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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
Dj paru /already published :
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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
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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

Abstract

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


ABSTRACT

disseminated high sulfidation epithermal system and 18O from-3 to -6 ) indicative of meteoric
(Oro Marcapunta) gave furnace and laser derived input. The elongated field fits with the meteoric
40
Ar/39Ar plateau ages in the range of 11.90.07 to water-magmatic water mixing trend defined at the
11.100.06 Ma at 2. This is a particularly long contemporaneous Julcani system, located 300 km to
lifespan and it is interpreted in terms of several the south. The magmatic end-member was most likely
shorter episodes of mineralization sustained by a magmatic vapor plume, from which SO2 interacted
multiple intrusive and/or thermal episodes related with water and condensed to form H2SO4, the main
to a large magma reservoir. The existence of several acid agent in the formation of the vuggy silica and
episodes of mineralization finds support by linking quartz-alunite alteration. S isotope compositions of
individually the 40Ar/39Ar ages with observed alunite (34S from 21.5 to 22.4 ) support this
crosscutting relationships between dated alunite and origin in which sulfate has equilibrated with H2S
periods of gold deposition defined by the sulfide- formed through disproportionation of SO2 within
and oxide-bearing veinlets. At least two recurrent a condensing vapor plume. Limited fluid inclusion
episodes of acid alteration-gold deposition took data from the productive Au-(Ag) stage define a
place during the activity of the Au-(Ag) epithermal mixing trend that broadly fits with that of the early
system. Seven laser and furnace derived 40Ar/39Ar acid barren stage suggesting similar end-member
ages obtained on alunite that predate, are coeval, and fluids. The available data cover a temperature range
post-date different generations of enargite-bearing between 190C to 260C and salinities from ~1 to ~5
and sphalerite-bearing assemblages, indicating that NaCl wt % equivalent. A number of fluid inclusions
the sulfide-rich Cordilleran Smelter and Colquijirca hosted in quartz from veinlets located 90 m below
deposits were formed several hundred thousand years the summit of Marcapunta record boiling. The
later than the Au-(Ag) disseminated mineralization at microthermometric results indicate that the boiling
Oro Marcapunta which lasted from 11.9 to 11.1 Ma. curve adjusts for a 200-300 m depth equivalent,
The obtained values (plateau ages) from Cordilleran indicating that erosion of the system was minor.
ores in Smelter and Colquijirca define a relatively Most of the fluid inclusion and stable isotope
narrow period of hydrothermal activity between data on the polymetallic Cordilleran deposits were
10.830.06 and 10.560.08 Ma (2). Additionally, obtained on the productive stage. Fluid inclusions
three K/Ar ages were obtained from the Cordilleran gave homogenization temperatures from 165.9C to
San Gregorio deposit by means of conventional 298.2C and salinities between ~0 and ~7 NaCl wt %
whole rock analysis. Two ages resulted similar at equivalent. Significant variations of Th are correlated
13.1-13.22.2 Ma (2) and the third at 13.94.0 Ma with the distance to the Marcapunta volcanic
(2). Ruled out an excess of inherited argon caused complex. In the inner enargite zones, homogenization
by detrital mica in the alunite-rich concentrates and temperatures reached 300C whereas in more distal
supported by the concordance of two of the ages parts (i.e., at Colquijirca) temperatures declined to
at 13.1-13.22.2 Ma, it is not excluded that the San as low as ~170C. In contrast to temperature, no
Gregorio deposit formed earlier than the other systematic variation in salinities from Smelter to
Cordilleran ores of the district. Alternatively, given Colquijirca is distinguished. The gradual temperature
the large errors on the K-Ar ages, the San Gregorio decrease from Smelter to Colquijirca is in agreement
deposit could also form coetaneously with Smelter with drilling correlation indicating that these deposits
and Colquijirca. are part of a single and continuous mineralized
Fluid inclusions from the Au-(Ag) disseminated corridor which was formed from a single process
mineralization at Oro Marcapunta show that vuggy of mineralization during the productive stage.
silica and quartz-alunite alteration entrained fluids In the Smelter-Colquijirca corridor, the strong
that reached temperatures in the range of 210C and zonal pattern, including the notable decrease in
280C. These fluids were of low salinity with typical the sulfidation states of sulfides assemblages from
values ranging from ~0 to ~4 NaCl wt % equivalent. high (enargite-pyrite) to intermediate (chalcopyrite-
These data examined on the basis of mineralogical pyrite) seems to respond to mainly a temperature
and zonal patterns suggest that the early barren decrease. Such temperature decrease could probably
stage fluids derived from a mixing process which be reinforced by local mixing with meteoric fluids
involved variable amounts of two end member particularly in the external sphalerite-galena zones.
cold fluids (210C-240C) of nearly zero salinities Two relatively contrasting Th vs. salinity trends may
with hot slightly saline fluids (250C-280C and 3 be discriminated from the available fluid inclusion
%-4 NaCl wt % equivalent). Stable isotope data are data of the productive stage. A first trend defined
in agreement with this conclusion. The calculated by quartz-hosted inclusions from alunite-bearing
isotope compositions of water (D and 18OSO4) in assemblages comprises salinity values between ~0
equilibrium with alunite define an elongated field and ~4 NaCl wt % equivalent and homogenization
whose extreme values are on the one side (with D and temperatures in the range of 221C and 273C.
18O values from -45 to -55 and from 7 -7.5 This trend is nearly identical to that delineated
) typical of magmatic signatures, respectively and by the early barren acid stage during the Au-(Ag)
on the other (with D from around -75 to -90 disseminated mineralization at Oro Marcapunta. The


ABSTRACT

mineralogical observations combined with stable the main degassing cupola(s) of the magma chamber
isotope data allow the interpretation that this trend (suggested by the shallow nature of porphyry Cu
reflects mixing between a magmatic end-member, mineralization related to other Cordilleran deposits
likely a SO2-bearing vapor plume, with meteoric of Per), the single-phase vapor fluids during their
water. The estimated 18O and D compositions ascent could prevent vapor contraction permitting
of water in equilibrium with Main ore stage alunite breaching of the two phase field below 450C. The
range from values around-41 D and 7 18O resulting two fluids, independently of the mechanism
to progressively isotopically lighter fluids down to of phase separation (i.e., boiling or condensation),
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 generation of the acid alteration-gold deposition
unexchanged meteoric fluids. These values fit with recurrent pulses recognized during the Au-(Ag)
the mixing line deduced for the acidic fluids that high sulfidation epithermal mineralization at Oro
generated the vuggy silica and quartz-alunite zones Marcapunta. The low Ag/Au ratios (10 to 40) from
at Oro Marcapunta. By projecting the regression the Au-(Ag) disseminated bodies similar to values
mixing line representing the entire population of obtained from quantitative microanalysis of single-
alunite D and 18O values of the Colquijirca district phase vapor fluid inclusions in other porphyry-related
it is possible to estimate a composition of around - systems are in agreement with this view.
14010 D and -181 18O for the 10.6-11.9 While the vapor phase ascended, the brine
Ma Colquijirca meteoric water. These values are similar (hypersaline fluid) probably remained largely within
to meteoric water composition estimated for other the brittle-ductile transition and then gradually
Miocene systems of central Per. Entrainment of a liberated as this transition retracted downward with
SO2 magmatic plume in the formation of the alunite time. It is in these instances, perhaps up to tens of
fluids, is also suggested by the 34S values for alunite thousands of years later, when meteoric waters that
(21.1 to 26.4 ) from the Main ore stage quartz- had exchanged isotopically with mainly sedimentary
alunite assemblages which are typical of hydrothermal rocks of the Excelsior and Mitu Groups through
magmatic fluids in which sulfate has equilibrated convection, could mix with the brines. At Colquijirca,
with H2S formed through disproportionation of SO2 modeling based on the isotopic composition of
within a condensing vapor plume. ore-related kaolinite and dickite predicts that these
The second Th vs salinity trend defined exchanged waters could acquire the obtained
by fluid inclusions representing enargite-bearing isotopic compositions at moderate to high total mass
assemblages, largely devoid of alunite, covers a larger water/rock ratios (between 0.3 and 1). On the other
salinity interval between 0.35 and as high as 7.2 NaCl hand, stable isotope evidences (D, O, S) pointing to
wt % equivalent and temperatures from 218C to extensive mixing between magmatic and exchanged
286C. These data combined with stable isotope data meteoric water have the implication that the 2 to 7
suggest mixing of magmatic fluids with exchanged NaCl wt % equivalent salinities of the Cordilleran
meteoric waters. The entrainment of exchanged ore fluids at Colquijirca can be best explained by
meteoric waters is indicated by the estimated 18O dilution of magmatic brines. The hypothesis that
and D compositions of water in equilibrium with diluted magmatic brines originated the Cordilleran
kaolinite and dickite, minerals recognized to have co- ore-forming fluids is also supported by key element
precipitated with the ores. These compositions plot concentration ratios of the ore samples and of the
following a pattern typical of meteoric waters that bulk Smelter-Colquijirca mineralized corridor notably
have exchanged isotopically with host rocks displaying Ag/Au (~50->300), Cu/Au (~7x104-~9x104), and
a positive 18O shift and a minimal shift in D. Fe/Au (~2x107-~5x107), which are similar to ratios
Modeling of isotopic equilibrium through convection observed in brines from microanalysis of fluid
suggests that 10.5-11.9 Ma Colquijirca meteoric inclusions from other porphyry-related localities and
water exchanged with host rocks, predominantly with different from the ratios measured in single-phase
sedimentary rocks. The exchanged meteoric waters vapor fluid inclusions coexisting with the brine fluid
then most likely experienced mixing with magmatic inclusions. As mentioned before, the Ag/Au, Cu/
waters. 34S compositions of sulfides of the whole Au, and Fe/Au ratios of the Au-(Ag) disseminated
Smelter-Colquijirca corridor, with average values bodies at Oro Marcapunta are, in turn, similar to those
close to zero, support such magmatic component. measured on single-phase vapor fluid inclusions in
The modeling predicts that the isotopic exchange several porphyry-related systems.
could take place only if the integrated water/rock Acidic fluids were common during the period
mass ratio attained values between 0.3 and 1. of Cordilleran mineralization. They manifested
A genetic model based on the integrated most prominently through assemblages exempt
geological, mineralogical, and microanalytical data of ore minerals, though less pronounced, they
may be broadly proposed. The model supposes also precipitated alunite accompanied by enargite-
the coexistence at depth, near the brittle-ductile (sphalerite). The isotopic evidence indicates that,
transition, of hypersaline fluid and single-phase vapor. as at Oro Marcapunta, these acidic fluids formed
Because of the probable shallow emplacement of 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.


RESUME ETENDU

RSUM TENDU

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


RESUME ETENDU

un assemblage chalcocine-tennantite superposant de minralisations lis plusieurs intrusions et/ou


de larges portions du corridor minralis de Smelt- dpisodes thermiques, le tout associ un large r-
er-Colquijirca. Les rapports Ag/Au de la totalit du servoir de magma. Lexistence de plusieurs pisodes
corridor de Smelter-Colquijirca atteignent des val- de minralisation est indique part la mise en relation
eurs entre 30 et 50 dans les zones internes (Figure h) individuelle des ages 40Ar/39Ar avec les relations de
et >250 dans les zones externes. 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
DURE DE VIE DU SYSTME daltration acide-dposition de lor a eu lieu pendant
MAGMATO-HYDROTHERMAL lactivit du systme pithermal Au-(Ag) (Figure e).
Sept ges 40Ar/39Ar four et laser obtenus sur
Les relations de recoupement indiquent que de lalunite prcdent, contemporaine et postdatant
lors du stade productif, les zones internes Cu ont diffrente gnrations dassemblages enargite et
empit sur les zones Zn-Pb, enregistrant ainsi un dassemblages sphalrite, indiquent que les min-
avancement progressif avec le temps du front de mi- ralisations de type Cordilleran riches en sulfures
nralisation riche en sulfure sur au moins 1.5 km. A Smelter et Colquijirca ont t forms quelques cen-
linverse, les assemblages tardifs chalcosine et ceux taines de milliers dannes plus tard que la minrali-
tennantite sont interprts comme rsultant de la sation pithermale de type high sulfidation Oro
rtraction du front minralisateur, probablement lors Marcapunta, persistant de 11.9 11.1 Ma (Figure e).
du dclin du systme hydrothermal lorsque le rapport Les ges plateau sur alunite du gisement de type Cor-
eau mtorique/eau magmatique tait plus lev dilleran Smelter et Colquijirca dfinissent un temps
Sept chantillons dalunite provenant du sys- dactivit hydrothermale relativement court, allant
tme pithermal Au-(Ag) dissmin de type high de 10.830.06 10.560.08 Ma (2

) (Bendez et
sulfidation ont t analyss par la mthode 40Ar/ al., 2003). De plus, trois ges K/Ar ont t obtenus
39
Ar furnace et laser et donnent des ges plateau sur roche totale dans le gisement de type Cordilleran
de 11.90.07 11.100.06 Ma 2 (Figure e). Ce San Gregorio (Figure e). Deux ges ont t obte-
laps de temps est particulirement long et est inter- nus 13.1-13.22.2 Ma (2

) et un troisime ge
prt comme rsultant de plusieurs pisodes courts 13.94.0 Ma (2

). En liminant la possibilit dun

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 Au-(Ag) disseminated


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 e: Diagramme rsumant les donnes gochronologiques (K/Ar et 40Ar/39Ar) disponibles dans le district de Colqui-
jirca.

10
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 Deux tendances de la temprature dhomognisation
(Figure g). Le champ allong est en accord avec une versus salinit peuvent tre mises en vidence partir
droite de mlange deau magmatique et mtorique des donnes dinclusions fluides disponibles des sta-
la composition de celle-ci tant dfinie Julcani, gise- des productifs. Une premire tendance se dessine par
ment contemporain au District de Colquijirca, situ les inclusions fluides dans le quartz des assemblages
400 km vers le sud (Deen et al., 1994). Le ple deau alunite-quartz, caractrise par des salinits entre ~0
magmatique tait vraisemblablement un panache de ~4 % poids NaCl quivalent et des tempratures
vapeur magmatique, duquel SO2 a interagi avec de dhomognisation allant de 221 273C (Figure f).
leau puis condens pour former H2SO4, lagent ma- Cette tendance est presque identique celle dfinie
jeur dacidit dans la formation de vuggy silica et de par le stade prcoce strile acide lors de la minralisa-
laltration quartz-alunite (e.g., Rye, 1993). La com- tion Au-(Ag) dissmine Oro Marcapunta (Figure
position isotopique du soufre dans lalunite (34S de f).
21.5 22.4 ) est en accord avec une origine dans Les observations minralogiques combines
laquelle le sulfate a quilibr avec H2S form travers aux rsultats disotopes stables permettent dinter-
la disproportionation de SO2 au sein dun panache de prter cette tendance comme le rsultat dun mlan-
vapeur subissant une condensation (e.g., Rye, 1993). ge entre un ple magmatique, vraisemblablement un
Des donnes limites dinclusions fluides du stade panache de vapeur riche en SO2, avec de leau m-
productif Au-(Ag) sont dfinis par une droite de torique. Les compositions de leau en quilibre avec
mlange qui est grossirement en accord avec celle lalunite du stade principal de minralisation ont des
du stade prcoce strile, suggrant des ples de flui- valeurs allant de -41

D et 7 18O progressi-
des similaires (Figure f). Les donnes disponibles vement des fluides isotopiquement plus lgers ayant
couvrent une variation allant de 190 260 C et des des valeurs autour de -99

D et -6 18O le
salinits de ~1 ~5 % poids NaCl quivalent (Fi- long dune tendance linaire suggrant un mlange
gure f). Un certain nombre dinclusions fluides dans de fluides magmatiques avec des fluides mtoriques

11
RESUME ETENDU

A B
350 350

300 300
a b
a
ThC

ThC
250 250

200 200

150 150

100 100
0.0 1.0 2.0 3.0 4.0 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0
Salinity (wt % NaCl eq.) Salinity (wt % NaCl eq.)

Type of Early barren stage: Type of Early silica-pyrite stage fluid inclusions:
primary in quartz from vuggy silica zones Isolated in quartz
primary in quartz from quartz-alunite zones Fracture-controlled in quartz
secondary in quartz from vuggy silica zones
secondary in quartz from quartz-alunite zones Type of Main ore stage fluid inclusions:
primary in alunite from quartz-alunite zones Primary in quartz from enargite-bearing assemblage
Secondary in quartz from enargite-bearing assemblage
Type of First gold stage fluid inclusions: Primary in sphalerite from sphalerite-bearing assemblage
primary in quartz from First gold stage Secondary in sphalerite from sphalerite-bearing assemblage
secondary in quartz from First gold stage 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 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 tendance couvre un intervalle de salinit plus large
avec la ligne de mlange dduite des fluides acides qui entre 0.35 7.2 % poids NaCl quivalent et des tem-
ont donns lieu aux zones vuggy silica et quartz- pratures dhomognisation de 218 286 C (Figure
alunite Oro Marcapunta. Par projection rgressive f). Ces donnes combines aux isotopes stables sug-
de la ligne de mlange reprsentant la totalit de la grent un mlange de fluides magmatiques avec des
population des valeurs

D et 18O de lalunite pr- eaux mtoriques isotopiquement changes avec les
sente dans le District de Colquijirca, il est possible roches encaissantes. Lentranement de ces fluides
destimer la composition de leau mtorique pr- mtoriques changs est indiqu par les estimations
sente Colquijirca entre 10.6-11.9 Ma caractrise des compositions en 18O et

D de leau en quili-
par des valeurs de -14010

D et -181 18O bre avec la kaolinite et la dickite, ces dernires ayant
(Figure g). Ces valeurs sont similaires la composi- co-prcipits avec la minralisation (Figure d). Ces
tion de leau mtorique pour dautres systmes du compositions suivent un patron typique deaux m-
Miocne au Prou central. Limplication dun pana- toriques ayant subit un change isotopique avec les
che de SO2 magmatique dans la formation des fluides roches encaissantes, traduit par un dcalage en 18O
en quilibre avec lalunite est aussi suggre par les et un dcalage minimal en

D (Figure g). La modli-
valeurs de 34S de lalunite (21.1 26.4 ) prsent sation dun quilibre isotopique par convection sug-
dans lassemblage quartz-alunite du stade principal. gre que leau mtorique 10.5-11.9 Ma de Colqui-
Celui-ci est typique dun fluide hydrothermal dori- jirca subit un change avec les roches encaissantes,
gine magmatique o le sulfate a quilibr avec H2S principalement des roches sdimentaires. Les eaux
form lors de la disproportionation de SO2 au sein mtoriques changes ont subit vraisemblablement
dun panache de vapeur en phase de condensation un mlange avec des eaux magmatiques. Les com-
(e.g., Rye, 1993). positions isotopiques en 34S des sulfures dans la to-
talit du corridor Smelter-Colquijirca, avoisinant des
La seconde tendance caractrise par la temp- valeurs proches de zro, confirment une composante
rature dhomognisation versus la salinit est dfinie magmatique. La modlisation prdit que lchange
par les inclusions fluides reprsentant les assembla- isotopique a eu lieu seulement si la valeur du rapport
ges enargite, largement dpourvus dalunite. Cette eau/roche se situe entre 0.3 et 1 (Figure g).

12
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 high sulfidation Oro Marcapunta. Les faibles rap-
ports Ag/Au (10 40) des corps de Au-(Ag) dis-
Un modle gntique bas sur des donnes smins sont similaires aux valeurs obtenues laide
gologiques, minralogiques et microanalytiques peu de mthodes microanalytiques quantitatives sur la
tre propos. Le modle suppute la coexistence en vapeur monophase dans dautres systmes lis aux
profondeur, proche de la transition ductile-cassante, porphyres cuprifres et sont en accord avec cette
dun fluide hypersalin et dune vapeur monophase prise de position (e.g., Ulrich et al., 1999).
(e.g., Heinrich, 2005). Du fait de la probable mise en Alors que la vapeur remonte, la saumure mag-
place peu profonde dune coupole de dgazage de matique reste trs probablement en retrait dans la
la chambre magmatique (suggr par la nature de la transition ductile-cassante et est libre graduellement
minralisation de porphyre cuprifre li dautres lors de la rtraction de cette transition en profondeur
gisements de types Cordilleran au Prou), la vapeur avec le temps. Dans ce cas, quelques dizaines de mil-
monophase na pas pus se contracter, permettant ai- liers dannes plus tard, lorsque les eaux mtoriques
nsi la vapeur dempiter dans le champ biphas au ont subit un change isotopique par convection avec
dessous de 450C lors de sa remonte. Les deux flu- les roches sdimentaires du groupes de lExcelsior et
ides en rsultants, indpendamment du mcanisme du Mitu, ces eaux ont pu tre mlanges avec la sau-
de sparation de phase (i.e. bullition ou condensa- mure magmatique. A Colquijirca, la modlisation, ba-
tion), sont probablement les prcurseurs des fluides se sur la composition isotopique de la kaolinite et de
responsables de la gnration de laltration acide- la dickite lis la minralisation, prdit que les eaux
dpt dor issu de pulses rcurrents reconnus lors changes peuvent obtenir des compositions isoto-
de la minralisation pithermale dissmine de type piques calcules, lorsque le rapport total eau/roche
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

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

Generalities, historical sketch and production

Colquijirca is one of the numerous examples body surrounding the Marcapunta volcanic center.
of mining districts related to Miocene intrusions of Projects and/or prospects include the so-called here
the high Cordillera of central and northern Per. It Cobre Marcapunta Sur and Oeste and the Cobre
contains several deposits which together constitute Marcapunta (Norte) or Smelter deposit.
one of the largest accumulations of Zn-Cu-Ag-Au-
Pb ores of the world. The district contains two main 3. Zn-Pb-Ag(Cu-Bi) sulfide-rich
ore types: (1) disseminated Au-(Ag) high sulfidation replacements in carbonate rocks of the Calera
epithermal mineralization, similar to the Yanacocha Member. Represented by the historic Colquijirca
and Pierina deposits of northern Per and Rodalquilar deposit, this style of mineralization displays the
in Spain and (2) large zoned sulfide-rich polymetallic strongest resemblance to many of the classic
deposits only comparable in tonnage to the ores of polymetallic Zn-Pb-Cu-Ag deposits of central and
the nearby giant Cerro de Pasco system. This second northern Per.
type is economically important and similar in many
respects to one of the most prominent deposit types 4. Zn-Pb(Ag-Bi) fine-grained sulfide-
of the porphyry-related family in the American rich replacements in carbonate rocks of the Pucar
cordilleras, the so called and characterized by Einaudi Group. This prominent style of mineralization was
(1977) Cordilleran deposits. virtually unknown in other parts of the world prior
Classical papers on this second ore type by noted to the discovery of San Gregorio. It is, indeed, the
geologists such as Ahlfeld (1929), Lindgren (1935) economically most important in the district and one
and McKinstry (1936) reflected the major economic of the largest Zn-Pb deposits of any type in the
importance of this district during the first decades of Andes.
the 20th century. It is from these works that we have
the first epigenetic postulations on the genesis of the Colquijirca is one of the earliest known silver
mineralization, all of them linking the Marcapunta mining centers of the Americas. According to
volcanic complex with the source of the ore fluids. several archeological surveys (e.g., Atalaya, 2000),
In the seventies, and diametrically opposed, Lehne the pre-incaic Tinyahuarco ethnic group lived on the
(1977) and Lehne and Amstutz (1982) proposed Colquijirca hill and worked silver between the 5th
a syngenetic model for the mineralization. More and 8th centuries.
recently, however, several workers including Arroyo It is believed that some of the silver goods
(1983), Vidal et al. (1984, 1997), Bendez (1997), transported by hundreds of llamas to pay the rescue
Fontbot and Bendez (1999) and Bendez et al. of the Inca king Atahualpa, and found in 1533 by
(2003), among others, argued, based on new data, for Spanish conquerors near Colquijirca (Miguel de
a magmatic-related epigenetic origin. Astete, 1533 in Markham, 1872) had their origin in the
Colquijirca mines. Some decades after and following
The ores of the Colquijirca district occur in the the route of Miguel de Astete, the Spaniards re-
following four distinctive types or styles: discovered Colquijirca and began mining as early as
1567 (Fisher, 1977). Mining since then, and until the
1. Disseminations, patches and veinlets end of the 19th century was intermittent, mainly using
of Au-(Ag)-bearing oxide minerals exclusively small-scale open-pit techniques. Unfortunately, there
hosted in the volcanic rocks of the Marcapunta is scarce available documentation for this period.
diatreme-dome complex. This style represented by In the 1890s the mine passed to Mr. Eulogio
the Marcapunta prospect, is a characteristic example Fernandini who started underground workings and
of high sulfidation Au epithermal mineralization. an economically very successful production period
from the early 1900s. For several years the mine was
2. Cu(Au-Ag-Sn) sulfide-rich the most productive in silver of the continent, with
replacements essentially in carbonate rocks of the an annual peak of nearly 7.5 million ounces in 1925
Pocobamba Formation and diatreme breccias. This (the Bonanza Epoch). From 1905, bismuth mining
type of mineralization consists of enargite and was at San Gregorio, some 6 km south of Colquijirca.
chalcocite-rich veins and mantos. Several projects and For several decades it was the most important mine
prospects of this style form a large funnel-shaped of this metal in Per before its closure in 1959. From

17
GENERALITIES

the end of the 1950s, mining was concentrated at REFERENCES


Colquijirca and production not only of silver but also
of zinc and lead increased considerably. This period Ahlfeld, F., 1932, Die Silberlagersttte Colquijirca,
of polymetallic production ceased in 1976, and with it Per. Zeitschrift Praktischer Geologie, v. 40, p. 81-87.
the underground workings in the historic Colquijirca
mines. From 1972 until the late seventies, mining Arroyo, F.,1983, Ocurrencia de minerales uranferos en
in the district was almost exclusively for copper (at el yacimiento de Colquijirca. Boletin Sociedad Geolgica
Smelter, 2 km south of Colquijirca). Since 1981, once del Per, 72, p. 75-88.
again, mining for zinc, lead and silver characterizes
the Colquijirca district, this time through modern Atalaya, E., 2000, Private archeological report for So-
open-pit operations. ciedad minera El Brocal S.A.A.
The lack of information during the Colonial
and early Republican periods precludes a precise Bendez, R., 1997, Caractersticas geolgicas miner-
evaluation of the total historical silver production algicas y geoqumicas de los yacimientos de Zn-Pb (Ag)
from the Colquijirca district. A rough and conservative de San Gregorio y Colquijirca emplazados en unidades
figure for the pre-Fernandini period is estimated sedimentarias en los bordes del sistema epitermal de alta
to be 30 million ounces. The registered data for sulfuracin de Marcapunta. Tesis Ingeniero, Universidad
the 20th account for 100 million ounces (compiled Nacional de Ingeniera, Lima, 60 p.
from Hutchinson, 1920 and available government
statistics), which indeed represent an underestimate Bendez, R., Fontbote, L., Cosca. M. 2003. Relative

age
since the production of a significant number of years of Cordilleran base metal lode and replacement deposits,
is undocumented. The total silver production of the and high sulfidation Au-(Ag) epithermal mineralization in
Colquijirca district may therefore approximate no the Colquijirca mining district, central Per. Mineralium
less than 150 million ounces. Deposita, 38, 683-694.
Although it is also difficult to calculate the total
zinc and lead production, the figure for the tonnage Einaudi, M.T., 1977, Environment of ore deposition
mined is simpler. It can be estimated that some 20 to at Cerro de Pasco, Per. Economic Geology, 72, p. 893-
25 Mt of ore at 6% Zn, 3% Pb and 3-4 oz/t Ag were 924.
extracted since the beginning of the 20th century.
The bismuth production at San Gregorio probably Fisher, J.R., 1977, Silver mines and silver miners in co-
exceeded 200000 tones (t) at 1 to 3 % Bi. The amount lonial Per, 1776-1824. Centre for Latin-American stud-
of copper ore treated from Smelter was insignificant ies, University of Liverpool, Monographs series N 7, 150
(<1 million tones) considering probable resources p.
of a minimum of 50 Mt at 1.9 % Cu (Yaringao et
al., 1997) in the northern sector of the district in Fontbot, L and Bendez, R., 1999, The carbonate
addition to another 50 Mt grading 1.8 % Cu recently hosted Zn-Pb San Gregorio deposit, Colquijirca District,
estimated in the western sector of the district (Vidal central Per, as a high sulfidation epithermal system, in
and Ligarda, 2004). Stanley et al., (eds.), Fifth Biennial SGA Meeting, Mineral
Deposits: Processes to Processing, 1, p. 495-498.

