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Thesis

Magmatic and hydrothermal fluid processes at the origin of the giant


porphyry-related epithermal polymetallic deposit of Cerro de Pasco
(Central Peru)

ROTTIER, Bertrand

Abstract

Le district du Miocène moyen de Cerro de Pasco, situé au centre du Pérou, contient le


second plus grand gisement épithermal polymétallique lié à un système porphyrique. Ce
travail consiste en une étude du magmatisme, des évènements hydrothermaux de hautes
températures consistant de minéralisation de type porphyrique, ainsi que de l'étude des
évènements hydrothermaux de basse température formant le gisement géant épithermal
polymétallique de Cerro de Pasco. Les nouvelles données obtenues permettent de
contraindre le lien entre le magmatisme et les différentes minéralisations hydrothermales, d'un
point de vue temporel, géochimique et pétrographique.

Reference
ROTTIER, Bertrand. Magmatic and hydrothermal fluid processes at the origin of the
giant porphyry-related epithermal polymetallic deposit of Cerro de Pasco (Central
Peru). Thèse de doctorat : Univ. Genève, 2016, no. Sc. 5086

URN : urn:nbn:ch:unige-955694
DOI : 10.13097/archive-ouverte/unige:95569

Available at:
http://archive-ouverte.unige.ch/unige:95569

Disclaimer: layout of this document may differ from the published version.
UNIVERSITÉ DE GENÈVE FACULTÉ DES SCIENCES
Section des Sciences de la Terre et de l’environnement Directeur : Prof. Lluís Fontboté
Département des Sciences de la Terre Co-directeur : Dr. Kalin Kouzmanov

Magmatic and hydrothermal fluid processes


at the origin of the giant porphyry-related
epithermal polymetallic deposit of Cerro de
Pasco (Central Peru)

THÈSE

Présentée à la Faculté des sciences de l’Université de Genève pour obtenir le


grade de Docteur ès Sciences, mention Sciences de la Terre

Par

Bertrand Rottier
De France

Thèse n°5086

GENÈVE
Atelier d’impression “ReproMail”, Université de Genève
2017
Table of Contents

Abstract ix
Résumé xiii

Chapter 1: Crystallization and rejuvenation cycles of a silicic magmatic


chamber at the origin of the magmatic-hydrothermal system of Cerro de Pasco,
Peru: geochronological and petrological evidence

Abstract 1
Introduction 3
General geology 4
District geology and mineralization 4
Description of the dated porphyry-type mineralization occurrences 7
Porphyry-type mineralization PM1 and PM2 7
Porphyry-type mineralization PM3 9
Methods 9
Results 15
Timing of magmatic and high-temperature hydrothermal events 15
Trace element signatures of zircon 17
Mineral composition and textures of magmatic rocks from the Cerro de Pasco district
19
Dacitic tuff 19
Dacitic domes 21
Rhyodacitic domes 21
Quartz-monzonite dykes 21
Porphyritic trachyte intrusions 22
Feldspar chemistry 23
Whole rock geochemistry 24
Silicate melt inclusions 31
Composition 31
Zircon saturation 33

i
Ti-in quartz thermobarometry 34
Discussion 35
New geochronological constraints on the hydrothermal mineralization at Cerro de Pasco
35
Magmatic evolution at deep crustal levels 37
Magma storage and rejuvenation 37
Conclusions 41
Acknowledgements 42
References 42
Supplementary tables 48

Chapter 2: Hydrothermal evolution of hidden porphyry-type mineralization


related to the large epithermal polymetallic deposit of Cerro de Pasco (Peru)

Abstract 78
Introduction 80
Geological settings 81
Recently recognized porphyry mineralization at Cerro de Pasco 85
Analytical methods 87
Sample selection and SEM-CL petrography 87
Microthermometry 87
Raman microspectroscopy 88
SIMS analyses 88
LA-ICP-MS analyses 88
Mineral thermobarometers 89
Ti in quartz 89
Zr in rutile 90
Zr in titanite 90
Results 90
Mineralized clast petrography 90
HT1 veins 92
HT2 veins 92
Pre-diatreme polymetallic mineralization 94
Trace element analysis of quartz, rutile and titanite 94

ii
Quartz 94
Rutile 95
Titanite 96
In-situ SIMS oxygen isotope analyses of different quartz generations 96
Fluid inclusions 97
Petrography, microthermometry and Raman analysis 97
Fluid composition 102
Melt inclusions 104
Petrography and description 104
Melt inclusions composition 104
Discussion 107
Comparison of the mineral thermobarometers 107
Pressure temperature reconstruction 108
HT1 veins 108
HT2 veins 110
Low temperature fluids 110
Origin and evolution of the fluids 111
Oxygen isotope signatures of the different events 112
Significance and origin of silicate melt inclusions in hydrothermal veins 114
Cerro de Pasco mineralizing system 115
Summary and conclusions 117
Acknowledgements 118
References 118
Supplementary figures 123
Supplementary tables 127

Chapter 3: Heterogeneous melt and hypersaline liquid inclusions in shallow


porphyry type mineralization as markers of the magmatic-hydrothermal
transition (Cerro de Pasco district, Peru)
(Published as Rottier, B., Kouzmanov, K., Bouvier, A.-S., Baumgartner, L., Wälle, M., Rezeau, H., Bendezú, R., Fontboté,
L., 2016, Heterogeneous melt and hypersaline liquid inclusions in shallow porphyry type mineralization as markers of the
magmatic-hydrothermal transition (Cerro de Pasco district, Peru): Chemical Geology, doi:
10.1016/j.chemgeo.2016.10.032)

iii
Abstract 146
Introduction 147
Geological setting 147
Porphyry mineralization at Cerro de Pasco 149
Analytical methods 149
Results 152
Trachyte porphyry and associated alteration 152
Vein petrography and SEM-CL quartz textures 152
In-situ SIMS oxygen isotope analyses of quartz 153
SIMS and LA-ICP-MS trace element analyses in quartz 154
Petrography and microthermometry of HSMIs and fluid inclusions 155
LA-ICP-MS analyses of fluid inclusions 157
Hypersaline liquid inclusions 157
Aqueous L-V inclusions 158
Composition of heterogeneous silicate melt inclusions (HSMIs) 158
Characterization HSMIs after heating using back-scattered electron imaging 158
EPMA 158
LA-ICP-MS analyses 158
Cation diffusion through quartz 161
Discussion 163
Origin of HSMIs in porphyry veins: supercritical melt versus heterogeneous entrapment
163
Fluid evolution 164
Origin of the fluid and ore precipitation 165
Cu and Ag diffusion through quartz 166
Implications for ore formation processes at Cerro de Pasco 166
Summary and conclusions 167
Acknowledgements 167
References 167
Supplementary tables 170

iv
Chapter 4: Sulfide replacement processes revealed by textural and LA-ICP-MS
trace element analyses: example from the early mineralization stages at Cerro
de Pasco, Peru
(Published as Rottier, B., Kouzmanov, K., Wälle, M., Bendezú, R., and Fontboté, L., 2016, Sulfide replacement processes
revealed by textural an LA-ICP-MS trace element analyses: example from the early mineralization stages at Cerro de
Pasco, Peru: Economic Geolology, v.111, p. 1347-1367.)

Abstract 179
Introduction 179
Geology and mineralization at Cerro de Pasco 180
Analytical methods 183
Pyrrhotite pipes and their rims (Stage A) 183
Pyrite-quartz body (Stage B) 184
Mineral textures at pyrrhotite pipe - pyrite-quartz body contacts 184
Trace element analysis by LA-ICP-MS 188
EMP analyses of sphalerite 192
Discussion 192
Textures 192
Trace elements 193
New interpretation of fluid evolution during mineralization at Cerro de Pasco 196
Conclusions 196
Acknowledgments 197
References 197
Supplementary tables 201

Chapter 5: Cyclic tapping of metal-rich hypersaline magmatic fluids at the


origin of the giant Miocene epithermal polymetallic deposit of Cerro de Pasco,
Peru
Abstract 209
Introduction 211
Geology and mineralization 212
Analytical methods 217
Results 221
Fluid inclusion petrography and microthermometry 221
P-T conditions 232

v
Element concentrations in fluid inclusions 233
Trace elements in sulfides 237
Discussion 243
Fluid mixing and origin of the mineralizing fluids 243
Fluid evolution and nature of the mineral assemblages 248
Trace elements in sulphides 249
Fluid inclusions in ore and gangue minerals 253
Conclusions 253
Acknowledgments 254
References 254
Supplementary tables 261

Chapter 6: Various fluid sources at the large epithermal polymetallic deposit


of Cerro de Pasco (Peru): constraints from radiogenic and stable isotope (Sr,
Pb, Cl) tracing on inclusion fluids and in-situ δ18O analyses of hydrothermal
quartz

Abstract 313
Introduction 315
Geological setting 316
Porphyry-type mineralization 319
Epithermal mineralization 319
Analytical methods 321
SEM-CL 321
SIMS 322
LA-ICP-MS 323
Crush-leach analyses 323
Results 325
Trace element ICP-MS analyses of inclusion fluids 325
Anion content and Cl isotopic composition 328
Sr and Pb isotopic compositions 329
In-situ oxygen isotope and trace element analyses in hydrothermal quartz 332
In-situ oxygen isotopes 332
Stage A 332
Stage B1 333
Stage B2 334

vi
Stage C2 336
Trace elements in quartz 337
Discussion 340
Trace elements in hydrothermal quartz 340
Application of Ti-in-quartz thermobarometer at low temperatures and pressures 340
Trace element and hydrogen distribution in quartz 340
Various fluid sources at the large epithermal polymetallic deposit of Cerro de Pasco 342
Role of meteoric water in the magmatic-hydrothermal system at Cerro de Pasco 342
Equilibrated fluids 346
Metal content of the mineralizing fluids 348
Chlorine isotopic composition 350
Conclusions 350
Acknowledgement 351
References 351
Supplementary figures 357
Supplementary tables 361
Appendix A.1 377

Chapter 7: Trace element diffusion and incorporation in quartz during heating


experiments
(Published as Rottier, B., Rezeau, H., Casanova, V., Kouzmanov, K., Moritz, R., Schlöglova, K., Wälle, M., Fontboté, L.
(2017). Trace element diffusion and incorporation in quartz during heating experiments. Contributions to Mineralogy and
Petrology, v.172, 20p.)

Abstract 381
Introduction 381
Sample and analytical procedure 382
Analytical methods 384
Results 385
Phase transition during heating experiments 385
EPMA profiles and maps 386
Magmatic quartz 386
Hydrothermal quartz from porphyry vein HVA 386
Hydrothermal quartz from porphyry vein HVB 389
LA-ICP-MS results 390
Trace element composition of magmatic quartz and melt inclusions 390

vii
Trace element composition of quartz and HSMI from porphyry vein HVA 390
Trace element composition of hydrothermal quartz from porphyry vein HVB 392
Discussion 393
Discrepancy between EPMA and LA-ICP-MS measurements 393
Diffusion of elements into SMIs and HSMIs 395
Cations incorporation in the quartz structure 395
Source of the diffusive elements 396
Conclusions and implications 398
Acknowledgements 398
References 398
Supplementary figures 401
Supplementary tables 405

Acknowledgements 431

viii
Abstract

The mid-Miocene Cerro de Pasco district, central Peru, hosts the second known largest
porphyry-related epithermal polymetallic ("Cordilleran") deposit after Butte in Montana, USA. The
epithermal polymetallic mineralization mainly replaces carbonate rocks of the Mesozoic Pucará
Group along the eastern border of a large diatreme-dome complex. Previous works had proposed an
affiliation to a porphyry-system, but no direct evidence of porphyry mineralization was found.
During the present study, three porphyry-type mineralization styles were identified as clasts in the
diatreme (PM1), outcropping at surface (PM2), and as clasts in quartz-monzonite dykes (PM3).
Large pervasive alteration zones (pyrophyllite-quartz-pyrite; illite-smectite-muscovite-pyrite;
chlorite-calcite-pyrite) have been also identified in the central and the northern parts of the diatreme-
dome complex probably resulting from interaction with relatively acidic magmatic vapors, generated
by degassing of the deeper part of the porphyry system. These new findings give the opportunity to
study the porphyry system from its deeper to shallower parts. The broad aim of the present
contribution is to bring a new comprehensive study of the porphyry system at the origin of the large
Cerro de Pasco epithermal polymetallic deposit, starting with its magmatic evolution, then studying
the fluid processes leading to the porphyry-type mineralization, and to the formation of the large
epithermal polymetallic deposit.
Chapter 1 is devoted to the magmatic system and its relationship with the different
mineralization styles. The newly obtained CA-ID-TIMS U–Pb ages of magmatic zircons from the
porphyry manifestations suggest continuous magmatic activity during more than 300 ka punctuated
by high-temperature porphyry-type mineralization events. The epithermal polymetallic
mineralization occurs after the first one but to some extent could also overlap it, a maximum gap of
0.9 Ma between the two events has been estimated. The sub-volcanic and volcanic rocks of Cerro de
Pasco were studied using petrographic, geochemical (whole-rock and mineral), isotopic (Pb, Sr, Nd)
methods combined with the study of silicate melt inclusions hosted in quartz phenocrysts. All
magma batches underwent a period of evolution in the deep crust (> 8 kbar) as reflected by their
typical subduction-related and garnet-fractionation chemical signatures. Prior to their emplacement
at shallow levels, magmas were stored at upper crustal level at high degree of crystallinity (up to
90% crystals) at pressures between 2 and 4.4 kbar and temperatures between 675° and 750°C. At
such conditions magmas past the point of rheological lock-up, therefore several events of
rejuvenation of this high-crystallinity silicic magmatic body were necessary to allow ascent of the
parental magma for the various subvolcanic and volcanic bodies at Cerro de Pasco. The energy
necessary to rejuvenate this high-crystallinity silicic magmatic body was provided by circulation of
hot magmatic volatiles in the not fully crystallized magma chamber, as suggested by the presence of
different high-temperature porphyry-type mineralization styles. Our results show complex transient

ix
regimes of crystallization and rejuvenation of a stored high-crystallinity silicic magmatic body where
episodes of rejuvenation could be as short as 85 ka.
Chapters 2 and 3 are dedicated to the study of newly found porphyry type mineralization.
Chapter 2 is focused on the high-temperature porphyry-type veins in hornfels and magmatic clasts
in the diatreme breccia (PM1). Such veins allow studying porphyry-type mineralization originated
from deep portion of the magmatic-hydrothermal system. They contain hydrothermal quartz that
hosts silicate melt inclusions as well as fluid and solid mineral inclusions. Two types of quartz-
molybdenite-(chalcopyrite)-(pyrite) veins were identified an early HT1-type veins crosscut by HT2-
type veins. Fluid inclusion microthermometry and the various mineral thermobarometers applied
reveal that HT1 veins were formed at temperatures >700°C and at pressures between 500 and 1300
bars, and that HT2 veins were formed at temperature ~600°C and pressure between 710 and 850
bars. Both vein types are locally crosscut and/or reopen by a late polymetallic event consisting of
pyrite, sphalerite with “chalcopyrite disease”, galena, chalcopyrite, fahlore group minerals, and
minor quartz. Crosscutting relationships indicate that the polymetallic event recognized in the clasts
took place before the one that formed the giant post-diatreme polymetallic deposit. The silicate melt
inclusions trapped in the veins represent melt droplets transported in the ascending hydrothermal
fluids. LA-ICP-MS analyses of the mineral inclusions and the fluid inclusions hosted in HT1 and
HT2 veins, and in-situ SIMS oxygen isotope analyses of vein quartz reveal a strong magmatic
signature of the mineralizing fluids with minor meteoric water input, and allow reconstructing the
chemical evolution of fluids forming these veins. Chapter 3 focuses on the stockwork of banded
quartz-magnetite-chalcopyrite-(pyrite) porphyry-type veinlets (PM2) crosscutting the trachyte
porphyritic intrusions cropping out at surface in the central part of the diatreme-dome complex. This
porphyry-type mineralization is emplaced at shallow level (depth < 1 km, P < 270 bars), implying
rather unusual low-pressure and high-temperature environment for the formation of porphyry-style
mineralization. The banded porphyry-type veinlets record a multiphase history of formation with two
successive high-temperature (>600°C) stages, followed by a lower-temperature (<350°C) stage.
Stage 1 is characterized by the entrapment of heterogeneous inclusions containing variable
proportions of evolved silicate melts and hypersaline liquid. These unusual inclusions result from
fluid exsolution at low pressure (270 bars) and high temperature (>600°C) from an evolved hydrous
rhyolitic melt ascending to shallow levels. During stage 2 only magmatic hypersaline liquid
inclusions are trapped. The low-temperature stage 3 (<350°C) is associated with the precipitation of
a chalcopyrite-pyrite-sphalerite-(pyrite) assemblage possibly favored by mixing of minor meteoric
water with magmatic-dominated fluids, as indicated by the in-situ SIMS 18O/16O isotope analyses.
The hypersaline liquid inclusions found in the porphyry-type mineralization PM1 and PM2
have similar Pb/Zn ratios to those of the bulk ore extracted from the epithermal polymetallic ore
bodies at Cerro de Pasco, thus suggesting a common source for the fluids associated with the
different mineralization styles at Cerro de Pasco.

x
Chapters 4, 5, and 6 are focused on the large epithermal polymetallic mineralization. The
latter results from the following three successive mineralization stages characterized in general terms
by an evolution from low- to high-sulfidation mineral assemblages: (i) pyrrhotite pipes grading
outwards to Fe-rich sphalerite and galena replacement bodies (stage A), (ii) deep quartz-pyrite veins
(stage B1) and a massive funnel-shaped pyrite-quartz replacement ore-body (stage B2) with quartz-
sericite alteration, and (iii) well-zoned Zn-Pb-(Bi-Ag-Cu) carbonate-replacement ore-bodies (stage
C1) and E-W- trending Cu-Ag-(Au-Zn-Pb) enargite-pyrite veins (stage C2); stages C1 and C2 are
spatially associated with zones of advanced-argillic alteration. Chapter 4 is focused on the relative
chronology of stages A and B. A detailed study of mineral replacement textures combined with LA-
ICP-MS analyses shows that the pyrrhotite pipes and associated polymetallic mineralization of stage
A predates the pyrite-quartz-body (stage B) and not the contrary as proposed in previous works. The
mineral textures and compositions indicate progressive increase of fS2, fO2, and decrease of pH of
the mineralizing fluids from stage A to B and within stage B. Chapter 5 deals with the evolution
(temperature, pressure and composition) of the mineralizing fluids during mineralization stages A, B,
and C. It is based on a detailed microthermometric and LA-ICP-MS study of fluid inclusions hosted
in gangue and opaque ore minerals and available bulk and in-situ SIMS oxygen isotope analyses of
hydrothermal quartz. Mineralizing fluids of the three stages were trapped at moderate temperatures
(~150°–280°C) and display wide range in salinity (1.2 to 19 wt % NaCl equiv.) without evidence of
phase separation; in stage C2, FIAs display a more restricted salinity range, mainly between 1.2 and
2.7 wt% NaCl eq. Fluids forming mineralization stages A, B1, B2 and C1 result from a mixing
between high-salinity metal-rich (> 1 wt% Mn, Fe, Zn, and Pb and up to several 1000s of ppm Sb)
magmatic fluids and low-salinity less metal-rich fluids also of magmatic origin. Our results suggest
the existence of a homogeneous reservoir of hypersaline metal-rich porphyry-type fluids stored at
depth, that has been repeatedly remobilized by ascending newly exsolved condensed magmatic
vapor-like fluids. The resulting mixed fluid rose to form mineralization stages A, B1, B2 and C1,
whereby in this latter stage fluids were also strongly mixed with meteoric water as indicated by bulk
and in-situ (SIMS) oxygen isotope analyses on quartz. The enargite-pyrite veins of stage C2 were
formed by the ascent of CO2-bearing contracted vapor, subsequently mixed with meteoric water; no
evidence of mixing with the hypersaline metal-rich magmatic fluids has being found for this
mineralization stage. The repeated remobilization of metal-rich high-salinity magmatic fluids stored
at depth recognized in stages A, B1, B2 and C1 is a distinctive feature of the formation of the giant
polymetallic deposit of Cerro de Pasco. Chapter 6 is dedicated to the definition of the various fluid
sources and the relative proportion of different fluid types involved in the formation of the
epithermal polymetallic mineralization at Cerro de Pasco. Application of Sr, Pb and Cl isotope
analysis, in combination with ion chromatography and ICP-MS analyses of fluid inclusion leachates
from 2 samples of porphyry-type mineralization and 12 samples of epithermal mineralization allows
recognizing radiogenic Sr and Pb signatures and high Br/Cl ratio (> 2 x 10-3) in the fluid forming the

xi
epithermal polymetallic deposit. These signatures have been interpreted as interaction of the
ascending mineralizing fluids with the Excelsior shales and phyllites. Potential mixing between this
upcoming magmatic fluids and meteoric water at shallower level was tracked using in-situ δ18O
SIMS analyses of quartz crystals from stages A, B1, B2 and C2. Only minor input of meteoric water
was recorded by quartz from stages A, B1 and B2, and no correlation with the obtained δ18O, trace
element content and the SEM-CL textures of the quartz crystals was observed. In contrast, quartz
crystals from the enargite-veins of stage C2 registered involvement of meteoric water as suggested by
growth zones associated with low δ18O, low trace element content and dark CL intensity.

Chapter 7 investigates the diffusion and incorporation of trace elements (derived from surrounding
minerals and inclusions, as well as from the heating stage itself) in quartz and quartz-hosted melt
inclusions during high-temperature heating experiments using a Linkam stage TS1500. Heated
magmatic and hydrothermal quartz crystals reveal significant modification of their Cu, Li, Na, and B
content and modification of the Cu, Li, B, Na, Ag, K, Cs, and Rb concentrations of their melt
inclusions. Heated magmatic quartz crystals display only discrete Cu and Na enrichments (few ppm),
mostly incorporated by substitution for Li. In contrast, heated hydrothermal quartz shows enrichment
in Cu, Li, and Na up to several hundreds of ppm. These elements are incorporated by substitution of
H+ cations present in the quartz structure prior to heating. Our results suggest that the composition of
quartz and quartz-hosted melt inclusions may significantly be modified upon heating experiments,
which may subsequently lead to erroneous elemental concentration determinations. In addition, this
study reveals the existence of a sub-surface layer being significantly enriched in Cu during heating.
We propose that this sub-surface enrichment, easily detectable by EMPA, can be used to track Cu
diffusion in quartz from an external source.

xii
Résumé
Le district du Miocène moyen de Cerro de Pasco, situé au centre du Pérou, contient le
second plus grand gisement épithermal polymétallique lié à un système porphyrique. Ce dernier se
situe à la bordure Est d’un complexe dôme-diatrème et remplace principalement les roches
carbonatées du Trias supérieur – Jurassique inferieur appartenant à la formation du Pucará. Des
travaux antérieurs ont proposé une affiliation de ce gisement à un système porphyrique mais aucune
évidence directe d’un tel lien n’avait été trouvée. Lors de cette étude, trois différentes occurrences de
minéralisation de type porphyre ont été identifiées. Elles consistent en : des clastes trouvés dans la
brèche de diatrème (PM1), affleurant à la surface (PM2) et en des clastes inclus dans un dyke de
quartz-monzonite. Une large altération (pyrophyllite-quartz-pyrite; illite-smectite-muscovite-pyrite;
chlorite-calcite-pyrite) a aussi été identifiée dans la partie centrale et nord du complexe dôme-
diatrème. Cette altération est probablement liée à l’interaction des roches avec de vapeurs
magmatiques acides générées par un dégazage des parties profondes du système porphyrique. Ces
nouvelles découvertes nous donnent l’opportunité d’étudier le système porphyrique des parties les
plus profondes jusqu’à celles les plus proches de la surface. Le thème de cette étude est d’apporter
une compréhension nouvelle du système porphyrique lié au grand gisement épithermal
polymétallique de Cerro de Pasco, en commençant par l’étude du système magmatique, puis par
celle des minéralisations de type porphyre et enfin par l’étude du gisement épithermal
polymétallique.
Le Chapitre 1 est dédié au système magmatique et à sa relation avec les minéralisations de type
porphyres. Les nouvelles datations U–Pb des zircons magmatiques par CA-ID-TIMS suggèrent une
activité magmatique continue sur plus de 300 ka, ponctuée par différents évènements de
minéralisation de type porphyre. Les minéralisations épithermales polymétalliques se forment suite à
cette première période mais dans une certaine mesure peuvent temporellement chevaucher cette
dernière, un écart maximum de 0.9 Ma entre les deux périodes. Une étude pétrographique,
géochimique (roches totales et minérales) et isotopique (Pb, Sr, Nd) a été conduite sur les roches
volcaniques et sub-volcaniques du district, ainsi qu’une étude des inclusions vitreuses contenues
dans le quartz. Cette étude montre que l’ensemble des magmas ont subi une première période
d’évolution dans la croûte inférieure (> 8 kbar) comme illustré par leurs signatures chimiques
typiques de magma de subduction ayant fractionné du grenat. Avant leurs emplacements, les
magmas ont été stockés à un haut degré de cristallinité, à une pression entre 2 et 4.4 kbar et à basse
température entre 675° et 750°C. Dans de tels conditions, les magmas ne peuvent pas être mobilisés.
Ainsi, plusieurs évènements de refonte de cet amas de cristaux ont été nécessaires pour permettre
ponctuellement l’ascension du magma formant les roches magmatiques visibles aujourd’hui.
L’énergie nécessaire à la refonte a été fournie par de nouvelles intrusions et la circulation de volatiles
magmatiques chauds comme suggéré par la présence des minéralisations de type porphyre de haute

xiii
température. Nos résultats montrent un régime transitoire complexe alternant des périodes de
cristallisation et de refonte du corps magmatique fortement cristallisé stocké en profondeur, celle-ci
pouvant être rapides (< 85 ka).
Les chapitres 2 et 3 sont consacrés à l’étude des minéralisations de type porphyre. Le
Chapitre 2 est dédié aux veines de haute température recoupant des clastes de cornéennes et de
roches magmatiques incorporées dans la brèche de diatreme (PM1). Ces veines offrent l’opportunité
d’étudier les minéralisations de porphyres de haute température mises en place dans les parties
profondes du système. Elles contiennent des cristaux de quartz présentant des inclusions vitreuses et
ainsi que des inclusions fluides et solides. Deux types de veines à quartz- molybdenite-
(chalcopyrite)-(pyrite) ont été identifiées : des veines précoces « HT1 » recoupant des veines
« HT2 ». L’étude par microthermométrie des inclusions fluides et l’application de différents
géothermobaromètres ont révélé que les veines HT1 ont été formées à des températures > 700°C et
des pressions entre 500 et 1300 bars, et que les veines HT2 ont été formées à des températures
~600°C et des pressions entre 710 and 850 bars. Ces veines (HT1 et HT2) sont parfois recoupées par
une minéralisation polymétallique formée de pyrite, de sphalerite avec des exsolutions de
chalcopyrite, de galène, de chalcopyrite, de fahlore et de quartz en de moindre proportion. Les
relations de recoupement indiquent que la minéralisation polymétallique observée dans les veines est
différente et plus ancienne que celle constituant le large gisement épithermal polymétallique. Les
inclusions vitreuses piégées dans les veines représentent des gouttes de magmas transportées par les
fluides hydrothermaux ascendants. L’analyse par LA-ICP-MS des différents inclusions fluides et
solides présente dans les veines HT1 et HT2 ainsi que les analyses in-situ des isotopes d’oxygène du
quartz montrent une origine magmatique des fluides minéralisateurs et permettent de reconstituer
leurs évolutions chimiques. Le chapitre 3 se concentre sur le stockwork de veinules de type
porphyre à quartz-magnétite-chalcopyrite-(pyrite) recoupant une intrusion de trachyte porphyrique
affleurant à la surface au centre du complexe dôme-diatrème. Cette minéralisation de type
porphyrique s’est formée proche de la surface à une profondeur inférieure à 1 km (P < 270 bars),
impliquant des conditions inhabituelles pour ce type de minéralisation qui consistent en une faible
pression et une température élevée. Les veinules de type porphyre enregistrent une histoire
polyphasée comprenant deux épisodes de haute température (>600°C) suivit par un épisode de plus
faible température (<350 °C). Plus de 90% du quartz des veinules s’est formé durant les épisodes de
haute température. La période 1 se caractérise par le piégeage dans les quartz hydrothermaux
d’inclusions contenant, en différentes proportions, un magma silicaté et un liquide hypersalin riche
en métaux (>90 wt % NaCl eq. ; nommées HSMIs). Ces inclusions inhabituelles sont formées par le
piégeage hétérogène d’un magma rhyolitique et d’un fluide hypersalin à basse pression et haute
température (270 bar, >600°C). Durant la deuxième période, seules des inclusions hypersalines sont
piégées. La troisième période (< 350°C) est associée à la précipitation de chalcopyrite, de pyrite, et

xiv
de sphalerite, potentiellement favorisée par le faible mélange d’eau météorique au fluide magmatique
comme suggéré par les analyses in-situ des isotopes d’oxygène du quartz associés à cette période.
Les inclusions hypersalines observées au sein des veines des minéralisations de type
porphyres PM1 et PM2, présentent un ratio Pb/Zn similaire à celui du minerai extrait des corps
minéralisés du gisement polymétallique de Cerro de Pasco. Cette observation suggère une source
commune des fluides minéralisateurs à l’origine des différents types de minéralisations présentes à
Cerro de Pasco.

Les chapitres 4, 5 et 6 sont dédiés à l’important gisement épithermal polymétallique. Il est formé
par trois épisodes minéralisateurs successifs caractérisés en général par une évolution allant
d’associations minérales de basse à haute sulfidation : (i) plusieurs pipes de pyrrhotite entourés de
corps de remplacement dominés par de la sphalerite et de la galène (épisode A) ; des veines
profondes de quartz et de pyrite (épisode B1), ainsi qu’un important corps de remplacement formé de
pyrite et de quartz (épisode B2), de plusieurs corps de remplacement (épisode C1) bien zonés à Zn-
Pb-(Bi-Ag-Cu) ainsi que des veines E-W riche en Cu-Ag-(Au-Zn-Pb) formées de pyrite et d’énargite
(épisode C2). Les deux derniers épisodes sont associés à une altération argilique avancée. Le
chapitre 4 est concentré sur l’étude de la relation chronologique des épisodes A et B. Il consiste en
une étude détaillée des textures de remplacement minérales associées à l’analyse par LA-ICP-MS
des minéraux remplacés et nouvellement formés. Les observations montrent que les pipes de
pyrrhotite et leurs minéralisations polymétalliques (épisode A) sont précoces par rapport au corps de
pyrite et de quartz (épisode B) contrairement à ce qui avait été proposé dans les travaux antérieurs.
Les textures minérales ainsi que leurs compositions indiquent une progressive augmentation de fs2,
fo2, et une diminution du pH des fluides minéralisateurs de l’épisode A à l’épisode B, ainsi que au
sein de l’épisode B lui-même. Le chapitre 5 est consacré à l’étude de l’évolution (température,
pression et composition) des fluides minéralisateurs formant les différents épisodes de
minéralisations A, B and C. Il consiste en une étude microthermométrique détaillée et en l’analyse
par LA-ICP-MS des inclusions fluides présentes dans les minéraux de gangues et les sulfures
opaques des différents épisodes minéralisateurs utilisant la microscopie classique et proche
infrarouge. Cette étude se base notamment sur les résultats précédemment des isotopes stables (O
and H) obtenus sur cristaux entiers et des isotopes d’oxygènes obtenus in-situ par SIMS sur des
cristaux de quartz. Le fluide minéralisateur à l’origine des trois épisodes était à une température
modérée (~150°–280°C) mais présentait une large gamme de salinité (entre 1.2 et 19 wt % NaCl
equiv.). Aucune évidence de séparation de phase n’a été observée. Pour l’épisode C 2, les
assemblages d’inclusions fluides sont caractérisés par des salinités entre 1.2 et 2.7 wt % NaCl equiv.
Les fluides formant les épisodes A, B1, B2 et C1 sont le résultat d’un mélange entre un fluide
magmatique de forte salinité et riche en métaux (> 1 wt% Mn, Fe, Zn, and Pb et jusqu’à plusieurs
milliers de ppm de Sb) et un autre fluide magmatique peu salin et moins riche en métaux. Nos

xv
résultats suggèrent l’existence d’un réservoir de fluide hypersalin, riche en métaux de type porphyre
stocké en profondeur. Ce réservoir a été mobilisé de façon répétée par l’ascension de vapeurs
magmatiques condensées nouvellement exsolvées. Le fluide résultant de ce mélange remonte et
forme les épisodes de mineralizations A, B1, B2 et C1. Pour l’épisode C1, le fluide ascendant est aussi
mélangé à de l’eau météorique comme indiqué par les isotopes d’oxygène précédemment obtenus.
Les veines d’énargite et de pyrite de l’épisode C2 ont été formées par l’ascension de vapeurs
magmatiques condensées contenant du CO2 mélangées avec de l’eau météorique proche de la
surface. Aucune interaction avec les fluides hypersalins de porphyres n’a été observée. La
mobilisation répétée de fluide hypersalin, riche en métaux de type porphyre stocké en profondeur,
identifié pour les épisodes de mineralizations A, B1, B2 et C1, est une caractéristique distinctive dans
la formation du gisement épithermal polymétallique géant de Cerro de Pasco. Le chapitre 6 est
dédié à la détermination des sources potentielles des fluides minéralisateurs ainsi qu’une estimation
de leurs relatives importances. Dans cet objectif, nous avons déterminé les signatures isotopiques du
Sr, Pb et du Cl, ainsi que le contenu en anions et éléments traces de deux lessivages d’inclusions
fluides, de deux échantillons de minéralisations porphyriques et de 12 échantillons provenant des
différents épisodes de la minéralisation épithermale. Les analyses montrent un contenu en métaux
plus important dans les lessivages d’inclusions fluides des épisodes de la minéralisation épithermales
que dans les minéralisations porphyriques. Elles indiquent que le fluide formant le gisement
épithermales polymétallique de Cerro de Pasco présente une signature isotopique de Sr et Pb plus
radiogéniques et un ratio Br/Cl élevé (> 2. 10-3). Ces signatures ont été interprétées comme résultant
de l’interaction de fluides minéralisateurs ascendants avec les phyllites et les argiles noires de
l’Excelsior. Le possible mélange entre ce fluide et une eau météorique dans la partie supérieure du
système minéralisé a été investigué grâce à plusieurs analyses in-situ d’isotope d’oxygène par SIMS
sur les cristaux de quartz des épisodes minéralisateurs A, B1, B2 and C2. Seulement de faibles
additions d’eaux météoriques ont été enregistré dans les cristaux de quartz des épisodes
minéralisateurs A, B1, and B2, et aucune corrélation entre les signatures isotopiques, le contenu en
éléments traces et la texture (SEM-CL) des cristaux de quartz a été observée. En contraste, les
cristaux de quartz provenant des veines à enargite et pyrite de l’épisode C2, présentent des zones
caractérisées par de faible signature en δ18O, un faible contenu en élément traces et couleur sombre
de luminescence (SEM-CL). Nous interprétons ces parties de cristaux comme étant formées par un
fluide dominé par de l’eau météorique.

Le chapitre 7 consiste en l’étude de la diffusion et de l’incorporation de certains éléments traces


(provenant des minéraux voisins, des inclusions du quartz et aussi de la platine elle-même) dans les
cristaux de quartz ainsi que de leurs inclusions, à travers un chauffage séquentiel avec une platine
Linkam TS1500. Les cristaux de quartz hydrothermaux et magmatique et leurs inclusions ayant été
chauffés présentent respectivement une modification de leurs concentrations en Cu, Li, Na, and B et

xvi
en Cu, Li, B, Na, Ag, K, Cs, et Rb. Les quartz magmatiques chauffés présentent seulement un faible
enrichissement en Cu et Na, majoritairement incorporé par substitution du Li. En revanche, les
quartz hydrothermaux chauffés présentent un fort enrichissement en Cu, Li and Na, jusqu’à quelques
centaines de ppm. Ces derniers sont incorporés par remplacement de l’hydrogène présent
initialement dans la structure du quartz avant chauffage. Nos résultats montrent que la composition
du quartz et de leurs inclusions vitreuses peut être modifiée de manière significative durant leurs
chauffages. De plus, notre étude démontre l’existence d’une couche supérieur au sein des cristaux
pouvant être enrichie en Cu de manière significative pendant le chauffage. Nous suggérons que
l’enrichissement de cette couche supérieure peut être utilisé pour identifier la diffusion du cuivre
d’une source externe vers les cristaux de quartz.

xvii
Chapter 1

Crystallization and rejuvenation cycles of a silicic


magmatic chamber at the origin of the magmatic-
hydrothermal system of Cerro de Pasco, Peru:
geochronological and petrological evidence

Bertrand Rottier*, Kalin Kouzmanov*, Maria Ovtcharova*, Alexey Ulianov** Markus

Wälle***†, Dave Selby****, and Lluís Fontboté*

*Departement of Earth Sciences, University of Geneva, 1205 Geneva, Switzerland

(Bertrand.Rottier@unige.ch)

**Institute of Mineralogy and Geochemistry, University of Lausanne, 1015 Lausanne,

Switzerland

*** Institute of Geochemistry and Petrology, ETH Zürich, 8092 Zürich, Switzerland

present address: Memorial University of Newfoundland, CREAIT, CRC and CFI Services
(CCCS), Bruneau Centre for Research and Innovation, St. John’s, NL, Canada, A1C 5S7
**** Department of Earth Sciences, University of Durham, Durham DH1 3LE, United
Kingdom
Corresponding author: Bertrand.Rottier@unige.ch

Abstract
Cerro de Pasco district in central Peru hosts the second world largest porphyry-related
epithermal polymetallic deposit. The district is centered onto a large diatreme-dome complex
crosscut by numerous dacite to rhyodacite bodies showing domal structures and dykes.
Recently, three temporally distinct high-temperature porphyry-type mineralization events
have been established (PM1, PM2, and PM3). New dating of the first porphyry-type

1
mineralization event PM1 (15.59 ± 0.12 Ma, molybdenite Re-Os) indicates that it slightly
predates volcanic activity (15.36 ± 0.03 and 15.16 ± 0.04 Ma, zircon U-Pb, published
previously). Crosscutting relationships and new and available zircon U-Pb ages of magmatic
rocks allow bracketing the two other porphyry-type mineralization events: PM2 was formed
between 15.286 ± 0.018 and 15.158 ± 0.035 Ma, and PM3 between 15.165 ± 0.043 and
15.158 ± 0.035 Ma. These dates suggest continuous magmatic activity during more than 400
ka punctuated by three high-temperature porphyry-type mineralization events that are
precursor (maximum gap of 0.9 Ma) of the large epithermal polymetallic mineralization at
Cerro de Pasco.
New petrographic, geochemical (whole-rock and mineral), isotopic (Pb, Sr, Nd) data
and the study of silicate melt inclusions hosted in quartz phenocrysts indicate that the magmas
at the origin of the sub-volcanic and volcanic rocks of Cerro de Pasco underwent a period of
evolution in the deep crust, as indicated by typical subduction-related and adakite-like
signatures. Our results suggests that magmas prior to their emplacement at shallow level were
stored at depth with a high degree of crystallinity (up to 90% crystals) at pressures between 2
and 4.4 kbar and at temperatures between 675° and 750°C. At such conditions, the magmas
are beyond the point of rheological lock-up and are not eruptible. Several events of
rejuvenation of this high-crystallinity silicic magmatic body were necessary to allow ascent of
the parental magmas of the various subvolcanic and volcanic bodies at Cerro de Pasco. Our
results point to complex transient cycles of crystallization and rejuvenation of a stored high-
crystallinity silicic magmatic body with circulation of hot magmatic volatiles. Episodes of
rejuvenation and porphyry-type mineralization could be as short as 85 ka.

2
Introduction
Vertical extent of porphyry systems, from deep underlying plutons to near-surface,
where epithermal deposits are formed, is between 5 and 15 km (Sillitoe 2010). Reconstruction
of the spatial and temporal connection between the different parts of the system (i.e., plutonic
intrusions, volcanic bodies, and porphyry-type and epithermal mineralizations) is complex
and requires good knowledge of the magmatic system and geochronological data. Classical
models imply that magmatic volatiles are exsolved from a deep crystallizing and convecting
large silicic magma chamber (e.g. Burnham 1997, Shinohara 1995, Shinohara and Hedenquist
1997). Volatile saturation is reached by primary boiling due to decompression and by
secondary boiling linked to crystallization, and when the fluid percolation threshold is
reached, fluids are able to migrate upwards and potentially to form porphyry and epithermal
deposits (Burnham 1997, Shinohara 1995, Shinohara and Hedenquist 1997, Sillitoe 2010).
Growing evidence that silicic magmas in upper crustal chambers are stored at high-
crystallinity (> 60 % crystals) degree and under a fundamentally immobile, non-convective
state as a mush (e.g. Bachmann and Bergantz, 2004; Buret et al., 2016 and 2017: Cashman
and Blundy, 2013; Cashman et al., 2017; Cooper and Kent, 2014; Cooper 2017; Deering et
al., 2016; Schoene et al., 2012; Spark and Cashman 2017) brings new challenges in the
comprehension of magmatic systems associated to porphyry copper formation (Buret et al.,
2016 and 2017; Tapster et al., 2016). Addition of energy, generally provided by new magma
injections, is required to rejuvenate the silicic mush and to form the volcanic products (e.g.
Cashman et al., 2017; Halter et al., 2004; Hattori and Keith, 2001). Cooling of these magmas
at the contact of the silicic reservoir provides large amounts of magmatic fluids having the
potential of generating porphyry-type mineralization and to trigger volcanic eruptions (Buret
et al., 2017; Tapster et al., 2016).
This study is part of a comprehensive study on the world-class porphyry-related
epithermal polymetallic deposit of Cerro de Pasco (Baumgartner et al., 2008 and 2009; Rottier
et al., 2016a, 2016b, submitted). The present work focuses on the temporal and genetic link of
volcanic and subvolcanic rocks, the recently found porphyry-type mineralization events, and
the epithermal polymetallic mineralization at Cerro de Pasco. New CA-ID-TIMS U-Pb zircon
dating of mineralized magmatic rocks and molybdenite Re-Os age of porphyry-type
mineralization complement previous geochronological work and demonstrates the existence
of successive short-lived episodes (<0.1 Ma) of near-surface magmatic activity and porphyry-
type mineralization. The dynamics of the upper-crustal silicic magma chamber has been

3
reconstructed by petrographic and geochemical studies of the volcanic and subvolcanic rocks
including LA-ICP-MS analyses of silicate melt inclusions hosted in quartz phenocrysts. Our
findings support a close causative relationship between rejuvenation of the upper-crustal
magma chambers and the high-temperature porphyry-type mineralization events.

General geology
The Cerro de Pasco district is part of the Miocene metallogenic belt of Peru which
includes a large number of polymetallic epithermal, Au-Ag high-sulfidation epithermal and
Cu-Mo porphyry deposits (Noble and Mckee 1999; Bissig et al., 2008; Bissig and Tosdal,
2009, Bendezú and Fontboté 2009; Catchpole et al., 2015). The central Peruvian segment of
the belt (~10.2-12°S) is part of the flat slab subduction segment of the Andes associated with
the subduction of the Nazca ridge that started at 15 Ma (Gutscher et al., 1999, Hampel et al.,
2002, Rosembaum et al., 2005). Cenozoic volcanism in the area is scattered from ~41 Ma to
~5 Ma (Bissig et al., 2008; Bissig and Tosdal, 2009) and is characterized by the emplacement
of isolated and small shallow-level intrusions, subaerial domes and volcanic deposits (Bissig
and Tosdal, 2009). Igneous rocks are high-K calc-alkaline and range from basalt to rhyolite,
evolved compositions (dacite to rhyolite) being strongly dominant (Bissig and Tosdal, 2009).
Central Peruvian ore-deposits are genetically associated with this magmatism and show a
similar age range from ~39 Ma to ~5 Ma, with a more intense Mid- to Late-Miocene
productivity between 16 and 5 Ma (Noble and McKee, 1999; Bissig and Tosdal, 2009).

District geology and mineralization


The geology of the Cerro de Pasco district is dominated by a thick deformed
sedimentary sequence consisting of Palaeozoic slates and phyllites (Excelsior Group),
overlain by sandstones and conglomerates of the Middle-Late Triassic Mitu Group (Fig. 1;
Rosas et al., 2007; Spikings et al., 2016), covered by up to 1000 m of carbonate rocks
belonging to the Late Triassic Chambará Formation, part of the Pucará Group (Angeles 1999;
Baumgartner et al. 2008). Sandstones of the Goyllarizquizga Group (Cretaceous) and
limestones and marls of the Pocobamba formation (Eocene) overlie discordantly the other
formations. At Cerro de Pasco, a regional N15° W-striking reverse fault, named Longitudinal
Fault juxtaposes the Excelsior Group and the Pucará Group (Fig. 1; Angeles 1999;
Baumgartner et al. 2008).

4
Figure 1: Geological map and cross-section of the diatreme dome complex and different epithermal mineralization styles
at Cerro de Pasco; slightly modified from Rottier et al. 2016b compiled from field observations and previous work of
Rogers (1983), Baumgartner et al. (2008) and the Volcan’s geological staff. A) Location of the Cerro de Pasco district; B)
Geological map; C) Porphyritic trachyte outcrop, affected by porphyry-type mineralization PM2.

5
The diatreme-dome complex of Cerro de Pasco, directly emplaced to the west of the
Longitudinal Fault, is 2.5 km in diameter and was formed by a succession of
phreatomagmatic, magmatic, and phreatic events (Fig. 1; Einaudi 1968; Rogers 1983;
Baumgartner et al. 2009; Rottier et al., submitted). An early phase of explosive activity
produced a diatreme-breccia known locally as Rumiallana Agglomerate, which is the most
common lithology in the diatreme-dome complex. The exact geometry of the breccia is not
known, the deepest level reached by exploration drilling is at 3300 m.a.s.l. corresponding to a
vertical extent superior to 1150 m; the horizontal extent is close to 2000 m. Three different
facies form the diatreme breccia: i) a lower facies of non-stratified breccia, ii) an upper facies
of stratified breccia, and iii) a top facies of fined-grained stratified lapilli tuff (Rottier et al,
submitted). One sample of lapilli tuff was dated at 15.36 ± 0.03 Ma (zircon U-Pb ID-TIMS)
by Baumgartner et al. (2009). The phreatomagmatic activity is followed by a period of
volcanic and subvolcanic magmatism characterized mainly by emplacement of: i) dacite to
rhyodacite bodies showing domal structures and emplaced along the western margin of the
diatreme breccia, dated at 15.40 ± 0.07 Ma (zircon U-Pb ID-TIMS; Baumgartner et al. 2009);
ii) small (each less than 10x10 m) porphyritic trachyte intrusions cropping out in the central
part of the diatreme breccia and iii) E-W trending quartz-monzonite porphyry dykes cutting
the diatreme breccia and the dacitic to rhyodacitic magmatic domes (Fig. 1A), two of them
being dated at 15.35 ± 0.05 Ma and 15.16 ± 0.04 Ma (zircon U-Pb ID-TIMS; Baumgartner et
al. 2009). Following the magmatic activity, numerous, 20 cm to 3 m-wide, E-W trending,
milled-matrix fluidized breccia dykes were emplaced in various parts of the diatreme-dome
complex crosscutting the diatreme breccia, the dacitic and rhyodacitic domes and the quartz-
monzonite dykes (Rottier et al., submitted). Based on the morphology of the diatreme-dome
complex and the occurrence of lapilli tuff, the total erosion since the formation of the
diatreme-dome complex has been estimated at < 1 km (Baumgartner 2007, Baumgartner et
al., 2008; Rottier et al., 2016a).
The large Cerro de Pasco epithermal polymetallic mineralization is mainly hosted by
carbonate rocks along the eastern margin of the diatreme-dome complex (Einaudi, 1977,
Baumgartner et al., 2008; nomenclature and event succession according to Rottier et al.,
2016b). It is formed during three main successive mineralization stages: A) pipe-like
pyrrhotite-dominated bodies grading outwards into Fe-rich sphalerite (up to vol. 80%) and
galena (stage A), B) quartz-pyrite veins with minor chalcopyrite, hematite, magnetite, pale-
brown sphalerite, galena and tennantite-tetrahedrite (stage B1) and by a large N-S trending
funnel-shaped massive pyrite-quartz body (stage B2), and C) high-sulfidation mineralization

6
consisting of large well-zoned Zn-Pb-(Bi-Ag-Cu) carbonate replacement ore bodies in the
eastern part of the deposit (stage C1) and a set of E-W–trending Cu-Ag-(Au-Zn-Pb) enargite-
pyrite veins hosted by the diatreme breccia (stage C2).
Large pervasive pyrophyllite-quartz-pyrite alteration grading to illite-smectite-muscovite-
pyrite and more externally to chlorite-calcite-pyrite alteration affects the central and the
northern part of the diatreme-dome complex (Fig. 1). This pervasive alteration is spatially
disconnected from the epithermal polymetallic mineralization and is probably linked to
degassing in a deeper part of the porphyry system (Rottier 2017).

Description of the dated porphyry-type mineralization


occurrences
A genetic relationship between the large epithermal polymetallic mineralization and a
porphyry system had been already proposed by Baumgartner et al (2008). Recently, three
temporally distinct occurrences of minor porphyry type mineralization have been discovered
at Cerro de Pasco. A brief description of the dated porphyry type mineralization occurrences
(PM1, PM2 and PM3) recently discovered at Cerro de Pasco is given in this section. Detailed
studies of PM1 (Rottier et al. submitted), and PM2 (Rottier et al., 2016a) have already been
published and only their main characteristics are summarized below. Porphyry-type
mineralization PM3 has not been described so far and the relevant characteristics are reported
here.

Porphyry-type mineralization PM1 and PM2

PM1 consists of porphyry-type veins crosscutting hornfels and porphyritic igneous clasts
incorporated in the diatreme-breccia (Fig. 2A, B and C). Quartz-molybdenite-(chalcopyrite)-
(pyrite) are formed at high temperatures (>600°C) and pressures (> 500bar) and host highly-
evolved rhyolitic silicate melt inclusions in hydrothermal quartz (Rottier et al., submitted). A
molybdenite separate obtained from one large hornfels clasts crosscut by numerous quartz-
molybdenite-(chalcopyrite)-(pyrite) veins (CP-16-BR-X4) has been dated by the Re-Os
method.

7
Figure 2: A-C) Magmatic (A) and hornfels (B-C) clasts found in the diatreme breccia crosscut by HT1-type (A and C) and
HT2-type (B) sulfide-poor quartz-molybdenite-(chalcopyrite)-(pyrite) veins belonging to the porphyry-type mineralization
PM1. D) Magmatic clast found in a quartz-monzonite dyke and affected by porphyry-type mineralization PM3 (sample
CP-14-BR-X1). The clast is affected by pervasive silicifiation and crosscut by A- and B-type quartz-magnetite-
chalcopyrite-pyrite veins with potassic alteration halo. Sample selected for U-Pb zircon dating; E) Sample of the dated
porphyritic trachyte intrusion crosscut by quartz-magnetite-chalcopyrite-pyrite veinlets (porphyry-type mineralization
PM2).

8
PM2 occurs as a network of up to 1 cm-thick quartz-magnetite-chalcopyrite-(pyrite)
porphyry veinlets (Fig. 2E) centered on porphyritic trachyte intrusions cropping out in the
central part of the diatreme-dome complex (Figs. 1B and C). The quartz-magnetite-
chalcopyrite-pyrite porphyry veinlets and the trachyte intrusions are crosscut by a quartz-
monzonite dyke. The porphyry veinlets have been formed in three steps at low pressure (<
270 bar): i) a high-temperature event (>> 600°C), characterized by inclusions formed by a
silicate phase and a hypersaline liquid; ii) a high-temperature event (>600°C), marked by
hypersaline fluid inclusions (~70 wt.% NaCl eq.); iii) a low-temperature event (<350°C),
marked by entrapment of liquid-rich fluid inclusions and sulfide precipitation. One sample of
mineralized porphyritic trachyte has been dated by U-Pb zircon in the present work and the
crosscutting dyke was previously dated by Baumgartner et al. (2009).

Porphyry-type mineralization PM3


Porphyry-type mineralization PM3 occurs in large clasts (up to 20 cm) of porphyritic
igneous rocks and hornfels found in a quartz-monzonite dyke in the central part of the
diatreme dome complex (Figs. 1B and 2D). Both porphyritic magmatic rocks and hornfels are
crosscut by a network of A- and B-type quartz-magnetite-chalcopyrite-pyrite veins (Fig. 2D)
and massive quartz-magnetite-chalcopyrite veins. The porphyritic igneous clasts are affected
by pervasive silicification and the veins display a potassic alteration halo with K-feldspar and
shreddy biotite (Fig. 2D). The hornfels clasts are formed by quartz, K-feldspar, minor albite,
secondary hydrothermal biotite, and disseminated pyrite and chalcopyrite. Microthermometric
analyses of two fluid inclusion assemblages (supplementary table A.1) and the high Ti content
of the hydrothermal quartz (51-121 ppm, mean = 79 ppm, n=33, LA-ICP-MS data,
supplementary table A.2) suggest that these veins formed at high temperature (> 600°C) by
fluid undergoing phase separation into a low-density vapor and high-salinity brine (> 57 wt%
NaCl equiv.). All hydrothermal quartz veins show occurrence of glassy silicate melt
inclusions (SMIs) similar to the ones found in porphyry-type mineralization PM1.

Methods
The samples were collected from surface outcrops (list of the samples and their
location is available in supplementary table A.3). A particular attention was paid on selecting
the least altered rock samples for analyses. Samples selected for whole rock analysis were
crushed and powdered with an agate mill. Fused glass beads (fluxed with Li2B4O7) and

9
pressed powder pellets were analyzed for major, minor and some trace elements by X-ray
fluorescence (XRF) at the University of Lausanne. Additionally, trace elements were analyzed
by LA-ICP-MS at the ETH Zurich on fragments of fused glass beads, previously used for
XRF analyses.
Five representative samples were analyzed for their Sr, Nd and Pb isotopic
composition at the University of Geneva. 120 mg of powdered rock was dissolved over 7 days
using a mixture of 4 ml concentrated HF and 1 ml 15M HNO3 in Teflon vials on a hot plate
(140°C). Samples were then dried and dissolved again in 3 ml of 15M HNO3 in closed Teflon
vials at 140°C, and dried down again. Separation of Sr, Nd and Pb was carried out using
cascade columns with Sr-spec, TRU-spec and Ln-spec resins following a modified method
after Pin et al. (1994). Lead was further purified with an AG-MP1-M anion exchange resin in
hydrobromic medium. Lead, Sr and Nd isotope ratios were measured using a Thermo
NEPTUNE Plus mass spectrometer at the University of Geneva, following methods described
by Chiaradia et al. (2014).
For the different studied rocks, solid inclusions trapped in minerals were identified by
Raman spectroscopy using a confocal LABRAM equipped with a 532.12 -nm Nd-YAG Laser
coupled with an Olympus BX51 microscope at the University of Geneva.
Feldspar phenocrysts from selected rocks were analyzed for their major and minor
elements. Sodium, Mg, Al, Si, K, Ca, Ti, Mn, Fe, Sr were quantified by electron microprobe
analyses (EMPA) using a Jeol JXA 8200 Superprobe WD/ED combined microanalyzer at the
University of Lausanne. Operating conditions were: accelerating voltage of 15 kV, beam
current of 15 nA, and beam diameter of 1 µm. Measuring time was fixed between 10 and 30 s
on peak and half of it on the respective backgrounds before and after the peak position. Both
natural and synthetic silicate, oxide and sulfate standards were used for calibration. Similar
feldspar phenocrysts were then analyzed by LA-ICP-MS at ETH Zurich. Quartz grains from
representative samples were picked from size fraction < 2mm and mounted in epoxy. SMIs
inclusions hosted in quartz were analyzed by LA-ICP-MS at ETH Zurich. Suitable SMIs were
glassy, between 15 and 40 µm in size and not outcropping at the surface.
Automated mineral analysis and textural imaging of the studied samples were
performed using an FEI QEMSCAN® Quanta 650F facility at the Department of Earth
Sciences, University of Geneva. The system is equipped with two Bruker QUANTAX light-
element energy dispersive X-ray spectrometer (EDS) detectors. Analyses were conducted at
high vacuum, accelerating voltage of 25 kV, and a beam current of 10 nA on carbon-coated
polished thin sections. FieldImage operating mode (Pirrie et al., 2004) was used for analyses.

10
In total 221 individual fields were measured per sample, with 1500 µm per field, and point
spacing of 5 µm. The standard 1000 counts per point were acquired, yielding a limit of
detection of approximately 2wt% per element for mineral classifications. Measurements were
performed using iMeasure v5.3.2 software and data processing using iDiscover® v5.3.2
software package. Final results consist of: i) high-quality spatially resolved and fully
quantified mineralogical maps; ii) BSE images with identical resolution as the mineral maps;
iii) X-ray element distribution maps.
A sample of a porphyritic trachyte intrusion affected by PM2 porphyry-type
mineralization (CP-14-BR-305) and a clast of porphyritic igneous rock crosscut by PM3
porphyry-type mineralization (CP-14-BR-X1; Fig. 2D) were selected for U-Pb zircon dating.
The mineralized (PM3) clast of porphyritic igneous rock was carefully isolated from its host
quartz-monzonite dyke to avoid contamination. Both samples were crushed and fractions <
0.3 mm were processed using a Wilfley table, a Frantz magnetic separator and gravimetric
separation in methylene iodide to concentrate zircons. Zircon grains were handpicked and
mounted on epoxy and polished to expose their internal structure. SEM-CL images were
acquired at the University of Lausanne using a CamScan MV2300 SEM equipped with a
panchromatic CL detector. In-situ dating by LA-ICPMS was carried out using a Thermo
ELEMENT XR sector-field ICPMS interfaced to an UP-193FX ArF excimer laser ablation
system at the Institute of Earth Sciences of the University of Lausanne following protocols
outlined in Ulianov et al. (2012). Trace elements composition of some zircon grains were then
analysed by LA-ICP-MS at ETH Zurich. Zircon displaying homogenous CL textures, no
xenocrystic core, and young LA-ICP-MS date were selected for ID-TIMS to resolve the
relative emplacement ages of the two rocks. Selected grains were plucked out of the epoxy
mount using a stainless steel scalpel, and then individually annealed and chemically abraded
(CA) following Mattinson (2005), and processed and analysed employing established
protocols outlined in Schoene et al. (2012) and Wotzlaw et al. (2013). Each single zircon
grain was loaded for dissolution into pre-cleaned Savillex capsules, spiked with 5 mg of the
202
EARTHTIME Pb-205Pb-233U-235U tracer solution (ET 2535, http://www.earthtime.org/
Condon et al., 2015). The isotopic analyses were performed at University of Geneva on a
TRITON mass spectrometer equipped with a MasCom discrete dynode electron multiplier.
The linearity of the multiplier was calibrated using U500, Sr SRM987, and Pb SRM982 and
SRM983 solutions. The deadtime for the SEM was determined to be constant at 23ns for up to
1.3 Mcps and at a Faraday/SEM yield between 93–94%. Lead isotopic fractionation was
202
corrected based on the certified value of Pb/205Pb = 0.99924±0.03%, 1σ of the

11
202
EARTHTIME Pb-205Pb-233U-235U tracer. The U mass fractionation for the same analyses
233
was calculated using the U-235U ratio of the double spike solution (0.99506 ± 0.01%, 1σ).
202
The average Pb and U fractionation factors determined by EARTHTIME Pb-205Pb-233U-
235
U tracer were 0.16±0.02%/amu and 0.10±0.02%/amu (1σ) respectively. Pb and U (as UO2)
isotope compositions were measured on the electron multiplier. Isobaric interference of
233
U18O16O on 235
U16O16O was corrected using a 18
O/16O ratio of 0.00205. The measured
238
uranium isotopic ratios were corrected assuming a sample U/235U ratio of 137.818 ± 0.045
(2σ, Hiess et al., 2012). All common Pb in the zircon analyses was attributed to the procedural
206
blank with the following lead isotopic composition: Pb/204Pb = 17.62±2.09, 207
Pb/204Pb =
208
14.73±3.06, Pb/204Pb = 35.77±2.99 (1-sigma %). The initial statistics, data reduction and
age calculation were done using the TRIPOLI and Redux software (Bowring et al., 2011). All
206
Pb/238U and 207
Pb/206Pb ratios were corrected for initial disequilibrium in 230
Th/238U using
Th/U [magma] calculated from the lattice strain model for zircon-melt partitioning of Th and
U (Blundy and Wood, 2003). The accuracy of the measured data was assessed by repeated
analysis of the 100Ma synthetic solution (Condon et al., 2008) and the international R33
zircon standard (Black et al., 2004), which was pre-treated by chemical abrasion (Mattinson,
206
2005). Both yielded an internal reproducibility in Pb/238U dates of better than 0.05%. All
uncertainties reported are at the 2 sigma level, following x/y/z systematic of Schoene et al.
(2006). All data are reported in the table with internal errors only, including counting
statistics, uncertainties in correcting for mass discrimination, and the uncertainty in the
common (blank) Pb composition. The MSWD values of weighted mean from all samples are
within the range of acceptable values at 95% confidence level and for (n-1) degrees of
freedom, defined by Wendt and Carl (1991).
One hornfels clast crosscut by numerous quartz-molybdenite-(chalcopyrite)-(pyrite)
veins of porphyry mineralization PM1 (CP-16-BR-X4) sampled in the southeastern part of the
diatreme breccia was selected for molybdenite Re-Os dating. The veins are sulfide-poor (<1
vol.%) and molybdenite crystals size was < 200 µm. Around 2 kg of mineralized sample were
ground using a hydraulic press and an agate mill, and then sieved to collect the 100- to 300-
µm fraction. Molybdenite was then concentrated using heavy liquids (DIM) and several steps
of Franz magnetic separation to optimize the concentration of molybdenite. The final mineral
separate (few grams) consisted of more than 99 % pyrite and <1% molybdenite. A total of 7
mg of molybdenite grains have been hand-picked under a binocular microscope and used for
dating. Rhenium and Os abundance and isotopic composition were determined on 5.56 mg of
this separate. Analysis was conducted at the University of Durham (U.K.) in the TOTAL

12
laboratory for source rock geochronology and geochemistry, following previously published
187
protocols (Selby and Creaser, 2001a, b). Molybdenite dates were calculated using the Re
decay constant of 1.666 x 10-11 a-1 (Smoliar et al., 1996; Begemann et al., 2001).
LA-ICP-MS analyses of XRF pellets, feldspar, zircon, and silicate melt inclusions
(SMIs) hosted in quartz were carried out using a 193 nm ArF Excimer laser with an energy
homogenized beam profile coupled with an ELAN 6100 DRC ICP quadrupole mass
spectrometer (QMS) at ETH Zurich (Günther et al., 1997, 1998; Heinrich et al., 2003).
Operating conditions, data acquisition parameters and list of isotopes analysed are
summarized in Table 1. Data have been treated using the Sills software (Guillong et al.,
2008). The SMIs and host quartz were ablated using a progressive manual increase of the
laser beam diameter to limit explosion of the quartz (Günther et al., 1998) using an iris
diaphragm (Guillong and Heinrivh, 2007); other materials – XRF pellets, feldspar and zircons
were ablated with a constant beam diameter. The SRM NIST 610 glass standard was used as
an external standard for the different analyses. For XRF pellets Al content previously
determined by XRF was used as an internal standard and for each sample three points were
measured and results are reported as a mean average value (supplementary table A.9). For
feldspar and zircon Si was used as an internal standard, using for feldspar the Si content
previously determined by EPMA, and for zircon a fixed value at 31.6 wt.% SiO2.
Quantification of the SMIs was done following the method of Halter et al. (2002) - Al content
was used as an internal standard and fixed at 16 wt.% Al2O3, that corresponds to the
calculated mean Al2O3 content obtained from whole rock analyses (mean=15.9 ± 0.7 wt%
Al2O3, n=15). Fixed 99.5 wt.% SiO2 was used for host correction (i.e., quartz).

13
Table 1: LA-ICP-MS machine and data acquisition parameters for analysis of SMIs and trace element
analyses of XRF pellets, feldspar and zircon.

LA-ICP-MS on
Excimer 193 nm
fragment of fused glass SMIs hosted in
ArF laser Compex Feldspar Zircon
bead previously used Quartz
110I
for XRF analyses

Energy density 23 J/cm2 25-30 J/cm2 23 J/cm2 23 J/cm2


Repetition rate 10 Hz 10-15 Hz 5-10 Hz 5 Hz
Crater size 60 µm 20-60 µm 40-60 µm 20 µm
In-house built In-house built
In-house built epoxy In-house built glass
aluminium chamber aluminium
chamber with anti- aluminium with anti-
Ablation cell with anti-reflection chamber with anti-
reflection coated silica reflection coated
coated silica glass reflection coated
glass window silica glass window
window silica glass window
Cell He gas
1.1 l/min He 1.1 l/min He 1.1 l/min He 1.1 l/min He
flow
Cell H gas
flow 5 ml/min H2 5 ml/min H2 5 ml/min H2 5 ml/min H2

Data acquisition parameters


Readings per
replicate 400 400 400 400
Points per
1 per mass 1 per mass 1 per mass 1 per mass
peak
Oxide tuned to <0.5 % tuned to <0.5 %
tuned to <0.5 % ThO tuned to <0.5 % ThO
production rate ThO ThO
Dwell time per 30 ms for Cu, Zn 30 ms for Cu, Zn
10 ms for all elements
isotope and Pb and Pb 30 ms for Ti
10 ms for the
10 ms for the others 10 ms for the others
others
9 23 25 27
Be, Na, Mg, Al,
29
Si, 31P, 34S, 39K, 42Ca, 7
45 Li, 11B, 23Na, 25Mg,
Sc, 49Ti, 51V, 53Cr, 7
Li, 11B, 23Na, 25Mg, 27
55 Al, 29Si, 31P 34S, 27
Al, 29Si, 31P, 49Ti,
Mn, 57Fe, 59Co, 62Ni, 27
Al, 29Si, 31P 34S, 39
65 K, 42Ca, 49Ti, 85
Rb, 88Sr, 89Y, 91Zr,
Cu, 66Zn, 71Ga, 39
K, 42Ca, 49Ti, 55
72 Mn, 57Fe, 65Cu, 93
Nb, 137Ba, 139La,
Ge,75As, 85Rb, 88Sr, 55
Mn, 57Fe, 65Cu, 66
89 Zn, 75As, 85Rb, 140
Ce, 141Pr, 146Nd,
Y, 90Zr, 93Nb, 95Mo, 66
Zn, 75As, 85Rb, 88
118 Sr, 89Y, 90Zr, 147
Sm, 151Eu, 157Gd,
Isotopes analyzed Sn, 121Sb, 125Te, 133Cs, 88
Sr, 89Y, 90Zr, 93Nb, 93
137 Nb, 98Mo, 159
Tb, 163Dy, 165Ho,
Ba, 139La, 140Ce, 141Pr, 98
Mo, 107Ag,118Sn, 107
146 Ag,118Sn, 121Sb, 167
Er, 169Tm, 173Yb,
Nd, 147Sm, 151Eu, 121
Sb, 133Cs, 137Ba, 133
157 Cs, 137Ba, 139La, 175
Lu, 178Hf, 181Ta,
Gd, 159Tb, 163Dy, 139
La, 140Ce, 147Sm, 140
165 Ce, 147Sm, 163Dy, 206Pb, 207Pb, 208Pb,
Ho, 167Er, 169Tm, 163
Dy, 173Yb, 182W, 173
173 Yb, 182W, 208Pb, 232
Th, 238U
Yb, 175Lu, 178Hf, 182W, 208
Pb, 232Th, 238U, 232
205 Th, 238U,
Tl, 208Pb, 209Bi, 232Th,
238
U,

14
Results

Timing of magmatic and high-temperature


hydrothermal events
SEM-CL images of magmatic zircons show no textural differences between crystals
from the mineralized porphyritic trachyte intrusion (PM2; n=85 grains) and from the studied
mineralized porphyritic igneous clast (PM3; n=78 grains). Zircon crystals from both samples
are euhedral to subhedral and almost all of them present fine well-developed oscillatory and
sector zoning (Fig. 3). Dissolution textures between core and rim are rare. No xenocrystic
cores were observed in zircon grains from the mineralized trachyte and only two were
observed in zircon grains from the mineralized clast.

Figure 3: Typical SEM-CL images of zircons from the trachyte porphyry (CP-14-BR-305) (A) and from the mineralized
magmatic clast (CP-14-BR-X1) (B) with corresponding LA-ICPMS 206Pb/238U ages (large circles). Scale bar in all pictures
corresponds to 50µm. The CA-ID-TIMS age for each crystal is reported on top of the CL pictures. Discrepancy between
the CA-ID-TIMS and the LA-ICP-MS ages are mainly due to the absence of common lead and lead loss corrections for
the LA-ICP-MS ages.

15
Figure 4: Geochronology of the various magmatic events at Cerro de Pasco. (A) LA-ICPMS 206Pb/238U ages with
weighted mean age and the corresponding probability density plot for each sample. (B) CA-ID-TIMS 206Pb/238U ages
with weighted mean values of statistically equivalent zircon populations (red vertical bars); previous data published by
Baumgartner et al. (2009) are also reported for comparison. All uncertainties are reported at the 95% (2σ) confidence
level. (C) Re-Os dates for a molybdenite separate (sample CP-16-BR-X4), uncertainty includes all sources of analytical
uncertainty and the one related to the decay constant (Smoliar et al., 1996; Begemann et al., 2001).

16
LA-ICP-MS zircon U-Pb ages from the mineralized trachyte porphyry and the
mineralized clast are unimodal indicating that they may represent a single zircon population
(Fig. 4A, all data are in supplementary table A.4). The trachyte porphyry and the mineralized
206
clast yield weighted mean Pb/238U ages of 14.974 ± 0.047 Ma (MSWD = 1.3, n=88) and
14.919 ± 0.063 Ma (MSWD = 1.3, n=58), respectively.
High-precision CA-ID-TIMS dating was performed on 5 and 7 zircons from
respectively the mineralized porphyritic trachyte and the studied mineralized porphyritic
igneous clast (all data are in supplementary table A.5). This new dataset completes the
previous dating performed by Baumgartner et al. (2009) on one sample of lapilli tuff, one
sample of dacitic dome and two samples of quartz-monzonite dyke (Fig. 4B). The five zircon
crystals from the mineralized porphyritic trachyte span a time range from 15.284 ± 0.009 Ma
to 15.439 ± 0.026 Ma (Fig. 4B), the four youngest grains being statistically equivalent (Fig.
206
4B) and yielding a weighted mean Pb/238U date of 15.286 ± 0.018 Ma (MSWD = 0.27,
n=4). From the 7 zircon grains from the mineralized clast one was dated at 23.972 ± 0.067
Ma; the remaining 6 grains formed two clusters of 3 statistically equivalent zircons each (Fig.
206
4 B). The weighted mean Pb/238U date of the youngest cluster is 15.165 ± 0.043 Ma
(MSWD = 1.4, n=3), which is interpreted to best approximate the emplacement age.
Re-Os dating was performed on one molybdenite separate from sulfide-poor quartz-
molybdenite-(chalcopyrite)-(pyrite) veins crosscutting a hornfels clast and belonging to the
first event of porphyry-type mineralization (PM1). The obtained Re-Os date is 15.59 ± 0.12
Ma (complete data set is available in supplementary table A.6).

Trace element signatures of zircon

Core and rim of zircon grains from the porphyritic trachyte and the studied
mineralized porphyritic igneous clast were analyzed by LA-ICP-MS for trace elements;
results are reported in supplementary table A.7. Rare earth elements (REE) patterns of zircon
are similar for grains from both samples with MREE and HREE systematically depleted in the
rim compared to the core of the crystals (Fig. 5A). The REE budget of the magma and
therefore the REE composition of zircon are strongly controlled by the crystallization of
accessory minerals. According to the mineral abundances of the trachyte porphyry, as
determined by Qemscan (Fig. 6), the REE budget (except for Eu) of the melt is controlled at
more than 80% by a titanite-apatite accessory assemblage (Fig. 5B).

17
Figure 5: A) Chondrite-normalized (Sun and McDonough, 1995) REE pattern for rims and cores of zircon crystals from
the mineralized magmatic clast and the mineralized trachyte porphyry. B) Importance of REE Kd of each mineral
compared to the bulk REE Kd of the mineral assemblages constituting the magmatic rock, considering the mineral
composition of the trachyte porphyry, as determined by Qemscan analysis. C) Trace element signatures of analyzed
zircons, Yb/Dy ratio versus Th/U ratio, Ce content and Σ HREE. Core and rim of each zircon grains analyzed from the
mineralized clast and the trachyte porphyry are connected with a grey line. Normally zoned (circle) and reversely zoned
(diamond) zircons are separated (see text). D) SEM-CL image of a reversely zoned zircon from the trachyte porphyry
showing dissolution episode between core and rim. The black circles refer to locations of LA-ICP-MS analyses.

The zircon cores found in the two studied samples have similar evolution trends
marked by a decrease of HREEs, Ce, Th/U ratio in parallel to an increase of the Yb/Dy ratio
(Figs. 5B and C), the latter ratio indicating crystallization of titanite and apatite, minerals that

18
incorporate preferentially Dy compared to Yb. Two distinct core-to-rim evolution trends are
observed: a “normal evolution” where rims show higher Yb/Dy ratio, lower Ce concentration
and strong depletion in HREE compared to the cores and a “reverse trend” where rims present
a lower Yb/Dy ratio and a higher Ce concentration, and only a weak depletion in HREE (Fig.
5C). Zircons having a “reverse evolution” present occasionally resorption textures between
the core and the rim of the grains (Fig. 5C), most probably linked to a reheating event and
resorption of apatite and apatite.
Titanium concentrations in the analyzed zircon grains were below detection limit
(MaxLOD = 5.4 ppm, MinLOD = 3.1 ppm, MeanLOD = 4.2, n=31), except three analyses
revealing a Ti content between 3.3 and 3.7 ppm (supplementary table A.6). Ti-in-zircon
thermometer was applied using the calibration of Ferry and Watson (2007) and the limit of
detection of Ti was used to determined maximal crystallization temperature. We use αSiO2 of
1 because of the presence of quartz in the rocks and αTiO2 of 0.7, considering the presence of
titanite. Calculated maximum crystallization temperatures were below 725°C (Max ≈ 722°C ,
Min ≈ 675 °C, Mean ≈ 700°C, n=31).

