Ore Geology Reviews 147 (2022) 104964

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Ore Geology Reviews

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Rapid transition to fertile magma and promotion of porphyry

mineralization: A case study from the Don Javier deposit
Nian Chen a, Jingwen Mao a, b, *, Zhenchao Ye a, Zheng Duan c, d, Hongying Li b
a
MNR Key Laboratory for Exploration Theory & Technology of Critical Mineral Resources, China University of Geosciences, Beijing 100083, China
b
Ministry of Natural Resources (MNR) Key Laboratory of Metallogeny and Mineral Assessment, Institute of Mineral Resources, Chinese Academy of Geological Sciences
(CAGS), Beijing 100037, China
c
Nanjing Center of China Geological Survey, Nanjing 210016, China
d
Chinese Academy of Geological Sciences(CAGS), Beijing 100037, China

A R T I C L E I N F O A B S T R A C T

Keywords: The Don Javier porphyry Cu–Mo deposit formed contemporaneously with the Incaic I orogeny (~60 Ma) in
Southern Peru southern Peru. The causative dacite porphyry is hosted by the Yarabamba Superunit, which is the youngest
Orogeny batholithic unit in the Toquepala arc. In this study, we conducted elemental and isotopic analyses on samples
Porphyry deposit
from the dacite porphyry and Yarabamba Superunit in an effort to clarify the origins and formation mechanism
Magmatic oxygen fugacity
of the deposit. Zircon U–Pb dating shows that the young part of the Yarabamba Superunit was emplaced at 65.4
Magmatic volatile
± 0.7 to 63.5 ± 0.8 Ma, and the causative dacite porphyry was emplaced at Don Javier between 59.9 ± 0.4 and
59.2 ± 1.1 Ma. The Yarabamba Superunit and dacite porphyry have similar εHf(t) and δ18O isotope values,
ranging from –4.6 to +1.9 and 5.1‰ to 6.4‰, respectively. The Yarabamba Superunit has initial Sr and Nd
isotope values of 0.70533–0.70579 and 0.51242–0.51244, respectively. Isotopic data suggest that the Yar­
abamba Superunit and dacite porphyry evolved from an isotopically homogeneous magma reservoir with minor
crustal assimilation. However, the dacite porphyry has whole-rock and zircon Eu/Eu* values of 0.9 and 0.34,
respectively, higher than those of the Yarabamba Superunit (0.6 and 0.13).
Additionally, the dacite porphyry has significantly higher apatite S content (0.07 wt%) and XCl values (0.21)
than those of the Yarabamba Superunit (apatite S: 0.01 wt%; XCl values: 0.15). The calculated magmatic
oxidation state shows that the dacite porphyry has a significantly higher magmatic oxygen fugacity (ΔFMQ +1.1)
than the Yarabamba Superunit (ΔFMQ –0.5).
Together, the data suggest that the magmas formed the Yarabamba Superunit and causative dacite porphyry
are characteristics of distinct tectonic regimes. The magma of the Yarabamba Superunit was generated during
normal subduction and underwent low-pressure, H2O-poor, plagioclase-dominated fractionation while the
magma of the dacite porphyry was generated during arc compression and underwent high-pressure, H2O-rich,
amphibole-(garnet) dominated fractionation, which led to a high oxidation state and volatile-rich magma that
promoted porphyry mineralization at Don Javier. This rapid elevation of the magmatic oxidation state and
volatile content occurred synchronously with the Incaic I orogeny (~60 Ma), which indicates that this orogeny
had a significant impact on the formation of the very large–super-giant porphyry ore systems in southern Peru.

1. Introduction spatial-temporally related with shallowly emplaced normal calc-alkaline

Magmatic–hydrothermal ore deposits, which include porphyry ore
systems, are important sources of metals such as copper, gold, molyb­
denum, and rhenium (Sillitoe, 2010). Sulfide-rich porphyry ore systems
(e.g., containing pyrite, chalcopyrite, and molybdenite) are often
to adakitic magmas (Chiaradia et al., 2012; Richards, 2011a; Richards
et al., 2012). These ore-related magmas are generally oxidized and hy­
drous with high Sr/Y ratios (Meng et al., 2021; Rezeau and Jagoutz,
2020; Richards, 2015; Zhu et al., 2018). High Sr/Y magmas were
initially thought to derive from the partial melting of hydrated oceanic

* Corresponding author at: MNR Key Laboratory for Exploration Theory & Technology of Critical Mineral Resources, China University of Geosciences, Beijing
100083, China.
E-mail address: jingwenmao@263.net (J. Mao).

