You are on page 1of 15

EconomicGeology

Vol. 79, 1984, pp. 1818-1832

A Hydrogen and Oxygen Isotope Study of the San Cristobal Mine, Peru:
Implicationsof the Role of Water to Rock Ratio
for the Genesisof Wolframite Deposits
ANDREW CAMPBELL,*
Departmentof Geology,Harvard University,24 OxfordStreet,Cambridge,Massachusetts
02138
DANNY RYE,
Departmentof Geology,Yale University,Box6666, New Haven,Connecticut
06511
AND ULRICH

PETERSEN

Departmentof Geology,Harvard University,24 Oxford Street,Cambridge,Massachusetts


02138
Abstract

Oxygenand hydrogenisotoperatioswere measuredfrom vein mineralsand extracted


fluidinclusionwatersfromthe SanCristobalwolframite-base
metaldepositin Peru. Oxygen
isotopevaluesfor quartzrangefrom 9.8 to 14.4 per mil andfor wolframitefrom 0.6 to 4.6
per mil. The calculatedi values at 300C for water in equilibrium with quartz and
wolframiteare ilSO-- 2.8 to 7.3 per mil for quartzand 1.4 to 5.4 per mil for wolframite.
Hydrogenisotopevaluesshowan overallrange of iD -- -58 to -148 per mil, but the
rangefor any givenmineralis muchsmaller.Thesedataare interpretedin light of a model
whichexaminesthe effectof temperatureandwaterto rockratioon the isotopiccompositions
of meteoricwaters exchangingwith granite. In a rock-dominatedsysteman isotopically

exchanged
water becomes
depletedin isOand enrichedin iD as the temperature
of
exchangedecreases.
When the water to rock ratio is alsoallowedto vary, a wide varietyof
water compositions
is generated.The isotopiccomposition
of mineralsfrom SanCristobal
canbe interpretedasthe resultof depositionfrom a meteoricwaterwhichhasundergone
isotopicexchangewith a graniteat 400C, with a water to rock ratio rangingfrom 0.01 to
0.003. Isotopicdata takenfrom two other wolframitedeposits,PastoBueno(Landis,1972)
and Panasquiera
(Kelly and Rye, 1979) are reinterpretedusingthe modeldevelopedfor
SanCristobal.Bothsetsof dataare consistent
with the hypothesis
that wolframitedeposits
are formedby meteoricwaterswhichhaveexperiencedexchangeat very low water to rock
ratios(<0.05). The importanceof the low water to rock ratio maybe relatedto the way in
whichtungstenis leachedfrom a crystallizedpluton.
Introduction

IN the pastten yearsthere havebeen a numberof


moderngeochmical
studiesof wolframite-quartz
vein
deposits.Theseincludestudiesof the PastoBueno
(LandisandRye, 1974), CarrockFells (Shepherdet
al., 1976), Panasquiera
(Kelly and Rye, 1979), and
TungstenQueen(Casadevall
andRye, 1980) deposits. In this paper we presentoxygenand hydrogen
isotopedata from anotherwolframite deposit,the
SanCristobalminein centralPeru (Fig. 1). In order
to explainthe originof the mineralizingsolutionsat

The model developedfor San Cristobalis applied


to Pasto Bueno and Panasquiera(the only other
depositsfor which the appropriateisotopicdata
exist) to examineto what extent the water to rock
ratio in the sourcearea may be important in the
genesisof wolframitedeposits.
GeologicSetting
Stratigraphy

LowerDevonianto Tertiaryrocksare exposedin

SanCristobal,a modelis presentedwhich examines the San Cristobalregion.The rocksfrom the Dethe effect of isotopicexchangebetweenhydrother- vonianExcelsiorGroup are the oldestexposedin
mal solutions
andgraniticrocksasa functionof the the area. They consistprimarily of phylliteswith
temperatureof exchange
andthe waterto rockratio. minorlimestone,basalt,andquartzite.The thickness
of the Excelsiorphyllitesis diScult to estimate,not
* Present address:Department of Geoscience,New Mexico
Institute of Mining and Technology, Socorro, New Mexico
87801

0361-0128/84/363/1818-1552.50

onlybecausethey are intenselydeformedbut also


becausethe base of the section is not exposed.

Harrison(1943)estimates
the thickness
to be 2,000

1818

H & 0 iSOTOPESTUDY,SANCRiSTOBALMINE, PERU

lgHot18
Fock$
Equado'.',..,Colombia

I
o ,

1819

The igneousrocksin the area consistof Tertiary


quartz monzoniteplugsand alaskitedikes.The two
mostimportantplugsin the areaare the Carahuacra
and Chumpe intrusions.The Carahuacraintrusion
cropsout 2 km north of SanCristobalover an area

\'

Peu ',, Brazil

of about2 km2. The Chumpeintrusioncropsout

Colqui

near the San Cristobalvein but is not well mapped


becauseit is in part covered by a glacier. The
alaskite dikes, which Pastor (1970) relates to the
Chumpe intrusion,consistof quartz and orthoclase

LoOroya

with small amounts of mafic minerals, sericite, and

pyrite. Thesedikesrangein width from 2 to 30 m.


Structure

The Yauli dome is the predominant structural


featureof the SanCristobalregion.The center of
this domeis formedby the Chumpeanticline.The
core of the anticline is occupiedby the Excelsior
Group phyllites(Fig. 2). The area has experienced

Central
;', Railroad

Peru

LocationMap

50 Km

FIG. 1. Map of central Peru showingthe location of some


of the principal cities and mines.

Kc

?San Cristobal

m at Tarma, 50 km east of San Cristobal. Uncon-

Vein

formablyoverlyingthe phyllitesare 300 to 700 m


of Catalina Volcanics of the Lower to Middle Permian

Mitu Group.Thesestrataconsistof coarselybedded

volcanicrocksof andesitic
andrhyoliticcomposition
whichare commonly
porphyritic.Abovethe volcanic
rockslie the Upper Triassicto Lower Jurassic
limestonesof the PucaraGroup.Thesedensegray- to
buff-colored limestones have a total thickness of 250
to 400 m. Interbedded with the Pucara limestone
are trachite and basalt flows. Above the Pucara

Groupis the Cretaceous


Goyllarisquisga
Formation.
It consistsmainly of sandstonewith minor basalt,

Chulec Fm.(Kc]

limestone,
andshale;in the SanCristobalregionit
is about220 m thick(Wilson,1963).Overlyingthe

GollarisquisgaFrn,(Kq]
Pucaro Fro.(dp]

Goyllarisquisga
Formationare the ChulecLimestone,
the Pariatambo
Shales,andthe Jumasha
Limestone,
all of Cretaceousage.Thesethree Cretaceousfor-

Mifu Fro,(Prn]
Excelsior Fm.(Oe]

mations have a total thickness of 530 to 730 m. In

Quartz monzonite(qmp]

general,the stratigraphic
thicknessof the post-

Veins

Devonian stratigraphicsection is less in the San


Cristobal region than elsewherebecausethe Yauli

Replacement bodies

domehasbeena topographic
highsincethe Devonian (Lepry, 1981).

kilometers

2. Generalized
gelogic
mapof the SanCristobal
district

(modifiedfrom Petersen,1965).

1820

CAMPBELL,RYE,AND PETERSEN

two periods of deformation:one in which the ExcelsiorGroupbasementrockswere deformedduring


the Hercynian and the other which affected both
the basementand cover rocks during the Tertiary
Andean deformation.

