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Porphyry deposits and oxidized magmas

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DOI: 10.1016/j.oregeorev.2014.09.004

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 Ore Geology Reviews 65 (2015) 97–131

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Review

Porphyry deposits and oxidized magmas

Weidong Sun a,⁎, Rui-fang Huang b,c, He Li a, Yong-bin Hu a,c, Chan-chan Zhang a,c, Sai-jun Sun a,c,
Li-peng Zhang a,c, Xing Ding b, Cong-ying Li a, Robert E. Zartman a, Ming-xing Ling b
a
CAS Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, 511 Kehua Street, Wushan, Guangzhou 510640, China
b
State Key Laboratory of Isotope Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, 511 Kehua Street, Wushan, Guangzhou 510640, China
c
University of the Chinese Academy of Sciences, Beijing 100049, China

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

Article history: Porphyry deposits supply most of the world's Cu and Mo resources. Over 90% of the porphyry deposits are found
Received 17 June 2014 at convergent margins, especially above active subduction zones, with much fewer occurrences at post-
Received in revised form 19 August 2014 collisional or other tectonic settings. Porphyry Cu–(Mo)–(Au) deposits are essentially magmatic–hydrothermal
Accepted 2 September 2014
systems, which are generally initiated by injection of oxidized magmas saturated with metal-rich aqueous fluids,
Available online 16 September 2014
i.e., the parental magmas need to be water rich and oxidized with most of the sulfur appearing as sulfate in the
Keywords:
magma. Sulfur is the most important geosolvent that controls the behavior of Cu and other chalcophile elements,
Porphyry deposit due to high partition coefficients of chalcophile elements between sulfide and silicate melts. Small amount of
Oxidized magmas residual sulfides can hold a large amount of Cu. Therefore, it is essential to eliminate residual sulfides to get
Oxygen fugacity high Cu contents in magmas for the formation of porphyry deposits. Sulfate (SO2− 4 ) is over 10 times more soluble
Adakite than sulfide (S2−), and thus the solubility of sulfur depends strongly on sulfur speciation, which in turn depends
Slab melts on oxygen fugacities. The magic number of oxygen fugacity is log fO2 N FMQ + 2 (i.e., ΔFMQ + 2), where FMQ is
Arc magmas the fayalite–magnetite–quartz oxygen buffer. Most of the sulfur in magmas is present as sulfate at oxygen fugac-
Plate subduction
ities higher than ΔFMQ + 2. Correspondingly, the solubility of sulfur increases from ~1000 ppm up to N 1 wt.%.
Ridge subduction
Oxidation promotes the destruction of sulfides in the magma source, and thereby increases initial chalcophile
element concentrations, forming sulfur-undersaturated magmas that can further assimilate sulfides during as-
cent. Copper, Mo and Au act as incompatible elements in sulfide undersaturated magmas, leading to high
chalcophile element concentrations in evolved magmas. The final porphyry mineralization is controlled by
sulfate reduction, which is usually initiated by magnetite crystallization, accompanied by decreasing pH and
correspondingly increasing oxidation potential of sulfate. Hematite forms once sulfate reduction lowers the pH
sufficiently, driving the oxidation potential of sulfate up to the hematite–magnetite oxygen fugacity (HM) buffer,
which is ~ΔFMQ + 4. Given that ferrous iron is the most important reductant that is responsible for sulfate re-
duction during porphyry mineralization, the highest oxygen fugacity favorable for porphyry mineralization is
the HM buffer. In addition to the oxidation of ferrous iron during the crystallization of magnetite and hematite,
reducing wallrock may also contribute to sulfate reduction and mineralization. Nevertheless, porphyry deposits
are usually mineralized in the whole upper portion of the pluton, whereas interactions with country rocks are
generally restricted at the interface, therefore assimilation of reducing sediments is not likely to be a decisive con-
trolling process. Degassing of oxidized gases has also been proposed as a major process that is responsible for sul-
fate reduction. Degassing, however, is not likely to be a main process in porphyry mineralization that occurs at
2–4 km depths in the upper crust. Sulfide formed during sulfate reduction is efficiently scavenged by aqueous
fluids, which transports metals to shallower depths, i.e., the top of the porphyry and superjacent wallrock. Ac-
cording to traditional views, sulfide saturation and segregation during magma evolution is not favorable for
the formation of porphyry Cu ± Au ± Mo deposits. This is the main difference between porphyry deposits and
Ni–Cu sulfide deposits. Nevertheless, in places with thick sections of reducing sediments, e.g., the western
North America, sulfide saturation and segregation may occur during evolution of the magma, forming Cu-rich cu-
mulates at the base of plutons. These Cu-rich sulfides may evolve into porphyry mineralization or even control
the ore-forming process. Their contribution depends heavily on subsequent oxidation, i.e., a major contribution
can be expected only when the sulfide cumulates are oxidized to sulfate, liberating the chalcophile elements. Sul-
fate reduction and ferrous Fe oxidation form H+, which dramatically lowers the pH values of ore-forming fluids
and causes pervasive alteration zones in porphyry Cu deposits. The amount of H+ released during mineralization
and the alkali content in the porphyry together control the intensity of alterations. In principle, H2 and methane

⁎ Corresponding author.
E-mail address: weidongsun@gig.ac.cn (W. Sun).

http://dx.doi.org/10.1016/j.oregeorev.2014.09.004
0169-1368/© 2014 Published by Elsevier B.V.
98 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131

form during the final mineralization process of porphyry deposits, but are mostly oxidized by ferric Fe during
subsequent processes. Some of the reduced gases, however, may survive the highly oxidizing environment to es-
cape from the system, or even to get trapped in fluid inclusions. Therefore, small amount of reduced gases in fluid
inclusions cannot argue against the oxidized feature of the magmas. Reduced magmas are not favorable for por-
phyry mineralization. Reduced porphyry deposits so far reported are just mineralization that has either been re-
duced in host rock away from the causative porphyry or through assimilation of reducing components during
emplacement.
© 2014 Published by Elsevier B.V.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
2. Brief introduction of major oxygen buffers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
2.1. Fayalite–magnetite–quartz (FMQ) oxygen buffer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
2.2. Hematite–magnetite (HM) oxygen buffer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
2.3. Ni–NiO(NNO) oxygen buffer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
2.4. Pyrite + pyrrhotite + magnetite (PPM) oxygen buffer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
3. The association of porphyry deposits with oxidized magmas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
3.1. Large porphyry deposits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
3.1.1. Porphyry Cu and Au deposits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
3.1.2. Porphyry Cu–Mo deposits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
3.1.3. Porphyry Mo deposits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
3.2. Linkage between oxidized magmas and porphyry deposits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
3.2.1. Sulfur oxidation, sulfide under saturation and residual sulfide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
3.2.2. Sulfate reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
3.2.3. Hematite–magnetite intergrowth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
3.3. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
4. The association of porphyry deposits with reduced magmas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
4.1. Reduced magmas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
4.1.1. Evidence for reduced magmas of Catface porphyry deposit . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
4.1.2. Evidence for reduced magma in the Baogutu porphyry deposit . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
4.2. Source of copper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
4.3. Formation of reduced porphyry deposits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
4.3.1. The formation of the Catface porphyry deposit . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
4.3.2. The formation of the Baogutu porphyry deposit . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
4.4. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
5. Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
5.1. The oxygen fugacities at convergent margins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
5.2. The difference between porphyry and epithermal in terms of oxygen fugacity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
5.2.1. Magnetite crisis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
5.2.2. Oxygen fugacity and open systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
5.3. Adakite, slab melting, ridge subduction and porphyry Cu deposits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
5.3.1. Adakite and porphyry Cu deposits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
5.3.2. Ridge subduction and porphyry Cu deposits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
5.4. Alterations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
6. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127

1. Introduction The consensus is that most of the porphyry Cu ± Mo ± Au systems

Porphyry deposits are hosts to one of the most important economic
mineral associations (Cooke et al., 2005; Halter et al., 2005; Heinrich
et al., 2004; Mutschler et al., 2010; Sillitoe, 2010), accounting for ~80%
Cu and ~95% Mo of the world's total reserves. It is also an important re-
source of Au, Ag, Zn, Sn and W. Most porphyry deposits are found above
active subduction zones (Fig. 1) (e.g., Chiaradia, 2014; Chiaradia et al.,
2012; Gonzalez-Partida et al., 2003; Hedenquist et al., 1998; Kesler,
1997; Lee, 2014; Richards, 1999, 2013; Sillitoe, 2010; Sun et al., 2011;
Wilkinson, 2013), with a few occurrences at post-collisional or other
tectonic settings (Sillitoe, 2010), e.g., porphyry Mo deposits in the east-
ern Qinling orogenic belt (Chen, 2013; Li et al., 2012a; N. Li et al., 2013)
and, arguably porphyry Cu–Mo deposits in Gangdese belt on the south
Tibetan Plateau (Hou et al., 2009; Qu et al., 2004; Xiao et al., 2012)
and some porphyry Cu deposits in Iran (Calagari, 2003; Castillo, 2006;
Haschke et al., 2010; Shafiei et al., 2009).
are initiated by injection of oxidized adakitic magma saturated with
aqueous fluids that are S- and metal-rich, i.e., the parental magmas
must be water rich and oxidized (e.g., Ballard et al., 2002; Burnham
and Ohmoto, 1980; Garrido et al., 2002; Imai, 2002; Liang et al., 2006;
Mungall, 2002; Sillitoe, 2010; Stern et al., 2007; Sun et al., 2013b). It is,
however, still controversial as regards to: why high oxygen fugacity is
favorable for the mineralization of porphyry deposits, how oxidized
the magma could be, whether adakitic magma is essential for porphyry
mineralization or whether the porphyry deposits can be associated with
normal arc rocks (Fig. 2), and why the pure porphyry Mo deposits are
also closely associated with highly oxidized magmas.
Copper, Au and Mo are chalcophile elements, which are strongly
controlled by the behavior and speciation of sulfur. Therefore, the less
the quantity of residual sulfide, the higher the initial Cu contents in pri-
mary magmas (Fig. 3) (Lee et al., 2012; Sun et al., 2004a, 2013b). Exper-
iments show that sulfate is much more soluble than sulfide in magmas
 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131
Fig. 1. Worldwide distribution of porphyry Cu deposits. Note, most of the porphyry deposits are distributed along convergent margins. Porphyry Mo deposits are not shown.
Modified after Sun et al. (2013b). Data sources: Mutschler et al. (2010).
(Beermann et al., 2011; Jugo, 2009). Therefore, considerably more sulfur
is removed in the form of sulfate under higher oxygen fugacity (Lee
et al., 2012; Liang et al., 2009; Sun et al., 2013b). Meanwhile, sulfide is
kept undersaturated during the evolution of oxidized magmas, such
that no sulfide segregation is expected (Sun et al., 2012a; Sun et al.,
2013b). Therefore, Cu, Mo and Au act as moderately incompatible ele-
ments (McDonough and Sun, 1995; Sun et al., 2003a,b,c), which become
enriched during the early stage of magma evolution, and suddenly go
into magmatic fluids during magnetite crystallization (Sun et al.,
2004a, 2013a). It has been proposed that oxygen fugacity of log
fO2 N FMQ + 2 (i.e., ΔFMQ + 2, where FMQ is the fayalite–magnetite–
quartz oxygen buffer) is the magic number for porphyry mineralization
(e.g., Mungall, 2002; Sun et al., 2013b). Sulfate is the dominant species
at log fO2 N FMQ + 2, which is much more soluble than sulfide in
magmas (Jugo, 2009). Therefore, residual sulfides are more efficiently
destroyed at oxygen fugacities higher than FMQ + 2, releasing their
chalcophile elements (Sun et al., 2013b). Others have argued that SO2
is the main sulfur species dissolved in porphyry magmas (Richards,
2014; Smith et al., 2012), not sulfate nor sulfide. It was further argued
that variations in oxidation state over typical ranges for arc magmas
(ΔFMQ = 0 to +2) have no major effects on the potential of magmas
to form porphyry Cu–(Mo) deposits during plate subduction
(Richards, 2011b). The implication is that ΔFMQ + 2 is not of impor-
tance for porphyry Cu mineralization. Instead, water is the most impor-
tant factor that controls porphyry mineralization (Richards, 2011a). The
question then becomes that most arc plutons are water saturated and
highly oxidized, why do only a very small fraction of special magmas
(mostly adakitic characterized by high Sr/Y and high Sr) in arc settings
form porphyry deposits. For example, there are essentially no porphyry
deposits in Japan (Fig. 1). Note that Japan arc is associated with older
and presumably wetter subducting plate, such that arc rocks are pre-
sumably wetter than subduction related rocks along the eastern margin
of the Pacific Ocean (Sun et al., 2012a,b, 2013a,b).
A recent study has suggested that the source region for arc magmas
is probably neither unusually oxidized nor enriched in economic ele-
ments of interest, such as Cu, as has been shown by studies of primitive
arc magmas (Lee et al., 2010, 2012). This is seemingly consistent with
the moderate incompatibility of Cu during mantle magmatism (Sun
99
et al., 2003a,b), which leads to Cu depletion in the mantle wedge.
Also, the moderate mobility of Cu during plate subduction (J.L. Li et al.,
2013) can compensate for the depletion caused by previous melting.
The implication thus is that normal arc rocks, i.e., peridotitic melts, are
not favorable for porphyry Cu mineralization.
Still other authors have argued that, instead of high oxidation, sul-
fide saturation of the magma and consequent pre-enrichment through
sulfide accumulation are the most important step for porphyry ore de-
posits (Chiaradia, 2014; Lee, 2014; Wilkinson, 2013). This is probably
true along the western margin of the North American continent and
other places where reduced sediments are well developed (see more
in Section 4). However, this hypothesis raises several other questions.
Why are porphyry deposits usually associated with oxidized magmas,
which is a situation so different from Ni–Cu sulfide deposits that clearly
experienced sulfide saturation? How does porphyry remain oxidized
after collecting sulfide from the pre-enriched sulfide accumulates?
Why are the grades of porphyry deposits much lower than sulfide satu-
rated Ni–Cu sulfide deposits? Why is there no Ni in porphyry deposits?
Moreover, some porphyry deposits are apparently associated with
reduced magmas at ΔFMQ − 0.5 to − 3 (Cao et al., 2014; Rowins,
2000; Smith et al., 2012). Although reduced porphyry deposits are
rare, with tonnages much smaller than oxidizing porphyry deposits
(Cao et al., 2014), the mechanism needs to be clarified.
This contribution focuses on the controlling factors of porphyry min-
eralization. Major controversies to be discussed here are: (1) Why do
most of the porphyry deposits associated with oxidized magmas occur
at convergent margins? (2) What is the most favorable oxygen fugacity
range for porphyry mineralization? (3) What is the genetic connection
between high oxygen fugacity magmas and porphyry deposits?
(4) Why are some porphyry deposits associated with reducing
magmas? (5) What are the connections between porphyry deposits
and reduced magmas, if there is any?
2. Brief introduction of major oxygen buffers
Oxygen fugacity (fO2) is an important geological parameter affecting
the stability of minerals, the evolution of magmas, and ore-forming pro-
cesses. It is an equivalent of the partial pressure of oxygen in a particular
100 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131

Fig. 2. Two different models for porphyry Cu ± Au ± Mo deposits. A. Porphyry deposits are formed in normal arc rocks (after Richards, 2011a). According to this model, even the formation
of giant porphyry deposits is nothing special but optimization of normal ore-forming processes, controlled by distinct tectonic configurations, reactive host rocks, or focused fluid flow that
have helped to enhance the overall process (Richards, 2013). B. Porphyry deposits are associated with slab melts (modified after Wilkinson, 2013), which have high initial Cu contents (Sun
et al., 2011).

environment (atmosphere, magmas, rocks, etc.) corrected for the non-
ideal character of the gas. Oxygen fugacity is very important to the be-
haviors of elements, but it is not a very precise term because in some
cases, oxidation–reduction reactions do not involve any oxygen and
the oxygen fugacity changes with pressure and temperature (Sun
et al., 2014a,b). “Redox state” is a better term to describe the relative
proportions of an element among its different oxidation states. Never-
theless, oxygen fugacity is popularly used in Earth sciences.
Oxygen fugacity is usually notated as variations relative to a certain
oxygen buffer. Oxygen buffer refers to an assemblage of minerals or com-
pounds that constrains oxygen fugacity as a function of temperature and
pressure (Fig. 4), i.e., the oxygen fugacity of equilibration at a fixed pres-
sure is defined by one of the curves in oxygen fugacity versus tempera-
ture diagrams. The concept of oxygen fugacity and oxygen fugacity
buffer have been well developed and widely used in high pressure
experiments.
Oxygen fugacity is of critical importance for the behaviors of ele-
ments. Therefore, it is crucial to know the oxygen fugacity of a geochem-
ical process and to control oxygen fugacity during experiments. There
are several ways to control oxygen fugacity of experiments in the labo-
ratory. Gas-mixing techniques have been commonly used for control-
ling oxygen fugacity of experiments conducted at high temperature
 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131 101

Fig. 3. Copper contents during partial melting of mantle peridotite under different oxygen fugacities modeled by Lee et al. (2012). (A) Variation of aggregated melt and residual mantle
composition with degree of partial melting (F) at 2GPa, 1350 °C and fO2 at FMQ + 0, assuming initial S content of 200 ppm, i.e. 0.06 wt.% of sulfide. (B) Copper contents in primary
melt as a function of F and log fO2 (ΔFMQ); same P–T conditions as in (A). (C) Cu content of aggregate liquids versus fO2 for different F. Gray field refers to Cu in primitive MORB and
arc magmas (Lee et al., 2012).

Fig. 4. Comparison of log fO2–T relationships for the Ni–NiO, Co–CoO, FMQ, MnO–Mn3O4,
and HM oxygen buffers at 1 bar.
The log fO2 of Co–CoO, FMQ and HM are taken from Chou (1978). The log fO2 of Ni–NiO
and MnO–Mn3O4 are taken from Huebner and Sato (1970).
(above 1300 K) and 1 atm pressure (Huebner, 1987). The gas mixtures
mostly used are CO2–CO and CO2–H2. At higher pressure, oxygen fugac-
ity can be controlled by the oxygen buffer technique (Eugster, 1957)
and the Shaw membrane (Shaw, 1963), and measured with the hydro-
gen fugacity sensor technique (Chou, 1978). This oxygen buffer tech-
nique was first developed by Eugster in 1957 to prevent oxidation of
iron during growth of hydrous ferrous silicates and then later to deter-
mine the stability of annite (Eugster, 1957; Eugster and Wones, 1962;
Wones and Eugster, 1965). The oxygen buffers commonly used in
high pressure and high temperature experiments are fayalite–
magnetite–quartz (FMQ), Co–CoO, Ni–NiO (NNO), hematite–magnetite
(HM), and MnO–Mn3O4. These buffers are also useful as notations in the
measurement of the oxygen fugacity of natural rocks and magmas. A
comparison of the log fO2–T relationship for these buffers is shown in
Fig. 4. In experiments using the conventional double-capsule method,
the mixture of buffer materials and water is loaded in the outer capsule
and the sample is sealed in the inner capsule. Hydrogen gas forms
during the reaction between buffer materials and water in the outer cap-
sule, then diffuses through the inner capsule wall and equilibrates with
the hydrogen in the inner capsule. Capsules with high hydrogen diffusiv-
ity are usually taken as the inner capsule (e.g., Pt), whereas that with low
hydrogen diffusivity is used as the outer capsule (e.g., Ag). The
102 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131

prerequisite for using the double-capsule technique is that the buffer

materials themselves do not diffuse into the inner capsule. Therefore,
they cannot be used for system with haplogranitic melts and H2SO4
solutions because Co and Ni diffuse into the inner capsule, resulting in
formation of nickel sulfide or cobalt sulfide (Keppler, 2010).
The other way to regulate the oxygen fugacity of sample assem-
blages is to control the hydrogen fugacity using the Shaw membrane,
which introduces variable amount of hydrogen gas into the system
(Shaw, 1963). The advantage of this technique is that the hydrogen fu-
gacity can be varied independently and continuously. Moreover, the
Ag–AgCl–H2O–HCl acid buffer can be used as a fH2 sensor by loading
the acid-buffer assemblage in a small Pt capsule and putting the capsule
in a larger capsule containing the sample assemblages (Chou, 1978). In
this case, the measured concentration of HCl in the sensor indicates the
fH2 of the outer sample system.

2.1. Fayalite–magnetite–quartz (FMQ) oxygen buffer

The FMQ oxygen buffer is widely used in studies of natural samples,

as well as for experiments. Given that the oxygen fugacity of most igne-
ous rocks plot within several log units of the FMQ buffer, the oxygen fu-
gacities of natural samples are often noted as log unit variations from
the FMQ buffer, i.e., in ΔFMQ units. For example, ΔFMQ + 2 means ox-
ygen fugacity 2 log units higher than the values defined by the FMQ
buffer. The FMQ equilibrium has been determined experimentally by
many researchers, e.g., Chou (1978), Myers and Eugster (1983) and
Eugster and Wones (1962). The oxygen fugacity is controlled through
reaction (1):

3Fe2 SiO4 þ O2 ¼ 3SiO2 þ 2Fe3 O4 : ð1Þ

As shown in Fig. 5, the pressure dependence of log fO2 for this buffer
is not significant, but log fH2 changes greatly from 1 bar to 10 kbar.

2.2. Hematite–magnetite (HM) oxygen buffer
The HM (hematite + magnetite) equilibrium has been determined
by several researchers (e.g., Chou, 1978; Eugster and Wones, 1962;
Hemingway, 1990; Myers and Eugster, 1983). Oxygen fugacity is con-
trolled through reaction (2) or (3):
4Fe3 O4 þ O2 ¼ 6Fe2 O3 ð2Þ
2Fe3 O4 þ H2 O ¼ 3Fe2 O3 þ H2 : ð3Þ
Eq. (3) better describes the system with water present. As shown in
Fig. 6, the pressure dependence of log fO2 is quite small, while log fH2 in-
creases rapidly at low pressures but less at higher pressures. For high
pressure experiments, the HM buffer is more oxidized than the intrinsic
oxygen fugacity of the hydrothermal vessel. Thus, hematite was con-
sumed quite fast, e.g., in some experiments around 3.73 mg Fe2O3 was
consumed in the buffer assemblage every hour under steady-state con-
ditions, and 100 mg of Fe2O3 lasted only 26.8 h (Chou, 1986). Therefore,
the HM buffer is not suitable for experiments conducted in hydrother-
mal vessels with water as the pressure medium. In natural systems,
the oxygen fugacity of the HM buffer is usually much higher than that
of magmas. Most of the porphyry deposits, however, reach the HM
buffer value during mineralization.
Fig. 5. Pressure dependence of log fO2 and log fH2 of FMQ oxygen buffer. The log fO2 of Ni–
NiO buffer is taken from Chou (1978). Method for calibrating log fH2 of FMQ buffer is the
same as that of the HM buffer.
Ni þ H2 O ¼ NiO þ H2 : ð5Þ
As shown in Fig. 7, the pressure dependence of log fO2 is not signif-
icant, but log fH2 increases rapidly at low pressures but less at higher
pressures. The Ni–NiO buffer is commonly used in experiments, bring-
ing with it distinct advantages. First, the oxygen fugacity of Ni–NiO is
quite close to the intrinsic oxygen fugacity of the hydrothermal vessel
(NiNiO + 0.5). Thus, even quite small amounts of Ni and NiO powder
could last for a long time during experiments, e.g., around 200 mg of
Ni and NiO is enough for around a 10-day experiment. Moreover,
oxygen fugacity controlled by the Ni–NiO buffer is quite important
for the oxidation states of many elements, e.g., sulfur in the fluids is
mostly as H2S at the oxygen fugacity of NNO, but SO2 and SO3 appear
when the oxygen fugacity increases by 0.5 log unit (Binder and
Keppler, 2011).
2.4. Pyrite + pyrrhotite + magnetite (PPM) oxygen buffer
The PPM (pyrite + pyrrhotite + magnetite) equilibrium controls
f S2 and fO2 through reactions (6)–(8):

2.3. Ni–NiO(NNO) oxygen buffer 2Fe1−x S þ ð1−2xÞS2 ¼ 2ð1−xÞFeS2 ð6Þ

The Ni–NiO oxygen buffer has been experimentally determined by

Huebner and Sato (1970) and O'Neil and Pownceby (1993). The oxygen 6Fe1−x S þ 4O2 ¼ 2ð1−xÞFe3 O4 þ 3S2 ð7Þ
fugacity is controlled through reactions (4) and (5):

