Lithos 233 (2015) 27–45

Contents lists available at ScienceDirect

Lithos
journal homepage: www.elsevier.com/locate/lithos

Invited review article

The oxidation state, and sulfur and Cu contents of arc magmas:

implications for metallogeny
Jeremy P. Richards ⁎
Dept. Earth and Atmospheric Sciences, University of Alberta, Edmonton, Alberta, Canada T6G 2E3

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

Article history: Global data for measured Fe2O3/FeO ratios and Cu contents in unaltered volcanic and intrusive arc rocks indicate
Received 8 July 2014 that, on average, they are slightly more oxidized than other magmas derived from depleted upper mantle (such
Accepted 11 December 2014 as MORB), but contain similar Cu contents across their compositional ranges. Although Cu scatters to elevated
Available online 26 December 2014
values in some intermediate composition samples, the bulk of the data show a steady but gentle trend to
lower concentrations with differentiation, reaching modal values of ~ 50–100 ppm in andesitic rocks. These
Keywords:
Oxidation state
data suggest that Cu is mildly compatible during partial melting and fractionation processes, likely reflecting
Magma minor degrees of sulfide saturation throughout the magmatic cycle. However, the volume of sulfides must be
Sulfur small such that significant proportions of the metal content remain in the magma during fractionation to inter-
Copper mediate compositions. Previous studies have shown that andesitic magmas containing ~50 ppm Cu can readily
Gold form large porphyry-type Cu deposits upon emplacement in the upper crust.
Porphyry A review of the literature suggests that the elevated oxidation state in the asthenospheric mantle wedge source of
arc magmas (ΔFMQ ≈ +1 ± 1) derives from the subduction of seawater-altered and oxidized oceanic crust, and
is transmitted into the mantle wedge via prograde metamorphic dehydration fluids carrying sulfate and other
oxidizing components. Progressive hydration and oxidation of the mantle wedge may take up to ~10 m.y. to
reach a steady state from the onset of subduction, explaining the rarity of porphyry deposits in primitive island
arcs, and the late formation of porphyries in continental arc magmatic cycles. Magmas generated from this
metasomatized and moderately oxidized mantle source will be hydrous basalts containing high concentrations
of sulfur, mainly dissolved as sulfate or sulfite. Some condensed sulfides (melt or minerals) may be present
due to the high overall fS2, despite the moderately high oxidation state. These sulfides may retain some highly
siderophile elements in the source, but are unlikely to be sufficiently voluminous to significantly affect the budget
of more modestly sulfide-compatible and more abundant elements such as Cu and Mo. These primary magmas
can therefore be considered to be largely Cu-Mo-undepleted, although highly siderophile elements such as Au
and platinum group elements (PGE) may be depleted unless no sulfides remain in the source. The latter condition
seems unlikely during active subduction because of the continuous flux of fresh sulfur from the slab, but may
occur during post-subduction re-melting (leading to potentially Au-rich post-subduction porphyry and alkalic-
type epithermal systems).
Lower crustal differentiation of main-stage arc magmas results in some loss of Cu to residual or cumulate sulfides,
but again the amount appears to be minor, and does not drastically reduce the Cu content of derivative
intermediate-composition melts. Fractionation and devolatilization affect the oxidation state of the magma in
competing ways, but, while crystallization and segregation of Fe3+-rich magnetite can cause reduction in re-
duced to moderately oxidized evolved magmas, this effect appears to be outweighed by the oxidative effects of
degassing reduced or weakly oxidized gaseous species such as H2, H2S, and SIVO2, and preferential solvation
and removal of Fe2+ in saline hydrothermal fluids. Consequently, most arc magmatic suites show slight increases
in oxidation state during differentiation, reaching typical values of ΔFMQ = +1 to +2.
This oxidation state is significant, because it corresponds to the transition from dissolved sulfide to sulfate dom-
inance in magmas. It has been shown that Cu and Au solubilities in silicate magma increase up to this level
(ΔFMQ ≈ +1), but while Cu solubility continues to increase at higher oxidation states, Au shows a precipitous
drop as sulfide, which solvates Au in the melt, is converted to sulfate. This may explain the somewhat restricted
distribution of Au-rich porphyry Cu deposits, but the general association of porphyry Cu deposits with relatively
oxidized magmas.
Exsolution of a saline, high temperature aqueous fluid enables metals to partition from the magma into a highly
mobile volatile phase. Sulfur also partitions strongly into this fluid phase, predominantly as SO2 at ΔFMQ = +1

⁎ Tel.: +1 780 492 3430.

E-mail address: Jeremy.Richards@ualberta.ca.

http://dx.doi.org/10.1016/j.lithos.2014.12.011
0024-4937/© 2014 Elsevier B.V. All rights reserved.
28 J.P. Richards / Lithos 233 (2015) 27–45

to +2. However, as the fluid cools below ~400 °C, SIVO2 disproportionates to form reduced H2S−II and oxidized
H2SVIO4. The H2S bonds with metals in solution to precipitate as Cu- and Mo-sulfides, while the H2SO4 (and HCl)
generates progressively acidic wallrock alteration (phyllic, argillic, advanced argillic). Gold may precipitate with
early Cu/Mo-sulfides, but some may also stay in solution as bisulfide complexes, eventually reaching the
epithermal environment.
Thus, three components, [S], [H2O], and fO2 work together throughout subduction and arc magmatic processes to
transport chalcophile and siderophile metals from the mantle into the upper crust, where they may be concen-
trated by hydrothermal processes to form ore deposits. These processes are far from 100% efficient, and metals
(especially highly siderophile elements such as Au and PGE) may be left behind at various stages of the passage
of arc magmas through the lithosphere, where they may form potentially metalliferous source rocks for partial
melts and subsequent magmatic-hydrothermal ore deposits generated during later tectonomagmatic events.
© 2014 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
2. Evidence for, and causes and effects of oxidation in sub-arc mantle and arc magmas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.1. Methods of estimating magmatic fO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.1.1. Whole-rock Fe3 +/Fe2 + ratios . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.1.2. Whole-rock chemical ratios . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.1.3. Rare earth elements in rocks and minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.1.4. Mineral equilibria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.2. Oxidation state of sub-arc mantle xenoliths and orogenic peridotites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.3. Oxidation state of arc magmas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.4. Redox effects of subduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2.5. Partial melting in the mantle wedge and the calc-alkaline trend . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2.6. Redox effects on metallogeny during partial melting and magmatic differentiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
2.7. The role of sulfur on metal solubility during partial melting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
2.8. The source of sulfur in arc magmas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
3. Lower crustal MASH processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
4. Fractional crystallization and devolatilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
5. The magmatic to hydrothermal transition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
6. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39