The details of the structural

developmentof the region have been discussedby


Lepry (1981).
Mineralization

The Chumpeanticlineis cut at nearlyright angles


by a seriesof fractureswhich were mineralizedto
form the ore veins at San Cristobal. The San Cristobal

vein systemis composedof two major veins, the


Main vein and the Siberia I vein. In addition, there

are numeroussmallersubsidiary
branchesfrom these
veins. This study focusesonly on the Main vein,
which has been mined for a horizontal

distance of

2.5 km and to a depth of up to 500 m. It cutsboth


the Devonian phyllites and the Permian volcanic
rocks. The vein changescharacter from a welldefined vein with sharp walls in the structurally
competentvolcanicsto a poorly defined vein zone
in the lesscompetentphyllites (Pastor,1970).
Mineralization occurred in three major stages
(Fig. 3): the first was a tungstenstage,consistingof
pyrite, wolframite, and quartz with trace amounts
of sericite and augelite (A12PO4OH2);
the second
was a base metal stage with pyrite, chalcopyrite,
sphalerite,galena,and barite; and the final stage
was predominantlycarbonatewith minor amounts
of sphaleriteand galena.Movementalongthe fracture between the stagesresulted in brecciationof
the vein minerals.

Pyrite, wolframite,and quartz occurtogether.In


general,pyrite wasdepositedbeforewolframiteand
wolframite before quartz. However, these periods
of mineraldepositionoverlapin time and space;this
overlapproducesa wide rangeof mineraldeposition
sequences,which has not been studied in detail.
The wolframite occursas crystalswhich are up to 8
cm long;the crystalsare frequentlytwinned. Chemically the wolframite,(Fe, Mn)WO4, rangesin cam-

PARAGENESIS

Augehte

--

Muscovite

Pyrite

Wolf remote

@uortz
holcopyrfte

I
--I

Spholerfte
Galena
Barite
Carbonate

....

I
I
I
!

FirstStage
Tungsten

Mnerolzoton

I
I

T
T

Bose Metal

MinerolizoOon

Carbonate

FIO. 3. Paragenesisfor the San CristobalMain vein. Dashed

verticallinesindicatebrecciationbetweenstages.

mineralscontinuedto be depositedwith the carbonate. The carbonateis predominantlyFe and Mn


rich, ranging from 64 to 96 mole percent FeCOa
with minor amountsof Ca and Mg.
Fluid inclusions

Fluid inclusions
at SanCristobaloccurasprimary,
pseudosecondary,
and secondaryinclusions.Many
of the primaryinclusions
are large,isolatedinclusions
and are commonlyfound in the cores of crystals.
Another mode of occurrenceof primary inclusions
is in milky growthbands.These trainsof crystallographicallycontrolledinclusionsradiate out from
the cores of the crystals.The abundanceof these
small inclusionsassuresthat a high proportion of
the inclusionsin each crystalare of primary origin.
This is an importantfactorwhen extractinginclusion
fluidsfor isotopicanalysis.
The pseudosecondary
and secondaryinclusions
both occur as planesof inclusionscutting the cores
of crystals.Althoughit wasnot possibleto distinguish
between planesof secondaryand pseudosecondary
inclusionson a texturalbasis,they canbe separated
by their range of homogenizationtemperatures
(Campbell,1983).
Homogenizationtemperaturesfor all inclusions
fromaugelite,quartz,sphalerite,barite, andcarbonate are shownin Figure 4. The main populationof
homogenizationtemperaturesfor primary inclusions
in quartzoccursbetween230 and330C. A smaller
populationof homogenizationtemperatureswhich
occurs between

I Second
Stage I Third
Stage
I

positionfrom 27 to 94 mole percent FeWO. Indi-

vidualcrystalsare zonedwith compositional


ranges
up to 60 mole percent FeWO. No other elements
in the wolframite were detected with energy dispersiveanalysis(Campbell, 1983).
Most of the chalcopyritewas depositedafter the
end of the first stage.It oftenformedan essentially
monomineralicband which was followedby sphalerite and galenadeposition.Occasionallyeuhedral
crystalsof pyrite are foundwithin the chalcopyrite.
Sphaleriteand galenadepositioncommonlyoccurred
at the sametime, but in somelocationssphalerite
deposition preceded galena deposition. In other
areasbarite was depositedalong with the galena.
The bariteoccursascrystalsup to severalcentimeters
in length and usuallyis associatedwith ore which
has a high silver content. Although the carbonate
was depositedafter the main period of sphalerite,
galena,andbarite deposition,smallamountsof these

150 and 230C

is attributed

to

secondaryinclusions.The rangeof homogenization


temperaturesmeasuredfrom individual quartz samples is almostas large as the overall temperature
range. Therefore, it is difficult to correlate the
variationsin isotopiccompositionof the quartzwith
changesin temperature of deposition.For the pur-

H & 0 ISOTOPESTUDY,SANCRISTOBALMINE, PERU


Augelite

1821

their constituents.For this reasona study of the


hydrogenand oxygenisotopecompositions
of minerals and fluid inclusion waters from San Cristobal

20
16

12

Quarfz

Spholerite

was undertaken.In this study we measuredthe


oxygenisotopecompositionof quartz, wolframite,
and siderite;the hydrogenisotopecompositionof
fluid inclusionwaters extractedfrom quartz, wolframitc, siderite, pyrite, sphalerite, chalcopyrite,
and barite, and the oxygenisotopecompositionof
fluid inclusion water extracted from pyrite and
sphalerite.
Samplesof sphaleriteand quartzwere examined
in polishedthick sectionand only those samples
with a high proportionof primary inclusionswere
chosenfor water extraction.For the opaqueminerals
thisprecautionwasnot possible.Standardtechniques
for extractionandanalysis
were used,assummarized
by Rye and Sawkins(1974) and Landis and Rye
(1974). Details of the proceduresare given in
Campbell(1983). Isotopicanalyses
were performed
with Nuclide 6- and 3-inch, 60-degree ratio mass
spectrometers.
All isotopicvaluesare reported in
the standard/i notation relative to the Vienna SMOW

2 -1_ i

Siderite

standard.The standarderror of eachanalysisis +_0.1


per mil for oxygenand +__1
per mil for hydrogen.In
HOMOGENIZATION
TEMPERATURE (C)
the percentyieldreportedfor the oxygenextractions,
perFIG. 4. Histogramshowinghomogenizationtemperatures the manometerreadingswere accurateto +__2
I00

'

200

$00

400

measured from fluid inclusions in vein minerals from San Cris-

cent.

tobal.Mineralsare arrangedparagenetically
startingat the top
with augelite.

Oxygen and Carbon IsotopeStudies


Quartz

poseof calculations
the temperatureat the peakin
The fi80 valuesfor 35 quartzsamplesare sumthe distribution
of temperatures,
300C,is assumed marizedin Table 1. As a check,mostsampleswere
to be the depositionaltemperaturefor quartz. analyzedat least twice. The averagevariationof
Freezing-point depressionmeasurementson fluid
thesemultiple analysesis about ___0.2
per mil. The
inclusionsyield freezing temperaturesof-1.6 to averageof the two, or three, analysesis used in
-3.9C whichcorrespond
to salinitiesof 2.7 to 6.3 latercalculations.
Thesefi80 valuesrangefrom9.8
equivalentweight percentNaC1.
to 14.4 per mil. In order to calculatethe isotopic
Alteration
composition
of water whichwouldbe in equilibrium
with
the
quartz
of theseisotopiccompositions,
the
Within the phyllites,wall-rockalterationnearthe
temperature
of
deposition
must
be
known.
As
stated
vein can be separatedinto three types.Closestto
the vein is a zone of silicification(2 m), the next above, a temperatureof 300C was used in this
zone consists
of sericiticand argillicalteration(3-5 calculationbecauseit representsthe peak in the
temperaturesfrom
m), and the outermostzone is characterized
by distributionof homogenization
fluid
inclusions
in
quartz.
Using
the oxygenisotope
abundantchlorite(7-14 m). The zoneof alteration
fractionation
equation
for
the
quartz-water
system
can be up to 20 m wide. In the volcanicrocksthe
from
Clayton
et
al.
(1972),
it
is
possible
to
calculate
silicifiedzoneis absentandthe sericiticandargillic the/isO values for water. The calculated values at
zone is only 3 m wide. However, the chlorite zone

is greaterthan 30 m thick,with the percentage


of 300C rangefrom 2.8 to 7.4 per mil. Changingthe
chlorite decreasingaway from the vein (Pastor, temperatureof quartz depositionby _+25Cwould
shiftthe calculatedrangeof water compositions
by
1970).
approximately+__1
per mil.

