Economic Geology

Vol. 82, 1987, pp. 1431-1452

Quiruvilca,Peru' Mineral ZoningandTiming of Wall-RockAlteration Relative to Cu-Pb-Zn-Ag Vein-Fill Deposition

PAUL J. BARTOS
ASARCO lnc., Rocky MountainExploration Division,9305 WestAlamedaParkway,Suite202, Lakewood, Colorado80226
Abstract

Quiruvilca district Cu-Pb-Zn-Agveins have producedover 8 million tons of ore since 1789. The veinsoccupytensiongashes associated with left-lateralstrike-slip faultsthat cut the central facies of a Miocene andesitic stratovolcanocomplex. The district has four broadly concentricmineralogiczones from district center to edgeswhich are based on dominantvein fill: enargite,transition, lead-zinc,andstibnite.All veins,regardless of zonal positionin the district, share the samefour grossparageneticstages: pyrite, base metal, sulfosalt, and carbonate.Veins closest to the center of the districtcontainrelatively greater proportionsof the earlier assemblages. Mineralogiczoning commonlyis focusedon vein intersections and on a local scalereflectschanges in vein width. Wall-rock alterationtypesfrom the vein marginoutwardand from mostintenseto least intenseare intensesericitic,strongsericitic,moderatesericitic,strongargillic,weak argillic, andpropylitic.Petrographic observations indicatethat at anygivenlocation,propylitic alterationis oldest,followedby argillic, and then sericiticalteration.The zoned alteration halosformed as each inner assemblage advanced,overprinted, and replacedits adjacent outerprecedent. The width andintensity of alteration halosenclosing veinsincrease with depth and toward the district center. Correlationbetweenparagenetic stages of vein fill andwall-rockalterationis basedupon the mineralogyandwall-rockalterationof single-stage veinletsthat are zonedaboutmajor veins.The veinlet sequence in time correlates with the veinlet distributionin space; this also matchesthe time-spacesequencedocumentedfor major veins. Most alteration occurred contemporaneously with the pyrite stageof mineralization.Ore deposition followedin the basemetal stage.Thus, ore depositionin the veinsin large part postdatedformationof the alterationhalosassociated with thoseveins.This time sequence is corroborated by breccia dikeswhich cut alterationhalosbut precedethe basemetal stage. Temperatures of ore deposition, deducedfrom the stabilityof variousmineral assemblages, decreased throughtime from 320 to <230C. Fugacityof sulfur(rs2)decreased

(from ' 10-6to <10-12'5) both withtimeand laterally away from thedistrict center. ThepH
is inferred to have increased laterally away from the center of the district and to have decreased in time at any one spotin the wall rock.
Introduction

THE Quiruvilca district is located in north-central Peru, 80 km east of the city of Trujillo (Fig. 1). Mining at Quiruvilcahasbeen documented asearly as 1789 (Santolalla, 1909) and the total recorded production of the district has exceeded 8 million tons. Reserve grades are 2.85 percent Cu, 1.97 percent Pb, 5.78 percent Zn, and 7.25 Troy oz/ shortton Ag (Wippman, 1984). Veinsat Quiruvilcaare zoned(Fig. 1) from a copper-rich, enargite-bearing central zone to leadzinc-silver-manganese outer zones (Lewis, 1956);
the district resembles other base metal lode de-

tailed mapping and petrography of vein-fill paragenesis, mineralogic zoning,and temporalrelations between veinlets and pervasive alteration halos aboutlarge veins.
General Geology

positssuchas Julcani,Peru (Petersenet al., 1977; Benavides,1983), and Butte, Montana (Meyer et al., 1968).

A selectedarea (Coco-LuzAngelicaarea) in the southeastern portion of the district (Fig. 2) was mation, an extensive Miocene intrusive-extrusive chosen asthe focalpoint for studies involvingde- andesitcpile with an estimated thicknessin excess
0361-0128/87/718/1431-22 $2.50 1431

The oldest rocks exposedin the Quiruvilca area are Lower Cretaceous clastic sedimentary rocks that were folded and affectedby regionallow-grade metamorphism during the early Tertiary, 40 to 65 m.y. ago(Benavides, 1956; Hollister, 1977). Extensive Jurassic saline depositsexposedapproximately 150 km northeastof Quiruvilca (Benavides,1968, fig. 4) may underliethe districtandhavebeen proposedas the sourceof sulfur (Petersen,1970). The mineralizationis hostedby the Calipuy For-

1432

PUL J. 15RTO$

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QUIRUVILCA, PERU: MINERAL ZONINGAND TIMING

1433

Legend

x'" '

79600E/ '
/ 72

% 05
I0 80

80yVein, showing dip

[] Andesitc flows,
flow breccias

RIGHT .-

0 .-' -".'_' --. 7

88, -""
j,.r88

Andesire
intrusions
lacustrine
sediments

- ^ 87

?[] Tuffaceous

LA MERCED +2 /--

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!800N
.'"./0

LAMERCED / ./ 80 6 ?

80 65

5
.oo
J
LINE

VERDUN.-,

OF SECTION

850N

lOOm

FIG. 2. Surfacegeology,Coco-LuzAngelicaarea. Modified after Corporacion Minera Nor Peru

maps.

of 2,000 m (Cossio, 1964). At Quiruvilca,the Cali- and on the radial orientations of flows, flow brecpuy Formation consists of porphyritic andesitc cias, and tuffs which dip away from andesiticplugs flowsand flow breccias interlayeredwith thin basalt (Bartos,1984, fig. 6). flows and occasional tuffaceous lacustrine sediRegional left-lateral strike-slip faults controlled ments (Lewis, 1956; Bartos, 1984). Zoned, euhe- the localizationof dikes,domes,and veinsat Quirudral to subhedralplagioclase (An47to An54)com- viica. Veins are principally containedin two steeply prises 95 to 99 percent of the phenocrystpopula- dipping fracture sets,one trending N 60o-70 E, tion of the andesites and averages 20 percent of the the other N 85 E-S 85 E (Figs. 1 and 2). The N rockvolume.Mafic phases are hornblende andpyr- 85 E-S 85 E fracture set is part of a group of oxene,with pyroxenepredominating. The ground- regional strike-slip faults, centered at Quiruvilca massis orthophyric, composed dominantlyof equi- and extending for at least 16 km in strike length granular hypidiomorphic plagioclasemicrocrysts (Giesecke,1978). Mineralization is preferentially located in the N 60o-70 E fracture set, which is with pyroxeneand minoraltered glass. Intrusive rocks include andesitc stocks,dikes, and interpreted as a set of tension gashesrelated to plugs; a premineralization-alterationquartz mon- east-westleft-lateral shearingon the N 85 E-S 85 zonite porphyry stockexposed2.5 km north of the E faults (Lewis, 1956). district (not shown) which is cut by several small Faulting occurred before, during, and after minPb-Zn-Ag veins;a seriesof intenselysericitizedda- eralization.Evidencefor premineralizationfaulting cite (quartz porphyry) stocksand dikes in the cen- consists of: (1) breccia dikes and quartz porphyry tral enargite zone that are believed genetically stocks and dikeswhich intruded alongfracturesthat linked to mineralization(Lewis, 1956); and a zone later served as sites f)r veins, and (2) veins deposof unmineralized,slightlypropyliticallyaltered da- ited in faults which cut and offset earlier faults cite domesthat postdate mineralization(Fig. 1). (Lewis, 1956). Local brecciatedsulfidegrainsand

The geologicenvironment of the Quiruvilcadis- vein fragments cemented by late carbonate suggest
trict is interpreted as the central facies of an andes- minor synmineralization faulting. Minor postminer-

itic stratovolcano complex basedon the presence of alizationfaultingis shown by sheared vein material, andesiticplugs,numerousdikes, and smallstocks of fault gouge, and slickensides; the last two occur in andesiticand dacitic (quartz porphyry) composition veins of all orientations.

1434
Mineralization

PAUL J. BARTOS

Veinsin the Coco-LuzAngelicaarea In the Coco-Luz Angelica area, there are two major vein systems: Coco and Luz Angelica (Figs. 2 and 3). The Coco vein systemconsists of Coco, the Cocosplits,the Elbas,and the Right veins.The Luz Angelica vein systemconsists of Luz Angelica, the Luz Angelica splits, the La Merceds, and perhaps the La Compania veins.The Luz Angelicavein fills a major east-west shearzone. The veinsin the Luz Angelicavein systemappear to coalesceat its western end. In the Coco-Luz Angelica area, the only other vein with significantdevelopmentis the Verdun vein whosewesternportion strikesN 60 E. To the east, the Verdun vein changesorientation to N 15 E and intersects the eastern portion of Luz Angelica.

