Mineral.

Deposita 22, 42-46 (1987) MINERALIUM

DEPOSITA
© Springer-Verlag 1987

A sulfur isotopic study of the San Cristobal

tungsten-base metal mine, Peru
A. R. Campbell
Department of Geoscience, New Mexico Institute of Mining and Technology, Socorro, New Mexico 87801, USA

Abstract. The San Cristobal tungsten-base metal deposit sic limestones, and Cretaceous sandstones, limestones and
differs from other quartz-wolframite vein deposits in that shales. There are also several intrusive plugs of quartz
it has a major period of base metal mineralization con- monzonite porphyry. Structurally the San Cristobal region
sisting of pyrite, chalcopyrite, sphalerite, and galena. is dominated by the Chumpe anticline. The San Cristobal
Homogenization temperatures of primary and pseudosec- Main Vein cuts perpendicularly across the core of the
ondary inclusions were measured in augelite (260-400°C), anticline and the ore minerals occur as fracture filling
quartz (230-350 °C) and sphalerite (180-220 °C). The 63% within both phyllites and volcanic rocks (Fig. 2).
values of H2S in solution in equilibrium with the vein Mineralization in the Main Vein occurred in three
minerals range from 1.6 to 9.0 permil increasing through major stages (Fig. 3). The first was a tungsten stage con-
the paragenesis. The relatively heavy 634SH~s values sug-
gest a nonmagmatic source for the sulfur. Evaporitic
sulfates are a likely source of heavy sulfur and sedimen-
tary anhydrite is known to occur near the San Cristobal
region. In contrast to San Cristobal are three similar
quartz-wolframite vein deposits, Pasto Bueno, Panasqueira, I ,,,
and Tungsten Queen. They each have an average 63%
value for sulfides of about 0 permil, suggesting a sulfur of
magmatic origin. At San Cristobal an influx of sedimen- %1\ Cerro de
",.Peru
"~
,.(
',,,Brazit
.
tary sulfur could not only account for the distinctive •,o "'--'; ..---"
isotopic signature of the sulfides but also for the presence Pasco ~o.~ L i rno ~',,
of the base metal mineralization.
-oo "-,<~ -~

One feature of the San Cristobal deposit which sets it t

apart from other wolframite deposits is the presence of a
major period of base metal mineralization which occurs Colqui ,._ J~ La Oroya
paragenetically later than the typical quartz-wolframite o
vein type mineralization. At San Cristobal the amount of Casapalca
base metals mined is about ten times greater than the
amount of tungsten mined. This is in contrast to many % o
other wolframite deposits which have only minor associ-
ated base metal sulfides (Casadevall and Rye 1980). In
order to understand why San Cristobal has a higher pro-
portion of base metal sulfides, a sulfur isotope study was
undertaken. This study compares the sulfur isotopic com-
position of sulfides from the early pyrite-wolframite-quartz
stage with those from the later base metal stage. The ", Huancavelic~..
results from San Cristobal will be compared with studies
from other wolframite deposits.
76o /
Central Peru
Geologic setting
Location Map L

The San Cristobal tungsten-base metal deposit is located J J i i Railroad 50 Km

in the central Andes of Peru, about 120 km ENE of Lima
(Fig. 1). The Sedimentary rocks in the area consist of Fig. 1. Map of central Peru showing the location of some of the
Devonian phyllites, Permian volcanic rocks, Triassic-Juras- principal cities and mines
 43

PARAGENESIS
I
400m-260"C I
Aafolite
Muscovite I
I
Pyrite
Wolfromite
330-230"C I
Ouortz
I I
Cbolcopjrite
$phalerife I 220-180"C I
I I
6alone
I I
Barite
I
Carbonate
I
First $toQe I Second Stole I Third Stage
I I
Tunfsfen Sole Wotol I Carbonate
Mineralization iI Mineralization [

Fig. 3. Paragenesis diagram with fluid inclusion temperature. The

average depositional temperatures used in the isotopic calculations
are 300°C for the first stage pyrite; 200°C for the sphalerite and
galena and 250 °C for the second stage pyrite and chalcopyrite

Table 1. Fluid inclusion homogenization temperatures

Mineral Range Average

(°c) (oc)

