2015 Society of Economic Geologists, Inc.

Economic Geology, v. 110, pp. 3971

Zoned Base Metal Mineralization in a Porphyry System:

Origin and Evolution of Mineralizing Fluids in the Morococha District, Peru
Honza Catchpole,1,,* Kalin Kouzmanov,1 Benita Putlitz,2 Jung Hun Seo,3,** and Llus Fontbot1
1 Earth and Environmental Sciences, University of Geneva, Rue des Marachers 13, 1205 Geneva, Switzerland
2 Institute of Mineralogy and Geochemistry, University of Lausanne, 1015 Lausanne, Switzerland
3 Institute of Geochemistry and Petrology, Department of Earth Sciences, ETH Zurich, 8092 Zurich, Switzerland

Abstract
Porphyry-related base metal vein and replacement mineralization (i.e., Cordilleran polymetallic mineraliza-
tion) in the Morococha district, central Peru, is part of a large magmatic-hydrothermal system associated with
the emplacement of several late Miocene porphyry intrusions and formation of important Cu-Mo mineraliza-
tion. Zn-Pb-Ag-Cu veins overprint the giant Toromocho porphyry Cu-Mo deposit in the center of the district
and display a typical concentric base metal zonation (Cu Zn, Pb Ag) covering an area of approximately
50km2.
A detailed fluid inclusion study supports the hypothesis that base metal mineralization precipitated from
cooled and evolved metal-rich, intermediate-density porphyry-type fluids. In early stages of Cordilleran base
metal vein formation, fluid inclusions have low salinities of ~2 to 5 wt % NaCl equiv, CO2 contents of 3 to
10mol %, and homogenization temperatures (Th) of 380 to 340C. They are similar to intermediate-density
fluid inclusions trapped in a milky quartz vein predating Cordilleran polymetallic mineralization, with similar
low salinities (3.03.8 wt % NaCl equiv) and low CO2 contents (6.58 mol %), but higher Th of ~420 to 410C.
During cooling of the intermediate-density fluids from 400 to 300C, the lithostatic pressure regime changed
to a hydrostatic one. The fluids underwent pressure drop as well as phase separation (i.e., unmixing) and lost
most of their CO2. They acquired moderate salinities, in some cases intermediate (~up to 16 wt % NaCl) to
brine compositions. However, the bulk of the magmatic fluid retained low salinity while it continued to cool
under open-system conditions and precipitated tennantite-tetrahedrite, chalcopyrite, enargite, sphalerite, and
galena. Upon cooling below 270C, the fluids deposited abundant rhodochrosite and quartz, while following the
boiling curve toward lower P-T conditions. These data record an evolution of mineral precipitation from deep
(minimum depth of 21.5 km) to shallow environments (300800 m). Oxygen, hydrogen, and carbon stable
isotope data indicate that the hydrothermal fluids have a dominantly magmatic signature and were diluted by
meteoric waters during the carbonate stage.
Copper (5,00018,000 g/g), sulfur (up to 12,000 g/g), and iron (2,1006,000 g/g) concentrations in the
intermediate-density fluid inclusions in the milky quartz veins are approximately 5 to 10 times higher than in
intermediate-density inclusions of the early Cordilleran base metal veins. The base metals Zn, Pb, and Mn have
comparable concentrations between 100 and 1,000 g/g for both types of fluid. These findings suggest that
the fluids identified in Cordilleran polymetallic veins are compositionally similar to the porphyry-type fluids
and could have derived from the latter after precipitation of Cu- and Fe-bearing sulfides in a deeper porphyry
environment.
The new data explain the commonly observed base and precious metal zonation patterns encountered in
porphyry-centered districts (e.g., Bingham, Butte) and show that both porphyry and polymetallic mineralization
can precipitate from similar magmatic-hydrothermal fluid pulses.

Introduction
Porphyry-related base metal vein and replacement miner-
alization (i.e., Cordilleran polymetallic mineralization) can
constitute economically important Zn, Pb, Ag, and Cu mining
districts that are centered on porphyry Cu Au Mo depos-
its. The geochemical footprint of the hydrothermal systems
can comprise areas larger than 50 km2 with a district-scale
metal zonation of Cu, Mo Zn, Pb Ag, Au (Meyer et al.,
1968; Dilles and Einaudi, 1992; Babcock et al., 1995; Seedorff
et al., 2005; Sillitoe, 2010).
A close spatial and temporal relationship between por-
phyry and polymetallic mineralization has been recognized in
Corresponding author: e-mail, catchpole@gmx.de
*Current address: Vale Exploration Canada Inc., 2060 Flavelle Boulevard,
Mississauga, Ontario L5K 1Z9, Canada.
**Current address: Department of Energy Resources Engineering, Inha
University, 402-751 Incheon, Republic of Korea.
0361-0128/15/4275/39-33 39
several mining districts: the Main Stage veins of Butte, USA
(Meyer et al., 1968; Lund et al., 2002; Rusk et al., 2008a, b;
Reed et al., 2013); the Victoria deposit at Lepanto, Philip-
pines (Arribas et al., 1995; Hedenquist et al., 1998; Sajona
et al., 2002; Chang et al., 2011); the El Rosario veins at Col-
lahuasi, Chile (Masterman et al., 2005); and the base metal
vein and replacement bodies at Morococha, Peruthe sub-
ject of this study (McLaughlin and Graton, 1935; Cerro de
Pasco Copper Corporation, 1948; Petersen, 1965; Catch-
pole, 2011; Catchpole et al., 2012). Base metal mineraliza-
tion in these deposits occurs in the periphery of, adjacent to,
or superimposed on mineralized porphyry systems (Sillitoe,
1994; Seedorff et al., 2005; Sillitoe, 2010). The Morococha
district is among the best examples of overprinting (tele-
scoping, Sillitoe, 1994) of base metal mineralization onto
earlier, deeper, and higher-temperature porphyry-style min-
eralization in Peru.
Submitted: June 5, 2011
Accepted: March 30, 2014
40 CATCHPOLE ET AL.
Only a few studies have addressed fluid evolution of por-
phyry-related base and precious metal epithermal deposits by
using laser ablation-inductively coupled plasma-mass spec-
trometry (LA-ICP-MS) analysis of fluid inclusions (Heinrich
et al., 2004; Wallier et al., 2006; Pudack et al., 2009; Kouz-
manov et al., 2010; LeFort et al., 2011), and the origin and
compositional evolution of mineralizing fluids in such depos-
its are not entirely understood (Sillitoe and Hedenquist, 2003;
Simmons et al., 2005; Sillitoe, 2010). A pilot study (Catch-
pole et al., 2011) based on fluid inclusion microthermometry
and LA-ICP-MS analysis on a single zoned Cordilleran base
metal vein from Morococha revealed that early fluids precip-
itating Cu sulfides were moderately saline (45 wt % NaCl
equiv), CO2 bearing, and had minimum temperatures of 340
to 380C. Fluid temperatures, salinities, and CO2 and metal
contents decreased during Zn, Pb, and Ag sulfide precipita-
tion and the mineralizing fluid is interpreted to have been a
single-phase magmatic fluid of intermediate salinity and den-
sity that cooled to an aqueous liquid (Catchpole et al., 2011).
In this contribution we expand the previous study to district
scale. The fluid evolution in Morococha is traced in space and
time from the Cu-rich core outward to increasingly Zn, Pb,
and Ag rich zones in the periphery of the district. Oxygen,
hydrogen, and carbon stable isotope compositions of hydro-
thermal gangue minerals from the base metal veins are used
to constrain the source(s) of the metal-bearing fluids. The new
data allow direct comparison of mineralizing fluids in both the
porphyry and meso- to epithermal base metal environment
and contribute to the understanding of how these two deposit
types are related.
Geologic Setting
The Morococha district (1135'S, 7620'W) is located
~150km northeast of Lima in the Western Cordillera of the
central Peruvian Andes (Fig. 1). It is part of the Miocene poly-
metallic belt of central Peru (Noble and McKee, 1999), which
hosts a number of economically important zoned polymetallic
districts such as Yauricocha, Julcani, Quiruvilca, Hualgayoc,
Huaron, Colquijirca, and Cerro de Pasco. The oldest unit in
the district consists of Permian(?)-Triassic volcanosedimentary
rocks (alkaline lavas and pyroclastic flows) of the Mitu Group,
locally known as Catalina volcanics (Rivera and Kobe, 1983;
Mgard, 1984). Upper Triassic-Jurassic carbonate rocks of
the Pucar Group unconformably overlie the Mitu Group
rocks (Rosas et al., 2007), and are overlain by Cretaceous
sandstones and limestones of the Goyllarisquizga Group and
Upper Cretaceous limestones that are locally known as the
Machay Series (Chlec, Pariatambo, Jumasha formations).
The Montero Basalt and Sacracancha Trachyte volcanic units
are interlayered with carbonate rocks of the Pucar Group.
The Galera rhyolitic dome and pyroclastic flows and Tertiary
Casapalca red beds in the southern part of the district uncon-
formably overlie Upper Cretaceous limestone formations.
Multiple mid- to late Miocene intrusions (14.37.3 Ma) were
emplaced into the Triassic to Cretaceous sedimentary units
(Eyzaguirre et al., 1975; Beuchat, 2003; Kouzmanov et al.,
2008b; Bendez et al., 2012). Miocene magmatic activity in the
Morococha district started with the emplacement of the small
barren microdiorite intrusion in the northeastern part of the
district at 14.3 Ma, followed by the large barren laccolite-like
Anticona diorite intrusive at 14.1 Ma (Beuchat, 2003; Kouz-
manov et al., 2008b), which dominates the northwestern part
of the study area (Fig. 1). Late Miocene dioritic, granodioritic,
and quartz monzonitic porphyry stocks intruded the sedimen-
tary sequences and the Anticona diorite. These mineralized
porphyry intrusions have been described in detail and dated
by U-Pb TIMS method on zircons (Beuchat, 2003; Bendez et
al., 2008, 2012; Kouzmanov et al., 2008b). They comprise the
San Francisco stock (9.11 0.1 Ma), the Gertrudis stock, the
Yantac stock (8.81 0.06 Ma), the Codiciada and Toromocho
composite stocks (Figs. 1, 2), and the Ticlio stock in the west-
ernmost part of the Morococha district. A dacitic dike swarm
(7.26 0.02 Ma) trending NW-SE is the most recent magmatic
event and cuts the entire sequence in the Morococha district.
Porphyry-Type Mineralization
The giant Toromocho porphyry Cu-Mo deposit, with proven
and probable reserves of 1.38 Bt at 0.51% Cu, 0.018% Mo,
and 7.06 g/t Ag (Peru Copper Inc., 2006), is the only known
economic porphyry-type deposit in the Morococha district
and occupies its central part (Alvarez, 1999; Lowell and Alva-
rez, 2005; Kouzmanov et al., 2008b). It is part of a complex
magmatic-hydrothermal system that produced multiple intru-
sive events and was active for more than 2 m.y. Extensive
potassic and phyllic alteration zones host typical stockwork
mineralization of quartz-chalcopyrite chalcocite, quartz-
pyrite-chalcocite, and quartz-pyrite-molybdenite veins. Dis-
seminated Cu mineralization with potassic alteration is hosted
by breccia pipes in the central part of the deposit. The young-
est hydrothermal event that produced porphyry-type miner-
alization at Toromocho took place at about 7.0 Ma (Beuchat,
2003; Kouzmanov et al., 2008a; Catchpole, 2011). The San
Francisco porphyry stock (Fig. 2) is mineralized by quartz-
molybdenite veins associated with pervasive potassic altera-
tion and a phyllic alteration overprint.
Milky quartz veins cutting the San Francisco stock post-
date the quartz-molybdenite vein mineralization. The milky
quartz veins are up to 15 cm wide and have sericitic alteration
envelopes (Fig. 3a) and, occasionally, small muscovite crystals
in vugs. Recent 40Ar/39Ar dating of muscovite separated from
vugs in one milky quartz vein showed that the muscovite cool-
ing age postdates the last porphyry-type hydrothermal event
at Toromocho and San Francisco by at least 1 m.y. and over-
laps with Cordilleran polymetallic mineralization at 5.7 Ma
(adularia and muscovite cooling ages; Catchpole, 2011). The
milky color of the quartz veins results from repeated reopen-
ing of the vein, indicated by abundant fluid inclusion trails
aligned parallel to the strike of the vein (Fig. 4a). Muscovite
may have precipitated directly from these fluids, which is
supported by small muscovite flakes accidentally trapped in
some fluid inclusions. Alternatively, the muscovite may have
precipitated earlier and been thermally reset by the later flu-
ids that deposited quartz. Based on crosscutting relationships,
the milky quartz veins postdate porphyry-type mineralization
(i.e., molybdenite-bearing quartz veins) and predate Cordil-
leran polymetallic veins in the central Morococha district.
Cordilleran Polymetallic Mineralization
Cordilleran polymetallic (Zn-Pb-Ag-Cu) mineralization is
the youngest style of mineralization, overprints all porphyry


Gy
2 km LEGEND
Gy
Pu STRATIGRAPHY
Ch
Ju Q.al

Q
Q.al Alluvial deposits

374 000 E
378 000 E
382 000 E
ANTICONA Gy
Pu
Ga Galera volcanic rocks
Codiciada Cu-Mo Vt Tertiary volcanic rocks
Q.al E-N
composite stock Ca Casapalca formation
Huacracocha Lake Q
Codiciada open pitQ.al
Huascacocha
mor Lake
8 718 000 N Ju Jumasha formation
Q.al Gertrudis Duvaz Pa Pariatambo formation
Ju mor San Francisco
K

porphyry mor Ch Chulec formation

Q.al
Cu-Mo porphyry
mor Goyllarisquizga group
Gy
Ticlio Basalt interbedded flows
Sulfurosa
TICLIO porphyry San Florencio c-bx
Pu
Pu
mor ant
Toromocho Montero Basalt
Mt Pucar
Ju Sacracancha
Cu-Mo porphyry Pu
T-J

i-pcz TOLDOJIRCA Trachyte group

mor Manuelita SAN TADEO
Ticlio
fault c-bx mor Basal breccia
Mt Pu
San T
Toromocho open pit a
T

Mt Mitu group
deo
Pu fault
CentralQ.al
Morococha district
d-pdt
Miocene intrusive and intrusion
related rocks
Dacitic porphyry
Ca
dyke Breccia pipes
Pa c-bx
Gy d-pdt
Mt Dacite dykes
Vt Yantac d-pdt
M

Galera porphyry mor Late Miocene intrusions

Porvenir open pit Mid Miocene intrusions
(skarn)
Pu Mt
mor
YACUMINA
Mt SYMBOLS
PERU Ga
8 714 000 N mor Pu Unconformity
Mt Overthrust
Ch
Q.al Anticline
Vt
Gy Mt Syncline
Ca Strike & dip
Ju
Sulfide body
Pu Mt Vein
Lima Morococha Pa Mt Fault
Inferred Vein
Pu Inferred Fault
Mining zone
Road
ZONED BASE METAL MINERALIZATION IN A PORPHYRY SYSTEM, MOROCOCHA DISTRICT, PERU

Fig. 1. Geologic map of the Morococha district modified after Bendez et al. (2008), based on Lepry (1981), Alvarez (1999), maps of the Cerro de Pasco Corporation
(1965) and Centromin Peru (2002), and maps produced during this study.
41
42 CATCHPOLE ET AL.