Mineral composition and textures of magmatic rocks


from the Cerro de Pasco district
This section presents an update of the main petrographic and geochemical features of
the magmatic rocks cropping out in the Cerro de Pasco District (Fig. 1B). Descriptions of
Rogers (1983) and Baumgartner et al. (2009) have been integrated. Despite the effort to
sample the freshest possible outcrops, most analyzed rock samples show weak hydrothermal
alteration. The following section used rocks nomenclature adapted from the one of
Baumgartner et al. (2009).

Dacitic tuff
Dacitic tuffs crop out in the northern and southern parts of the diatreme-dome complex
(Fig. 1). They present rough layering showing broadly centroclinal dips (Roger 1983) and
locally display accretionary lapilli texture. The phenocrysts are plagioclase (~26 mol.% An),
quartz, biotite, apatite, and magnetite (Fig. 6A). The matrix is devitrified glass recrystallized
to fined-grained (<20 µm) quartz, K-feldspar, albite, rare plagioclase, and an unidentified Si-
K-rich matrix. Titanite phenocrysts are commonly replaced by leucoxene, ilmenite and rutile

19
(Fig. 6A). Quartz phenocrysts are always resorbed and present inclusions of apatite and
zircon.

Figure 6 : Mineral composition and texture of volcanic and subvolcanic magmatic rocks from Cerro de Pasco -
transmitted light photomicrograph, QEMSCAN mineral map and QEMSCAN Ca distribution map (intensity of the green
color reflects the Ca-content in plagioclase and yellow color indicates presence of apatite and titanite): A) Dacitic tuff, B)
Dacitic lava-dome complex, C) Rhyodacitic lava-dome complex, D) Quartz-monzonite dyke. Quantitative mineralogy of
the rocks is based on the area% of each mineral determined from the QEMSCAN maps.

20
Dacitic domes
Dacitic domes crop out in the western part of the diatreme breccia (Fig. 1). The rocks
are porphyritic, the main phenocrysts consisting of plagioclase (~26 mol.% An), biotite,
apatite, and rarely quartz. The matrix is fine-grained and consists of K-feldspar, quartz,
unidentified Si-K-rich matrix, and minor albite (Fig. 6B). Numerous crystals with a diamond
shape (up to 500 µm in size) are replaced by a fine-grained mixture of quartz and rutile with
minor magnetite. Since titanite, a mineral typically rhomb-shaped, is mostly replaced by
leucoxene and rutile without quartz in the other rocks investigated, we rather suggest that the
diamond shape reflects a hornblende precursor. Based on the weak alteration, we conclude
that this replacement occurred at the magmatic stage or was caused by high temperature
hydrothermal fluids. Like in the dacitic tuff, all quartz phenocrysts are resorbed and present
solid inclusions of apatite and zircon.

Rhyodacitic domes
The rhyodacitic domes crop out in the western part of the diatreme breccia south of the
dacitic domes (Fig. 1). The relative chronology between the rhyodacitic and the dacitic lava-
dome complexes is not known. The rock is porphyritic; the main phenocrysts are plagioclase
(~24 An mol.%), quartz, biotite, and rare K-feldspar and apatite, whereas the matrix is formed
mainly by an unidentified Si-K-rich matrix and K-feldspar (Fig. 6). No hornblende or
replaced hornblende crystal was observed. Sites of titanite phenocrysts are mostly totally or
partially removed during polishing, as shown by elongated diamond shapes with empty holes
partially filled with leucoxene and rutile. Quartz phenocrysts are resorbed and host solid
inclusions of zircon and apatite.

Quartz-monzonite dykes
The quartz-monzonite dykes are porphyritic, main phenocrysts being sanidine (up to 8
cm), plagioclase (oligoclase), quartz, biotite and apatite. Sanidine phenocrysts commonly host
inclusions of biotite, quartz, and plagioclase and show rims of fine-grained plagioclase (Fig.
6). The matrix consists of K-feldspar, plagioclase, quartz and an unidentified Si-K-rich matrix
(Fig 6). Small diamond-shaped crystals replaced mainly by muscovite are interpreted as
former hornblende. Titanite is also replaced by a mixture of muscovite, leucoxene, and rutile.
Quartz phenocrysts are strongly resorbed and host inclusions of apatite and zircon. Solid
inclusions of quartz, zircon, magnetite, anhydrite, and calcite have been identified in apatite
(Fig. 7). Both calcite and anhydrite are not spatially associated with cracks or secondary melt

21
or fluid inclusions trails and are considered to be primary. Anhydrite solid inclusions are
euhedral to subhedral, up to 300 µm-long, and generally aligned along growth bands of
apatite (Fig. 7). Calcite is less common than anhydrite and usually forms smaller crystals (up
to 100 µm). No anhydrite nor calcite have been identified in the matrix of the dyke.

Figure 7: (A) Photomicrograph of an apatite crystal with inclusions of magmatic calcite and anhydrite (transmitted light,
//N). (B) Raman spectrum of calcite inclusion in apatite. (C) Raman spectrum of anhydrite inclusion in apatite.

Porphyritic trachyte intrusions


The porphyritic trachyte intrusions crop out in the central part of the diatreme-dome
complex. Most of them are crosscut by quartz-magnetite-chalcopyrite-pyrite porphyry style
stockwork of PM2 event and affected by pervasive chlorite-epidote-sericite-calcite alteration.
The rock is porphyritic; the main phenocrysts are plagioclase (~26 An mol.%), quartz, biotite,
K-feldspar, and apatite (Fig. 8). The matrix is formed by K-feldspar, unidentified Si-K-rich
matrix, quartz and albite (Fig. 8). Phenocrysts of hornblende are almost totally altered to
chlorite by the late pervasive chlorite-epidote-sericite-calcite alteration (Fig. 8). Compared to
the other lithologies, the trachyte porphyry is enriched in apatite and titanite, and depleted in
quartz. Titanite phenocrysts are only weakly altered and are not transformed to leucoxene as
observed in the other rock types.

22
Figure 8: Mineral composition and texture of the porphyritic trachyte - transmitted light photomicrograph, QEMSCAN
mineral map and QEMSCAN Ca distribution map (intensity of the green color reflects the Ca-content in plagioclase and
yellow color indicates presence of calcite, apatite, titanite and epidote). Chlorite, epidote and calcite result from a low-
temperature hydrothermal alteration associated with the quartz-magnetite-chalcopyrite-(pyrite) stockwork.

Feldspar chemistry
Calcium maps generated from the Qemscan analyses for the different rocks indicate
that most plagioclase phenocrysts are weakly zoned and that only few of them present
resorbed Ca-rich cores (Figs. 6 and 8). EPMA profiles and spot analyses indicate one main
population of plagioclase with a median composition of ~An26 for the dacitic tuff, dacitic
lava-dome complexes, and the trachyte porphyry, and of ~An24.5 for the rhyodacitic lava-
dome complex (Fig. 9). No EPMA analyses have been done on plagioclase from the quartz-
monzonite dyke, but Qemscan calcium maps show no difference compared to the other rock
types (Fig. 6D). Plagioclase LA-ICP-MS trace element analyses show a large similarity
among the different rock types (supplementary table A.8), with plagioclase from the trachyte
porphyry showing slightly higher Sr (up to 4000 ppm), Fe (up to 1800 ppm), and Mg contents
(up to 30 ppm) than plagioclase from the other rocks. In all samples, Pb and Zn content of
plagioclase varies from 9 to 14.5 ppm and from 2.75 to 6 ppm, respectively; Cu concentration
was always below the detection limit (<1.1 ppm).
EPMA of sanidine phenocrysts from the quartz-monzonite dykes show a constant
composition of Or72 (σ=0.42, n= 23). LA-ICP-MS analyses of the sanidine crystals (n=4)
reveal high Ba contents ranging from 9’990 to 12’583 ppm. Lead concentration varies from
22 to 26 ppm, Zn from 4.9 to 5.3 ppm, and Cu from 4.2 to 11.4 ppm, (supplementary table
A.9).

23
Figure 9: Density distribution plots of plagioclase anorthite content from selected representative magmatic rocks, based
on EPMA.

Whole rock geochemistry


The Cerro de Pasco magmatic rocks display a narrow range of compositions - from
60.6 to 69.7 wt% SiO2 and all rocks fall into the high-K calc-alkaline field (Fig. 10;
supplementary table A.10). TiO2, Fe2O3tot, MgO, MnO, and CaO show a negative correlation
with SiO2 (Fig. 10). No correlation between the U-Pb ages of the rock and the concentrations
of any chemical element is observed.

24
Table 2: Representative geochemical and isotopic data for Cerro de Pasco magmatic rocks (complete data set is reported
in supplementary table A.10)

Rock-type: Dacitic tuff Dacitic dome Rhyodacitic dome Trachyte porphyry Quartz-monzonite dyke

Sample n°: BR-201 BR-235 BR-230 BR-301 BR-232


sample type Outcrop Outcrop Outcrop Outcrop Outcrop
Easting 360721 360674 360320 361389 360235
Northing 8821388 8821148 8819640 8820680 8820778
Major elements (wt.%)

SiO2 67.3 67.3 67.9 62.6 65.4


TiO2 0.70 0.70 0.66 0.96 0.82
Al2O3 16.3 16.0 16.3 16.0 15.6
Fe2O3 tot 3.16 3.34 2.58 4.53 3.54
MnO 0.02 0.03 0.03 0.11 0.05
MgO 0.77 0.49 0.90 1.90 0.84
CaO 2.07 2.17 2.17 3.96 3.31
Na2O 4.24 4.44 4.15 4.25 3.98
K2O 3.39 3.88 3.88 3.38 3.33
P2O5 0.28 0.27 0.23 0.47 0.37
LOI 1.25 0.93 1.02 1.40 2.19
Total 99.5 99.6 99.8 99.5 99.4
Trace elements (ppm)
Sc 5.43 5.51 4.62 6.99 5.03
V 50.1 53.2 52.0 75.7 61.2
Cr 9.01 28.2 11.0 13.9 13.9
Mn 140.7 231.6 173.9 n.d. 323.9
Co 4.28 5.79 3.56 8.47 6.48
Ni 5.53 4.85 8.44 5.64 n.d.
Cu 9.15 7.20 7.04 150.9 8.90
Zn 41.9 44.3 47.1 101.8 46.4
Ga 18.7 19.8 20.2 18.6 19.4
Ge n.d. 1.51 n.d. n.d. 2.13
As 3.39 3.23 1.61 3.43 0.88
Rb 82.5 103.5 109.0 67.0 83.0
Sr 775.5 829.8 822.5 1225 1118
Y 7.04 7.79 9.09 10.8 8.43
Zr 162.1 153.9 159.5 166.0 168.9
Nb 14.4 14.9 14.3 16.8 10.6
Mo 0.74 3.02 0.54 1.78 0.70
Sn 2.83 2.55 2.82 3.38 2.18
Sb 0.43 0.85 0.55 0.20 0.09
Cs 6.11 2.38 4.68 0.95 1.78
Ba 531.7 683.7 787.1 937.7 815.1
La 42.9 40.5 40.2 54.2 51.4
Ce 82.8 83.4 81.7 107.7 104.8
Pr 9.25 9.18 9.48 12.4 12.3

25
Nd 35.1 35.0 34.9 49.7 47.3
Sm 4.96 5.54 5.59 7.67 7.28
Eu 1.23 1.30 1.26 1.91 1.75
Gd 3.35 3.40 3.74 4.92 3.84
Tb 0.32 0.35 0.41 0.48 0.42
Dy 1.65 1.86 1.90 2.32 2.00
Ho 0.25 0.22 0.30 0.37 0.31
Er 0.70 0.65 0.75 0.95 0.74
Tm 0.09 0.09 0.09 0.12 0.09
Yb 0.54 0.54 0.63 0.72 0.50
Lu 0.08 0.08 0.06 0.10 0.11
Hf 3.95 4.19 4.21 4.23 4.26
Ta 0.96 1.02 1.01 0.91 0.66
W 0.84 2.14 0.74 1.11 1.28
Tl 0.30 0.24 0.18 0.15 0.19
Pb 15.2 14.1 14.0 17.2 12.6
Bi 0.08 0.02 n.d. 0.03 0.09
Th 10.1 10.1 11.3 9.83 9.75
U 3.63 3.71 3.05 2.59 3.06
Radiogenic isotope ratios*
87 86
Sr/ Sri 0.705416 0.70542 0.70556 0.705256 0.705426
143 144
Nd/ Ndi 0.51253 0.512534 0.512517 0.512571 0.512536
206 204
Pb/ Pbi 18.770 18.772 18.778 18.748 18.750
207 204
Pb/ Pbi 15.640 15.643 15.640 15.637 15.640
208 204
Pb/ Pbi 38.810 38.812 38.817 38.773 38.786

*: age correction has been applied

LOI: loss on ignition; n.d.: not detected.

The P2O5 content, from 0.47 wt% to 0.15 wt%, displays also a negative correlation
with SiO2. Such P2O5 content is elevated but similar to the one of Oligocene and Miocene
magmatic rocks from central Peru compiled by Bissig and Tosdal (2009) and consistent with
the observed high content of apatite of the analyzed rocks (Figs. 6 and 8). Al2O3, K2O, Rb and
Pb contents tend to increase when increasing the SiO2 content from 60.6 to ~67 wt%, and are
constant or display a slight decrease for SiO2 contents from ~67 to 69.7 wt%. Such evolution
is probably due to a limited K-feldspar fractionation taking place in the more evolved
compositions (Fig. 10). Na2O contents range between 2.7 and 4.5 wt% without any correlation
with SiO2 (Fig. 10). Strontium content is elevated, from 1250 to 650 ppm, and Y is relatively
low, from 14 to 6.5 ppm, and both display a rough decrease with SiO2 (Fig. 10). Sr/Y ratios
are elevated, from 54 to 148, and present no correlation with SiO2; all the rocks fall in the
geochemical “adakite” field in the Sr/Y versus Y diagram (Fig. 11).

26
Figure 10: Harker variation diagrams for whole-rock samples of the Cerro de Pasco magmatic suite (all data are in
supplementary table A.9). Grey dots refer to Oligocene and Miocene magmatic rocks from the central Peruvian Cordillera
Occidental compiled by Bissig and Tosdal (2009).

27
The primitive mantle normalized spidergram (Fig. 11) shows well-defined Nb and Ta
(as well as Y and Ti) negative anomalies and enrichment in large ion lithophile elements
(LILE), typical of arc magmas. The REE plot shows a strong depletion of HREE compared to
LREE, leading to high La/YbN ratios (25 to 73); they also fall in the geochemical “adakite”
field in the La/Yb versus Yb diagram (Fig. 11). Rocks display also a strong fractionation
between MREE and HREE illustrated by high Gd/YbN ratios (4.2 to 6.6), and a lack of Eu
anomaly indicating limited plagioclase fractionation. La/Gd ratios (10.3-17.9) positively
correlate with the La/YbN ratio indicating decreasing LREE/MREE ratios with increasing
LREE/ HREE fractionation. La/YbN and Gd/YbN ratios display no correlation with SiO2 (not
shown). Compared to published compositions of Oligocene and Miocene magmatic rocks
from central Peru compiled by Bissig and Tosdal, (2009), the magmatic suite at Cerro de
Pasco display a more important enrichment in LREE, and a more pronounced depletion in
HREE (Fig. 11).

Figure 11: (A) Chondrite-normalized REE patterns (chondrite composition from Sun and McDonough, 1995); (B)
Primitive mantle-normalized trace element patterns (chondrite composition from Sun and McDonough 1995). For A and
B the red fields correspond to the range of compositions of whole-rock samples from Cerro de Pasco and the grey field - to
compositions of Oligocene and Miocene magmatic rocks from the central Peruvian Cordillera Occidental compiled by
Bissig and Tosdal (2009); C) Sr/Y vs Y; D) La/Yb vs Yb. In C and D, the dashed lines represent the adakite field (all data
are in supplementary table A.10).

Strontium, Pb and Nd isotopic compositions were investigated in selected samples


representing the main lithologies: one lapilli tuff (BR-201), one quartz-monzonite dykes (BR-
232), one dacitic dome (BR-235), one rhyodacitic dome (BR-230) and one sample from the

28
porphyritic trachyte stock (BR-301). Results obtained on the last sample should be considered
with caution regarding its alteration (Fig. 8). For all samples, an age correction has been
applied considering the previously published and the newly obtained zircon U-Pb ages
87
reported above. Isotope ratios display small variations: Sr/86Sri varies from 0.70526 to
206
0.70556, Pb/204Pbi from 18.747 to 18.812, 207
Pb/204Pbi from 15.637 to 15.644, 208
Pb/204Pbi
from 38.773 and 38.858, and 143Nd/144Ndi from 0.512515 to 0.512571 (Fig. 12). These values
are in the range of Sr, Nd and Pb isotopic compositions reported for Miocene magmatic rocks
in the central Peruvian Cordillera Occidental (Soler and Rotach-Toulhoat, 1990; Beuchat
2003; Bissig and Tosdal 2009). Despite the small range of variation, Sr and Pb isotope ratios
follow a trend towards more radiogenic compositions and Nd toward less radiogenic
composition with increasing SiO2 content (Fig. 12), which is consistent with a progressive
assimilation of host rocks concomitant with the magmatic differentiation.

29
Figure 12: Radiogenic isotope ratios versus SiO2 for the magmatic suite at Cerro de Pasco.

30
Silicate melt inclusions

Composition
A total of 37 silicate melt inclusions (SMIs) hosted in quartz phenocrysts were
analyzed by LA-ICP-MS: 6 from a dacitic lapilli tuff (BR-201), 5 from a dacitic dome (BR-
235), 15 from a rhyodacitic dome (BR-230), and 11 from a quartz-monzonite dyke (BR-232).
In all samples, analyzed melt inclusions were glassy, from 15 to 40 µm in size, and isolated.
No SMIs from the trachyte porphyry and mineralized clasts were analyzed because of the
occurrence of numerous secondary fluid inclusions crosscutting the SMIs that made them not
suitable for LA-ICP-MS analyses.
The studied SMIs in quartz phenocrysts are rhyolitic in composition, with calculated
SiO2 contents of 69-72.3 wt% (SiO2 wt.% = 100-wt%(K20)-wt%(Na2O)-wt%(Fe2O3)-
wt%(Al2O3)-wt%(MgO)) and are strongly enriched in K2O and Na2O with respectively 5.4 to
8.3 wt% and 3.3 to 4.9 w%; within each sample, SMIs display a restricted range of
compositions (Fig. 13 and supplementary table A.11). All SMIs show an evolved composition
with an elevated content of incompatible elements (Fig. 13 and supplementary table A.11).
Compared to whole rock compositions, SMIs are depleted in Ca, Fe, Mg, Ti, Sr, Ba, Y, Zr,
Nb, La, Ce, Yb, and Dy, due to crystallization of biotite, plagioclase, K-feldspar, apatite,
zircon, and titanite. In contrast, SMIs are enriched in Na, K, and in incompatible elements like
Cs, Rb, W, Pb, Th, and U (Fig.13). Metal contents are coherent with the rhyolitic composition
of the SMIs; Cu ranges from 0.1 to 6 ppm in the lapilli tuff, the dacite and the rhyodacite
domes, and from 5 to 15 ppm in the quartz-monzonite dykes (Fig. 13). Zinc and Pb vary in all
rock types from 24 to 75 ppm (one higher value: 112 ppm; Fig. 13) and from 23 to 43 ppm
(one higher value: 57 ppm; Fig. 13), respectively. These Cu contents are slightly lower and
the Pb and Zn concentrations similar to previously published metal contents of SMIs hosted in
quartz, plagioclase, amphibole and pyroxene from andesitic to rhyolitic arc magmas (Cu: 9-
100 ppm, Pb: 12-105 ppm, Zn: 10-150 ppm; Mandeville et al., 1996, Price et al., 2005,
Mustard et al., 2006, Borisova et al., 2008, Nadeau et al., 2013, Johnson et al., 2013).
Molybdenum and W contents range from 0.5 to 5.3 ppm and from 1.9 to 4.5 ppm (with one
value at 9.8 ppm, Fig. 13), respectively.

31
Figure 13. K2O and selected trace elements versus Cs plots for quartz-hosted SMIs from studied samples compared to
whole-rock analyses of Cerro de Pasco magmatic rocks (all data are available in supplementary table A.10 and A.11).

Cesium is the element that behaves most incompatibly during magma evolution and
can be used as an indicator of the degree of crystallization of a magma (Audétat and Pettke
2003; Bachmann et al., 2005; Audétat, 2015). Cesium concentrations of the SMIs varies from
11.5 to 19.6 ppm for the dacitic lapilli tuff, from 13.6 to 14.3 ppm for the dacitic dome, from
12.8 to 16.0 ppm for the rhyodacitic dome, and from 14.8 to 19.1 ppm in quartz monzonite

32
dyke (Figs. 13 and 14). Considering the Cs content of the whole rock samples (from 1.8 to 6.1
ppm; Fig. 13 and supplementary table A.10) as a proxy of the initial Cs concentration of the
melt, and fractional crystallization in a closed system, between 45 and 93 % of crystallization
are necessary to explain the Cs concentrations measured in the melt inclusions (Fig. 14). In an
open system, the obtained degree of crystallinity would be underestimated if a less evolved
(Cs-poor) magma is injected (Fig. 14A), and would be overestimated if Cs-rich rocks or melts
are assimilated. Taking into account that only few mineral disequilibrium textures indicative
of magma mixing were observed and the generally low Cs content of crustal rocks (<6 ppm;
McLennan 2001), the estimation based on fractional crystallization in a closed system is
considered to be an adequate approximation.

Figure 14: A) Median Cs content of volcanic rocks classified by rock types. Diamonds are the median of compiled rocks
from the entire Andean arc (data from Georoc database: http://georoc.mpch-mainz.gwdg.de/georoc/) and hexagons are
the median of Oligocene and Miocene magmatic rocks from the central Peruvian Cordillera Occidental compiled by
Bissig and Tosdal (2009). B) Distribution of Cs content of quartz-hosted SMIs from different magmatic rocks at Cerro de
Pasco. The grey bar represents the range of Cs contents of all magmatic rocks at Cerro de Pasco (supplementary table
A.10). Colors refer to rock types as defined in C. C) Evolution of Cs concentration of the melt versus crystallinity,
considering a fractional crystallization in a closed system and the whole-rock Cs content as a starting concentration. The
color bars along the X-axis correspond to the crystallinity ranges necessary to explain the Cs concentration measured in
the quartz-hosted SMIs.

Zircon saturation
Zircon saturation temperatures were calculated using the Zr content of the analyzed
SMIs and the equation of Watson and Harrison (1983). Zirconium saturation of the melt is
indicated by the presence of zircon inclusions in all investigated quartz phenocrysts, moreover
all SMIs are metaluminous to weakly peraluminous which is one other condition required for

33
the application of this thermometer. Zircon saturation temperatures range from 688° to 693°C
for SMIs from the lapilli dacitic tuff, from 692° to 706 °C for SMIs from the dacitic dome,
692° to 710°C for SMIs from the rhyodacite dome, and from 713° to 734 °C for SMIs from
the two quartz-monzonite dykes (supplementary table A.11).

Ti-in quartz thermobarometry


The Ti-in-quartz thermobarometer was used as insight to pressure conditions during
quartz phenocryst crystallization. Calculated pressures were obtained following the approach
described by Audétat (2013). First TiO2 activity was determined using (i) the composition of
SMIs, (ii) the TiO2 solubility model of Kularatne and Audétat (2014), and (iii) the
temperatures obtained from the zircon saturation thermometry. The Ti content of quartz
adjacent to each SMI obtained by LA-ICP-MS was recalculated based on the TiO2 activity
obtained for each SMI. Finally, pressures were calculated using (i) the equation of Huang and
Audétat (2012), (ii) the recalculated Ti content in quartz, and (iii) the temperatures obtained
from the zircon saturation thermometry. For the lapilli dacitic tuff, pressure ranges from 3.8 to
4.2 kbar (n=3), for the dacitic dome from 3 to 4.2 kbar (n=5), for the rhyodacite dome (n=11)
the values are between 3.7 and 4.8 kbar except three values between 2.1 to 3.2 kbar, and for
the quartz-monzonite dyke the values are uniformly distributed between 2 and 4.4 kbar (Fig.
15). Calculated pressure is highly sensitive to temperature and thus a temperature variation of
± 20°C (the error range of the zircon saturation thermometer) induces a shift of calculated
pressures between 0.5 and 1 kbar; therefore the calculated pressures should be considered
with caution. Presence of magmatic calcite in apatite phenocrysts from a quartz-monzonite
dyke could be also used as a pressure indicator because the lowest pressure where a dacitic
silicate melt and calcite could coexist is ~3.8 kbar assuming a αCO2 = 0.2 of the coexisting
fluid phase (Audétat et al., 2004).

34
Figure 15. Recalculated Ti content in quartz taking in account the αTiO2 calculated using the equation of Kularatne and
Audétat (2014), versus the zircon saturation temperature calculated based on Zr contents of SMIs and using the equation
of Watson and Harrison (1983). The pressure isopleths were constructed using the equation of Huang and Audétat
(2012). Temperature variation of ± 20°C (the error range of the zircon saturation thermometer) induces a shift of
calculated pressures between 0.5 and 1 kbar

Discussion

New geochronological constraints on the


hydrothermal mineralization at Cerro de Pasco
The obtained U-Pb and Re-Os ages combined with field observations and previous
geochronological data offer a new comprehension of the evolution of the magmatic-
hydrothermal system of Cerro de Pasco.
Three temporally distinct porphyry-type mineralization events have been recognized.
The age of the first one (PM1) is determined by the Re-Os date of 15.59 ± 0.12 Ma obtained
from one molybdenite separate of the mineralized clast CP-16-BR-X4 hosted in the
southeastern part of the diatreme breccia (Fig. 16). This age is coherent with the 15.36 ± 0.03
Ma U-Pb zircon age of the dacitic tuff interpreted to be synchronous to the formation of
diatreme-breccia (Baumgartner et al., 2009). These two ages suggest a minimum time gap of
80 ka between the first porphyry event (PM1) and the first outcropping expression of the
magmatic system (diatreme breccia, Fig 16). The second event of porphyry-type

35
mineralization PM2 is bracketed by the host trachyte porphyry dated at 15.286 ± 0.018 Ma,
and the crosscutting post-PM2 quartz-monzonite dyke dated at 15.158 ± 0.035 Ma
(Baumgartner et al., 2009). Therefore the maximum lifespan of PM2 mineralization is ~160
ka (Fig. 16). The age of the last recognized porphyry event (PM3), occurring as mineralized
clasts hosted in a quartz monzonite dyke, is bracketed by the age of 15.165 ± 0.043 Ma
(MSWD = 1.4, n=3) of the mineralized magmatic clast and that of 15.158 ± 0.035 Ma
(MSWD = 1.03, n=6) of the host quartz-monzonite dyke (Fig. 16), i.e., a maximum time span
of 85 ka (Fig. 16). These new ages reveal a period of approximately 400 ka during which at
least three porphyry-type mineralization events and volcanic to sub-volcanic activities
occurred alternatively drawing three cycles of porphyry-type mineralization event follow by
magmatic activities.

Figure 16: Compilation of ID-TIMS U-Pb ages of magmatic rocks obtained in this study and by Baumgartner et al.
(2009), the obtained Re-Os ages of molybdenite separate from PM1, the potential age range based on cross-cutting
relationships for the hydrothermal events and the 40Ar/39Ar ages of alunites attributed to the enargite-pyrite veins
(Baumgartner et al., 2009).

The age of the large epithermal polymetallic deposit and its mineralization stages A,
B1, B2, C1 and C2 is not well constrained. The quartz-monzonite dyke dated at 15.35 ± 0.05
Ma (Baumgartner et al., 2009) is affected by the mineralization stages and alunite of the last
stage (C2) yields ages between 14.54 ± 0.06 and 14.41 ± 0.07 Ma (Ar/Ar; Baumgartner et al.,
2009). Therefore, all the epithermal polymetallic mineralization stages should have been
formed over a maximum lifespan of 1 my, between 15.4 and 14.4 Ma (Fig. 16).

36
Magmatic evolution at deep crustal levels
Magmatic rocks at Cerro de Pasco display typical chemical signatures of subduction-
related magmas: Nb and Ta negative anomaly, enrichment in LILE and LREE, and depletion
in HREE (Fig. 11). The lack of Eu anomaly and the high Sr and Al2O3 contents of the rocks
suggest a limited plagioclase fractionation (Figs. 10 and 11). The strong depletion in HREE
compared to LREE leading to high La/YbN (25 to 73) and La/Gd ratio (10.3-17.9) suggest a
first magma fractionation at mid- to lower crust level, which is consistent with modeling of
fertile magmatic systems by Chiaradia and Caricchi (2017). REE patterns of Oligocene and
Miocene magmatic rocks from central Peru (Bissig and Tosdal, 2009), show a more
pronounced "listric shape" and are less depleted in HREE than magmatic rocks from Cerro de
Pasco pointing towards a predominance of amphibole over garnet as a fractionating mineral
(Fig. 11). Bissig and Tosdal (2009) found that igneous rocks with the strongest HREE
fractionation (Sm/Yb > 4) are associated with the largest ore-deposits; this observation is
confirmed at Cerro de Pasco where Sm/Yb ratio is between 4.16 and 16.3.

Magma storage and rejuvenation


The temperatures obtained by the zircon saturation and the Ti-in-zircon thermometer
indicate that magma had cooled prior to emplacement at temperature as low as 675°C, i.e., at
temperatures close to the water-saturated solidus for a dacitic magma (Caricchi and Blundy,
2015). Storage pressure is estimated at between 2 and 4.4 kbar based on the Ti-in-quartz
thermobarometer and the presence of magmatic calcite in apatite phenocrysts from the quartz-
monzonite dykes. The Cs concentrations measured in the SMIs in quartz phenocrysts,
indicating evolved compositions, require that the magmas forming the different volcanic and
subvolcanic rocks have been stored with a high crystallinity degree, between 45 and 92%
before their eruption (assuming, as noted above, fractional crystallization in a closed system,
Fig. 14C). The crystallinity degree directly controls magma mobility; at crystallinity >50%
magma is considered to behave as a rigid body unable to move in the crust (Bachmann and
Bergantz 2004 and 2006; Huber et al., 2010). Storage of a large quantity of magma at high
crystallinity (crystal mush) during several 100s ka at mid or upper crustal level prior to
eruption was proposed for several systems (Bachmann and Bergantz, 2004; Buret et al., 2017;
Cashman and Blundy, 2013; Cooper and Kent, 2014; Cooper 2017; Deering et al., 2016;
Schoene et al., 2012; Spark and Cashman 2017). The spread of 100 to 300 ka observed within
the single zircon grains of each dated (U-Pb) sample reflects a continuous zircon growth in a

37
stable zircon-saturated magma chamber (Fig. 4). The lifespan of ~300 ka of the magmatic
system at Cerro de Pasco is similar to the time scales recorded in other felsic magmatic
systems (Bachman et al., 2007; Buret et al., 2016 and 2017; Deering et al., 2016; Guillong et
al., 2014; Schoene et al., 2012, Wotzlaw et al., 2013).
Addition of thermal energy is required to rejuvenate the silicic mush and to make
possible the ascension of magmas forming the sub-volcanic and volcanic rocks of Cerro de
Pasco. Several models of rejuvenation of silicic crystal mush exist, the most important ones
are the following (Parmigiani et al. (2014): the gas sparging model (Bachman and Bergantz
2006), the unzipping model (Burgisser and Bergantz 2011), and the thermomechanical model
(Huber et al., 2011). In all of them, thermal energy necessary to reheat the crystal mush is
provided by both mafic magma recharge and circulation of hot MVPs (Magmatic volatile
phase). These models do not imply a rejuvenation of the entire magma chamber, but rather
localized mafic recharge and MVP circulation triggering rejuvenation of parts of the crystal
mush. Recharge of more mafic magma into magmatic chambers underneath porphyry systems
has been recognized in other porphyry copper systems (e.g., Bajo de l’Allumbrera: Halter et
al., 2004a, 2004b and 2005; Bingham Canyon: Hattori and Keith 2001; Maughan et al., 2002).
Newly injected mafic to intermediate magma is blocked and crystallizes below the highly
crystalline silicic magma body due to their contrast in density and rheology and therefore may
reach fluid saturation and exsolution of magmatic volatile phases (MVP; Fig. 17). During its
rejuvenation, the crystal mush changes from brittle (when crystals > 50 vol. %) to plastic
(when crystals < 50 vol. %) behavior. In a first stage, the rigid behavior allows circulation and
upward migration of the exsolved MVP (Fig.17; Parmigiani et al., 2014; Tapster et al., 2016,
Buret et al., 2016). Subsequently, these fluids build up the potential to form porphyry-type
mineralization in the shallow part of the system. Further reheating and melting of the mush
lead to a crystallinity decrease (< 50%), and to acquisition of plastic behavior. As a
consequence, fluid migration is interrupted and the lower crystallinity degree places the
crystal mush in the eruptive window (Fig. 17). Rejuvenated crystal mush may then emplace at
shallow depth forming dykes or domes. Subsequently, the deeply exsolved volatiles will be
blocked and stored at the base of the silicic body probably as a volatile-enriched hybrid melt,
until the magmatic body reaches again the suitable crystallinity (>55-60 %) for fluid
migration (Huber et al., 2010; Parmigiani et al., 2014; Tapster et al., 2016).

38
Figure 17: Conceptual model of crystal mush rejuvenation by circulation of MVP exsolved from an underplating
andesitic magma.

Presence of three temporally distinct porphyry-type mineralization events (PM1, PM2,


PM3) alternating with emplacement of sub-volcanic and volcanic rocks (Fig. 16) is coherent
with the proposed rejuvenation dynamic of a silicic magma chamber. Moreover, presence of
evolved rhyolitic silicate melt inclusions in hydrothermal quartz of porphyry-type veins of the
event PM1, is an evidence of MVP circulation through a silicic crystal mush (Rottier et al.,
submitted). These SMIs similar in morphology to those hosted in magmatic quartz have been
interpreted as melt droplets transported by hydrothermal fluids. LA-ICP-MS analyses
performed by Rottier et al., (submitted) on such SMIs hosted in hydrothermal quartz have

39
been included on Figure 18. Their large compositional range (Fig. 18) is thought to represent
the varying compositions of the residual melt in the crystal mush sampled as droplets by the
ascent of the magmatic volatile phase through the silicic mush. In other words, the
hydrothermal quartz-hosted SMIs found previously in the different porphyry-type
mineralizations constitute direct evidence for hot magmatic volatile circulation through a
highly crystalline silicic body. Silicate melt inclusions hosted in hydrothermal quartz and
showing similar characteristic (e.g. glassy and isolated) have been observed during the present
work in veins from PM3, but their chemical compositions have not been determined.
Therefore, we proposed that fluid forming porphyry-type mineralization events (at least PM1
and PM3) are exsolved from mafic to intermediate magma newly injected below the highly
crystalline silicic magma body. It is consistent with the high-temperature (> 600°C) of
formation of the porphyry-type veins and occurrence of CO2-rich and sulfur-rich fluid
inclusions. The fact that the PM3 porphyry-type mineralization has been formed less than 85
ka before emplacement of the quartz-monzonite dykes indicates that crystal mush
rejuvenation could be as fast as <100 ka.

Figure 18: Rb and Sr versus Cs contents in quartz-hosted SMIs from the magmatic rocks and from hydrothermal veins of
porphyry-type mineralization PM1 (for more details see Rottier et al., submitted and Rottier 2017)

40
Magmatic rocks at Cerro de Pasco show a similar phenocryst mineral assemblage
consisting of plagioclase with a similar An content (~25 mol.%), biotite, K-feldspar, quartz,
titanite, apatite +/- amphibole that represents the composition of the crystal mush (Fig. 9).
Varying phenocryst proportions may be due to differences in the phenocryst sampling during
ascent of the eruptible magma batches. Such hypothesis is coherent with the absence of
correlation between the U-Pb ages of the magmatic rocks, their chemical composition, their
radiogenic isotopic signatures, and the degree of crystallization indicated by SMI
compositions. Circulation of MVPs, rich in sulfur and CO2, through the silicic mush could
explain the occurrence of solid inclusions of anhydrite and calcic in apatite phenocryst from
the quartz-monzonite dykes. Presence of anhydrite and lack of magmatic sulfides indicate that
the magmas were saturated in (SO4)2- implying a high oxygen fugacity of the melt (log fO2 >
NNO + 2; Baker and Moretti, 2011), and a sulfur amount in the range of several 100s of ppm
(for a dacite; Baker and Moretti, 2011). No anhydrite was observed in the matrix, suggesting a
later destabilization of the mineral, most probably due to magma ascents because pressure
decrease lead to an increase of sulfur solubility.

Conclusions
New geochronological data focused on the porphyry-type mineralization events
present in the Cerro de Pasco district reveal a first period of at least 400 ka where magmatic
activity and minor porphyry-type mineralization took place alternating with each other. The
large epithermal polymetallic mineralization occurs after this first period but to some extent
could also overprint it, a maximum gap of 0.9 Ma between the two mineralization styles being
estimated. Geochemistry of the magmatic rocks successively emplaced at volcanic to
subvolcanic level at Cerro de Pasco, display typical subduction-related signature and require a
first fractionation in the mid- to lower crust. Study of magmatic quartz phenocryst-hosted
SMIs, application of the zircon saturation thermometer, and the Ti-in-quartz barometer on
selected samples representing the main lithologies, show that magma prior emplacement was
stored at mid-crustal conditions (2 to 4.4 kbar) in a highly crystalline (up to 90 %) non
eruptible state, close to the solidus at temperatures as low as 675°C. High precision U-Pb
geochronology indicates a lifetime of more than 300 ka of this crystal mush punctuated by
repeated episodes of rejuvenation allowing magma to escape towards surface, followed by
period of re-crystallization. Three high-temperature (>600°C) porphyry-type mineralization
events took place during the crystal mush lifespan, displaying veins where evolved SMIs were

41
trapped in hydrothermal quartz. They constitute direct evidence of hot magmatic volatile
circulation through a highly crystalline silicic body. Thus, a direct relationship between a
silicic crystal mush undergoing cyclic rejuvenation and porphyry system formation is
proposed.

Acknowledgements
This study was supported by the Swiss National Science Foundation (project FN
200020_134872). We thank Volcan Companía Minera S.A. for providing financial and
logistical support. Special thanks to Hugo Alvarez and David Cuellar from the Cerro de Pasco
Geology staff. We gratefully acknowledge Hervé Rezeau for assistance during microprobe
analyses, and Jean-Marie Boccard, Fabio Capponi and Michèle Senn for their help with
sample preparation. Early discussions with Vincent Casanova, Cyril Chelle-Michou and
Hervé Rezeau, helped to improve this paper.

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Table A.1: Microthermometry data of the studied fluid inclusions

Assembl Degree of Tm halite Salinity NaCl


Sample n° Chip n° FI n° Type1 2 Th final(°C)3 Tm solid (°C)4 5
age n° fill (°C) equiv6

Solid 60 vapor
x2 1 3 1 Secondary > 600 176/338 522 62.8
30 liquid 10

Solid 60 vapor
x2 1 3 2 Secondary > 600 522 62.8
30 liquid 10

Solid 60 vapor
x2 1 3 3 Secondary > 600 180/272 >570
30 liquid 10

Solid 60 vapor
x2 1 3 4 Secondary > 600 180 >570
30 liquid 10

Solid 60 vapor
x2 1 3 5 Secondary > 600 546 66.2
30 liquid 10

Solid 60 vapor
x2 1 3 6 Secondary > 600 176/265 515 61.8
30 liquid 10

Solid 60 vapor
x2 1 3 7 Secondary > 600 562 68.5
30 liquid 10

Solid 60 vapor
x2 1 3 8 Secondary > 600 545 66
30 liquid 10

Solid 60 vapor
x2 1 3 9 Secondary > 600 289 552 67
30 liquid 10

Solid 60 vapor
x2 1 4 1 Secondary > 600 153/304 476 56.6
30 liquid 10

Solid 60 vapor
x2 1 4 2 Secondary > 600 481 57.2
30 liquid 10

Solid 60 vapor
x2 1 4 3 Secondary > 600 480 57.1
30 liquid 10

Solid 60 vapor
x2 1 4 4 Secondary > 600 473 56.2
30 liquid 10

Solid 60 vapor
x2 1 4 5 Secondary > 600 475 56.4
30 liquid 10

Solid 60 vapor
x2 1 4 6 Secondary > 600 492 58.7
30 liquid 10

Solid 60 vapor
x2 1 4 7 Secondary > 600 488 58.1
30 liquid 10

Solid 60 vapor
x2 1 4 8 Secondary > 600 248 487 58
30 liquid 10

Solid 60 vapor
x2 1 4 9 Secondary > 600 484 57.6
30 liquid 10

Solid 60 vapor
x2 1 4 10 Secondary > 600 481 57.2
30 liquid 10

(1): Classified following Roedder rules


(2): Nature and Vol.% of the different phases present in the fluid inclusions

(3) 600°C correspond to the upper temperature which can be reached by the Linkam stage used for microthermomtery measurment

(4): Melting temperatures of the different solids (other than halite). The first recorded temperature between 153 and 180°C is attributed
to melting of Fe-chloride salt, the second temperature between 248 and 338°C is attributed to melting of sylvite.

(5): Melting temperature of halite


(6): Salinity calculated using melting of halite using equation published in Bodnar (2003)

48
Table A.2: LA-ICP-MS analyses of quartz from
of a magmatic clast with porphyry veining (sample X2; PM3)
Li B Na Mg Al P K Ti Mn Fe Cu Zn As Rb Sr Y Zr Nb Mo
Quartz Analyse # Si (ppm)
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)
Quartz X2 1 15.7 B.D.L B.D.L 1.73 124 465128 25.2 B.D.L 90.4 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0.03 B.D.L B.D.L
Quartz X2 2 8.5 B.D.L 10 B.D.L 102 465128 23.5 B.D.L 78.2 B.D.L B.D.L 0.76 B.D.L B.D.L B.D.L 0.02 B.D.L B.D.L B.D.L B.D.L
Quartz X2 3 11.7 B.D.L 35.1 2.54 122 465128 30.2 B.D.L 94.1 2.02 36.1 6.77 4.48 B.D.L 0.15 0.1 B.D.L B.D.L 0.01 B.D.L
Quartz X2 4 18.6 B.D.L 31.2 2.53 455 465128 20.6 177 160 B.D.L B.D.L B.D.L B.D.L B.D.L 0.85 0.15 B.D.L B.D.L B.D.L B.D.L
Quartz X2 5 20.4 B.D.L 19.5 4.33 482 465128 25.1 229 103 B.D.L 37.3 B.D.L B.D.L B.D.L 1.08 0.17 B.D.L B.D.L B.D.L B.D.L
Quartz X2 6 9.08 B.D.L 2.61 B.D.L 118 465128 B.D.L B.D.L 94.3 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 7 9.08 B.D.L 2.61 B.D.L 118 465128 B.D.L B.D.L 94.3 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 8 12.6 B.D.L 3.63 2.06 128 465128 26.1 B.D.L 40.4 B.D.L B.D.L B.D.L B.D.L B.D.L 0.08 0.01 B.D.L 0.06 B.D.L B.D.L
Quartz X2 9 B.D.L B.D.L B.D.L B.D.L 118 465128 B.D.L B.D.L 92.4 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 10 13.7 B.D.L 4.35 4.6 117 465128 29.9 B.D.L 72 B.D.L B.D.L 1.99 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 11 13.5 B.D.L 0.83 B.D.L 123 465128 22 B.D.L 77.3 B.D.L B.D.L 0.77 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 12 7.68 B.D.L 5.55 B.D.L 116 465128 B.D.L B.D.L 52.7 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 13 8.41 B.D.L 10.3 B.D.L 135 465128 22.6 B.D.L 72.5 B.D.L B.D.L 1.26 B.D.L B.D.L 0.13 0.06 B.D.L B.D.L B.D.L B.D.L
Quartz X2 14 11.3 B.D.L 1.77 B.D.L 130 465128 25.5 B.D.L 75.7 B.D.L B.D.L 1.24 B.D.L B.D.L B.D.L 0.03 B.D.L B.D.L B.D.L B.D.L
Quartz X2 15 8.5 B.D.L 0.98 B.D.L 124 465128 23.9 B.D.L 122 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0.04 B.D.L
Quartz X2 16 10.6 B.D.L 0.88 B.D.L 118 465128 27.6 B.D.L 103 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 17 13.8 B.D.L 5.77 B.D.L 168 465128 33.6 B.D.L 72.1 B.D.L B.D.L 2.09 B.D.L B.D.L 0.18 B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 18 12.1 B.D.L B.D.L 2.14 116 465128 23.6 B.D.L 79.4 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 19 10.6 B.D.L B.D.L B.D.L 115 465128 28.9 B.D.L 63.5 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 20 10.5 B.D.L B.D.L B.D.L 122 465128 26.5 B.D.L 85.4 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 21 8.89 B.D.L 1.26 2.29 106 465128 29.2 B.D.L 55.5 B.D.L 73.6 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 22 12.4 B.D.L 1.44 2.27 117 465128 21.4 B.D.L 92.7 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 23 11 2.66 6.11 1.03 116 465128 19.1 B.D.L 70.3 B.D.L 7.65 B.D.L B.D.L B.D.L B.D.L 0.01 B.D.L B.D.L B.D.L B.D.L
Quartz X2 24 9.86 B.D.L 8.64 3.17 176 465128 22 B.D.L 62.9 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0.09 0.03 B.D.L B.D.L B.D.L
Quartz X2 25 10.4 B.D.L 0.32 0.9 108 465128 22.8 B.D.L 70.7 B.D.L 13.1 0.53 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 26 12.2 B.D.L 20.6 B.D.L 146 465128 B.D.L B.D.L 51.1 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 27 12.2 B.D.L 20.6 B.D.L 146 465128 B.D.L B.D.L 51.1 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 28 11.8 B.D.L 1.8 B.D.L 183 465128 B.D.L B.D.L 55.7 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 29 7.51 B.D.L B.D.L B.D.L 108 465128 B.D.L B.D.L 81.9 B.D.L 76.5 3.89 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 30 7.65 B.D.L 2.2 B.D.L 138 465128 B.D.L B.D.L 75.7 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 31 19.4 B.D.L B.D.L B.D.L 133 465128 42.1 B.D.L 58.1 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L

49
Table A.2: LA-ICP-MS analyses of quartz from
of a magmatic clast with porphyry veining (sample X2; PM3)
Ag Sn Sb Te Cs Ba La Ce Yb W Au Pb
Quartz Analyse #
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)
Quartz X2 1 B.D.L 37.4 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 2 B.D.L 34.4 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0.2
Quartz X2 3 B.D.L 46.7 B.D.L B.D.L 0.03 B.D.L 0.02 0.03 B.D.L B.D.L B.D.L 1.54
Quartz X2 4 B.D.L 37.1 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 5 B.D.L 36.4 B.D.L B.D.L B.D.L B.D.L 0.02 B.D.L B.D.L B.D.L B.D.L 0.13
Quartz X2 6 B.D.L 38.1 B.D.L B.D.L 0.02 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 7 B.D.L 38.1 B.D.L B.D.L 0.02 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 8 B.D.L 34.7 B.D.L B.D.L B.D.L B.D.L B.D.L 0.01 B.D.L B.D.L B.D.L B.D.L
Quartz X2 9 B.D.L 37.8 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 10 B.D.L 41.7 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 11 B.D.L 34.1 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 12 B.D.L 43 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 13 B.D.L 34.3 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0.22
Quartz X2 14 B.D.L 38.6 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0.31
Quartz X2 15 B.D.L 39.6 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 16 B.D.L 38.5 B.D.L B.D.L B.D.L B.D.L B.D.L 0.01 B.D.L B.D.L B.D.L 0.07
Quartz X2 17 B.D.L 45.9 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 18 B.D.L 31.7 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 19 B.D.L 33.6 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 20 B.D.L 33.7 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 21 B.D.L 38.1 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 22 B.D.L 29.8 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 23 0.01 28.7 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0.04
Quartz X2 24 B.D.L 36.8 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 25 B.D.L 31.9 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 26 B.D.L 39.1 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 1.62
Quartz X2 27 B.D.L 39.1 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 1.62
Quartz X2 28 B.D.L 37.7 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 29 B.D.L 35 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0.15 B.D.L B.D.L
Quartz X2 30 B.D.L 39.8 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 31 B.D.L 39.6 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L

50
Table A.2: LA-ICP-MS analyses of quartz from
of a magmatic clast with porphyry veining (sample X2; PM3)
Li B Na Mg Al P K Ti Mn Fe Cu Zn As Rb Sr Y Zr Nb Mo
Quartz Analyse # Si (ppm)
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)
Quartz X2 32 16.7 B.D.L B.D.L B.D.L 110 465128 B.D.L B.D.L 79.3 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 33 16.7 B.D.L B.D.L B.D.L 110 465128 B.D.L B.D.L 79.3 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
B.D.L: Below detectiom limit

51
Table A.2: LA-ICP-MS analyses of quartz from
of a magmatic clast with porphyry veining (sample X2; PM3)
Ag Sn Sb Te Cs Ba La Ce Yb W Au Pb
Quartz Analyse #
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)
Quartz X2 32 0.06 36.8 B.D.L 0.72 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
Quartz X2 33 0.06 36.8 B.D.L 0.72 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
B.D.L: Below detectiom limit

52
Table A.3: Sample descriptions

Echantillon Sampler System East North Elevation Comments

Dacitic tuff sampled in the


CP-14-BR-201 Rottier UTM-PSAD56 360721 8821388 northern part of the diatreme-
dome complex

Fresh dacitic dome samplein


CP-14-BR-203 Rottier UTM-PSAD56 360536 8821340 the northern part of the
diatreme-dome complex

CP-14-BR-207 Rottier UTM-PSAD56 360821 8821336 Fresh quartz-monzonite dyke

CP-14-BR-225 Rottier UTM-PSAD56 360290 8821050 4363 Fresh quartz-monzonite dyke

CP-14-BR-229 Rottier UTM-PSAD56 360198 8820460 4374 Fresh dacitic dome

CP-14-BR-230 Rottier UTM-PSAD56 360320 8819640 4358 Fresh rhyodacitic dome

CP-14-BR-232 Rottier UTM-PSAD56 360235 8820778 4372 Fresh quartz-monzonite dyke

CP-14-BR-241 Rottier UTM-PSAD56 360634 8820804 4396 Fresh quartz-monzonite dyke

Slightly altered trachyte


CP-14-BR-301 Rottier UTM-PSAD56 361389 8820680 4444
porphyry

Dacitic dome sampled at the


CPR 603 Baumgartner UTM-PSAD56 360255 8820377 4404 SW margin of the diatreme-
dome complex

Quartz-monzonite dyke
CPR 604 Baumgartner UTM-PSAD56 360838 8820315 4401 sampled in the southern part of
the diatreme-dome complex
Quartz-monzonite dyke
CPR 472 Baumgartner UTM-PSAD56
2nd ramp tajo Raul Rojas E sampled in the open pit

Quartz-monzonite dyke
CPR 389 Baumgartner UTM-PSAD56 sampled in the northern-part of
the diatreme dome complex

53
Table A.4: Results of LA-ICPMS U-Pb dating

Sample Isotopic ratios Dates (Ma)


206 238 207 235 207 206 206 238 207 235 207
Spot # Pb/ U ±1σ (%) Pb/ U ±1σ (%) Pb/ Pb ±1σ (%) Pb/ U ±2σ (abs) Pb/ U ±2σ (abs) Pb/206Pb ±2σ (abs)
Mineralized trachyte
301 T1 1 0.0024 1.37% 0.0158 7.30% 0.04901 7.70% 15.16 0.41 15.95 2.31 148 318
301 T1 2 0.0023 1.24% 0.0163 5.54% 0.05154 5.85% 15.05 0.37 16.46 1.81 264 268
301 T1 3 0.0023 1.11% 0.0158 6.55% 0.05082 6.48% 14.54 0.32 15.88 2.07 232 300
301 T1 4 0.0024 1.44% 0.0169 10.51% 0.05115 10.55% 15.47 0.44 17 3.54 246 472
301 T2 1,1 0.0023 1.26% 0.0146 5.18% 0.04655 5.37% 14.65 0.37 14.74 1.51 26 150
301 T2 1,2 0.0024 1.14% 0.0142 5.88% 0.04384 6.20% 15.32 0.35 14.3 1.67 0 26
301 T3 1,1 0.0023 1.10% 0.0155 5.66% 0.04859 5.43% 14.97 0.33 15.64 1.76 128 250
301 T3 1,2 0.0023 1.18% 0.0172 6.02% 0.05376 5.86% 15.02 0.35 17.32 2.07 360 264
301 T3 2,1 0.0023 1.11% 0.0166 6.00% 0.05216 6.23% 15 0.33 16.69 1.99 292 286
301 t4 1,1 0.0023 1.07% 0.0157 4.96% 0.04976 5.40% 14.91 0.3 15.79 1.6 182 252
301 t4 1,2 0.0023 0.93% 0.0166 4.55% 0.05221 4.47% 15.12 0.3 16.71 1.5 294 204
301 T4 2,1 0.0023 1.12% 0.0171 5.75% 0.05401 5.80% 14.88 0.3 17.18 2 370 262
301 T4 2,2 0.0024 1.10% 0.0169 5.40% 0.05248 5.54% 15.19 0.3 17.05 1.8 306 254
301 T4 3,1 0.0023 1.09% 0.0148 5.44% 0.04776 5.62% 14.67 0.3 14.92 1.6 86 214
301 T4 3,2 0.0024 1.08% 0.0147 5.58% 0.04541 5.69% 15.31 0.3 14.83 1.6 0 98
301 T4 4 0.0024 0.93% 0.0169 4.77% 0.05219 5.12% 15.31 0.3 17.01 1.6 292 234
301 T5/T6 1,1 0.0023 1.16% 0.0153 5.20% 0.04839 5.51% 14.86 0.3 15.42 1.6 118 242
301 T5/T6 1,2 0.0023 1.03% 0.0167 4.52% 0.05293 4.79% 15.06 0.3 16.84 1.5 324 218
301 T5/T6 2,1 0.0023 1.64% 0.0155 5.88% 0.05006 5.96% 14.58 0.5 15.63 1.8 196 278
301 T5/T6 2,2 0.0023 1.61% 0.0155 6.67% 0.04995 6.37% 14.81 0.48 15.61 2.07 192 298
301 T5/T6 3,1 0.0023 1.28% 0.0145 6.77% 0.04654 6.82% 14.68 0.37 14.64 1.97 24 180
301 T7 1,1 0.0023 1.56% 0.0155 6.26% 0.04842 6.32% 15.02 0.47 15.66 1.95 118 262
301 T7 1,2 0.0023 1.56% 0.0144 6.42% 0.04522 7.03% 14.91 0.46 14.55 1.85 0 118
301 T8 1,1 0.0024 1.76% 0.0158 3.51% 0.05002 4.26% 15.33 0.54 15.9 1.11 194 198
301 T8 1,2 0.0024 2.05% 0.0157 5.40% 0.04863 5.32% 15.13 0.62 15.81 1.69 128 250
301 T8 2,1 0.0024 2.05% 0.0159 4.76% 0.04938 5.11% 15.39 0.63 16.06 1.52 164 238
301 T8 2,2 0.0023 1.86% 0.015 6.14% 0.04683 6.29% 15.09 0.56 15.08 1.84 40 184
301 T8 3 0.0024 2.09% 0.014 6.09% 0.04263 6.65% 15.15 0.63 14.15 1.71 0 0
301 t8 4 0.0023 1.86% 1.49% 4.82% 4.74% 4.63% 14.97 0.56 15.01 1.44 68 176
301 T9 1 0.0024 2.31% 1.52% 6.73% 4.50% 7.37% 15.56 0.72 15.33 2.05 0 112

54
Table A.4: Results of LA-ICPMS U-Pb dating

Sample Isotopic ratios Dates (Ma)


206 238 207 235 207 206 206 238 207 235 207
Spot # Pb/ U ±1σ (%) Pb/ U ±1σ (%) Pb/ Pb ±1σ (%) Pb/ U ±2σ (abs) Pb/ U ±2σ (abs) Pb/206Pb ±2σ (abs)
301 T9 2 0.0023 1.91% 1.42% 6.27% 4.42% 6.66% 14.98 0.57 14.32 1.78 0 56
301 T9 3 0.0023 2.06% 1.51% 6.42% 4.74% 6.24% 14.77 0.61 15.25 1.94 66 208
301 T10 1 0.0024 1.65% 1.52% 4.42% 4.63% 4.63% 15.38 0.51 15.3 1.34 14 120
301 T 10 2,1 0.0023 1.94% 1.58% 6.32% 4.90% 6.14% 14.96 0.58 15.9 2 146 284
301 T10 2,2 0.0023 2.32% 1.40% 7.15% 4.26% 7.09% 15.08 0.7 14.1 2 0 0
301 T10 4 0.0023 1.84% 1.61% 4.88% 5.04% 4.82% 15.07 0.55 16.25 1.57 212 224
301 T11 1 0.0023 1.63% 1.60% 6.46% 4.99% 6.72% 15.02 0.49 16.16 2.07 188 314
301 t11 2 0.0023 1.67% 0.0154 6.30% 0.0485 7.04% 14.59 0.49 15.53 1.94 122 280
301 t11 3,1 0.0023 1.48% 0.017 5.49% 0.05322 5.56% 15 0.44 17.13 1.86 338 252
301 t11 3,2 0.0023 1.59% 0.0169 6.19% 0.05311 6.29% 14.79 0.47 17.06 2.09 332 286
301 t12 1 0.0024 1.07% 0.0165 5.03% 0.05062 5.00% 15.26 0.33 16.6 1.66 222 232
301 T12 2 0.0023 1.33% 0.0177 5.03% 0.05526 5.40% 15.01 0.4 17.82 1.78 422 242
301 T12 3,1 0.0023 1.20% 0.0164 4.44% 0.05166 4.55% 14.9 0.36 16.55 1.46 270 208
301 T12 3,2 0.0024 0.99% 0.0165 5.11% 0.05116 5.24% 15.13 0.3 16.64 1.69 246 242
301 T12 4 0.0023 1.47% 0.0154 6.64% 0.04877 6.96% 14.85 0.44 15.5 2.04 136 292
301 T13 1 0.0024 0.97% 0.0162 4.71% 0.0507 4.83% 15.22 0.29 16.36 1.53 226 224
301 T13 2 0.0023 1.04% 0.0157 5.03% 0.05118 5.18% 14.65 0.3 15.83 1.58 248 240
301 T13 4 0.0023 1.28% 0.0135 6.48% 0.04219 6.88% 15.06 0.38 13.64 1.76 0 0
301 T14 1 0.0024 0.92% 0.0163 3.87% 0.05107 3.78% 15.18 0.28 16.4 1.26 242 174
301 T14 2 0.0023 1.12% 0.0156 5.14% 0.05004 5.27% 14.67 0.33 15.74 1.6 196 246
301 T14 3 0.0023 1.01% 0.017 5.00% 0.05272 5.04% 15.05 0.3 17.08 1.69 316 230
301 T15 1 0.0024 1.81% 0.0172 5.24% 0.0528 5.07% 15.2 0.55 17.31 1.8 320 230
301 T15 2 0.0024 0.87% 0.0166 3.89% 0.05165 4.01% 15.23 0.26 16.69 1.29 268 184
301 T15 4 0.0023 1.25% 0.0153 4.60% 0.04841 4.49% 15.13 0.38 15.4 1.41 118 212
301 T15 3 0.0023 1.28% 0.0154 5.53% 0.04982 5.95% 14.71 0.38 15.54 1.71 186 278
301 T16 1 0.0023 1.14% 0.0166 5.72% 0.05307 6.44% 14.99 0.34 16.74 1.9 330 292
301 T16 3 0.0024 1.32% 0.0157 5.06% 0.04883 5.08% 15.17 0.4 15.84 1.59 138 238
301 t16 4 0.0023 1.60% 0.0164 6.24% 0.05125 6.10% 15.03 0.48 16.55 2.05 252 282
301 T17 2,1 0.0023 1.87% 0.0141 6.13% 0.0434 5.97% 15.09 0.56 14.21 1.73 0 0
301 T17 2,2 0.0023 2.33% 0.0159 6.99% 0.04904 6.68% 15.04 0.7 16.06 2.23 148 298
301 T17 3,1 0.0023 2.11% 0.0156 4.81% 0.05082 4.70% 14.82 0.63 15.68 1.5 232 216

55
Table A.4: Results of LA-ICPMS U-Pb dating

Sample Isotopic ratios Dates (Ma)


206 238 207 235 207 206 206 238 207 235 207
Spot # Pb/ U ±1σ (%) Pb/ U ±1σ (%) Pb/ Pb ±1σ (%) Pb/ U ±2σ (abs) Pb/ U ±2σ (abs) Pb/206Pb ±2σ (abs)
301 T17 3,2 0.0024 2.14% 0.0166 6.42% 0.05081 6.25% 15.3 0.65 16.71 2.13 232 290
301 T18 1,1 0.0023 1.45% 0.0154 6.45% 0.04876 6.73% 15.12 0.44 15.56 1.99 136 286
301 T18 1,2 0.0025 1.47% 0.0172 6.42% 0.05043 6.36% 15.93 0.47 17.3 2.2 214 294
301 T18 2 0.0023 1.62% 0.021 6.05% 0.06499 6.36% 14.9 0.48 21.12 2.53 774 268
301 T18 4 0.0023 0.99% 0.0159 4.79% 0.05094 4.79% 14.92 0.3 16.01 1.52 236 222
301 T19 1 0.0023 0.97% 0.0166 4.71% 0.05305 4.59% 14.74 0.29 16.7 1.56 330 208
301 t19 2 0.0023 1.11% 0.0159 5.04% 0.0506 5.53% 14.76 0.33 15.97 1.6 222 256
301 T19 4 0.0023 1.13% 0.0168 5.26% 0.05411 5.34% 14.63 0.33 16.93 1.77 374 240
301 T20 2 0.0023 0.88% 0.016 3.45% 0.05037 3.53% 14.96 0.26 16.07 1.1 210 162
301 T20 3 0.0023 1.22% 0.0195 5.26% 0.06081 5.42% 14.95 0.36 19.58 2.04 632 234
301 T20 4 0.0023 1.03% 0.016 5.16% 0.04979 5.75% 14.9 0.31 16.11 1.65 184 270
301 T21 1 0.0023 1.32% 0.0174 5.33% 0.0563 5.65% 14.57 0.38 17.52 1.85 464 252
301 T21 2 0.0023 1.16% 0.0155 4.49% 0.04923 4.88% 14.87 0.34 15.67 1.4 158 228
301 T21 3 0.0023 1.07% 0.0154 5.37% 0.04905 5.72% 14.66 0.31 15.48 1.65 150 268
301 T21 4 0.0023 1.47% 0.0165 5.68% 0.05177 6.05% 14.82 0.44 16.58 1.87 274 278
301 T22 1 0.0023 1.39% 0.0155 5.36% 0.04905 5.64% 14.91 0.41 15.6 1.66 150 264
301 T22 2 0.0023 1.39% 0.0153 6.50% 0.04831 6.89% 14.71 0.41 15.47 2 114 268
301 T22 3 0.0023 1.61% 0.0141 5.75% 0.04407 6.20% 15.11 0.49 14.24 1.63 0 38
301 T22 4,1 0.0023 1.38% 0.0164 7.14% 0.05261 7.05% 14.61 0.4 16.57 2.35 310 322
301 T22 4,2 0.0023 1.01% 0.0154 5.01% 0.04826 5.26% 14.98 0.3 15.53 1.54 112 230
301 T23 1 0.0023 2.00% 0.0153 6.32% 0.04711 6.04% 15.01 0.6 15.46 1.94 54 192
301 T23 2 0.0024 1.70% 0.0166 5.60% 0.05104 5.82% 15.23 0.52 16.72 1.86 242 268
301 T23 4 0.0024 2.10% 0.014 6.92% 0.04329 6.78% 15.22 0.64 14.11 1.94 0 8
301 T24 1 0.0023 2.06% 0.0153 5.60% 0.0476 4.97% 14.79 0.61 15.39 1.71 78 192
301 T25 1 0.0024 1.73% 0.0164 4.61% 0.0498 4.85% 15.39 0.53 16.54 1.51 184 226
301 T25 2 0.0023 1.48% 0.0145 5.14% 0.04561 5.18% 14.93 0.44 14.6 1.49 0 98
301 T25 3,1 0.0024 1.81% 0.0142 6.58% 0.04328 6.96% 15.35 0.56 14.28 1.87 0 12
301 T25 3,2 0.0023 2.01% 0.017 6.34% 0.05285 6.56% 15.02 0.6 17.13 2.16 322 298
Mineralized clasts
X1 T28 1 0.0023 1.58% 0.0169 6.38% 0.05317 7.19% 14.94 0.47 16.98 2.15 336 326
X1 T28 2 0.0023 1.78% 0.0182 7.48% 0.05572 7.23% 15.06 0.54 18.27 2.71 440 324

56
Table A.4: Results of LA-ICPMS U-Pb dating

Sample Isotopic ratios Dates (Ma)


206 238 207 235 207 206 206 238 207 235 207
Spot # Pb/ U ±1σ (%) Pb/ U ±1σ (%) Pb/ Pb ±1σ (%) Pb/ U ±2σ (abs) Pb/ U ±2σ (abs) Pb/206Pb ±2σ (abs)
X1 T28 3 0.0023 1.63% 0.017 5.58% 0.05301 5.87% 15.09 0.49 17.1 1.89 328 266
X1 T28 4 0.0024 1.32% 0.017 5.37% 0.05261 5.42% 15.3 0.4 17.13 1.82 310 248
X1 T29 1 0.0023 1.75% 0.0162 4.80% 0.05115 5.24% 14.92 0.52 16.32 1.55 246 242
X1 T29 2 0.0023 1.80% 0.016 6.74% 0.05055 6.58% 14.79 0.53 16.09 2.15 220 304
X1 T30 1,1 0.0023 2.22% 0.0159 6.38% 0.05006 6.46% 14.76 0.66 16.02 2.03 196 300
X1 T30 1,2 0.0023 2.35% 0.0138 7.87% 0.04364 7.86% 14.55 0.68 13.87 2.17 0 52
X1 T30 2 0.0023 1.70% 0.0166 6.18% 0.05211 5.90% 14.81 0.5 16.67 2.04 290 270
X1 T30 3 0.0024 1.82% 0.0162 5.17% 0.05045 4.98% 15.17 0.55 16.29 1.67 214 230
X1 T30 4 0.0023 2.09% 0.0151 6.42% 0.0473 6.21% 14.99 0.63 15.2 1.94 64 206
X1 T31 1 0.0023 1.88% 0.0149 5.63% 0.04702 5.40% 14.84 0.56 15.05 1.68 50 174
X1 T31 2 0.0022 1.81% 0.0155 5.50% 0.05095 6.35% 14.38 0.52 15.61 1.7 238 294
X1 T31 3 0.0023 1.72% 0.0167 8.36% 0.05181 7.37% 15.04 0.52 16.78 2.78 276 338
X1 T32 1 0.0023 1.22% 0.0159 5.39% 0.05036 5.47% 14.91 0.36 15.99 1.71 210 254
X1 T32 2 0.0023 1.26% 0.0165 4.73% 0.05167 4.89% 15.09 0.38 16.65 1.56 270 224
X1 T33 1,1 0.0023 1.21% 0.0156 5.29% 0.05063 5.54% 14.53 0.35 15.69 1.65 224 256
x1 t33 1,2 0.0023 0.66% 1.44% 2.35% 4.61% 2.28% 14.75 0.2 14.48 0.68 4 58
X1 T33 2 0.0024 1.30% 1.53% 6.31% 4.66% 6.79% 15.45 0.4 15.4 1.93 26 182
X1 T333 3,1 0.0023 1.10% 1.64% 5.12% 5.13% 5.30% 14.96 0.33 16.49 1.68 252 244
X1 T33 3,2 0.0024 1.30% 1.60% 4.98% 4.98% 5.01% 15.26 0.4 16.08 1.59 184 234
X1 T34 1 0.0023 1.92% 1.56% 8.01% 4.91% 7.77% 14.88 0.57 15.72 2.5 150 322
X1 T34 2 0.0023 1.53% 1.45% 6.49% 4.60% 6.55% 15.01 0.46 14.65 1.89 0 146
X1 T34 3 0.0024 1.15% 1.70% 5.19% 5.25% 5.53% 15.27 0.35 17.11 1.76 306 252
X1 T34 4 0.0023 1.29% 1.83% 5.92% 5.73% 5.66% 15.11 0.39 18.43 2.16 502 250
X1 T35 1 0.0023 1.34% 1.67% 4.48% 5.36% 4.76% 14.68 0.39 16.83 1.49 352 216
X1 T35 2 0.0023 1.68% 1.66% 5.61% 5.24% 6.04% 14.75 0.49 16.67 1.86 300 276
X1 T35 3 0.0023 1.22% 0.0175 5.39% 0.05472 5.55% 14.99 0.37 17.58 1.88 400 250
X1 T36 3 0.0023 1.41% 0.0167 6.26% 0.05292 6.31% 14.83 0.42 16.86 2.09 324 288
X1 T36 4 0.0023 1.48% 0.0192 5.50% 0.06095 5.65% 14.75 0.43 19.36 2.11 636 244
X1 T37 2 0.0023 1.13% 0.0152 5.01% 0.04705 4.93% 15.02 0.34 15.32 1.52 50 164
X1 T37 4 0.0023 1.41% 0.0171 5.65% 0.05355 5.61% 14.91 0.42 17.18 1.92 352 254
X1 t38 1 0.0023 0.86% 0.0151 3.32% 0.04792 3.20% 14.98 0.26 15.26 1.01 94 152

57
Table A.4: Results of LA-ICPMS U-Pb dating

Sample Isotopic ratios Dates (Ma)


206 238 207 235 207 206 206 238 207 235 207
Spot # Pb/ U ±1σ (%) Pb/ U ±1σ (%) Pb/ Pb ±1σ (%) Pb/ U ±2σ (abs) Pb/ U ±2σ (abs) Pb/206Pb ±2σ (abs)
x1 T38 2 0.0024 1.36% 0.0172 6.88% 0.05275 7.48% 15.27 0.42 17.28 2.36 318 340
X1 T38 3 0.0023 1.05% 0.0157 5.52% 0.04973 5.84% 14.98 0.31 15.83 1.74 182 272
X1 T40 1 0.0024 1.05% 0.0159 4.61% 0.04944 4.91% 15.26 0.32 16.06 1.47 168 230
X1 T40 2.1 0.0023 1.18% 0.0164 4.66% 0.05247 4.94% 14.56 0.34 16.47 1.52 304 226
X1 T40 2.2 0.0023 1.44% 0.0141 8.42% 0.04408 9.18% 15.02 0.43 14.27 2.39 0 104
X1T40 3 0.0023 1.23% 0.015 7.39% 0.04706 7.56% 14.95 0.37 15.12 2.22 52 222
X1 T41 1 0.0023 1.46% 0.0157 6.04% 0.04976 6.58% 14.91 0.43 15.84 1.9 182 308
X1 T41 2 0.0023 1.21% 0.0156 5.08% 0.05004 5.44% 14.54 0.35 15.69 1.58 196 254
X1 T41 3 0.0023 1.02% 0.0139 4.58% 0.04495 4.65% 14.75 0.3 14.04 1.28 0 50
X1 T42 1 0.0022 1.34% 0.0172 6.41% 0.05622 6.31% 14.35 0.38 17.3 2.2 460 280
X1 T42 2 0.0024 2.09% 0.0141 7.02% 0.0436 6.60% 15.27 0.64 14.23 1.98 0 22
X1 T42 3 0.0024 1.55% 0.0165 6.00% 0.05125 5.74% 15.17 0.47 16.61 1.98 250 264
x1 t42 4 0.0023 1.13% 0.0153 5.54% 0.04844 5.67% 14.79 0.33 15.37 1.69 120 248
X1 43 1 0.0024 2.46% 0.0152 6.13% 0.04696 6.68% 15.22 0.75 15.27 1.86 46 198
X1 T43 3 0.0023 2.37% 0.0156 6.01% 0.04901 6.30% 15.06 0.71 15.72 1.87 148 288
X1 T44 1 0.0024 2.18% 0.0165 8.14% 0.05098 7.80% 15.18 0.66 16.6 2.68 240 362
X1 T45 1 0.0023 2.32% 0.0168 5.78% 0.05373 6.03% 14.84 0.69 16.93 1.94 358 274
X1 T45 2 0.0024 1.89% 0.0194 6.42% 0.05947 6.20% 15.21 0.57 19.5 2.48 584 270
X1 T46 1 0.0023 1.83% 0.0184 7.40% 0.05725 7.69% 14.8 0.54 18.55 2.72 500 338
X1 T46 2 0.0023 1.48% 0.0152 7.21% 0.04824 7.36% 14.75 0.44 15.32 2.19 110 276
X1 T46 3 0.0023 1.60% 0.0149 5.94% 0.04635 6.16% 15.1 0.48 15.01 1.77 16 156
X1 T47 1.1 0.0023 1.27% 0.0153 5.02% 0.04775 5.24% 14.94 0.38 15.4 1.53 86 206
X1 T47 1.2 0.0023 1.24% 0.0157 4.82% 0.05 4.73% 14.8 0.4 15.8 1.5 194 220
standard plesovice
std1 0.0537 1.49% 0.3832 1.43% 0.05217 1.18% 337.1 9.8 329.4 8 292 54
std2 0.0541 1.34% 0.3942 1.33% 0.05309 0.85% 339.7 8.8 337.4 7.7 332 40
std3 0.0538 1.36% 0.3968 1.31% 0.05404 0.93% 337.51 8.9 339.32 7.6 372 42
std4 0.0533 1.29% 0.3908 1.27% 0.05384 0.94% 334.65 8.4 334.97 7.2 364 42
std5 0.0554 1.26% 0.4046 1.11% 0.05273 0.94% 347.67 8.55 345.01 6.49 316 44
std6 0.0538 1.25% 0.3891 1.24% 0.0527 1.12% 338.03 8.25 333.74 7.03 314 50
std7 0.0539 1.35% 39.18% 1.30% 5.29% 0.97% 338.71 8.91 335.71 7.4 324 44