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

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

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 Lower Paleozoic times with a terrigenous strata of
centers, the geology of the central Peruvian Andes probable Cambrian to Devonian age (Mgard, 1978).
has received particular attention since the early McLaughlin (1924) recognized several well exposed
decades of the 20th century. McLaughlin (1924), occurrences of slates, phyllites and quartzites in
Steinmann (1929), Noble (1931), Harrison (1943), different parts of the region, including the Cerro
Boit (1949, 1962, 1964, 1966), Jenks (1951), Haas de Pasco district. He termed these units collectively
(1953), Johnson (1955), and Mgard (1968, 1978, the Excelsior Series, now known as the Excelsior
1984), and Angeles (1993, 1999) established the Group. Most of these units have been ascribed
basis of the stratigraphy and tectonic evolution of to the Ordovician, based on paleofauna found in
central Peruvian Andes. Other papers focused on several areas of the region including Chaupihuaranga
magmatism, including those of Noble et al. (1974, (Dalmayrac, 1978; Figure 1a.1). However, as discussed
1979, 1985, 1990), Soler (1987, 1991), Soler and by Mgard (1978), the age and history of the Lower
Bonhomme (1988), Soler and Rotach-Toulhoat Paleozoic rocks in the region remain uncertain.
(1990) and Noble and McKee (1999), among others. At a more local scale, the Excelsior Group
The following is an integration of all of the works crops out over appreciable areas of the Cerro de
mentioned above, complemented by my own data at Pasco district, where according to retrieved data from
the scale of the Colquijirca district. ancient mining operations, it would attain at least
The Colquijirca district is located on the 400 m in thickness. There, it is composed mainly of
Meseta de Bombon high plateau (at 4,300 m.a.s.l) reddish brown slates and phyllites with abundant thin
of the central Peruvian Andes near 11S and 76W. intercalations of quartzites. Sandstones grading along
From a tectonic point of view, it lies on a 1500 km strike to quartzites and arkoses were documented
long segment (from 2S to 15S) of flat subduction by Bowditch (1935) near the Cerro de Pasco mine.
in which the Nazca plate dips eastwards beneath Outcrops of the Excelsior Group in the Colquijirca
the Andes (e.g., Pilger, 1981). This segment is sector are scarce and present only in the northern
distinguished by the absence of modern and recent part of the district, at Vista Alegre and Condorcayn
volcanism. This Peruvian Andean segment developed (Figure 1a.2). In these places the main rocks of this
a considerable crustal thickness of 55-60 km (Couch group are slightly sericitized and chloritized reddish
et al., 1981; Gutscher et al., 1999), concomitant brown phyllites with centimetric slump structures,
with major Neogene uplift to nearly 4000 m.a.s.l. similar to those present at Cerro de Pasco (Angeles,
on average. The Colquijirca district is part of the 1993).
westernmost belts of Miocene magmatism in central
and northern Per (~360 km from the Peruvian
trench), with which most of the largest mining Ambo, Tarma and Copacabana Groups
districts are temporally and spatially associated (e.g.,
Noble and McKee, 1999). Metallogenetically, the 6 to In contrast to other parts of the Junin-
14S latitude region is characterizeed by development Goyllarizquisga region, the southeastern and eastern
of polymetallic deposits of the class known as areas near Carhuamayo (Figure 1a.1) presents
Cordilleran deposits (sensu Einaudi, 1977) which outcrops of Mississippian to Lower Permian rocks
coincide with the flat subduction segment. of the Ambo, Tarma and Copacabana Groups. The
Ambo Group (Mississippian) is composed dominantly
of sandstones and shales with intercalations of
Paleozoic conglomerates. Similar lithologies characterize the
Stratigraphy Tarma Group (Pennsylvanian) which, in addition,
Excelsior Group includes a few intervals of carbonate rocks. The
Copacabana Group (Lower Permian), which in other
The known geologic history of the Junin- parts of the Andes is known for its thick sequences
Goyllarizquizaga region (Figure 1a.1) commences in 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
CHAPTER 1

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

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
CHAPTER 1

Mesozoic frequently observed in the form of irregular masses


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

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

At these places, basaltic flows up to several hundred Pasco-Colquijirca sector (Figures 1a.2, 1a.3 and 1a.5).
meters thick are intercalated with the Goyllarisquizga Drilling, notably at Colquijirca, showed it to be over
sandstones (Johnson, 1955). Soler (1991) studied a large area concealed beneath the Calera Member.
some of these intercalations and concluded that the In the Cerro de Pasco district, the Shuco Member
basalts may represent early stages of rifting. 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
Cenozoic 1a.4) and the Excelsior Groups (at Condorcayn).
Stratigraphy Chambar Formation pebbles, cobbles and boulders
dominate as clasts. Clast size and clast/matrix ratio
Over large areas of the central Peruvian Andes, as well as relatively subtle variations in the lithology
a relatively thick continental sequence composed of clasts and matrix reflect distance from the
mostly of conglomerates, sandstones, sedimentary Longitudinal fault (e.g., Jenks, 1951; Angeles, 1999).
breccias, marls and limestones of Upper Cretaceous- Close to the fault, in the Cerro de Pasco district,
Eocene age rests unconformably on the Paleozoic the largest boulders, some up to 3 m in diameter
to Lower Cretaceous rocks (e.g., Mgard, 1978; are found. The clasts near the fault are invariably
Figure 1a.4;). Part of this sequence constitutes the Chambar limestones and generally are angular to
Pocobamba Formation in the Cerro de Pasco and subangular. Interclast spaces consist of a mixture
Colquijirca districts. of angular to subrounded granuled- to cobbled-
sized material, including sandstone, cemented by
calcite. Westward from the Longitudinal fault, the
Pocobamba Formation clasts display increased rounding and decreased
size. Other lithologies are locally abundant, as in the
The Pocobamba Formation was first described easternmost exposures of the Shuco Member in the
by McLaughlin (1924). Jenks (1951) divided the Cerro de Pasco district. There, west of the RSJV
Pocobamba Formation into three members: Lower (Rio San Juan-Venenococha; Figure 1a.2) fault more
Member (or Cacun Member; Angeles, 1999) at the than half of the clasts consist of dolostones of the
bottom, Shuco Member in the middle and Calera western Chambar domain (see section 1.2.1.1)
Member at the top (Figure 1a.4). with the remaining fraction from the eastern
Chambar domain (Angeles, 1999). Poorly stratified
Cacun Member. The Cacun Member, named beds, mostly composed of pebbles, tend to occupy
after the type locality near Cacun (Angeles, 1999), distal positions relative to the Longitudinal fault
consists of a sequence of up to 300 m thick of (Angeles, 1999), as in the Colquijirca district, west
shales, sandstones, conglomerates and limestones. In of the operating open pits. There, the presence of
the Colquijirca district, the Cacun Member is poorly incipient bedding is accompanied by a dominance
exposed and limited to the western block between of subrounded clasts, the majority not >20 cm in
the Lachipana and Puca Ingenio hills (Figure 1a.2). diameter (Figure 1a.5).
It can, in general, be characterized as a typical red The Shuco Member is considered as a
bed sequence. Its lower parts are composed of fanglomerate or piedmont deposit (Jenks, 1951;
reddish sandstones, siltstones, and mudstones, often Angeles 1993, 1999), with the above mentioned
displaying cross-bedding. Channel-fill conglomerates, characteristics being consistent with this interpretation.
breccias and other coarse-grained detrital rocks also The Longitudinal is the eastern limit of the main
typify these intervals. The clasts, <5 cm long, mostly uplifted block, largely made up of the Chambar
subrounded and cemented by calcareous material, Formation which is the erosional source for most
consist of Pucar-derived limestones (Angeles 1993, of the Shuco material. As stated by Angeles (1993,
1999), with minor sandstones, siltstones and locally 1999), variations in the thickness of this unit are also
milky quartz. controlled by distance from the uplifted blocks, and
The upper intervals of the Cacun Member hence, from the Longitudinal fault (Figure 1a.4).
comprise metric beds of whitish limestones, with
some chert, pellets and biogenic structures. According Calera Member. McKinstry (1936), Noble
to Angeles (1999), these limestones are lacustrine (1992) and Angeles (1999) assigned the status of
in origin. The same author estimated the thickness Formation to the carbonate and detrital rocks resting
of the Cacun Member as no less than 100 m. At on the Shuco Member (Figure 1a.4). In this review,
Colquijirca, the Cacun Member is exposed locally at use of the classical sub-division proposed by Jenks
Lachipana hill (Angeles, 1999). (1951) is preferred which refers, and refer to this
sequence as part of the Pocobamba Formation,
Shuco Member. The Shuco Member consists namely the Calera Member. According to Jenks (1951),
principally of poorly sorted monomictic, clast- the Calera Member is estimated to be composed of
supported breccias and conglomerates (Figure 1a.5). about 70 per cent argillites, limestones, siltstones
Its outcrops cover considerable areas in the Cerro de 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 consist of pebbles of black limestones in an argillic
calcareous component, many of them marls. Angeles matrix. Similarly, several intervals with no exposure
(1993) divided the Calera Member into three members, complete this first 50-m-thick section. The sub-
here sub-members, based mainly on differences in member is completed by a thin interval characterized
lithofacies: Lower, Middle and Upper sub-members. by marls, calcareous argillites and limestones, the last
The following is an abstract of his work. with characteristic relicts of rhizoconcretions and
Lower sub-member: The first 10-20 m above roots. This interval is also interbedded with detrital
the Shuco Member are not exposed. There follows a sediments, similar to the lower part, although in this
sequence dominated by detrital sediments, including case subordinate. The total thickness of the lower
tuffs, sandy siltstones and lesser conglomerates. The sub-member is estimated to be 64 m.
conglomerate beds are of decimetric thickness and Middle sub-member: This part of the Calera

30
CHAPTER 1

Member is the best exposed, both as natural outcrops and Colquijirca districts. In the Colquijirca district,
in several parts of the district in the open pits (Figure Angeles (1999) linked the Cacun Member deposits
1a.5). It is characterized, in contrast to the other sub- to tectonic movements related to the Longitudinal
members, by an abundance of nearly pure carbonate fault. The abundance of coarse sediments in the lower
rocks. In the old La Calera quarry, limestones grade intervals of this member, and the predominance of
from mudstone to coarse grainstone, usually with calcareous material at the top, have been attributed
biogenic structures and, in some cases, fossiliferous. to waning of tectonism, possibly linked to this major
Intercalations of large concretions of chert and thin structure. A similar process could have occurred
beds of argillite complete the interval. There follows during deposition of most of the Shuco Member
a generally finer-grained interval consisting of an with variations in lithofacies and thickness being
alternation of multicoloured argillites and limestones, related to distance from the Longitudinal fault.
generally mudstones to wackestones. Exposure of this The formation of a lacustrine basin during the
sub-member in the open pits reveals that it is much Upper Eocene marked the beginning of a period of
richer in chert compared with the unaltered rocks relative tectonic quiescence. The interpretation by
beyond the limits of mineralization. This suggests Angeles (1999) implies an early ephemeral basin, with
that at least part, if not probably most, of the chert periodic incursions of fluvial material (Lower sub-
in this part of the district has a hydrothermal origin. member), followed by the establishment of a more
Angeles (1993) estimated the thickness of the middle stable basin occupied by the Calera lake. The Calera
sub-member to be nearly 55 m. lake, according to the same author, evolved from a
Upper sub-member: In contrast to the lower shallow holomictic to shallow ectogenic meromictic
sub-members, it appears to be present only south lake, in which sediments either poor and rich in
of the Cuchis Grande lake (Figure 1a.2), and thus, organic matter and typical of the Middle and Upper
restricted to the Colquijirca district. The most sub-members, respectively, accumulated. Variations
complete stratigraphic interval is exposed in the in facies were controlled by climatic changes and by
open pits where intercalations of argillites, siltstones, a possible extension of the hydrographic net rather
marly dolostones and some volcanosedimentary beds, than by tectonic processes (Angeles, 1999)
including tuffs, occur. According to Angeles (1993), Tectonics in central Per during Cenozoic
this sub-member exceeds 150 m in thickness. were essentially compressive (e.g., McLaughlin,
Considering the measurements made by Angeles 1929; Mgard, 1978), and consisted of discrete,
(1993), the total thickness of the Calera Member short, intense periods of deformation with probable
attains a minimum of 250 m. However, exploration peaks at 100-38 (not well defined; e.g., Myers, 1975;
drilling immediately northeast of Marcapunta hill Cobbing et al., 1981), 26, 17, 10, 7 and 2 Ma (e.g.,
reveals an up to 500 m thick sequence. The Calera Mgard, 1984). Indeed, most of the structural
Member is thought to be of Upper Eocene age on features currently observable in the Cerro de Pasco-
the basis of K-Ar age of ~36-37 Ma for biotite from Colquijirca sector formed or were active during this
a tuff layer located near the base of the Lower sub- Cretaceous-Tertiary interval (Jenks, 1951; Angeles,
member (Noble et al., 1999). 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
Paleogeography, tectonic evolution and Quechua III (7 Ma) tectonic pulses. At Colquijirca,
structures the major tectonic phases occurred subsequent to
Pocobamba Formation sedimentation, that during
Mgard (1978) stated that the abundant Lower the Aymara (26 Ma) or Quechua I (17 Ma, Angeles
Cenozoic red beds of central Per were products (1993, 1999) events.
of extensive erosion from essentially two emerged The major north-south Longitudinal and
blocks. One was located along the present coast and FRSJV faults display evidence for reverse motion
isolated the Andean platform from marine influences. coherent with the nearly east-west main shortening
The second passed approximately through Cerro de direction for the region at 26 and/or 17 Ma (Figures
Pasco, parallel to the general alignment of the Andean 1a.1, 1a.2, and 1a.3). A strike-slip fault system present
Cordillera. Much of the continental material present throughout the Cerro de Pasco-Colquijirca sector
in the Cerro de Pasco-Colquijirca sector, including (F1 and F2 system in Figure 1a.3) is directionally
the deposits of the Cacun and Shuco Members, consistent with first-order breaks in a similar stress
was formed by erosion of this second block. This regime, suggesting that this system was also formed
same scenario apparently existed since the Upper as a response to compression. Both the folding and
Cretaceous, although at that time the presence of F1-F2 fault system occurred prior to hydrothermal
marine deposits suggests an ephemeral marine mineralization and as will be shown later, constituted
incursion. important controls on the channeling of mineralizing
According to Mgard (1978), major faults solutions, particularly in the northern part of the
strongly influenced the spatial distribution of these Colquijirca district.
high-energy Eocene deposits, as in the Cerro de Pasco

31
CHAPTER 1

Magmatism and Mineralization


composition, all of them texturally porphyritic. The
largest hydrothermal sulfide concentration related to
As in large parts of the Peruvian high Cordillera, a single intrusive center took place at Cerro de Pasco.
the most important period of magmatism took place There, even after extensive erosion, the mining camp
during Cenozoic. Several periods of magmatic activity still records a minimum of 2.5 billion tones containing
are recorded in the Junin-Goyllarizquizga region, more than 50 volume % of sulfides, largely pyrite,
with which virtually all the recognized hydrothermal but also rich zoned polymetallic ores of Cordilleran
mineralization is related. base metal lode type (Einaudi, 1977).
On the basis of radiometric dating, mostly South of Cerro de Pasco is the smaller
using the K/Ar method (Soler and Bonhomme, Yanamate dacitic volcanic center (~15 Ma; Soler and
1988; Cobbing et al., 1981), a long early event from Bonhomme, 1988). A survey carried out by Angeles
the Upper Eocene at ~ 39 Ma and Upper Oligocene (1993) revealed similar characteristics to those of
at ~ 29 Ma can be roughly defined. The apparently Cerro de Pasco, including development of a diatreme
unmineralized dacitic to rhyodacitic stocks at Huangoc associated with a dome-dike system. Hydrothermal
(38.5 Ma), Raco (35.2 Ma) and Huancayn (33 Ma), alteration is recognized in the vicinity of the volcanic
in the central and northern part of the region belong center, although its economic significance has not
to this early period. Those east of Cerro de Pasco at been evaluated in any detail.
Mariac and Sunkullo (31 Ma; Soler and Bonhomme, Further to the south, about 10 km from Cerro
1988; Figure 1a.1) are of rhyodacitic composition de Pasco, is the Marcapunta volcanic complex (~12
and younger. The earliest recognized hydrothermal Ma; Vidal et al., 1984), in the center of the Colquijirca
event in the region, possibly related to the Huangoc district (Figure 1a.5). As at Yanamate, it also shares
and Raco intrusions, generated a 37.5 Ma epithermal many similarities with Cerro de Pasco including
Au deposit within a volcanic dome at Quicay (Noble diatreme development, multistage superimposition
and McKee, 1999; Figure 1a.1). The nearby Pacoyn of a dome-lava complex and important collapse of
Au prospect as well as tuff deposits of the Calera the sedimentary pile surrounding the main diatreme
Member dated at ~36 Ma may be related to this same neck. Geochemical reconnaissance of unaltered and
~37 Ma pulse (Figure 1a.1). slightly altered rocks, presented in the next Chapter,
At the end of this major magmatic event, at reveals homogeneous dacitic composition. Several
~ 29 Ma, a dacitic intrusive center was active in the lines of evidences, discussed in detail in this thesis,
vicinity of Atacocha. An important hydrothermal indicate that the mineralization is related to the
system associated with it produced polymetallic veins Marcapunta magmatic center. Mineralization consists
and skarn-related deposits of the Milpo-Atacocha of disseminated high sulfidation epithermal Au-(Ag)
district. At ~28 and ~15 Ma there is no evidence mineralization and zoned base metal bodies similar
of magmatic activity in the region, although it was to those at Cerro de Pasco, i. e., Cordilleran base
intense elsewhere in Per, including nearby parts of metal lodes.
the Western Cordillera. Perhaps the last important magmatic expression
A second major magmatic event occurred in the region are the widespread late Miocene (~6.4-
between 15 and 11 Ma in the Cerro de Pasco- ~5.2 Ma) rhyolitic ash-flow tuffs of Huayllay (40
Colquijirca districts, and was one of the richest and km southwest of Colquijirca) deposited along the
most mineralized in the world. In contrast to the western border of the high plateau of the central
earlier magmatism in the region, there was important Peruvian Andes (Harrison, 1943; Cobbing et al.,
development of several diatreme-dome volcanic 1981; Figure 1a.1).
complexes emplaced along the major north-south
reverse faults (Figure 1a.1). This fault-controlled
magmatic-hydrothermal belt seems to extends at REFERENCES
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32
CHAPTER 1

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Cox, L.R., 1949, Moluscos del Trisico Superior del Noble, J.A., 1931, Colquijirca examination, 1930-31.
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p.
Dalmayrac, B., 1978, Gologie des Andes Pruviennes.
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924.
Noble, D.C., McKee, E.H., and Mgard, F., 1979, Ear-
Gutscher, M.A., Aslanian, D., Eissen, J.P., Olivet, J.L., ly Tertiary Incaic tectonism, uplift, and volcanic activ-
Maury, R., 1999, The lost Inca Plateau; cause of flat ity, Andes of central Per. Geological Society of America
subduction beneath Per?. Earth and Planetary Science Bulletin, 90, p. 903907.
Letters, 171; 3, p. 335-341.
Noble, D.C., Sebrier, M., Mgard, F., and McKee, E.H.,
Haas, O., 1953, Mesozoic invertebrate faunas of Per. 1985, Demonstration of two pulses of Paleogene defor-
Bulletin of the American Museum of Natural History, mation in the Andes of Per. Earth and Planetary Science
101, 328 p. Letters, 73, p. 345-349.

Harrison, J.V. 1943, The geology of Central Andes in Noble, D.C., McKee, E.H., Mourier, T., and Mgard,
part of the province of Junin, Per. Quarterly Journal of F., 1990, Cenozoic stratigraphy, magmatic activity, com-
the Geological Society of London, 99, p. 1-36. pressive deformation, and uplift in northern Per. Geo-

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logical Society of America Bulletin, 102, p. 1105-1113. of America, Special Paper, 241, p. 161-172.

Noble, D.C., and McKee, E.H., 1999, The Miocene Stanley, G.D., 1994, Early Mesozoic carbonate rocks
metallogenic belt of central and northern Per, in Skin- of the Pucar Group in northern and central Per. 1994.
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Andes. Society of Economic Geologists Special publica-
tion, 7, p. 155-193. Steinmann, G., 1929, Geologie von Per. Carl Winters
Universittsbuchhandlung, Heidelberg, p. 1-448.
Noble, D.C., 1992, Informes privado varios. Compa-
a de Minas Buenaventura. Szekely, T.S., and Grose, L
.T., 1972, Stratigraphy of
the carbonate black shale and phosphate of the Pucar
Pilger, R.H., 1981, Plate reconstructions, aseismic Group (Upper Triassic-Lower Jurassic), Central Andes,
ridges, and low-angle subduction beneath the Andes. Per. Geological Society of America Bulletin, 83, p. 407-
Geological Society of America Bulletin, 92, p. 448-456. 428.

Prinz, P., and Hillebrandt, A., 1994, Stratigraphy and Vidal, C., Mayta, O, Noble, D.C., and McKee, E. H.,
ammonites of the north Peruvian Pucar Group. Paleon- 1984, Sobre la evolucin de las soluciones hidrotermales
tographica Abt. a., 233, p. 33-42. dentro del centro volcnico Marcapunta en Colquijirca-
Pasco. Volumen Jubilar Sociedad Geolgica del Per, 10,
Rosas, S., 1994, Facies, diagenetic evolution, and se- p. 1-14.
quence analysis along a SW-NE profile in the southern
Pucar basin (Upper Triassic-Lower Jurassic), central
Per. Heidelberger Geowiss. Abh., Ruprecht-Karls-Uni-
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Rosas, S., Fontbot, L., and Tankard, A., 2007, Tec-


tonic evolution and paleogeography of the Mesozoic Pu-
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Sciences, v. 23.