StableIsotopeStudies

Wolframite

Manystudies
in therecentpasthavedemonstrated The sO valuesfor 14 wolframitesamples
are
the usefulness
of stableisotopesin elucidatingthe summarizedin Table 2. These values range from
origin and history of hydrothermalsolutionsand 0.6 to 4.6 per mil. If one assumes
that the wolframite

1822

CAMPBELL,
RYE,AND PETERSEN
TABLE

Sample
no.
SC-1

SC-2

% yield

1.

Oxygen Isotope Compositionsof Quartz from San Cristobal

80
(%0)

98

12.6

100

12.5

90

14.6

103

12.2

AvgbO

Sample

()

no.

12.6

13.3

SC80-7

SC80-8

SC80-10

92

11.9
12.0

12.0

SC80-12

89
88

10.3
10.5

10.4

SC80-14

98
100

13.3
14.1

13.9

13.1

99

13.8

SC-5

102
93

13.4
13.5

13.5

SC-6

87

13.9

13.9

SC-7

100

11.1

11.2

98

11.3

SC-8

97
97

13.4
13.1

13.3

SC-9

98

12.8

12.7

SC80-16

96

12.5

94
98

13.1
13.2

13.2

SC80-21

98

14.3

14.2

SC-13

SC-16

SC-17

13.9
14.3

98

11.2

103

11.5

98

11.6

95

12.7

94

13.8

100

12.5

13.8

SC80-15

11.4

12.7

97

13.8

97

13.8

97

12.8

97

12.8

94

14.3

94

14.4

SC80-6

100

12.7

93

13.1

14.4

88

14.4

101
80

94

100

14.3

9.7

9.8

12.7

12.6

9.9

12.4

SC80-26

98

13.0

13.1

98

13.1

96

13.7

98

14.0

98

13.9

14.0

12.8

12.8

SC80-29

SC80-33

12.5
13.8
12.8

14.4
SC80-47

wasdepositedat the sametemperature(300C) as


the quartz with which it occurs(even thoughthey
may not be contemporaneous),
then it is possibleto
calculatethe equilibriumwatersusingthe empirically
derivedwolframite-water
fractionation
equationfrom
Landisand Rye (1974). At 300C, the calculated

92

12.2

SC80-34

12.9

14.0

12.2

SC80-45
SC80-4

14.2

94

100

SC80-42
SC-25

94

11.6

SC80-23

SC80-40
SC-18

11.8

11.6

13.8

99

11.7
11.9

(%o)

11.6

97

96

97
95

AvgbO

96

99

SC-10B

(%0)

97

SC-4

SC-10A

bO
% yield

SC80-49

92

102

14.1

95

12.8

93

12.8

97

11.7

94

12.9

97

12.5

13.9

12.3

12.7

96

11.3

96

12.7

12.0

97

10.7

10.7

99

13.0

13.0

95

12.9

resentsequilibrium.At 300Cthe quartz-wolframite


equationyieldsan equilibriumvalue of 7.7 per mil.
At San Cristobal the fi80 values obtained from

quartz-wolframitepairsfrom the samehand samples


range from 7.5 to 12.5 per mil. In these quartzwolframite pairs there appearsto be only a very
fi180valuefor waterrangesfrom1.4 to 5.4 per mil. vaguecorrelationbetween the oxygenisotopecomThe quartz-waterequationcanbe combinedwith position of the quartz and that of the associated
the wolframite-waterequationto yield a quartz- wolframite(Fig. 5). It thereforeappearsthat quartz
wolframitefractionation
equationassuming
that the and wolframitewere not in isotopicequilibrium,or
empiricallydeterminedfractionationequationrep- at least that it is difilcult to samplemineral pairs

H & 0 ISOTOPESTUDY, SAN CRISTOBALMINE, PERU


TABLE2.

Oxygen Isotope Compositionsof Wolframites

TABLE3.

from San Cristobal

Carbon and OxygenIsotopeCompositionsof

Carbonates from the San Cristobal Mine

Sampleno.

Sample

no.

% yield

SC80-16
SC80-21
SC-25
SC-10
SC80-33
SC-18
SC-9
SC80-45
SC-2
SC80-4
SC80-8
SC80-7
SC80-4
SC-8

1823

baC(%0)

bsO(%0)

lSo (%0)
SC80-35
SC80-38
SC80-26
SC80-42
SC80-21
SC80-44

0.6
1.0
1.0
1.5
1.5
1.6
1.7
2.3
3.3
3.6
4.1
4.1
4.6
4.6

89
98
98
98
97
98
101
95
93
104
100
97
100

-3.3
-3.3
-4.2
-4.8
-5.5
-6.3

2.5
4.1
2.7
4.5
3.4
2.4

ited. Table 3 also lists the j13C values for the

siderite. These values rangesfrom -6.2 to -3.3


per mil.
Inclusion water

The blSO values for water extracted from three

pyrite and one sphaleritesampleare summarizedin

Table4. All foursamples


have/51sO
valuesbetween

that were truly contemporaneous


owing to the iso- 4.5 and 4.7 per mil.
topic compositionalzoning in both quartz and wolframite.
Hydrogen IsotopeStudy
Inclusion

Carbonate

The/51sO
valuesfor sixsideritesamples
are summarizedin Table 3. Thesevaluesrangefrom 2.4 to
4.5 per mil. Homogenizationtemperaturesfrom
inclusionsin two samplesindicatethat the siderite
wasdepositedat about 140C. Usinga fractionation
factor for FeCOa-H20 from Becker and Clayton

(1976), the /51sOof the water in equilibriumwith


the carbonate

can be calculated

at 140C.

This

fluids were

extracted

from

TABLE4.

Hydrogenand OxygenIsotopeCompositions
of

Fluid Inclusion Waters Extracted from Various

calculationyields a range of blSOvaluesfor the


Vein Minerals from San Cristobal
water of-7.1 to -9.8 per mil. Thesewatersappear
to have been isotopicallylighter than the waters Sample
no.
Mineral
bD (%0) b80 (%0)
from whichthe quartzand wolframitewere deposI

14

I0

$10(%0) WOLFRAUITE
FIG. 5. Oxygenisotopecompositions
of quartzandwolframite
"pairs" (i.e., from the samehand sample)from San Cristobal
showingno correlation.

22 mono-

mineralic samplesof vein minerals.These waters


were analyzed for hydrogen isotope composition
and CO2/HO ratio. A few of the water samples
extractedfrom sulfidemineralswere alsoanalyzed
for oxygen isotope composition.The results are
shownin Table 4. The overall rangeof/SD valuesis

CO._
X 100

H20

SC-9
SC80-40

py
py

-82
-84

0.3
0.8

SC-9
SC80-33
SC-2

wolf
wolf
wolf

-60
-69
-84

1.0
1.1
0.7

SC-2
SC80-40
SC-10
SC80-47
SC80-42
SC80-5
SC80-29
SC80-29
SC80-38

qtz
qtz
qtz
ep
sp
sp
sp
sp
sp

-96
-107
-112
-96
-58
-74
-81
-84
-90

1.2
1.4
0.7
0.4
0.7
1.4
0.2
1.9
0.1

SC80-27
SC80-28
SC80-38
SC80-54

bar
bar
carb
carb

-128
-148
-86
-89

0.4

SC80-29
SC80-27
SC80-26
SC80-50

sp
sp
sp
py

-85
-89
-91
-56

12.5
20.0

4.5
4.7
4.5
4.6

0.2
0.3
0.2
0.4

Abbreviations:
bar = barite, carb -- carbonate,cp = chalcopyrite, py = pyrite, qtz = quartz, sp = sphalerite,wolf = wolframRe

1824

CAMPBELL,RYE, AND PETERSEN

from -148 to -58 per mil, but the range for each
mineral is much smaller.The most negativevalues
are from barite and are thought to representlate
fluids trapped in secondaryinclusions.These late
fluidsprobablyrepresentmeteoricwater which inflitrated the systemafter mineralization.In Figure
6, the/tD valuesare shownasa functionof paragenesis.The relation of/tD valuesto paragenesisis not
montonicbut is rather more complex.The interpretationof thesedatawill be givenin the next section.
The CO./H.Oratiosshowthat CO.is a very minor
constituent(<2%) of the ore solution,exceptin the
carbonatestagewhen the CO./H.Omolarratio was
as high as 0.2.

mineral-waterpairs with the mineral abundanceof


the different mineralsto get a whole rock-water
fractionation

factor.

