Economic Geology Vol.94, 1999, pp.

1067-1092

An Evaluation of theInorganic andOrganic Geochemistry of the San Vicente Mississippi Valley-Type Zinc-Lead District, Central Peru: Implications forOreFluidComposition, Mixing Processes, andSulfate Reduction
JORGE E. SPANGENBERG, t
Institut deMindralogie et Pdtrographie, Universitd deLausanne, BFSH-2, CH-1015 Lausanne, Switzerland
LLUiS FONTnOTE,

Ddpartement deMingralogie, Universitd deGenve, 13,ruedes Maralchers, CH-1211 GenOve 4, Switzerland

AND STEPHEN A. MACKO

Department ofEnvironmental Sciences, University ofVirginia, Charlottesville, Virginia 22903

Abstract

Mississippi Valley-type zinc-lead deposits andoreoccurrences in the San Vicente beltarehosted in dolostones oftheeastern Upper Triassic to Lower Jurassic Pucar5 basin, central Peru. Combined inorganic andorganic geochemical data from22 sites, including themain San Vicente deposit, minor oreoccurrences, andbarrenlocalities, provide better understanding of fluidpathways andcomposition, oreprecipitation mechanisms, Eh-pHchanges during mineralization, and relationships between organic matter and oreformation. Ore-stage dark replacement dolomite and white sparry dolomite areFe and rare earth element (REE)depleted, andMn enriched, compared to thehost dolomite. In themain deposit, theydisplay significant negative Ce andprobablyEu anomalies. Mixing of anincoming hot,slightly oxidizing, acidic brine(H2CO3 being thedominant dissolved carbon species), probably poor in REEand Fe,withlocal intraformational, alkaline, reducing waters explains theoverall carbon andoxygen isotope variation andthedistributions of REE andother trace elements in thedifferent hydrothermal carbonate generations. Theincoming orefluidflowed through major aquifers, probably basal basin detrital units, withlimited interaction withthecarbonate host rocks. Thehydrothermal carbonates show a strong regional chemical homogeneity, indicating access oftheorefluids byinterconnected channelways neartheoreoccurrences. Negative Ce anomalies in themain deposit, thatareabsent at thedistrictscale, indicate local ore-fluid chemical differences. Oxidation ofbothmigrated andindigenous hydrocarbons bytheincoming fluidprovided thelocal reducing conditions necessary forsulfate reduction to H2S, pyrobitumen precipitation, andreduction of Eu3+ to Eu2+. Fe-Mncovariations, combined withtheREE contents ofthehydrothermal carbonates, areconsistent withthemineralizing system shifting fromreducing/rock-dominated tooxidizing/fluid-dominated conditions following oredeposition. Sulfate and sulfide sulfur isotopes supportsulfide origin fromevaporite-derived sulfate bythermochemical organic reduction; further evidence includes thepresence oflaC-depleted calcite cements (--12%o 81C) assulfate pseudomorphs, elemental sulfur, altered organic matter in thehost dolomite, and isotopically heavier, late,solid bitumen. Significant alteration of theindigenous andextrinsic hydrocarbons, withabsent bacterial membrane biomarkers (hopanes) is observed. Thelight 8a4S ofsulfides from small mines andoccurrences compared tothemain deposit reflect alocal contribution of isotopically lightsulfur, evidence of local differences in theore-fluid chemistry.

Thiscommunication summarizes anextensive geochemical investigation of the host rocks of the San Vicente Mississippi MULTIPLE fluidmixing andfluid-rock interaction during forValley-type district hosted in the Upper Triassic to Lower mation of Mississippi Valley-type deposits induces composiPucari basin, central Peru, andpresents newdata on tional changes in thefluidandhost carbonates. The elemen- Jurassic carbonate trace elements and sulfur isotopes. Recent extental andisotopic composition of thehydrothermal carbonates activities towards the northof the maindeandassociated organic matter mayrecord thenature andex- sionof mining posit, as well as the ongoing intense exploration in thewhole tentof these interactions. In particular, variations in Mg, Sr, has opened upnewareas formapping andgeochemNa, Fe, Mn, and rare earth elementsin carbonates associated district, Surface outcrops andunderground drillcores withbase metal deposits may provide valuable information on icalsampling. at the San Vicente main deposit, minor ore occurrences, and theflowdirection ofdolomitizing andmineralizing fluids, the barren localities were systematically sampled to characterize extent of fluid-rockinteraction, and oxidation potential geochemistry and its spatial relationship to changes (e.g.,M/511er andMorteani, 1983; Vietset al., 1983; the host-rock orebodies. Thegeochemical approach includes studies Graf, 1984,1988;Buelter and Guillemette, 1988;Gregg, known 13 12 18 16 87 6 1988; Shulda, 1988; Gregg andShelton, 1989; Meyers, 1989; of carbonatetrace elements, C/ C, O/ O, and Sr/sSr data,fluid inclusion studies, andorganic geochemical and Farr, 1992). isotopic (13C/12C, lSN/14N) investigations of the associated organic matter (Spangenberg, 1995;Moritz et aI., 1996; Corresponding author: email, Jorge. Spangenberg@imp.unil.ch
0361-0128/99/3001/1067-26 $6.00 1067

Introduction

1068

SPANGENBERG ET AL.

Spangenberg et al., 1995,1996;Spangenberg and Macko,

1998). The two aims of this contributionare: to discuss con-

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straints setby the carbonates' REE andtraceelement (Fe, Mn, Sr,Na,Ba,Zn) composition onthesource andcompositionof theoresolutions andtheprocesses controlling sulfide precipitation; andto reevaluate published isotopic investigations of the carbonates andassociated organic matter using thenewdata. Given thepoor knowledge concerning thebehavior of REE andtraceelements in complex hydrothermal systems (e.g.,M611er, 1983;BauandM611er, 1991),the observed REE distributions in San Vicente carbonates were

xxxxxxxxx x xxxxxxxx

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Y+++++++

evaluated using quantitative modeling of the 13C/2C and lsO/160 covariations in thehydrothermal carbonates (Spangenberg et al., 1996), andusing anorganic geochemical and isotopic study of the hydrocarbons staining the SanVicente rocks (Spangenberg and Macko,1998).New isotopic data fromSanVicente district sulfides arepresented. The combined inorganic, organic, and isotopic geochemical data recordthe fluid/fluidand fluid/rock mixing processes involved during sulfide precipitation at SanVicente, andgive insights into the composition of the ore fluid(s), the fluid pathways, andthesulfur sources andreduction mechanisms.
Geologic Setting

San Vicente

mine

-11o15 '

Location andstratigraphic setting TheSan Vicente Mississippi Valley-type Zn-Pb district islocated 300 km east of Lima in central Peru, at an altitude be-

tween 1,000 and2,500m, in theCejade Selva--the eastern flankof theAndes covered by tropical rainforest. The accumulated production andreserves areabout 20 million metric tons(Mt) of oregrading 10wt percent zincand0.8wt percent lead (Fontbot et al., 1995).

Legend

3 km

post Uncush 1 Units Uncush Limestonel Pucara Group

/ Lower uurassc)

[ Units pre Uncush [!Upper ,Triassi. c.Undifferentiated J

[l Red Sandstone andMitu Group

The UpperTriassic to Lower Jurassic Pucar5 basin, which [ San Ramn Granite (UpperPermian - Lower Triassic) hosts theSan Vicente deposit andother unmined Mississippi Tarma Granodiorite (Upper Permian Lower Triassic) Valley-type occurrences (Fig.1), is a carbonate platform at Group Copacabana Limestone thewestern margin of the Brazilian Shield. The basin devel(LowerPermian) opedat the startof the Andean cycle with a marine trans- Lower Paleozoic rocks gression overclastic sediments andvolcanic andvolcaniclas- Precambrian schists tic rocks of the LatePermian to EarlyTriassic Mitu Group. Major tectonic lineament J'Thrust fault Recent sedimentological, carbonate S7Sr/S6Sr, 13C/inC, lsO/lO, Closed mine OStudied occurrences andmetallogenetic studies of the Pucart basin arediscussed
in Fontbot6 (1990), Rosas(1994), and Moritz et al. (1996).
Fzc.1. Geological mapof San Vicente beltshowing thestudied localities
andmineralized areas). QP = Quebrada Pifi6n; RO = Rondayacu; YS Thegeology oftheSan Vicente main deposit was described (barren = Yanachuro Sur; SI = Sillapata; UT = Utcuyacu; QU= Quebrada Utcuyacu; by Schulz(1971),Levin (1975),Fontbot6 and Gorzawski AY= Aynamayo; CH = Chilpes; AC --Afioramiento Campana; US = Uncush (1990), andFontbot6 et al.(1995). In theSan Vicente mining Sur;UN = Uncush; sJ= San Judas; SV= San Vicente mine; SO= Quebrada VI = Vilcapoma; AR = Arcopunco; MA = Machuyacu; QS = Quearea, theNorian to Hettangian carbonate sequence ofthePu- Solitaria; Seca; PA= Palmapata; PJ= Puntayacu Junior; QC = Quebrada Cascas; car5 Group isabout 1,300 m thick, andischaracterized byfa- brada SP = Sur Pichita;P1 = Pichita. ciesdeveloped in locally isolated basins on a shallow-marine shelf(Fig. 2). Pseudomorphs of evaporitic sulfates occur in (Fig.1). Detailed sedimentological studies ofthePusome horizons. Three dolomitic units, theSan Judas Dolomite, horizon

the San Vicente Dolomite, and the Alfonso Dolomite, host

the orebodies. Most of the economic mineralization is within

car5 basin in the San Vicente district (Fontbot and Gorza-

wski,1990; Rosas, 1994; Hasler, 1998)indicate important fachanges in themining area. Subtidal shallow-water facies the San VicenteDolomite. The bituminous silty Uncush cies Limestone is a black limestone richin organic matter(total with rare restricted shelf intercalations characterize the oredolomitic units. organic carbon, TOC, ranges from0.1to 4.5wt %, Spangen- bearing bergandMacko, 1998)andveryfinecrystalline pyrite(total Mineralization sulfur up to 1.2wt %),withshaly to silty intercalations. This Theoreoccurs mainly aslens-shaped bodies (mantos) comunit (Fig. 2) overlies the majorore-bearing dolomitic unit conformable withbedding onthe deposit scale, up to (San Vicente Dolomite) andprovides a stratigraphic reference monly

INORGANIC & ORGANIC GEOCHEMISTRYOF SANVICENTE, PERU

UNIT
DESCRIPTION

1069

Mediumto very coarsely crystalline dolomite with

abundant WSD.

Bituminous, laminated,black limestone with shalyto silty

intercalations.

Main ore-bearingunit. Fine to

verycoarsecrystalline dolomite.
AbundantWSD and evaporite pseudomorphs. Subtidaloolitic barrierfacieswithlagoonand supratidal intercalations.

Dolomitelayers in part
dedolomitized and karstified.

Shaly intercalations.

Fine to very coarse crystalline

dolomite. Abundant WSD and

evaporitepseudomorphs.
Subtidal oolitic barrier facies with

lagoonand supratidal
intercalations.

(Fig. 4). Theyinclude darkreplacement dolomite-I, white sparry dolomite-II, latevoid-filling dolomite-IIId or calciteIIIc, andcalcite or dolomite replacing evaporitic sulfate. The following description andclassification of thecarbonate generations aresummarized fromSpangenberg (1995). The darkreplacement dolomite-I is a fine- to mediumcrystalline dolomite, withTOC ranging from0.02to 1.49wt percent (Spangenberg andMacko, 1998). Thisdolomite has been hydrothermally altered tovarying degrees, andhas been classified asIvt: fine-tovery finegrained (15-60/am, Fig.3C, D); If: fine-grained (40-100 /am, Fig. 3E, F); and Im: medium-grained (100-400/am, Fig.3G, H). The veryfine grained dolomite isnonluminescent, indicating a high Fe/Mn ratio(Fig.3D), andrepresents thebestavailable approximationtothepreore host dolostone (Fig.4). In dolomites Iwand If, it ispossible to recognize relics of primary textures, especially ghosts of former ooliths, whereas the primary texture preservation is poorer in the red-luminescent darkreplacementdolomite-Im. The changes in cathodoluminescence intensity suggest thatthehost dolomite was depleted in Fe and enriched in Mn during alteration.
In advanced metasomatic alteration,the white dolomitere-

