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Magnetite-hematite, oxygen fugacity, adakite

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Richards

Article in Geochimica et Cosmochimica Acta · January 2014

DOI: 10.1016/j.gca.2013.07.037

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Response

Magnetite–hematite, oxygen fugacity, adakite

and porphyry copper deposits: Reply to Richards
Wei-dong Sun a,⇑, Rui-fang Huang b,c, Hua-ying Liang a,⇑, Ming-xing Ling b,
Cong-ying Li a, Xing Ding b, Hong Zhang b, Xiao-yong Yang d, Trevor Ireland e,
Wei-ming Fan b
a
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
d
Key Laboratory of Crust–Mantle Materials and Environments, University of Science and Technology of China, Hefei 230026, China
e
Research School of Earth Sciences, Australian National University, Canberra 0200, Australia

Received 29 May 2013; accepted in revised form 28 July 2013; available online 8 August 2013

We thank Richards (2013) for the comment, which pro-
vides us a chance to better explain our concept and model.
Porphyry Cu deposits are closely associated with oxidized
adakitic magmas, the connection behind these association
is still in debate.
1. The title of Sun et al. (2013) is based on the obser-
vation that sulfate is the dominant S species in the
parental magma, but sulfides are dominant in
porphyry deposits. Richards claims that sulfide-
dominant porphyry deposits are more oxidized
than their sulfate-dominant parental magmas,
which does not make sense. The S6+/Stotal ratio is
sensitive to oxygen fugacity (Matthews et al.,
1994; Metrich and Clocchiatti, 1996; Jugo et al.,
2005). The porphyry Cu system (both parental
magmas and deposits) is rich in sulfur, such that
its oxygen fugacity is usually controlled by sulfur
speciation. Sulfate is the dominant sulfur species
in magmas but is very rare in sulfide ores, with
scarce isolated anhydrite inclusions. We take this
as a clear sign that parental magmas are much
more oxidized than the ore bodies. We also would
like to point out that the magnetite–pyrite bound-
ary lies above the SO2–H2S (not sulfate) boundary
⇑ Corresponding authors. Tel.: +86 2085290215 (W. Sun).
E-mail addresses: weidongsun@gig.ac.cn (W.-d. Sun), lianghy@
gig.ac.cn (H. Liang).
at temperatures higher than 650 °C, which is much
higher than the mineralization temperature. More
importantly, both magnetite, pyrite are solid
states, whereas SO2 and H2S are not, such that
the SO2–H2S boundary assumes 1 unit concentra-
tions of both species.
When talking about the mechanism of porphyry miner-
alization, we are dealing with three things, parental mag-
mas, ore bodies and the linkage between them
(mineralization process). In general, the redox reactions
of Fe and S are the key controlling factors of porphyry
Cu deposits (Sun et al., 2004, 2013; Liang et al., 2009).
The most optimal oxygen fugacity of parental magmas is
higher than DFMQ+2 (Mungall, 2002), such that there is
sufficient sulfate in the magmas to obtain high initial Cu
contents, and lower than the HM buffer to maintain ferrous
iron for the reduction of sulfate during the mineralization
process (Sun et al., 2013). As discussed in detail in Sun
et al. (2013), the oxidation potential of sulfate increases
with decreasing pH during the mineralization process,
which eventually reaches the HM buffer (Sun et al., 2013).
We would like to point out also that the hematite-magnetite
assemblage is quite common in porphyry systems, which
has also been reported by many others, including (Sillitoe,
2010). Nevertheless, the pH values increase during altera-
tions that consume H+, consequently, the oxidation poten-
tial of sulfate decreases. The very low S6+/Stotal ratio in
porphyry ore bodies (sulfide rich) indicates oxygen fugacity
much lower than the FMQ buffer. Nevertheless, the reac-