Ni þ 1=2O2 ¼ NiO ð4Þ 3FeS2 þ 2O2 ¼ Fe3 O4 þ 3S2 : ð8Þ

 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131
Fig. 6. Pressure dependence of log fO2 and log fH2 for the HM buffer. The log fO2 of
HM buffer is taken from Chou (1978). The log fH2 is calculated using log K = log f H2 +
1/2log fO2, where K is the equilibrium constant of H2O = H2 + 1/2O2 determined by
Supcrt92 with the database DPRONS2003.
This buffer has been used in hydrothermal experiments, e.g., Spry
and Scott (1986) and Crerar et al. (1978). The fO2 of the PPM buffer
has been determined by Kishima (1989) and Shi (1992), and their re-
sults are in general agreement. Fig. 8. shows a comparison of the fO2–T
relationship of the PPM buffer with those of the NNO and HM oxygen
buffers. The log fO2 of the PPM oxygen buffer is located between those
of NNO and HM buffers, e.g., at 700 °C, the log fO2 of PPM oxygen buffer
is around 1 log10 unit lower than that of the HM buffer, but 3.3 log10 unit
higher than that of the NNO buffer. As shown in Fig. 8b, log fO2 decreases
slightly with increasing pressure (Kishima, 1989; Shi, 1992).
At high temperature, the assemblage PPM is replaced by magnetite
and pyrrhotite (MPo) because pyrite is not stable (Sun et al., 2013a,b;
Tomkins, 2010). Consequently, SO2 becomes the dominant species,
and fH2, fH2O, and fH2S decrease abruptly. The breakdown temperature
of pyrite increases with increasing pressures, e.g., at 2 kbar, the break-
down temperature is 745 °C, and increases to around 800 °C to
10 kbar (Shi, 1992).
3. The association of porphyry deposits with oxidized magmas
It has long been proposed that most porphyry deposits are closely
associated with oxidized magmas (Burnham and Ohmoto, 1980;
Candela, 1992; Hedenquist and Lowenstern, 1994; Liang et al., 2006;
Liang et al., 2009; Mungall, 2002; Sillitoe, 2010; Sun et al., 2012a,
2013b), also known as the magnetite-series magmas (Ishihara and
Terashima, 1989) (Fig. 9). These porphyry Cu–(Mo)–(Au) deposits are
103
Fig. 7. Pressure dependence of log fO2 and log fH2 (Ni–NiO oxygen buffer). The logfO2 of
Ni–NiO buffer is taken from Huebner and Sato (1970). Method for calibrating log f H2 of
Ni–NiO buffer is the same as that of HM buffer.
almost always attributable to the injection of an oxidized adakitic
magma that is saturated with S- and metal-rich aqueous fluids,
i.e., the parental magmas are water rich and oxidized (Ballard et al.,
2002; Mungall, 2002; Sillitoe, 2010). Several small “reducing porphyry
deposits” constitute the rare exceptions (Cao et al., 2014; Rowins,
2000; Sillitoe, 1999) (see detailed discussion in Section 4 below). Inter-
growths of magnetite and hematite indicate that oxygen fugacities of
porphyry deposits often reach the values defined by the HM buffer
(Fig. 10). In this section, we review the oxygen fugacities of a number
of famous deposits and then discuss the genetic connections between
oxidized magmas and porphyry deposits. The main questions discussed
in this section include that: whether oxygen fugacity is a controlling
factor that dictates the distribution of porphyry deposits. What is the
genetic link between high oxygen fugacity magmas and porphyry
deposits? What is the most favorable oxygen fugacity range for porphyry
mineralization? And how do oxygen fugacities change during porphyry
mineralization?
3.1. Large porphyry deposits
The close association between highly oxidized magmas and porphy-
ry deposits may best be illustrated by a FeO versus fO2 diagram (Fig. 9).
The highly oxidized nature of porphyry magmas have been reported in
essentially all types of porphyries (Mungall, 2002; Sillitoe, 2010; Sun
et al., 2013b; Vila et al., 1991), including porphyry Cu and Cu–Au
deposits (Sillitoe, 2010), porphyry Au deposits (Vila and Sillitoe, 1991;
Vila et al., 1991), to porphyry Cu–Mo deposits (Cuadra and Rojas,
2001; Lynch and Ortega, 1997; Stern et al., 2007) and pure porphyry
104 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131
Fig. 8. Comparison of the log fO2 of PPM (pyrite–pyrrhotite–magnetite) buffer with those
of Ni–NiO and hematite–magnetite buffer (A) and pressure dependence of the logfO2 of
PPM buffer.
The log fO2 of PPM buffer is calibrated from Shi (1992).
Mo deposits (Seedorff and Einaudi, 2004a,b). They are found in different
tectonic settings, ranging from continental arc (Sillitoe, 2010; Stern
et al., 2007, 2011) to island arc (Hedenquist et al., 1998; Imai and
Fig. 9. Schematic plot of Fe content in magmas versus oxidation state (fO2) for calc-alkaline
to alkaline magmas associated with porphyry Cu, Cu–Mo and Mo deposits and W, Sn de-
posits. The approximate boundary between magnetite- and ilmenite-series magmas
(Ishihara, 1977) is also shown. Nevertheless, the HM buffer is the upper limit of oxygen fu-
gacity favorable for porphyry deposits.
Modified after Thompson et al. (1999).
Ohno, 2005; Imai et al., 1993; Sun et al., 2013b), and from active subduc-
tion zones to post-collisional zones (Hou et al., 2004, 2007b, 2009; Li
et al., 2012a; Xiao et al., 2012).
One common indicator of the high oxygen fugacity of porphyry de-
posits is sulfate, i.e., both magmatic and hydrothermal sulfate,
e.g., hydrothermal anhydrite and magmatic anhydrite and gypsum are
abundant in essentially all large porphyry deposits (Cooke et al., 2011;
Zhang, Ling et al., 2013; Halter et al., 2005; Imai et al., 2007; Kavalieris
et al., 2011; Li et al., 2008; Liang et al., 2009; Stern et al., 2007; Vila
et al., 1991). In addition to sulfate, hypogene hematite and specularite
have also been reported in many porphyry deposits (Baker et al.,
1997; Hedenquist et al., 1998; Imai, 2001; Imai et al., 2007; Li et al.,
2008; Seedorff and Einaudi, 2004b; Sillitoe, 2010; Spry et al., 1996;
Vila and Sillitoe, 1991; Vila et al., 1991). The hematite–magnetite
(HM) oxygen buffer has been taken as the upper limit of oxygen fugac-
ities that are favorable for porphyry mineralization (Sun et al., 2013b).
Previous authors also have proposed that the oxygen fugacities of differ-
ent porphyry deposits are slightly different, in the order of: porphyry Cu
and porphyry Au deposits N porphyry Cu–Mo deposits N porphyry Mo
deposits (Fig. 9) (Thompson et al., 1999).
3.1.1. Porphyry Cu and Au deposits
Porphyry Cu and Au deposits almost do have systematically higher
oxygen fugacities and FeO contents compared to other porphyry de-
posits (i.e., Cu–Mo and Mo). The best examples are the Cenozoic por-
phyry Cu and Au deposits occurring in the southwestern Pacific
islands, and to a less extent, the Paleozoic porphyry Cu–Au deposits in
the Central Asian Orogenic Belt.
From this one could surmise that porphyry Cu–Au deposits are asso-
ciated with island arcs, whereas porphyry Cu–Mo deposits are associat-
ed with continental arcs. For example, Cenozoic porphyry deposits
located in island arcs in the southwestern Pacific are all Cu–Au deposits,
e.g., Grasberg and Batu Hijau in Indonesia; Panguna and Ok Tedi in
Papua New Guinea; Lepanto–Far South East, Tampakan, Atlas and
Sipilay in the Philippines (Cooke et al., 2005). Some researchers have
even argued that Cu comes from the mantle, whereas Mo comes from
the continental crust (Mao et al., 2011). This is not the case, however, al-
though porphyry Cu (±Au and ±Mo) deposits indeed do have higher
εNd isotopic values (Hou et al., 2007a), implying less contribution from
the continental crust. This observation, however, does not necessarily
support a mantle origin for Cu, either, because both the depleted mantle
and the oceanic crust have high εNd values, whereas enriched mantle
and the continental crust have low εNd values. As argued below
(Section 3.2.1), a strong case can be made that most of the Cu comes
from subducted oceanic crust. The distribution of porphyry deposits
does not support the premise that the Cu comes from the mantle.
Moreover, porphyry Cu–Au deposits are not always formed in island
arc environments, either. For example, there are also many porphyry
Cu–Au deposits (without economic levels of Mo) in the western
American continents, including some of the world's top 25 largest por-
phyry deposits, e.g., Cerro Casale in Chile; Minas Conga in Peru; Bajo
de la Alumbrera in Argentina; Pebble Copper in the USA; and Prosperity
in Canada. Here we give brief introductions to three famous porphyry
Cu–Au deposits.
3.1.1.1. Grasberg, Indonesia. Grasberg in Irian Jaya, Indonesia is one of the
largest high-grade hypogene porphyry Cu–Au deposit (38.32 Mt Cu @
1.12% and 3662 t Au @ 1.07 g/t) in the world, ranking no. 1 among por-
phyry Au deposits and among the top 10 porphyry Cu deposits (Cooke
et al., 2005). It was formed ~3 Ma ago. The presence of anhydrite and
hematite indicates very high oxygen fugacities (Cooke et al., 2005;
Mathur et al., 2000), near the HM buffer. This deposit is related to the
closure of a small backarc basin between Indonesia and the South
China Sea. As is characteristic of Cenozoic porphyry deposits in south-
western Pacific, it contains no Mo.
 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131 105

Fig. 10. Images of magnetite–hematite intergrowths from major porphyry deposits in China, indicating that the oxygen fugacity reached the HM buffer (Zhang, Ling et al., 2013). A. Dexing
(Zhang, Ling et al., 2013), B. Xiongcun, C. Duobuza, D. Yulong (Sun et al., 2013a,b), E. Qulong, F. Zijinshan (Sun et al., 2013a,b).

3.1.1.2 . Far Southeast–Lepanto, Philippines. The Far Southeast–Lepanto
porphyry and epithermal Cu–Au deposits, Philippines, are parts of a
large epithermal–porphyry Cu–Au body with a total of 5.48 Mt Cu @
0.8 wt.% and 973 t Au @ 1.42 g/t (Table 1; Cooke et al., 2005;
Hedenquist et al., 1998). Sulfates, including anhydrite and alunite (likely
related to the epithermal mineralization) are abundant in the minerali-
zation system, and hematite formed during chlorite alteration, indicat-
ing high oxygen fugacity up to the HM buffer (Hedenquist et al., 1998).
3.1.1.3. Santo Tomas II (Philex), Philippines. The Santo Tomas II (Philex)
porphyry deposit, Philippines, has total reserves of 1.2 Mt Cu @
0.33 wt.% and 233 t Au @ 0.64 g/t (Table 1). It is also associated with
a highly oxidized magma, as indicated by anhydrite veinlets and a
magnetite–titanohematite assemblage, which indicates oxygen fu-
gacities near the HM buffer at nearly magmatic temperature (Imai,
2001).
In summary, essentially, most if not all, porphyry Cu–Au deposits are
highly oxidized (Figs. 9, 10). In addition to those mentioned above, he-
matite flakes in quartz veinlets have been reported in the Waisoi por-
phyry Cu deposit (Namosi district), Viti Levu, Fiji (Imai et al., 2007).
The Tongshankou porphyry skarn Cu–Au deposit, in the Lower Yangtze
River belt, central eastern China, also has primary hematite next to sul-
fides (Li et al., 2008). The euhedral characteristics of the hematite imply
a hydrothermal origin.
Porphyry Au deposits have oxygen fugacities similar to, if not higher
than, porphyry Cu deposits. For example, Marte, a large porphyry Au

Table 1
Age, grade and tonnages of major porphyry deposits discussed in the text.

Deposit Province Ref Age Tonnage Au Au Cu Cu Mo Mo

grade grade grade

(Ma) (Mt) (g/t) (t) (wt.%) (Mt) (wt.%) (Mt)

Cu–Au Grasberg Irian Jaya Cooke et al. (2005), Mutschler et al. (2010) 4–3 3409 1.07 3662 1.12 38.3
Lepanto-Far N. Luzon Cooke et al. (2005), Mutschler et al. (2010) 1.5–1.2 685 1.42 973 0.8 5.48
South East
Santo Tomas II Philippines Mutschler et al. (2010) 1 364 0.64 233 0.33 1.2
Cu–Mo El Teniente Central Chile Cooke et al. (2005), Mutschler et al. (2010) 7.1–4.6 11,845 0.0035 437 0.92 109 0.02 2.50
Chuquicamata Nothern Chile Cooke et al. (2005), Mutschler et al. (2010) 33.6 15,052 0.04 301 0.71 106 0.024 1.81
Dexing China Mutschler et al. (2010), Zhang, Ling et al. (2013), 170–148 1500 0.18 19 0.45 8.4 0.01 0.29
Zhang, Sun et al. (2013)
Qulong China Xiao et al. (2012) 14 0.5 10.4 0.03 0.5
Yulong China Mutschler et al. (2010), Liang et al. (2006) Paleogene 850 0.84 7.14 0.03 0.15
Sar-Cheshmeh Iran Cooke et al. (2005), Mutschler et al. (2010) 12 1200 0.27 324 1.20 14.4 0.03 0.36
Batu Hijau Indonesia Mutschler et al. (2010) 5 1644 0.35 572 0.44 7.26
Panguna Bougainville Cooke et al. (2005) 3.5 1415 0.57 799 0.46 6.51
Ok Tedi PNG Mutschler et al. (2010) 1.2–1.1 700 0.64 446 0.64 4.48
Tampakan Philippines Cooke et al. (2005) 3.3–2.2 1400 0.24 336 0.55 7.70
Atlas Philippines Cooke et al. (2005) 61 1380 0.24 331 0.50 6.90
Mo Henderson United States Mutschler et al. (2010) 30–27 727 0.17 1.24
Reduced Catface Canada Mutschler et al. (2010) Middle Eocene 308 0.37 1.14 0.01 0.02
Reduced Baogutu China Cao et al. (2014) 0.1 14 0.28 0.63 0.011 0.018
106 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131
deposit located in the Maricunga belt of the Andean Cordillera, northern
Chile, contains several percents of hematite, magnetite, anhydrite and
gypsum (Vila et al., 1991), clearly reaching the HM buffer (Figs. 10, 11).
It has also been argued that iron oxides–copper–gold (known as
IOCG) deposits are the low S version of porphyry Cu–Au deposits, con-
trolled by secular changes in oceanic sulfate content and the geothermal
gradients at the end of the Precambrian (Richards and Mumin, 2013).
This is still elusive. Nevertheless, IOCG deposits are all highly oxidized,
up to the HM buffer.
3.1.2. Porphyry Cu–Mo deposits
In general, porphyry Cu–Mo deposits have FeO contents systemati-
cally lower than porphyry Cu, but higher than pure porphyry Mo de-
posits, with oxygen fugacities also falling between them (Fig. 8). Many
porphyry Cu–Mo deposits have high sulfate contents, with much less
magnetite. No hypogene hematite has yet been reported in some of
the supergiant porphyry Cu–Mo deposits, partially due to severe super-
gene oxidation, which makes it difficult to identify primary hematite.
Porphyry Cu–Mo deposits have Cu and Au grades comparable to
those of porphyry Cu ± Au deposits, with low Mo grades, ranging
from 0.01 to 0.03 wt.% (Table 1) (Cooke et al., 2005). Some of the super-
giant deposits may have large Mo reserves of several million tons
(Cooke et al., 2005). The Cu–Au and Mo mineralizations that occur in
the same ore bodies usually do not happen at the same time, indicating
different sources and/or different mineralization processes. Consistent-
ly, the Mo/Cu ratios of these deposits are generally more than 20 times
higher than the primitive mantle ratio value (McDonough and Sun,
1995), suggesting that Mo has been added to the porphyry deposits
from different sources.
One of the most important geologic processes that enriches Mo is the
oxidation–reduction cycle operating during chemical weathering at the
Earth's surface, i.e., Mo is mobilized during oxidation and then enriched
in organic-rich sediments due to reduction (Li et al., 2012a,b). The
Fig. 11. Stability domains of the trisulfur ion S−
3 , sulfate, and sulfide in an aqueous solution,
as a function of oxygen fugacity (log10 fO2) and acidity (pH = −log10 mH+, in mol per kg)
at 350 °C and 0.5 GPa illustrating sulfate reduction (modified after Pokrovski and
Dubrovinsky, 2011; Sun et al., 2013a,b). Also shown is the oxygen fugacity of the major
mineral buffers (HM, thick horizontal orange line; NNO and FMQ, horizontal dashed
lines) and the neutrality point of pure water (the vertical dashed line). The orange field be-
tween HM and ΔFMQ +2 is the optimum condition for porphyry Cu, Au, Mo mineraliza-
tion (Sun et al., 2013b). Lines E1, E2, E3 and E4, show trajectories for sulfur reduction (Sun
et al., 2013b). Stability domains of trisulfur ion S− 3 at total dissolved sulfur concentrations
of 1 wt.% and 0.1 wt.% are shown.
involvement of such reducing agents as organic matter seemingly ex-
plains the system's lower oxygen fugacity. The most famous porphyry
Cu–Mo deposits are the Cenozoic ones located along the eastern Pacific
margin.
3.1.2.1. El Teniente. The supergiant El Teniente deposit in Chile is the
largest porphyry Cu–Mo–Au deposit in the world, with total reserves
of ~ 109 Mt Cu @0.92%, 2.5 Mt Mo @ 0.02% and 437 t Au @0.035 g/t
(Table 1; Cooke et al., 2005; Mutschler et al., 2010). The deposit spatially
corresponds to the Juan Fernandez Ridge (Cooke et al., 2005), and thus
has been attributed to slab melting during ridge subduction (Sun et al.,
2010). Others argued that ridge subduction is not responsible for mak-
ing the supergiant porphyry deposit based on the inferred migration
history of the arc (Kay et al., 2005). El Teniente is a nested porphyry sys-
tem that, according to different authors, was active for ~ 1 Ma (Baker
et al., 2011; Cannell et al., 2003) up to more than 7 Ma (14.2–6.5 Ma)
(Barra, 2011; Stern et al., 2011; Vry et al., 2010). High Fe2O3/FeO values
of 1 to 3 (Garrido et al., 2002), quartz anhydrite veins and anhydrite-
cemented breccias as well as gypsum clearly indicate high oxygen fu-
gacities (Klemm et al., 2007; Vry et al., 2010). Although it is not spelled
out, the high Fe2O3/FeO ratios of 1 to 3 (Garrido et al., 2002) indicate
abundant hematite, reaching the HM buffer. Hydrothermal rutile also
indicates high oxygen fugacity (NNO + 1.3) (Rabbia et al., 2009),
which is however much lower than the HM buffer, though. Neverthe-
less, the oxygen fugacity undoubtedly fluctuated during porphyry min-
eralization (Liang et al., 2009; Sun et al., 2013b), and the hydrothermal
rutile only records the oxygen fugacities under which it crystallized.
Most of the Cu in El Teniente was emplaced during the late magmat-
ic stage (Cannell et al., 2005). A small sulfur- (N 3 wt.%) and copper-rich
(N0.5 wt.%) fine-grained igneous rock known as “Porphyry A” stock
(b1 km3, 6.09 ± 0.18 Ma) (Stern et al., 2011) has abundant igneous an-
hydrite, with varied textures ranging from interstitial to poikilitic and
corresponding modal abundances from 10 to 20%, respectively. These
igneous anhydrite grains with planar crystal boundaries, occur along
with fresh and unaltered biotite, feldspars, quartz, and Fe-oxides
(Stern et al., 2007). Because the anhydrite-rich stock is isotopically sim-
ilar to all the other igneous rocks of the late Miocene deposit (Baker
et al., 2011; Stern et al., 2007) formed at a time of regional compressive
deformation, it has been proposed that an oxidized parent magma in the
large productive magma chamber was undergoing igneous fraction-
ation at that time. During a period of recharge by mantle-derived
mafic magmas into the base of the chamber and associated volatile
transfer and concentration near its roof, the opportunity arose to pro-
duce the Cu- and S-rich magmas that formed the anhydrite-bearing in-
trusive rocks (Stern et al., 2007).
3.1.2.2. Chuquicamata. Chuquicamata is another supergiant porphyry
deposit in Chile, with a total reserve of ~ 106 Mt Cu @ 0.71%, 1.81 Mt
Mo @ 0.024% and 301 t Au @ 0.04 g/t (Table 1. Cooke et al., 2005;
Mutschler et al., 2010). Similar to El Teniente, the formation of the
Chuquicamata porphyry Cu deposits also lasted for several million
years, between 36 and 31 Ma (Ballard et al., 2001; Ossandon et al.,
2001). It is closely associated with highly oxidized adakite (Oyarzun
et al., 2001, 2002). Because quantitative oxygen barometers based on
Fe–Ti oxides are prone to resetting, and primary whole rock Fe(III)/
Fe(II) ratios and anhydrite, if originally present, are unlikely to have
survived the hydrothermal alteration and surficial weathering of this
deposit, the zircon Ce4+/Ce3+ ratio has been used to indicate its high
oxygen fugacity (Fig. 12) (Ballard et al., 2002).
3.1.2.3. Dexing. The Dexing porphyry Cu deposit is located in southeast-
ern China, with total reserves of 8.4 Mt Cu @ 0.45%, 0.29 Mt Mo @ 0.01%
and 19 t Au @ 0.18 g/t (Table 1. Zhang, Ling et al., 2013; Zhu et al., 1983).
The deposit consists of a cluster of three porphyries, with Tongchang as
the largest in the center, Fujiawu the second in the southeast and
Zhushahong, a small deposit in the northwest (Li et al., 2007; X.F. Li
 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131
Fig. 12. Ce4+/Ce3+ and (Eu/Eu*)N ratios of zircon grains for Dexing and Shapinggou
porphyry deposits as well as ore-bearing and ore-barren porphyries from Chile. High
Ce4+/Ce3+ signifies high oxygen fugacity. Data of ore-bearing and ore-barren samples in
Chile from Ballard et al. (2002), Dexing from Zhang, Ling et al. (2013) and Shapinggou
from Zhang, Li et al. (2013).
et al., 2013; Zhou et al., 2013). The ore minerals comprise pyrite, chalco-
pyrite, molybdenite, minor tetrahedrite, bornite and chalcocite. Gangue
minerals include quartz, muscovite, chlorite, calcite, minor epidote and
anhydrite. The porphyry is an adakite formed at ~170 Ma (Zhang, Ling
et al., 2013; Wang et al., 2006a,b). Another poly-metal deposit, Yinshan,
formed roughly at the same time and may be paragenetically related
(Wang et al., 2013). The Dexing porphyry deposit is closely associated
with highly oxidized magmas (Zhang, Ling et al., 2013; Li and Sasaki,
2007), e.g., it is famous for abundant specular hematite, which mostly
formed during late stage hydrothermal alteration (Fig. 13). Inter-
growths of magnetite and hematite indicate its oxygen fugacity reached
the magnetite–hematite buffer (Fig. 11). Hematite is also found in fluid
inclusions in Dexing (Liu et al., 2011).
3.1.2.4. Qulong. The Qulong porphyry Cu–Mo deposit is now the largest
porphyry-type deposit in China, with reserves of 10.4 Mt Cu @ 0.5%
and 0.5 Mt Mo @ 0.03% (Table 1. Xiao et al., 2012). It is located in the
Gangdese orogenic belt in southern Tibet. In addition to abundant hy-
drothermal anhydrite of up to 10% or more, magmatic anhydrite is
also reported in unaltered granodiorite porphyry. These anhydrite oc-
currences indicate that the Qulong magmatic–hydrothermal system
was highly oxidized and sulfur-rich, with abundant sulfates (Xiao
et al., 2012; Yang et al., 2009) (Fig. 14). Given that it formed at
~ 14 Ma, which post-date the initial collision between Indian and
Fig. 13. An image of specularite from the Tongchang deposit in the Dexing porphyry Cu
deposits. Specularite cutting across carbonate veins, indicating that it was formed very
late, likely through hydrothermal alteration.
107
Eurasian continents, Qulong is taken as a typical post-collisional por-
phyry deposit. Nevertheless, the Indian plate is still subducting north-
ward. It is not clear whether the portion of the subducting slab
underneath Qulong was continental or oceanic. Intergrowths of hema-
tite and magnetite (Fig. 10) indicate the oxygen fugacity of Qulong
reached the HM buffer. Adakites found in the Qulong deposit are mix-
tures of continental and slab melts (Sun et al., 2012a).
3.1.2.5. Yulong. The Yulong porphyry Cu–Au deposit belt is distributed
along the northwestern extension of the Red River–Ailao Shan fault sys-
tem, at the eastern margin of the Tibetan Plateau (Hou et al., 2007b;
Jiang et al., 2006; Liang et al., 2006), and covers an area of ~ 300 km
long and ~ 20 km wide. Five major porphyries, which contain most of
the Cu reserves so far discovered in the belt, are located in a narrow,
elongated domain of approximately 50 km long and 10 km wide and
are closely associated with Cenozoic high potassium intrusive rocks
(Liang et al., 2006, 2007). The Yulong porphyry is the largest one in
the Yulong copper deposit belt, with reserves of N7.14 Mt of Cu @
0.84% and 0.15 Mt of Mo @ 0.028% (Table 1; Liang et al., 2006;
Mutschler et al., 2010). All five known porphyry deposits all together
contain a total of more than 8 million tons of Cu and Mo reserves. Zircon
U–Pb dating shows that the formation ages of deposits within the
Yulong ore belt range from 41.2 to 36.9 Ma, extending over a period of
similar to 4.3 Ma, with formation ages decreasing systematically from
northwest to southeast (Liang et al., 2006). Zircon grains from the
Yulong ore-bearing porphyries have higher Ce4 +/Ce3 + values than
those from barren porphyries in the region (Liang et al., 2006). Abun-
dant magnetite and hematite suggest that the ore-bearing porphyries
are highly oxidized, reaching the HM buffer (Figs. 10, 11) (Sun et al.,
2013b).
Fig. 14. Images of magmatic anhydrite from the Qulong giant porphyry deposit in the
Gangdese porphyry belt, south Tibetan Plateau. Bi = biotite; Anh = anhydrite; Kf =
K-feldspar; Py = pyrite; Cpy = chalcopyrite; Ap = apatite.
108 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131
3.1.2.6. Sar-Cheshmeh. The Sar-Cheshmeh is one of the top 20 largest
porphyry Cu–Au–Mo deposit in the world with reserves of 14.4 Mt Cu
@ 1.2%, 0.36 Mt Mo @ 0.03%, and 324 t Au @ 0.27 g/t (Cooke et al.,
2005). It is located in southwestern Iran and is associated with several
intrusive pulses of Miocene stocks (~12.2 Ma) (Mutschler et al., 2010),
ranging in composition from diorite through granodiorite to quartz–
monzonite (Hezarkhani, 2006). Molybdenum enrichment and deposi-
tion took place before Cu. Anhydrite is a popular mineral identified in
most veins (Hezarkhani, 2006). Hematite has been reported, but it oc-
curs as a secondary supergene ore forming mineral (Shahabpour,
1991). The Sar-Cheshmeh and several other giant Miocene porphyry
deposits of Iran and Pakistan are located in a region undergoing conti-
nent–continent collision. The geodynamic and architectural controls
on porphyry formation in this complex tectonic zone are unclear
(Cooke et al., 2005). The ore-forming magmas in this section of the
Tethys margin have high Sr contents (N 500 ppm) and Sr/Y (N 50)
(Haschke et al., 2010), which are clearly adakitic (Defant and
Drummond, 1990). Previous studies suggested that these magmas are
a product of continental arc-style magmatism (Cooke et al., 2005).
They were attributed to either the attempted subduction of the Arabian
plate beneath the Eurasian plate, or the change from subduction of
oceanic to continental crust (Cooke et al., 2005), or partial melting of a
fertile copper- and sulfur-enriched arc crustal keel (Haschke et al.,
2010). Further studies are needed on the formation of Sar-Cheshmeh
and other Cenozoic porphyry deposits in the belt.
3.1.3. Porphyry Mo deposits
Porphyry Mo deposits generally have higher SiO2 and lower FeO
contents. It also has been proposed that porphyry Mo deposits have sys-
tematically lower oxygen fugacities than porphyry Cu (Au) and Cu–Mo
deposits (Fig. 9). There are three major porphyry Mo deposit belts in the
world, the Henderson–Climax (Klemm et al., 2008; Pettke et al., 2010;
Seedorff and Einaudi, 2004a,b; Singer, 2008), Qinling–Dabie (Chen,
2013; Chen et al., 2000; Li et al., 2012a; Mao et al., 2008; Stein et al.,
1997; Yang et al., 2013; Zeng et al., 2013; Zhang, Li et al., 2013) and
Xing'an–Mongolia belts (Wu et al., 2011; Y. Zhang et al., 2013; Zeng
et al., 2013). The oxygen fugacity can also reach the HM buffer during
sulfate reduction and mineralization (Fig. 10), likely because of the
lower FeO contents.
3.1.3.1. Henderson. Henderson porphyry Mo deposit is located in the Cli-
max–Henderson Mo belt, Colorado. It consists of 12 Oligocene rhyolitic
stocks in three centers, Henderson (oldest), Seriate, and Vasquez
(deepest and youngest), at depths of ~ 1 km below the surface at the
Red Mountain (Seedorff and Einaudi, 2004a), with a reserve of
1.24 Mt Mo @ 0.17 wt.% (Table 1). Previous studies proposed that, in
the Henderson porphyry Mo deposit, Fe was leached at high to moder-
ately high temperatures and then fixed in the rock at lower tempera-
tures, first mainly as magnetite and then as pyrite and minor
pyrrhotite and specular hematite (Seedorff and Einaudi, 2004a). Other
porphyry deposits in the Climax–Henderson belt also contain hematite,
indicating these deposits reached the HM buffer.
3.1.3.2. Shapinggou. The Shapinggou porphyry Mo deposit is the largest
Climax-type Mo deposit in the world, with total proven Mo reserves
of over 2.2 million metric tons @ 0.17 wt.% (Zhang, Li et al., 2013). It is
located in the western Dabie Mountains, along the east extension of
the East Qinling Mo mineralization belt (Chen, 2013; Chen et al., 2013;
Gao et al., 2010; H.Y. Li et al., 2012; Han et al., 2013; N. Li et al., 2013;
Stein et al., 1997; Yang et al., 2013; Zeng et al., 2013; Zhu et al., 2010),
to the north of the Triassic suture between the north and south China
blocks (Sun et al., 2002). Both Re–Os isochron and U–Pb zircon dating
give the same age of ~111 Ma (Zhang, Li et al., 2013), which assigns it
to the third mineralization pulse of the East Qinling Mo belt (Li et al.,
2012a; Mao et al., 2008, 2011). High zircon Ce4+/Ce3+ ratios indicate
very high oxygen fugacity, comparable to those of Chuquicamata
(Fig. 12) (Zhang, Li et al., 2013).
3.2. Linkage between oxidized magmas and porphyry deposits
Copper, Au and Mo are all chalcophile elements, the behaviors of
which are mainly controlled by reduced sulfur, e.g., sulfide, hydrosulfide
−
complexes (Sun et al., 2004a), or polysulfide (e.g., S2− 2 , S3 ) complexes
(Sun et al., 2013b). Although most geologists agree that porphyry de-
posits are closely associated with oxidized magmas (Sillitoe, 2010;
Sun et al., 2013b), it is still hotly debated as regarding to why oxidized
magmas favor porphyry mineralization and how oxidized the ore-
forming magmas should be. Major disagreements include: (1) What is
the most favorable oxygen fugacity for porphyry mineralization?
Some workers proposed that ΔFMQ + 2 is a magic number for porphyry
mineralization (Mungall, 2002), whereas ΔFMQ + 2 to +4 is the most
favorable range of oxygen fugacity for porphyry deposits (Sun et al.,
2013b). Yet others claimed that variations in oxidation state over typical
ranges for arc magmas formed during plate subduction (ΔFMQ = 0
to +2) have no major effects on the potential to form porphyry Cu ±
Au ± Mo deposits during plate subduction (Richards, 2011b). It is
even argued that some porphyry deposits formed in reduced magmas
(Cao et al., 2014; Rowins, 2000; Smith et al., 2012). (2) What is the
main sulfur species in porphyry? Some workers concluded that sulfate
is the predominant sulfur species in ore-forming porphyries (Cooke
et al., 2011; Field et al., 2005; Liang et al., 2009; Sotnikov et al., 2004;
Sun et al., 2013a,b), whereas others argue that the main sulfur species
is SO2 dissolved in porphyry magmas (Richards, 2014; Smith et al.,
2012), i.e., neither sulfate nor sulfide. (3) Is sulfide saturation during
magma evolution important for porphyry mineralization? Some
workers proposed that sulfide undersaturation is important for porphy-
ry mineralization, i.e., no residual sulfide remains in the source (Li et al.,
2012b; Liang et al., 2009; Sun et al., 2013b), whereas others argued that
sulfide saturation and accumulation are of critical importance for por-
phyry mineralization (Wilkinson, 2013).
In general, the porphyry mineralization process consists of 3 major
phases: (1) source, i.e., extraction of chalcophile elements from the
source; (2) transportation and concentration of ore-forming elements;
and (3) deposition and fixation of the ore forming elements into
orebodies. The relationship between oxidized magmas and porphyry
deposits during these three steps are discussed below.
3.2.1. Sulfur oxidation, sulfide under saturation and residual sulfide
Copper, Au and Mo are all chalcophile elements, with high partition
coefficients between sulfide and melts, e.g., DCu = 1334 ± 210 (Patten
et al., 2013), DAu = 4500 –11,200 (Mungall and Brenan, 2014), and
DMo = 0.15–5.15 (Li and Audetat, 2013), respectively. Some experi-
ments suggest that DMo increases with decreasing oxygen fugacities
(Li and Audetat, 2013). Therefore, the behaviors of Cu and Au are
strongly controlled by sulfide, whereas Mo is much less sensitive to sul-
fide, especially at high oxygen fugacities. During mantle melting, Cu as
well as Au and Mo are all moderately incompatible elements, with par-
tition coefficients ranging between those of Yb and Ce (McDonough and
Sun, 1995; Sun et al., 2003a,b, 2004a). The estimated Cu abundance in
the primitive mantle is 30 ppm (McDonough and Sun, 1995), whereas
the Cu concentrations in MORB so far published range from 70 to
150 ppm (Hofmann, 1988; Sun et al., 2003b). When there is no residual
sulfide in the mantle source, Cu and also other chalcophile elements be-
come highly incompatible (Lee et al., 2012; Liu et al., 2014). Partial melt-
ing of mantle peridotite may form melts with high Cu contents up to
350 ppm at high oxygen fugacities, at very low degree of partial melting
(Fig. 3) (Lee et al., 2012). Nevertheless, most arc magmas formed at
much N 10% partial melting, resulting in much lower Cu contents
(e.g., 100 ppm), which is not favorable than reducing magmas for por-
phyry mineralization. In contrast to mantle peridotite, MORB has sulfur
abundances of about 1000 ppm, the effects of oxygen fugacity on
 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131 109