58
Table A.4: Results of LA-ICPMS U-Pb dating

Sample Isotopic ratios Dates (Ma)


206 238 207 235 207 206 206 238 207 235 207
Spot # Pb/ U ±1σ (%) Pb/ U ±1σ (%) Pb/ Pb ±1σ (%) Pb/ U ±2σ (abs) Pb/ U ±2σ (abs) Pb/206Pb ±2σ (abs)
std8 0.0543 1.66% 39.13% 1.55% 5.32% 1.04% 340.80 11 335.31 8.85 336 48
std9 0.0539 1.77% 0.3885 1.61% 0.05302 1.06% 338.42 11.7 333.25 9.13 328 48
std10 0.0549 1.60% 0.4004 1.39% 0.05341 1.10% 344.62 10.75 341.95 8.08 346 50
std11 0.0535 1.58% 0.395 1.33% 0.0537 1.17% 336 10.35 338.02 7.62 358 54
std12 0.0531 1.72% 0.3854 1.54% 0.05303 1.04% 333.42 11.21 331 8.72 330 46
std13 0.0534 1.67% 0.3943 1.63% 0.05416 1.16% 335.09 10.93 337.49 9.34 376 52
std14 0.0534 1.68% 0.3917 1.35% 0.05399 1.05% 335.48 10.98 335.64 7.74 370 48
std15 0.0545 1.48% 0.3997 1.27% 0.05373 0.90% 341.83 9.86 341.47 7.35 358 42
std16 0.0538 1.19% 0.3958 1.32% 0.05299 1.01% 338 7.83 338.62 7.58 328 46
std17 0.0543 1.56% 0.3925 1.72% 0.05311 1.11% 340.91 10.38 336.21 9.87 332 52
std18 0.0533 1.51% 0.3965 1.53% 0.05341 1.20% 334.68 9.83 339.14 8.85 346 54
std19 0.053 1.17% 0.3936 1.34% 0.05373 1.03% 332.75 7.6 337.01 7.71 358 46
std20 0.0523 1.56% 0.3934 1.58% 0.05432 1.32% 328.46 10.02 336.83 9.03 384 58
std21 0.0533 1.06% 0.3881 1.29% 0.05335 1.10% 335.03 6.95 333 7.32 342 50
std22 0.0538 0.92% 0.3936 1.34% 0.05366 1.08% 337.83 6.08 336.97 7.67 356 48
std23 0.0536 0.86% 39.63% 1.16% 5.37% 0.96% 336.56 5.63 338.94 6.68 356 44
std24 0.053 1.00% 38.75% 1.20% 5.33% 1.00% 332.77 6.49 332.57 6.79 340 46
std25 0.0534 0.33% 0.3905 0.82% 0.05335 0.77% 335.33 2.17 334.74 4.69 342 34
std26 0.053 0.33% 0.3912 0.87% 0.05359 0.75% 332.78 2.11 335.27 4.96 354 34
std27 0.0531 1.20% 0.3858 1.07% 0.05304 1.02% 333.76 7.81 331.28 6.07 330 46
std28 0.053 1.60% 0.3844 1.67% 0.0537 1.17% 333 10.41 330.27 9.39 358 54
std29 0.0529 1.09% 0.4058 1.14% 0.05564 0.92% 332.08 7.06 345.84 6.66 436 42
std30 0.0534 1.30% 0.3912 1.25% 0.05289 0.95% 335.62 8.49 335.24 7.12 324 42
std31 0.0531 0.98% 0.3875 1.06% 0.05286 0.88% 333.27 6.35 332.58 5.99 322 40
std32 0.0529 0.74% 0.3907 1.17% 0.05326 0.98% 332.39 4.77 334.89 6.65 340 46

59
Table A.5: Results of ID-TIMS U-Pb dating

Composition Isotopic Ratios Dates (Ma)


Sam 206Pb/
Fraction
ple Th/ Pb* Pbc Pb*/ 206Pb/ 207Pb/ 207Pb/ 206Pb/ Corr. 207Pb/ ±2σ 207Pb/ ±2σ 206Pb/ ±2σ 238U ±2σ
Ua (pg) b (pg) c Pbc d 204Pb f 206Pb g ±2σ % 235U g ±2σ % 238U g ±2σ % coef. 206Pb h abs 235U h abs 238U h abs <Th> i abs % disc j
301
301 301_z1 0.41 8.17 0.42 19 1155.278 0.045535 1.71 0.01482 1.8 0.0023609 0.063 0.717 -28 41 14.93 0.26 15.2015 0.0096 15.2840 0.0093 154.22
301 301_z5 0.83 5.19 0.32 16 865.644 0.04653 2.28 0.01514 2.3 0.0023613 0.11 0.660 24 55 15.26 0.36 15.204 0.017 15.286 0.017 36.99
301 301_z4 0.57 6.59 0.41 16 930.561 0.047011 2.10 0.01531 2.2 0.0023625 0.16 0.469 49 50 15.42 0.33 15.212 0.024 15.294 0.024 68.77
301 301_z7 0.83 2.34 0.43 5 307.439 0.04741 6.47 0.0154 6.7 0.0023628 0.28 0.734 69 150 15.6 1.0 15.213 0.043 15.296 0.042 77.88
301 301_z3 0.57 2.03 0.22 9 541.233 0.04713 3.65 0.01549 3.8 0.0023851 0.17 0.688 55 87 15.61 0.58 15.357 0.027 15.439 0.026 71.90

X1
X1 X1_z3 0.76 1.78 1.44 1 84.534 0.0497 26.3 0.0160 27 0.002340 1.1 0.750 182 610 16.2 4.4 15.07 0.17 15.15 0.16 91.72
X1 X1_z2 0.62 2.00 0.61 3 202.150 0.04782 9.96 0.0154 10 0.0023421 0.41 0.744 89 240 15.6 1.6 15.080 0.061 15.162 0.060 83.08
X1 X1_z5 0.65 2.22 0.57 4 236.480 0.04719 8.57 0.0152 8.8 0.0023419 0.37 0.723 58 200 15.3 1.3 15.079 0.056 15.168 0.055 73.94
X1 X1_z1 0.65 2.61 0.21 12 702.147 0.04749 2.76 0.01550 2.8 0.0023688 0.13 0.692 73 66 15.62 0.44 15.252 0.020 15.333 0.020 79.10
X1 X1_z6 0.52 14.0 0.59 24 1384.405 0.047278 1.37 0.01544 1.4 0.0023690 0.071 0.612 62 33 15.55 0.22 15.254 0.011 15.347 0.011 75.48
X1 X1_z4 0.69 2.29 0.42 5 312.574 0.04793 6.25 0.0157 6.4 0.0023731 0.27 0.726 95 150 15.8 1.0 15.280 0.041 15.367 0.040 83.88
X1 X1_z7 0.81 3.85 0.74 5 290.934 0.05306 6.04 0.0271 6.2 0.003713 0.28 0.727 330 140 27.2 1.7 23.888 0.068 23.972 0.067 92.77

a Th contents calculated from radiogenic 208Pb and the 207Pb/206Pb date of the sample, assuming concordance between U-Th and Pb systems.
b Total mass of radiogenic Pb.
c Total mass of common Pb.
d Ratio of radiogenic Pb (including 208Pb) to common Pb.
e Th/U ratio of magma from which mineral crystallized.
f Measured ratio corrected for fractionation and spike contribution only.
g Measured ratios corrected for fractionation, tracer and blank.
h Isotopic dates calculated using the decay constants λ238 = 1.55125E-10 and λ235 = 9.8485E-10 (Jaffey et al. 1971).
i Corrected for initial Th/U disequilibrium using radiogenic 208Pb and Th/U[magma] specified.
j % discordance = 100 - (100 * (206Pb/238U date) / (207Pb/206Pb date))

60
Table A.6: LA-ICP-MS analyses of trace elements in magmatic zircon

Al Si Ti Rb Sr Zr Nb Ba La Ce Pr Nd Sm Eu Gd Tb Dy Ho
Sample P (ppm) Y (ppm)
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)

Mineralized trachyte
301 Z1 Rims 14.1 147719 201 B.D.L 0.14 0.94 165 405644 3.02 B.D.L 0.96 18.9 0.24 1.24 1.59 0.45 5.45 1.16 15.4 4.96
301 Z1 CORE 12.9 147719 79.7 B.D.L B.D.L 0.24 246 392247 2.71 0.34 0.09 13.3 B.D.L 0.47 0.86 0.49 4.69 1.32 18.4 6.92
301 Z2 Rims B.D.L 147719 67.8 B.D.L 0.1 0.15 217 411231 2.93 B.D.L B.D.L 22.3 0.04 0.61 0.96 0.63 6.33 1.6 17.3 6.05
301 Z2 CORE B.D.L 147719 123 3.31 B.D.L 0.16 401 421787 3.35 B.D.L B.D.L 27.5 0.09 1.44 2.31 1.06 11.9 3.09 35.6 12
301 Z3 Rims B.D.L 147719 65.8 3.34 B.D.L 0.1 151 395615 2.29 B.D.L B.D.L 16.3 0.03 0.45 1.03 0.47 4.92 1.02 11.2 4.14
301 Z3 CORE 46.1 147719 87.1 B.D.L 0.48 0.23 339 386463 3.48 0.29 B.D.L 27.4 0.03 0.77 1.71 0.69 9.19 2.42 28.1 9.99
301 Z4 Rims B.D.L 147719 76.7 B.D.L B.D.L 0.13 221 398405 2.92 B.D.L 0.02 24.4 B.D.L 0.54 1.07 0.55 6.71 1.59 16.9 6.58
301 Z4 CORE B.D.L 147719 83.3 B.D.L B.D.L 0.1 298 423787 2.61 B.D.L B.D.L 16.6 B.D.L 0.86 1.46 0.57 6.98 1.97 22.1 8.38
301 Z5 Rims B.D.L 147719 65.8 B.D.L B.D.L 0.09 172 399381 2.92 B.D.L 0.02 17.7 0.02 0.5 0.82 0.38 4.06 1.14 12.2 4.83
301 Z5 CORE B.D.L 147719 73.4 B.D.L B.D.L B.D.L 219 416184 2.68 B.D.L B.D.L 13.2 B.D.L 0.72 0.92 0.5 5.39 1.37 16.6 6.47
301 Z6 Rims B.D.L 147719 117 B.D.L B.D.L 0.27 156 407826 2.45 B.D.L 0.36 17.9 0.09 0.71 1.03 0.47 4.47 1.07 12.3 4.31
301 Z6 CORE B.D.L 147719 92.5 B.D.L B.D.L 0.12 408 401304 3.61 B.D.L B.D.L 26.6 0.07 0.74 2.19 1.04 10.5 3.21 35.7 12.1
301 Z7 Rims B.D.L 147719 68.2 0 B.D.L B.D.L 229 393044 3.22 B.D.L B.D.L 20.1 0.03 0.61 1.14 0.49 6.73 1.85 19.5 6.67
301 Z7 CORE B.D.L 147719 78.9 B.D.L B.D.L B.D.L 202 383461 2 B.D.L 0.06 11 B.D.L 0.22 0.57 0.2 4.23 1.13 14.6 5.45
301 Z8 Rims B.D.L 147719 77.2 B.D.L B.D.L B.D.L 223 400722 3.38 B.D.L B.D.L 21.8 0.03 0.7 1.67 0.6 6.56 1.85 18.7 6.58
301 Z8 CORE B.D.L 147719 146 B.D.L B.D.L 0.21 648 418440 5.05 B.D.L B.D.L 33.6 0.09 1.49 3.83 1.81 20.7 5.21 61 19.4
Mineralized clast
X1 Z1 Rims B.D.L 147719 72.5 B.D.L B.D.L 0.23 135 403103 2.29 B.D.L 0.12 16.8 0.04 0.69 0.97 0.4 4.06 1.12 10.2 3.91
X1 Z1 Core B.D.L 147719 72.9 B.D.L B.D.L B.D.L 144 388159 2.58 B.D.L B.D.L 14.8 B.D.L B.D.L 0.54 0.3 2.96 1.03 9.78 4.01
X1 Z2 Rims B.D.L 147719 84.7 3.74 B.D.L 0.18 160 410524 2.72 0.21 0.23 21.1 0.05 0.75 0.9 0.48 4.9 1.21 12.6 4.38
X1 Z3 Rims B.D.L 147719 70.6 B.D.L B.D.L B.D.L 159 420259 2.93 B.D.L 0.13 20.3 0.04 0.48 1.09 0.27 5.15 1.29 13.9 4.39
X1 Z3 Core B.D.L 147719 70.1 B.D.L 0.14 0.09 403 410477 4.31 B.D.L B.D.L 35.5 0.1 1.28 2.81 1.11 11 3.12 31.8 11.3
X1 Z4 Rims B.D.L 147719 76.5 B.D.L 0.13 0.11 302 420476 3.37 B.D.L 0.04 28.2 0.06 1.12 1.92 0.78 8.8 2.26 25.6 8.56
X1 Z4 Core 12.1 147719 139 B.D.L B.D.L 0.28 652 403432 3.83 B.D.L B.D.L 41.2 0.15 2.49 4.74 2.05 23.1 5.7 60.6 20.1
X1 Z5 Rims B.D.L 147719 67.3 B.D.L B.D.L 0.14 124 441042 2.6 B.D.L 0.08 15.9 0.03 0.52 0.62 0.31 2.91 0.9 9.04 3.41
X1 Z5 Core B.D.L 147719 263 B.D.L B.D.L 0.19 508 412460 5.31 0.16 B.D.L 5.35 0.1 1.33 2.47 0.53 10.5 3.29 43.3 15.8
X1 Z6 Rims B.D.L 147719 73.3 B.D.L B.D.L 0.08 180 405431 2.35 B.D.L B.D.L 22.5 0.04 0.61 1.26 0.65 5.71 1.39 15.1 5.35
X1 Z6 Core B.D.L 147719 90.2 B.D.L B.D.L 0.11 268 416886 2.7 B.D.L 0.06 15.4 0.05 0.8 1.39 0.57 4.62 1.79 20.7 7.59
X1 Z7 Rims B.D.L 147719 59.7 B.D.L B.D.L 0.22 149 438802 2.48 B.D.L B.D.L 13.1 0.05 B.D.L 0.43 0.3 3.01 0.81 10.5 3.89

61
Table A.6: LA-ICP-MS analyses of trace elements in magmatic zircon

206 207 208 Temperature (°C) calculated using


Er Tm Yb Lu Hf Ta Pb Pb Pb Th
Sample U (ppm) the Ti-in-quartz equation of Ferry
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)
and Watson (2007)
Mineralized trachyte
301 Z1 Rims 23.5 4.91 55.2 12.5 8478 0.23 3.47 0.49 0.34 222 326 <722
301 Z1 CORE 38.5 8.61 102 25.7 7869 0.2 3.12 B.D.L B.D.L 109 273 <676
301 Z2 Rims 31 7.25 80.7 19 8427 0.25 4.63 B.D.L 0.43 337 475 <698
301 Z2 CORE 58.7 12.8 137 30.3 8323 0.4 4.75 B.D.L 0.45 299 455 680
301 Z3 Rims 21.3 4.94 52.2 12.7 7896 0.16 3.34 B.D.L 0.24 170 271 681
301 Z3 CORE 49.1 10.5 116 27.1 7897 0.37 5.54 B.D.L 0.8 318 500 <710
301 Z4 Rims 30.1 7.06 78.1 18.3 8043 0.25 6.41 B.D.L 0.66 429 572 <693
301 Z4 CORE 45.3 10.1 119 28.3 8233 0.22 3.08 B.D.L 0.21 140 320 <705
301 Z5 Rims 25.1 5.61 65.9 16.6 8129 0.15 4.37 B.D.L 0.36 246 408 <691
301 Z5 CORE 32.4 7.35 84.4 19.4 8526 0.13 2.24 B.D.L B.D.L 87.4 209 <720
301 Z6 Rims 23.7 4.74 55.8 13.6 8174 0.12 3.02 B.D.L 0.26 194 304 <688
301 Z6 CORE 61.7 12.9 136 31.8 7915 0.29 3.89 B.D.L 0.47 211 347 <702
301 Z7 Rims 32.5 7.03 76.5 17.3 8070 0.26 3.71 B.D.L 0.34 194 331
301 Z7 CORE 31 7.78 89.9 23 7918 0.14 3.07 B.D.L B.D.L 94.7 252 <718
301 Z8 Rims 33.7 6.59 73.7 16.6 8217 0.36 4.76 B.D.L 0.56 281 438 <684
301 Z8 CORE 93 19.1 185 39.7 7952 0.61 6.52 B.D.L 0.56 296 543 < 708
Mineralized clast
X1 Z1 Rims 18.6 4.09 44.9 10.5 8040 0.13 2.75 B.D.L 0.25 160 252 <700
X1 Z1 Core 21 4.89 58.3 14.4 8090 0.21 4.86 B.D.L B.D.L 213 409 <702
X1 Z2 Rims 22.1 4.89 53.3 13.1 8247 0.12 3.62 B.D.L 0.46 229 322 690
X1 Z3 Rims 21.4 4.95 53.1 12.9 8432 0.23 3.68 B.D.L 0.31 212 307 <704
X1 Z3 Core 56.3 11.9 133 30.8 8550 0.4 16.4 0.86 1.57 957 1361 <704
X1 Z4 Rims 43.7 8.82 99.2 24.3 8064 0.29 4.16 0.33 0.42 293 394 <709
X1 Z4 Core 98.6 19.6 204 45.1 7568 0.4 5.79 B.D.L 0.77 380 518 <706
X1 Z5 Rims 16.6 3.86 45 11.2 8963 0.21 2.83 0.38 0.39 156 265 <706
X1 Z5 Core 83 19.2 213 46.3 9333 9.78 86.9 7.32 3.4 37.5 737 <711
X1 Z6 Rims 25 5.44 57.8 13.5 8151 0.2 3.68 0.22 0.47 231 303 <703
X1 Z6 Core 39 9.06 99.8 25.2 8355 0.23 3.01 B.D.L B.D.L 108 264 <702
X1 Z7 Rims 20.8 5.36 59.8 15.6 8903 0.13 2.98 B.D.L B.D.L 103 227 <701

62
Table A.6: LA-ICP-MS analyses of trace elements in magmatic zircon

Al Si Ti Rb Sr Zr Nb Ba La Ce Pr Nd Sm Eu Gd Tb Dy Ho
Sample P (ppm) Y (ppm)
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)

X1 Z7 Core B.D.L 147719 75 B.D.L B.D.L 0.12 279 452373 2.65 B.D.L B.D.L 15 0.07 1.04 1.76 0.73 7.23 2.02 23.2 8.41
X1 Z8 Rims B.D.L 147719 62.6 B.D.L B.D.L B.D.L 182 402879 2.36 B.D.L B.D.L 23.2 0.05 0.97 1.26 0.45 5.22 1.53 15.9 5.19
X1 Z8 Core B.D.L 147719 84.6 B.D.L B.D.L B.D.L 312 409086 3.02 B.D.L 0.02 21.1 0.04 0.66 1.28 0.56 7.96 2.16 25.1 8.83
301 Z9 Rims B.D.L 147719 62.6 B.D.L B.D.L B.D.L 129 429339 2.37 B.D.L 0.04 14.4 B.D.L 0.53 0.66 0.35 2.86 0.9 9.38 3.37
"B.D.L": Below detection limit

63
Table A.6: LA-ICP-MS analyses of trace elements in magmatic zircon

206 207 208 Temperature (°C) calculated using


Er Tm Yb Lu Hf Ta Pb Pb Pb Th
Sample U (ppm) the Ti-in-quartz equation of Ferry
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)
and Watson (2007)
X1 Z7 Core 41.3 9.69 106 25.5 8868 0.19 2.93 B.D.L B.D.L 112 258 <690
X1 Z8 Rims 26.7 5.45 60.1 14 7990 0.16 3.69 B.D.L 0.43 267 336 <717
X1 Z8 Core 45.3 9.91 110 26.2 8009 0.23 3.79 B.D.L 0.31 185 327 <691
301 Z9 Rims 18.7 4.1 49.3 12.4 8565 0.19 2.77 B.D.L 0.24 122 234 <687
"B.D.L": Below detection lim

64
Table A.7: LA-ICP-MS analyses of trace elements in plagioclase crystals

Li B Na Mg P K Ca Ti Mn Fe Cu Zn Rb Sr Y Zr Nb Mo
Sample # Analyse # Al (ppm) Si (ppm)
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)
201 1 18.1 19.9 58969 19.1 125993 292680 37.7 7205 35280 25 9.7 1192 B.D.L 4.91 1.3 2038 B.D.L B.D.L B.D.L B.D.L
201 2 4.77 17.7 60759 17.9 125793 293560 36.1 7667 33750 25.2 8.04 1159 B.D.L 5.62 1.35 1827 B.D.L B.D.L B.D.L B.D.L
201 3 2.25 19.1 60301 17.2 126983 294339 33.2 7593 34227 21.8 8.05 1154 B.D.L 4.79 1.39 1899 B.D.L B.D.L B.D.L B.D.L
201 4 10.2 16.1 55234 16.3 124430 288196 70.5 6039 36821 26.5 10.4 1020 B.D.L 4.25 1.12 2017 0.04 B.D.L B.D.L B.D.L
201 5 5.02 16.2 56938 14.1 124698 290220 51.5 6539 35533 27.3 8.81 964 B.D.L 3.01 1.3 2044 0.05 0.13 0.06 B.D.L
201 6 12.3 22.1 55738 18.7 129688 288660 40.2 6146 39592 32.9 10.5 972 B.D.L 2.76 1.32 2111 B.D.L B.D.L B.D.L B.D.L
201 7 23.3 19.9 58315 16.8 131994 288250 69.5 7179 36280 32.3 8.95 991 B.D.L 3.42 1.27 1861 0.04 B.D.L B.D.L B.D.L
201 8 15.2 18.6 57230 15.5 125977 288440 62.1 7375 33546 35.3 9.86 1003 B.D.L 2.86 3.31 1755 0.06 0.47 0.05 B.D.L
201 9 7.86 15.8 58494 19.1 121339 289210 94.2 7730 30208 27.4 7.62 1003 B.D.L 3.3 1.42 1651 0.05 0.1 0.02 B.D.L
201 10 13.8 11.7 55480 18.4 124447 289210 89.7 7135 32254 28.7 9.52 1066 B.D.L 3.32 2.2 1759 B.D.L 0.33 0.05 B.D.L
230 11 69.4 15.2 55804 16.9 124934 291064 46.1 6609 34336 20.4 8.85 979 B.D.L 4.55 1.2 1870 0.05 B.D.L B.D.L B.D.L
230 12 74.3 12.4 56704 21 127735 291871 41.9 7183 35244 29.6 8.25 1102 B.D.L 3.8 1.34 1902 0.02 0.02 B.D.L B.D.L
230 13 71.3 16.5 55432 18.2 125477 292349 47 6693 34543 22.6 8.24 1059 B.D.L 4.51 1.2 1863 0.02 B.D.L B.D.L B.D.L
230 14 72.5 13.7 57294 19.6 125689 294342 46.7 7276 33983 26.6 8.53 1128 B.D.L 5.02 1.46 1906 B.D.L B.D.L B.D.L B.D.L
230 15 65 13.1 53146 20.4 131254 289103 45.4 5762 40386 38.2 10.9 1142 B.D.L 4.95 0.86 2186 B.D.L 0.05 0.02 B.D.L
230 16 64.6 15.9 51626 17.8 138212 290000 50.3 4903 45300 51 16.1 1265 B.D.L 5.32 1.63 2253 B.D.L 0.07 0.06 B.D.L
230 17 73.9 14.4 57327 18.8 127811 291080 41.8 7547 33471 21.6 9.38 1118 B.D.L 4.13 1.69 1962 0.03 B.D.L B.D.L B.D.L
230 18 78.4 13.7 58026 11.6 128610 291708 40 7467 33387 20.7 7.92 1143 B.D.L 3.28 1.61 1898 0.03 B.D.L B.D.L B.D.L
235 19 36.1 16 57456 18.7 131544 292900 54.3 6795 35904 32.2 8.79 1106 0.65 4.55 1.39 2100 0.05 0.07 0.01 B.D.L
235 20 28.9 14 59210 16.3 131265 292968 35.8 6432 36344 23.3 10.8 1134 B.D.L 4.87 1.28 2097 0.03 0.01 B.D.L B.D.L
235 21 34.7 15 56937 16 125739 291348 39.7 6178 34245 21.2 10.6 1124 B.D.L 4.44 1.12 2018 0.03 B.D.L B.D.L B.D.L
235 22 46.5 15 56887 21.9 125009 292968 40.8 7245 33651 14.9 7.87 1161 B.D.L 4.76 1.3 2026 B.D.L B.D.L B.D.L B.D.L
235 23 38.7 15.2 56694 16.5 123429 291348 41 7096 33017 19.3 8.84 1096 B.D.L 3.98 1.26 2044 B.D.L B.D.L B.D.L B.D.L
235 24 50.9 10.3 57573 13.9 122321 290530 42.1 7227 30475 17.5 7.68 927 B.D.L 4.04 1.43 1600 0.07 B.D.L B.D.L B.D.L
235 25 52.9 8.43 57697 16.7 123762 292778 52.4 7224 30586 19 7.7 933 B.D.L 3.65 1.32 1603 0.05 B.D.L B.D.L B.D.L
235 26 8.11 B.D.L 57106 11 126842 292630 39.8 6839 31396 14.6 8.16 809 B.D.L B.D.L 1.32 1794 B.D.L B.D.L B.D.L B.D.L
235 27 40 10.6 56674 10.2 120987 285658 38 7192 29681 17.4 7.37 864 B.D.L 4.15 1.54 1780 0.02 B.D.L 0.03 B.D.L
235 28 62.5 15.1 56220 11.4 121680 285542 38.2 6974 30633 17 7.46 881 B.D.L 3.74 1.5 1830 B.D.L B.D.L B.D.L B.D.L
235 29 62 10.6 52477 15.6 133405 282929 47.3 5160 42206 34.2 11.8 928 B.D.L 3.8 0.82 2269 0.07 B.D.L B.D.L B.D.L
235 30 17.6 16.4 53865 14.6 125803 285895 44.6 5614 35024 22.3 9.99 1097 B.D.L 4.88 0.96 2073 0.03 B.D.L B.D.L B.D.L
305 31 B.D.L 22.6 54720 22.7 134665 285836 46.7 6446 36964 32 8.71 1230 B.D.L 4.03 1.19 2103 0.03 B.D.L B.D.L 0.11

65
Table A.7: LA-ICP-MS analyses of trace elements in plagioclase crystals

Ag Sn Sb Cs Ba La Ce Sm Dy Yb W Pb Th U
Sample # Analyse #
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)
201 1 B.D.L 2.74 B.D.L B.D.L 345 7 8.6 0.64 B.D.L B.D.L 0.16 10 B.D.L B.D.L
201 2 B.D.L 3.29 B.D.L B.D.L 239 3.88 3.73 0.42 B.D.L B.D.L B.D.L 10.4 B.D.L B.D.L
201 3 B.D.L 3.19 B.D.L B.D.L 261 3.82 3.99 0.24 0.01 B.D.L B.D.L 11.2 B.D.L B.D.L
201 4 B.D.L 2.54 B.D.L B.D.L 190 6.43 8.19 0.61 B.D.L B.D.L B.D.L 12.9 0.01 B.D.L
201 5 0.05 3.43 B.D.L B.D.L 211 5.19 6.61 0.55 B.D.L B.D.L B.D.L 12.3 0.02 B.D.L
201 6 B.D.L 2.86 B.D.L 0.04 233 7.04 8.96 0.91 B.D.L B.D.L B.D.L 12.9 0.01 B.D.L
201 7 0.04 3.1 B.D.L B.D.L 207 8.6 9.87 1.04 B.D.L B.D.L B.D.L 11.8 B.D.L B.D.L
201 8 0.05 3.72 B.D.L 0.14 212 8.29 10.1 0.56 0.04 B.D.L B.D.L 12.1 0.07 0.02
201 9 0.03 2.74 B.D.L B.D.L 235 6.14 7.23 0.55 B.D.L B.D.L B.D.L 11.6 0.02 0.01
201 10 0.07 3.62 B.D.L B.D.L 222 6.19 6.76 0.59 B.D.L B.D.L B.D.L 12.3 0.04 0.05
230 11 B.D.L 3.09 B.D.L 0.03 180 3.72 4.26 0.38 B.D.L B.D.L B.D.L 12.5 0.01 0
230 12 0.04 3.5 B.D.L B.D.L 235 4.26 4.71 0.25 B.D.L B.D.L B.D.L 10.7 B.D.L B.D.L
230 13 B.D.L 3.44 B.D.L 0.02 217 3.48 3.93 0.27 B.D.L B.D.L B.D.L 11.6 B.D.L 0
230 14 B.D.L 3 B.D.L B.D.L 260 4.04 4.5 0.16 B.D.L B.D.L B.D.L 11.1 B.D.L 0.03
230 15 B.D.L 3.01 B.D.L B.D.L 289 6.19 6.3 0.42 B.D.L B.D.L B.D.L 11.1 B.D.L B.D.L
230 16 B.D.L 3.5 B.D.L B.D.L 277 8.33 9.43 0.6 B.D.L B.D.L B.D.L 12.7 B.D.L 0.02
230 17 0.09 3.23 B.D.L B.D.L 256 3.62 3.58 0.13 B.D.L B.D.L B.D.L 10.7 B.D.L B.D.L
230 18 B.D.L 2.84 B.D.L B.D.L 247 3.48 3.58 0.21 B.D.L B.D.L B.D.L 10.7 B.D.L B.D.L
235 19 B.D.L 3.18 B.D.L 0.01 296 6.34 7.21 0.58 0.01 B.D.L B.D.L 11.8 0.02 0.01
235 20 B.D.L 2.92 B.D.L 0.01 303 4 4.71 0.31 B.D.L B.D.L B.D.L 13.1 B.D.L 0
235 21 B.D.L 2.61 B.D.L B.D.L 299 3.62 4.16 0.24 B.D.L B.D.L B.D.L 14.6 B.D.L B.D.L
235 22 B.D.L 2.28 B.D.L B.D.L 314 3.38 2.83 0.11 B.D.L B.D.L B.D.L 11 B.D.L B.D.L
235 23 B.D.L 3.02 B.D.L B.D.L 339 3.86 3.11 0.13 B.D.L B.D.L B.D.L 11 B.D.L B.D.L
235 24 B.D.L 3.35 B.D.L B.D.L 181 2.77 3.9 0.34 B.D.L B.D.L B.D.L 11.7 B.D.L B.D.L
235 25 B.D.L 3.16 B.D.L B.D.L 205 3.42 4.41 0.4 B.D.L B.D.L B.D.L 12.9 B.D.L B.D.L
235 26 B.D.L 2.33 B.D.L B.D.L 152 2.07 2.33 0.43 B.D.L B.D.L B.D.L 13.3 B.D.L B.D.L
235 27 0.05 3.12 B.D.L B.D.L 196 2.07 2.51 0.4 B.D.L B.D.L B.D.L 12.7 B.D.L B.D.L
235 28 B.D.L 2.33 B.D.L B.D.L 204 2.77 3.5 0.41 B.D.L B.D.L B.D.L 12.5 B.D.L B.D.L
235 29 0.06 3.28 B.D.L B.D.L 224 7.2 9.02 0.97 B.D.L B.D.L B.D.L 14 B.D.L B.D.L
235 30 B.D.L 2.46 B.D.L 0.02 285 4.74 6.33 0.57 B.D.L B.D.L B.D.L 12.9 B.D.L B.D.L
305 31 0.06 2.09 B.D.L B.D.L 301 7.21 7.31 0.42 B.D.L B.D.L B.D.L 9.31 B.D.L B.D.L

66
Table A.7: LA-ICP-MS analyses of trace elements in plagioclase crystals

Li B Na Mg P K Ca Ti Mn Fe Cu Zn Rb Sr Y Zr Nb Mo
Sample # Analyse # Al (ppm) Si (ppm)
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)
305 32 2.28 20.1 56302 21.6 126624 293956 44.9 8554 28792 27.1 6.56 1252 B.D.L 3.25 2.22 1977 0.02 0.12 B.D.L B.D.L
305 33 1.53 31.4 53197 24.5 128142 288191 52.3 7018 35944 40.3 9.52 1397 B.D.L 5.28 2.4 2580 B.D.L B.D.L B.D.L B.D.L
305 34 B.D.L 29.3 53510 27.1 133230 287581 43.2 6736 38390 36.8 9.48 1392 B.D.L 5.8 1.3 2686 B.D.L B.D.L B.D.L B.D.L
305 35 B.D.L 27.8 55160 30.3 132126 287660 73 6987 38062 39.3 10.4 1376 B.D.L 5.97 1.26 2666 0.04 B.D.L B.D.L B.D.L
305 36 B.D.L 24.6 52684 25.4 136521 287643 45 6979 37113 34.8 9.58 1501 B.D.L 5.77 1.43 2730 0.04 0.21 B.D.L B.D.L
305 37 B.D.L 23.8 59273 29.5 131303 291047 43.7 8267 34657 36.2 7.98 1476 B.D.L 4.34 1.55 2418 0.05 B.D.L B.D.L B.D.L
305 38 2.12 23.6 56428 25.7 132680 287031 42.5 6678 36980 36.5 10.2 1269 B.D.L 4.16 1.38 2056 0.01 B.D.L B.D.L B.D.L
305 39 B.D.L 20.4 57970 27.2 126368 291609 43.1 8678 28671 21.3 6.35 1287 B.D.L 3.78 2.29 1964 B.D.L B.D.L 0.03 B.D.L
305 40 B.D.L 20.4 57970 27.2 126368 291609 43.1 8678 28671 21.3 6.35 1287 B.D.L 3.78 2.29 1964 B.D.L B.D.L 0.03 B.D.L
305 41 B.D.L 18.4 60079 20.8 127609 291112 36.2 11282 29165 22.5 7.44 1313 B.D.L 3.95 4.86 1996 0.03 0.13 0.03 B.D.L
201 42 23.1 21.3 58786 17.6 151223 289425 32.8 6667 42634 26.9 10.9 1129 B.D.L 4.74 1.12 3120 0.03 B.D.L B.D.L B.D.L
201 43 5.94 19.3 54752 21.9 124617 289425 44.1 6465 34948 24.5 10 1203 B.D.L 5.05 1.3 2021 0.02 B.D.L B.D.L 0.17
201 44 22 24.8 61165 15.1 132610 289425 43.3 7428 31018 19.7 6.7 1063 B.D.L 4.11 1.59 1603 B.D.L B.D.L B.D.L B.D.L
201 45 17.3 B.D.L 61232 16.7 134335 289425 71.3 7492 29994 16.2 7.48 1170 B.D.L B.D.L 2.08 1596 B.D.L B.D.L B.D.L B.D.L
201 46 21.9 B.D.L 61388 B.D.L 133333 289425 B.D.L 7478 31141 B.D.L 6.82 1079 B.D.L B.D.L 1.6 1597 B.D.L B.D.L B.D.L B.D.L
201 47 5.01 B.D.L 59618 18.1 133581 288216 70.8 6468 33357 24 9.15 988 B.D.L 3.6 1.05 2061 B.D.L B.D.L B.D.L B.D.L
B.D.L: Below detection limit

67
Table A.7: LA-ICP-MS analyses of trace elements in plagioclase crystals

Ag Sn Sb Cs Ba La Ce Sm Dy Yb W Pb Th U
Sample # Analyse #
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)
305 32 0.05 2.14 B.D.L 0.03 341 3.91 3.59 0.21 B.D.L B.D.L B.D.L 8.8 0.03 B.D.L
305 33 B.D.L 2.1 B.D.L 0.1 321 9.24 8.68 0.51 B.D.L B.D.L B.D.L 11.4 B.D.L B.D.L
305 34 B.D.L 2.47 B.D.L B.D.L 345 9.6 9.73 0.79 B.D.L B.D.L B.D.L 10.8 B.D.L B.D.L
305 35 B.D.L 2.73 B.D.L B.D.L 340 10.1 10.4 0.89 B.D.L B.D.L B.D.L 10.3 0.02 0.01
305 36 0.08 2.39 B.D.L B.D.L 359 8.03 7.71 0.57 B.D.L B.D.L B.D.L 12.1 0.05 0.03
305 37 B.D.L 2 B.D.L B.D.L 316 7.8 6.78 0.33 B.D.L B.D.L B.D.L 9.6 B.D.L B.D.L
305 38 B.D.L 2.54 B.D.L B.D.L 297 7.34 7.62 0.33 B.D.L B.D.L B.D.L 9.37 B.D.L 0.01
305 39 B.D.L 1.89 B.D.L B.D.L 339 3.98 3.32 0.16 B.D.L B.D.L B.D.L 9.45 B.D.L B.D.L
305 40 B.D.L 1.89 B.D.L B.D.L 339 3.98 3.32 0.16 B.D.L B.D.L B.D.L 9.45 B.D.L B.D.L
305 41 B.D.L 2.22 B.D.L 0.05 491 4.21 3.61 B.D.L B.D.L B.D.L B.D.L 9.54 0.02 0.02
201 42 B.D.L 2.49 0.06 B.D.L 362 6.62 7.04 0.51 0.01 B.D.L B.D.L 12.5 B.D.L B.D.L
201 43 B.D.L 3.26 B.D.L 0.01 406 5.61 4.84 0.17 0.06 B.D.L B.D.L 13.5 0.01 B.D.L
201 44 0.05 3.5 0.53 B.D.L 182 3.16 4.23 0.44 B.D.L B.D.L 0.59 12.8 B.D.L B.D.L
201 45 B.D.L 9.05 B.D.L B.D.L 184 3.13 5.15 B.D.L B.D.L B.D.L B.D.L 13.9 B.D.L B.D.L
201 46 B.D.L 3.53 B.D.L B.D.L 180 3.12 4.17 B.D.L B.D.L B.D.L B.D.L 12.5 B.D.L B.D.L
201 47 B.D.L 2.18 B.D.L B.D.L 254 4.35 5.36 0.43 B.D.L B.D.L B.D.L 12.2 B.D.L B.D.L
B.D.L: Below detecti

68
Table A.8: LA-ICP-MS analyses of trace elements in sanidine crystals
(sample BR 232)

Li B Na Mg P K Ca Ti Mn Fe Cu Zn Rb Sr Y Zr Nb Mo Ag
Sample # Analyse # Al (ppm) Si (ppm)
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)
232 1 10.8 15.2 21464 4.74 105798 302000 36.6 99586 3516 58 2.49 937 11.4 5.2 148 1904 0.28 B.D.L B.D.L 1.08 0.04
232 2 13.3 17.6 21422 3 107078 300900 37.1 96770 3686 54.5 1.99 823 5.6 5.14 140 2143 0.31 B.D.L B.D.L B.D.L B.D.L
232 3 11.7 16.6 21775 4.05 106862 299700 37.1 99784 3585 52 1.39 823 5.4 5.26 144 2075 0.22 B.D.L B.D.L 0.2 0.03
232 4 10.9 14.7 22003 6.75 109974 300400 34.5 101854 3619 53.1 1.92 877 4.25 4.91 144 2009 0.24 B.D.L 0.02 B.D.L B.D.L
Sn Sb Cs Ba Sm Dy Yb W Pb Th U
Sample # Analyse # La (ppm) Ce (ppm)
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)
232 1 3.82 B.D.L 0.54 9989 1.78 0.73 B.D.L B.D.L B.D.L 0.95 23.6 B.D.L B.D.L
232 2 4.13 B.D.L 0.3 12584 1.76 0.73 B.D.L B.D.L B.D.L B.D.L 25.8 0.01 B.D.L
232 3 4.31 B.D.L 0.36 11578 1.63 0.66 B.D.L B.D.L B.D.L B.D.L 22.4 B.D.L B.D.L
232 4 4.05 B.D.L 0.32 10650 1.56 0.73 B.D.L B.D.L B.D.L B.D.L 22.3 B.D.L B.D.L
B.D.L: Below detection limit

69
Table A.9: Whole rock trace element and isotopic compositions

Sample number 201 203 207 225 229 230 232 235 241 301 CPR 603* CPR 604* CPR 372* CPR 389*
Rock-type DT DD QM QM DD RDD QM DD QM TP DD QM QM QM
Easting 360721 360536 360821 360290 360198 360320 360235 360674 360634 361389 360255 360838

Northing 8821388 8821340 8821336 8821050 8820460 8819640 8820778 8821148 8820804 8820680 8820377 8820315

XRF+LAICP XRF+LAICP XRF+LAICP XRF+LAICP XRF+LAICP XRF+LAICP XRF+LAICP XRF+LAICP XRF+LAICP XRF+LAICP XRF+LAICP XRF+LAICP XRF+LAICP
analyse- type XRF+LAICPMS
MS MS MS MS MS MS MS MS MS MS MS MS MS

SiO2 (wt.%) 67.3 69.7 67.9 65.4 64.6 67.9 65.4 67.3 61.6 62.6 64.9 64.1 60.6 65.5

TiO2 (wt.%) 0.7 0.67 0.73 0.77 0.74 0.66 0.82 0.7 0.78 0.96 0.76 0.79 0.98 0.72

Al2O3 (wt.%) 16.3 16.1 15.9 17.7 17 16.3 15.6 16 14.7 16 15.3 15.5 15.5 15.3

Fe2O3 (wt.%) 3.16 1.15 3.19 2.6 3.43 2.58 3.54 3.34 3.64 4.53 3.35 3.87 4.37 3.14

MnO (wt.%) 0.02 0.01 0.05 0.02 0.03 0.03 0.05 0.03 0.06 0.11 0.07 0.06 0.07 0.06

MgO (wt.%) 0.77 0.39 0.67 0.73 0.86 0.9 0.84 0.49 1.96 1.9 1.67 1.81 1.87 1.08

CaO (wt.%) 2.07 1.96 1.41 2.3 3.09 2.17 3.31 2.17 4.85 3.96 3.16 3.79 4.56 2.92

Na2O (wt.%) 4.24 4.25 3.92 4.11 2.71 4.15 3.98 4.44 3.56 4.25 4 3.44 4.05 3.41

K2O (wt.%) 3.39 3.7 3.77 3.99 3.64 3.88 3.33 3.88 3.29 3.38 3.05 3.15 2.39 3.57

P2O5 (wt.%) 0.28 0.16 0.31 0.28 0.3 0.23 0.37 0.27 0.34 0.47 0.34 0.31 0.45 0.32

LOI (wt.%) 1.25 1.01 1.59 1.5 3.04 1.02 2.19 0.93 4.87 1.4 3.7 3.77 5.05 3.43

Be_ppm 4.63 5.56 5.35 4.05 4.29 4 2.34 3.51 3.56 3.63 N.A. N.A. N.A. N.A.
Na_ppm 25522 25682 23581 24142 17528 25073 24408 27269 21870 25468 N.A. N.A. N.A. N.A.
Mg_ppm 4405 2149 3761 3962 4983 5125 4854 2826 10682 10093 N.A. N.A. N.A. N.A.
Al_ppm 86211 85258 83988 93620 90022 86052 82559 84729 77743 84570 N.A. N.A. N.A. N.A.
Si_ppm 259440 277256 260739 250256 251131 264559 258831 267235 239717 239104 N.A. N.A. N.A. N.A.
P_ppm 786 476 919 801 899 631 1117 734 994 1382 N.A. N.A. N.A. N.A.
K_ppm 23777 26783 26649 28295 25531 27318 24137 27492 23005 B.D.L N.A. N.A. N.A. N.A.
Ca_ppm 13940 12970 9275 15169 20927 14389 22232 14101 32707 B.D.L N.A. N.A. N.A. N.A.
Sc_ppm 5.43 4.65 5.11 4.85 3.77 4.62 5.03 5.51 6.37 6.99 N.A. N.A. N.A. N.A.

70
Table A.9: Whole rock trace element and isotopic compositions

Sample number 201 203 207 225 229 230 232 235 241 301 CPR 603* CPR 604* CPR 372* CPR 389*

Ti_ppm 3652 3424 3757 3922 3798 3431 4324 3809 4188 4971 N.A. N.A. N.A. N.A.
V_ppm 50.1 54.3 49.6 49.1 49.4 52.2 61.2 53.2 66.4 75.7 76 91 108 70
Cr_ppm 9.01 16.4 8.58 8.71 5.6 11 13.9 28.2 19.9 13.9 17 17 13 13
Mn_ppm 141 34.1 348 96.1 167 174 324 232 391 B.D.L N.A. N.A. N.A. N.A.
Fe_ppm 17080 6886 17534 14759 18750 14154 20175 18573 20103 24865 N.A. N.A. N.A. N.A.
Co_ppm 4.28 1.9 5.27 3.98 4.58 3.56 6.48 5.79 6.79 8.47 8 10 31 8
Ni_ppm 5.53 3.92 5.27 5.62 8.38 8.44 B.D.L 4.85 2.55 5.64 7 9 6 3
Cu_ppm 9.15 5.47 10.1 5.22 4.88 7.04 8.9 7.2 9.57 151 17 79 14 12
Zn_ppm 41.9 15.3 49.9 51.4 48.5 47.1 46.5 44.3 48.9 102 159 78 84 105
Ga_ppm 18.7 19.8 18.8 20.8 22 20.2 19.4 19.8 17.8 18.6 21 22 22 23
Ge_ppm B.D.L B.D.L B.D.L 0.98 B.D.L B.D.L 2.13 1.51 1.57 N.A. N.A. N.A. N.A. N.A.
As_ppm 3.39 2.6 3.2 1.33 3.14 1.61 0.88 3.23 B.D.L 3.43 10 0 4 28
Rb_ppm 82.5 99.5 86.6 114 88.1 109 83 104 87.4 67 96 110 67 109
Sr_ppm 776 1018 656 1067 851 823 1118 830 1024 1226 944 650 1260 1088
Y_ppm 7.04 6.92 8.77 7.55 6.52 9.09 8.43 7.79 9.08 10.8 11 12 14 11
Zr_ppm 162 152 187 176 171 160 169 154 164 166 173 169 176 169
Nb_ppm 14.4 13.3 10.1 15.3 15.3 14.3 10.6 14.9 10.3 16.8 10 12 12 10
Mo_ppm 0.74 1.65 0.8 2.25 B.D.L 0.54 0.7 3.02 2.61 1.78 N.A. N.A. N.A. N.A.
Sn_ppm 2.83 2.92 3.13 3.23 2.87 2.82 2.18 2.55 1.84 3.38 N.A. N.A. N.A. N.A.
Sb_ppm 0.43 0.37 0.31 0.94 0.54 0.55 0.09 0.85 1.93 0.2 N.A. N.A. N.A. N.A.
Te_ppm B.D.L B.D.L B.D.L 0.56 0.46 B.D.L 0.88 B.D.L B.D.L B.D.L N.A. N.A. N.A. N.A.
Cs_ppm 6.11 2.22 4.84 4.26 5.01 4.68 1.78 2.38 3.5 0.95 N.A. N.A. N.A. N.A.
Ba_ppm 532 1397 777 770 625 787 815 684 870 938 990 741 909 883
La_ppm 42.9 45 57.7 40.7 42.7 40.3 51.4 40.5 51.4 54.2 50.7 60.8 51.3 49.4
Ce_ppm 82.8 94.9 115 83 82.8 81.7 105 83.5 107 108 102 101 115 103
Pr_ppm 9.25 10.9 13.5 9.31 9.26 9.48 12.3 9.18 12.2 12.4 11.7 10.8 13.2 11.3
Nd_ppm 35.1 43.9 51.2 36.2 35.3 34.9 47.3 35 48.4 49.7 45.1 40.6 55.6 46
Sm_ppm 4.96 7.22 7.8 5.49 5.24 5.59 7.28 5.54 7.2 7.67 5.56 6.88 9.8 8
Eu_ppm 1.23 1.73 1.75 1.27 1.2 1.26 1.75 1.3 1.67 1.91 1.33 1.31 2.02 1.72
Gd_ppm 3.35 4.24 4.8 3.08 2.87 3.74 3.84 3.4 4.02 4.92 4.92 3.4 3.8 3.2
Tb_ppm 0.32 0.4 0.44 0.33 0.3 0.41 0.42 0.35 0.47 0.48 0.41 0.4 B.D.L B.D.L
Dy_ppm 1.65 1.95 1.88 1.54 1.38 1.9 2 1.86 2.13 2.32 2.53 2.36 2.1 2

71
Table A.9: Whole rock trace element and isotopic compositions

Sample number 201 203 207 225 229 230 232 235 241 301 CPR 603* CPR 604* CPR 372* CPR 389*

Ho_ppm 0.25 0.25 0.31 0.26 0.22 0.3 0.31 0.22 0.35 0.37 0.2 0.42 0.43 0.37
Er_ppm 0.7 0.63 0.76 0.68 0.52 0.75 0.74 0.65 0.82 0.95 0.89 1.07 1 0.9
Tm_ppm 0.09 0.08 0.08 0.08 0.07 0.09 0.09 0.09 0.1 0.12 0.22 0.23 0.15 0.12
Yb_ppm 0.54 0.56 0.59 0.57 0.4 0.63 0.5 0.54 0.7 0.72 0.9 1.65 0.6 0.6
Lu_ppm 0.08 0.08 0.08 0.11 0.06 0.06 0.11 0.08 0.1 0.1 0.18 0.15 0.08 0.09
Hf_ppm 3.95 3.88 4.76 4.67 4.55 4.21 4.26 4.19 4.31 4.23 7 5 7 8
Ta_ppm 0.96 0.89 0.59 0.95 1.05 1.01 0.66 1.02 0.69 0.91 N.A. N.A. N.A. N.A.
W_ppm 0.84 1.15 0.56 0.93 0.96 0.74 1.28 2.14 1.48 1.11 N.A. N.A. N.A. N.A.
Tl_ppm 0.3 0.14 0.19 0.26 0.52 0.18 0.19 0.24 0.09 0.15 N.A. N.A. N.A. N.A.
Pb_ppm 15.2 11.5 14.6 14.1 17.9 14 12.6 14.1 15.7 17.2 17 20 12 27
Bi_ppm 0.08 0.04 0.06 0.04 0.21 B.D.L 0.09 0.02 B.D.L 0.03 N.A. N.A. N.A. N.A.
Th_ppm 10.2 9.9 11.5 10.4 10.4 11.3 9.75 10.1 10.7 9.83 9 9 6 11
U_ppm 3.63 2.96 2.93 2.8 2.66 3.05 3.06 3.71 3.49 2.59 N.A. N.A. N.A. N.A.
FC87Sr/86Sr
0.705416 N.A. N.A. N.A. N.A. 0.70556 0.705426 0.70542 N.A. 0.705256 N.A. N.A. N.A. N.A.
corrected

FC 143Nd/144Nd
0.51253 N.A. N.A. N.A. N.A. 0.512517 0.512536 0.512534 N.A. 0.512571 N.A. N.A. N.A. N.A.
corrected

206Pb/204Pb
18.769532 N.A. N.A. N.A. N.A. 18.77816 18.74969 18.77198 N.A. 18.74751 N.A. N.A. N.A. N.A.
corrected
207Pb204Pb
15.640434 N.A. N.A. N.A. N.A. 15.64038 15.64047 15.64272 N.A. 15.63692 N.A. N.A. N.A. N.A.
corrected
208Pb/204Pb
38.809427 N.A. N.A. N.A. N.A. 38.81715 38.78579 38.81154 N.A. 38.77317 N.A. N.A. N.A. N.A.
corrected
DT: dacitic tuff; DD: dacitic dome; QM: Quartz-monzonite dyke; RDD: rhyodacitic dome; TP: Trachyte porphyry
*: Data from Baumgartner et al., 2009
B.D.L: Below detection limit
N.A.: Not Analyzed

72
Table A.10: LA-ICP-MS analyses of the SMIs

SiO2 Al2O3 K2O Na2O CaO TiO2 MgO FeO MnO Mg_ Ti_pp Mn_
Sample # rock type host Analyse# Li_ppm B_ppm Na_ppm Al_ppm K_ppm P_ppm Ca_ppm
(wt.%)* (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) ppm m ppm

Quartz-monzonite
232 quartz Q1 MI 4 70.1 16.3 8.35 3.37 0.79 0.12 0.08 0.84 0.04 201 B.D.L 25141 495 84676 69544 B.D.L 5680 716 324
dyke
Quartz-monzonite
232 quartz Q4 MI1 71.9 16.3 5.4 4.66 1.07 0.09 0.04 0.58 0.03 589 87.1 34785 236 84676 45015 B.D.L 7649 557 271
dyke
Quartz-monzonite
232 quartz Q4 MI2 70.7 16.3 7.17 4.12 0.85 0.09 0.08 0.76 0.03 477 70 30725 473 84676 59741 B.D.L 6064 512 264
dyke
Quartz-monzonite
232 quartz Q4 MI3 70.2 16.3 7.41 3.72 1.24 0.14 0.1 0.88 0.04 424 53 27730 606 84676 61735 B.D.L 8880 851 315
dyke
Quartz-monzonite
232 quartz Q4 MI5 68.9 16.3 7.65 3.75 2.36 0.13 0.08 0.86 0.04 791 B.D.L 28016 499 84676 63717 B.D.L 16858 794 314
dyke
Quartz-monzonite
232 quartz Q6 MI 1 70.8 16.3 6.73 4.12 1.16 0.18 0.06 0.67 0.03 276 82.4 30733 358 84676 56073 B.D.L 8276 1055 254
dyke
Quartz-monzonite
232 quartz Q7 MI 1 70.2 16.3 7.31 3.9 1.08 0.16 0.14 0.88 0.04 B.D.L 74.4 29120 829 84676 60904 B.D.L 7739 982 324
dyke
Quartz-monzonite
232 quartz Q7 MI 2 70.5 16.3 7.05 4.25 0.91 0.13 0.09 0.76 0.04 306 80.3 31745 536 84676 58745 B.D.L 6534 753 275
dyke
Quartz-monzonite
232 quartz Q8 MI 1 71.6 16.3 6.16 4.14 0.82 0.1 0.08 0.76 0.04 617 81.1 30883 480 84676 51361 43.2 5838 611 280
dyke
Quartz-monzonite
232 quartz Q9 MI 2 71.3 16.3 6.64 3.82 0.81 0.1 0.1 0.92 0.04 488 76.6 28544 632 84676 55340 B.D.L 5817 588 331
dyke
235 Dacitic dome quartz Q1 MI1 71.5 16.3 5.77 4.74 0.99 0.06 0.06 0.57 0.03 B.D.L B.D.L 35392 347 84676 48103 B.D.L 7073 389 244
235 Dacitic dome quartz Q2 MI2 70.7 16.3 6.05 4.87 1.3 0.08 0.06 0.62 0.03 183 64.7 36338 339 84676 50419 B.D.L 9301 483 252
235 Dacitic dome quartz Q2 MI3 70.5 16.3 6 4.61 1.84 0.09 0.08 0.62 0.03 172 B.D.L 34433 452 84676 49981 B.D.L 13132 519 251
235 Dacitic dome quartz Q2 MI4 71.6 16.3 5.8 4.5 1.06 0.07 0.06 0.58 0.03 178 B.D.L 33604 374 84676 48312 B.D.L 7607 403 243

230 Rhyodacitic dome quartz Q2 MI 1 70.9 16.3 7.26 3.69 1.08 0.09 0.07 0.64 0.03 690 71.9 27551 440 84676 60482 B.D.L 7748 523 258

230 Rhyodacitic dome quartz Q2 MI 2-3 70.6 16.3 7.41 3.77 1.09 0.09 0.07 0.64 0.03 615 81.7 28151 429 84676 61764 B.D.L 7779 517 261

230 Rhyodacitic dome quartz Q2 MI 2-3 71.9 16.3 6.94 3.79 0.25 0.11 0.07 0.65 0.04 413 B.D.L 28254 416 84676 57826 B.D.L 1788 633 282

230 Rhyodacitic dome quartz Q1 MI 1 70.6 16.3 7.09 4.19 1.03 0.08 0.07 0.61 0.04 720 32.5 31238 408 84676 59095 B.D.L 7358 496 293

230 Rhyodacitic dome quartz Q1 MI 2 70.6 16.3 6.82 4.03 1.5 0.09 0.06 0.58 0.03 781 40.5 30096 350 84676 56866 B.D.L 10712 550 256

230 Rhyodacitic dome quartz Q1 MI 3 70.6 16.3 6.95 4.35 0.96 0.08 0.06 0.68 0.04 687 78.9 32461 364 84676 57917 B.D.L 6867 492 280

73
Table A.10: LA-ICP-MS analyses of the SMIs

Zircon saturation temperature


Fe_pp Cu_pp Zn_pp Rb_p Sr_p Zr_pp Nb_pp Mo_p Ag_pp Sn_pp Sb_pp Cs_pp Ba_p La_pp Ce_pp Yb_pp Sm_pp Dy_pp W_pp Pb_pp Th_pp U_pp (°C) obtained using the
Analyse# Y_ppm
m m m pm pm m m pm m m m m pm m m m m m m m m m equation of Watson and
Harrison 1983

Q1 MI 4 6559 5.29 74.9 256 219 1.67 82.4 5.88 3.18 B.D.L B.D.L 1.65 17.5 262 39.4 43 0.45 3.29 0.1 3.12 40.1 21.8 7.66 722

Q4 MI1 4521 7.13 32.7 182 225 0.9 81.4 5.39 2.24 B.D.L B.D.L 0.63 18.1 203 19 22.9 0.17 1.67 0.16 2.31 39.2 23.6 8.95 726

Q4 MI2 5887 8.96 38.5 231 237 1.3 82.5 4.87 3.7 B.D.L B.D.L 1.18 16 330 32.4 36.8 0.28 1.96 0.14 3.02 30.1 23.8 8.49 722

Q4 MI3 6829 7.2 112 253 184 3 79.5 7.71 2.02 B.D.L B.D.L 0.64 19.1 287 38.4 55.4 0.36 5.03 0.78 4.09 57.6 25 10.6 717

Q4 MI5 6677 13.7 50.9 251 293 2.2 94.1 7.17 4 B.D.L B.D.L B.D.L 15.5 506 B.D.L 51.8 0.12 5.51 B.D.L 2.83 31.5 20.9 7.53 713

Q6 MI 1 5238 B.D.L 51.2 223 304 1.34 95.4 6.31 1.73 B.D.L B.D.L B.D.L 14.9 490 41.2 49.2 0.29 3.67 0.54 2.89 35.2 26.8 8.92 733

Q7 MI 1 6864 9.71 64 251 286 1.61 78.5 7.09 2.88 B.D.L B.D.L B.D.L 15.7 632 B.D.L 45.1 0.21 4.07 0.47 3.66 33.2 21.7 7.47 717

Q7 MI 2 5891 6.6 44.2 239 243 1.53 92 7.05 3.6 0.08 B.D.L 0.67 16.6 451 41.1 49.2 0.26 3.03 0.35 3.16 33.6 24.9 8.5 729

Q8 MI 1 5891 8.59 44.7 225 228 1.54 82.2 6.82 3.11 B.D.L B.D.L 0.76 16.2 297 36.6 44.7 0.23 3.32 0.25 4.02 29.6 23.6 8.9 730

Q9 MI 2 7154 7.98 40 252 236 1.31 79.4 6.65 3.92 B.D.L B.D.L 0.46 16.8 244 37.6 42.4 0.22 2.91 0.17 4.55 27.5 24.7 9.85 727

Q1 MI1 4413 1.65 29 201 281 2.98 53.5 11.1 1.85 B.D.L B.D.L 0.25 13.6 347 12.2 22.4 0.36 3.08 0.37 2.31 27.6 13.5 7.95 692
Q2 MI2 4798 2.19 35.7 206 261 5.93 59.7 14.7 2.75 B.D.L B.D.L 0.53 14.3 375 14 33.3 0.51 5.44 0.67 2.16 26.5 14.2 9.19 692
Q2 MI3 4793 18.4 52.2 199 260 5.52 63.9 14.9 1.91 B.D.L B.D.L B.D.L 14.1 432 B.D.L 32.8 1.01 4.43 0.86 2.74 27.5 14.4 8.94 694
Q2 MI4 4531 4.79 33.6 196 260 5.26 63.2 14.5 1.08 B.D.L B.D.L B.D.L 14 417 14.9 30.1 0.25 4.82 1.31 2.74 24.4 14.7 8.83 706

Q2 MI 1 4978 1.89 41.9 201 266 1.77 56.9 8.99 2.69 B.D.L 3.63 0.59 14 506 39.1 28.8 0.26 2.69 0.36 2.85 28.7 15.8 7.5 696

Q2 MI 2-3 5002 0.93 40.2 202 272 2.06 60.6 10.8 1.11 B.D.L B.D.L B.D.L 12.8 533 21.9 29.9 0.24 2.21 0.24 2.38 27.4 15.2 8.39 698

Q2 MI 2-3 5090 B.D.L 29.1 193 274 1.02 51.8 9.31 0.63 B.D.L B.D.L B.D.L 15.1 484 20.2 30.1 0.31 1.24 0.16 2.78 37.1 16 7.79 700

Q1 MI 1 4780 6.33 43 220 332 4.81 61.3 14.1 2.85 B.D.L B.D.L 0.1 14.1 453 18.2 33.2 0.29 5.37 0.76 2.39 32.8 13.9 8.01 697

Q1 MI 2 4534 0.2 36 208 319 4.95 68.9 13.6 0.54 0.18 B.D.L B.D.L 13 423 17.4 34.8 0.42 5.97 0.95 1.93 25.5 13.3 8.26 704

Q1 MI 3 5304 B.D.L 46 227 352 4.25 61.1 13.9 0.66 B.D.L B.D.L B.D.L 15 525 15.4 30.5 0.34 4.34 0.66 3.8 35.8 13.7 8.55 697

74
Table A.10: LA-ICP-MS analyses of the SMIs

SiO2 Al2O3 K2O Na2O CaO TiO2 MgO FeO MnO Mg_ Ti_pp Mn_
Sample # rock type host Analyse# Li_ppm B_ppm Na_ppm Al_ppm K_ppm P_ppm Ca_ppm
(wt.%)* (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) ppm m ppm

230 Rhyodacitic dome quartz Q1 MI 4 71 16.3 6.5 4.32 1.11 0.07 0.06 0.68 0.03 451 B.D.L 32217 364 84676 54180 B.D.L 7903 435 271

230 Rhyodacitic dome quartz Q5 MI2A B.D.L 16.3 6.68 3.61 0.96 B.D.L 0.06 0.54 0.03 673 B.D.L 26970 336 84676 55684 B.D.L 6860 B.D.L 260

230 Rhyodacitic dome quartz Q5 MI2B 71.3 16.3 6.94 3.66 1 0.08 0.06 0.62 0.03 601 81.9 27316 350 84676 57850 B.D.L 7175 498 270

230 Rhyodacitic dome quartz Q4 MI 2 70.8 16.3 6.14 4.11 1.72 0.07 0.11 0.75 0.05 186 65.5 30677 648 84676 51140 1325 12307 447 354

230 Rhyodacitic dome quartz Q4MI 1 71.3 16.3 6.32 4.47 0.86 0.06 0.05 0.61 0.03 697 67.4 33340 305 84676 52652 B.D.L 6170 358 246

230 Rhyodacitic dome quartz Q7MI 1A 72.3 16.3 6.34 3.28 1.02 0.07 0.06 0.6 0.03 731 54 24498 382 84676 52809 B.D.L 7324 439 255

230 Rhyodacitic dome quartz Q7 MI 1B 71.5 16.3 6.93 3.48 1.03 0.07 0.06 0.6 0.03 832 49 25944 389 84676 57749 B.D.L 7346 446 247

230 Rhyodacitic dome quartz Q7MI 1C 71.8 16.3 6.75 3.42 1.01 0.09 0.06 0.61 0.03 780 B.D.L 25537 381 84676 56233 B.D.L 7228 544 256

201 Dacitic tuff quartz Q1MI3 70.8 16.3 6.33 4.55 1.07 0.09 0.12 0.7 0.06 77.2 B.D.L 33982 700 84676 52756 106 7618 512 472

201 Dacitic tuff quartz Q4 MI 1-2 71 16.3 6.36 4.63 0.86 0.11 0.07 0.65 0.03 B.D.L B.D.L 34549 414 84676 52996 B.D.L 6135 661 250

201 Dacitic tuff quartz Q4MI 3 B.D.L 16.3 5.67 4.34 B.D.L 0.24 0.08 0.59 0.02 B.D.L B.D.L 32412 499 84676 47282 B.D.L B.D.L 1443 174
201 Dacitic tuff quartz Q4 MI 4 71 16.3 6.39 4.8 0.77 0.16 0.1 0.44 0.03 B.D.L B.D.L 35793 604 84676 53283 B.D.L 5539 944 241
201 Dacitic tuff quartz Q4 MI3 B.D.L 16.3 6.49 4.52 B.D.L 0.19 0.13 0.81 0.03 215 B.D.L 33725 807 84676 54125 B.D.L B.D.L 1156 233
B.D.L: bellow dtection limit

75
Table A.10: LA-ICP-MS analyses of the SMIs

Zircon saturation temperature


Fe_pp Cu_pp Zn_pp Rb_p Sr_p Zr_pp Nb_pp Mo_p Ag_pp Sn_pp Sb_pp Cs_pp Ba_p La_pp Ce_pp Yb_pp Sm_pp Dy_pp W_pp Pb_pp Th_pp U_pp (°C) obtained using the
Analyse# Y_ppm
m m m pm pm m m pm m m m m pm m m m m m m m m m equation of Watson and
Harrison 1983

Q1 MI 4 5323 B.D.L 34.7 215 405 4.91 66.4 15.5 5.32 B.D.L B.D.L B.D.L 13.6 517 16.9 32.2 0.43 3.28 1.19 B.D.L 27.6 14.8 7.84 705

Q5 MI2A 4191 1.94 45.1 202 248 1.2 53.6 9.23 B.D.L B.D.L B.D.L B.D.L 15 428 19.2 31.5 B.D.L 2.23 0.45 1.94 25.3 16.6 8.76

Q5 MI2B 4820 0.58 35.6 214 240 2.38 55 10.6 1.51 0.14 B.D.L B.D.L 16 269 15.4 24.6 0.18 2.08 0.36 3.17 27.7 16.8 9.87 697

Q4 MI 2 5836 B.D.L 43.9 193 267 3.62 67.2 9.83 1.51 B.D.L B.D.L B.D.L 13.3 487 33.5 62.1 0.57 6.72 0.88 2.49 23.2 17.5 8.51 704

Q4MI 1 4726 0.33 37 217 222 3.07 53.5 12 1.94 B.D.L B.D.L B.D.L 16 299 15.4 30.6 0.09 4.22 0.74 3.41 27.8 15.4 9.38 692

Q7MI 1A 4692 0.6 27.9 192 263 2.15 58 9.43 2.55 B.D.L B.D.L B.D.L 14 370 18.2 28.6 0.3 2.62 0.2 2.92 22.9 16.8 8.91 710

Q7 MI 1B 4704 1.21 33.4 208 243 2.07 57.6 9.52 3.44 0.11 B.D.L B.D.L 15.8 367 19.7 30.2 0.47 2.58 0.3 3.16 25.7 16.2 8.52 703

Q7MI 1C 4714 B.D.L 30.6 200 259 1.85 56.3 8.92 3.41 B.D.L B.D.L B.D.L 13.9 465 22 30.4 0.22 1.96 0.47 2.11 24.7 17.3 8.45 703

Q1MI3 5461 1.38 71.2 210 237 7.01 56.9 16.9 2.76 B.D.L B.D.L B.D.L 14.5 340 15.6 36.7 0.48 8.08 1.1 2.43 28.8 15.7 8.8 693

Q4 MI 1-2 5039 5.35 23.8 203 266 4.97 51.8 14 0.56 0.23 B.D.L 2.82 13 355 13.8 30.5 0.19 5.07 0.29 3.02 25 14.4 8.66 688

Q4MI 3 4622 B.D.L 69 205 259 4.99 38.4 18.2 B.D.L B.D.L B.D.L B.D.L 14.7 370 7.8 23.9 B.D.L 1.88 B.D.L 8.98 40.9 11.6 6.72
Q4 MI 4 3421 B.D.L B.D.L 248 303 5.46 56.2 9.28 B.D.L 1.43 B.D.L B.D.L 19.6 363 B.D.L 82.1 0.63 13.5 B.D.L 4.1 30.4 35.7 7.4 692
Q4 MI3 6329 B.D.L B.D.L 197 277 4.36 56.3 11.3 2.03 1.86 B.D.L B.D.L 11.5 507 13.7 43.4 1.08 6.01 1.93 2.64 43.8 14.1 6.29

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Table A.11: Isotopic compositions of the sedimentary rocks

Sample number Rock type Alteration rock type Sr88 Pb208 FC87Sr/86Sr 206Pb/204Pb 207Pb/204Pb 208Pb/204Pb
Excelsior
BR133 phyllite fresh 76.3 36.7 0.761779 18.6808 15.6671 38.9090
group
Excelsior
BR134 phyllite fresh 56.6 31.6 0.755644 18.6188 15.6593 38.8595
group
Excelsior
BR278 phyllite aletered 23.1 11.7 0.826161 19.1016 15.6942 39.6367
group

Sandstone* fresh Mitu group 50 4 0.725701 18.6582 15.6358 39.4170

* data from Chelle-Michou, C., Chiaradia, M., Béguelin, P., & Ulianov, A. (2015). Petrological evolution of the magmatic
suite associated with the coroccohuayco Cu (–Au–Fe) porphyry–skarn deposit, Peru. Journal of Petrology, 56(9), 1829-
1862.

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Chapter 2

Hydrothermal evolution of hidden porphyry-type


mineralization related to the large epithermal
polymetallic deposit of Cerro de Pasco (Peru)

Bertrand Rottier*, Kalin Kouzmanov*, Vincent Casanova* Anne-Sophie Bouvier**, Lukas P.