Augefite 260-400 340

[] (
[] (
[] Mitu Fm.(Pm)
[] Excelsior Fm.(De)
[] Quortzmonzonite(qmp)
[] Veins 0 I 2 mineralizing solutions at San Cristobal. Of the vein min-
[] Replocementbodies kllometers
Fig. 2. Generalized geologic map of the San Cristobal district
(modified from Petersen, 1965)
sisting of 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 predominantly
carbonate with minor amounts of sphalerite and galena.
Tectonic reactivation of the vein between the stages
resulted in brecciation of the vein minerals.
Pyrite, wolframite and quartz generally occur together,
although the onset of pyrite deposition slightly precedes
wolframite deposition. Most of the chalcopyrite was depos-
ited after the end of the first stage but prior to the
deposition of sphalerite and galena. Pyrite of the second
stage is found as euhedral crystals within the chalcopyrite.
Sphalerite and galena deposition commonly occurred at
the same time, but in some locations sphalerite did
precede galena. Barite, where it occurs, was deposited with
the galena.
Detailed descriptions of the general geology and the
mineralization can be found in Pastor (1970), Lepry
(1981), and Campbell (1983).
Quar~ 230-350 300
Sphalerite 180-220 200
Siderite 135-140 140
Fluid inclusion study
A study of fluid inclusions in vein minerals was under-
taken to examine the temperature and salinity of the
erals, augelite, quartz, sphalerite, barite, and siderite were
found to be suitable for fluid inclusion analysis. Fluid
inclusions occur as primary, pseudosecondary and second-
ary inclusions. The majority of the measurable, recogniz-
ably primary, inclusions occur as large isolated inclusions
in the cores of quartz crystal, although others occur as
crystallographically controlled trails of tiny inclusions.
Texturally it was not possible to distinguish between the
planes of secondary and pseudosecondary inclusions, so
their separation was based on the range of homogenization
temperatures. The homogenization temperatures resulting
in fluid inclusion analysis are summarized in Table 1. Only
temperatures from inclusions thought to be primary or
pseudosecondary are included. The "average" listed is
essentially the peak in the temperature distribution and is
the temperature used for further calculations.
In addition one fluid inclusion was measured in wol-
framite using an infrared microscope (Campbell et al.
1984). It has a homogenization temperature of 298°C.
This is in the middle of the range of temperatures mea-
sured in the quartz which occurs with the wolframite.
Fluid inclusion salinities based on freezing point de-
pression are low, ranging from 2.7 to 6.3 equivalent weight
percent NaC1.
Isotope measuremen ts
The isotopic composition of sulfur (634S) in pyrite, chalco-
pyrite, sphalerite, galena and barite samples from the vein
were measured. For sulfur isotopic analysis, samples were
either hand picked or drilled out to assure reasonably pure
44

1st stage pyrite ! ~ ~ d ~ 1st stage pyrite (3000C)

=3 I 2n°,toge,r,,e I 2 na stagepyrite(2500C)
• • • •
•
o
chalcopyrile(2500C)
re.J• cha~copyr,e ~ ~t m.J •

.Q

mm mm
soha,er,te z il • m ~ll • sph°lerite(200°C)
Z

I I
n m
I i l
m
n
•
l l
•
I
•
, I i I i
oo,eoo
I
:I m m
m
I i
galena(200"C)
i , ,
10
1,0 2,0 3,O 4,0 5.0 6.0 ~0 8,0 9,0 100
7,0 8.0 9,0 IOD

5 s4 $ (%0) 8s4SH2s (%01

Fig. 4. Histogram showing sulfur isotopic ,analyses of vein min- Fig. 5. The sulfur isotopic composition of H2S in solution which is
erals from San Cristobal in equilibrium with the mineral analyses in Figure 4 at the tem-
peratures indicated. The isotopic fractionation factors are taken
from Ohmoto and Rye (1979)

