Economic Geology Vol. 85, 1990, pp.

1044-1058

The BolivianTin Provinceand RegionalTin Distribution

in the Central Andes: A Reassessment
BERND LEHMANN,

FreieUniversitd't Berlin,Wichernstrasse 16, 1000Berlin33, Federal Republic of Germany

SHUNSO ISHIHARA,

Government Industrial Research Institute, Tohoku 2-1, Nigatake 4, Sendai 983,Japan

HUBERT MICHEL,
Fabeckstrasse 46, 1000 Berlin33, Federal Republic of Germany

JIM MILLER,
TheOpenUniversity, Department of EarthSciences, Walton Hall, MiltonKeynes, MK7 6AA,England
CARLOS RAPELA, Centro de Investigaciones GeolSgicas, Calle1, no. 644, 1900La Plata,Argentina
ALBERTO SANCHEZ,
Universidad Mayor de SanAndrds,Casilla11152, La Paz, Bolivia

MICHAEL TISTL,
MisiSnGeolSgica Alemana,c/o INGEOMINAS,A. A. 65160, Medellfn,Colombia
AND LOTHAR WINKELMANN

Misidn Geoldgica Alemana, Casilla 18-1374, Lima, Perk

Abstract

Tin distribution patterns in granitic andrhyolitic rocksuites fromthecentral Andes (northern Chile,northwestern Argentina, Bolivia) implya regionally variable bulktin distribution coefficient, withsystematic tin enrichment trends asa function ofmagmatic evolution in theBolivian tin belt, andlittle or notin enrichment outside of the tin province. The tin enrichment trends in theigneous rocks of theBolivian tinbeltcanbe understood asa consequence oftheilmenite series affiliation of these rocks, i.e., theirlowoxidation state, andof fractional crystallization. A geochemical tin anomaly in either thesource orthecountry rocks oftheBolivian tingranites and tin porphyries isnotlikely. Thetinoredeposits areseen asaresult ofeffective hydrothermal redistribution (fo2 belowto magnetite-pyrite-pyrrhotite buffer)of magmatically preenriched
tin in a shallow environment.

Introduction

the limited latitudinal extent of the tin belt, which

stretches for about 900 km from southeasternmost

THEcentralAndes arewidelyregarded asa type area PeruthroughBoliviato northern Argentina (Fig. 1). for continental marginmetallogeny alonga conver- Outside of this well-defined Bolivian tin belt, which gentplateboundary. Thereis a distinct asymmetrical hasproduced about15 percentof the historic world metal zonationperpendicularto the Andeanstrike, tin output, only a few scattered economic concentrawith majorsubparallel beltscharacterized fromwest tionsof tin andtungsten are foundin Argentina, and to eastby Cu-Mo-Au-Fe(WesternCordillera),Cu- sometungstenoccursin central Peru. This restricted Pb-Zn-Ag-Au (Altiplano), and Sn-W-Bi-Sb-Ag-Au distributionpattern contrasts with the continentwide mineralization in the EasternCordillera(Petersen, extent of the copperbelt and hasbeen discussed in 1970; Sillitoe, 1972, 1976). A specificfeature of terms of either metal inheritance from tin-rich source this--grosso modo--copper versus tin belt pattern is rocks by multistage igneous processes (Ahlfeld,1967;
0361-0128/90/1087/1044-1553.00 1044

REGIONAL TIN DISTRIBUTION, CENTRAL ANDES

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n(] tin ore depositsin the central Andes.

Schuiling,1967; Clark et al., 1976; Schneider and orite/tourmaline generally <1. Detailedaccounts of Lehmann, 1977;Routhier,1980), or by sequential the Boliviantin deposits are givenby Ahlfeld and release of metals along a shallow-dipping subduction Schneider-Scherbina (1964), Kelly and Turneaure zonewith the generation of tin-bearing calc-alkaline (1970), Sillitoeet al. (1975), andGrantet al. (1977). magmas at depths in excess of 200 km (Sillitoe,1972, The existence of metallogenic provinces, i.e., clus1976).

ters of ore deposits of similarmetal-mineralassem-

The ore deposits of the Bolivian tin belt are associatedwith Permo-Triassic tin granites in the northern partof thebelt andwithTertiarytin granites andtin porphyries whichoccurmainlyin centralandsouthern Bolivia(Evernden et al., 1977; Grantet al., 1979;

blages ona regional scale, suggests thatthe ultimate control of theformation of oredeposits isby regional geologic environments or processes. The criticalrole of large-scale factors is the subject of metallogenic studies. Thisbroader regional approach offers anim-

Clark et al., 1983; McBrideet al., 1983). Boron portantsupplement to the more commonstudies on (tourmaline) is a characteristic and very abundant detailed relations withinindividual oredeposits. The component of the hydrothermal tin ore systems of identification of regional element abundance patterns bothmineralization epochs. Fluorine (asfluorite) is is one way to elucidatethe problemof metal source
concentrated onlylocally, with the proportion of flu- in ore deposits geology. In the centralAndes, igneous

1046

LEHMANN ET AL.

rocksof variouspetrogeneticaffiliations canbe used asa windowinto the unexposed portions of that crustmantle segment. A first regionalaccountof tin abundances in volcanic and granitic rocksin and around the Bolivian tin belt was given by Lehmann and Pichler (1980). The meantin contents of rhyolitic rocksfrom Chile and northwestern Argentinawere found to be about 2 ppm,fromthe Bolivian Altiplano3 ppm, andfrom the Bolivian Eastern Cordillera (Los Frailes Ignimbrite) 4.5 ppm. Somedataon the Triassic tin granites

along the coast and in the interior; the MesozoicCenozoicplutohie rocksare distributedextensively
to the east of the late Paleozoie coastal batholiths.