A more general and convenient,althoughsimplified, approachgiven by Taylor (1978) is to assume


that the isotopiccompositionof plagioclase(Ana0)

is a reasonable
approximation
for the/taO valueof
the whole rock. The feldspar-water fractionation
factor

1,000 In a = 2.68 X 106/T' - 3.53


from O'Neil and Taylor (1967) indicatesthat at the
lower end of the magmatictemperaturerangethere
is only minor oxygenisotopefractionationbetween

rock and water. Therefore,the rangein the /tiao

valuesfor magmaticwater is alsoabout 6 to 9 per


Interpretation of IsotopicResults
mil. The hydrogenisotopefractionationfactor for
Theoretical considerations
rock-water at magmatictemperaturesis estimated
Magmaticwater hasbeen definedaswater which to be about -10 per mil (Sheppardet al., 1969).
has equilibrated with igneous rock at magmatic Thus,the/tD valuesfor magmaticwater rangefrom
temperatures(Sheppardet al., 1969; Taylor, 1979). approximately-40 to -80 per mil.
Therefore, by this definition, magmaticwater can
Temperatureof exchange
be either water released from a magma during
The procedure outlined in the preceding paracrystallizationor any subsurfacewater which has
been exchangedisotopicallyand chemically with graph can be used to determinethe isotopiccomigneousrocksat temperaturesnear 800C. Because positionof meteoric water which has undergone
magmaticwatercannotbe sampledwith anycertainty exchangewith an averagegranite at temperatures
of purity, the range of isotopic compositionsof lower than magmatic.If the "magmaticwater box"
magmaticwater mustbe calculatedfrom the range is consideredto show the range of water composiof isotopiccompositions
of igneousrocksand the tionsin exchangeequilibriumwith graniteat 800C
rock-waterfractionationfactors.The usualrange of in a rock-dominatedsystem,then Figure 7 shows
/tD and/taOvaluesof graniticrocksis -50 to -90 how the centerpoint of the "exchangedwater box"
per mil and 6 to 9 per mil, respectively.The most movesas the temperature of exchangedecreases.
precisemethod for calculatingthe isotopiccompo- This calculationwas carried out assumingthat the
sitionof water in equilibriumwith granitein a rock- center point of the magmaticwater box represents
dominatedsystemwould be to combineindividual equilibrationat 800C. The relative movementof
the centerpointwasthen calculatedusingthe slope
of the fractionationcurve for hydrogenbetween
biotite and water,

-40'

PY

$p

A = Dbiot-- fiDI-io= -21.3 X 106/Te - 2.8,


from Suzuokiand Epstein (1976), and for oxygen
between plagioclaseand water,

-8O

A = 18Oplag
-- 18OH
O= 2.68X 10a/T2 - 3.53,

-120

Bar (secondary

from O'Neil and Taylor (1967). The choiceof the


fractionation
equationfor biotiteto approximate
the
isotopicfractionation
of the wholerockisnot crucial
becausein thismodelonly the slopeof the fractionationequationis usedand,accordingto experimental
data from Suzuokiand Epstein(1976), the slopesof

inclusions)

the fractionation curves for biotite,

-160

Parogenesis

>

FIG. 6. Hydrogen isotopecompositionsof waters extracted

muscovite,

phlogopite,and hornblendeare very similar.However, the magnitudesof the fractionationfactorsfor


the varioushydrousmineralsare different, soit was

from various vein minerals from San Cristobal as a function of

assumed that at 800C the fractionation

paragenesis.

hydrogenin granite and hydrogenin H9.Owas -10

between

H & 0 ISOTOPESTUDY,SANCRISTOBALMINE, PERU


Water

1825

to rock ratio

In addition to the temperature of exchange,the


isotopiccompositionof an exchangedwater is also
dependenton the water to rock ratio (W/R, mole
ratio). Usingthe equationderivedby Taylor (1974)

/SMOW

c'
oo.

Wfwater -1
t- R6rock= Wfwater+ Rfrock,

600

70o % I

Grant

oho

we calculatedthe effect of different W/B on the


isotopiccompositionof an exchangedwater.
If equilibrium is reachedbetween the water and
rock, then

-I0

--

f -- frock
i
frock
i
f -- hrock-water)
'
fwater(frock

where W is the atom percent meteoric water oxygen


-160

in the total systemand R is the atom percent


exchangeablerock oxygenin the bulk system,f is
final, i is initial, A is the rock-water fractionation
ii

-0

-I0

I0

20

factor for either hydrogenor oxygen,and f is the


did or f80 value. The above equation can be
rearranged to solve for the isotopic compositionof
water in equilibriumwith graniteat a giventemper-

btSO
(%,)
FIG. 7. Calculation of the effect of temperature on the
isotopic equilibrium between water and granite in a rockdominatedsystem.The pointsrepresentthe movementof the
center point of the exchangedwater box as the temperatureof
exchangedecreases.

ature:

ffwater
-- --

w + zr

i
fwater
q- --

zr

w + zr

-- Arock-water).

In thisequation,w (water)andr (rock)are in weight

per mil. This is an approximateaveragefor the units, and z has been added to correct for the
fractionation
factorsof the varioushydrousminerals differentamountsof oxygenandhydrogenper weight
and agreeswell with the analysesfrom natural unit in water and rock. Water contains89 weight
systems
whichhavebeenusedto definethemagmatic percent oxygen,whereasgranite typically contains

water box. In the caseconsideredhere, the fD and only 45 to 50 weight percent, so the z for oxygen
is equalto 45 dividedby 89, or about0.5. A typical
f80 of the granitearefixedsothat
granitecontainsabout0.6 weight percentwater, so
06Owate
r 42.6 X 106
the z for hydrogenis equalto about0.006. A similar
0T
Ta
equationfor the effect of temperatureand water to
and
rock ratio on the isotopic compositionof water
0618Owater--5.3 X 106
exchangingwith rock is given by Ohmoto and Rye
(1974) with their discussionof Kuroko deposits.
OT
Ta
Figure 8 showsthe exchangecurvesfor meteoric
--

--

Therefore,

OOwate
r

--

42.6 X 106

01aOwater--5.3 X 106--

--8.

water (fD =-140%0, f80 =-20%0) exchanging


with granite(bD = -70%o,f80 = 7.5%o)at different
temperatures.These curves show the isotopiccompositionof water in equilibrium with granite as a

The aboveequations
showthat the slopeof the line functionof w/r. At high w/r, the water experiences
whichexpresses
the changein isotopiccomposition only an oxygenshift,but at low w/r, the fD is also
of exchanged
water asa functionof temperatureis affected.Furthermore,with increasing
w/r the water
constant.As the temperatureof exchangedecreases, compositioncurvesdiverge, whereas the rock comthe water becomesdepletedin 80 and enrichedin position curves converge.
deuterium
andtrendstowardthe isotopic
composi- It is interestingto note in Figure 8 the different
tion of seawater.
isotopiccompositions
for waterswhich can be genThissimplemodelis applicablenot onlyto granite erated by the water-rock interaction. Considerthe
but also to other related leucocratic rocks because exchange
curvefor 400C.At very low w/r (<0.001),
of the general nature of the fractionation factors the resultant water will have a fD heavier than
used.
magmaticwater. At w/r between 0.001 and 0.005