Central Morococha district: B

mine level 400 - 4375 m.a.s.l. Manto Italia
N-8719000 Sierra Nevada
Ag - Pb Brecha Rosita

Montero basalt
Duvaz
Zn-Pb-Ag
Huamachuco

? Codiciada
composite
Zn - Cu stock
Riqueza 100 ore body

N-8718000 Ombla, Brecha Riqueza

Ombla,
lower upper

Cu
Sulfurosa
pyrite bodies

Gertrudis
porphyry
San Francisco
Toromocho
porphyry
Churruca
Sulfurosa
Rectificad

Legend
ora

N-8717000 San Francisco

E-375000

fluid inclusion
sample location ?
base metal vein
massive base metal
mineralization Toromocho
massive pyrite composite
replacement bodies stock
porphyry intrusions ?
(dioritic - granodioritic)
A
Triassic-Jurassic Pucar
carbonate rocks, skarn N-8716000
?
E-376000

E-378000
E-377000

Triassic-Jurassic Pucar carbonate rocks

Triassic Mitu volcanic rocks
0 0.5 Km
Manuelita

1 km Codiciada
SSW composite stock NNE
4800 m
Anticona
1
intrusion
Anticona
intrusion 2

1 3

A 1 4
B
Lithologies 5
4375 m
quartz feldspar porphyry 2 base metal sulfide bodies
Toromocho 1
pipe breccia 6 pyrite-quartz bodies
composite
porphyry intrusions 1 porphyry-type mineralization
stock
(dioritic - granodioritic)
Anticona diorite ? 2 contact skarn
Triassic-Jurassic Pucar carbonate rocks, skarn 3 3 pyrite bodies
Jurassic Montero basalt San Francisco 4 skarn-hosted sulfide bodies (Manto Italia)
Triassic-Jurassic Pucar carbonate rocks, silicified intrusion 4000 m 5 tube-like replacement bodies
Triassic-Jurassic Pucar carbonate rocks 6 Cordilleran polymetallic veins
Triassic Mitu volcanic rocks
Fig. 2. Geologic map of mining level 400 (4,375 m.a.s.l.) showing the distribution of massive sulfide mineralization (com-
piled from multiple mining levels) and schematic cross section in the central Morococha district. Compiled from unpublished
geologic maps of the Cerro de Pasco Copper Corp. (19201960), Centromin Peru, Pan American Silver Corp., and Len
Pimentel (2006).
 ZONED BASE METAL MINERALIZATION IN A PORPHYRY SYSTEM, MOROCOCHA DISTRICT, PERU 43

San
Francisco
porphyry 1cm
sericite

qz - py stage
base metal stage
milky Zn-Pb sub-stage
quartz vein Cu-Zn sub-stage
a 2 cm b Fe-Cu-As-Sn sub-stage
carbonate stage

c 25 cm qz
rhc

pyrite body

sl + gn

quartz-(pyrite)
quartz-tennantite
vein veinlets cross-cutting
(Fe-Cu-As-Sn)

e 2 cm
cp+sl+py

enargite
Cu-Zn sub-stage
Cu-Zn
sub-stage quartz-pyrite vein
quartz

pyrite

quartz-(pyrite) San
sub-stage
Francisco
porphyry
sericite
pyrite stage
1.5 cm
f
25 cm
chalcopyrite
quartz-pyrite
stage
py

qz tn
qz
pyrite

2 cm
2 cm
d g
Fig. 3. Vein textures: (a) Polished slab photograph of porphyry-type milky quartz vein with sericite halos. (b) Zoned
Cordilleran polymetallic vein formed during successive stages and substages of mineralization. (c) Crosscutting relationships
of individual base metal stages and substages in the Brecha Riqueza massive sulfide body. (d) Polished slab photograph of a
quartz-pyrite vein from the early stage of mineralization; small amounts of tennantite precipitate during the base metal stage;
the red box indicates the location of a crystal used for fluid inclusion work presented in Figure 4e. (e) Automorphous pink
rhodochrosite and quartz crystals that overgrow greenish sphalerite and galena (Zn-Cu zone). Earlier quartz-pyrite veinlets
with Cu minerals of the Fe-Cu-As-Sn substage crosscut altered andesite of the Mitu Group. (f) Pyrite-enargite vein (Cu
zone) that crosscuts sericitically altered San Francisco porphyry intrusion, reopening an earlier quartz-pyrite vein. (g) Pyrite-
chalcopyrite-sphalerite carbonate replacement from the Ombla massive sulfide body (Zn-Cu zone): the original carbonate
stratification is still visible. Abbreviations: cp = chalcopyrite, gn = galena, py = pyrite, qz = quartz, rhc = rhodochrosite, sl =
sphalerite, tn = tennantite.
44 CATCHPOLE ET AL.

milky quartz vein Cordilleran polymetallic vein

quartz
tennantite

pyrite

1 mm 0.5 mm opaque
a b phase

rhc c
carb. CL TL
stage L2
qz
gn
sl L1-CO2
base sl
metal
stage L2
L1-interm
host 1 cm
L1-interm
1 mm

TL
CL
L2
L2
B1

L1-interm
L1-CO2
L2 L1-CO2
L1-interm

L2
d e 3 mm

f
L1-CO2

L1-interm

L1-interm L1-CO2

1 mm
CL TL
Fig. 4. Hydrothermal quartz textures: (a) Transmitted light microphotograph of the milky quartz vein with fluid inclu-
sion trails parallel to the strike of the vein. (b) Reflected light microphotograph with tennantite-bearing fractures in pyrite
and SEM-CL image of the quartz crystal superimposed, indicating growth zones and healed fractures crosscutting; an inset
shows intermediate-density fluid inclusions with large opaque daughters. (c) Thin section of a well-zoned base metal vein;
one primary L2 fluid inclusion assemblage (FIA) hosted by transparent sphalerite is indicated in the lower right corner. (d-f)
Transmitted light (TL) photomicrographs and SEM-CL images of Cordilleran polymetallic veins. (d) Quartz crystal from the
quartz-pyrite stage. (e) Quartz crystal from the quartz-pyrite stage as seen in the red box in Figure 3d. (f) Well-zoned quartz
crystal cut perpendicular to the c-axis. Quartz growth occurs during the later base metal stage. Abbreviations: gn = galena, py
= pyrite, qz = quartz, rhc = rhodochrosite, sl = sphalerite, tn = tennantite.
 ZONED BASE METAL MINERALIZATION IN A PORPHYRY SYSTEM, MOROCOCHA DISTRICT, PERU 45
intrusions in the district, and postdates porphyry mineral-
ization, skarn, and massive pyrite bodies (Fig. 2). Cordille-
ran base metal veins are hosted by steeply dipping NNE- to
ENE-trending fractures. They exceed 1 km in vertical extent,
ranging from 5,100 m at the highest points of the district to
4,000m at the lowest mining levels, and continue at depth
(Fig. 2). Four base metal zones are distinguished in the dis-
trict: a Cu-rich central zone, a Zn-Cu intermediate zone, and
Zn-Pb-Ag Ag-Pb outer zones (McLaughlin and Graton,
1935; Cerro de Pasco Copper Corporation, 1948; Petersen,
1965; Titley, 1993; Catchpole et al., 2012).
The Cordilleran polymetallic mineralization formed dur-
ing three main paragenetic stages. The first stage is charac-
terized by barren quartz-pyrite veins with sericitic alteration
halos (Figs. 3b-d, 5). Zinc, Pb, Ag, and Cu minerals precipi-
tated during several substages of the second stage (Fig. 5).
Abundant rhodochrosite and quartz mark the third stage (Fig.
3e). A well-developed internal zonation of the veins (Fig. 3b)
provides evidence of telescoping during the lifetime of the
hydrothermal system. The relative mineral proportions in the
base metal substages depend on location within the district
and change from the inner Cu-rich to the outer Zn-Pb-Ag and
Ag-Pb zones (Fig. 5). Sulfidation state of the mineral assem-
blages varies as a function of base metal zone and paragenetic
stage. In general, intermediate to high initial sulfidation states
characterize the Cu and Zn-Cu zones, and low to intermedi-
ate initial sulfidation states are typical for the Zn-Pb-Ag zone
(Catchpole et al., 2012). The most abundant base metal sul-
fides in the Cu-rich zone are tennantite-tetrahedrite, chalcopy-
rite, and enargite (Fig. 3f, g). Sphalerite and galena abundance
increases toward the outer zones. Silver is mostly present in
tennantite-tetrahedrite, with increasing tenor toward the outer
zones. A minor amount occurs as Ag tellurides (hessite and
sttzite) and, rarely, as acanthite and polybasite (Ageneau et
al., 2009). Most galena is Ag poor (Catchpole, 2011).
Methodology
Seven key samples from different locations in the central
Morococha district were chosen for the fluid inclusion study
after an initial petrographic study of 150 samples and 30 dou-
bly polished thick sections. The samples were taken from
several base metal zones and cover most of the central poly-
metallic mining district (Fig. 2). Additionally, fluid inclusions
from a milky quartz vein from the core area of the district
were studied (Cu-rich zone; Fig. 3a).
Fluid inclusion assemblages were examined in doubly pol-
ished thick sections (Fig. 4). Around 400 inclusions from
64fluid inclusion assemblages (FIAs)1 were analyzed by
microthermometry (214 fluid inclusions per assemblage).
Scanning electron microscopy cathodoluminescence (SEM-
CL) images of hydrothermal quartz were obtained to clarify
the paragenetic context of the studied fluid inclusion assem-
blages. SEM-CL images were acquired at the University of
Lausanne using a CamScan MV2300 SEM equipped with a
panchromatic CL detector.
1 The term fluid inclusion assemblage (FIA) was introduced by Goldstein
and Reynolds (1994) to describe a group of fluid inclusions that were simul-
taneously trapped (cogenetic) and can be identified by a petrographic feature
(e.g., crystal growth zone, healed fracture).
Heating and freezing experiments were conducted on a
Linkam heating-freezing stage (THMSG 600) calibrated
using SYN FLINC synthetic fluid inclusions (Sterner and
Bodnar, 1984). Salinities in wt % NaCl equiv and minimum
pressures of entrapment were calculated using equations of
Zhang and Frantz (1987) and Bodnar and Vityk (1994), using
the SoWat (Driesner, 2007) and Flincor software (Brown,
1989). For CO2-bearing fluid inclusions with optically dis-
tinguishable clathrate formation (clathrate dissociation tem-
perature higher than ice melting temperature), salinities (wt
%), CO2 content (mol %), and pressures (bar) were calculated
using the ICE and LONER15 software and equations from
Bakker (1997) and Duan et al. (1992). Estimation of the l/v
ratios is the biggest source of error in these equations and is
therefore calculated with a 10% variation above and below the
actual observed ratio. The presence of CO2 was determined
by Raman spectroscopy at the University of Geneva using
a LABRAM with 632.8-nm He-Ne laser. Chemical compo-
sitions of single fluid inclusions (Na, S, K, Ca, Mn, Fe, Cu,
Zn, As, Mo, Ag, Sb, Cs, Au, and Pb) were measured using a
193-nm Excimer ArF laser (Geolas, ETH prototype) coupled
with an Elan 6100 DRC quadrupole ICP-MS at ETH Zurich
(Gnther et al., 1998; Heinrich et al., 2003).
Two tourmaline samples were separated from Toromocho
D veins (i.e., pyrite-tourmaline-quartz-sericite veins), and two
samples of muscovite from a quartz-molybdenite and a milky
quartz vein. Forty-three samples of Cordilleran polymetallic
veins, covering most of the district and stages of vein forma-
tion, were taken for stable isotope analyses: six samples of mus-
covite (for O and H isotopes) from vugs in the quartz-pyrite
(Fig. 3d) and base metal stages (Figs. 3b, c), 20 samples of
rhodochrosite, calcite, and siderite (for O and C isotopes) from
the carbonate stage (Fig. 3b, e), and 17 samples of individual
quartz crystals (for O isotopes) from all paragenetic stages of
the veins. Fifty percent of the samples chosen for isotopic
study were also analyzed during the fluid inclusion study.
A bulk-rock crushing protocol was used for separation of
muscovite and, where possible, muscovite samples were
handpicked from vugs in the veins. Final separates were
tested for purity by powder X-ray diffraction (Philips XPert
APD, University of Geneva) of a crushed aliquot of each sepa-
rate. Quartz samples are petrographically characterized pure
quartz wafers used for fluid inclusion analyses. The carbonate
samples are mainly rhodochrosite handpicked from carbon-
ate-stage Cordilleran polymetallic veins, and very late calcite
and siderite handpicked from vugs in the veins.
Hydrogen isotope compositions of muscovite and tourmaline
were measured using high-temperature (1,450C) reduction
methods with He carrier gas and a continuous-flow tempera-
ture conversion elemental analyzer (TC-EA) coupled to a
Thermo-Finnigan Delta Plus XL mass spectrometer, applying
methods presented by Sharp et al. (2001). The results were
measured as duplicates with reproducibility below 1.5 and
given in the standard notation, expressed relative to Vienna-
standard mean ocean water (V-SMOW) in . The results are
normalized to two in-house standards (kaolinite 17, DV-SMOW
= 125; biotite G1, DV-SMOW = 66), calibrated against
NBS-30 biotite (DV-SMOW = 65).
Oxygen isotope compositions of quartz, tourmaline, and
muscovite were measured using a method similar to that
 46

Cordilleran polymetallic veins - Zn-Cu and Cu-zone Cordilleran polymetallic veins - Zb-Pb-Ag / Ag-Pb
base metal stage carbonate base metal zone
quartz-pyrite quartz
qz Fe-Cu-As-Sn Cu-Zn Zn - Pb
pyrrhotite stage
stage stage -pyrite carbonate
sub-stage sub-stage sub-stage sub-stage stage
stage Zn-Pb Zn-Cu-Pb-Ag-W
pyrite sub-stage sub-stage stage
chalcopyrite (inclusion)
pyrrhotite (inclusion) quartz P S P S
galena (inclusion) magnetite
bornite (inclusion) hematite
digenite (inclusion)
enargite (inclusion) pyrrhotite
stannoidite (inclusion) marcasite
emplectite (inclusion) pyrite
tetradymite (inclusion) chalcopyrite (inclusion)
rare Au
native Au pyrrhotite (inclusion)
arsenopyrite S galena (inclusion)
quartz S S muscovite
adularia P
chlorite sphalerite (FeS: 15-20 mol%)
hbnerite sphalerite (FeS: 1-10 mol%)
scheelite (inclusion) sphalerite (FeS: <1 mol%)
scheelite P S
chalcopyrite
fluorapatite
rutile galena
dolomite white carbonate
APS minerals chlorite
pyrophanite
arsenopyrite
muscovite
U-Ti oxide bismuthinite
uraninite native Bi
xenotime Bi-Ag-Sb sulfosalt
CATCHPOLE ET AL.

monazite stannite
sphalerite (FeS: <2 mol%) S
enargite scheelite
tennantite siderite
tennantite - tetrahedrite fluorapatite
stannoidite
tennantite - tetrahedrite
colusite ?
nekrasovite rhodonite
vinciennite ?
green gangue
mawsonite ?
stannite rhodochrosite
kesterite adularia
arcubisite ?
alabandite
native Bi
sttzite
galena
chalcopyrite native Te
hessite huebnerite
Cu-Pb-sulfosalt seligmannite
fluorite
rhodochrosite barite
P
S Secondary fluid inclusion assemblage P Primary fluid inclusion assemblage Boiling fluid inclusion assemblage

