ECONOMIC

AND THE

GEOLOGY
OF ECONOMIC GEOLOGISTS

BULLETIN

OF THE

SOCIETY

VOL. 81

JUNE-JULY, 1986

No. 4

Sedimentaryand Diagenetic Controlson Red-Bed Ore Genesis: The Middle Tertiary SanBartolo Copper Deposit, Antofagasta Province, Chile
S. FLINT*

Departmentof Earth Sciences, University of Leeds,LeedsLS2 9JT, UnitedKingdom Abstract

The middleTertiary Pacencia Group of Antofagasta Province,northernChile, consists of over 2 km of continental sediments. Theseincludealluvialfan, playa,and lacustrine facies, representing deposition in an arid, closed basin. Coppermineralization ishosted by sheetand ribbonsandstone bodies, whichwere deposited in a high-energy playa-marginal sandfiat environment.Ore minerals occurdominantly asa matrixto theselithic arkoses, replacing earlier
carbonate and sulfate cements.

The mainore minerals arenativecopper,cuprite,andatacamite, although thereisanalongstrikepassage into coppersulfidecements. In a structurally complex zone,copper-iron and copper sulfides weredeposited in crosscutting fractures, commonly replacing evaporite veins. Primary chalcopyrite andbornitcexhibitprogressive oxidation to anilite,digenite, anddjurleite.
Chalcocite is not found. Much of this material has oxidized further to covellite of normal and

blaubleibender varieties.Galenaand nativesilverare presentin uneconomic amounts. Atacamite has a complex paragenesis, representing, at least locally, the earliest copperbearingphase. Provenance studies of the hostsediments andlead isotopedatafor the sulfides indicatethat boththe sandstones andthe metals werederived froma calc-alkaline volcano-plutonic complex to the eastof the basin,an area now obscured by the recentvolcanic Andes.Sulfurisotope

results for copper sulfides show verylighttSa4S values (-33%0),indicative of biogenic sulfate reduction underconditions of unrestricted sulfate supply.

(Gustafson andWilliams, 1981). Formationof many is thoughtto havebeeninfluSTRATIFORM, strata-bound depositsof copper and of the largerexamples enced by early rifting events within intracratonic bauranium are well documented in all continents. The sins (Brown, 1981, 1984; Sawkins, 1984) wherein an larger examples occurin siltstones and shales which associated baare almostinvariablyassociated with continentalred appealcanbe madeto the commonly in suchenvironments to provide a beds. Some famousorebodiesare, however, hosted saltic volcanism metal source. by the red beds themselves (e.g., Nacimientoand Althoughthis theory mightbe true for certainocCorocoro). Thesered-beddeposits are commonly of there are important, albeitsmaller deposhigh grade,but in manycases their smallsizemakes currences, its, found in avolcanic, late orogenic molasse basins. large-scale mining operations uneconomic. Copper sulfides are the dominant ores,commonly associated Andean examplesinclude the historically famous district of the Bolivianaltiwith organic matterandcharacterized by isotopically Corocorocopper-silver and Gouin, 1955; Ljunggren light, biologically reducedsulfur.Associated phases planobasin(Entwistle Coloso are nativesilver,gold,uraninite,nativecopper,and and Meyer, 1964), the conglomerate-hosted deposit in northern Chile (Flint et al., 1986) and the secondary oxidesand carbonates. minesat SanBartolowhich form the subjectof this Several recent studies have been concerned with the identification of commongeologicsettings for paper. The purposeof this paper is to describefor of what is essentially a manydocumented sediment-hosted copperdeposits the firsttime the occurrence high-grade oxideorebody anditsrelationship to sedof alluvial fan and playa * Presentaddress: Koninklijke/Shell Exploratieen Produktie imentationand diagenesis
Laboratorium, Volmerlaan 6, Rijswijk,The Netherlands.
0361-0128/86/536/761-1852.50 761 sediments in an arid zone molasse basin.

Introduction

762

s. FLINT

The SanBartolocopperdepositlies at an altitude of about3,000 m in the foothillsof the High Andes of Antofagasta Province,Chile (Fig. 1). Abandoned mine workingsare situatedin the gorge of the Rio Grande(Fig. 2), some 20 km to the northof the oasis
town of San Pedro de Atacama. The area forms a to-

the knowledge of Tertiary stratigraphy in this area, defining a series of lithostratigraphic members within thePacencia Groupwhichrepresents the wholebasinfill sequence (Fig. 3). The Pacencia Groupliesunconformably overcontinental clastics of the Cretaceous Purilactis Forma-

pographicdepression between the Cordillera Domeykoto the west and the Andeancordillerato the east. Much of this basinis occupiedby the recent Salarde Atacama, a largesaltpanwhichhasrecently becomean importantlithium producer.

tion. After deposition of over2 km of alluvialfanand playasediments, a compressive Andean tectonic event caused widespread foldingwhich includesrare recumbant structures. Following thisdeformation, a series of ignimbriteflowsof the PlioceneSanBartolo Formation were deposited with angular unconformity GeologicSetting onthe clastic succession (Hollingsworth andRutland, The SanBartolocopperdepositis hosted by con- 1968). Postignimbrite thrustinghas causedlocally tinental clastics ofthemiddle TertiaryPacencia Group repeated sequences, some involving the Pacencia (Fig.2). The stratigraphy of theareaaround San Pedro sediments. de Atacama was first described by Bruggen(1934) Recenttectonicmodels(Coira et al., 1982) favor and subsequently modified by Harrington (1961), a period of molasse basinformationduringthe OliDingman (1967), and Hollingsworthand Rutland gocene. Radiometric datingof the overlyingignim(1968). Recentwork by Flint (1985a) hasextended brites has yielded Upper Miocene-Pliocene ages

FIC. 1. The SanPedroregion,showing mainphysiographic features of the centralAndes.Contour heightsgiven in meters.

ORE GENESIS CONTROLS, SANBARTOLO DEPOSIT

763

cate a crustal thickness of some 70 km in this sector

of the Andes, andvolcanological studies document an eastward shiftin the focus of subduction-related magmatism,from the present-day Pacificcoast(Jurassic)
to the recent stratovolcanoes that mark the border

between Chile and Argentina (Farrar et al., 1970; Coiraet al., 1982; Pilger,1984). Coppermineralization at SanBartolooccurs in the ArtollaMemberof the Pacencia Group.Thismember overliesunmineralizedsalt pan faciessediments of the Palicaye Memberwhichcropout asthe SanBartolodome(Fig. 4). The junctionof the Palicaye Member with the overlyingArtolla sediments in the Rio Grandevalley is tectonically modified,althoughits
nature is unclear because the contact zone has been eroded to form much of the course of the Rio Grande

and Palicaye stream.The structurehas been interpreted as an anticline,faulted alongits axial plane, which hasbroughtsediments of the older Palicaye Memberintojuxtaposition with the Artolla Member (Hollingsworthand Rutland, 1968). The Artolla Memberis conformably andgradationally overlain by

San Bartolo FM
E
SAN BARTOLO FM

':':-::-Pacencia group undifferentiated

--- Purilactis FM
A B

3500
3250 '-

L ITHOLOGY

-_-.::,.:...,.,,._ ,

RIO SALADO :./;111 .'-:.:.:?'...'....'..'....'.'? MEMBER

!! RIO SAL
MEMBER

SEDI,ENT,RY STRUCTURES

CONCLOMFRATE-CLAS1 SUP[r>ORTEO CONVOIUI{ IlMINllION

CEMENTARIO
MEMBER

ARTOLLA MEMBER

Cu
BARROS
ARANA MEMBER

C. 2. Generalizedgeologicmap of the ea ound SanBarrolo.

X X PALIC
X X MEMBER

(Dingman,1965; Guest,1969) and thusassigns the PacenciaGroup to the Oligocene-Miocene (Flint, 1985a).Geophysical studies overrecentyears (James, 1971; Ocolaand Meyer, 1973; Stauder,1975) indi-

PURiLACTIS FM

FIG. 3. Stratigraphyof the SanPedrobasin(after Flint, 1985a).

