mean Ocean Wa-
pitchandfiat depositsandthat geochemical datahave ter.

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 Pb-Zn & BASEMETAL MINERALIZATION, UMV•IA, WI, IL 2151

(3) thosewith valuesof •34Swhichclusteraround0 trict. Two quarries near Moline, Illinois, approxi-
per mil. The generalcontentionof their studywas mately 80 km from the main district(Midway and
that group 1 occurrences,which have parageneses NortheastMoline), and someminor occurrencesalong
similarto pitch and fiat depositsin the maindistrict, the Plum River fault zone have sulfurisotoperatios
are cogeneticwith mainUpper Mississippi Valleysul- for sphaleritewhichare similarto thosereportedby
fide mineralization.Their group2 occurrences, which McLimans(1977) for the main district.
have parageneses most dissimilarto pitch and fiat Sulfurisotopedataof sulfidesfrom the gashvein
orebodiesin the maindistrict,are diageneticin origin, Fesslermine, Iowa, at the edge of the main Upper
with sulfursuppliedthroughleachingof preexisting Mississippi Valley districtshowa very narrowrange
sedimentaryiron sulfides.The third groupconsisted and an averageof 1 per mil (Ludvigsonand Millen,
of gashveins at the Mount Carroll lead minesand, 1988). These data are significantbecausethey are
althoughthe paragenesis issimilarto the maindistrict, lighterthansulfurisotopevaluesobtainedfrompitch
Garvin et al. (1987) suggestedthat this occurrence andfiat deposits by McLimans(1977). Sulfurisotope
formedfrom a mineralizingeventwhichwasdistinct analyses of sulfidesfromminoroutlyinggashveinoc-
from thoseeventsthat formedother outlyingoccur- currences(Lansing,Mount Carroll, and Demby-
rences. Weist)fromthisstudy,Garvinet al. (1987), andLud-
Despite this classificationscheme,severalfactors vigsonandMillen (1988) rangefrom -16.1 to +7.3
suggestthat three distincttypes of outlying Upper per mil and are alsolighterthanthoseobtainedby
MississippiValley occurrencescannot be distin- McLimansfor pitch and fiat deposits.Considerably
guished withanydegreeofcertainty.First,$34S values moredata,however,arerequiredto establish whether
determinedby Garvin et al. (1987) do not fall into gashveindeposits in the maindistrictaresignificantly
three statisticallydistinctgroupsas they imply (Fig. differentfrom thosein outlyingregionsandwhether
7). The data collected in this study, in conjunction all gashveindeposits exhibitsulfurisotopevaluesthat
with their data, suggestalmosta continuumof values are lighter than thoseof pitch andfiat deposits.
from-20 to 30 per mil (particularlyfor ironsulfides). Whelan et al. (1988) obtaineda rangeof -12 to 0
Second,parageneticdataare limitedandit is difficult per mil for $a4Svaluesfrompyrite,sphalerite, and
to classifymany depositsinto the parageneticse- organicmatterfromcoalsof the Illinoisbasinandthe
quencesproposedby Garvinet al. (1987). Third, al- centralandsouthernForestCity basin.In the north-
thoughparageneticdata are availablefor somede- ernForestCity basinmanysamples have$a4S values
posits,they do not necessarilyfall into the isotopic between8 and 19 per mil. Becauseof the similarity
classificationof Garvinet al. (1987). With the excep- of valuesof $a4Sof sphaleriteand pyrite from the
tion of a minor amountof late pyrite at the Collinson main district and the northern Forest City basin,
Brothersquarry, this occurrence,in additionto that Whelanet al. (1988) suggested thatsphaleriteformed
from the Fergusonquarry, fits into the paragenetic from fluids similar to, if not the same as, those that
groupi of Garvinet al. (1987), yet the sulfurisotope formedMississippi Valley-typedeposits.Despitethis
characteristics of bothoccurrences are clearlydiffer- suggestion,it shouldbe pointed out that valuesof
ent from thoseof the pitch and fiat depositsof the $34S of sulfidesin minoroutlyingoccurrences in car-
main district ores and the sulfur isotopegroup i of bonatesbetweenthe northernedgeof the ForestCity
Garvin et al. (1987). basinin Iowa and the main district are isotopically
A comparison of sulfurisotopecompositions of the lighter than sulfidesin coalsin the northern Forest
outlying occurrences(this study and Garvin et al., City basin.
1987) with thoseobtainedby McLimans(1977) for Likely sourcesof sulfur for the outlying occur~
pitch and fiat depositsfrom the main districtreveal rences are connateseawatersulfate and diagenetic
two generalities: $a4Svaluesfor bariteare strongly (sedimentary)sulfur.Seawatersulfateisotopiccom-
positiveregardless of locationor positionin the para- positionsvariedfrom 17 to 30 per mil for the interval
genetic sequence;and outlying minor occurrences Late Cambrianto EarlyMississippian (Claypoolet al.,
immediatelyadjacentto the northwesternportionof 1979).In general,valuesof $a4S forbariteandsome
the maindistrictin Wisconsinhavesulfurisotopeval- sulfidesfrom the outlyingoccurrences lie within this
ueswithin the rangedeterminedby McLimans(1977) range (Fig. 7). In addition, marine evaporiteswere
for the maindistrict(e.g.,Woodmanlead mine,Little periodically depositedduring Paleozoicsedimenta-
KickapooIndian Cavernslead mines),whereasminor tion andhavebeenpartiallyor completelydissolved.
outlyingoccurrences northeastof the maindistrictin The Middle DevonianWapsipiniconand Cedar Valley
Wisconsin(e.g., StateHighwayandCamelHill quar- Groupshave been cited as possiblesourcesfor the
ries), and depositsmore than 60 km from the main outlying mineral occurrences(Garvin et al., 1987).
districtin Iowa (e.g.,WaterlooSouth,Ferguson,Pint's Hansen(1983) reportedvaluesof $a4Sfor gypsum
and Fairbankquarries),have sulfurisotopecompo- fromthe Wapsipinicon Groupwhichrangefrom18.7
sitionslighterthanthosereportedfromthe maindis- to 21.3 per mil. Thesevaluesare closeto the lowest