https://doi.org/10.1016/j.oregeorev.2022.104964
Received 15 March 2022; Received in revised form 24 May 2022; Accepted 1 June 2022
Available online 4 June 2022
0169-1368/© 2022 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
N. Chen et al.
crust in subduction zones (Mungall, 2002; Oyarzun et al., 2001; Sajona
and Maury, 1998; Sun et al., 2010). However, they were later proposed
to originate from mantle-derived magma which underwent long-term
and high-pressure evolution at deeper crustal magma reservoirs
(Chiaradia, 2009; Chiaradia et al., 2009a, 2009b; Loucks, 2021;
Richards, 2011a; Rohrlach and Loucks, 2005; Chiaradia and Caricchi,
2017) such as hot zone (Annen et al., 2006) or MASH (melting, assim­
ilation, storage, and homogenization) zone (Hildreth and Moorbath,
1988).
Ore-related magmas emplaced at the upper crustal levels (i.e., 5–15
km) are widely recognized to have high sulfur (mainly S6+) and chlorine
contents, as indicated by the presence of S6+- and Cl-rich apatite and
igneous anhydrite (Chambefort et al., 2008; Li et al., 2021; Meng et al.,
2021; Zhu et al., 2018). In addition, they often have high water content,
as indicated by the presence of amphibole (Naney, 1983; Wang et al.,
2014a; Zhou et al., 2020). Sulfur-rich and oxidized magmas are
commonly emplaced in the Cenozoic in thick continental magmatic arcs,
such as the Gangdese belt (Tang et al., 2020) and the Andes (Chambefort
et al., 2008; Chen et al., 2022a). However, porphyry mineral deposits
are generally rare and discrete in these mature magmatic arc segments,
which indicates that their formation is controlled by specific tectonic
events (Cooke et al., 2005; Sillitoe and Perelló, 2005; Tosdal and
Richards, 2001; Wilkinson, 2013; Chen et al., 2022b). Such tectonic
events may rapidly promote magmatic maturation at various crustal
levels and subsequent emplacement at the upper crustal levels
Fig. 1. Maps showing the (A) location of the San Felix Ridge at ~60 Ma; (B) locations of the Toquepala and Andahuaylas–Anta arcs; and (C) geology of the
Paleocene–Eocene southern Peru metallogenic belt. Maps modified from IGEMMENT (2015) and mineralization ages are from Quang et al. (2003), Simmons (2013),
Martínez et al. (2017), and Ye et al. (2022). Abbreviation: SFR = San Felix Ridge.
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Ore Geology Reviews 147 (2022) 104964
(Chiaradia et al., 2009a; Loucks et al., 2020; Chen et al., 2022b).
The Paleocene–Eocene metallogenic belt of southern Peru contains
numerous giant–super-giant porphyry Cu deposits (Fig. 1) based on the
classification of Clark (1993). These include the Toquepala, Cerro Ver­
de–Santa Rosa, Quellaveco, Cuajone, and Los Calatos deposits (Ale et al.,
2020; Martínez et al., 2017; Shatwell, 2021; Simmons, 2013; Zweng
et al., 1995), as well as the very large Don Javier deposit (Ye et al.,
2022). These deposits formed during the Incaic I orogeny (~60 Ma),
which marked a period of tectonic transition from normal subduction to
strong arc compression (Nathwani et al., 2021; Simmons et al., 2013).
This makes them suitable for surveying magmatic responses to changes
in the geodynamic regime.
The Don Javier porphyry Cu–Mo deposit is in southern Peru and is
estimated to contain 303 Mt of mineral resources (indicated and infer­
red) with grades of 0.43 wt% Cu, 0.017 wt% Mo, and 2.6 g/t Ag
(Webster et al., 2013). We studied the evolution of the magmatic
oxidation state and of the volatiles in pre-mineralization and syn-
mineralization intrusions from Don Javier, by analyzing the whole-
rock elements, whole-rock Sr–Nd, zircon Hf–O isotopes, and minerals
elements (amphibole, plagioclase, apatite, and zircon). Our study may
help to clarify the conditions that lead to the formation of porphyry
mineral deposits in mature magmatic arc segments and facilitate their
exploration.
N. Chen et al.
2. Geologic setting
The Don Javier deposit is located in the boundary area spanning from
the Western Cordillera to the Atico–Mollendo–Tacna domain (Fig. 1B).
The Cincha–Lluta–Incapuquio fault system (SFCLLI; Jacay et al., 2002)
bounds these two tectonic domains (Fig. 1C). The oldest rocks are the
Precambrian metamorphic basement complex of the Arequipa Massif
(Coira et al., 1982), which is exposed mainly in the Ati­
co–Mollendo–Tacna domain. This basement complex is unconformably
overlain by Jurassic–Early Cretaceous marine, continental, and volcanic
sediments (Boekhout et al., 2012; Manrique, 2011; Sempere et al.,
2002). These Mesozoic sediments are in turn unconformably overlain by
Late Cretaceous–Paleogene volcanic and continental sediments of the
Toquepala Group (75–55 Ma), which mainly crops out in the Western
Cordillera (Decou et al., 2011; Manrique, 2011). Local developments of
unconformity suggest that tectonic compression events occurred during
this period. The specific tectonic event discussed here is the Incaic I
orogeny (~60 Ma) in southern Peru (Noble et al., 1979; Noble et al.,
1985; Roperch et al., 2011). Magmatism during this period formed the
Toquepala arc which includes several superunits (also referred as
batholiths) such as the Linga, Tiabaya, Toquepala, and Yarabamba
Superunits (Demouy et al., 2012; Manrique, 2011; Mukasa, 1986; Santos
et al., 2019). The youngest plutons are generally grouped in the Yar­
abamba Superunit, which hosts the causative porphyries for Cerro
Verde–Santa Rosa, Don Javier, Cuajone, Quellaveco, and Toquepala
porphyry deposits (Manrique, 2011; Sillitoe and Mortensen, 2010;
Simmons, 2013). These deposits occur in belts along or near the SFCLLI
and its secondary faults (Fig. 1). Subsequently, magmatism migrated to
the northeast by ~150 km to the Andahuaylas–Anta arc (Fig. 1B;
Mamani et al., 2010; Perelló et al., 2003). Since the Paleogene–Neogene,
this region has been dominated by forearc basin (Moquegua Basin)
sediments, comprising mudstone, sandstone, conglomerate, and ignim­
brite of the Moquegua Group (Decou et al., 2011). The Quaternary
mainly comprises pyroclasts, fluvial, and eolian deposits (Manrique,
Fig. 2. Simplified geologic map of the Don Javier deposit based on Chen et al. (2017) and Ye et al. (2022). Data Source: * = Ye et al. (2022).
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Ore Geology Reviews 147 (2022) 104964
2011).
3. Geology of the Don Javier deposit
The Don Javier deposit was discovered in the 2010s (Webster et al.,
2013), and its geology was preliminarily described by Jin (2010), Zhang
(2011), Gao (2012), Wu et al. (2013), Wu (2014), and Chen et al. (2017).
The geological and geochronological constraints on the deposit were
recently established by Ye et al. (2022). This deposit is hosted by the Don
Javier porphyry complex, which intrudes into the Yarabamba Superunit.
The Yarabamba Superunit is the youngest plutonic unit of the Coastal
Batholith in the region, which intrudes the Jurassic Labra Formation of
the Yura Group (Manrique, 2011; Fig. 2). The porphyry complex is
tabular, elongated, and northwest-striking; it is approximately 2 km long
and 300–800 m wide (Fig. 2). The northwest trend of the porphyry
complex indicates that it was controlled by the regional SFCLLI (Ye
et al., 2022).
The porphyry complex is a composite of intermineralization dacite
porphyry and late- to post-mineralization dikes (Chen et al., 2017; Ye
et al., 2022). The intermineralization dacite porphyry contains pheno­
crysts of plagioclase, quartz, and biotite with a microgranular ground­
mass. Although Chen et al. (2017) noted that the intermineralization
intrusion may have several pulses, no intrusive contacts were observed
within the dacite porphyry (Ye et al., 2022). Laser ablation–inductively
coupled plasma–mass spectrometry (LA–ICP–MS) of the dacite porphyry
yielded a zircon U–Pb age of 59.9 ± 0.4 to 59.5 ± 0.3 Ma (Ye et al.,
2022). Two swarms of late- to post-mineralization dikes (i.e., andesite
and aplite) were observed at Don Javier that are generally northwest- to
east-striking and have been obviously subjected to faulting (Fig. 2).
However, only weak mineralization was observed within these dikes.
Hydrothermal breccia is widespread development at Don Javier (Ye
et al., 2022; Fig. 2). They are pipe-like (Fig. 3) with subrounded to
subangular clasts of the Yarabamba Superunit and dacite porphyry in­
trusions. The cement contains tourmaline, quartz, sulfides (i.e., pyrite,
N. Chen et al.
Fig. 3. Geological cross-section along line A–A′ (see Fig. 2) looking northeast.
chalcopyrite, and molybdenite), local galena and sphalerite. The sulfide-
cemented hydrothermal breccia generally developed within the orebody
and shows high grades of Cu and Mo. Rare veins cut the sulfide-
cemented hydrothermal breccia, but locally the clast contains trun­
cated quartz veins. Tourmaline-cemented hydrothermal breccia was
also observed within the orebody and its peripheries.
Previous studies have identified potassic, sericite–chlorite, sericitic,
and propylitic alterations at Don Javier (Ye et al., 2022). The potassic (i.
e., biotite and K–feldspar) relicts are only preserved at depth in the
plutonic rocks (Fig. 3). This alteration is characterized by assemblages of
hydrothermal K–feldspar, biotite, and minor quartz. The potassic alter­
ation is overprinted by a sericite–chlorite alteration (Fig. 3).
The sericite–chlorite alteration is characterized by the replacement
of plagioclase by sericite and of mafic minerals (i.e., biotite and
amphibole) by chlorite. This alteration zone is preserved at depths of
500–1500 m and has higher Cu and Mo grades than the potassic alter­
ation zone. One sample from this alteration zone had a molybdenite
Re–Os model age of 59.6 ± 0.8 Ma, but two other deeper samples had
model ages of 45.4 ± 1.4 and 44.4 ± 1.6 Ma (Ye et al., 2022).
The sericitic alteration (0–100 m depth) is shallower than the ser­
icite–chlorite alteration and mainly developed in the dacite porphyry
(Fig. 3). The plagioclase and mafic minerals (i.e., biotite and amphibole)
were generally replaced by sericite (mainly illite and muscovite) and by
minor quartz. The primary quartz generally survived. Two molybdenite
samples from this alteration zone had Re–Os model ages of 60.5 ± 1.4
and 60.3 ± 1.0 Ma (Ye et al., 2022).
The propylitic alteration developed at the periphery of the ser­
icite–chlorite and sericitic alterations in both the dacite porphyry and
plutonic rocks. This alteration is characterized by an assemblage of
hydrothermal chlorite, epidote, and calcite. This alteration zone is
generally barren; veins are rare and only contain disseminated pyrite
and chalcopyrite.
Previous studies have identified at least five types of veins/veinlets at
Don Javier (Ye et al., 2022). The earliest biotite and magnetite veins
mainly developed in the potassic and propylitic alteration zones, but
they can also be observed in the sericite–chlorite alteration zone. Early
quartz and sulfide–quartz veins are the widest (44 vol% of drill cores)
and contain abundant Cu and Mo. The last stage D-type vein is also
widely developed (41 vol% of drill cores) but contains less chalcopyrite
and molybdenite than sulfide–quartz veins, and thus yields lower Cu and
Mo grades.
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Ore Geology Reviews 147 (2022) 104964
4. Sampling and analytical methods
4.1. Sampling
Four samples of the Yarabamba Superunit and four samples of the
dacite porphyry were collected from Don Javier (Figs. 2, 4A–C). For the
Yarabamba Superunit sample set, three fresh samples of the Yarabamba
Superunit (Fig. 5A–C) were collected from the surface and distal from
mineralization centers. These three rock samples (DJ01, DJ03, and
DJ04) contain plagioclase (50%–80%), K–feldspar (5%–20%), quartz
(5%–20%), hornblende (5%–10%), biotite (5%–10%), and minor cli­
nopyroxene (0%–5%) and orthopyroxene (0%–2%). One drill core
sample (S34) of the Yarabamba Superunit was collected from the
mineralized orebody and contains propylitic alteration.
For the dacite porphyry sample set, one texturally intact surface
sample (Figs. 2, 4D) was selected from the periphery of the orebody. This
sample (DJ02) contains phenocrysts of plagioclase (40%–60%), biotite
(5%–20%), and quartz (5%; Fig. 5). Three drill core samples (S30, S31,
and S32) were collected from the mineralized dacite porphyry with
texturally fragmented sericitic or propylitic alterations. Table 1 sum­
marizes the sample information.
4.2. Analytical methods
Whole-rock element and Sr–Nd isotope analyses were conducted on
the three fresh samples of the Yarabamba Superunit (DJ01, DJ03, and
DJ04). Whole-rock element analysis was also conducted on the textur­
ally intact dacite porphyry sample (DJ02). Because the dacite porphyry
samples were generally altered, no whole-rock Sr–Nd isotope analysis
was conducted on them (Table 1). Fresh amphibole and plagioclase
grains in samples DJ01, DJ03, and DJ04 of Yarabamba Superunit were
also selected for electron probe microanalysis (EPMA; Table 1). Zircon
grains were separated from the samples and mounted in epoxy resin. In
situ U–Pb dating (LA–ICP–MS) was conducted on DJ01–DJ04 (Table 1).
The remaining four samples (S30–S32 from the dacite porphyry and S34
from the Yarabamba Superunit) were previously dated by Ye et al.
(2002). Zircon Hf–O analysis was conducted on DJ01 and DJ04 of the
Yarabamba Superunit and DJ02 of the dacite porphyry. Zircon trace
element analysis was conducted on all eight samples.
Apatite is vulnerable to hydrothermal fluid (Cao et al., 2021). Thus,
we performed EPMA on the apatite inclusions in fresh plagioclase from
DJ01, DJ03, and DJ04 of the Yarabamba Superunit (Fig. 5E) and in
highly refractory zircon from DJ02 of the dacite porphyry (Fig. 5F).
Analyses of whole-rock geochemistry and Sr–Nd isotopes, and of
mineral elemental geochemistry (EPMA) were carried out at the Wuhan
N. Chen et al.
Fig. 4. Collected samples of the Yarabamba Superunit and dacite porphyry: (A) DJ01, (B) DJ03, and (C) DJ04 from the Yarabamba Superunit and (D) DJ02 from the
dacite porphyry. DJ03 has a low magnetite content. Abbreviations: amp = amphibole, bt = biotite, kf = K–feldspar, pl = plagioclase, qtz = quartz, sul = sulfide
(pyrite and chalcopyrite).
Sample Solution Analytical Technology Co. Ltd. Zircon U–Pb dating and
trace element analyses were conducted by using laser abla­
tion–inductively coupled plasma–mass spectrometry (LA–ICP–MS). Hf
isotope analysis was conducted by using laser abla­
tion–multicollector–inductively coupled plasma–mass spectrometry
(LA–MC–ICP–MS) at Nanjing FocuMS Technology Co. Ltd. Zircon O
isotope analysis was conducted by using secondary ion–mass spec­
trometry (SIMS) at the Beijing Research Institute of Uranium Geology.
Details on the analytical methods are given in Electronic Appendix A.
5. Results
5.1. Zircon U–Pb dating
Some spot analyses have high common Pb contents, as revealed by
the arrays of high 207Pb/206Pb ratios. Thus, the zircon U–Pb results are
presented in inverse Concordia diagrams (Fig. 6). Scattered ages that
may have been caused by inherited zircons or antecrysts (resulting in
older 238U/206Pb ages than that of their population group) or by
radiogenic Pb loss (resulting in younger 238U/206Pb ages than that of
their population group) were discarded. These include values from the
Yarabamba Superunit samples DJ01 (n = 1), DJ03 (n = 13), and DJ04 (n
= 9) and from the dacite porphyry sample DJ02 (n = 2). DJ01, DJ03,
and DJ04 yielded intercept ages of 65.4 ± 0.7 Ma (mean squared
weighted deviation; MSWD = 1.2, n = 26), 63.5 ± 0.8 Ma (MSWD = 0.5,
n = 14), and 63.9 ± 0.6 Ma (MSWD = 0.9, n = 16), respectively. DJ02
yielded an intercept age of 59.2 ± 1.1 Ma (MSWD = 1.4, n = 23).
5.2. Whole-rock geochemistry
Because of the scarcity of the Yarabamba Superunit and dacite por­
phyry samples in this study, we supplemented them with geochemical
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Ore Geology Reviews 147 (2022) 104964
data from Gao (2012). Based on the criterion of the analytical total being
>96% (i.e., volatile-free basis), two of the three available samples from
the Yarabamba Superunit and one of the five available samples from the
dacite porphyry were selected (Table 2). Overall, the igneous rocks in
the samples are diorite (monzonite) to granodiorite and vary from low-K
calc-alkaline to shoshonitic (Fig. 7). All samples are characterized by
enrichment of large-ion lithophile elements (LILEs; e.g., Rb, Ba, Th, and
K), depletion of high field-strength elements (HFSEs; e.g., Nb and Ta),
and negative Ti anomalies (Fig. 8A), which are typical of subduction-
related magma. Four of the Yarabamba Superunit samples are metal­
uminous with average molar Al2O3/(CaO + Na2O + K2O) (ASI) values of
0.9. One Yarabamba Superunit sample from Gao (2012) is peraluminous
(ASI = 1.2). Two dacite porphyry samples are peraluminous (ASI =
1.1–1.2; Table 2).
The chondrite-normalized rare earth element (REE) plots (Fig. 8B)
showed that the Yarabamba Superunit rocks have flatter patterns than
the dacite porphyry from the middle REEs (MREEs) to heavy REEs
(HREEs). The Yarabamba Superunit samples show a significantly
negative Eu anomaly (Table 2) with average Eu/Eu* (EuN/(0.5 × (SmN
+ GdN))) values of 0.64 ± 0.08 (SD, n = 5). Meanwhile, the dacite
porphyry samples have slightly negative to no Eu anomalies (Table 2)
with an average Eu/Eu* value of 0.93 ± 0.14 (SD, n = 2). DJ03 has a low
content of light REEs (LREEs) and high content of HREEs. This distinc­
tion was probably caused by significant fractionation of LREE-rich
magnetite (Schock, 1979; Mahood and Hildreth, 1983), which is
further supported by the low Fe2O3* (total iron as Fe3+), Co, Ni, and V
contents of this sample (Table 2).
5.3. Zircon Hf–O isotopes
The zircon Hf and O isotopic compositions of the Yarabamba
Superunit and dacite porphyry samples are similar (Fig. 9). The
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Fig. 5. Photomicrographs (crossed polarizers) of samples (A) DJ01, (B) DJ03, and (C) DJ04 from the Yarabamba Superunit and (D) DJ02 from the dacite porphyry.
Backscattered electron (BSE) images of apatite inclusions in (E) plagioclase and (F) zircon. Abbreviations: amp = amphibole, ap = apatite, bt = biotite, cpx =
clinopyroxine, kf = K–feldspar, pl = plagioclase, qtz = quartz, ser = sericite, zrn = zircon.