placing thedark host dolomite-I exhibits increased grain size, Limestone with dolomite. anda coarse subhedral whitesparry dolomite (0.4-2.5mm) Up to 35% detritalmaterial, mainly at the basis which is which wasprecipitated fromthe hydrothermal fluidin the enriched in clastic material. Facies:mainlyof open sea shelf available porosity. This altered dark replacement dolomite-Im with few intercalations of is intergrown withthefirstgeneration of fine-crystalline anshallower facies hedral sphalerite andoccasionally withpyrite andmicrocrystalline quartz (Fig.4). Whitesparry dolomite-II is themost extensive hydrotherRed Clastic facies consisting ofred Sandstone silt andsandstone withmassive maldolomite cement andoccurs throughout the entireSan Vicente belt.The whitesparry dolomite-II is a subhedral, whiteor grayish (dueto sulfide andorganic matterincluI 2 3 4 5 6 7 8 9 10 11 sions), sparry dolomite occurring as open-space fillingin FIG.2. Stratigraphic column ofthePucara Group in theSan Vicente minspots, in millimeterto centimeter-thick bands replacingarea(afterRosas, 1994).1: red sandstone; 2 = marly limestone; 3 = small marly dolomite; 4: limestone; 5: dolomite; 6: dolomite withwhite sparry ingthedarkreplacement dolomite-I, andasbreccia cement dolomite; 7: partly dedolomitized dolomite; 8 = bituminous silty limestone; (Fig.3A,B).Typically, white sparry dolomite-II postdates sul9: subvolcanic rocks; 10: gypsum lenses; 11: ore. fideprecipitation andfillsopen spaces. An exception where white sparry dolomite-II islargely lacking istheSan Vicente 1.3kmlong, 200to300mwide, andseveral meters thick. The Techo manto, located in the upperandnorthern margin of sulfide minerals largely replace dolomitized, subtidal, oolitic themain oredeposit. Alternating repetition of darkreplacegrainstones interlayered withdolomitized, organic-rich mud- mentdolomite-I andwhitesparry dolomite-II bands gives zebratextureof the ore rock,a comstones with cryptalgal laminations and evaporitic sulfate riseto the characteristic pseudomorphs. Ore occurs aszebra ore,replacements, and monfeature of Mississippi Valley-type deposits (e.g., Beales Fontboth, 1993).Fluidinclusion studies on occasionally ascements in breccias or veinlets (Fig.3A, B; andHardy,1980; Fontbotd and Gorzawski, 1990;Spangenberg et al., 1995, thewhitesparry dolomite-II indicate precipitation fromhot 1996). Themain oreminerals aresphalerite and galena, with (115-162C) saline (9.5-26wt % NaC1 equiv) fluids (Moritz trace pyriteandmarcasite. et al., 1996).The latevoid-filling carbonate occurs within Theore-bearing solutions arebelieved tohave gained heat white sparry dolomite-II ascoarseorvery coarse grained inandmetals bymigration through, andleaching of,theunder- terstitial open-space fillings, mainly asanhedral milky-white lying detrital rocks andPermo-Triassic intrusions. These solu- dolomite (late void-filling dolomite-IIId) orcalcite (late voidtions may have been channeled upwards bynortheast-southfilling calcite-IIIc). Another carbonate phase occurs assulfate west-to north-south-trending faultsystems andbasement pseudomorphs in thedarkreplacement dolomite-I. Themain highs inthevicinity oftheorebodies (Spangenberg, 1995; e.g., minerals replacing evaporitic sulfate (gypsum or anhydrite) LowerPaleozoic phyllites andquartzites nearMonobamba,arecalcite, cherty quartz, andsubordinate dolomite. Fig.1). Organic matter in theSanVicente deposit Hostandgangue carbonates In San Vicente, asin almost all Mississippi Valley-type deDifferent generations of syn-andpostore hydrothermal posits, the ore is associated in timeandspace with organic carbonates are distinguished in the ore-bearing dolostones matter(e.g.,Macqueen andPowell, 1983; Anderson, 1991;

1070

SPANGENBERG ET AL.

INORGANIC & ORGANIC GEOCHEMISTRY OF SANVICENTE, PERU

1071

occurs in the upperandnorthern margin of the Giz and Barnes,1994). The organicmatter occurs as marcasite, oredeposit. Pyrite isotherwise only present in traces. (hydro)thermally altered kerogen disseminated in the host main rockand/or asliquidor solid bitumen staining theore.Four Summary of Previous Geochemical Studies distinct types oforganic matter areassociated withcarbonates in the SanVicente district (Spangenberg andMacko, 1998). andoxygen isotope geochemistry Theycanbe classified, using paragenetic andtextural rela- Carbon of the hydrothermal carbonates tionships, as(1) organic matter disseminated in the Uncush andoxygen isotope studies of thehost andgangue Limestone; (2) organic matter disseminated in thehost dolo- Carbon stones (darkreplacement dolomite-Iv ); (3) organic matter carbonates were used to constrain ore formation models between thegrain boundaries of sulfides in darkreplacement(Spangenberg, 1995;Spangenberg et al., 1996).A mixing an incoming hot, saline, slightly acidic dolomite-Im (Fig.5A);and(4) solid hydrothermal black bitu- modelbetween the maindissolved carbon species), radiogenic (Pb, menoccurring asopen-space filling, coating thelatevoid-fill- (H,2CO3 formation waterexplains the overall ingcalcite (Fig.5B). Types 1 to 3 organic matter are fine- Sr) fluid,andthe local variation in the carbonate generations (al3CrD = grained, very maturemeta-bituminite (equivalent vitrinite isotopic anda18OsMow = 18.0to 24.3%0; Spangenberg reflectance (Ro)upto 2.8%mean) indicating a strong degree -11.5 to 2.5%0 Themain ore-stage white sparry dolomites show ofcoalification (Spangenberg andMacko, 1998). Thethermal et al.,1996). range (al3c= -0.1 to 1.7%o anda180= 18.7to maturity of most samples corresponds to semianthracite to a narrower which is explained byexchange between themineranthracite stages. The meta-bituminite is anamorphous con- 23.4%o) fluids andthe carbonate host rocks, combined with tinuum occurring asa fine-grained micritized solid, occurring alizing and pressure changes (Spangenberg et al., in veins,fracturefillings,and disseminated alonggrain temperature 1996). Thisfluid-rock interaction model explains thepervaboundaries. It formed during diagenesis and postdepositional alteration ofthehost dark replacement dolomite-Ivf. The alteration of bituminite, a decomposition product of algae, sive fannalplankton, and bacteria (Teichmiiller, 1982). Some open-space filling white sparry dolomite-II and thecoexisting are considered to havebeenformed by prograins show mosaic structure and peripheral alteration rims of sphalerite-II longed fluid-host dolomite interaction andlimited CO2dehigher orlower reflectance thanthecore. These observations in anopen anddynamic system (Spangenberg et al., are compatible with organic matteralteration duringpro- gassing Latevoid-filling dolomite-IIId, latevoid-filling calcitelonged interaction of hydrothermal fluids withhostcarbon- 1996). very minor, sphalerite III formed as ates(Spangenberg et al., 1996,Spangenberg and Macko, IIIc, andtheassociated, of CO2degassing andconcomitant pH in1998). The type4 organic matter is a solid pyrobitumen in- a consequence soluble in organic solvents. Locally, in thevicinity of subvol- crease in a slightly acidic orefluid(Spangenberg et al.,1996). alSOcovariations in the darkreplacement canic rocks, thepyrobitumen isglassy and very hard withcon- The al3Cversus choidal fractures. dolomite-(Iv, If, andIm)andwhitesparry dolomite-II show thatthe isotopic composition of boththe orefluidandthe Sulfur minerals in theSanVicente deposit host dolomite wereprogressively modified by fluid-rock inThesulfur minerals include sulfates (gypsum oranhydrite), teraction processes untiltheyattained isotopic equilibrium et al., 1996).The late void-filling native sulfur, and sulfides (sphalerite, galena, and pyrite). Sul- (fig. 7 in Spangenberg fate lenses occur in the basal Red Sandstone of the Pucar5 dolomite-IIId isotopic composition confirms that this late Group. Native sulfur occurs intergrown withcalcite in sulfate dolomite precipitated in open spaces froma fluidnotequilithat these pseudomorphs. The mainore minerals are sphalerite and bratedwith the hostrock.It is, therefore,assumed dolomites arerepresentative of the incoming galena. Sphalerite occurs in thesame paragenetic position as hydrothermal (Spangenberg et al.,1996). white sparry dolomite (Fig.4) as: (1)fine-crystalline anhedral oresolution sphalerite intergrown withdark replacement dolomite-Im; (2) geochemistry studies coarse, open-space-filling, subhedral sphalerite predating Organic and/or intergrown withwhitesparry dolomite-II onthe perA detailed organic geochemical andisotopic investigation (organic-extractable organic matter)and vasively altered dark dolomite; and(3)as very coarse euhedral of the bitumens crystals withinthe late void-filling dolomite-III, mostly as kerogens (organic-insoluble organic matter) of the SanVibreccia cement. Galena occurs mainly ascoarse-crystalline, cente district provides insights into thesource oforganic matbetween organic-matter alteration open-space fillings.Massive pyrite,pseudomorphic after ter andthe relationship
FIG.3. A. Zebra ore,hydraulic breccias, anddifferent carbonate generations (San Vicente N mine, manto Ayala, level 1570, cut600).Themineralization consists mainly of sphalerite (I andII) andgalena. B. Handspecimen (manto 3, sample FSV-657B) showing different carbonate generations: dark replacement dolomite (dark replacement dolomite-I) and textural subgenerations of whitesparry dolomite (whitesparry dolomite-II). C-H. Photomicrographs of the darkreplacement dolomite-I of theSan Vicente dolostones showing thethree subgenerations defined according to thedegree of hydrothermalalteration. C. Very finegrained dark replacement dolomite-I exhibiting oolites under normal light (uncrossed polars). D. Same fieldunder cathodoluminescence. Notereplacement oftheblack nonluminescent host bya dullredluminescence. The yellow rims indicate therecrystallization boundaries. E. Fine-grained dark replacement dolomite-I withoolites, partially replaced by dolomite-II. F. Same fieldof viewasin E under cathodoluminescence. The dull-red luminescent dolomite replaced thedolomite-I fromthecenter outwards. Bright yellow luminescence indicates exsolved organic matter. G. Mediumgrained, darkreplacement dolomite-I. H. Same fieldasin G under cathodoluminescence. Thehost dolomite was pervasive replaced bytheredluminescent dolomite. Noteghosts of oolites. 200-/zm scale barin photomicrographs C-H.

1072

SPANGENBERG ET AL.

Dolomite

Ivf

DRD I If Irn I
I

WSD-II

I I
I

LFD-III
--

I
Calcite I

I
I

LFC-III

Carbonate
replacing

EPC
-- -- -

I
I

I
I

sulfate
Quartz ,-

I
I I I I

I
I I I I

pyrite

sll
Sphalerite

I
I

sl II

I
i

sl III

Galena
Native sulfur --

I
I -- -- I
I

-- -- -- I-- 'I I
I

'

Organic matter

Kerogen
I

Free HC
I

Bitumen

FIG.4. Paragenetic sequence of thehydrothermal gangue minerals and orein the SanVicente district. Abbreviations: DRD = darkreplacement dolomite (DRD-I,4. very fine grained; DRD-If: fine-grained; DRD-Im: medium-grained); WSD= white sparry dolomite-II; LFD = late void-filling dolomite-IIId; LFC= late void-filling calcite-Illc; slI, slII, and slIII= sphalerite generations; EPD = dolomite replacing evaporitic sulfate; EPC= calcitereplacing evaporitic sulfate; HC = hydrocarbons.

o
i ! ! i !

5
cm.

valuesof the individualn-alkanes,indicatethat the rocksin

FIG.5. A. Bitumen infilling thegrain boundaries ofsphalerite in thefully and oreformation (Spangenberg andMacko, 1998). Isotopic hydrothermally altered dark replacement dolomite (sample FSV-915, manto data(aiscandSlSN) fromkerogens andassociated extracts,Ayala, level 1570, crosscut 600). 200-tzm scale bar. B.Solid hydrothermal bicombined withorganic molecular parameters andthe SlaC tumen occurs asvoidfilling andappears to beyounger thancalcite (manto
Ayala, level1750, crosscut 1240E).

themineralized areas were stained bya mixture ofindigenous hydrocarbons (--27%o)withextrinsic, laC-depleted, microSamples andAnalytical Methods bially derived hydrocarbons (--40%o). These extrinsic hydrocarbons wereprobably introduced to themineralization site Sampling bytheorefluidor,less likely, bylaterfluids using thesame Carbonate hostrocks weresampled at district andmine permeability network (Spangenberg andMacko, 1998). scales in mineralized andbarren areas along a 32-km, northThe pyrobitumen 5]aC values (Spangenberg et al., 1996; south traverse centered in the maindeposit (Fig. 1). AddiSpangenberg andMacko, 1998) from thesmaller Mississippi tionalsampling details are givenin Spangenberg (1995). Valley-type deposits andoccurrences (-26.9to -29.4%0) are Nineteen district-scale sampling localities include mined ore approximately 3 per mil lower thanthepyrobitumens from occurrences, surface outcrops, anddiamond-drill exploration the maindeposit (-23.0 to -28.2%0,median = -25.2%0). holes. Forty-two samples, mainly of theore-bearing dolomite There aretwopossible explanations fortheisotopic differ- units (Alfonso Dolomite, San Vicente Dolomite, and San ences between the pyrobitumens in the maindeposit and Judas Dolomite), wereanalyzed for major, minor, andtrace those in thesmaller Mississippi Valley-type deposits, butno elements. Forty-one samples from13 oreoccurrences were discriminating evidence. Eitherfacies differences in themain analyzed for REE. Forty-three samples fromtheSan Vicente ore-bearing horizons caused different mixing ratios which mine wereanalyzed formajor, minor, andtrace elements, and werereflected in thecomposition of themigrating hydrocar- 27 for REE. bons, or more intense water-washing and(hydrothermal) alpreparation teration removed isotopically light compounds from thepyro- Sample bitumens at the San Vicentemain deposit. The first Thinsections ofrepresentative samples ensured thecorrect explanation iscompatible withthesedimentological control classification of thecarbonate generations, in particular dark onthemain orehorizons attheSan Vicente deposit, whereas replacement dolomite-Ix, darkreplacement dolomite-It, and thesecond explanation suggests local differences in theore- darkreplacement dolomite-Ira (Fig. 3C-H). Selected thin fluidchemistry. sections wereexamined under cathodoluminescence, using a