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by Society of Economic Geologists, Cesar Ricardo Vargas
 2152 K. B. KUTZAND P. G. SPRY

valueof •34Sfor bothoutlyingandmaindistrictbar- the host rocks. Values of •i•aC and •i•SOobtained from
ites. More important, however, is the large number calcitejoint fillingsin coalsin the ForestCity and
of sulfidesfromthe outlyingminormetaloccurrences Illinois basins(-2.7 to -12.4%0; 21.1 to 25.8%0,re-
that have •i34Svalues which are close to the sulfate spectively)by Whelanet al. (1988) are similarto val-
•i34Svaluesreportedby Hansen(1983).Thisobser- uesdeterminedfor calcitefrom outlyingbasemetal
vation supportsthe suggestion that evaporitesmay occurrences rather than calcite from the main district.
havesuppliedsomesulfurto the outlyingsulfideoc- Thereis anoverlapin 6180and•iDvaluesof fluids
currences.The Middle Devonianevaporitesmayalso in inclusionsin sphaleriteand calcite from the main
have been a source of metals for these occurrences. districtandthe outlyingoccurrences; however,data
Pyrite (probablyof diageneticorigin) is found in fromthe outlyingoccurrences areconsiderably more
manyof the carbonatestrataof the upperMississippi scattered(Fig. 9). This scattermayin part be due to
Valley and within paleokarstfills within Devonian the incorporationof fluidsof differentages,but it is
strata(GarvinandLudvigson,1988). Pyritetypically likelythatvaluesof •i•SOfromfluidinclusions in cal-
has•i•4Svaluesthatare stronglyvariableandusually cite also reflect reequilibrationwith calcite upon
negativeandwasproducedby bacterialreductionin cooling.By combining •iiSovaluesof fluidsin calcite
anoxicenvironmentsby the oxidationof organiccar- (Table5) with •iXSo valuesof calcitesamples FG-CC-
bon.The rangeof •i•4Svaluesfor sulfides withinor- 6, ML-23, PT-l, andPT-3 (Table 4), temperaturesof
ganic-richrocksis -22.3 to -6.3 per mil. It is sug- 29 ø, 41 ø, 22 ø, and 51øC, respectively,are obtained
gestedthat thesesulfidesmay have producedisoto- usingthe calcitewater curveof O'Niel et al. (1969).
picallylight sulfurfor later mineralizingevents.The These temperaturesare lower than homogenization
entire rangeof sulfurisotopevaluesobservedfor the temperaturesobtainedfrom primary inclusionsin
outlyingoccurrences canbe producedby an evapo- calcite (Table 2).
rite-derivedsulfide-richbrinereactingto varyingde- Despitethe evidencefor reequilibrationof •i•SO
greeswith isotopicallydepleteddiageneticpyrite. valuesfor fluidsin calcitefromoutlyingoccurrences,
Valuesof •iXSofor calcitesfrom outlyingoccur- thesevaluesare significantlydisplacedfrom the me-
rencesare generallyenrichedby 1 to 7 per mil over teoric water line and indicate that fluids which formed
the earliestmain district calcite stages.Enrichment the outlyingoccurrences couldnothavebeenentirely
in •sOis greaterwith respectto later stagesof main meteoric in origin. Althoughfew in number, these
districtcalcitemineralization.Carbonisotopestend valuesare consistentwith the hypothesisthat fluids
to be lighter,overall,with respectto all stagesof main were derivedprimarilyfroma basinalbrine.The data
districtcalcite;however,mostof the outlyingcalcite do not indicatefromwhichbasinthe fluidsmayhave
has•i•C valuessimilarto thoseof McLimans(1977) been derived.The large variationin •iD valuesindi-
stageI and II main district calcite. Carbon isotopes catesthat a numberof differentfluidsmayhavebeen
and fluid inclusionTh data indicate that calcite from responsiblefor the formationof the outlyingoccur-
the outlyingminorbasemetal occurrencesis similar Fences.
to the two earlieststagesof maindistrictcalcitemin- Valuesof •iD and •ilSOobtainedfrom sphalerite,
eralization. kaolinitc, and calcite in coal beds in the Illinois and
Therangeof •i•C valuesforthemaindistrictcalcite Forest City basins(Whelan et al., 1988) are similar
(-4.4 to -2.1 per mil for stagesI and II; -12.6 to to valuesobtainedhereinandare considerably more
-10.0 per mil for stagesIII and IV) indicatesthat scattered than values determined by McLimans
both marinebicarbonateand reducedcarbon(from (1977) on sphaleriteandcalcitefromthe maindistrict.
groundwateror oxidationof organiccompounds) may Conclusions
have been incorporated into main district calcite
(McLimans,1977). Carbonisotopedatafor outlying The mainconclusions fromthisstudyarethatthere
occurrences indicate that carbon was derived from are at least two types of outlyingbasemetal occur-
the sametype of sourcesassuggested by McLimans rences:(1) thosethat occurnortheastof the mainUp-
(1977) for the main district mineralization.Most of per MississippiValley district in Wisconsin,as well
the •i13Cvaluesfor calcitefromthe outlyingoccur- assomealongthe Plum River fault zone,which show
renceslie in the rangetypicallyexhibitedby marine paragenetic,mineralogical,and stableisotope(par-
limestones(-4 to +4%0;Ohmoto and Rye, 1979). ticularly sulfur)characteristics similarto occurrences
However,calciteswith morenegativevaluesof •ix•c associated with the pitch andflat depositsin the main
mayhavederiveda light carboncomponentfrom re- district;and (2) thosethat occurnorth andnorthwest
ducedsourcesof carbonthat are presentin someof of the mainUpper Mississippi Valley districtin Wis-
the hostrocks.In view of the similaritybetweenthe consin and to the southeast in Iowa which exhibit
•i•C and •iXSo values of calcite and associated host paragenetic,mineralogical,and somefluid inclusion
rocksin someof the outlyingoccurrences, calcitewas and stableisotope(particularlysulfur, carbon,and
probablyderivedlocallyasa productof diagenesis of oxygen) characteristicssignificantlydifferent from