764

s. FLINT

? ?
7
&3118

HEAD

OF

PALICAYE

MINES

/o

3020

BCEMENTARIO
2910

N
?

/SAN BARTOLO.

\
.!

[

/

/ Major Workings
Subsidiary Mines

, Rimof Gorge
Anticline

+-+San Bartolo Fm . Rio Salado Member J Cementario Member ':: Artolla Member

/ ARTOLLA MINE

Palicaye Member

r ]

Thrust Fault

Km

FIG. 4. Planof the SanBartolo miningdistrictshowing the principalmines andstructural features. Inset shows the localrelationships betweeninternalmembers of the Pacencia Group.

unmineralized, shallow lacustrine sediments of the

Cementario Member. This unit is known to contain

distal alluvial fan channels,spread out over an unconfined subaerial sandfiat. This process results in the

thin ashbeds(Flint, 1985a). Sedimentology of the Artolla Member

The Artolla sediments consist of over 400 m of red

deposition of clasticmaterial under conditions of waning flow (Flint, 1985a). Numerousdesiccation cracks attestto dominantly subaerial conditions. Detailed measurements of directional sedimentary
structures indicate that the mineralized Artolla sands

mudstones and interbeddedred and gray sandstone bodies(Figs.5 and 6A). The growthof primarynodular anhydritein the mudstones indicates highly arid conditions. Many secondary gypsumveinletscut the succession at highangles to bedding. Sand bodies tend to be laterally extensive with erosivebases andbedforms indicative of high-energy sedimentation. These internal structuresinclude the commonupward passage from upperphase planebedding,throughtrough crossbedding to climbingripple crosslamination. The mudstones are interpreted as subaeriallyexposed playa mud-fiat material, depositedwhere shallow, high-energysheetsof unconfinedflood water encounteredstorm-expanded, ephemerallake waters. Sandstones, exhibitingboth sheetand ribbon geometries, represent a more proximal playa-marginal

were derivedfrom provenance areasto the eastand southeast (Fig. 5). Higher in the succession, transport directionsswingto dominantlyfrom the south,possiblyrelatedto a change in drainage pattern(Flint, 1985a).Provenance areas to the eastof the basinare now obscured by the recentvolcanicAndes.
Mineralogy of the Host Sediments
The sandstones of the Artolla Member are medium

to fine grained,consisting of poorly sorted,angular grains of low sphericity. Dominant minerals arequartz and sodicplagioclase feldspar with subordinate orthoclase and rare microclines. Biotite and muscovite

micasare common,the former commonlyshowing chloritization. Detrital ferromagnesian minerals insandfiat. Periodic storms or seasonal climatic variacludehornblende andrare augite.Heavyminerallaynoticeably pickingoutcrossbedding tions are envisaged to have produced high-energy, ersarecommon, ephemeralflood waters which, after emergingfrom foresetsand dewatering structures.These opaque

ORE GENESIS CONTROLS, SAN BARTOLO DEPOSIT

765

SHALLOW
CEMENTARIO MEMBER LAKE

EPHEMERAL

suggested that hematite is derived from the breakdown of unstable,iron-rich mineralssuchas pyrox-

400

300

Cu

ARTOLL,
MEMBER 200

DRY

PLAYA

MUDFLAT

Cu

Cu
]oo

MARGINAL

SANDFLAT

Cu

enesand amphiboles. Suchmineralsare only rarely found asintact, detrital phases in the Artolla sands. UnderSEM,plagioclase feldspars show progressive dissolution with subsequent replacementby clay minerals, ultimatelyresulting in complete claypseudomorphs. Following earlydissolution events, a suite of authigenic mineralswasprecipitatedas syntaxial overgrowthsand discretephases(Fig. 6B and C). Well-developedsilicaovergrowths in optical continuity with the hostdetrital graincommonly preserve earlier hematitecoatings. Much of the sodium released duringdissolution of plagioclase feldspars androckfragments wasprecipitatedassmall, euhedral, authigenic grains of analcime whichhavea distinctive cubo-octahedral morphology (Fig. 6B, D, and E). Analcimecommonly nucleates on detrital quartz and feldspargrainsand tendsto line porespaces. Formation of analcime fromvolcanic rockfragments isfavored by relativelyalkalineinterstitial solutions (Aoyakiand Asakawa,1984). These
authors have also documented the transformation of

analcime to albiteat temperatures above138C.Authigenic albiteispresent in the Artollasandstones but PALICAYE occurs asovergrowths whichpredateanalcime (Fig. MEMBER SALINE MUDFLAT 7), indicatingthat temperatures never reachedthis level in the hostrocksto the ores.Thusthe presence of abundant analcime in the hostrocksallowsan apFIC. 5. Representative sedimentary log throughthe Artolla proximate upper temperature constraint to be placed Memberat SanBartolo showing principal ore-bearing sandstones. on the diagenesis and indirectlyon the later mineralizingevents. The earliest pore-filling cementin thesesandstones in a coarsely crystalline grains arewell rounded andcommonly include mag- is calcite(Fig. 6B). It occurs netite, titanomagnetite, and illmenite which com- form and possibly represents the reprecipitation of monlyexhibitcomplex exsolution textures. Other ac- calcium fromdissolved feldspars. Associated gypsum cements indicatecontinued highlyarid conditions. cessory minerals are rutile andapatite. A characteristic feature of these sandsis the abunLaterin diagenesis the alkalifeldspars show partial dance of igneous rockfragments, whichtend to be to complete dissolution,with subsequent potassic on detritalandearlier authigenic phases. subrounded and heavilyweathered. They include overgrowths volcanic andplutonicmaterialof andesitic-dioritic to This paragenetic sequence of dissolution, replacegranodioritic compositions, andlocally account for 20 ment, and authigenesis hasbeen observed in many percent of the mode. The Artolla sandshave been arid-zonered-bedlithofacies (Walker et al., 1978;

interpreted aslithicarkoses, immature erosion prod- Turner, 1980). changes arefoundfollowing uctsof intermediate to acidic crystalline complexes No furtherdiagenetic
(Flint, 1985a). PremineralizationDiagenesis of
the Host Sediments

alkali feldsparovergrowthsin unmineralizedsediments;this is at variancewith the main ore-bearing sands andspatially related,slightly mineralized beds,
in which the most noticeable feature in both field and

Microscopy, SEM, and microprobestudieshave microscopic studies is the partialto complete removal established a diagenetic scheme covering theperiod of hematite, givingthe rocks a characteristic bleached, fromdeposition untilafterthe mineralizing events. pale gray appearance. This color changeassociated The earliest recorded diagenetic changes involve the with mineralization has beennotedin manyotherredreddening ofthestrata by production of thinhematite bed-typecopperdeposits suchasCorocoro (Ljungrimson detritalgrains. Studies of thisphenomenongren and Meyer, 1964), Nacimiento(Woodwardet in recentdesert alluvium (Walkeret al., 1978) have al., 1974), andCaletaColoso (Flint et al., 1986). A

'I
Cal

An
Cup

II

II

At

E
FIG. 6. A. Abandoned workingsat SanBartoloin steeplydipping playasandstones and mudstones of the ArtollaMember.B. Photomicrograph of sandstone from the Artoilamine.This bed hasnot been subjected to the secondary porositygeneration; early calcitecement(c) is preserved. Note the small, pore-lining analcimes(An). The large detrital grain in the center is a plagioclase feldsparshowing advanced dissolution. The voidssoproduced are filled by atacamite (dark).Planepolarizedlight. Scale bar = 0.5 mm. (2. Photomicrograph ofmineralized sandstone, Artoila mine. Note syntaxial overgrowth on centralquartz grain.The opaquecuprite matrix encloses earlier atacamite .(gray materialat tip of arrow) whichremains ascorrodedisletsand early pore linings.Planepolarizedlight. Scalebar = 0.5 mm. D. Cuprite cement ((2up) enclosingearlier authigenicanalcime(Ab) and calcite matrix ((2al).