INORGANIC & ORGANIC GEOCHEMISTRY OF SANVICENTE, PERU

1073

isotopes Technosyn 8200MKII instrument, operated at 16kV anda Sulfur 60 mA guncurrent. Sulfur minerals sampled forisotopic analyses include sulWeathered surfaces oftherock samples were removed by fates,native sulfur, and sulfides (sphalerite, galena, and sawing about 2-cm-thick slabs. These slabs were roughly pol- pyrite). Thesulfur isotope analyses were performed at the ished,washed with distilledwater,rinsedin acetone, and Department of Environmental Sciences, University of Virdried.The different carbonate generations wereseparatedginia, using an on-line elemental analyzer (EA)-continuous using a diamond-drill tablepress, andground in an agate flow-isotope ratio mass spectrometer (IRMS). TheEA-IRMS mortar to <250mesh. Thepowders wereanalyzed by stan- system consists ofa Carlo Erba 1108 elemental analyzer coudard X-ray diffraction methods toverify thepresence ofnon- pled byacontinuous flow interface totheMICROMASS-OPcarbonate minerals (quartz, clays, andsulfides) andto check TIMA IRMS. The EA oxidizes all the sample compounds forpossible crosscontamination between distinct carbonateunder a stream ofhelium andoxygen byflash combustion in phases. Samples containing visible or XRD-detected spha- a single oxidation-reduction quartz tube filled with oxidizing lerite were discarded. (tungsten trioxide) and reducing (elemental copper) agents at

1,030C. Water isremoved using anhydrous magnesium perchlorate, andthe gases entera chromatographic column QS)forseparation ofSOs which isisotopically anaA 0.5-g portion ofthedried sample powder was digested in (Poropak byIRMS(Giesemann et al.,1994). Thesulfur isotope 50 ml 1N HC1 at 50Cfor 2 hours,duringwhichtime lyzed arereported relative to the Canyon Diablo troilite dolomite reacts completely with the acid(e.g.,Robinson,values (CDT) standard. The reproducibility, assessed by replicate 1980). Afterdigestion, the solutions werefiltered through of a laboratory standard (barium sulfate, working Whatman No. 42 filters. The filters werewashed, ignited at analyses = +12.5%o $34S) was better than0.2per mil(1 s). 500C, andweighed to determine thewt percent insolublevalue residue (IR). The solutions wereanalyzed for Ca, Mg, Fe, Results Mn, Sr,Na, Zn, andBa using a Perkin-Elmer 3005inductively coupled plasma-atomic emission spectrometer (ICP- Major, minor, andtrace elements AES).Multielemental calibration standards wereprepared Major, minor, and trace (excluding rare earth) element confrom single element Alfa Aesar specpure ICP-standard solu- centrations in thegangue carbonates fromthemain deposit tions.Replicate analyses of the reference samples JLs-1 andoccurrences in theSan Vicente district aregiven in Table (limestone), JDo-1 (dolomite), and NBS-88b (dolomitic lime- 1.Thehydrothermal dolomites (dark replacement dolomitestone) indicated average reproducibilities forCaandMgbet- I, white sparry dolomite-II, andlatevoid-filling dolomiteterthan2percent (2 s),andforMn,Fe, Sr,Zn ofabout +__8 IIId) display a trend towards a more stoichiometric Mg conpercent. Thebarium (due to very lowconcentrations) and centration withadvancing paragenetic stage (Fig.6). Dark sodium reproducibilities varied significantly, occasionally ex- replacement dolomite-Ix isCa-enriched, with CaCO3 ranging ceeding 15percent. 55.9 to 60.2 mole percent (median = 58.1 mole %), and MgThe insoluble residue mass was used to convert the raw depleted (39.5-43.5 mole % MgCO3). Thealtered dark redatato 100percent of thewhole rock. Theacidinsolubleplacement dolomite (It, Ira), the open-space-filling white sparry residue in thebituminous silty Uncush Limestone was 30wt dolomite-II, and thelate void-filling dolomite-IIId areslightly percent, the darkreplacement dolomite ranged 2 to 3 wt morestoichiometric, with MgCO3medians of 42.7, 43.1, percent (upto 8 wt % in chert-rich samples), andthehy- 43.2,and43.4mole percent, respectively (Fig.6). A similar drothermal carbonates yielded only trace residues. XRD in- trend in the MgCO3/CaCO3 ratio was obtained by electron dicated that the mainnoncarbonate minerals were quartz microprobe analyses in selected ore-stage dolomites (Spanand sulfides.
Majorandtrace element analyses genberg, 1995). Thetrace element concentration ranges in thehydrotherRareearthelement analysis malcarbonates areshown in Figure 7.Thesoluble fraction of siltyUncush Limestone is poorin Fe, Mn, Rareearth elements andyttrium wereanalyzed byinduc- the bituminous

in the dark re(n = 5) analyses of a Uncush Limestone sample (FSV-524) The Mn, Sr, Na, and Ba concentrations dolomite-I increase during advancing alteration wasno greater than14percent, except for Tm (26%).At placement 7).TheSrenrichment in late void-filling dolomite-IIId highREE concentrations, thereproducibility is better than (Fig. to theunaltered dark replacement dolomite-Ix coin10percent. ForREEatconcentrations near thelower detec- relative withthetrendtowards higher Mg concentrations. tionlimit,theuncertainty is typically about 20 percent. The cides REE weredetermined in ninemine-scale carbonate samples Fe and Zn increaseto a maximum concentration in the dark replacement dolomite-It, thendecrease andarelowin the byICP-MSoftheacid-soluble fraction and bywhole-sample sparry dolomite-II and late void-filling dolomite-IIId. instrumental neutron activation analysis (INAA). The two white The overall increase in MrdFeratios through time(darkreprocedures evaluated thecontribution of thenoncarbonate
(acidnonsoluble) fractionto the total REE concentration.

Zncompared todark replacement dolomite-Ix, and tivelycoupled plasma-mass spectrometry (ICP-MS). The Na,and thehighest Sr(790/_g/g) andBa(30/_g/g) concensamples weredigested using theabove 1N HC1procedure.displays These high Srand Baconcentrations may reflect the Theaccuracy oftheREEanalyses was assessed byanalysis of trations. a standardreference material (XRAL Laboratories,written fact that the Uncush Limestone generally hasnot been commun.). Theanalytical uncertainty, monitored byreplicate dolomitized.

placement dolomite -It,dark replacement dolomite -Ira, white

1074

SPANGENBERGET AL.

TABLE 1. Geochemical Composition oftheAcid Soluble Fraction from Carbonates oftheSan Vicente District (including theSan Vicente Main Deposit)
CaCO3 MgCO3
42.88 42.00
43.43

Fe

Mn

Na

Sr

Zn4

Ba 4

Sample
FSV-984 FSV-985
FSV-952

Loc)
QP QP
RO

Lith. 2
SVD SVD
SVD

Carb. 3
WSD WSD
WSD

(mole %) (mole %)
56.53 57.40
56.30

(4ug/g)
476 1,284
262

(;ug/g)
2,358 1,674
982

(4ug/g)
436 551
303

(4ug/g)
93 74
113

(;ug/g)
12 3
41

(4ug/g)

FSV-953 FSV-953B
FSV-1001

RO RO
YS

SVD SVD
SVD

WSD WSD
WSD

56.48 56.43
55.90

43.04 43.08
43.81

185 628
534

2,022 1,617
850

399 375
358

72 88
66

24 37
13

6 6
6

FSV-1003
FSV-956

YS
UT

SVD
SVD

WSD
WSD

55.70
56.16

43.97
43.58

326
375

1,275
806

283
384

92
51

60
9

5
5

FSV-957

UT

SVD

WSD

56.43

43.34

555

535

327

60

FSV-652 FSV-653C FSV-1057 FSV-1059

QU QU QU QU

SVD SVD UL UL

WSD WSD

55.74 56.62 98.78 98.58

43.85 42.76 0.78 1.10

621 1,801 690 728

1,247 962 820 262

330 397 104 169

107 37 254 625

26 9,343 68 5

7 2 28 49

FSV-988 FSV-989 FSV-988 FSV-989

FSV-992 FSV-990 FSV-992

AY AY AY AY
AY AY AY

SJD SJD SJD SJD

SVD SVD SVD

DRD (I,) DRD (I,) WSD WSD

DRD (It) WSD WSD

56.10 55.56 56.34 55.62

56.35 55.44 55.77

43.36 43.66 42.95 44.02

43.22 44.13 43.73

1,657 2,523 2,251 398

988 608 808

982 1,213 1,195 1,299

1,013 1,409 1,558

415 402 378 364

323 349 517

68 97 60 67
59 136 102

19 90 22 44
3,581 48 164

7
6
71 19 12

FSV-754 FSV-753 FSV-754 FSV-754

FSV-982 FSV-755 FSV-759 FSV-755 FSV-759 FSV-761
FSV-982

CH CH CH CH
CH CH CH CH CH CH
CH

SJD SJD SJD SJD

SVD SVD SVD
SVD SVD SVD
SVD

DRD (I,) WSD WSD LFC

DRD (Im) DRD (I,) DRD (It) WSD WSD WSD
LFC

56.55 56.38 56.26 99.15

56.02 56.24 56.47 56.33 56.26 56.39
99.64

42.80 43.14 42.67 0.67

43.18 43.19 42.79 43.31 43.00 43.24
0.25

2,103 1,327 3,367 57

2,676 366 2,558 234 2,452 310
51

1,001 970 1,768 720

1,230 2,291 1,016
1,501 1,134 1,412
445

274 312 377 481

418 360 392 542 289 537
171

39 76 44 599
57 46 50 66 49 56
507

12 13 12 13
19 7

4 19 3 7
2 4
4 2 3

7 6
11

FSV-981 FSV-979 FSV-981 FSV-976

FSV-978

AC AC AC US
US

AD AD AD AD
AD

DRD (It) WSD WSD WSD

LFC

55.99 56.20 55.92 55.95

99.18

42.99 43.06 43.09 43.81

0.70

3,899 2,532 3,738 64

48

1,017 1,081 1,070 1,095

480

340 322 422 378

129

35 163 34 49
249

1,476 145 1,779

FSV-971 FSV-972
FSV-654 FSV-665
FSV-665

US US
SV SV
SV

SJD SJD
AD AD
AD

WSD WSD
WSD WSD
LFC

56.11 56.39
54.97 56.91
99.41

43.68 43.36
44.65 43.09
0.48

205 435
576 2,391
50

799 767
1,189 1,082
422

476 456
483 282
127

48 49
57 70
473

80 137
3

4 3
1

FSV-801 FSV-806 FSV-807

FSV-807

SV SV SV
SV

AD AD AD
AD

DRD (Ivf) WSD WSD

LFC

60.20 57.05 56.88

89.68

39.48 42.60 42.58

10.14

746 429 1,204

323

605 1,158 1,233

522

581 205 390

184

67 62 46
320

263 7 1,362
16

2 1 1 2 1
1

FSV-811 FSV-811
FSV-816

SV SV
SV

AD AD
AD

DRD (Ivf) DRD (If)

WSD

59.03 57.67
58.20

40.42 41.79
41.56

1,609 1,797
302

566 682
757

160 286
373

56 44
51

22 760
12

FSV-830 FSV-015 FSV-017 FSV-1101 FSV-1102 FSV-1103 FSV-659 FSV-038 FSV-657B FSV-020 FSV-022 FSV-029 FSV-213-2 FSV-913 FSV-914 FSV-919 FSV-919 FSV-921 FSV-004
FSV-902

SV SV SV SV SV SV SV SV SV SV SV SV SV SV SV SV SV SV SV
SV

AD UL UL UL UL UL SVD SVD SVD SVD SVD SVD SVD SVD SVD SVD SVD SVD SVD
SVD

WSD

WSD DRD (If) WSD DRD (Ivf) WSD EPC WSD WSD WSD WSD LFD WSD WSD
LFC

58.06 95.48 98.91 97.08 97.17 93.28 56.76 56.45 56.72 57.23 57.61 65.83 56.26 54.92 55.15 54.61 55.65 55.86 54.67
99.18

41.32 3.94 0.61 2.43 0.87 6.04 41.77 42.68 42.56 42.08 41.18 33.90 42.39 43.81 44.42 44.95 43.94 43.66 44.67
0.76

643 1,448 1,436 1,104 1,446 1,484 4,749 2,778 301 1,652 3,551 261 4,770 3,358 696 536 30 1,075 1,432
12

2,125 300 379 168 154 414 1,991 1,278 3,022 1,259 2,031 995 1,486 2,207 1,182 1,349 1,684 1,127 1,514
277

349 161 212 88 146 151 480 391 455 318 446 213 448 314 364 366 272 422 299
171

47 1,406 793 566 393 1,036 73 53 83 73 92 213 42 56 50 61 153 68 45

305

12 17 i 2 5 4 2,919 890 8 134 3,842 3,656 149 22 11 129 40 10,646 32

2

2 71 32 21 6 114 3 3 9 2 4 7 2 2 3 3 3 3 2
2

INORGANIC& ORGANICGEOCHEMISTRY OF SANVICENTE,PER U

T^mv. 1. (Cont.)