Bothrock groups havebeen sampled in two transeets: the Antofagasta-Chuquieamata transeetand the Copiap6-E1 Salvador transeet. Sample locations andpetrographiealand chemical data are given in Ishihara et al. (1984). The upper Paleozoie granitoids are mostlycoarsegrainedbiotite granitescharacterizedby microcline and metasedimentary xenoliths.Magnetic suseeptiof the Bolivian Cordillera Real defined a mean around bilities are partly typical of ilmenite series rocks, 9 ppmSn.Thesedataindicated a positive tin gradient partly of magnetiteseriesrocks;both I- and S-type are present.Initial Sr ratiosof <0.706 of regionalscale towardthe Boliviantin provinceand characteristics were taken to reflect a primary tin anomalyin the argue against a substantialcrustal contribution to metamorphic basement of this metal province(Leh- these granites(MeNutt et al., 1975; Shibataet al.,
1984). mann and Pichler, 1980). plutohie rocksare charThe regionaltin andboronbackground abundances The Mesozoic-Cenozoic

of the Paleozoiccountry rocksof the tin belt have acterizedby a predominance of more marierocks, astonalite,quartzdiorite,anddiorite,andbelong subsequently been studied(Lehmannet al., 1988). such The Ordovician and Silurian clastic metasediments did to a eale-alkaline suiteof mainlyquartz-monzodioritie composition, with very importantasnot reveal any tin or boron anomalies relative to to granodioritie eopper-molybdenum mineralizations. Farrar equivalentrock typeselsewhere.Therefore, models sociated of metal inheritancehave to postulateeither the an- et al. (1970) and Clark et al. (1976) found by K-Ar atexisof tin-richPrecambrian basement (cf. Schuiling, datingin the Copiap6areathat the locusofplutonism from 0.6 mm/yr 1967) or the existence of a subcrustal tin anomaly (cf. shiftedeastwardat a rate increasing in the Mesozoicto 1.0 mm/yr in the Cenozoic.Initial Clark et al., 1976). A new attempt to identify regionalgeochemical Sr ratios are 0.704 to 0.706 in the 195- to 128-Ma trends in the Bolivian tin belt is presented here, rocks near the coast and 0.703 to 0.707 in the 128drawing on recently determinedanalyticaldata on to 10-Ma rocksin the interior (McNutt et al., 1975). tin abundances in the central Andes (Winkelmann, Porphyrycopper-related rocksare known, sofar, to and 1983; Gardeweget al., 1984; Ishiharaet al., 1984; have low initial ratios around 0.704 (Gustafson et al., 1984). The Tistl, 1985; Miller, 1988) andthe concept of Lehmann Hunt, 1975; Halpern, 1979; Shibata granitoidsare generally of the (1982, 1987) which aimsat a quantification of the Mesozoic-Cenozoic influenceof geochemical heritagein graniticdiffer- magnetite series with Fe2Oa/FeO > 0.5 (Ishihara, entiation suites. 1977), are hornblende-bearing, andcorrespond to the I-type group of the classification of Chappell and GeologicSettings of SamplePopulations White (1974). Graniticrock samples are from north-central Chile, the northernpart of the Boliviantin belt, and north- Granites of the northern Bolivian tin belt The granitic rocksfrom the northern part of the western Argentina. Data on rhyolitic and andesitic biosamplescome from rock suitesfrom the Western Boliviantin belt rangefrom hornblende-bearing to biotite-muscovite syenogranites. Cordillera (northern Chile and westernmost Bolivia), tite granodiorites and peraluminous, mostlywith from the Guatiquinaarea (borderzone of Chile, Bo- They are subalkaline livia, and Argentina), from the Altiplano of south- a molecularratio A1203/NaeO+ KeO + CaO m 1.1. a Middleto Late westernand northernBolivia,and the LosFrailesIg- K-Ar agedatadefinetwo agegroups, nimbrite on the peripheryof the centralBoliviantin Triassicgranitegroup (225-202 Ma), and a late Olito early Miocenegroup(28-19 Ma) (McBride belt (Fig. 1). Some chemicalparametersand refer- gocene ences for these sample suites are compiled in Ta- et al., 1983). ble 1. Triassicgranite intrusions are widespreadin the CordilleraReal and havebeen sampled--fromnorth North-centralChile granites to south--in the Huato,Illampu,Zongo-Yani, Huayna About20 percentof the totallandareaof the Chi- Potos,Chacaltaya,Unduavi, and Taquesi plutons. lean Andesconsists of plutonicrocksof graniticaffil- Samplelocations andpetrographical and geochemical iation (Visteliuset al., 1970), conventionally divided data can be foundin Lehmann(1979), Winkelmann into an upper Paleozoicgroup and a Mesozoic-Ce- (1983), and Tistl (1985). The Triassicgranitesin nozoic group. The upper Paleozoicgranitoidsoccur northernBoliviaare part of a 1,200-km-longPermo-

