Genesis of Giant San Rafael Tin Deposit Peru-Pervasive Alteration

Economic Geology
Vol. 97, 2002, pp. 17411777
Genesis of the Giant, Bonanza San Rafael Lode Tin Deposit, Peru:
Origin and Significance of Pervasive Alteration
DANIEL J. KONTAK
Nova Scotia Department of Natural Resources, P.O. Box 698, Halifax, Nova Scotia B3J 2T9, Canada
AND
ALAN H. CLARK
Department of Geological Sciences and Geological Engineering, Queens University, Kingston, Ontario K7L 3N6,Canada
Abstract
The San Rafael Sn-Cu deposit, located at lat 1413'58" S, long 7019'18" W, on the upper slopes of the
Cordillera de Carabaya, northern Puno Department, southeastern Peru, yielded 38,182 t of fine tin in 2001
and, with reserves of 14.460 Mt at 5.14 percent Sn, the main San Rafael Lode constitutes, both at present and
historically, the largest-known bonanza-grade cassiterite repository. Sn and subordinate Cu mineralization were
confined to laterally and vertically extensive brittle shear zones generated by regional tectonism that transect a
small 24.65 0.20 Ma, epizonal stock of strongly peraluminous, Lachlan S-type cordierite-biotite monzogranite and granodiorite. Early, barren, stage I quartz-tourmaline veins and breccias were emplaced at 24.10 0.15
Ma by high-temperature (580C), boiling, saline fluids that plausibly directly exsolved from the granitic melt,
whereas both cassiterite (stage II) and, at higher elevations, chalcopyrite (stage III) ores were precipitated from
largely nonboiling, cooler (Th = 215420C), and less saline (020 wt % NaCl equiv) fluids at 21.9 to 22.7
circa 0.5 Ma.
Only narrow (2 m) envelopes of chlorite and weaker sericite and silica are associated with stages II and III
veins, but more than 80 percent of the upper 750 m of the San Rafael stock experienced quasipervasive hydrothermal alteration. Early K metasomatism is recorded by widespread replacement of magmatic plagioclase
and perthitic alkali feldspar by Na-free orthoclase, while broadly coeval alteration to albite more erratically affected groundmass plagioclase and the rims of alkali feldspar phenocrysts. Despite the intensity of the alkali
metasomatism, only minor redistribution of dispersed, magmatic Sn occurred, largely during alteration to orthoclase. Other petrographically similar granitic bodies in the region experienced more intense Na metasomatism, and they host argentian base metal rather than Sn-dominated veins. Superimposed hydrolytic alteration,
most intense within 20 to 30 m of the San Rafael Lodes, converted biotite to Fe-rich chlorite and converted alkali feldspar and plagioclase to fine-grained muscovite, but there is no significant dispersed cassiterite or chalcopyrite.
Secondary fluid inclusions trapped in quartz phenocrysts of the granitic rocks range in salinity from 0 to 65
wt percent NaCl equiv and in Th from 200 to 530C; fluid boiling is evident in the higher-temperature populations. First-melting temperatures and decrepitate analyses reveal, in addition to NaCl, widely variable concentrations of KCl, CaCl2 (attaining 40 wt % of the solute) and, apparently most abundant in proximity to the
lodes, FeCl2. Entrapment pressures are estimated to have fluctuated in the range 150 to 615 bars for much of
the hydrothermal history, but fluid overpressuring to at least 2 kbar occurred, probably cyclically, during the
evolution of the hydrothermal system. The salinity vs. homogenization temperature range for the phenocrysthosted inclusions closely matches that of primary inclusions in quartz and cassiterite in the lodes and, remarkably, small clusters of the former record the entire thermal and compositional trajectory of the mineralizing fluids. Early magmatic brines are inferred to have permeated much of the stock whereas, circa 2 m.y. later, Snand Cu-rich, lower-temperature, lower-pH fluids were largely channeled along the evolving shear zones where
they mixed with cool, nonsaline, tectonically driven ground water. In conjunction with fluid neutralization
through hydrolytic alteration, this channeling resulted in catastrophic precipitation of botryoidal and coarsely
crystalline cassiterite and, subsequently, chalcopyrite. The hiatus between initial retrograde boiling and ore deposition, a feature documented in several world-class, high-grade lithophile-element deposits, may record protracted storage of metal-rich brines at depth, perhaps in association with small volumes of highly fractionated
melt, such as is represented by small bodies of tourmaline leucogranite exposed on the upper margin of the
San Rafael stock. However, the parallel evolution in temperature and salinity exhibited by the early nonmineralizing and later fertile hydrothermal fluids may also indicate that Sn and Cu were largely introduced into the
subjacent magma chamber at a late stage.
Introduction
HYDROTHERMAL alteration assemblages have long been recognized as providing a record of the compositional evolution
and migration paths of magmatic-hydrothermal aqueous fluids,
as well as enlarged and, ideally, systematically zoned targets in
Corresponding author: e-mail, charbon@geol.queensu.ca
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mineral exploration. Predictably, therefore, they have been

extensively documented (e.g., Lentz, 1994). Less attention
has been paid to the interrelationships between the nature
and intensity of alteration and the scale of ore metal concentration although, in the lithophile-metal field, the subject of
the present discussion, Eugster and Wilson (1985) and, in
more detail, Halter et al. (1996) modeled the deposition of
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KONTAK AND CLARK
cassiterite as a direct result of proton metasomatism (greisening) of quartzofeldspathic host rocks and concomitant fluid
neutralization. In such systems, a broad correlation between
the intensity and/or extent of feldspar-destructive alteration
and Sn ore-grade and/or tonnage would be predicted. Heinrich (1990), however, emphasized the limitations inherent in
such a cassiterite precipitation mechanism, and the deposits
(e.g., East Kemptville, Nova Scotia) on which the modeling
was based are indeed either small or low grade (Kontak et al.,
1995), and they would probably not now constitute realistic
exploration targets. Heinrich also noted that such constraints
could be overridden by the abrupt mixing of a Sn-bearing
magmatic brine with cool meteoric water, under which circumstances there are essentially no chemical limitations on
tin ore grade..... (op. cit., p. 457).
Herein we document aspects of the hydrothermal alteration associated with a giant, bonanza lode tin deposit, i.e.,
San Rafael, southeastern Peru, by far the most important single hard-rock source of cassiterite during the past decade.
Minsur S.A.s underground mine yielded 37,409 and 38,182
tonnes of fine tin-in-concentrate in 2000 and 2001, respectively, and it has reported in situ reserves (Dec. 31, 2001) of
14.460 Mt at 5.14 percent Sn and 0.04 percent Cu, at a cutoff
grade of 2.63 percent Sn; the mineable ore grades are probably at least 5.6 percent Sn. This study represents part of an
ongoing investigation (Palma, 1981; Kontak, 1985; Yamamura, 1990; Sandeman, 1995) of the geologic history, metallogeny, and ore genesis of the southeast Peru segment of the
central Andean inner arc (Clark et al., 1983a, 1984). An
overview of this region and the great variety of ore deposits
therein is provided by Clark et al. (1990a). The petrogenesis
of parental magmas, the structural and mineralogic evolution
of the lode system, and the stable isotopic chemistry of the
ores and host rocks are topics that await further investigation.
The granitoid rocks that host the mineralized structures at
San Rafael superficially appear unaltered but are extensively
and intensely metasomatized. As emphasized by Kontak and
Clark (1988), the field recognition of such cryptic alteration
permits a preliminary evaluation of the economic potential of
the numerous felsic intrusions of the region. The alteration
both preceded and accompanied the deposition of cassiterite,
and it developed quasipervasively through at least 1.5 km3 of
the epizonal San Rafael granite stock. However, no dispersed,
porphyry-style Sn mineralization has been documented (cf.
Sillitoe et al., 1975), and the genetic relationships between
widespread alteration and structurally focused ore deposition
require definition, representing a key facet of the ore-genetic
model for an exceptionally rich hydrothermal center.
The geology of this exceptional deposit has been outlined
by Arenas (1980), Palma and Clark (1982), Clark et al.
(1990a) and Kontak et al. (1995). Arenas (1999) provides a
succinct overview but does not document the alteration that
is the main subject of the present contribution. Because the
tectonic and petrogenetic setting and evolution of the San
Rafael Lodes differ markedly from those of the widely documented greisen-associated cassiterite vein systems (e.g., Halter et al., 1996), we summarize the salient features of the deposit and its surroundings to provide a basis for discussion of
the alteration relationships.
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The San Rafael Deposit

The San Rafael deposit is centered at lat 1413' 58" S., long
7019'18" W, in northern Puno Department, southeast Peru
(Fig. 1a). The vein system crops out at altitudes of up to 5,000
m a.s.l. on the southern slopes of the Cordillera de Carabaya,
a segment of the central Andean Cordillera Oriental. The deposit lies close to the apparent northwestern termination of
the Bolivian Sn-Ag belt (Fig. 1a), which flanks the eastern
border of the Altiplano (Turneaure, 1971). All economic cassiterite deposition occurred within a series of broadly northwest-striking brittle shear zones (Fig. 1b) that transect the
San Rafael stock (Arenas, 1980; Clark et al., 1983b). This
small epizonal granitic body, which has an outcrop of less than
1 km2 on the glaciated southern slopes of Nevado San Bartolom de Quenamari, the southwest spur of Nevado San
Francisco de Quenamari (5,284 m a.s.l.), is a member of the
upper Oligocene-lower Miocene (2226 Ma) Picotani intrusive suite, the hypabyssal component of the volcano-sedimentary Picotani Group, which records the initiation of Cenozoic
magmatism in the region (Clark et al., 1990a; Sandeman et
al., 1997). It is hosted (Palma, 1981) by clastic rocks of the Ordovician Sandia Formation, which had experienced prehnitepumpellyite facies regional metamorphism and polyphase deformation in the Early Carboniferous, early Hercynian
orogeny (Laubacher, 1978; Clark et al., 1990b). Southeast of
the mine, the contact between the lower Paleozoic metaclastic rocks and the overlying diagenetic-grade (A.H. Clark,
unpub. data) and openly folded Mississippian Ambo Group is
interpreted, on the basis of minor structures in the former
(A.H. Clark, unpub. data), as a thrust fault that dips southsoutheastsoutheast at circa 15 to 20(Fig.1b). Steeply dipping, broadly northwest-striking transcurrent faults delimit
the eastern and western boundaries of the inlier (Fig. 1b),
and the San Rafael stock and lode system were thus emplaced
into a tectonic dome or arch.
Intrusion of granitoid magma took place in the latest
Oligocene, at 24.6 to 24.7 0.2 Ma (respectively, 206Pb/238U
single zircon and monazite dates: Clark et al., 2000), while
40
Ar/39Ar age spectra show that the upper 500 m of the stock
cooled through the Ar-retention temperature of biotite (ca.
310C : Harrison et al., 1985) at 23.7 0.2 Ma (all dates
herein are quoted at 2 error). The intrusion is dominated by
coarse, porphyritic monzogranitic and finer-grained, less porphyritic monzogranitic to granodioritic facies (Fig. 1b, c),
both characterized by phenocrysts of alkali feldspar, quartz,
biotite and, a striking feature in outcrop, pinitized cordierite.
The strongly peraluminous granitoid rocks conform closely to
Chappell and Whites (1974) original S-type clan, termed
Lachlan S-type by Sylvester (1998) and peraluminous S-type
by Patio-Douce (1999), in contradistinction to lower-temperature and more hydrous Himalayan-type muscovite-rich
leucogranites.
Ore-metal zonation
The mineralized structures in the San Rafael mine (Fig.
1b), among which the Veta San Rafael (San Rafael Lode) is
by far the most important, possess (Arenas, 1980; Palma,
1981; Clark et al., 1983b) a dramatic vertical ore-metal
zonation (Fig. 2a), comparable to that of the lodes of the
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ALTERATION & HIGH-GRADE Sn MINERALIZATION, SAN RAFAEL, PERU
a)
b)
68
72W
12S
200 km
Study area
14
Bolivia
Sn
-A
g
Peru
16
km
B
t
el
18
Altiplano
Pacific
Ocean
Veta San Rafael
Chile
QG
Mina Quenamari
moraines, scree, ice

tourmaline leucogranite
granitic dikes
SRG
fine- to medium-grained
monzogranite/granodiorite
coarse-grained monzogranite
Ambo Group (Mississippian)
veins
faults
Mina
San Rafael
Sandia Formation (Ordovician)
c)
Quenamari
206
213
217,218
244
195,194,196
203
187A
FIG. 1. (a) Location of the San Rafael Sn-Cu deposit at the apparent northwest extremity of the central Andean Sn-Ag-polymetallic belt. (b) Simplified
geologic map of the San Rafael-Quenamari mining district (after Arenas,
1980, 1999; Palma, 1981; A.H. Clark, unpub. data). The San Rafael (SRG)
and Quenamari (QG) stocks are considered to represent cupolas on a single
steep-walled pluton, circumscribed by the granitic ring dikes. The coarsegrained facies is largely monzogranitic, while the finer straddles the monzogranite-granodiorite field boundary. The largely north-northweststriking
lodes and veins developed during thrusting of the Ambo Group over the Sandia Formation. The northwest-verging thrust in the southeast sector is poorly
exposed but its location and sense of displacement are in conformity with
structures in the underlying Sandia Formation rocks. (c) Sketch maps showing the locations of surface granitoid samples specifically cited herein. N.B.
San Rafael samples 140, 141, and 156 are from the small bodies of tourmaline leucogranite at the margin of the main stock. The majority of underground samples were taken from the 4533 m level. Surface samples in which
fluid inclusions were studied in most detail are in italic type.
202
197
198
190
239
1 km
193
154
403,406
156
248
150,151
165,166A
408
249A
140,141
250,252
San Rafael
major Camborne-Redruth district of the Cornubian province,

southwest England (Dines, 1956; Clark et al., 1995), in which
a chalcopyrite-rich zone overlies one dominated by cassiterite. This clear relationship is not known in other major deposits in the central Andean tin belt and is indeed unusual
globally. Sphalerite, galena, and Ag sulfides and sulfosalts, as
well as ankerite, siderite, and calcite, are modestly enriched at
the lateral, particularly the southern (Cuerpo Polimetalico:
Fig. 2a), extremities of the vein system, but the vein becomes
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narrow and discontinuous in the hornfelsic rocks adjacent to

the stock. The San Rafael Lode has been developed throughout a vertical interval of more than a kilometer, from immediately above 5,000 m to 3,950 m a.s.l., and along a horizontal
distance of 2.4 km (Fig. 2a). It yielded chalcopyrite concentrates above circa 4730 m, but almost all recent mining has
been restricted to the underlying Sn zone, where Sn/Cu ratios
exceed 25 (Arenas, 1999). Palma (1981) and Palma and Clark
(1982) demonstrated that the ore-metal zoning records the
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KONTAK AND CLARK
a)
SSE
NNW
500 m
San Rafael
Stock
5
3
Sandia Fm.
4500 m
1
150-S
Brecha Rampa
410
150 310-S
Ore Shoot
%
.2%
t@ 66.2
0.6M
%
.6%
44.6
1.6Mt@
6.0%
1.9Mt@
2%
3.2%
0.8Mt@3.
Cuerpo
Polimetalico
(Pb,Zn,Cu,
Sn,Ag)
Cuerpo
Contacto
Sur
5000 m
(a.s.l.)
5.8Mt@5.5 %
250-S Cuerpo
Contacto
Brecha
4000 m
Cu grade contours (%)

(%)
b)
N
437
0m
7,2
00
Brecha
-E
8,4
28
,20
0N
35
Ore Shoot
FIG. 2. (a) Longitudinal section of the San Rafael Lode showing Cu isograde lines and the main Sn orebodies, each of which is located within a dilational fault-jog controlled by combined sinistral-transcurrent and reverse
displacement during paragenetic stage II (see Fig. 3; simplified after Minsur
S.A., unpub. reports, 2000). (b) Level plans (42004370 m) showing the form
of the Ore Shoot and contiguous Brecha orebodies on the San Rafael Lode.
The Ore Shoot comprises, from northeast to southwest, a high-grade hanging wall cassiterite-quartz-chlorite vein; polyphase hydrothermal breccias;
central stockwork; hydrothermal breccias; and a weak footwall vein (simplified after Minsur S.A., unpub. reports, 2000; R. Mason and D.J. Kerr, unpub.
report to Minsur S.A., 2000).
431
0m
420
100m
8,4
28
,40
0N
0m
juxtaposition of earlier cassiterite-dominated and later chalcopyrite-rich assemblages (Fig. 3), concentrated in, respectively, the deeper and shallower intervals of the lode.
The San Rafael Lode system occupies the southwest half of
a mining district that also incorporates the much smaller Quenamari, or Carabaya, mine, 3.5 km to the northeast (Fig. 1b).
Chalcopyrite-cassiterite ore occurs in the latter area but is
subordinate to Ag-rich chalcopyrite-sphalerite-galena(-carbonate) veins comparable to the distal zones of the San Rafael
Lode (Hannington, 1983; Kontak, 1985; Clark et al., 1990a).
Ore at Quenamari is associated with a series of granitoid
stocks and dikes (Fig. 1b), petrographically similar to, but
probably representing a shallower erosion level than, the San
Rafael stock. The San Rafael and Quenamari granites almost
certainly represent cupolas of a single pluton. Several other
Sn-base metal vein systems, coeval with San Rafael, are exposed on the southern slopes of the Cordillera de Carabaya
(Clark et al., 1983b, 1990a, Kontak et al., 1987) but, with the
possible exception of Santo Domingo, 22 km west of San
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Rafael (Bateman, 1982), none has been shown to be of economic importance. The large and high-grade Palca 11 (Regina)
ferberite-scheelite lode (Clark et al., 1990a; Yamamura,
1991), formerly mined in the eastern part of the broader
Cordillera de Carabaya district, is coeval with the San Rafael
deposit (Farrar et al., 1990), but only traces of scheelite and
wolframite have been confirmed from the San Rafael Lode
(Palma, 1981; A.H. Clark, unpub. data), although the darker
zones of cassiterite grains are enriched in W as well as in Fe
(M.S.J. Mlynarczyk, unpub. report for Minsur S.A., 1999).
Alteration-mineralization relationships
The paragenetic evolution of the San Rafael Lode system,
first established by Palma (1981) and modified by A.H. Clark
(unpub. data), is illustrated in Figure 3. The initial mineralization in the San Rafael stock, assigned to stage I (Palma, 1981;
Fig. 3), generated swarms of tourmaline-quartz veins and hydrothermal breccias, with minor arsenopyrite, lllingite, and
hexagonal pyrrhotite (Palma, 1981; A.H. Clark, unpub. data)
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Hypogene Paragenetic Relationships of San Rafael Lode

and its Immediate Envelope
Tourmaline
Quartz
Arsenopyrite
Lllingite
Pyrrhotite
Muscovite
Chlorite
Cassiterite (botryoidal)
Cassiterite (coarse-grained)
Scheelite
Wolframite
Chalcopyrite
Pyrite
Cassiterite (acicular)
Sphalerite
Galena
Stannite
Acanthite
Matildite
Bismuth
Adularia
Marcasite
Siderite
Ankerite
Calcite
Amethyst
Fluorite
Stibnite
Gudmundite
Mackinawite
STAGE I
24.10 0.15 Ma
STAGE II
22.4 - 22.7 0.7 Ma
STAGE III
21.9 - 22.0 0.2 Ma
STAGE IV
FIG. 3. Paragenetic and age relationships of the San Rafael and associated lodes (Palma, 1981; Kontak, 1985; A.H. Clark,
unpub. data). N.B. Stages I (precursor tourmaline-quartz veins) and II (main cassiterite veins) are shown as a continuum but
probably represent discrete events. 40Ar/39Ar ages determined by Y. Chen and E. Farrar (Clark et al., 2000).
but neither cassiterite nor chalcopyrite. These veins and breccias are most widely developed in the upper part of the stock
but persist at depth at least to 3,850 m a.s.l.. Narrow (generally < 50 cm) alteration selvages exhibit a temporal evolution
from pervasive tourmalinization to intense quartz > muscovite alteration, evidence for strong leaching of Ca, Na, Al,
and K (cf. Zweng and Clark, 1995). The superimposed stage
II assemblages (Fig. 3) incorporate more than 97 percent of
the cassiterite in the San Rafael and associated lodes. In the
upper circa 150 m of the Sn zone of the San Rafael Lode
(4,3104,460 m a.s.l.), cassiterite occurs (Palma, 1981) predominantly as botryoidal, finely laminated estao madera
(wood-tin), intimately intergrown with chlorite and quartz.
The remarkable development of such textures, unparalleled
elsewhere in extent, probably indicates that the early stage II
fluids were markedly supersaturated in Sn. Below circa 4,310
m, coarsely crystalline cassiterite predominates, but crudely
boytroidal forms are widespread, and reversion to the woodtin habit occurred episodically as stage II evolved. The
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youngest stage II assemblages, dominating the San Rafael