residual sulfides, and, consequently, the Cu content in the melts, be-

comes much more obvious when considering partial melting of
subducted oceanic slabs.
The S abundance in the primitive mantle is estimated to be about
200–250 ppm (McDonough and Sun, 1995), and about 150 ppm in de-
pleted mantle (Lorand, 1990; Mavrogenes and O'Neill, 1999). Mainly,
the sulfur speciation in magmas is controlled by oxygen fugacity. Sulfide
is the predominant sulfur species at oxygen fugacities lower than the
FMQ buffer. Sulfate proportions start to climb up above the FMQ buffer.
Most of the sulfur in the magmas is present as sulfate at ΔFMQ + 2
(Fig. 11) (Jugo, 2009; Jugo et al., 2005, 2010). Experiments show that
sulfate is much more soluble than sulfide in magmas. The sulfur content
at sulfide saturation (SCSS) increases solely as a function of increasing
fO2 (Jugo, 2009):

h i
2–
SCSS ¼ S ð1 þ expð2:23ΔFMQ –2:89ÞÞ ð9Þ

and

 h i h i
6þ 2–
ΔFMQ C ¼ 1:29 þ 0:45 ln S – ln S ð10Þ

where ΔFMQC refers to the critical fO2 for simultaneous saturation of

sulfide and sulfate (Jugo, 2009).
The predicted SCSS content at sulfide saturation in basalts ranges
from 1300 ppm at ΔFMQ − 1 and 1500 ppm at ΔFMQ + 0.5, to
7500 ppm at ΔFMQ + 2 and 1.4 wt.% at ΔFMQ + 2.3 (Fig. 15) (Jugo,
2009). At oxygen fugacities of ΔFMQ 0 to + 2.5, the more oxidizing
the system, the higher the S contents in the magmas, and thus high ox-
ygen fugacity is the most efficient way to eliminate residual sulfides
(Lee et al., 2012; Sun et al., 2013b). The solubility of sulfide in magmas
is independent of oxygen fugacity below the FMQ buffer (Mavrogenes
and O'Neill, 1999), implying that most of the sulfur is removed in the
form of sulfate under high oxygen fugacity (Jugo, 2009), and with its re-
moval releasing much more of the chalcophile elements (Lee et al.,
2012; Liang et al., 2009; Sun et al., 2004b).
The average S concentration in MORB is ~ 1000 ppm (O'Neill and
Mavrogenes, 2002), while laboratory experimental measurements
have determined the S content at sulfide saturation in basalts to be Fig. 15. Sulfur speciation curve vs. fO2 for basaltic glasses based on the S6+/ΣS estimates of
1300 ppm at oxygen fugacities of ΔFMQ 0 (Jugo, 2009). The small differ- XANES (in bold), EPMA (dashed line) (Jugo, 2009; Jugo et al., 2005, 2010). Also shown are
fields of different tectonic settings, (A) Japan arc and Mexican arc; (B) MORB, OIB and
ence between the average MORB and experimental values is likely due
mantle wedge, and arc. MORB = mid-ocean ridge basalt; IAB = Island arc basalt;
to slight differences in oxygen fugacities and pressure effects, i.e., sulfide BABB = Back arc basin basalt; OIB = Oceanic island basalt.
is less soluble under higher pressures (Mavrogenes and O'Neill, 1999).
Given that most MORB forms through ~ 10% partial melting of the
depleted MORB mantle, it extracts about 100 ppm of sulfur from
the mantle source, leaving behind ~ 150 ppm of sulfur as residual sul-
fide. In case all the sulfur is present as sulfide, ~ 25% partial melting is Nevertheless, normal arc rocks are not favorable materials for por-
needed to eliminate all the residual sulfides from the mantle source phyry Cu mineralization. Arc magmas are probably neither unusually
at ΔFMQ 0 (Fig. 3) (Lee et al., 2012). Such large degrees of partial oxidized nor enriched in economic elements of interest, such as Cu
melting would dilute the released Cu and produce picrite or even (Lee et al., 2010; Lee et al., 2012). Instead, most porphyry Cu deposits
komatiite, not basalt. are closely associated with adakite (Oyarzun et al., 2001; Sajona and
For the mantle wedge above subducting slabs, the estimated S con- Maury, 1998; Sun et al., 2010, 2012a; Thieblemont et al., 1997), or so
tent at sulfide saturation ranges from 1500 ppm (at ΔFMQ + 0.4) to called high Sr/Y porphyries (Chiaradia et al., 2012; Richards, 2011a).
4500 ppm (at ΔFMQ + 1.7) (Jugo, 2009). As shown in Fig. 16, the Most of the ore forming adakites were formed through slab melting
highest oxygen fugacity in arc magmas may be NΔFMQ + 3, which (Sun et al., 2011, 2012a), deriving from the subducting oceanic crust
allows up to 1.4 wt.% of S at sulfide saturation (Jugo, 2009). At oxygen itself rather than the overlying mantle wedge. MORB has higher Cu
fugacities below ΔFMQ + 1, 10% or less partial melting of the mantle contents (70–150 ppm) (Hofmann, 1988; Sun et al., 2003b) than
wedge allows preservation of residual sulfides, assuming that the S other portions of the subducted oceanic slab, and thus is likely the
abundances in the mantle wedge is also 250 ppm. At higher oxygen fu- main contributor to mineralization. Therefore, partial melting of
gacity, no residual sulfides can be expected unless there is additional subducted oceanic slabs forms magmas with high Cu contents (Sun
sulfur added from the subducting slab, which in actuality is probably et al., 2011, 2012b), which plausibly explains the close associations
the case. During metamorphism of the subducting slab, S is mobile between adakites, especially formed during ridge subductions, and por-
from metamorphic rocks ranging in grade from blueschist to amphibo- phyry Cu deposits. These papers, however, did not consider the effects
lite (Sun et al., 2013a; Tomkins, 2010), such that they can release S and of oxygen fugacity and dramatically underestimated the contributions
chalcophile elements to the mantle wedge (J.L. Li et al., 2013). of slab melting.
110 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131
Fig. 16. Oxygen fugacity of different tectonic settings. Note the range of oxygen fugacity for
continental peridotite is much less than that of Bryant et al. (2007), after removing perido-
tite samples from arc settings. The oxygen fugacities of convergent margin magmas are
systematically higher than those of intraplate settings. Magmas from intraplate settings
without influence from plate subduction are too reduced for mineralization (Sun et al.,
2013b).
Modified after Bryant et al. (2007).
Slab melts formed at oxygen fugacities higher than ΔFMQ + 2 are fa-
vorable for porphyry Cu mineralization. MORB has an average S content
of ~1000 ppm (O'Neill and Mavrogenes, 2002), from which it is easy to
get the 22% and 10% partial melting needed to eliminate residual sul-
fides at ΔFMQ + 1.7 and ΔFMQ + 2, respectively. Correspondingly,
the Cu contents of such melts would be 450 and 1000 ppm, respectively.
Slab melts formed at ΔFMQ + 2 would have Cu contents more than
twice as high as those formed at ΔFMQ + 1.7, and thus are considerably
more favorable for Cu porphyry mineralization than mantle wedge
melts. Only four times greater enrichments of Cu are needed to reach
economic porphyry deposit proportions of ~ 4000 ppm. This ought to
be easily achieved through magma evolution plus hydrothermal pro-
cesses. At oxygen fugacities of ΔFMQ + 2.3 or higher, only 5% partial
melting is needed to remove all the residual sulfides, forming melts
with initial Cu contents of ~ 2000 ppm. In contrast, unrealistic N50%
partial melting is needed to eliminate all residual sulfides at oxygen
fugacities lower than ΔFMQ + 1, corresponding to a Cu content of
less than 200 ppm in the melt. Residual sulfide would exist until
the entire slab melted, in which case sulfide would remain the pre-
dominant sulfur species in both melt and slab (under reducing con-
ditions of b ΔFMQ 0).
In order to form supergiant porphyry deposits, e.g., El Teniente, up to
600 km3 of magma with a Cu content of 100 ppm would be needed to
get the necessary amount of metal (Stern et al., 2011). Note that most
porphyry deposits have very small surface exposures, ranging in area
from less than 1 km2 (mostly) to ~ 5 km2 (in rare cases). Thus, the
magma chamber would need to be unrealistically thick, e.g., thicker
than the continental crust. Alternatively, the magma must scavenge
laterally for distances over 10 km and concentrates the Cu at one rel-
atively small spot. None of these scenarios are practical. For adakitic
melts with initial Cu contents of ~ 1000 ppm, the amount of magma
needed measures only 60 km3 for the supergiant El Teniente. A
magma chamber extending to a depth of several kilometers is
sufficient.
Slab melts need to pass through the mantle lithosphere before they
eventually are emplaced in the upper crust, and thus may lose or collect
chalcophile elements by interactions with the mantle. Sulfide saturated
melts would lose some chalcophile elements. For slab melts formed at
melting degrees higher than that require for SCSS, they would be under-
saturated in sulfide and thus could assimilate more sulfides and
chalcophile elements from the surrounding mantle while ascending, de-
pending on the partitioning relationships between melt and residual
sulfide in the mantle. For example, 10% partial melting of MORB with
a S content of 1000 ppm at ΔFMQ N 2.3, would form a melt with a S con-
tent of ~1 wt.%, which is only half of its SCSS. This melt then would have
the capacity to assimilate large amounts of sulfide. This plausibly ex-
plains the common association between high-Mg adakites and porphy-
ry Cu deposits.
Meanwhile, sulfide is kept undersaturated during the evolution
of the oxidized magma, such that no sulfide segregation occurs,
and Cu, Mo, and Au act as moderately incompatible elements.
They would become enriched at an early stage of magma evolution,
and dissolve into fluids following reduction accompanying magne-
tite crystallization (Sun et al., 2004a, 2013b), or other reduction
processes.
It has long been proposed that oxygen fugacities higher than ΔFMQ +
2 have reached the magic number for porphyry mineralization
(Mungall, 2002; Sun et al., 2013b). As discussed above, this is exactly
the point at which residual sulfide is eliminated by ~10% partial melting
of a subducted slab, forming melts with initial Cu contents up to
1000 ppm. In contrast, at oxygen fugacity even only slightly lower,
e.g., ΔFMQ + 1.7, the highest Cu contents that can be reached through
slab melting is ~450 ppm.
The systematically low oxygen fugacities in Japan arc volcanic rocks
(bΔFMQ + 2) compared to those from the western American conti-
nents (up to ΔFMQ + 3) (Fig. 16), is an important factor controlling
the distribution of Cu porphyry deposits, i.e., abundant porphyry Cu de-
posits are located in the western American continents, whereas none
occur in Japan (Fig. 1) (Sun et al., 2012b, 2013b).
3.2.2. Sulfate reduction
At oxygen fugacities higher than ΔFMQ + 2, most of the sulfur in
magmas is present as sulfate, and such magmas usually have higher con-
tents of total S and chalcophile elements. Copper however, is a
chalcophile element, and its final deposition during mineralization
should be controlled mainly by the behavior of reduced sulfur (Liang
et al., 2009; Sun et al., 2004a, 2013b). Therefore, the final stage of miner-
alization inevitably requires the reduction of sulfate (S6+: HSO− 2−
4 /SO4 )
2− − 2−
in the oxidized source magmas to sulfides (S : H2S/HS /S ) or
−
polysulfides (e.g., S2−
2 , S3 ) (Sun et al., 2013b).
In principle, there are several ways to lower the oxygen fugacities
during magma evolution. Among them are degassing of oxidized vola-
tile species (i.e. CO2, SO3), assimilation of reducing country rocks
(Ishihara and Matsuhisa, 1999; Smith et al., 2012), and reduction of sul-
fate by other elements, e.g., fractional crystallization of magnetite and
even hematite (Liang et al., 2009; Sun et al., 2004a, 2013b).
It has also been proposed that degassing of SO2 may lower the oxy-
gen fugacity (Kelley and Cottrell, 2012). As illustrated in Eq. (11),
degassing of SO2 indeed consumes oxygen, such that it may lower the
oxygen fugacity of the system. However, degassing of SO2 cannot reduce
 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131 111

sulfate to sulfide in the magmas. Instead, it drives the reaction (Eq. (11))
to the right, which leads to the oxidation of sulfide.

2H2 S þ 3O2 ¼ 2H2 O þ 2SO2 ð11Þ

Degassing of CO2 may reduce sulfate to sulfide, through a process

similar to that described by Eq. (12).

2C þ SO3 þ H2 O ¼ 2CO2 þ H2 S ð12Þ

As shown in Fig. 17, however, the C–CO2 buffer is lower than the SSO
buffer (Mungall, 2002), therefore there is little C in the system at SSO
buffer. Moreover, degassing of any type is not likely to be a key process
during porphyry mineralization, which is usually occurring at depths of
~2–4 km (Sillitoe, 2010).
Assimilation of reducing sediments may lead to sulfate reduction as
proposed by previous authors (Shen and Pan, 2013; Smith et al., 2012)
(also see Section 4). Nevertheless, assimilation occurring during the
emplacement of porphyries would result in heterogeneous reduction,
because reduction is mainly focused along the porphyry–country rock
interface. This kind of reduction process has been reported for Baogutu
(Shen and Pan, 2013), which was classified as a reduced porphyry Cu
deposit associated with ilmenite-series magmas (Cao et al., 2014) (see
detailed discussion in Section 4.3). Assimilation during magma chamber
development may be better mixed and more homogenized. However, it
would result in early sulfide saturation and segregation from the melt.
Because sulfide is denser than silicate melt, it would tend to sink,
which is more likely to occur during the mineralization of Cu–Ni
deposits, rather than porphyry deposits. Fig. 18. Ferric/ferrous Fe ratios and estimated oxygen fugacities of Manus glasses (Sun
Elements that can exist in variable oxidation states and that are pres- et al., 2004a). Oxygen fugacity of Manus glasses was calculated using the following equa-
 
ent in sufficient abundances to affect the redox state of the silicate Earth tion: ln XFe 2 O3
XFeO ¼ a lnƒO2 þ bT þ c þ ΣdiXi, where, a = 0.196, b = 1.1492 × 104, c =
are C, H, S, and Fe (Mungall, 2002). In highly oxidized porphyry −6.675, dAl2O3 = −2.243, dFeO = − 1.828, dCaO = 3.201, dNa2O = 5.854, dK2O =
6.215 (Kress and Carmichael, 1991).
magmas, sulfate, CO2 and H2O are the dominant species, which are al-
ready oxidized and thus cannot reduce sulfate to sulfide, leaving ferrous
iron as the only probable reducing agent (Sun et al., 2013b). Iron is a ferrous iron is coupled with the reduction of sulfate to sulfide
major element, with about 20 to 30% of the total Fe in a typical porphyry (Eqs. (13), (14)). Magnetite crystallization at Manus and many other
occurring as ferrous iron, corresponding to an oxygen fugacity of less arc volcanic rock series is coupled with dramatic decreases in Cu and
than ΔFMQ + 2 (Fig. 18). Magnetite contains 66.7% ferric iron, whereas Au (Sun et al., 2004a), which is an important factor in understanding
hematite contains 100% ferric iron. Therefore, the crystallization of mag- Au and Cu mineralization (Sun et al., 2004a). The reduction in the
netite and hematite tends to lower the proportions of ferric iron in the amount of Cu and Au during magma evolution is well-known in arc
magma, which apparently would lower the oxygen fugacity. In the magmas (Moss et al., 2001; Sun et al., 2011; Togashi and Terashima,
case of the Manus deposit in volcanic rocks, the Fe3 +/(total Fe) did 1997), and has been referred to as the magnetite crisis (Jenner et al.,
not change much during magnetite crystallization (Fig. 18). This was at- 2010). Indeed, magnetite crystallization/alteration is often taken as
tributed to sulfate buffering (Sun et al., 2004a), i.e., the oxidation of the controlling process for porphyry Cu and Au mineralization by caus-
ing sulfate reduction and presumably also oxygen fugacity fluctuations
(Liang et al., 2009).
There are several ways to describe the oxidation of ferrous Fe. In
magma system, this is better described as oxidation of FeO by sulfate
or another oxidant (Eq. (13)) (Sun et al., 2004a):
2− 2−
SO4 þ 8FeO ¼ 4Fe2 O3 þ S : ð13Þ

Eq. (13) is simplified, Fe2O3 represents the ferric Fe in Fe3O4. This re-
action can be more precisely described by Eq. (14):
2− 2−
SO4 þ 12FeO ¼ 4Fe3 O4 þ S : ð14Þ

These reactions have no effects on the pH value of the system. This is

one reason why the oxygen fugacity of the Manus magma did not
change much (Sun et al., 2004a), or even decrease slightly during the
crystallization of magnetite and sulfate reduction (Jenner et al., 2010)
(see also Section 5).