General vein characteristics

Mineralization at the Quiruvilca district occursin over 100 veins, including about 60 that have been developed for mining. Mineable vein widths average 0.3 m and locally may reach widths of 2.5 m (Giesecke,1978). Veins at Quiruvilca tend to have extensivelateral and vertical continuity, though with abundant splits,cymoidloops,andpinch and swellstructures. In places,a vein may consist of a seriesof thick ore shoots connectedby thinner, subeconomic to noneconomic crossings. In general,however.ore-grade mineralization is present throughout the entire vein, a condition similar to Anaconda-ageveins at Butte, Montana (Meyer et al., 1968). At depth, veins within the central enargite zone widen, but zoningof veinfill gradesdecreaseowing to increasing proportionsof District-scale pyrite (Watson,1966; W. Eberhart, pers.commun., Mineral zonesof the Quiruvilcadistrictare based 1981). The gradesat depth in outer zone veins are on the mineralogyof the vein filling, which varies unknown because those veins have not been suffi- laterally on a district scale(Lewis, 1956). From the center of the district outward, these zones are the ciently explored. Veins at Quiruvilea typically are coarsegrained enargite, transition, lead-zinc, and stibnite zones zonesappearto and massivebut locally may be vuggy. In many (Fig. 1, Table 1). Thesemineralogic placesthere is well-developedasymmetrical band- expandwith depth (Lewis, 1956, p. 56). Descriping. The bandsare usuallyxenomorphie aggregates tion of the transition and lead-zinc zones is based on of sulfidesand gangue,commonlywith gangue- relations seen in the Coco-Luz Angelica area; description of the enargite and stibnite zonesis based filled vugs. Contacts between vein and wall rock are comprincipallyon Lewis (1956), supplemented by samat selectedsitesoutsidethe monly sharp and slickensided(Lewis, 1956). The ples and observations dominantprocess of deposition wasby open-space Coco-Luz Angelica area. filling; replacementoccurredto a much smallerexFor simplicity, veins can be divided into three tent. typesbasedon the dominantvein fill: pyrite, sphalN20W LOOKING NORTHEASTERLY S20E

'" .000
LEVEL

79 )OE

,8DON

-130

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3870
LEVEL
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-... . .... ,:...

LEVEL

3720
LEVEL

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PROJECTED VEIN

3600m

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VERTICAL

EXAGGERATION

FIG. 3. Cross section of the CocoandLuz Angelica veinsystems in the Coco-Luz Angelica area.Line of section shown in Figure 2. Levels(exceptfor the 220) correspond to the elevationabovesealevel in meters.ModifiedfromCorporacion MineraNor Peru maps.

QUIRUVILCA, PERU:MINERAL ZONING AND TIMING

1435

TABLE l.

Definition of Mineralogic ZoneBoundaries andAccompanying Vein Types(based in partonLewis,1956)

Zone
Enargite
Transition

Innerboundary
Absenceof enargite Presenceof megascopic galena
Presence of abundant stibnite

Outerboundary
Absenceof enargite Presenceof megascopic galena
Presence of abundant stibnite

Vein types I
Pyritic

Lead-zinc Stibnite

Pyritic, sphalerite-galena, (carbonate-base metal), (calcite-clinozoisite) (Pyritic), sphalerite-galena, carbonate-base metal, (calcite-clinozoisite) Sphalerite-galena, carbonate-base metal, calciteclinozoisite?, quartz-stibnite

1Vein typesin parentheses are uncommon

erite-galena,and ganguedominant--the latter are principallyfilled by carbonate but locallyare dominatedby quartz.The centralenargitezonehasonly pyrite veins. Within the transition zone, pyrite veins are the most common,but minor sphaleritegalenaandcarbonate veinsare present. Theselatter two mayrepresentdistalportionsof pyrite veins(as at Coco). In the lead-zinczone, all three vein types are found. The looselydefined stibnite zone consistsof quartz-dominatedveins with stibnite and gangue-dominated basemetal veins (Table 1).
Pyrite veins

vol percent and averages 25 to 30 vol percent. Sphalerite-galena veinsshowconsiderable variation in the relative proportionof vein-fill mineralsalong strike.Alongsuchveinsare bandsof distinctlydifferent mineralogicabundanceseparatedby fault gougeor highly altered sliversof wall rock. Generally the bandsare 15 to 25 cm wide and consist of varying proportionsof sphalerite, pyrite, galena, tetrahedrite-tennantite, manganocalcite, rhodochrosite, quartz, dolomite,calcite,and inclusions
of wall rock that have been altered to a white seri-

cite + kaolinitcgouge.Pyrite ___ quartz is commonly found at the marginof sphaleritebands.

Gangue-dominant veins

veins occur in all but the central enargite zone. In the transitionand lead-zinc zonesthey contain pyrite, sphalerite,galena,and tetrahedrite-tennantite asthe principal sulfides. Arsenopyrite,stibnite,and marcasiteoccur sparinglyin the lead-zinc zone and rarely in the transitionzone. Carbonate-base metal veins in the stibnite zone have greater amountsof amounts of rhodochrosite and calcite. stibnite and arsenopyritebut still maintain signifiTypically, pyrite veins are composedof several cant concentrationsof pyrite, sphalerite, and gathick pyritic strandsseparatedby intervals of py- lena. Caleite-elinozoisite veins have the same sulfides rite-rich gouge. The vein filling is coarsegrained andlocallyvuggy.Most other sulfides occurin vugs, and textures as carbonate-base metal veins but also interstitialbetweenpyrite grains,or assmallclotsor contain elinozoisite and manganaxinite. Caleitestringerscutting through the pyrite; the last is par- elinozoisite veins are generally thinner than earticularly commonfor tetrahedrite-tennantite. Enar- bonate-basemetal veins, averaging 8 to 15 cm in gite is commonlyconcentratedinto massive mono- width. Alteration immediately adjacent to ealeitemineralic bands which meander through the vein, elinozoisiteveins is strongargillie rather than serierie. Caleite-elinozoisite veins occur in the transitending to favor the vein walls (Watson, 1966). tion, the lead-zinc, and probably the stibnite zones. Sphalerite-galena veins

Pyrite veins are here defined as containing>50 vol percent pyrite, but they typically have a much greater pyrite content.In the central enargitezone, pyrite veins also contain enargite, with minor amounts of sphalerite, tetrahedrite-tennantite, chalcopyrite, and orpiment. Gangue includes quartz, calcite, and barite. In the transition zone, pyrite veinshave no enargite, major sphaleriteand tetrahedrite-tennantite, and traces of galena and chalcopyrite. Gangue includes quartz, dolomite, and manganocalcite. In the lead-zinc zone, pyritic veinscontainmajor galenaand sphaleriteand minor tetrahedrite-tennantite, stibnite, arsenopyrite, chalcopyrite, and marcasite. Gangue includes quartz, manganocalcite, dolomite, and limited

Gangue-dominant veinsare here definedasveins

in which the sulfide content is less than the nonsul-

fide content.Generally,the nonsulfide is carbonate; quartz-dominantveins are uncommon.Carbonatedominant veins include carbonate-base metal veins and calcite-clinozoisite veins. Carbonate-base metal

Sphalerite-galena veins are here defined as con- Paragenetic sequence The paragenetiesequenceat Quiruvilca was detaining <50 vol percent pyrite and with sulfides > nonsulfides. Sphalerite content is generally >15 rived from four monthsof undergroundmappingat

1436

P,4ULJ. BARTOS

30.0
_

'

4oo

mC

.)
.,.

PY

E
FIG. 4. Reflected light photomicrographs showing sulfidemineraltextures. A. Pyrite (py, white), breeeiated; replacedby tetrahydrite-tennantite (tt, light gray) and sphalerite (sl, dark gray). Sphalerite appears to have replacedtetrahedrite-tennantite and pyrite. Calcite (ca, black), veined and replaced all sulfides. Suggested paragenetic sequence: (1) pyrite, (2) tetrahedrite-tennantite, (3) sphaleritc, (4) calcite.B. Pyrite(py, light gray),surrounded by arsenopyrite (asp, white).Galena(gl, graywith triangularpits) replacedarsenopyrite. Sphalerite(sl, mediumgray)with ehalcopyrite inclusions (small white spots) locallyreplacedgalenaand arsenopyrite. Quartz (qz, dark gray) replacedgalenaalong cleavage and sphalerite. Suggested paragenetie sequence: (1) pyrite, (2) arsenopyrite, (3) galena,(4) sphalerite, ehalcopyrite, (5) quartz.C. Pyrite (py, light white), eraeke&veinedby ehalcopyrite (ep, white).Galena (gl,lightgraywithtriangular pits)replaced pyrite;replaced by sphalerite (sl,darkgray). Tetrahedrite-tennantite (tt, mediumgray)veinedsphalerite. Chaleopyrite veinedsphalerite and replaced(?) tetrahedrite-tennantite. Calcite(ca, very dark gray)breeeiated, veined,and replacedall sulfides. Suggested paragenetie sequence: (1) pyrite, (2) galena,(3) sphalerite, (4) tetrahedrite-tennanrite,(5) ehaleopyrite, (6) calcite.D. Pyrite (py, white),replaced by sphalerite (sl,darkgray)andby

