Genesis of The Mississippi Valley-Type ZN-PB Deposit of San Vicente

EconomicGeology Vol. 85, 1990, pp.
1402-1437
Genesis of the Mississippi Valley-TypeZn-PbDepositof SanVicente, Central Peru' Geologicand Isotopic(Sr, O, C, S, Pb) Evidence
LLUIS FONTBOTh*
Mineralogisch-Petrographisches Institute, Im Neuenheimer Feld236, D-6900Heidelberg, Germany

AND HENDRIK GORZAWSKI
Max Planck Institut fdr Chemie, Postfach 3060, 6500 Mainz,Germany

Abstract
The SanVicenteZn-Pbore deposit is situated 300 km eastof Lima in centralPeru, within
the UpperTriassic-Lower Jurassic carbonate platform (Pucarft Group) at the western margin of the BrazilianShield.Production duringthe last20 yearsandpresent reserves exceed12 milliontons of oreassaying about12 percent Zn and1 percent Pb.Sphalerite andgalena, the onlyore minerals, occuraslens-shaped bodies generally parallelto the bedding. Within the 1,400-m-thickPucarfi sequence three ore-bearing dolomiteunitsoccur.The ore lenses are boundto dolomitized tidal fiat andlagoon facies with cryptalgal lamination andevaporite
moldsandto adjacent oolithicgrainstones of barrier facies. Strontium, carbon, oxygen, andsulfur isotope geochemistry wascarried outonconsecutive
crystallization generations. Theresults obtained display systematic trends. The87Sr/S6Sr ratios rangebetween 0.7077 and0.7084. The firstgenerations display values verysimilar to those of UpperTriassic-Lower Jurassic ocean water.Latergenerations are slightly enriched in radiogenic strontium. The degreeof enrichment in radiogenic strontium is low compared to otherMississippi Valley-type deposits. The b180 values range between -6 and-10 per mil PDB,and theb3C values between +2 and-1 permilPDB.Thelatecrystallization generations are enrichedin the light isotopes of oxygenand carboncompared to the first generations. The sulfurisotope ratios of sphalerite are relatively homogeneous, ranging between 9.9 and 13.0 per mil. A trendto lightersulfur isotope ratios with advancing diagenetic stage canalso
be recognized.
The SanVicentelead-zinc deposit formedduringburialdiagenesis. The temperatures indicated by sulfur isotope geothermometry (75-92C)wouldbeconsistent withtemperatures reached at a burialdepthof about 2 to 3 kin.Thismighthavebeenreached by the endof the
Jurassic. A model basedon abiogenicreductionof sulfatesat or near the ore site, and the
introduction of a zinc-andlead-bearing basinal brinecharacterized by strontium isotope ratios slightly higherthancontemporaneous seawater andhighlyradiogenic lead,is favored. The association of the orebodies with peritidalfacies with abundant sulfate moldsis important evidence favoring the existence of two separate reservoirs for sulfurandmetals. Leaching of detrital material derived fromPrecambrian uppercrust fromtheBrazilian Shield wouldexplain both strontium andlead isotope ratios.
Introduction
Lead and zinc occurrences in Pucart rocks and as
THE strata-boundZn-Pb deposit of San Vicente (11014' lat S, 75021' longW, provinceof Chanchamayo,department of Junin) islocated 328 kmby road eastof Lima, in the Chanchamayo area, 10 km south of SanRam6n,in the tropicalrain forestof the Ceja de Selva,which is the sub-Andean highlandbetween the Andean cordillera andthe Amazon forest(Fig. 1). SanVicente is the best knownexampleof a belt of Zn-Pb-(Ba-F) deposits of the Mississippi Valleytype in the easternpart of the Upper Triassic-Lower Jurassic Pucart basin.At present, it is the onlymine in production.
* Present address:Department de Mineralogie, 13, rue des
Maraichers, CH-1211 Geneve 4, Switzerland.
sulfide-bearing pebbles in riversin the Chanchamayo areahavebeen reportedfrequentlysince1950. The Pichita Calugalead-zinc deposit,6 km northwestof SanRam6n, was the first one to be mined (between 1951 and 1965 by the CompafilaMinera Chanchamina, S.A). Amstutz (1956) reported on the carbonate-hostedMaria Esperanzalead mine, 11 km west of SanRam6n, and comparedit to the Missourilead belt deposits. The SanVicentemine wasstaked by J. CarpenaMonroy in 1955 which wasthe beginning of a small-scale lead operation. The Compafila Minera San Vicente was created in 1960 as a subsidiary of Mauricio Hochschild, S.A., and Compaia Minera Chanchamina. Subsequent explorationwith participation of the Cerro de PascoCorporationled to re-
0361-0128/90/1132/1402-3653.00
1402
Zn-PbDEPOSIT, SAN VICENTE, CENTRALPERU
1403
San
Roque'( '<' x..-i
Oxapmpa
de
Shalipayco
Tamb M
Pichita La Merced"
Caluga 75' 11 S a n Ram6n

n Vicente belt
ba)
Mal
Carahuac
San Crist6bal-I
Huaripampa
de Yauli
[]Tr-J
PUCARA
(in part massive sulfides}
la Zn-Pb-(Cu-Ag) volcanic.associated ore deposits. lb MVT Zn- Pb deposits at the baseof the Pucarsequence
O Ic MVT Zn - Pbdeposits
Town
within the Pucara sequence
o. lO 20 30 km
75'
i
FIC. 1. Locationof the SanVicenteminein an outcropmapof the PucarGroup.Geologyaccording to SzekelyandGrose(1972) and to the JapanInternationalCooperation Agency(1979) for the central and easternparts of the basin,respectively.The locationof the main Pucar-hostedstrata-bound ore deposits is indicated(modifiedfrom Fontboth, 1990).
serves of 850,000 metrictonswith 18 percentZn. In 1969 the Compafila Minera SanIgnaciode Morococha,S.A. (SIMSA)acquired partialcontrolof the San Vicente depositand by 1973 had total control.The presentproduction is 3,000 metric tons/day,which makesSanVicentethe largestzinc-producing mine
metric
cent Zn.
Fontbot et al. (1981), Gonzalez and Fontbot (1986), andFontbotandGorzawski (1988). Thispaper summarizes the geology,palcogeography, facies analyses, andtraceelementandisotopic(C, O, S and Sr) geochemistry of the SanVicentedeposit. The formation of the ore depositis studiedin the frame of in Peru. Accumulatedproduction is about 6 million the diageneticevolutionof the host rock and of the
tons. Reserves exceed 5.1 million metric evolution of the Pucarf basin.
The Pucar Basin: An Extensive Carbonate
tonsore with a gradeof 0.8 percentPb and 12.6 perAspectsof the San Vicente mine have been dis-
Platform at the Beginningof the Andean Cycle
cussed by Schulz(1971), Levin andAmstutz (1973), The Zn-Pbdeposit of SanVicenteis hosted by carLevin (1975), Lavado (1980), Fontbot (1981), bonaterocksbelonging to the Upper Triassic-Lower
1404
L. FONTBOTIAND H. GORZAWSKI
Jurassic PucarfiGroup. The Pucarfibasindeveloped ritic characteristics, depositedin sabkhalike facies. as a wide carbonate platform at the westernmargin Thesemostlikely interfingerwith clasticand evapof the Brazilian Shield in northern and central Peru. oritic sediments sourcedby the emergedBrazilian Formationasdefined The largeextentandthickness of carbonate sediments Shield(the Lower Sarayaquillo deposited in peritidalenvironments makes the Pucarft by Mgard, 1978). This easternbelt hosts the Zn-Pb basinunique amongthe Andeanbasins.The mainly deposits of SanVicenteandShalipayco, aswell asnucarbonatesediments of the Pucart Group represent merous other carbonate-hosted Zn-Pb-(Ba) occura transgression over Paleozoicterranesand red-bed rences(Figs. 1 and 2). The second paleogeographic molasse seriesand alkalineand peralkalinelavasof area is representedby the central Pucarftbasin. It the Mitu Group (Permian-LowerTriassic). alsois characterized by neritic sediments, but in genRegional aspects of the Pucarft Groupare described eral terms, deposition occurredin relatively deeper than the time equivalents in the eastern by Mgard (1968, 1978), SzekelyandGrose(1972), environments Loughmanand Hallam (1982), Prinz (1985a), and Pucarft basin. In Pliensbachian to Toarcian times shalFontbot (1990). Figure 2 shows a schematic corre- low-water facieswith increasingclasticcomponents from eastto westandfinallydominated the lation of selectedstratigraphic sequences in the Pu- advanced
carft basin.
Pucarft sedimentation in the entire basin.
Importantdifferences existbetweenthe facies developmentin the eastern(sub-Andean zone andEastern Cordillera) and in the centralpart of the Pucarft basin (Altiplano region). As discussed by Fontbot (1990), the followingtwo paleogeographic areas can be distinguished up to the Hettangian (Figs.2 and3).
The first area is an eastern belt with extensive devel-
Despitethe differentlithologic development in the

eastern and in the central Pucarftbasin, similar facies
trendscanbe tracedin both parts(Fig. 2). The peritidal carbonatesequence of the Tambo Maria Formation (Upper Triassic-Hettangian, 600 m thick) correlates with the Chambarft neritic carbonate rocks in the central Pucarft basin. The bituminous shales and
of the UlcumanoFormation (Sinemurian, opmentofperitidal dolomites, in part with preevapo- limestones

Western
Pucara Eastern
equivalents
Eastern
Toarcian
share sfrafabound Zn-Pbore deposmf, [-- elastic sediments : limesf one ,I-'- evaporifes dolomife
ore occurr'ence;> V oc[urr.
relief ofevaporific mineral
-
I
voltanits luff orpyrodastic rock

no deposition
FIG.2. Schematic correlation of selected stratigraphic sequences in the Pucarfi basin (fromFontboth,
Zn-Pb DEPOSIT, SAN VICENTE, CENTRAL PERU

/
ECUADOR / /
1405
'\
sabkha
facies
dostic
sedimentation
advances to the
west '1 Pliensb. (Oxapampa Fm.,
Chdrobamba Fm andCondorsinga
BRAZ IL
LO Leche R.
BRAZIL
i -
..i
PAC IF IC
OCEAN
L../.
'\.\
J
PACIFIC
i
\
\
Q UPPER TRIASSIC
--- probehie basin limit outcrop limit V synsimentory lcanism A evapadres
sediments' mer?
OCEAN
.!
O LIASSIC
area
Socosaoi Fm 'Areu!P'. ' '-

(Sinera?).
0 75'W 500 km
clast siments ''
(Tarclan /. '.' I
.v ...5
Chocole (r J
-. 'W (
FIG. 3. Paleogeographic schemes of the Pucarftbasin during (a) the Upper Triassic,and (b) the Hettangian-Toarcianperiod (from Fontboth, 1990).
350 m thick) can be compared to the euxinicfacies of the AramachayFormation.The Oxapampa Formation(shallow-water dolomiteand limestone,some gypsumand sandstone layers, 800 m thick) can be correlatedwith the regressive episodewhich characterizesthe Condorsinga Formation. The morphology of the westerncontinuation of the
Pucart basin remains uncertain because in the western
basins, whichare ofteninfluenced by arc-related volcanism. The mainsimilarities includerapidsubsidence rates(probably favoredby extensional blocktectonics), the predominantcarbonatesedimentation with extensive peritidaldeposition anddolomite formation, and the locationat the marginof an emergedcontinent.
Altiplano regionpossible Pucar/t sediments havebeen eroded in pre-Cretaceoustimes. A communication with the paleo-Pacific is documentedin the Ro de La LecheValley (near6 o S) wherean Upper TriassicLower Jurassic carbonate sequence similarto the Pucar/tsequence is described (Figs.2 and 3; Pardoand Sanz, 1979; Pardo, 1983; Prinz, 1985a). It hasbeen suggested that the Pucarftbasinwas limited to the westby a subduction-related volcanic arc (Audebaud et al., 1973).Available evidence indicates thatactivity
of a calc-alkaline volcanic arc started not earlier than
Strata-Bound Ore Depositsin the PucarfiGroup
Different typesof strata-bound ore deposits occur in sedimentary rocksof the PucarfiGroup (Dunin,
1975; Kobe, 1977, 1982; Dalheimer, 1990; Fontbot(,
Sinemurian-Toarcian times (Fontboth, 1990). This means that onlythe upperpart of the westernPucart basin could have been influenced by a volcanic arc.
The evolutionary styleof the eastern Pucar/t basin is moresimilarto that of carbonate platforms in pericratonic areas than to that of other Mesozoic Andean
1990). In the westernpart of the basinvolcanogenic and exhalativefactorsappear to predominate.This appliesto the Zn-Pb(-Ag-Cu)deposits, in part with massive sulfideparageneses, locatednear the baseof the PucarfiGroup in sequences with significant volcanicand/or volcaniclastic intercalations (e.g., Carahuacra,Huaripampa,and Manto Katy). In the easternpart of the Pucarft basinMississippi Valley-typeore deposits prevail.The SanVicenteand Shalipayco Zn-Pb depositsare the more important ones, but additional Zn-Pb-(F-Ba) occurrences and prospects are knownalong a north-south belt at least 200 km long (Fig. 1). They include undeveloped ore occurrences near Chaglla (lat 9o50' S, long
1406
L. FONTBOTI AND H. GORZAWSKI
75o48' W, about 90 km north of Oxapampa), Oxapampa,TamboMaria, andthe Ulcumayo andPichita Calugamines,and severalore showings southof San Vicente (Fig. 1). Huayanay,5 km south of Monobamba, is the southernmost known zinc-lead occur-
renee (Fig. 1; Tayler, 1962). Most of the occurrences are in dolomiticrocks,mainly in the Tambo Maria
Formation.
The EasternCordilleraandthe sub-Andean region are fairly inaccessible andpoorlyknown.The known ore deposits and occurrences and the persistence of facies and diageneticcharacteristics indicate that a large Mississippi Valley-type provinceis located in
the easternPucarfbasin. Therefore, this shallow-wa-
ter carbonate platformat the westernmarginof the BrazilianShieldconstitutes an interesting exploration

target.
RegionalGeology of the SanVicenteDeposit

San Vicente is located between the Cordillera Ori-
ental and the sub-Andeanzone. Figure 4 gives an overviewof the regionalgeologyof the SanVicente miningareawhichintegrates the dataof Levin (1975),
Capdevilaet al. (1977), Mgard (1978), Japan InternationalCooperationAgency (1979), internal mine reports,and our own observations. The oldeststratigraphicunit is comprised of micaschists andgneisses and is assigned to the Precambrian. It is overlainby Paleozoic sediments, including carbonate rocks of the PermianCopacabana Group, and by sandstones and conglomerates of the Permian-LowerTriassicMitu Group,whichin thisareaconsists mainlyof terrestrial elasticsediments, in part volcaniclastic, but without the lavasobserved in other partsof the Mitu Group. The transitionbetweenthe Mitu and Pucar5Groups in the SanVicente miningarea will be discussed below. Carbonaterocks of the PucarfGroup (up to 1,900 m thick) trace a north-south-trending belt. Dogger and Maim elasticrocks (the Upper Sarayaquillo Formation, about 1,000 m), as well as continental Cretaceoussediments(the Oriente Group, about 1,000 m and the Chonta Group, about 1,900 m), occurnorth of SanRamGn. Tertiary (?) rhyolitic and ignimbriticflowsare described by Levin (1975) in severallocalitiesnear SanVicente,.includingone eastof Vitoc (Fig. 4).
75025 '
+ +
75015 '
+ +
..+
110
STRATIGRAPHIC UNITS
+
+
+
+
+
+
+
--
--
Quaternary alluvium
Tertiary (?)volcanic rocks
Dogger, Nalm and Cretaceous (clastic sediments)
'.+
+ + +
+
+
+
+
.A MER[ED ++ + + + +
+ + +
+
+
+
Carbonate rocks - Pucar Group

x
xXxXxXxx
x x x x x x x
+ + +
+
and
lowermost
rueertl
Group
(Lower Permian} Limestones Copacabana Group

metamorphic
Precambrian and/or Paleozoic

rocks
+ + + + + + ++
+
+
Gabbroid rocks (undated)

(Upper Permian - Lower Triassicl Utcuyacu Granodiorite (Upper Permian - Lower Triassic} San RamGn Granite
x x XxXxXx
x
X X X
X X
SAN
X X X
X
V V.?+++++++ +
X X X
+ + + + + . + + +
X X
V V.+
X X Xx -X X X X
'%.4
;13+
+
+
+ +
+
+ +
+
+ +
+
+ +
+
+
Fault
+
+ +
+
+
+
+
+
+
Thrust Fault
c)+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
Zn soil anomaly
Zn-Pb occurrence (ME Naria
LL Llanco Cateador, CLClody, HU Huacrash, R Rondayacu}