1075

Sample
FSV-904

Loc.
SV

Lith. 2
SVD

Carb. 3
EPC

CaCOa MgCO3 (mole %) (mole %)

99.31 0.64

Fe (/ag/g)
75

Mn (/ag/g)
126

Na (ug/g)
391

Sr qug/g)
391

Zn 4 (/ag/g)
14

Ba 4 (ug/g)
3

FSV-905
FSV-909

SV
SV

SVD
SVD

DRD (If)
WSD

55.15
55.00

44.14
44.57

2,147
1,309

1,035
569

300
456

54
35

4
17 4 5,097

1
1

FSV-423
FSV-673 FSV-673

SV
SV SV

SVD
SVD SVD

DRD (I,)
WSD WSD

55.88
54.27 54.32

43.53
45.33 44.93

2,021
1,296 1,495

849
527 1,794

331
330 377

47
89 53

1
4 3

FSV-674

SV

SVD

WSD

54.48

43.81

5,226

2,273

303

69

4,979

F SV-675
FSV-851

SV
SV

SVD
SVD

LFC 5
LFC

64.89
96.94

34.73
2.93

140
110

1,504
458

221
297

190
503

26
71

4
3

FSV-853
FSV-854 FSV-856

SV
SV SV

SVD
SVD SVD

DRD (If)
LFC LFC

57.40
88.90 98.31

42.37
10.96 1.61

392
119 94

653
471 269

463
308 930

151
347 930

16
774 13

4
2 94

FSV-857 FSV-862

SV SV

SVD SVD

LFC WSD

99.79 57.10

0.12 42.54

104 503

285 1,017

141 271

1,080 136

5,104

33 4

FSV-713 FSV-714 FSV-714 FSV-718 FSV-718 FSV-719

FSV-779
FSV-776
FSV-779

SV SV SV SV SV SV
AR
AR
AR

SJD SJD SJD SJD SJD SJD

SVD
SVD
SVD

DRD (If) WSD LFD WSD DRD (Im) WSD

DRD (Im)
WSD
WSD

57.14 56.14 56.77 55.99 55.69 56.13

56.90
57.31
56.50

42.37 43.19 42.78 43.54 43.40 43.38

42.92
41.95
43.22

1,338 1,478 275 931 2,760 920

230
2,700
384

880 1,618 1,757 1,206 1,383 1,375

620
821
909

372 417 516 379 355 346

651
339
511

47 53 54 41 58 74
62
52
69

5 4 7 1,207 998 6
6
5

4 2 4 4 4 4
3
4
2

Fsv-780
FSV-959 FSV-960

AR
MA MA

SVD
SVD SVD

WSD
WSD WSD

56.43
56.80 57.52

43.11
42.97 42.26

1,012
149 287

1,115
909 722

270
660 531

54
100 58

14
4

5
5 4

FSV-964
FSV-964
FSV-965

PA
PA
PA

SVD
SVD
SVD

DRD (I)
WSD
WSD

56.30
56.71
56.53

43.46
42.95
43.22

533
328
405

653
1,266
763

494
521
458

35
41
37

4,039
5,772
251

3
4
1

FSV-967 FSV-969
FSV-983

PJ PJ
SP

SVD SVD
SVD

WSD WSD
WSD

56.75 56.39
56.42

42.82 42.59
43.34

279 3,506
418

1,677 1,249
769

479 436
579

46 36
53

i
7

3 3

Locality: seeFigure1 for abbreviations, SV= San Vicente maindeposit 2Lithologies: AD = Alfonso Dolomite; UL = Bituminous silty Uncush Limestone; SVD= San Vicente Dolomite; SJD= San Judas Dolomite aDRD = dark replacement dolomite (I4:very finegrained; If:fine-grained; Im: medium-grained); WSD= white sparry dolomite (II); LFD = late voidfilling dolomite (IIId); LFC = latevoid-filling calcite (IIIc); EPC= calcite replacing evaporitic sulfate
4 blank = not detected

5XRD results indicate a mixture of 75percent dolomite and 25 percent calcite

sparry dolomite-II) supports thecathodoluminescence obser- SanVicente maindeposit vations. Calcite pseudomorphs display slightly higher Na and TheREE results fromthe San Vicente deposit aregiven in Bacompared withthelatevoid-filling calcite-IIIc. Thismay Tables 4 and 5. The distribution of the REE contents in the indicate a supply of bothcations fromthereplaced sulfate. different carbonate generations isillustrated in Figure 9. The distribution of Fe, Mn, Na, Sr, Zn, and Ba in hyThebituminous silty Uncush Limestone shows thehighest drothermal dolomites at the district scale is summarized in REE concentration (REE about 72/g/g).In thehydrotherTable2 andFigure 8. The following canbe recognized: (1) maldolomites, the REE content is <12/a,g/g. The REE conMn and Fe are enriched in localities between San Vicente centration in the ore-stage dolomites decreases from the andQuebrada Utcuyacu; (2) the highest Mn (up to 2,360 darkreplacement dolomite-I tothewhitesparry dolomite-II. /a,g/g) andSr (upto 110/g/g)concentrations occur in locali- The latecarbonates show a widerange of REE concentratiessouth of Chilpes, andcorrelate withmajor tectonic linea- tions(latevoid-filling dolomite-IIId: 0.90 0-2.51/a,g/g; late ments (e.g.,Yanachuro Sur,Rondayacu) andbasement highs void-filling calcite-IIIc:1.13-12.35/g/g). Late void-filling (e.g.,Quebrada Pifi6n); and(3) Machuyacu is characterizeddolomite-IIIdin the unmineralized cements of hydraulic by anomalous Sr (upto 100/a,g/g) andNa (upto 660/g/g) breccias(FSV-919, FSV-714) has similar low REE concenconcentrations, andby low Mn andFe (820/a,g/g and220 trations (0.89-2.54/g/g), but different REE patterns relative to the dolomite cements in dissolution breccias containRare earth elements

ing sphalerite-IIIat the boundaries of the orebodies (samples FSV-695, FSV-1092). Translucent calcite infilling Theresults ofthecomparative study between theanalysesvoidsin dissolution porosity (samples FSV-857,FSV-856) of the acid-soluble fraction andthewhole-rock samples are differs in itsREE abundances andpatterns (see below) comgiven in Table3. The REE results arepresented in twosec- paredto the commoner whitecalcites fillinglarge vein-like tions: San Vicente maindeposit andSan Vicente district. openspaces in hydraulic breccias (FSV-856, FSV-902). The

1076

SPANGENBERG ET AL.

minimum O outlier

percentlies

o o

La/Yb ratio ofthehydrothermal dolomites (Table 5) decreases in theorder: dark replacement dolomite-If, dark replacement dolomite-Ira, whitesparry dolomite-II, andlate void-filling
dolomite-IIId. These indicate a trend towards more fraction-

0.80

0.76

-0.72

ated precipitates withadvancing mineralization. The REE abundances andpatterns of the latevoid-filling calcite-IIIc vary extensively in slope, fromstrongly negative to weakly positive (Fig.10C).Threesamples of thetranslucent calcite infilling voids in the darkreplacement dolomite-I (samples FSV-856, FSV-857, andFSV-665 in Fig. 10C and Table5) haveREE patterns roughly similar to those of the white sparry dolomite-II. Twoofthese samples (FSV-665 and FSV-857) arecalcite intergrown withsphalerite-III cementingdissolution breccias. Theyaredepleted in Ce (Ce/Ce*=
0.35 and0.43,where(Ce*= [(2LacN + NdcN)/3], CN = chondrite normalized)and their Eu contentis lower than the deDRD-Ivf
n=4

0.68

DRD-If
n=8

DRD-I m
n=8

WSD-II
n=58

LFD-III
n=2

tection limit (Table 5). Sample FSV-856 is depleted in light REE (LREE) (La/Sm= 0.68,Ce/Ce*= 0.97)but hasa significant positive Eu anomaly (Eu/Eu* = 2.14,whereEu* = FSV-902 in Fig. 10C andTable5) shows a pronounced enrichment in REE, with REE concentrationsi to 10 times

FIc. 6. Ranges andmedians of the MgCOa/CaCOa molar ratioof the [(SmcN + GdcN)/2]). hydrothermal dolomites in San Vicente dolostones. See Figure 4 forabbreviCalcite froma largeveinin a hydraulic breccia (samples
ations.

greater than chondrite. In contrast totheother hydrothermal theREE patterns of these calcites arecharactercalcite replacing evaporitic sulfate has a REE between 5.12 carbonates, and6.50/xg/g. ized bya steep increase in theLREE.Calcite atthevein marTheY concentrations display similar trends to those of the gin(sample FSV-902m), only a fewmillimeters away from the total REE contents (Table4). In the UncushLimestone, the contact with the dark replacement dolomite-I, hasa flat Y concentration ranges from20.4to 22/xg/g,anddecreasesHREE pattern, in contrast to calcite fromthe veincenter whichis strongly enriched in the middleREE in the ore-stage dolomites. The late void-filling (postore) (FSV-902c) dolomite-IIId shows higher Y concentrations (IIId: 0.7-1.2 (MREE). In thislattersample, MREE andHREE enricharemore pronounced than those in LREE,resulting in /xg/g). Thelate void-filling calcite-IIIc (IIIc: 0.7-24/xg/g) and ments the calcite replacing evaporitic sulfate (2-5/xg/g)areY-en- anoverall concave-up REEpattern. In addition, thecalcite at richedcompared to the hydrothermal (ore and postore) the vein center exhibitsa Tb maximum,andthe calciteat the dolomites. margin shows a Tb minimum. Asdiscussed byM611er (1983), The chondrite-normalized REE patterns of the different a Tb maximum in Ca minerals indicates anacidic parent socarbonate generations areillustrated in Figure 10.TheREE lution, and a Tb minimum indicatesan alkaline solution. that the calciteat the cenpatterns ofcalcite from theUncush Limestone cluster within Thus,the Tb enrichmentindicates a narrow range andparallel theshale distribution (Fig.10A). terwas crystallized froma moreacidic fluid.Thecalcites reTheREEpatterns ofthevery finegrained, dark replacementplacing evaporitic sulfate have theflattest REEpatterns (Fig. dolomite aresimilar to the Uncush Limestone. Thissuggests10C);theyareslightly Ce-enriched (Ce/Ce*= 1.30)andEuthatthe hostdarkreplacement dolomite-Ivf inherited REE depleted (Eu/Eu*= 0.76). from a rock with REE similar to those in the Uncush LimeThe REE patterns normalized to the average hostdolostone. Themost significant feature oftheREE distribution in stone areshown in Figure 10D.This normalization procedure eliminates the REE distribution characteristics inherited thedark replacement dolomite subgenerations isa systematic in the REE distributions depletion of alltheREE,particularly Ce,withadvancing hy- from the hostrock.Thus, deviations drothermal alteration (Fig.10A, Table 5). Moreover, theper- in thehydrothermal carbonates reflect subsequent alteration vasively recrystallized dark replacement dolomite-Ira displaysprocesses, including the ore-forming events. All the hya slightly flattened pattern in theNd-Dyregion compared to drothermal carbonates aremarkedly depleted in LREE comtheunaltered dolomite darkreplacement dolomite-Ivf. pared to HREE.Thewhite sparry dolomite-II andlatevoidThewhitesparry dolomite-II is relatively depleted in the filling dolomite-IIId show pronounced negative Ceanomalies. middle REE, anddisplays REE patterns similar to the dark This may represent precipitation conditions (as discussed not necessarily implya LREE-depleted inreplacement dolomite-Im (Fig. 10B).The late void-fillinglater)anddoes dolomite-IIId exhibits twotypes of REE patterns (Fig.10B). coming orefluid. Furthermore, theextensive depletion ofthe Thelatevoid-filling dolomite-IIId in unmineralized hydraulic ore-stage dolomites compared to thehost dolomite indicates breccia cements (FSV-919, FSV-714) hasessentially similar thatno extensive REE exchange occurred between the ore REE patterns compared to thewhitesparry dolomite. How- fluid and the REE-rich Uncush Limestone. This is consistent ever, thedolomite infillings in dissolution breccias withspha- withthestable isotope evidence which suggests thatUncush lerite (FSV-695, FSV-1092) show a flatter heavy REE (HREE) Limestone didnotprovide ore-forming components or actas distribution without a negative Ceanomaly. Furthermore, the a fluidpathway (Spangenberg, 1995).

INORGANIC ORGANIC GEOCHEMISTRY OF SAN VICENTE, PERU

1077

B
UL

DRD-Ivf

DRD-Ivf
DRD-If

DRD-I m
QX30 O0 0

WSD
LFD

ILFC IEPC
c
UL

I
i I

LFC

o]o
i

o
I

Fe (p,g/g)
i i

EPC
75O
1500

Mn (p,g/g)
I I

1250

2500

3750

5000

2250

3000

D
i i i

DRD-Ivf DRD-If DRD-I m

WSD
LFD

I i io

DRD.Ivf

DRD-If DRD-I m
WSD
LFD

LFC EPC

o
i i i i

LFC EPC
i

H
300

t---Sr(!zg/g)
900 1200
i ,

Na (!zg/g)
i

600

150

300

450

500

F
UL UL

DRD-Ivf
DRD-If DRD-I m
WSD
LFD

DRD-Ivf DRD-If DRD-I m

WSD LFD LFC EPC
I I

H o
o o

LFC EPC

Ba (!zg/g)
I I

Zn (p.g/g)
I

25

50

75

100

750

1500

2250

FIG. 7. Ranges and medians oftheminor and trace elements in thehydrothermal carbonates of San Vicente district. A. Iron.B. Manganese. C. Strontium. D. Sodium. E. Barium. F.Zinc. See Figure 4 forabbreviations. UL = bituminous silty
Uncush Limestone, n = 7; DRD-If, n -- 4; DRD-Ir, n = 8; DRD-Im, n -- 8; WSD, n = 58; LFD, n -- 2; LFC, n = 11;EPC,
n--3.

dolomites areextremely poor in most REE, andseveral valuesare belowthe analytical detection limit. Nevertheless, The REE concentrations and the chondrite-normalized certain trends arepresent. oftheUncush Limestone inthedistrictREE ratios for the carbonate samples fromthe SanVicente TheREEpatterns scale samples have shapes similar to thesamples of thesame district aregiven in Tables 6 and 7. Thechondrite-normalized unitin theSan Vicente mining area (Fig.11A). REE diagrams are shown in Figure11. The hydrothermalstratigraphic
San Vicente district

1078

SPANGENBERG ET AL.