Silberman, M.L., and Noble, D.C., 1977, Age of igne-


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-
914.

Soler, P., 1991, Contribution ltude du magmatisme


associ aux marges actives ptrographie, gochimie iso-
topique du magmatisme Crtac Pliocne le long dune
transversale des Andes du Prou Central Implications
godynamiques et mtallogniques. Thse de Doctorat
des Sciences Naturelles, Paris, Universit Pierre et Marie
Curie, Paris VI, 832 p.

Soler, P., and Bonhomme, M.G., 1988, New K-Ar age


determinations of intrusive rocks from the Cordillera Oc-
cidental and Altiplano of central Per. Identification of
magmatic pulses and episodes of mineralization: Journal
of South American Earth Sciences, 1, p. 169-177.

Soler, P., and Rotach-Toulhoat, N., 1990, Implications


of the time-dependent evolution of Pb- and Sr-isotopic
compositions of Cretaceous and Cenozoic granitoids
from the coastal region and the lower Pacific slope of the
Andes of central Per, in Kay, S.M., et Rapela, C.W., eds.,
Plutonism from Antarctica to Alaska. Geological Society

34
CHAPTER 1

1b. The Marcapunta diatreme-dome complex

The Marcapunta volcanic complex, as drill holes have revealed a large body of polymictic
introduced above, is an intrusive center (Figure breccias below the summit of Marcapunta hill (Figure
1b.1) consisting of multiple dome-lava bodies of 1b.2). In accordance with Noble (1992), Barba (1992),
mainly dacitic composition, which pre- and post- and Sillitoe (2000) these breccias represent the upper
date several episodes of explosion brecciation and fingers of a major diatreme conduit at depth.
pyroclastic accumulation typical of diatremes. The There is no detailed map of the original volcanic
overall internal construct of the volcanic complex, facies of the Marcapunta volcanic complex, however,
including the vent structure, is as yet poorly defined. based on integration of available maps, including
Only recently, an intense exploration diamond those currently in progress by Brocal-Buenaventura
drilling campaign along the western flank of the geologists, the fragmental rocks of the Unish Tuff unit
complex, coupled with similar exploration data from can be assigned to two main sectors, north and east of
the northern sector, is providing the first constraints the center of the volcanic complex (Figure 1a.3). In
on the three-dimensional internal configuration. both places the pyroclastic deposits comprise lapilli-
Some of these data are preliminarily presented here. tuff and less abundant lapilli-tuff breccias (Figure
Also preliminary is the reconnaissance study of the 1b.2). Outcrops within the high parts of Marcapunta
chemical composition of the volcanic rocks presented hill comprise lapilli-tuff, commonly displaying well-
in this section. developed internal stratification (including cross-
bedding), considerable variation in the grain size and,
although rare, accretionary lapilli. These features are
Main volcanic facies and spatial typical of base surge deposits which are generally
configuration near-vent pyroclastic manifestations, suggesting that
at Marcapunta the main vent was located below the
Topographically, the Marcapunta diatreme- present-day topographic high (Figure 1b.1). Drill holes
dome complex resembles a centralvolcano, with located in the upper portions of Marcapunta (e.g.,
typical gently dipping flanks and the center of the Brocal-548), intercepted, besides lapilli-tuff deposits,
complex as a topographic high (Figure 1b.1). The important intervals of breccias. Such breccias consist
complex is exposed within a slightly elliptical area of monomictic and polymictic angular clasts, up to
and has major axis north-south and nearly parallel to several decimeters in sizes, a fine-grained matrix
the main direction of Cenozoic compressive stress. composed of milled dacitic rock and juvenile
Most of the outcrops are strongly altered material. These breccias are interpreted as products
due to a widespread and intense hydrothermal of phreatomagmatic explosions. Also typical of the
alteration; however, a broad lithological distinction central outcrops of the volcanic complex are thin
can be drawn on the basis of remnant textures and dike-like bodies of massive fine-grained tuffaceous
evidences provided by limited areas of less-altered material. According to several workers (e.g., Corbett
rocks (Figure 1b.1). The early work by Noble (1931) and Leach, 1998), these are tuffisite injections, i.e.,
was the first reconnaissance mapping carried out another phreatomagmatic product. Drill hole SD-
at Marcapunta and his nomenclature is often used 11 intercepted several intervals of milled polymictic
in the present work. More detailed work, although breccias up to nearly 100 m of vertical extension. In
focused on hydrothermal features, as conducted by contrast to the phreatomagmatic breccias described
Barba (1992) and Vidal (1992), and some additional above, these contain smaller clasts, generally several
details of the Marcapunta volcanic complex can be centimeters across. Although strongly leached, it
found therein. is still possible to recognize original clast lithology
The outcrops of the Marcapunta volcanic which includes laminated limestone, milky quartz
complex can be divided into two main units: and phyllite from the Pocobamba Formation, Mitu
one constituted by a variety of fragmental rocks Group and Excelsior Group respectively. Such varied
(according to the nomenclature of Schmid, 1981), lithology suggests a major phreatomagmatic process
largely pyroclastic, known as Unish Tuff and a second originating at depths of at least 1 km, which accords
and more important in terms of volume, dominated with the idea that a relatively large diatreme conduit
by dacitic lava domes and flow rocks. In addition, exists in the inner parts of the Marcapunta volcanic

35
CHAPTER 1

S N
D C B A

SD-11 Brocal-548
100 m

200 m
CM2-604

Unconformity
Collapse-related fault
Diamond drill hole
3800 masl

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 As shown below, the chemistry of the scarce unaltered
the breccia body at 450 m depth, but considering rocks indicates an exclusively dacitic composition.
other holes located in the surroundings, the diatreme However, comparatively higher abundances of relict
conduit may have a ramified, flared geometry and resorbed quartz in some rocks indicates that besides
gain continuity downward, with only its upper parts dacite, rhyodacitic or less probably rhyolitic rocks
encountered. The phreatomagmatic breccia also may have been originally present (Yacila, pers. comm.,
developed laterally to the north and south, with 2002). These less common rocks were mainly observed
offshoots recognized as far as 600 m from the main within the volcanic units of the central diatreme
vent. neck. Mineralogically, all the unaltered dacitic rocks
In the northern block (Figure 1b.1), beyond consist of blocky sanidine crystals, as large as 12 cm
the main explosive center, extensive drilling has (Figure 1b.2), besides smaller plagioclase (probably
intercepted lapilli-tuff accumulations of ill-defined andesine; Harvey, 1936 in McKinstry, 1936) and
origin, which are often associated with, volumetrically resorbed quartz (Figure 1b.2). Also distinctive are
more important, block and ash deposits up to 200 m euhedral biotite, hornblende and clinopyroxene. The
thick. The block and ash deposits are topographically aphanitic matrix is mainly composed of orthoclase,
controlled and consist of monomictic, subangular to quartz and minor biotite. Accessory minerals include
subrounded dacitic porphyry clasts in an ash-sized apatite, zircon and magnetite. Harvey (1936) also
matrix of feldspar and pyroxene? grains, and aphanitic reported rutile.
lithic fragments. A relatively common feature of Lava flows dominate over lava domes at
these deposits is their reverse grading. The block and surface. Flow banding (Figure 1b.2) is thus much
ash deposits in this sector are tentatively interpreted more common than blocky spherulitic lava typical of
as formed by collapse of lava-domes, more likely by the central portions of domes (Self, 1982). Drilling
gravitational instability than by explosive triggering. information indicates that lava flows are present
The majority of the exposures of the throughout the volcanic pile that is from the erosional
Marcapunta volcanic complex comprise lava flows discordance over the Eocene Calera sequence up to
and lava-dome facies (according to the nomenclature the current top of the Marcapunta complex. The
of Self, 1982). Again, despite the fact that the rocks flows overlie either lapilli or block and ash deposits.
are strongly altered, it is still possible to recognize Recognized thicknesses of the lava flows attain 100
many of the original characteristics of these m. Based on well-preserved features, such as flow
facies. Macroscopically, virtually all these rocks are banding and spherulitic textures, lava dome diameters
homogeneously porphyritic in texture (Figure 1b.2). vary from a few tens of meters to as large as 500 m

36
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
CHAPTER 1

east of Smelter, although most of those recognized those observed microscopically are considered too
are generally <50 m. strongly altered.
Based mainly on surface observations from Four of the six unaltered samples were
several places, Angeles (1999) provided several analyzed for rare earth elements (REE) (PBR-148,
lines of evidence for subsidence or collapse of an PBR-185c, PBR-216 and PBR-216a; Appendix
important part of the Marcapunta volcanic complex. 1b.2). In addition, in order to obtain REE patterns
He recognized normal faults along the northern, representative of the central portions of the volcanic
southern and southwestern borders of the complex complex, the diatreme itself, two samples from the
(Figure 1b.1) in what seems to be a ring fault outermost haloes of mineralized zones were also
pattern similar to the peripheral structures of many selected (PBR-145 and PBR-199). Although these
much larger caldera systems (e.g., Lipman, 1997). last samples display a weak to moderate propylitic
Moreover, he deduced from measured strikes and alteration under the microscope, they were analyzed
dips that the lapilli-tuff deposits (surge deposits) and included in the study following several papers in
are spatially disposed in a centripetal arrangement which it has been shown that REE concentrations
coherent with central subsidence. The observations in igneous rocks affected by such alteration remain
of Angeles (1999) are supported by a preliminary virtually unchanged and faithfully represent the
three-dimensional correlation based on recent original values in their unaltered equivalents (e.g.,
drilling information (Figure 1b.1). In the northern Fulignati et al., 1999).
sector of Marcapunta, for example, a grid of drill
holes, spaced no more than 150 m from each other, Major and trace element compositions:
allows precise delineation of the Mitu-Pocobamba Major and trace element compositions are broadly
discordance 1km from Smelter to the innermost homogeneous in all the analyzed samples. Major
portions of the Marcapunta center. What was found element contents are invariably high in silica (>65
is a generalized deepening of the discordance on %) and alumina (>15 %), whereas contents of MgO
approach to the main vent (Figure 1b.1). While (0.76-1.25 %) and CaO (1.16-2.77 %) are low. At
the deepening is rather gentle in the external parts, the level of trace elements, the most remarkable
it steepens in proximity to the diatreme conduit, characteristics are the high concentrations of Sr (up
indicating an increase in downsag ging. Drill hole
Brocal-548 gives an idea of the maximum magnitude  A seventh analyzed sample, not included in this set,
of such movement, with a relief on the discordance from a dome affected by more advanced hydrothermal alteration
of at least 300 m between holes Brocal-548 and CM2- (moderate to strong phyllic alteration) displays a nearly identical
604 (Figure 1b.1). A similar configuration is indicated profile, although with slightly higher values (Sample PBR-215,
when other stratigraphic or lithological markers Appendix 1b.2). This sample was finally not taken into account
such as the conglomeratic Lower sub-member of due to the possibility of REE enrichment by hydrothermal fluid
the Pocobamba Formation, are delineated. The introduction.
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 14
volcanic complex, being most prominent in the near-
vent parts. The geometry of the main subsidence 12
structures remain ill-defined. Nevertheless, a
generalized system of semi-vertical fractures, some
Trachyte
10
of them normal faults with minor displacements, are
Na2O+K2O wt %

observed in the Smelter underground mine (Figure 8 Trachydacite

1b.1). Trachyandesite
Rhyolite

6
Colquijirca district
General Chemistry 4
Andesite

Basaltic Dacite
The scarcity of unaltered rocks makes Basalt
Andesite

2
petrologic characterization of the Marcapunta
volcanic rocks difficult. However, seven samples
were found to be exempt from alteration and were 0
40 50 60 70
analyzed for major and trace elements using the classic
XRF technique (Appendix 1b.1). These samples were SiO2 wt %
collected exclusively from flanking domes where Figure 1b.3
hydrothermal alteration was minor or non-existent. Figure 1b.3: Total alkalis versus silica discrimination dia-
Neither pyroclastic rocks nor breccias were analyzed gram of Le Maitre et al. (1989) showing the volcanic and
in the present reconnaissance, mainly because all subvolcanic rocks of the Colquijirca district.

38
CHAPTER 1

Abundance/chondrite 1000 150

100
Adakite field
100

LaN/YbN
Colquijirca district Classical island
dacitic rocks
10 arcs dacite field
50

1
La Ce Pr Nd Sm Eu Gd Dy Ho Er Tm Yb Lu
0
0 10 20 30 40 50
Figure 1b.4:1b.4
Figure REE abundances of dacitic domes and lavas YbN
of the Colquijirca district normalized to chondrite values of
Nakamura (in Potts et al., 1981). Note that REE patterns Figure 1b.5: Dacites
Figure 1b.5 of the Colquijirca district plotted on
of two slightly altered samples are indistinguishable from those a discrimination diagram for the adakitic and typical mod-
that are unaltered. ern island arc dacitic field (after Martin 1999). N: normal-
ized to chondrite values of Nakamura, 1981 (in Potts et al.,
1981).
to ~1200 ppm) and low contents of Y (<12 ppm)
(Appendix 1b.1). In accordance with preliminary direct melting of young subducted oceanic crust as
classification based on microscopic observations, all their source. However, more recently, some of these
the unaltered samples plotted on the classical total adakite-like signatures have also been found in rocks
alkalis versus silica diagram of Le Maitre et al. (1989) at several latitudes in the Andes where the isotopic
lie in the dacite field (Figure 1b.3). Complementary evidence suggests an important crustal contribution
plots using the K20 versus SiO2 diagram of Peccerillo to their formation. Detailed geochemical and
and Taylor (1976) show the unaltered rocks to be isotopic studies in conjunction with geotectonic
centered on the high-K subalkaline field of Le Maitre reconstructions, along various segments of the
et al. (1989) or high-K calc-alkaline field of Rickwood southern Andes led to some researchers (e.g., Kay et
(1989). al., 2005) to propose that these Chilean adakite-like
The set of REE profiles, normalized to rocks could have been formed from mantle-derived
chondrite values of Nakamura in Potts et al. (1981), magmas with an important involvement of crustal
show regular distribution and parallelism (Figure material, most likely by processes of subduction and
1b.4), suggesting a cogenetic and comagmatic origin erosion of forearc crust and/or tectonic thickening
for all the analyzed samples. Such parallelism is and assimilation of Andean crust.
consistent, as mentioned above, with the negligible The adakite-like rocks of the Cerro de Pasco-
mobility of REE in rocks affected by low degrees of Colquijirca volcanic belt are included in this latter
hydrothermal alteration. In terms of composition, the category if we take into account the non MORB-
most outstanding feature is the high LREE/HREE like 87Sr/86Sr isotopic composition (>0.705) from
(light/heavy) fractionation with steep La/Yb ratios Yanamate (Soler, 1991) and Cerro de Pasco (Noble
ranging between 42 and 63 (or LaN/YbN ratios of and McKee, 1999). It remain to be shown if similar
~30-40) related to strong depletion of HREE (e.g., or alternate processes can explain the genesis of
0.6-0.8 ppm Yb). Also remarkable is the absence of these anomalous dacitic rocks in the Cerro de Pasco-
negative Eu anomalies in all the analyzed samples Colquijirca magmatic belt, where two of the largest
(Figure 1b.4). polymetallic deposits occur.

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 REFERENCES
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and Drummond (1990, 1993; Figure 1b.5). According Cerro de Pasco: estrastigrafa, sedimentacin y tectnica.
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Al2O3>15% and MgO<3%, in addition to Sr/Y>22, 103-118.
Sr>400 ppm, Y<18 ppm and La/Yb>20. Indeed,
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the whole Cerro de Pasco-Colquijirca belt including Cerro Marcapunta. Informe privado Sociedad Minera El
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39
CHAPTER 1

Rim gold-copper systems: structure, alteration and miner- tivation analysis a critical appraisal of calibration errors.
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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

Chapter 2
Description of the mineralization types

Introduction
Main terminology
The goal of Chapters 2a, 2b, 2c, 2d, and 2e The following terms are employed in the sense
is to document physically, mineralogically and of Barton (1963, 1970), Hemley and Hunt (1992),
geochemically the main characteristics of the two and Einaudi et al. (2003).
mineralization types in the district: (a) sulfide-rich
polymetallic deposits (Chapters 2a, 2b, and 2d) and Mineral assemblage: A grouping of minerals
(b) disseminated Au-(Ag) mineralization (Chapter occurring in direct contact and displaying no evidence
2c). Additionally, these two mineralization types are of reaction with one another (Einaudi et al., 2003).
compared in Chapter 2e. Although Hemley and Hunt (1992) applied this
term when chemical equilibrium is implied, in this
work, if not specifically discussed, the term mineral
Field and laboratory methods of study assemblage is strictly descriptive.

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

43
CHAPTER 2

44
CHAPTER 2

2a. The Smelter deposit

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

Thus, the entire section of the Pocobamba Formation responsible for the silica-pyrite replacement. From
(up to > 150 m thick) including poorly reactive beds these permeable horizons, fluids spread into the
of sandstone, argillite, and siltstone, was extensively immediately over- and underlying beds.
replaced. The great intensity of mineralization in this As shown in Figure 2a.3, the silica-pyrite
area is also reflected by the fact that, in addition to the replacements separate into two or, in places,
Pocobamba Formation, intervals up to several tens three branches. With increasing distance from the
of meters thick, of the underlying Mitu Group red diatreme conduit, narrowing of the replaced interval
beds and overlying volcanic units of the Marcapunta is recognized, and north of line 644 replacement is
complex were also replaced. It is likely that normal confined to the middle portion of the Pocobamba
faults related to the subsidence-collapse of the Formation. In this sector, the Shuco Member is
sedimentary pile surrounding the volcanic center not replaced (Figure 2a.3). Normal faults probably
played a major role as fluid channelways. channeled the fluids into higher stratigraphic positions
In contrast to the virtually total replacement of the Pocobamba Formation, as suggested by
in areas close to the intrusive center, northward abrupt jumps of the replaced intervals coinciding
from line 580 (Figure 2a.3) replacement is largely with projected faults between lines 588 and 628
controlled by the receptivity of the original lithology. (Figure 2a.3). Several thinly mineralized (silica and
Preferred lithologies are fine-grained limestones, pyrite), high-angle normal faults recognized in old
highly permeable coarse-grained sediments such as underground workings at Smelter support this view
packstones, several types of coarse sandstones, and (e.g., SD CM4-588).
monomictic to polymictic breccias of granule to On the basis of drill core correlations, it can
pebble size, all of them typical of the lower series be stated that the fluids that formed the silica-pyrite
of the Calera Member. The non-replaced intervals replacements migrated outwards from the inner
are dominated by massive, fine-grained argillites and parts of the Marcapunta volcanic complex, where
marls, usually rich in organic matter. The lithological they formed essentially veins. As the fluids flowed
contrast between replaced non-replaced intervals upward, they encountered a thick pile of mainly
suggests that permeability exerted a primary control carbonate rocks where they formed mantos but
in channeling of the early hydrothermal fluids also cross-cutting structures (Figure 2a.3). In this

W
4,400
E
4,400
CM4-588-95 CM9-588-05 CM8-588-96
CM1-588-95 4,350.479 242.05m.
4,348.257 227.30m.
4,344.225 218.00m.
CM6-588-96 CM10-588-06
4,348.732 261.55m.
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 4,200

221.95
E - 361,400
E - 361,000

0 10 50 100

4,000 METERS

MINERALIZATION GEOLOGICAL UNITS

Silica-pyrite replacement Calera Formation carbonates (Eocene)

Cu-(Au-Ag) zone Shuco Member (Eocene)

Zn-Pb-(Ag) zone
Dome

Mitu Group (Permian-Triassic)

Figure 2a.4: East-West cross section of the Smelter deposit as indicated in Figure 2a.2.

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
CHAPTER 2

northern sector, from Marcapunta to Colquijirca, of the district, has allowed discrimination of three
fluid movement was essentially from south to mineral stages. They developed their own zoning
north, possibly controlled by faults related to the patterns, each of which consists of distinct and
compressive tectonism (Chapter 1a). The pronounced contrasting zones. These stages are: (i) an Early silica-
flatness of the manto-like silica-pyrite replacements pyrite stage which produced the large silica-pyrite
in cross and longitudinal sections (Figures 2a.3 and replacements; (ii) a Main ore stage which deposed
2a.4) demonstrates that hydrothermal fluids, once arsenical Cu-(Au) minerals surrounding the volcanic
introduced into the carbonate unit, were restricted complex and rich Zn-Pb-(Ag) ores in their external
to lateral migration within the Pocobamba sequence. parts (Figures 2a.2 and 2a.4); and (iii) a Late ore stage
A similar general longitudinal migration pattern is which generated gold-free copper minerals.
recorded in the southern sector of the district where In general, a given mineralized portion is
the fluids seem to have been controlled by the north- constituted by a sequence of overlapping mineral
south fold axes toward the Zn-Pb-(Ag) deposit at associations and/or assemblages corresponding
San Gregorio (Figure 2a.1). to at least two of these three stages. For example,
The available drill core data indicate that the Late ore stage is found to overprint internal or
besides the main longitudinal fluid flow to the north external zones of the Main ore stage, which in turn
and south, fluids also spread in all directions from may overprint early silica-pyrite replacements. More
the central portion of the volcanic center, possibly, as complex associations may be related to processes of
early postulated by McKinstry (1936), following the zonal migration typical of these classes of sulfide-
margins of the sub-volcanic conduit. Paraphrasing rich deposits (e.g., Sales and Meyer, 1949).
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 Early silica-pyrite stage
entered along the beds from the margins of the stock, traveling
gently upward along the pitch. Only recently, has it been In virtually any portion of the Smelter deposit,
proved, using old drill-hole evidence that the entire an early pre-ore stage composed essentially by silica
western sector of the Marcapunta center hosts a and pyrite is evident. This stage, although economically
significant Cu-(Au) resource (Vidal et al., 2004). uninteresting, is by far the most important in terms
The copper orebodies are mostly hosted by the of volume. An estimated 800-1,000 millions tones
early silica-pyrite replacements. Because of the widely containing an average of 40-50 volume % pyrite
spaced nature of the drilling, delineation of individual exist in the Smelter deposit, and a similar volume
structures is difficult (Figure 2a.3). Available drill probably exists in the recently defined Marcapunta
hole and underground evidence indicates that the Oeste resource.
orebodies are distributed irregularly within the silica- The Early silica-pyrite stage displays distinct
pyrite replacements and that they commonly display textures depending basically on the lithofacies of
crosscutting geometry. Veins mostly reopen the early the host rock. In carbonate rocks of the Pocobamba
silica-pyrite veins within the volcanic complex (DDH Formation, the silica-pyrite stage formed a wide
BROCAL 524, 450-500 m depth). Copper mantos range of textures. In terms of volume, the most
also occurs within the silica-pyrite replacements, important are those formed by simple replacement
apparently constrained by inherited barriers. Relict of limestones and/or dolostones, marls, calcareous
bedding in the Calera Member appears determinant argillites and conglomerates, in which some of the
in the upper mineralized sequence, whereas it seems original fabric of the host rock is preserved (Figure
less important in the lower sequence where the 2a.5). Finely laminated textures composed of alternate
probable main barriers were the Calera-Shuco and pyrite- and quartz-rich bands are characteristic of
Shuco-Mitu contacts. many intervals, particularly toward the top of the
The silica-pyrite replacements themselves, mineralized sequence (Figure 2a.5). Lamination is
which developed extensive intergrain microcavities observed even at a microscopic scale with individual
(up to > 1 mm wide), provided secondary permeability bands as thin as a few tens of microns. Judging by
along which fluids flowed, enhancing the lateral their stratigraphic position above the top of the Mitu
fluid migration which controlled the shape of the Group, these banded intervals correspond to varved
mantos. carbonaceous dolostones and limestones, typical
of the upper sub-member of the lacustrine Calera
Member. Other textures also mimic the original fabric
Mineral deposition history: stages and of the carbonate rocks, and it is relatively common
zoning to observe biogenic textures completely replaced by
silica-pyrite.
The spatial configuration of ore bodies, Strongly silicified and pyritized conglomeratic
crosscutting relationships at different scales and the beds characterize the sequence below the Calera
study of more than 180 polished and thin sections Member. This sequence consists of alternating
distributed systematically along the northern block 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
CHAPTER 2