Baumgartner**, Markus Wälle***† and Lluís Fontboté*

*Department of Earth Sciences, University of Geneva, 1205 Geneva, Switzerland

**Institute of Mineralogy and Geochemistry, University of Lausanne, 1015 Lausanne,

Switzerland

*** Institute of Geochemistry and Petrology, ETH Zürich, 8092 Zürich, Switzerland

present address: Memorial University of Newfoundland, CREAIT, CRC and CFI Services (CCCS),
Bruneau Centre for Research and Innovation, St. John’s, NL, Canada, A1C 5S7
Corresponding author: Bertrand.Rottier@unige.ch

Abstract
Cerro de Pasco (Peru) is known for its large epithermal polymetallic (Zn-Pb-Ag-Cu-Bi)
mineralization emplaced at shallow level, ~ 500 m below the paleo-surface, at the border of a large
diatreme breccia complex. Porphyry-style veins crosscutting hornfels and magmatic rock clasts were
recently found in the diatreme breccia and in quartz-monzonite porphyry dykes. Such mineralized
veins in clasts allow investigation of high-temperature porphyry-style mineralization located in deep
portions of the hydrothermal system. Porphyry-style vein quartz contains silicate melt inclusions as
well as fluid and solid mineral inclusions. Two types of high temperature (>600°C) quartz-
molybdenite-(chalcopyrite)-(pyrite) veins are found in the clasts. Early, thin (1-2 mm) and sinuous
HT1 veins are crosscut by slightly thicker (up to 2 cm) and more regular HT2 veins. The HT1 vein
quartz hosts CO2- and sulfur-rich high-density vapor inclusions. Two subtypes of the HT1 veins have
been defined based on the nature of mineral inclusions hosted in quartz: (i) HT1bt veins with inclusions

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of K-feldspar, biotite, rutile and minor titanite, and(ii) HT1px veins with inclusions of actinolite, augite,
titanite, apatite and minor rutile. Fluid inclusion microthermometry and multiple mineral
thermobarometers applied reveal that HT1 veins were formed at temperatures >700°C and at pressures
between 500 and 900 bars (HT1bt veins) and between 700 and 1300 bars (HT1px veins). HT2 veins
host assemblages of polyphase brines, generally coexisting with low-density vapor-rich inclusions,
trapped at temperatures around 600°C and pressures between 710 and 850 bars. Rhyolitic silicate melt
inclusions were found in both HT1 and HT2 veins. Quartz from both HT1 and HT2 veins also contain
secondary low-temperature (~ 300°C) brine and aqueous fluid inclusions that record the cooling of the
system. Both vein types are locally crosscut and/or reopened by a pre-diatreme polymetallic event
consisting of pyrite, sphalerite with “chalcopyrite disease”, galena, chalcopyrite, tetrahedrite-
tennantite, and minor quartz.
Silicate melt inclusions represent melt droplets transported by the ascending hydrothermal fluids;
LA-ICP-MS analyses reveal a chemical evolution trend coherent with the crystallization of an evolved
rhyolitic melt. LA-ICP-MS analyses of the mineral and fluid inclusions hosted in HT1 and HT2 veins,
and in-situ SIMS oxygen isotope analyses of vein quartz are indicative of magmatic signature of the
mineralizing fluids with no major meteoric water input, and allow reconstruction of the source and
chemical evolution of fluids that formed these porphyry-style veins as snapshots of the early, deep,
and high-temperature mineralization at Cerro de Pasco
This detailed study of the newly found porphyry-type mineralization hosted in clasts offer a
unique opportunity to reconstruct the late magmatic and early hydrothermal evolution of the deep
portion of the porphyry system associated with the world-class Cerro de Pasco epithermal polymetallic
(Zn-Pb-Ag-Cu-Bi) deposit.
Keywords: porphyry, breccia clasts, fluid inclusions, silicate melt inclusions, hydrothermal quartz,
LA-ICP-MS, trace elements, oxygen isotopes, SIMS, Cerro de Pasco

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Introduction
Mineralized porphyry systems are the main global suppliers for Cu and Mo, and are important
for Au, Re, Ag, Pd, Zn, Pb and many other economic elements (Sillitoe, 2010). Porphyry systems
consist of large volumes of hydrothermally altered, veined and mineralized rocks centered on
porphyry stocks. A large variety of mineralization styles including skarn, carbonate-replacement,
sediment-hosted, and high- and intermediate-sulfidation epithermal base and precious metal
mineralization can be found together or separately in such systems (Sillitoe, 2010). The
comprehension of their temporal, spatial and genetic relationships is a key for understanding the
dynamics and the complexity of the magmatic-hydrothermal system.
Close spatial and temporal relationship between polymetallic mineralization (i.e., Cordilleran
polymetallic deposits; Fontboté and Bendezú, 2009) and porphyry-style mineralization has been
reported in several telescoped systems where polymetallic mineralization spatially overprints higher-
temperature porphyry-style mineralization; like the Main stage veins at Butte, USA (Meyer et al.,
1968; Lund et al., 2002; Rusk et al., 2008a, b; Reed et al., 2013), El Rosario veins at Collahuasi, Chile
(Masterman et al., 2005), and the polymetallic vein and replacement bodies at Morococha, Peru
(Catchpole et al., 2012 and 2015a).
Cerro de Pasco is a large epithermal polymetallic (Zn-Pb-Ag-Cu-Bi) deposit emplaced at
shallow level, ~ 500 m below paleo-surface, at the border of a large diatreme breccia complex
(Einaudi, 1977, Baumgartner et al., 2008, 2009, Rottier et al., 2016b). Rottier et al. (2016a) and Rottier
(2017), recently provided direct evidence of three temporally distinct porphyry events at Cerro de
Pasco: (i) porphyry-style veins hosted by hornfels and porphyritic igneous clasts in the diatreme
breccia (PM1); (ii) shallow porphyry mineralization outcropping in the central part of the diatreme
(PM2); (iii) porphyry-style veins hosted by hornfels and porphyritic igneous clasts in east-west
trending quartz-monzonite porphyry dykes (PM3). This porphyry-style mineralization in clasts (PM1
and PM3) at Cerro de Pasco offers a unique opportunity to study the relationships between world class
epithermal polymetallic deposit and the deeper porphyry mineralizations in a system without
evidences of telescoping.
The present study focuses on the oldest identified porphyry event (PM1) at Cerro de Pasco,
recognized in the diatreme breccia and characterized by quartz-molybdenite-(chalcopyrite)-(pyrite)
veins hosted by hornfels and porphyritic igneous clasts. We apply a multi-analytical approach to
reconstruct the time-temperature-pressure relationships and the origin and composition of the fluids
associated with the porphyry-style high-temperature hydrothermal veins. The study is based on: i)
detailed petrography combined with SEM-CL imaging of hydrothermal quartz veins; ii) application of
three independent mineral thermobarometers (Ti in quartz, Huang and Audétat, 2012; Zr in rutile,
Tomkins et al., 2007; Zr in titanite, Hayden et al., 2008); iii) fluid inclusion microthermometry and
LA-ICP-MS analyses, iv) in-situ SIMS oxygen isotope analyses of the hydrothermal vein quartz. The

80
porphyry-style veins were formed at high temperatures (> 600°C) and host CO2-rich high-density
vapor inclusions and polyphase brine inclusions. A prominent feature of the studied veins is the
presence of crystallized or glassy rhyolitic silicate melt inclusions (SMIs) in the hydrothermal quartz.
Occurrence of SMIs in porphyry veins is rarely reported in the literature and their significance is still
not fully understood (Pintea, 1995 and 2014; Harris et al., 2003; Ivascanu et al., 2003; Stefanova et al.,
2014; Rottier et al., 2016a). Chemical composition of these SMIs has been determined by LA-ICP-MS
and their genetically features are discussed.
This contribution studies the physical and chemical complexity of the deep porphyry
environment of the magmatic-hydrothermal system associated with world class Cerro de Pasco
epithermal polymetallic deposit. Studying the link between hidden deep porphyry mineralization and
an epithermal polymetallic deposit in a non-telescoped system, provides significant new data that fill a
gap in the understanding of fluid processes at the magmatic-hydrothermal transition.

Geological settings
Cerro de Pasco is one of the largest epithermal polymetallic ("Cordilleran") deposits in the world.
Historical production and remaining resources aggregate more than 200 million tons (Mt) at around 7
wt% Zn, 2 wt% Pb, and 3 oz/t Ag in addition to at least 100 Mt at 1.3 wt% Cu and 1 g/t Au.
Furthermore, Cerro de Pasco produced more than 1 billion ounces (Moz) of Ag during Colonial times
(Baumgartner et al., 2008 and references therein). The Cerro de Pasco District is located 300 km
north-east of Lima in the Western cordillera of Peru (Fig. 1A). It is part of the mid-Miocene
metallogenic belt recognized in Central and Northern Peru (Noble and McKee, 1999, Bissig et al.,
2008; Bissig and Tosdal, 2009).
The Cerro de Pasco district is characterized by a large diatreme-dome complex 2.5 km in
diameter emplaced along a major N15° W-striking reverse fault, named Longitudinal Fault (Fig. 1B).
West of this fault, the diatreme-dome complex crosscuts metamorphosed Middle Paleozoic shales
(Excelsior Group) and conglomerates and sandstones of the Middle-Late Triassic Mitu Group (Fig. 1;
Rosas et al., 2007, Spikings et al., 2016). East of the Longitudinal fault, the diatreme-dome complex is
emplaced in a up to 1000 m sequence of carbonate rocks belonging to the Late Triassic Chambará
Formation, part of the Pucará Group (Angeles 1999; Rosas et al., 2007).

81
Figure 1: Geological map and cross-section of the diatreme dome complex and the different mineralization styles at
Cerro de Pasco, compiled from field observations and previous work of Rogers (1983), Baumgartner et al. (2008) and
the Volcan’s geological staff. Location of the drill holes where mineralized clasts were found is indicated by the green
and orange circles, in the eastern part of the diatreme breccia. * Few clasts correspond to 1-3 clasts every 10 meters of
intercepted breccia and numerous correspond to > 3 clasts every 10 meters of intercepted breccia.

82
The diatreme-dome complex was formed during a succession of mid-Miocene phreatomagmatic
and magmatic events spanning 0.3 My (Fig. 1B, Einaudi 1968; Rogers 1983; Baumgartner et al. 2009;
Rottier et al., 2016b). An early phase of explosive activity produced a diatreme-breccia known locally
as the Rumiallana Agglomerate, the most widespread lithology in the magmatic complex, dated by
isotope dilution thermal ionization mass spectrometry (ID-TIMS) zircon U-Pb at 15.36 ± 0.03 Ma
(Baumgartner et al. 2009). The geometry of the breccia body is not well constrained; the deepest level
reached by drilling is ~3300 m above sea level corresponding to a vertical extent greater than 1150 m;
the horizontal extent is close to 2000 m at the present-day surface (Fig. 1).
Three different facies forming the diatreme breccia have been observed in the studied drill holes
and at the surface: i) a lower facies consisting of a non-stratified breccia, ii) an intermediate facies
marked by stratified breccia, and iii) an upper facies corresponding to a fine-grained stratified tuff.
The lower facies is only intercepted in drill holes and consists of massive non-stratified matrix-
supported polymictic breccia. The clasts are angular and generally range from 2 to 10 cm in size but
locally can reach a few meters and are dominantly of phyllites from the Excelsior Group, Mitu
sandstone, carbonate rocks from the Pucará Group, and subordinately altered dacite, porphyritic
igneous rocks, and hornfels. The matrix makes up 20 to 50 vol.% of the breccia and is comprised of
mud- to sand-sized fragments. Crosscutting relationships are indicative of multiple breccia-forming
events (Fig. 2 A and B). The stratified breccia is the most common outcropping facies (Fig. 2 F). It is a
matrix-supported and polymictic breccia with the nature and size of the clasts similar to those of the
lower facies. The bed thickness is strongly variable, from a few centimeters to several decimeters;
some beds are well-sorted while others are completely un-sorted; no grading was observed (Fig. 2 E
and F). The top facies of the diatreme breccia corresponds to fine-grained well-sorted dacitic tuffs
(Fig. 2 D and C) and crops out only in the northwestern and the southwestern part of the diatreme-
dome complex (Fig. 1). It often shows crossbedding and locally numerous accretionary lapilli (0.2–1
cm diameter; Fig. 2 D). This facies was interpreted as base surge deposits by Baumgartner et al.
(2008).
The phreatomagmatic activity was followed by a period marked by volcanic and subvolcanic
magmatism that formed i) dacitic to rhyodacitic lava-dome complexes emplaced along the western
margin of the diatreme breccia, dated at 15.40 ± 0.07 Ma (zircon U-Pb ID-TIMS; Baumgartner et al.
2009); ii) a rhyodacitic porphyry stock cropping out in the northern part of the diatreme-dome
complex; iii) several small (each less than 10 x10 m) porphyritic trachyte intrusions cropping out in
the central part of the diatreme breccia that are crosscut by low-density stockwork porphyry style
mineralization (Rottier et al., 2016a); and iv) east-west trending quartz-monzonite porphyritic dykes
cutting the diatreme breccia and the dacitic to rhyodacitic magmatic domes (Fig. 1A). Two of these
dykes have been dated at 15.35 ± 0.05 Ma and 15.16 ± 0.04 Ma (zircon U-Pb ID-TIMS; Baumgartner
et al. 2009).

83
Figure 2: A-B) Drill cores showing different generations of massive non-stratified breccias (drill hole#: A: DDH-S-CE-
13-208, B: DDH-S-CE-14-194); C) Outcrop of fine-grained stratified tuff (northwestern part of the diatreme-dome

84
complex); D) Accretionary lapillis found in the fine-grained stratified tuff (northwestern part of the diatreme-dome
complex); E-F) Outcrops of the stratified breccia (central part of diatreme-dome complex).
Numerous, 20 cm to 3 m-wide, E-W trending, milled-matrix fluidized breccia dykes were
emplaced in various parts of the diatreme-dome complex crosscutting the diatreme breccia, the dacitic
and rhyodacitic domes, and the quartz-monzonite dykes. According to the morphology of the
diatreme-dome complex, the occurrence and the type of the pyroclastic rocks (e.g., lapilli tuff), the
total erosion since the formation of the diatreme-dome complex is estimated at < 1 km (Baumgartner,
2007; Baumgartner et al., 2008; Rottier et al., 2016a).
Crosscutting relationships indicate that the economic epithermal polymetallic mineralization
occurred after the emplacement of the diatreme complex. It is developed mainly in carbonate rocks
along the eastern margin of the diatreme-dome complex (Einaudi, 1977, Baumgartner et al., 2008). As
reinterpreted by Rottier et al. (2016b), the following three main successive mineralizing stages are
recognized: A) pipe-like pyrrhotite-dominated bodies grading outwards into Fe-rich sphalerite and
galena, B) a large N-S trending funnel-shaped massive pyrite and quartz body, and C) high-sulfidation
polymetallic mineralization consisting of a set of E-W–trending Cu-Ag-(Au-Zn-Pb) enargite-pyrite
veins hosted by the diatreme breccia, and large well-zoned Zn-Pb-(Bi-Ag-Cu) carbonate replacement
ore bodies in the eastern part of the deposit (Fig. 1). The enargite-pyrite veins have been dated at 14.54
± 0.08 and 14.41 ± 0.07 Ma (Ar-Ar on alunite; Baumgartner et al., 2009).

Recently recognized porphyry mineralization at Cerro


de Pasco
A link between the large epithermal polymetallic mineralization and a porphyry system at
depth was already suggested by Baumgartner et al. (2008). Recently, large pervasively altered areas
typical for a porphyry lithocap environment and minor occurrences of porphyry-type mineralization
have been identified at Cerro de Pasco (Rottier et al., 2016a; Rottier 2017). The pervasive alteration
permeates the central and the northern parts of the diatreme-dome complex as well as sedimentary
rocks north of it. It includes mainly areas with pyrophyllite-quartz-pyrite mineral association grading
outward to illite-smectite-muscovite-pyrite and peripherally to chlorite-calcite-pyrite (Fig. 1B). These
alteration zones are spatially disconnected from the main epithermal base metal mineralization. Our
field observations and those of geological staff of the Volcan Compañía Minera S.A (R. Bendezu,
personal communication) show that they affect the quartz-monzonite dyke dated at 15.158 ± 0.035 Ma
(Baumgartner et al., 2009) and are overprinted by quartz-alunite alteration spatially associated to the
E-W oxidized veins dated between 14.54 ± 0.06 and 14.41 ± 0.07 Ma (Ar-Ar on alunite; Baumgartner
et al., 2009, Fig. 16). The E-W oxidized veins are assumed to represent enargite-pyrite veins
(Baumgartner et al., 2009).

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Three temporally distinct events of porphyry mineralization have been recognized at Cerro de
Pasco, the main characteristics of each event are reported in Table 1. The first event (PM1), the one to
which this contribution is devoted, consists of porphyry veins crosscutting hornfels and porphyritic
igneous clasts that are found in the southeast part of the diatreme-breccia (Fig. 1B). It takes place
before the emplacement of the breccia dated at 15.36 ± 0.03 Ma (zircon U-Pb ID-TIMS; Baumgartner
et al. 2009). Two types of quartz-molybdenite-(chalcopyrite)-(pyrite) veins are found in the clasts.
Early, thin (1-2 mm) and sinuous HT1 veins are crosscut by slightly thicker (up to 2 cm) and more
regular HT2 veins.
Table 1: Summary of the main characteristics of the different porphyry events at Cerro de Pasco.

Porphyry
PM1 PM2 PM3
events
Between 15.286 ±
15.165 ± 0.043 Ma2 (clast)
Age 15.59 ± 0.12 Ma1 0.018 Ma2 and 15.158
15.158 ± 0.035 Ma1 (host)
± 0.035 Ma1
Veins crosscutting
Stockwork of veins Veins crosscutting
hornfels and
crosscutting Hornfels and porphyritic
Occurrence porphyritic igneous
porphyritic trachyte igneous clasts hosted in a
clasts in the
intrusions quartz monzonite dyke
diatreme breccia
High-temperature
Recognized sodic (albitization)
Potassic and phyllic Potassic
alteration and low-temperature
sodic(-calcic)
quartz-molybdenite- quartz-magnetite-
quartz-magnetite-
Type of veins (chalcopyrite)- chalcopyrite-pyrite
chalcopyrite-(pyrite) veins
(pyrite) veins veins

Quartz 1st generation: >


precipitation >600°C 600°C; 2nd >600°C
temperature generation:≈350°C

Sulfide
precipitation >600°C ≈350°C >600°C
temperatures
Pressure of
500-1300 bars < 290 bars > 600 bars
formation
References this study Rottier et al., (2016a) Rottier (2017)
(1) (2)
Baumgartner et al. (2009); Rottier (2017)

Rottier et al. (2016a) recently provided a detail description of the second event (PM2). It is
characterized by quartz-magnetite-chalcopyrite-pyrite porphyry-style veinlets hosted by small trachyte
porphyry bodies cropping out in the central part of the diatreme dome complex (Fig. 1C). This event
takes place after emplacement of the trachyte intrusions dated at 15.286 ± 0.018 Ma and is older than a

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quartz-monzonite dyke dated at 15.158 ± 0.035 Ma (zircon U-Pb ID-TIMS; Baumgartner et al., 2009)
which crosscuts the quartz-magnetite-chalcopyrite-pyrite porphyry-style veinlets (Rottier 2017).
The last porphyry event (PM3) corresponds to quartz-magnetite-chalcopyrite-(pyrite) veins
crosscutting porphyritic igneous and hornfels clasts found in the quartz monzonite dykes. One of the
mineralized porphyritic igneous clasts has been dated at 15.165 ± 0.043 Ma (zircon U-Pb ID-TIMS;
Rottier 2017), an age very close to that obtained for the quartz-monzonite dyke hosting it (15.158 ±
0.035 Ma, Baumgartner et al., 2009).

Analytical methods

Sample selection and SEM-CL petrography


A total of 8 clasts crosscut by HT1 or HT2 veins were selected for this study. Doubly polished
thick sections (200 µm) were examined using a standard petrographic microscope to characterize fluid
and silicate melt inclusions in quartz from the porphyry-type veins. Scanning-electron microscopy-
cathodoluminescence (SEM-CL) was used in order to identify different quartz generations constituting
the veins, their relative time relationships, and the paragenetic context of the studied fluid and melt
inclusions. SEM-CL images were acquired at the University of Lausanne using a CamScan MV2300
SEM and at the University of Geneva using a JEOL JSM7001F, both equipped with a panchromatic
CL detector.

Microthermometry
Around 300 fluid inclusions grouped in 33 fluid inclusion assemblages (FIAs) were analyzed
by microthermometry. Microthermometric data were acquired using a THMSG 600 Linkam heating–
freezing stage mounted on a DMLB Leica microscope regularly calibrated using SynFlinc standards at
−56.6 °C, 0.0 °C, and 374.1 °C (Sterner and Bodnar, 1984). For CO2-bearing fluid inclusions,
salinities were calculated using the CO2 clathrate melting temperature and total homogenization of the
CO2 phase using the equations of Diamond (1992). CO2 contents (mol %), densities and isochores were
determined using Q2 and ISOC software (Bakker and Brown, 2003), and the equation of Duan et al.
(1992). Estimation of the liquid/vapor ratios is the largest source of error in this approach and
therefore it was determined using the ImageJ software. For halite-saturated and liquid-rich fluid
inclusions salinities in wt% NaCl equiv., densities and isochores were determined using the SoWat
software (Driesner, 2007; Driesner and Heinrich, 2007).

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Raman microspectroscopy
Raman microspectroscopy was used to identify minor mineral phases, solid inclusions trapped
in minerals or hosted by fluid inclusions, gas composition of the vapor phase, and the presence of
SO42- ion in the aqueous phase of fluid inclusions. Measurements were performed using a confocal
LABRAM instrument at the University of Geneva equipped with a 532.12 -nm Nd-YAG Laser and an
Olympus BX51 microscope. Gas compositions were determined using a x100 objective and the
following Raman settings: 500 µm confocal aperture, 100 µm slit, and an acquisition time of 2x120
sec. The limit of detection for this setting is better than 0.13 mol% CO2 (Rosso and Bodnar, 1995).
Presence of SO42- ion in the aqueous phase was determined using a x50 objective, 500 µm confocal
aperture, 100 µm slit, and acquisition time of 60 sec. Measurements were done from room temperature
up to 450°C; heating was performed using the THMSG 600 Linkam heating–freezing stage.

SIMS analyses
Three different porphyry veins were selected for SIMS oxygen isotope analyses: one HT1bt,
one HT1px, and one HT2 vein. A total of 22 18O/16O isotopic ratio analyses were performed on quartz
chips placed in indium mounts that included two grains of the reference material (UNIL-Q1 for δ18O
measurements, Seitz et al., 2016). Measurements were performed at the SwissSIMS ion probe national
facility at the University of Lausanne, using a Cameca IMS180-HR. Samples were coated with a 40
nm-thick layer of gold. A 10kV Cs+ primary beam with a ~2 nA current was used for oxygen isotopes
measurements, resulting in a ~10 µm beam size. The electron flood gun was used to compensate
charge. 16O and 18O secondary ions, accelerated at 10kV, were analyzed at a mass resolving power of
2400 and collected on a Faraday cup (FC) each in multi-collection mode. All data were obtained
during a single session of 12h. FCs were calibrated at the beginning of the session. Mass calibration
was performed at the beginning of the session and a nuclear magnetic resonance probe was used to
lock in the magnetic field. Details of the analytical settings are described in Seitz et al. (2016). Each
analysis takes less than 4 minutes, including pre-sputtering (30 sec) and automated centering of
secondary ions. This setting allowed an average reproducibility better than 0.3‰ (2 standard
deviation: 2σ) on the UNIL-Q1 reference material (Seitz et al., 2016), and the internal error for each
analysis was lower than 0.3‰ 2σ (standard error of the mean). Sets of 4 analyses of the UNIL-Q1
standard were obtained every 15-20 analyses for monitoring instrument stability. The variation of
UNIL-Q1 over the entire session was < 0.3‰ (2σ). The error reported for samples reflects the 2σ
bracket from the surrounding 4 standard analysis.

LA-ICP-MS analyses
LA-ICP-MS has been used to determine the composition of fluid (n=134) and silicate melt
inclusions (n=53), as well as the trace element contents of quartz (n=168), rutile (n=23) and titanite

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(n=5). Analyses were performed using a 193 nm ArF Excimer laser with an energy homogenized
beam profile coupled with an ELAN 6100 DRC ICP quadrupole mass spectrometer (QMS) at ETH
Zurich (Günther et al., 1997, 1998; Heinrich et al., 2003). Table A.1 provides a summary of analytical
conditions, data acquisition parameters and list of isotopes analyzed during each session. To limit
explosion of the analyzed quartz, an iris diaphragm was used (Guillong and Henrich, 2007), allowing a
progressive increase of the laser beam diameter during ablation (Günther et al., 1998); final ablation
pits were between 20 and 50 µm in diameter. Rutile and titanite were measured with a beam diameter
from 20 to 40 µm when they were cropping out at the surface and otherwise by ablation through
quartz following similar procedures as for SMIs and fluid inclusions (Pettke, 2006). LA-ICP-MS
transient signals were reduced using the SILLS software (Guillong et al., 2008). The NIST SRM 610
glass standard was used as an external standard and analyzed two times between a maximum of 20
unknowns to correct the instrument drift by linear regressions. For fluid inclusion analyses, Na
concentration derived from the estimated salinity was used as an internal standard; an empirical
correction for major dissolved cations other than sodium: K, Fe, Mn, Zn, Cu and Pb, was applied.
Quantification of the SMIs has been done following the method of Halter et al. (2002). Fixed Al value
of 16 wt % Al2O3 was used as an internal standard for all analyzed melt inclusions. This value
corresponds to the calculated mean Al2O3 content obtained from whole rock XRF analyses of the
volcanic and sub-volcanic rocks from the district, ranging in composition from dacite to rhyolite
(mean=15.97 ± 0.87 wt% Al2O3, n=12; Rottier et al., 2016a). The silica content of each SMI is
calculated based on the equation SiO2 wt.%= 100 - wt%(K20) - wt%(Na2O) - wt%(Fe2O3) -
wt%(Al2O3) - wt%(MgO).For host correction (i.e., quartz) and quartz trace element analyses 99.5
wt.% SiO2 was assumed as an internal standard. Stoichiometric Ti (59.31 wt.%) and Ca (19.25 wt.%)
were respectively used as internal standards for analyses of rutile and titanite.

Mineral thermobarometers

Ti inquartz
Titanium concentrations determined by LA-ICP-MS were used as proxy for quartz
precipitation temperatures. The experimentally calibrated thermobarometer of Huang and Audétat
(2012) was applied to calculate quartz precipitation temperature. The activity of TiO2 (αTiO2) is
assumed to be equal to 1, considering the presence of rutile in the hydrothermal veins and also in the
host hornfels and igneous clasts. The main limit of this thermobarometer is the important effect of
growth rate on the Ti concentration in quartz (Huang and Audétat 2012), their thermobarometer being
calibrated for a growth rate of 2-4 µm/day. If growth rate is faster or slower, the calculated
temperature will be respectively overestimated (up to 250°C, Huang and Audétat, 2012) or
underestimated. This effect cannot be quantified, and all obtained temperatures should be considered
as approximate. Titanium diffusion could also affect the original Ti concentration and therefore the

89
calculated temperatures. At 600°C, Ti diffuses by ~15 µm over a million years (Cherniak et al.,
2007a). According to the low Ti diffusion rate and the LA-ICP-MS spot size (20 to 50 µm) used, the
potential effect of Ti diffusion is considered as negligible, detailed discussion on this issue could be
found in Mercer et al., (2013).

Zr in rutile
Hydrothermal rutile precipitation temperatures were calculated using the experimental
thermobarometer of Tomkins et al. (2007). Presence of zircon and quartz are necessary to satisfy
equilibrium controlling the Zr content in rutile (Tomkins et al. 2007). Analyzed rutile grains were
located at the margin or inside the veins, and were always intergrown with or included in quartz. No
zircon was found inside the veins, but in all studied clasts (hornfels or igneous) numerous small zircon
grains (< 50 µm) are present at the border of the vein or in the immediate vicinity of the veins (<100
µm from the border). We assumed that analyzed rutile grains were precipitated from a Zr saturated
hydrothermal fluid. Therefore calculated temperatures have to be considered minimum temperatures.
The error (2σ) derived from the analytical and calibration uncertainties (Tomkins et al. 2007), is <
30°C. Zirconium diffusion in rutile is three orders of magnitude slower than Ti in quartz (Cherniak et
al., 2007b), and therefore the effect of Zr diffusion on calculated temperatures is assumed to be
negligible.

Zr in titanite
Hydrothermal titanite precipitation temperatures were calculated using the experimental
thermobarometer of Hayden et al. (2008). This thermobarometer was calibrated for a titanite-rutile-
quartz-zircon assemblage. Analyzed titanite crystals were always included in quartz forming the veins.
Rutile in the studied sample is common either directly in the quartz veins or in the host lithology, and
as already mentioned small zircon grains were present in all clasts. Therefore, αTiO2 and αSiO2 were
fixed at 1. Calibration uncertainty associated with this thermobarometer is < ± 20°C and analytical
uncertainty is close to 0°C due to the high sensitivity of the thermobarometer (Hayden et al., 2008).
Zirconium diffusion in titanite is similar or slower than diffusion in rutile (Cherniak et al., 2007b),
therefore, as with rutile, the effect of Zr diffusion on calculated temperatures is negligible.

Results

Mineralized clast petrography


Studied clasts range from 2 to 10 cm in size; they are mostly rounded, and were found
exclusively in the massive non-stratified matrix-supported polymictic breccia, the basal unit of the
diatreme. A total of 18 different holes drilled in the eastern part of the diatreme-breccia were

90
investigated (Fig. 1B). Porphyry veins have been found in 10 of them, all in hornfels clasts except one
clast where the veinlets crosscut an porphyritic igneous rock (Fig. 3 C); more details (drill hole
number, location, depth, and relative abundance) are reported in supplementary table A.2.
Observations on the studied drill holes suggest that mineralized clasts are more abundant in the
southeastern part of the diatreme complex (Fig. 1B).

Figure 3: Mineralized clasts in the massive non-stratified breccia from drill cores. A) Hornfels clast affected by a
high-temperature potassic alteration and crosscut by an HT1px-vein (sample BR-259); B) Hornfels clast affected by a
high-temperature potassic alteration and crosscut by an HT1bt-vein (sample BR-257); C) Porphyry clast crosscut by
an HT1px-vein (sample BR-300); D) Hornfels clast affected by a lower-temperature argillic alteration (kaolinite-
dickite-(illite) assemblage) overprinting an early potassic alteration, and crosscut by an HT2-vein (sample BR-260); E)
Hornfels clast strongly affected by a phyllic alteration and crosscut by a HT2-vein(sample BR-267); F) Hornfels clast
affected by a lower-temperature argillic alteration (kaolinite-dickite-(illite) assemblage) overprinting an early potassic
alteration, and crosscut by a HT2-vein (sample BR-261).

Mineralized hornfels clasts have a fine-grained texture. Their compositions were determined
combining classical petrography, XRD, and Raman microspectroscopy. Based on their mineral
compositions three different types of hornfels clasts could be distinguished. The first type is
characterized by a mineral assemblage typical for potassic alteration, including quartz, K-feldspar,
biotite, andalusite, albite and pyrite (Fig. 3A). The second one is interpreted to result from
overprinting of lower-temperature argillic alteration on early potassic alteration and consists of quartz,
K-feldspar, albite, kaolinite, dickite, and pyrite, (Figs. 3B and D). The third one results from phyllic

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alteration and includes quartz, muscovite, illite, siderite, and pyrite (Fig. 3E). In addition all the clasts
contain grains of apatite, rutile, and zircon. HT1 veins have been observed in the first two types of
clasts, and HT2 veins in the last two types of clasts.
The thin sinuous HT1 and the slightly thicker more regular HT2 quartz-molybdenite-
(chalcopyrite)-(pyrite) veins by their morphological and textural features, as well as their mineral
compositions (see below), share common characteristics with A- and B-type veins defined by
Gustafson and Hunt (1975). Considering the fact that the studied veins are restricted to small clasts
(<10 cm), and therefore the observations are limited, we prefer to use the more general terminology
HT1 and HT2, with “HT” referring to high temperature.

HT1 veins
The 1-2 mm thin, commonly sinuous HT1 are sulfide-poor (<< 1%), the main sulfides are
molybdenite, pyrite, and chalcopyrite (Fig. 3). SEM-CL reveals a single highly luminescent quartz
generation contemporaneous with the sulfide precipitation event and characterized by sub-rounded
oscillatory growth zoning (Figs. 4 B, C). Molybdenite grains vary from 20 µm to 100 µm in size,
occur principally along the contact of the veins with the host clasts (Fig. 5C), and subordinately are
intergranular between quartz crystals or as inclusions in the latter. Two distinct subclasses of HT1
veins were defined based on the nature of mineral inclusions in the hydrothermal quartz: i) HT1bt veins
commonly host numerous inclusions of K-feldspar, biotite, rutile, and minor titanite (Fig. 5A), and ii)
HT1px veins host numerous inclusions of actinolite, augite, titanite, apatite, and minor rutile (Fig. 5B).
In both vein subclasses mineral inclusions are small, range in size from few to tens of micrometers,
and are randomly distributed in quartz. Numerous fluid inclusions and few glassy silicate melt
inclusions are commonly observed in quartz crystals from both HT1 vein subtypes.

HT2 veins
The less sinuous morphology of the to 2 cm-thick HT2 veins (Fig. 3D, E, and F) suggests that
they are formed under more brittle conditions compared to HT1 veins. In one hornfels clast, HT2 veins
are observed to crosscut HT1 veins. This supports an early formation of HT1 compared to HT2 veins
(Fig. 4A). HT2 veins are also sulfide-poor (<1%), containing mainly pyrite and rare molybdenite
grains. In contrast to HT1 veins, HT2 veins are formed by quartz almost free of mineral inclusions;
only scarce rutile inclusions, from 10 to 50 µm in size, were found. HT2 veins host numerous fluid
inclusions and some rare, crystallized or glassy SMIs. SEM-CL imaging revealed i) a main quartz
generation characterized by euhedral crystals with oscillatory growth zoning, and ii) a second quartz
generation, minor in volume, overgrowing and showing subtle sub-rounded oscillatory growth zoning
and, locally, dissolution textures over the first one (Fig. 4A). Sulfides (molybdenite and pyrite) are
intergrown with both quartz generations.

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Figure 4: A) SEM-CL image of a HT2-vein crosscutting HT1bt-veins (Sample BR-312); B-C) SEM-CL images showing
typical quartz textures from HT1-veins.

Figure 5: A) Typical solid inclusion assemblage found in quartz forming HT1bt-veins (sample BR-261); B) Typical
solid inclusion assemblage found in quartz from HT1px-veins (sample BR-300); C) Molybdenite grain at the contact of
an HT1px- quartz vein with the hornfels (sample BR-259); D) Typical sulfide assemblage associated with the late
polymetallic mineralization (sample BR-267). Abbreviations: Act – actinolite, Aug – augite, Bt – biotite, Cpy –
chalcopyrite, Fh – fahlore group minerals, Gn – galena, K-Fsp – K-feldspar, Mo – molybdenite, Py – pyrite, Rt –
rutile, SMI – silicate melt inclusion, Sp – sphalerite.

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Pre-diatreme polymetallic mineralization
Commonly, HT1 and HT2 veins in diatreme clasts are crosscut by late 100 to 200 µm-thick
sulfide-rich veinlets mainly formed by pyrite, sphalerite with “chalcopyrite disease”, galena,
chalcopyrite, and tetrahedrite-tennantite (Fig. 5D), associated occasionally with low-luminescent
quartz, as revealed by SEM-CL imaging. In part, these sulfide-rich veinlets are emplaced by re-
opening of HT1 and HT2 veins. Based on the sulfide assemblages and the low CL-luminescence of the
quartz, we conclude that the polymetallic veinlets in diatreme clasts are probably formed at
intermediate temperatures < 350°C. These intermediate-temperature sulfide-rich veinlets are restricted
to the mineralized clasts, and therefore are pre-diatreme and earlier than the large epithermal
mineralizing event at Cerro de Pasco that crosscuts the diatreme (Baumgartner et al., 2008; Rottier et
al., 2016b).

Trace element analysis of quartz, rutile and titanite


LA-ICP-MS analyses were performed in areas devoid of solid and fluid inclusions. For quartz
and direct analyses of rutile grains, only analyses with flat LA-ICP-MS transient signals were
considered. For rutile and titanite present as solid inclusions in quartz, only signals clearly not
disturbed by other potential solid or fluid inclusions were considered. Potential contamination of the
ablation signals by fluid, melt, and not desired solid inclusions were carefully checked by tracking the
signals of Cs, Sr, Rb, Zr, W and Fe.

Quartz
Quartz crystals from 8 porphyry-type veins (3 HT1bt veins, 2 HT1px veins and 3 HT2 veins)
were analyzed by LA-ICP-MS. Analytical data are reported in supplementary table A.3. Quartz of the
different vein types display Ti and Al concentration ranges (Figs. 6 and 7A), comparable with
concentration ranges from quartz veins of other porphyry Cu-Mo deposits reported by Rusk et al.
(2008).
In each vein type, the Ti concentration in quartz grains of the same generation is highly
variable. In HT1bt and HT1px veins, SEM-CL images reveal just one quartz generation with small
differences of CL-intensity (Figs. 4B and C), that do not correlate with the Ti content in quartz. HT1bt
veins show the most important variation in Ti, from 32 to 176 ppm, while the Ti concentration in
HT1px veins varies from 19 to 64 ppm (Fig. 7A).
Quartz from HT2 veins generally has lower Ti contents (from 2 to 31 ppm) than quartz from
HT1 veins (from 81 to 114 pm), except sample BR-312 that has higher Ti content. No differences in
Ti contents were observed between the two quartz generations that form the HT2 veins. Quartz from
HT2 veins is also characterized by significant enrichment in Al (up to 2000 ppm) compared to HT1
veins (Fig. 6).

94
LA-ICP-MS profiles in quartz displaying oscillatory growth zoning in SEM-CL images reveal
only a weak correlation between CL intensity and Ti content (Fig. A.1). An elevated Ti content has
been considered to be the main reason for high CL-intensity in high-temperature quartz (Rusk et al.,
2008; Muller et al., 2010; Mercer et al., 2013 and 2015). The weak correlation observed in our
analyses may be attributed to the different volume of material analyzed by SEM-CL and by LA-ICP-
MS. Only the first micrometers of the quartz are involved in generating the SEM-CL light intensity,
whereas LA-ICP-MS spot depth is typically in excess of 100 µm.

Figure 6: Concentrations of Ti and Al in quartz from HT1bt, HT1px, and HT2 veins. Inset shows the large range of Al
concentrations in HT2 veins. Data from Rusk et al., (2008) of hydrothermal quartz from porphyry veins of various
porphyry deposits are plotted for comparison.

Rutile
Rutile crystals analyzed by LA-ICP-MS are from two HT1bt veins, two HT1px veins, and two
HT2 veins. The analyzed grains were small (< 50µm) and most of the time totally included in quartz.
In most LA-ICP-MS analyses, the entire rutile grain was ablated, by this way problems related to
chemical zoning and diffusion inside the grains are avoided.
Rutile contains up to several wt% Fe and W and several 1000s of ppm of Nb and Zr. Results
are reported in supplementary table A.3. Zirconium concentrations are quite similar in rutile from HT1
veins, with 836 to 1953 ppm for HT1bt veins and 699 to 3280 ppm for HT1px veins, whereas they are
much lower in rutile from HT2 veins, with 153 to 277 ppm (Fig. 7B). In rutile from HT1 veins, a weak
positive correlation of Nb, Mo, and Au with Zr is recognized, probably due to co-precipitation of these

95
elements during cooling of the fluid. In rutile from HT2 veins, no correlation between any element and
Zr has been noted.

Figure 7: A) Box plots of Ti concentrations in quartz from the different samples analyzed. B) Box plots of Zr
concentration in rutile from the different samples analyzed. Number of analyses is indicated above each box plot.
Box’s height represents the interquartile range (i.e. representing the most frequent 50% of the distribution). The
black lines dividing the boxes are the mean while the black dots represent the median value. “Whiskers” of each box
extend to the extremum values lying within 1.5 times the interquartile range beyond the edges of the box. The empty
circles and triangles represent outliers deviating more than ±2.7σ. Full circles represent isolated values.

Titanite
Five titanite grains included in quartz were analyzed: one from an HT1bt vein (sample BR-
261) and four from an HT1px vein (sample BR-300). The analyzed titanite grains were small (< 30
µm), and were entirely ablated during LA-ICP-MS analyses; compositions are reported in
supplementary table A.3. Zirconium content in titanite is 803 ppm for the HT1bt vein (sample BR-
261), and varies between 402 and 824 ppm for the HT1px vein (sample BR-300). Titanite contains
several 1000s of ppm of Al, Fe, La, and Ce and several 100s of ppm of Mg, Y, and P. A positive
correlation between Nb, La, and Ce with Zr exists, potentially indicating a preferential incorporation
of these elements in high-temperature titanite.

In-situ SIMS oxygen isotope analyses of different


quartz generations
A total of 22 in-situ SIMS oxygen isotope analyses of quartz from porphyry-type veins were
performed on samples BR-257 (HT1bt vein), BR-259 (HT1px vein) and BR-267 (HT2 vein). The
results are nearly identical in the three samples and show no correlation with the textures revealed by
SEM-CL (Fig. 8): δ18O HT1bt vein=12.0 ± 0.3 ‰ (n=4), δ18O HT1px vein=12.1 ± 0.3 ‰ (n=7), δ18O

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HT2 vein=12.4 ± 0.2 ‰ (n=7). Two analyses on quartz associated with the pre-diatreme polymetallic
mineralization gave δ18O values of 17.4 and 16.8 ‰ (Fig. 8).

Figure 8: Summary of δO18 SIMS analyses of quartz from HT1bt (A), HT1px (B), HT2 vein (blue values) and from the
late polymetallic mineralization (orange values, C; similar to Fig. 5D).

Fluid inclusions

Petrography, microthermometry and Raman analysis


Five fluid inclusion types were identified according to the number, the nature, and the volume
proportion of phases present at room temperature. They are: i) CO2-rich high-density vapor inclusions
(Figs. 9 A and B), ii) polyphase brine inclusions (Figs. 9C and D), iii) low-density vapor inclusions,
iv) brine inclusions (Fig. 9 E), and v) aqueous inclusions (Fig. 9 F).
The CO2-rich high-density vapor inclusions were found exclusively in HT1bt and HT1px veins,
whereas the polyphase brine and the low-density vapor inclusions are restricted to HT2 veins. Brine
and aqueous inclusions are low temperature, secondary and found in all vein types.
Microthermometric results are summarized in Table 2.
The CO2-rich high-density vapor inclusions are between 5 and 35 µm in size, most of them
contain one hematite flake and one anhydrite crystal (Figs. 9A and B). They are mostly organized as
patches in the core of the quartz, and also form secondary trails. At room temperature, only liquid and
vapor phases are visible; during cooling, liquid CO2 appears at around +12°C. In the absence of liquid
CO2, the inclusions contain 55 to 90% vapor and their L/V ratio is constant within the same
assemblage. The measured melting point of CO2 varies from -56.0° to -56.5°C; CO2 was the only gas
detected by Raman microspectroscopy. Clathrate melting occurs between -1.0° and +9.2°C and CO2
homogenizes to vapor between 10.2° and 14.0°C. Total homogenization occurs by the disappearance
of liquid between 382° and 421°C, except for one FIA which homogenizes at around 550°C (Fig. 10;

97
purple and red diamonds). Calculated salinities are different in FIAs from HT1bt veins, with values
between 1.8 and 12.4 wt% NaCl equiv., and in FIAs from HT1px veins, with values between 11.5 and
16.6 wt% NaCl equiv. (Fig. 10). Raman analyses of the liquid phase in CO2-rich inclusions reveal the
presence of SO42- ion in solution (Fig. A.2). Analyses where performed from room temperature to
450°C, and an increase of the area of SO42- peak at 980 cm-1 was observed with increasing temperature,
probably due to the progressive dissolution of the anhydrite crystals present in the fluid inclusions
(Figs. 9B and A.2). HSO42- ions and H2S have not been detected in the liquid and the vapor phase,
respectively. Presence of detectable SO42- indicates that the fluid was sulfur-rich and in combination
with the presence of hematite this is indicative of the oxidizing nature of the fluid trapped in the
inclusions. Such oxidizing conditions may not represent the initial composition of the trapped fluid
and could also be related to post-entrapment H2 diffusion out of the inclusions (Mavrogenes and
Bodnar, 1994).

Figure 9: A) CO2-rich high-density vapor inclusions hosted in an HT1bt vein; B) CO2-rich high-density vapor
inclusion in an HT1px vein; C-D) Polyphase brine inclusions hosted in a HT2 vein; E) Low-temperature brine in an
HT1bt vein; F) Low-temperature aqueous fluid inclusions in an HT1bt vein.

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Table 2: Microthermometry data for fluid inclusion assemblages.
(1) (2) (3) (4) (6) (7)
FIA veins n Type L% TmCO2 σ Tmchl σ ThCO2 σ TmIce
(5)
σ TmSyl? σ TmHal σ

300L_8 HT1px # LlCO2 30 -56,2 0,1 3,2 1,6 10,2 1,9


300I_2 HT1px # LlCO2 20 -56,5 0,1 2,9 2,0 11,5 1,9
300E_9 HT1px # LlCO2 45 -56,2 0,3 -0,3 1,1 10,5 1,2
300L_6 HT1px 9 LlCO2 25 -56,4 0,1 -0,8 1,0 11,0 2,1
259C4_1 HT1px 7 LlCO2 15 -56,1 0,1 0,6 3,4 14,0 1,1
259C4_2 HT1px 7 LlCO2 10 -56,0 0,0 -1,0 0,5 13,5
259C2_2 HT1px 9 LlCO2 15 -56,3 0,1 2,3 1,8 12,5
257C4_1 HT1bt 7 LlCO2 10 -56,0 0,0 2,6 1,1 12,5
311C_1 HT1bt 7 LlCO2 45 -56,4 0,0 9,1 0,5 12,0
311E_2 HT1bt 8 LlCO2 15 -56,5 0,0 7,4 0,8 12,5
311D_5 HT1bt 6 LlCO2 45 -56,5 0,1 7,6 0,8 12,0
311B_1 HT1bt 5 LlCO2 10 -56,3 0,0 6,2 0,9 11,5
10-
267C2 HT2 # P. Brine 20 141 3,8 377 11,0
10-
267C3 HT2 # P. Brine 20 132 6,8 408 23,6
10-
267C6_1 HT2 8 P. Brine 20 137 2,8 364 5,0
10-
267C6_3 HT2 # P. Brine 20 140 4,4 378 9,8
10-
267C6_2 HT2 7 P. Brine 20 145 6,7 369 2,5
10-
267C7_2 HT2 # P. Brine 20 136 4,7 318 11,5
10-
313A2 HT2 8 P. Brine 20 153 11,4 273 10,9
10-
313A2b HT2 6 P. Brine 20 145 12,2 306 12,9
10-
313A1 HT2 8 P. Brine 20 165 12,7 393 9,6
10-
312_2 HT2 # P. Brine 20 Nd Nd 344 19,7
10-
312_1 HT2 7 P. Brine 20 118 0,8 338 8,1
261_2_2C HT1bt 7 aqueous 80 -16,0 0,9
261_2_3 HT1bt 9 aqueous 80 -23,4 2,5
257_C4_2 HT1bt # aqueous 80 -15,2 0,7
257_C2_1 HT1bt 9 aqueous 80 -3,6 0,2
257_C3_1 HT1bt 7 aqueous 80 -1,1 0,1
75-
257_C4_3 HT1bt 4 Brine 222 21,9
80
75-
257_C4_4 HT1bt 3 Brine 251 18,5
80
75-
257_C4_5 HT1bt 2 Brine 191 9,9
80
75-
257_C3_2 HT1bt 8 Brine 274 19,0
80
75-
257_C3_3 HT1bt 6 Brine 253 14,2
80

99
(8) (9) salinity eq (11) (12) Pmin
FIA veins n Thtotal σ mode (10) σ XCO2 σ d(g/cm3) (13)
(Bar)
300L_8 HT1px 11 421 8,0 V 11,5 2,2 0,14 0,008 ≈0.38 360
300I_2 HT1px 13 382 13,6 V 11,8 2,8 0,22 0,004 ≈0.31 290
300E_9 HT1px 14 550 12,0 V 15,8 1,1 0,07 0,003 ≈0.6 1470
300L_6 HT1px 9 412 15,0 V 16,3 1,0 0,17 0,003 ≈0.35 230
259C4_1 HT1px 7 391 11,0 V 14,4 3,7 0,28 0,004 ≈0.27 205
259C4_2 HT1px 7 399 9,1 V 16,6 0,4 0,37 0,001 ≈0.23 217
259C2_2 HT1px 9 386 14,4 V 12,6 2,2 0,27 0,006 ≈0.27 298
257C4_1 HT1bt 7 Nd Nd V 12,4 1,4 0,38 0,000 ≈0.23 Nd
311C_1 HT1bt 7 394 25,4 V 1,8 1,0 0,10 0,000 ≈0.53 590
311E_2 HT1bt 8 384 20,9 V 5,0 1,5 0,29 0,000 ≈0.28 370
311D_5 HT1bt 6 395 10,8 V 4,7 1,4 0,10 0,001 ≈0.53 540
311B_1 HT1bt 5 Nd Nd V 7,0 1,5 0,38 0,001 ≈0.23 Nd

267C2 HT2 15 L? 44,7 1,1 0.9* 748*


267C3 HT2 14 L? 48,0 2,6 0.93* 709*
267C6_1 HT2 8 L? 43,3 0,5 0.88* 763*
267C6_3 HT2 14 L? 44,7 1,0 0.90* 757*
267C6_2 HT2 7 L? 43,8 0,2 0.88* 747*
267C7_2 HT2 14 L? 39,1 1,0 0.83* 810*
313A2 HT2 8 L? 35,8 0,7 0.80* 790*
313A2b HT2 6 L? 38,2 1,0 0.82* 785*
313A1 HT2 8 L? 42,3 1,0 0.91* 728*
312_2 HT2 14 L? 41,4 1,8 0.86* 843*
312_1 HT2 7 L? 40,9 0,7 0.85* 819*
261_2_2C HT1bt 7 264 13,4 L 19,4 0,7 0,96 44
261_2_3 HT1bt 9 235 6,3 L 24,5 1,7 1,03 25
257_C4_2 HT1bt 11 231 9,6 L 18,8 0,6 0,99 25
257_C2_1 HT1bt 9 226 12,5 L 5,8 0,2 0,88 25
257_C3_1 HT1bt 7 245 5,4 L 1,9 0,2 0,82 36
257_C4_3 HT1bt 4 239 9,2 L** 30,8 4,0 1,1 24
257_C4_4 HT1bt 3 277 22,6 L** 34,8 1,2 1,1 45
257_C4_5 HT1bt 2 226 11,3 L** 31,4 0,5 1,1 19
257_C3_2 HT1bt 8 275 19,0 H** 36,3 1,3 1,2 1756
257_C3_3 HT1bt 6 256 10,2 L* 34,9 0,9 1,1 31
Data are reported as an average for each fluid inclusion assemblage with 1σ standard deviation. Host mineral of all studied inclusions is
quartz. * densities and pressures calculated assuming an homogenization temperatures of 600°C. ** principal homogenization behavior of
the FIAs. (1) Mean volume percent of the liquid phase in the inclusions. (2) Temperature of melting of solid CO2. (3) Temperature of melting
of CO2 clathrate. (4) Temperature of the total homogenization of the CO2 phase. (5) Ice melting temperature. (6) Temperature of melting of
solid phase identified as sylvite. (7) Halite melting temperature. (8) Temperature of total homogenization. (9) Mode of homogenization: V –
vapor, L – liquid, H – Halite. (10) Calculated salinity in wt % NaCl equiv. (11) Measured CO2 concentration (12) Calculated density. (13)
Calculated minimal pressure of entrapment.

The polyphase brine inclusions and low-density vapor inclusions form secondary trails
through quartz crystals. A few clear boiling assemblages with coexisting polyphase brine and low-

100
density vapor in the same trail are observed. The polyphase brine inclusions range from 10 to 25 µm in
size and always contain two transparent crystals and rarely an opaque crystal and/or a hematite flake
(Figs. 9C and D). The vapor phase composes 30 to 50% of the inclusion volume. One transparent
crystal is rounded, pale green in color, and melts between 118° and 165°C; it has been interpreted as
sylvite. The other transparent mineral is halite and melts between 273° and 408°C. Salinities were
calculated based on halite melting temperatures and vary between 35.8 and 48.0 wt % NaCl equiv.
(Fig. 10; blue circles). The polyphase brine inclusions were heated up to 580°C without reaching total
homogenization; a very small vapor bubble remained. Judging from the remaining bubble size, total
homogenization of such inclusions most likely occurs at temperature around 600°C or slightly above.
Raman analyses of the vapor phase of polyphase brine inclusions yield presence of CO2 (Fig. A.2). No
microthermometric measurements were done on the low-density vapor inclusions.

Figure 10: Microthermometric results on salinity (wt. % NaCl equiv.) versus temperature of homogenization (°C)
diagram. Each FIA is represented by its mean value and the error bars represent ± 1σ. Purple and red diamonds are
CO2-rich high-density vapor FIAs respectively hosted in HT1px-veins and HT1bt-veins. Blue circles represent
polyphase brine FIAs hosted in HT2-veins, homogenization temperatures were fixed at 600°C. Green and yellow
squares are respectively brine and aqueous FIAs in HT1bt-veins.

Low temperature brine inclusions occur in secondary trails. They are generally small, around 5
µm with a few larger inclusions up to 25 µm in size (Fig. 9E). The vapor phase typically occupies
~20% of the inclusion volume. Around 50 % of the measured brine inclusions homogenized by vapor
disappearance and 50% by halite disappearance, and both types of homogenization behavior were
observed in some FIAs. Total vapor disappearance occurs from 183° to 277°C and halite dissolution
temperatures vary between 191° and 275°C, corresponding to salinities from 30.8 to 36.3 wt% NaCl
equiv. (Fig. 10; green squares). Total homogenization by halite dissolution is common for brine
inclusions in porphyry systems (e.g., Rusk et al., 2008; Lecumberri-Sanchez et al., 2015) and is
commonly interpreted as due to high trapping pressures (Becker et al., 2008; Lecumberri-Sanchez et

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al., 2012) or as indicative of heterogeneous entrapment of fluid saturated in halite (Lecumberri-
Sanchez et al., 2015). Raman analyses of these inclusions did not detect gas (e.g. CO2, CH4…) in the
vapor phase.
Aqueous inclusions form secondary trails. Inclusions range in size from 5 to 40 µm. Vapor
occupies ~20 vol. % of the inclusions. No solids were observed (Fig. 9F). The ice melting
temperatures occur between -1.1° and -23.4°C corresponding to salinities of 1.9 to 24.5 wt % NaCl
equiv. (Fig. 10; yellow squares). One FIA shows ice melting temperature below -21.2°C, in metastable
absence of hydrohalite. Total homogenization of aqueous inclusions occurs by vapor disappearance at
temperatures between 226° and 264°C (Fig. 10). Raman analyses of these inclusions indicate the
presence of small amounts of CO2.

Fluid composition
Results of LA-ICP-MS analyses of fluid inclusions are plotted as selected element
concentration ratios [(X / (Na+K+Fe)]. They are classified by fluid inclusion and vein types and sorted
by salinity decrease (Fig. 11). Only element concentration ratios [(X / (Na+K+Fe)] are plotted and
discussed to avoid errors induced by the determination of sodium content from microthermometry
measurements. The fluid composition of CO2-rich high-density vapor inclusions is similar in HT1bt
and HT1px veins for most elements except for Au, Cu, and Zn that show higher concentration ratios in
fluid inclusions in HT1bt veins (Figs. 11and A.3). Fluid compositions of the polyphase brine inclusions
from HT2 veins show lower concentration ratios for Zn, Sr, Mo, Cu, Au, Li and Cs than in those in
HT1 veins (Fig. 11). Concentration ratios in the late fluids (the low-temperature brine and aqueous
fluid inclusions, Fig. 11) are generally scattered with a large standard deviation for each FIA.
Compared to the CO2-rich high-density vapor inclusions and polyphase brine inclusions from HT1 and
HT2 veins, concentration ratios of B, Li, Ca, Sr, Cs and Ba are significantly higher whereas those of
Pb, Zn and Fe are lower (Fig. 11). Mo/(Na+K+Fe) ratios show important variations from 6,3.10-3 to
4,9.10-5 and tend to decrease with the relative timing from HT1bt veins, to HT1px veins and to HT2
veins (Fig. 11). The obtained values are in the range of published data from Cu-Mo and Mo porphyry
systems (Ulrich et al., 2002; Landtwing et al., 2005 and 2010; Klemm et al., 2007 and 2008;
Kouzmanov and Pokrovski, 2012; Lerchbaumer and Audétat, 2013). Like Mo, concentration ratios for
Cu show important variations and range from 0,05 to 2,6.10-4, except for one FIA from an HT1px vein
showing a higher concentration ratio of 0.24 (Fig. 11); no systematic variations according to salinity or
homogenization temperature are observed. A general decrease of Cu concentration ratios in FIAs is
recognized from HT1 to HT2 veins. Obtained Cu concentration ratios in CO2-rich high-density vapor
inclusions from HT1 veins are lower by one order of magnitude or more compared to published data
for intermediate-density fluid inclusion compositions from other Cu-Mo and Mo porphyry systems; in
contrast, Zn concentration ratios are higher up to one order of magnitude (Ulrich et al., 2002;
Landtwing et al., 2005 and 2010; Klemm et al., 2007 and 2008; Stefanova et al., 2014).

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Figure 11: Element concentration ratios relative to Na, K and Fe (X/Na+K+Fe) of individual fluid inclusion
assemblages obtained from LA-ICP-MS analyses. Fluid inclusions are sorted by fluid type and by salinity decrease.

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Melt inclusions

Petrography and description


Small silicate melt inclusions (SMIs), generally 5-10 µm in diameter but locally up to 25 µm
(Fig. 12), were identified in HT1 and HT2 veins. They mainly occur as isolated inclusions, rarely
grouped in melt inclusion assemblages (MIAs). Classical petrography combined with SEM-CL
imaging reveal no spatial relationship between the distribution of silicate melt inclusions and the
position of fluid inclusions or the quartz growth banding. SEM-CL images do not reveal xenocryst
quartz grains and suggest that all quartz was grown locally (Figs. 4, 8 and A.2).
In HT1 veins, the SMIs are glassy and contain a shrinkage bubble filling ~10 vol. % of the
inclusion, and rarely a crystal occupying <5 vol. % of the SMI (Figs. 12A, B, C and D). In HT2 veins
the SMIs are either glassy like in HT1 veins or totally crystallized forming a dark mass of fine-grained
crystals with no discernable vapor bubble (Figs. 12E and F).

Figure 12: A-D) Glassy silicate melt inclusions hosted in quartz from HT1bt- or HT1px-veins. E-F) Crystallized silicate
melt inclusions hosted in quartz from HT2-veins

Melt inclusions composition


A total of 53 melt inclusions from HT1 and HT2 veins were analyzed by LA-ICP-MS, 39
from HT1bt veins, 4 from HT1px veins, and 10 from HT2 veins; results are reported in supplementary
table A.4. Only inclusions fully enclosed by quartz and not intersected by any crack or fluid inclusion

104
trail were selected for analysis. The analyzed SMIs have been compared to whole rock data of dacite
and rhyodacite domes and quartz monzonite dykes of Cerro de Pasco district (Rottier et al., 2016a) and
also to published data of SMI compositions hosted in quartz from miarolitic cavities from various
barren granitic systems (Zajacz et al., 2008) and to SMIs found in porphyry-type quartz veins from the
Elatsite porphyry Cu-Au deposit (Bulgaria; Stefanova et al., 2014); only SMI compositions classified
by the authors as not affected by the hydrothermal fluid were selected for comparison (Fig. 13).
All analyzed SMIs are rhyolitic (calculated SiO2 content ranges from 71.2 to 76.5 wt. %), K2O
is strongly enriched and varies from 4.2 to 7.9 wt. %, Fe2O3 varies from 0.2 to 1.6 wt.%, and CaO,
MgO, TiO2, MnO are always below 0.5 wt. %. The Na2O content of the SMIs varies from 2.8 to 4.1
wt. % except for SMIs hosted in HT2 veins where Na2O is strongly depleted < 1.5 wt. % (Fig. 13).
Such Na2O depletion is due probably to post-entrapment loss of Na (Zajacz et al., 2009), possibly
related to a slower cooling rate of the SMIs hosted in HT2 veins than the one hosted in HT1 veins,
which is also suggested by the fact that the SMIs tend to be coarsely crystallized (Bodnar and Student
2006).
The strong incompatible behavior of Cs was used as a proxy for the degree of crystallization
and fractionation of the residual melt (Audétat et al., 2008). Silicate melt inclusions show an increase
in incompatible element concentrations like Rb, W, Mo, Sb and a decrease in compatible element
concentrations like Sr and K, with the increase of the fractionation degree of the trapped melt (marked
by the increase of Cs content). Similar evolution trends were reported in SMIs from miarolitic cavities
(Zajacz et al., 2008) and from porphyry veins at the Elatsite porphyry Cu-Au-PGE deposit (Stefanova
et al., 2014). Base metal concentrations in SMIs range from 20 to 200 ppm (with three values above
300 ppm) for Zn, from 0.7 to 84 ppm (with two values above 200 ppm) for Pb, and from 1.3 to 194
ppm for Cu. Few SMIs from HT1bt veins present higher Cu values (up to 800 ppm Cu; Fig. 13), these
values are likely due to post-entrapment Cu diffusion through quartz (Zajacz et al., 2009; Rottier et al.,
2016a; Rottier et al., 2017). Base metal concentrations of the SMIs are slightly enriched compared to
the whole rock analyses of dacite and rhyodacite domes and quartz monzonite dykes, but relatively
similar to base metal concentrations of SMIs hosted in miarolitic cavities from barren granitic systems
(Zajacz et al. 2008; Fig. 13). Copper presents a rough positive correlation with Cs discarding the high
values attributed to post-entrapment diffusion, whereas Zn and Pb show no correlation with Cs and
their concentrations are roughly constant (Fig. 13). Tungsten, Sb, and Mo are enriched compared to
the whole rock data and show a weak positive correlation with Cs (Fig. 13); W varies from 0.10 to 290
ppm, Sb from 0.26 to 195 ppm, and Mo from 1 to 35 ppm. As for Cu, Zn, and Pb, these values are
relatively similar to the ones from miarolitic cavities from granitic systems (Zajacz et al. 2008). Zinc,
Pb, Cu, W, and Sb are enriched compared to SMIs hosted in quartz veins from Elatsite (Stefanova et
al., 2014; Fig. 13). Elevated silver concentrations from 0.2 to 11.7 ppm were detected in 15 SMIs.

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Figure 13: Plot of selected elements or element ratios against Cs concentration obtained from LA-ICP-MS analyses of
individual SMI and whole-rock LA-ICP-MS data. Black squares represent whole rock analyses (LA-ICP-MS) of
dacite and rhyodacite domes and quartz-monzonite dykes from Cerro de Pasco (data from Rottier et al, 2016a). Full
red, purple, and blue circles represent SMIs hosted in HT1bt-, HT1px- and HT2-veins, respectively. Gray diamonds are
SMIs hosted in quartz from miarolitic cavities from various barren granitic systems from Zajacz et al. (2008). Gray
triangles and empty gray reversed triangles are respectively SMIs homogenized in an autoclave and SMIs not
homogenized prior to LA-ICP-MS analyses, hosted in quartz from porphyry-type veins from the Elastite Cu-Au-PGE
porphyry deposit (Bulgaria), data are from Stefanova et al. (2014).

106
Discussion

Comparison of the mineral thermobarometers


Effect of pressure on the Zr in rutile and Zr in titanite thermobarometers is small (~5°C for 1
kbar and ~10°C for 1 kbar, respectively, Figs. 15 and A.4, Tomkins et al., 2007; Hayden et al., 2008),
this effect is more important for the Ti in quartz thermobarometer (~70°C for 1 kbar, Figs. 15 and A.4,
Huang and Audétat 2012).
The Zr in rutile and the Zr in titanite thermobarometers are considered to be robust
thermometers due to the weak effect of pressure estimates, the very low diffusion rate of Zr in rutile
and titanite and their independence relative to mineral growth rate (Tomkins et al., 2007; Hayden et
al., 2008), when compared to that of Ti in quartz. The Zr in rutile thermobarometer was successfully
used to reconstruct vein formation temperatures in the Butte porphyry Cu-Mo deposit (Mercer et al.,
2013).
To estimate formation temperatures, and considering the weak effect of pressure on the Zr in
rutile thermobarometer, pressure of formation of the HT1bt veins and HT1px veins was fixed (Figs 14
and 15) to respectively 900 and 1300 bars using the intersection of Zr in rutile isopleths and the
constructed isochores for CO2-rich high-density vapor inclusions (see next section). For HT2 veins,
pressure was fixed at 850 bars (Fig. 14), corresponding to the entrapment pressure of the polyphase
brine inclusions (see next section). At these assumed pressures i) the Ti in quartz thermobarometer
yields temperatures of formation between 626° and 639°C for HT1bt veins, between 578° and 600°C
for HT1px veins, and between 433° and 462°C for HT2 veins excepted sample BR-312 that returns
higher values ranging from 647° to 681°C (Fig. 14); ii) the Zr in rutile thermobarometer gives
temperatures of formation between 696° and 771°C for HT1bt veins, 736° and 756°C for HT1px, and
between 587° and 592°C for HT2 veins (Fig. 14); iii) the Zr in titanite thermobarometer gives
temperatures of formation of 750°C for HT1bt veins and between 716° and 751°C for HT1px (Fig. 14).
We obtained similar temperatures using the Zr in rutile and the Zr in titanite thermobarometers (Figs.
14, 15) whereas the temperatures obtained with Ti in quartz thermobarometers are up to 150°C lower
(and up to 100°C higher for sample BR-312; Fig. 14). Such differences could indicate (i) that quartz
grows in disequilibrium with the fluid or (ii) that quartz growth rate during vein formation is actually
slower (or higher for sample BR-312) than the one used for the calibration of the thermobarometer (2-
4 µm/day; Huang and Audétat, 2012).

107
Figure 14: Box plots of isobaric temperature, obtained at pressure fixed at 0.9 kbar for HT1bt veins, at 1.3 kbar for
HT1px and 0.85 kbar for HT2 veins, using the Ti in quartz thermobarometer of Huang and Audétat (2012) indicated
by Qz at the bottom of each column, the Zr in rutile thermobarometer of Tomkins et al. (2007) indicated by Rt at the
bottom of each column and the Zr in titanite thermobarometer of Hayden et al. (2008) indicated by Tnt at the bottom
of each column, for the different samples analyzed. Boxes height represents the interquartile range (i.e. representing
the most frequent 50% of the distribution). The black lines dividing the boxes are the mean while the black dots
represent the median value. “Whiskers” of each box extend to the extremum values lying within 1.5 times the
interquartile range beyond the edges of the box. The empty circles and triangles represent outliers deviating more
than ±2.7σ. Full circles represent isolated values.

Pressure temperature reconstruction

HT1 veins
Isochores for the CO2-rich high-density vapor inclusions hosted in HT1bt and HT1px veins are
quite similar (Fig. 15). Two to three isochores were constructed per FIA to illustrate the existing range
inside one FIA. Both, for HT1bt and HT1px veins, two distinct families of isochores could be discerned:
i) “steep” isochores, and ii) “gentle inclined” isochores (Fig. 15). Formation pressures were estimated
using the intersection between Zr in rutile isopleths and the isochores. For the “steep” isochores, the
obtained pressures are between 1800 and 2300 bars for HT1bt veins and between 1500 and 2750 bars
for HT1px veins. Whereas for the “gentle inclined” isochores the obtained pressures are between 500
and 900 bars for HT1bt veins and between 700 and 1300 bars for HT1px veins. Existence in both vein
types of two isochore families yielding distinctly different pressure estimations is difficult to interpret.
SEM-CL images reveal only one quartz generation forming HT1px and HT1bt veins, and a drop or an
increase of pressure of almost 1kbar during the formation of the HT1 veins is not supported by textural
evidence. The obtained high pressure would suggest an emplacement depth between 5.5 and 10 km,
which is significantly higher than classical emplacement depth reported for porphyry deposits (e.g.,
Lecumberri-Sanchez et al., 2015), whereas the emplacement depth of 2 to 5 km obtained by the
“gentle inclined” isochores is consistent with that of most for porphyry systems.

108
Figure 15: Pressure-temperature diagram, the black lines represent isochores calculated for CO2-rich high-density
vapor inclusions in HT1bt-veins (A) and HT1px-veins (B); two or three isochores were constructed per FIAs. Coloured
thick lines and shaded fields are Zr isopleths of rutile, Zr isopleths of titanite and Ti isopleths of quartz from HT1bt-
veins (A) and HT1px-veins (B). Solid lines represent the mean value and shaded fields represent the mean ± 1σ range
of values of Zr concentration of rutile and titanite and Ti concentration of quartz from HT1bt-veins(A) and HT1px-
veins (B).

Geological data can contribute to constrain the emplacement depth of the porphyry veins. The
mineralized clasts are hosted in a diatreme breccia that has been recognized to a depth of 1150 m
below present surface. Post diatreme erosion is assumed to be less than 1 km (Baumgartner 2007;

109
Baumgartner et al., 2008). This vertical extent is in line with the generally assumed vertical extent of
diatreme breccia bodies formed during large phreatomagmatic eruptions that is considered to not
exceed 2 km (e.g, White and Ross, 2011; Valentine and White, 2012). If this vertical extent range of
the diatreme breccia is realistic, an emplacement depth between 5.5 and 10 km, as obtained by the
“steep” isochores, would require erosion of 3.5 to 7.5 km of material between formation of the
porphyry mineralization and the phreatomagmatic eruption, a time lapse of less than 300.000 years
(Table 1, Baumgartner et al., 2009; Rottier 2017). Such an erosion rate is not supported by the
existence of related Late Miocene detrital units in the area, nor by other geological evidences. In
contrast, the formation depths suggested by the “gentle inclined” isochores between 2 to 3.5 km for
HT1bt veins, 2.6 to 5 km for HT1px veins, requires only erosion of 0.5 km to 3 km of material between
porphyry mineralization formation and the phreatomagmatic eruption and are probably close to the
true formation pressures. Considering these pressure estimations, the HT1bt-veins formed between 500
and 900 bars and between 710° and 770°C, and of HT1px-veins between 700 and 1300 bars and
between 680° and 810°C (Figs. 14 and 15).
The pressures obtained with the "steep" isochores could result from i) post-entrapment
modification leading to a density overestimation, or ii) a local overpressure. Local fluid overpressure
can occur in magmatic-hydrothermal systems where sealed fracture networks reach the magmatic
chamber underneath, leading to an overpressure (P ≈ magmatic pressure; Carrigan et al., 1992).

HT2 veins
Homogenization of the polyphase brine inclusions hosted in HT2 veins was not reached at
580°C and homogenization temperatures are estimated to be slightly above 600°C. In places,
polyphase brine FIAs are spatially associated with low-density vapor inclusions and interpreted as
boiling assemblages. Thus, temperatures, densities, and pressures obtained correspond to the true
trapping conditions. Zr in rutile temperatures obtained for HT2-veins are between 587° and 592°C and
are in a good agreement with homogenization temperatures of polyphase brine FIAs. Pressure of
entrapment for the polyphase brine inclusions estimated from phase relations in the H2O-NaCl system
(Driesner and Heinrich, 2007) are between 710 and 850 bars, assuming a homogenization temperature
of 600°C (Table 2). Real entrapment pressures would have been somewhat higher considering the
minor presence of CO2. Nonetheless, the determined pressure range is consistent with the one obtained
for the HT1bt and HT1px veins using the “gentle inclined” isochores.

Low temperature fluids


Calculated pressures, using the SoWat software (Driesner 2007; Driesner and Heinrich, 2007),
for the low-temperature brines in secondary trails homogenizing by halite disappearance are higher
than 1700 bars. Such high pressures are not compatible with the pressure estimations for the HT1 and
HT2 veins. Such inclusions probably result from a heterogeneous entrapment of fluid and halite, as

110
proposed by Lecumberri-Sanchez et al. (2015). The reconstructed isochores, using the SoWat software
(Driesner and Heinrich, 2007), for aqueous and brine inclusions homogenizing by vapor disappearance
are steep, and assuming a similar entrapment pressure as we used for HT1 and HT2 veins (~800 bars)
the obtained entrapment temperatures are between 270° and 320°C. These temperatures indicate
cooling of the system which is also supported by the occurrence of the pre-diatreme polymetallic
mineralization inside the veins.

Origin and evolution of the fluids


Occurrence of CO2-rich high-density vapor inclusions as those observed in HT1bt and HT1px
veins is not common in most porphyry Cu-(Mo)-(Au) deposits (Kouzmanov and Pokrovski, 2012).
These CO2-rich inclusions are also strongly enriched in sulfur as indicated by the presence of
anhydrite daughter crystals and the detectable amount of SO42- ions in the fluid phase of the inclusions
(Figs. 9B and A.2). CO2 and sulfur strongly partition into the vapor phase during magmatic fluid
exsolution; if magmas reach fluid saturation deep in the crust, CO2-rich fluids exsolve and the residual
magma is depleted in CO2 (Lowenstern, 2001). A dacitic magma moderately enriched in CO2, around
500 ppm, and with a normal water content of 5 wt%, will reach fluid saturation at shallower levels (~2
kbar) and the exsolved fluid will contain around 0.3 XCO2 (Fig. 3 in Lowenstern, 2001), similar to the
values measured in the studied CO2-rich high-density vapor inclusions (Table 2). Our CO2- and sulfur-
rich high-density vapor inclusions could represent the first fluid exsolved from a dacitic magmatic
body at ~2 kbar. Such interpretation is also coherent with the high formation temperatures of the HT1bt
and HT1px veins (>700°C) which is in agreement with the solidus of dacitic magmas (Caricchi and
Blundy, 2015). An alternative possibility is that the CO2-rich high-density vapor inclusions in HT1bt
and HT1px veins result from fluid exsolution due to injection of more CO2- and sulfur-rich mafic
magmas into the underlying magmatic chamber as suggested in other porphyry deposits (Halter et al.,
2005).
The relatively wide ranges of salinity values of CO2-rich high-density vapor inclusions (1.8 to
12.4 wt% NaCl equiv in HT1bt veins and from 11.5 to 16.6 wt% NaCl equiv in HT1px veins), probably
record minor phase separation during fluid ascent, even if no direct evidence of this process was
observed.
HT2 veins crosscut HT1 veins and are formed at lower temperature (~600°C). LA-ICP-MS
analyses show that concentration ratios of Na, K, and Fe and also of Zn and Cs are different in CO2-
rich high-density vapor inclusions from the HT1 veins and in polyphase brine inclusions from the HT2
veins (Figs. 11 and A.3). If the polyphase brine inclusions trapped in HT2 veins had been formed by
phase separation of CO2-rich high-density vapor inclusions trapped in the HT1 veins, their
concentration ratios of Na, K, Fe, Zn and Cs would be similar, as it has been reported in other
porphyry deposits (Ulrich et al., 2002; Landtwing et al., 2005 and 2010; Klemm et al., 2007;
Stefanova et al., 2014). The consistency observed in these deposits would suggest that concentration

111
ratio [(X / (Na+K+Fe)] of Mn, Cs, Rb, Pb and Zn are not affected by phase separation, this point is
coherent with the fact that vapor-liquid partition coefficients is almost similar for Na, Fe and Zn
(Kouzmanov and Pokrovski 2012 and references therein); no experimental data are available for the
other elements. Therefore, the different concentration ratios observed between the CO2-rich high-
density vapor and the polyphase brine inclusions suggest that fluid trapped in the HT2 veins results
from a different fluid exsolution event. Cesium concentration ratios are lower in polyphase brine
inclusions from HT2 veins than in the CO2-rich high-density vapor inclusions from HT1 veins (Fig.
11) suggesting that fluid is exsolved from a less differentiated magma than the one that exsolved the
fluid forming the HT1 veins (Audétat et al., 2008). Such decrease of the differentiation degree could
be linked to injection of mafic magmas into the underlying magmatic chamber which is also coherent
with the increase of Fe concentration ratios and decrease of Zn concentration ratios in polyphase brine
inclusions (Fig. 11). To summarize, the polyphase brine inclusions trapped in HT2 veins are formed
by phase separation occurring at around 800 bars and 600°C of an intermediate-density fluid exsolved
from a chemically less differentiated magma than the one that exsolved the fluids forming the HT1-
veins.
The scattered salinities and concentration ratios and the strong enrichment in Sr, Ba and Ca of
the low-temperature brine and aqueous secondary inclusions are typical for fluid linked to feldspar
destabilization during phyllic alteration. We cannot totally discard the possibility that these secondary
low-temperature fluid inclusions are trapped in quartz after the emplacement of the diatreme-breccia.
But no similar inclusions have been observed in quartz phenocryst in the diatreme-breccia surrounding
the mineralized clasts, suggesting that the low-temperature brine and aqueous secondary fluid
inclusions were trapped before the breccia formation. They would, thus, record the cooling of the
hydrothermal system at depth, as also suggested by the occurrence of pre-diatreme polymetallic
mineralization in reopenings of HT1 and HT2 veins.