Yarabamba Superunit samples have zircon δ18O values ranging from
5.2‰ to 6.4‰ (average: 6.0 ± 0.3‰, SD, n = 21) for DJ01 and ranging
from 5.1‰ to 5.8‰ (average: 5.5 ± 0.2‰, SD, n = 15) for DJ04. The
dacite porphyry sample (DJ02) has zircon δ18O values ranging from
5.3‰ to 6.1‰ (average: 5.7 ± 0.2‰, SD, n = 22). Regarding the Hf
isotopic composition, the Yarabamba Superunit samples yielded zircon
εHf(t) values ranging from –4.6 to +0.5 (average –1.8 ± 1.2, SD, n = 22)
for DJ01 and from –0.6 to +1.9 (average +0.4 ± 0.6, SD, n = 15) for
DJ04. The dacite porphyry sample (DJ02) yielded εHf(t) values ranging
from –2.3 to –0.4 (average –1.3 ± 0.5, SD, n = 21).
Fig. 10 represents no contribution from the subducted slab, was taken
from sample 126175 (Søager and Holm, 2013; Søager et al., 2013). The
trace elemental composition was taken from the average depleted mid-
ocean ridge basalt (MORB) mantle (Workman and Hart, 2005). We
found that the Yarabamba Superunit samples comprise a mixed array of
MDM and metamorphic basement rocks with a total crustal contamina­
tion of 15%. Note that this value represents the maximum degree of
assimilation because the MDM represented the mostly depleted isotopic
end-member in the Andes.

5.5. Major and trace elemental compositions of minerals

5.4. Whole-rock Sr–Nd isotopes
For the whole-rock Sr–Nd isotope data (Fig. 10), three samples of the
Yarabamba Superunit have homogeneous 87Sr/86Srt (0.70533–0.70579),
and 143Nd/144Ndt (0.51242–0.51244) values. To estimate the magma
source contributions (mantle vs. crust), we chose a rear-arc sample
126175 (37.3◦ S, Chile; Fig. 10) to represent mantle-derived magma
(MDM) with minimal input from the subducted slab and continental crust
(Søager and Holm, 2013; Søager et al., 2013). The isotopic composition of
the depleted end-member, where the baseline ambient mantle (BAM) in
Elemental compositions of zircon, amphibole, plagioclase, and
apatite from the Yarabamba Superunit and zircon and apatite from the
dacite porphyry are listed in Electronic Appendix Table B. The data were
used to estimate the magmatic oxygen fugacity (fO2), water and sulfur
contents, and mineral crystallization pressure and temperature.
5.5.1. Amphibole
Amphiboles from the three Yarabamba Superunit samples have
relatively low Al2O3 contents (0.4 wt%–5.8 wt%) but relatively high

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Table 1
Sample description of Yarabamba Superunit and dacite porphyry.
Unit Sample Location Description Zrn Whole-rock Whole- Zrn Mineral composition
U–Pb major and trace rock Hf–O
Latitude S Longitude Z Zrn1 Amp2 Pl2 Ap2
dating element Sr–Nd
(◦ ) W (◦ ) (m)

Yarabamba DJ01 16.6844 71.5705 2902 Fresh, no alteration £ £ £ £ £ £ £ £

Superunit DJ03 16.6246 71.5535 2630 Fresh, no alteration £ £ £ £ £ £ £
DJ04 16.5949 71.5287 2578 Fresh, no alteration £ £ £ £ £ £ £ £
S34 16.7540 71.5149 2808 Propylitic alteration, £
texture partly
destroyed

Dacite DJ02 16.7181 71.4981 2932 Sericitic alteration, £ £ £ £ £

porphyry texture intact
S30 16.6276 71.4639 2885 Sericitic alteration, √ £
texture destroyed
S31 16.7496 71.5221 2300 Sericitic alterationn, √ £
texture partly
destroyed
S32 16.6284 71.4772 2912 Sericitic alteration, √ £
texture destroyed

Analytical method: 1 = LA–ICP–MS (laser ablation–inductively coupled plasma–mass spectrometry); 2 = EPMA (electron probe microanalysis). Abbreviation: Amp =
amphibole; Ap = apatite; Pl = plagioclase; Zrn = zircon; £ = analyzed sample; √ = dated by Ye et al. (2022).

Fig. 6. Zircon U–Pb concordia plots for samples from Don Javier: (A) DJ01, (B) DJ02, (C) DJ04, and (D) DJ02.

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N. Chen et al. Ore Geology Reviews 147 (2022) 104964

Table 2
Whole-rock element and isotopic compositions of Don Javier intrusions.
Unit Yarabamba Superunit Dacite porphyry
a a
Sample DJ01 DJ03 DJ04 33–364 36–653 DJ02 17A-500a

SiO2 (wt%) 61.78 66.59 59.90 61.56 58.88 63.42 68.22

TiO2 0.79 0.66 0.74 0.68 0.68 0.40 0.46
Al2O3 16.14 16.68 16.65 15.61 15.83 15.96 14.88
Fe2O3* 6.15 1.19 6.84 8.06 7.38 4.02 2.32
MnO 0.10 0.05 0.13 0.12 0.26 0.13 0.21
MgO 2.41 2.32 3.01 1.97 2.8 1.29 1.82
CaO 4.86 5.52 5.74 2.24 4.91 2.97 2.8
Na2O 3.44 5.04 3.09 2.92 3.16 1.90 4.28
K2O 3.36 0.42 2.85 3.94 4.56 4.28 1.53
P2O5 0.19 0.15 0.16 0.17 0.15 0.17 0.06
LOI 0.78 1.13 0.73 / / 4.66 /
SUM 99.99 99.73 99.84 / / 99.19 /
FeO 3.10 0.68 3.32 4.46 4.08 1.68 1.28
Li (ppm) 15.65 1.97 7.57 / / 11.94 /
Be 1.31 1.67 1.20 / / 0.89 /
Sc 16.60 10.97 20.62 / / 5.19 /
V 134.66 67.52 166.51 / / 57.89 /
Cr 11.38 8.06 11.90 / / 2.91 /
Co 15.14 3.56 18.53 / / 7.03 /
Ni 8.33 4.07 8.64 / / 3.47 /
Cu 96.92 6.80 95.48 / / 76.37 /
Zn 35.90 32.83 101.72 / / 176.74 /
Ga 18.70 15.38 19.28 / / 17.68 /
Rb 167.07 15.97 123.46 142 32.1 167.98 64.9
Sr 357.81 423.94 424.36 357 508 252.48 401
Y 25.10 43.83 22.58 24.9 19.1 8.17 8.8
Zr 194.93 233.84 135.19 279 127 86.87 201
Nb 8.20 7.46 5.07 7.6 4.2 3.90 4.5
Sn 1.91 3.01 1.52 / / 0.72 /
Cs 11.68 1.93 9.88 / / 9.88 /
Ba 591.69 153.82 600.45 763 99.8 905.04 208
La 26.69 8.76 20.56 23.8 15.8 17.75 12.4
Ce 56.07 29.82 43.79 51.8 35.6 34.30 26.6
Pr 6.86 5.44 5.44 6.57 4.86 4.09 3.05
Nd 26.64 29.26 21.61 26.3 20.2 15.43 10.9
Sm 5.72 9.46 4.91 5.81 4.51 2.80 1.91
Eu 1.07 1.71 1.06 1.04 1.06 0.67 0.61
Gd 4.81 8.75 4.10 4.91 3.97 1.95 1.63
Tb 0.72 1.32 0.69 0.76 0.59 0.25 0.24
Dy 4.27 8.03 3.86 4.41 3.4 1.39 1.4
Ho 0.88 1.69 0.79 0.91 0.67 0.28 0.29
Er 2.47 4.70 2.25 2.6 1.92 0.74 0.9
Tm 0.37 0.69 0.34 0.4 0.29 0.11 0.15
Yb 2.41 4.68 2.21 2.57 1.81 0.72 1.07
Lu 0.36 0.69 0.34 0.38 0.27 0.12 0.18
Hf 5.71 6.64 3.81 8.2 3.7 2.50 6.2
Ta 0.55 0.56 0.39 0.6 0.3 0.26 0.4
Tl 0.52 0.11 0.68 / / 1.31 /
Th 22.40 21.37 13.96 31.4 9.83 4.38 24.6
U 5.05 4.14 2.96 4.46 2.48 1.15 4.57
ASI 0.9 0.9 0.9 1.2 0.8 1.2 1.1
Eu/Eu* 0.61 0.56 0.70 0.58 0.75 0.83 1.03
Sr/Y 14.25 9.67 18.80 14.34 26.60 30.90 45.57
Dy/Yb 1.77 1.71 1.75 1.72 1.88 1.92 1.31
87
Sr/86Sr 0.70676 0.70588 0.70605 / / / /
143
Nd/144Nd 0.51249 0.51250 0.51249 / / / /

Note: a = data from Gao (2012); / = no data.