1. Introduction
A major proportion of the world’s Cu, Mo, and Au is mined from hy-
drothermal ore deposits (typically porphyry and epithermal deposits)
associated either directly or indirectly with subduction-related
magmas. While all volcanic arcs feature hydrothermal systems, large
mineral deposits tend to form in clusters or age-related belts within
these arcs, or as isolated deposits in back-arc settings. Cline and
Bodnar (1991; updated in Cline, 1995) convincingly demonstrated
that an average arc andesite containing 50 ppm Cu has the potential
to form an economic porphyry Cu deposit, but clearly not all do. A ques-
tion therefore remains as to what conditions convert potential to actual
ore formation?
The formation of a large porphyry ore deposit requires the consecu-
tive, cumulative, and optimized execution of numerous steps, starting
with the generation of sufficient volumes of fertile magma, and ending
with efficient hydrothermal transport and ore depositional processes.
Malfunctioning or omission of any one of these steps can reduce or
eliminate the potential for subsequent ore formation within an individ-
ual deposit, but failure of an early step is most likely to lead to belt-scale
barren systems (Richards, 2013).
Cline and Bodnar (1991) modeled the partitioning of Cu and Cl
between hydrothermal fluids and andesitic melt with an initial compo-
sition of 2.5 wt.% H2O, Cl/H2O = 0.1, and 50 ppm Cu, at various pres-
sures as a function of the degree of magmatic crystallization. They
concluded that ≤30 km3 of magma with this composition could gener-
ate an economic porphyry deposit (≥250 million tons of 0.75 wt.% Cu)
if emplaced at moderate depths (2 kb), with larger deposits potentially
being formed from larger volumes of magma. A caveat to this model,
however, is that Cu must behave incompatibly in such magmas: in
other words, it must not be lost significantly from the melt phase
through crystallization or early (deep) fluid exsolution prior to
shallow-level partitioning into a magmatic-hydrothermal system
(Spooner, 1993). Compatible behavior rapidly strips Cu from the
magma, and reduces the potential to form porphyry-type ore deposits
(or requires larger volumes of magma to form an equivalent sized de-
posit). Copper does not partition strongly into most igneous silicate
and oxide minerals, but is readily sequestered by sulfide phases
(melts, or minerals such as pyrrhotite and intermediate solid solution,
ISS; Jugo et al., 1999). Consequently, the quickest way to reduce
the economic potential of a magma is to saturate it with a sulfide
phase, and allow the dense sulfides to settle out at depth prior to hydro-
thermal fluid exsolution (unless of course the objective is to form an
orthomagmatic sulfide deposit; e.g., Hamlyn and Keays, 1986; Hamlyn
et al., 1985).
Arc magmatic systems are characteristically S-rich (de Hoog et al.,
2001; Wallace, 2005; Wallace and Edmonds, 2011), and therefore
might be expected to undergo early sulfide saturation were it not for an-
other key characteristic: their relatively high (but variable) oxidation
state, compared to most other mantle-derived magmas (Evans, 2012;
Evans et al., 2012; Gill, 1981; Kelley and Cottrell, 2009; Laubier et al.,
2014; Stamper et al., 2014a). Under relatively oxidizing conditions
(ΔFMQ ≥ +1, where ΔFMQ is the log fO2 difference between the sample
value and the fayalite–magnetite-quartz mineral buffer), the bulk of the
sulfur will be present in the melt as SVIO2−4 or SIVO2 rather than S2−,
and there will therefore be less tendency to exsolve large volumes of
 J.P. Richards / Lithos 233 (2015) 27–45
sulfide melt or precipitate sulfide minerals (Carroll and Rutherford,
1985; Métrich and Clocchiatti, 1996; Métrich et al., 2002; Nilsson and
Peach, 1993). Thus, relatively oxidized arc magmas, with average con-
centrations of H2O, Cl, Cu, and S, should meet the primary criteria
for porphyry ore formation of Cline and Bodnar (1991). However,
unlike the concentrations of these chemical components, which might
be expected to control ore potential in a proportional fashion, magmatic
redox state appears to have an almost stepwise effect, with porphyry Cu
ore potential falling suddenly at oxidation states below ΔFMQ ≈ + 1
(Botcharnikov et al., 2011; Zajacz et al., 2012). Thus, it is particularly im-
portant to understand what is controlling the overall redox state of arc
systems, and what conditions might cause changes around the critical
value of ΔFMQ ≈ +1.
This paper explores the controls on this parameter from oxidative
seafloor alteration, through mantle wedge metasomatism and partial
melting, deep crustal magmatic processes, and finally to shallow-level
crystallization and devolatilization. Many of the arc-scale variations in
arc magma fertility can be understood in terms of the effects of fO2 on
these processes.
2. Evidence for, and causes and effects of oxidation in sub-arc mantle
and arc magmas
Subduction zones have long been thought to generate relatively ox-
idized magmas (ΔFMQ = +0.5 to + 2; Ballhaus et al., 1991; Brounce
et al., 2014; Gill, 1981; Rowe et al., 2009; Zimmer et al., 2010), compared
with other depleted mantle-derived magmas such as tholeiitic mid-
ocean ridge basalts (e.g., MORB, ΔFMQ = −1 to 0; Bézos and Humler,
2005; Christie et al., 1986; Frost and McCammon, 2008; Laubier et al.,
2014). However, estimating the oxidation state of magmas and source
rocks from chemical information stored in cooled rocks is complex,
and is based on numerous assumptions of equilibrium and estimates
of partitioning relationships. The methods most commonly used to esti-
mate fO2 in magmas are reviewed below, together with the various lines
of evidence for sub-arc mantle and magma oxidation state. These data
confirm the elevated but variable oxidation state of the sub-arc mantle
and derived magmas.
2.1. Methods of estimating magmatic fO2
2.1.1. Whole-rock Fe3+/Fe2+ ratios
Wet-chemical analysis of FeO concentrations in whole-rock samples
can be used to calculate actual Fe2O3 concentrations from Fe2O3(total)
data commonly generated by X-ray fluorescence or inductively coupled
plasma analyses. Whole-rock Fe3+/Fe2+ ratios can then be used to esti-
mate the oxidation state of rock samples (Blevin, 2004; Carmichael and
Ghiorso, 1986). A problem with this method, however, is that Fe2O3/FeO
ratios in igneous rocks are highly susceptible to weathering, alteration,
and redox changes due to near-solidus degassing. Glasses tend to yield
the best estimates of original magmatic fO2, but even otherwise fresh
crystalline rocks may yield results 1–2 log units higher than comagmatic
glasses due to processes such as degassing (Christie et al., 1986). Alter-
native approaches to measuring whole-rock Fe3 +/Fe2 + ratios are
Mössbauer spectroscopy (Mysen et al., 1985; Wood and Virgo, 1989),
and micro X-ray absorption near-edge structure (μ-XANES; Cottrell
et al., 2009); the latter method permits direct microbeam-scale mea-
surement on glasses, thereby avoiding alteration, crystals, etc.
2.1.2. Whole-rock chemical ratios
In addition to Fe, V and Cr occur in igneous rocks and magmas in
multiple valence states, with different partitioning behaviors between
melts and minerals (Canil, 1999). When normalized to a chemically
similar, but non redox-dependent element such as Sc or Yb, empirical
indications of magmatic oxidation state can be inferred (Laubier et al.,
2014; Lee et al., 2005; Li and Lee, 2004). However, it is unclear how ac-
curately these trace element proxies reflect actual magmatic oxidation
29
state, and to what degree they are independent of other processes
such as original (pre-subduction) source composition and partitioning
effects (Brounce et al., 2013).
2.1.3. Rare earth elements in rocks and minerals
The rare earth elements (REE) Eu and Ce also occur in two valence
states in magmas (Eu2+ and Eu3+, and Ce3+ and Ce4+) with different
partition coefficients into minerals such as plagioclase (in which only
Eu2 + is compatible as a substitution for Ca2 +; Frey et al., 1978;
Hanson, 1980) and zircon (in which Eu2+ is excluded and Ce4+ is pref-
erentially accommodated as substitutions for Zr4+; Ballard et al., 2002;
Dilles et al., 2015). Consequently, relatively reduced magmas that frac-
tionate Eu2+-rich plagioclase will show negative Eu anomalies on nor-
malized rare-earth-element diagrams, but oxidized magmas will not.
Rare earth element analyses of zircons will also show negative Eu anom-