Oxygen isotope signatures of the different events


δ18O of the fluid in equilibrium with the different quartz generations was calculated using
high- and low-temperature fractionation curves of Matsuhisa et al. (1979) assuming a temperature of
700°C for HT1bt- and HT1px-veins, 600°C for HT2-vein, based on the mineral thermobarometers and
the fluid inclusion microthermometry (Fig. 16). The temperature of the pre-diatreme polymetallic
mineralization has been fixed at 300°C based on the sulfide assemblage (Fig. 16).
The obtained values are δ18OFluid HT1bt vein=11.0 ‰ (n=4, σ=±0.3), δ18OFluid HT1px
vein=11.1‰ (n=7, σ=±0.3), δ18OFluid HT2 vein=10.9‰ (n=7, σ=±0.2), and δ18OFluid=10.2‰ (n=2,
σ=±0.4) for the pre-diatreme polymetallic mineralization Fig. 16). δ18O signature of fluids in
equilibrium with the different quartz generations (around 11‰) are slightly shifted towards heavier
compositions compared to the typical signature for primary magmatic fluids (6-9 ‰; Taylor, 1997).
Similar enriched compositions were also calculated for magmatic fluids forming porphyry Cu-Mo

112
mineralization in the Morococha district (up to 12‰; Catchpole et al., 2015a) located 100 km south of
Cerro de Pasco and also for fluids forming the Pasto Bueno tungsten-polymetallic deposit (up to 10‰;
Landis and Rye 1974) located 200 km north of Cerro de Pasco. Such elevated signatures for magmatic
fluids and therefore for the magma itself could reflect significant assimilation of crustal rocks enriched
in δ18O (Bindeman, 2008; Auer et al., 2009). Strong contamination by old continental crust of the
magmas at Cerro de Pasco has been evidenced by the Hf isotope signatures of zircons with εHf
ranging from -1 to -4 (Baumgartner et al., 2009), a typical feature of Miocene magmatism in central
Peru (Bissig and Tosdal, 2009; Rottier, 2017).
The constant δ18O composition of the fluid in equilibrium with quartz from HT1bt, HT1px and
HT2 veins and also with quartz associated to the pre-diatreme polymetallic mineralization points
towards a similar δ18O composition of the magmas from which the fluids are exsolved. The high δ18O
values of the mineralizing fluids exclude significant input of meteoric waters into the system, even
when the latter cooled down to ~300°C.

Figure 16: Summary δO18 SIMS analyses of quartz from HT1bt-, HT1px-, HT2-vein and from the late polymetallic
mineralization, and the calculated δO18 values of the fluid in equilibrium with quartz using the equation of Matsuhisa
et al. (1979) at temperatures of 700°C for HT1bt- and HT1px-veins, 600°C for HT2-veins based on microthermometry
and results obtained from the thermobarometers, and 300°C for pre-diatreme polymetallic mineralization based on
the sulfide assemblage.

113
Significance and origin of silicate melt inclusions in
hydrothermal veins
No spatial relationship has been observed between the SMIs and the CO2-rich high-density
vapor inclusions from the HT1 veins or with the polyphase brine inclusions from the HT2 veins. In the
absence of evidence of a genetic link our data cannot be used to determine fluid/melt partition
coefficients. The SMIs are hosted in hydrothermal quartz and therefore the silicate melt forming the
inclusions were transported by the high-temperature hydrothermal fluids and surprisingly no or only
weak evidence of interaction between the melt and the hydrothermal fluid has been observed. Indeed,
no depletion in elements strongly compatible in the fluid phase such as Na, Pb, Zn, and Cu was
recorded in the SMIs. Moreover, the chemical evolution drawn by the SMIs is marked by an
enrichment of elements incompatible in igneous minerals like Rb and a depletion of compatible
elements like Sr, suggesting that the chemical variations observed in the SMIs are controlled by
igneous processes.
SMIs trapped in vein quartz present a large range of Cs contents, from 3 to 102 ppm. It could
be interpreted as entrapment of melt droplets at different degrees of crystallization and differentiation
(Audétat et al., 2008; Audétat and Lowenstern 2014). Cesium, Sr and Rb concentrations in SMIs have
been reconstructed using a simple crystallization model of an evolved felsic melt in closed system
(Fig. 17). Crystal proportions chosen for this model are 50% of plagioclase, 35 % K-feldspar and 15%
quartz, in agreement with products crystallizing from a granitic melt (Whitney 1988); the starting
composition was fixed at 3.7 ppm Cs, 90 ppm Rb and 400 ppm Sr, based on composition of Andean
rhyolites (http://georoc.mpch-mainz.gwdg.de/georoc/).
The concentration of an element X in the residual melt was calculated assuming an
equilibrium fractional crystallization using the equation CL= Ci/[D-F(1-D)], where CL is the
concentration of the element of interest in the residual melt, Ci is the initial concentration of the
element of interest, D is the bulk partition coefficient of the element between minerals and melt, and F
is the amount of remaining magmatic liquid. Bulk partition coefficient was fixed at 0.026 for Cs, 0.214
for Rb and 8.12 for Sr based on compiled data from the GERM database (http://earthref.org/GERM/).
The model is able to reproduce the compositional evolution recorded in the studied SMIs. Strontium
concentrations of the SMIs are more depleted than the ones estimated by the model, such discrepancy
could be linked to minor crystallization of Sr-rich phases, such as apatite, not taken in account in the
model.
No systematic chemical evolution between SMIs hosted in HT1bt, in HT1px and in HT2 veins
was observed; moreover the entire range of Cs concentrations (from 10 to 100 ppm) is observed in
almost all veins. It has been even observed that the SMIs of a same quartz crystal yield Cs contents
differing up to 30 ppm. These results suggest that there is no correlation between the relative timing of

114
SMI entrapment and the initial silicate melt composition. Thus, we interpret the investigated SMIs as
melt droplets sampled at various isolated, not solidified parts of the underlying magma chamber (like
miarolitic cavities) by the ascending high-temperature magmatic hydrothermal fluids. This hypothesis
could explain the absence of systematic patterns in the chemical composition of the SMIs. No direct
relationship could be established between the SMIs and the magma from which the mineralizing fluids
were exsolved, and therefore they cannot be used for the quantification of the efficiency of ore-
forming processes. Nonetheless these SMIs are direct indication of the occurrence of heterogeneously
crystallized silicic plutonic bodies at depth.

Figure 17: A) Rb vs Cs and B) Sr vs Cs diagrams of the SMIs analyzed by LA-ICP-MS, the empty ellipses represent
the results of the crystallization model in closed system of an evolved felsic melt.

Cerro de Pasco mineralizing system


This study, combined with other recent results obtained on the porphyry-type and polymetallic
epithermal mineralizations of the Cerro de Pasco district (Baumgartner et al., 2009, Rottier et al.,
2016a and b, Rottier, 2017), indicates a complex history with at least three temporally distinct
porphyry-type and one polymetallic mineralization events before the formation of the large epithermal
polymetallic deposit. It confirms that the large epithermal polymetallic deposit of Cerro de Pasco is
formed in the upper part of a polycyclic porphyry system, as observed in other districts such as
Morococha (Catchpole et al., 2015a and 2015b).
Fluid inclusion and oxygen stable isotope studies conducted on the epithermal mineralization
point to an involvement of high-salinity magmatic fluids to explain the formation of the large
epithermal polymetallic deposit (Baumgartner et al., 2008; Rottier 2017). The Pb/Zn ratio of the bulk
ore from the epithermal polymetallic mineralization is similar to the Pb/Zn ratio of the polyphase brine
inclusions found in (i) HT2 veins (studied here), (ii) quartz-magnetite-chalcopyrite-pyrite porphyry-
style veinlets (PM2; Rottier et al., 2016a), and (iii) the quartz-magnetite-chalcopyrite veins
crosscutting clasts found in the quartz monzonite dykes (PM3; Rottier 2017; Fig. 18). As reported by
Kouzmanov and Pokrovski (2012), this ratio is not affected by phase-separation processes, and thus

115
reflects the original ratio of the silicate melt at the timing of fluid exsolution. The similar Pb/Zn ratios
found at Cerro de Pasco do not imply a direct genetic link, but may indicate that fluids forming the
epithermal polymetallic mineralization and the ones recorded in the different porphyry-type
mineralization events share common features; the similarity could potentially reflect a common
source. It is also interesting to note that the Pb/Zn ratios from the whole rock analyses of dacite,
rhyolite domes and quartz-monzonite dykes are similar (Fig. 18). Zinc and Pb have similar partition
coefficients between melt and hydrothermal fluid (Zajacz et al., 2008). Therefore, taking in account
the similar Pb/Zn ratios found in the magmatic rocks, in the polyphase brines from the different
porphyry-type mineralization events, and in the bulk ore of the shallow large epithermal
mineralization, a common source from a similar deep magmatic reservoir can be suggested.

Figure 18: Cu-Zn-Pb ternary diagram. Red and purple full circles are mean values of CO2-rich high-density vapor
FIAs respectively from HT1bt-veins and HT1px-veins. Blue circles represent mean values of polyphase brine FIAs
from HT2-veins. Empty red, purple and blue circle represent SMI compositions in HT1bt-, HT1px- and HT2-veins,
respectively. Light and dark gray full circle represent mean values polyphase brine FIAs respectively from the
quartz-magnetite-chalcopyrite-(pyrite) porphyry-style veinlets (PM2; Rottier et al., 2016) and from the quartz-
magnetite-chalcopyrite. Black squares represent LA-ICP-MS whole rock analyses of dacitic and rhyodacite domes
and quartz-monzonite dykes from Cerro de Pasco (Rottier et al., 2016a). Blue star represents the Cu-Pb-Zn ratio
calculated for the bulk ore of the epithermal polymetallic deposit using values published by Baumgartner et al. (2008).

116
Summary and conclusions
Our detailed study of porphyry-type quartz veins crosscutting hornfels and porphyritic igneous
clasts found in the phreatomagmatic diatreme breccia, allows reconstructing the different
hydrothermal events occurring below the large epithermal polymetallic mineralization of Cerro de
Pasco. Oxygen isotope data indicate a magmatic origin for the fluids forming the quartz from the
HT1bt, HT1px and the HT2 veins and also from the pre-diatreme polymetallic mineralization
reopenings. Fluid inclusion microthermometry and multiple mineral thermobarometers indicate that
HT1bt and HT1px quartz-molybdenite-(chalcopyrite)-(pyrite) veins were formed at temperatures above
700°C and at pressures varying from 500 to 900 bars for HT1bt veins, and from 700 to 1300 bars for
HT1px veins, i.e., pressures typical for porphyry Cu-Mo deposits. Fluids forming the HT1 veins, are
CO2-rich (XCO2 between 0.1 and 0.4) and S-rich, and are exsolved from a magma which never
reached fluid saturation before. HT2 quartz-molybdenite-(chalcopyrite)-(pyrite) veins are formed at
lower temperature (~600°C) and at pressures between 710 and 850 bars. Cesium concentrations of the
polyphase brine inclusions indicate that fluids forming the HT2 veins were exsolved from a less
differentiated magma than the one that exsolved the fluids forming the HT1 veins, suggesting injection
of mafic magmas into the underlying magma chamber. Fluid inclusions trapped in both HT1 and HT2
veins show lower Cu but similar Mo and higher Zn concentration ratios ([X] / [Na+K+Fe]) compared
to other porphyry Cu-Mo deposits (Ulrich et al., 2002; Landtwing et al., 2005 and 2010; Klemm et al.,
2007 and 2008; Stefanova et al., 2014). The SMIs found in hydrothermal quartz from HT1bt, HT1px.
and HT2 veins represent droplets of melts from various isolated not solidified parts of the deeply
seated magma chamber sampled by the high-temperature magmatic fluids during their ascent. Cooling
of the system down to 300°C prior to the formation of the diatreme breccia is indicated by the
occurrence of polymetallic mineralization in veins restricted to the clasts and also by the P-T-X
characteristics of the low-temperature brines and aqueous fluid inclusions. The latter exhibit the
typical signature of fluids associated to feldspar–destructive phyllic alteration.
The present results demonstrate existence of porphyry mineralization (including a polymetallic
stage) at depth that pre-dates formation of the diatreme at Cerro de Pasco and the formation of the
large shallow epithermal polymetallic Cerro de Pasco deposit. The Pb/Zn ratios observed in the
studied hypersaline fluid inclusions from the different porphyry-type events are similar and overlap
with the bulk Pb/Zn ratio of the large shallow polymetallic mineralization, and to those from the
different magmatic rocks. This similarity suggests a similar deep magmatic reservoir of the fluids
responsible for the different mineralization styles at Cerro de Pasco.

117
Acknowledgements
The present investigation was carried out with the support of the Swiss National Science
Foundation (FN 200020_134872). Funding for the SwissSIMS facility was provided by the KIP 6
“CASA” to LPB. We thank Volcan Companía Minera S.A. for providing logistical support and
geological data. We gratefully acknowledge Jean-Marie Boccard and Fabio Capponi for their help
with sample preparation and XRF analyses. We are grateful to Celeste Mercer and an anonymous
reviewer for their constructive comments.

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122
Figure A.1:

SEM-CL image of quartz crystals from HT2 veins showing os-


cillatory growth zones (sample BR-267). Blue circles indicate the
location of LA-ICP-MS ablation pits, Ti and Al concentrations are
indicated in red and black, respectively. Bracket values represent
the limit of detection (LOD) and were indicated when analyzed
elements were below LOD. Q1 and Q2 are the two generations
observed in HT2-veins, the dashed yellow lines mark the between
the two generations.

123
Figure A.2:

A) CO2-rich high-density vapor inclusion in an HT1px vein, the red cross represents position of the laser
during Raman analysis. B) Raman spectra of the aqueous phase of the CO2-rich high-density vapor inclu-
sion done at different temperatures (A). The spectra show detectable amount of SO42- ion in solution; C)
Polyphase brine inclusion in a HT2 vein, the red cross represents the position of the laser during Raman
analysis; D) Raman spectrum of the vapor phase of a polyphase brine inclusion done at room temperature
(C). The spectrum has the characteristic CO2 double peaks

124
Figure A.3:

Ternary Na-K-Fe diagram. Each circle represents the mean value of a fluid inclusion assemblage. Purple
and red circle are CO2-rich high-density vapor FIAs respectively in HT1px-veins and HT1bt-veins. Blue
circles represent polyphase brine FIAs in HT2-veins. Green and yellow circles are respectively low-tem-
perature brine and aqueous FIAs in HT1- and HT2-veins.

125
Figure A.4:
Pressure-temperature diagrams, the
black lines represent A) Ti-in-quartz
isopleths calculated from the thermoba-
rometer of Huang and Audétat (2012),
B) Zr-in-rutile isopleths calculated from
the thermobarometer of Tomkins et
al. (2007), C) Zr-in-titanite isopleths
calculated from the thermobarometer of
Hayden et al. (2008). Blue lines repre-
sent the mean value and blue shaded
fields represent the mean ± 1σ range of
values of Ti (A) or Zr (B)concentration
of quartz (A) and rutile (B) from HT2-
veins. Purple line represents the mean
value and purple shaded field represent
the mean ± 1σ range of values of Ti
(A) and Zr (B and C) concentration
of quartz (A), rutile (B) and Titanite
(C) from HT1px-veins. Red line rep-
resents the mean value and red shaded
field represents the mean ± 1σ range of
values of Ti (A) and Zr (B and C) con-
centration of quartz (A), rutile (B) and
Titanite (C) from HT1bt-veins.

126
Table A.1: LA-ICP-MS machine and data acquisition parameters

Fluid inclusions Silicate melt Trace element


Excimer 193 nm ArF laser Compex 110I
hosted in Quartz inclusions quartz/rutile/titanite

Output energy 24-30 mJ 24-26 mJ 24-30 mJ


Repetition rate 10 Hz 10 Hz 10Hz
Crater sizes 15-60 µm 15-40 µm 20-60 µm
In-house built In-house built
glass chamber glass chamber In-house built glass
with anti- with anti- chamber with anti-
Ablation cell
reflection coated reflection coated reflection coated silica
silica glass silica glass glass window
window window
Cell He gas flow 1.1 l/min He 1.1 l/min He 1.1 l/min He
Cell H gas flow 5 ml/min H2 5 ml/min H2 5 ml/min H2

Data acquisition parameters


Readings per replicate 400 400 400
Points per peak 1 per mass 1 per mass 1 per mass
Oxide production rate tuned to <0.5 % ThO
tuned to <0.5 % ThO tuned to <0.5 % ThO
Dwell time per isotope 40 ms fo Fe, 30 ms for Ag 10 ms for all isotops 10 ms for all isotops
10 ms for the others

7
7 Li, 11B, 23Na,
Li, 11B, 25
23 Mg, 27Al, 29Si,
Na,27Al,29Si, 34S, 34
7
Li, 11B, 23Na, 25Mg, 27Al,
39 44 49 S, 39K, 44Ca, 49Ti, 29
K, Ca, Ti, 55 Si, 34S, 39K, 44Ca, 49Ti,
55 57 65 Mn, 57Fe, 65Cu, 55
Mn, Fe, Cu, 66 Mn, 57Fe, 65Cu, 66Zn,
66 75 85 Zn, 75As, 85Rb, 75
Zn, As, Rb, 88 As, 85Rb, 88Sr, 89Y, 90Zr,
Isotopes analyzed (fluid inclusions programme) 88 98 Sr, 89Y, 90Zr, 93 98
Sr, Mo 93 98 Nb, Mo, 107Ag,118Sn,
107 118 Nb, Mo, 121 133
Ag, Sn, 107 Sb, Cs, 137Ba, 139La,
121 125 133 Ag,118Sn, 121Sb, 140 173
Sb, Te, Cs, 133 Ce, Yb, 184W, 197Au,
137 184 197 Cs, 137Ba, 139La, 208
Ba, W, Au, 140 Pb
208 Ce, 173Yb, 184W,
Pb 197
Au, 208Pb

127
Table A.2: Coordinates, azimut, inclinaison of the drillholes where mineralized clasts were found

Drillhole# Z N E Azimuth Inclination interval* Clasts**


DDH-S-CE-14-001 4237,6 9409,7 8899 180,5 -61 0-84,60 Numerous clasts
DDH-S-CE-14-002 4195 9667,5 8858,7 183,1 -25 36-86,5 Few clasts
DDH-S-CE-14-004 4296 9402,6 8905,3 174,9 -65 0-78,4 Numerous clasts
DDH-S-CE-14-005 4297 9515 8860,4 319,5 -88 46,8-112,55 Numerous clasts
19,45-48 Few clasts
DDH-S-CE-14-006 4244 9477 8882,7 178,2 -46 48-68,3 Numerous clasts
92,2-152,5 No clast
DDH-u-CE-14-007 4110 10248,6 8824,4 180,35 37 14,7-41,60 No clast
14,5-49 No clast
DDH-u-CE-14-008 4110 10248 8821,4 177,5 35
49-127,6 Numerous clasts
DDH-S-CE-14-009 4246 9513,667 8860,959 188,8 -45 69-217 Numerous clasts
DDH-S-CE-14-010 4238 9400 8898,4 270,1 -22 31-115 Few clasts
DDH-S-CE-13-054 4196 9680 8860 177,9 -59 38,20-74 No clast
DDH-S-CE-13-170 4304 10390 8780 0,1 -50 No clast
7,10-19,6 Few clasts
DDH-S-CE-13-181 4309 10309 8799,8 0,9 -44
47,1-92,2 Few clasts
DDH-S-CE-13-192 4308 10308,9 8800 184,8 -59 21-79,5 No clast
DDH-S-CE-13-194 4309 10298 8780 194,3 -66 nd No clast
DDH-S-CE-13-208 4192 9634 8880 179,5 -49 0-36,3 Few clasts
DDH-S-CE-13-217 4197 9830 8861 179,9 -40 84,25-99,1 Few clast
DDH-S-CE-13-220 4291 10150 8874 91,5 -48 100,9-122,95 No clast

* Interval where the breccias were intercepted


** Few clasts correspond to 1-3 clast every 10 of meters of breccia intercepted and numerous

128
Table A.3: LA-ICP-MS analyses of quartz, titanite and rutile crystals

Li B Na Mg P K Mn Fe Cu Zn As Rb Sr Y Zr Nb Mo
Sample # Vein-type mineral Al (ppm) Si (ppm) Ca (ppm) Ti (ppm)
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)

257 HT1bt quartz 9,9 B.D.L. B.D.L. B.D.L. 165 465128 33,3 B.D.L. 847 83,2 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
257 HT1bt quartz 17,8 B.D.L. 2,1 B.D.L. 197 465128 B.D.L. B.D.L. 850 64,3 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
257 HT1bt quartz 13,5 B.D.L. 4,4 2,4 206 465128 32 B.D.L. 889 49,1 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
257 HT1bt quartz B.D.L. B.D.L. 2,8 B.D.L. 239 465128 59,2 B.D.L. 687 32,3 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
257 HT1bt quartz 11,9 B.D.L. 5,1 B.D.L. 197 465128 B.D.L. B.D.L. 663 74,7 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
257 HT1bt quartz 4,7 B.D.L. B.D.L. B.D.L. 172 465128 23,1 B.D.L. 943 142 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
257 HT1bt quartz 9,1 B.D.L. 21,9 B.D.L. 229 465128 27,1 B.D.L. 363 72,5 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,21 0,08 B.D.L. B.D.L. B.D.L. B.D.L.
257 HT1bt quartz 12,4 B.D.L. B.D.L. 2,9 183 465128 33,1 B.D.L. 263 51,3 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,33 B.D.L. B.D.L. B.D.L.
257 HT1bt quartz 6,5 B.D.L. 78,4 4,1 349 465128 37,2 B.D.L. B.D.L. 176 5,1 194 B.D.L. B.D.L. B.D.L. 0,73 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
257 HT1bt quartz 6,5 B.D.L. 78,4 4,1 349 465128 37,2 B.D.L. B.D.L. 176 5,1 194 B.D.L. B.D.L. B.D.L. 0,73 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
257 HT1bt quartz 8,9 B.D.L. B.D.L. 0,9 158 465128 29,8 B.D.L. 348 54,1 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
257 HT1bt quartz 8,3 B.D.L. B.D.L. B.D.L. 152 465128 34,1 B.D.L. 420 52,9 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
257 HT1bt quartz 7 B.D.L. B.D.L. B.D.L. 167 465128 26,1 B.D.L. 369 48,3 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
257 HT1bt quartz B.D.L. B.D.L. 6,3 B.D.L. 181 465128 B.D.L. B.D.L. B.D.L. 44,9 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
257 HT1bt quartz 7,6 B.D.L. 2,4 N.A. 207 465128 N.A. B.D.L. 854 79,7 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,14 0,07 N.A. N.A. N.A. B.D.L.
257 HT1bt quartz 4,3 B.D.L. 3,3 N.A. 168 465128 N.A. B.D.L. 785 120 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.
257 HT1bt quartz 5,7 B.D.L. 7,8 N.A. 155 465128 N.A. B.D.L. 865 116 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,22 0,09 N.A. N.A. N.A. B.D.L.
257 HT1bt quartz 5,3 B.D.L. 2,5 N.A. 173 465128 N.A. B.D.L. 741 133 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,06 N.A. N.A. N.A. B.D.L.
257 HT1bt quartz 5,8 B.D.L. 0,57 N.A. 118 465128 N.A. B.D.L. 763 68,2 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.
257 HT1bt quartz B.D.L. B.D.L. 33,8 N.A. 154 465128 N.A. B.D.L. B.D.L. 94,1 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,35 N.A. N.A. N.A. B.D.L.
257 HT1bt quartz 6 B.D.L. 3,7 N.A. 93,8 465128 N.A. B.D.L. 919 57,3 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.
257 HT1bt quartz 6,6 B.D.L. 5,7 N.A. 179 465128 N.A. B.D.L. 827 50,3 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,08 N.A. N.A. N.A. B.D.L.
261 HT1bt quartz 4,6 B.D.L. B.D.L. B.D.L. 79,3 465128 38,9 B.D.L. 329 44,5 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
261 HT1bt quartz 3,7 B.D.L. B.D.L. B.D.L. 72,9 465128 29,7 B.D.L. B.D.L. 50,7 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
261 HT1bt quartz 3,6 B.D.L. B.D.L. B.D.L. 84,9 465128 34,3 B.D.L. 295 69,2 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
261 HT1bt quartz B.D.L. B.D.L. 3,7 B.D.L. 59,6 465128 B.D.L. B.D.L. B.D.L. 59,3 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
261 HT1bt quartz 3,6 B.D.L. 5 B.D.L. 135 465128 B.D.L. B.D.L. 458 100 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 1,6 B.D.L. B.D.L. B.D.L. B.D.L.
261 HT1bt quartz 3 B.D.L. B.D.L. 1,3 77,9 465128 22 B.D.L. 309 54,3 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
261 HT1bt quartz 4,3 B.D.L. 10,4 B.D.L. 82,4 465128 26,4 B.D.L. B.D.L. 70,7 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
261 HT1bt quartz 3,8 B.D.L. B.D.L. B.D.L. 71,8 465128 35,9 B.D.L. 242 55,4 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.

129
Table A.3: LA-ICP-MS analyses of quartz, titanite and rutile crystals

Ag Sn Sb Te Cs Ba La Ce Yb W Au Pb
Sample # Vein-type mineral
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)

257 HT1bt quartz B.D.L. 41,7 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
257 HT1bt quartz B.D.L. 43,9 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
257 HT1bt quartz B.D.L. 40 0,35 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
257 HT1bt quartz B.D.L. 46 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
257 HT1bt quartz B.D.L. 42,2 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
257 HT1bt quartz B.D.L. 39,1 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
257 HT1bt quartz B.D.L. 34,2 B.D.L. B.D.L. B.D.L. 0,76 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
257 HT1bt quartz B.D.L. 23,2 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,13 B.D.L. B.D.L. B.D.L. B.D.L.
257 HT1bt quartz B.D.L. 33,8 B.D.L. B.D.L. 0,15 0,93 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
257 HT1bt quartz B.D.L. 33,8 B.D.L. B.D.L. 0,15 0,93 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
257 HT1bt quartz B.D.L. 29,9 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,04 B.D.L. B.D.L. B.D.L.
257 HT1bt quartz B.D.L. 33,4 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
257 HT1bt quartz B.D.L. 30,9 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
257 HT1bt quartz B.D.L. 37,5 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 4,9 B.D.L. B.D.L.
257 HT1bt quartz B.D.L. 37,5 B.D.L. B.D.L. 0,36 B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. N.A.
257 HT1bt quartz B.D.L. 38,5 B.D.L. B.D.L. B.D.L. 0,29 N.A. N.A. N.A. B.D.L. B.D.L. N.A.
257 HT1bt quartz B.D.L. 38,6 B.D.L. B.D.L. 0,22 B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. N.A.
257 HT1bt quartz B.D.L. 39,2 B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. N.A.
257 HT1bt quartz B.D.L. 37,5 B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. N.A.
257 HT1bt quartz B.D.L. 131 B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. N.A.
257 HT1bt quartz B.D.L. 38,6 B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. N.A.
257 HT1bt quartz B.D.L. 42,5 B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. N.A.
261 HT1bt quartz B.D.L. 30,2 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
261 HT1bt quartz B.D.L. 29,3 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
261 HT1bt quartz B.D.L. 31,3 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
261 HT1bt quartz B.D.L. 28 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
261 HT1bt quartz B.D.L. 31,7 B.D.L. B.D.L. B.D.L. 2,2 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
261 HT1bt quartz B.D.L. 30,6 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
261 HT1bt quartz B.D.L. 30,1 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
261 HT1bt quartz B.D.L. 30,9 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.

130
Table A.3: LA-ICP-MS analyses of quartz, titanite and rutile crystals

Li B Na Mg P K Mn Fe Cu Zn As Rb Sr Y Zr Nb Mo
Sample # Vein-type mineral Al (ppm) Si (ppm) Ca (ppm) Ti (ppm)
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)

261 HT1bt quartz 5 B.D.L. B.D.L. B.D.L. 80 465128 22,9 B.D.L. 382 171 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,09 B.D.L. B.D.L.
261 HT1bt quartz 3,8 B.D.L. B.D.L. B.D.L. 71,8 465128 21,3 B.D.L. 458 97,5 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
261 HT1bt quartz 5,3 B.D.L. 8,8 3,2 196 465128 27,7 B.D.L. 330 138 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,28 0,1 B.D.L. B.D.L. B.D.L. B.D.L.
261 HT1bt quartz 3,4 B.D.L. B.D.L. B.D.L. 69,6 465128 32,9 B.D.L. 417 67 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
261 HT1bt quartz 4,1 B.D.L. B.D.L. B.D.L. 69,9 465128 40,2 B.D.L. 248 41,6 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
261 HT1bt quartz 3,7 B.D.L. B.D.L. B.D.L. 77,8 465128 26,5 B.D.L. 288 66,1 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
261 HT1bt quartz 4,4 B.D.L. B.D.L. B.D.L. 75,6 465128 22,1 B.D.L. 289 55,8 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
261 HT1bt quartz 5,2 B.D.L. 2,8 N.A. 164 465128 N.A. B.D.L. 288 96,6 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,26 0,05 N.A. N.A. N.A. B.D.L.
311 HT1bt quartz 3,5 5,8 0,76 B.D.L. 142 465128 29,9 B.D.L. 629 78,1 B.D.L. B.D.L. B.D.L. 1,6 8 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
311 HT1bt quartz 2,3 5 0,35 B.D.L. 106 465128 33,3 B.D.L. 655 73,5 B.D.L. B.D.L. B.D.L. B.D.L. 7,8 B.D.L. B.D.L. 0,01 B.D.L. B.D.L. B.D.L.
311 HT1bt quartz 2,4 3,2 8,8 1,3 131 465128 25,2 B.D.L. 365 73,8 1,5 7,3 B.D.L. 2,4 5,8 0,06 0,17 B.D.L. B.D.L. B.D.L. B.D.L.
311 HT1bt quartz 2,7 6,5 3 B.D.L. 136 465128 29,7 B.D.L. 364 57,7 B.D.L. B.D.L. B.D.L. 2 7,1 B.D.L. 0,03 B.D.L. B.D.L. B.D.L. B.D.L.
311 HT1bt quartz 3,6 5,8 0,33 B.D.L. 168 465128 27,1 B.D.L. 582 61,5 B.D.L. B.D.L. B.D.L. 1,3 4,1 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
311 HT1bt quartz 2,9 6,4 0,69 B.D.L. 138 465128 27,7 B.D.L. 456 64,9 B.D.L. B.D.L. B.D.L. B.D.L. 4,9 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
311 HT1bt quartz 4,1 B.D.L. 1,8 B.D.L. 194 465128 32,1 B.D.L. 426 77 B.D.L. B.D.L. B.D.L. B.D.L. 7,2 B.D.L. 0,03 B.D.L. B.D.L. B.D.L. B.D.L.
311 HT1bt quartz 3,7 8,4 5,4 N.A. 211 465128 N.A. B.D.L. 635 69,1 B.D.L. B.D.L. B.D.L. 4,6 5,3 B.D.L. 0,03 N.A. N.A. N.A. B.D.L.
311 HT1bt quartz 3,2 B.D.L. 1,8 N.A. 126 465128 N.A. B.D.L. 805 87,2 B.D.L. B.D.L. B.D.L. B.D.L. 9,1 B.D.L. 0,06 N.A. N.A. N.A. B.D.L.
311 HT1bt quartz 1,4 B.D.L. 0,89 N.A. 112 465128 N.A. B.D.L. 612 50,8 B.D.L. B.D.L. B.D.L. B.D.L. 2,2 B.D.L. 0,05 N.A. N.A. N.A. B.D.L.
311 HT1bt quartz 3,5 6,4 7,1 N.A. 122 465128 N.A. B.D.L. 906 76,1 B.D.L. B.D.L. B.D.L. 6,9 4,9 B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.
311 HT1bt quartz 1,9 4,2 0,49 N.A. 122 465128 N.A. B.D.L. 631 72,7 B.D.L. B.D.L. B.D.L. B.D.L. 6,2 B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.
311 HT1bt quartz 2,4 7,7 17,6 N.A. 136 465128 N.A. B.D.L. 508 83,5 B.D.L. 9,6 0,63 B.D.L. 8,5 0,09 0,04 N.A. N.A. N.A. B.D.L.
311 HT1bt quartz 5,2 11,6 17,2 N.A. 249 465128 N.A. B.D.L. 431 72,5 B.D.L. B.D.L. B.D.L. B.D.L. 9,8 0,14 0,68 N.A. N.A. N.A. B.D.L.
311 HT1bt quartz 3,9 10,2 14,4 N.A. 213 465128 N.A. B.D.L. 432 65,2 B.D.L. B.D.L. 0,88 B.D.L. 6,9 B.D.L. 0,22 N.A. N.A. N.A. B.D.L.
311 HT1bt quartz 2,8 B.D.L. 4 N.A. 190 465128 N.A. B.D.L. 440 73,2 B.D.L. B.D.L. B.D.L. B.D.L. 6,6 B.D.L. 0,1 N.A. N.A. N.A. B.D.L.
311 HT1bt quartz 2,4 B.D.L. 2,1 N.A. 159 465128 N.A. B.D.L. 335 76,7 B.D.L. B.D.L. B.D.L. B.D.L. 9,5 B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.
311 HT1bt quartz 2,5 7 2,4 N.A. 186 465128 N.A. B.D.L. 420 70,2 B.D.L. B.D.L. B.D.L. 0,68 5,5 B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.
311 HT1bt quartz 2 14,2 1,2 N.A. 181 465128 N.A. B.D.L. 326 45 B.D.L. B.D.L. B.D.L. B.D.L. 7,5 B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.
311 HT1bt quartz 1,4 B.D.L. 2,7 N.A. 161 465128 N.A. B.D.L. 347 65 B.D.L. B.D.L. B.D.L. B.D.L. 5,6 B.D.L. 0,01 N.A. N.A. N.A. B.D.L.
311 HT1bt quartz 1,6 7,8 0,76 N.A. 134 465128 N.A. B.D.L. 350 60,4 B.D.L. B.D.L. B.D.L. 4,1 7,4 B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.
311 HT1bt quartz 1,9 5,8 B.D.L. N.A. 138 465128 N.A. B.D.L. 392 61,7 B.D.L. B.D.L. B.D.L. 1,8 6,3 B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.
311 HT1bt quartz 1,8 5,3 0,64 N.A. 118 465128 N.A. B.D.L. 432 62,1 B.D.L. B.D.L. B.D.L. 0,9 3,7 B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.

131
Table A.3: LA-ICP-MS analyses of quartz, titanite and rutile crystals

Ag Sn Sb Te Cs Ba La Ce Yb W Au Pb
Sample # Vein-type mineral
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)

261 HT1bt quartz B.D.L. 28 B.D.L. B.D.L. B.D.L. B.D.L. 0,05 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
261 HT1bt quartz B.D.L. 27,2 B.D.L. B.D.L. 0,03 B.D.L. 0,03 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
261 HT1bt quartz B.D.L. 30,1 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
261 HT1bt quartz B.D.L. 27,7 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,22 B.D.L. B.D.L.
261 HT1bt quartz B.D.L. 30,2 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
261 HT1bt quartz 0,11 26,4 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
261 HT1bt quartz B.D.L. 30,5 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
261 HT1bt quartz B.D.L. 30,4 B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
311 HT1bt quartz B.D.L. B.D.L. 0,14 B.D.L. B.D.L. B.D.L. 0,01 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
311 HT1bt quartz B.D.L. B.D.L. 0,17 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
311 HT1bt quartz 0,01 B.D.L. B.D.L. B.D.L. 0,05 B.D.L. N.A. B.D.L. B.D.L. B.D.L. B.D.L. 0,22
311 HT1bt quartz B.D.L. B.D.L. B.D.L. B.D.L. 0,01 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
311 HT1bt quartz B.D.L. 0,69 B.D.L. 0,1 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
311 HT1bt quartz B.D.L. 0,61 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
311 HT1bt quartz B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,32 0,01 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
311 HT1bt quartz 0,21 B.D.L. 0,47 B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. 564
311 HT1bt quartz B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
311 HT1bt quartz B.D.L. B.D.L. B.D.L. B.D.L. 0,08 B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
311 HT1bt quartz B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. 0,23
311 HT1bt quartz B.D.L. 0,87 0,1 B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
311 HT1bt quartz B.D.L. B.D.L. 0,2 B.D.L. 0,03 B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
311 HT1bt quartz B.D.L. B.D.L. B.D.L. B.D.L. 0,11 0,54 N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
311 HT1bt quartz B.D.L. B.D.L. B.D.L. B.D.L. 0,04 B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
311 HT1bt quartz B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
311 HT1bt quartz B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. 0,12
311 HT1bt quartz B.D.L. 0,39 B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
311 HT1bt quartz B.D.L. B.D.L. B.D.L. 0,49 B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
311 HT1bt quartz B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
311 HT1bt quartz B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
311 HT1bt quartz B.D.L. B.D.L. B.D.L. 0,18 B.D.L. 0,04 N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
311 HT1bt quartz B.D.L. 0,47 B.D.L. B.D.L. N.A. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.

132
Table A.3: LA-ICP-MS analyses of quartz, titanite and rutile crystals

Li B Na Mg P K Mn Fe Cu Zn As Rb Sr Y Zr Nb Mo
Sample # Vein-type mineral Al (ppm) Si (ppm) Ca (ppm) Ti (ppm)
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)

311 HT1bt quartz 1,7 B.D.L. 1,1 N.A. 131 465128 N.A. B.D.L. 338 61,6 B.D.L. B.D.L. B.D.L. B.D.L. 5,4 B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.
259 HT1px quartz 5 10,8 10,4 1,6 121 465128 33,6 B.D.L. 420 27,2 B.D.L. B.D.L. B.D.L. B.D.L. 4,1 0,16 0,18 B.D.L. B.D.L. B.D.L. B.D.L.
259 HT1px quartz 5,2 10,2 16,2 37,5 187 465128 36,4 B.D.L. 449 20,9 B.D.L. 22,9 B.D.L. B.D.L. 5,3 0,33 0,37 B.D.L. B.D.L. B.D.L. B.D.L.
259 HT1px quartz 4,4 7,3 0,79 10 111 465128 32,6 B.D.L. 261 39,2 B.D.L. B.D.L. 0,52 B.D.L. 3,4 0,04 B.D.L. B.D.L. B.D.L. 0,02 B.D.L.
259 HT1px quartz 6,5 6,8 12,7 2,2 182 465128 34,2 B.D.L. 447 35,7 B.D.L. B.D.L. B.D.L. B.D.L. 3,5 0,22 1,2 B.D.L. B.D.L. B.D.L. B.D.L.
259 HT1px quartz 4,6 6,4 3,6 1,3 112 465128 31,1 B.D.L. 422 30,1 B.D.L. B.D.L. B.D.L. B.D.L. 5,4 B.D.L. 0,56 B.D.L. B.D.L. B.D.L. B.D.L.
259 HT1px quartz 4,7 7,8 0,21 1,6 80,6 465128 30,6 B.D.L. 482 31,4 B.D.L. B.D.L. B.D.L. B.D.L. 4,4 B.D.L. B.D.L. 0,01 B.D.L. B.D.L. B.D.L.
259 HT1px quartz 10,2 B.D.L. 8,1 43,1 389 465128 B.D.L. 75,5 849 52,1 7,5 150 B.D.L. B.D.L. B.D.L. 1,1 0,07 0,04 B.D.L. B.D.L. B.D.L.
259 HT1px quartz 7 B.D.L. 1,7 4,8 134 465128 28,2 B.D.L. 835 34,8 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
259 HT1px quartz 11,5 B.D.L. B.D.L. B.D.L. 95,2 465128 B.D.L. B.D.L. 929 38,6 B.D.L. B.D.L. 2,5 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
259 HT1px quartz 4,5 B.D.L. 11,4 6,9 89,5 465128 24,7 B.D.L. 1085 37,9 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,46 B.D.L. B.D.L. B.D.L. B.D.L.
259 HT1px quartz 3,6 11,1 2,4 N.A. 77,5 465128 N.A. B.D.L. 381 44,1 B.D.L. B.D.L. B.D.L. B.D.L. 4,2 B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.
259 HT1px quartz 4 B.D.L. B.D.L. N.A. 97,9 465128 N.A. B.D.L. 438 47 B.D.L. B.D.L. B.D.L. B.D.L. 4,5 B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.
259 HT1px quartz 4,7 6,4 1,2 N.A. 85,2 465128 N.A. B.D.L. 478 38,6 B.D.L. B.D.L. B.D.L. B.D.L. 4,2 B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.
259 HT1px quartz 4,6 B.D.L. 28,2 N.A. 606 465128 N.A. 177 140 41,3 1,7 155 B.D.L. B.D.L. 5,7 1,8 0,18 N.A. N.A. N.A. B.D.L.
259 HT1px quartz 5,3 B.D.L. 37,4 N.A. 135 465128 N.A. B.D.L. 477 56,4 B.D.L. B.D.L. B.D.L. B.D.L. 4,3 B.D.L. 0,13 N.A. N.A. N.A. B.D.L.
259 HT1px quartz 4,1 B.D.L. 0,77 N.A. 115 465128 N.A. B.D.L. 393 64,6 B.D.L. B.D.L. B.D.L. B.D.L. 3,8 0,12 0,05 N.A. N.A. N.A. B.D.L.
259 HT1px quartz 6,6 B.D.L. 8,9 N.A. 172 465128 N.A. B.D.L. 248 52,7 B.D.L. B.D.L. B.D.L. B.D.L. 5,2 0,17 0,06 N.A. N.A. N.A. B.D.L.
259 HT1px quartz 7,9 5,8 2,9 N.A. 476 465128 N.A. 162 406 44,2 1,9 35,4 0,48 B.D.L. 3,9 1,5 0,07 N.A. N.A. N.A. B.D.L.
259 HT1px quartz 5,6 B.D.L. 24,8 N.A. 116 465128 N.A. B.D.L. 232 75,7 0,58 B.D.L. B.D.L. 1,3 3,8 0,06 0,02 N.A. N.A. N.A. B.D.L.
259 HT1px quartz 3,3 B.D.L. 30,9 N.A. 79,2 465128 N.A. B.D.L. 767 35,7 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,06 N.A. N.A. N.A. B.D.L.
300 HT1px quartz 4,4 4,1 B.D.L. N.A. 61,2 465128 N.A. B.D.L. 447 38,8 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.
300 HT1px quartz 4,8 8,7 1,1 N.A. 71,1 465128 N.A. B.D.L. 343 51,9 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.
300 HT1px quartz 4 B.D.L. 9,1 N.A. 60,7 465128 N.A. B.D.L. 300 19 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.
300 HT1px quartz 4,8 B.D.L. B.D.L. N.A. 67,6 465128 N.A. B.D.L. 284 23,5 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.
300 HT1px quartz 3,6 B.D.L. 7,6 N.A. 73,9 465128 N.A. B.D.L. 336 20,3 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,1 0,04 N.A. N.A. N.A. B.D.L.
300 HT1px quartz 3,5 B.D.L. 8,4 N.A. 58 465128 N.A. B.D.L. 446 29,7 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.
300 HT1px quartz 3,5 B.D.L. 5,6 N.A. 55,6 465128 N.A. B.D.L. 436 32,8 B.D.L. B.D.L. 4,1 B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.
300 HT1px quartz 2,6 B.D.L. B.D.L. B.D.L. 46 465128 25,9 B.D.L. 248 30,1 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
300 HT1px quartz 2,8 B.D.L. B.D.L. B.D.L. 58 465128 33 B.D.L. 396 46,5 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
300 HT1px quartz 2,6 B.D.L. B.D.L. B.D.L. 59,3 465128 23,8 B.D.L. 279 46,9 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.

133
Table A.3: LA-ICP-MS analyses of quartz, titanite and rutile crystals

Ag Sn Sb Te Cs Ba La Ce Yb W Au Pb
Sample # Vein-type mineral
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)

311 HT1bt quartz B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
259 HT1px quartz B.D.L. B.D.L. 0,42 B.D.L. 0,16 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
259 HT1px quartz B.D.L. B.D.L. 0,67 B.D.L. 0,29 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
259 HT1px quartz B.D.L. B.D.L. 1,1 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
259 HT1px quartz B.D.L. B.D.L. 0,23 0,53 0,13 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
259 HT1px quartz B.D.L. B.D.L. 0,71 B.D.L. 0,04 0,54 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
259 HT1px quartz B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
259 HT1px quartz B.D.L. 39,2 0,4 B.D.L. 0,17 B.D.L. B.D.L. 0,07 B.D.L. B.D.L. B.D.L. B.D.L.
259 HT1px quartz B.D.L. 34 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
259 HT1px quartz B.D.L. 45,9 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
259 HT1px quartz B.D.L. 38,2 1,1 B.D.L. 0,05 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,14
259 HT1px quartz B.D.L. B.D.L. 0,53 B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
259 HT1px quartz B.D.L. B.D.L. 1 B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
259 HT1px quartz B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. 0,07 B.D.L. B.D.L.
259 HT1px quartz B.D.L. B.D.L. 3,6 B.D.L. 0,19 0,55 N.A. N.A. N.A. B.D.L. B.D.L. 0,45
259 HT1px quartz B.D.L. B.D.L. 0,52 B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
259 HT1px quartz 0,06 B.D.L. B.D.L. B.D.L. 0,07 B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
259 HT1px quartz B.D.L. B.D.L. B.D.L. B.D.L. 0,16 B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
259 HT1px quartz B.D.L. B.D.L. 0,69 B.D.L. 0,19 0,91 N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
259 HT1px quartz B.D.L. B.D.L. 0,72 B.D.L. 0,02 0,07 N.A. N.A. N.A. B.D.L. B.D.L. 0,18
259 HT1px quartz B.D.L. 35,9 0,24 0,06 B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. 0,14 N.A.
300 HT1px quartz B.D.L. 16,7 B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
300 HT1px quartz B.D.L. 18,9 B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
300 HT1px quartz B.D.L. 23,9 B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
300 HT1px quartz B.D.L. 25,9 B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
300 HT1px quartz B.D.L. 24,1 B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
300 HT1px quartz B.D.L. 32,7 B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
300 HT1px quartz B.D.L. 29,4 B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
300 HT1px quartz B.D.L. 24,4 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
300 HT1px quartz B.D.L. 31,1 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
300 HT1px quartz B.D.L. 25 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.

134
Table A.3: LA-ICP-MS analyses of quartz, titanite and rutile crystals

Li B Na Mg P K Mn Fe Cu Zn As Rb Sr Y Zr Nb Mo
Sample # Vein-type mineral Al (ppm) Si (ppm) Ca (ppm) Ti (ppm)
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)

300 HT1px quartz B.D.L. B.D.L. B.D.L. B.D.L. 53,6 465128 B.D.L. B.D.L. 334 34,9 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
300 HT1px quartz 4,1 B.D.L. B.D.L. B.D.L. 63,3 465128 23,7 B.D.L. 392 54,4 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
300 HT1px quartz 3,3 B.D.L. 4,6 B.D.L. 54,7 465128 20,6 B.D.L. 422 70,9 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,09 B.D.L.
300 HT1px quartz 3,2 B.D.L. B.D.L. B.D.L. 45,5 465128 B.D.L. B.D.L. B.D.L. 24,8 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
300 HT1px quartz 3,2 B.D.L. B.D.L. B.D.L. 56,4 465128 20,9 B.D.L. 391 34,6 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
300 HT1px quartz 2,8 5 2,1 0,74 64,7 465128 20 B.D.L. 337 36,3 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,03 B.D.L. B.D.L. B.D.L. B.D.L.
300 HT1px quartz 9,1 B.D.L. 1,9 B.D.L. 107 465128 25,3 B.D.L. 324 22,5 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
300 HT1px quartz 7,9 B.D.L. 22,6 B.D.L. 69,1 465128 B.D.L. B.D.L. B.D.L. 26,1 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
300 HT1px quartz 6,1 B.D.L. 11,4 B.D.L. 151 465128 23,1 B.D.L. 418 25,1 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,17 0,32 B.D.L. B.D.L. B.D.L. B.D.L.
300 HT1px quartz 4,7 B.D.L. 18,2 B.D.L. 208 465128 24,1 B.D.L. 401 28,8 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,3 0,18 B.D.L. B.D.L. B.D.L. B.D.L.
300 HT1px quartz 2,6 B.D.L. B.D.L. B.D.L. 57,4 465128 28,4 B.D.L. 360 28,9 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
300 HT1px quartz 18,3 B.D.L. 11,5 1,1 262 465128 20,5 B.D.L. 317 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,31 0,64 B.D.L. B.D.L. B.D.L. 2,9
300 HT1px quartz 7,4 B.D.L. 28,7 1,1 171 465128 20,9 B.D.L. 347 27,1 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,21 B.D.L. B.D.L. B.D.L. B.D.L.
300 HT1px quartz 2,3 B.D.L. B.D.L. B.D.L. 72,1 465128 28,9 B.D.L. 367 35,4 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz 6,2 B.D.L. B.D.L. 3,9 281 465128 27,5 B.D.L. 344 16,6 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,09 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz 3,8 B.D.L. B.D.L. 6,1 255 465128 29,7 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz 4,2 B.D.L. B.D.L. B.D.L. 262 465128 19,9 B.D.L. 351 7,8 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,2 B.D.L. B.D.L. 0,06 B.D.L. B.D.L.
267 HT2 quartz 6,2 B.D.L. B.D.L. 2 390 465128 32,9 B.D.L. 359 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,43 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz 10 9,8 18,1 3,7 574 465128 33,9 B.D.L. 445 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,33 0,49 B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz 5,9 B.D.L. 1,5 9 600 465128 26,4 B.D.L. 382 31,2 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 1,3 0,07 B.D.L. 1,2 B.D.L. B.D.L.
267 HT2 quartz 7,6 B.D.L. B.D.L. 6,1 760 465128 23,4 82,5 415 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 1,6 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz 10,7 B.D.L. 1,5 B.D.L. 1285 465128 22,6 307 475 9,1 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 1,9 0,09 B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz 7,1 B.D.L. B.D.L. B.D.L. 840 465128 32,5 114 282 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 1,7 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz 7,4 B.D.L. 2,1 3,8 711 465128 20,7 76,5 384 20,5 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 1,8 0,09 0,02 B.D.L. B.D.L. B.D.L.
267 HT2 quartz 11,4 B.D.L. 1,2 B.D.L. 1055 465128 27,5 259 424 4,5 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 2,2 B.D.L. B.D.L. 0,07 B.D.L. B.D.L.
267 HT2 quartz 12,2 B.D.L. 2,4 4,3 2540 465128 29,8 945 419 20,4 B.D.L. B.D.L. B.D.L. B.D.L. 2,8 4 0,09 B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz 4,3 B.D.L. B.D.L. 7,4 215 465128 24,9 B.D.L. 385 5,1 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz 1,4 B.D.L. B.D.L. B.D.L. 96,1 465128 26,5 B.D.L. 367 3,9 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz 8,2 B.D.L. 0,94 B.D.L. 1756 465128 33 673 323 16,3 B.D.L. B.D.L. 1,2 B.D.L. B.D.L. 0,41 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz 9,6 B.D.L. 1,9 B.D.L. 2579 465128 24 1107 401 20,6 B.D.L. B.D.L. 1,6 B.D.L. 2,6 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz 10,7 B.D.L. 0,74 B.D.L. 827 465128 26,8 137 314 4,9 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,3 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.

135
Table A.3: LA-ICP-MS analyses of quartz, titanite and rutile crystals

Ag Sn Sb Te Cs Ba La Ce Yb W Au Pb
Sample # Vein-type mineral
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)

300 HT1px quartz B.D.L. 30,3 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
300 HT1px quartz B.D.L. 26,7 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
300 HT1px quartz B.D.L. 23,2 B.D.L. B.D.L. B.D.L. B.D.L. 0,03 0,42 B.D.L. B.D.L. B.D.L. B.D.L.
300 HT1px quartz B.D.L. 25,6 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
300 HT1px quartz B.D.L. 23,2 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
300 HT1px quartz B.D.L. 23,5 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
300 HT1px quartz B.D.L. 28,5 1,8 B.D.L. B.D.L. 0,55 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
300 HT1px quartz B.D.L. 35,6 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
300 HT1px quartz B.D.L. 31 2,4 B.D.L. 0,22 0,2 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 4
300 HT1px quartz B.D.L. 31,9 0,88 B.D.L. 0,1 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
300 HT1px quartz B.D.L. 33,9 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
300 HT1px quartz 0,07 28,8 4,6 B.D.L. 0,27 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
300 HT1px quartz 0,06 29,2 10,6 B.D.L. 0,08 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
300 HT1px quartz B.D.L. 29 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz B.D.L. 35,6 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz B.D.L. 37,9 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz B.D.L. 29 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz B.D.L. 34,2 B.D.L. B.D.L. 0,05 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz B.D.L. 35,5 1,1 B.D.L. 0,14 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz B.D.L. 28,3 0,73 B.D.L. 0,15 0,41 B.D.L. 0,1 B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz 0,42 33,1 1,6 B.D.L. B.D.L. B.D.L. B.D.L. 0,11 B.D.L. 0,34 B.D.L. B.D.L.
267 HT2 quartz B.D.L. 33,4 4,1 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,27 B.D.L. B.D.L.
267 HT2 quartz B.D.L. 35,4 2,5 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz B.D.L. 30,7 1,4 B.D.L. 0,1 0,29 0,04 0,12 B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz B.D.L. 34,3 3,4 B.D.L. 0,04 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz B.D.L. 37,6 10,1 B.D.L. 0,03 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz B.D.L. 31,7 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz B.D.L. 31,5 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz B.D.L. 35,9 2,2 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz B.D.L. 35,1 10,6 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz B.D.L. 30,7 4,9 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.

136
Table A.3: LA-ICP-MS analyses of quartz, titanite and rutile crystals

Li B Na Mg P K Mn Fe Cu Zn As Rb Sr Y Zr Nb Mo
Sample # Vein-type mineral Al (ppm) Si (ppm) Ca (ppm) Ti (ppm)
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)

267 HT2 quartz 8,5 B.D.L. B.D.L. B.D.L. 849 465128 27,8 161 388 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz 1,4 B.D.L. B.D.L. B.D.L. 88,7 465128 21,8 B.D.L. 368 4,5 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz 2,7 B.D.L. B.D.L. B.D.L. 96 465128 24,6 B.D.L. 331 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz 2,6 B.D.L. B.D.L. N.A. 192 465128 N.A. B.D.L. 311 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.
267 HT2 quartz 2,8 B.D.L. 0,81 N.A. 199 465128 N.A. B.D.L. 341 3,6 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.
267 HT2 quartz 3,8 B.D.L. 3,6 N.A. 186 465128 N.A. B.D.L. 354 B.D.L. B.D.L. 35,8 1,8 B.D.L. B.D.L. 0,15 B.D.L. N.A. N.A. N.A. B.D.L.
267 HT2 quartz B.D.L. B.D.L. B.D.L. N.A. 120 465128 N.A. B.D.L. 301 4,8 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.
267 HT2 quartz 1,5 B.D.L. 2,9 N.A. 168 465128 N.A. B.D.L. 325 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.
267 HT2 quartz B.D.L. B.D.L. 3,8 N.A. 63,3 465128 N.A. B.D.L. 346 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 7,1 B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.
267 HT2 quartz B.D.L. B.D.L. B.D.L. N.A. 66,3 465128 N.A. B.D.L. 210 B.D.L. B.D.L. B.D.L. 7,4 B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.
267 HT2 quartz B.D.L. B.D.L. 1,4 N.A. 62 465128 N.A. B.D.L. 314 B.D.L. B.D.L. B.D.L. 5,4 B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.
267 HT2 quartz 1,7 B.D.L. 10,2 N.A. 100 465128 N.A. B.D.L. 571 10,7 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,22 N.A. N.A. N.A. B.D.L.
267 HT2 quartz 3,6 B.D.L. 2,8 N.A. 245 465128 N.A. B.D.L. 384 9,7 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,35 0,13 N.A. N.A. N.A. B.D.L.
267 HT2 quartz 7,2 B.D.L. 17,3 N.A. 962 465128 N.A. 333 285 22,6 4,3 B.D.L. B.D.L. B.D.L. B.D.L. 1,5 0,2 N.A. N.A. N.A. B.D.L.
267 HT2 quartz 1,1 B.D.L. 24 N.A. 63,9 465128 N.A. B.D.L. 358 B.D.L. B.D.L. 35 B.D.L. B.D.L. B.D.L. 0,23 0,07 N.A. N.A. N.A. B.D.L.
312 HT2 quartz B.D.L. B.D.L. 2,9 13,3 2536 465128 B.D.L. B.D.L. B.D.L. 82 B.D.L. B.D.L. B.D.L. B.D.L. 9,1 0,34 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
312 HT2 quartz B.D.L. B.D.L. 0,98 3,6 425 465128 27,4 52,8 227 116 B.D.L. B.D.L. B.D.L. B.D.L. 4,4 0,77 0,07 B.D.L. B.D.L. B.D.L. B.D.L.
312 HT2 quartz B.D.L. B.D.L. B.D.L. 4,8 363 465128 40,7 B.D.L. 289 107 B.D.L. B.D.L. B.D.L. B.D.L. 7,3 0,8 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
312 HT2 quartz B.D.L. B.D.L. B.D.L. 6 350 465128 36,9 B.D.L. 229 96,5 B.D.L. B.D.L. B.D.L. B.D.L. 6,5 0,45 B.D.L. 0,04 B.D.L. B.D.L. B.D.L.
312 HT2 quartz B.D.L. B.D.L. B.D.L. 6,4 283 465128 31,2 B.D.L. 252 81,5 B.D.L. B.D.L. B.D.L. B.D.L. 6,4 0,59 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
312 HT2 quartz B.D.L. B.D.L. 3 6,9 340 465128 25,9 B.D.L. 299 83,1 B.D.L. B.D.L. B.D.L. B.D.L. 7,4 0,55 B.D.L. B.D.L. 0,06 B.D.L. B.D.L.
312 HT2 quartz B.D.L. B.D.L. 16,2 35 347 465128 31,2 113 448 86,4 B.D.L. B.D.L. B.D.L. B.D.L. 4,1 1 0,06 B.D.L. B.D.L. B.D.L. B.D.L.
312 HT2 quartz B.D.L. B.D.L. 3,1 B.D.L. 389 465128 24,9 B.D.L. 292 118 B.D.L. B.D.L. B.D.L. B.D.L. 7,4 0,61 0,06 B.D.L. B.D.L. B.D.L. B.D.L.
312 HT2 quartz B.D.L. B.D.L. B.D.L. N.A. 267 465128 N.A. B.D.L. B.D.L. 115 B.D.L. B.D.L. B.D.L. B.D.L. 9,7 0,86 B.D.L. N.A. N.A. N.A. B.D.L.
312 HT2 quartz B.D.L. 48,7 13 N.A. 436 465128 N.A. B.D.L. B.D.L. 114 B.D.L. 120 9,4 35,3 22,9 0,93 0,42 N.A. N.A. N.A. B.D.L.
312 HT2 quartz B.D.L. B.D.L. 3,9 N.A. 336 465128 N.A. B.D.L. 329 108 B.D.L. B.D.L. B.D.L. B.D.L. 7,4 0,89 B.D.L. N.A. N.A. N.A. B.D.L.
313 HT2 quartz B.D.L. 11,1 1,7 B.D.L. 63,1 465128 32,1 B.D.L. 471 2,3 B.D.L. B.D.L. B.D.L. B.D.L. 4,7 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
313 HT2 quartz B.D.L. B.D.L. 2,1 B.D.L. 54,7 465128 26,6 B.D.L. 592 9,7 B.D.L. B.D.L. B.D.L. 3,2 5,4 B.D.L. 0,06 B.D.L. B.D.L. B.D.L. B.D.L.
313 HT2 quartz B.D.L. 7,3 4,9 B.D.L. 42,1 465128 31,8 B.D.L. 392 5,7 B.D.L. B.D.L. B.D.L. B.D.L. 4,1 B.D.L. 0,08 B.D.L. B.D.L. B.D.L. B.D.L.
313 HT2 quartz 0,64 B.D.L. 16,5 N.A. 124 465128 N.A. B.D.L. 609 10,7 2,8 83,2 0,75 11 11,3 0,29 0,73 N.A. N.A. N.A. B.D.L.
313 HT2 quartz B.D.L. B.D.L. 5,3 N.A. 36,8 465128 N.A. B.D.L. B.D.L. 17,7 B.D.L. B.D.L. 4,5 B.D.L. 11,1 B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.

137
Table A.3: LA-ICP-MS analyses of quartz, titanite and rutile crystals

Ag Sn Sb Te Cs Ba La Ce Yb W Au Pb
Sample # Vein-type mineral
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)

267 HT2 quartz B.D.L. 32,8 1,8 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz B.D.L. 31,3 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz B.D.L. 30,3 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
267 HT2 quartz B.D.L. 30,8 B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
267 HT2 quartz B.D.L. 27,8 B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
267 HT2 quartz B.D.L. 29,6 B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. 0,54
267 HT2 quartz B.D.L. 29,3 B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
267 HT2 quartz B.D.L. 30,5 4 B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
267 HT2 quartz B.D.L. 31,6 11 B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
267 HT2 quartz B.D.L. 40,5 B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
267 HT2 quartz B.D.L. 66,7 B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
267 HT2 quartz B.D.L. 31,9 B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
267 HT2 quartz B.D.L. 31,4 0,6 B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
267 HT2 quartz B.D.L. 38,4 B.D.L. B.D.L. 0,13 B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. 1,9
267 HT2 quartz B.D.L. 30 B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. 0,6
312 HT2 quartz B.D.L. B.D.L. 3,7 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 1,1
312 HT2 quartz B.D.L. B.D.L. 0,61 B.D.L. 0,11 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
312 HT2 quartz B.D.L. B.D.L. 1,2 B.D.L. 0,06 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
312 HT2 quartz B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,13 B.D.L. B.D.L.
312 HT2 quartz B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,18 B.D.L. B.D.L.
312 HT2 quartz B.D.L. B.D.L. 2,9 B.D.L. 0,08 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
312 HT2 quartz 0,26 B.D.L. B.D.L. B.D.L. 0,1 0,37 0,06 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
312 HT2 quartz B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0,03 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
312 HT2 quartz B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
312 HT2 quartz B.D.L. B.D.L. 3,6 B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. 14,4
312 HT2 quartz B.D.L. B.D.L. 0,86 B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. 0,88
313 HT2 quartz B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
313 HT2 quartz B.D.L. B.D.L. 0,93 B.D.L. 0,06 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
313 HT2 quartz B.D.L. 0,96 B.D.L. B.D.L. 0,03 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
313 HT2 quartz B.D.L. B.D.L. 2,3 0,4 0,13 0,75 N.A. N.A. N.A. B.D.L. B.D.L. 2,7
313 HT2 quartz B.D.L. B.D.L. 2,2 B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.