Mg# (molar Mg/(Mg + Fetotal); 0.57–0.87, average: 0.70, n = 34) and
Al# (AlVI/AlT; 0.09–1.99, average: 0.44, n = 34). The high amphibole
Al# (>0.21) suggests that thermodynamic formulas using a thermom­
eter, hygrometer, or oxybarometer (Ridolfi, 2021; Ridolfi and Renzulli,
2012; Ridolfi et al., 2010) were not suitable for these samples. The
crystallization pressure of these low-Al2O3 amphiboles was estimated by
using the method developed by Mutch et al. (2016) for granodioritic
rocks. This yielded an overall average crystallization pressure of 81 ±
28 MPa (SD, n = 31) for the three samples of the Yarabamba Superunit
(DJ01, DJ03, and DJ04), which corresponds to a depth of 3.0 km and
rock density of 2.75 g/cm3.
5.5.2. Plagioclase
Plagioclase grains from the Yarabamba Superunit samples have
anorthite (An) contents ranging from 34 mol. % to 57 mol. %, with
averages of 47 ± 4 mol. % (SD, n = 12), 42 ± 5 mol. % (SD, n = 6), and
50 ± 8 mol. % (SD, n = 6) for DJ01, DJ03, and DJ04, respectively. The
average FeOT contents for these samples averaged 0.33 ± 0.04 wt% (SD,
n = 12), 0.35 ± 0.1 wt% (SD, n = 6), and 0.34 ± 0.08 wt% (SD, n = 6),
respectively.
The magmatic water content is difficult to determine accurately but can
be estimated from the plagioclase An content as a function of the magmatic
temperature, pressure, water content, and chemical composition. The
plagioclase–liquid hygrometer is based on the plagioclase–liquid exchange

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N. Chen et al. Ore Geology Reviews 147 (2022) 104964

Fig. 7. (A) (Na2O + K2O) versus SiO2 (Le Bas et al., 1986) and (B) K2O versus SiO2 (Rollinson, 2014).

Fig. 8. (A) Primitive mantle-normalized trace element patterns and (B) chondrite-normalized REE patterns for the Yarabamba Superunit and dacite porphyry.
Igneous rocks from the Toquepala arc are also shown (Simmons, 2013; Demouy et al., 2019; Nathwani et al., 2021). Primitive mantle and chondrite normalization
values are taken from Sun and McDonough (1989).

between anorthite and albite components and can be used to estimate the
magmatic water content (Lange et al., 2009; Waters and Lange, 2015). The
presence of apatite inclusions in plagioclase indicates that apatite was
saturated when the plagioclase crystallized (Zhu et al., 2018), which suggests
that the apatite saturation temperature (AST) is a potential parameter for
calculating the magmatic H2O content based on the method of Waters and
Lange (2015). The Yarabamba Superunit samples yielded AST values of
887℃, 921℃, and 849℃ for DJ01, DJ03, and DJ04, respectively (Harrison
and Watson, 1984). We assumed that the amphibole crystallization pressure
represents the pressure in the magma chamber. Thus, we used the AST and
pressure from the amphibole barometer to estimate the magmatic water
content via the updated method of Waters and Lange (2015). DJ01, DJ03,
and DJ04 yielded average magmatic H2O contents of 4.3 ± 0.05 wt% (SD, n
= 12), 5.3 ± 0.07 wt% (SD, n = 6), and 5.6 ± 0.11 wt% (SD, n = 6),
respectively. Because the apatite is generally crystallized at the early stage of
magmatic evolution (Chen et al., 2022b) and the result of plagioclase–liquid
hygrometer is negative related with temperature parameter (Waters and
Lange, 2015). Thus, these results represent the minimum values of magmatic
H2O content.
5.5.3. Zircon
Among the obtained data, fifty-nine out of 202 were discarded
because of the presence of mineral inclusions (e.g., apatite and titanite),
high common Pb content, and/or because the zircon crystal was pene­
trated by the laser ablation. Zircon grains from both the Yarabamba
Superunit and dacite porphyry samples display positive Ce and negative
Eu anomalies (Figs. 11, 12). Zircon from DJ01, DJ03, DJ04, and S34 of
the Yarabamba Superunit have average Ce/Ce*zircon (CeN/(0.5 × (LaN +
PrN))) values ranging from 17 to 48 (Electronic Appendix Table B), with
an overall average value of 38 ± 29 (SD; n = 70). The zircon from the
dacite porphyry samples have average Ce/Ce*zircon values ranging from
57 to 113, with an overall average value of 88 ± 78 (SD; n = 73), which
is slightly greater than that from the Yarabamba Superunit.
The Yarabamba Superunit samples have average Eu/Eu*zircon (EuN/
(0.5 × (SmN + GdN))) values ranging from 0.10 to 0.15, with an overall
average value of 0.13 ± 0.03 (SD; n = 70). The dacite porphyry samples
have average Eu/Eu*zircon values ranging from 0.31 to 0.36, with an
overall average value of 0.34 ± 0.08 (SD; n = 73), which is higher than
for the Yarabamba Superunit samples.
We used Loucks et al.’s (2020) oxybarometer to estimate the
magmatic fO2. The initial U contents in zircon were calibrated by using

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N. Chen et al.
Fig. 9. (a) Initial εHf(t) and (b) δ18O values plotted against zircon U–Pb age of
various intrusive rocks at Don Javier. CHUR = chondritic uniform reservoir.
The δ18O value of the mantle is taken from Valley et al. (1998).
Fig. 10. 143Nd/144Ndt versus 87
Sr/88Srt diagram. Global subducting sediment
(GLOSS) from Plank (2014).
the zircon age. The four Yarabamba Superunit samples yielded
magmatic fO2 values ranging from ΔFMQ (log fO2 relative to the faya­
lite–magnetite–quartz redox buffer) –1.0 to +0.1 (Fig. 12B), with an
overall average fO2 value of ΔFMQ –0.5 ± 0.6 (SD, n = 70). The four
dacite porphyry samples yielded average fO2 values ranging from ΔFMQ
+0.8 to +1.5, with an overall average fO2 value of ΔFMQ +1.1 ± 0.6
(SD, n = 73).
The Ti-in-zircon temperature was estimated by using the pressure-
calibrated method of Loucks et al. (2020) with values of αSiO2 = 1 and
αTiO2 = 0.6. The zircon crystallization pressures of both the Yarabama
Superunit and dacite porphyry samples were calibrated by using an
average amphibole crystallization pressure of 81 MPa. Both the Yar­
abamba Superunit and dacite porphyry samples show a decrease in the
Ti-in-zircon temperature with increasing magmatic fO2 (Fig. 12B), and
the Yarabamba Superunit samples have a higher average temperature
(878–970℃) than the dacite porphyry samples (800–840 ◦ C).
5.5.4. Apatite
The igneous apatite compositions of the Yarabamba Superunit and
Don Javier porphyry samples are listed in Electronic Appendix Table B.
The apatite S content and XCl (molar proportions of Cl in hydroxyl sites
in apatite) values are illustrated in Fig. 13. For the Yarabamba Superunit
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Ore Geology Reviews 147 (2022) 104964
samples, twenty apatite measurements have S contents below the
detection limit (Fig. 13B), while the remaining measurements yielded
average S contents of 0.017 ± 0.017 wt% (SD, n = 3), 0.011 ± 0.006 wt
% (SD, n = 5), and 0.009 ± 0.003 wt% (SD, n = 3) for DJ01, DJ03, and
DJ04, respectively. The average XCl values are 0.16 ± 0.04 (SD, n = 21),
0.11 ± 0.06 (SD, n = 6), and 0.18 ± 0.01 (SD, n = 4), respectively.
Overall, all of the apatite grains from the Yarabamba Superunit samples
have an average S content of 0.01 ± 0.01 wt%, (SD, n = 11) and XCl
value of 0.15 ± 0.05 (SD, n = 31). All apatite S measurements in the
dacite porphyry sample (DJ02) are above the detection limit (Fig. 13B)
and yielded an average S content of 0.07 ± 0.05 wt% (SD, n = 31) and
XCl value of 0.21 ± 0.03 (SD, n = 31).
Igneous apatite can be used to estimate the melt S content (Parat and
Holtz, 2004; Parat and Holtz, 2005; Peng et al., 1997; Piccoli and
Candela, 2002), but accurate estimation is difficult because Kdapatite/melt
S
(the sulfur partition coefficient between the apatite and melt) is a
function of the magma temperature, fO2, and sulfur content (Parat and
Holtz, 2004). We used the temperature-fO2-calibrated Kdapatite/melt
S
developed by Meng et al. (2021) to estimate the melt S content
(Fig. 13C). The results suggest that the dacite porphyry has a signifi­
cantly higher melt S content (average: 0.07 ± 0.04 wt%, SD, n = 31)
than the Yarabamba Superunit (average: 0.02 ± 0.01 wt%, n = 11), i.e.,
average 0.03 ± 0.03 wt% (SD, n = 3), 0.02 ± 0.008 wt% (SD, n = 5), and
0.01 ± 0.004 wt% (SD, n = 3) for DJ01, DJ03, and DJ04, respectively.
6. Discussion
6.1. Geochronology
The three samples from the Yarabamba Superunit yielded nearly
identical zircon U–Pb ages ranging from 65.4 ± 0.7 to 63.5 ± 0.8 Ma,
which are consistent with the results of Ye et al. (2022) (S34: 64.6 ± 0.3
Ma). The dacite porphyry sample yielded a zircon U–Pb age of 59.2 ±
1.1 Ma, which is also consistent with the results of Ye et al. (2022) (S30,
S31, and S32: 59.9 ± 0.4 to 59.5 ± 0.3 Ma). These ages indicate a period
of approximately 3 m.y. with a magmatic lull (age gap between the
youngest pluton and the oldest porphyry intrusion) at Don Javier. This
magmatic lull is slightly longer than that of other porphyry deposits in
the Andes (Sillitoe, 2010), such as ~0.9 m.y. at the Rio Blanco deposit in
northern Peru (Chen et al., 2022a) and ~0.5 m.y. at the El Teniente
deposit in central Chile (Maksaev et al., 2004). The zircon U–Pb ages and
molybdenite Re–Os age (60.5 ± 1.4 to 59.6 ± 0.8 Ma) indicate that the
main mineralization was spatial-temporally related with the dacite
porphyry (Fig. 3). However, the youngest molybdenite Re–Os ages of
45.4 ± 1.4 to 44.4 ± 1.6 Ma (Ye et al., 2022) appear to indicate that
another magmatic–hydrothermal event occurred at Don Javier. The
causative intrusion of this seemingly second mineralization event was
not observed at Don Javier, and the details are unclear (Ye et al., 2022).
Additionally, samples from the Quellaveco deposit, which is 100 km
southeast of Don Javier, also indicated sporadic magmatism persisting
around 47.0–45.9 Ma based on whole-rock K–Ar isotopes of the
Toquepala arc (Zimmermann and Collado, 1983).
6.2. Igneous geochemistry and petrogenesis
The Yarabamba Superunit and dacite porphyry samples have similar
zircon Hf–O isotopic data (Fig. 9), which suggests that both evolved
from an isotopically composition-stable magma reservoir. The whole-
rock Sr–Nd isotopes indicate a maximum crustal rock assimilation of
15% (Fig. 10). The Yarabamba Superunit samples have significant
negative Eu anomalies (Fig. 8), which indicate low-pressure, H2O-poor,
plagioclase-dominated fractionation (Drake and Weill, 1975; Green,
1970; Müntener et al., 2001). This is further supported by the low Sr/Y
ratios of these samples (9.7–18.8; Table 2). This results from the fact that
fractionating plagioclase preferentially incorporates Sr and Eu over Y,
which would have led to the low Sr/Y ratio and negative Eu anomaly in
N. Chen et al. Ore Geology Reviews 147 (2022) 104964

Fig. 11. Chondrite-normalized rare-earth elements for zircons from the (A–D) Yarabamba Superunit and (E–H) dacite porphyry. Normalization values are taken from
Sun and McDonough (1989).

the residual melt (Drake and Weill, 1975). Plagioclase-dominated frac­
tionation may be common in magmas generated in normal subduction
zones, even in thick-crustal magmatic arcs such as the San
Pedroe–Linzor volcanic chain in northernmost Chile (~22◦ S; Godoy
et al., 2014).
Compared with the Yarabamba Superunit samples, the dacite porphyry
samples have higher Sr/Y (average: 38) and higher Eu/Eu* values (average:
0.9). The higher Sr/Y and Eu/Eu* values may indicate that the magma of the
dacite porphyry underwent high-pressure, H2O-rich, amphibole-(garnet)
dominated fractionation in the magma reservoirs (Davidson et al., 2007).