Lode below circa 4,050 m, record a marked overall increase
in quartz deposition and concomitant decreases in cassiterite
and, less pervasively, chlorite as vein minerals. However, the
succeeding Stage III sulfide-dominated assemblages again incorporate abundant chlorite (Fig. 3). This stage is characterized by chalcopyrite, largely hexagonal pyrrhotite, pyrite, and
minor stannite above 4,730 m, but the iron sulfides predominate below that elevation. Acicular cassiterite (needle-tin)
occurs in direct association with chalcopyrite in the lower part
of the Cu-rich zone. Stage III therefore exhibits single-pass
(monoascendant) ore-metal zoning. Numerous lode segments
exposed on the intermediate levels of the mine contain both
coarse cassiterite and sulfides, including chalcopyrite, but
megascopic and microscopic relationships indicate that in
such cases the sulfides occur as veinlets cutting brecciated
cassiterite, or as axial or marginal reopenings of cassiteriterich veins. Locally, chalcopyrite-acicular cassiterite veins cut
bodies rich in wood-tin. Stages II and III are not, therefore,
1745
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KONTAK AND CLARK
considered gradational at the scale of the overall lode structure. The final stage III event was the development of quartzchlorite veins lacking sulfides and was most intense below
circa 4,300 m. A minor terminal veining event, Stage IV
(Palma, 1981), emplaced (Fig. 3) veins dominated by calcite
and quartz (in part amethystine), with erratic fluorite, stibnite, gudmundite, and exceptionally Ni- and Cr-rich mackinawite (A.H. Clark, unpub. data).
The abundance of vein chlorite associated with stage II cassiterite and stage III chalcopyrite is paralleled by moderate to
intense alteration to chlorite of the granitic host rocks, but
this hydrolytic alteration only locally extends more than 2 m
from the lodes. Mass exchange calculations have not been
carried out for the alteration envelopes, but the abundance
(to 40 modal %) and Fe-rich composition of the chlorite (see
below) imply that, in addition to almost complete leaching of
Ca, K, and Na, intense Fe-metasomatism occurred (Palma,
1981). A decrease in the deposition of cassiterite toward the
termination of stage II is paralleled by a decrease in the degree and extent of chloritization, but there is no systematic relationship overall between the local abundance of cassiterite
and such hydrolytic alteration. These proximal chloritic zones
grade outward to weak to moderate sericitic alteration, largely
affecting plagioclase in the host granites. Muscovite-quartz
assemblages, however, locally replace plagioclase adjacent to
stage II cassiterite-rich veinlets lacking evidence for either
stage I or III activity. Silicified envelopes also occur locally on
both stage II and stage III veins.
Structural relationships
In the upper 300 m of the San Rafael stock, stage I vein systems and breccia bodies widely possess either stockwork or
sheeted structures (Palma, 1981); their crudely radial and
concentric orientations suggest a control by cooling stresses
in the pluton. Late in stage I, however, tourmaline-quartz deposition became largely restricted to steeply dipping, quasicontinuous, conjugate shears striking on average 300 (westsouthwest dipping) and 335 (east-northeast dipping). Several
late stage I tourmaline-quartz vein segments record dextraltranscurrent displacement, but it is unclear whether vertical
movement was normal or reverse.
Stage II fractures and Sn deposits were preferentially, but
not exclusively, developed along the stage I 335 structures
(tourmaline leaders), although at depth both 300 and 335
orientations host economic concentrations of cassiterite on
the San Rafael Lode, and the extremely high-grade northern
segment of the lode is developed along an intermediate C
shear that strikes 310 to 325. The lode dips east-northeast
at 40 to 70 (Fig. 2b), averaging 60, but steepens to subvertical below 4,000 m a.s.l.
That stage II cassiterite mineralization in the San Rafael
Lode took place during left-lateral strike-slip movement was
demonstrated by Palma (1981): the southern contact of the
stock is offset by 5 to 30 m on various levels. Vertical displacement during stage II was reverse. Much of the cassiterite in the San Rafael Lode is hosted by major orebodies
(Fig. 2a) plunging east-northeast at 60 to 70 and exhibiting
classic dilational jog geometries (Fig. 2b; cf. Cox et al., 2001)
resulting from largely sinistral-transcurrent displacement, a
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relationship first documented by J. Alvarez (unpub. report to

Minsur S.A., 1978) and substantiated by Palma (1981) and
D.J. Kerr (unpub. report to Minsur S.A., 2002). It has been
estimated (D.J. Kerr, unpub. report to Minsur S.A., 2001)
that 80 to 82 percent of the Sn ore reserves occurs in these
orebodies. The form of the first to be discovered, and hence
termed the Ore Shoot, is illustrated in Figure 2b. The orebodies record multistage hydrothermal brecciation and cassiterite deposition, and they incorporate zones, particularly in
the hanging wall, attaining more than 35 percent Sn over
widths of at least 3 m. Structural relationships, therefore,
played a major role in the development of the large bonanza
orebodies that are responsible for the preeminence of San
Rafael among hard-rock Sn deposits.
Kontak and Clark (1988) and Clark et al. (1990a) emphasize that the San Rafael Lode and associated brittle shear
zones formed in response to regional, northwest-southeast
contraction. This contraction was initiated in the closing
phases of stage I, and structural relationships in the Quenamari mine area demonstrate that shear propagation and at
least stage III mineralization were contemporaneous with the
thrusting of the Carboniferous cover rocks over the Ordovician lower plate (A.H. Clark, unpub. data). On a smaller scale,
R. Mason and D.J. Kerr (unpub. report to Minsur S.A., 2000)
argue that the left (west)-stepping dilational jogs on the San
Rafael Lode were controlled by the intersection of the developing shear and preexisting, early stage I, radial and concentric fractures concentrated close to the eastern margin of the
stock.
Ore formation conditions
Fluid-inclusion microthermometric studies of vein quartz
(Palma, 1981; Kontak, 1985; A.H. Clark, unpub. data)
demonstrate that stage I fluids were highly saline and boiled
at temperatures of up to 580C, becoming cooler and less
saline with time. The most intense quartz > muscovite alteration is associated with the cooler fluids. Stages II (Sn) and
III (Cu Sn) formed at lower temperatures, each possessing
an overall homogenization temperature range of 215 to
420C. The predominant ore-depositing fluids were nonboiling brines with moderate to very low salinity (<220 wt %
NaCl equiv). Quartz coprecipitated with both botryoidal
wood-tin and coarsely crystalline cassiterite in stage II, and
stage III acicular cassiterite was deposited from fluids with
circa 10 to 20 wt percent NaCl equiv and Th = circa
300420C. However, microthermometric data for alternating bands of coarse cassiterite and quartz from the Ore Shoot
(4310 m level) indicate that the cassiterite was deposited from
significantly hotter (ca. 2030C) and more saline (ca. 510
wt % NaCl equiv) fluids than the associated quartz (A.H.
Clark, unpub. data). Palma (1981) demonstrated that, unexpectedly, no major changes in fluid temperature, i.e., Th, or
salinity attended the transition from Sn- to Cu-dominant mineralization in the upper part of the San Rafael Lode. However, the local occurrence of vapor-rich inclusions indicates
that the fluid sporadically boiled during chalcopyrite deposition, a feature not evident in stage II cassiterite assemblages.
Stage IV veins formed at lower temperatures (Th =
170300C) and from dilute fluids (5 wt % NaCl equiv).
1746
Age relationships of ore deposition

The best of several 40Ar/39Ar age plateaus for hydrothermal
muscovites directly associated with stage I tourmaline-quartz
veins yields an age of 24.10 0.15 Ma, in permissive agreement with an origin through retrograde boiling of the granitic
magma. However, incremental-heating 40Ar/39Ar age spectra
of aggregates of muscovite (2M1) flakes that replace plagioclase in proximity to stage II-dominated segments of the San
Rafael Lode yield markedly younger plateau ages in the range
22.4 to 22.7 0.7 Ma (Clark et al., 2000). These dates overlap with the troughs, 22.1 to 23.3 Ma, in the age spectra of
magmatic K feldspar (orthoclase structure) in the stock (Clark
et al., 2000), suggesting that cassiterite mineralization, at
420C, occurred when the upper part of the stock had cooled
to circa 230C (Berger and York, 1981). The evidence that
economic hydrothermal activity significantly postdated emplacement (24.624.7 Ma) and initial cooling of the epizonal
intrusion is supported by 40Ar/39Ar plateau dates of 21.9 to
22.0 0.2 Ma determined for hydrothermal adularia (lowsanidine structure) from a stannite-bearing stage III assemblage from the Jorge lode, which is contiguous with the San
Rafael Lode (Clark et al., 2000).
These age data imply that the upper part of the San Rafael
stock experienced retrograde boiling and high-T, barren hydrothermal activity shortly after its emplacement, but that
economic mineralization was significantly delayed and was,
moreover, thermally prograde with respect to the contiguous
granitic host rocks. Stages II and III in the San Rafael deposit
were contemporaneous with terminal Picotani Group intrusive and volcanic activity in the wider Carabaya district
(Sandeman et al., 1997).
Focus of the study
In the present contribution, the hydrothermal evolution of
this immensely fertile system is examined on two bases: the
secondary fluid inclusions widely trapped in quartz phenocrysts of the granitic host rocks, and the concomitant subsolidus mineralogic and geochemical processes in the upper
300 m of the stock. Particular attention is paid to evidence for
the involvement of plausibly magmatic brines, on the one hand,
and meteoric waters on the other (Kontak and Clark, 1997a).
The San Rafael and Quenamari Granites
Almost all exposures of the San Rafael and Quenamari
granitoid rocks exhibit phenocrysts of alkali feldspar (to 12 cm
in length), quartz (average 0.8 cm), extensively pinitized and
hence megascopically melanocratic cordierite (average 0.8
cm), and biotite (average 0.4 cm). Plagioclase, an abundant
matrix constituent, locally occurs as phenocrysts attaining 0.6
cm in length. None of the major minerals exhibits significant
vertical changes in modal percent within the 1 km exposure
interval of the SG stock. The euhedral forms of the original
cordierite grains (Fig. 4b, h), as well as the overall sparsity of
metasedimentary xenoliths, strongly imply a phenocrystic origin (Palma, 1981). However, sillimanite, an erratic minor constituent, occurs as both magmatic microphenocrysts and as fibrolitic aggregates intergrown with spinel in extremely rare
mineral clots, plausibly of restitic origin (Palma, 1981; Kontak, 1985). Muscovite does not occur as a magmatic phase.
0361-0128/98/000/000-00 $6.00
1747
The San Rafael granite stock and similar Quenamari granite

intrusions (Fig. 1b) are circumscribed by fine-grained, variably porphyritic ring dikes. These dikes are petrologically
similar to the central granites, exhibiting megacrysts of K
feldspar, cordierite and biotite (Fig. 4d, e, g).
Outcrop (Arenas, 1980) and underground exposures reveal
that the upper 750 m of the San Rafael granite is dominated
by two granitoid facies (Fig. 1b): an abundantly phenocrystic
monzogranite with a coarse-grained felsic matrix; and a more
sparsely phenocrystic phase with a finer-grained, mesocratic
matrix, which straddles the monzogranite-granodiorite
boundary in the alkali feldspar-plagioclase-quartz modal diagram and dominates the higher-elevation, northeastern outcrops of the stock. (Fig. 1b). These facies, however, occur
widely as mutual enclaves whose diameters range from 5 cm
to hundreds of meters and whose contacts range from planar
and sharp, through protrusive and gradational, to cuspate-sinuous (cf. Powell et al., 1999). Such relationships strongly suggest that the facies represent two distinct magmas, with varying rheology contrasts, that commingled in the upper part of
the stock. In addition, both facies widely incorporate mesocratic to melanocratic ellipsoidal enclaves, averaging 10 to 20
cm in maximum diameter. These enclaves include (A.H.
Clark, unpub. data) microgranular biotite granodioritic to
monzodioritic, as well as less abundant dioritic, diabasic/gabbroic, lamprophyric (minette, in part vesicular), and moderately micaceous to surmicaceous (>65% dark mica) members.
The enclave relationships demonstrate that the two major
granitoid magmas making up much of the San Rafael stock
additionally incorporated pillows of diverse mafic magmas
(A.H. Clark, unpub. data). This intimate coexistence of mantle-derived and anatectic magmas is a salient characteristic of
the Picotani Group and intrusive suite (Kontak et al., 1986;
Sandeman and Clark, 1993; Sandeman et al., 1997; Kontak
and Clark, 1997b). Sandeman et al. (1995) propose that this
igneous suite, emplaced during the Aymar tectonic event
prior to major mid-Miocene, Quechuan crustal contraction
and thickening, records shallow crustal anatexis caused by the
incursion of mafic melts generated largely in the lithospheric
mantle, in turn resulting from perturbation of the underlying
asthenosphere above a foundering detached slab. High heat
flow in relatively thin crust was focused along major structures relict from the Incaic, upper Eocene-lower Oligocene,
Zongo-San Gabn tectonic zone (Kontak et al., 1990; Sandeman et al., 1995).
The porphyritic granitoid rocks at San Rafael are associated
with small bodies of distinctive tourmaline leucogranite, exposed along the northwest roof and wall of the stock (Fig. 1b,
c; samples COCA [herein abbreviated CC]-156), and on its
southwest margin (too restricted to indicate in Fig. 1b, c; CC141), as well as in scattered locations in Sandia Formation
country rocks above the main stock (also too small to be
recorded in Fig. 1b). The absence of tourmaline veinlets and
clots argues against a metasomatic origin for this rock (e.g.,
Fig. 4f), which has potential implications for the evolution of
the granitic magmas and hence for ore genesis. The contact
of the leucogranite and the main intrusive phases is obscured
on surface, but its main exposure is probably plug like; however, a single 6 cm vein has been observed to cut monzogranite in drill core from circa 4,300 m a.s.l.
1747
1748
KONTAK AND CLARK
5 cm
5 cm
5 cm
5 cm
5 cm
g
5 cm
5 cm
5 cm
FIG. 4. Hand samples of San Rafael and Quenamari granites. (a) Medium-grained, K feldspar-megacrystic cordierite-biotite monzogranite. Coin for scale is 2 cm in diameter; (b) cordierite-rich monzogranite from main San Rafael granite intrusion with abundant pinitized cordierite (dark subequant grains). (c) Fine-grained nonphenocrystic phase of the San Rafael
granite; (d) Porphyritic granite from ring dike at the southwest margin of the San Rafael granite (see Fig.1b). Three dark
grains at upper left are subhedral cordierite. (e) Sample of fine-grained dike rock from Quenamari area showing sparse phenocrysts. (f) Fine-grained tourmaline-bearing leucogranite (CC-156) phase of the San Rafael granite, from the upper contact of the intrusion. Small dark grains are tourmaline. (g, h, i) Porphyritic Quenamari granite from central intrusion (see Fig.
1b) showing the variable replacement of K feldspar phenocrysts (pale gray) by secondary albite (white), resulting in pseudorapakivi texture, as discussed in the text.
The petrography and chemistry of the least-altered samples

of the San Rafael granite provide a datum for the identification
and delimitation of metasomatic processes. All accessible outcrops of the San Rafael granite and most exposures of the Quenamari granite were studied herein (Kontak, 1985). Underground exposures of the San Rafael granite are documented by
Palma (1981) and A.H. Clark (unpub. data). Most samples
specifically cited herein are from outcrop (Fig. 1c). Petrographic study reveals that approximately 15 percent of the
upper 400 m of the intrusion preserves little-modified magmatic relationships. The texture of both monzogranite and granodiorite is porphyritic overall (Fig. 4) with subhedral to euhedral grains of quartz, plagioclase, alkali feldspar, biotite, and
0361-0128/98/000/000-00 $6.00
cordierite in a hypidiomorphic granular matrix with variable