138
Table A.3: LA-ICP-MS analyses of quartz, titanite and rutile crystals

Li B Na Mg P K Mn Fe Cu Zn As Rb Sr Y Zr Nb Mo
Sample # Vein-type mineral Al (ppm) Si (ppm) Ca (ppm) Ti (ppm)
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)

313 HT2 quartz B.D.L. B.D.L. 3,5 N.A. 79,8 465128 N.A. B.D.L. 604 6,3 B.D.L. B.D.L. B.D.L. 12 2,4 B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.
313 HT2 quartz B.D.L. B.D.L. 2,8 N.A. 63,7 465128 N.A. B.D.L. B.D.L. 4,1 B.D.L. B.D.L. B.D.L. B.D.L. 5,1 B.D.L. B.D.L. N.A. N.A. N.A. B.D.L.
257 HT1bt Rutile N.A. N.A. 100 90,2 882 N.A. B.D.L. N.A. N.A. 596128 352 2328 8,8 7,9 11,3 0,79 41,5 9,5 1220 2662 14,4
257 HT1bt Rutile N.A. N.A. 2258 69,1 3099 N.A. B.D.L. N.A. N.A. 596128 55,6 4649 8,2 10,4 14,6 0,61 46,7 4,9 1406 3632 39,8
257 HT1bt Rutile N.A. N.A. B.D.L. 6860 20502 N.A. B.D.L. N.A. N.A. 596128 11392 B.D.L. B.D.L. B.D.L. B.D.L. 338 B.D.L. B.D.L. 1129 513 273
257 HT1bt Rutile N.A. N.A. 1923 148 1094 N.A. 34626 N.A. N.A. 596128 1811 4227 10,3 13,5 41,2 0,31 410 51,8 1953 4665 22,4
257 HT1bt Rutile N.A. N.A. 55,4 422 5963 N.A. 26,6 N.A. N.A. 596128 35,6 5399 10,3 10,8 12,7 21 16,8 6,3 1707 5043 33,2
261 HT1bt Rutile N.A. N.A. B.D.L. B.D.L. B.D.L. N.A. B.D.L. N.A. N.A. 593133 46,4 24560 B.D.L. B.D.L. B.D.L. B.D.L. 0,6 13,1 837 1759 B.D.L.
259 HT1px Rutile N.A. N.A. 8304 2350 65870 N.A. 997 N.A. N.A. 593133 137 9327 10,1 B.D.L. 22,1 179 56,2 134 699 3091 5,2
259 HT1px Rutile N.A. N.A. 3125 8609 177633 N.A. 242 N.A. N.A. 593133 719 15654 B.D.L. 47,1 B.D.L. 661 47,6 9,4 836 2411 6,7
259 HT1px Rutile N.A. N.A. 14,5 73,3 413 N.A. 13,5 N.A. N.A. 596128 23 5564 8,6 15,9 B.D.L. B.D.L. 6,4 77,5 949 2947 13,9
259 HT1px Rutile N.A. N.A. 23,9 569 1036 N.A. 141 N.A. N.A. 596128 91,9 5883 7,7 14,8 B.D.L. B.D.L. 11,2 91,4 1198 3282 17,7
259 HT1px Rutile N.A. N.A. 111 3845 4352 N.A. B.D.L. N.A. N.A. 596128 1753 30059 B.D.L. 225 16,7 3,2 13,5 30,6 1780 5183 25,7
259 HT1px Rutile N.A. N.A. 60 99,5 556 N.A. 145 N.A. N.A. 596128 15,1 8736 B.D.L. 17,2 B.D.L. B.D.L. 7,8 11,5 2629 5114 15,6
259 HT1px Rutile N.A. N.A. 170 3519 1953 N.A. B.D.L. N.A. N.A. 596128 3432 50348 9,2 201 45,8 1,1 53,3 158 3279 6586 13,8
259 HT1px Rutile N.A. N.A. 75,5 131 2021 N.A. B.D.L. N.A. N.A. 596128 40,8 4131 8,3 B.D.L. B.D.L. 9,8 9 2,3 1330 3705 17,2
300 HT1px Rutile N.A. N.A. 90,1 103 5218 N.A. 197 N.A. N.A. 593133 45,1 3810 B.D.L. B.D.L. 17,4 B.D.L. 93,7 428 1571 2490 24,6
312 HT2 Rutile N.A. N.A. 84,8 73,5 120 N.A. 15,7 N.A. N.A. 593133 357 5868 8,7 34,7 11,6 0,42 4,6 9 189 7152 3,8
312 HT2 Rutile N.A. N.A. 81,6 72,1 110 N.A. 35 N.A. N.A. 593133 291 5144 10,5 30,8 13,9 B.D.L. 5,7 16,9 153 6680 6,8
312 HT2 Rutile N.A. N.A. B.D.L. 165 34874 N.A. 614 N.A. N.A. 593133 B.D.L. 273 B.D.L. B.D.L. B.D.L. B.D.L. 18,3 31,5 192 3145 19,3
313 HT2 Rutile N.A. N.A. 35,5 107 21939 N.A. B.D.L. N.A. N.A. 593133 237 4820 B.D.L. 576 28,1 2,2 12,8 79,3 246 3688 9,6
313 HT2 Rutile N.A. N.A. 17,2 88,3 535 N.A. 68,3 N.A. N.A. 593133 85 4779 12,3 B.D.L. 13,4 0,85 8,3 17,2 152 2596 B.D.L.
313 HT2 Rutile N.A. N.A. 29,6 75,9 844 N.A. 115 N.A. N.A. 593133 216 7961 20,5 B.D.L. 22,3 B.D.L. 10,8 39,1 278 3078 6,1
261 HT1bt Titanite 82,4 B.D.L. 289 1322 8406 B.D.L. 293 3887 192538 182641 1461 18348 51,9 462 61,5 6,6 71,2 1938 803 875 25,6
300 HT1px Titanite 12,1 40,2 3141 68006 14221 B.D.L. 187 1398 192538 142864 1966 64477 B.D.L. 151 20,7 2,1 104 411 402 489 3,4
300 HT1px Titanite 30 1076 251 1391 7953 B.D.L. 884 B.D.L. 192538 205906 792 14773 94,7 659 118 12 105 416 562 611 220
300 HT1px Titanite 25,7 371 300 1180 8212 B.D.L. 107 7237 192538 208636 435 9256 193 B.D.L. B.D.L. B.D.L. 56,3 387 824 1608 74,7
300 HT1px Titanite B.D.L. 18,3 164 111 7190 B.D.L. 130 B.D.L. 192538 199274 398 5628 7 9,2 7,3 0,25 31,7 244 440 792 5,2

N.A.: not analyzed; B.D.L.: below detection limit

139
Table A.3: LA-ICP-MS analyses of quartz, titanite and rutile crystals

Ag Sn Sb Te Cs Ba La Ce Yb W Au Pb
Sample # Vein-type mineral
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)

313 HT2 quartz B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. 0,54 B.D.L. B.D.L.
313 HT2 quartz B.D.L. B.D.L. 1,3 B.D.L. B.D.L. B.D.L. N.A. N.A. N.A. B.D.L. B.D.L. B.D.L.
257 HT1bt Rutile N.A. 112 152 N.A. 0,69 19,7 5,1 16,7 0,77 85,3 B.D.L. 45,9
257 HT1bt Rutile N.A. 329 196 N.A. 0,3 19,3 2 9,8 0,42 167 0,17 38,2
257 HT1bt Rutile N.A. B.D.L. 649 N.A. B.D.L. 328 B.D.L. B.D.L. 139 28844 B.D.L. B.D.L.
257 HT1bt Rutile N.A. 313 545 N.A. 0,39 76,5 203 410 7,2 24,5 0,41 172
257 HT1bt Rutile N.A. 372 208 N.A. 3,2 25,9 0,71 4,6 1,3 35,6 0,31 37,7
261 HT1bt Rutile N.A. 1576 B.D.L. N.A. 13,8 B.D.L. 139 75,6 38,4 2114 B.D.L. 85
259 HT1px Rutile N.A. 513 15,2 N.A. 42,1 93,2 681 1536 5,9 1308 B.D.L. 5,8
259 HT1px Rutile N.A. 382 15,5 N.A. 226 489 6,9 14,2 1,8 6390 B.D.L. 28,5
259 HT1px Rutile N.A. 202 1 N.A. 0,1 B.D.L. 10,4 43,3 5 567 0,13 0,11
259 HT1px Rutile N.A. 310 3,7 N.A. 0,73 B.D.L. 78,1 291 7,5 244 B.D.L. 7,1
259 HT1px Rutile N.A. 260 9,6 N.A. 1,2 4 33,8 97,6 3,6 5579 B.D.L. 9,1
259 HT1px Rutile N.A. 165 2,6 N.A. 0,43 0,72 20 59,7 0,9 20164 0,69 4,6
259 HT1px Rutile N.A. 110 26,7 N.A. 2,5 25,5 92,5 209 37,5 40166 1,2 94,1
259 HT1px Rutile N.A. 245 2,3 N.A. 0,23 57,4 0,87 2,5 B.D.L. 254 B.D.L. 1,2
300 HT1px Rutile N.A. 376 B.D.L. N.A. 0,75 564 2472 5732 29,8 288 B.D.L. 535
312 HT2 Rutile N.A. 122 21,8 N.A. 0,36 1,5 4,7 10,2 1,1 7575 0,79 6,9
312 HT2 Rutile N.A. 161 35 N.A. 0,31 2,9 10,6 21,8 2,5 9755 0,9 8,7
312 HT2 Rutile N.A. 118 152 N.A. B.D.L. 35,6 11,3 22,9 B.D.L. 22115 1,7 B.D.L.
313 HT2 Rutile N.A. 2297 78,1 N.A. B.D.L. 11,6 36,3 68,6 12,1 10669 B.D.L. 30,7
313 HT2 Rutile N.A. 282 20,2 N.A. 0,24 3,2 10,3 17,5 3,3 1780 B.D.L. 8,5
313 HT2 Rutile N.A. 370 42,2 N.A. 0,29 8,5 21 47,5 4,5 8240 0,52 29,9
261 HT1bt Titanite B.D.L. 279 B.D.L. 14,8 11,1 B.D.L. 1792 4708 203 90,3 1,8 36,7
300 HT1px Titanite B.D.L. 134 1,9 B.D.L. 0,09 6,6 1314 3498 41,7 91,7 B.D.L. B.D.L.
300 HT1px Titanite B.D.L. 334 B.D.L. 88,9 2,4 20,5 2291 5205 16,4 54,2 B.D.L. B.D.L.
300 HT1px Titanite 1,8 160 12,1 39,5 1,4 13,8 1955 5819 34,3 11,6 B.D.L. B.D.L.
300 HT1px Titanite 0,16 151 1,9 1,4 B.D.L. B.D.L. 1223 2991 28,2 33,2 B.D.L. 3,7

N.A.: not analyzed; B.D.L.: be

140
Table A.4: LA-ICP-MS analyses of SMI hosted in hydrothermal quartz

SiO2 K2O Na2O Al2O3 FE2O3 MgO Li B Na Mg Al K Ca Ti Mn Fe Cu Zn As Rb Sr Y Zr


Vein type
(wt%)* (wt%) (wt%) (wt%) (wt%) (wt%) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)

HT1bt veins N.C. 6,2 3,4 16 B.D.L. 0,07 B.D.L. B.D.L. 25002 421 84676 51603 B.D.L. B.D.L. 192 B.D.L. B.D.L. B.D.L. B.D.L. 424 72,6 5,4 7,1
HT1bt veins N.C. 5,6 3,4 16 B.D.L. B.D.L. B.D.L. B.D.L. 25194 B.D.L. 84676 46138 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 395 17 6,2 36,2
HT1bt veins 72,3 6,9 3,4 16 1,2 0,06 200 B.D.L. 25657 355 84676 57677 B.D.L. B.D.L. 248 8502 B.D.L. B.D.L. B.D.L. 318 38,4 64 93
HT1bt veins 74,2 6,1 3,1 16 0,62 0,04 B.D.L. B.D.L. 23198 236 84676 50355 B.D.L. B.D.L. B.D.L. 4321 B.D.L. B.D.L. B.D.L. 295 52,6 17,7 218
HT1bt veins N.C. 5,1 2,8 16 B.D.L. 0,15 B.D.L. B.D.L. 21215 900 84676 42406 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 412 63 8,4 217
HT1bt veins 74 5,5 3,2 16 1,3 0,08 50,1 B.D.L. 23872 461 84676 45298 B.D.L. B.D.L. B.D.L. 8797 47,3 B.D.L. B.D.L. 287 77,5 36,6 149
HT1bt veins N.C. 5,8 3,1 16 B.D.L. 0,02 B.D.L. B.D.L. 23052 113 84676 48207 B.D.L. 963 B.D.L. B.D.L. 47,2 B.D.L. B.D.L. 263 42,8 B.D.L. B.D.L.
HT1bt veins N.C. 7,7 3,9 16 B.D.L. B.D.L. 428 B.D.L. 28758 B.D.L. 84676 63865 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 299 85,3 B.D.L. 14,1
HT1bt veins 73,7 6 3,2 16 0,9 0,07 56,1 B.D.L. 24208 414 84676 50171 B.D.L. B.D.L. B.D.L. 6254 B.D.L. B.D.L. B.D.L. 384 58,8 3,8 64,1
HT1bt veins 73,8 6,4 3,1 16 0,7 0,02 66,3 429 22813 128 84676 53406 B.D.L. B.D.L. 185 4876 B.D.L. B.D.L. B.D.L. 315 38,9 72,8 56,8
HT1bt veins N.C. 11,2 3 16 B.D.L. B.D.L. B.D.L. B.D.L. 22527 B.D.L. 84676 92801 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 127 372 1,8 B.D.L.
HT1bt veins 72,5 6,5 3,6 16 1,4 0,07 B.D.L. B.D.L. 26680 436 84676 54149 B.D.L. B.D.L. 208 9442 658 182 12,1 297 50,4 7,1 93,2
HT1bt veins 73,7 6 3,4 16 0,78 0,05 B.D.L. B.D.L. 25734 290 84676 49623 2769 B.D.L. 197 5434 201 B.D.L. B.D.L. 242 58 3,3 15,9
HT1bt veins 74,4 5,4 3,2 16 0,83 0,18 B.D.L. B.D.L. 24222 1112 84676 44470 B.D.L. B.D.L. 224 5760 399 327 B.D.L. 242 65,2 6,4 23,3
HT1bt veins 73,9 5,4 4 16 0,56 0,03 B.D.L. B.D.L. 30214 190 84676 44943 824 B.D.L. 373 3911 99,8 351 10,8 426 55,9 6,7 39,2
HT1bt veins 72,4 6,4 4 16 1,1 0,08 B.D.L. B.D.L. 29714 497 84676 53334 B.D.L. B.D.L. 1140 7399 796 595 B.D.L. 300 76,7 3,8 47,9
HT1bt veins 72,2 7,2 3,9 16 0,54 0,17 129 B.D.L. 29148 1048 84676 59747 B.D.L. B.D.L. 184 3742 12,9 59,2 B.D.L. 291 62,5 5,2 35,5
HT1bt veins 74,3 5,9 3,1 16 0,63 0,07 B.D.L. B.D.L. 23267 439 84676 49036 B.D.L. B.D.L. 114 4380 26 B.D.L. B.D.L. 215 56,1 7,6 31,6
HT1bt veins 73,3 6,4 3,5 16 0,67 0,09 B.D.L. B.D.L. 26490 565 84676 52926 B.D.L. B.D.L. 155 4681 29,1 194 B.D.L. 252 47,5 6,2 26,1
HT1bt veins 73,4 6,5 3,3 16 0,72 0,09 B.D.L. B.D.L. 24997 550 84676 53821 B.D.L. B.D.L. 169 5009 B.D.L. 54,6 B.D.L. 229 49,1 5,8 55,1
HT1bt veins 73,1 7 3,2 16 0,64 0,05 B.D.L. B.D.L. 24083 313 84676 58171 B.D.L. B.D.L. 102 4471 38,7 66,7 B.D.L. 159 196 1,6 7,4
HT1bt veins 74 6,1 3,2 16 0,62 0,08 B.D.L. B.D.L. 23870 483 84676 50384 B.D.L. 666 B.D.L. 4334 B.D.L. 127 B.D.L. 268 50,7 5,8 56,5
HT1bt veins 74,3 5,9 3,2 16 0,54 0,08 B.D.L. B.D.L. 24064 488 84676 48663 B.D.L. B.D.L. B.D.L. 3782 17,5 100 B.D.L. 248 48,6 0,88 29,2
HT1bt veins 73,2 6,5 3,5 16 0,71 0,05 B.D.L. 56,2 25909 321 84676 54324 4153 791 145 4931 2,6 124 12,2 256 47,3 7 33,5
HT1bt veins 73,6 6,1 3,4 16 0,77 0,06 B.D.L. B.D.L. 25220 379 84676 51025 B.D.L. B.D.L. 160 5390 B.D.L. 33,3 B.D.L. 267 55,1 8,9 66,1
HT1bt veins B.D.L. 6,3 4,1 16 B.D.L. 0,04 B.D.L. B.D.L. 30691 212 84676 52364 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 326 98,9 2,6 10,8
HT1bt veins 73,4 6,2 3,7 16 0,58 0,05 B.D.L. 59,6 27816 273 84676 51615 3804 550 126 4021 1,3 46,9 B.D.L. 251 47 5 17,2
HT1bt veins 73,2 6,4 3,7 16 0,54 0,03 B.D.L. B.D.L. 27933 179 84676 53519 B.D.L. B.D.L. 122 3750 B.D.L. 62,5 B.D.L. 272 44,1 6 49,6
HT1bt veins 71,2 7,7 4,2 16 0,9 0,05 B.D.L. B.D.L. 30977 313 84676 63810 B.D.L. B.D.L. 172 6266 435 104 B.D.L. 264 65,1 B.D.L. 3,2
HT1bt veins 72,4 7,7 3 16 0,83 0,05 B.D.L. B.D.L. 22120 330 84676 64152 B.D.L. B.D.L. B.D.L. 5778 B.D.L. B.D.L. B.D.L. 262 110 1,7 6,9

141
Table A.4: LA-ICP-MS analyses of SMI hosted in hydrothermal quartz

Nb Mo Ag Sb Te Cs Ba W La Ce Yb Au Pb
Vein type
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)

HT1bt veins 3,7 12,1 B.D.L. B.D.L. 13,1 55,9 227 B.D.L. 13 16,6 B.D.L. B.D.L. 3,4
HT1bt veins 15,2 B.D.L. B.D.L. 41,4 B.D.L. 91,5 67,8 222 B.D.L. 6,2 1,6 B.D.L. 8,1
HT1bt veins 21 B.D.L. B.D.L. B.D.L. B.D.L. 74,1 72,4 B.D.L. 41,3 90,4 13,1 B.D.L. 14,5
HT1bt veins 18,2 B.D.L. B.D.L. B.D.L. B.D.L. 52,9 122 B.D.L. 26,1 65,5 11,8 B.D.L. 5,1
HT1bt veins 20 B.D.L. B.D.L. 106 B.D.L. 71,8 194 15,7 19,4 41 B.D.L. 6,3 36,3
HT1bt veins 26,5 B.D.L. B.D.L. B.D.L. B.D.L. 47 66,2 B.D.L. 54 42,1 10,2 B.D.L. 30,9
HT1bt veins B.D.L. B.D.L. 4,1 B.D.L. B.D.L. 31 118 B.D.L. 28,7 12,3 10,5 B.D.L. 17,3
HT1bt veins 13,9 B.D.L. B.D.L. B.D.L. B.D.L. 56,5 83,8 147 26,1 13,8 B.D.L. 25,6 B.D.L.
HT1bt veins 7 B.D.L. 7,5 53,2 B.D.L. 55,6 116 4,3 26,5 42,4 6,4 B.D.L. 6,6
HT1bt veins 19 B.D.L. B.D.L. B.D.L. B.D.L. 63 178 15,1 43,9 90,2 9,1 B.D.L. B.D.L.
HT1bt veins B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 342 18,2 2,6 2,7 1,2 B.D.L. 17,1
HT1bt veins 36,9 3,4 4,3 5,4 B.D.L. 22,1 56,3 1,2 13 39,6 1,6 B.D.L. 58,9
HT1bt veins 10,8 B.D.L. B.D.L. B.D.L. B.D.L. 13,1 64 B.D.L. 8,5 18,8 B.D.L. B.D.L. 21,1
HT1bt veins 18,6 2,1 4,8 5 B.D.L. 17,9 63,9 B.D.L. 10,4 19,4 B.D.L. B.D.L. 84,7
HT1bt veins 13,2 11,1 B.D.L. 0,73 B.D.L. 22,2 31,9 3,5 10,9 20,5 B.D.L. B.D.L. 61,7
HT1bt veins 19 21,1 2,4 B.D.L. B.D.L. 31,7 97,8 1 10,8 18,6 B.D.L. B.D.L. 300
HT1bt veins 19,1 5,1 1,7 B.D.L. B.D.L. 22,2 55 B.D.L. B.D.L. 21,2 0,65 B.D.L. 17
HT1bt veins 16,2 B.D.L. B.D.L. 0,26 B.D.L. 15,1 47,4 B.D.L. 13,4 32,1 1,4 B.D.L. 23,1
HT1bt veins 10,5 B.D.L. B.D.L. B.D.L. B.D.L. 19,6 45,7 0,1 10,8 29,8 0,42 B.D.L. 23
HT1bt veins 24,6 2,1 B.D.L. B.D.L. B.D.L. 12,9 23,8 B.D.L. 10,7 30,2 B.D.L. B.D.L. 20,6
HT1bt veins 4,2 B.D.L. B.D.L. B.D.L. B.D.L. 3,2 303 2,2 6,3 10,4 B.D.L. B.D.L. 32,5
HT1bt veins 13,3 5,8 B.D.L. B.D.L. B.D.L. 23,3 28,3 8,7 B.D.L. 14,4 B.D.L. B.D.L. 20,3
HT1bt veins 13,6 11,2 B.D.L. B.D.L. B.D.L. 21,9 19,9 1,5 9,7 13,1 B.D.L. B.D.L. 20,6
HT1bt veins 23,6 1 0,29 0,46 B.D.L. 23,7 33,3 0,53 9,3 22,4 0,83 B.D.L. 31,1
HT1bt veins 23,9 3 B.D.L. 3,9 B.D.L. 18,5 49,7 B.D.L. 8,2 28,3 0,68 B.D.L. 26,1
HT1bt veins 20,5 B.D.L. B.D.L. 22 B.D.L. 42,9 73,5 B.D.L. 21,1 29,2 B.D.L. B.D.L. 123
HT1bt veins 15,1 B.D.L. B.D.L. B.D.L. B.D.L. 19,6 30,6 0,15 10,8 22,8 0,27 B.D.L. 21,1
HT1bt veins 28,8 1,5 0,22 2,2 B.D.L. 19,7 33,4 0,74 10 24,2 0,99 B.D.L. 29,8
HT1bt veins 13,2 B.D.L. B.D.L. B.D.L. B.D.L. 6,6 103 9,8 3,7 2,5 2,8 B.D.L. 54,4
HT1bt veins 3,4 8,7 B.D.L. B.D.L. B.D.L. 5,9 125 0,2 4,1 3,3 B.D.L. B.D.L. 18,3

142
Table A.4: LA-ICP-MS analyses of SMI hosted in hydrothermal quartz

SiO2 K2O Na2O Al2O3 FE2O3 MgO Li B Na Mg Al K Ca Ti Mn Fe Cu Zn As Rb Sr Y Zr


Vein type
(wt%)* (wt%) (wt%) (wt%) (wt%) (wt%) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)

HT1bt veins 73,8 6,2 3,5 16 0,53 0,07 B.D.L. B.D.L. 25816 404 84676 51130 B.D.L. B.D.L. 112 3678 B.D.L. 31 B.D.L. 251 48,3 6,4 9,2
HT1bt veins 72 7 4,1 16 0,86 0,1 B.D.L. B.D.L. 30569 596 84676 57727 B.D.L. B.D.L. 178 6020 53,9 B.D.L. B.D.L. 183 37,7 2,4 7,7
HT1bt veins N.C. 7,9 3,1 16 B.D.L. B.D.L. B.D.L. B.D.L. 23246 B.D.L. 84676 65432 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 176 125 2,6 8,4
HT1bt veins 75,7 4,2 3,2 16 0,79 0,1 B.D.L. B.D.L. 24173 585 84676 34518 B.D.L. B.D.L. 388 5495 12,9 B.D.L. B.D.L. 323 15,5 11,8 29,4
HT1bt veins 74,9 4,7 3,5 16 0,81 0,09 B.D.L. B.D.L. 26322 558 84676 38924 B.D.L. B.D.L. 302 5664 B.D.L. B.D.L. B.D.L. 331 12,5 5 35
HT1bt veins N.C. 6,1 3,7 16 B.D.L. 0,03 B.D.L. B.D.L. 27924 208 84676 50953 B.D.L. B.D.L. 524 B.D.L. 33,3 137 B.D.L. 362 8,1 1,3 31,1
HT1bt veins 74,5 4,5 3,5 16 1,3 0,13 B.D.L. B.D.L. 26138 798 84676 37711 B.D.L. B.D.L. B.D.L. 9171 B.D.L. 192 B.D.L. 338 26,5 15,3 47,8
HT1bt veins 74,5 4,8 4,2 16 0,53 0,06 B.D.L. B.D.L. 31229 373 84676 39563 B.D.L. B.D.L. 275 3698 B.D.L. 75,5 B.D.L. 319 14,8 17,6 38,2
HT1bt veins 73,5 5,2 4 16 1,1 0,14 B.D.L. B.D.L. 30065 862 84676 42993 B.D.L. B.D.L. B.D.L. 7692 B.D.L. B.D.L. B.D.L. 315 18,7 0,79 30,9
HT1px veins N.C. 5,1 3,6 16 B.D.L. B.D.L. B.D.L. B.D.L. 27120 B.D.L. 84676 42290 34903 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 92 190 1,1 2,6
HT1px veins N.C. 5 4 16 B.D.L. B.D.L. B.D.L. B.D.L. 29754 B.D.L. 84676 41712 B.D.L. B.D.L. B.D.L. B.D.L. 83,3 82,9 138 372 27 12 9,3
HT1px veins 74,6 5,2 3,6 16 0,58 0,07 B.D.L. B.D.L. 26689 421 84676 43262 B.D.L. 1401 B.D.L. 4066 B.D.L. B.D.L. B.D.L. 454 17,8 13,4 59,1
HT1px veins N.C. 5,1 3,6 16 0,32 B.D.L. 184 B.D.L. 26856 B.D.L. 84676 42543 B.D.L. B.D.L. 214 2264 25,2 B.D.L. B.D.L. 373 B.D.L. 7,9 17,7
HT2 veins N.C. B.D.L. 0,07 16 B.D.L. 0,05 91,5 B.D.L. 512 283 84676 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 144 B.D.L. B.D.L. 403 8 28 21,1
HT2 veins N.C. 4,5 0,06 16 B.D.L. 0,03 68,2 B.D.L. 446 168 84676 37170 B.D.L. B.D.L. B.D.L. B.D.L. 188 B.D.L. B.D.L. 364 5,3 34 27,2
HT2 veins N.C. 6,8 0,5 16 B.D.L. 0,07 96 162 3759 397 84676 56319 B.D.L. B.D.L. 366 B.D.L. 194 191 B.D.L. 461 11,3 33,8 33,6
HT2 veins N.C. 5,6 0,74 16 1,6 B.D.L. B.D.L. 418 5554 B.D.L. 84676 46875 B.D.L. B.D.L. 554 10989 174 B.D.L. B.D.L. 397 6,8 39,6 17,3
HT2 veins 77,5 4,8 0,89 16 0,85 0,03 305 B.D.L. 6630 201 84676 39521 B.D.L. B.D.L. B.D.L. 5924 B.D.L. B.D.L. B.D.L. 346 1,4 5,9 13,6
HT2 veins 76,5 5,6 1,5 16 0,37 0,03 B.D.L. B.D.L. 11041 162 84676 46305 B.D.L. 358 69,8 2582 B.D.L. 201 155 510 5,9 32,9 59,2
HT2 veins 78,1 5,1 0,06 16 0,6 0,18 B.D.L. B.D.L. 469 1111 84676 42195 B.D.L. B.D.L. 53,3 4155 B.D.L. B.D.L. B.D.L. 292 12 3,6 10
HT2 veins N.C. 4,4 B.D.L. 16 0,29 0,13 B.D.L. B.D.L. B.D.L. 755 84676 36394 B.D.L. B.D.L. B.D.L. 1991 13,1 B.D.L. B.D.L. 168 14,7 0,9 0,49
HT2 veins 78,4 5 0,1 16 0,21 0,3 B.D.L. B.D.L. 754 1828 84676 41436 B.D.L. B.D.L. 53 1460 8,5 22,1 B.D.L. 230 21,4 1,7 17,2
HT2 veins 77,7 5,4 0,14 16 0,66 0,12 117 282 1023 731 84676 44678 B.D.L. B.D.L. 79,2 4618 44,6 150 139 466 19,3 31,5 42,5
t.%= 100 -wt%(K20)-wt%(Na2O)-wt%(Fe2O3)-wt%(Al2O3)-wt%(MgO)
N.C.: Not calculated; B.D.L. : Below detection limit

143
Table A.4: LA-ICP-MS analyses of SMI hosted in hydrothermal quartz

Nb Mo Ag Sb Te Cs Ba W La Ce Yb Au Pb
Vein type
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)

HT1bt veins 12,3 1,2 B.D.L. B.D.L. B.D.L. 20,5 26,1 B.D.L. 11,1 28,2 0,6 B.D.L. 21,9
HT1bt veins 5,4 B.D.L. B.D.L. B.D.L. B.D.L. 20,1 24,9 2,3 7,9 15,6 1,5 B.D.L. 30,8
HT1bt veins B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 7,4 743 25,3 0,54 1,1 B.D.L. B.D.L. 17,6
HT1bt veins 2,2 B.D.L. B.D.L. 8 B.D.L. 56,1 50,6 232 3,2 4,1 B.D.L. B.D.L. 6,5
HT1bt veins 13,1 B.D.L. B.D.L. 25,4 B.D.L. 66,4 85,5 164 2,1 3,3 B.D.L. B.D.L. 3,7
HT1bt veins 13,5 25,1 B.D.L. B.D.L. B.D.L. 36,1 B.D.L. 194 3 4,3 B.D.L. B.D.L. B.D.L.
HT1bt veins 15,4 B.D.L. B.D.L. 42,8 B.D.L. 60 72,7 287 3 13,2 14,5 B.D.L. 13,1
HT1bt veins 5,6 B.D.L. B.D.L. 8,8 B.D.L. 27,3 51,8 B.D.L. 8,2 11 3,5 B.D.L. 0,7
HT1bt veins 11,2 B.D.L. B.D.L. B.D.L. B.D.L. 57,6 21,1 114 1,8 1,9 B.D.L. B.D.L. 1,6
HT1px veins B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 1444 B.D.L. B.D.L. B.D.L. B.D.L. 8,8 58,1
HT1px veins B.D.L. B.D.L. B.D.L. 190 B.D.L. 57,1 106 B.D.L. 11,4 24,1 B.D.L. B.D.L. 29
HT1px veins 2,4 B.D.L. 2,9 131 B.D.L. 89,8 137 12,4 4,3 21,4 B.D.L. B.D.L. B.D.L.
HT1px veins B.D.L. B.D.L. B.D.L. 54,5 B.D.L. 33,4 231 1,4 20,1 25,1 B.D.L. B.D.L. B.D.L.
HT2 veins B.D.L. B.D.L. 2,2 95,1 B.D.L. 86,8 6,7 25,8 7,8 22,7 B.D.L. B.D.L. B.D.L.
HT2 veins B.D.L. B.D.L. 3,2 138 B.D.L. 83,1 B.D.L. B.D.L. 8,7 49,3 B.D.L. B.D.L. B.D.L.
HT2 veins 1 B.D.L. B.D.L. 94,6 B.D.L. 102 B.D.L. 69 16,5 35,6 B.D.L. B.D.L. 58,7
HT2 veins 0,99 B.D.L. 11,7 136 B.D.L. 78,1 28,5 39,2 8,1 34,8 B.D.L. B.D.L. 84,6
HT2 veins B.D.L. 8,4 8,6 B.D.L. B.D.L. 19,7 B.D.L. 25,9 8,1 7,7 B.D.L. B.D.L. 16,7
HT2 veins B.D.L. 35,3 B.D.L. 44,3 B.D.L. 61,3 35,6 30,4 11,6 47 11,8 B.D.L. B.D.L.
HT2 veins 1 8,9 0,89 195 B.D.L. 15,1 52,7 1,2 2,2 3,3 1 B.D.L. 38
HT2 veins B.D.L. 9,5 B.D.L. 4,1 B.D.L. 24,6 328 3,7 13,2 12,4 1,1 B.D.L. 14,7
HT2 veins 0,96 B.D.L. 0,85 B.D.L. B.D.L. 22 231 11 6,2 6,4 0,14 B.D.L. 16,1
HT2 veins B.D.L. 9,8 4,2 65,2 B.D.L. 19,8 22,3 17,3 15,3 50,6 5,1 B.D.L. 2,9
t.%= 100 -w
N.C.: Not ca

144
Chapter 3:

Heterogeneous melt and hypersaline liquid inclusions

in shallow porphyry type mineralization as markers of

the magmatic-hydrothermal transition (Cerro de

Pasco district, Peru)


Bertrand Rottier*, Kalin Kouzmanov*, Anne-Sophie Bouvier**, Lukas P. Baumgartner**, Markus
Wälle***†, Hervé Rezeau*, Ronner Bendezú ****, and Lluís Fontboté*
*Department of Earth Sciences, University of Geneva, 1205 Geneva, Switzerland
**Institute of Mineralogy and Geochemistry, University of Lausanne, 1015 Lausanne, Switzerland
*** Institute of Geochemistry and Petrology, ETH Zürich, 8092 Zürich, Switzerland
**** Volcan Compañía Minera S.A.A., Lima, Peru

present address: Memorial University of Newfoundland, CREAIT, CRC and CFI Services (CCCS),
Bruneau Centre for Research and Innovation, St. John’s, NL, Canada, A1C 5S7

Published in Chemical Geology

145
CHEMGE-18125; No of Pages 24
Chemical Geology xxx (2016) xxx–xxx

Contents lists available at ScienceDirect

Chemical Geology

journal homepage: www.elsevier.com/locate/chemgeo

Heterogeneous melt and hypersaline liquid inclusions in shallow


porphyry type mineralization as markers of the magmatic-hydrothermal
transition (Cerro de Pasco district, Peru)
Bertrand Rottier a,⁎, Kalin Kouzmanov a, Anne-Sophie Bouvier b, Lukas P. Baumgartner b, Markus Wälle c,1,
Hervé Rezeau a, Ronner Bendezú d, Lluís Fontboté a
a
Department of Earth Sciences, University of Geneva, 1205 Geneva, Switzerland
b
Institute of Mineralogy and Geochemistry, University of Lausanne, 1015 Lausanne, Switzerland
c
Institute of Geochemistry and Petrology, ETH Zürich, 8092 Zürich, Switzerland
d
Volcan Compañía Minera S.A.A., Lima, Peru

a r t i c l e i n f o a b s t r a c t

Article history: Recently identified occurrences of porphyry-style mineralization evidence the link of the world's second largest
Received 22 July 2016 known epithermal base metal Cerro de Pasco deposit (Peru) to a porphyry system emplaced at depth. They con-
Received in revised form 14 October 2016 sist of (i) quartz-monzonite dykes and (ii) the south-western part of the large diatreme-dome complex adjacent
Accepted 25 October 2016
to the main ore bodies of Cerro de Pasco, and (iii) stockwork of banded quartz-magnetite-chalcopyrite-(pyrite)
Available online xxxx
porphyry-type veinlets crosscutting trachyte porphyritic intrusion cropping out at surface in the central part of
Keywords:
the diatreme-dome complex. The latter porphyry-type mineralization observed at the same erosion level as
Melt inclusions the main epithermal base metal carbonate-replacement ore bodies is the subject of this work. Geological con-
Fluid inclusions straints indicate a shallow emplacement level (depth b 1 km, P b 270 bar), implying rather unusual low-pressure
Porphyry-epithermal and high-temperature environment for the formation of porphyry-style mineralization.
LA-ICP-MS The banded porphyry-type veinlets record a multiphase history of formation with two successive high-temper-
SIMS ature (N600 °C) stages, followed by a lower-temperature (b350 °C) stage. More than 90% of the quartz in veinlets
Quartz precipitates during the first two high-temperature stages. Stage 1 is characterized by the entrapment in hydro-
SEM-CL
thermal quartz of inclusions containing variable proportions of both silicate melt and metal-rich hypersaline
(N90 wt% NaCl eq.) liquid, hereafter referred to as heterogeneous silicate melt inclusions (HSMIs). The latter
are rarely described in porphyry-type mineralization. We suggest that during stage 1, the inclusions result
from heterogeneous entrapment of an evolved hydrous rhyolitic melt mixed with a hypersaline fluid phase at
low pressure (270 bar) and high temperature (N600 °C). The stage 2 is marked by the entrapment of metal-
and sulfur-rich hypersaline liquid inclusions, with salinity around 70 wt% NaCl eq., originated from the adiabatic
ascent of magmatic hypersaline fluids transferred from deeper parts of the system. The lower-temperature stage
3 is characterized by an important temperature drop from N600 °C to b 350 °C as revealed by microthermometry
of aqueous two-phase liquid-vapor (L-V) inclusions. Quartz textures revealed by SEM-CL imaging allow ascribing
the sulfide precipitation to the low-temperature mineralization stage 3. In-situ SIMS 18O/16O isotope analyses of
quartz across the veinlets are indicative of a magmatic signature of the fluids during the first two stages; while
quartz from stage 3 has oxygen isotopic compositions suggestive of minor contribution of meteoric waters to a
predominantly magmatic aqueous fluid (~10 vol.% of meteoric input), which probably triggered Cu-Fe sulfide
precipitation in the stockwork. High metal and sulfur contents of HSMIs and hypersaline liquid inclusions deter-
mined by LA-ICP-MS are interpreted to represent the fluid composition prior to the main sulfide precipitation
event. The similar Pb-Zn ratio of the bulk ore extracted from the epithermal ore bodies at Cerro de Pasco and
the HSMIs and hypersaline liquid inclusions suggest a common source of the fluids associated with the different
mineralization styles at Cerro de Pasco.
© 2016 Elsevier B.V. All rights reserved.

⁎ Corresponding author.
E-mail address: Bertrand.Rottier@unige.ch (B. Rottier).
1
Present address: Memorial University of Newfoundland, CREAIT, CRC and CFI Services (CCCS), Bruneau Centre for Research and Innovation, St. John's, NL A1C 5S7, Canada.

http://dx.doi.org/10.1016/j.chemgeo.2016.10.032
0009-2541/© 2016 Elsevier B.V. All rights reserved.

Please cite this article as: Rottier, B., et al., Heterogeneous melt and hypersaline liquid inclusions in shallow porphyry type mineralization as
markers of the magmatic-hydrotherm..., Chem. Geol. (2016), http://dx.doi.org/10.1016/j.chemgeo.2016.10.032
146
2 B. Rottier et al. / Chemical Geology xxx (2016) xxx–xxx

1. Introduction Catchpole et al., 2015; Noble and McKee, 1999). It is the second largest
known epithermal base metal (“Cordilleran”) deposit after Butte in
Spatial and temporal link between porphyry-type mineralization Montana, USA. Historical production and remaining resources aggre-
and epithermal base metal deposits (i.e., Cordilleran polymetallic gate N 200 million tons (Mt) at around 7 wt% Zn, 2 wt% Pb, and 3 oz/t
deposits) is recognized in several telescoped systems where base Ag in addition to at least 100 Mt at 1.3% Cu and 1 g/t Au. Furthermore,
metal mineralization directly overprints high-temperature porphyry- Cerro de Pasco produced N 1 billion oz of Ag during Colonial times
style mineralization (e.g., Catchpole et al., 2011, 2015; Masterman et (Baumgartner et al., 2008 and references therein).
al., 2005; Reed et al., 2013; Rusk et al., 2008a). At the world-class (Zn- The Cerro de Pasco mining district is divided in two parts by a re-
Pb-Ag-Cu-Bi) Cerro de Pasco Cordilleran deposit a genetic link with a gional N15° W-striking reverse fault, locally known as Longitudinal
hidden porphyry system at depth has already been evoked by Fault. West of this fault, a large diatreme-dome complex of 2.5 km diam-
Baumgartner et al. (2008), but no direct evidence reported. Recently, eter crosscuts metamorphosed Middle Palaeozoic shales (Excelsior
Rottier et al. (2015a) described porphyry-style mineralization in clasts Group), which is the oldest exposed unit in the district, and younger
contained in (i) quartz-monzonite dykes and (ii) the large diatreme- conglomerates and sandstones of the Middle-Late Triassic Mitu Group
dome complex adjacent to the main part of Cerro de Pasco deposit, as (Fig. 1; Spikings et al., 2016). The eastern part of the district consists
well as (iii) porphyry-type stockwork mineralization occurring at sur- of a thick sequence (up to 1000 m) of carbonate rocks belonging to
face in the central part of the diatreme. The present study focuses on the Late Triassic Chambará Formation, part of the Pucará Group
the latter occurrence where shallow trachyte porphyry is crosscut by a (Angeles, 1999; Baumgartner et al., 2008; Rosas et al., 2007). The
stockwork of banded quartz-magnetite-chalcopyrite-(pyrite) veinlets. epithermal base metal mineralization mainly occurs hosted in carbon-
A striking characteristic of this porphyry-style mineralization is the ate rocks along the eastern margin of the diatreme-dome complex
occurrence of inclusions in the hydrothermal quartz consisting of vari- (Fig. 1; Baumgartner et al., 2008; Einaudi, 1977). The base metal miner-
able proportions of silicate melt and non-silicate chlorine-rich fluid, alization is emplaced at shallow level (its upper part b 1 km below the
hereafter referred to as heterogeneous silicate melt inclusions paleo-surface), and was formed by three main successive mineralizing
(HSMIs). HSMIs have been observed occasionally in various occurrences events, as summarized by Rottier et al. (2016): A) pipe-like pyrrho-
in quartz phenocrysts from intrusive rocks, miarolitic cavities and peg- tite-dominated bodies grading outwards into Fe-rich sphalerite (up to
matites (Campos et al., 2002, 2006; Davidson et al., 2005; Davidson 80 vol.%) and galena, B) a large N-S trending funnel-shaped massive py-
and Kamenetsky, 2007; Frezzotti, 1992; Fulignati et al., 2005; Harris et rite-quartz body, and C) high- to intermediate-sulfidation E-W–
al., 2004; Kamenetsky et al., 2004; Kamenetsky and Kamenetsky, trending Cu-Ag-(Au-Zn-Pb) enargite-pyrite veins hosted by the
2010; Lowenstern, 1994; Thomas and Davidson, 2013, 2016; Zajacz et diatreme breccia, and in the eastern part of the deposit large, well-
al., 2008). By contrast, HSMIs have been reported in porphyry-type hy- zoned Zn-Pb-(Bi-Ag-Cu) carbonate replacement ore bodies, mainly
drothermal quartz veins only from a few localities: Bajo de la Alumbrera striking N20° and N60° (Fig. 1).
porphyry Cu-Au deposit in Argentina (Harris et al., 2003), Elatsite por- The diatreme-dome complex was formed by a succession of
phyry Cu-Au deposit in Bulgaria (Stefanova et al., 2014), Deva porphyry phreatomagmatic, magmatic and phreatic events (Fig. 1; Baumgartner
Cu-Au deposit in the South Apuseni Mountains, Romania (Ivascanu et et al., 2009; Einaudi, 1968; Rogers, 1983). An early phase of explosive
al., 2003; Pintea, 1995, 2012), and Biely Vrch shallow porphyry-Au de- activity produced a diatreme-breccia body locally known as Rumiallana
posit in the Javorie belt, Slovakia (Koděra et al., 2013a, b), and their sig- Agglomerate, which is the most common lithology in the magmatic
nificance and origin are still controversial and not fully understood. complex. The upper part of the diatreme breccia is stratified and in-
In the frame of the present study we performed: i) a detailed optical cludes dacitic accretionary lapilli (0.2–0.5 cm diameter) tuffs showing
petrography complemented by SEM-CL imaging of quartz and Qemscan cross-bedding, interpreted as a base surge deposit and dated by isotope
quantitative mineralogical and textural definitions, ii) microthermometry dilution thermal ionization mass spectrometry (ID-TIMS) zircon U-Pb at
and LA-ICP-MS analyses of fluid inclusions, iii) LA-ICP-MS analyses of 15.36 ± 0.03 Ma (Baumgartner et al., 2008, 2009). The lower part of the
HSMIs, and iv) in-situ SIMS oxygen isotope analyses of hydrothermal diatreme, only accessible by drill-holes, consists of a massive non-strat-
quartz. We provide the first description of a shallow porphyry-type min- ified breccia. Following the phreatomagmatic events, magmatic activity
eralization spatially associated with the large Zn-Pb-(Ag-Cu-Bi) can be summarized as follow: i) dacitic to rhyodacitic lava-dome com-
epithermal base metal mineralization at Cerro de Pasco and the first de- plexes emplaced along the western margin of the diatreme and dated
tailed description of HSMIs trapped in porphyry-type veinlets. The results at 15.40 ± 0.07 Ma (zircon U-Pb ID-TIMS; Baumgartner et al., 2009);
allow discussing the origin of the HSMIs trapped in the early stages of for- ii) a rhyodacitic porphyry stock cropping out in the northern part of
mation of the porphyry-type veinlets and their significance as markers of the diatreme-dome complex; iii) several small trachyte porphyries
fluid processes that occur at the magmatic-hydrothermal transition. The (three identified, each b 10 × 10 m) cropping out in the central part of
metal contents of the HSMIs and hypersaline liquid inclusions are placed the diatreme breccia and crosscut by low-density stockwork porphyry
into the framework of the evolution of the whole mineralizing system at style mineralization, and iv) east-west trending quartz-monzonite
Cerro de Pasco and are interpreted to be equivalent of the parental/orig- porphyry dykes cutting the diatreme breccia and the dacitic to
inal fluid composition before the main low-temperature sulfide precipita- rhyodacitic lava-dome complexes (Fig. 1A) yield ID-TIMS zircon U-Pb
tion at Cerro de Pasco. dates of 15.35 ± 0.05 Ma and 15.16 ± 0.04 Ma (Baumgartner et al.,
2009; Fig. 1). The last phreatic event at Cerro de Pasco is marked by
the emplacement of numerous, 20 cm to 3 m-wide, mainly E-W
2. Geological setting trending, milled-matrix fluidized breccia dykes, occurring in various
parts of the diatreme-dome complex.
The Cerro de Pasco mining district is located 300 km north-east of Total erosion since the formation of the diatreme-dome complex is
Lima in the Western Cordillera of Peru. It is part of the mid-Miocene estimated to be b1 km on the basis of field relationships and textural
metallogenic belt recognized in Central and Northern Peru (Bendezú characteristics of pyroclastic rocks (e.g., occurrence of lapilli tuff:
and Fontboté, 2009; Bissig et al., 2008; Bissig and Tosdal, 2009; Baumgartner, 2007; Baumgartner et al., 2008).

Fig. 1. Geological map and cross-section of the diatreme-dome complex. The different epithermal mineralization styles at Cerro de Pasco were compiled from field observations and
previous work of Rogers (1983), Baumgartner et al. (2008) and the Volcan's geological staff. A) Location of the Cerro de Pasco district. B) Geological map, black arrows show location
of small trachyte porphyries. C) Zoom of one of the trachyte porphyry outcrops.

Please cite this article as: Rottier, B., et al., Heterogeneous melt and hypersaline liquid inclusions in shallow porphyry type mineralization as
markers of the magmatic-hydrotherm..., Chem. Geol. (2016), http://dx.doi.org/10.1016/j.chemgeo.2016.10.032
147
B. Rottier et al. / Chemical Geology xxx (2016) xxx–xxx 3

Please cite this article as: Rottier, B., et al., Heterogeneous melt and hypersaline liquid inclusions in shallow porphyry type mineralization as
markers of the magmatic-hydrotherm..., Chem. Geol. (2016), http://dx.doi.org/10.1016/j.chemgeo.2016.10.032
148
4 B. Rottier et al. / Chemical Geology xxx (2016) xxx–xxx

3. Porphyry mineralization at Cerro de Pasco performed using a confocal LABRAM equipped with a 532.12 nm Nd-
YAG Laser coupled with an Olympus BX51 microscope at the University
Evidence of three porphyry mineralization types was recently re- of Geneva. Gas composition was determined using an × 100 objective
ported at Cerro de Pasco (Rottier et al., 2015a). The two first types con- and the following Raman settings: 500 μm confocal aperture, 100 μm
sists of hornfels and magmatic clasts crosscut by typical A- and B-type slit, and acquisition time of two times 120 s. The limit of detection of
quartz-molybdenite and quartz-chalcopyrite-pyrite-magnetite veins the method is ~0.13 mol% CO2 (Rosso and Bodnar, 1995).
hosted in (i) quartz-monzonite dykes and (ii) the large diatreme brec- Microthermometric data of hypersaline liquid and aqueous L-V in-
cia. The third type consists of outcropping porphyry-style mineraliza- clusions were acquired up to temperature of 600 °C, using a THMSG
tion hosted by several small trachyte porphyries emplaced in the 600 Linkam heating–freezing stage mounted on a DMLB Leica micro-
Rumiallana Agglomerate in the central part of the diatreme-dome com- scope calibrated using SYNFLINC standards at − 56.6 °C, 0.0 °C, and
plex and is the subject of this research (Fig. 1). 374.1 °C (Sterner and Bodnar, 1984). Heating experiments above
The studied trachyte porphyry represents, based on its major ele- 600 °C were done using a Linkam TS 1500 stage mounted on a DMLB
ment composition, one of the less evolved magmatic rock analyzed in Leica microscope. All experiments were conducted in nitrogen atmo-
the Cerro de Pasco mining district (Baumgartner et al., 2008 and addi- sphere to minimize oxidation of the sample. The stage was calibrated
tional rock analyses in supplementary material, Table A.1). It crops out using a SYNFLINC standard at 374.1 °C, as well as the melting points of
at higher elevation than the main carbonate replacement polymetallic AgI at 558 °C and NaCl at 801 °C. Salinities (wt% NaCl equiv.) were deter-
bodies (Fig. 1). Its continuation and shape at depth are not known. mined based on ice melting or salt melting temperatures using the
Two other porphyry bodies displaying similar texture and veining SoWat software (Driesner, 2007).
were recently identified by the Geological staff of Volcan Compañía Heating experiments on HSMIs trapped in quartz from the porphy-
Minera at 100 m north of the one reported in this study. Pervasive pyro- ry-type veinlets were conducted to produce a homogeneous glass and
phyllite-quartz-pyrite alteration grading to illite-smectite-muscovite- to observe the phase behavior of melt inclusions during heating. Quartz
pyrite and more externally to chlorite-calcite-pyrite alteration affects chips were heated using the same Linkam TS 1500 stage in nitrogen at-
the diatreme-breccia in the immediate vicinity to the trachyte porphyry. mosphere at room pressure. Samples were heated up to 900 °C with a
Fig. 1 shows the outline of these alteration zones mapped using Raman heating rate of 50 °C/min, and then up to 1150 °C with a heating rate
spectroscopy, X-ray diffraction, and optical petrography. In the trachyte of 5 °C/min. Samples were cooled to 300 °C at a rate of 200 °C/min in
porphyry itself, plagioclase is altered to sericite and chlorite (mainly order to quench the HSMIs, and to produce a homogeneous glass. Tem-
along veinlets) and biotite and amphibole to chlorite, epidote and cal- peratures reported in the paper for the melt inclusions are indicative
cite (Figs. 2 and 3). and do not represent true temperatures of phase transition and homog-
Both the trachyte porphyry and the surrounding diatreme-breccia enization because temperatures recorded during heating experiments
up to a distance of around 2–5 m are crosscut by a network of up to with a Linkam stage TS 1500 are strongly influenced by the rate of
2 cm-thick quartz-magnetite-chalcopyrite-pyrite porphyry-style vein- heating (Student and Bodnar, 1999) and overestimate the homogeniza-
lets with no visible alteration halo over a distance of 2 to 5 m (Figs. 1 tion temperature compared to experiments performed under pressure
and 2). The veinlets are widespread and locally densely distributed (Student and Bodnar, 2004). After rapid cooling, the quenched HSMIs
with up to 10 veinlets per square meter, they are polydirectional with presented a homogeneous silicate phase containing one or several
two main preferential orientations, N-S and E-W. Microscopic observa- small globules of salts, opaque crystals and vapor phase of variable
tions reveal high chalcopyrite/pyrite ratio with up to 5% chalcopyrite in size. Heated quartz chips were separated into two groups: one for direct
some veinlets; both sulfides being affected by supergene alteration. LA-ICP-MS analyses of the HSMIs and a second one mounted in epoxy,
Minor amounts of sphalerite, generally as inclusions in chalcopyrite, sequentially polished in order to expose on surface the HSMIs, for SEM
are observed as well. Pyrite and chalcopyrite are also present as dissem- and electron microprobe analyses.
inations in the altered trachyte porphyry. Both the trachyte porphyry Electron probe microanalyses (EPMA) were conducted at the Uni-
and the quartz-magnetite-chalcopyrite-(pyrite) banded veinlets are versity of Lausanne using a Jeol JXA 8200 Superprobe. For analyses of sil-
crosscut by E-W trending quartz-monzonite porphyry dykes. Three icate glass, the operating conditions were: accelerating voltage 15 kV,
samples were analyzed for Cu and Au by Volcan Compañía Minera, all beam current 10 nA, and beam diameter 2 μm. Standards and X-ray
display a constant Cu-Au ratio of ~10,000:1 and the richest mineralized emission lines were set up as follows: albite (Na-Kα, Al-Kα), apatite
sample graded 0.23 wt% Cu and 0.26 ppm Au. (F-Kα), bytownite (Ca-Kα), bornite (Cu-Kα), MnTiO3(Mn-Kα, Ti-Kα),
olivine (Mg-Kα, Fe-Kα), orthoclase (Si-Kα, K-Kα), celestine (S-Kα),
4. Analytical methods sphalerite (Zn-Kα). Counting times of 10 s on peak and 5 s on back-
ground on both sides of the peak were used for Si, Al, and K; 20 s on
Ten samples of the trachyte porphyry crosscut by quartz-magnetite- peak and 10 s on background on both sides of the peak were used for
chalcopyrite-pyrite porphyry-style veinlets were examined using trans- Na, Mg, Ti, Mn, Zn, Fe, Ca and Cu, and 30 s on peak and 15 s on back-
mitted- and reflected-light microscopy. No differences in mineralogy ground on both sides of the peak were used for F and S.
and alteration styles were observed between the ten samples. Five sam- For analyses of quartz, the operating conditions were: accelerating
ples with hydrothermal quartz veinlets were selected for a detailed voltage 20 kV, beam current 80 nA, and beam diameter 5 μm. Standards
study. Doubly polished 200 μm-thick sections were examined using a and X-ray emission lines were set up as follows: albite (Al-Kα), bornite
standard petrographic microscope to characterize heterogeneous sili- (Cu-Kα), and MnTiO3 (Ti-Kα). Counting times of 60 s on peak and 30 s
cate melt inclusions (HSMIs), hypersaline liquid, and aqueous liquid- on background on both sides of the peak were used for Ti and Cu, 40s on
vapor (L-V) inclusions hosted in quartz. Scanning electron microscopy peak and 20s on background on both sides of the peak were used for Al.
cathodoluminescence (SEM-CL) was used in order to texturally charac- Limits of detection were 54 ppm for Al, 74 ppm for Ti and 64 ppm for Cu.
terize the different quartz generations in the veinlets and the paragenet- A total of 15 heated HSMIs, 34 hypersaline liquid, and 10 aqueous L-
ic context of the studied HSMIs and fluid inclusions. SEM-CL images V inclusions were analyzed using a 193 nm ArF Excimer laser with an
were acquired at the University of Lausanne using a CamScan MV2300 energy homogenized beam profile coupled with an ELAN 6100 DRC
SEM and at the University of Geneva using a JEOL JSM7001F SEM, both ICP quadrupole mass spectrometer (QMS) at ETH Zurich (Günther et
equipped with panchromatic CL detectors. al., 1997, 1998; Heinrich et al., 2003). Table 1 summarizes the analytical
Raman microspectroscopy was used to identify solid inclusions conditions, data acquisition parameters, and list of isotopes analyzed
trapped in minerals or as daughter phases in fluid inclusions and the during laser ablation inductively coupled plasma mass spectrometry
composition of the gas phase of fluid inclusions. Measurements were (LA-ICP-MS) analytical sessions. Inclusions were ablated using an iris

Please cite this article as: Rottier, B., et al., Heterogeneous melt and hypersaline liquid inclusions in shallow porphyry type mineralization as
markers of the magmatic-hydrotherm..., Chem. Geol. (2016), http://dx.doi.org/10.1016/j.chemgeo.2016.10.032
149
B. Rottier et al. / Chemical Geology xxx (2016) xxx–xxx 5

Fig. 2. A) Outcrop of the trachyte porphyry intruding the diatreme breccia. B) Quartz-magnetite-chalcopyrite-(pyrite) veinlet in the trachyte porphyry. C) Quartz-magnetite-chalcopyrite-
(pyrite) veinlets in the diatreme breccia. D) Polished slab showing a quartz-monzonite dyke crosscutting the trachyte porphyry and the quartz-magnetite-chalcopyrite-(pyrite) veinlets
(arrows). E) Transmitted light microphotograph of a banded quartz-magnetite-chalcopyrite-(pyrite) veinlet crosscutting the trachyte porphyry. The dark bands close to the veins walls
visible also in B, C, and D correspond to the botryoidal quartz bearing micrometric magnetite inclusions.

diaphragm for progressive manual increase of the laser beam diameter were coated with a 40 nm-thick layer of gold. For oxygen isotope
to limit explosion of the host quartz (Guillong and Heinrich, 2007). LA- measurements, we used a 10 kV Cs+ primary beam, a ~ 2 nA current,
ICP-MS transient signals were reduced using Sills software (Guillong et resulting in a ~10 μm beam size. The electron flood gun, with normal in-
al., 2008). The NIST glass standard SRM 610 was used as an external cidence, was used to compensate charges. 16O and 18O secondary ions,
standard and analyzed two times bracketing a maximum of 20 un- accelerated at 10 kV, were analyzed at a mass resolving power of 2400
knowns to correct the drift by linear regressions. For aqueous L-V and and collected on Faraday cups (FCs) multi-collection mode. The data
hypersaline liquid inclusions, Na concentration derived from the have been obtained during the same session of 12 h. FCs are calibrated
microthermometric measurements was used as an internal standard at the beginning of the session. Mass calibration was performed at the
for each ablated fluid inclusion. For hypersaline liquid inclusions, an em- beginning of the session and a nuclear magnetic resonance was used
pirical correction for major dissolved cations other than Na (e.g., K, Fe, to lock the magnetic field. Details of the analytical settings are described
Mn, Zn, Cu, and Pb) was applied (Heinrich et al., 2003). Quantification in Seitz et al. (accepted for Geostandards and Geoanalytical Research).
of the HSMIs has been done following the method of Halter et al. Each analysis takes b4 min, including pre-sputtering (30 s) and auto-
(2002). Internal standardization of all melt inclusions analyzed was mated centering of secondary ions. This setting allowed an average re-
based on 16.7 wt% Al2O3, derived from EPMA, which is in agreement producibility better than 0.3‰ (2SD) on UNIL-Q1 reference material at
with the calculated mean Al2O3 content obtained from whole rock geo- the beginning of the session, and internal error for each analysis lower
chemistry of the volcanic and sub-volcanic rocks of the district than 0.3‰ 2σ. A set of 4 analyses of UNIL-Q1 standard, inserted in
(mean = 15.6 ± 0.6 wt% Al2O3, n = 13, XRF analyses, supplementary each mounts, has also been measured every 15–20 analyses for moni-
material Table A.1). For host correction (i.e. quartz), 99.5 wt% SiO2 was toring the instrument stability, and accuracy by correcting the instru-
assumed as an internal standard. mental mass fractionation, as it can slightly differ from mount to
A total of 41 18O/16O isotopic ratio analyses and 12 in-situ trace ele- mount. The variation of UNIL-Q1 over the entire session was b 0.3‰
ments analyses (Ti, Al, Fe and Li) were performed on quartz chips placed (2SD). The error reported for samples reflected the 2SD bracket be-
in indium mounts that included grains of two quartz reference materials tween the surrounding standard sessions. Also, a total of 12 spot analy-
(UNIL-Q1 for δ18O measurements (Seitz et al., 2016) and BGS-Q1 ses for trace element (Ti, Al, Fe and Li) were measured at the SwissSIMS
for trace elements (Audétat et al., 2015)). Measurements were per- using an O− primary beam of 1.1 nA accelerated at 13 kV to bombard
formed at the SwissSIMS ion probe national facility at the University the sample surface. Secondary ions were accelerated at 10 kV into the
of Lausanne, using a Cameca IMS180-HR. For both sessions, samples mass spectrometer. 7Li+, 27Al+, 30Si+, 48Ti+ and 56Fe+ were analyzed

Please cite this article as: Rottier, B., et al., Heterogeneous melt and hypersaline liquid inclusions in shallow porphyry type mineralization as
markers of the magmatic-hydrotherm..., Chem. Geol. (2016), http://dx.doi.org/10.1016/j.chemgeo.2016.10.032
150
6 B. Rottier et al. / Chemical Geology xxx (2016) xxx–xxx

Please cite this article as: Rottier, B., et al., Heterogeneous melt and hypersaline liquid inclusions in shallow porphyry type mineralization as
markers of the magmatic-hydrotherm..., Chem. Geol. (2016), http://dx.doi.org/10.1016/j.chemgeo.2016.10.032
151
B. Rottier et al. / Chemical Geology xxx (2016) xxx–xxx 7

Table 1
LA-ICP-MS machine and data acquisition parameters.

Fluid and hypersaline inclusions hosted in quartz HSMIs hosted in quartz

Excimer 193 nm ArF laser Compex 110I


Energy density ~20 J/cm2 ~20 J/cm2
Repetition rate 10 Hz 10 Hz
Crater sizes 15–60 μm 15–40 μm
Ablation cell In-house built glass chamber with anti-reflection In-house built glass chamber with anti-reflection coated silica
coated silica glass window glass window
Cell He gas flow 1.1 l/min He 1.1 l/min He
Cell H gas flow 5 ml/min H2 5 ml/min H2

Data acquisition parameters


Readings per replicate 400 400
Points per peak 1 per mass 1 per mass
Oxide production rate tuned to b0.5% ThO tuned to b0.5% ThO
Dwell time per isotope 40 ms for Fe, 30 ms for Ag and Ca 10 ms for all isotopes
10 ms for the others
7
Isotopes analyzed (fluid inclusions program) Li, 11B, 23Na, 27Al, 29Si, 34S, 39K, 44Ca, 49Ti, 55Mn, 7
Li, 11B, 23Na, 25Mg, 27Al, 29Si, 34S, 39K, 44Ca, 49Ti, 55Mn, 57Fe, 65Cu,
57
Fe, 65Cu, 66Zn, 75As, 85Rb, 88Sr, 98Mo, 107Ag, 118Sn, 66
Zn, 75As, 85Rb, 88Sr, 89Y, 90Zr, 93Nb, 98Mo, 107Ag, 118Sn, 121Sb, 133Cs,
121
Sb, 133Cs, 137Ba, 184W, 197Au, 208Pb 137
Ba, 139La, 140Ce, 173Yb, 184W, 197Au, 208Pb

on mono-collection mode using the axial electron multiplier (EM). The quartz Q2 characterized by entrapment of hypersaline liquid inclusions.
field aperture was set to 4000 μm and the energy slit to 50 μm. The en- Quartz Q2 is mostly intergrown with Q1 and it overgrows Q1 grains in
trance slit was closed to 61 μm and the exit slit to 405 μm, allowing sep- rare cases only. No difference in CL light intensity and in most cases nei-
arating the measured ions from any interference. Before each analysis, a ther in texture, between Q1 and Q2 is discernible. Hence, we have cho-
pre-sputtering of 120 s using a raster beam of 30 μm was used to clean sen to join these two early quartz generations under the
the sample surface. Automatic calibration on 30Si and centering of field denomination Q1–2. Quartz Q1–2 shows (Fig. 4) roughly-zoned
aperture were made before each analysis, just after the pre-sputtering. subhedral crystals (Q1–2a), botryoidal (Q1–2b), and subhedral comb-
Measurements were done without any raster, with a 15–20 μm beam. like textures with well-developed oscillatory growth zoning (Q1–2c).
Each analysis consists of 15 cycles of the peak-stepping sequence 7Li+ Both, Q1–2a and Q1–2b are observed close to the contacts of the veinlets,
(5 s), 27Al+ (3 s), 30Si+ (2 s), 48Ti+ (5 s) and 56Fe+ (8 s). Reproducibility whereas Q1–2c forms the core of the veinlets. Quartz Q1–2a and Q1–2b are
(in 2SD) was 11% for Li, 7% for Al, 6% for Ti and 11% on Fe on BGS-Q1. rich in micron-sized magnetite inclusions, small HSMIs, and hypersaline
Background on the EM was b 2 counts per hour. liquid inclusions resulting in the banded texture of the veinlets (Fig. 2B).
Botryoidal quartz is commonly observed in shallow porphyry deposits
and is interpreted to form from recrystallization of an amorphous silica
5. Results
gel due to rapid fluid decompression (Herrington and Wilkinson, 1993;
Koděra et al., 2014; Muntean and Einaudi, 2000; Vila and Sillitoe, 1991).
5.1. Trachyte porphyry and associated alteration
Locally, Q1–2a and Q1–2c grains are overgrown, and in part also resorbed
by quartz Q1–2d with similar or lower CL-luminescence (Fig. 4C). Similar
The trachyte porphyry is mainly composed of phenocrysts
textures are documented in porphyry quartz veins (Müller et al., 2010;
(~40 vol.%) of plagioclase, K-feldspar, quartz and biotite within a Si-K-
Penniston-Dorland, 2001; Redmond et al., 2004; Rusk et al., 2008b). In
rich matrix (~60 vol.%). The accessory phases mainly consist of apatite,
one sample, quartz sub-generations Q1–2a–d are crosscut by a quartz
sphene, hornblende, zircon and Fe-oxides.
vein (Q1–2e), that has similar CL light intensity and texture, and hosts
Albitization halos occur along the quartz veinlets and are illustrated
melt and fluid inclusions (Fig. 4C). The different textures indicate that
by the Qemscan maps (Fig. 3). Late pervasive alteration resulting in ep-
the different Q1–2 generations were formed during successive hydro-
idote-chlorite-sericite-calcite assemblage mainly replacing biotite and
thermal episodes. Despite textural differences, all Q1–2 sub-generations
hornblende, the previously formed albite, and to a lesser extent the pla-
display high CL intensity and host the same types of fluid and melt inclu-
gioclase, affects the entire volume of the exposed trachyte porphyry
sions and therefore in the following will not be differentiated. None of
(Fig. 3F and G).
the Q1–2 sub-generations has been observed to contain sulfide inclu-
sions or to be in direct contact with sulfide minerals; therefore Q1–2 is
5.2. Vein petrography and SEM-CL quartz textures considered to be pre-sulfide.
The next quartz generation Q3 is volumetrically minor and it was ob-
The investigated quartz-sulfide veinlets consist of three quartz gen- served in all studied samples in microfractures crosscutting Q1–2 and,
erations (Fig. 4). The first two quartz generations (Q1–2) are character- subordinately, in voids resulting from the dissolution of Q1–2 (Fig. 4A,
ized by high CL intensity. They represent N90% of the veinlets volume B and D). Quartz Q3 hosts only aqueous L-V and low-density vapor in-
(Fig. 4A) and hosts HSMIs, hypersaline liquid, and, rarely, low-density clusions; HSMIs and hypersaline liquid inclusions are not observed.
vapor and aqueous L-V inclusions. The fluid inclusion petrography indi- The contact between quartz generations Q1–2 and Q3 is marked by an
cates that quartz Q1–2 is formed during two distinct episodes. Most of abrupt change in CL intensity, Q3 showing low CL intensity with black,
the quartz grains were formed during the first episode (Q1) marked dark gray, and gray well-formed oscillatory growth zones (Fig. 4A, B
by entrapment of HSMIs. It is followed by precipitation of subordinate and D).

Fig. 3. A) QEMSCAN map of a trachyte porphyry sample crosscut by quartz-magnetite-chalcopyrite-(pyrite) veinlets, one of them showing albite in-fill; insets indicate the position of
photomicrographs F and G. Distribution maps of albite and quartz (B), chlorite, epidote, calcite, and quartz (C), X-ray elemental map of Na (D), and Ca (E). In E the intensity of the
green color corresponds to variable Ca-content in plagioclase grains and yellow color indicates presence of calcite, apatite, epidote, and sphene. F) Transmitted light photomicrograph
of amphibole and biotite phenocrysts replaced by chlorite and calcite (//N). G) Transmitted light photomicrograph (xN) of plagioclase phenocrysts replaced by sericite and/or albite.
Abbreviations: Ab - albite, Ap - apatite, Chl - chlorite, Cc - calcite, Ep - epidote, Qz - quartz, Mag - magnetite, Le - leucoxene, Ser - sericite, Spn - sphene. (For interpretation of the
references to color in this figure legend, the reader is referred to the web version of this article.)

Please cite this article as: Rottier, B., et al., Heterogeneous melt and hypersaline liquid inclusions in shallow porphyry type mineralization as
markers of the magmatic-hydrotherm..., Chem. Geol. (2016), http://dx.doi.org/10.1016/j.chemgeo.2016.10.032
152
8 B. Rottier et al. / Chemical Geology xxx (2016) xxx–xxx

Fig. 4. A) SEM-CL images of an entire quartz veinlet showing different quartz textures and generations (sample CP-14-BR-305); B and C) zoom of the SEM-CL image A; D) SEM-CL images of
a veinlet (sample CP-14-BR-305) the white arrows pointing to quartz Q1–2d overgrowing and partly overprinting Q1–2a and Q1–2c.

Chalcopyrite, pyrite, and rare sphalerite grains are systematically 5.3. In-situ SIMS oxygen isotope analyses of quartz
intergrown with Q3 suggesting that sulfides postdate Q1–2 and precipi-
tate contemporaneously with or after Q3. The veinlets are locally In-situ SIMS oxygen isotope analyses were performed on quartz Q1–2
reopened and filled with calcite, epidote, and chlorite, i.e., the same and Q3 from two samples (supplementary material, Table A.2). The two
mineral assemblage pervasively altering the host trachyte porphyry quartz generations display significantly different oxygen isotope com-
(Fig. 3A). position: δ18OQ1–2 = + 10.2‰ (n = 30, 2σ = ± 0.5) and δ18OQ3 =

Please cite this article as: Rottier, B., et al., Heterogeneous melt and hypersaline liquid inclusions in shallow porphyry type mineralization as
markers of the magmatic-hydrotherm..., Chem. Geol. (2016), http://dx.doi.org/10.1016/j.chemgeo.2016.10.032
153
B. Rottier et al. / Chemical Geology xxx (2016) xxx–xxx 9

+12.8‰ (n = 10, 2σ = ±1.8). The δ18O values throughout the different 5.4. SIMS and LA-ICP-MS trace element analyses in quartz
Q1–2 textures are nearly homogeneous within error (2σ on UNIL-Q1 ref-
erence material is ±0.3‰), whereas δ18OQ3 values are more scattered Lithium, Al, Ti, and Fe contents were analyzed by SIMS on 6 spots in
and an increase toward the center of the veinlets from 10.4 to 13.3‰ Q1–2 and 6 spots in Q3 (Fig. 5, Table 2). In both quartz generations, Al
is recognized (Fig. 5A, C). content is similar (Q1–2 = 333–958 ppm, Q3 = 345–1100 ppm),

Fig. 5. A) SEM-CL image of a quartz-magnetite-chalcopyrite-(pyrite) veinlet with location (red spots) and results of SIMS oxygen isotope analyses and with location and number of SIMS
trace element analyses (blue spots). B) Zoom of the SEM-CL image showing the contrasting Ti contents between quartz generations Q1–2 and Q3 and the location of the profile plotted in C.
C) Plot, along the profile shown in B, of δ18O of quartz determined by SIMS analyses, and of calculated δ18O of fluid in equilibrium with quartz, using the equation of Matsuhisa et al. (1979)
at 650 °C for quartz Q1–2 and at 315 °C for quartz Q3 (see text for discussion). Titanium content in the two quartz generations determined by SIMS is also plotted. (For interpretation of the
references to color in this figure legend, the reader is referred to the web version of this article.)

Please cite this article as: Rottier, B., et al., Heterogeneous melt and hypersaline liquid inclusions in shallow porphyry type mineralization as
markers of the magmatic-hydrotherm..., Chem. Geol. (2016), http://dx.doi.org/10.1016/j.chemgeo.2016.10.032
154
10 B. Rottier et al. / Chemical Geology xxx (2016) xxx–xxx

Table 2 former solids are molten and the two distinct liquid phases are still pres-
SIMS trace element results of quartz generations Q1–2 and Q3. ent. Following rapid cooling, HSMIs quench into a silicate glass including
Analysis Quartz Li 1σ%a Al 1σ%a Ti 1σ%a Fe 1σa one or several small globules crowded with salt crystals, opaque min-
# generation ppm ppm ppm ppm erals, and a vapor bubble. If the globules are heated again, the salt
4 Q1–2 12.2 6 958 4.3 193 1.3 9.1 7.3 phases melt between 280° and 350 °C forming a chloride melt, and
5 Q1–2 5.7 10 514 12.3 156 2 15.8 2.9 an unidentified opaque crystals melt at temperature above 500 °C
6 Q1–2 6.3 6.6 523 11.4 358 1.7 145 2.5 (Fig. 7); above 800 °C, the inclusions melt completely. The salts and
7 Q1–2 4.1 8.4 333 12.8 224 0.54 137 1.5
the chloride melt react and change color from pale green to reddish-
10 Q1–2 20.5 7 627 6.3 126 1 6.2 6.8
11 Q1–2 7.5 6.8 746 3.7 144 1 7.5 9.6 brown under the green laser light of the Raman, making impossible
Mean 9.4 617 200 53.4 the identification of the different phases. Raman analyses of the vapor
Min 4.1 333 126 6.2 phase do not reveal presence of CO2 nor of other gases (e.g., CH4, N2…).
Max 20.5 958 358 145 Most hypersaline liquid inclusions are between 5 and 25 μm in size.
12 Q3 23.7 3.3 1100 5.1 7.6 4.8 4.1 17.4
8 Q3 20.8 8.6 439 9.5 3 15.4 5 12.7
They form rare primary assemblages and often pseudo-secondary and
9 Q3 64.2 2.5 956 3.9 9.2 3.9 16.3 1.3 secondary trails in Q1–2, but are never observed in Q3. They crosscut pri-
1 Q3 nd 348 0.67 4.7 0.56 14.4 0.47 mary HSMIs and seldom are spatially associated with the silicate melt
2 Q3 6.1 10 345 10.7 2.4 17.3 4.5 17.7 inclusions; therefore they are interpreted to postdate the HSMIs entrap-
3 Q3 4 12 348 9.2 2.9 12.8 3.5 17.3
ment. The hypersaline liquid inclusions contain a dense aggregate of
Mean 23.8 589 5 7.9
Min 4 345 2.4 3.5 transparent crystals, one or two unknown opaque crystals, and often a
Max 64.2 1100 9.2 16.3 hematite flake (Fig. 8A–C). They contain also deformed vapor bubbles
nd: not detected.
that fill 25 to 40 vol.% of the inclusions, whereas a liquid phase makes
a
Internal error (error on the different cycle of an analysis). b10 vol.% of the inclusion, frequently much less. The transparent crys-
tals include: (1) pale-green weakly anisotropic rounded crystals build-
ing up to 30 vol.% of the inclusion, tentatively identified as Fe-chloride
whereas that of Li is slightly higher in Q3 (Q1–2 = 4–20 ppm, Q3 = 4– species although uncertainty remains because of their strong reaction
64 ppm). Iron content is low in Q1–2 and Q3, ranging from 3 to under the Raman monochromatic light; (2) small cubic to rounded
16 ppm, with the exception of two values in botryoidal quartz Q1–2b daughter crystals, possibly KCl; (3) large cubic daughter crystals
(136 and 144 ppm). Titanium content is significantly higher in Q1–2 interpreted as NaCl, and (4) green birefringent rectangular crystals, de-
than in Q3 (Fig. 5B, C), with the highest values recorded in the botryoidal termined as anhydrite by Raman, that fill up to 10 vol.% of the fluid in-
quartz (Q1–2 = 126–358 ppm, Q3 = 2–9 ppm). Titanium is a CL activa- clusion. Raman analyses of the vapor phase reveal the presence of CO2
tor (e.g., Rusk et al., 2008b), thus observed differences in Ti content may with no H2O. Microthermometry results of these hypersaline liquid
explain the differences. inclusions can be summarized as follows: (1) the pale-green weakly
A total of 68 LA-ICP-MS trace element analyses of quartz hosting anisotropic rounded crystals (Fe-chloride?) melt between 268° and
HSMIs, hypersaline liquid and aqueous L-V inclusions (Table 3) were 323 °C; when cooling below 120 °C, they reprecipitate as an aggregate
obtained. The LA-ICP-MS results confirm the higher Li and lower Ti of tiny irregular grains. (2) Melting temperature of the possible KCl crys-
content in Q3 measured by SIMS. No major differences in trace element tals mainly occurs between 294° and 320 °C, just after melting of the
content between the two quartz generations have been observed except first solid; exceptionally temperatures up to 380 °C were also recorded.
for Sn, which is systematically lower in Q3. (3) NaCl melting temperature occurs between 552° to 620 °C. (4) Anhy-
drite is the last solid to melt; in one assemblage melting temperatures
5.5. Petrography and microthermometry of HSMIs and fluid inclusions ranged between 625° to 765 °C. Owing to stretching and decrepitation,
total homogenization temperatures could only be measured for one
The studied quartz-hosted inclusions belong to the following four hypersaline liquid inclusion assemblage with vapor disappearance be-
major types: i) heterogeneous silicate melt inclusions (HSMIs), ii) hy- tween 660° and N800 °C. These temperatures could be affected by mod-
persaline liquid inclusions, iii) aqueous L-V inclusions, and iv) low-den- ification of density related to the α-β quartz transition (Bodnar, 2003),
sity vapor inclusions. Detailed mapping of melt and fluid inclusions and should be taken with caution. Opaque minerals decreased in size
revealed that HSMIs and hypersaline liquid inclusions are exclusively during heating, rarely reaching complete dissolution. The common
hosted in Q1–2, whereas aqueous L-V and low-density vapor inclusions presence of anhydrite and hematite in the hypersaline liquid inclusions
occur as primary fluid inclusion assemblages (FIAs; Goldstein and could indicate H2 diffusion out of the inclusions (Mavrogenes and
Reynolds, 1994) in Q3 and as secondary trails in Q1–2. Bodnar, 1994). Salinities of these inclusions, determined from halite
The HSMIs are small, mostly below 2 μm, some up to 20 μm in size final melting using the equation of Bodnar and Vityk (1994), range be-
and therefore difficult to recognize at room temperature. They form tween 68 and 77 wt% NaCl eq. (Table 4).
masses of several finely crystallized transparent minerals and a de- The aqueous L-V inclusions observed in Q3 as primary and secondary
formed vapor bubble (Fig. 6A, C and E). HSMIs are primary, exclusively FIAs and rarely as secondary FIAs in Q1–2 are irregularly shaped and gen-
trapped in the core of Q1–2 grains that frequently has a hexagonal shape erally small, between 5 and 30 μm in size (Fig. 8D–F). The vapor phase
(Fig. 6). Rare secondary HSMI trails crosscut the quartz. During heating occupies between 20 and 25 vol.% of the inclusion cavities and no CO2
experiments, the progressive melting of different minerals is observed. was detected by Raman spectroscopy. A total of 8 FIAs each including
At around 900 °C, two distinct liquid phases appear. At 1150 °C, all 5 to 14 individual fluid inclusions were measured (Fig. 9, Table 4)

Table 3
Summary of trace element compositions (Min-Max; Mean ± 1σ) of Q1-2 and Q3 determined by LA-ICP-MS analyses.

Quartz generation Li (ppm) Na (ppm) Al (ppm) K (ppm) Ti (ppm) Fe (ppm) Rb (ppm) Sr (ppm) Sn (ppm)

Q1–2 (n = 64) 2.9–43.3 0.5–257 22.6–1570 53.9–318 107–318 14–1422 0.1–5.7 0.01–2.1 23–50
17 ± 9.9 41.3 ± 63.1 340 ± 206 190 ± 59.5 201 ± 51 223 ± 263 1/1.2 0.46 ± 0.61 26.2 ± 6.4
Q3 (n = 4) 33.4–54.1 8.9–24.1 607–960 nd 2.9–13.3 nd nd 0.17–0.31 21.8–25.4
47.8 ± 9.8 15.3 ± 6.9 844 ± 164 6.9 ± 4.7 0.24 ± 0.1 23.3 ± 1.5

nd: not detected.

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markers of the magmatic-hydrotherm..., Chem. Geol. (2016), http://dx.doi.org/10.1016/j.chemgeo.2016.10.032
155
B. Rottier et al. / Chemical Geology xxx (2016) xxx–xxx 11

yielding average homogenization temperatures (Th) between 272° and eq. (Bodnar and Vityk, 1994). Since no detectable liquid phase is present
329 °C and ice melting temperatures (Tmice) between − 22.6° and at room temperature, no microthermometric measurements could be
−0.3 °C, corresponding to salinities between 24.12 and 0.46 wt% NaCl performed in the low-density vapor inclusions.

Fig. 6. A) Transmitted light photomicrograph of primary not heated HSMIs in a quartz crystal core (Q1–2). B) Corresponding SEM-CL image, showing a well-developed oscillatory growth
zoning (quartz sub-generation Q1–2c overgrown by quartz sub-generation Q1–2d); most HSMIs are located in the high CL intensity core. Examples of hexagonal-like (Q1–2) cores (C and D)
and not hexagonal (E) with abundant primary not heated HSMIs (transmitted light photomicrographs). F) The same quartz Q1–2 core than in (E) after heating at 1150 °C; the HSMIs display
now silicate glass and globules crowded with salt and opaque crystals. H–I) Zoom of HSMIs after heating at 1150 °C showing a silicate phase and one or several globules with abundant salt
and opaque crystals.

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12 B. Rottier et al. / Chemical Geology xxx (2016) xxx–xxx

Fig. 7. Step heating of an HSMI at 22 °C (A), 200 °C (B), 250 °C (C), 350 °C (D), 450 °C (E), and 550 °C (F). The black bar corresponds to 10 μm.

5.6. LA-ICP-MS analyses of fluid inclusions Poor reproducibility for some elements can be explained partly by inho-
mogeneous entrapment of some opaque and transparent solids in the
5.6.1. Hypersaline liquid inclusions hypersaline liquid inclusions during their formation (Fig. 10). For
A total of 34 hypersaline liquid inclusions from 6 different FIAs were instance, variations of S, Ca, Sr, and Ba contents might be mainly linked
analyzed by LA-ICP-MS. Average element concentrations and standard to entrapment of anhydrite crystals and of Cu, S, Mo, Ag, and W - to
deviations for each FIA are summarized in Table 5. The reproducibility trapped opaque minerals. Variations may also be related to post-entrap-
of element concentrations within FIAs is good (1σ b 25% of the mean ment modifications, including diffusion. Post-entrapment diffusion
value of the FIA) for Na, K, Rb, and Cs, acceptable (1σ b 35% of the of Cu and Ag through the host quartz has been well documented
mean value of the FIA) for Pb, Mn, and Zn, and relatively poor (1σ = by Kamenetsky and Danyushevsky (2005), Li et al. (2009) and
35–80% of the mean value of the FIA) for S, Ca, Cu, Sr, Mo, Ag, and Ba. Lerchbaumer and Audétat (2012). Abundances of Na, K, and Fe of

Fig. 8. Transmitted light photomicrographs of different fluid inclusion types in Q1–2 and Q3: A) primary hypersaline liquid inclusions hosted in Q1–2. B–C) Secondary hypersaline liquid
inclusions hosted in Q1–2. D–F) Aqueous L-V inclusions hosted in Q3.

