Landis & Rye 1974 Geologic Fluid Inclusion and Stable Isotope Studies PDF

ECONOMIC GEOLOGY
AND TH!r-
BULLETIN OF THE SOCIETY OF ECONOMIC GEOLOGISTS
VOL.'69 NOVEMBER, 1974 NO. 7
Geologic,Fluid Inclusion,and StableIsotopeStudiesof

the PastoBuenaTungsten-Base Metal Ore Deposit,
Northern Peru
GARY P. LANDIS AND ROBERT O. RYE

Abstract
The Pasto Bueno tungsten-basemetal ore deposit is situated at an elevation of ---•

4,000 meters in the north-central Andes of Peru. Mineralization occurs in near-vertical
quartz vein systemsthat span several hundred meters on either side of the upper intru-
sive contactof a 9.5-m.y.-old quartz monzonitestock eraplacedin a Jurassic-Cretaceous
shale and quartzite sequence. The stock exhibits four pervasive and rougMy zoned
alteration assemblagesfrom core to periphery: (1) alkalic, (2) phyllic-sericitic,(3)
argillic, and (4) propylitic. Greisen assemblagesof zinnwaldite, fluorite, pyrite, and
minor topaz and tourmalineoccurwithin the phyllic zone.
The principalvein mineralsare wolframite,tetrahedrite/tennantite, sphalerite,galena,
and pyrite in a gangue of quartz, fluorite, sericite, and carbonate. Detailed studiesof
the hydrothermalmineral paragenesisestablishedthree major recognizabledivisions:
Greisen(60 to 70 percentof deposition),Vein (25 to 35 percentof deposition),and
Vug (<5 percentof deposition).
Fluid inclusionstudiessuggestthat Greisenand early Vein stagefluids were very
saline (>40 equivalentweight percentNaC1), high-temperature(400ø to 500øC) solu-
tions of magmaticderivation. The subsequent main Vein stage ore fluids attaineda
temperaturerange of 175ø to 290øCand a salinityrangeof :2 to 17 equivalentweight
percentNaC1. Boiling of the ore solutionsis indicatedonly for the Greisenand early
Vein stagesof hydrothermalactivity.
The resultsof stableisotopestudieson water in primary fluid inclusionsindicate
that the $D•.o of the ore fluidsvariedfrom --29 per mil to --88 per mil (SMOW).
Analysesof watercontained in secondary inclusionsindicatethe $Da•.oof the fluids
attainedvaluesas low as --145 per mil prior to the cessationof hydrothermalactivity.
The $•80,,•.o of the hydrothermalfluids,as calculated
from the $x80quartzandcarbon-
atedataandthetemperature data,rangefrom+7.8 per mil to +0.0 per rail (SMOW).
The $D valueof present-day meteoricwater is --96 per rail.
The patternsfor $D,,•.o and $•sO,,•ovaluesof the hydrothermal fluidsindicatethat
mixingof a meteoricandpossibly a metamorphic or otherwater component with water
of magmaticderivationoccurr.ed duringVein stagedeposition.Major variationsin the
deuteriumcontentof the ore solutionsare not reflectedby fluctuationsin the •sO con-
tent, indicatingthat meteoricwater circulateddeepinto the hydrothermal plumbing
system. Wolframite depositionwas associated with episodesof meteoricwater influx
that are reflectedin the temperature,salinity,and $D valuesof the water in fluid in-
clusions.Sulfidemineralization,
on the otherhand,wasassociated
with waterof mag-
matic derivation.
The$xaCdatafor hydrothermal
CO2rangefrom--4.1 perrailto --11.9perrail (PDB)
and are interpretedto indicate that the carbon in the ore fluids was derived from both
sedimentary anddeep-seated sources.$•S valuesof pyritedataexhibita narrowrange
of values(--2.5 per rail to +3.9 per rail) with an averageof +0.6 per rail, indicating
that the sulfurwas derivedfrom a deep-seated
or mantlesource.
Most of the componentspresentin the PastoBuenoore depositsappearto be of
magmaticorigin. Clearlyhowever,significant
volumes of meteoricwaterandpossibly
otherwaterwereinvolvedin somestagesof the ore deposition
process.
1025
1026 G. P. LANDIS AND R. O. RYE
Introduction Wolframite was discovered at Pasto Bueno in
Ta•. classichypothesis
for the derivationof postmag- 1910. In 1934 the present Peruvian mining com-
maticore deposits(Lindgren,1933; Holland,1972) pany, Fermin Malaga Santolallae Hijos, was estab-
has comeunder increasingscrutinyin recentyears. lished. The Pasto Bueno camphas not beenopera-
The geneticconceptthat hot aqueousfluidscontain- tional sincethe early mining days. Presentmining
ing metals and salts are releasedfrom crystallizing activityis basedat Consuzo;Regionde Maria Ofelia,
magrnas,and that thesefluidsmoveupward and out- Region de Huaura, Region de Huayllapofi, and
Mundo Nuevo are subordinate settlements in the
ward from their sourceto depositmetalsin suitable
structuraland chemicalsites,hasbeenquestionedas Pasto Buenomining district (Figs. 2, 3).
beingan oversimplification. A generalizedgeologicand vein map for the Pasto
.Consideration of stableisotopedata from several Bueno district with the recognizedregionalgeologic
ore deposits(Rye and Sawkins, 1974; Sheppard units (as describedby Wilson et al., 1967) is shown
et al., 1969, 1971; Ohmotoand Rye, 1970; Hall and in Figure 3. Mineralization occursin near-vertical
Friedman,1963; Rye et al., 1974; Garlick and Ep- quartz veins associatedwith the upper Tertiary
stein, 1966; Engel et al., 1958) has indicatedthat quartz monzonite Consuzo stock (Wilson et al.,
watersof nonmagmatic origin canplay an important 1967; Tarnawiecki, 1911; Miller and Singewald,
role in the formationof somepostmagmatic ore de- 1919; Steinmann, 1929; Malaga S., 1954; Landis,
posits. Integrated fluid inclusionand stableisotope 1972). 'Sedimentarycountry rocks recognizedin
studiesare of major importancein the assessment of the areacomprisepart of the Jurassicand Cretaceous
the relativerolesplayedby primary magmaticwater stratigraphicsequence of shale,quartzite,and lime-
versus meteoric water or other water in the forma- stoneof northern and central Peru (Wilson, 1963;
tion of specifichydrothermalore deposits. Wilson et al., 1967). No rocks older than late
Hydrothermalvein tungstenmineralizationis gen- Jurassic crop out in the map area, but gneissand
erallythoughtto be closelyassociatedwith magmatic schist,conglomerate, and some volcanic-pyroclastic
processes(Kelly and Turneaure, 1970; Krauskopf, units of Precambrian, early Paleozoic,Mississippian,
1967; Lindgren,1933; ttosking, 1967). The Pasto and Permian age have beenreportedapproximately
15 kilometers to the east in the Marafion Valley
Buenotungsten-basemetal ore depositin the north-
central Andes .of Peru is especiallysuitablefor a (Fig. 6) andin the CordilleraCentral (Wilson et al,.
studyto help elucidatethe evolutionof the aqueous 1967). These older rock units may or may not ex-
tend to the west under the Pasto Bueno area, a ques-
fluidsinvolvedin latemagmaticprocesses andhydro-
thermal ore deposition. Pasto Bueno affords well- tion of someimportanceto later discussions.
exposed,geologicfield relationsand substantialtopo- Sedimentaryrocks
graphic relief throughout the intrusive body and The Upper JurassicChicamaFormationis a black
mineralizedarea. Simplemineralizationassemblages carbonaceous, pyrite-bearingshale which contains
in open"vuggy"veinsystems provideamplematerial coarsesilty lenses. The baseof this oldestunit is
for multipurposefluid inclusionstudiesand enable not observed in the area and its thickness not deter-
precise parageneticcontrol on all samples. The mined because of extensive d•collement and other
high elevationof the mining region coupledwith a structural deformation above an unknown basement
"young" age of the depositassurea likelihoodof (Wilson et al., 1967). The ChicamaFormation is
present-daymeteoricwaters being isotopicallydis- described by Wilson et al. (1967) as formingin the
tinguisablefrom deep-seated or magmaticwatersand westernPeru trough, a depositionalbasin trending
permit an assessment of the probableisotopiccom- northwest.-southeast and existing from about the
positionof local ground water at the time of min- Middle Triassic to the Late Cretaceous. This trough
eralization.
was likely the inner-arc basin of a Jurassicisland-
arc system. The maskinginfluenceof contactmeta-
Geology
morphic effects near the Consuzostock prohibits
Pasto Bueno (Fig. 1) is on the northernmostex- positive detectionof a definite volcano-pyroclastic
tensionof the CordilleraBlancabatholith (approxi- componentto the sediment. Upper Jurassicpillow
mate longitude77ø41.5'W; latitude 8ø7.5'S), just lavas crop out on the west coast and are possible
below and west of the Continental Divide. The volcanicfaciesequivalentsto the ChicamaFormation.
miningcampis 180 kilometersby roadfrom Trujillo A sequenceof interlayed quartzites and are-
on the coast,580 kilometersby roadfrom Lima, and naceous silitites150to 200 metersthickcomprises
the
nearly 90 kilometers due east of the Pacific Coast. Chimfi Formation lying unconformablyabove the
Elevationvaries from about 3,300 metersto nearly ChicamaFormation. Brown-graymassivequartzites
5,000 meters(16,500 feet). interbeddedwith shalegradeupward into very thick
P.dSTOBUENOTUNGSTEN-BASE
METAL OREDEPOSIT 1027
massivewhite quartzitesconsistingof fine-grained,

equigranular,well-sortedquartz, stronglyrecrystal-
lized into a tightly interlocking texture. Graded
COMP•CCH•
bedding, crossbedding,and cut-and-fill features are
commonin the upper members,whereascarbon and
anthracitecoal seamsare typical of the lower mem-
ber andbasalportionof the upperChimfiFormation.
The Santa and Farrat Formationsare, respectively,
brown-gray limestones,thin gray-to-red shales,and
fine-grained white quartzite interbeddedwith red
lutite. The Chimfi, Santa, and Farrat Formations
collectivelymake up the GoyllarisquizgaGroup and
represent shallow marine and transgressivebeach S•elogofo$
depositionalenvironments.
The sediments thin 25 to 30 kilometers east of ,•,,I•• J/S TR,,•L
PastoBuenoas they onlapa paleotopographic
high,
the Marafion geanticline. Farther east the Chicama Conch•
Formation is not present and the Goyllarisquiza

Group is a thin undifferentiatedunit. To the east
of Pasto Bueno the Goyllarisquizgasedimentsare
80 ø 78 ø 76 ø 74ø ?E,• 70 ø 66 ø
ILLERA
COLOMBIA BLANCA
o IO KILOMETERS
I , I
/ /
Fro. 2. Map of the Pasto Buenoregion. The Consuzo
stock (patterned) is located northeastof the northernmost
contiguous portionof the CordilleraBiancabatholith. Rio
Pelagatosdissectsthe stock in an E-W direction. Other
mineral occurrences discussed in the text are shown. Box
indicatesmap area of Figure 3.
BRAZIL
dominantlycoarse,angular, locally derived, fluvial,
and deltaicsedimentsinterspersedwith fine-grained,
I0 o
brackish-watersedimentsandgypsum(Wilson et al.,
1967).
The PariatamboFormation consistsof black-gray
12ø
\ shales and limestones and occurs to the southeast of
\
the map area.
14ø Igneous rocks
Igneousrocksobservedin the areaconsistof lower
16ø Tertiary volcanicdikesand sills,the Consuzoquartz
monzonite stock, and upper Tertiary hypabyssal
rocks that are probablycomagmaticwith the stock.
lB o The Consuzostockis a biotite-bearingporphyritic
quartz monzonitewith a total outcroparea of nearly
0 800 KILOMETERS 40 square kilometersand a maximum vertical ex-
posureof 1,100 metersobtainedin the Rio Pelagatos
Canyon. Although the Consuzoquartz monzonite
Fro. 1. Map showing location of Pasto Bueno. National stock can be considereda single intrusion,its min-
and departmental boundaries are shown, as well as the eralogy,composition,and texture are variable. In-
Andean Cordilleran mountain systems (patterned). Pasto
Bueno is situated near the crest of the Cordillera Blanca tense, pervasive deuteric•greisenalteration of the
countain chain of the Cordillera Occidental. stockmakesit difficultto distinguishprimary varia-
I I I
ß
ß ß
EXPLANATION
Oualernary alluvium
Ouarlz monzanile {Consuzo

Slock-- 9.5 + 0.:) m.y.)
Volcanic dikes and sills
Normal fault--Dashed where

approximatelylocated;queried
where inferred. Bor ond bari
on downthrown side
ß ß ß
Thrust fault--Dashed where
approximately letoted. Sawteeth
on upper plate
Strike and dip of beds

tJO Ihclined
..•83 Vertical
Overturned
._•0 Strikeanddipof folioSion

NI7000 -- Vein
ß Sample location
ES9000 1:'20000 E21000 E22 000 E23 000
0I , I 2I KILOMETERS
Fro. 3. Geologic map of the :Pasta Buena tungsten-basemetal ore deposit (modified from Landis, 1972).
tiens from later alteration-greisenoverprints. The history of the Consuzostockand its major features
mineralogyof the Consuzostockconsistsof quartz, (Landis, 1972) are listed in Table 2. This inter-
sodicplagioclase,orthoclase,microcline,and biotite, pretation is based on observationsin the Consuzo
with accessory apatite,sphene,magnetite,and zircon. and Consuelodrifts and at outcrops in the Rio
It is typically porphyritic, with K-feldspar mega- PelagatosCanyon.
crysts1 to 10 cm long in a medium-grainedground- Surface exposureof the Consuzostock is five
mass. Typical rangesof mineral mode of the stock kilometers to the northeast of the northernmost
are presentedin Table 1. The complexformatlanai contiguousexposureof the Cordillera Blancabatho-
lith. Studies of the main body of the Cordillera
TABLE 1. Consuzo Stock Mineral Mode
Blanca batholith show that a quartz monzonitephase
Volume
was emplacedafter the volumetricallymore signif-
Mineral (percent) icant tonalite and granodioritephases(Egeler and
deBooy,1956; Coney,1971). A sphenefission-track
Quartz 5 •20
15 •20
age determination(C. Naeser,oral commun.,1972)
Orthoclase(microcline)phenocrysts
Plagioclase(An•0 to Ana,) 25 •45 dates the stock at 9.5-----0.2 m.y. This age is in
Orthoclase 10 •20 goodagreementwith a K-Ar biotite age of 9.1 m.y.
Biotite 3 --8
Sphene 0.5-- 1.0 obtainedfor a granodioritephaseof southernCordil-
Other minor accessories(total): 0.5-- 1.0 lera Biancabatholith(Giletti and Day, 1968).
Hornblende,apatite, spessartite,
zircon, magnetite, pyrite, Rock alteration
pyrrhotite, topaz, tourmaline,
beryl, axinite The conventionalterms alkalic, phyllic, argillic,
and propylitic (Meyer and Hemley, 1967; Rose,
PASTO BUENO TUNGSTEN-BASE METAL ORE DEPOSIT 1029
1970; Creasey,1966; Lowell and Guilbert,1970) T,•m•E 2. Formational Events of the Consuzo Stock and
Associated Mineralization
describepervasivemajor alterationmineral assem-
blageswithin the intrusive. A generalconcentric I. Emplacement of magma
distributionof the hydrothermalalteration assem- A. Forceful injection of magma with doming and asso-
blagesis observed(Fig. 4). However, the altera- ciated faulting in Chicama Formation and overlying
tion pattern imposedby fracture control is more units.
conspicuous
than the crude concentriczonation. As B. Minor, but discerniblestoping:
determinedby studiesof sequential,zonal, and Stope blockssink maximum of 300 to 600 meters
(e.g., 9F-100); contact hybridization by assimila-
crosscuttingrelations, the alteration of the Consuzo tion not significant.
stockcanbedocumented asa singledynamic
episode C. Developmentof broad irregularzonesof textural and
that evolvedfrom pervasivelate magmaticto in- mineralogical variations with fissure formation in
creasingly restricted postmagmatichydrothermal "honeycombed"crystal mush.
processes. D. Solidificationof 800 to 900 metersupper portionof
stock.
Theconceptof greisenization
in thisstudyfollows E. Continued uplift of stock.
theusageof Shcherba(1970a andb) andis defined
as a high-temperature,postmagmatic alterationof I I. Emplacementof dikes, alteration, and faulting
rocksaffectedby residualvolatile-richacid solutions
A. Coolingand fracturing of outer marginsof the stock
associated
withthecooling of alkalic-rich
graniticin- while final silicate melts and volatiles concentrate at
trusives.As such,alkalic,phyllic,andargillicalter- depth.
ationsare specific
aspects of the all-inclusive
grei- B. Development of pervasive alkalic metasomatism:
senization.In a more restrictedsense,greisen Microclinizationand albitization, microclinepheno-
alterationis recognizedin graniticrocksby an cryst porphyroblasts;continuationof processuntil
about II-E.
anomalousenrichmentin Li, B, Be, P, rare earths,
C. Influx of meteoricwater developingpropylitic altera-
and rare metalsandis typifi.ed at PastoBuenoby tion assemblagesat intrusivemarginsand alongcross-
thepresence of zinnwaldite, fluorite,topaz,tourma- cutting major zones of recurrent movement (e.g.
Loma Bianca and 9F-105); secondary hornblende.
line,beryl,apatite,axinite,wolframite, chalcopyrite,
andmolybdenite largelywithinan otherwise quartz- D. Intrusion of aplitic dikes of similar compositionto
parent rock:
sericite
ñ pyriterock. No attempthasbeenmade Phenocrystsof biotite and K-feldspar, 0.2 to 1.0
to distinguish
between phyllicandgreisenalteration cm across, occur in sugary textured aphanitic
althoughtheymaynot havebeencoevalevents.The groundmass; no wall rock alteration associatedwith
this stage; orientation of dikes predominantly
quartz-sericite
alterationcontainingtheabovegreisen northeast-southwest;upper 1,500 meters of stock
mineral assemblages is tabular and vertical and completely crystalline.
parallelsveinsphylli.calterationis generallycon- E. Emplacement of crosscutting, coarse-grainedfeld-
centric. spar-quartz aplites with no phenocrysts:
Increase in the feldspar content of the aplites;
Alkalic metasomatism, the innermostalteration, weak bleachingof wall rock from circulatingfluids;
producedanassemblage of K-feldspar,
biotite,quartz shift in dike orientation to north-south and ulti-
ñ sericite,and plagioclase
(Ana0-Ans). Clearevi- mately to northwest-southeast,vertical, and in line
with regional structural and mineralogicaltrends.
denceis presentfor the development of secondary F. Pegmatiticveinletsand pods:
K-feldspar.Microclinization developed withinthe Pyrite, purple-brown fluorite, and zinnwaldite in
innerportionof theintrusion,
whereas slightlyabove matrix of clay mineralsand quartz; claysoriginally
the microclinedevelopment, but totallygradational adularia; aplite dike developmentdiminishes.
with it, is a zone of albitization. G. Phyllic-argillicalterationof uppercoolerportionof
stock:
Phyllicalteration
(quartz-sericite-pyrite
alteration Developmentof quartz-sericiterock alongincreas-
of Creasey,1966) produced a quartz-sericite
rock. ingly restrictedfracture systems;quartz ovoid to
Plagioclaseand K-feldsparwere alteredto sericite anhedralovergrowth;strongestperiodof greiseniza-
t/on (topaz, tourmaline, axinite, zinnwaldite); de-
andquartz,andbiotitewaschloritizedorcompletely- velopment of pyrite-pyrrhotite-magnetiteassem-
removed.Largeovoidgreisen quartzmegacrysts 2 blage in wall rock.
to 9 mm in diameterare commonin this alteration.
Pyrite, in most instances,is disseminatedin the I I I. Eraplacementof veins
A. Continuation of events in II-E and II-F.
phylliczoneandlocatedalongveinletfeathercracks
in the rock. Pyriteandphyrrhotite,
formedat the B. Development of barren early quartz veins and
expense of magnetite, occur in the rock near min- quartz-pyrite veins.
eralizedveins. The zonesof phyllicalterationat C. Formation of northwest-southeast Huaura Quartz
Ridge (initial temperatures400ø to 350øC).
depthbecome increasingly
confined,
tabularandfin-
D. D.eposition
of hydrothermal
vein mineralparagene-
ger-like,as reaction
fluidswererestricted
to major sts; continuedargillic alteration.
fissures.The greisen
minerals
zinnwaldite,
topaz,
$E
o 2 KILOMETERS
I • I
EXPLANATION
Quaternary alluvium
-- Quartz monzonite(Consuzo
TERTIARY
•, Stock 9.5+_.0.Z m.y.)
Pariatambo Formation
Farrat
Formation
1 Cretaceous
Lower
CRETACEOUS
SantaFormation
LGøyllarisquizga
__ Chimfi
FormationJ
Group
Chicama Formation Upper JURASSIC
Jurassic
Fro. 4. Crosssectionof the Consuzostock (Landis, 1972). Places of interest projectedonto the plane of the cross
sectionare shown along the top margin.
beryl, tourmaline,and fluorite are presentand minor mon mineral products. Weak propylitizationcon-
amounts of disseminatedwolframite, molybdenite, verted the plagioclaseto chlorite and clinozoisite.
chalcopyrite,bornite,pyrite, and other ore minerals Intensepropyliticalterationtransformedthe rock to
are common. Phyllicalterationis everywheregrada~ green knottedchlorite and clay. Propylite doesnot
tional with the inner alkalic and outer argillic zones reachdeepwithin the stock,exceptalongmajor near-
of alteration,but the width affectedby phyllicaltera- vertical structural zones trending northwest-south-
tion is variable. Argillic alteration products are east, and is otherwise confined to border zones of
clay minerals,chlorite_--4-sericite,_--4-
fluorite-----
pyrite,
the intrusion. Feldsparsin these rocks are quite
and quartz. Pervasive argillic alteration is weak turbid. As discussed in the isotopesection,an early
and muchlesssignificantthan phyllicalteration. influx of meteoricwater into the stockis thought to
Propylitic alteration involves the addition to the
have producedthis alteration.
rock of H20 and CO2 without strong leachingor Hydrothermal vein alteration related to hydro-
loss of alkalis or alkaline earths to the solutions thermal mineralizationis superimposed on the above
(Rose, 1970). Chlorite,epidote,and albiteare corn~ alterationand is localizedaround quartz veins and
PASTO BUENO TUNGSTEN-BASEMETAL ORE DEPOSIT 1031
rarely extendsfarther than 1 to 3 metersbeyondthe in a matrix of black carbonaceous material,in part

