Rottier 2016

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
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
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
References 167
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
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
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
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
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
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
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
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
References 398
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.
References
Angeles, C., 1999. Los sedimentos cenozóicos de Cerro de Pasco: Estratigrafia,
sedimentación y tectónica, in Macharé, J., Benavides-Caceres, V., and Rosas, S., eds.,
Sociedad Geológica del Perú 5, 103–118.
Audétat, A., and Pettke, T., 2003. The magmatic-hydrothermal evolution of two barren
granites: a melt and fluid inclusion study of the Rito del Medio and Canada Pinabete
plutons in northern New Mexico (USA). Geochimica et Cosmochimica Acta, 67, 97-121.
Audétat, A., Pettke, T. Dolejs, D. 2004. Magmatic anhydrite and calcite in the ore-forming
quartz-monzodiorite magma at Santa Rita, New Mexico (USA): genetic constraints on
porphyry-Cu mineralization. Lithos 72, 147–161.
Audétat, A. 2013. Origin of Ti-rich rims in quartz phenocrysts from the Upper Bandelier Tuff
and the Tunnel Spring Tuff, southwestern USA. Chemical Geology 360–361, 99–104.
Audétat, A., 2015. Compositional evolution and formation conditions of magmas and fluids
related to porphyry Mo mineralization at Climax, Colorado. Journal of Petrology 56, 1519-
1546.
Bachmann, O., Bergantz, G.W., 2004. On the origin of crystal-poor rhyolites: extracted from
batholithic cristal mushes. Journal of Petrology 45, 1565-1582.
Bachmann, O., Dungan, M.A., Bussy, F., 2005. Insights into shallow magmatic processes in
large silicic magmabodies: the trace element record in the Fish Canyon magma body,
Colorado. Contribution to Mineralagoy and Petrology 149, 338-349.
Bachmann, O., Bergantz, G.W., 2006. Gas percolation in upper-crustal silicic crystal mushes
as a mechanism for upward heat advection and rejuvenation of near-solidus magma bodies.
Journal of Volcanology and Geothermal Research 149, 85-102.
Bachmann, O., Charlier, B.L.A., Lowenstern, J.B., 2007. Zircon crystallization and recycling
in the magma chamber of the rhyolitic Kos Plateau Tuff (Aegean Arc). Geology 35, 73-76.
Baker, D.R., Moretti, R., 2011. Modeling the solubility of sulfur in magmas: a 50-year old
geochemical challenge. Review in Mineralogy and Geochemistry 73, 167–213.
42
Baumgartner, R., 2007. Sources and evolution in space and time of hydrothermal fluids at the
Cerro de Pasco Cordilleran base metal deposit, Central Peru. Terre & Environnement 66,
167 p.
Baumgartner, R., Fontboté, L., Vennemann, T., 2008. Mineral zoning and geochemistry of
epithermal polymetallic Zn-Pb-Ag-Cu-Bi mineralization at Cerro de Pasco, Peru.
Economic Geology 103, 493–537.
Baumgartner, R., Fontboté, L., Spikings, R., Ovtcharova, M., Schneider, J., Pace, L., Gutjahr
M., 2009. Bracketing the age of magmatic-hydrothermal activity at the Cerro de Pasco
epithermal polymetallic deposit, central Peru: a U-Pb and 40Ar/39Ar study. Economic
Geology 104, 479-504.
Black, L. P., Kamo, S. L., Allen, C. M., Davis, D. W., Aleinikoff, J. N., Valley, J. W., et al.
2004. Improved 206Pb/238U microprobe geochronology by the monitoring of a trace-
element-related matrix effect; SHRIMP, ID–TIMS, ELA–ICP–MS and oxygen isotope
documentation for a series of zircon standards. Chemical Geology 205, 115–140.
Blundy, J., Wood, B., 2003. Partitioning of trace elements between crystals and melts. Earth
and Planetary Science Letters 210, 383-397.
Bendezú, R., Fontboté, L., 2009. Cordilleran epithermal Cu-Zn-Pb-(Au-Ag) mineralization in
the Colquijirca district, Central Peru: Deposit-scale mineralogical patterns: Economic
Geology 104, 905–944.
Beuchat, S. 2003. Geochronological, structural, isotope and fluid inclusion constraints of the
polymetallic Domo de Yauli district, Peru. Terre & Environnement 41, 130 p.
Bissig, T., Ullrich, T.D., Tosdal, R.M., Friedman, R., Ebert, S., 2008. The time-space
distribution of Eocene to Miocene magmatism in the central Peruvian polymetallic
province and its metallogenetic implications. Journal of South American Earth Sciences
26, 16–35.
Bissig, T., Tosdal, R.M., 2009. Petrogenetic and Metallogenetic Relationships in the Eastern
Cordillera Occidental of Central Peru. The Journal of Geology 117, 499–518.
Boehnke, P., Watson, E.B., Trail, D., Harrison, T.M., Schmitt, A.K., 2013. Zircon saturation
re-revisited. Chemical Geology 351, 324-334.
Borisova, A.Y., Freydier, R., Polvé, M., Salvi, S., Candaulap, F., Aigouy, T., (2008) In Situ
Multi-Element Analysis of the Mount Pinatubo Quartz-Hosted Melt Inclusions by NIR
Femtosecond Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry.
Geostandards and Geoanalytical Research 32, 209-229.
Bowring, J.F., Mclean, N.M., Bowring, S.A., 2011. Engineering cyber infrastructure for U-Pb
geochronology: Tripoli and U-Pb_Redux. Geochemistry Geophysics Geosystems, 12,
Q0AA19. doi:10.1029/2010GC003479
Buret, Y., Von Quadt, A., Heinrich, C., Selby, D., Wälle, M., Peytcheva, I. 2016. From a
long-lived upper-crustal magma chamber to rapid porphyry copper emplacement: Reading
the geochemistry of zircon crystals at Bajo de la Alumbrera (NW Argentina). Earth and
Planetary Science Letters 450, 120-131.
Buret, Y., Wotzlaw, J.F., Roozen, S., Guillong, M., von Quadt, A., Heinrich, C.A. 2017.
Zircon petrochronological evidence for a plutonic-volcanic connection in porphyry copper
deposits. Geology, G38994-1.
Burgisser, A., Bergantz, G.W., 2011. A rapid mechanism to remobilize and homogenize
highly crystalline magma bodies. Nature 471, 212–215.
Burnham, C.W., 1997. Magmas and hydrothermal fluids. In: Barnes, H.L. (Ed.), Geo-
chemistry of Hydrothermal Ore Deposits, 3rd edn. John Wiley & Sons, New York, pp.63–
123.
43
Carrichi, L., Blundy, J., 2015. Experimental petrology of monotonous intermediate magmas.
In: Chemical, Physical and Temporal Evolution of Magmatic Systems. Geological Society
of London, 2015. p. 26
Cashman, K.V., Blundy, J.D., 2013. Petrological cannibalism – the chemical and textural
consequences of incremental magma body growth. Contributions to Mineralogy and
Petrology 166, 703–729.
Cashman, K.V., Sparks, R.S.J., Blundy, J.D., 2017. Vertically extensive and unstable
magmatic systems: A unified view of igneous processes. Science, 355, eaag3055.
Catchpole H., Kouzmanov K., Putlitz B., Seo J., Fontboté L., 2015. Zoned Base Metal
Mineralization in a Porphyry System: Origin and Evolution of Mineralizing Fluids in the
Morococha District, Peru. Economic Geology 110, 39–71.
Chelle-Michou, C., Rottier, B., Caricchi, L., Simpson, G., 2017. Tempo of magma degassing
and the genesis of porphyry copper deposits. Scientific Reports, 7, 40566.
Chiaradia, M., Müntener, O., Beate, B., 2014. Quaternary sanukitoid-like andesites generated
by intracrustal processes (Chacana caldera complex, Ecuador): implications for Archean
sanukitoids. Journal of Petrology 55, 769–802.
Condon, D., Mclean, N., Schoene, B., Bowring, S., Parrish, R., Noble, S.R., 2008. Synthetic
U-Pb ‘standard’ solutions for ID-TIMS geochronology. Geochimica et Cosmochimica
Acta 72, 175-175.
Condon, D., Schoene, B., Mclean, N., Bowring, S., Parrish, R. 2015. Metrology and
Traceability of U-Pb Isotope Dilution Geochronology (EARTHTIME Tracer Calibration
Part I). Geochimica et Cosmochimica Acta, 164, 464–480.
Cooper, K.M., Kent, A.J.R., 2014. Rapid remobilization of magmatic crystals kept in cold
storage. Nature 506, 480–483
Cooper, K. M. 2017. What Does a Magma Reservoir Look Like? The “Crystal's-Eye” View.
Elements 13, 23-28.
Couch, S., Sparks, R.S.J., Carroll, M.R., 2001. Mineral disequilibrium in lavas explained by
convective self-mixing in open magma chambers. Nature 411, 1037–1039.
Deering, C.D., Keller, B., Schoene, B., Bachmann, O., Beane, R., Ovtcharova, M., 2016.
Zircon record of the plutonic-volcanic connection and protracted rhyolite melt evolution.
Geology 44, 267-270.
Einaudi, M.T., 1968. Pyrrhotite-pyrite-sphalerite relations at Cerro de Pasco, Peru.
Unpublished Ph.D. thesis, Cambridge, MA, Harvard University, 381 p.
Einaudi, M.T., 1977. Environment of ore deposition at Cerro de Pasco, Peru. Economic
Geology 72, 893–924.
Ferry, J.M., Watson, E.B., 2007. New thermodynamic models and revised calibrations for the
Ti-in-zircon and Zr-in-rutile thermometers. Contributions to Mineralogy and Petrology
154, 429–437.
Guillong M., Meier D.L., Allan M.M., Heinrich C.A., Yardley B.W.D., 2008, SILLS: a
Matlab-based program for the reduction of Laser Ablation ICP-MS data of homogeneous
materials and inclusions. In: Sylvester, P. (Ed.), Laser-ablation-ICPMS in the earth
sciences: current practices and outstanding issues. Mineralogical Association of Canada,
Vancouver, B.C., pp. 328–333.
Guillong, M., von Quadt, A., Sakata, S., Peytcheva, I., Bachmann, O., 2014. LA-ICP-MS Pb-
U dating of young zircons from the Kos-Nisyros volcanic centre, SE Aegean arc. Journal
of Analytical Atomic Spectrometry 29, 963–970.
Günther, D., Frischknecht, R., Heinrich, C.A., Kahlert, H.J., 1997. Capabilities of an Argon
Fluoride 193 nm excimer laser for laser ablation inductively coupled plasma mass
spectrometry microanalysis of geological materials. Journal of Analytical Atomic
Spectrometry 12, 939-944.
44
Günther, D., Audétat, A., Frischknecht, R., Heinrich, C. A., 1998. Quantitative analysis of
major, minor and trace elements in fluid inclusions using laser ablation–inductively
coupled plasmamass spectrometry. Journal of Analytical Atomic Spectrometry 13, 263-
270.
Gutscher, M.A., Olivet, J.L., Aslanian, D., Eissen, J.P., Maury, R., 1999. The “lost Inca
Plateau’’: Cause of flat subduction beneath Peru? Earth and Planetary Science Letters 171,
335–341.
Halter, W.E., Pettke, T., Heinrich, C.A., and Roten-Rutishauser, B., 2002. Major to trace
element analysis of melt inclusions by laser-ablation ICP-MS: methods of quantification.
Chemical Geology 183, 63-86.
Halter, W.E., Bain, N., Becker, K., Heinrich, C.A., Landtwing, M., Von Quadt, A., Clark,
A.H., Sasso, A.M., Bissig, T., Tosdal, R.M., 2004a. From andesitic volcanism to the
formation of a porphyry Cu–Au mineralizing magma chamber: the Farallón Ne-gro
Volcanic Complex, northwestern Argentina. Journal of Volcanology and Geothermal
research 136, 1–30.
Halter, W.E., Heinrich, C.A., Pettke, T., 2004b. Laser-ablation ICP-MS analysis of sili-cate
and sulfide melt inclusions in an andesitic complex II: evidence for magma mixing and
magma chamber evolution. Contribution to Mineralagoy and Petrology147, 397–412.
Halter, W.E., Heinrich, C.A., Pettke, T., 2005. Magma evolution and the formation of
porphyry Cu–Au ore fluids: evidence from silicate and sulfide melt inclusions. Mineralium
Deposita 39, 845–863.
Hampel, A., 2002. The migration history of the Nazca Ridge along the Peruvian active
margin: a re-evaluation. Earth and Planetary Science Letters 203, 665–679.
Hattori, K.H., and Keith, J., 2001. Contribution of mafic melt to porphyry copper
mineralization: Evidence from Mount Pinatubo, Philippines, and Bingham Canyon, Utah,
USA. Mineralium Deposita 36, 799–806.
Heinrich, C.A., Pettke, T., Halter, W.E., Aigner-Torres, M., Audétat, A., Günther, D.,
Hattendorf, B., Bleiner, D., Guillong, M., and Horn, I., 2003. Quantitative multi-element
analysis of minerals, fluid and melt inclusions by laser-ablation inductively-coupled-
plasma mass-spectrometry. Geochimica Cosmochimica Acta 67, 3473–3496.
Hiess, J., Condon, D.J., McLean, N., Noble, S.R., 2012. 238U/235U Systematics in Terrestrial
Uranium-Bearing Minerals. Science 30, 1610-1614.
Huang, R., and Audetat, A., 2012. The titanium-in-quartz (TitaniQ) thermobarometer: a
critical examination and re-calibration. Geochimica Cosmochimica Acta 84, 75–89.
Huber, C., Bachmann, O., and Manga M., 2010. Two competing effects of volatiles on heat
transfer in crystal-rich magmas: Thermal insulation vs defrosting. Journal of Petrology 51,
847–867.
Huber, C., Bachmann, O., and Dufek, J., 2011. Thermo-mechanical reactivation of locked
crystal mushes: Melting-induced internal fracturation and assimilation processes in
magmas. Earth and Planetary Science Letters 304, 443–454.
Johnson, E.R., Kamenetsky, V.S. and McPhie, J., 2013. The Behavior of Metals (Pb, Zn, As,
Mo, Cu) During Crystallization and Degassing of Rhyolites from the Okataina Volcanic
Center, Taupo Volcanic Zone, New Zealand. Journal of Petrology 54, 1641-1659.
Kularatne, K., and Audétat, A., 2014. Rutile solubility in hydrous rhyolite melts at 750–900°C
and 2 kbar, with application to titanium-in-quartz (TitaniQ) thermobarometry. Geochimica
et Cosmochimica Acta 125, 196–209.
Lowenstern, J.B., 2001. Carbon dioxide in magmas and implications for hydrothermal
systems. Mineraliun Deposita 36, 490–502.
45
Mandeville, C.W., Carey, S., and Sigurdsson, H., 1996. Magma mixing, fractional
crystallization and volatile degassing during the 1883 eruption of Krakatau volcano,
Indonesia. Journal of Volcanology and Geothermal Research 74, 243-274
Mattinson, J.M., 2005. Zircon U–Pb chemical abrasion (“CA-TIMS”) method: combined
annealing and multi-step partial dissolution analysis for improved precision and accuracy
of zircon ages. Chemical Geology 220, 47-66.
Maughan, D.T., Keith, J.D., Christiansen, E.H., Pulsipher, T., Hattori, K., and Evans, N.J.,
(2002). Contributions from mafic alkaline magmas to the Bingham porphyry Cu–Au–Mo
deposit, Utah, USA. Mineralium Deposita, v. 37, p. 14-37.
McLennan, S.M., 2001. Relationships between the trace element composition of sedimentary
rocks and upper continental crust. Geochemistry, Geophysics, Geosystems 2, 1021.
Mustard, R., Ulrich, T., Kamenetsky, V.S, and Merbagh T., 2006. Gold and metal enrichment
in natural granitic melts during fractional crystallization. Geology 34, 85-88.
Nadeau, O., Stix, J. and Williams-Jones, A.E., 2013 The behavior of Cu, Zn and Pb during
magmatic–hydrothermal activity at Merapi volcano, Indonesia. Chemical Geology 342,
167-179.
Noble, D.C., and McKee, E.H., 1999. The Miocene metallogenic belt of central and northern
Peru. Society of Economic Geologists Special Publications 7, 155–193.
Parmigiani, A., Huber, C., and Bachmann, O., 2014. Mush microphysics and the reac-tivation
of crystal-rich magma reservoirs. Journal of Geophysical Research: Solid Earth 119, 6308–
6322.
Pin, C., Briot, D., Bassin, C. and Poitrasson, F. 1994. Concomitant separation of strontium
and samarium–neodymium for isotopic analysis in silicate samples, based on specific
extraction chromatography. Analytica Chimica Acta 298, 209–217.
Pirrie, D., Butcher, A.R., Power, M.R., Gottlieb, P., Miller, G.L. 2004. Rapid Quantitative
Mineral and Phase Analysis Using Automated Scanning Electron Microscopy
(QEMSCAN); Potential Applications in Forensic Geoscience. Geological Society, London,
Special Publication 232, 123-136.
Price, R.C., Gamble, J.A., Smith, I.E.M., Stewart, R.B., Eggins, E. and Wright, I.C., 2005 An
integrated model for the temporal evolution of andesites and rhyolites and crustal
development in New Zealand’s North Island. Journal of Volcanology and Geothermal
Research 140, 1-24.
Rogers, R., 1983. Structural and geochemical evolution of a mineralized volcanic vent at
Cerro de Pasco, Peru: Unpublished PhD thesis, Tucson, University of Arizona, 116 p.
Rosas S, Fontboté L, Tankard A, (2007) Tectonic evolution and paleogeography of the
Mesozoic Pucará Basin, central Peru: Journal South American Earth Sciences, v. 26, p. 16–
35.
Rosenbaum, G., Giles, D., Saxon, M., Betts, P.G., Weinberg, R.F., and Duboz, C., 2005,
Subduction of the Nazca Ridge and the Inca Plateau: Insights into the formation of ore
deposits in Peru. Earth and Planetary Science Letters 239,. 18–32.
Rottier. B., 2017, Magmatic and hydrothermal fluid processes at the origin of the giant
porphyry-related epithermal polymetallic deposit of Cerro de Pasco (Central Peru), PhD
thesis. Univ. Geneva.
Rottier, B., Kouzmanov, K., Bouvier, A.S., Baumgartner, L., Wälle, M., Rezeau, H.,
Bendezú, R., Fontboté, L., 2016a, 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 447, 93-116.
Rottier, B., Kouzmanov, K., Wälle, M., Bendezú, R., and Fontboté, L., 2016b, Sulfide
replacement processes revealed by textural an LA-ICP-MS trace element analyses:
46
example from the early mineralization stages at Cerro de Pasco, Peru. Economic
Geolology111, 1347-1367.
Rottier, B., Kouzmanov, K., Casanova, C., Bouvier, A.S., Baumgartner, L., Wälle, M.,
Fontboté, L., (submitted), Hydrothermal evolution of a hidden porphyry-type
mineralization related to the large epithermal polymetallic deposit of Cerro de Pasco
district (Peru): Mineralium Deposita (submitted)
Schoene, B., Crowley, J., Condon, D., Schmitz, M., Bowring, S., 2006. Reassessing the
uranium decay constants for geochronology using ID-TIMS U–Pb data. Geochimica et
Cosmochimica Acta, 70, 426–445.
Schoene, B., Schaltegger, U., Brack, P., Latkoczy, C., Stracke, A., and Günther, D., 2012.
Rates of magma differentiation and emplacement in a ballooning pluton recorded by U–Pb
TIMS-TEA, Adamello batholith, Italy. Earth and Planetary Science Letters 355–356, 162–
173.
Shinohara, H., Kazahaya, K., and Lowenstern, J. B. 1995. Volatile transport in a convecting
magma column: implications for porphyry Mo mineralization. Geology 23, 1091-1094.
Shinohara, H., and Hedenquist, J.W., 1997. Constraints on magma degassing beneath the Far
Southeast porphyry Cu–Au deposit, Philippines. Journal of Petrology 38, 1741-1752.
Sillitoe, R.H., 2010. Porphyry copper systems. Economic Geology, 105, 3-41.
Sparks, R.S.J., Cashman, K.V. 2017. Dynamic Magma Systems: Implications for Forecasting
Volcanic Activity. Elements, 13, 35-40.
Spikings, R., Reitsma, M.J., Boekhout, F., Mišković, A., Ulianov, A., Chiaradia, M., Gerdes,
A., Schaltegger, U., 2016. Characterization of Triassic rifting in Peru and implications for
the early disassembly of western Pangaea: Gondwana Research, v. 35, p. 124–143.
Soler, P., and Rotach-Toulhoat, N. 1990. Sr-Nd isotope compositions of Cenozoic granitoids
along a traverse of the central Peruvian Andes. Geological Journal 25, 351–358.
Tapster, S., Condon, D.J., Naden, J., Noble, S. R., Petterson, M.G., Roberts, N.M.W., and
Smith, D.J. 2016. Rapid thermal rejuvenation of high-crystallinity magma linked to
porphyry copper deposit formation; evidence from the Koloula Porphyry Prospect,
Solomon Islands. Earth and Planetary Science Letters, 442, 206-217.
Ulianov, A., Müntener, O., Schaltegger, U. and Bussy, F. 2012. The data treatment dependent
variability of U–Pb zircon ages obtained using mono-collector, sector field, laser ablation
ICPMS. Journal of Analytical Atomic Spectrometry 27, 663–676.
Watson, E.B., and Harrison, T.M., 1983. Zircon saturation revisited: temperature and
composition effects in a variety of crustal magma types. Earth and Planetary Science
Letters 64, 295-304.
Wendt, I., Carl, C., 1991. The statistical distribution of the mean squared weighted deviation.
Chemical Geology, Isot. Geosci. Sect, 86, 275–285.
Wotzlaw, J.F., Schaltegger, U., Frick, D.A., Dungan, M.A., Gerdes, A., and Günther, D.,
2013. Tracking the evolution of large-volume silicic magma reservoirs from assembly to
supereruption. Geology 41, 867-870.
47
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 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 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 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 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
49
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 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 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 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 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 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
50
Li B Na Mg Al P K Ti Mn Fe Cu Zn As Rb Sr Y Zr Nb Mo
Quartz Analyse # Si (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
Quartz Analyse #
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
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
CPR 472 Baumgartner UTM-PSAD56
2nd ramp tajo Raul Rojas E sampled in the open pit
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

206 238 207 235 207 206 206 238 207 235 207
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

206 238 207 235 207 206 206 238 207 235 207
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

206 238 207 235 207 206 206 238 207 235 207
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

206 238 207 235 207 206 206 238 207 235 207
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

206 238 207 235 207 206 206 238 207 235 207
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)
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
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)
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
Al Si Ti Rb Sr Zr Nb Ba La Ce Pr Nd Sm Eu Gd Tb Dy Ho
Sample P (ppm) Y (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
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)
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 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 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 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
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
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 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 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
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 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 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
66
Li B Na Mg P K Ca Ti Mn Fe Cu Zn Rb Sr Y Zr Nb Mo
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 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
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 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 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 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
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
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
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
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
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
corrected
206Pb/204Pb
corrected
207Pb204Pb
corrected
208Pb/204Pb
corrected
DT: dacitic tuff; DD: dacitic dome; QM: Quartz-monzonite dyke; RDD: rhyodacitic dome; TP: Trachyte porphyry
*: Data from Baumgartner et al., 2009
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
73
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
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
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
76
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.
77
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
†
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
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
78
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
79
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).
85
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
86
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).
87
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
88
(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
91
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.
92
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.
93
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
96
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.
98
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
101
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).
102
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.
103
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.
105
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.
References
Angeles C (1999) Los sedimentos cenozóicos de Cerro de Pasco: Estratigrafia, sedimentación y
tectónica, in Macharé, J., Benavides-Cáceres, V., and Rosas, S., eds., Sociedad Geológica del
Perú, 5:103–118.
Audétat A, Pettke T, Heinrich CA, Bodnar RJ (2008) The composition of magmatic–hydrothermal
fluids in barren and mineralized intrusions. Econ Geol 103:877–908.
Audétat A, Lowenstern JB (2014) Melt inclusions. In Geochemistry of mineral deposits (ed. S. D.
Scott). Treatise on Geochemistry 2nd ed. 13:143-173.
Auer S, Bindeman I, Wallace P, Ponomareva V, Portnyagin, M (2009) The origin of hydrous, high-
δ18O voluminous volcanism: Diverse oxygen isotope values and high magmatic water contents
within the volcanic record of Klyuchevskoy volcano, Kamchatka, Russia. Contrib Mineral Petr
157:209–230.
Baker T (2002) Emplacement depth and carbon dioxide-rich fluid inclusions in intrusion-related gold
deposit Econ Geol 97:1111–1117.
Bakker RJ, Brown PE (2003) Computer modelling in fluid inclusion research: In I. Samson, A.
Anderson, & D. Marshall, eds. Fluid Inclusions: Analysis and Interpretation. Mineralogical
Association of Canada, Short Course Series, 32, pp. 175-204.
Baumgartner R (2007) Sources and evolution in space and time of hydrothermal fluids at the Cerro de
Pasco Cordilleran base metal deposit, Central Peru. Terre & Environnement, 66.
Baumgartner R, Fontboté L, Vennemann T (2008) Mineral zoning and geochemistry of epithermal
polymetallic Zn-Pb-Ag-Cu-Bi mineralization at Cerro de Pasco, Peru. Econ Geol 103:493–537.
Baumgartner R, Fontboté L, Spikings R, Ovtcharova M, Schneider J, Pace L, Gutjahr M (2009)
Bracketing the age of magmatic-hydrothermal activity at the Cerro de Pasco epithermal
polymetallic deposit, central Peru: a U-Pb and 40Ar/39Ar study: Econ Geol 104:479-504.
Becker SP, Fall A, Bodnar RJ (2008) Synthetic fluid inclusions. XVII. PVTX properties of high
salinity H2O–NaCl solutions (>30 wt% NaCl): application to fluid inclusions that homogenize
by halite disappearance from porphyry copper and other hydrothermal ore deposits. Econ Geol
103: 539–554.
Bindeman I (2008) Oxygen isotopes in mantle and crustal magmas as revealed by single crystal
analysis. Rev Mineral Geochem 69: 445–478.
Bissig T, Ullrich TD, Tosdal RM, Friedman R, Ebert S (2008) The time-space distribution of Eocene
to Miocene magmatism in the central Peruvian polymetallic province and its metallogenetic
implications. J South Am Earth Sci 26:16–35.
Bissig T, Tosdal RM (2009) Petrogenetic and Metallogenetic Relationships in the Eastern Cordillera
Occidental of Central Peru. J Geol 117:499–518.
Bodnar RJ, Student JJ (2006) Melt inclusions in plutonic rocks: Petrography and microthermometry.
In Melt Inclusions in Plutonic Rocks (J. D. Webster, ed.) Mineral.Assoc. Canada, Short Course
36, pp 1-26.Carrigan CR, Schubert G, Eichelberger J, (1992) Thermal and dynamical regimes of
single-and two-phase magmatic flow in dikes. J Geophys Res 97: 377–392.
118
Caricchi L, Blundy J (2015) Experimental petrology of monotonous intermediate magmas. Geological
Society, London, Special Publications 422:105-130
Catchpole H, Kouzmanov K, Fontboté L, Guillong M, Heinrich CA (2011) Fluid evolution in zoned
Cordilleran polymetallic veins — insights from microthermometry and LA-ICP-MS of fluid
inclusions. Chem Geol 281:293–304.
Catchpole H, Kouzmanov K, Putlitz B, Seo J, and Fontboté L (2015a) Zoned Base Metal
Morococha District, Peru. Econ Geol 110:39-71.
Catchpole H, Kouzmanov K, Bendezú A, Ovtcharova M, Spikings R, Stein H, Fontboté L (2015b)
Timing of porphyry (Cu-Mo) and base metal mineralisation (Zn-Pb-Ag-Cu) in a magmatic-
hydrothermal system – Morococha district, Peru. Miner Deposita 50:895-922.
Cherniak DJ, Watson EB, Wark DA (2007a) Ti diffusion in quartz. Chem Geol 236:65−74.
Cherniak DJ, Manchester J, Watson EB (2007b) Zr and Hf diffusion in rutile. Earth Planet Sci Lett
261: 267−279.
Diamond LW (1992) Stability of CO2 clathrate hydrate + CO2 liquid + CO2 vapour + aqueous KCl-
NaCl solutions: Experimental determination and application to salinity estimates of fluid
inclusions. Geochim Cosmochim Acta 56: 273–280.
Driesner T (2007) The system H2O-NaCl. Part II: Correlations for molar volume, enthalpy, and
isobaric heat capacity from 0 to 1000°C, 1 to 5000bar, and 0 to 1 XNaCl. Geochim Cosmochim
Acta 71:4902–4919.
Driesner T, Heinrich CA (2007) The system H2O-NaCl. I. Correlations for molar volume, enthalpy,
and isobaric heat capacity from 0 to 1000 degrees C, 1 to 5000 bar, and 0 to 1 X-NaCl.
Geochim Cosmochim Acta 71:4880–4901.
Duan Z, Møller N, and Weare JH (1992) An equation of state for the CH4-CO2-H2O system: II.
Mixtures from 50 to 1000°C and 0 to 1000 bar. Geochim Cosmochim Acta 56:2619–2631.
Einaudi MT (1968) Pyrrhotite-pyrite-sphalerite relations at Cerro de Pasco, Peru. Unpublished Ph.D.
thesis, Cambridge, MA, Harvard University, 381 p.
Einaudi MT (1977) Environment of ore deposition at Cerro de Pasco, Peru. Econ Geol 72: 893–924.
Guillong M, Heinrich CA (2007) LA-ICP-MS analysis of inclusions: Improved ablation and detection:
European Current Research On Fluid Inclusions (ECROFI-XIX), At Bern, p. 82.
Guillong M, Meier DL, Allan MM, Heinrich CA, Yardley BWD (2008) SILLS: a Matlab-based
program for the reduction of Laser Ablation ICP-MS data of homogeneous materials and
inclusions. In: Sylvester, P. (Ed.), Laser-ablation-ICPMS in the earth sciences: current practices
and outstanding issues. Mineralogical Association of Canada, Vancouver, B.C., pp 328–333.
Günther D, Frischknecht R, Heinrich CA, Kahlert HJ (1997) Capabilities of an Argon Fluoride 193
nm excimer laser for laser ablation inductively coupled plasma mass spectrometry
microanalysis of geological materials. J Anal At Spectrom 12:939-944.
Günther D, Audétat A, Frischknecht R, Heinrich CA (1998) Quantitative analysis of major, minor and
trace elements in fluid inclusions using laser ablation–inductively coupled plasma mass
spectrometry. J Anal At Spectrom 13:263-270.
Gustafson LB, Hunt JP (1975) The porphyry copper deposit at El Salvador, Chile. Econ Geol 70: 857-
912.
Halter WE, Pettke T, Heinrich CA, Roten-Rutishauser B (2002) Major to trace element analysis of
melt inclusions by laser-ablation ICP-MS: methods of quantification. Chem Geol 183:63-86.
Halter WE, Heinrich CA, Pettke T (2005) Magma evolution and the formation of porphyry Cu–Au ore
fluids: evidence from silicate and sulfide melt inclusions. Min Dep 39:845-863.
Harris AC, Kamenetsky VS, White NC, van Achterbergh E, Ryan CG (2003) Melt inclusions in veins:
Linking magmas and porphyry Cu deposits. Science 302:2109–2111.
Hayden LA, Watson EB, Wark DA (2008) A thermobarometer for sphene (titanite). Contrib Mineral
Petr 155:529-540.
Heinrich CA, Pettke T, Halter WE, Aigner-Torres M, Audétat A, Günther D, Hattendorf B, Bleiner D,
Guillong M, Horn I (2003) Quantitative multi-element analysis of minerals, fluid and melt
inclusions by laser-ablation inductively-coupled-plasma mass-spectrometry. Geochim
Cosmochim Acta 67:3473–3496.
119
Huang R, Audétat A (2012) The titanium-in-quartz (TitaniQ) thermobarometer: a critical examination
and re-calibration. Geochim Cosmochim Acta 84:75–89.
Ivascanu PM, Pettke T, Kouzmanov K, Heinrich CA, Pintea I, Rosu E, Udubasa GH (2003) The
magmatic to hydrothermal transition: Miocene Deva porphyry copper-gold deposit, South
Apuseni Mts, Romania. Society for Geology Applied to Mineral Deposits, SGA Biennial
Meeting, 7th, Athens, Greece, 2003, Proceedings, pp 283–286.
Klemm LM, Pettke T, Heinrich CH (2007) Hydrothermal evolution of the El Teniente deposit, Chile:
Porphyry Cu-Mo ore deposition from low-salinity magmatic fluids. Econ Geol 102:1021–1045.
Klemm LM, Pettke T, Heinrich CA (2008) Fluid and source magma evolution of the Questa porphyry
Mo deposit, New Mexico, USA. Miner Deposita 43:533–552.
Kouzmanov K, Pokrovski GS (2012) Hydrothermal controls on metal distribution in porphyry Cu (-
Mo-Au) systems. Society of Economic Geologists Special Publication 16: 573–618.
Landis GP, Rye RO (1974) Geologic, fluid inclusion, and stable isotope studies of the Pasto Bueno
tungsten-base metal deposit, northern Peru. Econ Geol 69:1025–1059.
Landtwing MR, Pettke T, Halter WH, Heinrich CA, Redmond PB, Einaudi MT, Kunze K (2005)
Copper deposition during quartz dissolution by cooling magmatic-hydrothermal fluids: The
Bingham porphyry. Earth Planet Sci Lett 235: 229–243.
Landtwing MR, Furrer C, Redmond PB, Pettke T, Guillong M, Heinrich CA (2010) The Bingham
Canyon porphyry Cu-Mo-Au deposit. III. Zoned copper-gold ore deposition by magmatic vapor
expansion. Econ Geol 105:91–118.
Lecumberri-Sanchez P, Steele-MacInnis M, Bodnar RJ (2012) A numerical model to estimate trapping
conditions of fluid inclusions that homogenize by halite disappearance. Geochim Cosmochim
Acta 92:14–22.
Lecumberri-Sanchez P, Steele-MacInnis M, Weis P, Driesner T, Bodnar RJ (2015) Salt precipitation
in magmatic-hydrothermal systems associated with upper crustal plutons. Geology 43:1063-
1066.
Lerchbaumer L, Audétat A (2013) The metal content of silicate melts and aqueous fluids in
subeconomically Mo mineralized granites: implications for porphyry Mo genesis. Econ Geol
108:987-1013.
Lowenstern JB (2001) Carbon dioxide in magmas and implications for hydrothermal systems. Miner
Deposita 36:490–502.
Lund K, Aleinikoff JN, Kunk MJ, Unruh DM, Zeihen GD, Hodges WC, du Bray EA, O’Neill JM
(2002) SHRIMP U-Pb and 40Ar/39Ar age constraints for relating plutonism and mineralization
in the Boulder batholith region, Montana. Econ Geol 97:241–267.
Masterman GJ, Cooke DR, Berry RF, Walshe JL, Lee AW, Clark AH (2005) Fluid chemistry,
structural setting, and emplacement history of the Rosario Cu-Mo porphyry and Cu-Ag-Au
epithermal veins, Collahuasi district, northern Chile. Econ Geol 100:835–862.
Matsuhisa Y, Goldsmith JR, Clayton RN (1979) Oxygen isotopic fractionation in the system quartz-
albite-anothite-water. Geochim Cosmochim Acta 43:1131-1140.
Mavrogenes JA, Bodnar R-J (1994) Hydrogen movement into and out of fluid inclusions in quartz:
Experimental evidence and geologic implications. Geochim Cosmochim Acta 58:141-148.
Mercer CN, Reed MH (2013) Porphyry Cu-Mo stockwork formation by dynamic, transient
hydrothermal pulses: Mineralogic insights from the deposit at Butte, Montana. Econ Geol
108:1347–1377.
Mercer CN, Reed MH, Mercer CM (2015) Time scales of porphyry cu deposit formation: insights
from titanium diffusion in quartz. Econ Geol 110:587-602.
Meyer C, Shea E, Goddard C (1968) Ore deposits at Butte, Montana, in Ridge, J.D., ed., Ore deposits
of the United States 1933–1967, 2. New York, American Institute of Minerals, Metals, and
Petroleum Engineers, pp 1373–1416.
Noble D, McKee EH (1999) The Miocene metallogenic belt of central and northern Peru. In Skinner,
B. J., ed. Geology and ore deposits of the central Andes. Society of Economic Geology Special
Publication 7:155–193.
Pettke T (2006) In-situ laser-ablation-ICP-MS chemical analysis of melt inclusion and prospects for
constraining subduction zone magmas. In: Webster, J. D. (ed.) Melt Inclusions in Plutonic
Rocks. Mineralogical Association of Canada, Short Course Series 36, pp 51–80.
120
Pintea I (1995) Fluid inclusions evidence for liquid magmatic immiscibility between hydrous salt melt
and silicate melt as primary source of ore metals in porphyry copper systems from Apuseni
Mountains (Romania). Bol Soc Esp Mineral 18:184–185.
Pintea I (2014) The magmatic immiscibility between silicate-, brine-, and Fe-S-O melts from the
porphyry (Cu-Au-Mo) deposits in the Carpathians (Romania): a review: Rom J Earth Sci, 87:1-
32.
Reed M, Rusk B, Palandi J (2013) The Butte magmatic-hydrothermal system: One fluid yields all
alteration and veins. Econ Geol 108:1379–1396.
Rogers R (1983) Structural and geochemical evolution of a mineralized volcanic vent at Cerro de
Pasco, Peru. Unpublished PhD thesis, Tucson, University of Arizona, pp 116.
Rosso K, Bodnar R (1995) Microthermometric and Raman spectroscopic detection limits of CO2 in
fluid inclusions and the Raman spectroscopic characterization of CO2. Geochim Cosmochim
Acta 59:3961-3975.
Rosas S, Fontboté L, Tankard A (2007) Tectonic evolution and paleogeography of the Mesozoic
Pucará Basin, central Peru. J South Am Earth Sci 26:16–35.
Rottier B, (2017) Magmatic and hydrothermal fluid processes at the origin of the giant porphyry-
related epithermal polymetallic deposit of Cerro de Pasco (Central Peru), Phd thesis, University
of Geneva 434p.
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. Contrib
Mineral Petrol 172:23.
Rottier B, Kouzmanov K, Bouvier AS, Baumgartner L, Wälle M, Rezeau H, Bendezú R, Fontboté L
(2016a) Heterogeneous melt and hypersaline liquid inclusions in shallow porphyry type
mineralization as markers of the magmatic-hydrothermal transition (Cerro de Pasco district,
Peru). Chem Geol 447:93-116.
Rottier B, Kouzmanov K, Wälle M, Bendezú R, Fontboté, L (2016b) Sulfide replacement processes
revealed by textural an LA-ICP-MS trace element analyses: example from the early
mineralization stages at Cerro de Pasco, Peru. Econ Geol 111:1347-1367.
Rusk BG, Reed MH, Dilles JH (2008a) Fluid inclusion evidence for magmatic-hydrothermal fluid
evolution in the porphyry copper-molybdenum deposit at Butte, Montana. Econ Geol
103:307−334.
Rusk BG, Miller BJ, Reed MH (2008b) Fluid inclusion evidence for the formation of Main stage
polymetallic base-metal veins, Butte, Montana, USA. Ariz Geol Soc Dig 22:573–581.
Seitz S, Baumgartner LP, Bouvier A-S, Putlitz B, Vennemann T (2016) Quartz Standards for Oxygen
Isotope and Trace Element Analysis by SIMS. Geost. Geoanal. Res. In press (doi:
10.1111/ggr.12133).
Sillitoe RH (2010) Porphyry copper systems. Econ Geol 105:3–41.
Stefanova E, Driesner T, Zajacz Z, Heinrich CA, Petrov P, Vasilev Z (2014) Melt and Fluid Inclusions
in Hydrothermal Veins: The Magmatic to Hydrothermal Evolution of the Elatsite Porphyry Cu-
Au Deposit, Bulgaria. Econ Geol 109:1359-1381.
Sterner SM, Bodnar RJ (1984) Synthetic fluid inclusions in natural quartz I. Compositional types
synthesized and applications to experimental geochemistry. Geochim Cosmochim Acta
48:2659-2668.
Taylor HP (1997) Oxygen and hydrogen isotope relationships in hydrothermal mineral deposits. In
Geochemistry of hydrothermal ore deposits 3, pp 229-302.
Tomkins HS, Powell R, Ellis J (2007) The pressure dependence of the zirconium-in-rutile
thermometer. J Metamorph Geol 25:703−713.
Ulrich T, Günther D, Heinrich CA (2002) The evolution of a porphyry Cu-Au deposit, based on LA-
ICP-MS analysis of fluid inclusions: Bajo de la Alumbrera, Argentina. Econ Geol 97:1888–
1920.
Valentine GA, White JDL (2012) Revised conceptual model for maar-diatremes: Subsurface
processes, energetics, and eruptive products. Geology 40:1111-1114.
White JDL, Ross P-S (2011) Maar-diatreme volcanoes: A review. J Volcanol Geotherm Res 201:1–29.
Whitney JA (1988) The origin of granite: The role and source of water in the evolution of granitic
magmas. Geol Soc Am Bull 100:1886-1897.
121
Zajacz Z, Halter WE, Pettke T, Guillong M (2008) Determination of fluid ⁄ melt partition coefficients
by LA-ICPMS analysis of coexisting fluid and silicate melt inclusions: Controls on element
partitioning. Geochim Cosmochim Acta 72:2169–97.
Zajacz Z, Hanley JJ, Heinrich CA, Halter WE, Guillong M (2009) Diffusive reequilibration of quartz-
hosted silicate melt and fluid inclusions: Are all metal concentrations unmodified?. Geochim
Cosmochim Acta 73:3013–3027.
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

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 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.
129
Sample # Vein-type mineral
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. 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. 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. 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. 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.
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.
130
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 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 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 1,9 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.
131
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. 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 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. 30,4 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. 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. 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. 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
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
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.
134
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 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 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 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.
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
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. 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. 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 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.
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. 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.
136
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
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. 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. 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. 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. 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 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. 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
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
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 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
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
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 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
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*
**Institute of Mineralogy and Geochemistry, University of Lausanne, 1015 Lausanne, Switzerland
**** Volcan Compañía Minera S.A.A., Lima, Peru
†
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.
147
B. Rottier et al. / Chemical Geology xxx (2016) xxx–xxx 3
148
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
149
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
150
151
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

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
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.)
152
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 =
153
+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.)
154
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.
155
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.
156
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.
157
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
158
14
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
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
160
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).
161
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
162
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.)
163
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;
164
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.
165
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
166
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
7. Summary and conclusions Angeles, C., 1999. Los sedimentos cenozóicos de Cerro de Pasco: Estratigrafia,
sedimentación y tectónica. In: Machare, J., Benavides-Caceres, V., Rosas, S. (Eds.),
Sociedad Geológica del Perú. 5, pp. 103–118.
Detailed petrography combined with analyses of HSMIs, hypersaline Audétat, A., Pettke, T., 2003. The magmatic-hydrothermal evolution of two barren gran-
liquid, and aqueous L-V inclusions and their host banded quartz veins ites: a melt and fluid inclusion study of the Rito del Medio and Canada Pinabete plu-
from shallow porphyry type mineralization cropping out at the pres- tons in northern New Mexico (USA). Geochim. Cosmochim. Acta 67, 97–121.
Audétat, A., Garbe-Schönberg, D., Kronz, A., Pettke, T., Rusk, B., Donovan, J.J., Lowers, H.A.,
ent-day surface allow to trace fluid processes at the magmatic-hydro- 2015. Characterisation of a natural quartz crystal as a reference material for microan-
thermal transition at Cerro de Pasco, one of the largest Cordilleran alytical determination of Ti, Al, Li, Fe, Mn, Ga and Ge. Geostand. Geoanal. Res. 39,
base metal deposits on Earth, in which a link with a porphyry system 171–184.
Baumgartner, R., 2007. Sources and evolution in space and time of hydrothermal fluids at
had been proposed but not yet evidenced. the Cerro de Pasco cordilleran base metal deposit, central Peru. Terre &
Early quartz Q1–2 from banded quartz-magnetite-chalcopyrite-(py- Environnement 66 (167 pp.).
rite) porphyry-type veinlets records two high-temperature stages Baumgartner, R., Fontboté, L., Vennemann, T., 2008. Mineral zoning and geochemistry of
epithermal polymetallic Zn-Pb-Ag-Cu-Bi mineralization at Cerro de Pasco, Peru. Econ.
(N600 °C) in the magmatic-hydrothermal evolution (Fig. 18). Stage 1 Geol. 103, 493–537.
is characterized by the entrapment of heterogeneous inclusions con- Baumgartner, R., Fontboté, L., Spikings, R., Ovtcharova, M., Schneider, J., Pace, L., Gutjahr,
taining variable proportions of evolved silicate melts and hypersaline M., 2009. Bracketing the age of magmatic-hydrothermal activity at the Cerro de
Pasco epithermal polymetallic deposit, central Peru: a U-Pb and 40Ar/39Ar study.
liquid whereas during stage 2 only magmatic hypersaline liquid inclu- Econ. Geol. 104, 479–504.
sions are trapped. Precipitation of quartz Q3 records a low-temperature Bendezú, R., Fontboté, L., 2009. Cordilleran epithermal Cu-Zn-Pb-(Au-Ag) mineralization
stage 3 (b 350 °C) associated with the precipitation of a chalcopyrite-py- in the Colquijirca district, central Peru: deposit-scale mineralogical patterns. Econ.
Geol. 104, 905–944.
rite-sphalerite-(pyrite) assemblage possibly favored by mixing of minor
Bissig, T., Tosdal, R.M., 2009. Petrogenetic and metallogenetic relationships in the eastern
meteoric water with magmatic-dominated fluids, as indicated by the in- cordillera occidental of central Peru. J. Geol. 117, 499–518.
situ SIMS 18O/16O isotope analyses. Bissig, T., Ullrich, T.D., Tosdal, R.M., Friedman, R., Ebert, S., 2008. The time-space distribu-
The entrapment of HSMIs is not common in classical porphyry Cu- tion of Eocene to Miocene magmatism in the central Peruvian polymetallic province
and its metallogenetic implications. J. S. Am. Earth Sci. 26, 16–35.
Mo deposits. It requires anomalously high temperature for a given pres- Bodnar, R.J., 2003. Re-equilibration of fluid inclusions. In: Samson, I., Anderson, A.,
sure to allow phase exsolution below the miscibility field of vapor and Marshall, D. (Eds.), Fluid Inclusions: Analysis and Interpretation. Mineralogical Asso-
hypersaline liquid. At Cerro de Pasco, this is facilitated by the shallow ciation of Canada, Short Course Ser. 32, pp. 213–230.
Bodnar, R., Vityk, M.O., 1994. Interpretation of microthermometric data for H2O-NaCl fluid
emplacement of the trachyte porphyry, indicating that temperatures inclusions. In: De Vivo, B., Frezzotti, M.L. (Eds.), Fluid Inclusions in Minerals: Methods
N700 °C at b 1 km depth were reached. Our results lead to a better un- and Applications. Virginia Tech, Blacksburg, VA, pp. 117–130.
derstanding of the significance and origin of the HSMIs. We show that Campos, E., Touret, J.L.R., Nikogosian, I., Delgado, J., 2002. Overheated, Cu-bearing magmas
in the Zaldívar porphyry-Cu deposit, northern Chile. Geodynamic consequences.
primary HSMIs are abundant in early Q1–2 and are formed by heteroge- Tectonophysics 345, 229–251.
neous entrapment of an evolved silicate melt and hypersaline liquid (sa- Campos, E., Touret, J.L.R., Nikogosian, I., 2006. Magmatic fluid inclusions from the Zaldívar
linity around 90 wt% NaCl equiv., Fig. 16). The trapped phases are deposit, northern Chile: the role of early metal-bearing fluids in a porphyry copper
system. Resour. Geol. 56, 1–8.
interpreted to be the result of exsolution at low pressure (270 bar) Catchpole, H., Kouzmanov, K., Fontboté, L., Guillong, M., Heinrich, C.A., 2011. Fluid evolu-
and high temperature (N600 °C) from a hydrous evolved rhyolitic tion in zoned cordilleran polymetallic veins - insights from microthermometry and
melt ascending to shallow levels. Vapor that, under these conditions LA-ICP-MS of fluid inclusions. Chem. Geol. 281, 293–304.
Catchpole, H., Kouzmanov, Putlitz, B., Hun Seo, J., Fontboté, L., 2015. Zoned base metal
should have also exsolved is thought to have escaped and was not
mineralization in a porphyry system: origin and evolution of mineralizing fluids in
trapped in the early Q1–2. the Morococha district, Peru. Econ. Geol. 110, 39–71.
SEM-CL imaging of the studied veins reveals that sulfide precipita- Cline, J.S., Bodnar, R.J., 1991. Can economic porphyry copper mineralization be generated
tion occurs during or after the precipitation of quartz Q3. High sulfur by a typical calc-alkaline melt? J. Geophys. Res. 96, 8113–8126.
Cline, J.S., Vanko, D.A., 1995. Magmatically Generated Saline Brines Related to Molybde-
and metal contents of HSMIs and hypersaline liquid inclusions are num at Questa, New Mexico, USA. Mineralogical Association of Canada Short Course
interpreted to reflect the fluid composition before the main sulfide pre- Series 23 pp. 153–174.
cipitation, and, therefore, their metal ratios can be used as tracers of the Davidson, P., Kamenetsky, V.S., 2007. Primary aqueous fluids in rhyolitic magmas: melt
inclusion evidence for pre- and post-trapping exsolution. Chem. Geol. 237, 372–383.
magmatic body from which they are exsolved at depth. The similar Pb- Davidson, P., Kamanetsky, V., Cooke, D., Frikken, P., Hollings, P., Ryan, C., van Achterbergh,
Zn ratio of the bulk ore extracted from the epithermal ore bodies at E., Mernagh, T., Skarmeta, J., Serrano, L., Vargas, L., 2005. Magmatic precursors of hy-
Cerro de Pasco and from the HSMIs and hypersaline liquid inclusions drothermal fluids at the Rio Blanco Cu-Mo deposit, Chile: links of silicate magmas and
metal transport. Econ. Geol. 100, 963–978.
suggest a common source of the fluids responsible for the different min- Driesner, T., 2007. The system H2O-NaCl. Part II: correlations for molar volume, enthalpy,
eralization styles at Cerro de Pasco. and isobaric heat capacity from 0 to 1000 °C, 1 to 5000 bar, and 0 to 1 XNaCl.
Geochim. Cosmochim. Acta 71, 4902–4919.
Driesner, T., Heinrich, C.A., 2007. The system H2O-NaCl. Part I. Correlation formulae for
Acknowledgements phase relations in temperature–pressure–composition space from 0 to 1000 °C, 0 to
5000 bar, and 0 to 1 X-NaCl. Geochim. Cosmochim. Acta 71, 4880–4901.
The present investigation was carried out with the support of the Einaudi, M.T. (Ed.), 1968. Pyrrhotite-pyrite-sphalerite Relations at Cerro de Pasco, Peru.
Harvard University, Cambridge, MA (Unpublished Ph.D. thesis). (381 pp.).
Swiss National Science Foundation (FN 200020_134872). Funding for
Einaudi, M.T., 1977. Environment of ore deposition at Cerro de Pasco, Peru. Econ. Geol. 72,
the SwissSIMS facility was provided by the KIP 6 “CASA” to LPB. We 893–924.
thank Volcan Companía Minera S.A. for providing logistical support. Fournier, R.O., 1999. Hydrothermal processes related to movement of fluid from plastic
We gratefully acknowledge Jean-Marie Boccard and Fabio Capponi for into brittle rock in the magmatic-epithermal environment. Econ. Geol. 94,
1193–1211.
their help with sample preparation. Early discussions with Vincent Ca- Frezzotti, M.L., 1992. Magmatic immiscibility and fluid phase evolution in the Mount
sanova helped to improve the quality of this paper. P. Voudouris and Genis granite (southeastern Sardinia, Italy). Geochim. Cosmochim. Acta 56, 21–33.
167
Fulignati, P., Kamenetsky, V.S., Marianelli, P., Sbrana, A., 2005. Fluid inclusion evidence of Li, Y., Audétat, A., Lerchbaumer, L., Xiong, X.L., 2009. Rapid Na, Cu exchange between syn-
second immiscibility within magmatic fluids (79AD eruption of Mt. Vesuvius). Peri- thetic fluid inclusions and external aqueous solutions: evidence from LA-ICP-MS
od. Mineral. 74, 43–54. analysis. Geofluids 9, 321–329.
Goldstein, R.H., Reynolds, T.J., 1994. Systematics of Fluid Inclusions in Diagenetic Min- Lowenstern, J.B., 1994. Chlorine, fluid immiscibility, and degassing in peralkaline magmas
erals: SEPM Short Course. 31. Society for Sedimentary Geology (199 pp.). from Pantelleria, Italy. Am. Mineral. 79, 353–369.
Götze, J., Plotze, M., Graupner, T., Hallbauer, D.K., Bray, C.L., 2004. Trace element incorpo- Masterman, G.J., Cooke, D.R., Berry, R.F., Walshe, J.L., Lee, A.W., Clark, A.H., 2005. Fluid
ration into quartz: a combined study by ICP-MS, electron spin resonance chemistry, structural setting, and emplacement history of the Rosario Cu-Mo porphy-
cathodoluminescence, capillary ion analysis, and gas chromatography. Geochim. ry and Cu-Ag-Au epithermal veins, Collahuasi district, northern Chile. Econ. Geol. 100,
Cosmochim. Acta 68, 3741–3759. 835–862.
Grove, T.L., Elkins-Tanton, L.T., Parman, S.W., Chatterjee, N., Müntener, O., Gaetani, G.A., Matsuhisa, Y., Goldsmith, J.R., Clayton, R.N., 1979. Oxygen isotopic fractionation in the sys-
2003. Fractional crystallization and mantle-melting controls on calc-alkaline differen- tem quartz-albite-anorthite-water. Geochim. Cosmochim. Acta 43, 1131–1140.
tiation trends. Contrib. Mineral. Petrol. 145, 515–533. Mavrogenes, J.A., Bodnar, R.J., 1994. Hydrogen movement into and out of fluid inclusions
Guillong, M., Heinrich, C.A., 2007. LA-ICP-MS analysis of inclusions: improved ablation in quartz: experimental evidence and geologic implications. Geochim. Cosmochim.
and detection. European Current Research On Fluid Inclusions (ECROFI-XIX), at Acta 58, 141–148.
Bern, p. 82. Müller, A., Herrington, R., Armstrong, R., Seltmann, R., Kirwin, D., 2010. Trace elements
Guillong, M., Meier, D.L., Allan, M.M., Heinrich, C.A., Yardley, B.W.D., 2008. SILLS: a Matlab- and cathodoluminescence of quartz in stockwork veins in Mongolian porphyry-
based program for the reduction of laser ablation ICP-MS data of homogeneous ma- style deposits. Mineral Deposits 45, 707–727.
terials and inclusions. In: Sylvester, P. (Ed.), Laser-ablation-ICPMS in the Earth Sci- Muntean, J.L., Einaudi, M.T., 2000. Porphyry gold deposits of the Refugio district,
ences: Current Practices and Outstanding Issues. Mineralogical Association of Maricunga belt, northern Chile. Econ. Geol. 95, 1445–1472.
Canada, Vancouver, B.C., pp. 328–333. Noble, D.C., McKee, E.H., 1999. The Miocene metallogenic belt of central and northern
Günther, D., Frischknecht, R., Heinrich, C.A., Kahlert, H.J., 1997. Capabilities of an argon Peru. In: Skinner, B.J. (Ed.), Geology and Ore Deposits of the Central Andes. Society
fluoride 193 nm excimer laser for laser ablation inductively coupled plasma mass of Economic Geology Special Publication 7, pp. 155–193.
spectrometry microanalysis of geological materials. J. Anal. At. Spectrom. 12, Penniston-Dorland, S.C., 2001. Illumination of vein quartz textures in a porphyry copper
939–944. ore deposits using scanned cathodoluminescence: Grasberg igneous complex, Irian
Günther, D., Audétat, A., Frischknecht, R., Heinrich, C.A., 1998. Quantitative analysis of Jaya, Indonesia. Am. Mineral. 86, 652–666.
major, minor and trace elements in fluid inclusions using laser ablation–inductively Pintea, I., 1995. Fluid inclusions evidence for liquid magmatic immiscibility between hy-
coupled plasma mass spectrometry. J. Anal. At. Spectrom. 13, 263–270. drous salt melt and silicate melt as primary source of ore metals in porphyry copper
Halter, W.E., Pettke, T., Heinrich, C.A., Roten-Rutishauser, B., 2002. Major to trace element systems from Apuseni Mountains (Romania). Bol. Soc. Esp. Mineral. 18, 184–185.
analysis of melt inclusions by laser-ablation ICP-MS: methods of quantification. Pintea, I., 2012. The magmatic immiscibility between silicate-, brine-, and Fe-S-O melts
Chem. Geol. 183, 63–86. from the porphyry (Cu-Au-Mo) deposits in the Carpathians (Romania): a review.
Harris, A.C., Kamenetsky, V.S., White, N.C., van Achterbergh, E., Ryan, C.G., 2003. Melt in- Rom. J. Earth Sci. 87.
clusions in veins: Linking magmas and porphyry Cu deposits. Science 302, Redmond, P.B., Einaudi, M.T., Inan, E.E., Landtwing, M.R., Heinrich, C.A., 2004. Copper de-
2109–2111. position by fluid cooling in intrusion-centered systems: new insights from the Bing-
Harris, A.C., Kamenetsky, V.S., White, N.C., Steele, D.A., 2004. Volatile phase separation in ham porphyry ore deposit. Utah Geol. 32, 217–220.
silicic magmas at Bajo de la Alumbrera porphyry Cu-Au deposit, NW Argentina. Reed, M., Rusk, B., Palandi, J., 2013. The butte magmatic-hydrothermal system: one fluid
Resour. Geol. 54, 341–356. yields all alteration and veins. Econ. Geol. 108, 1379–1396.
Heinrich, C.A., Pettke, T., Halter, W.E., Aigner-Torres, M., Audétat, A., Günther, D., Robelin, C., Chartrand, P., Pelton, A.D., 2004. Thermodynamic evaluation and optimization
Hattendorf, B., Bleiner, D., Guillong, M., Horn, I., 2003. Quantitative multi-element of the (NaCl + KCl + MgCl2 + CaCl2 + MnCl2 + FeCl2 + CoCl2 + NiCl2) system.
analysis of minerals, fluid and melt inclusions by laser-ablation inductively- J. Chem. Thermodyn. 36, 809–828.
coupled-plasma mass-spectrometry. Geochim. Cosmochim. Acta 67, 3473–3496. Rogers, R., 1983. Structural and Geochemical Evolution of a Mineralized Volcanic Vent at
Herrington, R., Wilkinson, J., 1993. Colloidal gold and silica in mesothermal vein systems. Cerro de Pasco, Peru. (Unpublished PhD thesis). University of Arizona, Tucson (116
Geology 21, 539–542. pp.).
Hu, G., Clayton, R.N., 2003. Oxygen isotope salt effects at high pressure and high temper- Rosas, S., Fontboté, L., Tankard, A., 2007. Tectonic evolution and paleogeography of the
ature and the calibration of oxygen isotope geothermometers. Geochim. Cosmochim. Mesozoic Pucará basin, central Peru. J. S. Am. Earth Sci. 26, 16–35.
Acta 67, 3227–3246. Rosso, K., Bodnar, R., 1995. Microthermometric and Raman spectroscopic detection limits
Huang, R., Audétat, A., 2012. The titanium-in-quartz (TitaniQ) thermobarometer: a critical of CO2 in fluid inclusions and the Raman spectroscopic characterization of CO2.
examination and re-calibration. Geochim. Cosmochim. Acta 84, 75–89. Geochim. Cosmochim. Acta 59, 3961–3975.
Ivascanu, P.M., Pettke, T., Kouzmanov, K., Heinrich, C.A., Pintea, I., Rosu, E., Udubasa, Rottier, B., Kouzmanov, K., Casanova, C., Bendezú, R., Cuellar, D., Fonboté, L., 2015a. Mul-
G.H., 2003. The magmatic to hydrothermal transition: Miocene Deva porphyry tiple porphyry events at Cerro de Pasco, central Peru. Mineral Resources in a Sustain-
copper-gold deposit, south Apuseni Mts, Romania. Society for Geology Applied able World, 13th SGA Biennial Meeting, Volume 1: Nancy, France, Society for Geology
to Mineral Deposits, SGA Biennial Meeting, 7th, Athens, Greece, 2003, Proceedings, Applied to Mineral Deposits, pp. 351–354.
pp. 283–286. Rottier, B., Kouzmanov, K., Wälle, M., Fontboté, L., 2015b. Cyclic injection of metal-rich
Kamenetsky, V.S., Danyushevsky, L.V., 2005. Metals in quartz-hosted melt inclusions: nat- high-salinity magmatic fluids leading to the formation of the giant base metal deposit
ural facts and experimental artefacts. Am. Mineral. 90, 1674–1678. of Cerro de Pasco, Peru. European Current Research On Fluid Inclusions (ECROFI-
Kamenetsky, V.S., Kamenetsky, M.B., 2010. Magmatic fluids immiscible with silicate XXIII), at Leeds, pp. 156–157.
melts: examples from inclusions in phenocrysts and glasses, and implications for Rottier, B., Kouzmanov, K., Wälle, M., Bendezú, R., Fontboté, L., 2016. Sulfide replacement
magma evolution and metal transport. Geofluids 10, 293–311. processes revealed by textural an LA-ICP-MS trace element analyses: example from
Kamenetsky, V.S., Naumov, V.B., Davidson, P., van Achterbergh, E., Ryan, C.G., 2004. Im- the early mineralization stages at Cerro de Pasco, Peru. Econ. Geol. 111, 1347–1367.
miscibility between silicate magmas and aqueous fluids: a melt inclusion pursuit Rusk, B.G., Miller, B.J., Reed, M.H., 2008a. Fluid inclusion evidence for the formation of
into the magmatic-hydrothermal transition in the Omsukchan granite (NE Russia). main stage polymetallic base-metal veins, Butte, Montana, USA. Ariz. Geol. Soc. Dig.
Chem. Geol. 210, 73–90. 22, 573–581.
Klemm, L.M., Pettke, T., Heinrich, C.H., 2007. Hydrothermal evolution of the El Teniente Rusk, B.G., Lowers, H.A., Reed, M.H., 2008b. Trace elements in hydrothermal quartz: rela-
deposit, Chile: porphyry Cu-Mo ore deposition from low-salinity magmatic fluids. tionships to cathodoluminescence textures and insights into vein formation. Geology
Econ. Geol. 102, 1021–1045. 36, 547–550.
Koděra, P., Lexa, J., Konečný, P., 2013a. Application of CL-imaging and mineral Seitz, S., Baumgartner, L.P., Bouvier, A.-S., Putlitz, B., Vennemann, T., 2016. Quartz stan-
geothermometry on the porphyry gold deposit Biely Vrch, Slovakia. Mineral Deposit dards for oxygen isotope and trace element analysis by SIMS. Geostand. Geoanal.
Research for a High-tech World: Proceedings, 12th SGA Biennial Meeting, Volume 2: Res. http://dx.doi.org/10.1111/ggr.12133 (In press).
Uppsala, Sweden, Society for Geology Applied to Mineral Deposits, pp. 817–820. Spikings, R., Reitsma, M.J., Boekhout, F., Mišković, A., Ulianov, A., Chiaradia, M., Gerdes, A.,
Koděra, P., Heinrich, C.A., Wälle, M., Lexa, J., 2013b. Salt melt and vapor inclusions – evo- Schaltegger, U., 2016. Characterization of Triassic rifting in Peru and implications for
lution of fluids in near-surface porphyry gold deposits. European Current Research on the early disassembly of western Pangaea. Gondwana Res. 35, 124–143.
Fluid Inclusions (ECROFI-XXII), Antalya-Turkey, 4–9 June, 2013, Abstract Book, Stefanova, E., Driesner, T., Zajacz, Z., Heinrich, C.A., Petrov, P., Vasilev, Z., 2014. Melt and
pp. 153–154. fluid inclusions in hydrothermal veins: the magmatic to hydrothermal evolution of
Koděra, P., Heinrich, C.A., Wälle, M., Lexa, J., 2014. Magmatic salt melt and vapor: extreme the Elatsite porphyry Cu-Au deposit, Bulgaria. Econ. Geol. 109, 1359–1381.
fluids forming porphyry gold deposits in shallow subvolcanic settings. Geology 42, Sterner, S.M., Bodnar, R.J., 1984. Synthetic fluid inclusions in natural quartz I. Composi-
495–498. tional types synthesized and applications to experimental geochemistry. Geochim.
Kouzmanov, K., Pokrovski, G.S., 2012. Hydrothermal controls on metal distribution in por- Cosmochim. Acta 48, 2659–2668.
phyry Cu (-Mo-Au) systems. Society of Economic Geologists Special Publication. 16, Student, J.J., Bodnar, R.J., 1999. Synthetic fluid inclusions: XIV. Microthermometric and
pp. 573–618. compositional analysis of coexisting silicate melt and aqueous fluid inclusions
Landtwing, M.R., Pettke, T., Halter, W.H., Heinrich, C.A., Redmond, P.B., Einaudi, M.T., trapped in the haplogranite–H2O–NaCl–KCl system at 800 °C and 2000 bars. J. Pet.
Kunze, K., 2005. Copper deposition during quartz dissolution by cooling magmatic- 40, 1509–1525.
hydrothermal fluids: the Bingham porphyry. Earth Planet. Sci. Lett. 235, 229–243. Student, J.J., Bodnar, R.J., 2004. Silicate melt inclusions in porphyry copper deposits: iden-
Landtwing, M.R., Furrer, C., Redmond, P.B., Pettke, T., Guillong, M., Heinrich, C.A., 2010. tification and homogenization behavior. Can. Mineral. 42, 1583–1599.
The Bingham Canyon porphyry Cu-Mo-Au deposit. III. Zoned copper-gold ore deposi- Thomas, R., Davidson, P., 2013. The missing link between granites and granitic pegma-
tion by magmatic vapor expansion. Econ. Geol. 105, 91–118. tites. J. Geosci. 58, 183–200.
Lerchbaumer, L., Audétat, A., 2012. High Cu concentrations in vapor type fluid inclusions: Thomas, R., Davidson, P., 2016. Revisiting complete miscibility between silicate melts and
an artifact? Geochim. Cosmochim. Acta 88, 255–274. hydrous fluids, and the extreme enrichment of some elements in the supercritical
168
state — consequences for the formation of pegmatites and ore deposits. Ore Geol. Rev. Wark, D.A., Watson, E.B., 2006. TitaniQ: a titanium-in-quartz geothermometer. Contrib.
72, 1088–1101. Mineral. Petrol. 152, 743–754.
Thomas, J.B., Watson, E.B., Spear, F.S., Shemella, P.T., Nayak, S.K., Lanzirotti, A., 2010. Webster, J.D., 2004. The exsolution of magmatic hydrosaline chloride liquids. Chem. Geol.
TitaniQ under pressure: the effect of pressure and temperature on the solubility of 210, 33–48.
Ti in quartz. Contrib. Mineral. Petrol. 160, 743–759. Weis, P., Driesner, T., Heinrich, C.A., 2012. Porphyry-copper ore shells form at stable pres-
Ulrich, T., Günther, D., Heinrich, C.A., 2002. The evolution of a porphyry Cu-Au deposit, sure-temperature fronts within dynamic fluid plumes. Science 338, 1613–1616.
based on LA-ICP-MS analysis of fluid inclusions: Bajo de la Alumbrera, Argentina. Zajacz, Z., Halter, W.E., Pettke, T., Guillong, M., 2008. Determination of fluid/melt partition
Econ. Geol. 97, 1888–1920. coefficients by LA-ICPMS analysis of coexisting fluid and silicate melt inclusions: con-
Veksler, I.V., 2004. Liquid immiscibility and its role at the magmatic–hydrothermal tran- trols on element partitioning. Geochim. Cosmochim. Acta 72, 2169–2197.
sition: a summary of experimental studies. Chem. Geol. 210, 7–31. Zajacz, Z., Hanley, J.J., Heinrich, C.A., Halter, W.E., Guillong, M., 2009. Diffusive
Veksler, I.V., Thomas, R., Schmidt, C., 2002. Experimental evidence of three coexisting im- reequilibration of quartz-hosted silicate melt and fluid inclusions: are all metal con-
miscible fluids in synthetic granitic pegmatites. Am. Mineral. 87, 775–779. centrations unmodified? Geochim. Cosmochim. Acta 73, 3013–3027.
Vila, T., Sillitoe, R.H., 1991. Gold-rich porphyry systems in the Maricungabelt, northern Zhang, L., Jingxiu, L., Huanbo, Z., Zhensheng, C., 1989. Oxygen isotope fractionation in the
Chile. Econ. Geol. Bull. Soc. Econ. Geol. 86, 1238–1260. quartz-water-salt system. Econ. Geol. 84, 1643–1650.
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_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
-5.10
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
-5.10 0.33
-5.17 0.30
171
Table A.2a 18O/16O isotopic ratios measurement by SIMS
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
-5.11 0.27
-5.06 0.24
-5.10 0.26
-5.21 0.32
-5.31 0.21
-5.22 0.23
172
Table A.2b 18O/16O isotopic ratios measurement by SIMS
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
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
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
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.
186
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.
188
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
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
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.
190
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
192
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
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
T(°C)
100 200 300 400 500 600 800 1000
0 py po
En-Py veins and n
+ b Andesitic
Zn-Pb-(Bi-Ag-Cu) replacement ore bodies py cp
-2 s fl ux” magma
" “SO 2 g a
TE
bn y
t+ cp
-4 TA tion
m m+
nsa
S de
enar
con
h
N , fm
luz
fur
Sul
TIO
en, tt
-6 tn
D A C
F I G H
lo sp
-8
UL HI
o
+p
a
.0
.0
"S RY
20
10
VE
.0
cv
30
-10 Py-Qz body
log fS2
dg 1
t y
m +p
0. By po
hm
GHn
p
-12 HpI y+b
cp A Po pipes W and Fe-rich
O
p+ppyy
-14 cp Sp andL Gn rims
asttnn++
E Y
IAT +As R
ED VE
iro o
py asp
p
-16
n
E RM py o
p o
NT " W qz+pe
-18 I
bu
ffer LOmt+ ya
lit
k fa
"roc Modified from Einaudi et al. 2003
2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 1.0 0.8
1000/T (K)
Fig. 13. B. Log fS2-1000/T diagram (modified from Einaudi et al., 2003, and Baumgartner et al., 2008), illustrating fluid
properties evolution during mineralization stages A to C. Temperature and fS2 estimates are based on fluid inclusions data
(Rottier et al., 2015) and stability of different sulfide assemblages, as described in the text. Arrows indicate lateral and time
evolution of the mineralizing fluid for the individual stages of mineralization, with all three showing similar initial tempera-
ture, but having initial progressively higher fS2. Mineral abbreviations: asp = arsenopyrite, bn = bornite, cp = chalcopyrite, cv
= covellite, dg = digenite, en = enargite, fm = famatinite, hm =hematite, lo = lollingite, mt = magnetite, po = pyrrhotite, py
= pyrite, qtz = quartz.
with the textural interpretation. The different mineral gen- and logistical support. Special thanks to Hugo Alvarez and
erations show distinct trace element signatures that, to a large David Cuellar from the Cerro de Pasco Geology staff. We
extent and according to typical element associations, appear gratefully acknowledge Vincent Casanova for fruitful discus-
to be contained in micro- or nanoscale solid inclusions of sul- sions. Reviews by Steve Kesler and Thomas Ulrich have con-
fosalts and sulfides. Similarly to findings of other works, the tributed to significantly improve the manuscript.
trace element concentration is coherent with the physico-
chemical evolution of the fluid, including pH and sulfur and REFERENCES
oxygen fugacity. In addition, the present work shows that trace Angeles, C., 1999, Los sedimentos Cenozoicos de Cerro de Pasco: Estratigra-
element signatures of newly formed minerals depend on the fia, sedimentación y tectónica, in Machare, J., Benavides-Caceres, V., and
nature of replaced minerals and the dissolving neighboring Rosas, S., eds., Sociedad Geológica del Perú, v. 5, p. 103–118.
Bartos, P.J., 1989, Prograde and retrograde base metal lode deposits and their
phases. This is particularly well recorded by the trace element relationship to underlying porphyry copper deposits: Economic Geology,
composition of the different pyrite types (PyB1-po, PyB2-mrc, PyB2- v. 84, p. 1671–1683.
asp, and PyB-PQB) interpreted to be contemporaneous but that Barton, P., and Bethke P., 1987, Chalcopyrite disease in sphalerite: Pathology
replace different previous stage A minerals and lithologies. and epidemiology: American Mineralogist, v. 72, p. 451–467.
Baumgartner, R., 2007, Sources and evolution in space and time of hydro-
Therefore, careful determination of replacement textures, and thermal fluids at the Cerro de Pasco Cordilleran base metal deposit, Cen-
of the nature of the replaced and dissolved phases, is necessary tral Peru: Terre & Environnement, v. 66, 167 p.
to correctly interpret trace element contents in sulfides. Baumgartner, R., Fontboté, L., and Vennemann, T., 2008, Mineral zoning
and geochemistry of epithermal polymetallic Zn-Pb-Ag-Cu-Bi mineraliza-
Acknowledgments tion at Cerro de Pasco, Peru: Economic Geology, v. 103, p. 493–537.
Baumgartner, R., Fontboté, L., Spikings, R., Ovtcharova, M., Schneider, J.,
The present investigation was carried with the support of the Pace, L., and Gutjahr M., 2009, Bracketing the age of magmatic-hydrother-
Swiss National Science Foundation (FN 200020_134872). We mal activity at the Cerro de Pasco epithermal polymetallic deposit, central
thank Volcan Companía Minera S.A. for providing financial Peru: A U-Pb and 40Ar/39Ar study: Economic Geology, v. 104, p. 479–504.
197
1366 ROTTIER ET AL.
Bendezú, R., and Fontboté, L., 2009, Cordilleran epithermal Cu-Zn-Pb-(Au- Haeberlin, Y., Moritz, R., Fontboté, L., and Michael, C., 2004, Carbonif-
Ag) mineralization in the Colquijirca district, Central Peru: Deposit-scale erous orogenic gold deposits at Pataz, Eastern Andean Cordillera, Peru:
mineralogical patterns: Economic Geology, v. 104, p. 905–944. Geological and structural framework, paragenesis, alteration, and 40Ar/39Ar
Beuchat, S., Moritz, R., and Pettke, T., 2004, Fluid evolution in the W-Cu- geochronology: Economic Geology, v. 99, p. 73–112.
Zn-Pb San Cristobal vein, Peru: Fluid inclusion and stable isotope evi- Heinrich, C.A., 1990, The chemistry of hydrothermal tin(-tungsten) ore
dence: Chemical Geology, v. 210, p. 201–224. deposition: Economic Geology, v. 85, p. 457–481.
Bissig, T., and Tosdal, R.M., 2009, Petrogenetic and metallogenetic relation- Heinrich, C.A., and Eadington, P.J., 1986, Thermodynamic predictions of the
ships in the Eastern Cordillera Occidental of central Peru: The Journal of hydrothermal chemistry of arsenic and their significance for the paragenetic
Geology, v. 117, p. 499–518. sequence of some cassiterite-arsenopyrite-base metal sulfide deposits: Eco-
Bissig, T., Ullrich, T.D., Tosdal, R.M., Friedman, R., and Ebert, S., 2008, The nomic Geology, v. 81, p. 511–529.
time-space distribution of Eocene to Miocene magmatism in the central Heinrich, C.A., Pettke, T., Halter W.E., Aigner-Torres, M., Audétat, A., Gün-
Peruvian polymetallic province and its metallogenetic implications: Journal ther, D., Hattendorf, B., Bleiner, D., Guillong, M., and Horn, I., 2003,
of South American Earth Sciences, v. 26, p. 16–35. Quantitative multi-element analysis of minerals, fluid and melt inclusions
Catchpole, H., 2011, Porphyry-related polymetallic mineralization in the by laser-ablation inductively-coupled-plasma mass-spectrometry: Geochi-
Morococha district, Central Peru: Mineralisation styles, timing and fluid mica Cosmochimica Acta, v. 67, p. 3473–3496.
evolution: Terre & Environnement, v. 102, 192 p. Kelly, W.C., and Rye, R.O., 1979, Geologic, fluid inclusion, and stable isotope
Catchpole, H., Kouzmanov, K., Fontboté, L., Guillong, M., and Heinrich, studies of the tin-tungsten deposits of Panasqueira, Portugal: Economic
C.A., 2011, Fluid evolution in zoned Cordilleran polymetallic veins— Geology, v. 74, p. 1721–1822.
insights from microthermometry and LA-ICP-MS of fluid inclusions: King, J., Williams-Jones, A.E., Van Hinsberg, V., and Williams-Jones, G.,
Chemical Geology, v. 281, p. 293–304. 2014, High-sulfidation epithermal pyrite-hosted Au (Ag-Cu) ore formation
Catchpole, H., Kouzmanov, K., Putlitz, B., Seo, J., and Fontboté, L., 2015, by condensed magmatic vapors on Sangihe Island, Indonesia: Economic
Zoned base metal mineralization in a porphyry system: Origin and evolution Geology, v. 109, p. 1705–1733.
of mineralizing fluids in the Morococha district, Peru: Economic Geology, Kouzmanov, K., Pettke, T., and Heinrich, C.A., 2010, Direct analysis of ore-
v. 110, p. 39–71. precipitating fluids: Sombined IR microscopy and LA-ICP-MS study of fluid
Deditius, A.P., Utsunomiy,a S., Reich, M., Kesler, S.E., Ewing, R.C., Hough, inclusions in opaque ore minerals: Economic Geology, v. 105, p. 351–373.
R., and Walshe, J., 2011, Trace metal nanoparticles in pyrite: Ore Geology Lacy, W., 1949, Types of pyrite and their relations to mineralization at Cerro
Reviews, v. 42, p. 32–46. de Pasco, Peru: Unpublished Ph.D. thesis, Cambridge, MA, Harvard Uni-
Einaudi, M.T., 1968, Pyrrhotite-pyrite-sphalerite relations at Cerro de Pasco, versity, 193 p.
Peru: Unpublished Ph.D. thesis, Cambridge, MA, Harvard University, Large, R., Maslennikov, V., Robert, F., Danyushevsky, L., and Chang, Z.,
381 p. 2007, Multistage sedimentary and metamorphic origin of pyrite and gold in
——1971, The intermediate product of pyrrhotite alteration: American Min- the giant Sukhoi Log deposit, Lena gold province, Russia: Economic Geol-
eralogist, v. 56, p. 1297–1302. ogy, v. 102, p. 1232–1267.
——1977, Environment of ore deposition at Cerro de Pasco, Peru: Economic
Large, R., Bull, S., and Maslennikov, V., 2011, A Carbonaceous sedimentary
Geology, v. 72, p. 893–924.
source-rock model for Carlin-type and orogenic gold deposits: Economic
Einaudi, M.T., Hedenquist, J., and Inan, E., 2003, Sulfidation state of fluids
Geology, v. 106, p. 331–358.
in active and extinct hydrothermal systems: Transition from porphyry to
Lusk, J., and Calder, B., 2004, The composition of sphalerite and associated
epithermal environments: Society of Economic Geology Special Publica-
sulfides in reactions of the Cu-Fe-Zn-S, Fe-Zn-S and Cu-Fe-S systems at 1
tion 10, p. 285–313.
bar and temperatures between 250 and 535°C: Chemical Geology, v. 203,
Fleet, M.E., 1978, The pyrrhotite-marcasite transformation: The Canadian
p. 319–345.
Mineralogist, v. 16, p. 31–35.
Marcoux, E., Belkabir, A., Gibson, H., Lentz, D., and Ruffet, G., 2008, Draa
Fontboté, L., and Bendezú, R., 2009, Cordilleran or Butte-type veins and
replacement bodies as a deposit class in porphyry systems: Proceedings of Sfar, Morocco: A Visean (331 Ma) pyrrhotite-rich, polymetallic volcano-
the 10th Biennial Society of Geology Applied to Ore Deposits Meeting, genic massive sulphide deposit in a Hercynian sediment-dominant terrane:
Townsville, Australia, 2009, p. 521–523. Ore Geology Review, v. 33, p. 307–328.
Franchini, M., McFarlane, C., Maydagán, L., Reich, M., Lentz, D.R., Mein- Maydagán, L., Franchini, M.B., Lentz, D., Pons, J., McFarlane, C., 2013,
ert, L., and Bouhier, V., 2015, Trace metals in pyrite and marcasite from Sulfide composition and isotopic signature of the Altar Cu–Au deposit,
the Agua Rica porphyry-high sulfidation epithermal deposit, Catamarca, Argentina: constraints on the evolution of the porphyry-epithermal system:
Argentina: Textural features and metal zoning at the porphyry to epithermal Canadian Mineralogist, v. 51, p. 813–840.
transition: Ore Geology Reviews, v. 66, p. 366–387. Merino, E., and Canals, À., 2011, Self-accelerating dolomite-for-calcite
Fuertes-Fuente, M., Martin-Izard, A., Nieto, J., Maldonado, C., and Varela, replacement: Self-organized dynamics of burial dolomitization and associ-
A., 2000, Preliminary mineralogical and petrological study of the Ortosa ated mineralization: American Journal of Science, v. 311, p. 573–607.
Au-Bi-Te ore deposit: A reduced gold skarn in the northern part of the Murowchick, J., 1992, Marcasite inversion and the petrographic determina-
Rio Narcea gold belt, Asturias, Spain: Journal of Geochemical Exploration, tion of pyrite ancestry: Economic Geology, v. 87, p. 1141–1152.
v. 71, p. 177–190. Noble, D.C, and McKee, E.H, 1999, The Miocene metallogenic belt of cen-
Genkin, A., Bortnikov, N., Cabri, L., Wagner, F., Stanley, C., Safonov, Y., tral and northern Peru, in Skinner, B.J., ed. Geology and ore deposits of
McMahon, G., Friedl, J., Kerzin, A., and Gamyanin, G., 1998, A multi- the central Andes: Society of Economic Geologists Special Publication 7,
disciplinary study of invisible gold in arsenopyrite from four mesothermal p. 155–193.
gold deposits in Siberia, Russian Federation: Economic Geology, v. 93, Pals, D.W, and Spry, P.G, 2003, Telluride mineralogy of the low-sulfidation
p. 463–487. epithermal Emperor gold deposit, Vatukoula, Fiji: Mineralogy and Petrol-
Graton, L.C., and Bowditch, S.I., 1936, Alkaline and acid solutions in hypo- ogy, v. 79, p. 285–307.
gene zoning at Cerro de Pasco: Economic Geology, v. 31, p. 651–698. Pačevski, A., Moritz, R., Kouzmanov, K., Marquardt, K., Zivkovic, P., and
Gray, N., Mandyczewsky, A., and Hine, R., 1995, Geology of the zoned gold Cvetkovic, L., 2012, Texture and composition of Pb-bearing pyrite from
skarn system at Junction Reefs, New South Wales: Economic Geology, the Coka Marin polymetallic deposit, Serbia, controlled by nanoscale inclu-
v. 90, p. 1533–1552. sions: The Canadian Mineralogist, v. 50, p. 1–20.
Guillong, M., Meier, D.L., Allan, M.M., Heinrich, C.A., and Yardley, B.W.D., Pokrovski, G., Kara, S., and Roux, J., 2002, Stability and solubility of arse-
2008, SILLS: A Matlab-based program for the reduction of laser ablation nopyrite, FeAsS, in crustal fluids: Geochimica Cosmochimica Acta, v. 66,
ICP-MS data of homogeneous materials and inclusions, in Sylvester, P. ed., p. 2361–2378.
Laser ablation-ICPMS in the earth sciences: Current practices and out- Qian, G., Xia, F., Brugger, J., Skinner, W., Bei, J., Chen, G., and Pring, A.,
standing issues: Mineralogical Association of Canada, p. 328–333. 2011, Replacement of pyrrhotite by pyrite and marcasite under hydrother-
Günther, D., Frischknecht, R., Heinrich, C.A., and Kahlert, H.J., 1997, mal conditions up to 220°C: An experimental study of reaction textures and
Capabilities of an Argon Fluoride 193 nm excimer laser for laser ablation mechanisms: American Mineralogist, v. 96, p. 1878–1893.
inductively coupled plasma mass spectrometry microanalysis of geological Ramdohr, P., 1980, The ore minerals and their intergrowths: Oxford, Per-
materials: Journal of Analytical Atomic Spectrometry, v. 12, p. 939–944. gamon, 1205 p.
198
Reed, M.H., and Palandri, J., 2006, Sulfide mineral precipitation from hydro- Souza, D.C.S., Pralong, V., Jacobson, A.J., and Nazar, L.F., 2002, A reversible
thermal fluids: Reviews in Mineralogy and Geochemistry, v. 61, p. 609–631. solid-state crystalline transformation in a metal phosphide induced by redox
Reich, M., Deditius, A., Chryssoulis, S., Li, J., Ma, C., Parada, M., Barra, F., chemistry: Science. v. 296, p. 2012–2014
and Mittermayer, F., 2013, Pyrite as a record of hydrothermal fluid evo- Spikings R., Reitsma. M.J., Boekhout, F., Mišković, A, Ulianov, A, Chiaradia,
lution in a porphyry copper system: A SIMS/EMPA trace element study: M., Gerdes, A., and Schaltegger , U ., 2016, Characterization of Triassic rift-
Geochimica et Cosmochimica Acta, v. 104, p. 42–62. ing in Peru and implications for the early disassembly of western Pangaea:
Rogers, R., 1983, Structural and geochemical evolution of a mineralized vol- Gondwana Research, v. 35, p. 124–143.
canic vent at Cerro de Pasco, Peru: Unpublished PhD thesis, Tucson, Uni- Thomas, H.V., Large, R.R., Bull, S.W., Maslennikov, V., Berry, R.F., Fraser,
versity of Arizona, 116 p. R., Froud, S., and Moye, R., 2011, Pyrite and pyrrhotite textures and com-
Rosas, S., Fontboté, L., and Tankard, A., 2007, Tectonic evolution and paleo- position in sediments, laminated quartz veins, and reefs at Bendigo gold
geography of the Mesozoic Pucará Basin, central Peru: Journal of South mine, Australia: Insights for ore genesis: Economic Geology, v. 106, p. 1–31.
American Earth Sciences, v. 26, p. 16–35. Tomkins, A., Frost, R., and Pattison, D., 2006, Arsenopyrite melting during
Rottier, B., Kouzmanov, K., Wälle, M., and Fontboté, L., 2015, Cyclic injec- metamorphism of sulfide ore deposits: The Canadian Mineralogist, v. 44,
tion of metal-rich high-salinity magmatic fluids leading to the formation of p. 1045–1062.
the giant base metal deposit of Cerro de Pasco, Peru: European Current Vaughan, D.J., and Rosso, K.M., 2006, Chemical bonding in sulfide minerals:
Research on Fluid Inclusions (ECROFI-XXIII), Leeds, June 27–29, 2015, Reviews in Mineralogy and Geochemistry, v. 61, p. 231–264.
Extended Abstracts, p. 156–157. Ward, H., 1961, The pyrite body and copper orebodies, Cerro de Pasco mine,
Sillitoe, R., and Hedenquist, J., 2003, Linkages between volcanotectonic set- central Peru: Economic Geology, v. 56, p. 402–422.
tings, ore-fluid compositions, and epithermal precious metal deposits: Soci- Wilson, S.A., Ridley, W.I., and Koenig, A.E., 2002, Development of sulfide
ety of Economic Geologists Special Publication 10, p. 285–313. calibration standards for the laser ablation inductively-coupled plasma mass
Simmons, S., White, N., and John, D., 2005, Geological characteristics of spectrometry technique: Journal of Analytical Atomic Spectrometry, v. 17,
epithermal precious and base metal deposits: Economic Geology 100th p. 406–409.
Anniversary Volume, p. 485–522.
199
200
Table A.1: LA-ICP-MS analyses of the different sulphides
Mineralization Cr Fe Ni Zn As Se Mo
Mineral Analyse # Na (ppm) S (ppm) V (ppm) Mn (ppm) Co (ppm) Cu (ppm) Ga (ppm) Ag (ppm) Cd (ppm)
stage (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)
Marcasite A 1 25.1 552129 B.D.L. B.D.L. 4.2 465000 B.D.L. B.D.L. B.D.L. B.D.L. 0.48 213 B.D.L. B.D.L. B.D.L. B.D.L.
Marcasite A 2 54.4 538590 B.D.L. B.D.L. 5.3 465000 B.D.L. B.D.L. 2.9 B.D.L. 0.78 1018 B.D.L. B.D.L. 0.26 B.D.L.
Marcasite A 3 25.8 583724 0.16 B.D.L. 6 465000 B.D.L. B.D.L. 1.2 B.D.L. 1.1 233 B.D.L. B.D.L. 0.15 B.D.L.
Marcasite A 4 48 574706 B.D.L. 6.6 5.2 465000 B.D.L. B.D.L. 1.1 B.D.L. 0.47 379 B.D.L. B.D.L. 0.06 B.D.L.
Marcasite A 5 57.8 569296 0.25 B.D.L. 6.6 465000 B.D.L. B.D.L. 0.49 B.D.L. 0.72 340 5.2 B.D.L. B.D.L. B.D.L.
Marcasite A 6 36 574418 B.D.L. B.D.L. 4.9 465000 0.07 B.D.L. 0.76 B.D.L. 0.52 286 B.D.L. B.D.L. B.D.L. B.D.L.
PyB2-asp A 7 30.4 682421 B.D.L. B.D.L. 15.8 465000 9.8 5.8 1131 12.3 0.48 13063 B.D.L. B.D.L. 560 1.4
PyB2-asp A 8 35.9 585717 B.D.L. B.D.L. 25.2 465000 4 25.8 2046 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 2835 B.D.L.
PyB2-asp A 9 33.2 597142 B.D.L. B.D.L. 36.1 465000 11.4 6.5 1394 191 1.2 B.D.L. B.D.L. B.D.L. 1317 2.2
PyB2-asp A 10 24.6 683286 B.D.L. B.D.L. 14.2 465000 5.8 2.4 1388 8.1 1.1 1288 6.6 B.D.L. 1298 2.6
PyB2-asp A 11 14.4 699425 0.85 B.D.L. 11.3 465000 39.3 3.5 900 11.1 3.1 1602 B.D.L. 3 415 B.D.L.
PyB2-asp A 12 18.8 712109 B.D.L. B.D.L. 17 465000 107 72.2 774 14.7 1 3677 B.D.L. B.D.L. 430 B.D.L.
PyB2-asp A 13 23.5 654571 B.D.L. B.D.L. 8.5 465000 6.2 14 1259 19.1 4.9 883 B.D.L. B.D.L. 855 1
PyB2-asp A 14 38 686477 0.22 B.D.L. 11 465000 25.6 10.2 870 57.9 8.8 22427 B.D.L. B.D.L. 373 B.D.L.
PyB2-asp A 15 18.5 712433 B.D.L. B.D.L. 19.4 465000 374 110 1471 B.D.L. 1.8 105540 7.9 B.D.L. 934 B.D.L.
Arsenopyrite A 16 1.8 314812 B.D.L. B.D.L. 5 343000 356 216 B.D.L. B.D.L. 0.28 1E+06 11.3 1.7 3.4 B.D.L.
Arsenopyrite A 17 1.1 316262 B.D.L. B.D.L. 5.5 343000 281 71 B.D.L. B.D.L. B.D.L. 2E+06 B.D.L. B.D.L. 0.78 B.D.L.
Arsenopyrite A 18 1.5 300578 B.D.L. B.D.L. 4.1 343000 351 184 0.82 B.D.L. B.D.L. 2E+06 11.9 B.D.L. 0.25 B.D.L.
Arsenopyrite A 19 0.9 312305 B.D.L. B.D.L. 5.4 343000 145 177 B.D.L. B.D.L. B.D.L. 2E+06 B.D.L. B.D.L. 0.91 B.D.L.
Arsenopyrite A 20 1.2 327171 B.D.L. B.D.L. 4.1 343000 247 61.9 B.D.L. B.D.L. 0.25 1E+06 B.D.L. 1.2 0.85 B.D.L.
Arsenopyrite A 21 13.1 306521 B.D.L. B.D.L. 4.5 343000 146 36.4 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0.93 0.6
Arsenopyrite A 22 4.2 294212 B.D.L. B.D.L. 3.7 343000 10.4 B.D.L. 5.2 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 2.9 B.D.L.
Arsenopyrite A 23 1.4 281789 B.D.L. B.D.L. B.D.L. 343000 1.8 B.D.L. 4.2 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 1.7 B.D.L.
Arsenopyrite A 24 6.1 418029 B.D.L. B.D.L. 7.6 465000 287 227 B.D.L. B.D.L. 0.51 2E+06 B.D.L. B.D.L. 47.4 1.8
PYB1-po A 25 3.2 676817 0.14 B.D.L. 4.5 465000 B.D.L. B.D.L. 2.4 B.D.L. B.D.L. 158 B.D.L. B.D.L. 2.5 B.D.L.
PYB1-po A 26 0.5 667764 0.23 B.D.L. 6.4 465000 0.72 B.D.L. 0.73 B.D.L. 0.48 2774 B.D.L. B.D.L. 0.63 B.D.L.
PYB1-po A 27 0.61 702042 B.D.L. B.D.L. 4.7 465000 B.D.L. B.D.L. 2.1 B.D.L. B.D.L. 8273 B.D.L. B.D.L. 4.2 B.D.L.
PYB1-po A 28 2.2 815651 B.D.L. B.D.L. 6.2 465000 B.D.L. B.D.L. 1.6 B.D.L. B.D.L. 4286 B.D.L. B.D.L. 0.74 B.D.L.
PYB1-po A 29 0.42 723922 0.54 B.D.L. 14.4 465000 8.4 2 2.2 B.D.L. 0.47 2422 B.D.L. B.D.L. 2.1 B.D.L.
PYB1-po A 30 0.22 752078 B.D.L. B.D.L. 4.5 465000 0.42 B.D.L. 2.1 B.D.L. B.D.L. 7937 B.D.L. B.D.L. 1.5 B.D.L.
PYB1-po A 31 3.1 702131 4.6 10.4 23.9 465000 0.28 19.2 8.3 9.6 4.5 3321 B.D.L. B.D.L. 2.8 B.D.L.
201
Mineralization Sb Pb Bi
Mineral Analyse # In (ppm) Sn (ppm) Te (ppm) W (ppm) Au (ppm) Hg (ppm) Tl (ppm)
stage (ppm) (ppm) (ppm)
Marcasite A 1 B.D.L. B.D.L. 6.5 0.14 2.8 B.D.L. B.D.L. 0.75 9.5 0.13
Marcasite A 2 B.D.L. 1.4 9.4 B.D.L. 3.9 B.D.L. B.D.L. 0.31 45.8 0.78
Marcasite A 3 B.D.L. 2.3 12.5 B.D.L. 4.6 B.D.L. B.D.L. 0.27 187 1.3
Marcasite A 4 B.D.L. B.D.L. 10.8 0.18 3.6 B.D.L. B.D.L. 1.3 34.7 0.11
Marcasite A 5 B.D.L. 3.2 10.5 B.D.L. 3.9 B.D.L. B.D.L. 1.2 38.9 0.72
Marcasite A 6 B.D.L. 1.2 4.6 0.13 2.7 B.D.L. B.D.L. 0.52 24.8 0.21
PyB2-asp A 7 0.18 5.6 251 7.4 0.15 2 B.D.L. 0.96 6520 262
PyB2-asp A 8 0.22 7.8 341 10.8 B.D.L. 8.2 B.D.L. 2.2 41467 453
PyB2-asp A 9 0.25 9.8 451 12.5 1.1 7.6 B.D.L. 1.3 56798 521
PyB2-asp A 10 0.05 6.2 192 4.1 1.6 2.6 B.D.L. 0.54 3787 267
PyB2-asp A 11 B.D.L. 5.6 174 3.7 5.4 1.4 B.D.L. 0.75 2541 153
PyB2-asp A 12 0.09 5.3 189 4.7 B.D.L. 1.7 B.D.L. 0.66 3981 194
PyB2-asp A 13 B.D.L. 6 188 3.9 0.95 2.1 B.D.L. 1 2141 185
PyB2-asp A 14 0.28 8.1 325 6 1.3 2.5 B.D.L. 0.87 3401 264
PyB2-asp A 15 0.87 33.6 454 11.3 7 3.9 B.D.L. 2.6 2423 417
Arsenopyrite A 16 8.3 B.D.L. 15542 B.D.L. B.D.L. 1.6 1.4 0.05 7.2 82.3
Arsenopyrite A 17 8.7 B.D.L. 15818 0.55 B.D.L. 1.2 B.D.L. B.D.L. 5.2 81
Arsenopyrite A 18 8.5 B.D.L. 18051 B.D.L. B.D.L. 0.76 B.D.L. B.D.L. 11.4 23.6
Arsenopyrite A 19 8.6 3.2 31366 B.D.L. B.D.L. 0.9 B.D.L. B.D.L. 23.6 24.4
Arsenopyrite A 22 8.3 B.D.L. 19313 B.D.L. B.D.L. 6.3 B.D.L. B.D.L. 39 324
Arsenopyrite A 23 8.6 B.D.L. 6390 B.D.L. B.D.L. 24.1 B.D.L. B.D.L. 33.8 99.4
Arsenopyrite A 24 11.7 B.D.L. 14767 5.7 B.D.L. 6.8 B.D.L. B.D.L. 256 179
PYB1-po A 25 B.D.L. B.D.L. 13.9 7.3 0.08 B.D.L. B.D.L. B.D.L. 526 5.7
PYB1-po A 26 B.D.L. B.D.L. 21 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 351 8
PYB1-po A 27 B.D.L. B.D.L. 13.3 18.9 B.D.L. 1.1 B.D.L. B.D.L. 1124 10.3
PYB1-po A 28 B.D.L. B.D.L. 15.6 30.3 B.D.L. 0.34 B.D.L. B.D.L. 154 4.4
PYB1-po A 29 B.D.L. B.D.L. 31.3 1.1 3 0.08 B.D.L. 0.04 988 14.3
PYB1-po A 30 0.11 B.D.L. 11 21.3 B.D.L. 1.3 B.D.L. B.D.L. 393 5.9
PYB1-po A 31 0.15 5.8 133 4.7 3.7 B.D.L. B.D.L. 0.15 1331 32.4
202
PYB1-po A 32 1.6 688253 B.D.L. B.D.L. 4.7 465000 1.4 28.4 1.6 B.D.L. B.D.L. 6067 B.D.L. B.D.L. 7.2 B.D.L.
PYB1-po A 33 0.84 695807 0.49 B.D.L. 7.6 465000 B.D.L. 1 5.1 B.D.L. 1.1 9494 B.D.L. B.D.L. 0.45 B.D.L.
PYB1-po A 34 5.4 685249 5.8 B.D.L. 26 465000 B.D.L. 0.78 0.72 10.7 14.9 616 B.D.L. B.D.L. 0.04 B.D.L.
PYB1-po A 35 2.1 721194 0.53 B.D.L. 5.4 465000 B.D.L. B.D.L. B.D.L. B.D.L. 1 1347 B.D.L. B.D.L. 0.07 B.D.L.
PYB1-po A 36 0.99 707103 0.86 B.D.L. 7.8 465000 B.D.L. B.D.L. 4.3 B.D.L. 1.5 1952 B.D.L. B.D.L. B.D.L. 0.39
PYB1-po A 37 3.1 676947 4.8 B.D.L. 15.4 465000 B.D.L. 16.7 6 5.9 24.1 B.D.L. B.D.L. B.D.L. 0.95 B.D.L.
PYB1-po A 38 2.4 692861 6.5 B.D.L. 14.3 465000 B.D.L. 22.8 4.5 B.D.L. 9 B.D.L. B.D.L. B.D.L. 1.1 B.D.L.
PYB1-po A 39 1 657330 1.5 B.D.L. 9 465000 B.D.L. 2.3 9.7 B.D.L. 2.1 B.D.L. B.D.L. B.D.L. 0.85 B.D.L.
PYB1-po A 40 1.4 720418 B.D.L. B.D.L. 5.2 465000 0.4 40.5 2.4 B.D.L. B.D.L. 1661 B.D.L. B.D.L. 1.9 B.D.L.
PYB1-po A 41 0.72 773764 0.19 B.D.L. 5.7 465000 B.D.L. 18.1 2 B.D.L. 0.18 6671 B.D.L. B.D.L. 1.3 B.D.L.
PYB1-po A 42 0.36 811549 B.D.L. B.D.L. 5.3 465000 B.D.L. 4.9 3.6 B.D.L. B.D.L. 7616 B.D.L. B.D.L. 0.61 B.D.L.
PYB1-po A 43 1.6 702140 B.D.L. B.D.L. 6.2 465000 0.12 18.9 B.D.L. B.D.L. B.D.L. 328 B.D.L. B.D.L. 3.5 B.D.L.
PYB1-po A 44 0.47 734323 B.D.L. B.D.L. 5 465000 B.D.L. 2.1 2.2 B.D.L. B.D.L. 10317 B.D.L. B.D.L. 0.24 B.D.L.
PYB1-po A 45 0.3 711587 B.D.L. B.D.L. 4.7 465000 B.D.L. 1.4 2.9 B.D.L. B.D.L. 718 B.D.L. B.D.L. 0.3 B.D.L.
PYB1-po A 46 2.6 789470 2.5 B.D.L. 16.8 465000 B.D.L. 38.4 2.8 B.D.L. 11.6 6010 B.D.L. B.D.L. 1.4 B.D.L.
PYB1-po A 47 0.29 678224 0.79 B.D.L. 4.9 465000 0.96 B.D.L. 1.7 B.D.L. B.D.L. 3453 B.D.L. B.D.L. 0.62 B.D.L.
Pyrrhotite A 48 5.6 479296 B.D.L. B.D.L. 7.3 623000 B.D.L. B.D.L. B.D.L. 157 B.D.L. B.D.L. B.D.L. B.D.L. 0.35 B.D.L.
Pyrrhotite A 49 0.54 476964 0.37 B.D.L. 5.7 623000 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0.41 B.D.L.
Pyrrhotite A 50 1.8 470710 B.D.L. B.D.L. 5.4 623000 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0.26 B.D.L.
Pyrrhotite A 51 4.6 472873 B.D.L. B.D.L. 6.3 623000 B.D.L. B.D.L. 16 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0.23 1.2
Pyrrhotite A 52 B.D.L. 481121 B.D.L. B.D.L. 6.6 623000 B.D.L. B.D.L. B.D.L. 19.3 B.D.L. B.D.L. B.D.L. B.D.L. 0.74 B.D.L.
Pyrrhotite A 53 1.3 481050 0.72 B.D.L. 5.6 623000 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.
Pyrrhotite A 54 B.D.L. 503209 B.D.L. B.D.L. 4.7 623000 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0.44 B.D.L. B.D.L.
Pyrrhotite A 55 5.4 496367 1.1 B.D.L. 8.2 623000 B.D.L. B.D.L. B.D.L. B.D.L. 1 B.D.L. B.D.L. B.D.L. 0.15 B.D.L.
Pyrrhotite A 56 7.5 481190 0.7 B.D.L. 4.9 623000 B.D.L. B.D.L. B.D.L. B.D.L. 1.9 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
Pyrrhotite A 57 0.48 468835 B.D.L. B.D.L. 5.4 623000 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
Pyrrhotite A 60 1 472847 B.D.L. B.D.L. 4.4 623000 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 B.D.L.
Pyrrhotite A 61 2.8 542351 B.D.L. B.D.L. B.D.L. 623000 B.D.L. B.D.L. B.D.L. 13.6 B.D.L. 142 B.D.L. B.D.L. 0.57 B.D.L.
Pyrrhotite A 62 1.1 510611 B.D.L. B.D.L. 5.3 623000 B.D.L. B.D.L. 3.7 B.D.L. B.D.L. 15.3 B.D.L. B.D.L. B.D.L. B.D.L.
203
PYB1-po A 32 B.D.L. 2.7 77.3 B.D.L. 0.22 0.31 B.D.L. B.D.L. 2715 77.5
PYB1-po A 33 0.08 B.D.L. 51.9 3.4 0.98 B.D.L. B.D.L. B.D.L. 344 8.6
PYB1-po A 34 B.D.L. 1.8 28.4 B.D.L. B.D.L. B.D.L. B.D.L. 0.04 127 12.4
PYB1-po A 35 B.D.L. B.D.L. 10.1 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 58.5 4.4
PYB1-po A 36 B.D.L. 2.8 4 1.2 6.2 B.D.L. B.D.L. B.D.L. 14.4 0.78
PYB1-po A 37 0.11 4.6 111 0.83 1.8 B.D.L. B.D.L. 0.17 690 31.5
PYB1-po A 38 0.15 5.6 85 2.1 18.2 0.1 B.D.L. 0.02 779 22.1
PYB1-po A 39 0.17 4.9 61.8 5.1 3.9 B.D.L. B.D.L. 0.27 941 13.3
PYB1-po A 40 0.06 4.3 91.2 B.D.L. B.D.L. 0.17 B.D.L. 0.02 1271 47.8
PYB1-po A 41 0.13 5.5 132 B.D.L. 0.65 0.13 B.D.L. B.D.L. 1048 41.3
PYB1-po A 42 0.1 2 31.1 B.D.L. 2.1 0.11 B.D.L. B.D.L. 569 25.9
PYB1-po A 43 B.D.L. 2.4 61.5 B.D.L. 0.05 B.D.L. B.D.L. 0.01 1683 38.4
PYB1-po A 44 0.13 B.D.L. 14.5 B.D.L. 0.22 0.15 B.D.L. B.D.L. 203 16.5
PYB1-po A 45 B.D.L. 3.3 19 0.78 0.35 B.D.L. B.D.L. B.D.L. 232 13.2
PYB1-po A 46 0.1 4 125 0.3 B.D.L. 0.25 B.D.L. B.D.L. 1139 44.5
PYB1-po A 47 0.11 B.D.L. 35.8 0.95 0.14 0.14 B.D.L. B.D.L. 338 12.8
Pyrrhotite A 48 B.D.L. B.D.L. 15.6 0.4 B.D.L. B.D.L. B.D.L. B.D.L. 44.7 3.2
Pyrrhotite A 49 B.D.L. B.D.L. 1 0.44 0.24 B.D.L. B.D.L. B.D.L. 91.3 1
Pyrrhotite A 50 B.D.L. B.D.L. 0.39 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 2.4 0.26
Pyrrhotite A 52 B.D.L. B.D.L. 1 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 6.9 1.2
Pyrrhotite A 53 B.D.L. B.D.L. 0.94 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 3 0.43
Pyrrhotite A 56 B.D.L. B.D.L. 2.1 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 11 0.21
Pyrrhotite A 57 B.D.L. B.D.L. 0.42 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 5.2 B.D.L.
Pyrrhotite A 58 B.D.L. B.D.L. 1.7 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 96.4 B.D.L.
Pyrrhotite A 59 B.D.L. B.D.L. 0.92 B.D.L. B.D.L. B.D.L. B.D.L. 0.11 6.2 B.D.L.
Pyrrhotite A 62 B.D.L. B.D.L. 0.83 0.47 B.D.L. B.D.L. B.D.L. B.D.L. 4 0.24
204
Pyrrhotite A 63 0.35 510251 B.D.L. B.D.L. 5.3 623000 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0.27 B.D.L.
Pyrrhotite A 64 B.D.L. 520303 B.D.L. B.D.L. 6.8 623000 B.D.L. B.D.L. B.D.L. 9 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
Pyrrhotite A 65 1.6 513992 0.38 B.D.L. 5.6 623000 B.D.L. B.D.L. B.D.L. B.D.L. 0.78 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
Pyrrhotite A 66 B.D.L. 507108 B.D.L. B.D.L. 5.4 623000 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L.
Pyrrhotite A 67 B.D.L. 513283 B.D.L. B.D.L. 5.7 623000 B.D.L. B.D.L. 1 B.D.L. B.D.L. 0 B.D.L. B.D.L. 0.13 B.D.L.
PyB2-mrc A 68 9.6 634765 1.1 B.D.L. 40.4 465000 0.63 B.D.L. 18.3 5.3 29.3 3951 B.D.L. B.D.L. 2.8 B.D.L.
PyB2-mrc A 69 4.4 625666 0.55 7.5 20.9 465000 1.6 0.97 6.5 B.D.L. 4.4 4204 B.D.L. B.D.L. 2.5 B.D.L.
PyB2-mrc A 70 8.7 604576 1.9 B.D.L. 45.8 465000 1.1 B.D.L. 8.8 10.3 5 4407 B.D.L. B.D.L. 2.9 0.28
PyB2-mrc A 71 6.5 681188 0.2 B.D.L. 25 465000 0.7 0.82 5.3 B.D.L. 1.1 1321 B.D.L. B.D.L. 3.1 B.D.L.
PyB2-mrc A 72 20.7 524428 40.1 12.9 1449 465000 B.D.L. B.D.L. 98.6 15 25.1 2904 B.D.L. B.D.L. 8.5 B.D.L.
PyB2-mrc A 73 9.6 593122 26.6 15.4 482 465000 B.D.L. 2.4 125 9.5 26.2 3014 B.D.L. B.D.L. 2.5 B.D.L.
PyB2-mrc A 74 1 647933 0.74 B.D.L. 7.3 465000 1.1 141 2 B.D.L. 1.7 2711 B.D.L. B.D.L. 9.7 B.D.L.
PyB2-mrc A 75 2.2 611863 9.4 57 28.1 465000 0.82 24.6 85.8 B.D.L. 14.1 4439 B.D.L. B.D.L. 6.6 0.5
PyB2-mrc A 76 1.3 672923 0.25 B.D.L. 4 465000 1.9 133 2.6 B.D.L. 0.8 1045 B.D.L. B.D.L. 2.6 B.D.L.
PyB2-mrc A 77 1.1 710029 B.D.L. B.D.L. 4.9 465000 11 215 2.6 B.D.L. B.D.L. 12236 B.D.L. B.D.L. 20.7 B.D.L.
PyB2-mrc A 78 0.83 530087 B.D.L. B.D.L. 5.9 465000 B.D.L. B.D.L. B.D.L. B.D.L. 0.65 8.1 B.D.L. B.D.L. 0.1 B.D.L.
PyB2-mrc A 79 5.7 698736 B.D.L. B.D.L. 9.9 465000 B.D.L. B.D.L. 8.1 B.D.L. B.D.L. 129 B.D.L. B.D.L. 0.55 B.D.L.
PyB2-mrc A 80 1.8 669201 1.7 B.D.L. 6 465000 0.34 34.5 8.4 9.9 19.8 3824 B.D.L. B.D.L. 2.7 0.53
PYB-PQB B2 81 0.32 721565 B.D.L. B.D.L. 3.9 465000 B.D.L. B.D.L. 1.6 B.D.L. B.D.L. 2840 B.D.L. B.D.L. 0.7 B.D.L.
PYB-PQB B2 82 B.D.L. 674019 B.D.L. B.D.L. 4.4 465000 B.D.L. B.D.L. 2.2 B.D.L. B.D.L. 1450 9.8 B.D.L. 3 B.D.L.
PYB-PQB B2 84 B.D.L. 672542 B.D.L. B.D.L. 5.2 465000 B.D.L. B.D.L. 1.6 B.D.L. B.D.L. 29.6 B.D.L. B.D.L. 0.84 B.D.L.
PYB-PQB B2 85 0.65 721583 0.42 B.D.L. 5.1 465000 B.D.L. 1.4 4.3 B.D.L. B.D.L. 979 B.D.L. B.D.L. 5.6 B.D.L.
PYB-PQB B2 86 B.D.L. 722092 0.2 B.D.L. 5.2 465000 B.D.L. B.D.L. 23.6 B.D.L. B.D.L. 3048 16.6 B.D.L. 6.6 B.D.L.
PYB-PQB B2 87 B.D.L. 692693 B.D.L. B.D.L. 5.4 465000 B.D.L. B.D.L. 0.78 B.D.L. B.D.L. 112 B.D.L. B.D.L. 2.3 B.D.L.
PYB-PQB B2 88 0.19 695335 B.D.L. B.D.L. 4.1 465000 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 217 B.D.L. B.D.L. 5.3 B.D.L.
PYB-PQB B2 89 B.D.L. 673073 B.D.L. B.D.L. 5.5 465000 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 461 B.D.L. B.D.L. 0.11 B.D.L.
PYB-PQB B2 90 B.D.L. 682299 B.D.L. B.D.L. 5.2 465000 B.D.L. B.D.L. 0.91 B.D.L. B.D.L. 1150 B.D.L. B.D.L. 2.2 B.D.L.
PYB-PQB B2 92 B.D.L. 726432 B.D.L. B.D.L. 5 465000 B.D.L. B.D.L. 0.99 B.D.L. B.D.L. 1537 B.D.L. B.D.L. 0.99 B.D.L.
PYB-PQB B2 93 B.D.L. 692926 B.D.L. B.D.L. 3.7 465000 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 1707 B.D.L. B.D.L. 0.32 B.D.L.
205
Pyrrhotite A 64 B.D.L. B.D.L. 0.69 B.D.L. 0.09 B.D.L. B.D.L. B.D.L. 15.7 0.49
Pyrrhotite A 65 B.D.L. B.D.L. 1.6 B.D.L. B.D.L. B.D.L. B.D.L. 0.04 7.4 0.46
Pyrrhotite A 66 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 1.3 0.18
Pyrrhotite A 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. 0.81 0.21
PyB2-mrc A 68 0.96 206 170 1.7 0.34 0.15 B.D.L. 0.03 2823 23.9
PyB2-mrc A 69 0.39 73.4 93.2 1.7 0.28 0.19 B.D.L. 0.02 1501 17.3
PyB2-mrc A 70 0.44 95.5 118 0.97 0.74 0.12 B.D.L. 0.04 1725 22.5
PyB2-mrc A 71 0.28 54.6 95 0.72 B.D.L. 0.12 B.D.L. B.D.L. 1239 15.8
PyB2-mrc A 72 0.17 14.7 402 17.4 15.3 B.D.L. B.D.L. 0.65 923 22.8
PyB2-mrc A 73 0.32 46.9 190 5.2 4.5 B.D.L. B.D.L. 0.19 637 8.1
PyB2-mrc A 74 B.D.L. 3.6 38 B.D.L. 0.81 0.4 B.D.L. 0.79 3787 57.9
PyB2-mrc A 75 0.15 22.5 114 4.9 10.9 0.23 B.D.L. 0.7 1728 39.5
PyB2-mrc A 76 B.D.L. 1.7 31.7 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 914 27.1
PyB2-mrc A 77 0.13 4.5 40.1 B.D.L. B.D.L. 2 B.D.L. B.D.L. 7636 95.9
PyB2-mrc A 78 B.D.L. B.D.L. 1.4 B.D.L. 3.4 B.D.L. B.D.L. 0.32 26.2 0.32
PyB2-mrc A 79 B.D.L. 2.9 31.3 B.D.L. 1.7 B.D.L. B.D.L. 6.1 196 10.1
PyB2-mrc A 80 0.09 6.4 50.1 0.29 B.D.L. B.D.L. B.D.L. B.D.L. 1071 26.6
PYB-PQB B2 81 B.D.L. B.D.L. 4.7 B.D.L. B.D.L. 0.13 B.D.L. B.D.L. 5.5 0.04
PYB-PQB B2 82 0.05 B.D.L. 18.3 B.D.L. B.D.L. 0.13 B.D.L. B.D.L. 28 0.3
PYB-PQB B2 83 B.D.L. B.D.L. 2.9 B.D.L. B.D.L. B.D.L. B.D.L. 0.01 3.7 0.06
PYB-PQB B2 84 B.D.L. B.D.L. 3.4 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 4.9 B.D.L.
PYB-PQB B2 86 B.D.L. 2.3 147 0.13 B.D.L. 0.15 B.D.L. B.D.L. 672 1.6
PYB-PQB B2 87 B.D.L. B.D.L. 7.2 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 10.5 2.9
PYB-PQB B2 88 B.D.L. 1.4 24.7 B.D.L. B.D.L. B.D.L. B.D.L. 0.01 40.3 6.9
PYB-PQB B2 92 B.D.L. B.D.L. 2.9 0.18 0.05 0.04 B.D.L. B.D.L. 4.4 1
206
PYB-PQB B2 94 0.35 740972 B.D.L. B.D.L. 4.5 465000 B.D.L. B.D.L. 0.7 B.D.L. B.D.L. 274 9.1 B.D.L. 5.7 B.D.L.
PYB-PQB B2 95 0.22 755161 B.D.L. B.D.L. 5 465000 B.D.L. B.D.L. 0.72 B.D.L. B.D.L. 346 B.D.L. B.D.L. 2.8 B.D.L.
PYB-PQB B2 96 4.6 754118 B.D.L. B.D.L. 5.9 465000 B.D.L. B.D.L. 8.1 B.D.L. B.D.L. 803 10 B.D.L. 9.8 B.D.L.
PYB-PQB B2 97 2.2 755044 B.D.L. 8 5.1 465000 B.D.L. B.D.L. 8 B.D.L. B.D.L. 942 B.D.L. B.D.L. 2.9 B.D.L.
PYB-PQB B2 98 1 720004 B.D.L. B.D.L. 3.8 465000 B.D.L. B.D.L. 3.8 B.D.L. B.D.L. 66.3 7.3 B.D.L. 7.2 B.D.L.
PYB-PQB B2 100 B.D.L. 700192 B.D.L. B.D.L. 4.6 465000 B.D.L. 1.5 13.8 B.D.L. B.D.L. 36.7 B.D.L. B.D.L. B.D.L. B.D.L.
PYB-PQB B2 101 0.22 647410 B.D.L. B.D.L. 4.9 465000 0.99 1.8 2.2 B.D.L. B.D.L. 46.5 B.D.L. B.D.L. 0.5 B.D.L.
PYB-PQB B2 102 B.D.L. 710379 B.D.L. B.D.L. 5.3 465000 B.D.L. 0.13 B.D.L. B.D.L. B.D.L. 20.8 B.D.L. B.D.L. 0.07 B.D.L.
PYB-PQB B2 103 B.D.L. 713608 B.D.L. B.D.L. 3.7 465000 0.52 B.D.L. B.D.L. B.D.L. B.D.L. 795 B.D.L. B.D.L. B.D.L. B.D.L.
PYB-PQB B2 104 0.99 725054 B.D.L. 8.3 4.5 465000 B.D.L. B.D.L. 1.3 B.D.L. B.D.L. 1929 B.D.L. B.D.L. 0.11 B.D.L.
PYB-PQB B2 105 0.8 717929 B.D.L. B.D.L. 4.6 465000 B.D.L. 0.78 3.6 B.D.L. 0.44 668 B.D.L. B.D.L. 1.5 B.D.L.
PYB-PQB B2 107 0.23 656538 B.D.L. B.D.L. 3.6 465000 0.28 2.5 46.5 B.D.L. B.D.L. 42.5 B.D.L. B.D.L. 0.11 B.D.L.
PYB-PQB B2 108 0.17 764453 B.D.L. 7.3 4.4 465000 B.D.L. B.D.L. 5.4 B.D.L. 0.36 186 B.D.L. B.D.L. 0.35 B.D.L.
PYB-PQB B2 109 B.D.L. 701967 B.D.L. B.D.L. 4.1 465000 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 5.4 B.D.L. B.D.L. 0.16 B.D.L.
PYB-PQB B2 110 0.29 711359 0.19 B.D.L. 4.1 465000 B.D.L. B.D.L. 3 B.D.L. B.D.L. 1969 B.D.L. B.D.L. 1.3 B.D.L.
PYB-PQB B2 111 B.D.L. 749924 B.D.L. B.D.L. 4.1 465000 B.D.L. 0.16 0.85 B.D.L. B.D.L. 468 B.D.L. B.D.L. 0.23 B.D.L.
207
PYB-PQB B2 94 B.D.L. B.D.L. 31.2 B.D.L. B.D.L. B.D.L. B.D.L. 0.01 39 2.5
PYB-PQB B2 95 B.D.L. B.D.L. 18.9 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 30.7 1
PYB-PQB B2 96 B.D.L. B.D.L. 66.4 0.33 B.D.L. 0.09 B.D.L. 0.27 115 24.6
PYB-PQB B2 97 B.D.L. B.D.L. 25.1 B.D.L. 0.21 0.09 B.D.L. 0.09 307 6
PYB-PQB B2 98 B.D.L. B.D.L. 52.2 B.D.L. B.D.L. B.D.L. B.D.L. 3.5 39.9 6.2
PYB-PQB B2 99 0.08 1.5 21.1 B.D.L. B.D.L. 2 B.D.L. 0.04 335 12.4
PYB-PQB B2 100 B.D.L. B.D.L. B.D.L. 0.4 0.11 B.D.L. B.D.L. B.D.L. B.D.L. 0.12
PYB-PQB B2 101 B.D.L. B.D.L. 1.6 0.23 B.D.L. B.D.L. B.D.L. B.D.L. 5.6 6.1
PYB-PQB B2 103 B.D.L. B.D.L. B.D.L. 0.47 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0.08
PYB-PQB B2 104 B.D.L. B.D.L. 2.9 2.5 B.D.L. 0.09 B.D.L. B.D.L. 6.6 2.7
PYB-PQB B2 105 B.D.L. 1.6 20.5 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 113 1.6
PYB-PQB B2 106 B.D.L. 2.9 26.9 B.D.L. 0.17 B.D.L. B.D.L. B.D.L. 150 2.2
PYB-PQB B2 107 B.D.L. B.D.L. 0.92 0.38 B.D.L. B.D.L. B.D.L. B.D.L. 0.18 0.84
PYB-PQB B2 108 0.01 1.3 3.2 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 52 3.1
PYB-PQB B2 109 B.D.L. B.D.L. 1 0.58 B.D.L. B.D.L. B.D.L. B.D.L. 1.2 1.2
PYB-PQB B2 110 B.D.L. 1.5 13 B.D.L. B.D.L. 0.1 B.D.L. B.D.L. 102 4
PYB-PQB B2 111 B.D.L. B.D.L. 4.2 B.D.L. B.D.L. B.D.L. 0.67 B.D.L. 12.6 1.8
208
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
Rottier B.*, Kouzmanov K.*, Casanova V.*, Wälle M.**†, Fontboté L.*
* Department of Earth sciences, University of Geneva, 1205 Geneva, 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@gmail.com
Abstract
The giant mid-Miocene Cerro de Pasco Cordilleran polymetallic (Zn-Pb-Ag-Cu-Bi) deposit
(central Peru) formed during three successive mineralization stages resulting in low- to high-
sulfidation mineral associations: i) several pyrrhotite pipes grading outwards to 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 ± kaolinite 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 accompanied by advanced-argillic
alteration. Recently, field evidence has confirmed that the epithermal polymetallic mineralization is
part of a Miocene porphyry system.
A detailed microthermometric and LA-ICP-MS study of fluid inclusions hosted in gangue and,
using near-infrared microscopy, opaque minerals from the different mineralization stages as well as
available bulk and in-situ SIMS stable isotope data allow reconstructing the evolution and tracing the
source(s) of the mineralizing fluid. Studied fluid inclusions are two-phase (L+V), homogenize to
liquid at moderate temperatures (~150°–280°C) and show a wide range of salinity (1.2 to 19 wt %
NaCl eq.) without evidence of phase separation. Fluids during mineralization stages A, B1, B2 and C1
result of mixing between high-salinity metal-rich (> 1 wt% Mn, Fe, Zn, and Pb and up to several
1000s 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
209
fluids stored at depth that has been repeatedly mobilized ("brine mining") by ascending newly
exsolved condensed magmatic vapor-like fluids. The mixed fluid rose to form mineralization stages A,
B1, B2, and C1, whereby in this latter stage, bulk and in-situ oxygen isotope analyses on quartz indicate
involvement of meteoric water. In contrast, the enargite-pyrite veins of stage C2 were formed by the
ascent of a CO2-bearing contracted vapor, subsequently mixed with meteoric water.
The similarity of initial fluid compositions and evolution during stages A, B1, B2 and C1
contrasts with their significantly different mineral assemblages and metals endowment. Trace element
LA-ICP-MS analyses of sphalerite, pyrite and enargite reveal also important compositional
differences. The trace elements in the measured minerals reside to a significant extent in micro- to
nano-scale solid sulfide and/or sulfosalt inclusions. A direct parallel between fluid composition
recorded in the FIAs and the measured trace element composition of sphalerite, pyrite and enargite has
not been found in most cases. The difference in mineralogy and trace element composition is mainly
due to different temperature, fO2, pH, and fs2 conditions prevailing during the subsequent
mineralization stages, rather than to differences in the initial metal concentrations of the fluid itself.
The cyclic mobilization 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. Such a mechanism may also explain high fluid salinities recorded in other
polymetallic epithermal deposits worldwide.
210
Introduction
Porphyry-related epithermal polymetallic deposits, also called Cordilleran, occur in the same
environment as epithermal high-sulfidation Au-(Ag) deposits and are an important Zn–Pb–Ag–Cu ore
type. They are formed under sub-epithermal to epithermal conditions between 350° to 150°C and
occur as veins in silicic host rocks and as replacement ore-bodies in carbonate sequences (Fontboté
and Bendezú 2009; Bendezú and Fontboté 2009). They are sulfide-rich (up to 50% total sulfide) and
typically have complex mineral associations with a large range of metals (Zn-Pb-Cu-Ag-(Au-Bi-Sb)).
The spatial and temporal link between Cordilleran mineralization and porphyry Cu deposits
has been pointed out by previous studies in both telescoped and non-telescoped systems (Arribas et al.,
1995; Hedenquist et al., 1998; Sajona et al., 2002; Baumgartner et al., 2008, Rusk et al., 2008a, b;
Chang et al., 2011; Reed et al., 2013; Catchpole et al., 2011, 2015a and 2015b). Few studies were
focused on the composition and evolution of mineralizing fluids leading to the formation of porphyry-
related epithermal base and precious metals deposits (Heinrich et al., 2004; Wallier et al., 2006;
Pudack et al., 2009; LeFort et al., 2011, Catchpole et al., 2011 and 2015, Wilkinson et al. 2013). In
contrast to the previous studies, conducted on gangue minerals only (e.g., quartz, carbonate),
Kouzmanov et al. (2010), and Ortelli (2015) reported LA-ICP-MS analyses of fluid inclusions trapped
also in opaque minerals (e.g., sphalerite, enargite and pyrite) minerals from polymetallic vein deposits
respectively at Rosia Poieni porphyry Cu-Au deposit (Romania) and at the Butte district (Montana,
US). The latter results demonstrate that fluid inclusions trapped in gangue minerals are not always
representative of the ore-forming fluids and therefore parallel studies on both ore and gangue minerals
are necessary to resolve the compositional evolution of mineralizing fluids in a given system.
The origin and compositional variations of mineralizing fluids leading to the formation of
Cordilleran deposits still remain not completely understood. Based on LA-ICP-MS analyses of quartz-
hosted fluid inclusions, Catchpole et al. (2011) and Catchpole et al. (2015a) proposed that the
Cordilleran deposits telescoping multiple porphyry events in the Miocene Morococha district of
central Peru were formed by cooled and evolved metal-rich, intermediate-density porphyry-type fluids.
No LA-ICP-MS fluid inclusion study has been published so far on a non-telescoped Cordilleran
deposit and all published work is concentrated on vein type mineralization mainly hosted in magmatic
rocks and not on carbonate replacement ore-bodies.
The fluids that formed the various epithermal ore-bodies in the large Cerro de Pasco
Cordilleran polymetallic (Zn-Pb-Ag-Cu-Bi) deposit are the main focus of our study that is
complemented by other studies focusing on the porphyry mineralization at Cerro de Pasco (Rottier et
al., 2016b and submitted). The deposit was formed during three main mineralization stages by fluids
with contrasting fS2, fO2, and pH (Einaudi, 1977, Baumgartner et al., 2008; Baumgartner et al., 2009;
Rottier et al., 2016a). In this contribution, we combine microthermometry and LA-ICP-MS analyses
on fluid inclusions hosted in gangue (carbonate and quartz) and ore minerals (Fe-rich and Fe-poor
211
sphalerite and enargite) using classical and near-infrared (NIR) transmitted-light microscopy and use
also previously published bulk O and H stable isotope data (quartz, kaolinite and alunite; Baumgartner
et al. 2008) and in-situ (SIMS) oxygen isotope analyses of quartz crystals (Rottier 2017) The results
demonstrate that the three successive stages recognized at Cerro de Pasco were formed each by
tapping of previously stored high-salinity metal-rich magmatic fluids (> 1 wt% Mn, Fe, Zn, and Pb
and up to several 1000s of ppm Sb) diluted by low-salinity and less metal-rich fluids also largely of
magmatic origin except for the third stage where significant meteoric input is recognized.
Geology and mineralization