1826

CAMPBELL, RYE, AND PETERSEN

exchangeable.
Different fractionationfactorscan be
usedto approximateother rock types.
Figure 8 alsoshowsthe composition
of granitein
equilibriumwith water at a different w/r. Dotted
linesconnectcoexisting
water androckcompositions.
Taylor (1978) has examinedthe effect of meteoric
water alteration on severallarge granitic batholiths

-40

from western North America. These include the


Idaho and Boulder batholiths in the northwestern

o -80

United States and the Coast Range batholith of


British Columbia. He finds that these batholiths have

undergoneexchangewith meteoric water over a


rangeof water to rock ratios.Taylor'sdata plot on

a iD - i80 diagramin a mannerwhich mimics

-120

-160

-20

-/0

&O(%)
FIC. 8. Exchangecurvesfor meteoricwater (/iD = -140%o,

almostperfectlythe theoreticallycalculatedcurves.
Many of the analysesplot in the regionof the curve
whichcorresponds
to low w/r (0.01 - 0.001). These
values come from an area that is geographically
separatedfrom the area which hashigh w/r values.
The batholithsshow evidence of exchangeat low
w/r over a distanceof 10 to 20 km. This evidence
from naturalsystemsindicatesthat meteoricwater
canbe extensivelymodifiedisotopicallyby exchange
with graniticrocks.

/i80 = -18%o)withgranite(/iD = -70%0,/i80 = 7%0)at 400


and 600C asa functionof water to rock ratio (w/r). The w/r is
Applicationto Natural Systems
givenin weightunits.Solidlinesare water compositions,
dashed
San
Cristobal
linesarerockcompositions,
anddottedlinesconnectequilibrium
water and rock compositions.

the water will have a iD equalto typical magmatic


water but with a lower /i80. Waters of this com-

positioncould alsobe generatedby meteoricwater


with a/iD similarto magmaticwater and which has
undergoneexchangeat a moderatew/r (the classic
oxygenshift) or mixedwith somemagmaticwater.
Exchangeat w/r = 0.01 will producea water with
a/iD value lessthan that of magmaticwater. This
couldalsobe producedby an oxygen-shifted
meteoric water that had the appropriateinitial/iD. This
composition,however,couldnot be producedsolely
by mixing magmaticand meteoric water owing to
its relatively negative /iD value. In general the
waterswhich are generatedby exchangewith a low
but fluctuatingw/r will have a relatively constant

The isotopicevidencefrom SanCristobalsupports


the hypothesisthat ore depositscan be generated
by meteoricwaterswhichare modifiedby exchange
with granite under conditionsof low w/r.
The /iD of waterstrapped in barite rangesfrom
-130 to -150 per mil. This is thought to represent
meteoricgroundwater trappedafter mineralization
in secondaryinclusions.We will assumethat the
local meteoric water near the time of mineralization

was -140 per mil. This agreeswith estimatesof


palcometeoric
watersfor other ore depositsformed
at about the same time

in the Peruvian

Andes.

LandisandRye (1974) proposethat the composition


of palcometeoric
water responsible
for formingthe
PastoBuenodeposithad a/iD of about -145 per
mil. Pasto Bueno is located about 250 km north of

SanCristobalandmineralizationis datedat 9.5 m.y.


/i80 and a variable/iD. These waters will therefore
At Casapalca,40 km to the west of San Cristobal
appearasa verticalswathon a/iD -/i80 diagram. and closer to the coast,Rye and Sawkins(1974)
This contrastswith meteoric water exchangedat a proposethat the palcometeoricwater had a
moderate(2.0-0.2) but fluctuatingw/r which will rangingfrom -100 to -140 per mil. For Colqui(10
havea constant/iDbut a variable/i80andwill plot m.y.), 60 km northwestof San Cristobaland even
closer to the coast, Kamilli and Ohmoto (1977)
asa horizontalswathon a/iD - /i80 diagram.
The model presentedhere is rather simple, but proposedthat the meteoricwater at the time of
it can be adaptedto take into accountother situa- mineralizationhad a/iD value near -100 per mil.
tions.For example,the z valuescan be changedto All of thesedepositsare locatedat elevationsgreater
simulatean alteredgranitewhichhasa higherwater than 4,000 m.
Figure 9 showsthe range of calculatedoxygen
contentowing to the presenceof chlorite, or a rock
for the quartz
in which only the oxygencontainedin feldsparis and hydrogenisotopecompositions

H & 0 ISOTOPESTUDY,SANCRISTOBALMINE, PERU


,

[]

Pymte
Spholerte

1827

exchangecurve for these conditions is shown in


Figure 9.

SMOW
400C

-40

//

??

.'

-/

I Water

//Wolfram'de
L,51 I

Carbonate
/

Four individualwater compositionsare alsoplotted in Figure 9. These represent fluid inclusion


watersextractedfrompyrite andsphaleritefor which
both the hydrogenand oxygenisotopecompositions
were measured.The oxygen isotope compositional
range of these four samplesis very small, 4.6 +_0.1
per mil, whereasthe hydrogenisotopecomposition
rangesfrom -56 to -91 per mil. This confirmsthe
trend exhibitedby the waterswhich depositedthe

quartz and wolframite:a narrow range of


valuesanda large rangeof D values.One problem
with determiningthe isotopiccompositionof waters
which depositedoxygencontainingmineralssuchas

-120

silicates or oxides is that the D value is measured

directly on the extracted fluid inclusionwater and

-160

the sO valueis calculated


fromthe isotopiccompositionof the mineral.In this situationit is possible

thatthesO recordsthe composition


of the original
i

-20

-I0 61e0(%0o) I0

water, but that the D recordsthe compositionof


some later water trapped in secondaryinclusions.
The fact that the SO of the fluid inclusion waters

[;'lc. 9. Isotope compositionalranges [or waters depositing extracted from San Cristobal sulfides falls within the
quartz, wolramite,and carbonate at San Cristobal. The solid sO rangeof the waterscalculated
to havedeposited
line is the exchangecurve or400C. '['he meteoric-magmatic the quartz and wolframite lends support to the
water mixing line (long dashes)is shown for comparison.The
that the D valuesmeasuredfor quartz
carbonatefluidscan be explainedby mixing of exchangedand assumption
andwolframitedo reflectthe originalwater responunexchangedmeteoric water.

and wolframite waters from San Cristobal and the


presumed meteoric water at the time of mineraliza-

tion.The isotopiccomposition
of the waterin equilibrium with wolframite was calculated with the

wolframite-water
fractionation
equationfromLandis
andRye (1974). Because
thisfractionation
equation
is empirically derived, it is not well known and

thereis a fair rangeof uncertaintyattachedto the

estimated 6180 values. The a80 and D values

sible for deposition.The compositionof the waters


which depositedthe carbonatemineralsdoesnot fit
this simple model and will be discussedin a later
section.