REGIONAL TIN DISTRIBUTION, CENTRAL ANDES

1047

Triassicgranite chain of the Eastern Cordillera ex- The Cafayate Graniteis a medium-grained rockwhich tendingup to centralPeru, interpretedas rift-asso- variesgraduallyfrom biotite tonalitcto biotite-musciatedintracratonic magmatism (McBrideet al., 1983; covite granite. It has a peraluminous,calc-alkaline well-definedvariationtrendsin major Kontak et al., 1984a). Initial Sr isotopedata from composition; southern Peru are in the rangeof 0.7081 to 0.7170 and traceelements over a wide rangeof composition a magmatic differentiation sequence (Rapela (Kontak et al., 1984a), preliminary data from the suggest CordilleraRealgive0.7079 to 0.7087 Sr initial ratios and Shaw, 1979). An initial Sr ratio of around0.705, (McNutt and Clark, 1983). Fe203/FeO ratios in much lower than the Sr ratiosof the metamorphic southern Peru and in the Cordillera Real are <0.2 country rocks, suggeststhat the, in part, highly of (Kontaket al., 1984b; Lehmann,unpub.data),con- evolvedgranitewasderivedfrom a parentmagma sistent with the predominance ofilmenite asthe iron- deep origin (Saavedraet al., 1987). The Cafayate Granite is associated with tourmaline-muscovite bearingoxidephase. which are tin barren.The CuchiThe graniticrocksin the Zongo-Yani area are lo- granitepegmatites cally foliatedand are surrounded by extensive syn- yaco Granodiorite has a relatively homogeneous and is mostlya medium-grained biotiteto postkinematic metamorphicaureoleslocally at- composition tainingsillimanitegrade(Bardet al., 1974). Martinez muscovite granodiorite. (1980) hasarguedthat,by analogy with similarrocks rocksof the WesternCordillera of Chile in the CordilleraOrientalof Peru, thesegranites rep- Rhyolitic and Bolivia resent synkinematic or late synkinematic intrusions associated with the early Carboniferousepisodeof Location,petrography,and geochemistry of our the Hercynian orogeny. Rb-Sr geochronology by sample suiteof upperCenozoic ignimbritic sheets and Miller (1988) definesan isochron age of 284 _ 16 rhyolitic stocksof the Western Cordillera (Rhyolite Ma. Discordant K-Ar and4Ar-39Ar agedatarecord Formation;Zeil and Pichler, 1967) is given in Pichler pervasivehydrothermaloverprint during the mid- andZeil (1969, 1972) and in Zeil andPichler (1967). exhibitSr isotope Tertiary (McBride et al., 1987). The Zongo-Yani The rhyoliticrocksare calc-alkaline, graniteswith sr(T) 80 and Na(T) = --6.0 can be ratiosof 0.705 to 0.713, and havevariableRb/Sr ramodeledascrustalmeltsfrom a maturesedimentary tios.They covera compositional field of alkalirhyolite source(Miller and Harris, 1989). ' to dacitewith a frequencymaximumat rhyolite comImportantvein- andmanto-type tin-tungsten min- position.Fe2Oa/FeO ratiosare >2 (magnetiteseries eralizations are associated with the chemicallymost rocks).The CenozoiccentralAndeanvolcanic rocks evolvedpartsof the CordilleraRealgranites, suchas are enriched in potassium, rubidium, S7Sr, andlsO, at the Chacaltaya graniteporphyrystock(Lehmann, comparedto equivalentvolcanicrocksof both the 1985) and the Chojlla mine granite (Winkelmann, northern and southernAndes.The petrogenesis of 1983; Harwood, 1985). the central Andean volcanic rocks is generally unA second granitepopulation of Oligocene-Miocene derstood asmixing betweenuppermantleandcrustal age occurs mainly in the Cordillera Quimsa Cruz material combined with crystal fractionation processes southeast of theTaquesi pluton(McBride et al., 1983), (Klerkx et al., 1977; Hawkesworth et al., 1982; Hilbut hasalsobeen reportedfrom the SanRafaeltin- dreth and Moorbath, 1988). copper mine in southernmostPeru (Clark et al., rocks from the Guatiquina 1983). Our granite samples are from the area around Rhyoliticand andesitic the tin-tungstenmine of Viloco in the north of the area, Chile A samplesuiteof 23 rhyolitic and andesitic rocks QuimsaCruz batholith (K feldsparmegacrystic biotite-muscovite granite), and farther southfrom the comesfrom the Guatiquinaarea in the Chilean high border triangle. Mina Argentina district (equigranular, medium- Andesof the Chile-Argentina-Bolivia grainedbiotite granite;Miller, 1988). The emplace- Thesesamples havebeen described and analyzed by mentof the Tertiarygranitic plutons coincided in their Gardeweg et al. (1984). The rock suite is of upper lateststages with widespread volcanism in the south- Miocene to Plioceneage and comprises ignimbrite ward extension of the granitebelt whichgaveriseto sheetsof daciticcomposition, stratovolcano-related the tin porphyrysystems in centralandsouthern Bo- lavasof andesitic to rhyoliticcomposition, and sublivia. volcanicporphyries of daciticand rhyolitic composition. All are magnetiteseriesrocks.The dividing Granitesof the Pampean Ranges, northwestern line for rhyolitic and andesitic rock groupsfrom this Argentina area (Table 1) was arbitrarily set at 68 wt percent A sample suitefrom the Ordovician Cafayateand SiOgcontent,althoughthere is continuous variation Cuchiyaco granitoids of the Pampean Ranges, which in major and trace elementsbetween both groups.

has been described in detail by Rapelaand Shaw S7Sr/S6Sr datavaryfrom0.707 to 0.713 (Gardeweg (1979) andRapelaet al. (1982), wasanalyzed for tin. et al., 1984); Ndvalues range from --1.6 to --8.1

1048

LEHMANN ET AL.

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REGIONALTIN DISTRIBUTION, CENTRAL ANDES

1049

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1050

LEHMANN ET AL.

-8 suggest a lowercrustal source for the Los (Hawkesworth et al., 1982).The chemical andisotope around datasuggest a petrogenetic modelof dominantly in- Frailesvolcanicrocks(Schneider,1985). tracrustal meltingwith minorinvolvement of mantlederived magma.
Results and Discussion

Rhyodacitic rocks from southwestern Bolivia Meantin contents (_1o-)of the sample populations The Mioceneto Holocene ignimbrites andstrato- are compiledin Table 1, togetherwith somepetrovolcano-related lavas andpyroclastics in southwestern chemicalindicatorsusedin the followingdiagrams. Boliviaare mainly of rhyodaciticcomposition, with Tin analyses of the Chileangranitesamples andof the rocksfrom the Guatiquina area,Chile, were transitions to rhyolite anddacite. Thethickness ofthe volcanic spectrometry at the volcanic sequences exceeds 1,000 m andtheirvolume performedby atomicabsorption in southwestern Bolivia is estimated to be about 8,000 Geological Surveyof Japan. The analytical technique a detection limit of 0.2 ppmSnandisdescribed km3(Kussmaul et al., 1977).Some ofthemiddle Mio- allows cenevolcaniccentersin the easternmost part of the by Terashima(1975). The remainderof the samples by X-rayfluorescence spectrometry in sample areahostvein-type polymetallic mineraliza- wereanalyzed
tion with silver, bismuth, lead, and zinc in addition Berlin. Matrix correction was by the background to tin (Chorolque, Tatasi,Tasna).The ore deposits scatter technique and calibration againstsynthetic The detection limit of thismethodisusually are part of extensive zones of argillicandphyllical- standards. teration (Ahlfeld and Schneider-Scherbina, 1964; 3 to 4 ppm Sn and hasbeen reducedby extended Grant et al., 1980). counting timesto 2 to 3 ppmin samples with low tin The analyticalerror at the detectionlimit The southernAltiplano rhyodacitesare docu- contents. mented by Fernandez et al. (1973) andKussmaul et is estimatedto be around 100 percent. The tin dataof the granitesample suites areplotted al. (1977). Petrochemical dataonthese rocks aswell asinitial Sr isotope ratiosof 0.706 to 0.713 (Klerkx asa functionof Rb/Sr and TiO2 in Figures2 and 3, The parameters TiO= and Rb/Sr were et al., 1977) suggest an originby partialmeltingof respectively. continentalcrustwhich hasan exceptionalthickness chosen as two independentindicators of the degree of magmaticdifferentiation in granitic rock suites, of up to 80 km in southwestern Bolivia. behavior of titaniumunder A second sample suitecomes from the Chorolque with the largelyimmobile contrasting with the sensimine (Sanchez, unpub.data).Polymetallic tin min- hydrothermalconditions eralizationis vein controlledin a pervasively quartz- tivity of strontium and rubidiumtowardfluid intertourmaline-altered volcanicvent, surrounded by ex- action. Other fractionation indices could be used as tensive sericitic and chloritic alteration zones in volwell. However, the availabilityof Ti, Rb, andSr data canicandlower Paleozoic countryrocks.The sericitic in mostroutine geochemical studies maketheseelealteration hasbeendatedat 12 Ma (Grantet al., 1977). mentsparticularlyusefulwhen comparing different The sample suitecomes fromunderground exposures data sets.An interpretativeproblem arisesfrom the of the tourmaline- and sericite-dominated alteration changein behaviorof titanium from compatible to zonesandis includedhere asan examplefor the non- incompatibletoward mafic rock compositions which magmatic distribution patternof tin (scatter distri- is the reasonfor the positionof the "Upper Mantle" referencefield in Figure 3. bution)in hydrothermal tin ore systems. The graniticsamplesuitesgive two differentdisTheLosFrailesIgnimbrite,centralBolivia tributionpatterns (Figs.2 and3): oneof positive linear Polymetallic vein- andporphyry-type tin-tungsten correlationof log Sn versuslog Rb/Sr (Fig. 2) or of mineralization in the central and southern Bolivian negativelinearcorrelation of log Snversus TiO= (Fig. tin belt is associated with pervasively alteredrhyoda- 3), respectively,and one of no or little correlation