vein-wall rock contact. This alteration is very in- graphite,and detritalquartzgrains. Large opaque
tense, changing the local host ro.ck to very fine- grains of pyrrhotite (after pyrite) are common.
grained sericite,kaolinite-montmorillonite,-+-pyrite, Spottedslatesand hornfelsrocksare typicalin the
-----fluorite.Pyritized and silicifiedenvelopesencase Huayllap6n region. In all but a few localities,
veins that penetratethe shaleand quartzitecountry original macroscopic sedimentarytexturesare dis-
rock. cernible.
Mineralization
Minor intrusive rocks
Ore mineralizationoccurswithin vein systemsthat
Andesite,rhyodacite,and rhyolite dikesand sills span severalhundredmeters on both sidesof the
are numerous in the area. Field relations for the
upper intrusive.contactbetweenthe ChicamaFor-
majority of volcanicrocks within the ChicamaFor- mation and the quartz monzonite. A low-grade
mation at Mundo Nuevo and Huayllap6n indicate (currently sub-economic) stockworkwith dissemi-
that they are pre-Consuzostockin ageand definitely nated molybdenite,chalcopyrite,and wolframiteoc-
premineralization. The fact that these rocks were
curs within the deepestexposedcore of the stock. •
involved in early structural deformationand actual The principal minerals of economicinterest in the
metamorphism in contact aureoles around the Con-
veinsare wolframite,tetrahedrite/tennantite,sphale-
suzo stockstronglysupportsthis conclusion.These rite, and galena. The gangue minerals are quartz,
rocksare likely intrusiveequivalents of lower Terti- fluorite, sericite,pyrite, and carbonate. Present in
ary Calipuy Volcanics or of the Miocene Lavasen minor amountsare molybdenite,chalcopyrite,born-
Volcanics(Wilson et al., 1967; Wilson and Reyes, ite arsenopyrite, enargite (luzonite), stolzite
1964; CossioN. 1964). (PbWO4), scheelite,zinnwaldite [K2(Fe, Li, A1)2
(Si6Al,,) (F, OH4], topaz, tungstite (WOs'
Structure and contactrnetamorphism
H,), and nativearsenic. Monthly concentrate
pro-
The structural aspectsof the region may be ductionfor 1969 (average: WOs = 25 tons, Cu =
viewed as a pattern of high-angleblock faulting 40 tons, Pb = 45 tons, Ag= 6,217 ounces) was
superimposed on the Late Cretaceousto Early Terti- derived from three principal veins discussedbelow
ary gravity tectonicthrust sheetsand nappes. The (averagemill-headassay:WOa = 0.53 weightper-
thrust zones are much older than the mineralization cent, Cu = 0.60 weight percent, Pb = 0.70 weight
and in general,near the stockand within the aureole percent,and Ag = 2.30 ounces/ton;Companyfiles).
of contactmetamorphism, haveremainedessentially
Principleveins
closedto the later fluids. Away from contactmeta-
morphic zones both thrust faults and high-angle The Chabucavein at Huayllap6n (Figs. 3, 5A)
faultsare openplumbingsystems for modernthermal is a 0.5-to-3.0-meter-widevein which strikes ap-
waters (40øC, CochaConchucos). Someof these proximatelynorth and dips 75øE to vertical. Vugs
faultscertainlywere openstructures at the time of as large as 80 centimetersin diameter are common.
mineralization. Most major high-anglefault move- Pinch and swell of the vein, as well as wall rock
ment in the Andes is po.stmineralization. brecciaand "sliver" fragmentsof older vein material
The intrusion of the Consuzo stock was ac- in the veins,suggestsrecurrentfault movementdur-
companied by gentleupwarpingof the countryrocks ing mineralization. The vein is trun.cated to the
into an elliptical domal structure. Evidence for north by a systemof northeast-southwest block and
stopingand assimilation is minimal,but aplitesfeed- shear faults. The southern end of the vein is less
ing into the ChicamaFormationshalelocallyob- well mineralizedand has not beendevelopedby min-
scuredthe contactrelationships. ing operations. The Chabucavein cutsacrossseveral
A contactmetamorphicaureole200 to 400 meters early Tertiary thrust faults that placedthe Chicama
in width developedwithin the ChicamaFormation Formation above the Chimfi Formation. Mineraliza-
in responseto emplacementof the Consuzostock. tion does not follow these structures; neither is there
Immediatelyadjacentto the intrusion,shaleis trans- any variation in ore grade which might indicate an
formedinto an andalusite-chlorite/biotite muscovite- influenceof the Chicamashale or Chimfi quartzite
quartz rock. Cordierite was observednear the con- host rocks. However, open joint faulting in the
tact to the west in Rio Plata Canyon,but none was competentquartzitecomparedto very tight shearing
recognizedat Pasto Bueno. The andalusite is the • A low-grade molybdenite porphyry at Compaccha (Fig.
chiastolitevariety, with crystals0.5 to 2.0 mm long, 2) was extensivelystudied by AMAX in the 1960s (T.
and in most instancesexhibitsan advanceddegree Schassberger, AMAX Exploration, Inc., oral commun.,
1971) and is describedas having many of the features char-
of sericitization.Theseporphyroblasts are embedded acteristicof the inner core of the ,Consuzostock.
4320 m
Sta. Isabel 430!
4182 m
0 IO0 200 METERS

I ) I
N Huaura 4360m s
\
? , ,(•0 2?0
METER$
NW •/• I:, SE
i-,
PONCE.•.
<•;_
,,•t '-' .,•
L/SE/7F4Z2-
3648 m /•(•C•
U' •'•'
•U•n• x•86m •'l•-,•
HOBrENSI• -353 ../; __., _•. _ . /•::t. :1
I- ./.1• - m • I /x '• ' • - -- , '- •- x•- ' x-/ •-- - - I x/ •
ß.;,? t •2AIkolic
• ._,,,.-
oilerorion
- •_- _..-
.,. ,,•.,,l'"Propylitic olterotion• J
Fro.5. Principle
veincross
sectional
levelmaps
showing
sample locations.
A. Chabuca (Huayllap6n)
vein(N-S cross
section),
B. Consuelo-Manuelita
veinsystem (N-S crosssection),andC. Consuzo
(Loreto)veinsystem(NW•SEcrosssection)
shown.Dotsindicate
samplelocalities.
Mapsaremodi-
fied from companyfiles.
79 ø 78 ø 77 ø
.4-O
Trujillo
Z• +
Z•+
CHIMBOT
Cos!
EXPLANATION
A Tungsten 9.I n•y,+

ß Molybdenum
io ø
ß Trn
+ Leod, zincs ond silver

O Copper
O Gold ond silver ++
0 50 • I00 KILOMETERS
FIG. 6. Metallogenicmap of northern Peru. The Cordillera Bianca batholith and as-
sociatedstocksare stippled;the Late Cretaceous Coastalbatholithand plutonicbodiesof
uncertainageare shaded.A 65-m.y.agefor the PeruvianCoastalbatholith(near Casma)
anda 9.1-m.y.agefor the CordilleraBlancapluton(near Recuay)are datesdetermined by
GilettiandDay (1968). Alsoindicateis a 9.5-m.y.agefor the Consuzo stockat PastoBueno
on thenorthernextensionof the CordilleraBlanca. Notethe regionaltrendof mineralization
as well as the extentof tungsten(A) mineralization
1NIWand SE of PastoBueno.
in the shale has restrictedmajor vein development t-he Huaura camp, tabular wolframite, arsenic-rich
largelyto the Chimfi Formation. The Chabucasys- tetrahedrite,and iron-rich sphaleritecomefrom one
tem contains material characteristic of late mineraliza- principal vein, Veta Pueblo. La Victoria and Tam-
tion (see later section). boras,no longer in production,are mineralogically
The Consuelovein below Huaura (Figs. 3, 5B) similar to Mundo Nuevo. Compacchais a low-
consists of the Consuelo-Colorado veins and of the grademolybdeniteporphyrywith associated wolfra-
Manuelita-Consuelo,Nor.-Este, Peligro, and other mite-quartz veins. Mineralization at Pushas and
veins within the Chicama shale host rock on the Huaccaralies in the zoneof an early Tertiary north-
north flank of the intrusive dome. The greatest south thrust fault approximatelyseven kilometers
volume of mineralized rock is located within several eastof the Consuzocamp. At Pushasas smalllime-
hfindred meters of either side of the intrusive-shale stone replacementore body contains chalcopyrite,
contact. Vertical veinscontinuein depthwithin the pyrrhotite, pyrite, epidote,and magnetite, whereas
stock but are massive poorly mineralized quartz the Huaccara system embodies numerous small
veins,more than 200 to 600 meters away from the galena-tetrahedritemantos in quartzite. Four kilom-
contact. Within the intrusive,subparallelveins2 to eters directly southof Huaccarais a contactskarn
6 meterswide separateand rejoin, and locallyattain near Campo Majistral containingscheelite,chalco-
a total width of as much as 25 meters. Vertical pyrite, and other tactite minerals in a limestonead-
veins within the intrusive rocksmerge with shallow- jacent to a hornblendegranodiorite. The Churvilca
dippingveinsalongfoliationplanesand innumerable scheeliteprospectis north of the Pushasore body.
higher angle fractureswithin the sedimentaryunits. These depositsform a line of mineralizationmarking
At the intrusive contact, massive quartz contains the easternmostore depositionin the Pasto Bueno-
fragmentsof altered shaleand quartz monzonitein Consuzoarea. No granitic intrusivesof the Cordil-
breccia zones as much as 15 meters wide. As vein lera Blanca Miocene-Pliocene suite and no occur-
extension into the Chicama Formation is controlled rencesof mineralizationare known east of Majistral
by tight fracturingand foliation,theseveinsare only and Churvilca.
3 to 20 cm wide and most are bandedparallel with The regional mineralizationpattern parallels the
the vein walls. The ore is rich but the veins are thin Cordillera Blanca batholith in its northwest-south-
and not continuousover great distances. Major ore easttrend (Fig. 6) and is positionedjust east of the
mineralsin the Consuelovein systemare wolframke topographicdivide. Copper, tungsten,and molyb-
and tetrahedrite,in a gangmeassemblage of quartz, denurn mineralization occur in a 30-to-40-kilometer
sericite,and minor pyrite and fluorite. band that also geographicallycontains the main
In most respects,the Consuzomineralizationre- CordilleraBlancaplutonicbody. Ore depositsoccur
semblesthat presentin the Consueloveins. Adits to the northwestand southeastalong the Cordillera
and vein drifts at eleven levels extend nearly one Blanca trend where the felsic intrusives"dip" be-
kilometer into the intrusive toward its southern con- neath sedimentarycover.
tact and provide valuableinternal exposureof the
stock (Fig. 5C). The southernintrusive contact Mineral paragenesis
has not been reached. Veins are normally 2 to 3 The PastoBuenomineralparagenesls(Fig. 7A)
meters in width, but mine files record past exposure is basedon more than two monthsof underground
of unusualveins 8 to 10 meters wide. Very few mine observations, mapping,and sampling,and sub-
rugs were found in the veins of Consuzoand ad- sequentdetailedstudy of more than 80 hand speci-
jacent systems. Bandedore occursparallel with mens. Thirty polishedore sectionswere studied
vein walls in the back drifts of levels 3,384 m and with the reflectinglight microscope,but crustification
3,421 m. Outer bandsof quartz and bladedbrown and veining relationsin rug vein material form the
wolframite enclosean inner assemblageof tetrahe- basisof the paragenesis sequencepresented. De-
drite, galena,sphalerite,pyrite, and quartz. In some tailed quartz zone"stratigraphy"permittedexcellent
instances this symmetricalbandingis repeatedseveral parageneticcontrolof somesamples(Fig. 7B).
times across the vein width, possibly indicating The observational data are based on studies of
multiplevein openingand mineralizationduring this severalvein systemsin the area, someseparatedby
phaseof the paragenesis.Marked ore bandingwas three to four kilometers, and on studies of Mundo
not observed elsewhere. Nuevo, Compaccha,Huaccara, Pushas, Majistral,
Mining localitiesperipheral to the central map and other lesser localities. No one vein contains the
area includeMundo Nuevo (Bellido and Manrique, entire parageneticsequence, but adjacentveins com-
1954), La Victoria and Tamboras, Compaccha, monly have overlappingand telescopingsegmentof
Pushas,Huaccara,Majistral, and Churvilca (Fig. the mineralizationsequence.A crudezonalarrange-
2). At Mundo Nuevo,20 kilometersnorthwestof ment of mineralizationfrom the intrusive quartz
P.dSTO BUENO TUNGSTEN-BASE METAL ORE DEPOSIT 1035
GREISENllEARLY VEIN LATE