Fig. 5. Generalized mineral paragenesis of Cordilleran polymetallic veins in different zones. The carbonate stage is absent in the Cu zone. The paragenetic positions
of measured fluid inclusion assemblages are indicated as a function of host mineral and base metal zone.
 ZONED BASE METAL MINERALIZATION IN A PORPHYRY SYSTEM, MOROCOCHA DISTRICT, PERU 47

reported by Sharp (1990) and Rumble and Hoering (1994),
described in more detail in Kasemann et al. (2001). Between
0.5 and 2 mg of sample was loaded onto a small platinum
sample holder and pumped to about 106 mbar. After pre-
flourination of the sample chamber overnight, the samples
were heated with a CO2 laser in 50 mbar of pure F2. Excess
F2 was separated from the O2 produced by conversion to Cl2
using KCl held at 150C. The extracted O2 was collected on
a molecular sieve (5A) and subsequently expanded into the
inlet of a Finnigan MAT 253 isotope ratio mass spectrometer.
Oxygen isotope compositions are reported in the standard
dnotation, expressed relative to V-SMOW in . The results
are normalized to the NBS-28 quartz standard (18OV-SMOW =
9.6) and the LS-1 quartz standard (18OV-SMOW = 18.1;
Valley et al., 1995). Replicate oxygen isotope analyses of the
standards used (n = 3) have an average precision of 0.1
for d18O. The accuracy of d18O values is better than 0.2.
Measured platinum tray sample batches contained one or
two duplicate samples to test individual sample quality and
repeatability of the analytical procedure.
The carbonate oxygen and carbon isotope compositions were
measured according to Spoetl and Vennemann (2003) using a
continuous-flow Gas Bench coupled to a Finnigan MAT Delta
Plus XL mass spectrometer. The carbonates were dissolved at
90C with H3PO4 to produce CO2. The results are normalized
to an in-house calcite standard (CM-STD; 13CV-PDB = 2.5
0.12; 18OV-PDB = 1.70 0.14), which was calibrated
using the NBS-19 calcite standard (13CV-PDB = 1.95; 18OV-
PDB = 2.20). To correct for acid-CO2 oxygen fractionation
at this temperature, several published equations for rhodo-
chrosite, calcite, and siderite were applied (Rosenbaum and
Sheppard, 1986; Swart et al., 1991; Bttcher, 1996; Gilg et
al., 2003). Oxygen isotope compositions are reported in the
standard notation, expressed in relative to V-SMOW for
oxygen and Vienna-Pee Dee belemnite (V-PDB) for carbon.
Results
Fluid inclusions petrography and microthermometry
Milky quartz veins: Secondary fluid inclusion trails are
numerous and often aligned parallel to the strike of the vein,
indicating repeated cracking and sealing. In areas where trail
density is lower, several types of fluid inclusion assemblages
are distinguished (Fig. 4a). Many intermediate-density (ID)
fluid inclusions have negative crystal shapes and range from
15 to 35 m in size (Table 1). Most have a triangular opaque
daughter phase, identified as chalcopyrite by Raman micro-
spectrometry (Fig. 6a, b). Most vapor bubbles occupy 50 to
65vol %. Vapor-rich (V) fluid inclusions are less common, have
70 to 90vol % vapor bubbles and frequently a chalcopyrite
daughter phase. Brine fluid inclusions (B0) are far less com-
mon than intermediate-density fluid inclusions, and the B0/
intermediate-density fluid inclusion frequency ratio is less
than 1/100 (Fig. 6c). Vapor bubbles typically occupy between
20 and 30 vol % of the fluid inclusions, and inclusions are up
to 10 to 20 m in size. They contain a salt solid and up to two
opaque phases, and small sylvite crystals can be occasionally
distinguished. Between 30% and 40% of all fluid inclusions in
brine-rich fluid inclusion trails did not contain salt solids before
the heating experiments. After heating, these fluid inclusions
formed salt solids upon cooling to room temperature. Failure
of salt crystals to nucleate upon cooling is a metastable effect
typically observed in inclusions with salinities between 26 and
35 wt % NaCl equiv and is not an indicator of postentrap-
ment modification (Roedder, 1984; Bodnar, 2003). Brine-rich
fluid inclusions postdate vapor and intermediate-density fluid

Table 1. Summary of Fluid Inclusion Characteristics

Stage at time FI Vapor bubble

Vein type of entrapment group volume (%) Solids CO2 content Size1 (m) Comment

Milky quartz vein ID 50 to 65 One opaque Observable 15 to 35 Often negative crystal shape
daughter clathrate
V 70 to 90 One opaque Liquid CO2 15 to 35 Apart from l/v ratio, very similar to ID
daughter
B0 20 to 30 Two salt and Not 10 to 20 Crosscuts ID FIAs, isometric to
two opaque detectable roundish inclusion shapes, frequently
daughters, metastable, less common than ID
sometimes
trapped
phyllosilicate

Cordilleran Base metal stage L1-CO2 35 to 60 Frequently Observable 10 to 30 L1-CO2 and L1-interm can only be
polymetallic veins opaque clathrate distinguished by microthermometry;
daughters L1-CO2 has CO2 clathrate formation
L1-interm 25 to 45 - Not 10 to 30 and low salinities, L1-interm has
detectable moderate to intermediate salinities,
but no clathrate formation
B1 20 to 25 One salt and Not 10 to 20 Only one found in similar paragenetic
one opaque detectable position as L1 FIAs
daughter

Base metal and L2 10 to 30 Often trapped Not 10 to 25 Mostly occurring in well-zoned

carbonate stage phyllosilicate detectable quartz crystals of the carbonate stage

Abbreviations: B = brine fluid, FI = fluid inclusion, ID = intermediate-density aqueous fluid, L = aqueous fluid, V = vapor fluid
1Maximum range of fluid inclusion size observed and used for measurements
48 CATCHPOLE ET AL.

ID a e
Fluid inclusion
types 30 m
ID FIA

B0 FIA
c
20 m
B0 d

ID FIA B0
b 100 m 25 m 60 m

f g h i muscovite

L1-CO2 B1

L1 FIAs L2

120 m 30 m 25 m 50 m

vapor-rich
liquid-rich

L2-boiling FIA 40 m j
Fig. 6. Fluid inclusion types and fluid inclusion assemblages: (a) Intermediate-density (ID) fluid inclusion with clearly vis-
ible chalcopyrite daughter crystals with triangular outlines. (b) Intermediate-density fluid inclusion assemblages with negative
crystal shapes. (c) B0 fluid inclusions with two visible solids. (d) B0 fluid inclusion with metastable absence of the salt daughter.
(e) One B0 fluid inclusion assemblage crosscutting an intermediate-density fluid inclusion assemblage. (f) Several sinuous
secondary liquid-rich L1 fluid inclusion assemblages crosscut a dark zone of decrepitated and small primary fluid inclusions in
the quartz-pyrite stage quartz growth zone (Fig. 4f). (g, h) Samples of typical L1-CO2 and B1 fluid inclusions. (i) L2 fluid inclu-
sions of the carbonate stage. (j) L2 boiling fluid inclusion assemblage (Fig. 4d).

inclusions, as indicated by crosscutting relationships (Fig. 6e).
Fluid inclusion types are summarized in Table 1 and micro-
thermometry results are reported in Table 2.
Microthermometry of intermediate-density fluid inclusion
assemblages yielded similar results with ice melting tempera-
tures of 4.0 to 1.9C, clathrate dissociation temperatures
at 5.3 to 7.7C, and homogenization temperatures of 408 to
423C (Fig. 7). No liquid CO2 was observed. Salinities of 3.0
to 3.8 wt % NaCl equiv and a moderate CO2 content of 6.6
to 7.9 mol % were calculated (Fig. 8). No consistent results
could be obtained for the vapor fluid inclusion assemblage,
because ice melting and clathrate dissociation could not be
observed due to the large size of the vapor phase. All inter-
mediate-density and vapor-rich inclusions homogenize to
vapor phase. All brine inclusions homogenize by salt disso-
lution before total homogenization via bubble disappearance
and plot below the halite saturation curve in Figure 7. The
individual melting temperatures of halite and sylvite were
not resolved during the experiments. The brine fluid inclu-
sion assemblages have halite melting temperatures of 120 to
194C, salinities of 28.6 to 31.6 wt % NaCl equiv, and Th val-
ues which are clearly lower than those of intermediate-density
fluid inclusions, clustering between 258 and 265C for two
fluid inclusion assemblages and 295 and 317C for another
three. Calculated minimum pressures of entrapment for the
intermediate-density fluid inclusions are 460 to 530 bar and
34 to 96 bar for B0 fluid inclusions.
Cordilleran polymetallic veins: Fluid inclusions in the
quartz-pyrite stage of the Cordilleran polymetallic veins are
scarce. In a few samples, small primary and secondary fluid
inclusions are preserved but are too small for reliable micro-
thermometric measurements (<5 m). Identifiable fluid
inclusions are liquid rich with approximately 30 to 60 vol %
vapor. In addition, traces of small, dark-colored decrepitated
primary fluid inclusions were identified (Fig. 4e).
The earliest fluid inclusion trails attributed to the base metal
stage (second stage of mineralization) are secondary inclusions
that crosscut idiomorphic quartz crystals of the quartz-pyrite
stage. The secondary trails are irregular and sinuous and are
not always traceable on SEM-CL images (Fig. 4d-f). These
 ZONED BASE METAL MINERALIZATION IN A PORPHYRY SYSTEM, MOROCOCHA DISTRICT, PERU 49

36
rve
n cu ID pre-base
34 atio 34 metal stage
tur B0
sa
lite B1
ha

Cordilleran polymetallic veins

32 32
L1- CO2-bearing
30
L1- intermediate sal.30 base
metal
L2- boiling stage
28 28
L2 central
zones
Sulfurosa
San Francisco
Salinity (wt% NaCl eq.)

L2 Codiciada (4875m)

L2 Zn-Pb-Ag Codiciada (4520m) carbonate

outer zone
16 16
L2 Codiciada (4335m)
stage

L2 Ag-Pb Sierra Nevada

14 distal zone 14

12 12

10 10

8 8

6 6

4 4

2 2

0 0
200 250 300 350 400 450

Th (C)
Fig. 7. Homogenization temperature vs. salinity diagram for different groups of fluid inclusion assemblages. Values for
each fluid inclusion assemblage are plotted as average with 1 error bars.

16

14

12

10
Mole% CO2

Fig. 8. CO2 content of fluid inclusion assem-

0 blages from this study and, additionally, L1 fluid
inclusion assemblages from the Veta Jackeline poly-
metallic vein in orange (Catchpole et al., 2011). Val-
200 250 300 350 400 450 ues for each fluid inclusion assemblage are plotted
as average with 1 error bars. Symbols correspond
Th (C) to legend in Figure 7.
50 CATCHPOLE ET AL.

Table 2. Microthermometric Data for 64 Fluid Inclusion Assemblages

Daughter
Sample no. Assemblage Type Host minerals Origin1 Tmice (C)2 n Thalite (C)3 n
KMO-8-414 17-A ID qz cp S 3.9 0.3 9
KMO-8-414 20-A ID qz cp S 4.0 0.1 5
KMO-8-414 21-A ID qz cp S 1.9 0.6 6
KMO-8-414 6-A ID qz cp S 3.6 0.2 10
KMO-8-414 6-B ID qz cp S 3.6 0.1 3
KMO-8-414 4-A B0 qz h + cp + op S 194 6 3
KMO-8-414 5-A B0 qz h + cp + op S 166 8 8
KMO-8-414 9-A B0 qz h + cp + op S 173 6 15
KMO-8-414 16-A B0 qz h + cp + op S 120 1
KMO-8-414 5-B B0 qz h + cp + op S 182 25 2
KMO-8-414 17-B L1-interm qz cp S 3.0 0.2 5
KMO-8-414 22-A L1-interm qz - S 2.3 0.1 3
KMO-8-414 4-B L2 central zones qz - S 1.4 0.1 5
KMO-6-288 C14 B1 qz op S 35 <0.1 6
KMO-6-288 A2 L1-CO2 qz op S 3.8 0.3 7
KMO-6-288 C11 L1-CO2 qz op S 4.3 0.2 5
KMO-6-288 C13 L1-CO2 qz op S 4.6 5
KMO-6-288 B5 L1-interm qz cp S 6.4 0.3 12
KMO-6-288 B6 L1-interm qz - S 8.8 0.1 6
KMO-6-288 B7 L1-interm qz - S 9.1 0.1 5
KMO-6-288 B8 L1-interm qz - S 3.8 0.3 7
KMO-6-288 C10 L1-interm qz op S 3.4 0.2 8
KMO-6-288 C12 L1-interm qz - S 4.8 0.3 8
KMO-6-288 C9 L2 central zones qz - S 0.9 0.1 12
KMO-6-288 A1 L2 central zones qz - S 1.9 0.8 6
KMO-6-288 A3 L1-interm qz - S 2.5 0.5 9
KMO-7-244 2-A L1-CO2 qz cp S 3.0 0.3 3
KMO-7-244 2-C L1-CO2 qz cp S 3.8 0.1 5
KMO-7-244 2-B L1-interm qz cp S 11.3 0.8 3
KMO-7-244 2-A L1-interm qz cp S 11.6 0.1 4
KMO-7-256 16-A L1-interm qz - P 3.4 0.1 6
KMO-7-256 16-B L1-interm qz - P 2.8 0.8 4
KMO-7-256 16-D L1-interm qz - S 3.2 0.1 2
KMO-7-256 16-C L2 central zones qz - S 1.0 4
KMO-6-286 1-AA L2-Codiciada (4875m) qz - S 1.4 0.2 2
KMO-6-286 1-A-Boil L2-Codiciada (4875m) qz - P-boiling 1.3 0.3 4
KMO-6-286 1-B L2-Codiciada (4875m) qz - S 1.0 0.3 9
KMO-6-286 1-C-Boil L2-Codiciada (4875m) boiling qz - P-boiling 0.5 0.3 12
KMO-6-286 1-E L2-Codiciada (4875m) qz - P 0.5 0.2 13
KMO-6-286 1-G-Boil L2-Codiciada (4875m) boiling qz - P-boiling 0.7 0.1 5
KMO-6-286 1-H L2-Codiciada (4875m) qz - P 1.1 0.4 5
KMO-6-286 3-A L2-Codiciada (4875m) qz - S 0.3 5
KMO-6-286 3-B L2-Codiciada (4875m) qz - S 0.9 0.1 3
KMO-6-286 3-C L2-Codiciada (4875m) qz - S 0.6 <0.1 4
KMO-6-295 10-A L2-Codiciada (4335m) sl - P 3.5 0.4 5
KMO-6-295 2-A L2-Codiciada (4335m) qz - S 2.0 0.2 10
KMO-6-295 3-A L2-Codiciada (4335m) qz - S 1.7 6
KMO-6-295 3-B L2-Codiciada (4335m) qz - S 1.7 0.1 6
KMO-6-295 3-BB L2-Codiciada (4335m) qz - S 1.7 0.1 7
KMO-6-295 3-C L2-Codiciada (4335m) qz - S 1.8 0.1 4
KMO-6-295 6-A L2-Codiciada (4335m) sl - S 2.3 0.1 5
KMO-6-295 7-A L2-Codiciada (4335m) qz - S 2.4 0.1 6
KMO-6-295 7-B L2-Codiciada (4335m) qz - S 2.4 0.2 3
MO-06-KK-32 1-B L2-Codiciada (4520m) qz - P 2.6 0.1 14
MO-06-KK-32 1-D L2-Codiciada (4520m) qz - P 2.6 0.1 5
MO-06-KK-32 1-E-Boil L2-Codiciada (4520m) boiling qz - P-boiling 2.6 0.3 5
MO-06-KK-32 1-H-boil L2-Codiciada (4520m) boiling qz - P-boiling 2.3 0.3 6
MO-06-KK-32 1-I L2-Codiciada (4520m) qz - P 1.6 0.2 6
MO-06-KK-32 5-A L2-Codiciada (4520m) qz - S 1.7 0.2 14
MO-06-KK-32 5-B L2-Codiciada (4520m) qz - S 1.9 0.1 6
MO-06-KK-32 5-C L2-Codiciada (4520m) qz - S 2.0 0.1 5
KMO-7-221b A L2-Sierra Nevada qz - S 1.6 0.1 5
KMO-7-221b B L2-Sierra Nevada qz - S 1.7 0.1 4
KMO-7-221b C L2-Sierra Nevada qz - S 1.0 0.1 5
Total: 8 64 64 58 356 35