monomineralic separates. Analyses were performed on a non are the gradual addition of sulfur from an isotopically
Nuclide 6-60 mass spectrometer at Yale University. Sul- heavy source to an originally light, possibly magmatic
fides were oxidized to SO2 by heating to 1,100°C in a sulfur or an originally heavy source with a decreasing
vacuum with excess cupric oxide in the presence of copper oxygen fugacity with time. The term "magmatic sulfur" is
metal. The precision of the analyses is _+0.1 permil. The somewhat ambiguous. It is used here to mean sulfur
analyses are reported relative to the Canyon Diablo derived from a deep seated source either during crystal-
Troilite standard. lization or leached from an intrusive rock later by mete-
These results are compiled in Fig. 4. Although the 634S oric or other water and is assumed to have a d34S value of
values for the minerals can be used for geothermometry, 0 _+2 permil.
in order to determine the source of the sulfur it is neces- In a solution which contains both H2S and SO4 in
sary to know the ~34S value of the sulfur species in solu- equilibrium, the H2S will be isotopically lighter than the
tion (H2S) from which the minerals precipitated. Assuming SO4 and the proportions of total reduced sulfur to total
equilibrium, it is possible to calculate 634SH2s using the oxidized sulfur are controlled by the pH and fO2 (Ohmoto
634S values of the minerals, their temperatures of deposi- 1972). The pH at the time of ore deposition at San
tion and the corresponding isotopic fractionation factors. Cristobal is not explicitly known however, most hydro-
These fractionation factors are taken from the compilation thermal fluids tend to be acid and within 2 or 3 pH units
in Ohmoto and Rye (1979). The temperature of deposition of neutral (Barton 1981). That pH range is reasonable for
is not directly known for all of the sulfide minerals, but San Cristobal because of the destruction of feldspar and
can be estimated using the known temperatures and para- the growth of sericite in the hydrothermally altered volca-
genetic constraints shown in Fig. 3. The average tem- nic wall rock. The presence o f vein muscovite suggests a
perature of deposition for the first stage pyrite is assumed pH range of 3.5 to 5, assuming a concentration of
to be 300 °C, that of the quartz with which it occurs. For K ÷ = 0 . 1 m (Montoya and Hemley 1975). Within that
sphalerite and galena, the average of the fluid inclusion general pH constraint, as the oxygen fugacity drops the
homogenization temperatures for sphalerite, 200°C, is solution will change from being sulfate-rich to sulfide-rich.
used. The temperature of deposition for chalcopyrite is As the isotopically heavy sulfate reacts to form sulfide, the
more difficult to estimate. Inasmuch as most of the chalco- sulfide will become isotopically heavier.
pyrite occurs after the first stage mineralization and before At San Cristobal it is not possible to use the mineral
the main period of sphalerite deposition, an intermediate assemblages in the vein to tightly constrain the fugacity of
temperature of 250 °C is assumed for the chalcopyrite and oxygen during ore deposition. With the available parage-
associated second stage pyrite. Even if the temperature of netic information, the oxygen fugacity could have de-
deposition for chalcopyrite was as low at 200 °C or as high creased with time but was not constrained to have done
as 300 °C, the subsequent sulfur isotopic fractionation cal- so. Therefore, it is not possible to distinguish between
culations change by only __ 0.05 permil. The results of this these two alternatives.
calculation are shown in Fig. 5, which is a histogram of However, both of the two aforementioned possibilities
634S~s values in equilibrium with the various minerals at do require the presence of a source for heavy sulfur. In the
the temperatures given. second case it is needed for the entire paragenetic sequence
There are two major features to observe in Fig. 5. The and in the first case it is needed for at least the base metal
first is the overall range of 634Sit,s values from 1.6 to 9.0 stage. A common source of heavy sulfur is sedimentary
permil; the other is the trend towards heavier ds4SH2s sulfate. This seems to be a reasonable source of heavy
values with "paragenetic time." sulfur at San Cristobal. Sedimentary anhydrite is known to
The trend to heavier 634S values with time will be con- occur at the nearby Morococha mine at the base of the
sidered first. Two possible explanations for this phenome- Triassic Pucara Group. This same stratigraphic unit occurs
 45