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N. Chen et al.
Fig. 12. Zircon Ce/Ce* versus Eu/Eu* values.
The Eu/Eu*zircon value can also be employed to evaluate magmatic
evolution because it is positively correlated with the Eu/Eu*melt value
but is only weakly effected by the melt fO2 (Nathwani et al., 2021). The
dacite porphyry samples have higher Eu/Eu*zircon values (average: 0.34;
Fig. 12) than the Yarabamba Superunit samples (average: 0.13), which
indicates that the Eu/Eu*melt values in the melt were high when the
zircon crystallized in the dacite porphyry. This is consistent with the
observed whole-rock geochemistry at Don Javier.
The analysis of the whole-rock geochemistry and zircon trace ele­
ments, coupled with radiometric dating, indicates that the transition
from plagioclase- to amphibole-(garnet) dominated fractionation at Don
Javier occurred contemporaneously with the Incaic I orogeny (~60 Ma)
in southern Peru (Noble et al., 1979; Noble et al., 1985; Roperch et al.,
2011). This transition was also observed at the Quellaveco deposit
(Nathwani et al., 2021).
6.3. Magmatic oxygen fugacity and volatile content
The zircon grains collected from the dacite porphyry have higher Ce/
Ce* values than those from the Yarabamba Superunit (Fig. 12), which
may indicate that the former have high magmatic fO2 (Munoz et al.,
2012; Trail et al., 2012). However, Loader et al. (2022) recently argued
that the zircon Ce/Ce* value is also a function of the temperature and
melt composition. In this study, we calculated the magmatic fO2 by
using the method of Loucks et al. (2020), which is independent of the La
and Pr elemental measurements of zircon and provides more precise
constraints for the oxidation state (Fig. 13). The results show that the fO2
(average: ΔFMQ +1.1) of the dacite porphyry is significantly higher
than that of the Yarabamba Superunit (average: ΔFMQ –0.5). These
calculations suggest that the magma of the causative dacite porphyry
was moderately oxidized, which is comparable to those of many por­
phyry deposits worldwide (Cao et al., 2018; Meng et al., 2016; Meng
et al., 2021; Munoz et al., 2012; Rezeau et al., 2019; Richards, 2015;
Wang et al., 2014b; Zhu et al., 2018).
Calculating the magmatic H2O content of the dacite porphyry is
difficult because this intrusion is altered. The presence of amphibole in
the Yarabamba Superunit suggests that the magmas contained >4 wt%
H2O in the shallow crustal magma chambers based on Naney’s (1983)
phase equilibrium experiment on granodioritic rocks at 200 MPa. This
estimation is consistent with the results from the plagioclase–liquid
hygrometer (4.3 wt%–5.6 wt% H2O). The dacite porphyry samples have
higher Eu/Eu* values than the Yarabamba Superunit samples, which
may have been caused by high magmatic H2O content suppressing
plagioclase fractionation in the magma reservoirs (Loucks, 2021;
Richards, 2011a). However, plagioclase fractionation can also be sup­
pressed by high pressure (Green, 1970). This prevented us from
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Ore Geology Reviews 147 (2022) 104964
comparing the magmatic H2O contents of the Yarabamba Superunit and
dacite porphyry, although the higher Eu/Eu* value of the latter may
indicate that it have a higher magmatic H2O content.
Sulfur occurs mainly as S6+ in relatively oxidized melts, and a high
apatite S content generally reflects high fO2 and melt S contents (Jugo
et al., 2010; Konecke et al., 2019). The apatite from the dacite porphyry
has an S content of 0.07 wt%, which is significantly higher than that of
the Yarabamba Superunit at 0.01 wt%–0.02 wt% (Fig. 13). This may
reflect the high fO2 and melt S contents in the magma of the dacite
porphyry. These results agree with the high magmatic fO2 and melt S
contents calculated via zircon oxybarometry and the apatite/melt
partition coefficient (Fig. 13).
The Kdapatite/melt
cl value is mainly controlled by the melt composition
and Cl concentration (Mathez and Webster, 2005). The high apatite XCl
values of the dacite porphyry may indicate a high melt Cl content
(Webster et al., 2009; Zhu et al., 2018; Fig. 13B).
Overall, these results indicate that the causative magma for Don
Javier deposit has a higher oxidation state and is richer in volatile than
the pre-mineralization Yarabamba Superunit, which is less-oxidized and
volatile-poorer. The uniform zircon Hf–O isotopes preclude the possi­
bility that external fertile sources were responsible for the higher
oxidation state and volatile-richer dacite porphyry magma, and rather
suggest that the transition to a more oxidized and volatile-rich magma
occurred during evolution in deep reservoirs (Chiaradia et al., 2009a,
2009b; Loucks, 2021; Rohrlach and Loucks, 2005).
6.4. Implications for metallogenesis
The causative magmas for magmatic–hydrothermal deposit forma­
tion are generally recognized as oxidized and rich in volatile (Rezeau
and Jagoutz, 2020; Richards, 2011b; Richards et al., 2012). A high
magmatic oxidation state favors the dissolution of oxidized sulfur,
suppresses sulfur saturation, and transfers the oxidized sulfur to shallow
magma chambers during porphyry deposit formation (Lee and Tang,
2020; Richards, 2015; Tang et al., 2020). If this is the case, then the
magmas of the Yarabamba Superunit and other older plutons (>60 Ma)
such as the Linga, Tiabaya, and Toquepala Superunits have low potential
for porphyry mineralization because these intrusions generally have
significant whole-rock negative Eu anomalies (Fig. 8; Boekhout et al.,
2012; Demouy et al., 2019; Manrique, 2011; Simmons, 2013). A whole-
rock negative Eu anomaly indicated H2O-poor, low-pressure, plagio­
clase-dominated fractionation (Green, 1970; Müntener et al., 2001;
Ulmer et al., 2018) rather than H2O-rich, high-pressure, amphibole-
(garnet) dominated fractionation. This is because plagioclase is rich in
ferric iron (Lundgaard and Tegner, 2004), and amphibole and garnet are
rich in ferrous iron (Lee and Tang, 2020; Zhang et al., 2022). Magmas
N. Chen et al.
Fig. 13. (A) Zircon fO2 versus apatite S content. (B) Apatite XCl versus S con­
tent. (C) Zircon fO2 versus melt S content.
absent of amphibole-(garnet) dominated fractionation will produce a
low Fe3+/Fe2+ ratio in residual melt and thus obtain a low oxidation
state when extracted from mid- to lower-crustal magma reservoirs. A
low oxidation state would facilitate sulfide saturation and ultimately
sulfur depletion in the residual melt (Lee and Tang, 2020). This plausibly
explains the scarcity of porphyry deposits in the Toquepala arc before
60 Ma because a high magmatic S content is considered a precondition
for their formation (Richards, 2015; Richards et al., 2017). The causa­
tive magma for Don Javier was moderately oxidized and rich in S, and
the transition from barren to fertile magma occurred at ~3 m.y. This
rapid transition to very large–super-giant porphyry deposits formation
occurred contemporaneously with the Incaic I orogeny (~60 Ma) in
southern Peru (Noble et al., 1979; Noble et al., 1985; Roperch et al.,
2011).
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Ore Geology Reviews 147 (2022) 104964
Therefore, we suggest that explorations of the Toquepala arc should
target the oxidized and volatile-rich magmas (<60 Ma) that were
emplaced during the Incaic I orogeny. Based on our results, the whole-
rock geochemistry and igneous zircon and apatite may be useful in­
dicators for porphyry Cu deposits: no or weak whole-rock Eu anomalies
(Eu/Eu* >0.83), fO2 >ΔFMQzircon +0.8 (Loucks et al, 2020), Eu/
Eu*zircon >0.32, and apatite S >0.07 wt%. The >60 Ma magmas in the
Toquepala arc are barren with typical characteristics of a low oxidation
state (fO2 <ΔFMQzircon +0.1; Loucks et al, 2020) and low volatile con­
tent (apatite S <0.017 wt%), and they have Eu/Eu*zircon values of <0.15
and significant whole-rock Eu anomalies (Eu/Eu* <0.75).
7. Conclusion
In this study, we comprehensively surveyed the magmatic oxidation
states and volatile contents in both pre-mineralization and syn-
mineralization intrusions at Don Javier. The results show that the pre-
mineralization intrusions have low oxidation state and volatile deple­
tion. The syn-mineralization intrusion is moderately oxidized and rich in
volatile. This transition from barren to fertile magma occurred at ~3 m.
y. at Don Javier and possibly took much less time in other contempo­
raneous porphyry deposits. This rapid transition in the magmatic
oxidation state and volatile content occurred synchronously with the
Incaic I orogeny (~60 Ma) in southern Peru, which indicates that this
orogeny had a significant impact on the formation of the porphyry ore
system.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgement
This research was supported by the National Natural Science Foun­
dation of China (No. 41820104010). We thank Guangyu Shi for EMP
analysis at Wuhan SampleSolution Analytical Technology Co., Ltd., Qian
Wang for zircon LA-ICP-MS trace element analysis at CAGS, and Sheng