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157
B. Rottier et al. / Chemical Geology xxx (2016) xxx–xxx 13

Table 4 5.6.2. Aqueous L-V inclusions


Homogenization temperature and salinity determined by microthermometric measure- Twenty-two aqueous L-V inclusions were selected for LA-ICP-MS
ments of 6 hypersaline liquid inclusion assemblages in Q1–2 and 8 aqueous L-V inclusion
assemblages in Q1−2 and Q3.
analyses. Due to their relatively small size and/or their low salinity,
only 10 analyses of fluid inclusions from 4 FIAs are considered to be an-
FIA FI type n Salinity (wt% 1σ Th (°C) 1σ Pa alytically representative although the data present low reproducibility
NaCl eq.) (bar)
within each FIA. Concentrations of Cu (192–1231 ppm), Zn (683–
CP-14-BR-305″-E-1 Hypersaline 9 70.9 1.5 680–N800 861 ppm), Ag (1-3 ppm), Pb (11–446 ppm), and Mo (2–83 ppm) are
CP-14-BR-305″-D-1 Hypersaline 9 72.2 2.1 N600
moderate to low. Cesium and Rb contents are low, with 4–20 ppm
CP-14-BR-305″-F-1 Hypersaline 6 70 2.2 N600
CP-14-BR-305′-2-3 Hypersaline 21 73.2 2.1 N600 and 8–33 ppm, respectively, compared to the relatively high Sr concen-
CP-14-BR-305′-2-4 Hypersaline 11 71.2 1.9 N600 trations ranging from 82 to 205 ppm. Lithium, B, Al, S, Ca, Ti, As, Sn and
CP-14-BR-305′-2-5 Hypersaline 4 72.5 1.8 N600 Sb have concentrations below the detection limit.
CP-14-BR-305′-4-1 L-V 8 0.5 0.3 308 9 96
CP-14-BR-305′-4-2 L-V 10 0.7 0.2 297 17 82
CP-14-BR-305′-3-1 L-V 7 1.6 0.2 329 12 126
5.7. Composition of heterogeneous silicate melt inclusions (HSMIs)
CP-14-BR-305′-3-2 L-V 14 6.1 0.3 281 8 63
CP-14-BR-305′-2-1 L-V 9 24.1 1.0 272 6 48 5.7.1. Characterization HSMIs after heating using back-scattered electron
CP-14-BR-305′-2-2 L-V 6 6.8 0.5 311 12 96 imaging
CP-14-BR-305-A-2 L-V 9 2.0 0.2 292 5 76
Prior to EPMA, quartz chips heated up to 1150 °C were polished until
CP-14-BR-305-A-3 L-V 5 11.4 0.1 300 8 80
HSMIs were exposed. Polished HSMIs were classified into four different
a
Average minimum pressures of the FIA calculated using the SoWat software types based on back-scattered electron (BSE) images. Type 1 is the most
(Driesner, 2007; Driesner and Heinrich, 2007).
common and corresponds to a homogeneous silicate glass with one or
several lighter circular spots (Figs. 11A and D). These lighter spots cor-
around 45%, 35%, and 20% (±5%), respectively, correspond to common respond to globules crowded with salt and opaque crystals observed
compositions for porphyry brines (Fig. 10A; Kouzmanov and Pokrovski, using the petrographic microscope. EDS analyses of these globules re-
2012). Metal contents are elevated with Mn and Zn ranging from 5000 veal elevated concentrations for Cu and Cl and occasionally weak signals
to 25,000 ppm, Pb from 1000 to 7000 ppm, Mo mainly from 250 to for S and Ag. Type 2 inclusions correspond to homogeneous silicate melt
1000 ppm, W from 13 to 370 ppm, and Ag from 10 to 142 ppm (Table with numerous tiny (b100 nm) white spots dominantly formed by Cu
5). Copper concentrations are heterogeneous with a group with values and Cl according to the EDS analyses performed (Fig. 11B). Type 3
between 5000 and 60,000 ppm and a second group between 13 and inclusions represent homogeneous silicate melt inclusions (Figs. 11A
1000 ppm. Sulfur content varies between 9000 and 57,000 ppm. The and E). Type 4 inclusions are HSMIs with some remnant silicate crystals
positive correlations of S with Cu and Ca (not shown) suggest that (Fig. 11C).
part of the sulfur is present as Cu-sulfide solid inclusions and as anhy-
drite. Several elements, including B, Al, Ti, As, Sn, and Sb were not accu- 5.7.2. EPMA
rately detected due to low signal/background ratio and/or their high A total of 60 EPMA were performed including 41 on silicate glass
concentration in the host quartz. from HSMIs of types 1, 2 and 3, and 19 on Cu- and Cl-rich globules
Rubidium and Cs contents in the fluid inclusions can be used as a from HSMIs of type 1. Since HSMIs are mostly b2 μm in size, i.e., a similar
proxy for the degree of differentiation of the melt from which hydro- volume than that excited by the electron beam, it is challenging to get
thermal fluids are exsolved (Audétat and Pettke, 2003). The ranges of accurate silicate glass-only compositions (supplementary material,
Cs and Rb contents measured in the hypersaline liquid inclusions may Table A.3). The main contamination sources during analyses of the sili-
reflect a progressively increasing differentiation of the melt from cate phase were (1) contamination by small Cu-rich globules, and (2)
which they are exsolved. Positive correlations of K, Pb, Mn, Mo, Zn, contamination by the host quartz. The latter can be due to partial melt-
and W with Rb and Cs possibly reflect enrichment of these elements ing of the host quartz boundary during the heating experiments, or to
in the melt during magmatic differentiation and subsequently in the partial excitation of the host quartz by the electron beam.
exsolved fluids (Fig. 10). The trend observed on the Al2O3 vs. SiO2 plot in Fig. 12 can be
interpreted as reflecting different degrees of contamination of the
melt inclusion analyses by the host quartz. It can be assumed that the
analysis showing the highest Al2O3 value corresponds to the less con-
taminated composition. The chemical composition revealed by this
analyses is rhyolitic (73.04 wt% SiO2, 16.73 wt% Al2O3, 6.96 wt% K2O,
1.99 wt% Na2O, 1.67 wt% FeO, 0.4 wt% TiO2, 0.25 wt% CaO, b0.1 wt%
MgO). It has SiO2 content of 73 wt% that is geologically meaningful
and its composition is coherent with the evolution trend outlined by
the compositions of least altered surrounding magmatic rocks from
the Cerro de Pasco district (Fig. 12; supplementary material, Table
A.1), we therefore consider the obtained composition as representative
for the composition of the silicate melt during entrapment of the HSMIs.
The analyses of Cu- and Cl-rich globules are also contaminated by
the surrounding silicate glasses and the host quartz as shown by the
data provided in the supplementary material, Table A.3. The quantita-
tive EPMA and qualitative EDS measurements reveal positively correlat-
ed high Cu (up to 40 wt%) and Cl (up to 19 wt%) concentrations. Sulfur
content is commonly below 1.25 wt% with the exception of one mea-
surement giving a value at 6.4 wt%.

Fig. 9. Homogenization temperature vs. salinity diagram for the hypersaline liquid and
5.7.3. LA-ICP-MS analyses
aqueous L-V FIAs; the black arrow right to the hypersaline liquid FIAs indicates that The LA-ICP-MS data on heated HSMIs were treated using as an inter-
homogenization temperatures were not reached and are superior to 600 °C. nal standard the Al2O3 content of 16.7 wt% obtained from EPMA for the

Please cite this article as: Rottier, B., et al., Heterogeneous melt and hypersaline liquid inclusions in shallow porphyry type mineralization as
markers of the magmatic-hydrotherm..., Chem. Geol. (2016), http://dx.doi.org/10.1016/j.chemgeo.2016.10.032
158
14
markers of the magmatic-hydrotherm..., Chem. Geol. (2016), http://dx.doi.org/10.1016/j.chemgeo.2016.10.032
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Table 5
Composition of 6 hypersaline liquid inclusion assemblages in Q1–2 and 4 aqueous L-V inclusion assemblages in Q1–2 and Q3 obtained by LA-ICP-MS analysis.

FIA Type n Li (ppm) Na (ppm) S (ppm) K (ppm) Ca (ppm) Mn (ppm) Fe (ppm) Cu (ppm)

Mean 1σ Mean 1σ Mean 1σ Mean 1σ Mean 1σ Mean 1σ Mean 1σ Mean 1σ

305′-S-1 Hypersaline 3 nd 186,035 11,322 15,329 127,553 30,367 48,679 28,576 9903 8058 77,030 10,760 499 687
305‴-D-1 Hypersaline 7 138 62 161,828 9620 39,868 12,487 142,482 17,304 50,258 14,655 14,149 1952 88,710 12,425 26,507 18,264
305‴-F-1 Hypersaline 6 307 64 152,904 19,706 21,027 12,364 151,700 15,949 36,614 10,048 14,457 1614 109,123 46,624 9184 6910
305‴-E-1 Hypersaline 6 nd 171,916 10,328 26,073 12,550 131,103 20,527 45,417 27,915 14,510 4787 83,197 25,478 15,144 8596
305′-2-3 Hypersaline 7 nd 168,538 20,495 19,485 10,825 135,624 24,140 56,095 30,556 13,198 5183 77,487 35,449 230 243
305′-2-4 Hypersaline 5 nd 175,869 18,047 9401 124,252 9627 44,790 25,257 9795 1695 99,831 45,234 524 155
305b-3-1 L-V 3 nd 6176 0 nd 2833 nd 565 7155 9097 1231
305′-4-2 L-V 5 nd 7435 6713 nd nd nd 93 1372 192 233
305′-3-2 L-V 1 nd 23,643 nd nd nd nd nd nd
305′-4-1 L-V 1 nd 4131 nd nd nd nd nd nd

B. Rottier et al. / Chemical Geology xxx (2016) xxx–xxx


nd: not detected.

Table 5 (continued)

FIA Zn (ppm) Rb (ppm) Sr (ppm) Mo (ppm) Ag (ppm) Cs (ppm) Ba (ppm) W (ppm) Au (ppm) Pb (ppm)

Mean 1σ Mean 1σ Mean 1σ Mean 1σ Mean 1σ Mean 1σ Mean 1σ Mean 1σ Mean 1σ Mean 1σ

305′-S-1 4646 1874 513 486 1066 697 577 205 37 1 33 33 1266 1454 109 99 3.5 2272 482
305‴-D-1 12,540 5474 1191 265 793 275 611 247 58 22 89 14 298 110 172 73 0.6 0.2 3314 1042
305‴-F-1 16,515 2003 1402 144 818 263 510 215 65 39 156 10 756 105 86 18 1.4 0.9 4057 1350
305‴-E-1 12,656 1373 1101 143 1946 927 941 572 54 25 113 4 888 448 258 83 1.8 0.8 2980 532
305′-2-3 10,549 8131 943 631 1326 888 458 351 64 59 52 35 834 634 100 109 1.4 2282 1587
305′-2-4 13,675 4787 696 59 916 517 362 86 55 8 37 9 465 288 45 24 0.9 1 2751 413
305b-3-1 861 270 33 4 90 54 83 86 nd 5 1 20 5 20 8 nd 98 93
305′-4-2 683 317 8 8 86 115 22 19 1 7 8 23 10 34 1 0.2 0.03 11 6
305′-3-2 nd 24 207 2 3 20 nd nd 1.5 nd
305′-4-1 nd 17 82 7 nd 4 nd nd nd 446

nd: not detected.

159
B. Rottier et al. / Chemical Geology xxx (2016) xxx–xxx 15

Fig. 10. Composition (LA-ICP-MS microanalysis) of hypersaline liquid inclusions in Q1–2. Each point is a single analysis, the different colors corresponding to different FIAs. A) Mass
variation of major cations (Na, K and Fe) of the hypersaline liquid inclusions in a ternary Na-K-Fe diagram. Crystallization of NaCl-KCl solid solution during ascent of the hypersaline
fluid may explain the evolution marked by the blue arrow (see text). Published compositions of hypersaline fluids from Cu ± Au ± Mo porphyry deposits (gray circle; compiled by
Kouzmanov and Pokrovski, 2012) and compositions of hypersaline fluids from the Biely Vrch deposit (gray diamonds; Koděra et al., 2014) are also plotted for comparison. B–H)
Concentration of selected elements versus Rb in the hypersaline liquid inclusions. (For interpretation of the references to color in this figure legend, the reader is referred to the web
version of this article.)

sample considered to be the most representative for the composition of The different elements can be classified as a function of their behavior
the silicate melt (see above), value which is also consistent with the av- versus Zn. Manganese, Fe, Mo, W, and Pb strongly correlate (linear cor-
erage content of 15.72 ± 0.46 wt% Al2O3 obtained from whole rock geo- relation coefficient r N 0.9) with Zn, indicating that they are mostly
chemistry (n = 13, XRF analyses; electronic supplementary material, hosted in the chlorine-rich globules (Fig. 13). Moderate positive correla-
Table A.1) of rocks ranging from dacitic to rhyolitic composition from tions (0.9 N r N 0.7) between K, Ca, Mg, Rb, Sr, La, Ce and Zn suggest that
the Cerro de Pasco mining district. The LA-ICP-MS results have been they are also subordinately hosted in the silicate phase (Fig. 13). By con-
summarized in Table 6 and plotted versus Zn in Fig. 13, using the affinity trast, Na, Ba, Cs, Cu, Ag, and Au show no linear correlations with Zn indi-
of this element to chlorine as a proxy for the abundance of chlorine-rich cating that they are mostly hosted in the silicate phase (Fig. 13).
globules in the analyzed HSMIs. For most elements, a large composition- Analyses of HSMIs prior to heating experiments are difficult because
al spread is observed. To a large extent it is due to the coexistence in the without heating it is almost impossible (i) to recognize HSMIs, (ii) to
HSMI of different proportions of silicate glass and hypersaline globules. identify properly individual versus a group of HSMIs, and (iii) to identify

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16 B. Rottier et al. / Chemical Geology xxx (2016) xxx–xxx

Fig. 11. BSE images of HSMIs heated at 1150 °C and then exposed at surface by polishing: A) HSMIs of type 1 and 3; B) HSMIs of type 2; C) HSMI of type 4; D) HSMI of type 1; E) HSMIs of
type 3.

small solid inclusions (b1 μm) hosted in quartz close to or attached to 5.8. Cation diffusion through quartz
them. Nevertheless, four analyses were conducted on non-heated
spots that are thought to represent HSMIs (supplementary material, As highlighted by several studies, quartz-hosted fluid and melt in-
Table A.4). Analyses reveal high FeO contents, up to 19 wt%, probably clusions can, after entrapment, diffusively loose or gain some elements
due to contamination by small magnetite inclusions; therefore analyses
could not be considered as representative. Notwithstanding these limi- Table 6
tations, it was recognized that Cu and Ag contents were constantly 1 to 2 Summary of the HSMIs compositions in Q1–2 obtained by LA-ICP-MS analysis.
orders of magnitude lower than those in heated HSMIs.
Zn b 1000 ppm All the data

n Mean 1σ n Mean 1σ

K2O (%) 6 7.0 1.1 14 9.0 2.7


Na2O (%) 6 2.8 1.3 14 3.7 2.1
MgO (%) 5 0.08 0.04 12 0.11 0.04
CaO (%) 4 0.6 0.27 10 1.2 0.81
FeO (%) 6 1.6 0.7 13 2.2 1
Mn (ppm) 6 686 201 14 1930 1357
Zn (ppm) 5 554 157 13 1557 1011
Cu (ppm) 6 33,494 19,976 14 64,580 57,719
Rb (ppm) 6 576 46.5 14 659 133
Sr (ppm) 6 94.9 30.9 14 179 142
Mo (ppm) 6 26.1 20.6 14 78.1 54.5
Ag (ppm) 6 696 645 14 1874 2792
Cs (ppm) 6 48.6 10.8 14 56.1 16.9
Ba (ppm) 6 85.5 52.6 14 143 139
W (ppm) 6 4.1 2.6 14 15.1 13.8
Au (ppm) 4 0.27 0.13 8 0.26 0.09
Pb (ppm) 6 110 53.6 14 317 258
Mg (ppm) 5 471 210 12 682 267
Y (ppm) 6 5.4 1.8 14 6.2 3.1
Zr (ppm) 6 149 84.9 13 153 77.6
Nb (ppm) 6 59.6 52.1 13 55 37.4
La (ppm) 6 16.3 5.4 14 36.9 24.7
Fig. 12. Al2O3 vs. SiO2 content of HSMIs heated at 1150 °C obtained by EPMA and whole
Ce (ppm) 6 37.1 7.3 14 74.1 43.3
rock composition (XRF analyses) of magmatic rocks from the Cerro de Pasco district
Yb (ppm) 4 0.93 0.56 10 1.1 0.72
(n = 13, supplementary material, Table A.1).

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161
B. Rottier et al. / Chemical Geology xxx (2016) xxx–xxx 17

Fig. 13. Concentrations of selected elements versus Zn obtained by LA-ICP-MS analyses of single HSMIs and hypersaline liquid inclusions.

including H, He, Li, Na, Cu, and Ag (Kamenetsky and Danyushevsky, by X-ray Cu concentration maps. The Cu content of a grain that was
2005; Lerchbaumer and Audétat, 2012; Li et al., 2009; Mavrogenes heated at 1150 °C at room pressure under nitrogen atmosphere, ranged
and Bodnar, 1994; Zajacz et al., 2008, 2009). To test if this diffusion phe- between below detection limit (64 ppm) and 291 ppm (Fig. 14).
nomenon applies to the studied HSMIs, profile of Cu concentrations of In contrast, an unheated quartz grain yielded constantly Cu
two quartz grains were acquired by EPMA and subsequently imaged contents below detection limit. The Cu concentration map shows a

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18 B. Rottier et al. / Chemical Geology xxx (2016) xxx–xxx

Fig. 14. EPMA of quartz: A) location of EPMA spots on a SEM-CL image of Q1–2 hosting HSMIs. B) and C) Elemental Cu-Kα and Al-Kα maps. D) Plot of Al and Cu concentrations obtained by
EPMA, LOD of Cu = 64 ppm.

strong positive correlation between Cu and Al in the heated quartz,


suggesting increased Cu diffusion in quartz growth zones and sectors
with lattice defects generated by Al3 + incorporation into the struc-
ture (Fig. 14B and C). LA-ICP-MS analyses of quartz crystals hosting
HSMIs and hypersaline liquid inclusions having been heated at
1150 °C and below 600 °C, respectively, show a strong enrichment
in Cu, Ag, Na, Rb and Li in quartz heated at 1150 °C compared to un-
heated quartz (Fig. 15).

6. Discussion

6.1. Origin of HSMIs in porphyry veins: supercritical melt versus heteroge-


neous entrapment

In contrast with the porphyry environment, where, as mentioned


above, they have been rarely recognized, heterogeneous melt inclusions
consisting of coexisting silicate phase and water-rich phase have been
well documented in pegmatites and aplites associated with S-type gran-
ites (e.g., Thomas and Davidson, 2013, 2016; Veksler et al., 2002). In
pegmatites, HSMIs are interpreted to result from entrapment of “super-
critical melt” containing up to 33 wt% H2O (Thomas and Davidson,
Fig. 15. Trace element concentrations determined by LA-ICP-MS microanalyses of Q1–2
2013). Such heterogeneous melt inclusions are strongly enriched, up heated at 1150 °C (in red), and of Q1–2 heated at b600 °C (in blue). (For interpretation
to several weight percent, in B, F, Cs, Rb and P (Thomas and Davidson, of the references to color in this figure legend, the reader is referred to the web version
2016, and references therein); elements acting as fluxing agents in the of this article.)

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163
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melt and thus increasing the miscibility gap between silicate melt and
water, allowing the formation of such water-rich melts at the magmat-
ic-hydrothermal transition (Veksler, 2004).
In contrast, the HMSIs in early stage porphyry stockwork quartz
at Cerro de Pasco do not show a significant enrichment in incompat-
ible elements such as B, F, Cs and Rb (below 500 ppm, Figs. 12 and 13;
Table 6). These results discard the hypothesis that the studied HSMIs
are the entrapment product of a single “supercritical melt” and favor
the heterogeneous entrapment of two fluids including a silicate melt
and a chlorine-rich fluid. Heterogeneous entrapment has already
been proposed by several authors to explain presence of HSMIs in
magmatic quartz phenocrysts and miarolitic cavities (Campos et al.,
2002, 2006; Davidson et al., 2005; Davidson and Kamenetsky,
2007; Frezzotti, 1992; Fulignati et al., 2005; Harris et al., 2004;
Kamenetsky et al., 2004; Kamenetsky and Kamenetsky, 2010;
Lowenstern, 1994; Zajacz et al., 2008) and in quartz from porphyry
quartz veins (Harris et al., 2003; Pintea, 1995, 2012). At Cerro de
Pasco, a heterogeneous entrapment scenario is supported by (1) an
extremely variable melt/globule ratio in the HSMIs (Figs. 6H and I),
(2) the positive correlation of elements compatible with the chlo-
rine-rich fluid phase in the HSMIs (e.g., K, Fe, Ca, Mn, Pb, Sr, Rb) Fig. 16. Pressure-composition cross section of the H2O-NaCl phase diagram (modified
outlining mixing trends between two hypothetical end members - from Driesner and Heinrich, 2007) illustrating the fluid pathways for the high-
temperature events at Cerro de Pasco. Stage 1 corresponds to magmatic-hydrothermal
an evolved silicate melt and a magmatic fluid (Fig. 13). Since in the
transition conditions, and the HSMIs reflect injection of a hot and evolved silicate melt
studied HSMIs, the presence of globules does not allow determining to shallow levels. During its ascent, the melt decompresses by conserving its high
the exact trace element composition of the silicate phase, the melt temperature (N600 °C) triggering separation of a chlorine rich phase “red B” with
inclusions with the lowest Zn content (b 1000 ppm) have been salinity N90% wt% NaCl eq. and a low-salinity and low-density vapor phase “red V”.
taken as the best available proxy for the composition of the silicate During stage 2, the hydrothermal fluid has to have exsolved at greater pressure.
Assuming a magmatic temperature for the melt (≈750 °C), a pressure of above 700 bar
phase (Table 6, Fig. 13), whereas hypersaline liquid inclusions are is necessary (Driesner and Heinrich, 2007) to separate a brine (green “B″), with salinity
used as a proxy for the magmatic fluid end-member. around 70 wt% NaCl eq. as it has been measured in the hypersaline liquid inclusions
Two different scenarios can explain the heterogeneous entrap- (Fig. 9, Table 4). (For interpretation of the references to color in this figure legend, the
ment of a silicate phase and a hypersaline fluid. First, residual melt reader is referred to the web version of this article.)
and hypersaline fluids could be transported as a heterogeneous mix-
ture of two immiscible fluids toward shallow levels and then trapped
together. This model implies ascent of both liquids having contrast-
ing densities (e.g., 2.6 g/cm3 for the melt and b1.5 g/cm 3 for the 6.2. Fluid evolution
hypersaline fluid; Driesner, 2007) and viscosity along narrow struc-
tures in the shallow portion of a porphyry system, which may be not The presence of simultaneously trapped HSMIs and hypersaline liq-
realistic considering their contrasting physical properties. An alter- uid inclusions in quartz Q1–2 indicates high temperatures of formation
native, more plausible, model is the ascent of a hydrous evolved (N600 °C) consistent with the few obtained total homogenization tem-
melt as a single phase to shallow upper crustal levels, which subse- peratures of both inclusion types (Table 4). Taking into account that the
quently exsolves an aqueous fluid at P-T conditions below the misci- maximum erosion does not exceed 1 km after the trachyte porphyry
bility field of a vapor phase and a hypersaline fluid (Fig. 16). The emplacement (Baumgartner, 2007; Baumgartner et al., 2008), the max-
evolved melt and the newly formed hypersaline fluids are then imum lithostatic pressure for the formation of the porphyry-type min-
trapped together to form the HSMIs, while the low-density vapor eralization can be estimated at 270 bar.
phase tends to escape the site of exsolution by density contrast. Titanium incorporation in quartz is temperature and pressure de-
This exsolution below the miscibility field of vapor and hypersaline pendent (Huang and Audétat, 2012; Rusk et al., 2008b; Thomas et al.,
liquid requires anomalously high-T for a given pressure; such hot 2010; Wark and Watson, 2006), and also depends on the quartz growth
environment is ideally provided by shallow porphyry intrusions rate (Huang and Audétat, 2012). However, the latter parameter ap-
like the trachyte porphyry subject of the present study. This model peared to be strongly variable in the studied hydrothermal quartz vein-
implies a genetic link between the silicate phase and the hypersaline lets as suggested by the variety of textures revealed by SEM-CL. We
fluids trapped as globules in the latter; the existence of such link is recognize that the application of the Ti-in-quartz thermometer is prob-
supported by similar Cs and Rb content in the analyzed HSMIs, lematic and therefore temperatures calculated using the Ti contents in
independently from their melt/globule ratio (Cs and Rb being ele- quartz (Tables 2 and 3) and the equation of Huang and Audétat
ments with fluid/melt partition coefficient close to 1: Zajacz et al., (2012) at P = 0.27 kbar and αTiO2 = 1, can only be used as indicative
2008). of high temperature quartz Q1–2 precipitation (T N 600 °C) and lower
Our hypothesis could be also applied to the formation of abundant temperature quartz Q3 precipitation (T b 450 °C).
primary HSMIs with similar characteristics to those at Cerro de Pasco, Early quartz Q1–2 hosting the HSMIs and the hypersaline liquid inclu-
described in porphyry quartz veins at Deva (Pintea, 1995, 2012, sions is formed during two consecutive stages. Stage 1 corresponds to
Ivascanu et al., 2003) and Bajo de la Alumbrera (Harris et al., 2003) por- magmatic-hydrothermal transition conditions whereby the HSMIs re-
phyry Cu-Au systems. By contrast, our hypothesis probably fails to be flect injection of a hot and evolved silicate melt to shallow crustal levels
applied to the melt inclusions described by Stefanova et al. (2014) in (i.e., b 1 km ≈ 270 bar under lithostatic pressure). It implies that the sur-
quartz from porphyry veins at Elatsite, since they are volumetrically rounding environment is hot enough to prevent complete solidification
minor, secondary, and only few of them contain globules of chlorine- of the melt. During its ascent, the melt decompresses by conserving its
rich fluid. Stefanova et al. (2014) propose that the Elatsite silicate melt high temperature (N 600 °C) triggering separation of a chlorine-rich
inclusions correspond to droplets of residual melts transported by the phase with salinity N 90% wt% NaCl eq. and a low-salinity and low-den-
hydrothermal fluids. sity vapor phase (Fig. 16; Fournier, 1999; Driesner and Heinrich, 2007;

Please cite this article as: Rottier, B., et al., Heterogeneous melt and hypersaline liquid inclusions in shallow porphyry type mineralization as
markers of the magmatic-hydrotherm..., Chem. Geol. (2016), http://dx.doi.org/10.1016/j.chemgeo.2016.10.032
164
20 B. Rottier et al. / Chemical Geology xxx (2016) xxx–xxx

Weis et al., 2012). Rapid quartz precipitation following the decompres- for Q1–2 and 315 °C for Q3 (the mean entrapment temperature assuming
sion and phase separation (Fournier, 1999) allows heterogeneous en- a pressure of 270 bar of aqueous L-V inclusions, Fig. 5C). Applying the
trapment of the silicate phase and the chlorine-rich fluid. equation of Matsuhisa et al. (1979), fluid in equilibrium with Q1–2 and
Stage 2 corresponds to a hydrothermal stage without silicate melt Q3, would have compositions of δ18OfluidQ1–2 = 8.9‰ (n = 30, 2σ =
injection in the shallow environment, in parallel to the thermal 0.4) and δ18OfluidQ3 = 6.5‰ (n = 10, 2σ = 1.8), respectively (Fig. 5C).
retraction of the magmatic-hydrothermal system. Assuming a magmat- The calculated δ18Ofluid in equilibrium with Q1–2 could be interpreted,
ic temperature for the melt (≈750 °C), a pressure N 700 bar is necessary considering the presence of melt inclusions in this quartz generation,
(Driesner and Heinrich, 2007) to separate a brine (green “B2” in Fig. 16), to represent the magmatic oxygen isotope signature. The drop of 2.4‰
with salinity around 70 wt% NaCl eq. as measured in the hypersaline liq- of δ18Ofluid between Q1–2 and Q3 may be attributed to input of around
uid inclusions (Fig. 9, Table 4). The high temperatures registered by 11% of meteoric water (considering δ18O of −13 ± 1‰ for local meteor-
microthermometry and the high Ti content in Q1–2 suggest that the hy- ic water during mineralization: Baumgartner et al., 2008). The above
persaline liquid trapped in Q1–2 is expelled toward shallower levels with calculations of oxygen isotopic composition of fluid in equilibrium
a minimum loss of heat (i.e., almost adiabatically). During its decom- with quartz Q1–2 do not consider the potential influence of high-salinity
pression, the ascending fluid reaches halite saturation in the H2O-NaCl (N70 wt% NaCl eq.) of the fluid on isotope fractionation. Hu and Clayton
system at around 390 bar (Fig. 16; Driesner and Heinrich, 2007), i.e. be- (2003) have shown, at pressures N5 kbar and temperatures N 750 °C,
fore arriving to a pressure of b270 bar (b 1 km), as assumed for the for- that the oxygen isotope fractionation factor in highly saline fluids
mation of the studied porphyry-type mineralization. In a more realistic could decrease up to 0.7‰ compared to the fractionation factor in
complex system H2O-NaCl-KCl-FeCl-(ZnCl)-(CuCl)-(MnCl)-(PbCl), the low-salinity fluids. In contrast, Zhang et al. (1989) did not detect any dif-
phase that would first crystallize is a NaCl-KCl solid solution (Robelin ference of the fractionation factor at atmospheric pressure depending
et al., 2004; Koděra et al., 2014). Therefore, it is suggested that small on the salinity. Even if a fractionation decrease in the range proposed
amounts of NaCl-KCl solid solution have crystallized and been lost by by Hu and Clayton (2003) was considered, the influence on the propor-
the fluid during its ascent. This provides an explanation for the trend ob- tion of meteoric water input for the present study would be marginal
served in the Na-K-Fe diagram toward more Fe-rich compositions of (up to 14% instead of 11%).
HSMIs inclusions, up to 55 wt% Fe (Fig. 10A). The measured hypersaline The textural relationship between Cu-bearing minerals and quartz
liquid inclusions are not so enriched in Fe as the ones reported by suggests that sulfides co-precipitate with or post-date Q3 (Fig. 4). As-
Koděra et al. (2014) at the Biely Vrch shallow porphyry (up to 70% suming that the fluid from which Q3 precipitated represents the ore-
wt% Fe; Fig. 10A), where important NaCl-KCl precipitation is thought forming fluid, it can be concluded that sulfides precipitated from a mod-
to have occurred during fluid ascent. erate temperature (b 350 °C) magmatic-dominated fluid mixed with
The high-temperature vapor inclusions (green and red V in Fig. 16) minor contribution of meteoric waters. LA-ICP-MS analyses of aqueous
that could have been trapped with the HSMIs and the hypersaline liquid L-V inclusions reveal a low to moderate metal content of this fluid
inclusions are not observed. Direct exsolution of hypersaline liquid by (Cu = 92–1231 ppm, Zn = 683–861 ppm, Ag = 1–3 ppm and Pb =
magma is often argued to explain a lack of vapor inclusions (Cline and 1–446 ppm), compared to fluids associated with Q1–2 (Figs.10 and 13).
Bodnar, 1991; Cline and Vanko, 1995; Ulrich et al., 2002; Webster, Similar precipitation of Cu-Fe sulfides spatially associated with late
2004), a process that would require a high Cl/H2O ratio of the melt quartz generations (commonly with lower CL intensity) has been re-
(N0.35 considering a latite composition, Webster, 2004), implying an ported from other porphyry systems (Klemm et al., 2007; Landtwing
anhydrous or an extremely Cl-rich magma (Webster, 2004). Such a et al., 2005, 2010; Müller et al., 2010; Redmond et al., 2004), suggesting
high Cl/H2O ratio is not compatible with the typical water content in decoupling between the high-temperature events (N 500 °C) responsi-
arc magmas (N 4.5 wt%; e.g., Grove et al., 2003). We prefer to explain ble for most of the quartz precipitation and the lower-temperature
the absence of vapor inclusions by fast ascent and decoupling of the events (b 450 °C) linked to sulfide precipitation. By contrast, Harris et
low density vapor phase (b 0.2 g/cm3 at 270 bar, Driesner, 2007) from al. (2003) and Rusk et al. (2008a) proposed that metal precipitation is
the dense hypersaline liquid and the associated silicate phase in such associated with high-temperature quartz at Bajo de la Alumbrera and
a shallow environment. Butte porphyry deposits, respectively.
Presence of aqueous L-V fluid inclusions recorded in Q3 indicates
temperature drop to b 350 °C. The time gap between formation of Q1–2
and Q3 is not known. Minimum entrapment pressures of the aqueous
L-V inclusions, calculated using SoWat software (Driesner, 2007;
Driesner and Heinrich, 2007), range from 48 to 126 bar (Table 4). Con-
sidering the FIAs with the highest Pmin of entrapment, minimum em-
placement depth of 475 m under lithostatic conditions, and of 1750 m
under hot hydrostatic conditions is required. Based on the depth of for-
mation of b1 km as indicated by field evidence (Baumgartner, 2007;
Baumgartner et al., 2008), it can be concluded that quartz Q3 precipitat-
ed under lithostatic or supra-hydrostatic regime. Calculated entrapment
temperatures, using the SoWat software (Driesner, 2007; Driesner and
Heinrich, 2007) and considering a pressure of 270 bar, are between
287° and 346 °C. The observed large salinity range (0.46 to 24.11 wt%
NaCl eq.) could result from local boiling and/or a mixing of magmatic
fluid with minor hot meteoric water, as suggested by oxygen stable iso-
tope analyses discussed below.

6.3. Origin of the fluid and ore precipitation

Oxygen isotopic signatures of the mineralizing fluids in equilibrium


with quartz generations Q1–2 and Q3 were calculated using the in-situ
(SIMS) oxygen isotope analyses of quartz (mean values of δ18OQ1–2 = Fig. 17. LA-ICP-MS microanalyses of HSMIs, hypersaline liquid and aqueous L-V inclusions
10.2‰ and δ18OQ2 = 12.8‰) and precipitation temperatures of 650 °C plotted in a Cu-Zn-Pb ternary diagram.

Please cite this article as: Rottier, B., et al., Heterogeneous melt and hypersaline liquid inclusions in shallow porphyry type mineralization as
markers of the magmatic-hydrotherm..., Chem. Geol. (2016), http://dx.doi.org/10.1016/j.chemgeo.2016.10.032
165
B. Rottier et al. / Chemical Geology xxx (2016) xxx–xxx 21

Fig. 18. Schematic representation of the mineralization stages distinguished in the quartz-magnetite-chalcopyrite-(pyrite) veinlets hosted by the shallow trachyte porphyry at Cerro de
Pasco. As explained in the text, Q1 and Q2 are not easily discernible, and in most cases both quartz generations have been merged under the common denomination Q1–2. The stage 2
quartz overgrowth is exaggerated for the scope of clarity.

6.4. Cu and Ag diffusion through quartz 6.5. Implications for ore formation processes at Cerro de Pasco

The reported Cu and Ag diffusion through quartz into the HSMIs ex- The banded quartz-magnetite-chalcopyrite-(pyrite) veining affect-
plains their extreme enrichment in these two metals (respectively up to ing the trachyte porphyry is the first described porphyry-type mineral-
20 wt% Cu and up 1 wt% Ag). Diffusion during heating experiment was ization spatially associated with the world's second largest epithermal
fast and efficient at experimental conditions of 1150 °C and 1 atm dur- base metal Cerro de Pasco deposit. The epithermal base metal mineral-
ing heating runs of b90 min (Fig. 14). The good correlation between ization is attributed to be formed by dilution of high-salinity magmatic
Al and Cu distribution (Fig. 14), suggests that Cu is incorporated into fluids stored at depth (Baumgartner et al., 2008; Rottier et al., 2015b).
the quartz structure by replacement of monovalent cations, likely H+, Even if there is a temporal gap between formation of the porphyry-
present in an interstitial position as charge compensation for Al3 + type veinlets and base metal epithermal mineralization, study of high-
(Götze et al., 2004). Source of the copper is probably the chalcopyrite temperature fluids trapped in the veinlets provides information on the
present in the veinlets. In the present study, the high Cu contents mea- parental fluid composition likely exsolved from an underlying active
sured in quartz and their good correlation with Al, point directly to cop- magmatic system. The studied HSMIs and hypersaline liquid inclusions
per diffusion without need of comparing analyses of fluid or melt are unusually enriched in sulfur and metals (including Zn, Pb, Mo and
inclusions before and after heating as done in the previous studies by W; Cu concentrations cannot be considered because of post entrapment
Kamenetsky and Danyushevsky (2005), Zajacz et al. (2008, 2009), Li diffusion). The absence of sulfides associated with Q1–2 is easily ex-
et al. (2009), and Lerchbaumer and Audétat (2012). plained by the high temperature and salinity of the mineralizing fluids

Please cite this article as: Rottier, B., et al., Heterogeneous melt and hypersaline liquid inclusions in shallow porphyry type mineralization as
markers of the magmatic-hydrotherm..., Chem. Geol. (2016), http://dx.doi.org/10.1016/j.chemgeo.2016.10.032
166
22 B. Rottier et al. / Chemical Geology xxx (2016) xxx–xxx

resulting in high metal solubility that prevents sulfide precipitation. an anonymous reviewer are thanked for the constructive reviews of
Therefore metal ratios recorded by HSMIs and hypersaline liquid inclu- the manuscript.
sions are not affected by sulfide precipitation and are direct indicators of
the composition of the ore-related magmatic system. The Zn / (Pb + Zn) Appendix A. Supplementary data
ratio of the bulk ore extracted from the epithermal base metal deposit
~0.78 is similar to the ratio measured in the HSMIs and the hypersaline Supplementary data to this article can be found online at http://dx.
liquid inclusions yielding ~0.82 (σ = 0.03) and ~ 0.80 (σ = 0.06), re- doi.org/10.1016/j.chemgeo.2016.10.032.
spectively. This similarity points to a unique source at depth for the
magma at the origin of the epithermal mineralization and the HSMIs
and the hypersaline liquid inclusions (Fig. 17). References

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markers of the magmatic-hydrotherm..., Chem. Geol. (2016), http://dx.doi.org/10.1016/j.chemgeo.2016.10.032
169
Table A.1:XRF analyses of the magmatic rocks of Cerro de Pasco

Sample SiO2 (wt TiO2 (wt Al2O3 (wt Fe2O3 (wt MnO (wt MgO (wt CaO (wt Na2O (wt K2O (wt P2O5 Total (wt
Description LOI (wt%)
number %) %) %) %) %) %) %) %) %) (wt %) %)
Porphyritic
BR301 62.58 0.96 15.98 4.53 0.11 1.90 3.96 4.25 3.38 0.47 1.40 99.52
trachyte stock
BR201 Lapilli dacitic tuff 67.32 0.70 16.29 3.16 0.02 0.77 2.07 4.24 3.39 0.28 1.25 99.48

BR203 Dacitic dome 69.73 0.67 16.11 1.15 0.01 0.39 1.96 4.25 3.70 0.16 1.01 99.14
Rhyodacite
BR230 67.91 0.66 16.26 2.58 0.03 0.90 2.17 4.15 3.88 0.23 1.02 99.79
dome
Quatz-monzonite
BR235 67.31 0.70 16.01 3.34 0.03 0.49 2.17 4.44 3.88 0.27 0.93 99.57
dyke

Quatz-monzonite
BR243 68.51 0.64 15.73 2.68 0.02 0.38 1.66 3.92 3.77 0.48 2.09 99.88
dyke

Quatz-monzonite
BR249 67.84 0.68 15.72 3.88 0.01 0.73 0.12 0.26 4.37 0.27 5.47 99.36
dyke

Quatz-monzonite
BR207 67.86 0.73 15.87 3.19 0.05 0.67 1.41 3.92 3.77 0.31 1.59 99.36
dyke

Quatz-monzonite
BR232 65.40 0.82 15.60 3.54 0.05 0.84 3.31 3.98 3.33 0.37 2.19 99.42
dyke

Quatz-monzonite
BR239 60.58 0.91 14.45 4.08 0.09 1.62 4.68 3.54 3.65 0.46 5.45 99.50
dyke

Quatz-monzonite
BR241 61.60 0.78 14.69 3.64 0.06 1.96 4.85 3.56 3.29 0.34 4.87 99.63
dyke

Quatz-monzonite
BR310 63.73 0.76 14.86 3.27 0.05 1.42 3.95 3.75 3.48 0.32 3.98 99.56
dyke

Quatz-monzonite
BR236 63.94 0.78 15.11 7.73 0.17 0.73 0.51 3.52 3.24 0.37 3.06 99.16
dyke

170
Table A.2a 18O/16O isotopic ratios measurement by SIMS
All standard measured in the session
18 16
O/16O 16
O/Coeff. 18
O/Coeff. O count sdt bracket Sample
primary rate / 18
Sample 18
O count rate 16
O count δ O 2σ IMF
intensity 1s% 1s% 18
O count rate 1s% primary IMF moy 2σ δ18O VSMOW
16
/ O count rate rate intensity
Painetest_1 1.95 2.01E-03 8.54E-03 2.00E+09 5.35E-02 4.04E+06 5.21E-02 1.03E+09 4.36 0.17
Painetest_2 1.97 2.01E-03 5.58E-03 1.99E+09 7.62E-02 4.01E+06 7.65E-02 1.01E+09 4.36 0.11
Painetest_3 1.96 2.01E-03 1.01E-02 1.99E+09 7.05E-02 4.01E+06 6.80E-02 1.01E+09 4.80 0.20
Painetest_4 1.97 2.01E-03 9.84E-03 2.00E+09 8.93E-02 4.03E+06 9.26E-02 1.02E+09 4.67 0.20
Painetest_5 1.97 2.01E-03 1.04E-02 1.99E+09 5.95E-02 4.01E+06 6.30E-02 1.01E+09 4.88 0.21
Painetest_6 1.95 2.01E-03 7.69E-03 1.98E+09 8.19E-02 3.99E+06 8.00E-02 1.02E+09 4.63 0.15 -5.15
Painetest_7 1.95 2.01E-03 8.73E-03 1.98E+09 8.62E-02 4.00E+06 8.84E-02 1.02E+09 4.75 0.17 -5.03
Painetest_8 1.96 2.01E-03 9.67E-03 1.98E+09 8.80E-02 4.00E+06 9.06E-02 1.01E+09 4.64 0.19 -5.14
Painetest_9 1.96 2.01E-03 7.44E-03 1.98E+09 6.44E-02 3.99E+06 6.40E-02 1.01E+09 4.58 0.15 -5.20
Painetest_10 1.96 2.01E-03 7.85E-03 1.98E+09 8.42E-02 4.00E+06 8.42E-02 1.01E+09 4.75 0.16 -5.03
Painetest_11 1.96 2.01E-03 6.94E-03 1.98E+09 8.74E-02 3.99E+06 8.56E-02 1.01E+09 4.48 0.14 -5.30
Painetest_12 1.95 2.01E-03 7.93E-03 1.98E+09 8.37E-02 3.98E+06 8.31E-02 1.01E+09 4.81 0.16 -4.97
Painetest_13 1.96 2.01E-03 7.32E-03 1.98E+09 9.31E-02 3.99E+06 9.46E-02 1.01E+09 4.68 0.15 -5.10
-5.10
Painetest_14 1.89 2.01E-03 1.02E-02 1.92E+09 8.19E-02 3.87E+06 8.27E-02 1.01E+09 4.84 0.20 -4.94
Painetest_15 1.90 2.01E-03 9.56E-03 1.93E+09 9.33E-02 3.88E+06 8.98E-02 1.01E+09 4.59 0.19 -5.19
Painetest_16 2.00 2.01E-03 7.00E-03 1.92E+09 7.36E-02 3.87E+06 7.29E-02 9.59E+08 4.61 0.14 -5.17
Painetest_17 1.91 2.01E-03 9.50E-03 1.92E+09 9.68E-02 3.87E+06 9.81E-02 1.01E+09 4.73 0.19 -5.05
Painetest_18 1.90 2.01E-03 7.83E-03 1.92E+09 1.09E-01 3.87E+06 1.03E-01 1.01E+09 4.61 0.16 -5.17
Painetest_19 1.90 2.01E-03 1.01E-02 1.92E+09 7.28E-02 3.86E+06 7.21E-02 1.01E+09 4.88 0.20 -4.90
Painetest_20 1.90 2.01E-03 9.67E-03 1.92E+09 8.96E-02 3.87E+06 9.28E-02 1.01E+09 4.87 0.19 -4.91
Painetest_21 1.90 2.01E-03 7.30E-03 1.92E+09 7.43E-02 3.86E+06 7.60E-02 1.01E+09 4.46 0.15 -5.32
Painetest_22 1.87 2.01E-03 7.66E-03 1.90E+09 6.17E-02 3.82E+06 6.11E-02 1.01E+09 4.88 0.15 -4.90 10.03
Painetest_23 1.87 2.01E-03 7.76E-03 1.88E+09 6.29E-02 3.79E+06 6.24E-02 1.01E+09 4.46 0.16 -5.31 9.61
-5.10 0.33
Painetest_24 1.85 2.01E-03 7.12E-03 1.87E+09 6.68E-02 3.77E+06 6.69E-02 1.01E+09 4.46 0.14 -5.31 9.61
Painetest_25 1.84 2.01E-03 6.68E-03 1.86E+09 7.22E-02 3.75E+06 7.53E-02 1.01E+09 4.71 0.13 -5.07 9.85
Painetest_26 1.76 2.01E-03 9.63E-03 1.79E+09 9.43E-02 3.61E+06 9.97E-02 1.02E+09 4.57 0.19 -5.21 9.71
Painetest_27 1.77 2.01E-03 9.00E-03 1.79E+09 7.65E-02 3.61E+06 7.76E-02 1.01E+09 4.73 0.18 -5.05 9.88
-5.17 0.30
Painetest_28 1.76 2.01E-03 7.60E-03 1.79E+09 8.40E-02 3.61E+06 8.65E-02 1.02E+09 4.55 0.15 -5.23 9.70
Painetest_29 1.76 2.01E-03 6.69E-03 1.79E+09 7.69E-02 3.60E+06 7.54E-02 1.01E+09 4.49 0.13 -5.28 9.64

171
Table A.2a 18O/16O isotopic ratios measurement by SIMS
All standard measured in the session
18 16
O/16O 16
O/Coeff. 18
O/Coeff. O count sdt bracket Sample
primary rate / 18
Sample 18
O count rate 16
O count δ O 2σ IMF
intensity 1s% 1s% 18
O count rate 1s% primary IMF moy 2σ δ18O VSMOW
16
/ O count rate rate intensity
Painetest_30 2.02 2.01E-03 7.60E-03 2.05E+09 7.52E-02 4.14E+06 7.69E-02 1.02E+09 4.82 0.15 -4.96 10.05
Painetest_31 2.02 2.01E-03 9.03E-03 2.06E+09 7.23E-02 4.14E+06 7.53E-02 1.02E+09 4.87 0.18 -4.91 10.10
-5.11 0.27
Painetest_32 2.03 2.01E-03 1.03E-02 2.05E+09 6.69E-02 4.13E+06 6.36E-02 1.01E+09 4.58 0.21 -5.20 9.80
Painetest_33 2.02 2.01E-03 8.31E-03 2.05E+09 6.87E-02 4.13E+06 7.24E-02 1.01E+09 4.72 0.17 -5.06 9.94
Painetest_34 2.01 2.01E-03 9.66E-03 2.04E+09 8.27E-02 4.11E+06 8.04E-02 1.02E+09 4.80 0.19 -4.98 10.02
Painetest_35 2.01 2.01E-03 1.08E-02 2.08E+09 1.72E-01 4.20E+06 1.70E-01 1.04E+09 4.57 0.22 -5.21 9.79
-5.06 0.24
Painetest_36 2.00 2.01E-03 1.02E-02 2.03E+09 7.17E-02 4.09E+06 7.43E-02 1.01E+09 4.82 0.20 -4.97 10.04
Painetest_37 2.00 2.01E-03 1.21E-02 2.02E+09 7.13E-02 4.07E+06 7.19E-02 1.01E+09 4.62 0.24 -5.16 9.84
Painetest_38 1.99 2.01E-03 8.81E-03 1.97E+09 8.02E-02 3.97E+06 8.04E-02 9.91E+08 4.49 0.18 -5.29 9.71
Painetest_39 1.95 2.01E-03 1.10E-02 1.97E+09 8.15E-02 3.98E+06 7.84E-02 1.01E+09 4.84 0.22 -4.94 10.07
-5.10 0.26
Painetest_40 1.96 2.01E-03 9.72E-03 1.99E+09 7.75E-02 4.02E+06 8.21E-02 1.02E+09 4.68 0.19 -5.10 9.90
Painetest_41 1.95 2.01E-03 1.21E-02 1.99E+09 7.62E-02 4.01E+06 7.79E-02 1.02E+09 4.61 0.24 -5.17 9.83
Painetest_42 1.93 2.01E-03 1.04E-02 1.97E+09 8.13E-02 3.98E+06 7.90E-02 1.02E+09 4.64 0.21 -5.14 9.86
Painetest_43 1.94 2.01E-03 6.55E-03 1.97E+09 9.06E-02 3.97E+06 9.17E-02 1.02E+09 4.30 0.13 -5.47 9.52
-5.21 0.32
Painetest_44 1.94 2.01E-03 1.04E-02 1.97E+09 7.39E-02 3.97E+06 7.42E-02 1.02E+09 4.50 0.21 -5.28 9.72
Painetest_45 1.94 2.01E-03 9.36E-03 1.97E+09 8.47E-02 3.97E+06 8.55E-02 1.02E+09 4.49 0.19 -5.29 9.71
Painetest_46 1.93 2.01E-03 8.88E-03 1.96E+09 9.10E-02 3.95E+06 9.53E-02 1.02E+09 4.44 0.18 -5.34 9.66
Painetest_47 1.93 2.01E-03 1.19E-02 1.96E+09 5.99E-02 3.95E+06 5.69E-02 1.02E+09 4.47 0.24 -5.30 9.70
-5.31 0.21
Painetest_48 1.92 2.01E-03 1.15E-02 1.96E+09 7.17E-02 3.95E+06 7.40E-02 1.02E+09 4.54 0.23 -5.24 9.77
Painetest_49 1.93 2.01E-03 9.73E-03 1.95E+09 7.11E-02 3.93E+06 7.17E-02 1.01E+09 4.35 0.19 -5.43 9.57
Painetest_50 1.91 2.01E-03 8.31E-03 1.94E+09 8.09E-02 3.91E+06 8.18E-02 1.02E+09 4.54 0.17 -5.24 9.76
Painetest_51 1.91 2.01E-03 9.35E-03 1.94E+09 7.09E-02 3.91E+06 6.90E-02 1.02E+09 4.70 0.19 -5.08 9.92
Painetest_52 1.91 2.01E-03 6.92E-03 1.94E+09 8.13E-02 3.91E+06 8.31E-02 1.02E+09 4.65 0.14 -5.13 9.87
Painetest_53 1.91 2.01E-03 8.66E-03 1.94E+09 9.26E-02 3.90E+06 9.41E-02 1.01E+09 4.73 0.17 -5.05 9.95
-5.22 0.23
Painetest_54 1.90 2.01E-03 1.15E-02 1.93E+09 2.03E-01 3.89E+06 2.02E-01 1.02E+09 4.54 0.23 -5.24 9.76
Painetest_55 1.99 2.01E-03 7.67E-03 1.94E+09 2.19E-01 3.91E+06 2.20E-01 9.74E+08 4.47 0.15 -5.31 9.69
Painetest_56 1.90 2.01E-03 6.45E-03 1.94E+09 1.42E-01 3.91E+06 1.41E-01 1.02E+09 4.66 0.13 -5.12 9.89
Painetest_57 1.91 2.01E-03 7.80E-03 1.93E+09 8.12E-02 3.89E+06 8.46E-02 1.01E+09 4.61 0.16 -5.17 9.83

172
Table A.2b 18O/16O isotopic ratios measurement by SIMS
All standard measured in the session
18
O/16O 16
O/Coeff. 18
O/Coeff. 16
Sample
O count rate /
primary Quartz
Sample# 18
O count rate primary δ18O 2σ
intensity 1s% 16
O count rate 1s% 18
O count rate 1s% δ18O VSMOW 2σ generation
/16O count rate intensity

BR305_1 1.79 2.02E-03 8.40E-03 1.81E+09 7.16E-02 3.66E+06 6.47E-02 1.01E+09 5.25 0.17 10.48 0.30 Q1
BR305_2 1.79 2.02E-03 8.53E-03 1.80E+09 6.84E-02 3.62E+06 6.59E-02 1.01E+09 4.93 0.17 10.15 0.30 Q1
BR305_3 1.78 2.02E-03 8.87E-03 1.80E+09 7.83E-02 3.63E+06 7.61E-02 1.01E+09 5.15 0.18 10.38 0.30 Q1
BR305_4 1.78 2.02E-03 9.44E-03 1.80E+09 6.23E-02 3.62E+06 6.44E-02 1.01E+09 4.96 0.19 10.18 0.30 Q1
BR305_5 1.78 2.01E-03 5.89E-03 1.79E+09 8.15E-02 3.60E+06 8.06E-02 1.00E+09 4.83 0.12 10.05 0.30 Q1
BR305_6 1.77 2.01E-03 1.06E-02 1.79E+09 6.89E-02 3.61E+06 6.82E-02 1.01E+09 4.82 0.21 10.05 0.30 Q1
BR305_7 1.77 2.02E-03 7.69E-03 1.79E+09 7.41E-02 3.62E+06 7.38E-02 1.02E+09 4.92 0.15 10.14 0.30 Q1
BR305_8 1.78 2.02E-03 8.98E-03 1.80E+09 6.55E-02 3.63E+06 6.87E-02 1.01E+09 4.96 0.18 10.18 0.30 Q1
BR305_9 1.77 2.02E-03 1.06E-02 1.79E+09 7.53E-02 3.60E+06 7.57E-02 1.01E+09 5.01 0.21 10.24 0.30 Q1
BR305_10 1.77 2.02E-03 1.09E-02 1.78E+09 7.69E-02 3.60E+06 7.82E-02 1.01E+09 5.12 0.22 10.34 0.30 Q1
BR305_14 1.76 2.02E-03 5.88E-03 1.79E+09 7.64E-02 3.61E+06 7.53E-02 1.02E+09 5.22 0.12 10.38 0.27 Q1
BR305_15 1.76 2.02E-03 7.21E-03 1.78E+09 7.02E-02 3.59E+06 6.65E-02 1.01E+09 4.99 0.14 10.16 0.27 Q1
BR305_16 1.76 2.02E-03 1.18E-02 1.78E+09 7.78E-02 3.59E+06 7.79E-02 1.01E+09 4.91 0.24 10.08 0.27 Q1
BR305_17 1.76 2.02E-03 1.04E-02 1.84E+09 1.90E-01 3.70E+06 1.91E-01 1.05E+09 4.89 0.21 10.06 0.27 Q1
BR305_18 1.82 2.01E-03 9.20E-03 1.89E+09 1.03E-01 3.81E+06 1.05E-01 1.04E+09 4.82 0.18 9.98 0.27 Q1
BR302_06 2.02 2.02E-03 7.05E-03 2.07E+09 9.33E-02 4.18E+06 9.00E-02 1.03E+09 5.21 0.14 10.37 0.27 Q1
BR302_07 2.02 2.02E-03 7.77E-03 2.07E+09 7.35E-02 4.18E+06 7.51E-02 1.03E+09 5.03 0.16 10.13 0.24 Q1
BR302_08 2.02 2.02E-03 5.53E-03 2.07E+09 7.08E-02 4.18E+06 6.90E-02 1.03E+09 5.20 0.11 10.30 0.24 Q1
BR302_09 2.02 2.02E-03 7.99E-03 2.09E+09 1.26E-01 4.21E+06 1.23E-01 1.03E+09 5.07 0.16 10.17 0.24 Q1
BR302_10 2.03 2.01E-03 9.28E-03 2.08E+09 1.12E-01 4.18E+06 1.14E-01 1.02E+09 4.67 0.19 9.77 0.24 Q1
BR302_11 2.00 2.02E-03 6.89E-03 2.06E+09 9.83E-02 4.15E+06 9.73E-02 1.03E+09 5.74 0.14 10.85 0.24 Q1
BR302_12 2.00 2.02E-03 6.99E-03 2.06E+09 8.11E-02 4.14E+06 8.33E-02 1.03E+09 5.08 0.14 10.19 0.24 Q1
BR302_13 2.00 2.02E-03 9.88E-03 2.07E+09 8.05E-02 4.16E+06 8.42E-02 1.03E+09 5.04 0.20 10.14 0.24 Q1
BR302_14 2.01 2.02E-03 9.83E-03 2.08E+09 9.31E-02 4.19E+06 9.28E-02 1.03E+09 5.56 0.20 10.67 0.24 Q1
BR302_17 2.01 2.02E-03 8.53E-03 2.05E+09 8.68E-02 4.14E+06 8.93E-02 1.02E+09 5.82 0.17 10.94 0.24 Q1
BR302_18 2.01 2.02E-03 9.12E-03 2.06E+09 9.18E-02 4.14E+06 9.07E-02 1.02E+09 5.02 0.18 10.12 0.24 Q1
BR302_19 2.01 2.02E-03 8.25E-03 2.06E+09 7.31E-02 4.14E+06 7.32E-02 1.02E+09 4.94 0.16 10.04 0.24 Q1
BR302_20 2.01 2.02E-03 8.18E-03 2.07E+09 7.14E-02 4.16E+06 7.31E-02 1.03E+09 4.94 0.16 10.04 0.24 Q1
BR302_21 2.01 2.01E-03 8.71E-03 2.05E+09 8.25E-02 4.14E+06 8.65E-02 1.02E+09 4.82 0.17 9.92 0.24 Q1

173
Table A.2b 18O/16O isotopic ratios measurement by SIMS
All standard measured in the session
18
O/16O 16
O/Coeff. 18
O/Coeff. 16
Sample
O count rate /
primary Quartz
Sample# 18
O count rate primary δ18O 2σ
intensity 1s% 16
O count rate 1s% 18
O count rate 1s% δ18O VSMOW 2σ generation
/16O count rate intensity

BR302_22 2.00 2.02E-03 1.19E-02 2.05E+09 7.57E-02 4.14E+06 7.92E-02 1.02E+09 5.24 0.24 10.35 0.24 Q1
BR302_1 1.88 2.02E-03 1.07E-02 1.97E+09 2.64E-01 3.98E+06 2.67E-01 1.05E+09 8.15 0.21 13.33 0.27 Q2
BR302_2 1.95 2.02E-03 8.06E-03 2.04E+09 1.25E-01 4.11E+06 1.29E-01 1.05E+09 7.61 0.16 12.79 0.27 Q2
BR302_3 2.00 2.02E-03 6.81E-03 2.06E+09 8.79E-02 4.16E+06 8.85E-02 1.03E+09 7.23 0.14 12.41 0.27 Q2
BR302_4 2.01 2.02E-03 6.74E-03 2.08E+09 1.05E-01 4.19E+06 1.05E-01 1.03E+09 5.25 0.13 10.42 0.27 Q2
BR302_15 2.01 2.02E-03 8.26E-03 2.05E+09 7.08E-02 4.13E+06 6.83E-02 1.02E+09 7.68 0.17 12.80 0.24 Q2
BR302_16 2.01 2.02E-03 8.40E-03 2.04E+09 8.50E-02 4.14E+06 8.84E-02 1.02E+09 8.76 0.17 13.88 0.24 Q2
BR302_23 2.00 2.02E-03 7.02E-03 2.06E+09 2.03E-01 4.17E+06 2.05E-01 1.03E+09 8.32 0.14 13.49 0.26 Q2
BR305_11 1.76 2.02E-03 1.13E-02 1.79E+09 8.29E-02 3.61E+06 8.48E-02 1.01E+09 7.74 0.23 12.98 0.30 Q2
BR305_12 1.76 2.02E-03 1.02E-02 1.79E+09 6.67E-02 3.61E+06 6.71E-02 1.02E+09 7.60 0.20 12.84 0.30 Q2
BR305_13 1.76 2.02E-03 9.75E-03 1.80E+09 6.01E-02 3.63E+06 5.88E-02 1.02E+09 7.86 0.19 13.04 0.27 Q2
BR302_05 2.02 2.02E-03 7.38E-03 2.07E+09 6.73E-02 4.17E+06 6.62E-02 1.02E+09 6.22 0.15 11.39 0.27 Q1/Q2

174
Table A.3:
EPMA analyses performed on the HSMIs

Al2O3 (wt SiO2 K2O (wt CaO TiO2 FeO (wt Na2O (wt MgO MnO (wt
Sample name Type* F (wt %) S (wt %) Cl (wt %) Cu (wt %) Total
%) (wt %) %) (wt %) (wt %) %) %) (wt %) %)

Q1-Mi8c Silicate 16.03 71.17 4.05 0.31 0.40 0.98 0.74 0.09 0.13 0.32 b.d. 94.23
Q3_M5b Silicate 16.73 73.04 6.96 0.25 1.67 1.99 0.11 0.23 100.98
Q3_M7b Silicate 12.58 73.96 3.29 0.19 0.18 0.84 1.65 0.07 0.20 5.06 98.03
Q3_M7a Silicate 7.77 75.82 3.90 0.49 0.15 1.14 1.35 0.03 0.61 5.85 97.12
Q3_M4a2 Silicate 11.48 77.60 4.73 0.53 0.22 0.93 2.56 0.34 0.59 98.98
Q5-MI8a Silicate 10.56 77.77 3.90 0.35 0.31 1.83 1.48 0.07 0.25 2.04 98.59
Q1-MI5a Silicate 10.22 77.92 2.67 0.47 0.20 0.11 0.43 0.10 0.47 92.59
Q1-Mi8a Silicate 12.36 79.53 4.62 0.32 0.37 1.69 0.09 0.03 0.67 99.68
Q5-MI8b Silicate 11.10 80.15 3.80 0.33 0.18 1.08 2.75 0.20 1.51 101.09
Q3_M4a Silicate 12.32 81.01 3.00 0.57 0.26 0.94 1.04 0.07 0.33 0.61 100.16
Q2_M3b Silicate 7.41 81.27 3.84 0.17 0.13 0.45 1.43 0.19 5.14 100.03
Q3_M4d Silicate 9.13 81.43 3.78 0.15 0.13 0.68 1.85 0.05 0.25 0.79 98.23
Q4_M2a2 Silicate 6.54 82.20 2.29 0.51 0.13 1.11 1.39 0.17 0.23 4.28 98.84
Q5-MI6a Silicate 7.10 82.39 3.36 0.14 0.17 0.71 1.04 0.19 3.63 98.73
Q3_M5a Silicate 9.47 82.59 2.83 0.54 0.13 1.05 1.37 0.23 1.18 99.39
Q2_M2a Silicate 10.84 82.61 3.21 0.29 0.00 2.62 2.17 101.74
Q3_M4c Silicate 9.13 82.90 2.91 0.53 0.13 0.73 1.43 0.11 0.49 98.37
Q4_M1a1 Silicate 8.16 83.94 4.41 0.30 0.20 1.00 1.52 0.06 0.06 0.32 0.40 100.39
Q3_M1c Silicate 8.30 84.00 2.39 0.26 0.89 1.62 0.48 1.68 99.62
Q2_M1a Silicate 6.49 84.30 3.26 0.17 0.26 1.39 0.10 5.40 101.38
Q2_M3c Silicate 3.61 84.82 1.66 0.04 0.21 1.16 0.34 3.83 95.68
Q4_M2a1 Silicate 5.93 85.18 2.57 0.43 0.15 0.98 0.71 0.13 0.19 2.76 99.05
Q5-MI6c Silicate 6.21 85.95 2.11 0.11 0.15 0.48 1.22 0.13 4.40 100.76
Q5-MI8c Silicate 6.24 86.24 2.86 0.21 0.15 0.66 0.86 0.13 2.58 99.93
Q2_M2bc Silicate 6.50 86.26 2.36 0.16 0.15 0.48 2.15 0.08 4.76 102.89
Q4_M1b Silicate 7.63 86.55 2.99 0.19 0.54 2.22 0.09 0.74 100.94
Q2_M5a Silicate 5.53 87.55 2.29 0.10 0.16 0.42 1.26 0.14 4.03 101.48
Q5-MI8bis_a Silicate 5.91 89.09 1.78 0.12 0.14 0.59 1.63 0.09 1.62 100.98
Q4_M2b Silicate 5.70 89.41 2.39 0.11 0.16 0.38 1.61 0.12 2.73 102.61
Q2_M1b Silicate 3.40 89.52 1.74 0.08 0.26 0.33 1.02 0.15 7.44 103.94
Q5-MI8bis_b Silicate 5.41 89.54 2.24 0.08 0.13 0.53 1.08 0.06 1.43 100.50
Q3_M3a Silicate 5.78 89.83 1.82 0.19 0.14 0.65 0.69 0.06 0.61 99.76
Q3_M6 Silicate 4.71 90.41 1.50 0.17 0.57 0.67 0.10 1.22 99.35
Q5-MI9a Silicate 4.35 90.75 1.81 0.08 0.51 1.01 0.04 2.04 100.59
Q5-MI8bis_c Silicate 3.39 91.25 1.54 0.60 1.59 1.04 0.23 0.09 0.74 100.46
Q2_M3a1 Silicate 3.54 91.67 0.57 0.08 0.39 0.42 0.17 0.15 96.99
Q5-MI7a Silicate 2.08 92.47 1.21 0.42 1.00 0.42 0.19 0.14 2.41 100.34
Q3_M1b Silicate 3.86 92.66 2.22 0.14 0.57 1.10 0.10 0.19 0.05 0.30 101.19

175
Table A.3:
EPMA analyses performed on the HSMIs

Al2O3 (wt SiO2 K2O (wt CaO TiO2 FeO (wt Na2O (wt MgO MnO (wt
Sample name Type* F (wt %) S (wt %) Cl (wt %) Cu (wt %) Total
%) (wt %) %) (wt %) (wt %) %) %) (wt %) %)

Q4_M1d Silicate 4.38 92.89 1.71 0.15 0.63 1.53 0.05 0.19 101.53
Q4_M2c Silicate 3.71 93.57 1.22 0.06 0.34 0.42 0.10 2.75 102.16
Q4_M1c Silicate 2.76 96.53 0.76 0.09 0.30 0.30 0.06 0.68 101.48
Q3_M4b Silcate + globule 6.17 77.19 3.51 1.12 0.20 2.14 1.28 0.26 0.10 2.37 2.46 96.79
Q3_M4a2_bul Silcate + globule 9.73 65.10 2.52 0.37 0.14 0.62 0.81 0.39 7.04 18.25 104.95
Q4_M1a3_bul Silcate + globule 7.62 67.38 3.47 0.21 0.21 0.83 0.99 0.12 1.13 2.70 14.48 99.15
Q5-MI5a Silcate + globule 4.71 67.92 2.21 0.38 0.95 1.44 0.06 0.07 0.50 78.24
Q1-Mi9a Silcate + globule 30.67 57.70 3.83 0.78 0.89 2.43 0.66 0.31 0.11 0.00 0.90 98.27
Q2_M3a2 Silcate + globule 28.28 61.59 2.92 0.36 0.33 2.22 1.71 0.26 0.46 0.65 98.79
Q1-Mi8b Silcate + globule 21.14 69.28 4.36 0.52 0.13 0.37 0.69 0.07 0.62 97.19
Q5-MI6b Silcate + globule 6.48 71.07 2.24 0.16 0.19 0.51 1.81 0.06 0.13 0.83 18.67 102.16
Q3_M5a_bul1 Silcate + globule 6.26 50.10 2.40 0.22 0.52 2.38 0.05 19.04 24.10 105.07
Q3_M5a_bul2 Silcate + globule 4.03 52.64 1.21 0.09 0.44 0.88 6.39 2.45 40.39 108.52
Q4_M1a4_bul Silcate + globule 2.50 87.52 0.96 0.16 0.22 0.23 0.39 3.45 9.99 105.42
Q3_M7a_bul Silcate + globule 3.64 44.44 1.65 0.18 0.40 1.31 0.10 1.22 19.20 30.59 102.74
Q3_M1a3_bul Silcate + globule 2.14 88.80 0.93 3.73 0.36 1.79 0.07 0.59 98.42
Q2_M5b Silcate + globule 3.55 73.04 2.10 0.59 0.97 1.17 0.56 4.22 15.05 101.23
Q5-MI8bis_d Silcate + globule 6.67 71.58 4.85 0.26 0.19 1.15 0.62 0.07 0.06 0.43 8.70 94.58
Q3_M1c_bul Silcate + globule 7.68 77.93 3.15 0.21 0.75 1.61 0.14 1.52 7.45 100.43
Q2_M2b Silcate + globule 5.86 83.61 2.75 0.13 0.43 1.82 0.27 7.72 102.60
Q4_M1a2 Silcate + globule 8.07 79.83 3.95 0.29 0.24 1.00 1.29 0.24 1.44 4.00 100.36
Q3_M6_bul Silcate + globule 2.40 90.99 0.92 0.09 0.25 0.30 0.14 0.80 6.15 102.04
* Silicate refers to analyses of the silicate phase of the HSMI and Silicate + globule refers to analyses focused Cu and Cl rich globules

176
Table A.4: LA-ICP-MS analyses of not heated HSMIs (polluted by magnetite inclusions)
All results are in ppm

Sample# Li(7) B(11) Na(23) Mg(25) Al(27) Si(28) P(31) S(34) K(39) Ca(44) Ti(49) Mn(55) Fe(57) Cu(65) Zn(66) As(75) Rb(85)
HSMIs_NH_1 n.d n.d 58610 2491 84676 n.d n.d n.d 58480 15565 n.d 2880 141160 <0.28 1442 n.d 209
HSMIs_NH_2 n.d n.d 61490 2445.583722 84676 n.d n.d 6982 63890 16300 n.d 3262 146800 241 1729 n.d 229
HSMIs_NH_3 n.d n.d 62030 1064 84676 n.d n.d 3521 90170 12080 n.d 3175 58060 14.2 1849 n.d 316
HSMIs_NH_4 n.d n.d 48510 1715 84676 n.d n.d <246 96140 18160 n.d 4919 41270 6380 3446 n.d 741
Sample# Sr(88) Y(89) Zr(90) Nb(93) Mo(95) Ag(107) Sn(118) Sb(121) Te(125) Cs(133) Ba(137) La(139) Ce(140) Yb(172) W(182) Au(197) Pb(208)
HSMIs_NH_1 820 4.1 54.6 17.5 106 6.1 n.d n.d n.d 10.9 768 28.6 54.1 n.d 46.8 n.d 266
HSMIs_NH_2 878 4.2 55.9 17.4 117 6.9 n.d n.d n.d 11.2 860 31.4 60.3 n.d 49 n.d 324
HSMIs_NH_3 405 6.8 94.6 8.8 117 5.3 n.d n.d n.d 16.8 1163 30.3 62.6 n.d 51.5 n.d 460
HSMIs_NH_4 431 5.2 174 19.3 215 16.4 n.d n.d n.d 53.5 466 90.9 178 n.d 86.9 n.d 1126

177
Chapter 4:

Sulfide replacement processes revealed by textural and


LA-ICP-MS trace element analyses: example from the
early mineralization stages at Cerro de Pasco, Peru

Rottier B.*, Kouzmanov K.*, Wälle M.,** Bendezú, R.***, Fontboté L.*

* Department of Earth sciences, University of Geneva, 1205 Geneva, Switzerland


** Institute of Geochemistry and Petrology, ETH Zürich, 8092 Zürich, Switzerland
*** Volcan Compania Minera S.A.A., Av. Gregorio Escobedo 710, Lima
Corresponding author: Bertrand.Rottier@unige.ch, +41 223 796 826

Published in Economic Geology

178
©2016 Society of Economic Geologists, Inc.
Economic Geology, v. 111, pp. 1347–1367

Sulfide Replacement Processes Revealed by Textural and


LA-ICP-MS Trace Element Analyses:
Example from the Early Mineralization Stages at Cerro de Pasco, Peru*
B. Rottier,1,† K. Kouzmanov,1 M. Wälle,2 R. Bendezú,3 and L. Fontboté1
1 Department of Earth Sciences, University of Geneva, 1205 Geneva, Switzerland
2 Institute of Geochemistry and Petrology, ETH Zürich, 8092 Zürich, Switzerland
3 Volcan Compania Minera S.A.A., Lima, Peru

Abstract
The large Cerro de Pasco Cordilleran base metal deposit in central Peru is the result of three successive mineral-
izing stages comprising both low- and high-sulfidation mineral associations: (A) several pyrrhotite pipes grading
outward to sphalerite and galena replacement bodies, (B) a massive, funnel-shaped pyrite-quartz replacement
orebody, and (C) E-W–trending Cu-Ag-(Au-Zn-Pb) enargite-pyrite veins and well-zoned Zn-Pb-(Bi-Ag-Cu)
carbonate-replacement orebodies. This superposition of hydrothermal events leads to complex replacement
textures and crosscutting relationships. A detailed study of the textures and mineral composition of the up to
15-m-wide replacement front existing between the pyrrhotite pipes and the pyrite-quartz body allows for clari-
fication of the relative chronology of the hydrothermal events. The results show that, in contrast to previous
interpretations, the emplacement of the pyrrhotite pipes and their Zn-Pb mineralized rims precedes that of the
pyrite-quartz body. The replacement textures affecting pyrrhotite and arsenopyrite and the nature of the newly
formed minerals have been used as a qualitative way to track the evolution of fS2, fO2, and pH of the mineral-
izing fluids. Two steps of pyrrhotite replacement have been recorded. The first one takes place under moderate
acidity and relatively reduced to moderately oxidized conditions and is marked by replacement of pyrrhotite by
euhedral nonporous pyrite. The second step occurs under more acidic and oxidized conditions and is character-
ized by replacement of pyrrhotite by porous marcasite and replacement of arsenopyrite by pyrite. Subsequently,
marcasite is partly replaced by fine-grained euhedral nonporous pyrite. LA-ICP-MS trace element analyses of
the replaced pyrrhotite and arsenopyrite and of the newly formed marcasite and pyrite support dissolution-
reprecipitation as the main mechanism for replacement. Positive correlations between some of the elements
(e.g., Pb-Sb, Pb-Ag) are indicative of the possible presence of nanoscale solid inclusions as main carriers for
those elements; however, coupled substitutions and incorporation of some of the elements at a ppm level into
the pyrite and marcasite structures cannot be excluded. The obtained As, Sb, Pb, and Bi values in pyrite are
systematically higher than published data of pyrite in epithermal and porphyry systems. Nature and trace ele-
ment content of the newly formed minerals yield information on the physicochemical conditions during their
precipitation, the initial trace element content of replaced minerals, and the subsequently dissolved neighbor-
ing phases. The results show that the metal concentration of the fluid is locally influenced by the composition
of the dissolved minerals. This study leads to a simpler interpretation of the fluid evolution than previously
proposed, with a progressive increase of fS2, fO2, and pH as a result of decreasing wall-rock buffering during the
three successive mineralizing stages at Cerro de Pasco.