The Cerro de Pasco district is located 300 km north-east of Lima in the Western Cordillera of
Peru. 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 divided
into two parts by a major high-angle N 15° W-striking reverse fault (named Longitudinal Fault). The
western part consists of a large diatreme-dome complex of 2.5 km in diameter, which was built up by
a succession of phreatomagmatic, magmatic and phreatic events dated from 15.36 ± 0.03 Ma to 15.16
± 0.04 Ma (U-Pb ID-TIMS on zircon; Baumgartner et al. 2009). The diatreme-dome complex
crosscuts, in the western part, weakly metamorphosed Mid-Palaeozoic slates (Excelsior Group) and
conglomerates and sandstone of the Mid-Late Triassic (Rosas et al., 2007; Spikings et al., 2016) Mitu
Group (Fig. 1). The eastern part of the district is formed by a thick sequence (up to 1000 m) of
massive carbonate rocks, mainly limestones, with locally sandy intercalations, black bituminous
limestone, and beds with chert nodules belonging to the Late Triassic Chambará Formation, part of the
Pucará Group (Angeles 1999; Rosas et al. 2007). This carbonate sequence is affected by the N-S-
striking and north-plunging Cerro Anticline (Fig. 1, Baumgartner et al., 2008). A recent study on the
deep and upper crustal evolutions of sub-volcanic and volcanic rocks at Cerro de Pasco indicate that
all rocks present typical subduction-related and an adakite-like signatures (Rottier 2017)
The epithermal polymetallic deposit is located along the eastern margin of the diatreme-dome
complex and it is mainly hosted in the carbonate sequence (Fig. 1). The characteristics of the three
main stages that formed the deposit are summarized as follows according the new stage succession
established by Rottier et al., (2016a) and integrating previous studies, namely by Einaudi (1968a and
1977) and Baumgartner et al. (2008 and 2009).
212
Figure 1: Geological map and cross-section of the diatreme-dome complex and mineralization at Cerro de Pasco (slightly
modified from Rottier et al., 2016b and submitted). The different epithermal mineralization styles were compiled from
field observation during the present study 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) Zoom of one of the trachyte
porphyry outcrops.
213
Stage A consists of at least five pyrrhotite pipe-like bodies with up to 150 m horizontal and up
to 650 m vertical extension that grade outwards into massive Fe-rich sphalerite and galena rims. These
pipes are structurally controlled, mainly by the NNW-SSE longitudinal fault corridor, and
subordinately by N35° and N120° faults. The Fe-rich sphalerite-galena rims form broadly concentric
bodies centered on the pyrrhotite pipes and can extend laterally up to several tens of meters; up to 600
m above level 3900 (Einaudi 1968a and 1977; Baumgartner et al., 2008, Rottier et al., 2016a). The
pipe core is formed by massive pyrrhotite and quartz with traces of wolframite, cassiterite and it is
surrounded by a zone composed of pyrrhotite, quartz, Fe-rich sphalerite, chalcopyrite, and stannite. In
the most external zone of the pipes pyrrhotite, Fe-rich sphalerite, arsenopyrite, chalcopyrite, and quartz
occur. The transitional zone between the pipes and their iron-rich sphalerite-galena rims is
characterized by a progressive increase of Fe-rich sphalerite (up to 90% in volume) to the detriment of
pyrrhotite and arsenopyrite. Galena content increases progressively outwards but remains below 10%
in volume. Inclusions of Ag-rich tetrahedrite, argentite, and polybasite are common in galena.
Sphalerite from the transitional zone and the rims is strongly zoned. Our electron microprobe analyses
(EMPA) confirm previous results (Einaudi 1977; Baumgartner 2007; Baumgartner et al., 2008)
indicating that Fe content in sphalerite varies from 29 to 12 mole % FeS (mean at 21 mole % FeS,
n=100) with a general decrease of the Fe content towards the border of the grains (Rottier et al.,
2016a).
Stage B consists of two types of mineralization; stage B1 consists of quartz-pyrite veins with
minor amount of chalcopyrite, hematite, magnetite, clear-brown sphalerite, galena, and tetrahedrite-
tennantite crosscutting the diatreme-dome complex. These veins have only been observed in drill cores
including those of the deepest drill hole available (DDH 1800_07_01), down to 1200 m below the
present surface. The veins are up to 50 cm wide but mainly below 5 cm, according the present
observations roughly oriented N-S, and show kaolinite-sericite-pyrite and sericite-pyrite alteration
haloes. Stage B2, the volumetrically by large most important, is formed by a massive pyrite (90%)-
quartz (10%) body emplaced at the contact between the diatreme breccia and Pucará carbonate rocks.
It occurs as a large N-S trending funnel-shaped, ~1.5 km in length, 250 m wide and more than 550 m
deep, massive body replacing mainly the Pucará carbonate rocks and locally the diatreme breccia.
Following the contour of the pyrite-quartz body up to a distance of 50 m from the contact, sericite-
quartz-pyrite alteration affects the diatreme-dome complex (Einaudi 1968a; Baumgartner et al. 2008).
The fluids that formed the pyrite-quartz body (stage B2) also affect the previously formed pyrrhotite
pipes and their polymetallic rims (mineralization stage A) leading to complex replacement textures
(mainly by pyrite) and crosscutting relationships. Textural analyses and LA-ICP-MS trace element
analyses of replaced and newly formed minerals indicate an increase of fS2, fO2, and a decrease of pH
of the mineralizing fluids during stage B2 and compared to stage A (Rottier et al., 2016a).
Stage C is characterized by two types of ore-bodies considered to be contemporaneous: high-
to intermediate-sulfidation Zn-Pb-(Bi-Ag-Cu) carbonate replacement ore-bodies (stage C1) and, in the
214
diatreme-dome complex, a set of E-W trending Cu-Ag-(Au-Zn-Pb) enargite-pyrite±quartz veins (stage
C2). The Zn-Pb-(Bi-Ag-Cu) replacement ore-bodies (stage C1) were formed in the western part of the
deposit on carbonate rocks of the Pucará group following mainly regional N35, N120, and N170
structures. They form large irregular upward-flaring pipe-like shape bodies plunging toward the East
with a dip from 25 to 60°, their diameter varies from 50 cm to 50 m and they can be up to 400 m thick
(Baumgartner et al. 2008). The ore-bodies present the following mineralogical zoning: (1) a core zone
consisting of famatinite, pyrite, kaolinite and alunite; (2) an intermediate zone characterized by pyrite,
tetrahedrite, Bi- and Ag-bearing sulfosalts, kaolinite, alunite and APS minerals; (3) an outer zone
composed by Fe-poor sphalerite (up to 90%), galena, kaolinite and rare APS minerals; and (4) an
outermost zone containing magnetite, hematite, Fe-Mn-Zn carbonates and traces of sphalerite, galena
and pyrite (Baumgartner et al. 2008). The Cu-Ag-(Au-Zn-Pb) enargite-pyrite veins (stage C2)
overprint and crosscut the two previous mineralization stages (A and B). The veins are mainly sub-
vertical with strike N70-90°E, i.e., following new tectonic structures compared to those of stage C1,
because the regional faults that control the latter have been obliterated by the diatreme breccia. Vein
thickness varies from few cm to 2.5 m, their vertical extension has not been precisely determined but it
is superior to 760 m (Baumgartner et al. 2008). Three mineral assemblages could be defined in the
veins: (i) early enargite-pyrite, followed by (ii) an assemblage dominated by tennantite and pyrite, and
(iii) a late assemblage formed by Fe-poor sphalerite and galena (Baumgartner et al. 2008). In the
widest veins, these assemblages can develop a clear zoning, but in most veins the enargite-pyrite
assemblage is largely dominant and the two others absent or marked by late veinlets crosscutting
enargite and pyrite crystals. Stage C2veins have been dated from 14.54 ± 0.08 to 14.41 ± 0.07 Ma (Ar-
Ar on alunite; Baumgartner et al. 2009).
Three temporally distinct porphyry-type mineralization events have been recognized, at depth
and also at surface (PM1, PM2, and PM3; Rottier 2017, Rottier et al., 2016b and submitted). They
include (i) hornfels and porphyritic igneous clasts crosscut by high-temperature quartz-molybdenite-
chalcopyrite-pyrite veins (PM1), a detailed study of these clasts and their hosted mineralizations is
provided by Rottier et al. (submitted). The mineralization was restricted to the clasts and not found in
the matrix of the diatreme-breccia and therefore pre-date the emplacement of the breccia assumed
cotemporaneous of the dacitic tuff dated at 15.36 ± 0.03 Ma (zircon U-Pb ID-TIMS; Baumgartner et
al. 2009; Fig. 2). An Re-Os date of 15.59 ± 0.12 Ma obtained from one molybdenite separate extracted
from high-temperature quartz-molybdenite-chalcopyrite-pyrite veins (PM1) is consistent with this
crosscutting relationships (Rottier, 2017). The second porphyry-type mineralization (PM2) is
described in detail by Rottier et al. (2016b) and consists of at least two stockworks of quartz-
magnetite-chalcopyrite-pyrite porphyry-style veinlets centered on small (<20 m diameter) porphyritic
trachyte bodies emplaced in the central part of the diatreme-dome complex (Rottier et al., 2016b). One
of the porphyritic trachyte bodies has been dated at 15.286 ± 0.018 Ma (zircon U-Pb ID-TIMS; Rottier
215
2017; Fig.2). The third porphyry-type mineralization is represented by hornfels and porphyritic
igneous clasts crosscut by high-temperature quartz-magnetite-chalcopyrite-(pyrite) veins hosted in the
quartz-monzonite dykes (PM3). One of the magmatic clasts crosscut by quartz-magnetite-
chalcopyrite-(pyrite) veins and hosted in the quartz monzonite dykes has been dated at 15.165 ± 0.043
Ma (zircon U-Pb ID-TIMS; Rottier 2017). These porphyry-type mineralization events provide the
evidence of a spatial and broadly temporal link between the epithermal polymetallic deposit and
porphyry-type mineralization at Cerro de Pasco (Fig. 2).
Large pervasive pyrophyllite-quartz-pyrite alteration grading to illite-smectite-muscovite-
pyrite and more externally to chlorite-calcite-pyrite alteration affects the outcropping central and the
northern part of the diatreme-dome complex (Fig. 1). These alteration zones are spatially disconnected
from the main epithermal polymetallic mineralization (stages A, B1, B2, C1 and C2). Our field
observations and those of geological staff of the Volcan Compañía Minera S.A (R. Bendezu, personal
communication, 2016) 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 E-W
oxidized veins interpreted to represent the enargite-pyrite veins of stage C2 dated between 14.54 ± 0.06
and 14.41 ± 0.07 Ma (Ar-Ar on alunite; Baumgartner et al., 2009, Fig. 2).. The geological staff of
Volcan Compañía Minera S.A. found E-W oxidized veins crosscut by the mineralized trachyte
porphyry suggesting that an early stage of veins older than 15.286 ± 0.018 Ma also exists. These veins
have not been studied.
Figure 2: Compilation of (i) ID-TIMS U-Pb ages of magmatic rocks and Re-Os age of a molybdenite separate obtained by
Baumgartner et al. (2009) and Rottier (2017), (ii) the potential age range based on cross-cutting relationships for the
hydrothermal events and (iii) 40Ar/39Ar ages of alunites attributed to the enargite-pyrite veins (Baumgartner et al., 2009).
216
Analytical methods
33 samples from the different epithermal polymetallic mineralization stages (A, B1, B2, C1 and
C2) and mineralogical zones were chosen for a fluid inclusion study. Samples are from drill cores
(n=18), the open pit mine (n=14), and from the underground mine (n=1). Description and locations of
the studied samples are available in supplementary Table A.1. Their actual depth varies from 0 to 900
m relative to the present-day surface. Fluid inclusion assemblages (FIAs; Goldstein and Reynolds,
1994) were defined and studied using doubly polished 150-250 µm-thick sections of mineralized
samples and crystal mounts of separate crystals. A total of 122 FIAs, including from 3 to 20 individual
fluid inclusions (n=1030), hosted in quartz, Fe-poor and Fe-rich sphalerite, enargite, and Fe-Zn-Mn
carbonates were measured using both transmitted visible and near-infrared (NIR) microscopy for
gangue and ore minerals, respectively.
Heating and freezing experiments were conducted using a THMSG 600 Linkam heating–
freezing stage mounted on a DMLB Leica microscope for transparent minerals (quartz, Fe-poor
sphalerite, and Fe-Zn-Mn carbonates). For opaque minerals (Fe-rich sphalerite and enargite)
measurements were performed using an FTIR-600 Linkam heating–freezing stage mounted on an
Olympus BX51 microscope equipped with IR Olympus objectives. The microscope is equipped with a
1100 nm low-pass filter placed at the exit of the light source. The NIR observation, petrography and
image acquisition were done using an Olympus XM10 camera controlled by CellP software. The light
source power (up to 100 W) is adjusted by an Olympus TH4-200 controller and recorded by a
voltmeter mounted in parallel (Casanova et al., 2014, Casanova et al., submitted; Ortelli et al.,
submitted). As shown by Moritz (2006), Casanova et al. (2014) and (submitted), Ortelli (2015) and
Ortelli et al., (submitted), during microthermometric experiments a shift of temperature could be
observed as a function of the light power and diaphragms aperture used. This shift, which has an
exponential trend, has been recorded for fluid inclusions hosted in various opaque minerals (including
Fe-rich sphalerite and enargite) by Casanova et al. (submitted) and Ortelli et al., (submitted). A set of
deviation curves of recorded ice melting temperature as function of light source voltage for 3 different
field diaphragm apertures were obtained on a single FI from a Fe-rich sphalerite sample (Fig. 3).
Considering recommendations from the studies of Casanova et al. (submitted) and Ortelli et al.,
(submitted), and obtained deviation curves, all subsequent measurements have been done operating the
light source at a low voltage (below 2.5 V) and with a maximum field diaphragm aperture of 10%, so
as to avoid shifts in measured temperatures.
217
Figure 3: Deviation curves between recorded final ice melting temperatures of a fluid inclusion hosted in a Fe-rich
sphalerite crystal as function of light source voltage (V) for different diaphragm apertures (50%, 10%, and 1%), using
NIR microscopy.
Both Linkam heating–freezing stages were regularly calibrated using SynFlinc standards at
−56.6 °C, 0.0 °C, and 374.1 °C (Sterner and Bodnar, 1984). Ice melting and homogenization
temperatures (Th) obtained by microthermometry on individual fluid inclusions are repeatable. No
CO2 clathrate melting has been observed.
Scanning electron microscopy cathodoluminescence (SEM-CL) images of quartz were used to
clarify the paragenetic context of the studied FIAs. 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.
Raman spectroscopy was used to identify solid inclusions trapped in minerals and gas
composition of fluid inclusions. The measurements were done using a confocal LABRAM with a
532.12 -nm Nd-YAG laser coupled with an Olympus BX51 microscope at the University of Geneva.
Gas composition analyses were done using an x100 objective, Raman setting was 500 µm for the
confocal aperture and 100 µm for the slit, analysis time was fixed to 120s repeated two times. The
limit of detection of such method is below 0.13 mol% CO2 (Rosso and Bodnar, 1995). CO2 has been
detected only in fluid inclusions hosted in quartz from the enargite-pyrite veins (Stage C2). When it
was possible, CO2 content was quantified using the area ratio of the 1388 cm-1 CO2 peak and the 3600
218
cm-1 H2O peak at 300°C following the method described by Azbej et al. (2007). Areas were calculated
using the Peakfit software, using a baseline correction and a peak deconvolution according to the
Gaussian-Lorentzian peak fitting equations. For fluid inclusions of stages A, B1 and B2 and C1, CO2
peaks have been observed just in a few fluid inclusions, with no consistency within a single FIA and
with intensities always below three times the background.
Sphalerite from the different mineralization stages was analyzed for its major and minor
elements. Sulfur, Zn, Fe, Mn, Cu, Se, Ag, Cd and In were quantified by electron microprobe analysis
(EMPA) at the University of Lausanne using a Jeol JXA 8200 Superprobe WD/ED combined
microanalyzer. Operating conditions were: accelerating voltage of 20 kV, beam current of 20 nA, and
beam diameter of 1 µm. Standards and radiations used were as follows: FeS2 (Fe-Kα), ZnS (Zn-Kα, S-
Kα), Cu5FeS4 (Cu-Kα), CdSe (Cd-Lα, Se-Lα), MnS (Mn-Kα), Ag metal (Ag-Lα), InP (Ag-Lα).
Counting times of 20 s on peak and 10 s on background on both sides of the peak were used for all
elements. Overlap and matrix corrections were carried out following the established protocol and
software in the laboratory. Sphalerite crystals were systematically analyzed above each fluid inclusion
position prior to LA-ICP-MS analyses in order to use the determined Zn content as an internal
standard for host correction (Ortelli, 2015). This method has been used due to the high Fe content
variability in the studied sphalerite.
LA-ICP-MS analyses were performed on more than 600 fluid inclusions from 91 FIAs hosted
in quartz, Fe-poor and Fe-rich sphalerite, and enargite crystals. Selected grains of sphalerite, enargite,
and pyrite were also analysed for their trace element content. Analyses were conducted on 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 1 provides a summary of the analytical conditions, data acquisition parameters, and list
of the isotopes analyzed during LA-ICP-MS sessions. Fluid inclusions in sphalerite and enargite were
ablated using a constant laser beam diameter, while for quartz-hosted fluid inclusions a progressive
increase of the laser beam diameter was applied to limit quartz explosion (Günther et al., 1998), using
an iris diaphragm (Guillong and Heinrich, 2007).
NIST glass SRM 610 was used as external standard and analyzed two times between a
maximum of 20 unknowns to correct for drift by linear regressions. For fluid inclusions hosted in
sulfides, Mass-1 standard (Wilson et al., 2002) was also measured two times, after the first two and
before the last two NIST 610 SRM measurements, in order to quantify correctly the host composition.
Fluid inclusion salinity determined from microthermometry measurements, assuming Na as the only
salt present, was used as internal standard. An empirical correction for K and Mn content was applied
systematically and additionally a Fe correction was applied for high-salinity (>10wt% NaCl eq.)
inclusions (Heinrich et al., 2003). Internal standards for host correction were (i) 99.5 wt% SiO2 for
quartz, (ii) 48.0 wt% Cu (stoichiometric value) for enargite, and (iii) Zn content of sphalerite
corresponding to each fluid inclusion position (determined by EMPA). The results are reported as
219
element concentrations and also as element/(Na+K+Mn) ratios. For trace element analyses of sulfides,
46.55 wt% Fe for pyrite, 48.0 wt% Cu for enargite, and previously measured by EMPA Zn content for
sphalerite were used as internal standard. LA-ICP-MS analyses were reduced using the SILLS
software (Guillong et al., 2008).
Table 1: LA-ICP-MS machine and data acquisition parameters
Excimer 193 nm ArF laser

Quartz Sphalerite Enargite Pyrite
Compex 110I
Energy density 24-30 J/cm2 2 to 3 J/cm2 2 to 3 J/cm2 2 to 3 J/cm2
Repetition rate 10 Hz 10 Hz 5-10 Hz 5 Hz
Crater sizes 15-60 µm 20-40 µm 20-40 µm 40 µm
In-house built
In-house built glass In-house built glass In-house built glass
glass chamber
chamber with anti- chamber with anti- chamber with anti-
Ablation cell with anti-reflection
reflection coated silica reflection coated reflection coated silica
coated silica glass
glass window silica glass window glass window
window
Cell He gas flow 1.1 l/min He 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 5 ml/min H2

Readings per replicate 400 500 400 300
Points per peak 1 per mass 1 per mass 1 per mass 1 per mass
tuned to <0.5 % tuned to <0.5 %
Oxide production rate tuned to <0.5 % ThO tuned to <0.5 % ThO
ThO ThO
40 ms fo Fe, 30 ms for 30 ms for Ag and
Dwell time per isotope 10 ms for all
Ag and Ca; 20 ms for Te Au; 20 ms for Ca
isotopes
10 ms for the
others
7
7 Li, 11B, 23Na, 32S,
Li, 11B, 23Na, 29Si, 39
7 K, Ca, 55Mn,
44
Li, 11B, 23Na, 29Si, 32S, 32
S, 39K, 44Ca, 55Mn, 57
39 Fe, 65Cu, 66Zn,
K, 44Ca, 55Mn, 57Fe, 65Cu, 57
Fe, 65Cu, 67Zn, 75
Isotopes analyzed ("Fluid 66 As, 85Rb, 88Sr,
Zn, 75As, 85Rb, 88Sr, 75
As, 85Rb, 88Sr, 107
inclusions" program) 107 Ag, 118Sn, 121Sb,
Ag, 121Sb, 125Te, 133Cs, 107
Ag, 111Cd, 121Sb, 125
137 Te, 133Cs, 137Ba,
Ba, 205Tl, 208Pb, 209Bi 125
Te, 133Cs, 137Ba, 197
205 Au, 205Tl, 208Pb,
Tl, 208Pb, 209Bi 209
Bi
Readings per replicate 300 300 300
30 ms for Ga; 20
30 ms for Ag and 30 ms for Ag and Au; 20
Dwell time per isotope ms V, Ge, Ag, and
Au; 20 ms for V ms for V
Au
10 ms for the
10 ms for the others 10 ms for the others
others
23 28 32 51 23
Na, Si, S, V, Na, 28Si, 32S, 51V,
53
Cr, 55Mn, 57Fe, 53
Cr, 55Mn, 57Fe, 23
59 Na, 28Si, 32S, 51V, 53Cr,
Co, 60Ni, 65Cu, 59
Co, 60Ni, 65Cu, 55
66 Mn, 57Fe, 59Co, 60Ni,
Zn, 69Ga, 72Ge, 66
Zn, 69Ga, 75As, 65
75 Cu, 66Zn, 69Ga, 75As,
Isotopes analyzed ("Trace As, 77Se, 95Mo, 77
Se, 95Mo, 109Ag, 77
109 Se, 95Mo, 109Ag, 111Cd,
elements" program) Ag, 111Cd, 115In, 111
Cd, 115In, 118Sn, 115
118 In, 118Sn, 121Sb, 125Te,
Sn, 121Sb, 125Te, 121
Sb, 125Te, 182W, 182
182 W, 197Au, 202Hg, 205Tl,
W, 197Au, 202Hg, 197
Au, 202Hg, 205Tl, 208
205 Pb, 209Bi, 232Th, 238U
Tl, 208Pb, 209Bi, 208
Pb, 209Bi, 232Th,
232
Th, 238U 238
U
220
Results
Fluid inclusion petrography and microthermometry

Fluid inclusions from the three mineralization stages are all aqueous, liquid-rich with 20-30
vol% vapor phase. The microthermometry results are reported in Table 2 and plotted in Figure 4 that
also includes microthermometry measurements of Baumgartner et al. (2008).
Pyrrhotite pipes and their Fe-rich sphalerite-galena rims (stage A)

Quartz grains used for the fluid inclusion study were sampled in the different zones of the
pipes and their rims (Table A.1); they are small (< 500 µm) and euhedral. Quartz crystals from the
pipe cores often present inclusions of rutile and occasionally of wolframite and cassiterite, whereas
those from the external zone of the pipes and from the Fe-rich sphalerite-galena rims presents solid
inclusions of apatite, rutile, and anatase. CL-textures are similar for the different quartz grains studied
and SEM-CL images show regularly fine zoning marked by low to moderate CL-intensity. Areas rich
in apatite are highly luminescent; rare dissolution textures were observed. Fluid inclusions studied are
primary, aligned along growth bands or pseudo-secondary forming arrays of elongated fluid inclusions
from the center toward the external part of the crystals. The studied fluid inclusions in quartz are small
between 5 and 25 µm and have an irregular shape.
Iron-rich sphalerite crystals are almost always transparent in the NIR light and reveal a regular
zoning (Fig. 5A). Fluid inclusions studied are primary and pseudo-secondary, ranging from 10 to 40
µm in size and having a regular to irregular shape (Fig. 5A).
Microthermometry results are similar for quartz- and sphalerite-hosted FIAs (Fig. 4A).
Homogenization temperatures vary from 185° to 280°C, for more than 80 % of the FIAs between 220°
and 260°C (Fig. 4A, Table 2). One FIA presents a higher homogenization temperature at 322°C. When
possible, eutectic temperatures were measured and range between -21° and -23°C indicating a NaCl-
KCl dominated system (Goldstein and Reynolds 1994). Final ice melting temperatures range between
-12° and -1.5°C. Salinities were calculated ignoring the effect of KCl and using the equation of Bodnar
and Vityk (1994). Obtained salinity varies between 2.5 and 16 wt% NaCl eq., no correlation between
salinity and homogenization temperature exists.
No systematic difference of homogenization temperatures or ice melting temperature was
observed, neither as a function of the position of the sample in the considering mineral zonations of
the pyrrhotite pipes and their rims nor as a function of the sampling depth.
221
Figure 4: Homogenization temperature vs. salinity diagrams for studied fluid inclusion assemblages from the different
mineralization stages. Values for each FIA are plotted as mean values with 1σ error bars. FIAs from Baumgartner et al.
(2008), are plotted with error bars representing the obtained minimum and the maximum values of Th and salinity. All
results are available in supplementary Table A.2
Deep pyrite-quartz veins (stage B1)

Quartz crystals from the deep pyrite-quartz veins are euhedral, from 500 µm up to 3 mm long.
They contain solid inclusions of pyrite and are interpreted as coeval with the pyrite precipitation.
SEM-CL images show very regular fine zoning with low to moderately luminescent bands (Fig. 6F).
Fluid inclusions are small, between 5 to 25 µm, and secondary in origin (Figs. 6D and F). Trails of
fluid inclusions spatially associated with small pyrite solid inclusions were selected for
microthermometric measurement and were interpreted as coeval to pyrite precipitation.
222
Microthermometry measurements of quartz-hosted FIAs yield homogenization temperatures from
234° to 360°C and final ice melting temperatures between -14.6° and -1.8°C (Fig. 4B). No eutectic
temperature was measured. Salinities calculated using the equation of Bodnar and Vityk (1994) range
from 3.1 to 18.5 wt% NaCl eq. FIAs showing homogenization temperatures above 280°C present
higher salinities, above 10 wt% NaCl eq. compared to the other FIAs (Fig. 4B). Below 280°C FIAs
present no correlation between measured homogenization temperature and salinity, like for FIAs from
stage A.
Pyrite-quartz body (stage B2)
Selected quartz crystals are euhedral and up to 1 cm in size (Figs. 6A, C, and E); they host
solid inclusions of apatite, rutile, and anatase, up to 100 µm. SEM-CL images show regular fine
zoning with low to moderate CL-intensity bands with local high-luminescent bands (Figs. 6A, B, C
and E). Studied fluid inclusions are primary, trapped along the growth bands (Figs. 6A, B and C) and
pseudo-secondary, forming array of elongated fluid inclusions from the core toward the external part
of the crystals (Fig. 6G). Fluid inclusions are small, from 5 to 25 µm, and irregular in shape.
Microthermometry measurements on selected FIAs yield homogenization temperatures from 192° to
282°C, from them, more than 80% between 220° and 280°C. FIAs presenting the lowest
homogenization temperature values (from 192° to 220°C) are from the upper part of the pyrite-quartz
body and therefore may record the cooling of the system (Fig. 4C). Final ice melting temperatures
range from -12.2° to -1.6°C. Few eutectic temperatures were measured, mainly around -23°C with
some values around -27°C, indicating a NaCl-KCl dominated system with possibly a low amount of
CaCl2 or MgCl2 (Goldstein and Reynolds 1994). Salinities were calculated ignoring the effect of KCl
and other salts using the equation of Bodnar and Vityk (1994). Calculated salinities range from 2.7 to
16.2 wt% NaCl eq. and no correlation exists between homogenization temperature and salinities (Fig.
4C).
In some quartz crystals with abundant primary fluid inclusions, it was possible to study
homogenization and ice melting temperature evolution of different FIAs as a function of their position
in the crystal. An increase of ice melting temperature towards the periphery of the grain is observed in
most cases (Fig. 7A), whereas homogenization temperatures show no clear evolution.
223
Figure 5: Typical fluid inclusion assemblages observed in Fe-rich sphalerite, Fe-poor sphalerite and enargite. All pictures
have been taken in NIR transmitted light, except (E): A) Pseudo-secondary FIA hosted in Fe-rich sphalerite (> 20 mole %
FeS) from stage A; B) Primary FIA in Fe-rich core (> 13 mole % FeS) of sphalerite from stage C1; C) Fe-rich core (> 23
mole % FeS) of sphalerite from stage C1; D) Primary FIA in Fe-rich core of the sphalerite crystal from C; E) Primary
FIA in Fe-poor (< 1.6 mole % FeS) core of sphalerite from stage C1; F) Pseudo-secondary FIA hosted in Fe-poor (< 2.5
mole % FeS) growth band of sphalerite; G-H) Elongated fluid inclusions parallel to the c-axis of the enargite crystals.
224
Figure 6: A) Transmitted light photomicrograph of a quartz crystal from stage B2; B) SEM-CL image of the same crystal;
C) Primary FIA hosted in a growth band of this quartz. D) SEM-CL image of a quartz crystal from stage B1. E) SEM-CL
image of quartz crystals from stage B2. F) Secondary FIAs from the quartz crystal from (B). G) Transmitted light
photomicrograph of the quartz crystals from (C). H) Zoom on the elongated pseudo-secondary FIAs from the quartz
crystal from (E) and (G).
225
Table 2: Microthermometric data for the 123 FIAs studied from the different mineralization stages at Cerro de Pasco
P
Stage FIA # Host FI TmIce Salinity Th CO2 n Density
min
3
mineral type (°C) σ (wt% NaCl eq.) σ (°C) σ (mol%) (g/cm ) (bar)
A 73_L_1 Sl P -3.3 0.3 5.5 0.5 262 4 <0.13 6 0.83 44
A 130_E_2A Sl P -4.0 0.1 6.5 0.1 219 9 <0.13 9 0.90 19
A 130_E_2B Sl P -4.0 0.1 6.4 0.1 227 9 <0.13 8 0.89 23
A 69_C_1 Sl P -7.2 0.2 10.8 0.2 224 11 <0.13 14 0.93 21
A 111_G_1 Sl P -11.3 0.1 15.2 0.1 262 13 <0.13 3 0.92 44
A 111_G_2 Sl P -11.0 1.5 14.9 1.5 258 14 <0.13 6 0.93 41
A 116_H_FIA3 Sl P -12.1 0.2 16.0 0.2 233 1 <0.13 8 0.96 26
A 175_E_1A Sl P -1.8 0.1 3.0 0.1 186 2 <0.13 7 0.91 9
A 175_E_1B Sl P -1.6 0.2 2.7 0.3 226 8 <0.13 7 0.86 22
A 175_E_2 Sl P -11.3 0.4 15.3 0.4 255 11 <0.13 7 0.93 39
A CPR464_2_2 Sl P -2.9 0.1 4.7 0.1 280 5 <0.13 15 0.80 60
A CPR464_2_1 Sl P -2.9 0.1 4.7 0.1 281 6 <0.13 8 0.79 61
A CPR464_2_4 Sl P -2.7 0.1 4.5 0.1 249 9 <0.13 3 0.84 35
A 175_E_3 Sl PS -9.7 0.5 13.6 0.5 242 10 <0.13 4 0.93 31
A 130_E_2C Sl S -4.0 0.1 6.4 0.2 224 1 <0.13 8 0.89 21
A 111_G_3 Sl S -8.2 0.2 11.9 0.2 261 7 <0.13 5 0.90 44
A 116_H_FIA4 Sl S -3.5 0.2 5.7 0.4 230 3 <0.13 7 0.88 24
A 47_F_1 Sl S -2.1 0.2 3.5 0.4 248 3 <0.13 5 0.83 34
A 59_2_A Qz P -2.0 0.1 3.4 0.2 245 9 <0.13 9 0.84 33
A 59_2_B Qz P -6.8 0.1 10.3 0.1 322 1 <0.13 8 0.80 111
A 73_F_2 Qz P -5.3 0.4 8.3 0.5 247 7 <0.13 8 0.88 34
A 73_F_3 Qz P -5.7 0.5 8.8 0.6 249 9 <0.13 8 0.88 35
A 67_A_1 Qz PS -2.3 0.2 3.9 0.4 252 16 <0.13 15 0.83 37
A 67_A_2 Qz PS -1.6 0.1 2.7 0.2 250 14 <0.13 17 0.82 36
A 111_F2_1 Qz S -4.3 0.1 6.9 0.2 249 7 <0.13 6 0.87 35
B1 05_1_1 Qz P -5.0 0.1 7.9 0.1 248 4 < 0.13 10 0.88 34
B1 05_1_5 Qz P -4.6 0.2 7.3 0.2 274 9 < 0.13 10 0.87 60
B1 05_1_5b Qz P -7.9 0.1 11.5 0.1 280 4 < 0.13 4 0.84 54
B1 12_2_1 Qz P -3.8 0.2 6.2 0.3 240 9 < 0.13 12 0.87 29
B1 05_3_1 Qz P? -1.8 0.0 3.1 0.0 261 5 < 0.13 10 0.81 44
B1 05_3_2 Qz P? -1.9 0.1 3.3 0.1 287 13 < 0.13 9 0.76 67
B1 05_2_1 Qz PS -2.9 0.3 4.7 0.5 234 8 < 0.13 7 0.86 26
B1 05_4_2a Qz PS -5.4 0.1 8.4 0.1 271 2 < 0.13 4 0.85 52
B1 05_4_2b Qz PS -4.0 0.2 6.4 0.3 263 6 < 0.13 6 0.84 45
B1 05_4_2c Qz PS -7.0 0.2 10.5 0.3 288 3 < 0.13 3 0.85 68
B1 12_5_1 Qz PS -14.7 1.1 18.3 0.9 358 11 < 0.13 8 0.90 173
B1 05_1_3 Qz S -14.7 0.4 18.4 0.3 306 7 < 0.13 7 0.91 89
B1 05_1_4 Qz S -3.2 0.3 5.3 0.5 271 6 < 0.13 10 0.82 52
B1 05_2_2 Qz S -5.4 0.2 8.4 0.2 248 12 < 0.13 15 0.88 34
B1 05_3_3 Qz S -2.5 0.4 4.1 0.6 275 3 < 0.13 5 0.80 55
B1 05_4_1 Qz S -5.9 0.0 9.1 0.0 253 2 < 0.13 6 0.88 38
B2 105_4_1 Qz P -3.0 0.1 4.9 0.1 200 9 < 0.13 9 0.91 12
B2 80_G_2 Qz P? -1.8 0.2 3.0 0.2 242 12 < 0.13 10 0.84 31
B2 84_J_2 Qz P? -3.2 0.6 5.6 0.6 250 19 < 0.13 8 0.85 36
B2 173_I_1 Qz P? -3.4 0.1 5.6 0.2 235 9 < 0.13 8 0.87 27
B2 174_G2_1 Qz PS -6.5 0.1 8.6 3.4 207 11 < 0.13 7 0.93 15
B2 174_G2_2 Qz PS -6.0 0.1 9.2 0.1 192 14 < 0.13 9 0.95 11
B2 80_N_1 Qz PS -10.5 0.4 14.9 0.9 230 17 < 0.13 5 0.95 24
B2 84_J_1 Qz PS -3.1 0.1 5.1 0.2 261 17 < 0.13 7 0.83 43
B2 84_J_3b Qz PS -4.8 0.4 7.5 0.6 235 13 < 0.13 6 0.90 26
B2 84_J_3a Qz PS -1.6 0.1 2.7 0.2 240 13 < 0.13 6 0.84 29
B2 105_4_2 Qz PS -2.4 0.1 4.1 0.1 239 11 < 0.13 10 0.96 5
B2 105_7_1 Qz PS -12.2 0.5 16.1 0.5 270 15 < 0.13 10 0.93 51
B2 126_10_1 Qz PS -3.0 0.0 4.9 0.0 259 5 < 0.13 10 0.83 43
B2 126_10_1b Qz PS -4.1 0.2 6.6 0.3 241 6 < 0.13 8 0.87 30
B2 126_5_2 Qz PS -6.5 0.4 9.9 0.5 242 8 < 0.13 6 0.90 31
B2 126_6_1 Qz PS -3.7 0.2 5.8 0.4 250 4 < 0.13 8 0.85 36
226
B2 CV11A_10_1 Qz PS -5.1 0.1 8.0 0.1 269 6 < 0.13 10 0.85 49
B2 CV11A_10_2 Qz PS -5.1 0.3 8.0 0.4 263 8 < 0.13 6 0.86 45
B2 CV11A_10_3 Qz PS -7.3 0.0 10.9 0.0 221 4 < 0.13 10 0.93 20
B2 CV11A_7_1 Qz PS -3.3 0.1 5.5 0.2 264 5 < 0.13 9 0.83 46
B2 CV11A_6_1 Qz PS -1.9 0.1 2.9 0.9 261 2 < 0.13 11 0.80 44
B2 CV11B_1_1 Qz PS -4.3 0.1 6.8 0.1 229 15 < 0.13 16 0.89 24
B2 CV11B_4_1 Qz PS -5.3 0.1 8.3 0.1 219 5 < 0.13 11 0.91 19
B2 CV11B_5_1 Qz PS -3.8 0.1 6.2 0.1 261 15 < 0.13 11 0.84 44
B2 CV11B_6_4 Qz PS -2.8 0.2 4.6 0.2 209 7 < 0.13 11 0.89 15
B2 CV11B_6_3 Qz PS -5.6 0.1 8.6 0.1 243 13 < 0.13 9 0.89 32
B2 CV11B_6_1 Qz PS -4.5 0.7 7.1 1.0 228 10 < 0.13 12 0.89 23
B2 CV11B_6_6 Qz PS -6.2 0.5 8.1 0.6 224 4 < 0.13 6 0.91 21
B2 CV11B_6_5 Qz PS -3.0 0.1 4.4 1.6 250 12 < 0.13 8 0.84 36
B2 CV11B_6_2 Qz PS -4.2 0.1 5.9 2.2 245 13 < 0.13 8 0.86 33
B2 173_F_1 Qz PS -3.0 0.1 5.0 0.1 243 7 < 0.13 7 0.86 31
B2 173_F_1b Qz PS -3.9 0.1 6.2 0.2 239 6 < 0.13 8 0.87 30
B2 173_G_1 Qz PS -2.1 0.3 3.6 0.4 207 12 < 0.13 10 0.89 15
B2 174_G2_4 Qz S -3.8 0.1 6.2 0.1 204 5 < 0.13 9 0.91 14
B2 80_G_3 Qz S -2.5 0.0 4.2 0.0 282 3 < 0.13 4 0.79 62
C1 180-G-1 Cb PS -4.9 0.2 7.7 0.2 172 5 < 0.13 14 0.95 7
C1 198-D-1C Cb P -8.5 0.5 12.3 0.5 225 1 < 0.13 4 0.94 22
C1 198-D-1 Cb P -2.8 0.2 4.7 0.3 199 7 < 0.13 12 0.91 12
C1 198-D-1B Cb P -5.8 0.0 8.9 0.0 195 3 < 0.13 4 0.94 11
C1 140-F2-1 Sl P -14.9 0.8 18.6 0.6 266 10 < 0.13 8 0.95 47
C1 140-M-2 Sl P -2.7 0.2 4.4 0.2 207 3 < 0.13 8 0.90 15
C1 471-3-1 Sl P -11.9 0.0 15.9 0.0 235 10 < 0.13 10 0.95 27
C1 196-F1-1 Sl P -3.2 0.1 5.2 0.2 190 1 < 0.13 6 0.92 10
C1 196-F2-1A Sl P -2.0 0.1 3.4 0.2 172 1 < 0.13 3 0.92 7
C1 196-F2-1B Sl P -3.3 0.2 3.4 0.2 197 6 < 0.13 3 0.99 12
C1 138-A-1 Sl P -4.1 0.1 6.6 0.2 173 5 < 0.13 8 0.94 7
C1 140-J-1 Sl PS -4.3 0.9 6.8 1.3 216 8 < 0.13 6 0.90 18
C1 140-J-2 Sl PS -1.4 0.1 2.5 0.1 171 2 < 0.13 6 0.92 7
C1 140-F2-2 Sl PS -2.9 0.1 4.8 0.2 199 2 < 0.13 11 0.91 12
C1 140-M-1 Sl PS -0.8 0.0 1.4 0.0 207 6 < 0.13 9 0.87 15
C1 140-F1-1 Sl PS -3.6 0.1 5.8 0.2 235 4 < 0.13 11 0.87 27
C1 471-5-1 Sl PS -4.0 0.1 6.4 0.1 185 5 < 0.13 10 0.93 9
C1 471-2-2 Sl PS -2.9 0.0 4.8 0.0 198 3 < 0.13 10 0.91 12
C1 431-2-1 Sl PS -2.1 0.1 3.5 0.1 155 9 < 0.13 10 0.94 5
C1 431-3-3 Sl PS -0.6 0.1 1.1 0.1 160 8 < 0.13 7 0.92 6
C1 431-3-5 Sl PS -1.2 0.1 2.1 0.1 156 7 < 0.13 9 0.93 5
C1 77-1-1 Sl PS -4.4 0.1 7.0 0.2 208 6 < 0.13 4 0.91 15
C1 422-1-1 Sl PS -2.6 0.1 4.3 0.1 170 6 < 0.13 20 0.93 7
C1 196-F2-2 Sl PS -3.1 0.1 5.0 0.1 185 7 < 0.13 11 0.92 9
C1 196-U-2 Sl PS -2.2 0.1 3.6 0.2 177 4 < 0.13 7 0.92 8
C1 180-N-1A Sl S -2.6 0.1 4.4 0.1 178 4 < 0.13 13 0.93 8
C1 180-N-1B Sl S -1.7 0.0 2.9 0.1 167 5 < 0.13 9 0.93 6
C1 77-7-1 Sl S -3.9 0.1 6.4 0.1 164 4 < 0.13 9 0.95 6
C1 CPR26-2-1 Sl S -3.4 0.1 5.5 0.1 153 7 < 0.13 15 0.95 5
C2 143-2-3 En P? -1.1 0.2 1.8 0.3 226 12 n.a. 20 0.85 22
C2 143-2-3b En P? -1.2 0.0 2.1 0.1 219 4 n.a. 5 0.86 19
C2 152-1-2 En P? -1.5 0.1 2.6 0.2 196 9 n.a. 8 0.89 12
C2 152-2-5 En P? -1.1 0.1 2.0 0.2 206 12 n.a. 8 0.88 14
C2 152-2-5B En P? -5.3 0.1 8.2 0.1 199 11 n.a. 3 0.93 12
C2 152-2-3 En P? -3.0 0.3 4.9 0.5 202 4 n.a. 4 0.90 13
C2 152-3-6A En P? -1.2 0.2 2.0 0.3 201 11 n.a. 8 0.88 13
C2 152-3-6B En P? -2.3 0.2 3.9 0.3 217 8 n.a. 8 0.88 18
C2 439-1-1 Qz P -2.0 0.1 2.7 (3.4) 0.10 262 3 0.5* 9 0.77 44**
C2 439-9-1 Qz P -1.9 0.1 2.4 (3.2) 0.10 263 4 0.5* 11 0.77 45**
C2 439-9-2 Qz P -1.9 0.1 2.4 (3.2) 0.10 261 3 0.5* 5 0.77 44**
C2 24-E-4C Qz P -1.7 0.2 2.1 (3.0) 0.30 265 15 0.5* 5 0.76 47**
C2 24-E-4B Qz P -1.7 0.2 2.5 (2.8) 0.30 280 1 0.3 3 0.76 60**
C2 439-1-1 Qz PS -1.2 0.1 1.2 (2.1) 0.20 212 18 0.5* 15 0.86 16**
227
C2 24-C-2 Qz PS -1.2 0.1 1.1 (2.1) 0.10 294 1 0.66 16 0.76 75**
C2 24-E-3 Qz S -7.3 0.1 10.2 (10.8) 0.20 262 6 0.5* 5 0.81 44**
C2 24-E-2 Qz S -12.1 2.0 15.6 (15.9) 1.90 291 19 0.52 6 0.84 71**
C2 24-E-4 Qz S -3.6 0.1 5.5 (5.8) 0.10 224 6 0.26 3 0.78 21**
For FIAs hosted in quartz from stage C2: * assumed CO2 content, not-calculated content, ** Minimum pressure of entrapment ignoring CO2
content; Salinity values in bracket are calculated ignoring the CO2 content. Abbreviations used: Sl- sphalerite, Qz - quartz, Cb - carbonate,
En - enargite; P - primary, PS - pseudo-secondary, S - secondary; n.a. - not analyzed
High- to intermediate-sulfidation Zn-Pb-(Bi-Ag-Cu) carbonate replacement ore-bodies (stage C1)

Only in the outer zone of the carbonate replacement bodies, sphalerite and Fe-Mn-Zn
carbonate crystals (> 200 µm) suitable for fluid inclusion study were found. Sphalerite crystals used
for fluid inclusion studies were <1 mm in size and euhedral. Some of the studied crystals present three
distinct zones (Figs. 5B, C and 7 B): i) an Fe-rich core with FeS contents between 31 to 10 mole %
showing a general decrease towards the border; ii) an intermediate with 20 to 5 mole % FeS; iii) an
external zone consisting of yellow, white or purple in transmitted light, Fe-poor sphalerite with FeS
contents between 5 to 0 mole %. Contacts between the different zones are sharp (Fig. 8). Frequently,
sphalerite grains show only the most external Fe-poor growth zone (Fig. 5E). Within each zone, cyclic
changes in the crystal morphology as well as dissolution surfaces are commonly observed (Fig. 8B).
Studied fluid inclusions are primary (aligned along growth bands, Figs. 5B, C, and D) and pseudo-
secondary. All are from 10 to 40 µm in size and have an irregular shape (Fig. 5F).
Four FIAs hosted in Fe-Mn-Zn carbonate were also studied. Carbonate crystals are euhedral,
from 500 µm up to few millimeters in size. Fluid inclusions studied were primary, forming clusters
along growth bands, from 15 to 45 µm in size and have an irregular shape.
Microthermometry results are similar for FIAs hosted in sphalerite and in Fe-Mn-Zn carbonate
crystals. Homogenization temperatures vary from 153° to 276°C and final ice melting temperatures
range from -15° to -0.8°C. No eutectic temperature was measured. Salinities calculated using the
equation of Bodnar and Vityk (1994) range from 1.1 to 19.1 wt% NaCl eq. A positive correlation
between homogenization temperatures and salinities exists (Fig. 4D). In well-zoned sphalerite crystals,
it can be recognized that both salinity and homogenization temperature decrease from core to rim
(Fig.7B).
228
Figure 7: A) SEM-CL image of a quartz crystal from stage B2; different sub-generations (1, 2 and 3) have been defined
based on CL textures. Green lines show the location of the different primary FIAs. The graph shows the evolution of
salinity (red line) and homogenization temperature (blue line) recorded in the FIAs from the different quartz sub-
generations. B) Transmitted and reflected light photomicrographs of a sphalerite crystal from stage C1 showing a
zonation, marked by a core, an intermediate and an external zone, and a homogenization temperature vs. salinity diagram
showing for FIAs hosted in the different zones.
229
Figure 8: A) Electron microprobe profiles showing the distribution of Fe (mole % FeS) and Cd (wt%) content through the
ore, intermediate and external zones of a stage C1 sphalerite crystal. B) BSE image of the studied sphalerite with the
location of the profiles. Note the change in crystal morphology between the different zones and the presence of dissolution
surfaces in each of them.
Enargite-pyrite veins (Stage C2)

Quartz crystals are rare in the veins of stage C2 and crystallized before enargite and pyrite
(Figs. 9A and C); the studied quartz crystals are euhedral and up to 1 mm in size. SEM-CL images
reveal commonly resorbed magmatic cores characterized by high CL intensity crosscut and overgrown
by later hydrothermal quartz showing a lower CL intensity and a regular fine-zoning (Fig. 9B).
Contacts between magmatic and hydrothermal quartz are marked by numerous inclusions of rutile.
Studied fluid inclusions are primary in the hydrothermal overgrowths (Figs. 9C and D) and secondary
in cracks crosscutting the magmatic cores (Figs. 9A and B). They are small, between 10 and 25 µm in
size and have an irregular shape.
230
Figure 9: A) Transmitted-light photomicrograph of a euhedral quartz crystal associated with enargite from stage C2. B)
SEM-CL image of the same quartz crystal showing a magmatic core crosscut and overgrown by late epithermal-stage
quartz. C) Transmitted-light photomicrograph of a euhedral epithermal-stage quartz crystal showing a clear magmatic
core (with melt inclusions) surrounded by primary fluid and rutile inclusions. D) Zoom on the primary fluid inclusions.
Enargite is euhedral, up to 1 cm in size, and commonly transparent using NIR light. BSE
images and NIR microscopy reveal poor zoning. Fluid inclusions are between 10 and 60 µm in size,
elongated, and aligned along the c-axis of the crystals (Figs. 5G and H). No clear petrographic criteria
were found to determine the primary or secondary origin of the studied FIAs.
Quartz- and enargite-hosted FIAs present different microthermometric results. Primary FIAs
hosted in hydrothermal quartz overgrowths yield homogenization temperatures from 260° to 295°C
and ice melting temperatures from -2° to -1.2°C. The homogenization temperatures of secondary FIAs
hosted in cracks through magmatic cores and in the hydrothermal overgrowths, range from 224 to
295°C and ice melting temperatures from -12.1° to -3.6°C. Few eutectic temperatures were measured;
all of them were around -21°C and indicate a NaCl-dominated fluid. The presence of CO2 was
identified by Raman spectroscopy in the vapor phase of fluid inclusions from both primary and
secondary FIAs. CO2 was quantified using the method describes by Azbej et al. (2007) on 4 FIAs;
results are summarized in Table 2. Calculated CO2 content is low, from 0.26 to 0.66 mol% (1σ = 0.2 to
0 .37 mole %). Effect of CO2 on salinity was calculated using a modified version of Ternary software
developed by Akinfiev and Diamond (2010). Ignoring the effect of CO2 content has a small impact
(less than 10%) on the calculated salinity for the secondary FIAs but for the primary FIAs, salinity
could be overestimated by 50% (Table 3) if the CO2 effect is ignored. For all quartz-hosted FIAs
where CO2 was not quantified, 0.5 mol. % was chosen as an approximation to correct the salinity.
231
After CO2 correction, salinities range from 1.2 to 2.7 wt% NaCl eq. for primary FIAs and from 5.4 to
15.1 wt% NaCl eq. for secondary FIAs (Fig. 4E, Table 3).
Table 3: CO2 content calculated for different fluid inclusion assemblages following the method described by Azbej et al.
(2007).
# mol.%
FIA FI type n Salinity (wt% NaCl eq.) 1σ
CO2
24C_FIA2 Primary 5 2.1 0.66 0.27
24E_FIA4B Primary 2 2.9 0.30 0.21
24E_FIA2 Secondary 1 15.2 0.52 0.20
24E_FIA4 Secondary 1 5.9 0.26 0.37
Microthermometry measurements on enargite-hosted FIAs yield homogenization temperature

from 196° to 228°C and final ice melting temperatures from -5.3° to -1.1 °C, and for more than 50%
of the FIA from -1.5° to -1.1°C. No eutectic temperature was measured. Salinities calculated using the
equation of Bodnar and Vityk (1994) range from 1.8 to 8.2 wt% NaCl eq. and more than 60% of the
FIA present salinities between 1.8 to 2.6 wt% NaCl eq. (Fig. 4E). Raman spectroscopy cannot be used
on opaque mineral-hosted fluid inclusions and content of CO2 in the enargite-hosted fluid inclusions
could not be determined, Since no CO2 clathrate was recognized, potential CO2 contents should be
below 1.75 mol.%. CO2 content may potentially affect the calculated salinity and therefore the element
concentrations determined by LA-ICP-MS.
P-T conditions
No boiling assemblage was observed during the present study, making impossible precise
determination of entrapment pressure. Minimal entrapment pressure based on fluid density was
calculated using the BULK software (Bakker 2003) with the equations of Zhang and Frantz (1987)
and Bodnar and Vityk (1994). For all mineralization stages, the majority of the minimum entrapment
pressures are between 5 and 65 bar. Such pressures are consistent with the present depth of the
samples (0 to 900 m) and an erosion of less than 1 km since the ore deposit formation (Baumgartner et
al., 2008, Rottier et al., 2016b). High-temperature and saline FIAs of mineralizing stage B1 (deep
pyrite-quartz veins) record minimum entrapment pressure from 89 to 173 bars corresponding to a
minimum formation depth between 1200 and 2470 m under hot hydrostatic gradient. Considering the
present depth of the samples, more than 1700 m of erosion would be necessary to explain these values.
Assuming lithostatic conditions, a minimum depth of formation from 330 to 650 m is sufficient. These
FIAs indicate that suprahydrostatic to lithostatic conditions were reached in the deep portion of the
system at Cerro de Pasco during the lifespan of the epithermal system.
232
Minimum entrapment pressure estimations for CO2-bearing fluid inclusions of stage C2 have
not been calculated because no equation of state exists for CO2-bearing fluid inclusions below 300°C.
Element concentrations in fluid inclusions
The average element concentrations and corresponding ratios ([X]/(Na+K+Mn)) with their
standard deviation determined for all FIAs by LA-ICPMS are reported in supplementary Table A.2
and A.3 and in Fig. 10. As most metal contents in the FIAs do not correlate with homogenization
temperature but with salinity, results are only plotted in diagrams concentration vs. salinity (Fig. 10),
except for Ag and Sb where also a correlation with temperature has been recorded (Fig. 11). Within
each mineralization stage (A, B1, B2, C1, and C2) the values are ordered according to decreasing
salinity from left to right. Quartz- and enargite-hosted FIAs from stage C2 have been separated for
clarity. Lithium, B, Na, K, Mn, Rb, Sr, Ag, Cs, Ba, Pb, and Bi are present in detectable concentrations
in all analyzed FIAs. Iron, Cu, and Zn concentrations in sphalerite-hosted FIAs and Cu, Sb, As, and Fe
concentrations in enargite-hosted FIAs could not be detected due to their high concentration in the
respective host minerals, whereas they were detectable in quartz-hosted FIAs. Sulfur, Ca, Cd, Te, and
Tl and Si, Ca, Cd, Te, and Tl were systematically below the limit of detection for respectively quartz-
hosted, and for sphalerite- and enargite-hosted FIAs.
For almost all analyzed elements, there are no or slight differences in concentrations and ratios
([X]/(Na+K+Mn)) for FIAs of similar salinity from the different mineralization stages, and also for
FIAs hosted in quartz and sphalerite (Fig. 10). Sodium, K, Rb, and Sr contents decrease with salinity
whereas the ratios ([X]/(Na+K+Mn)) tend to be constant. The Mn, Fe, Zn, Pb, Sb, Bi, and Cu contents
and ratios generally tend to decrease with salinity (Fig. 10). The Li, B, and Cs contents and ratios do
not present any correlation with salinity and tend to be constant (Fig. 10).
Antimony contents decrease with homogenization temperature for stages A, B1, C1 and C2
(Fig. 11), and not or little with salinity decrease, suggesting that in the considered temperature interval
(300-200°C) Sb is transported as hydroxide species rather than chloride complexes (Pokrovski et al.,
2006; Catchpole et al., 2015a). Silver concentrations in FIAs from stages A, B1 and B2 range between
5 and 500 ppm (measured mainly in quartz). In stage C1, silver concentrations in sphalerite-hosted
FIAs that decrease with homogenization temperature, whereby the highest value (1.5 wt% Ag)
probably corresponds to solid sulfosalt inclusions (Fig. 11).
Enargite-hosted compared to quartz-hosted FIAs from stage C2, present higher concentrations
and ratios [X]/(Na+K+Mn) for all analyzed elements except for Na and B. Enargite-hosted FIAs show
high metal (Ag, Pb, and Bi) concentrations and concentration ratios, with Ag/(Na+K+Mn) up to 26,
Pb/(Na+K+Mn) up to 0.65 and Bi/(Na+K+Mn) up to 0.07 (Fig. 10). We consider at least part of these
values as too high to be realistic. Similar high Ag concentrations and Ag/(Na+K+Mn) concentration
ratios were observed in fluid inclusions hosted in enargite at Butte by Ortelli (2015); she interprets
233
these high values as the result of trapped small unidentified solid inclusions of Ag-bearing sulfosalt in
the analyzed fluid inclusions. We also consider that our high Ag, Pb, and Bi concentration are linked
to the presence of small unidentified solid inclusions of Ag-Pb-Bi sulfosalt trapped in the analyzed
fluid inclusions, and therefore that they are not representative of the mineralizing fluid. Obtained alkali
(Li, Rb, Sr, Ba, and Cs) concentrations from the FIAs hosted in enargite, not affected by the
potentially trapped sulfosalt inclusions are higher than in quartz-hosted FIAs of stage C2 but similar
than the ones obtained from FIAs of the other stages (A, B1, B2 and C1; Fig. 10). These differences
might be due to the lack of CO2 correction for enargite-hosted compared to quartz-hosted FIAs
inducing an overestimation of the salinity, but this hypothesis does not explain the difference observed
also in the element ratios [X]/(Na+K+Mn). The petrography study shows that quartz precipitates
before enargite, and therefore they could have trapped different fluids with different compositions.
234
235
236
Figure 10: Element concentrations and element ratios X/(Na+K+Mn) for studied fluid inclusion assemblages from the
epithermal ore-bodies at Cerro de Pasco. Within each mineralization stage (A, B1, B2, C1, and C2) the values are ordered
according to decreasing salinity from left to right. Quartz- and enargite-hosted FIAs from stage C2 have been separated
for clarity. Same color codes are used in the following figures. (*) Values for Ag, Bi, and Pb are considered to be
unrealistic, see text. All results are available in supplementary Table A.3 and A.4
Figure 11: Ag and Sb concentrations and element X/(Na+K+Mn) ratios for the studied fluid inclusion assemblages.
Within each mineralization stage (A, B1, B2, C1, and C2) the values are ordered according to decreasing homogenization
temperature from left to right. Quartz- and enargite-hosted FIAs from stage C2 have been separated for clarity. All results
are available in supplementary Table A.3 and A.4
Trace elements in sulfides
Sphalerite from stages A and C1, pyrite from stage B2, C1, and C2 and enargite from stage C2
were analyzed by LA-ICP-MS to determine their trace element contents. For sphalerite and enargite,
host compositions obtained during the treatment of the LA-ICP-MS signals of fluid inclusions were
also considered. In-situ LA-ICP-MS analysis allows the quantification of a large set of trace and minor
elements at low to very low concentrations. Limiting factor of such method is the low spatial
resolution (tens of micrometers), not allowing determination of whether a particular trace element is
incorporated into the mineral structure or if it is present as micro- or nano-scale solid inclusions (e.g.,
Deditius et al., 2011, Pačevski et al., 2012). Electron microprobe data for sphalerite of stages A, B2
and, C1, are reported in supplementary Table A.4. Additional EMPA data for sphalerite of stages A
and C1 and for pyrite of stage C2 have been published by Einaudi (1968a, 1968b, 1977) and
Baumgartner et al. (2008).
Sphalerite
In total 282 analyses of sphalerite were performed: 95 from 7 different samples for stage A
and 187 from 13 different samples for stage C1 (size of the sphalerite grains occurring in stage B is too
237
small for LA-ICP-MS analysis). The results are summarized in Figure 12 and all data are available in
supplementary Table A.5. For most analyzed elements LA-ICP-MS transient signals of sphalerite from
both stages stay flat with time and present no spikes. Only Sn, Sb, Pb, and Ag present occasionally
spiky LA-ICP-MS transient signals.
Figure 12: Trace element composition (in ppm) of sphalerite from stages A and C1. The circles are the mean values and
dots are individual analyses; the gray lines represent the range of values, and the black horizontal line the mean LOD. All
results are available in supplementary Table A.5
Sphalerite from both stages yield mean values > 10 ppm for Mn, Cu, Ga, Ag, In, Sn, Sb, and
Pb, whereas the mean values of As and Hg (between 10 and 1 ppm) and V, Co, Ni, Mo, Te, W, Tl, and
Bi (< 1 ppm) are lower (Fig.12). The main differences between sphalerite from stages A and C1 are the
higher Mn, Ag, Sb, and Pb and the lower Fe and Cu contents of sphalerite from stage C1 and the
existence of a large number of samples with Fe contents below 1000 ppm where the stage A sphalerite
contains Fe in the percent range (Fig. 12; Table A.4). Manganese and Fe contents display a positive
correlation for sphalerite from both stages (Fig. 13A). Cadmium contents display a double correlation
with Fe, it shows a negative correlation from 100 to 3000 ppm Fe and then it presents a positive
correlation from 3000 ppm to 15 wt% Fe (Figs. 8A and 13B). Lead concentration is more elevated in
sphalerite from stage C1, up to 2080 ppm (Fig. 12). Sphalerite from both mineralization stages (A and
C1) display a positive correlation between their Sb and Pb contents and for sphalerite from stage C1 a
rough positive correlation between Ag and Pb exits (Figs. 13C and D).
238
Figure 13: Correlation diagrams of various trace-elements in sphalerite from stages A and C1: A) Mn - Fe; B) Cd - Fe; C)
Ag - Pb; D) Sb - Pb; E) Cu+Ag – Sn+In; F) Cu+Ag – Sn+In+Ga. Published data from distal Pb-Zn skarn and epithermal
Au deposits from Cook et al. (2009) are plotted for comparison. All results are available in supplementary Table A.5
Enargite
A total of 71 LA-ICP-MS trace element analyses were performed in enargite from three
samples of mineralization stage C2. Results are summarized in Figure 14 and all data are available in
supplementary Table A.6. For most analyzed elements LA-ICP-MS, transient signals stay flat with
time and present no spikes. Some elements (Te, Bi, and Pb) show smooth count variations, indicating
minor chemical zonations. The most common minor and trace elements in the analyzed enargite
samples are Sb (up to 65’000 ppm), Sn (up 5’700 pm), and Te (up to 2’300 ppm). The samples yield
also mean values > 10 ppm for Mn, Fe, Zn, Ag, Hg, Pb, and Bi, whereas the mean values of Na and
Cd (between 10 and 1 ppm) and Au and Tl (< 1 ppm) are lower (Fig.14). A good positive correlation
exists between Sn and Sb contents (Fig. 15A) whereas Ag and Te contents show a rough positive
239
correlation (Fig. 15B). When Sn content is superior to 100 ppm, it shows a clear positive correlation
with Zn + Pb (Fig. 15C).
Figure 14: Trace element composition (in ppm) of enargite from stage C2. The circle corresponds to the mean value and
empty circles - to individual analyses; the gray lines represent the range of values, and the black horizontal line the mean
LOD. All results are available in supplementary Table A.6
Figure 15 : Correlation diagrams of various trace elements in enargite from stage C2: A) Sb - Sn; B) (Pb+Zn) - Sn; C) Ag
- Te; D) Bi – Au. Published data on trace element concentrations in enargite from high-sulfidation epithermal
mineralization are plotted for comparison. All results are available in supplementary Table A.6
240
Pyrite
LA-ICP-MS spot analyses of stage B2 pyrite (n=32) have been previously published (Rottier et
al., 2016a). In the present work, pyrite from stages C1 (5) and C2 (15) have been analyzed. The result
are available in supplementary Table A.7 and in Figure 16 that does not include LA-ICP-MS spot
analyses of pyrite and marcasite that replaced during stage B1 pyrrhotite and arsenopyrite from the
pyrrhotite pipes and their Pb-Zn rims (stage A) reported by Rottier et al. (2016a) because the values
depend largely on the replaced mineral.
Figure 16: Trace element composition of pyrite from stage B2, C1, and C2. The circles are the mean values and unfilled
circles are individual analyses; the gray lines represent the range of values, and the black horizontal line the mean LOD.
All results are available in supplementary Table A.7
Trace element compositions of pyrite from stages B2, C1 and C2 show important differences
(Fig. 16). LA-ICP-MS transient signals obtained from pyrite of stage B2, display a stable and flat
pattern for As, and spiky patterns for Pb, Sb, Ag, and Bi. For the majority of analyses, Pb, Sb, Ag, and
Bi signals on the LA-ICP-MS transient signals are parallel. Pyrite of stage B2 shows high values for Pb
and Sb (up to 521 and 147 ppm, respectively), and displays positive correlations between Pb and Sb
(Fig. 17A), Pb and Bi, Sb and Bi, Ag and Sb, Ag and Pb, and, Ag and Bi (not shown).
LA-ICP-MS transient signals obtained from pyrite of stage C1, are stable and generally flat
with time for As, Sb, Tl, Ag and In, and strongly spiky for Pb. Pyrite from stage C1 compared to pyrite
from the others stages (B2 and C2) is enriched in Tl, Sb and In and poor in Au, Bi, Co, Ni, and Cu (Fig.
17). Clear positive correlations between Tl and As, Tl and Sb, and, Sb and As exist (Fig. 17).
241
Figure 17: Correlation diagrams of various trace elements in the studied pyrite from stage B2, C1 and C2: A) Sb - Tl; B) Sb
- Pb; C) Bi - Pb; D) Sb - Ag; E) Cu - Ag; F) Cu – Bi; G) Au-As. The red line corresponds to the solubility limit of Au as a
function of As concentrations, as determined by Reich et al. (2005). H) Au – Bi.
242
LA-ICP-MS transient signals obtained from pyrite of stage C2 are stable and stay flat with
time for Cu, Bi, Ni, and Co and present a more spiky pattern for As Sb, Te, Ag, and Pb. The LA-ICP-
MS analysis confirm the high Cu contents of C2 pyrite (up to 1.8 wt. %), already reported, based on
EMPA analyses, by Einaudi (1968b) and by Henry (2005). The gold concentration is around 1 ppm
and shows a positive correlation with Bi (Fig. 17H) but no correlation with As (Fig. 17G). Lead
concentration correlates positively with Bi (Fig. 17C) and to a lesser extent with Sb. Silver shows
rough positive correlations with Sb, Te, and As (not shown).
Discussion
Fluid mixing and origin of the mineralizing fluids
Stages A, B1, B2 and C1