development of granophyre (Fig. 5a, b). Plagioclase widely preserves fine-scale oscillatory zones (Fig. 5c, d) as well as sievetextured zones (Fig. 5e, f), features characteristic of hypabyssal
and volcanic rocks. Alkali feldspar is variably perthitic, and film
perthite is more widely developed than flame and bleb types
(Fig. 5g, h). Rare grains of apparently uniform, unexsolved alkali feldspar are observed. The igneous mica varies from dark
red-brown to orangey brown and encloses accessory phases, including apatite, zircon, and monazite (Fig. 5i). Cordierite, locally an abundant phase, is invariably pinitized and hence dark
green at shallow levels of the stock, but fresh, pale blue and
mauve cores and sectors are preserved in phenocrysts at depth.
1748
1749
Crd
1mm
0.3 mm
0.6 mm
0.5 mm
1 mm
1 mm
1 mm
0.2 mm
0.4 mm
FIG. 5. Photomicrographs of polished thin sections illustrating salient magmatic petrographic features of the San Rafael
granite. (a) Graphic texture characteristic of much of the upper part of the San Rafael granite. Note pinitized cordierite (Crd)
grain at left and strongly zoned, euhedral plagioclase grain at upper left. (b) Hypidiomorphic granular texture typical of fresh
San Rafael granite. (c) Zoned plagioclase grains with incipient white mica alteration along a fracture in otherwise fresh granite. (d) Strongly zoned plagioclase with very calcic core (dark). In detail, this grain incorporates numerous reversals in zonation (calcic spikes). Note the xenomorphic texture of the surrounding matrix. (e, f) Glomerocryst of plagioclase with sieve
texture in all grains. Close-up of the area is shown in f. (g) Orthoclase megacryst in dike rock, exhibiting film and flame
perthite. Note the fracture localizing abundant and coarser perthite and the irregular nature of the grain boundary, that
shows intergrowth between the megacryst and matrix. (h) Detail of previous field showing the phenocryst margin inundated
with fluid inclusions. Inset shows well preserved film perthite adjacent to the area where coarsening to flame perthite occurs. (i) Typical dark red-brown biotite grain with radiation halos about accessory phases.
0361-0128/98/000/000-00 $6.00
1749
1750
KONTAK AND CLARK
Despite the epizonal context of the San Rafael granite,

there are no miarolytic cavities, and there is therefore no evidence that the volume of magma making up the stock experienced retrograde boiling.
Whole-rock geochemistry
Examination of more than 200 polished thin sections from
outcrop and the upper 600 m of the underground exposures
in the San Rafael granite, and from the Quenamari granite,
permits the distinction of rocks with negligible, minor, moderate, and strong hydrothermal alteration. It should, however,
be emphasized that sanidine, the magmatic alkali feldspar
species in entirely fresh epizonal members of the Picotani intrusive suite (Kontak and Clark, 1988; Sandeman, 1995), is
absent in the San Rafael granite and Quenamari granite; in
this respect, therefore, none of the San Rafael granite or
7
5
1.2
K2O wt. %
2
9
7
5
3
e)
1.4
1.6
20
1.8
40
60
80
Sn (ppm)
A/CNK
f)
K2O wt. %
d)
CaO wt. %
9
7
5
3
200
300
g)
h)
K2O wt. %
9
7
5
3
200
100
Sr (ppm)
400
200
300
600
Rb (ppm)
Sr (ppm)
40
i)
Nb (ppm)
100
K2O wt. %
c)
K2O wt. %
Field of
fresh SRG
Ba (ppm, X1000)
b)
K2O wt. %
Na2O wt. %
a)
Quenamari granite samples represents a pristine igneous assemblage. Reference is also made below to the broadly coeval
rocks of the Santo Domingo center and to the Antauta
granitic dike, which crops out 12 km south-southeast of San
Rafael (Kontak and Clark, 1988; Sandeman et al., 1997).
Analysis of the negligibly altered granitoid rocks (Table 1;
Figs. 6, 7) reveals (1) a range of SiO2 content from 64.4 to
70.7 wt percent in the larger stocks, but with some dike rocks
exceeding 72 wt percent; (2) K2O/Na2O significantly exceeding unity (Fig. 6a); (3) an aluminum saturation index (moles
Al2O3/moles CaO + Na2O + K2O) of 1.1 to 1.25 overall (Fig.
6b), the most Ca-Fe-Mgrich granodioritic samples having
the lower values (1.11.15: Palma, 1981); (4) continuous
trends in Harker-type variation diagrams, such as are typical
of felsic suites (Kontak, 1985); (5) both whole-rock and biotite
compositions indicating very reduced conditions, the latter
7
5
30
Fractionation
20
10
3
2000
1000
Ba (ppm)
Alteration
Alteration
Index
Index
100
200
100
200
Zr (ppm)
Zr (ppm)
Negligible
Negligible
Moderate
Moderate
Minor
Minor
Strong
Strong
FIG. 6. Binary element plots for major and trace element data for fresh and variably altered San Rafael and Quenamari
granites. The circled field in each plot is for fresh San Rafael granite. The arrow in the Nb-Zr plot shows the fractionation
inferred to be responsible for two samples of tourmaline leucogranite (CC-141, 156), on the basis of the apparent immobility of these trace elements. A/CNK (b) is the aluminum saturation index, i.e., moles Al2O3/moles CaO + Na2O + K2O. The
symbols refer to the different groupings of samples defined on the basis of the degree of alteration, determined petrographically as discussed in the text.
0361-0128/98/000/000-00 $6.00
1750
0361-0128/98/000/000-00 $6.00
1751
4.2
1.3
3.6
1.3
3.6
1.2
4.4
1.3
4.0
1.3
3.9
1.3
135.3
137.9
106.5
80.4
48.6
19.2
20.1
9.7
10.7
7.0
9.0
7.0
5.0
3.0
3.8
1.2
58.0
52.6
46.4
41.4
28.4
21.0
16.3
13.0
10.8
19.1
9.5
8.0
9.9
9.0
3.2
1.2
44.4
46.8
44.1
37.0
25.7
7.4
14.8
13.0
13.9
10.0
9.6
7.0
5.0
5.0
4.2
1.3
163.7
149.4
108.8
76.9
45.0
17.6
21.3
19.1
14.3
14.9
9.4
6.0
3.3
6.6
5.0
1.4
160.3
164.8
126.7
84.8
57.7
17.4
30.3
16.7
18.1
10.4
11.9
9.0
5.0
7.8
3.5
1.3
40.4
39.0
29.9
29.5
18.3
0.5
9.7
9.0
7.0
10.0
9.6
9.0
8.0
11.0
4.4
1.3
6.0
1.6
77.2
67.6
45.8
43.1
24.9
7.8
12.4
19.3
9.7
8.0
5.1
5.0
5.1
9.9
4.1
1.3
4.1
3.7
1.3
85.3 4.0
76.3 5.6
54.2 3.7
52.8 2.0
30.8 3.7
9.4 8.5
18.8 3.8
26.3 3.0
15.8 1.3
9.5 6.4
12.6 3.5
7.0 6.0
5.1 8.0
7.0 15.0
9
32
371 124
45 NA
183 630
264
32
174
28
NA NA
NA 40
NA 49
NA
98
11
15
52 NA
4.7
1.4
7.6
1.8
15.0
16.0
20.0
19.5
13.5
30.8
10.4
19.4
15.5
14.1
9.7
7.0
5.5
6.0
39
11
118 1,502
NA
32
162 502
87 105
24 128
NA
10
14
15
670 675
925
56
21
36
NA NA
5.3
1.5
104.7
84.6
54.4
46.8
27.5
6.8
11.4
6.6
7.8
8.6
5.7
4.0
2.7
1.2
7
918
45
588
84
168
NA
NA
NA
NA
4
NA
74.39
0.11
15.23
0.18
0.56
0.06
1.04
0.49
2.22
3.06
0.32
97.66
68.10
0.38
15.12
2.70
NA
0.03
1.26
0.40
2.57
5.73
0.20
96.49
8.1
1.9
4.4
1.4
141.9
121.9
80.1
71.1
39.2
13.1
19.7
12.1
11.9
10.0
8.6
6.0
4.0
3.2
5.2
1.4
187.4
191.6
144.9
103.8
65.2
24.4
29.2
18.6
14.9
13.3
11.5
8.0
7.2
7.0
4.6
1.4
68.50
0.39
15.36
2.86
NA
0.07
1.31
0.37
1.20
7.11
0.21
97.38
68.70
0.33
16.27
2.90
NA
0.10
1.20
0.34
1.12
5.84
0.18
96.98
64.90
0.50
15.67
3.40
NA
0.06
2.36
0.27
0.01
7.28
0.19
94.64
66.60
0.42
14.52
3.78
NA
0.45
1.77
0.48
0.46
7.45
0.27
96.20
65.90
0.36
15.19
2.99
NA
0.14
1.61
0.30
0.36
8.62
0.22
95.69
5.4
1.5
94.3
86.0
57.7
51.6
30.1
11.5
14.9
7.0
9.5
5.9
8.2
6.0
3.2
4.1
7.9
1.9
82.6
77.9
52.0
46.8
28.6
8.5
14.9
14.9
10.7
5.6
8.7
7.0
3.7
4.0
7.7
1.9
5.5
1.5
5.3
1.5
8
9
8
9
9
946 1,392 1,839 1,777 1,317
46
37
82
58
64
460 478 462 465 509
78 100 156 201 197
154 149 193 146 166
NA NA NA NA NA
NA NA NA NA NA
NA NA NA NA NA
NA NA NA NA NA
38
32
18
50
13
50
44 137 195 118
68.40
0.43
15.77
3.49
NA
0.12
1.46
1.25
3.91
2.68
0.19
97.70
7
512
64
188
120
173
NA
NA
NA
NA
85
43
66.80
0.48
15.60
2.95
NA
0.08
2.14
0.55
2.05
6.17
0.26
97.08
6
6
357 1,023 1,221
NA
51
71
446 380 376
13 226 191
23 135 167
10 NA NA
7 NA NA
69 NA NA
60 NA NA
61
22
14
NA
62 115
69.05 68.40 73.67 74.11 69.61 69.80

0.37 0.38 0.12 0.10 0.33 0.40
15.74 15.90 14.85 14.41 15.66 15.14
2.28 2.60 0.27 ND 0.28 2.55
NA
NA 0.48 2.11 2.90 NA
0.08 0.12 0.01 0.02 0.12 0.09
1.21 0.98 0.79 0.86 1.06 0.79
0.92 1.42 0.27 0.62 0.27 0.33
4.72 4.45 3.72 4.95 0.03 0.48
2.45 2.16 4.84 1.13 7.40 8.28
0.19 0.18 0.28 0.32 0.21 0.21
97.01 96.59 99.30 98.63 97.87 98.07
8
438
47
183
255
153
NA
NA
NA
NA
11
54
70.20
0.35
15.14
2.56
NA
0.12
1.03
0.54
3.47
2.68
0.20
96.29
9
711
37
200
186
138
NA
NA
NA
NA
4
52
68.40
0.46
16.58
0.20
2.47
0.05
1.56
1.40
3.09
4.80
0.24
99.25
14
762
54
321
285
156
12
28
79
203
4
NA
70.47
0.36
15.47
0.27
1.87
0.03
1.29
1.31
2.84
4.86
0.19
98.96
16
503
42
354
167
119
10
6
1
194
13
NA
68.50
0.37
15.80
2.57
NA
0.05
1.23
1.02
2.46
4.96
0.19
97.15
7
530
40
308
168
134
NA
NA
NA
NA
17
56
64.40
0.38
15.61
2.27
NA
0.05
1.30
0.95
4.08
3.23
0.18
92.45
9
560
45
230
256
143
NA
NA
NA
NA
7
61
68.10
0.40
15.31
3.07
NA
0.07
1.17
1.14
3.24
4.78
0.18
97.46
F = fresh, M = moderately altered, NA = not analyzed, ND = not detected, S = strongly altered, W = weakly altered
%C
3.7
A/CNK 1.3
Chondrite-normalized REE values

La
219.6
Ce
203.2
Pr
158.0
Nd
111.0
Sm
64.3
Eu
25.0
Gd
24.4
Tb
22.3
Dy
14.5
Ho
16.8
Er
6.3
Tm
5.0
Yb
3.0
Lu
3.0
68.34
0.45
16.65
0.30
2.38
0.07
1.57
1.45
3.47
4.70
0.25
99.63
Sample number and degree of alteration of granite

COCA COCA COCA COCA COCA COCA COCA COCA COCA COCA COCA COCA COCA COCA COCA COCA COCA COCA COCA COCA COCA
166A 403 203 151 195 249A 244 150 156 141 250 252 140 198 217 213 239 190 187A 218 206
W
W
W
M
M
M
M
M
M
S
S
S
S
S
S
S
S
S
S
S
S
13
9
870 1,573
NA
42
306 322
298 168
158 147
12
10
28 NA
93 NA
314 NA
8
23
NA
51
68.40
0.43
15.32
2.74
NA
0.10
1.10
1.10
2.81
4.79
0.16
96.95
9
856
51
308
256
156
NA
NA
NA
NA
13
47
69.11
0.40
16.29
0.34
2.17
0.05
1.63
1.54
2.91
4.83
0.21
99.48
17
553
NA
329
227
122
10
16
59
130
9
NA
66.50
0.49
15.91
3.27
NA
0.10
1.44
0.78
2.71
5.64
0.21
97.05
8
911
57
358
209
187
NA
NA
NA
NA
4
48
66.40
0.48
16.10
2.62
NA
0.07
1.55
1.34
3.41
4.59
0.21
96.77
Trace elements (ppm)

Nb
7
10
6
7
Ba
602 455 479 1,193
V
38
39
38
63
Rb
317 377 351 310
Sr
174 142 165 294
Zr
135 135 127 186
Ni
NA NA NA NA
Cu
NA NA NA NA
Pb
NA NA NA NA
Zn
NA NA NA NA
Sn
7
23
12
20
Cr
34
42
33
65
70.00
0.40
15.22
2.31
NA
0.05
1.02
1.07
3.00
4.82
0.18
98.07
70.70
0.35
14.67
2.06
NA
0.07
0.91
0.89
2.86
4.66
0.16
97.33
SiO2
TiO2
Al2O3
Fe2O3
FeO
MnO
MgO
CaO
Na2O
K2O
P2O5
Total
69.50
0.34
15.50
2.74
NA
0.03
1.12
1.04
2.79
4.96
0.21
98.23
COCA COCA COCA COCA COCA COCA COCA COCA

154 165 248 406 408 194 202 197
F
F
F
F
F
F
F
W
Compound
or element
TABLE 1. Compositions of Fresh and Altered Granites, San Rafael-Quenamari Granite District, Southeast Peru
1751
1752
KONTAK AND CLARK
a)
Ab
Ab
Or
An
c)
Ab
d)
Or
C
Or Ab
Ba
e)
Sn
b)
f)
Or
Zr
Rb
Rb Sr
Sr
Alteration
Index
Negligible
Moderate
Minor
Strong
FIG. 7. Ternary plots of normative (CIPW) proportions of minerals calculated for variably altered San Rafael and Quenamari granites.
corresponding to the Ni-NiO buffer in ternary Fe+2-Fe+3-Mg+2

space (Kontak, 1985), compatible with the occurrence of rare
ilmenite as the sole Fe-Ti oxide phase, and its stoichiometric
(Fe,Mg)TiO3 composition (A.H. Clark, unpub. data); and (6) a
clustering in terms of both quartz-albite-orthoclase (Fig. 7a)
and anorthite-albite-orthoclase (Fig. 7c) normative proportions
close to minimum melting compositions. In its whole-rock
chemistry, the San Rafael granite is more cafemic than other
strongly peraluminous, S-type granites (White and Chappell,
1983; Tischendorf et al., 1987; Stimac et al., 1995).
Rb contents fall in the narrow range of 350 50 ppm (Fig.
6f), and K/Rb ratios are confined to 120 to 140, values typical
of granites (Shaw, 1968). Ba shows the greatest variation
among the trace elements (479 to 1,193 ppm, and one very
weakly altered rock at 1,573 ppm: Fig. 6g), whereas Sr exhibits a much narrower range (142294 ppm: Fig. 6d). There
is limited dispersal of the data in ternary plots, and the fresh
samples cluster tightly in Ba-Sr-Rb and Zr-Sr-Rb diagrams
(Fig. 7e, f). Two moderately altered leucocratic granite samples (CC-141 and 156), however, are strongly enriched in
both Zr and Nb (Fig. 6i), a relationship interpreted as evidence for strong fractionation of the melt.
The rare earth element (REE) abundances (Fig. 8a) are
similar to those of unaltered peraluminous granites in general
0361-0128/98/000/000-00 $6.00
(e.g., Muecke and Clarke, 1981), and the patterns are indistinguishable from those of other peraluminous granites of similar
age in southeast Peru (Kontak and Clark, 1988). The granites
exhibit chondrite-normalized light rare earth element (LREE)
values of 80 to 120, strongly fractionated REE overall [(La/Yb)N
= 2040], and negative Eu anomalies (EuN/Eu* = 0.50.9).
Fluorine contents in the San Rafael granite and Quenamari
granite are 0.08 to 0.18 wt percent (A.H. Clark, unpub. data),
much lower than those in many granites associated with
lithophile-metal mineralization (Tischendorf, 1977), but in
conformity with the low and consistent F contents in biotite
(Fig. 9). The Sn contents of the fresh rocks are anomalous, attaining 23 ppm (Table 2; Fig. 6c) and contrasting with the
Clarke value of circa 4 ppm for granites sensu lato. It is, however, significant that neither of the analyzed samples of tourmaline leucogranite (CC 141 or 156) is Sn-enriched relative
to the main monzogranites and granodiorites (Table 2).
Mineral chemistry
The compositions of biotite, plagioclase, and alkali feldspar
in the freshest samples of the San Rafael granite and Quenamari granite provide a basis for the recognition of the effects
of superimposed fluid-rock interaction. Phenocrystic biotite
in the upper part of the stock (Table 2; Fig. 9) shows a limited
1752
1753
Ce Nd Eu Tb Ho Tm Lu
b)
1000
c)
1000
Santo Domingo
CC-406
100
CC-202
10
moderate alteration
CC-203
CC-403
CC-197
CC-166A
100
10
field of fresh
SRG
CC-150
CC-249A
CC-151
CC-156
100
10
tourmaline
leucogranite
1
La Pr Sm Gd Dy Er Yb
Ce Nd
Ce
Nd Eu
Eu Tb
Tb Ho
Ho Tm
Tm Lu
Lu
c)
d)
1000
minor alteration
Rock/Chondrite
Rock/Chondrite
least altered granite (SRG)
Rock/Chondrite
a)
d)
1000
CC-217
CC-198
CC-239
CC-190
CC-252
CC-250
100
10
FIG. 8. Chondrite-normalized rare-earth element plots for various populations of the

San Rafael (SRG) and Quenamari granites, classified on the basis of the degree of alter1 ation related to metasomatism. A fresh sample of the petrologically similar Santo Domingo
granite is included in (a). Plots (c) and (d) illustrate the distinct pattern of a late-stage tourmaline leucogranite (CC-156), inferred to represent a more evolved melt fraction.
a)
Si per formula unit
b)
3.2
= Mineral
separates
Si per formula unit
Rock/Chondrite
strong K alteration
(COCA-156)
3.0
2.8
2.6
0.5
0.6
0.7
2.8
2.6
1.0
30
wt. % Al2O3
3
2
1
5.0
3.0
wt. % TiO2
d)
wt. % F
3.0
0.8
Fe/(Fe+Mg)
c)
3.2
S-type granites
20
S/I-type granites
10
0.5
0.6
0.7
0.8
Fe/(Fe+Mg)
CC-17
CC-156
10
12
wt. % MgO
CC-408
CC-154
CC-244
CC-151
CC-150
FIG. 9. Binary element plots for magmatic biotite in eight samples of San Rafael granite, as determined by electron microprobe and bulk analysis of mineral separates. Note that the data for the tourmaline leucogranite (no. 156) occupy distinct fields in all plots. The fields delineated for S- and I-type granites are based on data for well characterized granite suites
elsewhere.
0361-0128/98/000/000-00 $6.00
1753
0361-0128/98/000/000-00 $6.00
1754
36.34
3.28
19.72
0.10
16.86
0.22
9.73
0.13
0.86
8.89
0.56
96.69
0.24
96.45
Antauta
COCA-17
1
Structural formula (11 oxygens)