Nine
Closed mine
Esperanza,
+
+ + + + +
0
I
5
I
1Okra
i
7525 '
75'15'
FIG. 4. Regionalgeologic map of the Chanchamayo area (compiledfrom Levin, 1975; Capdevila et al., 1977; JapanInternational CooperationAgency, 1979; internal mine repts.; and our own observations).The locationof the detailed map of SanVicente (Fig. 8) is indicated.
1407
Three intrusiveunits are distinguished. The San formation phases affecting thisareawerethe Quechua Ram6n(or La Merced) batholithoccurs at the eastern 1 and 2 phases (Oligocene and Miocene).However, part of the studiedarea (Fig. 4). It is made up of a overthrust faultslike the Utcuyacufault are typical red coarse-grained to porphyritic biotite-bearing for the Quechua3 phase(upperMiocene). granitewhichhasbeen datedat 246 ___ 10 Ma (Capin the San Vicenteminingarea devilaet al., 1977; Rb-Sragerecalculated according The Pucardsequence corresponding in part to the to Lancelot et al., 1978) andat 255 ___ 1 Ma (Gunnesch A clasticsequence carbonate rocksin et al., 1990). This uppermost Permianto lowermost Mitu Group underliesthe Pucart areyellow Triassic ageis consistent with the occurrence of peb- the SanVicentearea.The lowesthorizons
blesof the red SanRam6ngranitein the Mitu Group and brown sandstones and marls several hundred meconglomerates (for instance, nearVitoc). A K-Ar age tersthick (Schulz,1971). A red-violethorizona few and conglomdetermination of the pebbles themselves yieldsa sim- metersthick with arkosicsandstones Theseconglomerates alsocontain the ilar age (238 ___ 16 Ma; JapanInternationalCooper- eratesfollows. pebblesof the SanRam6ngranite. ation Agency, 1976). The San Ram6n batholith be- aforementioned hasa charlongs to an extensive Permo-Triassic magmatic prov- The upper part of this clasticsequence incein the EasternCordillerawhichareallycoincides acteristic red color and consists of sandstones and gypsiferous marlswith a thickness of at with the red-bedseries and alkalineand peralkaline subordinate lavasof the Mitu Group.This geologic settingis in- least 100 m. Figure 5 shows a generalized stratigraphic northterpretedasa Permo-Triassic ensialic rift zone (Konsouth cross section over 5 km in the San Vicente area. tak et al., 1985). West of SanVicente a highly tectonizedwhitish No discordance is observed between the red sandbiotite and hornblende granodiorite (Utcuyacu stonesand the overlying thick Upper Triassicto granodiorite) overthrusts the Pucart Group. Thisfault Lower Jurassiccarbonate sequenceof the Pucart contactdipsbetween20 and 40 W andcanbe fol- Group.In internalminereportsthe "Red Sandstone" included in the Permo-Triassic Mitu Group. lowednorth-south for several kilometers (Fig.4). The isusually Utcuyacu granodiorite (in the minereports also called However, Mgard (1978) indicatesthat frequently Group is detritic and is "Tarma granite")wasreportedto intrudethe Pucart the lower part of the Pucart very similarto the Mitu Group.This is rocks (Levin,1975, p. 35) andthereforeshould have lithologically by the a Jurassic or Cretaceousage. As already noted by probablythe casein SanVicente, asindicated lithologicchangeof alternatingbedsof Capdevilaet al. (1977), Levin's statement is ques- transitional
tionable on the basis of additional field evidence. A
red sandstone and carbonate rocks over about 30 m
imLower Triassicage (240 ___ 4 Ma) of the Utcuyacu (Schulz,1971; Levin, 1974). The Red Sandstone granodiorite asindicated by anRb-Srfeldspar-biotite mediately below the carbonatesequenceshould, whole-rock isochron seems to be morerealistic(Gun- therefore, be considered aspartof the Pucart Group. neschet al., 1990). It couldalsobe considered to be an interdigitation of Formation.Thus the contact Gabbroid anddioriticrocksrepresent the third in- the Lower Sarayaquillo trusiveunit in the area.Gabbroidrocksare reported between the Mitu andPucar5 groups wouldbe located northof theTarmaRiverin contact with the Utcuyacu below this lithologicchange,perhapsbetween the granodiorite (Capdevilaet al., 1977). Dioritic stocks conglomerate level andthe overlying red sandstone. intruding the Mitu andPucart Groups havebeendeThe carbonate sequence in the SanVicentemining scribed near the ore occurrence of Huacrash, south area is up to 1,300 m thick and extendsfrom Norian of San Vicente (JapanInternational Cooperation to Hettangian(Fig. 6). It strikesN 10 W and dips Agency,1976). The altered subvolcanic and volcanic between 30 and 45 E (Fig. 7). The followinglithrocks, which intercalated with Pucar5 sediments at ologic unitshavebeendistinguished (thestandardized San Vicente (see below), could be correlated with stratigraphic heightsusedin Figure 6 and in all the
these dioritic stocks. Xenoliths of carbonate rocks occur within the San
tables, as well as the abbreviationsused henceforth, are given in parentheses).
Ram6ngranite.Theseare well-beddedlimestones of-
ten displaying contact metamorphic effects (asfor examplein the Orquideas mine,wheregarnets occur). They probablyrepresentroof pendants of Copacabanalimestone (LowerPermian).
The Basal Series(BS, 0-442 m): This sequence consists of fine-grained limestone(mainlymudstone
andwackestone ) anddolomite intercalations. There
is abundantdetrital material (up to 35% detritic quartz).The dolomitic bedscoincide with the maxima San Vicente lies on the western limb of an anticline of detrital material (Gonzdez,1987). This unit retrending N 170 E. Numerousnormal faults strike cordsthe Upper Triassictransgression over the red mainly N 50 E and N 140 E. In addition, the Utcuyacuoverthrustfault is a major tectonic element. Mudstone, wackestone, packstone, andgrainstone according According to Mgard (1984) the firstsignificant de- to the carbonatetexture classificationof Dunham (1962).
1408
R. Siete Jeringos
Uncush Sur
Terropin Son Vicente
t. / / Chilpes '2i
/I
..'

-.... _----4--,--;""':Hettangian
SAN VICENTE DOL.
ALFONSO - I '
/I
1000rn
"'"',,....
/1,
7Zi
I
/.,... ,-./
/- -/'
,..-.
.,.-./.,.-. /.,... / ,,./,.,
....
"-"
NEPTUNO LIM.
'
'- I
/
/ 1--.
SAN JUDAS DOLONITE i1 -// .I..-.__.L
I " / ,,.*., /,,.*.,
500 rn
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I "/
I
I
I
I
I I
I
I
I I
I
I
I
I
I
I
I I
I
I
I I
BASAL SERIES I I
I I
I I
Norian
Om
1-1 Ii.i
'- '='-'-.
-I' I-I .i.
I I- I
RED SANDSTONE ............... '.', .. -;--
,I,
.... -'---"--,.... '...... - -.r
4,
FIG. 5. Generalizedstratigraphic sequences of the SanVicente area.The localitiesare indicated in Figure8. 1 = redsandstone; 2 = limestone; 3 = dolomite; 4 = dolomite withdiagenetic crystallization rhythmites and relatedstructures; 5 = ore horizon;6 = bituminous, laminated, silty limestone; 7 = volcanic andsubvolcanic rocks, oftenwhollycarbonatized; and8 = poorexposure.
coastal dolomitic facies with abundant detrital ma-
sandstone detrital facies at the base of the Pucarfi se- with megascopically distinguishable diagenetic crysquence. Thealepositional environments varybetween tallizationgenerations. Despitethe strongcrystalli-
zation the original depositional fabric can often be
terialandbasinal facies with fine-grained limestone. recognized in thin section usingthe "light diffusor" In two samples fromthe upperpart of thismember described by Delgado(1977). The originaltextures smallphosphate noduleshave been detectedwith a are mainlyooliticpackstone and grainstone (barrier microprobe. At thetopofthismember a slope breccia facies). Detritalquartzis absent, except in the upper
is recognized.
part.
The SanJudasDolomite(SJD,442-723m): This The Neptuno Limestone (NL, 723-801m): This dolomite consists mainly ofmedium to coarsely crys- limestone is only partly dolomitizedand serves asa talline dolomite. Thisisthefirstofthreeore-bearingfield reference horizon in the San Vicente area. A massive dolomite unitsdisplaying very similar pet- detailedstudyof the NeptunoLimestone (Gonzfilez, rographicand geochemical properties.It is char- 1987) hasshown that thisunit displays distinctive faacterized by the presence of abundant diagenetic cieschanges. The detritalproportion canreachup to crystallization rhythmites (formed by crystallization10 percent. The upperpartof the Neptuno Limestone duringdiagenesis), geodelike textures, hydraulic contains significant marlintercalations, probably inbreccias, diagenetic veinlets, and,in general, fabrics eluding tuffaceous material.Fromtop to bottom,the
1409
I 52040 '1 2 3 4 5 6 7 6 9'

A L FON SO DOLOMITE
BITI
(der.Q FACIESTYPE
SILTY LIMESTONE
-slope breccin
slopebreccla
I
SAN VICENTE DOLOM I TE
'
NEPTI
slope breccla
SAN
JUDAS
DOLOM I T!
--
slope breccla
--- slope breccln
I'
I
I
I
I
.BASAL SERIES
I
I
RED
$
LF & EG 1986
FIG. 6. Stratigraphic sequence in the SanVicente mine. Symbols asin Figure 5. Under faciestype an evolutioncurve of the deposition environment hasbeen represented(1 = open basin,4 = slope;5 = platformedge,6 -- barrier, 7 = lagoon,8 = tidal flat, and9 = continental). Starindicates occurrence of evaporites.
2000m
FIG. 7. Geologiceast-west profile through the San Vicente mine. AD = AlfonsoDolomite; BSL = Bituminous Silty Limestone; SVD = SanVicente Dolomite;NL = NeptunoLimestone; SJD = San Judas Dolomite;BS = BasalSeries; RS = Red Sandstone. Symbols asin Figure 5.
1410
L. FONTBOTtAND H. GORZAWSKI
TABLE 1. Ore Manto in the North San Vicente Dolomite
San Vicente Whole
Neptuno Limestonecomprises the followingdepositionalenvironments: top--dolomitized barrier facies(SanVicenteDolomite),partly dolomitized barrier facies, foreslope in thebasin facies, foreslope with slope breccias,and nondolomitizedbarrier facies; bottom--dolomitized barrier facies(SanJudasDolomite).
Dolomite
carbonate
(lowerpart)
Manto
sequence
(m)
961
(m)
160
Jesus
Thisdocuments a firstcollapse of the veryconstant platformsedimentation conditions which characterized the SanJudas Dolomite. The San Vicente Dolomite (SVD, 801-1,109m): This is the mainore-bearing unit. It is very similarto the SanJudas Dolomiteandconsists mainlyof dolomitized barrier calc-arenites(oolitic packstones to grainstones) with significantintercalations of bituminous, very fine to fine crystalline dolomite deposited in lagoonand tidal fiat environments. Thesehorizonsare characterized by the occurrence of pellets, abundant algalmats,chert (in part chalcedony), and frequentevaporitemolds.This memberwill be described later in more detail.
Ayala 3t (techo = top) 3i (intermedio= intermediate) 3p (piso-- bottom)

2
142 122 95 80
52
953 923 896 881

853
Levin (1975) describes an olivine basaltwithin the San Vicente Dolomite in a part of the San Vicente mine which is at present not accessible. The crosscuttingcharacterof someof thesevolcanic rocksis clear(Fontboth, 1981). However,the presence of as-
TheBituminous Silty Limestone (BSL, 1,109-1,189m):

This unit is a bituminous,laminated, black limestone
with shalyto silty intercalations. Abundant organic materialoccurs in thin bands andproduces the characteristic lamination of thisrock(totalorganic carbon between0.74 and1.59%;Lavado, 1980).The detrital proportion canbe over15 percent. The detritalgrains consist almost exclusively of quartz,but some grains
of tourmaline and white mica were also observed. The
sociated tuffaceous material couldindicate that they are in part roughlycoeval with the Pucart sediments. Based on ammonite identifications, Prinz (1985b) datesthe middle part of the BasalSeriesas Norian andthe Bituminous SiltyLimestone asHettangian. In addition,the presenceof Sinemurianin the area is proven by Prinz(1985b) onthebasis of anArnioceras foundin a bituminous silty rock in a faultedblock. Because of tectoniccomplications and poor outcrop
conditions it cannot be elucidated if this bituminous
facies belongs to the Bituminous SiltyLimestone or

to a similar unit above the Alfonso Dolomite.
quartzgrains aresubangular to subroundish andrange up to 200 # in diameter. X-raydiffraction reveals that

illitc is the main mica mineral. Its abundant Hettan-
Palacios (1980) defineda "Formaci6n SanVicente"
rocks in SanVicente.Prinz (1985b) dismissed Levin's assumptionand establishedthat the carbonate sequencein SanVicente beginswith the Norian, asin otherpartsof the Pucari basin,andconsequently, the indicating a veryhighevolution stage (meta-anthraciteso-called "Formaci6nSanVicente" of Palacios (1980) stage; Teichmiiller,1981, writ. commun.). This unit, corresponds to the Paucartambo and Tambo Maria with clear basinal facies, constitutesthe secondin- Formations (Norian-Hettangian). terruptionof the carbonate platformsedimentation. of the dolomiticore-bearing units The transitions towardplatformsedimentation at the Sedimentology bottom(San VicenteDolomite)andthe top (Alfonso All three dolomiticunits (the San Judas,San ViDolomite)are markedby slope breccias. cente,and Alfonso Dolomites)are ore bearingand TheAlfonsoDolomite(AD, about 70 m in thick- displayvery similarpetrographic and geochemical ness): This unit is the third ore-bearing dolomiteho- characteristics. The main ore horizons occur within rizon and displays similarcharacteristics to the San the SanVicenteDolomite(Figs.5 and8). The present Judasand SanVicente Dolomites. It was not studied studyhasshownthat thesethree dolomiteunitswere in detail. deposited in a peritidalplatformcomprising (1) the Tuffaceous, volcanicand/or subvolcanic interca- innermarginof the lagoon (tidalfiat subenvironment) lations occurin the upper part of the SanJudas Do- with partly preevaporitic conditions, (2) the lagoon lomite, in the NeptunoLimestone,and in the lower sensu stricto,and(3) the outermarginof the lagoon partof the SanVicente Dolomite. Although theyare (barrier subenvironment). generallyalmostcompletelycarbonatized (seeXRF The barrier subenvironment predominates and is analyses in Table 1) vesicular microlithictextures can represented by completelydolomitizedooliticpackbe recognized frequently (Fontboth, 1981, p. 98). stones andgrainstones. The identification of thesefa-
gianammonites havebeendescribed by Levin (1975) and Prinz (1985b). The Bituminous Silty Limestoneis a pyrite-rich hydrocarbon source rock (kerogene, type 2) characterized by the presence of abundant metabituminites
because a publication by Levin (1974) assigned a Ladinian ageto thelowerpart of thePucart carbonate
1411
coarselycrystallinedolomite of calcareniticbarrier faciesis lighter in color(grayto dark gray). Totalorganic carbon analyses givevalues up to 3.46 percent (Lavado,1980). Part of the organiccarbon occurs asschlieren betweendolomitegrainsandpart as massive patchesof bitumenin geodelikecavities. Detrital particlesare extremelyrare. Insolubleresidues in dolomiteinclude mainly quartz, in part as
chert, and subordinate illitc.
One interestinggeochemical characteristic is the low Sr contentof all three dolomiticunitscompared

with the Sr contents of the limestones of the Basal
Seriesor of the Bituminous SiltyLimestone (seebelow). This may indicateearly diagenetic dolomitization.
Detailed sedimentologic work (Gonzdez,1987; Fontbot6and Gorzawski,1987) suggests that in the San Vicente Dolomite there is a strongassociation
between the occurrence of ore and certain host-rock
facies. The dolomitic horizons hosting the orebodies consist mainly of barrier calcarenites. However, the ore lenses do not occurrandomlyin all partsof the barrier calcarenites. They showa clear link with in-
tercalations of fine-grained dolomite with cryptalgal lamination andmoldsof evaporites attributedto tidal fiat andlagoonfacies.
Basinevolutionand paleogeographic settingwithin
the Pucard basin
At a regionalscalethe SanVicenteore depositoccupies a characteristic palcogeographic position at the edgeof the Pucarfi basin, whichiscommon with other
0
I
1kin
I
similar ore occurrences in the eastern Pucarfi and
Ore
Occurrence
confacf
Mine
confact
---
inferred
comparable alsoto that of other Mississippi Valleytype deposits. The SanVicenteore occurs in dolomitic units depositedin evaporite-bearing peritidal environments locatedat the westernmarginof the Brazilian Shield.
FIG. 8. Geologic mapof the SanVicenteminingarea.A-A' = the profile in Figure 7.
The lithostratigraphic sequenceof San Vicente presents two partswhichcorrespond to differenttypes of basinevolution. The lower part canbe assigned to cies is difficult because of the extensive dolomitization the Paucartambo Formationand is a typical transandrecrystallization. Relictprimaryfabrics anddo- gressivesequencewhich ranges from continental lomitegrainsizeareused for thispurpose. Figure9b sedimentation (red sandstone) to marineconditions shows a typicalexample of dolomitized grainstone with carbonatedepositionand relatively abundant with a dolomitegrain sizeof about400 . The tidal detritalmaterial(basal series). The dolomitic portions
fiatandlagoon facies arecharacterized byveryfinely
of this unit coincide with maximum amounts of ter-
to finelycrystalline dolomite withrelictmudstone and rigenous particles andprobably correspond to a shore pellet-grainstone fabrics thataredifficult torecognize. environment.In general the limestones(mudstone Cryptalgal lamination (Fig. 10b andh) andevaporite andwackestone) represent subtidal to basinal facies. molds(Fig. 1l a-d) are frequentin tidal flat facies. The upper part of the sequence, which canbe inSmallpyritegrains occurintergranularly andin the eluded in the Tambo Mara Formation,comprises frequent stylolite seams. The tidalfiatandlagoon fa- three units deposited on a peritidal carbonate platciesdolomiteis very dark, almost black,due to its form virtuallyfree of detrital components (the San small grainsizeandthe presence of abundant finely Judas, SanVicente,andAlfonso Dolomites). Theyare disseminated inclusions oforganic matter. Medium to separated by two episodes of deeperwater sedimen-
1412
L. FONTBOT AND H. GORZA WSKI
i
.o
FIG. 9. a. Massive bitumen (black)in generationIII of a geodelikecavity. Note the idiomorphic terminationsof the dolomite crystalsof generationII (white) toward the massive bitumen. The dark graypartsare fineto mediumcrystalline dolomite with dispersed organic matter(height20 era,sublevel 1,630 N, ramp 235 S). b. Thin section (parallelnicolssample FSV-49) of a dolomitic diagenetic crystallization rhythmitc from generationI. The oolithic grainstone fabric is still recognizable.Note the disseminated organicmatter (gray). c. and d. Mine wall and hand specimenviews (sublevel1,640 N, crosscut 530 E, sample FSV-10a)of a sulfide layerdisplaying sequence repetitions (fd = finelycrystalline dolomite,cd = coarsely crystalline dolomite,sl = sphalerite, gn = galena). e. Polished section (parallel nicols,air, sampleFSV-44) of a similarsulfidelayer. Note the lack of corrosion betweendolomite(dark gray) and sphalerite(light gray). Galenais white. f. Disseminated, very fine inclusions of pyrite in sphalerite (parallelnicols, oil, sample FSV-10a).This sphalerite presents obvious problems in separation by flotation.
] 413
tation(the NeptunoandBituminous SiltyLimestones). The transitionfrom platform to basinsedimentation is clearly indicated by slope breccias.It appears therefore that the three dolomite ore-bearingunits representa cyclicrepetitionof large-scale tidal fiat, lagoon,andbarrier sedimentation on a platformseparated by episodesof deeper sedimentation. A dynamic model explainingthis evolution is shown in Figure 12. The peritidalfacies belongto the shallowwater carbonateplatform mentionedabove, which developed in the easternpart of the Pucar5basin(at the edgeof the BrazilianShield). Although in the SanVicenteareaunitsstratigraphically above the Tambo Maria Formation are not known becauseof the overthrust of the Utcuyacu granodiorite, it is assumed from regionalcomparisons
that marine Pucar5 sediments with a thickness of about
are reportedby Levin (1975). This simpleparagenesis, typical of Mississippi Valley-type deposits, differs significantly fromthe Pucart-hosted ore deposits associated with igneous activity(e.g.,Huaripampa and
Carahuacra). The ore in the SanVicentemineformslens-shaped bodies located in certain horizons(Fig. 13). These horizons, containing one or morelens-shaped bodies, are called mantos.The lens-shaped orebodiesare in general parallelto the stratification anddo notdisplay a great lateral continuity;the maximumlength of a singleore lens rarely extendsover 300 m. Mine reports indicatethat the maximumelongation of the ore lensesis usually north-south.Their thickness rangesbetween a few decimetersand a few meters. The top andbottomcontacts of the high-grade lenses with the enclosing dolomiteare sharp.The mantos in the northern part of the SanVicente mine are given
in Table 1.
1,200 m formed up to the Toarcian (Ulcumano,Oxapampa,and Chorobamba Formations).Subsequent clastic sediments of the Upper Sarayaquillo Formation (Middle to Upper Jurassic) resultedin a burial depth exceeding 2,000 m. By the end of the Jurassic the formerPucarbasinwasdissected by the uplift of the north-south-trending Mara6n geoanticline.Continental Cretaceous sediments (the Oriente Group, about 1,000 m, and the ChontaGroup, about 1,900 m) increased the burialdepthto about5,000 m before the Quechua1 and 2 deformation phases, which affectedthe EasternCordilleraandsub-Andean region in Oligoceneand Miocene times (Mgard, 1984).
The ore lenses are locallyaffectedby severalnormal faults.The mostimportant faults strike N 45 50 E and N 130-150 E. Recent karst dissolution
hasproduced majorunconsolidated collapse breccias containingimportantamounts of ore (Fig. 13).