Important fluid salinity variations from 20 to 3 wt% NaCl eq. with no significant temperature
loss for stages A, B1, and B2, can be explained by mixing of two fluids of different salinity having
similar temperatures, or by phase separation. Since no evidence of phase separation like “boiling
assemblages”, vapor-rich inclusions, and of mineral textures indicators of boiling (e.g., Morisson et
al., 1990; Dong et al., 1995; Moncada et al., 2012) were observed, the former hypothesis is preferred,
although "gentle boiling" in the sense of Moncada et al. (2012) cannot be fully excluded. For stage C1,
salinity from 18 to 1 wt% NaCl eq. and homogenization temperature variations (280° to 150°C) are
best explained by mixing of a “high-salinity” fluid with a cooler and lower-salinity fluid. Therefore,
we suggest that the observed variations of salinity in FIAs from mineralization stages A, B1, B2, and C1
are mostly due to mixing of (i) a high-salinity metal-rich fluid and (ii) a low-salinity less metal-rich
fluid. The low-salinity fluid was at similar temperature as the high-salinity fluid for mineralization
stages A, B1, and B2 and at lower temperature for mineralization stage C1. FIAs from these
mineralization stages (A, B1, B2, C1) display similar progressive decreases of metal and alkali
concentrations with salinity and most metal (Mn, Fe, Cu, Zn, Sb, Pb) concentration ratios
([X]/(Na+K+Mn)) also decrease with salinity (Fig. 10).
In-situ SIMS oxygen isotope analyses performed by Rottier (2017) on eight quartz crystals
from mineralization stages A, B1, and B2 indicate heavy oxygen isotopic signatures: δ18Oquartz = 16.2 ‰
for stage A (median of n = 30, 1σ = 1.6); δ18Oquartz = 14.0 ‰ for stage B1 (median of n = 56, 1σ = 1.9);
δ18Oquartz = 15.3 ‰ for stage B2 (median of n = 30, 1σ = 2.0). The corresponding δ18O of water in
equilibrium with the quartz crystals is δ18Ofluid equal to 7.3, 5.1, and 6.4 ‰ respectively for stage A, B1,
and B2 (calculated at 250°C; using the equation of Zheng 1993). Baumgartner et al. (2008) also
reported similar heavy oxygen isotope signatures from bulk analyses of hydrothermal quartz from
stage A (δ18Oquartz = 15.3 and 15.8‰) and B2 (δ18Oquartz = 16.0 - 17.2‰, n=3). Considering a local
Miocene meteoric water oxygen isotopic composition of -13 ‰ (Baumgartner et al., 2008) and a local
magmatic water of ~ 9‰ (Rottier et al., 2016b, submitted and Rottier 2017), the oxygen isotopic
243
signature of quartz of stages A, B1 and B2 can be considered as dominantly magmatic with only a
minor, < 20 wt%, meteoric input. Therefore, the salinity variations observed in FIAs from stages A, B1
and B2 cannot be explained by mixing with meteoric water because they would require a
meteoric/magmatic water ratio close to 8:1, incompatible with the stable isotope results. The heavy
oxygen isotopic signatures of quartz are also unlikely to be due to mixing with equilibrated meteoric
water considering the high water/rock ratios necessary to form the ore-bodies (Rottier, 2017).
Therefore, (i) the heavy oxygen isotopic signature of quartz, (ii) the fact that no decrease of
homogenization temperature with salinity is recorded in the FIAs, and (iii) the high metal
concentrations of the FIAs with the highest salinity (up to several wt% of Mn, Fe, Zn, and Pb and up
to several 1000s of ppm of Cu and Sb; Fig. 10) allow suggesting that mineralization stages A, B1, and
B2 were formed by mixing of a high-salinity metal-rich magmatic fluid and a low-salinity less metal-
rich fluid also of magmatic origin, likely a condensed vapor or an intermediate-density fluid. For
mineralization stage C1, the observed clear decrease of homogenization temperature with salinity (Fig.
4D) and the existing oxygen and hydrogen isotopic data on hypogene kaolinite and oxygen isotopic
data on quartz (Baumgartner et al., 2008) point to mixing between magmatic and meteoric fluids.
Considering that the high metal concentrations of the FIAs with the highest salinity are similar to those
from stages A, B1, and B2, we suggest that during stage C1 mixing between hypersaline magmatic
fluids and meteoric water took place. However, the presence of mineral assemblages (e.g., famatinite-
alunite-kaolinite) in the core of stage C1 replacement bodies requires very acidic (pH <2) and high-
sulfidation state conditions (Baumgartner et al., 2008). They cannot be met with only mixing of
hypersaline magmatic fluids and meteoric water and we propose that condensed magmatic vapor or an
intermediate-density magmatic fluid, as identified for stages A, B1, and B2, is also involved.
Hypersaline inclusions (salinity > 45 wt% NaCl eq.) have been observed in the veins from the
different porphyry-type mineralization events (PM1, PM2 and PM3; Rottier et al., 2016b and
submitted; Rottier 2017) spatially and broadly temporally linked to the epithermal polymetallic deposit
(Figs. 1 and 2). The Pb/Zn ratios (LA-ICP-MS data) of these hypersaline inclusions (~ 0.3; Rottier et
al., 2016b and submitted; Rottier 2017) are similar to those of the bulk polymetallic mineralization
(~0.3; Baumgartner et al., 2008), and close to the Pb/Zn ratio of the analyzed FIA (~0.4;
FIA#:BR_12_5_1, stage B1) with the highest Zn (2.7 wt%) and Pb (1.1 wt%) contents that is
considered to be the best approximation for the high-salinity end-member fluid. These similarities do
not imply a direct genetic link between the identified porphyry-type mineralization events and the
mineralization stages of the large polymetallic deposit but they evidence that Cerro de Pasco magmatic
system was able to generate episodically magmatic brines, similar to those at the origin of the
polymetallic mineralization. In addition, numerical modeling of magma chambers emplaced at shallow
to moderate level (from 2 to 4 km depth) suggests that most of the chlorine expulsed from a magmatic
intrusions is stored at depth as hypersaline fluids or solid halite in primary and secondary (e.g., cracks)
rock porosities, after phase separation (Weis et al., 2012; Gruen et al., 2014; Blundy et al., 2015; Scott
244
et al., 2017). The presence of stored hypersaline fluids in pores and cracks in the upper part of young
and hot felsic bodies found by deep drilling in the Kakkonda (Japan; Kasai et al., 1998) and the
Larderello (Italia; Valori et al., 1992) geothermal fields can be considered as a direct evidence for such
phenomenon. Extensive formation of hypersaline fluids at around 2 to 4 km depth allows partition of
large amounts of Zn, Pb, Fe and other metals in the chlorine-rich phases during phase separation.
Tapping of these stored metal-rich saline fluids by low-salinity fluids, i.e., “brine mining”, has been
proposed by Simmons (1991) and Wilkinson et al. (2013) at the Fresnillo epithermal Ag-Pb-Zn
deposit and by Gruen et al. (2014) at the Brothers volcano submarine hydrothermal system. Gruen et
al. (2014) model suggests that only fluids that, after mixing, have bulk salinities lower than 20 wt%
NaCl can be mobilized to shallow levels whereas fluids with higher salinities, more dense, stay at
depth. This threshold value of 20 wt% NaCl is similar than the highest salinity observed in the studied
FIAs at Cerro de Pasco.
Therefore, we suggest that the saline (up to 20 wt% NaCl eq.) metal-rich magmatic fluids
identified at Cerro de Pasco result from episodic dilution of stored hypersaline porphyry-type fluids
previously generated by phase separation at the upper part of a magmatic intrusion (Fig. 18 and 19)
We propose that the relatively low salinity (~3 wt% NaCl eq.) and low metal content (10s to 100s
ppm) magmatic fluid end-member, interpreted as magmatic vapor-like, episodically mobilized the
stored hypersaline fluids. The resulting mixed fluids rose to form the mineralization stages A, B1, B2,
and C1 (Fig. 18 and 19). The progressive salinity decrease with time detected in some quartz crystals
from stage B2 and sphalerite from stage C1 (Fig. 7) suggests local exhaustion of the hypersaline fluid
reservoir along the magmatic vapor-like fluids up-flow zone. Considering the highest Zn (2.7 wt%)
and Pb (1.1 wt%) contents measured in the studied FIAs as the best proxies for the metal content of
the stored high-salinity magmatic fluid at depth (which should be around two times metal-richer
because the measured FIAs record already diluted fluids) and assuming 50% metal precipitation
efficiency, a volume of 1 km3 of this high-salinity metal-rich fluid is sufficient to form the giant
epithermal polymetallic mineralization at Cerro de Pasco (200 Mt resource at 7 wt% Zn and 2 wt%
Pb; Baumgartner et al. 2008, Rottier et al., 2016a).
Stage C2
In contrast to the other mineralization stages, formation of the W-E trending enargite-pyrite
veins of stage C2 characterized by CO2-bearing quartz- and enargite-hosted FIAs with salinity ranging
mainly between 1.2 and 2.7 wt% NaCl eq., does not require mixing with hypersaline fluids (Fig. 4E).
Existing oxygen and hydrogen isotopic data on hypogene alunite and bulk oxygen isotopic data on
quartz (Baumgartner et al., 2008), and in-situ oxygen SIMS isotope analyses by of hydrothermal
quartz crystals from the enargite-pyrite veins (Rottier 2017), suggest a mixing between a magmatic
fluid and meteoric water. Thus, we interpret the mineralizing fluid forming stage C2 as condensed
245
magmatic acidic vapors which did not interact with the stored hypersaline porphyry-type fluids, but
mixed with meteoric waters in the upper part of the system.
Comparison with other Cordilleran polymetallic deposits

The model based on episodic tapping of hypersaline magmatic fluids proposed at Cerro de
Pasco for the stages A, B1, B2 and C1 could be applied to other Cordilleran polymetallic deposits
where saline (up to 20 wt% NaCl eq.) metal-rich fluids were observed, such as at the Julcani Ag-Cu-
Pb-W-Bi-Au deposit (Peru; Deen et al., 1994), Uchucchacua Ag-Mn-Pb-Zn deposit (Peru; Bussel et
al., 1990), Fesnillo (Wilkinson et al., 2013) and many other Mexican Zn-Pb-Ag epithermal deposits
(Camprubi and Albinson 2007). Nonetheless, the proposed model is possibly not applicable to some
Cordilleran polymetallic deposits, such as Morococha (Catchpole et al., 2011 and 2015) and Butte
(Rusk et al., 2008a; Ortelli 2015), where salinities measured in fluid inclusions do not exceed 8 wt%
NaCl eq. These authors proposed that the polymetallic epithermal mineralization at Morococha and
the Butte Main Stage veins are formed by cooling of intermediate-density porphyry-type fluids. Thus
the proposed “brine mining” model is not a prerequisite to the formation of all polymetallic
Cordilleran deposits. Morococha and Butte are telescoped porphyry systems whereas at Cerro de
Pasco and in the Mexican deposits where “brine mining” is proposed, no evidence of significant
telescoping was found. It can be hypothesized that telescoping, typically related to dynamic
environments, does not allow storage of hypersaline fluids at depth.
246
Figure 18: Sketch with time and space evolution of mineralization at Cerro de Pasco. A) Formation and storage of
hypersaline and metal-rich magmatic fluids above numerous porphyry stocks. B) Formation of stage A: emplacement of a
new porphyry stock exsolving magmatic vapor or intermediate density fluids interacting with the stored hypersaline fluids,
fluid resulting of the mixing will form the pyrrhotite pipes and their Zn-Pb rims. Low sulfidation assemblages are
explained by interaction of the fluids with Excelsior shales and slates. C) Formation of stage B, following a similar
process than for stage A, reduction by the Excelsior shales and slates is less intense. D) Formation of stage C1 and C2:
reactivation of previous tectonic structures, stage C1 is formed by a similar process than stage A and B, but ascending
mixed fluid will be diluted by meteoric water in the upper level of the system. Stage C2 is formed by direct ascent of the
low-salinity CO2-bearing contracted magmatic vapor which doesn’t interact with stored hypersaline fluids. Exsolved low-
salinity CO2-bearing contracted magmatic vapor is mixed with meteoric water in the upper part of the system.
247
Figure 19: A) Schematic model of local tapping of the stored hypersaline fluid reservoir by vapor-like magmatic fluid (cf.
Fig. 18). B) Schematic evolution of fluid salinities and metal concentrations for stage A, B1, B2 and C1 in response to the
episodic local tapping of the stored hypersaline fluids reservoir. In stage C2 (not represented) there is no evidence of
tapping of the hypersaline fluid reservoir (see Fig. 18).
Fluid evolution and nature of the mineral assemblages

The parallel changes of absolute element concentrations and of concentration ratios
([X]/(Na+K+Mn)) in the analyzed FIAs indicate that the compositional changes are mainly caused by
combination of dilution and precipitation of minerals. Some of these concentration and concentration
ratio ([X]/(Na+K+Mn)) drops could be associated to minerals precipitation, like the drop by up two
orders of magnitude of Pb and Sb during stage A, and of Fe, Cu, Zn, Pb, and Sb during stage B1, due to
precipitation of galena and Sb-bearing sulfosalts (stage A) and of pyrite, chalcopyrite, sphalerite,
galena, and tennantite-tetrahedrite (stage B1). For stage B2, LA-ICP-MS analyses reveal elevated Fe
concentrations (> 1.8 wt%) for the FIAs with the highest salinity. For FIAs with salinity below 10
wt% NaCl eq., Fe concentrations are one order of magnitude lower and are relatively constant (Fig.
10). This Fe concentration drop could record period of massive pyrite precipitation followed by a
period of no-sulfide precipitation, due to exhaustion of reduced sulfur in the mineralizing fluid. In the
studied FIAs, Cu and Zn concentration variations are moderate, of less than one order of magnitude
248
(Fig. 10). This indicates limited or absence of chalcopyrite and sphalerite precipitation, hypothesis
coherent with petrographic observations. At the conditions prevailing during stage B2, the elevated Cu
and Zn concentrations recorded in FIA, up to 700 and 8000 ppm, respectively, would be above the
saturation level if the fluid was rich in reduced sulfur (Kouzmanov and Pokrovski 2012). The absence
of significant chalcopyrite and sphalerite precipitation in stage B2 indicates exhaustion of reduced
sulfur in the mineralizing fluid. In stage C1, the Sb and Ag concentrations and concentration ratios
([X]/(Na+K+Mn)) decrease with that of homogenization temperatures (Figs. 10 and 11), is likely
linked to Sb-Ag sulfosalt precipitation, in concordance with petrographic observation.
In contrast with the metals mentioned above, elements not or only slightly affected by sulfide
precipitation such as Li, B, Na, K, Mn, Rb, Cs, and Ba display concentration decreases with salinity
but keeping the concentration ratios almost constant for FIAs from stages A, B1, B2, and C1. This
suggests that their concentration variations result from to the dilution process.
LA-ICP-MS analyses of the FIAs of similar salinity from mineralization stages A, B1, B2, and
C1, have close or similar concentrations for most of the analyzed elements. These data indicate that a
high-salinity metal-rich fluid end-member of remarkably similar composition is at the origin of the
mineralization stages A, B1, B2 and C1. This similarity contrasts with different mineralogical
assemblages spanning from low- to high-sulfidation conditions and the different metal endowment of
these stages. It suggests that the mineralogical and geochemical differences observed are not due to
fluid composition changes (except probably S content, which has not been determined in the present
study), and are rather attributed to changes in pH, fO2 and fS2 of the ore-forming fluids, largely triggered
by the mixing processes discussed above. In addition, during all stages except C2, a strong interaction
of the mineralizing fluids with the host rock is recorded. As proposed by Baumgartner et al. (2008),
Rottier et al. (2016a), and Rottier (2017), mineral assemblages from stage A to stage C1 are indicative
of an increase of fO2 and fS2, following a progressive interaction decrease with the reduced bituminous
shales and slates of the Excelsior Group (Fig. 19; Baumgartner et al., 2008; Rottier et al., 2016a;
Rottier 2017). Interaction with carbonate rocks of the Pucará Group also contributes to the
mineralogical zoning that characterizes the ore-bodies of stage A and C1 (Baumgartner et al., 2008).
Trace elements in sulfides

Sulfides and sulfosalts may contain low to moderate concentrations of numerous “critical” elements
such as Ga, Ge, Au, Ag, Te, In, Sb, Tl, Cd, These elements may significantly increase or decrease the value of
the ore concentrate (e.g., Fontboté et al., 2017). Incorporation of a specific element in sulfides/sulfosalts
structure depends of the interplay of several factors such as temperature, fO2, pH, fs2 and fluid
composition. Moreover, only elements directly incorporated into the sulfide structure can be used to
infer fluid characteristics. As shown above for the different mineralization stages, the temperature
range is similar (mainly between 220° to 280°C) except the lower temperature recorded in stage C1
(down to 150°C). All stages, except C2, are formed by dilution of a saline (up to 20% NaCl eq.) and
249
metal-rich fluids. Despite these similarities, the LA-ICP-MS results show important differences in the
trace element composition of sphalerite, pyrite and enargite. These variations are mainly due to
different fO2, pH, and fs2 conditions prevailing during the low sulfidation stage A, intermediate
sulfidation stage B and the high to intermediate (partly also low) sulfidation stage C. Therefore, a
direct relationship between fluid composition recorded in the FIAs and the measured trace element
composition of sphalerite, pyrite and enargite cannot be expected. Indeed, as discussed below,
potential correlation between fluid and trace element composition could only be detected in few cases,
and even so, ambiguity remains.
Sphalerite. Compared to sphalerite compositions from different skarn and epithermal deposits
reported by Cook et al. (2009), sphalerite from stages A and C1 at Cerro de Pasco presents lower trace
elements contents except for Ga, Ge, In, Sn, and Ag whose concentrations are in the same order of
magnitude. In the analyzed sphalerite, values (mol/t) of (Cu+Ag) vs those of (Sn + In) and of (Sn + In
+ Ga) plot along the 1:1 line (Figs. 13E and F) due to coupled substitutions (2Zn2+) ↔ (X++Y3+) and
(3Zn2+)↔(2X++Z4+), with X: Ag+ or Cu+; Y: In3+ or Ga3+ and Z: Sn4+ or Ge4+, as already proposed by
Murakami and Ishihara (2013) and Belissont et al. (2014). Thus, we propose for the analyzed samples,
that Cu, Ag, In, Sn, and Ga are mostly incorporated into the sphalerite structure. The lack of similar
correlations for the sphalerite compositions compiled from Cook et al. (2009) may suggest that their
results were affected by solid inclusions hosted in sphalerite (Figs. 13E and F). It is generally accepted
that Pb is preferentially hosted in solid inclusions (galena and/or sulfosalts) rather than in the structure
of sphalerite (e.g. Cook et al., 2009, Ye et al., 2011, Lockington et al., 2014). The good correlation
between Sb and Pb recognized for sphalerite from both stages A and C1 suggests the presence of
micro- to nano-scale solid inclusions of Sb-Pb sulfosalt in sphalerite, that are likely more abundant in
stage C1 owing the one order of magnitude larger Pb and Sb contents in sphalerite from this stage.
Silver content in sphalerite from stage C1 shows a rough correlation with Pb (Fig. 13C), which could
indicate that in addition to silver incorporated in the structure, part of the silver might be located in
micro- to nano-scale inclusions of Ag-bearing Pb-Sb sulfosalts.
Sphalerite from stage A presents higher Fe, Cd, and Cu and lower Mn, Ag, Sb, Pb and Bi
concentrations than sphalerite from stage C1, whereby values of stage C1 show, in general, a larger
spread. Only elements incorporated into the structure (Fe, Mn, Cd, Cu, Ag, Ga, and Sn) could be used
to infer fluid characteristics. It is well known that Fe content of sphalerite depends mainly of fs2 and
temperature variations (e.g., Lusk and Calder 2004), These parameters explain the relatively
homogenous and high Fe-content of sphalerite from stage A precipitated by reduced fluid at
temperature between 280 and 220°C (Fig. 4A; Rottier et al., 2016a) and the larger spread of Fe content
observed in sphalerite from stage C1 precipitated from fluids shifting from reduced conditions and
temperatures up to 280°C toward oxidized, acidic and lower temperature conditions (down to 150°C;
Fig. 4C and 8). The good positive correlation of Fe and Mn (Fig. 13A) indicates that both elements
250
behave similarly. The higher Mn concentrations and the larger spread observed in sphalerite from
stage C1 compared to the one from stage A is not reflected by the fluid composition recorded by
sphalerite-hosted FIAs yielding similar Mn contents in both stages (Fig. 10). This suggests that Mn
incorporation into the sphalerite structure, similar to Fe, largely depends on fs2 and temperature, and
that Mn concentration in the fluid has only a limited effect. The striking double correlation, positive
and negative, of Cd and Fe contents (Fig. 13B) suggests that different factors influence its
incorporation in the sphalerite structure. On the one hand, in the low-temperature and Fe-poor rims of
zoned sphalerite crystals of stages C1, Cd negatively correlate with Fe (Figs. 8 and 13B), which is
compatible with observations in other deposits that low-temperatures favor Cd incorporation (e.g., Ye
et al., 2011). On the other hand, the positive correlation between Cd and Fe contents observed in Fe-
rich sphalerite of stages A and C1 (Fig. 13B), suggests that reduced conditions favors Cd incorporation
in sphalerite. Silver is the only element where a correlation between its higher contents in FIAs and as
trace element in sphalerite has been recognized. This correlation is not conclusive because, as
discussed above, part of the Ag is hosted in nano-scale solid inclusions. Factors controlling
incorporation of Cu, Ga and Sn in the sphalerite structure cannot be discussed because they do not
correlate with Fe, proxy for temperature and fs2, and they have not been detected in sphalerite-hosted
FIAs.
Pyrite. Pyrite from the three stages displays contrasting trace element compositions (Figs. 16 and 17).
As already suggested by Rottier et al., (2016a) for pyrite of stage B2, the positive correlation between
Pb, Sb, Ag, and Bi concentrations, and the spiky patterns of LA-ICP-MS transient signals for these
elements suggest presence of micro- to nano-scale Pb-Sb-(Bi)-(Ag) sulfosalts inclusions. The clear
positive correlations between Tl and As, Tl and Sb, and Sb and As in pyrite from stage C1, suggest the
presence of micro- to nano-scale Sb-As-Tl sulfosalt inclusions. However, incorporation of these three
elements into the pyrite structure cannot be fully discarded, considering that substitution of S by Sb
and As favors the incorporation of Tl in the pyrite structure (Deditius and Reich, 2016). The high Tl
content (up to 450 ppm) in C1 is not fully understood because no Tl was detected in the fluid
inclusions (LOD < 1ppm). Pyrite from stage B2 is enriched in Bi and depleted in Tl, Sb, Ag, and Pb
compared to pyrite from stage C1. Insight to the composition of the mineralizing fluids forming pyrite
from these stages may be given by LA-ICP-MS analyses of FIAs hosted in quartz from stage B2 that
are enriched in Bi and depleted in Sb, Ag, and Pb compared to sphalerite-hosted FIAs from stage C1.
Therefore for pyrite of both stages a paralle between Bi, Sb, Ag and Pb concentration in pyrite and the
hydrothermal fluids could be drawn. As most of these elements may also reside in solid inclusions any
conclusion should be taken with caution.
Pyrite from stage C2 differs of the pyrite from the two other stages by its higher Cu (up to 1.8
wt%), Bi, Te, Ag and Au content. Copper concentration shows no clear correlation with other
analyzed elements which favor the hypothesis proposed by Einaudi (1968b) that Cu is structurally
251
bounded replacing Fe in the octahedral sites of the pyrite structure; Cu might be also present as micro-
to nano-scale Cu or Cu-Fe sulfide inclusions which are not discernable by LA-ICP-MS analyses
(Deditius et al., 2011). Good correlations between As, Sb, Bi, Te, Ag, and Pb, content in pyrite from
stage C2 as well as spiky LA-ICP-MS transient signals of these elements possibly indicate the presence
of micro- to nano-scale solid inclusions of Ag-Sb-Te-As and Pb-Sb-Bi sulfosalts. As metal
concentrations of enargite-hosted FIAs are clearly discriminated by the presence of solids trapped in
the fluid inclusion cavities (see above) and quartz from this stage (hosting particularly metal-poor
FIAs) predates pyrite precipitation both enargite- and quartz-hosted fluid inclusions cannot be used as
proxies for the mineralizing fluids precipitating pyrite. However, composition of stage C2 pyrite shares
common features (high Cu, Ag, Co, Ni, Se, Bi and Te) with pyrite from other high-sulfidation deposits
formed by low-density fluids (Fig. 13; Kouzmanov et al., 2010; Maydagan et al., 2013; Reich et al.,
2013; King et al., 2014 and Franchini et al., 2015). This similarity could be due to the fact that these
ore type in various magmatic-hydrothermal systems is formed by similar hydrothermal fluids: an
acidic CO2-bearing low-salinity magmatic fluids interpreted as condensed magmatic vapor or directly
ascending intermediate-density fluids (Hedenquist et al., 1998; Heinrich et al., 2004).
Enargite. Compared to the few studies reporting LA-ICP-MS trace element analyses of
enargite (Sutupo et al., 2007; Deyell and Hedenquist 2011; Maydagan et al., 2013; King et al., 2014;
Dekov et al., 2016), enargite from Cerro de Pasco is depleted in Fe, Bi, V, Se and Au and enriched or
having concentrations in the same order of magnitude for Sb, Ag, Sn, Te, Zn, Pb, W, Cd, and Ba. The
negative correlation between As and Sb is coherent with the fact that Sb is incorporated (here up to 6.5
wt%) into the enargite structure replacing As (e.g., Posfai and Buseck, 1998). The positive correlations
between Sn and Sb (Fig. 15A) and, when Sn concentration is > 100 ppm, between Sn and (Zn + Pb)
(Fig. 15B) could result from the substitution Sn4+ + (Zn2+ or Pb2+) ↔ (As5+ or Sb5+) + Cu+; a similar
mechanism for Zn incorporation has been proposed by Deyel and Hedenquist (2011) and also for Fe
incorporation by Kouzmanov et al. (2004), Deyel and Hedenquist (2011), and Borgheresi et al. (2013).
These observations suggest that Sb, Sn, Pb, and Zn are incorporated into the enargite structure. In
contrast, Ag and Te contents result probably from micro- to nano-scale solid inclusions of Te-Ag-
bearing sulfosalt, explaining the higher Ag and Te contents of the Cerro de Pasco enargite compared
to previously published compositions. Gold concentrations in stage C2 enargite (from 0.2 to 1.5 ppm)
are comparable to published compositions elsewhere (Deyell and Hedenquist 2011; Maydagan et al.,
2013; King et al., 2014; Dekov et al., 2016).
Trace element distribution in enargite from the Lepanto high-sulfidation Cu-Au deposit in the
Philippines is attributed to systematic variations in homogenization and ice-melting temperatures
(respectively, salinity) in enargite-hosted fluid inclusions (Deyell and Hedenquist, 2011). In our study,
no correlation between homogenization or ice-melting temperatures measured in enargite-hosted FIAs
and the trace element contents of the host enargite was recognized. Trace element variations in one
252
enargite grain are in the same range as the one of the entire studied set of samples. Only Mn, Ag, Pb
and Bi were above the limit of detection during LA-ICP-MS analyses of FIAs hosted in enargite and
no correlation between their concentrations and the composition of the host enargite could be
established.
Fluid inclusions in ore and gangue minerals

The recorded differences of the microthermometric measurement and LA-ICP-MS analyses in
FIAs hosted in quartz and in enargite of stage C2 (Figs. 4 and10), suggest that quartz and enargite are
formed by different hydrothermal pulses. This finding is consistent with petrographic observation
indicating that quartz precipitates earlier than enargite in the veins. In contrast, our data show no
difference in microthermometric measurements between FIAs trapped in sphalerite and in gangue
minerals (quartz and carbonate) from the carbonate replacement ore-bodies of stages A and C1 (Fig. 4).
Unfortunately, not enough quartz-hosted FIAs from stage A and no carbonate-hosted FIAs from stage
C1, could be analyzed by LA-ICP-MS to allow a comparison between the composition of FIAs hosted
in gangue minerals and sphalerite from these stages. Nonetheless, for a similar salinity, composition of
the sphalerite-hosted FIAs from stage A and C1 is similar to that of the quartz-hosted FIAs from stage
B1 and B2, except for Ag (Fig. 10).
Our LA-ICP-MS analyses of FIAs hosted in opaque minerals allow tracing mineralizing fluid evolution
when transparent minerals were absent and/or not cogenetic with ore-mineral precipitations. This is an additional
example to those presented by Kouzmanov et al. (2010) and Ortelli (2015) of the utility of performing
microthermometric measurement of FIAs hosted in opaque minerals using near-infrared (NIR) transmitted-light
microscopy combined with their LA-ICP-MS analyses if the precautions discussed above are taken.
Conclusions
The different mineralization stages A, B1, B2, C1, and C2 in the giant Cerro de Pasco epithermal
polymetallic deposit, formed in the upper part of a porphyry system, took place at relatively low
temperatures, mainly between 280° and 150°C and mineralizing fluids had variables salinities -
between 19 wt% NaCl eq. and 1.2 wt% NaCl eq. No evidence of phase separation was found in the
studied fluid inclusions. The microthermometric and LA-ICP-MS analyses of fluid inclusions suggest
that mineralization stages A, B1, B2, and C1, were the result of mixing of high-salinity metal-rich fluids
with low-salinity less metal-rich fluids. As supported by stable isotope data for stage A, B1, and B2,
both high- and low- salinity fluid end-members are magmatic. In stage C1, in addition to the magmatic
high- and low- salinity fluids, important contribution of meteoric water has been recognized.
According to the composition of the analyzed FIAs, the high-salinity metal-rich magmatic fluid end-
member presents similar composition for mineralization stages A, B1, B2, and C1, with metal contents
of > 1 wt% Mn, Fe, Zn, and Pb and up to several 1000s of ppm Sb. Our results suggest the existence
253
of a homogeneous reservoir of hypersaline metal-rich porphyry-type fluids stored at depth, which has
been repeatedly mobilized 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) stable
isotope data on quartz. In contrast, the enargite-pyrite veins of stage C2 were formed by the ascent of
CO2-bearing contracted vapor that did not interact with the stored hypersaline metal-rich porphyry-
type fluids, and that similarly to stage C1, has been mixed with meteoric water at shallow level.
The similar fluid compositions recorded for mineralization stages A, B1, B2, and C1 contrast
with their different mineral assemblages. Trace element contents in sphalerite, pyrite and enargite
show also large variations. Differences in mineralogy and trace element content are mainly due to
different fO2, pH, fs2 and temperature (stage C1), conditions prevailing during the subsequent
mineralization stages, and these, in turn, resulting mainly from water-rock interaction and mixing with
low-salinity fluid, rather than to fluctuations of the initial metal concentrations of the saline fluid
The mobilization of the deeply stored hypersaline metal-rich porphyry-type fluid recognized
as an important ingredient in the formation of the Cordilleran Cerro de Pasco deposits may also
explain high fluid salinities recorded in other epithermal polymetallic deposits where no evidence of
phase separation was observed.
Acknowledgments
The present investigation was supported by the Swiss National Science Foundation (FN
200020_160071; 200020_155928; 200020_168996). We thank Volcan Companía Minera S.A. and its
geological staff including César Farfán and Ronner Bendezú for logistical support and fruitful
discussions. We gratefully acknowledge Hervé Rezeau for EPMA analyses, and Jean-Marie Boccard
for his help with sample preparation.
REFERENCES
Akinfiev, N.N., and Diamond, L.W., 2010, Thermodynamic model of aqueous CO2–H2O–NaCl
solutions from − 22 to 100°C and from 0.1 to 100MPa: Fluid Phase Equilibria, v. 295, p. 104-124.
Angeles C., 1999, Los sedimentos Cenozoicos de Cerro de Pasco: Estratigrafia, sedimentación y
tectónica, in Machare, J., Benavides-Caceres, V., and Rosas, S., eds., Sociedad Geológica del Perú,
v. 5, p. 103–118.
Arribas Jr., A., 1995, Characteristics of high-sulfidation epithermal deposits, and their relation to
magmatic fluid, in Thompson, J. F. H., ed., Magmas, fluids, and ore deposits: Victoria, British
Columbia, Mineralogical Association of Canada, Short Course Series, v. 23, p. 419–454.
254
Audétat, A., and Pettke, T., 2003, The magmatic-hydrothermal evolution of two barren granites: a
melt and fluid inclusion study of the Rito del Medio and Canada Pinabete plutons in northern New
Mexico (USA): Geochimica et Cosmochimica Acta, v. 67, p. 97-121.
Audétat, A., Pettke, T., Heinrich, C.A., and Bodnar, R.J., 2008, Special paper: the composition of
magmatic-hydrothermal fluids in barren and mineralized intrusions: Economic Geology, v. 103, p.
877-908.
Azbej, T., Severs, M.J., Rusk, B.G., and Bodnar, R.J., 2007, In situ quantitative analysis of individual
H2O–CO2 fluid inclusions by laser Raman spectroscopy: Chemical Geology, v. 237, p. 255-263.
Bakker, R J., 2003, Package FLUIDS 1. Computer programs for analysis of fluid inclusion data and
for modelling bulk fluid properties: Chemical Geology, v. 194, p. 3-23.
Bartos, P J., 1989, Prograde and retrograde base metal lode deposits and their relationship to
underlyingporphyry copper deposits: Economic Geology, v.84, p. 1671-1683.
Baumgartner, R., 2007, Sources and evolution in space and time of hydrothermal fluids at the Cerro de
Pasco Cordilleran base metal deposit, Central Peru. Terre & Environnement, v. 66, 167 p.
Baumgartner, R., Fontboté, L., Vennemann, T., 2008, Mineral zoning and geochemistry of epithermal
polymetallic Zn-Pb-Ag-Cu-Bi mineralization at Cerro de Pasco, Peru: Economic Geology, v. 103,
p. 493–537.
Baumgartner, R., Fontboté, L., Spikings, R., Ovtcharova, M., Schneider, J., Pace, L., Gutjahr, M.,
2009, Bracketing the age of magmatic-hydrothermal activity at the Cerro de Pasco epithermal
polymetallic deposit, central Peru: a U-Pb and 40Ar/39Ar study: Economic Geology, v. 104, p. 479-
504.
Bendezú, R., and Fontboté, L., 2009, Cordilleran epithermal Cu-Zn-Pb-(Au-Ag) mineralization in the
Colquijirca district, Central Peru: Deposit-scale mineralogical patterns: Economic Geology, v. 104,
p. 905–944.
Beuchat, S., Moritz, R., and Pettke, T., 2004, Fluid evolution in the W-Cu-Zn-Pb San Cristobal vein,
Peru: Fluid inclusion and stable isotope evidence: Chemical Geology, v. 210, p. 201–224.
Bissig, T., Ullrich, T.D., Tosdal, R.M., Friedman, R., and Ebert, S., 2008, The time-space distribution
of Eocene to Miocene magmatism in the central Peruvian polymetallic province and its
metallogenetic implications: Journal of South American Earth Sciences, v.26, p. 16–35.
Bissig, T., and Tosdal, R.M., 2009, Petrogenetic and Metallogenetic Relationships in the Eastern
Cordillera Occidental of Central Peru: The Journal of Geology, v.117, p.499–518.
Blundy, J., Mavrogenes, J., Tattitch, B., Sparks, B., Sparks, S., and Gilmer, A., 2015, Generation of
porphyry copper deposits by gas–brine reaction in volcanic arcs: Nature Geoscience, v.8, p.235-24.
Bodnar, R., and Vityk, M.O., 1994, Interpretation of microthermometric data for H2O-NaCl fluid
inclusions. in Fluid inclusions in Minerals: Methods and applications, B. De Vivo an M.L.
Frezzotti, eds., pub. By Virginia Tech, Blacksburg, VA, p. 117-130.
Borgheresi, M., Buccianti, A., Di Benedetto, F., and Vaughan, D.J., 2013, Application of
compositional techniques in the field of crystal chemistry: a case study of luzonite, a Sn-bearing
mineral: Mathematical Geosciences, v. 45, p. 183-206.
Casanova, V., Kouzmanov, K., Audétat, A., and Fontboté, L., 2014, Synthetic fluid inclusions in
opaque ore minerals as potential standards for NIR-light microthermometry experiments:
12thBiennial Conference Pan-American Current Research On Fluid Inclusions, June 2-6 2014,
(Denver), p.13-14.
Casanova, V., Kouzmanov, K., Audétat, A., Wälle, M., Ubrig, N., Ortelli, M., Fontboté, L. (submitted)
Fluid inclusion studies in opaque ore minerals : II. A comparative microthermometry study of
synthetic fluid inclusions hosted in quartz and opaque minerals: Geochimica et Cosmochimica
Acta, submitted.
Catchpole, H., Kouzmanov, K., Fontboté, L., Guillong, M., and Heinrich, C.A., 2011, Fluid evolution
in zoned Cordilleran polymetallic veins - Insights from microthermometry and LA-ICP-MS of fluid
inclusions: Chemical Geology, v. 281, p. 293-304.
Catchpole H., Kouzmanov K., Putlitz B., Seo J., and Fontboté L., 2015a, Zoned Base Metal
Morococha District, Peru: Economic Geology, v. 110, p. 39–71.
255
Catchpole, H., Kouzmanov, K., Bendezú, A., Ovtcharova, M., Spikings, R., Stein, H., Fontboté, L.,
2015b, Timing of porphyry (Cu-Mo) and base metal mineralisation (Zn-Pb-Ag-Cu) in a magmatic-
hydrothermal system – Morococha district, Peru: Mineralium Deposita, v. 50, p. 895-922.
Chang, Z., Hedenquist, J.W., White, N.C., Cooke, D.R., Roach, M., Deyell, C.L., Carcia, J., Gemmell,
B., McKnight, S., and Cuison, A.L., 2011, Exploration tools for linked porphyry and epithermal
deposits: Example from the Mankayan intrusion-centered Cu-Au district, Luzon, Philippines:
Economic Geology, v. 106, p. 1365–1398.
Cline, J.S., and Bodnar, R.J, 1994, Direct Evolutiono f Brine from a CrystallizingS ilicicM elt at the
Questa,New Mexico, Molybdenum Deposit: Economic Geology, v. 89, p. 1780–1802.
Cook, N.J., Ciobanu, C.L., Pring, A., Skinner, W., Shimizu, M., Danyushevsky, L., Saini-Eidukat, B.,
and Melcher, F., 2009, Trace and minor elements in sphalerite: A LA-ICPMS study: Geochimica et
Cosmochimica Acta, v. 73, p. 4761-4791.
Deditius, A.P., Utsunomiya, S., Ewing, R.C., Chryssoulis, S.L., Venter, D., and Kesler S.E., 2009,
Decoupled geochemical behavior of As and Cu in hydrothermal systems: Geology, v. 37, p. 707-
710.
Deditius, A.P., Utsunomiya S., Reich, M., Kesler, S.E., Ewing, R.C., Hough, R., and Walshe, J., 2011,
Trace metal nanoparticles in pyrite: Ore Geology Reviews, v. 42, p. 32–46.
Deditius, A.P., and Reich, M., 2016, Constraints on the solid solubility of Hg, Tl, and Cd in arsenian
pyrite: American Mineralogist, v. 101, p. 1451-1459.
Dekov, V.M., Rouxel, O., Kouzmanov, K., Bindi, L., Asael, D., Fouquet, Y., and Wälle, M., 2016,
Enargite-luzonite hydrothermal vents in Manus Back-Arc Basin: submarine analogues of high-
sulfidation epithermal mineralization: Chemical Geology, v. 438, p. 36-57.
Deyell, C., and Hedenquist, J., 2011, Trace element geochemistry of enargite in the Mankayan district,
Philippines: Economic Geology, v. 106, p. 1465-1478.
Di Benedetto, F., Bernardini, G.P., Costagliola, P., Plant, D., and Vaughan, D.J., 2005, Compositional
zoning in sphalerite crystals: American Mineralogy, v. 90, p. 1384–1392.
Dong, G., Morrison, G.W., Jaireth, S., 1995, Quartz textures in epithermal veins, Queensland –
classification, origin, and implication: Economic Geology, v. 90, p. 1841-1856.
Einaudi, M.T., 1968a, Pyrrhotite-pyrite-sphalerite relations at Cerro de Pasco, Peru. Unpublished
Ph.D. thesis, Cambridge, MA, Harvard University, 381 p.
Einaudi M.T., 1968b, Copper zoning in pyrite from Cerro de Pasco, Peru. American Mineralogist, v.
53, p. 1748-1752.
Einaudi, M.T., 1977, Environment of ore deposition at Cerro de Pasco, Peru: Economic Geology, v.
72, p. 893–924.
Einaudi, M.T., Hedenquist J., and Esra Inan, E., 2003, Sulfidation state of fluids in active and extinct
hydrothermal systems: transition from porphyry to epithermal environments: Society of Economic
Geology Special Publication, v. 10, p. 285–313.
Fontboté ,L., Bendezú, R., 2009,Cordilleran or Butte-type Veins and Replacement Bodies as a Deposit
Class in Porphyry Systems, Proceedings of the 10th Biennial Society of Geology Applied to Ore
Deposits Meeting. Townsville (Australia). 2009, p. 521-523.
Fontboté, L., Kouzmanov, K., Chiaradia, M., Pokrovski, G.S., 2017, Sulfide minerals in hydrothermal
deposits: Elements, v. 13, p. 97-103.
Fournier, R.O., 1999, Hydrothermal processes related to movement of fluid from plastic into brittle
rock in the magmatic-epithermal environment: Economic Geology, v. 94, p. 1193-1211.
Franchini, M., McFarlane, C., Maydagán, L., Reich, M., Lentz, D.R., Meinert, L., and Bouhier, V.,
2015, Trace metals in pyrite and marcasite from the Agua Rica porphyry-high sulfidation
epithermal deposit, Catamarca, Argentina: Textural features and metal zoning at the porphyry to
epithermal transition: Ore Geology Reviews, v. 66, p. 366–387.
Goldstein, R.H., and Reynolds, T.J., 1994, Systematics of fluid inclusions in diagenetic minerals:
SEPM Short Course 31: Society for Sedimentary Geology, p. 199.
Gruen, G., Weis, P., Driesner, T., Heinrich, C.A., and de Ronde, C.E. 2014, Hydrodynamic modeling
of magmatic–hydrothermal activity at submarine arc volcanoes, with implications for ore
formation: Earth and Planetary Science Letters, v. 404, p. 307-318.
Guillong, M., and Heinrich, C.A., 2007, LA-ICP-MS analysis of inclusions: Improved ablation and
detection: European Current Research On Fluid Inclusions (ECROFI-XIX),at Bern, p. 82.
256
Guillong, M., Meier, D.L., Allan, M.M., Heinrich, C.A., Yardley, B.W.D., 2008, SILLS: a Matlab-
based program for the reduction of Laser Ablation ICP-MS data of homogeneous materials and
and outstanding issues. Mineralogical Association of Canada, Vancouver, B.C., pp. 328–333.
Günther, D., Frischknecht, R., Heinrich, C.A., and Kahlert, H.J., 1997, Capabilities of an Argon
Fluoride 193 nm excimer laser for laser ablation inductively coupled plasma mass spectrometry
microanalysis of geological materials: Journal of Analytical Atomic Spectrometry, v.12, p. 939-
944.
Günther, D., Audétat, A., Frischknecht, R., and Heinrich, C.A., 1998, Quantitative analysis of major,
minor and trace elements in fluid inclusions using laser ablation–inductively coupled plasmamass
spectrometry: Journal of Analytical Atomic Spectrometry, v. 13, p. 263-270.
Hedenquist, J.W., Arribas, A., and Reynolds, T.J., 1998, Evolution of an intrusion-centered
hydrothermal system; Far Southeast-Lepanto porphyry and epithermal Cu-Au deposits, Philippines:
Economic Geology, v. 93, p. 373-404.
Heinrich, C.A., Pettke, T., Halter, W.E., Aigner-Torres, M., Audétat, A., Günther, D., Hattendorf, B.,
Bleiner, D., Guillong, M., and Horn, I., 2003, Quantitative multi-element analysis of minerals, fluid
and melt inclusions by laser-ablation inductively-coupled-plasma mass-spectrometry: Geochimica
Cosmochimica Acta, v. 67, p. 3473–3496.
Heinrich, C.A., Driesner, T., Stefánsson, A., and Seward, T.M., 2004, Magmatic vapor contraction and
the transport of gold from the porphyry environment to epithermal ore deposits: Geology, v. 32, p.
761–764.
Henry, M., 2006, The Marcapunta Oeste prospect, Colquijirca district, and the Santa Rosa prospect,
Cerro de Pasco district, Peru: Gold occurrence types: Unpublished M.Sc. thesis, Switzerland,
University of Geneva, 132 p.
Kasai, K., Sakagawa, Y., Miyazaki, S., Akaku, K., and Uchida, T., 1998, Supersaline and metal-rich
brine obtained from the Quaternary Kakkonda Granite by NEDO WD-1a in the Kakkonda
geothermal field, Japan: Mineralalium Deposita, v. 33, p. 298-301.
Kelley, K.D., Leach, D.L., Johnson, C.A., Clark, J.L., Fayek, M., Slack, J.F., Anderson, V.M., Ayuso,
L.E., and Ridley, W.I., 2004, Textural, compositional, and sulfur isotope variations of sulfide
minerals in the Red Dog Zn–Pb–Ag deposits, Brooks Range, Alaska: implications for ore
formation: Economic Geology, v. 99, p. 509–1532.
King, J., Williams-Jones, A.E., Van Hinsberg, V., and Williams-Jones, G., 2014, High-Sulfidation
Epithermal Pyrite-Hosted Au (Ag-Cu) Ore Formation by Condensed Magmatic Vapors on Sangihe
Island, Indonesia: Economic Geology, v. 109, p. 1705–1733.
Klemm, L.M., Pettke, T., and Heinrich, C.A., 2008, Fluid and source magma evolution of the Questa
porphyry Mo deposit, New Mexico, USA: Mineralium Deposita, v. 43, p. 533–552.
Kouzmanov, K., Ramboz, C., Bailly, L., and Bogdanov, K. (2004). Genesis of high-sulfidation
vinciennite-bearing cu–as–sn (< au) assemblage from the Radka epithermal copper deposit,
Bulgaria: evidence from mineralogy and infrared microthermometry of enargite. The Canadian
Mineralogist, 42(5), 1501-1521.
Kouzmanov, K., Pettke, T., Heinrich, C.A., 2010. Direct analysis of ore-precipitating fluids: combined
IR microscopy and LA-ICP-MS study of fluid inclusions in opaque ore minerals: Economic
Geology v. 105, p. 351–373.
Kouzmanov, K., and Pokrovski, G.S., 2012, Hydrothermal controls on metal distribution in porphyry
Cu (-Mo-Au) systems: Society of Economic Geologists Special Publication, v. 16, p. 573–618.
LeFort, D., Hanley, J., and Guillong, M., 2011, Subepithermal Au-Pd mineralization associated with
an alkalic porphyry Cu-Au deposit, Mount Milligan, Quesnel terrane, British Columbia, Canada:
Economic Geology, v. 106, p. 781–808.
Lusk, J., and Calder, B., 2004, The composition of sphalerite and associated sulfides in reactions of
the Cu-Fe-Zn-S, Fe-Zn-S and Cu-Fe-S systems at 1 bar and temperatures between 250 and 535°C:
Chemical Geology, v. 203,
p. 319–345.
Lockington, J.A., Cook, N.J., and Ciobanu, C.L., 2014, Trace and minor elements in sphalerite from
metamorphosed sulphide deposits: Mineralogy and Petrology, v. 108, p. 873-890.
257
Maydagán, L., Franchini, M.B., Lentz, D., Pons, J., McFarlane, C., 2013, Sulfide composition and
isotopic signature of the Altar Cu–Au deposit, Argentina: constraints on the evolution of the
porphyry-epithermal system: Canadian Mineralogist, v. 51, p. 813–840.
Moncada, D., Mutchler, S., Nieto, A., Reynolds, T.J., Rimstidt, J.D., and Bodnar, R.J., 2012, Mineral
textures and fluid inclusion petrography of the epithermal Ag–Au deposits at Guanajuato, Mexico:
Application to exploration: Journal of Geochemical Exploration, v. 114, p. 20-35.
Morisson, G., Guoyi, D., and Jareith, S., 1990, Textural zoning in epithermal quartz vein: Amira
Project P247, Gold Research Group, James Cook University of North Queensland, p. 33.
Moritz, R., 2006, Fluid salinities obtained by infrared microthermometry of opaque minerals:
Implications for ore deposit modeling—A note of caution: Journal of Geochemical Exploration, v.
89, p. 284-287.
Murakami, H., Ishihara, S. 2013, Trace elements of Indium-bearing sphalerite from tin-polymetallic
deposits in Bolivia, China and Japan: a femto-second LA-ICPMS study: Ore Geology Reviews, v.
53, p. 223-243.
Noble, D.C, and McKee, E.H, 1999, The Miocene metallogenic belt of central and northern Peru. In
Skinner, B. J., ed. Geology and ore deposits of the central Andes: Society of Economic Geology
Special Publication, v. 7, p. 155–193.
Ohmoto, H., and Rye, R. O., 1974, Hydrogen and Oxygen Isotopic Compositions of Fluid Inclusions
in the Kuroko Deposits, Japan: Economic Geology, v. 69, p. 947-953.
O'Neil, J.R., Clayton, R.N., Mayeda, T.K., 1969, Oxygen isotope fractionation in divalent metal
carbonates: The Journal of Chemical Physics, v. 51, p.5547–5558.
Ortelli, M., Kouzmanov, K., Dilles, J.H., Rusk, B.G., 2012, Fluid inclusion study in coexisting quartz
and enargite from Main Stage veins at Butte, Montana. – Pan-American Current research on Fluid
Inclusions (PACROFI-XI), University of Windsor, Windsor, Ontario, Canada, June 18-20, 2012,
Abstract Volume, p. 69-70.
Ortelli, M., 2015, Chemistry and physical properties of ore-forming fluids trapped in ore and gangue
minerals: new insights into mineralization processes in magmatic-hydrothermal systems with
special focus on the Butte mining district (USA): Terre et Environnement; v. 132, 279p.
Ortelli M., Kouzmanov K., Wälle M., Ubrig N. (submitted) Fluid inclusion studies in opaque ore
minerals: I. Trace element content and physical properties of ore minerals controlling textural
features in transmitted near-infrared light microscopy: Geochimica et Cosmochimica Acta,
submitted.
Pačevski, A., Moritz, R., Kouzmanov, K., Marquardt, K., Zivkovic, P., and Cvetkovic, L., 2012,
Texture and composition of Pb-bearing pyrite from the Coka Marin polymetallic deposit, Serbia,
controlled by nanoscale inclusions: The Canadian Mineralogist, v. 50, p. 1–20.
Pokrovski, G.S., Borisova, A.Y., Roux, J., Hazemann, J.-L., Petdang, A., Tella, M., and Testemale, D.,
2006, Antimony speciation in saline hydrothermal fluids: A combined X-ray absorption fine
structure and solubility study: Geochimica et Cosmochimica Acta, v. 70, p. 4196–4214.
Posfai, M., and Buseck, P.R., 1998, Relationships between microstructure and composition in enargite
and luzonite: American Mineralogist, v. 83, p. 373–382.
Pudack, C., Halter, W.E., Heinrich, C.A., and Pettke, T., 2009, Evolution of magmatic vapor to gold-
rich epithermal liquid: The porphyry to epithermal transition at Nevados de Famatina, northwestern
Argentina: Economic Geology, v. 104, p. 449–477.
Reich, M., Kesler, S.E., Utsunomiya, S., Palenik, C.S., Chryssoulis, S.L., and Ewing, R.C., 2005,
Solubility of gold in arsenian pyrite: Geochimica et Cosmochimica Acta, v. 69, p. 2781–2796.
Reich, M., Deditius, A., Chryssoulis, S., Li, J., Ma, C., Parada, M., Barra, F., and Mittermayer, F.,
2013, Pyrite as a record of hydrothermal fluid evolution in a porphyry copper system: A
SIMS/EMPA trace element study: Geochimica et Cosmochimica Acta, v. 104, p. 42–62.
Reed, M., Rusk, B., and Palandi, J., 2013, The Butte magmatic-hydrothermal system: One fluid yields
all alteration and veins: Economic Geology, v. 108, p. 1379–1396.
Rosas, S., Fontboté, L., Tankard, A., 2007, Tectonic evolution and paleogeography of the Mesozoic
Pucará Basin, central Peru: Journal of South American Earth Sciences, v. 26, p. 16–35.
Rosso, K., and Bodnar, R.J., 1995, Microthermometric and Raman spectroscopic detection limits of
CO2 in fluid inclusions and the Raman spectroscopic characterization of CO2: Geochimica et
Cosmochimica Acta, v. 59, p. 3961-3975.
258
Rottier. B., 2017, Magmatic and hydrothermal fluid processes at the origin of the giant porphyry-
related epithermal polymetallic deposit of Cerro de Pasco (Central Peru), Phd thesis, University of
Geneva
Rottier, B., Kouzmanov, K., Wälle, M., Bendezú, R., and Fontboté, L., 2016a, 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 Geology, v.111, p. 1347-1367.
Rottier, B., Kouzmanov, K., Bouvier, A.-S., Baumgartner, L., Wälle, M., Rezeau, H., Bendezú, R.,
Fontboté, L., 2016b, 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
Rottier, B., Kouzmanov, K., Casanova, C., Bouvier, A.-S., Baumgartner, L., Wälle, M., Fontboté, L.,
(Submitted) Hydrothermal evolution of a hidden porphyry-type mineralization related to the large
epithermal polymetallic deposit of Cerro de Pasco district (Peru): Mineralium Deposita
Rusk, B.G., Miller, B.J., and Reed, M.H., 2008a, Fluid inclusion evidence for the formation of main
stage polymetallic base-metal veins, Butte, Montana, USA, in Spenser, J. E., and Titley, S.R.
(eds.), ed., Circum-Pacific tectonics, Geological Evolution, and Ore Deposits Digest 22: Tucson,
Arizona Geological, p. 573-581.
Rusk, B.G., Reed, M.H., and Dilles, J.H., 2008b, Fluid inclusion evidence for magmatic-hydrothermal
fluid evolution in the porphyry copper-molybdenum deposit at Butte, Montana: Economic
Geology, v.103, p. 307-334.
Sajona, F.G., Izawa, E., Motomura, Y., Imai, A., Sakakibara, H., and Watanabe, K., 2002, Victoria
carbonate-base metal gold deposit and its significance in the Mankayan mineral district, Luzon,
Philippines: Resource Geology, v. 52, p. 315–328.
Scott, S., Driesner, T., and Weis, P., 2017, Boiling and condensation of saline geothermal fluids above
magmatic intrusions: Geophysical Research Letters, v. 44, (doi:10.1002/2016GL071891).
Simmons, S.F., White, N.C., and John, D.A., 2005, Geological characteristics of epithermal precious
and base metal deposits: Economic Geology 100th anniversary volume, v.29, p. 485-522.
Sterner, S.M. and Bodnar, R.J., 1984. Synthetic fluid inclusions in natural quartz I. Compositional
types synthesized and applications to experimental geochemistry: Geochimica Cosmochimica Act,
v. 48, p. 2659-2668.
Spikings, R., Reitsma, M.J., Boekhout, F., Mišković, A., Ulianov, A., Chiaradia, M., Gerdes, A.,
Schaltegger, U., 2016,Characterization of Triassic rifting in Peru and implications for the early
disassembly of western Pangaea. Gondwana Researchs, v. 35, p. 124–143.
Sutopo, B., Gemmell, B.J., and Levet, B.K., 2007, Characteristics of Sub-Microscopic Gold and Trace
Element Geochemistry of Enargite in the Martabe High-Sulphidation Epithermal Deposits, North
Sumatra, Indonesia: Proceedings of the 9th Biennial Society of Geology Applied to Ore Deposits
Meeting. Dublin (Ireland)., p. 773-776.
Valori, A., Cathelineau, M. & Marignac, C., 1992, Early fluid migration in a deep part of the
Larderello geothermal field: A fluid inclusion study of the granite sill from well Monteverdi 7.
Journal of Volcanology and Geothermal Research, v. 51, p. 115-131.
Wallier, S., Rey, R., Kouzmanov, K., Pettke, T., Heinrich, C.A., Leary, S., O’Connor, G., Tamas¸,
C.G., Vennemann, T., and Ullrich, T., 2006, Magmatic fluids in the breccia-hosted epithermal Au-
Ag deposit of Rosia Montana, Romania: Economic Geology, v. 101, p. 923–954.
Weis, P., Driesner, T., and Heinrich, C.A., 2012, Porphyry-copper ore shells form at stable pressure-
temperature fronts within dynamic fluid plumes: Science, v. 338, p. 1613-1616.
Wilkinson, J.J., Simmons, S.F., and Stoffell, B., 2013, How metalliferous brines line Mexican
epithermal veins with silver: Scientific Reports, v. 3, p. 2057.
Williams-Jones, A.E., Samson, I.M., Ault, K.M., Gagnon, J.E., and Fryer, B.J., 2010, The genesis of
distal zinc skarns: Evidence from the Mochito deposit, Honduras: Economic Geology, v. 105, p.
1411–1440.
Wilson, S.A., Ridley, W.I., and Koenig, A.E., 2002, Development of sulfide calibration standards for
the laser ablation inductively-coupled plasma mass spectrometry technique: Journal of Analytical
Atomic Spectrometry, v.17, p. 406–409.
259
Zhang, Y.-G., and Frantz, J.D., 1987, Determination of the homogenization temperatures and densities
of supercritical fluids in the system NaCl-KCl-CaCl2-H2O using synthetic fluid inclusions:
Chemical Geology, v. 64, p. 335-350.
Zheng, Y.F., 1993, Calculation of oxygen isotope fractionation in anhydrous silicate minerals:
Geochimica Cosmochimica Acta, v. 57, p. 1079-1079.
260
Table A.1: sample descriptions and locations
(*) UTM WGS84 coordinare valid in 2012, not updated
Sample# Sampler Stage# system Drillhole# East* North* Elevation Description
Massive Fe-rich sphalerite

Rottier replacement body affected
CP_12_BR_47 A UTM 1800_08_18 362218 8819755 3851
2012 by the pyrite-quartz body
(stage B2)
Rottier Pyrrhotite-rich and quartz

CP_12_BR_59 A UTM 1600_08_12 362205 8819715 3831
2012 replacement body
Rottier Pyrrhotite-rich and quartz

CP_12_BR_67 A UTM 1600_08_14 362202 8819878 3883

CP_12_BR_69 A UTM 1600_08_20 362193 8820075 3852
(stage B2)

CP_12_BR_73 A UTM 1600_08_20 362190 8820113 3845
(stage B2)

CP_12_BR_111 A UTM 1200_08_22 362170 8819515 3950
(stage B2)

CP_12_BR_116 A UTM 1600_08_07 362205 8820353 3779
(stage B2)

CP_12_BR_130 A UTM 1800_08_16 362275 8819769 3769
(stage B2)
Massive Fe-rich sphalerite-

Rottier
CP_12_BR_175 A UTM outcrop 362304 8819648 4145 galena-pyrrhotite
2012
replacement body
Baumgar
CPR 464 tner A 4nd ramp W, bottom open pit / Tajo Raul Rojas W Fe-rich sphalerite
2007
Quartz-pyrite vein with
Rottier
CP_12_BR_5 B1 UTM 1800_07_01 362094 8820149 3773 euhedral well formed
2012
quartz
Quartz-pyrite vein with
Rottier
CP_12_BR_12 B1 UTM 1800_07_01 362091 8820148 3564 euhedral well formed
2012
quartz
Rottier Massive pyrite-(quartz)
CP_12_BR_80 B2 UTM Js_800_07_05 362265 8820217 4137
Rottier Massive pyrite-quartz
CP_12_BR_84 B2 UTM Js_800_07_10 362274 8820294 4098
Massive pyrite-quartz
Rottier
CP_12_BR_105 B2 UTM 1200_08_05 362263 8819572 3934 replacement body with well
2012
formed quartz
261
Rottier replacement body with with
CP_12_BR_126 B2 UTM 1800_08_09 362179 8820358 3813
2012 euhedral well formed
quartz in cavities
Rottier
CP_12_BR_173 B2 UTM outcrop 362225 8819596 4203 replacement body with well
2012
formed quartz
Rottier Massive pyrite-quartz
CP_12_BR_174 B2 UTM outcrop 362316 8819356 4189
Casanova replacement body with with
CP-12-CV-11 B2 UTM outcrop Tajo Raul Rojas W
2012 euhedral well formed
quartz in cavities
Carbonate-sphalerite-
Rottier
CP_12_BR_138 C1 UTM 1000_07_19 362361 8819992 4065 galena vein in silicified
2012
pucara limestone
Sphalerite-galena-
Rottier carbonate-hematite vein
CP_12_BR_140 C1 UTM 1000_07_19 362367 8819980 4026
2012 crosscuting the pyrite-
quartz body (stage B2)
Carbonate-sphalerite-
Rottier
CP_12_BR_180 C1 UTM outcrop 362764 8819882 4192 galena vein in silicified
2012
pucara limestone
Massive Galena-Fe-poor
Rottier
CP_12_BR_196 C1 UTM outcrop 362646 8819592 4210 sphalerite-carbonate
2012
replacement body
Massive Galena-Fe-poor
Rottier
CP_12_BR_198 C1 UTM outcrop 362591 8819548 4167 sphalerite-carbonate
2012
replacement body
Baumgar
Zn-Pb ore with galena,
CPR 26 tner C1 Bench 4310 Tajo Matagente CN
sphalerite and kaolinite
2007
Baumgar marmatite-blende-kaolinite
CPR77 tner C1 DDH CP-00-108 (13.00m) / Tajo Raul Rojas E and pyrite, sphalerite,
2007 galena, anglesite
banded vein with sphalerite-

Baumgar pyrite-carbonates-
CPR 422 tner C1 Diamante, 4200 / Tajo Raul Rojas E magnetite-hematiteand
2007 kaolinite. 2nd min. stage,
outer most zone.
Baumgar
Fe-poor sphalerite from a
CPR431 tner C1 Diamante, 4200 / Tajo Raul Rojas E
galena-rich vein.
2007
Baumgar
Fe-Mn-Zn carbonte and
CPR471 tner C1 3180 ramp under Diamante /Tajo Raul Rojas E
quartz (outermost zone)
2007
Enargite-pyrire-
Rottier
CP_12_BR_24 C2 UTM outcrop 362029 8819252 (chalcopyrite) vein with well
2012
formed quartz
Rottier
CP_12_BR_143 C2 UTM Py_07_11 362156 8819203 4287 crosscuting the pyrite-
2012
quartz body (stage B2)
Rottier
CP_12_BR_152 C2 UTM PY_08_43 362208 8820494 4132 crosscuting the diatreme
2012
breccia
262
Baumgar
enargite vein with well
CPR 439 tner C2 2nd ramp W / Tajo Raul Rojas W
formed quartz
2007
263
Table A2: Mean trace element concentrations of the different FIAs determined by LA-ICP-MS
Mean Li B Na K Mn Fe Cu Zn
Mean Th
Sample # FIA # Stade host salinity n
(°C) mean 1σ mean 1σ mean 1σ mean 1σ mean 1σ mean 1σ mean 1σ mean 1σ
(wt.% NaCl
BR-116 H_1 A Sl 233 16.1 8 495 258 1'663 959 45'638 14'473 30'610 2'832 4'721 4'962 host B.D.L. host
BR-111 G_1 A Sl 260 15.2 6 757 839 1'572 44'156 21'653 B.D.L. B.D.L. host B.D.L. host
BR-111 G_2 A Sl 257 14.7 5 163 79 1'517 401 41'282 7'470 36'898 11'121 8'905 3'271 host B.D.L. host
BR-111 G_3 A Sl 256 12.0 9 407 256 2'416 863 42'343 3'293 B.D.L. 9'651 5'845 host B.D.L. host
BR-69 C_1 A Sl 224 10.9 9 336 112 919 312 32'480 6'187 27'289 2'461 5'037 1'456 host B.D.L. host
BR-73 L_1b A Sl 263 9.0 4 275 12 2'095 2'531 30'965 2'841 12'622 9'053 2'580 2'052 host B.D.L. host
BR-73 F_3 A Qz 240 8.5 2 B.D.L. B.D.L. 28'713 3'627 15'472 919 529 2'843 127 143 3'017
BR-130 E_2a A Sl 214 6.5 9 460 297 B.D.L. 16'039 4'975 18'882 B.D.L. host B.D.L. host
BR-130 E_2b A Sl 228 6.4 5 250 75 774 2'610 15'103 2'987 17'428 1'821 1'194 602 host B.D.L. host
BR-130 E_2c A Sl 224 6.4 4 397 207 422 18'168 4'015 15'669 3'298 3'975 3'166 host B.D.L. host
BR-116 N_1 A Sl 229 5.9 11 125 93 514 215 11'781 5'093 31'584 5'653 1'321 381 host B.D.L. host
BR-73 L_1 A Sl 262 5.4 8 213 122 374 188 14'935 4'250 9'176 5'180 B.D.L. host B.D.L. host
BR-69 C_1b A Sl 269 5.4 2 338 234 838 835 17'038 3'127 13'920 3'629 1'253 host B.D.L. host
CPR 464 2_3 A Sl 254 5.3 3 180 57 B.D.L. 17'873 363 11'922 B.D.L. host B.D.L. host
CPR 464 2_1 A Sl 278 4.8 4 236 191 B.D.L. 18'735 295 B.D.L. B.D.L. host B.D.L. host
CPR 464 2_2 A Sl 278 4.7 9 241 175 B.D.L. 18'621 311 B.D.L. B.D.L. host B.D.L. host
BR-67 1_1 A Qz 253 3.9 6 B.D.L. B.D.L. 4'610 5'307 B.D.L. B.D.L. host 15'484 B.D.L. 312 346 308
BR-47 F_1 A Sl 254 2.7 3 65 37 B.D.L. B.D.L. B.D.L. B.D.L. host B.D.L. host
BR-67 2_1 A Qz 261 2.6 5 88 333 225 9'501 661 B.D.L. 329 402 846 1'128 42 407 192
BR-12 5_1 B1 Qz 355 18.5 10 933 861 3'703 30'895 18'408 45'873 5'949 6'040 6'476 48'336 28'819 1'103 494 27'275 21'607
BR-5 1_3 B1 Qz 279 18.4 3 120 1'450 17'585 10'263 5'105 30'081 13'871 56'758 23'352 552 12'278 5'150
BR-5 4_1 B1 Qz 252 9.1 1 B.D.L. B.D.L. 17'864 47'612 B.D.L. B.D.L. B.D.L. 1'736
BR-5 2_2 B1 Qz 240 8.4 6 B.D.L. 787 450 16'923 4'217 12'006 3'352 2'595 1'682 14'974 4'015 176 84 5'730 3'462
BR-5 1_1 B1 Qz 247 7.9 5 261 321 3'476 4'967 21'954 6'531 14'377 6'765 2'091 1'520 10'543 963 402 343 3'319 2'597
BR-5 5_4_2 B1 Qz 203 6.4 3 116 529 15'625 4'949 23'257 1'467 177 6'393 1'446 148 109 3'668 2'856
BR-5 4_2bb B1 Qz 288 6.4 1 950 732 39'047 2'784 1'476 7'427 319 2'809
BR-5 4_2b B1 Qz 263 6.1 3 B.D.L. 509 20'073 5'397 18'565 852 126 5'701 2'500 185 221 414 336
BR-5 1_4 B1 Qz 264 5.0 2 364 B.D.L. 19'229 240 B.D.L. 1'006 1'943 40 2'865
BR-5 2_1 B1 Qz 228 4.5 2 168 B.D.L. 4'108 4'962 1'655 104 82 B.D.L. 56 236
BR-5 3_3 B1 Qz 274 3.9 4 294 354 567 193 11'465 973 7'837 3'565 1'319 1'105 3'585 1'070 33 31 1'234 516
264
As Rb Sr Ag Sb Cs Ba Pb Bi
Sample # FIA #
mean 1σ mean 1σ mean 1σ mean 1σ mean 1σ mean 1σ mean 1σ mean 1σ mean 1σ
BR-116 H_1 B.D.L. 159 62 53 17 471 174 624 491 115 18 136 74 1'013 744 10 10
BR-111 G_1 B.D.L. 140 48 163 94 303 5'558 9'450 25 42 794 1'291 9'303 13'973 12 6
BR-111 G_2 B.D.L. 170 70 275 227 275 178 3'683 5'002 62 56 94 86 4'717 3'977 94 141
BR-111 G_3 B.D.L. 161 62 194 105 296 136 2'106 3'016 39 42 466 8'288 12'376 40 32
BR-69 C_1 B.D.L. 182 57 223 348 B.D.L. 5'118 4'550 79 25 84 78 1'709 985 41 35
BR-73 L_1b B.D.L. 189 90 133 119 B.D.L. 880 503 42 21 74 21 285 180 B.D.L.
BR-73 F_3 133 66 13 66 46 6 5 B.D.L. 21 6 B.D.L. 265 59 B.D.L.
BR-130 E_2a 206 374 136 92 71 63 311 217 62 31 80 31 59 55 2'927 2'894 105 116
BR-130 E_2b 205 311 104 44 82 66 B.D.L. 241 282 105 44 124 46 1'884 1'776 9 4
BR-130 E_2c B.D.L. 125 33 23 30 B.D.L. 97 86 134 104 167 226 1'577 1'412 50 16
BR-116 N_1 B.D.L. 76 44 142 167 24 14 283 188 22 16 52 40 359 304 7 3
BR-73 L_1 B.D.L. 80 37 42 30 B.D.L. 818 689 37 26 51 79 381 211 3
BR-69 C_1b 28 137 57 77 28 B.D.L. 223 55 35 75 47 175 22 1
CPR 464 2_3 B.D.L. 61 22 46 23 B.D.L. B.D.L. 24 30 68 65 180 251 11 7
CPR 464 2_1 B.D.L. 67 17 72 51 B.D.L. B.D.L. 40 53 203 11 779 736 60
CPR 464 2_2 1'187 67 52 66 66 B.D.L. B.D.L. 47 56 153 27 2'078 1'472 14 4
BR-67 1_1 550 565 37 36 26 34 5 5 B.D.L. 7 7 55 71 31 9 11 17
BR-47 F_1 B.D.L. 39 43 48 68 B.D.L. 323 292 74 25 61 124 70 3
BR-67 2_1 B.D.L. 21 9 49 37 B.D.L. B.D.L. 33 33 29 16 129 181 12 3
BR-12 5_1 5'139 3'540 232 97 69 53 75 40 6'185 3'237 24 11 1'112 1'638 11'369 11'461 34 42
BR-5 1_3 844 453 194 74 28 36 12 3 2'349 48 8 439 362 1'011 522 57 11
BR-5 4_1 B.D.L. 498 B.D.L. 66 B.D.L. 31 B.D.L. B.D.L. 47
BR-5 2_2 252 132 93 42 14 7 9 4 110 41 33 45 25 146 128 14 9
BR-5 1_1 86 339 380 7 7 76 120 265 82 76 101 185 74 134 35 1
BR-5 5_4_2 35 76 55 43 17 24 49 6 34 26 143 176 828 277 14 23
BR-5 4_2bb 80 42 23 10 58 99 1 B.D.L. 1
BR-5 4_2b B.D.L. 95 52 11 7 8 B.D.L. 27 3 119 328 164 9
BR-5 1_4 159 24 3 18 16 B.D.L. 423 4'355 15 8 60 B.D.L. B.D.L.
BR-5 2_1 134 1'087 32 42 33 36 53 72 18 14 62 47 16 #DIV/0! 5 2
BR-5 3_3 145 215 65 14 26 9 8 2 861 26 15 54 33 286 101 6
265
Mean Th
(wt.% NaCl
BR-5 3_2 B1 Qz 276 3.3 6 256 200 716 4'516 1'757 B.D.L. B.D.L. 1'195 62 57 705 466
BR-80 N_1 B2 Qz 231 14.7 5 237 43 1'848 33'052 25'774 28'831 7'086 B.D.L. 1'175 1'193 12'497 15'757
BR-174 Z_1 B2 Qz 201 10.1 8 1'047 1'096 1'866 20'647 7'053 38'204 21'066 3'656 1'387 18'425 B.D.L. 2'128 1'402
BR-174 Z_2 B2 Qz 199 9.1 5 2'282 1'034 750 879 25'063 10'534 28'558 371 1'887 1'311 1'592 589 646 3'038 742
CV-11 10_1 B2 Qz 267 8.0 3 214 207 B.D.L. 15'354 5'076 32'796 1'730 45 1'687 142 3'117 1'676
BR-174 Z_4 B2 Qz 207 6.5 1 1'818 B.D.L. 24'415 B.D.L. B.D.L. B.D.L. B.D.L. 1'036
BR-173 F_1 B2 Qz 234 6.3 2 1'409 1'206 B.D.L. 20'794 4'817 18'315 1'170 B.D.L. 236 B.D.L.
BR-173 I_1 B2 Qz 234 5.7 4 129 133 B.D.L. 13'815 9'907 32'259 1'160 374 B.D.L. 280 84 3'047 2'556
CV-11 7_1 B2 Qz 265 5.6 2 276 16 B.D.L. 21'740 188 B.D.L. B.D.L. B.D.L. 710 8'387 3'468
CV-11 10_3 B2 Qz 234 5.7 1 548 B.D.L. 10'551 B.D.L. B.D.L. B.D.L. B.D.L.
BR-126 6_1 B2 Qz 230 5.4 7 72 27 1'330 865 12'929 5'955 13'959 1'629 364 3'126 1'747 44 34 684 215
BR-126 10_1 B2 Qz 257 5.0 3 190 1'046 19'162 607 B.D.L. 682 B.D.L. 213 924
BR-84 J_1b B2 Qz 264 5.0 3 536 187 B.D.L. 29'190 22'941 10'221 790 413 B.D.L. 324 213 1'761 1'801
BR-84 J_1 B2 Qz 252 4.3 5 415 249 B.D.L. 12'419 5'749 B.D.L. B.D.L. 1'434 74 58 719 543
BR-80 G_3 B2 Qz 284 4.2 2 139 B.D.L. 7'905 3'642 B.D.L. 691 2'208 250 310 5'692 6'816
BR-173 G_1 B2 Qz 196 3.3 3 349 245 75 8'466 5'666 20'537 942 26 1'970 151 740 203
CV-11 6_1 B2 Qz 261 3.2 2 B.D.L. B.D.L. 10'020 3'611 B.D.L. B.D.L. 1'169 152 170 4'995 5'554
BR-80 G_2 B2 Qz 243 3.0 2 B.D.L. B.D.L. 7'304 5'805 B.D.L. B.D.L. B.D.L. 290 1'585 1'247
BR-80 J_3 B2 Qz 253 2.6 2 59 B.D.L. 5'575 4'506 B.D.L. B.D.L. B.D.L. B.D.L. 441
BR-174 Z_3 B2 Qz 220 1.9 2 154 B.D.L. 5'981 3'881 173 3'310 508 1'155
BR-140 F2_1 C1 Sl 266 18.9 8 262 172 578 87 58'485 7'413 30'322 1'340 15'168 6'931 host B.D.L. host
6A_471 C3 C1 Sl 236 15.9 9 213 156 2'024 44'656 3'959 30'079 10'598 16'383 11'294 host B.D.L. host
BR-140 j_1b C1 Sl 226 14.1 2 401 359 1'205 27'996 15'571 18'758 B.D.L. host B.D.L. host
3A_77 C1 C1 Sl 210 7.0 4 451 227 1'505 22 22'557 3'882 11'054 2'817 6'230 2'687 host B.D.L. host
BR-140 j_1b C1 Sl 216 6.8 8 242 197 661 470 21'745 3'669 7'871 5'253 5'822 6'812 host B.D.L. host
BR-138 1 C1 Sl 174 6.7 7 316 75 2'381 1'033 24'367 2'394 11'073 B.D.L. host B.D.L. host
6A_471 C5_1 C1 Sl 182 6.7 14 158 99 430 265 20'171 4'302 10'415 3'796 2'225 834 host B.D.L. host
3A_77 C7 C1 Sl 162 6.5 8 181 92 B.D.L. 22'618 7'502 8'502 3'003 5'865 host B.D.L. host
3a_26 C2_1 C1 Sl 158 5.5 10 451 565 366 326 15'378 5'803 8'509 1'051 781 host 325 host
BR-196 F2_1b C1 Sl 197 5.3 4 119 45 2'026 16'338 4'917 15'449 2'915 853 host B.D.L. host
BR-196 F1_1 C1 Sl 190 5.2 4 253 224 370 97 14'525 3'852 15'591 955 774 219 host B.D.L. host
266
Sample # FIA #
BR-5 3_2 116 140 39 30 9 9 12 4 B.D.L. 24 18 83 48 40 41 24 23

BR-80 N_1 2'516 495 380 648 984 43 16 B.D.L. 108 19 115 1'948 4'035 68 96
BR-174 Z_1 B.D.L. 118 81 95 39 46 39 383 77 87 138 117 B.D.L. 167 148
BR-174 Z_2 10 195 264 142 150 57 33 17 34 23 141 147 B.D.L. 11 12
CV-11 10_1 916 68 29 35 15 36 B.D.L. 7 5 590 523 947 458 347 23
BR-174 Z_4 B.D.L. 158 40 B.D.L. B.D.L. 32 326 1'314 26
BR-173 F_1 21 B.D.L. 41 36 B.D.L. B.D.L. B.D.L. 162 B.D.L.
BR-173 I_1 B.D.L. 82 48 23 26 23 129 23 14 10 33 7 100 64 2
CV-11 7_1 B.D.L. 529 34 246 249 353 280 B.D.L. 122 1'960 2'615 1'115 1'181 179
CV-11 10_3 B.D.L. 67 42 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 18
BR-126 6_1 567 376 117 39 60 35 37 6 177 91 33 19 343 274 82 64 9
BR-126 10_1 412 297 381 61 44 B.D.L. B.D.L. 68 25 139 139 1'078 1'156 26 30
BR-84 J_1b B.D.L. 130 127 30 16 33 28 B.D.L. 45 18 312 428 452 40 45 20
BR-84 J_1 B.D.L. 125 47 85 96 25 6 B.D.L. 41 49 298 236 319 179 44 51
BR-80 G_3 B.D.L. 67 9 B.D.L. B.D.L. 24 13 43 548 650 38 30
BR-173 G_1 B.D.L. 92 48 13 11 11 11 B.D.L. 25 17 B.D.L. 172 177 8
CV-11 6_1 B.D.L. 36 40 7 60 25 B.D.L. 16 21 618 654 17 11
BR-80 G_2 B.D.L. B.D.L. 197 235 439 B.D.L. 93 121 546 594 49 11
BR-80 J_3 B.D.L. 18 26 5 17 1 B.D.L. 47 56 84 51 B.D.L.
BR-174 Z_3 265 21 19 40 225 4 28 429 28
BR-140 F2_1 B.D.L. 242 77 115 65 B.D.L. 5'843 556 37 20 274 412 12'752 5'692 2
6A_471 C3 B.D.L. 198 78 109 52 5'024 4'012 2'161 1'750 33 18 80 45 3'802 3'135 16 14
BR-140 j_1b B.D.L. 106 73 118 58 2'287 800 2'424 159 21 4 31 B.D.L. 15 19
3A_77 C1 B.D.L. 119 7 71 8 B.D.L. B.D.L. 38 29 130 62 B.D.L. B.D.L.
BR-140 j_1b 41 88 22 56 14 1'152 1'554 3'855 4'126 36 17 74 69 3'005 2'602 12 20
BR-138 1 B.D.L. 288 248 57 42 240 114 735 447 75 29 26 18 1'914 1'628 31 24
6A_471 C5_1 131 62 25 43 18 1'654 1'008 1'082 615 23 13 80 44 1'023 955 4 5
3A_77 C7 191 140 40 89 53 68 16 224 137 102 55 64 12 593 449 6
3a_26 C2_1 217 101 90 48 61 53 59 475 414 45 39 63 46 653 861 19
BR-196 F2_1b 275 85 88 34 82 62 B.D.L. 185 181 20 9 98 53 B.D.L. 19 4
BR-196 F1_1 695 379 40 21 48 19 B.D.L. B.D.L. 10 5 75 44 B.D.L. 2 3
267
Mean Th
(wt.% NaCl
BR-196 F2_2 C1 Sl 186 5.0 3 B.D.L. B.D.L. 18'392 1'715 B.D.L. B.D.L. host B.D.L. host
BR-140 F2_2 C1 Sl 197 4.8 11 183 72 308 266 11'579 5'386 3'896 B.D.L. host B.D.L. host
5A_471 C2_2 C1 Sl 196 4.8 6 254 162 B.D.L. 13'378 4'057 B.D.L. B.D.L. host B.D.L. host
BR-140 M_2 C1 Sl 206 4.4 5 153 149 444 15'301 2'152 2'663 468 host B.D.L. host
BR-180 N_1 C1 Sl 177 4.4 8 180 124 933 14'860 1'661 B.D.L. 2'088 518 host B.D.L. host
3A_422 C1_1 C1 Sl 170 4.3 11 118 83 B.D.L. 9'378 4'646 2'681 B.D.L. host B.D.L. host
BR-196 U_1 C1 Sl 178 3.7 4 212 B.D.L. 13'234 2'752 B.D.L. B.D.L. host B.D.L. host
1A_431 431_2 C1 Sl 156 3.5 9 134 85 B.D.L. 13'747 547 10'627 434 host B.D.L. host
BR-196 F2_1b C1 Sl 172 3.4 4 173 93 259 75 14'552 5'952 7'281 5'515 464 284 host B.D.L. host
180_N_1 N_1 C1 Sl 165 2.9 8 209 B.D.L. 5'490 1'406 B.D.L. B.D.L. host B.D.L. host
1A_431 5 C1 Sl 156 2.1 9 137 52 B.D.L. 8'229 396 B.D.L. B.D.L. host B.D.L. host
BR-140 M_1 C1 Sl 204 1.7 9 82 78 1'155 6'269 2'130 B.D.L. B.D.L. host B.D.L. host
1A_431 3 C1 Sl 162 1.1 5 109 55 B.D.L. 4'139 481 B.D.L. B.D.L. host B.D.L. host
BR-24 E_2 C2 Qz 297 14.8 4 622 141 797 198 32'883 5'234 36'482 8'209 2'064 390 20'441 2'581 1'142 597 3'235 932
BR-24 E_3 C2 Qz 266 10.9 2 385 B.D.L. 27'430 38'022 2'206 16'651 B.D.L. 5'461
3a_439 9_2 C2 Qz 264 4.7 5 136 64 335 163 11'151 959 5'088 1'453 563 384 B.D.L. 116 125 143 60
3a_439 1_1 C2 Qz 265 3.4 6 41 22 B.D.L. 11'039 2'278 2'851 51 24 1'139 559 55 42 30 10
3a_439 9_1 C2 Qz 261 3.2 6 49 75 B.D.L. 11'347 1'354 3'820 4'715 109 108 1'926 1'146 166 132 577 68
BR-24 C_4b C2 Qz 281 3.0 2 25 15 B.D.L. 9'883 1'324 1'548 19 396 225 99
BR-24 e_2b C2 Qz 272 2.6 2 B.D.L. B.D.L. 5'297 1'568 9'940 4'592 257 169 2'172 176 195 141 281 24
BR-24 C_4b C2 Qz 263 2.3 3 76 B.D.L. 4'910 2'335 11'406 B.D.L. 422 291 279 255 295
BR-24 C_2 C2 Qz 294 2.2 3 B.D.L. B.D.L. 7'933 1'601 B.D.L. B.D.L. B.D.L. 367 318 433
BR-152 C2_5b C2 En 199 8.2 3 287 344 B.D.L. 5'618 2'665 B.D.L. 117 B.D.L. host 8'488 5'070
BR-152 C2_3 C2 En 201 5.1 4 350 123 1'520 7'305 2'562 B.D.L. 1'342 B.D.L. host B.D.L.
BR-152 C3_6b C2 En 224 4.0 6 510 348 630 746 16'100 5'117 B.D.L. 4'471 2'054 B.D.L. host B.D.L.
BR-152 C1_2 C2 En 197 2.6 6 850 722 B.D.L. 28'682 434 B.D.L. 8'154 957 B.D.L. host B.D.L.
BR-152 C3_6a C2 En 198 2.2 7 317 411 288 5'205 2'746 B.D.L. 6'343 6'360 16'837 host 228 244
BR-152 C2_5a C2 En 219 2.0 6 381 178 511 93 7'750 2'429 B.D.L. 2'831 B.D.L. host B.D.L.
2B_439 1 C2 En 209 1.9 7 230 476 15'249 1'148 B.D.L. 928 189 B.D.L. host B.D.L.
BR-143 C2_3 C2 En 225 1.9 8 449 104 B.D.L. 6'814 2'772 B.D.L. B.D.L. B.D.L. host B.D.L.
lage; Abbreviations: En - enargite, Sl - sphalerite, Qz - quartz
268
Sample # FIA #
BR-196 F2_2 1'153 226 188 146 147 57 B.D.L. 306 196 42 223 668 82 B.D.L.
BR-140 F2_2 B.D.L. 75 38 53 32 410 300 347 155 49 43 55 47 427 375 3 2
5A_471 C2_2 660 67 49 97 65 4'130 5'163 2'482 1'702 45 8 229 2'137 143 11 4
BR-140 M_2 B.D.L. 70 57 44 51 B.D.L. B.D.L. 43 12 22 19 B.D.L. 11 14
BR-180 N_1 B.D.L. 56 36 51 30 B.D.L. 634 23 11 65 52 2'297 7 2
3A_422 C1_1 B.D.L. 59 36 22 12 326 257 172 8 10 113 162 1'077 951 13 6
BR-196 U_1 B.D.L. 188 85 328 449 B.D.L. 735 97 71 78 B.D.L. 3
1A_431 431_2 B.D.L. 101 87 60 81 449 149 1'824 2'826 23 20 228 248 B.D.L. 100 114
BR-196 F2_1b 55 51 53 33 23 8 B.D.L. 44 12 5 10 6 237 2
180_N_1 N_1 B.D.L. 2 11 12'151 376 31 10 179 B.D.L. B.D.L.
1A_431 5 B.D.L. 25 18 24 8 824 530 479 494 15 9 42 24 1'483 982 8 5
BR-140 M_1 B.D.L. 64 95 27 16 1'566 1'797 1'500 2'055 45 32 87 177 964 1'099 33
1A_431 3 B.D.L. 15 9 46 33 157 2'010 858 10 6 338 354 B.D.L. 0
BR-24 E_2 2'573 283 32 18 7 12 7 664 41 11 16 6 1'248 23
BR-24 E_3 B.D.L. 177 16 12 B.D.L. 36 101 798 37
3a_439 9_2 B.D.L. 26 17 5 5 2 B.D.L. 14 17 17 19 39 25 5 7
3a_439 1_1 1'744 1'422 8 8 B.D.L. 16 25 5 9 8 1'175 1'782 827 864 3 1
3a_439 9_1 476 242 5 4 7 7 35 43 116 89 2 3 12 8 763 426 29 28
BR-24 C_4b B.D.L. 3 6 5 113 4 30 19 54 29 6 7
BR-24 e_2b B.D.L. 28 22 B.D.L. 7 4 B.D.L. 8 3 B.D.L. B.D.L. 3
BR-24 C_4b 3'181 13 19 90 2 18 9 38 3 85 35 4 4
BR-24 C_2 B.D.L. 35 2 10 7 25 35 B.D.L. 5 4 38 16 165 178 38 59
BR-152 C2_5b B.D.L. 64 85 31 32 2'231 3'008 B.D.L. 20 13 79 47 405 315 339 297
BR-152 C2_3 B.D.L. 73 54 55 56 3'491 1'105 B.D.L. 15 15 539 765 5'388 9'018 367 379
BR-152 C3_6b B.D.L. 83 68 39 38 778 B.D.L. 93 57 143 6'138 5'436 8
BR-152 C1_2 B.D.L. 74 68 135 5 B.D.L. B.D.L. 129 41 302 201 1'436 817 198 63
BR-152 C3_6a B.D.L. 74 103 58 74 B.D.L. B.D.L. 11 7 279 341 808 549 642 1'227
BR-152 C2_5a B.D.L. 87 94 50 29 1'752 67 B.D.L. 42 25 309 173 924 594 549 676
2B_439 1 B.D.L. 66 69 43 63 1'774 1'087 B.D.L. 76 24 25 5 1'139 226 212 0
BR-143 C2_3 B.D.L. 139 91 52 82 12'697 4'987 B.D.L. 20 27 360 464 3'701 3'536 130 72
lage; Abbreviations
269
Table A3: Mean trace element concentration ratios of the different FIAs determined by LA-ICP-MS
n - number of fluid incusions analyzed per assemblage; Abbreviations: En - enargite, Sl - sphalerite, Qz - quartz
Salinity Li/(Na+K+Mn) B/(Na+K+Mn) Na/(Na+K+Mn) K/(Na+K+Mn) Mn/(Na+K+Mn) Fe/(Na+K+Mn) Cu/(Na+K+Mn) Zn/(Na+K+Mn)