Notes: Data are reported as averages of fluid inclusion assemblages with 1 standard deviation; host minerals of fluid inclusions are quartz (qz) and sphal-
erite (sl)
Abbreviations: cp = chalcopyrite, h = halite, op = opaque phase, qz = quartz, sl = sphalerite
1 Fluid inclusion trails are primary (P), secondary (S), primary boiling (P-boiling), or secondary boiling (S-boiling)
2 Final ice melting temperature
3 Final salt melting temperature
4 Final CO clathrate dissociation temperature
2
 ZONED BASE METAL MINERALIZATION IN A PORPHYRY SYSTEM, MOROCOCHA DISTRICT, PERU 51

from Morococha Porphyry and Cordilleran Polymetallic Vein Samples

Minimum
Salinity Density Vapor bubble pressure
Tmclath (C)4 n (wt % NaCl equiv)5 (g/cm)6 CO2 (mol %) (vol %)7 Th (C)8 n Mode9 (bar)10
7.7 0.2 5 3.0 0.1 0.51 <0.01 7.92 0.2 5055 408 5 9 V 529 22
6.5 0.3 5 3.0 0.2 0.41 <0.01 8.46 0.3 65 421 7 4 V 458 25
7090
5.7 0.2 7 3.6 0.1 0.46 0.01 6.84 0.1 60 422 12 11 V 496 49
5.3 0.5 3 3.8 0.2 0.46 0.01 6.60 0.4 60 423 3 4 V 467 7
31.6 0.3 1.08 0.01 2530 258 6 6 L 34 4
29.9 1.3 0.99 0.02 20 317 27 7 L 96 27
30.6 0.3 1.00 0.02 25 316 17 13 L 85 19
28.6 0.99 25 295 12 9 L 81
31.0 1.2 1.06 0.01 20 265 4 2 L 39 3
40 310 10 7 L
3.8 0.1 0.68 0.01 45 333 2 4 L 127 5
2.4 0.1 0.75 0.01 3035 289 4 6 L 68 4
34.7 <0.1 0.99 <0.01 2025 364 3 5 L 143 4
8.7 0.1 5 3.5 0.1 0.73 0.02 6.35 0.3 3540 345 5 7 L 734 82
9.2 0.0 4 2.2 0.1 0.58 0.03 9.40 0.3 5060 345 7 6 L 397 48
9.4 0.1 3 2.4 0.1 0.64 <0.01 8.76 0.1 4045 352 6 4 L 513 16
9.7 0.3 0.79 <0.01 2025 325 2 10 L 115 3
12.6 0.1 0.77 0.01 35 358 9 7 L 173 15
13.0 0.1 0.80 0.02 35 346 10 5 L 151 17
6.1 0.5 0.76 0.01 25 307 5 6 L 91 7
5.6 0.3 0.61 0.01 40 375 4 7 L 211 8
7.5 0.4 0.70 0.02 35 351 12 7 L 161 22
1.6 0.1 0.72 0.01 20 299 5 12 L 81 6
3.2 1.2 0.80 0.02 25 265 8 5 L 47 6
4.2 0.7 0.70 0.02 30 325 8 6 L 116 12
6.8 0.9 3 2.6 1.4 0.43 0.15 10.01 4.2 6080 345 4 4 L 240 12
6.5 0.0 4 4.0 0.1 0.59 0.02 5.71 0.2 45 339 6 5 L 267 31
15.3 0.7 0.83 0.01 2535 342 16 4 L 123 3
15.6 0.1 0.82 0.01 3040 343 8 4 L 138 13
5.5 0.1 0.77 0.01 3035 298 8 8 L 81 8
4.6 1.2 0.80 0.02 30 276 5 5 L 56 5
5.3 0.2 0.76 0.01 3035 304 3 3 L 87 3
1.7 0.80 0.01 2530 258 5 4 L 41 4
2.3 0.4 0.83 <0.01 25 240 2 2 L 29 1
2.2 0.5 0.77 0.02 25 275 7 5 L 55 6
1.8 0.5 0.79 0.01 20 260 7 8 L 43 5
0.8 0.5 0.80 0.02 2025 251 9 13 L 37 7
0.8 0.3 0.78 0.01 20 262 6 9 L 45 5
1.3 0.1 0.82 0.01 1015 239 4 5 L 28 2
1.8 0.6 0.81 0.01 20 247 4 6 L 35 3
0.5 0.80 25 245 1 5 L 32
1.5 0.1 0.78 <0.01 25 265 1 2 L 47 1
1.0 0.1 0.81 <0.01 25 243 1 4 L 31 1
5.7 0.6 0.84 0.01 30 263 2 6 L 45 1
3.4 0.3 0.84 0.01 1015 245 7 10 L 33 4
2.5 0.84 0.01 20 241 1 5 L 30 1
2.9 0.1 0.83 <0.01 20 243 2 8 L 31 1
2.8 0.1 0.83 0.02 20 247 13 8 L 33 10
3.0 0.1 0.83 0.02 20 251 11 5 L 34 9
3.9 0.2 0.82 0.01 20 256 4 5 L 40 3
4.0 0.1 0.82 0.02 20 264 9 7 L 45 8
4.0 0.2 0.80 0.01 20 273 3 4 L 53 3
3.7 1.5 0.80 0.01 25 276 7 19 L 56 7
4.4 0.1 0.82 0.01 25 265 4 8 L 46 4
4.3 0.5 0.79 0.01 20 286 7 7 L 63 7
3.9 0.5 0.83 0.01 20 255 4 6 L 39 3
2.4 1.1 0.78 0.01 25 277 6 7 L 56 4
2.9 0.3 0.78 0.01 20 276 2 11 L 56 1
3.2 0.1 0.78 <0.01 25 275 6 L 55
3.5 0.1 0.76 <0.01 25 288 3 4 L 68 3
2.8 0.1 0.84 0.02 1520 235 10 6 L 27 6
2.9 0.1 0.85 0.02 1520 232 13 4 L 26 7
1.8 0.1 0.83 0.01 2025 235 6 4 L 26 3
39 405
5 Salinitycalculated using equations by Bodnar and Vityk (1994)
6 Density of homogenized fluid inclusions
7 Observable vapor/liquid ratio or vapor bubble size
8 Total homogenization temperature
9 Mode of homogenization by bubble disappearance (to liquid = L) or by bubble growth (to vapor = V)
10 Calculated minimum pressure of entrapment; absolute pressures obtained calculated from boiling FIAs are set in bold
52 CATCHPOLE ET AL.
fluid inclusion trails postdate the quartz-pyrite stage and
are interpreted to be coeval with Cu precipitation because
cracks crosscutting pyrite are filled by tennantite and con-
tinue as healed fractures with fluid inclusion trails into quartz,
as observed in SEM-CL images (Fig. 4b). These secondary
fluid inclusions are liquid rich (L1), with 30 to 60 vol % vapor,
and sometimes have an opaque daughter mineral (Fig. 6f-h).
Zoned quartz and sphalerite crystals contain primary liquid-
rich fluids also trapped during the base metal stage (Fig. 4c). A
single brine fluid inclusion trail (B1) crosscuts the quartz-pyrite
stage quartz in the same crystal as the liquid-rich fluid inclu-
sion trails (Fig. 4e). Liquid-rich fluid inclusions (L2) hosted in
quartz, sphalerite, and rhodochrosite correspond to the final
base metal stage or the carbonate stage (Fig. 4c, d). About
50% of all those fluid inclusion trails are primary. The vapor
bubbles are smaller compared to those of L1, range from 10
to 30 vol % of the fluid inclusion volume, and have no opaque
daughter minerals (Fig. 6i). Several fluid inclusion assem-
blages consist of liquid-rich two-phase fluid inclusions coexist-
ing with vapor-rich fluid inclusions, indicating boiling (Fig. 6j).
Two different groups of L1 inclusion trails are distinguished
based on composition (Table 1): fluid inclusion assemblages
composed of a low-salinity, CO2-bearing fluid (L1-CO2), and
a moderate to intermediate-salinity fluid with no detectable
CO2 (L1-interm). Both L1-CO2 and L1-interm fluid inclusion assem-
blages occur together in the same samples (Fig. 4e) and are
not distinguishable by petrography. Five CO2-bearing L1-CO2
fluid inclusion assemblages yield ice melting temperatures of
4.6 to 3.0C, clathrate dissociation temperatures of 6.5 to
9.4C (5.79.4 mol % CO2), salinities of 2.2 to 4.0 wt % NaCl
equiv, and homogenization temperatures of 339 to 352C
(Fig. 7). The L1-CO2 inclusions are comparable to L1 fluid inclu-
sions reported in a recent study of one zoned base metal vein
from the Zn-Cu base metal zone in Morococha (Catchpole et
al., 2011). Eleven intermediate-salinity L1-interm fluid inclusion
5000
Codiciada mines - present day surface
4900
4800
elevation m.a.s.l.
4700
470
4600
4500
4400
4300
240 260 280
Th (C)
Fig. 9. Th and salinity of L2 fluid inclusion assemblages from three samples from different levels of the same mine in the
Codiciada area. Values for each FIA are plotted as average with 1 error bars.
assemblages have a wide range of ice melting temperatures
between 11.3 and 2.8C, salinities from 4.6 to 15.6 wt %
NaCl equiv, and Th of 276 to 375C. Variation of the individ-
ual fluid inclusion salinity within an assemblage ranges from
0.1 to 1.2 wt % NaCl equiv; variation of Th is mostly less than
10C. All liquid-rich fluid inclusions homogenize to liquid
phase. The B1 fluid inclusion trail has a salinity of 34.7 wt %
NaCl equiv and homogenization temperature of 364C. Total
homogenization of these fluid inclusions occurs by vapor dis-
appearance. The L2 fluid inclusions have ice melting tempera-
tures of 3.5 to 0.5C and low to moderate salinity in the
range of 0.5 to 5.7 wt % NaCl equiv; 90% of all fluid inclusion
assemblages have salinities between 1.8 and 4.0 wt % NaCl
equiv. Among all L2 inclusions, homogenization temperatures
range from 235 to 300C. Microthermometric results of most
fluid inclusion types do not vary as a function of base metal
zone; however, liquid-rich L2 fluid inclusions vary depending
on location within the district. L2 fluid inclusions from the Cu-
rich and Zn-Cu zones have the highest homogenization tem-
peratures, from 260 to 300C, and salinity between 1.5 and
4.5 wt % NaCl equiv. L2 fluid inclusions reported from a zoned
base metal vein from the Zn-Cu base metal zone (Catchpole et
al., 2011) have similar salinities (2.05.5 wt % NaCl equiv) but
lower homogenization temperatures of 220 to 265C. Liquid-
rich fluid inclusions from the distal Sierra Nevada Ag-Pb zone
have salinities between 1.8 and 2.8 wt % NaCl equiv and low
Th of 232 to 235C.
Fluid inclusions from a sample of the shallowest vein outcrop
(4,880 m.a.s.l.) in the Codiciada area yield salinities between
0.5 and 2 wt % NaCl equiv and homogenization temperatures
between 240 and 260C. The fluid inclusions from deeper
mining levels up to 550 m below the surface (4,330m.a.s.l.)
yield increasingly higher salinities of 2.8 to 4.5 wt % NaCl
equiv, whereas homogenization temperatures do not show a
clear trend and plot between 240 and 290C (Fig. 9). Boiling
5000
Vertical zonation
in the Codiciada area 4900
(Zn-Pb-Ag zone)
L2- boiling
4800
L2 Codiciada (4875m)
L2 Codiciada (4520m)
4700
L2 Codiciada (4335m)
4600
4500
4400
4300
1 2 3 4 5 6
salinity (wt% NaCl eq.)
 ZONED BASE METAL MINERALIZATION IN A PORPHYRY SYSTEM, MOROCOCHA DISTRICT, PERU 53
L2 fluid inclusion trails were observed in several samples in the
Codiciada area and suggest that similar Th values measured
for other liquid-rich (nonboiling) L2 inclusions in Codiciada
probably represent the real temperature of entrapment.
Raman spectroscopy reveals that phyllosilicates trapped in L2
inclusions are mainly muscovite and, occasionally, chlorite.
Calculated minimum pressures of entrapment for the L1-CO2,
L1-interm, and L2 fluids are 240 to 730 bar, 56 to 210 bar, and 26
to 80 bar, respectively. Boiling L2 fluid inclusions yield absolute
pressures of entrapment ranging from 28 to 63 bar.
Fluid composition by LA-ICP-MS analyses
For the sake of completeness, results from the previous
LA-ICP-MS fluid inclusion study of a Morococha Cordilleran
polymetallic vein sample (Catchpole et al., 2011) have been
added to the results of the present study (Fig. 10).
Intermediate-density fluid inclusion assemblages have
very high Cu and S concentrations that range from 5,000 to
18,000g/g for Cu and 8,000 to 12,000 g/g for S (see Appen-
dix). These concentrations are comparable with high concen-
trations of Cu and S in B0 fluid inclusions that range from
300 to 9,400 g/g for Cu and 6,000 to 9,000 g/g for S. B0
fluid inclusions have Fe, Zn, Mn, Pb, and Cs concentrations
about one order of magnitude higher than intermediate-
density fluid inclusions. Intermediate-density fluid inclusions
contain 2,100 to 6,000 g/g Fe, 210 to 310 g/g Zn, 200 to
340g/g Mn, 70 to 90 g/g Pb, and 4 to 6 g/g Cs, in contrast
to the brine fluid inclusions that contain 37,000 to 78,000 g/g
Fe, 2,000 to 6,000 g/g Zn, 4,700 to 9,200 g/g Mn, 500 to
1,000g/g Pb, and 60 to 180 g/g Cs. Molybdenum and Au
concentrations range from 2 to 11 g/g and 1.5 to 7.3 g/g for
intermediate-density inclusions, and 3 to 10 g/g and 0.3 to
22g/g for B0 inclusions, respectively (Appendix).
Copper, S, Fe, Zn, Mn, and Pb concentrations drop with
decreasing homogenization temperatures. Absolute concen-
trations of these elements are up to two orders of magnitude
higher in the L1-interm and B1 fluids than in the L1-CO2 fluids.
The effect of fluid salinity on element concentration is most
notable for Fe, Zn, Mn, Pb, Ag As, Sb, and Cs. The B1 fluid
inclusions have the highest measured Zn (3.0 wt %), Pb and
Mn (both 2.5 wt %), and As (1,120 g/g) concentrations and
the highest Fe (1.8 wt %) and Ag (81 g/g) concentrations
among all Cordilleran polymetallic vein fluid inclusions. The
L1-interm fluids contain 610 to 14,000 g/g Fe, 34 to 3,000 g/g
Zn, 450 to 1,600 g/g Mn, 15 to 4,000 g/g Pb, 3 to 32 g/g
Ag, and 31 to 176 g/g Cs. Because of the wide range of mod-
erate to intermediate salinities, there is a stronger variation
of these element concentrations among the fluid inclusion
assemblages as function of salinity. Copper concentrations
in L1-CO2, L1-interm, and B1 fluid inclusions are similar at 140
to 340 g/g, 90 to 900 g/g, and 300 g/g, respectively. The
wide variability in fluid salinity does not appear to control the
copper content in the Th range of 320 to 380C. Sulfur is
the only element that has higher concentrations in the L1-CO2
fluid inclusions (1,5003,600 g/g) than in the L1-interm fluid
inclusions, where S concentrations are mostly below detec-
tion limits (8602,180 g/g). L1-CO2 fluid inclusions have Zn
(30300 g/g), Mn (120300 g/g), Pb (1370 g/g), and As
(2280 g/g) concentrations that are comparable to those
of intermediate-density fluid inclusions; Fe (150270 g/g)
concentrations in L1-CO2 fluid inclusions are mostly one order
of magnitude lower than in intermediate-density fluid inclu-
sions, but Fe concentrations (803,000 g/g) from the CO2-
bearing L1 fluids from Veta Jackeline (Catchpole et al., 2011)
are closer to those found in the intermediate-density fluid
inclusions. Gold concentrations for the majority of L1-interm
and L1-CO2 fluid inclusion assemblages are below the detection
limits of 0.1 to 7g/g, but several L1-interm fluid inclusions have
high concentrations of 14 to 20 g/g and one L1-CO2 fluid inclu-
sion has 12.9 g/g. L2 fluid inclusions have distinctly lower base
metal concentrations, including Cu (136g/g), Zn (175g/
g), Pb (150 g/g), Mn (2100 g/g), and Ag (0.213g/g).
Concentrations for As (13133 g/g) and Sb (6400g/g) are
comparable in L1-interm and L1-CO2 fluid inclusions. Iron and Zn
are below detection limit (~700 and ~100g/g, respectively)
in most L2 fluid inclusions. Sulfur is consistently below detec-
tion limit for all L2 fluid inclusions.
Stable isotopes
The 18O and D compositions of two micas and the 18O
compositions of quartz extracted from a quartz-pyrite-molyb-
denite and the milky quartz veins yield values of 9.1, 10.4, and
12.1 18O (Fig. 11), and 95 and 89 D, respectively
(Table 3). Two tourmaline samples from Toromocho pyrite-
tourmaline-quartz-sericite veinlets yield 10.0 and 12.0
18O and 64 D. Values for muscovite and quartz from the
quartz-pyrite stage of the Cordilleran polymetallic veins range
from 10.3 to 15.6 18O (Fig. 11) and 92 to 69 D.
Muscovite and quartz from the base metal stages yield values
between 9.6 and 13.9 18O, with one outlier at 17.6 (for
quartz), and D of muscovite is 96 and 94. Quartz of
the carbonate stage has a similar range of compositions with
18O values between 9.4 and 13.8 (Fig. 12). Two samples
of Morococha present-day lake water yield 18O of 12.0 and
11.9 and D of 97 (Table 3). Sixteen samples of hydro-
thermal rhodochrosite vary widely in 18O and range from 6.4
to 20.4 (Table 4). Samples with depleted 18O compositions
(6.412.8 18O) have 13C values between 7.9 and 9.0,
while enriched ones (15.420.1 18O) also have higher 13C
values, between 4.7 and 6.4. Three calcite and one sider-
ite sample yield mostly depleted 13C values of up to 2.8.
Discussion
Fluid evolution from a stable isotope perspective
The isotopic compositions of the mineralizing hydrother-
mal fluids (18O and D) are derived from quartz (18O),
tourmaline (18O and D), muscovite (18O and D), and
rhodochrosite (18O) using equations by Zheng (1993a, b,
1999), Kotzer et al. (1993), Vennemann and ONeil (1996),
and Suess (1949). All calculations are based on temperatures
obtained by microthermometry of primary and secondary
fluid inclusions in the different paragenetic stages of this
study and Catchpole et al. (2011): milky quartz veins (450
400C), and quartz-pyrite stage (400350C), base metal
stage (350270C), and carbonate stage (270230C) of
Cordilleran polymetallic veins.
Muscovite in Morococha precipitated during the quartz-
pyrite and base metal stages at temperatures between 270
and 400C. No muscovite is observed in the carbonate stage
54 CATCHPOLE ET AL.