alies in reduced rocks because Eu2+ is preferentially excluded from zir-
con (and the magma may already have been depleted in Eu by
plagioclase fractionation). In contrast, Ce will show positive anomalies
in zircons from oxidized magmas because Ce4 + is preferentially
partitioned into this mineral. Ballard et al. (2002), Trail et al. (2011,
2012) and Burnham and Berry (2012, 2014) have provided empirical
relationships to estimate magmatic oxidation state from the magnitude
of Ce and Eu anomalies in zircon, which offer insights into relatively
late stage conditions during crystallization of intermediate-to-felsic
magmas.
2.1.4. Mineral equilibria
Electron microprobe analyses of coexisting mineral pairs are widely
used to estimate conditions of crystallization such as pressure, temper-
ature, and fO2, assuming chemical equilibrium and lack of recrystalliza-
tion or exsolution. One of the most commonly used mineral pairs is
magnetite–ilmenite, whose compositions, corrected stoichiometrically
for Fe3+/Fe2+ distribution (Droop, 1987), can be used to estimate fO2
from the equilibrium reaction:
SiO2 þ 2Fe2 TiO4½Usp ¼ 2FeTiO3½ilmenite þ Fe2 SiO4½Fay ð1Þ
where Usp is the ulvospinel component in magnetite, and Fay is the
fayalite component in olivine, or equivalent in pyroxenes (Andersen
et al., 1993; Lepage, 2003). The great advantage of this method is that
it uses cheap and quick analytical techniques with microbeam resolu-
tion. However, the relatively low precision and accuracy of electron mi-
croprobe analyses, combined with assumptions of chemical equilibrium
and stoichiometry, mean that this method is likely only accurate to
± 0.15 log fO2 units at best (Andersen et al., 1993; Sauerzapf et al.,
2008). Moreover, coexisting magnetite and ilmenite are not present in
all igneous rocks, and even where present they are commonly not clear-
ly in textural equilibrium (e.g., magnetite microphenocrysts, but ilmen-
ite crystallites in the matrix), or have experienced exsolution or
oxidation reactions during cooling (e.g., Saito et al., 2004).
Amphibole compositions have also been used as an oxybarometer,
based on an empirical relationship between magmatic fO2 and a Mg
index (Ridolfi et al., 2010). This method has the advantage that amphi-
bole is commonly present in arc plutonic and volcanic rocks, but its de-
pendence on multiple element electron microprobe analyses, and the
commonly complex history of amphiboles in igneous rocks leads to a
relatively high degree of uncertainty in the interpretation of the results.
2.2. Oxidation state of sub-arc mantle xenoliths and orogenic peridotites
Direct estimates of oxidation state in the sub-arc mantle have been
obtained from ultramafic xenoliths in primitive arc magmas from a
number of locations around the world, and from orogenic peridotites
thought to represent obducted fragments of sub-arc mantle wedge. Rel-
atively high oxidation states are indicated in the majority of cases (Arai
and Ishimaru, 2008; Frost and McCammon, 2008). Examples are
30 J.P. Richards / Lithos 233 (2015) 27–45
summarized in Fig. 1, and include: spinel lherzolite xenoliths from
Ichinomegata, Japan, with ΔFMQ = 0 to + 1.2 (Wood and Virgo,
1989); spinel peridotite xenoliths from Simcoe volcano, Washington,
USA, with ΔFMQ = + 0.3 to + 1.4 (Brandon and Draper, 1996);
hornblende-bearing spinel lherzolite and websterite xenoliths in andes-
ites from central Mexico with ΔFMQ = + 1.5 to + 2.4 (Blatter and
Carmichael, 1998a); spinel peridotite xenoliths from several arcs with
ΔFMQ = + 0.3 to + 2.5 (Parkinson and Arculus, 1999; Parkinson
et al., 2003); metasomatized peridotite xenoliths from Lihir Island,
Papua New Guinea, with ΔFMQ = + 1.8 to + 2.0 (McInnes et al.,
2001); peridotite xenoliths from Shiveluch volcano, Kamchatka, with
ΔFMQ = +1.4 to +2.6 (Bryant et al., 2007); and orogenic peridotites
from the Sulu belt of eastern China and the Italian Alps with ΔFMQ =
0 to +2 (Malaspina et al., 2009). However, there are also a few exam-
ples of lower oxidation states, such as spinel harzburgite and websterite
xenoliths from Patagonia, with ΔFMQ = –1.1 to –0.2 (Wang et al., 2007;
see also Malaspina et al., 2010).
These data suggest that the asthenospheric mantle wedge is com-
monly up to 3 log units more oxidized than typical MORB-depleted
mantle (ΔFMQ = − 1 to 0), but that more reducing conditions may
occur locally. Wang et al. (2007), Song et al. (2009) and Malaspina
et al. (2010) have suggested that subduction of reduced, organic
carbon-bearing sediment may be responsible for these lower values,
but the data suggest that this is not a widespread condition in arcs. In-
stead, as reviewed below, subduction (at least since deep ocean oxida-
tion following the Neoproterozoic Oxygenation Event: Evans and
Tomkins, 2011; Prouteau and Scaillet, 2013; Richards and Mumin,
2013a; Shields-Zhou and Och, 2011; or earlier: Jagoutz, 2013) appears
to be associated with variable degrees of oxidation of the overlying
mantle.
2.3. Oxidation state of arc magmas
As noted above, arc magmas have long been recognized as being
more oxidized than typical tholeiitic magmas, typically in the range
ΔFMQ = +0.5 to +2, and locally up to or above +3 (Ballhaus, 1993;
Eggins, 1993; Luhr, 1992; Mullen and McCallum, 2013; Pichavant and
Macdonald, 2007; Stamper et al., 2014a). Relatively few suites of geo-
chemical data for arc rocks include direct estimations of oxidation
state, but where separate chemical analyses of FeO have been made,
the Fe2O3/FeO ratio can be used as a proxy. A compilation of 10,104
Fig. 1. Histogram of ΔFMQ values for mantle peridotite xenoliths in arc magmas. Data from
Blatter and Carmichael (1998a; Central Mexico), Parkinson and Arculus (1999; various
locations), Parkinson et al. (2003; Grenada), Bryant et al. (2007; Shiveluch volcano,
Kamchatka), Wang et al. (2007; Cerro del Fraile, Patagonia) and Malaspina et al. (2010;
Bardane, Norway).
analyses of arc volcanic and plutonic rocks that include analytical data
for both FeO and Fe2O3 have been selected from the GEOROC database
(http://georoc.mpch-mainz.gwdg.de/georoc/), filtered for alteration to
exclude any samples where alteration is noted, or that have LOI
≥1.0 wt.% (see caption to Fig. 2 for details on selection procedures; de-
spite these precautions, it is acknowledged that some altered samples
are likely still present in the datasets). The arc samples are divided
into continental plus mature island arc (hereafter referred to as “mature
arc”) and island arc suites. They are compared to a similarly selected
suite of 1147 non-arc tholeiitic (MORB) volcanic and plutonic rocks,
presumed to be derived from normal depleted upper mantle.
The median log(Fe2O3/FeO) value is highest in the mature arc suite
(− 0.22 ± 0.39, n = 7672), lower in the island arc suite (− 0.27 ±
0.33, n = 2432), and lowest in the tholeiitic suite (− 0.69 ± 0.30,
n = 1147) (Fig. 2). When plotted against FeOTotal, the arc rocks predom-
inantly plot in the “moderately oxidized” to “strongly oxidized” fields of
Blevin (2004), whereas the tholeiites are centered on the “moderately
reduced” field (Fig. 3). Blevin (2004) suggests that the boundary be-
tween the “moderately reduced” and “moderately oxidized” fields ap-
proximates the FMQ buffer curve, which is consistent with the
majority of tholeiites being at or below FMQ, and arc magmas lying
above this buffer.
Mathez (1984), Mallmann and O'Neill (2009) and Lee et al. (2010)
have suggested that whole-rock Fe3+/Fe2+ ratios may be affected by
late stage differentiation or degassing processes, but the clear relative
difference between these two major magma suites, which is largely in-
dependent of degree of differentiation (the weak inverse correlation
with [FeOTotal] is accounted for in the slope of the field boundary lines
in Fig. 3) indicates that this is a source feature and not a process over-
print (Carmichael, 1991; Crabtree and Lange, 2012; De Hoog et al.,
2004; Kelley and Cottrell, 2012). Kelley and Cottrell (2009) further
showed that Fe3+/ΣFe ratios in arc magmas increase towards the trench
and correlate with concentrations of H2O and fluid-mobile elements
(e.g., Ba/La), indicating that the oxidation effect is a function of the
3500
Mature arc Median values
Island arc
3000 Mature arc
Tholeiite
Island arc
2500
Tholeiites
Frequency
2000
1500
1000
500
0
-2.0 -1.5 -1.0 -0.50 0.0 0.50 1.0 1.5 2.0
log10 (Fe2O3/FeO)