QUIRUVILCA, PERU: MINERAL ZONING AND TIMING

SULFOSALT

1437

PYRITE

STAGE

BASE

METAL

STAGE

STAGE

CARBONATE

STAGE

PYRITE

ENARGITE/LUZONITE TETRAHEDRITE/ TENNANTITE SPHALERITE

GALENA

CHALCOPYRITE

ARSENOPYRITE
STIBNITE
MARCASITE

ORPIMENT/REALGAR

NATIVE

ARSENIC

ALABANDITE

STANNITE,

CHATKALITE
BOURNONITE

JAMESONITE
HUTCHINSONITE PB-AS-S GLASS

PB-AS-SB-S

SULFOSALTS
BARITE

MANGANAXINITE CLINOZOISITE QUARTZ RHODOCHROSITE MANGANOCALCITE DOLOMITE

CALCITE

TIME

FIG. 5. Generalized paragenetic sequence of hypogene vein minerals, Quiruvilca district. Line
metal stage.

thicknesses proportional to phase abundances. Phases of economic interest (enargite, tetrahedrite [principally foritssilver content], sphalerite, and galena) arealmost exclusively deposited in thebase

a 1:250 or 1:500 scalecoupled with detailed study Uncommoncrosscutting vein relationsmimic the of more than 180 polished blocks, polished thin paragenesis. At the 3800 level of the Luz Angelica sections, andthin sections. Vug sequences andobvi- drift, severalsplitscan be seen divergingfrom the ousreplacementrelationships suchasrelict islands, main Luz Angelicavein to form the Verdun vein. At cleavageveining, overgrowthrims, etc. (Fig. 4) this point, Luz Angelicais a sphalerite-galena vein formed the basisof the parageneticsequence. Ad- with the sulfidescontainedwithin a quartz matrix. ditional informationcanbe found in Bartos(1984). Yet the Verdun vein is composedprincipally of All veinsin the Quiruvilcadistrict, regardless of manganocalcite with minor quartz at the outer marzonal position, display a paragenesis in which four gins;this cutsthe quartz-base metal sulfides of Luz grossstages are present: a pyrite stage,a base metal Angelica.The inferenceis that the carbonate-domistage, a sulfosalt stage, and a carbonate stage nant Verdun vein postdatesthe sphalerite-galena (Fig. 5). Luz Angelicavein.

galena (gl,lightgray,left-hand sideof picture). Tetrahedrite-tennantite (tt, medium gray)surrounded

pyrite. Bournonite (b, slightlylighter), intergrownwith tetrahedrite-tennantite. Sphalerite(sl, dark

gray) replaced tetrahedrite-tennantite along cleavage. Chalcopyrite (cp,verylightgray) veined sphalerite andreplaced tetrahedrite-tennantite. No obvious relations between galena andtetrahedrite-tennantite. Suggested paragenetic sequence: (1)pyrite, (2)galena, tetrahedrite-tennantite, bournonite, (3) sphalerite, (4) chalcopyrite. E. Pyrite(py,white), replaced by sphalerite (sl,gray), andlocally, stibnite (sb,lightgray). Twovarieties of pyritearepresent: "wormy" andeuhedral. Stibnite, replaced (?)by manganocalcite (mc,darkgray). No obvious relations between sphalerite andstibnite. Suggested paragenetic sequence: (1) pyrite,(2) sphalerite, stibnite, (3) manganocalcite. F. Pyrite(py,white),replaced by stibnite (sb, gray). Uncertain relations between stibnite andmanganocalcite (mc,darkgray). Quartz (qz,slightly darker graybleb),surrounded andreplaced (?)by manganocalcite andstibnite. No relations between quartzandpyrite.Suggested paragenetic sequence: (1) pyrite,quartz,(2) manganocalcite,
stibnite.

1438

PAULJ. BARTOS

Another locality where apparentcrosscutting re- of sphaleriteand galenareachesa maximumin the lationsbetween differentvein types occuris along intermediate lead-zinc zone; and the abundance of strike of the Coco vein on the 3800 level, west of arsenopyrite and stibnitereachesa maximumin the the Coco split. There the vein changes from pyrite outer stibnite zone (Fig. 6). The proportion of nonto sphalerite-galena. At the point of change,splits sulfideganguemineralsalsochanges laterally from principally composedof sphaleritewith mangano- the center of the district. Barite is most abundant in calcite, dolomite vug fill cut the pyritic main vein the enargite zone; dolomite reachesa maximumin the transition zone; manganocalciteis most abunsegment. These field relationssuggest a time sequence of dant in the lead-zinc zone; and rhodochrosite and early pyrite veins, intermediate sphalerite-galena quartz are most abundant in the stibnite zone veins, and late carbonate veins, a time sequence (Fig. 6). that is consistent with the parageneticrelationsof Changesin mineral speciesalso occur outward vein fill (Fig. 5) and crosscutting veinlet relations from the district center. Of the copper sulfosalts, enargite is restricted to the central enargite zone, (discussed below).
Zonal distributionof vein-formingminerals
whereas tetrahedrite-tennantite occurs in the outer

zones. Of the arsenic minerals, orpiment and realThe district-scale lateral zoning in the vein fill gar only occurwithin the enargitezone;nativearseinvolves both changes in the proportions of the min- nic and arsenopyriteare principally found in the erals and changesin the mineralogicspecies(Fig. stibnite zone; Pb-As-S glass(Milton and Ingham, 6). Because the different species are from different 1959; Burkart-Baumann and Otteman, 1972) and paragenetic stages, this zoning also involves sulfosalts are found in the interveningtransitionand

changes in proportions of the differentstages from

zone to zone.

lead-zinc

zones.

Changes in mineralogic proportions are striking. The abundanceof pyrite strongly decreases outward; coppersulfosalts are the mostabundantin the inner enargite and transitionzones;the abundance

In short, all paragenetic stages are present in majorveinsof any zone,but the relative abundance of late-stagemineralsincreases toward the periphery of the district (Bartos,1983). The district-scalezoning is also marked by tex-

*--

ENARGITE ___,,,,..__

ZDN

TRANSITION

ZON

LEAD-ZINC

ZON

STIBNITE

ZON

.... ENARGITE TETRAHEDRITE/

TENNANTITE

>o

TO

1%

/ / / /

/:"---

------

>1 TO 5%

SP.LER,TE .......
CHALCOPYRITE

.__///////
o

S8.OYIT

..............

....

ORPIMENT/REALGAR

NATWE

ARSENIC

HOTCHINSONITE -S-S GLSS PB-SB-S-S SULFOSALTS

'

...........................

BARITE MANAAXNTE/ CLINOZOISITE

..................

'

T
MANGANOCALCITE
DOLOMITE
CALCITE

-- /

/ / / / , / / /////

--

FIG. 6. Zonal distribution of vein-forming minerals,Quiruvilcadistrict.Certain minor phases not shownowingto insufficient data.The relativeproportionof vein fill in eachrespective zone is semiquantitative andwasderivedfromthe average of visual estimates of veinfill takenwhenmapping and fromsamples collected by R. Lewisandthe author.Note similarityin appearance to districtparagenesis diagram (Fig. 5). At a givenpoint, earlyphases that characterize morecentralzonesare replacedby later phases that characterizemore distalzones.

QUIRUVILCA, PERU: MINERAL ZONINGAND TIMING

1439

with depth whereasthe tural changes. Typically,the averagegrain size of perhapsdolomiteincreases abundance of spalerite,quartz, and manganocalcite the district.In addition,vein bandingbecomes finer decreases(Fig. 7). In other words, those phases and better developedaway from the center of the more characteristic of veins from inner district-scale district,becomingmostevident in the stibniteand horizontal zones are more abundant with depth. lead-zinc zones. Further, the phaseswhich increase in abundance with depth typically tend to be early in the paraVein-fill zoningin individual veins geneticsequence (Fig. 5). Individual veins commonly show considerable The consistent zoningpatternsseenat all scales, variationin mineralogic abundance alongstrikeand when coupled with the consistentparagenetic sewith depth. An excellentexampleis the transition quence seen in vein fill throughout the district, zone Coco vein, which exhibitsroughlybilaterally suggest that the Quiruvilca veins formed during a symmetriczoningaway from a pyritic core. Later- singlemineralizationevent. ally from the pyritic core, the pyrite and tetraheAlteration drite contentsdecrease,whereas the sphalerite-galena, total carbonate, and perhaps quartz contents with major veins increase (Fig. 7). Vein intersections are clearlythe Pervasivealteration associated foci of the localzoningat Coco;thisis alsoreflected Six distinct types of alteration, based on major by metalratioswhich in additionindicatenear-ver- mineralassemblages andtextures,canbe discerned. tical fluid flow (Bartos,1984; and in prep.). Each alterationtype gradesinto the next so that The lateral variation in Coco mineralogyin part sharp boundaries betweenthemcannot be mapped. corresponds to changes in the vein width. An abrupt From the vein margin outward, these alteration changefrom pyrite to sphalerite-galena dominance typesare intensesericitic,strongsericitic,moderin the Coco vein on the 3870 level (Fig. 7) occurs ate sericitic,strongargillic, weak argillic, and prowhere the vein width constricts eastward from 1.5 pylitic (Fig. 9, Table 2). The firstthree types,comm to 10 to 17 cm. Farther east, the Coco vein lo- prising sericitic alteration, are the following: incallyreaches widthsup to 35 cm andis still sphaler- tense,where wall-rock texture is destroyedand the ite dominant; local areaswith widths greater than assemblage is sericite+ quartz+ kaolinite+ pyrite; this are pyrite dominant. Similarstructural correla- strong,where texture is preservedand the assemtionsto vein mineralogy are observed elsewhere on blage is quartz + sericite+ pyrite; and moderate, the Coco vein (Fig. 8) and on the Right and Elba 3 where texture is preservedand the assemblage is veins (Bartos, 1984). sericite+ quartz+ brownkaolinire+ pyrite + calVertical changes in vein-scale zoningare lessdra- cite. The next two typesmakeup argillicalteration: matic but still significant: at the Coco vein, the strong, consistingof sericite + brown kaolinite abundanceof pyrite, tetrahedrite-tennantite, and + calcite+ pyrite _ quartz, and weak, which con4000m

ore minerals decreases outward from the center of

700W

I OOW

PYRITIC CORE

'