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

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

elongate and <10 m long, of electrum grains minute inclusions, exclusively in enargite. In similar
within enargite (Figure 2a.7). The grains are mainly form, unidentified Bi and Ag minerals, shown by EDS
located either along the cleavage or between grains tests, may have been introduced coevally. Economic
of enargite, suggesting that the gold precipitated argentiferous intervals may in part be explained by
together with enargite or postdated it. In a few these Ag-bearing phases. The observations indicate
examples, the grains partially fill minute cavities that all of these extremely fine-grained phases tend
in enargite without any apparent crystallographic to be more abundant in late enargite generations.
control; again the gold could have precipitated with As mentioned above, alunite, quartz and zunyite
or later than enargite. The tiny gold inclusions were are also found in pyrite II veins. Alunite occurs largely
likely deposited relatively late in the Main ore stage as platy euhedral grains intimately intergrown with
because most of the electrum occurs with the latest quartz and zunyite (Figure 2a.8). The best developed
enargite generations. and largest grains, up to 5 mm in size are pinkish and
A second occurrence of gold deposition is translucent and found in small geodes and fractures.
associated with blebs, up to 50 m in diameter, of Te- Whitish grains are also common but usually do not
bearing phases, including locally abundant goldfieldite exceeds 1 mm in size. Massive friable blades of fine-
and tennantite. The blebs replace late generations of grained alunite and variable amounts of minute
enargite and seem to have fed along grain boundaries. euhedral quartz grains, typically less than 2 mm
The gold occurs chiefly as tellurides, with minor across are locally volumetrically important. Reversals
amounts of extremely fine-grained electrum (<5 m in crystallization sequences without evidence of
in size) as inclusions in goldfieldite. The identified reaction between pyrite II-alunite and pyrite II-quartz
gold tellurides are kostovite and nagyagite (Figure pairs, are common. Euhedral pyrite II grains are
2a.7). Goldfieldite is observed in places to be zoned encapsulated in alunite and vice versa (Figure 2a.8).
and alternating with bands of tennantite (Figure 2a.7). These observations suggest that alunite, pyrite II and
Overgrowths of Te-bearing phases and tennantite on quartz were precipitated essentially coetaneously and
enargite grains have are also observed (Figure 2a.7). in chemical equilibrium (see also chapter 4).
Silver tellurides also occur in such blebs. Approximately 40 % of the enargite in the
Microprobe analyses (Table 2a.4) prove the presence Cu-(Au-Ag) zone is found in direct contact with
of stutzite and combined EDS tests and polished alunite. Commonly, alunite accompanied by quartz
section properties suggest the presence of hessite and subordinate pyrite comprises veinlets that cut
(Appendix 2a.3). Other gold- and/or silver-bearing and/or replace enargite. A reversed paragenetic
tellurides seem to occur but they were not tested via sequence is also common and mainly occurs as
microprobe. These silver tellurides occur intricately enargite filling intergranular spaces within alunite.
intergrown with the gold tellurides, goldfieldite and Most of the enargite in contact with the alunite that
native tellurium (Figure 2a.7). It seems that these precipitated paragenetically late displays the effects of
silver minerals do not contribute substantially to the strong corrosion and recrystallization using infrared
silver values found in most argentiferous intervals. imagery, commonly with no evidence of the original
Two inclusions of native iridium in enargite, grain morphology. Subordinately, enargite occurs as
both only a few microns in size were recognized intimate intergrowths with euhedral grains of alunite
through EDS tests (Appendix 2a.3) and polished in open spaces (Figure 2a.6).
section. Like the tiny electrum inclusions in enargite, Under the microscope, alunite displays highly
iridium deposition is assigned to the Main ore variably birefringence with a relatively well defined
stage. Ferberite is common in the Cu-(Au-Ag) pattern depending on the distance to the main
zone, particularly within 500 m of the Marcapunta Marcapunta magmatic center. The birefringence
complex. Euhedral prismatic grains, sometimes attains second-order blue in the innermost parts, with
twinned and up to >100 m in size, were observed a tendency to lower first-order grey to yellow in the
in numerous enargite-rich samples. Ferberite mainly rest of the zone. Observation with the SEM shows
occurs paragenetically later than enargite and Main that alunite usually consists of two discernable phases
ore stage quartz (quartz II, see below). Tungsten of APS (aluminum phosphate sulfate) group minerals
concentrations determined by ICP analysis indicate (Figure 2a.8). Cores identified with microprobe
that it correlates well with Cu and As, thereby further analysis are dominated by the woodhouseite series
supporting this view. Tungsten values may attain whereas rims are composed largely by the alunite
0.6 wt. %, but more typically 0.05-0.2 wt. % (see W series, essentially pure alunite. The cores, although
concentrations up to >4000 ppm in Appendix 2a.2). sometimes corroded in appearance, generally displays
Other accessory minerals precipitated during well-developed oscillatory zoning. Seen in detail,
the Main ore stage are bismuthinite, which may be the core is made up of dense bands, which became
locally abundant (up to 0.5 volume %), and more progressively less abundant towards the borders of
rarely, emplectite and stannoidite. They occur as the grains (Figure 2a.8).
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 Cu-(Au-Ag) zone. It consists of euhedral tetragonal
pure gold and pure silver end members. pyramids (Figure 2a.8), sometimes truncated with an

59
CHAPTER 2

octahedral form. The grains can reach 2 mm wide Enargite compositions are nearly stoichiometric
and are translucent. Occurrence of zunyite without (Table 2a.1). All measured antimony contents are
alunite is uncommon. Mutual relations of the pyrite below 1.5 wt. %, but in general between 0.5 and 1.0
II-zunyite pair are similar to those of pyrite II-alunite. wt. %. Sn displays similar concentrations (0.3-1.5 wt.
For example, euhedral pyrite grains are encapsulated %). Less abundant elements are Zn and Fe (<0.3 wt.
within zunyite but the reverse, although rarer, has %), and more rarely Bi (<0.3 wt. %). Another minor
also been noted. element detected in some cases to be economically
Quartz occurs mostly as an accompaniment significant is Ag (mainly in the range of 0.1 to 0.3
to alunite-(zunyite). In common with the distinction wt. %, up to 0.6 wt %). Luzonite compositions are
made between Early stage pyrite I and Main ore also close to stoichiometric. The mineral shows
stage pyrite II, quartz deposited during the Main considerably higher Sb contents than enargite, ranging
ore stage is called quartz II. This quartz II is grossly steadily from 0.5 to 2 wt. %. The minor elements, Sn
euhedral and highly variable in size. Tiny grains occur and Fe, are equally more concentrated in luzonite (up
in intricate intergrowths with alunite and zunyite as to 3.0 and 1.0 wt. %, respectively).
part of pyrite II veinlets. Larger quartz grains are Main ore stage pyrite II is largely nearly
observed intergrown with enargite but lacking the stoichiometric (e.g., Table 2a.2 and Appendix 2a.1).
alunite-zunyite pair. Minor amounts of clays are As recognized in pyrite I grains from the Early
observed locally accompanying this quartz. Quartz- silica-pyrite stage, the main elements responsible
enargite lacking alunite characterizes up to 60 % of for the zoning in pyrite II are arsenic and copper.
the enargite resource of the entire Smelter deposit. However, in contrast to pyrite I, copper is, by far,
Quartz with enargite is typically corroded where in more abundant. Copper contents were found to be
contact with later alunite. as high as 4.0 wt. %, but in general are between 0.5
Small amounts of dickite, kaolinite and, in and 1.5 wt. %. Similar high copper values in pyrite
places, smectite and illite are present throughout the were reported by Einaudi (1968) at Cerro de Pasco.
Cu-(Au-Ag) zone, particularly in portions devoid of Arsenic, in contrast, does not surpass 0.6 wt. %.
alunite-bearing assemblages. These clays typically Pyrite II as inclusions in enargite was found to be
fill intergranular spaces in enargite, pyrite II, and more frequently rich in copper (up to 3.2 wt. %).
quartz II. Where kaolinite and dickite are in contact Silver contents in pyrite II vary from below detection
with enargite, no reaction is observed (Figure 2a.6). limit in most of the analyses to 0.4 wt. %.
Furthermore, kaolinite, dickite, and apparently also Based on two analyzed samples, goldfieldite,
illite as inclusions in enargite have been observed to the Te-rich end member of the tennantite series,
display no reaction effects. A reconnaissance study contains up to 23.6 wt. % Te (Table 2a.2, Figure
of clay minerals carried out by Cominco in 1999 2a.7). Sb substitution for arsenic is important
suggests that most of the alunite-free enargite (main population between 1.5 and 5.2 wt. %); well-
bodies contain minor amounts of clays including, developed zoning observed in some cases is likely
besides kaolinite and dickite, some pyrophyllite, due to such Sb variations. Bismuth concentrations
illite and smectite. Observed in detail, again virtually are significant in all analyses (between 0.2 and 2.0
no reaction effects are observed between enargite wt. %). Other minor elements detected in significant
and clays and no alunite is observed to have co- concentrations are silver and vanadium, up to 0.8 wt.
precipitated with the enargite-clay assemblages. It is % and 0.3 wt % respectively.
therefore likely that important parts of the enargite Five samples indicate that tennantite associated
bodies macroscopically exempt of alunite (~60 % of with goldfieldite and gold-silver tellurides is ferriferous
the Smelter deposit) contain trace to minor amounts containing up to 7 wt. %. Antimony substitution by
of clays. As is generally <1.5 wt. %. No other element was
Significant amounts of hematite are observed detected to be a significant component of the Main
partially replaced by pyrite II. However, as explained ore stage tennantite. Ag contents are in general <0.1
later and based on observations at district-scale, the wt. % (Table 2a.2).
hematite is thought to be a remnant mineral from Only 16 grains of electrum were sufficiently
external parts of the system, i.e., from Zn-Pb-(Ag) large for microprobe analysis. All of them belong
parts, that have been almost entirely replaced by to the first gold deposition period of the Cu-Au-
mineral associations from the internal Cu-(Au-Ag) (Ag) Main ore stage. The results show a relatively
zone. 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
Composition of minerals of the Cu-(Au-Ag) zone grains, copper values were found to be appreciable
(up to 4 wt. %).
A selection of representative microprobe Native tellurium (App. 2a.3) is virtually pure.
analyses of enargite, luzonite, pyrite II, tennantite, Only insignificant concentrations of Cu and Au were
goldfieldite and accessory minerals is given in Table detected in the five analyzed points (<0.4 and 0.3 wt.
2a.1. %, respectively). A few quantitative data on kostovite,

60
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 also alunite with similar Na/K values (<0.1). These
Table 2a.3. Similarly, limited data on other accessory compositional variations recorded in single grains
minerals from the Main ore stage of the Cu-(Au-Ag) seem to characterize perhaps nearly half of those
zone, including stannoidite, are shown in Table 2a.2. recognized in alunite from the inner Cu zones of the
and Appendix 2a.1. Smelter deposit, including the Cu-Au-(Sn-Ag) and Cu-
Over 50 analyses from six widely spaced (Ag) zones. In the remaining examples the grains are
alunite samples from the Cu-(Au-Ag) zone were alunite with Na/K ratios ranging typically from 0.03
analyzed using the electron microprobe. Table 2a.4 to 0.08, and rarely, >0.20 (Table 2a.4). Birefringence
presents a selection of the alunite compositions changes observed in thin sections seem to bear no
found in this survey. High-energy bands, observed evident relation to compositional changes of either
in the cores of grains in SEM images are generally major or minor elements.
rich in P2O5 (0.12-0.20 wt. %), with the A site largely Limited microprobe analysis was conducted
occupied, to varying degrees, by Sr, Ca and Pb on a few grains of zunyite from two alunite-bearing
(woodhouseite series). These woodhouseite-series samples. The analyses revealed nearly stoichiometric
bands are the most enriched in fluorine (up to 2.1 compositions. Zunyite has chlorine contents between
wt. %; Table 2a.4). Towards the rim, the high-energy 2.65 and 3.4 wt. %.
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 Cu-(Ag-Sn-Bi) zone
free of Sr, Ca, and Pb. In instances in which instead
of oscillatory bands, the cores of the grains consist The enargite Cu-Au-(Ag-Sn-Bi) zone displays
of a single zone, usually corroded, it is even more essentially the same associations and assemblages as
enriched in P2O5 (up to 0.46 wt %) but Pb-free and, the enargite Cu-Au-(Ag) zone, but with significantly
more rarely, Ca-free. In such examples, the core may higher tin and bismuth concentrations. This zone is
reach the svanbergite end-member composition. A recognized mainly between 588 and 628 lines (Figure
particular feature of this second type of core is its 2a.2). Typical tin concentrations range between 500
high cerium content. The rim in this second case is 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. The relationship between the strong zoning and
Gold contents in this zone (~0.6 ppm) are slightly compositional variations has not been investigated;
lower than in the Cu-(Au-Ag) zone. Bismuth however, elemental substitution in the R site (Sn,
concentrations are generally on the order of 100 ppm, As, Sb) suggests that such a relationship exists. For
but numerous intervals of a few meters may exceed example, Sn ranges from 4.9 to 9.2 wt. % in a single
0.3 wt. %. In many mineralized intervals, these high grain, coincident with decrease in As+Sb from 10.4
bismuth values are linearly correlated with high silver to 5 wt. %. Antimony contents of colusite are >2.3
concentrations, which can be up to >10 oz/t. wt. % (typically 0.8-1.6 wt. %). The few analyzed
Colusite is the most important tin mineral, not grains of stannoidite are essentially stoichiometric
only in this zone but in the whole Smelter deposit. It (Table 2a.2). The minor elements Zn, As, and Sb
mainly occurs as strongly zoned euhedral grains up to together account for <4 wt. % (<2.6, 1.2 and 0.8,
1mm wide (Figure 2a.7). The grains are pyritohedral respectively).
in form although cubes are occasionally discernable. Two analyzed electrum grains from this zone,
Colusite shows sector zoning and stronger reflection with Au and Ag contents of ~96 wt. % and 4 wt. %,
pleochroism than that described by Ramdohr (1980). respectively, yielded higher gold contents compared
Colusite typically replaces enargite and especially to those encountered in the Cu-(Au-Ag) zone. Copper
pyrite II (Figure 2a.7). Only locally does enargite is also very low (Table 2a.3). Alunite compositions in
replace colusite along fractures, cleavage, and three samples from the Cu-Au-(Sn-Ag) zone show
growths planes. Some pyrite II shows no reaction no significant compositional change from those
effects against colusite suggesting that, in places, they described from the inner Cu-Au-(Ag) zone.
may constitute an equilibrium assemblage. Moreover, Some drill holes effectuated in the Cu-(Ag-Sn-
much of the colusite is observed to be in reaction- Bi) zone (e.g., DDH-CM5-580) intercepted Zn-Pb-
free contact with alunite, zunyite, and quartz (Figure (Ag) bodies consisting largely of sphalerite, galena,
2a.8). pyrite, siderite, hematite and kaolinite. This mineral
Stannoidite is a minor to trace tin mineral often, association predated that typical of the Cu-(Ag-Sn-
but not necessarily, associated with colusite. It occurs Bi) zone. The contacts between Zn-Pb-(Ag) and
as irregular blebs on the edges of quartz, enargite, enargite-bearing assotiations are sharp with clear
or alunite clusters. In general, where stannoidite and evidences that the latter overprints and cuts the
colusite are in contact, the former replaces the latter. sphalerite-galena bodies. It is possible to appreciate
A second extremely fine-grained phase accessory how thin veinlets of enargite or pyrite-alunite
is intergrown with colusite. Optically it resembles penetrate the sphalerite-galena bodies in the vicinity
vinciennite, but a definitive identification is lacking. 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 The enargite Cu-(Ag-Bi) zone roughly
Cu-Au-(Ag-Sn-Bi) zone, including enargite, coincides with the sector between lines 644 and 700
luzonite, pyrite II, tennantite and goldfieldite, were lines and extends to the Colquijirca deposit, where
quantitatively analyzed from several representative it contains lesser amounts of bismuth (Figure 2a.2).
samples. No major variations in compositions relative At Smelter, a mineralogical characterization of this
to the Cu-(Au-Ag) zone were detected. zone is difficult because of the pervasive overlap
Colusite compositions are close to of the Late ore stage, particularly well developed in
stoichiometric and are summarized in Table 2a.1. 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 substantially contribute to the silver enrichment of
minor replacement by the Late ore stage. any given zone.
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 Zn-Pb-(Ag) zone
(<0.15 ppm) and Sn contents (<100 ppm)(Appendix
2a.2). Copper and Ag values are, on the other hand, Laterally, surrounding considerable portions
higher than those in the inner zones (~2.5 wt. % of the copper-rich core of the Smelter deposit,
and 40 ppm, respectively). In accordance with the economically interesting Zn-Pb-(Ag) intervals have
metal contents of this zone, tin minerals are much been drilled. They become richer northward from
less abundant than in the Au-(Ag-Sn-Bi) zone. Only line 668 as well as both eastward and westward, as
occasionally is some minor colusite observed. shown in Figure 2a.4. Some of these intervals, such
Mineralogically, the Cu-(Ag-Bi) zone does as those located in the most external portions of
not differ much from the other inner copper zones. the sector between lines 572 and 580 (Figure 2a.4),
Enargite-(luzonite) is always the main copper mineral constitute true Zn-Pb-(Ag) orebodies with average
and minor phases are generally the same as those grades of 6 wt. % Zn, 2.3 wt. Pb and 2.0 oz/t Ag .
present in the inner zones. Similarly, in terms of The characteristics of the transition from the
chemical composition, no significant variations in the Cu-(Ag-Bi) to the Zn-Pb-(Ag) zone are unknown
main minerals were found. because the drill holes cut the Zn-Pb-(Ag) ore some
A particular feature of the Cu-(Ag-Bi) zone 150 to 200 m beyond the outermost hole in the Cu-
compared to the other enargite zones is the greater (Ag) zone.
abundance of Ag-and Bi-rich intervals. Silver grades The Zn-Pb-(Ag) zone largely comprises
rarely surpass 10 oz/t over metric intervals (generally siderite, sphalerite, galena, specular hematite, pyrite,
~1.5 oz/t compared to 0.7-0.9 oz/t in the other and kaolinite-(dickite). The contacts with the host
copper zones). Bismuth values measured by AAS rock are sharp and strongly controlled by bedding,
increase to >0.5 wt. % over metric intervals (e.g., suggesting that they form manto-like bodies (Figure
DDH SM-676, 136-143 m). Silver and Bi values 2a.4). The mineralized intervals alternate with partly
show good linear correlations. As is the case in the unaltered carbonate rocks and, most importantly,
Cu-(Ag-Sn-Bi) zone, these values have their origin with intervals having significant copper contents.
in extremely fine-grained unidentified Bi- and Ag- These cupriferous intervals are roughly located in the
bearing minerals present as inclusions in enargite- central portions of the mineralized body, strongly
(luzonite), as recognized through EDS tests. Another suggesting that the Zn-Pb-(Ag) mineralization
plausible possibility is substitution of copper by constitutes particularly well-developed peripheral
silver in the enargite lattice. As Ag concentrations Zn-Pb-rich zones in a classic zone pattern, in which
in enargite are as high as 0.6 wt. %, they could the Cu ores occupy the central parts.

63
CHAPTER 2

Sphalerite and galena are coarse-grained and the chalcocite-dominated ones, in relatively distal
fill intergrain spaces within siderite or are intricately positions. One such zone, the most important in
intergrown with it. Sphalerite-galena textural terms of volume, is located at Smelter Norte, a sector
relationships are relatively complex. The most comprised between lines 636 and 700 (Smelter Norte
obvious case is where sphalerite replaces galena sector; Figure 2a.2). In this sector, there is pervasive
or coats cleavage surfaces within it. Sphalerite and replacement of the three enargite-bearing zones of
galena typically replace pyrite and, in some places, the the Main ore stage by tennantite-bearing associations,
replacement may be complete. Pyrite in the Zn-Pb- including combinations of chalcopyrite, chalcocite,
(Ag) zone is of two main types: one coarse-grained covellite, digenite, bornite and rare copper sulfosalts.
and generally replaced by sphalerite and galena, and Tennantite displays intricate intergrowths with these
the other generally fine-grained. Marcasite is observed copper various minerals.
in contact with pyrite either as rims or replacing it. Also at Smelter Norte, thin sphalerite veins
Kaolinite and, rarely, dickite are observed to replacing chalcocite (covellite) have been observed
fill any free space left after sphalerite and galena in a few places (e.g., DDH CM-668, at 163 m),
precipitation. No textural evidence of reaction although in none of them is galena volumetrically
between kaolinite-(dickite) and siderite or kaolinite- significant. No microprobe data are available from
(dickite) and sphalerite-galena was observed. 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
Composition of minerals of the Zn-Pb-(Ag) zone of sphalerite from the outer Zn-Pb-(Ag) zone.
Economically important Late ore stage
A few grains of sphalerite in this zone were chalcocite bodies were recently found in the
analyzed (Table 2a.1). FeS contents range from 1.6 Marcapunta Oeste project area. The bodies appear, as
to 3.4 wt. mol %, with insignificant amounts of Mn at Smelter, to be structurally controlled by subvertical
and Cd. 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
Late ore stage white sericite.

The three enargite-bearing mineral associations


and assemblages from the Main ore stage are Composition of minerals of the Late ore stage
overprinted by two main cupriferous mineral
associations, one dominated by chalcocite and the A few quantitative chalcocite analyses were
other by tennantite. The temporal relation in time obtained. Several chalcocite grains occurring as
between these two associations are not clear but, on an overprint to the Cu-(Au-Ag) zone yielded
the basis of irrefutable crosscutting relationships compositions close to stoichiometric. In contrast,
indicative of a late timing, may be assigned to a single chalcocite from the Cu-(Ag-Bi) zone at Smelter Norte
Late ore stage. The outermost Zn-Pb-(Ag) zone of shows considerable compositional deviation from
the Main stage is not affected by this overprinting. stoichiometry, with Cu/S ratios most commonly
A chalcocite-bearing association is recognized between 1.7 and 1.9, as well as under reflected light
throughout the entire Smelter deposit, but generally and in reflected light being anisotropic.
it does not constitute ore. Chalcocite forms irregular Compositionally, tennantite from the Late
masses and is never observed to be well crystallized. ore stage differs significantly from that in the Main
Typically, chalcocite replaces enargite along fractures stage Cu-(Au-Ag) zone in both tellurium and zinc
and veinlets no more than a few centimeters thick. contents. No significant tellurium values were found
From these veinlets, chalcocite penetrates into the in any of the analyzed samples and zinc contents are
Main ore stage mineralization and may eventually remarkable high, commonly in excess of 2 wt. %. In
extensively replace not only enargite, but also pyrite general, Sb substitution for As is minor. Microprobe
II and other phases, including late gold-bearing analyses reveal generally low Sb concentrations (<1
tennantite. Chalcocite is also observed coating wt. %, though in one case up to 2.6 wt. %).
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,
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associations are best developed, in contrast to Barton, P.B., Jr., Bethke, P.M., and Toulmin, P., III,

64
CHAPTER 2

1963, Equilibrium in ore deposits. Symposium on the


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


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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
CHAPTER 2

2b. The Colquijirca deposit

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

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

76
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
CHAPTER 2

atmospheric oxidation. A remarkable similarity with developed than at Smelter, and a wider range of
pyrite I from the Smelter deposit, which serves as a zones as well as more generalized superimposition
distinction from later pyrite, is the octahedral shape. of them adds considerable complexity to the pattern
It usually occurs as subhedral and relatively rare found at Smelter. The Main ore stage (Figure 2b.6) is
euhedral grains, mostly slightly corroded. divided in four zones based on the main economically
The different textures observed at Smelter are interesting elements, from an innermost Cu-(Ag)
extraordinarily similar to those present in this inner zone to a Cu-(Ag-Bi) zone, a Zn-Pb-(Ag-Cu-Bi)
massive silica-pyrite manto at Colquijirca (Chapter zone, a Zn-Pb-(Ag) zone, and to an outermost Pb-
2.a). Among the most remarkable are the brecciated Zn-(Ag) zone.
and distinctly laminated textures. The brecciated
textures seem to be generated by multigenerational Cu-(Ag) zone
precipitation of silica-pyrite without any evidence of
ore deposition. This zone roughly mimics the Early silica-
From line 740 northeastward, only dark pyrite replacement body, but when observed in detail
decimetric beds characterize the silica-pyrite stage. the Cu-(Ag) zone is usually restricted to only the
These thin beds are, however, numerous, widespread internal parts of the silica-pyrite body (Figure 2b.3).
and persistent along the most external parts of the The Cu-(Ag) zone can be divided into three well-
Colquijirca deposit as well as at Condorcayn. The defined sub-zones, which are: an enargite-dominant
beds, known locally as chert, are most commonly core, a bornite-dominant sub-zone and a tennantite-
composed of dark to black cryptocrystalline material, dominant outer part.
including finely crystallized quartz, which, in general,
makes up no more than 30 volume % of the rock. Enargite-dominant sub-zone: Enargite
Under the microscope, these beds are seen to contain represents >95 volume % of the copper phases in this
<5 volume % of pyrite inclusions, <100 m in size. zone. Luzonite is only occasionally as significant as
The pyrite is slightly corroded. that in the Smelter deposit. Enargite is coarse grained
A generation of finely crystallized euhedral but not as coarse as that at Smelter. Commonly,
quartz forming small geodes is fairly common in striated acicular grains were observed to be as long
these thin outer dark silicified beds. The intimate as 4 cm. Most of the well-formed grains are found
intergrowths with sphalerite and galena, as well as in small druses in breccias. Typically, enargite is
fluid inclusion data, show that the euhedral quartz observed replacing Early silica-pyrite stage pyrite I to
was deposited during the subsequent Main Ore various degrees.
Stage. The bulk of the enargite is present cementing
Mineralogically this stage is very simple. hydraulic breccias, incipient crackle breccias, and
Sporadically, minute rutile grains (<40 m) are in veinlets. In all cases, deposition of enargite was
observed in the silica-pyrite mass. A significant contemporaneous with the brecciation. Enargite
difference with the silica-pyrite stage of the Smelter in hydraulic breccias can form massive aggregates,
deposit is the local presence of tiny sphalerite grains, which under the microscope appear as mosaics of
which like the rutile, appear to also be part of the anhedral grains without any sign of development
matrix. of crystal faces and showing abundant corrosion
Microprobe analyses of pyrite I show only and recrystallization features. In crackle breccias
minor amounts of As and Cu in its structure (up to and veinlets, enargite often occurs as coatings and
1 wt. % for both). No SEM study was performed on clusters, frequently with euhedral crystals, and with
this early pyrite but presumably, based on the similar corrosion being less common. Again, as in the case
composition to that of pyrite I from the Smelter of the Smelter deposit, an apparent relationship is
deposit, these elements would be largely responsible observed between dissolution and recrystallization of
for the marked zoning, which becomes visible upon enargite and the presence of alunite. At Colquijirca,
surface oxidation. 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,
Main ore stage which constitutes assemblages with quartzpyrite
II (see below), occurs without enargite (Figure 2b.3).
Interpretation of the main zoning of the In contrast, euhedral enargite is most commonly
Colquijirca deposit as the product of a single observed in contact with kaolinite and/or dickite
mineralization stage, postdating the silica-pyrite (see below).
stage, is supported by time-integrated elemental, Main ore stage pyrite in the enargite-dominant
mineralogical and geometric relationships similar zone (pyrite II) is volumetrically more important than
to those documented for the Smelter deposit. A at Smelter. It typically occurs as euhedral pentagonal
discussion of this interpretation is presented at the dodecahedral crystals up to 5 mm in size. Again, as at
end of this chapter. Smelter, pyrite II is strongly zoned. The largest pyrite
The zoning in Colquijirca is much better II grains are intimately intergrown with enargite,

