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The Cuajone copper porphyry-type deposit

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11th Biennial SGA Meeting, Antofagasta,. 26–29 september 2011
The Cuajone copper porphyry-type deposit (Perú):
Characterization and correlation of solid inclusions in
pyrite with types of hydrothermal alteration
Carmen Juli Sucapuca Goyzueta
Instituto de Geociências, Universidade de São Paulo, Rua do Lago 562, 05508-080 – São Paulo -SP, Brazil
Silvio Roberto Farias Vlach
Instituto de Geociências, Universidade de São Paulo, Rua do Lago 562, 05508-080 – São Paulo -SP, Brazil
Abstract. The Cuajone mine (Moquegua, Perú)
corresponds to a porphyry copper-type deposit formed in
the Toquepala Group volcanic. Hydrothermal alteration
and mineralization were developed in connection with the
late emplacement of quartz monzonite, quartz latite,
porphyritic micrograno-diorite, microtonalite and
porphyries. Both the Toquepala Group and the intrusive
rocks are affected by potassic, propylitic, and sericitic
type of hydrothermal alteration. Pyrite, containing either
micrometer-sized intergrowths of chalcopyrite and
pyrrhotite, cubanite and mackinawite or pyrrhotite alone,
as solid inclusions, were the subject of this study. The
intergrowth types were classified according to their
morphological properties. When considering frequency
and relative abundance of the sulfide assemblages that
constitute inclusions in pyrite, a correlation with the type
of hydro-thermal alteration can be established. Pyrrhotite
occurs in all types of hydrothermal alteration, but it is
predominant in the potassic zone. Cubanite, even if far
less abundant, is typically associated with the sericitic
alteration but it also occurs in the potassic and propylitic
zones. Mackinawite is most common in the propylitic
zone. The observed sulfide mineral associations
suggests that they evolved in a temperature range from
500°C down to 180°C.
Keywords. pyrite, solid inclusions, porphyry copper,
hydrothermal alteration, sulfide intergrowth types.
1 Introduction
The Cuajone mine is located in the Pacific Cupriferous
Province, in the western Andes, between 3150 to 3500
m.a.s.l, Moquegua State – southern Perú (17º 02’ S and
70º 42’ W).
Pyrite (py) and chalcopyrite (cp) are the most
abundant primary sulfides, followed by supergene
covellite and chalcocite. Other sulfides occur in very
small quantities, such as pyrrhotite (po), cubanite (cb)
and mackinawite (mck). These sulfides typically occur
as solid inclusions in pyrite and chalcopyrite, forming
morphologically varied intergrowths in pyrite. The
literature on solid inclusions in primary sulfides in
copper porphyry-type deposits is relatively scarce,
particularly regarding the Peruvian deposits. The only
detailed work on the subject is by Canchaya (1993).
Petrography of 77 samples from 22 drill cores placed
along three sections of the open pit were studied to
define the morphology of pyrite solid inclusions and
correlate sulfide mineralogy with alteration type.
2 Hydrothermal alteration types
The host rocks of the Cuajone deposit are andesitic
and rhyolitic volcanics of the Toquepala Group. The
hydrothermal alteration types that affect the andesite
are: - vein-filling potassic, represented by K-feldspar
and quartz veins. Pervasive and selectively pervasive
biotitization may be associated with this type of
alteration and is characterized by biotite-
magnetite±anhydrite±chlorite±sericite. – propylitic,
characterized by the chlorite-carbonate-epidote-
biotite±clays±sericite±quartz±zeolites assemblage.
Some samples present quartz±sericite, wich is
considered a sericitic type alteration. However the
possibility that it represents silicification is not ruled
out. In fact, a spatial superimposition of these three
types of alteration appears to occur in the andesite.
In the rhyolite, the sericitic alteration is dominant and
appears as either pervasive, selectively pervasive, or as
the vein-filling type. It is characterized by sericite-
quartz±clays and sericite-quartz-pyrite. Propylitic
alteration was recognized in an altered rhyolite sample
by the presence of carbonate and chlorite.
The intrusive bodies responsible for the hydrothermal
alteration and mineralization belong to the first
magmatic pulse and described below. A second pulse
occurred but will not be further considered.
The microgranodiorite porphyry is hydrothermally
affected by a combination of selectively pervasive to
vein-filling propylitic and potassic alterations. The
former contains the assemblage chlorite-sericite-
carbonate-epidote, while quartz-K feldspar appears in
the later. Four samples tentatively classified as
microgranodiorite to microtonalite porphyry contain
sericite-quartz and carbonate-clays-chlorite±epidote,
characterizing the combination of selectively pervasive
sericitic and propylitic alterations.