3900rn

LU---'

3755

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--

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--

dl m%

sl--gl PY

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JUNCTION
COCO

WITH
SPLIT

JUNCTION

WITH ELBA

00m

FIG. 7. Longitudinal section, lookingnorthof the Cocoveinshowing lateralandverticalvariations in veinfill. The Cocoveinis a transition zonevein,markedlyzonedalongstrike.Pyriticcoreshown with stronghachures. Horizontalaxisis true scaledistance; verticalaxisis volumepercentvein-fillminerals from 0 to 100 percentestimated at differentsitesalongstrikeof vein. No verticalexaggeration. Abbreviations: ca = calcite,clz = clinozoisite, dl -- dolomite, gl -- galena, ma = manganaxinite, mc = manganocalcite, py = pyrite, qz = quartz, sl = sphalerite, tt = tetrahedrite-tennantite.

1440

PAUL J. BARTOS LINE OFSECTION sl dl

//

//

Ii
sl

PY
, I az IqzJ I sl -py ----g

tt II

VEIN TYPES

oaaSSoA/ N 3720 LEVEL

50 m

CROSS-CUTS &LATERALS,,?

0PYRITIC
SPHALERITE-GALENA

DRIFTS//

CARBONATE-BASE METAL

FIG. 8. Variationsin relative abundance of vein fill for differentvein types alongstrike, Coco-Luz Angelicaarea, 3720 level. Each box represents a visualestimationof total vein fill at that site with vertical scalerepresenting0 to 100 vol percent. See Figure 7 captionfor mineral abbreviations. The changein vein type from pyritic to sphalerite-galena at the Coco vein accompanies a changein vein width (from 35 cm to a seriesof 3-4-cm-wide stringers). At point A, severalstringers have coalesced into a pod 80 cm wide, whichexplains the pyrite-dominant mineralogy. At B, the pyritic Cocovein has narrowed down to a thin gougy zone owing to a strike change;the mineralogylocally changesto sphalerite-galena.

sists ofbrownkaolinite + calcite + pyrite.The sixth

type, propylitic alteration, consists of chlorite

Tourmalineis fairly common in the centralpart of the district (Entwistle and Hollister, 1957) but is + calcite+ pyrite_ illite, brownkaolinite, andepi- absentfrom the Coco-Luz Angelicaarea. The closdike intersected in drill core 75 m north of the Coco
vein.

dote. Relict plagioclase phenocrysts exist in both est known occurrence of tourmaline to the Cocoargillic and propylitic alteration; relict chlorite Luz Angelica area is a tourmaline-bearing breccia

(frompropylitic alteration) exists in weakargillic

alteration(Fig. 9, Table 2). In additionto the three main kinds of alteration, chloritic alteration, concrease in vein width.

Montmorillonites are conspicuousby their ab-

sisting of chlorite + quartz + calcite, occurs locally sencein argillicallyaltered rocksat Quiruvilca. Inbrown, low-relief clay asa distal alteration effector in areas of abruptde- stead,there is a translucent
mineralhere termed "brown kaolinite." X-ray dif-

QUIRUVILCA, PERU: MINERAL ZONING AND TIMING

DISTANCE FROM VEIN

1441

Petrographic textures suggestthat at any one area,propyliticalterationwasearliest,followedby TEXTURE LxAvxv WEAK STRONG IODERATE STRONG INTENSE argillic and then sericiticalteration.In weak argillic LAGIOCLAS RELICT alteration,maficsitesare almostentirely composed CHLORITE ::;= ..... of chlorite (from propyliticalteration)with cloudy patchesof brown kaolinite intermixedwith and apO VARTZ parently replacing the chlorite. Plagioclaseis reCALCITE / placedby calcite,brown kaolinite, and very minor amounts of sericite,illite, and chloritealongcracks and cleavageplanes.In strongargillic alteration, sericiteandpyrite replacethe chloritealongmicroKAOLINITE : // /,/./ fracturesand in patchyzones.Sericite,calcite,and
MINERALS/ & ROCK PROPYLITIC ARGILLIC ,fiERICITIC
ILLITE

KAOLINITE
PYRITE ..........
.EUCOXENE ..... RUTILE

BROWN

/r'////

'//'">

--

brown kaolinite

occur within certain zones of the

..................................

.....................................................

oscillatory zonedplagioclase or fill microfractures. In moderatesericiticalteration,plagioclase sites commonlycontaina center of coarsecalciteplates

with outer sericite and brown kaolinite. Near the

CLINOZOISITE
EPIDOTE ..........................

--

..........

RELICT TEXTURE

.......... '''''''

,,., ''''''''

....

, ...................... '''''''' '''',,

''','

RC WHITE
KO GRAY I

DO)LT. GRA*

C LMED-DARK

+- ; : : ', ; ',', '1'+

i i ' i i i i i i i iiii '' .............. iIii J-'{ -

', ',;',',',I',

strongto moderatesericiticboundary,the calcite plateshaveraggededges andare beingreplaced by sericiteand brown kaolinitealongtheseedgesand alsoalongcleavage cracks.Sericiteandbrown kaolinite appear to coexiststably in moderate sericitic alteration. However, where relations can be discernedin strongsericiticalteration,sericiteappears

LEGEND

0 TO 1% 5o
I TO 5%
25
lo

10%

+ + - MAY BE PRESENT

5 T010%

IIII PRESENT

FIC. 9. Generalized ranges andamounts of the mostcommon

alteration minerals in wallrock,Coco-Luz Angelica area.

to replacebrown kaoliniteby rimmingit or by microveiningit. Sericiteand kaolinite occurtogether in the groundmass of strongsericiticalterationand within intense sericitic alteration. Typically, these minerals are too fine grainedto determinewhether a reactionrelationship is present.However, locally
in intense sericitic alteration, microveinlets of kao-

fraction suggests thatbrownkaolinite is a mixtureof linite cut and may possibly replacesericite.
Freshpyrite at or within a few metersof the sur- Veinlets and their associated alteration face throughoutthe area of the depositindicates Surrounding the major veins are myriad minor that alterationmineralsassociated with the pyrite veinlets.Like majorveins,the dominant process of are primaryandnot relatedto supergene processes. deposition in thesewasopen-space fillingwith little about major fractures(Fig. 11A). Within the alterationhaloabouta majorveinthe entirerockis pervasivelyaltered. All wall rock in the Coco-LuzAngelicaareais alteredto somedegreebut wasoriginally chemically and physically homogeneous. Differencesin mineralizationand alteration style
cannot be attributed composition. to differences in wall-rock chlorite and kaolinite.

Alteration types are distributedsymmetrically evidence for wall-rock replacement. Veinletsmay be anastomosing or through-going; larger veinlets
are generallythrough-going and have orientations subparallel to the nearestmajor vein. As a result,
crosscutting relations between different veinlet types are uncommon. Veinlets are zoned about

Width andintensityof alterationhalosare related to vein type (Figs. 10 and 11A), lateral distance

from the center of the district, and depth (Fig.