TABLV. 2. Minor andTrace Element Ranges andMedian Values in theHydrothermal Dolomites oftheSan Vicente District
Locality Fe Mn Na Sr Zn Ba

(n)
QP

qug/g)
475-1283

qug/g)
1674-2358

qug/g)
436-551

qug/g)
74-93

qug/g)
3-9

qug/g)
5-6

(2)
RO

(879)
185-628

(2016)
982-2022

(493)
302-398

(84)
72-113

(7)
24-41

(3)
YS

(262)
326-534

(1617)
850-1275

(375)
283-357

(87)
66-91

(37)
13-60

(6)
4-6

(2)
UT

(430)
375-555

(1062)
535-805

(320)
327-384

(79)
50-60

(36)
8-9

(5)
5-6

(2)
QU

(465)
620-1801

(670)
961-1247

(356)
320-397

(55)
37-107

(8)
25
19-164

(6)
2-7

(2)
AY

(1104)
398-2522

(1105)
982-1557

(364)
322-516

(72)
19-164

(4)
6-70

(7)
CH

(988)
234-3367

(1213)
970-2291

(378)
274-542

(68)
39-76

(46)
6-18

(12)
2-19

(9)
AC

(2103)
2532-3899

(1230)
1017-1080

(377)
322-421

(50)
34-163

(12)
144-1779

(4)

(3)
US

(3758)
65-435

(1069)
766-1095

(340)
378-476

(34)
48-49

(1476)
4-2919 1-9

(3)
San Vicente

(205)
30-5226

(799)
527-3022

(455)
205-483

(49)
35-153

(28)
AR

(1325)
230-2700

(1313)
619-1115

(369)
270-650

(56)
52-69

(352)
5-14

(3)
2-5

(4)
MA

(698)
149-87

(865)
722-909

(425)
531-660

(58)
58-100

(6)
4 250

(3)
4-5

(2)
PA

(218)
327-533

(816)
635-1266

(596)
457-520

(79)
35-41

(5)
1-4

(3) PJ (2)
SP

(405) 279-3506 (1892)

418

(763) 1249-1677 (1463)

768

(494) 436-479 (458)

579

(37) 36-46 (41)

53 7

(3) 3

(1)

Themedian values aregiven in parentheses; n = number of analyzed samples Hydrothermal dolomites = altered dark replacement dolomite (Im: medium-grained), white spatry dolomite (II), and late void-filling dolomite (IIId) 2Locality: see Figure i forabbreviations

Threesamples fromQuebrada Utcuyacu show a positive Tm chemistry (see below). In summary, theREE patterns of the anomaly. The REE abundance of the Uncush Limestone is ore-stage dolomites, excepting the behavior of Ce andTm, markedly higher inVilcapoma relative to San Vicente andthe are mostly similar in samples at district anddeposit scales other localities. (Figs.10, 11). This supports the stable isotope evidence The altered darkreplacement dolomite (If, Ira)in the dis- (Spangenberg et al., 1994,1996;Spangenberg andMacko, trict-scale samples donothave a Ce anomaly, unlike the San 1998)of a common hydrothermal system controlling the Vicente samples. chemistry ofdolomites andassociated bitumens in theregion Thewhitesparry dolomite-II samples areextremely lowin asawhole, even though alteration ismore intense in themain REE (0.6-2.8 /xg/g)with REE concentrations generally mine area. However, theabsence ofnegative Ce anomalies in below theanalytical detection limit(Fig.11C). Thefollowing theore-stage dolomites atthedistrict scale compared tothose features, however, canbe recognized: the REE concentra-found at themain deposit maybe considered asevidence of tions andoverall patterns of thedistrict samples arebroadly localdifferences in the ore-fluid chemistry (possibly more similar to themain San Vicente deposit samples; theabsence oxidizing). of negative Ce anomalies in thewhitesparry dolomite-II of isotopes thedistrict samples (Ce/Ce*= 0.67-1.50) istheonly marked Sulfur difference to thewhitesparry dolomite-II of theSan Vicente Theisotopic composition oftheevaporite sulfate (15.6and deposit (Ce/Ce*= 0.25-0.53); andonesample fromQue- 20.9%0, Table 8, Fig.12)falls within theexpected range for brada Pifi6n shows a significant MREE enrichment, which is Middle Triassic throughLate Jurassic marineevaporites characteristic of latevoid-filling dolomite-IIId in dissolution(Claypool et al., 1980;Holser et al., 1988)andclearly indibreccias withsphalerite fromSan Vicente. cates a marine signature for the sulfur. The sphalerite (sl-I: Depletions in LREE (La-Sm) andHREE (Sm-Yb) in car- 8.1-12.1%o, median = 10.6%o;sl-II: 5.7-12.6%o, median = bonates donotshow any clear regional trends within theSan 10.6%o;sl-III: 5.9-14.2%o,median = 11.2%o),galena Vicente belt(Table 7). The great scatter shown by the ele- (2.5-9.8%0, median = 6.8%o), pyrite(8.1-12.2%o, median = mental ratios La/Sm, Sm/Yb, andCe/Ndof thehydrothermal10.3%o)and sulfur (7.6-9.7%0, median = 8.7%0) have unidolomites (dark replacement dolomite-I, white sparry formly similar isotope ratios withinthe San Vicente maindedolomite-II) isprobably dueto fluctuations in thepore-fluid posit (Fig.12).The8a4S values of sphalerites-I, -II, and-III

INORGANIC& ORGANICGEOCHEMISTRY OF SANVICENTE,PERU

1079

/
P P

//

/'PA
oA

//YPA //
ISan Vicente r;7 / .usLi ,/-Chilpes

ISan Vicente

Chilpes

,.,

Fe
> 2000

900 to 2000
< 900
5 km

1000 to 1500

YS

.jRO

0 < 1000

C
/

,-i,c
.,

/
P /

/
P

//

//

/PA//
'" hO AC//

ISan Vicente 1";7

/ ..us/'o /
' '--]o AC//

Ch,__,. ,/
O < 50 ./," ,
< 350

Chllffis , /

350 to460

/
j.o I

5 km

QP

FIc. 8. Distribution of the minorandtraceelements in the ore-stage hydrothermal dolomites (darkreplacement dolomite-If, dark replacement dolomite-Im, white sparry dolomite-II) oftheSan Vicente district. A. Iron.B. Manganese. C. Strontium. D. Sodium. Zincwas notincluded because thehighconcentrations areprobably dueto contamination during
analysis.

1080

SPANGENBERG ET AL.

eq

INORGANIC& ORGANICGEOCHEMISTRY OF SANVICENTE,PERU

1081

1082

SPANGENBERG ET AL.

T^BLE 5. REERatios fortheDifferent Generations ofCarbonates in San Vicente Deposit Normalized toChondrite Values from Hanson (1980)
Ce/Nd La/Yb LaJSm Sm/Yb Ce/Ce* Eu/Eu* Eu*

Sample
FSV-015 FSV-1101 FSV-1103

Carbonate '2 (CN)

UL UL UL 1.35 1.46 1.49

(CN)
8.38 8.76 9.63

(CN)
3.97 3.43 3.91

(CN)
2.11 2.55 2.46

(CN)
0.65 0.78 0.73

(CN)
0.64 0.57 0.65

(CN)
10.56 12.85 12.44

FSV-801 FSV-2508 FSV-2502 FSV-020 FSV-423 FSV-853 FSV-905 FSV-718

FSV-654 FSV-806 FSV-661 FSV-919 FSV-869 F SV-919 FSV-714 FSV-695 FSV1092 FSV-665 FSV-857 FSV-856 FSV-902c FSV-902m FSV-423 FSV-904

WSD WSD WSD WSD WSD LFD LFD LFD LFD LFC LFC LFC LFC LFC EPC EPC

DRD (I,) DRD (I,) DRD (If) DRD (Ivf) DRD(If) DRD(If) DRD (I.) DRD(I.)

1.70 1.19 1.37 1.28 1.74 1.68 1.70 1.21

1.91 1.13 1.50 1.20 1.18 0.83 1.47 0.73 1.10 0.91 0.82 0.73 0.52 0.69 0.82 0.84

19.39 21.52 19.08 8.35 12.16 10.69 26.21 17.91

26.87 12.27 17.91 2.72 20.24 1.15 6.45 0.46 0.66 21.90 17.91 0.72 0.33 0.88 1.09

4.58 4.94 4.83 2.88 5.16 4.02 6.88 6.58

8.23 7.52 6.58 2.78 3.38 1.98 4.61 0.60 1.22 2.51 2.74 0.68 0.39 0.30 0.61 0.67

4.23 4.35 3.95 2.90 2.36 2.66 3.81 2.72

3.27 1.63 2.72 0.98 5.99 0.58 1.40 0.76 0.54 8.71 6.53 1.85 1.09 1.45 1.63

0.76 0.47 0.60 0.81 0.70 0.82 0.53 0.23

0.48 0.25 0.44 0.58 0.53 0.47 0.60 0.95 1.14 0.35 0.43 0.97 0.49 1.28 1.30 1.33

0.72 0.69 0.70 0.65

1.53 1.21 1.18 1.49 0.59 0.94 0.34 0.25

0.31 0.08 0.23 0.45 0.48 0.30 0.35 0.34 0.25 0.71 0.52 0.39 6.53 2.91 1.81 1.36

2.14 0.81 0.81 0.76 0.71

CN = chondrite normalized

tienation of theHREE;(Eu/Eu)cs = Eucs/[(SmcN + Gdcs)/2], values >1 positive anomaly, <1 negative anomaly, = 1 no anomaly; (Ce/Ce)cs =

(Ce/Nd)cN = extent ofCedepletion; (LaYb)cN = fractionation ofLBEE from the HREE; (La/Sm)cs = fractionation ofthe LBEE, (Sm/Yb)c = frae-

2UL=bituminous silty Uncush Limestone; DRD= dark replacement dolomite (Ivf; very fine grained; If:fine-grained; Im: medium-grained); WSD = white sparry dolomite (II);LFD=late void-filling dolomite (IIId); LFC =late void-filling calcite (IIIc); EPC =calcite replacing evaporitic sulfate

Cecs/[((2Lac s + Ndcs)/3] since Prwas mostly notdetected

i/[ r I

Uncush limestone HI

(a)

(4)

(Ivf)

(2) HTH (if)

(2) (5) (Im) White sparry dolomite (11)

Dark replacement dolomite

(4)
I--II

Late filling dolomite (111d)

I (2)

I Late filling calcite (111c)

Calcite replacing sulfate evaporite (EPC)

7.5

0.0

2.5

5.0

10.0

12.5

I/I/

50.0

75.0

T_,REE (lag/g)

FIG. 9. Ranges and medians ofthe total rare earth element abundance ofthe carbonates from San Vicente deposit. See
Figure 4 for abbreviations.

INORGANIC & ORGANICGEOCHEMISTRY OF SANVICENTE, PERU

10 100.

1083

UL(FSV-015)
UL (FSV-1101)

_,.AS
10

UL (FSV-1103)

Dark replacement dolomite (I vf)

0.1

Dark replacementdolomite(DRD)
DRD-Ivf (FSV-801) [] DRD-Ivf (FSV-2502)

White sparrydolomite(II)
[] WSD-II (FSV-654) [] WSD-II (FSV-869) A WSD-II (FSV-661) v WSD-II (FSV-919) [] WSD-II (FSV-806) La Ce Pr Nd
lOO

Late filling dolomite(III)

o LFD-IIId(FSV-714) o LFD-IIId(FSV-919)
+ LFD-IIId (FSV-695) x LFD-IIId (FSV-1092) Lu

DRD-Ivf (FSV-2508) + DRD-If (FSV-853) []DRD-I m(FSV-905)

0.01

DRD-Ivf (FSV-020)x DRD-If (FSV-423)E]DRD-I m (FSV-718)

La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er TmYb Lu

0.01

Sm Eu Gd Tb Dy Ho Er TmYb

10:

C
0.01

o
[]EPC (FSV-904)
Lu Sm EuGd Tb Dy Ho Er TmYb

lO

o.1

Latefilling calcite (III) Calcitereplacing x LFC-IIIc (FSV-665) o LFC-IIIc (FSV-902c) sulfate (EPC)

/ LFC-IIIc (FSV-857) oLFC-IIIc (FSV-902m) [] EPC (FSV-423)

v LFC-IIIc (FSV-856)
La Ce Pr Nd

O.Ol

La Ce Pr Nd

Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

FIG.10. A.-C. Chondrite-normalized REE abundances in carbonates fromtheSan Vicente deposit; seeFigure 4 forabbreviations. A. Uncush Limestone andsubgenerations of darkreplacement dolomite (DRD) compared to NorthAmerican shale composite (NASC). B.Whitesparry dolomite-II and thelatevoid-filling dolomite-IIId. C. Latevoid-filling calcites-IIIc andcarbonates replacing evaporitic sulfates (EPC).D. Median REE patterns of theUncush Limestone, andthehydrothermalcarbonates normalized tothehost dolomite (DRD-Ivf).IIId A: Latevoid-filling dolomite-IIId in unmineralized cement ofhydraulic breccias (FSV-919, FSV-714); IIId B:Latevoid-filling dolomite-IIId in dissolution breccias withsphalerite (FSV695,FSV-1092); IIIc A: Latevoid-filling calcite-IIIc withsimilar REE patterns compared to thelatevoid-filling dolomite (IIId B);IIIc B:Latevoid-filling calcite-IIIc froma large veinin thehydraulic breccia (FSV-902).

