Ronner BENDEZ JUAREZ

Shallow polymetallic and precious metal

mineralization associated with a Miocene
diatreme-dome complex: the Colquijirca
district in the Peruvian Andes.

2007

Volume 64
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UNIVERSIT DE GENVE FACULT DES SCIENCES
Dpartement de minralogie Professeur Llus Fontbot

Shallow polymetallic and precious metal

mineralization associated with a Miocene diatreme-
dome complex: the Colquijirca district in the Peruvian
Andes

THSE

prsente la Facult des sciences de lUniversit de Genve

pour obtenir le grade de Docteur s sciences, mention sciences de la Terre

par

Ronner BENDEZU

du Prou

Thse N3779

GENVE
Atelier de reproduction de la Section de physique
2006

Bendez Juarez, R.: Shallow polymetallic and precious metal mineralization associated with a Miocene diatreme-dome
complex: the Colquijirca district in the Peruvian Andes.
Terre & Environnement, vol. 64, IV + 221 pp. (2007)

ISBN 2-940153-63-9
Section des Sciences de la Terre, Universit de Genve, 13 rue des Marachers, CH-1205 Genve, Suisse
Tlphone ++41-22-702.61.11 - Fax ++41-22-320.57.32
http://www.unige.ch/sciences/terre/
 TABLE OF CONTENTS

TABLE OF CONTENTS

Abstract 1

Rsum tendu 5

Generalities, historical sketch and production 16

Chapter 1a. The geology of the Colquijirca district in a regional and

local context. Some observations and contributions 21

Paleozoic 21
Stratigraphy 21
Paleogeographic and tectonic evolution 23
Magmatism 23
Mesozoic 25
Stratigraphy 25
Paleogeography, tectonic evolution and structures 27
Magmatism 27
Cenozoic 29
Stratigraphy 29
Paleogeography, tectonic evolution and structures 32
Magmatism and Mineralization 32
References 32

Chapter 1b. The Marcapunta diatreme-dome complex 35

Main volcanic facies and spatial configuration 35

General Chemistry 38
References 39

Chapter 2 Description of the mineralization types 43

Introduction 43
Field and laboratory methods of study 43
Main terminology 43

Chapter 2a: The Smelter deposit 45

Host rock 45
Spatial configuration of the mineralized bodies and controls on mineralization 45
Mineral deposition history: stages and zoning 51
Early silica pyrite stage 51
Main ore stage 55


 TABLE OF CONTENTS

Late ore stage 64

References 64

Chapter 2b. The Colquijirca deposit 73

Host rock 73
Spatial configuration of the ore bodies and controls on mineralization 73
Mineral deposition history: stages and zoning 76
Early silica pyrite stage 76
Main ore stage 78
Late ore stage 86
Interpretation on the observed patterns of relative ages of mineral assotiations in the Smelter and
Colquijirca deposits 87
References 89

Chapter 2c. The central sector. Disseminated Au-(Ag) mineralization

in the Oro Marcapunta prospect 93

Host rock 93
Breccias 93
Dome and lava flows 95
Spatial configuration of the orebodies and controls on mineralization 95
Mineral deposition history: stages and zoning 95
Early barren stage 97
Gold stage 99
Late stages 102
Massive oxide veins 103
References 103

Chapter 2.d The San Gregorio deposit 105

Host rock 105

Spatial configuration of the mineralized bodies and controls on mineralization 106
Mineral deposition history: stages and zoning 109
Ore stage 109
Other manifestations of hydrothermal activity in the San Gregorio deposit 114
Pre-Ore stage dolomitization and dissolution 114
Post-ore stage quartz-alunite-kaolinite alteration and silicification 114
Main differences with the Colquijirca deposit 115
References 115

ii
 TABLE OF CONTENTS

Chapter 2.e Similarities, differences and spatial relationships between

the Au(Ag) disseminated mineralization at Oro Marcapunta and
the Cordilleran base metal deposits of Smelter and Colquijirca. A
distinction base on field and mineralogical observations 117

Similarities 117
High level emplacement 117
High sulfidation mineral assemblages and acid-sulfate gangue mineral assemblages 117
Differences 117
Strong ore zoning 119
Economical metal suite 119
Maximum depth of formation 119
Decreasing vs. increasing oxidation state 120
Crosscutting relationships 120

Chapter 3a. Relative age of Cordilleran base metal lode and replacement
deposits and high sulfidation Au-(Ag) epithermal mineralization in the
Colquijirca mining district, central Peru 121

Abstract 121
Introduction 122
Geologic setting and mineralization 122
The Colquijirca Mining district 122
Dated samples 124
Analytic procedure 127
Results 128
Discussion and conclusions 131
Acknowledgements 132
References 132

Chapter 3b. Infra-red (CO2) laser 40Ar/39Ar analysis of alunites from

The Miocene Colquijirca District, central Peru. 139

Abstract 139
Introduction 140
Previous geochronologic data and scope of the present work 143
Dated samples 143
Analytic procedure 145
Results 148
Discussion 149
References 150

iii
 TABLE OF CONTENTS

Chapter 4 Basic features of the hydrothermal fluids in the Colquijirca

District. A record from fluid inclusions and stable isotopes. 157

I. The Oro Marcapunta Au(Ag) epithermal high sulfidation fluids 157

a. Fluid inclusion microthermometry 157
b. Stable isotopes analysis 163
Discussion 168
Early barren stage 168
Gold stage 172
Late stages 172
II. Polymetallic Cordilleran fluids 172
a. Fluid inclusions microthermometry 173
b. Stables isotopes 176
Discussion 185
b. Early silica-pyrite stage 186
Main ore stage 186
References 191

Chapter 5: Summary and final discussion 195

Geological setting 199
General genetic model 206
References 208

General Appendix 211

Remerciements 221

iv

Abstract
The Colquijirca District is located on the central
Andes of Per and displays two main mineraliza-
tion types: (i) basically carbonate-hosted Cordilleran
sulfide-rich Cu-(Au-Ag) and Zn-Pb-(Ag) deposits
(Smelter, Marcapunta Oeste, Colquijirca, and San
Gregorio), and a (ii) volcanic-hosted Au-(Ag) dis-
seminated high sulfidation epithermal prospect (Oro
Marcapunta). The two mineralization types are in
close spatial relation to the Marcapunta Miocene
diatrema-dome complex, which occupies the central
sector of the district.
The Marcapunta complex consists of multiple
porphyrytic dome-lava intrusions which pre- and
post-date several episodes of phreatomagmatic
breccias typical of diatreme conduits. Geochemical
data obtained in this study show that the lava-
dome facies of the Marcapunta volcanic complex
are of dacitic high-K subalkaline composition. In
addition, trace element concentrations of Sr, Y, and
REE indicate that Marcapunta dacites approach
adakite-like signatures. 40Ar/39Ar dating conducted
on magmatic biotite gave inverse isochron ages of
12.90.1 and 12.70.1 for two slightly propylitized
dome-lava bodies and a well defined plateau age of
12.430.06 for an unaltered dome. The last age is the
available best approximation to a magmatic episode
related to the hydrothermal activity which started at
the most ~0.5 My later (~11.9 Ma, see below).
Volcanic-hosted Au-(Ag) disseminated
mineralization at Oro Marcapunta was formed by
a recurrent succession of events consisting each of
an early barren acid alteration followed by Au-(Ag)
deposition. The barren acid alteration generated
cores of vuggy silica surrounded by quartz-alunite
assemblages. Au-(Ag) was largely deposited as
millimetric wide sulfide- and oxide-bearing veinlets
mainly in the highly permeable altered ledges of vuggy
silica. Portions including sulfide-bearing veinlets are
made up of pyrite, covellite, enargite, chalcocite, and
sphalerite in amounts that collectively are <5 volume
%. In contrast to the early barren stage, the presence
of kaolinite-(smectite-illite-sericite) associated with
the Au-(Ag) deposition indicates that the ore fluids
were not strongly acid. Typical gold and silver values
are on the order of 0.1-0.5 ppm and 5-15 ppm,
respectively (Ag/Au ratios from ~10 to ~30). Oxide-
bearing veinlets consist mainly of botryoidal hematite
and goethite with gold and silver grades in the range
of 0.5 and 2 ppm and 20 and 80 ppm, respectively
(Ag/Au ratios from ~10 to ~40).
ABSTRACT
Mainly carbonate-hosted sulfide-rich (30-
60 volume %) polymetallic replacement deposits
constitute the second main type of mineralization
developed in the Colquijirca district (Cordilleran
deposits). This mineralization type aggregates a
global resource of at least 300 Mt of Cu-Zn-Pb-(Au-
Ag) ores. The polymetallic ores were formed by a
sequence of processes that began with a widespread
replacement of the carbonate rocks surrounding
the Marcapunta complex during an early stage that
basically deposited silica and pyrite. Followed a
productive stage which was superimposed on most
of, and beyond, the silica-pyrite replacements. This
productive stage produced the well marked ore
metal and mineral zoning observed through the
entire Smelter-Colquijirca mineralized corridor. This
mineralized corridor contained prior to mining about
70 Mt at ~1.9 % Cu, ~0.3 g/t Au (Smelter deposit)
and 40 Mt at ~6 % Zn, ~3 % Pb, ~5 oz/t Ag, and
0.03-0.05 % Bi (Colquijirca deposit). The most
internal zone of this corridor consists of enargite-
(luzonite)-bearing assemblages accompanied in
part by abundant alunite-(zunyite). Much of the
internal zone is largely devoid of non-sulfide gangue
minerals (except for quartz) being observed only
locally small amounts of kaolinite-(dickite, illite,
smectite). The enargite-(luzonite)-bearing zone is
generally surrounded by chalcopyrite-bearing zones
and more externally by Ag-rich zones dominated by
sphalerite and galena which constitute the ores of
the historical Colquijirca mine. A late stage, generally
of sub-economic character, consisting mainly of
chalcocite- and tennantite-bearing assemblages was
superimposed on large portions of the Smelter-
Colquijirca mineralized corridor. Au/Ag ratios of the
ore samples range from around 60-80 in the internal
enargite-bearing parts up to >300 in the sphalerite-
galena zones at Colquijirca. The Ag/Au ratio of the
bulk Smelter-Colquijirca corridor is about 250 to 300.
Cross cutting relationships indicate that during the
productive stage, the inner Cu zones encroached on
the Zn-Pb zones recording a progressive advancing
of at least 1.5 km of the sulfide-rich mineralization
front with time. Conversely, the late chalcocite-bearing
and tennantite-bearing assemblages are interpreted
in terms of retraction of the mineralization front,
possibly during the waning stages of the hydrothermal
system activity when meteoric water/magmatic water
ratios were higher.
Seven alunite samples from the Au-(Ag)


disseminated high sulfidation epithermal system
(Oro Marcapunta) gave furnace and laser derived
40
Ar/39Ar plateau ages in the range of 11.90.07 to
11.100.06 Ma at 2. This is a particularly long
lifespan and it is interpreted in terms of several
shorter episodes of mineralization sustained by
multiple intrusive and/or thermal episodes related
to a large magma reservoir. The existence of several
episodes of mineralization finds support by linking
individually the 40Ar/39Ar ages with observed
crosscutting relationships between dated alunite and
periods of gold deposition defined by the sulfide-
and oxide-bearing veinlets. At least two recurrent
episodes of acid alteration-gold deposition took
place during the activity of the Au-(Ag) epithermal
system. Seven laser and furnace derived 40Ar/39Ar
ages obtained on alunite that predate, are coeval, and
post-date different generations of enargite-bearing
and sphalerite-bearing assemblages, indicating that
the sulfide-rich Cordilleran Smelter and Colquijirca
deposits were formed several hundred thousand years
later than the Au-(Ag) disseminated mineralization at
Oro Marcapunta which lasted from 11.9 to 11.1 Ma.
The obtained values (plateau ages) from Cordilleran
ores in Smelter and Colquijirca define a relatively
narrow period of hydrothermal activity between
10.830.06 and 10.560.08 Ma (2). Additionally,
three K/Ar ages were obtained from the Cordilleran
San Gregorio deposit by means of conventional
whole rock analysis. Two ages resulted similar at
13.1-13.22.2 Ma (2) and the third at 13.94.0 Ma
(2). Ruled out an excess of inherited argon caused
by detrital mica in the alunite-rich concentrates and
supported by the concordance of two of the ages
at 13.1-13.22.2 Ma, it is not excluded that the San
Gregorio deposit formed earlier than the other
Cordilleran ores of the district. Alternatively, given
the large errors on the K-Ar ages, the San Gregorio
deposit could also form coetaneously with Smelter
and Colquijirca.
Fluid inclusions from the Au-(Ag) disseminated
mineralization at Oro Marcapunta show that vuggy
silica and quartz-alunite alteration entrained fluids
that reached temperatures in the range of 210C and
280C. These fluids were of low salinity with typical
values ranging from ~0 to ~4 NaCl wt % equivalent.
These data examined on the basis of mineralogical
and zonal patterns suggest that the early barren
stage fluids derived from a mixing process which
involved variable amounts of two end member
cold fluids (210C-240C) of nearly zero salinities
with hot slightly saline fluids (250C-280C and 3
%-4 NaCl wt % equivalent). Stable isotope data are
in agreement with this conclusion. The calculated
isotope compositions of water (D and 18OSO4) in
equilibrium with alunite define an elongated field
whose extreme values are on the one side (with D and
18O values from -45 to -55 and from 7 -7.5
) typical of magmatic signatures, respectively and
on the other (with D from around -75 to -90

ABSTRACT
and 18O from-3 to -6 ) indicative of meteoric
input. The elongated field fits with the meteoric
water-magmatic water mixing trend defined at the
contemporaneous Julcani system, located 300 km to
the south. The magmatic end-member was most likely
a magmatic vapor plume, from which SO2 interacted
with water and condensed to form H2SO4, the main
acid agent in the formation of the vuggy silica and
quartz-alunite alteration. S isotope compositions of
alunite (34S from 21.5 to 22.4 ) support this
origin in which sulfate has equilibrated with H2S
formed through disproportionation of SO2 within
a condensing vapor plume. Limited fluid inclusion
data from the productive Au-(Ag) stage define a
mixing trend that broadly fits with that of the early
acid barren stage suggesting similar end-member
fluids. The available data cover a temperature range
between 190C to 260C and salinities from ~1 to ~5
NaCl wt % equivalent. A number of fluid inclusions
hosted in quartz from veinlets located 90 m below
the summit of Marcapunta record boiling. The
microthermometric results indicate that the boiling
curve adjusts for a 200-300 m depth equivalent,
indicating that erosion of the system was minor.
Most of the fluid inclusion and stable isotope
data on the polymetallic Cordilleran deposits were
obtained on the productive stage. Fluid inclusions
gave homogenization temperatures from 165.9C to
298.2C and salinities between ~0 and ~7 NaCl wt %
equivalent. Significant variations of Th are correlated
with the distance to the Marcapunta volcanic
complex. In the inner enargite zones, homogenization
temperatures reached 300C whereas in more distal
parts (i.e., at Colquijirca) temperatures declined to
as low as ~170C. In contrast to temperature, no
systematic variation in salinities from Smelter to
Colquijirca is distinguished. The gradual temperature
decrease from Smelter to Colquijirca is in agreement
with drilling correlation indicating that these deposits
are part of a single and continuous mineralized
corridor which was formed from a single process
of mineralization during the productive stage.
In the Smelter-Colquijirca corridor, the strong
zonal pattern, including the notable decrease in
the sulfidation states of sulfides assemblages from
high (enargite-pyrite) to intermediate (chalcopyrite-
pyrite) seems to respond to mainly a temperature
decrease. Such temperature decrease could probably
be reinforced by local mixing with meteoric fluids
particularly in the external sphalerite-galena zones.
Two relatively contrasting Th vs. salinity trends may
be discriminated from the available fluid inclusion
data of the productive stage. A first trend defined
by quartz-hosted inclusions from alunite-bearing
assemblages comprises salinity values between ~0
and ~4 NaCl wt % equivalent and homogenization
temperatures in the range of 221C and 273C.
This trend is nearly identical to that delineated
by the early barren acid stage during the Au-(Ag)
disseminated mineralization at Oro Marcapunta. The

mineralogical observations combined with stable
isotope data allow the interpretation that this trend
reflects mixing between a magmatic end-member,
likely a SO2-bearing vapor plume, with meteoric
water. The estimated 18O and D compositions
of water in equilibrium with Main ore stage alunite
range from values around-41 D and 7 18O resulting two fluids, independently of the mechanism
to progressively isotopically lighter fluids down to
around -99 D and -6 18O along a linear are possibly the precursor fluids responsible for the
trend that suggests mixing of magmatic fluids and
unexchanged meteoric fluids. These values fit with
the mixing line deduced for the acidic fluids that
generated the vuggy silica and quartz-alunite zones
at Oro Marcapunta. By projecting the regression
mixing line representing the entire population of
alunite D and 18O values of the Colquijirca district
it is possible to estimate a composition of around -
14010 D and -181 18O for the 10.6-11.9
Ma Colquijirca meteoric water. These values are similar
to meteoric water composition estimated for other
Miocene systems of central Per. Entrainment of a
SO2 magmatic plume in the formation of the alunite
fluids, is also suggested by the 34S values for alunite
(21.1 to 26.4 ) from the Main ore stage quartz-
alunite assemblages which are typical of hydrothermal
magmatic fluids in which sulfate has equilibrated
with H2S formed through disproportionation of SO2
within a condensing vapor plume.
The second Th vs salinity trend defined
by fluid inclusions representing enargite-bearing
assemblages, largely devoid of alunite, covers a larger
salinity interval between 0.35 and as high as 7.2 NaCl
wt % equivalent and temperatures from 218C to
286C. These data combined with stable isotope data
suggest mixing of magmatic fluids with exchanged
meteoric waters. The entrainment of exchanged
meteoric waters is indicated by the estimated 18O
and D compositions of water in equilibrium with
kaolinite and dickite, minerals recognized to have co-
precipitated with the ores. These compositions plot
following a pattern typical of meteoric waters that
have exchanged isotopically with host rocks displaying
a positive 18O shift and a minimal shift in D.
Modeling of isotopic equilibrium through convection
suggests that 10.5-11.9 Ma Colquijirca meteoric
water exchanged with host rocks, predominantly with
sedimentary rocks. The exchanged meteoric waters
then most likely experienced mixing with magmatic
waters. 34S compositions of sulfides of the whole
Smelter-Colquijirca corridor, with average values
close to zero, support such magmatic component.
The modeling predicts that the isotopic exchange
could take place only if the integrated water/rock
mass ratio attained values between 0.3 and 1.
A genetic model based on the integrated
geological, mineralogical, and microanalytical data
may be broadly proposed. The model supposes
the coexistence at depth, near the brittle-ductile
transition, of hypersaline fluid and single-phase vapor.
Because of the probable shallow emplacement of
ABSTRACT
the main degassing cupola(s) of the magma chamber
(suggested by the shallow nature of porphyry Cu
mineralization related to other Cordilleran deposits
of Per), the single-phase vapor fluids during their
ascent could prevent vapor contraction permitting
breaching of the two phase field below 450C. The
of phase separation (i.e., boiling or condensation),
generation of the acid alteration-gold deposition
recurrent pulses recognized during the Au-(Ag)
high sulfidation epithermal mineralization at Oro
Marcapunta. The low Ag/Au ratios (10 to 40) from
the Au-(Ag) disseminated bodies similar to values
obtained from quantitative microanalysis of single-
phase vapor fluid inclusions in other porphyry-related
systems are in agreement with this view.
While the vapor phase ascended, the brine
(hypersaline fluid) probably remained largely within
the brittle-ductile transition and then gradually
liberated as this transition retracted downward with
time. It is in these instances, perhaps up to tens of
thousands of years later, when meteoric waters that
had exchanged isotopically with mainly sedimentary
rocks of the Excelsior and Mitu Groups through
convection, could mix with the brines. At Colquijirca,
modeling based on the isotopic composition of
ore-related kaolinite and dickite predicts that these
exchanged waters could acquire the obtained
isotopic compositions at moderate to high total mass
water/rock ratios (between 0.3 and 1). On the other
hand, stable isotope evidences (D, O, S) pointing to
extensive mixing between magmatic and exchanged
meteoric water have the implication that the 2 to 7
NaCl wt % equivalent salinities of the Cordilleran
ore fluids at Colquijirca can be best explained by
dilution of magmatic brines. The hypothesis that
diluted magmatic brines originated the Cordilleran
ore-forming fluids is also supported by key element
concentration ratios of the ore samples and of the
bulk Smelter-Colquijirca mineralized corridor notably
Ag/Au (~50->300), Cu/Au (~7x104-~9x104), and
Fe/Au (~2x107-~5x107), which are similar to ratios
observed in brines from microanalysis of fluid
inclusions from other porphyry-related localities and
different from the ratios measured in single-phase
vapor fluid inclusions coexisting with the brine fluid
inclusions. As mentioned before, the Ag/Au, Cu/
Au, and Fe/Au ratios of the Au-(Ag) disseminated
bodies at Oro Marcapunta are, in turn, similar to those
measured on single-phase vapor fluid inclusions in
several porphyry-related systems.
Acidic fluids were common during the period
of Cordilleran mineralization. They manifested
most prominently through assemblages exempt
of ore minerals, though less pronounced, they
also precipitated alunite accompanied by enargite-
(sphalerite). The isotopic evidence indicates that,
as at Oro Marcapunta, these acidic fluids formed
from SO2 disproportionation by reaction with water,

 ABSTRACT

suggesting that multiple vapor plumes were released

during the lifespan of the Colquijirca hydrothermal
history. Most likely, SO2 would have derived from the
rising single-phase vapor fluids. Cordilleran fluids
could, subsequent to dilution, potentially mix with
the acidic fluids at different levels of the system
resulting most probably in oxidized acidic ore fluids.
Alternatively, Cordilleran fluids and acidic fluids
could enter the epithermal environment separately.
The mineralogical evidence suggest that this second
scenario was possibly more common.



RSUM TENDU
Le District de Colquijirca se situe dans les An-
des du Prou central (Figure a) et comporte deux
types de minralisations (Figures a et b): (i) des gise-
ments Cu-(Au-Ag) ainsi que Zn-Pb-(Ag) de type
Cordilleran riches en sulfures, encaisss dans des
roches carbonates et localiss Smelter, Marcapun-
ta Oeste, Colquijirca et San Gregorio (e.g., Ahlfeld,
1932; Lindgren, 1935; McKinstry, 1936; Bendez,
1997; Vidal et al., 1997) et (ii) le prospect pithermal
dissmin de type high sulfidation Oro Marca-
punta encaiss dans des roches volcaniques. Ces deux
types de minralisations ont une relation spatiale avec
le complexe de dme-diatrme de Marcapunta, dge
Miocne, occupant une place centrale dans le dis-
trict.
LE COMPLEXE VOLCANIQUE DE
MARCAPUNTA ET TYPES DE MINER-
ALISATIONS
Le complexe de Marcapunta est compos de
plusieurs dmes et coules pyroclastiques prcdant
et succdant plusieurs pisodes phratomagmatiques
donnant lieu des brches typiques de conduits de
diatrme (Figure b). Les donnes gochimiques ob-
tenues lors de cette tude rvlent que le facis de
lava-dome du complexe de Marcapunta possde
une composition dacitique subalkaline enrichi en K.
De plus, la concentration des lments traces tels
que Sr, Y et les terres rares suggre que les dacites
deMarcapunta sapprochent dune signature ada-
kitique. Une tude gochronologique 40Ar/39Ar sur
de la biotite magmatique de deux affleurements de
lava-dome lgrement propyllitiss ainsi que dun
dme frais, donne des ages disochrones inverses
12.90.1 et 12.70.1 et un ge plateau bien dfini
12.430.06 respectivement (Figure e). Ce dernier ge
est la meilleure estimation disposition dun pisode
magmatique li lactivit hydrothermale (Bendez
et al., 2003) qui sest manifeste au maximum 0.5 My
plus tard (~11.9 Ma, voir ci-dessous).
La minralisation Au-(Ag) encaisse dans les
roches volcaniques Oro Marcapunta (Figure b) a t
forme par une succession rcurrente dvnements
consistant chacun en une altration acide strile suivie
par la prcipitation dAu-(Ag). Laltration acide st-
rile a engendr des curs de vuggy silica entours
par des assemblages quartz-alunite (Figure c). LAu-
(Ag) a largement prcipit dans les zones altres trs
RESUME ETENDU
permables du vuggy silica dans des veinules mil-
limtriques riches en sulfures et oxides (Figure c). Les
veinules riches en sulfures sont composes de pyrite,
enargite, chalcosine et sphalrite en quantits infri-
eures 5 % vol. Contrairement au stade prcoce st-
rile, la prsence de kaolinite-(smectite-illite-sericite)
associe la prcipitation dAu-(Ag) indique que les
fluides ntaient pas extrmement acides. Les valeurs
typiques dAu et Ag sont de lordre de 0.1-0.5 ppm et
5-15 ppm respectivement (rapports Ag/Au de ~10
~30; Figure h). Les veinules riches en oxides sont
composes principalement dhmatite et goetite bot-
ryodale (Figure c) contenant de lAu et de lAg dont
les concentrations varient de 0.5 2 ppm et de 20
80 ppm respectivement (rapport Ag/Au de ~10
~30; Figure h).
Les gisements polymtalliques riches en sul-
fures (30-60 % vol.) de type Cordilleran en rem-
placement dans les roches carbonates constituent
le second type de minralisation dans le District de
Colquijirca (Figure b). Ce type de minralisation con-
stitue des ressources globales estimes non moins
de 300 Mt de minerai de Cu-Zn-Pb-(Au-Ag). Ce
minerai polymtallique rsulte dune succession de
processus dbutant par un stade prcoce de rem-
placement tendu des roches carbonates bordant
le complexe de Marcapunta et prcipitant essentiel-
lement de la silice et de la pyrite (Figure d). Le stade
productif sest ensuivit et a tlescop le remplace-
ment de silice-pyrite et mme parfois au-del. Ce
stade productif a engendr une zonation minrale et
mtallique bien dfinit qui est observ tout le long du
corridor minralis de Smelter-Colquijirca (Figure b).
Ce corridor minralis possdait, avant son exploita-
tion, environ 70 Mt ~1.9 % Cu, ~ 0.3 g/t Au (gise-
ment de Smelter) et 30 Mt ~6 % Zn, ~ 3 % Pb, ~
5 oz/t Ag, et 0.03-0.05 % Bi (gisement de Colquijir-
ca). La zone centrale est constitue par lassemblage
enargite-(luzonite) accompagn par endroits par
lassemblage abondant alunite-(zunyite)(Figure c). La
grande majorit de la zone centrale est gnralement
dpourvue de minraux de gangue except le quartz,
mais la prsence de kaolinite-(dickite, illite, smectite)
peut tre observe localement. La zone enargite-
(luzonite) est entoure dune zone chalcopyrite
qui est son tour entoure dune zone externe riche
en Ag domine par de la sphalrite et de la galne,
constituant ainsi le minerai historique de la mine
de Colquijirca. Un stade tardif, gnralement car-
actre sub-conomique, consiste principalement en

 RESUME ETENDU

0 79 75 71

E -360 000 (7616' W)

3 Km IQUITOS

N 4

CHICLAYO
CAJAMARCA

8
TRUJILLO
HUARAZ

AREA OF
GEOLOGICAL MAP

PA
12 LIMA

CI
FI
CUZCO
Cerro de Pasco

C
N-8820000 (1040' S)

O
16 AREQUIPA

C
E
A
N
Fault

Thrust and Yanamate

reverse faults

Fold axis

GEOLOGICAL UNITS

Colquijirca
Dacite diatreme-dome complex (Miocene)
B
Pocobamba Formation (E ocene),
mainly limestones and marls
Goyllarizquizga Group (C retaceous),
sandstones
Pucara Group (Upper T riassic-
L ower Jurassic), limestones
Mitu Group (Permian-T riasssic),
sandstones

E xcelsior Group (Devonian), phyllites

Marcapunta
MINERALIZATION TYPE

Au-(Ag) disseminated epithermal San Gregorio

Polymetallic Cordilleran deposits

Figure a
Figure a: Gologie gnrale du secteur Cerro de Pasco-Colquijjirca incluant les deux types principaux de mineralisations. Il est
noter que la couverture sdimentaire quaternaire a t volontairement te.


 S N
ORO MARCAPUNTA

SMELTER COLQUIJIRCA

gisements de Oro Marcapunta, Smelter et Colquijirca

GEOLOGICAL UNITS
100 m

200 m Dacite diatreme-dome complex (Miocene)

Calera Formation (Eocene), mainly limestones and marls

Shuco Member (Eocene), calcareous conglomerates

Mitu Group (Permian-Triasssic), sandstones

MINERALIZATION
Cordilleran ores Au-(Ag) disseminated ores
Cu-(Au-Ag) zone Quartz-alunite + vuggy silica
containing Au-bearing veinlets
Zn-Pb-Cu-(Ag-Bi) zone

Zn-Pb-(Ag) zone
RESUME ETENDU

Figure b: Section longitudinal Nord-Sud du secteur Nord du district de Colquijirca daprs la Figure a. La section inclut les


Figure 5.2
 RESUME ETENDU

quartz-alunite

I 1 cm II 1 cm

III 1 cm IV

PARAGENETIC SEQUENCE IN THE DISSEMINATED Au-(Ag) OCCURRENCE OF ORO

MARCAPUNTA

Figure c: Partie superieure, images representatives de differents assemblages minralogiques correspondants aux corps polym-
talliques du type Cordilleran. Partie infrieure, squence paragntique pour ce type de minralisation, tel quil est observ
Smelter et Colquijirca.


 RESUME ETENDU

enargite

dickite

I 1 cm II 1 cm

enargite

telluride

goldfieldite

pyrite
enargite tennantite

III 0.5 cm IV 50 m

PARAGENETIC SEQUENCE IN THE CORDILLERAN POLYMETALLIC DEPOSIT OF SMELTER

Figure d: Partie suprieure, images representatives des differents assemblages minralogiques des corps Au-(Ag) du type
pithermal high sulfidation. Partie infrieure, squence paragntique pour ce type de minralisation, tel quil est observ Oro
Marcapunta.



un assemblage chalcocine-tennantite superposant
de larges portions du corridor minralis de Smelt-
er-Colquijirca. Les rapports Ag/Au de la totalit du
corridor de Smelter-Colquijirca atteignent des val-
eurs entre 30 et 50 dans les zones internes (Figure h)
et >250 dans les zones externes.
DURE DE VIE DU SYSTME
MAGMATO-HYDROTHERMAL
Les relations de recoupement indiquent que
lors du stade productif, les zones internes Cu ont
empit sur les zones Zn-Pb, enregistrant ainsi un
avancement progressif avec le temps du front de mi-
nralisation riche en sulfure sur au moins 1.5 km. A
linverse, les assemblages tardifs chalcosine et ceux
tennantite sont interprts comme rsultant de la
rtraction du front minralisateur, probablement lors
du dclin du systme hydrothermal lorsque le rapport
eau mtorique/eau magmatique tait plus lev
Sept chantillons dalunite provenant du sys-
tme pithermal Au-(Ag) dissmin de type high
sulfidation ont t analyss par la mthode 40Ar/
39
Ar furnace et laser et donnent des ges plateau
de 11.90.07 11.100.06 Ma 2 (Figure e). Ce
laps de temps est particulirement long et est inter-
prt comme rsultant de plusieurs pisodes courts
Middle Miocene
Probable periods of gold deposition
12
Age (Ma) 11
Previous surveys
K/Ara
39
Ar/ Ar (furnace)b
40
This survey:
39
Ar/ 40Ar (infrared laser)
K/Ar whole rock
15 14
Figure e: Diagramme rsumant les donnes gochronologiques (K/Ar et 40Ar/39Ar) disponibles dans le district de Colqui-
jirca.
10
RESUME ETENDU
de minralisations lis plusieurs intrusions et/ou
dpisodes thermiques, le tout associ un large r-
servoir de magma. Lexistence de plusieurs pisodes
de minralisation est indique part la mise en relation
individuelle des ages 40Ar/39Ar avec les relations de
recoupement entre les analyses dates et les priodes
de prcipitation de lor dfinit par les veinules sul-
fures et oxides. Au moins deux pisodes rcurrents
daltration acide-dposition de lor a eu lieu pendant
lactivit du systme pithermal Au-(Ag) (Figure e).
Sept ges 40Ar/39Ar four et laser obtenus sur
de lalunite prcdent, contemporaine et postdatant
diffrente gnrations dassemblages enargite et
dassemblages sphalrite, indiquent que les min-
ralisations de type Cordilleran riches en sulfures
Smelter et Colquijirca ont t forms quelques cen-
taines de milliers dannes plus tard que la minrali-
sation pithermale de type high sulfidation Oro
Marcapunta, persistant de 11.9 11.1 Ma (Figure e).
Les ges plateau sur alunite du gisement de type Cor-
dilleran Smelter et Colquijirca dfinissent un temps
dactivit hydrothermale relativement court, allant
de 10.830.06 10.560.08 Ma (2
) (Bendez et
al., 2003). De plus, trois ges K/Ar ont t obtenus
sur roche totale dans le gisement de type Cordilleran
San Gregorio (Figure e). Deux ges ont t obte-
nus 13.1-13.22.2 Ma (2
) et un troisime ge
13.94.0 Ma (2
). En liminant la possibilit dun
Late Miocene
a
on biotite
a
on sanidine
a
on alunite
on alunitea
Dome emplacement
Au-(Ag) disseminated
epithermal mineralization
Cordilleran ores
of San Gregorio Cordilleran base metal deposits
13 12 11 10
Age (Ma)
 RESUME ETENDU

excs dargon hrit caus par des grains de mica d- le quartz des veinules situes 90 m en dessous du
tritique prsents dans les concentras riches en alunite, sommet de Marcapunta enregistre la prsence dbul-
ainsi quen supposant correcte la concordance des lition. La courbe dbullition issue des rsultats mi-
deux ges 13.1-13.2 2.2 Ma, il nest pas exclu que crothermomtriques correspond des profondeurs
le gisement de San Gregorio se soit form avant les de 200-300m, tmoignant ainsi une rosion mineure
autres gisement de type Cordilleran dans le district. du systme.
Alternativement, tant donn les larges erreurs sur
les ges K/Ar, le gisement de San Gregorio a gale- La plupart des donnes dinclusions fluides et
ment pu tre synchrone Smelter et Colquijirca. disotopes stables sur les gisements de type Cordille-
ran ont t obtenus dans les stades productifs. Les
inclusions fluides mesures dans le quartz donnent
FLUIDES MINERALISATEURS des tempratures dhomognisation allant de 165.9
298.2 C et des salinits variant entre ~0 ~7 %
Les inclusions fluides de la minralisation pi- poids NaCl quivalent (Figure f). Les variations si-
thermale de type high sulfidation Oro Marca- gnificatives des tempratures dhomognisation sont
punta montrent que laltration de type vuggy silica corrles avec la distance jusquau complexe de Mar-
et celle de type quartz-alunite ont t forms partir capunta. Dans les zones centrales enargite, les tem-
de fluides des tempratures allant de 210 280C pratures dhomognisation atteignent 300C alors
(Figure f). Ces fluides ont une salinit faible avec des que dans les parties plus distales (i.e. Colquijirca), les
valeurs typiques allant de ~0 4% poids NaCl qui- tempratures diminuent jusqu 170C. Contraire-
valent. Ces donnes examines sur la base de la com- ment aux tempratures, aucune variation systmati-
position minralogique et de la zonation existante que de salinits de Smelter Colquijirca nest tablie.
suggrent que les fluides striles du stade prcoce ont La diminution graduelle de temprature de Smelter
t issus dun processus de mlange impliquant une Colquijirca est en accord avec les corrlations de
quantit variable dun ple caractris par un fluide forages indiquant que ces gisements font partie dun
froid (210C-240C) salinit proche de zro, avec corridor minralis unique et continu, qui a t form
un ple dfini par un fluide chaud, lgrement salin par un processus de minralisation pendant le stade
(250C-280C et 3 % -4 % poids NaCl quivalent) productif. Dans le corridor de Smelter-Colquijirca,
(Figure f). Les donnes disotopes stables sont en ac- la forte zonation incluant la diminution des tats de
cord avec cette interprtation. En effet, la composi- sulfidation des assemblages de sulfures allant de haut
tion isotopique calcule de leau (

D et 18OSO4) en (enargite-pyrite) intermdiaire (chalcopyrite-pyrite),
quilibre avec lalunite dfinit un champ allong avec semble rpondre principalement une diminution de
des valeurs extrmes qui sont dun ct (avec

D et temprature. Ce genre de diminution de temprature
18O values de -45 -55 et de 7 -7.5 ) peut tre probablement amplifi localement par un
typique de signature magmatique et de lautre (avec mlange avec de leau mtorique, plus particuli-

D de ~-75 -90 et 18O de -3 -6 ), rement dans les zones externes sphalrite-galne.

caractristique dune contribution deau mtorique
(Figure g). Le champ allong est en accord avec une
droite de mlange deau magmatique et mtorique
la composition de celle-ci tant dfinie Julcani, gise-
ment contemporain au District de Colquijirca, situ
400 km vers le sud (Deen et al., 1994). Le ple deau
magmatique tait vraisemblablement un panache de
vapeur magmatique, duquel SO2 a interagi avec de
leau puis condens pour former H2SO4, lagent ma-
jeur dacidit dans la formation de vuggy silica et de
laltration quartz-alunite (e.g., Rye, 1993). La com-
position isotopique du soufre dans lalunite (34S de
21.5 22.4 ) est en accord avec une origine dans
laquelle le sulfate a quilibr avec H2S form travers
la disproportionation de SO2 au sein dun panache de
vapeur subissant une condensation (e.g., Rye, 1993).
Des donnes limites dinclusions fluides du stade
productif Au-(Ag) sont dfinis par une droite de
mlange qui est grossirement en accord avec celle
du stade prcoce strile, suggrant des ples de flui-
des similaires (Figure f). Les donnes disponibles
couvrent une variation allant de 190 260 C et des
salinits de ~1 ~5 % poids NaCl quivalent (Fi-
gure f). Un certain nombre dinclusions fluides dans
Deux tendances de la temprature dhomognisation
versus salinit peuvent tre mises en vidence partir
des donnes dinclusions fluides disponibles des sta-
des productifs. Une premire tendance se dessine par
les inclusions fluides dans le quartz des assemblages
alunite-quartz, caractrise par des salinits entre ~0
~4 % poids NaCl quivalent et des tempratures
dhomognisation allant de 221 273C (Figure f).
Cette tendance est presque identique celle dfinie
par le stade prcoce strile acide lors de la minralisa-
tion Au-(Ag) dissmine Oro Marcapunta (Figure
f).
Les observations minralogiques combines
aux rsultats disotopes stables permettent dinter-
prter cette tendance comme le rsultat dun mlan-
ge entre un ple magmatique, vraisemblablement un
panache de vapeur riche en SO2, avec de leau m-
torique. Les compositions de leau en quilibre avec
lalunite du stade principal de minralisation ont des
valeurs allant de -41
D et 7 18O progressi-
vement des fluides isotopiquement plus lgers ayant
des valeurs autour de -99
D et -6 18O le
long dune tendance linaire suggrant un mlange
de fluides magmatiques avec des fluides mtoriques

11

A B
350
300
a b
ThC
250
200
150
100
0.0 1.0 2.0 3.0
Salinity (wt % NaCl eq.)
Type of Early barren stage:
primary in quartz from vuggy silica zones
primary in quartz from quartz-alunite zones
secondary in quartz from vuggy silica zones
secondary in quartz from quartz-alunite zones
primary in alunite from quartz-alunite zones
Type of First gold stage fluid inclusions:
primary in quartz from First gold stage
secondary in quartz from First gold stage
Figure f: Diagramme montrant les resultats des mesures microthermomtriques effectues dans des inclusions fluides (salinit
versus temperature dhomognisation). A, dans les inclusions fluides appartenant la minralisation Au-(Ag) pithermale de
type high sulfidation. B, dans les inclusions fluides appartenant la minralisation polymtallique de type Cordilleran.
non-changs (Figure g). Ces valeurs sont en accord
avec la ligne de mlange dduite des fluides acides qui
ont donns lieu aux zones vuggy silica et quartz-
alunite Oro Marcapunta. Par projection rgressive
de la ligne de mlange reprsentant la totalit de la
population des valeurs
D et 18O de lalunite pr-
sente dans le District de Colquijirca, il est possible
destimer la composition de leau mtorique pr-
sente Colquijirca entre 10.6-11.9 Ma caractrise
par des valeurs de -14010
D et -181 18O
(Figure g). Ces valeurs sont similaires la composi-
tion de leau mtorique pour dautres systmes du
Miocne au Prou central. Limplication dun pana-
che de SO2 magmatique dans la formation des fluides
en quilibre avec lalunite est aussi suggre par les
valeurs de 34S de lalunite (21.1 26.4 ) prsent
dans lassemblage quartz-alunite du stade principal.
Celui-ci est typique dun fluide hydrothermal dori-
gine magmatique o le sulfate a quilibr avec H2S
form lors de la disproportionation de SO2 au sein
dun panache de vapeur en phase de condensation
(e.g., Rye, 1993).
La seconde tendance caractrise par la temp-
rature dhomognisation versus la salinit est dfinie
par les inclusions fluides reprsentant les assembla-
ges enargite, largement dpourvus dalunite. Cette
12
RESUME ETENDU
350
300
a
ThC
250
200
150
100
4.0 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0
Salinity (wt % NaCl eq.)
Type of Early silica-pyrite stage fluid inclusions:
Isolated in quartz
Fracture-controlled in quartz
Type of Main ore stage fluid inclusions:
Primary in quartz from enargite-bearing assemblage
Secondary in quartz from enargite-bearing assemblage
Primary in sphalerite from sphalerite-bearing assemblage
Secondary in sphalerite from sphalerite-bearing assemblage
Primary in quartz from alunite-bearing assemblage
Secondary in quartz from alunite-bearing assemblage
Secondary in quartz from sphalerite-bearing assemblage
Primary in barite from tennantite-bearing assemblage
Primary in enargite from enargite-bearing assemblage
tendance couvre un intervalle de salinit plus large
entre 0.35 7.2 % poids NaCl quivalent et des tem-
pratures dhomognisation de 218 286 C (Figure
f). Ces donnes combines aux isotopes stables sug-
grent un mlange de fluides magmatiques avec des
eaux mtoriques isotopiquement changes avec les
roches encaissantes. Lentranement de ces fluides
mtoriques changs est indiqu par les estimations
des compositions en 18O et
D de leau en quili-
bre avec la kaolinite et la dickite, ces dernires ayant
co-prcipits avec la minralisation (Figure d). Ces
compositions suivent un patron typique deaux m-
toriques ayant subit un change isotopique avec les
roches encaissantes, traduit par un dcalage en 18O
et un dcalage minimal en
D (Figure g). La modli-
sation dun quilibre isotopique par convection sug-
gre que leau mtorique 10.5-11.9 Ma de Colqui-
jirca subit un change avec les roches encaissantes,
principalement des roches sdimentaires. Les eaux
mtoriques changes ont subit vraisemblablement
un mlange avec des eaux magmatiques. Les com-
positions isotopiques en 34S des sulfures dans la to-
talit du corridor Smelter-Colquijirca, avoisinant des
valeurs proches de zro, confirment une composante
magmatique. La modlisation prdit que lchange
isotopique a eu lieu seulement si la valeur du rapport
eau/roche se situe entre 0.3 et 1 (Figure g).
 RESUME ETENDU

Au-(Ag) disseminated mineralization fluids VV

-20 alunite fluids

Cordilleran mineralization fluids PMW

-40
alunite fluids
D (, SMOW)

300C

L
dickite fluids 0.3

W
M
-60 kaolinite fluids
200C
exchange with
d 0.15
tren
Minerals sedimentary
-80 ing 400C rocks
alunite mix 300C
dickite 100C

ing
200C
1
-100 kaolinite

mix
300C exchange with
igneous rocks
100C 200C
-120
100C
1
300C 400C
200C
-140 100C

COLQUIJIRCA METEORIC WATER

-20 -15 -10 -5 0 5 10 15

18O (, SMOW)
Figure g: Diagramme rsumant les donnes disotopes stables de la minralisation Au-(Ag) de type high sulfidation et la
minralisation de type Cordilleran dans le district de Colquijirca. Les compositions isotopiques de D et 18O(SO4) des fluides
en quilibre avec lalunite ont t calcules partir des quations de Stroffregen et al. (1994) pour des tempratures obtenues
Figure
laide de la 5.5 des inclusions fluides. Les compositions isotopiques de D et 18O des fluides en quilibre avec
microthermomtrie
de la kaolinite et dickite ont t calcules avec les quations de Gilg and Sheppard (1996) et Sheppard and Gilg (1996). Les
tempratures utilises ont t obtenues par la microthermomtrie des inclusions fluides. Le diagramme comprend galement la mo-
dlisation isotopique des eaux mtoriques de Colquijirca 11.9-10.6 Ma change isotopiquement par convection avec des roches
sdimentaires et ignes. Plus de dtails sont donns dans le texte.

500

400

300
Ag (ppm)

200

100

0
0 1 2 3 4 5
Au (ppm)

Disseminated epithermal A u-(A g) mineralization

Polymetallic C ordilleran deposits

samples from supergene zone
samples from hypogene zone

Figure h: Rapports Ag-Au caractristiques pour les deux types de minralisations du district de Colquijirca. Le carr fond
Figure
blanc represente le rapport de h de Smelter (Marcapunta Norte).
tout le gisement

13
 RESUME ETENDU

MODELE GENETIQUE PROPOS
Un modle gntique bas sur des donnes
gologiques, minralogiques et microanalytiques peu
tre propos. Le modle suppute la coexistence en
profondeur, proche de la transition ductile-cassante,
dun fluide hypersalin et dune vapeur monophase
(e.g., Heinrich, 2005). Du fait de la probable mise en
place peu profonde dune coupole de dgazage de
la chambre magmatique (suggr par la nature de la
minralisation de porphyre cuprifre li dautres
gisements de types Cordilleran au Prou), la vapeur
monophase na pas pus se contracter, permettant ai-
nsi la vapeur dempiter dans le champ biphas au
dessous de 450C lors de sa remonte. Les deux flu-
ides en rsultants, indpendamment du mcanisme
de sparation de phase (i.e. bullition ou condensa-
tion), sont probablement les prcurseurs des fluides
responsables de la gnration de laltration acide-
dpt dor issu de pulses rcurrents reconnus lors
de la minralisation pithermale dissmine de type
Au-(Ag) disseminated ores
Cordilleran ores
high sulfidation Oro Marcapunta. Les faibles rap-
ports Ag/Au (10 40) des corps de Au-(Ag) dis-
smins sont similaires aux valeurs obtenues laide
de mthodes microanalytiques quantitatives sur la
vapeur monophase dans dautres systmes lis aux
porphyres cuprifres et sont en accord avec cette
prise de position (e.g., Ulrich et al., 1999).
Alors que la vapeur remonte, la saumure mag-
matique reste trs probablement en retrait dans la
transition ductile-cassante et est libre graduellement
lors de la rtraction de cette transition en profondeur
avec le temps. Dans ce cas, quelques dizaines de mil-
liers dannes plus tard, lorsque les eaux mtoriques
ont subit un change isotopique par convection avec
les roches sdimentaires du groupes de lExcelsior et
du Mitu, ces eaux ont pu tre mlanges avec la sau-
mure magmatique. A Colquijirca, la modlisation, ba-
se sur la composition isotopique de la kaolinite et de
la dickite lis la minralisation, prdit que les eaux
changes peuvent obtenir des compositions isoto-
piques calcules, lorsque le rapport total eau/roche
Au-(Ag) disseminated ores
Cordilleran ores

Marcapunta
diatreme-dome complex

Pocobamba Pocobamba
carbonate rocks carbonate rocks

mixing of diluted brines with acidic fluids

derived from SO2 disproportionation

Mitu red beds Mitu red beds

diluted brine isotopic diluted brine isotopic

exchange exchange
mixing mixing

brine brine

brine refluxing Excelsior slates brine refluxing Excelsior slates

magma chamber
Brittle-ductile transition magma chamber Brittle-ductile transition

a. Scenario 1 b. Scenario 2

Fluids 1 Km

brine

vapor plume ascent

meteoric water

Figure i: Schma prsentant le modle gntique global propos pour les minralisations du district de Colquijirca. Les possibles
processus impliqus dans chaque scnario sont dcrits dans le texte.

14
 RESUME ETENDU

est lev (entre 0.3 et 1). Les isotopes stables (H, O et Bendez, R., Fontbot, L., and Cosca, M. 2003, Relative
S) indiquent un mlange intense entre des eaux mag- age of Cordilleran base metal lode and replacement de-
matiques et des eaux mtoriques changes impli- posits and high sulfidation Au-(Ag) epithermal miner-
quant ainsi que les salinits des fluides de la minrali- alization in the Colquijirca mining district, central Peru.
sation de type Cordilleran Colquijirca, entre 2 et 7 Mineralium Deposita, 38, p. 683-694.
% poids NaCl quivalent, peuvent tre expliques par
une dilution de saumures magmatiques. Lhypothse Heinrich, C.A., 2005, The physical and chemical evolution
selon laquelle de saumures magmatiques sont les pr- of low-salinity magmatic fluids at the porphyry to epi-
curseurs des fluides ayant form la minralisation de thermal transition: a thermodynamic study. Mineralium
type Cordilleran est soutenue par les rapports cls Deposita, 39, p. 864-889.
des concentrations dans le corridor minralis de
Smelter-Colquijirca, principalement Ag/Au (~ 150- Lindgren, W., 1935, The silver mine of Colquijirca, Per.
~ 350), Cu/Au (~ 7x104 - ~ 9x104), and Fe/Au (~ Economic Geology, 30, p. 331-346.
2x107 - ~ 5x107). Ceux-ci sont similaires aux rapports
mesurs dans les saumures magmatiques par micro- McKinstry, H.E., 1936, Geology of the silver deposit at
analyses dans les inclusions fluides dans dautres lieux Colquijirca, Peru. Economic Geology, 31, p. 619-635.
lis un porphyre ainsi quaux rapports mesurs dans
des inclusions vapeur monophases coexistant avec Rye, R.O., 1993, The evolution of magmatic fluids in the
des inclusions fluides salines (e.g., Ulrich et al., 1999). epithermal environment; the stable isotope perspective.
Comme dj mentionn prcdemment, les rapports Economic Geology, 88, p. 733-752.
Ag/Au, Cu/Au, et Fe/Au dans les corps Au-(Ag)
dissmins Oro Marcapunta, sont similaires ceux Ulrich, T., Gnther, D., and Heinrich, C.A., 1999, Gold
mesurs dans des inclusions vapeur monophase concentrations of magmatic brines and the metal bud-
dans plusieurs systmes lis un porphyre. get of porphyry copper deposits. Nature (London), 399,
Des fluides acides taient frquents lors de la 6737, p. 676-679.
priode de minralisation de type Cordilleran. Ces
fluides acides ont produit des assemblages exempts Vidal, C., Proao, J., and Noble, N., 1997, Geologa y dis-
de minraux conomiques, toutefois avec parfois tribucin hidrotermal de menas con Au, Cu, Zn, Pb y Ag
une faible prcipitation dalunite accompagn par de en el Distrito Minero Colquijirca, Pasco. IX Congreso Pe-
lenargite-(sphalerite). Les vidences isotopiques in- ruano de Geologa, p. 217-219.
diquent qu Oro Marcapunta, ces fluides acides se
sont forms la suite de la disproportionation de
SO2 par raction avec de leau, montrant ainsi que
des panaches multiples de vapeur ont t librs tout
au long de lhistoire hydrothermale de Colquijirca.
SO2 a le plus probablement t deriv dune vapeur
monophase. Les fluides de la minralisation de type
Cordilleran, la suite de dilution, ont t potentiel-
lement mlangs diffrents niveaux du systme,
rsultant ainsi en fluides acides oxydants (scnario 1
dans Figure i). Alternativement, les fluides de la mi-
nralisation de type Cordilleran et les fluides acides
ont pu sincorporer dans lenvironnement pithermal
sparment (scnario 2 dans Figure i). Les vidences
minralogiques indiquent que ce second scnario a
t galement important.

BIBLIOGRAPHIE
Ahlfeld, F., 1932, Die Silberlagersttte Colquijirca, Per.
Zeitschrift Praktischer Geologie, 40, p. 81-87.

Bendez, R., 1997, Caractersticas geolgicas mineral-

gicas y geoqumicas de los yacimientos de Zn-Pb (Ag)
de San Gregorio y Colquijirca emplazados en unidades
sedimentarias en los bordes del sistema epitermal de alta
sulfuracin de Marcapunta. Tesis

Ingeniero, Universidad
Nacional de Ingeniera, Lima, 60 p.

15
 GENERALITIES

16

Generalities, historical sketch and production
Colquijirca is one of the numerous examples
of mining districts related to Miocene intrusions of
the high Cordillera of central and northern Per. It
contains several deposits which together constitute
one of the largest accumulations of Zn-Cu-Ag-Au-
Pb ores of the world. The district contains two main
ore types: (1) disseminated Au-(Ag) high sulfidation
epithermal mineralization, similar to the Yanacocha
and Pierina deposits of northern Per and Rodalquilar
in Spain and (2) large zoned sulfide-rich polymetallic
deposits only comparable in tonnage to the ores of
the nearby giant Cerro de Pasco system. This second
type is economically important and similar in many
respects to one of the most prominent deposit types
of the porphyry-related family in the American
cordilleras, the so called and characterized by Einaudi
(1977) Cordilleran deposits.
Classical papers on this second ore type by noted
geologists such as Ahlfeld (1929), Lindgren (1935)
and McKinstry (1936) reflected the major economic
importance of this district during the first decades of
the 20th century. It is from these works that we have
the first epigenetic postulations on the genesis of the
mineralization, all of them linking the Marcapunta
volcanic complex with the source of the ore fluids.
In the seventies, and diametrically opposed, Lehne
(1977) and Lehne and Amstutz (1982) proposed
a syngenetic model for the mineralization. More
recently, however, several workers including Arroyo
(1983), Vidal et al. (1984, 1997), Bendez (1997),
Fontbot and Bendez (1999) and Bendez et al.
(2003), among others, argued, based on new data, for
a magmatic-related epigenetic origin.
The ores of the Colquijirca district occur in the
following four distinctive types or styles:
1. Disseminations, patches and veinlets
of Au-(Ag)-bearing oxide minerals exclusively
hosted in the volcanic rocks of the Marcapunta
diatreme-dome complex. This style represented by
the Marcapunta prospect, is a characteristic example
of high sulfidation Au epithermal mineralization.
2. Cu(Au-Ag-Sn) sulfide-rich
replacements essentially in carbonate rocks of the
Pocobamba Formation and diatreme breccias. This
type of mineralization consists of enargite and
chalcocite-rich veins and mantos. Several projects and
prospects of this style form a large funnel-shaped
GENERALITIES
body surrounding the Marcapunta volcanic center.
Projects and/or prospects include the so-called here
Cobre Marcapunta Sur and Oeste and the Cobre
Marcapunta (Norte) or Smelter deposit.
3. Zn-Pb-Ag(Cu-Bi) sulfide-rich
replacements in carbonate rocks of the Calera
Member. Represented by the historic Colquijirca
deposit, this style of mineralization displays the
strongest resemblance to many of the classic
polymetallic Zn-Pb-Cu-Ag deposits of central and
northern Per.
4. Zn-Pb(Ag-Bi) fine-grained sulfide-
rich replacements in carbonate rocks of the Pucar
Group. This prominent style of mineralization was
virtually unknown in other parts of the world prior
to the discovery of San Gregorio. It is, indeed, the
economically most important in the district and one
of the largest Zn-Pb deposits of any type in the
Andes.
Colquijirca is one of the earliest known silver
mining centers of the Americas. According to
several archeological surveys (e.g., Atalaya, 2000),
the pre-incaic Tinyahuarco ethnic group lived on the
Colquijirca hill and worked silver between the 5th
and 8th centuries.
It is believed that some of the silver goods
transported by hundreds of llamas to pay the rescue
of the Inca king Atahualpa, and found in 1533 by
Spanish conquerors near Colquijirca (Miguel de
Astete, 1533 in Markham, 1872) had their origin in the
Colquijirca mines. Some decades after and following
the route of Miguel de Astete, the Spaniards re-
discovered Colquijirca and began mining as early as
1567 (Fisher, 1977). Mining since then, and until the
end of the 19th century was intermittent, mainly using
small-scale open-pit techniques. Unfortunately, there
is scarce available documentation for this period.
In the 1890s the mine passed to Mr. Eulogio
Fernandini who started underground workings and
an economically very successful production period
from the early 1900s. For several years the mine was
the most productive in silver of the continent, with
an annual peak of nearly 7.5 million ounces in 1925
(the Bonanza Epoch). From 1905, bismuth mining
was at San Gregorio, some 6 km south of Colquijirca.
For several decades it was the most important mine
of this metal in Per before its closure in 1959. From
17

the end of the 1950s, mining was concentrated at
Colquijirca and production not only of silver but also
of zinc and lead increased considerably. This period
of polymetallic production ceased in 1976, and with it
the underground workings in the historic Colquijirca
mines. From 1972 until the late seventies, mining
in the district was almost exclusively for copper (at
Smelter, 2 km south of Colquijirca). Since 1981, once
again, mining for zinc, lead and silver characterizes
the Colquijirca district, this time through modern
open-pit operations.
The lack of information during the Colonial
and early Republican periods precludes a precise
evaluation of the total historical silver production
from the Colquijirca district. A rough and conservative
figure for the pre-Fernandini period is estimated
to be 30 million ounces. The registered data for
the 20th account for 100 million ounces (compiled
from Hutchinson, 1920 and available government
statistics), which indeed represent an underestimate
since the production of a significant number of years
is undocumented. The total silver production of the
Colquijirca district may therefore approximate no
less than 150 million ounces.
Although it is also difficult to calculate the total
zinc and lead production, the figure for the tonnage
mined is simpler. It can be estimated that some 20 to
25 Mt of ore at 6% Zn, 3% Pb and 3-4 oz/t Ag were
extracted since the beginning of the 20th century.
The bismuth production at San Gregorio probably
exceeded 200000 tones (t) at 1 to 3 % Bi. The amount
of copper ore treated from Smelter was insignificant
(<1 million tones) considering probable resources
of a minimum of 50 Mt at 1.9 % Cu (Yaringao et
al., 1997) in the northern sector of the district in
addition to another 50 Mt grading 1.8 % Cu recently
estimated in the western sector of the district (Vidal
and Ligarda, 2004).
Two old images dating from 1919, from Hutchinson (1920). Left: small ancient Spanish pit. The Cerro de Pasco Copper
Corporations first smelter in the background. Right: the former San Gregorio Bi-(Ag) deposit located immediately northeast of
the San Gregorio Zn-Pb-(Ag) deposit.
18
GENERALITIES
REFERENCES
Ahlfeld, F., 1932, Die Silberlagersttte Colquijirca,
Per. Zeitschrift Praktischer Geologie, v. 40, p. 81-87.
Arroyo, F.,1983, Ocurrencia de minerales uranferos en
el yacimiento de Colquijirca. Boletin Sociedad Geolgica
del Per, 72, p. 75-88.
Atalaya, E., 2000, Private archeological report for So-
ciedad minera El Brocal S.A.A.
Bendez, R., 1997, Caractersticas geolgicas miner-
algicas y geoqumicas de los yacimientos de Zn-Pb (Ag)
de San Gregorio y Colquijirca emplazados en unidades
sedimentarias en los bordes del sistema epitermal de alta
sulfuracin de Marcapunta. Tesis Ingeniero, Universidad
Nacional de Ingeniera, Lima, 60 p.
Bendez, R., Fontbote, L., Cosca. M. 2003. Relative
age
of Cordilleran base metal lode and replacement deposits,
and high sulfidation Au-(Ag) epithermal mineralization in
the Colquijirca mining district, central Per. Mineralium
Deposita, 38, 683-694.
Einaudi, M.T., 1977, Environment of ore deposition
at Cerro de Pasco, Per. Economic Geology, 72, p. 893-
924.
Fisher, J.R., 1977, Silver mines and silver miners in co-
lonial Per, 1776-1824. Centre for Latin-American stud-
ies, University of Liverpool, Monographs series N 7, 150
p.
Fontbot, L and Bendez, R., 1999, The carbonate
hosted Zn-Pb San Gregorio deposit, Colquijirca District,
central Per, as a high sulfidation epithermal system, in
Stanley et al., (eds.), Fifth Biennial SGA Meeting, Mineral
Deposits: Processes to Processing, 1, p. 495-498.
 GENERALITIES

Hutchinson, W.S., 1920, The Fernandini properties,

province of Pasco, Per: Production costs and profits,
Colquijirca silver mine, Huaraucaca metallurgical plant, La
Curena copper mine, San Gregorio bismuth mine. Report
for the Fernandini Properties. 70 p.

Lehne, R.W., 1977, Nuevos aspectos acerca del

yacimiento de Colquijirca. CITEM Rev. Inst. Cient. Tec-
nol. Min., 3, 17-26.

Lehne, R.W. and Amstutz, G.C., 1982, Sedimentary

and diagenetic fabrics in the Cu-Pb-Zn-Ag deposit of
Colquijirca, Central Per. In: Amstutz, G.C., EL Goresy,
A., Frenzel, G., Kluth, C., Moh, G., Wauschkuhn, A., &
Zimmermann, R. (Eds.), Ore genesis, the state of the art.
Springer, Berlin, p. 161-166.

Lindgren, W., 1935, The silver mine of Colquijirca,

Per. Economic Geology, 30, p. 331-346

McKinstry, H.E., 1936, Geology of the silver deposit

at Colquijirca, Per. Economic Geology, 31, p. 619-635.

Markham, C., 1872, Reports on the discovery of Per.

Part II. Report of Miguel de Astete on the expedition to
Pachacamac. Hakluyt Society, London, 143 p.

Vidal, C., Mayta, O, Noble, D.C., and McKee, E.H.,

1984, Sobre la evolucin de las soluciones hidrotermales
dentro del centro volcnico Marcapunta en Colquijirca-
Pasco. Volumen Jubilar Sociedad Geolgica del Per, 10,
p. 1-14.

Vidal, C., and Ligarda, R., 2004, Enargite-Gold De-

posits at Marcapunta, Colquijirca Mining District, Central
Per: mineralogic and geochemical zoning in subvolcanic,
limestone-replacement deposits of High-Sulfidation Epi-
thermal Type. Economic Geology Special publications,
11, 231-242

Vidal, C., 1992, Exploraciones por oro en el Suroeste

del Cerro Marcapunta. Distrito Minero de Colquijirca
y Cerro de Pasco. Informe privado Sociedad Minera El
Brocal S.A.A., 26 p.

Yaringao, M., Arias, W., and Panz, M., 1997, Ex-

ploraciones y evaluacin de los yacimientos del Distrito
Minero de Colquijirca, Pasco: IX Congreso Perano de
Geologa, p. 231-236.

19
 GENERALITIES

20

Chapter 1
1a. The geology of the Colquijirca district in a
regional and local context. Some observations
and contributions
Mainly because of the wealth of its mining
centers, the geology of the central Peruvian Andes
has received particular attention since the early
decades of the 20th century. McLaughlin (1924),
Steinmann (1929), Noble (1931), Harrison (1943),
Boit (1949, 1962, 1964, 1966), Jenks (1951), Haas
(1953), Johnson (1955), and Mgard (1968, 1978,
1984), and Angeles (1993, 1999) established the
basis of the stratigraphy and tectonic evolution of
central Peruvian Andes. Other papers focused on
magmatism, including those of Noble et al. (1974,
1979, 1985, 1990), Soler (1987, 1991), Soler and
Bonhomme (1988), Soler and Rotach-Toulhoat
(1990) and Noble and McKee (1999), among others.
The following is an integration of all of the works
mentioned above, complemented by my own data at
the scale of the Colquijirca district.
The Colquijirca district is located on the
Meseta de Bombon high plateau (at 4,300 m.a.s.l)
of the central Peruvian Andes near 11S and 76W.
From a tectonic point of view, it lies on a 1500 km
long segment (from 2S to 15S) of flat subduction
in which the Nazca plate dips eastwards beneath
the Andes (e.g., Pilger, 1981). This segment is
distinguished by the absence of modern and recent
volcanism. This Peruvian Andean segment developed
a considerable crustal thickness of 55-60 km (Couch
et al., 1981; Gutscher et al., 1999), concomitant
with major Neogene uplift to nearly 4000 m.a.s.l.
on average. The Colquijirca district is part of the
westernmost belts of Miocene magmatism in central
and northern Per (~360 km from the Peruvian
trench), with which most of the largest mining
districts are temporally and spatially associated (e.g.,
Noble and McKee, 1999). Metallogenetically, the 6 to
14S latitude region is characterizeed by development
of polymetallic deposits of the class known as
Cordilleran deposits (sensu Einaudi, 1977) which
coincide with the flat subduction segment.
Paleozoic
Stratigraphy
Excelsior Group
The known geologic history of the Junin-
Goyllarizquizaga region (Figure 1a.1) commences in
CHAPTER 1
Lower Paleozoic times with a terrigenous strata of
probable Cambrian to Devonian age (Mgard, 1978).
McLaughlin (1924) recognized several well exposed
occurrences of slates, phyllites and quartzites in
different parts of the region, including the Cerro
de Pasco district. He termed these units collectively
the Excelsior Series, now known as the Excelsior
Group. Most of these units have been ascribed
to the Ordovician, based on paleofauna found in
several areas of the region including Chaupihuaranga
(Dalmayrac, 1978; Figure 1a.1). However, as discussed
by Mgard (1978), the age and history of the Lower
Paleozoic rocks in the region remain uncertain.
At a more local scale, the Excelsior Group
crops out over appreciable areas of the Cerro de
Pasco district, where according to retrieved data from
ancient mining operations, it would attain at least
400 m in thickness. There, it is composed mainly of
reddish brown slates and phyllites with abundant thin
intercalations of quartzites. Sandstones grading along
strike to quartzites and arkoses were documented
by Bowditch (1935) near the Cerro de Pasco mine.
Outcrops of the Excelsior Group in the Colquijirca
sector are scarce and present only in the northern
part of the district, at Vista Alegre and Condorcayn
(Figure 1a.2). In these places the main rocks of this
group are slightly sericitized and chloritized reddish
brown phyllites with centimetric slump structures,
similar to those present at Cerro de Pasco (Angeles,
1993).
Ambo, Tarma and Copacabana Groups
In contrast to other parts of the Junin-
Goyllarizquisga region, the southeastern and eastern
areas near Carhuamayo (Figure 1a.1) presents
outcrops of Mississippian to Lower Permian rocks
of the Ambo, Tarma and Copacabana Groups. The
Ambo Group (Mississippian) is composed dominantly
of sandstones and shales with intercalations of
conglomerates. Similar lithologies characterize the
Tarma Group (Pennsylvanian) which, in addition,
includes a few intervals of carbonate rocks. The
Copacabana Group (Lower Permian), which in other
parts of the Andes is known for its thick sequences
of carbonate rocks, has not been recognized in the
21
 CHAPTER 1

Geological Units Geographical points

Ch
AM Ambo
10 km
Main hydrographic basin

Am
AG El Aguila
Quaternary cover Gy
Vi
CA Cacun
Late Miocene-Early Pliocene
pyroclasts CH Chaupihuaranga

AM Ambo Ag
1030'
Miocene volcanic centers

GY Goyllarizquizga
Upper Eocene-Oligocene
intrusions
HU Huachn

Santonian-Eocene
HY Huancayn

Hy Ca
Milpo

76
Malm-Santonian Hll Huayllay

Upper Triassic-Lower Jurassic: MA Marcapunta

Pucar Group
Qu
MR Mariac
Upper Permian-Lower Triassic: Area of Figure 1.2
Mitu Group
PA Pacoyn Pa Su
Cerro de Pasco
Carboniferous QU Quinua Mr
Hu
Devonian: QY Quicay
Excelsior Group Qy
RA Raco Ya Sh
Precambrian
SH Shalipayco
Colquijirca

SU Sunkullo
Major fault Ra
VI Vinchos
Major erosional discordance
er Ma
Riv
Punrun lake
uan
YA Yanamate

N
Sa n J

logical Units Geographical points

Main hydrographic basin AM Ambo

AG El Aguila Bombon plateau

Quaternary cover
CA Cacun
Late Miocene-Early Pliocene
pyroclasts CH Chaupihuaranga
Hll Carhuamayo
Miocene volcanic centers AM Ambo

GY Goyllarizquizga Colombia
Upper Eocene-Oligocene Ecuador
intrusions
HU Huachn

Santonian-Eocene
HY Huancayn Per u Brasil

Malm-Santonian Hll Huayllay

A r ea of Junin lake
geological map
Upper Triassic-Lower Jurassic: MA Marcapunta
L ima
Pucar Group Pacific Ocean
MR Mariac
Upper Permian-Lower Triassic: Bolivia
Mitu Group
PA Pacoyn
Chile

Carboniferous QU Quinua

Devonian: QY Quicay
Excelsior Group
RA Raco
Figure 1 Junin

Precambrian
SH Shalipayco

SU Sunkullo
fault

VI Vinchos
erosional discordance
YA Yanamate

Fig. 1a.1: General geology of the Meseta de Bombon plateau region in the central Peruvian Andes. Modified from Mgard
(1978) and Dalmayrac (1978).

22

region, except at Ambo, in the northernmost part
(Steinmann, 1929).
At Cerro de Pasco and Colquijirca, the
presence of Upper Permian-Lower Triassic rocks
unconformably overlying the Excelsior Group
precludes the occurrence of Mississippian to Lower
Permian rocks (e.g., at Condorcayn; Figures 1a.2
and 1a.4). Furthermore, an ancient drill hole located
immediately southeast of Marcapunta (DDH-1,
Figure 1a.2), intercepted phyllites of the Excelsior
Group beneath Upper Permian-Lower Triassic and
Quaternary deposits (Angeles, 1993; Figure 1a.2).
This indicates that the Ambo, Tarma and Copacabana
Groups, in part carbonate sequences, are apparently
absent from the entire Cerro de Pasco-Colquijirca
sector.
Mitu Group
In the northern part of the Junin-
Goyllarizquizga region, the Excelsior Group is
overlaing unconformably by a sequence of essentially
continental red beds. McLaughlin (1924) assigned
these rocks to the Mitu Formation, which was
redefined later in a more regional sense as Mitu Group
by Newell et al. (1953). As is the case with the majority
of the Paleozoic rocks in central Per, the age of the
Mitu Group is not well defined. While Mgard (1978)
assigned an Upper Permian-Lower Triassic age, Boit
(1962) found supposedly Lower Permian paleofauna
near Colquijirca and Carhuamayo.
Some of the best exposures of the Mitu Group
in the region are present near Carhuamayo and
Shalipayco (Figure 1a.1). Newell et al. (1953) described
sections in both places and measured between 800
and 1500 m of predominantly sandy conglomerates
and sandstones. Conglomerates tend to occupy the
lower portion of the Group (between one third and
more than a half of the measured section), whereas
mainly sandstones and several thick volcanic flow
intervals constitute the upper Mitu Group.
In the Cerro de Pasco-Colquijirca sector, the
Mitu Group comprised two distinct lithological units
(Figure 1a.4) similar to those described by Newell
et al. (1953) at Carhuamayo and Shalipayco. The
lower unit is composed largely by poorly classified,
reddish sandy conglomerates with flat subangular
clasts of pebble and, less abundantly, cobble size.
Clasts are essentially quartzite, milky quartz, phyllite
and less common intrusive and extrusive igneous
rocks. As mentioned by McLaughlin (1924), this
material appears to have been derived largely from
the underlying Excelsior Group. The rock matrix
consists of coarse to fine arenaceous material, mostly
sandstone. At Colquijirca, Angeles (1993) reported
intercalations of mudstone and sandstone at the top
of the lower unit. The upper unit crops out mainly
in the Colquijirca area and is made up of reddish
sandstones and arkosic sandstones commonly
CHAPTER 1
displaying oblique lamination. Decimetric to metric
intercalations of sandy conglomerates, similar to
those of the lower unit, are present immediately
to the east of the current mining operations. Fine-
grained sediments ranging from siltstones to shaly
siltstones (Figure 1a.5) are also present in the Mitu
Group in several parts of the Colquijirca district
including the small valleys west of Smelter and south
of Marcapunta (Figures 1a.2 and 1a.3).
Paleogeographic and tectonic evolution
Except for the Ordovician transgression
which occurred over almost all the Peruvian territory
and deposited part of the Excelsior Group, the
paleogeographic and tectonic history of the region
during Lower Paleozoic times is unclear (Mgard,
1978).
According to Mgard (1978), during the
Mississippian an extensional episode led to the
establishment of intracontinental basins along the
present Andean cordillera, where sedimentation
was largely terrigenous (Ambo Group). Two
important transgressions in the Pennsylvanian and
Lower Permian followed and were responsible for
deposition of the Tarma and Copacabana sediments
respectively. The absence over most of the region of
Pennsylvanian to Lower Permian strata suggests that
the western limit of the marine transgressions was
approximately defined by a northwest-southeast line
passing through Carhuamayo and near the Cerro de
Pasco-Colquijirca sector (Figure 1a.1).
The Middle-Late Permian-Early Triassic
period characterized by intense terrigenous
sedimentation within a horst-graben system produced
by intracontinental rifting along the present central
Andes (e.g., Benavides, 1999). This tectonic event,
exempt from folding (Mgard, 1978), resulted in the
accumulation of nearly 3000 m thick of continental
red beds of the Mitu Group. Mafic volcanism resulted
from rifting (e.g., Benavides, 1999) and is identified
mainly towards the south-southeastern parts of the
region, southeast of Carhuamayo (Figure 1a.1).
Magmatism
Besides the intense rift-related mafic volcanism
during the Mitu sedimentation, magmatism in the
region is represented by intrusions dating from
Middle-Upper Paleozoic times. Granitic intrusions,
generally poorly dated, occur along the eastern edge of
the region considered here, within terranes attributed
to the Precambrian of the Eastern Cordillera.
Hydrothermal orogenic gold mineralization is partly
hosted by these intrusions as in the Huachn district
(Figure 1a.1).
23
 CHAPTER 1

E-360 000 (7616' W)

3 km
N
CA

VE

Cerro de Pasco

N-8820000 (1040' S)

Yanamate

Lo
Geographical points PI

ng
it u
BO Bohorquez SF
VA

din
VI

al f
CA Cacun
CD
a'

a
canic

ult
ter
CD Condorcayn

GU Gualquepaqui

HC Huaraucaca PU Colquijirca
obamba
mation
LA Lachipana a LA b'
RSJV fault

PI Puca Ingenio
SM
up PU Pumarrn

r Jurassic:
SF Sacra Familia
b
er Triassic: SG San Gregorio
MA
SM Smelter Fault
Group
VE Venenococha
Thrust or
sense VI Viscagaga HC c' reverse fault
observer

VA Vista Alegre
fault (in plan)
Fold axis
YM Yanque Mara c SG

aa'
Cross section Sections of Figure 1.4
Open pit
s
4300 Mesured altitude
Area of Figure 1.3
Drill hole

Figure 1a.2: General geology of the Cerro de Pasco-Colquijirca sector as indicated in Figure 1a.1. Main data from Jenks
(1951) and Angeles (1993, 1999). Note that sections shown in Figure 1a.4, were traced perpendicular to the folding axes. Note
also that Quaternary cover was removed.

24

Mesozoic
Stratigraphy
Pucar Group
Along the central Peruvian Andes, the Mitu
Group is covered by a thick sequence of carbonate
rocks, mainly limestones. McLaughlin (1924) termed
this sequence Pucar limestone but it was later
reclassified by Jenks (1951) as the Pucar Group.
The sequence has been studied by several workers,
including notably Harrison (1943), Mgard (1968),
Szekely and Grose (1972), Rosas (1994) and Stanley
(1994). The last of these suggested a division of the
Group into three formations, previously proposed
by Mgard (1968) as the Chambar Formation
(Norian-Rhaetian), Aramachay Formation (Rhaetian-
Sinemnurian) and Condorsinga Formation
(Sinemurian-Toarcian; ages according to Stanley,
1994). Since the upper formations are not identified
with certainty in the Cerro de Pasco-Colquijirca
sector, only the Chambar Formation is dealt with in
detail here. Paleontological studies indicate a Norian
age for the Chambar Formation (Cox, 1949; Haas,
1953; Prinz and Hillebrandt, 1994; Stanley 1994).
The base of the Chambar Formation is
constituted by detrital and calcareous sediments, which
are often mistaken for the Mitu Group sandstones.
East of Junn (Figure 1a.1), Mgard (1978) described
a rhythmic sequence of conglomerates, sandstones
and dolostones which grades upwards into calcareous
dolostones of Norian age and which in turn overlies
unconformably the Mitu Group red beds. He
mentioned similar intercalations in other localities
of central Per and concluded that they represent
the basal unit of the Norian Chambar Formation.
In the Colquijirca district, this basal unit is also
present as a generally <5 m thick bed of polymictic
breccia known locally as basal breccia. The bed is
composed of angular to subangular clasts of phyllites,
milky quartz, sandstones and quartzites within an
arenaceous matrix. In addition, exploration drilling
at San Gregorio encountered metric intercalations
of sandstones and calcareous dolostones, apparently
concordant with the carbonate rocks and overlying
unconformably the Mitu sandstones.
The Chambar Formation is composed
almost exclusively by gray limestones, dolomitic
limestones and dolostones, which were deposited
in shallow water, mainly as lagoonal and subtidal
barrier facies with thin intercalations of supratidal
and intertidal sediments. Thicknesses in general
range between 500 and 1000 m, but in some
tectonically controlled depocenters it exceeds 2000
m (Rosas, 1994). A general field description of
the Chambar Formation by Mgard (1978) which
applies to the area studied is summarized as follows:
The carbonate strata are variably bituminous and
include centimetric alternations of calcareous-
argillaceous sediments and diastems. Bioclastic rocks
and less common calcarenites displaying oblique
stratification are important lithofacies. Silicification is
CHAPTER 1
frequently observed in the form of irregular masses
of chert disposed parallel to bedding and in places
concentrated in metric intervals. Although rare
globally, intraformational monogenic breccias are
also present. The overall interval described includes
minor but varied intercalations of shales, siltstones
and subordinate cineritic sandstones besides rare
thin gypsiferous beds.
In the Cerro de Pasco-Colquijirca sector, the
Chambar Formation was studied in some detail by
Jenks (1951), who divided it into two domains eastern
and western, separated by a major fault now known
as the Longitudinal fault (Figures 1a.2, 1a.3 and 1a.4).
The eastern domain, nearly 3,000 m thick is one of the
thickest measured the Chambar Formation, whereas
in the western domain thicknesses range from 300-
500 m. This important thickness difference suggests
that the Longitudinal fault was active during Pucar
deposition. Both domains show similar lithofacies,
although in detail important differences exist.
In the Colquijirca district, only the western
domain of the Chambar Formation crops
out (Figure 1a.4). The exposures constitute the
Lachipana, Viscajaga and Pumarrn hills as well as the
small outcrops of strongly altered carbonate rocks
at Gualquepaqui, Yanque Maria and Bohorquez
(Figures 1a.2 and 1a.3). A generalized stratigraphic
section of the western domain is summarized from
Angeles (1993), complemented with personal data
for the San Gregorio area.
From bottom to the top, the sequence
comprises basal breccia, described briefly above,
and sandstones and calcareous dolostones equivalent
to the terrigenous basal unit of the Pucar Group
as defined by Mgard (1978). This is followed by a
sequence known locally as basal dolostones, which
consist of 15 to 30 m thick of finely laminated beige
dolostones (Figure 1a.5). Scarce concretionary chert,
possibly pseudomorphic after evaporite minerals,
is present in this interval (Angeles, 1993). The next
20 m are poorly exposed; however in the few places
where they occur (e.g., east of Huaraucaca; Figures
1a.2 and 1a.3) they comprise cinerites or sediments
derived from them. Drilling in the San Gregorio area
intercepted these sediments intercalated with relatively
thin intervals of dolostones and rarer limestones.
The rest of the sequence crops out outheast of Sacra
Familia (Figure 1a.2), where according to Angeles
(1993), it is composed of >200 m of whitish gray
finely laminated dolostones (Figure 1a.5). The first
40 m of this interval like the basal dolostones, are
characterized by concretionary chert. In the last few
meters of this interval, interstratified chert occurs
(Angeles, 1993).
The generalized section of the Chambar
Formation in the western domain, described by
Angeles (1993) at Cerro Lachipana, from the
meter 220, the sequence displays several meters of
arenaceous dolostones intercalated with milimetric
to centimetric layers of coarse-grained sandstones
25
 CHAPTER 1

E-360 000
4300
Condorcayn

45 70

F1
F1 25

PU 22

F2 50 4448 aa'
46
25 COLQUIJIRCA
N-8 811 000

F2 F1 4458
33

F1
35
4250
4200

F2
bb'
SMELTER
85

Huacchuacaja
60
4300

A
4336

4458
26

F1 MARCAPUNTA

Lachipana 4150

44

BO
N cc'
YM
D
GU
?
SAN GREGORIO
4179
Figure 1.4
4184
1 km

Figure 1a.3: General geology of the Colquijirca district as indicated in Figure 1a.2. Main sources from Jenks (1951), Angeles
(1993, 1999), Brocal staff, and personal data.

26

(west of Puca Ingenio hill, Figure 1a.2). In the
San Gregorio area, these lithofacies are more wide
spread. Most of drill holes intercepted these sandy
intercalations from 150 to 200 m above the contact
with the Mitu Group some of them with thicknesses
of >100 m (e.g., drill holes 22G, 41G). There follows
an interval of more than 50 m of beige laminated
dolostones with cinerite intercalations in the central
portions. Chert tends to increase towards the upper
parts of the interval, where laterally discontinuous
monogenic breccias are present. The upper 30 m of
this sequence consists of cream micritic dolostones
with abundant chert.
The Chambar sequence of the Formation at
Cerro Lachipana was measured by Angeles (1993) to
be near 360 m thickn; nevertheless, from exploration
drilling carried out since 1996 in the San Gregorio
area, it is known to exceed 400 m towards the south
and southeast.
Goyllarisquizga Formation
Clastic continental sedimentary rocks of
the Goyllarisquizga Formation disconformably
overlie the carbonate rocks of the Pucar Group.
These deposits crop out over relatively large areas
throughout the region, though in the Cerro de Pasco-
Colquijirca sector, they are restricted to the western
and eastern borders of the mineralized areas (Figures
1a.1 and 1a.2). The deposits consist of cross-bedded,
medium-grained sandstones and some thin pebble-
sized beds of mostly chert. Thick beds of red to
black shales are intercalated with the sandstones
at several levels. Coal horizons are common in the
Goyllarisquizga Formation (Broggi, 1922).
Chulec-Pariatambo-Jumasha Formations
Marine limestones of the Chulec, Crisnejas,
Pariatambo and Jumasha Formations (Albian to
Turonian) are exposed in the northwest and northeast
sectors of the region. They have not been recognized
in the Cerro de Pasco and Colquijirca districts.
Paleogeography, tectonic evolution and
structures
The presence of detrital sediments, including
Excelsior clasts, in the basal breccia (the terrigenous
basal unit of the Pucar Group, see above) implies
exposure of the basement due to uplift during the
Upper Permian-Lower Triassic. The uplift was
possibly related to extensional tectonism active when
the Triassic sea (in which the Pucar Group formed)
transgressed intracontinental basins (e. g., Mgard,
1978).
According to Rosas et al. (2004), the Pucar
CHAPTER 1
transgression is attributable to regional subsidence
that marked the transition from the Upper Paleozoic-
Lower Triassic Mitu rift to post-rift tectonism and
fault-controlled subsidence. The Pucar Group
succeeded the Mitu continental sediments and
subordinate alkaline volcanic rocks as a carbonate-
dominated blanket late in the rift stage, when the
various Mitu depocenters became yoked. The
carbonate cover grades landwards into clastic-
evaporitic continental deposits. The Pucar Group was
largely deposited in shallow water, with no evidence
for deep-water paleoenvironments during deposition
of the Chambar and Condorsinga Formations. Only
the Aramachay Formation (Hettangian-Sinemurian)
records generalized flooding of the basin. The
presence of several intercalations of alkaline volcanic
rocks supports the idea of a late-rift character for
the Pucar basin. The very thick (nearly 3000 m)
eastern Chambar domain, recognized west of the
Longitudinal fault in the Cerro de Pasco-Colquijirca
area, corresponds to one of the most important
tectonically controlled depocenters recognized in the
basin.
According to Mgard (1978), extensional
tectonism occurred in post Bajocian and pre-
Neocomian times, at the end of the Pucar
sedimentation, and represents the northern equivalent
of the Nevadian epirogeny widespread in southern
Per (Jenks, 1951; and Newell, 1949). At Rancas, in
the Cerro de Pasco-Colquijirca sector (Figure 1a.1),
an angular discordance between the western domain
sequences of the Pucar Group and the Cretaceous
Goyllarisquizga Formation could reflect these
movements.
Paleocurrent determinations in the region
indicate that the terrigenous sediments of the
Lower Cretaceous Goyllarisquizga Formation were
deposited from an emergent segment (Maran
geanticline), along what is now the Eastern Cordillera
(Angeles, 1993, 1999). A marine transgression starting
in the Albian gave rise to the Chulec, Pariatambo and
Jumasha Formations deposed. As stated by Angeles
(1993; 1999) variations in the thickness of this unit
are controlled by the distance to the source blocks,
and hence, the distance to the Longitudinal fault
(Figure 1a.4). The approximate thickness of 150 m at
Quivlacocha (Angeles, 1993) close to the Longitudinal
fault, combined with measured thicknesses of 80 to
100 m farther west (at Colquijirca, from logging of
exploration drill holes SD-88 and SP1-218), is in
general accordance with such a concept.
Magmatism
Important magmatic activity in the region
during the Mesozoic is restricted to Cretaceous
volcanism in the Atacocha mining district, some 10 km
northeast of Cerro de Pasco and, less importantly at
Cacun, 4 km north-norwest (Figures 1a.1 and 1a.2).
27
28
W E

from Angeles (1999).

a a'
Rio San Juan
Colquijirca
4500 4500 m.

4000 4000 m.

b b
R. San Juan

Marcapunta
4500 4500 m.

Zone of complicated block

4000 system due to collapse of the 4000 m.
Marcapunta volcanic
complex

c c

4500 4500 m.
San Gregorio

4000 4000 m.

2 Km

E-360,000
H=V

Figure 1a.4: General geological sections of the Colquijirca district as indicated in Figures 1a.2 and 1a.3. Slightly modified
CHAPTER 1

At these places, basaltic flows up to several hundred
meters thick are intercalated with the Goyllarisquizga
sandstones (Johnson, 1955). Soler (1991) studied
some of these intercalations and concluded that the
basalts may represent early stages of rifting.
Cenozoic
Stratigraphy
Over large areas of the central Peruvian Andes,
a relatively thick continental sequence composed
mostly of conglomerates, sandstones, sedimentary
breccias, marls and limestones of Upper Cretaceous-
Eocene age rests unconformably on the Paleozoic
to Lower Cretaceous rocks (e.g., Mgard, 1978;
Figure 1a.4;). Part of this sequence constitutes the
Pocobamba Formation in the Cerro de Pasco and
Colquijirca districts.
Pocobamba Formation
The Pocobamba Formation was first described
by McLaughlin (1924). Jenks (1951) divided the
Pocobamba Formation into three members: Lower
Member (or Cacun Member; Angeles, 1999) at the
bottom, Shuco Member in the middle and Calera
Member at the top (Figure 1a.4).
Cacun Member. The Cacun Member, named
after the type locality near Cacun (Angeles, 1999),
consists of a sequence of up to 300 m thick of
shales, sandstones, conglomerates and limestones. In
the Colquijirca district, the Cacun Member is poorly
exposed and limited to the western block between
the Lachipana and Puca Ingenio hills (Figure 1a.2).
It can, in general, be characterized as a typical red
bed sequence. Its lower parts are composed of
reddish sandstones, siltstones, and mudstones, often
displaying cross-bedding. Channel-fill conglomerates,
breccias and other coarse-grained detrital rocks also
typify these intervals. The clasts, <5 cm long, mostly
subrounded and cemented by calcareous material,
consist of Pucar-derived limestones (Angeles 1993,
1999), with minor sandstones, siltstones and locally
milky quartz.
The upper intervals of the Cacun Member
comprise metric beds of whitish limestones, with
some chert, pellets and biogenic structures. According
to Angeles (1999), these limestones are lacustrine
in origin. The same author estimated the thickness
of the Cacun Member as no less than 100 m. At
Colquijirca, the Cacun Member is exposed locally at
Lachipana hill (Angeles, 1999).
Shuco Member. The Shuco Member consists
principally of poorly sorted monomictic, clast-
supported breccias and conglomerates (Figure 1a.5).
Its outcrops cover considerable areas in the Cerro de
CHAPTER 1
Pasco-Colquijirca sector (Figures 1a.2, 1a.3 and 1a.5).
Drilling, notably at Colquijirca, showed it to be over
a large area concealed beneath the Calera Member.
In the Cerro de Pasco district, the Shuco Member
lies on the Cacun Member whereas in the vicinity
of Colquijirca it lies on different pre-Cenozoic rocks,
including the Mitu (west of the Principal pit; Figure
1a.4) and the Excelsior Groups (at Condorcayn).
Chambar Formation pebbles, cobbles and boulders
dominate as clasts. Clast size and clast/matrix ratio
as well as relatively subtle variations in the lithology
of clasts and matrix reflect distance from the
Longitudinal fault (e.g., Jenks, 1951; Angeles, 1999).
Close to the fault, in the Cerro de Pasco district,
the largest boulders, some up to 3 m in diameter
are found. The clasts near the fault are invariably
Chambar limestones and generally are angular to
subangular. Interclast spaces consist of a mixture
of angular to subrounded granuled- to cobbled-
sized material, including sandstone, cemented by
calcite. Westward from the Longitudinal fault, the
clasts display increased rounding and decreased
size. Other lithologies are locally abundant, as in the
easternmost exposures of the Shuco Member in the
Cerro de Pasco district. There, west of the RSJV
(Rio San Juan-Venenococha; Figure 1a.2) fault more
than half of the clasts consist of dolostones of the
western Chambar domain (see section 1.2.1.1)
with the remaining fraction from the eastern
Chambar domain (Angeles, 1999). Poorly stratified
beds, mostly composed of pebbles, tend to occupy
distal positions relative to the Longitudinal fault
(Angeles, 1999), as in the Colquijirca district, west
of the operating open pits. There, the presence of
incipient bedding is accompanied by a dominance
of subrounded clasts, the majority not >20 cm in
diameter (Figure 1a.5).
The Shuco Member is considered as a
fanglomerate or piedmont deposit (Jenks, 1951;
Angeles 1993, 1999), with the above mentioned
characteristics being consistent with this interpretation.
The Longitudinal is the eastern limit of the main
uplifted block, largely made up of the Chambar
Formation which is the erosional source for most
of the Shuco material. As stated by Angeles (1993,
1999), variations in the thickness of this unit are also
controlled by distance from the uplifted blocks, and
hence, from the Longitudinal fault (Figure 1a.4).
Calera Member. McKinstry (1936), Noble
(1992) and Angeles (1999) assigned the status of
Formation to the carbonate and detrital rocks resting
on the Shuco Member (Figure 1a.4). In this review,
use of the classical sub-division proposed by Jenks
(1951) is preferred which refers, and refer to this
sequence as part of the Pocobamba Formation,
namely the Calera Member. According to Jenks (1951),
the Calera Member is estimated to be composed of
about 70 per cent argillites, limestones, siltstones
and sandstones and about 30 per cent limestones.
29
 CHAPTER 1

A B

C D

Pocobamba
Formation

Figure 1a.5: Images of the main rocks of the Colquijirca-Cerro de Pasco area. A. Arkosic sandstone from the Upper Perm-
ian-Lower Triassic Mitu Group red beds on the southern flank of the Marcapunta volcanic complex. B. Finely laminated
dolostone from the Upper Triassic-Lower Jurassic Pucar Group at Lachipana hill. C. Calcareous conglomerate from the Upper
Cretaceous Shuco Member of the Pocobamba Formation, west of Colquijirca. D. Intercalations of limestones, shales, marls
and tuffs of the Eocene Calera Member of the Pocobamba Formation. These intercalations are exposed in the Principal pit at
Colquijirca. E. View from the north of the Marcapunta volcanic complex. An outcrop of the Pocobamba Formation is observed
which farther south is intruded by the volcanic complex.