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by Society of Economic Geologists, Cesar Ricardo Vargas
 Pb-Zn & BASEMETAL MINERALIZATION, UMV--IA, WI, IL 2153

thoseassociated
with pitch and fiat depositsin the BrothersStoneCompany,Martin-MariettaCorpora-
main district. tion (Fergusonquarry),Niemann-PaulConstruction
Thoseoutlyingbasemetal occurrenceswhich are (Fairbankquarry),and Weaver Construction Com-
similarto sulfidedepositsfrom the mainUpper Mis- pany(Pint'squarry)gaveusaccesstotheirproperties.
sissippiValleydistrictprobablyformedfromthe same EdRipleyattheGeology Department
ofIndianaUni-
fluidsthatgenerateddeposits in the maindistrict.The versityis gratefullyacknowledged
for collectingthe
generalconsensus in the literatureisthatfluidswhich stableisotopedata.Thispaperbenefitedconsiderably
formedUpperMississippi Valley-typedepositsflowed from the commentsof two EconomicGeologyre-
northwardfrom the Illinois basinduring the Paleo- viewers.The projectwasfinanciallysupportedpri-
zoic. Variousmodels,however,havebeen proposed marilyby the Iowa StateMining and MineralRe-
to accountfor the broad-scale migrationof the fluid: sources
Research Institutesprogramadministered
by
gravity-drivenflow (Ludvigsonet al., 1983; Bethke, the U.S. Bureau of Mines under allotment grants
1986), tectonicallyinducedflow (LeachandRowan, Gl164119 and Gl174119. Additional support was
1986), and compaction-drivenflow (Cathies and providedby the IowaScienceFoundation,theIowa
Smith,1983). Thesemodelshavebeenableto account StateUniversityAchievementFoundation,andStan-
for the relatively high temperatures(•150øC) de- dard Oil of California.
terminedfrom fluid inclusionsin sphaleritefrom the
main district. January19, July 7, 1989
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by Society of Economic Geologists, Cesar Ricardo Vargas