Si
2.699
Al(iv)
1.301
Al(vi)
0.426
Ti
0.183
Cr
0.006
Fe
1.047
Mn
0.013
Mg
1.077
Ca
0.010
Na
0.123
K
0.843
SiO2
TiO2
Al2O3
Cr2O3
FeO(T)
MnO
MgO
CaO
Na2O
K2O
F
Total
F=O
Total
Compound
or
element
2.649
1.351
0.412
0.175
0.008
1.104
0.017
1.081
0.008
0.122
0.836
35.73
3.15
20.17
0.13
17.81
0.28
9.79
0.11
0.85
8.84
0.88
97.74
0.37
97.37
Antauta
COCA-17
2
2.795
1.205
0.523
0.160
0.006
1.010
0.017
0.988
0.008
0.142
0.783
37.88
2.89
19.87
0.10
16.36
0.27
8.98
0.10
0.99
8.32
0.61
96.37
0.26
96.11
Antauta
COCA-17
3
2.687
1.313
0.338
0.190
0.007
1.217
0.017
1.058
0.011
0.053
0.849
36.10
3.41
18.83
0.12
19.54
0.26
9.54
0.15
0.37
8.95
0.61
97.88
0.26
97.62
San Rafael
COCA-150
12
2.680
1.320
0.355
0.190
0.009
1.172
0.014
1.078
0.007
0.056
0.858
35.98
3.41
19.08
0.16
18.81
0.24
9.71
0.09
0.39
9.03
0.73
97.63
0.31
97.32
San Rafael
COCA-150
13
2.680
1.320
0.332
0.197
0.009
1.253
0.018
0.999
0.008
0.053
0.891
35.38
3.46
18.51
0.15
19.78
0.28
8.85
0.10
0.36
9.22
0.80
96.89
0.34
96.55
San Rafael
COCA-150
14
3.227
0.773
1.380
0.081
0.009
0.347
0.008
0.308
0.006
0.043
0.889
46.61
1.57
26.37
0.18
5.99
0.13
2.98
0.08
0.33
10.06
2.24
96.54
0.94
95.60
San Rafael
COCA-156
23
Granite, sample number, and point
2.985
1.015
1.083
0.073
0.008
0.806
0.012
0.411
0.008
0.063
0.900
41.02
1.34
24.46
0.15
13.26
0.20
3.80
0.10
0.45
9.69
2.01
96.48
0.85
95.63
San Rafael
COCA-156
24
3.108
0.893
1.366
0.018
0.003
0.513
0.011
0.342
0.006
0.064
0.901
44.26
0.34
27.30
0.07
8.73
0.19
3.27
0.08
0.47
10.05
3.34
98.10
1.41
96.69
San Rafael
COCA-156
31
2.998
1.003
1.106
0.024
0.006
0.858
0.015
0.419
0.007
0.050
0.909
40.62
0.46
24.25
0.10
13.90
0.25
3.81
0.09
0.35
9.64
3.12
96.59
1.31
95.28
San Rafael
COCA-156
32
TABLE 2. Representative Electron Microprobe Analysis of Magmatic Biotite from the San Rafael and Antauta Granites, Southeast Peru
2.694
1.306
0.323
0.194
0.009
1.183
0.020
1.101
0.009
0.062
0.838
35.60
3.41
18.26
0.16
18.68
0.31
9.76
0.12
0.42
8.69
1.11
96.52
0.47
96.05
San Rafael
COCA-408
48
2.669
1.331
0.315
0.204
0.009
1.197
0.023
1.075
0.009
0.065
0.860
35.22
3.58
18.45
0.15
18.89
0.37
9.52
0.11
0.45
8.89
1.07
96.70
0.45
96.25
San Rafael
COCA-408
49
1754
KONTAK AND CLARK
variation in major element contents, with Fe/(Fe + Mg) = 0.5

to 0.55, <1 wt percent F, and 3 to 5 wt percent TiO2. The
micas, which contain 8 to 10 wt percent MgO, are distinctly
magnesian compared with those in the majority of peraluminous granitoids, including those of Lachlan S-type. However,
microscopically fresh biotite from a leucogranite, CC-156,
deviates markedly in all plots and possesses strong but variable enrichment in Fe, Al, Si, and F (3.5 wt %).
In the upper part of the San Rafael pluton, the majority of
the plagioclase phenocrysts are normally zoned, most falling
in the compositional range An2040 (Table 3, Fig. 10). Some,
however, contain cores as calcic as An55. Although these cores
are corroded and could represent restitic components, comparably Ca-rich compositions occur in the outer parts of phenocrysts in numerous samples from the 4200 m level of the
San Rafael granite, where there is unambiguous megascopic
evidence for commingling and mixing with mafic magmas
(A.H. Clark, unpub. data). Such calcic spikes overgrew strong
50An
least altered SRG
(COCA-156)
minor
alteration
moderate
alteration
strong alteration
20 analyses
Ab
Or
FIG. 10. Compositions of feldspars from variably altered San Rafael and
Quenamari granites plotted in part of the An-Ab-Or ternary. Plagioclase in
the leucocratic granite (no. 156) approaches end-member albite. Translucent
sanidine from a dike rock from the Antauta center (see text) is the Or75Ab25
phase in the first ternary plot. Note the progression toward more albitic plagioclase as the degree of alteration increases, culminating in end-member
albite in the most altered rocks.
0361-0128/98/000/000-00 $6.00
1755
internal corrosion surfaces recording complete dissolution,

but sieve textures indicative of partial magmatic corrosion are
present in groundmass and phenocrystic plagioclase throughout the intrusion (Fig. 5e, f), and core areas are commonly
less calcic than rims (Table 3). As noted above, scattered alkali feldspar phenocrysts in the upper part of the San Rafael
granite and in the Quenamari granite contain true rapakivi
texture, i.e., overgrowth by oligoclase, but this feature is again
more commonly observed below circa 4,300 m in the San
Rafael granite. Microscopically unaltered plagioclase in the
tourmaline leucogranite is markedly more sodic (An510) than
that in the main intrusion (Fig. 10).
Analyses of two separates of orthoclase perthite indicate
that alkali feldspar in the least-altered granites has a bulk
composition of Or74Ab23An3. Similar compositions are obtained both from separates and from single crystals of sanidine (Or75Ab25) from nearby intrusions of similar age and petrogenesis, i.e., Antauta and Santo Domingo (Fig. 10, Table 3).
The K-rich domains of perthitic orthoclase range from
Or89Ab11 to Or97Ab3 (Fig. 10). The abundances of Rb, Sr, Ba,
Li, and Pb (Table 4, Fig. 11) in the separates from the San
Rafael, Santo Domingo, and Antauta granites are also uniform, evidence for similar melt compositions (Ichenhower
and London, 1996). The REE data for alkali feldspar separates (Fig. 11) have chondrite-normalized abundances, fractionation patterns [(La/Lu)N = 3480] and positive Eu anomalies (EuN/Eu* = 2025 for the San Rafael granite and 317
for Santo Domingo and Antauta), such as are typical of alkali
feldspars in granites (Smith, 1974; Leeman and Phelps, 1981;
Kontak and Martin, 1997). Again, similar compositions are
shown by alkali feldspars from the San Rafael granite and
other nearby intrusions (Fig. 11).
The alkali feldspar is perthitic and exhibits strong (201)

sodium peaks in X-ray powder diffraction patterns (Fig.
12a). Film perthite is cut by later flame perthite that locally
coalesces into coarse bleb perthite (Fig. 5g, h). All alkali
feldspar is turbid and incorporates areas characterized in
thin section by pitted textures which, when viewed under
high magnification, are seen to result from swarms of fluid
inclusions. In contrast, the Antauta dike, interpreted as a
small, quenched intrusion only locally affected by hydrothermal activity, exhibits translucent phenocrystic sanidine, thus providing a basis for assessment of ordering relationships during alkali metasomatism at San Rafael. The
degree of Al/Si ordering of the alkali feldspar in the least altered granites in the wider San Rafael district, as summa
rized in the (060) vs. (204) diagram of Stewart and Wright
(1974; Fig. 12b), is variable. Whereas in the San Rafael
granite proper the feldspars plot in a distinct field straddling
the orthoclase tie-line, those from the Quenamari granite
and the granitic dikes exhibit structures ranging from orthoclase to an intermediate position between orthoclase and
sanidine, respectively, and stock- and dike-hosted samples
are distinctly separate. In the altered samples, the feldspars
invert to end-member K feldspar and plot at the boundary
of the field (see Fig. 12b and discussion below). The ordering relationships in the San Rafael granite alkali feldspars
and the extensive preservation of film perthite are strong evidence for rapid cooling and hence an epizonal emplacement level for the stock.
1755
0361-0128/98/000/000-00 $6.00
1756
37.7
60.3
2.0
End member (mol %)

An
25.4
Ab
71.9
Or
2.7
57.97
25.68
7.70
6.81
0.34
98.55
2.628
1.371
0.374
0.598
0.019
61.26
24.04
5.28
8.23
0.47
99.52
Plagioclase
Plagioclase

Si
2.736
Al
1.264
Ca
0.251
Na
0.711
K
0.026
SiO2
Al2O3
CaO
Na2O
K2O
Total
Compound
or
element
Antauta
COCA-17
4
Antauta
COCA-17
1
0.6
24.8
74.6
3.001
1.003
0.005
0.217
0.653
64.77
18.93
0.12
2.42
11.06
97.38
Sanidine
Antauta
COCA-17
13
0.2
24.4
75.4
3.002
1.043
0.002
0.208
0.643
64.08
18.90
0.07
2.30
10.77
96.12
Sanidine
Antauta
COCA-17
14
0.0
3.8
96.2
3.024
1.016
0.000
0.032
0.808
65.62
18.67
0.00
0.39
13.69
98.38
Orthoclase
San Rafael
COCA-151
1
7.8
90.3
1.9
2.976
1.072
0.064
0.744
0.016
67.37
20.51
1.34
8.68
0.31
98.23
San Rafael
COCA-151
2
Exsolved
albite
5.0
93.0
2.0
2.992
1.040
0.040
0.744
0.016
68.09
20.06
0.84
8.69
0.30
97.98
San Rafael
COCA-151
3
Exsolved
albite
6.8
92.4
0.8
2.944
1.072
0.064
0.872
0.008
67.20
20.83
1.33
10.27
0.17
99.80
San Rafael
COCA-151
4
Exsolved
albite
Granite, sample number, point, and phase
0.0
3.5
96.5
3.008
1.024
0.000
0.032
0.880
64.82
18.70
0.00
0.37
14.80
98.69
Orthoclase
San Rafael
COCA-151
5
29.2
67.9
2.9
2.705
1.296
0.288
0.669
0.028
59.87
24.37
5.95
7.66
0.50
98.58
Plagioclase
San Rafael
COCA-150
27
TABLE 3. Representative Analyses of Feldspars in Unaltered Antauta and San Rafael Granites, Southeast Peru
13.6
83.6
2.7
2.896
1.136
0.120
0.736
0.024
65.56
21.79
2.61
8.59
0.38
98.95
San Rafael
COCA-151
25
Core sieve
plagioclase
39.0
60.2
0.8
2.608
1.400
0.384
0.592
0.008
58.71
26.69
8.10
6.83
0.16
100.51
San Rafael
COCA-151
30
Rim sieve
plagioclase
15.3
82.0
2.7
2.880
1.144
0.136
0.728
0.024
65.91
22.24
2.94
8.62
0.43
100.16
San Rafael
COCA-151
31
Rim sieve
plagioclase
1756
KONTAK AND CLARK
1757

TABLE 4. Trace Element Content of Alkali Feldspar Separates, Picotani Intrusive Suite Granites, Southeast Peru
San Rafael
Sample
Mol % Or*
Li
Rb
Sr
Ba
Pb
Antauta
COCA
407
COCA
408A
COCA
249
COCA
249
COCA
190
COCA
198
COCA
165B
COCA
15
73.1
76.2
13.6
13.6
93.3
85.4
87.8
70.0
19.8
407
346
2,554
153
27.7
456
533
6,337
172
38.2
162
321
335
205
37.5
157
309
325
203
23.3
599
353
14,813
45.8
36.9
600
336
5,371
126
42.6
723
302
3,880
129
Rare-earth elements
La
Ce
Pr
Nd
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
4.55
7.65
0.79
2.74
0.52
3.63
0.65
0.04
0.22
0.04
0.11
0.01
0.08
0.008
6.16
10.14
1.04
3.53
0.63
6.59
1.04
0.04
0.21
0.04
0.08
0.01
0.04
0.008
9.92
20.80
2.47
9.33
1.82
0.80
1.25
0.17
0.92
0.15
0.44
0.06
0.35
0.03
9.76
20.60
2.42
8.99
1.87
0.82
1.37
0.20
0.97
0.16
0.42
0.05
0.31
0.04
4.88
9.89
1.18
4.25
0.92
0.08
3.68
0.07
0.41
0.08
0.25
0.03
0.08
0.02
7.59
12.89
1.38
4.60
0.91
4.25
1.06
0.07
0.31
0.05
0.12
0.01
0.08
0.01
4.61
8.35
0.89
3.06
0.54
3.53
0.53
0.04
0.25
0.03
0.08
0.009
0.015
0.008
Santo Domingo
SD
4
SD
5
76.0
251
485
352
2,518
179
171
485
334
1,976
155
7.52
13.70
1.50
5.09
0.88
1.22
0.90
0.06
0.36
0.05
0.21
0.03
0.15
0.02
75.3
169
519
334
1,818
143
3.65
5.89
0.63
2.08
0.39
2.37
0.43
0.02
0.13
0.02
0.06
0.01
0.05
0.01
SD
3
SD
6
86.3
89.7
28.9
509
509
6,841
186
44.8
690
579
6,612
85.2
4.77
8.32
0.92
3.17
0.59
2.57
0.55
0.05
0.28
0.05
0.14
0.01
0.09
0.01
5.41
7.82
0.98
3.30
0.69
0.82
1.31
0.05
0.27
0.05
0.12
0.02
0.07
0.015
10.60
14.00
1.95
6.72
1.29
3.64
1.88
0.10
0.52
0.09
0.28
0.03
0.16
0.03
*Mol % Or determined on mineral separates by X-ray fluoresence
Petrology of Metasomatized Granite

Outside of the chloritic alteration halos of the mineralized
veins, much of the upper parts of the San Rafael granite and
Quenamari granite appear unaltered in outcrop and hand
specimen, because of the widespread preservation of apparently fresh biotite and the mafic appearance of the pinite
pseudomorphs after cordierite (e.g., Fig. 4). The granites are

not bleached and contain little megascopic secondary white
mica. However, as emphasized by Kontak (1985) and Kontak
and Clark (1988), intense alkali metasomatism and weaker
hydrolytic alteration have affected much of the upper part of
the San Rafael stock and all accessible outcrops of the Quenamari area stock, as well as the dikes associated with each.
1000
1000
100
10
407
408A
249
249(D)
Or76
Or73
Or85
Or87
Or93
Or13
Or13
K-feldspar/Chondrite
K-feldspar/Chondrite
San Rafael &

Quenamari
165B
198
190
Santo Domingo &

Antauta
Or90
Or76
Or75
Or70
Or86
100
10
1
15
4
5
3
0.1
0.1
Li Sr Pb La Pr Sm Gd Dy Er Yb
Rb Ba
Li Sr Pb La Pr Sm Gd Dy Er Yb
Rb Ba
FIG. 11. Extended chondrite-normalized plots for trace- and rare-earth element data for alkali feldspar separates from
granites at San Rafael (CC-407, 408A, 249, 165B), Quenamari (190, 198), Antauta (15), and Santo Domingo (4, 5, 3, 6). Sample 249D is a duplicate of 249.
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KONTAK AND CLARK
a)
42.0
K
(041)
Sanidine
Orthoclase
Perthite
degree of development of specific microscopic alteration fabrics. We distinguish between negligibly, weakly, moderately,
and strongly altered facies, which possess approximate
preservation of igneous mineral assemblages and textural relationships of, respectively, 90 to 95 percent, 80 to 95 percent,
50 to 80 percent, and <50 percent. This combined petrographic and mineralogic approach is inherently subjective,
but it is, in our opinion, adequately robust.
b)
Orthoclase
Perthite
Na
metasom.
QG stock
(060)
K
(111)
K
K
(130) (201)
K
(131)
Na
(201)
QG dikes
SRG stock
Antauta
dike
metasomatism
SRG
41.5
50.5
51.0
(204)
c)
lin
se
ro
c
la
32
28
di
ne
or
th
oc
2 cm
ni
sa
K
metasom.
m
ic
Na
metasom.
(060)
42.0
Petrography of alkali-metasomatized granite