Fig. 17. Sulfate reduction and oxygen buffers. CCO = carbon dioxide–carbon oxide buffer;
3.2.3. Hematite–magnetite intergrowth
SSO = sulfide–sulfur oxide buffer. Interestingly, in addition to abundant magnetite in porphyry de-
After Mungall (2002) and Sun et al. (2014a,b). posits (Astudillo et al., 2010; Audetat et al., 2004; Baker et al., 1997;
112 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131

Dilles et al., 2011; Imai, 2005; Liu et al., 2011; Yang et al., 2002), hema-
tite and specularite (a hydrothermal variety of hematite) are common
in porphyry copper deposits (Figs. 10, 13) (Zhang, Ling et al., 2013;
Sillitoe, 2010; Sun et al., 2013b). As mentioned previously, primitive he-
matite–magnetite intergrowths have been reported in many porphyry
Cu deposits all over the world (Fig. 10), including nearly all major por-
phyry deposits in China (Sun et al., 2013b), as well as some deposits
in South America (Ballard et al., 2002; Patricio and Gonzalo, 2001; Vila
and Sillitoe, 1991) and the Southwest Pacific islands (Hedenquist
et al., 1998; Imai et al., 2007), and Mongolia (Khashgerel et al., 2008).
Most of the hematite and/or specularite formed during the late stages
of porphyry mineralization (Sillitoe, 2010; Sun et al., 2013b).
The occurrence of primitive hematite in closely association with
magnetite strongly suggests a very high oxygen fugacity (Fig. 11),
such that reaching the HM oxygen fugacity buffer (equivalent to
~ΔFMQ + 4) during porphyry Cu mineralization. This suggests that, in
contrast to hydrothermal systems in the Manus backarc basin (Jenner
et al., 2010; Sun et al., 2004a), the oxygen fugacity of porphyries
increases during magnetite crystallization (Sun et al., 2013b).
The further oxidation of magnetite is controlled by the pH values of
the system (Sun et al., 2013b). In contrast to the magma system, ferrous
Fe is mainly present as Fe2+ in aqueous fluids. In this case, the oxidation
of ferrous Fe is better described by Eq. (15):
2− 2þ 2− þ Such conditions will promote the formation of hematite and would be
SO4 þ 12Fe þ 12H2 O ¼ 4Fe3 O4 þ S þ 24H :
As shown in Eqs. (2) and (1), HM and FMQ oxygen fugacity buffers
do not change with pH. The oxidation potential of sulfate, however, de-
pends strongly on pH (Figs. 11). The oxidation of ferrous iron by sulfate
leads to a decreases in pH in ore-forming fluids within the porphyry
system (Eq. (15)), which drives up the oxidation potential of sulfate.
Consequently, the fO2 increases during the reduction of sulfate
(Fig. 11) (Pokrovski and Dubrovinsky, 2011; Sun et al., 2013b). It is es-
timated that the amount of H+, released during the reduction of sulfate
and oxidation of ferrous iron, may lower the pH down to +2, depending
on temperatures, and if there are no pH buffers in the system to signif-
icantly elevate the oxygen fugacity (Sun et al., 2014a,b) and oxidize
magnetite or ferrous Fe in hydrothermal fluids to hematite and/or
specularite (Eq. (16)).
The porphyry mineralization process requires a continuous reduc-
tion of sulfate to sulfide, coupled with consumption of oxygen and
even reduction of CO2 to CH4. Given that porphyry magmas are highly
oxidized, reaction (21) is not likely to occur. No significant amounts of
methane have been detected in most cases, except in reduced porphy-
ries (see details in Section 4).
Based on high pressure experiments, it was proposed that the tri-
sulfur ion S−
3 is an important sulfur species (Fig. 11) at pressures and
temperatures (Pokrovski and Dubrovinsky, 2011) that are common
for porphyry systems (Hedenquist and Lowenstern, 1994; Seo et al.,
2009; Sillitoe, 2010; Sun et al., 2014a,b). It has been further proposed
that in general geological processes where the tri-sulfur ion may have
been involved need to be reconsidered (Pokrovski and Dubrovinsky,
2011), and this would require the investigation of different reaction
pathways (Sun et al., 2013b). In fluids, the reactions can be described
by Eqs. (22) and (23)
2− 2þ − þ
6SO4 þ 52H2 O þ 57Fe ¼ 2S3 þ 19Fe3 O4 þ 104H ð22Þ
− 2þ 2− þ
2S3 þ 20H2 O þ 15Fe ¼ 6S þ 5Fe3 O4 þ 40H : ð23Þ
Both of these reactions (Eqs. (22), (23)) also would lower the pH of
the fluids, which in turn would elevate the oxidation potential of sulfate.
ð15Þ
favorable for porphyry mineralization. The oxidation potential of the
−
SO2−
4 –S3 reaction also rises with decreasing pH (Fig. 11), so that mag-
netite may be further oxidized to hematite by SO24 −, releasing OH−
(Eq. (24)). This in turn increases the pH and promotes magnetite forma-
tion (Sun et al., 2013b), which may explain magnetite and hematite in-
tergrowths (Fig. 10). In addition to direct oxidation of magnetite,
hematite and specularite may form directly from fluids (Eq. (25)), re-
leasing H+, which lowers pH and promotes further oxidation of ferrous
Fe. Pure hydrothermal hematite and specularite can often be deter-
mined to have formed during the late stages of porphyry mineralization
(Sillitoe, 2010), e.g., the specularite occurring in late stage veins at
Dexing (Fig. 13).
2−
38Fe3 O4 þ 6SO4 þ 5H2 O ¼ 57Fe2 O3 þ 2S3 þ 10OH
− −
ð24Þ

2þ 2− − þ
SO4
2−
þ 8Fe
2þ
þ 8H2 O ¼ 4Fe2 O3 þ S
2−
þ 16H
þ
ð16Þ 38Fe þ 6SO4 þ 33H2 O ¼ 19Fe2 O3 þ 2S3 þ 66H ð25Þ

In magmas, in contrast to fluids, FeO is more abundant than Fe2+. If

Or further oxidation of magnetite (Eq. (17)): S−
3 is indeed stable as proposed (Pokrovski and Dubrovinsky, 2011),
then the reduction of sulfate in magmas first leads to an increase in
2− 2−
SO4 þ 8Fe3 O4 ¼ 12Fe2 O3 þ S : ð17Þ pH (Eq. (26)), which is compensated by further reduction of S− 3
(Eq. (27)). Therefore, S−
3 may indeed cause more fluctuations in oxygen
The formation of hydrothermal hematite will further lower the pH, fugacities through a different reaction pathway, but it has no major in-
whereas further oxidation of magnetite will not change the pH. All the fluences on the final results (Sun et al., 2014a,b).
sulfate reduction reactions provide S2 −, which promotes mineraliza-
2− − −
tion, forming chalcopyrite (Eq. (18)) and more pyrite (Eq. (19)) 6SO4 þ 5H2 O þ 57FeO ¼ 2S3 þ 19Fe3 O4 þ 10OH ð26Þ
(Heinrich, 1990) and releasing H2. Hydrogen may further react with
CO2 and/or O2 (Eqs. (20), (21)) or escape from the porphyry system
− 2− þ
during degassing or diffusive loss (Sun et al., 2014a,b). 2S3 þ 5H2 O þ 15FeO ¼ 6S þ 5Fe3 O4 þ 10H ð27Þ

þ 2þ þ For large porphyry deposits, the reduction of sulfate inevitably re-

Cu þ Fe þ 2H2 S ¼ CuFeS2 þ 3H þ §H2 ð18Þ
sults in the oxidation of magnetite to hematite as the pH is lowered
(Figs. 10, 11). Therefore, the hematite –magnetite intergrowths may
2þ þ be taken as a possible ore indicator in future prospecting for copper
Fe þ 2H2 S ¼ FeS2 þ 2H þ H2 ð19Þ
deposits.

2H2 þ O2 ¼ 2H2 O ð20Þ

3.3. Summary

Sulfur is one of the most important geosolvents that controls the be-
4H2 þ CO2 ¼ CH4 þ 2H2 O ð21Þ havior of copper and other chalcophile elements, therefore it is essential
 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131 113

to the understanding of mineralization processes of copper and a variety

of other metal resources. Sulfate is the dominant sulfur mineral species
in porphyries associated with large copper deposits. This is because the
oxidation of sulfide to sulfate during partial melting is essential for the
efficient extraction of chalcophile elements out of the source region,
especially from subducted oceanic slabs, which have more than
5 times more sulfur than the mantle. In contrast, metals of porphyry
Cu deposits are hosted in sulfides, which require low oxygen fugacity
for their stabilization during the final stage of mineralization. Therefore,
the key process of porphyry mineralization is oxidation and reduction of
sulfur, controlled by ferrous/ferric Fe and pH values. Sulfate reduction in
hydrothermal fluids lowers the pH and consequently elevates the oxy-
gen fugacity of the system up to the HM buffer. The acid released during
sulfate reduction causes alterations. In contrast, sulfate reduction in
magmas does not change the pH, such that the oxygen fugacity is slight-
ly reduced. All types of porphyry deposits, ranging from Cu + Au,
Cu + Mo, and Mo deposits, may be oxidized sufficiently to reach the
redox states of the HM buffer.

4. The association of porphyry deposits with reduced magmas

Although most of the porphyry deposits are closely associated with

oxidized magmas, a small group of porphyry deposits are reported as
apparently related to reduced magmas with oxygen fugacities ranging
from ΔFMQ − 0.5 to − 3 (Fig. 19) (Cao et al., 2014; Rowins, 2000;
Smith et al., 2012). Reduced porphyry deposits so far reported are: 17
Mile Hill, Western Australia; the Minãs de San Anton, Mexico (Rowins,
2000); the Baogutu, northwestern China (Cao et al., 2014; Shen and
Pan, 2013; Shen et al., 2010a, 2012); North Fork Deposit, west Central
Cascades, western North America (Smithson and Rowins, 2005);
Catface; Vancouver Island, British Columbia (Smith et al., 2012); and a
few other small porphyry deposits (Rowins, 2000). Three criteria have
been proposed for the classification of reduced porphyry Cu deposits:
(1) lack of primary hematite and sulfate minerals, (2) rich in hypogene
pyrrhotite and CH4, and (3) oxides belongs to the ilmenite-series,
reduced, I-type granitoids (Rowins, 2000).
Instead of primary hematite, magnetite, and sulfate (e.g., anhydrite,
gypsum) that are frequently seen in oxidized porphyries, these
“reduced” porphyry Cu–Au deposits contain abundant hypogene pyr-
rhotite, and commonly have carbonic-rich ore fluids with substantial
proportions of CH4, clearly indicating a reducing condition (Cao et al.,
2014; Rowins, 2000; Smith et al., 2012). More importantly, they are as-
sociated with ilmenite-bearing, reduced I-type granitoids (Cao et al.,
2014; Rowins, 2000), in direct contrast to oxidized porphyries that are
related to a magnetite-series mineralogy (Ishihara and Sasaki, 1991; Fig. 19. Diagram of log fO2 versus temperature and 1000/T illustrating the oxygen
Thompson et al., 1999). For example, ilmenite is an end-member of fugacities of (A) oxidized porphyry deposits and (B) reduced deposits, Catface and
Baogutu. The systematic difference in oxygen fugacities is likely not primary. Baogutu is
the hematite–ilmenite solid solutions with a very low hematite compo- hosted in ilmenite-series diorites, containing native antimony (An and Zhu, 2010),
nent, varying from XHem (0.01–0.1), for the Catface phase and XHem hypogenepyrrhotite, and methane-rich fluid inclusions. Previous studies suggested that
(0.04–0.09) for the Hecate Bay phase (Smith et al., 2012). Magnetite is assimilation occurring during the emplacement of porphyries resulted in reduction,
nearly pure Fe3O4 with less than 2% Fe2TiO4 component for Catface which is mainly focused along the porphyry–country rock interface (Shen and Pan, 2013).
Modified after Oyarzun et al. (2001) and Cao et al. (2014) and Smith et al. (2012),
(Smith et al., 2012) and Baogutu (An and Zhu, 2010; Cao et al., 2014;
respectively.
Shen and Pan, 2013; Shen et al., 2010a,b). Ilmenite is more abundant
than magnetite in the reduced porphyries (Cao et al., 2014; Smith
process needs to be clarified. Some major questions to be answered
et al., 2012), e.g., all intrusive phases at Catface have accessory FeTi
are: How reduced magmas formed in an arc environment, where oxi-
oxides with ilmenite/magnetite ratios of ~9:1 (Smith et al., 2012), indi-
dized magmas are common, e.g., in western North America? In contrast,
cating a relatively reduced oxidation state, i.e., belonging to the
why are there no porphyry deposits in Japan, where the ilmenite-series
ilmenite-series (Ishihara, 2004). Experiments with apatite have shown
is well-developed (Ishihara and Murakami, 2006)? How do Cu and Au
that SO3 contents reflect the oxygen fugacity of the magmas (Peng
get enriched in reduced magmas? What's the relation between oxidized
et al., 1997). The uniform and low SO3 contents in apatite from reduced
and reduced porphyries?
magma deposits were used to argue that the low oxygen fugacity of
these porphyries is primary (Fig. 20) (Cao et al., 2014; Smith et al.,
2012). 4.1. Reduced magmas
The reduced porphyry deposits range in age from the Late Archean
to the Oligocene (Rowins, 2000). Although the tonnages of these re- Arc magmas usually have high oxygen fugacities (Fig. 16) (Arculus,
duced porphyry deposits are generally much smaller than oxidized por- 1994; Ballhaus, 1993; Carmichael, 1991; Kelley and Cottrell, 2009; Sun
phyry deposits, the mechanism that controls these mineralization et al., 2012a, 2013a,b), a condition that has been attributed to a variety
114 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131
Fig. 20. Diagram of Cl versus SO3 in apatite indicating the oxygen fugacities of Catface and
Baogutu. The SO3 contents of Catface apatite are all lower than 0.15 wt.%, corresponding to
oxygen fugacities below the NNO buffer. In contrast, the SO3 contents of Baogutu apatite
range from less than 0.1 wt.% to much higher than 0.2 wt.%, corresponding to varied
oxygen fugacities, ranging from below the NNO buffer to close to the NNO +1. HDP =
hornblende diorite porphyry; GDP = Granodiorite porphyry; D = diorite.
Modified after Cao et al. (2014) and Smith et al. (2012).
of mechanisms. The addition of subduction released oxidizing compo-
nents to the mantle wedge or directly to arc magmas is proposed as
the most straightforward way, e.g., water (Kelley and Cottrell, 2009),
oxidizing fluids and/or melts (Brandon and Draper, 1996), fluids with
oxidizing components, e.g., hematite, sulfate (X.M. Sun et al., 2007),
slab melts with high Fe3+/Fe2+ratios (Mungall, 2002), as well as other
oxidized components, e.g., carbonates, or other oxidized sediments.
Arc magmas may also get oxidized during their evolution and ascent
due to the following mechanisms (Ballhaus, 1993; Lee et al., 2005,
2010): (1) Changing oxygen buffers from graphite CO2 (CCO) equilibria
in the mantle source to Fe3 +–Fe2+ equilibria after graphite has been
eliminated by partial melting (Ballhaus, 1993); (2) Fractional crystalli-
zation of olivine and other minerals that favors ferrous iron over ferric
iron (Carmichael, 1991); (3) Assimilation of oxidizing country rocks
(Lee et al., 2005); (4) Degassing of reduced volatile species (e.g., H2,
H2S and CH4) (Ballhaus, 1993; Lee et al., 2005); (5) Changing pH
(e.g., lowering pH in a sulfate–sulfide system) (Sun et al., 2013a,b);
(6) Magma recharging which preferentially enriches ferric Fe (Lee
et al., in press).
There are also several mechanisms that, in principle, may lower the
oxygen fugacity of magmas: (1) Addition of reducing sediments from
plate subduction (Takagi, 2004); (2) Assimilation of reducing country
rocks (Ishihara and Matsuhisa, 1999; Smith et al., 2012); (3) Degassing
of oxidized volatile species (i.e. CO2, SO3); (4) Addition of subduction re-
leased reducing fluids (Song et al., 2009); and (5) Fractional crystalliza-
tion of magnetite and even hematite (Liang et al., 2009; Sun et al.,
2004a, 2013a,b). As discussed previously (Section 3.2.2), the magnetite
crystallization reduces the oxygen fugacity only in magmatic systems
(reactions (13) and (14)), and may only lower the oxygen fugacity to
the FMQ oxygen buffer. Here we discuss two reduced porphyry deposits
in detail.
4.1.1. Evidence for reduced magmas of Catface porphyry deposit
Catface is the largest reduced porphyry Cu deposit so far reported,
emplaced at 40.4–41 Ma, with an indicated reserve of 56.9 Mt @ 0.4%
Cu and an additional inferred resource of 262.4 million tons @ 0.38%
Cu. Three potential mechanisms for the formation of Catface reducing
magmas had been discussed before degassing was assigned as the caus-
ative process: (1) upwelling of the reducing asthenospheric mantle in-
duced by the opening of a slab window during ridge subduction,
(2) evolvement of subducted reducing sediments, and (3) assimilation
of reduced sediments during magma emplacement (Smith et al., 2012).
Previous studies suggested that a slab window introduces hot, up-
welling asthenospheric mantle in the subduction zone environment,
forming non-arc-like alkalic and adakitic magmatism in the volcanic
arc (Abratis and Worner, 2001; Groome and Thorkelson, 2009; H. Li
et al., 2011, 2012; Kinoshita, 1997). The Kula–Farallon ridge in the
northeastern Pacific began descending under the North American conti-
nent in Alaska in the Late Cretaceous (Madsen et al., 2006; Scharman
et al., 2012), and then between 62 and 11 Ma migrated southward
(Cole and Stewart, 2009; Cole et al., 2006; Liu et al., 2008), forming a
semi-continuous forearc magmatic belt from Alaska to Oregon
(Madsen et al., 2006). Ridge subduction forms oxidized adakites by
slab melting (Defant and Drummond, 1990; Ling et al., 2009, 2013),
followed by reduced A-type granites (Abratis and Worner, 2001; H. Li
et al., 2012; Thorkelson and Breitsprecher, 2005; Yogodzinski et al.,
1994). Interestingly, the Catface porphyry deposit is closely associated
with Mt Washington, which is an adakite (Smith et al., 2012) and seem-
ingly would support the slab window model. Nevertheless, adakites
formed by slab melting have much higher initial Cu contents than
mantle-derived melts, and thus are favorable for porphyry mineraliza-
tion (Sun et al., 2010, 2011), suggesting that the reduced Catface por-
phyry could be a country rock hosting the ore deposit, rather than the
causative porphyry.
Subduction of reducing sediments also reduces the oxygen fugacity of
arc magmas, as seen in the Japan arc (Takagi, 2004). Carbon rich sedi-
ments in the descending plate react with H2O to produce CH4 and CO2
(Ballhaus, 1993; Takagi, 2004), or directly releases CH4 by devolatilization
(Song et al., 2009). This process, however, was excluded from further
consideration based on the low 87Sr/86Sr of Catface (Smith et al.,
2012). Methane, however, may decouple from Sr, such that Sr isotopes
cannot give a conclusive answer. Nevertheless, the oceanic plate
subducting underneath Japan is Cretaceous in age, which has experi-
enced eight Ocean Anoxic Events (Jenkyns, 2010), and thus contains
abundant organic rich sediments. In contrast, the oceanic plates
subducting underneath the western North American continent are
younger and have experienced only one Ocean Anoxic Event. Moreover,
ocean ridges are young and generally sediment-poor. Therefore, sub-
duction of reducing sediments is not a plausible explanation for the
low fO2 shown by the Catface porphyry.
The third mechanism proposed for the reduced condition of the
Catface porphyry was by assimilation of reduced sediments. The Catface
porphyry may have ascended through and interacted with graphite-rich
reducing country rock known to exist in the region (Smith et al., 2012).
The reduction of ferric Fe through reaction with reducing materials,
e.g., graphite, in sediments was proposed as a potential factor responsi-
ble for the low fO2 of the parental Catface magma. This mechanism was
excluded based on Sr isotopes (see details below) (Smith et al., 2012).
The authors then proposed that the reduced Catface porphyry was
due to degassing of SO2 from the magma. This argument is based on
the low S content in the rock's apatite and a recent work by Kelley
and Cottrell (2012), which proposed that fractional crystallization
coupled with degassing of S in a sub volcanic arc magma chamber can
result in a reduction of N 2 log fO2 units in the magma. This calculated re-
duction was based on the rock's ferric iron content and S in melt inclu-
sions, and would hold true for magmas varying in composition from
basaltic andesite to dacite (Kelley and Cottrell, 2012). Degassing of
SO2 indeed has a significant influence on the oxygen fugacity in volcanic
systems. It is, however, not likely to be a major process in plutons, which
should experience much less degassing.
Moreover, apatite from the Catface has a homogenous S content
throughout the crystal (Smith et al., 2012), which argues against
major degassing induced S loss during magma evolution. Experiments
on felsic liquids showed that the SO3 content in apatite increase with in-
creasing fO2 from 0.04 wt.% at the FMQ buffer, up to N1.0 wt.% at the HM
buffer (Peng et al., 1997). As pointed out by Smith et al. (2012), apatite
 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131
crystallizes below 950 °C in silicic calc-alkaline magmas (Green and
Watson, 1982). If the magma at Catface was reduced during degassing
of SO3, there should be compositional zonation in the apatite, which is
not the case (Fig. 20) (Smith et al., 2012).
4.1.2. Evidence for reduced magma in the Baogutu porphyry deposit
Baogutu is located in West Junggar, Central Asian Orogenic Belt, and
is the second largest reduced porphyry Cu deposit so far reported,
with controlled reserves of 0.63 Mt Cu @ 0.28 wt.%, 14 t Au @
0.1 ppm, 1.8 × 104 t Mo @ 0.011 wt.% and 390 t Ag @ 1.8 ppm (Cao
et al., 2014). It contains native antimony (An and Zhu, 2010), abundant
hypogene pyrrhotite, and methane-rich fluid inclusions. The low apatite
SO3 content, whole rock Fe2O3/FeO, and fluid compositions indicate a
low fO2 of ~ NNO for the magma and NNO–NNO − 2 for associated
hydrothermal fluid (Cao et al., 2014; Shen et al., 2010b).
Based on H–O and sulfide S–Pb isotope data, it has been argued that
the methane-rich ore-forming fluids were derived from a deep mantle
source with little contamination from penetrated sediments (Cao
et al., 2014). The assimilation model, however, does not contradict
with a deep mantle source for the S, Pb, nor Cu. In fact, most Cu should
have come from slab melts (Sun et al., 2011, 2012b), as also should have
come the S and Pb, which are present in abundances similar to mantle
derived magmas. The H isotopes of fluid inclusions from Baogutu have
very low δD values (Shen et al., 2012; Zhang et al., 2010), which are
much lower than for either magmatic fluids or metamorphic fluids
(Fig. 21). This was interpreted as the main evidence for degassing
(Cao et al., 2014). Degassing, however, should result in heavier hydro-
gen and oxygen isotopes in the residual magmas. The authors used pub-
lished heavy H values from circum-Pacific volcanic gases (Giggenbach,
1992b) to argue that degassing should leave behind fluids with even
lighter H than contained in the magmatic and metamorphic fluids
(Cao et al., 2014). The heavy H of circum-Pacific volcanic gases, howev-
er, was originally explained as having arisen from the addition of seawa-
ter to the gases (Giggenbach, 1992a). Basic principles of isotope
geochemistry dictate instead that in degassing, i.e., evaporating, the re-
maining liquid becomes isotopically heavier in H and O. In addition,
Fig. 21. δD versus δ18O diagram and calculated isotopic composition of waters in hydro-
thermal fluids derived from measured isotopic composition of quartz and its fluid inclu-
sion for the Baogutu deposit from Cao et al. (2014). Reference lines and boxes are as
follow: meteoric water line (Craig, 1961), felsic magmatic water (Taylor, 1992), residual
water in intrusion after degassing and crystallization (Taylor, 1974), low-salinity vapor
discharges from high-temperature volcanic fumaroles (Giggenbach, 1992b), primary
magmatic water area, metamorphic water area and multiple formation water area
(Hoefs, 2004). H–O isotopic data are from (Zhang et al., 2010) and (Shen et al., 2012).
Low-salinity vapor shows strong seawater signals, which cannot represent “degassing”
fluids.
115
degassing cannot explain the decoupling between δD and O isotope
compositions. Moreover, the degassing of porphyries should be much
less pronounced than the degassing of volcanic rocks.
The systematically lighter H coupled with a slightly lighter O can
best be explained by the addition of meteoritic water. Baogutu is located
in the center of the Eurasian continent. Meteoritic water there should be
very light in H and O isotope composition. Addition of such water
should dramatically reduce the δD of the magma with a much lesser
effect on O because magmas have low hydrogen contents and abundant
oxygen contents.
4.2. Source of copper
For oxidized magmas, as discussed in Section 3, excess sulfur is pre-
cipitated in the form of sulfate, leaving behind less residual sulfide, such
that Cu, Au and other chalcophile elements become enriched in magmas
(Lee et al., 2012; Sun et al., 2012a, 2013a,b). In contrast, reduced
magmas usually retain residual sulfides, such that they have low prima-
ry Cu contents (Fig. 3) (Lee et al., 2012). Then, how do reduced magmas
get enriched in Cu?
As pointed out by previous authors, porphyry deposits associated
with reduced magmas are generally small (Cao et al., 2014). This was at-
tributed to the originally low Cu and Au contents of the magmas, less
magmatic fluids released due to deep emplacement, or tectonic settings
that are not favorable for porphyry mineralization (Cao et al., 2014).
They also argued that significantly lower sulfur solubility in reduced
melt (Jugo, 2009; Jugo et al., 2005, 2010) keeps S2− as the dominant
sulfur species, which potentially isolates sulfides from the magma dur-
ing its migration to the site of final emplacement, thus producing only
relatively small chalcophile endowments (Cao et al., 2014). None of
these arguments are convincing to us. First, lower Cu and Au contents
would first result in lower grade, not necessarily smaller tonnages.
The grades of porphyry Cu and Au deposits associated with reduced
magmas are comparable to, if not higher than, those associated with
oxidized magmas (Cooke et al., 2005; Rowins, 2000). Second, there is
no systematic difference in terms of emplacement depths and tectonic
settings between reduced and oxidized porphyry deposits. More impor-
tantly, compared to oxidized magmas, reduced magmas indeed have
lower sulfur contents with S2− occurring as the dominant sulfur species
(Jugo et al., 2010), but this does not necessarily mean higher S2− in re-
duced magmas as claimed by Cao et al. (2014). Given that the solubility
of sulfide is independent of oxygen fugacity, but increases with decreas-
ing pressure under reducing conditions (Mavrogenes and O'Neill,
1999), the high proportions of S2− cannot “isolate sulfides from the
magma during migration” as proposed.
Based on a synthesis of theoretical, experimental, and field data, it
has been proposed that Cu and Au can be transported via the vapor
phase to distal sites as far as several kilometers away from the causative
porphyry due to fluid boiling or immiscible phase separation. Conse-
quently, the source porphyry becomes a low-grade sub-economic Cu–
Au core or failed porphyry Cu system (Rowins, 2000), which is more
or less similar to an epithermal ore system. Experiments find that the
main transporting agents of Cu at the porphyry level are brines and
that models based on transporting copper in the vapor phase are incor-
rect (Lerchbaumer and Audetat, 2012). It is further demonstrated, using
experimental studies, that brine–vapor separation in porphyry deposits
does not cause selective Cu transfer to the vapor, but is more likely to
destabilize Cu complexes and promote copper ore deposition during de-
compression and unmixing of the two fluid phases. In contrast, Au may
be selectively transferred into the vapor phase, allowing its transport
from the deeper porphyry copper deposits to form shallower
epithermal gold deposits (Seo and Heinrich, 2013). This explains the
Au-rich capping feature of many reduced porphyry deposits. Mean-
while, Cu may be transported to distal sites through normal fluids.
Such a reduced porphyry Cu–Au mineralization model does not contra-
dict the current understanding of porphyry Cu–Au formation. In fact,
116 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131
the recognition of reduced porphyry Cu–Au systems encourages a
search for distal sites that are favorable for focusing and precipitating
Au and Cu-rich vapors (Rowins, 2000). This implies that such porphyry
deposits themselves are not genetically related to reduced magmas,
i.e., they are not the causative magma, but the host rock.
4.3. Formation of reduced porphyry deposits
Porphyry deposits related to reduced magmas have two other dis-
tinct characteristics. They are associated with carbonic-rich ore forming
fluids (Cao et al., 2014; Rowins, 2000; Smith et al., 2012), and multiple
intrusive events (Cao et al., 2014; Rowins, 2000; Smith et al., 2012). In
addition to the transportation of Cu and Au from the causal porphyry
to distal sites of deposition (Rowins, 2000), we propose two other
ways that may form reduced porphyry deposits: (1) by reduction of
oxidized magmas during their ascent in the crust, and (2) by using re-
duced magmatic rocks that are present only as country rocks to host
ore deposits originating from underlying oxidized magmas.
4.3.1. The formation of the Catface porphyry deposit
As discussed above (Section 3.2.2), assimilation of reduced sedi-
ments may have reduced the oxygen fugacity of the Catface porphyry,
a possibility that was excluded based on Sr isotopes. The 87Sr/86Sr
ratio of the Catface intrusions is 0.704, whereas those of the graphite-
rich metasediments of the Pacific Rim terrane range from 0.706 to
0.708 (Smith et al., 2012). We find such small differences in Sr isotopes
to be negligible, and thus do not argue strongly against the assimilation
model. Graphite and especially methane need not be considered
coupled with silicate minerals, such that the reducing action of the
graphite and methane is not proportionally related to the assimilation
of silicates nor sulfides, thereby decoupling them from the Sr, Pb, and
S isotopes. Relationship between Sr and C aside, the amount of C needed
is very small. The total iron (expressed as Fe2O3) content ranges from
2.25 wt.% to 5.53 wt.% for the Catface porphyry. One carbon atom re-
duces 4 ferric Fe atoms (Eq. (28)), assuming all the Fe in the parental
Catface magmas was ferric Fe, and all the ferric Fe was reduced by
graphite, then only 0.04 to 0.1 wt.% of graphite is required, which may
only have had a limited influence on Sr isotopes. More interestingly,
the Catface intrusions have fO2 values nearly identical to the C–CO–
CO2 buffer at similar pressure and temperature conditions (Smith
et al., 2012), which would support the assimilation of graphite-rich sed-
iments.
C þ 2Fe2 O3 ¼ 4FeO þ CO2 ð28Þ
Reduced sediments usually also contain methane (Cao et al., 2014),
which is a more efficient reductant, i.e., 1 methane molecule reduces 8
ferric Fe atoms (Eq. (29)), such that only ~0.02 to 0.05 wt.% of methane
is needed. Therefore, the parental Catface magmas may have acquired a
low fO2 during their ascent through the crust. The homogenous SO3 in
apatite may simply be due to an early reduction of the magmas, before
apatite crystallization.
CH4 þ 4Fe2 O3 ¼ 8FeO þ CO2 þ 2H2 O ð29Þ
Considering that the Catface porphyry is not adakitic, it may well be
simply the country rock that hosts the deposit. The Catface porphyry
deposit is closely associated with a nearby pluton on Mt Washington
(35–41 Ma), which is an adakite (Smith et al., 2012). The mineralization
(40.9 Ma) and the emplacement age of the Catface porphyry (40.4–
41 Ma) (Smith et al., 2012) are both within the age range of the Mt
Washington adakite. Adakites along the eastern Pacific rim are mostly
formed by slab melting (Liu et al., 2010; Sun et al., 2012a,b), which are
likely to have high initial Cu contents, and are thus favorable for porphy-
ry mineralization (Sun et al., 2010, 2011). In contrast, the Cu contents of
the asthenosphere (~ 30 ppm) (McDonough and Sun, 1995) and the
continental crust (~27 ppm) (Rudnick and Gao, 2003) are much lower
than MORB (~ 100 ppm) (Sun et al., 2003b), such that melt derived
from them should have much lower Cu contents and be less favorable
for porphyry Cu mineralization. Therefore, the reduced Catface porphy-
ry is likely to be a country rock that only hosts the deposit.
Based on the above discussion, we propose the following model for
the formation of the Catface porphyry. Intrusions in the Vancouver
Island range in age from 51 to 35.5 Ma (Madsen et al., 2006), spanning
the time during which the Kula–Farallon ridge collided with the conti-
nent. Accompanying the oblique subduction of the ridge (Madsen
et al., 2006), its two limbs separated, with a slab window opened in be-
tween. The first limb formed early through partial melting of the hot
subducting plate. The resulting adakites may then have been reduced
through reaction with the thick (maximum thickness of 4 km)
carbon-rich Cretaceous Nanaimo Group sediments (Madsen et al.,
2006) as they migrated upward. Consequently, sulfate is reduced to
sulfide, leaving behind Cu-rich sulfide accumulations in the lower
crust. This is followed by emplacement of the Catface porphyry at 41–
40.4 Ma (Smith et al., 2012), which took place at a time that the slab
window was open. The mantle derived parent magmas of the Catface
porphyry are expected to have been more reduced (near the FMQ
oxygen fugacity buffer) and drier than the adakite, and to have a
lower initial Cu contents. Nevertheless, it became wetter and even
more reduced (ΔFMQ − 0.3 to − 3) with a higher Cu content after
assimilating the Cu-rich sulfide accumulations in the lower crust. Mean-
while, ridge subduction induced compression and consequent uplift
and erosion occurred, which favored the exposure of the porphyry de-
posit. Oxidized Mt Washington adakite was emplaced at 41–35.3 Ma
during the subduction of the west limb of the ridge, bringing more ore
forming fluids into the Catface porphyry. We infer that large propor-
tions of these adakites are still buried due to the dramatically lessened
compression, uplifting and erosion following ridge subduction.
4.3.2. The formation of the Baogutu porphyry deposit
Based on previously obtained fluid inclusion H–O isotope data and
sulfide S–Pb isotope data, it was proposed that the methane-rich ore
forming fluids in the Baogutu porphyry deposit were derived from a
deep mantle source with little contamination from sedimentary compo-
nents (Cao et al., 2014). As discussed above (Section 4.1.2, Fig. 21), the
authors' understanding about H–O isotopes is in error, whereas only
small amount of C is enough to lower the oxygen fugacity of the Baogutu
low Fe magmas. Therefore, S–Pb isotopes cannot place any decisive con-
straints on the role of assimilation in forming the deposit. As pointed out
by the authors, detailed studies are needed to clarify the origin of the
CH4.
More importantly, there are three intrusive phases at Baogutu,
which from old to young are: (1) the main diorite phase, (2) dikes of di-
orite porphyry and granodiorite porphyry intruding the early diorite
stock, and (3) dikes of hornblende diorite porphyry intruding all the
three phases. All the samples with the exception of two were collected
from the diorite, which are not porphyry at all. The reduced diorite
magma may have no relation with the porphyry mineralization, except
to act as a host rock.
We propose that the reduced features of the Baogutu porphyry de-
posit are secondary and occurred during emplacement, thus having no
major influence on the mineralization process. A similar model has
been proposed based on geochemical and mineralogical studies by
Shen and Pan (2013), in which mineral composition data suggest that
the primary magma of the Baogutu porphyry deposit is oxidized. The
heterogeneous and reduced characteristics of the deposit are attributed
to significant country-rock contamination after emplacement (Shen
and Pan, 2013) in an arc setting (Shen et al., 2013a,b).
Similar to Catface, there are also adakites in Baogutu. The Baogutu
adakites have been attributed to the mixing of ~ 95% slab melt with
~ 5% sediment-derived melt in the Late Carboniferous close to a
subducting spreading ridge (Tang et al., 2010). Therefore, more work
 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131
on porphyry dykes are needed to clarify the origin of the Baogutu por-
phyry deposit.
4.4. Summary
Reduced magmas are not favorable for porphyry mineralization. The
reduced porphyry deposits so far reported are either simply distal host
rocks located as far as several kilometers away from or above the caus-
ative porphyry buried underneath, or originally oxidized magmas that
were reduced through assimilation of reducing components. Degassing
of SO2 is not likely to be a main process for forming porphyry deposits
because it cannot explain the features of reduced porphyries. Careful
studies are needed to identify the causative porphyries. Oxidized
adakitic (slab melts) rocks are overwhelmingly the most favorable can-
didates for porphyry mineralizations.
5. Discussion
5.1. The oxygen fugacities at convergent margins
The oxygen fugacity of the mantle and volcanic arc has been under
study for a long time (Ballhaus, 1993; Carmichael, 1991; Cottrell and
Kelley, 2013; Kelley and Cottrell, 2009; Lee et al., 2005, 2010;
Parkinson and Arculus, 1999). The consensus is that the oxygen fugacity
of arc magmas is systematically higher than that of MORB (Fig. 16)
(Carmichael, 1991; Kelley and Cottrell, 2009; Parkinson and Arculus,
1999; Sun et al., 2012a, 2013a,b). Nevertheless, it is still hotly debated
as regards to how arc magmas get oxidized. As mentioned in
Section 3, a variety of mechanisms have been proposed.
The most straightforward way to elevate the oxygen fugacity of arc
magmas is by the addition of oxidizing components to the mantle
wedge or directly to the magmas. Water is the most abundant volatile
component released during plate subduction. It has been proposed
that H2O reacts with FeO, forming Fe2O3 with the release of H2
(Eq. (30)) (Brandon and Draper, 1996; Kelley and Cottrell, 2009).
Most of the ferric Fe will be transferred into the melt because ferric Fe
is more incompatible than ferrous Fe (Lee et al., in press). This reaction,
however, is not controlled by water. Instead, it is controlled by ferrous
Fe, which is more stable under high pressure. Recent experiments
show that water and H2 can coexist as two immiscible phases. This
immiscibility implies that water is stable in the mantle under high
pressure (Bali et al., 2013).
More accurately, the ferrous Fe in fluids reacts with water, releasing
H2 and H+ (Eq. (31)). This is supported by the abundance of oxidized
components, e.g. magnetite–hematite and sulfates, found in the subduc-
tion released fluids of ultrahigh pressure quartz veins, which may ele-
vate the oxygen fugacity of the mantle wedge (X.M. Sun et al., 2007).
It has also been proposed that slab melts are the most efficient way to
transfer high Fe3+/Fe2+ ratios responsible for high oxygen fugacity in
adakites (Mungall, 2002) and arc magmas (Brandon and Draper, 1996).
H2 O þ 2FeO ¼ Fe2 O3 þ H2
2þ þ
3H2 O þ 2Fe ¼ Fe2 O3 þ H2 þ 4H
The addition of other oxidized materials, e.g., Fe3+, C4+, and S6 +,
from subducted sediments and oceanic crust to the mantle wedge
may elevate the redox states of the mantle as well (Fig. 18) (Evans
et al., 2012). Arc magmas may also get oxidized during their evolution
and ascent by processes accompanying melting, crystallization, assimi-
lation, degassing, etc (Ballhaus, 1993; Lee et al., 2005, 2010). For exam-
ple, graphite and diamond are stable in the deep mantle. During mantle
melting, CO2 is incompatible whereas C is compatible, and graphite may
be consumed through oxidation melting (Stagno et al., 2013). Most of
the C in magma occurs as CO2, therefore the oxygen buffer changes
117
from graphite–CO2 (CCO) equilibria in the mantle source to Fe3 +–
Fe2+ equilibria as the magma ascends (Ballhaus, 1993). Consistently,
it becomes more oxidizing with decreasing depths and pressures
(Stagno and Frost, 2010; Stagno et al., 2013). Moreover, most mantle
minerals, such as olivine, favor ferrous Fe over ferric Fe, and fractional
crystallization of these minerals elevates the Fe3+/Fe2+ (Carmichael,
1991). Given that ferric Fe is highly incompatible, magma recharging
will further enrich the ferric Fe (Lee et al., in press), resulting in higher
oxygen fugacities. In addition, assimilation of oxidizing country rocks
(Lee et al., 2005), degassing of reduced volatile species (e.g., H2, H2S
and CH4) (Ballhaus, 1993; Lee et al., 2005) and lowering of pH values
in a sulfate–sulfide dominated system (Sun et al., 2013a,b) may also el-
evate the oxygen fugacity of the magmas. Based on similar Zn/FeT ratios
of mantle peridotite and primitive arc magmas, it has been argued that
primary arc magmas are not necessarily oxidized (Lee et al., 2010). In-
creasing Zn/FeT ratios with decreasing MgO content argues that the
high oxygen fugacity of arc magmas is acquired through magma evolu-
tion (Lee et al., 2010), indicating that continuing chemical evolution
during magma transport and emplacement may have major effects on
the oxidized characteristics of arc magmas. This may equally explain
the diversity in oxygen fugacities at convergent margins. Nevertheless,
high oxygen fugacities developed during magma evolution may provide
little or no contribution to eliminating residual sulfides, and thus little
contribution to porphyry mineralization. This decoupling may partially
explain why most arc magmas are highly oxidized, whereas only a
small portion of them form porphyry Cu deposits.
5.2. The difference between porphyry and epithermal in terms of oxygen
fugacity
Most Cu porphyry deposits form at depths of 2–4 km, and are usually
associated with epithermal deposits at shallow depths if not removed
by erosion (Figs. 22d, 23a, b) (Cooke et al., 2011; Hedenquist et al.,
1998; Heinrich, 2005; Heinrich et al., 2004; Hollings et al., 2005;
Sillitoe, 2010). This seemingly implies that porphyry and epithermal de-
posits are closely related. Many epithermal deposits, however, are not
linked to porphyry deposits. For example, epithermal deposits formed
in the mid-ocean ridge and backarc basins usually do not have any asso-
ciated porphyry deposit. This is probably mainly because the crust in
backarc basins is too thin. Regardless, the oxygen fugacities of
epithermal deposits have a much larger ranges than porphyry deposits.
5.2.1. Magnetite crisis
The magnetite crisis (Jenner et al., 2010) refers to the dramatic de-
creases in Cu and Au during magnetite crystallization in arc volcanic
rocks (Sun et al., 2004a), which is a common phenomenon (Moss
et al., 2001; Sun et al., 2011; Togashi and Terashima, 1997). This magne-
tite crisis is taken as a main process that leads to the formation of ore-
forming fluids, responsible for the Au and Cu mineralization of both
epithermal and porphyry deposits (Liang et al., 2009; Sun et al., 2004a,
2013a,b) (see also Section 3): Sulfate is reduced to sulfide during mag-
netite crystallization, forming hydrosulfide complexes, which scavenge
ð30Þ
chalcophile elements into fluids and subsequently transport the metals
to favorable places for forming deposits (Sun et al., 2004a).
ð31Þ This mineralization model has been challenged by some later
studies. Although using the same set of samples (Jenner et al., 2012),
and essentially repeating the results of the previous study (Sun et al.,
2004a), it was proposed that magnetite fractionation triggers sulfide
saturation (Jenner et al., 2010). This conclusion was drawn based main-
ly on the behavior of Se, which was assumed as a proxy that follows S
closely during magmatic evolution except that it is not lost during
low-pressure (near sea-floor) degassing (Jenner et al., 2010). Fluid ex-
traction, however, is different from degassing, and thus Se provides no
constraints on the process. In fact, as shown in the supplementary infor-
mation, sulfide is undersaturated in Manus glasses (Fig. 24) (Sun et al.,
2004a).
118 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131