Discussion fromsample FSV-663 show anisotopic shift withparagenetic sequence (sl-I->sl-II:-1.0%o) and (sl-II->sl-III: -1.3%o). The incorporation of minorandtraceelements (including Fontbot andGorzawski (1990) noted a similar isotopic shift REE)intoCa-Mg-carbonates iscontrolled bythedistribution forthedifferent sphalerite generations in sphalerites-I and- coefficientDTE: II. Thesphalerites in thewhole sample setshow nostatistiDTE = (CTE/CM)c/(CTE/CM)f cally significant differences withparagenesis (Fig. 12).The sphalerite (3.8-7.0%,, median= 4.9%,), galena(-0.7of the trace element (TE) or 10.9%,, median = 0.9%,),andpyrite(6.1%o) fromthesmall Where C is the concentration cation (M, Ca + Mg in thecase of dolomites) in the mines andprospects aredepleted in 34S (onaverage byupto themajor 4.2%,)compared withthe maindeposit (Fig.12).Thissug- carbonate(c) or in the fluid (f). The few reliable distribution for carbonates at diagenetic temperatures which gests thatisotopically lightsulfur, probably of magmatic ori- coefficients ginorderived fromdegradation ofsedimentary pyrite and/or are available for minor and trace elements (Kretz, 1982; are organo-sulfur compounds (Ohmoto,1972; Ohmotoand Veizer, 1983) indicatethat the Fe, Mn, and Zn coefficients Goldhaber, 1997), was more important intheprecipitation of >1 (DFe= 1.18-23.6;DMn= 6.37-38.1;Dzn= 23.8-95.2), and

these sulfides.

forMg,Sr, Na,and Ba<1(DMg = 0.03-0.21; Dsr = 0.012-0.2;

1084

SPANGENBERG ET AL.

INORGANIC

& ORGANIC GEOCHEMISTRY OF SAN VICENTE, PERU

1085

TABLE 7. REE Ratios of theCarbonate Samples fromthe San Vicente District Normalized to Chondrite Values

Sample
F SV-684 FSV-685 FSV-984 F SV-985
FSV-681 FSV-2562
F SV-682

Loc. 2
QP QP QP QP
SI SI
SI

Carbonate 3
DRD (Lf) DRD (I) WSD WSD
DRD (Lf) DRD (Lf)
E PC

Ce/Nd
(CN)

La/Yb
(CN)

LaJSm
(CN)

Sm/Yb
(CN)

Ce/Ce '2
(CN)

Eu/Eu*
(CN)

Eu*
(CN)

1.39 0.60 1.10 1.17 1.48 3.12

1.93

9.11 1.33
6.80 4.06

2.30 0.24
1.14 2.12 1.66
7.70

3.96 5.48
3.21 2.45

1.00 0.74 1.14 0.83 1.05 1.66

0.86

0.19 0.21
0.26 0.23 0.25
0.27

1.64 6.60 0.00 1.20 5.58 0.91

1.05

FSV-1059-1 FSV-1059-2 FSV-1058 FSV-1136 FSV-2538 FSV-2545 FSV-754 FSV-759 FSV-763

FSV-754 F SV-759 FSV-753 FSV-754B FSV-982 FSV-978 FSV-979 FSV-2524-1 FSV-2524-2

QU QU QU QU CH CH CH CH CH
CH CH CH CH CH US AC UN UN

UL UL UL UL DRD DRD DRD DRD DRD

WSD WSD WSD LFD LFD LFD WSD UL UL

(Lf) (Lf) (Lf) (If) (Irn)

1.51 1.62 1.77 1.58 1.36 2.94 1.03 0.73 1.84

1.47 1.17 0.73 1.33 0.98 0.37 2.94 1.42 1.67

7.86 9.91 10.81 10.00

3.48 3.62 4.45 3.06 0.84 0.25 2.62 0.00 0.50

1.72 0.00 1.85 0.79 4.39 5.48

2.26 2.74 2.43 3.27

0.78 0.81 0.78 0.90 1.50 3.04 0.72 2.20 1.25

0.74 0.86 1.79 0.98 1.06 0.10 1.50 0.49 0.51

0.22 0.23 0.23 0.19 0.21 0.26 0.32 0.25 0.12

0.17 0.26 0.20 0.35 0.23 0.24

12.19 3.63 3.17 3.56 1.87 1.26 0.65 0.45 0.75

0.00 0.42 0.31 11.39 0.00 2.43 0.00 6.28 7.32

0.00 7.68

3.27 4.15

0.66 5.25 6.35

0.84 1.20 1.16

FSV-2550 FSV-2555 FSV-2558

FSV-1097

sJ sJ sJ
V!

UL DRD (Lf) DRD (If)

UL

1.67 1.65 2.94

0.73

11.57
3.98

2.90 1.30 1.03

1.36

3.99
2.93

0.74 1.25 1.39

0.60

0.21 0.20 0.16

0.22

4.87 0.94 0.49

35.39

FSV-1098 FSV-778 FSV-962 FSV-959 FSV-960 FSV-880 FSV-689 FSV-691 FSV-694 FSV-693
FSV-693 FSV-694

VI AR MA MA MA QS SP SP SP SP
SP SP

DRD DRD DRD DRD DRD DRD DRD DRD DRD DRD
WSD WSD

(Lf) (If) (If) (Im) (Im) (If) (Im) (Im) (Im) (Ira)

0.88 1.29 2.20 4.41 16.89 0.42 1.25 1.65 9.55 0.37
1.84 2.20

2.76

0.79 0.76

3.48

0.87 5.38 5.89 2.44 3.81 3.96 0.87

0.88 1.61 1.12 2.24 1.95 0.59 0.76 0.70 1.12 0.65
0.67 0.73

0.21 0.26

0.24 0.20 0.22

0.22

8.53 0.42 0.00 0.18 0.29 0.25 0.91 0.21 0.36 0.18

CN = chondrite normalized

(Ce/Nd)c N = extent of Ce depletion; (La/Yb)c N = fractionation of LREE fromtheHREE;(LaJSm)c N = fractionation of theLREE;(Sm/Yb)c N = fracrionation of the HREE; (Eu/Eu*)c m= EUCN/[(SmcN + Gdcm)/2], values >1 positive anomaly, <1 negative anomaly, =1 no anomaly; (Ce/Ce*)c m= CeCN/[((2LacN + NdcN)/3 ] since Prwas mostly notdetected sLocality: seeFigure 1 forabbreviations aUL = bituminous silty Uncush Limestone; DRD = dark replacement dolomite (I. very finegrained; If:fine-grained; Im: medium-grained); WSD= white sparry dolomite (II); LFD = latevoid-filling dolomite (IIId); LFC = latevoid-filling calcite (IIIc); EPC= calcite replacing evaporitic sulfate

DNa = 0.00003; DBa = 0.05-0.22). The apparent distributionincoming fluid. Possible sources ofMg arefrom theconversion values for the REE in foraminiferal calcite are>1, andgen- of highMg to low Mg calcite, dedolomitizakion of Ca-rich erally decrease (excepting Ce)withionic radii fromDLa = 125 dolomites, andsmeckite toillitcconversion (e.g., Richter, 1974; to Dyb = 73 (Palmer, 1985). Distribution of the trace ele- Pingitore, 1978;McHargue andPrice,1982;Leuchs, 1985). ments, moreover, is influenced by sorption onthecarbonate Theincoming fluid issuggested tohave leached underlying desurface(Zacharaet al., 1991), the concentration of the comtrital rocks (Fontbot6and Gorzawski, 1990,Moritz et al., 1996),

plexing ligands (e.g., Cantrell andByrne, 1987; M611er, 1991), andthe precipitation rate(Lorens, 1981). Vahrencamp and Swart (1990)suggested thatthe Sr distribution coefficient in dolomite isdependent onthedolomite stoichiometry.

andsmectite breakdown could bealocal Mg source. Thesmeckite toillitc transformation, and other processes including albikization, alkali feldspar and mica dissolution, and interlayer-cation exchange inclay minerals may also release significant quantities of Fe2+ andNa+(e.g., Price, 1982; McHargne and Posey et al., Mg,Fe,Mn, St,Na, andZn in thehydrothermal carbonates 1987; Jankowski and Jacobson, 1989). Theobserved relative increase of Mg in thehydrothermal TheFe-depletion in theore-stage hydrothermal dolomites dolomites (Fig.5) wouldrequire a highMg/Caratioin the (dark replacement dolomite-I m, white sparry dolomite-II, late

1086
lOO

SPANGENBERG ET AL.

AN. Bituminous silty Uncush Limestone

OlC
E

void-filling dolomite-IIId; Fig.7) suggests thatFe'+ may have beenremoved before dolomite precipitation. Since Fe, Mn, andZn haveD > 1, the fluidwould havebecome progressively depleted in these metals during precipitation of the dolomites unless externally recharged. In addition, bothZn and Fe wouldhavebeenextracted from the fluid during sphalerite precipitation. A major control onFe'*substitution
in carbonates is fluid redox conditions,as discussed later. The

x QU QU QU

UN ,!, UN O SJ

QU
1 80:

Vl

San Vicente deposit

m IuGd 'l:b [yIo Ir 'l:m b !'u
Dark replacementdolomite

!'a (e Ir Id

noncathodoluminescence of dolomite-Iv (Fig. 3D) andthe redluminescence of dolomite-II (Fig.3H) furthermore suggest thatthehigh-Fe host dolomite-Iv was altered bya fluid witha relatively highMn/Feratio,and/or thatFe'+ wasexcluded from precipitated carbonate (e.g., duetoredox conditions). A large external Mn source could be thedetrital sediments and volcaniclastic rocks oftheunderlying MituGroup, Permo-Triassic intrusives (San Ram6n granite andequivalent rocks), andthe LowerPaleozoic nearSan Vicente. Leaching ofthese could bring important amounts of Fe, Mn, Mg,and Sr intosolution. Strontium isotope studies indicate thatthe
Pertoo-Triassic intrusionsin the Pucar5 basin, or the clastic

B
10

rocks intheMituGroup oratthebase ofthePucarg sequence, area likely source ofradiogenic 87Sr (Moritz etal.,1996). The preferential enrichment of thefluidin Mn compared to Fe may beexplained byoxidizing conditions during migration (see below). The occurrence of massive marcasite, nowpseudomorphed bypyrite, at theborder of theupper margin of the main deposit (e.g., San Vicente Techo manto) suggests that the orefluidmay have become enriched in Fe during oreprecipitation. H* isliberated during precipitation ofsulfides (e.g., Ms*
+ H.S-> 2H + + MS, M '+= divalent metal).Thusthe orefluid

0.1

A If Ar 'lvfQP IvfCH If QS IvfSl ,I, IvfCH lvfSl O IvfCH A Im SP

x IvfQP
[] IvfVl M Ivf SJ !'a Ce 15rNd

may have become enriched inFebydissolution ofthedolomite host rocks (dark replacement dolomite-Ivt; Fig.7).

Ivf SP

DRD_Im Fractionation oftheREEduring mineralization

fractionation of REE in hydrothermal carbonSan Vicente deposit The overall

0.01
10:

' Im SP

m Iu(d b Oyo 'lr 'l:mb !'u

White sparrydolomite

ates canbeexplained using Yb/Ca versus Yb/La(Parekh and

Mi511er, 1977),in termsof assimilation andremobilization dur-

ingmineralization (Fig.13).TheYb/Ca ratio isrelated tothe

extent of interaction ("assimilation")between the host

0.1

dolomite andthefluidatincreasing water-rock ratios while the Yb/La ratio represents theoverall REE fractionation ("remobilization"). TheSan Vicente hydrothermal carbonates display a roughly diagonal trendin the Yb/Ca-Yb/La diagram (Fig. 13),indicating thatthey wereprecipitated from a fluidwhich increasingly fractionated theREE during mineralization. Thepronounced LREE depletion andscatter in theREE patterns of theore-stage dolomites (Im,II) reflect host-rock alteration bycirculation of large amounts of REE-poor solu.

tions. The carbonate-fluid

o II QP [] II QP + II CH ,e, II AC

distribution coefficients of the

[] II CH
V II CH
0.01

II SP
II SP

REE arelarge (70-120; Palmer, 1985). Thus, extremely high water/rock ratios arerequired to alter theREE distribution in carbonates during diagenesis (Banner et al., 1988;McLendocumented that the alSan Vicente depositnan, 1989). Graf (1984), however,

!'a CeIr Id

m u(d 'b[yo r rnb !'u

teredhost dolomites in theViburnum Trend Mississippi Valley-type district aresignificantly depleted in LREEcompared
to the unaltered host dolomite, as a result of host-rockinter-

FIG. 11. Chondrite-normalized BEE abundances. A. Bituminous silty UncushLimestone. B. Dark replacement dolomite-I. C. White sparry dolomite-II from theSan Vicente district. Compare withthefielddefined by

actions withLREE-depleted oresolutions.