Introduction deposits (e.g., Marcoux et al., 2008) and metamorphosed


Ore deposits are typically formed by multiple distinct hydro- sulfide ore deposits (e.g., Tomkins et al., 2006). It has been
thermal events, resulting in contrasting mineral assemblages shown that early pyrrhotite is often replaced by pyrite and/or
and complex crosscutting and replacement textures that can marcasite, resulting in particular replacement textures due to
be used to track variations of fS2, fO2, and pH of the ore-form- increase of fS2 and fO2 in parallel with a decrease of pH of the
ing fluid. The pyrrhotite-arsenopyrite mineral assemblage fluid (Murowchick, 1992; Qian et al., 2011).
commonly occurs during early mineralization phases of vari- Cerro de Pasco is a porphyry-related epithermal base
ous magmatic-hydrothermal systems, including polymetallic metal deposit (i.e., Cordilleran polymetallic mineralization:
vein and replacement deposits (e.g., Einaudi et al., 2003; Baumgartner et al., 2008). This type of mineralization occurs
Simmons et al., 2005; Baumgartner et al., 2008), Sn-W veins in an environment similar to the epithermal high-sulfidation
(e.g., Kelly and Rye, 1979), low-sulfidation epithermal depos- Au-(Ag) deposits. It is formed under subepithermal to epi-
its (e.g., Pals and Spry, 2003; Sillitoe and Hedenquist, 2003), thermal conditions between 350° to 150°C and occurs as veins
skarns (e.g., Gray et al., 1995; Fuertes-Fuente et al., 2000), in silicic host rocks and as replacement orebodies in a carbon-
as well as orogenic gold (e.g., Genkin et al., 1998; Haeberlin ate sedimentary sequence (Fontboté and Bendezú, 2009).
et al., 2004; Large et al., 2011), volcanogenic massive sulfide The mineralization is typically sulfide rich (up to 50 vol % total
sulfide) and includes a large range of metals—Zn-Pb-Cu-Ag-
† Corresponding author: e-mail, Bertrand.Rottier@unige.ch
(Au-Bi-Sb). Cerro de Pasco is the second largest known Cor-
*A digital Appendix for this paper is available at http://economicgeology.org/ dilleran base metal deposit after Butte (Montana). According
and at http://econgeol.geoscienceworld.org/. to the known resources plus the past production (post-1950),
Submitted: November 20, 2015
0361-0128/16/4421/1347-21 1347 Accepted: March 31, 2016

179
1348 ROTTIER ET AL.

the deposit is estimated at more than 175 million metric tons of zircon; Baumgartner et al., 2009). The phreatomagmatic
(Mt) at 7 wt % Zn and 2 wt % Pb, as well as 3 oz/t Ag. In addi- activity was followed by emplacement at 15.40 ± 0.07 Ma (zir-
tion, before 1950, 1,200 million ounces (Moz) Ag, 2 Moz Au, con U-Pb ID-TIMS; Baumgartner et al., 2009) of dacitic to
and about 50 Mt at 2 wt % Cu were mined (Baumgartner et rhyodacitic lava-dome complexes along the western margin of
al., 2008, and references therein). Cerro de Pasco is a part of the diatreme. East-west–trending quartz-monzonite porphyry
the Miocene metallogenic belt of central and northern Peru, dikes cut the diatreme breccia and the magmatic domes (Fig.
including world-class districts such as Colquijirca (Bendezú 1A). These dikes do not propagate into the Excelsior shales
and Fontboté, 2009), Morococha (Catchpole et al., 2011, west of the diatreme-dome complex; to the east they cross-
2015) and San Cristobal (Beuchat et al., 2004). cut locally the carbonate sequence. Two of these dikes have
The polymetallic mineralization at Cerro de Pasco results been dated at 15.35 ± 0.05 and 15.16 ± 0.04 Ma (zircon U-Pb
from a superposition of hydrothermal events linked to flu- ID-TIMS; Baumgartner et al., 2009). The end of the phreato-
ids with contrasting fS2, fO2, and pH. The present study uses magmatic and magmatic activity at Cerro de Pasco is marked
access to new mining areas and drill cores to describe sulfide by the emplacement of numerous, 20-cm- to 3-m-wide, E-W–
replacement features. Detailed petrographic observations trending, milled-matrix fluidized breccia dikes, occurring in
allow establishing of the sequence of replacement of pyrrho- various parts of the diatreme-dome complex.
tite, arsenopyrite, and galena by pyrite and marcasite, result- Following this event, epithermal base metal mineralization
ing from temperature, sulfur and oxygen fugacity changes, took place, mainly in carbonate rocks along the eastern mar-
and variations of pH. LA-ICP-MS analyses of pyrrhotite, gin of the magmatic complex (Einaudi, 1977; Baumgartner et
arsenopyrite, and their replacement products, pyrite and al., 2008). A striking feature of the Cerro de Pasco mineraliza-
marcasite, are combined with the petrographic observations tion is the occurrence of a N-S–trending, 1.5-km long, 250-m
and are coherent with the physicochemical evolution derived wide, and more than 550-m deep, funnel-shaped massive
from mineral stabilities; the influence of the protolith (ore pyrite-quartz body that replaced mainly carbonate rocks from
minerals and host rock) on the trace element signatures of the the Pucará Group, as well as, subordinately, the diatreme-
newly formed minerals is demonstrated. Based on the sulfide dome complex itself (Figs. 1A, 2; Graton and Bowditch, 1936,
replacement characteristics, we propose a revised sequence Lacy, 1949; Ward, 1961; Einaudi, 1968, 1977; Baumgartner,
of mineralization events at Cerro de Pasco, pointing to a much 2007; Baumgartner et al., 2008). At least five main pipelike,
simpler evolution of the mineralizing fluids than previously up to 150-m-wide, massive pyrrhotite-dominated bodies have
put forward. been recognized (Fig. 2). They grade outward into massive
Fe-rich sphalerite (up to 80% in volume) and galena. They
Geology and Mineralization at Cerro de Pasco are hosted by both the pyrite-quartz body and the Pucará
The Cerro de Pasco magmatic center is located 300 km carbonate rocks (Fig. 2), and locally crosscut the diatreme
northeast of Lima (Fig. 1A), in the high Andean plateau, at an breccia. According to previous studies (Einaudi, 1968, 1977;
elevation of 4,300 m.a.s.l. It is part of the mid-Miocene mag- Baumgartner et al., 2008), the emplacement of the pyrrhotite
matic belt recognized in central and northern Peru (Noble pipes postdated the massive pyrite-quartz body formation. In
and McKee, 1999; Bissig et al., 2008; Bissig and Tosdal, 2009). contrast, in the present study we report field evidence that
The magmatic center was emplaced directly west of a major the pyrrhotite pipes and their polymetallic rims (our stage
high-angle, N 15° W-striking reverse fault (“Longitudinal “A”; see below) predate the emplacement of the pyrite-quartz
fault”), mainly intruding weakly metamorphosed shales of body (our stage “B”).
the middle Paleozoic Excelsior Group, the oldest lithologi- Postdating the pyrite-quartz body, high-sulfidation miner-
cal unit in the area, and polymictic conglomerates and sand- alization took place (our stage “C”), as described previously
stones of the Middle-Late Triassic Mitu Group (Spikings et by Baumgartner et al. (2008, 2009). This mineralization stage
al., 2016; Fig. 1A). East of the Longitudinal fault there is a consists of a set of E-W–trending Cu-Ag-(Au-Zn-Pb) enargite-
thick sequence (about 1,000 m) of massive carbonate rocks, pyrite veins hosted by the diatreme breccia, as well as large,
mainly limestone with locally sandy intercalations, black bitu- well-zoned Zn-Pb-(Bi-Ag-Cu) replacement orebodies in the
minous limestone, and beds with chert nodules belonging to eastern part of the deposit. The latter mainly replaced carbon-
the Late Triassic Chambará Formation. The latter is part of ates and overprinted Fe-rich sphalerite and galena rims from
the Pucará Group that overlies Excelsior and Mitu Groups the previous stage A (Fig. 2). The enargite-pyrite veins have
(Angeles, 1999; Rosas et al., 2007). The sedimentary sequence been dated at 14.54 ± 0.08 and 14.41 ± 0.07 Ma (Ar-Ar on
was folded prior to the mid-Miocene magmatism, thus creat- alunite; Baumgartner et al., 2009). Existing age data for vari-
ing the main structural feature in the area, the Cerro anticline ous magmatic and hydrothermal events at Cerro de Pasco are
with a north-south axis and plunging to the north (Figs. 1, 2; summarized in Figure 1B.
Rogers, 1983; Angeles, 1999; Baumgartner et al., 2008) Temperatures of formation during the different mineraliz-
The Cerro de Pasco magmatic center consists of a large ing events have been constrained by fluid inclusion studies
diatreme-dome complex, 2.5 km in diameter, which was (Rottier et al., 2015). Fluid temperatures range between 220°
formed by a succession of phreatomagmatic and magmatic and 280°C for stages A and B, and between 140° and 295°C
events (Fig. 1A, B; Einaudi, 1968; Rogers, 1983; Baumgart- for stage C. Fluid salinities vary from 20 to 3 wt % NaCl equiv
ner et al., 2009). An early phase of explosive activity produced for stages A and B, and from 19 to 1.05  wt  % NaCl equiv
a diatreme-breccia known locally as Rumiallana agglomerate, for stage C. Mineralization of stages A and B was formed by
which is the most common lithology in the magmatic complex magmatic-dominated fluid according to oxygen isotopic sig-
and has been dated at 15.36 ± 0.03 Ma (U-Pb ID-TIMS dating natures of hydrothermal quartz (Baumgartner et al., 2008). In

180
SULFIDE REPLACEMENT REVEALED BY TRACE ELEMENT ANALYSES: CERRO DE PASCO, PERU 1349

E 9000
E 362 000
E 361 000
Colombia

E 360 000
Ecuador

N 8 822 000

Peru
Brasil

Cerro de
Lima Pasco
4460 m

ia
Pacific ocean

liv
Bo
N 8 821 000

4440 m

4080 m

N 8 820 000

N 8 819 000

250 m

: Sericite-pyrite alteration
Geological Units Mineralization with local
: Eocene Shuco Stage C
: Rhyodacite to rhyolite dome : E-W Cu-Ag-(Au-Zn-Pb) quartz-alunite±zunyite
conglomerate and
: Quartz monzonite Calera limestone enargite-pyrite vein : Pyrophyllite
porphyry dyke : Upper Triassic - Lower : Replacement Zn-Pb-(Ag) : Chlorite-sercite-pyrite
: rhyodacitic porphyry Jurassic Pucará Group and Ag-Cu-Bi body in
Mid-Miocene

(carbonate rocks) carbonate rock : Hydrothermal breccia


: Dacitic domes and Stage B
: Middle-Late Triassic : Collapse breccia
lava flows : Pyrite-quartz body
Mitu Group : Area with high density of milled-
: Rhyodacitic domes and
(conglomerates, sandstones) Stage A matrix fluidized breccia dykes
lava flows
: Devonian Excelsior Group : Zn-Pb-(Ag) replacement : Fault
: Dacitic tuffs
(Phyllites, shales, quartzites) body : Open pit limit (April 2014)
: Diatreme breccia
: Pipe-like pyrrhotite body : Stockpiles
B
15.6 15.4 15.2 15.0 14.8 14.6 14.4 14.2 (Ma)
Diatreme breccia
U-Pb ID-TIMS zircon (Baumgartner et al., 2009)
Dacitic domes and
lava flows 40
Ar/39Ar alunite (Baumgartner et al., 2009)
Quartz monzonite
porphyry dykes
Pyrrhotite pipes Potential age range*
and Zn-Pb rims
Pyrite-quartz body Potential age range*
Enargite-pyrite veins
*based on cross-cutting relationships

Fig. 1. A) Geologic map of the diatreme-dome complex and different epithermal mineralization styles at Cerro de Pasco,
compiled from field observations and the previous work of Rogers (1983), Baumgartner et al. (2008), and the Volcan’s geologi-
cal staff; B) Geochronology of the magmatic-hydrothermal system at Cerro de Pasco; data from Baumgartner et al. (2009).

181
1350 ROTTIER ET AL.

B B
A Level 1200 B Level 1600

E 362 200

E 362 800
E 362 200

E 362 800
3985 m 3864 m

N 8 820 500 N 8 820 500

N 8 820 000 N 8 820 000

C D C D

Not mapped
A A
N 8 819 500 N 8 819 500
100 m 100 m
A B
C (m.a.s.l) SSW NNE
4200 4200

4100 4100

4000 4000

3900 3900

3800 100 m 3800

C open pit shape 2012 D


D (m.a.s.l) W E
4200 4200

4100 4100

4000 4000

3900 3900

Not mapped
3800 3800
100 m
3700 3700

Geological Units Mineralization type


: Quartz monzonite porphyry dyke : Cu-Ag-(Au-Zn-Pb)
: Conduit of the dacitic domes and enargite-pyrite vein (stage C)
lava flows : Zn-Pb-Ag and Ag-Cu-Bi replacement
: Diatreme breccia body (stage C) Fig. 2. Geology of Cerro de Pasco: A) Geo-
: Upper Triassic - Lower Jurassic : Zn-Pb-Ag and Ag-Cu-Bi replacement body logical plan map of 1200 level; B) Geologi-
Pucará Group (carbonate rocks) (stage C) overprinting stage A Zn-Pb-(Ag) cal plan map of 1600 level; C) SW-NE cross
: Middle-LateTriassic Mitu Group replacement body section along A-B profile; D) E-W cross sec-
(Conglomerate and sandstone) : Pyrite-quartz body (stage B) tion along C-D profile, compiled from field
: Devonian Excelsior Group observations and previous work of Einaudi
(Phyllite, shale, quartzite) : Zn-Pb-(Ag) replacement body (stage A) (1968, 1977), Baumgartner et al. (2008), and
: Inferred fault : Pipe-like pyrrhotite bodiy (stage A) the Volcan’s geological staff.

182
SULFIDE REPLACEMENT REVEALED BY TRACE ELEMENT ANALYSES: CERRO DE PASCO, PERU 1351

contrast, stage C is characterized by mixing of magmatic and pits. The samples were loaded along with the synthetic poly-
meteoric waters (stable isotope analyses of alunite and kaolin- metallic sulfide standard MASS-1 (Wilson et al., 2002) in a
ite; Baumgartner et al., 2008). 1-cm3 ablation cell on a modified Zeiss petrographic micro-
scope. Sulfides and the standard were ablated in spot mode
Analytical Methods using a 40-µm craters and a 5-Hz repetition rate. Data reduc-
Sphalerite from the outer zone of the pyrrhotite pipes and tion was carried out with the SILLS software (Guillong et al.,
sphalerite present as inclusions (20–200 µm in diam) in pyrite 2008), using stoichiometric Fe content of the minerals as an
from the pyrite-quartz body were analyzed for their major internal standard.
and minor elements. Sulfur, Zn, Fe, Mn, Cu, Se, Ag, Cd, and
In were quantified by electron microprobe analyses (EMPA) Pyrrhotite Pipes and Their Rims (Stage A)
using a Jeol JXA 8200 Superprobe WD/ED combined micro- The massive pyrrhotite-carbonate replacement, high-angle,
analyzer at the University of Lausanne. Operating conditions pipelike bodies (stage A) extend vertically up to 650 m and
were as follows an accelerating voltage of 20 kV, beam current have horizontal extensions of up to 150 m. The pipes are
of 20 nA, and beam diameter of 1 µm. Standards and radia- structurally controlled, mainly by the NNW-SSE longitudi-
tions used were as follows: FeS2 (Fe-Kα), ZnS (Zn-Kα, S-Kα), nal fault corridor, and subordinately by N 35° and N 120°
Cu5FeS4 (Cu-Kα), CdSe (Cd-Lα, Se-Lα), MnS (Mn-Kα), Ag fault directions. In the deeper part of the mine (levels 3600
metal (Ag-Lα), InP (In-Lα). Counting times of 20 s on peak and deeper, Fig 2C) they are lithologically controlled by
and 10 s on background on both sides of the peak were used the bedding of the folded sedimentary sequence (Einaudi,
for all elements. 1977). The dip of the pipes flattens to the south in the north-
LA-ICP-MS analyses of pyrrhotite, arsenopyrite, pyrite, ern part and toward the north in the southern part of the
and marcasite from the pyrrhotite pipes and their rims (stage deposit. Iron-rich sphalerite-galena rims form broadly con-
A) and pyrite from the pyrite-quartz body (stage B) were centric bodies centered on the pyrrhotite pipes. The Fe-rich
conducted using a 193 nm ArF Excimer laser with an energy sphalerite and galena rims extend laterally from the pyrrho-
homogenized beam profile, coupled with an ELAN 6100 DRC tite pipes typically several tens of meters and up to 600 m in
ICP quadrupole mass spectrometer (QMS) at ETH Zurich places above level 3800.
(Günther et al., 1997; Heinrich et al., 2003). Table 1 provides Pyrrhotite pipes and their rims show a strong upward and
a summary of the analytical conditions and data acquisition outward zonation (Fig. 3). Five zones were defined (Einaudi,
parameters used for the LA-ICP-MS analyses. The optical 1968, 1977; Baumgartner et al., 2008). The pipe core (zone
imaging system allows for precise positioning of the ablation 1, Fig. 3) is formed by massive pyrrhotite and quartz, hosting
numerous inclusions of wolframite, cassiterite, and rutile, up
Table 1. LA-ICP-MS Machine and Data Acquisition Parameters to 100 µm in size. An intermediate zone (zone 2) is composed
of pyrrhotite, quartz, Fe-rich sphalerite, chalcopyrite, and
Excimer 193 nm ArF laser Compex 110I stannite. Iron-rich sphalerite and chalcopyrite are present as
Output energy 20 mJ small anhedral crystals and as blebs (up to 300 µm large) in
Homogeneous energy 2-4 J/cm2 pyrrhotite, making up to 5% and up to 2%, respectively, of the
  density on sample
Repetition rate 5 Hz sulfides. Rare stannite occurring mainly as blebs in chalcopy-
Ablation mode Single hole rite was described by Einaudi (1977). Quartz represents less
Crater sizes 40 µm than 10% of the intermediate zone and forms small euhedral
Ablation cell In-house built glass chamber with antireflection grains of 0.5 to 1 mm, containing numerous, up to 100 µm,
  coated silica glass window
large inclusions of apatite and rutile. The external zone of
Perkin Elmer ELAN 6100 DRC the pipes (zone 3) consists of pyrrhotite, Fe-rich sphalerite,
Rf-power 1550 W
arsenopyrite, chalcopyrite, and quartz. This zone differs from
Detector mode Dual the intermediate zone mainly by the presence of arsenopy-
Quadrupole setting time 3 ms rite, locally up to 10%. The transitional zone between the
Nebulizer gas flow 0.79 l/min Ar pipes and their rims (zone 4) is characterized by progressive
Auxiliary gas flow 0.85 l/min Ar increase of Fe-rich sphalerite and decrease of pyrrhotite and
Plasma gas flow 15.5 l/min Ar
Carrier gas flow 1.1 l/min He arsenopyrite. Galena occurs in small amounts (up to 5%) and
Additional gas flow 5 ml/min H2 forms anhedral crystals. The outer part of the rim (zone 5)
consists mainly of Fe-rich sphalerite, up to 90% of the total
Data acquisition parameters volume. Galena content increases progressively outward, but
Sweeps per reading 1 remains below 10% of the total volume. Numerous, up to
Readings per replicate 300 50 µm, inclusions of Ag-rich tetrahedrite, argentite, and poly-
Replicates 1
Dwell time per isotope 30 ms for Ag and Au; 20 ms for V
basite are present in galena. Pyrite appears locally; it forms
10 ms for all others anhedral to subhedral crystals and can reach up to 5% of zone
Points per peak 1 per mass 5. This pyrite is referred to as PyA. Quartz grains up to 4 mm
Oxide production rate Tuned to <0.5 % ThO in size represent less than 10% of zone 5 and host small inclu-
Isotopes analyzed 23Na, 28Si, 32S, 51V, 53Cr, 55Mn, 57Fe, 59Co, 60Ni,
sions (<100 µm) of apatite, rutile, and anatase. Locally, an out-
  65Cu, 66Zn, 69Ga, , 75As, 77Se, 95Mo, 109Ag, 111Cd,

  115In, 118Sn, 121Sb, 125Te, 182W, 197Au, 202Hg, ermost zone occurs and is characterized by massive magnetite
  205Tl, 208Pb, 209Bi, 232Th, 238U (up to 70% of the total volume), Fe-rich sphalerite, galena,
Fe-Mn-Zn carbonate, and chlorite.

183
1352 ROTTIER ET AL.

Not to scale
Legend
: Carbonate (Pucará formation) : Pyrrhotite, arsenopyrite, sphalerite,
chalcopyrite and quartz (zone 3)
: Pyrrhotite, quartz, wolframite,
cassiterite (zone 1) : Transition zone: sphalerite, galena, pyrrhotite,
arsenopyrite and quartz (zone 4)
: Pyrrhotite, sphalerite, chalcopyrite,
: Rims: sphalerite, galena, pyrite
stannite and quartz (zone 2)
and quartz (zone 5)
Fig. 3. Idealized mineral zoning of the pyrrhotite pipes and their Zn-Pb rims (based on Einaudi, 1977, Baumgartner et al.,
2008, and this study).

Alteration that could be attributed to the emplacement the pyrite grains. Sphalerite inclusions locally show chal-
of the pyrrhotite pipes and their rims was not observed in copyrite disease. Arsenopyrite and stannite inclusions have
the carbonate sequence owing to later overprinting. Strong been also reported (Lacy, 1949; Einaudi, 1977; Baumgart-
chloritization spatially associated with the pyrrhotite pipes ner et al., 2008). Rutile, hematite, and stibnite inclusions are
and their rims is observed in the phreatomagmatic breccia locally found in the external part of the pyrite grains, indicat-
(DDH-S-CE-14-009). ing an increase of fO2.
Massive black and red hematite-bearing chalcedony and
Pyrite-Quartz Body (Stage B) euhedral, up to 1-cm-long, quartz grains are also common in
The pyrite-quartz body (stage B) replaces mainly the Pucará the pyrite-quartz body. Quartz contains rutile, anatase, hema-
carbonate rocks, remnant sedimentary textures and locally tite, and apatite inclusions up to 100 µm in size. Anatase inclu-
pods, up to 100-m wide (Einaudi, 1968), of carbonate rock sions are restricted to the upper part, and rutile can be found
being preserved (Fig. 2A, C). The diatreme-dome complex in both the upper and lower part of the orebody.
is also crosscut by roughly N-S–trending pyrite-quartz veins,
up to 2 m wide. Locally, the diatreme breccia is affected by Mineral Textures at Pyrrhotite Pipe-Pyrite-Quartz
massive replacement of pyrite-quartz. Following the contour Body Contacts
of the pyrite-quartz body and up to a distance of 50 m sur- A 1- to 15-m-wide replacement front is recognized between
rounding it, a sericite-quartz-pyrite alteration halo was devel- the pyrite-quartz body and the pyrrhotite pipes and their
oped within the diatreme-dome complex (Einaudi, 1968; Zn-Pb rims (Fig. 4). From the pyrrhotite pipes to the pyrite-
Baumgartner et al., 2008). quartz body, the following main textural patterns are distin-
Pyrite constitutes more than 90% of the pyrite-quartz guished. Inside the pyrrhotite pipes, at up to 15 m from the
body. It forms both anhedral and euhedral (octahedral and contact with the pyrite-quartz body, patches of porous, fine-
occasionally cubic) grains up to 2 cm. In the inner part of the grained marcasite mark the beginning of the replacement
pyrite grains, numerous inclusions of pyrrhotite and chalco- front (Fig. 4A, B). In the immediate vicinity of the contact,
pyrite (<150 µm) are present. Frequently, these two miner- a 1- to 10-m-wide zone formed by porous fine-grained mar-
als occur in the same bleb and appear to be in equilibrium casite-pyrite with remnant patches of pyrrhotite occurs (Fig.
with each other and the host pyrite. Up to 200-µm-wide 4C). The pyrrhotite remnants progressively disappear, grad-
sphalerite inclusions are also common in the inner part of ing into the pyrite-quartz body characterized by the absence

184
SULFIDE REPLACEMENT REVEALED BY TRACE ELEMENT ANALYSES: CERRO DE PASCO, PERU 1353

A B C

Py Py
Py

Po

Py

Py Po
Py
Py

Po

Po

Po

Py Py
Py

Py

Po
5 cm 1 cm 0.5 cm

D Py E
Po Po

Py Py
Po Py

Po
Po

Py
Py
Po
Po
Po
Po

Po

2 cm 0.5 cm

Fig. 4. A) Drill core with the contact between a pyrrhotite pipe and the pyrite-quartz body (borehole no. 1800-08-18); B)
Progressive replacement of pyrrhotite by pyrite; C) Part of a core where pyrrhotite is replaced by fined-grained pyrite (sample
CP-12-BR-46). Note the spongy replacement texture of pyrite; D) Large euhedral pyrite crystals and centimetric veins of
pyrite-quartz in pyrrhotite (borehole no. 1600-08-12); E) Large euhedral pyrite in pyrrhotite (sample CP-12-BR-63). Abbre-
viations: Po = pyrrhotite, Py = pyrite.

of porous pyrite and by a slight increase of the quartz con- of the replacement of the pyrrhotite pipes and their rims
tent. Up to 1-cm-large euhedral pyrite crystals (PyB1-po in by pyrite and/or marcasite. At the microscopic scale differ-
the following) are present throughout the pyrrhotite pipes, ent types of pyrite/marcasite replacing pyrrhotite, arsenopy-
being more abundant in areas crosscut by pyrite-quartz vein- rite, and galena are distinguished; their description and their
lets (Fig. 4D-E) that are considered to also constitute part main characteristics are summarized in Table 2. Two types of

185
1354 ROTTIER ET AL.

Table 2. Description and Relative Timing of the Different Types of Pyrite and Marcasite

                      Timing

stageA stageB Mineral Einaudi’s


Name replaced Texture/size Solid inclusions1 pyrite types

PyA None Anhedral to subhedral crystals Sp, Gn Pyrite-1


From 50 μm to 1 mm   Figure 6B of
  Einaudi (1977)
PyB1-po2 Pyrrhotite Euhedral crystals Po, Apy, Cpy, Sp Pyrite-1
Up to 1 cm
Marcasite2 (Mrc) Pyrrhotite Anhedral to euhedral crystals Po
<1 μm
PyB2-mrc2 Marcasite Subhedral to euhedral crystals Not observed Pyrite-2-3-4-5
Up to 200 μm
PyB2-asp2 Arsenopyrite Anhedral to euhedral crystals Apy, Cu-Ag sulfosalt Pyrite-2-3-4-5
<1 μm
PyB2-gn Galena Anhedral to subhedral crystals Gn, Pb-Ag sulfosalt, Sp Pyrite-2-3-4-5
Up to 50 μm
PyB-PQB2 None Anhedral to eubhedral crystals Po, Cpy, Sp, Apy, Pyrite-1
From 50 μm to 2 cm Rt, Hm, Stbn

Notes: The comparison with Einaudi’s pyrite types is from Einaudi (1968, 1977); Mineral abbreviations: Apy = arsenopyrite, Cpy = chalcopyrite, Gn =
galena, Hm = hematite, Po = pyrrhotite, Rt = rutile, Sp = sphalerite, Stbn = stibnite
1 Solid inclusions above 1 µm in size, identified with reflected-light microscope
2 Minerals analyzed by LA-ICP-MS for their trace element content

replacement of pyrrhotite by pyrite and/or marcasite are rec- of this fine-grained marcasite. Fine-grained marcasite is then
ognized: (1) pyrrhotite replaced by euhedral pyrite (PyB1-po), replaced by euhedral crystalline PyB2-mrc aggregates. All transi-
and (2) pyrrhotite replaced by fine-grained marcasite (Fig. tions from nonreplaced marcasite to fully replaced marcasite
5A-F). As illustrated in Figure 5A, replacement by euhedral by PyB2-mrc are observed (Fig. 5C-E). The final products are
pyrite (PyB1-po) precedes that by fine-grained marcasite and is aggregates of non-oriented small (up to 200 µm), euhedral
visible throughout the pyrrhotite pipes, increasing in quan- nonporous pyrite (PyB2-mrc) and marcasite crystals (Fig. 5C-E).
tity toward the contact between the pyrrhotite pipes and the This pyrite (PyB2-mrc) is weakly anisotropic.
pyrite-quartz body. Replacement by fine-grained marcasite The fine-grained marcasite replacing pyrrhotite has been
accounts for the porous texture of the replacement front. observed by Einaudi (1971) and classified as “intermediate
Euhedral pyrite (PyB1-po) replacing pyrrhotite is rich in product,” or “Zwischenprodukt,” as defined by Ramdohr
inclusions (up to 250 µm), mainly of pyrrhotite and subor- (1980). “Intermediate product” was defined as very small
dinate arsenopyrite, chalcopyrite, and Fe-rich sphalerite, gray-whitish strongly anisotropic minerals with yellowish-
reflecting the initial mineralogy of the pyrrhotite pipes (Fig. brown to grayish blue polarization colors and interpreted by
5A, B). Pyrrhotite inclusions form blebs or are elongated Ramdohr (1980) as a mixture of marcasite with other min-
along the previous (100) pyrrhotite cleavage planes. Groups erals. Since our observations are consistent with the experi-
of pyrrhotite inclusions present synchronous extinction evi- mental studies of replacement of pyrrhotite by marcasite and
dencing that they are relicts of larger pyrrhotite single grains. pyrite that do not reveal the presence of other phases (Mur-
This pyrite (PyB1-po) has less than 5% porosity, having both owchick, 1992; Qian et al., 2011), and following the proposi-
non-oriented pores, and pores aligned along previous (100) tion of Fleet (1978), we prefer not to use the term proposed
pyrrhotite planes. by Ramdohr (1980).
The fine-grained (<1 µm) marcasite replacing pyrrho- Arsenopyrite occurring in the external zone of pyrrhotite
tite is locally intergrown with a few small (generally <5 µm) pipes is replaced by very small (<1 µm) pyrite (PyB2-asp) grains.
pyrite euhedral crystals. Marcasite replaces pyrrhotite along Numerous elongated pores, around 10% in volume, are pres-
the cleavage directions, small cracks, and around the euhe- ent; the pore volume being coherent with the volume cell
dral pyrites previously formed. Pores make up to 30 vol % difference between arsenopyrite and pyrite. The pores are

Fig. 5. Typical textural patterns observed in pyrrhotite pipes and their outer Fe-rich sphalerite-galena rims: A) Euhedral
pyrite surrounded by late marcasite replacing pyrrhotite; B) Euhedral pyrite with oriented pyrrhotite inclusions replac-
ing pyrrhotite; C-D) Fine-grained marcasite replacing pyrrhotite, partially replaced by pyrite; E) Fine-grained marcasite
replacing pyrrhotite almost fully recrystallized to pyrite; F) Fine-grained pyrite replacing galena; sphalerite is not affected;
G) Micrometer-scale pyrite replacing euhedral arsenopyrite crystals, resulting in highly porous texture. Pores orientation is
controlled by the former (001) and (100) planes of arsenopyrite. Sphalerite is not affected by replacement; H) Similar to G)
in crossed nicols.

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SULFIDE REPLACEMENT REVEALED BY TRACE ELEMENT ANALYSES: CERRO DE PASCO, PERU 1355

A B
Mrc
Mrc (Py)
Po

PyB1-Po PyB1-Po
Po

Po

50 μm 50 μm

C D
Mrc

Mrc

Mrc Mrc
PyB2-mrc

PyB2-mrc 50 μm 20 μm

E F

Gn

PyB2-gn
PyB2-mrc Sp

Po

Sp
Mrc Sp
200 μm 50 μm

G Sp H

(001
) PyB2-asp
(100)

PyB2-asp
Asp Asp

Sp
Sp
50 μm 50 μm

187
1356 ROTTIER ET AL.

distributed along the (100) and (001) arsenopyrite crystal- (Fig. 7A, Table 3). The obtained LA-ICP-MS transient sig-
lographic planes (Fig. 5G, H). This replacement by PyB2-asp nals (Fig. 8A), showing spiky patterns, and the trace elements
might be contemporaneous with the replacement of pyrrho- correlations suggest that, except for Mn, the detected trace
tite by the fine-grained marcasite. No marcasite has been element concentrations correspond most probably to small
observed replacing arsenopyrite (Fig. 5G, H). inclusions of galena and rare Sb-Bi-Ag-Pb sulfosalt.
Replacement fronts between the Fe-rich sphalerite-galena Euhedral pyrite replacing pyrrhotite (PyB1-po) presents ele-
rims and the pyrite-quartz body are less clear and are charac- vated contents in a large range of trace elements (Fig. 7B).
terized by partial to total replacement of pyrrhotite and galena Manganese, Cu, As, Ag, Sb, Pb, and Bi have been detected in
by a fine-grained porous marcasite-pyrite mixture toward more than 90% and V, Ni, Ga, Sn, Te, W and Au in more than
the pyrite-quartz body (Fig. 6). Galena in the Zn-Pb rims 50% of the analyzed spots; Co, Zn, and Tl have been detected
of the pyrrhotite pipes presents dissolution textures and in locally. Arsenic, Sb, Pb, Bi, in most of the samples show flat
some parts is replaced by fine-grained pyrite (PyB2-gn). Newly and smooth patterns and mean concentrations largely above
formed PyB2-gn generally follows the cleavage planes of galena 10 ppm; V, Ni, Ga, Sn, Ag, Te, and Au present similar patterns
and/or occurs in small cracks. This replacement results in but have lower concentrations. Tungsten, when detected,
more than 20 vol % porosity, the pores being generally filled shows a spiky pattern and absence of correlation with other
by late carbonate. Sphalerite seems unaffected by replace- elements; it probably occurs as minor inclusions of wolframite.
ment processes (Figs. 5E, F, 6). The 6 analyses of fine-grained marcasite (Mrc) have been
performed on spots containing groups of individual crystals
Trace Element Analysis by LA-ICP-MS of about 1 µm in diameter. The location of ablation spots
Two representative samples from the pyrrhotite pipes show- has been chosen where no interstitial pyrite crystals and pyr-
ing different replacement textures of pyrrhotite and arse- rhotite were visible. Fine-grained marcasite (Mrc) has lower
nopyrite and two samples from the pyrite-quartz body were trace element content than euhedral pyrite PyB1-po except for
selected for LA-ICP-MS analysis. A total of 111 analyses W and Tl (Fig. 7C). Manganese, Ga, As, Sb, W, Tl, Pb, and Bi
were performed, including 20 on pyrrhotite, 23 on euhedral values were over the detection limit in all the analyses and V,
pyrite replacing pyrrhotite (PyB1-po), 6 on fine-grained mar- Cu, Ag, Sn, and Te were detected locally. Most of the detected
casite replacing pyrrhotite, 13 on pyrite replacing marcasite trace elements present flat and smooth ablation signals.
(PyB2-mrc), 9 on arsenopyrite, 9 on pyrite replacing arsenopy- Fine crystalline pyrite replacing marcasite (PyB2-mrc), simi-
rite (PyB2-asp), and 31 on pyrite from the pyrite-quartz body larly to euhedral pyrite (PyB1-po), displays an elevated content
(PyB-PQB), the latter coming from two samples located at more in a large range of trace elements (Fig. 7D). Manganese, Cu,
than 70 m from any pyrrhotite pipe and its rim. The results As, Ag, Sn, Sb, Pb and Bi have been detected in all analy-
are summarized in Table 3 and illustrated in Figure 7. ses and V, Co, Ni, Ga, Te, W, Au, and Tl in more than 50%
Pyrrhotite has low trace element content: Mn, Sb, Pb, and of the analyzed spots. Chromium, Zn, and Cd have been
Bi are the only elements detected in more than 90% of the detected occasionally. Most detected elements have relatively
analyses, and Ag is detected in more than 50% of the analyses smooth patterns. Gallium shows a spiky signal (Fig. 8B) and

A B
Mrc (Py)

Sp
Po

Sp

Gn

Sp

Sp
0.5 cm 1 cm

Fig. 6. Typical textures of the Pb-Zn rims of the pyrrhotite pipes: A) Sample from an Fe-rich sphalerite-galena-pyrrhotite
zone of the pyrrhotite pipes not affected by the late emplacement of the pyrite-quartz body (sample CP-12-BR-37); B)
Similar zone of the pyrrhotite pipes affected by the late emplacement of the pyrite-quartz body. Note the disappearance of
pyrrhotite and galena (Sample CP-12-BR-129). Abbreviations: Gn = galena, Mrc = marcasite, Po = pyrrhotite, Py = pyrite,
Sp = sphalerite.

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Table 3. Summary of the LA-ICP-MS Trace Element Results

V Cr Mn Co Ni Cu Zn Ga As

Pyrrhotite n 5 0 19 0 0 3 4 3 2
(ntot=20) Min/Max 0.37/1.1 N.D 4.4/8.2 N.D N.D 1/16 9/157 0.78/1.9 15/142
Mean 0.67 ± 0.31 N.D 5.9 ± 0.96 N.D N.D 6.9 ± 8 50 ± 72 1.2 ± 0.59 79 ± 90
Mean LOD 0.32 17 3.6 0.38 1.6 1.2 12 0.46 39
Arsenopyrite
n 0 0 8 9 7 3 0 3 6
(ntot=9) Min/Max N.D N.D 3.7/7.6 1.8/356 36/226 0.82/5.2 N.D 0.25/0.51 1436200/2155100
Mean N.D N.D 5 ± 1.2 201 ± 134 139 ± 80 3.4 ± 2.3 N.D 0.35 ± 0.14 1631600 ± 265500
Mean LOD 0.29 15 3 0.32 1.6 1 10 0.37 243
PyB1-po n 14 1 23 8 15 21 3 12 20
(ntot=23) Min/Max 0.14/6.5 10 4.5/26 0.12/8.4 0.78/40 0.72/9.7 5.9/11 0.18/24 158/10320
Mean 2.1 ± 2.3 10 ± 0 9 ± 6.3 1.6 ± 2.8 14 ± 14 3.3 ± 2.3 8.7 ± 2.5 5.9 ± 7.6 4270 ± 3270
Mean LOD 0.16 6 1.8 0.2 0.83 0.6 6.1 0.21 34
Marcasite n 2 1 6 1 0 5 0 6 6
(ntot=6) Min/Max 0.16/0.25 6.6 4.2/6.6 0.07 N.D 0.49/2.9 N.D 0.47/1.1 212/1020
Mean 0.2 ± 0.07 6.6 ± 0 5.4 ± 0.86 0.07 ± 0 N.D 1.3 ± 0.93 N.D 0.7 ± 0.24 411 ± 304
Mean LOD 0.12 6 1.2 0.1 0.54 0.46 5.3 0.16 1.4
PyBw-mrc n 10 4 13 9 8 12 5 11 13
(ntot=13) Min/Max 0.19/40 7.5/57 4/1450 0.34/11 0.82/215 2/125 5.3/15 0.65/29 8.1/12240
Mean 8.3 ± 13 23 ± 23 164 ± 407 2.1 ± 3.4 69 ± 82 31 ± 45 10 ± 3.5 12 ± 11.5 4400 ± 3090
Mean LOD 0.16 8.4 1.7 0.18 0.79 0.59 5.7 0.19 27
PyB2-asp n 2 0 9 9 9 9 7 8 7
(ntot=9) Min/Max 0.22/0.85 N.D 3.5/36 4/373 2.3/110 774/2050 8.1/191 0.48/8.8 883/105540
Mean 0.53 ± 0.45 N.D 18 ± 8.5 65 ± 120 28 ± 38 1250 ± 392 45 ± 67 2.8 ± 2.8 21210 ± 38040
Mean LOD 0.15 8.2 1.6 0.17 0.72 0.56 6.2 0.21 38
PyB-PQB n 3 3 31 3 7 25 0 2 31
(ntot=31) Min/Max 0.19/0.42 7.3/8.3 3.6/5.9 0.28/0.99 0.13/2.5 0.7/46 N.D 0.36/0.44 5.4/7950
Mean 0.27 ± 0.13 7.9 ± 0.52 4.7 ± 0.64 0.6 ± 0.36 1.2 ± 0.9 6.2 ± 9.8 N.D 0.4 ± 0.05 110 ± 1590
Mean LOD 0.16 7.6 1.5 0.15 0.7 0.75 6.1 0.21 4.1

Ag Cd Sn Sb Te W Au Tl Pb Bi

Pyrrhotite n 11 1 0 18 3 2 0 2 20 17
(ntot=20) Min/Max 0.13/0.74 1.2 N.D 0.27/16 0.39/0.47 0.09/0.24 N.D 0.04 ± 0.11 0.81/96 0.18/3.2
Mean 0.33 ± 0.19 1.2 ± 0 N.D 2.6 ± 4 0.44 ± 0.04 0.16 ± 0.1 N.D 0.08 ± 0.05 25 ± 32 0.65 ± 0.77
Mean LOD 0.19 2.2 3.3 0.27 0.76 0.48 0.16 0.09 0.28 0.1
Arsenopyrite
n 9 2 1 9 4 0 9 1 9 9
(ntot=9) Min/Max 0.25/47 0.6/1.8 3.2 6390/118550 0.53/5.7 N.D 0.7/24 0.05 5.2/256 24/324
Mean 6.6 ± 15 1.2 ± 0.89 3.2 ± 0 27790 ± 34720 1.9 ± 2.6 N.D 5 ± 7.5 0.05 ± 0 47 ± 79 133 ± 105
Mean LOD 0.13 1.4 2.7 0.37 0.68 0.35 0.14 0.1 0.27 0.09
PyB1-po n 22 1 13 23 14 15 12 8 23 23
(ntot=23) Min/Max 0.04/7.2 0.39 1.8/5.8 3.96/133 0.3/30 0.05/18 0.08/1.3 0.01/0.27 14/2710 0.78/77
Mean 1.6 ± 1.7 0.39 ± 0 3.8 ± 1.4 51 ± 43 7 ± 9.5 2.8 ± 4.6 0.35 ± 0.4 0.09 ± 0.09 740 ± 634 21 ± 19
Mean LOD 0.08 1.2 1.6 0.15 0.42 0.2 0.09 0.03 0.14 0.04
Marcasite n 3 0 4 6 3 6 0 6 6 6
(ntot=6) Min/Max 0.06/0.26 N.D 1.2/3.2 4.6/12 0.13/0.18 2.7/4.6 N.D 0.27/1.3 10/187 0.11/1.3
Mean 0.15 ± 0.1 N.D 2 ± 0.94 9 ± 2.9 0.15 ± 0.03 3.6 ± 0.73 N.D 0.71 ± 0.43 57 ± 65 0.54 ± 0.47
Mean LOD 0.07 0.94 1.1 0.09 0.32 0.11 0.07 0.03 0.08 0.04
PyB2-mrc n 13 3 12 13 8 9 7 9 13 13
(ntot=13) Min/Max 0.1/21 0.28/0.53 1.7/206 1.4/402 0.29/17 0.28/15 0.12/2 0.02/6.1 26/7640 0.32/96
Mean 5 ± 5.5 0.44 ± 0.14 44 ± 60 106 ± 106 4.1 ± 5.7 4.2 ± 5.3 0.46 ± 0.68 0.98 ± 1.9 1860 ± 2010 28 ± 25
Mean LOD 0.1 1 1.6 0.15 0.36 0.18 0.08 0.05 0.14 0.05
PyB2-asp n 9 4 9 9 9 7 9 9 9 9
(ntot=9) Min/Max 373/2840 1/2.6 5.3/34 174/454 3.7/12 0.15/7 1.4/8.2 0.54/2.6 2140/56790 153/521
Mean 1000 ± 778 1.8 ± 0.72 9.8 ± 9.1 285 ± 113 7.2 ± 3.5 2.5 ± 2.6 3.6 ± 2.6 1.2 ± 0.71 13670 ± 20510 302 ± 130
Mean LOD 0.08 1.1 1.5 0.17 0.28 0.06 0.06 0.04 0.17 0.04
PyB-PQB n 29 0 7 29 9 4 12 7 9 30
(ntot=31) Min/Max 0.07/9.8 N.D 1.3/2.9 0.2/147 0.12/2.5 0.05/0.2 0.03/2 0.01/3.5 153/521 0.04/25
Mean 2.3 ± 2.6 N.D 1.8 ± 0.58 19 ± 29.8 0.6 ± 0.72 0.13 ± 0.07 0.27 ± 0.54 0.57 ± 1.3 302 ± 130 3.16 ± 4.9
Mean LOD 0.07 1.1 1.3 0.12 0.36 0.16 0.06 0.03 0.4 0.04

Notes: Results for pyrrhotite, arsenopyrite, marcasite, and PyB1-po, PyB2-mrc and PyB2-asp from samples CP-12-BR-44 and CP-12-BR-85 (located respectively at
362230E-8819782N and 362274E-8820293N), and PyB-PQB from samples CP-12-BR-80 and CP-12-BR-106 located at more than 70 m of any pyrrhotite
pipe and its rim (located, respectively, at 362265E-8820217N and 362181E-8819585N)
N total = Total number of spot analyses for each mineral; n = Number of analyses where the element has been detected; Min = Minimal value obtained,
Max = Maximal value obtained, Mean = mean of values obtained, 1σ = standard deviation, Mean LOD = Mean of the limit of detection

189
1358 ROTTIER ET AL.

105 Po A 105 Asp E

Concentration (ppm)
Concentration (ppm)

104 104

103 103

102 102

10 10

1 1

0.1 0.1

V Cr Mn Co Ni Cu Zn Ga As Ag Cd Sn Sb Te W Au Tl Pb Bi V Cr Mn Co Ni Cu Zn Ga As Ag Cd Sn Sb Te W Au Tl Pb Bi

PyB1-po B PyB2-asp F
105 105

Concentration (ppm)
104
Concentration (ppm)

104

103 103

102 102

10 10

1 1

0.1 0.1

V Cr Mn Co Ni Cu Zn Ga As Ag Cd Sn Sb Te W Au Tl Pb Bi V Cr Mn Co Ni Cu Zn Ga As Ag Cd Sn Sb Te W Au Tl Pb Bi

105 Mrc C 105


PyB-PQB G
Concentration (ppm)

Concentration (ppm)

104 104

103 103

102 102

10 10

1 1

0.1 0.1

V Cr Mn Co Ni Cu Zn Ga As Ag Cd Sn Sb Te W Au Tl Pb Bi V Cr Mn Co Ni Cu Zn Ga As Ag Cd Sn Sb Te W Au Tl Pb Bi

105 PyB2-mrc D
Concentration (ppm)

104

103

102

10

0.1

V Cr Mn Co Ni Cu Zn Ga As Ag Cd Sn Sb Te W Au Tl Pb Bi

Fig. 7. Trace element compositions of pyrrhotite, PyB1-po, marcasite, PyB2-mrc, arsenopyrite, PyB2-asp, and PyB-PQB. The black
hexagons correspond to the mean values and unfilled circles are individual analyses; the gray line represents the range of
values, and the black horizontal bar is the mean LOD.

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SULFIDE REPLACEMENT REVEALED BY TRACE ELEMENT ANALYSES: CERRO DE PASCO, PERU 1359

108
Po A 108
Asp As C
107 107
Fe Sb
Counts per second

Counts per second


106 106
Fe
105 105
Co
104 104 Pb
Bi Sb Pb
Ni
103 103
Au
Ag
10 2
10 2

10 10
0
0
50 100 150 200 250 300 0 50 100 150 200 250 300
Seconds Seconds

108 PyB2-mrc B 108 PyB2-asp D


107 107
Fe Fe
106 106
Counts per second

Counts per second

Pb Pb
Ag
105 105
Sb Bi Cu
104 Sn 104 Sb
Mn
103 Ga 103
Au
10 2
Ag 10 2

10 10
0 50 100 150 200 250 300 0 50 100 150 200 250 300
Seconds Seconds
Fig. 8. Typical LA-ICP-MS transient signals for selected elements obtained from the ablation of pyrrhotite (A), PyB2-mrc (B),
arsenopyrite (C), and PyB2-asp (D).

concentrations that do not correlate with those of other ele- crystals were visible. We also carefully selected areas that were
ments, suggesting the presence of Ga-bearing solid inclusions. as free as possible of small (~1-µm) visible solid inclusions of
Some LA-ICP-MS transient signals of Mn, Cu, Ga, Ag, and unidentified Cu-Ag-bearing sulfides or sulfosalts. PyB2-asp has,
Sn show smooth count variations, indicating minor chemical similarly to the original arsenopyrite, elevated trace element
zonation in the pyrite (Fig. 8B). contents, but for a larger range of elements (Fig. 7F). Man-
Arsenopyrite has an elevated content for certain trace ele- ganese, Co, Ni, Cu, Zn, Ga, Ag, Sn, Sb, W, Au, Tl, Pb, and Bi
ments (Fig. 7E). Manganese, Co, Ni, Ag, Sb, Au, Pb, and Bi have been detected in almost all the analyzed spots; V and Cd
were over the detection limit in almost all the analyses; Cu, have been detected in only a few analyses, close to the detec-
Ga, and Te were detected occasionally. Antimony presents flat tion limit. Copper, Ag and, to some extent, Sb present locally
and smooth patterns and concentrations up to 11 wt %, sug- spiky patterns (Fig. 8D). Silver and Cu show strong positive
gesting substitution for As. Nickel and Co show smooth varia- correlation, resulting from the presence of small inclusions
tions in transient signals, indicating chemical zonation (Fig. of Cu- and Ag-bearing sulfides or sulfosalts. Lead, Bi and, to
8C). Lead, Ag, and Au present mainly spiky patterns, indicat- some extent, Sb, also have spiky patterns and show positive
ing that they occur mostly as solid inclusions. Lead counts do correlations.
not correlate with other elements and are mainly attributed to Pyrite from the pyrite-quartz body (PB-PQB) shows a rela-
small inclusions of galena. tively high content of a restricted set of trace elements, but
The 13 analyses of fine-grained pyrite replacing arseno- for most elements PyB-PQB shows lower concentrations than
pyrite (PyB2-asp) like those for marcasite, were performed on observed in PyB1-po, PyB2-mrc, and PyB2-asp (Fig. 7G). Manga-
spots containing groups of individual crystals and ablation nese, As, Cu, Ag, Sb, Pb, and Bi values are above the detec-
spot locations were selected where no interstitial arsenopyrite tion limit in almost all analyses; Ni, Sn, Te, Au, and Tl are

191
1360 ROTTIER ET AL.

detected in more than 20% of the analyses. Vanadium, Cr, Co, decrease of the Fe content toward the border of the grain.
Ga, W, and Hg have been detected occasionally, in all cases Sphalerite is generally low in Mn (mean at 330 ppm, mean
with values close to the detection limit. Lead and Sb values LOD = 220 ppm, n>LOD =29), but relatively rich in In (mean
are high (up to 521 and 147 ppm, respectively). They display at 2,620 ppm, mean LOD = 490 ppm, n>LOD = 43) and in Cu
spiky patterns and have similar molar concentrations, suggest- (mean at 1,440 ppm, mean LOD = 300 ppm, n>LOD = 55).
ing probably the presence of small, nanoscale inclusions of Except for Cd, no correlations exist between the Fe content
Pb-Sb bearing sulfosalts. In places, Pb and Sb do not correlate and other trace elements in the studied sphalerites. A strong
strongly, thus suggesting instead the presence of galena inclu- correlation exists between Cu and In, most probably due to
sions. Copper and Ag values are about one order of magnitude the coupled substitution 2Zn2+→ Cu+ + In3+ (Fig. 9B).
lower than those of Sb and Pb and are positively correlated Sphalerite inclusions in pyrite from the pyrite-quartz body
with them; they are probably contained in tiny inclusions of (stage B) show relatively constant Fe contents, from 19 to
Pb-Sb-bearing sulfosalts. 24 mol % FeS (mean = 21 mol % FeS, σ = 1.2, mean LOD =
0.023 wt %, n>LOD = 43; Fig. 9A). Such Fe contents are consis-
EMP Analyses of Sphalerite tent with pyrite-pyrrhotite equilibrium, indicating a relatively
One hundred EPM analyses have been performed on stage A low sulfidation state, about –13 log fS2 at 250°C (calculated
Fe-rich sphalerite from the transition zone between the pyr- from Lusk and Calder, 2004). Sphalerite inclusions are gen-
rhotite pipes and their Zn-Pb rims, and 43 analyses on sphal- erally low in Mn (mean at 593 ppm, mean LOD = 230 ppm,
erite inclusions occurring in the core of pyrite crystals from n>LOD = 43), but rich in In (mean at 1,680 ppm, mean LOD
the pyrite-quartz body (stage B). = 470 ppm, n> LOD = 32) and Cu (mean at 3,719 ppm, mean
Stage A sphalerite grains are strongly zoned. Microprobe LOD =340 ppm, n>LOD= 41). In contrast to stage A sphalerite,
analyses confirm previous results (Einaudi, 1977; Baumgart- Cu does not show a good correlation with In (Fig. 9B). The
ner, 2007; Baumgartner et al., 2008), revealing Fe contents high Cu values measured are probably resulting from small
from 13 to 29 mol % FeS, with a mean at 21 mol % FeS, mean chalcopyrite inclusions (“chalcopyrite disease”; Barton and
LOD = 0.045  wt %, n>LOD = 100 (Fig. 9A), with a general Bethke, 1987).

Discussion
A
: Stage A Textures
15 : Stage B The observed textures outline a two-step pyrrhotite replace-
ment process. The first step is marked by replacement of
pyrrhotite by PyB1-po and the second one is characterized by
the replacement of pyrrhotite by marcasite, arsenopyrite by
PyB2-asp, and galena by PyB2-gn (Fig. 10). At the end of the sec-
Counts

10
ond step, marcasite that has replaced pyrrhotite is replaced by
PyB2-mrc (Fig. 10).
Einaudi (1968, 1977), based also on the work by Lacy
5 (1949), described five types of pyrite replacing the pyrrhotite
pipes and their rims. Einaudi’s (1968, 1977) type 1 pyrite is
the main constituent of the pyrite-quartz body (our PyB-PQB)
and also corresponds to the well-formed pyrite crystals pres-
0 ent in the pyrrhotite pipes (our PyB1-po). Einaudi (1968, 1977)
15 17 19 21 23 25 27 29 interpreted this pyrite to be formed before the emplacement
Mole % FeS
of the pyrrhotite pipe and their rims, and therefore the pyrite-
B quartz body was interpreted as the first mineralizing event at
0.009 Cerro de Pasco. Einaudi’s interpretation is, however, incom-
: Stage A patible with the field evidence that PyB1-po replaces the pyrrho-
0.008 : Stage B tite pipes, as demonstrated in the present study. The texture
1:1

0.007
shown in figure 6B of Einaudi (1977) can be easily interpreted
In apfu

0.006 as pyrrhotite crosscutting and replacing an early pyrite (PyA)


0.005 belonging to the same event that formed the pyrrhotite pipes
0.004 but having a more external position (Bartos, 1989). Einaudi’s
0.003
(1968, 1977) pyrite types 2, 3, 4, and 5 correspond to our PyB2-
mrc, PyB2-asp, and PyB2-gn (see Table 2).
0.002
The replacement of pyrrhotite by euhedral, relatively non-
0.001 porous pyrite crystals during the first step has been repro-
0.0 0.01 0.02 0.03 0.04 duced during experimental work done by Qian et al. (2011).
Cu apfu They point out that, at temperatures below 220°C, replace-
Fig. 9. Electron microprobe analyses of sphalerite from stage A and B: A) ment of pyrrhotite by relatively nonporous euhedral pyrite
FeS content (mol %) of sphalerite from stages A and B; B) Correlation In vs. without marcasite requires an external source of S2– (H2S) and
Cu diagram. Note the 1:1 correlation for sphalerite from stage A. pH > 2.5 to inhibit marcasite precipitation. The same authors

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SULFIDE REPLACEMENT REVEALED BY TRACE ELEMENT ANALYSES: CERRO DE PASCO, PERU 1361

Step 1 Step 2
PyB1-po Marcasite PyB2-mrc

H2S, pH > 2.5 H2S, pH < 2.5 pH or T


Pyrrhotite

PyB2-asp
Arsenopyrite

fO2 + H2 S

PyB2-gn

pH or T or fO2 or salinity
Galena

Fig. 10. Schematic diagram of textural relationships between different mineral phases during the replacement processes
affecting pyrrhotite, arsenopyrite, and galena.

demonstrate that replacement of pyrrhotite by pyrite is linked pH. Sphalerite seems unaffected (Fig. 5E, F), indicating that
to a coupled dissolution-reprecipitation mechanism. the fluid was already saturated in ZnS.
During a second step (Fig. 10), pyrrhotite crystals are In summary, during the first step, fluids probably were mod-
replaced by fine-grained marcasite. The replacement results erately acidic (pH >2.5) and relatively reduced to moderately
in a volume decrease of 28.7% (Qian et al., 2011), explain- oxidized; and during the second step, they were more acidic
ing the porous texture visible in hand samples and under the (pH <2.5) and oxidized. Replacement of marcasite by PyB2-mrc
microscope (Fig. 5C, D). According to Qian et al. (2011), at the end of the second step suggests a pH and/or tempera-
at temperatures below 220°C, marcasite rather than pyrite ture increase of the fluid (Fig. 10). A similar two-step evolu-
replaces pyrrhotite when the pH is <2.5 or when no external tion is also recorded in the pyrite-quartz body. Pyrite crystals
source of S2– (H2S) is available. At Cerro de Pasco, the first (PyB-PQB) contain in their inner parts inclusions of pyrrhotite,
possibility is favored as the absence of S2– (H2S) in the miner- chalcopyrite, and Fe-rich sphalerite. The Fe content of the
alizing fluid is unlikely taking into account that about 800 Mt sphalerite is consistent with equilibrium conditions; the pyrite-
of pyrite (Baumgartner et al., 2008) precipitated during stage pyrrhotite buffer indicates that fluids during the early pyrite
B to form the pyrite-quartz body. The recrystallization of fine- precipitation were reduced near the pyrite-pyrrhotite buffer.
grained marcasite to fine-grained (generally <50 µm) euhe- In the external part of the pyrite crystals, inclusions of hema-
dral pyrite (PyB2-mrc), suggests therefore a slight pH and/or tite often occur. Their presence is indicative of more oxidized
temperature increase. The observed replacement of arseno- conditions toward the end, following the reduced conditions
pyrite and galena by fine crystalline pyrite (PyB2-asp, PyB2-gn) during the early stage of formation of the pyrite-quartz body.
is interpreted to take place during the second step. Replace-
ment of arsenopyrite by pyrite is relatively independent of Trace elements
pH process (Heinrich and Eadington, 1986; Pokrovski et al., In situ LA-ICP-MS analyses allow content of a large set of
2002) and is essentially controlled by the following reaction: trace and minor elements to be quantified at low to very low
concentrations; however, a limiting factor of the method is
4FeAsS + 4H2S + 5O2(g) + 2 H2O = FeS2 + 4As(OH)30
the low spatial resolution (tens of micrometers) not allow-
This reaction requires a relatively oxidizing fluid to increase ing determination of whether a particular trace element is
As solubility as As(OH)30 complex, above NNO (nickel nickel incorporated in the structure itself or is present as micro- or
oxide) and below or around HM (hematite-magnetite) buf- nanoscale solid inclusions. Some recent studies (e.g., Deditius
fers to avoid hematite precipitation (Pokrovski et al., 2002). et al., 2011, Pačevski et al., 2012) revealed that many trace ele-
The reaction takes place only if enough H2S is available in the ments in pyrite are present as nano-inclusions of native met-
system. Replacement of galena indicates that the ore-forming als, sulfosalts, and sulfides. Only Ni, Co, As, and Se commonly
fluid was not saturated in PbS. Lead solubility is enhanced by occur structurally bound in the pyrite lattice (e.g., Vaughan
an increase of temperature, salinity, fO2, and/or decrease of and Rosso, 2006).

193
1362 ROTTIER ET AL.

The obtained trace element signatures show significant dif- A 103 PyB1-po Marcasite
ferences between replaced and newly formed minerals. Spe- Pyrrhotite Pyrrhotite
cifically, conversions of (1) pyrrhotite to PyB1-po and marcasite,
(2) marcasite to PyB2-mrc, and (3) arsenopyrite to PyB2-asp are 102
characterized by an important increase in most trace element
concentrations. Such chemical differences point toward dis-
solution-reprecipitation mechanisms (including the possibil- 10
ity of pressure-driven dissolution in the sense of Merino and
Canals, 2011) and against solid-state transformation as the lat-
ter process is accompanied by limited chemical exchange at 1
low temperature (250°C, e.g., Souza et al., 2002).
The recorded low trace element content of pyrrhotite
(Table 3; Fig. 7A), is consistent with observations made else- 0.1 V Mn Ni Zn As Cd Sb W Tl Bi
where (Large et al., 2007; Thomas et al., 2011), suggesting Cr Co Cu Ga Ag Sn Te Au Pb
that (1) the structure of low-temperature hydrothermal pyr- B 103 PyB2-mrc
rhotite is not favorable to the incorporation of trace elements, Marcasite
and (2) pyrrhotite is free of submicron- to nano-inclusions of
other phases. 102
Some elements, such as As, Sb, Te, W, Pb, Bi, included in
PyB1-po and marcasite replacing pyrrhotite, are enriched up
to 10 times whereas other elements are depleted compared 10
to the replaced mineral (Fig. 11A). The measured Sn and W
contents in PyB1-po and marcasite are best interpreted as the
result of local remobilization of solid inclusions of wolframite, 1
stannite, and cassiterite initially present in the pyrrhotite, as
both elements are hard to transport by a hydrothermal fluid at
temperatures of about 250°C (Heinrich, 1990). The high As 0.1 V Mn Ni Zn As Cd Sb W Tl Bi
content in pyrite and marcasite compared to those in pyrrho- Cr Co Cu Ga Ag Sn Te Au Pb
tite (Fig. 11A) and the fact that As concentration in PyB1-po and C 10 3
PyB2-asp

marcasite presents no correlation with any other element can Arsenopyrite

be attributed to the different oxidation state of sulfur in pyrite


(S–) and pyrrhotite (S2–), and the resulting easier incorpora- 102
tion of As as As– in the pyrite/marcasite structure (Vaughan
and Rosso, 2006). The enrichment of Pb, Sb, Ag, and Bi can
10
be due to the dissolution of galena and its solid inclusions of
Ag-Sb sulfosalt (Ag-rich tetrahedrite and/or polybasite). In
PyB1-po, the increased contents of Pb, Sb, Ag, and Bi compared 1
to those in the replaced pyrrhotite, the good correlation of
these elements (Fig. 12A, B, D), and the elevated Pb concen-
trations compared to other elements suggest that Pb, Sb, Ag, 0.1 V
and Bi contents are potentially linked to newly formed inclu- Mn Ni Zn As Cd Sb W Tl Bi
Cr Co Cu Ga Ag Sn Te Au Pb
sions of galena and, subordinate to that, of Pb-Sb-Ag sulfosalts.
The low content in trace elements of marcasite compared to D PyB1-po PyB2-mrc PyB2-asp
PyB1-po (Fig. 11a) is not fully understood. It could be linked 103 PyB-PQB PyB-PQB PyB-PQB
to enhanced metal solubility caused by pH decrease (<2.5, at
220°C; Qian et al., 2011), necessary for marcasite precipita-
tion, although structural limitations cannot be excluded. 102
The high contents of the majority of trace elements in PyB2-
mrc compared to pyrrhotite, marcasite, and PyB1-po (Figs. 7,
10
11B, D) can be interpreted as resulting from the combination
of (1) metal enrichment in the hydrothermal fluid following
the main dissolution event marked by pyrrhotite replace- 1
ment by marcasite and arsenopyrite and galena replacement
by pyrite (PyB2-asp, PyB2-gn), and (2) the solubility decrease
of most metals upon pH increase (e.g., Reed and Palandri, 0.1 V Mn Ni Zn As Cd Sb W Tl Bi
2006). Inferred solid inclusions in PyB2-asp are As-Pb-Ag-(Sb)-, Cr Co Cu Ga Ag Sn Te Au Pb
Cu-Sb-, and/or Au-Te-bearing, as shown by the positive cor- Fig. 11. Spider diagrams illustrating gain and loss of trace elements during
relations between these elements. Mole ratios of As and Pb various replacement processes: A) PyB1-po and marcasite over pyrrhotite; B)
(Fig. 12A) point to absence of or low content of galena inclu- PyB2-mrc over marcasite; C)PyB2-asp over arsenopyrite; D) PyB1-po, PyB2-mrc and
sions and in favor of As-Pb–bearing inclusions. PyB2-aspy over PyB-PQB.

194
SULFIDE REPLACEMENT REVEALED BY TRACE ELEMENT ANALYSES: CERRO DE PASCO, PERU 1363

PyB1-2
0
:1 :1 1:1 1:1 0
A 10
0 10 00 B 0:1 :1 1:
1 1:1
1:1 10 10 00
10
1 1:1
000
1 1:1 00
0
1:1
Pb (mol/t)

0 0.1
0.1 000
1:1

Sb (mol/t)
0
0 00
10-2 PyB-PQB
1:1
10-2
10-3
10-4 10-3

10-5
10-3 10-2 0.1 1 10 102 103 10-3 10-2 0.1 1 10 102
As (mol/t) Pb (mol/t)

:1 0:1
00 10
C 10 :1 D 0:1 10
:1
1:1
10 10 0
1 10 1:1
00
1:1 1:1
0.1 1 0
00
1:1
Ag (mol/t)
0
Bi (mol/t)

1:1 0.1
10-2
00 10-2
10-3 1:1

10-3
10-4
10-4
10 -5

10-5 10-4 10-3 10-2 0.1 10-4 10-3 10-2 0.1 1 10 102
Au (mol/t) Pb (mol/t)
1
E F 10: 1:1 1:1
0
10
00
10 1:1
Au0 1
000
1:1
1 0.1 0
Au (ppm)

Au+1 000
Ag (mol/t)

1:1
0.1 10-2
00
000
10-3 1:1
10-2
10-4
10-3
10-5

0.1 1 10 102 103 104 105 10-2 0.1 1 10 102


As (ppm) Cu (mol/t)

This study: PyB1-po Marcasite PyB2-mrc PyB2-asp PyB-PQB


Kouzmanov et al., 2010 Maydagan et al., 2013 Reich et al., 2013
King et al., 2014 Franchini et al., 2015
Fig. 12. Correlation diagrams of various trace elements in the studied sulfides (in mol/t) compared to published LA-ICP-MS
and SIMS data on trace elements in pyrite epithermal and porphyry systems: A) As-Pb; B) Pb-Sb; C) Au-Bi; D) Pb-Ag; E)
As-Au; and F) Cu-Ag. Marcasite is not plotted in C and E because Au concentrations are constantly below detection limit of
~0.1 ppm. Full data set from the present study is reported in Appendix 1.

195
1364 ROTTIER ET AL.

PyB2-asp is enriched in Mn, Cu, Ga, Ag, Cd, Sn, Te, Tl, in the major Fe sulfides with a limited number of elements
Pb, and Bi and depleted in Co, Ni, and Sb compared to the accommodated by the crystal structure and much larger set of
former arsenopyrite (Fig. 11C). Compared to PyB1-po and elements most probably present as micro- to nanoscale inclu-
PyB2-mrc, PyB2-asp is enriched in Co, As, Sb, and Au, elements sions, similar to results of other recently reported LA-ICP-
interpreted to be inherited from the arsenopyrite structure. MS and EPMA studies (Deditius et al., 2011, Pačevski et al.,
However, the depletion of Co and Au and, by two orders of 2012; Franchini et al., 2015). Trace element content of the
magnitude, of Sb and As in PyB2-asp compared to the replaced newly formed phases reflects major changes in the physico-
arsenopyrite suggests that these elements are mainly mobi- chemical evolution of the fluid from which they precipitate. It
lized into the hydrothermal fluid. also strongly depends on the nature of the replaced minerals
Figure 12 illustrates the main trends in trace element con- and their solid inclusions, as well as the geological environ-
tents in the various generations of replacement pyrite and mar- ment in which the replacement occurs.
casite from stage B (PyB1-po, marcasite, PyB2-mrc, PyB2-asp) and
pyrite from the pyrite-quartz body (PyB-PQB), in comparison New interpretation of fluid evolution during mineralization
with published data on pyrite from epithermal and porphyry at Cerro de Pasco
systems (e.g., Kouzmanov et al., 2010; Maydagan et al., 2013; The different trace element contents of replacing and replaced
Reich et al., 2013; King et al., 2014; Franchini et al., 2015). It minerals recognized in the present study are consistent with
should be noted that the studied pyrite and marcasite do not the textural interpretation and support it. A much simpler
belong to the high-sulfidation stage of mineralization at Cerro fluid evolution for the epithermal base metal mineralization
de Pasco (stage C, see above), but are formed during stage B, than previously published (Einaudi, 1968, 1977, Baumgart-
marked instead by low- to intermediate-sulfidation state (see ner et al., 2008) can be proposed (Fig. 13). According to this
next section). Our data set shows systematically the highest interpretation, mineralization starts with a stage of reducing
content in As, Sb, Pb and Bi in pyrite compared to published conditions marked by the formation of pyrrhotite pipes and
data. Positive correlations between some of the elements (Pb- their rims (stage A), followed by a progressive increase of the
Sb, Pb-Ag) are indicative of possible presence of nanoscale oxidation state and decrease of the pH of the fluid (pyrite-
solid inclusions as main carriers for those elements; however, quartz body, stage B), and terminating with a mineralizing
coupled substitutions and incorporation of part of the ele- event with highly oxidizing and acidic fluids (stage C). Such a
ments to a ppm level into the pyrite and marcasite structures scenario is consistent with a system dominated by reduced flu-
cannot be fully excluded. ids during the early ore precipitation due to strong wall-rock
Pyrite from the replacement textures and pyrite from the buffering (from the Excelsior shales and Pucará carbonates)
pyrite-quartz body form distinct fields in the diagrams (Fig. and relatively low fluid-to-rock ratio that progressively evolves
12A-D), PyB-PQB being systematically depleted in most trace to more oxidized and acidic conditions, with higher fluid-to-
elements. Petrographic and field observations suggest that rock ratio and weak wall-rock buffering toward the end of the
PyB-PQB precipitates at the same time as the replacement pro- replacement process.
cess affecting the pyrrhotite pipes and their rims that result
in the formation of PyB1-po, PyB2-apsy, marcasite and PyB2-mrc. Conclusions
The lower trace element content of most PyB-PQB compared to The field and microscopic observations as well as the geo-
the replacement pyrite is explained by chemical differences chemical data presented in this study indicate that the pyr-
of the hydrothermal fluids between sites where the replace- rhotite pipes and their rims at Cerro de Pasco were affected
ment process takes place over the Pucará carbonate rocks or by replacement processes contemporaneous with the forma-
in pyrrhotite pipes and their rims. Dissolution of pyrrhotite, tion of the large pyrite-quartz body. Therefore, and in contrast
arsenopyrite, galena, and their respective solid inclusions and to previous studies, we conclude that the emplacement of the
in particular, Ag-Sb-(Cu) sulfosalts, creates a local enrichment pyrrhotite pipes (stage A) and their Fe-rich sphalerite-galena
in a set of trace elements in the hydrothermal fluid that does rims preceded that of the pyrite-quartz body (stage B).
not take place by replacement of the Pucará Formation. The replacement textures resulting of the superposition of
Gold content in the studied sulfides ranges between 0.1 and hydrothermal events at Cerro de Pasco have been success-
1 ppm, corresponding to the average gold content in pyrite from fully used as a qualitative way to trace variations of fS2, fO2, and
epithermal and porphyry systems (Fig. 12E); at the same time, pH of the fluids. Two steps of replacement of the pyrrhotite
As is two to four orders of magnitude enriched. No correlation pipes and their rims have been recorded: (1) a first step trig-
between As and Au has been observed in pyrite and marcasite gered by moderately acidic, relatively reduced, and moder-
from Cerro de Pasco. In general, silver content is comparable ately oxidized fluids; and (2) a second step under more acidic
to the average Ag content of pyrite from epithermal and por- and oxidized conditions. The new sequence of hydrothermal
phyry systems, whereas Cu shows much lower concentrations events points to a much simpler fluid evolution than previ-
(Fig. 12F); the only exception is the PyB2-aspy, having among the ously proposed, with a progressive increase of fS2, fO2, and pH
higher Cu and Ag concentrations, again most probably due to of the mineralizing fluids. This evolution could be linked to a
the presence of nanoscale inclusions of Cu-Ag-bearing sulfo- decrease of the buffering effect, caused by the host rock, on
salt, resulting from local-scale reduction of the fluid following the acidic and oxidized magmatic fluid.
arsenopyrite dissolution (e.g., Pokrovski et al., 2002). This study combined textural and LA-ICP-MS trace ele-
Our detailed study of textural and mineral transformations ment analysis and has allowed tracing the replacement pro-
during the early mineralization stages at Cerro de Pasco reveals cess of pyrrhotite by pyrite and marcasite, and of arsenopyrite
complex mechanisms of incorporation of trace elements and marcasite by pyrite. LA-ICP-MS analyses are consistent

196
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T(°C)
100 200 300 400 500 600 800 1000