Cordilleran base metal veins milky Cordilleran base metal veins milky
quartz quartz
Carbonate Base metal stage Carbonate Base metal stage
vein vein
stage stage

L L1 ID L L1 ID
105 101
Cu Cu/(Na+K)
100
104

10-1
103
10-2
102
10-3

101
10-4

100 10-5
200 250 300 350 400 450 200 250 300 350 400 450
105 101
S S/(Na+K)
100
104

10-1

103
10-2

102 10-3
200 250 300 350 400 450 200 250 300 350 400 450
105 100
Concentration (g/g)

Zn Zn/(Na+K)
104 10-1

X / (Na+K)
103 10-2

102 10-3

101 10-4

100 10-5
200 250 300 350 400 450 200 250 300 350 400 450
105 100
Pb Pb/(Na+K)
104 10-1

103 10-2

102 10-3

101 10-4

100 10-5
200 250 300 350 400 450 200 250 300 350 400 450
105 100
Mn Mn/(Na+K)
104
10-1

103
10-2
102

10-3
101

100 10-4
200 250 300 350 400 450 200 250 300 350 400 450

Th (C) Th (C)
Fig. 10. Selected element concentrations and element ratios X/(Na + K) for fluid inclusion assemblages within the studied
porphyry and Cordilleran polymetallic vein samples. Element concentrations of L1 and L2 fluid inclusion assemblages from
the Veta Jackeline Cordilleran polymetallic vein (Catchpole et al., 2011) have been added for discussion.
 ZONED BASE METAL MINERALIZATION IN A PORPHYRY SYSTEM, MOROCOCHA DISTRICT, PERU 55

Cordilleran base metal veins milky Cordilleran base metal veins milky
quartz quartz
Carbonate Base metal stage Carbonate Base metal stage
vein vein
stage stage

L L1 ID L L1 ID
106
100

Fe Fe/(Na+K)
105

10-1
104

103
10-2

102

101 10-3
200 250 300 350 400 450 200 250 300 350 400 450
103 101
Ag Ag/(Na+K)
100
10 2
10-1

10-2
101
10-3

10-4
100
10-5

10-1 10-6
200 250 300 350 400 450 200 250 300 350 400 450
103 10-2
Concentration (g/g)

Cs Cs/(Na+K)

X / (Na+K)
10 2

10-3

101

10-4
100

10-1 10-5
200 250 300 350 400 450 200 250 300 350 400 450

104 10-1
As As/(Na+K)

103
10-2

102

10-3
101

100 10-4
200 250 300 350 400 450 200 250 300 350 400 450
104 100
Sb Sb/(Na+K)
10-1
103

10-2
102
10-3

10 1

10-4

100 10-5
200 250 300 350 400 450 200 250 300 350 400 450

Th (C) Th (C)
Fig. 10. (Cont.) Values for each fluid inclusion assemblage are plotted as mean with 1 error bars. For fluid inclusion
assemblages where only one measurement is available, no vertical error bars are shown. The gray dashed vertical lines sepa-
rate the temperature range of porphyry-type fluids and fluids from Cordilleran polymetallic veins.
56 CATCHPOLE ET AL.

Cordilleran base metal veins milky Cordilleran base metal veins milky
quartz quartz
Carbonate Carbonate Base metal stage
Base metal stage vein vein
stage stage

L L1 ID L L1 ID
102
10-2

Au Au/(Na+K)
101
10-3

100 10-4
Concentration (g/g)

10-1 10-5

X / (Na+K)
10-2 10-6
200 250 300 350 400 450 200 250 300 350 400 450

10 3
10 -2

Mo Mo/(Na+K)

102 10-3

101 10-4

100 10-5
200 250 300 350 400 450 200 250 300 350 400 450

Th (C) Th (C)

ID milky quartz
B0 vein

L1
Cordilleran polymetallic veins

Veta
Jackeline
L2 Catchpole
et al. 2011

B1
L1- CO2
L1- interm
L2

Fig. 10. (Cont.)

muscovite
porphyry-type veins quartz
tourmaline
Cordilleran polymetallic

quartz-pyrite
stage
veins

base metal
stage

carbonate
stage

8 10 12 14 16 18
18OVSMOW[]
Fig. 11. Oxygen isotope compositions of muscovite, quartz, and tourmaline sampled from porphyry-type veins and differ-
ent stages of Cordilleran polymetallic veins.
 ZONED BASE METAL MINERALIZATION IN A PORPHYRY SYSTEM, MOROCOCHA DISTRICT, PERU 57

Table 3. Oxygen and Hydrogen Isotope Compositions of Morococha Lake Water, Vein Gangue Minerals,
and Calculated Hydrothermal Fluid Compositions

18OH2O ()4 DH2O ()4

Sample code Location1 Mineral 2 18O ()3 D () 450C 400C 350C 270C 230C 450C 400C 350C 270C

Morococha present meteoric water

Kal-W1 Huacracocha lake - 12.0 <0.1 97 <1 - - - - - - - - -
Kal-W2 Huacracocha lake - 11.9 <0.1 97 0.2 - - - - - - - - -

Porphyry stage
TO-KK-77 Toromocho tur 12.0 64 <1 11.5 10.9 10.2 8.4 7.1 40 32 22 0
TO-KK-75 Toromocho tur 10.0 64 <1 9.5 9.0 8.3 6.5 5.2 40 32 22 0
KMO-8-203 San Francisco ms 10.4 <0.1 89 <1 10.8 10.4 9.8 8.2 7.1 - 46 45 47
KMO-8-414 San Francisco ms 9.1 95 <1 9.6 9.1 8.5 7.0 5.8 - 52 39 53
KMO-8-414 San Francisco qz 12.1 8.5 7.5 6.3 3.6 1.8 - - - -

Quartz-pyrite stage
KMO-6-252 Codiciada ms 10.3 76 <1 10.7 10.3 9.7 8.2 7.0 - 21 26 35
KMO-6-212 Codiciada ms 12.0 69 1 12.5 12.1 11.4 9.9 8.7 - 14 19 27
KMO-7-267 Codiciada ms 11.2 <0.1 78 2 11.7 11.2 10.6 9.1 7.9 - 22 28 36
KMO-6-280d Codiciada ms 11.1 92 1 11.5 11.1 10.5 8.9 7.8 - 36 42 50
KMO-6-280d Codiciada qz 14.7 11.1 10.1 8.9 6.2 4.3 - - - -
KMO-6-288_1 Codiciada qz 13.0 9.4 8.4 7.2 4.5 2.6 - - - -
KMO-6-288_2 Codiciada qz 14.5 10.9 9.9 8.7 6.0 4.2 - - - -
KMO-6-288_3 Codiciada qz 14.5 10.9 9.9 8.7 6.0 4.2 - - - -
KMO-7-256_21 Codiciada qz 15.0 11.4 10.4 9.2 6.5 4.7 - - - -
KMO-7-249 Sulfurosa qz 14.0 10.4 9.4 8.2 5.5 3.6 - - - -
KMO-7-244-1 Sulfurosa qz 15.6 0.3 12.0 11.1 9.8 7.1 5.3 - - - -

Base metal stage

MO-05-KK-02a Codiciada ms 9.6 96 1 10.0 9.6 9.0 7.4 6.2 - 41 44 52
MO-06-KK-32_1 Codiciada qz 17.6 0.4 13.9 12.9 11.7 9.0 7.1 - - - -
KMO-7-241a Sulfurosa ms 10.5 94 <1 11.0 10.5 9.9 8.4 7.2 - 38 44 52
KMO-7-241-Mid Sulfurosa qz 13.2 9.6 8.6 7.4 4.7 2.8 - - - -
KMO-7-241-Mid_2 Sulfurosa qz 13.9 10.3 9.4 8.1 5.5 3.6 - - - -
KMO-7-241-1_3 Sulfurosa qz 13.7 10.1 9.1 7.9 5.2 3.4 - - - -

Carbonate stage
KMO-6-286_3 Codiciada qz 13.8 10.2 9.2 8.0 5.3 3.5 - - - -
KMO-6-295 Codiciada qz 12.7 9.1 8.2 6.9 4.2 2.4 - - - -
KMO-6-280a Codiciada qz 12.9 9.3 8.3 7.1 4.4 2.6 - - - -
KMO-7-241-late Sulfurosa qz 9.6 <0.1 6.0 5.0 3.8 1.1 0.7 - - - -
KMO-7-229 Sulfurosa qz 9.4 5.8 4.8 3.6 0.9 1.0 - - - -
KMO-7-221 Sierra Nevada qz 11.2 7.6 6.6 5.4 2.7 0.8 - - - -

Notes: All values and reproducibility are in ; fluid compositions were calculated using equations from Zheng (1993a, b), Kotzer et al. (1993),
Vennemann and ONeil (1996), and Suess (1949)
1 Location coordinates can be found in Catchpole (2011)
2 ms = muscovite, qz = quartz, tur = tourmaline
3 All samples with errors for 18O are duplicate measurements
4 Values in bold font correpond to the temperature range of fluid in equilibrium

(<270C), and the presence of abundant rhodochrosite shows
that pH increases from slightly acidic to neutral (Bartos et
al., 2007), which is not favorable for muscovite precipitation
by feldspar hydrolysis (Barton et al., 1977). Calculated fluid
compositions in equilibrium with muscovite range from 7.4 to
12.1 18O and from 54 to 14 D, and for tourmaline
from 9.0 to 11.5 18O and from 40 to 32 D. These
values plot in the field typical for primary magmatic fluids
(Taylor, 1986, 1988, 1997), and are slightly shifted toward
more enriched compositions (Fig. 13a). Taylor (1974) dem-
onstrated that fluids derived from different granitic to tonal-
itic rocks can have 18O values of up to 13, exceeding the
typical values for primary magmatic fluids of 10. Magmatic
assimilation of a significant amount of crustal or supracrustal
rocks with an enriched 18O composition might produce a
magma with elevated 18O values (Bindeman, 2008; Auer
et al., 2009) and correspondingly high 18O magmatic fluids.
Miocene rocks at Morococha have Pb and Sr isotope signa-
tures that have been interpreted to represent magmatic mix-
ing of enriched upper mantle and radiogenic upper crustal
rocks as a result of crustal assimilation (MacFarlane et al.,
1990; Moritz et al., 2001; Bissig and Tosdal, 2009). Important
crustal assimilation by the late Miocene magmas is also sup-
ported by inherited zircon ages that range from Proterozoic to
Mesozoic in some of the porphyry stocks, as well as Hf isotope
compositions of zircon (Kouzmanov et al., 2008b). Alterna-
tively, the shift toward D and 18O enrichment could also be
explained if the magmatic fluid originates from degassing of
another magmatic fluid, as caused by deep fluid phase separa-
tion (Shinohara and Hedenquist, 1997). This is indicated by
58 CATCHPOLE ET AL.

-2

-4

13CVPDB[]
-6

-8 rhodochrosite
calcite
siderite
-10
4 6 8 10 12 14 16 18 20 22
OVSMOW[]
18

Fig. 12. Oxygen and carbon isotope compositions of rhodochrosite, calcite, and siderite from the carbonate stage of Cor-
dilleran polymetallic veins.

the results of the fluid inclusion analyses and discussed below.
A third possibility for the elevated 18O values is the involve-
ment of fluids with important radiogenic basement compo-
nent in the hydrothermal system at Morococha, as suggested
by high 87Sr/86Sr and low 143Nd/144Nd ratios of hydrothermal
anhydrite (Kouzmanov et al., 2011).
Fluids in equilibrium with quartz from the milky quartz
vein and the Cordilleran polymetallic veins (quartz-pyrite and
base metal stage) have 18O values of 7.5 to 11.5 and 4.7
to 11.7, respectively. These values overlap with 18O calcu-
lated for fluids in equilibrium with muscovite (Fig. 13b) and
show a similar trend to 18O values of magmatic waters and
heavier, possibly due to mixing with basement-derived waters.
One quartz-muscovite pair taken from a single base metal vein
sample (KMO-6-280d) yields a temperature of 350C (Chacko
et al., 1996), which agrees with the temperature range of vein
formation in the quartz-pyrite stage as outlined for by the fluid
inclusion study (400350C). Increasingly depleted 18O iso-
topic compositions were calculated for fluids in equilibrium
with quartz that precipitated below 270C in the carbonate
stage (1.0 to +5.3) as a result of progressive mixing with
meteoric water during cooling. Even the most depleted 18O
value of about 1.0 at 230C still shows that an important
proportion of the fluid must have been magmatic, assuming
that the meteoric paleowater end-member is similar to Moro-
cocha present-day lake water at 12 (Fig. 13a). We make

Table 4. Carbon and Oxygen Compositions of Hydrothermal Carbonates from Cordilleran Polymetallic Veins and
Calculated Hydrothermal Fluid Compositions

18OH2O ()

Sample no. Zone1 Host rock Depth (m) Mineral 2 18O () 13C () 270C 230C

KMO-6-294 Codiciada Porphyry intrusion 4,310 rhc 12.8 9.0 5.3 3.6
KMO-6-296 Codiciada Porphyry intrusion 4,360 rhc 17.5 5.4 10.1 8.4
KMO-6-282B Codiciada Porphyry intrusion 4,575 rhc 16.1 6.4 8.6 6.9
KMO-6-280A Codiciada Porphyry intrusion 4,680 rhc 12.5 7.9 5.0 3.3
KMO-6-298 Codiciada Carbonate rock 4,480 rhc 12.2 8.6 4.8 3.1
KMO-6-268B Codiciada Carbonate rock 4,375 rhc 18.4 5.6 10.9 9.3
KMO-7-200B Codiciada Carbonate rock 4,460 rhc 20.4 5.6 13.0 11.3
KMO-6-239 Codiciada Carbonate rock 4,615 rhc 6.4 8.2 1.1 2.8
MO-05-KK-05A Codiciada Carbonate rock 4,520 rhc 18.2 5.5 10.8 9.1
KMO-7-221 Sierra Nevada Carbonate rock 4,380 rhc 12.1 8.1 4.6 2.9
KMO-7-242B Sulfurosa Carbonate rock 4,240 rhc 18.2 4.7 10.7 9.0
KMO-7-242A Sulfurosa Carbonate rock 4,240 rhc 7.9 8.2 0.5 1.2
KMO-7-238A Sulfurosa Andesite 4,205 rhc 8.7 9.0 1.2 0.4
KMO-7-241 Sulfurosa Andesite 4,310 rhc 10.7 8.5 3.2 1.5
KMO-7-229 Sulfurosa Andesite 4,231 rhc 10.1 9.0 2.7 1.0
KMO-7-234A Sulfurosa Andesite 4,286 rhc 15.4 6.1 7.9 6.2