78
CHAPTER 2

with common reversals in crystallization sequence dominant sub-zone. As previously noted, kaolinite
observed between them. Irregular blebs of pyrite II and/or dickite occur in contact with euhedral
in enargite are less rare than at Smelter. The most enargite, commonly without any sign of corrosion
abundant pyrite II population accompanies alunite or recrystallization. They mainly occur filling
and fine-grained quartz but is free from enargite. intergranular spaces in enargite as in much of the
This pyrite II is also pyritohedral and always well Smelter deposit.
crystallized. It occurs in direct contact with alunite The enargite-dominant sub-zone contains
without evidence of reaction and shows reversed numerous thick decimetric lenses and thinner beds of
overgrowths with the latter mineral. Similarly, sphalerite-galena-pyrite-hematite-siderite-kaolinite
fine-grained quartz II, in places showing reversed (Figure 2b.3). Crosscutting relationships indicate that
crystallization with alunite, and thought to have this mineral association predates the enargite sub-
co-precipitated with it, shows no reaction where in zone. An interpretation of this observation in terms
contact with alunite. The absence of reaction is a of advancement of the copper front with time is
prominent difference from the fine-grained-quartz I discussed at the end of this chapter.
from the Early silica-pyrite stage and the coarse grains In a similar manner as at Smelter, considerable
of quartz II coetaneously precipitated with enargite, portions of the enargite-dominant sub-zone are
which in places displays strong corrosion leaving only overprinted by chalcocite-bearing associations. Again,
a skeletal vuggy mold. As previously mentioned, the as in the Smelter deposit, these associations are
detailed mapping shown in Figure 2b.3 shows that attributed to a Late ore stage, as described below.
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 Composition of minerals of the Cu-(Ag) zone
beyond (Figure 2b.3).
In polished section, luzonite is relatively rare and A quantitative data set for the main phases
replaces enargite along its cleavage. It is unmistakably observed in this sub-zone from microprobe analysis
distinguished from enargite by its polysynthetic is available in Table 2b.1.
twinning and pale pinkish colour. Other trace phases Enargite is largely stoichiometric. Antimony
occurring as minuscule wisps within enargite, and substitution for arsenic seems to be more important
more rarely, within pyrite I, are stibnite, emplectite, than at Smelter, but this assumption is not definitive.
and very small grains of unidentified bismuth-bearing Silver is concentrated in amounts as high as 1.1 wt. %,
minerals. similar to enargite in the outer Cu-(Ag) zone of the
Alunite is distributed throughout the entire Smelter deposit. No analyses were run for luzonite.
enargite-dominant sub-zone (Figure 2b.3). As A few analyzed grains of pyrite II show that it
previously mentioned, it occurs as an assemblage with is essentially stoichiometric. Copper and arsenic were
fine-grained euhedral pyrite II with which it displays found to be <0.2 wt. %.
reversed overgrowths and intricate intergrowths. Two widely-spaced alunite samples were
Alunite is typically platy and has a translucent whitish subjected to microprobe analysis. Multipoint
not pinkish tone in contrast to that in the inner zones traverses of several grains from core to rim show no
of the Smelter deposit. Relative to the Smelter alunite major compositional variations. The analyzed grains
it is finer grained and grains perpendicular to the c axis plot in the alunite end-member field, with typical
are much thinner. Alunite typically fills intergranular Na/K ratios of <0.1. Relatively minor substitution
spaces in enargite and quartz, both the quartz I from of K by P in the R site is sporadic. Similarly, no
the Early silica-pyrite stage and fine-grained quartz significant K substitution for Ca and Sr was found.
II (Figure 2b.4). In places, hydraulic breccias are More importantly, for purposes of comparison
cemented by the alunite-pyrite II-(quartz) assemblage, with alunite from the Smelter deposit, virtually no
suggesting that these minerals were deposited from Pb was encountered to occupy the A site of alunite
the introduced fluid. Detailed mapping shows that from this enargite-dominant sub-zone. Based on the
alunite-bearing assemblages are not restricted to the microprobe traverses, only subtle fluctuations in the
enargite-dominant sub-zone but extend upward into Na/K ratios are irregularly recorded.
the immediately overlying Zn-Pb-(Ag) zone, where
they coexist with sphalerite and galena, and into the
bornite-dominant sub-zone (Figure 2b.3). Bornite-dominant sub-zone: This zone
The absence of zunyite is a main difference appears to occur in gradational contact with the
between the enargite-dominant sub-zone of the enargite-dominant zone. Over an interval of <60
Colquijirca deposit and most of the enargite-bearing cm, bornite increases in volume and enargite virtually
zones in the Main ore stage of the Smelter deposit. disappears. In terms of tonnage, this zone makes up
Similarly, no significant pyrophyllite was detected in no more than 5 volume % of the entire Cu-(Ag)
this sub-zone. zone and forms small discontinuous pod-like bodies,
Kaolinite and dickite are common, though in part surrounding the enargite-dominant sub-zone
minor phases accompanying enargite in the enargite- (Figure 2b.3). These pod-like bodies measure up to 10

79
CHAPTER 2

m long, 4-6 m wide, and 2-3 m thick. Copper grades circulating prior to bornite formation. Pyrite showing
are high, in places exceeding 5 wt. %, but this sub- corrosion in contact with bornite is observed to be
zone is not mined for Cu because of its small tonnage. appreciably replaced by sphalerite, suggesting that it
The bornite-dominant sub-zone is observed only formed even earlier, possibly from the Early silica-
along the strike, both laterally, and most importantly, pyrite stage.
frontally relative to the main direction of ore fluid Among the minor phases observed in this sub-
movement (Figure 2b.3). Only at one point, a few zone, chalcopyrite occurs as blebs within bornite or
decimeters thick and 1 m long, a pod of bornite-rich sometimes as veinlets that seem to follow cleavage in
ore was observed to immediately overlie the enargite- the bornite. Enargite is present interstitial to quartz
dominant zone (perpendicular to bedding). grains in an undefined temporal position relative
The main mineral association in this sub-zone to bornite. Another minor phase observed in one
is bornite-tennantite-pyrite-sphalerite-quartz-barite, sample is thought based on its optical properties,
dickite-(kaolinite) and a phase presumed to belong to to be mawsonite,. It occurs between broken bornite
the APS group, possibly alunite. Minor components fragments which display matching contacts.
are covellite-chalcopyrite-chalcocite-digenite-galena- Accessory phases recorded with EDS tests
(siderite) plus other trace phases. In this association, are bismuth-antimony-copper-bearing grains. They
part of the pyrite, quartz, and sphalerite clearly occur as <10 m blebs in pyrite and occasionally in
predate bornite deposition, while the rest of the bornite.
minerals precipitated after bornite. Quartz in the bornite-rich sub-zone is
Bornite accounts for up to 30% of the rock, is abundant, and typically euhedral and relatively coarse
never observed in well crystallized form and typically grained (up to 1 cm). It constitutes up to >50 volume
occurs as irregular masses. At the microscopic scale, % in some portions of the bodies. According to the
bornite displays abundant dissolution voids, usually type of mutual contact with bornite and/or dickite-
filled with dickite-(kaolinite) (Figure 2b.4) and, more (kaolinite)-APS mineral?, quartz may be divided into
rarely, with a finely crystallized APS group mineral, two types. The first, and volumetrically most important
possibly alunite. In most places, bornite grew (70-90 %), shows no evidence of reaction in contact
interstitial to the silica matrix, largely euhedral quartz with these minerals. The second, less abundant
with open-space filling textures. These textures show type of quartz, shows significant corrosion when
that bornite either co-precipitated with quartz or in contact with both bornite and dickite-(kaolinite)-
postdated it. As described below, bornite infillings APS mineral?. Based on these relationships, it is
within pyrite and barite are also observed. considered that the quartz precipitated both earlier
Pyrite from the bornite-dominant sub-zone than bornite and contemporaneous or postdating it.
is typically pentagonal dodecahedral and relatively Resorption of quartz is more pronounced in contact
coarse grained (up to 0.5 cm). It often occurs as with dickite-(kaolinite-) and the APS mineral?. These
clusters rimmed by bornite. In most examples, pyrite facts, as mentioned above, suggest that the bulk of
shows no reaction effects in contact with bornite the quartz, together with pyrite and sphalerite, could
(Figure 2b.4). However, it is relatively common to well be product of same earlier surge of fluids that
observe pyrite slightly to moderately replaced by predated bornite deposition and argillic to advanced?
bornite. Where bornite cements brecciated pyrite argillic alteration minerals.
grains, which are angular and not resorbed, there is Apart from quartz, barite is the most
no reaction effects. Similarly, in bornite stockworks important gangue phase in this sub-zone, accounting
cutting euhedral pyrite, the fragments of the latter for between 2 and 10 volume %. Barite is euhedral
mineral have matching contacts and do not show and typically coarse grained (0.5 - 2 cm). Its form is
any evidence for reaction. A minor bornite fraction invariably tabular, although occurring in two habits.
occurs as late wisps in this pyrite, partially filling Predominantly, the barite is dispersed through a mass
minute fractures. of anhedral pyrite and/or bornite. Less frequently,
All the observed sphalerite and much of the barite occurs as overgrowths on pyrite, and more
quartz have a temporal position similar to or even rarely bornite. Minute bornite inclusions within barite
earlier than that of the pyrite showing no reaction are not rare. These occurrences of bornite are highly
when in contact with bornite (Figure 2b.4). Sphalerite, suggestive that barite co-precipitated from the same
extensively replaced by bornite, clearly predated this fluid stage which deposed bornite. As described above
mineral (Figure 2b.4). In places in which sphalerite kaolinite-(dickite) and the APS mineral? typically fill
is in contact with pyrite, no reaction is observed vugs in bornite and quartz.
between them. Similarly, common bornite-infillings Quantitative data obtained from electron
within quartz, as described below, are indicative of microprobe analysis is limited. Only one representative
earlier crystallization of the latter mineral. The early sample was studied by this technique. Bornite
timing of the bulk of the quartz, pyrite and sphalerite, showed mostly stoichiometric compositions (Table
combined with microprobe analyses typical of more 2b.1), although some analyses yield compositions
external Zn-Pb-bearing zones, suggests that these which deviate significantly from stoichiometry.
minerals were formed from the same fluid as that More precisely, an excess of copper was found

80
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
CHAPTER 2

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

82
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. Barite is the most important associated gangue
Native silver is relatively common in the mineral in this sub-zone. Besides clusters of perfectly
tennantite-dominant sub-zone, where it typically formed and translucent tabular grains of museum
occurs growing on tennantite and/or barite (Figure quality, it occurs in a similar habit to that in the bornite-
2b.4). Several undefined argentiferous sulfur-bearing rich sub-zone. Minuscule tennantite inclusions in
phases are associated with this form of native silver. barite are common. Reversed crystallization between
This particular sample reported nearly 23 oz/t Ag barite and tennantite is also observed. All these
in an atomic absorption analysis provided by the observations suggest that barite deposited coevally
company laboratory. with tennantite.
The extremely high silver contents (>40 oz/t Dickite and kaolinite may locally be important.
Ag) in significant parts of the tennantite-dominant The style is the same as that observed in the bornite
sub-zone are ascribed to associations containing sub-zone, where they fill all types of cavities including,
stromeyerite, native silver, rare Ag-bearing sulfides most importantly, dissolution vugs and intergranular
and, in places, Ag-rich tennantite. spaces. Where dickite and kaolinite are in contact

83
CHAPTER 2

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

84
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 particularly along the main NE-SW ore-fluid flow
in the Colquijirca deposit, which prior to mining may direction (Figure 2b.1, Figure 2b.5). In these places,
have exceeded 30 Mt at 6 % Zn, 3 % Pb, and 3.5 oz/t abundant siderite containing significant amounts of
Ag. zinc and manganese occurs in contact with kaolinite
In the inner parts of the Zn-Pb-(Ag) zone, and dickite without evidence for reaction (Figure
sphalerite and galena are accompanied by several 2b.5).
mineral assemblages depending on the spatial position The outer parts of the Zn-Pb-(Ag) zone are
and distance from the Cu-bearing zones. For example, mineralogically uniform. Besides sphalerite and
sphalerite and galena intergrown with alunite and galena, hematite is the characteristic mineral in this
barite are present immediately overlying the enargite- zone (Figure 2b.5). It typically occurs as relatively
dominant sub-zone in the Cu-(Ag) zone (Figures coarse-grained specular hematite intergrown with Zn-
2b.3 and 2b.5). On the other hand, sphalerite and bearingg siderite and kaolinite. Other characteristic
galena are accompanied by kaolinite and/or dickite but less abundant minerals from the outer portions
lateral to the Cu front (along the strike of bedding), 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 Ahfeld (1932) was the first to recognize
(Figure 2b.5). chalcocite to be of hypogene origin. He described it
The Zn-Pb-(Ag) zone displays gradational replacing enargite in the pyritic manto, very likely
mineralogical variations with increasing distance from in the enargite-dominant sub-zone. But chalcocite,
the Cu-bearing zones. An increase in the FeS content as defined in this study, is always associated to other
of sphalerite from ~0.1-0.3 wt. % in assemblages minor copper phases that systematically cut the
containing kaolinite-dickite-(alunite) to 1- 3 wt. % in components of the Main ore stage throughout the Cu-
siderite-kaolinite-bearing assemblages is noticeable in (Ag) zone. Other distinct associations also crosscut
the outer parts of the Zn-Pb-(Ag) zone (Table 2b.1). the mineral associations of the Main Ore Stage in
Another mineralogical variation is the prevalence of the outer Zn-Pb-bearing zones. This common late
galena over sphalerite in the external potions of the timing invites collective assignment of these late
Zn-Pb-(Ag). Some of these galena-rich portions are mineral associations to a Late ore stage.
highly argentiferous, with Ag contents as high as 30 Chalcocite-(covellite-digenite-chalcopyrite) are
oz/t in some thin mantos (up to 1 m thick). found more prominently in the bornite-dominant
An outermost Zn-bearing zone surrounds the sub-zone. There, they form thin veinlets <20 m wide
Zn-Pb-(Ag) ores but in contrast to the other Zn zones, cutting bornite (Figure 2b.5). In a second form, these
it is virtually devoid of sulfides. It basically consists phases coat dissolution vugs in which they typically
of Zn-bearing carbonates, including preponderantly form entire rims. In both cases, chalcocite constitutes
siderite and rhodochrosite, which may form mantos >50 volume % of the sulfides. Covellite comprises
up to 3 m thick with grades in excess of 5 % Zn. 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
CHAPTER 2

Interpretation of the observed patterns of algicas y geoqumicas de los yacimientos de Zn-Pb (Ag)
relative ages of mineral associations in the de San Gregorio y Colquijirca emplazados en unidades
Smelter and Colquijirca deposits sedimentarias en los bordes del sistema epitermal de alta
sulfuracin de Marcapunta. Tesis Ingeniero, Universidad
Analysis of crosscutting relationships between Nacional de Ingeniera, Lima, 60 p.
mineral assemblages and associations in the Smelter
and Colquijirca deposits suggests progressive advance Fowler, T.J., and Winsor, C.N., 1997, Characteristics
of the Main ore stage sulfide-rich mineralization front and occurrence of bedding-parallel slip surfaces and lami-
with time. An indication of the magnitude of the nated veins in chevron folds from the Bendigo-Castle-
advance is recorded in the central part of the Smelter maine goldfields: implications for flexural slip folding.
deposit where several bodies of sphalerite-galena- Journal of Structural Geology, 19, 799-815.
siderite-kaolinite float within the enargite-bearing
zones. Observed in detail, the sphalerite bodies Hemley, J.J., and Hunt, J.P., 1992, Hydrothermal ore-
are cut and partly replaced by the enargite-bearing forming processes in the light of studies in rock-buffered
assemblages. Also at Smelter, at the polished section systems; II, Some general geologic applications. Econom-
scale, numerous samples display residual sphalerite ic Geology, 87, p. 23-43.
and hematite surviving as inclusions in enargite-
bearing assemblages. These observations show that Hutchinson W.S., 1920, The Fernandini properties,
the inner Cu zone encroached on the Zn-Pb zone. province of Pasco, Per: Production costs and profits,
By the time the residual sphalerite-bearing zones had Colquijirca silver mine, Huaraucaca metallurgical plant, La
formed, the outer limit of the Cu mineralization was Curea copper mine, San Gregorio bismuth mine. Report
restricted to parts as near as 1 km to the Marcapunta for the Fernandini Properties, 70 p.
volcanic complex, that is ~1.5 km south of the final
Cu front exposed in the Principal pit at Colquijirca. Injoque, J., 1988, Estudio petromineragrfico de 52
A similar explanation in terms of progressive secciones de la mina Colquijirca, Per. Informe privado
advance of the mineralization front is also valid for Sociedad Minera El Brocal S.A.A., 90 p.
the Colquijirca deposit where numerous sphalerite- Lindgren, W., 1935, The silver mine of Colquijirca,
galena bodies float within the Cu-(Ag) and Cu-(Ag- Per. Economic Geology, 30, p. 331-346.
Bi) zones. Detailed mapping shows that these bodies
predated deposition of Cu-bearing sulfides and that McKinstry, H.E., 1929, Interpretation of concentric
they represent former external zones of the system textures at Colquijirca, Per. American Mineralogist, 14,
now largely overtaken and replaced by the Cu zones p. 431-433.
(Figure 2b.3). This process of progressive advance
of the mineralization front is described in detail for McKinstry, H.E., 1936, Geology of the silver deposit
other localities, notably for the large veins of the at Colquijirca, Per. Economic Geology, 31, p. 619-635.
Butte deposit (e.g. Sales and Meyer, 1969; Hemley
and Hunt, 1992). Meyer, C., and Hemley, J.J., 1967, Wall-rock alteration,
Late reversals in the temporal sequence of in Barnes, H.L., ed., Geochemistry of hydrothermal ore
mineral assemblages are observed at both Smelter deposits, 1st ed., New York, Holt, Rinehart Winston, p.
and Colquijirca, where veinlets composed largely 166-235.
of chalcocite, tennantite or sphalerite replace the
enargite-bearing assemblages. At Marcapunta Oeste, Orcel, J., and Rivera Plaza, G., 1920, Etude mi-
chalcocite replacing enargite in strongly fault- croscopique de quelques minerais mtalliques du Prou.
controlled bodies is interpreted in terms of retreat Bulletin Societ Franaise de Minralogie, 52, p. 91-107.
of the mineralization front, possibly during waning
of hydrothermal activity when meteoric water input Sales, R.H., and Meyer, C., 1949, Results from prelimi-
was higher. nary studies of vein formation at Butte, Montana. Eco-
nomic Geology, 44, p. 465-484.

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-

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
CHAPTER 2

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


mineralization in the Oro Marcapunta prospect

Disseminated Au-(Ag) mineralization at the generally consist of monomictic and polymictic


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

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
CHAPTER 2

Dome and lava flows


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

took place during several superimposed episodes. Up alteration, both of which display the effect of
to three main hydrothermal episodes or stages are corrosion (Figure 2c.3). This superimposition is
recognized (Figure 2c.5). These are described here interpreted not as the product of discrete stages
from earliest to latest. (i) An acid-leaching Early of mineralization but in terms of zonal migration
barren stage, mainly responsible for the formation (e.g., Sales and Meyer, 1949), in a similar manner to
of vuggy silica and peripheral advanced argillic and that observed between different mineral zones of
argillic zones. (ii) A Gold stage in the form of the Smelter and Colquijirca deposits. Following this
sulfide- and oxide-bearing veinlets, and finally (iii) interpretation, the outer vuggy silica zones encroach
local Late stages which generally are economically onto quartz-alunite zones as the acidic hydrothermal
uninteresting. 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
Early barren stage from the peripheral advanced argillic zone (described
below) both support this view. In both cases, alunite
Although essentially barren, this stage is by blades include pseudocubic cores of woodhouseite-
far the most prominent in the Marcapunta Au-(Ag) svanvergite composition (Figure 2c.4; Table 2c.1).
prospect. It effected >90 % of the outcropping Quartz occurs coating vugs left by former
central parts of the Marcapunta complex, where the sanidine, plagioclase and other coarse grains of the
Au-(Ag) mineralization took place. volcanic rock. It is typically euhedral and fine grained
The Early barren stage developed a well (up to a few hundred microns long). In centimetric
marked zoning outward from vuggy silica cores. As cavities after blocky sanidine crystals, the quartz
in many other high-sulfidation systems, larger zones crystals can be up to 1 cm long (Figure 2c.3).
of advanced argillic alteration, in turn, surrounded by Accessory minerals in the vuggy silica zones
zones of argillic alteration surround these vuggy silica include rutile and, according to EDS tests and
ledges. The most external zones consist of phyllic microscopic properties, also zircon. These minerals
alteration bordered by distal haloes of propylitic occur as part of the quartz matrix in form of minute
alteration. subhedral inclusions generally a few tens of microns
in size.
Vuggy silica. Strongly leached vuggy silica Occasionally, within vuggy silica, thin coatings
rocks retain their original texture and contain of alunite, native sulfur, and pyrite and traces of other
resorbed magmatic quartz as the only remnant minerals, such as covellite, as well as impregnations
magmatic mineral (Figure 2c.3). Vuggy silica ledges of enargite and chalcocite are observed (Figure 2c.3,
are recognized from surface to as deep as 300 m (e.g., 2e.2).
DDH CM4-444). Above 200 m depth, vuggy silica Microprobe analyses were performed on several
seems to configure large bodies possibly funnel- alunite grains from these thin coatings. In contrast
shaped, as intersected by hole SD-11, but below this to the zoned alunite described above, compositions
level they occur as veins no more than a few meters are homogeneous and close to that of stoichiometric
thick. alunite (Table 2c.1).
Vuggy silica bodies that are not overprinted by
subsequent mineralization stages are characterized by Advanced argillic alteration zone. The
an almost invariable absence of minerals other than advanced argillic alteration (AAA) zone envelopes
hydrothermal quartz (Figure 2c.3). Gold values in the vuggy silica cores and extends over much larger
such cases are generally <100 ppb and silver is <5 areas throughout the whole central sector of the
ppm (e.g., several intervals in the first 100 m of SD- Marcapunta volcanic complex (Figures 2c.1 and
11). 2c.2). The AAA zones can be collectively depicted
Within vuggy silica intervals, scarce massive as vertical funnel-shape structures (800-1000 m in
granular silica, largely consisting of quartz, are diameter) surrounding the east-west-orientated vuggy
observed. At several places, transitional contacts silica cores (Figure 2c.2). The maximum depths at
between vuggy silica and massive granular silica are which the AAA zones have been recognized do not
seen. The transition zones display incipient granular exceed 300 m (e.g., DDH SD-11 and CM3-444).
silica texture, consisting of fine-grained quartz Gold and silver values in these Early barren
partially filling the voids of the vuggy silica, and stage AAA zones are generally very low (several
suggest that the transitions are intermediate stages of tens of ppb and a few ppm, respectively). However,
textural destruction that in extreme cases transform there are also some intervals without recognizable
vuggy silica into massive granular silica (e.g., Simmons overprinting of the later Gold stage, which carry
et al, 2005). higher Au and Ag contents (up to several hundred ppb
Vuggy silica ribs also contain intervals of and 20 ppm, respectively). The existence of strongly
quartz-alunite alteration. Under the hand lens or anomalous Au-(Ag) intervals (up to 200 ppb Au)
microscope, it can be observed that vuggy silica within the AAA zones contrasts with their absence in
formation was superimposed on the quartz-alunite the inner vuggy silica ledges formed during the same