The microtonalite porphyry is also altered by a
combination of selectively pervasive to vein-filling
propylitic (chlorite-carbonate±epidote±quartz) and
potassic (K-feldspar-quartz) alterations.
The porphyry I (micro-quartz monzonite / micro-
monzogranite) presents combinations of selectively
pervasive to vein-filling alteration, with carbonate-
chloritesericite and quartz-K feldspar assemblages.
Silicification or sericitization (quartz and sericite) was
also observed in some samples.
The porphyry II (micro-leuco-quartz diorite / micro-
tonalite) presents superimposed events of selectively
pervasive to vein-filling alterations of the potassic,
propilic, and sericitic types and silicification.
11th Biennial SGA Meeting, Antofagasta,. 26–29 september 2011
3 Sulfide intergrowths in pyrite
Minute solid inclusions, particularly of chalcopyrite and
subordinately pyrrhotite, were identified in pyrite in
most samples. Chalcopyrite is typically intergrown with
pyrrhotite, cubanite, and mackinawite.
The observed intergrowths were morphologically
classified following Canchaya & Cardoso (written com.,
1984), which recognize simple and complex types. (Fig.
1) depicts such morphological types as well their
relative proportions as estimated. In addition, a new
intergrowth (type 4f), a variation between 1d and 1c
types, was incorporated to the classification. The simple
types are: cp/mck: 1b, 1e, 3b, 3c, 4f; cp/cb:1a, 3a;
cp/po:1a, 1b, 1e, 3a, 4f; po/cp:1a, 1b; py/po:1e (an
unique type formed directly in pyrite). The complex
types are: (cp/po:1b)/mck:1b; (cp/cb:3a)/po:1e;
(cp/po:1b)/mck:1e; (cp/po:1b)/cb:3a.
Figure 1. Sulfide intergrowth types (above) and their relative
percentages (below) in the Cuajone porphyry-type deposit.
cp=chalcopyrite, cb=cubanite, po=pyrrhotite, mck=macki-
nawite
4 Generation of the main intergrowths
The generation of the Cuajone sulfide assemblage may
be analysed considering experimental determined phase
relations in the Cu-Fe-S system (Fig 2). In the
temperature range 600 - 25 °C, relevant results were
presented by Fleet (2006), Amcoff (1981), Vaughan &
Craig (1978), Kaneda et al. (1978), Cabri (1973),
Mukaiyama & Izawa(1970), Sugaky et al.(1975) and
Yund & Kullerud (1966).
Figure 2. Phase relations among sulfide minerals at 600 to
25 C temperature range in the Cu-Fe-S system.
4.1 Simple intergrowth types
The pyrite/pyrrhotite intergrowth (py/po:1e) may be
related to pyrite replacing pyrrhotite as a result of ƒS2
increase (po + xS2 = py) or to the pyrrhotite exsolution
from a pyrrhotite solid solution in metastable
equilibrium with pyrite: ISS + py + poSS at 350 C, (Fig.
2). With decreasing temperature, the ISS-py tie line is
replaced by cpSS-po in the temperature interval of 323-
335C. At 300 C, the stable assemblage is cpSS + ISS +
po.
The chalcopyrite-cubanite intergrowths (cp/cb:1a,
3a) should have been originated from relatively Cu-rich
and Fe-poor solutions. At 300 °C, the assemblage cpSS +
ISS is not in equilibrium with pyrite. With decreasing
temperature, the assemblage would have been cpSS +
icbSS (isocubanite solid solution) about 235 C (Borchert
1934) or 210 °C (Kaneda et al. 1978). Chalcopyrite
firstly formed with decreasing temperature from the
initial chalcopyrite solid solution (cpSS). Below 235 C
(Mukaiyama & Izawa, 1970) or below 252 ± 3 C (Yund
& Kullerud, 1966), cubanite is formed as exsolution
lamellae (3a) or straight contact (1a) or ameboidal (1b)
intergrowths with chalcopyrite.