Althoughthe model presentedhere can explain


quite simplythe isotopiccompositionof the mineralizing solutionsat SanCristobal,it doesassumethe
existenceof a granitic rock at depth. There is no
direct evidenceof this igneousbody, suchas intersecting it in the mine workings, but the indirect
evidence is favorable. In order to have produced
the hot (up to 400C) aqueousfluid there must

plottedin Figure 9 indicatethat the water which


depositedthe wolframitecan be explainedas a

have been a heat source. The most reasonable heat

mixture of magmaticand meteoricwater; the water

sourceis the intrusionof a magma.The alaskite

from which the quartz was depositedcannotbe dikes found near the vein supportthe idea that a

explained
in thisfashion
because
it hasa relatively magma was present and suggestthat it was of
lowD andhighsO. However,the compositional
leucocraticcomposition.
Other igneousrocksin the
rangesfor both mineralscan be explainedby a area which were intruded during the Tertiary, the
modelin which the San Cristobalpaleometeoricpresumedtime of mineralization,are quartz monwater exchangedwith a graniticrock at 400C with

zonite porphyries.The closestof the quartz mon-

a w/r ranging
fromabout0.01to 0.003.Anexchangezonite porphyriesis only 1 to 2 km southof the San
temperature of 400C is reasonable because fluid

inclusion
homogenization
temperatures
in the early
stagesof mineralization
rangeup to 400C. One
wouldexpectthat the temperature
of isotopicexchangewith the graniticrockto be slightlyhigher

Cristobalvein, andalthoughits exposedsurfacearea


is small,it may expandat depth. In the absenceof
a granitic rock, the meteoric water could have
exchangedwith the basementphyllites. However,
in order to accountfor the isotopiccompositionof

than the depositional


temperatureof the minerals the waters calculated for San Cristobal, meteoric
in the vein becausethe exchange
takesplaceat a waters would have first had to exchangewith the
greater depth than the mineral deposition.The phyllites at a low w/r to achieve the proper D

1828

CAMPBELL,RYE,AND PETERSEN

value and then to mix with unexchangedmeteoric During eachcyclethe i80 remainsrelativelyconwater to obtain the correct /580 values, because stantandthe/SDincreases.
Betweencyclesthe/5180
phyllites are enriched in heavy oxygenrelative to decreasesmoderately and the/SD diminishesdrastically. One possibleexplanationfor this phenomenon
granite.
From the observations above it seems reasonable

is that there were three pulses of mineralizing


solution that exchangedwith a granitic rock at
successively
lower temperatures.The patternwithin
each
cycle
is
moredifficultto explainunambiguously.
Pasta Buena
It appearsto representa decreaseof w/r with time.
This water-rock interaction model can also be
This couldbe due to an increasingamountof fracusedto explainthe /SDand /580 data from Pasta turing with time. The greater degree of fracturing
Buena, Peru, and Panasqueira,Portugal. Figure 10, would create a greater surface area of rock for
modifiedfrom Landis(1972), is a D-180 plot for reaction,thusdecreasingthe w/r. Alternatively,this
Pasta Buena. The numbers refer to the sample pattern could be explained by a decreasingfluid
position in the parageneticsequence.The most velocity.At the beginningof each cycle the waters
strikingfeature of this diagramis its cyclicpattern. flow too fastto reachcompleteequilibriumwith the
Fromthe beginningof the paragenesis,
the/SDvalue rock and thereforethe apparentw/r is higher than
increases whereas the/580 value remains constant. the actualw/r. As time passes,
the velocitydecreases
Then, at sample5, the/580 decreases
and the /SD and a greaterdegreeof exchangeis realized.
drops back to near the original value. This drop
Landisand Rye (1974) proposedthree watersto
corresponds
to the first period of wolframite depo- account for the range of water compositions,a
sition.Asthe paragenesis
progresses,
the $80 again mixtureof meteoricandmagmatic
watersto generate
remainsrelatively constantand the /SD increases. the isotopiccompositions
to the left of the magmatic
Oncemore,at sample12 the $D and$80 decrease water box, and a connate~metamorphic
water to
and a new, althoughless well developed,cycle is explainthe analyses
whichplot abovethe magmatic
started. Sample 12 is also the beginning of the box. The modelpresentedhere can accountfor the
secondperiod of wolframitedeposition.Thesedata variation in water compositionsin a simpler way,
can be interpreted as consistingof three cycles. with water of just one origin: a meteoric water
which has exchangedhydrogenand oxygenwith a
graniticrockat variousvaluesof w/r anda decreasing
to assumethat a granitic rock was present with
whichthe meteoricwater couldexchange.

temperature.

The late carbonatestage (samples15-17) does


not fall within the pattern establishedby the earlier

/SMOW

mineralization. In fact, the trend of the carbonate

-4o-

""-'

stagesamplesis perpendicularto the previouspattern. These sampleshave essentiallyconstant$D

'0 II

4ve
--.4-.

,,,/ .7-7
:
.,::3
'-

'/
/

Magmatic

Wo,
,r

values and variable/580 values. This trend could be

interpreted as an oxygen-shiftedmeteoric water, a


mixtureof meteoricand magmaticwater, or a mixture of exchanged
andunexchanged
meteoricwaters.
These alternatives
later.

will be discussed in more detail

Panasqueira

Panasqueirashowsa pattern in water compositions


very similar to that of San Cristobal. The data of
Kelly andRye (1979) (Table 5) are plotted in Figure
11. With the exception of three out of fourteen
analysesfor quartz,for which Kelly andRye suspect
poor temperaturecontrol, and the carbonateanaly-

-120
to
Buena

-0

-/0

/0

tee eye]es,0 = Gsteye]e, = seeo. eyele, . V =

ses, which show the same anomalous behavior as

the carbonatesamplesfrom San Cristobal,the data


show a trend of relatively constant/580 and a
variable/SD.Again,becauseof thisdistinctivevertical
pattern,thesewater compositions
canbe interpreted
to be the result of a highly exchangedmeteoric
water. This meteoric water would have had an initial

H & 0 ISOTOPESTUDY,SANCRISTOBALMINE, PERU


TABLE5. CalculatedHydrogenand OxygenCompositions
of
Waters in Equilibrium with VariousVein Minerals at
Panasqueira,Portugal (after Kelly and Rye, 1979)

Mineral

6SO(%0)

Vein quartz

3 to 8

6D (%0)

in the

area at the

time

of ore

plot outsidethe range of the other waters, whereas


at Pasta Buena the trend of the data is different

even though the fields coincide.This characteristic


late-stagecarbonatepattern may be explained in
severalways. First, the carbonatewater could represent mixing of exchangedmeteoric with unexchangedmeteoricwater (Fig. 9) asthe hydrothermal
systemcollapsedin the late stages.At both San
Cristobaland Pasta Buena the geologicsetting is
suchthat the infiuxing meteoric waters might well
have traversedlimestone,a potentialsourceof carbonate.Second,it couldbe interpreted as a second
meteoricwater whichhad t.adergoneexchangewith

3.8 to 10.3

-47

Wolframite
Cassiterite

3.8 to 4.9 g
4.7 to 5.8 a

-71
-124

4 to 84

water

depositionand b80 valueswhich are intermediate


betweenthoseof meteoricand magmaticwaters.At
SanCristobaland Panasqueirathe carbonatewaters

-60 to -45

Vein muscovite

Main-stagesulfides

meteoric

1829

to -36

to -44
to -86

-87 to -47

Siderite

5.3 to 7.7

-60

Late-stagecarbonate

-4 to 5

-58 to -42

to -45

Assuming
a temperatureof 360C
Usingan empiricalfractionarian
factor
Assuming
no fractionbetweencassiteriteand water
Assumed
fromparagenetic
constraints

6D of -125 per mil or lessandwouldhaveexchanged the host rocks to changethe 80 values.The


between 400 to 500C with a w/r that fluctuated correspondingoxygen shift would be greatest at
but alwaysremainedbelow about 0.05. Although PastaBuena, intermediateat Panasquiera,and least
the overall range of water compositioncan be ex- at San Cristobal. Third, such carbonate water could
plainedin thisway, the difficultyof relatingisotopic result from mixingmagmaticwith meteoricwater.
compositionto paragenesison a detailed scale, as Note that the last two alternativesrequire the asdiscussed
by Kelly andRye, remainsa problem.This sumptionof a second,later, meteoric water with a
apparentproblemalsoexistsin the hydrogenisotope considerablyhigher 6D than that postulated for
datafromthe quartzandwolframiteat SanCristobal. meteoricwater during the time of the main minerAlthoughquartz and wolframite occur in the same alization. At both San Cristobal and Pasta Buena the
parageneticstage, are spatially associated,and are isotopic compositionof the present-daymeteoric
assumedto have been depositedat about the same water is closer to that of the waters postulatedfor
time, the hydrogenin the water extractedfrom their the main mineralization than to that of such assumed
fluid inclusions
has differentisotopiccompositions.
The results from San Cristobal do not offer a clearcut

answerto thisproblem,but with the modelpresented


here part of the enigma can be explained. One
inconsistency,
pointedout by Kelly andRye (1979)
when they proposedtwo alternatingwaters to accountfor the depositionof the mineralsfrom waters
of different 6D values,was that there was no concurrent fluctuationin either the temperature of
depositionor salinity.Accordingto the SanCristobal
modelno variationin temperatureor salinitywould
be expected,becausethe variationin bD is dueonly
to variation

o / SMOW
/ Late Stale

/ Crlbnate
/ Muscovite
_.-4o

*...