Fig. 22. Different models for the mineralization of porphyry deposits. After (A) Lee (2014): Mantle-derived magmas (red) intrude into the cold upper plate (black) of subduction zones,
generating crystallizing magma chambers. Thick continental arcs are more favorable for porphyry mineralization because of accumulation of copper-rich sulfide cumulates; (B) after
Wilkinson (2013), which also proposes that sulfide saturation and accumulation are very important for the formation of porphyry Cu deposits; (C) after Richards (2011b), illustrating
porphyry and epithermal mineralizations in arc and postcollisional settings; (D) after Richards (2013), highlighting features or processes that may result in supercharging of these systems
to form giant deposits.
 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131 119

Fig. 22 (continued).

There are indeed sulfide inclusions in mineral phenocryst from
Manus glasses (Fig. 25) (Sun et al., 2004a). The sulfide phase contains
high Au and Ag contents in addition to Cu in sulfides, but no other
chalcophile elements, such as Ni, Re, and Pt (Jenner et al., 2010). This
was used to argue that the sulfide phase is crystalline rather than an im-
miscible sulfide melt (Jenner et al., 2010).
Crystallization of sulfide cannot explain this phenomenon, because
Ni and Pt are even more chalcophile than Cu, with partition coefficients
between sulfide and silicate melts of several hundreds and more than
20 thousand, respectively (Table 2). We propose that these sulfides
formed directly from magmatic fluids. As shown in Fig. 25, sulfides in
phenocrysts are associated with fluid inclusions (Sun et al., 2004a).
It is very likely that the preferential enrichments of Cu and Au over
Ni and Pt are controlled by sulfide complexes in fluid. This may ex-
plain why there is no Ni and Pt in most porphyry and epithermal
deposits.
The lack of Re in these sulfides can be plausibly interpreted by the
high oxygen fugacity, under which most of the Re is Re6+, and thus be-
haves as lithophile rather than chalcophile elements. As shown in
Fig. 26, in contrast to Cu and Au (Sun et al., 2004a) and also V, Co, Pt,
and Se (Jenner et al., 2010), Re concentrations in Manus glasses keep in-
creasing when magnetite starts to crystallize, and then decrease gradu-
ally (Sun et al., 2003a). This can best be explained by the reduction of
Re6 + to Re4 + during magnetite crystallization. Correspondingly, Re
changes from incompatible (Sun et al., 2003a,b,c), to compatible
(Mallmann and O'Neill, 2007).
120 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131

Fig. 23. Cartoons illustrate the relationship between some epithermal deposits with porphyry deposits underneath. Modified after: (A) Hedenquist and Lowenstern (1994) and
(B) Heinrich (2005). Note, not all epithermal deposits are associated with porphyry deposits.

5.2.2. Oxygen fugacity and open systems
In contrast to the dramatically elevated oxygen fugacities during
magnetite crisis, the oxygen fugacity of the Manus magmas did not
change much, or even lessened slightly (Jenner et al., 2010) during the
crystallization of magnetite and sulfate reduction (Sun et al., 2004a).
This can be interpreted as a magmatic process, i.e., the magnetite crys-
tallization and sulfate reduction recorded in glasses occurred during
magma evolution. As mentioned in Section 3.2.2, magnetite crystalliza-
tion in magmas reduces sulfate without changing the pH values. The
solubility of sulfides in fluids is very high, with partition coefficients
of ~ 500 (Keppler, 2010). Sulfides formed through sulfate reduction
are released into magmatic fluids, where they scavenge chalcophile
elements (Jenner et al., 2010; Sun et al., 2004a). Meanwhile, the
reactions of Eqs. (16) and (17) are driven to the right, promoting
sulfate reduction.
Hydrothermal magnetite and even hematite may also form in fluids
released from arc volcanic magmas, e.g., Manus glasses, releasing H+.
Nevertheless, volcanic magma systems are much more open than por-
phyry systems, so that the formation of hydrothermal iron oxides does
not necessarily affect the oxygen fugacity of the arc magmas.
 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131
Fig. 24. Sulfide contents in Manus submarine volcanic glasses, showing that sulfide is far
below saturation (after Sun et al., 2004a). Therefore, sulfide segregation induced by sulfide
saturation as proposed by previous authors (Jenner et al., 2010) is not a feasible way to ex-
plain the magnetite crisis. Filled and open circles represent volcanic glasses analyzed by
different authors, filled triangles represent melt inclusions.
Given that volcanic systems are far more open, the initial Cu, Au con-
tents are not of critical importance to porphyry mineralization. Metals
can be leached out as far as there is enough water circulation. Therefore,
it does not require very high oxygen fugacities to eliminate residual
Fig. 25. Images of sulfide inclusion in an olivine phenocryst of Manus glass under
(A) reflected light and (B) and transparent light. Only one big sulfide globule is clearly
identified under reflected light, which seemingly indicates sulfide saturation. This grain
is actually associated with fluid inclusions as shown under transparent light. In addition,
there are several sulfide grains, which are all associated with fluid inclusions (Sun et al.,
2004a). The unique composition of sulfides in Manus glasses (low Ni, Pt, etc.) may be plau-
sibly interpreted by sulfides crystallized from magmatic fluids.
121
sulfides. This explains why epithermal deposits are distributed in a vari-
ety of tectonic settings, ranging from mid-ocean ridges and backarc ba-
sins to arcs.
5.3. Adakite, slab melting, ridge subduction and porphyry Cu deposits
Adakite was initially named for rocks formed through partial melt-
ing of subducted young oceanic crust (b25 Ma, represented by mid-
ocean ridge basalt, MORB) (Defant and Drummond, 1990; Kay, 1978).
In contrast to most other rock types, adakite is defined by geochemical
compositions (e.g., SiO2 ≥ 56 wt.%, Al2O3 ≥ 15 wt.%, Y ≤ 18 ppm,
Yb ≤ 1.9 ppm and Sr ≥ 400 ppm) without detailed petrographic con-
straints. Therefore, (1) both eruptive and intrusive rocks can be classi-
fied as adakites; and (2) adakites may be produced simply by partial
melting of mafic rocks in the presence of garnet and absence of plagio-
clase. Different mechanisms have been proposed to produce adakites,
e.g., partial melting of the lower continental crust (Chung et al., 2003;
Gao et al., 2004; Guo et al., 2006; Xu et al., 2002, 2006; Zhang et al.,
2001b) or underplated new crust (Hou et al., 2009; Martin, 1999), or
by fractional crystallization of normal arc magmas (Castillo, 2006;
Macpherson et al., 2006; Richards and Kerrich, 2007). Given that the
oceanic crust is very different from continental crust, slab melts can be
distinguished from lower continental crust melts using geochemical
criteria (Ling et al., 2011; Liu et al., 2010; Sun et al., 2012a).
5.3.1. Adakite and porphyry Cu deposits
Most porphyry Cu deposits are associated with adakites (Oyarzun
et al., 2001; Sajona and Maury, 1998; Sun et al., 2011, 2012a,b, 2013a,
b; Thieblemont et al., 1997), but the association is not true vice versa.
Many adakites, e.g., those from the Dabie Mountains, are not mineral-
ized at all (Huang et al., 2008; Ling et al., 2013; Liu et al., 2012; Wang
et al., 2007a). Partial melting of thickened eclogitic lower continental
crust (Wang et al., 2006a,b, 2007a,b; Zhang et al., 2001a) and fractional
crystallization of garnet (Macpherson et al., 2006) or amphibole
(Richards and Kerrich, 2007) may also form high Sr/Y magmas. The
lower continental crust melts have much lower Cu abundance and
lower oxygen fugacity than subducting slabs, such that they are not fa-
vorable for forming porphyry Cu deposits. Fractional crystallization of
garnet and/or amphibole plays no positive role in Cu mineralization, ei-
ther (Sun et al., 2011, 2012a).
Adakite formation through slab melting, on the other hand, does
favor porphyry Cu mineralization (Mungall, 2002; Sajona and Maury,
1998; Sun et al., 2011, 2012a; Thieblemont et al., 1997). Several differ-
ent explanations for the fertility of adakitic slab melts have been
proposed:
Oxidized. It has been argued that slab melts might be unusually oxi-
dized and rich in sulfur (Oyarzun et al., 2001), due to high Fe3+ con-
tent from oxidative sea-floor alteration. As a consequence, this
elevated fO2 state causes oxidation of chalcophile metal-bearing sul-
fide phases in the mantle wedge, releasing metals to the silicate melt
phase (Mungall, 2002). However, although oxidation is crucial to
porphyry mineralization, adakites are not systematically more oxi-
dized than normal arc magmas (Ballhaus, 1993; X.M. Sun et al.,
2007; Sun et al., 2013a,b). Normal arc melts are not systematically
more enriched in Cu than MORB, either (Lee et al., 2012).
Water: It has been proposed that slab melts might be unusually
water rich (Sajona and Maury, 1998). High water contents in
magmas may suppress the crystallization of plagioclase, and pro-
mote the formation of amphibole, resulting in high Sr/Y signatures
(Richards, 2011a, 2012). The problem with this model is that no
studies have ever demonstrated that adakites are more hydrous
than normal arc rocks. Moreover, the crystallization of amphibole
plays no role in Cu mineralization. Copper is incompatible in most
major silicate minerals, but could be compatible in amphibole, de-
pending on the composition of the magmas and amphibole (Sun
122 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131

Table 2
Summary of sulfide/silicate partition coefficients.

Cu Au Ag Ni Pt Re Mo References

212–278 – – 240–308 – – – Rajamani and Naldrett (1978)

1383 1.5E+4–1.9E+4 – 500–900 – – – Peach et al. (1990)
250–970 – – 540–4400 – – – Gaetani and Grove (1997)
330–1070 7E+3–1.3E+4 300–1680 210–1270 – – 0.20–14.48 Li and Audetat (2012, 2013)
1040–1624 – 853–1528 646–965 – – – Patten et al. (2013)
1050–1850 4.1E+03–1.12E+04 – – 2.41E+05–4.19E+05 361–960 – Mungall and Brenan (2014)

et al., 2012b, 2014a). Therefore, none of the arguments concerning magma in a non-erupting, closed-system pluton where sulfur
water abundance can be plausibly interpreted to explain an associa- might precipitate as hydrothermal sulfides and sulfates instead of
tion between adakites and porphyry deposits. Because of these un- being degassed as SO2 (Oyarzun et al., 2001, 2002). In addition, com-
certainties, it has been asserted that there is no single, obvious pression also results in uplifting and erosions, which are later favor-
reason why slab melts have an unusually high potential to form por- able for the exposure of porphyry deposits. The question is again
phyry deposits (Richards, 2013). why normal arc rocks in compressed environments do not form por-
Felsic: Adakite is formed by partial melting of basaltic rocks, such phyry deposits.
that they should logically be more felsic than peridotite melts High Cu contents. Oceanic crust has a much higher Cu abundance
(Sajona and Maury, 1998). It has been further proposed that adakites (~ 100 ppm) (Sun et al., 2003a,b) than the mantle (30 ppm)
might more readily crystallize as intrusive plutons because of their (McDonough and Sun, 1995) or the continental crust (~ 27 ppm)
viscous felsic nature, leading to the generation of a more efficient (Rudnick and Gao, 2003). It has been proposed that partial melting
crustal magmatic–hydrothermal systems (Sajona and Maury, of the subducted oceanic crust forms adakites with systematically
1998). In fact, adakites associated with porphyry Cu deposits are higher Cu initial contents—favorable for porphyry Cu mineralization
mostly intermediate in composition, not felsic. (Sun et al., 2011, 2012a,b). Previous studies, however, did not quan-
Compression. Adakites are often generated by flat subduction of titatively model the influence of oxygen fugacity, although its posi-
young oceanic crust with associated compressional stress in the tive effect has been emphasized (Sun et al., 2011, 2013a,b).
upper plate. Such an environment should be favorable for trapping
The effects of oxygen fugacity on normal arc magmas have been
nicely modeled (Fig. 3) (Lee et al., 2012). Normal arc rocks form by par-
tial melting of peridotite from the mantle wedge. The primitive mantle
contains ~250 ppm of S (McDonough and Sun, 1995), whereas depleted
mantle peridotite contains ~ 150 ppm of S (O'Neill and Mavrogenes,
2002). Partial melting of mantle peridotite can easily eliminate residual
sulfide even under reducing conditions, e.g., by ~20% partial melting at
ΔFMQ 0 (Fig. 3) (Lee et al., 2012). In contrast, oceanic crust has sulfur
abundances of over 1000 ppm (O'Neill and Mavrogenes, 2002), which
is about 4 times greater than the primitive mantle value (McDonough
and Sun, 1995). As discussed in Section 3, oxygen fugacities higher
than ΔFMQ + 2 are of critical importance to eliminate residual sulfides
during slab melting. However, at oxygen fugacities higher than ΔFMQ
+ 2, ~5–10% of partial melting is enough to eliminate residual sulfide
from the subducted oceanic crust, forming adakitic melts with high Cu
and S contents up to 2000 ppm and percent levels, respectively. Such el-
evated contents in the magma, of course, are consistent with the high
Cu, S contents present in ore bearing porphyries.