Ore Textures and Structures
Rhythmicstructures
A largepart of the SanVicenteore displays a characteristic rhythmicbanding(Fig. 10a-h). It is locally

known as "estructuras cebra." These structures are
comparable to fabrics observed in numerous carbonOre Occurrences ate-hostedore depositsand also in dolomitic rocks The SanVicente Dolomite is the main ore-bearing not directly associated with ore deposits. They are unit. It hoststhe exploited part of the San Vicente generallyreferred to as"zebra ore" or "zebra rock," mine, as well as other ore occurrences.to the north but manyother localnames are alsoused(e.g., "coon(Clody) and southof the SanVicente mine (particu- tail" ore in southernIllinois; "franciscana"in southern larly visiblein profilesalongthe Ro Chilpesandthe Spain;and "mineral rubann" in the French literathe rhythmicityis basically not inherRio SieteJeringas and in UncushSur, Figs. 4, 5, and ture). Because 8). Other ore occurrences are located in the SanJudas ited from an original sedimentaryrhythmicity but of crystallization and reDolomite (Chilpesprospect,SanJudasmantos)and rather createdby a process in the AlfonsoDolomite (Alfonso mantos). Ore show- crystallization,often during diagenesis, the terms ings with uncertain stratigraphicpositionare known "crystallization rhythmite" and "diageneticcrystalin (fromnorth to south) LlancoCateador(northwest lization rhythmite (DCR)" have been proposed of Vitoc), at the Huacrash Hill, in the Rondayacu Val- (Fontboth,1981; Fontbot and Amstutz, 1983). The term diagenesis includeslate diagenesis, i.e., ley, and north and south of Monobamba(Figs. 1 processes taking place under considerable burial. In and 4). The ore paragenesis is very simplewith sphalerite fact, diagenetic crystallization rhythmitesappearto and galenaas the only ore minerals.The Zn content be in most casesa product of burial diagenesis. In may rangeup to 30 percent.The averagegradesof earlier stages of the investigation (Fontbot( andAmthe ore are 11.8 percent Zn and 0.8 percent Pb, re- stutz, 1983) the working hypothesis was proposed reflecta process of differentiation spectively. Pyrite formspart of the paragenesis, but that the rhythmites is always presentin very smallamounts, exceptin one by crystallization fractionation during diagenesis in of AmstutzandPark (1971). Detailedgeohorizonof the Chilpesprospectwhere it occursin the sense two massive layersa few centimeters thick within fault chemical work carriedout on rhythmitesof numerous aroundthe world (FontbotandGorzawski, planes. Tracesof marcasite, chalcopyrite, bournonite, localities and other sulfosalts are present.Fluorite and barite 1987; Gorzawskiet al., 1989) only supports certain
1414
Zn-PbDEPOSIT, SANVICENTE,CENTRAL PERU
1415
s'l
lmm
,5o,
FIC. 11. Reticulate textureof galena (gn)andsphalerite (sl)in dolomite (do);evidence of vanished evaporites (1,452 N level,gallery405). a. View of minewall.The darkpartsconsist of sphalerite and galena, the lightpartsof dolomite. b. Handspecimen view.c. andd. Polished sections (parallel nicols, air). Galenaclearlydisplays pseudomorphic textures after a solfate mineral,probably gypsum. Thisis particularly clearin photo(d) whichis an enlargement of the upperleft areaof (c).
described in the present workarethought aspects of this hypothesis. In particular, it appears rhythmites of diagenesis, under that the process generally is not isochemical andin- to haveformedduringlate stages by a reaction eludes dissolution andreplacement phenomena. The a burialof abouttwo to threekilometers,
FIC. 10. Diageneticcrystallization rhythmites of SanVicente.a. Mine wall (mantoAyala, 1,652 N level, ramp 360). b. Hand specimen (sample FSV-60) ofdiageneticcrystallization rhythmiresfrom the same exposure shown in (a). The darkbands(generation I) consist of fine-grained sphalerite anddolomite with disseminated organicmatter. Cryptalgallaminationis still recognizable. The bipolar growth of yellow sphalerite (Ha), in part geopetal,canbe easilydistinguished. Two generations of dolomite(IIb andIII) are visible.c. Hand specimen (sample FSV-44) showing a complex texturewith somerepetitions in the crystallization sequence anddissolution features.d. Mine wall with anotheraspectof the manto Ayala (1652 N level, ramp 360). The lower part of the photo consists of dolomiticdiageneticcrystallizationrhythmires. The upperpart shows a transition betweenorbicularlikeandrhythmicore textures. e. Hand specimen of diagenetic crystallization rhythmitcore (sample FSV-I). f. Polished section (parallel nicols, air) of the sample shown in (e). I = darkfine-grained sphalerite (sl)anddolomite(do),II = brown sphalerite,and III= sparry dolomite and occasionally galena (gn). g. Hand specimenof aliagenetic crystallization rhythmireore showing high periodicity.h. Samesample,detail of the three generations forming a aliagenetic crystallizationrhythmire: I = fine-grainedsphaleriteand dolomite with algal lamination,II = brown-yellow sphalerite,and III= sparrydolomite.
1416
-E
-W / / / /"
~E /
/ /
/ /
/ /
/ /
/ /
/ /
/ /
/5
's
b/
'/
,/
/./
/1
Ore body
Slope breccia
.Location of studied stratigraphic column
Arrows indicate east- and westwards migration of barrier (b)
FIG. 12. Dynamicmodelexplaining the development of the carbonate platformin the SanVicente
I (Fig. 10f). The limit of the original carbonate rockwithaninfiuxing basinal aboveand below generation betweengenerations I andII is gradational in detail, Crystallization rhythmites canalso be produced by often displaying dissolution patterns.In contrast to processes other thanburial diagenesis and in other generation I, generation II contains few opaqueinthansedimentary environments. For example, similar clusions and is thereforeusuallylight colored.Zonal rhythmicbandedstructures are alsoproduced by crystal growthisoftenrecognized. Geopetal features metamorphic or magmatic crystallization andrecrys- are frequent.For examplein Figure 10b, c, andh, it tallization. canbe seenthatgeneration II sphalerite isbetterdeIn the diagenetic crystallization rhythmites from velopedabovethanbelow the bandsof generation I. SanVicenteand other localities it is possible to rec- Several subgenerations are oftenobserved (Fig. 10b). ognizetwo or three consecutive crystallization genGeneration III: This generation consists of the reerationsmegascopically. On the basisof geometric maining central spaceor its xenomorphous filling, criteria the followingthree generations are distin- which is coarse-or very coarsegrained dolomite or guished, with dolomite, sphalerite, andgalena asthe galena(Fig. 10e and f). Occasionally it consists of mainminerals (seealsoFig. 10e-h andTable 2). calciteor massive bitumen(Fig. 9a). The contact beGeneration I: Thisgeneration isa dark,fine-to me- tweengenerations II andIII does not show dissolution dium-grained aggregate of dolomite with or without features andis sharp in detail(Fig. 10f). The antipolar sphalerite with numerous disseminated opaquein- crystalsof generationII are often in direct contact clusions (mainlyorganic carbon, subordinate pyrite) and then generation III is missing. withinandbetweenthe grains. The smallgrainsize Inasmuchas these generations are distinguished andthe abundant opaque inclusions yielddarkcolors usinggeometric criteria,a stricttime correlation beevenin the cases in whichthisgeneration consists of tweendifferent partsof the deposit maynotbe correct dolomite. Although generation I is essentially a re- but constitutes a first approximation. crystallization product, relict primary depositional Diageneticcrystallization rhythmitesconsisting of features like ooliticgrainstone fabric (Fig. 9b) or dolomitealsooccurin ore-freepartsof the SanJudas, cryptalgal lamination (Fig.10b)canbestillrecognized San Vicente, and Alfonso Dolomite units. As in other in places. ore districts, they havebeen usedasan empiricalexGenerationII: This generationconsists of coarse plorationguidebecause of their frequentassociation or very coarse subhedral crystals of dolomite and/or with ore minerals.They reveal the interactionbesphalerite arranged in a bipolarpattern, growing tweena fluid anda sedimentary rock,usuallycarbonbrine.
1417
500
-400
-300
-200
-100
I 100 m
.200
19800 Prelection plane 20450

cI
19060 E 0
MINE
lOOm
I I Proj. plene 20300

N9oE
SECTION
SAN VICENTE
liOE
1900E
20(00 E
201hOE
Projection plane 20680
lOOm
FIG. 13. a. and b. Representative east-west sections of the San Vicente mine projected onto the projection planes20450 and 20680.
1418
TABLE 2.
L. FONTBOTtAND H. GORZAWSKI Compositionof RepresentativeExamplesof Diagenetic CrystallizationRhythmitesfrom SanVicente
Sample atin
FSV-I
IIa
IIb
III
Sphalerite + dolomite
[Pyrite (a) and (b)l

FSV-60 Dolomite q- sphalerite
Dark brown sphalerite ]Pyrite (a) and (c)

+ marcasite
Light brown sphalerite
Dolomite q- galena
(a) and (c)] Yellow sphalerite

Brown sphalerite
Gray dolomite
Yellow
White dolomite
Dolomite q- galena
{Pyrite(a)}
SV-7
SV-41
Sphalerite+ dolomite ]Authigenicquartz]
sphalerite
Dark brown sphalerite
{Pyrite (a)}
Dolomite
{Pyrite (a)}
Dolomite + sphalerite
SV-41 a
[Pyrite (a) and (c)] Sphalerite (ca. 75%)

+ dolomite
[Pyrite(c)l
Dark brown sphalerite
{Pyrite (a)}
Dolomite or
{Pyrite (a)}
occasionally
massive pyrite
]Pyrite (a)]
Abbreviations: (a) - euhedralto subhedral grainsrangingbetween 1 and 10 tt in size, occasionally up to 100 tt; (b) = very small inclusions disseminated in sphalerite; (c) -- smallinclusions orientedalongcrystallographic directions in sphalerite; [ ] -- accessory mineral;{ } = very smallamount
The formerpresence of evaporiteminerals is well documented in several partsof SanVicente,especially such a fluid in San Vicente are discussed later. in manto 3t (Table 1). The most commonevidence consists of pseudomorphs of coarsely crystallinedoOther structures lomiteafter gypsum nodules in dolomitized algalmat Generationscomparableto those in diagenetic laminatedwackestones and mudstones. Spectacular crystallization rhythmites are alsorecognized in other examplesof pseudomorphic textures after sulfate fabricsnot displaying a rhythmicbanding.They in- minerals are the reticulatetextures of galena in sphalcludeorbicularlike andcockade structures (Figs.10d erite and dolomiteshownin Figure 11a to d. and 14a). Variousfabricsindicate an overpressure regime Paragenetic sequence The parageneticsequence of SanVicente can be duringcrystallization fromthe ore fluid.Among these are hydraulicbreccias,upward veins,and tepeelike studiedeasilyin the megascopically observed crysstructures. Severalpartsof the SanVicente Dolomite tallizationgenerations of the rhythmitesand related and in crosshavehydraulicbreccias with fragments of dark fine- fabrics,aswell as in hydraulicbreccias sequence is simple and to medium-grained dolomite rimmed by subhedral cuttingveins.The paragenetic coarselycrystallinedolomite(Fig. 14e and f). The constantthroughoutthe deposit.It can be summaasfollows: (I) medium brecciamatrixconsists of sparrydolomiteand often rized in eachof the generations contains spots of massive bitumenin geodelikecavi- crystalline dolomiteand sphalerite,(II) sphalerite or ties. Brecciated ore fragments occurin a few places, sparrydolomite,and (III) galenaor sparrydolomite but ore mineralsgenerallydo not crystallizein the and subordinate massive bitumen and calcite. The matrixof the breccia.The hydraulicbreccias are con- paragenetic sequence observed in rhythmites isshown sidered to haveoriginated through breaking anddis- in more detail in Figure 15. solution of dolomiteunder overpressure conditions. Scarcepyrite crystallizesin generationI, mainly Thisis supported by their frequentoccurrence in ho- as very smallgrains,which are in part euhedral.In rizonsparallelto the beddingandby their association generationII, pyrite is still lessfrequent and forms in sphalerite anddolomite.Sometimes with crosscutting veinsproducedby escaping solu- smallinclusions of pyrite and alsoof marcasitefollow tions.The prevailing overpressure regimeis clearly the inclusions documented in Figure 14b, which showsone such crystallographic planes in sphalerite of generation II. crosscutting vein abovea brecciahorizonlocatedun- A thin rim of smalleuhedralpyrite crystals occurs at the border between sphaleriteII and der a layer of dark dolomite. In places, crosscutting sometimes veins break dolomite layers producingtepeelike dolomiteIII. In generation III, only very sparse and Pyrite occurs in structures that are always orientedupward(Fig. 14c smallgrainsof pyrite are observed. and d). placesasvery abundant and very small(1-0.1 #) in-
atic, resulting in dissolution,recrystallization,and crystallizationof new phases.The characteristics of
Zn-PbDEPOSIT,SANVICENTE,CENTRAL PERU
1419
C i
FIG. 14. a. Cockadelikestructurewith clear dissolution featuresand repetitionsin the paragenetic
sequence. I = fine-grained dolomite and sphalerite, IIa -- coarsely crystalline dolomite, IIb -- brown sphalerite, IIc = sparry dolomite, andIII= sparry dolomite withblackspots of massive bitumen (1652
N level, crosscut 610E). b. Vein of white sparry dolomite (III) formed during burial diagenesis by deposition fromthe upward-escaping brine.In SanVicentesuch veinsalways pointupward.The over-
pressure regimeis clearlyindicated by the formation of a stratiform breccia belowthe layer of dark dolomite(1652 level, gallery540 N). c. Exampleof tepeelikestructure produced by upward-escaping brines(sampled by P. Levin).The darkbrokenpartsconsist of fine-grained dolomite andsphalerite of generation I, the lightpartsof sparry dolomite (III). d. Similar tepeelikestructure (minewall, 1750 N level,ga1280S, 70-cmwidth).e. andf. Hydraulic breccia similar to thatshown in b. Subhedral coarsely crystalline dolomite of generation II surrounds the fragments of darkfine-grained dolomite. The matrix is white sparrydolomiteand includes a few spots of blackbitumen(1652 level, gal 490 N, (e) = 2-m
width).
1420
SAN VICENTE
ORE
rly IIB u r i a 1 d i a ge ne s i s
II
I
Gypsum
Dolomite
mll
Calcite
Quartz
Pyrite
?)b_ _
___ )L b
I
b
I
()
I
i
Marcasite
Sphalerite
Gale.a
Bitumen
((
IIb II--
( ()
I
I
)
I
I
I
I
__
Stylolitization
DCRfoation
II II
-'- -
Ii
II
I
I
Formation of
hydraulicbreccias
and veins
FIG. 15. Parageneticsequenceof the San Vicente ore. The crystallization generations I, II, andIII ofdiagenetic crystallization rhythmites (DCR) are used for reference and also for textures other than diageneticcrystallization rhythmites.Abbreviations: b = very finely disseminated grains,c = medium grained, d -- coarsely grained, h -- chert,i = inclusions in sphalerite following crystallographic directions, m -- massive bitumen,o -- only if galena is muchmore abundantthan sphalerite,r = in a thin rim of small euhedral crystalsbetween generations II and III, s -- occasionally containing bournoniteandother sulfosalts, x = coarsely to very coarsely grainedxenomorphic filling, andy = paleyellow. Only occasional occurrences are given in parenthesis.
ore structures. Featuresindicatingdissolution of previously formedore minerals are observed but are infrequent(Fig. 10c). However, dolomitedissolution is widespread, especially in hydraulic breccias (Fig. 14b, e, and f). The paragenetic positionof sphaleriteand galena is clearlybetweenthe finely to mediumcrystalline dolomiteof generation ! andthe coarsely crystallinedolomite of generation III. In places, especially in nonrhythmite structures, partialrepetitions of the parageneticsequenceare recognized(between dolomiteII andsphalerite II, but neverwith galena; Fig. 9c and d). This recognitionand the repeatedpeaks of Fe in generation I! sphalerite denotea minorscale pulsationin the physicochemical conditionsof the fluid duringore deposition, but cannot be compared, for instance, with the repetitions of the sequence described for the ViburnumTrend (Hagni, 1983), which indicatesequential mineralization phases. The simple and typical paragenetic sequence of SanVicente is consistent with the series of solubility products of iron, zinc, and lead sulfides(Anderson,1983; Anderson and Garven, 1987). The absenceof important sequencerepetitionsarguesfor a singleore-forming
event.
The coarsely crystalline dolomiteof generation andthe paragenetically slightlylater sparrydolomite forming the matrix of the hydraulic brecciasand crosscutting veinsare essentially postore. The patches
of massivebitumen are the latest to be formed, as
clusions in sphalerite(Fig. 9f). This sphaleritemay containrelatively high Fe valuesand is sometimes erroneously calledmarmatite. This pyrite cannotbe separated by flotation. Sphaleriteoccursin generations ! and II. In the first one it is fine grainedandintergrownwith dolomite.Sphalerite of generation I! iscoarsely crystalline, often displaying severalsubgenerations, the last of whichis oftenpale yellow. Microprobe analyses indicatethat generation ! sphalerite contains around1 to 2 percentFe. Profilesacross generation I! sphalerite shownumerous peaksof high iron content(up to 5 and 6% Fe) separated by low values.The last pale sphalerite is virtuallyiron free. Colloformsphalerite is seenin places(Fig. 9c). The greatest amount of galena occurin generation III (Fig. 10e and f). A smallamountis containedas intergranular space fillingsin prior generations (Fig. 9e). Galenais usually muchlessabundant thansphalerite (avgZn/Pbgrades about12/0.8); however, there are layers in which galena is more abundantthan sphalerite. In these layers galena generally crystallizes before the largestpart of sphalerite.Calcite,which is occasionally present,crystallizes in generation III. The paragenetic sequence of the diagenetic crystallizationrhythmites canusually be appliedto other
denoted by their occurrencein geodelike voids in sparry dolomite. Sparry dolomitealsopredatesthe regionalfault systems affectingthe area.
Trace Elements
Lithogeochemistry of the Pucardsequence A detailedlithogeochemical profile across the sedimentarysection at SanVicentehasbeen comileted (Gonzdez, 1987, Fontbot and Gorzawski, 1987).
The soluble fraction obtained with a standard HC1
and HNO3 dissolutionmethod was analyzed with atomicabsorption spectrophotometry for Fe, Pb, Zn,
Cu, Mn, Sr, and Na. Flameless AAS was used for the
Ag analyses. In addition,Si, A1,Ca, Mg, Fe, Ti, Sr, K, andBa were analyzed by XRF (pressed powdertablets). The main resultsof this investigation can be
summarized as follows.
In Table 3 the geometricmean valuesof the orefree samples (i.e., thosewith Zn or Pb valueslower than quantile9s) sortedby lithologicunits are presented. Samples whichpetrographically indicate volcanic influence (i.e., carbonatizedvolcanic-subvolcanicand tuffaceous rocks)havebeen groupedseparately. In general, the petrographiccharacteristics are reflectedclearlyby the lithogeochemistry. Thus, the limestoneunits--Basal Series,Neptuno Limestone, and BituminousSilty Limestone--have the
Zn-PbDEPOSIT, SAN VICENTE, CENTRALPERU