The chalcopyrite-pyrrhotite intergrowths (cp/po:
1a, 1b, 1e, 3a, 4f) represents relatively Fe-rich and Cu-
poor solutions. They may have originated: a) from the
py/po intergrowth and selective replacement of
pyrrhotite by chalcopyrite, resulting in po/cp: 1e and
then py/cp:1e, with pyrrhotite totally replaced by
chalcopyrite; b) from cpSS + ISS, because as temperature
decreases below 300 C, chalcopyrite + icbSS is formed
 11th Biennial SGA Meeting, Antofagasta,. 26–29 september 2011
(Kaneda et al. 1978), and below 255 C, pyrrhotite turns
stable, enabling the cp/po:1e, 3a, 1b and 1a intergrowth
types; c) from cpSS + poSS. Below 300 C pyrrhotite is
formed from poSS, generating the cp/po: 3a, cp/po:1e,
cp/po:1b and cp/po:1a intergrowth types. At even lower
temperatures, hexagonal pyrrhotite changes to
monoclinic at 250 C, according to Kissin (1982) or ca.
180 C, according to Lusk et al. (1993).
The chalcopyrite-mackinawite intergrowths
(cp/mck: 1b, 1e, 3b, 3c, 4f) should originated from the
original chalcopyrite solid solution (cp SS), which appears
below 500 C. The original assemblage could have been
cpSS in equilibrium with poSS. Intergrowths types 1e, 1b,
4f and 3b are explained by the previous formation of
chalcopyrite, which may co-exist in metastable
equilibrium with poSS at 255 C. Mackinawite would
exsolve from poSS at temperatures below 255 C,
originating any of the observed intergrowths. According
to Clark (1966), the upper limit of mackinawite stability
is 135 ± 5 C.
The cp/mck: 1c intergrowth indicates the
simultaneous formation of chalcopyrite and
mackinawite (similar to an eutectic crystallization), but
in solid state (Canchaya, pers. comm., 1994).
4.2. Complex intergrowth types
According to Barton (1973) and Cabri (1973),
chalcopyrite is dissolved in the initial intermediate solid
solution (ISS) at temperatures above 557°C (or 547 ±
5C, according to Yund & Kullerud 1966). Under these
conditions, the assemblage should be ISS + py + poSS, but
either ISS + poSS or ISS + py could also coexist. Thus,
under 557C, chalcopyrite would form from cpSS (Sugaki
et al. 1975) still in the ISS + py field, and would be
isolated from the other sulfides with decreasing
temperature. The coexisting phases at 400C could be
either ISS + py + cpSS or poSS+ISS.
At 300C, purer pyrrhotite may separate from the
pyrrhotite solid solution and a tie line would appear
between cpSS and po (Yund & Kullerud 1966). At lower
temperatures, icbSS appears as a metastable phase, from
which cubanite is generated as lamellae, fusiform or
ameboidal shapes. When cubanite separates from icbSS, it
becomes Fe-richer (Kaneda et al. 1978), with a
composition similar to poSS, promoting the formation of
mackinawite.
5 Correlation between hydrothermal
alteration types and sulfides from pyrite
intergrowths
A correlation between hydrothermal alteration and the
studied intergrowth types show that the most abundant
are: in the potassic zone, cp/po:1b and py/po:1e; in the
propylitic zone, cp/mck:4f and py/po:1e, and in the
sericitic zone, (cp/po:1b)/cb:3a, cp/po:1b and cp/mck:4f.
In addition, it was observed that pyrrhotite is the
most abundant solid inclusion in pyrite in the potassic
alteration zones, as well as in zones associated with
biotitization, while mackinawite, followed by pyrrhotite,
is most abundant in the propylitic alteration zones. In the
sericitc alteration zone pyrrhotite and mackinawite also
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occur, however even if cubanite is relatively scarce, it is
characteristic of this type of hydrothermal alteration.
6 Conclusions
It is possible to establish correlations between the
sulfides that compose the solid inclusions or
intergrowths in pyrite and hydrothermal alteration types
and, therefore, estimate the temperatures of the primary
copper mineralization in Cuajone.
The temperatures of precipitation of pyrrhotite,
cubanite and mackinawite were predominantly below
500, 200 and 180 °C, respectively. Thus, the primary
copper mineralization in Cuajone (chalcopyrite and
cubanite) is related to temperatures between 500 and a
tentatively lower limit between 300 and 200°C, in
dependence of chemical and structural detailed sericite
characterization (cf. Seedorff et al, 2005), which is in
progress.
Acknowledgements
We are greatly indebted to Dra. G. Garda for their critical
review and to Dr. J. Dilles for its constructive comments
that substantially improved our first manuscript draft.
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