Fig. 2. Histogram of log(Fe2O3/FeO) values for mature arc, island arc, and non-arc tholeiitic
volcanic and plutonic rocks from the GEOROC database (http://georoc.mpch-mainz.gwdg.
de/georoc/). All available files from the pre-compiled “Convergent margins” dataset were
used for the arc group, and the “Basalt tholeiitic”, “Tholeiite 1”, and “Tholeiite 2” files from
the pre-compiled “Rocks” dataset were used for the tholeiite group. In the latter case,
analyses reported to be from convergent margins and Archean settings were excluded
([Tectonic setting] column heading in GEOROC database files). The datasets were trimmed
by deleting analyses: (1) that were not of volcanic or plutonic rocks, identified in [Rock
Type] column; (2) that were recorded as being altered to any degree, identified in
[Alteration] column; (3) that did not have independently measured FeO, identified in
[FeO(wt%)] column; and (4) that had total volatile contents ≤0.0 or ≥1.0 wt.% (sum of col-
umns [H2O(wt%) to [LOI(wt%)]).
 J.P. Richards / Lithos 233 (2015) 27–45
3
Mature arcs
Island arcs
Tholeiites
2
log10 (Fe2O3 / FeO)
1 Johnson and Plank, 1999; Labanieh et al., 2012), supercritical fusions
Very strongly oxi
dized
0 the above at different depths in subduction zones. Mungall (2002) has
Strongly oxidized
Moderately oxidiz
ed
-1
Moderately red
uced
Strongly reduce
d
-2
-3
0 5 10 15
FeOTotal (wt.%)
Fig. 3. Log(Fe2O3/FeO) versus FeOTotal for mature arc (red), island arc (blue), and non-arc
tholeiitic (black) volcanic and plutonic rocks (sourced and selected as in Fig. 2). Relative
oxidation state boundaries are from Blevin (2004), who suggests that the thick black
line between the “moderately reduced” and “moderately oxidized” fields approximates
the FMQ buffer curve.
degree of subduction metasomatism (see also: Brounce et al., 2014;
Carmichael et al., 2006; Rowe et al., 2009; Zimmer et al., 2010).
Evidence from other redox-sensitive elements such as vanadium
have yielded conflicting results. Lee et al. (2005) interpreted relatively
uniform V/Sc ratios in both MORB and arc basalts to indicate fO2 values
of ΔFMQ = −1.25 to +0.5, and argued that the higher fO2 values calcu-
lated for many arc volcanic rocks by other methods might reflect differ-
entiation processes rather than source characteristics. Similar
arguments have been made by Mallmann and O'Neill (2009) and by
Lee et al. (2010) on the basis of Zn/Fe ratios. On the other hand,
Laubier et al. (2014) used V/Yb ratios to argue for increasing magmatic
oxidation state from MORB (ΔFMQ ≈ 0), through back-arc basins, to
arcs (~ ΔFMQ ≥ + 2). The reliability of these trace element ratios as
proxies for magmatic oxidation states is thus unclear at the present
time.
2.4. Redox effects of subduction
The source of the oxidizing signature in arc magmas is thought to be
subducting oceanic crust. Oxidation of the deep oceans since the
Neoproterozoic Oxygenation Event (Canfield et al., 2006) has led to ox-
idative alteration of oceanic crust at mid-ocean ridges, which generates
secondary hematite and anhydrite in altered basalts (Alt et al., 2013;
Bischoff and Dickson, 1975; Shanks et al., 1981; Staudigel et al., 1996),
and the deposition of relatively oxidized deep-ocean sediments (Chen
et al., 1996; Piper et al., 1984; Wilson et al., 1985; with the exceptions
of reduced sediment deposition as noted by Malaspina et al., 2010 and
Wang et al., 2007). The main carriers for oxygen are Fe3+, Mn4+, S6+,
C4+, and to a lesser extent H2O, in the form of dissolved Fe and Mn ox-
ides, sulfates, and carbonates (Andreani et al., 2013; Brandon and
Draper, 1996; Evans, 2012; Evans and Tomkins, 2011; Kelley and
Cottrell, 2009). Variability in the extent of oxidative alteration and the
amount of oxidized (or reduced) sediment may, therefore, be the pri-
mary cause of the wide range of oxidation states found in arc magmas,
from essentially unoxidized (MORB-like) to highly oxidized composi-
tions (Fig. 3).
Subduction of this seafloor-altered material and subsequent remobi-
lization during prograde high-pressure metamorphism introduces
these redox components into the metasomatized mantle wedge (Alt
et al., 2012, 2013; Andreani et al., 2013). Although there is considerable
debate in the literature about the exact mechanism of the slab-to-
31
wedge transfer process, the chief contenders are hydrothermal fluids
(Bali et al., 2011; Peacock, 1993; Perfit et al., 1980; Ringwood, 1977;
Tatsumi, 1989), partial melts of hydrated basalt (Defant and
Drummond, 1990; Kay, 1978; Rapp and Watson, 1995), partial melts
of sediments (Behn et al., 2011; Hermann and Spandler, 2008;
of these components (Bureau and Keppler, 1999; Kawamoto, 2006;
Kessel et al., 2005; Portnyagin et al., 2007), or combinations of all of
argued that slab melts would carry more iron, and in particular Fe3+,
than hydrothermal fluids, and would therefore potentially be stronger
oxidants than aqueous fluids. However, petrogenetic and geochemical
considerations suggest that slab melting only occurs in exceptional
circumstances in Phanerozoic arcs, such as the subduction of
young, hot oceanic lithosphere, or at slab windows or tears where hot
asthenosphere directly contacts subducted oceanic crust (Davies and
Stevenson, 1992; Defant and Drummond, 1990; Peacock et al., 1994;
20
Yogodzinski et al., 2001). Although some have argued that slab melting
might be uniquely linked to arc metallogeny because of this strong oxi-
dative effect (e.g., Mungall, 2002; Oyarzun et al., 2001; Sajona and
Maury, 1998; Sun et al., 2011), others have questioned the evidence
for this relationship (Rabbia et al., 2002; Richards, 2002, 2012;
Richards and Kerrich, 2007).
Regardless of the exact process, it is clear that both fluids and melts
are capable of transferring the oxidized signature of seafloor alteration
and sediments into the mantle wedge source of arc magmas, and that
the effect does not need to be extreme to raise the fO2 of these magmas
1 or 2 log units above normal MORB-depleted mantle values to the
range typical or arc magmas (Evans, 2012). Likely, this effect is also to
some extent cumulative, resulting in a progressive increase in oxidation
state of the supra-subduction zone mantle wedge from typical mantle
values (ΔFMQ = − 1 to 0) at the onset of subduction, to ΔFMQ ≥ + 1
after a few million years of static arc development (i.e., arc magmatism
focused along a fixed axis in the upper plate, implying steady-state sub-
duction conditions; Evans, 2012). This may explain why calculated oxi-
dation states of primitive magmas from nascent oceanic arcs are
commonly indistinguishable from MORB (e.g., Lee et al., 2005), but in-
crease with arc evolution (Evans et al., 2012).
Progressive mantle wedge oxidation may also be reflected in arc
metallogeny. Few large ore deposits occur in primitive island arcs, but
develop commonly after several million years of arc magmatism, sug-
gesting that the arc magmatic system requires time to evolve to a
more “fertile” state (Richards, 2003). These processes are discussed fur-
ther below.
2.5. Partial melting in the mantle wedge and the calc-alkaline trend
The primary control on partial melting in the asthenospheric mantle
wedge is the influx of water from the dehydrating subducting slab,
which lowers the solidus temperature of peridotite (Arculus, 1994;
Grove et al., 2006, 2012; Kushiro et al., 1968; Ringwood, 1977; Stolper
and Newman, 1994; Ulmer, 2001). The resulting primary magmas are
hydrous, tholeiitic, high-Mg basalts (Greene et al., 2006; Pichavant
et al., 2002; Smith et al., 2010; Thirlwall et al., 1996), which evolve
to calc-alkaline compositions by early fractionation of olivine,
clinopyroxene, and magnetite, and later crystallization of hornblende
and plagioclase (Grove and Kinzler, 1986; Grove et al., 2003; Moore
and Carmichael, 1998). Hamada and Fujii (2008) and Zimmer et al.
(2010) suggest that primary magmatic water contents of 2 wt.% sepa-
rate the “dry” tholeiitic olivine-plagioclase-orthopyroxene fractionation
trend from the “wet” calc-alkaline trend, which is consistent with esti-
mates of water contents in primary and primitive arc magmas of be-
tween 1 and 8 wt.% H2O (typically 2–6 wt.%; Carmichael, 2002;
Cervantes and Wallace, 2003; Edmonds et al., 2014; Grove et al., 2003;
Kimura and Ariskin, 2014; Pichavant et al., 2002; Plank et al., 2013;
Ruscitto et al., 2012; Sobolev and Chaussidon, 1996; Wallace, 2005).
32 J.P. Richards / Lithos 233 (2015) 27–45