---

Siderite

'

in the water to rock ratio in a rock-

dominatedsystem,not to the alternatinginflux of


two distinctlydifferentwaters.

Wolfrorbit

-80

Carbonate waters

It has been shown that at San Cristobal, Pasta


Buena,andPanasqueira
the isotopiccompositionof
the waters responsiblefor the major periods of
mineralizationcan be explainedby a water-rock
exchangemodel.However,the originof the water
that depositedthe anomalous
carbonatestageremainsto be explained.In all three examplescited
above, the relation of the later carbonate water to

Water
I I %....MainStaqe

-I0

I0

Sulfi
I

20

$eo(%0)
FIC. 11. Isotopicdata form Panasqueira
(Kelly and Rye,
1979). With the exceptionof three data pointsfrom quartz

the earlier water is consistent.They all have bD (shownby the dashedlines) and the analysesfrom the late
valueswhich are higherthan that of the presumed carbonatestage,the data plot as a vertical band.

1830

CAMPBELL,RYE,AND PETERSEN

meteoric carbonatewaters. In light of the young


age of these deposits,a temporary departure to
significantlyhigherD meteoricwaterswould seem
unlikely.The third alternativeappearslessplausible
because it involves three different water types.
Therefore, the most reasonableexplanationseems
to be mixing of more exchangedmeteoric water
with lessexchangedmeteoricwater.
Source of Metals

degree of alteration is achieved and the copper,


lead, and zinc, which are mostlikely containedin
sulfides,feldspars,and biotite, can alsobe leached.
The amount of solution which passesthrough a
volume of rock is an important factor, becauseof
the low concentrationof W in granite, about 1.5
ppm (Wedopohl, 1969). If the w/r is too high, the
resultant solution could be too dilute to be an ore

solutionfor tungsten.For Cu, Pb, and Zn the w/r is


not as crucial because these metals all have concen-

The three wolframite depositsdiscussedin this trationsin granitegreater than that of W by at least
study can be interpreted as having formed from an order of magnitude.Experimentaldata on the
meteoricwaterswhichhaveinteractedwith a granitic solubilityof wolframiteand the amountof tungsten
rock under conditions of low water to rock ratios.
which can be transported in solution is needed
What genetic significancemight this interpretation before a more quantitative argument may be adhaveconcerningthe generationof tungstendeposits vanced.
and how does this correlate with the observation
The aboveargumentassumes
that the wolframite
that most wolframite depositshave only minor as- was depositedfrom a solutionwhich containedno
sociatedbase metal sulfides?Another way to ask base metals rather than a solution which contained
thisquestionis, how mightsolutionsrich in tungsten basemetalsthat were not deposited.
but poor in basemetalsbe generated?This question
Size of Intrusion
can only be addressedspeculativelyuntil more inWhen dealingwith suchlow water to rock ratios,
formation is available on the behavior of tungsten
in magmaticand hydrothermalprocesses.The fol- the questionarisesasto whether the amountof rock
lowing discussionwill focus on the extraction of needed to generatean ore depositby this process
tungstenfrom granitic rocks and not considerthe is reasonable. The amount of water needed to transphyllites, which are another possiblesource. The port the coppercanbe calculatedfrom the tonnage
tungsten concentrationin shales and phyllites is of copperdepositedat SanCristobal.The SanCrissimilarto that in granite, althoughtungstenmay be tobal mine hasproducedabout5 million tonsof ore
concentratedin black shales as many metals are with an averagegrade of 1 percent copper. This is
(Vine and Tourtelot, 1970), but no pertinent data equal to 50,000 tons or 50,000,000 kg of copper.
are available.
Accordingto Crerar and Barnes(1976) it is possible
During magmatic crystallization tungsten seems to transportup to 1,000 ppm of copper in solution
to be excludedfrom the early crystallizingphases under conditions similar to those at San Cristobal.
(i.e., quartz, feldspar,and amphibole)and concen- This is supportedby fluid inclusionevidencefrom
trated in the residualmelt (Wedepohl, 1969). If the porphyry copper depositswhich indicatescopper
residualmelt doesnot migrateout of the granite to contentsin excessof 4,000 ppm (SawkinsandScherforma pegmatite,it will crystallizewithin the granite, kenbach,1981) and 2,000 ppm (Roberts,1975). If
a solutionwhichcandeposit
forming small veinlets and microveinletsbetween onearbitrarilyconsiders
crystals(Hibbard, 1980). Hibbard alsofeelsthat the 500 ppm of copper,then 10 kg of water are
ore metalstrapped in the late-stageveinletsmay be needed to transportthe copper. If we assumean
incorporated into sulfides, silicates, or alteration averagew/r of 0.005 from San Cristobal, then 2
mineralssuchassericiteor zeolites,dependingupon X 103 kg of rock are neededto alter the water
Volumetrically
thisis equalto 6 km3 of
what componentsare availablein the fluid. It may isotopically.
even be possiblefor tungstatesto form if the con- granite.
The amountof copper at San Cristobalwas used
centrationof tungstenis high enough.If this is true,
then later hydrothermalfluids passingthrough the in this calculation because there are better data for
rock may preferentiallyleach the metalswhich are the amount of copper which can be carried by
concentratedalongthesefracturesand grainbound- hydrothermalsolutionsthan of tungsten,and the D
aries becausethey are accessible.If only a small values of the waters extracted from chalcopyrite
amountof water passesthroughthe rock, then only indicate that it, too, was depositedfrom a highly
the most easily accessibleminerals are leached, exchangedwater. Becauseit accountsfor only the
10 kg of waterisa minimum
yieldinga solutionwhich is rich in tungstenbut not coppermineralization,
in basemetals.On the other hand, if a large amount estimate;an estimateof twice that, 2 X 10 kg of
of water is passedthroughthe rock, then a greater water maybe morerealisticfor depositingthe entire

H & 0 ISOTOPESTUDY,SANCRISTOBALMINE, PERU

SanCristobalorebody.This would require 12 km3


of graniteto accountfor the isotopicexchange.
One further

calculation

which can be made to

1831

ite depositsmay be related to the relativelylow


concentrationof tungstenin granite and the way in
which the tungstenis leachedfrom the granite.

assess
the reasonableness
of this processis to calculatethe amountof granitewhichmustbe leached
to obtain the required amountof tungsten.If one

Acknowledgments

The stableisotoperesearchin this investigation


was supportedby the NationalScienceFoundation
1 milliontonsof tungstenore with an averagegrade (INT 81-05037). Field work wassupportedby HarWe wouldlike
of 0.7 percentWO3, then 6 X 106 kg of tungsten vardUniversityandCentromin-Peru.
were deposited.Assuming50 percentextractionand to thank Centromin-Perufor the financialand logisan originalconcentrationof 1.5 ppm tungstenin the tical supportduringthe summersof 1978 and 1980.
granite,it wouldrequireabout10 kg of graniteto P. Candela, D. Converse, K. Shelton, G. Plumlee,
producethe amountof tungstenin the deposit.This and H. Holland receive thanks for reading various
calculationis in good agreementwith the previous draftsof this paper.
estimates that at the San Cristobal mine there were

calculation
of 2 X 10 kg of rocldneededto alter May 2, 1983; April 5, 1984

the water isotopically.Althoughthesecalculations


REFERENCES
are very general(and optimistic),they at leastindicate that it is possibleto leach the tungstenand Becker,R. H., and Clayton,R. N., 1976, Oxygenisotopestudy
of a Precambrian banded iron-formation, Hamersley Range,
isotopicallyalter the water with a reasonableamount
Western Australia: Geochim. et Cosmochim. Acta, v. 40, p.

of granite.