Reflected, planepolarized light.Scale bar = 0.5 mm.E. SEMbackscattered electron image of fibrous pore-filling atacamite (At),postdating authigenic analcime (Ab)whichhasnucleated ondetritalquartz (Qz). Scale bar = 0.5 mm.F. Detail of cuprite-cemented sand. Note the brecciation of silicates caused by displacive growthof the cuprite.Reflected, planepolarized light. Scale bar = 0.5 mm.
766

OREGEHESIS COHTROLS, SAH BARTOLO DEPOSIT

#IliERAL/VliT EARLY OXIDATIVE D1AGliE$I$ RDUCT1Oll LATE OXIDATIVE D IAGEI/ I$ RNOBILIZATIO

767

Hematite

Clay lilaerals
lclte

Gyum
Analcime Alblte

K Feldsr
ltite

artz

]obile
}RITY

rucnt
GE]ERAT I0

(? orEanic acid)

Chalcopyrite
rnite

]at lye Copr Chalcite Group Cuprite

vellite
Tenorire [alachite

TI#E

FIG.7. Apparent paragenetic relationships of diagenetic events in theArtolla sandstones.

similarbleaching is alsodevelopedin sandstone uraniumoccurrences such asthe Jackpile deposit in New Mexico(Adams et al., 1978; Turner-Peterson, 1985).

The full complement of mineralized beds is exposed only at thislatter location. They are foundover a stratigraphic intervalof some75 m (Fig. 8A). Althelateral continuity of individual orebodies A pervasive dissolution of the earlycalcite cement though owingto recentland slips,the appears to be temporally associated with thiscolor is difficultto assess change andcommonly results in large, isolated calcite available evidence indicates a strata-bound but not stratiform configuration. Mineralization isseen crystals in a later, mineralogically differentmatrix always instances to lie at an angleto bedding while (Fig. 6D). Thisdissolution of earlypore-filling min- in some erals caused a reduction of cementation in only beingrestricted to individual beds. operations, carried outbetween the midslightlymineralized sands. The main ore-bearing Mining centuryand 1925 (Travisany, 1978), insandstones arefullylithifiedowing to theprecipitation nineteenth
volveda combination of room andpillar andunderof later copper-bearing cements. stoping methods. Thisresulted in theextraction Theseevents mayindicate a change in ground-wa- hand

ter chemistry, prior to the introduction of copperbearingfluidsinto the sediments. The early calcite cements appear to be replaced by poikilotopic celestite whichis foundonlyin mineralized samples. This relatively uncommon cement could be relatedto the
release of strontium from the calcite lattice during

of almost complete mineralized beds,accessed directlyfromoutcrops, although several shafts appear to havebeensunk.The operation wasdiscontinued owing to waterproblems ratherthanfailing reserves.
Mineralized sands are recognizedby a pervasive

dolomitization, but dolomite isnotpresent in the Artollasandstones. A second possibility isthe derivation mented,unmineralizedstrata.Tracesof green malare commonly foundat outcrop. of Sr duringthe dissolution of alkali feldspar; the achiteandatacamite investigation hasrevealed twodifferent greater stability of thismineral overplagioclase feld- Underground ofmineralization. In thefirststyle,oreminerals spars in the diagenetic environment andthusitsrel- styles ativelylate dissolution wouldbe in accord with the occur as a matrix to detrital silicatesand commonly primary sedimentary structures such ascross lateparagenetic position of celestite asa matrixmin- highlight The secondstyle of mineralization is eral.The presence of celestite asanimmediately pre- stratification. observed only in the mines at the head of Quebrada copper cement possibly suggests that the change in wherethehost rocks, a stack of channel sand ground-water chemistry associated with bleaching Palicaye bodies, dip vertically in a structurally complex zone facilitatedthe dissolution of alkali feldspar.

bleaching andpoorcementation at outcrop. Thiscolor changecontrasts stronglywith the red, well-ce-

filledby evaporite andoreminerals in aveinlike mancanbe tracedovera The copper oresat SanBartolo are hosted by up ner. Thisstyleof mineralization thickness of about25 m in the exposed to 15 sandstone bodies whichrangein thickness from stratigraphic
0.5 to 2.5 m. These sands have been mined along a

Mineralization

and showlocal brecciation(Fig. 8A). Fractures are

strikelengthof about4 km fromthe Artollamineto the minesat the headof Quebrada Palicaye(Fig. 4).

lower half of the Artolla Member. The main mineralization is considered to have no

structural control. As discussed above, the main ore-

768

s. FL/NT

Dg

GR

,. Dg

FIG. 8. A. Verticallybedded,sulfide-bearing sandstones of the Artolla Member in the miningarea at the headof QuebradaPalicaye.B. Reflectedlight photomicrograph of early pyrite (Py) partially

replaced bydigenite (Dg). Thepresence ofparagenetically later covellite isconsistant withprogressive

oxidation. Planepolarized light. Scale bar = 0.5 mm. C. Backscattered electronphotomicrograph showing

ORE GENESIS CONTROLS, SANBARTOLODEPOSIT

769

bearingsandstones are locatednorth of the SanBartolo dome,an anticlinal structure whichexposes strata of the older, unmineralized Palicaye Member. However, one mineralizedbed is found in exposures of
the Artolla Member to the south of the dome in the

FunicaSanBartoloarea(Fig. 2), whichsuggests that the copperoresformedbefore the Pacencia succession was folded. The deformation occurred before

depositionof the SanBartoloignimbrites; assuming an Oligocene-lowerMiocene age for the Pacencia Group,thisrelationship constrains the timing of mineralizationto pre-upper Miocene times. The generalabsence of extensive bleachingand subsequent ore genesis in the Funica-San Bartoloarea couldindicatethat the fluidsresponsible for these events were concentrated in the SanBartolo-Palicaye area.This concentration is possibly due to the localizationof ribbonsandstones with some bed amalgamation,whichpossibly allowedthe passage of greater

tion. Texturally,the copperoxides occuraseuhedral, interlockingcrystalssurrounding detrital and early diageneticphases(Fig. 6D). They are also seen to envelopwhat appearsto be paragenetically earlier native copperand atacamite (Fig. 6C). Native copper is found only in unweatheredunderground samples. It occurs aslarge,sometimes poikilotopiccrystals andiscommonly rimmedby cuprite. This evidencefor an oxidativeoverprint on the primaryore minerals leadsto speculation that the larger volumes of oxide-cemented sandstone originallyhad a matrixof native copper. In sandbodieswhich carry uneconomic ore concentrations, ore minerals tend to occur as distinct

volumes of grounwater.
Ore mineralogy

Ore mineralswere depositedin pore spaces following the diageneticeventsoutlined above;their distribution wascontrolledby the generation of secondaryporosity. Matrix mineralization: This styleof mineralization, accounting for about 80 percent of observedoccurrencesis perhapsbest developedin the area of the Artolla mine (Fig. 6A). The important ore minerals in order of abundance are atacamite(Cu2[OH]3C1), tenoritc, cuprite, and native copper.Galenais widespreadin smallquantities.Native silver is associated