TABLE 3.
1421
Major andTrace ElementAnalyses of Host-Rock Samples

Fe
0.38 0.39
Unit n*
AD BSL SVD NL I 10 77 21
n
I 7 41 7
SiO2 AI20 CaO MgO Fe*

9.1 8.6 0.8 2.1 0.5 1.0 29.0 39.8 19.3 1.4 0.28 0.11
Ag*
1.00 0.01 <1 <1
Pb* Zn* Cu*

25 33
Mn*
1,000
Mn
1,040
Ti
33
Sr*
50
Sr
71
Na*
305
K
840
Ba
n.a.
141
20
0.1
0.3
31.5
39.0
20.6
11.0
0.17
0.12
0.43
0.24
32
30
20 42
14
11 7
12
365 1,333
112
228 1,333
122
43 323 6 68
18 81
556 84
108
204 170
208
1,786 169
678
86 20
32
SJD
BS RS
49
64 3
9
18 i
1.5
11.9 26.7
0.2
1.9 3.1
30.9
34.1 18.7
20.5
6.7 0.6
0.33
0.37 1.25
0.50
0.73 1.38
0.03
0.04 1
36
29 19
9 41 38
8 14 20
1,542 135 585
1,106 164 642
8 85 278
76 144 129
134 211 188
311 261 193
359 2,792 2,369
8 66 764
Volc 16
12 16.4
8.3
17.5 11.4 1.25 1.93
3.66 32
28
24
718
538 939
57
90 189 1,931 112
SiOe,AlcOa,CaO, MgO, andFe values in percent,all other values in ppm;AASanalyses of soluble fractionare indicated with an
asterisk; all othervalues areXRF analyses of totalsample; additional ICP analyses for Hg from3 limestone and11 dolomite samples yieldvalues between 25 and85 ppb.Abbreviations: AD = Alfonso Dolomite, BSL= Bituminous SiltyLimestone, SVD-- San Vicente
Dolomite, NL -- Neptuno Limestone,SJD = San JudasLimestone,BS -- BasalSeries,RS = Red Sandstone; Volc -- carbonatized
volcanic, subvolcanic, andtuffaceous rocks; n.a. = notanalyzed; n = number of samples analyzed. Analyses performed at Laboratory of the Instituteof Mineralogy, Heidelberg
highestCaO contents,whereasthe dolomites--San Mn valuesin the dolomitized portionof the sameooJudasDolomite, San Vicente Dolomite, and Alfonso litic barrier facies at the lower part of the SanVicente Dolomite--have the highestMgO and Mn contents. Dolomite (Fontbot(and Gorzawski,1987). Sr tendsto be enriched in limestones with respect to The mean valuesfor Zn of the group of ore-free dolomites. Ti and Fe appearto be diagnostic of vol- samples of the SanVicente Dolomite (42 ppm) and canicinfluence. Detrital input is indicated by highK SanJudas Dolomite (9 ppm) are not anomalous comandSr values coupled with Ti amounts clearlylower pared to the rest of the sequence or to dolomiticsethan those of volcanic-influenced rocks. The XRF quences in other partsof the world. The fact that the analyses yield higherSr andFe values thanAAS anal- zinc values in the wholesequence, includingthe oreysesbecause significant amountsof Sr are contained bearingunits,lie within the field of normalsedimenin insoluble detrital minerals and because only part tary rocksconfirms the visualobservation thatthe ore
of the pyrite wasdissolved. In contrast, usingboth lenses havevery sharp boundaries. Furthermore, the analytical methods, Mn values are similar,indicating positionof Levin (1975) that the whole Pucar/tis that Mn is mainlycontained in the carbonate soluble anomalous in Zn cannotbe supported.
fraction.
The Mn valuesare higherin the ore-bearing units (1,542 ppmin SanJudas Dolomite,1,333 ppmin San Vicente Dolomite) than in the other carbonateunits (135 ppm in the BasalSeries,112 ppm Mn in the Neptuno Limestone,and 365 ppm in the Bituminous Silty Limestone)and are alsohigher than in other shallow-water dolomitic rocks(e.g.,Bencini andTuri, 1974). Thesehigh Mn valuesbear no relationto volcanic activity and are either connectedwith the dolomitization process or areproduced by theinfiuxing basinal brine.The firstpossibility is favored by low
Mn values of the nondolomitized oolitic barrier facies
Trace elementcontentof the ore
Two types of trace element analyses of ores are available. Table 4 contains averages of XRF analyses of selectedore samples(P. Soler, writ. commun., Paris).Table 5 displays analyses on pure sphalerite grains carriedout by opticalemission spectrography
(E. Schroll, writ. commun.,Vienna). The low trace
elementcontentof the SanVicenteore is typicalfor Mississippi Valley-typeore deposits and is different from the trace elementpattern of the volcanogenic deposits in the centralpart of the Pucarfi basin(Soler,
1987).
in the upperpart of the NeptunoLimestone andhigh

TABLE 4.
Manto Manto Jesus(richores) Jesus(poorores) AyMa n 3 3 3 3
GeometricMean of XRF Analyses of SelectedOre Samples from SanVicente

Zn 28.4 29.7 8.7 34.1 Pb 4.0 4.8 6.3 0.7 Fe 1.17 0.58 0.50 1.05 Ag 20 19 17 52 Cu 367 67 150 183 Mn 1,133 900 1,300 833 Ge 116 34 79 38 Sn 43 40 20 20 Cd 17 33 30 10 Se 1,560 1,280 860 2,393
Zn, Pb, and Fe in percent;all other valuesin ppm; P. Soler,writ. commun.,Paris
1422
TABLE 5.
TraceElementAnalyses on Pure Sphalerite Samples from Oresin the SanVicenteDolomite
Sample
FSV-3 FSV-39 FSV-44-IIa FSV-44-IIb FSV-54-I FSV-79
Ag
29.0 23.0 n.a. n.a. n.a. 1.5
Co
7.5 8.8 n.a. 21.0 16.0 6.8
Cu
1 0 n.a. 73 23 I
Ga
8.1 1.3 50.0 40.0 28.0 2.8
In
0.33 0.1 0.57 0.72 0.16 0.10
Ge
11 36 62 44 49 29
Mn
152 52 n.a. 285 79 95
Mo
1.6 2.2 n.a. 1.7 65.0 2.0
Ni
1 1 n.a. 3.8 1 4.8
T1
11.0 7.4 11.0 8.0 7.3 3.7
Va
1.50 0.3 n.a. 2.00 0.55 0.73
All valuesin ppm; n.a. -- not analyzed.
Opticalemission spectrography, in part with doublearctechnique; E. Stroll,writ. commun., Vienna
Dolomite samples from the ore-bearinghorizons havea relativelyhigh Mn content,whichisconsistent This investigation hasfocused on possible isotopic with the XRF and AAS analyses of whole-rocksamdifferences in subsequent generations of carbonates pies.In Table 3 notethat the sample preparation and and sulfidesin order to characterize the diagenetic someof the analysis methods are differentfromthose evolutionof hostrock and ore. For this purposethe in Table 7, thereforea directcomparison of the results followingmain groupsof samples from the San Vi- is not possible. cente areawerecarefully selected. 2Groups B, C, and The strontium andrubidiumcontents of generation D correspond to specimens of the ore-bearing San I lie in the range expectedfor dolomiticrocks(WeVicenteDolomiteandSanJudas DolomiteandGroup depohl,1974). It appears that, with some exceptions, A alsoincludeshostrocksof other lithologicunitsfor Sr, Rb, and Na contentsare generallylower in dolocomparison: (A) hostrocks(sevenspecimens, seven mitesof generation I thanin corresponding dolomites samples); (B) rhythmites andrelatedtextures without of generationII. The other trace elements are not anomalous nor ore (nine specimens, 20 samples); (C) ore-bearing rhythmites(sevenspecimens, 15 samples); and (D) do they displaya systematic concentration trend besulfideminerals(sphaleriteand galena,sevenspeci- tween dolomite generations. mens,25 samples).
Isotopic Investigations
Fifty-three S7Sr/S6Sr ratios, 41 (13C and(sO val- Strontium isotopes
ues,and20 (34S values havebeendetermined. A clean Analyticalmethods: Strontiumfor isotopeanalyses fromcarbonate andsulfide samples usseparation of the differentcrystallization generations wasseparated wasobtained by using a modified dentaldrill andbin- ing standard techniques of dissolution andcationexocularmicroscope. The strontium isotope ratioswere change chromatography. Strontium isotope ratios determined at the B.R.G.M. (Orleans,France), and were measured on a FinniganMAT 261 solidsource the sulfurisotope analyses were performed by C. W. mass spectrometer equippedwith a doublecollector Field at OregonStateUniversity. The carbon andox- system. During the periodof analyses the meanvalue of NBS 987 standardwas 0.710277 ygen isotopeanalyses were performedby H. Gor- of 12 analyses zawskiat the Max-Planck-Institutf6r Chemic (Mainz, d-0.000022(2 0' ..... ) fortheSTSr/S6Sr ratio.TheS6Sr/ Germany). The rubidiumcontents in carbonates were SSSr isotope ratiosreportedin Tables7 and 8 were normalized to a value of 0.1194 for S6Sr/SSSr. The analyzed by AASby R. Sobott(Preussag-BerkhSpen, Germany), andfor comparison, in a few samples, by SVSr/S6Sr ratioswere obtained duringrunsof eight neutronactivation by E. Pernicka(Max-Planck-Insti- blocks with ten scans each. Error on these ratios is at the 2a level where 2a .... = 2 standard deviation tut fiir Kernphysik, Heidelberg,Germany). TheSTSr/S6Sr runs ofthesulfide samples A petrographic description of the specimens ana- n blocks. to thoseof carlyzedis givenin Table 6. The traceelementcontents were of similarquality and precision (seediscussion of reare givenin Table 7. The selected specimens include bonateandwhole-rocksamples the main facies,both ore and nonorebearing. suits below). Additionalanalyticdetailscanbe found The geochemical characterization includesAAS in Gorzawskiet al. (1989). analyses for Fe, Mn, Zn, Cu, Pb, Na, Rb, andSr. For Results anddiscussion: The results ofthe S7Sr/S6Sr this purposesamples were treated with cold NaC1 analyses on carbonate samples are givenin Table 7, (1N) in orderto avoidsulfide dissolution. thoseof sphalerite andgalena are contained in Table 8, and all resultsare plotted in Figure 16. Among the representativehost-rockspecimens, 2 For mostspecimens two or more subsequent crystallization two limestones andfour dolostones from differentpogenerations were analyzed separately. For thisreason the number sitions in the stratigraphic sequence were analyzed. of analyzedsamples in Table 7 largely exceeds that of specimens
listed in Table 6.
The S7Sr/S6Sr ratiosare remarkably similarfor all
Zn-PbDEPOSIT, SANVICENTE, CENTRALPERU

TABLE 6.
1423
Petrographic Descriptionof the Samples Usedfor IsotopicStudies Unit

SVD
SVD SVD SVD
Field no.
A-052
B-054 B-064 D-001
Anal. no.
HGA-118
HGA-117 HGA- 120 HGA-041
Height
0916
0907 0919 1035
Description
DCR, gen. I: mediumcrystallinedo (ooliticpackstone with somecryptalgallamination) Homogenous medium crystallinedo (oolitic packstone) Do DCR, medium crystallinedo (oolitic grainstone) Medium crystallinedo (well-sortedooliticbioclastic grainstone) Do DCR, gen. I: medium crystallinedo (oolitic packstone with cryptalgallamination) Do DCR, medium crystallinedo (well-sortedoolitic grainstone) with do veinlets Do DCR, medium crystallinedo (oolitic grainstonewith cryptalgallamination)with do veinlets Sl-doDCR, fine-grained sl and do (mudstone with cryptalgal lamination) Do DCR, finely crystallinedo and sl (packstone with algal
mats) Bituminoussilty limestonewith fossilfragments(mudstone) Bituminouslaminatedsandylimestone Do DCR, layersof finely crystallinedo (pellet wackestone with algallamination)and of mediumcrystallinedo (oolitic packstone) Sphaleritewith very coarsely crystallinedo Sl-doDCR, gen. I: sl + medium crystallinedo (oolitic grainstone, layersof laminatedpellets) Sl-doDCR, gen. I: sl-bearing finely crystallinedo (pelmicrite?) Sl-doDCR, gen. I: sl-bearingfinely crystallinedo (pelmicrite?) Do DCR, gen. I: medium crystallinedo (oolitic grainstone with somecryptalgallamination)
Gen. II: do Gen. III: calcite
D-009
E-037 E-038 FSV-007 FSV-009 FSV-015 FSV-018 FSV-038
HGA-049
HGA-042 HGA-051 HGA-059 HGA-122 HGA-038 HGA-039 HGA-044
SVD
SVD SVD SVD SVD BSL BSL SVD
1048.2
0862 0863 0923 0953 1117 1145 0853
FSV-039 FSV-041 FSV-044 FSV-044
HGAo046 HGAo061 HGA-063 HGA150
SVD SVD SVD SVD
0853 0881 0923 0923
FSV-052
HGA-053
SJD
0530?
FSV~052 FSV-052
FSV-073
FSV-079
HGA-054 HGA-055
HGA-056
HGA124
SJD SJD
SVD
SVD
0530? 0530?
0943
0953
FSV-210-5 FSV-215
K-043 MT-003
HGA-126 HGA-040 HGA-115
SVD SVD
NL RS
0854 0923
0755 -0028
Do DCR, gen. I: medium crystallinedo (well-sortedoolitic packstone) Do-sl DCR, gen. I: medium crystallinedo (packstone to grainstone) Finely crystalline do (mudstone) Sl-doDCR, fine- to medium-grainedsl with somedo and cryptalgallamination) Do (silty wackstone with lithoclasticfragments, foreslope breccia)
Calcite-cemented sandstone
NEP- 12
T-078
HGA- 187
HGA186
SJD
BS
0711
0420.7
T-090 T-103
HGA- 116 HGA-047
SJD SJD
0490 0569
Finely crystalline do Limestone(intramicrite-wackestone) Medium crystallinedo (oolitic grainstone) Do DCR, medium crystallinedo (bioclasticoolitic grainstone)
Metersabovethe bottomcontact of the carbonate sequence Abbreviations: DCR -- diageneticcrystallization rhythmites,do = dolomite,gen. = generation,sl = sphalerite;BS = BasalSeries, BSL = BituminousSilty Limestone,NL = Neptuno Limestone,RS = Red Sandstone, SJD -- SanJudasDolomite, SVD -- SanVicente
Dolomite
samples (avg= 0.70806, Fig. 16). All of thesesamples Materialof generation I (generally darkfine-crysare very slightly enriched in radiogenic strontium talline dolomite) and generationII (white coarsecompared to the estimated S7Sr/S6Sr ratioof 0.7075 crystalline dolomite) wasanalyzed separately for oreto 0.7078 for seawaterduring Upper Triassic and free diagenetic crystallization rhythmites andrelated Lower Jurassic times(Burkeet al., 1982). Sample MT- textures.The resultslie in the samerange as those 003, which was taken from the Red Sandstone at for the hostrocks.However,dolomite of generation the base of the transgressive sequence,is consid- II is always slightlymoreradiogenic thandolomiteof erablyenriched in radiogenic strontium (S?Sr/S6Sr generation I of the samesample(Fig. 16). In the ore=0.70889). bearingdiagenetic crystallization rhythmites the do-
1424
L. FONTBOT AND H. GORZA WSKI
Zn-Pb DEPOSIT,SAN VICENTE, CENTRALPERU TABLE 8. Resultsof S and Sr IsotopeDeterminations of SulfideSamples from SanVicente
1425
Field no.
FSV-039
Lithologic unit
SVD
Manto
2
Anal. no. (HGA-)