II VUG
ZONE
I-A ZONE
I-B ZONEFluo-Carbon-[•
I
Megacrysts
II-BB/C rite ate•
Quartz - Q
• I
I
MnT • ------ Wolframite
-W
- Molybdenite -
_I-- Chalcopyrite
Arsenopyrite
Bornire
Pyrite(Cubic)
: (Drusy) - A
-•p
•1 Pyrrhatire - Po
--.i-- -- Magnetite -- Enargite/Luzonite - E
--- Ruffle -- Galena _G
-- Stolzite Fe--I Sphalerite
Fe_
----Scheelite
(?)
Sericite
Sb
Sericite II
•]•.Tetrahedrite
i Arsenic(native)
-- SI
As
- Te
-S
?_egmatite
Fluorite------ Fluorite
------s•le-•-•
-- Zinnwaldite --Tungstite- T
Tourmaline
--Apatite
Rhodochrositei-r--
Catcite •---
ii- R
C
• Topaz Scheelite
-- Dolomite---D
Sc
, , , ,, , , , I , I ,J IT , , ,/,, ,, , , ,,,,r , , ,
• I O0 • 0 I I I I I I
, , ,, ,
o •"8
o o •• ,•, o, aura'<
•o r,).• ='•T,•• -0o9' •
•o 0 I• 0 C
65 85 90 95 97 99
VOLUME PERCENT OF DEPOSITION
9H-171
Brown
wolframite
T 9H-124
BASE
SLAB
IB,...:=•.
_••• .
IIt'•
•
..••/•1
•c•
,ont
'%'••,•,Fit
h ..•.•,etroh
_•,olfromit,
gl•k,••: solid
• •Block
m •
=o• 0 • •CM
o • •CM
-•,•mmc UPPERMOST SL•B
Fro. 7. zl. PastoBuenomineralparagenesis.The diagramis skewedto the right to better

illustratethe Vein and Vug periodsof hydrothermalactivity. The major periodpercentages
are estimatedat Greisen(60-70%), Vein (25-35%), and Vug (<5%). The lower borderof
the figureidentifiessamplesand positions of actualmineralspecimens usedin variousaspects
of this study. B. Diagram showingdevelopment of quartz crystalzones,which were estab-
lishedfrom basalsections cut from actualcrystals. WolframiteI----late ZoneI-A; ZoneI-A
:milky, massivequartz; Zone I-B- clear quartz,very vitreous,with a few large pseudo-
secondary fluid inclusionplanes;WolframiteII = ZoneIB; ZoneII-A boundary,occurswith
tetrahedriteand other sulfidesolidinclusions; Zone II-A = fluid inclusionsperpendicular
to
crystalgrowthplane,high inclusiondensity,"frothy"to milky; Zone II-B ----parallelmilky
fluidinclusion plane,first occurrencepost-II-A; ZoneII-B'= parallelplanes,wider thanZone
II-B zone;ZoneII-C--very lateclearquartz,no largefluidinclusions
visiblemicroscopically.
monzoniteto the edge of the area is: (a) molyb- letter prefix: GR = granite traverse, F -- field; H
denite-pyrite, (b) wolframite-tetrahedrite-chalco-
= Huayllap6n (Chabuca vein); Co -- Consuelo
and veins; Man - Manuelita veins; L = Consuzo
pyrite-pyrite, (c) galena-sphalerite-tennantite,
(d) fluorite-carbonates. (Loreto) veins; Mn -- Mundo Nuevo.
In hydrothermalsystems,evaluationof the spatial Zoning in the quartz is formed by unique fluid
variations in mineralization as a function of time, inclusionconfigurations,concentrationsof solid in-
temperature,pressure,and chemicalparametersis at clusions,and marked hiatusesin quartz deposition.
besta difficulttask. The Pasto Buenomineral para- The results,in most cases,are "phanton"crystals
genesisis empirical;basedupon observational data, within larger multizonedquartz. Figure 7B illus-
it conveysrelativetime only. Consistenttime se- tratesthe sequentialformationof Zone I-A through
quences of mineralization in differentlocations
have Zone II.-C in actualspecimens.Criticallyimportant
been constructed as outlined above. Individual time is the excellentparageneticcontrolaffordedby the
sequences with overlappingidenticalsegments have quartz crystalsand the relative positionsof wolfra-
been combined so as to describe the entire mineral mite and ferberite, e.g., wolframite I and II, in rela-
paragenesis.Material from the same quartz zone tion in the quartz "stratigraphy."
occurringin spatiallydifferentplacesyieldedsimilar Specificfeaturesof the paragenesis (Fig. 7A) in
fluid inclusionand isotopicdata. Therefore, the approximatechronologicorder are the following:
quartz zones have been used as assumedtime
markers in constructingthe mineral paragenesis.I. Greisen-earlyVein minerals:
The crudemineral zonationappearsto be largely A. Quartz megacrysts. Quartz megacrystsoccur
temperatureand time dependent(basedupon the with phyllic alteration assemblages as secondary
assumptionof absolutetime markersin the para- ovoidquartz,2 to 9 mm in diameter,and donsistof
genesis). compositecrystalsof both magmaticand alteration-
Mineralizationis divided into three main periods stagedeposition.
classifiedas Greisen, Vein, and Vug: the Vein B. Pyrite-pyrrhotite-magnetite. An increase in
periodis furtherdistinguishedasearlyandlate.The the hydrothermalfluid sulfur fugacityor a drop in
Vein and Vug periodsare subdivided on the basis temperaturein the quartz monzonitewall rock ad-
of major quartzzonesandthe finalfluoriteand car- jacent to veinsproducedpyrite or pyrite-pyrrhotite
bonatedeposition. The Greisenperiod represents in the alterationfrom the decomposition
of primary
latestagegreisenalterationof the stockpriorto for- magnetite. In a few localitiesall three minerals oc-
mationof earlybarrenquartzveins. Specifically this cur togetherbut not necessarilyin equilibrium.
stageincludesdevelopment of restricted
greisenalter- C. Early fluorite. Early fluorite is often very
ation patternsand disseminated mineralizationand coarse,nearly pegmatitic,highly sheared,and frac-
the formationof massivepods of early fluorite- turedandis blueto blue-green,purple,and brownin
adularia, here referred to as "pegmatitic"fluorite. color. It occurs(1) in greisenassemblages of fluo-
Many of the processes initiatedduringthe Greisen rite, sericite,zinnwaldite,pyrite, and quartz, (2)
periodcontinued into the Vein periodof hydrother- with pyrite in smallveinletsand feathercracks,and
mal activity. The Vein periodwasinitiatedby the (3) in massivepegrnatite-like pods0.4 to 1.5 meters
development of early barrenquartzveins--the first in width and severaltensof metersin length,which
evidenceof veiningin the stock--andincludesZone contain adularia (subsequentlyaltered to clay),
I-A throughZoneII-A and wolframiteI and II de- pyrite,and in a few occurrences,molybdenite.
position.The Vug periodwasa late phaseof vein D. Sericite I. Sericite I was producedduring
deposition that produced mineralscharacteristic
of pervasivealterationof the feldsparsthroughout large
final rug wall crustation. The distinctionbetween portionsof the stock. SericiteI is phyllicalteration
the Vein and Vug periodsis not meantto imply that sericiteand wall rock alterationsericiteadjacentto
onlyvein deposition
occurredfollowedby onlyvug early veins. It doesnot occuras a vein mineral.
formation. Open vugs are noted throughoutthe E. Other minerals. Tourmaline,topaz, apatite,
mineralparagenesis, but onlymineralscharacteristicsphene,rutile, stolzite,arsenopyrite,
bornite,chalco-
of final vug wall crustationtypify the Vug period pyrite, and molybdenitewere observedas minor dis-
of deposition.The estimatedpercentof mineral seminatedmineralsin the greisenaltered rock, as
deposition for eachperiodin Figure7A is included coatingin fractures,andas hightemperature sulfide
on the paragenesis diagram. Most datain the fol- veins.
lowing sectionshave been presentedwithin this
frameworkto affordeasycrosscomparison andposi- II. Wolframite I, II:
tioningwithin the paragenesis.Samplefield num- Tungstenmineralization occurredduringtwo dep-
bers indicateapproximatelocationand type by a ositional episodes.The economicallysignificant
PASTOBUENOTUNGSTEN-BASE
first periodproduceda wolframiteof thick stubby purple non-fluorescent crustifications

on rug and
brownblades(huebneriticwolframite,approximately fracturewalls. Wolframitereplacement by scheelite
75 weightpercentMnWO4) randomlypositioned in was not observed in the area.
massivevein quartz. The secondperiodwolframite IX. Carbonates:
first appearsat the end of quartzZoneI-B deposi-
tion and is a black, elongateand euhedralrug min- Rhodochrosite,calcite,and dolomiteof only ap-
eral (ferberite, <5 weightpercentMnWO4). proximatelyknown age relationsare extremelyrare
and were foundat only eight samplelocationsin the
III. Enargite-luzonite: mines. They occurin minor amountsas very late
Very minor quantitiesof enargite(CuaAsS•) are rug-filling material. Calcite I is a pearly white
foundin early sulfidevein assemblages with tetrahe- translucentcalcite, whereascalcite II has a rhombo-
drite, pyrite, and galena. X-ray analysis.of this hedralhabit and is .opticallyclear. Siderite (not ob-
material suggestspartial conversionto the low- servedby the authors) was reportedas a common
temperaturepolymorphluzonite (end member in- ganguemineral in the higher level low-temperature
versiontemperaturerange= 275ø to 320øC) (Skin- veins peripheralto the Consuzostock (Malaga S.,
ner, 1960; Maske and Skinner, 1971). 1954).
IV. Tetrahedrite-tennantite: Fluid Inclusion Studies
Early tetrahedriteis antimonyrich. Intermediate More than 85 polishedplates of representative

varietieshavehigh arseniccontentsand tennantiteis samples of quartz,fluorite,sphalerite,carbonates, and
typical of late mineralization. Botryoidal native wolframite were studied under the microscope. Se-
arsenicis foundas a very rare accessory to late sul- lection of material depended on its suitability for
fide vein assemblages. multipleusagein both fluid-inclusionand isotopein-
vestigationsand on its reliable placementin the
V. Galena-sphalerite: mineral paragenesis. Primary inclusions,and oc-
Galenawasprecipitated priorto andduringsphale- casionallypseudosecondary inclusions =, were selected
rite deposition.The changein the composition of for microscopic analysisin a heating stageand freez-
sphaleritethroughtime is reflectedin a colorchange ing stage. Platinum resistance probes positioned
from a dark brown to a light transparent green- within samplechambersenableddirect digital read-
brown,and finally,a very dark opaquebrown. out of temperaturesto ---0.5øC. Mettler thermo-
metric organicstandardsand pure metals for the
VI. Sericite II: heating stage and NaC1 solutionsfor the freezing
SericiteII is strictlya hydrothermalvein mineral stage establishedan overall calibrationaccuracyto
and is developedin late mineralization,commonly -----5øC and --+IøC,respectively.Individualheating-
clumpedwith tetrahedrite. It cuts early wolframite stage runs generally were reproducibleto +--IøC.
I bladesand in somecasesfills cleavagefractures in Sampleexaminationand selectionand prelim'mary
both wolframite I and earliestlate-stagegalenaand fluid-inclusion studiesprecededthe isotopeanalysis
work.
fluorite. It is depositedin fractured vein material
and at the baseof openvugsas coarseplates0.5 to Suitablefluid inclusionsin the large majority of
Pasto Bueno material were in the 15-to-35-micron-
6 mm in diameter. Locally sericite II actually
"closed"vug spacesin veins. It is clearly earlier diameterrange. Many very small inclusionsesti-
than the periodof major fluoritedeposition. matedto be approximately 0.1 to 0.5 /• in diameter
(unsuitablefor temperatureand salinitydetermina-
VII. Late fluorite: tions) which occurwithin magmaticquartz pheno-
Late fluorite is a late vein and rug ganguemineral crysts,greisenquartz megacrysts, and feldsparmin-
of substantial volume. Color zones in the fluorite en- erals were observedat 2,000 x magnification using
able paragenesiscontrol as an adjunct to the early oil immersion objectives.Rare inclusions nearly0.2
quartz zones. Oscillationsof green and colorless millimeterin diameteroccurin verylatefluoriterug
fluorite bandsare followed by a period of colorless crystals.
fluorite deposition,then by a brief episodeof purple Three main types of inclusionswere observedin
fluorite,and finallyby a major stageof greenfluorite. Pasto Bueno material:
VIII. Scheelite: Type I. Two-phaseinclusions
containinga liquid
Scheelite is observed at three minor localities in anda gasbubble(<30 volumepercentgas).
the Pasto Bueno-Consuzo area and at Churvilca. •An excellentdiscussionof primary, pseudosecondary,
and secondary inclusions and other fluid inclusion features
Scheeliteoccurs after wolframite II as yellow to is given by Roedder (1967).
TypeII. Polyphase inclusions

containinga liquid, data on anhydrite solubility (Blount and Dickson,
a gasbubble,andan assortmentof daughterminerals 1969). It should be noted that anhydrite is not
( < 30 volumepercentgas). observedas a separatealterationor ganguemineral.
TypeIII. Two-phase, gas-richinclusionscontain- The occurrenceof anhydritein somefluid inclusions
ing a gasbubble(70 to 90 volumepercentgas)and may resultfrom a shift in the aqueoussulfur species
a liquid (wettinginclusioncavitywall). equilibria with a drop in temperature (Ohmoto,
The great majority of fluid inclusionsin Pasto 1972) or with diffusionalhydrogenloss from the
Buenomineralsare of Type I. Type II fluid in- fluid inclusion. The amountof hydrogenlossneces-
clusions in materialof Greisen-early sary to shift the aqueoussulfur speciesequilibria
occurprincipally
Vein and in Zone I-B to Zone II-BB'C periods. is many orders of magnitude lower than that re-
Clearlyidentifiable
TypeIII gas-rich fluidinclusionsquired to effectthe •tDa2oof the fluid inclusions.The
were observed in material from the Greisen-early sulfur isotopedata (Isotope section) indicatethat
the SO4- concentrationin the hydrothermalfluids
Vein periodonly. In a few samples,
TypeIII gas- was low.
rich inclusion bubbles were observed to have nu-
In some fluid inclusionsseven or eight daughter
cleatedon simultaneously trappedsolidcrystals.
The
mineral grains were observed. As it is unlikely for
occurrence of closelyspaced Type I and Type III
more than onecrystalof the samemineral to nucleate
primaryinclusions in -samplesclearlyindicates
that in the samefluid inclusion,severaldaughtermineral
duringat leastthe.earlystage(Greisen throughearly
speciesother than those describedare presumably
Vein) of thehydrothermal activitythesolutions
were
at or closeto boilingconditions.The presence of a present in these inclusions. Nonmagneticopaque
few Type III fluidinclusions with Type I anl II daughter mineralshave also beenobserved,in some
instances two in the same fluid inclusion. In some
fluid inclusions suggests numerousminor boiling
eventsfor ZoneI-B throughZoneII-BB'C periods. Type II fluid inclusions a very smallred-brownmin-
Theselaterboilingevents arenotaswelldocumented eral flakeis present,
which is thoughtto be hematite.
as the early boilinghistory,nor do they represent Birefringent daughter minerals .of rhombohedral
shapeare rare but wherepresentare believedto be
largeperiodsin the paragenesis. But thesedata carbonate minerals.
do indicatethatfluidsmayhavebeencloseto boiling
duringthemajorperiods
of mineraldeposition.
Distributionof daughterminerals
Daughterminerals Daughtermineralsin fluid inclusionsoccurdomi-
Halite (NaC1), sylvite (KC1), anhydrite nantlyin materialfrom two major phasesof the para-
(CaSO4), and dawsonite[NaAI(COa)(OH)2] genesis. The first occurrenceis in materialof the
daughterminerals in Type II Greisenand early Vein periods. The greisenquartz
havebeenidentified
inclusionswith some reliability. Halite is present megacrysts
and magmaticphasemineralsstudiedin
in nearlyall TypeII inclusions ac- thin sectionwith high-poweroil objectivescontain
andis generally
companied by sylvite.Theyarebothisotropicand two populationsof fluid inclusions.The first group
colorless.Halite formssharpcubiccrystalswhich is of primaryType II inclusions that havedaughter
reactwith the water to form crystalsof the bire- mineral assemblages
which typically occupygreater
fringentdihydrate[NaC1-2H20]uponfreezingof than40 percent,and in a few cases60 percent,of
fluid. Sylviteis generallyroundedin the inclusion volume. The number and type of
the inclusion
form and of lower relief. daughterminerals,and the percentof total inclusion
Dawsonite (Coveney andKelly, 1971) commonlyvolumethey occupy,differ drasticallyamongad-
occursin TypeII inclusionsasbirefringent bundles jacent inclusions. This feature probablyreflects
of acicular whichtypicallyfill the inclusionsalinityfluctuationsresultingfrom volatile surging
crystals
cavityleavingroomforlittleelseexcept a verysmall andboilingduringthe late magmatic-early postmag-
halitecubeanda distortedvaporbubble. Dawsonite matic stageand is mostprevalentin greisenrocks
also occursas solid inclusionsin quartz. within phyllie alterationassemblages.A second
Elongaterectangular prismswith parallelextinc- group of Type I inclusionsin the greisenquartz
tion and moderatebirefringenceare observedin megacrysts occursalong late secondaryinclusion
some fluid inclusions in Pasto Bueno material and planes. These inclusionsare essentiallyfree of
arethought to beanhydrite crystals.Uponheating, daughtermineralsand fillingtemperatures are esti-
thesedaughtermineralswere observed to increase matedvisuallyto be 360ø to 400øC.
in dimension, suggesting that solubilityof the min- The second major occurrence of daughterminerals
eral decreased with increasingtemperature. This is in materialrepresentative of ZoneI-B (late Vein)
behavior is in basicagreement with theexperimentalthroughZoneII-BB'C (earlyVug) deposition.The
GREISENI
IEARLY VEIN LATEII V•/•
16
•)
o 6
hi
Fro. 8. A. Fluid-inclusion filling temperatures. Vertical lines indicate maximum range of