Numerous beds, other than true limestones, have a
calcareous component, many of them marls. Angeles
(1993) divided the Calera Member into three members,
here sub-members, based mainly on differences in
lithofacies: Lower, Middle and Upper sub-members.
The following is an abstract of his work.
Lower sub-member: The first 10-20 m above
the Shuco Member are not exposed. There follows a
sequence dominated by detrital sediments, including
tuffs, sandy siltstones and lesser conglomerates. The
conglomerate beds are of decimetric thickness and
consist of pebbles of black limestones in an argillic
matrix. Similarly, several intervals with no exposure
complete this first 50-m-thick section. The sub-
member is completed by a thin interval characterized
by marls, calcareous argillites and limestones, the last
with characteristic relicts of rhizoconcretions and
roots. This interval is also interbedded with detrital
sediments, similar to the lower part, although in this
case subordinate. The total thickness of the lower
sub-member is estimated to be 64 m.
Middle sub-member: This part of the Calera

30

Member is the best exposed, both as natural outcrops
in several parts of the district in the open pits (Figure
1a.5). It is characterized, in contrast to the other sub-
members, by an abundance of nearly pure carbonate
rocks. In the old La Calera quarry, limestones grade
from mudstone to coarse grainstone, usually with
biogenic structures and, in some cases, fossiliferous.
Intercalations of large concretions of chert and thin
beds of argillite complete the interval. There follows
a generally finer-grained interval consisting of an
alternation of multicoloured argillites and limestones,
generally mudstones to wackestones. Exposure of this
sub-member in the open pits reveals that it is much
richer in chert compared with the unaltered rocks
beyond the limits of mineralization. This suggests
that at least part, if not probably most, of the chert
in this part of the district has a hydrothermal origin.
Angeles (1993) estimated the thickness of the middle
sub-member to be nearly 55 m.
Upper sub-member: In contrast to the lower
sub-members, it appears to be present only south
of the Cuchis Grande lake (Figure 1a.2), and thus,
restricted to the Colquijirca district. The most
complete stratigraphic interval is exposed in the
open pits where intercalations of argillites, siltstones,
marly dolostones and some volcanosedimentary beds,
including tuffs, occur. According to Angeles (1993),
this sub-member exceeds 150 m in thickness.
Considering the measurements made by Angeles
(1993), the total thickness of the Calera Member
attains a minimum of 250 m. However, exploration
drilling immediately northeast of Marcapunta hill
reveals an up to 500 m thick sequence. The Calera
Member is thought to be of Upper Eocene age on
the basis of K-Ar age of ~36-37 Ma for biotite from
a tuff layer located near the base of the Lower sub-
member (Noble et al., 1999).
Paleogeography, tectonic evolution and
structures
Mgard (1978) stated that the abundant Lower
Cenozoic red beds of central Per were products
of extensive erosion from essentially two emerged
blocks. One was located along the present coast and
isolated the Andean platform from marine influences.
The second passed approximately through Cerro de
Pasco, parallel to the general alignment of the Andean
Cordillera. Much of the continental material present
in the Cerro de Pasco-Colquijirca sector, including
the deposits of the Cacun and Shuco Members,
was formed by erosion of this second block. This
same scenario apparently existed since the Upper
Cretaceous, although at that time the presence of
marine deposits suggests an ephemeral marine
incursion.
According to Mgard (1978), major faults
strongly influenced the spatial distribution of these
high-energy Eocene deposits, as in the Cerro de Pasco
CHAPTER 1
and Colquijirca districts. In the Colquijirca district,
Angeles (1999) linked the Cacun Member deposits
to tectonic movements related to the Longitudinal
fault. The abundance of coarse sediments in the lower
intervals of this member, and the predominance of
calcareous material at the top, have been attributed
to waning of tectonism, possibly linked to this major
structure. A similar process could have occurred
during deposition of most of the Shuco Member
with variations in lithofacies and thickness being
related to distance from the Longitudinal fault.
The formation of a lacustrine basin during the
Upper Eocene marked the beginning of a period of
relative tectonic quiescence. The interpretation by
Angeles (1999) implies an early ephemeral basin, with
periodic incursions of fluvial material (Lower sub-
member), followed by the establishment of a more
stable basin occupied by the Calera lake. The Calera
lake, according to the same author, evolved from a
shallow holomictic to shallow ectogenic meromictic
lake, in which sediments either poor and rich in
organic matter and typical of the Middle and Upper
sub-members, respectively, accumulated. Variations
in facies were controlled by climatic changes and by
a possible extension of the hydrographic net rather
than by tectonic processes (Angeles, 1999)
Tectonics in central Per during Cenozoic
were essentially compressive (e.g., McLaughlin,
1929; Mgard, 1978), and consisted of discrete,
short, intense periods of deformation with probable
peaks at 100-38 (not well defined; e.g., Myers, 1975;
Cobbing et al., 1981), 26, 17, 10, 7 and 2 Ma (e.g.,
Mgard, 1984). Indeed, most of the structural
features currently observable in the Cerro de Pasco-
Colquijirca sector formed or were active during this
Cretaceous-Tertiary interval (Jenks, 1951; Angeles,
1993). Mgard (1984) stated that the major Andean
structures in central and northern Per are related
to the Inca (50-38? Ma), Quechua I (17 Ma) and
Quechua III (7 Ma) tectonic pulses. At Colquijirca,
the major tectonic phases occurred subsequent to
Pocobamba Formation sedimentation, that during
the Aymara (26 Ma) or Quechua I (17 Ma, Angeles
(1993, 1999) events.
The major north-south Longitudinal and
FRSJV faults display evidence for reverse motion
coherent with the nearly east-west main shortening
direction for the region at 26 and/or 17 Ma (Figures
1a.1, 1a.2, and 1a.3). A strike-slip fault system present
throughout the Cerro de Pasco-Colquijirca sector
(F1 and F2 system in Figure 1a.3) is directionally
consistent with first-order breaks in a similar stress
regime, suggesting that this system was also formed
as a response to compression. Both the folding and
F1-F2 fault system occurred prior to hydrothermal
mineralization and as will be shown later, constituted
important controls on the channeling of mineralizing
solutions, particularly in the northern part of the
Colquijirca district.
31

Magmatism and Mineralization
As in large parts of the Peruvian high Cordillera,
the most important period of magmatism took place
during Cenozoic. Several periods of magmatic activity
are recorded in the Junin-Goyllarizquizga region,
with which virtually all the recognized hydrothermal
mineralization is related.
On the basis of radiometric dating, mostly
using the K/Ar method (Soler and Bonhomme,
1988; Cobbing et al., 1981), a long early event from
the Upper Eocene at ~ 39 Ma and Upper Oligocene
at ~ 29 Ma can be roughly defined. The apparently
unmineralized dacitic to rhyodacitic stocks at Huangoc
(38.5 Ma), Raco (35.2 Ma) and Huancayn (33 Ma),
in the central and northern part of the region belong
to this early period. Those east of Cerro de Pasco at
Mariac and Sunkullo (31 Ma; Soler and Bonhomme,
1988; Figure 1a.1) are of rhyodacitic composition
and younger. The earliest recognized hydrothermal
event in the region, possibly related to the Huangoc
and Raco intrusions, generated a 37.5 Ma epithermal
Au deposit within a volcanic dome at Quicay (Noble
and McKee, 1999; Figure 1a.1). The nearby Pacoyn
Au prospect as well as tuff deposits of the Calera
Member dated at ~36 Ma may be related to this same
~37 Ma pulse (Figure 1a.1).
At the end of this major magmatic event, at
~ 29 Ma, a dacitic intrusive center was active in the
vicinity of Atacocha. An important hydrothermal
system associated with it produced polymetallic veins
and skarn-related deposits of the Milpo-Atacocha
district. At ~28 and ~15 Ma there is no evidence
of magmatic activity in the region, although it was
intense elsewhere in Per, including nearby parts of
the Western Cordillera.
A second major magmatic event occurred
between 15 and 11 Ma in the Cerro de Pasco-
Colquijirca districts, and was one of the richest and
most mineralized in the world. In contrast to the
earlier magmatism in the region, there was important
development of several diatreme-dome volcanic
complexes emplaced along the major north-south
reverse faults (Figure 1a.1). This fault-controlled
magmatic-hydrothermal belt seems to extends at
least 15 km north of Cerro de Pasco and includes
the El Aguila polymetallic prospect. From north to
south, this belt includes the volcanic complexes at
Cerro de Pasco, Yanamate and, in the Colquijirca
district, Marcapunta.
The Cerro de Pasco diatreme-dome volcanic
complex (15-14 Ma; Silberman and Noble, 1977)
is the largest volcanic center in the belt. It consists
of a multistage dike-dome intrusion emplaced both
prior and subsequent to a major diatreme. Substantial
collapse of large portions of the volcanic edifice,
as well as development of a relatively complicated
fault block system, characterizes this magmatic
center. Compositionally, the rocks are chiefly dacitic
and, less importantly, trachydacitic and andesitic in
32
CHAPTER 1
composition, all of them texturally porphyritic. The
largest hydrothermal sulfide concentration related to
a single intrusive center took place at Cerro de Pasco.
There, even after extensive erosion, the mining camp
still records a minimum of 2.5 billion tones containing
more than 50 volume % of sulfides, largely pyrite,
but also rich zoned polymetallic ores of Cordilleran
base metal lode type (Einaudi, 1977).
South of Cerro de Pasco is the smaller
Yanamate dacitic volcanic center (~15 Ma; Soler and
Bonhomme, 1988). A survey carried out by Angeles
(1993) revealed similar characteristics to those of
Cerro de Pasco, including development of a diatreme
associated with a dome-dike system. Hydrothermal
alteration is recognized in the vicinity of the volcanic
center, although its economic significance has not
been evaluated in any detail.
Further to the south, about 10 km from Cerro
de Pasco, is the Marcapunta volcanic complex (~12
Ma; Vidal et al., 1984), in the center of the Colquijirca
district (Figure 1a.5). As at Yanamate, it also shares
many similarities with Cerro de Pasco including
diatreme development, multistage superimposition
of a dome-lava complex and important collapse of
the sedimentary pile surrounding the main diatreme
neck. Geochemical reconnaissance of unaltered and
slightly altered rocks, presented in the next Chapter,
reveals homogeneous dacitic composition. Several
lines of evidences, discussed in detail in this thesis,
indicate that the mineralization is related to the
Marcapunta magmatic center. Mineralization consists
of disseminated high sulfidation epithermal Au-(Ag)
mineralization and zoned base metal bodies similar
to those at Cerro de Pasco, i. e., Cordilleran base
metal lodes.
Perhaps the last important magmatic expression
in the region are the widespread late Miocene (~6.4-
~5.2 Ma) rhyolitic ash-flow tuffs of Huayllay (40
km southwest of Colquijirca) deposited along the
western border of the high plateau of the central
Peruvian Andes (Harrison, 1943; Cobbing et al.,
1981; Figure 1a.1).
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Noble, D.C., McKee, E.H., Farrar, E., and Peterson,
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 CHAPTER 1

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ous activity and mineralization, Cerro de Pasco, central
Per. Economic Geology, 72, p. 925-930.

Soler, P., 1987, Sur lexistence dun pisode de mta-

morphisme rgional dage Miocne infrieur dans la Cor-
dillre Occidentale des Andes du Prou central. Comptes
Rendus de l Acadmie des Sciences, Paris, 304, p. 911-
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Soler, P., 1991, Contribution ltude du magmatisme

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of the time-dependent evolution of Pb- and Sr-isotopic
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Plutonism from Antarctica to Alaska. Geological Society

34

1b. The Marcapunta diatreme-dome complex
The Marcapunta volcanic complex, as
introduced above, is an intrusive center (Figure
1b.1) consisting of multiple dome-lava bodies of
mainly dacitic composition, which pre- and post-
date several episodes of explosion brecciation and
pyroclastic accumulation typical of diatremes. The
overall internal construct of the volcanic complex,
including the vent structure, is as yet poorly defined.
Only recently, an intense exploration diamond
drilling campaign along the western flank of the
complex, coupled with similar exploration data from
the northern sector, is providing the first constraints
on the three-dimensional internal configuration.
Some of these data are preliminarily presented here.
Also preliminary is the reconnaissance study of the
chemical composition of the volcanic rocks presented
in this section.
Main volcanic facies and spatial
configuration
Topographically, the Marcapunta diatreme-
dome complex resembles a centralvolcano, with
typical gently dipping flanks and the center of the
complex as a topographic high (Figure 1b.1). The
complex is exposed within a slightly elliptical area
and has major axis north-south and nearly parallel to
the main direction of Cenozoic compressive stress.
Most of the outcrops are strongly altered
due to a widespread and intense hydrothermal
alteration; however, a broad lithological distinction
can be drawn on the basis of remnant textures and
evidences provided by limited areas of less-altered
rocks (Figure 1b.1). The early work by Noble (1931)
was the first reconnaissance mapping carried out
at Marcapunta and his nomenclature is often used
in the present work. More detailed work, although
focused on hydrothermal features, as conducted by
Barba (1992) and Vidal (1992), and some additional
details of the Marcapunta volcanic complex can be
found therein.
The outcrops of the Marcapunta volcanic
complex can be divided into two main units:
one constituted by a variety of fragmental rocks
(according to the nomenclature of Schmid, 1981),
largely pyroclastic, known as Unish Tuff and a second
and more important in terms of volume, dominated
by dacitic lava domes and flow rocks. In addition,
CHAPTER 1
drill holes have revealed a large body of polymictic
breccias below the summit of Marcapunta hill (Figure
1b.2). In accordance with Noble (1992), Barba (1992),
and Sillitoe (2000) these breccias represent the upper
fingers of a major diatreme conduit at depth.
There is no detailed map of the original volcanic
facies of the Marcapunta volcanic complex, however,
based on integration of available maps, including
those currently in progress by Brocal-Buenaventura
geologists, the fragmental rocks of the Unish Tuff unit
can be assigned to two main sectors, north and east of
the center of the volcanic complex (Figure 1a.3). In
both places the pyroclastic deposits comprise lapilli-
tuff and less abundant lapilli-tuff breccias (Figure
1b.2). Outcrops within the high parts of Marcapunta
hill comprise lapilli-tuff, commonly displaying well-
developed internal stratification (including cross-
bedding), considerable variation in the grain size and,
although rare, accretionary lapilli. These features are
typical of base surge deposits which are generally
near-vent pyroclastic manifestations, suggesting that
at Marcapunta the main vent was located below the
present-day topographic high (Figure 1b.1). Drill holes
located in the upper portions of Marcapunta (e.g.,
Brocal-548), intercepted, besides lapilli-tuff deposits,
important intervals of breccias. Such breccias consist
of monomictic and polymictic angular clasts, up to
several decimeters in sizes, a fine-grained matrix
composed of milled dacitic rock and juvenile
material. These breccias are interpreted as products
of phreatomagmatic explosions. Also typical of the
central outcrops of the volcanic complex are thin
dike-like bodies of massive fine-grained tuffaceous
material. According to several workers (e.g., Corbett
and Leach, 1998), these are tuffisite injections, i.e.,
another phreatomagmatic product. Drill hole SD-
11 intercepted several intervals of milled polymictic
breccias up to nearly 100 m of vertical extension. In
contrast to the phreatomagmatic breccias described
above, these contain smaller clasts, generally several
centimeters across. Although strongly leached, it
is still possible to recognize original clast lithology
which includes laminated limestone, milky quartz
and phyllite from the Pocobamba Formation, Mitu
Group and Excelsior Group respectively. Such varied
lithology suggests a major phreatomagmatic process
originating at depths of at least 1 km, which accords
with the idea that a relatively large diatreme conduit
exists in the inner parts of the Marcapunta volcanic
35

S N
D C
SD-11
100 m
200 m
Unconformity
Collapse-related fault
Diamond drill hole
Figure 1b.1
Figure 1b.1 Possible internal configuration of the Marcapunta diatreme-dome volcanic complex along a north-south ABCD
section as indicated in Figure 1.4. Data from drill holes and outcroppings.
complex (e.g., Noble, 1992). The SD-11 hole exited
the breccia body at 450 m depth, but considering
other holes located in the surroundings, the diatreme
conduit may have a ramified, flared geometry and
gain continuity downward, with only its upper parts
encountered. The phreatomagmatic breccia also
developed laterally to the north and south, with
offshoots recognized as far as 600 m from the main
vent.
In the northern block (Figure 1b.1), beyond
the main explosive center, extensive drilling has
intercepted lapilli-tuff accumulations of ill-defined
origin, which are often associated with, volumetrically
more important, block and ash deposits up to 200 m
thick. The block and ash deposits are topographically
controlled and consist of monomictic, subangular to
subrounded dacitic porphyry clasts in an ash-sized
matrix of feldspar and pyroxene? grains, and aphanitic
lithic fragments. A relatively common feature of
these deposits is their reverse grading. The block and
ash deposits in this sector are tentatively interpreted
as formed by collapse of lava-domes, more likely by
gravitational instability than by explosive triggering.
The majority of the exposures of the
Marcapunta volcanic complex comprise lava flows
and lava-dome facies (according to the nomenclature
of Self, 1982). Again, despite the fact that the rocks
are strongly altered, it is still possible to recognize
many of the original characteristics of these
facies. Macroscopically, virtually all these rocks are
homogeneously porphyritic in texture (Figure 1b.2).
36
CHAPTER 1
B A
Brocal-548
CM2-604
3800 masl
As shown below, the chemistry of the scarce unaltered
rocks indicates an exclusively dacitic composition.
However, comparatively higher abundances of relict
resorbed quartz in some rocks indicates that besides
dacite, rhyodacitic or less probably rhyolitic rocks
may have been originally present (Yacila, pers. comm.,
2002). These less common rocks were mainly observed
within the volcanic units of the central diatreme
neck. Mineralogically, all the unaltered dacitic rocks
consist of blocky sanidine crystals, as large as 12 cm
(Figure 1b.2), besides smaller plagioclase (probably
andesine; Harvey, 1936 in McKinstry, 1936) and
resorbed quartz (Figure 1b.2). Also distinctive are
euhedral biotite, hornblende and clinopyroxene. The
aphanitic matrix is mainly composed of orthoclase,
quartz and minor biotite. Accessory minerals include
apatite, zircon and magnetite. Harvey (1936) also
reported rutile.
Lava flows dominate over lava domes at
surface. Flow banding (Figure 1b.2) is thus much
more common than blocky spherulitic lava typical of
the central portions of domes (Self, 1982). Drilling
information indicates that lava flows are present
throughout the volcanic pile that is from the erosional
discordance over the Eocene Calera sequence up to
the current top of the Marcapunta complex. The
flows overlie either lapilli or block and ash deposits.
Recognized thicknesses of the lava flows attain 100
m. Based on well-preserved features, such as flow
banding and spherulitic textures, lava dome diameters
vary from a few tens of meters to as large as 500 m
 CHAPTER 1

2 cm
C

200 Pm
B D

3 cm
E F

Figure 1b.2 Images of the Marcapunta volcanic complex. A. General view of the Marcapunta complex looking south. Note
the marked peneplanation of the Altiplano beginning immediately south of Marcapunta. B. A satellite dome showing flow band-
ing. C. Typical porphyrytic texture of the Marcapunta dacitic domes and lava-domes facies. In this case, dacite underwent extreme
hydrothermal leaching with large voids after former K-feldspar phenocrysts D. Thin section image of a typical dacite displaying
resorbed quartz, plagioclases and ferromagnesian minerals in a quartz-rich matrix. E. Well-preserved flow banding in an eroded
altered dome. F. Typical fragmental rocks of the northern flank of Marcapunta, composed mainly of angular to subrounded
dome clasts in a lapilli tuff matrix.

37

east of Smelter, although most of those recognized
are generally <50 m.
Based mainly on surface observations from
several places, Angeles (1999) provided several
lines of evidence for subsidence or collapse of an
important part of the Marcapunta volcanic complex.
He recognized normal faults along the northern,
southern and southwestern borders of the complex
(Figure 1b.1) in what seems to be a ring fault
pattern similar to the peripheral structures of many
much larger caldera systems (e.g., Lipman, 1997).
Moreover, he deduced from measured strikes and
dips that the lapilli-tuff deposits (surge deposits)
are spatially disposed in a centripetal arrangement
coherent with central subsidence. The observations
of Angeles (1999) are supported by a preliminary
three-dimensional correlation based on recent
drilling information (Figure 1b.1). In the northern
sector of Marcapunta, for example, a grid of drill
holes, spaced no more than 150 m from each other,
allows precise delineation of the Mitu-Pocobamba
discordance 1km from Smelter to the innermost
portions of the Marcapunta center. What was found
is a generalized deepening of the discordance on
approach to the main vent (Figure 1b.1). While
the deepening is rather gentle in the external parts,
it steepens in proximity to the diatreme conduit,
indicating an increase in downsag ging. Drill hole
Brocal-548 gives an idea of the maximum magnitude
of such movement, with a relief on the discordance
of at least 300 m between holes Brocal-548 and CM2-
604 (Figure 1b.1). A similar configuration is indicated
when other stratigraphic or lithological markers
such as the conglomeratic Lower sub-member of
the Pocobamba Formation, are delineated. The
same configuration possibly characterizes the
southern sector of Marcapunta, although there the
available data are limited. Concluding, it appears that
important subsidence probably affected the overall
volcanic complex, being most prominent in the near-
vent parts. The geometry of the main subsidence
structures remain ill-defined. Nevertheless, a
generalized system of semi-vertical fractures, some
of them normal faults with minor displacements, are
observed in the Smelter underground mine (Figure
1b.1).
General Chemistry
The scarcity of unaltered rocks makes
petrologic characterization of the Marcapunta
volcanic rocks difficult. However, seven samples
were found to be exempt from alteration and were
analyzed for major and trace elements using the classic
XRF technique (Appendix 1b.1). These samples were
collected exclusively from flanking domes where
hydrothermal alteration was minor or non-existent.
Neither pyroclastic rocks nor breccias were analyzed
in the present reconnaissance, mainly because all
38
CHAPTER 1
those observed microscopically are considered too
strongly altered.
Four of the six unaltered samples were
analyzed for rare earth elements (REE) (PBR-148,
PBR-185c, PBR-216 and PBR-216a; Appendix
1b.2). In addition, in order to obtain REE patterns
representative of the central portions of the volcanic
complex, the diatreme itself, two samples from the
outermost haloes of mineralized zones were also
selected (PBR-145 and PBR-199). Although these
last samples display a weak to moderate propylitic
alteration under the microscope, they were analyzed
and included in the study following several papers in
which it has been shown that REE concentrations
in igneous rocks affected by such alteration remain
virtually unchanged and faithfully represent the
original values in their unaltered equivalents (e.g.,
Fulignati et al., 1999).
Major and trace element compositions:
Major and trace element compositions are broadly
homogeneous in all the analyzed samples. Major
element contents are invariably high in silica (>65
%) and alumina (>15 %), whereas contents of MgO
(0.76-1.25 %) and CaO (1.16-2.77 %) are low. At
the level of trace elements, the most remarkable
characteristics are the high concentrations of Sr (up
 A seventh analyzed sample, not included in this set,
from a dome affected by more advanced hydrothermal alteration
(moderate to strong phyllic alteration) displays a nearly identical
profile, although with slightly higher values (Sample PBR-215,
Appendix 1b.2). This sample was finally not taken into account
due to the possibility of REE enrichment by hydrothermal fluid
introduction.
14
12
Trachyte
10
Na2O+K2O wt %
8 Trachydacite
Trachyandesite
Rhyolite
6
Colquijirca district
4
Andesite
Basaltic Dacite
Basalt
Andesite
2
0
40 50 60 70
SiO2 wt %
Figure 1b.3
Figure 1b.3: Total alkalis versus silica discrimination dia-
gram of Le Maitre et al. (1989) showing the volcanic and
subvolcanic rocks of the Colquijirca district.

Abundance/chondrite 1000
100
10
1
La Ce Pr Nd Sm Eu Gd Dy
Figure 1b.4:1b.4
Figure REE abundances of dacitic domes and lavas
of the Colquijirca district normalized to chondrite values of
Nakamura (in Potts et al., 1981). Note that REE patterns
of two slightly altered samples are indistinguishable from those
that are unaltered.
to ~1200 ppm) and low contents of Y (<12 ppm)
(Appendix 1b.1). In accordance with preliminary
classification based on microscopic observations, all
the unaltered samples plotted on the classical total
alkalis versus silica diagram of Le Maitre et al. (1989)
lie in the dacite field (Figure 1b.3). Complementary
plots using the K20 versus SiO2 diagram of Peccerillo
and Taylor (1976) show the unaltered rocks to be
centered on the high-K subalkaline field of Le Maitre
et al. (1989) or high-K calc-alkaline field of Rickwood
(1989).
The set of REE profiles, normalized to
chondrite values of Nakamura in Potts et al. (1981),
show regular distribution and parallelism (Figure
1b.4), suggesting a cogenetic and comagmatic origin
for all the analyzed samples. Such parallelism is
consistent, as mentioned above, with the negligible
mobility of REE in rocks affected by low degrees of
hydrothermal alteration. In terms of composition, the
most outstanding feature is the high LREE/HREE
(light/heavy) fractionation with steep La/Yb ratios
ranging between 42 and 63 (or LaN/YbN ratios of
~30-40) related to strong depletion of HREE (e.g.,
0.6-0.8 ppm Yb). Also remarkable is the absence of
negative Eu anomalies in all the analyzed samples
(Figure 1b.4).
Brief comment on the dacitic rocks of the
Colquijirca District. The high Sr/Y (85-105) and La/
Yb (42-63) ratios of the dacitic rocks at Marcapunta
are similar to those found in rocks termed adakitic, as
characterized and defined for island arcs by Defant
and Drummond (1990, 1993; Figure 1b.5). According
to these authors, such rocks typically have SiO2>56%,
Al2O3>15% and MgO<3%, in addition to Sr/Y>22,
Sr>400 ppm, Y<18 ppm and La/Yb>20. Indeed,
this particular anomalous composition is present in
the whole Cerro de Pasco-Colquijirca belt including
Yanamate (Baumgartner, in prep.; Soler, 1991).
The first genetic interpretation of these particular
magmas was given by Kay (1978), who proposed
CHAPTER 1
150
Adakite field
100
LaN/YbN
Colquijirca district Classical island
dacitic rocks
arcs dacite field
50
Ho Er Tm Yb Lu
0
0 10 20 30 40 50
YbN
Figure 1b.5: Dacites
Figure 1b.5 of the Colquijirca district plotted on
a discrimination diagram for the adakitic and typical mod-
ern island arc dacitic field (after Martin 1999). N: normal-
ized to chondrite values of Nakamura, 1981 (in Potts et al.,
1981).
direct melting of young subducted oceanic crust as
their source. However, more recently, some of these
adakite-like signatures have also been found in rocks
at several latitudes in the Andes where the isotopic
evidence suggests an important crustal contribution
to their formation. Detailed geochemical and
isotopic studies in conjunction with geotectonic
reconstructions, along various segments of the
southern Andes led to some researchers (e.g., Kay et
al., 2005) to propose that these Chilean adakite-like
rocks could have been formed from mantle-derived
magmas with an important involvement of crustal
material, most likely by processes of subduction and
erosion of forearc crust and/or tectonic thickening
and assimilation of Andean crust.
The adakite-like rocks of the Cerro de Pasco-
Colquijirca volcanic belt are included in this latter
category if we take into account the non MORB-
like 87Sr/86Sr isotopic composition (>0.705) from
Yanamate (Soler, 1991) and Cerro de Pasco (Noble
and McKee, 1999). It remain to be shown if similar
or alternate processes can explain the genesis of
these anomalous dacitic rocks in the Cerro de Pasco-
Colquijirca magmatic belt, where two of the largest
polymetallic deposits occur.
REFERENCES
Angeles, C., 1999, Los sedimentos cenozoicos de
Cerro de Pasco: estrastigrafa, sedimentacin y tectnica.
Sociedad Geolgica del Per, Volmen Jubilar N 5, p
103-118.
Barba, G., 1992, Mapeo geolgico a escala 1:2000 del
Cerro Marcapunta. Informe privado Sociedad Minera El
Brocal S.A., 91 p.
Corbett, G.J., and Leach, T.M. 1998, Southwest Pacific
39
 CHAPTER 1

Rim gold-copper systems: structure, alteration and miner-
alization. Society of Economic Geologists, Special Publi-
cation No. 6, 237 p.
Defant, M.J., and Dummond, M.S., 1990, Derivation
of some modern arc magmas by melting of young sub-
ducted lithosphere, Nature, 347, p. 662-665
Defant, M.J., and Dummond, M.S., 1993, Mount St.
Helens; potential example of the partial melting of the
subducted lithosphere in a volcanic arc. Geology, 21, 547-
550.
Fulignati P., Gioncada A., and Sbrana A., 1999, REE
behaviour in the hydrothermal alteration facies of the ac-
tive high-sulfidation system of Vulcano (Aeolian Islands,
Italy). Journal of Volcanology and Geothermal Research,
88, p. 325-342.
Kay, R.W., 1978, Aleutian magnesian andesites-melts
from subducted pacific ocean crust. Journal of Volcanol-
ogy and Geothermal Research, 4, p. 117-132.
Kay, S.M., Godoy, E., and Kurtz, A., 2005, Episodic
arc migration, crustal thickening, subduction erosion, and
magmatism in the south-central Andes. Geological Soci-
ety of America Bulletin, 117, p. 67-88
tivation analysis a critical appraisal of calibration errors.
Chemical Geology, 34, 331-352.
Rickwood, P.C., 1989, Boundary lines within petrologic
diagrams which use oxides of major and minor elements.
Lithos, 22, p. 247-263.
Schmid, R., 1981, Descriptive nomenclature and clas-
sification of pyroclastic deposits and fragments: Recom-
mendations of the IUGS Subcommission on the System-
atics of Igneous Rocks. Geology, 9, p. 4143.
Self, S., 1982, Lava flows and domes, in Pyroclastic
Volcanism, L.D. Ayres, ed., Geological Association of
Canada, Short Course Notes, 2, p. 53-57.
Sillitoe, R. H., 2000, Zinc Exploration at Colquijirca,
Central Per. Private report for Compaa de Minas Bue-
naventura S. A., 9 p.
Soler, P., 1991, Contribution ltude du magmatisme
associ aux marges actives-ptrographie, gochimie iso-
topique du magmatisme Cretac a Pliocene le long dune
transversale des Andes du Prou Central-Implications
godynamiques et mtallogeniques. Unpublished thse de
Doctorat des Sciences Naturelles, Paris, Universit Pierre
et Marie Curie, Paris VI, 832 p.

Le Maitre, R.W., Bateman, P., Dudek, A., Keller, J., La
Meyre Le Bas, M.J., Sabine, P.A., Schmid, R., Sorensen,
H., Streckeisen, A., Wooley, A.R., and Zanettin, B., 1989,
A classification of igneous rocks and glossary of terms.
Oxford Blackwell Scientific Publications, 193 p.
Vidal, C., 1992, Exploraciones por oro en el Suroeste
del Cerro Marcapunta. Distrito Minero de Colquijirca
y Cerro de Pasco. Informe privado Sociedad Minera El
Brocal S.A., 26 p.

Lipman, P.W., 1997, Subsidence of ash-flow calderas:

relation to caldera size and magma-chamber geometry.
Bulletin of Volcanology, 59, 198-218.

McKinstry, H.E., 1936, Geology of the silver deposit

at Colquijirca, Per.
Economic Geology, 31, p. 619-635.
Noble, J.A., 1931, Colquijirca examination, 1930-31.
Informe privado Cerro de Pasco Copper Corporation, 34
p.
Noble, D.C., and McKee, E.H., 1999, The Miocene
metallogenic belt of central and northern Per, in Skin-
ner, B.J., ed., Geology and mineral deposits of the central
Andes. Society of Economic Geologists Special publica-
tion No. 7, p. 155-193.

Noble, D.C., 1992. Private report. Compaa de Minas

Buenaventura.

Peccerillo, A., and Taylor, S.R., 1976, Geochemistry of

Eocene calc-alkaline volcanic rocks from the Kastamonu
area, Northern Turkey. Contribution to Mineralogy and
Petrology, 58, p. 63-81.

Potts, P.J., Thorpe, O.W., and Watson, J.S., 1981, De-

termination of the rare earth element abundances in 29
international rock standards by instrument neutron-ac-

40
 CHAPTER 1

Appendix 1b.1. Major element composition of unaltered lava-dome rocks from the Marcapunta diatreme-dome complex. Analysis by
XRF.

Sample SiO2 Al2O3 Fe2O3 MnO MgO CaO TiO2 Na2O K2O P2O5 LOI Sum
PBR-148 67.00 15.51 4.51 0.08 0.90 1.93 0.74 3.11 3.09 0.27 2.14 99.28
PBR-185 c 65.59 17.72 3.47 0.02 0.73 1.16 0.92 2.96 4.06 0.36 3.03 100.02
PBR-199 67.37 15.57 4.71 0.09 0.87 1.95 0.67 2.87 3.10 0.26 2.25 99.72
PBR-216 67.15 15.35 3.51 0.04 1.25 2.66 0.72 4.15 3.45 0.61 1.09 99.98
PBR-216 a 66.97 15.23 3.54 0.04 1.25 2.66 0.72 3.76 3.42 0.59 1.10 99.28
PBR-216 b 66.80 15.18 3.56 0.04 1.25 2.67 0.73 3.78 3.42 0.58 1.15 99.15

Appendix 1b.2: Rare earth element concentrations in dacitic domes and lava-domes of the Marcapunta volcanic complex.
Sample La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm

PBR-145 33.5 75.8 9.3 41.8 6.5 1.37 2.8 n.d. 1.6 0.34 0.9 0.14 0.8 0.08
PBR-148 33 74.2 9.1 37.2 6.8 1.46 2.8 n.d. 1.9 0.39 0.9 0.13 0.7 0.1
PBR-185c 38.6 83.1 9.5 39.6 6 1.28 2.4 n.d. 1.6 0.32 0.8 0.11 0.7 0.09
PBR-200 35.4 77.8 9.3 38.3 5.7 1.43 2.7 n.d. 1.8 0.36 1 0.15 0.8 0.09
PBR-215 59.3 121.2 14.5 68.3 10.3 2.44 5 n.d. 2.9 0.62 1.5 0.21 1.2 0.15
PBR-216 42.7 90.5 10.8 45.7 6.6 1.65 2.9 n.d. 1.8 0.39 0.9 0.13 0.7 0.08
PBR-216a 37.8 82.6 9.7 42.4 6.2 1.54 2.8 n.d. 1.9 0.42 1 0.12 0.6 0.09

41
 CHAPTER 1

42

Chapter 2
Description of the mineralization types
Introduction
The goal of Chapters 2a, 2b, 2c, 2d, and 2e
is to document physically, mineralogically and
geochemically the main characteristics of the two
mineralization types in the district: (a) sulfide-rich
polymetallic deposits (Chapters 2a, 2b, and 2d) and
(b) disseminated Au-(Ag) mineralization (Chapter
2c). Additionally, these two mineralization types are
compared in Chapter 2e.
Field and laboratory methods of study
The field part of the present work was carried
out for more than 18 months while the writer was
a mine geologist at Colquijirca (1997-1998). During
that time and for an additional period of six months
as a PhD student (this study), the writer worked in
the different deposits and exploration projects of
Sociedad Minera El Brocal S.A.A. in the Colquijirca
district. Most of the time was spent logging 15000
m of drill core, and revising a similar number of
meters of core from each of the main deposits in the
district. Mapping of selected parts of the open pits
in the Colquijirca deposit and key areas in different
parts of the district was also undertaken. Another
important part of the study was integration of
available mine data as well as discussions with other
mine geologists (see acknowledgments at the end of
the manuscript).
Laboratory work comprised the study of nearly
450 representative samples from throughout the
district. Although the majority of them correspond
to mineralized areas, a number of them are fresh
rocks. Of this total, some 300 resulted in thin and
polished sections, which were studied by microscopy,
infrared microscopy, X-ray diffraction, electron
microprobe and scanning electron microscopy.
Major and trace element characterization of ores and
unaltered rocks were made using a combination of
several quantitative chemical techniques, basically
X-ray fluorescence, inductively coupled plasma and
neutron activation analysis. Details on each individual
analytical technique, such as operating parameters
and standardization are given in tables.
CHAPTER 2
Main terminology
The following terms are employed in the sense
of Barton (1963, 1970), Hemley and Hunt (1992),
and Einaudi et al. (2003).
Mineral assemblage: A grouping of minerals
occurring in direct contact and displaying no evidence
of reaction with one another (Einaudi et al., 2003).
Although Hemley and Hunt (1992) applied this
term when chemical equilibrium is implied, in this
work, if not specifically discussed, the term mineral
assemblage is strictly descriptive.
Mineral association: A grouping of minerals
occurring together but which are not necessarily all
in contact nor necessarily deposited at the same time
(Einaudi et al., 2003). The common non-equilibrium
conditions under which a mineral association was
often formed is evident here (Barton et al., 1963;
Hemley and Hunt, 1992).
Stage or single stage of mineralization: This
term is adopted in the sense of Barton (1970) for
a grouping of phases representing an interval of
deposition during which there is no discernable
chemical or physical change. In this work, single
stages of mineralization are discriminated from
space-integrated, crosscutting relationships.
Paragenesis: This term is used, following a
discussion by Hemley and Hunt (1992), for a group
of minerals implying contemporaneous formation.
It is used as an alternative term when referring to a
mineral assemblage in which two or more minerals
are believed to have precipitated from a single stage
of mineralization.
crystallization reversal: This informal term
refers to a particular mineral assemblage texture
consisting of two or more phases displaying
one or more repetitive sequences of reversed
crystallization.
43
 CHAPTER 2

44

2a. The Smelter deposit
The Smelter deposit is one of the sulfide-rich
polymetallic deposits of the Colquijirca District.
It is located immediately north of the Marcapunta
volcanic complex (Figure 2a.1). As described here,
corresponds to the mineralized area comprised
between grid lines 524 and 628 (Figure 2a.2). These
limits are informally used by Colquijirca geological
staff for resource calculation purposes. This work,
however, adds the sector comprised between grid
lines 628 and 700, this last the conventional southern
limit of the Colquijirca deposit (Figure 2a.2).
The Smelter deposit consists essentially
of enargite-rich bodies with significant gold
concentrations close to the Marcapunta volcanic
complex. The Smelter deposit contains approximately
50 Mt at 1.9 % Cu, 24 g/t Ag, and 0.35 g/t Au. Using
Ag/Au ratios as a characterizing parameter, the
whole Smelter deposit show a Ag/Au ratio of about
75. However, lower values (30-50) characterize the
internal parts of the deposit and, in strong contrast,
values of up to 500-1000 are present in more external
positions.
Host rock
Drill hole correlations indicate that the
enargite-bearing silica-pyrite replacements are largely
hosted by the carbonate rocks of the Pocobamba
Formation (Figures 2a.2 and 2a.3). Surrounding the
main diatreme conduit and the central volcanic and
subvolcanic domes of the Marcapunta complex,
replacement was extensive and affected the entire
Pocobamba Formation, including 150 meters of the
Calera and apparently also the Shuco Member (Figure
2a.3). With increasing distance toward the north, the
silica-pyrite bodies became progressively restricted
to intermediate stratigraphic positions within the
Pocobamba Formation. This is particularly evident
northward from line 596 (Figure 2a.3) where the
lower portions of the Shuco Member and/or Calera
Member are not mineralized (e.g., DDH, CM5-
596, CM2-604), and northward from approximately
the 612 line where the mineralized bodies occur
exclusively within the Calera Member (Figure 2a.3).
A matter of controversy is whether the lower
mineralized interval belongs to the Shuco Member
or to the lower part of the Calera Member. This
 DDH: Diamond drill hole. General Appendix 1 presents
UTM location coordinates for all drill holes cited in this work.
CHAPTER 2
controversy is mainly due to the fact that the two
units contain, though in different proportions,
conglomeratic sediments, and to the intense
replacement that considerably masks and in part
strongly obliterates the original lithological fabrics.
Numerous metric mineralized intervals display clast-
supported conglomerate of cobble size, often with
clasts > 10 cm long (DDH-CM2-604, CM5-596). This
feature has only been described previously for two
decimetric intervals in the lower series of the Calera
Member (Angeles, 1993), whereas it constitutes the
fundamental characteristic of the Shuco Member
(Angeles, 1993).
The silica-pyrite replacements also occur in the
volcanic rocks of the Marcapunta complex, though
in minor proportion. The drill holes located within
or in the vicinity of the diatreme conduit (e.g., DDH
Brocal 524, DDH CM9-548, and DDH CM7-564 in
Figure 2a.3) show largely lava domes and block and
ash deposits intensely replaced by silica and pyrite.
Finally, an apparently insignificant fraction of the
silica-pyrite mineralization affected the uppermost
beds of the Mitu Group red beds, particularly south
of line 588 (Figure 2a.3).
Spatial configuration of the mineralized
bodies and controls on mineralization
The following description is based almost
entirely on relatively wide-spaced diamond drilling
evidence. Only in a few places is a three dimensional
perspective obtained from limited data provided by
still accessible underground workings.
The spatial configuration of the early silica-
pyrite replacements is distinctly different from that of
the subsequent copper bodies (mainly enargite-rich).
At a district scale, the replacements can be roughly
depicted as a funnel-shaped structure surrounding at
least 75 per cent, if not entirely, the main volcanic
conduit (Figures 2a.1 and 2a.3). Collectively, the
silica-pyrite replacement geometry is controlled in
parts close to the Marcapunta volcanic complex by
the configuration of the contact between the main
intrusive conduit and the carbonate host sequence. In
more external sectors, bedding was the determinant.
In the Smelter sector, within an area of about
700-800 m radius from the approximate contact
between the conduit and the intruded sedimentary
rocks, replacement of the host rock was virtually total.
45
 CHAPTER 2

E-360 000
4300
Condorcayn

45 70

25 A
22

50 4448 COLQUIJIRCA

46
25
The northern block
N-8 811 000

4458
33

35
4250
4200

SMELTER OR COBRE
MARCAPUNTA
85

Huacchuacaja
60
4300

A
4336

4458
26

MARCAPUNTA OESTE
Lachipana ORO MARCAPUNTA
4150

44

500 m
?
Sulfide-rich 4179
mineraliaztion SAN GREGORIO
4184

A
Figure 2a.1: Geological map of the Colquijirca district showing the extension of the sulfide-rich polymetallic mineralized area.
Except for the recently defined Marcapunta Oeste project, all deposits are included in this work.

46
 N-8812000

N-8811000

N-8810000

N-8809000
E-360000
To
Hua
rau o
a sc
cac
a deP
ro
Cer

and old underground workings.

To
C

524 line
548 line
580 line
612 line
644 line
676 line
708 line
740 line
772 line
804 line

700 line

4,3
60
4,400

Principal pit Condorcayan

40
4,3
E-361000 B
Marcapunta 4,500

4,50
0
Colquijirca
0
4,4
8
A Smelter
4,460 Mercedes-Chocayoc pit
4,440

4,420

4,400

4,380

4,360

4,340
D
4,320
4,300
E-362000 4,280

MINERALIZATION
workings Colquijirca
Cu-(Au-Ag) zone Cu-(Ag-Bi) zone
0 500
Cu-(Ag-Sn-Bi) zone Outer limit of the Zn-Pb-(Ag) zone
meters

47
Figure 2a.2: Plan view of the Smelter-Colquijirca mineralized corridor showing the main ores zones as described in the text
CHAPTER 2
48
A B
SORO MARCAPUNTA N
SMELTER COLQUIJIRCA

the silica-pyrite replacements and ore zones are drawn.

GEOLOGICAL UNITS
100 m
200 m Dacitic diatreme-dome complex (Miocene)

Calera Formation (Eocene), mainly limestones and marls

Shuco Member (Eocene), calcareous conglomerates

Mitu Group (Permian-Triasssic), sandstones

MINERALIZATION
Cordilleran ores Au-(Ag) disseminated ores
Cu-(Au-Ag) zone Quartz-alunite + vuggy silica
containing Au-bearing veinlets
Zn-Pb-Cu-(Ag-Bi) zone

Zn-Pb-(Ag) zone

as indicated in Figure 2a.2. Because of the complexly ramified pattern of the manto-like ore bodies, only the external limits of
Figure 2a.3: North-South composite cross section of the Smelter and Colquijirca deposits along the main axis of the deposit
CHAPTER 2

Thus, the entire section of the Pocobamba Formation
(up to > 150 m thick) including poorly reactive beds
of sandstone, argillite, and siltstone, was extensively
replaced. The great intensity of mineralization in this
area is also reflected by the fact that, in addition to the
Pocobamba Formation, intervals up to several tens
of meters thick, of the underlying Mitu Group red
beds and overlying volcanic units of the Marcapunta
complex were also replaced. It is likely that normal
faults related to the subsidence-collapse of the
sedimentary pile surrounding the volcanic center
played a major role as fluid channelways.
In contrast to the virtually total replacement
in areas close to the intrusive center, northward
from line 580 (Figure 2a.3) replacement is largely
controlled by the receptivity of the original lithology.
Preferred lithologies are fine-grained limestones,
highly permeable coarse-grained sediments such as
packstones, several types of coarse sandstones, and
monomictic to polymictic breccias of granule to
pebble size, all of them typical of the lower series
of the Calera Member. The non-replaced intervals
are dominated by massive, fine-grained argillites and
marls, usually rich in organic matter. The lithological
contrast between replaced non-replaced intervals
suggests that permeability exerted a primary control
in channeling of the early hydrothermal fluids
W
4,400
CM4-588-95 CM9-588-05 CM8-588-96
CM1-588-95 4,350.479 242.05m.
4,348.257 227.30m.
4,348.732 261.55m.
4,200
E - 361,000
0 10
4,000
MINERALIZATION
Silica-pyrite replacement
Cu-(Au-Ag) zone
Zn-Pb-(Ag) zone
Figure 2a.4: East-West cross section of the Smelter deposit as indicated in Figure 2a.2.
CHAPTER 2
responsible for the silica-pyrite replacement. From
these permeable horizons, fluids spread into the
immediately over- and underlying beds.
As shown in Figure 2a.3, the silica-pyrite
replacements separate into two or, in places,
three branches. With increasing distance from the
diatreme conduit, narrowing of the replaced interval
is recognized, and north of line 644 replacement is
confined to the middle portion of the Pocobamba
Formation. In this sector, the Shuco Member is
not replaced (Figure 2a.3). Normal faults probably
channeled the fluids into higher stratigraphic positions
of the Pocobamba Formation, as suggested by
abrupt jumps of the replaced intervals coinciding
with projected faults between lines 588 and 628
(Figure 2a.3). Several thinly mineralized (silica and
pyrite), high-angle normal faults recognized in old
underground workings at Smelter support this view
(e.g., SD CM4-588).
On the basis of drill core correlations, it can
be stated that the fluids that formed the silica-pyrite
replacements migrated outwards from the inner
parts of the Marcapunta volcanic complex, where
they formed essentially veins. As the fluids flowed
upward, they encountered a thick pile of mainly
carbonate rocks where they formed mantos but
also cross-cutting structures (Figure 2a.3). In this
E
4,400
4,344.225 218.00m.
CM6-588-96 CM10-588-06
4,336.851 238.65m. 4,333.439 95.00m.
0.00
CM11-588-06
4,321.905 60.60m.
CM7-588-95
4,284.458 195.80m.
108.50
4,200
221.95
E - 361,400
50 100
METERS
GEOLOGICAL UNITS
Calera Formation carbonates (Eocene)
Shuco Member (Eocene)
Dome
Mitu Group (Permian-Triassic)
49
 CHAPTER 2

1 cm
A B

Jasperoidal
silica Opaline
silica
1 cm 1 cm
C D

E 1 cm F 1 cm

sheelite

rutile
rutile
pyrite
zircon

50 m
G H 30 m

Figure 2a.5: Images of typical occurrences of the Early silica-pyrite stage at Smelter. A. Nearly massive pyrite replacement
of a conglomeratic bed. B. Silica-pyrite replacement of laminated limestones of the Calera Middle sub-member. Possible biogenic
textures now replaced by pyrite. C. Silica-pyrite veinlets cutting silicified limestone. Jasperoidal silica on the borders of the thick
veinlet. D. Pyrite-poor silicified limestone. Part of the silica in the opaline variety. E. Typical sequence of silica-pyrite precipitation
from nearly pyrite-free replacement to younger pyrite-rich veinlets and replacements. F. Typical dark silica produced by argillite
replacement by chert. G. Polished section photomicrograph showing typical fine-grained pyrite disseminations within a quartz
matrix. Rutile and zircon as accessory phases. H. Polished section photomicrograph showing besides rutile, scheelite.

50

northern sector, from Marcapunta to Colquijirca,
fluid movement was essentially from south to
north, possibly controlled by faults related to the
compressive tectonism (Chapter 1a). The pronounced
flatness of the manto-like silica-pyrite replacements
in cross and longitudinal sections (Figures 2a.3 and
2a.4) demonstrates that hydrothermal fluids, once
introduced into the carbonate unit, were restricted
to lateral migration within the Pocobamba sequence.
A similar general longitudinal migration pattern is
recorded in the southern sector of the district where
the fluids seem to have been controlled by the north-
south fold axes toward the Zn-Pb-(Ag) deposit at
San Gregorio (Figure 2a.1).
The available drill core data indicate that
besides the main longitudinal fluid flow to the north
and south, fluids also spread in all directions from
the central portion of the volcanic center, possibly, as
early postulated by McKinstry (1936), following the
margins of the sub-volcanic conduit. Paraphrasing
his statement since no mineralized fractures that could
have served as feeders were found (despite ample crosscutting
under the ore bodies) the conclusion is that the ore-solutions
entered along the beds from the margins of the stock, traveling
gently upward along the pitch. Only recently, has it been
proved, using old drill-hole evidence that the entire
western sector of the Marcapunta center hosts a
significant Cu-(Au) resource (Vidal et al., 2004).
The copper orebodies are mostly hosted by the
early silica-pyrite replacements. Because of the widely
spaced nature of the drilling, delineation of individual
structures is difficult (Figure 2a.3). Available drill
hole and underground evidence indicates that the
orebodies are distributed irregularly within the silica-
pyrite replacements and that they commonly display
crosscutting geometry. Veins mostly reopen the early
silica-pyrite veins within the volcanic complex (DDH
BROCAL 524, 450-500 m depth). Copper mantos
also occurs within the silica-pyrite replacements,
apparently constrained by inherited barriers. Relict
bedding in the Calera Member appears determinant
in the upper mineralized sequence, whereas it seems
less important in the lower sequence where the
probable main barriers were the Calera-Shuco and
Shuco-Mitu contacts.
The silica-pyrite replacements themselves,
which developed extensive intergrain microcavities
(up to > 1 mm wide), provided secondary permeability
along which fluids flowed, enhancing the lateral
fluid migration which controlled the shape of the
mantos.
Mineral deposition history: stages and
zoning
The spatial configuration of ore bodies,
crosscutting relationships at different scales and the
study of more than 180 polished and thin sections
distributed systematically along the northern block
CHAPTER 2
of the district, has allowed discrimination of three
mineral stages. They developed their own zoning
patterns, each of which consists of distinct and
contrasting zones. These stages are: (i) an Early silica-
pyrite stage which produced the large silica-pyrite
replacements; (ii) a Main ore stage which deposed
arsenical Cu-(Au) minerals surrounding the volcanic
complex and rich Zn-Pb-(Ag) ores in their external
parts (Figures 2a.2 and 2a.4); and (iii) a Late ore stage
which generated gold-free copper minerals.
In general, a given mineralized portion is
constituted by a sequence of overlapping mineral
associations and/or assemblages corresponding
to at least two of these three stages. For example,
the Late ore stage is found to overprint internal or
external zones of the Main ore stage, which in turn
may overprint early silica-pyrite replacements. More
complex associations may be related to processes of
zonal migration typical of these classes of sulfide-
rich deposits (e.g., Sales and Meyer, 1949).
Early silica-pyrite stage
In virtually any portion of the Smelter deposit,
an early pre-ore stage composed essentially by silica
and pyrite is evident. This stage, although economically
uninteresting, is by far the most important in terms
of volume. An estimated 800-1,000 millions tones
containing an average of 40-50 volume % pyrite
exist in the Smelter deposit, and a similar volume
probably exists in the recently defined Marcapunta
Oeste resource.
The Early silica-pyrite stage displays distinct
textures depending basically on the lithofacies of
the host rock. In carbonate rocks of the Pocobamba
Formation, the silica-pyrite stage formed a wide
range of textures. In terms of volume, the most
important are those formed by simple replacement
of limestones and/or dolostones, marls, calcareous
argillites and conglomerates, in which some of the
original fabric of the host rock is preserved (Figure
2a.5). Finely laminated textures composed of alternate
pyrite- and quartz-rich bands are characteristic of
many intervals, particularly toward the top of the
mineralized sequence (Figure 2a.5). Lamination is
observed even at a microscopic scale with individual
bands as thin as a few tens of microns. Judging by
their stratigraphic position above the top of the Mitu
Group, these banded intervals correspond to varved
carbonaceous dolostones and limestones, typical
of the upper sub-member of the lacustrine Calera
Member. Other textures also mimic the original fabric
of the carbonate rocks, and it is relatively common
to observe biogenic textures completely replaced by
silica-pyrite.
Strongly silicified and pyritized conglomeratic
beds characterize the sequence below the Calera
Member. This sequence consists of alternating
clast- and matrix-supported breccias, both with well-
51
 CHAPTER 2

A 2 cm B

C 2 cm D 2 cm

alunite

pyrite II
pyrite
enargite
pyrite I 2 cm
E F 0.5 cm

enargite

dickite enargite

1 cm dickite 0.5 cm
G H

Figure 2a.6: Representative occurrences of the Main ore stage. A. Enargite and pyrite II cutting silica-pyrite replacement. B.
Massive sulfide sample consisting of pyrite from the Early silica-pyrite stage and enargite and pyrite II from the Main ore stage.
Note repetitive sequences of crystallization between bands of pyrite II and enargite. C. Enargite replacing matrix of a conglom-
eratic rock. Note that enargite in this sample, as well as in those shown in images A and B, show visually insignificant amounts
of gangue minerals other than pyrite and quartz. This type of occurrence represents more than half of the total enargite resource
in the Smelter Deposit. D. Main ore stage veinlets cutting dacitic rocks of a lava-dome. E. Undulant bands of pyrite II-alunite
replacing massive pyrite from the Early silica-pyrite stage. F. Enargite intergrown with alunite and pyrite in a small geode-like
cavity. G and H. Enargite in contact with dickite and kaolinite. In both cases no reaction effects are observed.

52

rounded monomictic clasts of various sizes. Most of
the brecciation is observed in this sequence, ranging
from relatively rare hydraulic breccias to more
common crackle breccias (Figure 2a.5). Another kind
of breccia consists of sulfide-poor breccias that show
internal sediments filling interclast spaces, suggesting
karstification pre-silica-pyrite formation (Figure 2a.5).
These latter breccias are characterized by monomictic
to heterolithic clasts consisting of centimetric clasts
of original carbonate and/or detrital rocks texturally
identical to the hanging-wall rock. Matrix accounts
for 40-60% of the breccia.
Replacement mineralogy
The main form of silica in the silica-pyrite
replacements is quartz, which typically accounts for >
60 %. The quartz occurs, depending on the grain size
of the original protore, in 30-2,000 m, subhedral
to subordinate euhedral grains. Coarser quartz grains
are rare and always coats cavities.
Other forms of silica are cryptocrystalline
and, in order of decreasing abundance, chalcedonic
chert, jasperoidal silica and much rarer opaline
masses. Chalcedonic chert appears dark in color,
commonly almost black (Figure 2a.5). Under the
microscope, dark chalcedonic chert, which accounts
for about 10 to 20% of the total, is composed of
quartz crystals 5-20 m in size along with variable
amounts of amorphous material. The fine grain size
and impurities derived from the replaced rock are
probably responsible for the dark color. Jasperoidal
silica can be locally important (Figure 2a.5). From
microscopic observations, hematite inclusions give
the typical reddish color. Rarer is the opaline silica
occurring with banded colloform textures and as
alternating colourless and white bands (Figure 2a.5).
Pyrite is most commonly octahedral, ranging
in size from 20 to 1000 m, but mainly between
50 and 400 m (Figure 2a.5). Grains are mainly
appreciably corroded, but the octahedral shape is still
recognizable. Other less common forms are cubes
and, more rarely, pentagonal dodecahedra. SEM
imagery reveals that pyrite is commonly finely zoned.
Arsenic and, to a lesser degree, copper concentrations
are responsible for the zoning. Microprobe analysis
reveals As concentrations up to 1.2 wt. percent,
typically between 0.2 and 0.6 (Table 2a.1). Measured
copper values do not surpass 0.3 wt percent and are
typically <0.2 wt percent. In subsequent sections this
early pyrite is called pyrite I.
Although, as described above, this early stage
is essentially composed by silica and pyrite, it also
includes several other minerals in minor to trace
quantities, including extremely fine grained rutile,
zircon, and scheelite. These three phases were
recognized from microscopic observations and/or
EDS electron dispersive system analysis (Appendix
2a.3).
CHAPTER 2
Rutile is the most abundant accessory mineral
and is found as very fine disseminations in the silica-
pyrite matrix. Subhedral and rarer euhedral grains are
generally elongate and vary in size between 10 and
80 m (Figure 2a.5). Twinning characterizes nearly
25% of the grains. It is common to observe rutile
encapsulated in nearly euhedral quartz, although more
often it occurs as part of the silica-pyrite matrix.
Zircon was recognized from EDS analysis. The
occurrence of zircon is similar to that of rutile in terms
of both grain size and morphology, although it is less
abundant. It is uncertain if zircon has a hydrothermal
origin. However, in view of its presence irrespective
of the host rock for the silica-pyrite bodies, including
both volcanic and Pocobamba sedimentary rocks and
even sandstones of the Mitu Group, it is likely that
the zircons formed hydrothermally.
Scheelite is a rare phase in the Early silica-pyrite
stage and occurs paragenetically with silica and pyrite,
in places crystallized before the quartz and in others
later (Figure 2a.5). Scheelite was mainly observed as
fine anhedral grains disseminated in the silica-pyrite
matrix. Common grain sizes are between 5 and 100
m.
More rarely, muscovite and occasionally also
chlorite were identified through Raman spectroscopy,
and occur as radial aggregates and isolated acicular
grains encapsulated in quartz. These phases are
too fine (usually < 10 m) and in concentrations
too low (< 1 volume %) to be studied by other
conventional techniques. The presence of muscovite
is consistent with the mineralogical composition of
the external haloes to the silica-pyrite replacements
at the deposit scale, which display remnant sericite-
quartz assemblages. These remnant haloes are only
observed around silica-pyrite replacements developed
in the volcanic host rocks in the upper parts of the
mineralized sequence, below the northern flank of
Marcapunta. In thin sections, these haloes display
essentially quartz-sericitepyrite, chlorites. As rare as
the muscovite-(chlorite) are chalcopyrite, sphalerite,
marcasite and pyrrhotite, all as minute inclusions in
pyrite.
The distribution of rutile-zircon-scheelite
defines a weak but definitive zoning within the
silica-pyrite replacements. These phases decrease in
abundance northward, with only rutile observed as
far as 2 km away close to the northern limit of the
silica-pyrite replacements.
Another important feature of the silica-pyrite
stage recognized in this study is its evolution in
time. The Early silica-pyrite stage displays a gradual
increase in pyrite with time. This is particularly well
recognized from crosscutting relationships in vein-
dominated zones where pyrite-rich veinlets cut pyrite-
poor ones (Figure 2a.5). Pyrite abundance as well as
grain size increase from traces to over 60 volume %
in the latest veinlet generations. The minor minerals,
scheelite, rutile and zircon, occur in the pyrite-rich
veins and bodies, suggesting that they were deposited
53
 CHAPTER 2

luzonite

A 100 m B 100 m

enargite

telluride

goldfieldite

tennantite
C 50 m D 50 m

hematite

electrum

E 50 m F 400 m

goldfieldite

Native
tellurium kostovite

G telluride 50 m H 20 m

Figure 2a.7: Polished section photomicrographs of ore minerals from the Main ore stage. A. Typical occurrence of enargite
and pyrite II in contact with later alunite. Compared with pyrite II, enargite displays a more pronounced corroded aspect. B.
Luzonite replacing pyrite II. C. Colusite-alunite assemblage. Note reaction between pyrite II and colusite but not between pyrite
and alunite. D. Tennantite-goldfieldite and associated tellurides growing on younger enargite. E. Hematite partially replaced by
Main ore stage pyrite. F. Electrum grain encapsulated in enargite. G. Goldfieldite associated to gold-bearing tellurides partially
replacing enargite. H. Oil immersion image of native tellurium partially replaced by kostovite.

54

together with the young pyrite generations.
The increasing abundance of pyrite with time
is also recognized in the breccias, where several
generations of matrix and veins are observed. The
late vein generations consist mainly of pyrite, whereas
the matrix and clasts replaced in the early stages show
only minor pyrite disseminations.
Main ore stage
In large parts of the Smelter deposit, the silica-
pyrite replacements are overprinted by several types
of enargite-bearing assemblages formed during the
Main ore stage. In addition, in external zones, drilling
indicates that the Main ore stage gave rise to significant
sphalerite-galena bodies. Broadly, the Main ore stage
enargite assemblages can be grouped into several ore
metal zones, which from internal to external parts
are: (i) Cu-(Au-Ag) zone, (ii) Cu-(Ag-Sn-Bi) zone,
(iii) Cu-(Ag-Bi) zone, and (iv) Zn-Pn-(Ag) zone.
Despite abundant crosscutting relations,
there is no clear evidence that there was a time gap
between them and the termination of the Early silica-
pyrite stage. Some samples display late silica-pyrite
veinlets accompanied by minor amounts of enargite,
suggesting that transition between the Early silica-
pyrite stage and the Main ore stage was gradational.
Cu-(Au-Ag) zone
The Cu-(Au-Ag) zone is volumetrically the
most important in the Smelter deposit. The Cu-(Au-
Ag) zone is developed in portions of the Pocobamba
near the main intrusive center of the Marcapunta
volcanic complex, and subordinately in some lava-
dome facies of the complex (e.g., 450-500 m depth
in DDH Brocal 524; Figure 2a.3). The mineralogy
of this zone, irrespective of its geometry as mantos
or veins, is relatively simple and is largely composed
of enargite(pyrite-luzonite-alunite-quartz-zunyite).
Average metal contents of this zone are 1.9 wt. %
Cu, 0.6 ppm Au, and 20 ppm Ag.
Enargite is the chief copper mineral and
constitutes near 90 volume % of the copper resources
of the Smelter deposit, and between 30-50 % of
the total sulfide content deposited during the Main
ore stage. Pyrite is the next most abundant mineral.
Enargite occurs intricately intergrown with its low-
temperature polytype, luzonite, which not exceeds 5
volume % of the total copper minerals of the stage.
Enargite, in most cases, is observed coarse-grained
and ranges in size from a few millimeters up to 8
cm. Coarse grains, commonly anhedral but locally
subhedral, fill inter-grain cavities between pyrite-rich
clusters typical of late generations of the silica-pyrite
stage (Figure 2a.6). This style accounts for up to 60
% of the enargite. Exceptional elongate prismatic
crystals are not uncommon and found in druse-like
CHAPTER 2
cavities in both veins and mantos.
Intervals of massive enargite (>90 volume %),
up to >2 m thick, are composed of multigenerational
anhedral grains in which dissolution and reprecipitation
of enargite are common. The enargite precipitates in
most instances with minor pyrite. It should be stressed
that if the main style of the enargite is filling pyrite
clusters and geodes, the pyrite generally belongs to
the Early silica-pyrite stage (pyrite I).
Luzonite is almost always observed intergrown
with coarse anhedral-subhedral grains of enargite. In
contrast to enargite, luzonite is generally anhedral and
is rarely found as well-formed crystals. In polished
section, luzonite is distinctly pinkish where in contact
with enargite. In most examples, the luzonite displays
fine polysynthetic twinning under crossed nicols.
Irregular masses of luzonite without evident twinning
also almost completely replace enargite (Figure 2a.7).
In some places, enargite clearly replaces luzonite along
twinning, more rarely luzonite infiltrates along enargite
grain contacts. In a single grain, both directions of
replacement were also noted. Infrared observations
show that enargite commonly underwent dissolution
and recrystallization (e.g., Figure 4.2).
Although much less abundant than in the
Early silica-pyrite stage, pyrite also precipitated
during formation of the Cu-(Au-Ag) zone. The
main style of this pyrite II filling veinlet is up to a
few centimeters thick, which partly grade into open
spaces following bedding. These open spaces and
veinlets are commonly poor or devoid of enargite and
contain, in order of decreasing abundance, alunite,
quartz, and zunyite. Pyrite II occurs also as repetitive
thin bands with enargite (Figure 2a.6). Pyrite II, in
general, is largely subhedral to euhedral and coarse-
grained (up to 1 cm in size). Pyrite II commonly
forms pyritohedra (Figure 2a.7), whereas octahedral
and cubic forms, typical of pyrite I, are only locally
important. In polished section, pyrite II displays
a remarkable zoned appearance of two types. The
first and most prominent is due to the alternation of
dense and porous bands, which contain minute voids
thought to be remnants of fluid inclusions. In some
places such voids reach several hundreds of microns
long. The second type, as seen below, is a product of
compositional variations, and can be observed using
SEM imagery or as a result of surface oxidation, the
latter occurring extremely fast.
Much of the pyrite II occurs in spatial
association with enargite-rich zones. Subordinately,
pyrite II occurs directly overprinting considerable
parts of early silica-pyrite bodies which are
essentially enargite-free. In such cases, only quartz is
macroscopically observed accompanying the pyrite
II. Around 2-5 volume % of the pyrite II is found
as tiny subhedral inclusions in enargite, which is
commonly a partial replacement product.
Gold deposition is recognized in two
paragenetic positions in the Cu-(Au-Ag) zone. Early
deposition occurred as irregular inclusions, usually
55
 CHAPTER 2

quartz

alunite

alunite

A 2 mm B 50 m

woodhouseite

svanbergite

C 50 m D 50 m

zunyite

luzonite

alunite
E 200 m F 100 m

200 m

colusite
enargite

G H 100 m
Figure 2a.8: Typical habits and assemblages of non-sulfide gangue minerals. A. Intimate intergrowth between alunite, quartz,
and pyrite revealed by backscattered electron image. B. Backscattered electron image showing detail of reversed crystallization
between alunite and quartz. Note quartz growing on alunite and alunite on quartz. C. EDS image showing grains of APS
group minerals consisting of corroded cores of the svanvergite series and rims of alunite. D. EDS image of APS grains made
up of cores of the woodhouseite series and rims of alunite. E. Polished section image showing a alunite-zunyite assemblage ac-
companied by luzonite filling intergrain spaces. F. Polished section photomicrograph of alunite grains as inclusions in enargite. G.
Photomicrograph in transmitted light of a quartz-alunite assemblage in contact with anhedral enargite. H. Alunite postdating
enargite. Note that colusite appear to have formed as a product of the reaction between enargite and alunite.

56
 CHAPTER 2

Table 2a.1. Composition of selected sulfur-bearing phases from the Smelter deposit based on electron microprobe analysis.
Sample Mineral stage/zone S Fe Cu As Ag Sb Bi Sn Zn Total
PBR-391 pyrite I Early silica-pyrite stage 54.72 46.07 0.54 0.07 0.02 0.05 0.00 0.00 n.a. 101.47
PBR-391 pyrite I Early silica-pyrite stage 54.85 45.76 1.31 0.12 0.00 0.00 0.00 0.00 n.a. 101.94
PBR-247 pyrite I Early silica-pyrite stage 54.68 45.71 0.32 0.21 0.01 0.00 0.00 0.00 n.a. 100.72
PBR-247 pyrite I Early silica-pyrite stage 54.66 45.88 0.41 0.13 0.02 0.00 0.02 0.02 n.a. 101.05
PBR-132 pyrite II Main ore stage/Cu-(Au-Ag) 54.71 45.58 0.04 0.02 0.04 0.00 0.00 0.00 n.a. 100.37
PBR-132 pyrite II Main ore stage/Cu-(Au-Ag) 54.40 46.02 0.09 0.12 0.01 0.01 0.00 0.00 n.a. 100.54
PBR-132 pyrite II Main ore stage/Cu-(Au-Ag) 54.77 45.94 0.19 0.04 0.01 0.00 0.00 0.00 n.a. 100.95
PBR-137 pyrite II Main ore stage/Cu-(Au-Ag) 54.35 45.43 0.08 0.08 0.01 0.00 0.11 0.02 n.a. 99.98
PBR-137 pyrite II Main ore stage/Cu-(Au-Ag) 54.02 45.16 0.17 0.01 0.01 0.00 0.00 0.01 n.a. 99.36
PBR-137 pyrite II Main ore stage/Cu-(Sn-Bi-Ag) 53.70 44.89 0.16 0.08 0.01 0.00 0.00 0.00 n.a. 98.77
PBR-137 pyrite II Main ore stage/Cu-(Sn-Bi-Ag) 53.38 44.62 0.16 0.12 0.01 0.00 0.00 0.00 n.a. 98.18
PBR-132 enargite Main ore stage/Cu-(Au-Ag) 32.64 0.06 49.27 17.68 0.00 0.42 0.00 0.08 n.a. 100.08
PBR-132 enargite Main ore stage/Cu-(Au-Ag) 32.12 0.05 49.65 18.22 0.00 0.27 0.00 0.18 n.a. 100.32
PBR-132 enargite Main ore stage/Cu-(Au-Ag) 32.55 0.25 48.49 17.33 0.00 0.45 0.00 0.00 n.a. 99.07
PBR-132 enargite Main ore stage/Cu-(Au-Ag) 32.89 0.05 48.66 16.80 0.31 0.74 0.00 0.30 n.a. 99.46
PBR-132 enargite Main ore stage/Cu-(Au-Ag) 33.36 0.00 48.88 17.32 0.09 0.26 0.00 0.67 n.a. 99.91
PBR-263 enargite Main ore stage/Cu-(Sn-Bi-Ag) 33.18 0.05 48.36 17.11 0.10 0.40 0.25 0.34 n.a. 99.20
PBR-263 enargite Main ore stage/Cu-(Sn-Bi-Ag) 33.08 0.01 49.02 17.11 0.03 0.89 0.00 0.23 n.a. 100.14
PBR-263 enargite Main ore stage/Cu-(Sn-Bi-Ag) 32.98 0.00 49.22 17.07 0.03 0.83 0.00 0.26 n.a. 100.13
PBR-263 enargite Main ore stage/Cu-(Sn-Bi-Ag) 32.77 0.03 48.59 17.01 0.09 0.81 0.00 0.43 n.a. 99.29
PBR-265 enargite Main ore stage/Cu-(Sn-Bi-Ag) 32.53 0.08 48.70 17.00 0.03 0.54 0.00 0.72 n.a. 98.88
PBR-265 enargite Main ore stage/Cu-(Sn-Bi-Ag) 33.19 0.02 48.82 17.22 0.07 0.50 0.00 0.27 n.a. 99.82
PBR-265 enargite Main ore stage/Cu-(Sn-Bi-Ag) 33.20 0.10 49.27 17.67 0.07 0.02 0.20 0.00 n.a. 100.33
PBR-265 enargite Main ore stage/Cu-(Sn-Bi-Ag) 33.25 0.12 48.66 17.38 0.11 0.44 0.00 0.47 n.a. 99.96
PBR-265 enargite Main ore stage/Cu-(Sn-Bi-Ag) 33.01 0.27 48.73 17.61 0.05 0.10 0.00 0.04 n.a. 99.77
PBR-137 enargite Main ore stage/Cu-(Au-Ag) 33.11 0.27 48.87 17.67 0.05 0.10 0.00 0.04 n.a. 100.07
PBR-137 enargite Main ore stage/Cu-(Au-Ag) 33.21 0.27 49.02 17.72 0.05 0.10 0.01 0.04 n.a. 100.37
PBR-137 enargite Main ore stage/Cu-(Au-Ag) 33.31 0.27 49.17 17.77 0.05 0.10 0.01 0.04 n.a. 100.68
PBR-137 enargite Main ore stage/Cu-(Au-Ag) 33.41 0.27 49.32 17.83 0.05 0.10 0.01 0.05 n.a. 100.98
PBR-132 luzonite Main ore stage/Cu-(Au-Ag) 31.97 0.14 47.78 16.25 0.00 1.16 0.00 1.61 n.a. 97.30
PBR-132 luzonite Main ore stage/Cu-(Au-Ag) 31.54 0.21 48.72 15.48 0.01 1.21 0.00 3.15 n.a. 97.18
PBR-132 luzonite Main ore stage/Cu-(Au-Ag) 32.34 0.00 49.03 17.04 0.01 1.81 0.00 0.06 n.a. 100.24
PBR-265 luzonite Main ore stage/Cu-(Sn-Bi-Ag) 32.61 0.05 48.39 17.02 0.00 0.86 0.00 0.36 n.a. 98.93
PBR-265 luzonite Main ore stage/Cu-(Sn-Bi-Ag) 33.03 1.09 47.19 16.37 0.10 1.24 0.00 0.91 n.a. 99.01
PBR-265 luzonite Main ore stage/Cu-(Sn-Bi-Ag) 33.36 1.10 47.66 16.53 0.10 1.25 0.00 0.76 n.a. 100.00
PBR-265 luzonite Main ore stage/Cu-(Sn-Bi-Ag) 33.69 1.11 48.14 16.69 0.10 1.26 0.00 0.59 n.a. 101.00
PBR-265 luzonite Main ore stage/Cu-(Sn-Bi-Ag) 34.03 1.12 47.71 16.86 0.10 1.28 0.00 0.54 n.a. 101.09
PBR-132 colusite Main ore stage/Cu-(Au-Ag) 30.60 0.64 54.25 7.41 0.00 0.02 0.00 7.03 n.a. 99.95
PBR-131 colusite Main ore stage/Cu-(Sn-Bi-Ag) 29.81 2.74 52.25 4.82 0.00 0.00 0.02 10.96 n.a. 100.61
PBR-131 colusite Main ore stage/Cu-(Sn-Bi-Ag) 30.73 0.58 55.00 7.42 0.00 0.00 0.00 7.34 n.a. 101.07
PBR-131 colusite Main ore stage/Cu-(Sn-Bi-Ag) 31.04 0.87 53.94 7.17 0.00 0.00 0.00 7.88 n.a. 100.91
PBR-131 colusite Main ore stage/Cu-(Sn-Bi-Ag) 30.85 0.59 54.51 8.10 0.00 0.00 0.00 6.55 n.a. 100.59
PBR-131 colusite Main ore stage/Cu-(Sn-Bi-Ag) 30.62 0.86 52.37 8.32 0.00 0.02 0.01 7.34 n.a. 99.54
PBR-430 sphalerite Main ore stage/Zn-Pb-(Ag) 32.64 0.48 n.a. n.a. n.a. n.a. n.a. n.a. 66.43 99.55
PBR-430 sphalerite Main ore stage/Zn-Pb-(Ag) 32.81 0.62 n.a. n.a. n.a. n.a. n.a. n.a. 66.02 99.45
Sulfides were analysed using a Cameca SX50 electron microprobe at the University of Lausanne. Instrumental conditions were:
accelerating voltage of 12 kV, beam current of 30 nA, and spot size of 10 mm.

57
58
Table 2a.2. Composition of some selected accesory minerals from the Smelter deposit.
Sample/mineral zone S Fe Cu Zn As Ag Sn Sb Bi Cd V Au Te sum
(wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%)

tennantite
PBR-132 Cu-(Au-Ag) 30.85 0.59 54.51 0.06 8.10 0.00 6.55 1.11 0.00 0.00 n.a. 0.00 n.a. 101.76
PBR-132 Cu-(Au-Ag) 28.41 2.53 67.93 0.07 0.03 0.39 0.01 0.02 0.00 0.05 n.a. 0.01 n.a. 99.45
PBR-263 Cu-(Au-Ag) 27.84 6.86 44.35 0.02 18.97 0.00 0.07 0.17 0.00 n.a. 0.00 n.a. 0.03 98.31
PBR-263 Cu-(Au-Ag) 28.99 8.59 42.87 1.09 1.36 0.00 15.40 0.00 0.00 n.a. 0.15 n.a. 0.01 98.46

stannoidite
PBR-132 Cu-(Au-Ag) 29.57 5.85 47.38 0.27 2.34 0.00 15.77 0.52 0.00 0.00 n.a. 0.02 n.a. 101.72
PBR-132 Cu-(Au-Ag) 29.61 8.35 41.30 2.10 0.99 0.00 16.83 0.00 0.00 0.01 n.a. 0.02 n.a. 99.20

covellite
PBR-132 Cu-(Au-Ag) 28.41 2.53 67.93 0.07 0.03 0.39 0.01 0.02 0.00 0.05 n.a. 0.01 n.a. 99.45
PBR-132 Cu-(Au-Ag) 30.62 0.86 47.37 0.55 8.32 0.00 7.34 2.13 0.00 0.02 n.a. 0.12 n.a. 97.33

hessite
PBR-263 Cu-(Au-Ag) 0.05 0.03 0.79 0.02 0.01 60.37 0.00 0.09 0.03 n.a. 0.24 n.a. 39.25 100.87
PBR-263 Cu-(Au-Ag) 0.03 0.01 0.75 0.00 0.00 57.52 0.00 0.13 0.00 n.a. 0.00 n.a. 42.21 100.64

golfieldite
PBR-263 Cu-(Au-Ag) 25.70 0.04 45.90 0.00 5.52 0.08 0.05 1.52 0.03 n.a. n.a. n.a. 19.90 98.74
PBR-263 Cu-(Au-Ag) 25.70 0.04 45.90 0.00 5.52 0.08 0.05 1.52 0.03 n.a. n.a. n.a. 20.90 99.74

kostovite
PBR-263 Cu-(Au-Ag) 0.05 n.a. 8.38 n.a. 0.00 3.35 0.00 0.24 n.a. n.a. n.a. 24.68 65.81 102.51
PBR-263 Cu-(Au-Ag) 0.00 n.a. 8.40 n.a. 0.00 0.52 0.00 0.28 n.a. n.a. n.a. 25.06 67.23 101.49

Native tellurium
PBR-263 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.42 n.d. n.d. n.d. 0.17 101.59 102.18

Sulfides were analysed using a Cameca SX50 electron microprobe at the University of Lausanne. Instrumental conditions were: accelerating voltage of 12 kV, beam
current of 30 nA, and spot size of 10 mm.
CHAPTER 2

elongate and <10 m long, of electrum grains
within enargite (Figure 2a.7). The grains are mainly
located either along the cleavage or between grains
of enargite, suggesting that the gold precipitated
together with enargite or postdated it. In a few
examples, the grains partially fill minute cavities
in enargite without any apparent crystallographic
control; again the gold could have precipitated with
or later than enargite. The tiny gold inclusions were
likely deposited relatively late in the Main ore stage
because most of the electrum occurs with the latest
enargite generations.
A second occurrence of gold deposition is
associated with blebs, up to 50 m in diameter, of Te-
bearing phases, including locally abundant goldfieldite
and tennantite. The blebs replace late generations of
enargite and seem to have fed along grain boundaries.
The gold occurs chiefly as tellurides, with minor
amounts of extremely fine-grained electrum (<5 m
in size) as inclusions in goldfieldite. The identified
gold tellurides are kostovite and nagyagite (Figure
2a.7). Goldfieldite is observed in places to be zoned
and alternating with bands of tennantite (Figure 2a.7).
Overgrowths of Te-bearing phases and tennantite on
enargite grains have are also observed (Figure 2a.7).
Silver tellurides also occur in such blebs.
Microprobe analyses (Table 2a.4) prove the presence
of stutzite and combined EDS tests and polished
section properties suggest the presence of hessite
(Appendix 2a.3). Other gold- and/or silver-bearing
tellurides seem to occur but they were not tested via
microprobe. These silver tellurides occur intricately
intergrown with the gold tellurides, goldfieldite and
native tellurium (Figure 2a.7). It seems that these
silver minerals do not contribute substantially to the
silver values found in most argentiferous intervals.
Two inclusions of native iridium in enargite,
both only a few microns in size were recognized
through EDS tests (Appendix 2a.3) and polished
section. Like the tiny electrum inclusions in enargite,
iridium deposition is assigned to the Main ore
stage. Ferberite is common in the Cu-(Au-Ag)
zone, particularly within 500 m of the Marcapunta
complex. Euhedral prismatic grains, sometimes
twinned and up to >100 m in size, were observed
in numerous enargite-rich samples. Ferberite mainly
occurs paragenetically later than enargite and Main
ore stage quartz (quartz II, see below). Tungsten
concentrations determined by ICP analysis indicate
that it correlates well with Cu and As, thereby further
supporting this view. Tungsten values may attain
0.6 wt. %, but more typically 0.05-0.2 wt. % (see W
concentrations up to >4000 ppm in Appendix 2a.2).
Other accessory minerals precipitated during
the Main ore stage are bismuthinite, which may be
locally abundant (up to 0.5 volume %), and more
rarely, emplectite and stannoidite. They occur as
The term electrum is used here following the definition of
Zunyite is widespread throughout the entire
Barton and Toulmin (1964) for natural Au-Ag alloys between
pure gold and pure silver end members.
CHAPTER 2
minute inclusions, exclusively in enargite. In similar
form, unidentified Bi and Ag minerals, shown by EDS
tests, may have been introduced coevally. Economic
argentiferous intervals may in part be explained by
these Ag-bearing phases. The observations indicate
that all of these extremely fine-grained phases tend
to be more abundant in late enargite generations.
As mentioned above, alunite, quartz and zunyite
are also found in pyrite II veins. Alunite occurs largely
as platy euhedral grains intimately intergrown with
quartz and zunyite (Figure 2a.8). The best developed
and largest grains, up to 5 mm in size are pinkish and
translucent and found in small geodes and fractures.
Whitish grains are also common but usually do not
exceeds 1 mm in size. Massive friable blades of fine-
grained alunite and variable amounts of minute
euhedral quartz grains, typically less than 2 mm
across are locally volumetrically important. Reversals
in crystallization sequences without evidence of
reaction between pyrite II-alunite and pyrite II-quartz
pairs, are common. Euhedral pyrite II grains are
encapsulated in alunite and vice versa (Figure 2a.8).
These observations suggest that alunite, pyrite II and
quartz were precipitated essentially coetaneously and
in chemical equilibrium (see also chapter 4).
Approximately 40 % of the enargite in the
Cu-(Au-Ag) zone is found in direct contact with
alunite. Commonly, alunite accompanied by quartz
and subordinate pyrite comprises veinlets that cut
and/or replace enargite. A reversed paragenetic
sequence is also common and mainly occurs as
enargite filling intergranular spaces within alunite.
Most of the enargite in contact with the alunite that
precipitated paragenetically late displays the effects of
strong corrosion and recrystallization using infrared
imagery, commonly with no evidence of the original
grain morphology. Subordinately, enargite occurs as
intimate intergrowths with euhedral grains of alunite
in open spaces (Figure 2a.6).
Under the microscope, alunite displays highly
variably birefringence with a relatively well defined
pattern depending on the distance to the main
Marcapunta magmatic center. The birefringence
attains second-order blue in the innermost parts, with
a tendency to lower first-order grey to yellow in the
rest of the zone. Observation with the SEM shows
that alunite usually consists of two discernable phases
of APS (aluminum phosphate sulfate) group minerals
(Figure 2a.8). Cores identified with microprobe
analysis are dominated by the woodhouseite series
whereas rims are composed largely by the alunite
series, essentially pure alunite. The cores, although
sometimes corroded in appearance, generally displays
well-developed oscillatory zoning. Seen in detail,
the core is made up of dense bands, which became
progressively less abundant towards the borders of
the grains (Figure 2a.8).
Cu-(Au-Ag) zone. It consists of euhedral tetragonal
pyramids (Figure 2a.8), sometimes truncated with an
59

octahedral form. The grains can reach 2 mm wide
and are translucent. Occurrence of zunyite without
alunite is uncommon. Mutual relations of the pyrite
II-zunyite pair are similar to those of pyrite II-alunite.
For example, euhedral pyrite grains are encapsulated
within zunyite but the reverse, although rarer, has
also been noted.
Quartz occurs mostly as an accompaniment
to alunite-(zunyite). In common with the distinction
made between Early stage pyrite I and Main ore
stage pyrite II, quartz deposited during the Main
ore stage is called quartz II. This quartz II is grossly
euhedral and highly variable in size. Tiny grains occur
in intricate intergrowths with alunite and zunyite as
part of pyrite II veinlets. Larger quartz grains are
observed intergrown with enargite but lacking the
alunite-zunyite pair. Minor amounts of clays are
observed locally accompanying this quartz. Quartz-
enargite lacking alunite characterizes up to 60 % of
the enargite resource of the entire Smelter deposit.
Quartz with enargite is typically corroded where in
contact with later alunite.
Small amounts of dickite, kaolinite and, in
places, smectite and illite are present throughout the
Cu-(Au-Ag) zone, particularly in portions devoid of
alunite-bearing assemblages. These clays typically
fill intergranular spaces in enargite, pyrite II, and
quartz II. Where kaolinite and dickite are in contact
with enargite, no reaction is observed (Figure 2a.6).
Furthermore, kaolinite, dickite, and apparently also
illite as inclusions in enargite have been observed to
display no reaction effects. A reconnaissance study
of clay minerals carried out by Cominco in 1999
suggests that most of the alunite-free enargite
bodies contain minor amounts of clays including,
besides kaolinite and dickite, some pyrophyllite,
illite and smectite. Observed in detail, again virtually
no reaction effects are observed between enargite
and clays and no alunite is observed to have co-
precipitated with the enargite-clay assemblages. It is
therefore likely that important parts of the enargite
bodies macroscopically exempt of alunite (~60 % of
the Smelter deposit) contain trace to minor amounts
of clays.
Significant amounts of hematite are observed
partially replaced by pyrite II. However, as explained
later and based on observations at district-scale, the
hematite is thought to be a remnant mineral from
external parts of the system, i.e., from Zn-Pb-(Ag)
parts, that have been almost entirely replaced by
mineral associations from the internal Cu-(Au-Ag)
zone.
Composition of minerals of the Cu-(Au-Ag) zone
A selection of representative microprobe
analyses of enargite, luzonite, pyrite II, tennantite,
goldfieldite and accessory minerals is given in Table
2a.1.
60
CHAPTER 2
Enargite compositions are nearly stoichiometric
(Table 2a.1). All measured antimony contents are
below 1.5 wt. %, but in general between 0.5 and 1.0
wt. %. Sn displays similar concentrations (0.3-1.5 wt.
%). Less abundant elements are Zn and Fe (<0.3 wt.
%), and more rarely Bi (<0.3 wt. %). Another minor
element detected in some cases to be economically
significant is Ag (mainly in the range of 0.1 to 0.3
wt. %, up to 0.6 wt %). Luzonite compositions are
also close to stoichiometric. The mineral shows
considerably higher Sb contents than enargite, ranging
steadily from 0.5 to 2 wt. %. The minor elements, Sn
and Fe, are equally more concentrated in luzonite (up
to 3.0 and 1.0 wt. %, respectively).
Main ore stage pyrite II is largely nearly
stoichiometric (e.g., Table 2a.2 and Appendix 2a.1).
As recognized in pyrite I grains from the Early
silica-pyrite stage, the main elements responsible
for the zoning in pyrite II are arsenic and copper.
However, in contrast to pyrite I, copper is, by far,
more abundant. Copper contents were found to be
as high as 4.0 wt. %, but in general are between 0.5
and 1.5 wt. %. Similar high copper values in pyrite
were reported by Einaudi (1968) at Cerro de Pasco.
Arsenic, in contrast, does not surpass 0.6 wt. %.
Pyrite II as inclusions in enargite was found to be
more frequently rich in copper (up to 3.2 wt. %).
Silver contents in pyrite II vary from below detection
limit in most of the analyses to 0.4 wt. %.
Based on two analyzed samples, goldfieldite,
the Te-rich end member of the tennantite series,
contains up to 23.6 wt. % Te (Table 2a.2, Figure
2a.7). Sb substitution for arsenic is important
(main population between 1.5 and 5.2 wt. %); well-
developed zoning observed in some cases is likely
due to such Sb variations. Bismuth concentrations
are significant in all analyses (between 0.2 and 2.0
wt. %). Other minor elements detected in significant
concentrations are silver and vanadium, up to 0.8 wt.
% and 0.3 wt % respectively.
Five samples indicate that tennantite associated
with goldfieldite and gold-silver tellurides is ferriferous
containing up to 7 wt. %. Antimony substitution by
As is generally <1.5 wt. %. No other element was
detected to be a significant component of the Main
ore stage tennantite. Ag contents are in general <0.1
wt. % (Table 2a.2).
Only 16 grains of electrum were sufficiently
large for microprobe analysis. All of them belong
to the first gold deposition period of the Cu-Au-
(Ag) Main ore stage. The results show a relatively
homogeneous composition for electrum, ranging
from 84 to 94 wt. % Au with the remaining fraction
consisting essentially of silver (Table 2a.3). In a few
grains, copper values were found to be appreciable
(up to 4 wt. %).
Native tellurium (App. 2a.3) is virtually pure.
Only insignificant concentrations of Cu and Au were
detected in the five analyzed points (<0.4 and 0.3 wt.
%, respectively). A few quantitative data on kostovite,
 CHAPTER 2

Early silica-pyrite stage Main ore stage Late ore stage

rutile
zircon
scheelite
muscovite
chlorite
mainly octahedral (pyrite I) mainly pentagonal dodecahedral (pyrite II)
pyrite
enargite
quartz
luzonite
colusite
zunyite
alunite (APS phases)
calcopyrite
tennantite
goldfieldite
native Au
ferberite
bismutinite
Au-Ag tellurides
native Te
dickite-(kaolinite)
illite-(smectite)
sphalerite
galena
siderite
chalcocite

volume %
<1 >1-<5 > 5 - < 10 > 10

Figure 2a.9: Mineral paragenetic sequence of the Smelter deposit. Consider simultaneous mineral precipitation of two or more
minerals during a given position in time. E.g., during the Main ore stage, whereas a batch of fluids is precipitating enargite in
internal zones of the deposit another batch is at the same time precipitating sphalerite in more external positions.

stutzite, and the unidentified tellurides are given in
Table 2a.3. Similarly, limited data on other accessory
minerals from the Main ore stage of the Cu-(Au-Ag)
zone, including stannoidite, are shown in Table 2a.2.
and Appendix 2a.1.
Over 50 analyses from six widely spaced
alunite samples from the Cu-(Au-Ag) zone were
analyzed using the electron microprobe. Table 2a.4
presents a selection of the alunite compositions
found in this survey. High-energy bands, observed
in the cores of grains in SEM images are generally
rich in P2O5 (0.12-0.20 wt. %), with the A site largely
occupied, to varying degrees, by Sr, Ca and Pb
(woodhouseite series). These woodhouseite-series
bands are the most enriched in fluorine (up to 2.1
wt. %; Table 2a.4). Towards the rim, the high-energy
bands are less abundant, giving rise to homogeneous
and ample low-energy bands which are rich in K
(alunite end member), with Na/K<0.1 and virtually
free of Sr, Ca, and Pb. In instances in which instead
of oscillatory bands, the cores of the grains consist
of a single zone, usually corroded, it is even more
enriched in P2O5 (up to 0.46 wt %) but Pb-free and,
more rarely, Ca-free. In such examples, the core may
reach the svanbergite end-member composition. A
particular feature of this second type of core is its
high cerium content. The rim in this second case is
also alunite with similar Na/K values (<0.1). These
compositional variations recorded in single grains
seem to characterize perhaps nearly half of those
recognized in alunite from the inner Cu zones of the
Smelter deposit, including the Cu-Au-(Sn-Ag) and Cu-
(Ag) zones. In the remaining examples the grains are
alunite with Na/K ratios ranging typically from 0.03
to 0.08, and rarely, >0.20 (Table 2a.4). Birefringence
changes observed in thin sections seem to bear no
evident relation to compositional changes of either
major or minor elements.
Limited microprobe analysis was conducted
on a few grains of zunyite from two alunite-bearing
samples. The analyses revealed nearly stoichiometric
compositions. Zunyite has chlorine contents between
2.65 and 3.4 wt. %.
Cu-(Ag-Sn-Bi) zone
The enargite Cu-Au-(Ag-Sn-Bi) zone displays
essentially the same associations and assemblages as
the enargite Cu-Au-(Ag) zone, but with significantly
higher tin and bismuth concentrations. This zone is
recognized mainly between 588 and 628 lines (Figure
2a.2). Typical tin concentrations range between 500
and 2,000 ppm (Appendix 2a.2), but metric intervals

61
 CHAPTER 2

Table 2a.3: Composition of electrum grains in three samples from the Smelter deposit
Sample stage/zone Au Ag Cu Cd Zn Fe S Total
PBR-132 Main ore stage/Cu-(Au-Ag) 81.32 16.21 2.17 0.57 0.06 0.11 0.09 100.53
PBR-132 Main ore stage/Cu-(Au-Ag) 82.04 16.44 1.89 0.49 0.09 0.19 0.11 101.26
PBR-132 Main ore stage/Cu-(Au-Ag) 80.67 15.88 3.23 0.42 0.46 0.12 0.08 100.85
PBR-132 Main ore stage/Cu-(Au-Ag) 82.70 16.01 1.21 0.50 0.02 0.16 0.13 100.73
PBR-245 Main ore stage/Cu-(Au-Ag) 83.05 15.33 2.94 0.23 0.03 0.14 0.13 101.85
PBR-245 Main ore stage/Cu-(Au-Ag) 82.28 15.49 2.43 0.21 0.03 0.03 0.05 100.52
PBR-245 Main ore stage/Cu-(Au-Ag) 81.79 15.40 2.42 0.21 0.03 0.03 0.05 99.92
PBR-265 Main ore stage/Cu-(Sn-Bi-Ag) 81.30 15.30 2.40 0.21 0.03 0.03 0.05 99.32
Minerals were analysed using a Cameca SX50 electron microprobe at the University of Lausanne. Instrumental
conditions were: accelerating voltage of 12 kV, beam current of 30 nA, and spot size of 10 mm.

containing in excess of 0.3 wt. % are not uncommon.
Gold contents in this zone (~0.6 ppm) are slightly
lower than in the Cu-(Au-Ag) zone. Bismuth
concentrations are generally on the order of 100 ppm,
but numerous intervals of a few meters may exceed
0.3 wt. %. In many mineralized intervals, these high
bismuth values are linearly correlated with high silver
concentrations, which can be up to >10 oz/t.
Colusite is the most important tin mineral, not
only in this zone but in the whole Smelter deposit. It
mainly occurs as strongly zoned euhedral grains up to
1mm wide (Figure 2a.7). The grains are pyritohedral
in form although cubes are occasionally discernable.
Colusite shows sector zoning and stronger reflection
pleochroism than that described by Ramdohr (1980).
Colusite typically replaces enargite and especially
pyrite II (Figure 2a.7). Only locally does enargite
replace colusite along fractures, cleavage, and
growths planes. Some pyrite II shows no reaction
effects against colusite suggesting that, in places, they
may constitute an equilibrium assemblage. Moreover,
much of the colusite is observed to be in reaction-
free contact with alunite, zunyite, and quartz (Figure
2a.8).
Stannoidite is a minor to trace tin mineral often,
but not necessarily, associated with colusite. It occurs
as irregular blebs on the edges of quartz, enargite,
or alunite clusters. In general, where stannoidite and
colusite are in contact, the former replaces the latter.
A second extremely fine-grained phase accessory
is intergrown with colusite. Optically it resembles
vinciennite, but a definitive identification is lacking.
The relationship between the strong zoning and
compositional variations has not been investigated;
however, elemental substitution in the R site (Sn,
As, Sb) suggests that such a relationship exists. For
example, Sn ranges from 4.9 to 9.2 wt. % in a single
grain, coincident with decrease in As+Sb from 10.4
to 5 wt. %. Antimony contents of colusite are >2.3
wt. % (typically 0.8-1.6 wt. %). The few analyzed
grains of stannoidite are essentially stoichiometric
(Table 2a.2). The minor elements Zn, As, and Sb
together account for <4 wt. % (<2.6, 1.2 and 0.8,
respectively).
Two analyzed electrum grains from this zone,
with Au and Ag contents of ~96 wt. % and 4 wt. %,
respectively, yielded higher gold contents compared
to those encountered in the Cu-(Au-Ag) zone. Copper
is also very low (Table 2a.3). Alunite compositions in
three samples from the Cu-Au-(Sn-Ag) zone show
no significant compositional change from those
described from the inner Cu-Au-(Ag) zone.
Some drill holes effectuated in the Cu-(Ag-Sn-
Bi) zone (e.g., DDH-CM5-580) intercepted Zn-Pb-
(Ag) bodies consisting largely of sphalerite, galena,
pyrite, siderite, hematite and kaolinite. This mineral
association predated that typical of the Cu-(Ag-Sn-
Bi) zone. The contacts between Zn-Pb-(Ag) and
enargite-bearing assotiations are sharp with clear
evidences that the latter overprints and cuts the
sphalerite-galena bodies. It is possible to appreciate
how thin veinlets of enargite or pyrite-alunite
penetrate the sphalerite-galena bodies in the vicinity
of their contacts.