92 149
153
Description
Massivesphalerite Massivesphalerite
Galena
(a4S (%0, CDT)

12.1 12.2
6.8
S7Sr/S6Sr
0.70838
0.70810
2a
0.00022
0.00004
FSV-041 FSV-007 FSV-044
SVD SVD SVD
3p 3t 3t
78 79 80 75 76 77 81 82 83 84 85 86 87 88 89 1,50 151
154
DCR: sphaleriteI DCR: sphaleriteII DCR: galena DCR: sphaleriteI DCR: sphaleriteIIa DCR: sphaleriteIIb Sphalerite Sphalerite Sphalerite Sphalerite Sphalerite Sphalerite Sphalerite Sphalerite Sphalerite DCR: sphalerite I DCR: sphalerite II
Galena
13.0 12.8 6.9 10.4 9.7 9.4 10.1 11.0 11.0 9.9 11.5 10.8 10.0 10.8 10.2
0.70816 0.70873
0.70798
0.00008 0.00003
0.00003
FSV-215
SVD
3t
FSV-009
SVD
Ayala
FSV-079
SVD
Ayala
122 148 124 152
DCR: sphaleriteI DCR: sphaleriteII DCR: sphalerite I DCR: sphaleriteII
10.6 9.9
0.70788 0.70803 0.70796 0.70809
0.00002 0.00002 0.00003 0.00001
See Table 6 for abbreviations
lomiteof generation II is generally alsoslightlymore radiogenic than that of generation I (Fig. 16). The lastset of samples comprises sulfideminerals (Table 8). In selected specimens different sulfide generations were separated. The analyticresults show
thanfor carbonates fromthe samespecimen. According to their positionin the crystallization sequence, the latersulfides areslightly but significantly enriched
in radiogenic 87Sr compared to the earlierdolomite

or sulfidegenerations. For this discussion, it is irrel-
strontium ratioscorrespond acthat87Sr/86Sr ratios for sulfides aregenerally higher evantif the measured
o. 7o88
.875 -
87Sr/ 8Sr
O dark dolomite colcitel I
0.70 87 865 '
I-I light dolomiteII

limestone
0.70 86855
spholerite 11
O.7O85
845
' x
57 121
galena (111') ore-bearing samples
0.7084
835 -
errorJ ,, ?
5O 43
limits! - - am
0.7083 825
0.7082
.815
58
5448
152 A
49
I
0.7081
.805
SVDI41I 153 38-SVDI V
9 150 I I I ,li ,I,

61 I 127
0.7080
795
0.7079.
.785 -
HOST [
-
0.70 78 .775
ROCKS Ill iI
x
124
x A122b
&
0.7077-
Dolomite
Limestone m2 m3p
mo
svs
ch
tu
FIG. 16. Results of strontium isotopeanalyses. Numberscorrespond to numbers in Tables7 and 8. m2 = manto2; m3p = manto3 pisa;3t -- manto3 techo;ma = mantoAyala;svs= SanVicente south; ch -- Chilpes;tu -- Uncushtunnel.
1426
tually to Sr bound in the sulfidelattice or to very moreradiogenic values late in the paragenesis. In situ minutefluidor carbonate inclusions. The pointisthat element exchangebetween silicate and carbonate thesedatareflectthe S7Sr/S6Sr ratio duringsulfide phasesduring burial diagenesis (as suggested by precipitation. A possible problem of the S7Sr/S6Sr ra- Veizer and Compston,1974) can play only a very tios in sulfides is that as the strontium content in sul- subordinate rolebecause of the extremely low content fidesis very low (lessthan 1 ppm), the influenceof of detritalparticlesin the SanVicenteDolomite.The the Sr blank is not negligible,and any Sr contami- measuredstrontiumisotoperatios are the result of nation wouldleadto anincrease ofthe878r proportion mixing and equilibration between the brine--relameasured. tively enriched in radiogenic strontium--and the Summarizing the results: (1) the valuesfor the four carbonate hostrockswhich have strontiumisotope groups studied lie in a relatively narrow range of 87Sr/ compositions very closeto Upper Triassicto Lower S6Sr ratios, between 0.70778 and0.70835; (2) the Jurassicseawater.The brine/host-rockratio deterlowestvalue of 0.70778 lies closeto the rangeof mining the strontium isotoperatio of the fluid from 0.7075 to 0.7078 presentedby Burke et al. (1982) which the coarse crystallinedolomites andsulfides of for Upper Triassicto Lower Jurassic seawater;and the late generations precipitated increases progres(3) despite the narrowvariation rangeof the strontium sivelyfromgeneration I, whereprimarysedimentary isotope values, there are systematic differences in the structurescan still be recognized.This is the main strontium isotoperatios.The dolomites (andsulfides) explanation for the higher proportionof radiogenic of generation I are alwayslessradiogenic than the strontiumin late generations. corresponding carbonates (and sulfides) of the later The exactstrontium isotope composition of the ingenerations II or III. Laboratory leaching of silicates fiuxingbrine is not known. Examination of the data (compare Banneret al., 1988) canbe excluded asthe in Figure16 suggests that the S7Sr/S6Sr ratioof the factorresponsible for this trend because generation brine should lie close to or above 0.7084 because 52 I, havingsomeinsolubleresidues,is alwayslessra- of the 53 ratiosare lower than this value.The only diogenic thangenerations II or III, whichare virtually exception (sphalerite, sample 151 with a value of free of insoluble residues. An additional test was car0.70873) has, however, some analytic uncertainty, ried outby analyzing the S7Sr/S6Sr ratioof the insol- as the possibilityof blank contamination cannotbe uble residuein one sample(FSV-052, generation I). ruled out. The strontium isotope ratio thusobtainedis slightly A basinalbrine that circulatedthroughdetrital higher than that of the coexisting dolomiteI, but still sediments couldbe the source of the relatively radiolower than the isotopicratio of the carbonate gen- genic strontium.Numerousinvestigations showthat erationsII and III of the samespecimen. recentbasinal brineshavea wide rangeof strontium Theoretically one might expect a dependenceof isotopecompositions and that there is evidenceinthe 87Sr/S6Sr ratioson the Rb contentof the carbon- dicating that the brinesbecame enriched in 878rby ates. This is only possibleif the Rb/Sr ratio is high exchangereactionswith detrital host sedimentsor enough.The data presentedhere indicate that the with basement rocks(Chaudhuri,1978; Sunwalland ratiosare very low (Table 7) and therefore this influ- Pushkar,1979; Starinsky et al., 1983; Walter et al., ence is negligible.Clauer (1976) and Moore (1985) 1987). Several reactionscan release radiogenic
obtained similar results.
strontium from detrital minerals to interstitial
solu-
There are only a few other publishedstudiesin tions,amongthe mostimportantare feldsparalterawhichstrontium isotope ratiosof differentdiagenetic tion andillitc formation(Stueberet al., 1984; Gieskes crystallization generationswere distinguished.In et al., 1986; Chaudhuri et al., 1987). Russell (1985) most cases where this distinction was made, the shows thatthe increase in theS7Sr/S6Sr ratios in brines strontiumratios increasewith the crystallizationsein southeastern Mississippican be correlated with quence (Kessenet al., 1981; Grant and Miranda, burial to a depthof 3,000 m andexplains thisby pro1983; Lange et al., 1983; Moore, 1985; Woronick gressive alteration of rubidium-bearing detrital minand Land, 1985; Kesler et al., 1988; Gorzawski et al.;
1989). It is therefore concludedthat the trend observedin this studycorresponds to the rule that the minerals formedat the end of a diagenetic crystallizationsequence are, in general,moreradiogenic than thoseformed at the beginning. The isotopiccomposition of the strontiumin San Vicente is dominated by strontium with seawater compositioncontained in carbonate rocks and releasedby the dolomite replacementof calcite and
sulfates. Therefore the introduction of a more radioerals.
The trend to S7Sr-enriched compositions in later

crystallization generations is alsoobservedin other Mississippi Valley-type ore deposits(Kessen et al., 1981; Langeet al., 1983; Medfordet al., 1983; Gorzawskiet al., 1989). However, the absoluteincrease
in those of the strontium ratios at San Vicente is much
lower than, for instance, in the iburnum Trend and
PinePoint(Fig. 17). The smallincrease of the S7Sr/ S6Sr ratios at SanVicentecouldindicate a relatively
genic brine is required to explain the shift toward low stageof maturityof the basinat the time of brine

galena
1427
,l,
.71300
.71200 .71100 .71000 .70900
.70800
talcire
containmoreRb-bearing clay minerals. This ideacan be discardedbecausethe oolitic grainstones of the barrier facies,characterized by more radiogenic values, are virtually free of clay minerals.A better explanation is that the faciesdependence of the strontium isotope values is due to a higherbrine/host-rock ratio in the more porousoolitic grainstones of the barrier faciesthan in the lessporousfine-grained faciesin the lagoonand tidal fiat.
Oxygenand carbonisotopes
.70700
Sor Aug Pug SV Atp Neu Etm 6ro [ov Sat Pal Pin Vib Locolity
0 Cnrbonnfernnge
O Ore rnnge
*Senwnfer
Analyticalmethods: The carbonate samples used for strontium isotopestudies were alsoanalyzed for carbon and oxygenisotopes.Carbon dioxide was evolvedfrompowdered samples by reaction with 100 percent phosphoric acid at 25C according to the procedure described by McCrea(1950) andanalyzed
on a modified Varian MAT CH5 massspectrometer equippedwith a doubleinlet and two collectorsystems.Standard correction procedures were employed
FIG. 17. Variation rangesof strontiumisotope compositions of SanVicente comparedto data for other Mississippi Valley-type districts. Sar = Caneli Aquas, Sardinia, Italy (Gorzawski et al., 1989); Aug = Auglaize quarry, Ohio; Pug = Pugh quarry, Ohio; SV = SanVicente (present study);Alp = Alpujarrides, southern Spain;Neu = Neuqun, Argentina;Elm = Elmwood,Tennessee; Gra -- Gratz - Lockport,Kentucky;Cav = Cave-in-Rock, Kentucky; Sal = Salem,Kentucky;Pal = Croix desPalires, southern France; Pin = Pine Point, Canada(Medford et al., 1983); Vib -- Viburnam Trend, Missouri(Large et al., 1983). Data for Ohio and Kentucky are from Kessenet al. (1981). The estimatedcomposition of contemporaneous seawaterfor each deposit is indicated with a star (seawateraccordingto data from Veizer and Compston, 1974; and Burke et al., 1982).
(Craig, 1957), but no correction wasappliedfor the possibledifferencesof the fractionationfactor between phosphoric acid and calcite or dolomite (Sharma and Clayton, 1965). The results are expressed in per mil differencefrom the PDB international standard. The reproducibilityof the resultsis
_+0.2 per mil for 6sCand_+0.3 per mil for 61sO.

Results and discussion: Results of oxygenandcarbonisotope analyses for SanVicenteare givenin Table 7 and Figures 19, 20, and 21.
migration and ore formation as discussed by Gorzawskiet al. (1989).

In San Vicente a basinal brine could have incor-
poratedradiogenic strontium from severalsources of detritalminerals. Theseare the Mitu Group,the Red Sandstone underlyingthe carbonate sequence, and the Lower SarayaquilloFormation which contains
clastic material eroded from the Brazilian Shield. The
The 1SOvalues of hostrocks plot very close in a rangeof-5.5 to -7.8 (Fig. 19). This corresponds to reported values for normal LowerJurassic carbonates (Veizer and Hoefs, 1976). Dolomite samples of generation I are in the same range as the host rocks.
87Sr/o6Sr
0.7083
OOIlllC
two lastpossibilities are favoredbecause the lead isotope evidence(seebelow)rulesout the Mitu Group as a significant sourceand indicatesthat the brineleacheddetrital materialerodedfrom an old upper
crust.
borrler
0.7081
In addition there is a facies dependenceof the strontium isotopes. Samples from lagoonal or tidal flat facieshave generallylower strontium isotoperatios 0.7079than samples from the oolitic barrier (Fig. 18). This waspreviously interpreted in termsof differentmixing ratiosbetween the radiogenicintraformational fluid andocean water in relativelyearlystages of aliagen0.7077esis,dependingon the faciesposition(Fontbot6and Gorzawski,1988). However,thishypothesis mustbe rejected because the mineralsappearto have crystallized underburial exceeding 2 km. The reason for 0.7075 the facies dependence of the strontium isotope ratios FIG. 18. Variation rangesof the strontiumisotoperatios acshouldthereforebe sought in the lithologiccharac- cording to the faciespositionof the analyzedsamples. I, II, and teristicsof the implicatedfacies.A theoreticalpos- III are the crystallizationgenerations observedin diageneticcryssibility would be that the more radiogenic samples tallization rhythmites.
lagoon - N
tidal flat J J
II -I1: I
1428
0.00
880(%o,PDB)
dark dolom,te I
- 1.00 ...,SO -
[] light dolomite]I
O calcite / limestone
-2.00
...50-
ore- bearing samples
-3.00
..50-
timits error -+2am
-4.OO ...50-
-5.00...50-
-6,00..50-
ISJDI IBSL I
SV _1 117 I
116I38 ISVD
56
122
- ?.oo ._50-
-8.00
...50-
Dolomite
Limestone
r5
45
;6
1
112& I
-9.00..50-
124
121
m2 m3p m3t
58 I
xI ' I I
I I 50 I
i 1
52
-10,00_.50-
55
ma svs ch tu
-11.00-
FIG. 19. Results of oxygen isotope analyses. Numberscorrespond to numbers in Table 7. m2 = manto 2; m3p = manto 3 piso;m3t = manto3 techo ma = mantoAyala; svs= San Vicente south;ch -Chilpes;tu = Uncushtunnel.
samples lie inthesame range ofaC values. However, with advancingdiagenesis there are con- Theother generation II dolomiteis alsistent differences in the oxygenisotopecomposition. Again,the light-colored depleted in aCrelativeto the correThe dolomiteof generation II is alwaysslightlyde- waysslightly pletedin 680 compared to generation I of the same spondingdolomiteI. In summary: (1) the carbonates from SanVicente sample. homogeneous in their carbon andoxThe diagramfor the carbonisotopecompositions are remarkably compositions; (2) although the variation (Fig. 20) showsa similarpattern. Host rocksyield ygenisotope in the isotopic compositions of carbon andoxbaCvalues whichvary within a narrowrangefrom ranges evolution to2.2 to 0.5, which againis a typical rangefor Lower ygen are relativelysmall,a significant with advancing Jurassic marinecarbonates (VeizerandHoefs,1976). ward a lighter isotopiccomposition
63C (%o,PDB)
$JDI/!38
+ 1.50 .25 -
116
SVDIBSL I
39 I
1 I
122
I
42
HOST
+ 1.00
,75
ROCKS SL I
Dolomite Limestone
613 :120: 124 I, ..... '-2om