citeporphyries andbreccias of earlyto middleMio- between tin content and the two differentiation inlow tin contentover wide ceneage(Grantet al., 1980).Thisperiodof igneous- dicators,i.e., a constantly hydrothermalactivity is postdatedby ignimbritic rangesof Rb/Sr andTiO=. Thesetin distributionpatthe nontin granite populations of sheetsof rhyolitic to rhyodacitic composition, of terns distinguish Argentinafrom the which the Los FrailesIgnimbritewith an extentof northernChile and northwestern
8,000 km2 and maximum thickness of up to 1,200 m isthe largest in centralBolivia. Our sample suitecovers a time sequence of volcanicactivityfrom 16 to 3.6 Ma and consists of rhyolitic rock samples which
havebeen collectedduringresearch on uraniummineralization in the Los Frailes area (Michel, in prep.; Michel and Schneider, 1978). Trace element data,
initial Sr ratios of 0.707 to 0.712, and Na values

tin granite populations of the northern Boliviantin belt. The correlation linesfor the tin granitesuiteare statistically significant at a confidence level of >99.9 percent, with a correlationcoefficientr(log Rb/Srlog Sn) = 0.78 and r(TiO=-log Sn) = -0.74, respectively. The geometricparameterswhich define these lines are very closeto those of tin granite suitesin other partsof the world (Lehmann,1982).

REGIONAL TIN DISTRIBUTION, CENTRAL ANDES

I I I I Illll I , J I JBlll I
i i i Jill
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1051

Illampu/Huato )
Zongo-Yanl

U.nduaw/Huayna Potore/ nacaltaya

Taquesi

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Quimsa Cruz

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100-

Gramtic rocks N Chile

[] Granitic rocks NChile

(< 68 wt%S,02)

(>68 wt % S02)

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Rb/Sr
FIC. 2. Rb/Sr-Sn variation diagram for granitic rocks of the central Andes. Tin granitesof the northernBoliviantin belt definea correlationline log (Sn) = 0.956 + 0.565 log (Rb/Sr)with r = 0.78 (n = 98). Hydrothermallyoverprintedgranitesamples from the Chacaltaya and Chojlla tin ore systems givescatter distributions at hightin levels.Nontingranites of northern Chile andnorthwestern Argentina (Pampean Ranges) havelow tin contents andgive no systematic tin enrichment trendduringmagmatic evolution.Bulk Crust andUpper Mantle referencefieldsaccording to Anderson (1983) andTaylor and McLennan (1985).

controlled by fractionalcrystallization andis different from the scatterpattern producedby alterationpropretations; slope and length of the linear variation cesses. Those sample groups from tin-mining areas trends in Figure 5 suggestsubstantial plagioclase which displaya nonsystematic behavior of tin probfractionation. Therefore, the two different tin distri- ably related to hydrothermalredistribution(particbution patternscan be understood in terms of a tin ularly the Chacaltayagreisensamples and the Chorbulkdistribution coefficient Ds, (crystals/melt) 1 olquetin porphyry)are alsocharacterized by anomin thenontin granite samples andDs, (crystals/melt)alousKsO/NasO ratios of >10; a feature which sets < 1 in the tin granitesamples (Lehmann, 1982). them clearly apart from the "magmatic"rock popuAlthoughany graniticrock will invariably be af- lationswhich haveKsO/Na20 ratiosof i ___ 0.5. fectedby fluid interaction duringits late-stage crysThe correlationlinesfor the tin granitesamples in tallizationand subsolidus evolution,the systematic Figures 2 and 3 extend toward averagecrustalcomtrendsin Figures 2 to 5 demonstrate thatmostsample positionand the least evolved samplesof this group groups(with the exception of thoseclassified ashy- approach bulk crustal composition.This situation
4 and 5 are in accordance with these earlier inter-

Fractional crystallizationhas been demonstrated to be the dominantpetrogenetic process controlling the magmatic evolutionin a largepart of the samples of both generaldistribution patterns. This is validfor the CordilleraReal granites in northernBolivia(Lehmann, 1979, 1985) and for the granitesof the Pampean Rangesof northwestern Argentina(Rapelaand Shaw,1979; Saavedra et al., 1987). The log Rb/SrTiO2 and log Rb-log Sr variationdiagrams in Figures

drothermallyoverprinted)still reflect a dominantly magmaticpattern with respectto Ti, Rb, Sr, and Sn. This conclusion is basedon the negativelinear correlation of data pairs in the TiO2-1og Rb/Sr (Fig. 4)

andlogRb-logSr diagrams (Fig. 5) aswell ason the linearcorrelation in thelogRb/Sr-log Sn(Fig.2) and TiOs-logSn diagrams (Fig. 3). This correlation behavior is in accordance with a chemical evolution

1052

LEHMANN ET AL.