Although difficult to see in outcrop, the widespread alkali
metasomatism in the San Rafael granite is clearly revealed by
the use of standard staining methods for K and Ca-bearing
feldspars. In Figure 13 a fresh granite (a) is contrasted with a
cryptically altered sample (b, c) that reveals the extent of K
metasomatism and plagioclase destruction only after being
stained (cf. b, c).
24
20
2 degrees Cu K
41.5
50.5
(204)
51.0
FIG. 12. X-ray powder diffraction data for alkali feldspars from stocks and
dike rocks in the San Rafael-Quenamari area (see Kontak et al., 1984, for details). Data are plotted in the orthoclase and microcline fields (i.e., degree of
Al/Si ordering: diagram of Wright, 1968); compositions are also a function of
Miller indices (i.e., increasing Or content toward the lower left of the plot).
The Quenamari dike samples retain a less-ordered structure than those from
the larger Quenamari and San Rafael intrusions. At San Rafael, the less-ordered samples occur at the roof of the stock, in the right-hand area of the outlined field, and the sanidine samples (diamonds) are from the Antauta dike.
The metasomatism has caused the feldspars to invert to end-member K
feldspar at the boundary of the field. The inferred trend with increasing alteration is from 1 to 6 (b). The corresponding diffractogram patterns are
shown in (a).
Our studies of outcrop and underground exposures demonstrate

that no circa 100 m3 volume of the San Rafael granite above the
4350 m level has escaped this alteration, which exhibits no control by megascopic fractures, including stage I veins and the
mineralized lodes. The pervasive nature of the alkali exchange
alteration precludes the preparation of maps or sections illustrating its extent and intensity, but overall it is evident that, in
the upper 600 m of the San Rafael granite, unaltered or weakly
altered granite is considerably less widespread within 500 m of
the eastern and northeastern contacts than in the western half
of the stock. The areal distribution of the hydrolytic alteration
is less well established, but we tentatively conclude that it is
most intense and pervasive within 20 to 30 m of the lodes.
Despite the wide dispersion of the both alkali and hydrolytic alteration, most mineralogic features are heterogeneously developed at both hand-specimen and thin-section
scales. In order to define the effects of metasomatism, therefore, samples have been assigned to alteration intensity
groups on the basis of estimates, in stained hand specimens
and in thin section, of the modal abundances of hydrothermal
orthoclase, albite, chlorite, and sericite, coupled with the
0361-0128/98/000/000-00 $6.00
a
3 cm
b
3 cm
c
FIG. 13. Slabs of fresh (a) and altered (b, c) San Rafael granite. (a) Fresh
granite with calcic plagioclase (stained red) and coarse megacrystic and matrix phase K feldspar (stained yellow). Small, dark equant grains are
cordierite and dark, platy grains are biotite. (b, c) Altered granite with stained
side shown in (b) and unstained in (c). Note the markedly diminished amount
of red color in this sample resulting from the albitization of the primary calcic plagioclase.
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1759
The dominant alteration process in the granitoid rocks

hosting the main San Rafael Lode system was the replacement both of perthitic orthoclase phenocrysts and of groundmass plagioclase by almost Na-free hydrothermal orthoclase,
with remarkably little change in megascopic appearance.
However, an increase in the turbidity of the igneous alkali
feldspar at grain boundaries (Fig. 5g, h) and along intragrain
fractures is evident at the hand-lens and microscopic scales in
the more weakly K-metasomatized rocks. With increasing alteration, the turbidity extends throughout the grains, with
concomitant development of abundant coarse perthite, fluid
inclusions, and micropores. In the most strongly K-metasomatized rocks, pitted textures become pervasive within K
feldspar grains, but perthite decreases. In rare cases, distinct
microscopic domains of Ba-rich feldspar develop, initially
along fractures and then invading the surrounding feldspar
(Fig. 14). The coarser grains of barian feldspar exhibit rhombic, adularia-like forms (Fig. 14c, d). Accompanying this replacement is the generation of porosity, irregular in places
(Fig. 14a, b), that assumes crudely rhombic outlines where
the adularia grains are concentrated; such cavities host
Fe-rich chlorite euhedra (Fig. 14c). Hydrothermal biotite has

not been observed.
In contrast to the potassic alteration, Na metasomatism, erratically distributed in the main San Rafael granite but predominant in the Quenamari granite as well as in the Santo
Domingo granite (A.H. Clark, unpub.), characteristically
takes the form of replacive rims of white albite on cream alkali feldspar megacrysts (Fig. 4g, h, i), although groundmass
plagioclase is also albitized. The rim development is a striking
feature in outcrop, particularly where the altered phenocrysts
exhibit rounded, ellipsoidal forms. Hence, some Na metasomatic domains are readily delimited although, without Ca
staining, the albite overgrowths are difficult to distinguish
from the much more locally developed true rapakivi textures.
Because the outer surfaces of both the phenocrysts and the
remnant K feldspar are rounded, it is possible that such textures are inherited from rapakivi-textured grains; they are
not, however, observed in most areas of relict fresh granite in
the upper part of the San Rafael stock. As in the K metasomatic domains, increased turbidity of magmatic K feldspar is
apparent adjacent to albite rims.
100
100
mm
25% FeO
20 100
mm
wt. % BaO
36% FeO
6.6%
2.8%
Chl
6.3%
6.1%
5.8%
29% FeO
d
100100m
m
5.4%
0%
20 100
mm
FIG. 14. Back-scattered electron images of K feldspar in altered San Rafael granite sample CC-190. (Note that the higher
the average atomic number of an area the brighter the image.) These images illustrate (a, b) the pitted texture of orthoclase
resulting from fluid-mediated alteration of magmatic K feldspar; (bright areas in a, c, d) the presence of celsian feldspar; (c,
d) zonation and euhedral forms of adularia-like grains; and (c) the late development of chlorite euhedra (chl) occluding pores
caused by formation of celsian felspar. Numbers in (d) are wt percent BaO in the K feldspar.
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Alteration of the quartzofeldspathic matrix of the granites

results in the development of an allotriomorphic assemblage
of subequant grains with sutured boundaries (Fig. 15a), contrasting markedly with the primary hypidiomorphic texture
(cf. Fig. 5b, c). Staining shows that this matrix consists of
widely variable proportions of pure orthoclase and albite, intergrown with quartz.
Petrography of hydrolytically altered granite

Development of fine-grained white mica after feldspars is
the most easily recognizable microscopic feature of hydrolytic
alteration in many rocks. In K feldspar phenocrysts, muscovite is either disseminated throughout or concentrated
along fractures (Fig. 15b). Replacement of plagioclase by
1.0 mm
0.4 mm
Kf
1.0 mm
1.0 mm
1.0 mm
1.0 mm
Tour
1.0 mm
1.0 mm
80 m
FIG. 15. Photomicrographs of altered San Rafael Granite. (a) Matrix showing extensive development of sutured grain
boundaries and allotriomorphic texture. (b) White mica in fracture cutting orthoclase. (c) Fine-grained white mica replacing
zoned plagioclase. (d) Incipient alteration of biotite along cleavage planes and formation of Ti-rich phases. (e) Extreme chloritization of biotite with formation of ragged edges and secondary minerals along cleavage traces. (f) Muscovite alteration of
quartzofeldspathic matrix with formation of rosette textures. (g) Anhedral tourmaline (Tour) and abundant quartz replacing
orthoclase (Kf). (h) Tourmaline (lower right) replacing fine-grained granitic matrix. Note that the tourmaline is much coarser
than the matrix material. (i) Disseminated acicular cassiterite in metasomatic tourmaline in altered granite, adjacent to a vein
exhibiting stages I and II mineral assemblages.
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fine-grained muscovite, generally in concentric zones about

the core area (Fig. 15c), is very common, but coarser muscovite rosettes form at more advanced stages. Secondary muscovite also develops within matrix feldspars and eventually
dominates the assemblage, and both fine-grained and coarse
rosettes of muscovite coexist with quartz (Fig. 15f). Igneous
quartz, both phenocrystic and in the matrix, responds to alteration by development of sutured outlines and internal subdomains as grain-size reduction proceeds, and it becomes inundated with fluid inclusions. Secondary quartz is associated
with tourmaline that replaces feldspars and in the matrix (Fig.
15g).
Biotite records the effects of hydrogen metasomatism
through progressive replacement by chlorite. The alteration
apparently occurred at constant volume, the subhedral-to-euhedral forms being retained (Figs.15e, 16). Initial alteration
along cleavage planes is associated with a change in color
Qtz
Kf
Alb
Chl
Kf
Qtz
250 m
Rutile
Chl
Il/Mus
100 m
FIG. 16. Back-scattered electron images of altered granite showing replacement of primary magmatic biotite by chlorite, rutile, and illite/muscovite. Alb = albite, Il = illite, Kf = K feldspar, Mus = muscovite, Qtz =
quartz.
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from dark red-brown to pale orange-brown (Fig. 15d). As alteration continues, biotite is transformed to an Fe-rich chlorite. The alteration generates secondary phases, predominantly rutile, which nucleates along cleavage planes (Fig. 16a)
and forms sagenite-like textures. Biotite is locally replaced by
a mixture of muscovite and illite (Fig. 16b). Chlorite also replaces feldspar, as radiating or vermicular-textured grains,
and is dispersed in the matrix. Beyond its intense development adjacent to some early stage I veinlets and breccia bodies, tourmaline occurs as subhedral to euhedral grains randomly dispersed within metasomatized granites, both within
the matrix and replacing coarse K feldspar megacrysts (Fig.
15g). There is a strong association of quartz with coarser tourmaline (Fig. 15g, h). In rare cases, small, apparently systematically oriented, acicular cassiterite euhedra occur within
metasomatic tourmaline grains (Fig. 15i). Although tourmaline is clearly a metasomatic phase in many areas, euhedral
grains in the matrix of the tourmaline leucogranite (COCA156) are interpreted as magmatic.
Whole-rock geochemistry of altered granites
Hydrothermal alteration of the San Rafael granite and
Quenamari granite, both alkali exchange and hydrolytic, was
attended by significant metasomatism. The resulting compositional trends in general correlate satisfactorily with the petrographic subdivisions discussed in the previous section. The
compositions of the altered rocks thus define arrays projecting away from the field delimited for the freshest San Rafael
granite, with enrichment or depletion in the alkalies (Figs.
6a, 7a, c) and associated mobilization of Ca, Ba, Rb, and Sr
(Fig. 6d, e, f). The K enrichment that affected large volumes
of the San Rafael granite was associated with an increase in
A/CNK ratio (Fig. 6b), which records the development of
feldspar-destructive muscovite or its normative equivalent
corundum (Fig. 7d), a feature not shown by the Na-metasomatized Quenamari granite. This difference in alkali enrichment in the two areas may reflect erosional level, in that the
Quenamari area, from the abundance of fine-grained granitic
dike rocks (Fig. 4) and Pb-Zn-Agrich mineralization, probably represents a higher section in the intrusive environment
than San Rafael, and would therefore have cooled more
abruptly.
Ba, Sr, and Rb were mobile during alkali metasomatism.
The positive correlation of K with both Rb (Fig. 6f: r = 0.80)
and Ba (Fig. 6g: r = 0.70) reflects uptake of Rb in muscovite
and of Ba in alkali feldspar. The poor correlation between Rb
and Ba (r = 0.39) is further evidence that these elements are
sequestered in different minerals. Depletion of both Ca and
Sr is plausibly related to destruction of magmatic plagioclase
(Fig. 6e). The positive correlation between Ba and Sr in the
most altered rocks (Fig. 6d) also suggests that Sr is enriched
in the samples with celsian-rich feldspar. However, rocks of
varying alteration intensity from the upper 500 m of the main
San Rafael stock do not have systematic differences in Zr or
Nb contents (Figs. 6h, i, 7f), and these elements are inferred
to have been relatively immobile during both alkali metasomatism and hydrolytic alteration.
Tin is enriched (Table 2) in only about 20 percent of the
analyzed altered rocks, attaining 61 ppm, and of these twothirds are enriched in K rather than Na (Fig. 6c). On this basis
1761
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KONTAK AND CLARK
we tentatively conclude that the apex of the largely K-metasomatized San Rafael granite experienced a significantly
stronger, albeit erratic, enrichment in originally magmatic Sn
than did the Quenamari intrusions. There was, in addition, an
inconsistent enrichment of the base metals, and Zn ranges
from 56 to 925 ppm and Pb from below detection to 675 ppm.
In contrast, there was very little enrichment in Cu; maximum
values do not exceed 40 ppm Cu despite the high Cu grades
in the veins in the upper San Rafael granite.
In Figure 8, REE spectra of selected altered rocks are
arranged in order of increasing alteration intensity and are
compared with the data for fresh San Rafael granite. In general, there is very little change in the overall abundances of
REE in the metasomatized samples, which retain the strongly
fractionated chondrite-normalized signature of the fresh
granite. This is not unexpected, given that REE are largely sequestered in robust accessory mineral phases (e.g., monazite,
zircon, xenotime, and apatite: Gromet and Silver, 1983; Bea,
1996). The Eu anomalies are similar to those in the fresh San
Rafael granite, implying that the metasomatic fluid was reduced, thereby limiting the mobility of Eu; this reduced
metasomatic fluid is in conformity with both the reduced
composition of the granitic magma and the abundance of
pyrrhotite in the veins. Samples with moderate alteration
(Fig. 8c) exhibit a consistent depletion in LREE compared
with both the fresh San Rafael granite and the more intensely
altered samples (Fig. 8d). The heavy rare earth elements
(HREE), in particular Yb and Lu, appear to deviate the most
from the trend for fresh San Rafael granite, implying either
greater mobility of these elements or their uptake in new
mineral phases. Only one sample (CC-250) deviates markedly
(Fig. 8d), and this for the LREE only, perhaps the result of a
reaction involving a LREE-rich accessory mineral such as

monazite.
Alteration mineral chemistry
Plagioclase: Plagioclase progresses toward more sodic compositions in increasingly altered rocks, and albite (An1) characterizes the most altered samples (Fig. 10). Where albite is
present, the grains commonly display a pitted texture. There
is a clear hiatus from An13 to An2 that separates the moderately from the most strongly altered samples and corresponds
closely to the peristerite gap (e.g., Moody et al., 1985). Alkali
feldspar is Or90100 in altered rocks, but the most important
feature is the erratic presence of barian feldspar. One hydrothermal orthoclase sample (CC-190) contains areas with
up to 6.6 wt percent BaO (Table 5), and back-scatter electron
imaging reveals a complex zonation with alternating zones
rich and poor in Ba (Fig. 14c, d). Bulk analyses of alkali
feldspar separates (Table 5) reveal both K and Na enrichment; compositions tend to Or93Ab6An1 and Or14Ab82An4, and
reflect subsolidus reequilibration (Smith, 1974). Trace element analyses of separates show that Li, Rb, and Sr abundances are surprisingly uniform and comparable to those in
fresh alkali feldspar (Fig. 11). In contrast, Ba shows extreme
variability, attaining circa 15,000 ppm in the most K-rich sample (CC-190: Or93) and greatest depletion (325 ppm) in an albitized sample (CC-249: Ab87). Similar Ba-enrichment occurs
in K feldspars in the Santo Domingo granite, where concentrations of 6,612 and 6,841 ppm are attained in rocks in which
the host feldspar compositions, Or89 and Or86, indicate that
postmagmatic processes have modified the primary magmatic
chemistry. The REE contents and chondrite-normalized patterns for altered K feldspar (Fig. 11), along with their bulk
TABLE 5. Representative Analyses of Alkali Feldspar in Altered San Rafael-Quenamari Granites, Southeast Peru
Compound
or
element
SiO2
Al2O3
Na2O
K2O
CaO
BaO
Total
Quenamari
COCA-190
23
Quenamari
COCA-190
25
Quenamari
COCA-190
26
Quenamari
COCA-190
31
San Rafael
COCA-141
21
San Rafael
COCA-151
3
San Rafael
COCA-151
4
San Rafael
COCA-165B
San Rafael
COCA-249
66.21
18.91
0.00
13.57
0.00
0.44
99.13
60.31
20.19
0.80
12.25
0.00
6.16
99.72
63.46
19.29
0.52
14.28
0.00
2.88
100.43
60.22
19.64
0.87
12.39
0.00
6.61
99.74
68.07
19.89
11.46
0.05
0.27
0.00
99.74
68.09
20.06
8.69
0.30
0.84
0.00
98.46
67.20
20.83
10.27
0.17
1.33
0.00
99.82
64.52
18.92
1.09
13.00
0.17
0.21
97.91
67.50
19.13
7.33
1.85
0.72
0.04
96.57

Si
3.032
Al
1.024
Na
0.000
K
0.792
Ca
0.000
Ba
0.008
End member (mol %)
Ab
0.0
Or
99.0
An
0.0
Cs
1.0
2.880
1.136
0.072
0.744
0.000
0.112
7.8
80.2
0.0
12.1
2.952
1.056
0.048
0.848
0.000
0.056
5.0
89.1
0.0
5.9
2.896
1.112
0.080
0.760
0.000
0.128
8.3
78.5
0.0
13.2
2.977
1.025
0.971
0.002
0.011
0.000
98.6
0.3
1.1
0.0
2.992
1.040
0.744
0.016
0.040
0.000
93.0
2.0
5.0
0.0
2.944
1.072
0.872
0.008
0.064
0.000
92.3
1.0
6.7
0.0
2.998
1.036
0.098
0.771
0.008
0.004
11.2
87.8
1.0
0.5
Data for samples COCA-165B and 249 derived from bulk analyses of mineral separates analyzed by X-ray fluorescence (Kontak, 1985)
Analyses of samples COCA-165B and 249 are bulk analyses of mineral separates determined by X-ray fluorescence (Kontak, 1985)
0361-0128/98/000/000-00 $6.00
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3.035
1.013
0.639
0.106
0.035
0.001
81.9
13.6
4.5
0.0
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Fe/(Fe+Mg)
a)
0.0
0.5
Pseudothuringite
Corundophilite
5
Sheridanite
Si
6
1.0
Ripidolite
Daphnite
Clinochlore Pycnochlorite
Brunsvigite
Penninite
7
Diabantite
Thuringite Chamosite Delessite
compositions expressed as mole percent Or, show that (1)

there is an overall enrichment in REE in altered San Rafael
granite samples, and two of the most altered samples (CC249, 190) show marked enrichment; (2) the chondrite-normalized patterns are nonetheless preserved during the alteration and enrichment; and (3) there is a notable decrease in
EuN, which may reflect removal of Eu through the conversion
of Eu2+ to Eu3+ during subsolidus fluid/rock interaction (Sverjensky, 1984). These observations would be consistent with
transport of REE in saline, high-temperature fluids as preserved in the quartz megacrysts in the altered granites (discussed in detail below).
Samples of alkali feldspar from variably altered granites
were selected for X-ray diffraction study for comparison of
their compositional and ordering relationships with those
from relatively fresh granite. The data (Fig. 12) show that
feldspar from metasomatized San Rafael granite differs
markedly from that in relatively fresh rocks. In the former,
the diffractograms reflect either Na or K metasomatism, as
indicated by the increase (samples 4 and 5) or decrease (sample 6) in the intensity of albite reflections. Further, the K-rich
domains in K feldspar subjected to either K or Na metasomatism have the composition Or100, as demonstrated by both
Orville
(1963) and Wright (1968), who contoured the (060)
/(2 04) diagram using Na-K exchange experiments. Finally, it

is evident that the dispersal of the metasomatized feldspar
data along the base of the plot reflects a variable Si/Al ordering, similar to that shown by feldspar in the least-altered granites. Thus, although K-rich domains were developed during
metasomatism via K-Na exchange, there was no accompanying migration of Al and Si within the feldspar structure.
Biotite: Biotite in altered rocks does not record any systematic chemical changes compared with biotite in fresh samples,
even in chloritized zones along cleavage traces. Chlorite was
analyzed (Table 6) in three samples that represent contrasted
modes of occurrence of this mineral, i.e., alteration zones in
primary biotite (CC-151); domains of extreme Fe metasomatism adjacent to mineralized veins (CC-177); and within
feldspar (CC-190). Electron microprobe analyses reveal two
Fe/(Fe + Mg) populations in the ripidolite and daphnite
fields (Fig. 17a, b). The most Fe-rich chlorite generally occurs in altered wall rock adjacent to stage II Sn ore, but similar compositions are also found in the latest chlorite overgrowths occluding secondary porosity in Ba-rich feldspar
(Fig.14c). The remaining, more magnesian, chlorites replace
primary biotite or are enclosed by feldspar. Minor Mn (to 1.5
wt % MnO) occurs in the chlorite.
Tourmaline: Tourmaline exhibits strong optical zoning, and
this zoning is reflected in both variable Fe (trace to 15 wt %
FeOT) and Mg (trace to 10 wt % MgO), and minor variation
in Na (trace to 2 wt % Na2O: Table 7). The compositional
variations plotted in Figure 18 are for two tourmalines from
altered San Rafael granite remote from a mineralized vein
(CC-151,154), one from intensely altered granite adjacent to
a mineralized vein (CC-177) and the other from the largest
tourmaline leucogranite plug (CC-156). The data define a
continuum between Fe-rich and Fe-poor compositions, the
tourmaline from sample CC-177 occupying both extremes.
The data also overlap with the compositions for tourmaline in
stage I stockwork veins recorded by Palma (1981).
Talc-chlorite
4
2+
12
3+
Fe + Fe
b)
CC-151
CC-177
CC-190
Fe
4
0.4
0.6
0.8
1.0
Fe/(Fe+Mg)
FIG. 17. Compositions of chlorite from moderately (CC-151) and strongly
(CC-190) altered granite, and from chlorite-tourmaline rock; CC-177) granite determined by electron microprobe analysis. (a) Binary plot of atomic
proportions of Si versus Fe/(Fe + Mg) in classification diagram of Hey
(1954). (b) Binary plot of atomic proportions of Fe versus Fe/(Fe + Mg).
Note that in these diagrams the chlorite in the strongly altered sample is the
most Fe rich; only minor amounts of such chlorite occur in the other samples, in which the Fe/(Fe + Mg) ratios are similar to those of fresh biotite (cf.
Fig. 9).
Fluid Inclusions in Quartz Phenocrysts