5.3.2. Ridge subduction and porphyry Cu deposits

Fig. 26. Diagrams of SiO2 versus Cu and Re. Note, in contrast to Cu, Re keeps increasing
when Cu drops suddenly at the point when magnetite starts to crystallize. Rhenium is
much less chalcophile than Cu under high oxygen fugacities. It is present mainly in the
form of Re6+ and acts as an incompatible element before magnetite crystallization and
was gradually reduced to Re4+ during magnetite crystallization.
Modified after Sun et al. (2003a, 2004a).
More than half of the world porphyry Cu deposits are located along
the western coasts of the North and South American continents com-
prising the eastern Pacific margin. The total resources there are estimat-
ed to be N1.8 billion tons, accounting for about 60% of the world's total
Cu resource estimation (Mutschler et al., 2010). Twenty out of the
world's top 25 giant porphyry Cu deposits are located there. In contrast,
there are essentially no porphyry Cu deposits located along the north-
western Pacific margin, e.g., Japan.
Many large porphyry Cu–Au deposits are connected to subduction of
spreading and aseismic ridges (Fig. 27) (Cooke et al., 2005; Sun et al.,
2010). As discussed above, slab melting is usually involved in creating
magmas with high Cu contents and adequately high oxygen fugacity,
which are the two main controlling factors for porphyry Cu mineraliza-
tion (Section 3). Subduction of young ridges, both spreading and
aseismic, in particular, produces adakites with high oxygen fugacity,
making it the best geological process for porphyry Cu deposits (Sun
et al., 2010, 2013a,b). There are several subducting ridges along the
east Pacific margin, e.g., in Chile and Peru in the South America. These
 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131
Fig. 27. Many large porphyry Cu deposits are closely associated with ridge subduction, because subduction of young ridges is the most favorable geologic process for slab melting in the
Phenozoic, forming highly oxidized melt with high initial Cu contents.
Modified after Sun et al. (2010).
ridges were mostly younger than 25 Ma when they began to subduct,
and are closely associated with large porphyry Cu–Au deposits (Fig. 27).
There are also several ridges (most of which are aseismic, i.e., island
chains) on the western Pacific plate (Fig. 28). Most of these ridges, how-
ever, are older than 100 Ma (W.D. Sun et al., 2007), and are not likely to
form adakites. In addition, the oxygen fugacities in Japan, Izu–Bonin–
Mariana, and other arcs along the northwestern Pacific margins, are sys-
tematically lower than ΔFMQ + 2 (Fig. 16a). For these reasons, we find
it not surprising that no economically viable porphyry deposits associat-
ed with volcanic arcs are known in the northwestern Pacific region.
There are porphyry ore deposits located at the southwestern Pacific
margin, which, however, are much less developed in terms of tonnage
and the number of deposits. It is noteworthy that these deposits are as-
sociated with the closure of backarc basins younger than 25 Ma
(Fig. 29).
Considering the geotherm's concave downward shape of subducting
slabs, ridge subduction is the most favorable tectonic setting for slab
123
melting in the Phanerozoic. Geochemical signatures of ridge subduction
are important exploration targets for large porphyry Cu–Au deposits.
5.4. Alterations
Porphyry deposits have very well developed alteration zones that
typically affect several cubic kilometers of rock (Lowell and Guilbert,
1970; Sillitoe, 2010; Titley, 1981) (Fig. 30), which is of critical impor-
tance to understanding porphyry mineralization processes and improv-
ing their exploration.
Alteration is mainly controlled by pH values of the ore-forming fluids
(Sillitoe, 2010). The amount of H+ released during mineralization
(e.g., Eqs. (15), (16), (18), (19), (22), (23), (25)) together with alkali con-
tents in the porphyry together control advanced argillic lithocap
formation and alteration (Sillitoe, 2010). For example, sericitic and
advanced argillic alteration are much less well developed in porphyry
Cu deposits associated with alkaline than with calc-alkaline intrusions
124 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131

Fig. 28. Distributions of aseismic ridges (island chains) in the Western Pacific. These aseismic ridges are all much older than 25 Ma, such that do not get melted during subduction.
Modified after W.D. Sun et al. (2007).

Fig. 29. Ages of backarc basins in the southwestern Pacific. Subduction of young backarc basin crust forms adakite, which is favorable for porphyry mineralization.
 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131 125

þ þ
(Lang et al., 1995; Sillitoe and Burrows, 2002), reflecting control of the 3KAlSi3 O8 þ2H ¼ KAl2 Si3 AlO10 ðOHÞ2 þ2K þ 6SiO2 ð33Þ
K+/H+ ratio by magma chemistry (Sillitoe, 2010). As summarized recent- Potassium feldspar sericite

ly (Sun et al., 2014b), the main alteration reactions are Eqs. (32)–(37):
þ þ þ
3NaAlSi3 O8 þK þ 2H ¼ KAl2 ½AlSi3 O10 ðOHÞ2 þ6SiO2 þ 3Na ð34Þ
þ Sodiumfeldspar sericite
2KðMg; FeÞ3 AlSi3 O10 ðOHÞ2 þ4H
Biotite
2þ þ þ þ
¼ AlðMg; FeÞ5 AlSi3 O10 ðOHÞ8 þðMg; FeÞ þ 2K þ 3SiO2 ð32Þ 2KAl3 Si3 O10 ðOHÞ2 þ2H þ 3H2 O ¼ 3Al2 Si2 O5 ðOHÞ4 þ2K ð35Þ
chlorite Sericite kaolinite