Composition of minerals of the Cu-(Ag-Sn-Bi) zone Cu-(Ag-Bi) zone

All of the other main phases of the enargite
Cu-Au-(Ag-Sn-Bi) zone, including enargite,
luzonite, pyrite II, tennantite and goldfieldite, were
quantitatively analyzed from several representative
samples. No major variations in compositions relative
to the Cu-(Au-Ag) zone were detected.
Colusite compositions are close to
stoichiometric and are summarized in Table 2a.1.
The enargite Cu-(Ag-Bi) zone roughly
coincides with the sector between lines 644 and 700
lines and extends to the Colquijirca deposit, where
it contains lesser amounts of bismuth (Figure 2a.2).
At Smelter, a mineralogical characterization of this
zone is difficult because of the pervasive overlap
of the Late ore stage, particularly well developed in
this sector. Nevertheless, the samples studied were

62
 CHAPTER 2

Table 2a.4: Representative microprobe composition of alunite from the Smelter deposit.
Cu-(Au-Ag) zone Cu-(Sn-Bi-Ag) zone
Sample PBR-245 PBR-262 PBR-329 PBR-298 PBR-322 PBR-208 PBR-238
K2O 9.59 9.54 8.87 10.08 8.85 9.21 8.83
Na2O 0.42 0.81 1.78 0.24 2.04 0.42 0.56
BaO 0.23 0.38 0.25 0.26 0.16 0.08 0.02
SrO 0.72 0.32 0.02 0.67 0.51 0.16 0.14
PbO 0.11 0.12 0.02 0.01 0.01 1.32 1.62
Al2O3 35.98 35.88 36.20 36.79 35.94 36.42 36.04
SO3 40.76 39.90 39.86 39.01 40.84 40.80 40.21
P 2O 5 0.12 0.23 0.46 0.14 0.24 0.82 0.35
H2O** 13.02 14.24 13.86 13.96 11.84 12.62 12.46
F- 0.18 2.42 0.76 0.69 0.16 0.38 0.86
Total 101.13 103.84 102.08 101.85 100.59 102.23 101.09
* Alunite was analysed using a Cameca SX50 electron microprobe at the University of Lausanne.
Instrumental conditions were: accelerating voltage of 12 kV, beam current of 10 nA, and spot size of 15
mm.

** Weight % H2O calculated based on observed values of sulfur, phosphorous, potassium, sodium,
strontium, barium, and fluorine, and alunite stoichiometry using the formula AR3(SO4)2(F, OH)6, in which
A refers to the large cations K+, Na+, Ba2+, Pb2+ and Sr2+, and R is Al3+

selected from points in which enargite shows only
minor replacement by the Late ore stage.
The mineral paragenesis of the Cu-(Ag-Bi) are
similar to those of the inner zones, with the most
remarkable feature being strong decreases in the Au
(<0.15 ppm) and Sn contents (<100 ppm)(Appendix
2a.2). Copper and Ag values are, on the other hand,
higher than those in the inner zones (~2.5 wt. %
and 40 ppm, respectively). In accordance with the
metal contents of this zone, tin minerals are much
less abundant than in the Au-(Ag-Sn-Bi) zone. Only
occasionally is some minor colusite observed.
Mineralogically, the Cu-(Ag-Bi) zone does
not differ much from the other inner copper zones.
Enargite-(luzonite) is always the main copper mineral
and minor phases are generally the same as those
present in the inner zones. Similarly, in terms of
chemical composition, no significant variations in the
main minerals were found.
A particular feature of the Cu-(Ag-Bi) zone
compared to the other enargite zones is the greater
abundance of Ag-and Bi-rich intervals. Silver grades
rarely surpass 10 oz/t over metric intervals (generally
~1.5 oz/t compared to 0.7-0.9 oz/t in the other
copper zones). Bismuth values measured by AAS
increase to >0.5 wt. % over metric intervals (e.g.,
DDH SM-676, 136-143 m). Silver and Bi values
show good linear correlations. As is the case in the
Cu-(Ag-Sn-Bi) zone, these values have their origin
in extremely fine-grained unidentified Bi- and Ag-
bearing minerals present as inclusions in enargite-
(luzonite), as recognized through EDS tests. Another
plausible possibility is substitution of copper by
silver in the enargite lattice. As Ag concentrations
in enargite are as high as 0.6 wt. %, they could
substantially contribute to the silver enrichment of
any given zone.
Zn-Pb-(Ag) zone
Laterally, surrounding considerable portions
of the copper-rich core of the Smelter deposit,
economically interesting Zn-Pb-(Ag) intervals have
been drilled. They become richer northward from
line 668 as well as both eastward and westward, as
shown in Figure 2a.4. Some of these intervals, such
as those located in the most external portions of
the sector between lines 572 and 580 (Figure 2a.4),
constitute true Zn-Pb-(Ag) orebodies with average
grades of 6 wt. % Zn, 2.3 wt. Pb and 2.0 oz/t Ag .
The characteristics of the transition from the
Cu-(Ag-Bi) to the Zn-Pb-(Ag) zone are unknown
because the drill holes cut the Zn-Pb-(Ag) ore some
150 to 200 m beyond the outermost hole in the Cu-
(Ag) zone.
The Zn-Pb-(Ag) zone largely comprises
siderite, sphalerite, galena, specular hematite, pyrite,
and kaolinite-(dickite). The contacts with the host
rock are sharp and strongly controlled by bedding,
suggesting that they form manto-like bodies (Figure
2a.4). The mineralized intervals alternate with partly
unaltered carbonate rocks and, most importantly,
with intervals having significant copper contents.
These cupriferous intervals are roughly located in the
central portions of the mineralized body, strongly
suggesting that the Zn-Pb-(Ag) mineralization
constitutes particularly well-developed peripheral
Zn-Pb-rich zones in a classic zone pattern, in which
the Cu ores occupy the central parts.

63

Sphalerite and galena are coarse-grained and
fill intergrain spaces within siderite or are intricately
intergrown with it. Sphalerite-galena textural
relationships are relatively complex. The most
obvious case is where sphalerite replaces galena
or coats cleavage surfaces within it. Sphalerite and
galena typically replace pyrite and, in some places, the
replacement may be complete. Pyrite in the Zn-Pb-
(Ag) zone is of two main types: one coarse-grained
and generally replaced by sphalerite and galena, and
the other generally fine-grained. Marcasite is observed
in contact with pyrite either as rims or replacing it.
Kaolinite and, rarely, dickite are observed to
fill any free space left after sphalerite and galena
precipitation. No textural evidence of reaction
between kaolinite-(dickite) and siderite or kaolinite-
(dickite) and sphalerite-galena was observed.
Composition of minerals of the Zn-Pb-(Ag) zone
A few grains of sphalerite in this zone were
analyzed (Table 2a.1). FeS contents range from 1.6
to 3.4 wt. mol %, with insignificant amounts of Mn
and Cd.
Late ore stage
The three enargite-bearing mineral associations
and assemblages from the Main ore stage are
overprinted by two main cupriferous mineral
associations, one dominated by chalcocite and the
other by tennantite. The temporal relation in time
between these two associations are not clear but, on
the basis of irrefutable crosscutting relationships
indicative of a late timing, may be assigned to a single
Late ore stage. The outermost Zn-Pb-(Ag) zone of
the Main stage is not affected by this overprinting.
A chalcocite-bearing association is recognized
throughout the entire Smelter deposit, but generally
it does not constitute ore. Chalcocite forms irregular
masses and is never observed to be well crystallized.
Typically, chalcocite replaces enargite along fractures
and veinlets no more than a few centimeters thick.
From these veinlets, chalcocite penetrates into the
Main ore stage mineralization and may eventually
extensively replace not only enargite, but also pyrite
II and other phases, including late gold-bearing
tennantite. Chalcocite is also observed coating
different generations of pyrite II. Covellite and, less
commonly, digenite may locally be just as abundant
as the chalcocite. These last phases occur as fuzzy,
fibrous aggregates within chalcocite or as rims to
enargite grains.
Just as widespread as the chalcocite-dominated
mineralization, although volumetrically less
important, are tennantite-dominated associations
identified throughout the Smelter deposit. These
associations are best developed, in contrast to
64
CHAPTER 2
the chalcocite-dominated ones, in relatively distal
positions. One such zone, the most important in
terms of volume, is located at Smelter Norte, a sector
comprised between lines 636 and 700 (Smelter Norte
sector; Figure 2a.2). In this sector, there is pervasive
replacement of the three enargite-bearing zones of
the Main ore stage by tennantite-bearing associations,
including combinations of chalcopyrite, chalcocite,
covellite, digenite, bornite and rare copper sulfosalts.
Tennantite displays intricate intergrowths with these
copper various minerals.
Also at Smelter Norte, thin sphalerite veins
replacing chalcocite (covellite) have been observed
in a few places (e.g., DDH CM-668, at 163 m),
although in none of them is galena volumetrically
significant. No microprobe data are available from
this late-stage sphalerite, but it can be presumed on
the basis of its color in transmitted light (red brown
to yellowish) to contains FeS contents similar to those
of sphalerite from the outer Zn-Pb-(Ag) zone.
Economically important Late ore stage
chalcocite bodies were recently found in the
Marcapunta Oeste project area. The bodies appear, as
at Smelter, to be structurally controlled by subvertical
faults. In this area, chalcocite hosted by the Mitu
Group red beds has been observed commonly to be
accompanied by appreciable amounts of fine-grained
white sericite.
Composition of minerals of the Late ore stage
A few quantitative chalcocite analyses were
obtained. Several chalcocite grains occurring as
an overprint to the Cu-(Au-Ag) zone yielded
compositions close to stoichiometric. In contrast,
chalcocite from the Cu-(Ag-Bi) zone at Smelter Norte
shows considerable compositional deviation from
stoichiometry, with Cu/S ratios most commonly
between 1.7 and 1.9, as well as under reflected light
and in reflected light being anisotropic.
Compositionally, tennantite from the Late
ore stage differs significantly from that in the Main
stage Cu-(Au-Ag) zone in both tellurium and zinc
contents. No significant tellurium values were found
in any of the analyzed samples and zinc contents are
remarkable high, commonly in excess of 2 wt. %. In
general, Sb substitution for As is minor. Microprobe
analyses reveal generally low Sb concentrations (<1
wt. %, though in one case up to 2.6 wt. %).
REFERENCES
Angeles, C., 1993, Geologa de Colquijirca y alrede-
dores. Informe privado Sociedad Minera El Brocal S.A.,
39 p.
Barton, P.B., Jr., Bethke, P.M., and Toulmin, P., III,
 CHAPTER 2

1963, Equilibrium in ore deposits. Symposium on the

mineralogy of sulfides--International Mineralogical As-
sociation, 3rd General Meeting, Washington DC, 1963,
p.171-185.

Barton, P.B., Jr., 1970, Sulfide petrology. Mineralogical

Society of America, Special Paper No. 3, p.187-198.

Barton, P.B., Jr., and Toulmin, P., III, 1964, The elec-
trum-tarnish method for determination of the fugacity of
sulfur in laboratory sulfide systems. Geochimica et Cos-
mochimica Acta, 28, p. 619-640.

Einaudi, M.T., 1968, Copper zoning in pyrite from

Cerro de Pasco, Per. American Mineralogist, 53, p. 1748-
1752

Einaudi, M.T., Hedenquist, J.W., and Inan, E., 2003,

Sulfidation state of fluids in active and extinct hydrother-
mal systems: transitions from porphyry to epithermal en-
vironments, in Simmons, S.F, ed., Volcanic, Geothermal,
and Ore-forming fluids: Roles and witnesses of processes
within the earth. Giggenbach memorial volume, Society
of Economic Geologists and Geochemical Society, Spe-
cial Publication, 10, 285-313.

Hemley, J.J., and Hunt, J.P., 1992, Hydrothermal ore-

forming processes in the light of studies in rock-buffered
systems, II. Some general geologic applications. Econom-
ic Geology, 87, p.23-43.

McKinstry, H.E., 1936, Geology of the silver deposit

at Colquijirca, Per. Economic Geology, 31, p. 619-635.

Monteagudo, I., 2000, Private report for Sociedad

Minera El Brocal S.A.A.

Ramdohr , P., 1980, The ore minerals and their inter-

growths. Pergamon Press, 1207 p.

Sales, R.H. and Meyer. C., 1949, Results from prelimi-

nary studies of vein formation at Butte, Montana. Eco-
nomic Geology, 44, p. 465-484.

Vidal, C., and Ligarda, R., 2004, Enargite-Gold De-

posits at Marcapunta, Colquijirca Mining District, Central
Per: mineralogic and geochemical zoning in Subvolcanic,
limestone-replacement deposits of high-sulfidation epith-
ermal type, Economic Geology Special publications, 11,
231-242.

65
66
Appendix 2a.1. Additional microprobe results obtained for some common phases from the Smelter deposit.
Label S (wt%) Fe (wt%) Cu (wt%) Zn (wt%) As (wt%) Ag (wt%) Sn (wt%) Sb (wt%) Bi (wt%) Cd (wt%) V (wt%) Au (wt%) Te (wt%) sum

covellite
PBR-132 28.41 2.53 67.93 0.07 0.03 0.39 0.01 0.02 0.00 0.05 n.d 0.01 n.d 99.45
PBR-132 30.62 0.86 47.37 0.55 8.32 0.00 7.34 2.13 0.00 0.02 n.d 0.12 n.d 97.33

electrum
PBR-132 0.11 0.19 4.33 0.09 0.00 15.44 0.00 0.01 0.05 0.49 n.d 83.02 n.d 103.73
PBR-132 6.67 0.68 12.69 0.46 2.38 11.41 0.00 0.27 0.01 0.42 n.d 67.74 n.d 102.73
PBR-132 0.13 0.16 3.59 0.02 0.02 15.01 0.00 0.00 0.00 0.50 n.d 83.41 n.d 102.85
PBR-132 0.13 0.14 3.47 0.03 0.04 14.33 0.00 0.01 0.01 0.23 n.d 83.17 n.d 101.55
PBR-132 3.83 0.55 8.15 0.03 1.74 12.50 0.00 0.09 0.11 0.21 n.d 75.35 n.d 102.58
PBR-132 0.13 0.14 3.47 0.03 0.04 14.33 0.00 0.01 0.01 0.23 n.d 83.17 n.d 101.55
PBR-132 3.83 0.55 8.15 0.03 1.74 12.50 0.00 0.09 0.11 0.21 n.d 75.35 n.d 102.58

enargite
PBR-132 32.55 0.25 48.49 0.00 17.33 0.00 0.16 0.45 0.18 0.01 n.d 0.11 n.d 99.54
PBR-132 31.97 0.14 47.78 0.11 15.99 0.00 1.61 1.16 0.00 0.01 n.d 0.20 n.d 98.98
PBR-263 32.89 0.05 48.66 0.04 16.80 0.31 0.30 0.74 0.00 n.d 0.00 n.d n.d 99.80
PBR-263 33.36 0.00 48.88 0.28 17.32 0.09 0.67 0.26 0.00 n.d 0.00 n.d n.d 100.86
PBR-263 33.18 0.05 48.36 0.00 17.11 0.10 0.34 0.40 0.25 n.d 0.00 n.d n.d 99.79
PBR-263 33.08 0.01 49.02 0.00 17.11 0.03 0.23 0.89 0.00 n.d 0.00 n.d n.d 100.37
PBR-263 32.98 0.00 49.22 0.03 17.07 0.03 0.26 0.83 0.00 n.d 0.02 n.d n.d 100.45
PBR-137 32.77 0.03 48.59 0.13 17.01 0.09 0.43 0.81 0.00 n.d 0.00 n.d n.d 99.85
PBR-137 32.53 0.08 48.70 0.08 17.00 0.03 0.72 0.54 0.00 n.d 0.01 n.d n.d 99.69
PBR-137 30.34 0.01 45.08 0.07 16.05 0.61 6.37 0.21 0.00 n.d 0.00 n.d n.d 98.73
PBR-137 33.19 0.02 48.82 0.04 17.22 0.07 0.27 0.50 0.00 n.d 0.00 n.d n.d 100.13
PBR-137 33.20 0.10 49.27 0.00 17.67 0.07 0.00 0.02 0.20 n.d 0.00 n.d n.d 100.54
PBR-137 30.79 0.05 45.35 0.04 18.46 0.09 0.23 0.75 0.00 n.d 0.02 n.d n.d 95.78
PBR-137 33.25 0.12 48.66 0.04 17.38 0.11 0.47 0.44 0.00 n.d 0.02 n.d n.d 100.49
PBR-137 33.01 0.27 48.73 0.07 17.61 0.05 0.04 0.10 0.00 n.d 0.00 n.d n.d 99.89
PBR-137 33.03 1.09 47.19 0.11 16.37 0.10 0.91 1.24 0.00 n.d 0.00 n.d n.d 100.03
PBR-137 32.81 0.62 47.14 1.11 16.52 0.27 0.37 0.00 0.00 n.d 0.07 n.d n.d 98.91
PBR-132 32.12 0.05 54.65 0.00 18.22 0.00 0.07 0.27 0.00 0.00 n.d 0.00 n.d 105.39
CHAPTER 2
 Appendix 2a.1 (cont.). Additional microprobe results obtained for some common phases from the Smelter deposit.
PBR-132 30.60 0.64 54.25 0.29 7.41 0.00 7.03 1.88 0.00 0.00 n.d 0.10 n.d 102.20
PBR-132 32.55 0.25 48.49 0.00 17.33 0.00 0.16 0.45 0.18 0.01 n.d 0.11 n.d 99.54
PBR-132 31.97 0.14 47.78 0.11 15.99 0.00 1.61 1.16 0.00 0.01 n.d 0.20 n.d 98.98
PBR-143 31.73 0.09 49.57 n.d 16.89 0.00 0.16 0.30 0.01 n.d 0.00 n.d 98.76
PBR-143 24.02 0.06 66.56 n.d 4.05 0.04 2.10 0.00 0.00 n.d 0.02 n.d 96.86
PBR-143 31.26 0.40 48.72 n.d 17.00 0.03 0.21 0.17 0.00 n.d 0.00 n.d 97.79

hessite?
PBR-263 0.05 0.03 0.79 0.02 0.01 60.37 0.00 0.09 0.03 n.d 0.24 n.d 39.25 100.87
PBR-263 0.03 0.01 0.75 0.00 0.00 57.52 0.00 0.13 0.00 n.d 0.00 n.d 42.21 100.64

luzonite
PBR-132 29.64 7.00 41.30 2.54 1.13 0.00 17.19 0.70 0.00 0.00 n.d 0.03 n.d 99.55
PBR-132 29.54 7.81 41.39 2.58 0.84 0.00 16.36 0.83 0.00 0.00 n.d 0.08 n.d 99.44
PBR-132 32.61 0.05 48.39 0.00 17.02 0.00 0.36 0.86 0.00 0.00 n.d 0.11 n.d 99.40
PBR-132 32.61 0.05 48.39 0.00 17.02 0.00 0.36 0.86 0.00 0.00 n.d 0.11 n.d 99.40

pyrite
PBR-132 53.45 46.86 0.82 0.01 0.04 0.00 0.03 0.03 0.00 0.00 n.d 0.00 n.d 101.22
PBR-137 54.66 46.88 0.54 0.00 0.03 0.02 0.03 0.00 0.00 n.d 0.00 n.d n.d 102.16
PBR-137 54.71 45.58 1.31 0.03 0.02 0.04 0.00 0.00 0.00 n.d 0.00 n.d n.d 101.67
PBR-137 54.40 46.02 0.32 0.02 0.02 0.01 0.02 0.01 0.00 n.d 0.02 n.d n.d 100.82
PBR-137 54.77 45.94 0.41 0.00 0.04 0.01 0.05 0.00 0.00 n.d 0.01 n.d n.d 101.23
PBR-137 54.72 47.07 0.04 0.00 0.07 0.02 0.06 0.05 0.00 n.d 0.01 n.d n.d 102.04
PBR-137 54.85 45.76 0.09 0.02 0.02 0.00 0.04 0.00 0.00 n.d 0.00 n.d n.d 100.78
PBR-137 54.68 46.71 0.29 0.02 0.01 0.01 0.04 0.00 0.00 n.d 0.01 n.d n.d 101.75
PBR-132 53.45 46.86 0.82 0.01 0.04 0.00 0.03 0.03 0.00 0.00 n.d 0.00 n.d 101.22
PBR-143 50.47 45.90 0.27 n.d 0.61 0.00 0.03 0.00 0.00 n.d 0.05 n.d 97.33
PBR-143 50.43 45.88 0.26 n.d 0.00 0.01 0.08 0.00 0.07 n.d 0.00 n.d 96.73
PBR-143 51.05 46.19 0.00 n.d 0.05 0.04 0.07 0.01 0.06 n.d 0.00 n.d 97.46
PBR-143 50.88 45.81 0.06 n.d 0.01 0.03 0.00 0.00 0.05 n.d 0.12 n.d 96.97
PBR-143 50.96 45.65 0.00 n.d 0.20 0.01 0.00 0.00 0.05 n.d 0.00 n.d 96.87
PBR-143 50.72 46.14 0.20 n.d 0.04 0.00 0.01 0.01 0.11 n.d 0.00 n.d 97.23
PBR-143 50.67 46.16 0.31 n.d 0.02 0.03 0.06 0.00 0.06 n.d 0.04 n.d 97.35

67
CHAPTER 2
68
Appendix 2a.1 (cont.). Additional microprobe results obtained for some common phases from the Smelter deposit.
PBR-143 50.37 45.24 0.17 n.d 0.45 0.02 0.06 0.00 0.06 n.d 0.04 n.d 96.40
PBR-143 51.20 45.70 0.13 n.d 0.07 0.01 0.02 0.00 0.08 n.d 0.10 n.d 97.30
PBR-143 51.33 45.73 0.10 n.d 0.02 0.03 0.00 0.00 0.05 n.d 0.00 n.d 97.26
PBR-143 51.32 45.13 0.97 n.d 0.00 0.02 0.06 0.00 0.00 n.d 0.08 n.d 97.58
PBR-143 50.50 45.45 0.50 n.d 0.00 0.05 0.03 0.00 0.00 n.d 0.05 n.d 96.58
PBR-143 51.06 46.04 0.18 n.d 0.04 0.00 0.00 0.00 0.08 n.d 0.13 n.d 97.53
PBR-143 51.08 44.83 1.84 n.d 0.03 0.03 0.01 0.00 0.12 n.d 0.00 n.d 97.95
PBR-143 50.97 45.52 0.55 n.d 0.03 0.02 0.00 0.00 0.09 n.d 0.02 n.d 97.19

stannoidite
PBR-132 29.61 8.35 41.30 2.10 0.99 0.00 16.83 0.00 0.00 0.01 n.d 0.02 n.d 99.20
PBR-132 29.56 7.87 47.97 1.38 1.47 0.00 15.96 0.32 0.00 0.00 n.d 0.00 n.d 104.53
PBR-132 28.80 6.92 47.11 1.59 1.03 0.00 16.78 0.29 0.00 0.00 n.d 0.00 n.d 102.51
PBR-132 29.57 5.85 49.38 0.27 2.34 0.00 15.77 0.52 0.00 0.00 n.d 0.02 n.d 103.72
PBR-132 29.61 8.35 41.30 2.10 0.99 0.00 16.83 0.00 0.00 0.01 n.d 0.02 n.d 99.20
PBR-132 29.64 7.00 41.30 2.54 1.13 0.00 17.19 0.70 0.00 0.00 n.d 0.03 n.d 99.55
PBR-132 29.54 7.81 41.39 2.58 0.84 0.00 16.36 0.83 0.00 0.00 n.d 0.08 n.d 99.44
PBR-263 28.74 8.22 43.62 0.40 1.72 0.00 14.82 0.89 0.00 n.d 0.06 n.d 0.04 98.51
PBR-263 28.04 4.17 39.78 1.17 1.43 0.00 24.11 0.00 0.00 n.d 0.00 n.d 0.06 98.75

tennantite
PBR-132 28.44 3.78 44.54 3.51 18.26 0.04 0.41 0.40 0.00 0.00 n.d 0.00 n.d 99.40
PBR-132 28.30 3.06 49.91 3.57 18.80 0.07 0.06 0.44 0.00 0.00 n.d 0.09 n.d 104.30
PBR-132 28.22 3.33 49.13 3.91 18.77 0.01 0.15 0.83 0.00 0.03 n.d 0.00 n.d 104.37
PBR-132 28.38 7.02 49.57 0.02 19.47 0.00 0.00 0.06 0.00 0.00 n.d 0.00 n.d 104.53
PBR-132 32.64 0.06 54.27 0.00 17.68 0.00 0.12 0.42 0.00 0.00 n.d 0.04 n.d 105.24
PBR-132 31.54 0.21 53.63 0.00 15.48 0.01 3.15 1.21 0.00 0.00 n.d 0.00 n.d 105.23
PBR-132 32.34 0.00 54.03 0.02 17.04 0.01 0.06 1.81 0.00 0.00 n.d 0.00 n.d 105.32
PBR-132 29.30 6.54 48.62 0.28 1.79 0.00 17.05 0.11 0.00 0.00 n.d 0.01 n.d 103.70
PBR-132 29.81 2.74 52.25 0.87 4.82 0.00 10.96 0.99 0.00 0.00 n.d 0.00 n.d 102.46
PBR-132 30.73 0.58 55.00 0.31 7.42 0.00 7.34 1.62 0.00 0.00 n.d 0.00 n.d 103.00
PBR-132 31.04 0.87 53.94 0.16 7.17 0.00 7.88 1.07 0.00 0.00 n.d 0.08 n.d 102.21
PBR-132 30.85 0.59 54.51 0.06 8.10 0.00 6.55 1.11 0.00 0.00 n.d 0.00 n.d 101.76
CHAPTER 2
 Appendix 2a.1 (cont.). Additional microprobe results obtained for some common phases from the Smelter deposit.
PBR-132 28.41 2.53 67.93 0.07 0.03 0.39 0.01 0.02 0.00 0.05 n.d 0.01 n.d 99.45
PBR-132 28.44 3.78 44.54 3.51 18.26 0.04 0.41 0.40 0.00 0.00 n.d 0.00 n.d 99.40
PBR-263 27.84 6.86 44.35 0.02 18.97 0.00 0.07 0.17 0.00 n.d 0.00 n.d 0.03 98.31
PBR-263 28.70 2.39 46.70 0.09 17.90 0.03 0.61 0.32 0.00 n.d 0.00 n.d 0.00 96.74
PBR-263 28.99 8.59 42.87 1.09 1.36 0.00 15.40 0.00 0.00 n.d 0.15 n.d 0.01 98.46
phases were analysed using a Cameca SX50 electron microprobe at the University of Lausanne. Instrumental conditions were: accelerating voltage of 12 kV, beam current of 30
nA, and spot size of 10 mm.

69
CHAPTER 2
70
Appendix 2a.2. Representative minor and major elemental composition of disseminated epithermal Au-Ag and Cordilleran polymetallic ore bodies in the Colquijirca District.
mineralization Disseminated Au-(Ag) occurrence Cordilleran polymetallic deposits
type

zone/sub-zone oxide-bearing vuggy quartz zone Cu-(Au-Ag) and Cu-(Ag-Sn-Bi) Cu-(Ag-Bi) and Zn-Pb-Cu-(Ag-Bi) Zn-Pb-(Ag)

location Oro Marcapunta Smelter (Marcapunta Norte) Colquijirca San Gregorio Colquijirca San Gregorio
Sample PBR-197 PBR-198 PBR-273 PBR-56 PBR-131 PBR-132 PBR-132b PBR-50 PBR-117 PBR-184 PBR-187 PBR-61b PBR-108 PBR-111 PBR-219 PBR-221 PBR-175
Sondaje SD-11 CM5-580 CM9-548 CM6-580 CM6-580 SD-3 Principal 14G 39G GN5-292
outcrop outcrop pit outcrop outcrop Principal Principal pit Principal pit
pit
depth (m) 144.00 101.50 247.30 104.20 116.40 39.70 294.00 173.20 93.50
Economically interesting metals
Zn (ppm) 25.9* 431* 37.8* 295* 119* 391* 45* >10000* 1290* 366* 88*** >10000* 83100*** 402000*** 102900*** 59500*** 341***
Pb (ppm) 332.0* 607* 4240* 532* 751* 534* 1330*** 77300* 583* 3790*** 5720* 14380* 284000*** 185600*** 25500*** 16800*** 13900***
Ag (ppm) 91.1* 30.2* 8.1* 61.9* 40.1* 15.4* 7.9* >100* 605* 148* 386*** >100* >100* >100* 2.4* 0.3* 4720***
Cu (ppm) 64.7* 43* 41.2* >30000* 34500*** 79500*** 41200*** 3380* 25100*** 16* n. d. 1200* 365* 1.4* 28.1* 9.8* 3470***
Au (ppm) 0.472** 1.101** 0.187** <0.05**** 0.64** 1.06** 10.08** <0.05****<0.005** <0.005** n. a.1 n. a.1 n. a.1 n. a.1 n. a.1 n. a.1 <0.005**
Bi (ppm) 21* <5* 19* 126* 95* 133* 149* 3010* 5370*** 3930*** 1660*** 14* 6* 19* 19* 10* 105*
Sn (ppm) 13* 13* 16* 1850* 424* 427* 168* <10* 21* 120* 280*** 11* <10* <10* <10* <10* 80*
W (ppm) 182* 37* 19* 114* 793* 978* 1360* <10* 1540* 2170* n. d. <10* 228* 80* 291* 465* 329*
Ir (ppm) <0.02** 0.021** <0.02** n. a. 0.103** 0.04** 0.12** n.a 0.108** <0.02** n. a. n. a. n. a. n. a. n. a. n. a. 0.023**
Other elements
Fe (%) 1.94*** 0.1* 1.05* 15.6* 17.91*** 5.13*** 1.17*** 4.9* 4.44*** 0.69* 0.84*** 17.7* 5.55*** 102600*** 1.96*** 0.51*** 41.02***
S (%) 0.13*** n. a. n. a. n. a. 21.54*** 10.21*** 6.53*** n. a. 5.70*** 0.75*** 0.87*** n. a. 12.51*** 26.17*** 6.22*** 2.52*** 35.48***
As (ppm) 152* 27* 2140* 25070* 12500*** 28900*** 15500*** 12* 6200*** 262* 335*** 39* 30* 157* 126* 18* 1150***
Sb (ppm) 26* <5* 128** 5480* 712* 500* 548* <5* 133* 703* 1200*** 7* 89* 213* 184* 69* 476*
Sr (ppm) 79.9* 606* 293* 347* 515* 334* 1730*** 10* 221* 2510* 3190*** 29.6* 109* 34.3* 1060*** 65.1* 2730***
Ba (ppm) 211* 376* 361* 25* 63* 132* 294* 35* 9700** 620* n. d. <1* 68* 55* 309* 105* 2990**
U (ppm) 3.4** 3.1** n. a. n. a. 14.6** 4.2** 6.3** n. a. 426** 3.2** n. a. n. a. n. a. n. a. n. a. n. a. 9.6**
Major elements***
SiO2(%) 94.48 n. a. 96.21 n. a. 50.23 70.94 60.47 n. a. 74.33 85.88 87.26 n. a. 37.37 2.09 51.42 78.62 3.17
Al2O3(%) 0.51 n. a. 0.46 n. a. 3.82 1.86 8.34 n. a. 0.38 3.47 3.16 n. a. 5.76 2.19 20.73 8.61 13.93
Fe2O3(%) 2.73 n. a. 1.87 n. a. n. d. n. d. 1.67 n. a. 6.34 0.90 1.74 n. a. n. d. n. d. 2.80 n. d. n. d.
CaO(%) 0.03 n. a. 0.05 n. a. 0.13 0.24 0.12 n. a. 0.02 1.38 0.14 n. a. 0.01 n. d. 0.16 0.10 0.03
K2O(%) 0.07 n. a. 0.11 n. a. 0.67 0.34 1.64 n. a. 0.03 0.33 0.33 n. a. 1.22 n. d. 0.29 0.14 1.89
TiO2(%) 0.73 n. a. 0.58 n. a. 0.17 0.04 0.15 n. a. 0.14 0.19 0.05 n. a. 0.01 0.02 0.28 0.12 n. d.
py: pyrite, en: enargite, lu: luzonite, wt: wolframite, co: colusita, cpy: chalcopyirite, bn: bornite, tn: tennantite, sl: sphalerite, ga: galena, st: stromeyerite, * ICP, Induced coupled plasma multi acid digestion analysis. As, Sb, Bi,
W may be affected for samples with >1.0 % Cu, Zn or >25 % Fe. ** Neutron activation, *** XRF UniQuant, **** cyanidation , n. a. no analized, n. a.1 not analized but analysis of equivalent samples indicates less than
0.1 ppm, n. d. no detected.
CHAPTER 2
 CHAPTER 2

Appendix 2a.3:

a: iridium b: bismutinite

c: hessite? d: native tellurium

e: unidentified f: unidentified
mineral mineral

71
 CHAPTER 2

72

2b. The Colquijirca deposit
The ores of Colquijirca occur almost totally
as mantos, which are Zn-Pb-(Ag) sulfide-rich ores
and range in general between 30 and 50 volume %
sulfides. Mining at Colquijirca takes place from two
open pits with a current production rate of ~4,000
tones (t) per day at 6.0 % Zn, 3.0 % Pb, and 4 oz/t
Ag. Reserves in 2005 rose to ~8 Mt at 5.5 % Zn, 3 %
Pb, and 3.5 oz/t Ag. Production to date aggregates at
least 20 Mt at 6 % Zn, 2.0 % Pb, and 5 oz/t Ag.
Notwithstanding the proximity of Colquijirca
to the Smelter deposit, a physical connection between
them was not recognized for a long time (Bendez,
1997). In this work, however, a connection is
established based mainly on stratigraphic correlation
of drill cores (Figure 2a.3). Recent exploration
drilling carried out in 2004-2005 demonstrated that
Colquijirca constitutes the northern extension of the
enargite-rich bodies of the Smelter deposit (Figure
2b.1).
Host rock
The ores at Colquijirca are exclusively hosted
in carbonate rocks of the Pocobamba Formation, in
which they specifically replace a 50-90 m thick interval
of the Middle sub-member of the Calera Member
(see Chapter 1 for details of the stratigraphy); in
contrast to the Smelter deposit (Chapter 2a), no
mineralization is found in the Shuco Member.
The original lithological sequence can be
observed in several nearly unmineralized drill holes
(e.g., DDH SP2-218) and consists of wide variety
of alternating carbonate rocks, including largely
limestones and marls as well as subordinate detrital
rocks such as argillites and tuffs. Figure 2b.2 shows
the three sub-members of the Calera Member as
well as three stratigraphic markers used in the mine
for exploitation and exploration purposes. These
markers are, at the deposit scale, widespread and easy
to identify, even beyond the limits of the Colquijirca
deposit (e. g., in Smelter deposit). The main markers
are labeled TGR1, TGR2, and CZMS and consist of
fallout tuff layers in the case of the first two and a
bed of argillite in the last.
In southern Colquijirca, in the area exposed
by the Principal pit, the mantos occupy a section
approximately 60 m thick from 10 m below the
CZMS argillite marker to the 30 m below the lower
TGR2 tuff marker (Figure 2b.2). The northernmost
CHAPTER 2
exposed area in the Mercedes-Chocayoc pit
(Mercedes Norte; Figure 2b.2) reveals that the
mineralized section is nearly 90 m thick and is
stratigraphically at least 30 m higher (from 10 m
above the TGR2 lower tuff marker to a few tens of
meters above the argillite marker; Figure 2b.2). Drill
holes at Mercedes Norte and others located 500 m
farther to the north, at Condorcayn (Figure 2b.1),
confirm the increasingly higher stratigraphic position
of the mineralized interval when advancing to the
north. The stratigraphic position of the mantos is
40 to 50 m higher at the northernmost recognized
occurrence at Condorcayn than at the southern part
of the Colquijirca deposit, i.e., over a total horizontal
distance of almost 1,500 m.
Spatial configuration of the ore bodies and
controls on mineralization
The spatial configuration of the ore bodies at
Colquijirca is primarily controlled by bedding. Mantos
are, therefore, the only economically important ore
structures. Collectively, these ore structures configure
a single large manto as illustrated in Figure 2b.2. This
single large manto shows a continuity over nearly
2 km of length, 50-70 m thickness and 500-800
m width along strike from the Principal pit to the
northernmost recognized occurrence at Condorcayn
(Figure 2b.1). The manto varies abruptly in strike
and dip due to the pronounced folding. Thus, it
is found either gently dipping, as in the case in
the La Pampa flank in the easternmost portion of
Colquijirca (Figure 2b.1), or emplaced semi-vertically
along flanks of anticlines and synclines as within the
tight Mercedes-Chocayoc anticline (Figure 2b.2). The
bedding also defines a characteristically sharp contact
between either fresh carbonate rocks and the mantos
or between individual mantos.
Compared with other important, although
local, controls on the mineralization (i.e., rupture
structures and fold axes), bedding defines the internal
structure of both the whole Colquijirca deposit and
individual ore mantos at kilometric, outcrop and, in
places, even smaller scales. The first is evidenced by
the extreme flatness of individual mantos, with many
being 2 to 4 m thick, tens of meters wide and more
than 600 m long along strike. Even at the microscopic
scale, the bedding control may be striking. In places,
replacement is observed to mimic bedding to such
73
 CHAPTER 2

Condorcayn

N
E 361500

300 m
S 820

Zn-Pb-Cu-(Bi-Ag) and Zn-Pb-(Ag)

E 362 000
S 796

c'
c
Cu-(Bi-Ag)

La Pampa flank
old workings
Cu-(Ag)
ORE ZONES

E 361 000

N 8 811 700
S 772
a'

S 748
Mercedes-Chocayoc pit
b

Colquijirca
N

S 724

N 8 811 000
b'

Principal pit

500 m

S 700
Smelter

Marcapunta
sample studied
a

Figure 2b.1: Plan view of the Colquijirca deposit showing the main ores zones described in the text. Samples studied in this
work are also shown. Note that old silver workings largely followed the main axis of the deposit.

74
 a a'
Principal pit
4300 masl

SP1-130 TN4-700
TN4-760 Mercedes Chocayoc pit
TN6-764
CZMS

ORE ZONES

ferent as shown individually.

Cu-(Ag)

Cu-(Bi-Ag)

Zn-Pb-Cu-(Bi-Ag)
Shuco Conglomerate Calera Limestones and Zn-Pb-(Ag)

Mitu Group 50 m

200 m

b b' c c'
CZMS Mercedes Chocayoc pit
Principal pit SD-B2 CZMS
20-P SD-84 24-P SD-38
SD-88 TN1-170 SD-B3
SD-92 TN3-163 SD-B4
TGR1
SD-21
TGR2

TN5-792
TN6-792

Shuco Member

100 m
TGR1

50 m

75
Figure 2b.2: Three selected cross sections of the Colquijirca deposit as indicated in Figure 2b.1. Scales in each section are dif-
CHAPTER 2

a degree that sulfide bands are only several tens of
micrometers thick. The influential role of bedding is
also reflected in the strong internal zoning throughout
the whole Colquijirca deposit, as shown in Figures
2b.2 and 2b.3. Each mineral zone, regardless of the
degree of replacement, has inherited the bedding
structures and displays a concentric flat tubular
geometry.
The southernmost segment of the high-grade
mantos in the Colquijirca deposit are oriented roughly
north-south (Figure 2b.1). Immediately to the north,
they display a markedly contrasting alignment of
around N45E, following a fracture set with this
same direction. Farther north, the mantos change to
a south southeast-north northwest direction, along
the axis of the Mercedes-Chocayoc anticline and
other folds of similar direction (Figure 2b.1).
The faults and fractures are apparently part of
a widespread fault system mapped in different parts
of the entire Cerro de Pasco-Colquijirca sector by
Angeles (1993) (F1-F2 fault system, Chapter 1a) and,
along with the Mercedes-Chocayoc anticlinal, are
probably related to the main Aymara or Quechua
I (Miocene) compressive tectonic phase. Fractures
and faults transverse to beddings were probably
responsible for the gradual channeling the ore fluids
into stratigraphically higher beds along the entire
fluid pathway, as shown in Figure 2b.2.
More important in terms of extension and
metal content of the mantos are the influence
provided by fold axes and other non-rupture
structures. A clearly discernable example is given
by the flexure portions of the Mercedes-Chocayoc
anticline and more open associated folds (particularly
northward from line 756; Figure 2b.2). North from
this point, the ore fluids were effectively channeled
by these structures in a style comparable to saddle
reef structures in some vein deposits (e.g., Bendigo,
Australia; e.g.,
Fowler and Winsor, 1997
). The ore
bodies in the flexure portions are considerably
thicker, and more prominently, the grades are higher.
Perhaps the most spectacular example is found along
the entire length of the flexure zone of the Mercedes-
Chocayoc anticline, from which most of the bonanza
silver grades were extensively exploited underground
during the early 20th century (Figure 2b.1). This style
of mineralization controlled by bedding openings
during flexure is a typical feature of mineralization
that postdates folding.
In the central portions of the Colquijirca
deposit, regardless of the original lithology, virtually
all beds were completely replaced to leave no
significant relicts (Figure 2b.3). Outermost individual
mantos are in many places separated from others by
relatively non-reactive units such as massive argillites
or argillaceous tuffs. Furthermore, even intervals of
fine-grained, massive dolostones intercalated with
the mineralized mantos are common in these external
portions. These observations suggest that the less
reactive units served as impermeable horizons that
76
CHAPTER 2
effectively ponded the ore solutions.
Mineral deposition history: stages and
zoning
Mineralization in the Colquijirca deposit is
particularly complex in terms of both mineralogical
and elemental patterns (Appendix 2b.2). Nearly 90
studied samples from throughout the Colquijirca
deposit show that three main mineral stages are
present, in a remarkably similar fashion to the Smelter
deposit (Figures 2b.3, 2b.4, 2b.5 and 2b.6). An Early
silica-pyrite stage (i) composed mainly of silica and
pyrite, a subsequent Main ore stage (ii) recognized
as responsible for the main zoning of the deposit
from Cu-(Ag) to Zn-Pb-(Ag), and a late Cu and/or
Zn stage (iii). As in the Smelter deposit, these stages
are respectively termed Early silica-pyrite stage, Main
ore stage, and Late ore stage.
Zoning in the Colquijirca deposit is well
marked and probably one of the best developed in
the whole Andes. In contrast to the Smelter deposit,
overprinting by the Late ore stage is volumetrically
less important.
Because of the great similarity between
the Smelter and Colquijirca deposits, much of
the description presented here is an inter-deposit
comparison.
Early silica-pyrite stage
Silica and pyrite are the main constituents of
the oldest recognized stage in Colquijirca (Figure
2b.6). Compared with the more extended Early silica-
pyrite stage of the Smelter deposit, at Colquijirca it is
confined only to the inner portions of the southern
segment of the Colquijirca deposit, where it developed
a continuous massive stratiform replacement body
20-25 m thick that extends for ~500 meters from the
southern limit of the Principal pit to line 740 (largely
the Cu-(Ag) zone in Figure 2b.2).
No major difference in the proportions of
the different silica types is observed between the
Colquijirca and Smelter deposits (see Chapter 2.1).
Thus, besides the dominant finely crystallized quartz
(quartz I), chalcedony, jasperoidal silica, and rarer
opaline masses constitute the main silica types. Silica
in its different forms usually composes more than
two-thirds by volume of the silica-pyrite stage; only
rarely does pyrite, the second major component,
surpass 50 volume %. In the massive core, quartz is
commonly fine grained (<100 m) and euhedral. It
is irregularly associated with minor cryptocrystalline
silica, which generally occupies interstices. Pyrite is
similarly fine-grained, but in rare cases grains can
attain 0.5 cm in size. Early pyrite, hereafter named
pyrite I, commonly displays pronounced zoning,
which rapidly becomes visible following brief
 CHAPTER 2

22

28

21

18

22
19
18

21 26
18

Outer limit of quartz-alunite-pyrite

assemblages (Main ore stage)
Bedding 28
20

27

Outer limit of the silica-pyrite

replacement body (Early silica-pyrite stage)

5m

Cu-(Ag) zone Cu-(Ag-Bi) zone

Enargite dominant sub-zone
> 2 vol. % enargite > 2 vol. % chalcopyrite

Enargite dominant sub-zone

< 2 vol. % enargite < 2 vol. % chalcopyrite

bornite dominant sub-zone

> 2 vol. % bornite Zn-Pb-(Ag) zone
bornite dominant sub-zone
> 10 vol. % sphalerite + galena
< 2 vol. % bornite

tennantite dominant sub-zone

< 10 vol. % sphalerite + galena
> 2 vol. % tennantite

Figure 2b.3: Map of a portion of the transition sector between the Cu-(Ag), Cu-(Ag-Bi), and Zn-Pb-(Ag) zones in the
Principal pit. The figure shows the outer limit of the silica-pyrite replacement body and external limit of the quartz-alunite-pyrite
assemblage. As discussed in the text, note the distribution of the alunite-bearing assemblage differs from that of the enargite-
Figure
dominant 2b.3
sub-zone.

77

atmospheric oxidation. A remarkable similarity with
pyrite I from the Smelter deposit, which serves as a
distinction from later pyrite, is the octahedral shape.
It usually occurs as subhedral and relatively rare
euhedral grains, mostly slightly corroded.
The different textures observed at Smelter are
extraordinarily similar to those present in this inner
massive silica-pyrite manto at Colquijirca (Chapter
2.a). Among the most remarkable are the brecciated
and distinctly laminated textures. The brecciated
textures seem to be generated by multigenerational
precipitation of silica-pyrite without any evidence of
ore deposition.
From line 740 northeastward, only dark
decimetric beds characterize the silica-pyrite stage.
These thin beds are, however, numerous, widespread
and persistent along the most external parts of the
Colquijirca deposit as well as at Condorcayn. The
beds, known locally as chert, are most commonly
composed of dark to black cryptocrystalline material,
including finely crystallized quartz, which, in general,
makes up no more than 30 volume % of the rock.
Under the microscope, these beds are seen to contain
<5 volume % of pyrite inclusions, <100 m in size.
The pyrite is slightly corroded.
A generation of finely crystallized euhedral
quartz forming small geodes is fairly common in
these thin outer dark silicified beds. The intimate
intergrowths with sphalerite and galena, as well as
fluid inclusion data, show that the euhedral quartz
was deposited during the subsequent Main Ore
Stage.
Mineralogically this stage is very simple.
Sporadically, minute rutile grains (<40 m) are
observed in the silica-pyrite mass. A significant
difference with the silica-pyrite stage of the Smelter
deposit is the local presence of tiny sphalerite grains,
which like the rutile, appear to also be part of the
matrix.
Microprobe analyses of pyrite I show only
minor amounts of As and Cu in its structure (up to
1 wt. % for both). No SEM study was performed on
this early pyrite but presumably, based on the similar
composition to that of pyrite I from the Smelter
deposit, these elements would be largely responsible
for the marked zoning, which becomes visible upon
surface oxidation.
Main ore stage
Interpretation of the main zoning of the
Colquijirca deposit as the product of a single
mineralization stage, postdating the silica-pyrite
stage, is supported by time-integrated elemental,
mineralogical and geometric relationships similar
to those documented for the Smelter deposit. A
discussion of this interpretation is presented at the
end of this chapter.
The zoning in Colquijirca is much better
78
CHAPTER 2
developed than at Smelter, and a wider range of
zones as well as more generalized superimposition
of them adds considerable complexity to the pattern
found at Smelter. The Main ore stage (Figure 2b.6) is
divided in four zones based on the main economically
interesting elements, from an innermost Cu-(Ag)
zone to a Cu-(Ag-Bi) zone, a Zn-Pb-(Ag-Cu-Bi)
zone, a Zn-Pb-(Ag) zone, and to an outermost Pb-
Zn-(Ag) zone.
Cu-(Ag) zone
This zone roughly mimics the Early silica-
pyrite replacement body, but when observed in detail
the Cu-(Ag) zone is usually restricted to only the
internal parts of the silica-pyrite body (Figure 2b.3).
The Cu-(Ag) zone can be divided into three well-
defined sub-zones, which are: an enargite-dominant
core, a bornite-dominant sub-zone and a tennantite-
dominant outer part.
Enargite-dominant sub-zone: Enargite
represents >95 volume % of the copper phases in this
zone. Luzonite is only occasionally as significant as
that in the Smelter deposit. Enargite is coarse grained
but not as coarse as that at Smelter. Commonly,
striated acicular grains were observed to be as long
as 4 cm. Most of the well-formed grains are found
in small druses in breccias. Typically, enargite is
observed replacing Early silica-pyrite stage pyrite I to
various degrees.
The bulk of the enargite is present cementing
hydraulic breccias, incipient crackle breccias, and
in veinlets. In all cases, deposition of enargite was
contemporaneous with the brecciation. Enargite
in hydraulic breccias can form massive aggregates,
which under the microscope appear as mosaics of
anhedral grains without any sign of development
of crystal faces and showing abundant corrosion
and recrystallization features. In crackle breccias
and veinlets, enargite often occurs as coatings and
clusters, frequently with euhedral crystals, and with
corrosion being less common. Again, as in the case
of the Smelter deposit, an apparent relationship is
observed between dissolution and recrystallization of
enargite and the presence of alunite. At Colquijirca,
the great majority of the euhedral enargite is free of
alunite. Indeed, detailed mapping of a portion of
the Cu-(Ag) zone shows that most of the alunite,
which constitutes assemblages with quartzpyrite
II (see below), occurs without enargite (Figure 2b.3).
In contrast, euhedral enargite is most commonly
observed in contact with kaolinite and/or dickite
(see below).
Main ore stage pyrite in the enargite-dominant
zone (pyrite II) is volumetrically more important than
at Smelter. It typically occurs as euhedral pentagonal
dodecahedral crystals up to 5 mm in size. Again, as at
Smelter, pyrite II is strongly zoned. The largest pyrite
II grains are intimately intergrown with enargite,

with common reversals in crystallization sequence
observed between them. Irregular blebs of pyrite II
in enargite are less rare than at Smelter. The most
abundant pyrite II population accompanies alunite
and fine-grained quartz but is free from enargite.
This pyrite II is also pyritohedral and always well
crystallized. It occurs in direct contact with alunite
without evidence of reaction and shows reversed
overgrowths with the latter mineral. Similarly,
fine-grained quartz II, in places showing reversed
crystallization with alunite, and thought to have
co-precipitated with it, shows no reaction where in
contact with alunite. The absence of reaction is a
prominent difference from the fine-grained-quartz I
from the Early silica-pyrite stage and the coarse grains
of quartz II coetaneously precipitated with enargite,
which in places displays strong corrosion leaving only
a skeletal vuggy mold. As previously mentioned, the
detailed mapping shown in Figure 2b.3 shows that
the alunite-quartz II-pyrite II assemblage spatially
mimics the silica-pyrite replacement body, but if
observed in more detail it is observed to spread
beyond (Figure 2b.3).
In polished section, luzonite is relatively rare and
replaces enargite along its cleavage. It is unmistakably
distinguished from enargite by its polysynthetic
twinning and pale pinkish colour. Other trace phases
occurring as minuscule wisps within enargite, and
more rarely, within pyrite I, are stibnite, emplectite,
and very small grains of unidentified bismuth-bearing
minerals.
Alunite is distributed throughout the entire
enargite-dominant sub-zone (Figure 2b.3). As
previously mentioned, it occurs as an assemblage with
fine-grained euhedral pyrite II with which it displays
reversed overgrowths and intricate intergrowths.
Alunite is typically platy and has a translucent whitish
not pinkish tone in contrast to that in the inner zones
of the Smelter deposit. Relative to the Smelter alunite
it is finer grained and grains perpendicular to the c axis
are much thinner. Alunite typically fills intergranular
spaces in enargite and quartz, both the quartz I from
the Early silica-pyrite stage and fine-grained quartz
II (Figure 2b.4). In places, hydraulic breccias are
cemented by the alunite-pyrite II-(quartz) assemblage,
suggesting that these minerals were deposited from
the introduced fluid. Detailed mapping shows that
alunite-bearing assemblages are not restricted to the
enargite-dominant sub-zone but extend upward into
the immediately overlying Zn-Pb-(Ag) zone, where
they coexist with sphalerite and galena, and into the
bornite-dominant sub-zone (Figure 2b.3).
The absence of zunyite is a main difference
between the enargite-dominant sub-zone of the
Colquijirca deposit and most of the enargite-bearing
zones in the Main ore stage of the Smelter deposit.
Similarly, no significant pyrophyllite was detected in
this sub-zone.
Kaolinite and dickite are common, though
minor phases accompanying enargite in the enargite-
CHAPTER 2
dominant sub-zone. As previously noted, kaolinite
and/or dickite occur in contact with euhedral
enargite, commonly without any sign of corrosion
or recrystallization. They mainly occur filling
intergranular spaces in enargite as in much of the
Smelter deposit.
The enargite-dominant sub-zone contains
numerous thick decimetric lenses and thinner beds of
sphalerite-galena-pyrite-hematite-siderite-kaolinite
(Figure 2b.3). Crosscutting relationships indicate that
this mineral association predates the enargite sub-
zone. An interpretation of this observation in terms
of advancement of the copper front with time is
discussed at the end of this chapter.
In a similar manner as at Smelter, considerable
portions of the enargite-dominant sub-zone are
overprinted by chalcocite-bearing associations. Again,
as in the Smelter deposit, these associations are
attributed to a Late ore stage, as described below.
Composition of minerals of the Cu-(Ag) zone
A quantitative data set for the main phases
observed in this sub-zone from microprobe analysis
is available in Table 2b.1.
Enargite is largely stoichiometric. Antimony
substitution for arsenic seems to be more important
than at Smelter, but this assumption is not definitive.
Silver is concentrated in amounts as high as 1.1 wt. %,
similar to enargite in the outer Cu-(Ag) zone of the
Smelter deposit. No analyses were run for luzonite.
A few analyzed grains of pyrite II show that it
is essentially stoichiometric. Copper and arsenic were
found to be <0.2 wt. %.
Two widely-spaced alunite samples were
subjected to microprobe analysis. Multipoint
traverses of several grains from core to rim show no
major compositional variations. The analyzed grains
plot in the alunite end-member field, with typical
Na/K ratios of <0.1. Relatively minor substitution
of K by P in the R site is sporadic. Similarly, no
significant K substitution for Ca and Sr was found.
More importantly, for purposes of comparison
with alunite from the Smelter deposit, virtually no
Pb was encountered to occupy the A site of alunite
from this enargite-dominant sub-zone. Based on the
microprobe traverses, only subtle fluctuations in the
Na/K ratios are irregularly recorded.
Bornite-dominant sub-zone: This zone
appears to occur in gradational contact with the
enargite-dominant zone. Over an interval of <60
cm, bornite increases in volume and enargite virtually
disappears. In terms of tonnage, this zone makes up
no more than 5 volume % of the entire Cu-(Ag)
zone and forms small discontinuous pod-like bodies,
in part surrounding the enargite-dominant sub-zone
(Figure 2b.3). These pod-like bodies measure up to 10
79

m long, 4-6 m wide, and 2-3 m thick. Copper grades
are high, in places exceeding 5 wt. %, but this sub-
zone is not mined for Cu because of its small tonnage.
The bornite-dominant sub-zone is observed only
along the strike, both laterally, and most importantly,
frontally relative to the main direction of ore fluid
movement (Figure 2b.3). Only at one point, a few
decimeters thick and 1 m long, a pod of bornite-rich
ore was observed to immediately overlie the enargite-
dominant zone (perpendicular to bedding).
The main mineral association in this sub-zone
is bornite-tennantite-pyrite-sphalerite-quartz-barite,
dickite-(kaolinite) and a phase presumed to belong to
the APS group, possibly alunite. Minor components
are covellite-chalcopyrite-chalcocite-digenite-galena-
(siderite) plus other trace phases. In this association,
part of the pyrite, quartz, and sphalerite clearly
predate bornite deposition, while the rest of the
minerals precipitated after bornite.
Bornite accounts for up to 30% of the rock, is
never observed in well crystallized form and typically
occurs as irregular masses. At the microscopic scale,
bornite displays abundant dissolution voids, usually
filled with dickite-(kaolinite) (Figure 2b.4) and, more
rarely, with a finely crystallized APS group mineral,
possibly alunite. In most places, bornite grew
interstitial to the silica matrix, largely euhedral quartz
with open-space filling textures. These textures show
that bornite either co-precipitated with quartz or
postdated it. As described below, bornite infillings
within pyrite and barite are also observed.
Pyrite from the bornite-dominant sub-zone
is typically pentagonal dodecahedral and relatively
coarse grained (up to 0.5 cm). It often occurs as
clusters rimmed by bornite. In most examples, pyrite
shows no reaction effects in contact with bornite
(Figure 2b.4). However, it is relatively common to
observe pyrite slightly to moderately replaced by
bornite. Where bornite cements brecciated pyrite
grains, which are angular and not resorbed, there is
no reaction effects. Similarly, in bornite stockworks
cutting euhedral pyrite, the fragments of the latter
mineral have matching contacts and do not show
any evidence for reaction. A minor bornite fraction
occurs as late wisps in this pyrite, partially filling
minute fractures.
All the observed sphalerite and much of the
quartz have a temporal position similar to or even
earlier than that of the pyrite showing no reaction
when in contact with bornite (Figure 2b.4). Sphalerite,
extensively replaced by bornite, clearly predated this
mineral (Figure 2b.4). In places in which sphalerite
is in contact with pyrite, no reaction is observed
between them. Similarly, common bornite-infillings
within quartz, as described below, are indicative of
earlier crystallization of the latter mineral. The early
timing of the bulk of the quartz, pyrite and sphalerite,
combined with microprobe analyses typical of more
external Zn-Pb-bearing zones, suggests that these
minerals were formed from the same fluid as that
80
CHAPTER 2
circulating prior to bornite formation. Pyrite showing
corrosion in contact with bornite is observed to be
appreciably replaced by sphalerite, suggesting that it
formed even earlier, possibly from the Early silica-
pyrite stage.
Among the minor phases observed in this sub-
zone, chalcopyrite occurs as blebs within bornite or
sometimes as veinlets that seem to follow cleavage in
the bornite. Enargite is present interstitial to quartz
grains in an undefined temporal position relative
to bornite. Another minor phase observed in one
sample is thought based on its optical properties,
to be mawsonite,. It occurs between broken bornite
fragments which display matching contacts.
Accessory phases recorded with EDS tests
are bismuth-antimony-copper-bearing grains. They
occur as <10 m blebs in pyrite and occasionally in
bornite.
Quartz in the bornite-rich sub-zone is
abundant, and typically euhedral and relatively coarse
grained (up to 1 cm). It constitutes up to >50 volume
% in some portions of the bodies. According to the
type of mutual contact with bornite and/or dickite-
(kaolinite)-APS mineral?, quartz may be divided into
two types. The first, and volumetrically most important
(70-90 %), shows no evidence of reaction in contact
with these minerals. The second, less abundant
type of quartz, shows significant corrosion when
in contact with both bornite and dickite-(kaolinite)-
APS mineral?. Based on these relationships, it is
considered that the quartz precipitated both earlier
than bornite and contemporaneous or postdating it.
Resorption of quartz is more pronounced in contact
with dickite-(kaolinite-) and the APS mineral?. These
facts, as mentioned above, suggest that the bulk of
the quartz, together with pyrite and sphalerite, could
well be product of same earlier surge of fluids that
predated bornite deposition and argillic to advanced?
argillic alteration minerals.
Apart from quartz, barite is the most
important gangue phase in this sub-zone, accounting
for between 2 and 10 volume %. Barite is euhedral
and typically coarse grained (0.5 - 2 cm). Its form is
invariably tabular, although occurring in two habits.
Predominantly, the barite is dispersed through a mass
of anhedral pyrite and/or bornite. Less frequently,
barite occurs as overgrowths on pyrite, and more
rarely bornite. Minute bornite inclusions within barite
are not rare. These occurrences of bornite are highly
suggestive that barite co-precipitated from the same
fluid stage which deposed bornite. As described above
kaolinite-(dickite) and the APS mineral? typically fill
vugs in bornite and quartz.
Quantitative data obtained from electron
microprobe analysis is limited. Only one representative
sample was studied by this technique. Bornite
showed mostly stoichiometric compositions (Table
2b.1), although some analyses yield compositions
which deviate significantly from stoichiometry.
More precisely, an excess of copper was found
 Table 2b.1: Composition of selected sulfur-bearing phases of the Main ore stage according to microprobe analysis.
Sample Mineral stage/zone S Fe Cu As Ag Sb Bi Sn Zn Total
PBR-218 pyrite II Main ore stage/Cu-(Ag) 54.71 45.48 0.04 0.02 0.04 0.00 0.00 0.00 n.a. 100.27
PBR-218 pyrite II Main ore stage/Cu-(Ag) 54.40 46.22 0.09 0.12 0.01 0.01 0.00 0.00 n.a. 100.54
PBR-218 pyrite II Main ore stage/Cu-(Ag) 54.77 45.94 0.19 0.04 0.01 0.00 0.00 0.00 n.a. 100.95
PBR-218 pyrite II Main ore stage/Cu-(Ag) 54.35 45.43 0.08 0.08 0.01 0.00 0.11 0.02 n.a. 99.98
PBR-244 pyrite II Main ore stage/Cu-(Ag) 54.02 45.16 0.17 0.01 0.01 0.00 0.00 0.01 n.a. 99.36
PBR-244 pyrite II Main ore stage/Cu-(Ag) 53.70 44.89 0.16 0.08 0.01 0.00 0.00 0.00 n.a. 98.77
PBR-244 pyrite II Main ore stage/Cu-(Ag) 53.38 44.62 0.16 0.12 0.01 0.00 0.00 0.00 n.a. 98.18
PBR-218 enargite Main ore stage/Cu-(Ag) 32.64 0.06 49.27 17.68 0.00 0.42 0.00 0.08 n.a. 100.08
PBR-218 enargite Main ore stage/Cu-(Ag) 32.55 0.25 48.49 17.33 0.00 0.45 0.00 0.00 n.a. 99.07
PBR-218 enargite Main ore stage/Cu-(Ag) 32.89 0.05 48.66 16.80 0.31 0.74 0.00 0.30 n.a. 99.46
PBR-244 enargite Main ore stage/Cu-(Ag) 33.18 0.05 48.36 17.11 0.10 0.40 0.25 0.34 n.a. 99.20
PBR-244 enargite Main ore stage/Cu-(Ag) 33.08 0.01 49.02 17.11 0.03 0.89 0.00 0.23 n.a. 100.14
PBR-244 enargite Main ore stage/Cu-(Ag) 32.77 0.03 48.59 17.01 0.09 0.81 0.00 0.43 n.a. 99.29
PBR-244 enargite Main ore stage/Cu-(Ag) 32.53 0.08 48.70 17.00 0.03 0.54 0.00 0.72 n.a. 98.88
PBR-244 enargite Main ore stage/Cu-(Ag) 33.19 0.02 48.82 17.22 0.07 0.50 0.00 0.27 n.a. 99.82
PBR-187 bornite Main ore stage/Cu-(Ag) 25.37 11.18 64.06 0.03 0.01 0.02 n.a. 0.11 n.a. 99.82
PBR-187 bornite Main ore stage/Cu-(Ag) 25.89 11.21 64.87 0.07 0.01 0.02 n.a. 0.14 n.a. 99.82
PBR-187 bornite Main ore stage/Cu-(Ag) 25.26 11.20 64.65 0.03 0.12 0.05 n.a. 0.04 n.a. 99.82
PBR-95 tennantite Main ore stage/Cu-(Ag) 28.22 3.33 46.13 18.77 0.01 0.83 0.00 0.15 3.91 101.34
PBR-95 tennantite Main ore stage/Cu-(Ag) 28.38 7.02 46.57 19.47 0.00 0.06 0.00 0.00 0.02 101.53
PBR-95 tennantite Main ore stage/Cu-(Ag) 28.44 3.78 44.54 18.26 0.04 0.40 0.00 0.41 3.51 99.40
PBR-123 chalcopyrite Main ore stage/Zn-Pb-Cu-(Ag-Bi) 34.63 29.50 34.74 0.03 0.06 0.07 0.09 0.03 0.00 99.15
PBR-123 chalcopyrite Main ore stage/Zn-Pb-Cu-(Ag-Bi) 34.37 29.93 34.65 0.01 0.00 0.00 0.00 0.06 0.14 99.17
PBR-123 chalcopyrite Main ore stage/Zn-Pb-Cu-(Ag-Bi) 34.44 29.43 34.56 0.02 0.03 0.05 0.00 0.06 0.32 98.91
PBR-285 sphalerite Main ore stage/Zn-Pb-(Ag) 32.24 2.41 n.d. n.d. n.d. n.d. n.d. 0.01 64.80 99.45
PBR-285 sphalerite Main ore stage/Zn-Pb-(Ag) 32.89 1.86 n.d. n.d. n.d. n.d. n.d. n.d. 65.23 99.98
PBR-241 sphalerite Main ore stage/Zn-Pb-(Ag) 32.34 0.18 n.d. n.d. n.d. n.d. n.d. n.d. 65.44 97.96
PBR-241 sphalerite Main ore stage/Zn-Pb-(Ag) 32.37 0.29 n.d. n.d. n.d. n.d. n.d. n.d. 65.60 98.26
PBR-247 sphalerite Main ore stage/Zn-Pb-(Ag) 32.15 0.14 n.d. n.d. n.d. n.d. n.d. n.d. 66.43 98.72
PBR-247 sphalerite Main ore stage/Zn-Pb-(Ag) 32.33 0.54 n.d. n.d. n.d. n.d. n.d. n.d. 66.23 99.10
PBR-247 sphalerite Main ore stage/Zn-Pb-(Ag) 32.93 0.13 n.d. n.d. n.d. n.d. n.d. n.d. 66.71 99.77
PBR-247 sphalerite Main ore stage/Zn-Pb-(Ag) 32.48 0.20 n.d. n.d. n.d. n.d. n.d. n.d. 67.13 99.82
PBR-255 sphalerite Main ore stage/Zn-Pb-(Ag) 32.48 1.06 n.d. n.d. n.d. n.d. n.d. n.d. 65.01 98.55
PBR-255 sphalerite Main ore stage/Zn-Pb-(Ag) 32.99 0.08 n.d. n.d. n.d. n.d. n.d. n.d. 65.92 98.99
Sulfides were analysed using a Cameca SX50 electron microprobe at the University of Lausanne. Instrumental conditions were: accelerating voltage of 12 kV, beam current of 30 nA, and spot size of 10 mm.

81
CHAPTER 2

locally. Similarly, most of the pyrite is believed to
have precipitated coevally with much of the quartz.
Sphalerite shows stoichiometric composition, but in
remarkable contrast to that in the Main ore stage in
the enargite-dominant sub-zone, neither arsenic nor
copper were found to be minor constituents (<0.3 wt.
%; Table 2b.1). No analyses were performed on the
pyrite showing corrosion in contact with bornite.
Tennantite-dominant sub-zone: A similar
transition to that observed between the enargite-
and the bornite-dominant sub-zones is observed
between the latter and the tennantite-dominant sub-
zone. Tennantite-rich parts are better developed than
bornite-rich ones. The tennantite-dominant sub-
zone may occur without an intermediate bornite-
dominant sub-zone, that is, directly rimming the
zone dominated by enargite (Figure 2b.3). Although
generally thin (at most 4 m thick and 6 m wide),
its remarkable continuity (hundreds of meters
surrounding the enargite and/or bornite sub-zones,
even perpendicular to bedding) resulted in this zone
being the most important silver source during the
first three decades of the 20th century. Typical grades
are in the order of 2-4 wt. % Cu, 10-80 oz/t Ag (up
to >100 oz/t), and variable amounts of Zn and Pb,
mainly economically insignificant.
Major constituents of this sub-zone are
tennantite, barite, pyrite, and quartz. Minor phases
include kaolinite, dickite, illite, smectite, enargite,
chalcopyrite, bornite, stromeyerite, and numerous
sulfosalts, only a few of them identified. Indeed,
the tennantite-dominant sub-zone is one of the
two mineralogically most complex of the whole
Colquijirca deposit.
The tennantite-dominant sub-zone contains
one of the three highest reported hypogene silver
grades in the Colquijirca deposit. It is still common to
find the prolongations of the tennantite-rich bodies
exploited early in the 20th century, where average
mined grades fluctuated between 50 and 80 oz/t
Ag (Hutchinson, 1920; Lindgren, 1935; McKinstry;
1936). The particularly high silver contents in the
Colquijirca deposit led many noted geologists during
the 19s, 20s and 30s to study its ores in detail. It is
presumed, based on mineralogy, that some of the
rich ores studied by Orcel and Rivera Plaza (1920),
Lindgren (1935), and McKinstry (1936) may well
correspond to the tennantite-dominant sub-zone.
A selection of classical mineralogical
characterizations of ores presumably belonging to
this sub-zone is presented in the following lines.
Orcel and Rivera Plaza (1920) described
falhore (tennantite)-rich samples in which this
mineral partially replaces pyrite. They describe
skeletal pyrite as textural evidence of this process.
Chalcopyrite inclusions in tennantite were also
noted. These observations were reproduced during
the present study with tennantite replacing pyrite
82
CHAPTER 2
being a common feature of this sub-zone. Possibly
such pyrite is a relict of an earlier hydrothermal stage.
Similarly, chalcopyrite is often the phase intimately
intergrown with tennantite, usually as blebs (Figure
2b.4).
The classical paper by Lindgren (1935, p. 335)
describes tennantite-rich samples. In one of them he
describes a breccia of brown chert containing a little pyrite
in minute grains; it is cemented by barite plates between which
is abundant black tennantite in minute tetrahedrons. This
type of tennantite-bearing sample is the commonest
in this sub-zone (Figure 2b.4). Often, druse- and
geode-like cavities are formed by opening of
fractures. Tennantite in open spaces in, as described
by Lindgren, present as euhedral tetrahedrons, usually
no more than a few millimeters across. Barite in these
samples presents perfectly formed crystals, typically
>1 cm wide, commonly twinned and perfectly
translucent. Tennantite typically overgrows barite
grains, but encapsulation of it and pyrite grains by
barite is also a common feature.
Another sample described by Lindgren
(1935) is very similar to the one just mentioned but
contains abundant chalcopyrite replacing tennantite.
In addition, he recorded stromeyerite and a mineral
that he deduced, from wet chemical analysis, to be
emplectite. This again is a typical association of the
tennantite-dominant sub-zone.
Under the microscope, clusters of apparently
monomineralic tennantite tetrahedrons contain
variable amounts of chalcopyrite, from traces to as
much as 20 volume % of the total copper-bearing
phases (Figure 2b.4). Chalcopyrite is found along
fractures and crystallographic planes. Chalcopyrite
also occurs as open-space fillings or as rims on
tennantite, which, in turn, is replaced by pyrite. Some
bornite has been observed in tennantite; in some
examples containing graticule-textured chalcopyrite
similar texturally to exsolution products (Figure
2b.4).
Stromeyerite has been observed commonly in
this study. In most cases, it replaces tennantite and
chalcopyrite. Another common habit of stromeyerite,
as described by Lindgren (1935), is as rims on these
last two phases, though particularly on chalcopyrite.
The last association is also found in bornite-bearing
samples of the tennantite sub-zone, in which wisps
of chalcopyrite occur within the bornite cleavage.
Considerable amounts of bornite are found
in parts close to the bornite-dominant sub-zone,
forming a sort of transition. The abovementioned
occurrence of chalcopyrite rimming stromeyerite in
a mass of bornite would belong to this category.
Emplectite is the most abundant accessory
sulphosalt in the tennantite-dominant sub-zone. It
mostly occurs as minute inclusions in tennantite or
rimming enargite blebs. Another uncommon mineral
inclusion in tennantite appears to be aikinite, but
its identification is not definitive. Injoque (1988)
described this mineral in a specimen rich in tennantite,
 CHAPTER 2

kaolinite
alunite

sphalerite

bornite

enargite 100 m
A B 100 m

aikinite ?

emplectite
bornite
tennantite
chalcocite

chalcopyrite
50 m
C 50 m D

Native silver
stromeyerite

tennantite

E 50 m F 1 cm

Figure 2b.4: Selected images of the Main ore stage Cu-(Ag) and the Cu-(Ag-Bi) zones in the Colquijirca deposit. A. Reflected
light image showing enargite (from the enargite-dominant sub-zone) in contact with alunite. Note anhedral character of enargite.
B. Reflected light microphotograph showing bornite (from the bornite-dominant sub-zone) replacing sphalerite. Minor kaolinite
filling voids. C. Same sample as in B in which bornite is cut by Late ore stage chalcocite. D. Sample from the tennantite-dominant
sub-zone containing relatively rare Bi-bearing phases. E. Stromeyerite associated to chalcopyrite and partly replaced by chalcocite.
Also chalcopyrite in exsolution-like texture. F. Native silver from the tennantite-dominant sub-zone growing on tennantite.

possibly collected from this sub-zone.
Native silver is relatively common in the
tennantite-dominant sub-zone, where it typically
occurs growing on tennantite and/or barite (Figure
2b.4). Several undefined argentiferous sulfur-bearing
phases are associated with this form of native silver.
This particular sample reported nearly 23 oz/t Ag
in an atomic absorption analysis provided by the
company laboratory.
The extremely high silver contents (>40 oz/t
Ag) in significant parts of the tennantite-dominant
sub-zone are ascribed to associations containing
stromeyerite, native silver, rare Ag-bearing sulfides
and, in places, Ag-rich tennantite.
Barite is the most important associated gangue
mineral in this sub-zone. Besides clusters of perfectly
formed and translucent tabular grains of museum
quality, it occurs in a similar habit to that in the bornite-
rich sub-zone. Minuscule tennantite inclusions in
barite are common. Reversed crystallization between
barite and tennantite is also observed. All these
observations suggest that barite deposited coevally
with tennantite.
Dickite and kaolinite may locally be important.
The style is the same as that observed in the bornite
sub-zone, where they fill all types of cavities including,
most importantly, dissolution vugs and intergranular
spaces. Where dickite and kaolinite are in contact

83

with tennantite, no reaction, , neither corrosion nor
recrystallization, is observed.
Quartz is euhedral and relatively fine-grained
(not >5 mm in size). In contrast to quartz in
the bornite-dominant sub-zone, it is not a major
component of the tennantite-dominant sub-zone,
with perhaps not >5 volume % of the minerals
believed to have precipitated contemporaneously
with tennantite. Evident reversed crystallization
between quartz and tennantite may be distinguished
in most samples. Hence tennantite along the borders
of quartz grains and quartz dispersed within masses
of tennantite are often observed.
Very minor zunyite in this sub-zone is observed.
It is the outermost known occurrence of this
mineral. It occurs as perfect tetrahedra as part of the
silica matrix in parts dominated by quartz. Another
mineral, to date unrecognized, occurs in pseudocubic
crystals associated with quartz and zunyite; it may be
an APS mineral.
Two representative samples from the
tennantite-dominant sub-zone were studied by
electron microprobe (Table 2b.1). No significant
deviation from stoichiometry was found in the
tennantite. Microprobe analyses demonstrate that
the tennantite compositions reported by Lindgren
(1935), based on wet chemical analysis were close
to those obtained by electron microprobe. Minor Sb
substitution for As characterizes the tennantite (<0.2
wt. %). In addition, the microprobe results confirm
Lindgrens (1935) statement that the high contents of
zinc and silver are true components in the tennantite
structure and not derived from mixtures with other
minerals. Zinc values attain 9 wt. %, though Lindgren
reported up to >12 wt. %. Silver has been found to be
as high as 3.2 wt. % in tennantite (Table 2b.1). On the
other hand, in slight disagreement with the analytical
results of Lindgren (1935), significant amounts of
bismuth were found (up to 1.3 wt. %). A few analyses
of stromeyerite and emplectite are available in this
study, with nearly perfect stoichiometry being found
for all analyzed points in both cases (Table 2b.1).
Cu-(Ag-Bi) zone
Immediately surrounding the Cu-(Ag) zone, a
volumetrically small, though more extensive, copper
zone extends for >500 m, from approximately line
740 to 796 (Figure 2b.1). Common ore grades for
at least 3-m-thick mantos are near 0.4 wt. % Cu (up
to 3 wt. %), 0.12 wt. % Bi (up to 1.5 wt. %), 6 wt.
% Zn (up to 15 wt. %), 3 wt. % Pb (up to 8 wt.
%) and 4 oz/t Ag (up to more than 40 oz/t). In
contrast to the Cu-(Ag) zone, the Cu-(Ag-Bi) zone
is mineralogically uniform, with chalcopyrite as the
chief copper phase.
The Cu-(Ag-Bi) zone consists of several
assemblages, including, besides chalcopyrite, pyrite,
dickite, kaolinite, barite, quartz, and siderite. Usually,
84
CHAPTER 2
the Cu-(Ag-Bi) zone contains significant sphalerite-
galena amounts that can constitute ore. However,
observed at the polished section scale, or even in
hand samples, it is recognized that the sphalerite and
galena are not really part of the Cu-(Ag-Bi) zone but
are residual assemblages typical of more external
portions of the system (see comments at the end of
this Chapter).
Pyrite is the main sulfide in the Cu-(Ag-Bi)
zone. It can attain >30 vol. % in entire orebodies.
Much of the pyrite is observed to predate the
chalcopyrite-bearing assemblages. Sphalerite and
galena are associated with such pyrite, suggesting
that a considerable proportion of the pyrite in the
Cu-(Ag-Bi) zone corresponds to assemblages formed
earlier when the mineralization front was farther
south. Tennantite is the second most abundant
copper mineral, although compared with that from
the Cu-(Ag) zone (tennantite-dominant sub-zone)
it is much less important. It typically occur as tiny
patches in chalcopyrite.
Kaolinite and dickite are main phases in the
Cu-(Ag-Bi) zone and can attain 30 volume % of the
rock, typically filling open spaces between quartz,
sulfides, and barite.
Zn-Pb-Cu-(Ag-Bi) zone
The Cu-(Ag-Bi) zone is surrounded by a
relatively widespread Zn-Pb-Cu-(Ag-Bi) zone in
which sphalerite, galena, pyrite, kaolinite, dickite,
siderite, barite, and quartz predominate. Subordinate
quantities of chalcopyrite plus accessory amounts
of Bi- and Ag- bearing sulfide-sulfosalt phases
also occur (Figure 2b.5). This zone is one of the
economically most valuable of the Colquijirca
deposit and is currently mined by its Zn, Pb, and Ag
contents which respectively average 7 %, 3.5 %, and
5 oz/t. Small internal portions of this zone are highly
enriched in silver (40-70 oz/t) and, in copper (up to
more than 3 %). The main observed Ag and Bi hosts
are matildite- and wittichenite-bearing assemblages
(Figure 2b.5). Other Ag- and Bi-bearing minerals are
presumably also present, but they are extremely fine-
grained (<10 m) and seem to represent very minor.
Microprobe analysis of matildite in a single sample
are given in Appendix 2b.2. These Ag-rich portions,
as well as the tennantite-rich sub-zone were mined
underground during the early 20th century during
the Bonanza Epoch (Chapter 0).
Zn-Pb-(Ag) zone
The Zn-Pb-Cu-(Ag-Bi) zone grades outward
to a chalcopyrite-free Zn-Pb-(Ag) zone composed
mainly of sphalerite, galena, pyrite, kaolinite, dickite,
alunite, and, more externally, sphalerite, galena,
pyrite, Zn-bearing siderite, kaolinite, and hematite.
 CHAPTER 2

galena
chalcopyrite

pyrite matildite

sphalerite

A 100 m B 50 m

kaolinite
chalcopyrite

sphalerite sphalerite

C 50 m D

sphalerite
hematite

galena
alunite
sphalerite
50 m 400 m
E F siderite

Figure 2b.5: Selected images from the Main ore stage Zn-Pb-Cu-(Ag-Bi) and Zn-Pb-(Ag) zones. A. Reflected light image
of a typical association in which chalcopyrite and sphalerite replace pyrite. B. Image from polished section of a sample rich in Ag
and Bi. Matildite as inclusions in galena. C. The sphalerite, chalcopyrite, galena, quartz association. D. Nearly massive kaolinite
sample containing euhedral sphalerite grains. E. Reflected light photomicrograph showing the sphalerite-galena-alunite assemblage
in a manto immediately overlying the Cu-(Ag) zone. F. Typical occurrence of an ore sample from the external parts of the Zn-
Pb-(Ag) zone. Hematite accompanied by sphalerite, galena, and siderite.

This zone comprises the largest Zn-Pb-(Ag) resource
in the Colquijirca deposit, which prior to mining may
have exceeded 30 Mt at 6 % Zn, 3 % Pb, and 3.5 oz/t
Ag.
In the inner parts of the Zn-Pb-(Ag) zone,
sphalerite and galena are accompanied by several
mineral assemblages depending on the spatial position
and distance from the Cu-bearing zones. For example,
sphalerite and galena intergrown with alunite and
barite are present immediately overlying the enargite-
dominant sub-zone in the Cu-(Ag) zone (Figures
2b.3 and 2b.5). On the other hand, sphalerite and
galena are accompanied by kaolinite and/or dickite
lateral to the Cu front (along the strike of bedding),
particularly along the main NE-SW ore-fluid flow
direction (Figure 2b.1, Figure 2b.5). In these places,
abundant siderite containing significant amounts of
zinc and manganese occurs in contact with kaolinite
and dickite without evidence for reaction (Figure
2b.5).
The outer parts of the Zn-Pb-(Ag) zone are
mineralogically uniform. Besides sphalerite and
galena, hematite is the characteristic mineral in this
zone (Figure 2b.5). It typically occurs as relatively
coarse-grained specular hematite intergrown with Zn-
bearingg siderite and kaolinite. Other characteristic
but less abundant minerals from the outer portions
of the Zn-Pb-(Ag) zone include magnetite, marcasite,

85
 CHAPTER 2

Early silica-pyrite stage Main ore stage Late ore stage

rutile
mainly octahedral (pyrite I) mainly pentagonal dodecahedral (pyrite II)
pyrite
enargite
quartz
luzonite
sphalerite
galena
siderite
hematite
?
magnetite
alunite (APS phases)
calcopyrite
tennantite
matildite
wittichenite
bornite
native Ag
marcasite
barite
dickite-(kaolinite)
illite-(smectite)
calcosite
covellite

volume %
<1 >1-<5 > 5 - < 10 > 10

Figure 2b.6. Mineral paragenetic sequence in the Colquijirca deposit. Consider simultaneous mineral precipitation of two or
more minerals during a given position in time. E.g., whereas a batch of fluids during the Main ore stage is precipitating enargite
in internal zones of the deposit another batch is at the same time precipitating sphalerite in more external positions.

Late Ore Stage

quartz, and fluorite. Of these the most important,
magnetite, typically replaces the specular hematite
(Figure 2b.5).
The Zn-Pb-(Ag) zone displays gradational
mineralogical variations with increasing distance from
the Cu-bearing zones. An increase in the FeS content
of sphalerite from ~0.1-0.3 wt. % in assemblages
containing kaolinite-dickite-(alunite) to 1- 3 wt. % in
siderite-kaolinite-bearing assemblages is noticeable in
the outer parts of the Zn-Pb-(Ag) zone (Table 2b.1).
Another mineralogical variation is the prevalence of
galena over sphalerite in the external potions of the
Zn-Pb-(Ag). Some of these galena-rich portions are
highly argentiferous, with Ag contents as high as 30
oz/t in some thin mantos (up to 1 m thick).
An outermost Zn-bearing zone surrounds the
Zn-Pb-(Ag) ores but in contrast to the other Zn zones,
it is virtually devoid of sulfides. It basically consists
of Zn-bearing carbonates, including preponderantly
siderite and rhodochrosite, which may form mantos
up to 3 m thick with grades in excess of 5 % Zn.
Ahfeld (1932) was the first to recognize
chalcocite to be of hypogene origin. He described it
replacing enargite in the pyritic manto, very likely
in the enargite-dominant sub-zone. But chalcocite,
as defined in this study, is always associated to other
minor copper phases that systematically cut the
components of the Main ore stage throughout the Cu-
(Ag) zone. Other distinct associations also crosscut
the mineral associations of the Main Ore Stage in
the outer Zn-Pb-bearing zones. This common late
timing invites collective assignment of these late
mineral associations to a Late ore stage.
Chalcocite-(covellite-digenite-chalcopyrite) are
found more prominently in the bornite-dominant
sub-zone. There, they form thin veinlets <20 m wide
cutting bornite (Figure 2b.5). In a second form, these
phases coat dissolution vugs in which they typically
form entire rims. In both cases, chalcocite constitutes
>50 volume % of the sulfides. Covellite comprises
between 10 and 40%, with the remaining fraction
being digenite and, subordinately, chalcopyrite. In a
few cases, decimetric pockets of massive chalcocite-
(digenite-covellite-chalcopyrite) are noted.