Petrography
The fluids responsible for the extensive alteration of the
granite, we propose, are represented by secondary inclusions
in quartz phenocrysts (Fig. 19). These are locally extremely
abundant, and occur both along healed fracture planes (Fig.
19a, d) and as isolated bodies. The inclusions are of irregular
or negative-crystal shapes and generally 10 to 30 m in maximum diameter, although some attain dimensions of 75 to 300
m. They may be subdivided (Fig. 19) into the following categories: (i) aqueous-liquid rich, (ii) vapor rich (>8090%
vapor), (iii) liquid-vapor- halite, (iv) liquid-vapor-sylvite, and
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21.94
0.00
21.05
40.39
0.84
1.28
0.00
0.00
85.50
San Rafael
COCA-177
17A
5.320
2.680
3.200
0.000
0.000
6.804
0.056
1.680
0.000
0.000
23.68
0.00
22.27
36.32
0.35
5.01
0.00
0.00
87.63
San Rafael
COCA-177
19
5.154
2.846
3.168
0.011
0.011
6.507
0.131
1.946
0.016
0.025
23.35
0.07
23.11
35.24
0.71
5.92
0.08
0.06
88.54
San Rafael
COCA-177
7
5.292
2.708
2.920
0.000
0.000
5.068
0.084
3.808
0.000
0.000
24.49
0.00
22.04
28.03
0.48
11.80
0.00
0.00
86.84
Quenamari
COCA-190
9
5.432
2.568
2.836
0.000
0.000
4.200
0.280
4.536
0.000
0.000
25.67
0.00
21.72
23.74
1.64
14.40
0.00
0.00
87.17
Quenamari
COCA-190
10
Sample COCA-190 is a zoned grain; columns 9 through 13 represent core to rim analyses
5.180
2.820
2.948
0.000
0.000
8.092
0.280
0.644
0.000
0.000
21.27
0.00
20.07
39.70
1.33
1.76
0.00
0.00
84.13
San Rafael
COCA-177
18

Si
5.236
Al(iv)
2.764
Al(vi)
3.144
Ti
0.000
Cr
0.000
Fe
8.036
Mn
0.168
Mg
0.448
Ca
0.000
Na
0.000
SiO2
TiO2
Al2O3
FeO
MnO
MgO
CaO
Na2O
Total
Compound
or
element
5.376
2.624
2.808
0.000
0.000
4.396
0.196
4.480
0.000
0.000
25.41
0.00
21.79
24.74
1.11
14.14
0.00
0.00
87.19
Quenamari
COCA-190
11
5.432
2.568
2.976
0.000
0.000
4.452
0.364
4.004
0.000
0.000
25.59
0.00
22.08
24.94
1.94
12.66
0.00
0.00
87.21
Quenamari
COCA-190
12
5.292
2.708
2.920
0.000
0.000
5.124
0.112
3.752
0.000
0.000
24.37
0.00
21.94
28.15
0.59
11.58
0.00
0.00
86.63
Quenamari
COCA-190
13
5.348
2.652
3.172
0.000
0.000
6.468
0.224
1.820
0.000
0.000
23.81
0.00
22.02
34.35
1.23
5.39
0.00
0.00
86.80
Quenamari
COCA-190
34
TABLE 6. Representative Analyses of Chlorite in Altered San Rafael-Quenamari Granite, Southeast Peru
5.628
2.372
2.808
0.000
0.000
4.816
0.056
4.088
0.000
0.000
26.12
0.00
20.33
26.66
0.31
12.72
0.00
0.00
86.14
San Rafael
COCA-151
10
5.572
2.428
2.780
0.000
0.000
4.844
0.056
4.116
0.000
0.000
25.68
0.00
20.42
26.70
0.32
12.76
0.00
0.00
85.88
San Rafael
COCA-151
15
5.964
2.036
2.864
0.000
0.000
4.340
0.056
3.920
0.000
0.000
28.21
0.73
19.73
24.63
0.33
12.42
0.00
0.00
86.05
San Rafael
COCA-151
3
1764
KONTAK AND CLARK
0361-0128/98/000/000-00 $6.00
35.78
0.00
36.16
12.13
0.00
0.74
0.24
1.13
86.18
36.36
0.00
35.95
11.49
0.00
0.69
0.00
1.24
85.73

Si
6.776
6.860
Al(iv)
1.224
1.140
Al(vi)
6.840
6.868
Ti
0.000
0.000
Fe
1.932
1.820
Mn
0.000
0.000
Mg
0.196
0.196
Ca
0.056
0.000
Na
0.420
0.448
SiO2
TiO2
Al2O3
FeO
MnO
MgO
CaO
Na2O
Total
35.76
0.00
34.62
13.21
0.00
0.97
0.00
1.59
86.15
6.832
1.168
6.616
0.000
2.100
0.000
0.280
0.000
0.588
37.29
0.00
32.62
4.29
0.00
8.21
0.61
2.39
85.41
6.888
1.112
5.972
0.000
0.672
0.000
2.268
0.112
0.868
6.860
1.140
6.280
0.000
0.728
0.000
1.988
0.056
0.728
37.22
0.00
34.14
4.76
0.00
7.19
0.26
2.07
85.64
37.14
0.00
38.74
0.47
0.00
6.88
0.00
1.73
84.96
6.692
1.308
6.924
0.000
0.084
0.000
0.168
0.000
0.616
35.67
0.30
32.12
14.56
0.00
1.07
0.17
1.76
85.65
6.916
1.084
6.252
0.056
2.380
0.000
0.308
0.028
0.672
37.76
0.30
34.20
0.47
0.00
10.15
0.48
2.69
86.05
6.804
1.196
6.084
0.028
0.084
0.000
2.744
0.084
0.952
6.692
1.308
6.924
0.000
0.084
0.000
0.168
0.000
0.616
37.14
0.00
38.74
0.47
0.00
6.88
0.00
1.73
84.96
32.67
0.43
37.47
12.48
0.33
0.88
0.22
2.18
86.66
6.216
1.784
6.644
0.056
1.988
0.028
0.224
0.028
0.784
34.57
0.68
34.70
13.10
0.14
1.39
0.18
2.20
86.96
6.580
1.420
6.364
0.084
2.072
0.000
0.392
0.028
0.812
36.96
0.00
40.26
0.85
0.00
5.75
0.00
1.16
84.98
6.664
1.336
7.204
0.000
0.140
0.000
1.540
0.000
0.420
0.6
36.96
0.00
40.26
0.85
0.00
5.75
0.00
1.16
84.98
6.664
1.336
7.204
0.000
0.140
0.000
1.540
0.000
0.420
6.412
1.588
6.504
0.056
1.932
0.000
0.392
0.028
0.784
34.08
0.45
36.44
12.31
0.13
1.41
0.19
2.19
87.20
35.47
1.06
32.39
8.87
0.00
5.59
0.62
2.18
86.18
6.692
1.308
5.888
0.140
1.400
0.000
1.568
0.140
0.812
35.54
0.87
33.84
9.61
0.00
4.35
0.31
2.13
86.65
6.664
1.336
6.140
0.112
1.512
0.000
1.204
0.056
0.780
Compound
Sample number and point
or
COCA-177 COCA-177 COCA-177 COCA-177 COCA-177 COCA-177 COCA-177 COCA-177 COCA-177 COCA-177 COCA-177 COCA-156 COCA-156 COCA-156 COCA-151 COCA-151
element
1
2
3
4
5
6
7
8
8
13
13
51
52
53
20
21
TABLE 7. Representative Analyses of Tourmaline in Altered San Rafael Granite, Southeast Peru
a)
Fe
0.4
b)
c)
0.0
0.0
1765
0.2
0.4
1765
1
CC-151
CC-154
CC-156
CC-177
1.0
Na
0.8
0.3
0.2
Ca
0.1
0.6
0.8
1.0
Fe/(Fe+Mg)
FIG. 18. Compositions of tourmaline from negligibly (CC-154), moderately (CC-151) and strongly altered (chlorite-tourmaline rock, CC-177) granites and the tourmaline leucogranite (CC-156), determined by electron microprobe analysis. Results are plotted in various binary element plots (atomic
proportions). Note that the extreme end-member compositions are represented by the most altered rock (CC-177) and that the tourmaline in the
leucogranite sample is extremely Fe rich, whereas that in the other granite
samples has an Fe/(Fe + Mg) ratio similar to that of fresh biotite (cf. Fig. 9).
(v) liquid-vapor-multiple solids, which, from optical properties and scanning electron microscopy (SEM) data include, in
addition to halides, Fe-rich mica, hematite, and sulfides. The
simple liquid-vapor inclusions possess a large range in salinity, but it is not possible to distinguish high- and low-salinity
(i.e., 023 wt % NaCl equiv) types on the basis of petrography. Petrographic evidence that fluid unmixing occurred within
the system (e.g., Bodnar et al., 1985b) includes the occurrence
of discrete fluid inclusion assemblages (i.e., FIA of Goldstein
and Reynolds, 1994) of the appropriate inclusion types
(e.g., Fig. 19c) along healed fractures, and the coexistence of
vapor-rich inclusions with inclusion types iii and iv. Moreover,
because phenocrysts containing the greatest number of
1766
KONTAK AND CLARK
300 m
200 m
100 m
20 m
100 m
d
B
100 m
30 m
30 m
30 m
H
H
15 m
30 m
FIG. 19. Photomicrographs of fluid inclusions in phenocrystic quartz of the San Rafael granite; all photos taken in planepolarized transmitted light. (a) Typical area of quartz phenocryst in San Rafael granite showing abundant healed fracture
planes decorated with fluid inclusions. (b) Typical area of quartz phenocryst inundated with liquid- and vapor-rich fluid inclusions. Two areas are enlarged to illustrate the contrasting nature of the fluid inclusion populations. (c) Healed fracture plane
inundated with negative-crystalshaped, vapor-rich fluid inclusions. Inset shows part of the area enlarged. (d) Multiple healed
fracture planes in quartz that are decorated with abundant fluid inclusions of liquid-vapor and liquid-vapor-solid types. Two
areas (g, j) are enlarged in Figures 19g and j. (e) Pair of multisolid fluid inclusions with halite (H), birefringent (B) phase and
other undetermined solids. Image is a mosaic with these inclusions forming part of a plane containing numerous such inclusions. (f) Pair of equant liquid-vapor fluid inclusions; (g) Multisolid, liquid-rich, negative-shaped fluid inclusions with halite
and other unidentified solids; (h) Healed fracture plane with two-phase liquid-vapor fluid inclusions of negative crystal shape;
(i) Healed fracture plane with two-phase liquid-vapor fluid inclusions of irregular shape; (j) vapor-rich, halite-bearing fluid inclusion; and (k) Plane of liquid-vapor halite fluid inclusions that are in close proximity to plane of liquid-vapor fluid inclusions
(large inclusion on the right). Image is mosaic to show the various inclusion populations represented.
0361-0128/98/000/000-00 $6.00
1766
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vapor-rich inclusions also host numerous hypersaline (liquidvapor-halite-sylvite) inclusions, commonly along the same
fracture planes, we infer that unmixing occurred within the
upper part of the stock.
Microthermometric relationships
Following reconnaissance examination of approximately 45
samples of granitic rocks from outcrop and underground exposures, eight surface samples (Fig. 1c) were selected for detailed microthermometric study. These samples represent
both the main San Rafael granite and Quenamari granite
stocks, as well as several of the flanking dikes, and embrace all
categories of pervasive alteration intensity. The data for heating and freezing experiments are summarized in Figure 20.
Ice was the last phase to melt in all two-phase (liquid-vapor)
aqueous inclusions, but in many cases the melting of hydrohalite could also be observed. First-melting or eutectic temperatures range from 65 to 0.5C (Fig. 20a), and distinct
populations occur at 20C, 30 to 45C, and 50C. As
emphasized by Kontak and Clark (1997a), these data show
that the fluid must contain solutes in addition to NaCl.
b)
60
50
Frequency
200
Mg, Fe
Frequency
a)
Nonsaline fluids (i.e., 0 wt % NaCl equiv) are also very widely

preserved. The lack of clathrate formation or freezing of the
vapor phase during cooling runs indicates that condensed
gases such as CO2, if present, occur in minor concentrations.
Fluid salinities, estimated from the last melting of ice and
dissolution of daughter minerals (Bodnar, 1994; Bodnar and
Vityk, 1994), range from circa 0 to 65 wt percent NaCl equiv,
but with two distinct groupings that correspond to liquidvapor and liquid-vapor-halite inclusion types (Fig. 20b). The
histogram indicates that the liquid-vapor inclusions exhibit a
continuum in salinity, but L/V ratios confirm that variable
salinities commonly occur within apparently coherent populations of such inclusions. This behavior is observed for liquid-vapor type inclusions with salinities below circa 10 wt
percent equivalent NaCl; thus, the last melting of ice varies
from 3 to 7C in such assemblages, indicating a range of 4 to
7 wt percent NaCl. For hypersaline inclusions, the
NaCl/(NaCl + KCl) ratio varies from 0.47 to 0.63, as determined from projection of the dissolution temperatures of
halite and sylvite into the NaCl-KCl-H2O ternary diagram.
Inclusion homogenization occurs at 205 to 540C (Fig. 20c)
40
30
Na, K
20
Ca
10
-70 -60 -50 -40 -30 -20 -10
first melting
( C)
Th(Halite )
Th(L)
Th(L)
Salinity
60
40
20
0
300
400
500
600
homogenization
20
30
40
50
60
70
80
Th(V)
80
200
10
Salinity (wt. % eq. NaCl)
d)
100
80
(wt. % eq. NaCl)
Frequency
c)
120
40
160
( C)
Th(Halite)
Th(V)
60
I
40
II
20
III
IV
0
100
200
300
400
500
o
homogenization
( C)
FIG. 20. Summary of microthermometric data for secondary fluid inclusions hosted by phenocrystic quartz in the San
Rafael granite, and a comparison with primary inclusions in quartz and cassiterite in the San Rafael Lode. (a) First-melting
or eutectic temperatures. The cations shown are the suggested dominant species in solution accounting for the first-melting
temperatures. (b) Salinity vs. wt percent NaCl equiv. (c) Final homogenization temperature for inclusions grouped according to the nature of homogenization, namely expansion of the liquid phase (Thliquid), expansion of the vapor phase (Thvapor),
and dissolution of halite (Thhalite); (d) Comparative plot of salinity vs. homogenization temperature for all inclusion types
hosted by quartz phenocrysts and lode minerals fields for stages I to IV (from Palma (1981) and A.H. Clark (unpub. data),
as discussed in the text).
0361-0128/98/000/000-00 $6.00
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KONTAK AND CLARK
T ( Halite) homogenization ( oC)
Th(H)>T(L)
500
(55 wt. %)
(50 wt. %)
400
(45 wt. %)
3 2
(40 wt. %)
300
(35 wt. %)
200
Th(H)<T(L)
200
300
400
500
600
T ( L) homogenization (C)
3.0
400
C
0
40
600
ni
200
C
0
45
ted gr
3 2
0
C
0
35
2.0
1.0
30
0C
0
C
25
20
C
4.0
L(50) + H
L
150
5.0
H 2O satura
Pressure (fluid) kbars
b)
i te
0361-0128/98/000/000-00 $6.00
600
Bea u voir g r a n
Solute compositions
The compositions of the fluids trapped in the inclusions
were herein estimated from the final melting temperatures of
ice and hydrohalite, the dissolution of solid phases, analysis of
decrepitates, and scanning electron microscopic analysis of
opened inclusions. The first two methods reveal a nearly continuous range of salinity from 0 to 65 wt percent NaCl equiv,
excluding a small gap in the 25 to 35 wt percent interval (Fig.
20b). Although much of the solute is inferred to be NaCl, the
low first-melting temperature, combined with melting of hydrohalite and ice (Oakes et al., 1990), indicates that CaCl2, although usually less than 10 wt percent, locally accounts for up
to 40 wt percent of the solute (Kontak and Clark, 1997a).
Phase relations in the system NaCl-MgCl2-H2O imply that
MgCl2 is also present (Crawford, 1981). In the few cases
where dissolution of both sylvite and halite was observed, the
bulk NaCl/KCl/H2O ratio (wt %) is estimated from the NaClKCl-H2O ternary to be 35:25:40; the maximum NaCl content
is 50 wt percent. Thus, the fluid component of some inclusions is inferred to contain significant quantities of both CaCl2
and KCl.
Fluid composition was also estimated by analysis of decrepitate mounds (Figs. 22, 23; cf. Haynes et al., 1988). Although no attempt has been made to quantify the data in
terms of the bulk fluid chemistry, the results of the analyses
can be used to characterize the composition of the fluid in the
quartz-hosted inclusions. Using both point- and raster-type
analyses, the detected cations, in order of decreasing abundance, are Na, K, Ca, Fe, Mn, and Mg. Traces of Sr and P
occur, but Ba was not detected in any analysis. The abundance of cations other than Na and K may account for the
massive nature of some mounds (Fig. 22), because more
equant shapes develop where the alkalies dominate (D.J.
a)
o
T(H)-T(L)=100 C
1:
1
through dissolution of solid phases (i.e., halite and sylvite),