temperaturesmeasured. Small horizontal bars bracket the temperature range of these inclu-
sions considered primary. Greisen and early Zone I-A temperatures are estimated from
geologicand oxygen isotopedata. Boxes A and B contain the range of secondaryinclusion
filling temperaturesfor Greisen and early barren quartz veins, respectively. The period of
fluid boilingdoesnot extendmuchbeyondthe time representedby samplenumber7Py-Consuzo.
B. Inclusionfluid salinity. Erratic salinity fluctuationsof 5 to > 40 equivalentweight percent
NaC1 occurearly in the paragenesis.The data from later dilute fluids suggesta dilution dur-
ing both phasesof wolframite deposition.
++ -7- ++ ++ -7- +++
++
++ +++++
I I I I
65•='''
METALOREDEPOSIT 1041
•7•77 •
•7777 •
daughtermineralsoccupyminorportionsof the total the Greisenperiod or from the early Vein-Zone I-A
inclusionvolume, in striking contrast to the earlier period (material older than sample9L-220). Fluid
period of daughter mineral occurrence. Dawsonite inclusionfilling temperaturesof 234ø-248øC were
is more commonthan halite in this secondperiod. obtainedfor secondary(?)inclusionsin highly frac-
tured Zone I-A early quartz veins (9F-108, 9F-109,
0 therfluid phases and PampasWatch Vein). Type I inclusionsin the
In additionto the aqueoussolutions,daughtermin- greisenquartz megacrystswere too smallfor homog-
erals, and the vapor bubble; a few other minor enizationstudiesbut wereestimatedvisuallyto repre-
phaseswere observedin the fluid inclusionsin Pasto sent360ø-400øCtrappingtemperatures. The filling
Bueno material. Within Zone II-A and Zone II- temperaturesof the extremelysalineType II inclu-
BB'C quartz,an immisciblefluid wasobservedwhich sionsin greisenmegacrysts couldnot be determined.
exhibitsa refractiveindex slightly less than that of The actual temperaturesduring the developmentof
the salt-saturatedaqueoussolution. This fluid is greisenmegacrysts(400ø to 450øC) were estimated
thoughtto be liquid H2S (Roedder,1971). In many from the quartz oxygenisotopedata (discussedin a
instances,the very conspicuous odor of H20 was following section).
detecteduponbreakingopeninclusions containedin
quartz and fluoritethat precipitatedduring the major Salinity data
episodeof sulfidedeposition(Figs. 7A-9A). CO2
H, molar ratios were measured (see Isotope sec- The freezing point depressionof inclusionfluids
in Pasto Bueno minerals was determined for 32
tion, Table 3, Fig. 10A) and the total partial pres-
sure of remaininggasesin fluid inclusionswere ob- primary inclusionsin minerals from 12 localities.
tained during vacuum crushing and extraction of The data indicatea general decreasein salinity of
water from the fluid inclusion samples. For a the fluids during mineralization(Fig. 8B, Table 3).
typical fluid inclusionextractionyielding approxi- Visual estimatesindicate that the salinity of very
mately 5 milligramsH,, the partial pressureof gas early Type II inclusionsin Greisen quartz mega,-
remainingafter condensation of H•O, CO2, and H•S crysts must certainly contain solutionsof salinity
in liquid nitrogen traps routinely measured10-" to greaterthan40 equivalentweightpercentNaC1. The
10-5 torr (or roughly 3 x 10-7 molesm 10-• mole drastic variations in the number and quantity of
fractionof total volatiles). The amountof dissolved daughtermineralsin these fluid inclusionssuggest
CO,in the fluids is moderate(averageCO2/H20 that the salinityof theseearly fluidsfluctuatedsub-
molar = 0.02). Flat, well-formed,primary fluid in- stantially. The range of the measuredfreezingpoint
clusionsexamined in samplesrepresentingthe en- depressionsduring the Vein and Vug periods are
tire paragenesisfailed to indicate the presenceof -13.5øC (17.6 equivalentweight percentNaC1) or
liquid CO, However, it is noted that these data less (Fig. 8B) and -1.2øC (2.0 equivalentweight
representaveragesextracted from many fluid in- percentNaC1) for late fluorite period fluid inclu-
clusionsof more than one generationcontainedin sions (9H-148, green fluorite). A suggestionof
the samplesanalyzed. Care was taken to minimize decreasedsalinity in primary fluid inclusionsis ap-
this problem,but some uncertaintycould not be parent from samples9L-220 to 9Co-238 and from
avoided. A comprehensive fluid-inclusiongas-analy- 9Co-112through9Co-221-1to 9H-124-1. The fluid
sisstudyis underwayto further elucidatethe chemi- inclusionsmeasuredare from samplesof well known
cal nature of Pasto Bueno hydrothermalfluids. age relations; a portion of the later salinity trend
was obtainedfrom a singlezonedquartz crystal. In
Filling temperaturesof fluid inclusions both seriesa decreasein fluid salinity of 5 to 8
Fluid inclusionfilling temperatures(Fig. 8A, equivalentweightpercentNaC1is followedby an in-
Table 3) were determinedfor 104 representative creaseof about 4 equivalentweight percent NaC1.
fluid inclusions contained in 63 sections of material This point will becomesignificantin a later discus-
from 22 localities. An overall drop in filling tem- sion of the isotopedata.
peratures during mineralization is noted (as dis- During freezing, the solutionsin several NaC1-
cussed earlier, this might involve time as well as bearinginclusions developedcrystalswhichare pre-
spacerelationships). Post-middleZone I-A (9L- sumedto be the NaC1.2H•O dihydrate (Roedder,
220) temperatures vary from 290øC for pre-wolfra- 1971). In three fluid inclusions (9Co-234,9Co-112,
mite I quartz to 175øC for late carbonatedeposition. and9H-124-3) onlyfaintlyvisiblecubeswith rounded
The temperatureincreasesfrom 160ø to 240øC dur- edgespersistedupon warmingof the fluid inclusion
ing the late fluorite period. to severaldegreesabovezero. The solidsare pos-
Filling temperaturemeasurementswere not ob- sibly the carbon dioxide hydrate CO2'5a• H20
tainedfrom primaryinclusions in the materialfrom described by Roedder(1963) and Takenouchi and
P.4STOBUENO TUNGSTEN-BASEMETAL ORE DEPOSIT 1043
Kennedy (1965a), thoughCO2 pressuresare gen- TABLE 4. Estimated Depth of Mineralization, Hydrostatic
Fluid Pressures,
and BoilingTemperaturesfor Ore Fluids
erally low and no liquid CO2 was recognized.Not-
ably,fluidinclusions
in theses
threemineralscontain Mine
large amountsof the dawsonitedaughtermineral. Huayl- Con- Con-
lap6n suelo suzo
Pressure Estimation
Puna surface 4,500 4,200 4,300
Type I fluid inclusionfilling temperaturesare (elevation in meters)
minimumtemperaturesof fluid entrapment,because Plus volcanic cover 6,000 5,700 5,800
(1,500 meters)
of compressibilityand thermalexpansioncharacter- Less ore level 4,130 4,050 3,400
isticsof aqueoussolutions. This fact necessitates a (elevation in meters)
correctionto the filling temperaturewhich depends Depth to mineralization 1,870 1,650 2,400
(meters)
upon the pressureand salinity of the fluids. The Pressure 155 136 198
pressureof hydrothermalfluids during ore deposi- (atmospheres)*
Temperaturesof boiling (øC):
tion is in most casesequal to, or greater than, the 15weightpercentNaCI 390 350 366
vaporpressure. At the boilingcurvefor a salt solu- 25 weightpercentNaCI 415 370 385
tion,thefluidpressure andvaporpressure are equiv-
alent for the temperatureof a homogeneous fluid. * Assumesolutiondensityof 0.8 gm/cc or 82.6 atm/km.
The filling temperatureof fluids entrappedin fluid
inclusionsat the boilingcurve would require no cor-4). At theseestimateddepths,boilingwouldoccur
rection. Nonboiling hydrothermalfluids will be at only at fluid temperatures
of 350ø to 415øC,assum-
pressuresgreaterthan the vapor pressurewith pres- ing botha 15 anda 25 weightpercentNaC1salinity
suresgenerallybetweenthe vapor pressureand the (Haas, 1971). Thesepressure-depth estimatesare
lithostaticpressure. In extremeconditionsof grout- compatiblewith the fluid inclusionevidencewhich
ing and choking of the vein system,fluid pressures indicatesthat boiling was restrictedlargely to the
may exceedlithostaticpressures. For fluid inclu- fluids associatedwith the high temperatureGreisen
sionsin material precipkatedfrom these fluids, a and early Vein periodsbut was absentat tempera-
pressurecorrectionto the measuredminimumfilling tures below 290øC in the post-Greisenand early
temperatureis necessary.Dependinguponthe pres- Zone I-A periods.
sure and salinityof the fluids,pressurecorrections If it is assumed that the water table were not at
as little as +5 øC to more than +100øC are required. the surfacebut rather near the baseof the permeable
An estimateof fluid pressuresduring mineraliza- pyroclasticcover (near the buriedPuna surface),the
tion is essential to the evaluation of fluid inclusion equivalentcolumn of brine would be nearly 850
filling temperatures.The fluid pressures in the Pasto metershighandhavea pressure of approximately 70
Bueno hydrothermal system are estimated in the atmospheres at its base. Boiling of thesefluidsunder
followingdiscussion by (1) geologicreconstruction hydrostaticconditionswould occur in a temperature
of the depth to mineralizationand cal.culation of the range of 300ø to 310øC. The presenceof only a
pressurelimitsat assumed lithostaticand hydrostatic small amount of ground water in the country rock
conditions,and (2) estimationof the pressureby above the intrusion is suggestedby the alteration
plottingthe fluid inclusioncompositional data in the patternsand isotopedata. The actualfluid pressures
NaC1-CO•-H•O system. were probablybetweenthe extremesof 70 and 200
atmospheres as determinedfrom the depth to min-
Hydrostatic-lithostaticpressure model eralization,assuminga hydrostaticmodel.
A maximum depth of 1,500 meters of volcanics Fluid pressuresequalto lithostaticpressuresprob-
(based on geologicarguments; Landis, 1972) is ably representapproximatemaximumpressuresfor
believed to have existed above the now-exhumed shallow epizonal hydrothermal systems. (Fluid
Mioceneerosionsurface(Puna surface;Wilson et "over-pressures" in excessof lithostaticare possible
al., 1967). Replacingthis 1,500 metersof volcanic but difficult to evaluate.) Assumingan average
cover yields the maximum depth to mineralization rock densityof 2.6 grn/cma for the pyroclastics and
(Table 4). To evaluatethe reasonableness of these sedimentaryrock cover, the lithostatic pressures
depths a hydrostatic model is assumed. In open would have been415 to 605 atmospheres.
vein systemsof shallowdepththe pressureson hy-
NaCI-CO•-H•O equilibrium pressuremodel
drothermal fluids can be equated to those of an
equivalentstandingcolumn of brine solution. As- The total vapor pressurein the Pasto Bueno hy-
sumingthe brine solutionhas an averagedensityof drothermal fluids can be estimated,provided the
0.8 gm/cma (or 82.6 atto/kin), the maximumfluid carbondioxide weight percentdissolvedin the in-
pressureswould be 136 to 198 atmospheres (Table clusionfluids,the temperature,and the fluid salinity
104:4 G. P. LANDIS AND R. O. RYE
are known. The CO2/H20 molar ratio of the fluid curred at relatively low temperatures (260 ø to
inclusionsaverages0.02 ---+ 25 percent (Table 3). 210øC) from aqueousfluidsof moderatesalinity (17
These ratios are the averagefor all inclusionsbroken to 2 equivalentweight percentNaC1). Halite, syl-
openin the vaccumextractionof the inclusionfluids. vite, dawsonite,anhydrite,and other minor daughter
The extent to which CO2/H•O varies among indi- mineralsoccurprincipallyduring the Greisen-early
vidual inclusionsin a given sampleis not known. Zone I-A periodand during a later sulfidemineral-
A few unusuallylarge CO2/H•O ratios are thought ization period. Erratic fluctuationsin the salinity
to be a combinationof boiling and volatile segrega- of the solutionsand the presenceof vapor-dominated
tion of CO2-richfluids (greisen,fluorite,pegmatite) inclusions,during the Greisenperiod and through
and of various decarbonizationreactions involving early Zone I-A barren quartz vein emplacement, in-
propyliticalterationand limestonecountryrock. dicate boiling of the early fluids. Although minor
At a temperature of 250øC, a solution with a boiling of the fluids may have occurred at subse-
salinity of 10 weight percentNaC1 and 3.2 weight quent periods in the paragenesis,apparentlymost
percentCO• (obtainedfrom an estimatednumberof of the later ore-forminghydrothermalfluids were at
fluid inclusions,typical fluid inclusiondimensions, pressuresgreaterthan their boilingcurve pressures.
and average CO•/H20 ratio and amount of I-I•O An 850-to-2,400-meterdepth to the site of min-
extracted)shouldhavea vaporpressureof approxi- eralization is postulatedfrom geologicaland geo-
mately 165 atmospheres, while at 15 weightpercent chemicalevidence. A typical fluid pressureof ap-
NaC1the samesolutionshouldhavea vapor pressure proximately150 atmospheres necessitates a pressure
of about245 atmospheres (Takenouchiand Kennedy, correctionto the fluid inclusionfilling temperatures
1965b). Assumingequilibrium,vapor pressuresof of +5 ø to +10øC (Klevtsov and Lemnlein, 1959)
the hydrothermalfluids were then 165 to 245 atmo- and +10 ø to --+20øC(Samoylovichand Khetchikov,
spheresthroughoutmostof the mineralization. 1968), dependingupon the filling temperatureand
An approximaterange of CO• pressuresin the the type and concentration of salt in the fluids. For
hydrothermalfluidscanbe calculatedfrom CO•/H•O the worst case•lithostaticpressuresof 500 atmos-
molar ratios of the fluid inclusions,the volume of a pheres,filling temperaturesof 300øC, and a salinity
typical inclusion,the quantity of water extracted, of approximately20 weight percentNaCl--a pres-
and the ideal gas law. Such calculationsindicatea surecorrectionof approximately+40øC is indicated.
range in CO• pressuresof 20 to 38 atmospheresat It was not possibleto determinethe pressurecor-
25øC. The occurrenceof pyrite, pyrrhotite,arseno- rection needed for each fluid inclusion studied.
pyrite, and high concentrations of FeS in sphalerite Greisenand early Vein fluid inclusionswere boiling
and the lack of siderite at Pasto Bueno are com- and therefore require no correctionsto their filling
patible with theseCO2 pressuresif Io2 valuesof the temperatures. However, filling temperaturesfrom
fluids were low (Holland, 1959, 1965).. CO•.5• fluid inclusionsin material post-early Vein in the
I-I20 pressurescouldnot be determinedbecausethe paragenesisdo require some pressurecorrection.
effectsof dissolvedsaltsare only qualitativelyknown. The magnitude of this correctionis believed to be
However,approximateC0• pressures obtainedby small (+5 ø to +10 ø) for most fluid inclusionsbe-
this methodTakenouchiand Kennedy,1965a,fig. 1, causeof the reasonableness of the hydrostaticopen
p. 384) are in reasonableagreementwith the cal- vein model. But large pressureexcursionsbetween
culated range. hydrostaticand lithostaticcannot be ruled out for
Fluid pressuresdetermined by the hydrostatic the Pasto Bueno fluids. In view of these uncer-
pressuremodelhave a maximumprobablerange of tainties and the ---+5øCaccuracyof the temperature
70 to 200 atmospheres,whereas the equilibrium measurements, no pressurecorrectionswere applied
NaC1.-CO2-I-I•O modelpredictsa rangeof 165 to 245 to the inclusionfilling temperatures.
atmospheres.A reasonable maximumpressurecase
Stable Isotope Studies
for the "open"shallowhydrothermalsystemat Pasto
Buenois the lithostaticpressurerangeof 415 to 604 Stable isotopestudiesof minerals and fluid in-
atmospheres.The most probablerange in pressure clusionsin hydrothermalore depositsand associated
from a geologicaland geochemicalviewpoint is ap- felsic intrusivescan aid considerablyin understand-
proximately 70 to 200 atmospheres;a reasonable ing the complexities of postmagmatic ore deposition.
typical value is postulatedto be about 150 atmo- The D/I-I data, and to a lesser extent, the x80/xøO
spheres. data from analysesof geologicalmaterials, are es-
sential to interpreting hydrothermalfluid histories
Summary of Fluid Inclusion Studies (e.g., Rye and Sawkins,1974; Sawkinsand Rye,
The fluid inclusion data from minerals at Pasto 1970; Sheppard et al., 1971; Ohmoto and Rye,
Buenoclearlyindicatethat main ore depositionoc- 1970). The •aC/•2C and the a•S/3•S ratio data
provide indicationsregarding the source of these materialas H•., CO2,and SO2, respectively. Analyses
chemicalcomponents in hydrothermalore fluidsand, weremadeon a modifiedNuclideCorporationRMS-
in some instances,regarding the physicochemical60, 6-inch, 60ø sectormass spectrometer.All ap-
environment (Ohmoto, 1972). In general, data plicable machine (instrumental), abundance,and
from stableisotopes promiseto shedlight on the de- standardscorrectionswere appliedto the raw analy-
gree of genetic linkage between Cordilleran-type ses (Craig, 1957, 1961b; Deines, 1970; Hulston,
ore deposits (as defined by Sawkins, 1972) and 1964) and in addition, deuterium analyseswere
spatiallyassociated felsicintrusives. specifically
correctedfor the formationof Ha+ in the
ion source. For referencespertainingto standard
Experimental Methods
vacuum techniquesused in samplepreparationfor
Notation the massspectrometer, seeRye and Sawkins(1974).
Routine analytical precision, as reported in the
Standard stableisotopenotationis usedthrough-
literaturefor stableisotopeanalyses,was maintained
out this report. All isotopevaluesare reportedas
during all analytical'procedures(Landis, 1972, Ap-
per mil differencein the ratio, R, betweenthe sample
(A) and a suitablestandard,
pendix B; Rye and Sawkins,1974).
$Mx = [Rx- R,ta)/Rsta] X 1,000 Sampleselection

andpreparation
whereR=(D/H), (180/•øO), (laC/12C), Pasto Bueno material intended for crushingand