KMO-7-260 Manuelita Andesite 4,184 cal 5.5 2.8 2.4 2.8

KMO-6-269B Codiciada Carbonate rock 4,375 cal 11.7 7.7 3.8 3.4
KMO-6-231E Codiciada Porphyry intrusion 4,370 cal 9.4 3.4 1.5 1.1
KMO-6-295 Codiciada Porphyry intrusion 4,335 sid 13.2 4.9 4.3 3.8

Note: Fluid compositions were calculated using equations from Zheng (1999)
1 Location coordinates can be found in Catchpole (2011)
2 cal = calcite, rhc = rhodochrosite, sid = siderite
 ZONED BASE METAL MINERALIZATION IN A PORPHYRY SYSTEM, MOROCOCHA DISTRICT, PERU 59

2008), Colquijirca (Bendez, 2007), Julcani (Deen, 1990;

a volcanic
vapor
-10
Deen et al., 1994), and Pasto Bueno (Landis and Rye, 1974),
water dissolved
in felsic magmas Fluids at
-30
to name a few.
270 - 450C 18O and 13C values of the rhodochrosite are clearly isoto-
tur
ms
-50
pically lighter than published compositions of marine Pucar
L

DVSMOW[]
MW

Group carbonates (the main host for the polymetallic miner-

Tourmaline
T alization in the district), which mostly plot in the range of 20
-70
Morococha PMW Muscovite to 29, and 1 to +3, respectively (Moritz et al., 1996;
present day Spangenberg et al., 1996; Baumgartner et al., 2008). There
lake water -90

L
is a clear correlation between the 18O and 13C values (Fig.

eW
12) but no correlation between sample location and isotopic

nit
Modeled paleo-water composition
-110

oli
of other deposits in the
composition, and no horizontal or vertical zonation pattern is

Ka
Miocene polymetallic belt
observed. Nor does the host rock type correlate with the iso-
-14 -12 -10 -8 -6 -4 -2 0 2 4 6 8 10 12 14 16 18 20 topic signatures of hydrothermal carbonates.
18OVSMOW[] The low 13C values (9.0 to 2.8) could result from
450 assimilation of 13C-depleted organic matter from bituminous
b horizons in the Pucar Group carbonate rocks. However, sul-
porphyry-type fides in the Morococha district consistently yield values of 1
veins to 4 34S (Moritz et al., 2001; Ageneau, 2008; Prez, 2009;
qz tur Catchpole, 2011; Kouzmanov et al., 2011), showing that sul-
400 fur was not derived from a bituminous source, which would
quartz-pyrite have much lower 34S values of 30 to 20 (Hoefs, 2009).
stage A magmatic fluid source is more plausible. Similar 13C val-
ues for rhodochrosite from polymetallic vein and replacement
Cordilleran polymetallic veins

qz ms 350 deposits have been published for the Sweet Home Mine,
USA (Bartos et al., 2007; Lders et al., 2009), Creede, USA
Temperature (C)

(Bethke and Rye, 1979), Butte, USA (Garlick and Epstein,

1966), and others. Associated fluids have been systematically
base metal interpreted to be dominantly of magmatic origin.
stage Fluid compositions derived from the calcite and siderite
qz samples have lighter 13C values (5 to 3) compared to
ms the rhodochrosite trend, and are likely due to meteoric water-
270
rhc dominated fluid circulation during the late carbonate stage.
carbonate Only one calcite sample coincides with the rhodochrosite
stage trend at 7.7 13C and 11.7 18O.
qz
PMW
230 18O values of the fluid in equilibrium with rhodochrosite
have a considerable spread that ranges from 2.8 to 13.0,
-4 -2 0 2 4 6 8 10 12 14 16 18 20 calculated for temperatures of 230 to 270C (Fig. 13b). The
18OVSMOW[] wide compositional spread may result from fluid/rock inter-
Fig. 13. (a) 18O and D compositions of muscovite and tourmaline action of a magmatic fluid with surrounding carbonate rocks.
from porphyry-type veins and muscovite from Cordilleran polymetallic veins A positive correlation trend can result from a high fluid/rock
(white ellipse) are plotted together with the hydrothermal fluid in equilib- ratio and was observed in several carbonate-bearing base
rium with both minerals at 300 to 450C (gray ellipse). The results were metal deposits for similar compositional ranges, compiled
plotted using the following for reference: the meteoric water line (Rozanski
et al., 1993), the kaolinite water line (Savin and Epstein, 1970; Sheppard and
and discussed by Hoefs (2009), and also theoretically mod-
Gilg, 1996), the primary magmatic water (PMW) box (Taylor, 1974, 1997), the eled by Zheng and Hoefs (1993). Alternatively, a trend with
volcanic vapor box (Giggenbach, 1992), the water dissolved in felsic magma depleted 18O and constant 13C can be achieved by mix-
box (Taylor, 1988). (b) Calculated 18O compositions of fluid in equilibrium ing of a magmatic fluid with meteoric waters. 18O of fluid
with quartz, tourmaline, muscovite, and rhodochrosite from veins at different in equilibrium with rhodochrosite corresponds well to 18O
mineralization stages. The dashed arrow indicates the evolution path of fluid
compositions from temperatures of 450 to 230C. Until the carbonate stage, of fluid in equilibrium with carbonate-stage quartz, which is
the fluids are dominantly magmatic. Upon reaching the carbonate stage at a function of decreasing temperature and increasing mixing
<~270 C, the fluids have increasingly lighter isotopic compositions due to with meteoric fluid. Apparently, rhodochrosite from differ-
mixing with meteoric water. Abbreviations: ms = muscovite, qz = quartz, rhc ent parts in Morococha precipitated from a hydrothermal
= rhodochrosite, tur = tourmaline.
fluid that had variable proportions of magmatic and meteoric
components.
this assumption because several polymetallic deposits in the Cs/(Na + K) fluid inclusion values decrease with decreasing
Miocene polymetallic belt of central Peru have modeled 18O homogenization temperatures of about 270 to 230C (Fig.
compositions of paleometeoric water (12 to 15) that 10). We interpret this trend as mixing of a magmatic-derived
are also similar to their respective present-day meteoric water fluid with a nonmagmatic, low-salinity fluid depleted in Cs,
composition. These include San Cristobal in the Yauli dome possibly of meteoric origin. Oxygen stable isotope composi-
(Campbell et al., 1984), Cerro de Pasco (Baumgartner et al., tions of quartz, fluid inclusion microthermometry, and element
60 CATCHPOLE ET AL.
concentration trends all indicate boiling and fluid mixing with
meteoric water during rhodochrosite precipitation.
P-T-salinity evolution of fluids
The salinity, pressure, and temperature evolution of hydro-
thermal fluids responsible for district-scale base metal min-
eralization in the Morococha district is reconstructed on
the basis of fluid inclusion microthermometry. These new
data are used to establish a model of fluid evolution in this
porphyry-centered district. Intermediate-density fluid inclu-
sions in the thick milky quartz veins of the central Moroco-
cha district have low salinities (3.03.8 wt % NaCl equiv),
low CO2 contents (~6.68.5 mol %), and homogenization
temperatures of 410 to 420C, i.e., typical features of inter-
mediate-density porphyry-type fluid inclusions reported for
well-studied porphyry Cu deposits such as Bingham (Roed-
der, 1971; Redmond et al., 2004; Landtwing et al., 2005, 2010;
Seo et al., 2012), El Teniente (Klemm et al., 2007), Bajo de la
Alumbrera (Ulrich et al., 2001), and pre-Main stage mineral-
ization in Butte (Rusk et al., 2004, 2008b). Real entrapment
temperatures of intermediate-density fluids are probably con-
siderably higher, as these types of fluids can directly exsolve
from a magmatic source or separate from a saline magmatic
fluid close to the source (Hedenquist et al., 1998; Redmond
et al., 2004; Rusk et al., 2004, 2011; Heinrich, 2007; Klemm
et al., 2007; Audtat et al., 2008). In the absence of evidence
for unmixing in the milky quartz vein or other independent
pressure constraints, an absolute temperature determination
is not possible. Applying a pressure correction that agrees
with reported or estimated entrapment temperatures of 500
to 600C for intermediate-density fluids in other porphyry
systems (Rusk et al., 2008b, 2011; Landtwing et al., 2010),
pressures would correspond to 700 to 1,000 bar (500C) and
1,000 to 1,500 bar (600C) following an isochoric fluid path
(Fig. 14a).
A small number of base metal-rich brine fluid inclusion
assemblages (2932 wt % NaCl equiv) with opaque daugh-
ters were identified in the milky quartz veins and postdate
the intermediate-density fluid trails. They have variable Th of
260, 300, and 320C. Phase separation of low- to moderate- rate fluid batch following an isochoric path at higher pressures
salinity magmatic fluid to low-salinity vapor and high-salinity
brine is commonly observed in porphyry environments and
interpreted to be responsible for typical porphyry Cu min-
eralization by most authors (Roedder, 1984; Bodnar, 1995;
Lerchbaumer and Audtat, 2012). The salinities measured
in the fluid inclusion assemblages here are, however, rather
low compared to typical porphyry brines (Klemm et al.,
2007; Landtwing et al., 2010). A pressure correction of up
to 2 kbar would correspond to entrapment temperatures of
400 to 520C (Bodnar, 1994; Bodnar and Vityk, 1994; Cline
and Bodnar, 1994). However, textural evidence shows that B0
inclusions postdate intermediate-density fluids. Therefore, it
is unlikely that pressures were higher than 1.5 kbar, because
this is the maximum pressure for the intermediate-density
fluids after a pressure correction at 600C (Fig. 14a). Assum-
ing there was no dramatic pressure increase during the cool-
ing of the fluids, a more realistic temperature of entrapment
can be therefore estimated at 360 to 430C, at a maximum
of 1.5 kbar (Fig. 14b). The presence of abundant cooler,
liquid-rich fluid inclusions in the milky quartz vein records
continued reopening of the veins, after fluids had cooled and
lost CO2.
Fluid inclusions identified in the base metal veins have
homogenization temperatures ranging from 220 to 380C,
with salinity mostly in the 2 to 4 wt % NaCl equiv range, and a
smaller amount of intermediate-salinity fluid inclusion assem-
blages with values up to 16 wt % NaCl equiv and a brine at
35wt % NaCl equiv. These values coincide with fluid inclu-
sion data from base metal mineralization from similar mining
districts. These usually have salinities between 1 and 5 wt %
NaCl equiv, but can reach intermediate compositions of 5 to
23 wt% NaCl equiv and salinities of >30 wt % NaCl equiv
(Rye and Sawkins, 1974; Campbell et al., 1984; Hildreth and
Hannah, 1996; Hedenquist et al., 1998; Beuchat et al., 2004;
Simmons et al., 2005; Baumgartner et al., 2008; Rusk et al.,
2008a; Bendez and Fontbot, 2009). Magmatic fluid-derived
base metal sulfides from such deposits are classically inter-
preted to have precipitated from magmatic brines diluted by
meteoric waters (Landis and Rye, 1974; Kamilli and Ohmoto,
1977; John, 1989; Simmons, 1991; Deen et al., 1994; Bendez
and Fontbot, 2009) or directly from small amounts of mag-
matic brine (Wilkinson et al., 2013).
Intermediate-density fluids in the milky quartz vein are
comparable to the CO2-bearing L1-CO2 fluids of the early stages
of Cordilleran base metal veins and also to the CO2-bearing
L1 fluids reported by Catchpole et al. (2011). These L1-CO2 and
L1 fluids have salinities (~25 wt % NaCl equiv) and CO2 con-
tents (310 mol %) similar to the intermediate-density fluids,
and only the homogenization temperatures (340380C) are
lower. Assuming a small pressure correction (path A in Fig.
14c), the liquid-rich L1-CO2 fluids could be produced by cool-
ing and contraction of the intermediate-density fluids (i.e.,
increasing the density with decreasing temperature and pres-
sure; Fig. 14c). This process has been outlined by Heinrich
et al. (2004) and discussed by Richards (2011), and can be
important in the transport of economic metals from porphyry
to epithermal environment (Heinrich, 2007; Pudack et al.,
2009). Alternatively (path B), the L1-CO2 fluids might require
a larger pressure correction if they were derived from a sepa-
(Fig. 14c). A fluid following such a path could have also led to
the phase separation of the B0 fluid inclusions upon cooling
below 430C.
All of the fluid inclusion types identified in the Cordille-
ran base metal veins, including liquid-rich CO2-bearing (L1-
CO2) and intermediate-salinity fluid inclusion assemblages
(L1-interm) and one brine assemblage (B1), crosscut quartz crys-
tals of the early quartz-pyrite stage with similar paragenetic
setting and textures and have similar minimum entrapment
temperatures of 300 to 380C (Fig. 4d-f). We therefore pro-
pose the following interpretation of fluid evolution to explain
the fluid inclusion data.
Healed cracks in the quartz crystals of the quartz-pyrite
stage provide evidence for repeated events of vein opening or
reopening that caused increased permeability and fluctuation
in fluid pressure and, possibly, changes from a lithostatic-dom-
inated pressure regime to a hydrostatic one (Fig. 4d-f). The
sudden pressure drop caused phase separation of CO2-bear-
ing fluid (L1-CO2). In the 400 to 300C temperature range,
repeated fluid phase separation events led to loss of most
 ZONED BASE METAL MINERALIZATION IN A PORPHYRY SYSTEM, MOROCOCHA DISTRICT, PERU 61

3000 3000

Wet gra
10 mol% CO2 3

cm
2500 g/ 2500

n
75

ite solid
0.
70
0.

us
2000 65
2000
Pressure (bar)

0.
0
0.6
5
1500 0.5 1500
0
0.5
5
0.4
0.40
1000 1000

5 mol% CO2

500 ID 500

a B0 b
0 0
200 250 300 350 400 450 500 550 600 650 700 200 250 300 350 400 450 500
Temperature (C) Temperature (C)
3000

Wet
10 mol% CO2

gr
3
m
2500 g/c

anite
5
0.7
?

solid
0
0.7
2000

us
B
Pressure (bar)

5
0.6
0
0.6
1500 0.55
0.50
0.45
?
0.40
1000
5 mol% CO2

500 L1-interm L1-CO2 ID A

L2
? c
0
200 250 300 350 400 450 500 550 600 650 700
Temperature (C)
Fig. 14. Fluid evolution in the pressure-temperature space: (a) Isochores for a fluid of 4 wt % NaCl with 5 mol % CO2
(straight lines) and 10 mol % CO2 (dashed lines). The dashed curved lines mark the solvi for fluids in the system H2O-6 wt %
NaCl-CO2 between 5 and 10 mol % CO2 (Gehrig, 1980; Gehrig et al., 1986). Data for the intermediate-density fluid inclu-
sions plot in the black field. The gray field marks the P-T field of stability after a pressure correction to a maximum of 600C.
(b) Isochores of B0 fluid inclusions with a salinity of 30 wt % NaCl equiv. A pressure correction is limited to 1.5 kbar, which is
the maximum pressure for the intermediate-density fluid at 600C (Fig. 14a). (c) The fields (a) and (b) are combined together
with the P-T fields of the different fluid inclusion groups. By contracting intermediate-density fluid inclusions with decreasing
temperature, L1-CO2 fluids are produced (path A). Alternatively, L1-CO2 fluids could have resulted from simple pressure correc-
tion (path B). Possible early intermediate-density fluid paths that correspond to results from Rusk et al. (2008b) for similar
fluids from Butte are included.

CO2, and small amounts of fluids with moderate, intermedi-
ate (L1-interm), and high salinity (B1) were generated (Figs. 15,
16). However, the bulk of the fluid retained low salinities of 2
to 5 wt % NaCl and cooled to temperatures of about 270C,
marked by precipitation of Mn-bearing carbonates at the
transition of the base metal to carbonate stage. Boiling aque-
ous L2 fluid inclusions with temperatures between 240 and
290C indicate that P-T conditions followed or were near the
boiling curve below 300C, while salinity slightly decreased
(14 wt % NaCl) as the result of mixing with a diluting fluid.
The occasional presence of adularia in the carbonate stage
provides additional support for boiling conditions.
Depth estimation: In order to achieve geologically reason-
able depth estimates, we apply a model with lithostatic pres-
sure conditions for intermediate-density fluid inclusions and
a transition to hydrostatic conditions for the CO2-bearing
liquid-rich and intermediate-salinity fluid inclusions in the
Cordilleran veins (Fig. 17). The estimated pressures of 500 to
1,500 bar for intermediate-density fluids (Fig. 14c) correspond
to a depth of 1,700 to 5,000 m at lithostatic pressures. Con-
sidering the model of fluid phase separation at temperatures
of 400 to 300C, and assuming a pressure regime change
from lithostatic to hydrostatic, the minimum pressure values
of 100 to 700 bar for the CO2-bearing liquid-rich fluids and
62 CATCHPOLE ET AL.