Since REE are more abundant in calcite than dolomite, it

samples fromSan Vicente mine(shaded area). See Figure I forlocation of thesample sites.

isnotsurprising to see higher MREE andHREE in thelate open-space filling calcite (IIIc). Therelatively lowLREE of

INORGANIC & ORGANIC GEOCHEMISTRY OFSAN VICENTE, PERU

1087

TABLE 8. Sulfur Isotope Composition ofSulfur Minerals from Deposits and Ore Occurrences inthe San Vicente District
Locality 1 Sample
FSV-1002
334S

(abbreviation)
PefiaBlanca (PB)

Lith. 2
SVD

Manto

Description/sulfur phase s
Galenain WSD

(%, CDT)

Yanachuro Sur (YS)

10.9

FSV-0995

SJD

FSV-0752 FSV-0765 FSV-0687 FSV-0873

FSV-2534A FSV-2534B FSV-0666 FSV-0667 FSV-0811 FSV-0815 FSV-0816 FSV-0818 FSV-0851
FSV-861 FSV-870 FSV-1092 FSV-2517 FSV-683 FSV-1090A FSV-1091 FSV-679 FSV-675 FSV-422 FSV-0794

Chilpes (CH) Chilpes (CH) Chilpes (CH) Chilpes (CH)

Uni6n Mantus (UM) Uni6n Mantus (UM) SanVicente (SV) SanVicente (SV) SanVicente (SV) SanVicente (SV) SanVicente (SV) SanVicente (SV) SanVicente (SV)
SanVicente (SV) SanVicente (SV) SanVicente (SV) SanVicente (SV) SanVicente (SV) SanVicente (SV) SanVicente (SV) SanVicente (SV) SanVicente (SV) SanVicente (SV) SanVicente (SV)

SJD SJD SVD SVD

RS RS AD AD AD AD AD AD SVD
SVD SVD SVD SVD SVD SVD SVD SVD SVD SVD SVD

Massive galena Pyrite incalcite

Galenain WSD II

-0.1 6.1
-0.7

Sphalerite II inWSD
Galenain WSD II Galenain WSD

3.8
4.9
0.9

Sphalerite II inWSD Sphalerite II inWSD

7.0
1.4

Evaporite sulfate lense Evaporite sulfate lense Alfonso Pyrite inWSD Alfonso Pyrite inWSD Alfonso Sphalerite III inLFD Alfonso Sphalerite III inLFD Alfonso Sphalerite III inLFD Alfonso Sphalerite II inWSD SV techo Sphalerite II inzebra ore
Galenain WSD

15.6 20.9 8.1 10.1 11.0 10.9 11.2 12.6 12.1

8.1

FSV-663

SanVicente (SV)

SVD

SV techo Sphalerite III inWSD SVtecho Massive pyrite Sphalerite III inWSD Sulfur inquartz Massive pyinWSD SV techo Sphalerite III inLFD/LFC SV techo Sphalerite I inWSD SV techo Sphalerite III inLFDand pyrobit. Jesus Sulfur incalcite Jesus Sphalerite II inzebra ore Ayala Sphalerite I inDRD(Im) Sphalerite II inWSD Ayala Sphalerite I inDRD(Im) Sphalerite II inWSD Sphalerite III inLFD
Galena
Galena

13.9 12.2 13.5 9.7 10.5 13.9 12.1 14.2 7.6 11.5 10.6 9.9 8.1 7.1 5.9
3.8
2.6

FSV-916

SanVicente (SV)

SVD

Ayala
Ayala

Sphalerite II inWSD
Sphalerite II inWSD
Galena

5.7
9.8

FSV-921
FSV-924 FSV-0074

SanVicente (SV)
SanVicente (SV) SanVicente (SV)

SVD
SVD SVD

8.0

Ayala
3t 3t 2 3i

Sphalerite III inLFD

Galena Galena

7.3
2.5 9.6

Sphalerite I inDRD(Im) Sphalerite II inWSD Sphalerite II inWSD Sphalerite II inWSD

Galena

10.4 10.6 12.2

6.8

FSV-0444 FSV-0394

SanVicente (SV) SanVicente (SV)

SVD SVD

Galena

FSV-031
FSV-0414

SanVicente (SV)
SanVicente (SV)

SVD
SVD

10.2
6.7

3p

Sphalerite I inDRD(Ira) Sphalerite II inWSD

Galena Sulfurin EPC Sulfur in EPC

12.1 12.2
6.9 10.3 10.2

FSV-680
FSV-690

Arcopunco (SR)
Pichita(PI)

SVD
SVD

The locations ofthe sample sites are shown inFigure 1,SV= San Vicente main deposit
(IIId);LFC= late void-filling calcite (IIIc);EPC= calcite replacing evaporitic sulfate
DatafromFontbot andGorzawski (1990) included forcomparison

Lithologies: AD =Alfonso Dolomite; UL=bituminous silty Uncush Limestone; SVD =San Vicente Dolomite; SJD =San Judas Dolomite Abbreviations: DRD (Im) =medium-grained dark replacement dolomite-Im); WSD =white sparry dolomite (II);LFD =late void-filling dolomite

1088
i i i i

SPANGENBERG ET AL.
i

(n=4)
(n=2)

Pyrite Sulfur
Sphalerite I (n=5)

main deposit

San Vicente

.--. 10 -71

10'61
,
UL

Sphalerite II
(n=10)

o I
I I I

Sphalerite Ill (n=9)

(n=8)

--H

o-91
I I I

Galena

] -
I I I

10-10/

...........
0.01

ti
0.1 1

DRD-Ivf DRD-If 13DRD-I m

[] WSD-II [] LFD-IIId

O LFC-IIIc

Galena
Sphalerite II
Sulfur

mi

San Vicente
Yanachuro

0.001

district
Sur

Yb/La (atomicratio)

[]Pefia Bianca
Chilpes

FIG.13. Yb/Ca vs.Yb/La plotforthehydrothermal carbonates in theSan Vicente district, showing thetrends of REEfractionation during mineralizationdefined byParekh andMOller (1977). SeeFigure 4 forabbreviations.

UniOn Mantus
O Arcopunco

Pyrite
sulfate

Pichita

Evaporite
i i i i i i i

i i

20.0

0.0

5.0

10.0

15.0

634S(%o, CDT)

FIG.12. Ranges andmedians of 1534S values of thesulfur minerals from San Vicente deposit andoccurrences in San Vicente district.

these latecalcites mayrecord minor fractionation during dissolution andprecipitation of thehydrothermal carbonates. Eh-p H considerations Thetrace elements thatoccur in aqueous solutions in multipleoxidation states, e.g.,Fe(II,III), Mn(II,IV), Ce(III,IV), andEu(II,III), arepotential tracers of Eh-pHchanges during aliagenetic processes. Thus, the distribution of Fe, Mn, Ce, andEu in thehydrothermal carbonates canbeconsidered in terms of theredox conditions during oreprecipitation.
Cerium andcuropium anomalies In a sedimentary environment, Ce 3+ may beoxidized tothe 13.9 percent smaller Ce 4+ cation, which islargely adsorbed by hydrolizates or suspended matter(e.g.,Piper,1974; Palmer, 1985; TligandM'Rabet, 1985) or retained in solution ascarbonate complexes (e.g., M611er, 1983; M611er et al.,1984). In such cases, precipitated carbonates mayhavea negative Ce anomaly. Thenegative Ce anomaly in theore-stage dolomites of the

have a negative chondrite-normalized Eu anomaly (Eu/Eu*: 0.57-0.65 for Uncush Limestone, 0.65-0.72 for darkreplacementdolomite-Ivf). The Eu concentration in the ore-stage hydrothermal dolomites (darkreplacement dolomite-If, dark replacement dolomite-Ira, whitesparry dolomite-II, latevoidfillingdolomite-IIId) is lowerthanthe analytical detection limit,(lower limitof detection, LLD: 0.05/xg/g; chondritenormalized LLD: 0.69).Thisdoes notnecessarily suggest a negative Eu anomaly (see theEu* values in Table 5) in these dolomites. Thelate-stage, void-filling calcites have less negative(0.81)or positive (2.14)Eu anomalies. ThisEu enrichmentin the late calcite-IIIcmerits an explanation. While 2+ Eu2+(1.17A) is larger thanCa (1.00A), it hasthe same charge andsize asSr +(1.18 A) thatisknown to substitute for Ca 2+. Thisargument mayexplain theless negative (or more positive) Eu anomalies in the latecalcites compared to the dolomites. Thus, changes in size of the Eu anomalies in the hydrothermal carbonates may reflect simple remobilization of thehost-rock REE,withlittlefractionation during dissolution andprecipitation.
Fe-Mn covariation

The Fe-Mn covariation (Fig. 14) in the hydrothermal dolomites displays a roughly L-shaped trend,characterized bya vertical field(A-B)withMn between 500and3,000/xg/g and lowFe (<1,500/g/g), andanoblique field(A-C;"dogleg" afterMeyers, 1989) covering a widerange of bothFe (1,500 to 5,000/xg/g) andMn (500to 2,250/xg/g) concentrations. The darkreplacement dolomite-I shows a general vertical
variation in Fe at low Mn concentrations whereas the white

San Vicente deposit (Fig.10A,B, Table 5) suggests thatthe sparry dolomite-II occurs in boththefields. Twosamples of incoming orefluidcontained dominantly Ce 4+ which was not thelatevoid-filling dolomite-IIId fallin thevertical field. incorporated during dolomite formation. Thisimplies a relaMeyers (1989)interpreted a similar L-shaped trendin Fetively oxidizing orefluid. Mn datafromdifferent calcite generations in the MississipThe Eu behavior in the SanVicentedeposit carbonatespianLake Valley Formation in NewMexico byfluid-rock in(Table 5) is summarized asfollows. The bituminous siltyUn- teraction combined with Eh changes. He pointed out that cush Limestone andthehost darkreplacement dolomite (Ivf) fluid-rock interaction canbe animportant control onMn and

INORGANIC& ORGANICGEOCHEMISTRY OF SANVICENTE,PERU

3500

1089

precipitation: thermochemical sulfate reduction (see sulfidesulfate Eh-pH boundary in Fig. 15) and pyrobitumen formaB tion(Spangenberg andMacko, 1998). The Mn'2+ andFe'2+ concentrations in theincoming oxidizing fluid were constant and low (e.g., in the range of <10 4 2500. ::::i:;::::; I /.;::;::. molar Mn2+ and<<10 molar Fe2+, see Fig.15); this explains whyFe andMn werenotincorporated in thedolomites in :..11:::::: :1 ' 2000/ ..... [] .... ' 'O ..... spite of distribution coefficients >1. An Eh decrease, due to :&.::i::::::61 ======================= theprocesses described above, would result in anincrease of free Mn2+in the fluidandlimited or no Feg+ increase (e.g., trend F-F' in Fig.15).In thisEh-pHfield, Mng+ would bein'Or' i:''' o" "' b: ;. ............ .... []....... L. ......... - corporated in the precipitates (whitesparry dolomite-II), whereas Fe3+ remains asa stable oxidized phase (trend A-Bin 1%:-J;fi. ;;;;.: ;:. ;? ;::;El; ;;;;;; DRD_iv f Fig.14).AstheEh continues to decrease, Fe3+ would bere500....; ;:;;;::;;;;;-.) DRD-If [] DRD-Im duced to mobile Feg+ (trend F'-F"in Fig.15).If theMn sup[] WSD [] LFD plywere unlimited, both divalent metals would beavailable in 0 0 1000 2000 3000 4000 50'00 6000 solution to coprecipitate withthecarbonates (resulting in the Fe (p,g/g) dogleg trend A-Cin Fig.15).If theMn orFe supply was limcarbonates wouldbe poorin Fe and Fc. 14. Mn vs.Fe plotforthehydrothermal dolomites fromtheSan Vi- ited,the precipitated thepervasively altered host dolomite could have centedistrict. Thereis an overall L-shaped trend,with a dogleg extension. Mn. Finally, Seetextfor discussion. SeeFigure 4 for abbreviations. become protected by overgrowths of hydrothermal white

i;t: :_'::: :01 .,"':::;;::. .'::; ::::::::: 'J

,... ............

1.0

Fe contents of diagenetic waters, in addition to Eh-pHvariations. A fluid-rock interaction model, assuming thatthe incoming fluidhadconstant Fe andMn concentrations, andby inference a constant supply, wasproposed to explain the Fe and Mn covariations of a single calcite generation. Under moderately reduced conditions Mng+ is incorporated in the precipitating carbonates whereas Fe3+ isnot,andthus defines the vertical trendin Mn-Fe of the calcite cements (Meyers, 1989). A decrease in the Eh of poresolutions in a carbonate environment withlargely buffered pH may account foranenrichment in theFe2+andMng+ concentration of theprecipitating carbonates, andwill define a Mn-Fedogleg extension (Meyers, 1989).
fluidis slightly acidic (pH -5 to 6, seeSpangenberg et al.,

H20 oxidized

0.8

0.6

'".

,.

.,..8..'

o.4
z:

""/A", % %

1% , ,[Fe2+l 10-'
'1o-4o'
I =,, 10 '8

In San Vicente, weassume that theincoming mineralizingg

1996) and as suggested by the Ce data, oxidizing atleast inthe LU 02

0

earlymigration stages. Interaction of the corrosive fluid(F) withthehost dolomite (R) decreases thefluidacidity andEh (trend F-R in Fig.15).ThepH changes aremainly controlled by carbonate dissolution untilcomplete buffering occurs by thehost dolomite (darkreplacement dolomite-Ivr). Reducing conditions areprovided byshort-chain hydrocarbons released during hydrous pyrolysis or cleavage of either indigenous or exogenic long-chain organicmolecules (e.g., Giz and Barnes, 1994). Theprocesses involved in thereduction at the siteof oredeposition requires some comments. Tworeduction mechanisms in the ore precipitation environment are known: (1) methane or otherlight hydrocarbons bleeding

% %10.6 oco Mn 2+, Fe 2+ O ,co %

20 10-4

I. Organ rbon . T bou I -o.z

-0.4

HO/
5.0

to thehost darkreplacement dolomite (a process similar to pH mesophase development in bitumen; e.g.,Giz, 1993), or alfor partof the system Fe-Mn-O-H,assuming teration of the indigenous hydrocarbons staining the host Fc. 15. Eh-pH diagram andMnOasstable phases forFe (III) andMn (III). Boundaries calrock; and(2) alteration of extrinsic bacterially reworked hy- FeO3 culatedfor molar concentrations of Fe+ and Mn + of 10-10, 10-8, 10-6, and drocarbons introduced by the ore fluid (Spangenberg and 10-4 afterequations for standard temperature andpressure of Pourbaix Macko, 1998). Thermal alteration of the San Vicente hydro- (1963). Thesulfide-sulfate boundary and organic carbon-carbonate boundary carbons, likely duringinteraction with the incoming hy- areafterBrookins (1988). F-R isa schematic representation oftheexpected during interaction oftheincoming fluid with thehost dolomite. drothermal ore fluids,explains two aspects relatedto ore Eh-pHtrend

during (hydro)thermal alteration of the bituminite indigenous 4.