and M = D, 180, •aC, s4S. Rsta is the reference fluid inclusionwater--extractiontechniqueswas se-
standardratio SMOW (StandardMean OceanWa- lected to avoid obviousplanesof secondaryinclu-
sions. All material was baked in an oven at 80 ø to
ter) for hydrogenandoxygen(Craig, 1957,1961b),
PDB (PeeDeeBelemnite)for carbon(Craig, 1953, 110øCfor 24 to 120 hoursand then placedin stain-
1957), and CationDiablotroilite for sulfur (Thode less steel crushingtubes and excavateduntil "out-
et al., 1961). gassing"of adsorbed gasesceased.Rye (1966) dis-
cussedimportantconsiderati6ns of sampleselection.
Fractionationequations Sulfides were selected and readied for combustion
by drilling out individual mineralsusing a dental
Pertinent experimentalisotopicfractionationdata
drillingtool, by handpickingof coarselycrushedore
are referencedin the following: sulfide-sulfide,
Kaji-
speciments, and by acid treatmentand conversionto
wara and Krouse (1971) and Czamanskeand Rye
Ag2S of very fine crystallinemixtures of sulfides.
(1974); feldspar.-muscovite-water,
O'Neil and Tay-
Most sampleswere estimatedto be >95 percentto
lor (1967, 1969); quartz-water, Clayton et al.,
100 percentpure and comtaminationgenerallycon-
(1972) and O'Neil (oral commun.,1971); calcite-
sistedof quartz.
water,O'Neil and Epstein(1966a) and O'Neil et al.
Mineral separationswere performedusinga stand-
(1969); dol.omite-water,Northrop and Clayton
ard heavy liquid and magnetictechniqueor hand
(1966); Co2-calciteand Co2-H20, Bottinga (1968,
pickingto obtainsuitableconcentrates.When neces-
1969) and Bottingaand Craig (1969); and hydrous
say, quar.tzand sulfideswere treated with hot HF
minerals-water, Suzuokiand Epstein(1970). Rho- to removethe feldsparsand otherssilicatesand with
dochrosite-waterfractionation was approximated
H2SO4 to removethe fluoride salt residue. Quartz
usingthe calcite-waterdata and data on other speci-
samplesalso were treatedwith a fluoboricacid solu-
fic metal .cationcarbonatesystems(O'Neil et al.,
tion to removeoxides(5 partsof 38 percentfluoboric
1969). Difficultiesin the quartz-water1•O curves
acid and 1 part eachof phosphoricacid and of ferric
are discussed in Clay.ton
et al. (1972) andTruesdell chloride). X-ray techniqueswere used to help
(1971). In this report,calculations are basedon an
maintainthe purity at >95 percent.
unpublishedexperimentalcurve of O'Neil (oral
commun.,1971), 1,000In, = 3.57 x 10ø/T• - 2.73, Hydrogen Isotopes of the Hydrogen Fluids
which appearsto describenatural systemsmostac- Fluid inclusion water
curately. Calculationsusing the most recent data
(Claytonet al., 1972) are presentedfor comparison The 8D value (Table 3) of waters containedin
but yieldcalculatedequilibriumwater $•O composi- fluid inclusionsfrom 34 PastoBuenosampleswhich
tionsmore enrichedin 1•O than the othercurveby are keyedto the mineralparagenesis vary from -29
approximately1 to 1.5 per mil. to -88 per mil (Fig. 9A). The major featuresof
Massspectrometer and extractionprocedures the data are the following. (1) $Da2ovaluesof the
hydrothermalfluidsvary somewhaterraticallyduring
The stableisotopesof hydrogen,oxygen,carbon, greisenformationand the early stagesof pegmatitic
and sulfurwere analyzedfrom selectedPastoBueno fluorite and Zone I-A barren quartz vein emplace-
GREISEN
IIEARLY !/E//V LATEII !/UG
ZONE
I-A I ZONE
I-B II-BB•rite ore
-20m • i i _ I •/ --
-ioo
• GR-6
--
0 5
u3 4
II '
I I I '•1 I I I I I I II II I I 1/11 II I I IIIII I IIII
,, ,,, ,,,
• o ,= o
65 85 90 95
VOLUME PERCENT OF DEPOSITION
FIG. 9. Pasto Bueno hydrothermalfluids isotopiccomposition. A. •D values of water in

fluid inclusions. Note deuterium depletion at periods of wolframite deposition. 9H-152, GR-6,
and 9oHuaccaraare secondaryinclusionwaters discussedin the text. B. Calculated •8Omo
values of the hydrothermalfluids. Shadedbar (+6.5 to +9.0 per mil) is the probablerange
of magmatic (deep-seated)8•8OH2o.Vertical bars indicate the range of uncertaintybased on
the maximum temperaturespread. Small horizontal bars limit the range of 8x•O•2ousing the
1971 (lower bar) and the 1972 (upper bar) quartz-water oxygen isotopeexperimentaldata
and the "best" primary inclusion filling temperature. Solid triangles indicate waters in isotopic
equilibrium with carbonates. Boxes A and B are waters calculated for those samples using
secondaryinclusionfilling temperatures. Solid circles are fluid inclusionwaters analyzed for
•80 and open triangles are calculatedwaters in equilibriumwith wolframite (see Table 3).
TABLE5. Hydrogen and Oxygen Isotopic Compositionof Hydrous Minerals
Geologicsetting Sampleno. Description (SMOW) (SMOW)

Biotite
Primary magmatic crystallization GR-8 Magmatic biotite; pyrite; no sericite -- 68.6 5.77
GR-8x Higher magneticsusceptibilityfrac- - 65.3
tion of GR-8 biotite
9L-199 Magmatic biotite cluster; biotite --68.7 5.78
phenocrystsin aphanitic dike
Alkalic alteration GR-6 Weak pervasivealteration; no pyrite -76.6 5.82
GR-9 Weak alteration; abundant pyrite -76.1 6.09
Propylitic alteration 9L-206 Propylitic alteration; clinozoisite -- 76.6 6.22
chlorite
Phyllic-argillic alteration GR-13 Intensealteration; pyrite, pyrrhotite, --82.9 6.64

magnetite, sericite
9F-105 Loma Bianca; water-rich zone near --94.2 6.01
intrusive margin; amphibolepres-
ent
Sericite
Product of pervasiverock alteration GR-6 Feldspar alteration sericite -54.5 9.65

GR-9 Feldspar alteration sericite --59.0
GR-13 Intense greisen; feldspar largely de- -55.2 10.99
stroyed; quartz-sericite rock
Product of hydrothermalvein fluids Auxilio II Wall rock alteration; vein selvage --56.3 11.00
9H-124 Hydrothermal gangue; large rug --55.8 12.82
crystals 1 to 2 mm in diameter
7Man-408 Hydrothermal gangue;near contact - 53.9
with Chicama Formation and
intrusive
9CO-239 Hydrothermal gangue; well within --48.8 11.76
the intrusive in the Consuelo sys-
tem
ment. Someof the variationresultedfrom sampling be -40 per mil. 9-Huaccarais situatedin a thrust
two populations of fluid inclusions,
as discussedpre- zone and consistsof a low-temperaturegalena-tetra-
viously. (2) Two significantdepressions in the I•D- hedrite aggregatewhich containsfluid inclusionwa-
paragenesiscurveoccurduringor immediatelyprior ters of •D = -144 per mil.
to wolframitedeposition. (3) Major sulfidedeposi- These three samplesof hydrothermalfluids, post-
tion is associatedwith hydrothermalwaters of •D Carbonateperiod in their parageneticposition,indi-
valuesof about-40 to -50 per mil. (4) I•D values cate that the deuterium content of the local surface
decreasedtoward the end of vein mineralization and, watersduring ore depositionwas lessthan Carbonate
during the fluorite and carbonatestages,the •D of periodwaters. Further, the 9-I-Iuaccaradata from a
the fluidsreached--75 per mil. localitynine kilometersfrom the Consuz.o vein (Fig.
Three samplesthat exhibit large negative •D 2) suggestsa spatialdependence, with low •D wa-
values of their inclusion fluids are believed to con- ters beingfarthestfrom the stockand central site of
tain secondaryfluid inclusionsthat formed along mineralization. These values suggestthat the I•D of
rehealedcracksat somelate stage(post ore deposi- the localmeteoricwatersat the time of ore deposi-
tion), but prior to completecoolingof the stock. tion was perhapsas low as --145 per mil.
GR-6 (•D = -111 per mil) is a whole-rockmineral
Hydrous mineral water
assemblageidentical to the material from which
quartz phenocrystswere hand pi.ckedfor fluid in- Eight biotitesand sevensericites(Table 5) se-
clusionwater analysis. Seemingly,althoughthe in- lected from the various rock alteration assemblages
clusionsin quartz phenocrysts containwater with a and localities in the Pasto Bueno intrusive and vein
•D value of --81 per mil, quantitiesof muchlighter, systems wereanalyzedfor •D (and •x80). •D values
meteoric water were incorporatedin this sample. in biotitesare systematically related to the type of
Coarsemassivecrystalsof tetrahedrite(9H-152) rock alteration and association with hornblende in
from I-Iuayllap6ncontainfluid inclusionwaters of water-rich zones (Loma Blanca). Rock alteration
•D = -113 per mil, thoughby comparison with this sericitesare more deuterium-depleted than hydro-
sample'sparagenetic position,the I•D value should thermal vein sericitesand sericitesof veins deep
T•,sLE6. QuartzOxygenIsotopeData within the stock interior are enriched in deuterium

relativeto intrusivemarginvein sericites.
Sample no. •sO
Assumingan approximatetemperatureof crystal-
Intrusive qum'tz lization for the biotites of 650øC, the calculated8D
(Interstitial and megacryst) valuesof the hydrothermal
watersin' equilibrium
GR-6 x -t-10.62
GR-7 +10.71
with the biotitesare --47 to --74 per mil. On the
GR-8 +9.90 other hand, a temperaturerange of 700ø to 450øC
GR-13 •
9L-206
+11.00 is suggested if the 8Da2owas --50 per mil. These
+10.26
8D valuesmay be reasonableinasmuchas the extent
Massive bull quartz veins of alterationbiotite formationat submagrnatic tem-
Pampas Watch veint -t-10.89
9F-108 x + 10.83 peraturesis not known. The •D of water in equi-
9F-109 a -t-10.61 librium with sericiteI (assumingno retrogradeex-
Mina de Oro-Pampas + 11.42 change)is --32 to --37 per mil, at an assumedtem-
7Co-Bull -t-13.36
9F-115 -3-14.20 peratureof 350ø to 400øC. A 240øC temperature
Quartz crystal zone studies
for sericiteII, implied from related fluid inclusion
(Inner zone to outer zone) filling temperatures,suggestsa 8D of --11 to --19
9H-175a -t-14.76 per mil. (•Da2o of --30 to --40 per mil is indicated
b -t-14.73
-t-14.97 by the 8Da2o-paragenesis data, Figure 9A, requires
d -t-15.26 an unacceptably hightemperatureof 325ø to 400øC.)
e -t-15.03 Thesecalculated dataare onlyasgoodasthe experi-
f -t-16.94
9H-124c -t-14.38 mentalfracti.onation equationsand the uncertaintyis
b -t-15.61 probablylarge.
9H-124-P -t-15.54
-2 • +15.29
.3 • +17.00
Oxygen Isotopesof the Hydrothermal Fluids
9H-141a +14.46
b + 14.84 Quartx
9H-107c -t-14.68
b -t-15.43 Quartz crystals,zones within crystals,greisen
+16.36 quartz megacrysts,magmatic quartz, and Chimfi
9H-154a +14.46
b + 14.84 quartzite sampleswere analyzedfor •xsO values
9Ma-166a + 12.92 (Table 6). The samequartz samplesthat were
b -t-14.96 crushedfor fluid inclusionwaterswere analyzedfor
Chimfi Formation 8•s0 (Table 3). 8•s0 valuesrangefrom about+10
(Quartzite) to +17 per mil. The generalincreasein the 'sO
Cocha Conchucos +13.24
contentof the quartzthroughtime reflectsa general
Individual quartz crystals dropin temperature. Reversalsof this trend indicate
Consuzo veins
9L-204 +13.54 either an increasein temperatureor a decreasein
9L-206
9L-220 •
+13.93 the x*Ocontentof the hydrothermal fluidsin equi-
+14.54
Manuelita veins librium with the precipitatingquartz. Data on
7Man-411 +13.55 fluid inclusionfilling.temperaturesshowno signif-
Consuelo
9Co-112 • +14.78
icantcorrelation with the 8•s0 reversals,
indicating
9Co-184 • +14.01 a decreasein •O contentof thefluidsto bethemajor
9Co-221-P + 13.49 factor.
-2 • +14.67
.3 • +13.58 Individualcrystalzonestudies showa progressive
9Co-226 +14.25 increasein xsOcontentof the quartzfromthe inner
9Co-234• +14.81
9Co-238 • -3-13.35
coreto the outertip of the crystal. One exception
9Co-245 +13.98 to this pattern is the decreasein •O contentbetween
Chabuca vein
9H-108 +14.78
ZoneI-B andZoneII-A, occurring
at thesameposi-
9H-155-8 • +14.87 tion as the deuteriumdepletionassociated
with
9H-175-P +15.26 wolframite II mineralization. A decrease in
7H-431 +15.30
7H-Chim 300 -t-15.91
contentis alsoindicatedfor ZoneI-A quartzof the
7H-Sta-Isabel +16.52 wolframiteI deposition period,wherethe deuterium
Mundo Nuevo contentof the fluidsalsodrops.
9Mn-127• +13.64
9Mn-128 -t-13.63 Hydrous •ninerals
9Mn-179 -t-15.93
The aD and 8•O values of selected biotites and
• Paragenesissample. sericites(Table 5) and their calculated
equilibrium
TABLe.7. Oxygen IsotopeValues of ConsuzoStock Mineral Separates
Mineral GR-6 GR- 13 9L-206 9F- 105 GR-8
Quartz q- 10.62 q- 11.00 q- 10.26 +9.90

K-Feldspar +9.35 q- 10.29 q- 10.09
Biotite +5.82 +6.64 +6.25 +6.01 +5.77
Sericite +9.65 q- 10.99
Magnetite +2.05 +2.59 +2.28
Biotite (D/H) -- 76.6 -- 82.9 -- 76.6 --94.2 --68.6
Sericite (D/H) -- 54.5 -- 55.2
watershavebeenpartially discussed above. Neither catethe calculated•xsOH2o

valuesusingdata on filling
biotitesnor sericitesshowa large total rangein temperaturesin secondaryinclusions. Assuming,
values, unlike the biotite •D data. The •x80 of the as previously discussed,that the material was
biotitesshowno significantpatternand are all rea- "flushed"by later fluidsand that the •x8Oa2oof the
sonablemagmaticvalues(Taylor and Epstein,1962, parent fluids was in the range of deep-seated values
a and b). The data suggestsmallerpositive•x80 (shadedarea), the 'temperaturesat isotopicequi-
values for sericite I than for sericite II, and an x80 librium can be calculated. These temperaturesare
enrichment is noted for sericite II in veins at the indicatedfor various8•80•o valueswithin the deep-
margin of the stockin comparisonto vein sericites seatedrange (+6.5 to +9.0 per mil) in Figure 9B.
fr.om the interior of the intrusive. These features This assumptionseemsreasonablein view .ofthe fact
are believedto be largelythe reflectionof tempera- that the quartz monzonitemineralshave •x•O values
ture effectson the isotopicsystems. The calculated typical of unalteredigneousrocks. Box B contains
•xsOH2oin equilibriumwith thesehydrousminerals the range calculatedfor the isot.opecompositionof
is somewhatlarge. The biotite-wateroxygeniso- waters for early barren quartz veins, based on
topefractionation is notknownbut hasbeenapproxi- secondary inclusionfilling temperature. Severalwa-
matedusingthe technique of Sheppardet al. (1971); ters in fluid inclusionsin non-oxygenminerals were
the uncertaintyin thesecalculatedvaluesis large. analyzeddirectlyby the BrF5 technique(O'Neil and
Carbonates
Epstein,1966b; Rye and O'Neil, 1968) and have a
•x•OH•ocompositioncompatiblewith waters of para-
Calcite I and II, rhodochrosite,and dolomitewere geneticallyadjacentsamples.
analyzed for •x80 values (Table 3). The x80
Carbon Isotopes of the Hydrothermal System
valuesof waters in equilibriumwith the carbonates
were calculatedusing the carbonateoxygen isotope Fluid inclusion C02
data; a substantial x80 decreasein •xsO values oc-
curred in the late waters.
Carbondioxidegasextractedfrom the fluid inclu-
sionsin a few sampleswas of sufficientquantityto
Quartz monzonitemineralseparates analyzein the mass spectrometer(Table 3). The
very smallquantityof gas handledin theseanalyses
Quartz, feldspar,biotite, sericite,and magnetite did not permit the normal analyticalprecision,but
separatesfrom crushedintrusiverock were analyzed all data are within --+0.5 per mil.
for •xsO (Table 7). In all casesthe values are
comparableto "magmatic"values (Taylor and Ep- Carbonates
stein, 1962, a and b) and only minor retrograde Dolomite,rhodochrosite, and calcitewere analyzed
oxygen isotope re-equilibration is noted. These for their 8xaC(Table 3). The 8•aCof hydrothermal
mineralsmust have crystallizedin the presenceof CO2 in equilibriumwith thesecarbonateswas calcu-
waters with magmatic8xsOvalues. lated using the appropriateexperimentaland theo-
Oxygenisotopecomposition of hydrothermalwater reticalfractionationequations.
The •x80 valuesof the hydrothermalwaters show Interpretationof the xaC/•C data
a generaldecreasewith time (Fig. 9B). Variations The carbonisotopecompositions of hydrothermal
in •x*O on the order of 2 to 2.5 per mil do occurand carbondioxide are plotted againstthe paragenesis
showsomegeneralsimilaritiesto the •D-paragenesis axis (Fig. 10B). The 8xaCvaluesrangefrom -4.1
pattern. Inasmuchas early Zone I-A and Greisen to -11.9 per mil, with substantially more negative
temperatures are not accurately known, several cal- valuesduring the late Vein (Zone I-B to carbonate)
culateddata are indicatedin Figure 9B. Vertical portionof the paragenesis.The 8xaCvaluesof deep-
lineswithouthorizontalends(within box .4) indi- seatedCO• in magmaticsystemsare consideredto
TAm.E 8. A. SulfurIsotope
Analyses
andCalculated
Temperatures
of Probable
sulfide
Equilibrium
Pairs
Sampleno. Mineral $a4S zkA-B a øC Comments
pyrite 0.55 px-gn 1.00447 223.6+ Sulfides at base of rug containing