Zimmer et al. (2010) also stress the additional effect of elevated fO2 in a 500
establishing the low-Fe calc-alkaline trend by early crystallization of Mature arc data plotted as a
Fe-rich spinels. function of log(Fe2O3/FeO)
These hydrous compositions predispose arc magmas to developing 400
<-0.5
“adakite-like” trace element signatures of Sr enrichment and heavy -0.5 to 0
rare earth element (HREE) depletion, through early and abundant crys- >0
Median (-0.5 to 0)

Cu (ppm)
tallization of pyroxene and hornblende (which preferentially partition 300
middle (MREE) and HREE), and late crystallization of plagioclase
(which would otherwise deplete the melt in Sr; Naney, 1983; Richards
and Kerrich, 2007; Ridolfi et al., 2010; Rutherford and Devine, 1988; 200
Stamper et al., 2014b).
In addition to elevated water contents and oxidation states (in many
100
cases, as noted above), primary arc magmas are also enriched in a suite
of volatile and fluid-mobile elements, including Cl (500–2000 ppm Cl;
Wallace, 2005), S (900–2500 ppm S; de Hoog et al., 2001; Wallace,
0
2005), large-ion lithophile elements (LILE: Rb, K, Cs, Sr, Ba, and U), 0 5 10 15 20
and Li, B, Pb, As, and Sb (Gill, 1981; Perfit et al., 1980; Wysoczanski MgO (wt.%)
et al., 2012). These magmas are also characteristically depleted (relative
to adjacent elements on primitive mantle- or MORB-normalized trace- b 500
element diagrams) in Ti, Ta, and Nb due to their low mobility in slab Island arc data plotted as a
fluids and/or retention in restite phases (Foley et al., 2000; Klemme function of log(Fe2O3/FeO)
et al., 2005; Ryerson and Watson, 1987; Schmidt et al., 2004, 2009). 400
<-0.5
Whether or not they are also enriched in metals is discussed below. -0.5 to 0
>0
Median (-0.5 to 0)