H20 reduced
5.5 6.0 6.5

7.0

7.5

8.0

8.5

1090

SPANGENBERG ET AL.

Ore-fluid flow pathandhost-rock interaction quently, recharge of the fluid-rock system with oxygenated The traceelement distributions in the hydrothermal carbasinal solutions would provide oxidizing conditions. Textural bonates indicate thattheincoming mineralizing fluidwasnot andstable isotope evidence (Spangenberg, 1995;Spangen- in chemical equilibrium with the Pucar5 Groupcarbonates. berget al.,1996) show thatthelatevoid-filling hydrothermalThesame conclusion was suggested onthebasis of stable isocarbonates precipitated froma fluid-buffered system, and the tope data (Spangenberg, 1995;Spangenberg et al., 1996). low Mn andFe concentrations in thelateinfilling dolomites Thisimplies thatthe Pucar5 carbonate hostrocks could not support thehypothesis of a return to oxidizing conditions in a have acted asthe mainaquifer for fluidflow,andthatfluids fluid-buffered system. Thus,the Ce anomalies andthe Fe- hadto be isolated fromthe Pucar5 rocks along their entire Mn covariations of the hydrothermal carbonates record the flowpath. We assume thatfluidflowwas through aquifers inchanges in Eh oftheincoming orefluid. Theevolved isotopic cluding detritalunitsat the baseof the Pucar5 basinand andelemental composition oftheepigenetic carbonates com- deeper permeable rocks assuggested by the localchemical paredto the host-rock points to a model thatrepresents an differences of the ore-fluid chemistry (e.g.,Fe concentraopen system in themineralized zone thatshifts fromrockto tions, REE data,81aC of the pyrobitumens, and8a4S data), fluid-dominated. Thisdynamic fluid-rock interaction system withverylittleinteraction withthePucar5 carbonates. Access includes multiple stages of epigenetic carbonate cementationto the ore deposition sites wasby interconnected channels and evolving rock-fluid interfaces (e.g.,dark replacement(faults, basement highs) near theoreoccurrences, where fluid dolomite-I/fluid; whitesparry dolomite-II/fluid; latevoid-fill- could flowupward without exchanging significantly withthe ingdolomite-IIId/fluid; andlatevoid-filling calcite-IIIc/fluid).surroundings rocks. Mixing oftheincoming fluid(slightly acidic, oxidizing, H2CO 3 dominant) and local pore fluids in the host Source of sulfur rocks (alkaline, reducing, HCO3-dominant), andinteraction The difference between the sulfur isotope composition of withthehost rocks, explains thegreat scatter oftheREE and the SanVicente sulfides andthose of the smallMississippiother trace elements in thehydrothermal carbonates. Valley-type occurrences suggests different sulfur sources. In Conclusions theSan Vicente main deposit the834S values indicate a dominantly MiddleTriassic to LateJurassic marine evaporitie sulMajorandtrace element (including REE) geochemistry of fatesoume. The negative trending 834S values found for the the hydrothermal carbonates of the SanVicente Mississippi sulfides fromminor occurrences (Chilpes, Pefia Blanea) sugdistrict, combined with carbon and oxygen isogest a localcontribution of magmatic sulfur (~0%0; Ohmoto, Valley-type topes, organic geochemical and organic isotope results of the 1972).A locally moreimportant contribution of isotopically bitumens and associated kerogens, and the sulfur isotopic vallightsedimentary sulfur (pyrite ororganic-sulfur compounds; uesof thedifferent sulfur minerals, provide a datasetwhich e.g.,Ohmoto andGoldhaber, 1997) cannot beexcluded. characterizes the fluid/fluid and fluid/rock mixing processes It hasbeenwell documented that dissimilatory bacterial involved during sulfide precipitation at San Vicente, andgives sulfate reduction entails a largeisotope fractionation (upto insights into the composition of the ore fluids, the fluid path-60%0). Accordingly, thebacteriogenic sulfides aregenerally way, and the soume and reduction mechanism of sulfur: identified bya marked shift toward a4S-depleted values compared to theparent sulfate, anda large scatter in their8a4S 1. Theincoming mineralizing fluidwas slightly acidic (pH values (e.g.,Holser et al., 1988). Thermochemical sulfate re- ~5),oxidizing, probably duetocirculation through underlying duction involves little or no net isotope fractionation (e.g., detrital rocks. Machel et al.,1995; Jones et al., 1996). Fontbot6 andGorza- 2. Theregional geochemical homogeneity ofhydrothermal wski(1990) interpreted thehigh8a4S values of San Vicente carbonates, combined withthelack ofgeochemical equilibrasphalerite andgalena asresulting fromthermochemical sul- tionbetween the incoming fluidandthe carbonate rocks of fatereduction. Our results suggest thatthe deposit sulfides the Pueara Group, constrain the regional-scale fluidflowto werederived fromabiogenic reduction of MiddleTriassic highpermeability channels (faults, basement highs) nearthe through LateJurassic marine evaporite-derived sulfate. Fur- ore occurrences. thersupport for thisconclusion is provided by depleted laC 3. The dissolution alteration of the hostdolomite by the calcite cements(~-12%o 81aC)in the San Vicente district corrosive incoming fluidexposed indigenous hydrocarbons, (Spangenberg et al., 1996) and the organic geochemicalandprovided the localredox conditions necessary to reduce analyses (Spangenberg andMacko, 1998). The introductionsulfate to sulfide, and Eu3+to Eu2+.In this earlyrockofbacterial-derived n-alkanes bytheorefluiddoes notimply buffered stage, thehost dolomite was replaced byhydrotherthatthe incoming fluids brought bacteria to the oresite.At maldolomites (dark replacement dolomite-If to whitesparry San Vicente, the relatively highcontent of n-alkanes andiso- dolomite-II) andsphalerite-I. prenoids, and absence of steranes, hopanes, and aromatic 4. Precipitation ofopen-space-filling white sparry dolomitecompounds, reflects thehighbitumen maturity andstrongly II and sphalerite-II occurred in acidic,reducing fluidsuggest thatbiota was notintroduced bytheincoming fluidat buffered conditions, asindicated bytheMn uptake andREEthe time of ore precipitation (Spangenberg and Macko, depletion of thewhitesparry dolomite-II. 1998). This,withthesulfur isotope dataandgeochemical ev5. The REE enrichment, the Mn depletion, andpositive idence discussed above, indicatesthat thermochemicalsul- Eu anomaly of the late-stage vug-filling carbonates indicate fatereduction wasthe mainhydrogen sulfide source to the thatthepostore, "residual" acidic fluid,was oxidizing (dueto ore fluid. influx of fresh basinal waters), andwould extensively enhance

dolomite, and could not further deliver reductants. Conse-

INORGANIC& ORGANICGEOCHEMISTRY OF SANVICENTE,PERU

1091

D.G., 1988,Eh-pH diagrams for geochemists: Berlin,Springerthe secondary porosity by carbonate dissolution until pH- Brookins, Verlag, 176p. buffering occurred. CO2degassing would cause precipitation Buelter, D.P., and Guillemettte, R.N., 1988,Geochemistry of epigenetic
of REE-rich late carbonates.
dolomiteassociated with lead-zincmineralizationof the Viburnum Trend,

6. The traceelement signature of the San Vicente carbon- southeast Missouri: a reconnaissance study, in Shukla, V.,andBaker, P.A., Sedimentology and Geochemistry ofDolostones: Society ofEconomic atessupports the genetic modelproposed by quantitative eds., andMineralogists, Special publication 43,p. 85-93. modeling of the stable isotope covariations, whichinvolves Paleontologists K.J.,andByrne, R.H., 1987,Rareearth element complexation by mixing of indigenous intraformational fluidandanincoming Cantrell, carbonate andoxalate ions:Geochimica et Cosmochimica Acta,v. 51, p. slightly acidic orefluid,andinteraction between thecorrosive 597-606.
fluid and the host dolostone.

Claypool, G.E., Holser, W.T., Kaplan, I.R.,Sakai, Z.,and ak,I., 1980, The

curves of sulfur and oxygen isotopes in marine sulfate and theirmutual 7. The absence of negative Ce anomalies in the ore-stage age interpretation: Chemical Geology, v.28,p. 199-260. dolomites at the district scale compared withthose found at Farr, M.R., 1992, Geochemical variation of dolomite cement within the themain deposit isin agreement withthe83C shift ofthepy- Cambrian Bonneterre Formation, Missouri: evidence for fluid mixing: robitumen in themining area. These factors areconsidered as Journal of Sedimentary Petrology, v.62,p. 636-651.
further evidence of local differences in the ore-fluid chem-

Fontbotf,L., 1990,Stratabound ore deposits in the Pucara basin: An

overview,in Fontbotf, L., Amstutz, G.C., Cardozo, M., Cedillo, E., and

istry, possibly of a moreoxidizing nature, combined withan intense hydrothermal alteration of the hostdolomite at the
main San Vicente mineralization site.

Frutos, J., eds.,Stratabound ore deposits in the Andes: Heidelberg,

Springer, p. 253-266.

--1993, Self-organization fabrics in carbonate-hosted oredeposits: theex8. The positive anduniform sulfur isotope composition of ample ofdiagenetic crystallization rhythmites (DCRs), in Fenoll Hach-Ali, J.,andGervilla, E, eds., Current research in geology apthe sulfide minerals, combined withthe presence of native P.,Torres-Ruiz, tooredeposits: Proceedings oftheSecond Biennial Society forGeolsulfur associated with extremely 83C-low calcites replacing plied ogy Applied to Mineral Deposits Meeting, University of Granada, Spain, evaporitic sulfates, altered native organic matter, isotopically September 9-13, 1993, p. 11-14. heavier hydrothermal bitumen, andabsence of hopanes in Fontbotf, L., andGorzawski, H., 1990, Genesis oftheMississippi Valley-type deposit of San Vicente, central Peru: Geological andisotopic (Sr,O, SanVicente hydrocarbons, pointto thermochemical reduc- Zn-Pb C, S) evidences: ECONOMIC GEOLOGY, v. 85, p. 1402--1437. tion of sulfate. Fontbotf, L., Spangenberg, J.,Oldham, L., andDavila, D., 1995, The Mississippi Valley-type zinc-lead mineof SanVicente, eastern Pucara basin, Acknowledgments
Peru: International Field conference on carbonate-hosted lead-zinc de-

Thorough reviews of the paperby A. Giz andthe Eco- posits, June 3-6, 1995,St.Louis, Missouri, Abstracts, p. 83-86. A., Jager, H.J., Normann, A.L., Krouse, H.R., and Brand, nomicGeology reviewers S.H. BottrellandJ. Wilkinson are Giesemann, 1994, On-linesulfur-isotope determination usingan elemental greatly appreciated andresulted in significant improvements W.A., analyser coupled to a mass spectrometer: Analytical Chemistry, v. 66,p. to thepaper. Thisstudy was supported bytheSwiss National 2816-2819.
ScienceFoundation (Grant No. 2000-040575.95 to L. FontGiz, A.P.,1993,The analysis of organic matter in oredeposits, in Parnell,
H., andLandais, P.,eds.,Bitumens in ore deposits: Springerbot6andNo.2100-47023.96 toZ. Sharp and J.Hunziker). We J., Kucha, p. 28-52. aregrateful to SanIgnacio de Morococha S.A.Mining Com- Verlag, A.P. andBarnes, H.L., 1994, Organic contributions to Mississippi Valleypany andthestaff of theGeology Department of San Vicente Giz, typelead-zinc genesis, in Fontbotf,L., and Boni,M., eds.,Sedimentminefortheirhelpin thefieldwork. The EA-IRMSfacilities hosted Zn-Pboredeposits: Berlin, Springer-Verlag, p. 13-26. at the Department of Environmental Sciences, University of Graf,J.L.,1984,Effects of Mississippi Valley-type mineralization on REE ofcarbonate rocks and minerals, Viburnum Trend, Southeast MisVirginia, weresupported bytheU.S.NSF.Theauthors thank patterns souri: Journal of Geology, v.92,p. 307-324. J. Buffle, J.C.Negre,andM. Martin(ICP-AESlaboratory), --1988, Rare earth element studies of Mississippi Valley-type (MVT),PbR. Martini(cathodoluminescence microscopy) of the Univer- Zn-Cudeposits in Kansas, Oklahoma, andMissouri, in P61issonier, H., and sity of Geneva, Ph.Th61in (XRD-analyses) and F. Bussy (elec- Sureau, J.E, eds., Mobilit6 et concentration desmftaux debase dans les sfdimentaires, Manifestations, mfcanismes, prospection: Butronmicroprobe) of the University of Lausanne for theirco- couvertures G6ologiques et MinireDocument 183,p. 75-88. operation during the analytical work. Thisstudy wascarried reauRecherches Gregg, J.M.,1988,Origins of dolomite in the offshore facies of the Bonoutin theframe oftheIGCP357Project "Organics andmin- neterre Formation (Cambrian), SoutheastMissouri,in Shukla,V., and eraldeposits." Baker, P.A., eds., Sedimentology andGeochemistry of Dolostones: Society
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