9H-176 sphal --0.09 sl-gn 1.00382 152.6 black wolframite (ferberite), iso-
galena -- 3.90 px-sl 1.00640 - 56.3 topic nonequilibrium
9H-176' pyrite 0.62 px-gn 1.00474 209.2+
galena -- 4.10
9H-175-2 sphal 0.30 sl-gn 1.00428 129.2 Sulfide pair wolframite I I
galena -- 3.96
9H-175 sphal 0.29 sl-gn 1.00360 165.2+ Sulfide pair wolframite I I
galena - 3.31
9H-148-A sphal 0.00 sl-gn 1.00280 224.2
+ Sulfidesin green/white fluorite
galena --2.79
7Chab-365-2 sphal - 0.03 sl-gn 1.00233 272.3+ Massive ore with huebnerite sulfides
galena -- 2.35 are later
9Mn-126 pyrite 3.92 px-sl 1.00109 252.4+ Veta Pueblo, baseof crystal grouping
sphal 2.83 in quartz rug
sphal --0.01 sl-gn 1.00230 275.8+ Base of rug that contains rhodo-
7H-431 galena -- 2.30 chrosite and calcite
tennantite -- 2.70
7H-500-1 pyrite 0.70 px-sl 1.00078 347.1 Quartz-sulfide rug, no wolframite

sphal -- 0.08
pyrite 1.01 px-gn 1.00363 277.9+ Quartz-sulfide rug, no wolframite
7H-500-2 sphal -- 0.07 sl-gn 1.00255 248.1+
galena --2.61 px-sl 1.00108 254.0+
pyrite 1.02 px-gn 1.00397 253.6+ Post-wolframite I depositionsulfides
9L-204 sphal -- 0.29 sl-gn 1.00266 237.1+
galena --2.94 px-sl 1.00131 205.5
tetra -- 0.80
pyrite 0.55 Pyrite associatedwith wolframite I
9H-124-1 sphal -- 1.08 sl-gn 1.00155 393.9 At baseof quartz crystal rug in silici-
galena --2.63 fled quartzite (Chimfi Formation)
pyrite 0.39 px-sl 1.00196 118.0 Small sulfidecrustationson quartz
9H-124-2 sphal -- 1.57
pyrite 0.66
tetra -- 1.70
pyrite 0.60 px-gn 1.00691 126.4 Sulfides enclosed by early vug

9H-124-3 sphal -- 0.01 sl-gn 1.00630 58.6 growth, at base of larger quartz
galena --6.27 px-sl 1.00061 428.2 crystals
pyrite 0.61 px-gn 1.00197 474.0+ Early Tertiary dacite dike with
9H-145 galena -- 1.36 pyrite-galenaintergrowthsulfide
patches
Indicates
anacceptable
temperature
=k•20øC
inagreement
withother
data.
rangefrom --5 to -7 per mil basedon the 8•aCdata At higher temperaturesearly in the paragenesis
for hydrothermal gangtie assemblages, carbonatites, (samplespre-9L-220) perhapsdecarbonizationof or
CO•. of geothermalareas, and fluid inclusionCO•. exchangewith limestonein the sedimentarysection
(Rye, 1966; Craig, 1963; Taylor et al., 1967; Deines, increasedthe •aC contentof the hydrothermalCO•..
1968). Larger and more erratic CO•./H•.O molar ratios
The recentwork of Ohmoto (1972) demonstrates (Fig. 10A) at this time probablyreflect an early
that the isotopiccomposition of hydrothermalcarbon boiling and volatile separationhistory of the fluids.
speciesis controlledlargelyby T, Io2, and pH of the The two generationsof fluid inclusionsobservedin
fluids. The degreeto which physicochemical con- thesesamples(Fluid Inclusionsection)and a vague
trols have influencedan initial deep-seated isotopic inversecorrelationof 8D and 8xaCsuggestthat the
composition has not been ascertained, but most dominant fluids sampled were second-generation
carbonin the Pasto Buenohydrothermalsystemis fluidsfrom the Zone I-A-wolframite I period.
probablyof deep-seated origin, inasmuchas CO•. is The 8•aC values for CO•. which are lower than
the dominant carbon speciesin the hydrothermal typicaldeep-seated carbonmay representa peculiar
fluids and its isotopiccompositiondoes not differ isotopiccomposition typicalfor Andeandeep-seated
significantlyfr.omdeep-seated
values. systems(Casapalca,
Peru; Rye and Sawkins,1974).
TABLE 8•( Continued)

B. Sulfur IsotopeAnalysesof Individual Sulfide Minerals
Sampleno. Mineral $a4S Comments
9Mn-127 sphal 2.85 Veta Pueble, dark sphalerite

7H-419 pyrite - 2.34 Pyrite-arsenopyrite pair in otherwise nonmineralized
apx - 1.96 portion of Santa Isabel
7EL-Plomo pyrite 1.20 Pyrite in Chicama Formation vein breccia
pyrite 2.07 Pyrite in bull quartz vein
7L-406 pyrite 0.55 Early pyrite molybdenitepair
moly -0.60
7Pelagatos pyrite - 0.26

0.62 Richly mineralizedvein float in Rio Pelagatos
moly
9Veta Bianca moly -- 0.90 Moly vein located up canyon from 7 Pelagatos
9-Huaccara galena - 0.58
1.47 Peripheral mineralization in soleof thrust, quartzite
tetra and limestone,no gangue
9L-193 pyrite 1.25 Pyrite associatedwith pegmatitic early purple
fluorite (9L-118)
7H-421 pyrite 0.52 South end Santa Isabel, associatedwolframite
9Ma-166 pyrite - 1.01 Disseminated stockwork in Chimfi Formation
9P-121-A pyrite 0.28 Limestonereplacementin samethrust, north of Hu-

pyrrhotite 0.19 accara deposit
9M-3 pyrite 0.46 Majistral skarn
po -0.10
GR-13 pyrite 1.30 Quartz-sericite greisen
po 1.50
7Py-Consuzo pyrite 1.12 Loreto Pyrite Concentrate D/H crush
9M n-Pyrite pyrit e 2.60 Large singlecrystal, D/H crush
GR-9 pyrite 1.44 Weak potassicalteration
7F-2 pyrite 1.09 Magmatic(?) pyrite in dacite dike
9Co-233 pyrite - 1.01 Vein sulfide pair
cpy - 1.64
pyrite - 0.44 Vein sulfide pairs
9Co-113 cpy - 1.65
cov-bn - 1.55
9L-118 pyrite 0.72 Pyrite associatedwith early pegmatitic fluorite

9L-119 pyrite 0.86 Pyrite associatedwith disseminatedmolybdenumin
Cortada Loreto
Vein sulfides
9Co-224 pyrite
tetra
-2.50
- 2.61
9H-152 tetra - 1.37 Vein sulfide
9L-204* tetra - 0.45 Vein sulfide
7H-500 tetra - 5.48 Vein sulfide
Alternatively,the CO•.may have exchangedwith a +3.9 to -2.5 per mil (average:+0.6 per mil); 14
x3C-depleted
graphiticmaterial in the basementrocks sphalerites ranged from 2.9 to -1.6 per mil
(Bottinga,1969; Craig, 1963). (average: +0.2 per mil), and 13 galenasranged
from -1.5 to -6.3 per mil (average:-3.1 per mil).
Sulfur Isotopesof the Hydrothermal System
In addition,severaltetrahedrite,molybdenite,pyr-
Sulfur isotopedata were obtainedfor sulfidemin- rhotite, chalcopyrite,covellite-bornite,and arseno-
eralsto determinethe sourceof sulfurin the deposit, pyrite sampleswere analyzed. (This extensive8•S
to evaluateparageneticand spatialvariationsin 834S coveragewas undertakenso as to be of use in a forth-
valuesin termsof chemicalchangeof the ore fluids, comingfluidchemistryandfluidinclusiongasstudy.)
and to utilize recently developedgeothermometric Becauseof the small isotopicfractionationbetween
techniques(Czamanskeand Rye, 1974; Kajiwara aqueousH•.S and pyrite, the isotopiccomposition of
andKrouse,1971). The dataare presented in Table the total sulfurin the hydrothermalsystem(Sa•Szs)
8A andB. 834Sanalyses
for 31 pyritesrangedfrom is about +0.5 per mil (Ault and Kulp, 1960;
GREISENI
IE•RLY I/E/A/ L•TEll •IUG
• ZONE
I-A ZONE
I-B II-BB/C
rite ate
20
--
--
.
0_.16 --
13::14 --
0 12
--
IO
o
o• 8
o• 6
--
o
(J 4
o - t
--
tiC)_(
-I0
ß ß
ß
-I• -- ß --
I I I Ill I I II I I II II I I I/ll II I I Illll I IIII
o
ø o • •o,• o& o•n.• r• r• •.• o•o•.• _
F',•::r o , :• 0
oo-. w10o'•' o o •ooo•oo o o •o oo o "•
65 85 90 95 97 99
VOLUME
PERCENT
OFDEPOSITION i
FIG. 10. A. CO•/H•O molar ratiosof fluid inclusions.B. 8•C valuesof hydrothermalCO..
Dots are fluid inclusion•Coo• data; triangles are calculated•Coo.• from carbonatedata.
Ohmoto,1972). The 8"Szs is near the meteoritic +1.3 per rail. "Pre-main sulfide"and molybdenite
standardand comparableto sulfur of known mantle ore are <0.0 to -2.5 per rail (Figs. 7A and 9A).
origin. Pasto Bueno probablyhad a deep well- Ohmoto (1970, 1972) has demonstrated that sulfur
homogenizedsource for the sulfur in the sulfide 'isotopiccompositions
are dependentupon fluid
minerals. physicochemical
parameterssimilar to carbon. The
Only smallsystematic
paragenetic
and spatial variatiohsnoted are probablythe result of changes
variations are observed in the 8•S values of indi-
in suchfluid parameters;but dataon the fluid chem-
vidual sulfides. For example,early pyritesin vol- istry are insufficient
to studyin detail.
canic dikes and altered rock together with fluorite Most mineral pairs did not give reasonablesulfur
pegmatites,greisens,and wolframite I ore are 0.0 to isotopetemperatures. This undoubtedlyreflectsthe
TAm.E 9. Hydrogenand OxygenIsotopicCompositionof Pasto BuenoSurfaceWaters
Elevation
Sample no. Date collected• (m) Remarks •80 •D
Precipitation waters
PB-W-1 rain--east 9/10/70 3,417 "Hotel"; temp. 17øC - 7.30 -46.0
PB-W-2 rain--west 10/27/70 3,384 Lab Quimico;temp. 17øC -4.19 - 21.3
PB-W-6 rain--east 6/29/69 3,421 Oficina; temp. 10øC - 10.30 -60.2
PB-W-8 lake 10/70 3,960 Laguna Pelagatos - 11.02 - 81.8
Thermal waters
PB-W-3 10/28/70 Cocha Conchucos; - 13.78 - 98.8
temp. 39.5øC
PB-W-4 10/28/70 Cocha Conchucos;60 m - 13.55 -97.4
from effluent;
temp. 39.5øC
Mine waters
PB-W-9 10/70 fault zone--surface water - 11.82 - 84.6•
PB-W-10 8/69 Cortada Sta. Isabel - 13.29 -94.9
PB-W-11 10/70 Cortada Chabuca II - 13.07 -92.9
PB-W-13 10/12/70 Manuelita; in Chicama - 12.82 -93.8
near intrusive contact
Averageof homogenized groundwaters -- 13.30 -- 95.6
(PB-W-3, 4, 10, 11, 13)
Analysesfor a•so performed4/71, for aD 8/71.

Water flowsfrom fault zonewhich taps surfacelake watersalongwater canal.
slightchangesthat occurredin the physical-chemical Meteoricwatersat the time of ore deposition ap-
stateof the ore fluidsfrom the precipitationof one parentlyhad a 8D value of --145 per mil which is
mineralto thenext. This is not.unusual in a mixing lower than that for present-daymeteoric waters.
situation. Thirteen pyrite-sphalerite-galena pairs This value compareswell with the 8D of meteoric
(Table 8A), however,gavecalculatedtemperatures water in Central Peru at approximatelythe same
from about200ø to 275øC(average:244øC), which time (Casapalcaarea; Rye and Sawkins,1974).
are in reasonablygoodagreementwith fluid inclusion Two explanationscan be given for the negative8D
filling temperaturesthroughoutthe paragenesisvaluesin meteoricwatersat the time of ore deposi-
(-----
20øCof fillingtemperature)(Rye, 1974). tion: (1) the ground water rechargeelevationof
the Pasto Buenoarea 10 million years ago was as
The Origin of the Hydrothermal Fluids great as or greater than today; or, (2) the Pasto
Past and present meteoricwater at Pasto Bueno Buenoarea lay in a rain shadowcausedby higher
than present-dayelevationsto the west.
The •t•80 and 8D valuesof precipitation waters, Ten millionyearsagothe now-eroded uppermost
thermal waters, and mine waters in the Pasto Bueno portions and cover rocks oœthe Coastal batholith of
region (Table 9, Fig. 11) plot on or closeto the Peru probablystoodat altitudesof nearly 4,000
meteoricwaterline (Craig, 1961a;Friedmanet al., meters (Fig. 12). Precipitationoriginatingfrom
1964;Dansgaard, 1964;Craig,1963). Noneof the the PacificOceanand crossingthe coastalbarrier
precipitationwaters collectedare sufficientlyde- couldhave beencharacterized by watersof low 8D
pletedin deuteriumto accountfor the mine water; and 8180values. This rain-shadow isotopiceffect
butthisis attributedto incomplete samplingcoverage behindthe Coastbatholithof Peru may havebeen
from storms of both Pacific Coast and Amazon Basin
comparable to that existingtoday to the east of the
derivation. The mine waters are considered well
central Sierra Nevadaof California,wherea large
homogenized and representative samples oœmodern negative8D is observed in present.-daymeteoricwa-
PastoBuenowater. The average isotopic
composi-ters (Sheppardet al., 1969).
tion of present-daymeteoricwater in the Pasto
Bueno region is 8D =--96 per mil and 8180•- Hydrothermalfluid evolution
--13.3 per mil. Of importanceto this studyis the 8D and 8180 values of all Pasto Bueno waters are
factthatthe isotopic
compositionof modernmeteoric presented in Figure 11. The isotopicrangeis large
waterlieswelloutside therangeconsidered for mag- andthe absence of a 8D-8'80correlation for the hy-
maticwaters(seebelow). drothermalfluidsindicatesa complexhistoryin-
+20 --
WATER (3) Magmatic. Water involvedin a magmatic
_ +Precipitation / system,whichexsolvedfrom sucha system,regard-
0
X Lakeandcanal
z. Thermal 4•,'"/-Yle
........
ß Mine &•/ "- Metamorphic connote lessof origin or ultimatenature of the water. Pre-
- ß Fluidinclusion •/ ..•• water
-20 Biø'i'e:650•C •/ B •..•(Wilbur Springs) sumably,magmaticwater would consistof juvenile,
• Sericife:
I=350øC,
X =240øC 7
- a a otife:700-600-550-450•C/ •' metamorphic,and/or subductioncomponents. The
-40 likelihood of meteoric and connate-formational con-
- / ,% ' ß • tributionsto magmaticwater is not known. The
-60
+/ w;' ' .,o
range in isotopiccomposition
of magmaticwater is
controversial;
the conceptmay be too inclusiveto be
-
A2•.
•'
ße'•'• •I -,• cagmatic.
(•ep-seated) isotopicallydefined. White (1968), from a survey
•-I00 &•'
•Avemge modern meteoric
weter
of availabledata, specifieda range of $D •-50 to
• weter(-95.6%•,- I•.•%•)
--120
--120 per mil; Rye (1966) obtainedvaluesof D =
--68 to -83 per mil and •'80 = +6.4 to +7.9 per
- 140 rail for Providencia fluids;Rye and Sawkins(1974)
AI --
• •owerlimitof meteoric
woter suggest8D valuesof -45 to -55 per mil for Casa-
/ ot time of minemlizetien
- 160
palcamagmaticwaters; Ep'steinand Taylor (1967)
• -145%•,-19.4%•) proposeda range of 8•sO• +8 to +10 per mil for
-180 --
high temperaturewatersin equilibriumwith crustal
-200 • I • I , I ] I i I i I , I , I i I silicaterocks. This report considersmagmaticwa-
-24 -20 -16 -i2 -8 •8-4 0 +4. +8 +12
ters to fall within a rangeof 8D = -45 to --85 per
80H20 mil and 8•sO= +6.5 to +9.0 per mil. Theselimits
Fro. 11. Isotopiccompositionof Pasto Buenowaters.The must be recognizedas arbitrary but reasonable.
6D and *•O of variouspresent-daylocal surficial waters are (4) Cormate (formational)--Metamorphic.Wa-
plottedin referenceto the meteoricwater line; lid- 8•O
+ 10 (SMOW). Average modern meteoricwater is lid- ter derivedfrom rocks during their metamorphism
--96 per mil and •80 =--13.3 per mil, and meteoricwater at and dehydration and connate-formationalinterstitial
time of mineralization is •D =--145 per mil and •O-- burial water driven off during compactionand early
--19.4 per mil. Shaded area A•, A•, B, and C are respec-
tively, meteoric water 1 and 2, metamorphic water, and metamorphism.Connate-formational watersmay re-
magmatic water; shaded areas I and II are periods of flect the compositionof burial waters or ambient
wolframite deposition. Numbered data points are isotopic meteoricwaters, with superimposed effectsof ex-
compositionof consecutivelylater hydrothermal fluids from
the paragenesis. changeand microporefractionation(Craig, 1963;
Hitchon and Friedman, 1969; Graf et al., 1965;
volving two or more waters. Modern precipitation Claytonet al., 1966). Metamorphicwatersderived
and mine waters are plotted for comparisonbut from dehydrationof deeplyburiedor subducted rocks
shouldnot be confusedwith waters existing at the probably have a wide range of values considering
time of mineralization. the possibleregion of expulsion of the fluids and
Possiblesourcesof water in hydrothermalsystems their evolutionthroughthe upper crust (Savin and
are of the following four basiccategories(White, Epstein, 1970a,1•). Metamorphicwatersmay have
1957aand b): D/H values as variable as meteoric water and a
rangein •80 from approximately 0.0 to +14 to +15
(1) Juvenile. Water that has not previouslybeen per mil (Epstein and Taylor, 1967). White et al.
a part of the atmospherichydrologiccycle, i.e., (1971) describedspring waters of the California
primary "outgassing"from the mantle. In their coast ranges that, from isotopicand chemicalevi-
study of phlogopites from alkalic intrusives,Shep- dence,they interlSretedas being metamorphic-con-
pard and Epstein (1970) suggested a range in iso- nate of 8D = --10 to --30 per mil and 8•80 = +1.0
topic compositionfor juvenile water of •D =--48 to +6.0 per mil.
-----20
and 8•80= +7 and +8 per mil. Isotopiccriteria
do not permit a distinctionbetween juvenile and Water in (3) and (4) may have very complex
magmaticor other deep-seatedwaters. Most deep- historiesand may themselves be derivedfrom oneor
seated water having evolved since early geologic more other water types. With the exceptionof (2)
time may be almost entirely recycledwaters with
and somesamplesof (4), all waters abovemay be
little or no juvenile additions.
(2) Meteoric. Water derived from atmospheric referredto as deep-seated water, a non-specificterm
precipitationand directlyinvolvedin the hydrologic- for water of deepcrustalor upper mantle derivation.
meteorologic cycle. These watersare usuallylimited The extent of exchangeor other interactionbetween
in their isotopiccompositionby the relationship8D deepcrustal and upper mantle reservoirsof "deep-
-88'80 + 10 (Craig, 1961a, 1963, 1966). seated" water is not known.
I•ll I METEORIC ' TCONSUZO /Volcanic cover