limits'-
+ 0.50
0.00
.25
606& 127
i
125
dark
dolomite I
- 0.50
.?5
O light dolomite]I
0 calcite/limestone
- 1.00.25 '
,5
121
x ore-bearing samples
- 1.50- 2.00-
m2 m3p
mt
mQ
SVS ch tu
FIG.20. Results of carbon isotope analyses. Numbers correspond to numbers in Table7. m2 -- manto 2; m3p -- manto3 piso;m3t = manto3 techo;ma = mantoAyala;svs= SanVicentesouth;ch =
Chilpes;tu = Uncushtunnel.
1429
+ 2.0
63C (%o,PDB)
11_6
38 e
+ 1.5
122
dork dolomite I
"
+ 1.0
/
7- '%" ...'_i'
124 n
571
3_9 .Bl18
51
+ 0.5
/
127 n n 45
El,,x. 40e. 120 /
/ /
/
58
n 123 n( 2 60/
n light dolomite ]
0 colcite/limestone
-0.5
i
/
/
/
- 1.0
121 n
- 1.5
880(%o,PDB)
- 2.0 -12 ' -11
I i I i i i
-10
-9
-8
-7
-6
-5
FIG. 21. Plot ]So/]60 versus 13C/12C.
diagenesis is observed; and (3) this evolutionis independent of the presence or absence of oreminerals. Several sedimentologic studies haverecentlybeen publisheddealing with stable isotopevariationsin carbonate cements and rocks. They establishthat small isotopicchangesof oxygen and/or carbonin sedimentary carbonates are common features that often provideusefultoolsto characterize the diagenetic evolution.During progressive diagenesis a decrease in (]soin subsequent diagenetic stages seems to be typical (Dickson and Coleman, 1980; Meyers and
Lohmann, 1985; Moore, 1985, Woronick and Land,
the differentcarbonate generations. The isotopic differences betweensubsequent generations should be similarwithin the depositbecausethe temperature increase shouldbe roughlythe samefor all samples in a comparable paragenetic position. This, however, is not the case(compare Figs. 19 and 20). Alsothe
differences in (]so and (]3C of the different dolomite
1985). These and other resultsobtainedin nonorebearingcarbonate sequences are similar to the pattern
observed at San Vicente.
The narrow range of oxygenisotopevariationis indicativeof a lackof in situmeteoricinfluence during the crystallization of generations I and II (Allan and Matthews, 1982). However, a meteoric component in the incomingbrine is not incompatible with the oxygenisotoperesults. Inasmuch asa burial environment is assumed, changingtemperatureconditions could becomean importantfactor for isotopefractionationprocesses. Crystallizationof the different carbonategenerationsat progressively increasing temperatures would resultin a progressive depletion
generations of singlesamples do not correlate(Fig. 21) aswell aswouldbe expected if the isotopic differences depended onlyon fractionation coefficients. A mixingmodelsimilarto that discussed for the strontium isotope compositions isnecessary to explain the carbonand oxygenisotopecompositions of the carbonates. The carbonandoxygen isotope ratiosof the precipitatedcarbonates probablychangedfor several reasons: (1) the circulating brinehada different carbonand oxygenisotopecomposition from the seawaterthat precipitatedthe original carbonates (generation I), (2) variablefluid/host rockmixingratios,and(3) temperature increases. Evenaninfiuxing
brine enriched in ]So wouldbe possible, provided
the temperatureof crystallization washigh enough. However, extremelyhigh temperatures are considered unrealisticbecause the normaltemperaturefor a burial depth of about2 to 3 km is estimated on the basis of sulfurisotopegeothermometry andfluid inof ]So in the crystallizing carbonate (Dickson and clusions. In addition,depletedoxygenisotope values Coleman,1980), although exactdatafor the equilib- appear to be a typical feature of burial diagenesis rium isotope fractionation betweendolomiteandwa- (Land, 1985). The influenceof temperatureon the ter at low temperaturesare not available. carbonisotopecomposition of dolomitebeing preTwo factsindicate that temperaturefractionation cipitatedfrom a fluid is not well known.A possible alonecannotexplainthe stableisotopeevolutionin additionalcarbonsourceis light carbonof organic
1430
L. FONTBOTI AND H. GORZA WSKI
matter dispersed in the hostrock or from other parts Sulfur isotopes of the basin.The oxidationof organicmatter, with Analytical methods: Analyses reported in thisstudy
(13Corganic = about -25 per mil/PDB, releases light are discussed in Gorzawski et al. (1990) and are carcarbon,which can contribute to the total HCO source ried out on 20 individual sulfide concentrates that
for carbonateprecipitation.The minor changeob- were extractedfrom five samples. The sulfidesulfur served for the i3Cvalues rulesout in situorganic in eachconcentrate wasconverted to SO2gas for mass carbonasa major sourcefor the carbonatecarbonof spectrametric analysis of the sulfurisotoperatio acgenerations II or III, sincegreater variationswith re- cording to the methoddescribed by OhmotoandRye spectto generationI and relative to the host rocks (1979). The sulfurisotope dataare givenin convential would be expected(Irwin et al., 1977). i34S values, representing thedeviation ofthesample Progressive in situdepletionof the heavierisotopic in partsper thousand (%0) relativeto the Canyon Diacomponents during crystallizationof the different blo meteoritestandard (CDT). Analyticprecision is generations couldplay a certainrole in the lastphases calculated to be better than _+0.2per mil. The data of crystallization in carbonate reservoirs. If the system are listedin Table 8 andare graphically displayed in eventuallybecameclosedto fluid migration,prefer- Figure 22 which also includesthe earlier resultsof ential concentration of the heavierisotopein earlier Nielsen(in Schulz,1971) for comparison.
formedcarbonates woulddepletethe 13Cof the re-
Results indicate that sulfides from San Vicente are
sidualfluid, which is the sourcefor the later generations(KeltsandMcKenzie, 1982; HannahandStein, 1984). In summary, the carbonisotopedataindicatea fluid changing slightlybut consistently during ore formation. The oxygenand carbonisotopecomposition of the fluid was mainly controlledby the introduction of a brine probablywith a differentisotopiccompositionandby mixingratiosbetweenthis fluid andthe hostrock. A possible subordinate contribution of organically derivedcarbon, andthe influence of slightly increasingtemperatures,is alsoconsistent with the carbonand oxygenisotoperesults.
isotopicallyremarkably homogeneous, are signifi-
cantly enriched in 34S, andexhibit a consistent though

weak isotopic trend with paragenesis. Many of these features are characteristic of otherMississippi Valleytype deposits as summarized by Heyl et al. (1974)
andOhmoto andRye (1979). The i34S values of 18

sphalerite samples rangenarrowlyfrom 9.4 to 13.0, and thoseof two galenasamples from 6.8 to 6.9. All
sulfides are enriched in 34S relativeto those of presumed magmatic or magmatic hydrothermal origin(0 _ 3%0), which impliesan isotopically heavysource of sulfurderivedfromsulfate in oceanic and/orconnate waters,or from marine evaporites.
63s(%.,COT)
?8
.13
19
.12
.11
75
12t,
86,88, 83, 82
81
8g
sphalerite I
Z sphalerite a
+1o
:
152
87
Zx sphaterite b
galena'm'
+9
,/ sphaterite
( generation not specified)
A resuVrs of NIELSEN
+8
V in SEHULZ (1971)
+7
z
8O
I I I FSV-7 FSV-&I FSV-79
v
153
I I FSV-39 FSV-&& sample no.
+6
FIG. 22. Results of the sulfurisotope analyses (fromGorzawski et al., 1990). Numbers correspond
to numbers in Table 8.
Zn-PbDEPOSIT,SANVICENTE, CENTRALPERU
1431
The isotopic homogeneity of sulfurin sulfides from SanVicente waspreviously notedby Schulz(1971), whoattributed thisto a laterhomogenization process. However,sucha process isconsidered unlikelybased onthe results of the present investigation andbecause of the absence of a metamorphic imprintonhostrocks
and ores at San Vicente.
icalreduction of sulfate by bitumenmayhaveformed the sulfideoresof the Pine Point deposit(Canada)at temperatures of about 100C. Because of the lack of successful laboratory experiments in reducing abiogenically sulfate below250C there is somedoubt about the significance of abio-
Our results demonstrate the genicsulfatereduction asan ore-forming process in existence of smallsystematic isotopic differences be- Mississippi Valley-type deposits(Trudinger et al., tweenconsecutive sphalerite generations. In the three 1985). However, Orr (1974) and Powell and Macspecimens where a proper separation was possible Queen(1984) havesuggested that extrapolation of the feasibility of thisprocess the firstsphalerite generation shows higher834S val- the kineticdataindicates uesthanthe later sphalerite generations (II, III). This at temperatures aslow as 80 to 120C in geologic trendtowardlighter834S values duringsulfide for- systems. Moreover,the likelihoodand speedof this mationmayreflect fractionation processes andmass- abiogenic reduction maybe enhanced by thepresence balanceeffectsrelatedto changing physicochemical of partly oxidizedintermediate sulfurspecies (Spiparameters of the system. Decreasing fractionation rakis, 1986). between ZnS and H2S with increasing temperature The consistency of the 34S values couldalternaduringprogressing diagenesis wouldbe onepossible tively be indicativefor H2S production and homogexplanation, but unrealistically hightemperature in- enizationelsewhereand migrationof this homogecreaseswould be required between consecutive neous H2S to the San Vicente site. However, as dissphaleritegenerations. cussed later, faciesconstraints make this possibility distributions Clear constraints canbe set regarding the source quite unlikely.Thus,the sulfurisotope from SanVicenteare interpretedasa result of sulfurfor the sulfides at SanVicente.According to in sulfides by abiogenic reduction of sulfates Claypoolet al. (1980) the sulfurisotope composition of H2Sproduction of marine sulfate ranged from about 12 to 18 presentin the hostcarbonate. Assuming equilibriumbetweenthe sulfides of genthroughout the Middle Triassic to Lower Jurassic. In II and III, isotopic temperatures of 75 and addition, Field et al. (1983) reported34S values of erations for two sphalerite-galena 13.1 and 13.8 for evaporiticanhydritewithin the 92C havebeen calculated equaMorococha districtin the westernpart of the Pucart pairs(FSV-41,FSV-39) usingthe fractionation basin. tions given by Ohmoto and Rye (1979). This temwith that indicatedby Abundantpetrographic data showthat in SanVi- perature range is consistent centesulfate minerals havebeenreplaced by carbon- scarcefluid inclusiondata (see below) and partly ates.In the temperaturerange of formationof Mis- overlapsthe temperature range at which the thersissippi Valley-typedeposits the replacement of sul- mochemical reduction of sulfate is considered to be fate by carbonate in the absence of other reactions possible. can be taken as evidencefor sulfatereduction(AnFluid Inclusionsand Organic Matter dersonand Garven, 1987). This is because the hyFluid inclusions in the San Vicente ore are chardrogenionsgenerated by sulfatereplacement would inhibit the precipitationof carbonate phases in the acterizedby their extremely small size. The Japan absence of sulfate reduction or other reactions such International Cooperation Agency (1976) reports as silicate alteration. from attemptsto studythree samples from the main The isotopically heavyanduniform 4S values of ore horizonin SanVicente,one from SieteJeringas, the sphalerites are inconsistent with a biogenic mech- and one from Uncush Sur. Most of the inclusions are anismfor the reductionof sulfatein place.Alsothe lessthan 1 to 2/ with very highfillingratios--about are sominute that only a generation of H2Sby thermaldegradation of organic 95 percent.The inclusions sulfur-bearing hydrocarbons isnotconsidered to pro- few dolomitesamples were actuallymeasured, giving ducereducedsulfurwith the requiredsulfurisotope a homogenization temperature range from 70 to composition for the fixationof metalsat SanVicente 140C. No freezing temperaturescould be deter(Gorzawskiet al., 1990). mined.In the present investigation the very smallsize Abiogenic reductionof sulfateby reactions with of the fluid inclusionsin sphalerite prevented the organic carbon, ferrous iron,or H2 maygenerate H2S gatheringof more precisedata. that isbut slightly to moderately fractionated relative Studies on organic matterincludereflectivitymeato the source of sulfur.Orr (1974, 1977) proposed surements andRock-Evalanalyses. Organicmaterial limestone consists mainlyof bituthat hydrocarbons in combination with H2S may re- in the bituminous ducesulfates at temperatures aslow as80C.Similarly minoussubstances showing high reflectance(R..... MacQueen and Powell (1984) and Powell and = 4.6%). Rock-Evalanalyses of bituminousorganic MacQueen(1984) have suggested that thermochem- matter from variouswall rocksalso indicatea high
1432
L. FONTBOTt AND H. GORZAWSKI
lb Shalpayco
(NVTcenfrat
[a Volcamc-assocated
western Pucar
Ic San Vcenfe
(MVT eastern Pucar)
39.0'
38.5'
/'
: "a
.bas,n
piafform
I Upper TriassicII Liasslc- Lower
!. arc [[[ 38.0 --IIa,b,c Magmaf,c

18.t+
158:
Liasslc (Pucar-13.) [refoceous
. back-arc III Upper [refoceous ................................. T.e.:t?r? .........

18.6 18.8 19.0 19.2 2o6pb/2o4pb
15.7
15.6'
dPPER [RUST l_error

bars
15.5
,,,(,,,,1
.........
EIToqu
Nantosde Cafemu
Cffuncho
19.2206pb/204p b
E[ Extra6o
Cateta
[otoso
Los leas
Ta[cuna
o Leore[a- 6race[a
Punta del [obre
Cercapuquo
Hua[gayoc
Machcn
Tmunfo-[aro[a, E[ Plomo, Jau[a, Las [a6as

[arohna de
E I Soldado
Shalpayco
Nanf os B[ancos
Santo Domingo
Buena Esperanza
S. Barrolo
San Vcenfe
[arahuacra-Huampampa El Jardin
FIG. 23. Lead isotoperatiosfrom SanVicente comparedto other strata-bound ore deposits in the Andes.The field of the Pucartratios is decidedlymore radiogenicthan fields for the other groupsof strata-bound ore deposits hostedby Pucarft rocks(seealsoFig. 1) and for other Andeanstrata-bound deposits (fromFontbot et al., 1990a). Data from Mukasa(1984); Flint (1986); Flint et al. (1986); Puig (1988); Macfarlane(1989); Fontbot et al. (1990a andb); and Gunnesch et al. (1990).
maturity,largelybeyondthe stage of oil andgasgeneration. This high evolution stageis interpreted to have been attained in postore stageswhen burial reacheddepthsover 5,000 m.
Lead IsotopeInvestigations
Gunnesch et al. (1990) reportleadisotope analyses of several galenasamples from the SanVicentemine. As seenin Figure 23, where theseanalyses are comparedto leadisotope ratiosfromAndeanstrata-bound ore depositslocated in other paleogeographic and geotectonic positions, the SanVicente oresare by far the most radiogenic.They are also different from otherPucar-hosted ore deposits, including volcanicassociated deposits at the Domo de Yauli, at Huaripampaand Carahuacra,and the Mississippi Valley-
type depositShalipayco, which is locatedat the base of the PucarhGroup near the contactwith volcaniclastic rocks of the Mitu Group.The highlyradiogenic values of San Vicente can be comparedto the still moreradiogenic J-leadrangein the Mississippi Valley districtwhich is characterized by negativeor future model ages.This is typical of upper crustallead in cratonicregionsand of many Mississippi Valley depositsin this environment(Doe and Zartman, 1979). Theseresults are thereforewhollyconsistent with the paleogeographic positionof SanVicente at the western marginof the BrazilianShield.An importantpart
of the lead in San Vicente could have been derived
from old upper crustfrom the BrazilianShield(Fontbot et al., 1990b). Geologic evidence, including the basin geometry, makes leaching of clastic rocks
Zn-PbDEPOSIT,SANVICENTE, CENTRALPERU
1433
at San Vicente) are the most probable erodedfrom the BrazilianShield(Lower Sarayaquillo Sandstone Formationandequivalents like the Red Sandstone at sourcefor the radiogenicstrontium. The association of the orebodies with definitealgal SanVicente)more probablethan direct leaching of characterized by the presence of crystalline rocks of the Precambrian basement. Mitu matperitidalfacies and abundantorganicmatter is the Groupvolcanic andvolcaniclastic rockscannot be a moldsof sulfates a geneticmodelbasedon main source because muchlessradiogenic values,in main evidencesupporting of two separate reservoirs for sulfurand the range of thosefound in Shalipayco (Fig. 23), the existence should be expected(Fontbot et al., 1990b). the metals,as proposed by Beales(1967) for Pine Gunnesch et al. (1990) havealso measured the lead Point, rather than a model basedon a singlebrine sulfurandthe cations (e.g., Barnes, isotopecomposition of host-rock carbonates in the whichintroduces 1984). This is also San Vicente sequencewithout directly associated 1983; Rickard, 1983; Sverjensky, with the sulfurisotopevalueswhich are orebodies. The leadin these carbonates issignificantly consistent andcoincide with lessradiogenic than the lead in the ore samples, thus relativelyheavyandhomogeneous basin. indicating differentsources. This observation is con- thoseof sulfatein other parts of the Pucart exclude bothmagmatic sulfurandin situ sistent with the strontium isotope results whichreveal Thesevalues reduction of sulfateas sources for sulfide an input from brines that were slightlyenrichedin biogenic Abiogenic reduction of sulfate with no or radiogenicstrontium.The SanVicente lead isotope formation. canbetter explainthe data. datatakenasa groupare muchmoreradiogenic than only minor fractionation with evaporite-bearing faciessuggests data for other Andean ore deposits(Fig. 23), but The association within the group they displaya significant scatter. that the sulfurwas reducedfrom the anhydriteand presentin andin the vicinityof the ore deThis couldpoint to mixingbetween a Precambrian gypsum by abundant sulfatepseuradiogeniccomponentand another less radiogenic positionsite, asevidenced Considering the evaporite-bearing facies component, assuggested for the ViburnumTrendby domorphs. at the districtscaleand the fact that sulfatepseudoCrocetti et al. (1988). morphs are alsoabundant in nonore-bearing partsof Conclusions
the dolomite units, the available amount of sulfur
The diageneticevolutionof the San Vicente ore deposithasbeen tracedcombining petrographic and isotopic data. Significant isotopic trendswere found andphysicochemical constraints concerning the genesisof the depositwere derived. The strontiumisotopedeterminations of hostrock
should have been sufficientfor ore deposition.Al-
thoughabiogenic reduction of sulfates hasnotbeen

achievedexperimentallyin the temperaturerange indicated by the sulfur isotope geothermometry (7592C) and the scarce fluid inclusion data (70 140C),thisis the mostsuitable possibility to explain the sulfurisotoperesultsat SanVicente. The alternativeof introducing a brine with sulfurhomogenized elsewhere in the basindoesnot explainthe association of the ore with evaporite-bearing facies. The range of oxygenand carbonisotoperatiosin carbonates is very narrow.However, a cleartrend to lighter isotoperatiosin the late crystallization generations is recognized. This isotopic shiftis regarded in terms of an evolving ore-formingfluid which changed its composition slowlybut continuously during crystallization underconditions of burial diagenesisand steadily increasingtemperature. The composition of thisfluid ismainlydetermined by the mixing ratios with the host rock as well as by the
introduction of a basinal brine. Subordinate incor-
and gangue and ore minerals yield 87Sr/86Sr ratios