Fig. 30. Alteration patterns of porphyry deposits. After: (A) Lowell and Guilbert (1970); (B) Sillitoe (2010) and (C), Richards (2011b).
126 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131
Fig. 30 (continued).
KFe3 AlSi3 O10 ðOHÞ2 þ1=2O2 ¼ KAlSi3 O8 þFe3 O4 þ H2 O
Biotite potassium feldspar
CaAl2 Si2 O8 þ2KCl þ 4SiO2 ¼ 2KAlSi3 O8 þCaCl2 :
Anorthite potassium feldspar
The alteration zone in porphyry Cu deposits starts from barren, early
sodic–calcic upward through potentially ore-grade potassic, chlorite–
sericite, and sericitic, to advanced argillic, and finally the lithocap
(Sillitoe, 2010). In general, the alteration–mineralization zones become
progressively younger upward (Fig. 30), consequently the shallower al-
teration–mineralization zones overprint deeper ones.
Sodic–calcic alteration is typically sulfide and metal poor (except for
Fe as magnetite) but can host mineralization in Au-rich porphyry Cu de-
posits. It is commonly located in the immediate wallrocks of the por-
phyry intrusion, or are found as a centrally located zone of some
porphyry Cu stocks (Sillitoe, 2010).
Potassic alteration is located in the center and deeper portions of the
porphyry. Dominant mineral changes from biotite in relatively mafic
porphyry intrusions and host rocks, to K-feldspar in more felsic, grano-
dioritic to quartz monzonitic settings (Sillitoe, 2010). Quartz-K ± Na-
feldspar overprints may destroy the more typical potassic assemblages.
The chalcopyrite ± bornite ore in many porphyry Cu deposits is largely
confined to potassic zones. Potassic-altered wallrocks may attain N 1 km
thickness. The potassic alteration generally becomes less intense from
the older to younger porphyry phases (Sillitoe, 2010). This is likely
due to a lowering of the pH as mineralization continues.
Chlorite–sericite alteration produces pale-green rocks and is wide-
spread in the shallower parts of some porphyry Cu deposits,
overprinting preexisting potassic assemblages. The alteration is charac-
terized by transformation of mafic minerals to chlorite, plagioclase to
sericite (fine-grained muscovite) and/or illite, and magnetite to hema-
ð36Þ
tite (martite and/or specularite), along with deposition of pyrite and
chalcopyrite (Sillitoe, 2010).
Sericitic alteration in porphyry Cu deposits normally overprints the
potassic and chlorite–sericite assemblages. It may be subdivided into
ð37Þ
two different types—a less common, early greenish to greenish-gray in
color alteration, and a far more common white alteration. The sericitic
alteration is commonly pyrite dominated, implying effective removal
of the Cu (±Au) present in the former chlorite–sericite and/or potassic
assemblages. It may also constitute ore with Cu either in the form of
chalcopyrite or as high sulfidation-state assemblages (Sillitoe, 2010).
The lower portion of argillic lithocaps may overprint the upper parts
of the porphyry Cu deposits, whereas the sericitic alteration transforms
upwardly to quartz–pyrophyllite. The advanced argillic alteration pref-
erentially affects lithologic units with low acid-buffering capacities
(Sillitoe, 2010).
6. Conclusion
The key processes of porphyry mineralization are oxidation and re-
duction of sulfur. Most of the porphyry deposits are closely associated
with oxidized magmas, with sulfate as the dominant sulfur mineral
species. Sulfur is one of the most important geosolvents that controls
the behaviors of copper and other chalcophile elements, therefore
knowledge of its geochemical behavior is essential to the understanding
of mineralization processes for copper and a variety of other metal re-
sources. Given that for most chalcophile elements, the partition coeffi-
cient between sulfide and melt is very high, elimination of residual
sulfide is essential for the extraction of chalcophile elements from the
source and thus the formation of porphyry deposits. The solubility of
sulfur depends strongly on sulfur speciation, which in turn depends
on oxygen fugacities. Sulfate is over 10 times more soluble than sulfide.
 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131
At oxygen fugacities higher than ΔFMQ + 2, most of the sulfur in melts
is present as sulfate, such that the solubility of sulfur increases from
~1300 ppm to 2 wt.%. Consequently, slab melts becomes sulfur under-
saturated at N5% partial melting, with Cu contents of over 1000 ppm.
Therefore, ΔFMQ + 2 is often considered the magic number for porphy-
ry mineralization.
Metals of porphyry Cu deposits are hosted in sulfides, which require
reduction of sulfate to sulfide during the final stage of mineralization. In
principle, sulfate can also be reduced by assimilation of reducing sedi-
ments or degassing of oxidizing gases. Porphyry deposits are usually
mineralized throughout the whole pluton, whereas interactions with
country rocks occur mainly at the interface, such that assimilation of re-
ducing sediments is not likely to be the controlling process. Degassing is
not the main process in deeply emplaced porphyry bodies, such that it is
not likely to be a major process for sulfate reduction, either. Ferrous iron
is the most important reductant that is responsible for sulfate reduction
during porphyry mineralization. The highest oxygen fugacity favorable
for porphyry mineralization is the HM buffer. Otherwise, there is no fer-
rous Fe in the system. The reduction of sulfate and oxidation of ferrous
Fe lower the pH value. This, in turn, elevates the oxidation potential of
sulfate, driving the oxygen fugacities up to the HM buffer. These
behaviors explain the popular occurrence of hypogene magnetite and
hematite (and specularite) in porphyry deposits.
Low pH fluids cause formation of pervasive alteration zones in por-
phyry Cu deposits, starting from barren, early sodic–calcic alteration up-
ward through potentially ore-grade potassic, chlorite–sericite, and
sericitic alterations, to advanced argillic alterations, and finally forming
the lithocaps. The amount of H+ released during mineralization and the
alkali content in the porphyry together control advanced argillic
lithocap formation and alterations.
Hydrogen and methane form during the final mineralization process
of porphyry deposits. Most of the hydrogen and methane should have
been oxidized by ferric Fe. In special cases, some of the reduced gases
may escape from the system, and even get trapped in fluid inclusions.
Therefore, small amount of reduced gases in fluid inclusions cannot
argue against the oxidized feature of the magmas.
Reduced magmas are not favorable for porphyry mineralization.
There are indeed several small porphyry deposits that appear to be re-
lated to reduced porphyries. In our opinion, the reduced porphyry de-
posits so far reported are either host rocks at distal sites as far as
several kilometers away from or above the causative porphyry lying
deep underneath, or a consequence of fluid transportation. Some of
the reduced porphyries were originally associated with oxidized
magmas but were reduced through assimilation of reducing compo-
nents during emplacement. Degassing of SO2 is not likely to be a main
process for porphyry deposit formation, and it doesn't reduce sulfate
to sulfide, either. Therefore, degassing of SO2 cannot explain the features
of reduced porphyries. Given that a large portion of metals in a porphyry
deposit are hosted in wall rocks, attention is needed to identify the caus-
ative porphyries.
Acknowledgments
We would like to thank Professor Cin-ty A. Lee for constructive
discussions. This study is supported by the National Natural Science
Foundation of China (nos. 41090374, 41121002, 41172080). This is con-
tribution no. IS-1939 from GIGCAS.
References
Abratis, M., Worner, G., 2001. Ridge collision, slab-window formation, and the flux of
Pacific asthenosphere into the Caribbean realm. Geology 29 (2), 127–130.
An, F., Zhu, Y.F., 2010. Native antimony in the Baogutu gold deposit (west Junggar, NW
China): its occurrence and origin. Ore Geol. Rev. 37 (3–4), 214–223.
Arculus, R.J., 1994. Aspects of magma genesis in arcs. Lithos 33 (1–3), 189–208.
127
Astudillo, N., Roperch, P., Townley, B., Arriagada, C., Chauvin, A., 2010. Magnetic polarity
zonation within the El Teniente copper–molybdenum porphyry deposit, central
Chile. Mineral. Deposita 45 (1), 23–41.
Audetat, A., Pettke, T., Dolejs, D., 2004. Magmatic anhydrite and calcite in the ore-forming
quartz–monzodiorite magma at Santa Rita, New Mexico (USA): genetic constraints
on porphyry–Cu mineralization. Lithos 72 (3–4), 147–161.
Baker, T., Ash, C.H., Thompson, J.F.H., 1997. Geological setting and characteristics of the
Red Chris porphyry copper–gold deposit, northwestern British Columbia. Explor.
Min. Geol. 6 (4), 297–316.
Baker, M.J., Cooke, D.R., Hollings, P.N., 2011. LA-ICP-MS U–Pb zircon ages and Nd isotope data
for the Teniente Plutonic Complex: implications for the evolution of the El Teniente
Porphyry Cu–Mo Deposit. Let's Talk Ore Deposits vols. I and Ii, (853–855 pp.).
Bali, E., Audetat, A., Keppler, H., 2013. Water and hydrogen are immiscible in Earth's man-
tle. Nature 495 (7440), 220–222.
Ballard, J.R., Palin, J.M., Williams, I.S., Campbell, I.H., Faunes, A., 2001. Two ages of porphy-
ry intrusion resolved for the super-giant Chuquicamata copper deposit of northern
Chile by ELA-ICP-MS and SHRIMP. Geology 29 (5), 383–386.
Ballard, J.R., Palin, J.M., Campbell, I.H., 2002. Relative oxidation states of magmas inferred
from Ce(IV)/Ce(III) in zircon: application to porphyry copper deposits of northern
Chile. Contrib. Mineral. Petrol. 144 (3), 347–364.
Ballhaus, C., 1993. Oxidation states of the lithospheric and asthenospheric upper mantle.
Contrib. Mineral. Petrol. 114, 331–348.
Barra, F., 2011. Assessing the longevity of porphyry Cu–Mo deposits: examples from the
Chilean Andes. Let's Talk Ore Deposits vols. I and Ii, (145–147 pp.).
Beermann, O., Botcharnikov, R.E., Holtz, F., Diedrich, O., Nowak, M., 2011. Temperature de-
pendence of sulfide and sulfate solubility in olivine-saturated basaltic magmas.
Geochim. Cosmochim. Acta 75 (23), 7612–7631.
Binder, B., Keppler, H., 2011. The oxidation state of sulfur in magmatic fluids. Earth Planet.
Sci. Lett. 301, 190–198.
Brandon, A.D., Draper, D.S., 1996. Constraints on the origin of the oxidation state of
mantle overlying subduction zones: an example from Simcoe, Washington, USA.
Geochim. Cosmochim. Acta 60 (10), 1739–1749.
Bryant, J.A., Yogodzinski, G.M., Churikova, T.G., 2007. Melt–mantle interactions beneath
the Kamchatka arc: evidence from ultramafic xenoliths from Shiveluch volcano.
Geochem. Geophys. Geosyst. 8 (4), Q04007. http://dx.doi.org/10.1029/2006GC
001443.
Burnham, C.W., Ohmoto, H., 1980. Late-stage processes of felsic magmatism. Min. Geol.
Spec. Issue 8, 1–12.
Calagari, A.A., 2003. Stable isotope (S, O, H and C) studies of the phyllic and potassic–
phyllic alteration zones of the porphyry copper deposit at Sungun, East Azarbaidjan,
Iran. J. Asian Earth Sci. 21 (7), 767–780.
Candela, P.A., 1992. Controls on ore metal ratios in granite-related ore systems — an ex-
perimental and computational approach. Trans. R. Soc. Edinb. Earth Sci. 83, 317–326.
Cannell, J., Cooke, D.R., Stein, H.J., Markey, R., 2003. New paragenetically constrained Re–
Os molybdenite ages for El Teniente Cu–Mo porphyry deposit, Central Chile. Mineral
Exploration and Sustainable Development vols. 1 and 2, (255–258 pp.).
Cannell, J., Cooke, D.R., Walshe, J.L., Stein, H., 2005. Geology, mineralization, alteration, and
structural evolution of the El Teniente porphyry Cu–Mo deposit. Econ. Geol. 100 (5),
979–1003.
Cao, M., Qin, K., Li, G., Jin, L., Evans, N.J., Yang, X., 2014. Baogutu: an example of reduced
porphyry Cu deposit in western Junggar. Ore Geol. Rev. 56, 159–180.
Carmichael, I.S.E., 1991. The redox states of basic and silicic magmas — a reflection of their
source regions. Contrib. Mineral. Petrol. 106 (2), 129–141.
Castillo, P.R., 2006. An overview of adakite petrogenesis. Chin. Sci. Bull. 51 (3), 258–268.
Chen, Y.J., 2013. The development of continental collision metallogeny and its application.
Acta Petrol. Sin. 29 (1), 1–17.
Chen, Y.J., Li, C., Zhang, J., Li, Z., Wang, H.H., 2000. Sr and O isotopic characteristics of por-
phyries in the Qinling molybdenum deposit belt and their implication to genetic
mechanism and type. Sci. China. Ser. D Earth Sci. 43, 82–94.
Chen, W., Xu, Z.W., Lu, X.C., Yang, X.N., Li, H.C., Qu, W.J., Chen, J.Q., Wang, H., Wang, S.H.,
2013. Petrogenesis of the Bao'anzhai granite and associated Mo mineralization, west-
ern Dabie orogen, east-central China: constraints from zircon U–Pb and molybdenite
Re–Os dating, whole-rock geochemistry, and Sr–Nd–Pb–Hf isotopes. Int. Geol. Rev. 55
(10), 1220–1238.
Chiaradia, M., 2014. Copper enrichment in arc magmas controlled by overriding plate
thickness. Nature Geosci. 7, 43–46.
Chiaradia, M., Ulianov, A., Kouzmanov, K., Beate, B., 2012. Why large porphyry Cu deposits
like high Sr/Y magmas? Sci. Rep. 2. http://dx.doi.org/10.1038/srep00685.
Chou, I.M., 1978. Calibration of oxygen buffers at elevated P and T using the hydrogen fu-
gacity sensor. Am. Mineral. 63, 690–703.
Chou, I.M., 1986. Permeability of precious metals to hydrogen at 2 kbar total pressure and
elevated temperatures. Am. J. Sci. 286, 638–658.
Chung, S.L., Liu, D.Y., Ji, J.Q., Chu, M.F., Lee, H.Y., Wen, D.J., Lo, C.H., Lee, T.Y., Qian, Q., Zhang,
Q., 2003. Adakites from continental collision zones: melting of thickened lower crust
beneath southern Tibet. Geology 31 (11), 1021–1024.
Cole, R.B., Stewart, B.W., 2009. Continental margin volcanism at sites of spreading ridge
subduction: examples from southern Alaska and western California. Tectonophysics
464 (1–4), 118–136.
Cole, R.B., Nelson, S.W., Layer, P.W., Oswald, P.J., 2006. Eocene volcanism above a de-
pleted mantle slab window in southern Alaska. Geol. Soc. Am. Bull. 118 (1–2),
140–158.
Cooke, D.R., Hollings, P., Walsh, J.L., 2005. Giant porphyry deposits: characteristics, distri-
bution, and tectonic controls. Econ. Geol. 100 (5), 801–818.
Cooke, D.R., Deyell, C.L., Waters, P.J., Gonzales, R.I., Zaw, K., 2011. Evidence for magmatic–
hydrothermal fluids and ore-forming processes in epithermal and porphyry deposits
of the Baguio District, Philippines. Econ. Geol. 106 (8), 1399–1424.
128 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131
Cottrell, E., Kelley, K.A., 2013. Redox heterogeneity in mid-ocean ridge basalts as a func-
tion of mantle source. Science 340 (6138), 1314–1317.
Craig, H., 1961. Isotopic variations in meteoric waters. Science 133, 1702–1703.
Crerar, D.A., Susak, N.J., Borcsik, M., Schwartz, S., 1978. Solubility of the buffer assemblage
pyrite–pyrrhotite–magnetite in NaCl solutions from 200 to 350 °C. Geochim.
Cosmochim. Acta 42, 1427–1437.
Cuadra, P., Rojas, G., 2001. Oxide mineralization at the Radomiro Tomic porphyry copper
deposit, northern Chile. Econ. Geol. Bull. Soc. Econ. Geol. 96 (2), 387–400.
Defant, M.J., Drummond, M.S., 1990. Derivation of some modern arc magmas by melting
of young subducted lithosphere. Nature 347, 662–665.
Dilles, J.H., Tomlinson, A.J., Garcia, M., Alcota, H., 2011. The geology of the Fortuna Grano-
diorite Complex, Chuquicamata district, Northern Chile: relation to porphyry copper
deposits. Let's Talk Ore Deposits. vols I and Ii, (398–400 pp.).
Eugster, H.P., 1957. Heterogeneous reactions involving oxidation and reduction at high
pressures and temperatures. J. Chem. Phys. 26, 1160.
Eugster, H.P., Wones, D.R., 1962. Stability relations of the ferruginous biotite, annite. J.
Petrol. 3, 82–125.
Evans, K.A., Elburg, M.A., Kamenetsky, V.S., 2012. Oxidation state of subarc mantle. Geol-
ogy 40 (9), 783–786.
Field, C.W., Zhang, L., Dilles, J.H., Rye, R.O., Reed, M.H., 2005. Sulfur and oxygen isotopic
record in sulfate and sulfide minerals of early, deep, pre-Main Stage porphyry Cu–
Mo and late Main Stage base-metal mineral deposits, Butte district, Montana.
Chem. Geol. 215 (1–4), 61–93.
Gaetani, G.A., Grove, T.L., 1997. Partitioning of moderately siderophile elements among
olivine, silicate melt, and sulfide melt: constraints on core formation in the Earth
and Mars. Geochim. Cosmochim. Acta 61 (9), 1829–1846.
Gao, S., Rudnick, R.L., Yuan, H.L., Liu, X.M., Liu, Y.S., Xu, W.L., Ling, W.L., Ayers, J., Wang, X.C.,
Wang, Q.H., 2004. Recycling lower continental crust in the North China craton. Nature
432 (7019), 892–897.
Gao, Y.L., Zhang, J.M., Ye, H.S., Meng, F., Zhou, K., Gao, Y., 2010. Geological characteristics
and molybdenite Re–Os isotopic dating of Shiyaogou porphyry molybdenum deposit
in the East Qinling. Acta Petrol. Sin. 26 (3), 729–739.
Garrido, I., Cembrano, J., Sina, A., Stedman, P., Yanez, G., 2002. High magma oxidation state
and bulk crustal shortening: key factors in the genesis of Andean porphyry copper
deposits, central Chile (31–34° S). Rev. Geol. Chile 29 (1), 43–54.
Giggenbach, W.F., 1992a. Isotopic shifts in waters from geothermal and volcanic systems
along convergent plate boundaries and their origin. Earth Planet. Sci. Lett. 113 (4),
495–510.
Giggenbach, W.F., 1992b. SEG distinguished lecture — magma degassing and mineral de-
position in hydrothermal systems along convergent plate boundaries. Econ. Geol.
Bull. Soc. Econ. Geol. 87 (7), 1927–1944.
Gonzalez-Partida, E., Levresse, G., Carrillo-Chavez, A., Cheilletz, A., Gasquet, D., Jones, D.,
2003. Paleocene adakite Au–Fe bearing rocks, Mezcala, Mexico: evidence from geo-
chemical characteristics. J. Geochem. Explor. 80 (1), 25–40.
Green, T.H., Watson, E.B., 1982. Crystallization of apatite in natural magmas under high-
pressure, hydrous conditions, with particular reference to orogenic rock series.
Contrib. Mineral. Petrol. 79 (1), 96–105.
Groome, W.G., Thorkelson, D.J., 2009. The three-dimensional thermo-mechanical signature
of ridge subduction and slab window migration. Tectonophysics 464 (1–4), 70–83.
Guo, F., Fan, W., Li, C., Zhang, S.-H., Zhao, Y., Song, B., Yang, Z., Hu, J.-M., Wu, H., 2006. Geo-
chemistry of late Mesozoic adakites from the Sulu belt, eastern China: magma genesis
and implications for crustal recycling beneath continental collisional orogens:
Carboniferous granitic plutons from the northern margin of the North China Block:
implications for a late Palaeozoic active continental margin. Geol. Mag. 143 (1), 1–13.
Halter, W., Heinrich, C., Pettke, T., 2005. Magma evolution and the formation of porphyry
Cu–Au ore fluids: evidence from silicate and sulfide melt inclusions. Mineral.
Deposita 39 (8), 845–863.
Han, Y.G., Zhang, S.H., Pirajno, F., Zhou, X.W., Zhao, G.C., Qu, W.J., Liu, S.H., Zhang, J.M.,
Liang, H.B., Yang, K., 2013. U–Pb and Re–Os isotopic systematics and zircon Ce4+/
Ce3+ ratios in the Shiyaogou Mo deposit in eastern Qinling, central China: insights
into the oxidation state of granitoids and Mo (Au) mineralization. Ore Geol. Rev.
55, 29–47.
Haschke, M., Ahmadian, J., Murata, M., McDonald, I., 2010. Copper mineralization
prevented by arc-root delamination during Alpine–Himalayan collision in central
Iran. Econ. Geol. 105 (4), 855–865.
Hedenquist, J.W., Lowenstern, J.B., 1994. The role of magmas in the formation of hydro-
thermal ore-deposits. Nature 370 (6490), 519–527.
Hedenquist, J.W., Arribas, A., Reynolds, T.J., 1998. Evolution of an intrusion-centered
hydrothermal system: Far Southeast–Lepanto porphyry and epithermal Cu–Au
deposits, Philippines. Econ. Geol. Bull. Soc. Econ. Geol. 93 (4), 373–404.
Heinrich, C.A., 1990. The chemistry of hydrothermal tin (–tungsten) ore deposition. Econ.
Geol. 85, 457–481.
Heinrich, C.A., 2005. The physical and chemical evolution of low-salinity magmatic fluids
at the porphyry to epithermal transition: a thermodynamic study. Mineral. Deposita
39, 864–889.
Heinrich, C.A., Driesner, T., Stefansson, A., Seward, T.M., 2004. Magmatic vapor contraction
and the transport of gold from the porphyry environment to epithermal ore deposits.
Geology 32 (9), 761–764.
Hemingway, B.S., 1990. Thermodynamic properties for bunsenite, NiO, magnetite, Fe3O4,
and hematite, Fe2O3 with comments on selected oxygen buffer reactions. Am. Miner-
al. 75, 781–790.
Hezarkhani, A., 2006. Hydrothermal evolution of the Sar–Cheshmeh porphyry Cu–Mo de-
posit, Iran: evidence from fluid inclusions. J. Asian Earth Sci. 28 (4–6), 409–422.
Hoefs, J. (Ed.), 2004. Stable Isotope Geochemistry. Springer, Germany.
Hofmann, A.W., 1988. Chemical differentiation of the Earth: the relationship between
mantle, continental crust, and oceanic crust. Earth Planet. Sci. Lett. 90, 297–314.
Hollings, P., Cooke, D., Clark, A., 2005. Regional geochemistry of tertiary igneous rocks in
central Chile: implications for the geodynamic environment of giant porphyry copper
and epithermal gold mineralization. Econ. Geol. 100 (5), 887–904.
Hou, Z.Q., Gao, Y.F., Qu, X.M., Rui, Z.Y., Mo, X.X., 2004. Origin of adakitic intrusives gener-
ated during mid-Miocene east–west extension in southern Tibet. Earth Planet. Sci.
Lett. 220 (1–2), 139–155.
Hou, Z.Q., Pan, X.F., Yang, Z.M., Qu, X.M., 2007a. Porphyry Cu–(Mo–Au) deposits no relat-
ed to oceanic-slab subduction: examples from Chinese porphyry deposits in conti-
nental settings. Geoscience 21 (2), 332–351 (in Chinese with English abstract).
Hou, Z.Q., Xie, Y.L., Xu, W.Y., Li, Y.Q., Zhu, X.K., Khin, Z., Beaudoin, G., Rui, Z.Y., Wei, H.A.,
Ciren, L., 2007b. Yulong deposit, eastern Tibet: a high-sulfidation Cu–Au porphyry
copper deposit in the eastern Indo-Asian collision zone. Int. Geol. Rev. 49 (3),
235–258.
Hou, Z.Q., Yang, Z.M., Qu, X.M., Meng, X.J., Li, Z.Q., Beaudoin, G., Rui, Z.Y., Gao, Y.F., Zaw, K.,
2009. The Miocene Gangdese porphyry copper belt generated during post-collisional
extension in the Tibetan Orogen. Ore Geol. Rev. 36 (1–3), 25–51.
Huang, F., Li, S.G., Dong, F., He, Y.S., Chen, F.K., 2008. High-Mg adakitic rocks in the Dabie
orogen, central China: implications for foundering mechanism of lower continental
crust. Chem. Geol. 255 (1–2), 1–13.
Huebner, J.S., 1987. Use of gas mixtures at low pressure to specify oxygen and other fu-
gacities of furnace atmospheres. Hydrothermal Experimental Techniques, pp. 20–60.
Huebner, J.S., Sato, M., 1970. The oxygen fugacity–temperature relationships of manga-
nese oxide and nickel oxide buffers. Am. Mineral. 55, 934–952.
Imai, A., 2001. Generation and evolution of ore fluids for porphyry Cu–Au mineralization
of the Santo Tomas II (Philex) deposit, Philippines. Resour. Geol. 51 (2), 71–96.
Imai, A., 2002. Metallogenesis of porphyry Cu deposits of the western Luzon arc,
Philippines: K–Ar ages, SO3 contents of microphenocrystic apatite and significance
of intrusive rocks. Resour. Geol. 52 (2), 147–161.
Imai, A., 2005. Evolution of hydrothermal system at the Dizon porphyry Cu–Au deposit,
Zambales, Philippines. Resour. Geol. 55 (2), 73–90.
Imai, A., Ohno, S., 2005. Primary ore mineral assemblage and fluid inclusion study of the
Batu Hijau porphyry Cu–Au deposit, Sumbawa, Indonesia. Resour. Geol. 55 (3),
239–248.
Imai, A., Listanco, E.L., Fujii, T., 1993. Petrologic and sulfur isotopic significance of highly
oxidized and sulfur-rich magma of Mt-Pinatubo, Philippines. Geology 21 (8),
699–702.
Imai, A., Ohbuchi, Y., Tanaka, T., Morita, S., Yasunaga, K., 2007. Characteristics of porphyry
Cu mineralization at Waisoi (Namosi district), Viti Levu, Fiji. Resour. Geol. 57 (4),
374–385.
Ishihara, S., 1977. The magnetite-series and ilmenite-series granitic rock. Min. Geol. 27,
930–941.
Ishihara, S., 2004. The redox state of granitoids relative to tectonic setting and earth his-
tory: the magnetite–ilmenite series 30 years later. Trans. R. Soc. Edinb. Earth Sci. 95,
23–33.
Ishihara, S., Matsuhisa, Y., 1999. Oxygen isotopic constraints on the geneses of the Mio-
cene Outer Zone granitoids in Japan. Lithos 46 (3), 523–534.
Ishihara, S., Murakami, H., 2006. Fractionated ilmenite-series granites in Southwest Japan:
source magma for REE–Sn–W mineralizations. Resour. Geol. 56 (3), 245–256.
Ishihara, S., Sasaki, A., 1991. Ore-deposits related to granitic magmatism in Japan — a
magmatic viewpoint. Episodes 14 (3), 286–292.
Ishihara, S., Terashima, S., 1989. Carbon contents of the magnetite-series and ilmenite-
series granitoids in Japan. Geochem. J. 23 (1), 25–36.
Jenkyns, H.C., 2010. Geochemistry of oceanic anoxic events. Geochem. Geophys. Geosyst.
11, Q03004. http://dx.doi.org/10.1029/2009GC002788.
Jenner, F.E., O'Neill, H.S.C., Arculus, R.J., Mavrogenes, J.A., 2010. The magnetite crisis in the
evolution of arc-related magmas and the initial concentration of Au, Ag and Cu.
J. Petrol. 51 (12), 2445–2464.
Jenner, F.E., O'neill, H.S.C., Arculus, R.J., Mavrogenes, J.A., 2012. The magnetite crisis in the
evolution of arc-related magmas and the initial concentration of Au, Ag and Cu (vol
51, pg 2445, 2010). J. Petrol. 53 (5), 1089-1089.
Jiang, Y.H., Jiang, S.Y., Ling, H.F., Dai, B.Z., 2006. Low-degree melting of a metasomatized
lithospheric mantle for the origin of Cenozoic Yulong monzogranite-porphyry, east
Tibet: geochemical and Sr–Nd–Pb–Hf isotopic constraints. Earth Planet. Sci. Lett.
241 (3–4), 617–633.
Jugo, P.J., 2009. Sulfur content at sulfide saturation in oxidized magmas. Geology 37 (5),
415–418.
Jugo, P.J., Luth, R.W., Richards, J.P., 2005. Experimental data on the speciation of sulfur as a
function of oxygen fugacity in basaltic melts. Geochim. Cosmochim. Acta 69 (2),
497–503.
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.
Kavalieris, I., Rinchin, O., Gombojav, J., Gombosuren, N., Crane, D., Orssich, C., Bat-Erdene,
K., 2011. Characteristics of the Oyu Tolgoi porphyry deposits, South Gobi, Mongolia.
Let's Talk Ore Deposits vols. I and Ii, (342–344 pp.).
Kay, R.W., 1978. Aleutian magnesian andesite: melts from subducted Pacific Ocean crust.
J. Volcanol. Geotherm. Res. 4, 117–132.
Kay, S.M., Godoy, E., Kurtz, A., 2005. Episodic arc migration, crustal thickening, subduction
erosion, and magmatism in the south-central Andes. Geol. Soc. Am. Bull. 117 (1–2),
67–88.
Kelley, K.A., Cottrell, E., 2009. Water and the oxidation state of subduction zone magmas.
Science 325 (5940), 605–607.
Kelley, K.A., Cottrell, E., 2012. The influence of magmatic differentiation on the oxidation
state of Fe in a basaltic arc magma. Earth Planet. Sci. Lett. 329, 109–121.
Keppler, H., 2010. The distribution of sulfur between haplogranitic melts and aqueous
fluids. Geochim. Cosmochim. Acta 74 (2), 645–660.
 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131
Kesler, S.E., 1997. Metallogenic evolution of convergent margins: selected ore deposit
models. Ore Geol. Rev. 12 (3), 153–171.
Khashgerel, B.E., Kavalieris, I., Hayashi, K., 2008. Mineralogy, textures, and whole-rock
geochemistry of advanced argillic alteration: Hugo Dummett porphyry Cu-Au depos-
it, Oyu Tolgoi mineral district. Mongolia. Mineral. Deposita 43, 913–932.
Kinoshita, O., 1997. Slab window-related magmatism caused by the Kula–Pacific ridge
subduction beneath the Eurasia continent in the Cretaceous. Episodes 20 (3),
185–187.
Kishima, N., 1989. A thermodynamic study on the pyrite–pyrrhotite–magnetite–water
system at 300–500 °C with relevance to the fugacity/concentration quotient of aque-
ous H2S. Geochim. Cosmochim. Acta 53, 2143–2155.
Klemm, L.M., Pettke, T., Heinbicth, C.A., Campos, E., 2007. Hydrothermal evolution of the
El Teniente deposit, Chile: Porphyry Cu–Mo ore deposition from low-salinity mag-
matic fluids. Econ. Geol. 102 (6), 1021–1045.
Klemm, L.M., Pettke, T., Heinrich, C.A., 2008. Fluid and source magma evolution of
the Questa porphyry Mo deposit, New Mexico, USA. Mineral. Deposita 43 (5),
533–552.
Kress, V.C., Carmichael, I.S.E., 1991. The compressibility of silicate liquids containing Fe2O3
and the effect of composition, temperature, oxygen fugacity and pressure on their
redox states. Contrib. Mineral. Petrol. 108, 82–92.
Lang, J.R., Lueck, B., Mortensen, J.K., Russell, J.K., Stanley, C.R., Thompson, J.F.H., 1995.
Triassic–Jurassic silica-undersaturated and silica-saturated alkalic intrusions in the
cordillera of British-Columbia — implications for arc magmatism. Geology 23 (5),
451–454.
Lee, C.-T.A., 2014. Copper conundrums. Nat. Geosci. 7, 10–11.
Lee, C.T.A., Leeman, W.P., Canil, D., Li, Z.X.A., 2005. Similar V/Sc systematics in MORB and
arc basalts: implications for the oxygen fugacities of their mantle source regions. J.
Petrol. 46 (11), 2313–2336.
Lee, C.T.A., Luffi, P., Le Roux, V., Dasgupta, R., Albarede, F., Leeman, W.P., 2010. The redox
state of arc mantle using Zn/Fe systematics. Nature 468 (7324), 681–685.
Lee, C.T.A., Luffi, P., Chin, E.J., Bouchet, R., Dasgupta, R., Morton, D.M., Le Roux, V., Yin, Q.Z.,
Jin, D., 2012. Copper systematics in arc magmas and implications for crust–mantle
differentiation. Science 336 (6077), 64–68.
Lee, C.-T.A., Lee, T.C., Wu, C.-T., 2014. Modeling the compositional evolution of recharging,
evacuating, and fractionating (REFC) magma chambers: implications for differentia-
tion of arc magmas. Geochim. Cosmochim. Acta http://dx.doi.org/10.1016/j.gca.
2013.08.009 (in press).
Lerchbaumer, L., Audetat, A., 2012. High Cu concentrations in vapor-type fluid inclusions:
an artifact? Geochim. Cosmochim. Acta 88, 255–274.
Li, Y., Audetat, A., 2012. Partitioning of V, Mn, Co, Ni, Cu, Zn, As, Mo, Ag, Sn, Sb, W, Au, Pb,
and Bi between sulfide phases and hydrous basanite melt at upper mantle conditions.
Earth Planet. Sci. Lett. 355, 327–340.
Li, Y., Audetat, A., 2013. Gold solubility and partitioning between sulfide liquid,
monosulfide solid solution and hydrous mantle melts: implications for the formation
of Au-rich magmas and crust–mantle differentiation. Geochim. Cosmochim. Acta 118,
247–262.
Li, X.F., Sasaki, M., 2007. Hydrothermal alteration and mineralization of middle Jurassic
Dexing porphyry Cu–Mo deposit, southeast China. Resour. Geol. 57 (4), 409–426.
Li, X.F., Watanabe, Y., Mao, J.W., Liu, S.X., Yi, X.K., 2007. Sensitive high-resolution ion mi-
croprobe U–Pb Zircon and 40Ar–39Ar muscovite ages of the Yinshan deposit in the
northeast Jiangxi province, South China. Resour. Geol. 57 (3), 325–337.
Li, J.W., Zhao, X.F., Zhou, M.F., Vasconcelos, P., Ma, C.Q., Deng, X.D., de Souza, Z.S., Zhao, Y.