86

Interpretation of the observed patterns of
relative ages of mineral associations in the
Smelter and Colquijirca deposits
Analysis of crosscutting relationships between
mineral assemblages and associations in the Smelter
and Colquijirca deposits suggests progressive advance
of the Main ore stage sulfide-rich mineralization front
with time. An indication of the magnitude of the
advance is recorded in the central part of the Smelter
deposit where several bodies of sphalerite-galena-
siderite-kaolinite float within the enargite-bearing
zones. Observed in detail, the sphalerite bodies
are cut and partly replaced by the enargite-bearing
assemblages. Also at Smelter, at the polished section
scale, numerous samples display residual sphalerite
and hematite surviving as inclusions in enargite-
bearing assemblages. These observations show that
the inner Cu zone encroached on the Zn-Pb zone.
By the time the residual sphalerite-bearing zones had
formed, the outer limit of the Cu mineralization was
restricted to parts as near as 1 km to the Marcapunta
volcanic complex, that is ~1.5 km south of the final
Cu front exposed in the Principal pit at Colquijirca.
A similar explanation in terms of progressive
advance of the mineralization front is also valid for
the Colquijirca deposit where numerous sphalerite-
galena bodies float within the Cu-(Ag) and Cu-(Ag-
Bi) zones. Detailed mapping shows that these bodies
predated deposition of Cu-bearing sulfides and that
they represent former external zones of the system
now largely overtaken and replaced by the Cu zones
(Figure 2b.3). This process of progressive advance
of the mineralization front is described in detail for
other localities, notably for the large veins of the
Butte deposit (e.g. Sales and Meyer, 1969; Hemley
and Hunt, 1992).
Late reversals in the temporal sequence of
mineral assemblages are observed at both Smelter
and Colquijirca, where veinlets composed largely
of chalcocite, tennantite or sphalerite replace the
enargite-bearing assemblages. At Marcapunta Oeste,
chalcocite replacing enargite in strongly fault-
controlled bodies is interpreted in terms of retreat
of the mineralization front, possibly during waning
of hydrothermal activity when meteoric water input
was higher.
REFERENCES
Ahlfeld, F., 1932, Die Silberlagersttte Colquijirca,
Per. Zeitschrift Praktischer Geologie, 40, p. 81-87.
Angeles, C., 1993, Geologa de Colquijirca y alrede-
dores. Informe privado Sociedad Minera El Brocal S.A.A.,
39 p.
Bendez, R., 1997, Caractersticas geolgicas miner-
CHAPTER 2
algicas y geoqumicas de los yacimientos de Zn-Pb (Ag)
de San Gregorio y Colquijirca emplazados en unidades
sedimentarias en los bordes del sistema epitermal de alta
sulfuracin de Marcapunta. Tesis Ingeniero, Universidad
Nacional de Ingeniera, Lima, 60 p.
Fowler, T.J., and Winsor, C.N., 1997, Characteristics
and occurrence of bedding-parallel slip surfaces and lami-
nated veins in chevron folds from the Bendigo-Castle-
maine goldfields: implications for flexural slip folding.
Journal of Structural Geology, 19, 799-815.
Hemley, J.J., and Hunt, J.P., 1992, Hydrothermal ore-
forming processes in the light of studies in rock-buffered
systems; II, Some general geologic applications. Econom-
ic Geology, 87, p. 23-43.
Hutchinson W.S., 1920, The Fernandini properties,
province of Pasco, Per: Production costs and profits,
Colquijirca silver mine, Huaraucaca metallurgical plant, La
Curea copper mine, San Gregorio bismuth mine. Report
for the Fernandini Properties, 70 p.
Injoque, J., 1988, Estudio petromineragrfico de 52
secciones de la mina Colquijirca, Per. Informe privado
Sociedad Minera El Brocal S.A.A., 90 p.
Lindgren, W., 1935, The silver mine of Colquijirca,
Per. Economic Geology, 30, p. 331-346.
McKinstry, H.E., 1929, Interpretation of concentric
textures at Colquijirca, Per. American Mineralogist, 14,
p. 431-433.
McKinstry, H.E., 1936, Geology of the silver deposit
at Colquijirca, Per. Economic Geology, 31, p. 619-635.
Meyer, C., and Hemley, J.J., 1967, Wall-rock alteration,
in Barnes, H.L., ed., Geochemistry of hydrothermal ore
deposits, 1st ed., New York, Holt, Rinehart Winston, p.
166-235.
Orcel, J., and Rivera Plaza, G., 1920, Etude mi-
croscopique de quelques minerais mtalliques du Prou.
Bulletin Societ Franaise de Minralogie, 52, p. 91-107.
Sales, R.H., and Meyer, C., 1949, Results from prelimi-
nary studies of vein formation at Butte, Montana. Eco-
nomic Geology, 44, p. 465-484.
87
88
Appendix 2b.1. Additional microprobe results obtained for some common phases from the Colquijirca deposit.
sphalerite
S (wt%) Mn (wt%) Fe (wt%) Cu (wt%) Zn (wt%) As (wt%) Ag (wt%) Cd (wt%) Sn (wt%) Sb (wt%) Pb (wt%) Bi (wt%) sum
PBR-311 32.32 0.02 0.84 0.65 64.98 0.02 0.03 0.16 0.00 0.01 0.00 0.00 99.03
PBR-311 32.55 0.00 0.57 0.40 65.69 0.01 0.01 0.13 0.02 0.05 0.00 0.09 99.52
PBR-311 32.85 0.00 0.93 0.30 65.80 0.02 0.08 0.18 0.01 0.00 0.00 0.00 100.18
PBR-311 32.82 0.02 0.40 0.10 67.20 0.00 0.14 0.21 0.04 0.04 0.00 0.00 100.97
PBR-312 32.74 0.00 0.15 0.03 66.85 0.00 0.00 0.02 0.01 0.01 0.00 0.00 99.83
PBR-312 32.78 0.00 0.11 0.01 67.04 0.01 0.00 0.04 0.04 0.04 0.00 0.00 100.06
PBR-312 32.24 0.00 0.80 0.14 65.77 0.03 0.05 0.00 0.03 0.00 0.00 0.05 99.11
PBR-116 32.78 0.00 0.14 0.00 66.99 0.00 0.00 0.00 0.08 0.00 0.00 0.00 99.99
PBR-116 32.83 0.00 0.27 0.01 66.14 0.00 0.02 0.00 0.00 0.00 0.00 0.00 99.28
PBR-116 32.89 0.06 0.53 0.03 66.03 0.01 0.06 0.00 0.00 0.02 0.00 0.13 99.76
PBR-116 32.91 0.60 0.22 0.01 66.67 0.00 0.07 0.00 0.04 0.04 0.00 0.00 100.55
PBR-116 32.68 0.00 0.64 0.00 66.61 0.00 0.00 0.02 0.01 0.00 0.00 0.20 100.14
PBR-116 32.89 0.00 0.60 0.01 66.53 0.00 0.01 n.a. 0.00 0.00 0.00 0.05 100.10
PBR-61b 32.45 0.00 0.43 0.09 66.38 0.02 0.04 n.a. 0.00 0.00 0.00 0.00 99.40
PBR-61b 32.52 0.01 0.08 0.01 67.22 0.00 0.05 n.a. 0.05 0.00 0.00 0.00 99.94
PBR-61b 32.50 0.04 0.06 0.08 67.35 0.01 0.00 n.a. 0.04 0.03 0.00 0.00 100.12
PBR-61b 32.61 0.00 0.16 0.10 67.86 0.01 0.04 n.a. 0.02 0.05 0.00 0.00 100.84
PBR-61b 33.04 0.01 0.05 0.03 67.28 0.00 0.02 n.a. 0.08 0.00 0.00 0.00 100.51
PBR-118 32.44 0.00 0.62 0.00 66.94 0.01 0.09 n.a. 0.00 0.04 0.00 0.06 100.19
PBR-118 32.59 0.02 0.43 0.00 67.25 0.00 0.06 n.a. 0.06 0.00 0.00 0.00 100.41
PBR-118 33.03 0.00 0.49 0.00 66.57 0.00 0.00 n.a. 0.00 0.01 0.00 0.04 100.15
PBR-118 32.60 0.00 0.28 0.07 66.91 0.00 0.00 n.a. 0.01 0.00 0.00 0.00 99.88
PBR-121 32.26 0.03 0.04 0.04 65.29 0.00 0.00 n.a. 0.00 0.00 0.00 0.00 97.67
PBR-108 33.01 0.00 0.24 0.00 67.33 0.00 0.01 n.a. 0.04 0.00 0.00 0.06 100.68
PBR-108 32.89 0.00 0.43 0.02 66.31 0.00 0.00 n.a. 0.00 0.06 0.00 0.00 99.72
PBR-108 32.84 0.01 0.48 0.02 66.86 0.00 0.00 n.a. 0.00 0.02 0.00 0.10 100.33
PBR-108 32.76 0.00 0.13 0.03 67.87 0.03 0.02 n.a. 0.05 0.04 0.00 0.00 100.93
PBR-108 32.50 0.02 0.46 0.09 67.09 0.00 0.05 n.a. 0.00 0.00 0.00 0.08 100.29
PBR-326 32.81 0.02 0.00 0.52 65.31 0.01 0.00 n.a. 0.03 0.00 0.00 0.00 98.70
PBR-326 32.09 0.00 0.11 1.88 62.37 0.00 1.28 n.a. 0.10 0.03 0.00 0.04 97.90
PBR-399 32.91 0.02 0.61 0.74 66.23 0.00 0.00 n.a. 0.03 0.05 0.00 0.00 100.59
CHAPTER 2
 Appendix 2b.1. (Cont.) Additional microprobe results obtained for some common phases from the Colquijirca deposit.
S (wt%) Mn (wt%) Fe (wt%) Cu (wt%) Zn (wt%) As (wt%) Ag (wt%) Cd (wt%) Sn (wt%) Sb (wt%) Pb (wt%) Bi (wt%) sum
PBR-399 32.91 0.00 0.62 0.66 66.63 0.00 0.00 n.a. 0.01 0.03 0.00 0.00 100.86
PBR-399 32.58 0.00 0.29 0.45 66.28 0.01 0.00 n.a. 0.01 0.00 0.00 0.00 99.62
PBR-399 32.85 0.02 0.22 0.42 66.22 0.03 0.00 n.a. 0.03 0.01 0.00 0.00 99.79
PBR-399a 32.74 0.00 0.26 0.39 65.43 0.01 0.05 n.a. 0.01 0.03 0.05 0.00 98.97
PBR-399a 32.83 0.00 0.77 0.85 66.19 0.01 0.00 n.a. 0.05 0.00 0.00 0.10 100.80
PBR-399a 32.92 0.00 0.27 0.46 66.44 0.01 0.00 n.a. 0.06 0.00 0.00 0.00 100.16
PBR-400 32.73 0.02 0.05 0.09 66.03 0.00 0.01 n.a. 0.03 0.03 0.00 0.00 98.99
PBR-400 32.73 0.00 0.02 0.15 66.74 0.00 0.01 n.a. 0.00 0.00 0.00 0.00 99.63
PBR-400 32.82 0.03 0.10 0.16 67.31 0.01 0.00 n.a. 0.01 0.00 0.00 0.03 100.45
PBR-400 32.22 0.01 0.04 0.13 66.03 0.00 0.00 n.a. 0.03 0.00 0.00 0.00 98.46
PBR-400 32.66 0.00 0.08 0.09 66.39 0.00 0.01 n.a. 0.05 0.05 0.00 0.08 99.39

galena
PBR-107 13.19 0.00 0.07 0.00 0.08 0.01 0.00 0.00 0.02 0.01 87.86 0.00 101.25
PBR-107 13.34 0.01 0.04 0.07 0.44 0.00 0.00 0.00 0.02 0.02 87.27 0.00 101.21
PBR-108 13.12 0.02 0.03 0.00 0.19 0.02 0.00 n.a. 0.06 0.01 87.62 0.00 101.07
PBR-108 13.22 0.00 0.03 0.00 0.00 0.01 0.00 n.a. 0.02 0.00 87.03 0.00 100.32
PBR-108 13.19 0.02 0.05 0.01 0.06 0.00 0.00 n.a. 0.05 0.05 86.22 0.00 99.66
PBR-108 13.15 0.00 0.05 0.07 0.00 0.01 0.00 n.a. 0.01 0.02 87.05 0.00 100.35
PBR-108 13.28 0.04 0.07 0.00 0.00 0.00 0.00 n.a. 0.00 0.05 87.29 0.00 100.73
PBR-399 13.14 0.00 0.08 0.19 0.64 0.00 0.16 n.a. 0.00 0.00 85.34 0.00 99.55
PBR-399 13.34 0.03 0.03 0.21 0.72 0.01 0.17 n.a. 0.07 0.00 86.53 0.00 101.11
PBR-399 13.53 0.00 0.00 0.34 0.04 0.00 2.43 n.a. 0.00 0.00 83.61 0.00 99.94
PBR-399 13.53 0.05 0.03 0.04 0.00 0.00 1.64 n.a. 0.00 0.00 84.23 0.00 99.51
PBR-399 13.50 0.02 0.00 0.10 0.00 0.00 1.34 n.a. 0.04 0.00 83.67 0.00 98.67
PBR-399 13.54 0.00 0.04 0.33 0.06 0.00 2.25 n.a. 0.00 0.00 82.67 0.00 98.90
PBR-399 13.39 0.00 0.06 0.27 0.00 0.00 1.33 n.a. 0.12 0.05 84.07 0.00 99.28
PBR-61b 13.07 0.00 0.05 0.24 0.28 0.01 0.07 n.a. 0.02 0.00 86.81 0.00 100.55
PBR-61b 13.24 0.00 0.04 0.04 0.07 0.03 0.00 n.a. 0.03 0.00 86.99 0.00 100.44
PBR-61b 13.29 0.00 0.43 0.96 0.09 0.01 0.03 n.a. 0.00 0.04 85.72 0.00 100.58
PBR-61b 13.30 0.00 0.00 0.16 0.91 0.00 0.00 n.a. 0.00 0.00 86.85 0.00 101.22
PBR-61b 13.40 0.03 0.03 0.00 0.08 0.02 0.00 n.a. 0.07 0.02 86.08 0.00 99.73
PBR-326 13.21 0.00 0.05 0.04 0.00 0.00 0.00 n.a. 0.02 0.00 86.78 0.00 100.11

89
CHAPTER 2
90
Appendix 2b.1. (Cont.) Additional microprobe results obtained for some common phases from the Colquijirca deposit.
S (wt%) Mn (wt%) Fe (wt%) Cu (wt%) Zn (wt%) As (wt%) Ag (wt%) Cd (wt%) Sn (wt%) Sb (wt%) Pb (wt%) Bi (wt%) sum
PBR-326 13.08 0.00 0.02 0.03 0.04 0.00 0.00 n.a. 0.03 0.00 86.23 0.00 99.42
PBR-326 13.23 0.00 0.07 0.05 0.00 0.02 0.00 n.a. 0.00 0.07 86.51 0.00 99.96
PBR-326 13.28 0.02 0.01 0.08 0.25 0.00 0.00 n.a. 0.01 0.00 86.83 0.00 100.48
PBR-399a 13.16 0.03 0.05 0.09 0.31 0.00 0.00 n.a. 0.01 0.00 86.21 0.00 99.86
PBR-399a 13.32 0.00 0.05 0.03 0.06 0.01 0.00 n.a. 0.03 0.00 87.66 0.00 101.16
PBR-399a 13.41 0.01 0.06 0.10 0.08 0.00 0.24 n.a. 0.05 0.00 86.51 0.00 100.45
PBR-399a 13.25 0.02 0.30 0.52 0.36 0.00 0.32 n.a. 0.00 0.00 84.68 0.00 99.45
PBR-399a 13.30 0.04 0.18 0.09 0.00 0.04 0.00 n.a. 0.01 0.00 85.45 0.00 99.12
PBR-399a 13.57 0.03 0.07 0.43 0.02 0.00 2.06 n.a. 0.00 0.00 82.30 0.00 98.47
PBR-400 13.39 0.00 0.11 0.09 0.10 0.00 1.93 n.a. 0.03 0.00 81.28 0.00 96.95
PBR-400 13.37 0.02 0.07 0.42 0.58 0.00 2.36 n.a. 0.00 0.00 82.18 0.00 98.00
PBR-400 13.43 0.00 0.05 0.30 0.02 0.00 2.14 n.a. 0.04 0.02 82.68 0.00 98.67
PBR-400 13.35 0.00 0.03 0.09 0.41 0.00 1.50 n.a. 0.00 0.00 82.61 0.00 97.99
Pyrite
PBR-107 53.95 0.00 46.69 0.08 0.02 0.02 0.00 0.00 0.03 0.02 0.00 0.00 100.82
PBR-107 53.37 0.00 46.35 0.00 0.86 0.05 0.01 0.03 0.02 0.01 0.00 0.06 100.76
PBR-107 53.59 0.00 46.59 0.02 0.84 0.01 0.01 0.02 0.00 0.00 0.00 0.00 101.09
PBR-107 53.46 0.04 46.32 0.00 0.99 0.06 0.00 0.00 0.09 0.00 0.00 0.00 100.97
PBR-108 52.88 0.00 46.35 0.08 0.50 0.04 0.15 0.00 0.06 0.00 0.00 0.07 100.13
PBR-108 53.06 0.13 46.55 0.27 0.11 0.03 0.18 0.00 0.00 0.00 0.00 0.00 100.32
PBR-108 53.18 0.01 46.78 0.12 0.06 0.00 0.11 0.00 0.00 0.04 0.00 0.04 100.32
PBR-108 53.04 0.02 45.99 0.00 0.32 0.29 0.04 0.09 0.02 0.00 0.00 0.00 99.82
PBR-108 32.89 0.00 0.08 0.33 66.87 0.02 0.14 n.a. 0.00 0.00 0.00 0.00 100.32
PBR-108 53.06 0.41 46.59 0.06 0.31 0.04 0.00 n.a. 0.00 0.01 0.00 0.00 100.48
PBR-108 53.60 0.00 47.09 0.05 0.14 0.03 0.05 n.a. 0.00 0.03 0.00 0.00 101.00
PBR-108 53.39 0.00 47.18 0.00 0.05 0.01 0.01 n.a. 0.07 0.00 0.00 0.03 100.75
PBR-116 53.73 0.00 46.48 0.02 0.51 0.02 0.00 n.a. 0.00 0.00 0.00 0.00 100.77
PBR-116 53.41 0.02 46.67 0.00 0.53 0.05 0.00 n.a. 0.01 0.07 0.00 0.00 100.76
PBR-61b 52.83 0.02 46.62 0.04 0.26 0.06 0.00 n.a. 0.00 0.00 0.00 0.02 99.85
PBR-61b 53.09 0.00 46.73 0.00 0.08 0.03 0.04 n.a. 0.07 0.01 0.00 0.00 100.04
PBR-61b 53.19 0.00 46.96 0.00 0.00 0.02 0.03 n.a. 0.03 0.00 0.00 0.00 100.23
CHAPTER 2

PBR-61b 53.33 0.00 46.58 0.02 0.37 0.05 0.00 n.a. 0.02 0.00 0.00 0.00 100.37
 Appendix 2b.1. (Cont.) Additional microprobe results obtained for some common phases from the Colquijirca deposit.
S (wt%) Mn (wt%) Fe (wt%) Cu (wt%) Zn (wt%) As (wt%) Ag (wt%) Cd (wt%) Sn (wt%) Sb (wt%) Pb (wt%) Bi (wt%) sum
PBR-118 53.63 0.00 46.70 0.01 0.65 0.04 0.00 n.a. 0.00 0.00 0.00 0.00 101.03
PBR-118 53.06 0.00 46.73 0.00 0.60 0.22 0.02 n.a. 0.05 0.00 0.00 0.00 100.68
PBR-118 53.67 0.02 47.00 0.00 0.58 0.08 0.05 n.a. 0.00 0.00 0.00 0.00 101.40
PBR-118 53.58 0.03 46.59 0.06 0.84 0.02 0.00 n.a. 0.02 0.05 0.00 0.01 101.21
PBR-121 53.89 0.00 46.80 0.03 0.91 0.03 0.09 n.a. 0.03 0.00 0.00 0.00 101.79
PBR-121 53.70 0.01 46.68 0.01 0.87 0.04 0.04 n.a. 0.07 0.00 0.00 0.00 101.42
PBR-121 53.65 0.02 47.11 0.00 0.39 0.04 0.00 n.a. 0.04 0.00 0.00 0.00 101.25
PBR-399a 53.46 0.02 46.30 0.22 0.00 0.04 0.02 n.a. 0.11 0.04 0.00 0.02 100.22
PBR-399a 53.02 0.03 45.80 0.20 0.21 0.02 0.12 n.a. 0.07 0.01 0.00 0.16 99.63
PBR-399a 53.58 0.03 46.52 0.04 0.19 0.01 0.03 n.a. 0.05 0.00 0.00 0.03 100.47
PBR-399a 52.86 0.00 45.65 1.00 0.04 0.05 0.00 n.a. 0.04 0.00 0.00 0.00 99.65
PBR-399a 53.25 0.00 46.93 0.04 0.08 0.04 0.02 n.a. 0.05 0.02 0.00 0.02 100.44
PBR-399a 53.07 0.01 46.16 0.00 0.03 0.00 0.01 n.a. 0.01 0.00 0.00 0.02 99.32
PBR-400 52.85 0.02 46.99 0.14 0.06 0.04 0.06 n.a. 0.04 0.00 0.00 0.07 100.28
PBR-400 52.91 0.01 46.39 0.57 0.00 0.05 0.05 n.a. 0.02 0.06 0.00 0.00 100.07
PBR-400 52.72 0.02 45.85 0.00 0.04 0.05 0.00 n.a. 0.00 0.00 0.00 0.00 98.68
PBR-400 52.98 0.03 45.09 0.15 0.02 0.02 0.09 n.a. 0.02 0.02 0.00 0.00 98.42
PBR-400 52.81 0.02 46.30 0.00 0.51 0.03 0.06 n.a. 0.05 0.00 0.00 0.00 99.76

matildite

S (wt%) Fe (wt%) Cu (wt%) Zn (wt%) As (wt%) Ag (wt%) Sb (wt%) Bi (wt%) Pb (wt%) sum
PBR-399a 16.59 0.08 1.01 0.33 0.00 27.88 0.00 53.80 0.00 99.70
PBR-399a 16.63 0.21 0.72 0.66 0.00 27.54 0.00 53.09 0.18 99.05
PBR-399a 16.17 0.08 0.27 0.13 0.00 27.72 0.00 55.06 0.00 99.46
PBR-399a 16.18 0.05 0.22 0.16 0.00 27.10 0.00 56.08 0.00 99.79
PBR-399a 16.50 0.05 0.24 0.04 0.00 27.67 0.04 54.86 0.00 99.40
PBR-399a 16.76 0.05 0.44 0.20 0.00 27.83 0.00 54.62 0.00 99.89
PBR-399a 16.40 0.03 0.23 0.04 0.00 27.39 0.00 55.00 0.00 99.09

phases were analysed using a Cameca SX50 electron microprobe at the University of Lausanne. Instrumental conditions were: accelerating voltage of 15 kV,
beam current of 25 nA, and spot size of 10 mm.

91
CHAPTER 2
92
Appendix 2b.2. Main minerals from the Main ore stage along the Smelter-Colquijirca corridor according to the metal zone as described in the text.
Cu-(Au-Ag) Cu-(Ag-Sn-Bi) Cu-(Ag-Bi) Cu-(Ag) Cu-(Ag-Bi) Zn-Pb-Cu-(Ag-Bi) Zn-Pb-(Ag)
enargite (a) enargite (a) enargite (a) enargite (a) chalcopyrite (a) sphalerite (a) sphalerite (a)
pyrite (m to a) pyrite (m to a) pyrite (m to a) pyrite (m to a) pyrite (a) galena (a) galena (a)
luzonite (m to t) luzonite (m to t) luzonite (m to t) luzonite (m to t) tennantite (m to t) chalcopyrite (a) pyrite (a)
ferberite (m to t) colusite (m to t) bismuthinite (m to t) tennantite (a) quartz (a) pyrite (a) quartz (a)
tennantite (t) ferberite (m to t) tennantite (t) bornite (a) kaolinite (m to t) tennantite (m to t) kaolinite (m to t)
bismuthinite (m
goldfieldite (m to t) to t) chalcopyrite (t) stromeyerite (a) dickite (m to t) matildite (m to t) siderite (a to m)
native Au (t) stannoidite (t) quartz (a) emplectite (m to t) illite (t) wittichenite (m to t) magnetite (t)
native Te (t) tennantite (t) alunite (a) native Ag (m to t) smectite (t) quartz (a) hematite (a to t)
Au-Ag-tellurides (t) goldfieldite (t) zunyite (a to m) quartz (a) barite (a to m) kaolinite (a to t) zincian siderite (a)
chalcopyrite (t) native Au (t) kaolinite (m to t) alunite (a) siderite (a to m) dickite (a to t) marcasite (m to t)
quartz (a) native Te (t) dickite (m to t) zunyite (t) barite (a to m) fluorite (m to t)
alunite (a) Au-Ag-tellurides (t) illite (t) kaolinite (m to t) siderite (a to m) muscovite (t)
zunyite (a to m) chalcopyrite (t) smectite (t) dickite (m to t) illite (m to t) illite (t)
kaolinite (m to t) quartz (a) muscovite (t) illite (t) smectite (m to t) smectite (t)
dickite (m to t) alunite (a) smectite (t)
illite (t) zunyite (a to m) barite (a to m)
smectite (t) kaolinite (m to t)
dickite (m to t)
muscovite (t)
illite (t)
smectite (t)

a. abundant (>4 vol. %)

m. minor (1-4 vol. %)
t. trace (< 1 vol. %)
CHAPTER 2

2c. The central sector. Disseminated Au-(Ag)
mineralization in the Oro Marcapunta prospect
Disseminated Au-(Ag) mineralization at the
Oro Marcapunta prospect consists of veinlets,
patches, and disseminations of oxide minerals hosted
exclusively by phreatomagmatic breccias, dome and
lava flows, and pyroclastic rocks of the central sector
of the Marcapunta diatreme-dome complex.
In contrast to the sulfide-rich polymetallic
orebodies of the Smelter and Colquijirca deposits,
this occurrence is poorly known. Only a few holes
were drilled during the 1970s and in the last few
years during exploration for porphyry copper and
enargite-rich bodies. No further exploration has been
conducted because of the existence of a pre-Inca
archeological reserve much of the area in which the
Oro Marcapunta Au-(Ag) mineralization occurs.
Host rock
The Marcapunta volcanic complex, as
introduced in Chapter 1, is an explosive-effusive
center with development of a large central diatreme
system and multiple stages of dome emplacement
and associated lavas and pyroclastic deposits. The
overall internal construct of the volcanic complex
is as yet poorly defined. Only parts of the northern
and western flanking portions of the complex have
been relatively well defined three dimensionally.
Conversely, the central portion, where most of the
Au-(Ag) mineralization occurs, remains ill-defined.
The central parts of the Marcapunta complex
displays two main units: (i) the most important in
terms of volume, is dominated by dacitic lava domes
and flow rocks, and (ii) a large body of polymictic
breccias below the top parts of Marcapunta hill
which following Noble (1992) and Sillitoe (2000),
among others, represents the upper fingers of a major
diatreme vent at depth. A cross section showing these
two units is constructed on the basis of available data
(Barba, 1992; Vidal, 1992; Vidal and Ligarda, 2004;
Sarmiento, 2004; and own data) as Figure 2c.1.
Breccias
Most of the economically interesting Au-(Ag)
intercepts occur within the breccias. Several types of
breccias recognized in the inner parts of the central
portion of the Marcapunta complex in drill holes
SD-11 and SD-MS-2 (Figure 2c.1). The breccias
CHAPTER 2
generally consist of monomictic and polymictic
angular clasts up to several decimeters in size in a
fine-grained matrix composed of milled dacitic rock
and juvenile material. These breccias are interpreted
phreatomagmatic in origin.
The most prominent interval of breccias was
intersected by SD-11 (Figure 2c.1), which cuts nearly
100 vertical meters of matrix-supported angular
centimetric clasts. Although strongly leached, it is still
possible to recognize the original lithology of most
of its clasts, which include, besides volcanic material,
laminated limestone, milky quartz, and phyllite
from the Pocobamba Formation, Mitu Group, and
Excelsior Group, respectively. Such varied lithologies
suggest a major phreatomagmatic event originated at
least 1km deep, which is coherent with the idea that
a relatively large diatreme conduit exists in the inner
part of the Marcapunta volcanic complex (e.g., Noble,
1992). The SD-11 hole left opened the continuity of
the breccia body at 450 m depth, but considering
other holes located in the surroundings (e.g., Brocal-
524), the diatreme conduit would have a ramified
flared geometry gaining continuity downward and
from which only its upper flares were encountered
(Figure 2c.1).
Rarer intervals consisting of other type of
breccias of limited vertical extension (less than
10 meters) host minor Au-(Ag) intercepts. These
breccias contain monomictic (volcanic) fragments in
a sandy matrix. They apparently lack primitive igneous
fragments. These have likely a phreatic origin. Also
typical of this inner portion of the central Marcapunta
complex is a swarm of thin dikes consisting of
massive fine-grained tuffaceous material, in part
mineralized (see tuffisite in Chapter 1b).
Subordinate pebble dikes occur also in the
central portions of Marcapunta. They are composed
of rounded fragments in a rock flour matrix.
Fragments consists of dacite domes, and basement
rocks including Mitu Group sandstones. Some of
these fragments can contain geodes of quartz. The
dikes, usually less than 2 m thick, are oriented mainly
in NS and NW directions. The pebble dikes crop
out mainly in the southern sector of the Marcapunta
volcanic complex (Figure 2c.3). They cut the lava-
domes facies and the Mesozoic and Cenozoic
carbonate rocks (Chambar and Pocobamba
formations).
93
 CHAPTER 2

Eocene Pocobamba Formation

Au-(Ag) disseminated mineralization

vuggy silica and quartz-alunite zones
B

containing Au-(Ag)-bearing veinlets

enargite ores at Marcapunta Oeste
carbonate rocks.

Cordilleran mineralization
CM4-444
68
76

76

SD-11

phreatomagmatic breccias
84
84
55

36

lava-domes
A
Marcapunta complex
A

of Figure 2c.2

400 m
B
N

area

Figure 2c.1 Block diagram illustrating the internal configuration of the disseminated Au-(Ag)bodies and related alteration zones
at Oro Marcapunta. The diagram was elaborated on the basis of surface geological mapping carried out by Brocal-Buenaventura
geological staff and data from drill holes SD-11, CM4-444, and CM3-444.

94

Dome and lava flows
These units, as well as their general chemistry,
are described in Chapter 1b. The majority of the
exposures of the Marcapunta volcanic complex
comprise lava flows and lava-dome facies (according
to the nomenclature of Self, 1982). Again, despite
the fact that the rocks are strongly altered, it is
still possible to recognize many of the original
characteristics of these facies. Macroscopically,
virtually all these rocks are homogeneously
porphyritic in texture (Figure 1b.2). As shown below,
the chemistry of the scarce unaltered rocks indicates
an exclusively dacitic composition. However,
comparatively higher abundances of relict resorbed
quartz in some rocks indicates that besides dacite,
rhyodacitic or less probably rhyolitic rocks may have
been originally present (Yacila, pers. comm., 2002).
These less common rocks were mainly observed
within the volcanic units of the central diatreme
neck. Mineralogically, all the unaltered dacitic rocks
consist of blocky sanidine crystals, as large as 12 cm
(Figure 1b.2), besides smaller plagioclase (probably
andesine; Harvey, 1936 in McKinstry, 1936) and
resorbed quartz (Figure 1b.2). Also distinctive are
euhedral biotite, hornblende and clinopyroxene. The
aphanitic matrix is mainly composed of orthoclase,
quartz and minor biotite. Accessory minerals include
apatite, zircon and magnetite. Harvey (1936) also
reported rutile.
Lava flows dominate over lava domes (Figure
1b.2) at surface. Flow banding (Figure 1b.2) is thus
much more common than blocky spherulitic lava
typical of the central portions of domes (Self, 1982).
Drilling information indicates that lava flows are
present throughout the volcanic pile, that is from
the erosional discordance over the Eocene Calera
sequence up to the current top of the Marcapunta
complex. The flows overlie either lapilli or block
and ash deposits. Recognized thicknesses of the lava
flows attain 100 m. Based on well-preserved features,
such as flow banding and spherulitic textures, lava
dome diameters vary from a few tens of meters to
as large as 500 m east of Smelter, although most of
those recognized are generally <50 m.
Spatial configuration of the orebodies and
controls on mineralization
The central portion of the Marcapunta Complex
shows numerous small outcrops of strongly leached
porous rock known as vuggy silica. It occurs in
high-sulfidation epithermal deposits as the result of
nearly total removal of the major constituents except
silica under the influence of strongly acidic and
oxidizing solutions (e.g, Stoffregen, 1987; Hedenquist,
1987). Vuggy silica crops out as irregular elongate
structures in the form of ribs (Figures 2c.1, 2c.2).
Tabular units, which pinch and swell along strike, are
CHAPTER 2
also observed. The largest continuous structure at
surface does not exceed 150 m long and 20 m wide.
The elongate character of the vuggy silica ledges is
clearly a response to faulting and fracturing, which
follow east-west and, subordinate, north-west and
north-east directions (Figure 2c.2).
The highest Au-(Ag) concentrations (up to 10
ppm Au) occur in vuggy silica containing swarms of
largely oxidized sulfide veinlets. At Oro Marcapunta,
vuggy silica free of veinlets, but containing minor
oxide and/or sulfide disseminations, reports
anomalous gold, typically between 50 and 200 ppb.
It is not clear, however, whether such disseminations
were deposited from the same fluids that formed the
vuggy silica or during later ore stages. In any case,
the available evidence indicates that vuggy silica
containing veinlets host most of the gold. In several
areas, gold-bearing veinlets extend beyond the limits
of the vuggy silica ledges, reaching peripheral zones
dominated by alunite-quartz-bearing assemblages,
but it is estimated that gold contents in such cases
are only minor.
Au-(Ag)-bearing veinlets sets structurally
mimic the fault-fracture patterns that controlled vuggy
silica formation (i.e., east-west and less commonly
north-east and north-east directions). Mapping by
Barba (1992), Vidal (1992) and, more recently, by the
Brocal and Buenaventura staff (2004) clearly show
this structural control.
At surface the Au-(Ag) veinlet sets and spatially
associated vuggy silica are generally emplaced in both
lava domes and flows, as well as locally in breccias,
without any significant geometric differences induced
by the lithology. However, locally, it may be observed
that the vuggy silica bodies extend perpendicular
to the fracture, considerably further in the breccias
than in the lava domes and flows. The geometry is
thus ultimately controlled by the fracture pattern and
permeable-dependent lithological variations as best
exemplified by core from hole SD-11.
In contrast to surface observations, SD-11
intercepted >100 m of vuggy silica in what were
originally phreatomagmatic breccias (Figure 2c.1).
Because hole SD-11 is the only one within an area of
about 300 x 300 m, the spatial configuration of the
body containing this vuggy silica interval is undefined
and, hence, only represented schematically in Figure
2c.1. However, this figure does illustrate how vuggy
silica formed selectively from breccias rather than
from the over- and underlying less-permeable lava
domes and flows. In the latter rocks, vuggy silica
intervals are unimportant, although locally well
developed, and are accompanied by Au-bearing
veinlets in the strongly fractured portions.
Mineral deposition history: stages and
zoning
Mineralization at the Oro Marcapunta prospect
95
 CHAPTER 2

E 361,100
N 8'808,600

fracture
fault

Au-(Ag)-bearing vuggy silica bodies

100 m Quartz-alunite zone. Largely uneconomic

Argillic alteration zone. Uneconomic

lava-dome

Figure 2c.2: Geological map of a selected area of strong hydrothermal alteration at Oro Marcapunta. The area of the map
is indicated in Figure 2c.1. Original lithology of the area is mainly constituted by lava-domes facies.

96

took place during several superimposed episodes. Up
to three main hydrothermal episodes or stages are
recognized (Figure 2c.5). These are described here
from earliest to latest. (i) An acid-leaching Early
barren stage, mainly responsible for the formation
of vuggy silica and peripheral advanced argillic and
argillic zones. (ii) A Gold stage in the form of
sulfide- and oxide-bearing veinlets, and finally (iii)
local Late stages which generally are economically
uninteresting.
Early barren stage
Although essentially barren, this stage is by
far the most prominent in the Marcapunta Au-(Ag)
prospect. It effected >90 % of the outcropping
central parts of the Marcapunta complex, where the
Au-(Ag) mineralization took place.
The Early barren stage developed a well
marked zoning outward from vuggy silica cores. As
in many other high-sulfidation systems, larger zones
of advanced argillic alteration, in turn, surrounded by
zones of argillic alteration surround these vuggy silica
ledges. The most external zones consist of phyllic
alteration bordered by distal haloes of propylitic
alteration.
Vuggy silica. Strongly leached vuggy silica
rocks retain their original texture and contain
resorbed magmatic quartz as the only remnant
magmatic mineral (Figure 2c.3). Vuggy silica ledges
are recognized from surface to as deep as 300 m (e.g.,
DDH CM4-444). Above 200 m depth, vuggy silica
seems to configure large bodies possibly funnel-
shaped, as intersected by hole SD-11, but below this
level they occur as veins no more than a few meters
thick.
Vuggy silica bodies that are not overprinted by
subsequent mineralization stages are characterized by
an almost invariable absence of minerals other than
hydrothermal quartz (Figure 2c.3). Gold values in
such cases are generally <100 ppb and silver is <5
ppm (e.g., several intervals in the first 100 m of SD-
11).
Within vuggy silica intervals, scarce massive
granular silica, largely consisting of quartz, are
observed. At several places, transitional contacts
between vuggy silica and massive granular silica are
seen. The transition zones display incipient granular
silica texture, consisting of fine-grained quartz
partially filling the voids of the vuggy silica, and
suggest that the transitions are intermediate stages of
textural destruction that in extreme cases transform
vuggy silica into massive granular silica (e.g., Simmons
et al, 2005).
Vuggy silica ribs also contain intervals of
quartz-alunite alteration. Under the hand lens or
microscope, it can be observed that vuggy silica
formation was superimposed on the quartz-alunite
CHAPTER 2
alteration, both of which display the effect of
corrosion (Figure 2c.3). This superimposition is
interpreted not as the product of discrete stages
of mineralization but in terms of zonal migration
(e.g., Sales and Meyer, 1949), in a similar manner to
that observed between different mineral zones of
the Smelter and Colquijirca deposits. Following this
interpretation, the outer vuggy silica zones encroach
onto quartz-alunite zones as the acidic hydrothermal
fluid front moved upward with time. The similar
composition and zoning of alunite in vuggy silica,
interpreted to be relict, and the well-defined alunite
from the peripheral advanced argillic zone (described
below) both support this view. In both cases, alunite
blades include pseudocubic cores of woodhouseite-
svanvergite composition (Figure 2c.4; Table 2c.1).
Quartz occurs coating vugs left by former
sanidine, plagioclase and other coarse grains of the
volcanic rock. It is typically euhedral and fine grained
(up to a few hundred microns long). In centimetric
cavities after blocky sanidine crystals, the quartz
crystals can be up to 1 cm long (Figure 2c.3).
Accessory minerals in the vuggy silica zones
include rutile and, according to EDS tests and
microscopic properties, also zircon. These minerals
occur as part of the quartz matrix in form of minute
subhedral inclusions generally a few tens of microns
in size.
Occasionally, within vuggy silica, thin coatings
of alunite, native sulfur, and pyrite and traces of other
minerals, such as covellite, as well as impregnations
of enargite and chalcocite are observed (Figure 2c.3,
2e.2).
Microprobe analyses were performed on several
alunite grains from these thin coatings. In contrast
to the zoned alunite described above, compositions
are homogeneous and close to that of stoichiometric
alunite (Table 2c.1).
Advanced argillic alteration zone. The
advanced argillic alteration (AAA) zone envelopes
the vuggy silica cores and extends over much larger
areas throughout the whole central sector of the
Marcapunta volcanic complex (Figures 2c.1 and
2c.2). The AAA zones can be collectively depicted
as vertical funnel-shape structures (800-1000 m in
diameter) surrounding the east-west-orientated vuggy
silica cores (Figure 2c.2). The maximum depths at
which the AAA zones have been recognized do not
exceed 300 m (e.g., DDH SD-11 and CM3-444).
Gold and silver values in these Early barren
stage AAA zones are generally very low (several
tens of ppb and a few ppm, respectively). However,
there are also some intervals without recognizable
overprinting of the later Gold stage, which carry
higher Au and Ag contents (up to several hundred ppb
and 20 ppm, respectively). The existence of strongly
anomalous Au-(Ag) intervals (up to 200 ppb Au)
within the AAA zones contrasts with their absence in
the inner vuggy silica ledges formed during the same
97

Early barren stage. This observation may suggest that
during the Early barren stage, very minor quantities
of gold were deposited in peripheral, cooler and less
acidic altered zones.
The advanced argillic alteration zone
characteristically consists of the quartz-APS minerals
group minerals assemblage accompanied by minor
amounts of zunyite, diaspore, pyrophyllite, native
sulfur, pyrite, enargite, covellite, chalcocite and other
rarer minerals.
The quartz-APS minerals group assemblage
is almost always fine-grained, ranging from a few
microns to clusters of perfectly hexagonal plates as
large as 4 mm across (typically between 0.5 and 1
mm). Quartz is the most abundant component of
the assemblage, constituting 60-70 volume %, with
the remainder composed essentially by alunite-group
minerals. However, alunite may locally dominate.
Several decimetric intervals containing >80 volume
% alunite are also observed (Figure 2c.3). Reversal
crystallization characterizes the quartz-alunite group
pair and is most evident in large voids produced by
leaching of sanidine phenocrysts. Alunite-group
minerals generally replace feldspar grains and more
rarely are disseminated within the rock matrix. In
this last case, the alunite has a sugary texture. Alunite
when not accompanied by oxidation phases is
characteristically pinkish in color. Yellowish tones are
apparently due to impregnations of goethite and/or
jarosite along cleavage and fractures. Translucent
specimens are rare. Alunite birefringence is highly
variable, from first-order to second-order purple
(Figure 2c.3).
In the outer AAA zone, alunite blades often
show under the microscope pseudocubic cores
displaying marked oscillatory zoning arrangement
(Figure 2c.3). The cores show compositions of
the woodhouseite series whereas the blades are
virtually pure alunite (see analytical details below).
In contrast, alunite immediately adjacent to vuggy
silica generally does not show pseudocubic cores and
is monomineralic. Zoning of the replacement and
filling geometry of former phenocryst sites is also
recognized. Phenocryst sites in outer AAA zone are
almost entirely replaced by alunite and quartz, and
the rock appears compact and lacks significant open-
space development. In contrast, in the inner zones,
adjacent to vuggy silica ledges, phenocryst sites show
voids and are only partially filled by the quartz-alunite
assemblage (Figure 2c.3).
Multipoint microprobe traverses from the
pseudocubic cores to the margins of alunite blades
show that the oscillatory cores approach the svanvergite
end-member of the woodhouseite series, with the A
site being occupied by highly variable amounts of
mainly Sr and Ca. Analyses range from 14.47 wt %
SrO and 3.1 wt % CaO, with minor amounts of BaO
and CeO, i.e., approaching the composition of the
svanvergite end-member, to values as low as 1.81 wt
% SrO, with CaO and CeO up to 6.5 and 5.2 wt
98
CHAPTER 2
%, respectively (Table 2c.a). The cores are virtually
devoid of K2O and Na2O. Comparable fluctuations
occur in the S ion site where phosphorous dominates
over sulfur in the most Sr-enriched zones (svanvergite
member). Thus, in a single pseudocubic core, P2O5
contents were found to range from 28.5 wt % to as
low as 12.2 wt %. Relatively high fluorine contents
were found in most analyzed alunite blades (up to
1.22 wt %).
In contrast to the cores, the envelope displays
no evident zonal pattern, neither in thin section
nor with SEM imaging. Microprobe results are
in accordance with this, revealing an almost pure
end-member alunite of relatively homogeneous
compositions. The only significant compositional
variation is due to some Na substitution for K (0.18-
1.4 wt % NaO). The fluorine contents do not differ
significantly from those characteristic of the alunite
rimming woodhouseite series cores (Table 2c.1).
Alunite in zones immediately adjacent to vuggy
silica bodies, which as explained above is largely devoid
of pseudocubic cores, shows similar compositions to
that in the envelopes, the only difference being that
Na substitution is lower (Na/K>0.1).
Argillic alteration zone. This zone is
distinguished by the dominance of kaolinite and/or
dickite. Locally pyrophyllite, alunite, sericite, and,
more rarely, cristobalite, native sulfur, pyrite and
smectite are volumetrically significant. The highest
precious metal concentrations found in this zone are
on the order of 50 ppb Au and a few ppm Ag (except
where overprinted by later gold-bearing veinlets).
The argillic alteration zone is mineralogically
the most complex of all of the alteration zones.
Two well-developed sub-zones may be defined: an
innermost sub-zone, adjoining the AAA zone, made
up mainly of kaolinite-(dickite)-alunite-quartz, and an
outer sub-zone containing kaolinite-(dickite)-sericite-
pyrophyllite-quartz and pyrite.
A distinctive feature of the alunite-bearing
argillic alteration sub-zone is that the original rock
textures are in most cases completely obliterated.
The presence of alunite accompanying the dominant
kaolinite-(dickite) seems to be related to this rock-
texture obliteration. Conversely, the sericite-bearing
argillic alteration sub-zone tends to preserve original
volcanic texture.
Phyllic alteration zone. The dominant
alteration assemblage is sericite, quartz, kaolinite,
and pyrite. Occasionally, pyrophyllite is present
in appreciable amounts. Phyllic alteration defines
irregular pockets, which collectively surround
the argillic zone. The available mining data show
insignificant precious metal concentrations in this
zone. Only occasionally does gold attain anomalous
levels (above 20 ppb).
Rocks affected by phyllic alteration largely
preserve their original texture. Nevertheless, with

the exception of quartz, all primary minerals have
been almost completely replaced. Feldspars are
entirely replaced by sericite plus another unidentified
phyllosilicate. Feldspar pseudomorphs consisting of
sericite plus kaolinite are also locally observed. In
general, the groundmass is replaced by microcrystalline
aggregates of sericite, kaolinite, quartz, and pyrite.
Locally, weak silicification of the matrix is observed
in rocks affected by phyllic alteration.
Propylitic alteration zone. Propylitic rocks
are the most distant expression of the pervasive
hydrothermal alteration associated with the
Marcapunta disseminated high sulfidation Au-(Ag)
prospect. Gold and silver contents are close to
background levels in unaltered dacitic rocks. Most
of the exposures of this alteration type are present
beyond the central parts of the Marcapunta complex.
At depth, hole Brocal 524, which is located ~200
m north of the advanced argillic zones intersected
irregular intercalations of phyllic and propylitic
alteration from near surface to as deep as 350 m,
suggesting that these zones collectively constitute
a enveloping funnel-shaped zone surrounding
the main Au-(Ag) mineralized core. The mineral
assemblages consist predominately of mixtures of
chlorite, kaolinite, calcite and, locally, minor epidote
and montmorillonite.
Feldspars are mainly altered to montmorillonite
and small amounts of kaolinite, whereas biotite
and hornblende are mainly altered to chlorite. The
groundmass is argillized (mainly montmorillonite)
and more rarely slightly silicified.
Gold stage
The Gold stage is characterized by the formation
of veinlets containing pyrite and minor amounts of
enargite, covellite, chalcocite, sphalerite, and other
minerals including clays. The spatial association of
gold with zones containing densely distributed sulfide
veinlets strongly suggests that significant amounts of
the gold in the Oro Marcapunta prospect are hosted by
the sulfides. Sulfides and clays occur as fracture filling
and veinlets, as matrix of hydrothermal breccias, and
as disseminations (Figure 2c.4). The sulfide content
typically ranges between 2 and 8 volume %. Gold
contents in intervals containing abundant veinlets
range from several hundred ppb to several ppm,
whereas silver typically ranges from 10 to 40 ppm
(e.g., DDH SD 11, 92.8 m-151.0 : 1.7 ppm Au and 43
ppm Ag; Vidal et al., 1997).
Several types of sulfide veinlets are recognized
to have formed during this early Gold stage. The
most important in terms of precious metal values
are straight siliceous veinlets. Much less abundant are
several types of sinuous veinlets.
Straight siliceous veinlets (up to 1-3 mm wide)
are dark in color and consist essentially of thin bands
CHAPTER 2
of anhedral quartz grains, commonly <500 m in
size, and sulfides, mainly pyrite, enargite, covellite,
chalcocite, and sphalerite. Clay minerals, including
kaolinite, illite, and smectite, occur as intergranular
fillings (e.g., Figure 2c.4). Accessory phases are
rutile, hematite and, more rarely, chalcopyrite and
magnetite. Pyrite occurs as disseminations, especially
in the central parts of the veinlets whereas enargite,
chalcocite and covellite coat fractures, typically
along the veinlet walls. Enargite is the second most
abundant sulfide phase in the straight siliceous
veinlets and generally in the Gold stage. It occurs
as subhedral prismatic crystals up to 2 mm long,
although massive aggregates and impregnations are
also common. Covellite occurs as tabular crystals
and irregular massive aggregates; it usually fills open
spaces with the other sulfides. Enargite, which also
fills open spaces, apparently postdates pyrite but, in
turn, is replaced by covellite and hypogene chalcocite.
Sphalerite, which occurs as disseminations together
with pyrite, is present only locally. Hematite occurs
as plates in voids, and magnetite forms tiny irregular
clusters. The well-defined walls of the straight banded
veinlets, suggest that they were formed under brittle
deformation conditions.
Straight siliceous veinlets display haloes
containing sulfide disseminations, essentially pyrite.
These disseminations are most abundant in the
highly permeable vuggy silica (Figure 2c.4) where
anhedral to subhedral pyrite, 50 to 500 m in size,
may completely fill voids.
In Au-(Ag) mineralized parts (i.e, 1-2 g/t
Au equivalent), straight siliceous veinlets typically
constitute between 1 and 5 volume % of the rock.
However, there are also densely veined zones which
contain uneconomic gold values (<300 ppb).
Thin (up to 0.5-1 mm wide), discontinuous
sinuous veinlets with poorly-defined walls, likely
formed under ductile conditions are more rarely
observed. These veinlets have a similar mineralogy
to the straight banded veinlets, although the sulfide
content is lower so explaining the paler color. There
are parts with 1-5 volume % sinuous veinlets, and
their precious metal contents do not differ greatly
from those containing comparable amounts of
straight siliceous veinlets. Given their volumetrically
minor abundance, it is estimated that sinuous veinlets
do not contribute significantly to the bulk precious
metal inventory of the Oro Marcapunta prospect.
In intervals with sulfide disseminations, mainly
in Early barren stage vuggy silica and quartz-alunite
zones, pyrite occurs as fine encapsulations in quartz.
In some of the samples more than one generation of
pyrite has been identified. An early pyrite generation
is locally intergrown with enargite and covellite. A
later generation occurs associated with quartz but
without other sulfides. Locally, the pyrite exhibits
growth zoning. Clays, largely kaolinite, but also
smectite and/or illite rarely occur coating voids in the
vuggy silica rocks as accompaniments to sulfides.
99
 CHAPTER 2

Resorbed magmatic quartz

A 1 cm B 0.5 cm

zunyite
C 0.2 cm D 1 cm

svanbergite

quartz
alunite

alunite
10 cm F
E

Figure 2c.3: Selected images from the alteration assotiations and assemblages from the Early barren stage. A. Typical vuggy
silica rock from originally porphyrytic lava-dome facies. Some voids are filled by native sulfur. B. Quartz-alunite alteration from
zones immediately surrounding vuggy silica cores. Alunite, commonly pinkish, almost entirely replaces former K-feldspar grains.
C. Zunyite coating fractures in vuggy silica rock. D. An example of the interface between vuggy silica and quartz-alunite altera-
tion. Vuggy silica contains coatings of fine-grained quartz and alunite. E. Corrosion of quartz-alunite assemblage occurring as
coatings in cavities of vuggy silica. F. Photomicrograph in transmitted light of a tiny void filled by alunite containing cores of
APS phases of the svanbergite series.

No definitive zoning has been recognized in
this stage. Only subtle mineralogical changes are
observed, the most noticeable perhaps being the
increase of sphalerite content with depth.
A second Au-(Ag) occurrence consists of
veinlets composed predominately of oxides, mainly
botryoidal hematite and goethite. Oxide veinlets
accounts typically between 2 and 10 volume % of
a given mineralized rock. The oxide veinlets cut
predominately vuggy silica bodies and, in much lesser
degree, rocks affected by quartz-alunite alteration.
Ore grades are generally higher than in sulfide-bearing
veinlets, with gold and silver values usually ranging
from 0.5 to 2.5 ppm and 20 and 70 ppm, respectively
(Ag/Au ratios from ~10 to ~30; Table 2c.2, Figure
5.5). A representative example of precious metal
enrichment in rocks containing oxide veinlets is given
by the DDH SD 11 which from 92.8 to 151 m depth
returned values of 1.7 ppm Au and 43 ppm Ag for
a Ag/Au ratio of ~25. Recent drilling, some 500 to
700 m south-west of DDH SD11, in the Marcapunta
Oeste project, intersected similar Au-(Ag) mineralized
intervals with Ag/Au ratios <30. Higher Ag/Au
ratios (up to >80) observed at Marcapunta Oeste

100
 CHAPTER 2

A 1 cm B 1 cm

hematite

C 0.5 cm D

plumose alunite

vuggy silica
E 10 cm Au-bearing F
quartz-alunite

Figure 2c.4: Main mineral occurrences of the Gold and Late stages. A. Au-(Ag)-bearing sulfide veinlets cutting quartz-alu-
nite assemblage. Note that sulfide dissemination haloes developed from the veinlets. B. Au-(Ag)-bearing oxide veinlets. Oxides are
largely hematite and goethite. C. Au-(Ag)-bearing botryoidal hematite coating voids in vuggy silica rock. D. Detail of C using
backscattered imagery. E. Late stage massive oxide vein cutting Au-(Ag)-bearing quartz-alunite alteration zone. F. Late stage
plumose alunite cementing rounded clasts of mineralized vuggy silica.

in oxide veinlet-bearing rocks are interpreted as the
effect of overprinting by Cordilleran mineralization,
which typically have Ag/Au ratios between 40 and
>100 (see Chapter 2a). Several lines of evidence,
including overprinting of sulfide-bearing and oxide-
bearing veinlets, suggest that oxides formed nearly
coetaneously with the sulfide-bearing veinlets.
Disseminated botryoidal hematite, and less
importantly goethite, typically coat the walls of voids in
vuggy silica rocks or overgrow euhedral hydrothermal
quartz (Figure 2c.4). The botryoidal hematite extends
in lesser amounts beyond the strongly leached cores
to the advanced argillic alteration zone. In these cases,
the hematite also overgrows alunite and/or quartz.
At levels below the base of supergene
oxidation (e.g., DDH SD-11, >300 m depth), this
oxidation process is particularly well observed. At
such depths, intervals containing pyrite and minor
sphalerite also contain botryoidal hematite within
distances of only several centimeters. Separates from
zones containing only botryoidal hematite and minor
goethite returned up to five times more gold (1.2-
2.5 g/t) than separates containing exclusively sulfides
(0.1-0.5 g/t), suggesting that the oxidation process
was the main Au-fixing event.

101
 CHAPTER 2

Early barren stage Gold stage Late stages

rutile
zircon
muscovite
chlorite
pyrite
enargite
quartz
Au-bearing hematite
Au-bearing goethite
zunyite
alunite (APS phases)
calcopyrite
tennantite
dickite-(kaolinite)
illite-(smectite)
sphalerite
calcosite
covellite
native sulfur

volume %
<1 >1-<5 > 5 - < 10 > 10

Figure 2c.5: Mineral paragenetic sequence in the Oro Marcapunta prospect. Consider simultaneous mineral precipitation of
two or more minerals during a given position in time. E.g., whereas a batch of fluids during the Early barren stage is precipitating
quartz in internal zones of the deposit another batch is at the same time precipitating alunite in more external positions.

Late stages Table 2c.1. Representative microprobe composition of alunite

Several vein and breccia sets were recognized from the disseminated Au-(Ag) mineralization at Oro
Marcapunta
to cut both the Early barren stage and the Ore
stage. Their relative timing is undefined so they are Sample PBR-214 PBR-335 PBR-338 PBR-336
considered collectively as late stages. K2O 8.34 8.60 8.31 8.22
A main expression of the late mineralization Na2O 1.73 1.79 0.18 1.78
is constituted of coarse-grained veinlet sets and BaO 0.71 0.60 0.11 0.25
breccias consisting dominantly of APS mineral(s)
SrO 0.47 0.79 0.20 0.02
and devoid of precious metals. More important in
terms of value, although volumetrically minor, are Al2O3 36.29 35.35 37.38 37.20
relatively thin veins and veinlets of fine-grained APS SO3 39.88 39.93 38.63 38.86
minerals carrying high silver and gold values. P2O5 0.39 0.43 0.54 0.24
Coarse-grained alunite-bearing veinlets H2O** 14.17 14.77 11.20 11.86
consist essentially of alunite similar in appearance
F- 0.33 0.21 2.15 0.76
to late plumose alunite of high-sulfidation
epithermal systems worldwide (e.g., Marysvale, Utah Total 102.30 102.45 98.69
Cunningham et al. 1998). Individual alunite grains, *. Alunites were analysed using a Cameca SX50 electron mi-
typically in clusters as open-space fillings, attain 2 cm croprobe at the University of Lausanne. Instrumental conditions
in length (Figure 2c.4). Veinlet sets are formed of were: accelerating voltage of 12 kV, beam current of 10 nA,
multiple individual veinlets, each no more than 3 cm and spot size of 15 mm. **. Weight % H2O calculated based
wide. Coarse-grained plumose alunite also cements on observed values of sulfur, phosphorous, potassium, sodium,
breccias containing rounded clasts of mineralized strontium, barium, and fluorine, and alunite stoichiometry using
vuggy silica (up to 1 ppm Au) (Figure 2c.4). Quartz, the formula AR3(SO4)2(F, OH)6, in which A refers to the large
in minor amounts, is the only accompanying phase cations K+, Na+, Ba2+, Pb2+ and Sr2+, and R is Al3+
and occurs encapsulated in the alunite clusters.
This generation of quartz is euhedral and occurs as
individual bipyramidal grains, never twinned, and as
large as 1 cm in.

102

Table 2c.2 Au and Ag contents of representative mineralized
intervals from the SD-11 drill hole in the disseminated Au-(Ag)
mineralization at Oro Marcapunta.
From - to (m) Au Ag
95-106 1.4 18
108-130 1.6 21
135-142 0.9 19
150-170 1.2 24
173-190 1.9 27
194-202 1.6 31
Analysis by fire assay and atomic absoption
Coarse-grained alunite in both veinlet sets and
breccias is buff to pale pink in color. Birefringence is
most commonly second-order pink to blue. A sample
analyzed using the electron microprobe gave relatively
heterogeneous compositions, the most important
feature being the dominance of the A site by K and
Na (together these elements account for not <10 wt
% with an average Na/K of nearly 0.2, Table 2c.1).
This composition places this APS mineral near the
alunite end member. Lead, Ba, and Ca in minor and
variable amounts complete the A site (up to 1.4 wt
% PbO, 0,85 wt % BaO, and 0,72 wt % CaO). Also
significant is the substitution of As by S, with As2O3
contents as high as 1.4 wt %.
Fine-grained late veining of undefined
mineralogy cuts the Gold stage. In contrast to the
coarse-grained alunite-bearing structures, these
veinlets display relatively high Au and Ag values
(between 0.2 and 1 Au g/t). The fine-grained veinlets
and veins are commonly <10 cm wide and display
a sugary texture. The most spectacular of these
structures was cut by hole CM1-436 at 231.40 m
depth. This vein, 1.1 m wide, contains an average of
28 oz/t Ag, 9.5 ppm Au, and 10 % Pb. Unexpectedly,
a single sample from this vein analyzed using
metaborate fusion yielded a very high value of
621 ppm thallium. Notwithstanding the uncertain
mineralogy of this vein, values obtained from whole-
rock analysis strongly suggest that it is chiefly made
up of one or more APS minerals rich in Pb and Fe
(corkite?).
Massive oxide veins
Massive oxide veins 0.2 to 2 m wide cutting
Au-(Ag)-bearing vuggy silica and quartz-alunite
alteration zones are another type of late veining. The
veins are relatively abundant at Oro Marcapunta and
consist largely of Fe-oxides, mainly goethite with
minor amounts of fine-grained quartz (Figure 3c.4).
Precious metal contents in these veins reach up to >1
% As, 1.5 ppm Au, 10 oz/t Ag (Ag/Au ratios >100).
These high As values and Ag/Au ratios suggest that
the massive oxide veins may represent an expression
of Cordilleran mineralization.
CHAPTER 2
REFERENCES
Barba, G., 1992, Mapeo geolgico a escala 1:2000 del
Cerro Marcapunta. Informe privado Sociedad Minera El
Brocal S.A.A., 91 p.
Corbett, G.J., and Leach, T.M., 1998, Southwest Pa-
cific Rim gold-copper systems: structure, alteration and
mineralization. Society of Economic Geologists, Special
Publication No. 6, 237 p.
Cunningham, C.G., Rasmussen, J.D., Steven T.A., Rye,
R.O., Rowley, P.D.,. Romberger, S.B, and Selverstone, J.,
1998, Hydrothermal uranium deposits containing molyb-
denum and flourite in the Marysvale volcanic field, west-
central Utah. Mineralium Deposita, 33, p. 477-494.
Hedenquist, J.W., 1987, Mineralization associated with
volcanic-related volcanic systems in the circum-Pacific ba-
sin. Circum-Pacific Energy and Mineral Resources Con-
ference, 4th, Singapore, Transactions, p. 513-524.
Noble, D.C., 1992, Informe privado Compaa de
Minas Buenaventura.
Sarmiento, J., 2004, Domos de lava relacionadas a la
diatrema principal en centro volcnico Marcapunta, Dis-
trito Minero de Colquijirca-Per Central. Tesis Ingeniero,
Universidad Nacional San Antonio Abad del Cuzco, 86
p.
Self, S., 1982, Lava flows and domes, in Pyroclastic
Volcanism, edited by L.D. Ayres. Geological Association
of Canada, Short Course Notes, 2, p. 53-57.
Sales, R.H., and Meyer, C., 1949, Results from prelimi-
nary studies of vein formation at Butte, Montana. Eco-
nomic Geology, 44, p. 465-484.
Sillitoe, R.H., 2000, Zinc Exploration at Colquijirca,
Central Per. Private report for Compaa de Minas Bue-
naventura S. A., 9 p.
Simmons, S.F., White, N.C., and John, D.A.,
2005, Geological characteristics of epither-
mal precious and base metal deposits. Econom-
ic Geology 100th Anniversary Volume, p. 485-523.
Stoffregen, R.E., 1987, Genesis of acid-sulfate altera-
tion and Au-Cu-Ag mineralization at Summitville, Colo-
rado. Economic Geology, 82, p. 1575-1591.
Vidal, C., 1992, Exploraciones por oro en el Suroeste
del Cerro Marcapunta. Distrito Minero de Colquijirca
y Cerro de Pasco. Informe privado Sociedad Minera El
Brocal S.A.A., 26 p.
Vidal, C., Proao, J., and Noble, N., 1997, Geologa y
distribucin hidrotermal de menas con Au, Cu, Zn, Pb y
Ag en el Distrito Minero Colquijirca, Pasco. IX Congreso
103
 CHAPTER 2

Peruano de Geologa, p. 217-219.

Vidal, C.E. and Ligarda, R., 2004, Enargite-Gold Deposits

at Marcapunta, Colquijirca Mining District, Central Per:
mineralogic and geochemical zoning in subvolcanic, lime-
stone-replacement deposits of high-sulfidation epither-
mal type. Economic Geology, Special Publication No 11,
p. 231-242

104

2.d The San Gregorio deposit
The blind San Gregorio Zn-Pb-(Ag) deposit is
located in the southern sector of the district, southwest
of a strongly oxidized hill at Gualquepaqui, ~3 km
south of the center of the Marcapunta volcanic
complex (Figure 2d.1). The name San Gregorio was
taken from the contiguous (Figure 2d.1) old mine at
the Gualquepaqui hill, where, during the first decades
of the 20th century, Bi-Ag and Cu were mined
(Hutchinson, 1920) . To avoid confusion the old Bi-
Ag mine will be referred to hereafter as Gualquepaqui
and the new Zn-Pb-(Ag) discovery as San Gregorio.
Two other areas, Bohorquez and Yanque Maria
(Figure 2d.1) were also mined for Bi and Ag between
Gualquepaqui and Marcapunta Sur.
In contrast to the northern part of the district
where continuous replacement unites Smelter
and Colquijirca, no continuity is so far recognized
between the Cordilleran deposits at San Gregorio
and Gualquepaqui and those in the southern part
of the volcanic complex (Marcapunta Sur prospect).
Continuity between the strongly oxidized Bi-Ag-Cu-
bearing zone at Gualquepaqui and the Cordilleran
ores in the Marcapunta Sur prospect is uncertain.
A continuity may be inferred between Bohorquez-
Yanque Maria and Marcapunta Sur as illustrated in
Figure 2d.2.
The San Gregorio deposit is made up of
irregular orebodies, several tens of m thick, replacing
almost entirely the nearly 400 m thick sequence of
carbonate rocks of the Pucar Group (Bendez,
1997; Fontbot and Bendez, 1999; Fontbot and
Bendez, 2000; Petersen and Canchis, 2000). The
bulk of the San Gregorio ores constitutes a material
locally called sulfide rock which, based on the
presence of relatively abundant amounts of alunite,
were formed from acidic fluids (Fontbot, 1997).
This material is typically very fine-grained (<100 m)
and is mineralogically simple. Sphalerite, galena, and
pyrite are the principal sulfide components, whereas
quartz, kaolinite, and alunite largely predominate in
the gangue fraction. The great abundance of alunite
in the San Gregorio ores differs from the Colquijirca
deposit, where alunite is restricted to small internal
zones immediately surrounding the enargite-bearing
core (Chapter 2b).
Except for the strongly oxidized rocks of the
Gualquepaqui hill, neither exposures of the orebodies
nor the host rock are present at San Gregorio. All data
presented in this chapter are based almost exclusively
on core from drill hole information. For this reason
CHAPTER 2
the following description does not achieve the level
of detail presented for the Smelter and Colquijirca
deposits.
Host rock
Different data, including paleontologic records
and drill core correlations (Bendez, 1997; Fontbot
and Bendez, 1999), indicate that the original host
lithology at San Gregorio consisted of nearly 400 m
thick dolostone and limestone sequence, immediately
overlying the Mitu Group, which is attributed to the
Chambar Formation (base of the Pucar Group.
Bendez (1997) made public results obtained by
Pardo (1997) whereby drill cores in carbonate rocks
from the immediate vicinity of the deposit and, in
partially decarbonatized dolostones in mineralized
intervals, preserve fauna characteristic of the Upper
Triassic-Lower Jurassic (Liassic). Among such species
are Lucina Goliat GOTTSCHE, Rhynchonella c. f.
tetraedora SOWERBY, and Pentacrinus cf. jurensis
QUENSTEDT. Moreover, an outcrop of silicified
dolostones at Gualquepaqui, around 50 m over the
contact with red beds of the Mitu Group, contains
Monotis Subcircularis, characteristic of Norian.
In addition, a lithogeochemical reconnaissance
conducted in relict carbonate beds in San Gregorio
resulted in compatible values with those obtained on
samples from the nearby Lachipana hill (approximately
3 km northwest of San Gregorio) where the Pucar
sequence overlies the Mitu Group red beds (Yacila,
2001).
The generalized stratigraphic section of the
Pucar Group in the mineralized sector of San
Gregorio (Figure 2d.3) was reconstructed on the
basis of a correlation of less altered rocks and rock
remnants. The lowermost 15 to 30 m consist of finely
laminated beige dolostones called basal dolostones
(Chapter 1a) which constitute the less altered unit of
the Pucar Group in the San Gregorio deposit and
chemically resemble the basal dolostones at the
Lachipana hill, 3-5 km north-west of San Gregorio
(Yacila, 2001).
Follow 200 m of mainly dolostones and
limestones with several thin intercalations of
cinerites at the base of the interval. Cinerites are also
recognized in the Chambar Formation in the nearby
Lachipana hill, 50 m above the contact with the
Mitu Group (Chapter 1). More than half of the San
105
 CHAPTER 2

N 8808000
N 8805000

N 8807000
N 8806000
4,185

E-360,000

a' SAN GREGORIO

85
4,1

Gualquepaqui hill
A
a
E-361,000
4,182.5

San Juan river MARCAPUNTA

4,460

4,4
40
4,4
20
4,4
00
4,3
80
4,3
60
4,3
40

4,32
0
4,30
0
4,28
0

E-362,000
4,260

4,240

4,220
folding 4,20
0

possible thrust fault 500 m

Figure 2d.1: Map of the southern sector of the Colquijirca district showing the different Cordilleran ore zones in relation to
the Marcapunta hill (the Marcapunta diatrema-dome complex). San Gregorio, as explained in the text, appears to constitute
the outer zone of a large mineralized corridor that extends from the Marcapunta complex. Similarly to the northern Smelter-
Colquijirca sector, inner portions of this southern corridor consist of enargite-dominant zones.

Gregorio resources are hosted in these lower 200 m
of dolostones and limestones. The upper 150-200 m
are composed of sandy dolostones intercalated with
milimetric to centimetric coarse-grained sandstone
layers (Figure 2d.3). These upper beds, as pointed
out in Chapter 1, are, in comparison to surrounding
Pucar outcroppings, particularly well developed in
San Gregorio, and host perhaps up to more than one
third of the Zn-Pb-(Ag) resources of the deposit.
A very minor fraction of the San Gregorio
ores is hosted by the detrital sediments of the basal
breccia (Chapter 1), a thin horizon of <5 m thick
considered to be the base of the Pucar Group.
Spatial configuration of the mineralized
bodies and controls on mineralization
The shape of the ore bodies at San Gregorio
seems to be controlled by several factors. The
external parts of most ore-bodies follow lithological
and structural patterns, whereas the acidic nature of
the hydrothermal fluids apparently played a more
influent role in their internal parts. In other words, an
entire mineralized orebody displays a geometrically
composite character, which notably differs from the
other Cordilleran deposits of the district, particularly
from the mantos at Colquijirca.
Correlations of drill cores located in a 100 m
spaced grid (in places down to 50 m apart) indicate that
irregular bodies that crosscut stratification represent
more than half of the deposit. These large structures
appear to be controlled by faults now unrecognizable
due to the extreme obliteration of the fabric, and
in part complete dissolution of the carbonate rocks
during the formation of the sulfide rock. One of
the most impressive irregular replacement bodies
was intersected by hole 39G which returned >300
m of continuous sulfide rock containing several
orebodies which collectively are >100 m grading 8%
Zn, and 2.5% Pb (Figure 2d.3). In addition, strongly
anomalous values in this hole (up to 3% Zn+Pb)
extend vertically down to the upper beds of the Mitu
Group red beds where multiple mineralized fractures
and faults can be recognized.
A generalized scheme showing the composite

106
 B A
S N

MINERALIZATION

Cordilleran ores Au-(Ag) disseminated ores

Cu-(Au-Ag) zone Quartz-alunite + vuggy silica
containing Au-bearing veinlets
Zn-Pb-Cu-(Ag-Bi) zone

Zn-Pb-(Ag) zone

San Gregorio deposit

GEOLOGICAL UNITS

Dacite diatreme-dome complex (Miocene)

Calera Formation (Eocene), mainly limestones and marls

100 m
Shuco Member (Eocene), calcareous conglomerates
200 m
Pucara Group (Upper Triasssic-Lower Jurassic), Limestones

Mitu Group (Permian-Triasssic), sandstones

section pass through the middle of the San Gregorio deposit. Correlations based on drill hole data and surface geology.
CHAPTER 2

107
Figure 2d.2: AB geological cross section of the southern sector of the Colquijirca district as indicated in Figure 2d.1. The
108
a' a
SW NE

?
39G 14G 37G 2N 34F

drill hole

quaternary deposits old workings

details on the mineralization at San Gregorio.

lower limit of oxidation

50 m
100 m

example of ore body

Zn-Pb-Cu-(Ag-Bi) zone

dissolution breccias Zn-Pb-(Ag) zone, largely sphalerite-galena

or "sulfide rock" subzone
intermediate dolostones economical interesting Zn-Pb-(Ag) interval

basal breccia
discordance
basaltic dike Post-Ore Stage silicification
3800 masl
fault-fracture Mitu Group red beds Post-Ore Stage
quartz-alunite-kaolinite alteration

Figure 2d.3: aa geological cross section as indicated in Figure 2d.1. The section is indeed part of section AB and gives more
CHAPTER 2

geometrical character of a mineralized body is
shown in Figure 2d.3. In this figure, it is interpreted
that sulfide rock intervals grade into sulfide rock economical mineralization at San Gregorio. A
veins or vein sets. External parts of sulfide rock partly
replace along bedding and form roughly conformable
manto-like shapes (up to >150 m long). Examples of
manto-like shapes are the ones encased above, below,
or in between various units of dissolution breccias
with argillaceous matrix, as shown in Figure 2d.3.
Permeability, and consequently, lithology was the main
parameter controlling replacement along bedding.
In a few cases, some manto-like bodies appear to
be limited by dolostone units, as several orebodies
located immediately above the basal dolostones
or between relict intermediate dolostones (Figure
2d.3). Parts in contact with relict dolostones are
constituted mainly by sphalerite, galena, and Mn-
Fe-Zn carbonates and are external relative to the
acidically-formed sulfide rock intervals. The
less acidic character of the fluids in external zones
probably favored selective replacement of more
reactive lithologies, for example limestone rather
than dolostone and resulted in flat manto-like bodies.
In contrast, in the internal zones, where more acidic
fluids prevailed, bulk replacement of the carbonate
rocks derived in irregular bodies of sulfide rock.
Veins are volumetrically less important than
mantos. There was no attempt to correlate the
different vein intercepts due to the wide-spaced
drilling. They are generally narrow (<2 m wide),
abundant, and located throughout the deposit.
The walls of the veins are irregular because of
replacement of the host rock. The replacement is
better developed toward the hanging wall. Most of the
veins are made up of friable, microgranular sulfide
rock composed of sphalerite-galena-pyrite-quartz-
kaolinite-alunite. Less abundant are veins consisting
of sphalerite-galena-pyrite-barite, and, even rarer,
thin veins of famatinite-(tetrahedrite) (DDH 20G at
232 m depth).
Mineral deposition history: stages and
zoning
The study of more than 80 polished and thin
sections distributed systematically throughout the San
Gregorio deposit has allowed to distinguish only one
mineral ore stage (Figure 2d.5). In strong contrast to
Smelter, Marcapunta Oeste, and Colquijirca, no early
silica-pyrite stage (Early silica-pyrite stage in Chapters
2a and 2b) has been recognized at San Gregorio.
San Gregorio ores also have characteristically more
weakly developed internal zoning of the mineralized
bodies and a virtual absence of volumetrically
important copper concentrations in the inner zones.
These and other differences are described at the end
of the chapter.
CHAPTER 2
Ore stage
The Ore stage is the responsible for the
visual summary of the Ore stage is documented in
Figure 2d.4. Most of the images show the intimate
relationships between alunite and sphalerite-galena
characteristic of most orebodies. The Ore stage
developed a relatively simple zoning process that
resulted in three main zones, which, from inner to
outer parts, are: (i) a Cu-(Ag) zone, (ii) a Zn-Pb-(Ag)
zone, and (iii) a barren outer zone.
Cu-(Ag) zone
The Cu-(Ag) zone is economically unimportant
and volumetrically minor. Only two narrow Cu-
(Ag) veins <0.3 m wide were observed (e.g., DDH
20 G at, 232 m depth). The main minerals are
famatinite?, pyrite, quartz, and tetrahedrite. Minor
minerals include alunite and chalcopyrite. Famatinite
is observed in the vein core as disseminations and a
band up to 5 cm wide. Famatinite occurs as anhedral
grains replacing pyrite, as rims around it, and as
matrix between breccia fragments. Quartz grains are
subhedral and most are <2 mm long. No quantitative
data on the composition of these minerals are
currently available.
Several small high grade copper orebodies
were mined at the Gualquepaqui hill (Figures 2d.1
and 2d.3; Hutchinson, 1920; Johnston, 1929, 1933
y 1935, holes 2C and 2B). Copper carbonates and
chalcocite are recorded as the main cupriferous
minerals in what seems to represent different parts of
a supergene enrichment profile. Immediately above
the copper ores, a cut had been opened in the first
decades of the past century for Bi-(Ag) mining from
strongly oxidized ores with bonanza grades. Atelestite
and bismite are the main recorded bismuth minerals
mined (3-6 % Bi and 10-40 oz/t Ag; Hutchinson,
1920). This zone appear to represent the southern
expression, now stronlgy oxidized, of the Cu-(Ag-Bi)
zone recognized in the Colquijirca deposit.
Zn-Pb-(Ag) zone
This zone is by far the volumetrically most
important of the deposit. It can be broadly divided
into two main sub-zones which in turn exhibit minor
mineralogical variations with increasing distance: an
inner sphalerite-galena sub-zone, and an outer Zn
carbonate sub-zone with rhodochrosite and siderite.
Table 2d.1 shows characteristic compositions of the
various classes of ores of the Zn-Pb-(Ag) zone.
Sphalerite-galena sub-zone
The sphalerite-galena sub-zone comprises
approximately between 90-95 % of the San Gregorio
Zn-Pb-(Ag) resource (70 Mt at 8 % Zn, 2.5 % Pb, and
109
 CHAPTER 2

alunite

A B 40 m pyrite

sphalerite
galena

C 50 m D 50 m
sphalerite-galena

alunite

alunite-kaolinite

E 100 m F 50 m

rhodochrosite

G 1 cm H 1 cm

Figure 2d.4: Selected images on ores and rocks from the San Gregorio deposit. A. Typical ore from the Zn-Pb-(Ag) zone con-
sisting of a unconsolidated microgranular material (sulfide rock). B. Photomicrograph in transmitted light of a sulfide rock
sample showing a typical alunite-pyrite assemblage. C and D. Backscattered electron images of typical sulfide rock samples
showing the extremely fine-grained habit of alunite. Note that no reaction is noticeable between sphalerite or galena and alunite.
E. Photomicrograph in transmitted light of a sulfide rock sample showing the usual grain size of sulfides, mainly pyrite, and
alunite. No reaction is observed between sulfides and alunite. F. Alunite-kaolinite-quartz-pyrite veinlet cutting sulfide rock
consisting of sphalerite, galena, quartz, and alunite. An uncommon large grain of alunite as part of the veinlet. G. Massive
consolidated ore consisting of coarse-grained sphalerite, galena, pyrite, barite, and kaolinite. H. Core drill sample from the Zn-
bearing carbonate sub-zone. Rhodochrosite as veinlets is accompanied by minor amounts of sphalerite.

110
 CHAPTER 2

Table 2d.1 Main mineralogical and elemental components of typical Zn-bearing samples from the San Gregorio deposit. The lost of
ignition (LOI) is an indirect indicator of sulfide (PBR-12, 15, 25 and 27) and carbonate (PBR-17 to 22) content.
Sample/ Zn Pb Ag Cu As SiO2 Al2O3 Fe2O3 MnO MgO CaO LOI Mineral association
depth (m) XRF XRF ICP ICP ICP XRF XRF XRF XRF XRF XRF (XRD)
% % ppm ppm ppm % % % % % % %
PBR-15 35* 3.57 > 100 14.9 274 20.61 7.98 11.2 0.01 0.01 0.07 19.93 qz, kaol, alunite
High sulfate
sulfide rock

236.15 sl, py -mc, gn

PBR-27 25* 2.82 <0.2 13.8 247 38.23 14.49 2.47 0.03 0.08 0.32 15.1 qz, kaol, alunite
383.4 sl, gn, py-mc
PBR-26 33* 4.99 <0.2 3.1 111 49.29 7.7 2.98 0.04 0.03 0.15 9.43 alunite, kaol, qz
High silica
sulfide rock

192 sl, gn, py-mc

PBR-25 6.28 0.7 <0.2 8.4 82 67.67 8.87 2.14 0.06 0.1 0.47 8.54 qz, kaol, alunite
372.45 sl, py-mc
PBR-17 6.84 0.49 <0.2 1 19 2.76 0.57 15.28 33.94 2.82 0.96 31.74 Fe-Zn rhodocrosite
Zn-bearing

264.1
carbonate
sub-zone

PBR-19 7.89 0.54 <0.2 1.2 85 0.81 0.52 16.23 32.97 2.65 1.53 31.05 Fe-Zn rhodocrosite
301.7

0.7 oz/t Ag, Yaringao et al., 1997).. In mineralogical
terms this sub-zone consists of sphalerite, galena,
pyrite, and minor quantities of marcasite make up
the sulfide portion. The other constituent minerals
are chiefly quartz(kaolinite, alunite).
Sphalerite, galena, pyrite, quartz(kaolinite,
alunite) constitutes almost invariably a highly friable
material called by the Colquijirca staff sulfide rock
following the informal denomination given by Owens
(1995). The microgranular texture of this rock, with
grain size usually <100 m in its largest dimension
(Table 2d.4), has the macroscopic appearance of an
unconsolidated detrital rock.
In the internal parts of the sulfide sub-zone,
quartz and kaolinite-(dickite) account for up to >70
wt % of the rock (high silica sulfide rock in Table
2d.1). Sphalerite, galena, and quartz in these cases
occur habitually as anhedral to subhedral grains
exhibiting irregular borders indicative of corrosion
(Table 2d.4). Kaolinite-(dickite) are abundant and
usually fill intergranular spaces (Table 2d.4).
Other parts of sulfide rock consist besides
sphalerite, galena, pyrite, alunite and minor other
APS minerals. In these cases, quartz, kaolinite and
dickite are largely subordinated (<10 volume %;
high sulfate sulfide rock in Table 2d.1).
Sphalerite and galena in sulfide rock occur
generally intimately intergrown displaying complex
textures (Table 2d.4). Galena commonly replaces
sphalerite, although sphalerite replacing galena is also
observed. Sphalerite displays characteristically deep
orange to yellowish to whitish internal reflections
under crossed nicols (Table 2d.4), suggesting low FeS
contents (consistent with microprobe quantitative
data reported below).
Alunite is typically platy and euhedral to
subhedral and occurs commonly as intergranular
fillings accompanied by much finer kaolinite (Table
2d.4). Alunite occurs as very fine grains ranging
generally from 5 to 30 m across and from 1 to 5
m thick. Under the polarizing microscope, alunite
reaches first order yellow to gray birefringence;
more rarely in large grains up to second order blue
(Table 2d.4). The most common habit of alunite
is as oriented grain aggregates. Alunite blades are
commonly encroached into pyrite and, more rarely,
sphalerite. Alunite also occurs encapsulated in quartz
or overgrowing it.
Compositionally, the sphalerite-galena sub-
zone displays small mineralogical variations from
core to rim. Pb, for example, increases toward the
margin of the sub-zone (from 1.5 wt % up to 8 wt
%).
Veins consisting of >80 volume % of
sphalerite, galena, pyrite, barite, and kaolinite occur
more frequently in the peripheral parts of the
sphalerite-galena sub-zone. These veins consist of a
compact material in contrast to the sulfide rock, in
which the grain size of most of their components is
coarse (up to several centimeters; massive ore in
Table 2d.1). Sphalerite, galena, and barite are typically
intimately intergrown, whereas kaolinite and minor
amounts of quartz fills intergranular spaces (Table
2d.4). Minor tiny grains of siderite locally overgrow
barite.
Relatively rare, Ag-rich intervals consisting
largely of pyrite were intersected in a few holes
surrounding Gualquepaqui (e.g., DDH 36G at 146
m depth). The intervals reach up to >30 oz/t Ag
without any other appreciable metal content of
economic interest. Macroscopically, the Ag-rich
intervals are made up of monomineralic masses of
subhedral coarse-grained pyrite. Gangue minerals are
exclusively quartz and kaolinite.
Barren alunite-quartz-(kaolinite-pyrite) veinlets

111
 CHAPTER 2

Ore stage Post-ore stage

pyrite
famatinite-tetrahedrite
quartz
sphalerite
galena
siderite
hematite
rhodochrosite
alunite (APS phases)
marcasite
barite
kaolinite-(dickite)
anatase

volume %
<1 >1-<5 > 5 - < 10 > 10

Figure 2d.5: Mineral paragenetic sequence in the San Gregorio deposit. Consider simultaneous mineral precipitation of two or
more minerals during a given position in time. E.g., whereas a batch of fluids during the Ore stage is precipitating sphalerite in
internal zones of the deposit another batch is at the same time precipitating rhodochrosite in more external positions.

in the sphalerite-galena sub-zone

Sulfide rock bodies in the sphalerite-galena
sub-zone display abundant veinlets of microgranular
assemblages of alunite, quartz, kaolinite and minor
erratic amounts of pyrite. Although the distribution
of these veinlets often mimics spatially the highest
concentrations of Zn-Pb-(Ag), the veinlets themselves
lack the economically interesting sulfides, sphalerite
and galena. Barren alunite, quartz, pyrite veinlets
also occur in intervals devoid of any appreciable ore
concentration (Figure 2d.4).
Similar textural relationships are observed in
the veinlets throughout the sulfide rock bodies.
Paragenetically, alunite follows quartz precipitation,
although it is common to find alunite encapsulated
in quartz. Rare minute (<5 m long) inclusions of
quartz in alunite are also found. Kaolinite occupies
intergranular spaces between alunite and quartz
(Figure 2d.4) and occasionally it replaces alunite,
and much more rarely quartz. Pyrite, the only sulfide
observed in the veinlets, occurs as minuscule grains
in the alunite, quartz and kaolinite microgranular
mass. Pyrite has been rarely observed as inclusions in
alunite (Figure 2d.4). %, respectively (Table 2d.2).
Composition of minerals of the sphalerite-galena
sub-zone
Microprobe analyses of more than sixty grains
of sphalerite from the sulfide rock from different
parts of the sphalerite-galena sub-zone are broadly
homogeneous. Sphalerite, irrespective of whether it
correspond to internal or external parts of sulfide
rock bodies, yielded low FeS contents (<1.2 wt %,
averaging 0.3 wt %). Mn contents in sphalerite were
below the instrumental detection limits (0.05 wt %,
Table 2d.2)
Galena grains gave essentially stoichiometric
compositions (Table 2d.2). No significant silver values
were detected. Pyrite, on the other hand, although
generally compositionally stoichiometric, gave silver
values of up to 0.8 wt % (Table 2d.2). This type
of argentian pyrite is possibly the main Ag-bearing
mineral in the silver-rich pyritic intervals detected
in the periphery of Gualquepaqui and mentioned
above (Ag-rich pyrite). Copper and arsenic contents
in pyrite were found to be generally <0.2 and <0.4 wt
Electron microprobe and SEM imaging of
14 alunite grains from the sphalerite-galena sub-

112
 CHAPTER 2

Table 2d.2. Composition of main Ore stage sulfides from the Zn-Pb-(Ag) zone San Gregorio deposit according to
microprobe analysis.
Sample mineral S Mn Fe Zn Cd Pb Ag Total
PBR-208 sphalerite 32.74 0.00 0.15 66.85 0.02 0.00 0.00 99.77
PBR-208 sphalerite 32.78 0.00 0.11 67.04 0.04 0.00 0.00 99.97
PBR-208 sphalerite 32.24 0.00 0.08 65.77 0.00 0.00 0.02 98.11
PBR-275 sphalerite 32.68 0.00 0.14 67.70 0.06 0.00 0.00 100.59
PBR-275 sphalerite 32.93 0.00 0.07 66.10 0.12 0.00 0.00 99.22
PBR-275 sphalerite 32.60 0.01 0.33 66.85 0.04 0.00 0.02 99.84
PBR-275 sphalerite 32.71 0.00 0.18 65.44 0.12 0.00 0.00 98.46
PBR-275 sphalerite 32.50 0.00 0.16 67.39 0.14 0.00 0.00 100.19
PBR-208 galena 13.39 0.03 0.12 0.95 0.00 87.99 0.00 102.48
PBR-208 galena 13.30 0.05 0.11 1.17 0.01 87.33 0.00 101.98
PBR-275 galena 13.34 0.03 0.08 1.37 0.00 87.90 0.00 102.72
PBR-275 galena 13.31 0.01 0.10 0.87 0.00 87.88 0.00 102.17
PBR-208 pyrite 52.88 0.00 46.35 0.50 0.00 0.00 0.15 99.87
PBR-208 pyrite 52.21 0.00 46.77 0.14 0.00 0.00 0.10 99.22
PBR-275 pyrite 52.56 0.63 45.49 0.03 0.00 0.00 0.55 99.25
PBR-275 pyrite 52.74 0.00 46.43 0.44 0.00 0.00 0.01 99.62
Sulfides were analysed using a Cameca SX50 electron microprobe at the University of Lausanne. Instrumental
conditions were: accelerating voltage of 12 kV, beam current of 30 nA, and spot size of 10 mm.

zone demonstrate alunite to be compositionally
homogeneous and stoichiometric, with uniform
Na/K ratios of 0.03-0.12 and wt % SO3 between 39
and 40%. Such homogeneous alunites are similar to
alunite at Colquijirca, but markedly different from
those at Oro Marcapunta.
Zn-bearing carbonate sub-zone
The Zn-bearing carbonate sub-zone envelopes
the sphalerite-galena sub-zone as relatively narrow
bodies generally <2 m thick and containing usually
between 3 and 5 wt % Zn and low values of Pb (<0.5
wt %) and Ag (<0.5 oz/t). Locally, these bodies may
attain up to 8 m thick and bear high Zn contents
(e.g., DDH 34G, from 156 to 164 m at 7 % Zn). It is
estimated that this sub-zone accounts for around 5 %
of the total Zn inventory of San Gregorio (between
3 and 4 million tons).
Mineralogically, this zone is dominated by
Zn-bearing rhodochrosite, siderite, and oligonite
(Fe(Mn,Zn)(CO3)2), are the main. Minrecordite
(CaZn(CO3)2), and smithsonite (ZnCO3) may also be
present based on XRD data.
Sphalerite (Figure 2d.4), pyrite, and lesser
galena, together account for less than 10 volume %
of the ore. Microprobe analyses of sphalerite yield
between 1 and 4 wt % FeS (Table 2d.2).
The Zn-bearing carbonate bodies, notably
when made up mainly of rhodochrosite and siderite
occur as nearly massive replacements (Table 2d.4).
Observed in detail, the carbonates commonly have
bands of rhodochrosite and sulfide disseminations,
mainly sphalerite. Anhedral, low-Fe sphalerite grains
averaging 2 mm in size occur locally within massive
rhodochrosite. The Zn-bearing carbonate sub-
zone develops not only at the external parts of the
sphalerite-galena sub-zone, but also at the contacts
of the latter with dolomite relicts preserved in the
sulfide rock.
Typical compositions of Zn-bearing carbonate
rocks are given in Table 2d.1. Besides the high Zn
concentrations in carbonates, the values reflect also
the relatively low volume contents of sulfides in
these types of intervals (<10 volume % collectively
of pyrite, galena, and sphalerite). Table 2d.1
summarizes the high MnO and FeO
values, indicative
of the predominance of rhodochrosite, siderite, and
oligonite.
Barren outer zone
The barren outer zone represents the
outermost recognized expression of hydrothermal
activity produced by the Ore stage. No economically
interesting metals are present in this zone. The barren
outer zone consists mainly of veins and patches of
dolomite surrounding the Zn-bearing carbonate sub-
zone and of calcite veinlets particularly above this
sub-zone. Calcite veinlets has been recognized up to
500 m away from the economical parts of the San
Gregorio deposit (e.g., DDH 36G and 12G at depths
between 40 and 100 m).

113
 CHAPTER 2

Table 2d.3. Representative microprobe composition of alunite from three samples from the San
Gregorio deposit.