which all lie in a very narrowrange(between0.7077 and0.7084), slightlyhigherthanthe estimated strontium isotopecomposition of seawaterduring Late Triassic-Lower Jurassic times.In detail, smallbut significant isotopic trendsarerecognized andreflectthe evolutionof the fluidsduringthe formation of the ore deposit. The latecrystallization generations are always slightlyenrichedin radiogenicstrontiumcompared
to the first ones. These results reveal the introduction
of a basinalbrine relatively enrichedin radiogenic strontium, probablydue to circulationthroughRbbearingdetritalrocks.Equilibration at differentmixing ratiosbetweenstrontium contained in the brine andin the hostrockcanexplain the observed patterns. For the last generations the brine/rock ratio was higher and thereforethe valuesare alsomore radiogenic.In addition,the strontiumisotopecomposition
of the basinal brine evolves with time toward more
porationof light organiccarbonis possible. In situ meteoric influence can be ruled out since sharper changes wouldbe expected.
It can be concluded that the San Vicente lead-zinc
radiogenicratios as a consequence of an increasing exchange reaction with Rb-bearing phases. Combined evidence of strontium andleadisotope determinations suggests that clasticrockserodedfrom the Precambrianuppercrustof the BrazilianShield(LowerSarayaquillo Formation and equivalentslike the Red
deposit formedduringlate stages of diagenesis under considerable burialby the introduction of a zinc- and lead-bearing basinal brinecharacterized by strontium isotoperatiosslightlyhigherthan contemporaneous seawaterand highly radiogeniclead isotoperatios. The temperaturesindicatedby sulfur isotopegeo-
1434
L. FONTBOTt AND H. GORZAWSKI
thermometry, andalsosupported by preliminary fluid 3. The sulfur appearsto have been abiogenically inclusion data,wouldbe consistent with temperatures reducednear the deposition siteandincorporated diattainedthroughthe normalgeothermal gradientat rectlyto the ore-forming fluid.Duringcrystallization a burial depth of about 2 to 3 km by the end of the the sulfur isotope composition changed toward Jurassic period. A burial depth of about 2 to 3 km slightly lighter34S ratios. wouldalsobe consistent with conditions requiredfor 4. Lead and by analogyzinc have been supplied oil generation.This process is necessary to explain almost entirelyby the basinal brine.Slightly scattering the deposition of massive bitumenin generation III. valuesalonga mixingline indicatecontributions from The oil generationcould either take place closeto at leasttwo lead sources. The scattering of the lead the ore deposit, becausethe host rocks are rich in isotope ratiosargues for compositional changes in the dispersed organic matter (the Bituminous SiltyLime- basinalbrine duringore formation. stonehasbeen identified as an oil sourcerock), or 5. The fluid becameenrichedin the laststages of hydrocarbons couldbe introduced by a basinal brine. crystallization in bitumen,asevidenced by deposition The geneticmodelof SanVicenteis envisaged es- of massive bitumenin generation III (always postdatsentiallyas a single-stage event characterized by a ing the ore minerals).Both oil generationnear the progressive ore fluid evolution.For discussion pur- ore depositandintroduction of bitumenwith the baposes, the existence of two fluidscanbe considered: sinai brine can be considered. a fluid at the site of the ore deposit,from whichthe 6. The fluid probably alsobecame richerin Sr,Rb, ore andgangue minerals precipitate,andan infiuxing and Na becausethe late crystallizationgenerations basinal brine. Whereasthe composition of the basinal are relatively enrichedin theseelements. brine canbe considered to be relatively constant or Petrographic observations, in particularthe almost to change onlyslowly,the composition of the fluid at the depositional site changeslocally dependingon total absenceof repetitionsin the parageneticsesupport the hypothesis of a single ore-forming various factors. The element content of this fluid is quence, event. This created manifold crystallization features, determinedby the steadycontribution of the basinal including diagenetic crystallization rhythmites and brine, but it alsochanges due to differentfluid/hosthydraulic breccias produced in an overpressure rerockmixing ratios in different partsof the oredeposit. gime. Dolomite dissolution features, observed in Other parameters alsoplay an importantrole, as,for breccias and in other structures, are probably due to instance, precipitationof new minerals,reductionof of hydrogenions liberated by SO -4 to S-, andeventually, incorporation of in situ the local abundance of sulfate by carbonate. organiccarbon. Oil generationnear the deposition the replacement Textural and isotopic evidence indicates unequivsiteis a further possibility which mustbe considered. ocally that the gangue of coarsely crystalline dolomite In addition,the physicochemical parameters (such as and the ore minerals essentially formed during the T, ell, and pH) of the ore fluid controlthe precipiprocess. However,thisdolomitemayhavebeen tationand/ordissolution of minerals and,in part,their same produced,at leastin part, by recrystallization of a isotopic ratios. former dolomite that originated during early stages The evolution of the fluid has been traced using of diagenesis. This is strongly suggested by the strict petrographic and geochemical evidence,including facies-bound character of the dolomitic units. The
isotopic determinations on samples from different lower strontium contentsand the favorable deposiparagenetic positions. The contributions to the ore tional environment would be consistent with the exmatter from the basinal brine and from the host rock
istenceof a former dolomiteproducedduring early diagenesis. 1. Duringthe process of ore formation the stronFinally, someconstraints canbe placedregarding tiumisotopes became progressively moreradiogenic. the time parameters and dynamics of the migration Thiswasdueessentially to higherbrine/host-rock ra- of the lead-andzinc-bearing brinethatproduced the tiosin the lastgenerations. In addition, the strontium SanVicenteore deposit. If the temperature rangeof of the basinal brine becameincreasingly more radio- 70 to 100C is confirmed,an Upper Jurassic age genic during basin evolution due to progressive could be envisaged,i.e., coevalwith the burial of about 2 to 3 km due to sedimentation of the Lower leachingof rubidium-bearing silicates. 2. The stable isotopes (C andO) precipitating from Sarayaquillo Formation. The subsequent deposition the fluid becameprogressively slightlylighter. This during the Cretaceousof thick clastic sequences trend results from a combination of temperature ef- would resultin higher temperatures (in the rangeof fects,differentmixingfluid/host ratios,andincorpo- up to 200C for a burial depthof 5,000 m). The only ration of organiccarbon,even without considering very slightradiogenic characterof the strontium isothe otherwise probable influence of the inputof the tope ratioscouldindicatea relativelyimmaturestage basinal brine. of the basin, although otherreasons couldalso explain
canbe envisaged asfollows:
1435
the Marafi6ngeoanticline, which dissected the Pucart batholite de San Ram6n, Cordill're Orientale du Prou central: Geol. Rundschau, v. 66, p. 434-446. basinat the endof the Jurassic, couldhaveinfluenced Chaudhuri,S., 1978, Strontiumisotopiccomposition of several the brine dynamics. oilfield brines from Kansas and Colorado: Geochim. et CosAcknowledgments
thisfeature. The epeirogenic movements thatuplifted
Capdevila,R., Mgard, F., Paredes,J., and Vidal, P., 1977, Le
We express our appreciation to the staffof SanIgnacio de Morococha, S.A., in SanVicente,especially to R. Tejada,JuanNeyra, andJuanCarlos Alcaldefor their support duringthe present investigation. In addition to the individuals and institutions mentioned
mochim.Acta, v. 42, p. 329-331. Chaudhuri, S., Broedel, V., and Clauer, N., 1987, Strontium isotopic evolutionof oil-fieldwatersfrom carbonate reservoirrocks in Bindley field, central Kansas,U.S.A.: Geochim. et Cosmochim. Acta, v. 51, p. 45-53.
in the isotopicchapters we would like to thank E.

Schroll, in Vienna, and in P. Soler, in Paris, for their permission to use unpublishedanalyticaldata. The present investigation hasbenefited by grants fromthe EuropeanCommunities (contractMSM-010-D). We
Clauer,N., 1976, Gochemieisotopique du strontium desmilieux sdimentaires. Application h la gochronologie de la couverture du cratonouest-africain: Sci.Geol., Paris,Mere. 45, 256 p. Claypool,G. E., Holser, W. T., Kaplan,I. R., Sakai,H., and Zak, I., 1980, The agecurves of sulfurandoxygen isotopes in marine sulfate andtheir mutualinterpretations: Chem.Geology, v. 28,
p. 199-260.
also acknowledge datafromthe unpublished Master's thesis of E. Gonzdez andillustration drafting by E. Gonzalez, H. SchiSnfelder, andS.Rosas, Heidelberg. The manuscript hasgreatlybenefitedfrom valuable
comments by DuncanLargeandtwo Economic Geology reviewers.
REFERENCES
Craig, H., 1957, Isotopicstandards for carbonand oxygenand correctionfactorsfor massspectrometric analysis of carbon dioxide:Geochim.et Cosmochim. Acta, v. 12, p. 133-149.
Crocetti, C. A., Holland, H. D., and McKenna, L. W., 1988, Isotopic composition of lead in galenas from the ViburnumTrend, Missouri: ECON. GEOL., v. 83, p. 355-376. Dalheimer, M., 1990, The Zn-Pb-Ag depositsHuaripampaand Carahuacra in the miningdistrictof SanCristobal,centralPeru, in Fontboth,L., Amstutz, G. C., Cardozo, M., Cedillo, E., and Frutos,J., eds.,Stratabound ore deposits in the Andes:Berlin-
Heidelberg-NewYork, Springer-Verlag, p. 279-291. Delgado,F., 1977, Primarytexturesin dolostones andrecrystalAllan, J. R., and Matthews,R. K., 1982, Isotopesignature asso lized limestones: A technique for their microscopic study: Jour. ciatedwith earlymeteoric diagenesis: Sedimentology, v. 29, p. Sed. Petrology, v. 47, p. 1339-1341. 797-817. Dickson,J. A.D., and Coleman,M. L., 1980, Changes in carbon Amstutz, G. C., 1956, Maria Esperanzamine--San Ram6n:La and oxygenisotopecomposition duringlimestonediagenesis: Aroya, Peru, Cerro de Pasco Corp., int. rept., 2 p. Sedimentology, v. 27, p. 107-118. Amstutz,G. C., andPark,W. C., 1971, The paragenetic position Doe, B. R., and Zartmann, R. E., 1979, Plumbotectonics: The Phanerozoic, in Barnes,H. L., ed., Geochemistry of hydroGeologists JapanSpec.Issue3, p. 280-282. thermalore deposits: New York, Wiley Intersci.,p. 22-70. Anderson, G. M., 1983, Some geochemical aspects of sulfide preDunham,R. J., 1962, Classification of carbonate rocksaccording cipitationin carbonate rocks,in Kisvarsanyi, G., Grant, S. K., to depositional texture:Am. Assoc. Petroleum Geologists Mem. Pratt, W. P., and Koenig,J. W., eds.,Internationalconference 1, p. 108-121. on Mississippi Valley type lead-zincdeposits. Proc.Vol.: Rolla, Dunin, E., 1975, Controllito16gico y estratigrSfico en la ubicaci6n Univ. Missouri-Rolla Press,p. 61-76. de losmantos con sulfuros de metalesno ferrosos en lascapas Anderson,G. M., and Garven, G., 1987, Sulfate-sulfide-carbonate calcreas del Per6 central:Soc.Geol. Per6 Bol., v. 50, p. 25associations in Mississippi Valley-typelead-zincdeposits: ECON. 52.
GEOL., v. 82, p. 482-488.
ofsulfides inthediagenetic crystallization sequence: Soc. Mining
Audebaud, E., Capdevila, R., Dalmayrac, B., Debelmas, J., Laubacher,G., Levevre, C., Marocco,R., Martinez, C., Mattauer, M., Megard, F., Paredes,J., and Tomasi,P., 1973, Les traits
Field, C. W., Rye, R. O., Dymond,J. R., Whelan, J. F., and Senechal, R. G., 1983, Metaliferous sediments of the East Pacific Rise, in Shanks, W. C., III, ed., Cameron volume of unconven-
ge61ogiques essentiels des Andes Centrales (Perou-Bolivie): Rev. Gog. Phys.GologieDynamique, v. 15, p. 73-113.
Banner, J. L., Hanson,G. N., and Meyers, W. J., 1988, Determination of initial Sr isotopic compositions of dolostones from
tional mineraldeposits: New York, Soc.Mining Engineers, p.