stringersand roughly spherical"concretions."The stringers are up to 1.5 cm wide, are commonlydiscordantto bedding,and causeno disruptionof the silicate fabric.Microscopic examination reveals abrupt lateral terminations to the stringers of matrixcuprite. Localbrecciationof silicategrainsis seenon a microscopicscale,suggesting that the ore mineralsgrew displacively in part (Fig. 6F). In rare casesorganic remains are associated with stringers andtend to trace the outlineof the structures. It is possible that these objects are the remainsof invertebrate burrows. In oneburrow,grains of earlypyritereplaced the organic material. The pyrite itself is partially replaced by coppersulfides (Fig. 8B). The roughly circular (0.5-2.5 cm) concretions of ore in bleachedsands consist commonly of a central coreof nativecopper,surrounded by smallinterlocking crystals of cuprite, againwith abrupt outer terminations against unmineralized, invariablycelestiterich host rock. These nodulelike concentrations have

with the nativecopperandcopperoxides. Secondary malachite is present but not common. Copperoxides were probably the mosteconomically importantore: black,oxide-cemented sands assay upto 28 wt percent Cu and containup to 30 ppm silver(G. Walls, pers. commun.,1983). Detailed optical and microprobe studies showthat two oxidemineralsare presentin this deposit.In subsurface samples, the oxideis red, contains 85 to 89 wt percent copper, andshows strong red internalreflections in polished specimens. These propertiesare consistent with cuprite.The black cementingmineralin sandstones contains lesscopper (78-80 wt %) and doesnot exhibit the red internal

been documented in other red-bed copperdeposits (Ljunggrenand Meyer, 1964) and are knownto correlate with the presence of local plant remains. To
date no suchdebrishasbeen identified at SanBartolo,

making interpretation of theseisolated patches of ore minerals problematical. Possibly originalorganic material could have been removedby diageneticoxidation. In fact work on modern sediments of the Great

SaltLake, Utah, shows that only 5 percentof the total organiccarbon originally depositedin these playa sediments is preserved (Eugster,1985). The green oxychlorideatacamite is widespread reflections. This mineral is considered to be tenoritc throughout the deposit; ontexturalgrounds it appears (CuO), developed asa response to prolonged oxida- to haveat leasttwo generations. This mineralis the

chalcopyrite (Cp)-bornite (Bn)botryoidal intergrowths rimmed by possibly supergene anilite-digenite (Dg).Palicaye mines. Scale bar = 0.5 mm.D. Galena (Gn)enclosing earlierdjurleite (Dj). Muchof the bounding djurleite isreplaced by atacamite (At).Palicaye mines. Backscattered electron image. Scale bar -- 0.5 min.E. Digenitelike sulfide phase replaced alongorthorhombic cleavages by atacamite. Palicaye mines. Backscattered electronimage.Scale bar -- 0.5 min. F. Rareoccurrence of insoluble organic residue (attip of arrow)marking the former presence of thepostulated organic mobile reductant which isthought to havepromoted sulfide precipitation. Notethe close association of copper sulfides (black). Palicaye mines. Transmitted, planepolarized light.Scale bar -- 0.5 mm.

770

$. FLINT

earliestcopperphasefoundin bleachedsandstones Artolla mine where copper sulfidesare common. andiscommonly the onlyore mineral in slightly min- Chalcocite-group mineralsare dominantalongwith eralizedrocks. It occurs asearlyrimsaround detrital secondary covellite,but in rare caseschalcopyrite grains, asintergrowths with authigenic silica,andfills formsan early cement.The sulfides have chemical earlydissolution voidsin calcicplagioclase feldspars compositions corresponding to anilite, digenite,and (Fig.6B).Earlyatacamite coexists with remaining he- djurleite; stoichiometric chalcociteis not present. matiteandencloses partiallydissolved relict crystals Theseminerals sharea paragenetic position identical of the early calcitecement.In more heavilyminer- to the volumetrically moreimportant cupriteandnaalizedsands, this early atacamite is commonly over- tive copper.They havethe formof smallinterlocking grown by later native copper and cuprite (Fig. 6C). crystals, invariablyshowinga strongorthorhombic Electronprobeanalysis shows thismineralto contain cleavage(Fig. 8B and C). Covellite commonly reapproximately 52 wt percent copper.Atacamitehas placesthe chalcocite-group mineralsand occursas never been synthesized. Its behavioris thoughtby overgrowths on theseearly coppersulfides. Rickard(1971) to be Similar to its polymorph paraThisore mineralogy, characterized by the complete tacamite,whichhe produced under acidpH condi- absence of sulfides in samples fromthe Artollamine, tionsby adding sodium hydroxide to cupricchloride marksan interesting departurefrom almostall docsolutions. Figure 9 shows that, given a chlorideion umented economic red-bed copper occurrences concentration of i M, atacamite couldprecipitate out whichare dominated by copperandcopper-iron sulof a chloridebrine in moderateto highly oxidizing fides(Gustafson andWilliams,1981). Despitethe exconditions and neutral pH conditions. This diagram amination of over 80 specimens of freshore, there is alsoindicates that with a fall in pH valuesto acidic no clear evidence of the nature of association between andmatrixnativecopper-cuprite. Sulground-water conditions, coppersulfides should pre- matrixsulfides cipitatefromthissamechloridesolution with little or fidemineralization tends to pass intotexturally similar mineralization alongstrike.In rare nochange in Eh values. A fullerdiscussion of atacam- nativemetal-oxide containing an association of all the above ite stabilityrelations is givenby Flint (1985b and c). specimens Galena,although widespread throughout the de- mineral types cuprite, occupying a paragenetically posit,neverattains economic quantities. Detailedmi- late position,occursas overgrowths to chalcocitecroscopic andSEMstudies haveshown it to haveboth groupminerals andcovellite. Thistentatively suggests that muchof the originalmatrixcouldhavebeensulearlyandlate paragenetic positions. A significant change in the mineralogy of matrix fide minerals. oresoccurs some3 km alongstrikenortheast of the Veinlet mineralization:The secondstyle of mineralizationoccursonly in the minesat the head of Quebrada Palicaye (Fig.4). Veinlets disrupt thefabric of host sandstones on a microscopic scale and are dominated by sulfideore minerals. Atacamite is less common thanin the matrixmineralization andcuprite .8 is absent. Microscopic andSEM studies indicate that the earliest phase to precipitate was coarsely crystalCu2+ line chalcopyrite. Towardthe edges of some veinlets, 6 Cu2(OH)3Ct bornite occursin botryoidal intergrowthswith the primary chalcopyrite (Fig. 8C). In many sedimenthosted copperdeposits borniteis commonly slightly sulfur rich (e.g., McCauley, 1964; Ripley et al., 1980). votts The borniteanalyses (Table1) show thatthe bornites

Eh.Z, cuo Cu2S

0

at San Bartolo are also sulfur rich.

-'2

Chalcopyrite andbornitearepresent onlyin small quantities in the veinletstyleofmineralization at Palicaye where they are replacedalongfractures by minerals of the chalcocite group(Fig. 8C). Thesere-

placement textures indicate progressive oxidation of copper-iron sulfides to coppersulfides, a process known to produce metastable blaubleibender covel-

pH
(CI- = 1.0 . MoiGe te Bose, 1976, n etes, 1977.

litesandeventually stable covellite. Peters(1977) and Potter(1977) support the abovetheoretical studies. Galenais presentin the veinletsbut in lower quantities than in the matrix ores (Fig. 8D).

OREGENESIS CONTROLS, SAN BARTOLO DEPOSIT

TABLE 1.