Sample PBR-208 PBR-275 PBR-211

K 2O 9.21 8.93 9.86 9.45 10.03 9.24

Na2O 0.42 0.65 0.82 0.54 0.65 0.01
BaO 0.08 0.03 0.03 0.02 0.01 0.03
SrO 0.16 0.22 0.18 0.34 0.11 0.08
PbO 1.32 2.03 1.34 1.42 0.89 0.72
Al2O3 36.42 37.03 35.89 36.56 37.01 37.62
SO3 40.80 40.20 39.43 40.65 40.28 41.28
P2O5 0.82 1.04 0.36 0.32 0.04 0.06
H 2O **
12.62 12.62 12.84 13.02 12.25 12.46
F -
0.38 0.42 0.10 0.14 0.46 0.56
Total 102.23 103.17 100.85 102.46 101.73 102.06

* Alunite samples were analysed using a Cameca SX50 electron microprobe at the University of
Lausanne. Instrumental conditions were: accelerating voltage of 12 kV, beam current of 10 nA, and
spot size of 15 mm. **. Weight % H2O calculated based on observed values of sulfur, phosphorous,
potassium, sodium, strontium, barium, and fluorine, and alunite stoichiometry using the formula
AR3(SO4)2(F, OH)6, in which A refers to the large cations K+, Na+, Ba2+, Pb2+ and Sr2+, and R
is Al3+

hundred of meters. The thickness of intermediate

Other manifestations of hydrothermal
activity in the San Gregorio deposit
In addition to the mineralization process
developed from the Ore stage described above, other
manifestations of hydrothermal activity, devoid
of economic mineralization, are observed closely
related in space to the main mineralized sector
of the San Gregorio deposit: an early process of
dolomitization and dissolution which formed the so
called intermediate dolostones and dissolution
breccias, and a late development of quartz-alunite-
kaolinite veins and silicification affecting the upper
part of the deposit.
Pre-Ore stage dolomitization and dissolution
Crosscutting relationships indicate that, prior
to the Ore stage mineralization, the Pucar carbonate
sequence underwent extensive dolomitization and
dissolution which are recorded in remnant beds
or irregular blocks. Of these remnants rocks, the
volumetrically most important constitute what
locally are known as intermediate dolostones and
dissolution breccias.
Relict intermediate dolostones consist of
dolostone and occasional remnants of limestone as
patches and thin beds. They have generally a flat shape,
following the spatial configuration of the sulfide
rock bodies (Figure 2d.3). Lateral dimensions (along
the strike of bedding) are on the order of tens to
dolostones bodies reaches >30 m in some drill holes
intercepts, although typically are <10 m. Drill holes
indicate that intermediate dolostones are commonly
cut by irregular subvertical bodies of sulfide rock.
MgCO3 contents in the intermediate dolostones fit
the typical compositions of dolostones with Mg/Ca
ratios >3 and unappreciable amounts of SiO2, Al2O3
and other components.
Dissolution breccias consist of sub-angular
to sub-rounded centimetric dolostones clasts in a fine-
grained limolitic matrix. Locally, reverse grading of
the clasts suggests a formation process comparable
to karstification. These intervals apparently form
stratiform bodies with generally constant thicknesses
up to several tens of m (Figure 2d.3). A strong
recrystallization of the clasts suggest that relatively
high temperatures accompanied dissolution,
presumably related to the hydrothermal fluids.
Dissolution breccias extend beyond intermediate
dolostones particularly west and south-west of the
San Gregorio deposit.
Dissolution breccias are rarely observed cut
by sulfide rocks, possibly due to the poor reactive
character of their matrix. However, in strongly
mineralized parts of the deposit, these are also cut
and completely replaced by the sulfide rock (e.g.,
S.D. 39G, S.D. 22G).
Post-ore stage quartz-alunite-kaolinite
alteration and silicification
The upper part of the San Gregorio deposit

114

display two nearly horizontal oxidized caps of
silicified and acidically altered rocks (Figure 2d.3).
A lower cap consist of a friable pale cream rock
quartz-alunite-kaolinite rock with variable amounts
of anatase, goethite, hematite and unidentified oxide
minerals. The upper cap is basically a jasperoidal
rock composed of quartz and minor amounts of
other cryptocrystalline forms of silica, including
cristobalite and opaline silica. In contrast to the lower
cap, hematite prevails over goethite in the silicified
cap.
Both caps display a flat shape of variable
thickness ranging from a few m to >30 m (Figure
2d.3). The contact between the quartz-alunite-
kaolinite and the silicified cap is sinuous. Under
microscope, it can be observed that the first cap
replaces the second, commonly from microveinlets.
Furthermore, numerous veins consisting of the
same mineralogical components, although richer in
anatase, originate in the roof of the quartz-alunite-
kaolinite cap and cut the lower parts of the silicified
cap (Figure 2d.3).
Most of the above features are highlighted in
Gualquepaqui. For example, quartz-alunite-kaolinite
veins cut the silicified cap in the western wall of the
Gualquepaqui open cut. The veins, <1 m wide, are
sub-vertical and strongly oxidized. They consist of
friable material containing besides quartz, alunite,
kaolinite, anatase and remnants of sphalerite (Figure
2d.3). In these cases the veins display sinuous walls,
suggesting migration of corrosive fluids.
Perhaps the most outstanding geochemical
feature of the lower quartz-alunite-kaolinite cap and
associated veins are the high content of strongly
immobile elements including Ti, Zr, and Nb (up to
>30000, >600 and >140 ppm, respectively).
Main differences with the Colquijirca
deposit
From the observational point of view, the
main differences between the San Gregorio and
Colquijirca Zn-Pb-(Ag) deposits include morphology,
the presence only at San Gregorio of a silicified
and quartz-alunite-kaolinite cap, the development
of extensive dissolution also only observed at San
Gregorio, and the absence in this last of an early
barren stage composed of silica-pyrite.
The different morphology of the ore bodies
at San Gregorio and Colquijirca may be due to the
difference nature of the host rock lithology. At
Colquijirca, the formation of sub-horizontal flat
elongated tube-like lenses is controlled by replacement
of carbonate beds limited by less permeable and
reactive marly and shaly horizons. In contrast, at
San Gregorio, the extensive and irregular ore bodies
geometry is primarily controlled by fractures while
lithology was important only in the external parts of
the mineralized bodies.
CHAPTER 2
San Gregorio lacks the development of the
Early silica-pyrite stage, a prominent mineralization
event present not only at Colquijirca but also in the
giant Cerro de Pasco deposit some 14 km to the
north. At this point of the investigation the possible
reasons for this are uncertain.
REFERENCES
Bendez, R., 1997, Caractersticas geolgicas miner-
algicas y geoqumicas de los yacimientos de Zn-Pb (Ag)
de San Gregorio y Colquijirca emplazados en unidades
sedimentarias en los bordes del sistema epitermal de alta
sulfuracin de Marcapunta. Tesis Ingeniero, Universidad
Nacional de Ingeniera, Lima, 60 p.
Fontbot, L., 1997, Memorandum del 4 de Noviembre
1997 a Sociedad Minera El Brocal S.A.A., 3 p.
Fontbot, L., and Bendez, R., 1999, The carbonate
hosted Zn-Pb San Gregorio deposit, Colquijirca District,
central Per, as a high sulfidation epithermal system. in
Stanley et al., (eds.), Fifth Biennial SGA Meeting, Mineral
Deposits: Processes to Processing, 1, p. 495-498.
Fontbot, L., and Bendez, R., 2000, Un nuevo tipo
de yacimiento epitermal de high sulfidation: Zn-Pb
Ag en rocas carbonatadas. Los ejemplos de San Gregorio
y Colquijirca. X Congreso Geolgico Peruano, Lima, julio
2000, Volumen de presentaciones, CD-ROM, doc. YM1,
15 p.
Hutchinson, W.S., 1920, The Fernandini properties,
province of Pasco, Per: Production costs and profits,
Colquijirca silver mine, Huaraucaca metallurgical plant, La
Curena copper mine, San Gregorio bismuth mine. Report
for the Fernandini Properties, 70 p.
Johnston, B.A., 1929, 1933 y 1935, Informe de los
sondajes diamantinos 2C y 2B, y otros informes internos.
San Gregorio, Cerro de Pasco. Informes privados Socie-
dad Minera El Brocal S.A.A.
Petersen, U., and Canchis, L., 2000, Geochemical zon-
ing and ore distribution in the San Gregorio zinc-deposit,
Central Per. Geological Society of America, November
2000, Annual Meeting, GSA Abstracts with Programs, 32,
No. 7.
Yacila, C., 2001, Internal private report for Sociedad
Minera El Brocal S.A., 5p.
Yaringao, M., Arias, W., and Panz, M., 1997, Ex-
ploraciones y evaluacin de los yacimientos del Distrito
Minero de Colquijirca, Pasco. IX Congreso Peruano de
Geologa, p. 231-236.
115
 CHAPTER 2

116

2.e Similarities, differences and spatial
relationships between the Au(Ag) disseminated
mineralization at Oro Marcapunta and the
Cordilleran base metal deposits of Smelter and
Colquijirca. A distinction base on field and
mineralogical observations
From an observational point of view,
differences (metal suite, total sulfide content, and
zoning) are greater than similarities (mineral alteration
assemblages and depth of emplacement) between, on
the one side, Au-(Ag) disseminated high sulfidation
epithermal mineralization at Oro Marcapunta and,
on the other, Cordilleran base metal deposits at both,
Smelter and Colquijirca. The differences justify why
each type is considered in this study separately and
has been classified into different ore deposit classes.
Furthermore, spatial relationships between these
ore types indicate that precious metal epithermal
mineralization at Oro Marcapunta predated those of
Smelter-Colquijirca.
Similarities
High level emplacement
The field evidences discussed above and
summarized in the cross-section of Figure 2e.1
indicate that the geometry of the ore district has
not experienced large changes since mineralization,
except perhaps collapse in the flanking parts of the
volcanic complex, which could be pre-, syn, and post
mineralization. Other significant post mineralization
tectonic displacement is not recognized. Post
mineralization erosion is also subordinate. The
present summit of Marcapunta which reaches 4500
m.a.s.l. approximates by several tens of meters the
one when volcanism was active. The main field
evidence lies on the fact that the some of the latest
extruded lava-dome units preserve parts their lave
effusive component near the summit of Marcapunta
and the lack of features indicating deep erosion. One
of these late lava-dome intrusions (Montura dome)
cuts mineralized lava-domes units near the southern
summit of Marcapunta (e.g., Sarmiento, 2005).
Disseminated epithermal Au-(Ag)
mineralization and Cordilleran hydrothermal activity
took place at a very high level, in part indicated by
the observation that the Montura dome which is
fresh and preserves its effusive component, cuts and
CHAPTER 2
immediately overlies domes hosting disseminated
Au-(Ag) ores which were emplaced between 4300
and 4500 m.a.s.l. (Figure 2e.1). The upper (and main)
part of Cordilleran hydrothermal activity at Smelter
and Colquijirca virtually reached the same shallow
level (up to around 4400 m.a.s.l.) as that which
produced disseminated Au-(Ag) mineralization, the
main part of the ore bodies occurring between 4200
and 4300 m.a.s.l. At San Gregorio, mineralization
is topographically lower, between 3900 and 4100
m.a.s.l.
High sulfidation mineral assemblages and acid-
sulfate gangue mineral assemblages
High sulfidation and acid-sulfate gangue
assemblages are the most evident sharing features
of Au-(Ag) epithermal and Cordilleran bodies.
At deposit scale, and without considering timing-
assemblage relationships, which will be discussed
below, in both mineralization types, enargite-pyrite is
the main assemblage indicating that high sulfidation
conditions prevailed in both hydrothermal systems.
More prominent is, nevertheless, the abundant
presence in both deposit types of the quartz-
alunitezunyite assemblage, or yet the development
of vuggy silica, indicative of acidic fluids. Again, this
last feature without considering timing-assemblage
relationships, which, as we will see below, are different
in each case.
Differences
Sulfide content. The sulfide content is one of
the main characteristics that make both mineralization
types different. Whereas at Oro Marcapunta it ranges
between 2 and 5 volume %, at Smelter and Colquijirca,
the sulfide content typically varies between 40-60
volume % (Chapters 2a, 2b and 2c).
This feature is irrespective of the host rock.
For example, the Gold stage (Chapter 2c), the
sulfide richest of the Oro Marcapunta disseminated
117
118
jirca).
S N
ORO MARCAPUNTA

SMELTER COLQUIJIRCA

GEOLOGICAL UNITS
100 m

200 m Dacite diatreme-dome complex (Miocene)

Calera Formation (E ocene), mainly limestones and marls

Shuco Member (E ocene), calcareous conglomerates

Mitu Group (Permian-T riasssic), sandstones

MINERALIZATION
Cordilleran ores A u-(A g) disseminated ores
Cu-(A u-A g) zone Quartz-alunite + vuggy silica
containing A u-bearing veinlets
Zn-Pb-Cu-(A g-B i) zone

Zn-Pb-(A g) zone

Figure 2e.1

complex (Oro Marcapunta prospect) and polymetallic Cordilleran deposits north of the volcanic complex (Smelter and Colqui-
2a.2. The figure shows the two mineralization types: disseminated Au-(Ag) bodies in the central part of the Marcapunta volcanic
Figure 2e.1. Geological north-south longitudinal section of the northern part of the Colquijirca district as shown in Figure
CHAPTER 2
 CHAPTER 2

A B
Quartz-
alunite-
pyrite

Enargite
1 cm -covellite 1 cm Quartz-alunite-pyrite

Figure 2e.2. Photographs of drill cores showing superimposition of Cordilleran mineralization on Au-bearing quartz-alu-
nite-sulfides assemblages from the Oro Marcapunta disseminated Au-(Ag) prospect. Cores correspond to the Marcapunta Oeste
project located immediately south-east of the Smelter deposit. Mine data show that sulfide-rich veinlets in photograph A and
sulfide-rich disseminations in B contains typical Ag/Au ratios of Cordilleran mineralization (between 40 and 60) in comparison
with quartz-alunite-sulfide portions of the rock which yield Ag/Au ratios significantly lower (between 5 and 20).

epithermal Au-(Ag) prospect, displays, at the most,
5-8 volume % sulfides, even in the highly porous
vuggy silica bodies formed during the Early barren
stage. In contrast, vuggy silica of the Smelter (and
also Colquijirca) Cordilleran deposits formed during
the Main ore stage (Chapter 2a), contain between 20
and 30 volume % sulfides, basically pyrite-(enargite).
Texturally, voids of vuggy silica formed during the
Gold stage at Oro Marcapunta, look virtually empty,
while voids of vuggy silica of the Main ore stage at
Smelter are largely filled with sulfides.
The approximate sulfide content of a given
representative hand sample of a Cordilleran ore
contain, in average 15-30 volume % of basically
pyrite from the Early silica-pyrite stage, 5-10 volume
% of enargite-pyrite from the Main ore stage and
variable amounts of sulfides (from nearly 0 to as high
as 10 volume %), mainly chalcocite, from the Late
ore stage.
On the other hand, in rare cases, disseminated
Au-(Ag) ores at Oro Marcapunta were originally
sulfide-rich. Now completely oxidized, as described
in Chapter 3c, they consist of veinlets, and narrow
veins containing nearly massive oxides, which are
typical remnant of sulfide-rich fabrics, likely >20
% in volume of sulfides. The absence of a copper
supergene enrichment zone suggests that the main
sulfide was pyrite. Such sulfide-rich veins are,
however, local and non representative of the bulk of
disseminated epithermal Au-(Ag) deposition.
Opaline
surface may be vaguely inferred. This is not the case
silica where a strong ore zoning,
of the Cordilleran deposits
particularly evident at Colquijirca but also present at
Smelter and San Gregorio, is recognized. Indeed,
zoning is a fundamental characteristic that distinguish
Cordilleran ores from other mineralization classes of
the porphyry-related family.
Economical metal suite
The economical metal suite is the third major
distinctive of each type of mineralization. Whereas at
Oro Marcapunta the metal suite is simple, consisting
invariably of Au-(Ag), in the Cordilleran deposits, the
main suite is variably polymetallic, mainly base metals
(Cu-Zn-PbBi) accompanied by appreciable amounts
of Au and/or Ag. The polymetallic character is weakly
recognized in enargite-rich internal parts, which are
always accompanied by significant amounts of Au-
(Ag) and, in some places, of Sn. Other internal zones,
as well as intermediate zones, carry copper mainly
as chalcocite and chalcopyrite and are commonly
associated with high values of Ag-Bi and Zn-Pb-Ag-
(Bi), respectively. The most external parts are clearly
polymetallic as that they are currently mined for Zn-
Ag-Pb.
Maximum depth of formation

As mentioned before, although generally

Strong ore zoning
As described in Chapter 2c, disseminated
epithermal Au-(Ag) bodies show no evident ore
zoning. Only a subtle increase in silver toward the
both ore types formed at very high levels, within a
few of hundreds of meters depth, the Cordilleran
ores are observed to persist considerably deeper
than disseminated Au-(Ag) bodies. As exemplified
in Figure 2e.1, Au-(Ag) disseminated bodies are

119

emplaced from surface to a maximum depth of 320
m (4200 m.a.s.l., DDH-SD11). Below this level, only
pyritic veinlets associated with sericitic alteration
and lacking advanced argillic alteration minerals are
observed (Chapter 2c).
The Smelter and Colquijirca Cordilleran bodies
are similarly shallowly emplaced, largely between
4400 and 4200 m.a.s.l.. However, relatively deep
drilling shows that these bodies root into enargite-
rich veins. The, so far, deepest hole Brocal-524
intersected enargite-rich veins at 3750 m.a.s.l. (Figure
2e.1), with mineralogical assemblages, in essence,
identical to the bulk of the internal parts of the
shallower Cordilleran mantos and veins of Smelter
and Colquijirca, including the presence of abundant
alunite.
Decreasing vs. increasing oxidation state
Different paths in the fluctuation of oxidation
state of the hydrothermal evolution is another
major difference between both mineralization types.
Disseminated Au-(Ag) epithermal mineralization
show a decrease in the oxidation state as suggested
by the change of the pH-indicative alteration and
gangue accompanying assemblages from mainly
quartz-alunitezunyite in the first hydrothermal
stage (Early barren stage) to mainly quartz-sericite
accompanying the later gold-bearing veinlets (Gold
stage).
In contrast, the Cordilleran hydrothermal
activity at Smelter (and presumably also at Colquijirca)
recorded by the accompanying gangue mineral
assemblages indicate that the oxidation state increased
with time and then during the retrograde history
decreased. During the Early silica-pyrite stage, the
associated alteration assemblage was sericite-quartz,
whereas the later Main ore stage records higher
oxidation states through the assemblage quartz-
alunitezunyite. A reverse path is recorded during the
latest observed ore stage of the Cordilleran deposits,
the Late ore stage, of which, the accompanying
mineral sericite suggest a drop in the oxidation state.
Similar contrasting fluctuations of the
sulfidation state of the fluids probably existed in
both mineralization types. However the lack of a
well defined sulfide mineralogical characterization at
Oro Marcapunta does not allow to reconstruct the
sulfidation paths in this deposit and compare them
with those observed in the Cordilleran deposits.
Crosscutting relationships
Direct crosscutting relationships between
precious metal mineralization at Oro Marcapunta and
Cordilleran ores in the northern block of the district
at Smelter and Colquijirca are difficult to recognize.
As described in some detail in Chapter 2c,
120
CHAPTER 2
drill hole Brocal-524 cut an interval of nearly 300
m. of phyllic to propylitic alteration which, together
with other intersections, seems to configure a nearly
vertical halo of the Au-(Ag)-bearing vuggy silica
zones at Oro Marcapunta, in the central portion
of the volcanic complex. The lower section of
this interval, in volcanic rocks, between 450 and
500 m depth, is overprinted (cut and replaced) by
strong quartz-alunite alteration as haloes of pyrite-
(enargite)-rich veinlets, in part silicified, characteristic
of Cordilleran mineralization in volcanic rocks of
the Smelter deposit. Under the microscope, sericite
is replaced by alunite, but it survives in places as
isolated grains, even at <5 cm of the pyrite-(enargite)
cores. Holes located more to the north that cut also
volcanic rocks, failed to encounter the phyllic to
propylitic alteration zone, suggesting that Brocal-524
would have intersected the outermost halo of the
disseminated Au-(Ag) mineralization.
Recent exploration at Marcapunta Oeste
has confirmed the late timing of Cordilleran
mineralization relative to the disseminated epithermal
Au-(Ag) ores. In the easternmost portion of the
Marcapunta Oeste project, Cordilleran veins cut the
precious metal veinlets and veins (Figure 2a.2). Drill
holes (e.g., CMO3-444) have encountered up to 350
m of vertical extension containing Au-(Ag) ledges
from the precious metal event at Oro Marcapunta,
which in the lowermost 50 m are superimposed by
Cordilleran ores. The most widespread example
consists of early barren stage quartz-alunite zones,
containing Au-(Ag) veinlets, being cut by centimeter-
wide pyrite-(enargite)-rich veinlets and less frequently
veins. Furthermore, intervals of vuggy silica display
phenocrysts containing intergranular infillings of
enargite of the Cordilleran stage which in part
destroy earlier Au-(Ag) veinlets bearing quartz-
alunite assemblage. It is also interesting to note that
chalcocite, presumably the western expression of
the Late ore stage of the Smelter deposit, occurs
as infillings in voids of vuggy silica of epithermal
precious metal mineralization.
 CHAPTER 3

Chapter 3
3A. Relative age of Cordilleranbase metal lode
and replacement deposits and high sulfidation
Au-(Ag) epithermal mineralization in the
Colquijirca mining district, central Peru
Ronner Bendez
Section des Sciences de la Terre, Universit de Genve, Switzerland
Sociedad Minera El Brocal S. A., Lima Peru

Llus Fontbot

Section des Sciences de la Terre, Universit de Genve, Switzerland

Mike Cosca
Institut de Minralogie et Ptrographie, Universit de Lausanne, Switzerland

e-mail: Ronner.Bendezu@terre.unige.ch
Telf. + 41 22 702 6645
Fax + 41 22 320 5732

Key words:

Epithermal, alunite, 40Ar/39Ar geochronology, Cordilleran, high sulfidation

Abstract
At Colquijirca, central Peru, a predominantly dacitic Miocene diatreme-dome complex (12.4 to 12.7 Ma
40
Ar/39Ar biotite ages) is spatially related to two distinct mineralization types. Disseminated Au-(Ag) associated
with advanced argillic alteration and local vuggy silica typical of high sulfidation epithermal ores are hosted
exclusively within the volcanic center at Marcapunta. A second economically more important mineralization
type, is characterized as Cordilleran base metal lode and replacement deposits. These ores are hosted in
Mesozoic and Cenozoic carbonate rocks surrounding the diatreme-dome complex and are zoned outward
from pyrite-enargite-quartz-alunite to pyrite-chalcopyrite-dickite-kaolinite to pyrite-sphalerite-galena-kaolinite-
siderite.
Alunite samples related to the Au-(Ag) epithermal ores have been dated by the 40Ar/39Ar method at
11.3-11.6 Ma and those from the Cordilleran base metal ores in the northern part of the district (Smelter and
Colquijirca) at 10.6-10.8 Ma. The significant time gap (~0.5 My) between the ages of the two mineralization
types in the Colquijirca district indicates they were formed by different hydrothermal events within the same
magmatic cycle.
The estimated time interval between the younger mineralization event (base metal mineralization) at
~10.6 Ma and the ages of ~12.5 Ma obtained on biotites from unmineralized dacitic domes flanking the
vicinity of the diatreme vent suggest a minimum duration of the magmatic-hydrothermal cycle in the district
of around 2 My.
This study on the Colquijirca district offers for the first time precise absolute ages indicating that
Cordilleran base metal lode and replacement deposits are formed by a late hydrothermal event in an intrusive-
related district, in this case post Au-(Ag) high sulfidation epithermal mineralization.

This chapter 3A is published in Mineralium Deposita (2003) 38: 683694

121

Introduction
Einaudi (1977, 1982, 1994) points out that
some sulfide-rich polymetallic ores form late in the
evolution of porphyry-related hydrothermal systems.
He noted that in certain systems these ores are well
developed (e. g., Yauricocha and Cerro de Pasco,
Peru and Bisbee, Arizona), whereas in others they are
only incipient or even barren (e. g., Ely, Nevada and
El Salvador, Chile respectively). Irrespective of the
degree of development, he refers to this late stage as
the lode stage and to the ores, if they are formed,
as Cordilleran base metal lode deposits. In order to
better integrate the frequent massive development of
replacements in carbonate rocks, as is the case of the
Colquijirca district, we extend here this denomination
to Cordilleran base metal lode and replacement
deposits.
The main characteristics of deposits formed
by this late Cordilleran stage include the following
(e.g., Einaudi, 1982): (i) high sulfidation and oxidation
states of the mineral assemblage with associated
advanced argillic to sericitic alteration, (ii) massive
texture and sulfide content of lodes up to more than
50 % in volume, considerably higher than in other
porphyry-related mineralization types, (iii) and a
common suite of economically interesting metals,
mainly Cu-Zn-Pb(Ag-Au).
Multi-disciplinary research over the past three
decades on epithermal deposits and their active
equivalents in volcanic arcs has helped decipher many
of the formation mechanisms of the Au-(Ag) high
sulfidation epithermal deposits (e.g., Hedenquist,
1987; Stoffregen, 1987). Recently their genetic links
with porphyry copper-gold deposits have been
supported (Hedenquist et al., 1998, Muntean and
Einaudi, 2001).
A review of existing literature shows that most
of the detailed studies on Cordilleran base metal
deposits were on deposits not spatially linked to the
presumed parental porphyry copper mineralization or
to any other recognizable ore forming environment.
This reflects the infrequent occurrence of Cordilleran
base metal lode and replacement deposits and
contemporaneous igneous activity, as was already
discussed by Guilbert and Park (1986, p. 465).
The Colquijirca District offers the rare
opportunity to study Cordilleran base metal lode and
replacement deposits closely related in space with
Au-(Ag) high sulfidation epithermal mineralization
produced within a Miocene diatreme-dome volcanic
complex. In this contribution we establish through
40
Ar/39Ar dating of hydrothermal alunite and
magmatic biotite, the timing of mineralization of
these two ore types and their relationship to the
magmato-volcanic activity in the district.
122
CHAPTER 3
Geologic setting and mineralization
The Colquijirca district is located 8-16 km
south of the world famous Cerro de Pasco mine
(Fig. 1). It contains one of the largest concentrations
of massive polymetallic ores within the Miocene
metallogenic belt of central and northern Peru (Vidal
et al., 1997), where numerous other Cordilleran base
metal lode and replacement deposits occur (e.g.,
Petersen, 1965; Einaudi, 1977, 1982, 1994; Guilbert
and Park, 1986; Bartos, 1988). Indeed, from a
metallogenetic point of view, the Colquijirca district
is part of a larger belt that also comprises the giant
ore concentrations of Cerro de Pasco. Spatially linked
with the ores, magmatism in the Colquijirca-Cerro
de Pasco districts is manifested through explosive
calc-alkalic volcanism of intermediate composition,
particularly as diatreme complexes accompanied by
subsequent multiple intrusion of porphyritic domes
(e. g., Bowditch, 1935; Lacy, 1952). The diatreme-
dome complexes of Cerro de Pasco, Yanamate and
Colquijirca (Fig. 1; e.g., Angeles, 1993, 1999; Sillitoe,
2000) intrude thick sequences of carbonate rocks
which host most of the ores.
The Colquijirca Mining district
In the center of the Colquijirca district, the
Marcapunta diatreme-dome complex intrudes an
Eocene sequence more than 300 m thick of folded
carbonate rocks, continental limestones, marls, and
detrital sediments (Pocobamba Formation) to the
north, and Triassic-Jurassic marine, nearly pure
limestones, and dolostones (Pucar Group) and
Permian red beds of the Mitu Group to the south
(Figs. 1, 2, 3). The sedimentary rocks around the
diatreme, including red beds of Permo-Triassic age
have subsided about 500 m into the diatreme neck
(Fig. 3).
Intense alteration, dominated by advanced
argillic and argillic alteration related to Au-(Ag)
epithermal mineralization is present in large parts
of the diatreme-dome complex (Figs. 2, 3). Mixtures
of quartz-alunite-dickite-kaolinite (zunyite,
pyrophyllite, illite) occur within or immediately
surrounding mineralized areas and kaolinite-illite
(smectite)-sericite-chlorite-calcite occur in weakly
mineralized or barren areas.
Au-(Ag) high sulfidation epithermal
mineralization is hosted within oxidized shallowly
emplaced vuggy silica bodies (Fig. 3) with vertical
dimensions of up to 100 m and gold values around 1
to 2 ppm (Vidal et al, 1997). Tonnage of the resources
are not known. The bodies have been recognized
mainly in the central portion of the complex,
mostly within the diatreme breccia and pyroclastic
infill. The morphology apparently is controlled by
both lithological and structural permeability. Less
abundant gold-bearing zones of completely oxidized

Ecuador
Colombia
Peru Brasil
Area of
geological map
Lima
Pacific Ocean
Bolivia
Chile
MINERALIZATION TYPE
Cu-Zn-Pb-(Ag-Au-Bi)
Cordilleran base metal deposits
Au-(Ag) volcanic-hosted high
sulfidation epithermal
GEOLOGICAL UNITS
Dacite diatreme-dome complex (Miocene)
Pocobamba Formation (Eocene),
mainly limestones and marls
Goyllarizquizga Group (Cretaceous),
sandstones
Pucara Group (Upper Triassic-
Lower Jurassic), limestones and dolostones
Mitu Group (Permian-Triasssic), sandstones
Excelsior Group (Devonian), phyllites
Figure 1: General geology and main mineralization types along the Miocene metallogenic belt at Cerro de Pasco and Colquijirca
districts. Geology compiled from Angeles (1999), Sociedad Minera El Brocal S. A. staff, and this study.
veinlets have been recognized, particularly toward
the surface. As in other high sulfidation epithermal
deposits (e. g., Summitville, Gray et al., 1994), deep
portions of unoxidized ores characteristically contain
less than 5 volume % of finely disseminated sulfides,
mainly pyrite-enargite and very minor sphalerite. The
original sulfide content of the oxidized veinlets is
estimated to be no more than 10 volume % .
Sulfide-rich polymetallic replacements
represent the other distinctive and economically most
important type of mineralization in the district. These
deposits aggregate of at least 150 Mt of carbonate-
hosted alunite, kaolinite-bearing Cu-Zn-Pb-Ag(Au-
Bi), in part massive, replacements (Ahlfeld, 1932;
Lindgren, 1935; McKinstry, 1936; Yaringao et al.,
1997; Vidal et al., 1997; Bendez, 1997; Fontbot and
Bendez, 1999, 2001; Bendez and Fontbot, 2002
CHAPTER 3
E-360 000 (7616' W)
3 Km
N
N-8820000 (1040' S)
Cerro de Pasco
Yanamate
Colquijirca
Smelter
Marcapunta
Fault
San Gregorio
Thrust and
reverse faults
area of Fig. 2
Fold axis
a, b, c). The sulfide-rich replacements include the
deposits of Colquijirca (30 Mt, at Zn+Pb~8 %) and
Smelter (50 Mt, at 2 % Cu) 3.5 km and 1.5 km north
of Marcapunta respectively and San Gregorio (70 Mt
at Zn+Pb~10 %) 3 km south of Marcapunta (Figs.
2, 3). Estimated temperatures from stabilities of
alteration assemblages range from around 300C close
to the diatreme-dome complex to 150C in external
portions of the system (Fontbot and Bendez,
2001). The sulfide-rich replacement ores at Smelter
and Colquijirca are hosted by Tertiary Pocobamba
Formation carbonate rocks and contain typically
between 25 and 50 volume % sulfides, mainly within
flat elongated mantos and irregular-shaped, stacked
orebodies developed from the external margins of
the diatreme vent into the carbonate rocks (Figs. 2,
3). Massive replacement characterizes these ores, but
123

open space filling and veins and breccias are locally
important. Exploration drilling indicates that the
bodies have their roots within the diatreme complex,
in deep subvertical narrow veins (from 500 m to
more than 750 m depth below the surface) composed
mainly of pyrite-enargite-quartz-alunite and minor
pyrophyllite (Fig. 2).
The sulfide-rich ores extend continuously
from Smelter for almost 4 km north to Colquijirca,
where they virtually attain the same shallow elevation
as the Au-(Ag) epithermal ores. Along its whole
extension, the mantos are zoned in all directions
from a core composed of pyrite-enargite-quartz-
alunite (luzonite, colusite, zunyite, barite; Zone I)
to the following main zones: pyrite-chalcopyrite-
dickite-kaolinite-siderite-quartz (tennantite, Bi-Ag
sulphosalts, bornite, alunite, barite, quartz; Zone
II), pyrite-sphalerite-galena-chalcopyrite-dickite-
kaolinite-quartz (siderite, hematite, magnetite,
alunite; Zone III), and the outermost known zone
of pyrite-galena-sphalerite-siderite (kaolinite,
dolomite, Zn-bearing carbonates; Zone IV) (Figs.
2, 3). A similar zoning is also present to the south
(Bendez, 1997; Fontbot and Bendez, 2001) where sample PBR-214 (Huacchuacaja, Fig. 2) comes from
bodies develop mainly into Lower Jurassic carbonate
rocks of the Pucar Group. This is also the host rock
of the recently discovered San Gregorio, one of the
largest known Zn-Pb deposits in Peru (> 70 Mt @
at Zn+Pb~10 %; Yaringao et al., 1997; Vidal et al.,
1997;).
Due to the absence of direct crosscutting
relationships between the Au-(Ag) epithermal and
sulfide-rich polymetallic mineralization types, it is
difficult to establish their relative timing. However,
in the eastern flank of the volcanic complex, thin
sphalerite-galena veins encased by argillic to phyllic
alteration haloes cut the external mostly propylitic
alteration zones peripheral to the vuggy silica-hosted
Au-(Ag) bodies. This perhaps represents the best field
relationship whereby it can be suggested that sulfide-
rich polymetallic ores were emplaced subsequent
to the Au-(Ag) epithermal mineralization. Other
observations in the northern flank of the volcanic
complex are consistent with this view, specifically
quartz-alunite selvages of the massive pyrite-enargite
bodies overprint and spatially, at deposit scale, overlap
the external argillic to phyllic to propylitic alteration
zones related to the Au-(Ag) mineralization.
Dated samples
In order to obtain quantitative data on the age
of igneous activity in the Colquijirca district and on
the timing of formation of the two mineralization
types recognized from field observations, we
conducted a 40Ar/39Ar study of three biotite samples
from fresh dacitic porphyry domes and seven
representative alunite-bearing ore samples. Three of
the alunite-bearing samples correspond to the Au-
124
CHAPTER 3
(Ag) epithermal bodies (Marcapunta) and four to
the sulfide-rich polymetallic replacements (Smelter
and Colquijirca). Because of the extremely fine
grained habit of alunite at San Gregorio (less than
20 m in length), attempts to concentrate sufficient
coarse-grained alunite grains for geochronology were
unsuccessful.
The three biotite samples correspond to three
unmineralized dacitic domes: PBR-148, PBR-215 and
PBR-216, and are located respectively one kilometer
north, some 0.7 kilometers west and 2.5 kilometers
northwest (Huacchuacaja) of the diatreme vent
(Figs. 2, 3). Rocks in these domes have a porphyritic
texture similar to those observed in the altered ones,
with large sanidine phenocrysts, smaller plagioclase,
resorbed quartz, minor biotite, and hornblende.
The microcrystalline groundmass is composed by
quartz, potassic feldspar, and plagioclase. Electron
microprobe analysis of biotite grains from sample
PBR-215 yield Fe/(Fe+Mg) molar ratios ranging
from 0.28 and 0.33.
In contrast to samples PBR-148 and PBR-215,
which apparently correspond to individual domes,
a fissure controlled, north-west aligned multiple
dome intrusion complex 1.3x0.25 km in horizontal
dimensions, with individual domes measuring less
than a hundred meters diameter. Thin sections from
samples PBR-148 and PBR-215 show biotite grains
which are slightly chloritized on the margins, although
no more than 2 and 5 volume %, respectively. In
addition, biotite grains in PBR-215 encapsulate
euhedral quartz representing up to 4 % of the total
volume.
The three alunite samples from the Au-(Ag) high
sulfidation epithermal bodies (PBR-198 and PBR-
214 from central Marcapunta and PBR-213 from two
kilometers south, Fig. 3) were extracted from altered
rocks that consist predominately of quartz-alunite
with minor zunyite, pyrite, and supergene minerals
such as goethite and hematite (Fig. 4a). As it is typical
for this mineralization type, dated alunite grains are
pink, euhedral, and dominantly potassic (8.3-8.7 wt.
% K20, Table 1).
Three of the four alunite-bearing samples
from the sulfide-rich polymetallic ores correspond
to zone I (samples PBR-131, PBR-137 from Smelter
and PBR-218 from Colquijirca, Fig. 2) and the fourth
is from zone III (sample PBR-108 from Colquijirca).
Alunite concentrates from zone I are virtually free of
inclusions. In accordance with the general composition
of alunite from this zone throughout the northern
part of the district, microprobe analyses reveal that
dated alunite samples from Smelter (PBR-131, PBR-
137) and Colquijirca (PBR-218 ) are more potassic
(9.0-10.5 % K2O, Table 1) than alunite samples from
the Au-(Ag) epithermal ores. Alunite from the base
metal ores is, in general, paragenetically earlier than
pyrite and enargite, although some alunite formed
after pyrite and enargite. This reversed crystallization
 CHAPTER 3

E-360 000
4300
Condorcayn

45 70

25

22 A

50 4448

46 COLQUIJIRCA
25 PBR-108
PBR-218 N-8 811 000
B
33
4458
N

35
4250
PBR-148 4200
C
C
PBR-216
SMELTER 500 m
85

Huacchuacaja PBR-137
60 GEOLOGICAL UNITS
4300

A
4336 PBR-131 Quaternary deposits

Mostly domes
and lavas Miocene
Marcapunta
4458 Mostly dacitic volcanic
26 pyroclastic complex
PBR-216 deposits
PBR-214 MARCAPUNTA
D Calera Member
limestones Lower
PBR-198 Pocobamba
Lachipana Shuco Formation
4150
Conglomerate

44
Pucar Group (Upper Triassic-Lower
E Jurassic), limestones and dolostones

?
Mitu Group (Permian-Triasssic),
sandstones

MINERALIZATION TYPES

Strike and dip of ? Au-(Ag) high sulfidation epithermal mineralization

sedimentary rocks PBR-214
Vuggy silica-quartz-alunite-dickite-kaolinite
Fault-strike slip (pyrophyllite-zunyite-illite)
F
Thrust and reverse faults
Cordilleran base metal replacement ores
Subsidence structure
(Normal fault) Enargite-pyrite-alunite (CuAu) in carbonate rocks.
? Cu>0.4 %, inner section more than 3 m thickness.
Open pit SAN GREGORIO
4179 Pyrite-calcopyrite-tennantite-bornite-dickite-kaolinite
Fold axis (alunite-Bi sulfosalts) in carbonates rocks. Cu>0.4 %,
4184 inner section more than3 m thickness.
Alunite samples from Cordilleran base Pyrite-sphalerite-galena-kaolinite-dickite(alunite-
metal replacement bodies
G siderite-ankerite-hematite) in carbonate rocks. Zn>2 %,
Alunite samples from Au-(Ag) inner section more than 3 m thickness.
high sulfidation epithermal mineralization

Biotite samples from fresh parts of

dacitic domes

Figure 2: Distribution of the principal mineralization types and alteration assemblages of the Colquijirca District as defined
during this study mainly by surface mapping and drill hole logging. Location of dated samples is given.

125
126
ages.
MARCAPUNTA

PBR-214, 11.290.12 My COLQUIJIRCA

SMELTER
PBR-198, 11.330.14 My PBR-215, 12.90.1 My
PBR-216, 12.70.1 My

PBR-131, 10.830.06 My PBR-218, 10.720.06 My PBR-108, 10.590.08 My

PBR-137, 10.560.08 My open pit

PBR-213, 11.630.08 My

Unconformity

Fault and subsidence structure PBR-148, 12.430.06 My

Hole Projected drill hole GEOLOGICAL UNITS MINERALIZATION TYPES

lower limit of intense oxidation
Quaternary deposits
Pyroclastic rocks
Au-(Ag) high sulfidation epithermal mineralization
Late Miocene-Pliocene?
Calcareous siltstones Vuggy silica-quartz-alunite-dickite-kaolinite
100 m Breccias and pyroclastic
(zunyite-pyrophyllite-illite)
rocks Miocene Marcapunta
200 m diatreme dome complex
Intrusives, mainly domes
Cordilleran base metal replacement ores
G Calera Member Eocene Pocobamba
Formation Pyrite-enargite-quartz-alunite(luzonite, colusite, zunyite
PBR-213, 11.630.08 My Shuco Member
barite; Zone I)
Pucar Group (Upper Triassic-Lower
Jurassic), limestones and dolostones
Mitu Group (Permian-Triasssic),
Pyrite-chalcopyrite-tennantite-bornite-Bi sulphosalts-
SAN GREGORIO
red beds dickite-kaolinite-siderite-quartz(alunite, barite,
? quartz; Zone II)
?40Ar/39Ar RADIOMETRIC AGES Pyrite-sphalerite-galena-chalcopyrite-dickite-kaolinite-
quartz(siderite, hematite, magnetite, alunite; Zone III),
Alunite ages from Cordilleran base metal replacement ores:
PBR-131, PBR-137, PBR-218 and PBR-108 and an outermost known zone of pyrite-galena-sphalerite
-siderite(kaolinite, dolomite, Zn-bearing carbonates;
Alunite ages from Au-(Ag) high sulfidation epithermal bodies:
PBR-213, PBR-198 and PBR-214 Zone IV).
Biotite ages from fresh parts of dacitic domes:
PBR-215, PBR-216 and PBR-148 Mainly as veins

section in Fig. 2). The section shows the main ore types, alteration assemblages, and location of samples with 40Ar/39Ar
CHAPTER 3

Figure 3: North-south longitudinal section of the Colquijirca district following the main recognized ore bodies (ABCDEFG
 CHAPTER 3

sequence and the intimate intergrowths of alunite Analytic procedure

and sulfides suggest that both are essentially coeval
(Fig. 4b, 4c).
In zone III, alunite and sulfides occur in intricate
intergrowth textures, and this is also evident in the
alunite-sphalerite-galena-bearing sample selected for
dating (PBR-108, Fig. 4d). Alunite from this sample
is colorless, euhedral and microscopically pure.
Microprobe analyses indicate that alunite from zone
III at Colquijirca ranges from 9.0 and 10.5 weight %
K2O. In comparison with alunites from zone I, the
PBR-108 alunite grains have in general considerably
higher F content and are slightly less sodic (Table 1).
Alunite and biotite grains were carefully
handpicked from previously crushed and washed
samples. Only grains of microscopically high purity
(< 2 volume % in of quartz/opaque contaminants)
were selected. The grain separates were additionally
treated by ultrasonic cleaning. Additional details
of the biotite and alunite samples, such as UTM
coordinates, average grain sizes, and sample amounts
are provided in Appendix 1.
Irradiation of mineral separates for 40Ar/
39
Ar analysis was carried out in the Triga reactor at
Oregon State University, USA. All mineral samples
were irradiated for 12 hours with the Fish Canyon
sanidine standard (28.02 Ma; Renne et al., 1998).
The 40Ar/39Ar analyses were done at the
University of Lausanne, Switzerland, using a low

Table 1: Representative electron microprobe composition of alunite from Au-(Ag) and base metal mineralization in the
Colquijirca district*
Au-(Ag) epithermal ores Cordilleran base metal replacement bodies
Zone I Zone I Zone I Zone III Zone III
Sample PBR-214 PBR-335 PBR-338 PBR-130 PBR-131 PBR-218 PBR-108 PBR-253

K 2O 8.34 8.60 8.31 9.40 9.30 10.48 9.66 10.28

Na2O 1.73 1.79 0.18 0.92 0.95 0.19 0.31 0.18
BaO 0.71 0.60 0.11 0.17 0.05 0.23 0.13 0.00
SrO 0.47 0.79 0.20 0.12 0.01 0.08 0.40 0.11
Al2O3 36.29 35.35 37.38 37.26 37.35 36.81 36.04 37.26
SO3 39.88 39.93 38.63 39.90 40.15 38.35 39.27 39.52
P2O5 0.39 0.43 0.54 0.06 0.12 0.00 0.38 0.26
H2O** 14.17 14.77 11.20 13.68 13.61 11.96 11.89 12.49
F -
0.33 0.21 2.15 0.36 0.63 0.97 2.48 1.31
Total 102.30 102.45 98.69 101.87 102.17 99.06 100.57 101.43

K 0.73 0.76 0.75 0.82 0.81 0.93 0.86 0.90

Na 0.23 0.24 0.02 0.12 0.12 0.03 0.04 0.02
Ba 0.02 0.02 0.00 0.00 0.00 0.01 0.00 0.00
Sr 0.02 0.03 0.01 0.00 0.00 0.00 0.02 0.00
A site 1.00 1.04 0.79 0.95 0.93 0.96 0.92 0.93

Al 2.94 2.88 3.13 3.00 3.00 3.02 2.98 3.02

R site 2.94 2.88 3.13 3.00 3.00 3.02 2.98 3.02

S 2.05 2.07 2.05 2.04 2.05 2.00 2.06 2.03

P 0.02 0.02 0.03 0.00 0.01 0.00 0.02 0.02

*. Alunites were analysed using a Cameca SX50 electron microprobe at the University of Lausanne.
Instrumental conditions were: accelerating voltage of 12 kV, beam current of 10 nA, and spot size of 15
m.
**. Weight % H2O calculated based on observed values of sulfur, phosphorous, potassium, sodium,
strontium,barium, and fluorine,+ and+alunite stoichiometry using the formula AR3(SO4)2(F, OH)6, in which
A refers to the large cations K , Na , Ba2+, and Sr2+, and R is Al3+

127
 CHAPTER 3

blank double vacuum resistance furnace and metal
extraction line connected to a MAP 215-50 mass
spectrometer using an electron multiplier. The
incrementally heated gas was expanded and purified
using activated Zr/Ti/Al getters and a metal cold
finger maintained at liquid nitrogen temperature.
Time zero regressions were fitted to data collected
from 8 scans over the mass range 40 to 36. Peak
heights above backgrounds were corrected for
mass discrimination, isotopic decay and interfering
nucleogenic Ca-, K- and Cl-derived isotopes of Ar.
Blanks were measured at temperature and subtracted
from the sample signal. For mass 40, blank values
ranged from 4x10-15 moles below 1350C to 9x10-
15
moles at 1650C. Blank values for masses 36-
39 were below 2x10-17 moles for all temperatures.
Isotopic production ratios for the Triga reactor were
determined from analysis of irradiated CaF2 and
K2SO4 and the following values have been used in the
calculations: 36Ar/37Ar(Ca)=0.00026400.0000017,
39
Ar/37Ar(Ca)=0.00067300.0000037, and 40Ar/
39
Ar(K)=0.000860.00023. A mass discrimination
correction of 1.008 amu was determined by online
measurement of air and was applied to the data. For
this investigation, an uncertainty on the neutron flux
(J) was determined with a precision of 0.5 percent,
and this uncertainty is propagated throughout the
uncertainties on the reported ages. All ages and
regressions in this paper are reported at the 95
percent level of confidence.
Results
The 40Ar/39Ar age spectra of the analyzed
samples are presented in Figure 4 and results of
the 40Ar/39Ar analyses are summarized in Figure 5.
Age plateaus were determined using the criteria of
Dalrymple and Lamphere (1971): the presence of at
least three contiguous incremental heating steps with
statistically indistinguishable ages and constituting
more than 50 percent of the total 39Ar released during
the experiment.
40Ar/39Ar data from magmatic biotite
Biotite sample PBR-148 provided a well
defined age plateau of 12.430.06 Ma (2) (Fig. 4).
The age is slightly older (but within 2 analytical

Table 2. Summary of 40
Ar/39Ar age data of the Colquijirca district
40/36 ratio

Plateau age Inverse isochron Isochron-derived of intercept

Sample Location Mineral (Ma2)1 age(Ma2)2 MSWD3 (2)

Dacitic domes

PBR-148 Northern Marcapunta Biotite 12.430.06 12.40.1 0.85 32222

PBR-215 Western Marcapunta Biotite 12.90.1 1.50 2902
PBR-216 Huacchuacaja Biotite 12.70.1 1.50 2702

Precious metal high sulfidation

epithermal ores

PBR-198 Central Marcapunta Alunite 11.330.14 11.40.1 4.60 2823

PBR-213 Southern Marcapunta Alunite 11.630.08 11.60.1 0.99 29129
PBR-214 Central Marcapunta Alunite 11.290.12 11.30.1 2.40 31940

Cordilleran base metal lode and

replacement bodies

PBR-108 Colquijirca Alunite 10.590.08 10.60.1 1.20 28937

PBR-131 Smelter Alunite 10.830.06 10.90.1 0.84 29110
PBR-137 Smelter Alunite 10.560.08 10.60.1 0.55 28724
PBR-218 Colquijirca Alunite 10.720.06 10.70.1 0.19 30713

Bold ages were selected for the interpretation discussed in the text
1
Plateau age calculated according to the criteria of Dalrymple and Lamphere (1971)
2
Age estimated by representing the temperature steps from the plateau or plateau-like segment on a
36
Ar/40Ar versus
39
Ar/40Ar plot
3
MSWD: mean square of weighted deviates. It can be calculated only for three or more points
128
 CHAPTER 3

Figure 4: Photomicrographs of some of the dated alunite-bearing ore samples showing their intergrown habits. Black scale bars
represent 100 m. A. Backscattered electron image of sample PBR-198 (Au-(Ag) high sulfidation epithermal ores) showing
tabular alunite intergrown with pyrite and quartz in a micro-cavity from vuggy silica. B. Photomicrograph in transmitted light
of sample PBR-131 (Cordilleran base metal ore from Smelter, zone I) showing the intimate association alunite-enargite. C.
Photomicrograph in reflected light of sample PBR-137 (Cordilleran base metal ore from Smelter, zone I). D. Polished section
image in reflected light of sample PBR-108 (Cordilleran base metal ore from Colquijirca, zone III) revealing intricate intergrowth
of alunite, galena and sphalerite.

uncertainties) than the age obtained previously on
biotite from the upper part of Marcapunta (11.90.8
Ma, 2; Vidal et al., 1984). Sample PBR-216 from a
Huacchuacaja dome (Fig. 2) gave a slightly disturbed
but generally flat apparent age spectrum whose initial
steps may reflect partial radiogenic Ar loss. The
inverse isochron age of sample PBR-216 at 12.70.1
Ma (MSWD of 1.5) is consistent with the PBR-148
age plateau (Table 2). Sample PBR-215, the least
pure of the three biotite samples (see above), does
not show any interpretable plateau-like segments. Its
inverse isochron age of 12.90.1 Ma derived with a
MSWD of 1.5 is, however, consistent with ages from
the other magmatic biotites.
Alunite 40Ar/39Ar data from Au-(Ag) epithermal
ores
All of the alunite samples related to the Au-(Ag)
mineralization (PBR-198, PBR-213 and PBR-214)
gave well defined age plateaus between 11.290.12
and 11.630.08 Ma (2) (Fig. 5). These ages are
slightly to significantly older than the 10.60.6 Ma
(2) K/Ar age obtained on an alunite sample from
the upper part of the Marcapunta volcanic complex
(Vidal et al., 1984). The age plateaus of 11.330.14
Ma and 11.290.12 Ma derived from samples PBR-
198 and PBR-214, respectively, are analytically
indistinguishable at the 2 confidence level. This may
indicate that in this part of the diatreme complex, close
to the diatreme vent, a single pulse of hydrothermal
activity generated the gold-bearing advanced argillic-
altered rocks. Alunite sample PBR-213 collected
two km south of the diatreme center (Figs. 2, 3)
yielded a flat age spectrum of multiple contiguous
steps defining an age plateau of 11.630.08 Ma (2).
This age is ~300,000 years older than the 40Ar/39Ar

129
 CHAPTER 3

16 16

14 14
Apparent age Ma 12 12

10 10

8 8
PBR-215 Biotite PBR-216 Biotite
6 6
Magmatic biotite from dacitic dome Magmatic biotite from dacitic dome
4 4

2 2

0 0
0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100

16 16
12.43 0.06
14 14
11.33 0.14
12 12
Apparent age Ma

10 10

8 8
PBR-148 Biotite PBR-198 Alunite
6 6
Magmatic biotite from dacitic dome Precious metal epithermal ores
4 4
0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100

16 16

14 14 11.29 0.06
11.63 0.08
12 12
Apparent age Ma

10 10

8 8
PBR-213 Alunite PBR-214 Alunite
6 6
Precious metal epithermal ores Precious metal epithermal ores
4 4
0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100

16 16

14 14
10.83 0.06
12 10.59 0.08 12
Apparent age Ma

10 10

8 8
PBR-108 Alunite
6 6 PBR-131 Alunite
Cordilleran base metal ores Cordilleran base metal ores
4 4

2 2

0 0
0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100

16 16

14 14

12 10.72 0.03 12 10.56 0.08

Apparent age Ma

10 10

8 8

6 PBR - 218 Alunite 6 PBR-137 Alunite

4 Cordilleran base metal ores 4 Cordilleran base metal ores
2 2
0 0
0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100
Cumulative %39Ar Released Cumulative %39Ar Released

Figure 5: 40Ar/39Ar age apparent age spectra from incremental heating analyses. Heating steps segments from which plateau
ages were calculated are shown in filled boxes

130

Middle Miocene
Cerro de Pasco district
on plagioclasea
on biotitea
K/Ar on plagioclasea
on biotitea
on sanidinea
Yanamate
on whole rock b
K/Ar
40Ar/39Ar, this study
15 14
Figure 6: Summary diagram of available geochronological data (K/Ar and 40Ar/39Ar) from the Colquijirca and Cerro
de Pasco districts: a, from Silberman and Noble (1977) at 2; b, from Soler and Bonhomme (1988) at 2; c, from Vidal et al.
(1984) at 2; d, Bendez et al. (this study) at 2 level of confidence.
age plateaus of PBR-198 and PBR-214 (between
80,000 and 540,000 years, considering 2). Such a
time gap indicates that high sulfidation fluids in this
southern part of the district were generated from a
hydrothermal pulse prior to the pulse at 11.3 Ma.
Alunite 40Ar/39Ar data from the sulfide-rich
polymetallic ores
As is the case for the Au-(Ag) epithermal
ores, the four alunite samples from the sulfide-rich
polymetallic ores yielded clear age plateaus ranging
between 10.830.06 and 10.560.08 Ma (2). These
new data are consistent with a previous K/Ar age
reported by Vidal et al. (1984) on an alunite sample
collected from massive enargite-pyrite ores (southern
Smelter) referred to here as zone I. No relation
between position (ore zone I or III) and age plateau
is recognized. Sample PBR-108 from Colquijirca
(zone III) gave an age plateau of 10.590.08 Ma
(2), analytically identical to sample PBR-137 from
Smelter (zone I) at 10.560.08 Ma (2). In this same
zone I age plateau have been obtained at 10.720.06
Ma (sample PBR-218) and at 10.830.06 Ma (sample
PBR-131). These ages argue for a protracted history
of hydrothermal activity that formed the Cordilleran
base metal ores through one or more pulses. On the
basis of the 40Ar/39Ar ages, the duration of this event
can be estimated to be ~0.27 My (0.13 to as much as
0.41 My considering 2).
CHAPTER 3
Late Miocene
Colquijirca district
on biotitec
on sanidinec
on alunitec
on alunitec
on magmatic biotited
on alunited
volcanic complex
formation
on alunited
Au-(Ag) high sulfidation
epithermal mineralization
Cordilleran base
metal lode and
replacement
mineralization
13 12 11 10
Age (Ma)
Discussion and conclusions
Volcanic and hydrothermal activity in the
Colquijirca district (between ~12.7 and 10.6 Ma)
took place two million years later than at the Cerro de
Pasco district (Fig. 6). At Cerro de Pasco, K/Ar ages
obtained on biotite, sanidine, and plagioclase indicate
that the volcanic and hydrothermal activity occurred
between 14-15(0.8-1.0) Ma at 2 (Silberman and
Noble, 1977). Similarly, one whole rock K/Ar analysis
from the nearby Yanamate diatreme-dome complex
(Fig. 1) gave an age of 15.20.8 Ma at 2 (Soler and
Bonhomme, 1988), which is more than two million
years earlier than magmatic ages obtained in the
Colquijirca district. On the basis of these available
geochronological data it is concluded that Colquijirca
represents the youngest expression of the Miocene
magmatism in the region.
The 40Ar/39Ar determinations on mineralization
in the Colquijirca district reveal that the two physically
separate ore types (Figs. 2, 3), Au-(Ag) disseminated
and the Cu-Zn-Pb-Ag-(Au-Bi) sulfide-rich ores,
formed at different times with a difference in age of
~0.5 My (0.28-0.64 My at the 2 level of confidence).
Such a long time gap possibly indicates that both ore
types deposited from different hydrothermal events
yet within the same magmatic cycle.
The older event is recognized through possibly
two pulses of advanced argillic alteration formation
at ~11.3 Ma and ~11.6 Ma. Typical disseminated Au-
(Ag) epithermal mineralization is related to this older
131

event in areas affected by vuggy silica alteration in
volcanic rocks of the Marcapunta diatreme-dome
complex.
During a second event (10.8-10.6 Ma),
sulfide-rich polymetallic mineralization formed
subhorizontal flat elongated tube-like lenses replacing
Eocene carbonate beds from the northern border of
the Marcapunta diatreme dome complex for 4 km
north. This mineralization has a definite zoning that
from internal to external parts displays the three
following general main assemblages:
- Cu-(Au) in enargite-pyrite ores, with alunite,
zunyite and/or dickite-kaolinite (zone I)
- Cu-(Ag-Bi) as chalcopyrite (tennantite-
bornite-Bi sulfosalts) with alunite-dickite-kaolinite
(zone II)
- Zn-Pb-(Ag) as sphalerite-galena with
kaolinitealunite, siderite (zone III)
The alunite 40Ar/39Ar ages from zones I and
III show that the sulfide-rich base metal ore types are
contemporaneous within errors. The geochronologic
data confirm the geometric observations suggesting
that the massive pyrite-enargite Cu-(Au) ores of
Smelter and the Colquijirca (mainly Zn-Pb-(Ag)
deposits) are parts of a continuous replacement
(Figs. 2, 3).
The recognized features of the sulfide-rich
polymetallic replacement ores, including mineral
zoning, the high sulfidation and oxidation states of
the sulfide assemblages in the internal parts, associated
advanced argillic alteration, and the late timing of
formation characterize them as Cordilleran lode and
replacement deposits in the sense of Einaudi (e.g.,
1982, 1994).
The Pucar-hosted San Gregorio deposit,
for which age determinations are not yet available, is
considered to be a low temperature and more acidic
and oxidizing equivalent of the sphalerite-galena-
bearing zones encountered in the northern part of
the district (Fontbot and Bendez, 2001).
From the current knowledge on the lifespan of
a single intrusion-related hydrothermal system (e. g.,
<50,000 years, Marsh et al., 1997; Henry et al., 1997;
Muntean and Einaudi, 2001), the period of activity
of the two mineralization events, Au-(Ag) (~340,000
years) and sulfide-rich polymetallic (~270,000 years)
are apparently representative of relatively long-lived
hydrothermal processes.
Multiple pulses of shallow intrusions are
identified at Colquijirca where several swarms of
porphyrytic dome intrusions, several a few hundred
meters long, are present around the diatreme neck
at Marcapunta. All which have been dated in this
study are several hundred thousand years older than
recognized hydrothermal processes.
If we consider that dome intrusions occurred
as early as 12.7 Ma and that the hydrothermal system
deposited ores as late as ~10.6 Ma (PBR-137) the
simplest conclusion is to assume that magmatic-
hydrothermal activity was active for a minimum
132
CHAPTER 3
period of 2 My. Intermediate ages within this
interval such as the earliest recognized hydrothermal
pulse at ~11.6 Ma (vuggy silica formation in
southern Marcapunta) and the earliest dated dome at
~12.4 Ma, (PBR-148) argue for this possibility. Two
million years of inferred magmatic activity represents
an interval of time long enough for the development
of a complex evolutionary history involving several
thermal and/or magmato-volcanic episodes related
to a single, fairly large magma chamber. Considering
the present results, the most plausible scenario for
the Colquijirca district is that the two recognized
hydrothermal events were linked to at least two
major thermal episodes within the same magmatic
cycle (Bendez and Fontbot, 2002).
In the Colquijirca district, the relative sequence
of events and the absolute ages obtained establish
for the first time that Cordilleran base metal lode and
replacements ores, mainly epithermal and formed at
high sulfidation and oxidations states, were emplaced
considerably later (~460,000 years) than the Au-(Ag)
high sulfidation epithermal mineralization, yet, both
mineralization types formed from fluids with high
sulfidation and oxidation states.
Acknowlegements
The present investigation is being carried out
with the support of the Sociedad Minera El Brocal
S.A. and the Swiss National Science Foundation (FN
2000-062000.00). We acknowledge also the great help
provided by the company geologists especially in the
early period of this investigation, in particular Juan
Proao, Carlos Yacila, Ivan Monteagudo, Mximo
Yaringao, and Lucio Canchis. Constructive reviews
and comments by Lewis Gustafson, John Dilles,
and an anonymous reviewer significantly improved
the manuscript. We wish to thank also the editorial
effort first by Richard Goldfard and finally by Larry
Meinert, this last who contributed in addition with
helpful comments and suggestions.
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Appendix 1. Additional details of analyzed samples of the Colquijirca district

UTM coordinates/drill hole grain size sample

Mineral Area/Deposit Ore grades2
Sample (DH), depth (m) (m) amount1

PBR-148 Biotite Northern Marcapunta DH:CM3-612 39 200-800 18.4 fresh

PBR-215 Biotite Western Marcapunta N-8809986 E-360020 250-500 10.9 fresh
PBR-216 Biotite Huacchuacaja N-8809626 E-358353 200-1000 14.5 fresh

Au-(Ag) high sulfidation epithermal ores

PBR-198 Alunite Central Marcapunta N-8808526 E-360850 150-400 10.5 0.1, 9, n.s3., n.s., n.s.
PBR-213 Alunite Southern Marcapunta N-8806020 E-359949 200-800 6.8 n.s., 9, n.s., n.s., n.s.
PBR-214 Alunite Central Marcapunta N-8808287 E-360811 150-400 11.2 0.2, 12, n.s., n.s., n.s.

Cordilleran base metal lode and replacement bodies

PBR-108 Alunite Colquijirca N-8811135 E-360915 80-300 10.7 n.a.4, 112, n.s., 8.2, 3.1
PBR-131 Alunite Smelter DH:CM9-548 247.3 150-600 12.4 0.7, 38, 3.6, n.s., n.s.
PBR-137 Alunite Smelter DH:CM5-580 110.4 250-600 12.8 n.s., 9, n.s., n.s., n.s.
PBR-218 Alunite Colquijirca N-8811122 E-360892 250-600 11.3 n.s., 14, 0.3, n.s., n.s.
1. in mg before irradiation.
2. ppm Au, ppm Ag, % Cu, % Zn, % Pb, respectively
3. n.s. Not significant, less than 0.1
4. n.a. Not analized

134
 CHAPTER 3

Appendix 2. Argon release data for magmatic biotite and hydrothermal alunite samples from the Colquijirca District
T (C) Ca/K 36
Ar/39Ar Ar*/39Ar
40 40
Ar(x10-14) 39
Ar(x10-14) %40Ar* Age (Ma) 2
(mole) (mole)

800 10.067 0.137 2.348 6.8 0.2 5.5 6.5 3.6

825 4.735 0.100 4.276 7.4 0.2 12.7 11.8 2.6
850 2.745 0.081 4.460 8.8 0.3 15.7 12.3 2.0
875 1.786 0.060 4.127 9.2 0.4 18.9 11.4 1.4
900 0.824 0.038 4.256 9.3 0.6 27.4 11.8 1.2
925 0.413 0.022 4.647 9.0 0.8 41.2 12.9 1.0
950 0.296 0.014 4.606 8.3 1.0 53.4 12.8 0.8
975 0.268 0.010 4.444 7.3 1.0 61.2 12.3 0.8
1000 0.246 0.009 4.511 6.5 0.9 63.1 12.5 0.8
1025 0.190 0.011 4.528 6.4 0.8 58.7 12.5 1.0
1050 0.133 0.013 4.608 6.3 0.8 55.2 12.8 1.0
1075 0.081 0.014 4.630 6.7 0.8 52.4 12.8 1.0
1100 0.143 0.012 4.858 6.5 0.8 58.0 13.4 1.0
1150 0.029 0.008 4.651 8.5 1.2 65.0 12.9 0.8
1300 0.000 0.004 4.649 39.0 6.5 78.0 12.9 0.8
1549 0.022 0.002 4.449 89.8 17.6 87.4 12.3 0.8
PBR-215 Biotite, J = 0.00154, wt.= 10.9 mg
Integrated total fusion age = 12.47 Ma
No age plateau

T (C) Ca/K 36
Ar/39Ar Ar*/39Ar
40 40
Ar(x10-14) 39
Ar(x10-14) %40Ar* Age (Ma) 2
(mole) (mole)

775 10.899 0.098 1.743 5.6 0.2 5.8 4.8 2.8

800 6.123 0.079 2.838 6.2 0.2 10.9 7.8 2.2
825 3.489 0.064 3.157 7.0 0.3 14.4 8.7 1.6
850 2.137 0.047 3.899 6.2 0.4 21.9 10.7 1.4
875 0.980 0.034 3.799 8.6 0.6 27.4 10.5 1.0
900 0.536 0.023 4.116 8.5 0.8 37.4 11.3 1.0
925 0.259 0.015 4.070 9.1 1.1 48.0 11.2 0.8
950 0.111 0.010 4.284 9.3 1.3 59.8 11.8 0.8
975 0.079 0.007 4.470 9.3 1.5 69.8 12.3 0.8
1000 0.079 0.005 4.465 8.8 1.5 74.5 12.3 0.8
1020 0.081 0.005 4.427 8.4 1.4 75.7 12.2 0.8
1040 0.082 0.004 4.466 7.8 1.4 77.8 12.3 0.8
1007 0.254 0.004 4.265 2.8 0.5 79.7 11.7 1.0
1080 0.002 0.004 4.566 9.3 1.6 79.0 12.6 0.8
1100 0.030 0.004 4.564 7.3 1.3 80.7 12.6 0.8
1120 0.032 0.003 4.557 6.3 1.1 82.3 12.5 0.8
1140 0.048 0.003 4.546 5.8 1.1 83.1 12.5 0.8
1160 0.000 0.003 4.632 5.5 1.0 85.1 12.7 0.8
1180 0.001 0.004 4.614 6.0 1.1 81.2 12.7 0.8
1200 0.000 0.004 4.661 6.8 1.2 79.8 12.8 0.8
1250 0.000 0.005 4.558 14.2 2.4 76.6 12.5 0.8
1300 0.000 0.005 4.535 16.0 2.7 75.9 12.5 0.8
1549 0.052 0.003 4.390 126.7 24.2 83.8 12.1 0.8
PBR-216 Biotite, J = 0.00153, wt.= 14.5 mg
Integrated total fusion age = 12.09 Ma
No age plateau

135
 CHAPTER 3

Appendix 2. (cont.) Argon release data for magmatic biotite and hydrothermal alunite samples from the Colquijirca District

T (C) Ca/K 36
Ar/39Ar 40
Ar*/39Ar 40
Ar(x10-14) 39
Ar(x10-14) %40Ar* Age (Ma) 2
(mole) (mole)
750 9.496 0.087 4.318 5.8 0.2 14.6 11.9 2.8
775 3.728 0.033 4.461 4.1 0.3 31.7 12.3 1.6
800 1.723 0.014 4.416 4.3 0.5 52.6 12.1 1.2
825 0.881 0.006 4.750 5.7 0.9 72.9 13.1 1.0
850 0.507 0.005 4.447 7.3 1.3 76.3 12.2 0.8
875 0.406 0.003 4.520 6.9 1.3 83.1 12.4 0.8
900 0.390 0.003 4.646 6.2 1.2 86.3 12.8 0.8
925 0.318 0.002 4.639 6.2 1.2 86.6 12.8 0.8
950 0.226 0.002 4.479 6.8 1.3 86.4 12.3 0.8
975 0.146 0.001 4.599 8.2 1.6 91.5 12.7 0.8
1000 0.085 0.001 4.591 11.1 2.3 93.6 12.6 0.8
1025 0.066 0.001 4.503 14.7 3.1 94.1 12.4 0.8
1050 0.016 0.001 4.502 19.6 4.1 95.2 12.4 0.8
1075 0.009 0.001 4.523 29.2 6.1 95.2 12.4 0.8
1100 0.014 0.001 4.515 51.4 10.8 94.6 12.4 0.8
1150 0.076 0.001 4.516 74.5 15.3 93.2 12.4 0.8
1300 0.079 0.001 4.544 28.0 5.9 95.0 12.5 0.8
1549 4.481 0.116 8.810 3.2 0.1 20.5 24.2 15.8
PBR-148 Biotite, J=0.00153, wt.= 18.7 mg
Integrated total fusion age = 12.46 Ma
Plateau age (1050-1549C) = 12.43 0.06 Ma

T (C) Ca/K 36
Ar/39Ar 40
Ar*/39Ar 40
Ar(x10-14) 39
Ar(x10-14) %40Ar* Age (Ma) 2
(mole) (mole)
650 17.590 0.094 3.115 8.1 0.3 10.3 8.2 2.4
700 6.731 0.017 4.248 3.7 0.4 46.7 11.2 1.2
720 2.410 0.011 4.094 6.5 0.9 56.3 10.8 0.8
740 0.922 0.007 4.101 13.5 2.2 65.7 10.8 0.8
760 0.280 0.005 4.349 19.6 3.4 75.4 11.5 0.8
780 0.121 0.004 4.240 29.6 5.4 77.6 11.2 0.8
800 0.056 0.001 4.295 30.7 6.7 93.6 11.4 0.8
PBR-198 Alunite, J=0.00147, wt.= 6.8 mg
Integrated total fusion age = 11.21 Ma
Plateau age (780-800C) = 11.33 0.14 Ma

T (C) Ca/K 36
Ar/39Ar 40
Ar*/39Ar 40
Ar(x10-14) 39
Ar(x10-14) %40Ar* Age (Ma) 2
(mole) (mole)
700 6.472 0.010 3.298 5.6 0.9 54.8 9.0 0.8
710 2.859 0.004 4.093 5.8 1.1 79.3 11.2 0.8
720 1.631 0.002 4.288 6.2 1.3 88.4 11.7 0.8
730 0.787 0.001 4.266 7.5 1.6 91.6 11.7 0.8
740 0.539 0.001 4.193 8.9 2.0 92.5 11.5 0.8
750 0.267 0.001 4.275 12.0 2.7 95.3 11.7 0.8
760 0.209 0.001 4.268 13.0 2.9 95.6 11.7 0.8
770 0.199 0.001 4.238 12.4 2.8 96.1 11.6 0.8
780 0.208 0.001 4.235 11.1 2.5 96.4 11.6 0.8
800 0.160 0.000 4.288 12.1 2.8 98.2 11.7 0.8
850 0.528 0.001 4.212 4.8 1.1 94.7 11.5 0.8
900 3.770 0.015 2.886 0.8 0.1 40.8 7.9 3.8
PBR-213 Alunite, J = 0.00152, wt.= 5.8 mg
Integrated total fusion age = 11.47 Ma
Plateau age (720-850C) = 11.63 0.08 Ma

136
 CHAPTER 3

Appendix 2. (cont.) Argon release data for magmatic biotite and hydrothermal alunite samples from the Colquijirca District
T (C) Ca/K 36
Ar/39Ar 40
Ar*/39Ar 40
Ar(x10-14) Ar(x10-14)
39
%40Ar* Age (Ma) 2
(mole) (mole)

700 12.253 0.007 4.382 2.5 0.4 72.5 11.5 1.2

710 4.794 0.005 4.300 3.5 0.6 75.8 11.3 1.0
720 2.639 0.005 3.988 3.8 0.7 74.2 10.5 0.8
730 1.309 0.002 4.331 5.4 1.1 88.8 11.4 0.8
740 0.736 0.000 4.576 6.7 1.4 97.6 12.0 0.8
750 0.441 0.001 4.260 10.5 2.3 94.3 11.2 0.8
760 0.241 0.000 4.270 14.7 3.3 97.0 11.2 0.8
770 0.182 0.000 4.321 15.0 3.4 97.7 11.3 0.8
780 0.097 -0.000 4.353 10.6 2.5 100.8 11.4 0.8
800 0.709 0.000 4.321 2.9 0.7 98.3 11.3 1.0
850 24.936 0.058 2.278 0.5 0.0 12.2 6.0 18.6
900 103.983 0.135 56.215 0.4 0.0 60.2 142.3 143.0
1000 64.793 0.300 7.539 0.6 0.0 7.9 19.7 146.0
PBR-214 Alunite, J = 0.00146, wt.= 6.3 mg
Integrated total fusion age = 11.36 Ma
Plateau age (770-1000C) = 11.29 0.12 Ma

T (C) Ca/K 36
Ar/39Ar 40
Ar*/39Ar 40
Ar(x10-14) 39
Ar(x10-14) %40Ar* Age (Ma) 2
(mole) (mole)

650 24.425 0.146 1.142 13.4 0.3 2.6 3.0 2.6

700 6.115 0.014 3.148 3.9 0.6 45.2 8.4 0.8
710 3.663 0.006 4.104 3.1 0.5 72.6 10.9 1.0
720 1.824 0.003 4.006 3.3 0.7 80.7 10.7 0.8
730 1.353 0.002 4.039 3.2 0.7 87.0 10.8 0.8
740 0.678 0.002 3.871 4.9 1.1 86.5 10.3 0.8
750 0.442 0.001 4.049 5.6 1.3 92.2 10.8 0.8
760 0.287 0.001 4.005 6.2 1.4 94.1 10.7 0.8
770 0.168 0.001 3.968 7.2 1.7 93.9 10.6 0.6
780 0.140 0.001 3.965 9.7 2.3 95.2 10.6 0.6
800 0.056 0.000 3.982 15.4 3.8 97.4 10.6 0.6
850 0.056 0.000 3.965 15.2 3.7 97.3 10.6 0.6
900 4.370 0.016 2.492 0.8 0.1 35.2 6.6 4.2
PBR-108 Alunite, J=0.00148, wt.= 5.4 mg
Integrated total fusion age = 10.38 Ma
Plateau age (750-850C) = 10.59 0.08 Ma

T (C) Ca/K 36
Ar/39Ar 40
Ar*/39Ar 40
Ar(x10-14) 39
Ar(x10-14) %40Ar* Age (Ma) 2
(mole) (mole)

650 13.066 0.092 1.770 14.1 0.5 6.2 4.7 1.6

700 6.288 0.012 2.545 2.2 0.4 43.0 6.7 1.2
720 2.307 0.006 3.810 4.4 0.8 68.1 10.1 0.8
740 0.981 0.004 3.980 7.1 1.4 76.1 10.5 0.8
760 0.393 0.003 4.068 13.4 2.7 80.5 10.8 0.8
780 0.142 0.003 4.089 20.8 4.2 83.2 10.8 0.6
800 0.056 0.001 4.115 27.9 6.2 91.9 10.9 0.6
820 0.066 0.001 4.083 17.8 4.2 96.4 10.8 0.6
840 1.516 0.002 4.176 0.9 0.2 89.4 11.0 2.2
PBR-131 Alunite, J=0.00147, wt.= 6.0 mg
Integrated total fusion age = 10.56 Ma
Plateau age (760-840C) = 10.83 0.06 Ma

137
 CHAPTER 3

Appendix 2. (cont.) Argon release data for magmatic biotite and hydrothermal alunite samples from the Colquijirca District
T (C) Ca/K 36
Ar/39Ar 40
Ar*/39Ar 40
Ar(x10-14) 39
Ar(x10-14) %40Ar* Age (Ma) 2
(mole) (mole)

650 15.409 0.016 2.988 0.7 0.1 42.0 7.9 4.2

675 5.647 0.007 4.582 1.7 0.3 71.8 12.0 1.6
700 2.466 0.007 3.621 4.2 0.8 65.9 9.5 0.8
725 1.139 0.003 3.994 9.4 2.0 84.4 10.5 0.6
750 0.544 0.002 4.030 15.5 3.4 87.8 10.6 0.6
775 0.261 0.001 4.022 33.2 7.7 92.8 10.6 0.6
800 0.204 0.000 4.113 20.0 4.7 97.1 10.8 0.6
825 0.698 0.000 4.276 2.8 0.7 98.8 11.2 1.0
PBR-137 Alunite, J=0.00146, wt.= 6.1 mg
Integrated total fusion age = 10.60 Ma
Plateau age (725-775C) = 10.56 0.08 Ma

T (C) Ca/K 36
Ar/39Ar 40
Ar*/39Ar 40
Ar(x10-14) 39
Ar(x10-14) %40Ar* Age (Ma) 2
(mole) (mole)

650 28.390 0.095 0.681 7.8 0.3 2.5 1.8 2.4

700 6.756 0.016 3.490 4.3 0.5 43.6 9.3 1.2
710 2.580 0.006 4.103 4.8 0.8 69.3 10.9 0.8
720 1.282 0.003 4.041 6.1 1.2 81.4 10.8 0.8
730 0.630 0.002 4.017 7.8 1.7 89.6 10.7 0.8
740 0.380 0.001 4.047 9.7 2.3 93.7 10.8 0.6
750 0.227 0.001 4.015 12.4 2.9 94.0 10.7 0.6
760 0.149 0.001 4.024 13.0 3.1 94.8 10.7 0.6
770 0.102 0.001 4.001 15.2 3.7 96.6 10.6 0.6
780 0.057 0.000 4.023 15.8 3.9 98.8 10.7 0.6
800 0.104 -0.000 4.051 10.2 2.5 100.2 10.8 0.6
850 0.904 0.000 4.484 1.5 0.3 99.2 11.9 1.4
900 7.173 0.031 5.277 0.5 0.0 37.4 14.0 14.0
PBR-218 Alunite, J = 0.00148, wt.= 6.5 mg
Integrated total fusion age = 10.60 Ma
Plateau age (710-850C) = 10.72 0.06 Ma

138
 CHAPTER 3

3b. Infra-red (CO2) laser 40Ar/39Ar analysis

of alunites from the Miocene Colquijirca
District, central Peru.

Ronner Bendez1,4, Laurence Page2, Richard Spikings1, Zoltan Pecksay3 & Llus Fontbot1

1
Section des Sciences de la Terre, Universit de Genve, Switzerland

2
Department of Geology, Lund University, Slvegatan 12, 22362 Lund, Sweden

3
Institute of Nuclear Research, Hungarian Academy of Sciences, Bemtr 18/C, H-4026 Debrecen, Hungary

4
Sociedad Minera El Brocal S. A., Lima Peru

Abstract

We present 40Ar/39Ar data acquired by infra-red (CO2) laser step-heating of alunite crystals from the
large, mining Miocene Colquijirca District, in central Peru. The district hosts two main ore types, i) high
sulfidation disseminated Au-(Ag) epithermal mineralization, and ii) sulfide-rich Cordilleran polymetallic
deposits. Previous 40Ar/39Ar age spectra, derived by furnace degassing (Bendez et al., 2002), suggested that
precious metal disseminated deposition predated the Cordilleran polymetallic mineralization by several hundred
thousand years. The present results confirm that Cordilleran base metal lodes, which are mainly epithermal and
posses high sulfidation mineral assemblages, post date the disseminated Au-(Ag) high sulfidation epithermal
mineralization. Collectively, the laser and furnace derived 40Ar/39Ar ages support the hypothesis that Cordilleran
ores formed during a single and relatively narrow time interval, between 10.830.06 and 10.590.06 Ma.
The duration of both mineralizing systems are indicative of multiple intrusive and/or thermal episodes
related to a large magma reservoir at depth. This is more evident in the Oro Marcapunta Au-(Ag) high
sulfidation epithermal system which lasted particularly longer (from 11.90.07 to 11.100.06 Ma). In this
system, combining the alunite datings with observed crosscutting relationships between alunite-bearing acid
barren alteration and periods of gold deposition defined by sulfide and oxide-bearing veinlets, it is concluded
that at least two recurrent acid alteration-gold mineralization events took place at Oro Marcapunta.

139

Introduction
The Colquijirca District, located 12 km south
of the Cerro de Pasco District in central Peru
(Figure 3b.1), comprises various Cordilleran sulfide-
rich polymetallic replacement deposits (Colquijirca,
Smelter, Marcapunta Oeste, San Gregorio) and a
disseminated high sulfidation Au-(Ag) prospect
(Marcapunta), all linked to a Miocene diatreme-dome
complex (Ahlfeld, 1932; Lindgren, 1935; McKinstry,
1936; Yaringao et al., 1997; Vidal et al., 1997;
Bendez, 1997; Fontbot and Bendez, 1999, 2001;
Bendez and Fontbot, 2002; Bendez et al., 2003).
The Marcapunta Miocene diatreme dome
complex, exposed in the center of the Colquijirca
district (Sillitoe, 2001; Bendez et al., 2002; Sarmiento,
2004), is one of a series of volcanic edifices, including
Cerro de Pasco and Yanamate (Figure 3b.1), which
consist of multiple dome-lava intrusions of mainly
dacitic composition. Injection and explosion breccias
and pyroclastic layers, typical of diatreme conduits,
are extensively recognized at depth (Figure 3b.2).
Inward-dipping normal faults located in peripheral
areas suggest that the entire edifice collapsed, possibly
prior to the main episodes of mineralization (Figure
3b.2).
As in large sectors of Central Peru, the district
is characterized by extensive exposures of carbonate
rocks of significantly varying ages. A 400 m thick
sequence of limestone and dolostone of the Upper
Triassic-Lower Jurassic Pucar Group occupies
the southern sector of Marcapunta. The Eocene
Pocobamba Fm., with a thickness up to 450 m, and
mainly composed of continental marls and limestones
(Angeles, 1993), covers most of the northern sector
of the Colquijirca District (Figure 3b.1).
The mining district was affected by Tertiary
folding (NNE fold axes), which pre-dates the
emplacement of the Marcapunta volcanic complex
(Angeles, 1993). The major N-S trending, Longitudinal
Fault, which has possibly been active since the Jurassic
(Angeles, 1993), defines the eastern border of the
Colquijirca District, and dissects the Cerro de Pasco
District to the north (Figure 3b.1). Other fracture
systems recognized in the Colquijirca District follow
NW and NE trends (Figure 3b.1). The Longitudinal
fault appears to control the emplacement of the
Miocene intrusive rocks. NW oriented fractures and
ring faults, related to the collapse of the Marcapunta
volcanic complex, probably played a significant role
in channeling the ore fluids in much of the district
(Figure 3b.2).
The district hosts two main types of
metallogenic mineralization: (i) disseminated high
sulfidation Au-(Ag) epithermal mineralization,
hosted within the volcanic complex of Marcapunta,
and (ii) Cordilleran base metal deposits hosted in the
carbonate rocks of both the Pucar Group and the
Pocobamba Formation.
Au-(Ag) high sulfidation epithermal
140
CHAPTER 3
mineralization consists of vuggy silica bodies,
with vertical dimensions of up to 100 m and gold
concentrations of 1 - 2 g/t (Vidal et al, 1997). The
bodies have been mainly recognized in the central
portion of the complex, associated with the diatreme
breccia and pyroclastic infill, where their morphology
is controlled by both lithological and structural
permeability. Less abundant gold-bearing zones of
completely oxidized veinlets have been recognized,
particularly towards the surface. These zones have
bulk Ag/Au ratios ranging from 10 to 20. As in other
high sulfidation epithermal deposits, deep portions
of unoxidized ores characteristically contain less than
5 vol% of finely disseminated sulfides, mainly pyrite-
enargite and very minor chalcocite, covellite, and
sphalerite. Pre- and post-ore hydrothermal alteration
includes vuggy silica ledges within E-W fractures
and tubular bodies within phreomagmatic breccias
(Figure 3b.2). The highest gold grades are found in
the vuggy silica bodies, which are strongly zoned,
forming dominantly quartz-alunite core assemblages
and outer zones of argillic alteration devoid of
economic gold concentrations.
Cordilleran base metal deposits mainly
consist of Cu-Zn-Pb-Ag(Au-Bi) zoned sulfide-
rich replacements and represent a distinct and
economically important type of mineralization in
the district. Cordilleran polymetallic mineralization
aggregates collectively amount to a resource of at
least 250 Mt. These aggregates include the Smelter
deposit (north of Marcapunta), where massive Cu-
(Au-Ag) ores were mined during the seventies, and
the Marcapunta Oeste project (west of Marcapunta;
Vidal and Ligarda, 2004). The historical Zn-Pb-(Ag)
Colquijirca mine is located further to the north and
has been an important silver producer in Peru since
pre-colonial times (Hutchinson, 1920; Lindgren,
1935; McKinstry, 1936). The San Gregorio deposit,
located 3 km south of Marcapunta, was discovered
during 1994-1995, and hosts at least 70 Mt @ 7.3%
Zn, 2.18% Pb, 0.57 oz/t Ag, (Yaringao et al., 1997),
constituting the largest undeveloped Zn-Pb-(Ag)
resource in the world. Mineralization at Colquijirca,
Smelter, and Marcapunta Oeste is mainly hosted by
the Pocobamba Fm., whereas the large San Gregorio
deposit replaces Pucar Group rocks.
A significant feature of the Colquijirca
Cordilleran deposits is the high total sulfide content,
which fluctuates between an average of 30 and
50 vol%. The most abundant minerals are pyrite,
which crystallized during an early silica-pyrite stage,
followed in abundance by enargite-pyrite from a
Main ore stage and, finally, chalcocite from a Late
ore stage (Bendez, 2006). Strongly oxidized zones,
originally composed of enargite-pyrite, display Ag/
Au ratios ranging from 80 to 120, much higher than
those found in the Oro Marcapunta disseminated
Au-(Ag) ores (10 to 20). Another major feature of
Cordilleran mineralization in the Colquijirca District
is the distinct ore zoning, defined by a Cu-(Au-Ag)
 CHAPTER 3

G E OL OG I C A L UNI T S
Quaternary deposits M I NE R A L I Z A T I ON T Y PE A tacocha

Diatreme-dome complex (Miocene)

calcic skarn-related Zn-Pb-A g
Dome complex (L ate E ocene-Oligocene)
Pocobamba Formation (E ocene), mainly Cordilleran base metal
limestones and marls (Zn-Pb-Cu-A gA u-B i)
C hicrn limestone (C retaceous)
A uA g high sulfidation
B asalt flows (C retaceous) epithermal
Goyllarizquizga Group (C retaceous), sandstones Milpo
Pucara Group (Upper T riassic-L ower Jurassic),

360 000
limestones and dolostones
Mitu Group (Permian-T riasssic), sandstones

E xcelsior Group (Devonian), phyllites

3 Km
Pacoyn
Cerro de Pasco 8820000

Quicay N

0 79 75 71
Y anamate

IQUITOS

CHICLAYO
CAJAMARCA A Colquijirca
8
TRUJILLO
HUARAZ Smelter
F ault
AREA OF
GEOLOGICAL MAP
PA

12 LIMA T hr usts and

CI

Marcapunta r ever se faults

B
FI

CUZCO
C

F olding axis

San Gregorio
O

16 AREQUIPA
C
E
A
N

Figure 3b.1: General geology and main mining centers in the Cerro de Pasco sector, central Peruvian Andes. Geology compiled
Johnson et al., (1955), Angeles (1999), Sociedad Minera El Brocal S. A. staff, and this study.

nucleus dominated by enargite; an intermediate Cu-
(Zn-Pb-Ag-Bi) zone where chalcopyrite, sphalerite
and galena predominate; and an outer Zn-Pb-(Ag)
envelope composed of sphalerite and galena. A
Zn-bearing Fe-Mn carbonate zone, which is almost
barren of sulfides, occurs in the outermost part.
Recent drilling in the western flank of
Marcapunta (Marcapunta Oeste project) revealed
crosscutting relationships, indicating that Cordilleran
mineralization post-dates the Au-(Ag) disseminated
epithermal hydrothermal activity. Cordilleran veins
systematically cut the precious metal veinlets and
veins in the easternmost portion of the Marcapunta
Oeste project. Several drill holes (e.g., CM3-
444 and CM4-452) encountered up to 350 m of
vertical section containing Au-(Ag) high sulfidation
epithermal ledges, which in the lowermost 50 m are
superimposed by Cordilleran ores. This superposition
comprises barren, early stage quartz-alunite zones,
containing Au-(Ag) veinlets, all of which are cut
by cm wide pyrite-(enargite)-rich veinlets and less
frequently veins. Furthermore, a majority of cavities
within the vuggy silica contain intergranular fillings
of enargite of the Cordilleran stage, which in part
destroy earlier Au-(Ag) veinlets with quartz-alunite-
bearing assemblages.

141
142
Freato-magmatic breccias.
400 m.
55

84
84

76
Au-(Ag) high sulfidation epithermal mineralization 76

43

Au-(Ag)-bearing vuggy silica

68

37 36

39
68

Eocene Pocobamba Formation carbonate rocks.

Td=442.9
B

Colquijirca (following the ABCDEF profile of Figure 1).

N
Dacitic lava-domes.

Eocene Pocobamba Formation carbonate rocks.