11A). Pyritic veinshavelarge sericitichalosincluding the intenseand strongsubtypes. Sphalerite-ga- veins. lena veins have thinner sericitic halos commonly Veinlet types are described in Table 3. Each with the strongand moderatesubtypes but locally veinlet type may have several different alteration with intense sericitic alteration. Carbonate-base selvages, but in a localareaof constant background metal veins have sericitic halos of the moderate alteration,eachveinlet type has only one type of subtype.Calcite-clinozoisite veinshave strongar- alterationselvage (Table 4). Crosscutting relations gillic alteration halos. betweenveinletsof differenttypesyield a consis-

majorpyrite veinswith quartz ___ pyrite, pyrite, and sphalerite +__ galenaveinletsin a proximalposition, followedby carbonate-base metal veinletsin an intermediate position, with calcite-clinozoisiteand calciteveinlets mostdistal(Figs.11 and12). Veinlet zoning has not been recognized in the walls of sphalerite-galena-dominant or carbonate-dominant

1442

P.4ULJ. BARTOS

TABLE 2. Mineralogyof Pervasive Alteration

Pervasive alteration Magnetiteilmenite

Important reaction

type
Intense
sericitic

Plagioclase sites

Maficsites
No relict
texture

sites

Groundmass
Sericite, quartz,

Typical assemblage
Sericite, quartz,

or texture
Sericite -

kaolinitc,pyrite, (clearrutile)
Sericite,
pyrite,

kaolinitc,pyrite, (rutile)
Quartz, sericite, pyrite

kaolinitc;no relict texture

Brown

Strong
sericitic

Sericite

Sericite,
pyrite,

Quartz, sericite,

pyrite, kaolinitc

kaolinitc-
sericite

(cloudy rutile)
Moderate sericitic Sericite, brown kaolinitc, calcite, ___illitc Sericite, brown kaolinRe,
pyrite,

cloudy rutile

Leucoxene, Quartz, sericite, iron pyrite,brown oxides, kaolinitc cloudy

rutile, pyrite
Leucoxene, iron oxides, Quartz, pyrite, sericite, brown kaolinitc or

Quartz, sericite, Calcite- sericite brownkaolinitc, andbrown pyrite, calcite, kaolinitc;no (rutlie), (leucoxene) relict plagioclase

(quartz)

Strong argillic

Brownkaolinitc, sericite,calcite, plagioclase*, +_clinozoisite,

+_illitc

Brown kaolinitc, sericite, pyrite,

calcite,

Brown kaolinitc, sericite, pyrite,

No visible chlorite

(hand sample)

cloudy
rutile

plagioclase*,
brown kaolinitc,

calcite +_quartz, (rutile), (leucoxene)

(cloudy rutile),
+_chlorite*,
_+clinozoisite

pyrite, calcite

Weak Plagioclase*, argillic calcite,brown

kaolinitc,

Chlorite*, calcite,
pyrite,

Leucoxene, Plagioclase*, calcite, Brownkaolinitc, iron pyrite, brown calcite,pyrite,

oxides,
rutile

Chlorite - brown
kaolinitc

kaolinitc,
chlorite*

(rutile), (leucoxene)

(sericite),(illitc), (chlorite) Propylitic Plagioclase*,

calcite, chlorite, _+illitc,+-epidote, +brown kaolinitc

brown kaolinitc,
sericite

Chlorite,
leucoxene, +_pyrite, +_epidote

Leucoxene, Plagioclase*, calcite, Chlorite, calcite, iron chlorite, leupyrite, (rutlie), oxides, coxene,pyrite, (leucoxene), +-illitc,
rutile +_brownkaolinitc, +_illitc sericite or +_brownkaolinitc, +-epidote

Chloritic

Chlorite, sericiteor Chlorite,

chlorite, brown calcite,

Leucoxene, Chlorite, quartz,

iron

Chlorite, quartz

Sericite -

chlorite

kaolinitc,calcite

brown kaolinitc,
pyrite

oxides, rutile

chlorite,brown kaolinitc, calcite

Key:( ) = minor, * = relicitphase, - = isreplaced by;phases listed in orderof relative abundance

associated with specific veinlet typescanbe tent agesequence (from oldestto youngest): quartz vages paragenetic stages of vein fill. +_pyrite, pyrite, sphalerite _ galena, carbonate- correlatedto specific base metal, calcite-clinozoisite, and calcite. Thus Figures11 and 12 compare distribution of pervathe veinlet sequencein time correlates with the sivealterationtypes aboutthe Coco vein systemto with individual veinlet-typedistribution in space awayfrom a major the alteration selvagesassociated pyrite vein; it alsomatchesthe time-spacesequence veinlets. Sericitic selvageson pyrite, sphalerite _ galena, and carbonate-base metal veinlets are documentedfor major veins. The similarity in time relationships and mineral- first visible near the outer boundaryof strongseriogybetweenveinsandveinletssuggests that depo- citic alterationon major veins (Figs. 11A and 12A, sition of both occurred during the sameperiod in B, C). Closer to the vein, the rock is pervasively on the veinlets the history of the hydrothermal systemand that sericitizedand no sericiticselvages pyrspecificstagesof vein fill can be correlated with are visible.This is the typical casefor quartz ___ specificveinlet types. If so, then the alterationsel- itc and sphaleriteveinlets (Table 4). Beyond the

QUIRUVILCA, PERU: MINERAL ZONING AND TIMING

N45W S45E

1443

LOOKIN

NORTHEASTERLY ___: __ __d___

__

_7

Calcite and calcite-clinozoisite veinlets only occur in argillically or propylitically altered rocks (Fig. 12D and E). Calcite-clinozoisiteveinlets are found in argillized rocks and have a characteristic brown kaolinitc selvage. Calcite veinlets are the mostdistalin the Coco-Luz Angelicaarea (Fig. 12); thesetypically do not containa discerniblealteration selvageeven in propylitically altered rocks (Table 4).
Table 5 summarizes the observations which allow

the correlationof the alterationstyle seenas selvageson veinlets to specificparageneticstagesof vein fill. The pyrite stageof vein fill can be correlated with sericitic alteration. The base metal and

= o

//

I-

--

.qz ............

3755

LEVEL

sulfosalt stages canbe correlatedwith both sericitic and argillic alteration, but sericitic alteration is interpreted to have remained dominant during those stages. The carbonatestagecan be correlated with sericitic,argillic, andpropylitic alteration(Table 5).
Breccia dikes and their associated alteration

.'

/
sl

/
dl 3720 LEVEL

Brecciadikes are thin tabular bodies containing angularto roundedclastsof sericiticallyaltered andesitcandminor quartzite, in a matrix of pulverized rock, clays, sericite, quartz, and pyrite (Fig. 13A).
Tourmaline occurs in the matrix of breccia dikes in

220
NO VERTICAL EXAGGERATION

LEVEL

the centralportion of the district. Many smallbreccia dikes occur within the Coco-Luz Angelica area, mostly associated with the Luz Angelica fault system. The dominant strike of Coco-Luz Angelica breccia dikes is east-west(_10 ) and the dips are usuallysteep.Widths average3 to 30 cm and vertical dimensions are unknown. In rare cases, the

smaller breccia dikes split and feather out toward the surface.Variation amongbrecciadikesis seenin the amount, size, and degree of rounding of the clasts.Relative timing between different types is (Fig. 13B). Among the types are finebetweenpyriticveinssuchasCocoand sphalerite-galena veins ambiguous grained breccia dikes consisting of a sericite-illite such asElba3 arereadilyapparent. Compare vein-fijiassemblage to width andtype of alteration halo(Fig. 11A). The Elba 3 veinon matrix with subordinateamounts of quartz, finethe 3870 level hasa mineralogy corresponding to a calcite-clino- grained pyrite (up to 15%), brown kaolinitc, and zoisitevein;thisis accompanied by strong argillicalteration. Else- small (0.75-2.5 mm) sericiticallyaltered andesitc wheretheveinhas a sphalerite-galena mineralogy withaccompa(?) rock fragments.Generally, the contact of the nying strongsericitic alteration. breccia with its walls is sharp but somewhat sheared,and the wall rock is sericiticallyaltered. frontof sericitic selvages, pyriteveinletabundance Fine-grainedbreccia dikes commonlydisplay flow docreases (Fig. l lB); theseveinletstypicallycon- layering oriented parallel to the wall-rock contact. tainno discernible alteration selvages withinargilli- Another variety containslathlike piecesof sericiticallyor propylitically alteredrocks(Table4). Car- cally alteredandesitc in a matrix similarto the finebonate-base metalveinlets contain chloriteand/or grained breccia dikes. These fragments comprise brownkaolinitc selvages in strongly argillized rock around 50 percent of the dike volume and have dior in moderately sericitized rocknearthe boundary mensions of 0.3 to 2.5 cm, with the long axissubof the strong argillicalteration type.The absence of parallel to the dike contact.Shape,angularity,and alteration selvages associated with carbonate-base orientation of the clasts suggestthat they were metal veinlets in argillized rock is also common spaliedoff from adjacentwall rock and underwent (Table 4). little transport.A third variety is true pebble dikes.
FIG. 10. Cross section of Cocovein showing verticalvariations in vein fill. Vertical axis in block diagrams representsvolume percentvein fill from 0 to 100 percent.Line of sectionshown in Figure 8. See Figure 7 for mineral abbreviations. Differences

2'5

51Ore

1444
A

PAUL]. BARTOS
B
N4SW

ALTE SERICITIC ":il

:......[] 'OOERATE
ARGILLIC

'?[] STRONG
[] WEAK
PROPYLITIC

..'::'!.:,

;v.:::.::: ./.:..':o

',4':.*:;. ;'

:. ::.:.::.:: .:

NO

VERTICAL

EXAGGERATION

25

50m

PYRITE

VEINLET

DENSITY

FI. 11. A. Cross section of alterationaboutthe Cocovein system. Enclosed ovoids are drifts;double dashed linesare crosscuts. Line of section shown in Figure 8; crosscuts projectedto thisline. The width of the intensesericiticalterationhalo istoo thin to be depictedat thisscale. The smallareaof anomalous propyliticalterationnearthe Cocovein on the 3870 level represents a late andesitc dike. Blankareasat eastern end of workings represent areaaffected by alterationhaloof the Luz Angelica vein system; this alterationhas not been shownfor purposes of clarity. B. Pyrite veinlet density about the Coco vein system. Note closecorrespondence of pyrite veinlet densityto alterationtype (A).