771

ElectronMicroprobeAnalyses of Ore Mineralsfrom SanBartolo

Mineral
Cp Cp Cp Cp Bn Bn An An An

Wt % Cu
34.295 34.060 34.197 34.277 60.610 61.125 77.324 77.093 77.018

Wt % Fe
29.611 30.562 30.487 30.358 13.075 12.906 0.181 0.025

Wt % Ag
0.003 0.019 0.007 0.026

Wt % Au

Wt % S
35.358 35.656 35.046 35.224 26.260 26.316 22.282 22.140 21.912

Total
99.940 100.919 100.725 100.064 100.249 101.261 100.472 100.792 100.283

Formula
Cuo.97Feo.96S2 Cuo.96Feo.ssS2 Cuo.9sFeo.9S2 Cuo.9seo.ssSa Cu4.66Fe.4S4 Cu4.6sFe. aS4 Cu.75S Cu.75S Cu.7sS

0.067 0.079 0.058

0.273 1.002 0.301

An/Dg An/Dg An/Dg An/Dg An/Dg

Dg Dg Dj Dj

77.035 77.900 77.753 77.469 78.029

77.262 77,124 78,685 79.801

0.039
0.357 0.201
0.487

0.219 0.221 0.129 0.117 0.019

0.178 0.165 0.296 0.226

0.080 0.329 0.278 0.007 0.145

0.007 0.006 0.021 0.191

22.042 21.924 22.042 21.995 22.325

21.610 21.212 20.139 20.120

99.415 100.374 100.202 99.945 100.719

99.057 99.360 99.141 100.338

Cu.76S Cu.7sS Cu.7sS Cu.7S Cu.76S

Cu.soS Cu.soS Cu.s6S Cu.o6S

Bb Cv2 Bb Cv Bb Cv Bb Cv
Cv Cv Cv

72.551 73.212 68.888 68.110

66.226 66.904 66.213

0.178

0.222 0.218 0.164 0.212

0.068 0.092 0.212

0.096 0.030 0.078 0.101

0.042 0.117 0.039

27.238 27.386 30.763 30.661

32.696 33.289 33.326

100.107 100.996 99.893 99.084

99.032 99.990 99.790

Cu.aaS Cu.aS Cu.aS Cu.zS

Cu.ooS Cu.ooS Cu.ooS

Abbreviations: Cp -- chalcopyrite, Bn -- bornite, An = anilite,Dg -- digenite, An/Dg -- intermediate phase between, or mixture of anilite anddigenite, Dj = djurleite, Bb Cv -- type 1 blaubleibender covellite, Bb Cva= type2 blaubleibender covellite, Cv
-- stoichiometric covellite

phases. Theseresultsmay be compared with microprobe data on coppersulfides from sediment-hosted copper depositsof varying ages(Goble and Smith, 1973; Ripley et al., 1980) in whichthe mostcommon Cu/S ratiosfall between Cu.76S and Cu.78S. Theoretical studiesof the copper-sulfursystem(Potter, 1977) indicate that no stable phase exists with a Cu/S ratio of 1.76 to 1.78. Two explanations havebeen offeredfor thesemeasuredratios,one being that the measured phases are in fact mixturesof anilite with digeniteand/or djurleite. Gobleand Smith(1973) suggest that originally Sulfide mineralchemistry compositions betweenchalcocite andcovelliteexsolve to givecompositions close to the preferredCu/Sratios Electron microprobestudieswere carried out to of 1.12, 1.32, and 1.76. These ratiosagreewith the characterize thecopper sulfide mineralogy andtode- electron probeanalyses presented in thispaper(Table termine if there were compositional differences be- 1). A secondexplanationfor the obtained ratios is tween matrix and veinlet sulfides. Electron microthat thesesulfides were originallyof anilite compoprobeanalyses (Table1) indicatethat,whereas there sition.As demonstrated by Sillitoe and Clark (1969), are no differences in mineralchemistry betweenma- anilite may be convertedto a digenite-typesolidsotrix and veinlet types,all sulfides are characterized lution by grindingat room temperatures. Therefore by lowerCu/Sratios thanarefound in many deposits specimen polishing waspossibly responsible for par(Ixer andVaughan, 1982). Several compositions are tially convertinganilite to slightlymore copper-rich common (Table1), corresponding to aniliteanddig- phases or for initiating limitedexsolution, assuggested enitewith minordjurleite.Compositions intermediate by Goble and Smith (1973). Anilite in the oxidized between anilite(Cu.75S) anddigenite (Cu.8oS) are zone of Chileanporphyrycopperdeposits hasbeen possibly dueto fine-grained intergrowths of these two interpreted as a product of supergeneenrichment

Underground investigation revealed the presence of thin (<1 cm), laterallyextensive sheets of native copperwhichfill tectonic fractures in the vertically beddedsandstones at Palicaye. Thisphenomenon is identicalto the sheets of nativemetalreportedfrom the limbs of tight folds in the Corocorodeposit. Ljunggren andMeyer (1964) interpreted thesesheets asa remobilization of earliermatrixoresduringdeformation.Probablythe veinlet and sheet material confined to the structurally complex areaat the Palicayemineshasa similarorigin.

772

s. FLINT

Many authorshave speculatedon the sourceof metals in sediment-hosted copperdeposits. Ideasinchalcocite are the mostabundantsulfides in many clude derivation from the mantle via hydrothermal Bartolosamples. Microproberesults(Table 1) show of earlierbasement deposits, andconthat two compositions of blaubleibender covelliteare fluids,erosion centration of ore minerals from trace amounts in present,with Cu/S ratiosof 1.1 and 1.4. This data is rock typesby sedimentary, diagenetic, and in striking agreement with compositions obtained by common metamorphic processes. Several workers have pointed Goble and Smith (1973) and is in accord with the electrochemical studiesof Potter (1977). Blaublei- out the higherthan averageCu valuesin tholeiitic andtried to fit red-beddeposits into earlyrift bendercovellites represent intermediate stages in the basalts settings. Clearly the San Bartolo deposit isnotrelated formation of normalcovellitefrom chalcocite. They to continental rifting and basaltic volcanism; as disform due to the difficultyin nucleating hexagonally cussed earlier, the San Pedro basin, although extenclose-packednormal covellite from cubic closesional, is situated on a sector of the world's thickest packedaniliteor digenite(Potter,1977). continental crust. The copper sulfides almostinvariablyexhibit a Derivation of metals through magmatic-related strongorthorhombic cleavage (Fig. 8E), whichindiprocesses is considered unlikely for the SanBartolo cates crystallization temperatures below 103C There is no record of igneous rocks (McCauley,1961; Roseboom, 1966). This is in accord mineralization. in the Pacencia Group or in the Cretaceous of the with the previously mentioned stability fieldof anilite area; the middle Tertiary of this sector of the Andes andthat of djurleite,whichconverts to highdigenite to havebeena periodof tectonicquiand high chalcociteat 93C. The absence of chalco- is considered following volcanism andcompression during cite suggests that thisreactionhasnot takenplacein escence Eocene times (Coira et al., 1982). The overlying dacthe Bartolosulfides. Low temperatures are alsoinitic ignimbrites have low copper values (B. Hooper, dicatedby the abundance of atacamite, whichis commonly paragenetically earlier than sulfides. Rose pers.commun.,1983) and mineralizationoccursconlower stratigraphically than the sediments (1976) showed that the atacamite stabilityfield on siderably in contact with these volcanics. Furthermore, minEh-pH diagrams virtuallydisappears above75C. eralization shows no relationship to any of the nuTable 1 shows that the secondary coppersulfides merous normal and thrust faults that cut the succesare enriched in bothsilverandgoldoverthe primary sion. Apart from the localized breccia-filling minercopper-iron sulfides. This enrichmenthasbeen docalization in Quebrada Palicaye, there is no significant umentedin other similardeposits suchas Alderley The simpleore minerEdge, Cheshire,England(Ixer andVaughan,1982), vein style of ore deposition. alogy and absence of gangue mineralsalso argues andCaletoColoso, Chile (Flint et al., 1986). against an igneous hydrothermal origin. Postmineralization Diagenesis Lead isotopestudies After mineralization and subsequent oxidationof copper-ironsulfides to "chalcocite"and covellite in In recent yearsthe measurement of lead isotope the vein ores and after oxidation of sulfides and native ratiosin sulfide orebodies hasprovided a potentially copperto cuprite in the matrix mineralization,a less useful tool for determining the ageof mineralization important pulse of copper-richchloride solutions is (applicable mainlyto Precambrian deposits) and for recordedby the precipitationof late atacamite over- fingerprinting possible sources of lead, andby impligrowths on diagenetically modifieddetrital minerals cation,other metalsin the deposit(Doe and Stacey, andorephases (Fig.6E). Coppersulfides wereclearly 1974; Sangster,1976). Sediment-hosted ores with out of equilibriumwith the latter diagenetic environ- highly radiogenic, anomalous leadsare commonly ment,commonly showing progressive replacement by considered to haveformed by remobilization of metals truly secondary atacamite (Fig. 8E). The presence of from olderuppercrustalsources. Mississippi Valleythis later atacamite suggests that later groundwater type lead-zincdeposits and certain red-bed copper wasat one stagechloriderich and highly oxidizing. occurrences are thoughtto haveformedin this way Afterthe termination of the mineralizing events, nor- (Doe and Delevaux, 1972; Sangster, 1976; Ruxton, mal diagenesis resumed in response to the physico- 1981; Bjorlykkeand Thorpe, 1982). chemical conditions of burial and ground-water cirLead isotopestudies were undertakento characculation.Further SEM studyhasindicatedthe pres- terize possiblesources for the metalsat SanBartolo. enceof silicaandalbite overgrowths on ore minerals, Possible source areas to the east of the basin are now alongwith increased quantitiesof authigenicalkali obscured by latervolcanics. Seven samples of copper feldspar whichcommonly overgrew earlierdiagenetic sulfides (four from veinlet mineralization and three phases (Fig. 7). frommatrixmineralization) were obtained by acom-