X., Wu, G., 2008. Origin of the Tongshankou porphyry-skarn Cu–Mo deposit, eastern
Yangtze craton, Eastern China: geochronological, geochemical, and Sr–Nd–Hf isotopic
constraints. Mineral. Deposita 43 (3), 315–336.
Li, H., Zhang, H., Ling, M.X., Wang, F.Y., Ding, X., Zhou, J.B., Yang, X.Y., Tu, X.L., Sun, W.D.,
2011. Geochemical and zircon U–Pb study of the Huangmeijian A-type granite: impli-
cations for geological evolution of the Lower Yangtze River belt. Int. Geol. Rev. 53
(5–6), 499–525.
Li, C.Y., Wang, F.Y., Hao, X.L., Zhang, H., Ling, M.X., Zhou, J.B., Li, Y.L., Fan, W.M., Sun, W.D.,
2012a. Formation of the world's largest molybdenum metallogenic belt: a plate-
tectonic perspective on the Qinling molybdenum deposits. Int. Geol. Rev. 54 (9),
1093–1112.
Li, C.Y., Zhang, H., Wang, F.Y., Liu, J.Q., Sun, Y.L., Hao, X.L., Li, Y.L., Sun, W.D., 2012b. The for-
mation of the Dabaoshan porphyry molybdenum deposit induced by slab rollback.
Lithos 150, 101–110.
Li, H., Ling, M.X., Li, C.Y., Zhang, H., Ding, X., Yang, X.Y., Fan, W.M., Li, Y.L., Sun, W.D., 2012c.
A-type granite belts of two chemical subgroups in central eastern China: indication of
ridge subduction. Lithos 150, 26–36.
Li, H.Y., Wang, X.X., Ye, H.S., Yang, L., 2012d. Emplacement ages and petrogenesis of the
molybdenum-bearing granites in the Jinduicheng area of East Qinling, China: con-
straints from zircon U–Pb ages and Hf isotopes. Acta Geol. Sin. Eng. Ed. 86 (3),
661–679.
Li, J.L., Gao, J., John, T., Klemd, R., Su, W., 2013a. Fluid-mediated metal transport in subduc-
tion zones and its link to arc-related giant ore deposits: constraints from a sulfide-
bearing HP vein in lawsonite eclogite (Tianshan, China). Geochim. Cosmochim. Acta
120, 326–362.
Li, N., Chen, Y.J., Pirajno, F., Ni, Z.Y., 2013b. Timing of the Yuchiling giant porphyry Mo sys-
tem, and implications for ore genesis. Mineral. Deposita 48 (4), 505–524.
Li, X.F., Hu, R.Z., Rusk, B., Xiao, R., Wang, C.Y., Yang, F., 2013c. U–Pb and Ar–Ar geochronol-
ogy of the Fujiawu porphyry Cu–Mo deposit, Dexing district, Southeast China: impli-
cations for magmatism, hydrothermal alteration, and mineralization. J. Asian Earth
Sci. 74, 330–342.
Liang, H.Y., Campbell, I.H., Allen, C., Sun, W.D., Liu, C.Q., Yu, H.X., Xie, Y.W., Zhang, Y.Q.,
2006. Zircon Ce4+/Ce3+ ratios and ages for Yulong ore-bearing porphyries in eastern
Tibet. Mineral. Deposita 41 (2), 152–159.
129
Liang, H.Y., Campbell, I.H., Allen, C.M., Sun, W.D., Yu, H.X., Xie, Y.W., Zhang, Y.Q.,
2007. The age of the potassic alkaline igneous rocks along the Ailao Shan–Red
River shear zone: implications for the onset age of left-lateral shearing. J. Geol.
115 (2), 231–242.
Liang, H.Y., Sun, W.D., Su, W.C., Zartman, R.E., 2009. Porphyry copper–gold mineralization
at Yulong, China, promoted by decreasing redox potential during magnetite alter-
ation. Econ. Geol. 104 (4), 587–596.
Ling, M.X., Wang, F.Y., Ding, X., Hu, Y.H., Zhou, J.B., Zartman, R.E., Yang, X.Y., Sun, W.D.,
2009. Cretaceous ridge subduction along the Lower Yangtse River Belt, Eastern
China. Econ. Geol. 104 (2), 303–321.
Ling, M.X., Wang, F.Y., Ding, X., Zhou, J.B., Sun, W.D., 2011. Different origins of adakites
from the Dabie Mountains and the Lower Yangtze River Belt, eastern China:
geochemical constraints. Int. Geol. Rev. 53 (5–6), 727–740.
Ling, M.X., Li, Y., Ding, X., Teng, F.Z., Yang, X.Y., Fan, W.M., Xu, Y.G., Sun, W.D., 2013. Destruc-
tion of the North China Craton induced by ridge subductions. J. Geol. 121 (2), 197–213.
Liu, L.J., Spasojevic, S., Gurnis, M., 2008. Reconstructing Farallon plate subduction beneath
North America back to the Late Cretaceous. Science 322 (5903), 934–938.
Liu, S.A., Li, S.G., He, Y.S., Huang, F., 2010. Geochemical contrasts between early Cretaceous
ore-bearing and ore-barren high-Mg adakites in central-eastern China: implications
for petrogenesis and Cu–Au mineralization. Geochim. Cosmochim. Acta 74,
7160–7178.
Liu, X., Fan, H.R., Hu, F.F., Hu, B.G., Zhu, X.Y., 2011. SEM-EDS investigation of daughter min-
erals of fluid inclusions at the Dexing porphyry Cu–Mo deposit, Jiangxi Province,
China. Acta Petrol. Sin. 27 (5), 1397–1409.
Liu, S.A., Li, S.G., Guo, S.S., Hou, Z.H., He, Y.S., 2012. The Cretaceous adakitic–basaltic–
granitic magma sequence on south-eastern margin of the North China Craton: impli-
cations for lithospheric thinning mechanism. Lithos 134, 163–178.
Liu, X., Xiong, X., Audétat, A., Li, Y., Song, M., Li, L., Sun, W., Ding, X., 2014. Partitioning of
copper between olivine, orthopyroxene, clinopyroxene, spinel, garnet and silicate
melts at upper mantle conditions. Geochim. Cosmochim. Acta 125, 1–22.
Lorand, J.P., 1990. Are spinel lherzolite xenoliths representative of the abundance of sulfur
in the upper mantle. Geochim. Cosmochim. Acta 54 (5), 1487–1492.
Lowell, J.D., Guilbert, J.M., 1970. Lateral and vertical alteration–mineralization zoning in
porphyry ore deposits. Econ. Geol. 65 (4) (373-).
Lynch, G., Ortega, S., 1997. Hydrothermal alteration and tourmaline–albite equilibria at
the Coxheath porphyry Cu–Mo–Au deposit, Nova Scotia. Can. Mineral. 35, 79–94.
Macpherson, C.G., Dreher, S.T., Thirlwall, M.F., 2006. Adakites without slab melting: high
pressure differentiation of island arc magma, Mindanao, the Philippines. Earth Planet.
Sci. Lett. 243 (3–4), 581–593.
Madsen, J.K., Thorkelson, D.J., Friedman, R.M., Marshall, D.D., 2006. Cenozoic to Recent
plate configurations in the Pacific Basin: ridge subduction and slab window
magmatism in western North America. Geosphere 2 (1), 11–34.
Mallmann, G., O'Neill, H.S.C., 2007. The effect of oxygen fugacity on the partitioning of Re
between crystals and silicate melt during mantle melting. Geochim. Cosmochim. Acta
71 (11), 2837–2857.
Mao, J.W., Xie, G.Q., Bierlein, F., Qu, W.J., Du, A.D., Ye, H.S., Pirajno, F., Li, H.M., Guo, B.J., Li,
Y.F., Yang, Z.Q., 2008. Tectonic implications from Re–Os dating of Mesozoic molybde-
num deposits in the East Qinling–Dabie orogenic belt. Geochim. Cosmochim. Acta 72
(18), 4607–4626.
Mao, J.W., Pirajno, F., Xiang, J.F., Gao, J.J., Ye, H.S., Li, Y.F., Guo, B.J., 2011. Mesozoic molyb-
denum deposits in the east Qinling–Dabie orogenic belt: characteristics and tectonic
settings. Ore Geol. Rev. 43 (1), 264–293.
Martin, H., 1999. Adakitic magmas: modern analogues of Archaean granitoids. Lithos 46
(3), 411–429.
Mathur, R., Ruiz, J., Titley, S., Gibbins, S., Margotomo, W., 2000. Different crustal sources
for Au-rich and Au-poor ores of the Grasberg Cu–Au porphyry deposit. Earth Planet.
Sci. Lett. 183 (1–2), 7–14.
Mavrogenes, J.A., O'Neill, H.S.C., 1999. The relative effects of pressure, temperature and
oxygen fugacity on the solubility of sulfide in mafic magmas. Geochim. Cosmochim.
Acta 63 (7–8), 1173–1180.
McDonough, W.F., Sun, S.S., 1995. The composition of the Earth. Chem. Geol. 120 (3–4),
223–253.
Moss, R., Scott, S.D., Binns, R.A., 2001. Gold content of eastern Manus basin volcanic rocks:
implications for enrichment in associated hydrothermal precipitates. Econ. Geol. Bull.
Soc. Econ. Geol. 96 (1), 91–107.
Mungall, J.E., 2002. Roasting the mantle: slab melting and the genesis of major Au and Au-
rich Cu deposits. Geology 30 (10), 915–918.
Mungall, J.E., Brenan, J.M., 2014. Partitioning of platinum-group elements and Au between
sulfide liquid and basalt and the origins of mantle–crust fractionation of the
chalcophile elements. Geochim. Cosmochim. Acta 125, 265–289.
Mutschler, F.E., Ludington, S., Bookstrom, A.A., 2010. Giant porphyryrelated metal camps
of the world—a database. USGS Open-File Report: 99-556. , (6 pp. (http://geopubs.wr.
usgs.gov/open-file/of99-556/)).
Myers, J., Eugster, H., 1983. The system Fe–Si–O: oxygen buffer calibrations to 1500 K.
Contrib. Mineral. Petrol. 82, 75–90.
O'Neil, H.St.C., Pownceby, M.I., 1993. Thermodynamic data from redox reactions at high
temperatures. Ι. An experimental and theoretical assessment. Contrib. Mineral. Petrol.
114, 296–314.
O'Neill, H.S.C., Mavrogenes, J.A., 2002. The sulfide capacity and the sulfur content at sul-
fide saturation of silicate melts at 1400 °C and 1 bar. J. Petrol. 43 (6), 1049–1087.
Ossandon, G., Freraut, R., Gustafson, L.B., Lindsay, D.D., Zentilli, M., 2001. Geology of the
Chuquicamata mine: a progress report. Econ. Geol. Bull. Soc. Econ. Geol. 96 (2),
249–270.
Oyarzun, R., Marquez, A., Lillo, J., Lopez, I., Rivera, S., 2001. Giant versus small porphyry
copper deposits of Cenozoic age in northern Chile: adakitic versus normal calc-
alkaline magmatism. Mineral. Deposita 36 (8), 794–798.
130 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131
Oyarzun, R., Marquez, A., Lillo, J., Lopez, I., Rivera, S., 2002. Reply to discussion on “Giant
versus small porphyry copper deposits of Cenozoic age in northern Chile: adakitic
versus normal calc-alkaline magmatism” by Oyarzun R, Marquez A, Lillo J, Lopez I,
Rivera S (Mineralium Deposita 36: 794–798, 2001). Mineral. Deposita 37 (8),
795–799.
Parkinson, I.J., Arculus, R.J., 1999. The redox state of subduction zones: insights from arc-
peridotites. Chem. Geol. 160 (4), 409–423.
Patricio, C.C., Gonzalo, R.S., 2001. Oxide mineralization at the Radomiro Tomic porphyry
copper deposit, northern Chile. Econ. Geol. 96, 387–400.
Patten, C., Barnes, S.J., Mathez, E.A., Jenner, F.E., 2013. Partition coefficients of chalcophile
elements between sulfide and silicate melts and the early crystallization history of
sulfide liquid: LA-ICP-MS analysis of MORB sulfide droplets. Chem. Geol. 358,
170–188.
Peach, C.L., Mathez, E.A., Keays, R.R., 1990. Sulfide melt silicate melt distribution coeffi-
cients for noble-metals and other chalcophile elements as deduced from MORB —
implications for partial melting. Geochim. Cosmochim. Acta 54 (12), 3379–3389.
Peng, G.Y., Luhr, J.F., McGee, J.J., 1997. Factors controlling sulfur concentrations in volcanic
apatite. Am. Mineral. 82 (11–12), 1210–1224.
Pettke, T., Oberli, F., Heinrich, C.A., 2010. The magma and metal source of giant porphyry-
type ore deposits, based on lead isotope microanalysis of individual fluid inclusions.
Earth Planet. Sci. Lett. 296 (3–4), 267–277.
Pokrovski, G.S., Dubrovinsky, L.S., 2011. The S− 3 ion is stable in geological fluids at elevated
temperatures and pressures. Science 331 (6020), 1052–1054.
Qu, X., Hou, Z., Li, Y., 2004. Melt components derived from a subducted slab in late oro-
genic ore-bearing porphyries in the Gangdese copper belt, southern Tibetan plateau.
Lithos 74 (3–4), 131–148.
Rabbia, O.M., Hernandez, L.B., French, D.H., King, R.W., Ayers, J.C., 2009. The El Teniente
porphyry Cu–Mo deposit from a hydrothermal rutile perspective. Mineral. Deposita
44 (8), 849–866.
Rajamani, V., Naldrett, A.J., 1978. Partitioning of Fe, Co, Ni, and Cu between sulfide liquid
and basaltic melts and composition of Ni–Cu sulfide deposits. Econ. Geol. 73 (1),
82–93.
Richards, J.P., 1999. Tectonomagmatic controls on localization of porphyry copper de-
posits, Chile. Mineral Deposits: Processes to Processing vols. 1 and 2, (425–428 pp.).
Richards, J.P., 2011a. High Sr/Y arc magmas and porphyry Cu ± Mo ± Au deposits: just
add water. Econ. Geol. 106 (7), 1075–1081.
Richards, J.P., 2011b. Magmatic to hydrothermal metal fluxes in convergent and collided
margins. Ore Geol. Rev. 40 (1), 1–26.
Richards, J.P., 2012. Discussion of Sun et al. (2011): ‘The genetic association of adakites
and Cu–Au ore deposits’. Int. Geol. Rev. 368–369.
Richards, J.P., 2013. Giant ore deposits formed by optimal alignments and combinations of
geological processes. Nat. Geosci. 6 (11), 911–916.
Richards, J.P., 2014. Discussion of : the link between reduced porphyry copper deposits
and oxidized magmas. Geochim. Cosmochim. Acta 126, 643–645.
Richards, J.P., Kerrich, R., 2007. Adakite-like rocks: their diverse origins and questionable
role in metallogenesis. Econ. Geol. 102 (4), 537–576.
Richards, J.P., Mumin, A.H., 2013. Magmatic–hydrothermal processes within an evolving
Earth: iron oxide–copper–gold and porphyry Cu ± Mo ± Au deposits. Geology 41
(7), 767–770.
Rowins, S.M., 2000. Reduced porphyry copper–gold deposits: a new variation on an old
theme. Geology 28 (6), 491–494.
Rudnick, R.L., Gao, S., 2003. Composition of the continental crust. In: Heinrich, D.H.,
Turekian, K.K. (Eds.), Treatise on Geochemistry. Pergamon, Oxford, pp. 1–64.
Sajona, F.G., Maury, R.C., 1998. Association of adakites with gold and copper mineraliza-
tion in the Philippines. C. R. Acad. Sci. IIA Earth Planet. Sci. 326 (1), 27–34.
Scharman, M.R., Pavlis, T.L., Ruppert, N., 2012. Crustal stabilization through the processes
of ridge subduction: examples from the Chugach metamorphic complex, southern
Alaska. Earth Planet. Sci. Lett. 329, 122–132.
Seedorff, E., Einaudi, M.T., 2004a. Henderson porphyry molybdenum system, Colorado: I.
Sequence and abundance of hydrothermal mineral assemblages, flow paths of
evolving fluids, and evolutionary style. Econ. Geol. Bull. Soc. Econ. Geol. 99 (1), 3–37.
Seedorff, E., Einaudi, M.T., 2004b. Henderson porphyry molybdenum system. Colorado: II.
Decoupling of introduction and deposition of metals during geochemical evolution of
hydrothermal fluids. Econ. Geol. Bull. Soc. Econ. Geol. 99 (1), 39–72.
Seo, J.H., Heinrich, C.A., 2013. Selective copper diffusion into quartz-hosted vapor
inclusions: evidence from other host minerals, driving forces, and consequences for
Cu–Au ore formation. Geochim. Cosmochim. Acta 113, 60–69.
Seo, J.H., Guillong, M., Heinrich, C.A., 2009. The role of sulfur in the formation of mag-
matic–hydrothermal copper–gold deposits. Earth Planet. Sci. Lett. 282 (1–4),
323–328.
Shafiei, B., Haschke, M., Shahabpour, J., 2009. Recycling of orogenic arc crust triggers por-
phyry Cu mineralization in Kerman Cenozoic arc rocks, southeastern Iran. Mineral.
Deposita 44 (3), 265–283.
Shahabpour, J., 1991. Some secondary ore formation features of the Sar–Cheshmeh por-
phyry copper–molybdenum deposit, Kerman, Iran. Mineral. Deposita 26 (4),
275–280.
Shaw, H.T., 1963. Hydrogen–water vapor mixtures: control of hydrothermal atmospheres
by hydrogen osmosis. Science 139, 1220–1222.
Shen, P., Pan, H.D., 2013. Country-rock contamination of magmas associated with the
Baogutu porphyry Cu deposit, Xinjiang, China. Lithos 177, 451–469.
Shen, P., Shen, Y.C., Pan, H.D., Wang, J.B., Zhang, R., Zhang, Y.X., 2010a. Baogutu porphyry
Cu–Mo–Au deposit, West Junggar, northwest China: petrology, alteration, and miner-
alization. Econ. Geol. 105 (5), 947–970.
Shen, P., Shen, Y.C., Wang, J.B., Zhu, H.P., Wang, L.J., Meng, L., 2010b. Methane-rich fluid
evolution of the Baogutu porphyry Cu–Mo–Au deposit, Xinjiang, NW China. Chem.
Geol. 275 (1–2), 78–98.
Shen, P., Shen, Y., Pan, H., Li, X.H., Dong, L., Wang, J., Zhu, H., Dai, H., Guan, W., 2012.
Geochronology and isotope geochemistry of the Baogutu porphyry copper deposit
in the West Junggar region, Xinjiang, China. J. Asian Earth Sci. 49, 99–115.
Shen, P., Pan, H.D., Xiao, W.J., Chen, X.H., Eleonorad, S., Shen, Y.C., 2013a. Two
geodynamic–metallogenic events in the Balkhash (Kazakhstan) and the West
Junggar (China): Carboniferous porphyry Cu and Permian greisen W–Mo mineraliza-
tion. Int. Geol. Rev. 55 (13), 1660–1687.
Shen, P., Pan, H.D., Xiao, W.J., Li, X.H., Dai, H.W., Zhu, H.P., 2013b. Early Carboniferous
intra-oceanic arc and back-arc basin system in the West Junggar, NW China. Int.
Geol. Rev. 55 (16), 1991–2007.
Shi, P.F., 1992. Fluid fugacities and phase equilibria in the Fe–Si–O–H–S system. Am. Min-
eral. 77, 1050–1066.
Sillitoe, R.H., 1999. Styles of high-sulphidation gold, silver and copper mineralisation in
porphyry and epithermal environments. Pacrim'99: International Congress on
Earth Science, Exploration and Mining Around the Pacific Rim, Proceedings. 99
(29–44 pp.).
Sillitoe, R.H., 2010. Porphyry copper systems. Econ. Geol. 105 (1), 3–41.
Sillitoe, R.H., Burrows, D.R., 2002. New field evidence bearing on the origin of the El Laco
magnetite deposit, northern Chile. Econ. Geol. Bull. Soc. Econ. Geol. 97 (5),
1101–1109.
Singer, D.A., 2008. Mineral deposit densities for estimating mineral resources. Math.
Geosci. 40 (1), 33–46.
Smith, C.M., Canil, D., Rowins, S.M., Friedman, R., 2012. Reduced granitic magmas in an arc
setting: the Catface porphyry Cu–Mo deposit of the Paleogene Cascade Arc. Lithos
154, 361–373.
Smithson, D.M., Rowins, S.M., 2005. Reduced I-type magmatism and porphyry Cu–Au
mineralization in the west Central Cascades, WA: the ca. 37 Ma North Fork Deposit.
Geochim. Cosmochim. Acta 69 (10), A566-A566.
Song, S.G., Su, L., Niu, Y.L., Lai, Y., Zhang, L.F., 2009. CH4 inclusions in orogenic harzburgite:
evidence for reduced slab fluids and implication for redox melting in mantle wedge.
Geochim. Cosmochim. Acta 73 (6), 1737–1754.
Sotnikov, V.I., Ponomarchuk, V.A., Pertseva, A.P., Berzina, A.P., Berzina, A.N., Girnon, V.O.,
2004. Evolution of sulfur isotopes in porphyry Cu–Mo ore-magmatic systems of
Siberia and Mongolia. Geol. Geofiz. 45 (8), 963–974.
Spry, P.G., Scott, S.D., 1986. The stability of zincian spinels in sulfide systems and their po-
tential as exploration guides for metamorphosed massive sulfide deposits. Econ. Geol.
81, 1446–1461.
Spry, P.G., Paredes, M.M., Foster, F., Truckle, J.S., Chadwick, T.H., 1996. Evidence for a ge-
netic link between gold–silver telluride and porphyry molybdenum mineralization
at the Golden Sunlight deposit, Whitehall, Montana: fluid inclusion and stable isotope
studies. Econ. Geol. Bull. Soc. Econ. Geol. 91 (3), 507–526.
Stagno, V., Frost, D.J., 2010. Carbon speciation in the asthenosphere: experimental mea-
surements of the redox conditions at which carbonate-bearing melts coexist with
graphite or diamond in peridotite assemblages. Earth Planet. Sci. Lett. 300 (1–2),
72–84.
Stagno, V., Ojwang, D.O., McCammon, C.A., Frost, D.J., 2013. The oxidation state of the
mantle and the extraction of carbon from Earth's interior. Nature 493 (7430)
(84–+).
Stein, H.J., Markey, R.J., Morgan, J.W., Du, A., Sun, Y., 1997. Highly precise and accurate Re–
Os ages for molybdenite from the East Qinling molybdenum belt, Shaanxi Province,
China. Econ. Geol. Bull. Soc. Econ. Geol. 92 (7–8), 827–835.
Stern, C.R., Funk, J.A., Skewes, M.A., Arevalo, A., 2007. Magmatic anhydrite in plutonic
rocks at the El Teniente Cu–Mo deposit chile, and the role of sulfur- and copper-
rich magmas in its formation. Econ. Geol. 102 (7), 1335–1344.
Stern, C.R., Skewes, M.A., Arevalo, A., 2011. Magmatic evolution of the Giant El Teniente
Cu–Mo Deposit, Central Chile. J. Petrol. 52 (7–8), 1591–1617.
Sun, W.D., Williams, I.S., Li, S.G., 2002. Carboniferous and triassic eclogites in the western
Dabie Mountains, east-central China: evidence for protracted convergence of the
North and South China Blocks. J. Metamorph. Geol. 20 (9), 873–886.
Sun, W.D., Arculus, R.J., Bennett, V.C., Eggins, S.M., Binns, R.A., 2003a. Evidence for rheni-
um enrichment in the mantle wedge from submarine arc-like volcanic glasses (Papua
New Guinea). Geology 31 (10), 845–848.
Sun, W.D., Bennett, V.C., Eggins, S.M., Arculus, R.J., Perfit, M.R., 2003b. Rhenium systemat-
ics in submarine MORB and back-arc basin glasses: laser ablation ICP-MS results.
Chem. Geol. 196 (1–4), 259–281.
Sun, W.D., Bennett, V.C., Eggins, S.M., Kamenetsky, V.S., Arculus, R.J., 2003c. Enhanced
mantle-to-crust rhenium transfer in undegassed arc magmas. Nature 422 (6929),
294–297.
Sun, W.D., Arculus, R.J., Kamenetsky, V.S., Binns, R.A., 2004a. Release of gold-bearing fluids
in convergent margin magmas prompted by magnetite crystallization. Nature 431
(7011), 975–978.
Sun, W.D., Bennett, V.C., Kamenetsky, V.S., 2004b. The mechanism of Re enrichment in arc
magmas: evidence from Lau Basin basaltic glasses and primitive melt inclusions.
Earth Planet. Sci. Lett. 222 (1), 101–114.
Sun, W.D., Ding, X., Hu, Y.H., Li, X.H., 2007. The golden transformation of the Cretaceous
plate subduction in the west Pacific. Earth Planet. Sci. Lett. 262 (3–4), 533–542.
Sun, X.M., Tang, Q., Sun, W.D., Xu, L., Zhai, W., Liang, J.L., Liang, Y.H., Shen, K., Zhang, Z.M.,
Zhou, B., Wang, F.Y., 2007. Monazite, iron oxide and barite exsolutions in apatite ag-
gregates from CCSD drillhole eclogites and their geological implications. Geochim.
Cosmochim. Acta 71 (11), 2896–2905.
Sun, W.D., Ling, M.X., Yang, X.Y., Fan, W.M., Ding, X., Liang, H.Y., 2010. Ridge subduction
and porphyry copper–gold mineralization: an overview. Sci. China Ser. D Earth Sci.
53 (4), 475–484.
Sun, W.D., Zhang, H., Ling, M.X., Ding, X., Chung, S.L., Zhou, J.B., Yang, X.Y., Fan, W.M., 2011.
The genetic association of adakites and Cu–Au ore deposits. Int. Geol. Rev. 53 (5–6),
691–703.
 W. Sun et al. / Ore Geology Reviews 65 (2015) 97–131
Sun, W.D., Ling, M.X., Chung, S.L., Ding, X., Yang, X.Y., Liang, H.Y., Fan, W.M., Goldfarb, R.,
Yin, Q.Z., 2012a. Geochemical constraints on adakites of different origins and copper
mineralization. J. Geol. 120 (1), 105–120.
Sun, W.D., Ling, M.X., Ding, X., Chung, S.L., Yang, X.Y., Fan, W.M., 2012b. The genetic asso-
ciation of adakites and Cu–Au ore deposits: a reply. Int. Geol. Rev. 54 (3), 370–372.
Sun, W.D., Li, S., Yang, X.Y., Ling, M.X., Ding, X., Duan, L.A., Zhan, M.Z., Zhang, H., Fan, W.M.,
2013a. Large-scale gold mineralization in eastern China induced by an Early Creta-
ceous clockwise change in Pacific plate motions. Int. Geol. Rev. 55 (3), 311–321.
Sun, W.D., Liang, H.Y., Ling, M.X., Zhan, M.Z., Ding, X., Zhang, H., Yang, X.Y., Li, Y.L., Ireland,
T.R., Wei, Q.R., Fan, W.M., 2013b. The link between reduced porphyry copper deposits
and oxidized magmas. Geochim. Cosmochim. Acta 103, 263–275.
Sun, W.D., Huang, R.F., Liang, H.Y., Ling, M.X., Li, C.Y., Ding, X., Zhang, H., Yang, X.Y.,
Ireland, T., Fan, W.M., 2014a. Magnetite–hematite, oxygen fugacity, adakite and por-
phyry copper deposits: reply to Richards. Geochim. Cosmochim. Acta 126, 646–649.
Sun, W.D., et al., 2014b. The genetic association between magnetite–hematite and por-
phyry copper deposits: reply to Pokrovski. Geochim. Cosmochim. Acta 126, 639–642.
Takagi, T., 2004. Origin of magnetite- and ilmenite-series granitic rocks in the Japan Arc.
Am. J. Sci. 304 (2), 169–202.
Tang, G.J., Wang, Q., Wyman, D.A., Li, Z.X., Zhao, Z.H., Jia, X.H., Jiang, Z.Q., 2010. Ridge sub-
duction and crustal growth in the Central Asian Orogenic Belt: evidence from Late
Carboniferous adakites and high-Mg diorites in the western Junggar region, northern
Xinjiang (west China). Chem. Geol. 277 (3–4), 281–300.
Taylor, H.P., 1974. The application of oxygen and hydrogen isotope studies to problems of
hydrothermal alteration and ore deposition. Econ. Geol. 69, 843–883.
Taylor, B.E., 1992. Degassing of H2O from rhyolite magma during eruption and shallow
inrusion, and the isotopic composition of magmatic water in hydrothermal systems.
Geol. Surv. Jpn. Rep. 279, 190–194.
Thieblemont, D., Stein, G., Lescuyer, J.L., 1997. Epithermal and porphyry deposits: the
adakite connection. C.R. Acad. Sci., Ser. IIa: Sci. Terre Planets 325 (2), 103–109.
Thompson, J.F.H., Sillitoe, R.H., Baker, T., Lang, J.R., Mortensen, J.K., 1999. Intrusion-relate
gold deposits associated with tungsten–tin provinces. Mineral. Deposita 34, 323–334.
Thorkelson, D.J., Breitsprecher, K., 2005. Partial melting of slab window margins: genesis
of adakitic and non-adakitic magmas. Lithos 79 (1–2), 25–41.
Titley, S.R., 1981. Porphyry copper. Am. Sci. 69 (6), 632–638.
Togashi, S., Terashima, S., 1997. The behavior of gold in unaltered island arc tholeiitic
rocks from Izu-Oshima, Fuji, and Osoreyama volcanic areas, Japan. Geochim.
Cosmochim. Acta 61 (3), 543–554.
Tomkins, A.G., 2010. Windows of metamorphic sulfur liberation in the crust: implications
for gold deposit genesis. Geochim. Cosmochim. Acta 74 (11), 3246–3259.
Vila, T., Sillitoe, R.H., 1991. Gold-rich porphyry systems in the Maricunga Belt, Northern
Chile. Econ. Geol. Bull. Soc. Econ. Geol. 86 (6), 1238–1260.
Vila, T., Sillitoe, R.H., Betzhold, J., Viteri, E., 1991. The porphyry gold deposit at Marte,
Northern Chile. Econ. Geol. Bull. Soc. Econ. Geol. 86 (6), 1271–1286.
Vry, V.H., Wilkinson, J.J., Seguel, J., Millan, J., 2010. Multistage intrusion, brecciation, and
veining at El Teniente, evolution of a nested porphyry system. Econ. Geol. 105 (1),
119–153.
Wang, Q., Wyman, D.A., Xu, J.F., Zhao, Z.H., Jian, P., Xiong, X.L., Bao, Z.W., Li, C.F., Bai, Z.H.,
2006a. Petrogenesis of Cretaceous adakitic and shoshonitic igneous rocks in the
Luzong area, Anhui Province (eastern China): implications for geodynamics and
Cu–Au mineralization. Lithos 89 (3–4), 424–446.
Wang, Q., Xu, J.F., Jian, P., Bao, Z.W., Zhao, Z.H., Li, C.F., Xiong, X.L., Ma, J.L., 2006b. Petro-
genesis of adakitic porphyries in an extensional tectonic setting, Dexing, South
China: implications for the genesis of porphyry copper mineralization. J. Petrol. 47
(1), 119–144.
Wang, Q., Wyman, D.A., Xu, J., Jian, P., Zhao, Z., Li, C., Xu, W., Ma, J., He, B., 2007a. Early Cre-
taceous adakitic granites in the Northern Dabie Complex, central China: implications
for partial melting and delamination of thickened lower crust. Geochim. Cosmochim.
Acta 71 (10), 2609–2636.
Wang, Q., Wyman, D.A., Xu, J.F., Zhao, Z.H., Jian, P., Zi, F., 2007b. Partial melting of thick-
ened or delaminated lower crust in the middle of eastern China: implications for
Cu–Au mineralization. J. Geol. 115 (2), 149–161.
Wang, G.G., Ni, P., Wang, R.C., Zhao, K.D., Chen, H., Ding, J.Y., Zhao, C., Cai, Y.T., 2013. Geo-
logical, fluid inclusion and isotopic studies of the Yinshan Cu–Au–Pb–Zn–Ag deposit,
View publication stats
131
South China: implications for ore genesis and exploration. J. Asian Earth Sci. 74,
343–360.
Wilkinson, J.J., 2013. Triggers for the formation of porphyry ore deposits in magmatic arcs.
Nat. Geosci. 6 (11), 917–925.
Wones, D.R., Eugster, H.P., 1965. Stability of biotite: experiement, theory, and application.
Am. Mineral. 50, 1228–1272.
Wu, H.Y., Zhang, L.C., Wan, B., Chen, Z.G., Zhang, X.J., Xiang, P., 2011. Geochronological and
geochemical constraints on Aolunhua porphyry Mo–Cu deposit, northeast China, and
its tectonic significance. Ore Geol. Rev. 43 (1), 78–91.
Xiao, B., Qin, K.Z., Li, G.M., Li, J.X., Xia, D.X., Chen, L., Zhao, J.X., 2012. Highly oxidized
magma and fluid evolution of Miocene Qulong giant porphyry Cu–Mo deposit, South-
ern Tibet, China. Resour. Geol. 62 (1), 4–18.
Xu, J.F., Shinjo, R., Defant, M.J., Wang, Q.A., Rapp, R.P., 2002. Origin of Mesozoic adakitic in-
trusive rocks in the Ningzhen area of east China: Partial melting of delaminated lower
continental crust? Geology 30 (12), 1111–1114.
Xu, W.L., Wang, Q.H., Wang, D.Y., Guo, J.H., Pei, F.P., 2006. Mesozoic adakitic rocks from
the Xuzhou–Suzhou area, eastern China: evidence for partial melting of delaminated
lower continental crust. J. Asian Earth Sci. 27 (4), 454–464.
Yang, X.Y., Wang, K.R., Yang, X.M., Sun, L.G., 2002. Characteristics of mineralization and
gold occurrence in Shaxi porphyry copper–gold deposit, central Anhui, China.
Neues Jahrb. Mineral. Abh. 177 (3), 293–320.
Yang, Z.M., Hou, Z.Q., White, N.C., Chang, Z.S., Li, Z.Q., Song, Y.C., 2009. Geology of the post-
collisional porphyry copper–molybdenum deposit at Qulong, Tibet. Ore Geol. Rev. 36
(1–3), 133–159.
Yang, L., Chen, F.K., Liu, B.X., Hu, Z.P., Qi, Y., Wu, J.D., He, J.F., Siebel, W., 2013. Geochemistry
and Sr–Nd–Pb–Hf isotopic composition of the Donggou Mo-bearing granite porphy-
ry, Qinling orogenic belt, central China. Int. Geol. Rev. 55 (10), 1261–1279.
Yogodzinski, G.M., Volynets, O.N., Koloskov, A.V., Seliverstov, N.I., Matvenkov, V.V., 1994.
Magnesian andesites and the subduction component in a strongly calc-alkaline series
at Piip Volcano, Far Western Aleutians. J. Petrol. 35 (1), 163–204.
Zeng, Q.D., Liu, J.M., Qin, K.Z., Fan, H.R., Chu, S.X., Wang, Y.B., Zhou, L.L., 2013. Types, char-
acteristics, and time–space distribution of molybdenum deposits in China. Int. Geol.
Rev. 55 (11), 1311–1358.
Zhang, Q., Wang, Y., Wang, Y.L., 2001a. Preliminary study on the components of the lower
crust in east China Plateau during Yanshanian Period: constraints on Sr and Nd isoto-
pic compositions of adakite-like rocks. Acta Petrol. Sin. 17 (4), 505–513.
Zhang, Q., Wang, Y., Qian, Q., Yang, J.H., Wang, Y.L., Zhao, T.P., Guo, G.J., 2001b. The char-
acteristics and tectonic–metallogenic significances of the adakites in Yanshan period
from eastern China. Acta Petrol. Sin. 17 (2), 236–244 (in Chinese with English
abstract).
Zhang, Z.X., Yang, F.Q., Yan, S.H., Zhang, R., Chai, F.M., Liu, F.L., Geng, X.X., 2010. Sources of
ore-forming fluids and materials of the Baogutu porphyry copper deposit in Xinjiang:
constrains from sulfur–hydrogen–oxygen isotopes geochemistry. Acta Geol. Sin. 26,
707–716 (in Chinese with English abstract).
Zhang, H., Ling, M.X., Liu, Y.L., Tu, X.L., Wang, F.Y., Li, C.Y., Liang, H.Y., Yang, X.Y., Arndt, N.T.,
Sun, W.D., 2013. High oxygen fugacity and slab melting linked to Cu mineralization:
evidence from Dexing porphyry copper deposits, southeastern China. J. Geol. 121 (3),
289–305.
Zhang, Y., Sun, J.G., Chen, Y.J., Zhao, K.Q., Gu, A.L., 2013. Re–Os and U–Pb geochronology of
porphyry Mo deposits in central Jilin Province: Mo ore-forming stages in northeast
China. Int. Geol. Rev. 55 (14), 1763–1785.
Zhang, H., Li, C.Y., Yang, X.Y., Sun, Y.L., Deng, J.H., Liang, H.Y., Wang, R.L., Wang, B.H., Wang,
Y.X., Sun, W.D., 2013. Shapinggou: the largest Climax-type porphyry Mo deposit in
China. Int. Geol. Rev. 56, 313–331.
Zhou, Q., Jiang, Y.H., Zhang, H.H., Liao, S.Y., Jin, G.D., Zhao, P., Jia, R.Y., Liu, Z., 2013. Mantle
origin of the Dexing porphyry copper deposit, SE China. Int. Geol. Rev. 55 (3),
337–349.
Zhu, X., Huang, C., Rui, Z., Zhou, Y., Zhu, X., Hu, C., Mei, Z., 1983. The Geology of Dexing
Porphyry Copper Ore Field. Geological Publishing House, Beijing (in Chinese).
Zhu, L.M., Zhang, G.W., Guo, B., Lee, B., Gong, H.J., Wang, F., 2010. Geochemistry of the
Jinduicheng Mo-bearing porphyry and deposit, and its implications for the
geodynamic setting in East Qinling, PR China. Chem. Erde 70 (2), 159–174.