0016-7037/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.gca.2013.07.037
 W.-d. Sun et al. / Geochimica et Cosmochimica Acta 126 (2014) 646–649
tions among solid minerals are very slow once fluids dried
out. This explains the coexistence of minerals that formed
under very different oxygen fugacities.
2. Richards misunderstood previous papers (Pokrov-
ski and Dubrovinsky, 2011; Sun et al., 2013). The
sulfur speciation is controlled by physicochemical
conditions. S3 was shown as the dominant sulfur
species by Raman spectroscopy at 25° to 450 °C
and 0.5 to 3.5 GPa and 1 < pH < 7 (Pokrovski
and Dubrovinsky, 2011). Sulfate, however, is more
abundant at higher pH and oxygen fugacities
(Fig. 3 of Pokrovski and Dubrovinsky, 2011),
especially in fluids under pressures of 0.3–1.0 GPa
and temperatures up to 700 °C (Ni and Keppler,
2012). Note, the lines separating the domains of
two neighboring species correspond to the concen-
tration ratio 1:1 of these species in solution.
Richards argues that SO2 is the principal form of sulfur
in magmatic volatile phases and the disproportionation of
aqueous SO2 upon cooling forms “coprecipitation” of mag-
netite with sulfide and anhydrite. The references cited by
(Richards, 2013) are all about hydrothermal systems. Sulfur
behaves differently in porphyry systems under much higher
pressures. High-pressure experiments show that sulfate is
the dominant sulfur species in magmas under high oxygen
fugacity, with some sulfite (S4+) (Jugo, 2009; Jugo et al.,
2010). High concentrations of SO2 are observed in volatile
phases (Einaudi et al., 2003; Heinrich, 2005). Therefore, the
dominant reaction among sulfur species is more likely to go
opposite to the direction proposed by Richards (2013), i.e.,
sulfide reacts with sulfate, forming SO2 (Eq. (1)). Moreover,
H2S tends to react with SO2, forming S (Eq. (2)). Note, na-
tive S is abundant in volcanic craters, but is not reported in
any porphyry deposits, yet. For the same reasons, the reac-
tions 2 and 3 of Richards (2013) are not likely to be the
main reactions that are responsible to the final mineraliza-
tion, either.
H2 S þ 3H2 SO4 ¼ 4SO2 þ 4H2 O2 ð1Þ
H2 S þ SO2 ¼ 3S þ 2H2 O ð2Þ
3. Richards criticized that reactions (1, 2, 4) of Sun
et al. (2013) because they are all very high posi-
tively charged. This is a misunderstanding. These
reactions were all ionic equations, simplified to
make it more straightforward. The apparent posi-
tive charge is actually balanced by Cl and other
anions, which are not shown in these reactions.
4. Richards and Kerrich set “MgO normally <3 wt
percent” as a criterion, but they set “Mg number
0.5” as well (Richards and Kerrich, 2007), which
is a far tighter constraint than the former and was
the main point of dissent of Sun et al., (2013). In
other words, the word “normally” does not make
647
much difference. Furthermore, as discussed in Sun
et al., (2013), they also set up Ni, Cr criteria that
go towards the opposite fractionation directions.
Richards further claims that slab melts react with over-
lying mantle through open system AFC-type processes,
such that it is very difficult to infer source processes from
geochemical data. This is very surprising to us. Essentially
all magmas experience AFC-type processes, as do adakites.
The slab-melting model is supported by high-pressure
experiments (Rapp and Watson, 1995; Rapp et al., 1999).
More importantly, reactions of adakite with surrounding
mantle peridotite and crusts tend to erase the unique char-
acteristics of adakite. In other words, adakites may be
changed to normal arc rocks through AFC-type processes
(Sun et al., 2012a). Therefore, adakitic characteristics are
indeed original.
5. Richards argues that the partition coefficients of
Cu between amphibole and magmas vary dramat-
ically from 0.05 to 16 or if only newer data were
used, from 0.49 to 1.8 (GERM). This gives us an
opportunity to clarify. Richards attributed the for-
mation of adakite to amphibole crystallization
(Richards and Kerrich, 2007). We argued that
amphibole cannot explain the association between
porphyry Cu deposits and adakites (Sun et al.,
2011, 2012a,b, 2013). Partition coefficient values
lower than 1 are either for basaltic andesite or
for rhyolite, whereas it is compatible in amphibole
for andesite (up to 16, GERM). Adakite with por-
phyry Cu deposits are mostly andesite, therefore
amphibole is not favorable for Cu mineralization
(Sun et al., 2011, 2012b).
6. Richards argued that high water contents is
responsible to Cu mineralization (Richards and
Kerrich, 2007; Richards, 2012). We don’t think
this is the case, because subduction of younger oce-
anic crusts has much (e.g., Chile) more porphyry
deposits, whereas subduction of older oceanic
crusts has much fewer (e.g., Japan) (Sun et al.,
2012b). This time he changed his mind and argued
that “most of the hydration occurred near the mid-
ocean ridges” based on the distribution of hydro-
thermal activities. This argument is inconsistent
with the observation that older oceanic crust is sys-
tematically more altered and wetter than young
oceanic crust. The effects of oxygen fugacity on
porphyry mineralization has been discussed in
detail in Sun et al. (2011, 2013).
Our main disagreement with Richards (2013) focuses on
the linkage between adakite and porphyry copper mineral-
ization. Adakite was originally proposed to represent slab
melts with characteristic high Sr/Y ratios (Defant and
Drummond, 1990). It has long been recognized that most
648 W.-d. Sun et al. / Geochimica et Cosmochimica Acta 126 (2014) 646–649
of the porphyry Cu deposits are genetically associated with
adakites (Thieblemont et al., 1997; Sajona and Maury,
1998; Oyarzun et al., 2001; Ling et al., 2009, 2011, 2013;
Sun et al., 2010; Zhang et al., 2013), or so called high Sr/
Y rocks (Richards, 2011; Chiaradia et al., 2012). This was
attributed to the high Cu concentrations in oceanic slabs
(which are about 3 times higher than the continental crust
and the mantle) and high oxygen fugacity during plate sub-
duction (Sun et al., 2011, 2012a). Alternatively, while agree-
ing that most porphyry Cu deposits are closely associated
with high Sr/Y rocks, the involvement of water was taken
as the key controlling factor (Richards, 2011; Chiaradia
et al., 2012). Addition of water cannot explain the charac-
teristics of adakite (high Sr/Y, Sr; low Y, Yb, etc.), nor
the distribution of Cu porphyry deposits (porphyry Cu
deposits are closely associated with the subduction of
young oceanic crust, whereas there are no porphyry Cu
deposits in Japan) (Sun et al., 2012b, 2013).
Richards (2013) argues that adakites have low Cu con-
centrations and therefore adakite is not favorable for Cu
porphyry mineralization. This is likely a misunderstanding
because slab melts initially have high Cu (Sun et al., 2011).
The Cu concentrations of adakitic volcanic rocks compiled
by Sun et al., (2011), however, are indeed lower than many
normal arc volcanic rocks. As discussed in detail previously,
essentially all those rocks have experienced degassing (where-
by Cu is lost), whereas Cu releases to fluids during sulfate
reduction (Sun et al., 2004, 2011). Therefore, magmas with
higher initial Cu concentration coupled with lower ultimate
concentration contribute more to mineralization, and there-
fore we maintain that adakites are more favorable for Cu
mineralization.
ACKNOWLEDGMENT
The study is supported by the National Natural Science Foun-
dation of China (Nos. 41090374, 41121002, 41172080). GIG Con-
tribution No. 1713.
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Associate editor: Edward Ripley