'";" , i i1 'i , 1 i i i i i i i i i "'i ...... i i I

Illarnpu/Huato
Zongo-Yani
Jnacallaya Taquesi
QuimsaCruz

........

U.ndua,v.i/Huayna Potosi/

Chojlla (alteration) Chacaltaya(alteration)

Granitic rocks N Chile

100.

o [3

(>68 wt % SiO2)
Granitic rocks N Chile

(<68 wt%SiO2)

10.

Ill'

111111111111111

0.8

TiO2 (wt%)
FIG. 3. TiO2-Snvariationdiagramfor the samesamples asin Figure 2 (for plot symbols see Fig. 2). Tin granites of the northernBoliviantin belt definea correlation line log (Sn): 1.581-1.252 (TiO2)
with r = -0.74 (n = 96).

The predominanceof magnetite or ilmenite in a suggests derivation of the tin granitesuitefromsource materialnot anomalous in tin. A crustaloriginof the graniticrock is a functionof oxygenfugacityduring tin granitesuite is indicatedby the peraluminous, S- its formation.Ishihara(1981) pointedto the fact that with iltype chemistry of the CordilleraReal granites(Clark Sn-W mineralizationis generally associated and Robertson, 1978; Lehmann, 1979; Winkelmann, menitcseries rocks (conditions of low oxygen fugacity) 1983; Tistl, 1985; Miller, 1988). Sr isotopedatafrom whereas Mo mineralization isrelatedto magnetitesethe Cordillera Real and from the extension of this riesgraniticrocks(highoxygen fugacity).The crustal asa major control granitebelt into southern Peruare in favorof a crustal carboncontenthasbeen proposed origin of these granites(Sr initial ratios of 0.708- on oxygenfugacity (Ishihara, 1981). Higher oxygen 0.717; McNutt andClark, 1983; Kontaket al., 1984a). fugacity favors the mineral association magnetite In contrast, low initial Sr isotope ratios in the + sphenerather than ilmenite + a calcium-bearing northernChile granites(Shibataet al., 1984) and in silicate(Lipman,1971; Wones,1989). Bothmagnetite those from northwesternArgentina (Rapela et al., and sphenehave exceptionallyhigh tin distribution 1982; Saavedra et al., 1987) suggest a mainlymantle coefficients with Dsphene (crystals/melt) 60, and
source for these rocks. Their tin contents are ex-

tremely low (Chile: 1.4 ppm Sn; Argentina:all 36 samples analyzed<3.5 ppm Sn), in between average valuesfor upper mantleandbulk crustcomposition. These nontin granitesare mainly magnetite series granitoids, i.e., have Fe203/FeO ratiosof more than 0.5 (Ishiharaet al., 1979) asopposed to the ilmenite series granitic rocks fromthe Cordillera Realin Bolivia which have Fe203/FeO ratiosof lessthan 0.1 (Lehmann,unpub.data).

Dmagnetite (crystals/melt) 4 to 12 (Antipin et al., 1982). This may explaina bulk tin distributioncoefficient
near unity in magnetiteseriesrocks. The hydrothermally altered granitesamples from the Chojlla andChacaltaya tin-tungsten minesdefine a scatter distributionin Figures 2 and 3. The Chacaltaya greisen samples arecharacterized by advanced plagioclase-destructive alterationwith the stablehydrothermal mineral assemblagequartz-muscovitetourmaline-apatite-fiuorite-cassiterite. In the Chojlla

REGIONAL TIN DISTRIBUTION, CENTRAL ANDES

1.0
i i i iiI i i i i f i f r[ P i P i i , ''1

1053

A ,8'

o o o

FIG. 4. Rb-Sr vs.TiO2 variationdiagramfor the graniticrocks

of the northern Bolivian tin belt and from northern Chile. The

Bolivianrock samples define a correlationline (TiO2) = 0.48-0.40 log (Rb/Sr) with r = -0.91 (n = 104).

ternsestablished by fractional crystallization but enhancedby fluid interaction(seebelow). The tin dataof the volcanic rocksuites are plotted asa functionof Rb/Sr in Figure 6. The TiO2 content in theserocks, with SiO2mostly around 66 wt percent and less,is not a reliableindicatorof magmatic evolution because of the changein behaviorof titanium from compatible to incompatible at intermediate rock compositions. The distribution patternof the volcanic rocks is similarto thoseof the plutonicrocksamples: little tin enrichmentduringmagmatic evolutionfor the tin-barren volcanicsand strong tin enrichment trends in the rock samplesfrom the central and southern Bolivian tin belt. The rhyoliticsamples from the WesternCordilleraof Chile plot mostly below3 ppmSn (the analytical detection limit for thissample population), some samples with highRb/Srratios have tin levelsof 3 to 5 ppm.Rhyoliticandandesitic samples from the Guatequinaarea have tin contentsof 1.3 to 3.7 ppm (the analytical detection limit for this sample population is 0.2 ppmSn).The compositional field for leastdifferentiated samples of the tin-barren volcanics can be tentativelylocatednear the Upper Mantlereference field,whereas the Rb/Sr-Sn pattern
of the volcanic rocks from the Bolivian tin belt would

extrapolate towardthe Bulk Crustreference field. The hydrothermally overprintedrhyodacitic rocks muscovite granite,oligoclase andmicrocline are stable from the Chorolquetin mine (tourmaline-sericite altogetherwith subsolidus muscovite, tourmaline,and teration) are characterized by high Rb/Sr ratios,asis apatite.Thisrockgrouphaselementdistribution pat- expectedwith plagioclase-destructive hydrothermal

lOOO

A Cafayate Granite/NW Argenlina

(Ordovican)

Cordillera Real gramtes/N Bohva

(Tr&asslc)

Ouimsa Cruz granltes/N Boliwa

(Tertiary)

ChojIla muscowte granile/N Bolivia

(Toassic)

lOO

'

'

' ' ' ' '160

.....
Sr (ppm)

' ' 1'000

FIG. 5. Rb-Sr variationdiagramfor rock samples of the tin-barrenCafayateGranite (Pampean Ranges, NW Argentina),the CordilleraReal tin granites, the QuimsaCruz tin granites, andthe muscovite graniteof the Chojllatin mine.Slopeandextentof the linearcorrelation trendsin log-logspace suggest substantial plagioclase fractionationin all samplesuites.