Table 2. d34S (%0) values and calculated temperatures for sulfide

San Cristobal pairs

Tungsten Queen I I, I Sample Pyrite Chalcopyrite A T °C

Panasqueira I SC80-3 6.1 5.2 0.9 433

I SC80-9 6.8 6.7 0.1 1,846
Pasto Bueno I- I SC-9 6.4 6.0 0.4 789
SC-9A 6.3 6.0 0.3 950
SC-3 6.0 5.3 0.7 527
I i T' I i I i
SC80-47 6.0 5.9 0.1 1,846
-6 --4 -2 0 2 4 6 8 IO SC80-42 6.2 5.9 0.3 950
34S H2 s
Sample Sphalerite Galena T°C
Fig. 6. Comparison of the sulfur isotopic composition of H2S in
solution for San Cristobal with other wolframite deposits. San SC80-42 7.8 4.4 3.4 188
Cristobal is considerably enriched in heavy sulfur SC80-25 6.7 4.1 2.6 254
SC80-35 6.8 4.9 1.9 344
SC80-9 7.0 6.5 0.5 1,202
in the San Cristobal area, and although evaporites have
not been specifically identified at this locality, they may Table 3. 6a4Svalues for sulfate-sulfide pairs at San Cristobal
have been largely leached out. The sulfur may also have
been transported a long distance in solution to the site of Sample Barite Sulfide A
deposition. Isotopic analysis of the Morococha sulfates
SC80-47 18.5 4.2 Gn 14.3
yields 6~4S values of around 12 permil (Petersen 1972), SC80-54 15.5 4.2 Gn 11.0
which is what would be expected for the isotopic com- SC80-28 15.5 4.2 Gn 11.3
position of sulfur in seawater sulfate from the early SC80-27 15.5 5.5 Sp 10.0
Triassic (Claypool et al. 1980). This sulfate is isotopically SC-2 15.3 5.7 Sp 9.6
heavy enough to account for the isotopic composition of
the hydrothermal sulfides and sulfates at San Cristobal
assuming that the sedimentary sulfate is partially reduced.
than the pyrite. Therefore, because of the increase in the
Comparison with other wolframite deposits 634SH2s with time, the chalcopyrite will be slightly heavier
Figure 6 compares the calculated d34SH~s values from San causing the py-cp to be smaller than required for equilib-
Cristobal to those from other wolframite vein deposits: rium. The same argument holds true for the sphalerite-
Pasto Bueno (Landis and Rye 1974), Panasqueira (Kelly galena pairs although to a lesser extent inasmuch as the
and Rye 1979) and Tungsten Queen (Casadevall and Rye relative change in 634SH~s was less. This results in some-
1980). These three deposits have 6~4S~2s values near 0 what more reasonable (except for sample SC 80-9) sphal-
permil and have been interpreted by the researchers erite-galena temperatures. This problem of unreasonable
temperatures due to noncontemporaneous deposition has
working on them to represent sulfur derived from a deep
seated source. San Cristobal, however, has 63~SH~s values been noticed at the Sunnyside mine (Casadevall and
Ohmoto 1980) and has been noted to be a particular
ranging from 2 to 9 permil, which are significantly heavier
problem in pyrite-sulfide pairs due to the extensive deposi-
than the sulfur from the other deposits (although it should
tion of pyrite over long intervals of many paragenetic se-
be noted that the pyrite at the time of wolframite deposi-
tion had a 634S value close to 2 permil, similar to that of quences (Ohmoto and Rye 1979).
the other three deposits mentioned). San Cristobal is also
different from the other deposits in that it has a major Sulfates
period of base metal sulfide deposition. For samples in which the ba4S value of both barite and
sulfides were measured the sulfate-sulfide values are
Sulfur isotope thermometry smaller than expected at equilibrium. The barite-sulfide
values range from 9.6 to 14.3 permil (see Table 3). Under
An attempt to use sulfide mineral pairs as geothermome- equilibrium conditions at 200 °C, the barite-sulfide values
ters yielded disappointing results. Both pyrite-chalcopyrite should be around 25 permil. This deviation from equilib-
and sphalerite-galena pairs yield temperatures that are rium is a very common observation in hydrothermal ore
unreasonably high (Table 2). The high temperatures calcu- deposits that form at temperatures lower than about
lated result from isotopic differences that are smaller than 350 °C (Ohmoto and Lasaga 1982).
the equilibrium fractionation.
The most likely reason for the unrealistic temperatures Conclusions
is the changing d34SH2s with time as discussed above.
Minerals which were not deposited contemporaneously Although it is not possible to arrive at an unambiguous
would have been deposited from solutions with different interpretation of the sulfur isotope results from San Cristo-
ba4S values. In equilibrium pyrite-chalcopyrite pairs, the bal, the most likely explanation seems to involve the
pyrite should be heavier than the associated chalcopyrite. reduction of sedimentary derived sulfate. This alone could
However, at San Cristobal the chalcopyrite is slightly later account for the isotopic pattern observed, but does not
46
rule out the participation of magmatic sulfur early in the
paragenesis. Early magmatic sulfur fits with the observa-
tion that the early wolframite mineralization is similar to
that of several other quartz-wolframite vein deposits, all o f
which contain sulfur from a magmatic source. The differ-
ence between San Cristobal and the other deposits is the
base metal stage which occurs at San Cristobal. An input
of heavy crustal sulfur derived from the leaching of
sedimentary sulfates by meteoric or other waters after the
wolframite mineralization could account not only for the
abundance of sulfides but also for their distinctive isotopic
composition. Therefore, the reason that San Cristobal is
slightly different from most "normal" quartz-wolframite
vein deposits is not that it is a genetically different type o f
deposit but rather results for a second pulse of mineraliza-
tion with the addition of extra sulfur from a different
source.
Acknowledgements. Tfiis study represents a portion of the author's
Ph.D. research at Harvard University. Sulfur isotope analyses
were made at Yale University and funded by National Science
Foundation Grant (INT 81-05037) to Ulrich Petersen. Field work
was supported by Harvard University and Centromin-Peru during
the summers of 1978 and 1980. I would like to thank my advisors,
U. Petersen, D. Rye, and H.D. Holland for their help and support.
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Received: August 5, 1986
Accepted: August 24, 1986