He for zircon SIMS oxygen isotopes analysis at the Beijing Research
Institute of Uranium Geology. We also thank Massimo Chiaradia, an
anonymous reviewer and editor Oliver Kreuzer for their constructive
comments that greatly improved the manuscript.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.oregeorev.2022.104964.
References
Ale, J.A., Huanacuni, D., Manrique, M.d.C., 2020. Base de datos de recursos y reservas de
operaciones y proyectos mineros del Perú. Instituto Geológico, Minero y
Metalúrgico, Lima, Peru https://www.gob.pe/institucion/ingemmet/informes-
publicaciones/1423541-base-de-datos-de-metalogenia (accessed 03 March 2022).
Annen, C., Blundy, J.D., Sparks, R.S.J., 2006. The genesis of intermediate and silicic
magmas in deep crustal hot zones. J. Petrol. 47, 505–539. https://doi.org/10.1093/
petrology/egi084.
Boekhout, F., Spikings, R., Sempere, T., Chiaradia, M., Ulianov, A., Schaltegger, U., 2012.
Mesozoic arc magmatism along the southern Peruvian margin during Gondwana
breakup and dispersal. Lithos 146, 48–64. https://doi.org/10.1016/j.
lithos.2012.04.015.
Cao, M.J., Hollings, P., Cooke, D.R., Evans, N.J., McInnes, B.I.A., Qin, K.Z., Li, G.M.,
Sweet, G., Baker, M., 2018. Physicochemical processes in the magma chamber under
the Black Mountain porphyry Cu-Au deposit, Philippines: Insights from mineral
chemistry and implications for mineralization. Econ. Geol. 113, 63–82. https://doi.
org/10.5382/econgeo.2018.4544.
Cao, M.J., Evans, N.J., Hollings, P., Cooke, D.R., McInnes, B.I.A., Qin, K.Z., 2021. Apatite
texture, composition, and O-Sr-Nd isotope signatures record magmatic and
N. Chen et al.
hydrothermal fluid characteristics at the Black Mountain porphyry deposit,
Philippines. Econ. Geol. 116, 1189–1207. https://doi.org/10.5382/econgeo.4827.
Chambefort, I., Dilles, J.H., Kent, A.J.R., 2008. Anhydrite-bearing andesite and dacite as
a source for sulfur in magmatic-hydrothermal mineral deposits. Geology 36 (9), 719.
https://doi.org/10.1130/G24920A.110.1130/2008181.
Chen, N., Mao, J.W., Fan, C.L., Chen, Y.M., 2017. Alteration-mineralization
characteristics and three-dimensional exploration model of Don Javier porphyry
copper-molybdenum deposit, Peru. Mineral Deposits 36, 705–718 in Chinese with
English abstract.
Chen, N., Pratt, W., Mao, J.W., Xie, G.Q., Moisy, M., Santos, A., Guo, W.M., Zheng, W.,
Liu, J.A., 2022a. Geology and geochronology of the Miocene Rio Blanco porphyry
Cu-Mo deposit, Northern Peru. Econ. Geol. 117, 1013–1042. https://doi.org/
10.5382/econgeo.4896.
Chen, N., Meng, X.Y., Mao, J.W., Xie, G.Q., 2022b. Genetic relationship between
subduction of slab topographic anomalies and porphyry deposit formation: Insight
from the source and evolution of Rio Blanco magmas. J. Petrol. 63, 1–28. https://
doi.org/10.1093/petrology/egac045.
Chiaradia, M., 2009. Adakite-like magmas from fractional crystallization and melting-
assimilation of mafic lower crust (Eocene Macuchi arc, Western Cordillera, Ecuador).
Chem. Geol. 265 (3-4), 468–487. https://doi.org/10.1016/j.chemgeo.2009.05.014.
Chiaradia, M., Merino, D., Spikings, R., 2009a. Rapid transition to long-lived deep crustal
magmatic maturation and the formation of giant porphyry-related mineralization
(Yanacocha, Peru). Earth Planet. Sci. Lett. 288 (3-4), 505–515. https://doi.org/
10.1016/j.epsl.2009.10.012.
Chiaradia, M., Müntener, O., Beate, B., Fontignie, D., 2009b. Adakite-like volcanism of
Ecuador: lower crust magmatic evolution and recycling. Contrib. Mineral. Petrol.
158 (5), 563–588. https://doi.org/10.1007/s00410-009-0397-2.
Chiaradia, M., Ulianov, A., Kouzmanov, K., Beate, B., 2012. Why large porphyry Cu
deposits like high Sr/Y magmas? Sci. Rep. 2, 685. https://doi.org/10.1038/
srep00685.
Chiaradia, M., Caricchi, L., 2017. Stochastic modelling of deep magmatic controls on
porphyry copper deposit endowment. Sci. Rep. 7, 1–11. https://doi.org/10.1038/
srep44523.
Clark, A.H., 1993. Are outsize porphyry copper deposits either anatomically or
environmentally distinctive? In: Whiting, B.H., Hodgson, C.J., Mason, R. (Eds.),
Giant Ore Deposits. Society of Economic Geologists, pp. 213–283. https://doi.org/
10.5382/SP.02.06.
Coira, B., Davidson, J., Mpodozis, C., Ramos, V., 1982. Tectonic and magmatic evolution
of the Andes of northern Argentina and Chile. Earth Sci. Rev. 18 (3-4), 303–332.
https://doi.org/10.1016/0012-8252(82)90042-3.
Cooke, D.R., Hollings, P., Walshe, J.L., 2005. Giant porphyry deposits: characteristics,
distribution, and tectonic controls. Econ. Geol. 100 (5), 801–818. https://doi.org/
10.2113/gsecongeo.100.5.801.
Davidson, J., Turner, S., Handley, H., Macpherson, C., Dosseto, A., 2007. Amphibole
“sponge” in arc crust? Geology 35 (9), 787. https://doi.org/10.1130/
G23637A.110.1130/2007196.
Decou, A., von Eynatten, H., Mamani, M., Sempere, T., Wörner, G., 2011. Cenozoic
forearc basin sediments in Southern Peru (15–18 S): Stratigraphic and heavy mineral
constraints for Eocene to Miocene evolution of the Central Andes. Sediment. Geol.
237 (1-2), 55–72. https://doi.org/10.1016/j.sedgeo.2011.02.004.
Demouy, S., Paquette, J.L., de Saint Blanquat, M., Benoit, M., Belousova, E.A.,
O’Reilly, S.Y., García, F., Tejada, L.C., Gallegos, R., Sempere, T., 2012. Spatial and
temporal evolution of Liassic to Paleocene arc activity in southern Peru unraveled by
zircon U-Pb and Hf in-situ data on plutonic rocks. Lithos 155, 183–200. https://doi.
org/10.1016/j.lithos.2012.09.001.
Demouy, S., Benoit, M., de Saint-Blanquat, M., Ganne, J., 2019. Evolution of a long-lived
continental arc: a geochemical approach (Arequipa Batholith, Southern Peru). Solid
Earth Discuss. 1–42, 2019. https://doi.org/10.5194/se-2019-43.
Drake, M.J., Weill, D.F., 1975. Partition of Sr, Ba, Ca, Y, Eu2+, Eu3+, and other REE
between plagioclase feldspar and magmatic liquid: an experimental study. Geochim.
Cosmochim. Acta 39 (5), 689–712. https://doi.org/10.1016/0016-7037(75)90011-
3.
Gao, X., 2012. Researchs on Geochemical Characteristics and Metallogenic Prediction of
Don Javier Porphyry Copper Deposit, Southern Peru (M.Sc thesis). Central South
University, Changsha, China.
Godoy, B., Wörner, G., Kojima, S., Aguilera, F., Simon, K., Hartmann, G., 2014. Low-
pressure evolution of arc magmas in thickened crust: The San Pedro-Linzor volcanic
chain, Central Andes, northern Chile. J. South Am. Earth Sci. 52, 24–42. https://doi.
org/10.1016/j.jsames.2014.02.004.
Green, T.H., 1970. High pressure experimental studies on the mineralogical constitution
of the lower crust. Phys. Earth Planet. Inter. 3, 441–450. https://doi.org/10.1016/
0031-9201(70)90086-5.
Harrison, T.M., Watson, E.B., 1984. The behavior of apatite during crustal anatexis:
equilibrium and kinetic considerations. Geochim. Cosmochim. Acta 48 (7),
1467–1477. https://doi.org/10.1016/0016-7037(84)90403-4.
Hildreth, W., Moorbath, S., 1988. Crustal contributions to arc magmatism in the Andes of
central Chile. Contrib. Mineral. Petrol. 98 (4), 455–489. https://doi.org/10.1007/
BF00372365.
IGEMMENT(Insitituto Geológico, Minero y Metalúrgico), 2015. Mapa geologico del Perú,
Escala 1: 3,000,000. Lima, Peru.
Jacay, J., Sempéré, T., Husson, L., Pino, A., 2002. Structural characteristics of the
Incapuquio fault system, southern Peru. https://horizon.documentation.ird.fr/exl-
doc/pleins_textes/divers16-05/010047938.pdf (accessed 03 March 2022).
Jin, W.Q., 2010. On Geological Features and Genesis Study of the Cercana-Don Javier
Porphyry Copper Deposit in Southern Peru (M.Sc thesis). Central South University,
Changsha, China.
14
Ore Geology Reviews 147 (2022) 104964
Jugo, P.J., Wilke, M., Botcharnikov, R.E., 2010. Sulfur K-edge XANES analysis of natural
and synthetic basaltic glasses: Implications for S speciation and S content as function
of oxygen fugacity. Geochim. Cosmochim. Acta 74 (20), 5926–5938. https://doi.
org/10.1016/j.gca.2010.07.022.
Konecke, B.A., Fiege, A., Simon, A.C., Linsler, S., Holtz, F., 2019. An experimental
calibration of a sulfur-in-apatite oxybarometer for mafic systems. Geochim.
Cosmochim. Acta 265, 242–258. https://doi.org/10.1016/j.gca.2019.08.044.
Lange, R.A., Frey, H.M., Hector, J., 2009. A thermodynamic model for the plagioclase-
liquid hygrometer/thermometer. Am. Mineral. 94 (4), 494–506. https://doi.org/
10.2138/am.2009.3011.
Le Bas, M.J., Maitre, R.W.L., Streckeisen, A., Zanettin, B., 1986. A chemical classification
of volcanic rocks based on the total alkali-silica diagram. J. Petrol. 27 (3), 745–750.
https://doi.org/10.1093/petrology/27.3.745.
Lee, C.-T., Tang, M., 2020. How to make porphyry copper deposits. Earth Planet. Sci.
Lett. 529, 115868. https://doi.org/10.1016/j.epsl.2019.115868.
Li, J.X., Li, G.M., Evans, N.J., Zhao, J.X., Qin, K.Z., Xie, J., 2021. Primary fluid exsolution
in porphyry copper systems: evidence from magmatic apatite and anhydrite
inclusions in zircon. Miner. Deposita 56 (2), 407–415. https://doi.org/10.1007/
s00126-020-01013-4.
Loader, M.A., Nathwani, C.L., Wilkinson, J.J., Armstrong, R.N., 2022. Controls on the