97
CHAPTER 2

Early barren stage. This observation may suggest that %, respectively (Table 2c.a). The cores are virtually
during the Early barren stage, very minor quantities devoid of K2O and Na2O. Comparable fluctuations
of gold were deposited in peripheral, cooler and less occur in the S ion site where phosphorous dominates
acidic altered zones. over sulfur in the most Sr-enriched zones (svanvergite
The advanced argillic alteration zone member). Thus, in a single pseudocubic core, P2O5
characteristically consists of the quartz-APS minerals contents were found to range from 28.5 wt % to as
group minerals assemblage accompanied by minor low as 12.2 wt %. Relatively high fluorine contents
amounts of zunyite, diaspore, pyrophyllite, native were found in most analyzed alunite blades (up to
sulfur, pyrite, enargite, covellite, chalcocite and other 1.22 wt %).
rarer minerals. In contrast to the cores, the envelope displays
The quartz-APS minerals group assemblage no evident zonal pattern, neither in thin section
is almost always fine-grained, ranging from a few nor with SEM imaging. Microprobe results are
microns to clusters of perfectly hexagonal plates as in accordance with this, revealing an almost pure
large as 4 mm across (typically between 0.5 and 1 end-member alunite of relatively homogeneous
mm). Quartz is the most abundant component of compositions. The only significant compositional
the assemblage, constituting 60-70 volume %, with variation is due to some Na substitution for K (0.18-
the remainder composed essentially by alunite-group 1.4 wt % NaO). The fluorine contents do not differ
minerals. However, alunite may locally dominate. significantly from those characteristic of the alunite
Several decimetric intervals containing >80 volume rimming woodhouseite series cores (Table 2c.1).
% alunite are also observed (Figure 2c.3). Reversal Alunite in zones immediately adjacent to vuggy
crystallization characterizes the quartz-alunite group silica bodies, which as explained above is largely devoid
pair and is most evident in large voids produced by of pseudocubic cores, shows similar compositions to
leaching of sanidine phenocrysts. Alunite-group that in the envelopes, the only difference being that
minerals generally replace feldspar grains and more Na substitution is lower (Na/K>0.1).
rarely are disseminated within the rock matrix. In
this last case, the alunite has a sugary texture. Alunite Argillic alteration zone. This zone is
when not accompanied by oxidation phases is distinguished by the dominance of kaolinite and/or
characteristically pinkish in color. Yellowish tones are dickite. Locally pyrophyllite, alunite, sericite, and,
apparently due to impregnations of goethite and/or more rarely, cristobalite, native sulfur, pyrite and
jarosite along cleavage and fractures. Translucent smectite are volumetrically significant. The highest
specimens are rare. Alunite birefringence is highly precious metal concentrations found in this zone are
variable, from first-order to second-order purple on the order of 50 ppb Au and a few ppm Ag (except
(Figure 2c.3). where overprinted by later gold-bearing veinlets).
In the outer AAA zone, alunite blades often The argillic alteration zone is mineralogically
show under the microscope pseudocubic cores the most complex of all of the alteration zones.
displaying marked oscillatory zoning arrangement Two well-developed sub-zones may be defined: an
(Figure 2c.3). The cores show compositions of innermost sub-zone, adjoining the AAA zone, made
the woodhouseite series whereas the blades are up mainly of kaolinite-(dickite)-alunite-quartz, and an
virtually pure alunite (see analytical details below). outer sub-zone containing kaolinite-(dickite)-sericite-
In contrast, alunite immediately adjacent to vuggy pyrophyllite-quartz and pyrite.
silica generally does not show pseudocubic cores and A distinctive feature of the alunite-bearing
is monomineralic. Zoning of the replacement and argillic alteration sub-zone is that the original rock
filling geometry of former phenocryst sites is also textures are in most cases completely obliterated.
recognized. Phenocryst sites in outer AAA zone are The presence of alunite accompanying the dominant
almost entirely replaced by alunite and quartz, and kaolinite-(dickite) seems to be related to this rock-
the rock appears compact and lacks significant open- texture obliteration. Conversely, the sericite-bearing
space development. In contrast, in the inner zones, argillic alteration sub-zone tends to preserve original
adjacent to vuggy silica ledges, phenocryst sites show volcanic texture.
voids and are only partially filled by the quartz-alunite
assemblage (Figure 2c.3). Phyllic alteration zone. The dominant
Multipoint microprobe traverses from the alteration assemblage is sericite, quartz, kaolinite,
pseudocubic cores to the margins of alunite blades and pyrite. Occasionally, pyrophyllite is present
show that the oscillatory cores approach the svanvergite in appreciable amounts. Phyllic alteration defines
end-member of the woodhouseite series, with the A irregular pockets, which collectively surround
site being occupied by highly variable amounts of the argillic zone. The available mining data show
mainly Sr and Ca. Analyses range from 14.47 wt % insignificant precious metal concentrations in this
SrO and 3.1 wt % CaO, with minor amounts of BaO zone. Only occasionally does gold attain anomalous
and CeO, i.e., approaching the composition of the levels (above 20 ppb).
svanvergite end-member, to values as low as 1.81 wt Rocks affected by phyllic alteration largely
% SrO, with CaO and CeO up to 6.5 and 5.2 wt preserve their original texture. Nevertheless, with
98
CHAPTER 2

the exception of quartz, all primary minerals have of anhedral quartz grains, commonly <500 m in
been almost completely replaced. Feldspars are size, and sulfides, mainly pyrite, enargite, covellite,
entirely replaced by sericite plus another unidentified chalcocite, and sphalerite. Clay minerals, including
phyllosilicate. Feldspar pseudomorphs consisting of kaolinite, illite, and smectite, occur as intergranular
sericite plus kaolinite are also locally observed. In fillings (e.g., Figure 2c.4). Accessory phases are
general, the groundmass is replaced by microcrystalline rutile, hematite and, more rarely, chalcopyrite and
aggregates of sericite, kaolinite, quartz, and pyrite. magnetite. Pyrite occurs as disseminations, especially
Locally, weak silicification of the matrix is observed in the central parts of the veinlets whereas enargite,
in rocks affected by phyllic alteration. chalcocite and covellite coat fractures, typically
along the veinlet walls. Enargite is the second most
Propylitic alteration zone. Propylitic rocks abundant sulfide phase in the straight siliceous
are the most distant expression of the pervasive veinlets and generally in the Gold stage. It occurs
hydrothermal alteration associated with the as subhedral prismatic crystals up to 2 mm long,
Marcapunta disseminated high sulfidation Au-(Ag) although massive aggregates and impregnations are
prospect. Gold and silver contents are close to also common. Covellite occurs as tabular crystals
background levels in unaltered dacitic rocks. Most and irregular massive aggregates; it usually fills open
of the exposures of this alteration type are present spaces with the other sulfides. Enargite, which also
beyond the central parts of the Marcapunta complex. fills open spaces, apparently postdates pyrite but, in
At depth, hole Brocal 524, which is located ~200 turn, is replaced by covellite and hypogene chalcocite.
m north of the advanced argillic zones intersected Sphalerite, which occurs as disseminations together
irregular intercalations of phyllic and propylitic with pyrite, is present only locally. Hematite occurs
alteration from near surface to as deep as 350 m, as plates in voids, and magnetite forms tiny irregular
suggesting that these zones collectively constitute clusters. The well-defined walls of the straight banded
a enveloping funnel-shaped zone surrounding veinlets, suggest that they were formed under brittle
the main Au-(Ag) mineralized core. The mineral deformation conditions.
assemblages consist predominately of mixtures of Straight siliceous veinlets display haloes
chlorite, kaolinite, calcite and, locally, minor epidote containing sulfide disseminations, essentially pyrite.
and montmorillonite. These disseminations are most abundant in the
Feldspars are mainly altered to montmorillonite highly permeable vuggy silica (Figure 2c.4) where
and small amounts of kaolinite, whereas biotite anhedral to subhedral pyrite, 50 to 500 m in size,
and hornblende are mainly altered to chlorite. The may completely fill voids.
groundmass is argillized (mainly montmorillonite) In Au-(Ag) mineralized parts (i.e, 1-2 g/t
and more rarely slightly silicified. Au equivalent), straight siliceous veinlets typically
constitute between 1 and 5 volume % of the rock.
However, there are also densely veined zones which
Gold stage contain uneconomic gold values (<300 ppb).
Thin (up to 0.5-1 mm wide), discontinuous
The Gold stage is characterized by the formation sinuous veinlets with poorly-defined walls, likely
of veinlets containing pyrite and minor amounts of formed under ductile conditions are more rarely
enargite, covellite, chalcocite, sphalerite, and other observed. These veinlets have a similar mineralogy
minerals including clays. The spatial association of to the straight banded veinlets, although the sulfide
gold with zones containing densely distributed sulfide content is lower so explaining the paler color. There
veinlets strongly suggests that significant amounts of are parts with 1-5 volume % sinuous veinlets, and
the gold in the Oro Marcapunta prospect are hosted by their precious metal contents do not differ greatly
the sulfides. Sulfides and clays occur as fracture filling from those containing comparable amounts of
and veinlets, as matrix of hydrothermal breccias, and straight siliceous veinlets. Given their volumetrically
as disseminations (Figure 2c.4). The sulfide content minor abundance, it is estimated that sinuous veinlets
typically ranges between 2 and 8 volume %. Gold do not contribute significantly to the bulk precious
contents in intervals containing abundant veinlets metal inventory of the Oro Marcapunta prospect.
range from several hundred ppb to several ppm, In intervals with sulfide disseminations, mainly
whereas silver typically ranges from 10 to 40 ppm in Early barren stage vuggy silica and quartz-alunite
(e.g., DDH SD 11, 92.8 m-151.0 : 1.7 ppm Au and 43 zones, pyrite occurs as fine encapsulations in quartz.
ppm Ag; Vidal et al., 1997). In some of the samples more than one generation of
Several types of sulfide veinlets are recognized pyrite has been identified. An early pyrite generation
to have formed during this early Gold stage. The is locally intergrown with enargite and covellite. A
most important in terms of precious metal values later generation occurs associated with quartz but
are straight siliceous veinlets. Much less abundant are without other sulfides. Locally, the pyrite exhibits
several types of sinuous veinlets. growth zoning. Clays, largely kaolinite, but also
Straight siliceous veinlets (up to 1-3 mm wide) smectite and/or illite rarely occur coating voids in the
are dark in color and consist essentially of thin bands 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 veinlets, with gold and silver values usually ranging
this stage. Only subtle mineralogical changes are from 0.5 to 2.5 ppm and 20 and 70 ppm, respectively
observed, the most noticeable perhaps being the (Ag/Au ratios from ~10 to ~30; Table 2c.2, Figure
increase of sphalerite content with depth. 5.5). A representative example of precious metal
A second Au-(Ag) occurrence consists of enrichment in rocks containing oxide veinlets is given
veinlets composed predominately of oxides, mainly by the DDH SD 11 which from 92.8 to 151 m depth
botryoidal hematite and goethite. Oxide veinlets returned values of 1.7 ppm Au and 43 ppm Ag for
accounts typically between 2 and 10 volume % of a Ag/Au ratio of ~25. Recent drilling, some 500 to
a given mineralized rock. The oxide veinlets cut 700 m south-west of DDH SD11, in the Marcapunta
predominately vuggy silica bodies and, in much lesser Oeste project, intersected similar Au-(Ag) mineralized
degree, rocks affected by quartz-alunite alteration. intervals with Ag/Au ratios <30. Higher Ag/Au
Ore grades are generally higher than in sulfide-bearing 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 At levels below the base of supergene
effect of overprinting by Cordilleran mineralization, oxidation (e.g., DDH SD-11, >300 m depth), this
which typically have Ag/Au ratios between 40 and oxidation process is particularly well observed. At
>100 (see Chapter 2a). Several lines of evidence, such depths, intervals containing pyrite and minor
including overprinting of sulfide-bearing and oxide- sphalerite also contain botryoidal hematite within
bearing veinlets, suggest that oxides formed nearly distances of only several centimeters. Separates from
coetaneously with the sulfide-bearing veinlets. zones containing only botryoidal hematite and minor
Disseminated botryoidal hematite, and less goethite returned up to five times more gold (1.2-
importantly goethite, typically coat the walls of voids in 2.5 g/t) than separates containing exclusively sulfides
vuggy silica rocks or overgrow euhedral hydrothermal (0.1-0.5 g/t), suggesting that the oxidation process
quartz (Figure 2c.4). The botryoidal hematite extends was the main Au-fixing event.
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.

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
CHAPTER 2

Table 2c.2 Au and Ag contents of representative mineralized REFERENCES


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

2.d The San Gregorio deposit

The blind San Gregorio Zn-Pb-(Ag) deposit is the following description does not achieve the level
located in the southern sector of the district, southwest of detail presented for the Smelter and Colquijirca
of a strongly oxidized hill at Gualquepaqui, ~3 km deposits.
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 Host rock
the Gualquepaqui hill, where, during the first decades
of the 20th century, Bi-Ag and Cu were mined Different data, including paleontologic records
(Hutchinson, 1920) . To avoid confusion the old Bi- and drill core correlations (Bendez, 1997; Fontbot
Ag mine will be referred to hereafter as Gualquepaqui and Bendez, 1999), indicate that the original host
and the new Zn-Pb-(Ag) discovery as San Gregorio. lithology at San Gregorio consisted of nearly 400 m
Two other areas, Bohorquez and Yanque Maria thick dolostone and limestone sequence, immediately
(Figure 2d.1) were also mined for Bi and Ag between overlying the Mitu Group, which is attributed to the
Gualquepaqui and Marcapunta Sur. Chambar Formation (base of the Pucar Group.
In contrast to the northern part of the district Bendez (1997) made public results obtained by
where continuous replacement unites Smelter Pardo (1997) whereby drill cores in carbonate rocks
and Colquijirca, no continuity is so far recognized from the immediate vicinity of the deposit and, in
between the Cordilleran deposits at San Gregorio partially decarbonatized dolostones in mineralized
and Gualquepaqui and those in the southern part intervals, preserve fauna characteristic of the Upper
of the volcanic complex (Marcapunta Sur prospect). Triassic-Lower Jurassic (Liassic). Among such species
Continuity between the strongly oxidized Bi-Ag-Cu- are Lucina Goliat GOTTSCHE, Rhynchonella c. f.
bearing zone at Gualquepaqui and the Cordilleran tetraedora SOWERBY, and Pentacrinus cf. jurensis
ores in the Marcapunta Sur prospect is uncertain. QUENSTEDT. Moreover, an outcrop of silicified
A continuity may be inferred between Bohorquez- dolostones at Gualquepaqui, around 50 m over the
Yanque Maria and Marcapunta Sur as illustrated in contact with red beds of the Mitu Group, contains
Figure 2d.2. Monotis Subcircularis, characteristic of Norian.
The San Gregorio deposit is made up of In addition, a lithogeochemical reconnaissance
irregular orebodies, several tens of m thick, replacing conducted in relict carbonate beds in San Gregorio
almost entirely the nearly 400 m thick sequence of resulted in compatible values with those obtained on
carbonate rocks of the Pucar Group (Bendez, samples from the nearby Lachipana hill (approximately
1997; Fontbot and Bendez, 1999; Fontbot and 3 km northwest of San Gregorio) where the Pucar
Bendez, 2000; Petersen and Canchis, 2000). The sequence overlies the Mitu Group red beds (Yacila,
bulk of the San Gregorio ores constitutes a material 2001).
locally called sulfide rock which, based on the The generalized stratigraphic section of the
presence of relatively abundant amounts of alunite, Pucar Group in the mineralized sector of San
were formed from acidic fluids (Fontbot, 1997). Gregorio (Figure 2d.3) was reconstructed on the
This material is typically very fine-grained (<100 m) basis of a correlation of less altered rocks and rock
and is mineralogically simple. Sphalerite, galena, and remnants. The lowermost 15 to 30 m consist of finely
pyrite are the principal sulfide components, whereas laminated beige dolostones called basal dolostones
quartz, kaolinite, and alunite largely predominate in (Chapter 1a) which constitute the less altered unit of
the gangue fraction. The great abundance of alunite the Pucar Group in the San Gregorio deposit and
in the San Gregorio ores differs from the Colquijirca chemically resemble the basal dolostones at the
deposit, where alunite is restricted to small internal Lachipana hill, 3-5 km north-west of San Gregorio
zones immediately surrounding the enargite-bearing (Yacila, 2001).
core (Chapter 2b). Follow 200 m of mainly dolostones and
Except for the strongly oxidized rocks of the limestones with several thin intercalations of
Gualquepaqui hill, neither exposures of the orebodies cinerites at the base of the interval. Cinerites are also
nor the host rock are present at San Gregorio. All data recognized in the Chambar Formation in the nearby
presented in this chapter are based almost exclusively Lachipana hill, 50 m above the contact with the
on core from drill hole information. For this reason 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 influent role in their internal parts. In other words, an
of dolostones and limestones. The upper 150-200 m entire mineralized orebody displays a geometrically
are composed of sandy dolostones intercalated with composite character, which notably differs from the
milimetric to centimetric coarse-grained sandstone other Cordilleran deposits of the district, particularly
layers (Figure 2d.3). These upper beds, as pointed from the mantos at Colquijirca.
out in Chapter 1, are, in comparison to surrounding Correlations of drill cores located in a 100 m
Pucar outcroppings, particularly well developed in spaced grid (in places down to 50 m apart) indicate that
San Gregorio, and host perhaps up to more than one irregular bodies that crosscut stratification represent
third of the Zn-Pb-(Ag) resources of the deposit. more than half of the deposit. These large structures
A very minor fraction of the San Gregorio appear to be controlled by faults now unrecognizable
ores is hosted by the detrital sediments of the basal due to the extreme obliteration of the fabric, and
breccia (Chapter 1), a thin horizon of <5 m thick in part complete dissolution of the carbonate rocks
considered to be the base of the Pucar Group. during the formation of the sulfide rock. One of
the most impressive irregular replacement bodies
was intersected by hole 39G which returned >300
Spatial configuration of the mineralized m of continuous sulfide rock containing several
bodies and controls on mineralization orebodies which collectively are >100 m grading 8%
Zn, and 2.5% Pb (Figure 2d.3). In addition, strongly
The shape of the ore bodies at San Gregorio anomalous values in this hole (up to 3% Zn+Pb)
seems to be controlled by several factors. The extend vertically down to the upper beds of the Mitu
external parts of most ore-bodies follow lithological Group red beds where multiple mineralized fractures
and structural patterns, whereas the acidic nature of and faults can be recognized.
the hydrothermal fluids apparently played a more 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
CHAPTER 2

Ore stage
geometrical character of a mineralized body is
shown in Figure 2d.3. In this figure, it is interpreted The Ore stage is the responsible for the
that sulfide rock intervals grade into sulfide rock economical mineralization at San Gregorio. A
veins or vein sets. External parts of sulfide rock partly visual summary of the Ore stage is documented in
replace along bedding and form roughly conformable Figure 2d.4. Most of the images show the intimate
manto-like shapes (up to >150 m long). Examples of relationships between alunite and sphalerite-galena
manto-like shapes are the ones encased above, below, characteristic of most orebodies. The Ore stage
or in between various units of dissolution breccias developed a relatively simple zoning process that
with argillaceous matrix, as shown in Figure 2d.3. resulted in three main zones, which, from inner to
Permeability, and consequently, lithology was the main outer parts, are: (i) a Cu-(Ag) zone, (ii) a Zn-Pb-(Ag)
parameter controlling replacement along bedding. zone, and (iii) a barren outer zone.
In a few cases, some manto-like bodies appear to
be limited by dolostone units, as several orebodies
located immediately above the basal dolostones Cu-(Ag) zone
or between relict intermediate dolostones (Figure
2d.3). Parts in contact with relict dolostones are The Cu-(Ag) zone is economically unimportant
constituted mainly by sphalerite, galena, and Mn- and volumetrically minor. Only two narrow Cu-
Fe-Zn carbonates and are external relative to the (Ag) veins <0.3 m wide were observed (e.g., DDH
acidically-formed sulfide rock intervals. The 20 G at, 232 m depth). The main minerals are
less acidic character of the fluids in external zones famatinite?, pyrite, quartz, and tetrahedrite. Minor
probably favored selective replacement of more minerals include alunite and chalcopyrite. Famatinite
reactive lithologies, for example limestone rather is observed in the vein core as disseminations and a
than dolostone and resulted in flat manto-like bodies. band up to 5 cm wide. Famatinite occurs as anhedral
In contrast, in the internal zones, where more acidic grains replacing pyrite, as rims around it, and as
fluids prevailed, bulk replacement of the carbonate matrix between breccia fragments. Quartz grains are
rocks derived in irregular bodies of sulfide rock. subhedral and most are <2 mm long. No quantitative
Veins are volumetrically less important than data on the composition of these minerals are
mantos. There was no attempt to correlate the currently available.
different vein intercepts due to the wide-spaced Several small high grade copper orebodies
drilling. They are generally narrow (<2 m wide), were mined at the Gualquepaqui hill (Figures 2d.1
abundant, and located throughout the deposit. and 2d.3; Hutchinson, 1920; Johnston, 1929, 1933
The walls of the veins are irregular because of y 1935, holes 2C and 2B). Copper carbonates and
replacement of the host rock. The replacement is chalcocite are recorded as the main cupriferous
better developed toward the hanging wall. Most of the minerals in what seems to represent different parts of
veins are made up of friable, microgranular sulfide a supergene enrichment profile. Immediately above
rock composed of sphalerite-galena-pyrite-quartz- the copper ores, a cut had been opened in the first
kaolinite-alunite. Less abundant are veins consisting decades of the past century for Bi-(Ag) mining from
of sphalerite-galena-pyrite-barite, and, even rarer, strongly oxidized ores with bonanza grades. Atelestite
thin veins of famatinite-(tetrahedrite) (DDH 20G at and bismite are the main recorded bismuth minerals
232 m depth). 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)
Mineral deposition history: stages and zone recognized in the Colquijirca deposit.
zoning
Zn-Pb-(Ag) zone
The study of more than 80 polished and thin
sections distributed systematically throughout the San This zone is by far the volumetrically most
Gregorio deposit has allowed to distinguish only one important of the deposit. It can be broadly divided
mineral ore stage (Figure 2d.5). In strong contrast to into two main sub-zones which in turn exhibit minor
Smelter, Marcapunta Oeste, and Colquijirca, no early mineralogical variations with increasing distance: an
silica-pyrite stage (Early silica-pyrite stage in Chapters inner sphalerite-galena sub-zone, and an outer Zn
2a and 2b) has been recognized at San Gregorio. carbonate sub-zone with rhodochrosite and siderite.
San Gregorio ores also have characteristically more Table 2d.1 shows characteristic compositions of the
weakly developed internal zoning of the mineralized various classes of ores of the Zn-Pb-(Ag) zone.
bodies and a virtual absence of volumetrically
important copper concentrations in the inner zones.
These and other differences are described at the end Sphalerite-galena sub-zone
of the chapter. 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 2d.4). Alunite occurs as very fine grains ranging
terms this sub-zone consists of sphalerite, galena, generally from 5 to 30 m across and from 1 to 5
pyrite, and minor quantities of marcasite make up m thick. Under the polarizing microscope, alunite
the sulfide portion. The other constituent minerals reaches first order yellow to gray birefringence;
are chiefly quartz(kaolinite, alunite). more rarely in large grains up to second order blue
Sphalerite, galena, pyrite, quartz(kaolinite, (Table 2d.4). The most common habit of alunite
alunite) constitutes almost invariably a highly friable is as oriented grain aggregates. Alunite blades are
material called by the Colquijirca staff sulfide rock commonly encroached into pyrite and, more rarely,
following the informal denomination given by Owens sphalerite. Alunite also occurs encapsulated in quartz
(1995). The microgranular texture of this rock, with or overgrowing it.
grain size usually <100 m in its largest dimension Compositionally, the sphalerite-galena sub-
(Table 2d.4), has the macroscopic appearance of an zone displays small mineralogical variations from
unconsolidated detrital rock. core to rim. Pb, for example, increases toward the
In the internal parts of the sulfide sub-zone, margin of the sub-zone (from 1.5 wt % up to 8 wt
quartz and kaolinite-(dickite) account for up to >70 %).
wt % of the rock (high silica sulfide rock in Table Veins consisting of >80 volume % of
2d.1). Sphalerite, galena, and quartz in these cases sphalerite, galena, pyrite, barite, and kaolinite occur
occur habitually as anhedral to subhedral grains more frequently in the peripheral parts of the
exhibiting irregular borders indicative of corrosion sphalerite-galena sub-zone. These veins consist of a
(Table 2d.4). Kaolinite-(dickite) are abundant and compact material in contrast to the sulfide rock, in
usually fill intergranular spaces (Table 2d.4). which the grain size of most of their components is
Other parts of sulfide rock consist besides coarse (up to several centimeters; massive ore in
sphalerite, galena, pyrite, alunite and minor other Table 2d.1). Sphalerite, galena, and barite are typically
APS minerals. In these cases, quartz, kaolinite and intimately intergrown, whereas kaolinite and minor
dickite are largely subordinated (<10 volume %; amounts of quartz fills intergranular spaces (Table
high sulfate sulfide rock in Table 2d.1). 2d.4). Minor tiny grains of siderite locally overgrow
Sphalerite and galena in sulfide rock occur barite.
generally intimately intergrown displaying complex Relatively rare, Ag-rich intervals consisting
textures (Table 2d.4). Galena commonly replaces largely of pyrite were intersected in a few holes
sphalerite, although sphalerite replacing galena is also surrounding Gualquepaqui (e.g., DDH 36G at 146
observed. Sphalerite displays characteristically deep m depth). The intervals reach up to >30 oz/t Ag
orange to yellowish to whitish internal reflections without any other appreciable metal content of
under crossed nicols (Table 2d.4), suggesting low FeS economic interest. Macroscopically, the Ag-rich
contents (consistent with microprobe quantitative intervals are made up of monomineralic masses of
data reported below). subhedral coarse-grained pyrite. Gangue minerals are
Alunite is typically platy and euhedral to exclusively quartz and kaolinite.
subhedral and occurs commonly as intergranular
fillings accompanied by much finer kaolinite (Table 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 Composition of minerals of the sphalerite-galena
sub-zone display abundant veinlets of microgranular sub-zone
assemblages of alunite, quartz, kaolinite and minor
erratic amounts of pyrite. Although the distribution Microprobe analyses of more than sixty grains
of these veinlets often mimics spatially the highest of sphalerite from the sulfide rock from different
concentrations of Zn-Pb-(Ag), the veinlets themselves parts of the sphalerite-galena sub-zone are broadly
lack the economically interesting sulfides, sphalerite homogeneous. Sphalerite, irrespective of whether it
and galena. Barren alunite, quartz, pyrite veinlets correspond to internal or external parts of sulfide
also occur in intervals devoid of any appreciable ore rock bodies, yielded low FeS contents (<1.2 wt %,
concentration (Figure 2d.4). averaging 0.3 wt %). Mn contents in sphalerite were
Similar textural relationships are observed in below the instrumental detection limits (0.05 wt %,
the veinlets throughout the sulfide rock bodies. Table 2d.2)
Paragenetically, alunite follows quartz precipitation, Galena grains gave essentially stoichiometric
although it is common to find alunite encapsulated compositions (Table 2d.2). No significant silver values
in quartz. Rare minute (<5 m long) inclusions of were detected. Pyrite, on the other hand, although
quartz in alunite are also found. Kaolinite occupies generally compositionally stoichiometric, gave silver
intergranular spaces between alunite and quartz values of up to 0.8 wt % (Table 2d.2). This type
(Figure 2d.4) and occasionally it replaces alunite, of argentian pyrite is possibly the main Ag-bearing
and much more rarely quartz. Pyrite, the only sulfide mineral in the silver-rich pyritic intervals detected
observed in the veinlets, occurs as minuscule grains in the periphery of Gualquepaqui and mentioned
in the alunite, quartz and kaolinite microgranular above (Ag-rich pyrite). Copper and arsenic contents
mass. Pyrite has been rarely observed as inclusions in in pyrite were found to be generally <0.2 and <0.4 wt
alunite (Figure 2d.4). %, respectively (Table 2d.2).
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 mainly sphalerite. Anhedral, low-Fe sphalerite grains
homogeneous and stoichiometric, with uniform averaging 2 mm in size occur locally within massive
Na/K ratios of 0.03-0.12 and wt % SO3 between 39 rhodochrosite. The Zn-bearing carbonate sub-
and 40%. Such homogeneous alunites are similar to zone develops not only at the external parts of the
alunite at Colquijirca, but markedly different from sphalerite-galena sub-zone, but also at the contacts
those at Oro Marcapunta. of the latter with dolomite relicts preserved in the
sulfide rock.
Zn-bearing carbonate sub-zone Typical compositions of Zn-bearing carbonate
The Zn-bearing carbonate sub-zone envelopes rocks are given in Table 2d.1. Besides the high Zn
the sphalerite-galena sub-zone as relatively narrow concentrations in carbonates, the values reflect also
bodies generally <2 m thick and containing usually the relatively low volume contents of sulfides in
between 3 and 5 wt % Zn and low values of Pb (<0.5 these types of intervals (<10 volume % collectively
wt %) and Ag (<0.5 oz/t). Locally, these bodies may of pyrite, galena, and sphalerite). Table 2d.1
attain up to 8 m thick and bear high Zn contents summarizes the high MnO and FeO