Cu (ppm)
2.6. Redox effects on metallogeny during partial melting and magmatic 300
differentiation

200
A perennial debate in economic geology revolves around whether
ore-generating magmas are unusually metal-rich at source, or whether
ore formation results from magmatic and/or hydrothermal processes
100
operating on otherwise “normal” magmas. Examples of such debates in-
clude the abundance of Au in lamprophyres (Rock and Groves, 1988;
Tilling et al, 1973; Wyman and Kerrich, 1989), and Cu and Au in arc
0
magmas (Cline and Bodnar, 1991; Core et al., 2006; Keith et al., 1997; 0 5 10 15 20
Richards, 2013; Timm et al., 2012; Wilkinson, 2013). To date, no con- MgO (wt.%)
vincing evidence has been found for the necessity of unusually metal-
rich magmas in most ore-forming environments, but it is also obvious c 500
Tholeiite data plotted as a
that unusually metal-poor magmas would not be optimal for ore forma- function of log(Fe2O3/FeO)
tion. Thus, processes that could deplete magmas in ore metals could sig-
400
nificantly reduce their fertility, and vice versa.
<-0.5
Several recent studies have compared the Cu contents of arc and -0.5 to 0
>0
mid-ocean-ridge basalts (MORB), and have generally concluded that
Cu (ppm)

there is little difference in the compositions of primitive magmas from
these distinct tectonic settings (Jenner et al., 2010; Lee et al., 2012), al-
though Timm et al. (2012) found that some mafic rocks from the
Kermadec arc extend to higher Cu contents than MORB. Using the
same dataset as for Figs. 2 and 3, Cu contents of least-altered mature
arc, island arc, and tholeiitic (MORB) igneous rocks are plotted against
MgO in Fig. 4. The data are subdivided by log(Fe2O3/FeO) range
(b −0.5, − 0.5 to 0, and N0, roughly corresponding to the moderately
reduced, moderately oxidized, and strongly oxidized ranges of Blevin,
2004) based on the distribution shown in Figs. 2 and 3. The distribution
of data in Fig. 4 is virtually indistinguishable for the three tectonic set-
tings, and also appears to be independent of oxidation state, as shown
by the similar distribution of data for rocks with low (b−0.5), medium
(− 0.5 to 0), and high (N 0) log(Fe2O3/FeO) values. Primitive rocks
(N10 wt.% MgO) from all settings have moderate Cu contents of
~ 75–100 ppm Cu: 78.0 ± 63.6 ppm Cu (n = 53) in mature arcs;
74.7 ± 33.9 ppm Cu (n = 41) in island arcs; and 97.2 ± 26.7 ppm Cu
(n = 52) in primitive tholeiites. More evolved rocks (10–5 wt.% MgO)
expand to lower and higher Cu concentrations (0 to N200 ppm Cu), be-
fore the higher values decrease again towards 0 ppm Cu at lower MgO
contents. (The tholeiite data are mainly for basaltic rocks, with few
data for more differentiated compositions.) Overall, the bulk of the
data from mature arcs show a steady decrease in Cu values from mafic
to felsic compositions, as illustrated by the distribution of median values
300
200
100
0
0 5 10 15 20
MgO (wt.%)
Fig. 4. Plots of Cu versus MgO content in (a) mature arc, (b) island arc, and (c) non-arc tho-
leiitic igneous rocks, subdivided by log(Fe2O3/FeO) b −0.5, −0.5 to 0, and N0 (roughly
corresponding to the moderately reduced, moderately oxidized, and strongly oxidized
ranges of Blevin, 2004; sources of data as in Fig. 2). The distribution of data are broadly
similar in all three petrogenetic cases, and for all oxidation states. Median Cu contents
(binned over 1 wt.% MgO ranges up to 10 wt.% MgO, and then between 10–12.5 wt.%,
and N12.5 wt.% MgO) are shown for the moderately oxidized arc suites in (a) and (b),
with a polynomial line fit: (a) y = − 3.50 + 16.68x − 1.42x2 + 0.04x3 (R = 0.93);
(b) y = −21.70 + 39.39x − 4.14x2 + 0.13x3 (R = 0.97).
calculated for moderately oxidized samples (log[Fe2O3/FeO] = −0.5 to
0) shown in Fig. 4a. Island arc data show a slight increase in median Cu
contents from primitive to intermediate compositions (up from
 J.P. Richards / Lithos 233 (2015) 27–45 33

~75 ppm Cu in primitive rocks to ~95 ppm Cu at ~7 wt.% MgO, although mean = 94.0 ± 58.9 ppm, median = 85.0 ppm, n = 372; tholeiite:
relatively few data constrain the primitive range; Fig. 4b), before de- mean = 117.5 ± 64.2 ppm, median = 110.0 ppm, n = 115).
creasing again towards 0 ppm Cu in felsic rocks. The distribution of data shown in Figs. 4 and 5 suggests that Cu con-
There is a broader scatter to higher Cu contents in tholeiitic and is- tents in mafic to intermediate magmas from both arc and ridge tectonic
land arc rocks in the range 3–7 wt.% MgO (which corresponds to the settings are similar and generally quite low (b200 ppm, similar to
peak in Cu concentration) compared with mature arcs (Fig. 5; mature values obtained by Lee et al., 2012, in mantle melting models). This sug-
arc: mean = 59.9 ± 42.6, median = 46.9 ppm, n = 1247; island arc: gests that magmatic Cu concentrations are moderated by the presence
of minor amounts of sulfides in the source, into which chalcophile and
siderophile metals (such as Cu, Au, and the platinum group elements;
a 400
Cu in mature arc rocks
PGE) will preferentially partition (Keays, 1987, 1995; Lee et al., 2012),
even for moderately to strongly oxidized rocks.
350 In somewhat more evolved rocks (3–7 wt.% MgO), the data scatter to
Mean = 59.9 ± 42.6 ppm Cu (n = 1247)
Median = 46.9 ppm Cu higher Cu contents in both arc and ridge settings, but the bulk of the
Skewness = 2.02
300 data remains below ~ 150 ppm Cu. This distribution is illustrated by
the skewness of the histograms in Fig. 5 (up to 2.02 in mature arc
250
Frequency