These contain 40 to 65 percent subangular to rounded,poorly sortedclasts of quartzite and seri-

Interpretation of the Space-TimeEvolution of

Alteration and Mineralization

tically altered andesitcin a matrix of sandto siltPetrographicrelationsindicatethat, for any given sizedpulverizedrock fragments, alongwith quartz, pyrite, sericite,and brown kaolinitc.The sedimen- location,propylitic alteration developedfirst, foltary rockclasts indicate upwardtransport of at least lowed by the argillic, and then the sericiticassem250 m. blages (Table 2). This sequencesuggests that the of the Baseand preciousmetal depositionwith accom- zonedalterationhalosformedby the advance panyingalterationoccurredafter the emplacement outer edge of a particular alterationzone while the
replaced of the breccia dikes.The Probablevein (Fig. 1) cuts inner edge was being contemporaneously a pebble dike and its wall-rock contact. Fragments by the next inner zone (GratonandBowditch,1936; of brecciated vein fill are absent from breccia dikes, Sales and Meyer, 1948). However, deposition of suggesting that deposition of vein fill occurredafter veinlet and vein fill largely postdatedthe developemplacement of brecciadikes.Veinletsof all types ment of the zoned pervasive wall-rock alteration of veinlet exceptquartz _ pyrite and rare pyrite veinlets cut adjacentto major veins.If the deposition with brecciadikes.Pyrite cubesin breccia dike matrices fill had occurredpreciselycontemporaneously typically surround clasts and are euhedral (una- the development of pervasivewall-rock alteration, braded)indicatingthat pyrite formed after the ma- then, for example, younger pyrite veinlets associated with sericitic alteration would necessarily trix was in place. veinlets assoBrecciadike clasts, matrix, and adjacentwall rock have cut older calcite-clinozoisite are consistentlypervasively sericitically altered. ciated with earlier argillic alteration. However, However, there are rare breccia dikesat Quiruvilca mapped field relations indicate that, instead, calin which the clastsare differentially altered, from cite-clinozoisite veinlets consistentlycut and disstrong argillic with 15 percent relict feldspar to place pyrite veinlets. Additionally, some veinlets and their associated alteration selvagescontradict stronglysericiticalteration.

QUIRUVILCA, PERU: MINERAL ZONING AND TIMING

B

1445

25

50m

25

50m

SPHALERITE

+/-

GALENA

CARBONATE

- BASE

METAL

ALTERATION

HALOS:

:[] NONE ] '.::[ SERICITE]

CHLORITE BROWN KAOLINITE

E

.![] REGION OF /
/
/

'
i!
,d

OCCURRENCE },/ II

;;[]OCCURRENCE REGION OF //

,p-----/b
! i

I
I

' t
; I
;

:'

Inz ......

/,
: I

... :

?
CALCITE

f:---::
0 25 50m

+ CLINOZOISITE

CALCITE

FIG. 12. A. Distribution of alterationselvages on pyrite veinletsabout the Coco vein system. Pyrite veinletslacking alteration selvages occur throughoutthe figure (Fig. 1lB). Line of sectionshownin Figure 8. B. Distributionof sphalerite-galena veinletsand accompanying alterationselvages aboutthe Cocovein system. C. Distributionof carbonate-base metalveinletsand accompanying alterationselvagesaboutthe Coco vein system. D. Distributionof calcite-clinozoisite veinletsabout the Cocoveiu system. Note absence of calcite-clinozoisite veinletsin regionof overlapwith high densityof pyrite veinletssoutheast of Elba vein on the 220 level (Fig. 1lB). E. Distributionof calciteveinletsaboutthe Coco vein system.Note restrictionof calciteveinletsto weakly altered rocksfar from major veins (Fig. 11A).

the simple model of outward-expanding pervasive alterationhalos;suchcontradictoryfeaturesinclude the sphalerite_+galenaand carbonate-base metal veinlets with chlorite or brown kaolinitc selvages which were observed within sericitically altered wall rock (Fig. 14).

The preferred interpretationof these field relations is that veinlet filling somewhat postdatedthe bulk of pervasive wall-rockalteration.If the deposition of veinlet fill was synchronous with the corresponding paragenetie stages of majorveinfill (Table 5), then depositionin the major veins must have

1446

PAUL J. BARTOS
TABLE 3. Characteristics of Individual VeinletTypes

Veinlet type Quartz _ pyrite

Pyrite

Description Thin(0.005-0.5mm), wispy tothroughgoing

Keyobservations Strongly sericitized fragments containing

cutoffquartz_ pyrite veinlets foundin
breccia dikes

Mostcommon veinlet type;widevariety of morphologies from Density of pyriteveinlets corresponds to

hairline thinto 5 cmthick, wispy to through-going

Sphalerite_ galena

distribution ofdifferent alteration types

Typically found in sericitically altered rock,in some cases, beyond an intervening interval of pyriteveinlets
Sericiteis a minor veinlet filling associated with sphaleriteeven in veinletswith argillicselvages

Dominantly composed of zoned, lightbrown to red-brown sphalerite plus minor pyrite; galena, if present, found at outer veinlet margin

Carbonate-base metal Carbonate mineralogy varieswith depth--upper levels: manganocalcite; lowerlevels: dolomiteor calcite;quartz occurs assinglyterminatedcrystalgrowingoutwardfrom vein margin;sulfides (sphalerite, pyrite _ galena,rare tetrahedrite-tennantite) innerto quartzmaybe replaced by late quartz;carbonate latest,fillinginnerportionof veinlet
Calcite-clinozoisite

Commonly anastomosing andthin (0.5-1.0 mm);clinozoisite typically occurs at outerveinletmargin separating brown kaolinitcselvage from calciteveinlet filling Veinletscomposed dominantly of calcitewith rare chlorite veinlet filling

Selvage of brownkaolinitc___ pyrite, rare

chlorite characteristic

Calcite

Typically contain no alteration selvage,

even in propyliticallyaltered rocks

postdatedthe bulk of pervasive alteration as well. Ore deposition which postdated pervasive alteration has been documented in other base metal lode

deposits(Farmin, 1934; Lovering, 1949; Tooker,

1963).

At Quiruvilea, there is strong evidence that a portion (exact amount unknown) of the alteration preceded vein fill ore deposition. Serieitie alterationwasinterruptedby breeeiadike eraplacement, (Fig. 13C), whereas ore mineralization dearly postdated breeeia dike formation. Mineralization which

appearsto have postdatedbreeeia dike formationis common at other basemetal andPb-Zn-Aglode deposits suchasEastTintie (Farmin, 1934; Morrisand zones are youngest. Lovering, 1979), Juleani (J. D. Benavides, 1983, A generalizedsequenceof alteration and minerpers. eommun.), Bisbee (Bryant and Metz, 1966; alization can be summarized as follows: Bryant,1968), Cerro de Pasco (Einaudi,1982, pers. eommun.,1983), Camp Bird (Spurt, 1925), Smug1. Initial developmentof the hydrothermalsysgler-Union(A. Colimain Spurt, 1925), and Bache- tem utilizing a preexisting fracture set. The hylor-Syracuse (KingandAllsman, 1950; Bartos, pers. drothermalsystemwas probably triggered by the observation,1983). igneousevent representedby the emplacementof The distributionof pervasivealterationstrongly quartz porphyry dikes. mimics the density of pyrite veinlets (Fig. 11). 2. Initial development of zoned alteration halos However, many of these pyrite veinlets lack alter- around major fractures. Accompanyinginitial deation selvages regardless of the background perva- velopmentof stronglysericiticalterationhaloswere sivewall-rock alterationin which they occur(Table quartz +_pyrite veinletswith sericiticselvages. No 4). Thus, the formation of pervasivealteration is significant depositionof vein fill occurred,as eviprobablyunrelatedto the deposition of pyrite vein- denced by the lack of vein fragments in breccia lets. Both phenomena reflect the distribution of dikes. fracturing andpermeability aboutmajorstructures. 3. Emplacementof breccia dikes. The front of serieitieselvages on pyrite, sphalerite4. Major developmentof zoned alteration halos galena, and carbonate-base metal veinlets in seriei- by intergranularinfiltrationand diffusion, probably

tized wall rock probably representsthe last minor outward expansionof the pervasive sericitic halo which wasprincipallydevelopedbefore theseveinlets and their alterationselvages were deposited. In summary, field and petrographic relations demonstratethat pervasivealteration formed as a seriesof contemporaneous zonesthat grew outward with time; inner zone mineralsreplaced outer zone minerals.Veinlet fillings and selvages were superimposedon this early pervasivealteration event. In contrastwith the development of pervasive alteration zones,veinlet zonesdid not grow contemporaneously;rather, inner zones are oldest and outer

QUIRUVILCA, PER U:MINERAL ZONINGAND TIMING

TABLE 4.