liquid expansion, and vapor expansion. Whereas homogenization by the first two processes occurs throughout this wide T
range, homogenization by vapor expansion is restricted to
370 to 480C, except for a few cases at 305C. In view of the
possibility of error in establishing the homogenization of
vapor-rich inclusions (Sterner, 1992), microthermometry was
undertaken only on inclusions with the appropriate shape
(i.e., reentrants, as discussed by Roedder (1984, p. 256)). The
fact that the highest value for Th-V is similar to that for Th-L
suggests that the observed measurements are close to the true
trapping temperature. For inclusions containing halite, final
homogenization occurred by either dissolution of halite or expansion of the liquid phase after halite had dissolved (Fig.
21a).
The relationship between salinity and homogenization temperature is shown in Figure 20d. Here, the data are compared
with the fields delimited for the lode mineralization for stages
I, II, III, and IV by Palma (1981) and A.H. Clark (unpub.
data). There is clearly a correspondence and overlap in the
data for fluid inclusions in the quartz phenocrysts and those
hosted by vein minerals. We emphasize the large range in
salinity for fluids homogenizing within the temperature range
300 to 500C, which strongly implies fluid mixing. In contrast, there is a relatively limited range in salinity for inclusions homogenizing below 300C.
L(40) + H
L
1768
te
800
Temperature (C)
FIG. 21. (a) Binary plot of homogenization temperatures for three-phase
liquid-vapor-halite inclusions. Circled numbers 1, 2, 3 represent the three
different homogenization behaviors for liquid-vapor-halite inclusions. The
area A refers to that part of the diagram for which there are no homogenization data (i.e., no Thliquid at <280C), the significance of which is discussed in
the text. The horizontal dashed lines with numbers refer to wt percent NaCl
inferred from dissolution temperature of halite (Bodnar and Vityk, 1994),
whereas the inclined dashed line is a reference line for inclusions displaying
homogenization of halite at 100C above Thliquid, a relationship that has implications for the minimum pressure of entrapment (see text for discussion).
(b) A pressure versus temperature plot for the system H2O-NaCl (after Bodnar, 1994) showing (1) lines of constant liquid-vapor homogenization temperature or iso-Th lines for fluid inclusions containing 40 wt percent NaCl;
(2) the liquidi for two relevant compositions (i.e., liquid[40, 50] + halite); and
(3) the 40 wt percent NaCl vapor-pressure curve for a 40 wt percent NaCl
system (liquid[40] + vapor). The circled numbers 1, 2, 3 represent different
homogenization behavior for liquid-vapor-halite inclusions, as in (a). The
horizontal dashed line refers to the inferred maximum pressure for fluid entrapment on the basis of the difference in homogenization of halite and liquid-vapor in three phase liquid-vapor-halite inclusions (i.e., T(H) T(L) =
5075C). The horizontal solid line with arrow indicates path of isobaric
cooling for the fluids. Also shown are the solidi for two relevant granite systems, one a volatile-rich (F, B) system (Beauvoir granite; Pichavant et al.,
1987), and the other the water-saturated haplogranite (Tuttle and Bowen,
1958). Note that the inclusion data are consistent with exsolution of a fluid
from a volatile-rich Beauvoir-type granite at low pressures with subsequent
isobaric cooling.
1768
1769
10 m
FIG. 22. Back-scattered electron image for fluid inclusion decrepitate
mound, released from a quartz phenocryst in the San Rafael granite. The
variation in brightness reflects compositional variability.
a)
Na
Kontak, unpub. data). In most cases the Na/K ratio is much

greater than unity, but K dominates in several mounds (Fig.
23a). There is a decoupling of K from Ca and Fe (Fig. 23a, b)
and also from Mn and Mg (not shown), whereas (4) Na is generally coupled with Fe (Fig. 23b) and to a lesser extent Ca
(Fig. 23a, c), although Fe appears to be decoupled from Na
in the most saline fluids (Fig. 23e). Finally, the existence of a
Ca-dominated fluid is confirmed, consistent with some lowtemperature first-melting and the hydrohalite-ice melting
relationships. The high concentrations of Fe in some fluid inclusions is also demonstrated by SEM analysis (A.J. Anderson, pers. commun., 1987) of several opened inclusions in
quartz phenocrysts in a single sample of weakly altered granite, which revealed numerous Fe chloride daughter crystals
and lesser numbers of Fe-Mn chloride crystals.
Because of the dispersed areal distribution of our observations on fluid inclusions in the quartz phenocrysts, it is difficult to correlate specific fluid cation contents with alteration
facies. However, Fe-rich fluids may be more prevalent in
proximity to the major lodes within the San Rafael granite, in
conformity with the Fe metasomatism recorded by their chloritized envelopes.
d)
wt. % Na
60
Ca
0
0
e)
20
30
40
50
60
40
20
0
10
20
30
40
50
wt. % Na
Na
f)
wt. % Ca
Fe
10
wt. % K
Na
Fe
c)
20
wt. % Fe
b)
40
8
6
4
2
0
Ca
10
20
30
40
50
wt. % Na
FIG. 23. Binary and ternary element plots for analyses of decrepitate mounds (results normalized to 100 wt %) released
from fluid inclusions hosted by quartz phenocrysts from the San Rafael granite.
0361-0128/98/000/000-00 $6.00
1769
KONTAK AND CLARK
Temperature-salinity relationships and correlation

with mineralization stages
The data for quartz phenocryst-hosted fluid inclusions may
be grouped (Fig. 20d) into three domains: a high-salinity
trend (>35 wt % NaCl equiv) with Th = 260 to 530C; a hightemperature (300480C), variable-salinity (323 wt % NaCl
equiv) group; and a lower-salinity (<10 wt % NaCl equiv) and
lower-temperature (200 to 300C) group. Although the highsalinity inclusions reflect saturation or near-saturation of the
fluid with respect to halite, it is significant that homogenization of these inclusions occurs either by dissolution of halite
or expansion of the L phase (Fig. 21a). From Figure 20d, it is
evident that the data for stage I barren quartz-tourmaline
veins are similar to those for the high-temperature, highsalinity quartz phenocryst-hosted inclusions of this study. The
main mineralizing stages, II and III, correspond to the majority of the fluid inclusion data in this study, although numerous inclusions in quartz phenocrysts homogenize at
higher temperatures than those recorded by Palma (1981)
and A.H. Clark (unpub. data) for the lodes (420C). Stage
IV of the lode paragenesis formed from fluids with uniformly
low salinities (5 wt % NaCl equiv) and temperatures
(170300C: Palma, 1981), overlapping with a large proportion of the data collected for quartz phenocryst-hosted inclusions in this study.
Pressure of fluid trapping
The pressure of entrapment for the earliest-stage fluids
preserved in the quartz phenocrysts is estimated to have varied from 150 to 615 bars (Kontak and Clark, 1997a), on the
basis of microthermometric observations on inclusions that
we infer record fluid unmixing in the uppermost levels of the
stock and for which the temperatures of halite dissolution and
homogenization to liquid are available, and by applying the
method of Bodnar and Vityk (1994; Fig. 24). We emphasize
that this does not imply that higher fluid pressures did not
occur, but that the fluids exhibiting appropriate homogenization behavior and recording these higher pressures have not
specifically been encountered. In fact, the homogenization
behavior of types iii and iv inclusions, where Th(H) exceeds
Th(L) by 50 to 100C, and rarely up to 200C, indicates that
pressures as high as 2 kbars must have been attained, as discussed below. Given the high-level setting of the San Rafael
granite, such elevated pressures plausibly record fluid overpressuring caused by the tensile strength of the overlying
rock, preventing fluid escape during second boiling. That
fluid pressure fluctuated at a later stage is implied by the multiphase hydrothermal brecciation textures characteristic of
the stage II assemblages in the veins (e.g., Palma, 1981).
As proposed by Cline and Bodnar (1994), and also discussed by Bodnar (1994), the three different modes of homogenization of the halite-bearing inclusions are also consistent with fluctuations in fluid pressure combined with cooling
of the fluid (Fig. 21a), as modeled for a 40 wt percent NaCl
fluid in Figure 21b. The higher-salinity fluids represented in
Figure 21a can also be modeled as for the 40 wt percent fluid
(e.g., Bodnar and Vityk, 1994); the L + H L plane was displaced to higher temperatures in P-T space with increasing
salinity. The retrograde evolution of similar high-salinity
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1500
Pressure (bars)
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wt. % NaCl
30
40
50
60
70
1000
500
CP
0
100
300
L+
V+
500
700
Temperature (C)
FIG. 24. Plot of pressure vs. temperature with vapor-pressure curves for
H2O-NaCl solutions with salinities of 30 to 70 wt percent (from Bodnar and
Vityk, 1994). Also shown are the liquid-vapor curve for H2O (0), the critical
point (CP) and the three phase (liquid + vapor + halite: L + V + H) curve in
the H2O-NaCl system. Plotted are homogenization data for fluid inclusions
from San Rafael that represent trapping in a two phase field (i.e., fluid unmixing demonstrated). See Bodnar and Vityk (1994) for details of this plot.
fluids has been discussed for the Capitan pluton, New Mexico (Ratajeski and Campbell, 1994; Campbell et al., 1995). In
Figure 21a, the three P-T regimes of entrapment, representing different fluid types in terms of bulk density, are distinguished on the basis of the mode of homogenization: by
vapor-phase disappearance, by simultaneous halite dissolution and inclusion homogenization, and by halite dissolution.
That homogenization occurs by all three processes is consistent with a model involving fluid evolution through a combination of cooling and overpressuring, given the shallow
crustal setting. The inclusions that homogenized at temperatures above circa 500C must have been trapped at no more
than 0.5 to 1 kbar for salinities of circa 40 wt percent NaCl
equiv, because the iso-Th lines intersect the solidus of a representative evolved granite at this point (e.g., Beauvoir granite in Fig. 21b). Higher pressures and by inference higher
temperatures are, we argue, inconsistent with the clearly secondary context of the fluids in a rock that had attained brittle
conditions that permitted development of microcracks along
which the fluids infiltrated. Cooling of this fluid with concomitant overpressuring would lead to trapping of inclusion
types 2 and 3. The absence of data in area A of Figure 21a indicates that when fluids of appropriate salinity (i.e., 35 wt %
NaCl) were circulating, overpressures could not have existed,
as occurred for fluid type 3, or the inclusions would exhibit
homogenization via Th (H) > Th (L). This is an additional argument favoring a generally low- pressure environment during mineralization, but with overpressuring accounting for inclusions (fluid 3) with Th(H) > Th(L).
The generally lower pressures of formation we infer are in
agreement with the low, epizonal pressures estimated from
fluid inclusion data for vein mineralization in both the San
Rafael and Quenamari sectors of the district. Hannington
1770
(1983) estimated that the pressures attending vein formation

at Quenamari (Veta Nazareth) may have been as low as 180
bars, whereas Palma (1981) concluded that the main lode
stage (stage II) at San Rafael formed at 165 bars. These estimates are in keeping with the shallow level of emplacement
of the San Rafael granite and Quenamari granite inferred
from the petrologic features and the intensely brecciated nature of the veins. An alternative model would involve quenching, perhaps through dilution with a cool fluid, as discussed
above to account for the salinity-Th correlations in Figure
20d. Given the structural features of the mineralized veins, a
model involving both pressure fluctuation and cooling is preferred. In view of the temporal hiatus between initial retrograde boiling and ore formation, it is plausible that the transition from highly saline stage I fluids to the more dilute,
cooler fluids that generated stages II and III coincided with a
change from dominantly lithostatic to dominantly hydrostatic
conditions.
Ore-Genetic Modeling
The large-scale hydrothermal alteration system we document herein introduces a new perspective to the ore-genetic
model for this world-class lithophile-metal deposit. We propose that the Sn-Cu mineralization was generated through an
exceptional conjunction of magmatic, regional and local tectonic, and hydrothermal processes, many of which are
broadly shared by other major sulfide-cassiterite centers
(Smirnov, 1937), a diversified but coherent clan that now
dominates prospective hardrock cassiterite mineralization
globally (Clark, 1995; Clark et al., 1993, 1995). Such common,
if not invariable, characteristics include parental peraluminous, reduced, granitoid magmas, generally of high-temperature Lachlan, rather than Himalayan type, that exhibit evidence of commingling and mixing with mantle-derived,
oxidized, mafic melts, and that widely include K-rich lamprophyric members. Subordinate volumes of strongly fractionated, commonly F- and/or B-enriched melts may have been
closely linked to ore formation, but their role remains uncertain. Second, chalcopyrite, iron sulfides and, less consistently,
sphalerite are abundant, representing integral constituents of
the ores. Third, the ore-forming fluids are of both magmatic
and nonmagmatic, most commonly meteoric, origin, and, finally, ore deposition significantly postdated the initiation of
retrograde boiling in an epizonal magma chamber, and it was
constrained by structures imposed by regional tectonism
(Clark et al., 2000). We regard these varied factors as ultimately responsible for the extreme shallow-crustal concentration of Sn, although the dilational jogs on the main San Rafael
Lode structure (Fig. 2) undoubtedly controlled the development of the enormous orebodies that dominate the deposit.
Despite the close association of hydrolytic wall-rock alteration with both Sn and Cu ore-zones, it is clear that the San
Rafael Lode system differs in almost all salient features from
the widespread low-grade, greisen-bordered, sulfide-poor,
cassiterite (-wolframite) vein swarms that have been the subject of most investigations of lithophile-metal mineralization.
In contrast, as was initially emphasized by Palma and Clark
(1982), the San Rafael deposit is remarkably similar to the
classic Cornwall-type Sn-Cu-polymetallic lodes, particularly
those of the Camborne-Redruth district (Clark et al., 1995).
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San Rafael does not conform to the tin porphyry model of Sillitoe et al. (1975), in that cassiterite deposition was entirely
focused within throughgoing brittle shear zones, and retrograde boiling processes did not immediately give rise to the
mineralization. The major goals of this contribution were to
determine whether the P-T-X evolution of the dispersed fluids documented herein corresponded to that of the Sn-Cu
lodes, and thereby to evaluate the extent to which the structurally localized ore formation process is reflected throughout
a considerably greater area by alteration assemblages and,
specifically, fluid inclusions trapped in the granitic host rocks.
Significance of cryptic pervasive alteration
The upper 700 m of the San Rafael stock widely preserves
coarsely phenocrystic megascopic textures and even mineral
associations, e.g., poorly ordered alkali feldspars exhibiting
film perthite lamellae, of unambiguous magmatic origin
(Brown and Parsons, 1989). However, the majority of surface
and underground exposures of both stocks and dikes, outside
of the well-defined alteration envelopes of the veins, record
moderate to intense alkali metasomatism and/or hydrolytic alteration. The presence of pervasive, alkali-dominant alteration within rare-element (Sn-W-Nb-Ta)mineralized felsic
systems has been documented globally (e.g., Pollard, 1983;
Witt, 1984, Pollard and Taylor 1986; Charoy and Pollard,
1989), and there is a consensus that alkali redistribution occurred during circulation of hydrothermal fluids, a process
manifested by a vertical zonation of alkalis in intrusive cupolas that contain Na-rich apices and K-rich cores (Orville,
1963; Lagache and Weisbrod, 1977; Pichavant, 1983; Lagache, 1984; Webster, 1995). Such metasomatism may be dispersed or concentrated along veins, and the geochemical and
mineralogic similarities of these alteration facies reveal a cogenetic origin (Pollard, 1983; Witt, 1988), the former recording entrapment of late magmatic or orthomagmatic fluids,
and the latter the involvement of hydrofracturing (Pollard
and Taylor, 1986; Titley, 1994). In addition, this early alkali
metasomatism is almost ubiquitously succeeded by hydrolytic
alteration.
The nature and distribution of the early alkali metasomatism in the San Rafael granite strongly support an origin
through the subsolidus infiltration of fluid rather than the in
situ retention of a late-stage magmatic brine, such as is inferred for the essentially closed systems represented by the
tourmaline orbicules in the Seagull batholith (Samson and
Sinclair, 1992) or the cassiterite pipes of the Zaaiplaats deposit (Pollard et al., 1989, 1991), the former barren and the
latter high grade, but modest in scale. The alteration in the
San Rafael granite is variable in both intensity and distribution, fluid infiltration having been controlled by parameters
such as fluid/rock ratio and permeability (cf. Ferry, 1979).
The lack of a relationship between the alteration and the
veinlets and the absence of vein-selvage alkali alteration, such
as is observed in porphyry deposits, indicate that fluid migration was not a consequence of fracture-controlled permeability. The selective replacement and incremental progression of
the alteration normally associated with porphyry deposits
would not have provided an efficient mechanism for formation of a large and high-grade tin deposit (Heinrich, 1990),
even if the temperatures were not excessive for cassiterite
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KONTAK AND CLARK
saturation. Whereas comparative relationships among the

various granitic stocks of the Picotani intrusive suite (Kontak
and Clark, 1988) strongly suggest that the K metasomatism
exhibited by the San Rafael granite is an inherently favorable
feature from the exploration standpoint, no significant areal
zonation in alteration intensity exists with respect to the major
lode concentration.
The Al/Si ordering relations in the alkali feldspar provide
insight into the conditions of the alkali metasomatism. The
absence of microcline, normally the dominant K-rich alkali
feldspar in similar settings (e.g., Martin and Bowden, 1981),
is consistent with temperatures above the orthoclase-microcline inversion at circa 450C (Smith, 1974). In contrast, the
compositions of the Na and K feldspar phases, inferred from
both microprobe (Fig. 10) and X-ray powder data, suggest
that equilibration persisted to temperatures as low as 300C.
There was evidently insufficient strain energy associated with
this lower-temperature alteration to promote ordering in the
feldspars (Brown and Parsons, 1989).
Magmatic versus nonmagmatic fluid components
and integration with paragenetic stages
The secondary fluid inclusions hosted by the quartz phenocrysts of the San Rafael granite provide evidence of the nature of the metasomatic fluid that infiltrated the stock. The
following three distinct fluid populations have been recognized: a spectrum of hypersaline Na-K fluids of 35 to 65 wt
percent NaCl equiv that homogenize between 280 and
540C; moderately saline fluids of 10 to 20 wt percent NaCl
equiv that homogenize at 300 to 470C; and a low-salinity
fluid of 0 to 10 wt percent NaCl equiv that homogenizes at
200 to 350C. Also present is a low-density, vapor-rich inclusion population for which limited thermometric data indicate
a salinity of range of 4.2 to 19.4 wt percent NaCl equiv (n =
10) and homogenization temperatures of 370 to 480C overall, most falling in the 380to 400C range. The Th values and
salinities of these inclusions overlap with the high-temperature limit of the vein stage II fluids. Petrographic observations strongly support the coexistence of all types of inclusions
along individual healed fracture planes, providing evidence
for fluid unmixing. The question that must therefore be addressed is whether the spectrum of fluid inclusion composition and temperature, in both the pervasive alteration and
lode environments, may be explained through the evolution
of a single magmatic brine or, alternatively, requires the involvement of two or more hydrothermal fluids of disparate
origin.
In the magmatic-hydrothermal model, associations of highand low-salinity aqueous fluids could record either unmixing
of an original moderate-salinity fluid or, at low pressure, direct exsolution of associated brine and vapor from the magma
(e.g., Bodnar et al., 1995a). Although these processes may
have contributed to the fluid inclusion populations at San
Rafael, it is significant that, in both the quartz phenocrysts
and veins, a significant proportion of the liquid-vapor inclusions that homogenize at 200 to 300C yielded ice-melting
temperatures of 0 to 0.5C, evidence for negligible salinity.
The various potential evolutionary paths of a magmatic brine
would not, according to phase equilibrium data for the system
H2O-NaCl (Bodnar et al., 1985a), yield fluids with less than 2
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to 3 wt percent NaCl. We therefore advocate the involvement