Sample
FIA # Stade host Th (°C) (wt.% NaCl n
# mean 1σ mean 1σ mean 1σ mean 1σ mean 1σ mean 1σ mean 1σ mean 1σ
equiv.)
BR-116 H_1 A Sl 233 16.1 8 0.0064 0.0043 0.0189 0.0147 0.4968 0.2861 0.2988 0.0779 0.0366 0.0525
BR-111 G_1 A Sl 260 15.2 6 0.0117 0.0144 0.0260 0.6512 0.4139
BR-111 G_2 A Sl 257 14.7 5 0.0021 0.0010 0.0173 0.0020 0.5254 0.1745 0.2512 0.2337 0.1169 0.0613
BR-111 G_3 A Sl 256 12.0 9 0.0079 0.0051 0.0470 0.0157 0.8346 0.1209 0.1471 0.1151 1.0908 0.2694
BR-69 C_1 A Sl 224 10.9 9 0.0062 0.0005 0.0537 0.0686 0.7383 0.1525 0.2720 0.1879 0.0421 0.0557
BR-73 L_1b A Sl 263 9.0 4 0.7961 0.2641 0.1803 0.2549 0.0236 0.0092 0.0331 0.0468 0.0031 0.0032 0.0352 0.0497
BR-73 F_3 A Qz 240 8.5 2 0.0114 0.0073 0.4349 0.2528 0.5029
BR-130 E_2a A Sl 214 6.5 9 0.0066 0.0021 0.0187 0.3734 0.1205 0.4791 0.0395 0.0330 0.0173
BR-130 E_2b A Sl 228 6.4 5 0.0114 0.0071 0.0107 0.5317 0.2141 0.4294 0.0379 0.0659 0.0818
BR-130 E_2c A Sl 224 6.4 4 0.0061 0.0028 0.0159 0.0046 0.5973 0.2308 0.4469 0.0290 0.0652 0.0234
BR-116 N_1 A Sl 229 5.9 11 0.0034 0.0039 0.0138 0.0090 0.3117 0.2470 0.6990 0.0613 0.0300 0.0121
BR-73 L_1 A Sl 262 5.4 8 0.0083 0.0068 0.0143 0.0125 0.5506 0.2475 0.2900 0.1912 0.3794 0.3065
BR-69 C_1b A Sl 269 5.4 2 0.0133 0.0111 0.0340 0.0370 0.6404 0.2398 0.2210 0.3126 0.1385 0.0727
CPR 464 2_3 A Sl 254 5.3 3 0.0072 0.0074 0.5602 0.1316
CPR 464 2_1 A Sl 278 4.8 4 0.0054 0.0034 0.4527 0.1587
CPR 464 2_2 A Sl 278 4.7 9 0.0086 0.0048 0.8101 0.2101 0.3945
BR-67 1_1 A Qz 253 3.9 6 0.3619 0.3167 4.4767 6.1151 0.0206 0.0118 0.0460 0.0400
BR-47 F_1 A Sl 254 2.7 3 0.0035 0.0020
BR-67 2_1 A Qz 261 2.6 5 0.0060 0.0286 0.0237 0.8292 0.1699 0.0232 0.0270 0.0660 0.0870 0.0033 0.0199 0.0222
BR-12 5_1 B1 Qz 355 18.5 10 0.0060 0.0059 0.0282 0.2175 0.1586 0.3411 0.0599 0.0503 0.0665 0.3388 0.1688 0.0069 0.0044 0.2333 0.1869
BR-5 1_3 B1 Qz 279 18.4 3 0.0007 0.0108 0.1289 0.0832 0.0381 0.2171 0.1204 0.4086 0.2053 0.0041 0.0876 0.0456
BR-5 4_1 B1 Qz 252 9.1 1 0.2728 0.7272 0.8167 0.0265
BR-5 2_2 B1 Qz 240 8.4 6 0.0155 0.0082 0.3200 0.1202 0.2405 0.0778 0.0475 0.0314 0.2780 0.0875 0.0032 0.0013 0.0997 0.0632
BR-5 1_1 B1 Qz 247 7.9 5 0.0032 0.0036 0.0937 0.1558 0.4158 0.2700 0.2353 0.1750 0.0469 0.0549 0.1700 0.0240 0.0084 0.0096 0.0713 0.0759
BR-5 5_4_2 B1 Qz 203 6.4 3 0.0022 0.0125 0.2810 0.1193 0.4257 0.0257 0.0175 0.1166 0.0223 0.0027 0.0014 0.0654 0.0369
BR-5 4_2bb B1 Qz 288 6.4 1 0.0187 0.0144 0.7696 0.0549 0.0291 0.1464 0.0063 0.0554
BR-5 4_2b B1 Qz 263 6.1 3 0.0113 0.5766 0.2363 0.2338 0.0237 0.0000 0.1658 0.0944 0.0057 0.0070 0.0124 0.0112
BR-5 1_4 B1 Qz 264 5.0 2 0.0165 0.7971 0.0975 0.0457 0.0883 0.0018 0.0000 0.1302 0.0000
BR-5 2_1 B1 Qz 228 4.5 2 0.0043 0.1047 0.1338 0.0524 0.0027 0.0020 0.0014 0.0000 0.0066
BR-5 3_3 B1 Qz 274 3.9 4 0.0112 0.0131 0.0262 0.0119 0.4935 0.0474 0.3423 0.1226 0.0556 0.0427 0.1677 0.0349 0.0016 0.0017 0.0551 0.0293
270
Sample As/(Na+K+Mn) Rb/(Na+K+Mn) Sr/(Na+K+Mn) Ag/(Na+K+Mn) Sb/(Na+K+Mn) Cs/(Na+K+Mn) Ba/(Na+K+Mn) Pb/(Na+K+Mn) Bi/(Na+K+Mn)
FIA #
# mean 1σ mean 1σ mean 1σ mean 1σ mean 1σ mean 1σ mean 1σ mean 1σ mean 1σ
BR-116 H_1 0.0018 0.0010 0.0007 0.0002 0.0052 0.0025 0.0075 0.0039 0.0013 0.0003 0.0018 0.0011 0.0145 0.0075 0.0001 0.0001
BR-111 G_1 0.0019 0.0011 0.0025 0.0018 0.0029 0.0881 0.1580 0.0003 0.0005 0.0125 0.0217 0.1509 0.2333 0.0001 0.0000
BR-111 G_2 0.0021 0.0010 0.0034 0.0028 0.0031 0.0018 0.0434 0.0578 0.0007 0.0009 0.0012 0.0010 0.0551 0.0438 0.0011 0.0016
BR-111 G_3 0.0030 0.0011 0.0037 0.0019 0.0058 0.0026 0.0395 0.0523 0.0008 0.0008 0.0027 0.1539 0.2146 0.0007 0.0006
BR-69 C_1 0.0046 0.0027 0.0034 0.0033 0.0206 0.0109 0.0010 0.0012 0.0017 0.0006 0.0065 0.0041
BR-73 L_1b 0.0031 0.0018 0.0000 0.0017 0.0009 0.0002 0.0002 0.0006 0.0000 0.0071 0.0001
BR-73 F_3 0.0076 0.0146 0.0038 0.0031 0.0015 0.0012 0.0067 0.0047 0.0014 0.0008 0.0021 0.0010 0.0013 0.0011 0.0722 0.0706 0.0025 0.0023
BR-130 E_2a 0.0041 0.0059 0.0026 0.0013 0.0020 0.0018 0.0048 0.0052 0.0026 0.0012 0.0032 0.0010 0.0464 0.0422 0.0002 0.0001
BR-130 E_2b 0.0035 0.0011 0.0006 0.0007 0.0024 0.0019 0.0034 0.0024 0.0056 0.0080 0.0415 0.0302 0.0015 0.0008
BR-130 E_2c 0.0034 0.0015 0.0039 0.0056 0.0898 0.0753 0.0015 0.0007 0.0015 0.0014 0.0319 0.0188 0.0007 0.0006
BR-116 N_1 0.0020 0.0015 0.0033 0.0033 0.0005 0.0003 0.0077 0.0083 0.0006 0.0007 0.0012 0.0008 0.0085 0.0065 0.0001 0.0000
BR-73 L_1 0.0031 0.0021 0.0017 0.0017 0.0291 0.0245 0.0015 0.0013 0.0022 0.0042 0.0137 0.0090 0.0001 0.0001
BR-69 C_1b 0.0009 0.0053 0.0031 0.0029 0.0016 0.0071 0.0022 0.0011 0.0030 0.0023 0.0066 0.0021 0.0000
CPR 464 2_3 0.0022 0.0010 0.0021 0.0018 0.0972 0.0808 0.0015 0.0020 0.0073 0.0007 0.0125 0.0142 0.0021
CPR 464 2_1 0.0344 0.0014 0.0009 0.0012 0.0011 0.0511 0.0574 0.0009 0.0009 0.0027 0.0004 0.0610 0.0636 0.0003 0.0002
CPR 464 2_2 0.0029 0.0017 0.0020 0.0009 0.0464 0.0529 0.0013 0.0017 0.0030 0.0032 0.0055 0.0095 0.0005 0.0004
BR-67 1_1 0.0628 0.1013 0.0030 0.0021 0.0019 0.0020 0.0004 0.0002 0.0006 0.0004 0.0045 0.0042 0.0038 0.0025 0.0009 0.0011
BR-47 F_1 0.0018 0.0015 0.0020 0.0024 0.0277 0.0327 0.0028 0.0012 0.0023 0.0070 0.0003 0.0002 0.0001
BR-67 2_1 0.0018 0.0006 0.0040 0.0025 0.0029 0.0033 0.0024 0.0010 0.0121 0.0178 0.0010 0.0001
BR-12 5_1 0.0440 0.0350 0.0017 0.0007 0.0005 0.0004 0.0005 0.0003 0.0658 0.0490 0.0002 0.0001 0.0110 0.0178 0.0909 0.1077 0.0003 0.0005
BR-5 1_3 0.0053 0.0020 0.0015 0.0006 0.0002 0.0002 0.0001 0.0000 0.0003 0.0028 0.0033 0.0000 0.0073 0.0001 0.0004
BR-5 4_1 0.0076 0.0000 0.0010 0.0005 0.0000 0.0000 0.0007
BR-5 2_2 0.0044 0.0023 0.0018 0.0008 0.0002 0.0001 0.0002 0.0001 0.0021 0.0008 0.0004 0.0008 0.0001 0.0028 0.0002 0.0003
BR-5 1_1 0.0074 0.0087 0.0001 0.0001 0.0020 0.0037 0.0038 0.0008 0.0019 0.0009 0.0034 0.0000 0.0025 0.0000 0.0000 0.0000
BR-5 5_4_2 0.0015 0.0011 0.0009 0.0003 0.0004 0.0007 0.0001 0.0006 0.0024 0.0026 0.0000 0.0147 0.0003 0.0003
BR-5 4_2bb 0.0016 0.0008 0.0005 0.0002 0.0011 0.0004 0.0020 0.0174 0.0000
BR-5 4_2b 0.0024 0.0015 0.0005 0.0002 0.0002 0.0007 0.0037 0.0096 0.0002
BR-5 1_4 0.0072 0.0010 0.0002 0.0007 0.0006 0.0192 0.1611 0.0007 0.0027
BR-5 2_1 0.0034 0.0303 0.0009 0.0012 0.0008 0.0009 0.0015 0.0020 0.0005 0.0014 0.0017 0.0002 0.0001 0.0001
BR-5 3_3 0.0056 0.0080 0.0029 0.0009 0.0011 0.0005 0.0003 0.0000 0.0324 0.0000 0.0011 0.0015 0.0024 0.0004 0.0123 0.0002 0.0002
271
Sample
equiv.)
BR-5 3_2 B1 Qz 276 3.3 6 0.0078 0.0038 0.0189 0.1623 0.0949 0.0531 0.0000 0.0018 0.0012 0.0235 0.0181
BR-80 N_1 B2 Qz 231 14.7 5 0.0016 0.0017 0.0237 0.5237 0.4804 0.3698 0.0909 0.0170 0.0227 0.2101 0.2879
BR-174 Z_1 B2 Qz 201 10.1 8 0.0161 0.0167 0.0369 0.3157 0.1573 0.5588 0.2106 0.0492 0.0323 0.2757 0.0280 0.0241
BR-174 Z_2 B2 Qz 199 9.1 5 0.0402 0.0217 0.0137 0.0151 0.4394 0.2705 0.5189 0.0083 0.0383 0.0113 0.0115 0.0633 0.0039
CV-11 10_1 B2 Qz 267 8.0 3 0.0039 0.0040 0.2670 0.1234 0.6134 0.0323 0.0049 0.0316 0.0000 0.0027 0.0550 0.0360
BR-174 Z_4 B2 Qz 207 6.5 1 0.0720 0.9675 0.0410
BR-173 F_1 B2 Qz 234 6.3 2 0.0416 0.0280 0.7104 0.3377 0.4967 0.0317 0.0093
BR-173 I_1 B2 Qz 234 5.7 4 0.0053 0.0060 0.5438 0.4650 0.7493 0.0336 0.0299 0.0092 0.0008 0.0972 0.0808
CV-11 7_1 B2 Qz 265 5.6 2 0.0125 0.0009 0.9867 0.0188 0.0320 0.3814 0.1614
CV-11 10_3 B2 Qz 234 5.7 1 0.0520 1.0000
BR-126 6_1 B2 Qz 230 5.4 7 0.0021 0.0003 0.0484 0.0372 0.3607 0.2612 0.4283 0.0450 0.0066 0.1021 0.0677 0.0011 0.0007 0.0153 0.0033
BR-126 10_1 B2 Qz 257 5.0 3 0.0090 0.0495 0.9579 0.0729 0.0323 0.0109 0.0437
BR-84 J_1b B2 Qz 264 5.0 3 0.0216 0.0055 0.7712 0.2089 0.3905 0.0222 0.0240 0.0098 0.0069 0.0429 0.0230
BR-84 J_1 B2 Qz 252 4.3 5 0.0416 0.0099 0.8135 0.3188 0.0798 0.0088 0.0031 0.0401 0.0288
BR-80 G_3 B2 Qz 284 4.2 2 0.0053 0.2760 0.1744 0.0263 0.0841 0.0073 0.0087 0.2128 0.2655
BR-173 G_1 B2 Qz 196 3.3 3 0.0196 0.0168 0.0048 0.4742 0.4138 0.8085 0.0322 0.0298 0.0776 0.0096 0.0359 0.0038
CV-11 6_1 B2 Qz 261 3.2 2 0.6744 0.4278 0.0583 0.0114 0.0139 0.3732 0.4526
BR-80 G_2 B2 Qz 243 3.0 2 0.5598 0.6226 0.0054 0.0077 0.1212 0.1343
BR-80 J_3 B2 Qz 253 2.6 2 0.0007 0.0011 0.3863 0.4611 0.0358
BR-174 Z_3 B2 Qz 220 1.9 2 0.0154 0.5960 0.3868 0.0172 0.3299 0.0507 0.1151
BR-140 F2_1 C1 Sl 266 18.9 8 0.0028 0.0017 0.0056 0.0011 0.5680 0.0911 0.2958 0.0132 0.1467 0.0620
6A_471 C3 C1 Sl 236 15.9 9 0.0023 0.0017 0.0222 0.5035 0.0736 0.3397 0.1164 0.1437 0.1406
BR-140 j_1b C1 Sl 226 14.1 2 0.0048 0.0048 0.0119 0.3279 0.2259 0.2345
3A_77 C1 C1 Sl 210 7.0 4 0.0075 0.0054 0.0182 0.0100 0.6926 0.2128 0.1825 0.1811 0.1574 0.1628
BR-140 j_1b C1 Sl 216 6.8 8 0.0137 0.0095 0.0397 0.0023 0.6598 0.2315 0.2176 0.1549 0.1226 0.0981
BR-138 1 C1 Sl 174 6.7 7 0.0082 0.0087 0.0234 0.8003 0.1956 0.1402 0.0246
6A_471 C5_1 C1 Sl 182 6.7 14 0.0123 0.0152 0.2097 0.8854 0.1542
3A_77 C7 C1 Sl 162 6.5 8 0.0041 0.0017 0.0584 0.6428 0.3221 0.2392 0.3383 0.1032 0.0082
3a_26 C2_1 C1 Sl 158 5.5 10 0.0069 0.0032 0.0108 0.0076 0.4693 0.3060 0.1880
BR-196 F2_1b C1 Sl 197 5.3 4 0.0093 0.0056 0.5631 0.2628
BR-196 F1_1 C1 Sl 190 5.2 4 0.0106 0.0118 0.0123 0.0029 0.5395 0.2539 0.5183 0.0282 0.0282 0.0108
272
FIA #
BR-5 3_2 0.0033 0.0036 0.0013 0.0011 0.0003 0.0003 0.0004 0.0001 0.0007 0.0015 0.0027 0.0008 0.0014 0.0009 0.0009
BR-80 N_1 0.0449 0.0055 0.0043 0.0112 0.0178 0.0005 0.0003 0.0011 0.0006 0.0015 0.0341 0.0723 0.0012 0.0017
BR-174 Z_1 0.0016 0.0012 0.0014 0.0006 0.0006 0.0004 0.0076 0.0011 0.0013 0.0021 0.0017 0.0027 0.0023 0.0022 0.0019
BR-174 Z_2 0.0014 0.0007 0.0015 0.0010 0.0008 0.0003 0.0004 0.0005 0.0001 0.0016 0.0018 0.0008 0.0004 0.0002 0.0002
CV-11 10_1 0.0171 0.0012 0.0007 0.0006 0.0003 0.0007 0.0001 0.0075 0.0094 0.0166 0.0007 0.0065
BR-174 Z_4 0.0063 0.0016 0.0013 0.0129 0.0521 0.0010
BR-173 F_1 0.0008 0.0011 0.0010 0.0063
BR-173 I_1 0.0033 0.0024 0.0010 0.0011 0.0009 0.0052 0.0005 0.0005 0.0003 0.0012 0.0004 0.0042 0.0030 0.0001
CV-11 7_1 0.0240 0.0018 0.0112 0.0114 0.0160 0.0125 0.0055 0.1196 0.0896 0.0509 0.0081
CV-11 10_3 0.0064 0.0040 0.0016
BR-126 6_1 0.0144 0.0088 0.0032 0.0010 0.0014 0.0009 0.0011 0.0045 0.0026 0.0007 0.0069 0.0091 0.0002 0.0018 0.0002 0.0003 9.2675
BR-126 10_1 0.0151 0.0196 0.0034 0.0072 0.0070 0.0547 0.0015 0.0013
BR-84 J_1b 0.0032 0.0015 0.0010 0.0007 0.0010 0.0010 0.0015 0.0009 0.0066 0.0069 0.0148 0.0054 0.0014 0.0006
BR-84 J_1 0.0059 0.0026 0.0049 0.0048 0.0015 0.0004 0.0022 0.0026 0.0151 0.0141 0.0214 0.0062 0.0026 0.0019
BR-80 G_3 0.0025 0.0003 0.0008 0.0006 0.0016 0.0205 0.0254 0.0012 0.0008
BR-173 G_1 0.0043 0.0014 0.0008 0.0007 0.0005 0.0005 0.0014 0.0012 0.0101 0.0117 0.0004
CV-11 6_1 0.0019 0.0018 0.0003 0.0041 0.0028 0.0008 0.0011 0.0459 0.0010 0.0012
BR-80 G_2 0.0165 0.0217 0.0384 0.0080 0.0108 0.0447 0.0566 0.0018 0.0004
BR-80 J_3 0.0015 0.0013 0.0008 0.0009 0.0006 0.0014 0.0011 0.0068 0.0041
BR-174 Z_3 0.0264 0.0021 0.0018 0.0039 0.0225 0.0004 0.0028 0.0428 0.0028
BR-140 F2_1 0.0024 0.0008 0.0012 0.0006 0.0619 0.0004 0.0002 0.0030 0.0044 0.0866 0.0000 0.0000
6A_471 C3 0.0023 0.0010 0.0012 0.0006 0.0546 0.0400 0.0241 0.0186 0.0004 0.0002 0.0009 0.0005 0.0418 0.0353 0.0002 0.0002
BR-140 j_1b 0.0013 0.0010 0.0014 0.0009 0.0263 0.0132 0.0273 0.0062 0.0002 0.0000 0.0003 0.0001 0.0002
3A_77 C1 0.0012 0.0029 0.0014 0.0018 0.0007 0.0251 0.0294 0.1129 0.1441 0.0012 0.0010 0.0018 0.0020 0.0697 0.0764 0.0005 0.0009
BR-140 j_1b 0.0034 0.0005 0.0019 0.0002 0.0012 0.0011 0.0039 0.0024
BR-138 1 0.0039 0.0035 0.0025 0.0031 0.0022 0.0008 0.0010 0.0008 0.0006 0.0008
6A_471 C5_1 0.0076 0.0093 0.0037 0.0025 0.1931 0.1895 0.1552 0.1892 0.0069 0.0061 0.0096 0.0171 0.1245 0.1196 0.0035 0.0030
3A_77 C7 0.0081 0.0021 0.0035 0.0021 0.0032 0.0023 0.0057 0.0074 0.0008 0.0005 0.0035 0.0015 0.0008 0.0004
3a_26 C2_1 0.0029 0.0017 0.0022 0.0016 0.0147 0.0119 0.0128 0.0073 0.0021 0.0023 0.0021 0.0022 0.0172 0.0179 0.0001 0.0001
BR-196 F2_1b 0.0028 0.0024 0.0043 0.0037 0.1697 0.2201 0.0952 0.0683 0.0018 0.0004 0.0121 0.0858 0.0110 0.0004 0.0001
BR-196 F1_1 0.0250 0.0158 0.0014 0.0008 0.0017 0.0008 0.0004 0.0002 0.0029 0.0024 0.0001 0.0001
273
Sample
equiv.)
BR-196 F2_2 C1 Sl 186 5.0 3 0.8771 0.1268
BR-140 F2_2 C1 Sl 197 4.8 11 0.0045 0.0030 0.0121 0.0077 0.5797 0.1584 0.2877 0.0692 0.0585 0.0235
5A_471 C2_2 C1 Sl 196 4.8 6 0.0144 0.8446 0.3033
BR-140 M_2 C1 Sl 206 4.4 5 0.0093 0.0057 0.0489 0.7479 0.1692 0.1044 0.0407
BR-180 N_1 C1 Sl 177 4.4 8 0.0112 0.0034 0.0750 0.0295 0.8470 0.1639 0.3358
3A_422 C1_1 C1 Sl 170 4.3 11 0.0099 0.0079 0.0161 0.0045 0.7526 0.1366 0.2195 0.1608 0.0279 0.0261
BR-196 U_1 C1 Sl 178 3.7 4 0.0054 0.0041 0.3768 0.2735 0.1430
1A_431 431_2 C1 Sl 156 3.5 9 0.0110 0.3018 0.1024
BR-196 F2_1b C1 Sl 172 3.4 4 0.0054 0.0028 0.7465 0.1100 0.2657 0.0965 0.1275
180_N_1 N_1 C1 Sl 165 2.9 8 0.0105 0.0045 0.3721 0.2645
1A_431 5 C1 Sl 156 2.1 9 0.0188 0.0258 0.0129 0.0133 0.5535 0.3519 0.3182 0.0219 0.0113 0.0122
BR-140 M_1 C1 Sl 204 1.7 9 0.0049 0.0042 0.6119 0.1953 0.4284 0.0175
1A_431 3 C1 Sl 162 1.1 5 0.0100 0.0064 0.5152 0.2499
BR-24 E_2 C2 Qz 297 14.8 4 0.0059 0.0039 0.0083 0.0059 0.4416 0.0525 0.5051 0.0135 0.0276 0.0036 0.2763 0.0460 0.0152 0.0048 0.0445 0.0154
BR-24 E_3 C2 Qz 266 10.9 2 0.0057 0.4054 0.5620 0.0326 0.2461 0.0807
3a_439 9_2 C2 Qz 264 4.7 5 0.0091 0.0046 0.0214 0.0109 0.7560 0.1119 0.3222 0.0846 0.0228 0.0288 0.0064 0.0084 0.0094 0.0038
3a_439 1_1 C2 Qz 265 3.4 6 0.0026 0.0016 0.6515 0.2463 0.1853 0.0084 0.0017 0.0670 0.0343 0.0030 0.0016 0.0016 0.0002
3a_439 9_1 C2 Qz 261 3.2 6 0.0030 0.0043 0.8800 0.1556 0.2254 0.2659 0.0052 0.0058 0.1004 0.0977 0.0083 0.0088 0.0393 0.0123
BR-24 C_4b C2 Qz 281 3.0 2 0.0016 0.0007 0.6973 0.2493 0.1249 0.0015 0.0319 0.0181 0.0080
BR-24 e_2b C2 Qz 272 2.6 2 0.3573 0.1670 0.6248 0.1812 0.0179 0.0142 0.1437 0.0379 0.0137 0.0116 0.0186 0.0050
BR-24 C_4b C2 Qz 263 2.3 3 0.0044 0.2628 0.0944 0.6616 0.0245 0.0135 0.0114 0.0126 0.0122
BR-24 C_2 C2 Qz 294 2.2 3 0.8485 0.2531 0.0388 0.0189 0.0317
BR-152 C2_5b C2 En 199 8.2 3 0.0231 0.0198 0.7790 0.0161 0.2201 0.0227
BR-152 C2_3 C2 En 201 5.1 4 0.0214 0.0126 0.0153 0.0187 0.7057 0.3358 0.1257 0.1096
BR-152 C3_6b C2 En 224 4.0 6 0.0146 0.0302 0.9540 0.0634 0.0572 0.0143
BR-152 C1_2 C2 En 197 2.6 6 0.0303 0.0191 0.0301 0.0138 0.6162 0.3251 0.1955
BR-152 C3_6a C2 En 198 2.2 7 0.0397 0.0293 0.7539 0.4203
BR-152 C2_5a C2 En 219 2.0 6 0.0248 0.0169 0.1876 0.7932 0.3432 0.1511
2B_439 1 C2 En 209 1.9 7 0.0409 0.0512 0.6630 0.4095 0.0132 0.6603 0.5387
BR-143 C2_3 C2 En 225 1.9 8 0.0314 0.0251 0.0144 0.5375 0.3796 0.4597 0.3165 1.6153 0.0286 0.0348
274
FIA #
BR-196 F2_2 0.0546 0.0097 0.0090 0.0075 0.0070 0.0028 0.0093 0.0099 0.0019 0.0099 0.0207 0.0180
BR-140 F2_2 0.0040 0.0018 0.0007 0.0013 0.0007 0.0440 0.0279 0.0303 0.0176 0.0006 0.0004 0.0023 0.0013 0.0257 0.0257 0.0001 0.0001
5A_471 C2_2 0.0126 0.0060 0.0235 0.0322 0.0263 0.0372 0.0069 0.0052 0.0053 0.0001
BR-140 M_2 0.0030 0.0020 0.0028 0.0018 0.0371 0.0012 0.0006 0.0029 0.0018 0.1122 0.0004 0.0001
BR-180 N_1 0.0100 0.0084 0.0019 0.0016 0.0082 0.0050 0.0254 0.0167 0.0026 0.0011 0.0009 0.0007 0.0654 0.0587 0.0012 0.0009
3A_422 C1_1 0.0034 0.0031 0.0026 0.0002 0.0009 0.0008 0.0020 0.0006 0.0002 0.0006 0.0004 0.0106 0.0001
BR-196 U_1 0.0022 0.0016 0.0010 0.0007 0.0174 0.0092 0.0071 0.0003 0.0004 0.0038 0.0050 0.0384 0.0526 0.0004 0.0002
1A_431 431_2 0.0001 0.0001 0.0006 0.0006 0.6382 0.0197 0.0017 0.0007 0.0098 0.0058
BR-196 F2_1b 0.0059 0.0050 0.0021 0.0031 0.0019 0.0030 0.0014 0.0094 0.0063 0.0033 0.0015 0.0023 0.0012 0.0242 0.0221 0.0002 0.0001
180_N_1 N_1 0.0006 0.0001 0.0033 0.0034 0.0115 0.2349 0.2521 0.0010 0.0000 0.0235 0.0280 0.5839 0.2904 0.0000
1A_431 5 0.0045 0.0040 0.0048 0.0019 0.0024 0.0019 0.0023 0.0174 0.0218 0.0017 0.0017 0.0017 0.0014 0.0110 0.0051 0.0006 0.0006
BR-140 M_1 0.0052 0.0056 0.0034 0.0051 0.0210 0.0112 0.0713 0.1219 0.0011 0.0010 0.0094 0.0099 0.1904 0.1460 0.0035 0.0031
1A_431 3 0.0014 0.0009 0.0011 0.0006 0.0412 0.0232 0.0221 0.0181 0.0011 0.0007 0.0024 0.0022 0.0875 0.0930 0.0006 0.0006
BR-24 E_2 0.0360 0.0030 0.0020 0.0002 0.0001 0.0002 0.0001 0.0093 0.0006 0.0001 0.0002 0.0002 0.0168 0.0050 0.0003 0.0001
BR-24 E_3 0.0026 0.0002 0.0002 0.0005 0.0015 0.0118 0.0005
3a_439 9_2 0.0017 0.0011 0.0003 0.0003 0.0001 0.0009 0.0011 0.0012 0.0013 0.0025 0.0016 0.0004 0.0005
3a_439 1_1 0.0685 0.0698 0.0005 0.0006 0.5026 0.5659 0.0007 0.0010 0.0003 0.0005 0.0006 0.0450 0.0677 0.0483 0.0471 0.0002 0.0000
3a_439 9_1 0.0251 0.0231 0.0003 0.0002 0.0004 0.0004 0.0022 0.0026 0.0059 0.0063 0.0001 0.0002 0.0008 0.0004 0.0485 0.0184 0.0019 0.0016
BR-24 C_4b 0.0002 0.0005 0.0004 0.0092 0.0002 0.0019 0.0008 0.0035 0.0011 0.0004 0.0006
BR-24 e_2b 0.0020 0.0018 0.0005 0.0003 0.0006 0.0003 0.0002 0.0002
BR-24 C_4b 0.1404 0.0006 0.0008 0.0063 0.0001 0.0010 0.0004 0.0014 0.0013 0.0030 0.0026 0.0002 0.0002
BR-24 C_2 0.0037 0.0006 0.0012 0.0010 0.0031 0.0043 0.0005 0.0003 0.0039 0.0008 0.0186 0.0223 0.0046 0.0073
BR-152 C2_5b 0.0020 0.0019 0.0036 0.0001 0.0035 0.0011 0.0082 0.0055 0.0389 0.0221 0.0054 0.0017
BR-152 C2_3 0.0036 0.0035 0.0018 0.0019 0.0210 0.0042 0.0033 0.0039 0.1983 0.2289 0.0002
BR-152 C3_6b 0.0048 0.0053 0.0027 0.0040 0.1071 0.0616 0.0050 0.0015 0.0015 0.0002 0.0702 0.0112 0.0131 0.0004
BR-152 C1_2 0.0071 0.0091 0.0038 0.0021 0.1199 0.0263 0.0033 0.0024 0.0246 0.0210 0.0718 0.0621 0.0541 0.0711
BR-152 C3_6a 0.0152 0.0125 0.0062 0.0103 1.0395 0.9989 0.0023 0.0034 0.0215 0.0421 0.4446 0.4483 0.0108 0.0059
BR-152 C2_5a 0.0077 0.0059 0.0068 0.0071 0.4162 0.1570 0.0016 0.0018 0.0531 0.0761 0.6441 1.1258 0.0400 0.0408
2B_439 1 0.0068 0.0080 0.0034 0.0028 0.2481 0.3434 0.0024 0.0017 0.0100 0.0069 0.0407 0.0407 0.0340 0.0377
BR-143 C2_3 0.0040 0.0044 0.0027 0.0027 28.3893 25.6743 0.0010 0.0008 0.0229 0.0381 0.0753 0.0618 0.0663 0.1281
275
Table A.4: Microprobe analyses of sphalerite from stage A. B2 and C1
B.D.L. : Below determination limit (S=0.047 wt%. Mn=0.015 wt%. Fe= 0.045 wt%. Cu=0.031 wt%. Zn= 0.071 wt%. Se= 0.09 wt%.
Ag=0.15 wt%. Cd=0.039 wt%. In=0.049 wt%
Sample# stage S (wt%) Mn (wt%) Fe (Wt%) Cu (wt%) Zn (wt%) Se (wt%) Ag (wt%) Cd (Wt%) In (Wt%) total
47 A 33.36 B.D.L 9.14 B.D.L 56.65 B.D.L B.D.L 0.11 B.D.L 99.3
47 A 33.38 0.03 11.51 0.04 54.26 B.D.L B.D.L 0.13 B.D.L 99.4
69 A 32.58 0.03 10.09 0.70 51.92 B.D.L B.D.L 0.11 B.D.L 95.4
69 A 32.87 B.D.L 10.97 0.30 51.30 B.D.L B.D.L 0.17 B.D.L 95.6
69 A 33.57 B.D.L 12.25 0.30 51.40 B.D.L B.D.L 0.15 B.D.L 97.7
69 A 33.52 0.02 12.40 0.20 51.42 B.D.L B.D.L 0.11 B.D.L 97.7
69 A 33.50 B.D.L 12.00 0.35 51.64 B.D.L B.D.L 0.15 B.D.L 97.6
69 A 33.38 B.D.L 11.87 0.23 51.78 B.D.L B.D.L 0.13 B.D.L 97.4
69 A 33.37 B.D.L 11.90 0.35 51.92 B.D.L B.D.L 0.14 B.D.L 97.7
73 A 33.82 0.04 13.73 0.04 51.52 B.D.L B.D.L 0.14 0.15 99.4
73 A 33.68 0.04 14.38 B.D.L 51.09 B.D.L B.D.L 0.15 B.D.L 99.3
73 A 33.97 0.05 15.26 B.D.L 49.87 B.D.L B.D.L 0.14 B.D.L 99.3
73 A 33.65 0.11 12.28 B.D.L 52.86 B.D.L B.D.L 0.10 B.D.L 99.0
73 A 33.54 0.04 11.41 B.D.L 54.20 B.D.L B.D.L 0.09 B.D.L 99.3
73 A 33.61 0.04 13.68 B.D.L 51.17 B.D.L B.D.L 0.12 B.D.L 98.6
73 A 33.40 B.D.L 10.01 0.06 55.33 B.D.L B.D.L 0.16 B.D.L 98.9
116 A 34.14 0.02 10.31 B.D.L 55.81 B.D.L B.D.L 0.13 B.D.L 100.4
130 A 34.02 B.D.L 14.24 0.09 51.30 B.D.L B.D.L 0.19 0.16 100.0
130 A 34.13 0.03 10.93 B.D.L 54.89 B.D.L B.D.L 0.17 B.D.L 100.2
130 A 34.10 0.02 14.39 0.10 50.80 B.D.L B.D.L 0.20 0.20 99.8
130 A 34.30 0.03 16.39 B.D.L 48.77 B.D.L B.D.L 0.28 B.D.L 99.8
130 A 34.35 0.02 14.86 0.09 50.75 B.D.L B.D.L 0.21 0.10 100.4
130 A 34.29 B.D.L 14.04 0.05 51.62 B.D.L B.D.L 0.22 B.D.L 100.2
130 A 34.31 0.03 15.41 0.09 50.09 B.D.L B.D.L 0.22 0.19 100.3
130 A 34.26 0.02 12.31 0.06 53.76 B.D.L B.D.L 0.18 B.D.L 100.6
130 A 34.36 B.D.L 14.58 0.06 51.15 B.D.L B.D.L 0.21 B.D.L 100.4
130 A 34.29 B.D.L 15.07 0.05 50.42 B.D.L B.D.L 0.25 0.11 100.2
276
130 A 34.22 B.D.L 14.20 0.08 51.14 B.D.L B.D.L 0.21 0.20 100.1
130 A 34.26 B.D.L 14.28 0.06 51.50 B.D.L B.D.L 0.22 0.09 100.4
130 A 34.39 B.D.L 16.82 0.10 48.29 B.D.L B.D.L 0.26 0.12 100.0
130 A 34.17 B.D.L 14.87 0.10 50.16 B.D.L B.D.L 0.23 0.11 99.6
130 A 34.39 B.D.L 16.57 0.09 48.47 B.D.L B.D.L 0.25 0.11 99.9
130 A 34.07 B.D.L 14.36 0.05 51.44 B.D.L B.D.L 0.24 0.07 100.2
130 A 34.32 B.D.L 15.21 0.08 50.48 B.D.L B.D.L 0.23 0.07 100.4
130 A 34.29 B.D.L 14.90 0.07 50.99 B.D.L B.D.L 0.21 0.07 100.5
130 A 34.39 B.D.L 15.27 0.04 50.59 B.D.L B.D.L 0.24 B.D.L 100.5
130 A 34.12 0.02 12.57 B.D.L 53.71 B.D.L B.D.L 0.16 B.D.L 100.6
130 A 34.15 B.D.L 13.98 0.08 51.87 B.D.L B.D.L 0.20 0.17 100.5
130 A 33.88 B.D.L 13.29 0.16 52.07 B.D.L B.D.L 0.20 0.41 100.0
130 A 34.21 B.D.L 12.68 0.12 53.24 B.D.L B.D.L 0.19 0.22 100.7
CPR 464 A 33.25 0.03 10.91 0.15 53.91 B.D.L B.D.L 0.19 0.30 98.7
CPR 464 A 33.10 B.D.L 9.49 0.17 55.72 B.D.L B.D.L 0.18 0.37 99.0
CPR 464 A 33.00 B.D.L 11.26 0.40 53.22 B.D.L B.D.L 0.24 0.99 99.1
CPR 464 A 33.14 B.D.L 11.72 0.21 53.64 B.D.L B.D.L 0.24 0.50 99.5
CPR 464 A 33.52 B.D.L 12.66 0.07 52.92 B.D.L B.D.L 0.18 0.09 99.4
CPR 464 A 33.32 B.D.L 11.51 0.21 53.10 B.D.L B.D.L 0.23 0.52 98.9
CPR 464 A 33.28 B.D.L 11.61 0.12 52.87 B.D.L B.D.L 0.32 0.29 98.5
CPR 464 A 33.12 0.02 11.85 0.15 53.53 B.D.L B.D.L 0.32 0.35 99.4
CPR 464 A 33.17 B.D.L 11.50 0.21 53.78 B.D.L B.D.L 0.28 0.44 99.4
CPR 464 A 33.46 0.03 12.32 B.D.L 53.63 B.D.L B.D.L 0.20 B.D.L 99.6
CPR 464 A 33.24 0.03 11.78 B.D.L 53.51 B.D.L B.D.L 0.18 0.07 98.8
CPR 464 A 33.21 B.D.L 12.17 0.10 52.65 B.D.L B.D.L 0.18 0.25 98.6
CPR 464 A 33.22 0.04 12.36 0.16 52.90 B.D.L B.D.L 0.22 0.40 99.3
CPR 464 A 33.02 B.D.L 11.50 0.20 53.87 B.D.L B.D.L 0.20 0.48 99.3
CPR 464 A 33.13 B.D.L 11.64 0.21 53.65 B.D.L B.D.L 0.16 0.52 99.3
CPR 464 A 33.05 B.D.L 11.53 0.15 53.45 B.D.L B.D.L 0.19 0.38 98.7
CPR 464 A 32.99 B.D.L 11.56 0.11 53.94 B.D.L B.D.L 0.18 0.27 99.1
CPR 464 A 33.02 0.03 11.38 0.11 54.27 B.D.L B.D.L 0.19 0.25 99.2
CPR 464 A 33.21 0.03 11.50 0.12 53.91 B.D.L B.D.L 0.19 0.25 99.2
CPR 464 A 33.19 0.03 11.46 0.11 53.68 B.D.L B.D.L 0.19 0.24 98.9
CPR 464 A 33.08 B.D.L 11.91 0.13 53.58 B.D.L B.D.L 0.18 0.29 99.2
CPR 464 A 33.15 0.04 12.27 0.06 52.80 B.D.L B.D.L 0.21 0.12 98.6
CPR 464 A 33.10 B.D.L 11.48 0.12 53.84 B.D.L B.D.L 0.20 0.25 99.0
CPR 464 A 33.33 0.03 12.41 0.09 52.74 B.D.L B.D.L 0.19 0.19 99.0
CPR 464 A 33.27 0.02 11.80 0.15 52.76 B.D.L B.D.L 0.22 0.36 98.6
CPR 464 A 33.30 B.D.L 12.05 0.05 52.55 B.D.L B.D.L 0.18 0.12 98.2
CPR 464 A 33.17 0.03 12.50 0.18 52.55 B.D.L B.D.L 0.20 0.42 99.1
138 C1 32.55 0.02 0.40 B.D.L 66.02 B.D.L B.D.L 0.12 B.D.L 99.1
138 C1 32.43 0.03 0.40 B.D.L 65.96 B.D.L B.D.L 0.19 B.D.L 99.0
138 C1 32.53 0.02 0.36 B.D.L 66.90 B.D.L B.D.L 0.13 0.02 100.0
138 C1 32.49 0.03 0.31 B.D.L 66.83 B.D.L B.D.L 0.11 0.01 99.8
138 C1 32.60 0.01 0.97 B.D.L 65.68 B.D.L B.D.L 0.15 0.05 99.5
138 C1 32.57 0.01 0.40 B.D.L 66.24 B.D.L B.D.L 0.20 B.D.L 99.4
138 C1 32.30 0.02 0.43 B.D.L 66.65 B.D.L B.D.L 0.21 B.D.L 99.6
138 C1 32.41 0.04 0.45 B.D.L 66.57 B.D.L B.D.L 0.19 B.D.L 99.7
140 C1 33.00 0.02 9.12 B.D.L 54.40 B.D.L B.D.L 0.15 B.D.L 96.7
140 C1 33.28 0.04 10.75 B.D.L 53.14 B.D.L B.D.L 0.13 B.D.L 97.4
140 C1 33.04 B.D.L 9.51 B.D.L 54.07 B.D.L B.D.L 0.13 B.D.L 96.8
140 C1 33.07 0.03 10.10 B.D.L 53.74 B.D.L B.D.L 0.10 B.D.L 97.0
140 C1 33.03 0.20 8.16 0.07 54.46 B.D.L B.D.L 0.13 B.D.L 96.1
140 C1 32.97 0.07 9.36 B.D.L 53.49 B.D.L B.D.L 0.12 B.D.L 96.0
140 C1 32.88 0.05 11.39 B.D.L 50.97 B.D.L B.D.L 0.17 B.D.L 95.5
277
140 C1 32.80 0.02 8.96 B.D.L 54.57 B.D.L B.D.L 0.08 B.D.L 96.4
140 C1 32.89 0.03 9.25 B.D.L 52.67 B.D.L B.D.L 0.16 B.D.L 95.0
140 C1 33.13 0.03 10.40 B.D.L 52.49 B.D.L B.D.L 0.14 0.09 96.3
140 C1 33.08 0.02 10.84 B.D.L 52.39 B.D.L B.D.L 0.15 0.09 96.6
140 C1 33.01 0.07 9.71 B.D.L 53.18 B.D.L B.D.L 0.13 0.08 96.2
140 C1 33.20 0.03 12.58 B.D.L 52.46 B.D.L B.D.L 0.17 B.D.L 98.4
140 C1 32.80 0.03 9.31 B.D.L 54.71 B.D.L B.D.L 0.14 0.11 97.1
140 C1 32.86 B.D.L 10.69 B.D.L 53.48 B.D.L B.D.L 0.13 0.05 97.2
140 C1 33.23 B.D.L 11.33 B.D.L 52.92 B.D.L B.D.L 0.12 0.05 97.6
140 C1 32.79 0.05 10.85 0.08 53.15 B.D.L B.D.L 0.14 0.14 97.2
140 C1 32.94 0.03 10.28 B.D.L 53.31 B.D.L B.D.L 0.13 0.08 96.8
140 C1 32.43 B.D.L 2.76 0.14 61.59 B.D.L B.D.L 0.19 0.17 97.3
140 C1 32.63 B.D.L 2.77 0.13 61.61 B.D.L B.D.L 0.17 0.26 97.6
140 C1 32.61 B.D.L 2.93 0.16 61.61 B.D.L B.D.L 0.16 B.D.L 97.5
140 C1 32.93 B.D.L 2.28 0.10 62.39 B.D.L B.D.L 0.15 B.D.L 97.8
140 C1 32.66 B.D.L 2.32 B.D.L 62.49 B.D.L B.D.L 0.16 0.05 97.7
140 C1 32.42 B.D.L 2.45 0.16 62.11 B.D.L B.D.L 0.15 0.31 97.6
140 C1 32.51 B.D.L 1.19 0.09 64.01 B.D.L B.D.L 0.24 B.D.L 98.0
140 C1 33.51 0.03 15.09 0.08 46.84 B.D.L B.D.L 0.27 0.06 95.9
140 C1 33.37 0.02 13.94 0.32 48.24 B.D.L B.D.L 0.27 B.D.L 96.2
140 C1 33.57 0.06 18.09 0.25 44.15 B.D.L B.D.L 0.32 B.D.L 96.4
140 C1 33.50 0.05 16.08 0.32 45.64 B.D.L B.D.L 0.31 B.D.L 95.9
140 C1 33.12 0.05 14.54 0.40 47.31 B.D.L B.D.L 0.26 B.D.L 95.7
140 C1 33.15 0.05 13.52 0.40 48.40 B.D.L B.D.L 0.31 B.D.L 95.8
140 C1 33.12 0.03 13.57 B.D.L 48.43 B.D.L B.D.L 0.26 B.D.L 95.4
180 C1 32.91 0.03 3.14 B.D.L 63.56 B.D.L B.D.L 0.10 B.D.L 99.7
180 C1 32.90 B.D.L 6.11 0.08 59.47 B.D.L B.D.L 0.13 B.D.L 98.7
278
180 C1 33.05 0.02 5.31 0.09 60.18 B.D.L B.D.L 0.10 B.D.L 98.8
180 C1 32.92 B.D.L 4.59 0.10 60.84 B.D.L B.D.L 0.09 B.D.L 98.6
180 C1 32.76 0.02 4.97 0.07 61.08 B.D.L B.D.L 0.11 B.D.L 99.0
180 C1 32.84 B.D.L 4.73 0.07 61.03 B.D.L B.D.L 0.12 B.D.L 98.8
180 C1 32.57 0.04 7.30 B.D.L 57.37 B.D.L B.D.L 0.05 B.D.L 97.3
196 C1 32.38 B.D.L 0.08 B.D.L 66.67 B.D.L B.D.L 0.55 0.06 99.7
196 C1 32.21 B.D.L 0.05 0.08 66.26 B.D.L B.D.L 0.84 0.31 99.8
196 C1 32.38 B.D.L 0.06 0.12 66.19 B.D.L B.D.L 0.53 0.67 99.9
196 C1 32.29 B.D.L B.D.L B.D.L 66.16 B.D.L B.D.L 0.34 B.D.L 98.8
CPR 26 C1 32.69 B.D.L 0.11 B.D.L 67.21 B.D.L B.D.L 0.23 B.D.L 100.2
CPR 422 C1 33.52 B.D.L 9.40 B.D.L 56.03 B.D.L B.D.L B.D.L B.D.L 99.0
CPR 422 C1 33.50 0.02 9.58 B.D.L 56.05 B.D.L B.D.L 0.07 B.D.L 99.2
279
CPR 431 C1 33.59 B.D.L 2.66 0.08 62.81 B.D.L B.D.L 0.18 B.D.L 99.3
CPR 431 C1 33.46 0.02 2.34 0.06 63.65 B.D.L B.D.L 0.20 B.D.L 99.7
CPR 471 C1 33.20 B.D.L 8.51 nd 57.18 B.D.L B.D.L 0.05 B.D.L 98.9
280
106 B2 33.45 0.03 11.27 0.30 54.14 B.D.L B.D.L 0.20 0.14 99.5
106 B2 33.51 0.03 11.76 0.25 53.09 B.D.L B.D.L 0.21 0.12 99.0
106 B2 33.50 0.03 11.83 0.20 53.30 B.D.L B.D.L 0.19 0.10 99.2
106 B2 33.42 0.04 12.55 0.05 52.73 B.D.L B.D.L 0.21 B.D.L 99.0
106 B2 33.42 0.04 12.92 0.09 52.02 B.D.L B.D.L 0.20 0.07 98.8
106 B2 33.37 0.03 12.25 0.04 53.72 B.D.L B.D.L 0.19 B.D.L 99.6
106 B2 33.44 0.04 12.09 B.D.L 53.35 B.D.L B.D.L 0.20 B.D.L 99.1
106 B2 33.49 0.03 12.06 0.03 54.02 B.D.L B.D.L 0.19 B.D.L 99.8
106 B2 33.31 0.03 11.68 B.D.L 53.33 B.D.L B.D.L 0.19 B.D.L 98.5
106 B2 34.65 0.04 12.04 B.D.L 52.87 B.D.L B.D.L 0.18 B.D.L 99.8
106 B2 33.77 0.04 12.39 B.D.L 52.50 B.D.L B.D.L 0.19 B.D.L 98.9
106 B2 33.40 0.04 11.83 B.D.L 53.11 B.D.L B.D.L 0.18 B.D.L 98.6
106 B2 33.20 0.04 11.34 0.14 53.33 B.D.L B.D.L 0.20 0.26 98.5
106 B2 33.77 0.03 11.12 0.05 53.82 B.D.L B.D.L 0.20 B.D.L 99.0
106 B2 33.40 0.03 11.38 0.12 53.43 B.D.L B.D.L 0.22 0.08 98.7
106 B2 33.41 0.03 11.28 0.15 53.82 B.D.L B.D.L 0.19 0.13 99.0
80 B2 33.49 0.07 11.45 0.70 51.32 B.D.L B.D.L 0.26 0.32 97.6
80 B2 33.48 0.08 11.25 0.35 52.54 B.D.L B.D.L 0.25 0.33 98.3
80 B2 33.52 0.07 11.57 0.76 51.34 B.D.L B.D.L 0.25 0.92 98.4
80 B2 33.62 0.08 11.89 0.68 51.57 B.D.L B.D.L 0.27 0.67 98.8
80 B2 33.45 0.06 12.24 0.43 51.48 B.D.L B.D.L 0.24 0.15 98.0
80 B2 33.54 0.06 12.53 0.34 51.34 B.D.L B.D.L 0.25 0.20 98.2
80 B2 33.45 0.13 12.13 0.66 51.82 B.D.L B.D.L 0.20 B.D.L 98.4
80 B2 33.47 0.12 11.92 0.56 52.47 B.D.L B.D.L 0.20 B.D.L 98.7
80 B2 33.37 0.12 12.28 0.58 51.77 B.D.L B.D.L 0.21 B.D.L 98.3
281
80 B2 33.37 0.07 12.12 0.17 51.80 B.D.L B.D.L 0.23 0.20 98.0
80 B2 33.33 0.06 12.19 0.13 52.24 B.D.L B.D.L 0.23 0.12 98.3
80 B2 33.25 0.07 12.76 0.49 50.52 B.D.L B.D.L 0.24 0.53 97.9
80 B2 33.34 0.07 12.53 0.40 50.55 B.D.L B.D.L 0.25 0.13 97.3
80 B2 33.20 0.07 11.82 0.17 52.86 B.D.L B.D.L 0.23 0.18 98.5
80 B2 33.50 0.08 12.14 0.37 51.85 B.D.L B.D.L 0.24 0.40 98.6
80 B2 33.45 0.07 12.40 0.42 51.42 B.D.L B.D.L 0.22 0.11 98.1
80 B2 33.28 0.04 11.94 0.14 52.98 B.D.L B.D.L 0.27 0.18 98.8
80 B2 33.15 0.04 12.35 0.27 52.53 B.D.L B.D.L 0.25 0.28 98.9
80 B2 32.99 0.05 11.92 0.16 52.55 B.D.L B.D.L 0.24 B.D.L 97.9
80 B2 33.79 0.05 12.52 0.23 51.88 B.D.L B.D.L 0.23 0.13 98.8
80 B2 33.21 0.10 13.33 1.23 49.83 B.D.L B.D.L 0.25 0.23 98.2
80 B2 33.10 0.09 12.65 0.30 51.01 B.D.L B.D.L 0.23 0.21 97.6
80 B2 33.44 0.08 15.92 2.60 45.62 B.D.L B.D.L 0.20 0.18 98.0
80 B2 33.81 0.06 20.00 1.31 42.33 B.D.L B.D.L 0.19 0.28 98.0
80 B2 33.41 0.08 13.88 0.06 51.32 B.D.L B.D.L 0.20 B.D.L 99.0
80 B2 33.28 0.08 14.02 0.07 51.06 B.D.L B.D.L 0.22 B.D.L 98.7
80 B2 34.43 0.06 13.47 0.24 50.97 B.D.L B.D.L 0.21 0.09 99.5
282
Table A.5: LA-ICP-MS analyses of sphalerite crystals from stage A and C1
(*): host composition obtained from the LA-ICP-MS analyses of the fluid inclusions
Ga Ge 72 Ge74
Mineralizati Li Na Si (ppm) K Ca V Cr Mn Fe Co Ni Cu Zn As
Mineral Sample # Analyses # B (ppm) (ppm (ppm) (ppm)
on stage (ppm) (ppm) (nist) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)
) (nist) (nist)
Sphalerite BR-111 1 A N.A. N.A. N.A. 50.3 N.A. N.A. B.D.L 2.05 29.4 43046 0.4 B.D.L 23.7 521333 13 3.38 B.D.L 2.83
Sphalerite BR-111 2 A N.A. N.A. N.A. 71.9 N.A. N.A. B.D.L 2.29 31.6 45774 0.44 B.D.L 23.6 521333 12.6 3.72 B.D.L 3.61
Sphalerite BR-111 3 A N.A. N.A. N.A. 86.7 N.A. N.A. B.D.L 1.56 32.4 39169 0.35 B.D.L 53.7 521333 49.1 3.79 0.47 15.1
Sphalerite BR-111 4 A N.A. N.A. N.A. 105 N.A. N.A. B.D.L 2.09 26.9 43462 0.36 0.04 45.6 521333 13.9 3.35 B.D.L 2.42
Sphalerite BR-111 5 A N.A. N.A. N.A. 101 N.A. N.A. B.D.L 2.2 29.5 40292 0.36 B.D.L 40.8 521333 26.3 3.54 B.D.L 2.79
Sphalerite BR-111 6 A N.A. N.A. N.A. 91.5 N.A. N.A. B.D.L 2.63 46.9 37305 0.35 0.04 32.1 521333 25.3 3.64 B.D.L 5.27
Sphalerite BR-111 7 A N.A. N.A. N.A. 78.9 N.A. N.A. B.D.L 2.33 35.4 39358 0.42 0.02 64.4 521333 78.5 3.32 0.47 12.6
Sphalerite (*) BR-111 8 A B.D.L 7.46 1.14 1160 31.2 597 N.A. N.A. 76.4 102160 N.A. N.A. 154 524604 N.A. N.A. N.A. 11.6
Sphalerite (*) BR-111 9 A B.D.L B.D.L 0.88 4727 274 9003 N.A. N.A. 78.9 109582 N.A. N.A. 163 524599 N.A. N.A. N.A. 6.57
Sphalerite (*) BR-111 10 A B.D.L 4.89 B.D.L 1754 90.1 3652 N.A. N.A. 82.8 113200 N.A. N.A. 117 525070 N.A. N.A. N.A. 6.33
Sphalerite (*) BR-111 11 A B.D.L B.D.L B.D.L B.D.L 89.5 2430 N.A. N.A. 78.5 120281 N.A. N.A. 211 517007 N.A. N.A. N.A. B.D.L
Sphalerite (*) BR-111 12 A B.D.L B.D.L B.D.L 6052 332 10878 N.A. N.A. 70.5 109471 N.A. N.A. 187 513517 N.A. N.A. N.A. B.D.L
Sphalerite (*) BR-111 13 A B.D.L B.D.L 1.43 6482 259 8734 N.A. N.A. 74.2 109578 N.A. N.A. 203 526510 N.A. N.A. N.A. 6.51
Sphalerite (*) BR-111 14 A B.D.L B.D.L 0.66 4089 226 5974 N.A. N.A. 79.7 117809 N.A. N.A. 272 524537 N.A. N.A. N.A. B.D.L
Sphalerite (*) BR-111 16 A B.D.L 12.5 3.33 5441 229 8145 N.A. N.A. 66.1 104885 N.A. N.A. 121 515213 N.A. N.A. N.A. 2.84
Sphalerite BR-116 19 A N.A. N.A. N.A. 60.8 N.A. N.A. B.D.L 1.95 41.5 38851 0.01 B.D.L 60.5 573958 47.4 3.56 B.D.L 1.38
Sphalerite BR-116 20 A N.A. N.A. N.A. 59.6 N.A. N.A. B.D.L 1.96 46.9 40503 0.03 B.D.L 67.5 573958 83 3.56 B.D.L 2.55
Sphalerite BR-116 21 A N.A. N.A. N.A. 59.1 N.A. N.A. B.D.L B.D.L 46.7 39677 B.D.L B.D.L 66.2 573958 64 3.64 B.D.L 1.88
Sphalerite BR-116 22 A N.A. N.A. N.A. 65.9 N.A. N.A. B.D.L B.D.L 56.6 41471 B.D.L 0.04 49.1 573958 27.4 3.62 B.D.L 2.28
Sphalerite BR-116 23 A N.A. N.A. N.A. 63.8 N.A. N.A. B.D.L B.D.L 18 28223 B.D.L B.D.L 34.2 573958 23.2 3.22 B.D.L 1.91
Sphalerite BR-116 24 A N.A. N.A. N.A. 58.8 N.A. N.A. B.D.L B.D.L 20.3 36324 B.D.L B.D.L 18.1 573958 0.54 3.43 B.D.L 1.92
Sphalerite BR-116 25 A N.A. N.A. N.A. 36.5 N.A. N.A. B.D.L B.D.L 21.7 36784 B.D.L B.D.L 18.5 573958 0.59 3.45 B.D.L 2.45
Sphalerite BR-116 26 A N.A. N.A. N.A. 56.3 N.A. N.A. B.D.L 2.19 45.4 37967 B.D.L B.D.L 28.3 573958 8.33 3.48 B.D.L 2.01
Sphalerite BR-116 27 A N.A. N.A. N.A. 71.8 N.A. N.A. B.D.L 2.33 40.8 39875 0.05 0.04 55 573958 42.8 3.7 B.D.L 2.08
Sphalerite BR-116 28 A N.A. N.A. N.A. 88.2 N.A. N.A. B.D.L 3.46 45.7 52527 B.D.L B.D.L 19.4 553555 2.53 4.26 0.86 1.71
Sphalerite BR-116 29 A N.A. N.A. N.A. 70.6 N.A. N.A. B.D.L B.D.L 43.6 51431 B.D.L B.D.L 18.1 553555 2.39 4.29 0.61 1.86
Sphalerite BR-116 30 A N.A. N.A. N.A. 37.2 N.A. N.A. B.D.L 3.45 43.3 49602 B.D.L B.D.L 18.6 553555 1.9 3.84 0.47 1.44
283
Rb Sr Au
Se Mo Ag Cd In Sn Sb Te W Hg Tl Pb Bi Th U
Mineral Sample # Analyses # (ppm) (ppm) (ppm)(
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)
(nist) (nist) nist)
Sphalerite BR-111 1 B.D.L B.D.L B.D.L B.D.L 0.34 1229 6.44 5.66 0.98 B.D.L B.D.L B.D.L 1.16 B.D.L 0.31 B.D.L B.D.L B.D.L
Sphalerite BR-111 2 B.D.L B.D.L B.D.L B.D.L 0.26 1275 9.47 1.38 B.D.L B.D.L B.D.L B.D.L 1.11 0.02 0.26 0.01 B.D.L B.D.L
Sphalerite BR-111 3 B.D.L B.D.L B.D.L B.D.L 0.54 1147 59.2 6.05 1.4 B.D.L B.D.L B.D.L 1.11 0.45 12.3 B.D.L B.D.L B.D.L
Sphalerite BR-111 4 B.D.L B.D.L 0.01 B.D.L 0.94 1379 61.7 18 2.07 B.D.L B.D.L B.D.L 0.96 0 2.15 0.02 B.D.L B.D.L
Sphalerite BR-111 5 B.D.L B.D.L 0.04 0.03 0.84 1284 28.9 15.6 1.64 B.D.L B.D.L B.D.L 0.89 0.02 4.83 0.02 B.D.L B.D.L
Sphalerite BR-111 6 B.D.L B.D.L B.D.L B.D.L 0.87 983 15.8 3.81 0.63 B.D.L 0.02 B.D.L 1.34 0.13 3.48 0.01 B.D.L 0.01
Sphalerite BR-111 7 B.D.L B.D.L B.D.L B.D.L 1.07 1234 46.9 8.91 1.22 B.D.L 0.02 B.D.L 1.11 0.41 10.3 0.01 B.D.L B.D.L
Sphalerite (*) BR-111 8 N.A. B.D.L B.D.L N.A. 1.81 4300 N.A. N.A. 3.02 1.71 N.A. N.A. N.A. B.D.L 4.26 0.05 N.A. N.A.
Sphalerite (*) BR-111 9 N.A. B.D.L B.D.L N.A. 1.48 4906 N.A. N.A. 2.42 B.D.L N.A. N.A. N.A. B.D.L 3.77 B.D.L N.A. N.A.
Sphalerite (*) BR-111 10 N.A. B.D.L B.D.L N.A. 0.93 3575 N.A. N.A. B.D.L B.D.L N.A. N.A. N.A. B.D.L 0.34 B.D.L N.A. N.A.
Sphalerite (*) BR-111 12 N.A. B.D.L B.D.L N.A. 1.83 5508 N.A. N.A. B.D.L B.D.L N.A. N.A. N.A. B.D.L B.D.L 0.13 N.A. N.A.
Sphalerite (*) BR-111 18 N.A. B.D.L B.D.L N.A. 1.61 5843 N.A. N.A. B.D.L B.D.L N.A. N.A. N.A. B.D.L B.D.L B.D.L N.A. N.A.
Sphalerite BR-116 19 B.D.L B.D.L B.D.L B.D.L 3.66 706 79.4 3.81 B.D.L B.D.L B.D.L B.D.L 3.76 0.01 0.18 B.D.L B.D.L B.D.L
Sphalerite BR-116 20 B.D.L B.D.L B.D.L B.D.L 3.29 859 58 1.85 B.D.L B.D.L 0.12 B.D.L 4.05 B.D.L 0.1 B.D.L B.D.L 0.02
Sphalerite BR-116 21 B.D.L B.D.L B.D.L B.D.L 2.04 859 74.6 1.4 B.D.L B.D.L B.D.L B.D.L 3.76 B.D.L 0.07 B.D.L B.D.L B.D.L
Sphalerite BR-116 22 B.D.L B.D.L B.D.L 0.04 2.2 839 68.7 1.69 B.D.L B.D.L B.D.L B.D.L 3.25 B.D.L 0.07 B.D.L B.D.L B.D.L
Sphalerite BR-116 23 B.D.L B.D.L B.D.L B.D.L 0.73 472 24.8 14.1 0.19 0.2 B.D.L B.D.L 3.6 B.D.L 0.21 0.01 B.D.L B.D.L
Sphalerite BR-116 24 B.D.L B.D.L B.D.L B.D.L 0.58 738 8.66 B.D.L B.D.L B.D.L B.D.L B.D.L 2.58 B.D.L 0.11 B.D.L B.D.L B.D.L
Sphalerite BR-116 26 B.D.L B.D.L B.D.L 0.03 1.16 764 30.8 B.D.L B.D.L 0.36 B.D.L B.D.L 2.57 B.D.L B.D.L B.D.L B.D.L B.D.L
Sphalerite BR-116 27 B.D.L B.D.L B.D.L B.D.L 2.22 860 71.6 1.04 B.D.L 0.24 B.D.L B.D.L 2.92 B.D.L 0.03 B.D.L B.D.L B.D.L
Sphalerite BR-116 28 B.D.L B.D.L B.D.L B.D.L 0.53 557 B.D.L B.D.L 0.08 0.14 B.D.L B.D.L 2.02 B.D.L 0.32 B.D.L B.D.L B.D.L
Sphalerite BR-116 29 B.D.L B.D.L B.D.L B.D.L 0.44 567 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 2.09 B.D.L 0.09 B.D.L B.D.L B.D.L
Sphalerite BR-116 30 B.D.L B.D.L B.D.L B.D.L 0.38 567 B.D.L B.D.L 0.1 B.D.L B.D.L B.D.L 1.94 B.D.L 0.4 0.01 B.D.L B.D.L
284
Ga Ge 72 Ge74
) (nist) (nist)
Sphalerite BR-116 31 A N.A. N.A. N.A. 50.2 N.A. N.A. B.D.L B.D.L 45.4 53452 B.D.L B.D.L 21.8 553555 2.81 4.31 0.79 1.53
Sphalerite (*) BR-116 32 A B.D.L B.D.L B.D.L 4690 271 10422 N.A. N.A. 59.7 71347 N.A. N.A. 92.5 570597 N.A. N.A. N.A. 2.82
Sphalerite (*) BR-116 33 A B.D.L 5.66 0.89 2250 120 4899 N.A. N.A. 56 79838 N.A. N.A. 86.9 578315 N.A. N.A. N.A. B.D.L
Sphalerite (*) BR-116 34 A B.D.L B.D.L B.D.L B.D.L 63 3339 N.A. N.A. 80.2 70189 N.A. N.A. 92.7 571113 N.A. N.A. N.A. B.D.L
Sphalerite (*) BR-116 35 A B.D.L B.D.L B.D.L 2175 99.6 3822 N.A. N.A. 126 86188 N.A. N.A. 198 573173 N.A. N.A. N.A. 2.81
Sphalerite (*) BR-116 36 A B.D.L B.D.L B.D.L 2006 148 4654 N.A. N.A. 70.3 78998 N.A. N.A. 85.7 577964 N.A. N.A. N.A. B.D.L
Sphalerite (*) BR-116 37 A B.D.L B.D.L B.D.L 2932 114 4458 N.A. N.A. 95.9 83675 N.A. N.A. 95.3 574199 N.A. N.A. N.A. B.D.L
Sphalerite (*) BR-116 38 A B.D.L 2.66 0.24 B.D.L B.D.L B.D.L N.A. N.A. 63.6 73673 N.A. N.A. 131 573948 N.A. N.A. N.A. 0.87
Sphalerite (*) BR-116 40 A B.D.L B.D.L B.D.L 24952 1216 27842 N.A. N.A. 90 105462 N.A. N.A. 65.9 503289 N.A. N.A. N.A. 25.8
Sphalerite (*) BR-116 42 A B.D.L B.D.L B.D.L 3049 191 B.D.L N.A. N.A. 92.9 104275 N.A. N.A. 67.5 509481 N.A. N.A. N.A. 34.1
Sphalerite (*) BR-116 43 A B.D.L B.D.L B.D.L 1183 66.7 1120 N.A. N.A. 91.5 104651 N.A. N.A. 67.1 478252 N.A. N.A. N.A. 25.4
Sphalerite (*) BR-116 44 A B.D.L B.D.L B.D.L 11971 748 16080 N.A. N.A. 93.7 105462 N.A. N.A. 107 497524 N.A. N.A. N.A. 26.9
Sphalerite BR-140 47 A N.A. N.A. N.A. 199 N.A. N.A. B.D.L B.D.L 189 94920 0.29 0.6 1578 519906 390 5.01 0.77 1420
Sphalerite BR-140 48 A N.A. N.A. N.A. 60.8 N.A. N.A. B.D.L B.D.L 126 65519 B.D.L 0.24 826 495891 423 3.86 B.D.L 4.32
Sphalerite BR-140 49 A N.A. N.A. N.A. 60.4 N.A. N.A. B.D.L 4.6 206 102967 0.11 0.27 418 495891 226 4.5 B.D.L 4.89
Sphalerite BR-140 50 A N.A. N.A. N.A. 61.3 N.A. N.A. B.D.L 4.16 229 90748 B.D.L 0.12 306 595251 155 4.55 B.D.L 3.85
Sphalerite BR-140 51 A N.A. N.A. N.A. 67.1 N.A. N.A. B.D.L 4.12 194 89318 0.05 0.52 1141 487957 254 4.96 0.86 5.2
Sphalerite BR-140 52 A N.A. N.A. N.A. 88.3 N.A. N.A. B.D.L 5 240 117467 0.05 0.24 510 539826 128 5.41 0.62 3.64
Sphalerite BR-140 53 A N.A. N.A. N.A. 67.8 N.A. N.A. B.D.L 3.2 593 79949 B.D.L B.D.L 248 622828 59.7 4.41 B.D.L 4.95
Sphalerite BR-140 54 A N.A. N.A. N.A. 85.6 N.A. N.A. B.D.L 2.94 961 52785 B.D.L B.D.L 730 505347 101 3.57 0.57 4.72
Sphalerite BR-140 55 A N.A. N.A. N.A. 49 N.A. N.A. B.D.L 4.04 466 69706 B.D.L B.D.L 168 543920 31.2 6.73 3.5 3.96
Sphalerite BR-140 56 A N.A. N.A. N.A. 54.7 N.A. N.A. B.D.L B.D.L 1045 56708 B.D.L B.D.L 118 543920 20.4 3.73 B.D.L 4.85
Sphalerite BR-140 57 A N.A. N.A. N.A. 50.9 N.A. N.A. B.D.L B.D.L 90.4 71916 B.D.L B.D.L 122 543920 5.12 4.12 B.D.L 3.21
Sphalerite BR-140 58 A N.A. N.A. N.A. 65 N.A. N.A. B.D.L B.D.L 1478 78648 B.D.L B.D.L 56.9 543920 22.2 3.7 B.D.L 3.87
Sphalerite BR-140 59 A N.A. N.A. N.A. 66.1 N.A. N.A. B.D.L B.D.L 3679 70204 B.D.L B.D.L 182 577924 12.2 4.03 B.D.L 4.63
Sphalerite BR-140 60 A N.A. N.A. N.A. 25.3 N.A. N.A. B.D.L 2.76 371 29946 0.03 0.24 250 612006 36.3 3.72 0.39 7.83
285
Rb Sr Au
(nist) (nist) nist)
Sphalerite BR-116 31 B.D.L B.D.L B.D.L 0.03 0.77 510 0.85 2.89 0.19 B.D.L B.D.L B.D.L 1.64 B.D.L 0.64 B.D.L B.D.L B.D.L
Sphalerite (*) BR-116 32 N.A. B.D.L B.D.L N.A. 1.55 2579 N.A. N.A. B.D.L B.D.L N.A. N.A. N.A. 0.04 0.42 B.D.L N.A. N.A.
Sphalerite (*) BR-116 37 N.A. B.D.L 0.02 N.A. 1.29 2414 N.A. N.A. B.D.L B.D.L N.A. N.A. N.A. B.D.L B.D.L B.D.L N.A. N.A.
Sphalerite (*) BR-116 40 N.A. B.D.L 0.06 N.A. 1.27 1591 N.A. N.A. 0.85 B.D.L N.A. N.A. N.A. B.D.L 2.04 0.08 N.A. N.A.
Sphalerite (*) BR-116 42 N.A. B.D.L 0.04 N.A. 1.07 1542 N.A. N.A. B.D.L B.D.L N.A. N.A. N.A. B.D.L B.D.L B.D.L N.A. N.A.
Sphalerite (*) BR-116 44 N.A. B.D.L B.D.L N.A. 1.64 1536 N.A. N.A. 0.81 B.D.L N.A. N.A. N.A. B.D.L 0.86 0.11 N.A. N.A.
Sphalerite BR-140 47 6.94 0.06 B.D.L B.D.L 740 2795 439 891 2629 2.29 B.D.L B.D.L 3.97 4.76 265802 B.D.L B.D.L B.D.L
Sphalerite BR-140 48 B.D.L B.D.L B.D.L B.D.L 91.7 2212 1387 413 227 B.D.L B.D.L B.D.L 5.76 0.06 517 B.D.L B.D.L B.D.L
Sphalerite BR-140 49 B.D.L B.D.L 0.02 B.D.L 63.4 2512 294 520 495 B.D.L B.D.L B.D.L 4.33 0.05 1143 B.D.L B.D.L B.D.L
Sphalerite BR-140 50 B.D.L B.D.L 0.01 B.D.L 34.5 2185 566 101 11.4 B.D.L B.D.L B.D.L 5.84 B.D.L 22.4 B.D.L B.D.L B.D.L
Sphalerite BR-140 51 B.D.L B.D.L B.D.L B.D.L 117 2281 1449 1157 30 B.D.L B.D.L B.D.L 6.28 0.03 72.4 B.D.L B.D.L B.D.L
Sphalerite BR-140 52 B.D.L B.D.L B.D.L B.D.L 103 2761 334 649 29.1 B.D.L B.D.L B.D.L 5.78 0.03 85.2 B.D.L B.D.L B.D.L
Sphalerite BR-140 53 B.D.L B.D.L B.D.L B.D.L 33.4 2242 337 220 2.03 0.52 B.D.L B.D.L 6.17 B.D.L 3.08 B.D.L B.D.L B.D.L
Sphalerite BR-140 54 B.D.L B.D.L B.D.L B.D.L 84 1379 801 488 25 B.D.L B.D.L B.D.L 5.85 0.02 1535 0.06 B.D.L B.D.L
Sphalerite BR-140 55 B.D.L B.D.L B.D.L B.D.L 23.1 1119 287 79.3 5.24 B.D.L B.D.L B.D.L 6.82 0.01 6.83 B.D.L B.D.L B.D.L
Sphalerite BR-140 56 B.D.L B.D.L B.D.L 0.1 13.6 1010 256 1 B.D.L B.D.L B.D.L B.D.L 6.01 B.D.L 0.08 B.D.L B.D.L B.D.L
Sphalerite BR-140 57 B.D.L B.D.L B.D.L B.D.L 10.5 1876 84.6 169 1.54 0.38 B.D.L B.D.L 6.97 B.D.L 1.63 B.D.L B.D.L B.D.L
Sphalerite BR-140 59 B.D.L B.D.L B.D.L 0.27 38.8 1073 175 204 3.02 B.D.L B.D.L B.D.L 5.47 B.D.L 2.63 B.D.L B.D.L B.D.L
Sphalerite BR-140 60 B.D.L B.D.L 0.02 0.11 155 1049 297 360 83.1 B.D.L B.D.L B.D.L 10.5 3.36 103 0.02 B.D.L B.D.L
286
Ga Ge 72 Ge74
) (nist) (nist)
Sphalerite BR-140 61 A N.A. N.A. N.A. 49.7 N.A. N.A. B.D.L B.D.L 15.5 13026 B.D.L 0.08 247 646598 23.6 3.26 B.D.L 4.76
Sphalerite BR-140 62 A N.A. N.A. N.A. 39.9 N.A. N.A. B.D.L B.D.L 12.6 14846 0.08 B.D.L 41.2 635020 0.96 3.14 B.D.L 4.47
Sphalerite BR-140 63 A N.A. N.A. N.A. 45.5 N.A. N.A. B.D.L B.D.L 15.3 17428 0.07 B.D.L 110 635020 1.11 3.16 B.D.L 4.97
Sphalerite BR-140 64 A N.A. N.A. N.A. 32.7 N.A. N.A. B.D.L B.D.L 20.4 11528 0.09 B.D.L 32.3 519906 0.91 2.94 B.D.L 3.24
Sphalerite BR-47 65 A N.A. N.A. N.A. 19.3 N.A. N.A. B.D.L 2.5 54.7 44741 B.D.L B.D.L 47 570000 13.4 3.67 B.D.L 0.9
Sphalerite BR-47 66 A N.A. N.A. N.A. 71.1 N.A. N.A. B.D.L 2.33 31 46563 0.01 B.D.L 60.3 570000 1.64 3.27 B.D.L 1.64
Sphalerite BR-47 67 A N.A. N.A. N.A. 109 N.A. N.A. B.D.L 2.11 32.1 46486 B.D.L B.D.L 60.7 570000 2.25 3.46 B.D.L 0.97
Sphalerite BR-47 68 A N.A. N.A. N.A. 175 N.A. N.A. 0.13 B.D.L 35.1 47560 B.D.L 0.05 62.2 570000 5.05 3.42 B.D.L 1.62
Sphalerite BR-47 69 A N.A. N.A. N.A. 739 N.A. N.A. B.D.L B.D.L 40.5 51072 B.D.L B.D.L 65.3 570000 9.88 3.77 B.D.L 2.93
Sphalerite BR-47 70 A N.A. N.A. N.A. 51 N.A. N.A. B.D.L 2.24 58 45263 B.D.L B.D.L 59.7 570000 18.3 3.55 B.D.L B.D.L
Sphalerite (*) BR-47 71 A B.D.L 5.11 0.09 1208 31 632 N.A. N.A. 88.5 70522 N.A. N.A. 145 524350 N.A. N.A. N.A. 51.5
Sphalerite (*) BR-47 72 A B.D.L B.D.L B.D.L 13773 527 11154 N.A. N.A. 86.4 103462 N.A. N.A. 108 628909 N.A. N.A. N.A. 50.2
Sphalerite (*) BR-47 73 A B.D.L B.D.L B.D.L 20444 708 19587 N.A. N.A. 125 115094 N.A. N.A. 124 724313 N.A. N.A. N.A. 57.6
Sphalerite BR-69 74 A N.A. N.A. N.A. 127 N.A. N.A. 0.03 2.15 30.6 42216 0.19 0.17 313 516262 27.1 3.48 0.26 2.59
Sphalerite BR-69 75 A N.A. N.A. N.A. 72.1 N.A. N.A. B.D.L 2.52 31.4 39661 0.31 0.12 246 516262 49.7 3.6 B.D.L 2.5
Sphalerite BR-69 76 A N.A. N.A. N.A. 71.9 N.A. N.A. B.D.L 2.45 30.5 40753 0.31 B.D.L 244 516262 50.1 3.89 0.32 2.98
Sphalerite BR-69 78 A N.A. N.A. N.A. 76 N.A. N.A. B.D.L B.D.L 29.6 41632 0.29 B.D.L 284 516262 58.5 3.75 B.D.L 2.33
Sphalerite (*) BR-69 81 A B.D.L 4.03 B.D.L 1838 58 1797 N.A. N.A. 90.1 90989 N.A. N.A. 3508 513025 N.A. N.A. N.A. 2.29
Sphalerite (*) BR-69 84 A B.D.L 4.04 0.22 598 10.5 B.D.L N.A. N.A. 88.9 147878 N.A. N.A. 2499 513992 N.A. N.A. N.A. 2.35
Sphalerite BR-73 86 A N.A. N.A. N.A. 37.1 N.A. N.A. B.D.L 1.97 34.5 53820 0.23 0.14 399 526795 241 19 16.2 1.93
Sphalerite BR-73 88 A N.A. N.A. N.A. 31 N.A. N.A. B.D.L B.D.L 28.3 40207 0.18 B.D.L 70.8 526795 22.1 31 28.6 1.8
Sphalerite BR-73 89 A N.A. N.A. N.A. 69.8 N.A. N.A. B.D.L 3.29 34.3 41058 0.12 0.06 71.4 526795 58 7.8 4.5 1.97
Sphalerite BR-73 90 A N.A. N.A. N.A. 42.4 N.A. N.A. B.D.L B.D.L 28.4 43200 0.24 B.D.L 51 526795 64 70.6 70 1.83
287
Rb Sr Au
(nist) (nist) nist)
Sphalerite BR-140 61 B.D.L B.D.L B.D.L B.D.L 26.6 2081 545 22.8 2.37 B.D.L B.D.L B.D.L 12.7 0.07 2.17 0.01 0.01 B.D.L
Sphalerite BR-140 62 B.D.L B.D.L B.D.L B.D.L 0.22 1409 28.5 B.D.L B.D.L B.D.L B.D.L B.D.L 9.56 B.D.L 0.09 0.02 B.D.L B.D.L
Sphalerite BR-140 63 B.D.L B.D.L B.D.L B.D.L 1.23 1296 245 B.D.L B.D.L B.D.L B.D.L B.D.L 8.46 B.D.L B.D.L B.D.L B.D.L B.D.L
Sphalerite BR-47 65 B.D.L B.D.L B.D.L B.D.L 0.91 800 64.6 22.4 B.D.L B.D.L B.D.L B.D.L 1 B.D.L 0.11 B.D.L B.D.L B.D.L
Sphalerite BR-47 66 B.D.L B.D.L B.D.L 0.06 1.38 536 92.6 54.4 0.59 B.D.L B.D.L B.D.L 1.25 B.D.L 0.93 B.D.L 0.09 0.05
Sphalerite BR-47 67 B.D.L B.D.L B.D.L B.D.L 1.15 575 96.7 69.7 0.33 B.D.L B.D.L B.D.L 1.02 B.D.L 0.9 B.D.L 0.54 0.06
Sphalerite BR-47 68 B.D.L 0.05 0.02 0.26 1.2 763 151 35.2 1.66 B.D.L 0.03 B.D.L 0.96 B.D.L 5.35 B.D.L 0.47 0.43
Sphalerite BR-47 69 B.D.L 0.08 0.02 0.12 2.37 992 45.4 136 5.17 B.D.L 0.04 B.D.L 1.03 0.02 8.13 B.D.L 0.23 0.2
Sphalerite BR-69 74 B.D.L B.D.L B.D.L B.D.L 2.72 696 62.2 632 0.43 0.2 B.D.L B.D.L 2.36 B.D.L 0.22 0.03 B.D.L B.D.L
Sphalerite BR-69 75 B.D.L B.D.L B.D.L B.D.L 2.61 637 156 389 0.24 B.D.L B.D.L B.D.L 1.96 B.D.L 0.2 0.02 B.D.L B.D.L
Sphalerite BR-69 76 B.D.L B.D.L B.D.L B.D.L 2.66 623 255 292 0.22 0.13 B.D.L B.D.L 2 B.D.L 0.16 B.D.L B.D.L B.D.L
Sphalerite BR-69 77 B.D.L B.D.L B.D.L B.D.L 3.25 753 120 545 0.42 0.2 B.D.L B.D.L 2.17 B.D.L 0.12 0.01 B.D.L B.D.L
Sphalerite BR-69 78 B.D.L B.D.L B.D.L B.D.L 3.76 677 255 380 0.28 0.17 B.D.L B.D.L 1.91 B.D.L 0.19 0.02 0.04 0.07
Sphalerite BR-69 79 B.D.L B.D.L B.D.L B.D.L 6.74 780 536 276 0.61 0.09 B.D.L B.D.L 2.07 0.01 0.53 0.05 B.D.L B.D.L
Sphalerite (*) BR-69 83 N.A. B.D.L 0.01 N.A. 13.9 1515 N.A. N.A. 0.65 0.42 N.A. N.A. N.A. B.D.L 1.02 B.D.L N.A. N.A.
Sphalerite (*) BR-69 84 N.A. B.D.L B.D.L N.A. 17.7 1996 N.A. N.A. 0.85 0.14 N.A. N.A. N.A. B.D.L 0.17 0.01 N.A. N.A.
Sphalerite (*) BR-69 85 N.A. B.D.L 0.01 N.A. 10.2 2066 N.A. N.A. 1.06 0.22 N.A. N.A. N.A. B.D.L 0.15 0.01 N.A. N.A.
Sphalerite BR-73 86 B.D.L B.D.L B.D.L B.D.L 26.6 1081 79.1 529 4.85 B.D.L B.D.L B.D.L 5.55 B.D.L 4.06 B.D.L B.D.L B.D.L
Sphalerite BR-73 87 B.D.L B.D.L B.D.L B.D.L 3.57 688 30.9 107 1.36 B.D.L B.D.L B.D.L 7.78 B.D.L 1.7 B.D.L B.D.L B.D.L
Sphalerite BR-73 88 B.D.L B.D.L B.D.L B.D.L 6.74 513 4.8 57.5 0.25 B.D.L B.D.L B.D.L 6.11 0.01 0.51 B.D.L B.D.L B.D.L
Sphalerite BR-73 89 B.D.L B.D.L B.D.L B.D.L 4.29 725 44 20.4 0.7 B.D.L B.D.L B.D.L 6.07 0.02 3.11 B.D.L B.D.L B.D.L
Sphalerite BR-73 90 B.D.L B.D.L B.D.L B.D.L 18 991 7.17 46.9 0.17 B.D.L B.D.L B.D.L 5.96 0.04 1.1 0.01 B.D.L B.D.L
288
Ga Ge 72 Ge74
) (nist) (nist)
Sphalerite BR-73 91 A N.A. N.A. N.A. 41.1 N.A. N.A. B.D.L 2.28 33.4 53090 0.15 0.05 148 526795 73.6 17.3 14.5 2.14
Sphalerite BR-73 92 A N.A. N.A. N.A. 35.3 N.A. N.A. B.D.L B.D.L 56.8 54712 0.37 B.D.L 71.8 526795 90.6 3.59 0.29 2.21
Sphalerite (*) BR-73 93 A B.D.L 7.78 0.33 313 5.91 B.D.L N.A. N.A. 369 99986 N.A. N.A. 320 541954 N.A. N.A. N.A. 1.01
Sphalerite (*) BR-73 94 A B.D.L 8.3 0.22 663 18.2 620 N.A. N.A. 143 79244 N.A. N.A. 337 511749 N.A. N.A. N.A. 0.88
Sphalerite (*) BR-73 95 A B.D.L 5.5 0.31 B.D.L 15.4 B.D.L N.A. N.A. 112 95172 N.A. N.A. 158 528607 N.A. N.A. N.A. 0.61
Sphalerite (*) BR-73 96 A B.D.L 8.19 0.11 898 16.2 416 N.A. N.A. 310 80184 N.A. N.A. 271 510873 N.A. N.A. N.A. 0.94
Sphalerite (*) 1A_464 98 C1 B.D.L B.D.L 0.15 B.D.L B.D.L B.D.L N.A. N.A. 71.7 101535 N.A. N.A. 3743 539118 N.A. N.A. N.A. B.D.L
Sphalerite (*) 1A_431 99 C1 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L N.A. N.A. 26.4 9529 N.A. N.A. 244 613660 N.A. N.A. N.A. B.D.L
Sphalerite (*) 1A_431 102 C1 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L N.A. N.A. 33.9 35794 N.A. N.A. 20.6 598043 N.A. N.A. N.A. B.D.L
Sphalerite (*) 1A_431 105 C1 B.D.L B.D.L 0.45 B.D.L B.D.L B.D.L N.A. N.A. 81.1 71401 N.A. N.A. 29.5 554993 N.A. N.A. N.A. B.D.L
289
Rb Sr Au
(nist) (nist) nist)
Sphalerite BR-73 91 B.D.L B.D.L B.D.L B.D.L 8.52 701 26.6 169 0.2 0.31 B.D.L B.D.L 8.21 0.08 0.53 B.D.L B.D.L B.D.L
Sphalerite BR-73 92 B.D.L B.D.L B.D.L B.D.L 3.32 634 25.9 4.57 B.D.L B.D.L B.D.L B.D.L 3.82 B.D.L B.D.L B.D.L B.D.L B.D.L
Sphalerite (*) BR-73 95 N.A. B.D.L B.D.L N.A. 4.36 776 N.A. N.A. 0.24 0.14 N.A. N.A. N.A. B.D.L 0.41 B.D.L N.A. N.A.
Sphalerite (*) BR-73 96 N.A. B.D.L 0 N.A. 7.72 1212 N.A. N.A. 1.36 B.D.L N.A. N.A. N.A. B.D.L 5 0.04 N.A. N.A.
Sphalerite (*) BR-73 97 N.A. B.D.L B.D.L N.A. 13 1399 N.A. N.A. 0.35 B.D.L N.A. N.A. N.A. B.D.L 0.47 B.D.L N.A. N.A.
Sphalerite (*) 1A_464 98 N.A. B.D.L B.D.L N.A. 119 1609 N.A. N.A. B.D.L B.D.L N.A. N.A. N.A. B.D.L 0.26 B.D.L N.A. N.A.
Sphalerite (*) 1A_431 99 N.A. B.D.L B.D.L N.A. 55.6 1191 N.A. N.A. 9.2 B.D.L N.A. N.A. N.A. B.D.L 14.2 B.D.L N.A. N.A.
Sphalerite (*) 1A_431 100 N.A. B.D.L B.D.L N.A. 538 697 N.A. N.A. 93.9 B.D.L N.A. N.A. N.A. B.D.L 92.3 B.D.L N.A. N.A.
Sphalerite (*) 1A_431 101 N.A. B.D.L B.D.L N.A. 94.4 1081 N.A. N.A. 13.9 B.D.L N.A. N.A. N.A. 0.03 18.9 B.D.L N.A. N.A.
Sphalerite (*) 1A_431 102 N.A. B.D.L B.D.L N.A. 0.53 662 N.A. N.A. B.D.L B.D.L N.A. N.A. N.A. B.D.L 1.66 B.D.L N.A. N.A.
Sphalerite (*) 1A_431 104 N.A. B.D.L B.D.L N.A. 11 855 N.A. N.A. 4 B.D.L N.A. N.A. N.A. B.D.L 6.89 B.D.L N.A. N.A.
Sphalerite (*) 1A_431 105 N.A. B.D.L B.D.L N.A. 1.45 676 N.A. N.A. 0.6 B.D.L N.A. N.A. N.A. B.D.L 2.08 0.05 N.A. N.A.
Sphalerite (*) 1A_431 107 N.A. B.D.L B.D.L N.A. 8 971 N.A. N.A. 2.01 B.D.L N.A. N.A. N.A. 0.04 2.52 B.D.L N.A. N.A.
Sphalerite (*) 1A_431 108 N.A. B.D.L B.D.L N.A. 1.67 1111 N.A. N.A. B.D.L B.D.L N.A. N.A. N.A. B.D.L B.D.L B.D.L N.A. N.A.
290
Ga Ge 72 Ge74
) (nist) (nist)
Sphalerite (*) 1A_464 129 C1 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L N.A. N.A. 104 67434 N.A. N.A. 765 527428 N.A. N.A. N.A. B.D.L
Sphalerite (*) 1A_464 135 C1 B.D.L B.D.L 0.07 B.D.L B.D.L B.D.L N.A. N.A. 117 111608 N.A. N.A. 702 536259 N.A. N.A. N.A. 0.16
Sphalerite (*) 3A_26 136 C1 B.D.L B.D.L 0.26 B.D.L B.D.L B.D.L N.A. N.A. B.D.L 937 N.A. N.A. 25.5 661686 N.A. N.A. N.A. B.D.L
Sphalerite (*) 3A_26 137 C1 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L N.A. N.A. B.D.L 743 N.A. N.A. 20.1 660474 N.A. N.A. N.A. B.D.L
Sphalerite (*) 3A_26 143 C1 B.D.L B.D.L 0.56 B.D.L B.D.L B.D.L N.A. N.A. B.D.L 937 N.A. N.A. 26.2 660322 N.A. N.A. N.A. B.D.L
Sphalerite 3A_26 146 C1 N.A. N.A. N.A. N.A. N.A. N.A. B.D.L B.D.L B.D.L 840 B.D.L B.D.L 21.2 660000 1.73 B.D.L N.A. B.D.L
Sphalerite 3A_26 147 C1 N.A. N.A. N.A. N.A. N.A. N.A. B.D.L B.D.L 13.2 9202 B.D.L B.D.L 19.7 660000 1.21 B.D.L N.A. B.D.L
Sphalerite (*) 3A_422 150 C1 B.D.L B.D.L B.D.L N.A. B.D.L N.A. N.A. N.A. 36.6 48931 N.A. N.A. 18.9 553380 N.A. N.A. N.A. B.D.L
291
Rb Sr Au
(nist) (nist) nist)
Sphalerite (*) 1A_464 130 N.A. B.D.L B.D.L N.A. 16.1 1257 N.A. N.A. 0.92 B.D.L N.A. N.A. N.A. B.D.L B.D.L B.D.L N.A. N.A.
Sphalerite (*) 1A_464 132 N.A. B.D.L B.D.L N.A. 100 1431 N.A. N.A. B.D.L B.D.L N.A. N.A. N.A. B.D.L 0.24 B.D.L N.A. N.A.
Sphalerite (*) 3A_26 137 N.A. B.D.L B.D.L N.A. B.D.L 1365 N.A. N.A. B.D.L B.D.L N.A. N.A. N.A. B.D.L 0.55 B.D.L N.A. N.A.
Sphalerite (*) 3A_26 140 N.A. B.D.L B.D.L N.A. B.D.L 953 N.A. N.A. 0.48 B.D.L N.A. N.A. N.A. B.D.L 0.8 B.D.L N.A. N.A.
Sphalerite 3A_26 146 B.D.L N.A. N.A. B.D.L 0.05 3049 15.3 B.D.L B.D.L B.D.L B.D.L B.D.L 3.09 B.D.L B.D.L B.D.L B.D.L B.D.L
Sphalerite 3A_26 147 B.D.L N.A. N.A. B.D.L B.D.L 3570 B.D.L 3.24 B.D.L B.D.L B.D.L B.D.L 4 B.D.L B.D.L B.D.L B.D.L B.D.L
Sphalerite 3A_26 148 B.D.L N.A. N.A. B.D.L 31.9 1857 1.99 2.55 43.4 B.D.L B.D.L B.D.L 5.34 0.11 44 B.D.L B.D.L B.D.L
Sphalerite 3A_26 149 B.D.L N.A. N.A. B.D.L 7.23 2148 B.D.L B.D.L 1.55 B.D.L B.D.L B.D.L 6.37 B.D.L 3.2 B.D.L B.D.L B.D.L
292
Ga Ge 72 Ge74
) (nist) (nist)
Sphalerite (*) 3A_422 151 C1 B.D.L B.D.L B.D.L N.A. B.D.L N.A. N.A. N.A. 37.7 50059 N.A. N.A. 17 585786 N.A. N.A. N.A. B.D.L
Sphalerite (*) 3A_422 152 C1 B.D.L B.D.L B.D.L N.A. B.D.L N.A. N.A. N.A. 33.8 52815 N.A. N.A. 16.2 560460 N.A. N.A. N.A. 22.1
Sphalerite (*) 3A_422 153 C1 B.D.L B.D.L 0.14 N.A. B.D.L N.A. N.A. N.A. 48 69345 N.A. N.A. 17.4 563358 N.A. N.A. N.A. 10.1
Sphalerite (*) 3A_422 154 C1 B.D.L B.D.L B.D.L N.A. B.D.L N.A. N.A. N.A. 48 67626 N.A. N.A. 14.4 560228 N.A. N.A. N.A. 8.04
Sphalerite (*) 3A_422 157 C1 B.D.L B.D.L 0.27 N.A. B.D.L N.A. N.A. N.A. 54.6 71483 N.A. N.A. 16.3 544362 N.A. N.A. N.A. 5.37
Sphalerite (*) 3A_CPR77 159 C1 B.D.L B.D.L 5.31 N.A. B.D.L N.A. N.A. N.A. 30.7 22033 N.A. N.A. 81.2 589926 N.A. N.A. N.A. B.D.L
Sphalerite (*) 3A_CPR77 160 C1 B.D.L B.D.L B.D.L N.A. B.D.L N.A. N.A. N.A. 82.3 22090 N.A. N.A. 93.5 552275 N.A. N.A. N.A. B.D.L
Sphalerite (*) 3A_CPR77 161 C1 B.D.L B.D.L B.D.L N.A. B.D.L N.A. N.A. N.A. 23 25571 N.A. N.A. 44.3 596590 N.A. N.A. N.A. B.D.L
Sphalerite (*) 3A_CPR77 170 C1 B.D.L B.D.L 0.81 N.A. B.D.L N.A. N.A. N.A. 57.1 31513 N.A. N.A. 22.3 574924 N.A. N.A. N.A. 5.29
Sphalerite (*) 5A_471 172 C1 B.D.L B.D.L 5.92 B.D.L B.D.L B.D.L N.A. N.A. 104 32947 N.A. N.A. 31.2 561751 N.A. N.A. N.A. B.D.L
Sphalerite (*) 5A_471 174 C1 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L N.A. N.A. 305 64689 N.A. N.A. 26.7 606897 N.A. N.A. N.A. B.D.L
293
Rb Sr Au
(nist) (nist) nist)
Sphalerite (*) 3A_422 151 N.A. B.D.L B.D.L N.A. B.D.L 753 N.A. N.A. B.D.L B.D.L N.A. N.A. N.A. B.D.L B.D.L B.D.L N.A. N.A.
Sphalerite (*) 3A_422 153 N.A. B.D.L B.D.L N.A. 2.32 741 N.A. N.A. B.D.L 0.12 N.A. N.A. N.A. B.D.L 0.09 B.D.L N.A. N.A.
Sphalerite (*) 3A_CPR77 159 N.A. B.D.L B.D.L N.A. 134 1144 N.A. N.A. 64.5 B.D.L N.A. N.A. N.A. 0.09 76.1 B.D.L N.A. N.A.
Sphalerite (*) 3A_CPR77 160 N.A. B.D.L B.D.L N.A. 65.6 658 N.A. N.A. 25.7 B.D.L N.A. N.A. N.A. B.D.L 9.42 B.D.L N.A. N.A.
Sphalerite (*) 3A_CPR77 161 N.A. B.D.L B.D.L N.A. 19.7 680 N.A. N.A. 4.05 B.D.L N.A. N.A. N.A. 0.15 3.89 B.D.L N.A. N.A.
Sphalerite (*) 3A_CPR77 162 N.A. B.D.L B.D.L N.A. B.D.L 758 N.A. N.A. B.D.L B.D.L N.A. N.A. N.A. B.D.L 1.49 B.D.L N.A. N.A.
Sphalerite (*) 3A_CPR77 163 N.A. B.D.L B.D.L N.A. 1.88 714 N.A. N.A. B.D.L B.D.L N.A. N.A. N.A. B.D.L B.D.L B.D.L N.A. N.A.
Sphalerite (*) 3A_CPR77 164 N.A. B.D.L B.D.L N.A. 0.35 704 N.A. N.A. B.D.L B.D.L N.A. N.A. N.A. B.D.L 0.98 B.D.L N.A. N.A.
Sphalerite (*) 3A_CPR77 167 N.A. B.D.L B.D.L N.A. 1.33 894 N.A. N.A. B.D.L B.D.L N.A. N.A. N.A. B.D.L B.D.L B.D.L N.A. N.A.
Sphalerite (*) 3A_CPR77 168 N.A. B.D.L B.D.L N.A. 50.8 2074 N.A. N.A. 24.1 B.D.L N.A. N.A. N.A. B.D.L 26 B.D.L N.A. N.A.
Sphalerite (*) 6A_471 179 N.A. B.D.L B.D.L N.A. 3.51 386 N.A. N.A. 4 B.D.L N.A. N.A. N.A. B.D.L 2.57 B.D.L N.A. N.A.
Sphalerite (*) 6A_471 180 N.A. B.D.L B.D.L N.A. 45 359 N.A. N.A. 29.3 B.D.L N.A. N.A. N.A. B.D.L 12.2 B.D.L N.A. N.A.
294
Ga Ge 72 Ge74
) (nist) (nist)
Sphalerite (*) 6A_471 181 C1 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L N.A. N.A. 108 48625 N.A. N.A. 28.9 596261 N.A. N.A. N.A. 1.79
Sphalerite (*) 6A_471 186 C1 B.D.L B.D.L 3.85 B.D.L B.D.L B.D.L N.A. N.A. 106 49711 N.A. N.A. 50 577478 N.A. N.A. N.A. B.D.L
Sphalerite (*) 6A_471 195 C1 B.D.L B.D.L 0.34 B.D.L B.D.L B.D.L N.A. N.A. 301 94187 N.A. N.A. 211 575906 N.A. N.A. N.A. B.D.L
Sphalerite 6A_CPR471 196 C1 N.A. N.A. N.A. N.A. N.A. N.A. B.D.L B.D.L 156 55170 B.D.L B.D.L 46.7 600000 0.81 B.D.L N.A. B.D.L
Sphalerite 6A_CPR471 197 C1 N.A. N.A. N.A. N.A. N.A. N.A. B.D.L B.D.L 136 56102 B.D.L B.D.L 38.9 600000 0.76 B.D.L N.A. B.D.L
Sphalerite 6A_CPR471 198 C1 N.A. N.A. N.A. N.A. N.A. N.A. B.D.L B.D.L 83.6 43436 B.D.L B.D.L 25.2 600000 1.05 B.D.L N.A. 34.1
Sphalerite 6A_CPR471 199 C1 N.A. N.A. N.A. N.A. N.A. N.A. B.D.L B.D.L 57.6 42277 B.D.L B.D.L 31.2 600000 0.78 B.D.L N.A. B.D.L
Sphalerite (*) BR_138 200 C1 B.D.L B.D.L B.D.L N.A. B.D.L N.A. N.A. N.A. 7.05 2260 N.A. N.A. 37.5 662425 N.A. N.A. N.A. B.D.L
Sphalerite (*) BR_138 201 C1 B.D.L B.D.L 1.18 N.A. B.D.L N.A. N.A. N.A. B.D.L 2363 N.A. N.A. 32.4 666806 N.A. N.A. N.A. B.D.L
Sphalerite (*) BR_138 202 C1 B.D.L B.D.L B.D.L N.A. B.D.L N.A. N.A. N.A. B.D.L 1105 N.A. N.A. 45 659555 N.A. N.A. N.A. B.D.L
Sphalerite (*) BR_138 205 C1 B.D.L B.D.L B.D.L N.A. B.D.L N.A. N.A. N.A. 56.8 1370 N.A. N.A. 22.3 668333 N.A. N.A. N.A. B.D.L
Sphalerite (*) BR_138 206 C1 B.D.L B.D.L 6.01 N.A. B.D.L N.A. N.A. N.A. 10.1 2482 N.A. N.A. 43.6 665663 N.A. N.A. N.A. 26.4
Sphalerite (*) BR-140 207 C1 B.D.L B.D.L 0.24 B.D.L B.D.L B.D.L N.A. N.A. 1295 76750 N.A. N.A. 1062 524562 N.A. N.A. N.A. B.D.L
Sphalerite (*) BR-140 210 C1 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L N.A. N.A. 163 44622 N.A. N.A. 139 524934 N.A. N.A. N.A. B.D.L
295
Rb Sr Au
(nist) (nist) nist)
Sphalerite (*) 6A_471 188 N.A. B.D.L B.D.L N.A. 26.8 539 N.A. N.A. 21.9 B.D.L N.A. N.A. N.A. B.D.L 13 0.18 N.A. N.A.
Sphalerite 6A_CPR471 196 B.D.L N.A. N.A. B.D.L 31.6 1025 0.44 33.4 13.1 B.D.L B.D.L B.D.L 2.68 0.04 6.85 0.12 B.D.L B.D.L
Sphalerite 6A_CPR471 197 B.D.L N.A. N.A. B.D.L 9.31 724 0.25 24.2 7.12 B.D.L B.D.L B.D.L 4.53 0.04 6.83 B.D.L B.D.L B.D.L
Sphalerite 6A_CPR471 198 B.D.L N.A. N.A. B.D.L 5.53 1389 3.63 10.8 5.21 B.D.L B.D.L B.D.L 4.69 B.D.L 20.1 0.61 B.D.L B.D.L
Sphalerite 6A_CPR471 199 B.D.L N.A. N.A. B.D.L 7.89 950 0.71 20.7 4.66 B.D.L B.D.L B.D.L 2.82 B.D.L 20 0.04 B.D.L B.D.L
Sphalerite (*) BR_138 200 N.A. B.D.L B.D.L N.A. 4.56 1270 N.A. N.A. B.D.L B.D.L N.A. N.A. N.A. B.D.L B.D.L B.D.L N.A. N.A.
Sphalerite (*) BR_138 201 N.A. B.D.L B.D.L N.A. 3.89 1481 N.A. N.A. B.D.L B.D.L N.A. N.A. N.A. B.D.L B.D.L B.D.L N.A. N.A.
Sphalerite (*) BR_138 202 N.A. B.D.L B.D.L N.A. 10.7 1850 N.A. N.A. 1.92 B.D.L N.A. N.A. N.A. B.D.L 6.58 B.D.L N.A. N.A.
Sphalerite (*) BR_138 204 N.A. B.D.L B.D.L N.A. 10.9 1300 N.A. N.A. B.D.L B.D.L N.A. N.A. N.A. B.D.L 2.67 B.D.L N.A. N.A.
Sphalerite (*) BR_138 205 N.A. B.D.L B.D.L N.A. 1.19 1066 N.A. N.A. 1 B.D.L N.A. N.A. N.A. B.D.L 2.71 B.D.L N.A. N.A.
Sphalerite (*) BR-140 207 N.A. B.D.L B.D.L N.A. 62.8 935 N.A. N.A. 7.07 B.D.L N.A. N.A. N.A. 0.04 6.93 B.D.L N.A. N.A.
296
Ga Ge 72 Ge74
) (nist) (nist)
Sphalerite (*) BR-140 212 C1 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L N.A. N.A. 86.5 103444 N.A. N.A. 125 529182 N.A. N.A. N.A. B.D.L
Sphalerite (*) BR-140 216 C1 B.D.L B.D.L 13.8 B.D.L B.D.L B.D.L N.A. N.A. 36.1 16347 N.A. N.A. 260 484312 N.A. N.A. N.A. B.D.L
Sphalerite (*) BR-140 218 C1 B.D.L B.D.L 12 B.D.L B.D.L B.D.L N.A. N.A. 40.4 14429 N.A. N.A. 498 441470 N.A. N.A. N.A. B.D.L
Sphalerite (*) BR-140 227 C1 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L N.A. N.A. 46.6 46312 N.A. N.A. 67.1 540723 N.A. N.A. N.A. B.D.L
Sphalerite (*) BR-140 229 C1 B.D.L B.D.L 0.36 B.D.L B.D.L B.D.L N.A. N.A. 810 94085 N.A. N.A. 305 347402 N.A. N.A. N.A. 24.3
Sphalerite (*) BR-140 230 C1 B.D.L B.D.L B.D.L 11991 255 12139 N.A. N.A. 731 103325 N.A. N.A. 260 466027 N.A. N.A. N.A. 37.7
Sphalerite (*) BR-140 234 C1 B.D.L B.D.L B.D.L 21785 754 25616 N.A. N.A. 171 101706 N.A. N.A. 202 368267 N.A. N.A. N.A. B.D.L
Sphalerite (*) BR-140 235 C1 B.D.L B.D.L B.D.L N.A. B.D.L N.A. N.A. N.A. 9.44 9328 N.A. N.A. 157 643252 N.A. N.A. N.A. B.D.L
Sphalerite (*) BR-140 237 C1 B.D.L B.D.L B.D.L N.A. B.D.L N.A. N.A. N.A. B.D.L 6832 N.A. N.A. 222 645729 N.A. N.A. N.A. 14.7
Sphalerite (*) BR-140 239 C1 B.D.L B.D.L B.D.L N.A. B.D.L N.A. N.A. N.A. 9.7 12006 N.A. N.A. 95.3 640525 N.A. N.A. N.A. 6.44
Sphalerite (*) BR-140 240 C1 B.D.L B.D.L B.D.L N.A. B.D.L N.A. N.A. N.A. 7.32 10319 N.A. N.A. 66.8 644579 N.A. N.A. N.A. B.D.L
297
Rb Sr Au
(nist) (nist) nist)
Sphalerite (*) BR-140 213 N.A. B.D.L B.D.L N.A. 18.2 999 N.A. N.A. 0.36 B.D.L N.A. N.A. N.A. 0.01 1.55 0.01 N.A. N.A.
Sphalerite (*) BR-140 226 N.A. B.D.L B.D.L N.A. 7.07 836 N.A. N.A. 0.78 B.D.L N.A. N.A. N.A. 0.06 0.66 0.01 N.A. N.A.
Sphalerite (*) BR-140 230 N.A. B.D.L B.D.L N.A. 37 2405 N.A. N.A. 1 B.D.L N.A. N.A. N.A. B.D.L B.D.L B.D.L N.A. N.A.
Sphalerite (*) BR-140 231 N.A. B.D.L 0.18 N.A. 35.3 2698 N.A. N.A. B.D.L B.D.L N.A. N.A. N.A. B.D.L B.D.L 0.19 N.A. N.A.
298
Ga Ge 72 Ge74
) (nist) (nist)
Sphalerite (*) BR-140 241 C1 B.D.L B.D.L B.D.L N.A. B.D.L N.A. N.A. N.A. B.D.L 4972 N.A. N.A. 131 635416 N.A. N.A. N.A. B.D.L
Sphalerite (*) BR-140 242 C1 B.D.L B.D.L B.D.L N.A. B.D.L N.A. N.A. N.A. 13 14082 N.A. N.A. 84.6 642434 N.A. N.A. N.A. 8.39
Sphalerite (*) BR-140 243 C1 B.D.L B.D.L B.D.L N.A. B.D.L N.A. N.A. N.A. 10.7 7552 N.A. N.A. 85.4 621137 N.A. N.A. N.A. 5.2
Sphalerite (*) BR-140 244 C1 B.D.L B.D.L B.D.L N.A. B.D.L N.A. N.A. N.A. 6.51 4926 N.A. N.A. 129 644005 N.A. N.A. N.A. 7.17
Sphalerite (*) BR-140 245 C1 B.D.L B.D.L B.D.L N.A. B.D.L N.A. N.A. N.A. 8 7254 N.A. N.A. 27.2 640117 N.A. N.A. N.A. 5.8
Sphalerite (*) BR-180 251 C1 B.D.L B.D.L B.D.L N.A. B.D.L N.A. N.A. N.A. 25 23069 N.A. N.A. 298 610799 N.A. N.A. N.A. B.D.L
Sphalerite (*) BR-180 252 C1 B.D.L B.D.L 3.98 N.A. B.D.L N.A. N.A. N.A. 27.2 15375 N.A. N.A. 26.4 610269 N.A. N.A. N.A. B.D.L
Sphalerite (*) BR-180 253 C1 B.D.L B.D.L B.D.L N.A. B.D.L N.A. N.A. N.A. 31 19778 N.A. N.A. 19.1 608439 N.A. N.A. N.A. B.D.L
Sphalerite (*) BR-180 254 C1 B.D.L B.D.L B.D.L N.A. B.D.L N.A. N.A. N.A. 23 14850 N.A. N.A. 19.1 594691 N.A. N.A. N.A. B.D.L
Sphalerite (*) BR-180 258 C1 B.D.L B.D.L 2.09 N.A. B.D.L N.A. N.A. N.A. 32.4 18405 N.A. N.A. 185 625009 N.A. N.A. N.A. B.D.L
Sphalerite (*) BR-196 261 C1 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L N.A. N.A. B.D.L 145 N.A. N.A. 62.6 671439 N.A. N.A. N.A. B.D.L
Sphalerite (*) BR-196 262 C1 B.D.L B.D.L 0.98 B.D.L B.D.L B.D.L N.A. N.A. B.D.L 365 N.A. N.A. 50.4 670332 N.A. N.A. N.A. B.D.L
Sphalerite (*) BR-196 263 C1 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L N.A. N.A. B.D.L 393 N.A. N.A. 67.8 658724 N.A. N.A. N.A. B.D.L
Sphalerite (*) BR-196 264 C1 B.D.L B.D.L 0.81 B.D.L B.D.L B.D.L N.A. N.A. 0.89 582 N.A. N.A. 58 659882 N.A. N.A. N.A. B.D.L
Sphalerite (*) BR-196 265 C1 B.D.L B.D.L 2.16 B.D.L B.D.L B.D.L N.A. N.A. B.D.L 217 N.A. N.A. 21 661610 N.A. N.A. N.A. B.D.L
Sphalerite (*) BR-196 266 C1 B.D.L B.D.L 2.23 B.D.L B.D.L B.D.L N.A. N.A. 0.9 704 N.A. N.A. 36.9 658475 N.A. N.A. N.A. 0.44
Sphalerite (*) BR-196 268 C1 B.D.L B.D.L 0.94 B.D.L B.D.L B.D.L N.A. N.A. 0.95 1178 N.A. N.A. 45.6 661610 N.A. N.A. N.A. B.D.L
Sphalerite (*) BR-196 270 C1 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L N.A. N.A. B.D.L 192 N.A. N.A. 55 667430 N.A. N.A. N.A. B.D.L
299
Rb Sr Au
(nist) (nist) nist)
Sphalerite (*) BR-140 241 N.A. B.D.L B.D.L N.A. 1.16 795 N.A. N.A. 0.75 B.D.L N.A. N.A. N.A. B.D.L B.D.L B.D.L N.A. N.A.
Sphalerite (*) BR-140 242 N.A. B.D.L B.D.L N.A. 0.84 786 N.A. N.A. B.D.L 0.23 N.A. N.A. N.A. B.D.L 1.74 B.D.L N.A. N.A.
Sphalerite (*) BR-140 248 N.A. B.D.L B.D.L N.A. 24.3 1058 N.A. N.A. 40 B.D.L N.A. N.A. N.A. B.D.L 12.7 B.D.L N.A. N.A.
Sphalerite (*) BR-180 259 N.A. B.D.L B.D.L N.A. 28.3 590 N.A. N.A. 3.31 B.D.L N.A. N.A. N.A. B.D.L 21 B.D.L N.A. N.A.
Sphalerite (*) BR-196 261 N.A. B.D.L B.D.L N.A. 326 2058 N.A. N.A. B.D.L B.D.L N.A. N.A. N.A. B.D.L 18.7 B.D.L N.A. N.A.
Sphalerite (*) BR-196 264 N.A. B.D.L B.D.L N.A. 105 2126 N.A. N.A. 1.8 B.D.L N.A. N.A. N.A. 0.23 21.4 B.D.L N.A. N.A.
Sphalerite (*) BR-196 265 N.A. B.D.L B.D.L N.A. 48 1825 N.A. N.A. B.D.L B.D.L N.A. N.A. N.A. B.D.L 376 0.14 N.A. N.A.
Sphalerite (*) BR-196 267 N.A. B.D.L B.D.L N.A. 216 2527 N.A. N.A. 3.53 B.D.L N.A. N.A. N.A. 0.55 54.3 0.02 N.A. N.A.
Sphalerite (*) BR-196 268 N.A. B.D.L B.D.L N.A. 118 1981 N.A. N.A. 0.61 B.D.L N.A. N.A. N.A. 0.04 2080 B.D.L N.A. N.A.
Sphalerite (*) BR-196 269 N.A. B.D.L B.D.L N.A. 75.4 1696 N.A. N.A. B.D.L B.D.L N.A. N.A. N.A. B.D.L 10 B.D.L N.A. N.A.
Sphalerite (*) BR-196 270 N.A. B.D.L B.D.L N.A. 156 1534 N.A. N.A. B.D.L B.D.L N.A. N.A. N.A. 0.1 13.6 B.D.L N.A. N.A.
300
Ga Ge 72 Ge74
) (nist) (nist)
Sphalerite BR-196 276 C1 N.A. N.A. N.A. N.A. N.A. N.A. B.D.L B.D.L B.D.L 1021 0.82 B.D.L 44 671000 1.69 B.D.L N.A. B.D.L
Sphalerite BR-196 277 C1 N.A. N.A. N.A. N.A. N.A. N.A. B.D.L B.D.L B.D.L 378 0.38 0.81 42.7 671000 0.89 B.D.L N.A. B.D.L
Sphalerite BR-196 278 C1 N.A. N.A. N.A. N.A. N.A. N.A. B.D.L B.D.L 5.56 2356 B.D.L B.D.L 64.4 671000 0.68 B.D.L N.A. B.D.L
Sphalerite BR-196 279 C1 N.A. N.A. N.A. N.A. N.A. N.A. B.D.L B.D.L B.D.L 206 B.D.L B.D.L 31.6 660000 0.7 1.23 N.A. B.D.L
Sphalerite BR-196 280 C1 N.A. N.A. N.A. N.A. N.A. N.A. B.D.L B.D.L B.D.L 485 0.61 B.D.L 53.6 660000 1.05 B.D.L N.A. B.D.L
Sphalerite BR-196 281 C1 N.A. N.A. N.A. N.A. N.A. N.A. B.D.L B.D.L B.D.L 708 0.29 B.D.L 35.6 660000 1.42 2.49 N.A. B.D.L
Sphalerite BR-196 282 C1 N.A. N.A. N.A. N.A. N.A. N.A. B.D.L B.D.L B.D.L 1367 1.55 B.D.L 36.1 660000 0.99 B.D.L N.A. B.D.L
301
Rb Sr Au
(nist) (nist) nist)
Sphalerite (*) BR-196 271 N.A. B.D.L B.D.L N.A. 192 1856 N.A. N.A. 0.52 0.44 N.A. N.A. N.A. B.D.L 23.2 B.D.L N.A. N.A.
Sphalerite (*) BR-196 272 N.A. B.D.L B.D.L N.A. 270 2764 N.A. N.A. B.D.L B.D.L N.A. N.A. N.A. B.D.L 4.62 B.D.L N.A. N.A.
Sphalerite (*) BR-196 273 N.A. B.D.L B.D.L N.A. 980 2426 N.A. N.A. 4.5 B.D.L N.A. N.A. N.A. 0.5 43.4 B.D.L N.A. N.A.
Sphalerite (*) BR-196 274 N.A. B.D.L B.D.L N.A. 444 2863 N.A. N.A. 2.02 0.51 N.A. N.A. N.A. 0.1 22.9 B.D.L N.A. N.A.
Sphalerite (*) BR-196 275 N.A. B.D.L B.D.L N.A. 776 1986 N.A. N.A. 2.39 B.D.L N.A. N.A. N.A. 0.4 347 B.D.L N.A. N.A.
Sphalerite BR-196 276 B.D.L N.A. N.A. B.D.L 106 4416 104 20.7 0.2 0.28 B.D.L B.D.L 7.1 B.D.L 15.7 B.D.L B.D.L B.D.L
Sphalerite BR-196 277 B.D.L N.A. N.A. B.D.L 123 3662 0.89 4.97 0.95 B.D.L B.D.L B.D.L 7.08 0.14 7.04 B.D.L B.D.L B.D.L
Sphalerite BR-196 278 B.D.L N.A. N.A. B.D.L 82.6 3866 31.3 3.3 B.D.L B.D.L B.D.L B.D.L 7.41 B.D.L 3.36 B.D.L B.D.L B.D.L
Sphalerite BR-196 279 B.D.L N.A. N.A. B.D.L 105 2454 20.1 7.28 0.35 B.D.L B.D.L B.D.L 3.87 B.D.L 65.6 B.D.L B.D.L B.D.L
Sphalerite BR-196 280 B.D.L N.A. N.A. B.D.L 70.6 4631 19.4 6.35 0.14 B.D.L B.D.L B.D.L 7.78 B.D.L 9.9 B.D.L B.D.L B.D.L
Sphalerite BR-196 281 B.D.L N.A. N.A. B.D.L 72.3 5549 85.7 7.01 B.D.L 0.26 B.D.L B.D.L 6.59 B.D.L 5.57 B.D.L B.D.L B.D.L
Sphalerite BR-196 282 B.D.L N.A. N.A. B.D.L 33.9 3171 3.65 7.79 B.D.L B.D.L B.D.L B.D.L 5.4 B.D.L 3.19 B.D.L B.D.L B.D.L
302
Table A.6: LA-ICP-MS analyses of enargite crystals from stage C2
Sampl analys Mineralizatio