Cordilleran base metal ores

Enargite-pyrite-quartz-alunite(luzonite, colusite, zunyite
barite)

Pyrite-chalcopyrite-dickite-kaolinite-siderite-quartz
(tennantite, bornite, Bi-Ag sulphosalts, alunite, barite,
quartz)
A
Pyrite-sphalerite-galena-chalcopyrite-dickite-kaolinite-
quartz(siderite, hematite, magnetite, alunite),
and an outermost known zone of pyrite-galena-sphalerite
-siderite(kaolinite, dolomite, Zn-bearing carbonates).

mal mineralization of Oro Marcapunta and the Cordilleran base metal deposits of Marcapunta Oeste, Smelter and
Figure 3b.2: Block diagram illustrating the spatial relationships between the precious metal high sulfidation epither-
CHAPTER 3

Previous geochronologic data and scope
of the present work
This work presents the results of a high
precision radiometric survey of alunite samples of
the Colquijirca District, which is complementary to
previous furnace 40Ar/39Ar dating results published in
Bendez et al. (2003). Three K/Ar ages obtained by
means of conventional whole rock analysis are also
presented. The later technique was used on samples
from San Gregorio, where, the extremely fine-grained
character of the alunite (Fontbot and Bendez,
1999) precluded the possibility of 40Ar/39Ar analyses.
The combined results are consistent with the timing
of mineralizing events indicated by crosscutting field
relationships (Bendez and Fontbot, 2002).
The previous 40Ar/39Ar dating in the Colquijirca
District indicated that Cordilleran base metal lode and
replacement deposits from the Smelter and Colquijirca
deposits were formed by a late hydrothermal event,
subsequent to Au-(Ag) high sulfidation epithermal
mineralization at Oro Marcapunta (Bendez et
al., 2003). Alunite samples related to the Au-(Ag)
epithermal ores were dated at 11.30.06 - 11.60.08
Ma (2) and those from the Cordilleran base metal
ores in the northern part of the district (Smelter
and Colquijirca) at 10.60.06 - 10.80.08 Ma. The
significant time gap (0.5 My) between the ages of the
two mineralization types in the Colquijirca District
was interpreted in terms of distinct hydrothermal
events within the same magmatic cycle (Bendez et
al., 2002).
According to the same survey, magmatic
biotite derived from flanking dacitic domes
yielded 40Ar/39Ar ages ranging from 12.40.04 to
12.90.10 Ma, which is ~0.8 My older than the
earliest recognized hydrothermal manifestation (e.g.
alunite PBR-213 from the Au-(Ag) high sulfidation
epithermal Oro Marcapunta event dated at 11.630.08
Ma). Baumgartner (2006), reports a U-Pb age of
12.120.03 Ma for zircons from a dacitic dome
from the western sector of the Marcapunta volcanic
complex. This age, though relatively younger, is fairly
consistent with the 12.4-12.9 Ma period of dacitic
doming, a period thought to be part of the magmatic
cycle associated with the mineralization in the whole
Colquijirca District.
The relatively long time gaps between the
two mineralizing events and between the youngest
dated magmatic dome and the oldest recognized
hydrothermal manifestation (0.5 and 0.8 My
respectively, Fig. 6 in Bendez et al., 2003) are
inconsistent with modern hypotheses of the longevity
of hydrothermal cells related to single intrusions
(Marsh et al., 1997; Henry et al., 1997; Muntean and
Einaudi, 2001). Consequently, the time-lags suggested
by Bendez et al. (2003) may be an artifact of the
low quantity of age data. The principal aim of this
study is to clarify the timing of mineralizing events
by acquiring a highly resolved geochronological
CHAPTER 3
database. If such lulls in hydrothermal activity exist,
then there may have been several discrete magmatic
events, each creating each their own mineralizing
systems. We also aim to determine the first absolute
mineralization ages of the large Cordilleran deposit of
San Gregorio, in the southern part of the district.
Dated samples
Seven platy, coarse grained alunite separates
were selected for infra-red (CO2) laser step-heating
40
Ar/39Ar analysis. The composition of six of the dated
alunite samples was quantified using a microprobe,
and all approach the theoretical alunite end-member
stoichiometry. Four samples belong to the Au-(Ag)
high sulfidation epithermal mineralization (Oro
Marcapunta) and three to the Cordilleran base metal
ores of the northern part of the district (Smelter and
Colquijirca).
Three whole-rock samples from San Gregorio,
in the southern part of the district, were dated using
the K/Ar method. This less precise method was
used because of the extremely fine grained habit of
alunite, which is intergrown with pyrite.
Alunite samples from the Au-(Ag) epithermal high
sulfidation mineralization
Alunites PBR-336 and PBR-338 of the Oro
Marcapunta Au-(Ag) epithermal mineralization were
collected from the southern flank of the southern
topographic high of Marcapunta, approximately 400
m meters south of samples PBR-198 and 214, which
were previously dated using furnace 40Ar/39Ar step-
heating. They represent internal parts of advanced
argillic alteration zones (AAA zones), which
immediately envelope leached vuggy silica cores. In
these AAA zones, alunite is euhedral and dominantly
accompanied by quartz (Figure 3b.3), though in some
cases pyrophyllite, diaspore, and zunyite are locally
important. Samples PBR-336 and PBR-338 are cut by
Au-bearing veinlets composed mainly of oxides and
minor jarosite and quartz, indicating that precious
metal deposition postdated the advanced argillic
alteration in the two points in which the samples were
collected. The dated alunite grains are less than 1 mm
long (Appendix 4b.2), corresponding to the typical
grain size of alunite in the internal part of the AAA
zones. In contrast to alunite from the external parts
of the AAA zones, the dated alunite from internal
zones is homogeneous and no pseudocubic cores
of the woodhouseite-svanvergite end-member were
observed in thin section (Figure 3b.3). The dated
samples display minor Na substitution by K (Na/K
between 0.1 and 0.6, Table 3b.1).
The third Oro-Marcapunta alunite separate
(PBR-335) was extracted from a vuggy silica rock,
in which alunite occurs as thin coatings on cavities
143
 CHAPTER 3

100 m 10 cm
A B

enargite
5 mm
1 cm
C D

sphalerite

quartz

E F

Figure 3b.3: Images from the distinct alunite samples dated in this study. A. Photomicrograph in transmitted light of sample
PBR-336 showing alunite from the precious metal high sulfidation epithermal mineralization of Oro Marcapunta. Note that
it is devoid of pseudocubic cores of the woodhouseite-svanvergite end-member. B. Photograph of an outcropping in southern
Marcapunta in which plumose alunite (sample PBR-273) cement Au-bearing rounded clasts (up to 2 ppm Au) of vuggy silica
formed from the precious metal epithermal system. C. Small geode displaying euhedral alunite from the Cordilleran ores of Smelter
intergrowth with enargite plus minor amounts of pyrophyllite and pyrite (sample PBR-322). D. Photograph showing the effect
of Cordilleran mineralization in volcanic rocks. A void left by former sanidine is filled by platy euhedral alunite intergrowth with
quartz, pyrite and enargite; these last two, in addition, in form of veinlets and as coatings in vugs. E. Intimate intergrown between
alunite and sphalerite revealed by backscattered electron image of sample PBR-298 from the Cordilleran deposit of Colquijirca.
F. Backscattered electron image of sample PBR-208 showing the typical extremely fine-grained habit of alunite from the large
Cordilleran deposit of San Gregorio.

left by former sanidine phenocrysts (Figure 3b.3).
Alunite grains are, in this sample, platy, euhedral,
transparent, pinkish and relatively coarse (up to 3
mm long). Microprobe analyses were performed
on several alunite grains from the same rock. They
are all compositionally homogeneous and close to
stoichiometric alunite (Table 3b.1).
Sample PBR-273 from Oro-Marcapunta
contains plumose alunite. Individual alunite grains,
which typically occur in clusters within open-space
fillings, are usually longer than 1 cm. Plumose alunite
in this sample cements a breccia which contain
rounded clasts of vuggy silica that bear oxide veinlets
(Figure 3b.3). Selective chemical analysis show that
veinlets-bearing vuggy silica clasts are mineralized
(up to 1 ppm Au), indicating that plumose alunite
postdated a period of gold deposition which in turn
postdated acid alteration. Minor quartz is the only

144
 CHAPTER 3

accompanying phase and occurs as euhedral grains adjacent to the Cu-bearing zones. The dated alunite
encapsulated within the clusters of alunite. An alunite occurs in open spaces intimately intergrown with
grain from sample PBR-273 was analyzed using an sphalerite, galena, pyrite, and quartz (Figure 3b.3).
electron microprobe and yielded compositions close The composition of alunite PBR-298 is similar to that
to the alunite end member, with an average Na/K of alunite PBR-108 (previously dated using the 40Ar/
below 0.1 (Table 3b.1). 39
Ar furnace step-heating technique), and represents
the pure K-rich end-member (Table 3b.1).
Alunite samples from Cordilleran base metal ores The third sample (PBR-322) from the
Two of the three dated alunite samples extracted Cordilleran ores was collected in the Smelter deposit
from the Cordilleran base metal ores were collected where alunite occurs together with silica (mainly
from the internal portions of the Colquijirca deposit. quartz), enargite, zunyitedickite. The dated alunite
Sample PBR-244 defines part of the Cu-(Au-Ag) displays reversal crystallization with pyrite (Figure
zone, which is dominated by enargite and includes 3b.3), which is proposed to have precipitated together
abundant alunite and quartz, along with minor zunyite with enargite from the Main ore stage. Microprobe
and accompanying phases (Figure 3b.3). The alunite analyses revealed that alunite PBR-322 contains
(PBR-244) is fine grained (< 500m; Appendix 4b.2) significantly more Na (up to 2.04 Na2O wt%) than
and fills open-spaces left by coeval pyrite, quartz and both samples PBR-244 and PBR-298 (Table 3b.1).
enargite. In places, minute inclusions of enargite float Three alunite-rich concentrates from San
within alunite masses. These relationships suggest Gregorio were prepared from samples where alunite
that alunite precipitated from the Main ore stage. was particularly abundant. Concentrates PBR-208
No microprobe data are available for these alunite and PBR-284a were sampled from sulfide rock, a
grains. fine-grained material composed of sulfides (sphalerite
Alunite blades from sample PBR-298 were and, subordinate galena and pyrite), kaolinite, quartz
separated from a rock belonging to the innermost and alunite. The grain size for all components is in
portion of the Zn-Pb-(Ag) zone (i.e, the sphalerite- the order of several tens of microns and alunite
galena rich part). This type of assemblage, composed does not exceed 30 m (Figure 3b.3; Appendix 4b.2).
of alunite-quartz-sphalerite-galena-pyrite(diaspore- Petrographic observation (Figure 3b.3) does not show
kaolinite), is solely found in portions immediately evidence of reaction between alunite and sulfides and
quartz. Furthermore, alunite appears encroached into
the sulfides and quartz, and the reverse relationship is
also recognized in other samples. These observations
Table 4b.1. Representative microprobe composition of alunite suggest that alunite, sulfides (including sphalerite-
from Au-(Ag) and base metal mineralization in the Colquijirca
district* galena) and quartz precipitated coevally, presumably
Au-(Ag) epithermal Cordilleran base metal
from the same ore fluids. The interpretation is
ores ores supported by fluid inclusion data from sphalerite
PBR PBR PBR PBR PBR PBR and quartz, which share similar homogenization
Sample 273 335 336 298 322 208 temperatures and salinities (Bendez, 2006).
Microprobe analyses of rare, large alunite grains
K2O 9.89 9.78 8.22 10.04 8.85 9.21 (up to 100 m) yielded bulk compositions close to
Na2O 0.82 0.81 1.78 0.24 2.04 0.42 stoichiometric predictions, although in some cases
BaO 0.43 0.38 0.25 0.26 0.16 0.08 the A site is occupied by significant amounts of Pb
(up to 1.32 wt%, Table 3b.1). Concentrate PBR-209
SrO 0.82 0.32 0.02 0.02 0.51 0.16
was obtained from a 50 cm thick vein, which cuts
PbO 0.00 0.02 0.01 0.01 0.01 1.32 oxidized sulfide rock. Estimates of the composition
Al2O3 35.98 35.88 37.20 36.79 35.94 36.42 of the three concentrates, made using an optical
SO3 40.21 39.90 38.86 39.01 40.84 40.80 binocular microscope, are (vol%): PBR-208, 85%
P2O5 0.12 0.23 0.24 0.14 0.24 0.82
alunite, 10% kaolinite-quartz, 5% pyrite; PBR-209,
80% alunite, 10% kaolinite, 5% anatase, 5% quartz;
H2O **
14.02 14.24 11.86 11.96 11.84 12.62 PBR-284a, 75% alunite, 15% pyrite-sphalerite, 10%
F -
0.18 0.07 0.76 0.69 2.42 0.38 quartz-kaolinite.
Total 102.47 101.63 99.20 99.16 102.85 102.23
*. Alunites were analysed using a Cameca SX50 electron
microprobe at the University of Lausanne. Instrumental Analytic procedure
conditions were: accelerating voltage of 12 kV, beam current
of 10 nA, and spot size of 15 m. Infra-red (CO2) laser 40Ar/39Ar analysis
**. Weight % H2O calculated based on observed values of
sulfur, phosphorous, potassium, sodium, strontium, barium, Step-heating 40Ar/39Ar analysis of alunite
and fluorine, and alunite stoichiometry using the formula grains using a laser have been reported by Mote et
AR3(SO4)2(F, OH)6, in which A refers to the large cations K+, al. (2001) and Vasconcelos and Conroy (2003). The
Na+, Ba2+, Pb2+and Sr2+, and R is Al3+ significantly lower amount of material (between 3

145

and 5 mg) required for laser degassing of alunite,
relative to conventional furnace heating, increases
the possibilities of dating epithermal mineralization
systems where the alunite yields for certain
mineralizing episodes may be low.
Alunite grains were individually handpicked
from crushed and washed samples following the
procedure adopted for the furnace 40Ar/39Ar analysis
(Bendez et al., 2003). Only grains of microscopically
high purity (< 2 vol% of quartz and opaque
contaminants) were selected. The grain separates were
subsequently cleaned for ten minutes in deionized
water in an ultrasonic bath. Further details of the
alunite samples, including UTM coordinates and
sample amounts are provided in Table 3b.2. Alunite
grains selected for 40Ar/39Ar analysis were irradiated
with the FCT sanidine standard (28.020.16 Ma;
Renne et al., 1998) for 8 hours in the 1 MW, Cd-
lined CLICIT facility at the University of Oregon.
The alunites and monitors were analysed at the 40Ar/
39
Ar laboratory at the University of Lund, Sweden.
The laboratory consists of a Micromass 5400 mass
spectrometer, equipped with a faraday and an electron
multiplier. The stainless steel extraction line includes
two SAES C50-ST101 Zr-Al getters, and extracted gas
was cooled to ~-150C by a Polycold P100 cryogenic
refrigeration unit mounted over a cold finger. Single
grains of alunite were step-heated using a defocused
50W CO2 laser rastered over the samples to provide
even-heating of the grains. Samples were measured
on the electron multiplier and time-zero regressions
were fitted to data collected from ten scans over the
m/e range 40-36. Peak heights and backgrounds were
corrected for mass discrimination, isotopic decay of
39
Ar and 37Ar and interfering nucleogenic Ca-, K- and
Cl-derived isotopes. 40Ar blanks were calculated before
every new sample and after every three heating steps.
40
Ar blanks were between 4.0 and 2.0E-16 moles.
Blank values for m/e 39 to 36 were all less than 7E-18
moles. Age plateaus were determined using the criteria
of Dalrymple and Lamphere (1971), which specify
the presence of at least three contiguous incremental
heating steps with concordant ages, that constitute
>50% of the total 39Ar released during the step-
heating experiment. The entire analytical process is
automated and utilizes software modified specifically
for this laboratory and originally developed at the
Berkeley Geochronology Center by Al Deino. 40Ar/
39
Ar step-heating data, including heating schedules,
are presented in Appendix 4b.1.
K/Ar analysis
As indicated above the fine-grained nature of
the material from San Gregorio prevented handpicking
and 40Ar/39Ar analysis. Therefore, alunite concentrates
from San Gregorio were prepared for K/Ar analysis.
Concentrates were achieved by centrifuging a crushed
material immersed within distillated water. Denser
146
CHAPTER 3
material rich in sulfide was removed. The remaining
fraction was then ultrasonically cleaned, which
additionally allowed separating part of the residual
contaminants, particularly pyrite. Any additional
treatment has not been carried out on the separates.
As a consequence the purity of the alunites is only
approximately 75-85%. Mineralogical composition
of the dated alunites is given in Appendix 4b.2.
For measurement of potassium concentration
in alunite, an aliquot of the final separate was
grounded and reacted in a Teflon container with
HNO3 and HF at ~120C. After evaporation of the
acids, the sample was diluted by HCl solution, and a
Na buffer was added and analyses have been made
by flame photometry. The analytical precision was 2
percent at the 1-sigma confidence level.
For gas extraction tantalum crucible was used
heated by high frequency. Before degassing 38Ar spike
was added for isotope dilution analysis. Purification
was carried out in a low-blank metallic line using
titanium and SAES 707 getters and cold trap.
Argon isotopic analyses were performed on-
line in a 15cm radius sector type mass spectrometer
equipped with a single collector system. In all
cases, mass discrimination factors for Ar isotopes
were determined using sample of atmospheric Ar.
Details of the instruments, the applied methods and
results of calibration have been described elsewhere
(Balogh 1985). Atomic constants suggested by
Steiger & Jger (1977) were used for calculating the
ages. All analytical errors represent one standard
deviation (ie. 68% analytical confidence level).
Since we base our analytical errors on the long term
stability of instruments and on the deviation of
our results obtained on standard samples from the
interlaboratory mean the analytical errors are likely
to be overestimated.
Table 4b.2. Summary of the dating results of the Colquijirca
district.
Dating results, Error (Ma2)
Sample Location inverse
Plateau age1
isochron age
Precious metal high sulfidation epithermal ores
PBR-273 Southern Marcapunta 11.510.06 11.440.13
PBR-338 Central Marcapunta 11.100.06 11.150.07
PBR-335 Central Marcapunta 11.600.06 11.730.07
PBR-336 Central Marcapunta 11.900.06 11.790.07
Cordilleran base metal lode and replacement bodies
PBR-322 Smelter 10.640.06
PBR-298 Colquijirca 10.760.06 10.750.07
PBR-244 Colquijirca 10.750.06 10.600.08
1
Plateau age calculated according to the criteria of Dalrymple and
Lamphere (1971)
 CHAPTER 3

PBR-273 PBR-322
18 18

11.510.06 Ma 10.640.09 Ma
16 16

14 14

12 12

10 10

8 8
0 20 40 60 80 100 0 20 40 60 80 100

PBR-338 PBR-298
Apparent Age (Ma)

18 18

11.100.06 Ma
16 16

14 14

10.760.06 Ma
12 12

10 10

8 8
0 20 40 60 80 100 0 20 40 60 80 100

PBR-336 PBR-335
18 18

11.900.07 Ma 11.600.06 Ma
16 16

14 14

12 12

10 10

8 8
0 20 40 60 80 100 0 20 40 60 80 100

PBR-244
18

16

14

12
10.750.06 Ma

10

8
0 20 40 60 80 100

Cumulative % 39 Ar released
Figure 3b.4: 40Ar/39Ar age apparent age spectra from analyses through laser degassing. Steps segments from which
plateau ages were calculated are shown in filled boxes.

147
 CHAPTER 3

Table 4b.3. K/Ar data obtained on alunite separates.

Alunite 40Ar/39Ar data from Au-(Ag) Oro
No. of 40
Ar rad 40
Ar rad K/Ar age
K/Ar
Sample K (%)
(%) (ccSTP/g) (Ma) Marcapunta epithermal mineralization
All four dated alunite samples related to Au-
6092 PBR-208. 7.76 18.1 3.975*10-6 13.1+/-1.1 (Ag) mineralization (PBR-338, PBR-336, PBR-
335 and PBR-273) yield age plateaus with ages
6095 PBR-284a 5.24 18.4 2.696*10-6 13.2+/-1.1 ranging between 11.100.06 and 11.900.07 Ma
(Figure 3b.4). These ages extend previous estimates
6093 PBR-209. 6.27
9.5 3.453*10-6 14.1+/-2.1 (11.290.12 - 11.630.08 Ma; Bendez et al. (2003))
10 3.404*10-6 13.9+/-2.0 of the duration of high sulfidation activity at Oro
Marcapunta by 0.5 My. Plateau ages of 11.690.06
Ma (PBR-335) and 11.510.06 Ma (PBR-273) are
broadly consistent with the period of acid-sulfate
Results alteration that was previously recognized by furnace
degassing.
Ar/39Ar data and age spectra are shown in
40

Table 3b.2 and Figure 3b.5 respectively. The inverse

isochron ages (Table 3b.2) and plateau ages are
indistinguishable (2) in six of the seven dated
samples and the plateau ages are used in the following
discussion. The 40Ar/36Ar intercepts on the inverse
isochrons suggest that the initial argon reservoirs in
the alunite grains were atmospheric.
Analytical data of conventional K/Ar dating
are presented in Table 3b.3 and errors are reported
at the 2 level.
Alunite 40Ar/39Ar data from the Smelter and
Colquijirca Cordilleran base metal ores
Three alunite samples from the Cordilleran
base metal ores yield age plateaus with ages ranging
between 10.640.06 and 10.760.06 Ma (PBR-244
from Colquijirca at 10.750.06 Ma; PBR-298 from
Colquijirca at 10.760.06 Ma; and PBR-322 from

Middle Miocene Late Miocene

a
on biotite
a
on sanidine
a
Probable periods of gold deposition on alunite
on alunitea

Dome emplacement

12
Age (Ma) 11

Previous surveys High sulfidation Au-(Ag)

K/Ara epithermal mineralization
39
Ar/ Ar (furnace)b
40

This survey:
39
Ar/ 40Ar (infrared laser)
K/Ar whole rock Cordilleran ores
of San Gregorio Cordilleran base metal deposits

15 14 13 12 11 10
Age (Ma)
Figure 3b.5: Summary diagram of available geochronological data (K/Ar and 40Ar/39Ar) from the Colquijirca district: a,
from Vidal et al. (1984) at 2; b, Bendez et al. (2003) at 2 level of confidence.

148

Smelter at 10.640.09 Ma; Figure 3b.4, Table 3b.2).
These new data are entirely consistent with the timing
of mineralization of the Cordilleran ores at Smelter
and Colquijirca (10.560.08 Ma, sample PBR-137
to 10.830.06 Ma, sample PBR-131), presented in
Bendez et al. (2003).
Alunite K/Ar data from the San Gregorio Cordilleran
deposit
Alunite concentrates PBR-208 and PBR-284a
of the San Gregorio Cordilleran deposit yield similar
ages of ~13.12.2 Ma (PBR-208 at 13.12.2 Ma
and PBR-284a at 13.22.2 Ma; Table 3b.3; Figure
3b.5). Alunite concentrate PBR-209, extracted
from a crosscutting vein, yielded in a first batch an
age of 13.94.0 Ma (2). For the sake of getting
confirmation about this apparent older age, a duplicate
analysis has been made (14.1 4.2, no 6094). On the
basis of investigation of mineralogical composition
(Table 3b.3), we can exclude the presence of excess/
inherited argon caused by some detrital mica in this
alunite concentrate.
Discussion
The 40Ar/39Ar ages of the Colquijirca District,
obtained by infra-red laser step-heating, are entirely
consistent with previous 40Ar/39Ar ages yielded by
furnace step-heating. The present results confirm
that Cordilleran base metal lodes, which are mainly
epithermal and posses high sulfidation mineral
assemblages, post date the Au-(Ag) high sulfidation
epithermal mineralization. Combining the present
results with previous furnace degassing 40Ar/39Ar
ages (Bendez et al., 2002) reinforces the hypothesis
that Cordilleran ores formed during a single event
over a relatively narrow interval of time, between
10.830.06 and 10.590.06 Ma.
Advanced argillic alteration from the
disseminated Au-(Ag) high sulfidation epithermal
system, which, via crosscutting relationships in
the field appears to pre and post-date the Au-(Ag)
deposition, appears to have lasted ~0.500.06
My longer (between 11.900.07 and 11.100.06
Ma) than previously recognized. There is no clear
relationship between geographical location and
age, which suggests that acid hydrothermal activity
indiscriminantly affected different portions of the
Marcapunta volcanic complex. Plumose alunite
cementing Au-bearing vuggy silica clasts (sample
PBR-273), yielded a plateau age of 11.510.06 Ma,
which is ~400 ky older than the youngest dated platy
alunite (PBR-338, 11.100.06 Ma.). Therefore, the
formation of plumose alunite, which is commonly
found in Au-(Ag) high sulfidation epithermal
deposits where it typically cuts early AAA zones
(e.g., Red Mountain, Colorado; Bove et al., 1990), is
CHAPTER 3
not indicative of the waning stages of hydrothermal
activity in disseminated precious metal high sulfidation
ore deposits.
Following recent studies of the longevity
of hydrothermal cells related to a single intrusion
(<50 ky; Marsh et al., 1997; Henry et al., 1997;
Muntean and Einaudi, 2001), we propose that both
mineralizing events, though particularly the Au-(Ag)
high sulfidation mineralization (with a duration of
~0.8 My), are indicative of multiple intrusive and/or
thermal episodes related to a large magma reservoir
at depth, probably continuously being fed by basaltic
magma (e.g., Marsh et al., 1997, Pcskay & Molnr,
2002). The best evidences of such multiple intrusive-
related cells are given by the high sulfidation Au-(Ag)
epithermal system. Samples PBR-336 and PBR-338,
dated at 11.90.07 and 11.10.06 respectively, are
cut by Au-bearing oxidized veinlets which implies
that at least one Au-(Ag) mineralizing period took
place as late as shortly after 11.1 Ma (Figure 3b.5).
Plumose alunite sample PBR-273 dated at 11.510.06
Ma cut Au-bearing vuggy silica clasts indicating
that a, similar, but earlier period of gold deposition
predated this age (Figure 3b.5). As all alunite-bearing
samples dated, including those by furnace degassing,
are cut by economic veinlets, several other periods of
gold deposition could happen, yet shortly postdating
the 11.9 Ma and 11.5 ma alunite formation given by
samples PBR-336 and PBR-273 respectively.
Despite the large errors, the concordance of
two of the three K-Ar ages at 13.12.0 Ma, opens the
possibility that the San Gregorio formation predates
the other known high sulfidation systems in the
Colquijirca district, including those of the Au-(Ag)
epithermal at Oro Marcapunta and the Cordilleran
deposits of Smelter, Colquijirca, and, as deduced
from cross-cutting relationships, Marcapunta Oeste.
According to this hypothesis, mineralization at San
Gregorio may have been contemporaneous with one
or more of the episodes of dacitic doming such as
that dated at 12.90.1 Ma in the western flank of the
Marcapunta complex (biotite 40Ar/39Ar, sample PBR-
215, Bendez et al., 2003).
The coeval nature of several episodes of
mineralization within the whole Cerro de Pasco-
Colquijirca district is striking. Baumgartner (2006)
reports numerous infra-red laser 40Ar/39Ar step-
heating plateau ages of alunite grains from most of
the strongly acid-sulfate altered areas of the Cerro de
Pasco district. Several samples from the Venenococha
area yield plateau ages spanning from 12.4 to 14.5
Ma, defining a long period of hydrothermal activity
that may have been contemporaneous with the
formation of San Gregorio. Similarly, one alunite
sample from an enargite Cordilleran vein at Cerro
de Pasco yields a plateau age of 10.90.1 Ma,
indistinguishable from the oldest age obtained from
the enargite-rich cordilleran deposit at Smelter in
the Colquijirca District (10.83 0.06 Ma). The clear
spatial synchronicity in mineralization supports the
149

hypothesis that a single, large magma chamber was
related to the generation of the giant polymetallic
concentrations of both, the Colquijirca and Cerro de
Pasco districts (Bendez et al., 2004).
Combining the new and previous 40Ar/39Ar
and K/Ar radiometric age data suggests the whole
hydrothermal history of the district had a lifespan of
at least 2 to 2.5 My. Such a long lifespan seems to be a
common feature in the formation of particularly large
ore concentrations (e.g., Chuquicamata, El Teniente,
Butte, Cerro de Pasco, La Escondida; Ossandn et al.
2001, Quiroz, 2003, Gustafson et al, 2001, Heather et
al. 2003, Maksaev et al 2003).
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151
152
Appendix 4b.1. 40Ar/39Ar Analysis of alunite samples from the Colquijirca district
% Step
Run ID Pwr/TC Ca/K Cl/K 36Ar/39Ar %36Ar(Ca) 40*Ar/39Ar Mol 39Ar E-14 Cum. % %40Ar* Age (Ma) 2 (Ma)
PBR-298 (J value = 0.0021008 0.00001):
1099-01B 1.2 3.450 0.009 0.006 7.2 2.842 0.589 3.5 3.5 61.5 10.738 0.245
1099-01C 1.2 5.671 0.006 0.005 15.1 2.921 1.180 6.9 10.4 69.5 11.038 0.110
1099-01D 1.2 1.616 0.005 0.003 7.2 2.829 2.541 12.9 23.2 77.1 10.689 0.055
1099-01E 1.3 3.305 0.006 0.004 11.8 2.833 1.551 9.1 32.3 74.1 10.706 0.074
1099-01F 1.3 3.983 0.007 0.003 16.2 2.845 1.139 6.7 39.0 77.5 10.750 0.093
1099-01G 1.5 2.202 0.006 0.003 10.4 2.854 2.570 13.7 52.7 78.9 10.783 0.051
1099-01H 1.7 2.057 0.006 0.002 13.3 2.856 3.855 20.6 73.4 84.2 10.792 0.039
1099-01I 2.0 2.157 0.005 0.002 12.1 2.847 2.682 14.0 87.3 81.9 10.756 0.055
1099-01J 2.5 1.778 0.006 0.006 3.8 2.848 2.373 12.7 100.0 61.5 10.762 0.075
Integrated Age= 10.77 0.06
Plateau Age = 89.6 10.76 0.06

PBR-244 (J value = 0.0021064 1.000000e-5):

1093-01A 1.2 12.092 0.013 0.053 3.1 3.094 0.160 1.8 1.8 17.0 11.719 0.545
1093-01B 1.2 6.967 0.009 0.013 7.4 2.966 0.419 4.7 6.5 45.9 11.237 0.205

1093-01C 1.2 6.015 0.006 0.007 11.4 2.953 0.686 7.7 14.2 61.2 11.187 0.140
1093-01D 1.2 5.214 0.008 0.007 10.2 2.952 0.827 9.3 23.5 61.5 11.182 0.120
1093-01E 1.3 4.215 0.006 0.006 9.6 2.825 0.724 8.1 31.7 63.9 10.705 0.153
1093-01F 1.3 5.269 0.006 0.007 10.9 2.844 1.188 13.4 45.0 62.2 10.773 0.085
1093-01G 1.3 2.060 0.005 0.003 10.4 2.834 2.044 23.0 68.0 79.9 10.737 0.052
1093-01I 1.7 4.626 0.006 0.003 21.3 2.840 1.485 16.5 84.5 80.5 10.759 0.062
1093-01J 2.5 1.502 0.005 0.006 3.3 2.835 1.376 15.5 100.0 61.9 10.742 0.088
Integrated Age= 10.86 0.06
Plateau Age = 76.5 10.75 0.06

PBR-338 (J value = 0.00209 1.000000e-5):

1092-01A 1.2 1.326 0.005 0.026 0.7 2.918 0.727 6.7 6.7 27.9 10.969 0.149
1092-01B 1.2 7.201 0.007 0.017 5.8 3.066 0.662 6.1 12.9 39.6 11.524 0.161
1092-01C 1.2 1.535 0.006 0.014 1.5 2.932 1.427 12.1 24.9 41.9 11.022 0.081
1092-01D 1.2 1.164 0.006 0.007 2.2 2.954 2.383 20.2 45.1 59.0 11.103 0.053
1092-01E 1.3 3.104 0.007 0.002 19.6 2.974 1.352 12.5 57.6 85.3 11.178 0.080
1092-01F 1.3 4.705 0.007 0.003 20.2 2.964 1.262 11.4 69.1 79.9 11.140 0.080
1092-01G 1.3 5.855 0.020 0.102 0.8 2.832 0.141 1.3 70.4 8.7 10.646 0.944
CHAPTER 3
 40
Appendix 4b.1.(cont.) Ar/39Ar Analysis of alunite samples from the Colquijirca district
1092-01H 1.4 0.275 0.012 0.014 0.3 3.175 0.108 1.1 71.4 42.9 11.932 1.138
1092-01J 2.2 0.635 0.006 0.005 1.9 2.959 1.448 13.4 84.8 69.2 11.122 0.075
1092-01K 2.8 15.939 0.024 0.015 14.5 3.255 0.058 0.5 85.4 46.3 12.231 1.711
1092-01L 3.5 2.431 0.006 0.009 3.5 2.942 1.750 14.6 100.0 52.1 11.059 0.075
Integrated Age= 11.13 0.07
Plateau Age = 87.1 11.1 0.06

PBR-335 (J value = 0.002091 1.000000e-5):

1090-01A 1.2 0.982 0.005 0.016 0.8 3.077 2.225 8.3 8.3 39.6 11.569 0.074
1090-01B 1.2 3.246 0.006 0.008 5.3 3.102 0.957 3.9 12.3 57.2 11.665 0.099
1090-01C 1.2 1.449 0.006 0.008 2.6 3.117 3.065 11.5 23.8 58.9 11.718 0.049
1090-01D 1.3 1.243 0.004 0.007 2.4 3.104 1.915 7.2 31.0 60.6 11.673 0.061
1090-01E 1.3 4.381 0.008 0.012 5.1 3.085 0.466 1.9 32.9 48.4 11.600 0.196
1090-01F 1.3 4.299 0.007 0.010 5.7 3.133 0.92 3.8 36.7 52.5 11.781 0.109
1090-01G 1.4 4.246 0.007 0.014 4.1 3.146 0.524 2.2 38.8 43.8 11.827 0.160
1090-01H 1.4 0.740 0.005 0.008 1.2 3.126 1.118 4.6 43.4 56.8 11.756 0.096
1090-01I 1.5 1.128 0.005 0.009 1.7 3.125 1.171 4.8 48.3 55.1 11.750 0.089
1090-01J 1.5 2.425 0.008 0.011 3.0 3.069 0.351 1.5 49.7 49.7 11.540 0.201
1090-01K 1.7 0.64 0.006 0.007 1.3 3.121 2.655 10.0 59.8 61.9 11.736 0.046
1090-01L 1.9 0.895 0.005 0.004 3.1 3.109 4.426 16.6 76.4 73.5 11.691 0.030
1090-01M 2.3 1.655 0.006 0.008 2.9 3.092 1.594 6.0 82.4 58.1 11.626 0.078
1090-01N 2.8 1.654 0.005 0.009 2.6 3.105 2.552 9.6 92.0 55.1 11.676 0.054
1090-01O 3.4 1.080 0.006 0.013 1.1 3.092 1.872 7.0 99.0 45.3 11.625 0.070
1090-01P 4.0 4.815 0.010 0.021 3.1 3.487 0.246 1.0 100.0 36.6 13.105 1.141
Integrated Age= 11.69 0.06
Plateau Age = 100.0 11.69 0.06

PBR-322 (J value = 0.002095 1.000000e-5):

1084-19-2A 1.2 1.131 0.008 0.007 2.1 2.823 0.774 27.7 27.7 57.2 10.640 0.108
1084-19-2B 1.2 0.590 0.008 0.006 1.4 2.907 0.312 11.3 38.9 62.7 10.953 0.224
1084-19-2C 1.2 8.461 0.011 0.001 86.1 3.061 0.036 1.2 40.1 98.3 11.533 2.553
1084-19-2D 1.3 2.259 0.009 0.006 4.8 2.739 0.451 16.2 56.4 60.4 10.322 0.173
1084-19-2E 1.3 1.652 0.005 0.006 3.9 2.647 0.104 3.9 60.3 61.6 9.977 0.683
1084-19-2G 1.4 2.776 0.006 0.002 18.7 2.836 0.294 10.8 71.0 85.5 10.687 0.176
1084-19-2H 1.4 7.896 0.009 0.004 30.4 2.754 0.092 3.0 74.0 79.1 10.378 0.493
1084-19-2J 1.5 -14.434 -0.020 0.007 -26.3 2.844 0.013 0.4 74.5 50.7 10.869 4.870

153
CHAPTER 3

1084-19-2K 1.6 4.632 0.007 0.004 14.7 2.872 0.146 5.4 79.8 72.6 10.822 0.399
 40
Appendix 4b.1.(cont.) Ar/39Ar Analysis of alunite samples from the Colquijirca district

154
1084-19-2L 1.7 2.253 0.009 0.002 13.3 2.886 0.251 9.2 89.0 83.1 10.874 0.228
1084-19-2M 2.4 2.285 0.009 0.002 19.6 3.184 0.104 3.3 92.4 89.5 11.993 0.473
1084-19-2N 2.8 1.083 0.005 0.003 4.8 2.669 0.146 5.4 97.8 75.6 10.058 0.445
1084-19-2O 3.3 -2.691 0.001 0.004 -9.4 2.633 0.069 2.2 100.0 67.8 9.922 1.139
Integrated Age= 10.63 0.1
Plateau Age = 89.0 10.64 0.09

PBR-336 (J value = 0.002084 1.000000e-5):

1083-22-2A 1.2 13.631 0.038 2.844 0.1 11.144 0.057 0.9 0.9 1.3 41.418 5.005
1083-22-2B 1.2 17.623 0.025 0.978 0.2 3.701 0.062 1.0 1.9 1.3 13.861 2.492
1083-22-2C 1.2 4.386 0.011 0.285 0.2 3.338 0.202 3.3 5.2 3.8 12.507 0.776
1083-22-2D 1.2 1.320 0.016 0.056 0.3 3.972 0.011 0.2 5.3 19.4 14.872 5.390
1083-22-2E 1.2 10.007 0.014 0.055 2.5 3.220 0.175 2.8 8.2 16.9 12.066 0.441
1083-22-2F 1.2 7.946 0.011 0.048 2.2 3.009 0.231 3.7 11.9 17.7 11.277 0.361
1083-22-2I 1.3 1.719 0.005 0.042 0.6 3.110 0.873 14.1 25.9 20.3 11.655 0.311
1083-22-2J 1.3 1.235 0.007 0.035 0.5 3.143 1.022 16.5 42.4 23.3 11.778 0.129
1083-22-2K 1.3 4.139 0.009 0.014 3.9 3.168 0.675 10.9 53.3 43.5 11.871 0.117
1083-22-2L 1.3 2.599 0.006 0.010 3.7 3.183 1.771 28.5 81.9 53.7 11.927 0.055
1083-22-2N 1.3 1.913 0.008 0.005 5.7 3.194 0.435 7.1 88.9 71.4 11.969 0.149
1083-22-2P 1.4 3.700 0.008 0.009 5.7 3.188 0.361 5.8 94.7 56.4 11.946 0.185
1083-22-2Q 1.4 5.788 0.011 0.021 3.7 3.157 0.238 3.8 98.6 34.3 11.832 0.284
1083-22-2R 1.4 15.207 0.004 0.039 5.3 3.397 0.089 1.4 100.0 23.5 12.727 0.772
Integrated Age= 12.16 0.13
Plateau Age = 99.1 11.9 0.07

PBR-273 (J value = 0.0021036 1.000000e-5):

1081-17-3C 1.2 0.668 0.031 0.343 0.0 3.312 0.063 2.2 2.2 3.2 12.526 1.799
1081-17-3E 1.4 3.817 0.011 0.028 1.8 3.102 0.448 15.7 18.0 27.5 11.736 0.257
1081-17-3F 1.4 0.771 0.006 0.014 0.8 3.041 1.208 42.5 60.5 42.9 11.504 0.092
1081-17-3G 1.5 1.410 0.007 0.004 5.0 3.060 0.211 7.4 67.9 74.1 11.574 0.586
1081-17-3H 1.5 9.223 0.011 0.065 1.9 3.268 0.181 6.4 74.2 14.6 12.361 0.622
1081-17-3I 1.7 1.485 0.005 0.010 2.0 2.974 0.285 10.0 84.3 50.3 11.250 0.397
1081-17-3J 3.0 3.800 0.008 0.008 6.7 3.012 0 15.7 100.0 58.6 11.507 0.017
Integrated Age= 11.57 0.12
Plateau Age = 100.0 11.51 0.06
CHAPTER 3
 CHAPTER 3

Appendix 4b.2. Additional details of analyzed alunite samples of the Colquijirca district
UTM coordinates grain size sample
Approximate mineralogical composition
Sample Area/Deposit
South West Altitude (m) of the final alunite separate2
(m) amount 1

Au-(Ag) high sulfidation epithermal ores

PBR-335 Central Marcapunta S-8808229 W-361117 4459 500-3000 2.8 al>99%; qz<0.5%
PBR-336 Central Marcapunta S-8808395 W-361116 4432 300-1000 3.2 al>99%; qz<0.5%
PBR-338 Central Marcapunta S-8808464 W-360818 4434 300-1000 3.4 al>99%; qz<0.5%; go<0.5%
PBR-273 Southern Marcapunta S-8807711 W-360867 4405 >20000 5.6 al>99%; go<0.5%

Cordilleran base metal lode and replacement bodies

PBR-298 Colquijirca S-8811058 W-360947 4258 300-1000 3.5 al>99%; dck<0.5%, qz<0.5%
PBR-244 Colquijirca S-8811061 W-360973 4252 150-500 3.4 al>99%; qz<0.5%
PBR-322 Smelter S-8809162 W-361189 4189 500-3000 2.1 al>99%; qz<0.5%
PBR-208. San Gregorio (DDH : 15G)
3
S-8804686 W-360278 3998 <30 410 al 80-85%, py>>sl 10%, qz-kao 10%
PBR-284a San Gregorio (DDH: 37G) S-8805044 W-360484 4006 <25 880 al 70-75%, py>>sl 15-20%, qz-kao <5%
PBR-209. San Gregorio (Gualquepaqui) S-8805463 W-360626 4209 <10 870 al 80%, kao 10%, qz 5%, an 5%

1. in mg before dating procedure.

2. al, alunite; py, pyrite; sl, sphalerite; qz, quartz; an, anatase; kao, kaolinite; go, goethite; dck, dickite
3. DDH: Diamond drill hole

155
 CHAPTER 3

156

Chapter 4
Basic features of the hydrothermal fluids in
the Colquijirca District. A record from fluid
inclusions and stable isotopes.
The recognition from field and microscope
evidences (Chapters 2a, 2b, 2c, 2d) as well as
radiometric data (Chapters 3a and 3b) of two main
ore-forming events, an early disseminated Au-(Ag)
epithermal high sulfidation and a 300.000 years
younger Cordilleran base metal mineralization,
invites to structure this chapter into two parts, one
per event, starting with the Au-(Ag) mineralization.
I. The Oro Marcapunta Au-(Ag) epithermal
high sulfidation fluids
Epithermal high sulfidation Au-(Ag)
mineralization occurs exclusively in the Marcapunta
volcanic complex. The system developed an early acid
leaching (Early barren stage) that mainly affected the
central parts of the volcanic complex and produced
residual vuggy silica zoned to quartz-alunite alteration
in inner parts and sericite-calcite in external parts.
With the aim to track the pristine nature of the
hydrothermal fluids, prior to major changes upon
neutralization, phases selected for fluid inclusions
microthermometry and stable isotope analysis
correspond only to the internal parts of altered
bodies, i.e., quartz and alunite from vuggy silica and
quartz-alunite zones. Precious metals precipitated
together with sulfides and quartz in veinlets during
the Gold stage in highly permeable structures
produced during the Early barren stage. Due to the
fine-grained character of the veinlet mineralogy, only
two quartz samples were suitable for fluid inclusions
and isotopic studies. A late occurrence of several
varieties of plumose alunite veins, and breccias,
occasionally accompanied by quartz (Late stages), is
observed at several places. Reconnaissance isotopic
analysis on two Late stages plumose alunite samples
were carried out.
According to high precision 40Ar/39Ar dating
on Early barren stage alunite samples, the epithermal
high sulfidation Au-(Ag) system lasted for no less than
0.8 My (from 11.9 to 11.1 Ma). At least two recurrent
hydrothermal events, each consisting of their own
sequence of stages, i.e. Early barren stage followed
CHAPTER 4
by a Gold stage and then by Late stages, took place
in the Marcapunta volcanic complex (Chapter 3b).
Consequently and considering the virtually identical
features of at least three events identified, the
fluid inclusion and stable isotope study represents
collectively the two (or more) recurrent events.
a. Fluid inclusion microthermometry
Grains sampled and method of study:
Sixteen doubled polished thin sections,
approximately 100 m thick, were prepared from
fine-grained quartz separates (Table 4.1). Of these,
14 represent the Early barren stage whereas only two
samples are from the Gold stage. These two samples
are the best available record of the economic stages
of the hydrothermal system responsible for the Au-
(Ag) epithermal mineralization.
In addition, seven grains of coarse-grained
platy alunite from the Early barren stage were found
to contain one to two fluid inclusions suitable for
microthermometry (Table 4.1). These platy grains,
up to 300 m across (parallel to c axis), were directly
studied without any additional treatment. From the
Early barren stage separates, three quartz-alunite
pairs were obtained in which reversal crystallization
between both minerals is observed (Figure 4.1D,E).
As described in Chapter 2c, such assemblage consists
typically of grains less of 2 mm in size. Two other
Early barren stage samples are large quartz grains (up
to 2 cm long) which were collected from vuggy silica
intervals without evidence of overprinting by veining
of the productive Gold stage. No other mineral is
observed to coexist with this quartz.
Measurements were performed using a Linkam
THMSG-600 heating-freezing stage mounted on a
DMLB Leica microscope equipped with 10x, 32x and
100x lens. The distribution of fluid inclusions and
the measurements were monitored using a camera
and recorded by a video digitizing system connected
to a computer.
The precision of the measurements was
157
 CHAPTER 4

quartz

botroidal
hematite

A B 50 m 1 cm
enargite

quartz
dickite

2 cm 1 cm
C D

alunite

quartz

1 mm
E F

Figure 4.1: Images from several associations and assemblages containing most of the main phases used for fluid
inclusions and stable isotope studies of the precious metal high sulfidation epithermal mineralization of Oro Marca-
punta. A. Backscattered electron image of sample PBR-213. The typical pattern of reversal crystallization between
quartz and alunite can be observed. B. Sample PBR-305 showing vuggy silica alteration consisting of fine-grained
euhedral quartz in voids partially coated by Au-bearing botroidal hematite. The small image shows a backscattered
electron image from sample PBR-408 showing a similar occurrence of Au-bearing botryoidal hematite C. Hand
sample from a southern Oro Marcapunta outcrop presented in Figure 2C.4F in which plumose alunite (sample
PBR-273) cement Au-bearing rounded clasts (up to 2 ppm Au) of vuggy silica from the disseminated epithermal
Au-(Ag) system. Some euhedral quartz grains floating in the plumose alunite matrix can be distinguished. D.
Dickite as open space filling in contact with euhedral enargite from the Cordilleran mineralization at Smelter. Note
that no reaction occurred. E. Backscattered electron image of sample PBR-238 from Smelter showing intimate
intergrown of Cordilleran Main ore stage quartz, pyrite, and alunite. F. Detail of reversal crystallization between
alunite and quartz from Cordilleran mineralization revealed by backscattered electron image of sample PBR-214.
Note quartz growing on alunite and then alunite on quartz.

0.1C in the freezing runs (<30) and 1C
in the heating runs (>30C). Temperature
measurements were calibrated using synthetic
fluid inclusions (SYN FLINC) for which known
phase transitions were -56.6C (triple point of
pure CO2), 0.0C (triple point of pure H2O) and
374.1C (critical point of pure H2O).
Fluid inclusions hosted in quartz were heated
and cooled at variable ratios (up to 50C/minute)
whereas fluid inclusions trapped in alunite had to be
studied at ratios below 8C/minute. The experiments
in this study show that higher ratios, particularly on
heating runs, provoke collapse of the fluid inclusions
in this particular host mineral.

158
 CHAPTER 4

Microthermometric measurements were made
in small groups of trails of fluid inclusions (2n6)
which displayed consistent liquid-to-vapor ratios.
In order to avoid analysis of fluid inclusions which
underwent leakage or decrepitation, fluid inclusion
groups with significantly variable liquid-to-vapor
ratios or dispersed homogenization temperatures
were discarded. One representative measure per
trail or group is presented in all diagrams involving
Th and Tm. An exception are alunite-hosted fluid
inclusions which in most grains are observed to
occur alone or accompanied by extremely fine fluid
inclusions (<5 m). In these cases, Th and Tm
given in diagrams and tables only represent one
measurement.
The presence of dissolved gases other
than H2O was tested in selected fluid inclusions
using a LabRam Raman Microprobe equipped
with an Olympus microscope.
Fluid inclusion types and occurrence:
In this study most of the fluid inclusions

A 100 m B 100 m

C 50 m D 100 m

200 m 100 m
E F

Figure 4.2: Selected images of typical fluid inclusion occurrences from the Colquijirca district. A. A typical cluster
of low salinity quartz-hosted primary fluid inclusions from the Early barren stage from the disseminated Oro Mar-
capunta Au-(Ag) mineralization. B. Primary fluid inclusion in Main ore stage quartz from the Smelter Cordilleran
deposit. C. Primary fluid inclusion in enargite from the Smelter Cordilleran deposit observed through infrared imag-
ery. Note corrosion of enargite controlled by growing and cleavage plans. D. Primary fluid inclusions arranged paral-
lel to the border of a quartz grain from the Smelter deposit. E. Primary fluid inclusion in barite from the Colquijirca
deposit. F. Sphalerite-hosted fluid inclusion oriented according to growing zones from the Colquijirca deposit.

159

selected for measurements are primary. However,
a considerable number are secondary inclusions.
Criteria taken for the selection of primary fluid
inclusions followed lines suggested by Roedder (1984)
including their distribution in a growth zone or an
isolated plane (Figure 4.2). The vast majority of the
inclusions observed in the samples studied consisted
only of liquid and vapor at room temperature
(Figure 4.2). On the basis of phase assemblages,
two main types of fluid inclusions were recognized
in all samples studied: L type inclusions and V type
inclusions with (vapor to liquid ratios <0.5 and >0.9,
respectively.
Fluid inclusions in quartz and alunite from the Early
barren stage
L type inclusions, primary and secondary in
origin, contain two fluid phases and constitute the
most abundant type. A liquid water solution and a
vapor bubble amounting generally to no more than
a third of the inclusion in volume (Figure 4.2), is
observed. These inclusions are found irrespective
of the host mineral, this is, in quartz from vuggy
silica rocks or in both minerals of quartz-alunite
assemblage (though only five fluid inclusions hosted
in alunite were studied). L type inclusions display
a variety of geometries, but an elliptical form
prevails. Size of the fluid inclusions ranges from
a few microns up to several hundreds of microns
(Figure 4.2E). L type inclusions are by far the most
abundant in quartz chips from the Early barren
stage in which display a relatively constant vapor-to-
liquid ratio of around 0.25 to 0.35.
V type inclusions consist of two (liquid and
vapor) visible phases at room temperature being the
vapor phase in most cases in excess of 90 volume %
and commonly up to >95 volume % (Figure 4.2A,
B). These inclusions tend to be more abundant in
alunite grains or in quartz grains in contact with
alunite (Figure 4.2D). In contrast to L type inclusions,
V type inclusions are typically smaller than 10 m.
Vapor-rich inclusions are also observed commonly
as secondary inclusions in quartz in nearly a third
of the studied samples following planar arrays that
suggest healed microfractures (Figure 4.2E). These
secondary inclusions are very fine (up to 5 microns
long) and display either negative crystals or irregular
shapes. The absence in the planar arrays of liquid-
rich inclusions and the consistence in the vapor-to-
liquid ratios suggest that the vapor-rich inclusions
trapped a steam phase.
Fluid inclusions in quartz from the First ore stage
In a similar distribution to fluid inclusions in
quartz from the Early barren stage, L type inclusions
are common in the two studied gold-bearing samples
from the Gold stage. Nevertheless, L type inclusions
tend to show, though not consistently, lower amounts
160
CHAPTER 4
of the liquid fraction (up to one forth of the inclusion,
Figure 4.2F). On the other hand, V type secondary
fluid inclusions were observed in one of the two Au-
bearing veinlets samples (PBR-452) in clusters where
they coexist with L type inclusions. Indeed, besides
V type and L type inclusions the clusters consist also
of fluid inclusions with distinct liquid-to-vapor ratios
suggesting boiling.
A more representative number of samples
from the Gold stage needs to be studied in order to
adequately constrain the distribution of the different
types of fluid inclusions and, therefore, the basic
features of the associated ore fluids of the productive
stage.
Microthermometry
Homogenization temperatures (Th) of 128
L type groups of fluid inclusions, and the final
melting point of ice (Tm) of 57 L type groups of
inclusions, in which ice was visible in freezing runs,
were obtained. The homogenization temperatures of
V type inclusions were not determined in this study
due to the difficulty involved with making visual
estimations when the vapor phase filled the inclusion
(Bodnar et al., 1985).
Vapor-rich inclusions (V type) were usually
frozen to determine if they contained gases other
than H2O, however, due to the extremely fine size
of the inclusions it was not possible to detect any
change of phase.
Tests using Raman microprobe were conducted
in a selection of several relatively large L type fluid
inclusions in order mainly to identify other possible
vapor phases present, particularly CO2, a phase
widely recognized in epithermal environments. The
tests failed to recognize CO2 in any of the selected
fluid inclusions suggesting that its concentration,
if present, is below the detection limit of the
instrument, i.e., <0.1 wt %. In general accordance, no
clathrate formation upon freezing was observed not
only in those inclusions tested via Raman, but in any
of the fluid inclusions in which microthermometric
measures were made.
Homogenization temperatures of both
primary and secondary fluid inclusions in quartz from
the Early barren stage vuggy silica and quartz-alunite
altered rocks, range collectively between 204C and
293.2C, with nearly 80 % of the values between 210
and 270 C (Figure 4.3). The five studied alunite-
hosted inclusions from quartz-alunite assemblages
gave similar Th values ranging between 230C and
272C (Table 4.1, Figure 4.3). Of these, four fluid
inclusion gave Th nearly identical (within 2C, Table
4.1) to those groupings of primary inclusions hosted
in coexisting fine grained quartz. Relatively hotter
fluids were recorded in several clusters of primary
fluid inclusions picked from the two vuggy silica
samples (up to 293.2C, sample PBR-375) though
 CHAPTER 4

Table 4.1. Summary of microthermometric results for fluid inclusions of the Oro Marcapunta occurrence.
Host Inclusion Salinity
Sample Stage Observations Tm ice C ThC
mineral type NaCl wt % eq
PBR-213 quartz Early barren stage Quartz-alunite zone. Qrt-alu as replacements. secondary -0.1 0.18 216.8
PBR-213 quartz Early barren stage Quartz-alunite zone. Qrt-alu as replacements. primary -0.2 0.35 209.5
PBR-213 quartz Early barren stage Quartz-alunite zone. Qrt-alu as replacements. secondary -0.2 0.35 232.4
PBR-335 quartz Early barren stage Quartz-alunite zone. Qrt-alu as replacements. primary -0.3 0.53 210.8
PBR-336 quartz Early barren stage Quartz-alunite zone. Qrt-alu as replacements. secondary -0.3 0.53 220.0
PBR-375 quartz Early barren stage Vuggy silica zone. secondary -0.3 0.53 224.8
PBR-375 quartz Early barren stage Vuggy silica zone. secondary -0.4 0.71 225.4
PBR-336 quartz Early barren stage Quartz-alunite zone. Qrt-alu as replacements. primary -0.5 0.88 232.2
PBR-213 quartz Early barren stage Quartz-alunite zone. Qrt-alu as replacements. secondary -0.5 0.88 238.4
PBR-338 quartz Early barren stage Vuggy silica zone. Qtz-alu coating void walls primary -0.5 0.88 238.9
PBR-338 quartz Early barren stage Vuggy silica zone. Qtz-alu coating void walls primary -0.5 0.88 240.7
PBR-284 quartz Gold stage Quartz-sulfides veinlets primary -0.5 0.88 257.0
PBR-336 alunite Early barren stage Quartz-alunite zone. Qrt-alu as replacements. primary -0.6 1.05 229.4
PBR-336 quartz Early barren stage Quartz-alunite zone. Qrt-alu as replacements. primary -0.6 1.05 230.3
PBR-336 quartz Early barren stage Quartz-alunite zone. Qrt-alu as replacements. secondary -0.7 1.23 228.4
PBR-213 quartz Early barren stage Quartz-alunite zone. Qrt-alu as replacements. secondary -0.7 1.23 239.9
PBR-338 quartz Early barren stage Vuggy silica zone. Qtz-alu coating void walls primary -0.7 1.23 244.6
PBR-338 quartz Early barren stage Vuggy silica zone. Qtz-alu coating void walls secondary -0.7 1.23 245.3
PBR-336 quartz Early barren stage Quartz-alunite zone. Qrt-alu as replacements. primary -0.7 1.23 254.0
PBR-409 quartz Gold stage Quartz-sulfides veinlets secondary -0.8 1.40 189.0
PBR-338 quartz Early barren stage Vuggy silica zone. Qtz-alu coating void walls primary -0.8 1.40 225.7
PBR-284 quartz Gold stage Quartz-sulfides veinlets primary -0.8 1.40 248.4
PBR-284 quartz Gold stage Quartz-sulfides veinlets secondary -0.8 1.40 224.6
PBR-338 quartz Early barren stage Vuggy silica zone. Qtz-alu coating void walls primary -0.9 1.57 212.8
PBR-338 quartz Early barren stage Vuggy silica zone. Qtz-alu coating void walls primary -0.9 1.57 227.2
PBR-336 alunite Early barren stage Quartz-alunite zone. Qrt-alu as replacements. primary -0.9 1.57 272.2
PBR-213 quartz Early barren stage Quartz-alunite zone. Qrt-alu as replacements. primary -1.0 1.74 204.2
PBR-213 alunite Early barren stage Quartz-alunite zone. Qrt-alu as replacements. primary -1.0 1.74 239.5
PBR-336 quartz Early barren stage Quartz-alunite zone. Qrt-alu as replacements. secondary -1.0 1.74 242.1
PBR-375 quartz Early barren stage Vuggy silica zone. primary -1.0 1.74 247.0
PBR-284 quartz Gold stage Quartz-sulfides veinlets primary -1.0 1.74 259.4
PBR-336 alunite Early barren stage Quartz-alunite zone. Qrt-alu as replacements. primary -1.0 1.74 248.1
PBR-338 quartz Early barren stage Vuggy silica zone. Qtz-alu coating void walls secondary -1.0 1.74 271.9
PBR-284 quartz Gold stage Quartz-sulfides veinlets secondary -1.0 1.74 246.8
PBR-336 quartz Early barren stage Quartz-alunite zone. Qrt-alu as replacements. primary -1.1 1.91 224.5
PBR-338 quartz Early barren stage Vuggy silica zone. Qtz-alu coating void walls secondary -1.1 1.91 241.9
PBR-375 quartz Early barren stage Vuggy silica zone. primary -1.1 1.91 284.7
PBR-336 quartz Early barren stage Quartz-alunite zone. Qrt-alu as replacements. primary -1.2 2.07 223.0
PBR-213 quartz Early barren stage Quartz-alunite zone. Qrt-alu as replacements. primary -1.2 2.07 238.7
PBR-336 alunite Early barren stage Quartz-alunite zone. Qrt-alu as replacements. primary -1.2 2.07 240.2
PBR-338 quartz Early barren stage Vuggy silica zone. Qtz-alu coating void walls secondary -1.2 2.07 250.6
PBR-375 quartz Early barren stage Vuggy silica zone. primary -1.2 2.07 281.3
PBR-375 quartz Early barren stage Vuggy silica zone. primary -1.2 2.07 293.2
PBR-338 quartz Early barren stage Vuggy silica zone. Qtz-alu coating void walls secondary -1.2 2.07 258.4
PBR-375 quartz Early barren stage Vuggy silica zone. primary -1.3 2.24 220.4
PBR-336 quartz Early barren stage Quartz-alunite zone. Qrt-alu as replacements. secondary -1.3 2.24 262.2
PBR-409 quartz Gold stage Quartz-sulfides veinlets secondary -1.3 2.24 251.5
PBR-338 quartz Early barren stage Vuggy silica zone. Qtz-alu coating void walls secondary -1.4 2.41 227.4
PBR-338 quartz Early barren stage Vuggy silica zone. Qtz-alu coating void walls secondary -1.4 2.41 258.9
PBR-284 quartz Gold stage Quartz-sulfides veinlets primary -1.4 2.41 259.7

161
 CHAPTER 4

Table 4.1 (cont.) Summary of microthermometric results for fluid inclusions of the Oro Marcapunta occurrence.
PBR-284 quartz Gold stage Quartz-sulfides veinlets secondary -1.4 2.41 246.2
PBR-213 quartz Early barren stage Quartz-alunite zone. Qrt-alu as replacements. secondary -1.5 2.57 252.0
PBR-213 quartz Early barren stage Quartz-alunite zone. Qrt-alu as replacements. primary -1.6 2.74 258.8
PBR-338 quartz Early barren stage Vuggy silica zone. Qtz-alu coating void walls primary -1.6 2.74 264.0
PBR-338 quartz Early barren stage Vuggy silica zone. Qtz-alu coating void walls primary -1.6 2.74 276.5
PBR-336 quartz Early barren stage Quartz-alunite zone. Qrt-alu as replacements. secondary -1.7 2.90 236.8
PBR-338 quartz Early barren stage Vuggy silica zone. Qtz-alu coating void walls secondary -1.8 3.06 252.4
PBR-335 quartz Early barren stage Quartz-alunite zone. Qrt-alu as replacements. primary -2.0 3.39 267.6
PBR-409 quartz Gold stage Quartz-sulfides veinlets secondary -2.1 3.55 248.3
PBR-338 quartz Early barren stage Vuggy silica zone. Qtz-alu coating void walls primary -2.3 3.87 265.9
PBR-409 quartz Gold stage Quartz-sulfides veinlets primary -2.4 4.03 257.0
Fluid inclusions groups displaying apparent boiling
PBR-139 quartz Early barren stage Vuggy silica zone secondary -0.2 to -4.6 0.35 to 7.31 248.0
PBR-409 quartz Gold stage Quartz-sulfides veinlets secondary -0.9 to -2.1 1.57 to 3.55 231.8
PBR-409 quartz Gold stage Quartz-sulfides veinlets secondary -1.1 to -2.3 1.91 to 3.87 238.3
Fluid inclusions in quartz from the Early barren stage overprinted by Second gold stage
PBR-305 quartz Gold stage/EBS Vuggy silica zone. Au-bearing hm coating qtz. secondary -0.4 0.71 182.1
PBR-305 quartz Gold stage/EBS Vuggy silica zone. Au-bearing hm coating qtz. secondary -0.8 1.40 198.3
PBR-306 quartz Gold stage/EBS Vuggy silica zone. Au-bearing hm coating qtz. secondary -1.0 1.74 245.5
PBR-306 quartz Gold stage/EBS Vuggy silica zone. Au-bearing hm coating qtz. secondary -1.4 2.24 206.4
PBR-306 quartz Gold stage/EBS Vuggy silica zone. Au-bearing hm coating qtz. secondary -1.4 2.24 209.8
PBR-306 quartz Gold stage/EBS Vuggy silica zone. Au-bearing hm coating qtz. primary -2.1 3.55 264.2
PBR-306 quartz Gold stage/EBS Vuggy silica zone. Au-bearing hm coating qtz. primary -2.2 3.71 243.9
qtz, quartz; alu, alunite; hm, hematite; EBS, Early barren stage

most inclusions in vuggy silica quartz overlap the
230-272C range defined by the inclusions hosted
in the quartz-alunite assemblages (Table 4.1). Also
noticeable are the slightly hotter fluids evidenced
by quartz samples from quartz-alunite assemblages
occurring as coatings in vuggy silica (from 225.4
to 271.9C). Quartz fillings in quartz-alunite zones
immediately contiguous to vuggy silica rocks
display similar and slightly lower homogenization
temperatures (from 204.2 to 267.6C).
NaCl equivalent salinities found in primary
inclusions from the Early barren stage vary between
0.18 and 3.87 NaCl equivalent wt % (Figure 4.4).
From them vuggy silica quartz chips show primary
fluid inclusions with NaCl equivalent salinities ranging
between 1.74 and 2.24 wt %. Primary fluid inclusions
hosted in quartz and alunite from samples containing
the quartz-alunite assemblage yield broadly similar
salinity intervals (quartz-hosted inclusions between
0.18 to 3.87 wt % NaCl equivalent and the five
alunite-hosted inclusions between 1.05 and 2.07 NaCl
equivalent (Figure 4.3). Individually, each of the five
primary alunite-hosted fluid inclusions gave salinities
close to those found in at least a group of primary or
secondary fluid inclusions in quartz.
As observed in histograms (Figure 4.3),
salinities measured in secondary fluid inclusions span
over a similar range of values than those found in
the primary inclusions, suggesting that at least part
of these secondary inclusions were formed by the
same fluids.
162
A vuggy silica quartz chip (sample PBR-139)
presented a trail of secondary fluid inclusions with
different vapor-to-liquid ratios, typical characteristics
of boiling fluids. The inclusions yield homogenization
temperatures nearly 248C and salinities ranging from
0.35 to as high as 7.31 wt % NaCl equivalent (Table
4.1). Such contrasting salinities in a same trail have
not been recognized in the other studied samples of
the Early barren stage.
The two quartz samples from the Gold stage
veinlets (PBR-284 and PBR-409) provided limited
microthermometric data. Representative Th of five
groups of primary fluid inclusions groups vary from
250 to 260C (Table 4.1). Secondary fluid inclusions
show a partly overlapping and generally slightly lower
range of Th from 251.5 down to 189C (Table 4.1).
Furthermore, secondary fluid inclusions from two
other quartz samples (PBR-305 and PBR-306), in
which quartz is overprinted by Au-bearing botryoidal
hematite from the Gold stage (Figure 4.1A) gave a
similar and lower range of Th from 182 to 245C
(Table 4.1).
Two groups of secondary fluid inclusions with
variable liquid-to-vapor ratios, suggesting boiling
(sample PBR-409), produced homogenization
temperatures clustered around 231.8 and 238.3C
(Table 4.1).
Salinities of primary and secondary fluid
inclusions hosted in quartz from the Gold stage are
distributed over a relatively narrow range of values
(between 1.74 and 4.03 NaCl wt % equivalent (Figure
 CHAPTER 4

Primary fluid inclusion: Secondary fluid inclusion:

in quartz from Gold stage in quartz-sulfide
in quartz from Gold stage quartz-sulfide
veinlets
veinlets
in quartz from Early barren stage in vuggy silica in quartz from Early barren stage in vuggy
zones silica zones
in alunite from Early barren stage in in quartz from Early barren stage in
quartz-alunite zones 6 quartz-alunite zones
in quartz from Early barren stage in
6 quartz-alunite zones
5
5
4
Frequency

Frequency
4
3
3

2 2

1 1

0
0 1 2 3 4 5 0
0 1 2 3 4 5
Salinity (wt% NaCl equ.)
salinity (wt% NaCl equ.)
5 6

4 5

4
3
Frequency

Frequency

3
2
2

1
1

0 0
200 220 240 260 280 300 180 200 220 240 260 280 300
Homogenization temperature (C) Homogenization temperature (C)

Figure 4.3: Histograms showing the distribution of fluid inclusions from the Early barren stage and Gold Stage from the Oro
Marcapunta disseminated mineralization according to their origin (primary and secondary) the zone, and the occurrence type they
represent vs. homogenization temperature (Th) and salinity (wt % NaCl equivalent).

b. Stable isotopes analysis

4.3, Table 4.1). The two groups of secondary fluid
inclusions thought to record boiling yield salinities
in the range of 1.57 and 3.87 NaCl wt % equivalent
(Table 4.1).
In order to provide further evidences on the
nature of the ore fluids responsible for the Early
barren stage and in a limited degree for the productive
stages responsible for the Au-(Ag) mineralization,
oxygen and hydrogen isotope analyses were carried
163

out on alunite and quartz samples. For most of the
selected samples fluid inclusion microthermometric
data are available. In addition, the sulfur isotope
composition of five alunite samples from the Early
barren stage has been measured. All isotope analyses
presented in this work were measured in the Stable
Isotope Laboratory of the University of Lausanne.
Analyzed samples and experimental procedure:
For the oxygen and hydrogen isotopes analysis of
alunite:
Analyzed alunite samples (n=9) correspond to
zones of quartz-alunite assemblages from the Early
barren stage and plumose alunite from the Late
stages. Of these, 7 samples correspond to the Early
barren stage from which samples PBR-198, PBR-
213, PBR-335, PBR-336, and PBR-337 belong to
quartz-alunite zones immediately surrounding vuggy
silica cores and two from vuggy silica zones in which
alunite is coatings cavities (PBR-214 and PBR-338).
The remaining two samples were collected from
crosscutting quartz-plumose alunite breccias from
the barren Late stages (PBR-273a and PBR-273b).
A visual record of these different habits is presented
in Figure 4.1, and in Chapter 2c). Pure alunite
separates (>95 %) were achieved by means of careful
handpicking. Fine-grained samples (<150 microns)
consisting of alunite accompanied mainly by clays
and sulfides were separated according procedures
described by Wasserman et al. (1992). Only samples
without recognizable (under the microscope)
pseudocubic cores of woodhouseite-svanvergite
composition were selected.
For 18O (SO4) analysis, alunite samples were
treated according to the procedure by Wasserman et
al. (1992). Summarizing, the samples are dissolved
in a heated solution of 0.5N NaOH and the
filtered solution is titrated with HCl, which avoids
coprecipitation of Al(OH)3 or alunite. Sulfate is
then precipitated as BaSO4 which subsequently
can be conventionally analyzed for oxygen isotope
compositions.
Measurement of the oxygen isotope
compositions of the BaSO4 precipitates were
made on 2 to 4 mg sized samples using high
temperature (1450C) reduction with a He-carrier
gas TC-EA continuous flow on a Delta Plus XL mass
spectrometer from Thermo-Finnigan according to
a method adapted after Vennemann et al. (2002).
Replicate analyses were conducted for all samples.
Three samples with significant deviated (>3 permil)
replicate values were reanalyzed together with other
batch of samples. The results are given in the standard
-notation expressed relative to VSMOW in permil
() (Table 4.2). The precision of the barite NBS-
127 standard oxygen isotope analyses was generally
better than 3 for the method used (average 18O
VSMOW of 9.5 compared to an expected value of
164
CHAPTER 4
9.3.
Hydrogen from alunite samples was extracted
following the method described by Sharp et al. (2001)
for hydrous minerals. Samples (0.3 to 0.6 mg) were
deposited into Ag-cups and flushed with He and
reacted with graphite at 1450C. Hydrogen isotope
compositions were then measured using a TC-EA
continuous flow linked to a Delta Plus XL mass
spectrometer. D values are presented in permil
units (relative to V-SMOW). An in-house kaolinite
standard (Kaol #17) was used to control the analysis
of the alunite samples, The calibration procedure of
this Kaol #17 standard is described in the section
of the stable isotopes analysis from the Polymetallic
Cordilleran samples. Generally, the precision of the
Kaol #17 resulted better than 2 (average D
VSMOW of -124.9 for n=23).
For the oxygen isotopes analysis of quartz:
Eight samples of fine-grained quartz (200-500
m long) were handpicked for analysis. From these, six
correspond to altered zones formed during the Early
barren stage and two to Au-bearing veinlets from the
Gold stage (PBR-284 and PBR-409) (Table 4.3). Of
the first group (Early barren stage) two samples were
collected from vuggy silica cores (PBR-408, PBR-
375), two from quartz-alunite surrounding zones
(PBR-336 and PBR-213), and two from vuggy silica
zones in which quartz occurs together with alunite
coating cavities (PBR-214 and PBR-338, see Figure
4.1). An additional coarse-grained quartz sample
collected from quartz-plumose alunite breccias from
the barren Late stages was also analyzed (PBR-
273a). Replicate analyses were performed for three
samples.
The oxygen isotope composition (16O, 17O,
18
O) was obtained using a method similar to that
described by Sharp (1990) and Rumble and Hoering
(1994) and described in more detail in Kasemann
et al. (2001). Amounts per sample ranging from 1.5
to 2.8 mg were loaded onto a Pt-sample holder and
pumped out to a vacuum of about 10-6 mbar. After
prefluorination of the sample chamber overnight, the
samples were heated with a CO2-laser in 50 mbars of
pure F2. Excess F2 is separated from the O2 produced
by conversion to Cl2 using KCl held at 150C. The
extracted O2 is collected on a molecular sieve (13X)
and subsequently expanded into the inlet of a
Finnigan MAT 253 isotope ratio mass spectrometer.
Oxygen isotope compositions are given in the
standard -notation, expressed relative to VSMOW
in permil (). Replicate oxygen isotope analyses of
the standards used (Ls-1 Qtz (n = 8); Valley et. al.,
1995) generally have an average precision of 0.2
for 18O.
For the sulfur isotope analysis of alunite:
Five alunite separates, which were analyzed for
their oxygen and hydrogen isotopic composition, were
 CHAPTER 4

Table 4.2. Hydrogen and oxygen isotope composition of alunite samples from the Oro Marcapunta Au-(Ag) epithermal high sulfidation
occurrence.
Sample Stage Mineralogical description D1 18O2 H 2O
( VSMOW) ( VSMOW) wt %
PBR-214 -48 12.34
Alunite-quartz as coatings in voids of vuggy silica zone.
PBR-214 Alunite displays reversal crystallization with quartz, -50 12.16
Early barren stage I.M.
PBR-214 both minerals euhedral and less than 400 m size. Minor -48 12.45
zunyite+native S.
-49

PBR-213 Alunite-quartz filling (replacing?) entirely former K- -95 3.3 12.42

PBR-213 felds phenocrysts and other magmatic grains in qtz-alu -95 2.5 12.23
Early barren stage zone peripheral to vuggy-silica ledge. Minor pyrophyllite
PBR-213 as intergrain disseminations. Reversal crystallyzation -96 12.14
between alunite and quartz. -95 2.9

PBR-198 -59 16.5 11.63

Alunite-quartz as coatings in voids of vuggy silica zone.
PBR-198 Alunite displays reversal crystallization with quartz, -60 14.6 11.13
Early barren stage
PBR-198 both minerals euhedral and less than 800 m size. Minor -60 11.45
zunyite and pyrophyllite?.
-60 15.6

PBR-338 -55 12.76

Alunite-quartz as coatings in voids of vuggy silica zone.
PBR-338 Alunite displays reversal crystallization with quartz, -53 12.64
Early barren stage I.M.
PBR-338 both minerals euhedral and less than 800 m size. Minor -53 12.98
zunyite.
-54

PBR-335 -81 5.7 13.02

Alunite-quartz filling (replacing?) almost completely
PBR-335 former K-feldspars phenocrysts and other magmatic -84 13.14
Early barren stage
PBR-335 grains in qtz-alu zone adjacent to vuggy silica core. -84 12.87
Reversal crystallyzation between alunite and quartz.
-83 5.7

PBR-336 -79 2.2 13.40

PBR-336 Idem to sample PBR-338. -79 2.6 13.20
Early barren stage
PBR-336 -77 13.57
-78 2.4

PBR-337 -84 13.05

PBR-337 Early barren stage Idem to sample PBR-335. -86 I.M. 13.02
-85

PBR-273a Plumose alunite-quartz cementing centimetric rounded -86 3.6 13.21

PBR-273a Late stages Au-bearing vuggy silica clasts. Quartz floating within -85 12.99
plumose alunite masses which attain up to 2-3 cm size. -86 3.6

PBR-273b -86 13.99

PBR-273b -83 14.11
Idem to sample PBR-273a.
PBR-273b Late stages -83 N.A. 14.16
PBR-273b -83 13.98
-84
I.M.; insufficient material obtained
N.A.; not analyzed
average values in bold case
1. Two replicate analysis per sample performed
2. A replicate analysis performed if enough remaining material
K-felds, K feldspars; qtz, quartz; alu, alunite;

165
 CHAPTER 4

selected for sulfur isotope analysis. Three of them
precipitated early from the acidic fluids of the Early
barren stage (Table 4.4). Of this group, two samples
correspond to quartz-alunite zones immediately
adjacent to strongly leached vuggy silica bodies (PBR-
198 and PBR-214) and one from vuggy silica bodies
in which alunite occurs accompanied by quartz as
coatings (PBR-338; Figure 4.1). The remaining two
alunite samples, collected from the same outcrop
but 15 m apart (PBR-273a and PBR-273b), consist
of Late stages plumose alunite occurring as breccia
matrix which cut rocks containing both, quartz-
alunite assemblages from the Early barren stage and
Au-bearing oxides from the Gold stage (e.g., Figures
4.1 and 3b.3).
The on-line analytical method couples a
Carlo Erba NA 1500 elemental analyzer column to
a Finnigan delta S mass spectrometer. Sulfates were
reduced to powder and encapsulated in tin vials.
They then are transferred to the column heated at
1020C where they are reacted with O2 to form SO2
in a continuous flow of He. This reaction is catalyzed
by tungsten incorporated in its oxide form in the
reactor. SO2 is purified in a chromatographic column
and directly transferred and analyzed in the mass
spectrometer using the carrier gas.
Oxygen and hydrogen isotope composition of
alunite
Oxygen and hydrogen isotope composition of
alunite exhibit a large range of values. D values range
from -49 to as low as -95 , whereas 18O (SO4)
does from 2.4 to 15.6 (Table 4.2). Per groups,
according to their stage, values range as follow:
From the Early barren stage alunite as coatings in
vuggy silica zones yields average D compositions
of -49 and -54 (samples PBR-214 and PBR-
338, respectively). No oxygen isotope analysis were
performed on these two samples because of the
insufficient amount of BaSO4 precipitate obtained.
Also from the Early barren stage, alunite samples
occurring in quartz-alunite zones, immediately
bordering vuggy silica cores produced a larger range
of D and 18O (SO4) values (Table 4.2). On one
hand sample PBR-198 gave average D and 18O
(SO4) values of, respectively -60 and 15.6 , on
the other, sample PBR-213 yielded D and 18O (SO4)
values, in this order, of -95 and 2.9 . As given
in Table 4.2, the remaining three samples (PBR-335,
PBR-336, and PBR-337) exhibit a relatively narrow
range (D from -78 to -85 and 18O (SO4)
from 2.4 to 5.7 ) within that defined by samples
PBR-198 and PBR-213.
Obtained D and 18O (SO4) values on alunite
define ranges considerably wider than those reported
for other similar localities, particularly from the
relatively nearby Julcani and Pierina deposits (Deen
et al., 1994; Fifarek and Rye, 2005), which share many
similarities with Marcapunta, including, besides key
metallogenic aspects, its age and magmatic setting.
All D and 18O (SO4) values from the precocious
acid stage at Julcani published by Deen et al. (1994)
demarcate a narrower range between 14.4 and 17.1
for 18O (SO4) values and from -46 to -49 for D
values. Nonetheless, at Marcapunta, nearly half of the
samples have D and 18O (SO4) values ranges that
fit with those defined for the precocious acid stage
at Julcani, providing a further level of confidence to
the values obtained in this work. Another baseline of
inter-district and inter-laboratory comparison are the
results obtained from the Pierina deposit from which
alunite samples yielded, nearly similar to Marcapunta,
a wide range of 18O (SO4) values from 6.3 to 14.6
(Fifarek and Rye, 2005).

Table 4.3. Oxygen isotope composition of quartz samples related to the epithermal high sulfidation Au-(Ag) mineralization at
Marcapunta
18O (
Sample Stage Description: Alteration zone, assemblage/association VSMOW)

PBR- 214 Early barren stage Vuggy silica zone. Quartz, alunite, and minor zunyite and native S coating cavities walls 15.1
PBR-338 Early barren stage Vuggy silica zone. Quartz, alunite, and minor zunyite and native S coating cavities walls 15.5
Quartz-alunite zone next to vuggy silica bodies. Qtz-alu replacing mainly plag and K
PBR-335 Early barren stage feld. 10.6
Quartz-alunite zone next to vuggy silica bodies. Qtz-alu replacing mainly plag and K
PBR-213 Early barren stage feld. 6.7
PBR-375 Early barren stage Vuggy silica zone. Only quartz is observed as coatings on former feldspars walls. 8.9
PBR-408 Early barren stage Vuggy silica zone. Only quartz is observed as coatings on former feldspars walls. 11.9
Quartz from oxidized veinlets accompanied by clay minerals, i.e. kaolinite, smectite,
illite.
PBR-409 First gold stage 7.3
Quartz from oxidized veinlets accompanied by clay minerals, i.e. kaolinite, smectite,
PBR-284 First gold stage illite. 6.7
PBR-273 Late stages Plumose alunite-quartz-rich breccias. Qtz-alu cementing Au-bearing vuggy silica clasts 9.3
Qtz, quartz; alu, alunite; feld, feldspar

166
 CHAPTER 4

The two plumose alunite samples representing
the basically uneconomic Late stages gave close
average D values of -83.8 and -85.6 . A unique
oxygen isotope analysis on sample PBR-273a yielded
a 18O (SO4) composition of 3.6 (Table 4.2). These
isotopic compositions contrast with values reported
for plumose alunite from the type locality for this
variety of coarse-grained alunite at Marysvale, Utah
(Rye, 1993) which has D and 18O (SO4) values of
around -70 and 10 , respectively. On the other
hand, 18O (SO4) values from plumose alunite from
the Pierina deposit seem to be more enriched in 18O
(SO4) (6.5 to 8.6 ) than the sole value obtained
from Oro Marcapunta at 3.6 (Table 4.2).
Oxygen isotope composition of quartz
The oxygen isotope composition of quartz
samples can be divided into three groups according
to the stages they represent (Table 4.3). A first group
of six samples (PBR-213, PBR-214, PBR-336,
PBR-338, PBR-375, and PBR-408), those separated
from alunite-bearing advanced argillic alteration
assemblages from the Early barren stage, comprise
18O values varying from 8.9 to 15.5 . The highest
of them at 15.1 and 15.5 correspond to quartz
precipitated together with alunite and minor zunyite
and native sulfur in the inner parts of vuggy silica
bodies. Quartz in these cases occurs as tiny euhedral
grains coating walls of what once were mainly K-
feldspar and plagioclase grains (PBR-214 and PBR-
338), a habit distinct to the widespread disseminated
style of quartz-alunite assemblages filling almost
entirely cavities of the original magmatic grains (as
replacements?) in contiguous zones to vuggy silica
core. Quartz belonging to this last style gave lower
and contrasting 18O values of 6.7 and 10.6
(samples PBR-213 and PBR-335, respectively). A
third sub-group of samples (PBR-375 and PBR-408)
produced 18O values of 8.9 and 11.9 . Both
quartz samples were obtained from walls of voids in
vuggy silica rocks after mainly former K-feldspars and
plagioclase and where no other mineral is observed
Table 4.4. Sulfur isotope composition of alunite samples related to the epithermal high sulfidation Au-(Ag) mineralization at Marcapunta
Sample Stage Description: Alteration zone, assemblage/association
to coexist (except zircon under microscope).
The second group of quartz samples
represents the stage responsible for the precious
metal deposition. Due mainly to their scarcity and
fine-grained size (commonly less than a few hundred
microns long) only two samples suitable for analysis
were obtained. Their 18O compositions, PBR-284 at
6.7 and PBR-409 at 7.3 , are considerably lower
than the values obtained from the 6 quartz samples
from the Early barren stage.
The last quartz sample represents the Late
stages which formed breccias and veins dominated
mineralogically by plumose alunite accompanied in
some cases by quartz. Quartz accompanying plumose
alunite from sample PBR-273a yields a 18O value of
9.3 , indistinguishable from the range of values
defined by the 6 samples from the also acidic Early
barren stage (Table 4.3).
Sulfur isotope composition of alunite
The five analyzed alunite samples from the
Early barren stage and Late stages exhibit a close
range of 34S values from 20.6 and 22.3
(Table 4.4). These data are lower than the average
composition reported for alunite from equivalent
quartz-alunite zones from several similar epithermal
Au-(Ag) deposits such as Pierina in northern Peru
and Rodalquilar in Spain which show 34S values as
high as 31 (Rainbow et al., 2005; and Arribas et
al., 1995). It cannot be ruled out, however, that the
analysis of additional samples may result in a wider
range of isotopic composition of alunite comparable
to these deposits, as it may be suggested by the
relatively large variations in the hydrogen and oxygen
isotope composition of other alunite samples.
The few available data for Early barren stage
alunite from quartz-alunite assemblages from both,
vuggy silica and quartz-alunite zones are almost
undistinguishable, between 21.5 and 22.4 .
Plumose alunite gave values slightly lower than this
interval at 20.6 -20.7 . These compositions are
broadly similar to those reported for plumose alunite
34S (, CDT)

Quartz-alunite zone adjacent to vuggy silica bodies. Qtz-alu replacing mainly

PBR-198 Early barren stage plag and felds 21.49
Vuggy silica zone. Quartz, alunite, and minor zunyite and native S partially filling
PBR-214 Early barren stage cavities 22.37
Vuggy silica zone. Quartz, alunite, and minor zunyite and native S partially filling
PBR-338 Early barren stage cavities 21.58
Plumose alunite-quartz-rich breccias. Alu and qtz cementing Au-bearing vuggy
PBR-273a Late stages silica clasts 20.67
Plumose alunite-quartz-rich breccias. Alu and qtz cementing Au-bearing vuggy
PBR-273b Late stages silica clasts 20.64

Qtz, quartz; alu, alunite; feld, feldspar

167

for the relatively nearby Pierina deposit which are in
the interval of 12.3 to 28.3 and different than
the nearly zero values of the locality type for this
variety of alunite at Marysvale, Utah (Rye, 1993).
Discussion
An Early barren stage generated a core of
vuggy-silica controlled by permeable units (mainly
phreatomagmatic breccias, but also lava-dome units)
at the central zones of the volcanic complex. This
core was surrounded, from internal to external
contiguous zones, by advanced argillic alteration type
assemblages, quartz+alunite, quartz+alunite+dickit
e+kaolinite, and dickite+kaolinite+pyrophyllite. As
discussed in Chapter 2c, systematic selective chemical
analyses indicate that during the Early barren stage no
economic Au-(Ag) precipitation took place. During
the Gold stage, the previous assemblages were
overprinted by a succession of Au-(Ag)-bearing sulfide
veinlets, patches and disseminations accompanied by
clay minerals. Au-(Ag)-bearing botryoidal hematite-
goethite assemblages which probably formed coeval
with the sulfide-bearing veinlets are attributed to the
Gold stage.
These mineralogical assemblages, the observed
zoning as well as the tectonic setting and the associated
calc-alkaline volcanic rocks (Chapter 1) classify
the Oro Marcapunta occurrence a precious metal
high sulfidation epithermal system in the sense of
Einaudi et al. (2003). In this work the denomination
Au-(Ag) disseminated high sulfidation epithermal
mineralization is used.
At this point, in order to better discuss the
fluid inclusions and stable isotope results, a general
genetic model of an intrusion-related hydrothermal
system is summarized. The model is developed from
the study of ore deposits formed in stratovolcanoes,
or in silicic domes in continental terrains (e.g.,
Henley and Ellis, 1983; Rye, 1993; Hedenquist and
Lowenstern, 1994; Fournier, 1999). The key spatial
reference is the brittle-ductile transition that occurs
above a crystallizing magma at about 400 C. Below
this transition, rocks behave quasiplastically and brittle
fracturing is restricted, penetration by meteoric water
is minimized, and lithostatic pressures dominate.
Above the transition, meteoric water may be present
in open fractures and interact with a condensing
magmatic vapor phase from a degassing magma
chamber. Because of the depth of the magmas
and possible equilibration of magmatic fluids with
crystalline calc-alkaline crystalline rocks below the
brittle-ductile transition, condensing vapor fluids will
typically have H2S/SO2 ratios >1 (Rye, 1993). During
times of high volcanic gas flux, fluids may be more
SO2 rich. (Heald et al., 1963). Residual saline liquids or
vapor both separated from magmatic-hydrothermal
fluids may become the source of precious and
base metal mineralization at higher levels. At even
168
CHAPTER 4
shallower levels, the vapor plume may encounter
water and below 400 C, SO2 disproportionates
according to the reaction 4SO2 + 4H2O = 3H2SO4 +
H2S. The H2SO4 leads to extreme acid leaching and
the formation of various zoned of vuggy silica and
quartz-alunite assemblages and argillic and propylitic
haloes in a typically epithermal acid-sulfate or high
sulfidation hydrothermal environment. It is this last
portion of the system which specifically concerns the
Oro Marcapunta system and it is discussed in terms
of the available fluid inclusions and isotope data in
what follows.
Fluid inclusions provide some information
on the hydrothermal fluids from the Oro Marcapunta
high sulfidation system. They are invariably two
phase inclusions, mostly liquid-rich, but also vapor-
rich inclusions are widespread. They indicates that
both the Early barren stage and the productive
Gold stage were formed by low salinity fluids
(below 4 wt % NaCl equivalent) and at epithermal
conditions (below 270C). These basic features of
the circulating fluids are common to other epithermal
high sulfidation systems including remarkably the
Pierina and Yanacocha localities in northern Peru
and Rodalquilar in Spain (e.g., Fifarek and Rye, 2005;
Arribas et al., 1995).
Early barren stage
Primary inclusions in hydrothermal quartz and
alunite from the acidic Early barren stage evidence
fluids with salinities ranging from 0.35 to 3.87 wt %
NaCl equivalent at temperatures mostly between 210
and 270C. Secondary fluid inclusions record similar
ranges of salinities and temperatures (Figure 4.4). The
relationships between homogenization temperatures
and the salinities of primary and secondary fluid
inclusions hosted in quartz and alunite (Figure 4.4)
may be explained largely by mixing and cooling.
Mixing was probably widespread in the
Oro Marcapunta hydrothermal system. The most
general presumption rises from the salinity vs Th
plot (Figure 4.4) in which a mixing trend may be,
though not markedly, inferred. A group of mainly
primary fluid inclusions with salinities ranging from
3 to 4 wt % NaCl equivalent and temperatures from
250 to 280C appears to record an end member of
hot fluids. The other end-member is represented
by mostly secondary fluid inclusions with salinities
from nearly zero to slightly higher than 1 wt % NaCl
equivalent. These inclusions evidence cold fluids
with discernible lower homogenization temperatures
down to nearly 180C. The remaining fluid inclusion
population, which indeed is the main and consists of
both primary and secondary types, defines relatively
narrow ranges of salinities and temperatures delimited
by these two end members i.e., between 1 and 3 wt
% NaCl equivalent and between 220C and 260C
(Figure 4.4). The simplest conclusion is that most of
 CHAPTER 4

the studied fluid inclusions are the result, in different
degrees, of a mixing process (line a in Figure 4.4)
which involves two end members, cold fluids with
nearly zero salinities with hot and slightly higher
saline fluids.
The low temperature gradient of this
probable mixing trend (around 50C over a range of
4 wt % NaCl equivalent) may be explained by the
fact that the studied quartz and alunite samples were
collected from inner parts of the mineralizing centers,
presumably from zones in which no major variation
of temperature is expected to occur. The several
temperature highs (up to 293 C) of mixed waters
detected in the 1 to 3 wt % NaCl equivalent interval
(Figure 4.4) are interpreted as produced by heating
by dome intrusions which in several places of the
Marcapunta volcanic complex occurred coetaneously
with the hydrothermal alteration (Chapter 2c).
The almost one million year lifespan of the
Oro Marcapunta high sulfidation system indicated
by the alunite 40Ar/39Ar ages (from 11.90.07 to
11.100.06 Ma) suggests that several hydrothermal
episodes took place (Chapters 3a and 3b). Cooling
likely dominated the waning stages of each of these
individual episodes. In such periods, the meteoric
component of the hydrothermal fluids became
predominant with only minor contribution, if any,
of a magmatic constituent. The meteoric component
is manifested by the highly diluted fluids recorded
as secondary (late) fluid inclusions which in our
case would constitute the low salinity cold end-
member.
Boiling is evidenced only locally. The paucity
in the studied samples of typical features of this
process (e.g., contrasting vapor-to-liquid ratios in a
same trail of inclusions) suggests that boiling was
confined to particular and perhaps small sectors of
the Oro Marcapunta system. This postulate finds
support in the plotting salinities vs. Th (Figure 4.4)
in which no systematic decrease of temperature with

350

300
a

250
ThC

200

150

100
0.0 1.0 2.0 3.0 4.0 5.0
Salinity (wt % NaCl eq.)

Type of Early barren stage:

primary in quartz from vuggy silica zones
primary in quartz from quartz-alunite zones
secondary in quartz from vuggy silica zones
secondary in quartz from quartz-alunite zones
primary in alunite from quartz-alunite zones

Type of First gold stage fluid inclusions:

primary in quartz from First gold stage
secondary in quartz from First gold stage

Figure 4.4: Homogenization temperature (Th) vs. salinity (wt % NaCl equivalent) diagram of fluid inclusions in quartz and
alunite samples from the Oro Marcapunta occurrence. Dashed gray line represents an inferred mixing trend, see text for discus-
sion.

169
 CHAPTER 4

0
alunite (mineral) VV

-20 alunite fluid 400C

Oro Marcapunta 500C

L
W
-40 alunite fluids .001 600C

M
D (, SMOW)

700C

-60 860C
PMW
Exchange trend of
Julcani primary
-80 magmatic fluids
.01

D
-100 REN

E
C
GT

LIN
00
IXIN
NI M

ITE
CA
JUL

AT
JMW

IN
RV

E
-120 CU

OL
WE
JULCANI M

KA
.1
1
-140

LS quartz from plumose alunite-quartz ass.