IACCARA
AMAZON
H•O Precambrian metomorphfc

MAGMATIC gneiss
andschist
CORDILLERA
• H20
BLANCA
'•MORPHIC
BATHOLITH
Fxc,.12. Hypothetical sourcemodelfor PastoBuenohydrothermalfluids. Precipitation-meteoric water behind

the elevatedCoastalbatholithof Peru [9.5 m.y. ago] providesnecessary
isotopically
depletedwaters.Thrustfaults
and high-angleblockfaultsextendingdeepinto the site of Consuzostock emplacementserve as the necessary
plumbingsystems.The permeable volcaniccoverabovePasto Buenomay have providedupper level meteoric
water infiltration. Precambrianand youngerbasementgneissand schistare possiblemetamorphicwater sources.
Subduction and juvenilewater sourcesare unknowns.Note the positionof Huaccara(D/H: --144 per mid in a
zone of early Tertiary thrusting.
Processesthat changethe isotopiccompositionof later case,the lid range of the magmaticwater was
a hydrothermalwater are the following: (1) varia- largei' than shownon Figure 11. The isotopedata
tions at the source; (2) isotopicfractionationbe- do not permit a distinctionbetweenthese two pos-
tweenwater and other solids,liquids,or vapors,any siblemodels:either the magmaticwater had a large
or all of which later can be separatedor isolated D/H range or a connate-metamorphic or other wa-
from the system;(3) exchangewith a large isotopic ter componentis indicated.
reservoir;and (4) mixing of waters derivedfrom Variations in 8Da2o of the fluids might also be
different and isotopicallydistinct sources. Inde- explainedby multiphasefluid fractionationof hy-
pendent,yet simultaneous, operationof two or more drogenbetweenwater and other phasesthat would
of these mechanismscan producevery complexhy- increase the deuterium content of the water from an
drothermal water isotopicdata. initial magmatic value. Hydrogen isotopeexchange
Figure 11 showsthe approximaterange of iso- between He-CH4, HeO-He, HeO-HeS, and pos-
topic compositionsof deep-seatedmagmatic (C), siblyHeO (liquid)-HeO (vapor) is capableof yield-
cormate-metamorphic (B), and meteoric (Ax) wa- ing large fluctuationsin 8Da2oof fluids at elevated
ter at the time of ore depositionin the PastoBueno temperatures(Bottinga, 1969; Bancroft, 1968).
area. The data on the Pasto Bueno hydrothermal However, CH4, He and HeS were not observedin
fluids lie within the area boundby the composition sufficient concentration in fluid inclusions to account
of the three types of water. The data suggesttwo for any of the D/H variationsby fractionationef-
interpretationsof the history of the hydrothermal fects. Further, there is no correlation between sa-
fluids at Pasto Bueno: (1) the fluids evolved as a linity, 8•80, and8D--a'swouldbe expected in boiling
mixture of magmatic, meteoric, and connate-meta- and remixingof residueand condensate fractions.
morphic waters with each of the three components In a two- or three-component water mixing model
becomingdominantat varioustimesduring the para.- proposedfor the evolutionof PastoBuenofluids,a
genesis,or (2) the fluids evolvedas a mixture of percentage mixing calculationclearlywouldinvolve
deep-seatedmagmaticand meteoricwater. In this a ternaryplot with three non-fixedand unspecified
endmembers.It is,therefore, notpossible to specify for meteoricwater that was incorporatedin the hy-
exactproportions of the variouscomponents. Added drothermalsystem. This fact suggeststhat meteoric
complexitydevelopswith the possibilityof two water circulationextendeddeepinto the hydrother-
meteoricwater components Ax and A2 in Figure 11 mal plumbingsystem.
(cf. OhmotoandRye, 1970).
A modelcalculationis possiblefor the minimum
totalvolumeof hydrothermal waternecessary to pro-
ducetheknownvolume(and inferredmaximumpos- 8D and 8x80 data obtainedin this study indicate
siblevolume)of quartzdeposited in the PastoBueno a mixing of watersfrom two or threedistinctsources
vein systems(Landis, 1972). Assumingthat the to producethe hydrothermalfluid---one magmatic,
hydrothermal fluidsderivedentirelyfromthemagma, one meteoric, and one possiblyof connate-meta-
a minimumintrusivemagmavolumecanbe assessed. morphicorigin. The •115Cand 8a4Sdata indicatea
A 360øC temperature,300 and 500 bar pressure, deep-seatedmagmaticsourcefor the bulk of these
elements.
and maximum SiO2 solubility and H•O magma
saturation are applied to the experimentaldata Meteoricwatersin all probabilitydescended along
(Kennedy, 1950; Kennedyet al., 1962; Burnham gravity thrust faults, high-angle faults, and other
and Jahns, 1962; Burnham, 1967). A calculated structures and became involvedin deep circulation
minimumof 1.1 (to 4.4) x 10•5 cubiccentimeters patterns. Some of these structuresextending into
of water initially containedin a stockvolumeof 27 the region of Consuzostockemplacement
may have
is requiredto producethe retaineda considerablehydrostatichead at the time
(to 107) cubickilometers
observed(and inferredmaximum) 1.3 (to 4.0) x of magma crystallizationand later mineralization.
10•2 gramsof quartz. Severaltensof squarekilom- Also, the 1,500metersof volcanicbrecciasand pyro-
clastics above the stock must have contained some
eters of Consuzo stock are observed in the field to
a depthof 800 to 1,000meters. Vein development volume of shallow-circulatingmeteoric water that
was confinedto the uppermostpart of this cupola; waspossiblylessdepletedin deuteriumthan thedeep
a sufficientvolume of intrusive magma was avail- circulating,more westerly derived meteoricwater.
able to have suppliedall hydrothermalfluids. The Upwarping and compactionand metamorphism as-
presenceof meteoricand/or metamorphicwatersin sociated with an intrusion would have liberated any
the magmatic-hydrothermal fluid system,of course, interstitialor hydrationwaters and permittedthem
permits the possibilityfor a substantiallysmaller to mix with meteoricwaters prior to or during in-
filtration into the stock.
volumeof magmato evolvethe requisite"magmatic"
hydrothermalcomponents. When fluid pressuresof watersof magmaticderi-
Meteoric (and connate-metamorphic) water was vation were greater than the hydrostaticpressures,
the migration of hot fluids outward from the in-
apparentlya very smallfluid componentduring late
trusive interior brought about the rapid coolingof
stagemagmaticand early stagehydrothermalevents.
the stockand the transportof many dissolvedcon-
Biotite 8D values relate to pre-hydrothermalrock
alteration and are thought to reflect in situ redox stituents. When fluid pressures of magmaticwaters
were equalto or lessthan the hydrostaticpressures,
reactions,exchange,and recrystallizationduring an thermal convection set in and meteoric and meta-
influx of shallow-circulating
low 8D meteoricwater
part of the stock (basedon two electronmicroprobe morphicwater infiltratedinto the coolingstockalong
analysesof major oxidesin biotitesGR-6 and 9F-105 major structures. Structural dislocationsand the
releasein pressureaccompanied by boiling facili-
having substantiallydifferent D/H ratios). Hy-
tated the influx of nonmagmaticwater into the base
drogenor water vapor streamingfrom depthis not
considereda viable mechanismto explain the biotite of the hydrothermalplumbingsystem.
Figure 12 illustratesin crosssectionthe geologic
data. As the biotiteand other magmaticcrystalliza-
setting for hydrothermalfluid mixing, including
tion phaseshavemagmatic
meteoric water from above was quite limited in isotopically permissiblewater from juvenile-subduc-
quantity. This meteoricwater couldrepresentmete- tion sources(Mitchell and Garson,1972; Sillitoe,
oric water Ax or 1972; Sawkins,1972).
Local meteoric water at the time of mineralization
Prior to or duringwolframiteI and II depositions,
(1) the deuteriumand •80 contentOf the ore solu-
of 8D = -145 per mil would have a 8•80 = -19.4 tionsassociated with wolframitedepositionwere rel-
per mil (Craig, 1961a). The 8D-8•80 pattern for ativelydepleted,(2) the salinity.of the ore solution
Pasto Bueno fluids (Fig. 11) indicatesa large •80 decreased to almost one-half of that normal for other
shift to near magmatic water values requiring an stagesof hydrothermalore deposition,and (3) a
extensivehistoryof thermaloxygenisotopeexchange drop in temperatureof the ore solutionsoccurred.
Theseobservations Bueno. This studyrepresents