magnitude of Ce anomalies in zircon. Geochim. Cosmochim. Acta. https://doi.org/
10.1016/j.gca.2022.03.024.
Loucks, R.R., Fiorentini, M.L., Henríquez, G.J., 2020. New magmatic oxybarometer using
trace elements in zircon. J. Petrol. 61, 1–30. https://doi.org/10.1093/petrology/
egaa034.
Loucks, R.R., 2021. Deep entrapment of buoyant magmas by orogenic tectonic stress: Its
role in producing continental crust, adakites, and porphyry copper deposits. Earth
Sci. Rev. 220, 103744. https://doi.org/10.1016/j.earscirev.2021.103744.
Lundgaard, K.L., Tegner, C., 2004. Partitioning of ferric and ferrous iron between
plagioclase and silicate melt. Contrib. Mineral. Petrol. 147 (4), 470–483. https://doi.
org/10.1007/s00410-004-0568-0.
Mahood, G., Hildreth, W., 1983. Large partition coefficients for trace elements in high-
silica rhyolites. Geochim. Cosmochim. Acta 47 (1), 11–30. https://doi.org/10.1016/
0016-7037(83)90087-X.
Mamani, M., Wörner, G., Sempere, T., 2010. Geochemical variations in igneous rocks of
the Central Andean orocline (13 S to 18 S): Tracing crustal thickening and magma
generation through time and space. Bulletin 122, 162–182. https://doi.org/
10.1130/B26538.1.
Maksaev, V., Munizaga, F., McWilliams, M., Fanning, M., Mathur, R., Ruiz, J.,
Zentilli, M., 2004. New chronology for El Teniente, Chilean Andes, from U-Pb,
40
Ar/39Ar, Re-Os, and fission-track dating: Implications for the evolution of a
supergiant porphyry Cu-Mo deposit. Soc. Econ. Geol. 11, 15–54. https://doi.org/
10.5382/SP.11.02.
Manrique, J.P.R., 2011. Magmatismo meso-cenozoico de la cordillera de la costa y borde
oeste de la cordillera occidental del sur de Perú (Tesis para optar el Título
Profesional de ingeniero geólogo). Universudad Nacional San Agustín, Arequipa,
Peru https://catalogobiblioteca.ingemmet.gob.pe/cgi-bin/koha/opac-detail.pl?
biblionumber=22008 (accessed 03 March 2022).
Martínez, W., Marchena, A.A., Otero, J.F., Cervantes, J., León, W.R., 2017. Geología y
controles tectonomagmáticos de los sistemas porfiríticos en el arco magmático
occidental sur del Perú. https://repositorio.ingemmet.gob.pe/handle/
20.500.12544/3533 (accessed 03 March 2022).
Mathez, E.A., Webster, J.D., 2005. Partitioning behavior of chlorine and fluorine in the
system apatite-silicate melt-fluid. Geochim. Cosmochim. Acta 69, 1275–1286.
https://doi.org/10.1016/j.gca.2008.10.034.
Meng, X., Mao, J., Zhang, C., Zhang, D., Kong, Z., Jia, F., 2016. The timing, origin and T-
fO2 crystallization conditions of long-lived magmatism at the Yangla copper deposit,
Sanjiang Tethyan orogenic belt: Implications for post-collisional magmatic-
hydrothermal ore formation. Gondwana Res. 40, 211–229. https://doi.org/10.1016/
j.gr.2016.09.005.
Meng, X., Kleinsasser, J.M., Richards, J.P., Tapster, S.R., Jugo, P.J., Simon, A.C.,
Kontak, D.J., Robb, L., Bybee, G.M., Marsh, J.H., Stern, R.A., 2021. Oxidized sulfur-
rich arc magmas formed porphyry Cu deposits by 1.88 Ga. Nat. Commun. 12 (1)
https://doi.org/10.1038/s41467-021-22349-z.
Mukasa, S.B., 1986. Zircon U-Pb ages of super-units in the Coastal batholith, Peru:
Implications for magmatic and tectonic processes. Geol. Soc. Am. Bull. 97, 241–254.
https://doi.org/10.1130/0016-7606(1986)97<241:ZUAOSI>2.0.CO;2.
Mungall, J.E., 2002. Roasting the mantle: Slab melting and the genesis of major Au and
Au-rich Cu deposits. Geology 30, 915–918. https://doi.org/10.1130/0091-7613
(2002)030<0915:RTMSMA>2.0.CO;2.
Munoz, M., Charrier, R., Fanning, C., Maksaev, V., Deckart, K., 2012. Zircon trace
element and O-Hf isotope analyses of mineralized intrusions from El Teniente ore
deposit, Chilean Andes: constraints on the source and magmatic evolution of
porphyry Cu–Mo related magmas. J. Petrol. 53, 1091–1122. https://doi.org/
10.1093/petrology/egs010.
Müntener, O., Kelemen, P.B., Grove, T.L., 2001. The role of H2O during crystallization of
primitive arc magmas under uppermost mantle conditions and genesis of igneous
pyroxenites: an experimental study. Contrib. Mineral. Petrol. 141 (6), 643–658.
https://doi.org/10.1007/s004100100266.
Mutch, E.J.F., Blundy, J.D., Tattitch, B.C., Cooper, F.J., Brooker, R.A., 2016. An
experimental study of amphibole stability in low-pressure granitic magmas and a
revised Al-in-hornblende geobarometer. Contrib. Mineral. Petrol. 171, 1–27. https://
doi.org/10.1007/s00410-016-1298-9.
Naney, M.T., 1983. Phase equilibriua of rock-forming ferromagnesian silicates in granitic
systems. Am. Jour. Sci. 283, 993–1033.
N. Chen et al.
Nathwani, C.L., Simmons, A.T., Large, S.J., Wilkinson, J.J., Buret, Y., Ihlenfeld, C., 2021.
From long-lived batholith construction to giant porphyry copper deposit formation:
petrological and zircon chemical evolution of the Quellaveco District, Southern Peru.
Contrib. Mineral. Petrol. 176, 1–21. https://doi.org/10.1007/s00410-020-01766-1.
Noble, D.C., McKEE, E.H., Mégard, F., 1979. Early Tertiary “Incaic” tectonism, uplift, and
volcanic activity, Andes of central Peru. Geol. Soc. Am. Bull. 90, 903–907. https://
doi.org/10.1130/0016-7606(1979)90<903:ETITUA>2.0.CO;2.
Noble, D.C., Sébrier, M., Megard, F., McKee, E.H., 1985. Demonstration of two pulses of
Paleogene deformation in the Andes of Peru. Earth Planet. Sci. Lett. 73 (2-4),
345–349. https://doi.org/10.1016/0012-821X(85)90082-2.
Oyarzun, R., Márquez, A., Lillo, J., López, I., Rivera, S., 2001. Giant versus small
porphyry copper deposits of Cenozoic age in northern Chile: adakitic versus normal
calc-alkaline magmatism. Miner. Deposita 36 (8), 794–798. https://doi.org/
10.1007/s001260100205.
Parat, F., Holtz, F., 2004. Sulfur partitioning between apatite and melt and effect of
sulfur on apatite solubility at oxidizing conditions. Contrib. Mineral. Petrol. 147 (2),
201–212. https://doi.org/10.1007/s00410-004-0553-7.
Parat, F., Holtz, F., 2005. Sulfur partition coefficient between apatite and rhyolite: the
role of bulk S content. Contrib. Mineral. Petrol. 150 (6), 643–651. https://doi.org/
10.1007/s00410-005-0041-8.
Peng, G., Luhr, J.F., McGee, J.J., 1997. Factors controlling sulfur concentrations in
volcanic apatite. Am. Mineral. 82 (11-12), 1210–1224. https://doi.org/10.2138/am-
1997-11-1217.
Perelló , J., Carlotto, V., Zá rate, A., Ramos, P., Posso, H., Neyra, C., Caballero, A.,
Fuster, N., Muhr, R., 2003. Porphyry-style alteration and mineralization of the
middle Eocene to early Oligocene Andahuaylas-Yauri belt, Cuzco region, Peru. Econ.
Geol. 98 (8), 1575–1605. https://doi.org/10.2113/gsecongeo.98.8.1575.
Piccoli, P.M., Candela, P.A., 2002. Apatite in igneous systems. Rev. Mineral. Geochem.
48 (1), 255–292. https://doi.org/10.2138/rmg.2002.48.6.
Plank, T., 2014. The chemical composition of subducting sediments. In: Turekian, K.K.
(Ed.), Treatise on Geochemistry (Second Edition). Elsevier, pp. 607–629.
Quang, C.X., Clark, A.H., Lee, J.K.W., Guillen B., J., 2003. 40Ar-39Ar ages of hypogene
and supergene mineralization in the Cerro Verde-Santa Rosa porphyry Cu-Mo
cluster, Arequipa, Peru. Econ. Geol. 98 (8), 1683–1696. https://doi.org/10.2113/
gsecongeo.98.8.1683.
Rezeau, H., Moritz, R., Wotzlaw, J.-F., Hovakimyan, S., Tayan, R., 2019. Zircon
petrochronology of the Meghri-Ordubad pluton, Lesser Caucasus: Fingerprinting
igneous processes and implications for the exploration of porphyry Cu-Mo deposits.
Econ. Geol. 114, 1365–1388. https://doi.org/10.5382/econgeo.4671.
Rezeau, H., Jagoutz, O., 2020. The importance of H2O in arc magmas for the formation of
porphyry Cu deposits. Ore Geol. Rev. 126, 103744. https://doi.org/10.1016/j.
oregeorev.2020.103744.
Richards, J.P., 2011a. High Sr/Y arc magmas and porphyry Cu±Mo±Au deposits: just
add water. Econ. Geol. 106, 1075–1081. https://doi.org/10.1016/j.
oregeorev.2020.103744.
Richards, J.P., 2011b. Magmatic to hydrothermal metal fluxes in convergent and collided
margins. Ore Geol. Rev. 40 (1), 1–26. https://doi.org/10.1016/j.
oregeorev.2011.05.006.
Richards, J.P., Spell, T., Rameh, E., Razique, A., Fletcher, T., 2012. High Sr/Y magmas
reflect arc maturity, high magmatic water content, and porphyry Cu±Mo±Au
potential: examples from the Tethyan arcs of central and eastern Iran and western
Pakistan. Econ. Geol. 107, 295–332. https://doi.org/10.2113/econgeo.107.2.295.
Richards, J.P., 2015. The oxidation state, and sulfur and Cu contents of arc magmas:
implications for metallogeny. Lithos 233, 27–45. https://doi.org/10.1016/j.
lithos.2014.12.011.
Richards, J.P., López, G.P., Zhu, J.-J., Creaser, R.A., Locock, A.J., Mumin, A.H., 2017.
Contrasting tectonic settings and sulfur contents of magmas associated with
Cretaceous porphyry Cu±Mo±Au and intrusion-related iron oxide Cu-Au deposits in
northern Chile. Econ. Geol. 112 (2), 295–318. https://doi.org/10.2113/
econgeo.112.2.295.
Ridolfi, F., Renzulli, A., Puerini, M., 2010. Stability and chemical equilibrium of
amphibole in calc-alkaline magmas: an overview, new thermobarometric
formulations and application to subduction-related volcanoes. Contrib. Mineral.
Petrol. 160 (1), 45–66. https://doi.org/10.1007/s00410-009-0465-7.