rocks; Fig. 5a). For mature and island arc suites, the overriding trend
200
of the data seems to be towards decreasing Cu contents with differenti-
ation (decreasing MgO content), and the scatter to higher values ap-
150 pears more random. It also does not correlate with Fe3+/Fe2+ ratios in
the rocks, and both relatively oxidized and relatively reduced rocks
100 can have high Cu contents, although this is not common in either case.
Copper therefore appears to behave mildly compatibly for the majority
50 of samples analyzed from arcs and ridges, indicating the continual pres-
ence of condensed sulfide phases that hold the Cu content of the melt to
0
0 100 200 300 400 500 relatively low and decreasing concentrations. The scatter to higher Cu
Cu (ppm) concentrations in some intermediate-composition samples might re-
flect local incompatible behavior (as described by Jenner et al., 2010;
b 60 Lee et al., 2012), or might be a product of sulfide accumulation or
Cu in island arc rocks subsolidus processes (despite efforts to screen for alteration).
50 Assuming that these high-Cu values do reflect magmatic composi-
Mean = 94.0 ± 58.9 ppm Cu (n = 372) tions, the reason for this incompatible behavior is not clear, but could
Median = 85.0 ppm Cu
Skewness = 1.37 be due either to low total sulfur fugacity (unlikely in most arc settings)
40
or unusually high oxidation states, such that sulfide solubility was not
Frequency

exceeded or sulfides were destabilized by oxidation (e.g., Ballhaus

30 et al., 1991; Jenner et al., 2010; Mungall, 2002). However, a clear corre-
lation with high magmatic oxidation state is not observed, and it cannot
therefore be concluded that oxidized magmas are inherently more fer-
20
tile (with respect to Cu content) than more reduced magmas. A similar
conclusion has been drawn for gold in arc magmas (Jégo and Pichavant,
10 2012). The data also do not support the notion that arc magmas in gen-
eral are fundamentally more fertile (Cu-rich) than other mantle-derived
0 magmas such as MORB tholeiites; if anything the opposite is true, which
0 100 200 300 400 500 must mean that other processes are involved in the relationship
Cu (ppm) between arc magmas and porphyry Cu deposits. On the other hand, it
is also clear that most arc magmas (whether relatively oxidized or
c 25 reduced) retain ~50 ppm Cu on average into the andesitic range of com-
Cu in MORB tholeiites positions, which is also the value used by Cline and Bodnar (1991) to
show that normal arc magmas are capable of generating large porphyry
20
Mean = 117.5 ± 64.2 ppm Cu (n = 115)
Cu deposits.
Median = 110.0 ppm Cu Contrary to the findings of Jenner et al. (2010), the data do not sup-
Skewness = 1.19
port a general and sudden switch from incompatible to compatible be-
Frequency

15
havior of Cu at intermediate compositions (suggested to be caused by
sulfide-saturation triggered by magnetite crystallization). While this
10
switch may occur in some cases, the broad arrays of data shown in
Fig. 4 are more consistent with mildly compatible behavior of Cu
throughout the differentiation range for the bulk of magmas, with in-
5 compatible behavior (as indicated by higher Cu contents) being the ex-
ception. It might be argued that it is these exceptions that give rise to ore
deposits, but the effect is not particularly large – rarely more than 2–3
0 times average Cu contents – and thus at most might be expected to af-
0 100 200 300 400 500 fect the size but not the existence of a deposit, and it occurs over a rela-
Cu (ppm) tively narrow range of intermediate magma compositions (3–7 wt.%
MgO). This narrow peak of Cu concentrations would not be expected
Fig. 5. Histograms of Cu concentrations in rocks between 3–7 wt.% MgO, which span the
peak of Cu contents, for (a) mature arcs, (b) island arcs, and (c) and non-arc tholeiites
to significantly enhance the net flux of Cu from the mantle source region
(MORB) (sources of data as in Fig. 2). MORB and island arc suites show higher mean because Cu contents of primitive magmas are uniformly moderate.
and median Cu contents than mature arcs. Moreover, these anomalously Cu-rich magmas (if these compositions
34 J.P. Richards / Lithos 233 (2015) 27–45

indeed reflect magmatic values) do not clearly correlate with known
porphyry Cu deposits.
In summary, Cu contents of arc magmas globally show a general
weak trend of decreasing concentration with differentiation, with a
scatter to higher concentrations in some intermediate composition
rocks. These trends appear to be independent of oxidation state, and
there is no clear correlation between rocks with higher Cu concentra-
tions and porphyry ore deposits. Intermediate composition arc magmas
reaching the upper crust typically contain 50–100 ppm Cu (Fig. 5),
which has been shown to be sufficient for the generation of large por-
phyry deposits from reasonable volumes of magma (Cline and Bodnar,
1991).
2.7. The role of sulfur on metal solubility during partial melting
In combination with oxygen fugacity, the sulfur fugacity of magmat-
ic systems plays a critical role in the behavior of chalcophile
and siderophile metals. For sulfur, an important transition occurs be-
tween dissolved sulfide and sulfate dominance in silicate melts at
ΔFMQ ≈ +1 (Carroll and Rutherford, 1985; Jugo et al., 2010; Nilsson
and Peach, 1993), with high concentrations of S (dissolved as SO24 −)
possible in more oxidized magmas (e.g., up to 1.5 wt.% S; Beermann
et al., 2011; Jugo et al., 2005a). This means that oxidized magmas dom-
inated by sulfate (ΔFMQ ≥ +1) will be less likely to become saturated in
sulfide phases. But sulfide saturation is also a function of the overall sul-
fur content of the system. Thus, sulfide minerals or melts may be stable
even in quite oxidized melts if fS2 conditions are high (Jugo, 2009),
which is a characteristic feature of arc systems. This may explain why
high Cu concentrations, reflecting the “burn-out” of condensed sulfide
phases in highly oxidized mantle sources and magmas (as predicted
by Jugo et al., 2005a; Mungall, 2002; Parkinson and Arculus, 1999;
Righter et al., 2008; Timm et al., 2012) is not clearly observed in the
datasets shown in Fig. 4. Instead, the data show that relatively reduced
magmas are just as likely to, but rarely do, contain anomalously high Cu
contents as more oxidized magmas. Sparsity of data for elements such
as Au and PGE means that it is not clear whether these metals behave
in the same way (see discussion below).
The distribution of the bulk of the data suggests that, under most
conditions, the mantle sources of arc and ridge magmas are sulfide-
saturated (Keays, 1995), and that most of these magmas remain satu-
rated or close to saturation throughout their differentiation history.
The net effect of sulfide saturation on metal concentration in the
coexisting melt depends on several factors, including: (1) the metal in
question; (2) the volume of the sulfide phase relative to the silicate
melt; and (3) the nature of the condensed sulfide phase (sulfide melt,
pyrrhotite, monosulfide solid solution, intermediate solid solution). An
additional factor may be the presence of platinoid metal alloys in the
mantle source, which can dramatically fractionate the PGE (Mungall
and Brenan, 2014; Park et al., 2013).
The metals of greatest economic interest in subduction zone
magmas are Cu, Au, and the PGE. Although these metals can all be char-
1999; Park et al., 2013; Righter et al., 2008; Widom et al., 2003). These
differences are explored further below.
Where condensed sulfide phases coexist with silicate magma, the
ratio of the volume of sulfide to silicate melt (inverse of the R-factor of
Campbell and Naldrett, 1979, where R = [mass of silicate melt]/[mass
of sulfide]) can affect the ratios of metals left in the magma, as well as
their abundance. As discussed by Richards (2009), the presence of mod-
erate amounts of residual sulfide relative to a large volume of silicate
melt (e.g., ~ 0.001–1 wt.% sulfide; intermediate R-factor of 102–105;
Fig. 6) will deplete the magma in low-abundance, high partition coeffi-
cient elements such as Au and PGE (highly siderophile elements) but
may have little effect on the concentration of more abundant elements
with lower partition coefficient such as Cu, leading to high Cu/Au, Cu/
PGE magmas (e.g., Park et al., 2013; Fig. 6). Such magmas should be con-
sidered Cu-undepleted but Au-PGE-depleted, rather than Cu-rich, and
may be typical of normal arc environments where several hundred to
a few thousand ppm S may be present (de Hoog et al., 2001; Jugo,
2009; Wallace, 2005). These magmas have the potential to form Cu-
rich porphyry-type deposits (Richards, 2009, 2011a).
If residual sulfide abundances are high relative to the volume of
magma (R b 102), all chalcophile and siderophile elements will be de-
pleted in the magma (Fig. 6; Keays, 1987). However, such high
sulfide/magma ratios are rarely achieved in nature (except during the
formation of some orthomagmatic sulfide deposits by bulk sulfide con-
tamination of S-undersaturated mafic melts; e.g., Naldrett, 1989; Keays,
1995). In contrast, under high R-factor conditions (R N 105), where van-
ishingly small amounts of (or no) residual sulfides are present in the
mantle source and during differentiation, derivative magmas will be
undepleted even in highly siderophile elements, and can thus potential-
ly lead to the formation of Au- or PGE-rich deposits (Fig. 6; Hamlyn
et al., 1985; Richards, 2009). Such conditions appear to be relatively
rare in normal arc settings, but may arise in alkaline back-arc magmas
(Métrich and Clocchiatti, 1996; Richards et al., 1991), and/or during
second-stage S-undersaturated melting of subduction modified mantle,
where a flux of fresh S from the subducting slab is no longer present
(Dale et al., 2012; Richards, 1995, 2009; Wyborn and Sun, 1994).
Finally, the nature of the restite or fractionating sulfide or alloy phase
also has a significant effect on metal partitioning. In particular, the pres-
ence of small amounts of Pt-Fe alloy as restite in the mantle source re-
gion may have a profound effect on PGE abundances and ratios in
partial melts (Kepezhinskas et al., 2002; Mungall and Brenan, 2014;
Park et al., 2013). In addition, Righter et al. (2004) have shown that,
Cu-undepleted Au-undepleted post-
arc magmas subduction magmas
106
d in
che ide
105 e nri l sulf
Au idua
res
104
de
103 ulfi
in s Cu maximized in
Cu e magma (R ≥ 103)
102 u lfid
ins
Au
Cu (ppm)
Au (ppb)