36 e 36
curv
ion
34 rat 34
s at u
lite
ha
32 32
Unmixing
30 30

28 28
Salinity (wt% NaCl eq.)

16 litho- to hydrostatic 16
regime change,
14 pressure drop, 14
phase separation,
12 CO2 loss 12
Unmixing
10 10

8 8

6 Cooling of 6
ID fluids
4 4

2 2

0 0
Cooling, mixing, dilution

200 250 300 350 400 450

Th (C)
Fig. 15. Intermediate-density fluids cool to Cordilleran polymetallic L1 fluids. B1 and moderate- to intermediate-salinity
L1-interm fluid inclusion assemblages are interpreted to result from phase separation (unmixing) of low-salinity, CO2-bearing
L1-CO2 fluids. This is a result of a change from hydrostatic to lithostatic fluid pressure regime as a consequence of vein opening
or reopening and sudden drop of pressure. The bulk of the fluids retain low salinities during cooling of the evolving fluid to L2
fluids in the carbonate stage. Color codes and symbols of the fluid inclusion assemblages correspond to the legend in Figure 7.

intermediate-salinity fluids correspond to a minimum depth
of formation of 1,500 to 2,000 m (Fig. 17) and a maximum of
10,000 m. However, a maximum depth of 5,000m should be
considered, assuming that early intermediate-density fluids
were subject to a lithostatic pressure regime. A depth of 1 to 2
km is achieved for evolved, lower-temperature intermediate-
salinity fluids under hydrostatic pressure conditions. Boiling
assemblages of several lower-temperature fluids (L2) provide
absolute pressure estimates (3060 bar) and indicate a depth
of emplacement of 300 to 600 m beneath the paleowater table.
A minimum erosion of ~1.5 km can be estimated from the
temporal evolution of early and deep fluids (liquid-rich fluid
inclusion assemblages) of the early base metal stage to near-
surface boiling fluids of the carbonate stage. No correlation
of boiling temperature and depth could be identified for the
near-surface fluid inclusions measured in samples that were
taken from a vertical section in the Codiciada mines (Fig. 9).
It is more likely that these temperatures and pressures record
random moments when the fluid moved along the boiling
curve in the P-T space.
Origin of magmatic fluids: Intermediate-density magmatic
fluids, such as those identified in the Morococha milky quartz
vein, can be generated by cooling and contraction of mag-
matic high-density vapors which separated at high pressures
and temperatures (e.g., 700800 bar and ~600C) from a
moderately saline (e.g., 10 wt % NaCl equiv), single-phase
fluid exsolved from a magmatic source (Heinrich, 2007).
Alternatively, the intermediate-density fluid inclusions can
represent a low-salinity, single-phase fluid which directly
exsolved from a silicate melt with supercritical to intermedi-
ate densities, as proposed by Rusk et al. (2004) and Reed at
al. (2013) for pre-Main stage veins in Butte, and Shinohara
and Hedenquist (1997) and Hedenquist et al. (1998) for the
FSE-Lepanto cluster. Hedenquist et al. (1998) argue that
the low-salinity magmatic fluids exsolved at a low rate after
the collapse of isotherms during magma crystallization and
 ZONED BASE METAL MINERALIZATION IN A PORPHYRY SYSTEM, MOROCOCHA DISTRICT, PERU 63

1200
a liquid side projection b 1200

l curve

cri
critica

tica
70
1000
00 1000
00

l cu
0
vapor
single phase

rve
liquid 60 field
800 0 800
Pressure (bar)

Pressure (bar)
C
ID ID L1-CO2
600 two-phase ? 600

L1-CO2 50
0C
surface
litho- to hydrostatic
400 400
regime change, pressure
drop, and phase
400C separation
200 unmixing 200
B1 halite-liquid-vapor surface
B1
L1-interm300C L1-interm
L2 L2
0 10 20 30 40 50 60 70 80 90 100 600 500 400 300 200 100
Salinity (wt% NaCl eq.) Temperature (C)
Fig. 16. Salinity-pressure (a) and liquid side temperature-pressure (b) projection of the three-dimensional H2O-NaCl
phase diagram after Driesner and Heinrich (2007), modified from Klemm et al. (2007). Gray arrows indicate a proposed
evolutionary path in P-T-X space for different fluid inclusion groups. Colors of the fluid inclusion assemblages correspond to
colors of symbols in Figure 7.

the decrease of an initially high fluid flux. Therefore, those Butte (Rusk et al., 2008b; Reed et al., 2013). The Main-stage
low-salinity magmatic fluids did not cross the two-phase field polymetallic mineralization is similar to the Morococha base
during cooling, i.e., did not separate into a vapor and brine metal mineralization presented in this study. From the avail-
phase. Metal-rich fluids from barren quartz-pyrite veins that able data it is not clear if the Morococha intermediate-den-
predate the polymetallic Main stage in Butte, Montana, are sity and liquid-rich L1 fluids represent an evolved vapor or a
interpreted to be single-phase low-salinity fluids exsolved fluid directly exsolved from a crystallizing magma. Important
at higher pressures from a magma source and to have con- parameters such as initial fluid salinity and initial metal con-
tributed to the rich ores of the Main-stage mineralization at centrations are not known.

-500 L2 lith
os
tat
ic
-1000
Depth (m)

-1500 ID
pre ID
-2000 L1-interm ss an
L1-CO2 + L1 ure d
+ B1 co B0
rre
cti
hot

-2500 on
?
hyd
ros

-3000
tati

?
c

-3500
0 200 400 600 800
minimum pressure (bar)
Fig. 17. Depth model for calculated minimum pressures of fluid inclusion assemblages plotted against depth as a function
of hot hydrostatic and lithostatic pressure regimes. The gray fields correspond to minimum depth-pressure conditions of the
fluids between lithostatic and hydrostatic pressure regimes.
64 CATCHPOLE ET AL.
Metal content of fluids
The B0 fluid inclusions from the milky quartz vein with
salinities of 29 to 32 wt % NaCl have concentrations of up
to 7.8 and 0.94 wt % Fe and Cu, respectively, and up to
9,000g/g sulfur. These concentrations are high compared to
lower concentrations of other base metals (2,0006,000 g/g
Zn, 5001,000 g/g Pb). If these brines derived from phase
separation of a low-salinity fluid, this fluid would have had to
have higher initial concentrations of Fe, Cu, and S compared
to Pb and Zn. Intermediate-density fluids with salinities of
about 4 wt % NaCl and Fe and Cu concentrations of thou-
sands and ten thousand g/g meet these conditions and pos-
sibly represent the fluid from which the B0 fluids separated.
This also agrees with petrographic evidence which shows
that intermediate-density fluid inclusion trails predate the B0
fluid inclusion trails. Similar brines have been documented in
detailed fluid inclusion studies of porphyry Cu deposits and
document fluid phase separation at relatively late stages at
about 400 to 300C (Masterman et al., 2005; Klemm et al.,
2007; Landtwing et al., 2010).
Fluid phase separation, however, does not appear to have
been an important mineralizing process in the polymetal-
lic veins in the Morococha district. Low-salinity (05 wt %
NaCl) fluid inclusion trails are far more common (<1:100)
than vapor-rich and intermediate- to high-salinity fluid inclu-
sions (535 wt % NaCl) in all veins studied in the district. The
metal concentration data rather support cooling and sulfide
precipitation from the bulk fluid at an overall constant low
salinity. Small-scale fluid phase separation took place during
gradual loss of CO2 from about 400 to 300C. The data con-
sistently show that Fe and Cu in intermediate-density fluid
inclusions and CO2-bearing L1 fluid inclusions (Catchpole et
pre-base metal stage
10
Intermediate-density Brine
(ID) (B0)
1 Pb/(Na+K)
X / (Na+K)
0,1
0,01
0,001
0,0001
Fig. 18. Metal/(Na + K) ratios of main fluid inclusion types from the Morococha district plotted for comparison. Note the
low Cu/(Na + K) and Fe/(Na + K) values of brine and intermediate- and low-salinity fluids in Cordilleran polymetallic veins,
compared to intermediate-density and brine fluids from the milky quartz vein (pre-base metal stage).
al., 2011) have concentrations of thousands and ten thousand
g/g (respectively) that drop one to two orders of magnitude
to about several hundreds of g/g while cooling from about
420 to below 350C (Fig. 10). This drop in Fe and Cu coin-
cides with pyrite and Cu sulfide precipitation (chalcopyrite,
tennantite-tetrahedrite, or enargite), depending on sulfur and
oxygen fugacity, temperature, and pH of the fluid, partly con-
trolled by the degree of reaction with the host rock (Barnes
and Kullerud, 1961; Einaudi et al., 2003; Catchpole et al.,
2012; Kouzmanov and Pokrovski, 2012).
Sulfur concentrations are up to 1 wt % in intermediate-den-
sity fluid inclusions and some CO2-bearing L1 fluid inclusions
(Catchpole et al., 2011). Below 340C Th, sulfur concentra-
tions are mostly under detection limits (~1,000 g/g), reflect-
ing the consumption of the majority of S during the earlier
precipitation of Fe and Cu sulfides. Nevertheless, the sulfur
content is sufficiently high to precipitate all the base metals
in solution, and sulfide formation at Morococha is not depen-
dent on an external sulfur source (Catchpole et al., 2011).
Between 400 and 300C Th intermediate-salinity (L1-interm)
and brine (B1) fluid inclusions record strongly elevated Pb,
Zn, and Mn of up to 2.5%, 3%, and 2.5%, respectively. These
fluids are most likely derived from magmatic fluids, because
such high base metal concentrations have only been reported
in magmatic-derived brines in other porphyry systems (Yard-
ley, 2005). In comparison, Fe and Cu concentrations (up to
18,000 and 900 g/g, respectively) in the intermediate-salinity
fluids (L1-interm) and brine (B1) fluid inclusions are quite low
and Fe/(Na + K) and Cu/(Na + K) ratios are one to two orders
of magnitude lower than concentrations in the B0 brines in the
milky quartz vein (Fig. 18). Because Fe and Cu are expected
to preferentially concentrate in brine, just like Pb, Zn, and
Mn, we conclude that Fe and Cu might have precipitated as
Cordilleran polymetallic vein
Intermediate salinity Brine Fe/(Na+K)
(L1-interm.) (B1) Cu/(Na+K)
Zn/(Na+K)
Mn/(Na+K)
CO2-bearing,
liquid rich
(L1-CO2)
 ZONED BASE METAL MINERALIZATION IN A PORPHYRY SYSTEM, MOROCOCHA DISTRICT, PERU 65
sulfides. The fluids might have also been derived from unmix-
ing of a parent fluid that had already been depleted in Fe and
Cu. Such a fluid would have lost most of its Fe, Cu, and S dur-
ing an earlier precipitation of Fe- and Cu-bearing minerals,
while keeping Pb, Zn, and Mn in solution. Such compositions
correspond to the CO2-bearing, low-salinity L1-CO2 fluids at
similar Th values (Fig. 18).
Zinc and Pb concentrations decrease from several hundreds
to tens of g/g to mostly below detection limit at temperatures
between 340 and 270C for Zn, while Pb decreases to con-
centrations under 10 g/g for L2 fluids at temperatures below
270C. As temperatures constantly decrease from 270 to
230C and rhodochrosite precipitates, Mn concentrations in
the liquid-rich L2 fluids drop from over 100 to below 10g/g.
Recent experimental studies show that high Cu concentra-
tions can be the result of fluid inclusion reequilibration caused
by Cu diffusion, artificially increasing the Cu content by sev-
eral orders of magnitude (Lerchbaumer and Audtat, 2012).
The possibility that some of the high Cu values reported in
this study (especially for intermediate-density fluid inclu-
sions) are artifacts of such postentrapment modification can-
not be excluded.
Summary and Conclusions
Fluids that produced the Cordilleran polymetallic (Zn-Pb-
Cu-Ag) vein and replacement-style mineralization in the cen-
tral Morococha district are interpreted as cooled and evolved
metal-rich, intermediate-density porphyry-type fluids, based
on fluid inclusion microthermometry, LA-ICP-MS, and stable
isotope data. This study supports the hypothesis that Cordil-
leran polymetallic mineralization in Morococha formed from
the same magmatic and metal-rich fluids that are responsible
for formation of porphyry Cu deposits. These fluids are either
contracted high-density vapor that resulted from unmixing
of moderately saline magmatic fluids at depth or directly
exsolved low-salinity, magmatic fluids.
Intermediate-density porphyry-type fluids cooled from
>420 to ~340C, corresponding to low-salinity (~25 wt %
NaCl), CO2-bearing (310 mol %) fluids that are recorded
in the polymetallic veins. During the transition of lithostatic
to hydrostatic pressure regime, the fluids underwent a pres-
sure drop, lost most of their CO2 during phase separation, and
acquired moderate salinities, in some cases intermediate (~up
to 16 wt % NaCl) to brine compositions. However, the bulk of
the magmatic fluid retained low salinity while it continued to
cool under open-system conditions, precipitating Cu miner-
als, sphalerite, and galena. Upon cooling below 270C, the
fluid precipitated abundant rhodochrosite and quartz, while
following the boiling curve toward lower P-T conditions. Cor-
relating oxygen, hydrogen, and carbon isotope compositions
of vein minerals indicates that the hydrothermal fluids have
dominantly magmatic signatures, and were only diluted by
meteoric waters upon cooling during the late carbonate stage.
Copper (5,00018,000 g/g), sulfur (up to 12,000 g/g), and
iron (2,1006,000 g/g) concentrations in the intermediate-
density porphyry-type fluids are high and approximately five
to 10 times higher than in low-salinity fluids of the Cordil-
leran base metal veins, while the base metals Zn, Pb, and Mn
have comparable concentrations between 100 and 1,000 g/g
for both types of fluids. These findings suggest that the fluids
identified in Cordilleran polymetallic veins are composition-
ally similar to the porphyry-type fluids, and could have derived
from the latter after cooling and partial loss of Cu, Fe, and S,
probably by precipitation of pyrite, chalcopyrite, or other Cu
minerals. Decrease of Cu, S, Zn, Pb, and Mn concentrations
in fluids that formed Cordilleran base metal veins correlates
with decreasing homogenization temperatures. Precipitation
was controlled by increasing pH and dropping temperatures
during reaction of the low-salinity fluid with country rock. The
decrease of base metal contents corresponds to the overall
paragenesis in the Morococha district showing mainly Fe, Cu
Zn, Pb Mn sequences of mineral deposition with drop-
ping temperature during the base metal and carbonate stage.
The new data can explain the commonly observed base and
precious metal zonation patterns encountered around por-
phyry Cu deposits (e.g., Bingham, Butte) and show that both
deposit types can precipitate from similar magmatic-hydro-
thermal fluid pulses.
Acknowledgments
This study was supported by the Swiss National Sciences
Foundation (Grant 20020-108026) and the Pan American
Silver Corp., which provided field and logistical support and
access to the mine area. The Pan American Silver Corp. Moro-
cocha staff is acknowledged for friendly assistance, Marcus
Wlle for help during part of the laser ablation work at the ETH
Zurich, and Kerstin Bauer and Torsten Vennemann for support
in the stable isotope laboratory at the University of Lausanne.
Reviews by Brian Rusk, Anthony C. Harris, David Burrows,
Michael Steinmann, and Tim Baker substantially improved the
quality of this paper, as did reviews of an earlier version of this
manuscript by John Dilles and Christoph Heinrich.
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APPE
Element Concentrations (g/g) and Element/(Na + K) Ratios Obtained by LA-