actingonhypogene chalcopyrite andbornitc(Sillitoe and Clark, 1969). Normal and blaubleibendercovellitesreplacing

Source of the Metals

ORE GENESIS CONTROLS, SANBARTOLODEPOSIT

773

binationof microdrilling andcrushing to - 150 mesh, followed by heavyliquidseparation. Afterhandpicking, 100 mg samples were dissolved in nitric acid. After centrifuging,residueswere dissolved in HBr and passed twice throughanionexchange columns. The lead wascollectedby 6M HC1, loadedon single rheniumfilaments with phosphoric acid,andfusedin silicagel. Measurements were carried out on a V. G. Micromass 30 solid-sourced massspectrometer operatedat 2.4 A and3.5 kG overa temperature range
of 1,150 to 1,400C.

from a calc-alkaline basin.

source area to the east of the

Without isotopicmeasurements of the now inaccessible crystalline source rocksit is difficultto rule out the possibility that the measured ratiosrepresent the mixingof lead from two sources. One alternative could involve the mixing of a mantle-derivedcomponent (e.g., midoceanic ridge basalt,MORB) with radiogenic leadfromthe hostarkoses. However,geologicevidence indicates that the metals were derived
from the same source as the host rocks. The Pacencia

Groupis of Oligocene-Miocene ageandthe timingof ore genesis is pre-upper Miocene. Thus, there was probablyinsufficient time for the sandstones to generatemuchradiogenic leadthroughthe decayof uranium or thorium. Therefore, while a mixing event been derived from an earlier sediment-hosted ore decannotbe dismissed on the availableisotopicdata, posit(Ruxton, 1981). The isotopic signatures obtained the similarityof lead in the oresto that of Andean suggest thatthe oreswerederivedfromvolcanogenic andesites supports a common source. sources which is in accordwith provenance studies In a recentisotopic studyof porphyrycopperdeshowing that the Artollahostsediments were derived posits in Colombia, SillitoeandHart (1984) discussed possible ultimatesources of lead in suchAndeanenvironments. Many of theseColombian porphyrydata (Fig. 10) lie in a field similarto the SanBartololeads. The descending Nazcaplate is discounted as a lead source, asis the overlyingmantlewedge(assuming it 38.5 doesnotpossess the unusually radiogenic leadisotope 208p b Sedimentssignatures of certainoceanicislands suchas St. He204- lena).SillitoeandHart pointedoutthatthe sediments overlyingthe Nazcaplate canbe isotopically divided intotwocategories. The basal metalliferous sediments overlying the basaltic crustcontain leadthatislargely derivedfromthe oceanic crustitselfthushaving mid37'5 oceanic ridgebasalt values. Theseare overlain by pe15.7 lagic sediments which containlead derived through the weathering of continental crust(Fig. 10). It isthis second lead which the aboveauthorsconcluderep15 '6 resents the major source of Pb in porphyrysystems in the oresfrom SanBartolo.Varia207pb *"*'**c "* Sedimentsand, it appears, tions from this field may be attributed to selective 204-p-pb contamination by uppercrustal leadsof variableiso15.5 topic characteristics. An exampleof suchcontaminationis givenby Barrieroand Clark (1984) where relativelynonradiogenic leadisotope ratiosin andes15'4 ites are explainedin terms of contamination from 18.2 18'4 18'6 18'8 19'0 metamorphic basement.

The isotopic valuesobtained(Fig. 10) are similar to thoseof Mesozoic to Paleogene calc-alkaline volcanics from southern Peru (BarrieroandClark, 1984) and the Copiapoarea of northernChile (McNutt et al., 1979).Theyarenotsufficiently radiogenic to have

39.0

38.0

204-js'-ff
FIG. 10. Lead isotopecompositions of coppersulfides from the SanBartolo deposit. Circles represent matrixsulfides whereas squares are the measuredcompositions of veinlet sulfides.The fieldsof leadisotope compositions for Nazcaplatebasalts (npb) and Mesozoic-Paleocene volcanics (sp)from Peru (Barrieroand Clark, 1984) and andesites from the Copiapoarea of northern Chile (ca,McNuttet al., 1979) are shown for comparison. Other fieldsinclude Colombian porphyry coppers (Cpc)andsediments fromthe subducting Nazcaplate(Pacific sediments) after Sillitoe
and Hart, 1984.