1054
100
,

LEHMANN ET AL.

E
'

IIr IIlrll
Andesires

(Guatequina/Chile) Rhyohtes (Guatequina/Chile) Rhyolites (N Chile) Rhyodactes (SW Bolivia)

Los Frades Igmmbrite

(CentralBolivia) ChorolqueMine (Trm-seralteration)

10

Western Cordillera

rhyohtes/Chile (30 samples < 3 ppm Sn)

0.01

0.1

10

100

Rb/Sr
FIG. 6. Rb/Sr-Snvariationdiagramfor volcanicrocksof the centralAndes.The referenceline gives the evolutiontrend of the tin granitesof the northernBoliviantin belt definedin Figure 2. Rhyolitic rocksfrom the Western Cordillera (Chile and westernmostBolivia) have low tin contentsand show no or very little tin enrichment duringmagmatic evolution. Rhyodacitic rocksfromthe LosFrailesIgnimbrite in centralBoliviaplot closeto leastevolvedtin granitesamples of the CordilleraReal. Hydrothermally overprintedrocksfrom the Chorolquetin porphyrysystem give a scatterdistributionat high tin levels. The stippledpattern enclosing the Bulk Crust referencefield locatesnorthernAltiplanorhyodacites (7 samples with <3 ppm Sn;Redwood,1986).

alteration.This fluid overprint is also characterized by tin enrichmentup to levels of low-gradetin mineralizationandthere is a tendencyfor a chemical (and maybetemporal)continuumbetween magmatic processes and fluid-rock interaction which makes it dif-

ficult to distinguishclearly these two stagesfrom chemicaldata alone.The sameappliesto granite systems where subsolidusrecrystallization processes tend to magnifychemicaltrendsestablished by fractionalcrystallization (seeChojllaminesamples in Figs. 2-4; Higginset al., 1985). It is interestingto note that the Miocene-Pliocene
Macusani ash-flow tuffs in southeastern Peru, about

thought to reflect the magmaticchemistry, give a range in tin content of 27 to 194 ppm (nine samples) with corresponding TiO2 values of 0.22 to 0.04 wt percent, and Rb/Sr of 3.4 to 710. These data would plot in the mostevolvedpart of the correlationtrends of Figures2 and 3. The highly fractionatednature of the Macusani volcanics is alsodisplayed in systematic and characteristic enrichmentanddepletionpatterns for other incompatible and compatible elements. These features,together with the ilmenite seriesnature of the rocks(Noble et al., 1984; Pichavantet al., 1988a),identifies the Macusani volcanic zoneasa very prospectivearea for tin mineralizationin a porphyry
environment.

60 km west of the San Rafael Sn-Cu deposit, have chemicalcharacteristics very similar to the highly evolvedportionsof the tin granitesof northernBolivia. The Macusanivolcanics have been studiedby Noble et al. (1984) andPichavant et al. (1987, 1988a, 1988b) andhavebeendiscussed in petrogenetic terms of fractionalcrystallization and partial melting, the latter processbeing favored by Pichavant et al. (1988b). The chemical datafromPichavant (1988b),

Conclusions

The tin distributionin both plutonic and volcanic

rock suites from the central Andes follows two dif-

ferent patterns, summedup in Figure 7. These are (1) low tin contentswith little variation in tin levels at differentmagmatic evolutionstages (Chile, northwesternArgentina),and (2) higher tin contents with

REGIONALTIN DISTRIBUTION, CENTRAL ANDES

[ I I I f I I II I I I I I I

1055

lOO
11

o o10

lO

/o22
20 ', 21
'"12

Tin gramtes

0
0

1 ICRUST

aULK '"16'"18
'"19

Tin gramtes/porphyrles (Hydrothermal alteration)

Los Frales Igmmbnte

Tin-barren gramtic and rhyolitic-andesiticrocks

i

lOO
RblSr

FIG. 7. SynopticRb/Sr-Snvariationdiagramfor arithmeticmeansof the samplepopulations studied. Tin-bearinggranites definea tin enrichment trend asa functionof degreeof magmatic evolution. This trend extends backto average crustal rockcomposition. The LosFrailesIgnimbritefromthe periphery of the central Boliviantin belt plots closeto the least evolvedpart of this trend. Hydrothermally modified samples from tin ore systems havehightin levels,in addition, they are alsothe mostevolved magmatically (compareTiO2 contentsin Fig. 3 and Table 1). Tin-barren granitic and rhyolitic rocks havelow tin contents whichdo not correlatewith the degreeof magmatic fractionation. i = Unduavi granodiorite, 2 -- Illampu granodiorite, 3 = Taquesi granodiorite-granite, 4 = Huato granite;5 = Quimsa Cruz granites,6 -- Huayna Potosigranite, 7 = Zongo-Yanigranite, 8 = Chacaltayagranite, 9 = Chojlla granite, 10 -- Chacaltaya greisen,11 = Chorolquerhyodacite,12 = northernChile granodiorites, 13 = northernAltiplanorhyodacites, 14 -- Cafayategranodiorite,15 = Guatequina andesites, 16 = southwesternBolivianrhyodacites,17 = Cuchiyacogranodiorite,18 = Guatiquinarhyolites, 19 -- northern Chile granites,20 = Cafayategranite,21 = WesternCordillera rhyolites,22 = LosFrailesIgnimbrite.

a pronounced tin enrichmenttrend duringmagmatic evolution (Eastern Cordilleraof Bolivia). The firstrock group is not associated with tin deposits, the second groupcomprises the tin granites or tin porphyries of the Bolivian tin belt. The magmatic evolution in both generalrock groupsis at leastin somebetter defined sample populations controlled by fractional crystallization.

isnot likely. There isa systematic tin-enrichment pattern related to degreeof magmatic evolutionin the northernBoliviantin belt, with hydrothermaltin ore systemsassociated with the most evolved granitic
rocks.