First gold stage quartz

18OH in equilibrium with: EBS quartz (qtz-alu fillings)

2O
EBS quartz (qtz-alu coatings)

EBS quartz (vuggy silica zone)

-20 -15 -10 -5 0 5 10 15

18O (, SMOW)

Figure 4.5: D and 18O (SO4) field of Early barren stage alunite fluids and 18O variations for quartz fluids of the Gold
stage. The upper portion illustrates besides alunite fluids field, alunite isotopic compositions. Isotopic compositions of water in
equilibrium with alunite were calculated for several representative temperatures mostly according to microthermometric measure-
ments selected from Table 4.1: 240C for alunite fillings from quartz-alunite zones, 260C for alunite coatings from vuggy silica
zones. A temperature of 250C was considered for plumose alunite from Late stages. Equations used in estimation of alunite
fluids compositions are of Stoffregen et al. (1994) and for quartz fluids of Zhang et al. (1989). The lower portion of the figure
show variations of 18O composition for water in equilibrium with quartz from different zones. Temperatures in this case also
derive from microthermometry: 250C for quartz from First gold stage sulfide veinlets, 270C for quartz from vuggy silica zones,
and other temperatures as cited for the upper portion of the figure. Other fields and lines are MWL: meteoric water line (Craig,
1961); VV: volcanic vapor (Giggenbach, 1997); the kaolinite line (Savin and Epstein, 1970); PMW: primary magmatic
water (Taylor, 1979). Julcani parameters from Deen et al., (1994). Other abbreviations: MWE: meteoric water exchange; LS:
Late stages; EBS: Early barren stage; qtz: quartz; alu: alunite; ass: assemblage.

increasing salinity is recognized for the set of fluid
inclusions studied. The only sample from the Early
barren stage with signs of boiling (PBR-139, Table
4.1) Figure 4.5to a vuggy silica ledge which is
corresponds
controlled by fracturing. The quartz sample displays
a grouping of secondary fluid inclusions with end
member salinity values at 0.35 and 7.31 wt % NaCl
equivalent and Th at nearly 240C. Such contrasting
salinities suggest a boiling process which, however,
is not recorded in samples which are located in
neighboring quartz-alunite alteration zones (PBR-
336 and PBR-338). Possibly, these inclusions with
variable vapor/liquid ratios evidence local channeled
depressurization within highly permeable vuggy silica
ledges controlled by fractures.
Therefore, and with previously mentioned
local exception(s), it can be concluded that the vapor-
rich inclusions trapped a steam phase and would
not represent boiling processes. The widespread
distribution of these vapor-rich inclusions throughout

170

the acid alteration zones might indicate that the steam
phase contains significant amounts of magmatic
SO2.
The stable isotope data offer additional clues
on the nature of the alteration fluids and processes
involved. The Oro Marcapunta alunite and quartz
samples from the Early barren stage exhibit sulfur,
oxygen and hydrogen isotope compositions (Figure
4.5, Tables 4.2-4.4) characteristic of the magmatic
hydrothermal environment (e.g., Rye et al., 1992).
The S isotope data for the three alunite
samples from the Early barren stage (34S from
21.5 to 22.4 , Table 4.4) point to a magmatic-
hydrothermal environment in which sulfate has
equilibrated with H2S from the disproportionation
of SO2 within a condensing vapor plume (e.g., Rye,
1993). Given the limited data, it cannot be excluded
that the analysis of additional samples may result in a
wider range of isotopic composition of alunite as is
reported for other epithermal high sulfidation systems
(e.g., Rainbow et al., 2005, Arribas et al., 1995). The
large variations in the hydrogen and oxygen isotope
composition of other Oro Marcapunta alunite
samples, as is discussed below, sustain this idea.
For seek of simplicity, all D and 18O (SO4)
values discussed hereafter correspond to water in
isotopic equilibrium with alunite and quartz and were
calculated using fractionation factors of Stoffregen
et al. (1994) and Zhang et al. (1989), respectively.
For samples PBR-214 and PBR-338, 18O values of
quartz, which is observed in reversal crystallization
with alunite, were used. The resulting values are
plotted in Figure 4.5, which additionally includes a
water-rock exchange curve calculated for meteoric
water in equilibrium with Julcani dacite at 400 C at
several water/rock ratios (Deen et al., 1994). Similar
exchange trends were amply documented through the
years (e.g., Criss and Taylor, 1983; Campbell, 1984)
and give to this work a framework of comparison
and discussion. The same figure also depicts isotopic
compositions of waters initially in equilibrium with
Julcani magmas at 860C with igneous rocks from
860 to 400C. These isotopic modelings were chosen
considering the nearly identical magmatic suite that
Julcani (Shelnut and Noble, 1985) and Marcapunta
(Chapter 1) share. In addition, the isotopic
composition field of the Miocene meteoric water
at Julcani and the deducted mixing trend between it
and exchanged magmatic water (Deen et al., 1994)
are represented in Figure 4.5. Again, this locality
was selected, given the proximity and similar age of
the Julcani (10 Ma; Noble and Silberman, 1984) and
Colquijirca (Oro Marcapunta) systems.
According to the zone they represent, Early
barren stage alunite fluids from vuggy silica cores
displays the most magmatic signatures with D and
18
O (SO4) values varying from -48.7 to -59.8
and from 15.1 to 15.6 , respectively. These
compositions were obtained from alunite occurring
together with quartz as coatings on walls of cavities.
CHAPTER 4
These values are compatible with some of the
highest deposition temperatures indicated by quartz
microthermometry (260-275C) and the presence of
zunyite (stable at T>250C, Henley et al., 1997) as
part of the high sulfidation assemblage (also native
sulfur). Alunite from quartz-alunite zones, typically
as fillings and bordering vuggy silica cores, produced
the more depleted D and 18O (SO4) compositions
of alunite fluids.
The calculated isotope compositions of water
(D and 18O (SO4)) in equilibrium with Early barren
stage alunite (alunite fluids in Figure 4.5) define two
relatively contrasting compositional fields. The first
field is characterized by typical magmatic signatures
and is represented by the vuggy silica cores samples
PBR-214, PBR-198, and PBR-338. 18O enrichment
of alunite fluids indicated by these group of samples
is as high as >7 . The second field lies over an
intermediate segment of a trend representing mixing
at Julcani between meteoric water and exchanged
magmatic water (Figure 4.5). Samples PBR-213,
PBR-335, PBR-336, and PBR-337 from quartz-
alunite zones conform this second alunite fluids field
with 18O values ranging from -3 to as depleted as
-6.5 (Figure 4.5).
Two broad conclusions can be derived from
these results:
(1) Both compositional fields of alunite fluids
from Oro Marcapunta fit consistently with the
Julcani mixing trend between exchanged magmatic
fluids and meteoric fluids. Meteoric waters at Oro
Marcapunta would approach consequently the
isotopic compositions to those recognized at Julcani.
This hypothesis gains support if considering besides
the nearly same age of both systems, the relatively
short distance between them (~300 km).
(2) Generally, and despite of the apparent
important and variable participation of meteoric
water in the formation of some of the alunite fluids,
the second field of values indicates a largely dominant
magmatic contribution in the generation of the
advanced argillic alteration fluids. The magmatic end-
member, evidenced by the alunite fluids, was most
likely a magmatic vapor plume, from which, SO2
interacted with water and condensated to form H2SO4,
the main acid agent in the formation of the vuggy
silica and quartz-alunite alteration. Water responsible
for the disproportionation of SO2 was most probably
meteoric fluids, as is indicated by the less magmatic
second field of compositions of the alunite fluids
which fit the Julcani mixing trend (Figure 4.5).
Meteoric fluids mixed with the magmatic fluid vapors
probably only when the vapor plume reached shallow
levels of the system, i.e. at the site of vuggy silica and
quartz-alunite alteration. Deep drilling (Chapter 2c)
showing that vuggy silica ledges are restricted to such
shallow levels is coherent with this conclusion. The
fact that the isotopic composition of the Early barren
stage alunite fluids probably indicates variable inputs
of meteoric water into the hydrothermal system are
171

indicated by the wide spectrum of calculated 18O
values of water in equilibrium with quartz from
quartz-alunite assemblages (18O values of quartz
waters from quart-alunite fillings and quartz-alunite
coatings in Figure 4.5). D of water in equilibrium
with quartz from quartz-alunite assemblages would
approach values defined by the Oro Marcapunta (or
Julcani) mixing trend because none of the alunite
samples, which co-precipitated with quartz, indicate
participation of exchanged meteoric waters (Figure
4.5).
Gold stage
Primary inclusions in hydrothermal quartz
from Gold stage sulfide veinlets probably represent
the fluids responsible for the deposition of the Au-
(Ag)-bearing sulfides, mainly pyrite and subordinate
enargite, because sulfides are observed to have
precipitated coevally with quartz lining vuggy silica. At
Oro Marcapunta, in spite of the limited information
on the productive Gold stage, the variations of the
salinities (0.88 to 5.11 wt % NaCl equivalent) and
temperatures (189 to 260C) of primary and secondary
fluid inclusions suggest, as in the case of the Early
barren stage, a sequence of events including mixing,
cooling and subordinate boiling. Unfortunately, no
end members may be representatively be traced but
again, possible cold fluids (meteoric) and hot and
significantly more saline fluids may conform a mixing
trend (Figure 4.4). The stable isotope data discussed
below, give additional keys in the characterization of
these productive fluids.
Evidence of boiling during the Gold stage
is suggested by the coexistence of several trends
of liquid-rich and vapor-rich fluid inclusions in
the Au-bearing sample PBR-409. These inclusions,
excepting true vapor-rich inclusions (V type) which
are difficult to measure, homogenize at nearly the
same temperatures per cluster. Boiling is recorded
at around 230 to 240C, a temperature close to the
average homogenization temperatures found for both
the Early barren stage and the Gold stage. However,
moderate variations of salinity and liquid-to-vapor
ratios suggest that boiling was not vigorous.
A first approximation of pressure conditions
during the Gold stage of the Oro Marcapunta system
may be derived from the fluid inclusion trapped from
the boiling fluid. On the basis of a model in which
part of the economic mineralization occurs from a
hydrostatically pressured CO2-free NaCl-H2O fluid,
total pressure at the Th was calculated according
to the procedure described by Haas (1976) and
Barton and Chou (1993). Using the homogenization
temperature of 240C and salinities from 1 to 2 wt
% NaCl equivalent, the boiling curve adjusts for a
few hundred meters depth equivalent. Quartz sample
PBR-409 recording boiling was collected from
surface, 90 m west of the Marcapunta summit. This
implies that erosion of the volcanic complex was
172
CHAPTER 4
minor, probably <300 m. A similar depth estimation
is obtained by using boiling data from the Early
barren stage quartz sample PBR-139 (Table 4.1)
collected almost 200 m below the present surface.
18O compositions of water in equilibrium
with quartz from the Gold stage (PBR-284 and PBR-
409) are estimated at -2.6 and -2.1 (Table 4.3). These
compositions may involve both mixing between
magmatic water and meteoric water or exchanged
meteoric waters.
Late stages
No microthermometric data are available for
the Late stages plumose alunite. By analogy with the
isotopically similar plumose alunite at Pierina (Fifarek
and Rye, 2005), a temperature of 250C was used to
calculate fractionation factors (Table 4.2). At Pierina,
a range of plumose alunite deposition temperatures
from 150C to 320C was estimated based on 18OSO4-
OH
fractionations (Fifarek and Rye, 2005).
Late stages plumose alunite samples yielded
34S values of 20.6 and 22.4 (Table 4.4). These
values differ from the nearly 0 compositions from
the type locality of this particular coarse-grained
alunite at Marisvale (e.g., Rye et al., 1993). These high
34S signatures, as concluded for the Pierina deposit,
suggest that precipitation of plumose alunite at Oro
Marcapunta was the product of disproportionation
of SO2 to H2S and H2SO4 within a condensing vapor
plume.
The two calculated D and 18O (SO4) values
of the Late stages plumose alunite fluids (samples
PBR-273a and PBR-273b) are comprised within the
mixed fluids field defined by the alunite fluids from
the Early barren stage (Figure 4.5). It is, therefore,
concluded that a significant contribution of meteoric
water interacted with exchanged magmatic waters
during the Late stages.
II. Polymetallic Cordilleran fluids
The sulfide-rich polymetallic Cordilleran ores
developed in carbonate rocks and are the economically
most important of the district. These ores form a large
mineralized corridor that includes the studied deposits
of Smelter, Colquijirca, and San Gregorio (Chapters
2a, 2b, 2d, and 3). The Cordilleran hydrothermal
history, at least for Smelter and Colquijirca, begins
with an early stage which basically deposed silica and
pyrite (Early silica-pyrite stage) which constituted the
precursor fluids prior to the productive, chiefly base
metal, Main ore stage. Very limited fluid inclusion
and isotope data was obtained from the Silica pyrite
stage basically because ubiquitous overprinting by
the Main ore stage (Chapter 2a and 2b). The Main
ore stage followed the barren precipitation of silica
and pyrite with the formation of enargite bodies in

internal parts of the system and sphalerite-galena
toward its periphery. 40Ar/39Ar dating indicates that
the Main ore stage took place relatively shortly (0.3 to
0.2 My) after the last recognized Au-(Ag) epithermal
high sulfidation event at Oro Marcapunta dated at
11.1 Ma (Chapter 3b). In contrast to the protracted
hydrothermal activity recognized at Oro Marcapunta
(at least 0.8 My), the productive Main ore stage fluids,
except perhaps those from San Gregorio, would have
circulated for <0.1 to 0.4 My, from 10.830.06 Ma
to 10.590.06 Ma. Based on detailed crosscutting
relationships, at both microscopic and macroscopic
scale, during this period multiple reversal overprintings
between ore deposition and acid precipitates (quart-
alunite-zunyite) took place in what collectively is
called the Main ore stage. Indeed, the great majority
of fluid inclusion and stable isotope data represent
this stage. A last recognized period of economic
mineralization (Second ore stage), mainly chalcocite,
was superimposed on large parts of the Main ore
stage enargite zones. Unfortunately no fluid inclusion
and isotopic measurements were performed for this
stage, mainly because of the fine-grained character
of their constituents.
a. Fluid inclusions microthermometry
Grains sampled and method of study:
Grains sampled from the polymetallic
Cordilleran deposits consist of well formed quartz
and enargite from internal parts of the system
(enargite-bearing zones) and sphalerite, barite, and
quartz from intermediate parts (Cu-(Ag), Cu-(Bi-
Ag),
Zn-Pb-Cu-(Ag-Bi)
zones). Most samples are
from the internal parts of the system with the aim of
getting insight into fluids as pristine as possible.
Sixteen quartz samples belong to the three
enargite-bearing internal zones, i.e., Cu-(Au-Ag),
Cu-(Ag-Sn-Bi), and Cu-(Ag-Bi) zones (Chapters 2a
and 2b). Of these, 11 quartz samples were separated
from assemblages containing enargite and 5 from
assemblages containing alunite without the presence
of sulfides other than pyrite. Samples were selected
from drill holes and are nearly uniformly distributed
along the main axis of a 3 km continuous mineralized
corridor that includes the Smelter and Colquijirca
deposits (Appendix 4.1). In order to facilitate
recognition of primary fluid inclusions, most grains
were cut along a crystallographic axis. Three groups
of grains of euhedral enargite coeval with quartz
separates were similarly cut following crystallographic
directions.
Ten samples including separates of quartz (3),
barite (2), and sphalerite (4), are representative of the
Cu-(Ag), Cu-(Bi-Ag), Zn-Pb-Cu-(Ag-Bi)
zones from
Colquijirca (Chapter 2b). The samples are distributed
from the Principal to the Mercedes-Chocayoc pit.
(Appendix 4.1).
CHAPTER 4
A similar protocol of sample preparation and
method study to that described for samples from
the Au-(Ag) epithermal high sulfidation fluids was
applied to all of the selected Cordilleran samples.
Enargite grains were studied using an infrared light
microscope equipped with an infrared-sensitive video
camera and a USGS heating-freezing stage.
Fluid inclusion types and occurrence:
The vast majority of the inclusions observed
consists of liquid and vapor at room temperature
(Figure 4.2). On the basis of phase assemblages, and
similarly to those observed in the Oro Marcapunta
high sulfidation epithermal Au-(Ag) samples, two
main types of fluid inclusions were recognized:
L type inclusions (L/V ratios below 0.5) and V
type inclusions (L/V ratios >0.9). Rare inclusions
containing, besides liquid and vapor phases, an
apparent irregular solid phase were observed only in
Early silica-pyrite stage quartz.
In quartz from the Early silica-pyrite stage at Smelter
Silica-pyrite replacements (Early silica-pyrite
stage) are extensively overprinted in variable degrees
by enargite-bearing assemblages from the Main ore
stage, at both, Smelter and Colquijirca (Chapters
2a and 2b). Most silica is massive and displays a
cryptocrystalline appearance (Chapter 2a). Quartz,
when present, is commonly anhedral and fine-grained
(<500 m) and usually contains not suitable fluid
inclusions (<5 m). Because of these limitations,
only two quartz samples were observed to host
some measurable fluid inclusions. These inclusions,
however, given the anhedral character of quartz,
and lacking cathodoluminiscence tests, cannot be
classified in terms of their primary, secondary, or
pseudosecondary nature.
Early silica-pyrite stage quartz-hosted fluid
inclusions are therefore categorized only in descriptive
terms. Two main types are observed. (1) Isolated
inclusions or group of inclusions without evident
control by any crystallographic plan or fracture and
(2) less abundant, inclusion trails following healed
fractures.
Most studied fluid inclusions are very small,
between 5 and 10 m. Two phase L type are typical
fluid inclusions in Early silica-pyrite stage quartz.
Vapor to liquid ratios are variable in a single grain,
or even in a same portion of the grain. Trails of
inclusions with vapor to liquid ratios between 0.20
to 0.35, mostly fracture-controlled, closely coexist
with groups of isolated inclusions, with V/L ratios
in excess of 0.3 and as high as 0.5. Some isolated
inclusions contain, in addition, an irregular translucent
solid phase, generally occupying less than a tenth of
the inclusion.
In quartz and enargite from the Main ore stage internal
173

zones at Smelter and Colquijirca
L type inclusions constitute by far the most
abundant quartz-hosted type representing internal
zones from the Main ore stage. These are primary
and secondary in origin and display two fluid phases.
A liquid water solution and a vapor bubble are in
almost all cases observed (Figure 4.2). According to
the position from the Marcapunta volcanic complex,
the proportion of each phase is observed to change
considerably. A broad decrease in the vapor-to-
liquid ratios is noticeable over a 2 km distance from
Smelter to Colquijirca from around 0.35-0.25 to 0.20-
0.15. Vertically, a systematic change is indiscernible,
though inclusions from a sample located 750 m deep
display high vapor-to-liquid ratios (0.4 to 0.45). L type
inclusions show several geometries, being elliptical
forms predominant. Size of the fluid inclusions
ranges from a few microns up to several hundreds of
microns (Figure 4.2).
V type inclusions consist of two (liquid and
vapor) visible phases at room temperature with the
vapor phase in most cases in excess of 90 volume
% and commonly filling almost entirely the cavity.
In contrast to L type inclusions, V type inclusions
are characteristically smaller than 10 m, but large
inclusions, up to 30 m have also been observed. V
type inclusions are found mostly in enargite-bearing
zones. Most of the observed V type inclusions follow
healed microfractures suggesting a secondary origin
(Figure 4.2).
Several groups of fluid inclusions displaying
a large range of vapor-to-liquid ratios, characteristic
of boiling fluids, are observed (e.g., PBR-144), their
distribution controlled by healed fractures point to
a pseudosecondary or secondary origin. Samples
containing such inclusions are located close to the
Marcapunta volcanic complex.
17 primary fluid inclusions were studied by
means of infra-red microthermometry. By discussing
these inclusions it has to be taken into account that
the measured homogenization temperatures may be
underestimated up to by 10C due to variations in
the intensity of the infrared light source (Moritz,
2006). A similar inconvenience appears in the melt
of ice temperature measurements. For this reason,
only three Th-salinity values which were obtained
using near to optimal instrumental parameters are
used. Enargite-hosted fluid inclusions display in
essence similar characteristics with quartz-hosted
fluid inclusions, i.e. two phase L type with vapor-to-
liquid ratios varying around 0.3.
In sphalerite, barite, and quartz, from intermediate
zones the Main ore stage at Colquijirca
Primary and secondary fluid inclusions in
sphalerite, barite, and quartz of the intermediate
zones are also mainly of the two phase L type. A
considerable decrease of the vapor-to-liquid ratios is
noticeable with increasing distance to the north from
0.25 to 0.05 over <1 km distance from the Principal
174
CHAPTER 4
pit to the Mercedes-Chocayoc pit. V type inclusions
are generally less abundant.
Microthermometry
Homogenization temperatures (Th) and the
final melting point of ice (Tm) of 107 L type groups
of mainly primary and secondary inclusions from the
Early silica-pyrite stage and the Main ore stage were
measured (Table 4.5). It was not possible to determine
the Th of V type inclusions. According to Raman
microprobe tests on a selection of representative
vapor-rich inclusions (V type) hosted in quartz from
the Main ore stage, no gases other than water vapor
are present in significant amounts. Accordingly, no
clathrate formation was observed during freezing in
any of the studied fluid inclusions, suggesting that
CO2, a common phase in high level hydrothermal
systems, is possibly present only at negligible levels
in most of Main ore stage fluid inclusions. However,
the tests were not conducted in quartz-hosted fluid
inclusions from the Early silica-pyrite stage and it is
not excluded that these contain significant amounts of
CO2 as be expected because of abundant carbonate
dissolution.
Homogenization temperatures of isolated
fluid inclusions in the two quartz samples from the
Early silica-pyrite stage range between 288C and
320C. Distinctly lower homogenization temperatures
were found in fracture-controlled inclusions ranging
from 264 to as low as 216C (Table 4.5). In contrast,
no significant variations in salinities were found
between the two types of fluid inclusions. Isolated
and fracture-controlled inclusions gave salinity
ranges of 2.24 and 4.65 and 1.91 and 3.87 NaCl wt
% equivalent, respectively.
Primary and secondary quartz-hosted fluid
inclusions from the Main ore stage from the
enargite-bearing internal zones from the Smelter
and Colquijirca deposits gave collectively Th values
ranging between 218C and 376C, though the
vast majority between 212C and 300C (Table
4.5, Figure 4.8). Both, primary and secondary fluid
inclusions cover almost entirely this last range of
homogenization temperatures (Figure 4.6). Salinities
obtained from primary and secondary inclusions vary
from nearly zero to around 7 NaCl wt % equivalent
(Figure 4.8). Again, both primary and secondary
fluid inclusions yield salinities spreading throughout
this interval. Primary and secondary fluid inclusions
groups hosted in sphalerite, barite, and quartz
from the Colquijirca Main ore stage bodies gave
homogenization temperatures from 232C to 146C
and salinities from 0.71 to 4.49 wt % NaCl equivalent
(Table 4.5, Figure 4.6).
Homogenization temperatures from 300C
to 376C (Table 4.5) were recorded in a few clusters
of irregular fluid inclusions in inner parts of one
quartz grain from the enargite-bearing Cu-(Au-Ag)
zone (PBR-391). These temperatures higher than
those found in quartz-hosted fluid inclusions from
 CHAPTER 4

Early silica-pyrite stage fluid inclusion: Main ore stage primary fluid inclusion:
in barite in tennantite-bearing
"Fracture-controlled" in quartz from assemblage (Colquijirca)
silica-pyrite stage at Colquijirca in enargite in enargite-bearing
assemblage (Smelter
"Fracture-controlled" in quartz from
8 in quartz in enargite-bearing
silica-pyrite stage at Smelter
assemblage (Colquijirca)
7 "Isolated" in quartz from silica-pyrite stage
in quartz in enargite-bearing
at Smelter assemblage (Smelter)
6 in quartz in quartz-alunite assemblage
8 (Smelter)
in sphalerite in sphalerite-bearing
5
Frequency

assemblage (Colquijirca)
7
4
6
3
5

Frequency
2 4

1 3

0 2
1 2 3 4 5 6 7 8 9 10
Salinity (wt% NaCl equ.) 1

4 0
0 2 4 6 8 10
Salinity (wt% NaCl equ.)
10
3 9
8
Frequency

7
2
6
Frequency

5
4
1
3
2
0 1
200 250 300 350 400
0
Homogenization temperature (C) 100 150 200 250 300 350 400
Homogenization temperature (C)

Figure 4.6: Histograms showing the distribution of fluid inclusions from the Main ore stage from the Cordilleran Smelter and
Colquijirca deposits according to their origin (primary or secondary), the zone, and the occurrence type they represent vs. homog-
enization temperature (Th) and salinity (wt % NaCl equivalent).

175
 CHAPTER 4

Main ore stage secondary fluid inclusion: fluid inclusions are presented. Obtained melt of ice
in quartz in enargite-bearing assemblage temperatures indicate salinities of 1.74, 3.55, and
(Colquijirca) 3.71 wt % NaCl equivalent and homogenization
in quartz in enargite-bearing assemblage temperatures of, respectively 260.4C, 286.4C and
(Smelter) 281.0C (Table 4.5).
in quartz in quartz-alunite assemblage Two quartz samples from the Main ore stage
(Smelter) from Smelter (PBR-144 and PBR-139) were observed
5 in sphalerite in sphalerite-bearing assemblage to contain several trails of secondary fluid inclusions
(Colquijirca) with contrasting vapor-to-liquid ratios suggesting
boiling. In one of these trails, the inclusions yield
4 homogenization temperatures around 249C and
salinities ranging from 0.35 to as high as 7.31 wt %
NaCl equivalent (Table 4.5). Two other fluid inclusion
3 trail of this type recognized in sample PBR-244
Frequency

produced homogenization temperatures close to

247C and 266C with salinities from 0.53 wt % to
2 5.56 wt % and from 2.74 wt % to 4.34 wt % NaCl
equivalent, respectively (Table 4.5).
1
b. Stable isotopes analysis
0 Samples for the oxygen and hydrogen isotopes analysis
0 2 4 6 8 10 of alunite and analytical procedure:
Salinity (wt% NaCl equ.) The oxygen and hydrogen isotopic composition
of 17 alunite samples from the Main ore stage was
9 measured. The alunite samples are nearly uniformly
distributed from Smelter to Colquijirca (Appendix
8 4.1) and nearly half of them were obtained from the
same samples that provided microthermometric data
7
through the study of quartz-hosted fluid inclusions.
6 According to the mineral association, 9 alunite
samples were separated from, generally, barren
Frequency

5 quartz-alunite assemblages and 8 from ore-bearing

assemblages (Table 4.6). Care was taken in selecting
4 only alunite grains without discernible cores of other
3 minerals of the APS group, particularly those widely
distributed at Smelter of the woodhouseite series
2 (Chapter 2a).
Preparation of separates as well as measurements
1 of oxygen and hydrogen isotopic compositions of the
0 alunite samples from the Cordilleran mineralization
100 200 300 400 were performed according to the methods described,
Homogenization temperature (C) respectively by Wasserman et al. (1992) and Sharp
et al. (2001) and summarized in the corresponding
Fig. 4.6: (Cont.) section related to the stable isotope analysis of alunite
from the Oro Marcapunta Au-(Ag) epithermal high
sulfidation occurrence.
the Early silica-pyrite stage (>320C, e.g., PBR-391)
and also higher than the other maximum recognized Samples for the hydrogen and oxygen isotopes analysis
homogenization temperatures from the most internal of kaolinite and dickite and analytical procedure:
parts of Main ore stage bodies (~300C e.g., PBR- Hydrogen and oxygen isotopes analysis were
295) may represent, however, given their irregularly performed on 18 kaolinite and dickite samples (Table
elongated morphology, inclusions having underwent 4.7). Of these, 4 correspond to Smelter and 14 to
necking down. Because of this uncertainty, in this the Colquijirca deposit. Two of the samples from
study, these high homogenization temperatures are Smelter were collected from sphalerite-galena bodies,
not considered for discussion. one encapsulated in enargite-bearing zones (PBR-
Owing to the instrumental uncertainties of 147) and the other from the Zn-Pb-(Ag) external
the infrared technique mentioned above, only the zone of the Smelter deposit (PBR-250). The other
micrometric results of three primary enargite-hosted two samples were separated from enargite-bearing

176
 CHAPTER 4

Table 4.5: Summary of microthermometric results for fluid inclusions of the Cordilleran deposits of the Colquijirca district.
Salinity
Sample Host mineral Deposit/Stage Inclusion type/Assemblage Tm ice C ThC
NaCl wt % eq

PBR-139 quartz Smelter/Main ore stage secondary/quartz-alunite ass. 0.0 0.00 259.7
PBR-144 quartz Smelter/Main ore stage secondary/quartz-alunite ass. -0.1 0.18 205.3
PBR-144 quartz Smelter/Main ore stage secondary/quartz-alunite ass. -0.1 0.18 238.6
PBR-139 quartz Smelter/Main ore stage secondary/quartz-alunite ass. -0.1 0.18 244.6
PBR-144 quartz Smelter/Main ore stage primary/enargite-bearing ass. -0.2 0.35 205.3
PBR-131 quartz Smelter/Main ore stage primary/quartz-alunite ass. -0.2 0.35 253.1
PBR-265 quartz Smelter/Main ore stage primary/quartz-alunite ass. -0.2 0.35 238.2
PBR-131 quartz Smelter/Main ore stage secondary/enargite-bearing ass. -0.3 0.53 240.4
PBR-144 quartz Smelter/Main ore stage secondary/quartz-alunite ass. -0.3 0.53 208.6
PBR-265 quartz Smelter/Main ore stage secondary/quartz-alunite ass. -0.3 0.53 222.4
PBR-131 quartz Smelter/Main ore stage secondary/quartz-alunite ass. -0.3 0.53 236.9
PBR-131 quartz Smelter/Main ore stage secondary/quartz-alunite ass. -0.4 0.71 253.3
PBR-265 quartz Smelter/Main ore stage primary/quartz-alunite ass. -0.7 1.23 219.3
PBR-50 sphalerite Colquijirca/Main ore stage primary/sphalerite-bearing ass. -0.8 1.40 180.4
PBR-246 sphalerite Colquijirca/Main ore stage primary/sphalerite-bearing ass. -0.8 1.40 196.2
PBR-144 quartz Smelter/Main ore stage secondary/enargite-bearing ass. -0.8 1.40 190.8
PBR-265 quartz Smelter/Main ore stage secondary/quartz-alunite ass. -0.8 1.40 243.2
PBR-50 sphalerite Colquijirca/Main ore stage primary/sphalerite-bearing ass. -0.9 1.57 172.9
PBR-144 quartz Smelter/Main ore stage primary/quartz-alunite ass. -0.9 1.57 231.7
PBR-144 quartz Smelter/Main ore stage primary/quartz-alunite ass. -0.9 1.57 235.2
PBR-256a quartz Smelter/Main ore stage secondary/enargite-bearing ass. -0.9 1.57 240.8
PBR-62 barite Colquijirca/Main ore stage primary/tennantite-bearing ass. -0.9 1.57 207.4
PBR-259 quartz Smelter/Main ore stage primary/enargite-bearing ass. -0.9 1.57 239.9
PBR-256a enargite Smelter/Main ore stage primary/enargite-bearing ass. -1.0 1.74 260.4
PBR-265 quartz Smelter/Main ore stage secondary/quartz-alunite ass. -1.0 1.74 240.5
PBR-144 quartz Smelter/Main ore stage secondary/enargite-bearing ass. -1.1 1.91 186.8
PBR-391 quartz Smelter/Early silica-pyrite stage fracture-controlled -1.1 1.91 222.8
PBR-62 barite Colquijirca/Main ore stage primary/tennantite-bearing ass. -1.1 1.91 214.2
PBR-256a quartz Smelter/Main ore stage secondary/enargite-bearing ass. -1.1 1.91 257.7
PBR-329 quartz Smelter/Main ore stage secondary/enargite-bearing ass. -1.2 2.07 224.4
PBR-240 sphalerite Colquijirca/Main ore stage primary/sphalerite-bearing ass. -1.2 2.07 192.3
PBR-256a quartz Smelter/Main ore stage secondary/enargite-bearing ass. -1.2 2.07 270.4
PBR-246 sphalerite Colquijirca/Main ore stage primary/sphalerite-bearing ass. -1.2 2.07 172.2
PBR-139 quartz Smelter/Main ore stage primary/quartz-alunite ass. -1.2 2.07 242.6
PBR-295 quartz Smelter/Main ore stage secondary/enargite-bearing ass. -1.3 2.24 272.3
PBR-255 quartz Smelter/Main ore stage secondary/enargite-bearing ass. -1.3 2.24 194.2
PBR-95 sphalerite Colquijirca/Main ore stage primary/sphalerite-bearing ass. -1.3 2.24 205.4
PBR-329 quartz Smelter/Main ore stage secondary/enargite-bearing ass. -1.3 2.24 202.5
PBR-112 sphalerite Colquijirca/Main ore stage primary/sphalerite-bearing ass. -1.3 2.24 200.7
PBR-391 quartz Smelter/Early silica-pyrite stage fracture-controlled -1.4 2.41 217.3
PBR-329 quartz Smelter/Main ore stage secondary/enargite-bearing ass. -1.4 2.41 165.9
PBR-240 sphalerite Colquijirca/Main ore stage secondary/sphalerite-bearing ass. -1.4 2.41 197.3
PBR-123 sphalerite Colquijirca/Main ore stage primary/sphalerite-bearing ass. -1.4 2.41 212.3
PBR-240 sphalerite Colquijirca/Main ore stage primary/sphalerite-bearing ass. -1.5 2.57 205.6
PBR-112 sphalerite Colquijirca/Main ore stage primary/sphalerite-bearing ass. -1.5 2.57 224.0
PBR-139 quartz Smelter/Main ore stage primary/quartz-alunite ass. -1.5 2.57 241.4
PBR-391 quartz Smelter/Early silica-pyrite stage fracture-controlled -1.5 2.57 222.6
PBR-259 quartz Smelter/Main ore stage secondary/enargite-bearing ass. -1.6 2.74 235.4
PBR-255 quartz Smelter/Main ore stage secondary/enargite-bearing ass. -1.6 2.74 192.8

177
 CHAPTER 4

Table 4.5(cont.) Summary of microthermometric results for fluid inclusions of the Cordilleran deposits of the Colquijirca district.

Salinity
Sample Host mineral Deposit/Stage Inclusion type/Assemblage Tm ice C ThC
NaCl wt % eq

PBR-190 sphalerite Colquijirca/Main ore stage primary/sphalerite-bearing ass. -1.6 2.74 200.5
PBR-112 sphalerite Colquijirca/Main ore stage primary/sphalerite-bearing ass. -1.6 2.74 214.2
PBR-123 sphalerite Colquijirca/Main ore stage primary/sphalerite-bearing ass. -1.7 2.90 204.6
PBR-268 quartz Smelter/Main ore stage secondary/quartz-alunite ass. -1.7 2.90 225.1
PBR-144 quartz Smelter/Main ore stage secondary/enargite-bearing ass. -1.7 2.90 171.3
PBR-268 quartz Smelter/Main ore stage secondary/quartz-alunite ass. -1.7 2.90 242.2
PBR-240 sphalerite Colquijirca/Main ore stage primary/sphalerite-bearing ass. -1.8 3.06 212.1
PBR-190 sphalerite Colquijirca/Main ore stage primary/sphalerite-bearing ass. -1.8 3.06 203.5
PBR-268 quartz Smelter/Main ore stage primary/quartz-alunite ass. -1.8 3.06 236.1
PBR-147 sphalerite Colquijirca/Main ore stage primary/sphalerite-bearing ass. -1.8 3.06 182.6
PBR-244 quartz Colquijirca/Main ore stage secondary/enargite-bearing ass. -1.8 3.06 231.3
PBR-244 quartz Colquijirca/Main ore stage secondary/enargite-bearing ass. -1.8 3.06 220.6
PBR-265 quartz Smelter/Main ore stage primary/quartz-alunite ass. -1.8 3.06 245.6
PBR-256a quartz Smelter/Main ore stage secondary/enargite-bearing ass. -1.9 3.23 256.9
PBR-144 quartz Smelter/Main ore stage primary/enargite-bearing ass. -1.9 3.23 217.2
PBR-391 quartz Smelter/Early silica-pyrite stage isolated -1.9 3.23 310.4
PBR-147 sphalerite Colquijirca/Main ore stage primary/sphalerite-bearing ass. -1.9 3.23 184.8
PBR-391 quartz Smelter/Early silica-pyrite stage isolated -1.9 3.23 302.4
PBR-391 quartz Smelter/Early silica-pyrite stage fracture-controlled -1.9 3.23 237.6
PBR-247 quartz Colquijirca/Early silica-pyrite stage fracture-controlled -1.9 3.23 266.4
PBR-247 quartz Colquijirca/Early silica-pyrite stage fracture-controlled -1.9 3.23 259.7
PBR-240 sphalerite Colquijirca/Main ore stage primary/sphalerite-bearing ass. -2.0 3.39 204.6
PBR-131 quartz Smelter/Main ore stage primary/quartz-alunite ass. -2.0 3.39 266.4
PBR-190 sphalerite Colquijirca/Main ore stage primary/sphalerite-bearing ass. -2.1 3.55 198.6
PBR-139 quartz Smelter/Main ore stage secondary/quartz-alunite ass. -2.1 3.55 246.1
PBR-256a enargite Smelter/Main ore stage primary/enargite-bearing ass. -2.1 3.55 286.4
PBR-247 quartz Colquijirca/Early silica-pyrite stage fracture-controlled -2.1 3.55 270.3
PBR-262 quartz Smelter/Main ore stage primary/enargite-bearing ass. -2.1 3.55 296.4
PBR-190 sphalerite Colquijirca/Main ore stage primary/sphalerite-bearing ass. -2.2 3.71 219.2
PBR-247 quartz Colquijirca/Early silica-pyrite stage fracture-controlled -2.2 3.71 267.3
PBR-256a enargite Smelter/Main ore stage primary/enargite-bearing ass. -2.2 3.71 281.0
PBR-139* quartz Smelter/Main ore stage secondary/enargite-bearing ass. -2.2 3.71 331.6
PBR-139* quartz Smelter/Main ore stage secondary/enargite-bearing ass. -2.3 3.87 340.1
PBR-64 quartz Smelter/Main ore stage primary/alunite-bearing ass. -2.3 3.87 272.4
PBR-139* quartz Smelter/Main ore stage secondary/enargite-bearing ass. -2.3 3.87 362.4
PBR-295 quartz Smelter/Main ore stage secondary/quartz-alunite ass. -2.4 4.03 268.1
PBR-262 quartz Smelter/Main ore stage primary/enargite-bearing ass. -2.4 4.03 281.3
PBR-249 quartz Smelter/Main ore stage primary/enargite-bearing ass. -2.4 4.03 243.2
PBR-391 quartz Smelter/Early silica-pyrite stage isolated -2.4 4.03 308.2
PBR-391 quartz Smelter/Early silica-pyrite stage isolated -2.5 4.18 320.0
PBR-329 quartz Smelter/Main ore stage primary/enargite-bearing ass. -2.6 4.34 228.6
PBR-139* quartz Smelter/Main ore stage secondary/enargite-bearing ass. -2.7 4.49 348.4
PBR-190 sphalerite Colquijirca/Main ore stage primary/sphalerite-bearing ass. -2.7 4.49 228.3
PBR-123 sphalerite Colquijirca/Main ore stage primary/sphalerite-bearing ass. -2.7 4.49 216.6
PBR-256a quartz Smelter/Main ore stage primary/enargite-bearing ass. -2.8 4.65 275.6
PBR-391 quartz Smelter/Early silica-pyrite stage isolated -2.8 4.65 288.6
PBR-139* quartz Smelter/Main ore stage secondary/enargite-bearing ass. -2.8 4.65 326.5
PBR-137 quartz Smelter/Main ore stage primary/enargite-bearing ass. -2.9 4.80 268.4
PBR-244 quartz Colquijirca/Main ore stage primary/enargite-bearing ass. -3.1 5.11 242.8

178
 CHAPTER 4

Table 4.5 (cont.) Summary of microthermometric results for fluid inclusions of the Cordilleran deposits of the Colquijirca district.
Salinity
Sample Host mineral Deposit/Stage Inclusion type/Assemblage Tm ice C ThC
NaCl wt % eq

PBR-262 quartz Smelter/Main ore stage secondary/enargite-bearing ass. -3.3 5.41 263.1
PBR-295 quartz Smelter/Main ore stage primary/enargite-bearing ass. -3.4 6.01 280.3
PBR-295 quartz Smelter/Main ore stage primary/enargite-bearing ass. -3.6 5.86 283.1

PBR-244 quartz Colquijirca/Main ore stage primary/enargite-bearing ass. -3.6 5.86 246.2
PBR-268 quartz Smelter/Main ore stage primary/enargite-bearing ass. -3.7 6.01 258.7
PBR-295 quartz Smelter/Main ore stage primary/enargite-bearing ass. -3.8 6.16 294.2
PBR-295 quartz Smelter/Main ore stage primary/enargite-bearing ass. -3.8 6.16 298.2
PBR-256a quartz Smelter/Main ore stage secondary/enargite-bearing ass. -4.0 6.45 260.9
PBR-131 quartz Smelter/Main ore stage primary/enargite-bearing ass. -4.4 7.02 258.4
PBR-256a quartz Smelter/Main ore stage secondary/enargite-bearing ass. -4.5 7.17 273.0

Fluid inclusions groups displaying apparent boiling

PBR-139 quartz Smelter/Main ore stage secondary/enargite-bearing ass. -0.2 to -4.6 0.35 to 7.31 249.0
PBR-144 quartz Main ore stage secondary/enargite-bearing ass. -0.1 to -1.3 0.18 to 2.24 247.0
PBR-144 quartz Main ore stage secondary/enargite-bearing ass. -1.6 to -2.6 2.74 to 4.34 266.0

*Irregularly elongated fluid inclusions. Possible necking down.

ass., assemblage;

assemblages (PBR-251 and PBR-255). Fifteen Measurements of the hydrogen isotope

samples correspond to the Colquijirca deposit and
mostly represent the internal to intermediate Cu-
(Ag), Cu-(Bi-Ag),
Zn-Pb-Cu-(Ag-Bi)
zones. Of these,
PBR-192, PBR-230, and PBR-249 were separated
from enargite-bearing assemblages (Cu-(Ag) zone),
PBR-123, PBR-151, PBR-62, PBR-95, PBR-112,
PBR-240, PBR-251, PBR-252, and PBR-241 from
chalcopyrite-bearing assemblages (Cu-(Bi-Ag) zone),
and PBR-50 and PBR-246 from the relatively external
Zn-Pb-(Ag) zone.
The oxygen isotope compositions of kaolinite
and dickite samples were measured according to the
method used to analyze quartz (Sharp, 1990; Rumble
and Hoering, 1994; and Kasemann et al., 2001) and
which has been previously described.
An in-house standard (Kaol #17) was
calibrated with a conventional silicate line against
NBS-28 quartz. The kaolinite was dried for two days
in a vacuum dessicator with P2O5 as drying agent and
then transferred into individual reaction vessels. It
gave an average of 8.24 permil 0.12, nearly identical
to the values obtained for the current laser analyses.
The samples were all dried at 70 C for 5 days, then
at 120 C for 5 hours and then evacuated for 12 to
15 hours before prefluorination and then reaction as
normal for silicates with the laser line. The precision
of the in-house kaolinite standard was within 0.2
for the method used.
Replicate oxygen isotope analyses of the
standards used Ls-1 Qtz (n = 8); Valley et. al., 1995)
generally have an average precision of 0.27
for 18O. The accuracy of 18O values is commonly
better than 0.3 compared to accepted 18O values
for Ls-1 Qtz of 9.50 .
compositions of kaolinite and dickite were made
using high temperature (1450C) reduction methods
with He-carrier gas a TC-EA linked to a Delta Plus
XL mass spectrometer from Thermo-Finnigan on 2
to 4 mg sized samples according to a method adapted
after Sharp et al. (2001). The results are given in the
standard -notation expressed relative to VSMOW in
permil (). The in-house standard Kaol #17 (n=17)
produced a mean D VSMOW value of -128.0
with a standard deviation of 1.9.
Samples for the oxygen analysis of quartz and
analytical procedure:
12 quartz samples were analyzed for oxygen
isotopes (Table 4.8). Three of them represent the
Early silica-pyrite stage and 9 the Main ore stage. One
of the Early silica-pyrite stage quartz samples was
separated from a rock that is cut by sub-economic
veinlets containing sphalerite-bearing assemblages
(PBR-247). The two other quartz samples (PBR-391
and PBR-399b) were separated from a completely
silicified limestone with minor pyrite disseminations
and no signals of later Main ore stage overprinting.
PBR-399b quartz is intergrown with opaline silica.
Of the Main ore stage samples, 5 were collected
from different enargite-bearing zones of the Smelter
deposit which in turn can be divided into two groups
according to the assemblage type they represent
(Table 4.8). Three of these correspond to enargite-
bearing assemblages (PBR-143, PBR-244, and PBR-
263) and two to assemblages containing alunite and
pyrite (PBR-131 and PBR-265). The other quartz
samples from the Main ore stage are distributed

179
 CHAPTER 4

Table 4.6. Hydrogen and oxygen isotope composition of alunite samples from the Cordilleran deposits of the Colquijirca district.
Sample Deposit Mineralogical description D1 18O2 H2O
( VSMOW) ( VSMOW) wt %

Nearly massive enargite rich ore. Coarse alunite grains in part intergrown -58 13.3 13.71
PBR-131 Smelter with pyrite II and minor tiny quartz as coatings and open space fillings. -56 12.7 13.67
No intergrown between alunite and enargite is observed. -57 13.0
-47 12.8 12.84
Massive quartz-alunite replacement of former limestone. Development -47 13.01
PBR-137 Smelter of centimetric geodes partially filled by coarse euhedral alunite grains.
Minute zunyite as part of the quartz-alunite replacement matrix. -45 12.89
-46 12.8
-83 14.87
Intergrowth of almost euhedral pyrite II, quartz, and alunite in minute -81 I.M. 14.54
PBR-238 Smelter cavities as selective replacement of clasts, possibly originally limestones
of a sedimentary breccia of the Calera Inferior sequence. -87 15.25
-84
-74 11.1 14.19
Massive enargite ore in radial aggregates (up to more than 10 cm -73 11.1 13.69
PBR-245 Smelter diameter). Postdating occurs subordinated pyrite II intimately associated
to well formed pink alunite as open space fillings. -74 13.91
-74 11.1

Intergrowth of almost euhedral pyrite II, enargite, alunite, and quartz in -76 11.8 13.66
PBR-262 Smelter fracture-controlled druse-like cavities. This assemblage cut a partially -76 11.7 13.66
silicified dolostone containing minor pyrite I disseminations. -76 11.8
-72 9.2 12.20
Massive enargite ore. Pyrite II and alunite accompanied by minor quartz -76 8.3 13.71
PBR-265 Smelter and zunyite partially replacing enargite. Some relictic chert from the
Early silica-pyrite stage. -71 13.82
-73 8.8
-66 11.3 14.21
PBR-269 Smelter Massive enargite replacement. Minor alunite as open space fillings. -68 12.6 14.17
-67 12.0
-79 11.5 15.53
Coarse euhedral enargite. Alunite posdating enargite as coatings around -79 15.72
PBR-329 Smelter
pyrite II-enargite masses. -79 14.72
-79 11.5
-54 13.7 12.24
Enargite impregnations in strongly silicifed shale (chert). Fine-grained -52 13.6 12.24
PBR-218 Colquijirca
alunite veinlets in part cutting enargite. -55 12.51
-54 13.6
-56 15.7 13.32
Matrix-supported hydrothermal breccia. Pyrite II and minor enargite and quartz -59 15.5 13.46
PBR-244 Colquijirca conform the matrix and are partially replaced by whitish sugary alunite plus
dickite. -60 13.49
-58 15.6
-44 12.80
Massive sphalerite, pyrite, galena replacement. Centimetric geodes coated by -46 I.M. 13.05
PBR-298 Colquijirca coarse-grained alunite euhedral grains. Alunite also as part of the matrix in reversal
-42 13.13
crystallization with sphalerite and galena.
-44
-58 13.03
-57 I.M. 12.99
PBR-217 Colquijirca Strongly silicified shale (chert) being cut by fine-grained whitish alunite veinlets.
-57 12.64
-57

180
 CHAPTER 4

Table 4.6. (cont.) Hydrogen and oxygen isotope composition of alunite samples from the Cordilleran deposits of the Colquijirca district.
Sample Deposit Mineralogical description D1 18O2 H2O
( VSMOW) ( VSMOW) wt %
-59 14.7 13.03
Massive sphalerite, galena, pyrite breccia. Druse-like cavities at the corners -59 15.5 12.77
PBR-253 Colquijirca of the the angular clasts with euhedral alunite, barite and minor diaspore
grains. Alunite in reversal crystallization with sphalerite. -62 12.46
-60 15.1
-55 12.94
Chert with intense pyrite I disseminations. Fine-grained alunite and -56 I.M. 12.50
PBR-114 Colquijirca
kaolinite in fractures. -55 12.62
-55
-105 7.9 14.19
Massive sphalerite, galena ore in a friable and microgranular texture -100 8.3 13.83
San
PBR-284a (sulfide rock). Extremely fine-grained alunite plus minor kaolinite as
Gregorio -94 13.66
thin veinlets.
-99 8.1
-103 5.0 14.70
San -104 4.9 13.60
PBR-208 Sulfide rock. Blebs of fine-grained alunite and minor quartz and kaolinite.
Gregorio -105 14.06
-104 5.0
-105 7.4 13.82
San -106 7.9 14.27
PBR-169 Idem to PBR-208
Gregorio -105 14.28
-105 7.7

as follow: PBR-262 from the Cu-(Ag) zone from
Colquijirca, PBR-283 from the Cu-(Bi-Ag) zone, also
from Colquijirca, and PBR-177 and PBR-208 from
the San Gregorio deposit.
Quartz separates were analyzed for their
oxygen isotopes compositions together with the same
batch of quartz samples from the Oro Marcapunta
Au-(Ag) epithermal high sulfidation occurrence.
The analytical method is described above in the
corresponding section.
Samples for the sulfur isotopes analysis of sulfides and
sulfates and analytical procedure:
Samples for sulfur isotopes analysis of sulfides
and sulfates represent the Main ore stage through
the entire Smelter-Colquijirca corridor (Appendix
4.1). From internal parts (enargite-bearing zones),
mainly from Smelter, individual minerals or pairs
of minerals consisting of enargite, pyrite, enargite-
pyrite, enargite-alunite, pyrite-enargite were selected.
Sphalerite-galena, pyrite-galena, pyrite-sphalerite,
pyrite-alunite, chalcopyrite-pyrite, chalcopyrite-
bornite, pyrite-barite, sphalerite-barite, galena-barite,
pairs were collected from intermediate and relatively
external parts of the system, i.e. from the Cu-
(Ag), Cu-(Bi-Ag),
Zn-Pb-Cu-(Ag-Bi) zones of the
Colquijirca deposit (Table 4.9).
The sulfur isotope analyses were effectuated
by means of an on-line elemental analyzer (Carlos
Erba 1108)-continuous flow-isotope ratio mass
spectrometer (Finnigan Mat Delta S), following the
technique described by Giesemann et al. (1994).
The sulfide samples (1 to 3 mg) were wrapped in tin
capsules together with 1 mg of V2O5. The sulfide
minerals were completely oxidized to SO2 by flash
combustion at 1020C in an oxidation-reduction
quartz column. A He stream served as gas separator
(CO2 and NO2 from SO2). Reproducibility was
better than 0.2 for 34S. Values are reported in
conventional permil () deviations relative to the
Canyon Diablo Troilite (CDT) standard.
Sulfur isotope analyses in alunite and barite
were performed according to the same method
to that described for alunite analysis from the Au-
(Ag) epithermal high sulfidation occurrence of
Marcapunta.
Oxygen and hydrogen isotope composition of
alunite
Oxygen and hydrogen isotope composition
of Cordilleran alunite samples yield an ampler range
of values compared to those analyzed from the Oro
Marcapunta Au-(Ag) disseminated occurrence. D
spans from -44 to as low as -105 , whereas 18O
(SO4) varies from 5.0 to 15.6 (Table 4.6, Figure
4.7).
The obtained values can be divided into two
groups according to the alunite-bearing assemblage.
A first group of samples in which alunite occurs
usually with fine-grained quartz, zunyite, and
pyrite as the only sulfide gave D and 18O (SO4)

181
 CHAPTER 4

Table 4.7. Hydrogen and oxygen isotope composition of kaolinite and dickite samples from the Cordilleran deposits of the Colquijirca
district.
Sample Location/Mineral Mineralogical description D1 d18O2 H2O
( VSMOW) ( VSMOW) wt %

-135.7 20.2 14.67

Zn-Pb massive sulfide replacement ore. Kaolinite occurs in
PBR-50 Colquijirca/Kaolinite -137.2 20.3 14.95
reversal crystallization with sphalerite within the matrix.
-136.5 20.3

-118.2 26.2 13.52

Fine grained subhedral to euhedral py-sl-ga-chalcopyrite -117.0 26.4 13.40
PBR-123 Colquijirca/Kaolinite
disseminations within massive, compact kaolinite. -117.3 25.9 12.73
-117.5 26.2

-141.4 14.96
Massive sphalerite, galena, siderite replacement. Minor -143.2 21.3 14.63
PBR-147 Colquijirca/Kaolinite
kaolinite filling intergranular spaces. -142.5 15.39
-142.4 21.3
-106.7 31.1 4.90
Chalcopyrite-supported breccia with minor barite and -99.8 31.0 4.65
PBR-151 Colquijirca/Kaolinite kaolinite as open space fillings. Clasts of strongly silicified
limestones with minor pyrite I. -105.6 5.20
-104.0 11.1
-108.7 14.04
Kaolinite disseminations intimately intergrown with nearly -109.4 27.0 14.10
PBR-192 Colquijirca/Kaolinite euhedral enargite. Minor pyrite II floating on kaolinite
agglomerations. -109.8 13.91
-109.3 27.0
-126.3 14.56
Strongly silicified limestone with pyrite I disseminations. -125.3 25.7 15.35
PBR-230 Smelter/Kaolinite Enargite and kaolinite filling intergrain cavities. No reaction
observed between them. -126.0 13.89
-125.9 25.7
-137.3 14.21
Specular hematite, siderite massive replacement. Kaolinite as -136.5 20.5
PBR-246 Colquijirca/Kaolinite
well as minor sphalerite and galena as open space fillings. -136.7 14.17
-136.8 20.5
-124.4 14.42
Kaolinite as open space fillings associated to sphalerite,
galene, barite, and minor hematite in lixiviated silicified -124.4 22.2 14.92
PBR-250 Smelter/Kaolinite
dolostones. Sample from a relictic Zn-Pb-(Ag) body -126.3 14.87
encassed within enargite bodies.
-125.0 22.2
-115.4 13.59
Similar to sample PBR-250 but located 200 m north from -114.1 24.2 13.51
PBR-255 Smelter/Kaolinite this. In addition, quartz is part of the sphalerite-bearing
assemblage. -114.0 13.64
-114.5 24.2
-109.8 13.64
Massive sulfide replacement in dolostone. Main components -113.2 22.3 15.16
PBR-62 Colquijirca/Dickite
are tennantite, chalcopyrite, dickite, and quartz. -111.3 14.70
-111.4 22.3
-101.1 13.32
Bi-rich ore. Fine-grained Bi-bearing sulphosalts intimately -103.7 25.7 13.24
PBR-95 Colquijirca/Dickite
associated to dickite and minor quartz and barite. -100.6 13.00
-101.8 25.7

182
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Table 4.7 (Cont.). Hydrogen and oxygen isotope composition of kaolinite and dickite samples from the Cordilleran deposits of the
Colquijirca district.
Sample Location/Mineral Mineralogical description D1 d18O2 H2O
( VSMOW) ( VSMOW) wt %
-118.6 14.53
Dickite replacement of dolostone in a typical speckled -114.9 23.4 14.72
PBR-112 Colquijirca/Dickite texture. Sphalerite disseminations within dickite without
observed reaction in the border of the former. -118.8 14.89
-117.4 23.4

-110.0 25.8 14.05

Strongly argillized ore. Pyrite, galene, sphalerite, -110.9 27.0 13.25
PBR-240 Colquijirca/Dickite
chalcopyrite, and dickite as botroidal aggregates. -111.0 14.38
-110.6 26.4

-96.9 19.15
Geode-like pockets filled by pyrite, galena, sphalerite, barite -94.6 30.2 8.35
PBR-241 Colquijirca/Dickite and dickite; this last possibly mixed with minor kaolinite
amounts. No reaction between dickite and sulfides. -99.9 14.23
-97.1 30.2

-112.1 14.39
Nearly massive chert partly recrystallized to tiny quartz -111.5 23.2 14.73
PBR-247 Colquijirca/Dickite grains. Galena and sphalerite floating within dickite in small
cavities. -111.9 14.82
-111.8 23.2

-94.6 14.32
Massive pyrite II-enargite-quartz replacement with abundant
dickite coating cavities left by sulfides. No reaction -94.3 29.2 14.23
PBR-249 Smelter/Dickite
observed. Under microscope, dickite as disseminations
within enargite.
-94.4 29.2

-102.3 13.95
Enargite-rich ore. Dickite coating euhedral enargite grains -102.4 26.0 13.13
PBR-251 Smelter/Dickite
without recognizable reaction. -102.2 14.36
-102.3 26.0

-101.5 14.5
Siderite, sphalerite, galena massive replacement. Dickite as -100.5 25.9 14.2
PBR-252 Colquijirca/Dickite
open space fillings. Minor euhedral fluorite on siderite. -104.6 14.4
-102.2 25.9

values between -47 and -84 and between 8.8
and 13.6 , respectively. The second group
includes alunite intimately intergrown, and often in
reversal crystallization with enargite (at Smelter and
Colquijirca) and sphalerite and galena (at Colquijirca
and San Gregorio, Table 4.6). Except for the San
Gregorio samples, and sample PBR-262, this group
characterizes by 18O (SO4) compositions (between
-44 and -67 , Table 4.8) which are similar to the
first group but with D compositions consistently
lower.
The 3 San Gregorio alunite samples yield
the lowest D and 18O (SO4) values of all of those
analyzed from the whole Colquijirca district, i.e.
from -99 to -105 and from 5 to 8.1 ,
respectively (Table 4.6).
Oxygen and hydrogen isotope composition of
kaolinite and dickite
Kaolinite displays a relatively wide range of
18O and D values from 1.9 to 12.8 and from -
104 to -137 , respectively. Dickite compositions
are comprised within these ranges (18O between 4.4
and 12.3 and D between -97 to -117 ).
In comparison with alunite compositions, whereas
the 18O of both kaolinite and dickite samples are
broadly similar, the D compositions are significantly
lower (Table 4.7, Figure 4.7).
According to the zone they represent, four
samples of kaolinite (PBR-50, PBR-147, PBR-246,
and PBR-250) from the relatively external Zn-Pb-
(Ag) zone
have the lowest 18O and D compositions
of, respectively 1.9 to 4.3 and 125 to 142.25
(Table 4.7). Conversely, the rest of the samples,

183
 CHAPTER 4

Table 4.8. Oxygen isotope composition of quartz samples from the Cordilleran deposits of the Colquijirca district.
Sample Location Stage/ Assemblage Mineralogical description 18O
(VSMOW)
Main ore stage /quartz- Nearly massive enargite rich ore. Coarse alunite grains in part intergrown
PBR 131 Smelter 10.8
alunite with pyrite II and minor tiny quartz mainly as coatings on enargite.
Strongly silicified rock with minor pyrite I and quartz disseminations. The
PBR 262 Smelter Main ore stage rock is cut by abundant fracture-controlled cavities partially filled by pyrite 18.7
II, en, and alu.
Main ore stage /quartz- Massive enargite ore. Pyrite II and alunite accompanied by minor quartz
PBR 265 Smelter 11.8
alunite and zunyite replacing partially enargite.
Main ore stage / Vuggy silica in dacitic subvolcanic rock. Cavities partly filled by en-py-qtz 12.7
PBR 143 Smelter
enargite-bearing ass. assemblages and then cut by quartz-alunite veinlets and associated diss. 9.9
Main ore stage / Massive enargite-pyrite-quartz replacement. Sobordinated alunite-dickite- 13.4
PBR 263 Smelter
enargite-bearing ass. quartz assemblage cutting the sulfides. 13.4
Massive quartz-pyrite replacement in carbonate-rocks. Coarse grained
PBR 391 Smelter Early silica-pyrite stage 10.2
quartz in geodes.
Strongly silicified rock limestone with pyrite and quartz mainly as
PBR
Smelter Early silica-pyrite stage disseminations, and veinlets. Opaline silica intergrown with quartz as open 26.0
399b*
space fillings.
Nearly massive chert partly recrystallized to tiny quartz grains. Galena and
PBR 247 Colquijirca Early silica-pyrite stage 20.1
sphalerite floating within dickite in small cavities.

Matrix-supported hydrothermal breccia. Pyrite II and minor enargite and 13.3

Main ore stage /
PBR 244 Colquijirca quartz conform the matrix and are partially replaced by whitish sugary
enargite-bearing ass.
alunite plus dickite. 13.4
Main ore stage /bornite- Bornite-quartz-kaolinite assemblage superimposed on silicified rock
PBR 283 Colquijirca 17.1
bearing assemblages containing in addition minor quartz disseminations.
Main ore stage /quartz- Sulfide rock. Micro-clusters of fine-grained alunite and minor quartz and
PBR 208 San Gregorio 7.0
alunite kaolinite.
Silicificated dolostone. Tiny grains of quartz, pyrite, and sphalerite as part
PBR 177 San Gregorio Main ore stage 8.3
of the silicified matrix.
qtz, quartz; alu, alunite; en, enargite; py, pyrite
ass, assemblage(s); diss, dissemination(s);
*quartz intergrow with opaline silica

which constitutes the majority and which are located
in the internal and intermediate Cu-(Ag) and Cu-(Bi-
Ag) zones,
display isotopically heavier compositions
(18O between 4.4 and 12.8 and D between
-125.9 and -94.4 ).
Oxygen isotope composition of quartz
The three quartz samples from the Early
silica-pyrite stage yield 18O values of 10.2 , 20.1
, and as 18O enriched as 26.0 (Table 4.8). In
contrast, most of the 18O values from the Main ore
stage quartz samples are less 18O-enriched, in the
range of 7 to 13.4 . Two exceptions, samples
PBR-262 and PBR-283 gave 18O values comparable
to the most 18O-enriched quartz samples from the
Early silica-pyrite stage (from 18.7 18O to 17.1
18O, respectively), but in both cases, and despite
an intense overprinting by the productive Main ore
stage, silica from the Early silica-pyrite stage remains
volumetrically important (Table 4.8). It is, therefore,
possible that these two values may, in part, record the
participation of quartz from the Early silica-pyrite
stage.
The oxygen isotope composition of Main
ore stage quartz samples from internal parts of the
system, i.e., enargite-bearing zones, can be divided
into two groups according to the assemblage they
represent (Table 4.8). A first group of samples which
consist of enargite-bearing assemblages (PBR-143,
PBR-244, and PBR-263) produced a narrow range
of values between 9.9 and 13.4 18O. The
second group represented by two samples consisting
of alunite-bearing assemblages (PBR-131, PBR-265)
produced lower 18O values of 10.8 and 11.8 ,
respectively.
The two quartz samples from the San
Gregorio deposit, PBR-208 and PBR-177, yield
the most 18O depleted compositions of the district
(between 7.0 18O and 8.3 18O, respectively).
These values are similar to those obtained in alunite
(Table 4.6), a mineral observed to have co-precipitated
with quartz.

184
 CHAPTER 4

Table 4.9. 34S composition of sulfides and sulfates from the Cordilleran deposits deposits of the Colquijirca district.
34S
Deposit/Sample Zone galena sphalerite pyrite enargite alunite barite cpy bornite

San Gregorio A B A B A B A B
PBR-16 Zn-Pb-(Ag) -7.2 -7.2 -5.7 -5.7
PBR-47 Zn-Pb-(Ag) -6.2 -6.2 -4.0 -4.1
PBR-68 Zn-Pb-(Ag) -4.9 -4.5 -4.3 -4.3
PBR-53 Zn-Pb-(Ag) -6.2 -6.8 -16.5 -17.6
PBR-158 Zn-Pb-(Ag) -5.2 25.4
PBR-162 Zn-Pb-(Ag) -8.2 24.9
PBR-161 Zn-Pb-(Ag) -5.5 -10.0
PBR-179 Zn-Pb-(Ag) -8.5 -4.9 25.9
PBR-284 Zn-Pb-(Ag) 24.3
PBR-208(284B) Zn-Pb-(Ag) 24.9

Smelter
PBR-104 Cu-(Au-Ag) -0.1 4.4
PBR-106 Cu-(Au-Ag) -1.5 -2.2 -2.7
PBR-54 Cu-(Au-Ag) -1.1 -1.2 -1.1
PBR-105 Cu-(Au-Ag) -1.4 -1.3
PBR-56 Cu-(Au-Ag) -0.8 -0.9 -1.9 -2.2
PBR-137 Cu-(Au-Ag) -6.6 21.1
PBR-100 Cu-(Au-Ag) -1.5 -3.0
PBR-101 Cu-(Ag-Sn-Bi) -0.7 2.0 -0.7
PBR-259 Cu-(Ag-Sn-Bi) 2.5 1.3
PBR-103 Zn-Pb-(Ag) -2.9 -3.1 2.5 2.1

Colquijirca
PBR-107 Cu-(Ag) -0.9 -1.9
PBR-102 Cu-(Ag) 0.7 -1.1
PBR-114 Cu-(Ag) 2.5 0.8 23.4
PBR-108 Zn-Pb-(Ag) -1.6 1.3 26.4 26.7
PBR-61b Zn-Pb-(Ag) -0.7 -0.9 1.5
PBR-63 Cu-(Bi-Ag) -1.0 -1.1 1.8 26.7
PBR-193 Cu-(Bi-Ag) -2.5 -0.1 26.8
PBR-60 Cu-(Bi-Ag) -0.8 -1.0 -0.1 -0.2
PBR-50 Cu-(Bi-Ag) -0.0 -0.3 1.1 0.6 26.8
PBR-244 Cu-(Bi-Ag) 2.1
PBR-286 Zn-Pb-(Ag) -0.8 0.2
PBR-310 Zn-Pb-(Ag) 0.2 -1.7
PBR-277 Zn-Pb-(Ag) -1.7 0.5 25.0 23.9
PBR-253 Zn-Pb-(Ag) 0.9 1.1 -0.1 27.9
cpy: chalcopyrite

Sulfur isotope composition of sulfides and sulfates

Sulfur isotope composition of sulfides of the
Smelter and Colquijirca Cordilleran deposits yield a
narrow range of values between -3 and 4 34S.
Significantly lower values were obtained in sulfides
from the San Gregorio deposit where compositions
varied from around -10 to -4 34S (Table 4.9).
Sulfates (alunite and barite) yield 34S compositions
in the relatively narrow range of 21 to 27
34
S.
Discussion
In the northern sector of the Colquijirca district,
the large carbonate-hosted Cordilleran deposits
hosted in mainly marls and limestones of Tertiary age

185

are characterized by a relatively complex sequence of
events and processes in comparison to those more
simple from the Au-(Ag) high sulfidation epithermal
mineralization (Chapter 2e). During an Early silica-
pyrite stage (Chapters 2a and 2b), a large replacement
body with pyrite contents between 20 and 50 volume
% was formed. No economical mineralization is
ascribed to this stage. The polymetallic ores were
precipitated later during the Main ore stage and less
importantly, during the Late ore stage. The Main ore
stage produced sulfide-rich assemblages which were
superimposed on the silica-pyrite replacements, and
in less degree, beyond these replacements (Chapters
2a and 2b). The Main ore stage was responsible for the
district-scale prominent zoning that extends outward
and in all directions from the Marcapunta volcanic
complex. In the northern sector, on which this work
focuses, the zoning is recognized from the Smelter
to the Colquijirca deposits. The Cu-(Au-Ag) cores
are dominated by enargite; in the intermediate Zn-
Pb-Cu-(Ag-Bi) zone predominate sphalerite-galena,
and chalcopyrite, and the outer Zn-Pb-(Ag) envelope
is composed mainly of sphalerite and galena. A
Zn-bearing Fe-Mn carbonate zone, which is almost
barren of sulfides, occurs in the outermost part. The
Late ore stage formed mainly calcosite bodies, largely
overprinting the enargite-bearing zones.
Early silica-pyrite stage
Due to the very fine size nature of the fluid
inclusions, limited data were obtained from the
quartz-hosted fluid inclusions from the Early silica-
pyrite stage. Isolated inclusions gave homogenization
temperatures between 288 and 320C and salinities
in the narrow range of 3.23 and 4.65 NaCl wt %
equivalent. These values are the only approximation
to the nature of the Early silica-pyrite stage
fluids. However, salinities may be significantly
underestimated for two reasons. They possibly contain
considerable amounts of dissolved CO2 (untested via
Raman), because it is expected that during this stage
dissolution of the carbonate rocks, generated large
quantities of rock-derived CO2. Rare and small fluid
inclusions containing a tiny solid phase less than a
tenth in volume of the inclusion could be indicative
of higher salinities. Because of their size, melting of
ice temperatures could not be obtained.
Fracture-controlled fluid inclusions yield
lower salinities ranging from 1.91 and 3.71 NaCl
wt % equivalent, and also lower homogenization
temperatures from around 217 to 270C. Because
of their lower salinities and homogenization
temperatures, these secondary inclusions possibly
represent Main ore stage fluids.
Using equations of Zhang et al. (1989), the
calculated 18O compositions of water in equilibrium
with three Early silica-pyrite quartz samples are 2.9
, 10.3 , and as high as 12.8 . In addition, two
186
CHAPTER 4
18
O-enriched quartz samples (PBR-262 and PBR-283)
from the Main ore stage, both visually containing
silica from the Early silica-pyrite stage, gave 11
and 4.4 18O for waters in equilibrium with quartz
(Figure 4.9). These observations and results support
the general 18O-enriched nature of the early fluids
responsible for the massive silicification and pyrite
precipitation during the Early silica-pyrite stage.
Lacking D values, this 3 -13 18O
compositional variation of Early silica-pyrite stage
quartz samples is ambiguously interpretable. The
values may indicate a predominance of primary
magmatic water with only minor contribution of
exchanged and/or non exchanged meteoric water. In
addition, the two 18O-rich values in excess of 10
18O (Figure 4.9 A) may be explained in two ways:
(1) By isotopic exchange of primary magmatic water
with a carbonate rock, a typical isotopically heavier
reservoir (e.g., modeling b in Figure 4.9 A). This
scenario is possible at the site of the silica-pyrite
replacements where the carbonate-rich nature of
the host rock and the minimal temperatures needed
to attain such enrichment (~250C) are given. (2)
Alternatively, meteoric fluids during convection
through sedimentary rocks may attain 18O
compositions close to 10 if the fluids approach
300C at water/rock ratios from 0.3 to 1 (Figure 4.9
B). A convection cell approaching these temperatures
is plausible only at deep levels or close to the central
intrusive center. This unlikely scenario is further
discussed in the next section.
Other explanations on the magnitude of such
18
O enrichment are less probable. For example,
meteoric water may attain a 10-11 18O value by
isotopic exchange with sedimentary rocks at 300C
or more only at very low water/rock ratios, 0.01 or
less (e.g., Field and Fifarek, 1985; and Seal and Rye,
1992). These very low water/rock ratios are unrealistic
in epithermal environments where typical values are
between 0.2 and 2 (e.g., Taylor, 1974).
Main ore stage
Main ore stage fluid inclusion data are
given in Table 4.5 and represented in Figure 4.8.
Collectively, primary and secondary fluid inclusions
gave homogenization temperatures characteristic
for epithermal systems (from 165.9C to 298.2C).
Primary inclusions alone homogenized largely
between this range (between 172.2C and 298.2C).
Primary and secondary fluid inclusions indicate that
the Main ore stage fluids were typically of low salinity
with values comprised between ~0 and ~7 NaCl
wt % equivalent, but with the vast majority (90 %)
ranging between ~1.5 to ~6 NaCl wt % equivalent.
Variations of Th in both primary and
secondary fluid inclusions, as visually suggested by
the liquid-to-vapor ratios described above, are clearly
related to the distance from the Marcapunta volcanic

Au-(Ag) disseminated mineralization
alunite
Cordilleran mineralization
-40
alunite
D (, SMOW)
dickite
-60
kaolinite
-80
-100
L
W
M
-120
-140
-20 -15 -10
Figure 4.7. Summary diagram of oxygen and hydrogen isotope compositions for minerals alunite, dickite, and kaolinite of the
Oro Marcapunta disseminated Au-(Ag) prospect and the Cordilleran deposits of the Colquijirca district.
Figure 4.8
complex. PBR-295 fluid inclusions from a sample
collected near the contact between the main diatrema
neck and the surrounding carbonate rocks yield the
highest recognized Main ore stage homogenization
temperature of 298.2C. Up to tens of degrees lower
are recorded in parts of the Smelter deposit between
1 and 3 km north from the main intrusive center
where homogenization temperatures are largely
comprised between 280C to 260C (e.g., PBR-262,
Table 4.5). Lower values, on the order of 240C-
230C, are recorded in samples collected between 2
and 3 km north from the intrusive center, including
several ones collected from the enargite-bearing inner
bodies of the Colquijirca deposit (e.g., PBR-244). A
more abrupt homogenization temperature decrease
is recorded in Main ore stage primary and secondary
fluid inclusions hosted in quartz, sphalerite, and
barite, from the Colquijirca deposit to the north.
There, over a distance between 3 and 4.5 km from
Marcapunta, homogenization temperatures decrease
from approximately 240C in the innermost enargite-
dominant sub-zone (e.g., PBR-244), to 230-200C in
the intermediate
Zn-Pb-Cu-(Ag-Bi) zone (e.g., PBR-
62),
to as low as around 170C in the most externally
mineralized
Zn-Pb-(Ag) zone (e.g., PBR-246). Th in
primary fluid inclusions associated with the currently
mined Zn-Pb-(Ag) ores from the Colquijirca deposit
are most in the range of 230C to 180C (Table
4.5). Summarizing, and considering no pressure
correction for the measured Th (see discussion
below), the Cordilleran ores of the northern sector
CHAPTER 4
PMW
E
LIN
ITE
IN
OL
KA
-5 0 5 10 15
18O (, SMOW)
of the Colquijirca district display a decrease of the
temperature of formation of up to 130C from
the most internal enargite-bearing parts at Smelter
at ~300C to the most distal sphalerite-galena ores
located up to >4 km northward, at Colquijirca,
where fluid inclusions recorded homogenization
temperatures as low as ~170C.
The microthermometric results in quartz-
hosted fluid inclusions, irrespective of their primary
or secondary origin, can be divided according to
the assemblage which quartz represents. Inclusions
hosted in quartz from assemblages containing ore
sulfides (i.e., mainly enargite, chalcopyrite, and
sphalerite-galena) yield homogenization temperatures
between 218C and 286C and salinities between
0.35 and as high as 7.17 NaCl wt % equivalent (fluid
inclusions represented by the trendline b in Figure
4.8). A similar range of Th was obtained in inclusions
hosted in quartz from assemblages containing alunite
but lacking ore sulfides (between 221 and 273C).
This second assemblage type yield, nevertheless, a
distinct narrower salinity range comprised between
~0 and ~4 NaCl wt % equivalent (fluid inclusions
represented by the trendline a in Figure 4.8).
A discussion is deserved on the basis of a
general comparison, including these fluid inclusion
data, between the quartz-alunite alteration during
the early stage at the Oro Marcapunta Au-(Ag)
epithermal high sulfidation system and the alunite-
bearing assemblages deposition at the Smelter and
Colquijirca Cordilleran deposits.
187
 CHAPTER 4

400.0

350.0

300.0
b
a
ThC

250.0

200.0

150.0

100.0
0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0
Salinity (wt % NaCl eq.)

Type of Early silica-pyrite stage fluid inclusions:

Isolated in quartz
Fracture-controlled in quartz

Type of Main ore stage fluid inclusions:

Primary in quartz from enargite-bearing assemblage
Secondary in quartz from enargite-bearing assemblage
Primary in sphalerite from sphalerite-bearing assemblage
Secondary in sphalerite from sphalerite-bearing assemblage
Primary in quartz from alunite-bearing assemblage
Secondary in quartz from alunite-bearing assemblage
Secondary in quartz from sphalerite-bearing assemblage
Primary in barite from tennantite-bearing assemblage
Primary in enargite from enargite-bearing assemblage

Figure 4.8: Homogenization temperature (Th) vs. salinity (wt % NaCl equivalent) diagram of fluid inclusions in several
mineral from the Cordilleran Smelter and Colquijirca deposits. Dashed gray line represents an inferred mixing trend, see text
for discussion.

As documented in other Au-(Ag) disseminated of Smelter and Colquijirca, the precipitation

systems, it was demonstrated that at Oro Marcapunta
the early fluids from which quartz-alunite alteration
was generated, were not the responsible direct for
the Au-(Ag) economical mineralization (Chapter
2c). Similarly, all the mineralogical and geochemical
evidences indicate that in the Cordilleran deposits
of the alunite-bearing assemblages was not
necessarily produced from the fluids responsible
for the polymetallic mineralization. In this second
mineralization type, the pristine ore fluids were likely
not that acid. As described in detail in Chapters 2a
and 2b most of enargite, chalcopyrite, and sphalerite-

188
 CHAPTER 4

A
-20 Au-(Ag) disseminated mineralization 400C 300C
0.01
alunite fluids 500C b

L
W
-40

M
0.1
D (, SMOW)

Cordilleran mineralization 1
ND 0.001 860C
-60 alunite fluids TRE
I XING Exchange trend of Julcani
M
dickite fluids primary magmatic fluids
0.01
-80 kaolinite fluids

-100

E
L IN
ITE
IN
-120

OL
0.1

KA
COLQUIJIRCA METEORIC WATER a
-140 350C

Early silica-pyrite stage

18OH2O in equilibrium with quartz from: Main ore stage

Smelter Colquijirca

Main ore stage San Gregorio

-20 -15 -10 -5 0 5 10 15

B VV

-20 Au-(Ag) disseminated mineralization

alunite fluids
PMW
L
W

-40
M
D (, SMOW)

Cordilleran mineralization 300C

0.3
-60 alunite fluids
200C
dickite fluids
0.15
-80 kaolinite fluids REN
D
400C
IN GT
MIX 300C
100C

-100 200C 1
E
IN

300C
L
ITE

100C 200C
IN

-120 1
OL

400C
KA

100C
300C
200C
-140 100C

COLQUIJIRCA METEORIC WATER

-20 -15 -10 -5 0 5 10 15

18O (, SMOW)
Figure 4.9
Figure 4.9. Summary diagram of oxygen and hydrogen isotope data from the Au-(Ag) disseminated mineralization and
Cordilleran deposits of the Colquijirca district. D and 18O (SO4) values of alunite fluids were calculated according to
equations of Stoffregen et al. (1994) using temperatures obtained from fluid inclusion microthermometry. D and 18O values
of kaolinite and dickite fluids were calculated using equation of Gilg and Sheppard (1996) and Sheppard and Gilg (1996).
Temperatures used in the calculations were taken from fluid inclusion microthermometric measurements. Part A of the diagram
includes modelings of isotopic exchange between: (1) magmatic water and sedimentary rocks at static conditions (line b from
Field and Fifarek, 1985) and (2) meteoric water and sedimentary rocks at also static conditions (line a from Seal and Rye,
1992). In contrast, part B of Figure 4.9 includes isotopic modeling of 11.9-10.6 Ma Colquijirca meteoric waters that ex-
changed isotopically through convection with sedimentary and igneous rocks.

189

galena precipitated visually devoid of alunite-
bearing assemblages. At Smelter enargite largely
precipitated only with minor amounts of kaolinite-
dickite(smectite-illite-sericite). Only around 10 %
of enargite is observed to have co-precipitated with
the more acidically formed alunite(zunyite-other
APS minerals). In these cases, based on hydrogen and
oxygen isotope data and discussed in Chapter 5, the
ore fluids would have acquired their low pH and high
to very high oxidation states only at shallow levels
of the system by mainly H2SO4 admixture following
SO2 disproportionation.
The non productive character of much of
the acid fluids responsible for the alunite-bearing
manifestations is recognized in both, the Au-(Ag)
disseminated and the polymetallic Cordilleran systems.
Fluid inclusion data from these two alunite-bearing
manifestations yield similar Th-salinitiy trendlines
(labeled a in Figures 4.8 and 4.4, respectively). The
Th-salinity trendline for the case of the quartz-alunite
alteration at Oro Marcapunta is interpreted in terms
of mixing between a 250-280C fluid of low salinity
(up to 4 NaCl wt % equivalent) with a colder 215C-
240C fluid of near-to-zero NaCl wt % equivalent
salinity, this last most probably of meteoric origin.
A similar mixing process with temperatures and
salinities close to these values may be proposed for the
generation of the alunite-bearing assemblages during
Cordilleran mineralization (trendline a in Figure 4.8).
In this case, end-members are recognized to be a
hot (up to ~290C) fluid with maximum salinities
of ~4 NaCl wt % equivalent and a significantly colder
fluid (as low as ~210C) of nearly zero NaCl wt %
equivalent salinity.
Concluding, several lines of evidences indicate
that the alunite-bearing assemblages from the
Cordilleran mineralization, even if they are closely
related in space with the enargite-bearing ores at
Smelter and Colquijirca, would have been formed not
directly from the fluids responsible for the polymetallic
ore deposition, but from fluids similar to those that
formed 0.3 to 1.0 My earlier the acid vuggy silica
and quartz-alunite alteration at the Oro Marcapunta
Au-(Ag) disseminated high sulfidation system. The
process, evidently, would have also involved, as in
the case of the Au-(Ag) high sulfidation system,
SO2 disproportionation within a water-saturated
shallow zone. Because of the general positive spatial
correlation, this zone would have been broadly the
same in which the Cordilleran mineralization took
place.
Entrainment of a SO2 magmatic plume in
the formation of the Cordilleran alunite fluids, is
suggested by the 34S values for alunite (21.1
to 26.4 ) from the Main ore stage quartz-alunite
assemblages which are typical of hydrothermal
magmatic fluids in which sulfate has equilibrated
with H2S formed through disproportionation of SO2
within a condensing vapor plume (e.g., Rye, 1993).
Using fractionation coefficients of Stoffregen
190
CHAPTER 4
et al. (1994), the estimated 18Oso4 and D
compositions of water in equilibrium with Main ore
stage alunite range from values around -41 D
and 7 18Oso4 to progressively isotopically lighter
fluids down to around -99 D and 6 18Oso4
along a linear trend that suggests mixing of magmatic
fluids and unexchanged meteoric fluids (Figure
4.9). These values fit with the mixing line deduced
for the acidic fluids that generated the vuggy silica
and quartz-alunite zones at Oro Marcapunta. By
projecting the regression mixing line representing the
entire population of alunite D and 18Oso4 values
of the Colquijirca district it is possible to estimate a
composition of around -14010 D and -181
18O for the 10.6-11.9 Ma Colquijirca meteoric
water. These values are similar to meteoric water
composition estimated for other Miocene systems of
central Peru (e.g., Deen et al., 1994). 18O composition
of water in equilibrium with quartz from alunite-
bearing assemblages comprise the same range of
values defined by the alunite fluids supporting that
magmatic fluids predominated during the generation
of the acidic fluids.
34S compositions of sulfides of the whole
Smelter-Colquijirca corridor show in essence a
magmatic origin for both the Early silica-pyrite stage
and the Main ore stage (Figure 4.10). The lack of
equilibrium between collected sulfide-sulfate pairs
did not allow to estimate H2S/SO4 ratios of the
hydrothermal fluids during the Main ore stage. These
ratios were probably highly variable based on the
mineralogical observations suggested on one side
by the alunite-dominant assemblages (highly oxidant
acidic fluids) and on the other by the absence of
sulfates accompanying most of the enargite ores
(fluids deficient in SO4).
Concerning the hydrogen and oxygen isotopic
composition of the fluids responsible for ore
precipitation, one of the best approximations may be
obtained by using the compositions of kaolinite and
dickite, minerals recognized to have co-precipitated
with enargite, bornite, chalcopyrite, and sphalerite.
Paragenetic and textural relationships suggesting
a co-genetic origin between these clays and ore
minerals have been described in detail in Chapters
2a and 2b, the main observation being that kaolinite
and dickite often occur in reversal crystallization with
ore sulfides.
Estimated 18O and D values of water
in equilibrium with kaolinite and dickite (using
equations of Gilg and Sheppard (1996) and Sheppard
and Gilg (1996); kaolinite-dickite fluids in Figure
4.9), plot in a field distinctly different that of most
of the alunite fluids of the Marcapunta Norte and
Colquijirca deposits. The kaolinite-dickite fluids plot
indeed below the mixing trend between meteoric and
magmatic waters (or exchanged magmatic waters)
represented by most of the alunite fluids (Figure 4.9).
These compositions display a positive 18O shift an
a minimal shift in D (Figure 4.9), is best explained

in terms of mixing with exchanged meteoric water.
Figure 4.9 B shows several modelings of isotopic
equilibrium of Miocene meteoric water during
convection through sedimentary rocks (Figure
4.9 B) or through igneous rocks (Figure 4.9 B). As
explained by Field and Fifarek (1985), in contrast to
static fluids, convected fluids equilibrate over a range
of temperatures and water/rock mass ratios. Details
in the modeling procedure are given in Field and
Fifarek (1985).
If equilibrated with igneous rocks, (Figure 4.9
B), meteoric water may attain values of 7 18O by
continuous isotopic exchange only if temperatures
exceeds 400C. These temperatures are unrealistic
because theoretically meteoric waters would not
across the brittle-ductile interface in which maximum
temperatures between ~370C 400C are estimated
(e.g., Fournier, 1999). If equilibrated with sedimentary
rocks similar 18O values are attained if the fluids
attain ~200C and the integrated water/rock mass
ratio attain around 1 (Figure 4.9 B). At Colquijirca the
geological conditions for this probable scenario of
isotopic exchange are given. Phyllites, conglomerates
and sandstones of the Excelsior and Mitu Groups
are the dominant rocks down to at least 2000 m
depth (Chapter 1a).
Therefore, a possible process which could
explain the isotopic composition of kaolinite and
dickite is mixing of magmatic waters, or exchanged
magmatic waters, with meteoric waters that exchanged
basically with sedimentary rocks. According to this
hypothesis, the isotopically most depleted kaolinite-
dickite fluids (the three kaolinite values around ~-4
18O in Figure 4.9) could indicate mixing between
exchanged and unexchanged meteoric waters in
the sense of Field and Fifarek (1985). The location
of these kaolinite samples in relatively external
zones of the system (Table 4.7) in which surface-
derived meteoric waters are likely to be a significant
component is consistent with such a mixing scenario.
Conversely and more importantly, the 18O-enriched
fluids (from ~2 to as high as ~7 18O) could
be indicative of mixing of magmatic hydrothermal
fluids with exchanged meteoric waters (e.g., Foley, et
al., 1990). The S isotopic compositions of Cordilleran
sulfides are consistent with the entrainment of
magmatic waters.
The conclusion that kaolinite dickite fluids may
record exchanged meteoric waters is supported by
fluid inclusion and element distribution data, which
also point to dilution of magmatic waters through
low-saline fluids as explained in Chapter 5.
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 CHAPTER 4

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studies. Economic Geology, 84, p. 410-424

193
194
N-8812000

N-8811000

N-8810000

N-8809000
E -360000
To
Hu o
a ra as c
uc eP
ac
a rr od
Ce
To
samples for stable isotope analysis

524 line
548 line
580 line
612 line
644 line
676 line
708 line
740 line
772 line
804 line

700 line

4, 3
0

60
4 ,4 0

C ondorc ayan

40
P rinc ipal pit

4, 3
E -361000 B C olquijirc a
Marc apunta 4, 50 0

0
4 ,5 0 A
80
4, 4 S melter
4,460

4,440

4,420

4,400
Merc edes -C hoc ayoc pit
4,380

4,3 60

4,3 40
D
4,320
4 ,3 0 0
E -362000 0
4 ,2 8

C olquijirc a
alunite samples
kaolinite and dickite samples
0 500
quartz samples
meters
Appendix 4.1: Map of the Smelter-Colquijirca mineralized corridor showing location of collected quartz, alunite, and kaolinite-dickite
CHAPTER 4

Chapter 5
Summary and final discussion
Geological setting
The Colquijirca District is located 12 km south
of the famous Cerro de Pasco District, on the cen-
tral Altiplano of Peru, at 4200-4500 m.a.s.l. (Figure
5.1). The district displays two main ore types, both
common of the central-northern segment of the
Peruvian Andean Cordillera: (i) basically carbonate-
hosted sulfide-rich Cu-(Au-Ag) and Zn-Pb-(Ag) de-
posits (Smelter, Marcapunta Oeste, Colquijirca, and
San Gregorio), and a (ii) Au-(Ag) disseminated high
sulfidation epithermal prospect (Oro Marcapunta).
The ores are in close spatial relation to a Miocene
magmatic center, the Marcapunta volcanic complex,
which occupies the central sector of the district (Ahl-
feld, 1932; Lindgren, 1935; McKinstry, 1936; Yarin-
gao et al., 1997; Vidal et al., 1997; Bendez, 1997;
Fontbot and Bendez, 1999, 2001; Bendez and
Fontbot, 2002; Bendez et al., 2003; Vidal and Li-
garda, 2004).
Carbonate rocks of different ages are intruded
by the Marcapunta volcanic complex (Figure 5.1). A
400 m thick marine sequence of basically limestone
and dolostone of the Upper Triassic-Lower Jurassic
Pucar Group is present mainly in the southern sector
of Marcapunta in which the Zn-Pb-(Ag) San Grego-
rio ores are entirely hosted. The Eocene Pocobamba
Fm., with a thickness up to 450 m, and, generally,
composed of limestone, marl, and dolostone, covers
most of the northern sector of the Colquijirca Dis-
trict but also occurs beneath the volcanic cover in the
western flank of the Marcapunta complex (Figure
5.1). In these sectors, the Pocobamba Fm. is repre-
sented by its two main members: a lower one, mostly
constituted by Pucar-derived conglomerates of the
Shuco Member and an upper member mainly made
up of limestones and marls of the Calera member
(Angeles, 1993). The Smelter (Marcapunta Norte),
Marcapunta Oeste, and the Colquijirca deposits are
encased in these Eocene carbonate rocks.
The district, and in general the region, was af-
fected by Tertiary folding (north north-east fold axes,
Figure 5.1), which pre-dates the emplacement of the
Marcapunta volcanic complex and the spatially asso-
ciated ores. Major nearly north-south trending faults
are together with the folding trends, the most out-
standing structural features of the district. Of these,
of major importance is the Longitudinal Fault which
seems to have controlled the emplacement of the vol-
canic complexes in this part of the region. This fault
CHAPTER 5
is virtually tangent, from north to south, to the Cerro
de Pasco, Yanamate, and, according to geophysical
data reported in Chapter 1a to the Marcapunta vol-
canic centers (Figure 5.1). Other important fracture
systems recognized in the Colquijirca District follow
north-west and north-east trends and are interpreted
to be related to the compressional tectonic event re-
sponsible for the generation of the Tertiary folding
(Figure 5.1).
The Marcapunta volcanic complex
The Marcapunta volcanic complex, exposed
in the center of the Colquijirca district, can be cat-
egorized as a diatreme-dome complex, (Sillitoe, 2000;
Bendez et al., 2002; Sarmiento, 2004). Physically,
Marcapunta displays a similar internal configuration
as that found in the nearby Cerro de Pasco and Yana-
mate complexes. It consists of multiple porphyritic
dome-lava intrusions of mainly dacitic composition
which pre- and post-date several episodes of explo-
sion breccias typical of diatreme conduits. Other
fragmental rocks, mainly lapilli tuff and block and
ash deposits are particularly abundant in the north-
ern flank of Marcapunta. The diatreme conduit de-
veloped mainly within the central part of the volca-
nic edifice, but ramifications have been recognized to
extend up to 1 km north and south from the central
main conduit (Figure 5.2). Inward-dipping normal
faults located in peripheral areas and drill core corre-
lation discussed in Chapter 1b suggest that the entire
edifice collapsed prior to the main episodes of min-
eralization. North-west oriented fractures and ring
faults related to this collapse later played a main role
in channeling the ore fluids in much of the district.
40
Ar/39Ar dating conducted on magmatic
biotite gave inverse isochron ages of 12.90.1 and
12.70.1 for two slightly propylitized dome-lava bod-
ies and a well defined plateau age of 12.430.06 for
an unaltered dome emplaced beyond the mineraliza-
tion limits (Chapter 3a). This last age is the available
best approximation on one of the episodes of the
magmatic history of the district related to the min-
eralization and which the present investigation has
shown to have spanned for at least ~2 My.
Geochemical data obtained in this study show
that the lava-dome facies of the Marcapunta volcanic
complex are invariably of dacitic high-K subalkaline
composition (Chapter 1b). In addition, trace element
concentrations of Sr, Y, and REE indicate that Mar-
195
 CHAPTER 5

0 79 75 71

E -360 000 (7616' W)

3 Km IQUITOS

N 4

CHICLAYO
CAJAMARCA

8
TRUJILLO
HUARAZ

AREA OF
GEOLOGICAL MAP

PA
12 LIMA

CI
FI
CUZCO
Cerro de Pasco

C
N-8820000 (1040' S)

O
16 AREQUIPA

C
E
A
N
Fault

Thrust and Yanamate

reverse faults

Fold axis

GEOLOGICAL UNITS

Colquijirca
Dacite diatreme-dome complex (Miocene)
B
Pocobamba Formation (E ocene),
mainly limestones and marls
Goyllarizquizga Group (C retaceous),
sandstones
Pucara Group (Upper T riassic-
L ower Jurassic), limestones
Mitu Group (Permian-T riasssic),
sandstones

E xcelsior Group (Devonian), phyllites

Marcapunta
MINERALIZATION TYPE

Au-(Ag) disseminated epithermal San Gregorio

Polymetallic Cordilleran deposits

Figure 5.1
Figure 5.1: General geology of the Cerro de Pasco-Colquijirca sector. Note that quaternary cover was removed.

196

capunta dacite approach an adakite-like signature
similar to volcanic and plutonic rocks recognized in
some of the economically most important Andean
mining districts (Chapter 1b).
As previously introduced, mineralization in
the Colquijirca district can be categorized into two
main types: (i) Au-(Ag) disseminated mineralization
developed in volcanic rocks and (ii) Polymetallic sul-
fide-rich deposits hosted mainly in carbonate rocks.
Despite evident similarities between these two ore
types in mineral alteration assemblages and depth of
emplacement, differences in metal suite, total sulfide
content, and ore zoning are more prominent. There-
fore, each type is considered in this study separately
and has been classified into different ore deposit
classes. Furthermore, spatial relationships between
these ore types indicate that precious metal epither-
mal mineralization at Marcapunta predated those of
Smelter-Colquijirca, an observation that is confirmed
in terms of absolute ages through two radiometric
surveys conducted in the present study (Chapters 3a
and 3b).
Au-(Ag) disseminated mineralization
Crosscutting relationships indicate that the Oro
Marcapunta volcanic-hosted Au-(Ag) disseminated
mineralization took place early in the hydrothermal
history of the district. From the same relationships, it
was deduced that this mineralization type developed
a recurrent succession of events, each composed of
several stages (Chapter 2c):
(i) An Early barren stage of highly acid char-
acter strongly leached important parts of the central
sector of the Marcapunta volcanic edifice producing
highly porous vuggy silica bodies. Morphology of
these bodies is for the most part controlled by sub-
vertical faults and more permeable lithologies result-
ing in vuggy silica ledges and irregular bodies, respec-
tively (Figure 5.2). The last bodies, which are mainly
hosted within fragmental rocks, are particularly well
developed in phreatomagmatic breccias. Vuggy silica
bodies are zoned to advanced argillic alteration zones
dominated by a quartz-alunite-(zunyite-svanvergite
series phases) assemblages which in turn are envel-
oped, from inner to outer zones, by argillic, phyllic,
and propylitic alteration haloes. Virtually no eco-
nomic concentration is attributed to the Early barren
stage. Locally native sulfur and pyrite are observed
in non supergene oxidized parts of vuggy silica and
quartz-alunite zones.
(ii) A Gold stage followed the acid leaching
and was responsible for the Au-(Ag) mineralization
at Oro Marcapunta. In contrast to the Early barren
stage, the presence of kaolinite-(smectite-illite-seric-
ite) associated with the Au-(Ag) deposition indicates
that the ore fluids were not of strongly acid character.
Economically interesting Au-(Ag) bodies are largely
hosted in highly permeable altered units formed dur-
ing the Early barren stage (i.e., vuggy silica and, to in
less degree, quartz-alunite rocks). They contain mil-
CHAPTER 5
limetric wide sulfide- and oxide-bearing veinlets geo-
metrically arranged in a sort of stockwork. Parts
consisting of sulfide-bearing veinlets are made up of
pyrite, covellite, enargite, chalcocite, and sphalerite in
amounts that collectively are below 5 volume % of
a given mineralized rock. Typical gold and silver val-
ues are on the order of 0.1-0.5 ppm and 5-15 ppm,
respectively (Ag/Au ratios from ~10 to ~30). Ox-
ide-bearing veinlets consist largely of hematite and
goethite of botryoidal texture. Oxide-bearing vein-
lets are volumetrically more important than those
carrying sulfides and are recognized from surface
down to levels deeper than the base of supergene
oxidation suggesting that the Fe oxides are hypogene
(see below). Gold and silver grades of oxide-bearing
veinlets zones range between 0.5 and 2 ppm and 20
and 80 ppm, respectively (Ag/Au ratios from ~10 to
~30). These grades are significantly higher than those
carrying sulfides with gold and silver values. Several
lines of evidences, including reversal overprintings
between patches of sulfide-bearing and oxide-bear-
ing veinlets suggest that oxides and sulfides formed
from a single ore event during the Gold stage.
(iii) Veins and breccias dominated by APS-
phases and veins composed of nearly massive Fe ox-
ides were recognized to cut both the Early barren
stage and the Gold stage and are placed collectively
as Late stages. To these stages are attributed pebble
dike-like breccias consisting of rounded mineral-
ized vuggy silica clasts cemented by plumose alunite.
Some veins composed basically of fine-grained APS-
phases show significantly high gold and silver values
(up to 9.5 ppm and 28 oz/t). Another type of vein
consists of nearly massive oxides carrying high con-
tents of Ag (100 to 500 ppm) and As (2000 to 10000
ppm). Gold contents in these veins are on the order
of several parts per million resulting in Ag/Au ratios
>100.
Sulfide-rich polymetallic deposits
Mainly carbonate-hosted sulfide-rich polyme-
tallic replacement deposits constitute the second main
type of mineralization developed in the Colquijirca
district (Chapters 2a, 2b, and 2d). This mineraliza-
tion type aggregates a global resource of at least 300
Mt of Cu-Zn-Pb-(Au-Ag) ores. In descriptive terms,
three distinctive features characterize these ores: (i)
high total sulfide content, (ii) economically interest-
ing polymetallic metal suite, and (iii) well-marked
metal and mineral zoning. These features, which are
well recognized in the Smelter and Colquijirca depos-
its and less pronounced at San Gregorio, can be de-
scribed in terms of three stages of mineralization:
(i) During an Early silica-pyrite stage, in
which no economical ore deposition occurred, pyrite
accompanied with silica strongly replaced mainly the
Eocene Pocobamba carbonate rocks surrounding the
Marcapunta volcanic complex. According to drilling
and geophysical surveys, the replacements entirely
surround the volcanic complex delineating a funnel-
197
198
S N
ORO MARCAPUNTA

SMELTER COLQUIJIRCA

the Oro Marcapunta, Smelter, and Colquijirca deposits.