Ridolfi, F., Renzulli, A., 2012. Calcic amphiboles in calc-alkaline and alkaline magmas:
thermobarometric and chemometric empirical equations valid up to 1,130◦ C and 2.2
GPa. Contrib. Mineral. Petrol. 163, 877–895. https://doi.org/10.1007/s00410-011-
0704-6.
Ridolfi, F., 2021. Amp-TB2: An updated model for calcic amphibole thermobarometry.
Minerals 11, 324. https://doi.org/10.3390/min11030324.
Rohrlach, B.D., Loucks, R.R., 2005. Multi-million-year cyclic ramp-up of volatiles in a
lower-crustal magma reservoir trapped below the Tampakan copper–gold deposit by
Mio-Pliocene crustal compression in the southern Philippines. In: Porter, T.M. (Ed.),
Super Porphyry Copper and Gold Deposits: A Global Perspective. PCG Publishing,
Adelaide, pp. 369–407.
Rollinson, H.R., 2014. Using Geochemical Data: Evaluation, Presentation, Interpretation.
Routledge, Abingdon.
Roperch, P., Carlotto, V., Ruffet, G., Fornari, M., 2011. Tectonic rotations and
transcurrent deformation south of the Abancay deflection in the Andes of southern
Peru. Tectonics 30 (2). https://doi.org/10.1029/2010TC002725.
Sajona, F.G., Maury, R.C., 1998. Association of adakites with gold and copper
mineralization in the Philippines. C. R. Acad. Sci.-Series IIA-Earth Planet. Sci. 326
(1), 27–34. https://doi.org/10.1016/S1251-8050(97)83200-4.
Santos, A., Guo, W., Rivera, F., Tassinari, C., Cerpa, L., Kojima, S., 2019. Early Jurassic
arc related magmatism associated with porphyry copper mineralization at Zafranal,
15
Ore Geology Reviews 147 (2022) 104964
Southern Peru unraveled by zircon U-Pb ages. Andean Geol. 0718–7106. https://hdl.
handle.net/20.500.12544/2322.
Schock, H.H., 1979. Distribution of rare-earth and other trace elements in magnetites.
Chem. Geol. 26 (1-2), 119–133. https://doi.org/10.1016/0009-2541(79)90034-2.
Sempere, T., Carlier, G., Soler, P., Fornari, M., Carlotto, Vı́ctor, Jacay, J., Arispe, O.,
Néraudeau, D., Cárdenas, J., Rosas, S., Jiménez, Néstor, 2002. Late Permian-Middle
Jurassic lithospheric thinning in Peru and Bolivia, and its bearing on Andean-age
tectonics. Tectonophysics 345 (1-4), 153–181. https://doi.org/10.1016/S0040-1951
(01)00211-6.
Shatwell, D., 2021. Mesozoic Metallogenesis of Peru: A Reality Check on Geodynamic
Models. SEG Discovery 15–24. https://doi.org/10.5382/SEGnews.2021-124.fea-01.
Sillitoe, R.H., Perelló, J., 2005. Andean copper province: Tectonomagmatic settings,
deposit types, metallogeny, exploration, and discovery. Econ. Geol. 100th
Anniversary 845–890. https://doi.org/10.5382/AV100.26.
Sillitoe, R.H., 2010. Porphyry copper systems. Econ. Geol. 105 (1), 3–41. https://doi.
org/10.2113/gsecongeo.105.1.3.
Sillitoe, R.H., Mortensen, J.K., 2010. Longevity of porphyry copper formation at
Quellaveco. Peru. Econ. Geol. 105 (6), 1157–1162. https://doi.org/10.2113/
econgeo.105.6.1157.
Simmons, A.T., 2013. Magmatic and Hydrothermal Stratigraphy of Paleocene and
Eocene Porphyry Cu-Mo Deposits in Southern Peru (M Sc thesis). University of
British Columbia, Vancouver, Canada, p. 359.
Simmons, A.T., Tosdal, R.M., Wooden, J.L., Mattos, R., Concha, O., McCracken, S.,
Beale, T., 2013. Punctuated magmatism associated with porphyry Cu-Mo formation
in the Paleocene to Eocene of southern Peru. Econ. Geol. 108 (4), 625–639. https://
doi.org/10.2113/econgeo.108.4.625.
Søager, N., Holm, P.M., 2013. Melt–peridotite reactions in upwelling eclogite bodies:
Constraints from EM1-type alkaline basalts in Payenia, Argentina. Chem. Geol. 360,
204–219. https://doi.org/10.1016/j.chemgeo.2013.10.024.
Søager, N., Holm, P.M., Llambías, E.J., 2013. Payenia volcanic province, southern
Mendoza, Argentina: OIB mantle upwelling in a backarc environment. Chem. Geol.
349, 36–53. https://doi.org/10.1016/j.chemgeo.2013.04.007.
Sun, S.-s., McDonough, W.F., 1989. Chemical and isotopic systematics ofoceanic basalts:
Implications for mantle composition and processes. Geol. Soc., London, Spec. Publ.
42 (1), 313–345. https://doi.org/10.1144/GSL.SP.1989.042.01.19.
Sun, W., Ling, M., Yang, X., Fan, W., Ding, X., Liang, H., 2010. Ridge subduction and
porphyry copper-gold mineralization: An overview. Sci. China Earth Sci. 53 (4),
475–484. https://doi.org/10.1007/s11430-010-0024-0.
Tang, M., Lee, C.-T.-A., Ji, W.Q., Wang, R., Costin, G., 2020. Crustal thickening and
endogenic oxidation of magmatic sulfur. Sci. Adv. 6, eaba6342. https://doi.org/
10.1126/sciadv.aba6342.
Tosdal, R.M., Richards, J.P., 2001. Magmatic and structural controls on the development
of porphyry Cu±Mo±Au deposits. Struct. Controls Ore Genesis 14, 157–181. https://
doi.org/10.5382/Rev.14.06.
Trail, D., Watson, E.B., Tailby, N.D., 2012. Ce and Eu anomalies in zircon as proxies for
the oxidation state of magmas. Geochim. Cosmochim. Acta 97, 70–87. https://doi.
org/10.1016/j.gca.2012.08.032.
Ulmer, P., Kaegi, R., Müntener, O., 2018. Experimentally derived intermediate to silica-
rich arc magmas by fractional and equilibrium crystallization at 1⋅0 GPa: an
evaluation of phase relationships, compositions, liquid lines of descent and oxygen
fugacity. J. Petrol. 59, 11–58. https://doi.org/10.1093/petrology/egy017.
Valley, J.W., Kinny, P.D., Schulze, D.J., Spicuzza, M.J., 1998. Zircon megacrysts from
kimberlite: oxygen isotope variability among mantle melts. Contrib. Mineral. Petrol.
133 (1-2), 1–11. https://doi.org/10.1007/s004100050432.
Wang, R., Richards, J.P., Hou, Z., Yang, Z., DuFrane, S.A., 2014a. Increased magmatic
water content—the key to Oligo-Miocene porphyry Cu-Mo±Au formation in the
eastern Gangdese belt, Tibet. Econ. Geol. 109, 1315–1339. https://doi.org/10.2113/
econgeo.109.5.1315.
Wang, R., Richards, J.P., Hou, Z.Q., Yang, Z.M., Gou, Z.B., DuFrane, S.A., 2014b.
Increasing magmatic oxidation state from paleocene to miocene in the eastern
Gangdese Belt, Tibet: implication for collision-related porphyry Cu-Mo±Au
mineralization. Econ. Geol. 109, 1943–1965. https://doi.org/10.2113/
econgeo.109.7.1943.
Waters, L.E., Lange, R.A., 2015. An updated calibration of the plagioclase-liquid
hygrometer-thermometer applicable to basalts through rhyolites. Am. Mineral. 100
(10), 2172–2184. https://doi.org/10.2138/am-2015-5232.
Webster, J.D., Tappen, C.M., Mandeville, C.W., 2009. Partitioning behavior of chlorine
and fluorine in the system apatite–melt–fluid. II: Felsic silicate systems at 200 MPa.
Geochim. Cosmochim. Acta 73 (3), 559–581. https://doi.org/10.1016/j.
gca.2008.10.034.
Webster, R., Pitman, C., Zamora, C., 2013. Don Javier Cu-Mo Project NI 43-101
Technical Report. Canada: Prepared by AMC Mining Consultants Ltd.
Wilkinson, J.J., 2013. Triggers for the formation of porphyry ore deposits in magmatic
arcs. Nat. Geosci. 6 (11), 917–925. https://doi.org/10.1038/ngeo1940.
Workman, R.K., Hart, S.R., 2005. Major and trace element composition of the depleted
MORB mantle (DMM). Earth Planet. Sci. Lett. 231 (1-2), 53–72. https://doi.org/
10.1016/j.epsl.2004.12.005.
Wu, B., Fang, Z., Ye, Z.C., 2013. Geological characteristics of Don Javier porphyry copper
molybdenum deposit. Mineral Deposits 32, 1159–1170 in Chinese with English
abstract.
Wu, B., 2014. Peruvian Don Javier Copper Deposit Metallogenic Geological
Characteristics, Economical Development Model and its Promotion (Ph. D thesis).
China University of Geosciences, Beijing, China.
Ye, Z., Mao, J., Lu, M., Zhu, X., Chen, N., Wei, H., Jin, W., Meng, X., 2022. Geology and
geochronology of the Don Javier Cu-Mo porphyry deposit, southern Peru. Ore Geol.
Rev. 143, 104777. https://doi.org/10.1016/j.oregeorev.2022.104777.
N. Chen et al.
Zhang, Y., 2011. Researches on Geology Characteristic and Metallogenic Prediction in
Don Javier Copper Deposit, Southern Region of Peru (M Sc thesis). Central South
University, Changsha, China.
Zhang, J., Wang, R., Hong, J., 2022. Amphibole fractionation and its potential redox
effect on arc crust: Evidence from the Kohistan arc cumulates. Am. Mineral.
Zhou, J.S., Wang, Q., Wyman, D.A., Zhao, Z.H., 2020. Petrologic reconstruction of the
Tieshan magma plumbing system: Implications for the genesis of magmatic-
hydrothermal ore deposits within originally water-poor magmatic systems. J. Petrol.
61, egaa056. https://doi.org/10.1093/petrology/egaa056.
Zhu, J.J., Richards, J.P., Rees, C., Creaser, R., DuFrane, S.A., Locock, A., Petrus, J.A.,
Lang, J., 2018. Elevated magmatic sulfur and chlorine contents in ore-forming
16
Ore Geology Reviews 147 (2022) 104964
magmas at the Red Chris porphyry Cu-Au deposit, northern British Columbia,
Canada. Econ. Geol. 113, 1047–1075. https://doi.org/10.5382/econgeo.2018.4581.
Zimmermann, J.L., Collado, A.K., 1983. Détermination par la Méthode K/Ar de l’âge des
Intrusions et des Minéralisations Associées dans le Porphyre Cuprifère de Quellaveco
(Sud Ouest du Pérou). Miner. Deposita 18, 207–213. https://doi.org/10.1007/
BF00206209.
Zweng, P.L., Clark, A.H., Pierce, F.W., Bolm, J.B., 1995. Hypogene evolution of the
Toquepala porphyry copper-molybdenum deposit, Moquegua, southeastern Peru.
Arizona Geological Society Digest 20, 566–612.