Mineral Na (ppm) V (ppm) Cr (ppm) Mn (ppm) Fe (ppm) Co (ppm) Ni (ppm) Cu (ppm) Zn (ppm) Ga (ppm) Se (ppm) Mo (ppm) Ag (ppm)
e # e # n stage
Enargite (*) BR-152 1 C2 B.D.L N.A. N.A. B.D.L B.D.L N.A. N.A. 480000 714 N.A. N.A. N.A. 177
Enargite (*) BR-152 4 C2 B.D.L N.A. N.A. B.D.L B.D.L N.A. N.A. 480000 281 N.A. N.A. N.A. 36.1
Enargite (*) BR-152 6 C2 B.D.L N.A. N.A. 46.8 B.D.L N.A. N.A. 480000 284 N.A. N.A. N.A. 86.3
Enargite (*) BR-152 8 C2 12.6 N.A. N.A. B.D.L B.D.L N.A. N.A. 480000 215 N.A. N.A. N.A. 38.8
Enargite (*) BR-152 13 C2 0.57 N.A. N.A. B.D.L B.D.L N.A. N.A. 480000 145 N.A. N.A. N.A. 16
Enargite (*) BR-152 16 C2 B.D.L N.A. N.A. B.D.L B.D.L N.A. N.A. 480000 46.8 N.A. N.A. N.A. 13
Enargite (*) BR-152 17 C2 B.D.L N.A. N.A. B.D.L B.D.L N.A. N.A. 480000 93.1 N.A. N.A. N.A. 14.6
Enargite (*) BR-152 20 C2 2.2 N.A. N.A. B.D.L B.D.L N.A. N.A. 480000 24.8 N.A. N.A. N.A. 85.6
Enargite (*) BR-152 21 C2 8.7 N.A. N.A. 37.9 B.D.L N.A. N.A. 480000 77.2 N.A. N.A. N.A. 181
Enargite (*) BR-152 22 C2 0.89 N.A. N.A. B.D.L B.D.L N.A. N.A. 480000 37.2 N.A. N.A. N.A. 22
Enargite (*) 2B_439 25 C2 B.D.L N.A. N.A. B.D.L 51.9 N.A. N.A. 480000 30.7 N.A. N.A. N.A. 60.9
Enargite (*) 2B_439 26 C2 1.4 N.A. N.A. B.D.L B.D.L N.A. N.A. 480000 11.8 N.A. N.A. N.A. 68
Enargite (*) 2B_439 27 C2 0.74 N.A. N.A. B.D.L 38.8 N.A. N.A. 480000 29.4 N.A. N.A. N.A. 65.6
Enargite (*) 2B_439 28 C2 B.D.L N.A. N.A. B.D.L B.D.L N.A. N.A. 480000 B.D.L N.A. N.A. N.A. 121
Enargite (*) 2B_439 29 C2 20 N.A. N.A. B.D.L B.D.L N.A. N.A. 480000 B.D.L N.A. N.A. N.A. 110
Enargite (*) 2B_439 30 C2 0.73 N.A. N.A. 3.3 B.D.L N.A. N.A. 480000 12.2 N.A. N.A. N.A. 69.2
Enargite (*) 2B_439 31 C2 0.84 N.A. N.A. B.D.L B.D.L N.A. N.A. 480000 10.6 N.A. N.A. N.A. 69.5
303

Mineral Cd (ppm) In (ppm) Sn (ppm) Sb (ppm) Te (ppm) Ba (ppm) W (ppm) Au (ppm)( Hg (ppm) Tl (ppm) Pb (ppm) Bi (ppm)
e # e # n stage
Enargite (*) BR-152 1 C2 N.A. N.A. 5749 19829 497 1.9 N.A. B.D.L N.A. B.D.L 26.5 3.2
Enargite (*) BR-152 2 C2 N.A. N.A. 4350 23082 911 B.D.L N.A. B.D.L N.A. B.D.L 14.5 3.6
Enargite (*) BR-152 3 C2 N.A. N.A. 4458 19607 577 B.D.L N.A. 1.5 N.A. B.D.L 19.7 2
Enargite (*) BR-152 6 C2 N.A. N.A. 2674 63086 167 7.5 N.A. B.D.L N.A. 1.2 26.8 22.8
Enargite (*) BR-152 8 C2 N.A. N.A. 2366 60297 130 B.D.L N.A. B.D.L N.A. B.D.L 813 18.4
Enargite (*) BR-152 10 C2 N.A. N.A. 4417 57453 197 11 N.A. B.D.L N.A. B.D.L 7.1 201
Enargite (*) BR-152 11 C2 N.A. N.A. 3802 38760 910 B.D.L N.A. B.D.L N.A. B.D.L 9.3 132
Enargite (*) BR-152 13 C2 N.A. N.A. 639 8463 92 1.3 N.A. B.D.L N.A. 0.1 2.3 3
Enargite (*) BR-152 14 C2 N.A. N.A. 864 17535 53.7 B.D.L N.A. B.D.L N.A. B.D.L 7.6 3.5
Enargite (*) BR-152 15 C2 N.A. N.A. 671 9659 80.7 1.1 N.A. B.D.L N.A. B.D.L 4.2 1.7
Enargite (*) BR-152 17 C2 N.A. N.A. 840 8718 52.1 2 N.A. B.D.L N.A. B.D.L 0.58 3
Enargite (*) BR-152 18 C2 N.A. N.A. 582 6626 32.3 B.D.L N.A. B.D.L N.A. B.D.L B.D.L B.D.L
Enargite (*) BR-152 19 C2 N.A. N.A. 336 4128 22.8 B.D.L N.A. B.D.L N.A. B.D.L B.D.L B.D.L
Enargite (*) BR-152 20 C2 N.A. N.A. 540 4088 220 2 N.A. 0.35 N.A. 0.26 11.3 1.6
Enargite (*) BR-152 21 C2 N.A. N.A. 1528 41035 43.3 B.D.L N.A. B.D.L N.A. B.D.L 110 B.D.L
Enargite (*) BR-152 23 C2 N.A. N.A. 450 12046 24.9 9.1 N.A. B.D.L N.A. 0.26 B.D.L 0.14
Enargite (*) 2B_439 25 C2 N.A. N.A. 37.2 2288 298 5.7 N.A. 0.23 N.A. B.D.L 1.7 1.1
Enargite (*) 2B_439 26 C2 N.A. N.A. 33 2209 258 B.D.L N.A. 0.59 N.A. B.D.L 3.5 0.81
Enargite (*) 2B_439 27 C2 N.A. N.A. 61.4 2006 224 B.D.L N.A. 0.34 N.A. B.D.L 3 1.2
Enargite (*) 2B_439 28 C2 N.A. N.A. 77.2 5012 825 B.D.L N.A. B.D.L N.A. B.D.L 3.5 B.D.L
Enargite (*) 2B_439 29 C2 N.A. N.A. 84.3 4442 557 B.D.L N.A. B.D.L N.A. B.D.L B.D.L 2.1
Enargite (*) 2B_439 30 C2 N.A. N.A. 37.9 2340 323 B.D.L N.A. 0.6 N.A. B.D.L 3.8 0.75
304
e # e # n stage
Enargite (*) BR-143 32 C2 B.D.L N.A. N.A. B.D.L B.D.L N.A. N.A. 480000 B.D.L N.A. N.A. N.A. 1339
Enargite (*) BR-143 33 C2 5.5 N.A. N.A. B.D.L B.D.L N.A. N.A. 480000 B.D.L N.A. N.A. N.A. 1146
Enargite (*) 2B_439 36 C2 14.1 N.A. N.A. 3.2 B.D.L N.A. N.A. 480000 13.1 N.A. N.A. N.A. 65.3
Enargite (*) 2B_439 37 C2 0.29 N.A. N.A. B.D.L 40.2 N.A. N.A. 480000 13.4 N.A. N.A. N.A. 61.7
Enargite (*) BR-143 39 C2 1.3 N.A. N.A. B.D.L 73.2 N.A. N.A. 480000 9.2 N.A. N.A. N.A. 589
Enargite (*) BR-152 47 C2 6.7 N.A. N.A. 63.4 B.D.L N.A. N.A. 480000 59 N.A. N.A. N.A. 47
Enargite (*) BR-152 49 C2 1.7 N.A. N.A. B.D.L B.D.L N.A. N.A. 480000 48.4 N.A. N.A. N.A. 15.8
Enargite BR-143 56 C2 0.81 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 484000 13.3 B.D.L B.D.L B.D.L 405
Enargite BR-143 57 C2 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 484000 68.1 B.D.L B.D.L B.D.L 85.8
Enargite BR-143 58 C2 0.99 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 484000 108 B.D.L B.D.L B.D.L 169
Enargite BR-143 59 C2 0.28 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 484000 21 B.D.L B.D.L B.D.L 80.8
Enargite 2B_439 62 C2 B.D.L B.D.L B.D.L B.D.L 32.3 B.D.L B.D.L 484000 14.5 B.D.L B.D.L B.D.L 144
305
e # e # n stage
Enargite (*) BR-143 32 C2 N.A. N.A. 675 35914 1631 B.D.L N.A. B.D.L N.A. B.D.L B.D.L B.D.L
Enargite (*) BR-143 34 C2 N.A. N.A. 437 19560 645 B.D.L N.A. B.D.L N.A. B.D.L B.D.L 0.96
Enargite (*) BR-143 39 C2 N.A. N.A. 119 4806 212 B.D.L N.A. B.D.L N.A. 0.15 2.4 1.1
Enargite (*) BR-143 41 C2 N.A. N.A. 87.2 3789 280 B.D.L N.A. B.D.L N.A. B.D.L 0.67 0.28
Enargite (*) BR-143 42 C2 N.A. N.A. 526 18839 1149 10.3 N.A. B.D.L N.A. B.D.L B.D.L 1.6
Enargite (*) BR-152 46 C2 N.A. N.A. 522 13634 13.2 6.8 N.A. B.D.L N.A. B.D.L 0.59 0.27
Enargite (*) BR-152 49 C2 N.A. N.A. 357 12518 77.5 5.9 N.A. B.D.L N.A. 0.03 1.7 0.5
Enargite (*) BR-143 51 C2 N.A. N.A. 182 8491 279 2.8 N.A. B.D.L N.A. B.D.L 0.79 B.D.L
Enargite (*) BR-143 53 C2 N.A. N.A. 102 4253 205 1 N.A. B.D.L N.A. 0.03 0.45 B.D.L
Enargite (*) BR-152 54 C2 N.A. N.A. 2258 21098 53.2 11.9 N.A. B.D.L N.A. 0.15 7.3 2.8
Enargite BR-143 56 C2 0.31 3.1 161 3970 706 N.A. B.D.L 0.27 9.2 0.03 0.63 0.68
Enargite BR-143 57 C2 2.3 5.6 859 10270 184 N.A. 2.7 0.96 73.5 0.11 1 3.1
Enargite BR-143 58 C2 2 5.8 1003 11683 256 N.A. 3.3 1 79.6 0.72 6.3 5.8
Enargite BR-143 59 C2 B.D.L 3.2 178 5349 95.2 N.A. 2.9 B.D.L 9.4 B.D.L 0.75 0.2
Enargite BR-143 60 C2 B.D.L 4.2 358 8414 622 N.A. 0.79 0.21 17.1 B.D.L 0.66 0.7
Enargite BR-143 61 C2 2.8 5.5 857 10695 140 N.A. 0.96 B.D.L 78.5 B.D.L 0.76 1.4
Enargite 2B_439 62 C2 B.D.L 2.8 19.9 1617 396 N.A. B.D.L 0.3 B.D.L B.D.L 1.6 0.25
306
e # e # n stage
Enargite 2B_439 63 C2 0.33 B.D.L B.D.L 4.2 B.D.L B.D.L B.D.L 484000 15.4 B.D.L B.D.L B.D.L 62.7
Enargite 2B_439 64 C2 2.2 B.D.L B.D.L 2.7 B.D.L B.D.L B.D.L 484000 97.5 B.D.L B.D.L B.D.L 62.3
Enargite 2B_439 65 C2 3.4 B.D.L B.D.L B.D.L 53 B.D.L B.D.L 484000 57.6 B.D.L B.D.L B.D.L 79.4
Enargite 2B_439 66 C2 5 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 484000 40.6 B.D.L B.D.L B.D.L 76.2
Enargite 2B_439 67 C2 0.51 B.D.L B.D.L B.D.L 81.2 B.D.L B.D.L 484000 63.5 B.D.L B.D.L B.D.L 66.5
Enargite 2B_439 68 C2 B.D.L B.D.L B.D.L 5.6 396 B.D.L B.D.L 484000 95.1 B.D.L B.D.L 0.7 61.2
Enargite 2B_439 69 C2 3.8 B.D.L B.D.L 5 222 B.D.L B.D.L 484000 548 B.D.L B.D.L B.D.L 103
Enargite 2B_439 70 C2 2.3 B.D.L B.D.L B.D.L 66.4 B.D.L B.D.L 484000 14.9 B.D.L B.D.L B.D.L 73.6
307
e # e # n stage
Enargite 2B_439 63 C2 1.3 2.7 26.3 1683 265 N.A. B.D.L 0.29 2.4 B.D.L 2.2 0.44
Enargite 2B_439 64 C2 B.D.L 3.3 26 1792 264 N.A. 0.24 0.47 2 0.14 8.6 1.9
Enargite 2B_439 65 C2 B.D.L 3.1 27.6 1759 217 N.A. B.D.L 0.47 2.6 0.3 18.4 14.5
Enargite 2B_439 66 C2 1.5 3.4 48.4 1970 184 N.A. 1 0.48 B.D.L 0.11 14.1 5.2
Enargite 2B_439 67 C2 B.D.L 2.6 25.4 1606 175 N.A. B.D.L 0.48 B.D.L 0.07 7.1 0.78
Enargite 2B_439 68 C2 B.D.L 3 31.6 1723 181 N.A. 0.22 0.82 2.9 0.43 9.8 1.1
Enargite 2B_439 69 C2 4.9 3.1 78.7 1980 250 N.A. 1.5 0.96 6.1 0.67 31 10.3
Enargite 2B_439 70 C2 B.D.L 3.4 31.1 2047 194 N.A. 2.2 0.41 2.4 0.12 5.1 1.9
308
Table A.7: LA-ICP-MS analyses of pyrite crystals from stages B2, C1 and C2
Analyses Mineralization
Mineral Sample # V (ppm) Cr (ppm) Mn (ppm) Fe (ppm) Co (ppm) Ni (ppm) Cu (ppm) Zn (ppm) Ga (ppm) As (ppm) Se (ppm) Mo (ppm) Ag (ppm)
# stage
Pyrite BR 80 1 B2 B.D.L. B.D.L. 11.2 465000 B.D.L. B.D.L. 1993 4962 2.4 707 13 B.D.L. 16
Pyrite BR 80 2 B2 B.D.L. B.D.L. 3.9 465000 B.D.L. B.D.L. 1.6 B.D.L. B.D.L. 2840 B.D.L. B.D.L. 0.7
Pyrite BR 80 3 B2 B.D.L. B.D.L. 4.4 465000 B.D.L. B.D.L. 2.2 B.D.L. B.D.L. 1450 9.8 B.D.L. 3
Pyrite BR 80 5 B2 B.D.L. B.D.L. 5.2 465000 B.D.L. B.D.L. 1.6 B.D.L. B.D.L. 29.6 B.D.L. B.D.L. 0.84
Pyrite BR 80 6 B2 0.42 B.D.L. 5.1 465000 B.D.L. 1.4 4.3 B.D.L. B.D.L. 979 B.D.L. B.D.L. 5.6
Pyrite BR 80 7 B2 0.2 B.D.L. 5.2 465000 B.D.L. B.D.L. 23.6 B.D.L. B.D.L. 3048 16.6 B.D.L. 6.6
Pyrite BR 80 9 B2 B.D.L. B.D.L. 4.1 465000 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 217 B.D.L. B.D.L. 5.3
Pyrite BR 80 13 B2 B.D.L. B.D.L. 5 465000 B.D.L. B.D.L. 0.99 B.D.L. B.D.L. 1537 B.D.L. B.D.L. 0.99
Pyrite BR 80 15 B2 B.D.L. B.D.L. 4.5 465000 B.D.L. B.D.L. 0.7 B.D.L. B.D.L. 274 9.1 B.D.L. 5.7
Pyrite BR 80 16 B2 B.D.L. B.D.L. 5 465000 B.D.L. B.D.L. 0.72 B.D.L. B.D.L. 346 B.D.L. B.D.L. 2.8
Pyrite BR 80 17 B2 B.D.L. B.D.L. 5.9 465000 B.D.L. B.D.L. 8.1 B.D.L. B.D.L. 803 10 B.D.L. 9.8
Pyrite BR 80 18 B2 B.D.L. 8 5.1 465000 B.D.L. B.D.L. 8 B.D.L. B.D.L. 942 B.D.L. B.D.L. 2.9
Pyrite BR 80 19 B2 B.D.L. B.D.L. 3.8 465000 B.D.L. B.D.L. 3.8 B.D.L. B.D.L. 66.3 7.3 B.D.L. 7.2
Pyrite BR-106 21 B2 B.D.L. B.D.L. 4.6 465000 B.D.L. 1.5 13.8 B.D.L. B.D.L. 36.7 B.D.L. B.D.L. B.D.L.
Pyrite BR-106 22 B2 B.D.L. B.D.L. 4.9 465000 0.99 1.8 2.2 B.D.L. B.D.L. 46.5 B.D.L. B.D.L. 0.5
Pyrite BR-106 23 B2 B.D.L. B.D.L. 5.3 465000 B.D.L. 0.13 B.D.L. B.D.L. B.D.L. 20.8 B.D.L. B.D.L. 0.07
Pyrite BR-106 24 B2 B.D.L. B.D.L. 3.7 465000 0.52 B.D.L. B.D.L. B.D.L. B.D.L. 795 B.D.L. B.D.L. B.D.L.
Pyrite BR-106 25 B2 B.D.L. 8.3 4.5 465000 B.D.L. B.D.L. 1.3 B.D.L. B.D.L. 1929 B.D.L. B.D.L. 0.11
Pyrite BR-106 26 B2 B.D.L. B.D.L. 4.6 465000 B.D.L. 0.78 3.6 B.D.L. 0.44 668 B.D.L. B.D.L. 1.5
Pyrite BR-106 27 B2 B.D.L. B.D.L. 5.5 465000 B.D.L. B.D.L. 7.1 B.D.L. B.D.L. 203 B.D.L. B.D.L. 1.6
Pyrite BR-106 28 B2 B.D.L. B.D.L. 3.6 465000 0.28 2.5 46.5 B.D.L. B.D.L. 42.5 B.D.L. B.D.L. 0.11
Pyrite BR-106 29 B2 B.D.L. 7.3 4.4 465000 B.D.L. B.D.L. 5.4 B.D.L. 0.36 186 B.D.L. B.D.L. 0.35
Pyrite BR-106 30 B2 B.D.L. B.D.L. 4.1 465000 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 5.4 B.D.L. B.D.L. 0.16
Pyrite BR-106 31 B2 0.19 B.D.L. 4.1 465000 B.D.L. B.D.L. 3 B.D.L. B.D.L. 1969 B.D.L. B.D.L. 1.3
309
Mineral Sample # Cd (ppm) In (ppm) Sn (ppm) Sb (ppm) Te (ppm) W (ppm) Au (ppm) Hg (ppm) Tl (ppm) Pb (ppm) Bi (ppm)
# stage
Pyrite BR 80 1 B2 37.1 23.3 56.6 156 0.17 B.D.L. B.D.L. 0.48 B.D.L. 939 4.3
Pyrite BR 80 2 B2 B.D.L. B.D.L. B.D.L. 4.7 B.D.L. B.D.L. 0.13 B.D.L. B.D.L. 5.5 0.04
Pyrite BR 80 3 B2 B.D.L. 0.05 B.D.L. 18.3 B.D.L. B.D.L. 0.13 B.D.L. B.D.L. 28 0.3
Pyrite BR 80 4 B2 B.D.L. B.D.L. B.D.L. 2.9 B.D.L. B.D.L. B.D.L. B.D.L. 0.01 3.7 0.06
Pyrite BR 80 5 B2 B.D.L. B.D.L. B.D.L. 3.4 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 4.9 B.D.L.
Pyrite BR 80 7 B2 B.D.L. B.D.L. 2.3 147 0.13 B.D.L. 0.15 B.D.L. B.D.L. 672 1.6
Pyrite BR 80 8 B2 B.D.L. B.D.L. B.D.L. 7.2 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 10.5 2.9
Pyrite BR 80 9 B2 B.D.L. B.D.L. 1.4 24.7 B.D.L. B.D.L. B.D.L. B.D.L. 0.01 40.3 6.9
Pyrite BR 80 13 B2 B.D.L. B.D.L. B.D.L. 2.9 0.18 0.05 0.04 B.D.L. B.D.L. 4.4 1
Pyrite BR 80 15 B2 B.D.L. B.D.L. B.D.L. 31.2 B.D.L. B.D.L. B.D.L. B.D.L. 0.01 39 2.5
Pyrite BR 80 16 B2 B.D.L. B.D.L. B.D.L. 18.9 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 30.7 1
Pyrite BR 80 17 B2 B.D.L. B.D.L. B.D.L. 66.4 0.33 B.D.L. 0.09 B.D.L. 0.27 115 24.6
Pyrite BR 80 18 B2 B.D.L. B.D.L. B.D.L. 25.1 B.D.L. 0.21 0.09 B.D.L. 0.09 307 6
Pyrite BR 80 19 B2 B.D.L. B.D.L. B.D.L. 52.2 B.D.L. B.D.L. B.D.L. B.D.L. 3.5 39.9 6.2
Pyrite BR 80 20 B2 B.D.L. 0.08 1.5 21.1 B.D.L. B.D.L. 2 B.D.L. 0.04 335 12.4
Pyrite BR-106 21 B2 B.D.L. B.D.L. B.D.L. B.D.L. 0.4 0.11 B.D.L. B.D.L. B.D.L. B.D.L. 0.12
Pyrite BR-106 22 B2 B.D.L. B.D.L. B.D.L. 1.6 0.23 B.D.L. B.D.L. B.D.L. B.D.L. 5.6 6.1
Pyrite BR-106 23 B2 B.D.L. B.D.L. B.D.L. 0.2 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0.46 0.25
Pyrite BR-106 24 B2 B.D.L. B.D.L. B.D.L. B.D.L. 0.47 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 0.08
Pyrite BR-106 25 B2 B.D.L. B.D.L. B.D.L. 2.9 2.5 B.D.L. 0.09 B.D.L. B.D.L. 6.6 2.7
Pyrite BR-106 26 B2 B.D.L. B.D.L. 1.6 20.5 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 113 1.6
Pyrite BR-106 27 B2 B.D.L. B.D.L. 2.9 26.9 B.D.L. 0.17 B.D.L. B.D.L. B.D.L. 150 2.2
Pyrite BR-106 28 B2 B.D.L. B.D.L. B.D.L. 0.92 0.38 B.D.L. B.D.L. B.D.L. B.D.L. 0.18 0.84
Pyrite BR-106 29 B2 B.D.L. 0.01 1.3 3.2 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. 52 3.1
Pyrite BR-106 30 B2 B.D.L. B.D.L. B.D.L. 1 0.58 B.D.L. B.D.L. B.D.L. B.D.L. 1.2 1.2
Pyrite BR-106 31 B2 B.D.L. B.D.L. 1.5 13 B.D.L. B.D.L. 0.1 B.D.L. B.D.L. 102 4
310
Mineral Sample # V (ppm) Cr (ppm) Mn (ppm) Fe (ppm) Co (ppm) Ni (ppm) Cu (ppm) Zn (ppm) Ga (ppm) As (ppm) Se (ppm) Mo (ppm) Ag (ppm)
# stage
Pyrite BR-106 32 B2 B.D.L. B.D.L. 4.1 465000 B.D.L. 0.16 0.85 B.D.L. B.D.L. 468 B.D.L. B.D.L. 0.23
Pyrite 196 U 33 C1 B.D.L. B.D.L. 15 465000 0.26 B.D.L. 5.7 B.D.L. B.D.L. 9 10275 B.D.L. B.D.L.
Pyrite 196 U 34 C1 B.D.L. B.D.L. 10 465000 B.D.L. B.D.L. 3.3 23 B.D.L. 10.9 8807 B.D.L. B.D.L.
Pyrite 196 U 35 C1 B.D.L. B.D.L. 9.2 465000 B.D.L. B.D.L. B.D.L. 19.7 B.D.L. 10.5 7180 B.D.L. B.D.L.
Pyrite 196 U 36 C1 B.D.L. B.D.L. 13.1 465000 B.D.L. 2.6 B.D.L. 41.8 B.D.L. 11.8 10024 B.D.L. B.D.L.
Pyrite 196 U 37 C1 B.D.L. B.D.L. 9.7 465000 B.D.L. B.D.L. 3.9 27.3 B.D.L. 12.1 11109 B.D.L. B.D.L.
Pyrite 143C2 38 C2 B.D.L. B.D.L. 3.4 465000 12.2 22.1 1416 B.D.L. B.D.L. 57.5 66.3 B.D.L. 4.2
Pyrite 143C2 39 C2 B.D.L. B.D.L. 5 465000 11.9 10.9 2351 B.D.L. B.D.L. 95.4 47.9 B.D.L. 9.9
Pyrite 143C2 40 C2 B.D.L. B.D.L. 5 465000 13.3 10.5 3782 B.D.L. B.D.L. 302 63.8 B.D.L. 85.3
Pyrite 143C2 41 C2 B.D.L. B.D.L. 6.3 465000 16.4 13.2 1823 8.9 B.D.L. 2598 55.6 B.D.L. 42.8
Pyrite 143C2 42 C2 B.D.L. B.D.L. 5.9 465000 5.3 8.8 2956 B.D.L. 0.08 322 7.7 B.D.L. 3.8
Pyrite 143C2 43 C2 B.D.L. B.D.L. 8.7 465000 32.1 32.3 4807 B.D.L. B.D.L. 537 63.3 B.D.L. 245
Pyrite 143C2 45 C2 B.D.L. B.D.L. 5.3 465000 B.D.L. B.D.L. 16836 B.D.L. B.D.L. 169 16.8 B.D.L. 22
Pyrite 143C2 47 C2 B.D.L. B.D.L. 4.9 465000 3 111 5784 B.D.L. B.D.L. 38 22.3 B.D.L. 7.3
Pyrite 143C2 48 C2 B.D.L. B.D.L. 5.2 465000 2.1 6.6 6729 B.D.L. B.D.L. 99 27 B.D.L. 6.5
Pyrite 143C2 49 C2 B.D.L. B.D.L. 11.3 465000 0.39 0.85 5946 13.1 B.D.L. 454 11.9 0.65 1708
Pyrite 143C2 50 C2 B.D.L. B.D.L. 6.4 465000 2.5 5.5 6515 B.D.L. B.D.L. 121 B.D.L. B.D.L. 333
Pyrite 143C2 51 C2 0.1 B.D.L. 7.1 465000 B.D.L. B.D.L. 18823 B.D.L. B.D.L. 285 17.5 B.D.L. 134
Pyrite 143C2 52 C2 B.D.L. 6.8 6.4 465000 B.D.L. 0.28 15876 7.1 B.D.L. 296 17.1 B.D.L. 248
311
Mineral Sample # Cd (ppm) In (ppm) Sn (ppm) Sb (ppm) Te (ppm) W (ppm) Au (ppm) Hg (ppm) Tl (ppm) Pb (ppm) Bi (ppm)
# stage
Pyrite BR-106 32 B2 B.D.L. B.D.L. B.D.L. 4.2 B.D.L. B.D.L. B.D.L. 0.67 B.D.L. 12.6 1.8
Pyrite 196 U 33 C1 30.4 B.D.L. 4.3 15.6 4521 B.D.L. B.D.L. B.D.L. 11.7 448 6.8
Pyrite 196 U 34 C1 13.1 0.54 2.8 6.7 3090 B.D.L. B.D.L. B.D.L. 7.8 310 3.9
Pyrite 196 U 35 C1 12.5 B.D.L. 3.1 5.5 1807 B.D.L. B.D.L. B.D.L. B.D.L. 130 23.5
Pyrite 196 U 36 C1 30.7 B.D.L. 4.6 6.7 2574 B.D.L. B.D.L. B.D.L. 4.5 201 29518
Pyrite 196 U 37 C1 25.5 B.D.L. 3.5 5 2587 0.49 0.25 B.D.L. 4.8 199 1069
Pyrite 143C2 38 C2 B.D.L. B.D.L. B.D.L. 34.9 34.6 B.D.L. 0.35 B.D.L. B.D.L. 2 24
Pyrite 143C2 39 C2 B.D.L. B.D.L. 2.4 37.6 59.8 B.D.L. 0.62 B.D.L. B.D.L. 7.3 43.4
Pyrite 143C2 40 C2 B.D.L. B.D.L. B.D.L. 238 603 B.D.L. 1.2 2.8 B.D.L. 2.2 37.6
Pyrite 143C2 41 C2 B.D.L. B.D.L. 5.3 76 86 B.D.L. 0.77 B.D.L. 0.42 8.1 57.7
Pyrite 143C2 42 C2 B.D.L. B.D.L. 1.9 8.2 2.6 B.D.L. 0.26 1.1 0.19 1.7 13.9
Pyrite 143C2 43 C2 0.23 B.D.L. 2.9 278 644 0.17 1.1 6.1 0.46 4.5 67
Pyrite 143C2 44 C2 B.D.L. B.D.L. B.D.L. 2.4 4.6 B.D.L. 0.57 B.D.L. B.D.L. 1.5 43.9
Pyrite 143C2 45 C2 B.D.L. B.D.L. 9.9 99.5 28.6 B.D.L. 1.8 2.8 0.22 36.1 143
Pyrite 143C2 46 C2 B.D.L. B.D.L. B.D.L. 5 12.8 B.D.L. 1.1 B.D.L. B.D.L. 1 51
Pyrite 143C2 47 C2 B.D.L. B.D.L. B.D.L. 5.2 11 B.D.L. 1.4 B.D.L. 0.02 2 49.5
Pyrite 143C2 48 C2 B.D.L. B.D.L. B.D.L. 37.5 6.9 B.D.L. 1.6 B.D.L. 0.08 20.6 117
Pyrite 143C2 49 C2 0.27 B.D.L. 13.7 146 15.6 B.D.L. 1.6 2.6 1.4 40 121
Pyrite 143C2 50 C2 B.D.L. B.D.L. 1.6 38.6 16.6 B.D.L. 1.7 1 0.31 8.5 59.4
Pyrite 143C2 51 C2 B.D.L. 0.09 19.6 127 30.3 B.D.L. 2.8 3.6 1.3 50.7 173
Pyrite 143C2 52 C2 B.D.L. 0.06 13.9 142 29.5 0.37 1.8 2.2 0.41 48 164
312
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
Bertrand Rottiera, Kalin Kouzmanova, Vincent Casanovaa, Anne-Sophie Bouvierb, Lukas P.
Baumgartnerb, Massimo Chiaradiaa, Markus Wällec†, Jaime D. Barnesd, John Potée and Lluís Fontbotéa
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
Department of Geological Sciences, Jackson School of Geosciences, The University of Texas at
Austin, TX 78712, Austin, USA
e
Département F.-A. Forel des sciences de l’environnement et de l’eau, University of Geneva, 1205
Geneva, Switzerland
†
Abstract
The Cerro de Pasco district in central Peru includes three occurrences of porphyry-type mineralization
and hosts the second largest porphyry-related epithermal polymetallic deposit in the world. The
deposit is formed during three successive mineralization stages comprising both low- and high-
sulfidation mineral associations. Stage A consists of pyrrhotite pipe-like bodies grading outwards to
sphalerite- and galena-dominated carbonate-replacement bodies. Stage B is characterized by quartz-
pyrite veins (B1) and by a massive, funnel-shaped pyrite-quartz replacement orebody (B2). The
mineralization of stage C consists of well-zoned Zn-Pb-(Bi-Ag-Cu) carbonate-replacement orebodies
(C1) and E-W–trending Cu-Ag-(Au-Zn-Pb) enargite-pyrite veins (C2). In order to constrain the
313
source(s) of the mineralizing fluids we studied the Sr, Pb, and Cl isotopic signatures as well as the
anion and trace element composition of fluid inclusion leachates from two samples of porphyry-type
mineralization and from 12 samples of different epithermal mineralization stages. The analyses reveal
higher metal contents in fluid inclusion leachates from the epithermal stages than from the non-strictly
coetaneous porphyry-type mineralization. They also indicate that hypersaline and low salinity
mineralizing fluids forming the epithermal polymetallic deposit have strongly interacted with the low-
metamorphic dark shales and phyllites of the Paleozoic Excelsior Group and possibly other basement
rocks of similar lithology. Only minor meteoric water input was recorded using in-situ δ18O SIMS
analyses of hydrothermal quartz from stages A, B1 and B2, with no correlation between the obtained
δ18O compositions, trace element content, and SEM-CL textures. In contrast, quartz from the enargite-
pyrite veins of stage C2, shows domains marked by low δ18O values, low trace element content and
low CL intensity. We interpret these parts of the crystals to be formed by a cooler, meteoric-dominated
fluid. Combination of fluid inclusion leachate analyses with in-situ δ18O SIMS analyses of quartz
allows identifying the role and the relative proportion of the different fluids involved in the epithermal
mineralization at Cerro de Pasco.
Keywords: fluid inclusions, SIMS, oxygen isotopes, strontium isotopes, lead isotopes, chlorine stable
isotopes, quartz, trace elements, Cerro de Pasco
314
Introduction
Identifying the origin and determining the type and relative proportions of fluids involved in
hydrothermal systems is essential for constructing conceptual models for the formation mechanisms of
a particular ore deposit type. Origin of fluids involved in the formation of Au-Ag high- and low-
sulfidation epithermal deposits has been intensively studied (e.g., Simmons et al., 2005 and references
therein; Pudack et al., 2009; Maydagan et al., 2015) and implication of magmatic and meteoric fluids
in their formation is now well constrained and accepted. In contrast, origin of fluids forming
epithermal polymetallic deposits is not so well constrained and involvement of various crustal fluids,
in addition to magmatic and meteoric end-members, in those systems has been often proposed (e.g.,
Camprubi and Albinson 2007; Simmons et al., 2005).
The Miocene metallogenic belt of central Peru hosts numerous porphyry-related epithermal
polymetallic deposits (i.e., Cordilleran polymetallic deposits), including the world-class Morococha
(Catchpole et al., 2011 and 2015), Colquijirca (Bendezú and Fontboté, 2009) and Cerro de Pasco
(Baumgartner et al., 2008 and 2009) deposits. Involvement of magmatic fluids in the formation of
Cordilleran polymetallic deposits has been first suggested based on the close temporal and spatial
relationship between porphyry-type and Cordilleran polymetallic mineralization and later confirmed
by various analyses of hydrothermal minerals and mineralizing fluids (e.g., Baumgartner et al., 2008;
Catchpole et al., 2011 and 2015; Deen et al., 1994). Meteoric water has been often identified or
invoked, but recognized meteoric water incursions occur mostly late in the ore systems and partly
disconnected from the ore precipitation events (Baumgartner et al., 2008, Beuchat et al., 2004; Bussel
et al., 1990; Catchpole et al., 2015; Deen et al., 1994; Norman and Landis, 1983; Rye and Sawkins
1974). Implication of crustal fluids (equilibrated meteoric or magmatic fluids, basinal brines) has been
identified using Sr and Pb radiogenic isotopes and /or fluid inclusion studies in several Cordilleran
polymetallic systems (Bussel et al., 1990; Kouzmanov et al., 2011; Macfarlane et al., 1990; Moritz et
al., 2001; Norman and Landis 1983), and have been proposed as potential metal providers in some
systems (Bussel et al., 1990; Macfarlane et al., 1990; Norman and Landis 1983).
The focus of this study is the large Cerro de Pasco epithermal polymetallic deposit, adjacent to
a Mid-Miocene diatreme-dome complex that includes at least three types of porphyry mineralization
(Rottier 2016; Rottier et al., 2016a). The large epithermal polymetallic deposit is formed by three
successive mineralization stages comprising both low- and high-sulfidation mineral associations
(Baumgartner et al., 2008; Rottier et al., 2016b). Recently, Rottier (2016, chapter 5) conducted a
detailed fluid inclusion study combining microthermometry and LA-ICP-MS on ore and gangue
minerals from the different mineralization stages. According to this study, most of the mineralizing
fluids forming the polymetallic mineralization result of a mixing between hypersaline metal-rich
porphyry-type fluids and low-salinity contracted magmatic vapor-like fluids. An aim of this study is to
315
assess the potential presence and quantify the importance of contribution of meteoric waters in the
different mineralization stages, including the late one where a meteoric input had been already
recognized by bulk stable isotope analysis (Baumgartenr et al., 2008). In-situ SIMS oxygen isotope
analyses were conducted on selected quartz crystals from the epithermal mineralization stages A, B1,
B2 and C2 with the purpose of tracking possible meteoric water incursions in the mineralizing system.
The second aim of this study is to track potential interaction of the mineralizing fluids with basement
rocks and also to identify potential other fluid sources. We have determined radiogenic Sr and Pb and
stable Cl isotopic signatures as well as the composition of anions and metal content of the fluid
inclusions leachates extracted by crush-leach method from ore and gangue minerals of the epithermal
mineralization and also from porphyry-type quartz veins in clasts in the diatreme breccia. Crush-leach
analyses do not allow differentiating different fluid inclusions families hosted in the crushed minerals
and therefore analyses provide a mixture of the fluid inclusions. To overcome this problem, this study
is complementary with the previous detailed inclusion study done by Rottier (2016, chapter 5) on the
same samples. Crush-leach technique allows determining radiogenic Sr and Pb and stable Cl isotopic
signatures of the fluid hosted in gangue and ore minerals, determination difficult by in-situ techniques
because of the small size of the fluid inclusions (mostly < 20 μm). Analysis of leachate fluids has been
allowed to track the source of mineralizing fluids in different epithermal ore deposit (e.g., Banks et al.,
2000a,b; Chiaradia et al., 2006; Germann et al., 2003 Gleeson et al., 2009; Lüders et al., 2002;
Nahnybida et al., 2009). At Cerro de Pasco, interaction with basement rocks, in particular with
reduced dark shales and phyllites of the Paleozoic Excelsior Group, had already been previously
invoked to explain the low sulfidation mineral assemblages of the early mineralization stages
(Baumgartner et al., 2008; Rottier 2016; Rottier et al., 2016b). Our results allow constraining and
quantifying such interaction and the role of various fluid types during the ~1 m.y. lifespan of the
magmatic-hydrothermal system.
Geological setting
Cerro de Pasco is one of the largest known porphyry-related epithermal polymetallic
("Cordilleran") deposits; it is located 300 km North-East of Lima in the Western Cordillera of Peru, at
an elevation of 4,300 m.a.s.l.. It is part of the mid-Miocene metallogenic belt recognized in central and
northern Peru (Bendezú and Fontboté, 2009; Bissig et al. 2008; Bissig and Tosdal, 2009; Catchpole et
al., 2015; Noble and McKee, 1999). Historical production and remaining resources aggregate more
than 200 million tons (Mt) at approximately 7 wt % Zn, 2 wt % Pb, and 3 oz/t Ag in addition to at
least 100 Mt at 1.3 % 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).
316
The Cerro de Pasco district hosts a large diatreme-dome complex of 2.5 km diameter
emplaced west of a major high-angle N 15° W-striking reverse fault, locally named Longitudinal fault.
The diatreme-dome complex intrudes weakly metamorphosed dark shales and phyllites of the middle
Paleozoic Excelsior Group and polymictic conglomerates and sandstones of the Middle-Late Triassic
Mitu Group (Spikings et al., 2016; Fig. 1). Locally the Eocene Shuco conglomerate and Calera
limestone crop out forming an angular unconformity on top of the shales and phyllites of the middle
Paleozoic Excelsior Group. East of the Longitudinal fault a thick sequence (about 1,000 m) of massive
carbonate rocks, mainly limestone with locally sandy intercalations, black bituminous limestone, and
beds with chert nodules, belonging to the Late Triassic Chambará Formation (Pucará Group), is
exposed of surface (Angeles, 1999; Rosas et al., 2007).
The diatreme-dome complex was formed by a succession of phreatomagmatic, magmatic, and

phreatic events (Fig. 1; Baumgartner et al., 2008, Baumgartner et al., 2009; Einaudi, 1968 and 1977;
Rogers, 1983; Rottier 2016; Rottier et al., 2016a). An early phase of explosive activity produced a
large diatreme-breccia of more than 1.3 km deep and 2 km width. The lower part of the breccia
consists of a massive non-stratified matrix-supported breccia. The upper part of the breccia body is
stratified and represents the most common outcropping lithology in the magmatic complex (locally
known as Rumiallana Agglomerate). North of the diatreme-dome complex, dacitic accretionary lapilli
(0.2–0.5 cm diameter) tuff showing cross-bedding is recognized and interpreted as a base surge
deposit (Baumgartner et al., 2008). It is dated by isotope dilution thermal ionization mass spectrometry
(ID-TIMS) zircon U-Pb at 15.36 ± 0.03 Ma (Baumgartner et al., 2008, 2009). Subsequently to its
formation, the diatreme breccia was intruded by a series of volcanic and subvolcanic bodies which can
be summarized as follow a: i) dacitic to rhyodacitic lava-dome complexes emplaced along the western
margin of the diatreme and 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 trachyte porphyries (three identified on surface, each less than 10x10 m)
cropping out in the central part of the diatreme breccia dated at 15.286 ± 0.018 Ma (zircon U-Pb ID-
TIMS; Rottier 2016); and iv) east-west trending quartz-monzonite porphyry dykes cutting the diatreme
breccia, the dacitic to rhyodacitic lava-dome complexes, and the trachyte porphyries (Fig. 1A) yield
ID-TIMS zircon U-Pb ages of 15.35 ± 0.05 Ma and 15.16 ± 0.04 Ma (Baumgartner et al. 2009; Fig. 1).
Marking the end of the phreatomagmatic and magmatic activity, several 20 cm to 3 m-wide, mainly E-
W trending, milled-matrix fluidized breccia dykes are emplaced in various parts of the diatreme-dome
complex.
317
Figure 1: Figure 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 during the present study 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) Zoom of one of the trachyte porphyry outcrops.
318
Porphyry-type mineralization
From the three occurrences of porphyry-type mineralization identified at Cerro de Pasco
(Rottier et al., 2016a and submitted), the first (PM1) consists of small hornfels and porphyry clasts (2
to 10 cm in size) present in the diatreme-breccia that are crosscut by quartz-molybdenite-
(chalcopyrite)-(pyrite) veins (HT1 and HT2 in Rottier et al., submitted). . The porphyry-type
mineralization affecting the clasts is older than the diatreme breccia dated at 15.36 ± 0.03 Ma (zircon
U-Pb ID-TIMS; Baumgartner et al. 2009). It is the oldest porphyry-type mineralization identified so
far at Cerro de Pasco. Two samples of HT2 veins have been used for crush-leach analysis. The second
porphyry-type mineralization (PM2) is characterized by a low-density stockwork of quartz-magnetite-
chalcopyrite-(pyrite) porphyry-style veinlets centered on small trachyte porphyries (Fig. 1, Rottier et
al., 2016a). One of the trachyte porphyries is dated at 15.286 ± 0.018 Ma (zircon U-Pb ID-TIMS;
Rottier 2016). The third occurrence of porphyry-type mineralization (PM3) consists of clasts of
hornfels and porphyritic magmatic rocks (up to 25 cm in size) crosscut by quartz-magnetite-
chalcopyrite-(pyrite) veins up to 2 cm-thick. One of the mineralized magmatic clasts is dated at 15.165
± 0.043 Ma (zircon U-Pb ID-TIMS; Rottier 2016).
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). These alterations are spatially disconnected to the epithermal
polymetallic mineralization, and are probably the result of the interaction with acidic magmatic
vapors, generated by degassing of the deeper part of the porphyry system.
Epithermal mineralization
The epithermal polymetallic mineralization occurs along the eastern margin of the diatreme-dome
complex and it is mainly hosted in the Pucará carbonates (Fig. 1; Baumgartner et al., 2008; Einaudi,
1977; Rottier et al., 2016b). The polymetallic mineralization is emplaced at shallow level (its upper
part < 1 km below the paleo-surface), and was formed by three main successive mineralization stages
(Baumgartner et al., 2008, Rottier et al. 2016b).
The first mineralization stage A is characterized by numerous pipe-like pyrrhotite-dominated

carbonate replacement bodies grading outwards into Fe-rich sphalerite (up to 80 vol.%) and galena
rims. These pipes are structurally controlled and replace the Pucará carbonates along the NNW-SSE
Longitudinal fault corridor, and subordinately by N 35° and N 120° secondary faults (Baumgartner et
al., 2008; Einaudi, 1977; Rottier et al. 2016b).
The second stage B consists of (i) a set of quartz-pyrite veins crosscutting the lower part of
diatreme-dome complex (stage B1), and of (ii) a large N-S trending funnel shaped pyrite-quartz body
319
(stage B2). The quartz-pyrite veins of stage B1 contain minor amount of chalcopyrite, hematite,
magnetite, light-brown sphalerite, galena and fahlore. The quartz-pyrite veins of Stage B1 have been
sampled in the deepest drill hole available (1800_07_01), between 600 m and 900 m below the present
surface. They are mostly below 10 cm-thick but can locally reach 50 cm, and are roughly oriented N-
S. They are spatially associated with a kaolinite-sericite-pyrite or a sericite-pyrite alteration affecting
the diatreme-dome complex. The pyrite-quartz body is formed of more than 90 vol % of pyrite and 10
vol % of quartz (stage B2). It is ~1.5 km in length, 250 m wide and more than 550 m deep. It is
emplaced along the contact between the carbonate rocks and the diatreme-dome complex, and it
replaces mainly the Pucará carbonates and locally the diatreme breccia (Fig. 1). The pyrite-quartz
body is associated with a sericite-pyrite alteration halo of up to 50 m affecting the diatreme-dome
complex (Einaudi 1968; Baumgartner et al. 2008)
The last mineralization stage C consists of two distinct types of orebodies considered
synchronous: high- to intermediate-sulfidation Zn-Pb-(Bi-Ag-Cu) carbonate replacement orebodies
(stage C1) and a set of E-W trending Cu-Ag-(Au-Zn-Pb) enargite-pyrite veins (stage C2). The Zn-Pb-
(Bi-Ag-Cu) orebodies (stage C1), replace the Pucará carbonates in the eastern part of the deposit. They
form large irregular upward-flaring pipe-like shape bodies plunging towards the east with a dip from
25 to 60°; their diameters are strongly variable, from 50 cm to 50 m, and they can reach thickness of
up 400 m (Baumgartner et al., 2008). These bodies are well zoned laterally; Baumgartner et al. (2008)
defined four different zones: (i) a famatinite-rich core with pyrite, kaolinite and alunite, (ii) an
intermediate zone formed by pyrite, tetrahedrite, Bi- and Ag-bearing sulfosalts, kaolinite, alunite and
APS minerals, (3) an outer zone composed by Fe-poor sphalerite (up to 90%), galena, kaolinite and
rare APS minerals, and (4) an outermost zone containing magnetite, hematite, Fe-Mn-Zn carbonate
and traces of sphalerite, galena and pyrite. The Cu-Ag-(Au-Zn-Pb) enargite-pyrite veins (stage C2) are
from few cm to 2.5 m-thick, subvertical and mainly oriented N70-90°E and N120°E in the southern
part. They crosscut the previously formed pyrrhotite pipes and their rims (stage A) and the pyrite-
quartz body (stage B2). The veins are mainly formed by enargite and pyrite with minor amount of
tennantite, Fe-poor sphalerite, galena, quartz, alunite and kaolinite (Baumgartner et al., 2008). Two of
these veins are dated at 14.54 ± 0.08 to 14.41 ± 0.07 Ma (Ar-Ar on alunite, Baumgartnter et al., 2009).
A detailed fluid inclusion study combining microthermometry and LA-ICP-MS was conducted by
Rottier (2016, chapter 5), and allows reconstructing the salinity, temperature and chemical evolution
of the mineralizing fluid of the different stages. Rottier (2016, chapter 5) suggest that mineralization
stages A, B1, B2 and C1 were formed by a periodic dilution of high-salinity and metal-rich fluids by
low-salinity less metal rich fluids. Both fluids were assumed to be magmatic in origin regarding
microthermometry results and previous stable isotope study (Baumgartner et al., 2008); whereby in
stage C1 fluids mixing with meteoric water were also identified. The enargite-pyrite veins of stage C2
were interpreted to be formed by the ascent of CO2-bearing contracted vapor, subsequently mixed with
320
meteoric water; no evidence of mixing with the high-salinity and metal-rich fluids has being found. A
summary of the microthermometric and LA-ICP-MS results reported by Rottier (2016, chapter 5) are
summarized in Table 1.
Table 1: Summary of the results of the fluid inclusion studies conducted on the porphyry-type veins (PM1) (data from
Rottier et al. submitted) and on gangue and ore minerals from the epithermal mineralization stages (data from Rottier
2016, chapter 5).
Number of Range of Range of Base

Range of
Mineralization fluid studied salinity metal Mineralizing fluid
homogenization
stage inclusions / minerals (wt. NaCl concentrations proposed
temperature (°C)
FIAs equiv.) (ppm)
Fe 91'000-135'000,
Porphyry-type Mn 9'600-4'800,
HT2-veins 115/11 Qtz > 600 35.8-48.0 Cu 1'700-80*, Magmatic fluid
(PM1) Zn 7'500-3'300*,
Pb 1'600-900
Fe 2'800-850*, Mixing between high-
Mn 9'600-300, salinity metal-rich
A 201 / 25 Sl, Qtz 220-280 2.5-16.0 Cu 130-50*, magmatic fluid and
Zn 3'000-350*, low-salinity less metal-
Pb 9'600-300 rich magmatic fluid
Fe 57'000-1200, Mixing between high-
B1 120 / 15 Qtz 230-360 3.1-18.5 Cu 1'100-50, magmatic fluid and
Zn 27'000-250, low-salinity less metal-
Fe 18'000-1400, Mixing between high-
B2 302 / 35 Qtz 220-280 2.7-16.2 Cu 1'100-50, magmatic fluid and
Zn 12'000-400, low-salinity less metal-
Mixing between high-
Fe N.D.**,
salinity metal-rich
Mn 16'000-400,
magmatic fluid and
C1 257 / 29 Sl, Cb 150-280 1.1-19.1 Cu N.D.**,
low-salinity less metal-
Zn N.D.**,
rich magmatic fluid
Pb 13'000-200
and meteoric water
Fe 17'000-400, Mixing between low-
Mn 8'000-100, salinity CO2-bearing
C2 142 / 18 En, Qtz 190-295 1.2-2.7 Cu 400-50, and acidic magmatic
Zn 8'500-200, fluid and meteoritic
Pb 6'000-50 water
(*) Data obtained only on Quartz

(**) N.D.: Not detected due to the high concentration of the element in the host mineral
Abbreviations: Qtz: quartz; Sl: sphalerite; Cb: Fe-Mn-Zn carbonate; En: Enargite
Analytical methods
SEM-CL
Scanning electron microscopy cathodoluminescence (SEM-CL) was used to characterize
texturally the studied quartz crystals. SEM-CL images were acquired at the University of Lausanne
321
using a CamScan MV2300 SEM and at the University of Geneva using a JEOL JSM7001F SEM, both
equipped with panchromatic CL detectors.
SIMS
A total of 170 in-situ SIMS 18O/16O analyses and 55 trace element analyses (Ti, Al, Fe and Li)
were performed on 10 quartz chips placed in indium mounts together with grains of two quartz
reference materials UNIL-Q1 for δ18O measurements (Seitz et al., 2016) and BGS-Q1 for trace
elements (Audétat et al., 2015). Measurements were performed at the SwissSIMS ion probe national
facilities at the University of Lausanne, using a Cameca IMS180-HR. Samples were coated with a 40
nm-thick layer of gold. For oxygen isotope measurements, we used a 10kV Cs+ primary beam, a ~2
nA current, resulting in a ~10 µm beam size. The electron flood gun, with normal incidence, was used
16 18
to compensate charges. O and O secondary ions, accelerated at 10kV, were analyzed at a mass
resolving power of 2400 and collected on Faraday cups (FCs) multi-collection mode. FCs are
calibrated at the beginning of the session. Mass calibration was performed at the beginning of the
session and a nuclear magnetic resonance was used to lock 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‰ (2σ) on UNIL-Q1 reference material at the beginning of the session,
and internal error for each analysis lower than 0.3‰ 2σ. A set of 4 analyses of UNIL-Q1 standard,
inserted in each mount, has also been measured every 15-20 analyses for monitoring the instrument
stability, and accuracy by correcting the instrumental mass fractionation, as it can slightly differ from
mount to mount. The variation of UNIL-Q1 over the sessions was < 0.3‰ (2σ). The error reported for
samples reflected the 2σ for the standard during sessions. Also, a total of 55 spots for trace element
analyses (Ti, Al, Fe and Li) were measured at the SwissSIMS using an O- primary beam of 1.1 nA
accelerated at 13 kV to bombard the sample surface. Secondary ions were accelerated at 10 kV into
the mass spectrometer. 7Li+, 27Al+, 30Si+, 48Ti+ and 56Fe+ were analyzed on mono-collection mode using
the axial electron multiplier (EM). The field aperture was set to 4000 microns and the energy slit to 50
µm. The entrance slit was closed to 61 µm and the exit slit to 405 µm, allowing separating the
measured ions from any interference. Before each analysis, a pre-sputtering of 120 seconds using a
30
raster beam of 30 µm was used to clean the sample surface. Automatic calibration on Si and
centering of field aperture were made before each analysis, just after the pre-sputtering. Measurements
were done without any raster, with a 15-20 microns beam. Each analysis consists of 15 cycles of the
peak-stepping sequence 7Li+ (5 sec), 27
Al+ (3sec), 30
Si+ (2sec), 48
Ti+ (5sec) and 56
Fe+ (8sec).
Reproducibility (in 2σ) was 11% for Li, 7% for Al, 6% for Ti and 11% on Fe on BGS-Q1.
Background on the EM was less than 2 counts per hour.
322
LA-ICP-MS
A total of 111 laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) spot
analyses on 9 different quartz samples were acquired 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 2
summarizes the analytical conditions, data acquisition parameters, and list of isotopes analyzed during
LA-ICP-MS sessions. Quartz grains were ablated using an iris diaphragm for progressive manually
controlled increase of the laser beam diameter to limit explosion of the host quartz (Guillong and
Heinrich, 2007). LA-ICP-MS transient signals were reduced using the Sills software (Guillong et al.,
2008). The NIST glass standard SRM 610 was used as an external standard and analyzed two times
bracketing a maximum of 20 unknowns to correct the drift by linear regressions and 99.5 wt % SiO2
was assumed as an internal standard.
Table 2: LA-ICP-MS machine and data acquisition parameters
Excimer 193 nm ArF laser

Compex 110I Quartz
Energy density ~24-30 J/cm2
Repetition rate 10 Hz
Crater size ~40 µm
In-house built aluminum chamber with
Ablation cell
anti-reflection coated silica glass window
Cell He gas flow 1.1 l/min He
Cell H gas flow 5 ml/min H2

Readings per replicate 400
Points per peak 1 per mass
Oxide production rate tuned to <0.5 % ThO
Dwell time per isotope 50 ms for Ti, 30 ms for K and Ca; 20 ms
for Li, B, Na, Mg, P, Ba; 10ms for the
others
7
Li, 11B, 23Na, 25Mg, 27Al, 29Si, 31P, 39K,
44
Ca, 57Fe, 65Cu, 66Zn, 71Ga, 72Ge, 75As,
Isotopes analyzed 85
Rb, 88Sr, 118Sn, 121Sb, 133Cs, 137Ba, 208Pb,
238
U
Crush-leach analyses
A total of 12 mineralized samples from mineralization stages A, B2, C1 and C2 of the
epithermal polymetallic deposit were selected for crush-leach analyses. In addition, two quartz-
molybdenite-(chalcopyrite-(pyrite) veins of porphyry-type mineralization PM1, were also analyzed.
Selected samples were crushed, the 0.5-1 mm fraction were used to carefully handpicked 2-5 g of
monomineral fractions of ore (pyrrhotite, pyrite, sphalerite, galena and enargite) and gangue (quartz
and Fe-Mn-Zn carbonate) minerals. For 7 samples two different mineral fractions were handpicked,
details on selected samples and mineral fractions are summarized in Table 3.
323
Detailed protocol followed during crush-leach analyses is available as a supplementary
electronic material (Appendix 1). Fluid samples extracted by crush-leach technique were split into 5
aliquots each: (i) two aliquots were analyzed by ICP-MS using an ICP-MS 7700 Agilent-Series at the
University of Geneva to determine the chemical composition of the extracted fluids; (ii) one aliquot
was analyzed by ion chromatography (Dionex ICS-3000) at the University of Geneva to determine the
Cl-, Br-, F-, PO42- and SO42- contents; (iii) Sr and Pb isotope ratios were measured in one aliquot using
a Thermo NEPTUNE Plus mass spectrometer at the University of Geneva, and (iv) Chlorine isotope
ratios were determined in the last aliquot using a Thermo Electron MAT253 mass spectrometer at the
Jackson School of Geosciences, University of Texas (USA).
Table 3: Description of samples selected for the crush-leach analyses.
Microthermometry data**
stage of weight
sample n° mineral
mineralization (g) Dominant type of host Number of measured salinity
inclusion mineral FIAs (wt. % NaCl equiv)
BR-312 PM1 Qtz 2.4 L-V-H Qtz 2 40.9-41.9

BR-267 PM1 Qtz 3.6 L-V-H Qtz 6 39.1-48.0
Po 3.7
BR-59 Stage A L-V Qtz 2 3.4-10.3
Qtz 3.0
Sl 3.8
BR-111 Stage A L-V Sl/Qtz 4 6.9-15.2
Qtz 3.0
BR-130 Stage A Sl 4.6 L-V Sl 3 6.3-6.4
BR-175 Stage A Sl 3.9 L-V Sl 4 2.7-15.3
BR-80 Stage B2 Py 5.4 L-V Qtz 3 3-14.9
Py 5.1
BR-106 Stage B2 L-V Qtz Not measured
Qtz 1.8
Py 4.4
BR-126 Stage B2 L-V Qtz 4 4.9-9.9
Qtz 2.2
Gn 4.7
BR-196 stage C1 L-V Sl 5 3.4-5.2
Cb* 4.0
BR-198 stage C1 Gn 4.4 L-V Sl/Cb 3 4.7-12.3
En 5.0
BR-24 stage C2 L-V Qtz 6 2.1-15.6
Qtz 3.3
BR-143 stage C2 En 4.0 L-V En 2 1.8-2.1
En 4.2
BR-152 stage C2 L-V En 6 2.0-4.9
Py 4.6
*Fe-Mn carbonate
**: Data from Rottier et al. (submitted) and Rottier (2016)
Abbreviations: L-V-H: liquid-vapor-halite (± other salts and daugther phases); L-V: liquid-vapor; Cb: Fe-Mn-Zn carbonate; En: Enargite;
Gn: Galena; Py: pyrite; Po: Pyrrhotite; Qtz: quartz; Sl: sphalerite.
324
Results
Trace element ICP-MS analyses of inclusion fluids

Each epithermal mineralization stage is assumed to be formed by mineralizing fluids resulting
from a mixing of two fluids with different salinities and metal content (Rottier 2016, chapter 6), thus
producing a large range of salinities and metal concentrations in the different FIAs from the studied
samples, as revealed by microthermometry and LA-ICP-MS analyses of individual fluid inclusions
(Table 3). Therefore, it is difficult to attribute a particular fixed salinity to the fluid inclusion leachates
that collect multiple FIAs, trapped at different time and representing different snapshots of the
evolution of the hydrothermal system. Thus, elemental concentrations obtained by ICP-MS analyses
are reported as concentration ratios against the sum of Na and K ([X]/[Na+K]). Selected element ratios
are reported in Table 4 and the complete data set in supplementary table A.1.
In seven samples, fluid inclusion leachates from one ore and one gangue mineral were
analyzed (table 4) allowing comparison between them (Fig. 2). For samples from carbonate
replacement orebodies of stages A, B2, and C1, fluid inclusion leachates from the two different mineral
fractions show similar concentration ratios ([X]/[Na+K]), almost all elements are aligned along or
close to the 1:1 line (Fig. 2). Discrepancies occur for elements strongly enriched in the respective host
minerals, and elemental ratios for elements such as Pb, Zn, Mn, Fe seem to be the more affected by the
nature of the host (Fig. 2). The leachate from the pyrite fraction of sample BR-106 shows a strong
enrichment in rare earth elements (REE) and Al, compared to the leachate from the quartz fraction
(Fig. 2C). This enrichment could be due to presence of small un-identified solid inclusions rich Al and
REE included in pyrite, such as clay or APS minerals.
For the enargite-pyrite veins of stage C2, fluid inclusion leachates from the quartz and enargite
fractions of sample BR-24 and from pyrite and enargite fractions of sample BR-152 display
significantly different element concentration ratios ([X]/[Na+K]), part of the elements strongly
deviating from the 1:1 line (Fig. 2F and G), indicating that fluids trapped are chemically distinct.
These results are in agreement with the previous fluid inclusions study of Rottier (2016, chapter 5) that
reported significant different compositions for fluid inclusions trapped in quartz and enargite crystals
from same samples.
Concentration ratios obtained from the gangue and ore mineral fractions of the different
epithermal mineralization stages and of the porphyry veins are in the same order of magnitude
compared to the ones obtained by LA-ICP-MS analyses of individual fluid inclusions (Rottier 2016,
chapter 5; Rottier et al., submitted).
325
Figure 2: Comparison of trace element concentration ratios obtained from fluid inclusion leachates from one ore and one
gangue mineral pairs of the same sample.
326
Table 4: Concentration ratios of the fluid inclusion leachates obtained by ICP-MS.
Sample # Stage Mineral Na/(Na+K) K/(Na+K) Ca/(Na+K) Mn/(Na+K) Fe/(Na+K) Zn/(Na+K) Rb/(Na+K) Sr/(Na+K) Cs/(Na+K) Ba/(Na+K) Pb/(Na+K)
BR-267 PM1 Qtz 3.69E-01 6.31E-01 1.02E-02 2.13E-02 3.54E-01 3.01E-02 9.83E-04 8.69E-04 5.82E-05 2.07E-02 2.82E-02
BR-315 PM1 Qtz 4.19E-01 5.81E-01 1.69E-02 3.13E-02 3.87E-01 2.34E-02 1.46E-03 3.26E-03 4.60E-04 2.07E-03 1.88E-03
BR-111 A Sl 6.38E-01 3.62E-01 1.91E-02 5.81E-02 2.57E-01 9.93E-01 1.34E-03 1.35E-03 1.71E-03 9.19E-04 N.D.
BR-111 A Qtz 5.86E-01 4.14E-01 4.14E-02 5.56E-02 5.28E-01 6.85E-02 1.49E-03 1.84E-03 1.14E-03 8.62E-03 3.04E-02
BR-130 A Sl 6.34E-01 3.66E-01 5.81E-02 5.06E-02 7.28E-02 6.50E-01 1.46E-03 6.79E-03 1.77E-03 1.70E-03 3.01E-03
BR-175 A Sl 6.43E-01 3.57E-01 9.61E-02 5.58E-02 1.35E+00 7.52E+00 1.05E-03 1.69E-02 1.43E-03 4.89E-04 1.17E+00
BR-59 A Po 5.96E-01 4.04E-01 4.65E-02 5.28E-02 1.24E+01 N.D. 1.24E-03 2.82E-03 9.83E-04 8.39E-04 N.D.
BR-59 A Qtz 6.05E-01 3.95E-01 7.86E-02 3.89E-02 4.05E-01 9.98E-03 1.17E-03 2.94E-03 6.00E-04 3.99E-04 N.D.
BR-106 B2 Py 5.99E-01 4.01E-01 1.08E-01 1.01E-01 1.44E+01 1.10E+00 1.45E-03 2.65E-02 1.41E-03 6.11E-03 8.63E-02
BR-106 B2 Qtz 5.29E-01 4.71E-01 1.46E-01 5.05E-02 3.77E-01 7.23E-02 1.54E-03 4.91E-02 1.17E-03 1.53E-02 2.12E-02
BR-126 B2 Py 5.79E-01 4.21E-01 4.94E-02 3.65E-02 1.01E+01 1.80E-01 8.05E-04 4.77E-03 9.49E-04 3.76E-03 1.04E-02
BR-126 B2 Qtz 5.47E-01 4.53E-01 2.34E-02 3.33E-02 1.38E-01 2.89E-02 1.65E-03 2.15E-03 1.69E-03 2.04E-03 5.11E-03
BR-80 B2 Py 1.00E+00 N.D. N.D. 9.67E-02 1.77E+01 2.92E-01 2.89E-03 1.39E-02 2.15E-03 9.40E-03 1.11E-01
BR-196 C1 Gn 5.95E-01 4.05E-01 3.24E-02 3.07E-01 1.62E-01 1.05E+00 1.07E-03 1.93E-03 1.35E-03 3.70E-03 2.67E+01
BR-198 C1 Gn 6.14E-01 3.86E-01 5.73E-02 4.33E-01 N.D. 1.24E+00 1.31E-03 5.40E-03 1.71E-03 7.85E-03 1.79E+01
BR-196 C1 Cb 6.14E-01 3.86E-01 9.13E-02 1.67E+00 1.49E-01 1.84E-01 1.41E-03 1.51E-03 2.00E-03 1.06E-02 1.42E-02
BR-24 C2 En 5.43E-01 4.57E-01 1.70E-02 1.30E-01 N.D. 2.78E-01 1.83E-03 4.35E-04 2.06E-03 8.73E-04 N.D.
BR-24 C2 Qtz 4.48E-01 5.52E-01 3.06E-02 5.76E-02 1.80E-01 7.57E-02 1.72E-03 3.14E-03 1.20E-03 1.04E-02 N.D.
BR-143 C2 En 5.55E-01 4.45E-01 3.40E-02 1.51E-01 2.46E+00 1.17E-01 1.65E-03 2.04E-03 3.91E-03 6.64E-04 N.D.
BR-152 C2 En 6.54E-01 3.46E-01 2.48E-02 8.89E-02 8.96E-01 4.90E-01 1.45E-03 9.53E-04 2.33E-03 3.73E-03 7.86E-01
BR-152 C2 Py 6.38E-01 3.62E-01 2.37E-01 6.45E-02 7.93E+00 4.15E-01 1.59E-03 5.34E-03 2.26E-03 1.91E-02 5.74E-01
Abbreviations: Cb: Fe-Mn-Zn carbonate; En: Enargite; Gn: Galena; Py: pyrite; Po: Pyrrhotite; Qtz: quartz; Sl: sphalerite; N.D.: not detected.
327
Anion content and Cl isotopic composition
Anion contents (Cl-, Br-, F-, SO42- and PO42-) of fluid inclusion leachates were determined by
ion chromatography and results are reported as F/Cl, Br/Cl, SO4/Cl and PO4/Cl ratios (Table 5).
Table 5: Results of ion chromatography and Cl, Sr and Pb isotopic composition of fluid inclusion leachates.
sample F/Cl Br/Cl PO4/Cl SO4/Cl