GEOLOGICAL UNITS
100 m

200 m Dacite diatreme-dome complex (Miocene)

Calera Formation (Eocene), mainly limestones and marls

Shuco Member (Eocene), calcareous conglomerates

Mitu Group (Permian-Triasssic), sandstones

MINERALIZATION
Cordilleran ores Au-(Ag) disseminated ores
Cu-(Au-Ag) zone Quartz-alunite + vuggy silica
containing Au-bearing veinlets
Zn-Pb-Cu-(Ag-Bi) zone

Zn-Pb-(Ag) zone

Figure 5.2: North-south longitudinal section of the northern sector of the Colquijirca district. The section includes
CHAPTER 5

Figure 5.2

like shape. The replacements, controlled by the NS
trending fold and fault systems, extended through a
3 km length corridor toward the north, to the center
of the Colquijirca deposit (Figure 5.2). It is estimat-
ed that the explored parts of the whole silica-pyrite
funnel-like replacements aggregate at least between
1.5 and 2.5 billion tons with pyrite grading between
30 % and 60 volume %. The remainder is basically
composed of silica, largely quartz. Throughout these
replacements, pyrite and quartz are fine grained (<1
mm). Compositionally pyrite is essentially stoichio-
metric and typically it contains between 0.2 wt % and
0.6 wt % As, and not rarely as high as 1 wt %-1.2 wt
%. Though rare, rutile, zircon, scheelite, muscovite,
and chlorite are phases ascribable to the Early silica-
pyrite stage.
(ii) The Main ore stage followed the Early
silica pyrite stage and was superimposed on most of
the silica-pyrite replacements (Figure 5.2). The Main
ore stage produced the well-marked ore metal and
mineral zoning observed through the entire Smelt-
er-Colquijirca mineralized sector. The most internal
zone of the system consists of Cu-(Au-Ag) ores in
form of enargite-(luzonite, colusite)-bearing assem-
blages in addition to significant amounts of pyrite.
The Smelter deposit is largely constituted by these
assemblages and constitutes a resource of at least 50
Mt at ~1.9 % Cu, ~0.4 g/t Au, and 25 g/t Ag. The
Cu-(Au-Ag) enargite-bearing zone at deposit scale
mimics the silica-pyrite corridor from Smelter to
Colquijirca, though in detail it is not entirely coinci-
dent.
Enargite, luzonite, and colusite are generally
accompanied by very minor amounts of sulfides,
sulfides-sulfosalts, tellurides, and tungstates, notably
wolframite and bismuthinite. Gold was deposited as
electrum and Au-(Ag)-bearing tellurides associated
with tennantite-goldfieldite. Enargite, luzonite, colu-
site, and pyrite are in essence nearly stoichiometric in
composition. Pyrite distinguishes from that precipi-
tated from the Early silica-pyrite stage by its high Cu
contents (0.5 to 1.5 wt %). Most of the enargite-
bearing ores are nearly exempt of significant amounts
of non-sulfide gangue minerals. They mainly occur
as assemblages dominated by alunite, quartz, zunyite,
and other APS phases, including notably those of the
woodhouseite series. It is estimated that the enargite-
bearing assemblages associated with these acidically
formed alunite-bearing assemblages constitute <40
volume % of the whole Cu-(Au-Ag) enargite-bear-
ing zone. In most of this fraction, the alunite-bearing
assemblages were introduced at several pulses during
the Main ore stage and though commonly in con-
tact with the ores, seen in detail, they mostly pre- and
post-date the enargite-bearing assemblages. Enar-
gite also occurs in assemblages with alunite and/or
zunyite but this occurrence does not represent >10
volume % of the global Cu-(Au-Ag) enargite-bearing
zone.
More rarely observed, very small amounts of
CHAPTER 5
kaolinite and dickite and occasionally illite and smec-
tite occur together with enargite in textures indicative
of co-precipitation (e.g., in reversal crystallization, in-
clusion of clays in enargite without reaction; Chapter
2a). Detailed mapping of enargite bodies in the cur-
rently mined Principal pit supports these co-precipi-
tation indications (Chapter 2b). Mapping shows in
detail a discordant distribution pattern of the alunite-
bearing and the enargite-bearing assemblages but a
positive correlation between ores and kaolinite-(dick-
ite-illite-smectite). These different patterns reinforce
the observation that parts of the enargite-(luzonite-
colusite) zone did not form under very acidic condi-
tions, at least not at levels defined by the stability field
of alunite-(zunyite) at epithermal conditions.
The enargite-bearing assemblages are transi-
tionally zoned outward to bornite-dominant and ten-
nantite-dominant sub-zones of local extent which
are best exposed in the Colquijirca deposit (Figure
5.2). These sub-zones, as also occur with all outer
zones, are external to the Early silica-pyrite stage re-
placements and typically conform mantos. Though
locally the bornite-dominant and tennantite-domi-
nant sub-zones may reach economical grades, the
bodies are generally small (<1000 t). Bornite and
tennantite are mainly accompanied by pyrite plus
minor to trace amounts of relatively rare sulfides
and sulfides-sulfosalts minerals. Gangue mineralogy
consists largely of assemblages containing mixtures
of kaolinite, dickite, barite, quartz, and locally illite,
smectite, and occasionally also alunite. Of these sub-
zones, the tennantite-dominant sub-zone carries bo-
nanza silver contents (>40 oz/t Ag) which are mainly
ascribed to associations containing stromeyerite, na-
tive silver, Ag-bearing rare sulfides, and in places to
Ag-rich tennantite.
The tennantite-dominant sub-zone is sur-
rounded by a relatively well-extended Zn-Pb-Cu-(Ag-
Bi) zone in which prevails sphalerite, galena, pyrite,
kaolinite, dickite, siderite, barite, and quartz. Subor-
dinately occur variable quantities of chalcopyrite plus
accessory amounts of Bi- and Ag- bearing phases of
the sulfide-sulfosalt group. This zone is one of the
economically most valuable of the Colquijirca de-
posit and are currently mined by its Zn, Pb, and Ag
contents which, respectively average 7 %, 3.5 %, and
5 oz/t (Figure 5.2). Small internal parts of this zone
are highly enriched in silver (40 and 70 oz/t), and in
part also in bismuth (up to >1 %) being the main
Ag and Bi hosts matildite-bearing and wittichenite-
bearing assemblages, respectively. These Ag-rich por-
tions, as well as the tennantite-rich sub-zone, were
mined underground during the early twenty century
constituting the Bonanza Epoch (Chapter 0).
The Zn-Pb-Cu-(Ag-Bi) zone grades outward
to a chalcopyrite-free Zn-Pb-(Ag) zone mainly com-
posed of sphalerite, galena, pyrite, kaolinite, dickite,
alunite, and more externally of sphalerite, galena,
pyrite, Zn-bearing siderite, kaolinite, and hematite.
Other characteristic but less abundant minerals in-
199

clude magnetite, marcasite, and quartz. This zone
comprises the largest Zn-Pb-(Ag) resources of the
Colquijirca deposit, which prior to mining possibly
exceeded 30 Mt at 6 % Zn, 3 % Pb, and 3.5 oz/t Ag.
The Zn-Pb-(Ag) zone displays gradual mineralogical
variations with increasing distance from the Cu zones.
FeS content in sphalerite increases from around 0.1-
0.3 wt % in assemblages containing kaolinite-dick-
ite-(alunite) to 1-2 wt % in siderite-kaolinite-bearing
assemblages from the outer parts of the Zn-Pb-(Ag)
zone. Another mineralogical variation is the preva-
lence of galena over sphalerite in the external potions
of the Zn-Pb-(Ag). Some of these galena-rich parts
are highly argentiferous with Ag contents as high as
30 oz/t for certain thin mantos (up to 1 m thick).
An outermost Zn-bearing zone surrounds the Zn-
Pb-(Ag) ores, but in contrast to the other Zn zones,
this is virtually devoid of sulfides. It basically consists
of Zn-bearing carbonates including preponderantly
siderite and rhodochrosite and can form mantos up
to 3 m thick with grades >5 % Zn.
The Main ore stage deposited highly variable
amounts of total sulfides. Sulfide contents increase
from 5 %-15 volume % in the Cu-(Au-Ag) enargite-
dominant zones to 30 %-60 volume % in most of
the sphalerite-galena-bearing zones. Then an abrupt
decrease is observed to 20 %-10 volume % in the
outer galena-dominant parts of the Zn-Pb-(Ag) zone
and to virtually zero in the Zn-carbonate zone.
(iii) A Late ore stage was the last recognized
episode of economical mineralization at Smelter and
Colquijirca. It deposited mainly chalcocite with mi-
nor amounts of covellite basically as veinlets cutting
and replacing the different zones of the Main ore
stage. Tennantite-(chalcopyrite-covellite) veinlets are
observed as the last sulfide-bearing manifestation in
some parts of both Smelter and Colquijirca and are
also attributable to the Late ore stage. Gangue min-
erals are rare and only minor amounts of sericite-
(quartz-illite-smectite) are observed to accompany
chalcocite.
Although the Late ore stage produced small
ore concentrations at Smelter, Late ore stage formed
large orebodies in the recently explored Marcapunta
Oeste project. In this last deposit, chalcocite exten-
sively replaces parts of enargite bodies that are im-
mediately adjacent to nearly vertical faults. Sectors
without evidence of faulting show virtually no enar-
gite replacement by chalcocite.
By combining the abovementioned mineral
assemblages (described in detail in Chapter 2) with
homogenization temperatures obtained from mi-
crothermometric measurements in fluid inclusions
(Chapter 4) it is possible to reconstruct approximately
the main sulfidation state path of the fluids respon-
sible for the formation of the sulfide-rich polymetal-
lic ores at Smelter and Colquijirca (from the Early
silica-pyrite stage to the Main ore stage). Assuming
cooling from 320C to 290C, the fluid environment
during the Early silica-pyrite stage may be represent-
200
CHAPTER 5
ed in Figure 5.3 (path A) by early hematite-pyrite-
bearing assemblages to late enargite-bearing assem-
blages (Chapter 2a). Similarly, in terms of cooling,
fluids evolved during the Main ore stage from high to
intermediate sulfidation states (path B, Figure 5.3) as
described by the assemblages dominated by: enargite
at ~300C (in the internal Cu zones), pyrite-bornite
and tennantite at 220C (in the intermediate zones),
and hematite-pyrite and magnetite at 180C (in the
external Zn-Pb zones). FeS mol % in sphalerite co-
precipitated with most of these assemblages are con-
sistent with this general path.
The general features of the sulfide-rich
polymetallic system are interpreted in terms of a se-
quence of processes that began with the widespread
replacement of the carbonate rocks during the Early
silica-pyrite stage. Fluids from this stage were only
moderately acidic as indicated by the presence of
muscovite and chlorite as accessory matrix miner-
als. According to Fournier (1985), at shallow levels,
fluids of moderately acid character may produce
massive replacement of limestone by simultaneously
dissolving calcite and precipitating silica. Because of
the absence of carbonate phases, the silica-pyrite re-
placements have a low acid-buffering capacity. Un-
der these conditions the subsequent, generally more
acid, Main ore stage fluids could circulate through
the silica-pyrite replacements at pH conditions nearly
invariable. This low acid-buffering capacity is most
remarkably indicated by the persistence of alunite-
bearing assemblages along the entire 3 km long from
Smelter to Colquijirca.
The analysis of crosscutting relationships of
mineral assemblages and associations at the Smelter-
Colquijirca corridor records a progressive advanc-
ing of the Main ore stage sulfide-rich mineralization
front with time (Chapters 2a and 2b). An indication
of the magnitude of such advancing is recorded in
the central part of the Smelter deposit where several
bodies of sphalerite-galena-siderite-kaolinite float
in the enargite-bearing zones. Observed in detail,
the sphalerite bodies are cut and in part replaced by
the enargite-bearing assemblages. Also in Smelter, at
polished section scale, numerous samples display re-
sidual sphalerite and hematite surviving as inclusions
in part replaced by enargite-bearing assemblages.
These observations indicate that the inner Cu zones
encroached on the Zn-Pb zone. By the time the re-
sidual sphalerite-bearing zones had formed, the outer
limit of the Cu mineralization was restricted to parts
as close as 1 km from the Marcapunta volcanic com-
plex, this is, around 1.5 km south of the final Cu
front exposed in the Principal pit at Colquijirca. Late
reversals in the temporal sequence of mineral assem-
blages are observed at both Smelter and Colquijirca,
where veinlets composed largely of chalcocite or ten-
nantite or sphalerite replace the enargite-bearing as-
semblages. At Marcapunta Oeste, chalcocite replac-
ing enargite in bodies strongly controlled by faults is
interpreted in terms of retraction of the mineraliza-
 CHAPTER 5

T(C)
100 200 300 400 500 600 800 1000

0 py po
n
+b p Andesitic
-2 py c magma

" "

TE
"SO2 gas flux

bn y
-4 ion

t+ p
sat
ST fur conden

m +c
hm
N Sul
, fm
-6 TIO A e n , tt
tn
A
FID GH
-8
UL HI

lo+ sp
po
a
.0
.0
log fS2

"S RY B

20
10
VE cv

.0
30
-10 dg 0.
1

m +py
hm
t
py p o
-12 GH
HI bn
+
py c p
W
-14 LO
p+ py
cp

TE
a s tn +

IA +As ERY
D V

po
-16 E p y sp

n
M

i ro
a
py o
TER p
W z +po
-18 I N r"
fe LOmt+qaya lite
uf
c kb f
"ro Modified from Einaudi et al. 2003

2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 1.0 0.8

1000/T (K)

Figure 5.3: Sulfidation state paths for the Early silica-pyrite stage (path A) and Main ore stage (path B) of the Cordilleran
mineralization in the Colquijirca district. Mineral assemblages and temperatures according to observations recorded in Chapters
2a and 4.
tion front, possibly during the waning of the hydro-
thermal system activity when meteoric water input
was higher.
In general, the above features are also rec-
ognized at the Zn-Pb-(Ag) San Gregorio deposit
(Chapter 2d). However, significant mineralogical dif-
ferences are also observed, notably, the microgranu-
lar mineralogical texture and the absence of Early
silica-pyrite stage replacements. The San Gregorio
ores display typically a microgranular and unconsol-
idated texture with grain sizes ranging between 20
and 60 m. Sulfides consists of sphalerite, galena,
and pyrite and minor amounts of marcasite. Gangue
minerals include mainly quartz, kaolinite, and APS
phases, largely alunite. Most of sphalerite and galena
occur associated with kaolinite-quartz, and in places,
with alunite-quartz. In the last case, alunite occurs
commonly in contact with sphalerite as intergranu-
lar fillings showing no apparent reaction. In parts
where alunite precipitated as microveinlets cutting
sphalerite clusters, no signs of dissolution or recrys-
tallization are observed. These observations indicat-
ing alunite-sphalerite equilibrium are consistent with
FeS contents in sphalerite which average ~0.3 wt %
though commonly are below the instrumental detec-
tion limits (<0.05 wt %). These sphalerite-galena-ka-
olinite-alunite-quartz assemblages and associations
constitute the dominant orebodies of the San Gre-
gorio deposit. At the deposit scale, they are part of
zoned structures that includes Cu-bearing ledges in
more internal eastern parts and Zn-bearing carbonate
zones in more external positions. The sulfide content
for the bulk San Gregorio deposit ranges between 20
% and 30 volume %, considerably lower than those
of the Zn-Pb-(Ag) Colquijirca deposit. This is due to
the low pyrite contents of the San Gregorio ore (5-
10 volume %) compared to 20-30 volume %. pyrite
in the Main ore stage at Colquijirca.
In the whole Smelter-Colquijirca mineralized
corridor, the total sulfide content in volume percent-
age are distributed, according to mineralization stag-
es, as follow: 85 %-90 % of the total sulfide content
of the Smelter-Colquijirca mineralized corridor cor-
respond to mainly pyrite from the Early silica-pyrite
stage; 10-15 % correspond to enargite, pyrite, sphal-
erite, and galena from the Main ore stage; and <1 %
to the Late ore stage, largely as chalcocite.
The features summarized above are typical of
Cordilleran deposits as characterized by Einaudi
(1977) or more recently re-termed by Einaudi et al.

201

Middle Miocene
Probable periods of gold deposition
12
Age (Ma) 11
Previous surveys
K/Ara
39
Ar/ 40Ar (furnace)b
This survey:
39
Ar/ 40Ar (infrared laser)
K/Ar whole rock
15 14
Figure 5.4: Summary diagram of available geochronological data (K/Ar and 40Ar/39Ar) from the Colquijirca district: a,
from Vidal et al. (1984) at 2; b, Bendez et al. (2003) at 2 level of confidence.
(2003) as zoned base metal veins. In this work we
adopt the first denomination.
Timing of mineralization
Several indirect field evidences suggest that the
Cordilleran mineralization at Smelter and therefore
Colquijirca occurred subsequent to the Au-(Ag) dis-
seminated mineralization. Only recently in the west-
ern flank of Marcapunta (Marcapunta Oeste project)
drilling encountered up to 350 m of vertical extension
containing Au-(Ag) high sulfidation epithermal ledg-
es, which in the lowermost 50 m are superimposed
by Cordilleran ores. This superposition is comprised
of barren, Early stage quartz-alunite zones, contain-
ing Au-(Ag) veinlets, which are cut by cm wide py-
rite-(enargite)-rich veinlets and less frequently veins.
Precise absolute ages of key hydrothermal
events were obtained through two 40Ar/39Ar dating
surveys performed on alunite from the two miner-
alization types. Step-heating degassing was induced
using a resistance furnace for the first survey and in-
fra-red (CO2) laser for the second one. Both surveys
yielded basically the same results (Chapters 3a and
3b) and are consistent with a hydrothermal magmat-
ic-related origin of the Colquijirca ores and with the
relative timing of mineralizing events indicated by
crosscutting relationships (Chapter 2), i.e., Au-(Ag)
mineralization predated polymetallic Cordilleran
202
CHAPTER 5
Late Miocene
a
on biotite
a
on sanidine
a
on alunite
on alunitea
Dome emplacement
Au-(Ag) disseminated
epithermal mineralization
Cordilleran ores
of San Gregorio Cordilleran base metal deposits
13 12 11 10
Age (Ma)
ores.
Seven Early barren stage alunite samples from
the Au-(Ag) disseminated high sulfidation epither-
mal system gave furnace and laser derived 40Ar/39Ar
plateau ages in the range of 11.90.07 to 11.100.06
Ma at2. This is a particularly long lifespan for a hy-
drothermal cell related to a single intrusion and it is
therefore interpreted in terms of several shorter epi-
sodes of mineralization sustained by multiple intru-
sive and/or thermal episodes (Cathless, 1997) related
to a large magma reservoir at depth. The existence of
several episodes of mineralization finds support by
linking individually the 40Ar/39Ar ages with observed
crosscutting relationships between dated alunite (Ear-
ly barren stage) and periods of gold deposition de-
fined by the sulfide- and oxide-bearing veinlets (Gold
stage). From these relationships, it is argued that at
least two, or more, recurrent episodes of acid altera-
tion-gold deposition took place during the activity of
the Au-(Ag) epithermal system (Chapter 3b).
Seven laser and furnace derived 40Ar/39Ar ages
obtained on alunite that predate, are coeval, and
post-date different generations of enargite-bearing
and sphalerite-bearing assemblages indicate that the
sulfide-rich Cordilleran Smelter and Colquijirca de-
posits were formed subsequent to the Au-(Ag) high
sulfidation epithermal mineralization at Oro Marca-
punta which lasted from 11.9 to 11.1 Ma (Figure 5.4).
 CHAPTER 5

The obtained values (plateau ages) define a relative-
ly narrow period of hydrothermal activity between
10.830.06 and 10.560.08 Ma (2). This period,
though considerably shorter than that recognized for
the Au-(Ag) high sulfidation system, is long enough
to allow a linkage to several intrusion and/or thermal
events.
Additionally, three K/Ar ages were obtained
from the Cordilleran San Gregorio deposit by means
of conventional whole rock analysis (Chapter 3b).
Two ages resulted similar at 13.1-13.22.2 Ma (2)
and the third at 13.94.0 Ma (2). Ruled out an ex-
cess of inherited argon caused by detrital mica in the
alunite-rich concentrates and supported by the con-
cordance of two of the ages at 13.1-13.22.2 Ma , it
is not excluded that the San Gregorio deposit may be
formed earlier than the other Cordilleran ores of the
district. Alternatively, given the large errors on the
K-Ar ages, the San Gregorio deposit could also form
contemporaneously with Smelter and Colquijirca.
Collectively, and without considering San Gre-
gorio, the radiometric data set from the Au-(Ag) dis-
seminated and from the Cordilleran mineralization
types indicate a long duration of the hydrothermal
activity in the Colquijirca district (up to ~1.5 My).
Similar long durations were also recognized else-
where in hydrothermal systems that produced very
large to giant ore concentrations (e.g., Chuquicamata,
El Teniente, Butte, La Escondida, El Salvador, El In-
dio; Ossandn et al. 2001, Quiroz, 2003, Gustafson
et al, 2001, Heather et al. 2003, Maksaev et al 2003).
Fluid inclusion and stable isotope results
Fluid inclusion and stable isotope data from
the Au-(Ag) disseminated mineralization at Oro
Marcapunta are characteristic of Au-(Ag) high sul-
fidation epithermal systems (e.g., Arribas et al, 1995;
Fifarek and Rye, 2005). Similarly, a fluid inclusion
and stable isotope study of the Colquijirca Cordil-
leran assemblages provided data similar to those ob-
tained in other Cordilleran deposits (e.g Deen et al.,
1994; Taylor, 1974). Because no significant erosion
affected the whole district (Chapter 4), and because
Raman tests failed to detect CO2 in a selection of
fluid inclusions (Chapter 4), no correction of the mi-
crothermometric results summarized in what follows
was undertaken.
Au-(Ag) high sulfidation epithermal system
Fluid inclusions show that vuggy silica and
quartz-alunite zones formed from the highly acidic

Au-(Ag) disseminated mineralization fluids VV

-20 alunite fluids

Cordilleran mineralization fluids PMW

-40
alunite fluids
D (, SMOW)

300C
L

dickite fluids 0.3

W
M

-60 kaolinite fluids

200C
exchange with
Minerals end 0.15 sedimentary
-80 ing tr 400C rocks
alunite mix 300C
dickite 100C
ing

200C
1
-100 kaolinite
mix

300C exchange with

igneous rocks
100C 200C
-120
100C
1
300C 400C
200C
-140 100C

COLQUIJIRCA METEORIC WATER

-20 -15 -10 -5 0 5 10 15

18O (, SMOW)
Figure 5.5: Summary diagram of oxygen and hydrogen isotope data from the Au-(Ag) disseminated mineralization and
Cordilleran deposits of the Colquijirca district. D and 18O (SO4) composition of alunite fluids were calculated according to
equationsFigure et al. (1994) using temperatures obtained from fluid inclusion microthermometry. D and 18O composi-
of Stoffregen5.5
tion of kaolinite and dickite fluids were calculated using equation of Gilg and Sheppard (1996) and Sheppard and Gilg (1996).
Most of temperatures used were taken from fluid inclusion microthermometric measurements. The diagram also includes isotopic
modeling of 11.9-10.6 Ma Colquijirca meteoric waters that exchanged isotopically through convection with sedimentary and
igneous rocks. Additional details are given in the text.

203

Early barren stage between 210C and 280C. These
fluids were of low salinity with typical values rang-
ing from ~0 to ~4 % NaCl equivalent. These data
examined on the basis of mineralogical and zonal
patterns suggest that the Early barren stage fluids de-
rived from a mixing process (mixing trend line in Fig-
ure 5.5) which involved variable amounts of two end
members (a) cold fluids (210C-240C) of nearly
zero salinities with hot slightly saline fluids (250C-
280C and 3 %-4 % NaCl equivalent).
Stable isotope data are in agreement with this
conclusion and provides additional clues on the na-
ture of these acidic fluids. The calculated isotope
compositions of water (D and 18O (SO4)) in equi-
librium with Early barren stage alunite (alunite flu-
ids in Figure 5.5) define two contrasting composi-
tional fields. The first field is characterized by typical
magmatic signatures with D and 18O values in
the approximate ranges of -45 to -55 and 7
-7.5 , respectively. The second field (D from
around -75 to -90 and 18O from -3 to -6
) fit with a meteoric water-magmatic water mixing
trend (Figure 5.5). 18O values from this second field
range from -3 to as depleted as -6.5 . The mag-
matic end-member was most likely a magmatic vapor
plume, from which SO2 interacted with water and
condensed to form H2SO4, the main acid agent in the
formation of the vuggy silica and quartz-alunite al-
teration. Sulfur isotope compositions of alunite (34S
from 21.5 to 22.4 ) support this origin in which
sulfate has equilibrated with H2S formed through
disproportionation of SO2 within a condensing va-
por plume (e.g., Rye, 1993). Water involved in the dis-
proportionation of SO2 was most probably meteoric
as indicated by the 18O depleted signatures of the
second compositional field. Variable meteoric water
inputs into the hydrothermal system are indicated by
the wide spectrum of calculated 18O values of water
in equilibrium with quartz collected from quartz-alu-
nite assemblages (18O values from ~- 3 to ~7
).
Limited temperature and salinity information
was obtained from fluid inclusions hosted in quartz
from the Au-(Ag) productive Gold stage. The data
broadly fit the mixing trend recognized for the Early
barren stage suggesting similar end-member fluids
with temperatures ranging from 190C to 260C
and salinities from ~1 to ~5 wt % NaCl equivalent.
A number of fluid inclusions hosted in Gold stage
quartz from 90 m below the summit of Marcapunta
record boiling. The microthermometric results indi-
cate that the boiling curve adjusts for a 200-300 m
depth equivalent, indicating that erosion of the sys-
tem was modest.
D and 18O (SO4) values of water in equilib-
rium with Late stage plumose alunite are comprised
within the mixed fluids field defined by the alunite
fluids from the Early barren stage (Figure 5.5). It is,
therefore, concluded that Late stages plumose alu-
nite was formed when magmatic waters interacted
204
CHAPTER 5
significantly with meteoric waters. This conclusion
is supported by the 34S compositions of plumose
alunite (20.6 and 22.4 ) which suggest that sul-
fur of this coarse-grained alunite type resulted from
disproportionation of SO2 to H2S and H2SO4 within
a condensing vapor plume.
Polymetallic Cordilleran system
Measurable fluid inclusions hosted in quartz
from the Early silica-pyrite stage yield homogeniza-
tion temperatures between 288C and 320C and sa-
linities in the narrow range of 3.23 and 4.65 NaCl
wt % equivalent. These values are the only available
approximation to the nature of the Early silica-py-
rite stage fluids. However, salinities could be in fact
significantly higher because of the likely presence of
dissolved CO2 (untested via Raman) and the occur-
rence of a solid phase in some trails of minute inclu-
sions. 18O value of water in equilibrium with Early
silica-pyrite quartz spans from around 3 18O to
as high as 13 18O. Considering the magmatic
signatures of sulfur from pyrite that co-precipitated
with quartz, the quartz fluid compositions >10
18O may be explained by isotopic exchange between
magmatic-dominant waters with the Pocobamba car-
bonate rocks.
Main ore stage fluid inclusion in quartz,
sphalerite, in a few cases in barite and enargite gave
homogenization temperatures characteristic for epi-
thermal systems (from ~160C to ~300C). The flu-
ids were typically of low salinity with values com-
prised between ~0 and ~7 NaCl wt % equivalent, but
with the vast majority (90 %) ranging between ~1.5
and ~6 NaCl wt % equivalent. Significant variations
of Th are correlated with the distance to the Mar-
capunta volcanic complex. In the inner Cu-(Au-Ag)
enargite zone, homogenization temperatures of up
to nearly 300C were obtained in adjacent positions
to the volcanic complex, whereas in more distal parts
(i.e., at Colquijirca) temperatures fluctuate between
~240C-~230C. A more abrupt temperature de-
crease is recorded in zones external to the enargite
zone in the Colquijirca deposit. Temperatures from
around 240C in the enargite zone and in the tennan-
tite-dominant sub-zone decline to ~230C-~200C
in the Zn-Pb-Cu-(Ag-Bi)
zone
and down to ~170C
in some parts of the kaolinite-dickite-bearing Zn-Pb-
(Ag)
zone. In contrast to temperature, no systematic
variation in salinities from Smelter to Colquijirca is
distinguished (Figure 4.7 in Chapter 4). An exception
is that most of the less saline studied fluid inclusions
(<1 % NaCl equivalent) occur more abundantly in
the Zn-Pb-(Ag) zone.
The gradual temperature decrease from Smelt-
er to Colquijirca is in agreement with drilling cor-
relation indicating that these deposits are part of a
single and continuous mineralized corridor which
was formed from a single process of mineralization
(Main ore stage). At Colquijirca, the strong zonal pat-
tern, including the notable decrease in the sulfidation
 CHAPTER 5

500

400

300
Ag (ppm)

200

100

0
0 1 2 3 4 5
Au (ppm)
Au-(Ag) disseminated epithermal mineralization

Polymetallic Cordilleran deposits

Figure 5.6: Ag/Au ratios of representative ore samples, mineralized intervals, and orebodies of the two mineralization types
of the district. Large open square represents the Ag/Au ratio of the bulk Smelter-Colquijirca mineralized corridor. The figure
also shows regression lines for the values of the two mineralization types.

states of sulfides assemblages from high (enargite-
pyrite) to intermediate (chalcopyrite-pyrite) seems to
respond to changes of chemical and physical vari-
ables mainly T decrease and subordinate pH increase.
The effect of T decrease is well illustrated along a
large mineralized segment that extends from the
chalcopyrite-dominant sub-zone to the inner sphal-
erite-bearing parts of the Zn-Pb-(Ag) zone. There
is no evidenced a significant pH variation, as sug-
gested by the uniformity of the non sulfide gangue
mineralogy (mainly dickite-kaolinite). In this case a
considerable temperature decrease is recorded from
~220C-210C in the chalcopyrite-dominant sub-
zone to ~190C-~170C in the sphalerite-bearing
zones. In accordance with theoretical assessments
(e.g., Hemley et al., 1992), the zonal pattern for this
segment, which includes the copper-zinc interface, is
therefore explained by cooling of the hydrothermal
fluids. Cooling could probably be reinforced by lo-
cal mixing with meteoric fluids which apparently was
pronounced in the outer parts of the system as indi-
cated by the fact that the secondary fluid inclusions
with the lowest salinities and temperatures are mainly
located in the Zn-Pb-(Ag) zone.
Two relatively contrasting Th vs. salinity
trends may be discriminated from the available fluid
inclusion data from the Main ore stage (Figure 4.7 in
Chapter 4). A first trend defined by quartz-hosted in-
clusions from alunite-bearing assemblages comprises
salinity values between ~0 and ~4 NaCl wt % equiv-
alent and homogenization temperatures in the range
of 221C and 273C. This trend is nearly identical
to that delineated by the Early barren stage fluid in-
clusions during Au-(Ag) disseminated mineralization.
Supported on mineralogical observations combined
with stable isotope data it is interpreted that this
trend reflects mixing between a magmatic end-mem-
ber, likely a SO2-bearing vapor plume, with meteoric
water. The estimated 18O and D compositions of
water in equilibrium with Main ore stage alunite range
from values around -41 D and 7 18O to pro-
gressively isotopically lighter fluids down to around
-99 D and -6 18O along a linear trend that
suggests mixing of magmatic fluids and unexchanged
meteoric fluids (Figure 5.5). These values fit with the
mixing line deduced for the acidic fluids that gener-
ated the vuggy silica and quartz-alunite zones at Oro
Marcapunta. By projecting the regression mixing line
representing the entire population of alunite D and
18O values of the Colquijirca district it is possible to

205
 CHAPTER 5

Au-(Ag) disseminated ores Au-(Ag) disseminated ores

Cordilleran ores Cordilleran ores

Marcapunta
diatreme-dome complex

Pocobamba Pocobamba
carbonate rocks carbonate rocks

mixing of diluted brines with acidic fluids

derived from SO2 disproportionation

Mitu red beds Mitu red beds

diluted brine isotopic diluted brine isotopic

exchange exchange
mixing mixing

brine brine

brine refluxing Excelsior slates brine refluxing Excelsior slates

magma chamber
Brittle-ductile transition magma chamber Brittle-ductile transition

a. Scenario 1 b. Scenario 2
1 Km
Fluids
brine vapor plume ascent meteoric water

Figure 5.7: Sketch representing the general genetic model proposed for the mineralization in the Colquijirca district. Processes
involved in each scenario are described in the text.

estimate a composition of around -14010 D
and -181 18O for the 10.6-11.9 Ma Colquijirca
meteoric water. These values are similar to meteoric
water composition estimated for other Miocene sys-
tems of central Peru (e.g., Deen et al., 1994).
Entrainment of a SO2 magmatic plume in the
formation of the alunite fluids, is also suggested by
the 34S values for alunite (21.1 to 26.4 ) from
the Main ore stage quartz-alunite assemblages which
are typical of hydrothermal magmatic fluids in which
sulfate has equilibrated with H2S formed through
disproportionation of SO2 within a condensing va-
por plume (e.g., Rye, 1993).
The second Th vs salinity trend (Figure 4.7
in Chapter 4) defined by fluid inclusions represent-
ing enargite-bearing assemblages, largely devoid of
alunite covers a larger salinity interval between 0.35
and 7.2 NaCl wt % equivalent and temperatures from
218C to 286C. These data combined with stable
isotope data suggest mixing of magmatic fluids with
exchanged meteoric waters. The entrainment of ex-
changed meteoric waters is indicated by the estimated
18O and D compositions of water in equilibrium
with kaolinite and dickite, phases recognized to have
co-precipitated with the ores. These compositions
plot following a pattern typical of meteoric waters
that have exchanged isotopically with host rocks
displaying a positive 18O shift and a minimal shift
in D (Figure 5.5). Modeling of isotopic equilibri-
um through convection suggests that 10.5-11.9 Ma
Colquijirca meteoric water exchanged with predomi-
nantly sedimentary host rocks. The exchanged mete-
oric waters then possibly experienced simple mixing
with magmatic waters. 34S compositions of sulfides
of the whole Smelter-Colquijirca corridor, with av-
erage values close to zero, support such magmatic
component. The modeling predicts that the isotopic
exchange could take place only if the integrated wa-
ter/rock mass ratio attained values close to 1.
General genetic model
A general genetic model on the main mineral-
ization processes that took place in the Colquijirca
district is proposed on the basis of the integrated
available geochronological, fluid inclusions, and sta-
ble isotope data coupled with geological and miner-

206

alogical observations. Besides the hydrothermal ore
processes that occurred at shallow levels, the model
includes general conceptual considerations for deep-
er parts of the system.
During a given period of the hydrothermal
history of the district, the model supposes the co-
existence at depth, near the brittle-ductile transition,
of hypersaline fluid and single-phase vapor (Ulrich
et al. 1999; Harris et al., 2003). Because of the prob-
able shallow emplacement of the main degassing
cupola(s) of the magma chamber (suggested by the
shallow nature of porphyry Cu mineralization related
to other Cordilleran deposits of Peru as for exam-
ple in Quiruvilca between 1 and 2 km; in Noble and
McKee, 1999), the single-phase vapor fluids during
their ascent should intercept the two-phase surface in
the liquid side of the critical curve preventing vapor
contraction (Figure 3, in Heinrich, 2005) and permit-
ting breaching of the two phase field below 450C.
The resulting two fluids, independently of the mech-
anism of phase separation (i.e., boiling or condensa-
tion), are possibly the precursor fluids responsible for
the generation of the acid alteration-gold deposition
recurrent pulses recognized during the Au-(Ag) high
sulfidation epithermal mineralization at Oro Marca-
punta (Figure 5.7). The very low to low salinities at
Oro Marcapunta (~0 to ~4 wt % NaCl equivalent)
suggests that phase separation was achieved through
condensation. In addition, low Ag/Au ratios (<30)
from the Au-(Ag) disseminated bodies (Figure 5.6)
are similar with values obtained from quantitative
microanalysis of single-phase vapor fluid inclusions
in other porphyry-related systems (e.g., Ulrich et al.,
1999).
While the vapor phase ascended, the brine (hy-
persaline fluid) probably remained largely within the
brittle-ductile transition and then gradually liberated
as this transition retracted downward with time (Fig-
ure 5.7). In these instances meteoric waters that had
exchanged isotopically with mainly sedimentary rocks
of the Excelsior and Mitu Groups through convec-
tion over perhaps tens of thousands of years, could
mix with the brines. At Colquijirca, modeling based
on the isotopic composition of ore-related kaolin-
ite and dickite predicts that these exchanged waters
could acquire the obtained isotopic compositions at
moderate to high total mass water/rock ratios (be-
tween 0.3 and 1). On the other hand, stable isotope
evidences (D, O, S) pointing to extensive mixing be-
tween magmatic and exchanged meteoric water have
the implication that the 2 to 7 wt % NaCl equivalent
salinities of the Cordilleran ore fluids at Colquijir-
ca may be best explained by dilution of magmatic
brines. The hypothesis that Cordilleran ore-forming
fluids formed by dilution of magmatic brines is sup-
ported by key element concentration ratios of the ore
samples and of the bulk Smelter-Colquijirca mineral-
ized corridor notably Ag/Au (~50 to >300, Figure
5.6), Cu/Au (~7x104-~9x104), and Fe/Au (~2x107-
~5x107), which are similar to ratios observed in
CHAPTER 5
brines from microanalysis of fluid inclusions from
other porphyry-related localities and different from
the ratios measured in single-phase vapor fluid inclu-
sions coexisting with the brine fluid inclusions (Ul-
rich et al. 1999; Harris et al., 2003). As mentioned
before, the Ag/Au, Cu/Au, and Fe/Au ratios of the
Au-(Ag) disseminated bodies at Oro Marcapunta are,
in turn, similar to those measured on single-phase va-
por fluid inclusions by Ulrich et al. (1999); Harris et
al. (2003) in several porphyry-related systems.
Acidic fluids were common during the pe-
riod of Cordilleran mineralization. They manifested
most prominently through assemblages exempt of
ore minerals, though less pronounced, they also pre-
cipitated alunite accompanied by enargite-(sphaler-
ite). The isotopic evidence indicates that, as at Oro
Marcapunta, these acidic fluids formed from SO2
disproportionation by reaction with water, suggest-
ing that multiple vapor plumes were released during
the lifespan of the Colquijirca hydrothermal history.
Most likely, SO2 would have derived from the rising
single-phase vapor fluids. Cordilleran fluids could,
subsequent to dilution, potentially mix with the acid-
ic fluids at different levels of the system resulting
most in oxidized acidic ore fluids. Alternatively, Cor-
dilleran fluids and acidic fluids could enter the epith-
ermal environment separately. Figure 5.7 illustrates
these two scenarios. Both scenarios presumably took
place repeatedly, though not necessarily cyclically, at
different periods during the recognized 11.9-10.6 Ma
hydrothermal history of the Colquijirca district. The
mineralogical evidence suggest that the second sce-
nario was more common.
In more detail, both scenarios can be described
as follows:
Scenario 1 (Figure 5.7.a). Mixing of Cordil-
leran fluids (diluted brines) with acidic fluids derived
from vapor plumes.
In this scenario the Cordilleran ore fluids could
mix with acidic fluids derived from vapor plumes at
several levels of the system, though most probably
at higher positions than the zone where presum-
ably took place the brine dilution by mixing with ex-
changed meteoric waters. This is supported on the
stable isotope data which indicate that most of the
alunite fluids did not entrain exchanged meteoric wa-
ters, probably because the SO2-bearing vapor plume
rose too fast to permit mixing with the exchanged
meteoric waters. This scenario explains the usual oc-
currence of alunite-enargite and alunite-sphalerite
assemblages.
Scenario 2 (Figure 5.7.b). Cordilleran fluids
and acidic fluids enter the epithermal environment
separately.
The association of Cordilleran ores with small
amounts of kaolinite-dickiteillite, smectite (and not
to alunite-bearing assemblages) suggests a scenario
in which Cordilleran fluids and acidic fluids also may
207

have entered the epithermal environment separately.
This scenario may be explained by SO2-bearing vapor
plumes raising rapidly while the brines could remain
re-mixing within or near the brittle-ductile transition
where some brines were diluted by exchanged mete-
oric waters. The diluted brines could then be tapped
and enter the ore deposition site when the acid pro-
duced by SO2 disproportionation was already partly
consumed.
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209
 CHAPTER 5

210
 General Appendix. Part A: Complete list of samples studied in this work. The table includes details such a macroscopic description and the type of analyse conducted. Part B: Sample Location.
PART A

Type of analyse
Sample Deposit/area Macroscopic description
XRD XRF ICP NA MP REE CY TS PS S C O H Pb Sr Dat. F. I.

PBR-1 San Gregorio Bitouminous mudstone rich in volcanic detritic grains. Post mineralization lacustrine sediments.

PBR-2 San Gregorio Breccia. Oxidized rock fragments in an argillaceous to arenaceous matrix. Sedimentary breccia (San Juan).

PBR-3 San Gregorio Oxidized material composed of 65 vol. % rounded detritic quartz in desagregated argillaceous matrix (in part kao) material.

PBR-4 San Gregorio Oxidized material composed of 50 vol. % rounded detritic quartz in desagregated argillaceous matrix (in part kao) material.

PBR-5 San Gregorio Oxidized material composed of 70 vol. % rounded detritic quartz in desagregated argillaceous matrix (in part kao) material.

PBR-6 San Gregorio Oxidized material composed of 70 vol. % rounded detritic quartz in desagregated argillaceous matrix (in part kao) material.

PBR-7 San Gregorio Black (bitouminous?) heavy argillite, some goethite and relictic sulfides (pyrite?).

PBR-8 San Gregorio Partly oxidized material composed of 35 vol. % rounded detritic quartz in an unconsolidated argillaceous cement (35 vol. %).

PBR-9 San Gregorio Partly oxidized material composed of 50 vol. % rounded detritic quartz in an unconsolidated argillaceous cement (35 vol. %).
General appendix

PBR-10 San Gregorio Strongly silicified and in part oxidized dolostone. It contain10 vol. % rounded detritic quartz.

PBR-11 San Gregorio Silicified and mineralized dolostone. Abundant pyrite (30 vol. %) besides some kaolinite (10 vol. %).

PBR-12 San Gregorio Friable material composed of 25 vol. % rounded detritic quartz in an unconsolidated argillaceous cement (70 vol. %).

PBR-13 San Gregorio Friable material composed of 30 vol. % rounded detritic quartz in an unconsolidated argillaceous cement. Some pyrite visible.

PBR-14 San Gregorio Friable argillaceous material. Some visible pyrite (5 vol. %) and kaolinite (<5 vol. %).

PBR-15 San Gregorio Friable argillaceous material. Some visible pyrite and galena (<5 vol. %).

PBR-16 San Gregorio Massive sulfide replacement. 30 vol. % galena, 40 vol. % sphalerite, 20 vol. % kaolinite, 10 vol. % carbonates (sid.?).

PBR-17 San Gregorio Dolostone containing up to 10 vol. % of pyrite as disseminations.

PBR-18 San Gregorio Slightly altered dolostone. Dolomite recristalizacion.

PBR-19 San Gregorio Partly decarbonatized dolostone. 5 vol. % of disseminated pyrite.

PBR-20 San Gregorio Slightly altered dolostone. Moderately heavy rock.

PBR-21 San Gregorio Slightly altered dolostone. 2 vol. % of pyrite finely disseminated.

PBR-22 San Gregorio Partly decarbonatized dolostone. friable (decarbonatized) fraction contains some kaolinite (5 vol. %).

PBR-23 San Gregorio Slightly altered dolostone. 2 vol. % of pyrite finely disseminated.

PBR-24 San Gregorio Breccia. Clasts of dolostone (45 vol. %) in argillaceous matrix. 5 vol. % of finely disseminated pyrite.

PBR-25 San Gregorio Friable argillaceous material. 2 vol. % of pyrite finely disseminated.

PBR-26 San Gregorio Friable argillaceous material. 2 vol. % of pyrite finely disseminated.

PBR-27 San Gregorio Friable argillaceous material. No visual evidence of sulfides.

PBR-28 San Gregorio Friable argillaceous material. 2 vol. % and 4 vol. % of finely disseminated pyrite and galena respectively.

PBR-29 San Gregorio Breccia. Clasts of dolostone (35 vol. %) in argillaceous matrix.

PBR-30 San Gregorio Breccia. Clasts of dolostone (20 vol. %) in argillaceous matrix.

PBR-31 San Gregorio Unmineralized finely laminated dolostone.

PBR-32 San Gregorio Unmineralized finely laminated dolostone.

PBR-33 San Gregorio Breccia. Excelsior phyllite and milky quartz clasts in arenaceous matrix (sedimentary breccia known as Brecha Basal).

PBR-34 San Gregorio Mitu redbed sandstone. 70 vol. % quartz, 20 vol. % lithic fragments, and 10 vol. % feldspar grains.

211
GENERAL APPENDIX
 General Appendix. (Cont.) Complete list of samples studied in this work. The table includes details such a macroscopic description and the type of analyse conducted. Part B: Sample Location.

212
Sample Deposit/area Macroscopic description Type of analyse

XRD XRF ICP NA MP REE CY TS PS S C O H Pb Sr Dat. F.I.

PBR-35 San Gregorio Strongly silicified and oxidized dolostone.

PBR-36 San Gregorio Strongly silicified and oxidized dolostone.

PBR-37 San Gregorio Strongly oxidized rock. Small amounts of carbonates (sid.?) are present.

PBR-38 San Gregorio Altered melanocratic greenish grey aphanitic volcanic rock. Probably andesitic to basaltic composition. 10 vol. % of diss. pyrite.

PBR-39 San Gregorio Melanocratic greenish grey aphanitic volcanic rock. Probably andesitic to basaltic composition. Slightly altered.

PBR-40 San Gregorio Melanocratic greenish grey aphanitic volcanic rock. Probably andesitic to basaltic composition.

PBR-41 San Gregorio Moderately oxidized (pyrolusite) dolostone.

PBR-42 San Gregorio Breccia. Excelsior phyllite and milky quartz clasts in arenaceous matrix (sedimentary breccia known as Brecha Basal).

PBR-43 San Gregorio Mitu redbed sandstone. 70 vol. % quartz, 20 vol. % lithic fragments and 10 vol. % feldspar grains.

PBR-44 San Gregorio Friable argillaceous material. 5 vol. % and 2 vol. % of finely disseminated galena and kaolinite respectively.

PBR-46 San Gregorio Friable argillaceous material. 1 vol. % and 10 vol. % of finely disseminated galena and kaolinite respectively.

PBR-47 San Gregorio Partly silicified, friable argillaceous rock. 3 vol. % of disseminated galena.

PBR-48 San Gregorio Friable argillaceous material. 2 vol. % and 20 vol. % of finely disseminated galena and kaolinite respectively.

PBR 50 Colquijirca Massive sulfide replacement in moderately silicified dolostone. py (15 vol. %), sl (10 vol. %), ga (8 vol. %), and kao (5 vol. %).

PBR-51 San Gregorio Breccia. Clasts of dolostone (30 vol. %) in argillaceous matrix. 8 vol. % and 2 vol. % of finely diss. kao and ga respectively.

PBR-52 San Gregorio Breccia. Clasts of dolostone (65 vol. %) in argillaceous matrix. Around 5 vol. % of oxides.

PBR-53 San Gregorio Friable argillaceous material. 5 vol. %, 2 vol. %, and 2 vol. % of disseminated pyrite, kaolinite and galena respectively

PBR-54 Smelter Massive sulfide replacement. 30 vol. % of pyrite, 35 vol. % of enargite and 25 vol. % of quartz. Minor tiny alunite grains.

PBR-55 Smelter Breccia. Dolostone clasts (40 vol. %) in calcareous matrix (40 vol. %) with some pyrite and sphalerite (5 vol. % of each one).

PBR-56 Smelter Massive sulfide replacement in. 30 vol. % of pyrite, 30 vol. % of enargite, 30 vol. % of quartz, and 10 vol. % of alunite.

PBR-57 Smelter Breccia. Dolostone clasts (30 vol. %) in calcareous matrix (60 vol. %). 5 vol. % of disseminated pyrite.

PBR-58 Smelter Argillaceous rock with relictic dolostone. 20 vol. % of pyrite replacement.

PBR-59 Colquijirca Strongly oxidized mineralized dolostone. Some relictic galena is present (2 vol. %).

PBR-60 Colquijirca Massive sulfide replacement in former dolostone. 5 vol. % ga, 5 vol. % py, 2 vol. % sl, 2 vol. % kao, and 10 vol. % sid.

PBR-61a Colquijirca Bitouminous mudstone. Galena (10 vol. %) and kaolinite (5 vol. %) in fractures and along stratification.

PBR 61b Colquijirca Massive sulfide replacement. 10 vol. % galena, 25 vol. % pyrite, 25 vol. % sphalerite, 5 vol. % falhore, 5 vol. % kaolinite.

PBR-62 Colquijirca Massive sulfide replacement in former dolostone.50 vol. % galena, 20 vol. % chalcopyrite, 15 vol. % kaolinite and 8 vol. % quartz.

PBR-63 Colquijirca Massive sulfide replacement in former dolostone. 60 vol. % galena, 25 vol. % pyrite and 10 vol. % kaolinite.

PBR-64 Smelter Highly mineralized and altered porphyrytic volcanic rock. Pyrite-rich vuggy quartz. 15 vol. % alunite and 10 vol. % pyrophyllite?.

PBR-65 Marcapunta Sur Strongly silicified and oxidized dolostone.

PBR-66 San Gregorio Moderately oxidized porous silicified dolostone.

PBR-67 San Gregorio Oxidized desagregated argillaceous (in part kaolinite) material.

PBR-68 San Gregorio Friable argillaceous material. 5 vol. % and 1 vol. % of disseminated kaolinite and galena respectively.

PBR-69 San Gregorio Friable argillaceous material. Disseminations of cubic euhedral galena grains.

PBR-70 San Gregorio Apparently unaltered grey fine cristaline limestone.

PBR-71 San Gregorio Apparently unaltered cream coarse cristaline limestone. High porosity and some clay content.

PBR-72 San Gregorio Fossiliferous and slightly bituminous limestone. Echinoideos (Radiolos de Cidarideos. Cidaris sp. , Alfredo Pardo, 1997).
GENERAL APPENDIX
 PBR-111 Colquijirca Galena-pyrite-barite massive replacement asociated to argillic alteration.

PBR-112 Colquijirca Massive dickite-kaolinite replacement in former dolostone. Minor disseminations of sphalerite and pyrite.

PBR-113 Colquijirca Massive galena-sphalerite-pyrite replacement in former dolostone. Moderate silicification.

PBR-114 Colquijirca Cherty rock with strong pyrite disseminations and alunite-kaolinite in fractures.

PBR-115 Colquijirca Galena, pyrite, sphalerite massive replacement in thin-bedded dolostone. Kaolinte in septarian filling.

PBR-116 Colquijirca Massive galena-pyrite-kaolinite assemblage replacing dolostone.

PBR-117 Colquijirca Silicified dolostone partly replaced by euhedral barite-enargite grains.

PBR-118 Colquijirca Galena-pyrite-barite massive replacement in former dolostone.

PBR-119 Colquijirca Massive argillic alteration minerals. Dickite-caolinita main constituents.

PBR-120 Colquijirca Dolostone with dissolution cavities and sphalerite-pyrite-barite in open space filling textures.

PBR-121 Colquijirca Pyrite-sphalerite-barite replacements along beddeing and as open space filling textures.

PBR-122 Colquijirca Cherty breccia with pyrite-galena-kaolinite replacing the matrix.

PBR-123 Colquijirca Fine-grained subhedral to euhedral pyrite-sphalerite-galena-chalcopyrite as disseminations in massive, kaolinite-rich rock.

PBR-124 Colquijirca Argilite with massive galena replacement. Remmnant of fossils?.

PBR-125 Colquijirca Cherty breccia with enargite-pyrite-quartz in geodes.

PBR-126 Marcapunta Este Dacite containing thin veins of pyrite-galena-sphalerite with selvages containing phyllic assemblages.

PBR-127 Smelter Recristalized dolostone with minor sphalerite-pyrite in cavities.

PBR-128 Smelter Oxidated fine-grained Miti Group sandstone. Flow? structures in Mitu red beds?.

PBR-129 Smelter Fine-grained pyrite disseminations. Minor pyrite replacement in former dolostone.

PBR-130 Smelter Breccia. Chert clasts with pyrite-kaolinite-alunite replacing the matrix. Minor sphalerite and zunyite.

PBR-131 Smelter Pyrite-enargite massive replacement in former dolostone. Coarse-grained alunite in open spaces.

PBR-132 Smelter Enargite massive replacement in former dolostone. According to mine analyse >5 g/t Au.

PBR-132b Smelter Strongly silicified dolostone. Some portions containing nearly euhedral grains.

PBR-133 Smelter Nearly euhedral grains of pyrite and enargite replacing silicfied dolostone.

PBR-134 Smelter Mineralized Mitu Group sandstone. Enargite-pyrite-kaolinite as thin veins. Minor sphalerite, galena and pyrite.

PBR-135 Smelter Enargite-pyrite massive replacement in former dolostone. Subordinated enargite-quartz in cockade textures.

PBR-136 Smelter Sphalerite-galena-pyrite replacement in dacitic volcanic rock (mainly replacing feldspars grains).

PBR-137 Smelter Silicified dolostone containing pink coarse-grained alunite in geodes.

PBR-138 Smelter Dolostone partly silicied with pyrite-enargite in tiny opaces.

PBR-139 Smelter Pyrite-enargite-quartz massive replacement in former dolostone.

PBR-140 Smelter Slightly mineralized dolostone. Tiny cavities containing well-formed enargite grains.

PBR-141 Smelter Slightly mineralized fine-grained sandstone?. Minor pyrite-enargite replacement. According to mine analyse >3 g/t Au.

PBR-142 Marcapunta Sur Sulfide rock(1) from former conglomeratic rock. Possible protore: Shuco conglomerate.

PBR-143 Smelter Vuggy silica. Vugs partially filled by enargite-pyrite-quartz assemblages.

PBR-143b Smelter Strongly silicified sandstone (Mitu Group). Enargite and minor amounts of pyrite as veins or as replacements along bedding.

PBR-144 Smelter Massive quartz-chalcopyrite-pyrite-enargite replacement in former dolostone (strong silicified).

PBR-145 Smelter Dacitic volcanic rock moderately chloritized.

PBR-146 Smelter Dolostone displaying enargite-pyrite-alunite replacement along bedding.

PBR-147 Smelter Nearly massive sphalerite-siderite-enargite-pyrite replacement in former dolostone. Minor kaolinite filling intergranular spaces.

PBR-148 Smelter Unaltered? biotite-rich dacitic volcanic rock.

PBR-149 Smelter Mitu Group sandstone showing slight reaction to HCl (minor amounts of calcite?).

213
GENERAL APPENDIX
 General Appendix. (Cont.) Complete list of samples studied in this work. The table includes details such a macroscopic description and the type of analyse conducted. Part B: Sample Location.

214
Sample Deposit/area Macroscopic description Type of analyse

XRD XRF ICP NA MP REE CY TS PS S C O H Pb Sr Dat. F.I.

PBR-150 Smelter Sphalerite-siderite-enargite massive replacement in former dolostone. Minor kaolinite filling intergranular spaces.

PBR-151 Colquijirca Chalcopyrite-supported breccia with minor barite and kaolinite. Clasts of strongly silicified limestones.

PBR-152 Smelter Breccia. Pyrite-enargite-kaolinite replacing the matrix.

PBR-153 San Gregorio Ag-rich sulfide rock(1).

PBR-155 San Gregorio Unaltered? Mitu Group sandstone.

PBR-157 San Gregorio Unmineralized? grey dolostone.

PBR-158 San Gregorio Strongly silicificated dolostone. Main assemblage: barite-pyrite-enargite.

PBR-159 San Gregorio Beige dolostone containing pyrite-galena disseminations assotiated to ankerite-dolomite?.

PBR-160 San Gregorio Strngly altered Mitu Group sandstone. Minor kaolinite and pyrite disseminations.

PBR-161 San Gregorio Nearly massive rodhochrosite replacement in former dolostone. Very fine-grained sphalerite disseminations in rodhochrosite.

PBR-162 San Gregorio Massive galena-sphalerite replacement in former dolostone.

PBR-163 San Gregorio Mineralized Basal Breccia. Kaolinite-sericite-pyrite? Replacing certain undefined clasts.

PBR-165 San Gregorio Crackle breccia dolostone in transtion to sulfide rock(1).

PBR-166 San Gregorio Sulfide rock(1).

PBR-167 San Gregorio Highly bituminous dolostone? asociated to some galena-sphalerite? disseminations.

PBR-169 San Gregorio Sulfide rock(1)

PBR-171 San Gregorio Mineralized Mitu Group sandstone.

PBR-172 San Gregorio Sulfide rock(1) from the basal dolostones.

PBR-173 San Gregorio Sulfide rock(1) . According to mine analyse minor amounts of Cu.

PBR-174 San Gregorio Sulfide rock(1) . According to mine analyse minor amounts of Cu.

PBR-175 San Gregorio Ag-rich Sulfide rock(1). Pyrite dissminations.

PBR-176 San Gregorio Dolostone displaying minor sericite? in fractures. Mine analyse show low Ag-Pb-Zn values.

PBR-177 San Gregorio Unmineralized? silicificated dolostone.

PBR-178 San Gregorio Breccia. Subangular centimetric dolostone clasts in dolomitic matrix.

PBR-179 San Gregorio Massive galena-sphalerite-barite replacement in former dolostone.

PBR-180 Colquijirca Mitu group argilite.

PBR-184 San Gregorio Strongly oxidized rock presumably containing Bi-bearing oxides. Protore: Pucara limestones.

PBR-185c San Gregorio Unaltered? biotite-rich dacitic volcanic rock.

PBR-186 San Gregorio Strongly oxidized rock presumably containing Bi-bearing oxides. Protore: Pucara limestones.

PBR-187 San Gregorio Strongly oxidized rock presumably containing Bi-bearing oxides. Protore: Pucara limestones.

PBR-188 Colquijirca Cherty rock. Alunite-pyrite in fractures.

PBR-189 Colquijirca Black cherty rock. Alunite-pyrite in fractures.

PBR-190 Colquijirca Cherty breccia. Tennantite-barite replacing the matrix.

PBR-191 Colquijirca Massive ore replacement in former dolostone. Minor tennantite is the only observed mineral.

PBR-192 Colquijirca Massive ore replacement. Dickite in speckled textures accompanied by minor pyrite and enargite disseminations.

PBR-193 Colquijirca Massive sphalerite-galena replacement ore. Unrecognized fine-grained green grains, possibly uranium minerals.

PBR-194 Smelter Dacitic lava-dome affected by advanced argillic alteration (quartz-alunite-bearing assemblages).

PBR-195 Smelter Dacitic lava-dome affected by advanced argillic alteration (aquartz-alunite-bearing assemblages).
GENERAL APPENDIX
 PBR-196 Smelter Dacite displaying moderate argillic alteration. Minor pyrite disseminations.

PBR-197 Marcapunta Vuggy silica. Small (<0.5 cm long) subhedral to euhedral quartz grains.

PBR-198 Oro Marcapunta Dacite displaying advanced argillic alteration. Quartz-alunite replacing mainly K feldspars.

PBR-199 Smelter Dacite with not discernable hydrothermal alteration.

PBR-200 Smelter Dacite slightly altered. Presence of smectite, according to PIMA II.

PBR-201 Smelter Dacite slightly altered. Presence of smectite, according to PIMA II.

PBR-202 Smelter Dacite affected by advanced argillic alteration. Quartz-alunite > 50 vol. % replacing mainly K feldspars.

PBR-203 Smelter Unoxidated vuggy silica. Minor pyrite disseminations.

PBR-204 Smelter Strongly kaolinized dacite.

PBR-205 Smelter Massive pyrite-enargite-alunite replacement in dacite.

PBR-206 Colquijirca Excelcior Group phyllite.

PBR-208 San Gregorio Sulfide rock(1) containing probably organic material.

PBR-209 San Gregorio Sample from oxidized sulfide rock(1) vein cutting silicified Pucar dolostones.

PBR-211 San Gregorio Sulfide rock(1).

PBR-213 Marcapunta Sur Dacite affected by advanced argillic alteration. Quartz-alunite replacing mainly K feldspars.

PBR-214 Oro Marcapunta Dacite affected by advanced argillic alteration. Quartz-alunite replacing mainly K feldspars.

PBR-215 Marcapunta Oeste Unaltered? dacite.

PBR-216 Huacchuacaja Unaltered dacite from dome.

PBR-216a Huacchuacaja Unaltered dacite from dome.

PBR-216b Huacchuacaja Unaltered dacite from dome.

PBR-217 Colquijirca Chert-alunite-enargite-pyrite semimassive replacement in former dolostone. Sulfides-alunite mainly in fractures.

PBR-218 Colquijirca Chert-alunite-enargite-pyrite semimassive replacement in former dolostone. Sulfides-alunite mainly in fractures.

PBR-219 San Gregorio Sulfide rock(1).

PBR-220 San Gregorio Sulfide rock(1).

PBR-221 San Gregorio Sulfide rock(1).

PBR-223 San Gregorio Silicified sulfide rock(1).

PBR-224 San Gregorio Oxidized sulfide rock in silified former Pucara limestone.

PBR-225 San Gregorio Massive galene-sphalerite replacement in former dolostone. Minor kaolinite and barite accompaning the sulfides.

PBR-226 San Gregorio Oxidized sulfide rock.

PBR-227 San Gregorio Sample from sulfide rock- oxidized sulfide rock interface.

PBR-228 San Gregorio Sample of oxidized sulfide rock? vein cutting Mitu Group red beds.

PBR-229 Marcapunta Sur Bismutinite/enargite?-pyrite replacement in former carbonate rock?. Several samples.

PBR-230 Colquijirca Chert y pyrita masiva, enargite and kaolinite in cavities

PBR-234 Smelter Massive enargite-pyrite ore accompanied with minor quartz.

PBR-238 Smelter Pyrite-enargite-alunite in geodes, replacing selective clasts in sedimentary breccia.

PBR-240 Colquijirca Strongly argillized ore. Pyrite-galene-sphalerite-chalcopyrite in botroidal aggregates and coarse disseminations.

PBR-241 Colquijirca Strongly argillized ore. Pyrite-galene-sphalerite-baritine in geode-like pockets.

PBR-244 Colquijirca Pyrite-supported breccia. Minor enargite-alunite-dickite? As accompaning minerals.

PBR-245 Smelter Massive enargite in radial aggregates. Subordinate pyrite associated to well-formed alunite.

PBR-246 Colquijirca Specular hematite associated to siderite. Kaolinite as open space filling.

PBR-247 Colquijirca Galena-sphalerite in a mass of dickite and as open space filling in chert. In this last case associated to quartz.

215
GENERAL APPENDIX
 General Appendix. (Cont.) Complete list of samples studied in this work. The table includes details such a macroscopic description and the type of analyse conducted. Part B: Sample Location.

216
Sample Deposit/area Macroscopic description Type of analyse

XRD XRF ICP NA MP REE CY TS PS S C O H Pb Sr Dat. F.I.

PBR-248 Colquijirca Galena-chalcopyrite-quartz in porous chert replacing former dolostone.

PBR-249 Colquijirca Massive pyrite-enargite replacement ore. Abundant dickite-kaolinite asscociated to the sulfides.

PBR-250 Smelter Kaolinite in open space filling textures. Sphalerite-galene-barite-hematite? in small geodes in silicified dolostones.

PBR-251 Smelter Monominerallic dickite sample from enargite-pyrite-bearing sample.

PBR-252 Colquijirca Siderite-ankerite-sphalerite massive replacement. Minor fluorite as well-formed grains.

PBR-253 Colquijirca Massive sphalerite-galene replacement. Alunite ad barite intimately intergrown with sulfides in vugs.

PBR-255 Smelter Sphalerite-galena-pyrite-hematite-kaolinite massive replacement in former dolostone.

PBR-256 Smelter Massive enargite-pyrite replacement in conglomeratic rock (Shuco member?). Minor alunite.

PBR-259 Smelter Massive chert-pyrite-enargite-alunite replacement in former dolostone.

PBR-260 Smelter Massive sphalerite-galena-siderite/ankerite replacement in former dolostone.

PBR-262 Smelter Enargite-pyrite-alunite as open space filling from semi-massive ore.

PBR-263 Smelter Massive enargite-pyrite-quartz-alunite-dickite replacement. Some chert clasts.

PBR-265 Smelter Massive enargite-pyrite-alunite-quartz replacement besides relictic chert.

PBR-266 Marcapunta Alunite replacing matrix in dacite.

PBR-267 Smelter Massive enargite-pyrite-chalcopyrite replacement. Minor alunite-kaolinite?.

PBR-269 Smelter Massive enargite-alunite replacement in former dolostone.

PBR-270 Smelter Massive pyrite-enargite-chalcopyrite?-sphalerite-galena? Replacement in former dolostone.

PBR-272 Smelter Strongly altered dacite. Alunite replacing groundmass.

PBR-273 Oro Marcapunta Oxidized breccia. Rounded vuggy silica clasts in a plumose alunite-supported matrix. Grain size of alunite >1 cm across.

PBR-277 Colquijirca Strongly silicified dolostone. Abundant siderite accompanied by minor galena and sphalerite.

PBR-281 San Gregorio Sulfide-rich silicified ore. Only fine-grained pyrite visible.

PBR-282 Colquijirca Massive sphalerite-galena-chalcopyrite replacement in former dolostone.

PBR-283 Colquijirca Quartz sample from bornite-rich zone.

PBR-284a San Gregorio Massive sphalerite, galena ore in a friable and microgranular texture (sulfide rock). Alunite as microgranular disseminations.

PBR-286 Colquijirca Massive sulfide replacement. Mainly pyrite and bornite and minor quartz.

PBR-288 Colquijirca Massive enargite-pyrite replacement associated to fine-grained alunite.

PBR-290 Colquijirca Massive enargite-pyrite replacement associated to fine grained alunite.

PBR-291 Colquijirca Sulfide-rich ore. Mainly pyrite and bornite associated to well cristallized quartz.

PBR-292 San Gregorio Oxidized sulfide rock from vein cutting strongly silicified Pucara limestone. Alunite-anatase rich? sample.

PBR-293 San Gregorio Oxidized sulfide rock.

PBR-294 San Gregorio Oxidized sulfide rock.

PBR-295 Marcapunta Enargite-pyrite thin veins cutting strongly silicified dolostone.

PBR-296 Marcapunta Enargite-pyrite thin veins cutting strongly silicified dolostone.

PBR-298 Colquijirca Massive sphalerite, pyrite, galena replacement. Centimetric geodes coated by alunite euhedral grains.

PBR-305 Oro Marcapunta Vuggy silica. Vugs partially filled by botroydal hematite and quartz.

PBR-310 Colquijirca Semi massive sulfide replacement. Chacopyrite-pyrite association accompanied by quartz.

PBR-311 Colquijirca Mineralized breccia. Strongly silicified angular clasts in a matrix dominated by kaolinite.

PBR-312 Colquijirca Mineralized breccia. Chert angular clasts in a chalcopyrite-rich matrix. Minor kaolinite filling cavities.
GENERAL APPENDIX
 PBR-313 Colquijirca Massive galena replacement. Siderite as spherical aggregates associated.

PBR-314 Smelter Massive enargite-luzonite-pyrite replacement.

PBR-321 Smelter Massive pyrite-enargite replacement in strongly silicified conglomerate (Shuco member?). Two pyrite generations.

PBR-322 Smelter Mineralized breccia. Matrix partially replaced by enargite and coarse-grained alunite.

PBR-324 Colquijirca Massive tennantite, chalcopyrite, pyrite replacement associated to argillic alteration (kaolinite?)

PBR-325 Colquijirca Massive tennantite and pyrite replacement associated to coarse grains of barite.

PBR-326 Colquijirca Massive pyrite and bornite replacement associated to argillic alteration (dickite?).

PBR-327 Smelter Massive enargite-pyrite replacement in former carbonate rock. Large acicular aggregates of enargite.

PBR-329 Smelter Nearly massive ore replacement. Coarse euhedral enargite. Alunite posdating enargite as coatings around pyrite.

PBR-332 Smelter Massive pyrite-enargite replacement in former dolostone. Two pyrite generations. Alunite as open space filling.

PBR-334 San Gregorio Moderately silicified dolostone. Apparently sulfide-rich ore. Some well cristallyzed barite.

PBR-335 Oro Marcapunta Strongly altered dacite. Alunite-quartz filling (replacing?) former mainly K-feldspars phenocrysts.

PBR-336 Oro Marcapunta Strongly altered dacite. Alunite-quartz filling (replacing?) former mainly K-feldspars phenocrysts.

PBR-337 Oro Marcapunta Strongly altered dacite. Advanced argillic alteration, mainly quartz-alunite assemblages accompanied by oxides.

PBR-338 Oro Marcapunta Strongly altered dacite. Advanced argillic alteration, mainly quartz-alunite assemblages replacing K feldspars.

PBR-339 Oro Marcapunta Strongly altered dacite. Advanced argillic alteration, mainly quartz-alunite assemblages accompanied by oxides.

PBR-340 Oro Marcapunta Strongly altered dacite. Advanced argillic alteration, mainly quartz-alunite assemblages accompanied by oxides.

PBR-350 Marcapunta oeste Sulfide-rich replacement. Enargite-supported breccia with silicified limestones clasts.

PBR-351 Marcapunta Oeste Massive pyrite-enargite replacement in carbonate rock. Well-formed enargite. Alunite filling cavities.

PBR-370 Marcapunta Oeste Dacitic dome altered to argillic alteration associations including kaolinite, sericite and pyrite.

PBR-371 Marcapunta Oeste Quartz-alunite-pyrite alteration in dacitic dome.

PBR-372 Marcapunta Oeste Quartz-alunite-pyrite alteration in dacitic dome.

PBR-373 Marcapunta Oeste Vuggy silica displaying pyrite and botroidal hematite coating vugs.

PBR-374 Marcapunta Oeste Vuggy silica containing pyrite and botroidal hematite as coatings in vugs.

PBR-375 Marcapunta Oeste Vuggy silica containing pyrite and botroidal goethite as coatings in vugs.

PBR-376 Marcapunta Oeste Vuggy silica containing pyrite and botroidal hematite as coatings in vugs.

PBR-391 Smelter Massive quartz-pyrite replacement in carbonate-rocks. Coarse grained quartz in geodes.

PBR-398 Colquijirca Massive siderite (and other unidentified carbonates) as botroidal aggregates in open spaces.

PBR-399a Colquijirca Massive sphalerite-galena replacement. Subordinate hematite and siderite plus minor kaolinite.

PBR-399b Smelter Strongly silicified rock limestone with pyrite and quartz mainly as disseminations and veinlets. Opaline silica accompanyies quartz.

PBR-400 Colquijirca Native silver overgrowing euhedral to subhedral galena-sphalerite aggregates.

PBR-409 Oro Marcapunta Dacite altered to advanced argillic alteration and cut by veinlets containing pyrite, quartz, and chalcosite?.

PBR-422 Marcapunta Sur Dacite displaying a weak propilytic alteration and, locally, sericitic alteration.

PBR-423 Oro Marcapunta Bonanza-type ore. Ag-Au-Pb-rich rock showing oxide minerals and alunite.

(1) sulfide rock: Usually sulfide-rich friable material. It consis of microgranular associations of APS minerals, kaolinite, sphalerite, galena, quartz, and minor amounts of pyrite, marcasite among other rarer minerals.

217
GENERAL APPENDIX
 GENERAL APPENDIX

General Appendix PART B: Sample location. General Appendix cont. PART B: Sample location.
Location UTM Coordinates Location UTM Coordinates
Sample Sample
Hole Depth Area E N Hole Depth Area E N
PBR-1 22G 114.7 San Gregorio 360499 8804553 PBR-59 TN7-724 119.5 Colquijirca 361785 8811066
PBR-2 22G 130.3 San Gregorio 360499 8804553 PBR-60 TN2-728 159.5 Colquijirca 361221 8811115
PBR-3 22G 134.3 San Gregorio 360499 8804553 PBR-61a Open pit Colquijirca N.A.
PBR-4 22G 139.3 San Gregorio 360499 8804553 PBR-61b Open pit Colquijirca N.A.
PBR-5 22G 146.0 San Gregorio 360499 8804553 PBR-62 Open pit Colquijirca N.A.
PBR-6 22G 151.3 San Gregorio 360499 8804553 PBR-63 TN3-776 92.9 Colquijirca 361199 8811712
PBR-7 22G 173.0 San Gregorio 360499 8804553 PBR-64 CM2-548 243.8 Smelter 360689 8808863
PBR-8 22G 177.1 San Gregorio 360499 8804553 PBR-65 Principal pit Marcapunta Sur N.A.
PBR-9 22G 178.2 San Gregorio 360499 8804553 PBR-66 Principal pit San Gregorio N.A.
PBR-10 22G 183.6 San Gregorio 360499 8804553 PBR-67 Principal pit San Gregorio N.A.
PBR-11 22G 186.3 San Gregorio 360499 8804553 PBR-68 29G 165.0 San Gregorio 360404 8805147
PBR-12 22G 192.0 San Gregorio 360499 8804553 PBR-69 21G 390.0 San Gregorio 360419 8804425
PBR-13 22G 203.5 San Gregorio 360499 8804553 PBR- 70 GN2-292 150.1 San Gregorio 359900 8805700
PBR-14 22G 218.3 San Gregorio 360499 8804553 PBR- 71 GN2-260 113.1 San Gregorio 359900 8805300
PBR-15 22G 236.2 San Gregorio 360499 8804553 PBR- 72 GN2-260 140.3 San Gregorio 359900 8805300
PBR-16 22G 251.2 San Gregorio 360499 8804553 PBR- 73 GN2-260 186.8 San Gregorio 359900 8805300
PBR-17 22G 264.1 San Gregorio 360499 8804553 PBR- 74 20G-95 269.8 San Gregorio 360057 8804820
PBR-18 22G 290.4 San Gregorio 360499 8804553 PBR- 75 19G-94 227.8 San Gregorio 360137 8804951
PBR-19 22G 301.7 San Gregorio 360499 8804553 PBR- 75a 19G-94 227.8 San Gregorio 360137 8804951
PBR-20 22G 302.3 San Gregorio 360499 8804553 PBR- 76 18G-95 195.9 San Gregorio 360206 8805085
PBR-21 22G 310.9 San Gregorio 360499 8804553 PBR- 77 13G-95 315.7 San Gregorio 360166 8804756
PBR-22 22G 324.7 San Gregorio 360499 8804553 PBR- 78 13G-95 320.9 San Gregorio 360166 8804756
PBR-23 22G 341.2 San Gregorio 360499 8804553 PBR- 79 41G-95 399.0 San Gregorio 360530 8804358
PBR-24 22G 348.6 San Gregorio 360499 8804553 PBR- 80 20G-95 247.2 San Gregorio 360057 8804820
PBR-25 22G 372.4 San Gregorio 360499 8804553 PBR- 80a 20G-95 247.2 San Gregorio 360057 8804820
PBR-26 22G 376.2 San Gregorio 360499 8804553 PBR- 81 13G-95 265.9 San Gregorio 360166 8804756
PBR-27 22G 383.4 San Gregorio 360499 8804553 PBR- 82 41G-95 323.9 San Gregorio 360530 8804358
PBR-28 22G 386.8 San Gregorio 360499 8804553 PBR- 83 41G-95 343.2 San Gregorio 360530 8804358
PBR-29 22G 402.4 San Gregorio 360499 8804553 PBR- 84 41G-95 426.0 San Gregorio 360530 8804358
PBR-30 22G 406.5 San Gregorio 360499 8804553 PBR- 85 41G-95 444.6 San Gregorio 360530 8804358
PBR-31 22G 425.3 San Gregorio 360499 8804553 PBR- 85a 41G-95 444.6 San Gregorio 360530 8804358
PBR-32 22G 436.4 San Gregorio 360499 8804553 PBR- 86 41G-95 468.9 San Gregorio 360530 8804358
PBR-33 22G 439.7 San Gregorio 360499 8804553 PBR- 87 41G-95 156.6 San Gregorio 360530 8804358
PBR-34 22G 442.4 San Gregorio 360499 8804553 PBR- 88 GN2-260 210.8 San Gregorio 359900 8805300
PBR-35 34F 27.4 San Gregorio 360552 8805104 PBR- 88a GN2-260 210.8 San Gregorio 359900 8805300
PBR-36 34F 63.9 San Gregorio 360552 8805104 PBR- 89 GN2-260 243.0 San Gregorio 359900 8805300
PBR-37 34F 136.4 San Gregorio 360552 8805104 PBR- 90 outcrop cerro Lachipana N.A.
PBR-38 34F 139.5 San Gregorio 360552 8805104 PBR- 91 outcrop cerro Lachipana N.A.
PBR-39 34F 147.6 San Gregorio 360552 8805104 PBR- 92 outcrop cerro Lachipana N.A.
PBR-40 34F 164.7 San Gregorio 360552 8805104 PBR- 93 outcrop cerro Lachipana N.A.
PBR-41 34F 189.9 San Gregorio 360552 8805104 PBR- 94 Mercedes Norte Pit Colquijirca N.A.
PBR-42 34F 211.1 San Gregorio 360552 8805104 PBR- 95 Mercedes Norte Pit Colquijirca N.A.
PBR-43 34F 218.8 San Gregorio 360552 8805104 PBR- 96 Mercedes Norte Pit Colquijirca N.A.
PBR-44 41G 271.7 San Gregorio 360530 8804358 PBR- 97 Mercedes Norte Pit Colquijirca N.A.
PBR-46 15G 254.0 San Gregorio 360280 8804687 PBR- 98 Mercedes Norte Pit Colquijirca N.A.
PBR-47 20G 295.6 San Gregorio 360057 8804820 PBR- 99 Mercedes Norte Pit Colquijirca N.A.
PBR-48 14G 161.1 San Gregorio 360437 8804942 PBR-100 underground adit Smelter N.A.
PBR- 50 S.D. # 3 39.7 Colquijirca 360967 8811762 PBR-101 SP2-98 195.5 Colquijirca sur 361218 8810162
PBR-51 2J 107.8 San Gregorio N.A. PBR-101b SP2-98 209.0 Colquijirca sur 361218 8810162
PBR-52 GN2-260 198.3 San Gregorio 359900 8805300 PBR-102 Principal pit Colquijirca N.A.
PBR-53 2M 119.5 San Gregorio N.A. PBR-103 SP2-130 187.5 Colquijirca sur 361251 8810563
PBR-54 BR.-524 548.5 Marcapunta 361090 8808563 PBR-104 CME2-468 152.8 Marcapunta este N.A.
PBR-55 CM8-580 201.9 Smelter 361588 8809263 PBR-105 CM13-564 260.5 Smelter este 361987 8809065
PBR-56 CM5-580 101.5 Smelter 361190 8809262 PBR-106 DDH7 236.4 Marcapunta sur N.A.
PBR-57 CM1-580 159.6 Smelter 360690 8809262 PBR-107 SP2-146 183.5 Colquijirca sur 361271 8810762
PBR-58 SM2-644 199.5 Smelter 361172 8810074 PBR-108 Principal pit Colquijirca 360915 8811135

218
 GENERAL APPENDIX

PBR-109 Principal pit Colquijirca N.A. PBR-167 39G 278.3 San Gregorio 360358 8804815

PBR-110 Principal pit Colquijirca N.A. PBR-169 39G 292.0 San Gregorio 360358 8804815

PBR-111 Principal pit Colquijirca N.A. PBR-171 39G 309.4 San Gregorio 360358 8804815

PBR-112 Principal pit Colquijirca N.A. PBR-172 39G 304.7 San Gregorio 360358 8804815

PBR-113 Principal pit Colquijirca N.A. PBR-173 GN4-276 74.8 San Gregorio 360500 8805500

PBR-114 Principal pit Colquijirca N.A. PBR-174 GN5-292 95.5 San Gregorio 360320 8805700

PBR-115 Principal pit Colquijirca N.A. PBR-175 GN5-292 93.5 San Gregorio 360320 8805700

PBR-116 Principal pit Colquijirca N.A. PBR-176 9G 404.5 San Gregorio 360466 8804749

PBR-117 Principal pit Colquijirca N.A. PBR-177 9G 112.9 San Gregorio 360466 8804749

PBR-118 Principal pit Colquijirca N.A. PBR-178 GN1-396 230.4 San Gregorio 358629 8806961

PBR-119 Principal pit Colquijirca N.A. PBR-179 14G 181.2 San Gregorio 360437 8804942

PBR-120 Principal pit Colquijirca N.A. PBR-180 outcrop Colquijirca N.A.

PBR-121 Principal pit Colquijirca N.A. PBR-184 outcrop San Gregorio N.A.

PBR-122 Principal pit Colquijirca N.A. PBR-185C outcrop San Gregorio N.A.

PBR-123 Principal pit Colquijirca N.A. PBR-186 outcrop San Gregorio N.A.

PBR-124 Principal pit Colquijirca N.A. PBR-187 outcrop San Gregorio N.A.

PBR-125 Principal pit Colquijirca N.A. PBR-188 Principal pit Colquijirca N.A.

PBR-126 CME2-468 276.9 Marcapunta Este N.A. PBR-189 Principal pit Colquijirca N.A.

PBR-128 CM5-580 265.0 Smelter 361190 8809262 PBR-190 Principal pit Colquijirca N.A.

PBR-129 CM5-596 148.8 Smelter 361189 8809262 PBR-191 Principal pit Colquijirca N.A.

PBR-130 CM5-580 189.2 Smelter 361190 8809262 PBR-192 Principal pit Colquijirca N.A.

PBR-131 CM9-548 247.3 Smelter 361184 8808858 PBR-193 Principal pit Colquijirca N.A.

PBR-132 CM6-580 104.2 Smelter 361391 8809263 PBR-194 CM10-548 201.8 Smelter 361290 8808863

PBR-132b CM6-580 116.4 Smelter 361391 8809263 PBR-195 CME2-468 329.4 Smelter N.A.

PBR-133 underground adit Smelter N.A. PBR-196 CM8-548 168.8 Smelter 361615 8808862

PBR-134 CM7-564 241.5 Smelter 361191 8809062 PBR-197 SD-11 144.0 Oro Marcapunta 361128 8808206

PBR-135 CM9-548 259.0 Smelter 361184 8808858 PBR-198 outcrop Oro Marcapunta 360850 8808526

PBR-136 CME2-468 355.4 Smelter N.A. PBR-199 CM6-548 230.4 Cobre Marcapunta 361389 8808860

PBR-137 CM5-580 110.4 Smelter 361190 8809262 PBR-200 CM9-548 66.2 Cobre Marcapunta 361184 8808858

PBR-138 CM5-596 53.3 Smelter 361189 8809262 PBR-201 CM9-548 196.0 Cobre Marcapunta 361184 8808858

PBR-139 CM5-596 140.4 Smelter 361189 8809262 PBR-202 CM10-548 214.8 Cobre Marcapunta 361290 8808863

PBR-140 CM10-564 316.3 Smelter 361590 8809064 PBR-203 CM10-548 191.3 Cobre Marcapunta 361290 8808863

PBR-141 CM4-564 351.6 Smelter 360890 8809063 PBR-204 CM2-468 80.0 Cobre Marcapunta 360440 8807863

PBR-142 DDH7 276.2 Marcapunta Sur N.A. PBR-205 CM8-564 126.7 Cobre Marcapunta 361291 8809063

PBR-143 Brocal-524 552.9 Smelter 361090 8808563 PBR-206 outcrop Colquijirca N.A.

PBR-143b Brocal-524 733.0 Smelter 361090 8808563 PBR-208 15G 186.0 San Gregorio 360280 8804687

PBR-144 underground adit Smelter N.A. PBR-209 outcrop San Gregorio 360626 8805463

PBR-145 CM5-580 285.5 Smelter 361190 8809262 PBR-211 15G 181.1 San Gregorio 360280 8804687

PBR-146 underground adit Smelter N.A. PBR-213 outcrop Marcapunta Sur 359949 8806020

PBR-147 CM7-564 266.0 Smelter 361191 8809062 PBR-214 outcrop Marcapunta 360811 8808287

PBR-148 CM13-564 39.0 Smelter 361987 8809065 PBR-215 outcrop Marcapunta Oeste 360020 8809986

PBR-148b underground adit Smelter N.A. PBR-216 outcrop Huacchuacaja 358353 8809626

PBR-149 CM10-564 Smelter 361590 8809064 PBR-216A outcrop Huacchuacaja N.A.

PBR-150 CM5-580 262.5 Smelter 361190 8809262 PBR-216B outcrop Huacchuacaja N.A.

PBR-151 CM11-572 211.9 Smelter 361884 8809178 PBR-217 Principal pit Colquijirca N.A.

PBR-152 MB-6 103.7 Smelter 361241 8809899 PBR-218 Principal pit Colquijirca 360892 8811122

PBR-153 14G 92.5 San Gregorio 360437 8804942 PBR-219 14G 294.0 San Gregorio 360437 8804942

PBR-155 GN1-343 293.4 San Gregorio 359439 8806311 PBR-220 39G 266.3 San Gregorio 360358 8804815

PBR-157 39G 186.5 San Gregorio 360358 8804815 PBR-221 39G 173.2 San Gregorio 360358 8804815

PBR-158 23G 275.2 San Gregorio 360576 8804680 PBR-223 39G 188.0 San Gregorio 360358 8804815
PBR-159 20G 205.8 San Gregorio 360057 8804820 PBR-224 39G 124.5 San Gregorio 360358 8804815
PBR-160 15G 314.5 San Gregorio 360280 8804687 PBR-225 39G 163.4 San Gregorio 360358 8804815
PBR-161 14G 146.5 San Gregorio 360437 8804942 PBR-226 39G 117.2 San Gregorio 360358 8804815
PBR-162 14G 161.0 San Gregorio 360437 8804942 PBR-227 39G 136.0 San Gregorio 360358 8804815
PBR-163 39G 308.6 San Gregorio 360358 8804815 PBR-228 outcrop Bohorquez N.A.
PBR-165 20G 211.2 San Gregorio 360057 8804820 PBR-229 outcrop Marcapunta Este N.A.
PBR-166 39G 269.0 San Gregorio 360358 8804815

219
 GENERAL APPENDIX

General Appendix (cont.) PART B: Sample location. General Appendix (cont.) PART B: Sample location.
Location UTM Coordinates Location
Sample Sample
Hole Depth Area E N Area

PBR-230 Principal pit Colquijirca N.A. PBR-338 outcrop Oro Marcapunta 360818 8808464

PBR-234 CM7-572 196.5 Smelter 361291 8809164 PBR-339 outcrop Oro Marcapunta N.A.

PBR-238 CM6-572 170.2 Smelter 361190 8809162 PBR-340 outcrop Oro Marcapunta N.A.

PBR-240 Principal pit Colquijirca N.A. PBR-350 CM1-432 221.3 Marcapunta Oeste 360525 8807410
PBR-241 Principal pit Colquijirca N.A. PBR-351 outcrop Marcapunta Oeste N.A.
PBR-244 Principal pit Colquijirca 360973 8811061 PBR-370 CM1-428 107.1 Marcapunta Oeste 360590 8807363
PBR-245 underground adit Smelter N.A. PBR-371 CM1-504 13.3 Marcapunta Oeste 360466 8808297
PBR-246 Choccayoc pit Colquijirca N.A. PBR-372 CM1-432 189.1 Marcapunta Oeste 360525 8807410
PBR-247 Choccayoc pit Colquijirca N.A. PBR-373 CM1-504 309.4 Marcapunta Oeste 360466 8808297
PBR-248 Principal pit Colquijirca N.A. PBR-374 CM1-504 289.0 Marcapunta Oeste 360466 8808297
PBR-249 Principal pit Colquijirca N.A. PBR-375 CM1-504 297.6 Marcapunta oeste 360466 8808297
PBR-250 Principal pit Colquijirca N.A. PBR-376 CM1-504 309.3 Marcapunta oeste 360466 8808297
PBR-251 Choccayoc pit Colquijirca N.A. PBR-391 outcrop Smelter N.A.
PBR-252 Choccayoc pit Colquijirca N.A. PBR-398 outcrop Colquijirca N.A.
PBR-253 Principal pit Colquijirca N.A. PBR-399a outcrop Colquijirca N.A.
PBR-255 CM8-580 205.7 Smelter 361588 8809263 PBR-399b outcrop Smelter N.A.
PBR-256 CM5-580 177.5 Smelter 361190 8809262 PBR-400 outcrop Colquijirca N.A.
PBR-259 SM1-676 81.3 Smelter 360920 8810463 PBR-409 CM1-432 175.0 Marcapunta 360525 8807410
PBR-260 MB-13 218.4 Smelter 360857 8809302 PBR-422 DDH-7 108.8 Marcapunta Sur N.A.
PBR-262 MB-7 287.5 Smelter 361200 8808950 PBR-423 CM1-436 231.6 Marcapunta 360605 8807469
PBR-263 CM4-588 160.2 Smelter 361190 8809362 N.A. Not available. Aproximate coordinates (20 m) may be requested to the author.
PBR-265 CM7-565 112.9 Smelter N.A.

PBR-266 CM6-572 97.1 Smelter 361190 8809162

PBR-267 SM2-676 137.5 Smelter 361030 8810458

PBR-269 CM6-572 119.8 Smelter 361190 8809162

PBR-270 SM1-676 104.7 Smelter 360920 8810463

PBR-272 CM7-564 109.5 Smelter 361191 8809062

PBR-273 outcrop Marcapunta 360867 8807711

PBR-277 SD-66 200.6 Colquijirca 361490 8811800

PBR-281 37G 194.7 San Gregorio N.A.

PBR-282 Mercedes Pit Colquijirca N.A.

PBR-283 Principal pit Colquijirca N.A.

PBR-284a 39G 78.0 San Gregorio 360484 8805044

PBR-290 Principal pit Colquijirca N.A.

PBR-291 Principal pit Colquijirca N.A.

PBR-292 San Gregorio San Gregorio N.A.

PBR-295 Brocal-524 742.0 Marcapunta N.A.

PBR-296 Brocal-524 742.5 Marcapunta N.A.

PBR-298 Principal pit Colquijirca 360947 8811058

PBR-305 outcrop Oro Marcapunta N.A.

PBR-310 Mercedes pit Colquijirca N.A.

PBR-311 Mercedes Norte Pit Colquijirca N.A.

PBR-312 Mercedes Norte Pit Colquijirca N.A.

PBR-313 Mercedes Norte Pit Colquijirca N.A.

PBR-314 underground adit Smelter N.A.

PBR-321 underground adit Smelter N.A.

PBR-322 DDH-37G 148.0 San Gregorio 361189 8809162

PBR-324 Principal pit Colquijirca N.A.

PBR-325 Principal pit Colquijirca N.A.

PBR-326 Principal pit Colquijirca N.A.

PBR-327 underground adit Smelter N.A.

PBR-329 underground adit Smelter N.A.

PBR-332 underground adit Smelter N.A.

PBR-334 39G 264.5 San Gregorio 360358 8804815

PBR-335 outcrop Oro Marcapunta 361117 8808229

PBR-336 outcrop Oro Marcapunta 361116 8808395

220
Remerciements
Agradecimientos

Este trabajo no habra sido posible sin el apoyo contnuo de muchas personas y organismos. Agradezco
primero y de la manera ms grande al profesor Lluis Fontbot por haberme dado la oportunidad de estudiar
Colquijirca. Llus, gracias por todo tu tiempo y paciencia, sobretodo cuando te toc revisar este trabajo. Parte
de este primer gran agradecimiento es tambin para la propietaria de Colquijirca, Sociedad Minera El Brocal
S.A.A., sin su apoyo, el desarrollo de este estudio se habra dificultado. Del mismo modo, mi profunda grati-
tud para la Confederacin Suiza para estudiantes extranjeros y para el Fonds National Suisse de la Recherche
Scientifique, proyecto 20020108026, sin cuyo apoyo este trabajo no habra salido adelante.
Estoy tambin muy agradecido, y por las razones que menciono en cada caso, a las siguientes perso-
nas:
A la profesora Silvia Rosas por haberme confiado su recomendacin e iniciado el contacto con la Uni-
versidad de Ginebra.
Al ingeniero Juan Proao por promover a que Sociedad Minera El Brocal S.A.A. apoye, y de la mejor
manera, este estudio.
Al ingeniero Ysaac Cruz por continuar con ese apoyo.
A los gelogos de El Brocal, particularmente a mi gran amigo Carlos Yacila por su ayuda incondicio-
nal.
A Torsten Vennemann por los anlisis y discusiones de istopos de H y O, a Robert Moritz y Jean Val-
lance por sus lecciones y discusiones sobre inclusiones fluidas, a Michel Cosca, Richard Spikings y Laurence
Page por las dataciones 40Ar/39Ar, a Zoltan Pecskay por las dataciones K/Ar de roca total, a George Morris
por los primeros anlisis via microsonda electrnica, a Bernhard Dold por los primeros anlisis a XRD, a Pia
Voldet por los primeros anlisis por REE, a Favio Capponi por los anlisis a XRF, a Yves Heaberlin por los
anlisis de istopos de S, a Jean-Marie por la preparacin de secciones pulidas-delgadas. Un agradecimiento
muy especial a Jacqueline Berthoud por su ayuda sin fin en el dia a dia.
Este trabajo fue sin duda mejorado con las revisiones de Richard Sillitoe y Kurt Friehauf. Mil gracias
por sus comentarios y discusiones. Ac aprovecho tambin para agradecer a Christoph Heinrich por sus ex-
plicaciones y discusiones.
Gracias tambin a mis amigos y compaeros; todo fue mas sencillo con ustedes: Katy, Katia, Anne,
Carolina (G. y R.), Agnes, Laure, Sabrine, Maria Fernanda, Karin, Melisse, Maria, Susanne, Carol, Isabelle
(G. y Ch.), Stephanie, Florice, Elizabeth, Monique, Laurie, Helene, Mareel, Isaline, Marc (P. y L.), Yves (J. y
H.), Massimo, Urs, Kalin, Fabien, Vincent, Charles, David, Stephane, Sebastian, Daniel (S. y A. ), Antoine,
Fernando, Cedric, Jean Lluis, Jean, Philippe, Laurent, Juan, Dave, Alex, Diego, Marco, Carlos, Cheik, Gotcha,
Mapate, Fred
Por supuesto, quiero tambin agradecer a mi familia por su cario y apoyo durante los aos que me toco
alejarme de ella. Igualmente a mi otra familia, Rita, Peter, Maya, Sabine, Steven, con ustedes siempre me sent
en casa. Finalmente, mi ms profundo agradecimiento a mi compaera de toda la vida Regina. Regina sin ti
todo habra sido mas difcil. Gracias por haber organizado tantas cosas, por tus traducciones, por ordenarme
un poco, incluso te debo la edicin de esta tesis. Por todo ello, pero sobretodo por ser la persona ms impor-
tante en mi vida, quiero dedicarte esta tesis.

221
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