206pb

Transportand Deposition Major problems in the understanding of low-temperaturebasemetaldeposits includesource of metals, the mechanism of transporting copper,and related constituents to sites of deposition andsubsequent fixation of the metal(s),commonly as sulfides, in what is generallya highlyoxidizingenvironment. Several authors (e.g.,Brown,1971; Rose,1976) haveshown that the solubility of copperin terrestrialground water at neutralpH levelsis ostensibly lessthan 1 ppm,

774

s. FLINT

but its solubility is considerably increased in chloride- sandstones andonlyovera restrictedstratigraphic inrich solutions. Dissolvedcoppervaluesof 6 ppm or terval, coincident with the unroofing of a favorable greatermay be quite adequatefor the eventualfor- source area. mationof an ore deposit,givena suitableconcentraThe paragenetic position of galenais interesting in tion mechanism. this discussion. In the first model, where copper is Almost without exception, economic sediment- released fromdetritalferromagnesian minerals during hosted copperdeposits are hosted by successions that arid weathering,lead, which is normallypresentin containevaporites(Gustafson and Williams, 1981); resistantalkali feldspars,is released later during this striking correlationhas led severalauthorsto deeper weathering (Bjorlykke and Thorpe, 1982). to weatheringof alkali feldsuggest thatthereisa genetic linkbetweenevaporites, This greater resistance chloride brines,andcoppermineralization (Davidson, sparscomparedto ferromagnesian mineralshas al1965; Renfro, 1974; Rose, 1976). In this contextthe readybeen notedin the Artolla sediments. This proearlyparagenetic position of the oxychloride atacam- cessshouldresult in lead being either lost from the due to its greater solubilitythan copper in ite is interesting. It hasrecentlybeen suggested that system (whichmaybe why leadvalatacamiterepresentsan early phasein certain red- terrestrialenvironments uneconomic in thisclass of deposit) bed deposits, precipitatedfrom an evaporite-derived uesare commonly cupric chloridesolutionunder conditions of high Eh or precipitatedas paragenetically late galena.The at SanBartoloappearto be both precopper andmoderate to low pH, with temperatures probably galenas and postcopper lessthan 50C (Flint, 1985b and c). As alreadydis- (foundin early evaporiticcements) to blue coppersulfides). cussed, evaporites forma significant proportion of the (assmallinterstitialgrains A third alternative model could involve the transsedimentarysuccession in the San Bartolo area and the entire distance from the atacamite, although occupying a complex paragenetic port of metalsin solution source areato the SanPedrobasin. A modposition,doesappearon textural groundsto be the crystalline ern exampleof thisprocess is foundin the La Exotica earliestcopperphasein manysandstones. A possible mechanism of coppertransportin this depositnear Calama (Fig. 1) where chrysocolla-cesetting could be via ferric oxide grain coatings mentedgravelswere mined for someyearsnear the (Holmes et al., 1983), derived through diagenetic giant porphyry deposit of Chuquicamata(Munoz, is thoughtto havebeen prebreakdown of copper-rich detritalminerals (e.g.,au- 1975). The chrysocolla groundwater derived gites and hornblendes), althoughsuchphases were cipitatedfrom copper-bearing probably uncommon in the granodioritic provenance throughweatheringof the adjacentporphyry(Newareasof the Artolla sediments.Furthermore, because berg, 1967). A similarprocess could have supplied of the low metal concentrations in such minerals, a copper in the San Pedro basin.However, when the and Exoticaare conlarge volumeof sedimentis neededfor scavenging relative sizesof Chuquicamata whetherthisprocess alone by chloridesolutions. Holmeset al. (1983) argued sidered,it is questionable that the redistribution of metalsduring red-beddia- could transport copper in solutionfor the much to form the muchhighergradeores genesis couldprovidean adequate source of copper greaterdistances to form ore deposits. In their example,a 100-m thick- at San Bartolo. It is the author's view that some form above,is necness of the SherwoodSandstone Group of central of particulatetransport,as discussed to introducethe metalsinto the basin.Fluid England, having anareal extent of3.4 X 109 mewould, essary duringthe assuming an averagecoppermobilization of 1 ppm, transportis certainlyan importantprocess later intrabasinal ground-water circulation. yield over 800,000 metrictonsof coppermetal.
An alternative model could involve the erosion of

largeareas of low-grade bed-rock mineralization. The Sulfur isotopestudies petrographyof the host sands and the lead isotope data fit with the erosion of a calc-alkaline volcanoSulfur isotopestudies were carried out on copper and evaporiteminerals in an attemptto eluplutonic complex.If this sourcearea carried por- sulfides phyry-style low-grademineralization, then suchma- cidate the mechanism of sulfide fixation in the sandterial would be reflected at an appropriatelevel in stonesof the Artolla Member and to test the theory the unroofing sequence. At SanBartolothere is,how- that the evaporites provideda sulfursource for later ever, no evidence ofmineralized clastsor detrital sul- diagenetic sulfide fixation. Samples were obtained by fides.Possibly the relatively distal sedimentological a combination of microdrillingand crushing to -150 settingwould make the continuedsurvivalof such meshfollowedby heavyliquid separation, in a manner Sulfurwasexmaterial unlikely, althoughdetrital bornite grains similarto that for lead isotopestudies. have been reported in graywackes of the Zambian tracted fromthe samples foranalysis asSO2.Sulfides copperbelt(Binda,1975). This modelwould explain were oxidized at 1,070Cwith cuprous oxide(RobandKusakabe, 1975) andsulfates wereprepared the apparentstratigraphic and sedimentological con- inson trols on mineralization with copper found only in for analysis asoutlined by Coleman andMore (1978).

OREGEHESIS COHTROLS, SAH BARTOLO DEPOSIT

Measurements were carried out on a V. G. Micromass

775

was derived from mixed sources which could include

602C gas-sourced massspectrometerfitted with a evaporites of the olderPurilactis Formation. heatedinlet system to avoidmachineisotopicfracof bleaching and reduction tionations. All gases were run against internal stan- Mechanism dards and the data were corrected for instrumental As statedat the beginning of this paper, the maand isotopiceffects(Coleman,1980). jority of the ores at San Bartoloare not obviously Results for coppersulfides (Table2) showa spread, associated with preservedorganic material. Nevthe sulfurisotoperesultsstronglysuggest but all are enriched in the light isotope. A wide range ertheless, were precipitated throughbiogenic of values wouldbe expected frombiogenic reduction that the sulfides of sulfur,whilethe isotopically lightsignatures would sulfatereduction. It is possible, therefore,that bacbe consistent with reduction under conditions of unteria canexistin sufficient abundance to reducelarge limited sulfur supply. There is minimal variation quantities of sulfatewithoutthe necessary preservaof organic substrate. The feeding in isotopic values between primary chalcopyrite tionof largevolumes (-33.788%0) anditschalcocite groupoxidation prod- trailsandrare algallaminae preserved astracefossils ucts(-33.527 to -33.786%0) in the veinlets,but ma- in the Artolla sandstones indicate that environmental on the playasurface-subsurface were not trix sulfides do appearto showgenerally heavierval- conditions ues (-12.634 to -27.603%0). A possiblereasonfor sufficiently hostileto inhibit the development of inthe heaviervalues in theseearlymatrixsulfides could vertebrate(andthereforeprobablybacterial)life. be the limited amountof sulfateavailablein preexSomeof the sulfideveinletsat Palicayeare, asdisisting intergranulargypsumand celestite cements. cussed above,an infilling of invertebrateburrows, With limited sulfateavailable, the system couldshift with localizationof ore due to the former presence toward closedsystemfractionation which is known of syngenetic organic material. The elongate stringers to resultin the production of progressively heavier and circular nodules of native metal-oxide ore were valuesasmore sulfateis usedup (Rye and Ohmoto, probably formedasa response to a reducing microen1974).The veinlets of oreminerals commonly replace vironment surrounding small concentrations of similar evaporite minerals deposited in the tectonic breccias syngenetic organicmaterial, as documented on a aroundthe Palicayemines.In these veins the rela- largerscale in otherdeposits (Woodward et al., 1974; tively large supplyof sulfateprobablyensuredthe Ripley et al., 1980). It is difficult,however,to explain preservation of an opensystem, leadingto light iso- the deposition of the greater fractionof the ore by this mechanism. There is no evidence of extensive tope enrichment. Isotopic results for the sulfateminerals are consis- syngenetic organic remains andyet extensive bleachtentwith thismodelof mineralization. The evaporites ing andsecondary porosity generation haveoccurred. are considerably lighterisotopically thanthosepro- As outlinedabove,copperdistribution is controlled ducedby evaporation of normalmarinewater. The by sedimentary facies andsubsequent diagenesis. The data supportthe sedimentological interpretation of mechanism of bleaching andreduction musttherefore thesedeposits as continental playa deposits; sulfur involvethe movement of a fluid,whose passage was
TAILE2. SulfurIsotopeCompositions of Copper Sulfides and Earlier EvaporiteMineralsin the SanBartoloDeposit