Stage mineral d37Cl 87
Sr/86Sr 87
Sr/86sri** 206
Pb/204Pb 207
Pb/204Pb 208
Pb/204Pb
# (M) (M) (M) (M)
4.61E-
BR-312 (PM1) Qtz 0.0043 N.D. 0.0214 0.7 0.71042 0.70975 18.781 15.661 38.884
04
1.16E-
BR-267 Qtz 0.0072 N.D. 0.0216 1.3 0.71041 0.71015 N.D. N.D. N.D.
(PM1) 03
Po 0.0048 N.D. N.D. 1.668* N.A. 0.71329 0.71303 N.D. N.D. N.D.
BR-59 A 1.38E-
Qtz 0.0202 0.0016 0.0994 2.0 0.71265 0.71241 N.D. N.D. N.D.
03
4.60E-
Sl 0.0056 N.D. 0.1720* 0.7 0.71393 0.71334 N.D. N.D. N.D.
BR-111 A 03
Qtz 0.0083 N.D. 0.0003 0.0156 1.2 0.71381 0.71333 18.696 15.608 38.714
1.06E-
BR-130 A Sl 0.0023 N.D. 0.193* N.A. 0.71124 0.71111 18.748 15.670 38.850
03
4.21E-
BR-175 A Sl 0.0069 N.D. 1.903* 1.3 0.71090 0.71087 18.778 15.656 38.862
04
BR-80 B2 Py 0.0044 N.D. N.D. 1.160* N.A. 0.71243 0.71230 18.785 15.664 38.878
Py 0.0047 N.D. N.D. 1.779* 0.0 0.71352 0.71349 18.769 15.661 38.859
BR-106 B2 2.08E-
Qtz 0.0139 0.0039 0.1221 1.0 0.71224 0.71222 18.699 15.612 38.718
03
Py 6.7926 N.D. N.D. 5.255* N.A. 0.71161 0.71151 18.779 15.696 38.899
BR-126 B2 1.36E-
Qtz 0.0050 N.D. 0.0178 1.9 0.71253 0.71208 N.D. N.D. N.D.
03
2.58E-
Gn 0.0121 N.D. 0.7561* N.A. 0.71221 0.71188 18.773 15.657 38.860
03
BR-196 C1
4.35E-
Cb* 0.0147 N.D. 0.1767 N.A. 0.71385 0.71329 18.784 15.708 38.935
03
2.21E-
BR-198 C1 Gn 0.0151 N.D. 0.9026* N.A. 0.71068 0.71053 18.774 15.655 38.857
03
En 15.9067 N.D. N.D. N.D. N.A. 0.71531 0.71279 N.D. N.D. N.D.
BR-24 C2
Qtz 5.9508 N.D. 0.0013 0.0850 N.A. 0.70970 0.70937 N.D. N.D. N.D.
BR-143 C2 En 0.0070 N.D. 0.0029 1.649* N.A. 0.71074 0.71026 N.D. N.D. N.D.
En 1.3995 N.D. N.D. 0.7576* 1.3 0.71230 0.71139 18.780 15.656 38.869
BR-152 C2
Py 0.0044 N.D. N.D. 2.231* 1.2 0.71199 0.71182 18.776 15.655 38.862
*: SO4/Cl ratio contaminated by the host mineral; **: Initial 87Sr/86Sr recalculated using the Rb/Sr ratio obtained by ICP-
MS and assuming age of 14.5 Ma for the epithermal and 15.5 Ma for the porphyry mineralization; Abbreviations: Cb: Fe-
Mn-Zn carbonate; En: Enargite; Gn: Galena; Py: pyrite; Po: Pyrrhotite; Qtz: quartz; Sl: sphalerite; N.D.: not detected;
N.A.: not analyzed
The SO4/Cl molar ratios of the fluid inclusion leachates from sulfide and sulfosalt mineral
fractions are strongly contaminated and are not representative of the fluids. The SO4/Cl molar ratio of
fluid inclusion leachates from quartz fractions varies from 0.0214 to 0.0216 for the porphyry-type
veins, from 0.0156 to 0.0994 for mineralization stage A, from 0.0178 to 0.1221 for stage B2, and is
0.0850 for stage C2 (table 5). Fluid inclusion leachate from the carbonate fraction of sample BR-196
(stage C1) yields SO4/Cl ratio equal to 0.1767 (table 5). Such ratios are elevated and show that fluids
forming the epithermal mineralization were rich in sulfur. The F/Cl molar ratios of most fluid
328
inclusion leachates range from 0.0023 to 0.0202 except four values showing unusually high F/Cl
molar ratios between 1.399 and 15.91 (table 5). These high F/Cl ratios are measured in inclusion fluids
from enargite and quartz fractions of sample BR-24, from enargite fraction of sample BR-152 (stage
C2) and from pyrite fraction of sample BR-126 (stage B2). The PO42- was detected in 5 samples (table
5) and obtained PO4/Cl molar ratios are low, between 0.0003-0.0039. Bromine was detected in 11
samples (table 5) and Br/Cl ratio varies from 0.42 to 4.6 10-3 (table 5; Fig 3 B).
A total of 11 samples were analyzed for chlorine isotopes (table 5; Fig. 3 A). The δ37Cl values
of fluid inclusion leachates from the two porphyry-type quartz veins are 0.7 and 1.3 ‰. Four samples
from stage A were analyzed yielding values between 0.7 and 2 ‰. Fluids inclusion leachates from
quartz and sphalerite fractions of sample BR-111 have compositions of 1.2 ‰ and 0.7 ‰, respectively
Fluids from pyrite and quartz fractions of sample BR-106 give distinct results with respectively 0.0
and 1.0 ‰, and fluids from the quartz fraction of sample BR-126 yield δ37Cl equal to 1.9 ‰. Fluids
from the enargite and pyrite fractions of sample BR-152 (stage C2) display similar δ37Cl signatures
with respectively 1.3 and 1.2 ‰.
Figure 3: δ37Cl signatures (A) and Br/Cl molar ratios (B) of fluid inclusion leachates from Cerro de Pasco, compared to
previously published data (1: Nahnybida et al., 2009; 2: Gleeson et al., 2009; 3: Banks et al., 2000a,b; 4: Chiaradia et al.,
2006; 5: Lüders et al., 2002; 6: Germann et al., 2003; 7: Chiaradia et al., 2007; 8: Barnes et al., 2009; 9: Barnes et al.,
2008; 10: Barnes and Straub 2010; 11: Irwin and Roedder 1995; 12: Kendrick et al., 2001; 13: Pytkowicz and Kester
1971).
Sr and Pb isotopic compositions

Table 5 summarizes the obtained Sr and Pb isotopic composition of the different fluid
87
inclusion leachates. The initial Sr/86Sr isotopic ratios of the fluid were calculated using the Rb/Sr
ratios obtained by ICP-MS and applying an age correction of 14.5 Ma for the epithermal
mineralization (Baumgartner et al., 2008) and 15.5 Ma for the porphyry mineralization (Rottier 2016).
329
Figure 4 illustrates the 87Sr/86Sr isotopic ratios of the fluid inclusion leachates from different
mineralization stages, compared to the isotopic ratios of the magmatic and sedimentary rocks of the
district and to previous data published by Baumgartner et al. (2008) on bulk sericite and pyrite. The
87
full data set is available in supplementary table A.2. The Sr/86Sri of the fluid inclusion leachates
87
varies from 0.70970 to 0.71352, it is significantly higher than the Sr/86Sr values of the magmatic
rocks ranging from 0.70529 to 0.70564 and those from the carbonate host rocks equal to 0.70827 for
the Calera carbonates and ranging between 0.70895 and 0.71003 for the Pucará carbonates (Fig. 4).
The 87Sr/86Sr ratios obtained for the Mitu sandstone (0.72570) and for the Excelsior shales and phyllite
(0.75564-0.82616) are higher than those obtained from the fluids. Fluid inclusion leachates from the
87
porphyry-type quartz-molybdenite-(chalcopyrite)-(pyrite) veins show lower Sr/86Sri values than the
epithermal mineralization stages (except one value from quartz fraction of sample BR-24) and are
between 0.70975 and 0.71015. The 87Sr/86Sri values of the fluid inclusion leachates from the different
epithermal mineralization stages are in the same range: from 0.71087 to 0.71334 for stage A, from
0.71151 to 0.71349 for stage B2, from 0.71053 to 0.71329 for stage C1 and from 0.70937 to 0.71279
for stage C2.
Figure 4: 87Sr/86Sr isotopic ratios of fluid inclusion leachates from the different epithermal mineralization stages and the
porphyry veins. An age correction has been applied for 14.5 Ma for the epithermal mineralization stages and 15.5 Ma for
the porphyry veins. Also plotted: (i) Data obtained from the magmatic rocks from Cerro de Pasco (*: data from Rottier
2016), Yanamate (barren magmatic center located 5 km south of Cerro de Paso) and Colquijirca (mineralized magmatic
center located 15 km south of Cerro de Pasco); (ii) previously published data by Baumgartner et al. (2008) (R: residue; L:
leachate); (iii) Data obtained on sedimentary rocks from the Cerro de Pasco district.
Lead isotopic composition of the fluid inclusion leachates from the different mineralization
stages are plotted in Figure 5 together with those from the different magmatic and sedimentary rocks
in the district (full data set is available in supplementary Table A.2), and also with previously
published data on bulk Galena (Mukasa et al., 1990) and pyrite (Baumgartner, 2007). The 206Pb/204Pb
330
207
ratio of the fluids is similar to the one of the magmatic rocks whereas the Pb/204Pb and 208
Pb/204Pb
are higher except for two fluid inclusion leachates from two quartz fractions of sample BR-111 (stage
A) and BR-106 (stage B2, Fig. 5). The obtained Pb isotopic signatures for the fluids are in agreement
with the previous data obtained on galena and pyrite (Baumgartner, 2007; Mukasa et al., 1990). No
distinct trend between the signatures of fluid inclusion leachates from the different epithermal
mineralization stages and/or those from the porphyry-type veins has been established (Fig.5).
Figure 5: 207Pb/204Pb and 208Pb/204Pb plots against 206Pb/204Pb of fluid inclusion leachates from the different epithermal
mineralization stages and the porphyry veins. Also plotted: (i) Data for magmatic rocks from Cerro de Pasco (*: data from
Rottier 2016), Yanamate (barren magmatic center located 5 km south of Cerro de Paso) and Colquijirca (mineralized
magmatic center located 15 km south of Cerro de Pasco) districts; (ii) Previous published data of Baumgartner et al.
(2008) and Mukasa et al. (1990) on pyrite and galena; (iii) Data obtained on sedimentary rocks from Cerro de Pasco
district; (iv) Pb isotopic composition of the province II defined by Macfarlane et al. (1990), see text for explanation.
331
In-situ oxygen isotope and trace element analyses in
hydrothermal quartz
In-situ oxygen isotopes

A total of 10 samples from mineralization stages A, B1, B2 and C2 were selected for in-situ
SIMS oxygen isotope analyses on quartz crystals (Table 6). No suitable quartz crystals from stage C1
were found.
Table 6: Summary of the obtained δ18O signatures of the studied quartz crystals.
Mineralization Number of range of measured

Sample # Figure
stage δ18O spots δ18O
BR-111 A 20 11.2-19.4 Fig. 6

BR-175 A 10 14.7-17.6 Fig. A.1*
BR-12 Q2 B1 38 4.65-16.12 Fig. 7
BR-12 Q5 B1 10 13.9-16.3 Fig. A.2*
BR-05 Q1 B1 6 14.0-17.9 Fig. A.2*
CV-11 Q6 B2 37 8.7-19.6 Fig. 8
CV-11 Q7 B2 8 12.0-19.2 Fig. A.3*
BR-126 B2 13 12.9-20.4 Fig. 9
BR-24 Q1 C2 23 7.6-18.5 Fig. 10
BR-24 Q2 C2 5 5.9-14.4 Fig. A.4*

*: Figures available as an electronic appendices
Stage A
Two samples from mineralization stage A were analyzed: BR-111 and BR-175, quartz crystals
from both samples are euhedral to subhedral and display fine oscillatory growth zoning characterized
by low- to high-CL intensity (Fig. 6 and supplementary Figure A.1). Sample BR-175 presents areas
with very high-CL intensity, which are due to apatite solid inclusions (supplementary Figure A.1). The
obtained δ18O values for quartz from sample BR-111 vary between 11.2 and 19.4 ‰ with most of
values ranging between 14.6 and 19.4 ‰ (Fig. 6 A). Detailed transect realized through one quartz
crystal shows a constant δ18O signature in the center of the quartz at ~ 19 ‰ (Fig. 6 A), followed by a
sharp drop of δ18O from 18.9 to 11.2 ‰ in less than 30 µm, then the δ18O signatures display a plateau
with values between 13.1 and 15.8 ‰ and the rim of the crystal is characterized by an increase of δ18O
to 18 ‰ (Fig. 6 A). Profiles by LA-ICP-MS and SIMS show no correlation between quartz trace
element composition and obtained δ18O (Fig. 6, C and D). Sample BR-175 shows smaller variations
than BR-111, the obtained δ18O values vary between 14.7 and 17.6 ‰ (supplementary Figure A.1). In
332
both samples no correlation between the obtained δ18O values and CL intensity were detected (Fig. 6,
A, and supplementary Figure A.1).
Figure 6: A) SEM-CL image of quartz grains from sample BR-111 from stage A; pink circles indicate locations and
results of SIMS oxygen isotope analyses; blue ellipses indicate locations and numbers of SIMS trace element analyses;
green circles refe to locations and numbers of LA-ICP-MS trace element analyses. B) δ18O composition of the quartz and
the corresponding δ18O composition of the fluid in equilibrium with quartz calculated using the equation of Zheng (1993)
and assuming a temperature of 250°C, along the profile A-B; PMW: primary magmatic water after Deen et al., (1994). C)
Trace element concentrations obtained by SIMS along the profile A-B. D) Selected trace element concentrations obtained
by LA-ICP-MS along the profile A-B.
Stage B1
Three quartz crystals from mineralization stage B1 were analyzed (BR-12 Q2, BR-12 Q5 and
BR-05 Q1). All quartz crystals are euhedral and present fine oscillatory growth zoning characterized
by low- to high-CL intensity (Fig. 7 A, supplementary Figure A.2).
A total of 38 δ18O spot analyses were performed on quartz crystal BR-12 Q2 (Fig. 7A). The
inner part of the crystal shows quite homogeneous δ18O composition between 11.9 to 16.1 ‰ except
one spot showing very low δ18O value of 4.6 ‰. The external zones of the grain are characterized by
lighter δ18O signatures, most values are between 10.5 and 13.9 ‰ with three lower values: 9.1, 6.8 and
5.8 ‰. Small solid inclusions of hematite are also present in the external part of the crystal. Trace
element composition of the quartz analyzed by LA-ICP-MS and SIMS reveals important variations in
Al, Ti, Li, and Sb concentrations (Fig. 7 C and D), but no correlation with the obtained δ18O
composition. The two other crystals studied display a range of δ18O values from 13.9 to 16.3 and from
14 to 17.9 ‰ for respectively BR-05 Q1 and BR-12 Q5 (supplementary Figure A.2). No correlation
between the measured δ18O of quartz and its CL intensity or quartz texture was noticed
333
Figure 7: A) SEM-CL image of quartz crystal BR-12 Q2 from stage B1; pink circles correspond to location and results of
SIMS oxygen isotope analyses; blue ovals represent location and numbers of SIMS trace element analyses; green circles
indicate location and number of LA-ICP-MS trace element analyses; B) δ18O composition of quartz along the profile A-B;
C) Trace element concentrations obtained by SIMS along the profile A-B-C; D) Selected trace element concentrations
obtained by LA-ICP-MS along the profile A-B-C.
Stage B2
Three quartz crystals from mineralization stage B2 were analyzed: CV-11 Q6, CV-11 Q7 and
BR-126. Like for stage B1, quartz crystals are euhedral and display fine oscillatory growth zoning
characterized by low- to high-CL intensity (Figs. 8 A and 9 A; supplementary Figure A.3). A total of
37 δ18O spot analyses were done on quartz crystal CV-11 Q6; the core of the crystal shows low δ18O
values varying between 8.7 and 11.4 ‰ (Fig. 8 A), whereas the intermediate and external zones
present higher δ18O values between 11.0 and 19.6 ‰ with most of them between 16 and19.6 ‰ (Fig.
8). Trace element concentrations obtained by LA-ICP-MS and SIMS, show strong variations in Al, Ti,
Sb, and Ge, but no correlation with the obtained δ18O values (Figs. 8 C, D, F, and H). Quartz crystal
CV-11 Q7 displays a similar pattern with a light δ18O core at ~12 ‰, and an external part
334
characterized with δ18O values varying between 14.2 and 19.2 ‰ (supplementary Figure A.3). Quartz
crystal BR-126 does not show a low δ18O core and obtained values vary between 12.9 and 20.4 ‰
with the majority being between 15 and 16.4 ‰ (Fig. 9). No correlation between the measured δ18O
values and the CL intensity of the quartz crystals was observed.
Figure 8: A) SEM-CL image of quartz crystal CV-11 Q6 from stage B2; pink circles refer to locations and results of SIMS
oxygen isotope analyses; blue ellipses correspond to locations and numbers of SIMS trace element analyses; green circles
indicate location and number of LA-ICP-MS trace element analyses. B-E-G) δ18O composition of the quartz and the
335
corresponding δ18O composition of the fluid in equilibrium with quartz calculated using the equation of Zheng (1993) and
assuming a temperature of 245°C, along the profiles F-G (B), A-B (E) and A-C-D-E (G); C-D) Selected trace element
concentrations obtained by LA-ICP-MS along the profile 1-12; F-H) Trace element concentrations obtained by SIMS
along the profile A-B (F) and A-C-D-E (H). PMW: primary magmatic water after Deen et al., (1994)
Figure 9: A) SEM-CL image of quartz crystal BR-126 from stage B2; pink circles correspond to locations and results of
SIMS oxygen isotope analyses; green circles refer to location and number of LA-ICP-MS trace element analyses. B-C)
δ18O composition of the quartz and the corresponding δ18O composition of the fluid in equilibrium with quartz calculated
using the equation of Zheng (1993) and assuming a temperature of 245°C, along the profile A-B (B) and C-D (C). PMW:
primary magmatic water after Deen et al., (1994)
Stage C2
Two quartz crystals from one enargite-pyrite vein (stage C2) were analyzed. Quartz crystal
BR-24 Q1 shows complex CL texture, with an un-zoned low CL intensity core, overgrown by
moderate to high CL intensity well zoned quartz (Fig. 10 A). Quartz core and its overgrowths are
crosscut by low CL intensity cracks filled by quartz (Fig. 10 A). The dark core displays homogeneous
low δ18O values varying between 9.7 to 10.4 ‰, whereas the overgrowths show more complex
signatures. The overgrowth visible on profile C-D (Fig. 10 D) shows a constant δ18O values at ~ 18.5
‰, decreasing to 14.3 ‰. The overgrowth from profile A-B (Fig. 10 B) presents highly variable δ18O
values between 9.8 to 18.3 ‰. Two analyses were done on the dark quartz filling cracks; they yield
the lowest δ18O values of 7.3 and 8.4‰ (Fig. 10 A). Trace element content obtained by LA-ICP-MS
and SIMS yields a low Al (< 100 ppm) and Ti (< 1ppm) concentrations for the dark crystal core,
whereas compositions of the moderate to high CL intensity overgrowths are strongly variable but are
higher in Al (up to 1600 ppm) and Ti (up to 5.9 ppm, Figs. 10 C and E). The dark healed fractures
display also a low Al and Ti concentrations with respectively 127 and 1.8 ppm (Fig. 10 C).
336
Figure 10: A) SEM-CL image of quartz grain BR-24 Q1 from stage C2; pink circles refer locations and results of SIMS
oxygen isotope analyses; blue ellipses indicate location and numbers of SIMS trace element analyses; green circles
correspond to location and number of LA-ICP-MS trace element analyses. B-D) δ18O composition of the quartz and the
corresponding δ18O composition of the fluid in equilibrium with quartz calculated using the equation of Zheng (1993) and
assuming a temperature of 270°C, along the profiles A-B (B) and C-D (D). C-E) Trace element content of quartz obtained
by SIMS along the profiles A-B (C) and C-D (E). PMW: primary magmatic water after Deen et al., (1994)
Quartz crystals from sample BR-24 Q2 present numerous cores formed by xenocrystic
magmatic quartz grains as revealed by their high CL intensity and their textures (supplementary Figure
A.4). These magmatic cores are crosscut and overgrown by low to moderate CL intensity well-zoned
quartz. The magmatic quartz grains display δ18O values of 10.4 and 10.5 ‰ (n=2) whereas the three
analyses done on the overgrowth yield δ18O values of respectively 14.4, 13.4 and 5.9 ‰
(supplementary Figure A.4).
Trace elements in quartz

Table 7 summarizes the obtained trace element concentrations of the quartz crystals studied
from the different epithermal mineralization stages.
337
Table 7: Summary of trace element concentrations of the studied quartz crystals (range between Min and Max values) –
SIMS and LA-ICP-MS analyses.
Stade A stade B1 Stade B2 Stade C2

Li* 4.8-17.9 1.1-16.4 0.4-5.6 1.0-1.7
B 8.4-15.2 2.9-16.4 4.2-11.4 <5.1-7.7
Na 1.6-49.7 0.3-4 0.7-14.5 1.0-2.7
Mg 1.0-35.7 <0.3-68.0 <0.5-1.8 <0.5
P 29.4-35.7 36.1-49.2 35.6-51.3 29.2-31.7
Al* 890-2910 43.4-1980 220-2100 21-1610
K <13.4-158 <9.6 <8.5-60.7 <10.2
Ti* <1.8-10.94 0.8-14.9 1.0-7.5 0.4-5.9
Fe* 4.8-29.7 1.1-12.9 0.8-44.8 1.7-98.3
Ga 4.3-15.8 <0.04-1.6 0.1-1.7 <0.04-0.5
Ge 6.5-23.6 <1.2-7.6 3.3-15.8 <0.8-2.6
As <1.5 0.3-8.6 <0.4-110 <0.6-10
Rb <0.04-1.4 <0.02-0.1 <0.03-0.8 <0.03-0.03
Sr <0.03-0.82 <0.02-0.03 <0.02-0.2 <0.02-0.2
Sn 0.9-1.7 1.1-2.5 0.9-4.1 1.0-1.5
Sb 24.8-59.84 0.6-81.8 2.2-100 1.1-4.9
* Values obtained by LA-ICP-MS and SIMS analyses
Trace element concentrations obtained by LA-ICP-MS and SIMS are comparable and
complete datasets are respectively available in supplementary tables A.3 and A.4. Aluminum is the
most abundant and variable trace element, with concentration varying between 21 and 2910 ppm.
Correlation plots of Li, Ti, Ge, Ga, Sb, Na, P and Fe against Al are shown in Figure 11. Lithium
content shows a good correlation with Al, quartz crystals from mineralization stages A, B1 and C2 plot
along the same trend whereas sample from stage B2 plot along a different trend characterized by a
lower Li content (Fig. 11). A rough correlation exists between Ti, Ge, Sb and Al for quartz from stage
B1, B2 and C2 (Fig. 11). A correlation between Al and Ga also exists for quartz from stage B2. No
correlation has been observed between Na, K (not shown), P, Fe and Al (Fig. 11).
338
Figure 11: Correlation plots of selected trace elements in quartz versus Al.
339
Discussion
Trace elements in hydrothermal quartz
Application of Ti-in-quartz thermometer at low temperatures and pressures

Several equations linking the Ti content of quartz to its temperature of formation have been
published (e.g., Huang and Audétat 2012; Thomas et al., 2010; Wark and Watson 2006). These
equations have been used to constrain quartz precipitation temperatures from different epithermal and
porphyry deposits (e.g., Kodera et al., 2014; Mercer et al., 2013; Müller et al., 2010; Tanner et al.,
2013). Quartz precipitation temperatures were calculated using the published equations of Thomas et
al. (2010) and Huang and Audétat (2012), where we chose a fixed pressure of 15 bars coherent with
the local geology and a TiO2 activity of 1 because of presence of solid inclusions of rutile and/or
anatase in the studied quartz crystals (Rottier et al., 2016b; Rottier 2016, chapter). Calculated
temperatures are: (i) 283-371°C and 273-366°C for stage A (Ti = <1.8- 10.9 ppm), (ii) 259-350°C and
248-344°C for stage B2 (Ti = 1-7.5 ppm), and (iii) 226-338°C and 214-331°C for stage C2 (Ti = 0.4-
5.9 ppm). Calculated temperatures are systematically higher, by up to 70°C, than the temperatures
indicated by the fluid inclusion study; therefore we suggest that results from Ti-in-quartz
thermometers in relatively low temperature hydrothermal quartz should be considered with caution as
recommended by Huang and Audétat (2012).
Trace element and hydrogen distribution in quartz

Fine oscillatory zoning and sharp variations of trace element concentrations (up to one order
of magnitude) in quartz crystals as observed in the studied quartz crystals are common for epithermal
ore deposits (Rusk et al., 2008 and 2011). No correlation between CL intensity and concentration of a
specific element in quartz was observed (Figs. 6, 7, 8, 9, and 10).
Incorporation of trace elements in quartz commonly results from a combination of different

factors such as temperature, pressure, pH, Eh, fluid composition and quartz growth rate (Huang and
Audetat 2012; Ihinger and Zink 2000; Jourdan et al., 2009b; Rusk et al., 2008). Influence of each
parameter, on incorporation of a specific trace element is not known, and one parameter can mask or
influence another. During the different mineralization stages, pressure is assumed to be constant and
temperature variations are small (≈ 60°C). Thus, other factors, like pH, Eh, composition of fluids, and
quartz growth rate should be more influent.
The most common substitution in quartz is replacement of a cation Si4+ by a trivalent cation
(Al3+, Fe3+, As3+) and to respect the charge neutrality a monovalent cation (Li+, Na+, K+) could be
incorporated in the structure in interstitial position (e.g., Gotze 2009), or a pentavalent cation (P5+,
Sb5+) could replace another cation Si4+. Quartz crystals from Cerro de Pasco show a lower molar
340
concentrations of monovalent and pentavalent cations (Li+, Na+, K+, P5+, Sb5+) than concentration of
trivalent cations (Al3+, Fe3+, As3+; Fig. 12). This lack of charge neutrality is commonly attributed to
incorporation of H+ in interstitial position (Gotze 2009; Jourdan et al., 2009b; Miyoshi et al., 2005;
Müller and Koch-Müller 2009). Estimation of H+ using the following equation H+ ≈ (Al3++Fe3++As3+) -
(Li++Na++K++P5++Sb5+) all in mol/t, returns a high quantity: 37-59 mol/t for stage A, 1-70 mol/t for
stage B1, 9-76 mol/t for stage B2, and 0.6-12 mol/t for stage C2 (1 mol/t of H+ = 1 ppm of H+; Fig. 12).
These values are higher than the 6 ppm inferred for quartz from the Bingham porphyry Cu-Au-Mo
deposit (Landtwing and Pettke 2005) and lower than the 22 to 167 ppm (0.02-0.15 wt.% H2O)
proposed for quartz from Mt. Leyshon Au porphyry deposit (Allan and Yardley, 2007). H+
concentration in quartz varies between the different mineralization stages, but does not correlate with
acidity of the mineralizing fluids estimated by alteration mineral assemblages affecting the diatreme
breccia: chlorite-sericite for stage A, sericite-pyrite for stage B1 and B2, and alunite-kaolinite for stage
C2 (Baumgartner et al., 2008; Rottier et al., 2016, chapter 5). Aluminum content of quartz was
proposed as a proxy of fluid acidity by Rusk et al. (2008); however, our dataset tends to support the
inverse correlation with a mean Al concentration progressively decreasing from stage A, stage B2,
stage B1 and then stage C2.
It should be noticed that exact valence state of Sb (Sb5+ vs Sb3+) incorporated in quartz is not
defined (Rusk et al., 2011; Tanner et al., 2013). For our calculations we assume incorporation as Sb5+,
Sb concentration in the hydrothermal quartz from Cerro de Pasco is relatively low compared to Al (up
to 100 ppm or 0.8 mol/t) and would influence only slightly the calculated H+ concentration.
Figure 12: Correlation plots of trace elements in hydrothermal quartz from Cerro de Pasco : (A) (Li + Na + K+ P + Sb)
versus (Al + Fe + As) contents (in mol/t) and (B) calculated H versus Al contents (mol/t).
341
Various fluid sources at the large epithermal polymetallic deposit of Cerro de
Pasco
Role of meteoric water in the magmatic-hydrothermal system at Cerro de Pasco
Bulk vs in-situ oxygen isotope analyses of hydrothermal quartz

Baumgartner et al. (2008) reported oxygen isotope analyses of single quartz crystals from
stage A (n=2), B2 (n=3) and C2 (n=4) by laser fluorination. Figure 13 compares the bulk analyses to
the density plot distributions of the obtained in-situ SIMS δ18O values for each mineralization stage
(Fig. 13). Previous bulk analyses were done on different grains than the ones studied here, but they
could be used as a proxy for the average δ18O composition of analyzed quartz crystals. For stage A,
δ18O signatures of the two quartz crystals analyzed by Baumgartner et al. (2008) are centered on the
peak of the density plot distribution of the in-situ δ18O values (Fig. 13). For stage B2, bulk analyses are
shifted towards heavier values (Fig. 13), this fact is consistent with the fact that lower δ18O values are
mainly recorded in the crystal cores (Fig. 13 and supplementary Fig. A.3), and cores are
volumetrically less abundant than the rims. For stage C2, the bulk analyses are distributed between the
two main peaks on the density plot distribution, showing the importance of these two distinct δ18O
signatures in the bulk analyses.
In-situ oxygen isotopes analyses of quartz crystals were used to track input of meteoric water
in a few magmatic-hydrothermal systems (Allan and Yardley 2007; Fekete et al., 2016; Tanner et al.,
2013). Several points need to be addressed to properly interpret oxygen isotopic composition of
hydrothermal quartz: (i) isotopic composition of the different fluids involved in the hydrothermal
system; (ii) temperature of precipitation of the quartz crystals; (iii) effect of the isotopic exchange
between hydrothermal fluids and the surrounding country rocks; (iv) oxygen diffusion in hydrothermal
quartz; (v) sector zoning effect.
Oxygen isotopic composition of the local Miocene meteoric waters was determined by
Baumgartner et al. (2008) at 13 ± 1 ‰. In our data set, oxygen isotopic signature of the magmatic fluid
could be approximated by the two δ18O values of magmatic quartz measured in sample BR-24 Q2,
respectively 10.4 and 10.5 ‰ (supplementary Fig. A.4). Fractionation between quartz and rhyolitic
melt at 700°C is ~1 ‰ (Zhao and Zheng, 2003), thus calculated δ18O signature of the rhyolitic melt
will be of ~ 9.4 to 9.5 ‰, and fluid in equilibrium with this melt will be equal to 9.1 to 9.2 ‰ at 700°C
(Zhao and Zheng, 2003). These values are close to calculated δ18O values of fluids in equilibrium with
quartz crystals from the porphyry-type mineralization ranging from 8.5 to 9.6 ‰ and 10.6 to 11.6 ‰
respectively for the quartz-magnetite-chalcopyrite-(pyrite) porphyry-style veinlets crosscutting small
trachyte porphyries (PM2 in Fig. 13; Rottier et al., 2016a) and for HT1- and HT2-type quartz-
molybdenite-(chalcopyrite)-(pyrite) veins found in clasts from the diatreme-breccia (PM1 in Fig, 13;
342
Rottier et al., submitted). Fluid injected to the shallow part of the system results from mixing at depth
between low-salinity magmatic fluids and stored hypersaline magmatic fluids; fluid resulting of this
mixing will be referred hereafter as “deep” fluid. The “deep” mineralizing fluid before reaching the
upper level of the system could have interacted with the country rocks during its storage and its ascent.
Effect of this interaction on oxygen composition of the “deep” fluid could not be quantified. However,
considering the slight peak shift on the density plots of recalculated δ18O fluid values compared to
magmatic fluid values (Fig. 13), we assume that the “contamination” effect of the country rocks is
relatively weak and the oxygen isotopic signature of the “deep” fluid is close to the original magmatic
signature of ~9 ‰.
Temperature of formation during mineralization stages A, B2 and C2 is constrained by

microthermometry measurements (Rottier, 2016, chapter 5). The temperature of formation is: (i)
between 220° and 280°C (mean ≈ 250°C) for stage A; (ii) between 220° and 280°C (mean ≈ 245°C)
for stage B2, and (iii) between 260° and 295°C (mean ≈ 270°C) for quartz from stage C2 (Rottier 2016,
chapter 5). Mean temperatures obtained for each mineralization stage were used to determine the
isotopic composition of fluids in equilibrium with quartz (Fig. 13), using the equation of Zheng
(1993). Recorded temperature variation for stage A and B2 is 60°C, in the considered temperature
range (220-280°C) such variation could lead to a difference of δ18Oquartz (precipitating from the same
fluid) of 2.7‰. For the range of temperatures measured in quartz crystals from stage C2 (260-295°C)
this difference is equal to 1.3 ‰ (Zheng, 1993). For stage B1, FIAs measured by Rottier (2016, chapter
5) were mainly pseudo-secondary and display a large range of homogenization temperatures from
230° to 360°C. No accurate precipitation temperature of the quartz crystals from this stage could be
defined.
The main part of the epithermal mineralization is hosted by the Pucará carbonate sequence,
displaying δ18O compositions between 19.1 and 24.7‰ (Baumgartner et al., 2008). Interaction of
mineralizing fluids with replace carbonate rocks can potentially lead to a shift of their oxygen isotopic
compositions. Oxygen isotopic signatures of quartz from the “deep” quartz-pyrite veins (stage B1)
hosted in the diatreme breccia display the same range of δ18O than quartz from the carbonate
replacement bodies (stage A and B2, Fig. 13). It suggests only a minor influence of the Pucará
carbonates on the δ18O signatures of quartz.
Diffusive exchange of oxygen isotopes in quartz is very effective at medium to high

temperatures (>400°C; Farver and Yund, 1991) and it affects several 10s of micrometers of quartz in
less than 10’000 y (at 500°C). At lower temperature (< 300°C), oxygen isotope diffusive exchange is
slower and requires more than 1 My to diffuse over <15 µm (Farver and Yund, 1991). Spot size of in-
situ oxygen isotope measurement by SIMS is 15 µm, therefore for our study diffusion effect could be
ignored.
343
Figure 13: Histograms of in-situ δ18O isotopic compositions of quartz obtained by SIMS (red curves) from porphyry-type
mineralization (data from Rottier et al., 2016b and Rottier, 2016) and from the different epithermal mineralizations stages
(A, B1, B2 and C2). The light blue bars are δ18O composition of the fluids in equilibrium with quartz (see text for
discussion); Color dots represent δ18O composition of single quartz crystals analyzed by Baumgartner et al. (2008); the
hexagons represent the calculated fluids in equilibrium with the respective quartz. Dark blue lines represent the
percentage of mixing of meteoric water (δ18O=-13‰) with magmatic fluids (δ18O=9‰) necessary to explain the obtained
δ18O compositions of the fluids.
344
Similarly, no evidence of influence of sector zoning on the δ18O signature of the analyzed
quartz has been noticed, effect studied by several authors using laser fluorination and/or SIMS
(Jourdan et al., 2009a; Klemm et al., 1990 and 1991; Onasch and Venneman 1995; Tanner et al.,
2013). Onasch and Venneman (1995) and Jourdan et al. (2009a) report evidence of isotope
fractionation of up to 2‰ as a function of the crystallographic face of a quartz crystal, but Onasch and
Venneman (1995) did not analyzed equivalent pieces of the same quartz crystal. The structurally
controlled variations proposed by Jourdan et al. (2009a) in an oscillatory-zoned quartz crystal could be
discussed considering the fact that they observed similar variations in structurally similar analyzed
growth bands (Figs. 2-3 in Jourdan et al., 2009a). In contrast, no or slight effect (<0.3‰) were
reported by Tanner et al. (2013) and Klemm et al. (1990) and (1991).
Importance of meteoric water in the mineralizing system at Cerro de Pasco

Most of the δ18O values measured in quartz from mineralization stages A, B1 and B2 could be
explained by an input of less than 20% meteoric water into the “deep” (magmatic) fluid (Fig. 13).
Two types of δ18O variations were observed inside the studied quartz crystals of the different
mineralization stages:
1. Weak progressive variations of δ18Oquartz illustrated by (i) progressive increase of δ18Oquartz

between the core and the intermediate part of quartz crystals from stage B2 (Fig. 8); (ii) and by
progressive decrease of δ18Oquartz in the quartz rims from stage B1 and B2 (Fig. 7, profile A-B-C and
Fig. 8 profile A-C-D-E). These δ18Oquartz variations could be interpreted as a progressive input of the
“deep” fluid in rocks saturated in meteoric water at the beginning of the mineralization stages, or as a
progressive input decrease of the “deep” fluid in parallel to increased incursions of meteoric waters
towards the final stages of mineralization. It should be noted that increase or diminution of
temperature could influence such variations (up to 2.7 ‰, see above). No correlation between SEM-
CL textures and trace element content with the δ18Oquartz was observed.
2. Sharp (at the scale of less than 100 µm) drops of δ18Oquartz, up to 10.4‰. These sharp
changes occur in different quartz crystals (Figs. 6 A and 7 A), and are followed by a sharp δ18Oquartz
increase, like in quartz crystal BR-12 Q2 (Fig. 7), or, like in quartz crystals BR-111 (Fig. 6), δ18Oquartz
increase progressively. We interpret these sharp drops as punctual, volumetrically important, and
probably fast incursions of meteoric water (up to 60 %). Mechanisms leading to this incursion are
most probably tectonic, allowing episodic connection between meteoric water and the mineralizing
system. The observed δ18O sharp drops are not associated with variations of SEM-CL textures or of
trace element concentrations.
Rottier (2016, chapter 5), proposes for stages A, B1 and B2 a mixing of hypersaline metal-rich
porphyry-type fluids by a low-salinity less metal-rich fluid to explain his microthermometric and LA-
345
ICP-MS data on single fluid inclusions. The minor contribution of meteoric water in mineralization
stages A, B1 and B2, recorded by the in-situ SIMS oxygen isotope quartz signatures recorded in the
present work is a key argument for a magmatic origin for the low salinity fluid.
Meteoric water involvement is higher in stage C2, where sharp contacts between quartz grain
areas strongly influenced by meteoric water and others strongly influenced by magmatic fluid are
detected (Fig. 10). In contrast with the δ18Oquartz variations observed in stages A, B1 and B2 clear
correlations between δ18Oquartz, CL intensity and trace element concentrations are recognized. Core of
C2 quartz crystals and re-healed cracks show low δ18Oquartz values, indicating they were formed by a
meteoric water dominated fluid; core and re-healed cracks display also lower CL intensity and a lower
Al and Ti concentrations compared to parts dominated by magmatic fluids. In stage C2, quartz
precipitation predates that of enargite and pyrite in the veins and therefore no direct link between
observed δ18O quartz signatures and precipitation of sulfide and sulfosalt could be established.
Equilibrated fluids
Typical Br/Cl ratios suggested for magmatic fluids range from ~0.5 to 1.8x10-3 M (Banks et
al., 2000a, b; Böhlke and Irwin 1992; Irwin and Roedder 1995; Kendrick et al., 2001; Nahnybida et
al., 2009), overlapping mantle values ranging from ~1 to 2x10-3 M (Jambon et al., 1995; Johnson et
al., 2000). Obtained Br/Cl molar ratios of fluid inclusion leachates from HT2 porphyry veins in PM1
(0.46 to 1.16x10-3 M) fit the range of magmatic fluids, whereas the ones from the epithermal
mineralization stages show wider scattering from 0.42 to 4.35 x10-3 M (Fig. 3).
The Br/Cl signatures of crustal fluids can be affected by liquid-vapor fractionation during
phase separation, leading to Br enrichment of the residual liquid phase (Berndt and Seyfried 1997;
Liebscher et al., 2006; Lüders et al., 2002). To explain the strong enrichment of Br observed at Cerro
de Pasco (up to 4.35 x10-3 M) extensive boiling would be required. However, no evidence of such
boiling has been recognized (Rottier 2016, chapter 5). Other possible scenarios to explain high Br/Cl
ratios include (i) involvement of evaporated sea water in the mineralizing fluid (residual bitterns:
Kesler et al., 1995) and (ii) interaction of the mineralizing fluid with Br-rich organic matter or graphite
(Kendrick et al., 2011; Marsala et al., 2013; Rauchenstein-Martinek et al., 2016). The first possibility
would imply a removal of > 60% of the initial Cl by halite precipitation from the initial sea water in
order to explain the highest measured Br/Cl ratio (4.35 x10-3 M). Such high degree of evaporation
would lead to formation of large evaporitic layers which have not been recognized in the sedimentary
rocks of the district and the surrounding areas (Angeles 1999) although evaporites are known from
other parts of the Pucará basin in central Peru (Rosas et a., 2007). The second possibility is coherent
with the predominance of the Excelsior dark shales and phyllites (rich in organic matter), in the
stratigraphic sequence below the epithermal ore deposit (Angeles 1999), and also explains the positive
correlation between Cl/Br and 87Sr/86Sri signatures of the fluid inclusion leachates (see below, Fig. 14).
346
Moreover interaction of the mineralizing fluids with the Excelsior dark shales and phyllites has been
already proposed by Baumgartner et al. (2008) and Rottier et al. (2016b) to explain the low sulfidation
mineral assemblages of mineralization stage A.
87
Figure 14: Correlation plot between Sr/86Sr isotope ratio and Br/Cl ratios obtained from fluid inclusion leachates of
mineralization stages A, B2 and C1.
87
Fluid inclusion leachates from quartz of the porphyry-type veins PM1 display Sr/86Sri
signatures between 0.70975 and 0.71015 (Fig. 4), largely above the values obtained for the Miocene
magmatic rocks (0.70529-0.70564). The porphyry veins are hosted in hornfels (their protoliths are not
determined), and therefore the Sr isotopic signature of the mineralizing fluids may have been affected
by fluid-rock interactions. Fluid inclusion leachates from the different epithermal mineralization stages
(A, B2, C1 and C2) show similar large spread of data between 0.70970 and 0.71531. They range
between values similar to the ones obtained from the porphyry veins and even more radiogenic
87
Sr/86Sri signatures (Fig. 4, table 5). Such radiogenic signatures require interaction of the mineralizing
with Rb-rich rocks like Mitu detrital rocks, Excelsior dark shales or phyllites, or other basement rocks.
The rough positive correlation between Br/Cl values and 87Sr/86Sri signatures (Fig. 14), is in favor of
large-scale interaction with the Excelsior Group or with similar lithologies as discussed above.
87
The Sr/86Sri isotopic signatures present a similar range for all the mineralization stages.
Therefore, the signatures can be attributed neither to stored hypersaline metal-rich porphyry-type fluid
nor to the low salinity less metal-rich contracted magmatic vapor-like fluid that are mixed to form the
87
"deep" fluid. The obtained radiogenic Sr/86Sri isotopic signatures are probably acquired during the
ascent of the mixed “deep” fluid through the basement and in particular through the thick sequence of
the Excelsior shales and phyllites.
347
Metal content of the mineralizing fluids
Single fluid inclusion compositions from porphyry and epithermal mineralization stages at
Cerro de Pasco, determined by LA-ICP-MS and reported by Rottier (2016) and Rottier et al. (2016a
and submitted) have similar range of concentrations compared to the fluid inclusion leachates obtained
in the present study (Fig. 13).
Figure 15: Mn, Zn, Pb, Ag, Sb, As ratios [X/(Na+K)] obtained by LA-ICP-MS of fluid inclusions from: (i) different types
of porphyry fluids (Rottier, 2016 and Rottier et al., 2016a); (ii) different epithermal mineralization stages (Rottier, 2016).
These ratios are compared to the data on fluid inclusion leachates from this study. (*) Fluid inclusion leachates from
sphalerite and galena have been excluded.
348
Mineralizing fluid from the epithermal mineralization stages (A, B1, B2, C1 and C2) show
higher Zn, Pb and Mn elemental ratios [X/(Na+K)] than the ones from the not strictly
contemporaneous porphyry-type mineralization (intermediate density fluids, polyphase brine and late
liquid-dominated fluid and brine inclusions, Fig. 13); similar relationships also exist for Ag, Sb and As
but these elements were not successfully quantified in the fluid inclusion leachates (Fig. 13). Porphyry
mineralization styles from where the fluid inclusions have been studied are not strictly coetaneous of
the epithermal polymetallic deposit. Therefore hypersaline fluids analyzed could not be considered as
strictly representative of the magmatic fluid transporting metals to the epithermal mineralization.
Nonetheless their concentrations in Mn, Zn and Pb are in the range the published compositions of
hypersaline fluids from porphyry deposits compiled by Kouzmanov and Pokrovski (2013). To explain
the high metal concentrations observed in the most metal rich FIAs (Zn = 2.7 wt.% and Pb = 1.13
wt.%) from the epithermal mineralizations taking in account the dilution by the low salinity magmatic
fluid indicated by the microthermometric and LA-ICP-MS study done by Rottier (2016, chapter 5)
there are two alternative possibilities. It could be that (i) the magmatic fluid carrying metals to the
epithermal mineralization is unusually rich in metals (Zn, Pb, Mn and Fe) or (ii) the magmatic fluid
forming the epithermal polymetallic mineralization has been enriched in metals coming from an
external source.
Involvement of metals from a non-magmatic source is suggested by the Pb isotopic signatures

of the fluid inclusion leachates which differ from the Miocene magmatic Pb signature (Fig. 5). Our
results are compatible with the province II defined by Macfarlane et al. (1990) based on the
compilation of Pb isotopic compositions of sulfides from epithermal base metal deposits of central
Peru (Fig. 5). These signatures were interpreted as a mixture of magmatic (itself also with a crustal
signature, "orogene" in the sense of Doe and Zartmann, 1979) and crustal Pb signatures
(Macfarlane et al., 1990). The magmatic fluid having interacted with the Excelsior Group or other
similar lithologies could have leached some metals from the basement rocks. Altered Excelsior
phyllites sampled in the southern part of the open-pit are depleted to various degrees in Mn, Zn, Pb
and Sr compared to fresh equivalent (sampled 2 km west of the diatreme-dome complex; Fig. 16). But
considering the few numbers analyses (2 fresh phyllites and 1 altered phyllite) and the potential
chemical heterogeneities into the Excelsior phyllite this observation should be taken with cautious.
Potential leaching of previously formed porphyry-type and base metal mineralizations at depth
(Rottier et al., submitted) could be an additional source of metals.
349
Figure 16: Comparison of selected trace element content between fresh and altered Excelsior phyllites (XRF analyses);
Fresh phyllite composition results of a mean of two samples (detailed in supplementary table A.5) .
Chlorine isotopic composition

The compilation of published chlorine isotopic composition of fluid inclusion leachates from a
variety of hydrothermal ore deposits displays no correlation between the type of ore deposits and the
δ37Cl signatures (Fig. 3A and references therein). The δ37Cl signatures of the analyzed fluid inclusion
leachates range from 0 to 2‰, and no correlation between the obtained δ37Cl, Cl/Br ratio, and 87Sr/86Sri
isotopic signatures is observed. This suggests that obtained δ37Cl isotopic variations are not related to
interaction with radiogenic material as previously suggested for other magmatic hydrothermal systems
(Banks et al., 2000a,b; Chiaradia et al., 2006). Similar variation of δ37Cl signatures without correlation
87
with Cl/Br ratios or the Sr/86Sri isotopic signatures were observed in porphyry copper, IOCG and
shear-hosted Cu deposits (Gleeson et al., 2009; Nahnybida et al., 2009). Isotope fractionation by phase
separation and by halite precipitation are negligible <0.3 ‰ (Eggenkamp et al., 1995; Liebscher et al.,
2006). The δ37Cl signatures of magmatic fluids are assumed to reflect the signature of their magmatic
sources (Barnes et al. 2008 and 2014; Sharp et al. 2010), and the obtained range of values are coherent
with arc magma signatures (Fig. 3A, Barnes et al., 2008; Barnes et al., 2009; Chiaradia et al., 2014).
The observed δ37Cl variations may reflect δ37Cl heterogeneity of the magmatic source rather than
fractionation by other processes. Similar variations (up to 2‰) were observed in magmatic rocks from
the same volcanoes in Ecuador by Chiaradia et al. (2014).
Conclusions
In-situ SIMS oxygen isotope analyses of hydrothermal quartz indicate that mineralizing fluids
in stages A, B1 and B2, consist dominantly of the “deep” fluid with a minor involvement of meteoric
350
water (mostly <20 vol.%). Therefore, range of salinities and metal concentrations recorded in FIAs
from these stages is inherent to the “deep” fluid (itself resulting for stages A, B1, B2 and C1 from
mixing at depth between low-salinity magmatic fluids and stored hypersaline magmatic fluids). Even
if meteoric water involvement is low, variations of δ18Oquartz indicate different mechanisms of mixing:
(i) progressive decrease/increase of meteoric water involvement (always < 20 vol.%) at the beginning
and/or at the end of the mineralization stages and (ii) transient and punctual incursion creating local
sharp drops in δ18Oquartz. For the three mineralization stages A, B1 and B2 no correlation is observed
between trace element concentrations, CL intensity and the obtained δ18Oquartz, and role of meteoric
water for ore mineral precipitation seems to be not important. For the enargite-pyrite veins (stage C2),
quartz has parts with δ18O signatures clearly indicating they were formed by meteoric water-
dominated fluids. These parts display low trace element contents and dark CL intensity.
The radiogenic Sr and Pb isotopic signatures combined with Cl/Br ratios of fluid inclusion
leachates reveal an important interaction of the “deep” fluid with the low-metamorphic dark shales and
phyllites of the Paleozoic Excelsior Group (or with similar basement lithologies) during it ascent. Our
results suggest that a minor part of the Zn, Pb and Mn could have been leached from the Excelsior
rocks, leading to a potential enrichment of the mineralizing fluid forming the giant epithermal
polymetallic deposit of Cerro de Pasco.
Acknowledgement
This study 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. We gratefully acknowledge
Jean-Marie Boccard for his help with sample preparation.
References
Allan, M., Yardley, B., (2007). Tracking meteoric infiltration into a magmatic-hydrothermal system: a
cathodoluminescence, oxygen isotope and trace element study of quartz from Mt. Leyshon,
Australia. Chem. Geol. 240, 343–360
Angeles, C., 1999, Los sedimentos Cenozoicos de Cerro de Pasco: Estratigrafia, sedimentación y
tectónica, in Machare, J., Benavides-Caceres, V., and Rosas, S., eds., Sociedad Geológica del
Perú, 5, 103–118.
Audétat, A., Garbe‐Schönberg, D., Kronz, A., Pettke, T., Rusk, B., Donovan, J.J., Lowers, H.A.,
(2015). Characterisation of a natural quartz crystal as a reference material for microanalytical
determination of Ti, Al, Li, Fe, Mn, Ga and Ge. Geostand. Geoanal. Res. 39, 171-184.
Banks, D.A., Green, R., Cliff, R.A., Yardley, B.W.D., (2000a). Chlorine isotopes in fluid inclusions:
determination of the origins of salinity in magmatic fluids. Geochim. Cosmochim. Acta 64,
1785–1789.
Banks, D.A., Gleeson, S.A., Green, R., (2000b). Determination of the origin of salinity in granite-
related fluids: evidence from chlorine isotopes in fluid inclusions. J. Geo. Expl. 69, 309–312.
351
Barnes, J.D., Prather, T.J., Cisneros, M., Befus, K., Gardner, J.E., Larson, T.E., (2014). Stable chlorine
isotope behavior during volcanic degassing of H2O and CO2 at Mono Craters, CA. Bull.
Volcanol.76, 1-13.
Barnes, J.D.,Straub, S.M., (2010). Chorine stable isotope variations in Izu Bonin tephra: implications
for serpentinite subduction. Chem. Geol. 272, 62–74.
Barnes, J.D., Sharp, Z.D., Fischer, T.P., (2008). Chlorine isotope variations across the Izu-Bonin-
Mariana arc. Geology 36, 883–886.
Barnes, J.D., Sharp, Z.D., Fischer, T.P., Hilton, D.R., Carr, M.J., (2009). Chlorine isotope variations
along the Central American volcanic front and back arc. Geochem. Geophys. Geosyst. 10, 1-17.
Baumgartner, R., (2007). Sources and evolution in space and time of hydrothermal fluids at the Cerro
de Pasco Cordilleran base metal deposit, Central Peru. Terre & Environnement, v. 66, 167 p.
Baumgartner, R., Fontboté, L., Vennemann, T., (2008). Mineral zoning and geochemistry of
epithermal polymetallic Zn-Pb-Ag-Cu-Bi mineralization at Cerro de Pasco, Peru. Econ. Geol.
103, 493–537.
Baumgartner, R., Fontboté, L., Spikings, R., Ovtcharova, M., Schneider, J., Pace, L., Gutjahr, M.,
(2009). Bracketing the age of magmatic-hydrothermal activity at the Cerro de Pasco epithermal
polymetallic deposit, central Peru: a U-Pb and 40Ar/39Ar study. Econ. Geol. 104, 479-504.
Bendezú, R., Fontboté, L., (2009). Cordilleran epithermal Cu-Zn-Pb-(Au-Ag) mineralization in the
Colquijirca District, Central Peru: deposit-scale mineralogical patterns. Econ. Geol. 104, 905–
944.
Berndt, M.E., Seyfried, W.E., (1997). Calibration of BrCl fractionation during subcritical phase
separation of seawater: possible halite at 9 to 10 N East Pacific Rise. Geochim. Cosmochim.
Acta 61, 2849-2854.
Beuchat, S., Moritz, R., Pettke, T., (2004). Fluid evolution in the W-Cu-Zn-Pb San Cristobal vein,
Peru: Fluid inclusion and stable isotope evidence. Chem. Geol. 210, 201–224.
Bissig, T., Ullrich, T.D., Tosdal, R.M., Friedman, R., Ebert, S., (2008). The time-space distribution of
Eocene to Miocene magmatism in the central Peruvian polymetallic province and its
metallogenetic implications. J. South Am. Earth Sci. 26, 16–35.
Bissig, T., and Tosdal R.M., (2009). Petrogenetic and Metallogenetic Relationships in the Eastern
Cordillera Occidental of Central Peru: J. Geol. 117, 499–518.
Böhlke, J.K., and Irwin, J.J., (1992). Laser microprobe analyses of Cl, Br, I and K in fluid inclusions –
implications for sources of salinity in some ancient hydrothermal fluids. Geochim. Cosmochim.
Acta 56, 203–225.
Bussell, M. A., Alpers, C. N., Petersen, U., Shepherd, T. J., Bermudez, C., & Baxter, A. N. (1990).
The Ag-Mn-Pb-Zn vein, replacement, and skarn deposits of Uchucchacua, Peru; studies of
structure, mineralogy, metal zoning, Sr isotopes, and fluid inclusions. Econ. Geol. 85, 1348-
1383.
Camprubí, A., Albinson, T., (2007). Epithermal deposits in México—Update of current knowledge,
and an empirical reclassification. Geological Society of America Special Papers 422, 377-415.
Catchpole, H., Kouzmanov, K., Fontboté, L., Guillong, M., Heinrich, C.A., (2011). Fluid evolution in
zoned Cordilleran polymetallic veins - Insights from microthermometry and LA-ICP-MS of
fluid inclusions. Chem. Geol. 281, 293-304.
Catchpole, H., Kouzmanov, K., Putlitz, B., Seo, J., Fontboté, L., (2015). Zoned Base Metal
Morococha District, Peru. Econ. Geol. 110, 39–71.
Chiaradia, M., Banks, D.A., Cliff, R., Marschik, R., de Haller A., (2006). Origin of fluids in iron
oxide–copper–gold deposits: constraints from delta Clδ37, Sr-87/Sr-86(i) and Cl/Br. Min. Dep.
41, 565–573.
Chiaradia, M., Barnes, J. D., Cadet-Voisin, S. (2014). Chlorine stable isotope variations across the
Quaternary volcanic arc of Ecuador. Earth and Planetary Science Letters, 396, 22-33.
Deen, J.A., Rye, R.O., Munoz, J.L., Drexler, J.W., (1994). The magmatic hydrothermal system at
Julcani, Peru; evidence from fluid inclusions and hydrogen and oxygen isotopes. Econ. Geol.
89, 1924-1938.
352
Doe, B.R., Zartman, R.E., (1979). Plumbotectonics, I. The Phanerozoic. In: HL Barnes (Editor),
Geochemistry of Hydrothermal Ore Deposits. Wiley-Interscience, New York, NY, 2nd ed., pp.
22-70.
Einaudi, M.T., (1968). Pyrrhotite-pyrite-sphalerite relations at Cerro de Pasco, Peru. Unpublished
Ph.D. thesis, Cambridge, MA, Harvard University, 381 p.
Einaudi, M.T., (1977). Environment of ore deposition at Cerro de Pasco, Peru. Econ. Geol. 72, 893–
924.
Farver, J. R., Yund, R.A., (1991). Oxygen diffusion in quartz: dependence on temperature and water
fugacity. Chem. Geol. 90, 55-70.
Fekete, S., Weis, P., Driesner, T., Bouvier, A-S., Baumgartner, L., Heinrich, C.A., (2016). Contrasting
hydrological processes of meteoric water incursion during magmatic–hydrothermal ore
deposition: An oxygen isotope study by ion microprobe. Earth Planet. Sci. Lett. 451, 263-271.
Gleeson, S.A., Smith, M.P., (2009). The sources and evolution of mineralising fluids in iron oxide–
copper–gold systems, Norrbotten, Sweden: constraints from Br/Cl ratios and stable Cl isotopes
of fluid inclusion leachates. Geochim. Cosmochim. Acta 73, 5658-5672.
Germann, K., Lüders, V., Banks, D.A., Simon, K., Hoefs, J., (2003). Late Hercynian polymetallic
vein-type base-metal mineralization in the Iberian Pyrite Belt: fluid-inclusion and stable-isotope
geochemistry (S–O–H–Cl). Min. Dep. 38, 953-967.
Götze, J., (2009). Chemistry, textures and physical properties of quartz–geological interpretation and
technical application. Min. Mag. 73, 645-671.
Guillong, M., Heinrich, C.A., (2007). LA-ICP-MS analysis of inclusions: Improved ablation and
detection: European Current Research On Fluid Inclusions (ECROFI-XIX), At Bern, p. 82.
Guillong, M., Meier, D.L., Allan, M.M., Heinrich, C.A., Yardley, B.W.D., (2008). SILLS: a Matlab-
based program for the reduction of Laser Ablation ICP-MS data of homogeneous materials and
and outstanding issues. Mineralogical Association of Canada, Vancouver, B.C., 328–333.
Günther, D., Frischknecht, R., Heinrich, C.A., and Kahlert, H.J., (1997). Capabilities of an Argon
Fluoride 193 nm excimer laser for laser ablation inductively coupled plasma mass spectrometry
microanalysis of geological materials. J. Anal. At. Spectrom. 12, 939-944.
Günther, D., Audétat, A., Frischknecht, R., Heinrich, C.A., (1998). Quantitative analysis of major,
minor and trace elements in fluid inclusions using laser ablation–inductively coupled
plasmamass spectrometry: J. Anal. At. Spectrom. 13, 263-270.
Heinrich, C.A., Pettke, T., Halter, W.E., Aigner-Torres, M., Audétat, A., Günther, D., Hattendorf, B.,
Bleiner, D., Guillong ,M., Horn, I., (2003). Quantitative multi-element analysis of minerals,
fluid and melt inclusions by laser-ablation inductively-coupled-plasma mass-spectrometry:
Geochim. Cosmochim. Acta 67, 3473–3496.
Huang, R., Audétat, A., (2012). The titanium-in-quartz (TitaniQ) thermobarometer: a critical
examination and re-calibration: Geochim. Cosmochim. Acta 84, 75–89.
Ihinger, P.D., Zink, S. I., (2000). Determination of relative growth rates of natural quartz crystals.
Nature, 404, 865-869.
Irwin, J.J., Roedder, E., (1995). Diverse origins of fluid in magmatic inclusions at Bingham (Utah,
USA), Butte (Montana, USA), St. Austell (Cornwall, UK), and Ascension Island (mid-Atlantic,
UK), indicated by laser microprobe analysis of Cl, K, Br, I, Ba+ Te, U, Ar, Kr, and Xe.
Geochim. Cosmochim. Acta 59, 295-312.
Jambon, A., Déruelle, B., Dreibus, G., Pineau, F., (1995). Chlorine and bromine abundance in MORB:
the contrasting behaviour of the Mid-Atlantic Ridge and East Pacific Rise and implications for
chlorine geodynamic cycle. Chem. Geol. 126, 101-117.
Johnson, L.H., Burgess, R., Turner, G., Milledge, H.J., Harris, J.W., (2000). Noble gas and halogen
geochemistry of mantle fluids: comparison of African and Canadian diamonds. Geochim.
Cosmochim. Acta 64, 717-732.
Jourdan, A. L., Vennemann, T.W., Mullis, J., Ramseyer, K., (2009a). Oxygen isotope sector zoning in
natural hydrothermal quartz. Min. Mag. 73, 615-632.
Jourdan, A.L., Vennemann, T.W., Mullis, J., Ramseyer, K., Spiers, C.J., (2009b). Evidence of growth
and sector zoning in hydrothermal quartz from Alpine veins. Eur. J. Min. 21, 219-231.
353
Kendrick, M.A., Burgess, R., Pattrick, R.A.D., Turner, G., (2001). Fluid inclusion noble gas and
halogen evidence on the origin of Cu-Porphyry mineralising fluids. Geochim. Cosmochim. Acta
65, 2651-2668.
Kendrick, M.A., Phillips, D., Wallace, M., Miller, J.M., (2011). Halogens and noble gases in
sedimentary formation waters and Zn–Pb deposits: A case study from the Lennard Shelf,
Australia. Appl. Geochem. 26, 2089-2100.
Kesler, S.E., Appold, M.S., Martini, A.M., Walter, L.M., Huston, T.J., Kyle, J.R., (1995). Na-Cl-Br
systematics of mineralizing brines in Mississippi Valley–type deposits. Geology 23, 641-644.
Klemm, A., Banerjee, A., Hoernes, S., (1990). A new intracrystalline isotope effect: 18O under the
faces of amethyst. Z. Naturforsch. A 45, 1374-1376.
Klemm, A., Banerjee, A., Hoernes, S., (1991). Fractionation of oxygen isotopes at the faces of smoky
quartz. Z. Naturforsch. A 46, 1133-1134.
Koděra, P., Heinrich C.A., Wälle M., Lexa J., (2014). Magmatic salt melt and vapor: Extreme fluids
forming porphyry gold deposits in shallow subvolcanic settings. Geology 42, 495-498.
Kouzmanov, K., Chiaradia, M., Fontboté, L., Spangenberg, J. E., (2011). Origin of massive anhydrite
bodies in the Morococha district, central Peru: insights from stable (O, S) and radiogenic (Sr,
Nd) isotope geochemistry. Dans Barra, F., Reich, M., Campos, F. and Tornos, F. (Ed.) Society
for Geology Applied to Mineral Deposits (SGA) 11th Biennial Meeting (p. 405-407).
Kouzmanov, K., and Pokrovski, G.S., 2012, Hydrothermal controls on metal distribution in porphyry
Cu (-Mo-Au) systems: Society of Economic Geologists Special Publication 16, 573–618.
Landtwing, M.R., Pettke, T., (2005). Relationships between SEM-cathodoluminescence response and
trace-element composition of hydrothermal vein quartz. Am. Min. 90, 122-131.
Liebscher, A., Lüders, V., Heinrich, W., Schettler, G., (2006). Br/Cl signature of hydrothermal fluids:
liquid–vapour fractionation of bromine revisited. Geofluids 6, 113-121.
Liebscher, A., Barnes, J., Sharp, Z., (2006). Chlorine isotope vapor–liquid fractionation during
experimental fluid-phase separation at 400 C/23 MPa to 450 C/42 MPa. Chem. Geol. 234, 340-
345.
Lüders, V., Banks, D.A., Halbach, P., (2002). Extreme Cl/Br and δ37Cl isotope fractionation in fluids
of modern submarine hydrothermal systems. Min. Dep. 37, 765-771.
Macfarlane, A.W., Marcet, P., LeHuray, A.P., Petersen, U., (1990). Lead isotope provinces of the
Central Andes inferred from ores and crustal rocks. Econ. Geol. 85, 1857-1880.
Marsala, A., Wagner, T., Wälle, M., (2013). Late-metamorphic veins record deep ingression of
meteoric water: A LA-ICPMS fluid inclusion study from the fold-and-thrust belt of the Rhenish
Massif, Germany. Chem. Geol. 351, 134-153.
Maydagán, L., Franchini, M., Rusk, B., Lentz, D.R., McFarlane, C., Impiccini, A., Rios, J.R., Rey, R.
(2015). Porphyry to Epithermal Transition in the Altar Cu-(Au-Mo) Deposit, Argentina, Studied
by Cathodoluminescence, LA-ICP-MS, and Fluid Inclusion Analysis. Econ. Geol. 110, 889-
923.
Mercer, C.N., Reed, M.H., (2013). Porphyry Cu-Mo stockwork formation by dynamic, transient
hydrothermal pulses: mineralogic insights from the deposit at Butte, Montana. Econ. Geol. 108,
1347-1377.
Miyoshi, N., Yamaguchi, Y., Makino, K. (2005). Successive zoning of Al and H in hydrothermal vein
quartz. Am. Min. 90, 310-315.
Moritz, R., Beuchat, S., Chiaradia, M., Stucky, P., Sallier, B., Lisboa,H., (2001). Zn–Pb mantos and
veins at Domo de Yauli, Central Peru: two products of one hydrothermal system with common
Pb and S sources, but contrasting fluid inclusion characteristics. 6th Biennial Meeting of the
SGA, Krakow, Poland. In: Mineral deposit at the beginning of the 21st century, Balkema,
Netherland, pp. 173–176.
Müller, A., Koch-Müller, M., (2009). Hydrogen speciation and trace element contents of igneous,
hydrothermal and metamorphic quartz from Norway. Min. Mag. 73, 569-583.
Müller, A., Herrington, R., Armstrong, R., Seltmann, R., Kirwin, D.J., Stenina, N.G., Kronz, A.
(2010). Trace elements and cathodoluminescence of quartz in stockwork veins of Mongolian
porphyry-style deposits. Min. Dep. 45, 707-727.
Mukasa, S.B., Injoque-Espinoza, J., (1990). Pb isotope bearing on the metallogenesis of sulfide ore
deposits in central and southern Peru. Econ. Geol. 85, 1438-1446.
354
Nahnybida, T., Gleeson, S.A., Rusk, B.G., Wassenaar, L.I., (2009). Cl/Br ratios and stable chlorine
isotope analysis of magmatic–hydrothermal fluid inclusions from Butte, Montana and Bingham
Canyon, Utah. Min. Dep. 44, 837-848.
Noble, D.C., McKee, E.H, (1999). The Miocene metallogenic belt of central and northern Peru. In
Skinner, B. J., ed. Geology and ore deposits of the central Andes: Society of Economic Geology
Special Publication, 7, 155–193.
Norman, D.I., Landis, G.P., (1983). Source of mineralising components in hydrothermal ore fluid as
evidenced by 87Sr/86Sr and stable isotope data from the Pasta Bueno deposit, Peru. Econ. Geol.
78, 451–465.
Ohmoto, H., Rye, R.O., (1974). Hydrogen and oxygen isotopic compositions of fluid inclusions in the
Kuroko deposits, Japan. Econ. Geol. 69, 947-953.
Onasch, C.M., Vennemann, T.W., (1995). Disequilibrium partitioning of oxygen isotopes associated
with sector zoning in quartz. Geology 23, 1103-1106.
Pudack, C., Halter, W.E., Heinrich, C.A., and Pettke, T., (2009). Evolution of magmatic vapor to gold-
rich epithermal liquid: The porphyry to epithermal transition at Nevados de Famatina,
northwestern Argentina. Econ. Geol. 104, 449–477.
Pytkowicz, R.M., Kester D.R., 1971 Physical chemistry of sea water. Oceanogr. Mar. Biol., 9, 11–60.
Rauchenstein-Martinek, K., Wagner, T., Wälle, M., Heinrich, C.A., Arlt, T., (2016). Chemical
evolution of metamorphic fluids in the Central Alps, Switzerland: Insight from LA-ICPMS
analysis of fluid inclusions. Geofluids, in press DOI: 10.1111/gfl.12194
Rosas, S., Fontboté, L., Tankard, A., (2007). Tectonic evolution and paleogeography of the Mesozoic
Pucará Basin, central Peru: J. South Am. Earth Sci. 26, 16–35.
Rottier. B., 2016, Magmatic and hydrothermal fluid processes at the origin of the giant porphyry-
related epithermal polymetallic deposit of Cerro de Pasco (Central Peru), Phd thesis, University
of Geneva
Rottier, B., Kouzmanov, K., Bouvier, A.-S., Baumgartner, L., Wälle, M., Rezeau, H., Bendezú, R.,
Fontboté, L., (2016a). Heterogeneous melt and hypersaline liquid inclusions in shallow
porphyry type mineralization as markers of the magmatic-hydrothermal transition (Cerro de
Pasco district, Peru):. Chem. Geol. doi: 10.1016/j.chemgeo.2016.10.032
Rottier, B., Kouzmanov, K., Wälle, M., Bendezú, R., and Fontboté, L., (2016b) Sulfide replacement
processes revealed by textural an LA-ICP-MS trace element analyses: example from the early
mineralization stages at Cerro de Pasco, Peru: Econ. Geol. 111, 1347-1367.
Rottier, B., Kouzmanov, K., Casanova, C., Bouvier, A.-S., Baumgartner, L., Wälle, M., Fontboté, L.,
(Submitted) Hydrothermal evolution of a hidden porphyry-type mineralization related to the
large epithermal polymetallic deposit of Cerro de Pasco district (Peru): Miner. Dep.
Rusk B.G., Lowers H.A., Reed M.H., (2008). Trace elements in hydrothermal quartz: relationships to
cathodoluminescence textures and insights into vein formation. Geology 36, 547–550.
Rusk, B., Koenig, A., Lowers, H., (2011). Visualizing trace element distribution in quartz using
cathodoluminescence, electron microprobe, and laser ablation-inductively coupled plasma-mass
spectrometry. Am. Min., 96, 703-708.
Rye, R. O., Sawkins, F.J., (1974). Fluid inclusion and stable isotope studies on the Casapalca Ag-Pb-
Zn-Cu deposit, central Andes, Peru. Econ. Geol. 69, 181-205.
Seitz, S., Baumgartner, L.P., Bouvier, A.-S., Putlitz, B., Vennemann, T., (2016). Quartz Standards for
Oxygen Isotope and Trace Element Analysis by SIMS, Geost. Geoanal. Res. In press
Sharp, Z.D., Barnes, J.D., Fischer, T.P., Halick, M., (2010). A laboratory determinationof chlorine
isotope fractionation in acid systems and applications to volcanic fumaroles. Geochim.
Cosmochim. Acta 74, 264–273
Simmons, S.F., White, N.C., John, D.A., (2005). Geological characteristics of epithermal precious and
base metal deposits. Economic Geology 100th anniversary volume, 29, 485-522.
Spikings, R., Reitsma, M.J., Boekhout, F., Miškovic´, A., Ulianov, A., Chiaradia, M., Gerdes, A.,
Schaltegger , U., (2016). Characterization of Triassic rifting in Peru and implications for the
early disassembly of western Pangaea: Gondwana Res. 35, 124–143.
Tanner, D., Henley, R.W., Mavrogenes, J.A., Holden, P., (2013). Combining in situ isotopic, trace
element and textural analyses of quartz from four magmatic-hydrothermal ore deposits. Contrib.
Miner. Petr. 166, 1119-1142.
355
Thomas, J.B., Watson, E.B., Spear, F.S., Shemella, P.T., Nayak, S.K., Lanzirotti, A., (2010). TitaniQ
under pressure: the effect of pressure and temperature on the solubility of Ti in quartz. Contr.
Miner. Petr. 160, 743-759.
Wark, D.A., Watson, E.B., (2006). TitaniQ: a titanium-in-quartz geothermometer. Contr. Miner.
Petr.152, 743-754.
Zhao, Z.F., Zheng, Y.F., (2003). Calculation of oxygen isotope fractionation in magmatic rocks.
Chem. Geol. 193, 59-80.
Zheng, Y.F., (1993). Calculation of oxygen isotope fractionation in anhydrous silicate minerals.
Geochim. Cosmochim. Acta 57, 1079-1079.
356
Figure A.1: SEM-CL images of quartz grains from sample BR-175 (stage A); pink circles are location
and results of SIMS oxygen isotope analyses
357
Figure A.2: SEM-CL images of quartz crystals BR-12 Q5 andBR-05 Q1 from stage B1; pink circles are
location and results of SIMS oxygen isotope analyses; green circles are location and number of LA-
ICP-MS trace element analyses.
358
Figure A.3: SEM-CL images of quartz crystal CV-11 Q6 from stage B2 pink circles are location and
results of SIMS oxygen isotope analyses; green circles are location and number of LA-ICP-MS trace
element analyses.
359
Figure A.4: SEM-CL images of quartz crystal BR-24 Q2 from stage C2; pink circles are location and
results of SIMS oxygen isotope analyses
360
Table A.1: Element concentration ratios obtained by ICP-MS analyses of the fluid inclusion leachates
Na/(Na+K Al/(Na+K Ca/(Na+ Sc/(Na+K Cr/(Na+K Mn/(Na+K Fe/(Na+K Co/(Na+ Ni/(Na+K Zn/(Na+K
Sample Stage Mineral ) ) K/(Na+K) K) ) Ti/(Na+K) V/(Na+K) ) ) ) K) ) )
BR-267 porphyry QUARTZ 3.688E-01 1.095E-02 6.312E-01 1.021E-02 N.D. N.D. N.D. N.D. 2.132E-02 3.536E-01 9.833E-05 N.D. 3.011E-02
BR-315 porphyry QUARTZ 4.186E-01 1.809E-02 5.814E-01 1.693E-02 N.D. N.D. 3.441E-05 N.D. 3.130E-02 3.869E-01 N.D. N.D. 2.336E-02
BR-111 A SPHALERITE 6.380E-01 N.D. 3.620E-01 1.913E-02 N.D. N.D. N.D. N.D. 5.809E-02 2.570E-01 2.850E-04 N.D. 9.930E-01
BR-111 A QUARTZ 5.864E-01 2.052E-02 4.136E-01 4.142E-02 N.D. N.D. 1.724E-04 N.D. 5.559E-02 5.278E-01 N.D. N.D. 6.853E-02
BR-130 A SPHALERITE 6.338E-01 N.D. 3.662E-01 5.811E-02 N.D. N.D. N.D. N.D. 5.063E-02 7.281E-02 1.643E-04 8.825E-04 6.502E-01
BR-175 A SPHALERITE 6.425E-01 7.957E-04 3.575E-01 9.607E-02 N.D. N.D. N.D. N.D. 5.575E-02 1.347E+00 1.336E-04 5.663E-04 7.521E+00
BR-59 A PYRRHOTITE 5.961E-01 N.D. 4.039E-01 4.646E-02 N.D. N.D. N.D. 6.540E-04 5.277E-02 1.240E+01 N.D. N.D. N.D.
BR-59 A QUARTZ 6.051E-01 8.748E-03 3.949E-01 7.856E-02 N.D. N.D. 7.930E-05 N.D. 3.891E-02 4.048E-01 N.D. N.D. 9.981E-03
BR-106 B2 PYRITE 5.991E-01 7.713E-02 4.009E-01 1.078E-01 N.D. N.D. N.D. N.D. 1.007E-01 1.435E+01 3.514E-04 N.D. 1.101E+00
BR-106 B2 QUARTZ 5.286E-01 1.729E-02 4.714E-01 1.455E-01 N.D. N.D. 1.914E-04 N.D. 5.052E-02 3.766E-01 N.D. N.D. 7.230E-02
BR-126 B2 PYRITE 5.790E-01 1.659E-02 4.210E-01 4.937E-02 N.D. N.D. N.D. N.D. 3.654E-02 1.007E+01 N.D. 2.652E-03 1.796E-01
BR-126 B2 QUARTZ 5.473E-01 8.133E-03 4.527E-01 2.339E-02 N.D. 2.174E-04 N.D. N.D. 3.330E-02 1.384E-01 N.D. N.D. 2.895E-02
BR-80 B2 PYRITE 1.000E+00 N.D. N.D. N.D. N.D. N.D. N.D. N.D. 9.668E-02 1.772E+01 N.D. N.D. 2.916E-01
BR-196 C1 GALENA 5.952E-01 N.D. 4.048E-01 3.236E-02 N.D. N.D. N.D. N.D. 3.065E-01 1.623E-01 5.132E-04 2.304E-03 1.051E+00
BR-196 C1 CARBONATE 6.139E-01 N.D. 3.861E-01 9.126E-02 N.D. N.D. N.D. N.D. 1.667E+00 1.489E-01 N.D. N.D. 1.843E-01
BR-198 C1 GALENA 6.141E-01 N.D. 3.859E-01 5.728E-02 N.D. N.D. N.D. N.D. 4.329E-01 N.D. 5.133E-04 2.233E-03 1.235E+00
BR-24 C2 ENARGITE 5.428E-01 N.D. 4.572E-01 1.704E-02 5.046E-06 N.D. N.D. N.D. 1.300E-01 N.D. N.D. N.D. 2.782E-01
BR-24 C2 QUARTZ 4.483E-01 2.245E-02 5.517E-01 3.057E-02 N.D. 1.535E-03 N.D. N.D. 5.758E-02 1.797E-01 N.D. N.D. 7.570E-02
BR-143 C2 ENARGITE 5.547E-01 4.395E-02 4.453E-01 3.401E-02 N.D. N.D. 1.994E-04 N.D. 1.514E-01 2.457E+00 N.D. N.D. 1.173E-01
BR-152 C2 ENARGITE 6.537E-01 6.074E-03 3.463E-01 2.476E-02 N.D. N.D. N.D. 8.608E-04 8.893E-02 8.957E-01 N.D. N.D. 4.903E-01
BR-152 C2 PYRITE 6.377E-01 2.274E-02 3.623E-01 2.370E-01 N.D. N.D. 6.082E-05 N.D. 6.451E-02 7.932E+00 2.144E-04 1.046E-03 4.151E-01
N.D. : Not detected, values bellow the mean values obtained by the ICP-MS analyses of the blanks (see methods supplementary file A1)
361
Se/(Na+K Rb/(Na+ Sr/(Na+K Mo/(Na+ Cs/(Na+ Ba/(Na+ La/(Na+K Ce/(Na+ Pr/(Na+K Nd/(Na+ Sm/(Na+ Eu/(Na+ Gd/(Na+
Sample Stage Mineral ) K) ) K) K) K) ) K) ) K) K) K) K)
BR-267 porphyry QUARTZ N.D. 9.828E-04 8.690E-04 N.D. 5.815E-05 2.074E-02 4.370E-06 N.D. N.D. N.D. N.D. 7.059E-06 N.D.
BR-315 porphyry QUARTZ N.D. 1.458E-03 3.261E-03 1.072E-02 4.598E-04 2.068E-03 1.809E-05 3.751E-05 3.124E-06 1.546E-05 N.D. N.D. N.D.
BR-111 A SPHALERITE N.D. 1.343E-03 1.354E-03 N.D. 1.713E-03 9.191E-04 N.D. N.D. N.D. N.D. N.D. N.D. N.D.
BR-111 A QUARTZ N.D. 1.487E-03 1.842E-03 N.D. 1.141E-03 8.616E-03 N.D. N.D. N.D. N.D. N.D. 5.080E-06 N.D.
BR-130 A SPHALERITE N.D. 1.459E-03 6.791E-03 N.D. 1.773E-03 1.696E-03 N.D. N.D. N.D. N.D. N.D. N.D. N.D.
BR-175 A SPHALERITE N.D. 1.054E-03 1.689E-02 N.D. 1.430E-03 4.892E-04 3.628E-05 5.722E-05 5.586E-06 2.841E-05 N.D. 3.574E-06 1.573E-05
BR-59 A PYRRHOTITE N.D. 1.240E-03 2.823E-03 N.D. 9.829E-04 8.391E-04 N.D. N.D. N.D. N.D. N.D. N.D. N.D.
BR-59 A QUARTZ N.D. 1.169E-03 2.944E-03 N.D. 6.005E-04 3.994E-04 N.D. N.D. N.D. N.D. N.D. N.D. N.D.
BR-106 B2 PYRITE 6.128E-04 1.449E-03 2.652E-02 N.D. 1.406E-03 6.110E-03 7.332E-04 1.765E-03 2.247E-04 1.025E-03 5.577E-04 3.007E-04 8.580E-04
BR-106 B2 QUARTZ N.D. 1.539E-03 4.913E-02 N.D. 1.166E-03 1.533E-02 3.965E-05 9.614E-05 1.246E-05 5.458E-05 1.782E-05 2.092E-05 4.418E-05
BR-126 B2 PYRITE N.D. 8.053E-04 4.773E-03 N.D. 9.488E-04 3.760E-03 N.D. 1.972E-05 N.D. 1.388E-05 N.D. 4.045E-06 N.D.
BR-126 B2 QUARTZ N.D. 1.649E-03 2.149E-03 N.D. 1.690E-03 2.039E-03 N.D. N.D. N.D. N.D. N.D. N.D. N.D.
BR-80 B2 PYRITE N.D. 2.893E-03 1.387E-02 N.D. 2.145E-03 9.404E-03 6.247E-05 1.069E-04 9.638E-06 4.651E-05 N.D. 1.716E-05 1.684E-05
BR-196 C1 GALENA N.D. 1.073E-03 1.931E-03 N.D. 1.352E-03 3.704E-03 N.D. 2.890E-05 N.D. N.D. 2.632E-05 N.D. N.D.
BR-196 C1 CARBONATE N.D. 1.415E-03 1.510E-03 1.321E-04 2.003E-03 1.063E-02 N.D. N.D. N.D. N.D. N.D. N.D. N.D.
BR-198 C1 GALENA N.D. 1.305E-03 5.399E-03 1.257E-04 1.714E-03 7.848E-03 N.D. 3.614E-05 N.D. N.D. N.D. 7.624E-06 2.890E-05
BR-24 C2 ENARGITE N.D. 1.832E-03 4.346E-04 N.D. 2.058E-03 8.726E-04 N.D. N.D. N.D. N.D. N.D. N.D. N.D.
BR-24 C2 QUARTZ N.D. 1.716E-03 3.144E-03 4.192E-04 1.205E-03 1.045E-02 N.D. N.D. N.D. N.D. N.D. N.D. N.D.
BR-143 C2 ENARGITE N.D. 1.649E-03 2.037E-03 N.D. 3.913E-03 6.642E-04 5.575E-05 N.D. N.D. N.D. N.D. N.D. N.D.
BR-152 C2 ENARGITE N.D. 1.452E-03 9.532E-04 1.238E-04 2.326E-03 3.729E-03 2.517E-05 1.641E-05 N.D. N.D. N.D. N.D. N.D.
BR-152 C2 PYRITE N.D. 1.587E-03 5.340E-03 6.632E-05 2.264E-03 1.912E-02 8.037E-04 1.484E-03 1.669E-04 5.877E-04 1.329E-04 3.257E-05 1.152E-04
N.D. : Not detected, values bellow the
362
Tb/(Na+K Dy/(Na+ Ho/(Na+ Er/(Na+K Tm/(Na+ Yb/(Na+ Pb/(Na+K

Sample Stage Mineral ) K) K) ) K) K) )
BR-267 porphyry QUARTZ N.D. 4.145E-08 9.637E-08 N.D. 1.944E-07 N.D. 2.822E-02
BR-315 porphyry QUARTZ N.D. N.D. 1.926E-07 N.D. N.D. N.D. 1.884E-03
BR-111 A SPHALERITE N.D. N.D. N.D. N.D. 1.137E-06 N.D. N.D.
BR-111 A QUARTZ N.D. N.D. N.D. N.D. 1.567E-06 N.D. 3.045E-02
BR-130 A SPHALERITE N.D. N.D. 5.534E-07 N.D. N.D. N.D. 3.009E-03
BR-175 A SPHALERITE 4.789E-06 3.892E-05 9.173E-06 3.825E-05 5.256E-06 1.900E-05 1.172E+00
BR-59 A PYRRHOTITE N.D. N.D. 9.853E-07 N.D. N.D. N.D. N.D.
BR-59 A QUARTZ 1.839E-06 N.D. 5.520E-07 N.D. 1.249E-06 N.D. N.D.
BR-106 B2 PYRITE 9.935E-05 3.503E-04 4.432E-05 9.776E-05 1.704E-05 8.378E-05 8.626E-02
BR-106 B2 QUARTZ 4.917E-06 1.885E-05 4.891E-06 8.637E-06 3.041E-06 4.381E-06 2.124E-02
BR-126 B2 PYRITE N.D. N.D. 1.499E-06 5.446E-06 1.686E-06 N.D. 1.043E-02
BR-126 B2 QUARTZ N.D. N.D. N.D. N.D. 5.884E-07 N.D. 5.110E-03
BR-80 B2 PYRITE 7.644E-06 2.385E-05 5.770E-06 1.483E-05 3.770E-06 N.D. 1.110E-01
BR-196 C1 GALENA 3.365E-06 9.217E-06 4.820E-06 N.D. 4.545E-06 N.D. 2.669E+01
BR-196 C1 CARBONATE N.D. N.D. N.D. N.D. N.D. N.D. 1.418E-02
BR-198 C1 GALENA 9.558E-06 5.715E-05 1.509E-05 3.379E-05 4.252E-06 2.291E-05 1.794E+01
BR-24 C2 ENARGITE N.D. N.D. N.D. N.D. 1.505E-06 N.D. N.D.
BR-24 C2 QUARTZ N.D. N.D. N.D. 1.176E-05 2.172E-06 N.D. N.D.
BR-143 C2 ENARGITE N.D. N.D. N.D. N.D. N.D. N.D. N.D.
BR-152 C2 ENARGITE N.D. N.D. N.D. N.D. 2.230E-06 N.D. 7.862E-01
BR-152 C2 PYRITE 1.789E-05 1.009E-04 2.374E-05 7.447E-05 1.180E-05 6.837E-05 5.737E-01
N.D. : Not detected, values bellow the
363
Table A.2a: Sr and Pb isotopic ratios of fluid inclusion leachates
87
Sr/ 86 Sr age 1σ 1σ
Sample Stage Mineral 87
Sr/ 86 Sr 1σ ( 87 Sr/ 86 Sr) 206
Pb/ 204 Pb 207
Pb/ 204 Pb 208
Pb/ 204 Pb 1σ ( 206 Pb/ 204 Pb)
corrected ( 207 Pb/ 204 Pb) ( 208 Pb/ 204 Pb)
BR-111 A SPHALERITE 0.71393 0.71334 8.30E-05 N.D. N.D. N.D. N.D. N.D. N.D.
BR-111 A QUARTZ 0.71381 0.71333 5.45E-05 18.696 15.608 38.714 4.13E-03 3.37E-03 8.27E-03
BR-130 A SPHALERITE 0.71124 0.71111 1.36E-05 18.748 15.670 38.850 7.04E-03 5.93E-03 1.47E-02
BR-175 A SPHALERITE 0.71090 0.71087 1.03E-05 18.778 15.656 38.862 1.69E-04 1.51E-04 4.11E-04
BR-59 A PYRRHOTITE 0.71329 0.71303 3.78E-05 N.D. N.D. N.D. N.D. N.D. N.D.
BR-59 A QUARTZ 0.71265 0.71241 3.56E-05 N.D. N.D. N.D. N.D. N.D. N.D.
BR-106 B2 PYRITE 0.71352 0.71349 1.07E-05 18.769 15.661 38.859 1.23E-03 9.71E-04 2.56E-03
BR-106 B2 QUARTZ 0.71224 0.71222 7.82E-06 18.699 15.612 38.718 3.16E-03 2.69E-03 6.51E-03
BR-126 B2 PYRITE 0.71161 0.71151 2.94E-05 18.779 15.696 38.899 8.22E-03 6.55E-03 1.65E-02
BR-126 B2 QUARTZ 0.71253 0.71208 4.47E-05 N.D. N.D. N.D. N.D. N.D. N.D.
BR-80 B2 PYRITE 0.71243 0.71230 2.28E-05 18.785 15.664 38.878 1.84E-03 1.59E-03 3.87E-03
BR-196 C1 GALENA 0.71221 0.71188 8.47E-05 18.773 15.657 38.860 1.97E-04 2.14E-04 6.57E-04
BR-196 C1 CARBONATE 0.71068 0.71053 4.86E-05 18.774 15.655 38.857 4.96E-03 4.16E-03 1.04E-02
BR-198 C1 GALENA 0.71385 0.71329 7.28E-05 18.784 15.708 38.935 1.05E-04 1.13E-04 3.60E-04
BR-24 C2 ENARGITE 0.71531 0.71279 1.47E-04 N.D. N.D. N.D. N.D. N.D. N.D.
BR-24 C2 QUARTZ 0.70970 0.70937 7.66E-05 N.D. N.D. N.D. N.D. N.D. N.D.
BR-143 C2 ENARGITE 0.71074 0.71026 6.56E-05 N.D. N.D. N.D. N.D. N.D. N.D.
BR-152 C2 ENARGITE 0.71230 0.71139 6.09E-05 18.780 15.656 38.869 2.42E-04 2.08E-04 5.30E-04
BR-152 C2 PYRITE 0.71199 0.71182 2.20E-05 18.776 15.655 38.862 3.15E-04 2.44E-04 6.24E-04
BR-267 porphyry QUARTZ 0.71042 0.70975 3.54E-05 18.781 15.661 38.884 9.06E-04 7.65E-04 1.89E-03
BR-315 porphyry QUARTZ 0.71041 0.71015 3.01E-05 N.D. N.D. N.D. N.D. N.D. N.D.
N.D. : not determined, signals too low
364
Table A.2b: Sr and Pb isotopic ratios of slected whole rock
Formation/district Rock type 87

Sr/ 86 Sr 1σ ( 87 Sr/ 86 Sr) 206
Pb/ 204 Pb 207
Pb/ 204 Pb 208
Pb/ 204 Pb 1σ ( 206 Pb/ 204 Pb) 1σ ( 207 Pb/ 204 Pb) 1σ ( 208 Pb/ 204 Pb)
Calera Carbonate 0.708267 0.000006 17.9194 15.5655 37.5127 0.0002 0.0002 0.0005
Pucará Carbonate 0.710028 0.000005 18.6100 15.6422 38.5831 0.0002 0.0002 0.0004
Pucará Carbonate 0.708952 0.000007 18.4237 15.6184 38.0735 0.0003 0.0003 0.0007
Mitu Sandstone 0.725701 0.000009 18.6582 15.6358 39.4170 0.0007 0.0006 0.0016
Excelsior Fresh dark phyllite 0.761779 0.000003 18.6188 15.6593 38.8595 0.0002 0.0002 0.0005
Excelsior Fresh dark phyllite 0.755644 0.000004 18.6808 15.6671 38.9090 0.0002 0.0002 0.0005
Excelsior Altered dark phyllite 0.826161 0.000005 19.1016 15.6942 39.6367 0.0003 0.0002 0.0007
Cerro de Pasco* Quartz-monzonite dyke 0.705472 0.000002 18.7864 15.6422 38.8243 0.0004 0.0004 0.0009
Cerro de Pasco* Dacite 0.705498 0.000002 18.8121 15.6446 38.8476 0.0003 0.0003 0.0007
Cerro de Pasco* Dacitic tuff 0.705483 0.000002 18.8062 15.6421 38.8432 0.0003 0.0003 0.0007
Cerro de Pasco* Quartz-monzonite dyke 0.705628 0.000002 18.7251 15.6351 38.7437 0.0003 0.0003 0.0007
Cerro de Pasco* Rhyodacite 0.705643 0.000003 18.8114 15.6419 38.8577 0.0004 0.0003 0.0008
Cerro de Pasco* Trachyte 0.705290 0.000002 18.7704 15.6380 38.8018 0.0004 0.0003 0.0009
1
Yanamate Dacite 0.705516 0.000002 18.8162 15.6494 38.8412 0.0005 0.0004 0.0010
1
Yanamate Dacite 0.705611 0.000002 18.7925 15.6440 38.8219 0.0003 0.0002 0.0006
Yanamate1 Dacite 0.705622 0.000002 18.7853 15.6352 38.7865 0.0002 0.0001 0.0004
2
Colquijirca Dacite 0.705615 0.000002 18.7289 15.6374 38.7459 0.0005 0.0004 0.0010
2
Colquijirca Dacite 0.705639 0.000005 18.7257 15.6357 38.7389 0.0002 0.0002 0.0005
*: Data from Rottier 2016