The volcanicrock samplesfrom the central and

southern Bolivian tin belt are close to the distribution

pattern of samples from the northernpart of the tin The reasonfor the contrasting behaviorof tin is belt. The rhyodaciticrockswith Sn > 10 ppm are, seenin a variable bulk tin distributioncoefficientDs, however,modifiedby fluid interaction-hydrothermal (crystals/melt) which mustbe 1 in nontin granites alteration. Bhyolitic and rhyodaciticrocksfrom the and <1 in tin granites (Lehmann,1982). The general Western Cordillera of Chile define a trend of modnature of tin granitesas part of the ilmenite series erate or no tin enrichment with increasingBb/Sr. granitoidfamily suggests the influenceof oxygenfu- Maximum tin contentsreach only 5 ppm. Similar to gacityon the bulk tin distributioncoefficient, with a the situation with the tin-barrengranitesample poplow oxygenfugacityfavoringa low Osn (Ishihara, u]ations,theserocksare of the magnetiteseries. 1981). A worldwidefeature of tin-tungsten deposits and The evolutionpath of the granitic rocks of the their associated igneousrocksis a distinctlycontinorthernBoliviantin belt (Sn-TiO.2, Sn-Bb/Sr) sug- nental setting.The tectogeneticenvironments of tingestsaveragesourcerock with respectto tin, i.e., bearing igneousrocks are (1) continentalcollision bulk crustal composition. A geochemical tin anomaly belts (Permo-Triassic tin granitesof southeast Asia, in the source rocks of the Cordillera Bea]tin granites Permo-Carboniferous tin granites of westernEurope,

1056

LEHMANN ET AL.

and Precambrian tin granitesof the Kibaranbelt in Pichler(Universit/tTiibingen).All X-ray fluorescence central Africa); (2) the innermostarcsof continental analyses on tin were donein the laboratories of Florian margins(Tertiary tin porphyriesof Bolivia, Creta- Kubanek(Hahn-MeitnerInstitut fiir Kernforschung ceous-Tertiary tin granitesof Burmaand Thailand); Berlin) and L. J. G. Schermerhorn (Freie UniversitSt (3) zonesof intracontinental rifting (Permo-Triassic Berlin). The manuscript benefitedfrom critical readtin granites of northernBolivia,Cretaceous tin-tung- ing by Ulrich Petersen(HarvardUniversity),Bruce stengranites of southern China,Cretaceous tin gran- Reed (U.S. Geological Survey),and two Economic itesof Nigeria,Precambrian Rond6nia tin granites of Geologyreviewers. Brazil). Tin granitesor porphyriesare high-level,strongly August29, 1989; February 8, 1990 fractionatedrockswhich crystallizedunder low oxREFERENCES ygen fugacitybetween the Ni-NiO and quartz-fayalite-magnetite buffers(ilmenite seriesrocks).Their Ahlfeld,F., 1967, Metallogenetic epochs andprovinces of Bolivia: Mineralium Deposita, v. 2, p. 291-311. continentalsettingcannotbe related to sourcerocks
anomalous in tin. However, carbon and boron con-

tents of thick shalesequences--typical of tin provinces-may have an important control on magma evolution by providing a low oxidation stateandprogressively depressing the solidustemperatureof a fractionating melt.The boroncontent of average shale (around 100 ppm) is distinctly different from the crustal average (10 ppm) (Taylor and McLennan, 1985). Tin granites and porphyries from Bolivia, Cornwall, and Portugal displayboron enrichment
trends with boron levels in least differentiated rock

Ahlfeld, F., and Schneider-Scherbina, A., 1964, Losyacimientos minerales y de hidrocarburos de Bolivia:[Bolivia] Depart. Nac. Geol. Bol. 5 (Especial),p. 1-388. Anderson, D. L., 1983, Chemicalcomposition of the mantle: Jour. Geophys. Research, v. 88, supp.,p. B41-B52.
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L. A., 1982, Distributioncoefficients for tin and tungstenin ore-bearingacid igneous rocks:Geochemistry Internat., v. 19,
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samples near shalecomposition (Lehmann,1982). The establishment of a tin ore system seems to be p. 1515-1522. relatedto large-scale hydrothermal circulation which Burnham, C. W., andOhmoto,H., 1980, Late-stage processes of actsupon fractionated granite phases magmatically felsicmagmatism: Soc.Mining Geologists JapanSpec.Issue8, preenrichedin tin (Lehmannand Mahawat, 1989). p. 1-11. Sucha tin redistribution process is likely to be de- Chappell,B. W., andWhite, A. J.R., 1974, Two contrasting granite types:PacificGeology,v. 8, p. 173-174. pendenton oxygenfugacity,with the solubilityof cassiterite orders of magnitude greater near the Clark, A. H., and Robertson, R. C. R., 1978, The evolution and origin of the northern plutonit subprovinces of the Boliviantin quartz-fayalite-magnetite buffercompared to the hebelt labs. I: Annexto Warta Geol., v. 4, p. 42-43. matite-magnetite buffer (Eugster,1986). The para- Clark, A. H., Farrar, E., Caelles, J. C., Haynes, S. J., Lortie, genetic studyof KellyandTurneaure (1970) indicates R. B., McBride, S. L., Quirt, G. S., Robertson, R. C. R., and
variations in the metallogenetic fo2conditions belowthe pyrite-magnetite-pyrrhotite Zentilli, M., 1976, Longitudinal of the centralAndes:A progress report: Geol. Assoc. bufferduring thetin-tungsten orestage in theBolivian evolution CanadaSpec. Paper 14, p. 23-58.

Bard, J.-P., Botello, M., Martinez, 4., and Subieta,T., 1974, Relationsentre tectonique,m(tamorphisme et miseen placed'un granite (ohercynien t deux micasdansla Cordill're Real de Bolivie (Massifde Zongo-Yani):ORSTOM Cahiers,S(r. G(ologic, v. 6, p. 3-18. Burnham,C. W., 1985, Energy releasein subvolcanic environments:Implicationsfor brecciaformation:ECON.GEOL.,v. 80,

ore deposits. This is a situationtypical of tin ore deposits worldwide and is different from the muchmore

Clark, A. H., Palma, V. V., Archibald, D. A., Fartar, E., Arenas,

oxidized copper porphyry andmolybdenum porphyry

ore environment (Burnham andOhmoto,1980). Hydrothermal circulation is controlled by rockpermeabilityandtheavailability of a fluidphase. Bothfactors are maximizedin a shallowenvironment(Burnham, 1985).The highemplacement levelof the tin granites of thenorthern Bolivian tin belt (1-4 kmdepthrange) and of the subvolcanic tin porphyryintrusions contrasts with the similarlychemically evolved,however much deeperemplaced Permo-Triassic granites of the
EasternCordillera of Peru (>6 km) which have little or no tin mineralization (Clark et al., 1984). Acknowledgments

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Peru: ECON. GEOL., v. 78, p. 514-520.