Sample no.
Assemblage
Group Na K S Mn Fe

KMO-8-414 17-A ID 9000 1000 3100 1500 12000 4000 190 70 3900 1200
KMO-8-414 20-A ID 8800 1400 4500 1100 11000 1600 210 90 2500 1400
KMO-8-414 6-A ID 11100 600 5900 1400 10000 4000 340 110 2100 1100
KMO-8-414 6-B ID 10000 1200 5000 1000 8000 1000 200 90 6000 4000
KMO-8-414 4-A B0 78000 9000 50000 20000 6000 2000 5400 1400 56000 9000
KMO-8-414 5-A B0 59000 11000 57000 11000 9000 5000 9200 1600 78000 19000
KMO-8-414 9-A B0 63000 12000 70000 20000 9000 5000 7400 1900 63000 16000
KMO-8-414 5-B-Brine B0 85000 4000 50000 30000 9000 5000 4700 1500 37000 13000
KMO-6-288 C14 B1 104000 7000 87000 19000 25000 8000 18000 3000
KMO-6-288 A2 L1-CO2 12300 700 3700 700 2600 800 180 30 170 90
KMO-6-288 C11 L1-CO2 8300 400 1300 600 3600 1100 130 50 270
KMO-6-288 C13 L1-CO2 8100 1300 2400 1900 1800 600 120 30 210 140
KMO-7-244 2-A L1-CO2 1100 4000 900 1870 170 130
KMO-7-244 2-C L1-CO2 15000 3000 2600 1800 1500 600 300 200 150 70
KMO-7-244 2-A L1-interm 55000 4000 17000 6000 860 1600 600 700 300
KMO-7-244 2-B L1-interm 52000 6000 16300 1300 2180 1400 400 14000 20000
KMO-6-288 B5 L1-interm 33600 1300 13000 3000 810 1500 600 610 180
KMO-6-288 B6 L1-interm 43000 5000 14000 3000 1300 200
KMO-7-256 16-A L1-interm 19400 1700 5000 4000 1920 170 450 90 800 800
KMO-7-256 16-B L1-interm 16000 6000 6000 8000 1100 500 400 3000 3000
KMO-6-286 1-A-Boil L2 8200 1200 1470 110 100 50 760
KMO-6-286 1-B L2 6800 2200 600 300 20 30
KMO-6-286 1-C-Boil L2 3000 1400 250 190 4 90 20
KMO-6-286 1-E L2 2700 800 70 30 5 880
KMO-6-286 1-H L2 6000 3000 3000 2000 21 8
KMO-6-286 3-A L2 1900 200 900 500 15 11
KMO-6-286 3-B L2 4500 4200 33
KMO-6-286 3-C L2 3700 300 450 2
KMO-6-295 3-A L2 9000 6000
KMO-6-295 3-BB L2 10500 700 500 600 18
 ZONED BASE METAL MINERALIZATION IN A PORPHYRY SYSTEM, MOROCOCHA DISTRICT, PERU 69

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NDIX
ICP-MS for 41 Fluid Inclusion Assemblages from Morococha Vein Samples

Cu Zn As Mo Ag Sb Cs Au

11000 4000 210 70 23 13 6 4 20.00 20.00 6.0 2.0 4.0 2.0 2.9 2.0
5000 2000 210 70 26 12 11 20.00 30.00 2.1 0.2 4.0 2.0 7.3
18000 7000 310 60 50 50 4 3 200.00 300.00 4.0 4.0 6.0 3.0 2.0 3.0
13000 4000 230 40 35 50 2 130.00 120.00 5.3 0.5 1.5
5000 3000 3500 1300 90 100 3 3 17.00 10.00 5.0 2.0 90.0 70.0 0.3
300 300 6000 2000 9 4 17.00 17.00 30.0 30.0 130.0 30.0
8000 5000 4300 1700 90 60 40 30 40.00 60.00 34.0 60.0 180.0 80.0 20.0 20.0
9430 140 2000 1000 230 90 10 37.00 15.00 5.0 4.0 59.0 18.0
300 100 30000 11000 1100 400 81.00 14.00 130.0 80.0 100.0 3.0
200 100 30 30 80 50 3.00 3.00 5.0 1.5 14.0 5.0
180 130 80 30 60 90 1.10 0.60 37.0 40.0 15.0 2.0
180 120 70 30 22 8 0.60 0.30 20.0 10.0 11.0 8.0
140 60 50 50 45 11 16 1.70 1.00 22.0 8.0 5.0 5.0 2.4
340 60 300 300 70 40 30 43 2.00 4.00 12.0 9.0 11.0 3.0 12.9
600 600 2100 1200 220 170 26.00 13.00 50.0 60.0 56.0 21.0 14.0 14.0
900 600 3000 1300 45 17 9 1 32.00 15.00 13.0 77.0 60.0 20.0 10.0
110 30 180 30 140 80 2 3 400.0 200.0 48.0 11.0
400 200 320 270 390 120 4 800.0 300.0 176.0 8.0
90 60 34 16 80 30 30 40 3.00 2.00 20.0 20.0 31.0 15.0 5.0 5.0
170 80 200 200 94 22.00 10.00 50.0 30.0 36.0 9.0 17.5 0.8
5 18 40 30 13.2 1.2 20.4
4 1 11 11 30 20 0.80 0.70 41.0 6.0 4.6 1.2 0.1
3 5 5 14 12 13.00 30.0 10.0 3.0 3.0
10 24 4 18 16 0.50 20.0 30.0 7.0 4.0 0.7 0.4
2 27 20 30 18.0 13.0 6.0 3.0
2 2 43 13 9 180.0 110.0 1.2 0.2
13 15.0 2.0
3 4 23 18 0.20 40.0 50.0 7.0 5.0
17 46 23.0 11.0 20.0 6.0
14 75 40 30 1.10 0.11 80.0 80.0 13.0 8.0
70 CATCHPOLE ET AL.

APPENDIX

Sample no.
Assemblage
Group Na K S Mn Fe

KMO-6-295 3-C L2 11000 1000 660 60 60

KMO-6-295 7-A L2 15600 300 550 38 11 600 400
KMO-6-295 7-B L2 15000 2000 55
MO-06-KK-32 1-B L2 16200 700 2590
MO-06-KK-32 1-D L2 17000 700 420 49 17 500 500
MO-06-KK-32 1-H-boil L2 15500 800 40 30 700 600
MO-06-KK-32 5-A L2 10300 1100 4000 1000 80 140 80
MO-06-KK-32 5-B L2 11100 400 3400 200 11 1 20
KMO-7-221b A L2 10900 300 310 50 590
KMO-7-221b B L2 11300 200
KMO-7-221b C L2 6600 400 2000 1000 43

Sample no. Assemblage Group Pb S/(Na + K) Mn/(Na + K) Fe/(Na + K) Cu/(Na + K)

KMO-8-414 17-A ID 70.0 30.0 1.000 0.30 0.0170 0.0050 0.3100 0.1100 1.0000 0.3000
KMO-8-414 20-A ID 60.0 40.0 0.800 0.12 0.0160 0.0060 0.1900 0.1100 0.4100 0.1800
KMO-8-414 6-A ID 90.0 40.0 0.600 0.20 0.0210 0.0080 0.1300 0.0700 1.1000 0.4000
KMO-8-414 6-B ID 80.0 18.0 0.500 0.04 0.0130 0.0050 0.4000 0.3000 0.9000 0.3000
KMO-8-414 4-A B0 700.0 300.0 0.044 0.02 0.0410 0.0090 0.4400 0.0800 0.0500 0.0300
KMO-8-414 5-A B0 500.0 300.0 0.0800 0.0200 0.7000 0.2000 0.0030 0.0020
KMO-8-414 9-A B0 1000.0 300.0 0.070 0.03 0.0570 0.0160 0.4900 0.1600 0.0600 0.0400
KMO-8-414 5-B-Brine B0 1000.0 300.0 0.071 0.06 0.0390 0.0170 0.3000 0.1400 0.0740 0.0130
KMO-6-288 C14 B1 25000.0 5000.0 0.1300 0.0300 0.0960 0.0120 0.0014 0.0005
KMO-6-288 A2 L1-CO2 13.0 3.0 0.130 0.0115 0.0014 0.0110 0.0060 0.0120 0.0060
KMO-6-288 C11 L1-CO2 36.0 11.0 0.130 0.0140 0.0050 0.0290 0.0190 0.0140
KMO-6-288 C13 L1-CO2 40.0 20.0 0.100 0.0120 0.0040 0.0200 0.0140 0.0170 0.0120
KMO-7-244 2-A L1-CO2 13.0 5.0 0.0105
KMO-7-244 2-C L1-CO2 70.0 40.0 0.0190 0.0080 0.0070 0.0030 0.0190 0.0030
KMO-7-244 2-A L1-interm 4000.0 3000.0 0.0200 0.0100 0.0090 0.0050 0.0080 0.0070
KMO-7-244 2-B L1-interm 3800.0 1700.0 0.0200 0.0060 0.0270 0.0040 0.0100 0.0060
KMO-6-288 B5 L1-interm 120.0 30.0 0.003 0.0330 0.0130 0.0130 0.0040 0.0024 0.0007
KMO-6-288 B6 L1-interm 400.0 200.0 0.0260 0.0050 0.0070 0.0030
KMO-7-256 16-A L1-interm 15.0 16.0 0.0180 0.0030 0.0400 0.0300 0.0040 0.0020
KMO-7-256 16-B L1-interm 40.0 50.0 0.0170 0.0020 0.0680 0.0046
KMO-6-286 1-A-Boil L2 40.0 6.0 0.0070 0.0040 0.0834 0.0005
KMO-6-286 1-B L2 4.0 4.0 0.0030 0.0030 0.0007 0.0001
KMO-6-286 1-C-Boil L2 1.3 1.1 0.0011 0.0753 0.0009
KMO-6-286 1-E L2 14.0 12.0 0.1948 0.0015
KMO-6-286 1-H L2 0.6 0.0024 0.0009 0.0003
KMO-6-286 3-A L2 15.0 0.0040 0.0040 0.0007 0.0009
KMO-6-286 3-B L2 0.0038
KMO-6-286 3-C L2 7.0 0.0005 0.0007
KMO-6-295 3-A L2 7.800
KMO-6-295 3-BB L2 7.0 3.200 0.0018 0.0012
KMO-6-295 3-C L2 4.0 3.500 0.0019 0.0023
KMO-6-295 7-A L2 13.0 5.0 37.200 0.0027 0.0196 0.0004
KMO-6-295 7-B L2 1.0 0.0033
MO-06-KK-32 1-B L2 50.0 20.0
MO-06-KK-32 1-D L2 5.1 1.6 0.0023 0.0152 0.0014
MO-06-KK-32 1-H-boil L2 2.7
MO-06-KK-32 5-A L2 3.0 3.0 0.0100 0.0100 0.0055 0.0001
MO-06-KK-32 5-B L2 0.0007 0.0001 0.0014 0.0001
KMO-7-221b A L2 2.0 0.0024
KMO-7-221b B L2
KMO-7-221b C L2 2.0 0.0053
 ZONED BASE METAL MINERALIZATION IN A PORPHYRY SYSTEM, MOROCOCHA DISTRICT, PERU 71

(Cont.)

Cu Zn As Mo Ag Sb Cs Au

36 5 133 12 400.0 200.0 15.0 8.0 4.6

15 12 47 16 1.00 2.00 40.0 20.0 16.0 8.0
21 6.0 14.0
60 30 180.0 120.0 50.0 30.0 16.0 9.0
26 17 26 6 53 16 1.10 0.80 100.0 60.0 42.0 19.0
30 30 90 20 1.80 1.10 100.0 80.0 18.0 5.0 5.0 5.0
1 1 90 50 0.60 0.70 80.0 100.0 21.0 5.0 0.4
1 2 18 8 0.20 0.02 14.0 6.0 27.0 7.0
28 17 88 16 30.0 8.0 6.0
8 40 20 160.0 190.0 8.0 5.0
14 21 12 12.0 10.0 7.0 2.0

Zn/(Na + K) As/(Na + K) Mo/(Na + K) Ag/(Na + K) Sb/(Na + K) Cs/(Na + K) Au/(Na + K) Pb/(Na + K)

0.0180 0.0060 0.00180 0.00110 0.0005 0.0003 0.0020 0.0020 0.0005 0.0002 0.0004 0.0002 0.0001 0.0001 0.0060 0.0030
0.0160 0.0060 0.00190 0.00090 0.0007 0.0020 0.0020 0.0001 0.0003 0.0002 0.0006 0.0040 0.0030
0.0190 0.0040 0.00300 0.00300 0.0002 0.0002 0.0140 0.0160 0.0002 0.0003 0.0004 0.0002 0.0001 0.0002 0.0050 0.0020
0.0150 0.0030 0.00200 0.00300 0.0001 0.0000 0.0090 0.0080 0.0003 0.0001 0.0050 0.0009
0.0260 0.0100 0.00070 0.00080 0.0001 0.0001 0.0007 0.0005 0.0060 0.0030
0.0520 0.0180 0.0001 0.0001 0.0001 0.0001 0.0002 0.0003 0.0012 0.0003 0.0003 0.0004 0.0050 0.0020
0.0330 0.0130 0.0003 0.0002 0.0003 0.0003 0.0003 0.0005 0.0014 0.0005 0.0002 0.0002 0.0070 0.0020
0.0190 0.0070 0.00180 0.00170 0.0001 0.0003 0.0001 0.0005 0.0001 0.0080 0.0040
0.1500 0.0500 0.00600 0.00140 0.0004 0.0001 0.0007 0.0004 0.0005 0.0001 0.1300 0.0200
0.0018 0.0016 0.00500 0.00300 0.0002 0.0002 0.0003 0.0001 0.0009 0.0003 0.0008 0.0002
0.0080 0.0040 0.00700 0.01000 0.0001 0.0001 0.0040 0.0040 0.0016 0.0002 0.0040 0.0012
0.0070 0.0030 0.00210 0.00080 0.0001 0.0020 0.0010 0.0011 0.0008 0.0040 0.0020
0.00485 0.0019 0.0002 0.0014
0.0130 0.0110 0.00400 0.00300 0.0016 0.0020 0.0001 0.0002 0.0007 0.0003 0.0007 0.0003 0.0040 0.0012
0.0300 0.0140 0.00300 0.00400 0.0004 0.0002 0.0010 0.0010 0.0007 0.0002 0.0001 0.0001 0.0600 0.0300
0.0340 0.0050 0.00060 0.00030 0.0001 0.0005 0.0002 0.0002 0.0007 0.0001 0.0003 0.0002 0.0500 0.0300
0.0040 0.0008 0.00300 0.00160 0.0090 0.0040 0.0011 0.0003 0.0030 0.0007
0.0050 0.0040 0.00600 0.00200 0.0106 0.0029 0.0002 0.0047 0.0003
0.0012 0.0005 0.00300 0.00140 0.0014 0.0016 0.0001 0.0001 0.0011 0.0008 0.0013 0.0005 0.0002 0.0002 0.0006 0.0006
0.00400 0.00160 0.0005 0.0005 0.0013 0.0001 0.0009 0.0004 0.0004
0.0017 0.00400 0.00300 0.0014 0.0001 0.0042
0.0016 0.0009 0.00300 0.00200 0.0001 0.0001 0.0060 0.0010 0.0006 0.0002 0.0006 0.0003
0.0014 0.0014 0.00300 0.00120 0.0042 0.0130 0.0110 0.0011 0.0006 0.0005 0.0003
0.0032 0.00320 0.00040 0.0001 0.0030 0.0020 0.0020 0.0011 0.0001 0.0170 0.0180
0.0027 0.00200 0.00200 0.0120 0.0019 0.0012 0.0007 0.0003 0.0001
0.0147 0.00500 0.00300 0.0500 0.0300 0.0005 0.0001 0.0473
0.00148 0.0017 0.0002
0.0011 0.00601 0.0008 0.0006 0.0159

0.00500 0.00300 0.0001 0.0100 0.0100 0.0008 0.0008

0.01171 0.0400 0.0006 0.0003 0.0003
0.00352 0.0021 0.0007
0.00126 0.0004 0.0008 0.0000

0.0015 0.00304 0.0089 0.0011

0.0001 0.00600 0.00300 0.0001 0.0001 0.0060 0.0060 0.0015 0.0003 0.0003 0.0003
0.0001 0.00120 0.00060 0.0010 0.0004 0.0019 0.0005
0.0015 0.00800 0.00180 0.0024 0.0007 0.0006 0.0002

0.00190 0.00070 0.0016 0.0015 0.0008 0.0003 0.0003