1
: Barren magmatic center located 5 km south of Cerro de Pasco
2
: Mineralized magmatic center located 15 km south of Cerro de Pasco
365
Table A.3: LA-ICP-MS analyses of quartz crystals from various epithermal mineralization stages
Sample Spot # Stage Li (ppm) B (ppm) Na (ppm) Mg (ppm) Al (ppm) Si (ppm) P (ppm) K (ppm) Ca (ppm) Ti (ppm) Fe (ppm) Cu (ppm) Zn (ppm) Ga (ppm) Ge (ppm)
BR-111 1 A 16 8.4 1.6 B.D.L 1389 465128 30.5 B.D.L 224 B.D.L B.D.L B.D.L B.D.L 6.7 23.6
BR-111 2 A 15.8 8.9 1.6 B.D.L 1459 465128 29.4 B.D.L 200 1.9 B.D.L B.D.L B.D.L 6.7 19.2
BR-111 3 A 14.6 B.D.L 5.1 1 1366 465128 31.8 B.D.L 214 B.D.L B.D.L B.D.L B.D.L 6.6 15.1
BR-111 4 A 12.5 15.2 44.3 4.2 1818 465128 34.8 149 203 B.D.L 22.9 B.D.L 3.2 15.8 15.4
BR-111 5 A 17.9 12.3 45.6 3 1743 465128 35.2 82 210 B.D.L B.D.L B.D.L 4.2 5.4 19.3
BR-111 6 A 8.9 B.D.L 7.6 2.1 1205 465128 34.9 75.7 189 B.D.L B.D.L B.D.L B.D.L 8.8 10
BR-111 7 A 8.5 9 32.4 5.5 1280 465128 34.1 124 239 2.1 23.9 B.D.L 2.1 4.4 6.5
BR-111 8 A 7.5 10.9 49.7 6.5 1237 465128 35.7 158 264 B.D.L 29.7 B.D.L 12 10.5 9.9
BR-05 Q1 1 B1 3.9 4.7 2.1 B.D.L 781 465128 43.6 B.D.L 283 2.2 B.D.L 3.3 B.D.L B.D.L 3.4
BR-05 Q1 2 B1 3.5 B.D.L B.D.L B.D.L 560 465128 41.9 B.D.L 288 3.1 B.D.L B.D.L B.D.L B.D.L 2.7
BR-05 Q1 3 B1 8.3 B.D.L B.D.L B.D.L 865 465128 49.2 B.D.L 271 3.8 B.D.L B.D.L B.D.L B.D.L 5.6
BR-05 Q1 4 B1 11.5 5.9 3.3 B.D.L 1981 465128 41.1 B.D.L 261 10 B.D.L B.D.L B.D.L B.D.L 7.6
BR-05 Q1 5 B1 2.4 B.D.L 0.3 B.D.L 363 465128 40.8 B.D.L 285 B.D.L B.D.L B.D.L B.D.L B.D.L 1.7
BR-05 Q1 6 B1 B.D.L B.D.L B.D.L 0.5 146 465128 43.8 B.D.L 278 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
BR-05 Q1 7 B1 B.D.L B.D.L 0.34 B.D.L 107 465128 43.5 B.D.L 293 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
BR-05 Q1 8 B1 3.6 B.D.L 0.66 B.D.L 682 465128 44.3 B.D.L 276 B.D.L B.D.L B.D.L B.D.L B.D.L 6.1
BR-05 Q1 9 B1 4.7 B.D.L 0.41 B.D.L 967 465128 42.9 B.D.L 278 1.9 B.D.L B.D.L B.D.L B.D.L 6.7
BR-05 Q1 10 B1 3 B.D.L 0.33 B.D.L 719 465128 40 B.D.L 280 1.6 B.D.L B.D.L B.D.L B.D.L 4.2
BR-12 Q2 1 B1 3.4 B.D.L B.D.L B.D.L 393 465128 46.3 B.D.L 282 B.D.L B.D.L 0.54 B.D.L B.D.L 2.1
BR-12 Q2 2 B1 B.D.L B.D.L B.D.L B.D.L 68.2 465128 44.7 B.D.L 268 B.D.L B.D.L B.D.L B.D.L B.D.L 2.1
BR-12 Q2 3 B1 B.D.L B.D.L B.D.L B.D.L 111 465128 44.1 B.D.L 295 1.9 B.D.L B.D.L B.D.L B.D.L 1.7
BR-12 Q2 4 B1 11 B.D.L 2.2 B.D.L 1274 465128 44.3 B.D.L 294 2.8 B.D.L B.D.L B.D.L B.D.L 3.7
BR-12 Q2 6 B1 B.D.L B.D.L 0.39 B.D.L 108 465128 40.7 B.D.L 303 B.D.L B.D.L B.D.L B.D.L B.D.L 1.7
BR-12 Q2 7 B1 B.D.L B.D.L B.D.L B.D.L 150 465128 44.1 B.D.L 268 B.D.L B.D.L B.D.L B.D.L B.D.L 2.3
BR-12 Q2 9 B1 13.9 2.9 1.6 B.D.L 1475 465128 40.9 B.D.L 276 4.8 B.D.L B.D.L B.D.L B.D.L 3.1
366
Sample Spot # Stage As (ppm) Rb (ppm) Sr (ppm) Sn (ppm) Sb (ppm) Cs (ppm) Ba (ppm) Pb (ppm) U (ppm)
BR-111 1 A B.D.L B.D.L B.D.L 1.5 40.6 B.D.L B.D.L B.D.L B.D.L
BR-111 2 A B.D.L B.D.L B.D.L 0.89 44.7 B.D.L B.D.L B.D.L B.D.L
BR-111 3 A B.D.L B.D.L 0.03 1.1 42.1 B.D.L B.D.L 0.1 B.D.L
BR-111 4 A B.D.L 1.3 0.49 0.87 59.8 0.5 1.4 1.5 B.D.L
BR-111 5 A B.D.L 0.74 0.23 1.3 24.8 0.3 0.75 1.2 B.D.L
BR-111 6 A B.D.L 0.8 0.27 1.3 27.4 0.35 0.65 B.D.L B.D.L
BR-111 7 A B.D.L 1.4 0.35 1.5 46.1 0.51 1.2 1.2 B.D.L
BR-111 8 A B.D.L 1.4 0.82 1.7 35.3 0.51 0.98 3.4 B.D.L
BR-05 Q1 1 B1 B.D.L B.D.L B.D.L 1.5 6.9 B.D.L B.D.L 0.09 B.D.L
BR-05 Q1 2 B1 B.D.L B.D.L B.D.L 1.6 6.5 B.D.L 0.04 B.D.L B.D.L
BR-05 Q1 3 B1 B.D.L B.D.L B.D.L 1.4 7.1 B.D.L B.D.L B.D.L B.D.L
BR-05 Q1 5 B1 B.D.L 0.03 B.D.L 1.7 1.2 B.D.L B.D.L B.D.L B.D.L
BR-05 Q1 7 B1 B.D.L B.D.L 0.01 1.8 1.4 B.D.L B.D.L B.D.L B.D.L
BR-05 Q1 8 B1 1.6 B.D.L B.D.L 1.3 1.5 0.01 B.D.L B.D.L B.D.L
BR-05 Q1 9 B1 B.D.L B.D.L 0.01 1.5 3 B.D.L B.D.L B.D.L B.D.L
BR-12 Q2 1 B1 1.6 B.D.L B.D.L 1.8 5.9 B.D.L B.D.L B.D.L B.D.L
BR-12 Q2 4 B1 B.D.L 0.04 B.D.L 1.1 14 B.D.L B.D.L B.D.L B.D.L
BR-12 Q2 6 B1 B.D.L B.D.L B.D.L 2 2.4 B.D.L B.D.L B.D.L B.D.L
BR-12 Q2 8 B1 B.D.L B.D.L B.D.L 1.5 6 B.D.L 0.11 B.D.L B.D.L
367
BR-12 Q2 17 B1 13.3 5.3 4 B.D.L 1693 465128 42 B.D.L 282 3.9 B.D.L B.D.L B.D.L B.D.L 4
BR-12 Q2 18 B1 5.8 4.7 0.6 B.D.L 634 465128 41.6 B.D.L 289 2 B.D.L B.D.L B.D.L B.D.L 3.7
BR-12 Q2 19 B1 2.5 B.D.L 0.84 54.3 384 465128 40.8 B.D.L 274 2.3 12.9 B.D.L B.D.L 0.16 3.6
BR-12 Q2 20 B1 6.7 B.D.L 2.2 68 624 465128 48.7 B.D.L 431 6.5 B.D.L B.D.L B.D.L B.D.L 3.1
BR-12 Q2 22 B1 4.5 4.1 0.78 B.D.L 342 465128 40.8 B.D.L 295 B.D.L B.D.L B.D.L B.D.L B.D.L 3.9
BR-12 Q2 24 B1 3.9 3.6 0.53 B.D.L 412 465128 42.4 B.D.L 274 4.6 B.D.L B.D.L B.D.L 0.05 2.4
BR-12 Q2 26 B1 6 B.D.L 0.56 B.D.L 540 465128 42.6 B.D.L 267 B.D.L B.D.L B.D.L B.D.L B.D.L 4.5
BR-12 Q2 27 B1 5.8 3.9 0.53 B.D.L 676 465128 41.4 B.D.L 258 B.D.L B.D.L B.D.L B.D.L B.D.L 6.4
BR-12 Q5 1 B1 2.8 B.D.L B.D.L B.D.L 250 465128 40.9 B.D.L 283 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
BR-12 Q5 3 B1 B.D.L 16.2 1.1 B.D.L 43.4 465128 41.7 B.D.L 285 B.D.L B.D.L B.D.L B.D.L 1.6 5.6
BR-12 Q5 4 B1 1.1 16.4 0.75 B.D.L 130 465128 41.2 B.D.L 281 B.D.L B.D.L B.D.L B.D.L 1.5 5.6
BR-12 Q5 5 B1 B.D.L B.D.L B.D.L B.D.L 103 465128 38.5 B.D.L 275 B.D.L B.D.L B.D.L B.D.L B.D.L 2
BR-12 Q5 6 B1 1.8 B.D.L B.D.L B.D.L 216 465128 41.8 B.D.L 263 B.D.L B.D.L B.D.L B.D.L B.D.L 2.6
BR-12 Q5 7 B1 2.1 4.8 B.D.L B.D.L 212 465128 42.6 B.D.L 271 B.D.L B.D.L B.D.L B.D.L B.D.L 1.6
BR-12 Q5 8 B1 5.9 B.D.L 0.58 B.D.L 655 465128 41.8 B.D.L 276 2 B.D.L B.D.L B.D.L B.D.L 2.9
BR-12 Q5 9 B1 14.6 3.7 3 B.D.L 1630 465128 39.3 B.D.L 262 6.6 B.D.L B.D.L B.D.L B.D.L 5.7
BR-12 Q5 11 B1 10.9 3.7 1.9 B.D.L 1225 465128 36.1 B.D.L 290 3.7 B.D.L B.D.L B.D.L B.D.L 5
BR-12 Q5 12 B1 4.6 B.D.L 1.4 B.D.L 517 465128 41.9 B.D.L 267 5 B.D.L B.D.L B.D.L B.D.L 3
CV-11 Q6 1 B2 4.2 9.7 3.1 1.8 1941 465128 38.1 59.5 299 3 B.D.L B.D.L 1.6 1.7 9
CV-11 Q6 2 B2 3.2 4.8 4.9 0.92 1577 465128 38.3 24.7 303 4.2 B.D.L B.D.L 0.84 1 5.7
CV-11 Q6 3 B2 1.9 5.4 0.98 B.D.L 1319 465128 39.3 B.D.L 272 5.6 B.D.L B.D.L B.D.L 0.72 4.9
368
BR-12 Q2 14 B1 B.D.L B.D.L B.D.L 1.4 5.5 0.03 B.D.L B.D.L B.D.L
BR-12 Q2 19 B1 8.6 0.03 0.03 1.4 18.9 0 0.42 0.1 B.D.L
BR-12 Q2 20 B1 5.1 B.D.L B.D.L 2.5 11.4 B.D.L 0.46 0.13 B.D.L
BR-12 Q2 21 B1 3.9 0.08 B.D.L 2.1 2.1 B.D.L B.D.L B.D.L B.D.L
BR-12 Q2 22 B1 2 B.D.L 0.01 1.5 1.7 0.03 B.D.L B.D.L B.D.L
BR-12 Q2 24 B1 2.2 B.D.L 0.01 1.6 4.9 B.D.L B.D.L B.D.L B.D.L
BR-12 Q2 25 B1 2.8 0.04 B.D.L 1.6 1.7 B.D.L B.D.L B.D.L B.D.L
BR-12 Q5 4 B1 B.D.L 0.09 0.02 1.4 27.4 0.01 B.D.L B.D.L B.D.L
BR-12 Q5 5 B1 B.D.L B.D.L B.D.L 1.6 2.4 0 B.D.L B.D.L B.D.L
BR-12 Q5 10 B1 1.7 B.D.L B.D.L 1.3 81.8 0.03 0.05 B.D.L B.D.L
BR-12 Q5 11 B1 0.28 B.D.L 0 1.1 7.1 B.D.L B.D.L B.D.L B.D.L
BR-12 Q5 12 B1 2.9 0.06 B.D.L 1.3 1.3 B.D.L B.D.L 0.09 B.D.L
CV-11 Q6 1 B2 20.1 0.55 0.16 1.8 100 0.15 1.2 0.18 B.D.L
CV-11 Q6 2 B2 0.99 0.25 0.11 1.1 45.4 0.06 0.81 0.39 B.D.L
CV-11 Q6 3 B2 B.D.L B.D.L B.D.L 1.1 29.6 B.D.L B.D.L B.D.L B.D.L
369
CV-11 Q6 5 B2 2.1 4.6 1 B.D.L 1570 465128 40.4 B.D.L 315 4.7 B.D.L B.D.L B.D.L 1 3.7
CV-11 Q6 6 B2 3.9 6.1 1.4 B.D.L 2098 465128 39.1 B.D.L 292 6.3 B.D.L 0.3 B.D.L 1 7.7
CV-11 Q6 7 B2 2 7.8 1.1 B.D.L 1697 465128 35.6 B.D.L 298 5 B.D.L B.D.L B.D.L 0.79 10
CV-11 Q6 8 B2 1.5 6 1.1 B.D.L 1537 465128 38.8 B.D.L 273 4 B.D.L 0.34 B.D.L 0.82 13.4
CV-11 Q6 9 B2 1.9 4.2 1.3 1.2 1575 465128 37.4 24.9 299 2.7 B.D.L B.D.L B.D.L 1.2 7.5
CV-11 Q6 10 B2 B.D.L 5.3 1 B.D.L 1028 465128 39.9 B.D.L 298 1.5 B.D.L B.D.L B.D.L 0.44 6.8
CV-11 Q6 11 B2 B.D.L 7.8 3.7 0.84 611 465128 36.8 27 295 1.1 B.D.L B.D.L B.D.L 0.57 5
CV-11 Q6 12 B2 B.D.L 6.9 2.3 B.D.L 409 465128 40.2 B.D.L 292 B.D.L B.D.L B.D.L B.D.L 0.16 3.6
CV-11 Q6 13 B2 B.D.L B.D.L 1.8 B.D.L 1541 465128 39.8 B.D.L 306 7.5 B.D.L B.D.L B.D.L 0.86 7.7
CV-11 Q6 14 B2 B.D.L B.D.L 1.4 0.92 1437 465128 37.8 15.3 299 3.5 B.D.L B.D.L B.D.L 0.99 7
CV-11 Q6 15 B2 B.D.L B.D.L 11.4 B.D.L 1185 465128 43.7 B.D.L 288 B.D.L 44.8 95 10.2 0.8 4.6
CV-11 Q6 16 B2 B.D.L B.D.L 7.2 B.D.L 1027 465128 44.1 B.D.L 296 B.D.L B.D.L B.D.L B.D.L 0.57 7.6
CV-11 Q6 17 B2 B.D.L 5.9 1.3 B.D.L 1111 465128 38.5 B.D.L 296 2.2 B.D.L B.D.L B.D.L 0.73 8.4
CV-11 Q6 18 B2 B.D.L 6.3 0.88 B.D.L 1038 465128 39.7 B.D.L 302 2.8 B.D.L B.D.L B.D.L 0.55 7.8
CV-11 Q6 20 B2 1.1 4.8 0.89 B.D.L 975 465128 38 B.D.L 302 3.2 B.D.L B.D.L B.D.L 0.58 4.4
BR-126 Q6 2 B2 1.1 B.D.L 0.73 B.D.L 1167 465128 45.6 B.D.L 365 1.8 B.D.L 0.32 B.D.L 0.19 4.7
BR-126 Q6 3 B2 B.D.L B.D.L 0.8 B.D.L 1183 465128 51.3 B.D.L 358 B.D.L B.D.L B.D.L B.D.L B.D.L 4.6
BR-126 Q6 4 B2 B.D.L B.D.L 1.5 B.D.L 1017 465128 45.7 B.D.L 357 3.5 B.D.L B.D.L B.D.L B.D.L 3.7
BR-126 Q6 5 B2 B.D.L 7 2.5 B.D.L 1021 465128 46.5 B.D.L 347 3.3 B.D.L B.D.L B.D.L 0.17 3.6
BR-126 Q6 6 B2 B.D.L 10 3 B.D.L 932 465128 44.5 B.D.L 325 2.6 B.D.L B.D.L B.D.L 0.11 3.7
BR-126 Q6 7 B2 0.69 9 4.1 B.D.L 973 465128 41.2 B.D.L 358 1.9 B.D.L B.D.L 5 0.11 3.5
BR-126 Q6 8 B2 1.3 6.3 14.5 1.1 833 465128 42.5 26.5 329 1.7 B.D.L 0.75 6.5 0.38 3.8
BR-126 Q6 9 B2 4.3 8.5 6.8 1 1385 465128 43.7 38.9 332 2 18 0.75 3.2 0.46 6.7
BR-126 Q6 11 B2 1.1 5.4 0.97 B.D.L 1447 465128 41.1 B.D.L 336 3 B.D.L 0.41 B.D.L 0.56 5.7
BR-126 Q6 12 B2 0.71 5.7 3 0.62 1347 465128 38.4 B.D.L 344 3.2 B.D.L B.D.L B.D.L 0.68 5.3
BR-126 Q6 13 B2 2.9 11.4 7 1 911 465128 41.3 60.7 333 B.D.L B.D.L B.D.L B.D.L 0.4 3.8
BR-126 Q6 14 B2 5.6 7.6 3.2 B.D.L 559 465128 43.5 B.D.L 336 B.D.L B.D.L B.D.L B.D.L 0.27 3.7
CV-11 Q7 1 B2 2.5 B.D.L 7 1 1407 465128 41.2 25.8 317 2.9 B.D.L B.D.L B.D.L 0.72 5.6
370
CV-11 Q6 4 B2 B.D.L 0.05 0.02 1.2 30.9 0.01 B.D.L 0.06 B.D.L
CV-11 Q6 5 B2 B.D.L B.D.L 0.02 1.1 27 B.D.L 0.07 B.D.L B.D.L
CV-11 Q6 6 B2 B.D.L 0.07 0.01 1.2 30.2 0.02 B.D.L B.D.L B.D.L
CV-11 Q6 7 B2 B.D.L B.D.L B.D.L 1.2 33 B.D.L B.D.L B.D.L B.D.L
CV-11 Q6 9 B2 B.D.L 0.22 0.18 1.3 7 0.05 0.42 B.D.L B.D.L
CV-11 Q6 10 B2 B.D.L 0.05 0.01 1.1 3.6 0.03 0.1 B.D.L B.D.L
CV-11 Q6 11 B2 20.1 0.31 0.01 1.6 49.1 0.09 B.D.L 0.14 B.D.L
CV-11 Q6 12 B2 9.5 0.05 0.01 1.6 34.3 0.04 B.D.L 0.45 B.D.L
CV-11 Q6 13 B2 B.D.L B.D.L B.D.L 1.1 32 B.D.L B.D.L 0.09 B.D.L
CV-11 Q6 14 B2 B.D.L 0.18 0.14 1.3 10.7 0.05 0.45 B.D.L B.D.L
CV-11 Q6 15 B2 5.5 B.D.L 0.16 1.9 14.1 0.94 B.D.L 6.3 B.D.L
CV-11 Q6 16 B2 B.D.L B.D.L 0.11 3.3 11.6 0.09 B.D.L 0.4 B.D.L
CV-11 Q6 17 B2 B.D.L 0.09 0.1 1.3 21.1 0.02 0.31 B.D.L B.D.L
CV-11 Q6 19 B2 B.D.L B.D.L B.D.L 1.3 15 0.01 0.12 B.D.L B.D.L
CV-11 Q6 20 B2 B.D.L 0.04 0.03 1.1 17 B.D.L 0.19 B.D.L B.D.L
BR-126 Q6 2 B2 B.D.L 0.17 0.05 1.7 2.2 0.05 0.31 B.D.L B.D.L
BR-126 Q6 3 B2 B.D.L 0.14 0.03 1.5 2.4 B.D.L 0.19 B.D.L B.D.L
BR-126 Q6 4 B2 25.4 0.14 0.01 1.8 11.5 0.05 B.D.L B.D.L B.D.L
BR-126 Q6 5 B2 32 0.12 B.D.L 1.9 10.5 0.05 B.D.L B.D.L B.D.L
BR-126 Q6 6 B2 18.7 0.18 B.D.L 1.3 19.7 0.13 B.D.L 0.1 B.D.L
BR-126 Q6 7 B2 12.8 0.25 0.01 4.1 23.1 0.16 B.D.L 0.28 B.D.L
BR-126 Q6 8 B2 4.4 0.58 0.05 3 3 0.33 0.15 0.73 B.D.L
BR-126 Q6 9 B2 10 0.57 0.02 3.8 4.3 0.32 B.D.L 0.29 B.D.L
BR-126 Q6 12 B2 110 0.21 0.02 1.5 17.1 0.08 B.D.L 0.09 B.D.L
BR-126 Q6 13 B2 11.3 0.8 B.D.L 2 7 0.45 B.D.L 0.12 0.01
BR-126 Q6 14 B2 9.7 0.28 B.D.L 1.7 3.9 0.09 B.D.L B.D.L B.D.L
CV-11 Q7 1 B2 1.1 0.27 0.2 1.4 36.9 0.06 1.6 0.19 B.D.L
CV-11 Q7 2 B2 B.D.L B.D.L B.D.L 1.1 28.3 0.01 B.D.L B.D.L B.D.L
371
CV-11 Q7 4 B2 B.D.L 4.9 1 B.D.L 1330 465128 40.3 B.D.L 313 4.7 B.D.L B.D.L B.D.L 0.59 13.5
CV-11 Q7 5 B2 1.6 6.1 1.3 1.2 1672 465128 42.4 B.D.L 316 5.9 B.D.L B.D.L B.D.L 1.2 8.7
CV-11 Q7 6 B2 1.8 8 1.6 B.D.L 1754 465128 41.7 B.D.L 309 4.4 B.D.L B.D.L B.D.L 0.61 8.2
CV-11 Q7 7 B2 1 5 1.8 B.D.L 910 465128 40.2 13.4 308 1.6 B.D.L B.D.L B.D.L 0.54 6
CV-11 Q7 8 B2 1.8 6.2 1 B.D.L 1523 465128 40.1 B.D.L 297 4.9 B.D.L B.D.L B.D.L 0.74 15.8
CV-11 Q7 9 B2 1.9 5.1 1.1 B.D.L 1575 465128 41.5 B.D.L 317 2.3 B.D.L B.D.L B.D.L 1.2 7
CV-11 Q7 10 B2 B.D.L B.D.L 0.87 B.D.L 932 465128 39.8 B.D.L 305 1.6 B.D.L B.D.L B.D.L 0.49 5.4
CV-11 Q7 11 B2 1.2 4.6 0.86 B.D.L 1266 465128 38.9 B.D.L 296 2 B.D.L B.D.L B.D.L 0.69 6.3
CV-11 Q7 12 B2 1.3 10 4.2 B.D.L 1452 465128 39 39.2 296 2.9 B.D.L B.D.L B.D.L 1 7.7
CV-11 Q7 13 B2 B.D.L 5.7 1.7 B.D.L 289 465128 40.1 B.D.L 313 1 B.D.L B.D.L B.D.L 0.23 3.3
BR-24 Q1 1 C2 B.D.L 6 B.D.L B.D.L 45.5 465128 29.4 B.D.L 220 B.D.L B.D.L B.D.L B.D.L 0.49 B.D.L
BR-24 Q1 2 C2 B.D.L B.D.L B.D.L B.D.L 66.5 465128 31.1 B.D.L 196 B.D.L B.D.L B.D.L B.D.L 0.38 1.4
BR-24 Q1 3 C2 1.2 B.D.L 1 B.D.L 351 465128 29.2 B.D.L 197 3.5 B.D.L B.D.L B.D.L B.D.L 1.1
BR-24 Q1 4 C2 B.D.L 7.2 B.D.L B.D.L 91.5 465128 31.2 B.D.L 196 B.D.L B.D.L B.D.L B.D.L 0.29 1.1
BR-24 Q1 5 C2 B.D.L 6.6 1.9 B.D.L 87.7 465128 29.7 B.D.L 226 B.D.L B.D.L B.D.L B.D.L B.D.L 1.1
BR-24 Q1 6 C2 1.7 5.3 1.2 B.D.L 285 465128 30.3 B.D.L 224 4.9 B.D.L B.D.L B.D.L B.D.L 1.8
BR-24 Q1 7 C2 0.96 7.7 2.7 B.D.L 221 465128 31.7 B.D.L 234 3.7 B.D.L B.D.L B.D.L B.D.L 2.6
BR-24 Q2 1 C2 B.D.L 8.3 18.1 1.3 97.9 465128 33.7 B.D.L 254 39.6 B.D.L B.D.L 1.7 B.D.L B.D.L
372
CV-11 Q7 5 B2 B.D.L 0.15 0.12 1.5 17.3 0.03 0.3 B.D.L B.D.L
CV-11 Q7 6 B2 B.D.L B.D.L B.D.L 1.6 10 B.D.L B.D.L B.D.L B.D.L
CV-11 Q7 7 B2 6.9 0.22 0.02 1.6 17.9 0.05 0.11 B.D.L B.D.L
CV-11 Q7 9 B2 B.D.L 0.1 0.07 1.4 5.8 0.03 0.34 B.D.L B.D.L
CV-11 Q7 10 B2 B.D.L B.D.L 0.01 1.6 3 B.D.L B.D.L B.D.L B.D.L
CV-11 Q7 11 B2 B.D.L 0.07 B.D.L 1.2 5.9 0.02 B.D.L B.D.L B.D.L
CV-11 Q7 12 B2 20.5 0.33 B.D.L 1.5 59.6 0.08 0.11 0.08 B.D.L
CV-11 Q7 13 B2 13.4 0.11 0.01 1.8 21.6 0.04 B.D.L B.D.L B.D.L
BR-24 Q1 1 C2 B.D.L B.D.L B.D.L 1.2 1.4 B.D.L B.D.L B.D.L B.D.L
BR-24 Q1 2 C2 B.D.L B.D.L B.D.L 0.98 2.5 B.D.L B.D.L B.D.L B.D.L
BR-24 Q1 3 C2 10 B.D.L B.D.L 1.2 3.7 B.D.L B.D.L B.D.L 0.03
BR-24 Q1 4 C2 B.D.L B.D.L 0.2 1.3 4.9 0.02 B.D.L B.D.L B.D.L
BR-24 Q1 5 C2 3.6 B.D.L B.D.L 1.2 1.1 B.D.L B.D.L 0.06 B.D.L
BR-24 Q1 6 C2 7.9 B.D.L B.D.L 1.2 2.3 B.D.L B.D.L B.D.L B.D.L
BR-24 Q1 7 C2 9.8 0.03 B.D.L 1.5 2.8 0.01 B.D.L B.D.L B.D.L
BR-24 Q2 1 C2 B.D.L 0.13 0.07 1.6 B.D.L 0.02 0.12 0.67 B.D.L
373
Table A.4: SIMS trace element analyses of quartz
Sample Spot number Stage Li (ppm) Al (ppm) Ti (ppm) Fe (ppm)

BR-111 1 A 4.78 1473.90 5.67 6.40
BR-111 2 A 6.23 1805.51 6.73 4.82
BR-111 3 A 14.46 2911.17 7.04 14.95
BR-111 4 A 6.39 1206.84 5.59 6.21
BR-111 5 A 6.71 1103.41 6.24 8.06
BR-111 6 A 6.61 1230.79 8.61 6.08
BR-111 7 A 4.84 892.41 5.94 8.46
BR-111 8 A 6.83 1314.45 10.95 13.29
BR-12 Q2 1 B1 1.27 210.70 1.37 1.47
BR-12 Q2 2 B1 8.08 1168.74 5.15 1.47
BR-12 Q2 3 B1 6.39 848.81 2.40 1.89
BR-12 Q2 4 B1 4.40 571.67 2.97 1.34
BR-12 Q2 5 B1 3.18 444.48 2.42 1.40
BR-12 Q2 6 B1 N.D 570.93 2.59 1.64
BR-12 Q2 7 B1 N.D 858.21 4.12 1.20
BR-12 Q2 8 B1 N.D 138.80 1.17 1.42
BR-12 Q2 9 B1 N.D 327.15 1.21 1.11
BR-12 Q2 10 B1 N.D 358.40 0.86 1.19
BR-12 Q2 11 B1 N.D 276.61 1.00 2.18
BR-12 Q2 12 B1 N.D 325.74 1.16 2.17
BR-12 Q2 13 B1 N.D 334.29 1.12 1.27
BR-12 Q2 14 B1 N.D 705.22 6.34 4.64
BR-12 Q2 15 B1 N.D 1487.44 14.95 2.38
BR-12 Q2 16 B1 N.D 148.85 1.04 1.23
BR-12 Q2 17 B1 N.D 228.64 3.27 3.58
CV-11 Q7 1 B2 2.89 1419.66 6.24 18.80
CV-11 Q7 2 B2 2.09 1145.75 7.16 1.55
CV-11 Q7 3 B2 1.75 986.95 4.54 1.30
CV-11 Q7 4 B2 1.50 712.96 1.86 1.18
CV-11 Q7 5 B2 2.00 796.60 3.01 1.65
CV-11 Q7 6 B2 3.21 526.25 1.32 2.02
CV-11 Q7 7 B2 1.65 1058.07 5.33 0.79
CV-11 Q7 8 B2 1.02 913.13 4.37 8.58
CV-11 Q7 9 B2 0.94 895.97 2.86 1.22
CV-11 Q7 10 B2 1.09 1313.10 3.15 0.77
CV-11 Q7 11 B2 0.89 1374.43 3.92 26.31
CV-11 Q7 12 B2 1.02 1043.74 2.61 1.58
CV-11 Q7 13 B2 0.42 219.51 1.32 3.57
CV-11 Q7 14 B2 1.14 514.77 4.17 8.47
CV-11 Q7 15 B2 1.62 749.48 5.45 10.98
CV-11 Q7 16 B2 0.86 1170.27 6.20 23.77
CV-11 Q7 17 B2 1.40 1526.36 5.79 3.86
BR-24 Q1 1 C2 N.D 20.62 0.35 1.72
BR-24 Q1 2 C2 N.D 143.48 2.06 6.46
BR-24 Q1 3 C2 N.D 252.48 5.86 12.93
BR-24 Q1 4 C2 N.D 342.70 4.45 3.98
BR-24 Q1 5 C2 N.D 127.41 1.82 1.84
BR-24 Q1 6 C2 N.D 202.12 4.62 2.16
374
Table A.4: SIMS trace element analyses of quartz
Sample Spot number Stage Li (ppm) Al (ppm) Ti (ppm) Fe (ppm)
BR-24 Q1 7 C2 N.D 134.61 4.22 3.51

BR-24 Q1 8 C2 N.D 32.37 0.62 2.30
BR-24 Q1 9 C2 N.D 36.07 0.75 2.99
BR-24 Q1 10 C2 N.D 41.06 0.59 98.34
BR-24 Q1 11 C2 N.D 976.81 1.69 2.62
BR-24 Q1 12 C2 N.D 1607.68 2.34 2.32
BR-24 Q1 13 C2 N.D 108.33 0.92 3.72
375
Table A.5: XRF analyses of fresh and altered phyllite samples from the Excelsior group
SiO2 TiO2 Al2O3( Fe2O3 MnO MgO CaO Na2O K2O P2O5 LOI Cr2O3 NiO Sc Cr
Sample Formation Rock V (ppm)
(wt.%) (wt.%) wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (ppm) (ppm)
BR-133 Excelsior Fresh dark phyllite 59.24 0.92 19.87 7.22 0.05 2.23 0.23 1.25 4.13 0.12 4.19 0.02 0.01 16 149 84
BR-134 Excelsior Fresh dark phyllite 62.83 0.92 17.48 7.32 0.09 2.18 0.18 1.59 3.65 0.13 3.24 0.01 0.01 16 145 74
BR-278 Excelsior Altered dark phyllite 58.51 0.81 18.34 7.74 0.04 2.35 0.47 0.77 4.18 0.12 5.96 0.01 0.01 14 101 69
Mn Co Ni Cu Zn Ga Ge As Se Rb Sr Zr Nb Mo Ag
Sample Formation Rock Y (ppm)
BR-133 Excelsior Fresh dark phyllite 372 19 36 18 122 27 <LLD 4 <LLD 197 76 36 157 17 <LLD <LLD
BR-134 Excelsior Fresh dark phyllite 637 20 33 25 98 24 2 <LLD <LLD 162 57 32 224 17 <LLD <LLD
BR-278 Excelsior Altered dark phyllite 245 23 37 29 52 25 2 4 <LLD 178 23 28 109 16 1 <LLD
Cd Sn Sb Te Cs Ba La Ce Nd Sm Yb Hf Ta W Hg
Sample Formation Rock I (ppm)
BR-133 Excelsior Fresh dark phyllite <LLD 4 <LLD <LLD <LLD 9 534 52 101 45 6 3 2 <LLD 2 <LLD
BR-134 Excelsior Fresh dark phyllite <LLD <LLD <LLD <LLD <LLD 7 464 47 90 38 4 3 5 <LLD 2 <LLD
BR-278 Excelsior Altered dark phyllite 4 <LLD <LLD <LLD <LLD 21 505 50 81 35 6 2 3 1 <LLD <LLD
Tl Pb Bi Th
Sample Formation Rock U (ppm)
(ppm) (ppm) (ppm) (ppm)
BR-133 Excelsior Fresh dark phyllite <LLD 37 <LLD 21 2
BR-134 Excelsior Fresh dark phyllite 1 32 <LLD 18 2
BR-278 Excelsior Altered dark phyllite <LLD 12 <LLD 19 2
376
Electronic Appendix A.1
Crushing and leaching

Selected mineralized samples were crushed using a hydraulic press and then sieved to
conserve the 0.5-1 mm fraction, that has been washed several times using a 18,2 MΩ water and then
dried. Between 2 and 5g of monomineral separates (quartz, carbonate, pyrrhotite, pyrite, sphalerite,
galena and enargite) were handpicked under a binocular. Handpicked quartz samples were pre-cleaned
in hot pure 12M HNO3 during ~1-2 days until no reaction was visible. To clean the samples (quartz
and others), they were heated up in 18,2 MΩ water at 200°C during 10 min three times. Samples were
subsequently dried and then gently crushed in a clean agate mortar and pestle. The obtained dry
powder was then transferred into a 13 ml cleaned centrifuge tube and 18,2 MΩ water was added up to
one third of centrifuge tube volume. Sample was then centrifuged at 7000 rpm during 20 mins. After
centrifugation, the upper 2/3 of water above the mineral slurry, was transferred in a clean 10 ml sterile
plastic syringe and then filtered through a 0.45 µm polytetrafluoroethylene (PTFE) syringe. The
obtained filtered water was split into 5 cleaned 10 ml polypropylene containers, forming 5 different
aliquots from the same handpicked mineral fraction.
Two different mortars and pestles were used: (i) one dedicated to quartz and carbonates, and
(ii) one to sulfides and sulfosalts. Between two samples, the mortar and pestle were cleaned by
crushing several times pure fused silica and rinsed with hot (80°C) 18,2 MΩ water. Between ore and
gangue mineral separations, mortar and pestle were cleaned in hot 2 M HNO3 during 12 to 24 h and
rinsed 3 times with 18,2 MΩ water.
Regularly fused silica was crushed and leached following the same protocol (Blank samples)
in order to monitor possible contaminations during sample preparation.
ICP-MS
Two aliquots of each sample were analyzed for their composition using a quadrupole-based
inductively coupled plasma mass spectrometry. Multi-element standard solutions at different
concentrations (0, 0.02, 1, 5, 20, 100 and 200 mg/l) were used for calibration. Total variation
coefficients of triplicate sample measurements are smaller than 10% and chemical blanks for the
procedure were less than 2% of the sample signal. Limit of determination were fixed at 2 times mean
values of the blank samples analyzed (n=4). Isotopes analyzed during the first session were: 11B, 23Na,
45
Sc, 47Ti, 51V, 52Cr, 55Mn, 57Fe, 59Co, 60Ni, 65Cu, 66Zn, 75As, 78Se, 85Rb, 88Sr, 89Y, 93Nb, 95Mo, 107
Ag,
111
Cd, 128Sn, 121Sb, 133Cs, 137Ba, 139La, 140Ce, 141Pr, 146Nd, 147Sm, 153Eu, 157Gd, 159Tb, 163Dy, 165
Ho, 166Er,
377
169
Tm, 172Yb, 175Lu, 197Au, 208Pb, and 209Bi; and during the second one: 23Na, 27Al, 39K, 43Ca, 44Ca, 206Pb,
207
Pb, 208Pb.
Sr and Pb isotopes
One aliquot was used for Sr and Pb isotopic ratio measurements. Sr and Pb separation was carried out
using cascade columns with Sr-spec, TRU-spec and Ln-spec resins following a modified method after
Pin et al. (1994). Pb was further purified with a AG-MP1-M anion exchange resin in a hydrobromic
medium. Pb and Sr isotope ratios were measured on a Thermo NEPTUNE Plus mass spectrometer at
the University of Geneva, following the methods described by Chiaradia et al. (2014).
Cl isotopes
Fluid inclusion leachate solutions were reacted with 10 ml of 50% HNO3 and gently heated on a hot
plate for 2 hours covered with a watch glass containing deionized water to remove the high
concentration of sulfur in the samples (Barnes et al., 2009). The samples are then prepared following
the methods detailed by Eggenkamp (1994), as modified by Barnes and Sharp (2006) and Sharp et al.
(2007). 4 ml of 1 M KNO3 is added to the sample solution to increase the ionic strength. 1 ml of 0.4
M AgNO3 is added to precipitate AgCl. The AgCl is allowed to precipitate overnight in the dark and
then filtered onto quartz filters. The AgCl and filter is placed in a Pyrex tube and reacted with excess
CH3I under vacuum to produce CH3Cl, the analyte introduced into the ThermoElectron MAT 253
mass spectrometer. δ37Cl values are reported in standard per mil notation versus Standard Mean
Oceanic Chloride (SMOC). Error on each analysis is ±0.2‰, based on the long-average of three
seawater standards.
Ion chromatography
Cl, Br, F, PO4 and SO4 content was determined in one aliquot using Dionex ICS-3000 at the
University of Geneva. Injected volume of solution were 50 µL and run time 26 min. The limit of
detection of such method is around 10 ppb.
References additional to the main Reference list

Barnes, J.D., Sharp, Z.D., 2006. A chlorine isotope study of DSDP/ODP serpentinized ultramafic
rocks: insight into the serpentinization process. Chem. Geol. 228, 246-265.
Eggenkamp, H.G.M., 1994. The geochemistry of chlorine isotopes. Ph.D. Thesis, University of
Utrecht, 151 pp.
Pin, C., Briot, D., Bassin, C., Poitrasson, F. (1994). Concomitant separation of strontium and
samarium-neodymium for isotopic analysis in silicate samples, based on specific extraction
chromatography. Analytica Chimica Acta, 298, 209-217.
378
Sharp, Z.D., Barnes, J.D., Brearley, A.J., Chaussidon, M., Fischer, T.P., Kamenetsky, V.S., 2007.
Chlorine isotope homogeneity of the mantle, crust and carbonaceous chondrites. Nature 446,
1062–1065
379
Chapter 7:
Trace element diffusion and incorporation in quartz

during heating experiments
B. Rottier*, · H. Rezeau*, · V. Casanova*, · K. Kouzmanov*, · R. Moritz*, K. Schlöglova**, · M.
Wälle**†, · L. Fontboté*.

† present address: Memorial University of Newfoundland, CREAIT, CRC and CFI Services (CCCS),
Published in Contributions to Mineralogy and Petrology
380
Contrib Mineral Petrol (2017) 172:23
DOI 10.1007/s00410-017-1350-4
ORIGINAL PAPER
Trace element diffusion and incorporation in quartz

during heating experiments
B. Rottier1 · H. Rezeau1 · V. Casanova1 · K. Kouzmanov1 · R. Moritz1 ·
K. Schlöglova2 · M. Wälle2,3 · L. Fontboté1
Received: 25 November 2016 / Accepted: 12 March 2017

© Springer-Verlag Berlin Heidelberg 2017
Abstract Heating of quartz crystals in order to study melt magmatic quartz records only small, up to a few ppm,
and high-temperature fluid inclusions is a common prac- enrichment in Cu and Na, mostly substituting for Li. By
tice to constrain major physical and chemical parameters of contrast, heated hydrothermal quartz shows enrichment up
magmatic and hydrothermal processes. Diffusion and mod- to several hundreds of ppm in Cu, Li, and Na, which sub-
ification of trace element content in quartz and its hosted stitute for originally present H. This study reveals that the
melt inclusions have been investigated through step-heating composition of both quartz and its hosted melt inclusions
experiments of both matrix-free quartz crystals and quartz may be significantly modified upon heating experiments,
crystals associated with sulfides and other minerals using a leading to erroneous quantification of elemental concentra-
Linkam TS1500 stage. Magmatic and hydrothermal quartz tions. In addition, each quartz crystal also becomes signifi-
were successively analyzed after each heating step for cantly enriched in Cu in the sub-surface layer during heat-
Cu, Al, and Ti using electron probe micro-analyzer. After ing. We propose that sub-surface Cu enrichment is a direct
the last heating step, quartz crystals and their hosted melt indication of Cu diffusion in quartz externally sourced from
inclusions were analyzed by laser ablation inductively cou- both the surrounding sulfides as well as the copper pins
pled plasma mass spectrometry and compared to unheated belonging to the heating device. Our study shows that the
samples. Heated samples reveal modification of Cu, Li, Na, chemical compositions of both heated quartz and its hosted
and B contents in quartz and modification of Cu, Li, Ag, inclusions must be interpreted with great caution to avoid
and K concentrations in melt inclusions. Our results show misleading geological interpretations.
that different mechanisms of Cu, Li, and Na incorpora-
tion occur in magmatic and hydrothermal quartz. Heated Keywords Diffusion · Trace elements · Copper ·
Hydrothermal and magmatic quartz · Melt inclusions ·
Communicated by Hans Keppler.
Porphyry systems
Electronic supplementary material The online version of this

article (doi:10.1007/s00410-017-1350-4) contains supplementary Introduction
material, which is available to authorized users.
* B. Rottier Quartz consists of three-dimensional network of

bertrand.rottier@gmail.com [SiO4]4− tetrahedra forming small and large channel-like
1
structures along the c-axis (Fig. 1; Weil 1984). Among the
Department of Earth Sciences, University of Geneva,
different point defects potentially affecting the quartz struc-
1205 Geneva, Switzerland
2
i4+ by a trivalent cation is the most
ture, substitution of a S
Institute of Geochemistry and Petrology, ETH Zürich,
important one, commonly with Al3+, and subordinately
8092 Zurich, Switzerland 3+ 3+ 3+ 3+
3
with Ga , Fe , B , and As (Fig. 1; Weil 1984; Götze
Present Address: Memorial University of Newfoundland,
2009). The charge deficit created by this substitution is bal-
CREAIT, CRC and CFI Services (CCCS), Bruneau Centre
for Research and Innovation, St. John’s, NL A1C 5S7, anced either by the incorporation of monovalent cations in
Canada interstitial positions (Fig. 1) or by the substitution of one
13
Vol.:(0123456789)
381
23 Page 2 of 20 Contrib Mineral Petrol (2017) 172:23
Fig. 1 Projection of right
(P3z21) of α-quartz atomic
positions onto the plane per-
pendicular to c-axis including
the most common defect types,
modified after Weil (1984).
Type of substituting cations is
from Götze (2009)
i4+ by a pentavalent cation (e.g., P5+; Götze 2009). The

S (e.g., Student and Bodnar 2004; Davidson and Kamenetsky
large channel-like structures incorporating monovalent 2007; Esposito et al. 2012) and high-temperature fluid and
cations have a diameter of ~1 Å (for β-quartz; Verhoogen melt inclusions in hydrothermal porphyry-type quartz veins
1952; White 1970; Zajacz et al. 2009) and favor the incor- (e.g., Ulrich et al. 2002; Harris et al. 2003; Campos et al.
poration of small cations such as H +, Li+, Na+, Cu+, and 2006; Stefanova et al. 2014; Koděra et al. 2014). We have
+
Ag (Fig. 1). Rapid diffusion of monovalent cations along addressed this issue using a Linkam TS1500 heating stage,
the c-axis through these large channel-like structures in one of the most common devices for such studies.
response to electric fields or chemical gradients has been Modifications of natural magmatic and hydrothermal
reported by previous studies (Verhoogen 1952; Milne and quartz composition and their hosted melt inclusions after
Gibbs 1964; Rybach and Laves 1967; Mortley 1969; Fris- step-heating were investigated using both electron probe
chat 1970; White 1970; McBrayer et al. 1986; Kronenberg micro-analyzer (EPMA) and laser ablation inductively cou-
and Kirby 1987; Raghavan et al. 1995; Poignon et al. 1996; pled plasma mass spectrometry (LA-ICP-MS) analyses.
Zelený et al. 2012; Seo and Heinrich 2013). Our results reveal the direct incorporation of C u+, Na+,
+ 3+
Quartz is the most commonly studied host mineral for Li , and B in the structure of heated quartz as well as the
fluid and melt inclusions due to its ubiquity, transparency, formation of a Cu-rich sub-surface layer. We also report
and hardness. Trace element compositions of hydrother- the diffusion of Cu, Li, Ag, and possibly K, leading to an
mal quartz have been used extensively to constrain vari- enrichment or a depletion of these elements in heated melt
ous parameters during crystallization such as temperature, inclusions. This study explicitly demonstrates the high
pressure, pH, fluid composition, and quartz growth rate mobility of trace elements during heating using a Linkam
(e.g., Ihinger and Zink 2000; Wark and Watson 2006; Rusk stage TS1500, but also the ability of both magmatic and
et al. 2008; Götze 2009; Jourdan et al. 2009; Thomas et al. hydrothermal quartz to incorporate diffusing cations. We
2010; Huang and Audétat 2012; Mercer et al. 2015). Sev- aim to propose a method to differentiate between natural
eral studies have shown that H, Li, Na, Cu, and Ag con- trace element content and analytically biased concentra-
centrations in quartz-hosted fluid and melt inclusions can tions, with an emphasis on Cu, which may result in errone-
be modified during heating experiments (e.g., Kamenetsky ous geological interpretations with respect to magmatic and
and Danyushevsky 2005; Li et al. 2009; Zajacz et al. 2009; hydrothermal ore-forming processes.
Lerchbaumer and Audétat 2012). However, no study to
date focuses on the potential effect of cation diffusion on
the trace element composition of quartz. Moreover, previ- Samples and analytical procedures
ous heating experiments were carried out using a muffle
furnace and/or a pressure vessel, but no studies report the The three samples studied in this contribution were col-
effect of experiments using the same heating stages com- lected from a mid-Miocene magmatic–hydrothermal sys-
monly used to study melt inclusions in magmatic quartz tem, which belongs to the Cerro de Pasco polymetallic
13
382
Contrib Mineral Petrol (2017) 172:23 Page 3 of 20 23
district, located in central Peru (Baumgartner et al. 2008; silicate melt inclusions (size <20 µm), similar to those
Rottier et al. 2016a, b). The analyzed samples contain described at the Elatsite porphyry Cu–Au deposit in Bul-
magmatic quartz crystals from a rhyodacitic dome (MAG; garia (Stefanova et al. 2014).
Fig. 2a) and hydrothermal quartz crystals from porphyry- The magmatic quartz from sample MAG is from a
type quartz-sulfide veins HVA and HVB (Fig. 2b, c). The non-mineralized unaltered rhyodacitic dome located
samples were prepared as 200- to 250-µm-thick double- in the SW part of the district. It displays a porphyritic
polished slabs from which portions up to 4 mm long were texture and consists of plagioclase, quartz, biotite phe-
broken apart and used for the study. Detailed descriptions nocrysts, and rare phenocrysts of K-feldspar, and apatite
of each slab portion used for this study are provided in surrounded by K-feldspar and a mineralogically unidenti-
Table 1. Four slabs are from the quartz vein HVA (HQA600, fied Si-K rich groundmass (Fig. 2a; Table 1). The whole-
HQA1200, HQA1200(HNO3), and H QA1200(T); Table 1), two rock Cu content of the rhyodacite is 7.0 ppm (Table
are from the quartz vein HVB (HQB900 and HQB900(T); A.1). Quartz crystals have a diameter of 0.5–2 mm and
Table 1), and four are from the rhyodacitic dome MAG exhibit common resorption textures (Fig. 2a). They host
(MQ600, MQ900, MQ900(MF) and MQ900(HNO3); Table 1). glassy silicate melt inclusions (SMIs) with a diameter of
Sample HVA is a porphyry-style quartz-magnetite-chal- 5–70 µm (Fig. 2d), but no fluid inclusions were observed.
copyrite-pyrite vein (~0.5 cm thick) crosscutting a trachyte Solid inclusions of biotite, zircon, apatite, and titanite are
porphyry (Fig. 2b) studied by Rottier et al. (2016b). This common.
vein was formed at low pressure (<290 bar) and high tem- Prior to heating experiments, slabs H QA1200(HNO3) and
perature (>600 °C). Quartz hosts numerous primary inclu- MQ900(HNO3) were heated to 80 °C in concentrated HNO3
sions containing variable proportions of both silicate glass (14 M) in a closed 10-ml Teflon® beaker for 24 and 72 h,
and globules consisting of a metal-rich hypersaline liquid respectively, in order to dissolve any sulfides, phosphates,
(>90 wt% NaCl eq.), hereafter referred to as heterogeneous and carbonates present in the samples.
silicate melt inclusions (HSMIs; Fig. 2e). It also hosts rare Heating experiments were carried out using a Linkam
metal- and sulfur-rich hypersaline liquid inclusions with a TS1500 stage mounted on a DMLB Leica microscope.
salinity of about 70 wt% NaCl Eq. All experiments were conducted at 1 atm in a nitrogen
The quartz vein HVB is a porphyry-type quartz-mag- atmosphere in order to minimize oxidation of the inves-
netite-chalcopyrite-pyrite vein crosscutting a strongly tigated samples. The stage was calibrated using a SYN-
silicified magmatic rock (Fig. 2c; Table 1). The hydrother- FLINC standard at 374.1 °C, and the melting points
mal quartz hosts hypersaline liquid inclusions (~57 wt% of AgI and NaCl at 558 and 801 °C, respectively. Each
NaCl eq., homogenization temperature >600 °C) and low- selected slab was heated from room temperature to the
density vapor inclusions, and also contains sparse glassy required one at a rate of 50 °C/min. The temperature was
Fig.  2 a Scan of a thin section of the rhyodacitic dome (cross- Table 1); d typical silicate melt inclusions hosted in quartz phe-
polarized transmitted light); b quartz-magnetite-chalcopyrite-pyrite nocrysts from the rhyodacitic dome; e typical heterogeneous silicate
vein crosscutting a trachyte porphyry (quartz vein in sample HVA, melt inclusions hosted in quartz from quartz vein A of sample HVA
Table 1); c quartz-magnetite-chalcopyrite-pyrite vein crosscut- (Table 1)
ting strongly silicified magmatic rock (quartz vein in sample HVB,
13
383
Table 1 Sample descriptions and heating experiment conditions

Sample Slab Description Inclusions in studied Pre-treatment Heating runs (°C)
quartz
Porphyry vein HVA HQA1200 Quartz-magnetite-chal- HSMIs and hypersaline None 400; 600; 700; 800; 1200
copyrite-pyrite vein liquid inclusions
HQA1200(T) Quartz-magnetite- HSMIs and hypersaline None 1200
chalcopyrite-pyrite liquid inclusions
vein + part of the host
trachyte porphyry
HQA1200(HNO3) Quartz-magnetite- HSMIs and hypersaline HNO3 (14 M) during 400; 600; 700; 800; 1200
chalcopyrite-pyrite liquid inclusions 24 h at 80 °C
trachyte porphyry
HQA600 Quartz-magnetite- HSMIs and hypersaline None 520; 600
chalcopyrite-pyrite liquid inclusions
trachyte porphyry
Porphyry vein HVB HQB900 Quartz-magnetite-chal- Chalcopyrite grain None 600; 900
copyrite-pyrite vein
HQB900(T) Quartz-magnetite-chal- Chalcopyrite grain and None 900
copyrite-pyrite vein hypersaline liquid
inclusions
Rhyodacitic dome MQ600 Quartz phenocryst with SMIs None 520; 600
a minor portion of the
magmatic matrix
MQ900 Quartz phenocryst with SMIs None 900
a minor portion of the
magmatic matrix
MQ900(MF) Quartz phenocryst Biotite grain and SMIs Rock matrix removed 900
mechanically
MQ900(HNO3) Quartz phenocryst with SMIs HNO3 (14 M) during 900
a minor portion of the 72 h at 80 °C
magmatic matrix
maintained for 6 h before cooling the slab down to room Analytical methods
temperature at a rate of 300 °C/min.
Several slabs ( HQA1200, HQA1200(HNO3), HQA600, Raman analyses were performed from room temperature
HQB900, and MQ600) were heated several times. After up to 1200 °C using a confocal LABRAM at the Univer-
each heating step, slabs were fixed onto a brass plug using sity of Geneva equipped with a 532.12-nm Nd-YAG Laser
Crystalbond® heated at ~120 °C. They were subsequently coupled to an Olympus BX51 microscope and a Linkam
cleaned using diamond paste (Ø = 0.25–0.5 µm), rinsed TS1500 heating stage.
with 18.2 MΩ water, and finally carbon coated. Quartz EPMA measurements were carried out at the University
was analyzed by EPMA for Cu, Ti, and Al (spot analysis of Lausanne using a JEOL JXA 8200 SuperProbe. Results
profiles and X-ray elemental maps). After each analytical were acquired using an 80 nA electron beam accelerated
session, the carbon coating was removed using diamond at 20 kV with a 5 µm beam diameter. Standards and X-ray
paste (Ø = 0.25–0.5 µm), and slabs were removed from emission lines were set up as follows: albite (Al-Kα), bor-
the brass plug, subsequently cleaned in acetone, and rinsed nite (Cu-Kα), and M nTiO3 (Ti-Kα). Counting times of
with 18.2 MΩ water, before being re-heated to higher tem- 40 s for the peak and 20 s for the background on both sides
peratures. In total, this procedure has been repeated up to of the peak were used for Al, while 60 s for the peak and
five times (Table 1). After the last heating step, the studied 30 s for the background on both sides of the peak were
quartz crystals and their hosted SMIs and HSMIs were ana- used for Cu and Ti. Following the definition of Currie
lyzed by LA-ICP-MS to acquire a wider spectrum of trace (1968), calculated limits of determination are Al = 56 ppm,
element compositions. After LA-ICP-MS analyses, the dif- Ti = 77 ppm, and Cu = 99 ppm. All the obtained elemental
ferent slabs were embedded in epoxy, polished down by maps were treated with ImageJ software (Schneider et al.
~10 µm, and subsequently re-analyzed by EPMA. 2012). For each map, we optimized the color gradient scale
13
384
and selected an adequate upper threshold. Minerals having is in agreement with the calculated mean A l2O3 content
a high content (>1 wt%) of Ti, and/or Al, and/or Cu will obtained from whole-rock geochemistry of the volcanic and
be above the fixed thresholds and will appear black on the sub-volcanic rocks of the district (Rottier et al. 2016b). For
treated maps. host correction (i.e., quartz), 99.9 wt% SiO2 was assumed
Quartz crystals and their hosted SMIs and HSMIs as an internal standard.
were analyzed using a 193-nm ArF Excimer laser with
an energy-homogenized beam coupled with an ELAN
6100 DRC ICP quadrupole mass spectrometer at ETH Results
Zurich (Günther et al. 1997, 1998; Heinrich et al. 2003).
Table 2 summarizes the analytical conditions, data acquisi- Phase transition during heating experiments
tion parameters, and the list of isotopes analyzed. Quartz
was ablated using an iris diaphragm that allows manual According to the phase diagram of silica at 1 atm, the
progressive increase of the laser beam diameter to limit phase transition from α- to β-quartz occurs at ~573 °C,
explosions out (Guillong and Heinrich 2007). LA-ICP- and the phase transition between β-quartz and HP-
MS transient signals were reduced using the Sills software tridymite at ~867 °C (Heaney 1994). Direct phase tran-
(Guillong et al. 2008). The NIST glass standard SRM 610 sition from β-quartz to β-cristobalite at ~1050 °C has
was used as an external standard and analyzed twice, brack- also been documented (Heaney 1994; Lakshtanov et al.
eting a maximum of 20 unknowns to correct instrumental 2007). The α- to β-quartz phase transition is displa-
drift by linear regressions. Concentration quantification of cive and results in a small rotation of S iO4 tetrahedra
the HSMIs and melt inclusions has been done following (Dolino 1990), whereas β-quartz to HP-tridymite and
the method described in Halter et al. (2002). A content of to β-cristobalite phase transitions are reconstructive and
16.7 wt% Al2O3 was used for the internal standardization occur by breaking of the chemical bonds (Heaney 1994;
of HSMIs (see details in Rottier et al. 2016b) and 16 wt% Lakshtanov et al. 2007). Reconstructive phase transitions
Al2O3 for melt inclusions in the magmatic quartz, which could affect the trace element composition of quartz
Table 2 LA-ICP-MS and data acquisition parameters
Excimer 193 nm ArF laser Complex 110I

Output energy 160 mJ
Homogeneous energy density on sample 20 J/cm2
Repetition rate 10 Hz
Ablation mode Single hole (iris diaphragm)
Crater sizes 30–70 µm
Ablation cell In-house-built glass chamber with anti-reflection coated silica glass window (volume of approx.
1 cm3)
Perkin-Elmer ELAN 6100 DRC
RF power 1550 W
Detector mode Dual
Quadrupole setting time 3 ms
Nebulizer gas flow 0.79 l min Ar
Auxiliary gas flow 0.89 l min Ar
Plasma gas flow 15.9 l min Ar
Carrier gas flow 1.9 l min He
Additional gas flow 5 ml/min H2
Sweeps per reading 1
Readings per replicate 300–350
Replicates 1
Dwell time per isotope 30 ms for Cu and Ag; 20 ms for Na and Ca, and Ti; 10 ms for all others
Points per peak 1 per mass
Oxide formation ratio (ThO+/Th) <0.5%
7
Isotopes analyzed Li, 11B, 23Na, 25Mg, 28Si, 31P, 39K, 44Ca, 57Fe, 65Cu, 71Ga, 72Ge, 75As, 85Rb, 88Sr, 89Y, 90Zr, 107Ag,
118
Sn, 121Sb, 133Cs, 139La, 140Ce, 173Yb, 182W, 208Pb, 238U
13
385
(Heaney 1994), and therefore identification of these Magmatic quartz

transitions is important. We performed Raman spectros-
copy analyses of one of the selected quartz crystals dur- A total of four magmatic quartz crystals from four slabs
ing heating experiments, from room temperature up to were studied. Slab M Q600 was analyzed before heating and
1200 °C, in order to identify phase transitions during our then after heating steps at 520 and 600 °C, whereas MQ900,
experiments (Fig. 3a). All acquired spectra are repre- MQ900(MF), and MQ900(HNO3) were only analyzed after heat-
sentative of α- and β-quartz (Shapiro et al. 1967), and no ing at 900 °C. Copper was only detected in M Q900 and
spectrum characteristic of HP-tridymite or β-cristobalite MQ900(MF) (Fig. 4; Table A.2). The EPMA profile and the
was observed. Phase transitions between α- and β-quartz Cu elemental map reveal a decrease of Cu content from
are recorded by a slight shift of the main quartz peak the border toward the core of the crystals (Fig. 4b, c).
position at ~460 cm−1 (Fig. 3b). The absence of HP- MQ900(MF) shows a decrease of Cu from 970 to 320 ppm
tridymite or β-cristobalite is due to the sluggish kinetic over 250 µm (Fig. 4b, c), and similar observation can be
rates of these phase transitions (Lakshtanov et al. 2007). made on MQ900 (Table A.2).
We are therefore confident that the studied crystals were EPMA measurements performed after polishing down
α-quartz below 573 °C and β-quartz at higher tempera- the slabs by ~10 µm along profiles previously analyzed on
tures during all heating experiments described below. each quartz crystal were systematically below the limit of
determination with respect to Cu (Table A.2).
EPMA profiles and elemental mapping Hydrothermal quartz from porphyry vein HVA
Only EPMA results discussed below are shown in the EPMA spot analyses along profiles and X-ray elemen-
following figures. The complete dataset is provided in tal maps (Al, Ti, and Cu; Fig. 5) were performed before
the supplementary Table A.2 and Figs. A.1, A.2, A.3, heating and after heating at 400, 600, 700, 800, and
and A.4. 1200 °C on HQA1200 and HQA1200(HNO3). No changes in
Fig.  3 a Raman spectra of a quartz crystal heated at different tem- decreases above 700 °C due to electromagnetic radiation emitted by
peratures using a Linkam TS1500 stage. Peaks related to the sap- the heated ceramic cup of the Linkam TS1500 stage. b Evolution
phire (Spr) window of the stage and the one from the quartz (Qz) of the main quartz peak position with heating temperature; the α/β
are indicated. Raman parameters were as follows: t = 60 s repeated quartz transition is indicated by the red line
twice, hole 500 µm, slit 100 µm, no filter. The quality of the spectra
13
386
Fig.  4 a SEM-CL image of the matrix-free magmatic quartz sam- profile 1–2; c Cu elemental map after heating at 900 °C; d Al elemen-
ple MQ900(MF) after heating at 900 °C. EPMA and LA-ICP-MS spot tal map after heating at 900 °C; e Ti elemental map after heating at
locations are reported and the red dashed frame indicates the EPMA 900 °C. Mineral abbreviation: Bt biotite
elemental map area; b Cu concentrations obtained by EPMA along
Al and Ti concentrations over the different heating steps A.2). By contrast, in HQA1200(HNO3) ~100 ppm of Cu was
were detected, while the Cu concentrations were found detected after heating at 700 °C, and Cu concentrations
to vary as a function of temperature (Figs. 5, A.1; Table slightly increased after each heating step from 800 to
A.2). In HQA1200, Cu was detected after the first heat- 1200 °C, but never exceeding 200 ppm (Fig. A.1). Cop-
ing step at 400 °C and shows a progressive increase of per elemental maps of H QA1200(HNO3) display no particu-
its concentration from 400 to 800 °C (Fig. 5). The high- lar Cu spatial distribution (Fig. A.1). Similar low Cu val-
est Cu concentrations are recorded after heating at 800 °C ues are recorded for H QA600 in which Cu was detected
with values up to 1100 ppm (Fig. 5b, c; Table A.2). Cop- by EPMA spot analyses after heating at 520 °C. After
per concentration decreases from the border toward the both 520 and 600 °C heating steps, only a small amount
center of the quartz crystal (Fig. 5b, c, e, f), similarly to of Cu (<180 ppm) was detected, and Cu elemental maps
MQ900 and M Q900(MF). After heating at 1200 °C, Cu con- revealed a uniform Cu distribution (Fig. A.3; Table A.2).
centration became more homogeneous throughout the Finally, all the investigated samples were polished
quartz, varying between 190 and 410 ppm (Fig. 5b, c, g). down by ~10 µm, and EPMA spot analyses were below
In addition, X-ray elemental maps reveal a correlation the limit of detection with respect to Cu, except for
between Al, Ti, and Cu contents at 1200 °C (Fig. 5g–i), HQA1200, in which concentrations between 110 and
which is also observed in HQA1200(T) at 1200 °C (Fig. 300 ppm correlate with Al concentrations (Table A.2).
13
387
Fig.  5 a SEM-CL image of HQA1200 after heating at 1200 °C, with at 400 °C (e), after heating at 800 °C (f), and after heating at 1200 °C
EPMA and LA-ICP-MS spot locations; b Cu concentrations obtained (g); h Ti elemental map after heating at 1200 °C; i Al after heating at
by EPMA along profile 1–2; c Cu concentrations obtained by EPMA 1200 °C
along profile 3–4; Cu elemental map before heating (d), after heating
13
388
Hydrothermal quartz from porphyry vein HVB A.4). Both samples host a solid inclusion of chalcopyrite
(<50 µm), from which two EPMA spot analysis profiles
Two quartz samples from porphyry vein HVB were stud- were performed perpendicular to the edge of the crystal
ied, including HQB900, which was analyzed before heating (Figs. 6, A.4). EPMA results obtained on H QB900 prior to
and after heating at 600 and 900 °C (Fig. 6), and HQB900(T) heating show that Cu content decreases from 1200 ppm to
which was only analyzed after heating at 900 °C (Fig. the determination limit along profile 3–4 (Fig. 6a, c), and
Fig.  6 a SEM-CL image of

HQB900 after heating at 900 °C,
with EPMA and LA-ICP-
MS spot locations; b copper
concentrations obtained by
EPMA along profile 1–2; c
copper concentrations obtained
by EPMA along profile 3–4; Cu
elemental map at room tempera-
ture (d), after heating at 600 °C
(e), and after heating at 900 °C
(f). On the Cu elemental maps,
the chalcopyrite inclusion was
above the threshold of concen-
tration gradient color scales and
appears black; g Al elemental
map after heating at 900 °C
13
389
from 380 ppm to below the determination limit along pro- Sodium and B concentrations in quartz increase with
file 1–2 (Fig. 6a, b). The potential presence of sub-surface temperature, with the exception of MQ900(HNO3) showing
chalcopyrite micro-inclusions cannot be ruled out and B concentrations higher than MQ0 but lower than MQ600
might explain high Cu concentrations near the sulfide inclu- (Fig. 7a). The Li content in quartz tends to decrease with
sion. After heating at 600 °C, Cu content strongly increases the heating experiment temperature (Figs. 7a, 9c).
and displays an exponential-like decrease from 1160 to A total of 32 silicate melt inclusions (SMIs) were ana-
280 ppm over a short distance along profile 3–4, whereas lyzed including 14 from MQ0, 6 from MQ600, 5 from
it shows a progressive decrease from 590 to 225 ppm along MQ900(HNO3), 2 from MQ900(MF), and 5 from MQ900. The
profile 1–2 (Fig. 6a–c). After heating at 900 °C, Cu concen- full dataset is provided in supplementary Table A.4. We
trations along profile 3–4 were similar to those measured obtained similar concentrations for almost all analyzed ele-
after heating at 600 °C, except for higher values close to ments except for Cu, Li, B, K, and Ag (Fig. 8). The most
the chalcopyrite grain (up to 2280 ppm; Fig. 6c). By con- important variations are shown by Cu concentrations rang-
trast, Cu concentrations along profile 1–2 after heating at ing from <0.2 to 6.3 ppm for SMIs hosted in M Q0, from
900 °C are always higher, decreasing from 900 to 330 ppm, 6 to 37 ppm (except one outlier at 115 ppm) for SMIs in
compared to the results obtained after heating at 600 °C MQ600, from 10 to 31 ppm for SMIs in MQ900(HNO3), from
(Fig. 6b). Nevertheless, both profiles show that Cu concen- 211 to 267 ppm in SMIs in MQ900(MF), and from 243 to
trations tend to reach a plateau between 350 and 400 ppm 557 ppm in SMIs in MQ900 (Fig. 8). Similar concentra-
away from the chalcopyrite grain (Fig. 6b, c). HQB900(T) tion range from 0.1 to 0.4 ppm is observed for Ag in SMIs
was analyzed only after heating at 900 °C and displays a hosted in MQ0 and M Q600, but higher values are meas-
similar range of Cu concentrations along the two profiles ured in SMIs from the other quartz samples with contents
(Fig. A.4). An exponential-like decrease from 1950 to between 0.2 and 6 ppm (Fig. 8). The Li content decreases
220 ppm of Cu in less than 120 µm is visible along both with temperature and varies between 410 and 830 ppm
profiles (Fig. A.4). in unheated SMIs from MQ0, from 100 to 700 ppm in
After polishing down the samples by ~10 µm, Cu was SMIs from MQ600, and from 53 to 220 ppm in SMIs from
rarely detected in HQB900, though HQB900(T) displayed up MQ900(HNO3). Lithium content is always below the detec-
to 300 ppm Cu (Table A.2). tion limit (except one analysis at 30 ppm) in heated SMIs
from MQ900 and M Q900(MF) (Fig. 8). The K concentration
LA‑ICP‑MS results decreases up to 1.5 wt% in heated SMIs, but no correla-
tion with temperature is observed (Fig. 8). The Na content
Trace element composition of magmatic quartz and melt in SMIs seems to be unaffected or only slightly affected by
inclusions heating experiments (Fig. 8). The measured B concentra-
tions, from 32 to 81 ppm in unheated SMIs in M Q0 and
Each magmatic quartz crystal (MQ600, MQ900, MQ900(MF), from 55 to 134 ppm in heated SMIs (with no correlation
and MQ900(HNO3)) was analyzed by LA-ICP-MS along to temperature, Fig. 8), may suggest a slight increase when
rim-to-core profiles. Unheated quartz, further referred to heating the SMIs. However, this potential increase has to be
as MQ0, was also analyzed in order to compare the results taken with caution considering that B was detected only in
with the heated samples. No correlation between trace ele- the largest heated SMIs (in 10 out of 18 SMIs) due to the
ment concentrations and distance to the crystal cores was high background signal. Therefore, the behavior of B will
observed. The complete dataset is available in the supple- not be further discussed.
mentary Table A.3. For all quartz samples, the most com-
mon trace elements are Al, Ti, P, Li, Na, B, Cu, and Mg. Trace element compositions of quartz and HSMI
The high background signal explains the high LOD (limit from the porphyry vein HVA
of detection; between 10 and 40 ppm) for K and Fe and
therefore the difficulty to correctly quantify the concentra- Unheated quartz (hereafter referred to as HQA0), HQA600,
tions of these elements. HQA1200, and HQA1200(HNO3) were analyzed by LA-
The Cu, Li, Na, and B concentrations vary from one ICP-MS. The full dataset is provided in the supplemen-
quartz crystal to another (Figs. 7a, 9a–c). Copper concen- tary Table A.3. To determine the trace element composi-
trations differ significantly from those obtained by EPMA tions of quartz, LA-ICP-MS analyses were performed
with the values ranging between 0.3 and 0.9 ppm, 0.6 and in areas devoid of solid and fluid inclusions and only
1.3 ppm, and 0.7 and 5 ppm for MQ600, MQ900(MF), and analyses with flat LA-ICP-MS transient signals were con-
MQ900, respectively (Table A.3). All Cu contents remain sidered (Fig. 7E). Potential contamination of the abla-
below the detection limit (<0.2 ppm) for M Q900(HNO3), tion signals by fluid and melt inclusions were carefully
whereas only one analysis in MQ0 exceeds it (0.7 ppm). checked by tracking the signals of Cs, Sr, and Rb. Copper
13
390
Fig. 7 Li, B, Na, and Cu contents of heated and unheated quartz values lying within 1.5 times the interquartile range beyond the edges
crystals obtained by LA-ICP-MS from a rhyodacitic dome (a), quartz of the box. The white circles and triangles represent the outliers devi-
vein HVA (b), and quartz vein HVB (c). In graphs a–c, the height of ating by more than ±2.7σ. Colored dots represent the single values.
the colored bars represents the interquartile range (i.e., representing The numbers in brackets (a–c) correspond to the number of analy-
the most frequent 50% of the distribution). The horizontal black lines ses; examples of selected LA-ICP-MS transient signals of MQ900 (d),
within the colored boxes are the mean and the black dots represent HQA1200 (e), and HQB900 (f)
the median value. “Whiskers” of each box extend to the extremum
13
391
Fig. 8 Comparison of Li, B, Cu, Ag, K, and Na contents of SMIs black lines within the boxes are the mean and the black dots represent
hosted in unheated and heated magmatic quartz crystals. The num- the median value. “Whiskers” of each box extend to the extremum
bers in brackets correspond to the number of SMIs analyzed. The values lying within 1.5 times the interquartile range beyond the edges
height of colored bars represents the interquartile range (i.e., repre- of the box. The white triangle represents an outlier deviating more
senting the most frequent 50% of the distribution). The horizontal than ±2.7σ. The red dot represents a single value
concentration in HQA0 varies between 0.7 and 3.4 ppm, in HQA1200(HNO3) are between 0.04 and 1.2 wt% (Fig. 10).
whereas HQA600 and HQA1200(HNO3) display only a subtle Sodium, Cs, and Rb are also enriched in HSMIs hosted in
Cu enrichment ranging from 1.2 to 10 ppm, and from 1.9 HQA1200 (Fig. 10). Lithium and boron were not detected in
to 10 ppm, respectively (Figs. 7b, 9e). HQA1200 shows sys- any HSMIs.
tematically higher Cu contents between 95 and 267 ppm
(Figs. 7b, 9e). Sodium concentration in quartz increases Trace element composition of hydrothermal quartz
with temperature as revealed by low values in HQA0 and from the porphyry vein HVB
HQA600 (0.5–31 ppm) and higher values for HQA1200 and
HQA1200(HNO3) (94–423 ppm; Figs. 7b, 9d). Similarly, Li Trace element composition of quartz from the porphyry
content increases in HQA1200(HNO3) and HQA1200 com- vein HVB was determined in quartz from an unheated
pared to HQA0 and HQA600 (Fig. 7b). Boron was only sample (hereafter referred to as HQB0), HQB900, and
detected in HQA600 (1 value at 9.9 ppm) and in HQA1200 HQB900(T), which were previously analyzed by EPMA. LA-
(3.5–9.9 ppm; Figs. 7b, 9f). Finally, HQA600, HQA1200, and ICP-MS analyses were performed in areas devoid of any
HQA1200(HNO3) reveal positive correlations between Al, Na, visible fluid, melt, or solid inclusions. LA-ICP-MS tran-
Li, and Cu concentrations (Fig. 9d–f), whereas HQA0 only sient signals display flat profiles for all elements (Fig. 7f).
shows a positive correlation between Al and Li concentra- LA-ICP-MS profiles were placed along the same EPMA
tions (Fig. 9f). profiles previously analyzed on H QB900. The high Cu con-
As described by Rottier et al. (2016b), compositions of centrations obtained by EPMA were not observed during
HSMIs are difficult to quantify due to the presence of both the LA-ICP-MS analyses (Figs. 6b, c, 7c). Additionally,
silicate glass and metal-rich hypersaline (>90 wt% NaCl the decreasing concentration pattern from the chalcopy-
eq.) liquid in variable proportions. A restricted number of rite inclusion toward the edge of the quartz crystal detected
HSMIs were analyzed, including 4 HSMIs from H QA0, by EPMA was not recognized. Heated quartz compared to
4 from HQA1200, and 3 from HQA1200(HNO3). Detailed unheated HQB0 displayed Cu, Na, and B enrichments with
results are provided in the supplementary Table A.5. The a similar Li content (Figs. 7c, 9d–f). No difference in trace
analyzed HSMIs show important variations of concentra- element composition was observed between HQB900 and
tion for most elements and the majority of them display a HQB900(T). Copper content ranges from 0.5 to 7 ppm in
strong correlation with Zn concentration. The latter is gen- HQB0, whereas it reaches 49 to 122 ppm in heated quartz
erally used as a proxy for the quantity of metal-rich hyper- (Figs. 7c, 9e). Sodium and B concentrations are between
saline (>90 wt% NaCl eq.) liquid in HSMIs (Rottier et al. <1.0 and 10 ppm in HQB0 and increase in heated quartz
2016b). Copper contents measured in HSMIs increase with the values between 4 and 28 ppm (Figs. 7c, 9d).
from 0.001 to 0.6 wt% for HSMIs hosted in H QA0 to 14 The Li content displays a slight decrease in heated quartz
to 27 wt% for those trapped in H QA1200, whereas the ones (Figs. 7c, 9f). Finally, Cu, Al, Na, and Li display positive
13
392
Fig. 9 Correlation diagrams of selected trace elements in the studied magmatic quartz crystals: Na vs. Al (a), Cu vs. Al (b), and Li vs. Al (c);
correlation diagrams of selected trace elements in the studied hydrothermal quartz crystals: Na vs. Al (d), Cu vs. Al (e), and Li vs. Al (f)
correlations amongst each other in heated quartz, whereas quartz MQ900(MF) in which Cu concentrations obtained by
no correlation is observed in unheated samples (Fig. 9d–f). EPMA fall between 970 and 310 ppm (Fig. 4a, b; Table
A.2), whereas LA-ICP-MS analyses yielded concentrations
around 1 ppm (Figs. 4a, 7a). Results obtained by LA-ICP-
Discussion MS analyses and EPMA should not be directly compared,
because of the different volume of material analyzed. The
Discrepancy between EPMA and LA‑ICP‑MS volume typically sampled by EPMA analysis is a few
measurements cubic microns and thus only provides sub-surface infor-
mation, whereas LA-ICP-MS analyzes a volume on the
Copper concentrations obtained by EPMA and by LA-ICP- order of tens of thousands of cubic microns. Once the heat-
MS analyses are different, with the exception of the quartz ing experiments are performed, the discrepancy between
vein HQA1200 after heating at 1200 °C (Figs. 5, 7b). The the two methods disappears after polishing the samples
best example of this discrepancy is illustrated by magmatic down by ~10 µm. This illustrates that the anomalous Cu
13
393
by EPMA compared to LA-ICP-MS analyses in our experi-

ments (Figs. 4, 5, 6, 7). Heating quartz at high temperature
(>1000 °C) heals damages produced by mechanical pol-
ishing (e.g., Freer and Dennis 1982; Cherniak et al. 2007;
Thomas et al. 2008; Farver 2010). This would explain the
marked decrease of Cu enrichment of the sub-surface layers
for samples heated at 1200 °C (HQA1200 and H QA1200T),
and consequently comparable Cu concentrations obtained
by both EPMA and LA-ICP-MS (Figs. 5g, h, A.2). Highly
damaged and reactive crystal sub-surface created by clas-
sical polishing could be avoided by a specific grinding
and polishing procedure, as demonstrated by Watson et al.
(2016), although it has not been tested in this study.
Fig. 10 Comparison of Na, K, Cu, Cs, Rb, and Ag contents of In quartz devoid of any surrounding mineral, exponen-
HSMIs hosted in heated and unheated quartz crystals from quartz tial-like Cu concentration gradients on the sub-surface
vein HVA. The numbers in brackets correspond to the number of layer decreasing from the border toward the center were
HSMIs analyzed. The height of colored bars represents the interquar-
tile range (i.e., representing the most frequent 50% of the distribu-
observed after the heating experiments (Figs. 4, 5, 6). The
tion). The horizontal black lines within the bars are the mean and the exact mechanism leading to these concentration gradients
black dots represent the median value. “Whiskers” of each box extend remains unconstrained. This could be a product of higher
to the extremum values lying within 1.5 times the interquartile range concentrations of crystallographic defects at the surface of
beyond the edges of the box
quartz grain borders as a result of polishing. Exponential-
like gradients with Cu decreasing from chalcopyrite inclu-
concentration is restricted to the sub-surface of each crys- sions to the surrounding quartz were also observed (Fig. 6,
tal, though the precise thickness of this layer could not be quartz HQB900 and HQB900T). As explained above, these
directly measured. The fact that no higher Cu signals are exponential-like concentration profiles mostly result from
observed in the LA-ICP-MS transient signals at the begin- adsorption processes and therefore they cannot be used to
ning of quartz ablation (Fig. 7d–f) suggests that the thick- estimate the diffusivity of Cu.
ness of the Cu-enriched sub-surface layer is around 1–2 µm. We have shown that Cu concentrations obtained by
If the enriched layer was thicker, it would be visible in the EPMA are not necessarily representative of the bulk sam-
LA-ICP-MS transient signals considering that our abla- ple, but further below we will show that Cu enrichment in
tion rate of quartz was around 1 to 2 µm/s (Fig. 7d–f). The the sub-surface layers can be used as an indication of Cu
concentrations of Cu measured in the sub-surface layers diffusion in both magmatic and hydrothermal quartz dur-
are higher than the sum of the concentrations of the triva- ing heating experiment. In magmatic quartz, LA-ICP-MS
lent cations (Al3+ + B3+). This indicates that Cu is not or analyses revealed high Cu concentrations in SMIs hosted in
only partly incorporated in the quartz structure as a charge MQ900 and MQ900(MF) and high Cu concentration has also
compensator (Cu+) and that an important amount of Cu is been detected in sub-surface layers of these crystals. By
probably enriched in the sub-surface layer by adsorption contrast, SMIs hosted in M Q600 and MQ900(HNO3) display
processes. no, or only limited, Cu enrichment, which also correlates
Standard polishing protocols using a variety of diamond with sub-surface layers devoid of Cu enrichment. In hydro-
abrasives, down to sub-micron particle size, on a rotating- thermal quartz, a similar correlation is observed between
lap cause physical modifications to the first hundreds of Cu sub-surface enrichment and Cu addition in the quartz
nanometers of the crystals (e.g., Vig et al. 1977; Laffey structure and the inclusions for quartz veins HVA and
et al. 1994; Pinilla et al. 2012). Such effect has been imaged HVB. In addition, a correlation between Cu-enriched sub-
on an olivine grain by Pinilla et al. (2012). These modifi- surface layers and Cu enrichment in the quartz structure
cations result from mechanical deformations, creation of and/or their hosted HSMIs is observed in HQA1200 for all
planar defects in the crystal structure, and the production heating steps below 1200 °C and for HQB900 and H QB900T
of dangling bonds and trapped electrons in the sub-surface (Figs. 7, 10). By contrast, negligible Cu sub-surface enrich-
(Rémond et al. 2002; Pinilla et al. 2012). As a consequence, ment is observed for H QA600 and HQA1200(HNO3), which
physical properties of a polished crystal differ within the points toward a limited Cu incorporation in their structures
first hundreds of nanometers from the bulk. Pinilla et al. and/or their hosted HSMIs (Figs. 7, 10).
(2012) showed by modeling that damaged surfaces of oli- To summarize, a systematic correlation is generally
vine and quartz have a high capacity to incorporate cations. observed between a Cu-rich sub-surface layers measured
This could explain the higher Cu concentrations detected by EPMA and subsequent LA-ICP-MS analyses revealing
13
394
Cu enrichment up to two orders of magnitude in their struc- quartz have only been reported for a temperature of 800 °C
tures and/or hosted inclusions (SMIs and HSMIs). There- (2.9 × 10−10 m2/s, Lerchbaumer and Audétat 2012). The Cu
fore, the detection of Cu by EPMA is an indirect indication diffusion coefficients at 600 and 900 °C were calculated
that Cu was added to the sample from an external source using a similar method to that of Lerchbaumer and Audétat
and that diffusion occurred. Although the detection of Cu (2012) by estimating the necessary flux of copper through
enrichment by EPMA is a reliable and fast way to diag- magmatic quartz to account for the increase of Cu concen-
nostic Cu addition and diffusion in the sample, its absence tration in heated SMIs from MQ600 and MQ900 and using
does not rule out Cu addition and diffusion as suggested by Fick’s first law of diffusion:
the results obtained in MQ900(HNO3) (Fig. 8).
𝜕𝜃
J = −D × ,
𝜕x
Diffusion of elements into SMIs and HSMIs
which relates the flux, J (e.g., mol/m2s), to the diffusion
LA-ICP-MS analyses of heated SMIs reveal both enrich- coefficient, D (m2/s), and the variation of concentration, 𝜕𝜃
ment and depletion of Cu, Li, Ag, and K concentrations (mol/m3), over a distance, 𝜕x (m), in the sample.
(Fig. 8). The recorded modifications of Cu, Li, and Ag As the diffusion of monovalent cations through quartz
concentrations in SMIs during heating experiments cor- occurs mostly perpendicular to the c-axis (along channel-
roborate previous studies (e.g., Kamenetsky and Danyush- like structures), Fick’s law of diffusion is reduced to its
evsky 2005; Zajacz et al. 2009). These elements are small simple one-dimensional form (reflecting only mass trans-
monovalent cations having ionic radii of ~1 Å or smaller. fer parallel to the c-axis). The melt inclusions are consid-
According to Verhoogen (1952), White (1970) and Zajacz ered to be spherical, with diameters of 40 µm, and to be
et al. (2009), they diffuse along the large open channel- localized 100 µm below the surface of the quartz crystal.
like structures (Ø ≈ 1 Å), which are parallel to the c-axis Based on LA-ICP-MS analyses of the host quartz, we have
of the quartz structure. Recent studies argued that there is estimated a Cu concentration of 1 ppm. Mean Cu concen-
no diffusion of K+ upon heating, assuming that they are trations of heated SMIs (35 and 330 ppm for SMIs from
immobile in the quartz structure due to their larger ionic MQ600 and MQ900, respectively) are used as the values
radius (1.38 Å; Kamenetsky and Danyushevsky 2005; Li for Cu gain within 6 h (considering initial Cu concentra-
et al. 2009; Zajacz et al. 2009; Lerchbaumer and Audétat tion of heated SMIs to be negligible). Calculated mini-
2012). Our study shows a decrease of K concentrations mum diffusion coefficients are 4.3 × 10−12 m2/s at 600 °C
in heated SMIs from MQ600, MQ900(HNO3), MQ900, and and 4.1 × 10−11 m2/s at 900 °C (Fig. 11). These values are
MQ900(MF) (Fig. 8); yet, no correlation with heating tem- lower than the one estimated by Lerchbaumer and Audétat
peratures has been observed. This suggests that K is able (2012), 2.9 × 10−10 m2/s at 800 °C, but they are not incon-
to diffuse through the quartz structure, which is in agree- sistent considering that they are minimum estimations
ment with the seminal studies of Verhoogen (1952), White (Fig. 11). The slope of Cu diffusivity as a function of tem-
(1970), and Kronenberg and Kirby (1987), which shows the perature constrained by the diffusion coefficients at 600 and
diffusion of K into quartz along the large open channel-like 900 °C is also consistent with the data of Lerchbaumer and
structures parallel to the c-axis. Audétat (2012) for Cu (Fig. 11) and the data of Verhoogen
A comparison of the composition of heated and (1952) and Frischat (1970) for Li and Na.
unheated HSMIs is difficult due to the limited number of
analyses and the nature of HSMIs that have variable pro- Cation incorporation in the quartz structure
portions of silicate glass and metal-rich hypersaline liquid
(Rottier et al. 2016b). Copper concentration in HSMIs is Monovalent cations are incorporated into the quartz struc-
clearly affected by heating (Fig. 10). The observed increase ture in interstitial sites located in large channel-like struc-
of Cs, Na, and, to a lesser extent, Rb concentrations could tures parallel to the c-axis with the net result of balancing
be attributed to both heating-related diffusion and natural the charge deficiency created by the substitution of triva-
chemical variability of the HSMIs. lent cations such as A l3+ or B
3+ for S
i4+ (Fig. 1; Weil 1984;
Our experiments were not aimed at determining dif- Götze 2009). Our results reveal a striking contrast of the
fusion coefficients, and therefore we can only attempt to behavior of trace elements between magmatic and hydro-
provide rough estimates. The speed at which an inclusion thermal quartz.
reequilibrates is governed by the diffusivity of the diffus- Heated magmatic quartz shows only minor composi-
ing species and its solubility in the host (Qin et al. 1992). tional modifications upon heating, including slight Cu, Na,
Thus, diffusivities of monovalent cations may only be and/or B enrichment together with a subtle depletion in Li
estimated for magmatic quartz where their solubility is (Figs. 7a, 9a–c). Unheated magmatic quartz contains higher
low and could be ignored. Copper diffusion coefficients in molar concentrations of pentavalent (P5+) and monovalent
13
395
characterized by a lack of monovalent (Li+, Na+, and C u+)