Clark, A. H., Kontak, D. J., and Farrar, E., 1984, A comparative studyof the metallogenetic andgeochronological relationships in the northern part of the central Andean tin belt, SE Peru and NW Bolivia, in Janelidze,T. V., and Tvalchralidze,A. G., eds., Proceedings of the sixthquadrennial IAGOD symposium held in Tbilisi, USSR, Sept. 6-12, 1982: Stuttgart, Schweizerbartische,p. 269-279. Evernden,J. F., Kriz, S.J., andCherroni,M. C., 1977, Potassiumargonages of some Bolivian rocks: ECON. GEOL., v. 72, p. 10421061.

Eugster,H. P., 1986, Mineralsin hot water: Am. Mineralogist, v.

71, p. 655-673.

This studyoriginatedfrom analyticalwork on the large samplecollectionof Andean rocks by Hans

Farrar, E., Clark, A. H., Haynes,S. J., Quirt, G. S., Corm, H., and Zentilli, M., 1970, K-Ar evidence for the post-Paleozoic migration of granitic foci in the Andesof northern Chile: Earth Planet. Sci. Letters, v. 10, p. 60-66. FernandezC., A., H6rmann,P. K., Kussmaul, S., Meave,J., Pichler, H., and Subieta,T., 1973, First petrologicdata on youngvol-

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canicrocksof SW-Bolivia: Tschermaks Mineralog.Petrog.Mitt.,
v. 19, p. 149-172.

10 5 7

Lehmann, B., 1979, Schichtgebundene Sn-LagerstStten in der Cordillera Real/Bolivien:Berliner Geowiss. Abh., v. A14, p. 1135.

Gardeweg,M., Ishihara,S., Matsuhisa,Y., Shibata,K., and Terashima,S., 1984, Geochemical studiesof upper Cenozoicigneous rocksfrom the A!tiplanoof Antofagasta, Chile: JapanGeol. Survey Bull., v. 35, p. 547-563. Grant, J. N., Halls, C., Avila, W., and Avila, G., 1977, Igneous geology and the evolution of hydrothermal systemsin some sub-volcanic tin depositsof Bolivia: Geol. So(,'. London Spec. Pub. 7, p. 117-126. Grant, J. N., Halls, C., Avila, S., W., and Snelling,N.J., 1979, KAr agesof igneousrocks and mineralizationin part of the Bolivian tin belt: ECON.GEOL.,v. 74, p. 838-851. Grant, J. N., Halls, C., Sheppard, S. M. F., and Avila, W., 1980, Evolutionof the porphyry tin deposits of Bolivia:Soc.Mining GeologistsJapan,Spec. Issue, v. 8, p. 151-173. Gustafson, L. B., and Hunt, J.P., 1975, The porphyry copper depositat E! Salvador,Chile: ECON.GEOL.,v. 70, p. 857-912. Halpern, M., 1979, Strontiur.q isotopecompositionof rocksfrom the Disputadacoppermine, Chile: ECON.GEOL.,v. 74, p. 129130.

1982, Meta!!ogenyof tin: Magmatic differentiationversus geochemicalheritage:ECON.GEOL.,v. 77, p. 50-59. -1985, Formationof the strata-bound Ke!!huani tin deposits, Bolivia:Mineralium Deposita,v. 20, p. 169-176. -1987, Tin granites,geochemicalheritage, magmaticdifferentiation: Geol. Rundschau,v. 76, p. 177-185. Lehmann,B., andMahawat,C., 1989, Metallogenyof tin in central Thailand: A genetic concept:Geology, v. 17, p. 426-429.
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--

dean volcanicrocks:Mineralium Deposita,v. 15, p. 35-39.

Lehmann, B., Petersen, U., Santivafiez, R., andWinkelmann,' L., 1988, Distribuci6n geoqulmica de estafio y boro en la secuencia
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Bo!., v. 77, p. 19-27. Lipman, P. W., 1971, Iron-titanium oxide phenocrystsin compositionally zonedash-flow sheets from southern Nevada: Jour. Geology, v. 79, p. 438-456. Martinez, C., 1980, Structure et volution de !a chaneHercynienne et de !a chane Andine dans le nord de la cordill're
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685-713.

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sammenhang mit den terti/iren Vulkaniten des !ateinamerikanischen Kordi!!erenzuges:Erzmeta!!, v. 31, p. 1-8. Miller, J. F., 1988, Granite petrogenesis in the Cordillera Real, Boliviaand crustalevolutionin the central Andes:Unpub. Ph.D. thesis,Milton Keynes, The Open Univ., 198 p. Miller, J. F., and Harris, N. B. W., 1989, Evolution of continental crust in the central Andes;constraints from Nd isotopesystematics: Geology, v. 17, p. 615-617. Noble, D.C., Vogel, T. A., Peterson,P.S., Landis,G. P., Grant, N. K., Jezek, P. A., and McKee, E. H., 1984, Rare-element enriched, S-type ash-flowtuffs containingphenocrysts of muscovite, andalusite,and sillimanite, southeastern Peru: Geology, v. 12, p. 35-39. Petersen, U., 1970, Meta!!ogenic provinces of South America: Geol. Rundschau,v. 59, p. 834-897. Pichavant, M., Valencia Herrera, J., Boulmier, S., Briqueu, L., Joron, J.-L., Juteau, M., Marin, L., Michard, A., Sheppard, S. M. F., Treuil, M., and Vernet, M., 1987, The Macusaniglasses, SE Peru: Evidence of chemical fractionationin peraluminous magmas:Geochem. Soc. Spec. Pub. 1, p. 359-373. Pichavant, M., Kontak, D. J., Valencia Herrera, J., and Clark, A. H., 1988a, The Miocene-Pliocene Macusani volcanics, SE Peru. I. Mineralogy and magmaticevolutionof a two-micaaluminosilicate-bearing ignimbrite suite: Contr. Mineralogy Petrology, v. 100, p. 300-324. Pithavant, M., Kontak, D. J., Briqueu, L., Valencia Herrera, J.,

1058

LEHMANN ET AL.

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initial 87Sr/86Sr ratiosof late Paleozoic graniticrocksfrom