of nonmagmatic, most plausibly meteoric, waters with salinities in the range 0 to 0.7 wt percent NaCl equiv, in agreement
with many other studies of epizonal magmatic-hydrothermal
environments (e.g., Norton, 1982; Dong and Zhou, 1996;
Hezarkhani and Williams-Jones, 1998). Indeed, the inferred
overall trajectory of hydrothermal evolution in the upper section of the San Rafael stock was similar in almost all salient respects to that defined in many magmatic-hydrothermal centers, including the great majority of porphyry copper
deposits, in which evidence of late-stage meteoric water incursion is almost ubiquitous.
As discussed previously, and illustrated in Figure 20d, there
is an excellent correlation between the fluid inclusion data
from this study and those for the vein stages. Interpretation of
the links between the dispersed fluids and those channeled by
the major lode structures must, however, take into account
the apparent circa 2 m.y. hiatus between mineralization stages
I and II. The formation of stage I quartz-tourmaline veins is
plausibly related to the high-salinity, high-temperature fluids
that have a signature typical of retrograde boiling and presumably coexisted with the vapor-rich fluids. These inclusions, therefore, preserve a record of an early period of fluid
infiltration into the San Rafael granite and its surrounding
ring dikes. The introduction of the moderately saline (25 wt
% NaCl equiv) fluids may have begun late in stage I but was,
we infer, largely coincident with stages II and III mineralization, at which time mixing with a more dilute fluid yielded the
observed trends in temperature-salinity space (Fig. 20d). The
separation of these fluid events in time, but not space, is supported in part by the apparent hiatus in the data of Figure
20d, a realistic inference given the substantial amount of data
collected from numerous samples. We note, however, that we
cannot discriminate between the stage II and III fluids and
potential candidates for the parental fluid of appropriate
composition that unmixed to give rise to the highly saline fluids of stage I. The terminal stage IV fluids, dominantly of lowsalinity nature, indicate that the magmatic contribution to the
hydrothermal system had waned by this time.
Implications of pervasive metasomatism
for Sn and Cu mineralization
The present study of quartz phenocryst-hosted secondary
inclusions has demonstrated that the San Rafael stock was
penetrated by a wide range of hydrothermal fluids that strikingly mimic the Th-salinity relationships of those that deposited quartz, cassiterite, and chalcopyrite in the major lodes
and very probably paralleled the overall evolutionary history
of the mineralization. Paradoxically, however, there is no economically significant disseminated or veinlet-controlled Sn or
Cu mineralization in either the San Rafael or Quenamari intrusive centers. This is, in our opinion, a problematic aspect
of the database. The lack of dispersed cassiterite is particularly striking where the initiation of semipervasive hydrolytic
alteration at temperatures below circa 450C paralleled the
fluid evolutionary event that generated the enormous stage II
orebodies of the San Rafael Lode (Fig. 2). In contrast, widespread development of sericite in the East Kemptville
leucogranite, Nova Scotia, was associated with the introduction of several hundred parts per million Sn through much of
1772
the intrusion (Kontak et al., 1995). The absence of such dispersal at San Rafael could reflect one of two factors: the fluids entering the San Rafael granite were depleted in Sn and
Cu, or the dispersed fluids were different in source and/or
composition from those related to lode mineralization. We
consider the first to be the more probable in view of our fluid
inclusion studies. Late fluid ingress to the upper part of the
San Rafael granite was overwhelmingly controlled by the
major, evolving shear zones, and particularly that which hosts
the San Rafael Lode, channeling both the rise of magmatic
Sn- and Cu-bearing brines and the incursion of cool, dilute
ground waters, thereby providing a constrained environment
in which abrupt mixing of the two fluids took place.
There are several potential corollaries to this model. First,
because the Th-salinity relationships of the resulting mixed
hydrothermal fluids involved in stages II and III were similar
and well within the range in which chalcopyrite is precipitated, e.g., porphyry Cu deposits (Hezarkhani and WilliamsJones, 1998), the absence of chalcopyrite and other sulfides in
stage II assemblages may indicate that neither Cu nor reduced S was present in significant amounts in either the hightemperature brine or the meteoric water at this time. This absence, in turn, predicates a late-stage process in which copper
and sulfur became available, perhaps involving the mixing of
residual granitic magmas with newly introduced, oxidized,
mafic melts, either lamprophyric or basaltic. It is also possible
that Sn was largely derived from the mafic melts, particularly
the minette (A.H. Clark, unpub. data), as has been proposed
for the major South Crofty lode system, Cornwall (Clark et
al., 1993; Chen et al., 1996). Second, the barren nature of the
stage I veins, stockworks and breccias reflects two, interrelated factors: in this widespread early episode, the magmatic
brines rising through the upper part of the San Rafael granite
stock did not encounter large volumes of meteoric water; and
this absence of meteoric water precluded both the large-scale
quenching and salinity reduction that were prerequisites for
cassiterite and chalcopyrite deposition.
Significance of age relationships
Stage I barren veining was broadly contemporaneous with
the cooling of the upper kilometer of the San Rafael granite
through the Ar-retention temperature of biotite and probably
took place less than 1 m.y. after granite intrusion at 24.65
0.2 Ma (Clark et al., 2000). In contrast, the economic lode was
emplaced at circa 21.9 to 22.7 Ma; the 40Ar/39Ar plateau dates
for stage II hydrothermal muscovites and stage III adularias
(low sanidine) were unresolvable within 2 error. By this
stage, the upper parts of the San Rafael granite and Quenamari granite stocks had cooled to at least 230C. Clark et al.
(2000) propose that such delays in the initiation of ore deposition, a feature also shown by the Cornubian Sn-Cu lodes
and the Pasto Bueno W-Cu-Ag veins, northern Peru, may be
characteristic of world-class lithophile-metal mineralization,
constituting a significant departure from, for example, porphyry Cu deposits in which retrograde boiling is immediately
responsible for stockwork development and ore metal deposition. Thus, in Cornubia, it is clear that the sparse deposition
of cassiterite and chalcopyrite in early veins associated with
retrograde boiling was not the result of excessive fluid temperatures or inappropriate Cl contents, and the hydrothermal
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fluids possessed Th and salinity ranges similar to those which

generated the later major Sn-Cu lodes (Chen, 1994; Chen et
al., 1996).
At San Rafael, cassiterite and chalcopyrite mineralization
was confined to brittle shear zones that formed in response to
regional tectonism rather than to cooling stresses related to
intrusion. Similarly, at Pasto Bueno, wolframite deposition
was initiated, some 2 m.y. after retrograde boiling and pervasive development of greisen in the host upper Miocene Consuzo stock, within dilatant structures that developed during
the initial uplift and unroofing of the contiguous Cordillera
Blanca batholith (Clark et al., 2000; A.H. Clark, unpub. data).
It is therefore proposed that intrusion-ore formation hiatuses
may play a major role in the concentration of the lithophile
and associated base and precious metals. This may be evidence for the accumulation of volumes of metal-enriched
dense brines in the interiors of the parental granitoid plutons,
where they may coexist with small bodies of specialized
magma, such as would be represented by the tourmaline
leucogranite at San Rafael. Upward expulsion of the ore
metal-rich brines would, in this model, be caused by regional
tectonic activity, involving uplift, exhumation and, probably,
renewed incursion of granitic and/or mafic melts.
Conclusions
Despite the absence of dispersed, porphyry-style Sn or Cu
mineralization at San Rafael, the semipervasive hydrothermal alteration of the upper 700 m of the host stock records
an evolution closely linked to that of the early barren and
later economic veins and lodes. On a district scale, as recognized by Kontak and Clark (1988), there is a correlation between the predominant alkali metasomatic facies and intensity of Sn-Cu mineralization, and enrichment in K, as at San
Rafael proper, was apparently more favorable than that in
Na, as at Quenamari and Santo Domingo. Intrusions, such as
the Antauta granite, that preserve magmatic sanidine are not
known to be associated with significant lithophile or basemetal mineralization.
Precipitation of cassiterite and, subsequently, chalcopyrite
at San Rafael was almost entirely confined to the major shear
zones, because only therein did the rising metal-rich brines
encounter pristine meteoric waters. Development of chlorite
in the lode envelopes may have promoted the deposition of,
particularly, cassiterite through fluid neutralization, but this
process is unlikely to have contributed more than marginally
to the extreme ore grades exhibited by the Veta San Rafael.
Whereas essentially undiluted high-temperature magmatic
fluids permeated much of the apex of the San Rafael stock before, and in the initial stages of, development of the northnorthweststriking fractures, migration of the lower-temperature, mixed fluids was largely channeled along these
structures and, we infer, only spent, Sn- and Cu-depleted effluent penetrated the surrounding granite.
The most remarkable observation made in the present
study is that, although the fluids that generated alkali and hydrogen metasomatism throughout much of the apex of the
San Rafael granite did not cause the deposition of disseminated cassiterite or chalcopyrite, their trajectory in Th-salinity
space mimicked that of the fluids responsible for the lode
mineralization. The microthermometric research documented
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KONTAK AND CLARK
herein focused on the largest, least problematic, fluid inclusions hosted by quartz phenocrysts in samples from the restricted outcrop (Figs. 1c, 2a) of the San Rafael granite, in
none of which cassiterite occurs as either disseminated grains
or in veinlets. Nonetheless, our experience suggests that the
evolutionary history of the hydrothermal system that generated the world-class San Rafael Lode could probably be established through study of a small number of quartz phenocrysts from many sites in the exposed depth interval of the
stock and its surrounding dikes. This observation has unambiguous implications for mineral exploration in this and other
comparable provinces.
Acknowledgments
This study, a contribution to the Queens University Central
Andean Metallogenetic Project (QCAMP), is an outgrowth of
the senior authors doctoral research. Funding was provided
by Natural Sciences and Engineering Research Council of
Canada grants to A.H. Clark and Edward Farrar. Field work
was supported logistically by Minsur S.A., Lima, through the
good offices of Fausto Zavaleta Cruzado and, latterly, Lucio
Pareja Chvez. Underground studies were unselfishly assisted
by former mine manager, Adolfo Mdico Bao, and by numerous mine geologists, particularly Jlver Alvarez Romero and
Pastor Luque Mlaga. QCAMP research in southern Peru
would not have been possible without the enthusiastic support and encyclopedic knowledge of Mario Arenas Figueroa,
consulting geologist.
Geochronologic data were determined by Edward Farrar
and Yanshao Chen, at Queens University, and by Hardolph
Wasteneys, Royal Ontario Museum, Toronto, in both cases
supported by NSERC. Our indebtedness to Vicente Palmas
pioneering contributions at the outset of this research is
clearly evident from our text. Alan Anderson is thanked for
carrying out SEM scans of daughter minerals. Discussions
with consulting geologists David Kerr and Robert Mason
have been particularly helpful. Bob McKay, Dalhousie University, is thanked for his assistance with the electron microprobe analysis, while Jim Reynolds provided advice on the interpretation of fluid inclusion relationships, determined at
the Nova Scotia Department of Natural Resources. Joan
Charbonneau expertly typed the manuscript, and Tom Ullrich assisted with the figures.
Nigel Grant, Jos Perell, Jean Cline, Roger Taylor, and an
anonymous referee, as well as the indefatigable editor, promptly
and constructively reviewed the original manuscript.
Minsur, S.A., has given permission for publication of this
manuscript, which is prepared in honor of Adolfo Mdico,
murdered at the San Rafael mine by members of the Sendero
Luminoso, December 15th, 1986.
July 31, August 21, 2002
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APPENDIX
Analytical Procedures
Whole-rock samples were analyzed at Queens University
for major and minor (Si, Ti, Al, Fe, Mg, Ca, Na, K, Mn, P) and
trace (Rb, Sr, Ba, Nb, V, Cr, Zr, Y, Sn) element content using
a Siemens Model VRS X-ray vacuum spectrometer. Additional analyses for trace elements (Cu, Pb, Zn, Ni) were carried out on an Instrumentation Laboratory Model 251 atomic
absorption spectrophotometer, and ferrous iron determinations were obtained using a modified titrametric method of
Wilson (1960). Full details of sample preparation and analyses, along with standards, duplicates, precision, and accuracy
are given in Kontak (1985). Rare-earth element abundances
were determined at Memorial University using the thin-film
X-ray fluorescence method of Fryer (1977).
Analysis of silicate minerals was carried out on polished
thin sections with a JEOL 733 Superprobe at Dalhousie University (Halifax, Nova Scotia) in the energy dispersive mode,
and using the following operating conditions: 1 to 3 m beam
diameter but defocused to 10 m for feldspars; 10 nA beam
current; and 15 kV accelerating voltage. F in biotite was determined using wavelength-dispersive spectrometry on the
same instrument. Back-scattered and secondary electron images were collected for examination of textural and mineralogic details of the samples, as discussed in the text. Major
and trace element compositions of high quality mineral separates (biotite, alkali feldspars) were obtained using the same
X-ray fluoresence analytical procedures as for the whole
0361-0128/98/000/000-00 $6.00
rocks. Trace elements (Li, Mo, Cs, Hf, Ta, Bi, Th, U, rare
earth elements) were measured for alkali feldspar separates
by solution chemistry inductively coupled plasma-mass spectrometer (Memorial University, Newfoundland) using the
method of Jenner et al. (1990). Fluid inclusion thermometric
measurements were obtained using a U.S. Geological Surveytype gas-flow heating/cooling stage housed at the Nova Scotia
Department Natural Resources, Halifax (see Kontak [1998]
for full details of operating conditions). Precipitate or decrepitate mounds generated from artificial thermal decrepitation of fluid inclusions (Haynes et al., 1988) were also analyzed in the energy dispersive spectrometer mode using the
JEOL 733 Superprobe with full imaging facilities, using the
operating conditions noted above. Alkali feldspars were analyzed for their Al/Si ordering/disorder relationships using a
Picker X-ray diffractometer with Ni-filtered Cu radiation ( =
1.5418 A; 40 kV; 18 mA). A single scan was made for each
sample from a 2 angle of 13o to 70o at a goniometer speed
of 1o per minute. A silicon internal standard was used to
check for and correct any peak shift. The order/disorder relationships and bulk compositions ofthe phases were determined with reference to the (060)-(204) diagram of (Wright,
1968; Stewart and Wright, 1974). Further details of the
methodology employed, including estimates of precision and
accuracy, are given in Kontak (1985).
1777

Genesis of Giant San Rafael Tin Deposit Peru-Pervasive Alteration

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Genesis of Giant San Rafael Tin Deposit Peru-Pervasive Alteration

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Economic Geology

Vol. 97, 2002, pp. 17411777

Corresponding author: e-mail, charbon@geol.queensu.ca

mineral exploration. Predictably, therefore, they have been

KONTAK AND CLARK

The San Rafael Deposit

ALTERATION & HIGH-GRADE Sn MINERALIZATION, SAN RAFAEL, PERU

Veta San Rafael

moraines, scree, ice

Ambo Group (Mississippian)

Sandia Formation (Ordovician)

major Camborne-Redruth district of the Cornubian province,

narrow and discontinuous in the hornfelsic rocks adjacent to

KONTAK AND CLARK

Cu grade contours (%)

ALTERATION & HIGH-GRADE Sn MINERALIZATION, SAN RAFAEL, PERU

Hypogene Paragenetic Relationships of San Rafael Lode

22.4 - 22.7 0.7 Ma

21.9 - 22.0 0.2 Ma

youngest stage II assemblages, dominating the San Rafael

KONTAK AND CLARK

relationship first documented by J. Alvarez (unpub. report to

ALTERATION & HIGH-GRADE Sn MINERALIZATION, SAN RAFAEL, PERU

Age relationships of ore deposition

The San Rafael granite stock and similar Quenamari granite

KONTAK AND CLARK

The petrography and chemistry of the least-altered samples

cordierite in a hypidiomorphic granular matrix with variable

ALTERATION & HIGH-GRADE Sn MINERALIZATION, SAN RAFAEL, PERU

KONTAK AND CLARK

Despite the epizonal context of the San Rafael granite,

69.05 68.40 73.67 74.11 69.61 69.80

Chondrite-normalized REE values

Sample number and degree of alteration of granite

Trace elements (ppm)

COCA COCA COCA COCA COCA COCA COCA COCA

ALTERATION & HIGH-GRADE Sn MINERALIZATION, SAN RAFAEL, PERU

KONTAK AND CLARK

corresponding to the Ni-NiO buffer in ternary Fe+2-Fe+3-Mg+2

ALTERATION & HIGH-GRADE Sn MINERALIZATION, SAN RAFAEL, PERU

least altered granite (SRG)

FIG. 8. Chondrite-normalized rare-earth element plots for various populations of the

Si per formula unit

Si per formula unit

Structural formula (11 oxygens)

Granite, sample number, and point

ALTERATION & HIGH-GRADE Sn MINERALIZATION, SAN RAFAEL, PERU

variation in major element contents, with Fe/(Fe + Mg) = 0.5

internal corrosion surfaces recording complete dissolution,

The alkali feldspar is perthitic and exhibits strong (201)

End member (mol %)

Structural formula (8 oxygens)

Granite, sample number, point, and phase

ALTERATION & HIGH-GRADE Sn MINERALIZATION, SAN RAFAEL, PERU

*Mol % Or determined on mineral separates by X-ray fluoresence

Petrology of Metasomatized Granite

pseudomorphs after cordierite (e.g., Fig. 4). The granites are

San Rafael &

Santo Domingo &

KONTAK AND CLARK

Petrography of alkali-metasomatized granite

Our studies of outcrop and underground exposures demonstrate