5+
and pentavalent ( P ) cations compared to trivalent cations
(B3+ and Al3+; Fig. 12b). The deficiency of monovalent
cations observed is attributed to the presence of H+, which
is commonly described in hydrothermal quartz (Miyoshi
et al. 2005; Götze 2009; Jourdan et al. 2009; Müller and
Koch-Müller 2009). The calculated concentration of H+
in quartz prior to heating is up to 16 ppm [Molar concen-
tration of H+ = Σ(Al3++B3+) − Σ(P5++Li++Cu++Na+)]
(Fig. 12; Landtwing and Pettke 2005; Allan and Yardley
2007). Heated hydrothermal quartz displays an increase of
Li, and/or Na, and/or Cu concentrations, and consequently
almost all charge defects created by A l3+ and B
3+ are bal-
+ + +
anced by Li , Na , and C u in H
QA1200, HQA1200(HNO3),
HQB900, and HQB900T (Fig. 11b). Both HQA1200 and
HQA1200(HNO3) display almost identical molar concentra-
tions of monovalent (Li+, Na+, and Cu+) and pentavalent
(P5+) cations compared to the molar concentrations of tri-
Fig. 11 Diffusion coefficient as a function of temperature. Red stars valent cations (B3+ and Al3+; Fig. 12b). The lack of Cu
represent the calculated minimum diffusion coefficients for Cu at 600 enrichment in H QA1200(HNO3) with respect to H QA1200 is
and 900 °C, and the red dashed line the extrapolation to other tem-
peratures (this study). The gray triangle and dashed line represent,
balanced by a more important incorporation and enrich-
respectively, the calculated minimum diffusion coefficients for Cu at ment of Na (Figs. 7b, 9d). Based on our results, we con-
800 °C and its extrapolation to other temperatures published by Ler- clude that H+ has been almost entirely replaced during
chbaumer and Audétat (2012). The figure also shows published dif- heating experiments in our hydrothermal quartz samples.
fusion coefficients for Li and Na published by Verhoogen (1952) and
Frischat (1970), respectively. The dashed blue line indicates the α- to
We therefore propose that monovalent cations are diffused
β-quartz transition and subsequently incorporated in quartz in interstitial sites
initially occupied by H+. The ability of quartz to incorpo-
rate diffusing elements seems to be directly correlated to
(Li+, Na+, and Cu+) cations in contrast to trivalent cations, the concentration of H+ cations initially present in quartz.
which results in a positive charge excess (Fig. 12a). This Based on our experiments, we conclude that the substitu-
excess is probably an artifact of the high detection limit tion of H + in hydrothermal quartz by diffusive monovalent
(~25 ppm) for the trivalent cation Fe3+. In order to satisfy cations, and their respective proportion, is largely depend-
the charge balance during heating experiments, the incor- ent on the temperature and the environment of the quartz
poration of new monovalent cations like Na+ and Cu+ in and to some extent chemical pre-treatment (Figs. 7c, 9d–f).
quartz should be associated with the coeval incorporation In comparison, we have shown that in magmatic quartz,
of complementary trivalent cations or by the replacement poor in H+, incorporation of diffusive monovalent cations
of monovalent cations initially present in the structure of is limited and mostly restricted to substitution of Li+.
the quartz (e.g., L i+). Boron is incorporated as B
3+ and its
concentration increases in heated quartz (Fig. 7a); however, Source of the diffusive elements
it is insufficient to balance the observed enrichment in N a+
and Cu+. Therefore, the incorporation of N a+ or C
u+ must The source of the elements enriched in SMIs, HSMIs, and
be accompanied by the substitution of another monovalent quartz could be external to the studied quartz (i.e., sur-
cation initially present in the structure. The best candi- rounding minerals, Linkam TS1500 stage) or from solid or
date among the monovalent cations is Li+ considering the fluid inclusions hosted in quartz. In hydrothermal quartz,
decreasing Li concentration in heated quartz and its sys- diffusion of Cu from Cu-bearing sulfides (mainly chalcopy-
tematic negative correlation with Na and Cu (Figs. 7a, 9c). rite) in quartz is demonstrated by Cu enrichment around the
The observed depletion in Li along with the increase in B chalcopyrite grain after heating the H
QB900 and HQB900(T)
contents is sufficient to compensate for the enrichment in samples (Figs. 6, A.4). The source of Cu in magmatic
Na and Cu observed in magmatic quartz (Fig. 12a). quartz could be assigned to the occurrence of unidenti-
In hydrothermal quartz, heating experiments resulted in fied sparse Cu-bearing magmatic sulfide blebs hosted by
more dramatic Li, Na, and Cu concentration changes com- igneous rock-forming minerals in the surrounding matrix.
pared to magmatic quartz (Figs. 7b, c, 9d, f). Unheated Previous studies have shown that the source of Cu and
hydrothermal quartz samples HQA0 and H QB0 are Ag enrichment in SMIs could be an external independent
13
396
Fig. 12 Correlation diagrams
of the calculated sum of P, Li,
Na, and Cu molar concentra-
tions vs. the sum of Al and B
molar concentrations (in molt/t)
for the analyzed magmatic
quartz (a) and the hydrothermal
quartz crystals (b)
source, most likely the heating device itself and probably dissolving potential sulfides, the effect of H
NO3 pre-treat-
carried by the gas phase (Kamenetsky and Danyushevsky ment results in chemical healing of surface defects created
2005; Zajacz et al. 2009). The external source of contami- during polishing. Chemical treatment of quartz to remove
nation is attributed to the heating device and more spe- defects created during mechanical polishing is common
cifically to the copper pins connecting the thermocouple practice in the polishing of quartz resonators using NH4
(Linkam TS1500 stage manual, version 1.0). F.HF, HF, HCl, or NaOH as chemical reactants (e.g., Vig
In order to test whether Cu is sourced from Cu-bear- et al. 1977; Tellier 1982; Laffey et al. 1994; Zhang 2001).
ing magmatic sulfides present in the surrounding rock- To date, no test using concentrated HNO3 has been carried
forming minerals or from the heating stage, we mechani- out. We suggest that pre-treatment with concentrated HNO3
cally removed the groundmass surrounding the magmatic leads to partial dissolution of the damaged surface gener-
quartz crystal MQ900(MF). Despite this, the Cu enrich- ating a chemical polishing of our quartz in a similar way
ment remained the same in both SMIs within matrix-free as it has been observed for chemical polishing by HCl (see
MQ900(MF) and within MQ900 (Fig. 8). Consequently, it above). As a consequence, Cu accumulation in the sub-
is unlikely that the magmatic groundmass and unidenti- surface is limited, thereby decreasing the Cu concentra-
fied Cu-bearing magmatic sulfide represent the exter- tion gradient between the surface and SMIs, and adversely
nal source of Cu. Thus, the main Cu source must be the affecting its diffusion rate (Zhang 2010).
Linkam TS1500 stage. Quartz MQ900(HNO3) pre-treated The sources of the Ag and Na, enriched in the quartz
with HNO3 showed only limited Cu enrichment in its structure and/or their hosted inclusions, remain uncon-
hosted SMIs and no copper enrichment in its structures strained. Silver could be sourced by the Linkam stage,
compared to untreated quartz heated at the same tempera- but additional investigations are necessary to confirm this
ture (MQ900 and M Q900(MF)). A similar effect of H
NO3 was hypothesis. We observe Na enrichment for both magmatic
also observed on quartz from HVA and hosted HSMIs. and hydrothermal quartz. Although unconstrained, we sug-
Therefore, we argue that HNO3 pre-treatment is a very effi- gest that potential sources of Na are (1) surrounding Na-
cient way to limit Cu diffusion. We believe that, aside from bearing minerals, (2) Na-bearing elements present in the
13
397
Linkam TS1500 stage (e.g., ceramic cup), and/or (3) Na- may result in erroneous geological interpretation of mag-
bearing inclusions in quartz (e.g., fluid inclusions, solid matic–hydrothermal processes. In particular, interpretation
inclusions). Sodium is known to diffuse out of fluid inclu- of re-homogenized SMIs and HSMIs must be undertaken
sions during heating experiments (Li et al. 2009; Zajacz with caution, especially when studying Cu transport and
et al. 2009; Lerchbaumer and Audétat 2012). Therefore, precipitation processes in the realm of Cu-porphyry deposit
for hydrothermal quartz, hypersaline fluid inclusions are a genesis.
good candidate for the source of Na.
Acknowledgements The present investigation was supported
by the Swiss National Science Foundation (FN 200020_160071;
200020_155928; 200020_168996). We gratefully acknowledge Jean-
Conclusions and implications Marie Boccard for his precious experience with sample preparation
and Aaron Lee Hantsche for his help. We are grateful to Daniele
EPMA analyses reveal that sub-surface Cu enrichment Cherniak and Andreas Audétat for their constructive comments and to
Hans Keppler for his editorial work.
increases with heating in quartz without HNO3 pre-treat-
ment. However, such results are not supported by LA-ICP-
MS analyses, or by EPMA, after re-polishing of the sam-
ple. We argue that EPMA analyses record a sub-surface
layer Cu enrichment in quartz crystals owing to defects cre-
References
ated during sample polishing. Regarding the high capacity Allan MM, Yardley BWD (2007) Tracking meteoric infiltration into
of sub-surface layers to incorporate Cu (up to 2300 ppm) a magmatic-hydrothermal system: a cathodoluminescence, oxy-
and the observed correlation with Cu enrichment in the gen isotope and trace element study of quartz from Mt. Leyshon,
bulk crystal and hosted inclusions detected by LA-ICP-MS Australia. Chem Geol 240:343–360
Baumgartner R, Fontboté L, Vennemann T (2008) Mineral zoning
analyses, we propose that Cu detection by EPMA analyses and geochemistry of epithermal polymetallic Zn–Pb–Ag–Cu–Bi
indicates Cu uptake from an external source. We propose mineralization at Cerro de Pasco, Peru. Econ Geol 103:493–537
that this approach could be used as a direct indication of Cu Campos E, Touret JLR, Nikogosian I, (2006) Magmatic fluid inclu-
diffusion into quartz from an external source and may help sions from the Zaldívar deposit, northern Chile. The role of early
metal-bearing fluids in a porphyry copper system. Resour Geol
avoid a biased geological interpretation by distinguishing 56:1–8
artificial from natural Cu enrichment in SMIs, HSMIs, or Cherniak DJ, Watson EB, Wark DA (2007) Ti diffusion in quartz.
fluid inclusions during heating experiments. Chem Geol 236:65–74
LA-ICP-MS analyses of quartz and hosted SMIs and Currie LA (1968) Limits for qualitative detection and quantita-
tive determination. Application to radiochemistry. Anal Chem
HSMIs reveal the diffusion of a large number of monova- 40:586–593
lent cations, including Cu+, Li+, Na+, Ag+, and possibly K
+ Davidson P, Kamenetsky VS (2007) Primary aqueous fluids in rhy-
3+
and the trivalent cation B . For the first time, we docu- olitic magmas: melt inclusion evidence for pre- and post-trap-
ment the modification of K concentration in heated SMIs. ping exsolution. Chem Geol 237:372–383
Dolino G (1990) The α-inc-β transitions of quartz: a century of
Furthermore, we demonstrate that some diffusing ele- research on displacive phase transitions. Phase Transit 21:59–72
ments (Cu, Li, Na, and B) could be accommodated by or be Esposito R, Klebesz R, Bartoli O, Klyukin Y, Moncada D, Doherty A,
removed from the quartz structure during heating experi- Bodnar R, (2012) Application of the Linkam TS1400XY heating
ments. In magmatic quartz, incorporation of Na and Cu stage to melt inclusion studies. Open Geosci 4:208–218
Farver JR, (2010) Oxygen and hydrogen diffusion in minerals. Rev
is limited to a few ppm and occurs by replacement of Li, Miner Geochem 72:447–507
whereas hydrothermal quartz is able to incorporate several Freer R, Dennis PF (1982) Oxygen diffusion studies 1. A preliminary
hundreds of ppm of Na and Cu in its structure by substitut- microprobe investigation of oxygen diffusion in some rock form-
ing for H+ during heating. The nature of monovalent cati- ing minerals. Miner Mag 45:147–179
Frischat GH (1970) Sodium diffusion in natural quartz crystals. J Am
ons incorporated in quartz depends on the availability of Ceram Soc 53:357–357
external sources, such as surrounding minerals or compo- Götze J (2009) Chemistry, textures and physical properties of quartz–
nents constituting the heating device. Pre-treatment of the geological interpretation and technical application. Miner Mag
samples with concentrated H NO3 appears to be an effective 73:645–671
Grant NE, McIntosh KR, (2009) Passivation of a (100) silicon surface
approach to limit Cu accumulation in the sub-surface and by silicon dioxide grown in nitric acid. IEEE Electron Device
its subsequent incorporation in quartz and hosted SMIs and Lett 30:922–924
HSMIs. Guillong M, Heinrich CA, (2007) LA-ICP-MS analysis of inclusions:
Finally, our experiments document compositional improved ablation and detection. European Current Research On
Fluid Inclusions (ECROFI-XIX), Bern, p 82
changes in quartz, SMI, and HSMI at temperatures as Guillong M, Meier DL, Allan MM, Heinrich CA, Yardley BWD
low as 600 °C using a Linkam stage TS1500. Failing (2008) SILLS. a Matlab-based program for the reduction of
to recognize diffusion and subsequent incorporation of Laser Ablation ICP-MS data of homogeneous materials and
the identified set of elements (Na, K, Li, Cu, Ag, and B) inclusions. In: Sylvester P (ed) Laser-ablation-ICPMS in the
13
398
earth sciences: current practices and outstanding issues. Mineral- Mortley WS (1969) Diffusion paths in quartz. Nature 221:359–360
ogical Association of Canada, Vancouver, pp 328–333 Müller A, Koch-Müller M (2009) Hydrogen speciation and trace ele-
Günther D, Frischknecht R, Heinrich CA, Kahlert HJ (1997) Capa- ment contents of igneous, hydrothermal and metamorphic quartz
bilities of an Argon Fluoride 193 nm excimer laser for laser abla- from Norway. Miner Mag 73:569–583
tion inductively coupled plasma mass spectrometry microanaly- Pinilla C, Davis SA, Scott TB, Allan NL, Blundy JD, (2012) Interfa-
sis of geological materials. J Anal At Spectrom 12:939–944 cial storage of noble gases and other trace elements in magmatic
Günther D, Audétat A, Frischknecht R, Heinrich CA (1998) Quantita- systems. ‎Earth Planet Sci Lett 319:287–294
tive analysis of major, minor and trace elements in fluid inclu- Poignon C, Jeandel G, Morlot G (1996) Study of ionic impurity
sions using laser ablation–inductively coupled plasma mass mobility in quartz crystals by impedance and thermionic current
spectrometry. J Anal At Spectrom 13:263–270 measurements. ‎J Appl Phys 80:6192–6197
Halter WE, Pettke T, Heinrich CA, Roten-Rutishauser B (2002) Qin Z, Lu F, Anderson AT (1992) Diffusive reequilibration of melt
Major to trace element analysis of melt inclusions by laser-abla- and fluid inclusions. Am Miner 77:565–576
tion ICP-MS: methods of quantification. Chem Geol 183:63–86 Raghavan G, Chiang C, Anders PB, Tzeng SM, Villasol R, Bai G,
Harris AC, Kamenetsky VS, White NC, van Achterbergh E, Ryan CG Fraser DB (1995) Diffusion of copper through dielectric films
(2003) Melt inclusions in veins: linking magmas and porphyry under bias temperature stress. Thin Solid Films 262:168–176
Cu deposits. Science 302:2109–2111 Rémond G, Nockolds C, Phillips M, Roques-Carmes C (2002) Impli-
Heaney PJ, (1994) Structure and chemistry of the low-pressure silica cations of polishing techniques in quantitative X-ray microanaly-
polymorphs. Rev Miner Geochem 29:1–40 sis. J Res Natl Inst Stand Technol 107:639–662
Heinrich CA, Pettke T, Halter WE, Aigner-Torres M, Audétat A, Rottier B, Kouzmanov K, Wälle M, Bendezú R, Fontboté L (2016a)
Günther D, Hattendorf B, Bleiner D, Guillong M, Horn I (2003) Sulfide replacement processes revealed by textural an LA-ICP-
Quantitative multi-element analysis of minerals, fluid and melt MS trace element analyses: example from the early mineraliza-
inclusions by laser-ablation inductively-coupled-plasma mass- tion stages at Cerro de Pasco, Peru. Econ Geol 111:1347–1367
spectrometry. Geochim Cosmochim Acta 67:3473–3496 Rottier B, Kouzmanov K, Bouvier AS, Baumgartner L, Wälle M,
Huang R, Audétat A (2012) The titanium-in-quartz (TitaniQ) thermo- Rezeau H, Bendezú R, Fontboté L (2016b) Heterogeneous melt
barometer: a critical examination and re-calibration. Geochim and hypersaline liquid inclusions in shallow porphyry type min-
Cosmochim Acta 84:75–89 eralization as markers of the magmatic-hydrothermal transition
Ihinger PD, Zink SI (2000) Determination of relative growth rates of (Cerro de Pasco district, Peru). Chem Geol 447:93–116
natural quartz crystals. Nature 404:865–869 Rusk BG, Lowers HA, Reed MH (2008) Trace elements in hydrother-
Jourdan AL, Vennemann TW, Mullis J, Ramseyer K, Spiers CJ (2009) mal quartz: relationships to cathodoluminescence textures and
Evidence of growth and sector zoning in hydrothermal quartz insights into vein formation. Geology 36:547–550
from Alpine veins. Eur J Miner 21:219–231 Rybach L, Laves F (1967) Sodium diffusion experiments in quartz
Kamenetsky VS, Danyushevsky LV (2005) Metals in quartz-hosted crystals. Geochim Cosmochim Acta 31:539–545
melt inclusions: natural facts and experimental artefacts. Am Schneider CA, Rasband WS, Eliceiri KW (2012) NIH image to
Miner 90:1674–1678 ImageJ: 25 years of image analysis. Nat Methods 9:671–675
Koděra P, Heinrich CA, Wälle M, Lexa J (2014) Magmatic salt melt Seo JH, Heinrich CA (2013) Selective copper diffusion into quartz-
and vapor: extreme fluids forming porphyry gold deposits in hosted vapor inclusions: evidence from other host minerals, driv-
shallow subvolcanic settings. Geology 42:495–498 ing forces, and consequences for Cu–Au ore formation. Geochim
Kronenberg AK, Kirby SH (1987) Ionic conductivity of quartz: DC Cosmochim Acta 113:60–69
time dependence and transition in charge carriers. Am Mineral Stefanova E, Driesner T, Zajacz Z, Heinrich CA, Petrov P, Vasilev Z
72:739–747 (2014) Melt and fluid inclusions in hydrothermal veins: the mag-
Laffey S, Hendrickson M, Vig JR, (1994) Polishing and etching lan- matic to hydrothermal evolution of the Elatsite porphyry Cu–Au
gasite and quartz crystals. In: Frequency Control Symposium, Deposit, Bulgaria. Econ Geol 109:1359–1381
1994. 48th., Proceedings of the 1994 IEEE International, pp Student JJ, Bodnar RJ (2004) Silicate melt inclusions in porphyry
245–250 copper deposits: Identification and homogenization behavior.
Lakshtanov DL, Sinogeikin SV, Bass JD (2007) High-temperature Can Miner 42:1583–1599
phase transitions and elasticity of silica polymorphs. Phys Chem Tellier CR (1982) Some results on chemical etching of AT-cut
Miner 34:11–22 quartz wafers in ammonium bifluoride solutions. J Mater Sci
Landtwing MR, Pettke T, (2005) Relationships between SEM- 17:1348–1354
cathodoluminescence response and trace-element composition of Thomas JB, Cherniak DJ, Watson EB (2008) Lattice diffusion and
hydrothermal vein quartz. Am Miner 90:122–131 solubility of argon in forsterite, enstatite, quartz and corundum.
Lerchbaumer L, Audétat A (2012) High Cu concentrations in vapor Chem Geol 253:1–22
type fluid inclusions: an artifact? Geochim Cosmochim Acta Thomas JB, Watson EB, Spear FS, Shemella PT, Nayak SK, Lanzi-
88:255–274 rotti A (2010) TitaniQ under pressure: the effect of pressure and
Li Y, Audétat A, Lerchbaumer L, Xiong XL (2009) Rapid Na, Cu temperature on the solubility of Ti in quartz. Contrib Miner Pet-
exchange between synthetic fluid inclusions and external aque- rol 160:743–759
ous solutions: evidence from LA-ICP-MS analysis. Geofluids Ulrich T, Günther D, Heinrich CA (2002) The evolution of a por-
9:321–329 phyry Cu-Au deposit, based on LA-ICP-MS analysis of fluid
McBrayer JD, Swanson RM, Sigmon TW (1986) Diffusion of metals inclusions: Bajo de la Alumbrera, Argentina. Econ Geol
in silicon dioxide. J Electrochem Soc 133:1242–1246 97:1888–1920
Mercer CN, Reed MH, Mercer CM, (2015) Time scales of porphyry Verhoogen J, (1952) Ionic diffusion and electrical conductivity in
cu deposit formation: insights from titanium diffusion in quartz. quartz. Am Miner 37:637–655
Econ Geol 110:587–602 Vig JR, Lebus JW, Filler RL, (1977) Chemically polished quartz. In:
Milne EL, Gibbs P (1964) Ag ion migration in α-quartz. ‎J Appl Phys Proceedings of IEEE 31st annual symposium on frequency con-
35:2364–2367 trol, pp 131–143
Miyoshi N, Yamaguchi Y, Makino K (2005) Successive zoning of Al Wark DA, Watson EB (2006) TitaniQ: a titanium-in-quartz geother-
and H in hydrothermal vein quartz. Am Miner 90:310–315 mometer. Contrib Miner Petrol 152:743–754
13
399
Watson EB, Cherniak DJ, Thomas JB, Hanchar JM, Wirth R (2016) inclusions: are all metal concentrations unmodified? Geochim
Crystal surface integrity and diffusion measurements on earth Cosmochim Acta 73:3013–3027
and planetary materials. Earth Planet Sci Lett 450:346–354 Zelený M, Hegedüs J, Foster AS, Drabold DA, Elliott SR, Nieminen
Weil JA (1984) A review of electron spin spectroscopy and its appli- RM, (2012) Ab initio study of Cu diffusion in α-cristobalite.
cation to the study of paramagnetic defects in crystalline quartz. ‎New J Phys 14:1130–1139
Phys Chem Miner 10:149–165 Zhang XG, (2001) Etching of oxides: in electrochemistry of silicon
White S (1970) Ionic diffusion in quartz. Nature 225:375–376 and its oxide, 1st edn. Springer, US, pp 131–165
Zajacz Z, Hanley JJ, Heinrich CA, Halter WE, Guillong M (2009) Zhang Y, (2010) Diffusion in minerals and melts: theoretical back-
Diffusive reequilibration of quartz-hosted silicate melt and fluid ground. Rev Miner Geochem 72:5–59
13
400
Figure A.1:
Figure A.1: SEM-CL image of studied quartz HQA1200(HNO3) after heating run at 1200°C, with EPMA and LA-ICP-
MS spots location; B) Copper concentration obtained by EPMA along profile 1-2; C) Al concentration obtained by
EPMA along profile 1-2; D) Cu Kα map after heating run at 1200°C; E) Ti Kα map after heating run at 1200°C; F)
Al- Kα map after heating run at 1200°C
401
Figure A.2:
Figure A.2: A) SEM-CL image of studied quartz HQA1200T after heating run at 1200°C, with EPMA and LA-ICP-MS
spots location; B) Copperb and Al concentration obtained by EPMA along profile 1-2; C) Cu Kα map after heating
run at 1200°C; E) Ti Kα map after heating run at 1200°C; F) Al- Kα map after heating run at 1200°C
402
Figure A.3:
Figure A.3: A) SEM-CL image of studied quartz HQA600 after heating run at 600°C, with EPMA and LA-ICP-MS
spots location; B) Al Kα map after heating run at 600°C; C) Al Kα map after heating run at 600°C.
403
Figure A.4:
Figure A.4: SEM-CL imagesof studied quartz HQB900T after heating run at 900°C, with EPMA and LA-ICP-MS
spots location; B) Copper concentration obtained by EPMA along profile 1-2; C) Copper concentration obtained by
EPMA along profile 3-4; D) Al Kα map after heating run at 900°C; E) Cu Kα map after heating run at 900°C.
404
Table A.1: Whole rock analyses (XRF + LA-ICP-MS)
of the Rhyodacitic dome
Sampl Rhyodacitic dome

Easting 360320
Northing 8819640
analyse- type XRF+LAICPMS
SiO2 (wt.%) 67,9
TiO2 (wt.%) 0,66
Al2O3 (wt.%) 16,3
Fe2O3 (wt.%) 2,58
MnO (wt.%) 0,03
MgO (wt.%) 0,9
CaO (wt.%) 2,17
Na2O (wt.%) 4,15
K2O (wt.%) 3,88
P2O5 (wt.%) 0,23
LOI (wt.%) 1,02
Be_ppm 4
Na_ppm 25073
Mg_ppm 5125
Al_ppm 86052
Si_ppm 264559
P_ppm 631
K_ppm 27318
Ca_ppm 14389
Sc_ppm 4,62
Ti_ppm 3431
V_ppm 52,2
Cr_ppm 11
Mn_ppm 174
Fe_ppm 14154
Co_ppm 3,56
Ni_ppm 8,44
Cu_ppm 7,04
Zn_ppm 47,1
Ga_ppm 20,2
Ge_ppm B.D.L
As_ppm 1,61
Rb_ppm 109
Sr_ppm 823
Y_ppm 9,09
Zr_ppm 160
Nb_ppm 14,3
Mo_ppm 0,54
Sn_ppm 2,82
Sb_ppm 0,55
Te_ppm B.D.L
Cs_ppm 4,68
Ba_ppm 787
La_ppm 40,3
Ce_ppm 81,7
405
Table A.1: Whole rock analyses (XRF + LA-ICP-MS)
of the Rhyodacitic dome
Pr_ppm 9,48
Nd_ppm 34,9
Sm_ppm 5,59
Eu_ppm 1,26
Gd_ppm 3,74
Tb_ppm 0,41
Dy_ppm 1,9
Ho_ppm 0,3
Er_ppm 0,75
Tm_ppm 0,09
Yb_ppm 0,63
Lu_ppm 0,06
Hf_ppm 4,21
Ta_ppm 1,01
W_ppm 0,74
Tl_ppm 0,18
Pb_ppm 14
Bi_ppm B.D.L
Th_ppm 11,3
U_ppm 3,05
N.A.: Not Analyzed
406
Table A.2: EPMA results from the different quartz crystals
Limit of determination*: Al = 0.0056 wt.%; Ti = 0.0077 wt.%; Cu = 0.0099 wt.%
Slabs N° spot Heating step Al (wt.%) Ti (wt.%) Cu (wt.%)
MQ600 1 22°C 0,006 B.D.L B.D.L
MQ600 2 22°C B.D.L B.D.L B.D.L
MQ600 3 22°C B.D.L B.D.L B.D.L
MQ600 1 520°C 0,007 B.D.L B.D.L
MQ600 2 520°C 0,007 B.D.L B.D.L
MQ600 3 520°C 0,010 B.D.L B.D.L
MQ600 4 520°C 0,009 B.D.L B.D.L
MQ600 5 520°C 0,006 B.D.L B.D.L
MQ600 1 600°C B.D.L B.D.L B.D.L
MQ600 2 600°C B.D.L B.D.L B.D.L
MQ600 3 600°C B.D.L B.D.L B.D.L
MQ600 4 600°C B.D.L B.D.L B.D.L
MQ600 5 600°C B.D.L B.D.L B.D.L
MQ600 1 after polishing B.D.L B.D.L B.D.L
MQ900 1 900°C B.D.L B.D.L 0,038
MQ900 2 900°C B.D.L B.D.L 0,045
MQ900 3 900°C B.D.L B.D.L 0,050
MQ900 4 900°C B.D.L B.D.L 0,071
407
MQ900 19 after polishing B.D.L 0,008 B.D.L
MQ900 24 after polishing B.D.L 0,008 B.D.L
MQ900 29 after polishing B.D.L B.D.L 0,018
MQ900(MF) 1 900°C 0,007 B.D.L 0,097
MQ900(MF) 2 900°C 0,008 B.D.L 0,072
MQ900(MF) 3 900°C 0,009 B.D.L 0,064
MQ900(MF) 4 900°C 0,006 B.D.L 0,047
MQ900(MF) 5 900°C 0,008 B.D.L 0,044
MQ900(MF) 6 900°C B.D.L B.D.L 0,032
MQ900(MF) 7 900°C 0,007 B.D.L 0,034
MQ900(MF) 8 900°C 0,032 B.D.L 0,031
MQ900(MF) 9 900°C 0,008 B.D.L 0,032
MQ900(MF) 10 900°C 0,035 0,013 0,032
MQ900(MF) 1 after polishing B.D.L B.D.L B.D.L
MQ900(MF) 5 after polishing 0,074 B.D.L B.D.L
408
MQ900(HNO3) 1 900°C B.D.L 0,009 B.D.L
MQ900(HNO3) 2 900°C B.D.L B.D.L B.D.L
MQ900(HNO3) 6 900°C 0,006 B.D.L B.D.L
MQ900(HNO3) 1 after polishing B.D.L B.D.L B.D.L
MQ900(HNO3) 2 after polishing 0,373 B.D.L B.D.L
MQ900(HNO3) 14 after polishing B.D.L 0,010 B.D.L
HQA1200 (profile 1-2) 1 22°C 0,034 B.D.L B.D.L
HQA1200 (profile 1-2) 4 22°C 0,035 0,016 B.D.L
HQA1200 (profile 1-2) 5 22°C 0,034 0,016 B.D.L
HQA1200 (profile 1-2) 6 22°C 0,060 0,032 B.D.L
HQA1200 (profile 1-2) 7 22°C 0,036 0,017 B.D.L
HQA1200 (profile 1-2) 8 22°C 0,033 0,018 B.D.L
HQA1200 (profile 1-2) 9 22°C 0,038 0,024 B.D.L
HQA1200 (profile 1-2) 10 22°C 0,031 0,014 B.D.L
HQA1200 (profile 1-2) 10 400°C 0,037 0,014 B.D.L
HQA1200 (profile 1-2) 9 400°C 0,033 0,017 B.D.L
HQA1200 (profile 1-2) 8 400°C 0,098 0,039 B.D.L
HQA1200 (profile 1-2) 7 400°C 0,132 0,044 B.D.L
HQA1200 (profile 1-2) 6 400°C 0,029 0,012 B.D.L
HQA1200 (profile 1-2) 5 400°C 0,036 0,018 B.D.L
409
HQA1200 (profile 1-2) 2 400°C 0,038 B.D.L 0,011
HQA1200 (profile 1-2) 1 400°C 0,032 B.D.L 0,015
HQA1200 (profile 1-2) 1 600°C 0,029 B.D.L 0,039
HQA1200 (profile 1-2) 2 600°C 0,038 B.D.L 0,033
HQA1200 (profile 1-2) 3 600°C 0,026 B.D.L 0,029
HQA1200 (profile 1-2) 4 600°C 0,026 0,012 0,022
HQA1200 (profile 1-2) 5 600°C 0,035 0,019 0,026
HQA1200 (profile 1-2) 6 600°C 0,022 0,010 0,017
HQA1200 (profile 1-2) 7 600°C 0,022 0,017 0,020
HQA1200 (profile 1-2) 8 600°C 0,027 0,018 0,020
HQA1200 (profile 1-2) 9 600°C 0,035 0,013 0,021
HQA1200 (profile 1-2) 10 600°C 0,032 0,011 0,018
HQA1200 (profile 1-2) 11 600°C 0,030 B.D.L 0,019
HQA1200 (profile 1-2) 12 600°C 0,038 B.D.L 0,018
HQA1200 (profile 1-2) 13 600°C 0,028 B.D.L 0,019
HQA1200 (profile 1-2) 1 700°C 0,028 B.D.L 0,042
HQA1200 (profile 1-2) 2 700°C 0,037 B.D.L 0,031
HQA1200 (profile 1-2) 3 700°C 0,023 B.D.L 0,025
HQA1200 (profile 1-2) 4 700°C 0,025 B.D.L 0,026
HQA1200 (profile 1-2) 5 700°C 0,033 0,022 0,021
HQA1200 (profile 1-2) 6 700°C 0,015 0,010 0,018
HQA1200 (profile 1-2) 7 700°C 0,122 0,040 0,018
HQA1200 (profile 1-2) 8 700°C 0,017 0,016 0,019
HQA1200 (profile 1-2) 9 700°C 0,029 0,019 0,016
HQA1200 (profile 1-2) 10 700°C 0,035 0,015 0,013
HQA1200 (profile 1-2) 11 700°C 0,032 B.D.L 0,020
HQA1200 (profile 1-2) 12 700°C 0,031 B.D.L 0,021
HQA1200 (profile 1-2) 13 700°C 0,029 B.D.L 0,022
HQA1200 (profile 1-2) 15 800°C 0,035 B.D.L 0,039
HQA1200 (profile 1-2) 14 800°C 0,054 B.D.L 0,037
HQA1200 (profile 1-2) 13 800°C 0,032 B.D.L 0,040
HQA1200 (profile 1-2) 12 800°C 0,031 B.D.L 0,042
HQA1200 (profile 1-2) 11 800°C 0,032 0,012 0,039
HQA1200 (profile 1-2) 10 800°C 0,039 0,017 0,035
HQA1200 (profile 1-2) 9 800°C 0,060 0,016 0,038
HQA1200 (profile 1-2) 8 800°C 0,034 0,021 0,046
HQA1200 (profile 1-2) 7 800°C 0,048 0,028 0,039
HQA1200 (profile 1-2) 6 800°C 0,035 0,021 0,043
HQA1200 (profile 1-2) 5 800°C 0,038 0,017 0,050
HQA1200 (profile 1-2) 4 800°C 0,028 0,015 0,043
HQA1200 (profile 1-2) 3 800°C 0,034 0,016 0,058
HQA1200 (profile 1-2) 2 800°C 0,048 B.D.L 0,066
HQA1200 (profile 1-2) 1 800°C 0,064 B.D.L 0,095
HQA1200 (profile 1-2) 1 800°C 0,020 B.D.L 0,111
HQA1200 (profile 1-2) 2 800°C 0,027 0,011 0,076
HQA1200 (profile 1-2) 3 800°C 0,030 0,017 0,047
HQA1200 (profile 1-2) 4 800°C 0,104 0,040 0,031
HQA1200 (profile 1-2) 5 800°C 0,029 0,017 0,027
HQA1200 (profile 1-2) 6 800°C 0,063 B.D.L 0,022
410
HQA1200 (profile 1-2) 1 1200°C 0,039 B.D.L 0,033
HQA1200 (profile 1-2) 2 1200°C 0,039 B.D.L 0,034
HQA1200 (profile 1-2) 3 1200°C 0,030 B.D.L 0,024
HQA1200 (profile 1-2) 4 1200°C 0,046 B.D.L 0,032
HQA1200 (profile 1-2) 5 1200°C 0,042 0,014 0,030
HQA1200 (profile 1-2) 6 1200°C 0,032 0,010 0,027
HQA1200 (profile 1-2) 7 1200°C 0,037 0,015 0,028
HQA1200 (profile 1-2) 8 1200°C 0,104 0,031 0,041
HQA1200 (profile 1-2) 9 1200°C 0,039 0,020 0,028
HQA1200 (profile 1-2) 10 1200°C 0,041 0,020 0,022
HQA1200 (profile 1-2) 11 1200°C 0,037 0,009 0,021
HQA1200 (profile 1-2) 12 1200°C 0,036 B.D.L 0,029
HQA1200 (profile 1-2) 13 1200°C 0,041 B.D.L 0,024
HQA1200 (profile 1-2) 14 1200°C 0,033 B.D.L 0,019
HQA1200 (profile 1-2) 1 1200°C 0,038 B.D.L 0,021
HQA1200 (profile 1-2) 2 1200°C 0,040 0,015 0,015
HQA1200 (profile 1-2) 3 1200°C 0,035 0,015 0,018
HQA1200 (profile 1-2) 4 1200°C 0,057 0,027 0,020
HQA1200 (profile 1-2) 5 1200°C 0,021 0,019 0,017
HQA1200 (profile 1-2) 6 1200°C 0,018 0,015 0,024
HQA1200 (profile 1-2) 7 1200°C 0,034 0,014 0,024
HQA1200 (profile 1-2) 8 1200°C 0,070 0,031 0,031
HQA1200 (profile 1-2) 9 1200°C 0,047 0,023 0,037
HQA1200 (profile 1-2) 10 1200°C 0,038 0,018 0,030
HQA1200 (profile 1-2) 11 1200°C 0,034 0,015 0,031
HQA1200 (profile 1-2) 12 1200°C 0,033 0,009 0,032
HQA1200 (profile 1-2) 13 1200°C 0,033 B.D.L 0,035
HQA1200 (profile 1-2) 14 1200°C 0,027 B.D.L 0,031
HQA1200 (profile 1-2) 15 1200°C 0,267 B.D.L 0,088
HQA1200 (profile 1-2) 1 after polishing 0,025 0,014 B.D.L
HQA1200 (profile 1-2) 5 after polishing 0,094 0,041 0,014
HQA1200 (profile 1-2) 19 after polishing 0,029 B.D.L B.D.L
HQA1200 (profile 1-2) 20 after polishing 0,016 B.D.L B.D.L
411
HQA1200(T) 1 1200°C 0,016 0,023 0,039
HQA1200(T) 2 1200°C 0,015 0,027 0,036
HQA1200(T) 3 1200°C 0,080 0,039 0,065
HQA1200(T) 4 1200°C 0,034 0,027 0,050
HQA1200(T) 5 1200°C 0,042 0,033 0,057
HQA1200(T) 6 1200°C 0,049 0,036 0,063
HQA1200(T) 7 1200°C 0,042 0,028 0,053
HQA1200(T) 8 1200°C 0,062 0,028 0,062
HQA1200(T) 9 1200°C 0,022 0,021 0,046
HQA1200(T) 10 1200°C 0,024 0,019 0,034
HQA600 1 22°C 0,046 0,015 B.D.L
HQA600 2 22°C 0,069 0,022 B.D.L
HQA600 3 22°C 0,062 0,015 B.D.L
HQA600 4 22°C 0,043 0,022 B.D.L
HQA600 5 22°C 0,047 0,025 B.D.L
HQA600 6 22°C 0,043 0,025 B.D.L
HQA600 7 22°C 0,029 0,013 B.D.L
HQA600 8 22°C 0,039 0,022 B.D.L
HQA600 1 520°C 0,040 0,027 0,015
HQA600 2 520°C 0,149 0,022 0,014
HQA600 3 520°C 0,145 0,029 0,013
HQA600 4 520°C 0,069 0,021 0,014
HQA600 5 520°C 0,068 0,026 0,018
HQA600 6 520°C 0,059 0,020 0,018
HQA600 7 520°C 0,051 0,024 0,012
HQA600 1 600°C 0,048 0,023 0,011
HQA600 2 600°C 0,054 0,020 0,013
HQA600 3 600°C 0,156 0,024 0,011
HQA600 4 600°C 0,067 0,022 0,016
HQA600 5 600°C 0,054 0,022 0,011
HQA600 6 600°C 0,070 0,018 B.D.L
HQA600 7 600°C 0,049 0,023 0,010
HQA600 8 600°C 0,048 0,017 0,014
HQA600 1 after polishing 0,026 0,013 B.D.L
412
HQA1200(HNO3) 1 22°C 0,032 B.D.L B.D.L
HQA1200(HNO3) 2 22°C 0,036 0,016 B.D.L
HQA1200(HNO3) 3 22°C 0,076 0,018 B.D.L
HQA1200(HNO3) 4 22°C 0,028 0,016 B.D.L
HQA1200(HNO3) 5 22°C 0,026 0,017 B.D.L
HQA1200(HNO3) 6 22°C 0,032 0,020 B.D.L
HQA1200(HNO3) 7 22°C 0,032 0,018 B.D.L
HQA1200(HNO3) 8 22°C 0,031 0,015 B.D.L
HQA1200(HNO3) 9 22°C 0,027 0,013 B.D.L
HQA1200(HNO3) 10 22°C 0,059 0,016 B.D.L
HQA1200(HNO3) 11 22°C 0,071 0,011 B.D.L
HQA1200(HNO3) 12 22°C 0,043 0,024 B.D.L
HQA1200(HNO3) 1 400°C 0,018 0,014 B.D.L
HQA1200(HNO3) 2 400°C 0,037 0,008 B.D.L
HQA1200(HNO3) 3 400°C 0,033 0,013 B.D.L
HQA1200(HNO3) 4 400°C 0,046 0,016 B.D.L
HQA1200(HNO3) 5 400°C 0,019 0,012 B.D.L
HQA1200(HNO3) 6 400°C 0,022 0,017 B.D.L
HQA1200(HNO3) 7 400°C 0,021 0,016 B.D.L
HQA1200(HNO3) 8 400°C 0,019 0,017 B.D.L
HQA1200(HNO3) 9 400°C 0,020 0,019 B.D.L
HQA1200(HNO3) 10 400°C 0,062 0,019 B.D.L
HQA1200(HNO3) 11 400°C 0,030 0,018 B.D.L
HQA1200(HNO3) 12 400°C 0,029 0,010 B.D.L
HQA1200(HNO3) 1 600°C 0,026 B.D.L B.D.L
HQA1200(HNO3) 2 600°C 0,023 0,015 0,013
HQA1200(HNO3) 3 600°C 0,024 0,014 B.D.L
HQA1200(HNO3) 4 600°C 0,105 0,040 B.D.L
HQA1200(HNO3) 5 600°C 0,107 0,040 B.D.L
HQA1200(HNO3) 6 600°C 0,135 0,043 B.D.L
HQA1200(HNO3) 7 600°C 0,119 0,042 B.D.L
HQA1200(HNO3) 8 600°C 0,020 0,010 B.D.L
HQA1200(HNO3) 9 600°C 0,036 0,018 B.D.L
HQA1200(HNO3) 10 600°C 0,046 0,016 B.D.L
HQA1200(HNO3) 11 600°C 0,033 0,011 B.D.L
HQA1200(HNO3) 12 600°C 0,034 0,029 B.D.L
HQA1200(HNO3) 1 700°C 0,051 0,018 B.D.L
HQA1200(HNO3) 2 700°C 0,031 0,015 B.D.L
HQA1200(HNO3) 3 700°C 0,033 0,020 0,010
HQA1200(HNO3) 4 700°C 0,027 0,019 B.D.L
HQA1200(HNO3) 5 700°C 0,085 0,030 0,010
HQA1200(HNO3) 6 700°C 0,054 0,024 0,011
HQA1200(HNO3) 7 700°C 0,080 0,032 B.D.L
HQA1200(HNO3) 8 700°C 0,036 0,022 B.D.L
HQA1200(HNO3) 9 700°C 0,022 0,014 0,010
413
HQA1200(HNO3) 10 700°C 0,022 0,014 B.D.L
HQA1200(HNO3) 11 700°C 0,026 0,011 0,012
HQA1200(HNO3) 12 700°C 0,060 0,012 B.D.L
HQA1200(HNO3) 13 700°C 0,071 0,016 0,012
HQA1200(HNO3) 14 700°C 0,029 nd B.D.L
HQA1200(HNO3) 1 800°C 0,047 0,011 0,013
HQA1200(HNO3) 2 800°C 0,031 0,009 0,014
HQA1200(HNO3) 3 800°C 0,029 0,019 0,010
HQA1200(HNO3) 4 800°C 0,138 0,021 0,013
HQA1200(HNO3) 5 800°C 0,019 0,014 0,016
HQA1200(HNO3) 6 800°C 0,087 0,031 0,011
HQA1200(HNO3) 7 800°C 0,060 0,024 0,012
HQA1200(HNO3) 8 800°C 0,036 0,017 0,014
HQA1200(HNO3) 9 800°C 0,026 0,014 0,013
HQA1200(HNO3) 10 800°C 0,023 0,013 0,014
HQA1200(HNO3) 11 800°C 0,059 0,019 0,012
HQA1200(HNO3) 12 800°C 0,032 0,015 0,013
HQA1200(HNO3) 13 800°C 0,071 0,016 0,018
HQA1200(HNO3) 14 800°C 0,051 B.D.L 0,017
HQA1200(HNO3) 1 1200°C 0,025 0,011 0,015
HQA1200(HNO3) 2 1200°C 0,031 0,012 0,011
HQA1200(HNO3) 3 1200°C 0,031 0,014 0,018
HQA1200(HNO3) 4 1200°C 0,029 0,021 0,016
HQA1200(HNO3) 5 1200°C 0,021 0,015 0,013
HQA1200(HNO3) 6 1200°C B.D.L B.D.L 0,016
HQA1200(HNO3) 7 1200°C 0,020 0,015 0,012
HQA1200(HNO3) 8 1200°C 0,021 0,013 0,015
HQA1200(HNO3) 9 1200°C 0,036 0,017 0,013
HQA1200(HNO3) 10 1200°C 0,046 0,018 0,019
HQA1200(HNO3) 11 1200°C 0,044 0,014 0,015
HQA1200(HNO3) 12 1200°C 0,062 B.D.L 0,018
HQA1200(HNO3) 1 after polishing 0,024 0,012 B.D.L
414
HQB900 profile (1-2) 1 22°C 0,008 0,010 0,038
HQB900 profile (1-2) 2 22°C 0,009 B.D.L 0,016
HQB900 profile (1-2) 3 22°C 0,008 0,010 0,011
HQB900 profile (1-2) 4 22°C 0,009 0,008 0,013
HQB900 profile (1-2) 5 22°C 0,006 B.D.L 0,018
HQB900 profile (1-2) 6 22°C 0,010 B.D.L B.D.L
HQB900 profile (1-2) 1 600°C 0,011 0,009 0,059
HQB900 profile (1-2) 2 600°C 0,007 B.D.L 0,055
HQB900 profile (1-2) 3 600°C 0,011 0,008 0,054
HQB900 profile (1-2) 4 600°C 0,009 0,009 0,042
HQB900 profile (1-2) 5 600°C 0,013 0,009 0,048
HQB900 profile (1-2) 6 600°C 0,012 0,013 0,047
HQB900 profile (1-2) 7 600°C 0,010 0,009 0,044
HQB900 profile (1-2) 8 600°C 0,015 0,008 0,044
HQB900 profile (1-2) 9 600°C 0,011 B.D.L 0,044
HQB900 profile (1-2) 10 600°C 0,011 B.D.L 0,041
HQB900 profile (1-2) 11 600°C 0,012 0,012 0,035
HQB900 profile (1-2) 12 600°C 0,011 0,009 0,033
HQB900 profile (1-2) 13 600°C 0,009 0,011 0,029
HQB900 profile (1-2) 14 600°C 0,011 B.D.L 0,026
HQB900 profile (1-2) 15 600°C 0,016 0,011 0,023
HQB900 profile (1-2) 1 900°C B.D.L B.D.L 0,091
HQB900 profile (1-2) 2 900°C 0,012 B.D.L 0,071
HQB900 profile (1-2) 5 900°C 0,007 B.D.L 0,049
HQB900 profile (1-2) 6 900°C 0,007 0,012 0,055
HQB900 profile (1-2) 7 900°C 0,007 0,011 0,058
HQB900 profile (1-2) 8 900°C 0,009 0,009 0,048
HQB900 profile (1-2) 9 900°C 0,008 B.D.L 0,056
HQB900 profile (1-2) 11 900°C 0,009 0,012 0,046
HQB900 profile (1-2) 12 900°C 0,008 B.D.L 0,042
HQB900 profile (1-2) 13 900°C 0,006 0,008 0,040
HQB900 profile (1-2) 14 900°C 0,008 B.D.L 0,033
HQB900 profile (1-2) 15 900°C 0,011 0,011 0,036
HQB900 profile (1-2) 1 22°C 0,011 B.D.L 0,119
HQB900 profile (1-2) 2 22°C 0,012 B.D.L 0,031
HQB900 profile (1-2) 3 22°C 0,007 B.D.L 0,016
HQB900 profile (1-2) 7 22°C 0,011 0,010 B.D.L
HQB900 profile (1-2) 1 600°C 0,018 B.D.L 0,167
HQB900 profile (1-2) 2 600°C 0,014 0,009 0,089
HQB900 profile (1-2) 3 600°C 0,015 B.D.L 0,068
415
HQB900 profile (1-2) 4 600°C 0,012 0,010 0,057
HQB900 profile (1-2) 5 600°C 0,015 B.D.L 0,057
HQB900 profile (1-2) 6 600°C 0,017 B.D.L 0,047
HQB900 profile (1-2) 7 600°C 0,020 B.D.L 0,050
HQB900 profile (1-2) 8 600°C 0,015 B.D.L 0,044
HQB900 profile (1-2) 9 600°C 0,013 0,008 0,039
HQB900 profile (1-2) 10 600°C 0,014 0,008 0,037
HQB900 profile (1-2) 11 600°C 0,013 0,009 0,033
HQB900 profile (1-2) 12 600°C 0,014 0,010 0,031
HQB900 profile (1-2) 13 600°C 0,016 0,014 0,028
HQB900 profile (1-2) 14 600°C 0,011 0,009 0,034
HQB900 profile (1-2) 1 900°C 0,011 0,010 0,228
HQB900 profile (1-2) 2 900°C 0,007 B.D.L 0,095
HQB900 profile (1-2) 3 900°C 0,006 B.D.L 0,069
HQB900 profile (1-2) 4 900°C 0,006 B.D.L 0,058
HQB900 profile (1-2) 5 900°C B.D.L 0,008 0,053
HQB900 profile (1-2) 6 900°C 0,008 B.D.L 0,050
HQB900 profile (1-2) 7 900°C 0,016 B.D.L 0,043
HQB900 profile (1-2) 8 900°C 0,008 B.D.L 0,046
HQB900 profile (1-2) 9 900°C 0,010 B.D.L 0,042
HQB900 profile (1-2) 10 900°C 0,012 B.D.L 0,035
HQB900 profile (1-2) 11 900°C 0,011 B.D.L 0,037
HQB900 profile (1-2) 12 900°C 0,012 B.D.L 0,037
HQB900 profile (1-2) 13 900°C 0,008 B.D.L 0,040
HQB900 profile (1-2) 14 900°C 0,009 B.D.L 0,030
HQB900 profile (1-2) 15 900°C 0,010 B.D.L 0,040
HQB900 profile (1-2) 1 after polishing B.D.L B.D.L B.D.L
HQB900 profile (1-2) 2 after polishing B.D.L 0,009 B.D.L
HQB900 profile (1-2) 5 after polishing B.D.L 0,009 B.D.L
HQB900 profile (1-2) 8 after polishing B.D.L 0,009 0,018
HQB900 profile (1-2) 9 after polishing B.D.L B.D.L 0,028
HQB900 profile (1-2) 10 after polishing 0,006 B.D.L 0,022
HQB900 profile (1-2) 11 after polishing B.D.L B.D.L 0,010
HQB900 profile (1-2) 15 after polishing 0,009 B.D.L B.D.L
416
HQB900 profile (1-2) 11 after polishing 0,007 0,012 B.D.L
HQB900T profile (1-2) 1 900°C B.D.L B.D.L 0,195
HQB900T profile (1-2) 2 900°C B.D.L 0,009 0,077
HQB900T profile (1-2) 3 900°C B.D.L 0,012 0,045
HQB900T profile (1-2) 4 900°C 0,014 B.D.L 0,027
HQB900T profile (1-2) 3 900°C B.D.L B.D.L 0,049
HQB900T profile (1-2) 1 after polishing 0,029 B.D.L B.D.L
HQB900T profile (1-2) 2 after polishing B.D.L B.D.L B.D.L
HQB900T profile (1-2) 3 after polishing B.D.L B.D.L 0,030
HQB900T profile (1-2) 4 after polishing B.D.L B.D.L 0,019
HQB900T profile (1-2) 5 after polishing B.D.L 0,008 B.D.L
HQB900T profile (1-2) 6 after polishing B.D.L B.D.L B.D.L
* Following the definition: Currie, L. A. (1968). Limits for qualitative detection and
quantitative determination. Application to radiochemistry. Analytical chemistry, 40(3), 586-
593.
417
Table A.3: LA-ICP-MS analyses of the different quartz crystals
Li B Na Mg Al P K Ca Ti Fe Cu Zn Ga Ge As Rb Sr Y
Quartz Analyse# Si (ppm)
MQ0 1 22,6 4,2 1,1 B.D.L 89,8 465128 31 B.D.L 282,9 41,4 3 B.D.L B.D.L B.D.L B.D.L B.D.L 0,02 0,01 B.D.L
MQ0 2 22,2 3,7 0,15 0,43 87,4 465128 28,3 B.D.L 268,3 43,2 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0 B.D.L
MQ0 3 22,1 4,9 1,5 B.D.L 86,9 465128 34,6 B.D.L 262,9 42,1 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
MQ0 4 23,8 3,3 1,5 0,35 88,9 465128 26,4 B.D.L 334,3 43,2 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,01 B.D.L
MQ0 5 23,6 3,2 1,4 0,39 88,9 465128 26,5 B.D.L 334,4 43,2 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,01 0
MQ0 6 21 3,5 1,6 0,53 88,4 465128 26,1 B.D.L 292,6 41,6 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,01 0,03 B.D.L
MQ0 7 20,8 3,4 0,97 B.D.L 84 465128 32,7 B.D.L 274,6 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
MQ0 8 18,5 3,3 5,5 0,99 92,7 465128 30,6 B.D.L 275 43,3 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,05 0,07 B.D.L
MQ0 9 21,1 3,6 17 1,9 140,1 465128 28,2 19,3 219 43 11,4 0,7 B.D.L B.D.L B.D.L B.D.L 0,15 0,19 B.D.L
MQ0 10 23 4,1 B.D.L 0,83 89,4 465128 31,1 B.D.L 290,4 42,9 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
MQ0 11 22,1 3,2 2 0,41 79,5 465128 25,6 B.D.L 304,6 36,5 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,02 B.D.L B.D.L
MQ0 12 19,5 B.D.L 3,2 B.D.L 98 465128 34,2 B.D.L 254,1 35,2 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,04 0,05 B.D.L
MQ0 13 24,7 3,4 10,6 0,63 121,3 465128 27,4 19,3 290 52,5 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,04 0,1 B.D.L
MQ0 14 21,7 3,2 0,71 0,47 93,6 465128 33,2 B.D.L 244,6 43,3 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
MQ0 15 14 B.D.L 12,4 B.D.L 112,5 465128 44,7 B.D.L 196,2 36,9 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
MQ600 16 17,9 6,8 3,3 0,72 83,7 466998 25,5 B.D.L 290,4 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
MQ600 17 18,2 B.D.L 1,5 B.D.L 83,1 466998 26 B.D.L 264,9 36,4 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,02 B.D.L
MQ600 18 18,3 5,7 1,8 1,4 83,4 466998 27,3 B.D.L 231 48,2 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
MQ600 19 19,7 5 1,9 B.D.L 88,5 466998 25,5 B.D.L 257,2 44,4 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
MQ600 20 18,9 6,1 1 B.D.L 77,8 466998 26,7 B.D.L 267,3 43 B.D.L 0,94 B.D.L B.D.L 0,8 B.D.L B.D.L B.D.L B.D.L
MQ600 21 21,3 4,1 0,83 B.D.L 91,1 466998 26 B.D.L 252 43,8 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,01 B.D.L
MQ600 22 17,2 5,8 13 0,88 118 466998 24 B.D.L 280,2 40,1 18,7 0,58 B.D.L 0,05 0,58 B.D.L B.D.L 0,12 B.D.L
MQ600 23 18,5 4,5 0,53 0,41 77,4 466998 28,4 39,8 323,4 32,5 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
MQ600 24 19,2 5,5 1,1 0,38 81,5 466998 26,9 B.D.L 355,4 35,6 B.D.L B.D.L B.D.L 0,03 0,51 B.D.L B.D.L 0,02 B.D.L
MQ600 25 19,6 5,4 4,2 0,37 88,4 466998 27,3 B.D.L 366,1 39,5 B.D.L 0,41 B.D.L B.D.L 0,53 B.D.L B.D.L B.D.L B.D.L
MQ600 26 17,6 5,4 6 B.D.L 85 466998 29,5 B.D.L 393,8 34 B.D.L B.D.L B.D.L B.D.L 0,39 B.D.L B.D.L B.D.L B.D.L
MQ600 27 19,8 6,2 7,7 B.D.L 90,2 466998 32,6 47,8 322,4 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
MQ600 28 18,4 4,9 3 0,44 87,3 466998 25,3 B.D.L 384,5 38,3 B.D.L 0,35 B.D.L 0,04 B.D.L B.D.L B.D.L 0,03 B.D.L
MQ600 29 19,6 5,8 16,9 0,82 155,1 466998 28,5 B.D.L 390,3 41,1 B.D.L B.D.L B.D.L B.D.L 0,55 B.D.L 0,1 0,32 B.D.L
MQ600 30 22,4 6,5 26,1 0,81 129,1 466998 25,9 38,5 370,6 40,9 B.D.L B.D.L B.D.L 0,1 B.D.L B.D.L 0,19 0,13 B.D.L
MQ600 31 18,4 6,4 4,3 0,28 91,1 466998 24,2 B.D.L 383,1 37,3 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
MQ900(HNO3) 32 17,5 5,3 11,1 1,2 91,3 466998 30 54,2 432,5 35,1 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
MQ900(HNO3) 33 16,5 3,4 3,7 B.D.L 85,8 466998 24 B.D.L 289,1 34,5 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
MQ900(HNO3) 34 20,3 5,4 4,2 B.D.L 87,3 466998 24,4 B.D.L 332,9 45,2 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,01 B.D.L
MQ900(HNO3) 35 18,1 6,7 4,2 B.D.L 83,6 466998 23,7 B.D.L 348,7 34,5 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
MQ900(HNO3) 36 18,2 5,2 3,3 0,29 83,2 466998 24,9 B.D.L 332,2 39,3 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
MQ900(HNO3) 37 15,2 3,5 7,7 0,41 88,4 466998 26,6 B.D.L 327,9 47,4 B.D.L B.D.L B.D.L B.D.L 0,49 B.D.L B.D.L 0,06 B.D.L
MQ900(HNO3) 38 14,3 4,9 10 B.D.L 103,9 466998 26,6 B.D.L 353,8 49,4 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,09 0,01
418
Zr Ag Sn Sb Cs Ba La Ce Yb W Pb U
Quartz Analyse#
MQ0 1 B.D.L B.D.L 1,2 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
MQ0 3 B.D.L B.D.L 1,5 B.D.L B.D.L 0,07 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
MQ0 4 B.D.L B.D.L 1,1 B.D.L B.D.L 0,02 B.D.L B.D.L B.D.L B.D.L 0,02 B.D.L
MQ0 5 B.D.L B.D.L 1,1 B.D.L B.D.L 0,02 B.D.L B.D.L B.D.L B.D.L 0,02 B.D.L
MQ0 6 B.D.L B.D.L 1,5 B.D.L 0 B.D.L B.D.L 0 B.D.L B.D.L 0,01 B.D.L
MQ0 9 0,04 B.D.L 3,7 0,21 0,15 0,45 0,02 0,03 B.D.L B.D.L 0,17 B.D.L
MQ0 13 B.D.L B.D.L 1,1 B.D.L B.D.L 0,12 0,01 0,02 B.D.L B.D.L B.D.L B.D.L
MQ0 15 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
MQ600 16 B.D.L B.D.L 7,8 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
MQ600 17 B.D.L B.D.L 7,2 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
MQ600 18 B.D.L B.D.L 8,1 B.D.L B.D.L B.D.L 0,02 0,01 B.D.L B.D.L B.D.L B.D.L
MQ600 22 B.D.L B.D.L 6,7 0,09 0,22 B.D.L 0,01 B.D.L B.D.L B.D.L B.D.L B.D.L
MQ600 24 0,02 B.D.L 7,4 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
MQ600 25 0,01 B.D.L 6,8 B.D.L 0,02 0,07 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
MQ600 26 0,01 B.D.L 7,3 B.D.L B.D.L 0,12 B.D.L 0,01 B.D.L B.D.L B.D.L B.D.L
MQ600 27 B.D.L B.D.L 8,5 B.D.L 0,04 B.D.L 0,02 B.D.L B.D.L B.D.L B.D.L B.D.L
MQ600 29 0,07 B.D.L 7,6 B.D.L B.D.L 0,34 0,04 0,03 0,03 B.D.L B.D.L B.D.L
MQ600 30 B.D.L B.D.L 6,7 B.D.L 0,05 0,38 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
MQ600 31 B.D.L B.D.L 7,7 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
MQ900(HNO3) 32 B.D.L B.D.L 8,5 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,39 B.D.L
MQ900(HNO3) 33 B.D.L B.D.L 7,7 0,13 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
MQ900(HNO3) 34 B.D.L B.D.L 8,1 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
MQ900(HNO3) 38 B.D.L B.D.L 8,3 B.D.L B.D.L 0,24 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
419
MQ900(HNO3) 39 17 4,4 8,9 B.D.L 92,1 466998 23,9 B.D.L 360,7 50,2 B.D.L B.D.L B.D.L B.D.L 0,28 B.D.L B.D.L 0,05 B.D.L
MQ900(HNO3) 40 16,5 5 21,1 0,71 104,2 466998 21,2 6,3 378,8 51 4,5 B.D.L B.D.L 0,02 0,34 B.D.L 0,13 0,11 0,01
MQ900(HNO3) 41 14,9 B.D.L 7,7 B.D.L 86,5 466998 30,6 B.D.L 290,4 41,6 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,07 B.D.L
MQ900(HNO3) 42 14,6 B.D.L 11,7 1,7 129,4 466998 40,2 B.D.L 287,4 40,2 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,23 0,19 B.D.L
MQ900(HNO3) 43 17,9 3,6 8,2 0,24 95,5 466998 22 B.D.L 392,6 51,1 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,04 0,04 0,01
MQ900(HNO3) 44 15 6,3 4,1 0,22 77,2 466998 26,3 B.D.L 365,5 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
MQ900(HNO3) 45 17,9 4,3 10,9 0,91 135,1 466998 23,3 B.D.L 384,1 46,1 B.D.L B.D.L B.D.L 0,02 B.D.L B.D.L 0,09 0,15 B.D.L
MQ900(HNO3) 46 16,1 6,9 4,1 B.D.L 93,4 466998 24,8 B.D.L 348,1 50,4 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,02 B.D.L
MQ900 47 17,7 10 4,8 0,59 83,4 466998 35,5 38,7 410,1 40,7 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
MQ900 48 18,2 9,3 10,7 4,8 93,3 466998 37,6 B.D.L 457,7 39,7 B.D.L 5,1 B.D.L B.D.L B.D.L B.D.L B.D.L 0,12 B.D.L
MQ900 49 18,6 9,1 7,7 0,41 90,4 466998 33,6 B.D.L 417,2 43,2 B.D.L 1,9 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
MQ900 50 19 7,7 7,1 B.D.L 84,5 466998 38,6 B.D.L 408,4 39,5 B.D.L 1,7 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
MQ900 51 18,7 6,9 7,4 B.D.L 88 466998 30,2 B.D.L 475,3 36,7 B.D.L 1,4 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,01
MQ900 52 19,9 5,8 8,2 0,38 95,8 466998 32,1 B.D.L 460,5 43,5 B.D.L 1 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
MQ900 53 15,3 B.D.L 6,3 B.D.L 79,2 466998 35,1 B.D.L 341,3 36,4 B.D.L 0,74 B.D.L B.D.L 0,8 B.D.L B.D.L B.D.L B.D.L
MQ900 54 17 5 6,6 B.D.L 85,1 466998 34,3 B.D.L 316,2 42,4 B.D.L 0,93 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
MQ900 55 18,2 B.D.L 7 B.D.L 84,9 466998 31,7 B.D.L 323,3 44,9 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
MQ900 56 18,2 5,6 6,9 B.D.L 93,4 466998 29,3 B.D.L 319,3 45,4 B.D.L 1,4 B.D.L B.D.L 0,78 B.D.L B.D.L B.D.L B.D.L
MQ900 57 15,6 8,2 4 0,54 77,4 466998 32,7 B.D.L 326,7 31,8 B.D.L 0,99 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,01
MQ900 58 16,5 8,2 8,5 0,65 94,3 466998 31,5 B.D.L 268,7 43,7 B.D.L 0,9 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
MQ900 59 19,8 4,1 12,8 0,45 100,6 466998 24,6 B.D.L 325,6 43,5 B.D.L 0,97 B.D.L B.D.L 0,52 B.D.L 0,04 0,02 B.D.L
MQ900 60 20,8 4,2 6,8 B.D.L 98,9 466998 31,7 B.D.L 309,4 51,3 B.D.L 0,86 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
MQ900 61 18,3 4,6 16,6 0,56 108,7 466998 31 B.D.L 329 50,3 B.D.L 1,2 B.D.L B.D.L B.D.L B.D.L 0,06 0,08 B.D.L
MQ900 62 19,3 B.D.L 2,9 B.D.L 90,6 466998 30,2 B.D.L 315,8 43,9 B.D.L 1,2 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
MQ900(MF) 63 18,5 B.D.L 5,5 B.D.L 83,7 466998 37,6 B.D.L 456,5 40,8 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
MQ900(MF) 64 17,4 8 6,1 B.D.L 87,5 466998 34,3 B.D.L 454,1 39 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
MQ900(MF) 65 14,9 9,3 7,3 B.D.L 84,7 466998 33,3 71,4 425,5 35,2 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
MQ900(MF) 66 15,7 10 27,8 B.D.L 138,9 466998 28 B.D.L 460 31,6 B.D.L 1,3 B.D.L B.D.L B.D.L B.D.L 0,28 0,25 B.D.L
MQ900(MF) 67 16,2 6,2 4,7 0,52 78 466998 26,6 B.D.L 436,4 40,1 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
MQ900(MF) 68 16,4 8,1 11,1 0,25 100 466998 26,9 B.D.L 452,5 48,8 B.D.L 0,65 B.D.L B.D.L B.D.L B.D.L B.D.L 0,06 B.D.L
MQ900(MF) 69 17,3 9,5 13,4 B.D.L 114,4 466998 26,2 B.D.L 483,2 45,2 B.D.L 1,1 B.D.L B.D.L B.D.L B.D.L B.D.L 0,09 B.D.L
MQ900(MF) 70 17,3 5,1 4,1 B.D.L 76,6 466998 25,1 B.D.L 437,3 43,5 B.D.L 0,97 B.D.L B.D.L B.D.L B.D.L B.D.L 0,01 B.D.L
MQ900(MF) 71 16,2 B.D.L 32,6 B.D.L 168,6 466998 33,2 86,2 525,9 46,4 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,31 B.D.L
MQ900(MF) 72 21,6 9,3 12,6 6,3 94,6 466998 27,4 B.D.L 483,3 52,6 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
MQ900(MF) 73 17,4 8,8 14,6 2,9 168,2 466998 26,3 B.D.L 569,5 40,4 B.D.L 1,1 B.D.L B.D.L 0,58 B.D.L 0,16 0,13 B.D.L
MQ900(MF) 74 15,7 8,5 14,7 0,32 113,1 466998 27,1 B.D.L 551,9 51 B.D.L 0,93 B.D.L B.D.L B.D.L B.D.L 0,09 0,1 B.D.L
HQA0 75 14,8 B.D.L 1,1 B.D.L 304,4 465128 B.D.L B.D.L 802,1 114,5 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
HQA0 76 17,3 B.D.L B.D.L B.D.L 318,8 465128 B.D.L B.D.L 807,3 152,8 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
420
Quartz Analyse#
MQ900(HNO3) 39 B.D.L B.D.L 7,3 B.D.L B.D.L B.D.L 0,01 0,01 B.D.L B.D.L 0,03 B.D.L
MQ900(HNO3) 40 0,01 B.D.L 5,5 B.D.L B.D.L 0,22 0 0,03 B.D.L 0,01 0,03 0,01
MQ900(HNO3) 42 B.D.L B.D.L 9,4 B.D.L B.D.L 0,98 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
MQ900(HNO3) 43 0,01 B.D.L 5,5 B.D.L B.D.L 0,14 0,01 0,01 B.D.L B.D.L B.D.L B.D.L
MQ900(HNO3) 45 0,02 B.D.L 7,1 B.D.L 0,04 0,23 0,01 0,01 B.D.L B.D.L B.D.L B.D.L
MQ900(HNO3) 46 B.D.L B.D.L 8,4 B.D.L B.D.L 0,13 B.D.L B.D.L B.D.L 0,08 B.D.L B.D.L
MQ900 48 B.D.L B.D.L 8 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,18 0,24 B.D.L
MQ900 55 0,03 B.D.L 7,7 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
MQ900 56 B.D.L B.D.L 8 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,07 B.D.L 0,02
MQ900 59 B.D.L B.D.L 5,2 B.D.L B.D.L B.D.L B.D.L 0,01 B.D.L 0,02 B.D.L B.D.L
MQ900 61 B.D.L B.D.L 7,1 B.D.L B.D.L B.D.L 0,01 0,04 B.D.L B.D.L B.D.L B.D.L
MQ900(MF) 63 B.D.L B.D.L 7,1 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
MQ900(MF) 64 B.D.L B.D.L 6,7 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,04
MQ900(MF) 65 B.D.L B.D.L 7,9 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,06 B.D.L B.D.L
MQ900(MF) 66 B.D.L B.D.L 7,3 B.D.L 0,21 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
MQ900(MF) 67 B.D.L B.D.L 6,5 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 1,3 B.D.L B.D.L
MQ900(MF) 68 B.D.L B.D.L 5,3 B.D.L B.D.L B.D.L B.D.L 0,01 B.D.L 0,04 B.D.L B.D.L
MQ900(MF) 69 0,03 B.D.L 6,6 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
MQ900(MF) 70 B.D.L B.D.L 6 B.D.L B.D.L 0,18 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
MQ900(MF) 71 B.D.L B.D.L 8 B.D.L B.D.L 0,54 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
MQ900(MF) 72 B.D.L B.D.L 49 B.D.L 0,19 B.D.L 1,6 0,13 B.D.L 1,1 B.D.L 0,22
MQ900(MF) 73 B.D.L B.D.L 5,5 B.D.L 0,08 B.D.L 0,02 B.D.L B.D.L B.D.L B.D.L B.D.L
MQ900(MF) 74 B.D.L B.D.L 5,9 B.D.L 0,02 B.D.L 0,01 0,01 B.D.L 0,02 B.D.L B.D.L
HQA0 75 B.D.L B.D.L 36 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
421
HQA0 81 17,5 B.D.L 3,2 B.D.L 359,1 465128 B.D.L B.D.L 434,9 88,2 151,2 0,99 2,8 B.D.L B.D.L B.D.L B.D.L 0,1 B.D.L
HQA0 82 18,7 B.D.L 0,87 B.D.L 363,2 465128 B.D.L B.D.L 806,9 158 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
HQA0 83 20,8 B.D.L 2,9 4,1 367,2 465128 25,2 B.D.L 842,3 172,4 83,8 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
HQA0 85 19,2 B.D.L 0,92 B.D.L 370,1 465128 B.D.L B.D.L 804 156,5 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
HQA0 86 19,2 B.D.L B.D.L B.D.L 375,4 465128 B.D.L B.D.L 782,6 171 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
HQA0 88 18,4 B.D.L 13 3 398,4 465128 20 B.D.L 797,8 98,4 53,3 3,5 11,4 B.D.L B.D.L B.D.L B.D.L 0,14 B.D.L
HQA0 89 26,8 B.D.L 2,4 5,2 400,3 465128 20,6 B.D.L 937,7 174 13,8 0,7 1,1 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
HQA0 90 21 B.D.L 1,1 3 421,8 465128 23,7 B.D.L 750,4 77,8 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
HQA0 91 25 B.D.L 4,8 B.D.L 429,6 465128 B.D.L B.D.L 476,7 93,1 24,7 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,06 B.D.L
HQA0 92 25,4 B.D.L 11,5 3,5 440,1 465128 22,9 B.D.L 825,9 88,1 39,4 2,8 3,8 B.D.L B.D.L B.D.L 0,08 0,1 B.D.L
HQA0 93 32,2 B.D.L 4,4 B.D.L 574,7 465128 B.D.L B.D.L 437 107,4 B.D.L B.D.L 6,8 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
HQA0 94 27,6 B.D.L 40,3 9,5 786,9 465128 B.D.L 403,5 885,5 169 B.D.L 10,2 B.D.L B.D.L B.D.L B.D.L 1,1 0,59 B.D.L
HQA600 95 22,5 9,9 31,4 6,3 503,9 466998 30,9 B.D.L 292,4 180,2 B.D.L 10,3 B.D.L B.D.L B.D.L B.D.L B.D.L 1 B.D.L
HQA600 96 18,5 B.D.L 23 8,2 547,3 466998 35,6 B.D.L 343 163,9 B.D.L 1,6 3,8 B.D.L 1,5 B.D.L 0,34 0,25 B.D.L
HQA600 97 15,8 B.D.L 11,3 5,6 320,7 466998 41 B.D.L 314,1 170,3 B.D.L 2,3 3,3 B.D.L 1,2 B.D.L 0,22 0,14 B.D.L
HQA600 98 18,2 B.D.L 5 3,8 304,9 466998 28,1 B.D.L 319,6 160,9 B.D.L 1,2 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,01
HQA600 99 13,6 B.D.L 5,5 3,9 325,6 466998 34,3 B.D.L 334,1 170,1 B.D.L B.D.L B.D.L 0,42 B.D.L B.D.L B.D.L B.D.L B.D.L
HQA1200(HNO3) 100 22,4 B.D.L 159,6 4,6 357,9 466998 45,6 B.D.L 313,5 176,3 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
HQA1200(HNO3) 102 27,3 B.D.L 181,5 6 383,7 466998 42,7 B.D.L 344,2 163 B.D.L 3,6 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
HQA1200(HNO3) 103 28 B.D.L 217,6 31,2 417,8 466998 30,4 26,5 225,6 177,3 35,5 3,8 B.D.L B.D.L B.D.L B.D.L B.D.L 0,08 B.D.L
HQA1200(HNO3) 104 26,4 B.D.L 194,5 13 359,3 466998 36,4 B.D.L 411,8 144,8 B.D.L 1,9 5,1 B.D.L B.D.L B.D.L 0,48 B.D.L B.D.L
HQA1200(HNO3) 105 25,3 B.D.L 214,2 5,8 461,2 466998 37,5 B.D.L 391,8 143,1 B.D.L 3,5 B.D.L B.D.L B.D.L B.D.L B.D.L 0,2 B.D.L
HQA1200(HNO3) 106 19,2 B.D.L 172,5 4,2 302,1 466998 31 B.D.L 216,7 143,6 B.D.L 9,7 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
HQA1200 108 26,7 5,1 143,3 6,4 394,1 466998 35,5 B.D.L 308,1 82,8 28,8 112,5 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
HQA1200 109 30,7 7,4 171,2 5,6 448,2 466998 35,9 B.D.L 318,5 153,7 42,4 122,1 B.D.L B.D.L B.D.L B.D.L 0,2 0,08 B.D.L
HQA1200 110 65,7 7,6 326,9 20,3 908,5 466998 33,1 B.D.L 294,5 275,5 37,6 262,7 B.D.L B.D.L 1,4 B.D.L 0,46 0,09 B.D.L
HQA1200 111 31,7 7,7 422,9 6,4 899,4 466998 32 236,1 307,4 154,5 58,2 238,7 B.D.L 0,13 B.D.L B.D.L 1,4 0,53 0,03
HQA1200 112 31 4 109,3 6,9 360,3 466998 32,2 B.D.L 323,2 79,7 23,4 125,2 B.D.L 0,07 B.D.L B.D.L B.D.L B.D.L B.D.L
HQA1200 113 23,3 B.D.L 94,2 7,7 332,9 466998 38,2 B.D.L 312,2 146,5 B.D.L 95,2 B.D.L B.D.L B.D.L B.D.L B.D.L 0,12 0,08
HQA1200 114 42,4 5,5 188,1 5,5 480 466998 28,1 B.D.L 326,6 179,6 28 116,5 B.D.L B.D.L B.D.L B.D.L 0,16 0,03 B.D.L
422
Quartz Analyse#
HQA0 77 B.D.L B.D.L 24,7 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
HQA0 78 B.D.L B.D.L 37,5 B.D.L B.D.L 0,5 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
HQA0 81 B.D.L B.D.L 36,3 B.D.L B.D.L 0,27 B.D.L B.D.L B.D.L B.D.L 0,47 B.D.L
HQA0 87 B.D.L B.D.L 35,1 B.D.L 0,09 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
HQA0 88 0,09 B.D.L 34,2 B.D.L B.D.L 0,42 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
HQA0 89 B.D.L B.D.L 26,8 0,18 0,04 B.D.L B.D.L 0,01 B.D.L B.D.L B.D.L B.D.L
HQA0 90 B.D.L B.D.L 35,8 B.D.L B.D.L 0,3 B.D.L B.D.L B.D.L 0,03 B.D.L B.D.L
HQA0 92 0,06 0,01 32,8 B.D.L B.D.L B.D.L 0,02 0,05 B.D.L B.D.L 0,22 B.D.L
HQA0 94 0,39 B.D.L 42,9 B.D.L B.D.L 0,7 0,1 0,16 B.D.L B.D.L 1 B.D.L
HQA600 95 0,15 B.D.L 11,1 B.D.L B.D.L 6,1 0,16 0,35 B.D.L B.D.L 5,5 B.D.L
HQA600 96 0,15 B.D.L 11 2,1 B.D.L B.D.L B.D.L 0,15 B.D.L B.D.L 47,1 B.D.L
HQA600 97 B.D.L B.D.L 11 0,6 B.D.L B.D.L B.D.L 0,04 B.D.L B.D.L 10,6 B.D.L
HQA600 98 B.D.L B.D.L 10,2 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
HQA600 99 B.D.L B.D.L 15,2 B.D.L B.D.L B.D.L 0,04 0,07 B.D.L B.D.L B.D.L B.D.L
HQA1200(HNO3) 100 B.D.L B.D.L 14,9 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
HQA1200(HNO3) 102 0,11 B.D.L 14,4 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
HQA1200(HNO3) 103 0,09 B.D.L 11,3 B.D.L B.D.L 0,31 B.D.L 0,03 B.D.L B.D.L B.D.L B.D.L
HQA1200(HNO3) 104 B.D.L B.D.L 10,9 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,4 0,61 B.D.L
HQA1200(HNO3) 105 0,15 B.D.L 11,3 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
HQA1200(HNO3) 106 B.D.L B.D.L 16,1 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,71 B.D.L
HQA1200 108 0,08 B.D.L 10 B.D.L B.D.L 0,48 0,04 0,09 B.D.L B.D.L B.D.L B.D.L
HQA1200 109 0,17 B.D.L 11,7 B.D.L B.D.L B.D.L B.D.L 0,08 B.D.L B.D.L B.D.L B.D.L
HQA1200 110 0,27 B.D.L 12,1 B.D.L B.D.L 0,15 B.D.L 0,03 B.D.L B.D.L B.D.L B.D.L
HQA1200 111 0,89 B.D.L 11,6 B.D.L B.D.L 2,3 0,09 0,24 B.D.L B.D.L B.D.L B.D.L
HQA1200 112 0,04 B.D.L 9,6 B.D.L B.D.L 0,16 B.D.L B.D.L B.D.L 0,03 0,09 B.D.L
HQA1200 113 B.D.L B.D.L 11 B.D.L B.D.L B.D.L 0,48 1,6 B.D.L B.D.L B.D.L B.D.L
423
HQA1200 115 27,8 9,2 139,1 5,3 366,8 466998 34,1 B.D.L 274,7 150,9 B.D.L 104,5 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
HQA1200 116 27,6 3,5 108,8 5 352,3 466998 27,1 B.D.L 315 142,2 16,9 116,7 B.D.L B.D.L 0,93 B.D.L B.D.L B.D.L 0,01
HQA1200 117 45 6,6 190,3 7,3 521,1 466998 30 B.D.L 365,5 208,6 B.D.L 132,3 B.D.L B.D.L 1,6 B.D.L B.D.L B.D.L B.D.L
HQA1200 118 41,5 5,1 184,8 9,4 521,8 466998 34 30,5 346,3 205,3 34,6 152,5 B.D.L B.D.L 1,2 B.D.L 0,15 B.D.L B.D.L
HQA1200 119 18,8 8 98,8 43,1 356,3 466998 31,9 B.D.L 279 200,8 B.D.L 126,6 5,6 0,17 B.D.L B.D.L B.D.L B.D.L B.D.L
HQB0 120 15,7 B.D.L B.D.L 1,7 124,1 465128 25,2 B.D.L 350,1 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 B.D.L
HQB0 121 8,5 B.D.L 10 B.D.L 102,2 465128 23,5 B.D.L 377,6 78,2 B.D.L 0,76 B.D.L B.D.L B.D.L B.D.L B.D.L 0,02 B.D.L
HQB0 122 11,7 B.D.L 35,1 2,5 122 465128 30,2 B.D.L 326,8 94,1 36,1 6,8 4,5 B.D.L B.D.L B.D.L 0,15 0,1 B.D.L
HQB0 123 9,1 B.D.L 2,6 B.D.L 118,1 465128 B.D.L B.D.L 330,3 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
HQB0 125 12,6 B.D.L 3,6 2,1 128,2 465128 26,1 B.D.L 362,8 40,4 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,08 0,01 B.D.L
HQB0 126 0 B.D.L B.D.L B.D.L 117,9 465128 B.D.L 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
HQB0 127 13,7 B.D.L 4,3 4,6 116,8 465128 29,9 B.D.L 367,1 72 B.D.L 2 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
HQB0 128 13,5 B.D.L 0,83 B.D.L 123 465128 22 B.D.L 363,7 77,3 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
HQB0 130 8,4 B.D.L 10,3 B.D.L 134,6 465128 22,6 B.D.L 364,5 72,5 B.D.L 1,3 B.D.L B.D.L B.D.L B.D.L 0,13 0,06 B.D.L
HQB0 131 11,3 B.D.L 1,8 B.D.L 130,4 465128 25,5 B.D.L 386,8 75,7 B.D.L 1,2 B.D.L B.D.L B.D.L B.D.L B.D.L 0,03 B.D.L
HQB0 132 8,5 B.D.L 0,98 B.D.L 124,3 465128 23,9 B.D.L 284,9 121,8 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
HQB0 133 10,6 B.D.L 0,88 B.D.L 117,6 465128 27,6 B.D.L 371,1 103,5 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
HQB0 134 13,8 B.D.L 5,8 B.D.L 168 465128 33,6 B.D.L 357,7 72,1 B.D.L 2,1 B.D.L B.D.L B.D.L B.D.L 0,18 B.D.L B.D.L
HQB0 135 12,1 B.D.L B.D.L 2,1 116 465128 23,6 B.D.L 418,8 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
HQB0 136 10,6 B.D.L B.D.L B.D.L 115,3 465128 28,9 B.D.L 347,1 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
HQB0 137 10,5 B.D.L B.D.L B.D.L 122,4 465128 26,5 B.D.L 350,8 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
HQB0 138 8,9 B.D.L 1,3 2,3 106,2 465128 29,2 B.D.L 245,2 55,5 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
HQB0 139 12,4 B.D.L 1,4 2,3 117,1 465128 21,4 B.D.L 344,9 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
HQB0 140 11 2,7 6,1 1 115,8 465128 19,1 B.D.L 413,2 70,3 7,7 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,01 B.D.L
HQB0 141 9,9 B.D.L 8,6 3,2 176 465128 22 B.D.L 354,5 62,9 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,09 0,03
HQB0 142 10,4 B.D.L 0,32 0,9 107,9 465128 22,8 B.D.L 440,8 70,7 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
HQB0 146 7,5 B.D.L B.D.L B.D.L 107,9 465128 B.D.L B.D.L 408,3 81,9 76,5 3,9 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
HQB0 147 7,6 B.D.L 2,2 B.D.L 138,2 465128 B.D.L 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
HQB0 148 19,4 B.D.L B.D.L B.D.L 133 465128 42,1 B.D.L 447,9 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
HQB0 149 16,7 B.D.L B.D.L B.D.L 110,3 465128 B.D.L B.D.L 467 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
HQB0 150 16,7 B.D.L B.D.L B.D.L 110,3 465128 B.D.L B.D.L 467 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
HQB900 151 14,4 B.D.L 14,2 3,1 177,7 466998 33,6 B.D.L 320,3 59 B.D.L 92 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
HQB900 152 11,7 B.D.L 12,8 2,8 172,4 466998 36,8 B.D.L 311,8 60,5 B.D.L 84,9 B.D.L B.D.L B.D.L B.D.L 0,17 B.D.L B.D.L
424
Quartz Analyse#
HQA1200 115 0,03 B.D.L 11,7 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
HQA1200 116 0,06 B.D.L 9,1 B.D.L B.D.L B.D.L 0,07 0,31 B.D.L B.D.L B.D.L B.D.L
HQA1200 117 0,06 B.D.L 11,6 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
HQA1200 118 0,14 B.D.L 9,6 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
HQA1200 119 B.D.L B.D.L 13,4 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,98 B.D.L
HQB0 120 0,03 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
HQB0 121 B.D.L 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
HQB0 122 B.D.L B.D.L 46,7 B.D.L 0,03 B.D.L 0,02 0,03 B.D.L B.D.L B.D.L B.D.L
HQB0 123 B.D.L B.D.L 38,1 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
HQB0 124 B.D.L B.D.L 38,1 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
HQB0 125 0,06 B.D.L 34,7 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
HQB0 129 B.D.L 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
HQB0 133 B.D.L B.D.L 38,5 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
HQB0 140 B.D.L 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
HQB0 146 B.D.L B.D.L 35 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
HQB900 152 B.D.L B.D.L 10,3 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,02
425
HQB900 153 9,7 5,5 10,1 1,3 135,4 466998 31,2 B.D.L 326,9 52,3 B.D.L 65,8 B.D.L 0,06 B.D.L B.D.L B.D.L B.D.L B.D.L
HQB900 154 10,6 4,7 11 1,2 136,9 466998 28,6 B.D.L 341,1 53,7 B.D.L 72,8 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
HQB900 155 10,3 B.D.L 9,1 B.D.L 144,1 466998 25,5 B.D.L 234,1 64,2 B.D.L 67,1 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
HQB900 156 7 5,6 7,2 0,65 123,2 466998 23,5 B.D.L 257,2 62,5 B.D.L 47,6 B.D.L B.D.L 1,5 B.D.L B.D.L B.D.L B.D.L
HQB900 157 8,4 4 7,7 1,6 121,6 466998 26,5 B.D.L 242,1 68,8 B.D.L 52,1 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
HQB900 158 6,4 6,5 7 1,4 114 466998 31,6 B.D.L 225,2 56,6 29 49,9 1,4 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
HQB900 159 15,4 B.D.L 24,7 13,2 222,5 466998 34,7 B.D.L 278,4 48,5 205,1 93,5 9,6 B.D.L B.D.L B.D.L B.D.L 0,11 B.D.L
HQB900 160 16,7 6 27,9 4 205,9 466998 36,1 B.D.L 267 59,4 52,7 122,5 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
HQB900 161 7,9 6,9 8,3 1,6 113,4 466998 27,5 B.D.L 232,8 52 B.D.L 54 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
HQB900 162 7,3 4,9 6,7 0,92 113,4 466998 28,4 B.D.L 274 42,7 B.D.L 48,5 B.D.L B.D.L 0,85 B.D.L B.D.L B.D.L B.D.L
HQB900 163 9,8 5,6 9,2 1,5 134,6 466998 27,9 B.D.L 262,3 45 B.D.L 69,7 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
HQB900 164 10,4 B.D.L 8,8 1,8 103,7 466998 26,9 B.D.L 253,3 58,2 B.D.L 78,4 B.D.L B.D.L 1,6 B.D.L B.D.L B.D.L B.D.L
HQB900 165 9,5 B.D.L 8,9 0,77 104,6 466998 26,1 B.D.L 264,6 52,3 B.D.L 73,3 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
HQB900(T) 166 9,8 B.D.L 15 3,1 117,5 466998 34,9 58,5 279,6 68,3 61,1 74 B.D.L B.D.L B.D.L B.D.L B.D.L 0,04 B.D.L
HQB900(T) 167 7,5 B.D.L 7,5 1 108,2 466998 26,8 B.D.L 275,4 62,3 B.D.L 49,6 B.D.L B.D.L 0,93 B.D.L B.D.L B.D.L B.D.L
HQB900(T) 168 11,3 B.D.L 12 2,3 157,5 466998 31,4 B.D.L 305,3 71,3 B.D.L 70 B.D.L B.D.L 1,1 B.D.L B.D.L B.D.L B.D.L
HQB900(T) 169 7 5,1 9,4 1,6 113,7 466998 27,2 B.D.L 288,7 56,4 B.D.L 72,5 B.D.L B.D.L 0,79 B.D.L B.D.L B.D.L B.D.L
HQB900(T) 170 9,6 B.D.L 9,3 B.D.L 119,6 466998 25,3 B.D.L 286,9 52,3 B.D.L 80,7 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L
426
Quartz Analyse#
HQB900 154 B.D.L B.D.L 9,9 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
HQB900 161 B.D.L B.D.L 9,4 B.D.L B.D.L 0,15 B.D.L B.D.L B.D.L B.D.L B.D.L 0,01
HQB900(T) 166 B.D.L B.D.L 9,6 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,09 0,35 B.D.L
HQB900(T) 167 B.D.L B.D.L 9,2 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
HQB900(T) 168 0,05 B.D.L 10,6 B.D.L B.D.L B.D.L B.D.L B.D.L B.D.L 0,08 0,13 B.D.L
427
Table A.4: LA-ICP-MS analyses of SMIs
Quartz Analyse# Li (ppm) B (ppm) Na (ppm) Mg (ppm) Al (ppm) Si (ppm) P (ppm) K (ppm) Ca (ppm) Ti (ppm) Fe (ppm) Cu (ppm) Zn (ppm) Ga (ppm) Ge (ppm)
MQ0 1 690 72 27551 440 84676 HOST B.D.L 60482 7748 523 4978 1,9 42 N.A N.A
MQ0 2 615 82 28151 429 84676 HOST B.D.L 61764 7779 517 5002 0,9 40 N.A N.A
MQ0 3 413 B.D.L 28254 416 84676 HOST B.D.L 57826 1788 633 5090 B.D.L 29 N.A N.A
MQ0 4 720 33 31238 408 84676 HOST B.D.L 59095 7358 496 4780 6,3 43 N.A N.A
MQ0 5 781 41 30096 350 84676 HOST B.D.L 56866 10712 550 4534 0,2 36 N.A N.A
MQ0 6 687 79 32461 364 84676 HOST B.D.L 57917 6867 492 5304 B.D.L 46 N.A N.A
MQ0 8 673 B.D.L 26970 336 84676 HOST B.D.L 55684 6860 B.D.L 4191 1,9 45 N.A N.A
MQ0 9 601 82 27316 350 84676 HOST B.D.L 57850 7175 498 4820 0,6 36 N.A N.A
MQ0 10 B.D.L 65 30677 648 84676 HOST 1325 51140 12307 447 5836 B.D.L 44 N.A N.A
MQ0 11 697 67 33340 305 84676 HOST B.D.L 52652 6170 358 4726 0,3 37 N.A N.A
MQ0 12 731 54 24498 382 84676 HOST B.D.L 52809 7324 439 4692 0,6 28 N.A N.A
MQ0 13 832 49 25944 389 84676 HOST B.D.L 57749 7346 446 4704 1,2 33 N.A N.A
MQ600 15 B.D.L B.D.L 24434 379 84676 HOST B.D.L 45645 7354 459 4197 114 32 20 0,9
MQ600 16 702 125 28058 386 84676 HOST 13 44550 7212 442 4310 5,9 32 20 0,4
MQ600 17 167 132 28186 370 84676 HOST B.D.L 51953 7351 581 4072 26 30 24 B.D.L
MQ600 18 99 96 24972 371 84676 HOST B.D.L 49856 6956 459 4648 38 38 23 B.D.L
MQ600 19 625 B.D.L 27335 370 84676 HOST B.D.L 44602 7110 451 4921 21 36 26 4,2
MQ600 20 542 88 28072 303 84676 HOST B.D.L 42686 8015 B.D.L 4052 6,1 34 25 B.D.L
MQ900(HNO3) 21 124 63 25842 428 84676 HOST B.D.L 41862 7860 497 4230 11 36 21 0,2
MQ900(HNO3) 22 223 79 30123 383 84676 HOST B.D.L 38125 7132 418 4433 9,9 36 22 1,3
MQ900(HNO3) 23 53 B.D.L 29820 385 84676 HOST B.D.L 41647 6846 B.D.L 5221 22 49 33 2
MQ900(HNO3) 24 B.D.L B.D.L 27044 454 84676 HOST B.D.L 45643 6653 B.D.L 4583 28 45 21 B.D.L
MQ900(HNO3) 25 B.D.L 113 24411 403 84676 HOST B.D.L 43599 B.D.L B.D.L 4019 31 52 27 B.D.L
MQ900 26 B.D.L 55 30586 484 84676 HOST B.D.L 44594 7871 432 4758 274 17 22 4,9
MQ900 27 B.D.L B.D.L 18610 1740 84676 HOST B.D.L 19160 B.D.L B.D.L 33990 316 B.D.L 31 78
MQ900 28 B.D.L 108 28595 359 84676 HOST B.D.L 44574 6565 411 4715 270 39 26 B.D.L
MQ900 29 30 134 30254 394 84676 HOST B.D.L 46015 7607 494 4770 244 24 22 B.D.L
MQ900 30 B.D.L B.D.L 26353 575 84676 HOST 17156 47259 55021 496 5714 557 46 32 3,9
MQ900(WM) 31 B.D.L B.D.L 26970 218 84676 HOST B.D.L 50084 6661 B.D.L 4446 211 28 18 B.D.L
MQ900(WM) 32 B.D.L B.D.L 25757 443 84676 HOST B.D.L 51823 B.D.L B.D.L B.D.L 267 B.D.L 37 11
428
Table A.4: LA-ICP-MS analyses of SMIs
Quartz Analyse# As (ppm) Rb (ppm) Sr (ppm) Y (ppm) Zr (ppm) Ag (ppm) Sn (ppm) Sb (ppm) Cs (ppm) Ba (ppm) La (ppm) Ce (ppm) Yb (ppm) W (ppm) Pb (ppm) U (ppm)
MQ0 1 N.A 201 266 1,8 57 B.D.L 3,6 0,6 14 506 39 29 0,3 2,8 29 7,5
MQ0 2 N.A 202 272 2,1 61 B.D.L B.D.L B.D.L 13 533 22 30 0,2 2,4 27 8,4
MQ0 3 N.A 193 274 1 52 B.D.L B.D.L B.D.L 15 484 20 30 0,3 2,8 37 7,8
MQ0 4 N.A 220 332 4,8 61 B.D.L B.D.L 0,1 14 453 18 33 0,3 2,4 33 8
MQ0 5 N.A 208 319 5 69 0,2 B.D.L B.D.L 13 423 17 35 0,4 1,9 25 8,3
MQ0 6 N.A 227 352 4,3 61 B.D.L B.D.L B.D.L 15 525 15 31 0,3 3,8 36 8,5
MQ0 7 N.A 215 405 4,9 66 B.D.L B.D.L B.D.L 14 517 17 32 0,4 B.D.L 28 7,8
MQ0 8 N.A 202 248 1,2 54 B.D.L B.D.L B.D.L 15 428 19 32 B.D.L 1,9 25 8,8
MQ0 9 N.A 214 240 2,4 55 0,1 B.D.L B.D.L 16 269 15 25 0,2 3,2 28 9,9
MQ0 10 N.A 193 267 3,6 67 B.D.L B.D.L B.D.L 13 487 34 62 0,6 2,5 23 8,5
MQ0 11 N.A 217 222 3,1 53 B.D.L B.D.L B.D.L 16 299 15 31 0,1 3,4 28 9,4
MQ0 12 N.A 192 263 2,1 58 B.D.L B.D.L B.D.L 14 370 18 29 0,3 2,9 23 8,9
MQ0 13 N.A 208 243 2,1 58 0,1 B.D.L B.D.L 16 367 20 30 0,5 3,2 26 8,5
MQ0 14 N.A 200 259 1,9 56 B.D.L B.D.L B.D.L 14 465 22 30 0,2 2,1 25 8,4
MQ600 15 10 209 255 3,1 53 0,1 B.D.L B.D.L 14 302 B.D.L 24 0,5 4 27 7,9
MQ600 16 5,9 198 246 2,2 57 0,3 B.D.L 0,4 14 426 B.D.L 32 0,1 3,1 28 8,2
MQ600 17 B.D.L 206 280 0,9 64 0 B.D.L B.D.L 14 717 23 32 B.D.L 3,2 29 7
MQ600 18 B.D.L 195 289 1,7 68 0,1 B.D.L B.D.L 13 708 24 35 0,2 2,9 30 7,4
MQ600 19 B.D.L 204 269 2 62 0,1 B.D.L B.D.L 14 463 22 34 0,1 2,9 34 9,4
MQ600 20 B.D.L 198 259 4,4 60 0,3 B.D.L B.D.L 18 328 13 21 0,8 4,2 33 10
MQ900(HNO3) 21 B.D.L 191 341 2 63 2,9 B.D.L B.D.L 10 672 29 33 0,4 1,8 26 7
MQ900(HNO3) 22 4,9 193 322 4,2 62 0,3 B.D.L B.D.L 12 691 20 31 0,4 2,1 28 6,6
MQ900(HNO3) 23 12 229 318 3,1 71 0,7 B.D.L 0,8 15 538 19 31 0,4 1,6 39 7,8
MQ900(HNO3) 24 3,6 233 289 3,3 78 4,6 B.D.L B.D.L 16 535 21 36 1,1 1,8 35 8,1
MQ900(HNO3) 25 B.D.L 206 312 1,2 61 1,4 B.D.L B.D.L 16 598 26 37 B.D.L 1,1 56 9
MQ900 26 5,2 198 262 4 64 1 B.D.L B.D.L 15 524 35 34 0,6 292 21 8,6
MQ900 27 B.D.L 266 317 13 34 B.D.L B.D.L B.D.L 289 767 73 107 4 B.D.L 1,8 3,2
MQ900 28 7,6 215 245 2,3 59 1 B.D.L B.D.L 16 304 18 28 0,5 2,3 27 9,5
MQ900 29 11 219 272 1,3 61 0,8 B.D.L B.D.L 17 473 22 35 0,2 2,4 29 9,2
MQ900 30 B.D.L 185 456 17 82 6,1 B.D.L B.D.L 13 768 139 272 5,4 3,5 20 8,9
MQ900(WM) 31 B.D.L 194 256 1,5 38 1,3 B.D.L B.D.L 13 431 15 26 B.D.L 1,6 27 5,5
MQ900(WM) 32 B.D.L 248 247 0,2 53 2,7 B.D.L B.D.L 16 442 9,9 23 B.D.L B.D.L 45 9,2
429
Table A.5: LA-ICP-MS analyses of the HSMIs
Quartz Li (ppm) B (ppm) Na (ppm) Mg (ppm) Al (ppm) Si (ppm) P (ppm) K (ppm) Ca (ppm) Ti (ppm) Fe (ppm) Cu (ppm) Zn (ppm) Ga (ppm) Ge (ppm)
HQA0 B.D.L B.D.L 58610 2491 84676 HOST B.D.L 58480 15565 B.D.L 141160 B.D.L 1442 N.A N.A
HQA0 B.D.L B.D.L 61490 2446 84676 HOST B.D.L 63890 16300 B.D.L 146800 241 1729 N.A N.A
HQA1200 B.D.L B.D.L 78863 982 88381 HOST B.D.L 63182 11821 1974 28174 238946 4147 27 B.D.L
HQA1200 B.D.L B.D.L 79743 2165 88381 HOST B.D.L 38803 9376 B.D.L 22920 207221 2492 46 B.D.L
HQA1200(HNO3) B.D.L B.D.L 53373 414 88381 HOST B.D.L 43042 B.D.L B.D.L 9811 1952 584 25 B.D.L
Quartz Rb (ppm) Sr (ppm) Y (ppm) Zr (ppm) Ag (ppm) Sn (ppm) Sb (ppm) Cs (ppm) Ba (ppm) La (ppm) Ce (ppm) Yb (ppm) W (ppm) Pb (ppm) U (ppm)
HQA0 209 820 4,1 55 6,1 B.D.L B.D.L 11 768 29 54 B.D.L 47 266 B.D.L
HQA0 741 431 5,2 174 16 B.D.L B.D.L 54 466 91 178 B.D.L 87 1126 B.D.L
HQA1200 925 309 7,4 210 4 B.D.L B.D.L 72 219 46 96 1 26 666 35
HQA1200 419 253 5,6 98 5,3 B.D.L B.D.L 62 268 57 108 B.D.L 20 439 19
HQA1200 1134 313 15 505 7,2 B.D.L B.D.L 79 176 68 121 4 19 798 18
HQA1200 785 134 10 406 4,5 B.D.L B.D.L 75 60 38 70 B.D.L 14 310 9,6
HQA1200(HNO3) 534 62 3,1 221 1,5 B.D.L B.D.L 46 B.D.L 16 31 B.D.L B.D.L 113 15
HQA1200(HNO3) 530 111 16 307 35 B.D.L B.D.L 49 144 135 227 B.D.L 78 662 37
HQA1200(HNO3) 258 95 5,2 224 0,7 B.D.L B.D.L 40 77 341 41 0,8 5,2 71 28
430
Acknowledgement
Over these years in Geneva, I had the opportunity and the chance to meet great people,
passionate scientists and good friends. During all the steps of this project, good interactions
with colleagues from Geneva improved the quality of the thesis and some of them have
evolved to new interesting projects.
I want first to express my gratitude to Lluís and Kalin for inviting me to Geneva and
for offering me this interesting project. I really appreciate their support and contributions
during this project and also the freedom that they gave me to develop it. The fourth man of is
the team is Vincent, who brought me a huge support and assistance in the field and all along
the fourth years we worked together. His scepticism and perfectionism pushed me to go
deeper in my investigation and interpretations. I thank Volcan Compañía Minera S.A.,
especially the exploration team of Cerro de Pasco for their logistical support during the field
campaigns, access to data and drill cores. I gratefully acknowledge Ronner Bendezú for his
contribution on some of the manuscripts and on the general understanding of the district
geology of Cerro de Pasco.
Maria is gratefully acknowledged for her major role in the U-Pb TIMS dating of
zircons. For their friendly reception at ETH Zurich and support during the LA-ICP-MS
sessions, I would like to thank Markus and Kateřina. Anne-Sophie and Lukas are also
gratefully acknowledged for the SIMS analyses and careful reviews of part of the
manuscripts. I am also grateful to Alexey, Pierre and Hervé for their help for the LA-ICP-MS,
SEM and microprobe analyses, respectively. The faculty members of the of Department Earth
Sciences are gratefully acknowledged for their constant support during my project.
This thesis would not have been possible without the precious technical help of Jean-
Marie, Agathe, Michèle, Pierre, and Fred and the administrative support by Elisabeth, Sofia,
and Christine.
During these four years, I also learned a lot from collaborations with Cyril, Hervé,
Luca and Guy, and also from many discussions with Mélissa, Antoine, Vincent, Line, Maria
Teresa, Thomas, Josh and many others.
This thesis was financed by a grant from the Swiss National Science Foundation.
During the project I received additional grants to attend international conferences by the
Société Académique de Genève and also by the Society of Economic Geologists (SEG).
Finally I wish to acknowledge the priceless moral support of Marion who always encouraged
me. And a big thank you to my family for their continuous encouragement.
431

Rottier 2016

Hochgeladen von

Dokumentinformationen

Originaltitel

Copyright

Verfügbare Formate

Dieses Dokument teilen

Dokument teilen oder einbetten

Freigabeoptionen

Stufen Sie dieses Dokument als nützlich ein?

Sind diese Inhalte unangemessen?

Copyright:

Verfügbare Formate

Rottier 2016

Hochgeladen von

Copyright:

Verfügbare Formate

Thesis

Magmatic and hydrothermal fluid processes at the origin of the giant

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

Magmatic and hydrothermal fluid processes

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

Chapter 1: Crystallization and rejuvenation cycles of a silicic magmatic

Chapter 2: Hydrothermal evolution of hidden porphyry-type mineralization

Chapter 3: Heterogeneous melt and hypersaline liquid inclusions in shallow

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

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

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

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

Crystallization and rejuvenation cycles of a silicic

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

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

District geology and mineralization

Description of the dated porphyry-type mineralization

Porphyry-type mineralization PM1 and PM2

Porphyry-type mineralization PM3

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

Data acquisition parameters

Timing of magmatic and high-temperature

Trace element signatures of zircon

Mineral composition and textures of magmatic rocks

Porphyritic trachyte intrusions

Whole rock geochemistry

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

SiO2 67.3 67.3 67.9 62.6 65.4

*: age correction has been applied

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

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

Ti-in quartz thermobarometry

New geochronological constraints on the

Magma storage and rejuvenation

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

Assembl Degree of Tm halite Salinity NaCl

(1): Classified following Roedder rules

(5): Melting temperature of halite

Echantillon Sampler System East North Elevation Comments

Dacitic tuff sampled in the

Fresh dacitic dome samplein

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

Dacitic dome sampled at the

Sample Isotopic ratios Dates (Ma)

Sample Isotopic ratios Dates (Ma)

Sample Isotopic ratios Dates (Ma)

Sample Isotopic ratios Dates (Ma)

Sample Isotopic ratios Dates (Ma)

Sample Isotopic ratios Dates (Ma)

Composition Isotopic Ratios Dates (Ma)

206 207 208 Temperature (°C) calculated using

206 207 208 Temperature (°C) calculated using

Zircon saturation temperature

Zircon saturation temperature

Sandstone* fresh Mitu group 50 4 0.725701 18.6582 15.6358 39.4170

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

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

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

Baumgartner, Markus Wälle† and Lluís Fontboté