Coppersulfides

Sample number
5904
44497 44620 45507
44620

Mineral
Chalcopyrite
Digenite Digenite-anilite Djurleite
Bornitc

Lithology
Brecciated sandstone
Brecciated sandstone Brecciated sandstone Brecciated sandstone
Brecciated sandstone

Del a4S (permil)

-33.788
-33.527 -33.786 -29.680
-36.483 Veinlets

5894 5879 45517

5895

Digenite-anilite Djurleite Digenite

Covellite

Undisturbedsandstone Undisturbedsandstone Undisturbed sandstone

Undisturbed sandstone

-27.603 -23.458 - 17.444

- 12.634

Matrix

Preore evaporateminerals 44618 45480

45459

Gypsum Anhydrite
Celestite

Vein in sandstone Nodular, bedded

Matrix to sandstone

2.445 4.572
6.589

45543

Gypsum

Bedded,after anhydrite

3.413

776

s. FLINT

rences,is interestingfor severalreasons. Firstly, it is at least economically, an oxide orebody,with only minor but geneticallyimportant sulfides.Secondly, the oxychlorideatacamiterepresents at leastlocally a primary phaseprecipitated from a cupric chloride transport fluid.There are strong sedimentological and terial indicate that this substance was introduced after diagenetic controls on mineralization, both of which with a geneticmodelof detritalcopperthe generationof the calcite-destroying secondary are in accord porosity. The paragenetic position of thisorganic ma- bearingmineralsderived from a volcanogenic crysterial, enclosing earlier, largelydissolved matrixce- talline source area to the east of the San Pedro basin. ments and following overgrowth formation is re- These mineralsexperiencedthe same sedimentary as other detrital phasesdepositedas part markablysimilarto that of similarsubstances docu- processes mented in sandstoneuranium deposits of the of the playa detritus of the Artolla Member. This southwestern United States. Bleaching hasbeenused modelis further reinforcedby lead isotopedata. asa field aidto identifyuraniferous sandstones in these During later diagenesis of the sedimentary pile, deposits (Grangeret al., 1961). Studiesof the host chloride-richgroundwater, derivedthroughrelated of the abundantevaporites in the successandstones in the Jackpileand other deposits of the diagenesis unecoLaguna district, New Mexico (Moench and Schlee, sionleachedcopperfrom thesedisseminated, detrital minerals andredepos1967), showthat the ore mineralsoccur as a matrix nomiccopper-bearing to detrital and earlier authigenic minerals. The fact ited the metal in the Artolla sandswhere physicothat the organicmatrixat SanBartoloencloses relict chemical conditions must have been favorable for the passage andconcentration of thesebrines. crystals of earlier calcitecementandembays the sil- continued was the formation icatessuggests that a similar preore secondary po- The result of the aboveprocesses The stabilityrelationsof atarositygeneration tookplacein thesehostrocks. The of high-gradedeposits. corrosive nature of this process pointsto a fall in pH camite (Fig. 9) indicatethat deposition is enhanced levelsfrom the relativelyalkalineinterstitialcondi- by medium to low pH values, low temperatures tions, characteristicof red-bed diagenesis,which (<50C), and high Eh. Given a high chlorideion ac-

controlledby thesehost-rockcharacteristics. The remainsof a brown, semiopaque organicsubstance is foundin rarespecimens (Fig. 8F). Thismaterial occurs asa precopper matrixwhichappears to replace earlier calcite. Textural relationshipsincluding rare, corrodedcalcitecrystals enclosed within the organic ma-

tivity it is possible that this mineralcouldrepresent The similarityof the SanBartolodepositto these a primaryore mineral (Flint, 1985b). The factthatthe ore deposits at SanBartolocontain uraniumoccurrences may indicatea related genesis. syngenetic organic material isat variance The porosity generation andlocalization of ore in the little obvious latter case was due to the introduction of acidic, re- with manydocumented red-beddeposits where such ducing ground water. The mobile (epigenetic)re- materialprovideda localizedreducingenvironment, ductant is considered to be a water-soluble humate promotingsulfide 'precipitation (Gustafson and Wilmany common feaderivedfromdecaying plantmatter.Much of thisma- liams,1981). The depositshares terial remains as an insoluble residue in the uranifertureswith somesandstone uraniumdeposits where a wasproducedthroughthe inoussandstones (Moenchand Schlee, 1967; Turner- reducingenvironment humates.In this Peterson,1985). As previouslystatedthere are only troductionof epigenetic,dissolved introducedorganicmatter smallamounts of a similarepigeneticorganicmatrix modelthe epigenetically for sulfate-reducing bacteria. in the SanBartolohostsandstones. In light of the oth- would act asa substrate cansurvive in lithified sediments at erwisegeneralsimilarities with the urahiferous sand- Theseorganisms of over 90C (B. Spiro,pers.commun., stones, possibly muchorganicmaterialhasbeen re- temperatures indicated movedduringlater oxidativediagenesis, which is in- 1985), which are similarto temperatures mineralassemblages presentin the dicated by late atacamite and alkali feldspar by the diagenetic Artolla host rocks.The evaporitesulfatecouldhave overgrowths to sulfides. biogenic Furthermore,the origin of dissolved humates has provideda sulfursourcefor the subsequent been attributed to a sourcein overlyingboggyma- reduction to sulfide, which would then combine with terial in the New Mexicoexample.The modernSalar the copperionsin the intrastratalchloridesolutions copper-bearing sulfides. de Atacama is hostto severallargeareas of vegetated to form the observed The paragenetic relationship amongother phases standing water which, duringburial, could act as a sourcefor dissolved humates. Thus,althoughthe San is more difficult to explain, particularly the alongPedro area is believed to have been arid since the strikepassage frommatrixoxideandnativemetalinto Cretaceous, this need not rule out the existence of sulfides. Whereasmuchof the cupritewasoriginally native copper,it is difficultto accepton the rare evboggyareas. idence of sulfides overgrown by cuprite that all the Discussion and Conclusions mineralization wasoriginallysulfide.Furthermore,if The SanBartolocopperdeposit, although smallby the deposit wasoriginallysulfidethen relict sulfides the standardsof economic red-bed copper occur- should be present in freshunderground materialfrom

would have favored the earlier calcite cementation.

OREGENESIS CONTROLS, SANBARTOLO DEPOSIT

777

analyses. Lead isotopework wascarriedout at Leeds with the help and adviceof Bob Cliff and JonDavidson. The original manuscriptwas improved greatly of the reviewersand the uated in similararid, highly oxidizingenvironments by the critical comments editorialboardof Economic Geology. This paper was (Woodwardet al., 1974; Ripley et al., 1980). Differing intrastratalconditionsalong strike pos- written during tenure of a Natural EnvironmentResiblyresultedin the precipitationof nativecopperat searchCouncil researchstudentship. Artolla and sulfidesat Palicaye. These differences could have been in Eh-pH relationships with lower November29, 1984;June4, 1985 pH valuesfavoringsulfideprecipitation.At constant REFERENCES temperatureand Eh conditions, the precipitation of native copper depends mainly on pH (Fig. 9). An
the Artolla mine, especially as these minerals are found in weathered outcrop in the Palicaye area. Copper sulfides are preservedin other deposits sitadded factor could have been local variations in the

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