1153-1165.

Conclusions

Campbell,A. R., 1983, Genesisof the tungsten-base


metalores
at San Cristobal, Peru: Unpub. Ph.D. thesis,Harvard Univ.,

176 p.
The resultsof the hydrogenand oxygenisotope
study show that the mineralizing solutionsat San Campbell,A. R., and Rye, D. M., 1982, Fluid inclusionand
stableisotopestudyof the San Cristobalmine, Peru [abs.]:
Cristobal have a distinctive isotopic pattern. The
Geol. Soc. America Abstractswith Programs,v. 14, p. 450.

watershavefairly constant/80valuesand a wide

rangeof/D values.Studieson two otherwolframitequartz vein deposits,PastoBueno (Landisand Rye,


1974) andPanasqueira
(Kelly andRye, 1979), demonstratethat thosedepositswere depositedby waters
which exhibit an isotopicpattern similarto that seen
at San Cristobal.

Casadevall,T., and Rye, R. O., 1980, The Tungsten Queen


deposit, Hamme district, Vance County, North Carolina: A
stable isotope study of a metamorphosedquartz-huebnerite
vein: ECON. GEOL., v. 75, p. 523-537.

Clayton, R. N., O'Neil, J. R., and Mayeda, T., 1972, Oxygen


isotopeexchangebetween quartz and water: Jour. Geophys.
Research,v. 77, p. 3057-3067.
Crerar, D. A., and Barnes,H. L., 1976, Ore solutionchemistry
V. Solubilitiesof chalcopyriteand chalcociteassemblages
in
hydrothermal solution at 200 to 350C: ECON. GEOL., v.
71, p. 772-794.
Harrison,J. V., 1943, The geologyof the centralAndesin part
of the provinceof Junin, Peru: Soc. Geol. Peru Bol., v. 16,

It is possibleto producesucha patternby isotopic


exchangeof water with granitesat low (0.05-0.005)
water to rock ratios.At higher (0.1) water to rock
ratios, only the oxygenisotopecompositionof the
97 p.
water is affected.For the purposesof this study,the
country rock is consideredto be granite, but the Hibbard, M. J., 1980, Indigenoussourceof late-stagedikesand

results should apply equally to most leucocratic


rocksbecauseof the generalnature of the fractionation factors considered.Meteoric ground waters
will, of course,passthroughother rock types,particularly in the recharge area, and any isotopic
exchangein that regionshouldessentially"pretreat"
the waterfor the exchange
with graniteby increasing
its/80 value.Althoughthe modelproposedhere
is not the only way to producethe observedwater
compositions,it does seem to be the most simple.
For example, with mixing, two or three different

veins in granitic plutons:ECON. GEOL.,v. 75, p. 410-423.


Kamilli, R. J., and Ohmoto, H., 1977, Paragenesis,
zoning, fluid
inclusion,and isotopicstudiesof the Finlandia vein, Colqui
district, central Peru: ECON.GEOL.,v. 72, p. 950-982.
Kelly, W. C., and Rye, R. O., 1979, Geologic,fluid inclusion,
and stable isotope studiesof the tin-tungstendepositsof
Panasqueira,Portugal:ECON. GEOL.,v. 74, p. 1721-1822.
Landis,G. P., 1972, Geologic,fluid inclusion,and stableisotope
studiesof a tungsten-basemetal ore deposit: Pasto Bueno,
northern Peru: Unpub. Ph.D. thesis,Univ. Minnesota, 160 p.
Landis, G. P., and Rye R. O., 1974, Geologic, fluid inclusion,
and stableisotope studiesof the PastoBueno tungsten-base
metal ore deposit, northern Peru: ECON. GEOL., v. 69, p.
1025-1059.

water types are needed to accountfor the variation Lepry, L. A., 1981, The structural geology of the Yauli dome
region, Cordillera Occidental,Peru: Unpub. M.S. thesis,Univ.
in water compositions.The model, as presented

Arizona, 100 p.
here, is relatively simple,but it is flexibleand may Ohmoto,
H., and Rye, R. O., 1974, Hydrogen and oxygen
be adjustedto modelthe isotopicexchangebetween
isotopiccompositions
of fluidinclusions
in the Kurokodeposits,
water and manytypesof rocks.The significanceof
Japan: ECON. GEOL., v. 69, p. 947-953.

low water to rock ratios in the formation of wolfram-

O'Neil, J. R., and Taylor, H. P., Jr., 1967, The oxygenisotopic

1832

CAMPBELL, RYE, AND PETERSEN

Oxygen and hydrogen isotope ratios of clay minerals from


porphyry copper deposits:ECON. GEOL.,v. 64, p. 755-777.
Pastor,J. A., 1970, The mineralizationin the San Cristobal Suzuoki, T., and Epstein, S., 1976, Hydrogen isotope fractionationsbetween OH-bearing mineralsand water: Geochim. et
mine: Unpub. M.S. thesis,Univ. Arizona, 117 p.
Cosmochim.Acta, v. 40, p. 1229-1240.
Petersen,U., 1965, Regionalgeologyand major ore depositsof
Taylor, H. P., Jr., 1974, The applicationof oxygenandhydrogen
central Peru: ECON. GEOL., v. 60, p. 407-476.
istopestudiesto problemsof hydrothermalalterationand ore
Roberts,S. A., 1975, Early hydrothermalalteration and minerdeposition:ECON. GEOL.,v. 69, p. 843-883.
alization in the Butte district, Montana: Unpub. Ph.D. thesis,
-1978, Oxygen and hydrogen isotopestudiesof plutonic
Harvard Univ., 173 p.
granitic rocks:Earth Planet. Sci. Letters, v. 38, p. 177-210.
Rye, R. O., and Sawkins,F. J., 1974, Fluid inclusionand stable
1979, Oxygen and hydrogen isotope relationshipsin
isotopestudieson the CasapalcaAg-Pb-Zn-Cudeposit,central
hydrothermal mineral deposits,in Barnes, H. L., ed., GeoAndes, Peru: ECON. GEOL., v. 69, p. 181-205.
chemistry of hydrothermal ore deposits:New York, Wiley
Sawkins,F. J., and Scherkenbach,D. A., 1981, High copper
and Sons,p. 236-277.
content of fluid inclusionsin quartz from northern Sonora: Vine, J. D., and Tourtelot, E. B., 1970, Geochemistryof black
Implicationsfor ore genesis:Geology,v. 9, p. 37-40.
shale deposits--a summary report: ECON. GEOL., v. 75, p.
253-271.
Shepherd,T. J., Beckinsale,R. D., Rundle, C. C., and Durham,
J., 1976, Genesisof CarrockFells tungstendepositsCumbria: Wedepohl, K. H., ed., 1969, Handbookof Geochemistry:New
Fluid inclusionand isotopic study: Inst. Mining Metallurgy
York, Springer Verlag.
Trans., v. 85, p. B63-B73.
Wilson,J. J., 1963, Cretaceousstatigraphyof centralPeru: Am.
Sheppard,S. M. F., Nielsen, R. L., and Taylor, H. P., Jr., 1969,
Assoc.Petroleum GeologistsBull., v. 47, p. 1-34.

andcationexchangechemistryof feldspars:Am. Mineralogist,


v. 52, p. 1414-1437.