14 4 7

Location of VeinletTypesandAssociated AlterationSelvages in Pervasive Alteration

Veinlets and their associated

alteration selvages

Background(pervasive)alteration

Veinlet type
Quartz _+pyrite

Alteration selvage
None Sericitic
None

Strongly sericitic
m

Moderately sericitic
--

Strongly argillic

Weakly argillic

Propylitic

Pyrite

Sericitic

c
r

M
r

Chloritic

Sphalerite _+galena

None Sericitic

Chloritic Brown kaolinite

r r

---

(argillic)
Carbonatebase metal
None
c c
r

c c
m

c r
m

Sericitic

Chloritic Brown kaolinite

--

(argillic)
Calciteclinozoisite Calcite
Brown kaolinite
M c

(argillic)
None

c
--

M
r

M
r

Chloritic

M = major
c -common

rare

- absent

m = minor

with the pyrite stageof synchronous with the early portion of the pyrite pyrite veinlets,synchronous vein fill. stageof vein fill. 6. Continued minor advance of pervasive alter5. Advanceof pervasivealterationhalosby coalescence of sericiticalteration selvages about some ation halos and formation of sphalerite _+galena
TABLE5. Correlationof Paragenetic Stageto AlterationType

Paragenetic stage
Pyrite

Alterationtype
Sericitic

Evidence Presence of sericiticselvages on pyrite veinletsin strongly argillizedrocks;association of sericiticalterationwith veinswhichcontainthe early pyrite stage; strongcorrelation of highpyrite veinlet densityto areal extentof pervasive strongsericiticalteration; absence of brown kaolinite alterationselvages on pyrite veinlets
Absence of alterationselvages on sphalerite_+galenaveinletsin pervasively sericitized rocks(implying stability with sericitic alteration); presence of sericitic selvages on sphalerite _+ galena veinlets in sericitized rocks, outboard of sphalerite _+ galena veinletswithoutvisiblesericiticselvages; direct association of sericitewith sphalerite in vein fill of carbonate-base metal veinletsregardless of alterationselvage Brownkaoliniteselvages on sphalerite _+galenaveinletsin strongly sericitizedrock

Base metal

Sericitic

Argillic
Sulfosalt
Sericitic

Argillic
Carbonate
Sericitic

Sericiticselvages associated with quartz-stibnite veins Brownkaoliniteselvages on calcite-clinozoisite _ pyrite, sphalerite, galenaveinsand veinletsin argillicallyaltered rocks
Sericitichaloson carbonate-base metal veins(i.e., Verdun, La Compafiia)and veinletsin sericitized andargillizedrocks Carbonate andbrownkaoliniteselvages associated with somecarbonate-base metal veinletswhich lack vein-fillingsericite;brown kaolinitealterationselvages associated with calcite_+ pyrite veinlets in argillically alteredrocks Absence of alterationhaloson calciteveinletsin propyliticallyalteredrocksimplying stabilitywith propyliticalteration

Argillic
Propylitic

1448

PAULJ. BARTOS

s!

FIG. 14. Sphalerite (sl,darkblack)veinletwith brownkaolinitc alteration selvage (bk,black)in strong sericitically alteredwall rock (s, speckled). Carbonate (c, white) fills vugsand separates the sphaleritefrom the brown kaolinitc.Veinlets suchas this constituteevidenceagainsta simpleoutward expanding pervasive alteration halo model.

veinlets with sericiticselvages, simultaneous with the basemetal stageof vein fill mineralization.
7. Formation of carbonate-base metal veinlets

with differing alteration selvages dependent upon spatialpositionwithin the pervasivealterationhalo abouta major vein. This correlatesin time with the later part of the basemetal stage, the sulfosalt stage, andthe initial portionof the carbonate stageof vein filling.
8. Formation of calcite-clinozoisite veinlets with

brown kaolinitcselvages, distalfrom major veinsin argillically altered rocks. This correlates to the sulfosaltand early to mid-carbonate stageof vein filling.
9. Formation of late, distal calcite veinlets with

no alteration halos in propylitically altered rocks, correlated to the late carbonate siageof vein filling.
GeochemicalEnvironment of Ore Deposition
Temperature constraints

FIG. 13. Brecciadikes.A. Typical brecciadike. The white, "spoRed," subround clasts are strongly sericitized andesitc fragments. The light gray,subangular clasts are quartzite.The matrix consists of sand-sized, pulverized,sericitically alteredrockfragments, quartz,sericite,pyrite, andbrownkaolinitc.Scale bar is 5 cm in length. B. Contactshowing a pebble dike (upper left), whichcontains rounded clasts andrelatively little matrix,curing mately16 cm.C. Drill corefragment of a breccia dikecontaining a breccia dikewith subangular clasts with relativelymorematrix. a sericitized clastwith truncated quartz+ pyrite veinlets.Since . Consistent crosscutting relationsbetween the varioustypes of brecciadikesare cut by vein mineralization, somesericiticalterbreccia dikes were not observed;however, vein mineralization ation mustbe early relativeto vein filling. Scalebar is 5 cm in consistenfiy cutsall brecciadikes.Length of pencil is approxi- length.

Temperature constraints for the environmentof ore depositionat Quiruvilca are basedon sulfide and silicatephaseequilibria.In the centralenargite zone, abundantenargite-luzoniteintergrowthsof the earlybasemetalstage(C. R. Patri, 1961, unpub. data)indicatea temperatureof formationin the regionof 300 to 320C, whichis the lower stability temperaturerangeof enargite(Maskeand Skinner, 1971; Feiss, 1974). The presenceof enargite and

QUIRUVILCA, PERU: MINERAL ZONING AND TIMING

1449

the absence of luzonite suggest that at somepoint temperatureswere higher than 300 to 320C, assuming end-member Cu-As-S composition(Lewis, 1956, p. 54). Temperatures at the end of the base metal stagein the central enargite zone were less

presence of chalcopyrite. The enargite-tennantite sulfidation curve in Figure 15 represents a minimum sulfidationboundaryfor the enargite zone, assuming no significant antimony in enargite

(Lewis, 1956, p. 54). than 307C, i.e., the maximum thermal stability of Constraints on the sulfidation boundary of the realgar (Barton and Skinner, 1979) which occurs transition zone are provided by the presence of late in the paragenesis. tennantiterather than enargite,andthe presenceof

In the transitionand lead-zinc zones,the pres- trace amountsof native arsenicwith apparentinof pyrite (Haagensen et al., 1979) rather ence of late Pb-As-Sglass,(As,Cu)-richpyrite and clusions The lower sulfidation boundary other sulfosalts indicatetemperatures of lessthan than arsenopyrite. 300C duringthe sulfosalt stage(Burkart-Baumann for the lead-zinc zone is the presenceof pyrite and Otteman, 1972). Within the transition zone, rather than pyrrhotite.The presence of arsenopythe presenceof jordanitc (Maier, 1981) indicates rite ratherthanpyrite + nativearsenic provides the that temperatures were greaterthan250C(Barton upper sulfidationlimit. and Skinner,1979). The possible presence of graArsenopyrite is commonin the stibnite zone; its tonitc (suspected by Lewis, 1956) in the lead-zinc presencerather than pyrite and native arsenicdefinesthe upper sulfidation limit of the stibnitezone. This is confirmedby the absenceof gratonite or jordanitcandthe presence of the assemblage galena + native arsenic(suggested by Lewis, 1956, p. 59). The lower sulfidation boundary for the stibnite zone is provided by the absenceof pyrrhotite and the presenceof pyrite. A decreasein sulfidationstatewith time at Quiwith the replacement of enarsphalerite and galenain the late sulfosalt stage, ruvilcais compatible basedon the lower thermalstabilityof clinozoisite gite by tennantite-tetrahedrite, the progressive in moderngeothermal systems (Seki, 1972; Cavar- darkening of sphalerite color with time, and the retta et al., 1982; Bird et al., 1984; Schiffmanet al., abundance of late arsenopyrite (Fig. 15). 1984). Late calciteoccurringat the end of the carbonatestage mayhaveformedat stilllowertemper- Alterationchemistry atures. Alteration assemblages are shownin Figure 16. In summary,mineralogyof vein filling and alter- For this diagram, constructed for conditions of ation pointsto a temperatureof formationof ap- 300C, the concentration of total sulfur was chosen proximately 350 (?) to 300C for the bulk of ore as0.01 m, within the range of valuesthoughtto be deposition (pyriteandbase metalstages). Tempera- boundary conditions for most sulfur-bearing hy(Barnesand Czamanske,1967; ture is believed to havedecreased in time through- drothermal systems out ore deposition as the sulfosaltand carbonate Ohmoto, 1972). Potassium content was chosenas stages probablyformed in the vicinity of 230 to 0.05 m; this fallswithin the range40 to 4,000 ppm fluid inclusion concentrations 300C, whereasthe carbonatestagecontinuedto which encompasses form at temperatures lower than approximately from other vein-type deposits(Roedder, 1972; Ka230C. This temperaturerange is comparable to milli and Ohmoto, 1977; Slack, 1980). Total carthoseof otherbasemetallode deposits asrevealed bonate and calcium both were chosen at 0.1 m; by fluid inclusions (Sims andBarton,1962; Meyer these values are bracketed by those determined at
zone suggests temperatures at one point may have

been below 250C (Roland,1968). In the Coco-Luz Angelica area of the transition and lead-zinczones,calcite +__ pyrite, sphalerite, and galena veinletscut and displace earlier calciteclinozoisite +__ pyrite, sphalerite,and galenaveinlets.Thisrelationsuggests thatthe temperature had decreased to below230Cduringthe deposition of

et al., 1968; Imai et al., 1985) or by sulfurisotope fractionation (Einaudi,1977). The very coarse grainedvein materialat Quiruviicasuggests that boilingdid not occur;declining temperatures probablyaccount for ore deposition.