values, indicative
(e.g., DDH 34G, from 156 to 164 m at 7 % Zn). It is of the predominance of rhodochrosite, siderite, and
estimated that this sub-zone accounts for around 5 % oligonite.
of the total Zn inventory of San Gregorio (between
3 and 4 million tons).
Mineralogically, this zone is dominated by Barren outer zone
Zn-bearing rhodochrosite, siderite, and oligonite
(Fe(Mn,Zn)(CO3)2), are the main. Minrecordite The barren outer zone represents the
(CaZn(CO3)2), and smithsonite (ZnCO3) may also be outermost recognized expression of hydrothermal
present based on XRD data. activity produced by the Ore stage. No economically
Sphalerite (Figure 2d.4), pyrite, and lesser interesting metals are present in this zone. The barren
galena, together account for less than 10 volume % outer zone consists mainly of veins and patches of
of the ore. Microprobe analyses of sphalerite yield dolomite surrounding the Zn-bearing carbonate sub-
between 1 and 4 wt % FeS (Table 2d.2). zone and of calcite veinlets particularly above this
The Zn-bearing carbonate bodies, notably sub-zone. Calcite veinlets has been recognized up to
when made up mainly of rhodochrosite and siderite 500 m away from the economical parts of the San
occur as nearly massive replacements (Table 2d.4). Gregorio deposit (e.g., DDH 36G and 12G at depths
Observed in detail, the carbonates commonly have between 40 and 100 m).
bands of rhodochrosite and sulfide disseminations,

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


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

114
CHAPTER 2

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

115
CHAPTER 2

116
CHAPTER 2

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, immediately overlies domes hosting disseminated


differences (metal suite, total sulfide content, and Au-(Ag) ores which were emplaced between 4300
zoning) are greater than similarities (mineral alteration and 4500 m.a.s.l. (Figure 2e.1). The upper (and main)
assemblages and depth of emplacement) between, on part of Cordilleran hydrothermal activity at Smelter
the one side, Au-(Ag) disseminated high sulfidation and Colquijirca virtually reached the same shallow
epithermal mineralization at Oro Marcapunta and, level (up to around 4400 m.a.s.l.) as that which
on the other, Cordilleran base metal deposits at both, produced disseminated Au-(Ag) mineralization, the
Smelter and Colquijirca. The differences justify why main part of the ore bodies occurring between 4200
each type is considered in this study separately and and 4300 m.a.s.l. At San Gregorio, mineralization
has been classified into different ore deposit classes. is topographically lower, between 3900 and 4100
Furthermore, spatial relationships between these m.a.s.l.
ore types indicate that precious metal epithermal
mineralization at Oro Marcapunta predated those of
Smelter-Colquijirca. High sulfidation mineral assemblages and acid-
sulfate gangue mineral assemblages

Similarities High sulfidation and acid-sulfate gangue


assemblages are the most evident sharing features
High level emplacement of Au-(Ag) epithermal and Cordilleran bodies.
At deposit scale, and without considering timing-
The field evidences discussed above and assemblage relationships, which will be discussed
summarized in the cross-section of Figure 2e.1 below, in both mineralization types, enargite-pyrite is
indicate that the geometry of the ore district has the main assemblage indicating that high sulfidation
not experienced large changes since mineralization, conditions prevailed in both hydrothermal systems.
except perhaps collapse in the flanking parts of the More prominent is, nevertheless, the abundant
volcanic complex, which could be pre-, syn, and post presence in both deposit types of the quartz-
mineralization. Other significant post mineralization alunitezunyite assemblage, or yet the development
tectonic displacement is not recognized. Post of vuggy silica, indicative of acidic fluids. Again, this
mineralization erosion is also subordinate. The last feature without considering timing-assemblage
present summit of Marcapunta which reaches 4500 relationships, which, as we will see below, are different
m.a.s.l. approximates by several tens of meters the in each case.
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 Differences
effusive component near the summit of Marcapunta
and the lack of features indicating deep erosion. One Sulfide content. The sulfide content is one of
of these late lava-dome intrusions (Montura dome) the main characteristics that make both mineralization
cuts mineralized lava-domes units near the southern types different. Whereas at Oro Marcapunta it ranges
summit of Marcapunta (e.g., Sarmiento, 2005). between 2 and 5 volume %, at Smelter and Colquijirca,
Disseminated epithermal Au-(Ag) the sulfide content typically varies between 40-60
mineralization and Cordilleran hydrothermal activity volume % (Chapters 2a, 2b and 2c).
took place at a very high level, in part indicated by This feature is irrespective of the host rock.
the observation that the Montura dome which is For example, the Gold stage (Chapter 2c), the
fresh and preserves its effusive component, cuts and 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).

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

As mentioned before, although generally


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

119
CHAPTER 2

emplaced from surface to a maximum depth of 320 drill hole Brocal-524 cut an interval of nearly 300
m (4200 m.a.s.l., DDH-SD11). Below this level, only m. of phyllic to propylitic alteration which, together
pyritic veinlets associated with sericitic alteration with other intersections, seems to configure a nearly
and lacking advanced argillic alteration minerals are vertical halo of the Au-(Ag)-bearing vuggy silica
observed (Chapter 2c). zones at Oro Marcapunta, in the central portion
The Smelter and Colquijirca Cordilleran bodies of the volcanic complex. The lower section of
are similarly shallowly emplaced, largely between this interval, in volcanic rocks, between 450 and
4400 and 4200 m.a.s.l.. However, relatively deep 500 m depth, is overprinted (cut and replaced) by
drilling shows that these bodies root into enargite- strong quartz-alunite alteration as haloes of pyrite-
rich veins. The, so far, deepest hole Brocal-524 (enargite)-rich veinlets, in part silicified, characteristic
intersected enargite-rich veins at 3750 m.a.s.l. (Figure of Cordilleran mineralization in volcanic rocks of
2e.1), with mineralogical assemblages, in essence, the Smelter deposit. Under the microscope, sericite
identical to the bulk of the internal parts of the is replaced by alunite, but it survives in places as
shallower Cordilleran mantos and veins of Smelter isolated grains, even at <5 cm of the pyrite-(enargite)
and Colquijirca, including the presence of abundant cores. Holes located more to the north that cut also
alunite. volcanic rocks, failed to encounter the phyllic to
propylitic alteration zone, suggesting that Brocal-524
would have intersected the outermost halo of the
Decreasing vs. increasing oxidation state disseminated Au-(Ag) mineralization.
Recent exploration at Marcapunta Oeste
Different paths in the fluctuation of oxidation has confirmed the late timing of Cordilleran
state of the hydrothermal evolution is another mineralization relative to the disseminated epithermal
major difference between both mineralization types. Au-(Ag) ores. In the easternmost portion of the
Disseminated Au-(Ag) epithermal mineralization Marcapunta Oeste project, Cordilleran veins cut the
show a decrease in the oxidation state as suggested precious metal veinlets and veins (Figure 2a.2). Drill
by the change of the pH-indicative alteration and holes (e.g., CMO3-444) have encountered up to 350
gangue accompanying assemblages from mainly m of vertical extension containing Au-(Ag) ledges
quartz-alunitezunyite in the first hydrothermal from the precious metal event at Oro Marcapunta,
stage (Early barren stage) to mainly quartz-sericite which in the lowermost 50 m are superimposed by
accompanying the later gold-bearing veinlets (Gold Cordilleran ores. The most widespread example
stage). consists of early barren stage quartz-alunite zones,
In contrast, the Cordilleran hydrothermal containing Au-(Ag) veinlets, being cut by centimeter-
activity at Smelter (and presumably also at Colquijirca) wide pyrite-(enargite)-rich veinlets and less frequently
recorded by the accompanying gangue mineral veins. Furthermore, intervals of vuggy silica display
assemblages indicate that the oxidation state increased phenocrysts containing intergranular infillings of
with time and then during the retrograde history enargite of the Cordilleran stage which in part
decreased. During the Early silica-pyrite stage, the destroy earlier Au-(Ag) veinlets bearing quartz-
associated alteration assemblage was sericite-quartz, alunite assemblage. It is also interesting to note that
whereas the later Main ore stage records higher chalcocite, presumably the western expression of
oxidation states through the assemblage quartz- the Late ore stage of the Smelter deposit, occurs
alunitezunyite. A reverse path is recorded during the as infillings in voids of vuggy silica of epithermal
latest observed ore stage of the Cordilleran deposits, precious metal mineralization.
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 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
CHAPTER 3

Introduction Geologic setting and mineralization

Einaudi (1977, 1982, 1994) points out that The Colquijirca district is located 8-16 km
some sulfide-rich polymetallic ores form late in the south of the world famous Cerro de Pasco mine
evolution of porphyry-related hydrothermal systems. (Fig. 1). It contains one of the largest concentrations
He noted that in certain systems these ores are well of massive polymetallic ores within the Miocene
developed (e. g., Yauricocha and Cerro de Pasco, metallogenic belt of central and northern Peru (Vidal
Peru and Bisbee, Arizona), whereas in others they are et al., 1997), where numerous other Cordilleran base
only incipient or even barren (e. g., Ely, Nevada and metal lode and replacement deposits occur (e.g.,
El Salvador, Chile respectively). Irrespective of the Petersen, 1965; Einaudi, 1977, 1982, 1994; Guilbert
degree of development, he refers to this late stage as and Park, 1986; Bartos, 1988). Indeed, from a
the lode stage and to the ores, if they are formed, metallogenetic point of view, the Colquijirca district
as Cordilleran base metal lode deposits. In order to is part of a larger belt that also comprises the giant
better integrate the frequent massive development of ore concentrations of Cerro de Pasco. Spatially linked
replacements in carbonate rocks, as is the case of the with the ores, magmatism in the Colquijirca-Cerro
Colquijirca district, we extend here this denomination de Pasco districts is manifested through explosive
to Cordilleran base metal lode and replacement calc-alkalic volcanism of intermediate composition,
deposits. particularly as diatreme complexes accompanied by
The main characteristics of deposits formed subsequent multiple intrusion of porphyritic domes
by this late Cordilleran stage include the following (e. g., Bowditch, 1935; Lacy, 1952). The diatreme-
(e.g., Einaudi, 1982): (i) high sulfidation and oxidation dome complexes of Cerro de Pasco, Yanamate and
states of the mineral assemblage with associated Colquijirca (Fig. 1; e.g., Angeles, 1993, 1999; Sillitoe,
advanced argillic to sericitic alteration, (ii) massive 2000) intrude thick sequences of carbonate rocks
texture and sulfide content of lodes up to more than which host most of the ores.
50 % in volume, considerably higher than in other
porphyry-related mineralization types, (iii) and a
common suite of economically interesting metals, The Colquijirca Mining district
mainly Cu-Zn-Pb(Ag-Au).
Multi-disciplinary research over the past three In the center of the Colquijirca district, the
decades on epithermal deposits and their active Marcapunta diatreme-dome complex intrudes an
equivalents in volcanic arcs has helped decipher many Eocene sequence more than 300 m thick of folded
of the formation mechanisms of the Au-(Ag) high carbonate rocks, continental limestones, marls, and
sulfidation epithermal deposits (e.g., Hedenquist, detrital sediments (Pocobamba Formation) to the
1987; Stoffregen, 1987). Recently their genetic links north, and Triassic-Jurassic marine, nearly pure
with porphyry copper-gold deposits have been limestones, and dolostones (Pucar Group) and
supported (Hedenquist et al., 1998, Muntean and Permian red beds of the Mitu Group to the south
Einaudi, 2001). (Figs. 1, 2, 3). The sedimentary rocks around the
A review of existing literature shows that most diatreme, including red beds of Permo-Triassic age
of the detailed studies on Cordilleran base metal have subsided about 500 m into the diatreme neck
deposits were on deposits not spatially linked to the (Fig. 3).
presumed parental porphyry copper mineralization or Intense alteration, dominated by advanced
to any other recognizable ore forming environment. argillic and argillic alteration related to Au-(Ag)
This reflects the infrequent occurrence of Cordilleran epithermal mineralization is present in large parts
base metal lode and replacement deposits and of the diatreme-dome complex (Figs. 2, 3). Mixtures
contemporaneous igneous activity, as was already of quartz-alunite-dickite-kaolinite (zunyite,
discussed by Guilbert and Park (1986, p. 465). pyrophyllite, illite) occur within or immediately
The Colquijirca District offers the rare surrounding mineralized areas and kaolinite-illite
opportunity to study Cordilleran base metal lode and (smectite)-sericite-chlorite-calcite occur in weakly
replacement deposits closely related in space with mineralized or barren areas.
Au-(Ag) high sulfidation epithermal mineralization Au-(Ag) high sulfidation epithermal
produced within a Miocene diatreme-dome volcanic mineralization is hosted within oxidized shallowly
complex. In this contribution we establish through emplaced vuggy silica bodies (Fig. 3) with vertical
40
Ar/39Ar dating of hydrothermal alunite and dimensions of up to 100 m and gold values around 1
magmatic biotite, the timing of mineralization of to 2 ppm (Vidal et al, 1997). Tonnage of the resources
these two ore types and their relationship to the are not known. The bodies have been recognized
magmato-volcanic activity in the district. 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

122
CHAPTER 3

E-360 000 (7616' W)


3 Km
Ecuador
Colombia N

Peru Brasil

Area of
geological map
Lima N-8820000 (1040' S)
Cerro de Pasco
Pacific Ocean

Bolivia
Chile

MINERALIZATION TYPE Yanamate


Cu-Zn-Pb-(Ag-Au-Bi)
Cordilleran base metal deposits
Au-(Ag) volcanic-hosted high
sulfidation epithermal

Colquijirca
GEOLOGICAL UNITS

Dacite diatreme-dome complex (Miocene)


Smelter

Pocobamba Formation (Eocene),


mainly limestones and marls
Goyllarizquizga Group (Cretaceous), Marcapunta
sandstones
Pucara Group (Upper Triassic-
Fault
Lower Jurassic), limestones and dolostones
San Gregorio
Mitu Group (Permian-Triasssic), sandstones Thrust and
reverse faults
Excelsior Group (Devonian), phyllites area of Fig. 2
Fold axis

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 a, b, c). The sulfide-rich replacements include the
the surface. As in other high sulfidation epithermal deposits of Colquijirca (30 Mt, at Zn+Pb~8 %) and
deposits (e. g., Summitville, Gray et al., 1994), deep Smelter (50 Mt, at 2 % Cu) 3.5 km and 1.5 km north
portions of unoxidized ores characteristically contain of Marcapunta respectively and San Gregorio (70 Mt
less than 5 volume % of finely disseminated sulfides, at Zn+Pb~10 %) 3 km south of Marcapunta (Figs.
mainly pyrite-enargite and very minor sphalerite. The 2, 3). Estimated temperatures from stabilities of
original sulfide content of the oxidized veinlets is alteration assemblages range from around 300C close
estimated to be no more than 10 volume % . to the diatreme-dome complex to 150C in external
Sulfide-rich polymetallic replacements portions of the system (Fontbot and Bendez,
represent the other distinctive and economically most 2001). The sulfide-rich replacement ores at Smelter
important type of mineralization in the district. These and Colquijirca are hosted by Tertiary Pocobamba
deposits aggregate of at least 150 Mt of carbonate- Formation carbonate rocks and contain typically
hosted alunite, kaolinite-bearing Cu-Zn-Pb-Ag(Au- between 25 and 50 volume % sulfides, mainly within
Bi), in part massive, replacements (Ahlfeld, 1932; flat elongated mantos and irregular-shaped, stacked
Lindgren, 1935; McKinstry, 1936; Yaringao et al., orebodies developed from the external margins of
1997; Vidal et al., 1997; Bendez, 1997; Fontbot and the diatreme vent into the carbonate rocks (Figs. 2,
Bendez, 1999, 2001; Bendez and Fontbot, 2002 3). Massive replacement characterizes these ores, but

123
CHAPTER 3

open space filling and veins and breccias are locally (Ag) epithermal bodies (Marcapunta) and four to
important. Exploration drilling indicates that the the sulfide-rich polymetallic replacements (Smelter
bodies have their roots within the diatreme complex, and Colquijirca). Because of the extremely fine
in deep subvertical narrow veins (from 500 m to grained habit of alunite at San Gregorio (less than
more than 750 m depth below the surface) composed 20 m in length), attempts to concentrate sufficient
mainly of pyrite-enargite-quartz-alunite and minor coarse-grained alunite grains for geochronology were
pyrophyllite (Fig. 2). unsuccessful.
The sulfide-rich ores extend continuously The three biotite samples correspond to three
from Smelter for almost 4 km north to Colquijirca, unmineralized dacitic domes: PBR-148, PBR-215 and
where they virtually attain the same shallow elevation PBR-216, and are located respectively one kilometer
as the Au-(Ag) epithermal ores. Along its whole north, some 0.7 kilometers west and 2.5 kilometers
extension, the mantos are zoned in all directions northwest (Huacchuacaja) of the diatreme vent
from a core composed of pyrite-enargite-quartz- (Figs. 2, 3). Rocks in these domes have a porphyritic
alunite (luzonite, colusite, zunyite, barite; Zone I) texture similar to those observed in the altered ones,
to the following main zones: pyrite-chalcopyrite- with large sanidine phenocrysts, smaller plagioclase,
dickite-kaolinite-siderite-quartz (tennantite, Bi-Ag resorbed quartz, minor biotite, and hornblende.
sulphosalts, bornite, alunite, barite, quartz; Zone The microcrystalline groundmass is composed by
II), pyrite-sphalerite-galena-chalcopyrite-dickite- quartz, potassic feldspar, and plagioclase. Electron
kaolinite-quartz (siderite, hematite, magnetite, microprobe analysis of biotite grains from sample
alunite; Zone III), and the outermost known zone PBR-215 yield Fe/(Fe+Mg) molar ratios ranging
of pyrite-galena-sphalerite-siderite (kaolinite, from 0.28 and 0.33.
dolomite, Zn-bearing carbonates; Zone IV) (Figs. In contrast to samples PBR-148 and PBR-215,
2, 3). A similar zoning is also present to the south which apparently correspond to individual domes,
(Bendez, 1997; Fontbot and Bendez, 2001) where sample PBR-214 (Huacchuacaja, Fig. 2) comes from
bodies develop mainly into Lower Jurassic carbonate a fissure controlled, north-west aligned multiple
rocks of the Pucar Group. This is also the host rock dome intrusion complex 1.3x0.25 km in horizontal
of the recently discovered San Gregorio, one of the dimensions, with individual domes measuring less
largest known Zn-Pb deposits in Peru (> 70 Mt @ than a hundred meters diameter. Thin sections from
at Zn+Pb~10 %; Yaringao et al., 1997; Vidal et al., samples PBR-148 and PBR-215 show biotite grains
1997;). which are slightly chloritized on the margins, although
Due to the absence of direct crosscutting no more than 2 and 5 volume %, respectively. In
relationships between the Au-(Ag) epithermal and addition, biotite grains in PBR-215 encapsulate
sulfide-rich polymetallic mineralization types, it is euhedral quartz representing up to 4 % of the total
difficult to establish their relative timing. However, volume.
in the eastern flank of the volcanic complex, thin The three alunite samples from the Au-(Ag) high
sphalerite-galena veins encased by argillic to phyllic sulfidation epithermal bodies (PBR-198 and PBR-
alteration haloes cut the external mostly propylitic 214 from central Marcapunta and PBR-213 from two
alteration zones peripheral to the vuggy silica-hosted kilometers south, Fig. 3) were extracted from altered
Au-(Ag) bodies. This perhaps represents the best field rocks that consist predominately of quartz-alunite
relationship whereby it can be suggested that sulfide- with minor zunyite, pyrite, and supergene minerals
rich polymetallic ores were emplaced subsequent such as goethite and hematite (Fig. 4a). As it is typical
to the Au-(Ag) epithermal mineralization. Other for this mineralization type, dated alunite grains are
observations in the northern flank of the volcanic pink, euhedral, and dominantly potassic (8.3-8.7 wt.
complex are consistent with this view, specifically % K20, Table 1).
quartz-alunite selvages of the massive pyrite-enargite Three of the four alunite-bearing samples
bodies overprint and spatially, at deposit scale, overlap from the sulfide-rich polymetallic ores correspond
the external argillic to phyllic to propylitic alteration to zone I (samples PBR-131, PBR-137 from Smelter
zones related to the Au-(Ag) mineralization. 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
Dated samples inclusions. In accordance with the general composition
of alunite from this zone throughout the northern
In order to obtain quantitative data on the age part of the district, microprobe analyses reveal that
of igneous activity in the Colquijirca district and on dated alunite samples from Smelter (PBR-131, PBR-
the timing of formation of the two mineralization 137) and Colquijirca (PBR-218 ) are more potassic
types recognized from field observations, we (9.0-10.5 % K2O, Table 1) than alunite samples from
conducted a 40Ar/39Ar study of three biotite samples the Au-(Ag) epithermal ores. Alunite from the base
from fresh dacitic porphyry domes and seven metal ores is, in general, paragenetically earlier than
representative alunite-bearing ore samples. Three of pyrite and enargite, although some alunite formed
the alunite-bearing samples correspond to the Au- after pyrite and enargite. This reversed crystallization