133-156.
hostedcopper mineralizationin Cretaceous Andean molasse: methods: Jour.Sed.Petrology, v. 58, p. 673-687. The Coloso Formation of northernChile: Geol. Mag., v. 123, Barnes, H. L., 1983, Ore-depositing reactions in Mississippi Valleyp. 525-536. type deposits, in Kisvarsanyi, G., Grant,S. K., Pratt, W. P., and Fontboth, L., 1981, Strata-bound Zn-Pb-F-Ba deposits in carbonKoenig,J. W., eds., Internationalconference on Mississippi ate rocks:New aspects of paleogeographic location,facies facValleytype lead-zincdeposits. Proc.:Rolla,Univ. Missouri-Rolla tors and diageneticevolution.(With a comparison of occurPress, p. 77-85. rences fromthe Triassic of southern Spain, the Triassic/Liassic Beales,F. W., 1967, Precipitation of lead-zincoresin carbonate of central Peruandotherlocalities): Unpub. Ph.D.dissert., Univ. reservoirsas illustratedby Pine Point ore field, Canada:Inst. Heidelberg, 193 p. Mining MetallurgyTrans.,v. 75, sec.B, p. B278-B285. Bencini, A., and Turi, A., 1974, Mn distribution in the Mesozoic -1990, Stratabound ore deposits in the PucarhGroup--an overview,in Fontboth,L., Amstutz,G. C., Cardozo,M., Cedillo, carbonate rocks fromLimaValley,northern Apennines: Jour. E., andFrutos,J., eds.,Stratabound ore deposits in the Andes: Sed.Petrology,v. 44, p. 774-782. Berlin-Heidelberg-New York, Springer-Verlag, p. 253-266. Burke,W. H., Denison, R. E., Hetherington, E. A., Koepnick, R. B., Nelson, H. F., andOtto,J. B., 1982, Variations of seawater Fontboth,L., and Amstutz,G. C., 1983, Faciesand sequence 87Sr/86Sr throughout Phanerozoic time: Geology, v. 10,p. 516analysis of diagenetic crystallization rhythmites in strata-bound
519.
the Burlington-Keokuk Formation (Mississippian): Constraints from cathodoluminiscence, glauconite paragenesis and analytical Flint, S., Clemmey,H., and Turner, P., 1986, Conglomerate-
Flint, S., 1986, Sedimentary and diageneticcontrolson red-bed ore genesis: The middle Tertiary SanBartolo copper deposit, Antofagasta province, Chile:ECON. GEOL., v. 81, p. 761-778.
Pb-Zn-(Ba-F) depositsin the Triassicof central and southern
1436
Europe, in Schneider,H. G., ed., Mineral deposits of the Alps andof the Alpine epochin Europe:Heidelberg,Springer-Verlag, p. 347-358. Fontbot$, L., and Gorzawski,H., 1987, Petrographicand geochemicalindicatorsfor the explorationof hidden ore deposits in sedimentary rocks: Brussels, Comm.EuropeanCommunities, unpub. final rept. contractMSM-010-D, 221 p. 1988, Isotope (Sr, C, O, S) tracing of diageneticore formation in carbonate-hosted depositsillustrated on the F-(PbZn) depositsin the Alpujarrides, Spainand the SanVicente ZnPb Mine, Per6:Soc.Geology Appl. MineralDeposits Spec. Pub.
Heyl, A. V., Landis, G. P., and Zartman, R. E., 1974, Isotopic evidencefor the origen of Mississippi Valley-type mineralde-
posits:ECON. GEOL., v. 69, p. 992-1006. Irwin, H., Curtis, C., and Coleman,M., 1977, Isotopicevidences for source of diagenetic carbonates formedduringburialof organic-richsediments: Nature, v. 269, p. 209-213. JapanInternationalCooperation Agency,1976, Report on geologicalsurveyof the CordilleraOriental, centralPeru: Lima, Japan Mining Agency, Japan Internat. Coop. Agency, unpub. rept., v. 2, p. 39-40. -1979, Reporton geological survey of the CordilleraOriental, 6, p. 465-484. centralPeru:Lima,Japan MiningAgency, Japan Internat.Coop. Fontboth,L., Amstutz,G. C., and Samaniego, A., 1981, Zur faAgency, unpub. rept., v. 8, 46 p. ziellenStellung und zum diagenetischen Kristallisationsprozess Kelts, K., and McKenzie, J. A., 1982, Diagenetic dolomite forvon Erzmineralien in schichtgebundenen Zn-Pb-LagerstStten mation in Quaternary anoxicdiatomaceous mudsof Deep Sea (am Beispiel von San Vicente, im zentralen Ostperu). Proc. Drilling ProjectLeg 64, Gulf of California, in Deep SeaDrilling Geowiss. Lateinamerika Koll., 7th, Heidelberg,1980: Zentralbl. Proj., Initial Repts., v. 64, p. 553-569. GeologiePa15ontologie, Jg. 1981, Teil I, p. 465-477. Kesler, S. E., Jones,L. M., and Ruiz, J., 1988, Strontiumisotopic Fontbot$, L., Calvez, J. Y., Pincheira, M., and Wolf, F., 1990a, geochemistry of Mississippi Valley-type deposits,eastTennesGeotectonic positionand metal sources of stratabound oresin see: Implications for ageandsource of mineralizing brines: Geol. the central Andes--lead isotopicconstraints: ORSTOM InterSoc.America Bull., v. 100, p. 1300-1307. nat. Symposium Andean Geodynamics, Grenoble, May 15-17, Kessen,K., Woodruff, M. S., and Grant, N. K., 1981, Gangue 1990, Collection Colloqueset Seminaires, p. 347-350. mineral 87Sr/86Sr ratios andtheorigin ofMississippi ValleyminFontbot$, L., Gunnesch,K. A., and Baumann,A., 1990b, Metal eralizations:ECON. GEOL.,v. 76, p. 913-920. sources in stratabound ore deposits in the Andes(Andeancycle): Kobe, H. W., 1977, El Grupo Pucart y su mineralizaci6n en el Lead isotopicconstraints, in Fontboth,L., Amstutz,G. C., CarPer6 central: Soc.Geol. Per6 Bol., v. 55-56, p. 61-84. dozo, M., Cedillo, E., and Frutos, J., eds., Stratabound ore de- -1982, E1ambientede la mineralizaci6n estratoligada de Znpositsin the Andes: Berlin-Heidelberg-New York, SpringerPb-Ag-Ba-Mn-Fe-Cu en lossedimentos de la cuenca occidental Verlag, p. 759-773. del Pucart,Per6 central:Soc.Geol. Per6 Bol., v. 69, p. 41-69. Gieskes,G. M., Elderfield, H., and Palmer, M. R., 1986, Strontium Kontak, D. J., Clark, A. H., Farrar, E., and Strong,D. F., 1985, and its isotopiccomposition in interstitialwatersof marinecarThe rift associated Permo-Triassic magmatism of the Eastern bonate sediments:Earth Planet. Sci. Letters, v. 77, p. 229Cordillera: A precursor of the Andean orogeny, in Pitcher, 235. W. S., Atherton, M.P., Cobbing,E. J., and Beckinsale, R. D., Gonzdez,E., 1987, Petrographische und geochemische Untereds.,Magmatism at a plate edge:The Peruvian Andes: Glasgow, suchungen an die Sedimentabfolge desPucaras in der schichtBlackie and Son, Ltd., p. 36-44. gebundenen Zn-Pn Lagerst/itte SanVicente,Per6: Unpub.Di- Lancelot,J. R., Laubacher,G., Marocco,R., and Renaud,U., 1978, plomarbeit,Univ. Heidelberg, 128 p. U/Pb radiogeochronology of two granitic plutons from the Gonzdez,E., and Fontboth, L., 1986, Petrographicand lithoEasternCordillera(Per6)--extent of Permianmagmatic activity geochemical investigations on the Pucart Group in the carbonand consequences: Geol. Rundschau, v. 67, p. 236-243. ate-hostedZn-Pb depositof SanVicente, Per6 labs. I: Berliner Land, L. S., 1983, The applicationof stableisotopes to studies of Geowiss. Abh., Reihe A, Sonderband, p. 126-127. the origin of dolomiteand to problemsof diagenesis of clastic Gorzawski,H., Fontbot$, L., Sureau,A., and Calvez, J. Y., 1989, sediments: Soc.Econ. Paleontologists Mineralogists, v. 10, p. Strontiumisotopetrendsduring diagenesis in ore-bearingcar41-4-22. bonate basins: Geol. Rundschau, v. 78, p. 269-290. Lange,S., Chaudhuri,S., and Clauer, N., 1983, Strontiumisotopic Gorzawski,H., Fontboth, L., Field, C. W., and Tejada, R., 1990, evidencefor the origin of baritesand sulfides from the MissisSulfurisotopestudies in the zinc-leadmine SanVicente,central sippi Valley-type ore depositsin southeast Missouri:ECON. Peru, in Fontbot$, L., Amstutz, G. C., Cardozo, M., Cedillo, GEOL., v. 78, p. 1255-1261. E., and Frutos, J., eds., Stratabound ore deposits in the Andes: Lavado,M., 1980, Geologicaspects of the ore occurrences at the Berlin-Heidelberg-NewYork, Springer-Verlag, p. 305-312. SanVicente mine, SanRamon,Central Per6: Unpub. M.Sc. theGrant, N. K., and Miranda, C. B., 1983, Strontiumisotopeand sis,Dallas, Univ. Texas, 127 p. rare earthelementvariations in non-sulphide minerals from the in Chanchamayo-Gebiet Elmwood-Gordonsville mines,centralTennessee, in Kisvarsanyi, Levin, P., 1974, Die Pucara-Sedimente in Ost-Per6: Geol. Rundschau, v. 63, p. 345-356. G., Grant, S. K., Pratt, W. P., and Koenig, J. W., eds., Inter1975, Der petrographisch-geologische Rahmendes Channational conference on MississippiValley type lead-zinc de- -chamayo-Gebietesin Ost- Peru und die Deutung seiner posits.Proc. Vol.: Rolla, Univ. Missouri-RollaPress,p. 206schichtgebundeneen Vererzungen. Entwurf einer Metallo210. genese der 6stlichen Zentral-Per6:Unpub.Ph.D. dissert., Univ. Gunnesch, K. A., Baumann, A., and Gunnesch, M., 1990, Lead Heidelberg, 242 p. isotope variations acrossthe central Peruvian Andes: ECON. Levin, P., andAmstutz,G. C., 1973, Neue Untersuchungen fiber GEOL., v. 85, p. 1384-1401. schichtgebundene LagerstStten im zentralen Ostperu:MiinHagni, R. D., 1983, Ore microscopy,parageneticsequence,trace stersche Forschungen Geologie Pal/iontologie, v. 31/32, p. 233elementcontent,andfluid inclusion studies of the copper-lead259. zinc depositsin the southeast Missourilead district, in KisvarD. L., and Hallam, A., 1982, A faciesanalysis of the sanyi,G., Grant, S. K., Pratt, W. P., and Koenig, J. W., eds., Loughman, Pucart Group(Norianto Toarcian carbonates, organic-rich shale International conferenceon Mississippi Valley type lead-zinc and phosphate) of central and northernPer6: Sed.Geology,v. deposits. Proc. Vol.: Rolla, Univ. Missouri-Rolla Press,p. 243256.
32, p. 161-194.
Hannah,J. L., and Stein, H. J., 1984, Evidence{br changing ore fluid composition: Stableisotopeanalyses of secondary carbonates, Bonneterre Formation, Missouri: ECON. GEOL., v. 79, p.
1930-1935.
Macfarlane, A. W., 1989, Lead, sulfur and strontiumisotopesin the Hualgayocarea, Per6, and lead isotopeprovinces of the centralAndes: Unpub.Ph.D. thesis, Cambridge, HarvardUniv.,
370 p.
1437
in LaisMacQueen, R. W., andPowell,T. G., 1983, Organicgeochemistry Rickard, D., 1983, Precipitationand mixingmechanisms of the Pine Point lead-zinc ore field and region, northwestern vail-type sandstone lead-zincdeposits in Kisvarsanyi, G., Grant, Territories, Canada:ECON. GEOL.,v. 78, p. 1-25. S. K., Pratt, W. P., and Koenig, J. W., eds., International conMcCrea, J. M., 1950, On the isotopicchemistryof carbonates ferenceonMississippi Valley type lead-zinc deposits. Proc.Vol.: Rolla, Univ. Missouri-RollaPress,p. 449-458. and a paleotemperaturescale:Jour. Chem. Physics,v. 18, p. 849-857. Russell,C. W., 1985, A strontiumisotopestudyof oil field brines Medford,G. A., Maxwell,R. J., andArmstrong, R. L., 1983, 87Sr/ and associated rocksin southeastern Mississippi: Unpub. M.S. 86Srratio measurementson sulfides,carbonates,and fluid inthesis,Florida State Univ., 176 p. clusions from Pine Point, Northwest Territories, Canada: An Schulz,G. G., 1971, Die schichtgebundene Zinkblende LagerS7Sr/S6Sr ratio increase accompanying the mineralization prostStteSanVicente in Ost-Per6und ihr geologischer Rahmen: cess:ECON. GEOL., v. 78, p. 1375-1378. Unpub. Ph.D. dissert.,Univ. Aachen, 165 p. Mgard, F., 1968, Geologa del Cuadr/ngulo de Huancayo: Ser- Sharma, T., andClayton,R. N., 1965, Measurement of SO/60 vicio Geol. Minero Bol., v. 18, 123 p. ratiosof total oxygenof carbonates: Geochim.et Cosmochim. -1978, Etude gologique des Andesdu Perou central: ORActa, v. 29, p. 1347-1353. STOM Mem., v. 86, 303 p. Soler,P., 1987, Variationsdesteneursen elementsmineurs(Cd, -1984, The Andeanorogenic period andits major structures In, Ge, Ga, Ag, Bi, Se, Hg, Sn) des mineraisde PbZn de la in central and northern Per6: Geol. Soc.LondonJour., v. 14, provincepolymtallique des Andesdu Prou central:Minerap. 893-900. lium Deposita, v. 22, p. 135-143. Meyers, W. J., and LohmannK. C., 1985, Isotope geochemistry Spirakis, C. S., 1986, The valence of sulfur in disulfides--an of regionallyextensivecalcite cement zonesand marine comoverlookedclue to the genesis of Mississippi Valley-type leadponentsin Mississippian limestones,New Mexico: Soc. Econ. zinc deposits: ECON.GEOL.,v. 81, p. 1544-1545. Paleontologists MineralogistsSpec. Pub. 36, p. 223-239. Starinski, A., Bielski, M., Lazar, B., Steinitz, G., and Raab, M., Moore, C. H., 1985, Upper Jurassic subsurface cements: A case 1983, Strontium isotopic evidence on the history of oilfield history:Soc.Econ. Paleontologists Mineralogists Spec.Pub. 36, brines, Mediterranean Coastalplain, Israel: Geochim. et Cosp. 291-308.
mochim. Acta, v. 47, p. 687-695.
Mukasa,S., 1984, Comparative Pb isotopesystematics andzircon U-Pb geochronology for the Coastal, SanNicolasandCordillera Bianca batholiths, Per6: Unpub. Ph.D. thesis, Santa Barbara, Univ. California,383 p. Ohmoto,H., andRye, R. O., 1979, Isotopes of sulfurandcarbon, in Barnes,H. L., ed., Geochemistryof hydrothermalore deposits:New York, Wiley Intersci., p. 509-567. Orr, W. L., 1974, Changesin sulfur contentand isotopicratios of sulfurduringpetroleum maturation--study of BigHorn basin Paleozoic oils: Am. Assoc.Petroleum GeologistsBull., v. 58,
p. 2295-2318.
Stueber,A.M., Pushkar,P., and Hetherington,E. A., 1984, A strontium isotopic study of Smackoverbrines and associated
solids, southern Arkansas:Geochim. et Cosmochim. Acta, v. 48, p. 1637-1649.
Sunwall,M. T., and Pushkar,P., 1979, The isotopiccomposition of strontiumin brines from petroleumfields of southeastern Ohio: Chem. Geology, v. 24, p. 189-197. -1984, Oil fieldbrines asore-forming solutions: F. CON. GEOL.,
v. 79, p. 23-37.
--
1977, Geological and geochemicalcontrolson the distribution of hydrogensulfidein natural gas,in Campos, R., and Goni, J., eds.,Advances in organicgeochemistry: Madrid, Empresa Nacional Adaro Investigaciones Mineras, SociedadAn-
6nima, p. 571-597. Palacios, O., 1980, E1GrupoPucar/ en la regi6n Subandina (Per6 central): Soc.Geol. Per6 Bol., v. 67, p. 153-162. Pardo,A., 1983, A faciesanalysis of the Pucar Group (Norian to Toarciancarbonates, organic-rich shaleandphosphate) of central andnorthernPer6--comment:Sed.Geology, v. 35, p. 215223.
Szekely,T. S., and Grose, L. T., 1972, Stratigraphyof the carbonateblack shaleand phosphate of the Pucar5Group (Upper Triassic-Lower Jurassic), central Andes, Per6: Geol. Soc. America Bull., v. 83, p. 407-428. Tayler, J. R., 1962, ExplorationUchubambaarea, Jauja,Junin: New York, EasternAndesCorporation,JuneRept., 2 p. (unpub. rept.). Trudinger, P. A., Chambers,L. A., and Smith,J. W., 1985, Low temperaturesulphate reduction: Biological vs.abiological: CanadianJour. Earth Sci., v. 12, p. 1910-1918.
Veizer,J., andCompston, W., 1974, S7Sr/S6Sr composition of seawater during the Panerozoic:Geochim. et Cosmochim.Acta, v. 38, p. 1461-1484.
Pardo, A., and Sanz,V., 1979, Estratigrafiadel cursomedio del Veizer,J., andHoers, J., 1976, The natureof Os/O 6 andCa/ Rio La Leche, Departamentode Lambayeque: Soc.Geol. Per6 C2 secular trendsin sedimentary carbonate rocks.Geochim. Bol., v. 67, p. 153-162. et Cosmochim.Acta, v. 40, p. 1387-1395. Powell, T. G., and MacQueen,R. W., 1984, Precipitationof ores Walter, L. M., Brannon,J. C., Moldovany,E. P., and Podosek, and organic matter: Sulfate reactionsat Pine Point, Canada: F. A., 1987, Sr andS isotopic dataon diagenetic sulfides, sulfates Science, v. 224, p. 63-66. and calcites(Smackover Fm., S. W. Arkansas): Implications for Prinz, P., 1985a, Stratigraphie und Ammonitenfauna der PucarSfluid sourcesand chemicalevolution [abs.]:Soc. Econ. PaleGruppe (Obertrias-Unterjura) von Nord-Per6:Stuttgart,Paontologists Mineralogists Ann. Midyear Mtg., Austin,Texas, leontographica,Abt. A., v. 188, p. 153-197. 1987, v. 4, p. 88. -1985b, Zur Stratigraphie und Ammonitenfauna der PucarS- Wedepohl, K. H., 1974, Handbook of geochemistry:Berlin, Gruppe bei San Vicente: Dept. Junin, Per6: Stuttgart-Berlin, Springer-Verlag, v. 11-4, p. 38K-1-38K-13. Newsl. Stratigr.,v. 14, p. 129-141. Woronick,R. E., and Land, L. S., 1985, Late burial diagenesis, Puig, A., 1988, The geologicand metallogenetic significance of Lower Cretaceous Pearsall and Lower Glen Rose Formations, leadisotope composition of leadin galena of the ChileanAndes: south Texas: Soc.Econ.Paleontologists Mineralogists Spec. Pub.
ECON. GEOL., v. 83, p. 843-858.
36, p. 265-275.

Genesis of The Mississippi Valley-Type ZN-PB Deposit of San Vicente

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Genesis of The Mississippi Valley-Type ZN-PB Deposit of San Vicente

Uploaded by

Copyright:

Available Formats

EconomicGeology Vol. 85, 1990, pp.

Mineralogisch-Petrographisches Institute, Im Neuenheimer Feld236, D-6900Heidelberg, Germany

Max Planck Institut fdr Chemie, Postfach 3060, 6500 Mainz,Germany

The SanVicenteZn-Pbore deposit is situated 300 km eastof Lima in centralPeru, within

Lead and zinc occurrences in Pucart rocks and as

Zn-PbDEPOSIT, SAN VICENTE, CENTRALPERU

Roque'( '<' x..-i

Caluga 75' 11 S a n Ram6n

within the Pucara sequence

Platform at the Beginningof the Andean Cycle

Pucarft sedimentation in the entire basin.

Despitethe differentlithologic development in the

of the UlcumanoFormation (Sinemurian, opmentofperitidal dolomites, in part with preevapo- limestones

relief ofevaporific mineral

voltanits luff orpyrodastic rock

Zn-Pb DEPOSIT, SAN VICENTE, CENTRAL PERU

west '1 Pliensb. (Oxapampa Fm.,

Socosaoi Fm 'Areu!P'. ' '-

clast siments ''

Strata-Bound Ore Depositsin the PucarfiGroup

L. FONTBOTI AND H. GORZAWSKI

ter carbonate platformat the westernmarginof the BrazilianShieldconstitutes an interesting exploration

RegionalGeology of the SanVicenteDeposit

Carbonate rocks - Pucar Group

(Lower Permian} Limestones Copacabana Group

Precambrian and/or Paleozoic

Gabbroid rocks (undated)

LL Llanco Cateador, CLClody, HU Huacrash, R Rondayacu}

Zn-Pb DEPOSIT, SAN VICENTE, CENTRAL PERU

red sandstone and carbonate rocks over about 30 m

tables, as well as the abbreviationsused henceforth, are given in parentheses).

Ram6ngranite.Theseare well-beddedlimestones of-

andwackestone ) anddolomite intercalations. There

Terropin Son Vicente

SAN JUDAS DOLONITE i1 -// .I..-.__.L

I " / ,,.*., /,,.*.,

-I' I-I .i.

.... -'---"--,.... '...... - -.r

coastal dolomitic facies with abundant detrital ma-

zation the original depositional fabric can often be

Zn-Pb DEPOSIT, SAN VICENTE, CENTRAL PERU

I 52040 '1 2 3 4 5 6 7 6 9'

SAN VICENTE DOLOM I TE

--- slope breccln

Ayala 3t (techo = top) 3i (intermedio= intermediate) 3p (piso-- bottom)

953 923 896 881

TheBituminous Silty Limestone (BSL, 1,109-1,189m):

facies belongs to the Bituminous SiltyLimestone or

quartzgrains aresubangular to subroundish andrange up to 200 # in diameter. X-raydiffraction reveals that

Palacios (1980) defineda "Formaci6n SanVicente"

Zn-Pb DEPOSIT, SAN VICENTE, CENTRAL PERU

One interestinggeochemical characteristic is the low Sr contentof all three dolomiticunitscompared

similar ore occurrences in the eastern Pucarfi and

FIG. 8. Geologic mapof the SanVicenteminingarea.A-A' = the profile in Figure 7.

fiatandlagoon facies arecharacterized byveryfinely

of this unit coincide with maximum amounts of ter-

L. FONTBOT AND H. GORZA WSKI

Zn-Pb DEPOSIT, SAN VICENTE, CENTRAL PERU

hasproduced majorunconsolidated collapse breccias containingimportantamounts of ore (Fig. 13).

A largepart of the SanVicenteore displays a characteristic rhythmicbanding(Fig. 10a-h). It is locally

L. FONTBOTI AND H. GORZAWSKI

Zn-PbDEPOSIT, SANVICENTE,CENTRAL PERU

Arrows indicate east- and westwards migration of barrier (b)

I " / ,,.., /,,..,