Sunnyside, Colorado (Casadevall and Ohmoto, 1977). The calciumvalue of 0.1 m is alsocompara-

ble to thosedeterminedfor lodesat Colqui, Peru;

Lake City, Colorado; and Rochester, Nevada (Kamilli and Ohmoto, 1977; Slack, 1980; Vikre, 1981). In Figure 16, region i represents the immediSul fidation ately adjacentwall rocksfrom the enargitezoneand Sulfideassemblages documentdecreasing sulfi- corresponds to the assemblage pyrite 4- kaolinitc dationlaterally away from the center of the district 4- quartz, with anhydriteabsent. (Fig. 15), a common characteristic of base metal Region 2 encompasses the environment of wall-

lode deposits (Petersen,1970). The upper sulfida- rock alteration for the transition, lead-zinc, and tion limit for the enargitezone is providedby the stibnitezones.Region2 hasbeen divided into three absence of the assemblage bornitc4- pyrite andthe subregions. Subregion2a, representingintense ser-

1450
O-

PAUL J. BARTOS

-2

-4

-6

/
/
-12

/
/

-14

-16

T(*C)
200 250 300 350

ENARGITE ZONE
TRANSITION
LEAD-ZINC

ZONE

ZONE

STIBNITE

ZONE

400

450

5O0

550

600

2 2

2.0

I8

1.6

1.4

i.2

103/T(K) FIG. 15. Univariant sulfidation curves(from Einaudi, 1977, fig. 13) applicableto Quiruvilcaores. Shaded areasrepresentthe stabilityfieldsof the four mineralogic zones.Arrow represents the evolutionary trend of the Quiruvilcasystem.

icitic alteration,is characterized by an assemblage ation is represented by the assemblagepyrite of pyrite + quartz + kaolinitc + sericitewith calcite + sericite+ quartz, with calcite and anhydriteaband anhydrite absent. Strong sericitic (2b) alter- sent. Moderate sericiticalteration(2c) is depicted by the assemblage pyrite + sericite+ quartz+ calo

cite.

KAOL

MUSC

pH
6
CALCITE

MUSC+QTZ
KSPAR
.

HSO;

ANHYDR tTE --- - C'--

8-

H2CO

io

12

-:58

-:36

-34

-32

-:30

-28

-26

-24

Argillic and propylitic alteration is represented by region3; calciteandpyrite are stableandsericite + quartz is absent. Sericite without quartz is presentin argillicalterationbut absent in propylitic alteration.At an assumed molality of Na+ of 0.1 m, albite is stable as part of the propylitic assemblage at pH valuesgreater than 5.6 (Montoyaand Hemley, 1975). The sequenceof regions 1 to 3 representsthe zonal pattern outward within the wall rock from a major vein in the enargite zone; the sequenceof regions2 to 3 is representativeof alteration selvagesin the rest of the district. A lateral decreasein H + activity (increasein pH) away from the center of the district is implied assumingthat the activitiesof potassium, sodium,and
calcium ions were constant and that alteration en-

velopes developed isothermallyabout fluid chanFIG. 16. IsothermalpH-logfo diagram,at 300C, showing nelways. proposed chemicalenvironments for alterationat Quiruvilca.InAt any one spot within the wall rock, pH dedividual assemblage regions (1-3) are discussed in text. Con- creasedwith time as propylitic alteration was restraints: ES = 0.01 m, Y.C = 0.1 m, K+ = 0.05 m, Ca+2 = 0.1 m. placedby argillic andthen sericiticalteration. Oxide, sulfide, sulfate, and carbonate boundaries based on data in
Crerar and Barnes(1976). The K silicatemineralboundaries are derived from Montoya and Hemley (1975). Abbreviations: Hm = hematite, KAOL = kaolinitc, Mt = magnetite,MUSC -- muscovite, Po = pyrrhotite,Py = pyrite; QTZ -- quartz.

log fo? '-

Summary

Overall the Quiruvilca base metal lode hydrothermal systemexhibits:(1) a temporal separation

QUIRUVILCA, PERU: MINERAL ZONING AND TIMING

1451

betweenthe formationof pervasive alterationhalos eds.,Geologyof the porphyrycopperdeposits, southwestern aboutmajorveinsandore deposition; (2) alteration North America:Tucson,Univ. ArizonaPress,p. 189-203. I., and Otteman,J., 1972, Uber niedugtherrelationswhich suggest decreasing pH with time at Burkart-Baumann, male Sulfidbildugen von Quiruvilca, Peru: Neues. Jahrb. any one spotwithin the wall rocks;(3) vein-filling Mines, Monatsh.H, v. 2, p. 541-551. relationswhich suggestdecreasing temperatures Casadevall, T., and Ohmoto, H., 1977, Sunnyside mine, Eureka of and sulfidation statethroughtime; and (4) mineral mining district, San JuanCounty, Colorado:Geochemistry gold and base metal ore in a volcanic environment: ECON. zoningwhich suggests decreasing sulfidationand GEOL., v. 72, p. 1285-1320. increasing pH laterally away from the center of the Cavarretta, G., Gianelli, G., and Puxeddu, M., 1982, Formation of
district.

Acknowledgments

Rosiers, insured a successful field season. Discus-

This paperrepresents muchof a Master'sthesis at 69 p. StanfordUniversityunder Marco Einaudi. I wish to V. thank DouglasM. Smith,Jr., managerof the Rocky Crerar, D. A., andBarnes,H. L., 1976, Ore solutionchemistry Solubilities of chalcopyrite and chalcocite assemblages in hyMountain Exploration Division of ASARCO, Inc., drothermal solution at 200 to 350C:ECON. GEOL., v. 71, p. who arrangedthe project andprovidedfunding.Sal 772-794. Anzalone, ASARCO's chief mine geologist, ar- Einaudi, M. T., 1977, Environmentof ore depositionat Cerro de rangedroomandboardat Quiruvilca.The generous Pasco,Peru: ECON. GEOL., v. 72, p. 893-924. Descriptionof skarns associated with porphyrycopcooperationof the CorporacionMinera Nor Peru, -- per1982, plutons,southwestern North America,in Titley, S. R., ed., in particular, Walter Eberhart and Dave DesAdvances in geologyof the porphyry copper deposits, southwestern North America: Tucson, Univ. Arizona Press, p.

authigenic mineralsand their use as indicators of the physiochemical parameters of the fluidin the Larderello-Travale geothermalfield:ECON.GEOL.,v. 77, p. 1071-1084. Cossio,A., 1964, Geologia de las cuadranglesde Santiagode Chuco y SantaRosa:Com. Carta Geol. Natl. [Peru], Bol. 8,

139-184. sionswith ASARCO personnel, including Darby Entwistle, L. P., and Hollister, V. F., 1957, Discussion--thegeolFletcher, Fred Graybeal,and Bill Kurtz, were helpogy and ore depositsof the Quiruvilca district, Peru: ECON. ful. Drafts of this manuscriptwere reviewed and GEOL., v. 52, p. 83-84. considerably improved upon by Marco Einaudi, Farmin, R., 1934, "Pebble dikes" and associatedmineralization at Tintic, Utah: ECON.GEOL.,v. 29, p. 356-370. Horacio Ferriz, Tim Hayes, and Eric Seedorff. of the tetrahedrite-tennanDiana ScheidleBartosprovidedmuchlove and sup- Feiss, P. G., 1974, Reconnaissance tite/enargite-famatinite phaserelationsas a possible geotherport. Lois Bormolini prepared the manuscript.Permometer: ECON. GEOL., v. 69, p. 383-390. mission to publishwasprovidedby ASARCO Inc. Giesecke, A., 1978, Geologyand exploration at the Quiruvilca

mine,Peru:Lima, Peru,Corporacion MineraNor Peru,unpub.

June 25, 1985; January 21, 1987

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