indicatea rather stronginflux part of Ph.D thesis
of meteoricwater associated submit.
with wolframitedeposi- tedby theseniorauthorto theUniversity of
tion and implyeither (1) that a nonmagmatic Minnesota.Specialthanksandappreciation
source are ex-
tendedto Prof.F. J. Sawkins
for the tungstenin wolframiteor (2) that tungsten for manyhelpfuldis-
cussions
is in solutionin magmaticfluidsand precipitationof and suggestions,
and for his generous fi-
wolframiteis contingenton mixing. Whether the nancialsupportduringthisstudy.'Criticalreviews
mechanismfor wolframite precipitationis purely and comments by D. E. White and P. B. Barton,
temperaturedependent,or whetherchemicalchanges U.S. Geological Survey,W. C. Kelly,University
that result from mixing are important,is not clear. of Michigan,and H. Ohmoto,Pennsylvania State
Conclusions
University,
measurably
enhanced
thequalityof this
manuscript.
The main conclusions
of this study may be sum- G.P.L
marized as follows: DEPARTMENT OF GEOLOGY
UNIVERSITY OF NEW MEXICO
(1) Pasto Bueno tungstenmineralizationoccur- ALBUfi}UERfi}UE,
NEW MEXICO87131
red at low temperatures(290ø to 175øC) and with R. O. R.
hydrothermalfluids of moderatesalinity (17 .to 2 U.S. GEOLOgiCAL SURVEY
equivalentweight percentNaC1). DENVER,COLORADO
80225
(2) /•3C and/•34Sdata are consistent
with a deep-
REFERENCES
seatedor mantle sourceand strengthenthe sugges-
tion of a genetictie betweenthe felsicintrusiveand Ault,W. U., andKulp,J. L., 1960,Sulfurisotopesandore
hydrothermalfluids. deposits:ECON.G•.OL.,
v. 55, p. 73-100.
(3) 8D and 8•80 data require a mixing of mag- Bancroft, A. R., 1968,The Canadian approach to cheaper
heavywater: Atomic Energyof Canada,Ltd., Rept.
matic and meteoric water componentsand possibly AECL-3044 (1967).
a metemorphicwater componentfor the variousore Bellido,B. E., andManrique,P. A., 1954,Geologia de los
solution waters. yacimientos
detungsteno
deMundoNuevoy La Victoria:
MinistrioFomentoMineros,Serviciode Geologiay Min-
(4) The major influx of meteoricwater did occur eria, Lima, Peru, Bol. 12.
until the hydrothermalevent was well underway; Blount, C. W., andDickson,
of anhydrite
F. W., 1969,The sollubility
(CaSO0in NaC1-H•O from100ø to 450øC
influx was not significantduring the earliest late- and1 to 1,000bars: Geochim. et Cosmochim. Acta,v. 33,
state magmaticcrystallization. p. 227-245.
(5) Wolframite depositionwas associatedwith Bottinga, Y., 1968,Calculation
carbonandoxygenisotopic
of fractionation
exchange
factorsfor
in thesystemcalcite-
meteoricwater influx, whichproduceda drop in the carbondioxide-water:Jour. Phys.Chem.,v. 72, p. 800.
temperatureand salinityof the hydrothermalfluids. 1969,Calculated fractionationfactorsfor carbonand
hydrogen isotope exchange in the systemcalcite-CO•-C-
(6) The relativepercentage mixing of water com- CH•-H-H•O vapor: Geochim. et Cosmochim. Acta,v. 33,
ponentscannotbe ascertained but may have reached p. 49-65.
25 to 50 percentmeteoricassuminga two-fluid mag- -- tween
and Craig, H., 1969,Oxygenisotopefractionation
CO2 and water, and the isotopiccomposition
be-
of
matic-meteoric water model. marine atmosphericCO2: Earth Planet. Sci. Letters, v.
(7) Sulfide mineralizationwas associatedwith 5, p. 285-295.
waters of deep-seatedisotopic composition. This Burnham, C. W., 1967,Hydrothermal fluidsat themagmatic
stage,in Barnes,H. L., ed.,Geochemistry of hydrothermal
supportsthe hypothesisthat the sulfur and sulfide ore deposits:New York, Holt, Rinehart,and Winston,
metals involved in ore depositionat Pasto Bueno Inc., p. 34-76.
• andJahns,R. H., 1962,A methodfor determining the
were of deep-seatedmagmatic derivation. solubility of waterin silicatemelts:Am. Jour.Sci.,v. 260,
p. 721-745.
Acknowledgments Clayton,R. N., Friedman,I., Graf, D. L., Mayeda,T. K.,
Meents,W. F., and Shimp,N. F., 1966,The origin of
This work was supportedin part by National saline formation waters, I, Isotopic composition:Jour.
ScienceFoundationGrant GA-4355 (F. J. Sawkins), Geophys.Research,v. 71, p. 3869-3882.
a Geological Society of America Penrose Bequest Clayton, R. N., O'Neil, J. R., and Mayeda,T. K., 1972,
Oxygenisotopeexchange betweenquartzandwater: Jour.
Grant No. 1486-71,and a ReserveMining Company Geophys.Research,v. 77, p. 3057-3067.
Fellowshipat the University of Minnesota. Thanks Coney,P. J., 1971, Structuralevolutionof the Cordillera
Huayhuash,Andesof Peru: Geol.Soc.AmericaBull., v.
are given to the Peruvian mining company,Fermin 82, p. 1863-1884.
Malaga Santolallae Hijos, and to the many friends CossioN., A., 1964,Geologiade los cuadrangulos de Santi-
at Consuzo,Peru, who providedtransportationand ago de Chucoy SantaRosa: ComisionCarta Geologica
Nacional, Lima, Peru, Bol. 8.
field support,affordedready accessto all mining Covehey,R. M., and Kelly, M. C., 1971,Dawsoniteas a
properties and company records, and whose gen- daughtermineralin hydrothermal fluid inclusions:Contr.
Mineralogy Petrology, v. 32, p. 334-342.
erosity and hospitality guaranteedsuccessfuland Craig, H., 1953, The geochemistryof the stable carbon
productivecompletionof two field seasonsat Pasto isotopes:Geochim.et Cosmochim. Acta, v. $, p. 55.
1957, Isotopic standards for carbon and oxygen and 1965, Some applicationsof thermochemicaldata to
correction factors for mass-spectrometricanalysis of car- problemsof ore deposits. II, Mineral assemblages and
bon dioxide: Geochim. et Cosmochim.Acta, v. 12, p. 133- me composition
of ore-formingfluids: Ecoa. G•.oI..,v. 60,
149. p. 1101-1166.
1961a, Isotopic variations in meteoric water: Science, 1972, Granites,solutions,and base metal deposits:
v. 133,p. 1702-1703. Ecoa. G•m.., v. 67, p. 281-301.
Hosking,K. F. G., 1967,The relationshipbetweenprimary
1961b, Standards for reporting concentrationsof deu-
terium and oxygen-18in natural waters: Science,v. 133,tin depositsand granitic rocks,in A TechnicalConference
p. 1833-1834. on Tin: Internat. Tin Council, London,.v. 1, p. 267-311.
-- Hulston, J. R., 1964, Variations in the ratios of the four
1963,The isotopicgeochemistryof water and carbonin
stable sulfur isotopesin meteoritesand their relation to
geothermal areas, in Tongiorgi, E., ed., Nuclear geology
on geothermalareas, Spo!eto: Pisa. ConsiglioNazionale chemicaland nuclear effects: UnpublishedPh.D. thesis,
delle Ricerche, Laboratorio di Geologia Nucleare. McMaster University.
1966, Isotopic compositionand origin of the Red Sea Kajiwara, Y., and Krouse, H. R., 1971, Sulfur isotope
and Salton Sea geothermal brines: Science, v. 154, p. partitioningin metallic sulfide systems: CanadianJour.
1544-1548. Earth Sci., v. 8, p. 1397-1408.
Creasey, S.C., 1966, Hydrothermal alteration, in Titley, Kelly, W. C., and Turneaure,F. S., 1970,Mineralogy,para-
S. R. and Hicks, C. L., eds., Geology of the porphyry genesis,and geothermometry of the tin and tungstende-
copper deposits, southwestern North America: Tucson positsof the easternAndes,Bolivia: EcoN. G•o•..,v. 65,
University Arizon Press, p. 51-74. p. 609-680.
Czamanske,G. K., and Rye, R. O., 1974, Experimentally Kennedy,G. C., 1950,A portionof the systemsilica-water:
determined sulfur isotope fractionations between sphale- Ecom GF.o•..,v. 45, p. 629-653.
rite and galena in the temperaturerange 600ø to 275øC: -- Wasserburg,G. J., Heard, H. C., and Newton,R. C.,
EcoN. G•m.., v. 69, p. 17-25. 1962, The upper three-phaseregion in the systemSiO2-
Dansgaard,W., 1964,Stableisotopesin precipitation.Tellus, H•O: Amer. Jour. Sci., v. 260, p. 501-521.
v. 16, p. 436. Klevtsov,P. V., and Lemmlein,G. G., 1959, Pressurecor-
Deines, P., 1968, The carbon and oxygen isotopiccomposi- rectionsfor the homogenization temperaturesof aqueous
tion of carbonatesfrom a mica periotite dike near Dixon- NaC1 solutions [in Russian]: Akad. Nauk. S.S.S.R.
ville, Pennsylvania: Geochim.et Cosmochim.Acta, v. 32, Doklady, v. 128, p. 1250-1253.
p. 613-625. Krauskopf,K. B., 1967, Source rocks for metal-bearing
1970, Mass spectrometercorrection factors for the de- fluids; in Barnes,H. L. ed., New York, Geochemistryof
termination of small isotopic compositionvariations of hydrothermalore deposits:Holt, Rinehart,and Winston,
carbon and oxygen: Internat. Jour. Mass Spectrometry Inc., p. 1-33.
Ion Phys., v. 4, p. 283-295. Landis,G. P., 1972, Geologic,fluid inclusion,and stable
Egeler, C. G., and de Booy, T., 1956,Geologyand petrology isotope studies of a tungsten-basemetal ore deposit:
of part of the SouthernCordillera Balanca, Peru: Geolo- Pasto Bueno, northern Peru: Unpubl. Ph.D. thesis,
gisch-Mijnbouw-kundig,Genootschap,NederlandschKon- University Minnesota, 172 p.
inklijk, GeologischSerie Deel XVII, p. 1-86. Lindgren, W., 1933, Ore Deposits: New York, McGraw-
Engel, A. E. J., Clayton, R. N., and Epstein, S., 1958, Hill, 644 p.
Variations in isotopic compositionof oxygen and carbon Lowell,J. D., and Guilbert,J. M., 1970,Lateral andvertical
in Leadville limestone(Mississippian,Colorado) and in its alteration-mineralization zoningin porphyryore deposits:
hydrothermaland metamorphicphases:Jour. Geology,v. Eco•;. GF•L., v. 65, p. 373-409.
66, p. 374-394. Malaga, S., F., 1954,E1 tungstenoen E1 Peru: Sociedad
GeologicaDel Peru, Bol. 27.
Epstein, S., and Taylor, H. P., Jr., 1967, Variation of OS/ Maske, S., and Skinner,B. J., 1971,Studiesof the sulfosalts
O •6 in minerals and rocks, in Abelson, P. H., ed., Re- of copperI. Phasesand phaserelationsin the systemCu-
searches in Geochemistry: New York, John Wiley and As-S: Ecoa. G•ot.., v. 66, p. 901-918.
Sons, Inc Meyer, C., and Hemley,J. J., 1967,Wall rock alteration,in
Friedman, I., Redfield, A. C., Schoen, B., and Harris, J., Barnes, H. L., ed., Geochemistryof Hydrothermal Ore
1964, The variation of the deuterium content of natural Deposits: New York, Holt, Rinehart, and Winston, Inc.,
waters in the hydrologic cycle: Rev. Geophysics,v. 2, p. 166-235.
p. 177-224. Miller, B. L., and Singewald,J. T., Jr., 1919, The mineral
Garlick, G. D., and Epstein, S., 1966, The isotopic com- depositsof South America: First Ed., New York, Mc-
position of oxygen and carbon in hydrothermalminerals Graw-Hill Book Co., Chap. 10, p. 438-515.
at Butte, Montana: EcoN. G•o•.., v. 61, p. 1325-1335. Mitchell, A. H. G., and Garson,M. S., 1972, Relationship
Giletti, B. J., and Day, H. W., 1968, Potassium-argonages of porphyry copper and circum-Pacifictin depositsto
of igneous intrusive rocks in Peru: Nature, v. 220, p. paleo-Benioffzones: Inst. Mining Metallurgy Trans., v.
570-572. 81, p. B10-25.
Graf, D. L., Friedman, I., and Meents, W. F., 1965, The Northrop, D. A., and Clayton, R. N., 1966, Oxygen-isotope
origin of saline formation waters, II: Isotopic fractiona- fractionationsin systemscontainingdolomite: Jour Geol-
tion by shale micropore systems: Illinois State Geol. Sur- ogy, v. 74, p. 174-196.
vey Circular 393, p. 1-32. Ohmoto, H., 1970, Influenceof pH and fo• of hydrothermal
Haas, J. L., Jr., 1971, The effect of salinity on the maximttm fluids on the isotopiccompositionof sulfur species[abs.]:
thermal gradient of a hydrothermal system at hydrostatic Geol. Soc. America, Ann. Mtg., Milwaukee, Wisconsin.
pressure: Ecoa. GEOL.,v. 66, p. 940-946. 1972, Systematicsof sulfur and carbon isotopesin hy-
Hall, W. E., and Friedman, I., 1963, Compositionof fluid drothermal ore deposits: Eco•r. G•-o•., v. 67, p. 551-578.
inclusions Cave-in-Rock fluorite district, Illinois and Upper and Rye, R. O., 1970, The Bluebell Mine, British
Mississippi Valley zinc-lead district: Ecoa. G•L., v. 58, Columbia--I, Mineralogy, paragenesis,fluid inclusions,
p. 886-911. and the isotopesof hydrogen, oxygen, and carbon: Eco•r.
Hitchon, B., and Friedman, I., 1969, Origin of formation G•o•., v. 65, p. 417-437.
waters in the Western Canada sedimentary basin--I: O'Neil, J. R., Clayton, R. I•., and Mayeda, T. IC, 1969,
Geochim. et Cosmochim.Acta, v. 33, p. 1321-1350. Oxygen isotopefractionation in divalent metal carbonates:
Holland, H. D., 1959, Some applications of thermochemical Jour. Chem. Phys., v. 51, p. 554?-5558.
data to problems of ore deposits: I. Stability relations O'Neil, Jr., and Epstein, S., 1966a, Oxygen isotopefractiona-
among the oxides, sulfides, sulfates and carbonates of ore tion in the systemdolomite-calcite-carbondioxide: Science,
and ganguemetals: Ecoa. Ggon, v. 54, p. 184-233. v. 152, p. 198--201.
P.4STO BUENO TUNGSTEN-BASE METAL ORE DEPOSIT 1059
• 1966b,A methodfor oxygen isotopeanalysisof milli- 1969,Oxygen and hydrogenisotoperatios of clay minerals
gram quantities of water and some of its applications: from porphyry copper deposits: Ecoa. GF•oL, v. 64, p.
Jour. Geophys. Research, v. 71, p. 4955-4961. 755-777.
-- and Taylor, H. P., Jr., 1967, The oxygen isotope and • 1971, Hydrogen and oxygen isotoperatios in minerals
cation exchangechemistry of feldspars: Am. Mineralogist, from porphyry copper deposits: Ecoa. G•oL., v. 66, p.
v. 52, p. 1414-1437. 515-542.
1969, Oxygen isotope equilibrium between muscovite Sillitoe, 1• H., 1972, A plate tectonic model for the origin
and water: Jour. Geophys.Research,v. 74, p. 6012-6022. of porphyry copperdeposits: Ecoa. GF. oL., v. 67, p. 184-
197.
Roedder, E., 1963, Studies of fluid inclusionsII: Freezing
data and their interpretion: Ecoa. GF.
oL., v. 58, p. 167-211. Skinner, B. J., 1960, Assemblage enargite-famatinite, a pos-
1967, Fluid inclusions as samples of ore fluids, in sible geologic thermometer [Abs.]: Geol. Soc. America
Barnes, H. L., ed., Geochemistryof hydrothermalore de- Bull., v. 71, p. 1975.
posits: New York, Holt, Rinehart, and Winston, Inc., p. Steinmann, G., 1929, Geologicyon Peru: Heidelberg, Carl
515-574. Winters Universitatsbuchandlung,Verlags-Nr 2064.
Suzuoki, T., and Epstein, S., 1970, Hydrogen isotopefrac-
1971, Fluid inclusions studies on the porphyry- tionation factors (a') between muscovite, biotite, horn-
typeore depositsat Bingham,Utah, and Butte, Montana: blende, and water [Abs.]: Am. Geophys. Union Trans.,
Ecoa. Gv.oL., v. 66, p. 98-120. p. 451-452.
Rose, A. W., 1970, Zonal relations of wallrocgk alteration Takenouchi, S., and Kennedy, G. C., 1965a, Dissociation
and sulfide distribution at porphyry copper deposits: pressuresof the phase CO•.5•} H•O: Jour. Geology, v.
Ecoa. G•o•., v. 65, p. 920-937.
73, p. 383-390.
Rye, R. O., 1966, The carbon,hydrogen,and oxygeniso- • 1965b,The soubilityof CO• in NaC1 solutionsat high
topic compositionof the hydrothermalfluids responsible temperaturesand pressures:Am. Jour. Sci., v. 263, p. 445-
for the lead-zincdepositsat Providencia,Zacatecas, 454.
Mexico: Eco•q.G•o•..,v. 61, p. 1399-1427. Tarnawiecki, H. C., 1911, The Huaura wolfram mines:
1974,A comparison of sphalerite-galenasulfurisotope Mining Journal [London], v. 94, p. 687-689.
temperatureswith filling temperaturesof fluid inclusions: Taylor, H. P., Jr., and Epstein, S., 1962a, Relationshipbe-
Ecoa. Gm•., v. 69, p. 26-32. tween x•O/•60 ratios in coexisting minerals of igneous
-- Hall, W. E., andOhmoto,H., 1974,Carbon,hydrogen, and metamorphicrocks: Part I, Principles and experi-
oxygen, and sulfur isotopestudy of the Darwin silver- mental results: Geol. Soc. America Bull., v. 73, p. 461-480.
lead-zincdeposit,southernCalifornia: Ecoa. Gv•o•..,
v. 1962b, Part II, Applications to petrologic problems:
69., p. 468-481. Geol. Soc. America Bull., v. 73, p. 675-694.
Ry..e,
R. O. andO'Neil,J. tL, 1968,The Ox8content of water Taylor, H. P., Jr., Frechen, J., and Degens, E. T., 1967,
m primaryfluid inclusionsfrom Providencia, north-central Oxygen and carbon isotope studies of carbonatites from
Mexico: Ecoa. Gv.o•.,v. 63, p. 232-238. the Laacher See District, West Germany and the Alno
and Sawkins, F. J., 1974, Fluid inclusionand stable District, Sweden: Geochim.et Cosmochim.Acta, v. 31,
isotope studiesin the Casapalca Ag-Pb-Zn-Cu deposit, p. 407-430.
Andes,Peru: Ecoa. Gv.o•..,
v. 69, 181-205. Thode, H. G., Monster,J., and Dunford, H. B., 1961,Sulfur
Samoy10vich,
L. A., andKhetchikov,
L. N., 1968,Pressure isotopegeochemistry:Geochim.et Cosmochim.Acta, v.
corrections
to thehomogenization
temperaturesof aqueous 25, p. 159-174.
saltsolutions:Geokhimiya,
no.12,p. 1462-1469. Truesdell, A. H., 1971, Nonideality of oxygen isotope
Savin,S. M., andEpstein,
S., 1970a,
Theoxygen
andhydro- fugacity in salt solutionsat elevatedtemperatures--Geo-
gen isotopegeothermometry of clay minerals:Geochim. chemicalimplications[abs.]: Geol. Soc. America, Abs.
et Cosmochim. Acta, v. 34, p. 25-42. Programs, v. 3, no. 7, p. 735.
• 1970b, Theoxygen andhydrogen isotopegeochemistry White, D. E., 1957a, Thermal waters of volcanic origin:
of oceansediments and shales:Geochim. et Cosmochim. Geol. Soc. America Bull., v. 68, p. 1637-1658.
Acta, v. 34, p. 43-64. 19571>,Magmatic, connate, and metamorphicwaters:
Sawkins,F. J., 1972,Sulfideore deposits in relationto Geol. Soc. America Bull., v. 68, p. 1659-1682.
platetectonics: Jour.Geology, v. 80,p. 377-397. 1968, Environmentsof generation of some base metal
• and Rye, R. O., 1970,The Casapalca silver-lead-zinc- ore deposits:Ecoa. Gv•o•..,v. 63, p. 301-355.
copper deposit, Peru:An oredeposit formedby hydro- Barnes, I., and O'Neil, J. R., 1971, Spring waters of
thermal solutions of deep-seated origin?[abs.]:Geol.Soc. non-meteoricorigin, California Coast Ranges labs.]:
Amer.,Ann.Mtg., Milwaukee, Wisconsin. Geol. Soc. America, Ann. Mtg., Washington,D.C.
Shcherba, G. N., 1970a,Greisens (Part 1): Internat.Geol. Wilson,J. J., 1963,Cretaceousstratigraphyof CentralAndes
Rev., v. 12, p. 114-150. of Peru: Am. Assoc.PetroleumGeologistsBull., v. 47,
p. 1-34.
• 1970b,Greisens
(Part 2): Internat.Geol.Rev.,v. 12, • andReyes,L., 1964,Geologiadel cuadrangulode Pataz:
p. 239-255.
ComisionCarta GeologicaNacional,Lima, Peru, Bol. 9.
Sheppard,S. M. F., and Epstein,S., 1970,D/H and x80/•60 • and Garayar,J., 1967,Geologiade los cuadrangulosde
ratios of minerals of possible mantle or lower crustal Mollebamba,Tayabamba,Huaylas, Pomabamba,Carhuaz
origin: Earth Planet. Sci. Letters, v. 9, p. 232-239. y Huari: Serviciode Geologicay Mineria, Lima, Peru,
Sheppard, S. M. F., Nielsen, R. L., and Taylor, H. P., Jr., Bol. 16.

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ECONOMIC GEOLOGY

BULLETIN OF THE SOCIETY OF ECONOMIC GEOLOGISTS

VOL.'69 NOVEMBER, 1974 NO. 7

Geologic,Fluid Inclusion,and StableIsotopeStudiesof

GARY P. LANDIS AND ROBERT O. RYE

The Pasto Bueno tungsten-basemetal ore deposit is situated at an elevation of ---•

Introduction Wolframite was discovered at Pasto Bueno in

massivewhite quartzitesconsistingof fine-grained,

Formation is not present and the Goyllarisquiza

Ouarlz monzanile {Consuzo

Volcanic dikes and sills

Normal fault--Dashed where

Strike and dip of beds

._•0 Strikeanddipof folioSion

ES9000 1:'20000 E21000 E22 000 E23 000

rarely extendsfarther than 1 to 3 metersbeyondthe in a matrix of black carbonaceous material,in part

Sta. Isabel 430!

0 IO0 200 METERS

•U•n• x•86m •'l•-,•

HOBrENSI• -353 ../; __., _•. _ . /•::t. :1

I- ./.1• - m • I /x '• ' • - -- , '- •- x•- ' x-/ •-- - - I x/ •

A Tungsten 9.I n•y,+

+ Leod, zincs ond silver

GREISENllEARLY VEIN LATE

Fro. 7. zl. PastoBuenomineralparagenesis.The diagramis skewedto the right to better

first periodproduceda wolframiteof thick stubby purple non-fluorescent crustifications

Early tetrahedriteis antimonyrich. Intermediate More than 85 polishedplates of representative

TypeII. Polyphase inclusions

Fro. 8. A. Fluid-inclusion filling temperatures. Vertical lines indicate maximum range of

++ -7- ++ ++ -7- +++

$Mx = [Rx- R,ta)/Rsta] X 1,000 Sampleselection

whereR=(D/H), (180/•øO), (laC/12C), Pasto Bueno material intended for crushingand

FIG. 9. Pasto Bueno hydrothermalfluids isotopiccomposition. A. •D values of water in

TABLE5. Hydrogen and Oxygen Isotopic Compositionof Hydrous Minerals

Geologicsetting Sampleno. Description (SMOW) (SMOW)

Phyllic-argillic alteration GR-13 Intensealteration; pyrite, pyrrhotite, --82.9 6.64

Product of pervasiverock alteration GR-6 Feldspar alteration sericite -54.5 9.65

T•,sLE6. QuartzOxygenIsotopeData within the stock interior are enriched in deuterium

TABLe.7. Oxygen IsotopeValues of ConsuzoStock Mineral Separates

Mineral GR-6 GR- 13 9L-206 9F- 105 GR-8

Quartz q- 10.62 q- 11.00 q- 10.26 +9.90

watershavebeenpartially discussed above. Neither catethe calculated•xsOH2o

pyrite 0.55 px-gn 1.00447 223.6+ Sulfides at base of rug containing

7H-500-1 pyrite 0.70 px-sl 1.00078 347.1 Quartz-sulfide rug, no wolframite

pyrite 0.60 px-gn 1.00691 126.4 Sulfides enclosed by early vug

TABLE 8•( Continued)

Sampleno. Mineral $a4S Comments

9Mn-127 sphal 2.85 Veta Pueble, dark sphalerite

7Pelagatos pyrite - 0.26

9P-121-A pyrite 0.28 Limestonereplacementin samethrust, north of Hu-

9L-118 pyrite 0.72 Pyrite associatedwith early pegmatitic fluorite

I I I Ill I I II I I II II I I I/ll II I I Illll I IIII

oo-. w10o'•' o o •ooo•oo o o •o oo o "•

TAm.E 9. Hydrogenand OxygenIsotopicCompositionof Pasto BuenoSurfaceWaters

Analysesfor a•so performed4/71, for aD 8/71.

I•ll I METEORIC ' TCONSUZO /Volcanic cover

H•O Precambrian metomorphfc

Fxc,.12. Hypothetical sourcemodelfor PastoBuenohydrothermalfluids. Precipitation-meteoric water behind

Theseobservations Bueno. This studyrepresents

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