124
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). Alunite and biotite grains were carefully
In zone III, alunite and sulfides occur in intricate handpicked from previously crushed and washed
intergrowth textures, and this is also evident in the samples. Only grains of microscopically high purity
alunite-sphalerite-galena-bearing sample selected for (< 2 volume % in of quartz/opaque contaminants)
dating (PBR-108, Fig. 4d). Alunite from this sample were selected. The grain separates were additionally
is colorless, euhedral and microscopically pure. treated by ultrasonic cleaning. Additional details
Microprobe analyses indicate that alunite from zone of the biotite and alunite samples, such as UTM
III at Colquijirca ranges from 9.0 and 10.5 weight % coordinates, average grain sizes, and sample amounts
K2O. In comparison with alunites from zone I, the are provided in Appendix 1.
PBR-108 alunite grains have in general considerably Irradiation of mineral separates for 40Ar/
higher F content and are slightly less sodic (Table 1). 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 (J) was determined with a precision of 0.5 percent,
extraction line connected to a MAP 215-50 mass and this uncertainty is propagated throughout the
spectrometer using an electron multiplier. The uncertainties on the reported ages. All ages and
incrementally heated gas was expanded and purified regressions in this paper are reported at the 95
using activated Zr/Ti/Al getters and a metal cold percent level of confidence.
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 Results
heights above backgrounds were corrected for
mass discrimination, isotopic decay and interfering The 40Ar/39Ar age spectra of the analyzed
nucleogenic Ca-, K- and Cl-derived isotopes of Ar. samples are presented in Figure 4 and results of
Blanks were measured at temperature and subtracted the 40Ar/39Ar analyses are summarized in Figure 5.
from the sample signal. For mass 40, blank values Age plateaus were determined using the criteria of
ranged from 4x10-15 moles below 1350C to 9x10- Dalrymple and Lamphere (1971): the presence of at
15
moles at 1650C. Blank values for masses 36- least three contiguous incremental heating steps with
39 were below 2x10-17 moles for all temperatures. statistically indistinguishable ages and constituting
Isotopic production ratios for the Triga reactor were more than 50 percent of the total 39Ar released during
determined from analysis of irradiated CaF2 and the experiment.
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/ 40Ar/39Ar data from magmatic biotite
39
Ar(K)=0.000860.00023. A mass discrimination
correction of 1.008 amu was determined by online Biotite sample PBR-148 provided a well
measurement of air and was applied to the data. For defined age plateau of 12.430.06 Ma (2) (Fig. 4).
this investigation, an uncertainty on the neutron flux 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 All of the alunite samples related to the Au-(Ag)
biotite from the upper part of Marcapunta (11.90.8 mineralization (PBR-198, PBR-213 and PBR-214)
Ma, 2; Vidal et al., 1984). Sample PBR-216 from a gave well defined age plateaus between 11.290.12
Huacchuacaja dome (Fig. 2) gave a slightly disturbed and 11.630.08 Ma (2) (Fig. 5). These ages are
but generally flat apparent age spectrum whose initial slightly to significantly older than the 10.60.6 Ma
steps may reflect partial radiogenic Ar loss. The (2) K/Ar age obtained on an alunite sample from
inverse isochron age of sample PBR-216 at 12.70.1 the upper part of the Marcapunta volcanic complex
Ma (MSWD of 1.5) is consistent with the PBR-148 (Vidal et al., 1984). The age plateaus of 11.330.14
age plateau (Table 2). Sample PBR-215, the least Ma and 11.290.12 Ma derived from samples PBR-
pure of the three biotite samples (see above), does 198 and PBR-214, respectively, are analytically
not show any interpretable plateau-like segments. Its indistinguishable at the 2 confidence level. This may
inverse isochron age of 12.90.1 Ma derived with a indicate that in this part of the diatreme complex, close
MSWD of 1.5 is, however, consistent with ages from to the diatreme vent, a single pulse of hydrothermal
the other magmatic biotites. activity generated the gold-bearing advanced argillic-
altered rocks. Alunite sample PBR-213 collected
two km south of the diatreme center (Figs. 2, 3)
Alunite 40Ar/39Ar data from Au-(Ag) epithermal yielded a flat age spectrum of multiple contiguous
ores 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
CHAPTER 3
Middle Miocene Late Miocene

Colquijirca district
on biotitec
Cerro de Pasco district
on sanidinec
on plagioclasea
on alunitec
on biotitea
on alunitec
on magmatic biotited
K/Ar on plagioclasea
on biotitea
on alunited
on sanidinea
volcanic complex
formation
Yanamate
on alunited
on whole rock b Au-(Ag) high sulfidation
epithermal mineralization
Cordilleran base
metal lode and
replacement
K/Ar mineralization
40Ar/39Ar, this study

15 14 13 12 11 10
Age (Ma)
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 Discussion and conclusions


80,000 and 540,000 years, considering 2). Such a
time gap indicates that high sulfidation fluids in this Volcanic and hydrothermal activity in the
southern part of the district were generated from a Colquijirca district (between ~12.7 and 10.6 Ma)
hydrothermal pulse prior to the pulse at 11.3 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
Alunite 40Ar/39Ar data from the sulfide-rich that the volcanic and hydrothermal activity occurred
polymetallic ores between 14-15(0.8-1.0) Ma at 2 (Silberman and
Noble, 1977). Similarly, one whole rock K/Ar analysis
As is the case for the Au-(Ag) epithermal from the nearby Yanamate diatreme-dome complex
ores, the four alunite samples from the sulfide-rich (Fig. 1) gave an age of 15.20.8 Ma at 2 (Soler and
polymetallic ores yielded clear age plateaus ranging Bonhomme, 1988), which is more than two million
between 10.830.06 and 10.560.08 Ma (2). These years earlier than magmatic ages obtained in the
new data are consistent with a previous K/Ar age Colquijirca district. On the basis of these available
reported by Vidal et al. (1984) on an alunite sample geochronological data it is concluded that Colquijirca
collected from massive enargite-pyrite ores (southern represents the youngest expression of the Miocene
Smelter) referred to here as zone I. No relation magmatism in the region.
between position (ore zone I or III) and age plateau The 40Ar/39Ar determinations on mineralization
is recognized. Sample PBR-108 from Colquijirca in the Colquijirca district reveal that the two physically
(zone III) gave an age plateau of 10.590.08 Ma separate ore types (Figs. 2, 3), Au-(Ag) disseminated
(2), analytically identical to sample PBR-137 from and the Cu-Zn-Pb-Ag-(Au-Bi) sulfide-rich ores,
Smelter (zone I) at 10.560.08 Ma (2). In this same formed at different times with a difference in age of
zone I age plateau have been obtained at 10.720.06 ~0.5 My (0.28-0.64 My at the 2 level of confidence).
Ma (sample PBR-218) and at 10.830.06 Ma (sample Such a long time gap possibly indicates that both ore
PBR-131). These ages argue for a protracted history types deposited from different hydrothermal events
of hydrothermal activity that formed the Cordilleran yet within the same magmatic cycle.
base metal ores through one or more pulses. On the The older event is recognized through possibly
basis of the 40Ar/39Ar ages, the duration of this event two pulses of advanced argillic alteration formation
can be estimated to be ~0.27 My (0.13 to as much as at ~11.3 Ma and ~11.6 Ma. Typical disseminated Au-
0.41 My considering 2). (Ag) epithermal mineralization is related to this older

131
CHAPTER 3

event in areas affected by vuggy silica alteration in period of 2 My. Intermediate ages within this
volcanic rocks of the Marcapunta diatreme-dome interval such as the earliest recognized hydrothermal
complex. pulse at ~11.6 Ma (vuggy silica formation in
During a second event (10.8-10.6 Ma), southern Marcapunta) and the earliest dated dome at
sulfide-rich polymetallic mineralization formed ~12.4 Ma, (PBR-148) argue for this possibility. Two
subhorizontal flat elongated tube-like lenses replacing million years of inferred magmatic activity represents
Eocene carbonate beds from the northern border of an interval of time long enough for the development
the Marcapunta diatreme dome complex for 4 km of a complex evolutionary history involving several
north. This mineralization has a definite zoning that thermal and/or magmato-volcanic episodes related
from internal to external parts displays the three to a single, fairly large magma chamber. Considering
following general main assemblages: the present results, the most plausible scenario for
- Cu-(Au) in enargite-pyrite ores, with alunite, the Colquijirca district is that the two recognized
zunyite and/or dickite-kaolinite (zone I) hydrothermal events were linked to at least two
- Cu-(Ag-Bi) as chalcopyrite (tennantite- major thermal episodes within the same magmatic
bornite-Bi sulfosalts) with alunite-dickite-kaolinite cycle (Bendez and Fontbot, 2002).
(zone II) In the Colquijirca district, the relative sequence
- Zn-Pb-(Ag) as sphalerite-galena with of events and the absolute ages obtained establish
kaolinitealunite, siderite (zone III) for the first time that Cordilleran base metal lode and
The alunite 40Ar/39Ar ages from zones I and replacements ores, mainly epithermal and formed at
III show that the sulfide-rich base metal ore types are high sulfidation and oxidations states, were emplaced
contemporaneous within errors. The geochronologic considerably later (~460,000 years) than the Au-(Ag)
data confirm the geometric observations suggesting high sulfidation epithermal mineralization, yet, both
that the massive pyrite-enargite Cu-(Au) ores of mineralization types formed from fluids with high
Smelter and the Colquijirca (mainly Zn-Pb-(Ag) sulfidation and oxidation states.
deposits) are parts of a continuous replacement
(Figs. 2, 3).
The recognized features of the sulfide-rich Acknowlegements
polymetallic replacement ores, including mineral
zoning, the high sulfidation and oxidation states of The present investigation is being carried out
the sulfide assemblages in the internal parts, associated with the support of the Sociedad Minera El Brocal
advanced argillic alteration, and the late timing of S.A. and the Swiss National Science Foundation (FN
formation characterize them as Cordilleran lode and 2000-062000.00). We acknowledge also the great help
replacement deposits in the sense of Einaudi (e.g., provided by the company geologists especially in the
1982, 1994). early period of this investigation, in particular Juan
The Pucar-hosted San Gregorio deposit, Proao, Carlos Yacila, Ivan Monteagudo, Mximo
for which age determinations are not yet available, is Yaringao, and Lucio Canchis. Constructive reviews
considered to be a low temperature and more acidic and comments by Lewis Gustafson, John Dilles,
and oxidizing equivalent of the sphalerite-galena- and an anonymous reviewer significantly improved
bearing zones encountered in the northern part of the manuscript. We wish to thank also the editorial
the district (Fontbot and Bendez, 2001). effort first by Richard Goldfard and finally by Larry
From the current knowledge on the lifespan of Meinert, this last who contributed in addition with
a single intrusion-related hydrothermal system (e. g., helpful comments and suggestions.
<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
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Einaudi, M.T., 1982, Description of skarns associ- Marsh T.M., Einaudi M.T. and McWilliams M., 1997,
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porphyry copper deposits, south western North America: ogy, 92: 784-806.
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635.
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tem, in Stanley et al., (eds.), Fifth Biennial SGA Meeting, 476.
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Owens, T.L. and DePaolo, D.J., 1998. Intercalibration of
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tion system. Proexplo 2001, Lima, Per, Abril 2001, CD- Renne, P.R., Deino, A.L., Walter, R.C., Turrin, B.D.,
ROM, doc. 18 p. Swisher III, C.C., Becker, T.A., Curtis, G.H., Sharp, W.D.,
and Jaouni, A.-R., 1994. Intercalibration of astronomical

133
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and radioisotopic time. Geology, 22: 783-786. Yaringao, M., Arias, W., and Panz, M., 1997, Ex-
ploraciones y evaluacin de los yacimientos del Distrito
Silberman, M.L. And Noble, D.C., 1977, Age of ig- Minero de Colquijirca, Pasco: IX Congreso Peruano de
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Sillitoe, R. H., 2000, Zinc Exploration at Colquijirca,


Central Peru. Private report for Compaa de Minas Bue-
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Soler, P., and Bonhomme M.G., (1988) Oligocene


magmatic activity and associated mineralization in the
polymetallic belt of central Peru: Economic Geology, v.
83, p. 657-663.

Stoffregen, R., 1987, Genesis of acid-sulfate alteration


and Au-Cu-Ag mineralization at Summitville, Colorado:
Economic Geology, v.82, p.1575-1591

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., 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
Peruano de Geologa, p. 217-219.

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
CHAPTER 3

Introduction mineralization consists of vuggy silica bodies,


with vertical dimensions of up to 100 m and gold
The Colquijirca District, located 12 km south concentrations of 1 - 2 g/t (Vidal et al, 1997). The
of the Cerro de Pasco District in central Peru bodies have been mainly recognized in the central
(Figure 3b.1), comprises various Cordilleran sulfide- portion of the complex, associated with the diatreme
rich polymetallic replacement deposits (Colquijirca, breccia and pyroclastic infill, where their morphology
Smelter, Marcapunta Oeste, San Gregorio) and a is controlled by both lithological and structural
disseminated high sulfidation Au-(Ag) prospect permeability. Less abundant gold-bearing zones of
(Marcapunta), all linked to a Miocene diatreme-dome completely oxidized veinlets have been recognized,
complex (Ahlfeld, 1932; Lindgren, 1935; McKinstry, particularly towards the surface. These zones have
1936; Yaringao et al., 1997; Vidal et al., 1997; bulk Ag/Au ratios ranging from 10 to 20. As in other
Bendez, 1997; Fontbot and Bendez, 1999, 2001; high sulfidation epithermal deposits, deep portions
Bendez and Fontbot, 2002; Bendez et al., 2003). of unoxidized ores characteristically contain less than
The Marcapunta Miocene diatreme dome 5 vol% of finely disseminated sulfides, mainly pyrite-
complex, exposed in the center of the Colquijirca enargite and very minor chalcocite, covellite, and
district (Sillitoe, 2001; Bendez et al., 2002; Sarmiento, sphalerite. Pre- and post-ore hydrothermal alteration
2004), is one of a series of volcanic edifices, including includes vuggy silica ledges within E-W fractures
Cerro de Pasco and Yanamate (Figure 3b.1), which and tubular bodies within phreomagmatic breccias
consist of multiple dome-lava intrusions of mainly (Figure 3b.2). The highest gold grades are found in
dacitic composition. Injection and explosion breccias the vuggy silica bodies, which are strongly zoned,
and pyroclastic layers, typical of diatreme conduits, forming dominantly quartz-alunite core assemblages
are extensively recognized at depth (Figure 3b.2). and outer zones of argillic alteration devoid of
Inward-dipping normal faults located in peripheral economic gold concentrations.
areas suggest that the entire edifice collapsed, possibly Cordilleran base metal deposits mainly
prior to the main episodes of mineralization (Figure consist of Cu-Zn-Pb-Ag(Au-Bi) zoned sulfide-
3b.2). rich replacements and represent a distinct and
As in large sectors of Central Peru, the district economically important type of mineralization in
is characterized by extensive exposures of carbonate the district. Cordilleran polymetallic mineralization
rocks of significantly varying ages. A 400 m thick aggregates collectively amount to a resource of at
sequence of limestone and dolostone of the Upper least 250 Mt. These aggregates include the Smelter
Triassic-Lower Jurassic Pucar Group occupies deposit (north of Marcapunta), where massive Cu-
the southern sector of Marcapunta. The Eocene (Au-Ag) ores were mined during the seventies, and
Pocobamba Fm., with a thickness up to 450 m, and the Marcapunta Oeste project (west of Marcapunta;
mainly composed of continental marls and limestones Vidal and Ligarda, 2004). The historical Zn-Pb-(Ag)
(Angeles, 1993), covers most of the northern sector Colquijirca mine is located further to the north and
of the Colquijirca District (Figure 3b.1). has been an important silver producer in Peru since
The mining district was affected by Tertiary pre-colonial times (Hutchinson, 1920; Lindgren,
folding (NNE fold axes), which pre-dates the 1935; McKinstry, 1936). The San Gregorio deposit,
emplacement of the Marcapunta volcanic complex located 3 km south of Marcapunta, was discovered
(Angeles, 1993). The major N-S trending, Longitudinal during 1994-1995, and hosts at least 70 Mt @ 7.3%
Fault, which has possibly been active since the Jurassic Zn, 2.18% Pb, 0.57 oz/t Ag, (Yaringao et al., 1997),
(Angeles, 1993), defines the eastern border of the constituting the largest undeveloped Zn-Pb-(Ag)
Colquijirca District, and dissects the Cerro de Pasco resource in the world. Mineralization at Colquijirca,
District to the north (Figure 3b.1). Other fracture Smelter, and Marcapunta Oeste is mainly hosted by
systems recognized in the Colquijirca District follow the Pocobamba Fm., whereas the large San Gregorio
NW and NE trends (Figure 3b.1). The Longitudinal deposit replaces Pucar Group rocks.
fault appears to control the emplacement of the A significant feature of the Colquijirca
Miocene intrusive rocks. NW oriented fractures and Cordilleran deposits is the high total sulfide content,
ring faults, related to the collapse of the Marcapunta which fluctuates between an average of 30 and
volcanic complex, probably played a significant role 50 vol%. The most abundant minerals are pyrite,
in channeling the ore fluids in much of the district which crystallized during an early silica-pyrite stage,
(Figure 3b.2). followed in abundance by enargite-pyrite from a
The district hosts two main types of Main ore stage and, finally, chalcocite from a Late
metallogenic mineralization: (i) disseminated high ore stage (Bendez, 2006). Strongly oxidized zones,
sulfidation Au-(Ag) epithermal mineralization, originally composed of enargite-pyrite, display Ag/
hosted within the volcanic complex of Marcapunta, Au ratios ranging from 80 to 120, much higher than
and (ii) Cordilleran base metal deposits hosted in the those found in the Oro Marcapunta disseminated
carbonate rocks of both the Pucar Group and the Au-(Ag) ores (10 to 20). Another major feature of
Pocobamba Formation. Cordilleran mineralization in the Colquijirca District
Au-(Ag) high sulfidation epithermal is the distinct ore zoning, defined by a Cu-(Au-Ag)
140
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- 444 and CM4-452) encountered up to 350 m of
(Zn-Pb-Ag-Bi) zone where chalcopyrite, sphalerite vertical section containing Au-(Ag) high sulfidation
and galena predominate; and an outer Zn-Pb-(Ag) epithermal ledges, which in the lowermost 50 m are
envelope composed of sphalerite and galena. A superimposed by Cordilleran ores. This superposition
Zn-bearing Fe-Mn carbonate zone, which is almost comprises barren, early stage quartz-alunite zones,
barren of sulfides, occurs in the outermost part. containing Au-(Ag) veinlets, all of which are cut
Recent drilling in the western flank of by cm wide pyrite-(enargite)-rich veinlets and less
Marcapunta (Marcapunta Oeste project) revealed frequently veins. Furthermore, a majority of cavities
crosscutting relationships, indicating that Cordilleran within the vuggy silica contain intergranular fillings
mineralization post-dates the Au-(Ag) disseminated of enargite of the Cordilleran stage, which in part
epithermal hydrothermal activity. Cordilleran veins destroy earlier Au-(Ag) veinlets with quartz-alunite-
systematically cut the precious metal veinlets and bearing assemblages.
veins in the easternmost portion of the Marcapunta
Oeste project. Several drill holes (e.g., CM3-

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
CHAPTER 3

Previous geochronologic data and scope database. If such lulls in hydrothermal activity exist,
of the present work then there may have been several discrete magmatic
events, each creating each their own mineralizing
This work presents the results of a high systems. We also aim to determine the first absolute
precision radiometric survey of alunite samples of mineralization ages of the large Cordilleran deposit of
the Colquijirca District, which is complementary to San Gregorio, in the southern part of the district.
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 Dated samples
presented. The later technique was used on samples
from San Gregorio, where, the extremely fine-grained Seven platy, coarse grained alunite separates
character of the alunite (Fontbot and Bendez, were selected for infra-red (CO2) laser step-heating
1999) precluded the possibility of 40Ar/39Ar analyses. 40
Ar/39Ar analysis. The composition of six of the dated
The combined results are consistent with the timing alunite samples was quantified using a microprobe,
of mineralizing events indicated by crosscutting field and all approach the theoretical alunite end-member
relationships (Bendez and Fontbot, 2002). stoichiometry. Four samples belong to the Au-(Ag)
The previous 40Ar/39Ar dating in the Colquijirca high sulfidation epithermal mineralization (Oro
District indicated that Cordilleran base metal lode and Marcapunta) and three to the Cordilleran base metal
replacement deposits from the Smelter and Colquijirca ores of the northern part of the district (Smelter and
deposits were formed by a late hydrothermal event, Colquijirca).
subsequent to Au-(Ag) high sulfidation epithermal Three whole-rock samples from San Gregorio,
mineralization at Oro Marcapunta (Bendez et in the southern part of the district, were dated using
al., 2003). Alunite samples related to the Au-(Ag) the K/Ar method. This less precise method was
epithermal ores were dated at 11.30.06 - 11.60.08 used because of the extremely fine grained habit of
Ma (2) and those from the Cordilleran base metal alunite, which is intergrown with pyrite.
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 Alunite samples from the Au-(Ag) epithermal high
two mineralization types in the Colquijirca District sulfidation mineralization
was interpreted in terms of distinct hydrothermal
events within the same magmatic cycle (Bendez et Alunites PBR-336 and PBR-338 of the Oro
al., 2002). Marcapunta Au-(Ag) epithermal mineralization were
According to the same survey, magmatic collected from the southern flank of the southern
biotite derived from flanking dacitic domes topographic high of Marcapunta, approximately 400
yielded 40Ar/39Ar ages ranging from 12.40.04 to m meters south of samples PBR-198 and 214, which
12.90.10 Ma, which is ~0.8 My older than the were previously dated using furnace 40Ar/39Ar step-
earliest recognized hydrothermal manifestation (e.g. heating. They represent internal parts of advanced
alunite PBR-213 from the Au-(Ag) high sulfidation argillic alteration zones (AAA zones), which
epithermal Oro Marcapunta event dated at 11.630.08 immediately envelope leached vuggy silica cores. In
Ma). Baumgartner (2006), reports a U-Pb age of these AAA zones, alunite is euhedral and dominantly
12.120.03 Ma for zircons from a dacitic dome accompanied by quartz (Figure 3b.3), though in some
from the western sector of the Marcapunta volcanic cases pyrophyllite, diaspore, and zunyite are locally
complex. This age, though relatively younger, is fairly important. Samples PBR-336 and PBR-338 are cut by
consistent with the 12.4-12.9 Ma period of dacitic Au-bearing veinlets composed mainly of oxides and
doming, a period thought to be part of the magmatic minor jarosite and quartz, indicating that precious
cycle associated with the mineralization in the whole metal deposition postdated the advanced argillic
Colquijirca District. alteration in the two points in which the samples were
The relatively long time gaps between the collected. The dated alunite grains are less than 1 mm
two mineralizing events and between the youngest long (Appendix 4b.2), corresponding to the typical
dated magmatic dome and the oldest recognized grain size of alunite in the internal part of the AAA
hydrothermal manifestation (0.5 and 0.8 My zones. In contrast to alunite from the external parts
respectively, Fig. 6 in Bendez et al., 2003) are of the AAA zones, the dated alunite from internal
inconsistent with modern hypotheses of the longevity zones is homogeneous and no pseudocubic cores
of hydrothermal cells related to single intrusions of the woodhouseite-svanvergite end-member were
(Marsh et al., 1997; Henry et al., 1997; Muntean and observed in thin section (Figure 3b.3). The dated
Einaudi, 2001). Consequently, the time-lags suggested samples display minor Na substitution by K (Na/K
by Bendez et al. (2003) may be an artifact of the between 0.1 and 0.6, Table 3b.1).
low quantity of age data. The principal aim of this The third Oro-Marcapunta alunite separate
study is to clarify the timing of mineralizing events (PBR-335) was extracted from a vuggy silica rock,
by acquiring a highly resolved geochronological 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). which typically occur in clusters within open-space
Alunite grains are, in this sample, platy, euhedral, fillings, are usually longer than 1 cm. Plumose alunite
transparent, pinkish and relatively coarse (up to 3 in this sample cements a breccia which contain
mm long). Microprobe analyses were performed rounded clasts of vuggy silica that bear oxide veinlets
on several alunite grains from the same rock. They (Figure 3b.3). Selective chemical analysis show that
are all compositionally homogeneous and close to veinlets-bearing vuggy silica clasts are mineralized
stoichiometric alunite (Table 3b.1). (up to 1 ppm Au), indicating that plumose alunite
Sample PBR-273 from Oro-Marcapunta postdated a period of gold deposition which in turn
contains plumose alunite. Individual alunite grains, 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
CHAPTER 3

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


K/Ar analysis
PBR-322 Smelter 10.640.06
As indicated above the fine-grained nature of
the material from San Gregorio prevented handpicking PBR-298 Colquijirca 10.760.06 10.750.07
and 40Ar/39Ar analysis. Therefore, alunite concentrates PBR-244 Colquijirca 10.750.06 10.600.08
from San Gregorio were prepared for K/Ar analysis. 1
Plateau age calculated according to the criteria of Dalrymple and
Concentrates were achieved by centrifuging a crushed Lamphere (1971)
material immersed within distillated water. Denser

146
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