acterized as chalcophile and siderophile in character, Au and the PGE are 10 ma

ag
considered to be highly siderophile, and partition strongly into most i nm ma
1 Cu ag Au maximized in
sulfide phases relative to silicate melts (Campbell and Naldrett, 1979; inm magma (R ≥ 106)
Laurenz et al., 2013; Peach et al., 1990), while the PGE also partition dif- 0.1 ted
ple
de Sulfide/silicate melt partition
ferentially into metal alloy phases (Kepezhinskas et al., 2002; Mungall 10–2 Au coefficients:
D(Cu) = 103
and Brenan, 2014). Consequently, the chemical behavior of these ele- a D(Au) = 105
10–3 gm
ments in the presence of sulfides and alloys can be expected to be sub- n ma Metal concentrations in
Aui magma in absence of sulfide:
stantially different, and this may explain the widely variable Cu/Au and 10–4 Cu = 50 ppm
Cu/PGE ratios in resultant ore deposits. Unfortunately, because of the Au = 5 ppb
10–5
difficulty and expense of obtaining accurate trace-level analyses of Au
1 10 102 103 104 105 106 107 108
and PGE in igneous rocks, there is very little information on their abun-
R = (mass of silicate melt)/(mass of sulfide)
dance in arc rocks (certainly compared to the wealth of data for Cu).
Nevertheless, the differential behavior of these elements has been doc- Fig. 6. Variations of Cu and Au contents in silicate melts and coexisting sulfides as a func-
umented by several studies (e.g., Hamlyn et al., 1985; Jégo and tion of the volume ratio of these two phases (the R-factor of Campbell and Naldrett, 1979);
Pichavant, 2012; Jégo et al., 2010; Li and Audétat, 2012; McInnes et al., modified from Richards (2009).
 J.P. Richards / Lithos 233 (2015) 27–45
while Re, Au and Pd are incompatible in Cr-spinel, Rh, Ru and Ir are
strongly compatible in this mineral, potentially leading to significant
fractionation between these elements. Copper, Au, and PGE also have
different partition coefficients between various sulfide phases (liquids
and minerals) and silicate melt. In general, partition coefficients seem
to be highest for sulfide liquids (Laurenz et al., 2013; Li and Audétat,
2012; Mungall and Brenan, 2014), followed by intermediate solid solu-
tion (ISS) for Cu and Au (Jugo et al., 1999; Kesler et al., 2002),
monosulfide solid solution (MSS; Li and Audétat, 2012), and pyrrhotite
(Jugo et al., 1999; Zajacz et al., 2013). Under mantle conditions, it would
seem likely that some sulfide liquid is present, and that it will have a
major control on the abundances and ratios of chalcophile and
siderophile elements in arc magmas, particularly if these sulfides are
preferentially left in the restite rather than being entrained in the
magma, due to their density and wetting properties (as suggested by
Mungall and Su, 2005).
2.8. The source of sulfur in arc magmas
In the preceding discussion, the high abundance of sulfur in arc mag-
matic systems has been noted. But because of its critical importance in
both the fixing and solvating of metals, it is worth briefly reviewing
the evidence for the source of this sulfur, and how its nature may have
changed over geological time.
Arc magmas are rich in sulfur relative to most other mantle-derived
magmas, and this has been referred to as the “excess sulfur” problem by
some authors (e.g., Sharma et al., 2004; Wallace, 2005), reflecting the
much larger volumes of SO2 emitted from some arc volcanoes than
would be predicted from the solubility of S in co-erupted felsic lavas.
It is now clear that the excess S comes from magma chamber recharge
by more mafic magmas with higher S solubility (De Hoog et al., 2004;
Hattori, 1993; Roberge et al., 2009; Van Hoose et al., 2013).
Sulfur isotopic compositions in arc magmas are typically higher than
depleted mantle values of δ34SVCDT ≈ 0‰ (up to and rarely above 13‰;
Alt et al., 1993; Ishihara and Sasaki, 1989), and this has been interpreted
to reflect a contribution from seawater sulfate, fixed in the subducted
oceanic crust during earlier seafloor hydrothermal alteration (Alt
et al., 2013; Debret et al., 2014; Evans et al., 2014; Sasaki and Ishihara,
1979; Shanks et al., 1981; Wallace and Edmonds, 2011) or in sulfate-
bearing sediments (De Hoog et al., 2001). As a consequence of the
Neoproterozoic Oxygenation Event, sulfate in oxidized deep ocean wa-
ters reacts with Fe2+ in basaltic oceanic crust to form Fe3+-oxides, sul-
fates, and some sulfides. Subduction of this material, along with sulfate-
bearing sediments, introduces a flux of oxidized sulfur (and other com-
ponents; Debret et al., 2014) into the mantle wedge that easily swamps
background mantle concentrations, with up to ~ 40% of the subducted
sulfur being transferred to the wedge via dehydration fluids (Jégo and
Dasgupta, 2013), and 15–30% of the flux reaching the surface in volcanic
emissions (Wallace, 2005). This flux of sulfate may be the main vector
for oxidation of the mantle wedge (Alt et al., 2012; Evans and
Tomkins, 2011; Jégo and Dasgupta, 2014; Kelley and Cottrell, 2009).
Evans and Tomkins (2011), Prouteau and Scaillet (2013) and
Richards and Mumin (2013a,b) have proposed that, prior to the
Neoproterozoic Oxidation Event, arc magmas were more reduced and
less S-rich, and thus less prospective for the formation of porphyry-
type magmatic-hydrothermal Cu ± Au deposits. In particular,
Richards and Mumin (2013a,b) suggested that this characteristic
might explain the relative rarity of Precambrian porphyry deposits (in
addition to preservation considerations; Kesler and Wilkinson, 2006).
3. Lower crustal MASH processes
Nascent island arcs are characterized by the eruption of primitive
tholeiitic basalts onto thin oceanic crust, and are associated with few
magmatic-hydrothermal ore deposits. Only after the arc crust has thick-
ened and differentiated to lower density compositions will significant
35
volumes of magma crystallize as plutonic rocks, with the potential for
subsurface volatile release and hydrothermal ore formation. The time
required for this transition can be expected to vary depending on the
subduction rate, angle of subduction, and other factors, but likely takes
on the order of 10 m.y. (Deering et al., 2012; Evans, 2012; Ishizuka
et al., 2011; Reagan et al., 2008). This timeframe is consistent with the
relatively late timing of porphyry systems in island arc settings and in
continental arc magmatic cycles (Kesler et al., 1977; Mitchell and Bell,
1973; Richards, 2003, 2005; Rohrlach and Loucks, 2005).
In addition to promoting plutonism, the thickening of arc crust has
multiple chemical effects on arc magmatism, including extending the
range of magmatic differentiation and interaction with older crustal ma-
terials. These processes have been collectively termed MASH, standing
for crustal melting, assimilation, storage, and homogenization of arc
magmas (Hildreth and Moorbath, 1988). Their effects on metallogenic
potential depend largely on whether they cause substantial loss of
metals from the magma to crystallizing phases, prior to ascent into the
upper crust and partitioning of those metals into an exsolving
magmatic-hydrothermal fluid (Spooner, 1993). The same principles
that were used to consider the loss of metals to restite in the mantle
wedge apply to fractionating minerals and melts. Although minor
amounts of Cu can be incorporated into igneous silicate and oxides
phases, partition coefficients are typically less than 1 indicating that
Cu behaves incompatibly with respect to these minerals (Cline and
Bodnar, 1991; Core et al., 2005; Lee et al., 2012; Liu et al., 2014); conse-
quently, their fractional crystallization will not significantly affect the
concentration of metals in the melt phase. On the other hand, segrega-
tion of sulfide melts and minerals will strongly partition chalcophile
and siderophile elements, and if large volumes of sulfide are fractionat-
ed they will strongly deplete the magma in these metals (potentially
forming orthomagmatic sulfide deposits within mafic cumulate rocks;
Spandler et al., 2000; Fig. 6). Sato (2012) and Tomkins et al. (2012)
have proposed that such conditions might occur where reduced, gra-
phitic rocks are present in the lower crust. Assimilation of this material
by oxidized S-rich arc magmas would cause reduction of SO2− 4 to S2−,
voluminous sulfide immiscibility, and depletion of metals in the melt,
with subsequent decreased potential for magmatic-hydrothermal ore
formation upon emplacement in the upper crust.
To date, no examples of large sulfide accumulations in lower crustal
arc magmatic systems have been reported, with the possible exception
of Alaskan-type PGE deposits (Batanova et al., 2005; Slansky et al., 1991;
Spandler et al., 2000; Thakurta et al., 2008, 2014). Nevertheless, small
amounts of sulfide minerals are commonly present in lithospheric man-
tle xenoliths (Szabó et al., 2004) and arc cumulate sequences (Lee et al.,
2012; Li et al., 2013; Peng et al., 2013; Richards, 2011a; Zhang et al.,
2014), indicating, as noted previously, that arc magmas remain close
to sulfide-saturation throughout much of their evolution. Core et al.
(2006), Hou et al. (2009, 2011), Richards (2009), Shafiei et al. (2009)
and Pettke et al. (2010) have suggested that such minor accumulations
of sulfides might represent easily remobilized sources of metals during
later, post-subduction magmatism and ore deposit formation, whereas
Chiaradia et al. (2009), Jenner et al. (2010), Lee et al. (2012), Sillitoe
(2012) and Chiaradia (2014) consider that these sulfides are an essen-
tial precursor concentration step for the formation of normal arc por-
phyry Cu systems. In the former case, numerous post-subduction
scenarios, such as collision or post-collisional rifting, can be envisaged
that would re-melt sulfide-bearing lower crustal rocks under sulfur-
undersaturated conditions, leading to redissolution of sulfides and
their metals, and the potential formation of post-subduction porphyry
Cu ± Au deposits. In contrast, in the latter case (preconcentration of
metals in lower crustal sulfide cumulates) it is not clear what would
cause a change from sulfide-saturated to sulfide-undersaturated condi-
tions if nothing else changed during a normal cycle of sulfur-rich arc
magmatism. The logical result of sequestering metals in cumulates at
the base of the crust would be to reduce the potential for the fractionat-
ed magmas subsequently to form magmatic-hydrothermal ore deposits,
36 J.P. Richards / Lithos 233 (2015) 27–45
rather than being a key step in their formation. Chiaradia (2014,
p. 44–45) explains this apparent contradiction by appealing to “a special
combination of regional to local scale conditions [to] allow the success-
ful transfer of the deep Cu accumulations to shallower levels and the
formation of large porphyry copper systems”, but calling upon unde-
fined special processes does not seem a very satisfactory model to ex-
plain the formation of a common and widespread ore deposit type.
Jenner et al. (2010, 2012), Sun et al. (2011), Lee et al. (2012) and
Chiaradia (2014) all note an apparent increase in Cu content with differ-
entiation in mafic arc magmas prior to a decrease once intermediate
compositions are reached (cf. Fig. 4). Jenner et al. (2010) attribute this
trend to initial incompatible behavior of Cu, followed by change to sul-
fide saturation triggered by the onset of magnetite crystallization (the
“magnetite crisis”), or volatile exsolution (Sun et al., 2004). Lee et al.
(2012) and Chiaradia (2014) further suggest that such processes could
lead to a significant accumulation of metals within the lower crust,
such that 70–80% of the Cu in the magma flux might be sequestered
in arc cumulate rocks (Lee et al., 2012). However, it is notable that this
proportion is similar to the volume of arc magma crystallized in plutons
versus being erupted at surface (~ 80% vs. ~ 20%, respectively; Barker
et al., 2013; Carmichael, 2002; Sadofsky et al., 2008). Consequently,
this Cu loss might simply reflect background-level disseminations of
sulfides in cumulate and plutonic rocks, and might not indicate signifi-
cant depletion of Cu in the residual magmas that reach the upper crust.
In summary, deep crustal MASH processes affecting arc magmas re-
sult in variable degrees of Cu loss to cumulate sulfides, the amount de-
pending on the oxidation state of the local lower crust. Large amounts
of sulfide (and contained metals) might be lost if the lower crust is re-
duced (e.g., graphitic), but lesser amounts are expected during interac-
tion with normal crustal rocks. The proportion of Cu lost from the
magma flux in the latter case is similar to the estimated proportion of
plutonic to extrusive rocks in arcs, and does not, therefore, indicate
that magmas ascending from MASH zones are significantly depleted in
Cu (or that lower crustal cumulate rocks are significantly enriched in
Cu). Few data exist for concentrations of other metals such as Au and
PGE in arc cumulates and magmas, but the higher partition coefficients
of these elements between sulfide phases and silicate melts suggest that
evolved arc magmas might indeed be relatively depleted, consistent
with the relatively low abundances of Au and particularly PGE in
many porphyry Cu deposits, and the occurrence of PGEs in Alaskan-
type layered intrusions (e.g., Batanova et al., 2005; Spandler et al.,
2000; Thakurta et al., 2014). Circumstances that give rise to more Au-
rich porphyry deposits either reflect late-stage magmatic and hydro-
thermal processes (e.g., Muntean and Einaudi, 2000; Murakami et al.,
2010; Sillitoe, 2000) or atypical arc, back-arc, or post-subduction pro-
cesses associated with more alkaline magmas (e.g., Jensen and Barton,
2000; Richards, 1995, 2009; Solomon, 1990; Wyborn and Sun, 1994).
In particular, Li and Audétat (2013) suggest that the mantle sources of
potassic magmas might be saturated in monosulfide solid solution
(MSS) rather than a sulfide liquid, into which Au has a lower partition
coefficient. Such alkaline magmas might therefore have a higher poten-
tial to form magmatic hydrothermal Au deposits upon upper crustal
emplacement.
4. Fractional crystallization and devolatilization
Fractional crystallization, along with other processes such as magma
mixing and wallrock (crustal) contamination, progressively affect the
compositions of arc magmas as they rise towards the surface. The
most profound effects likely occur in deep crustal MASH zones (or
“hot zones”; Annen et al., 2006), which transform and homogenize
the flux of basaltic arc magma from the asthenosphere into evolved,
intermediate-composition magmas (basaltic andesites to andesites,
and locally more felsic melts derived by crustal melting; Eichelberger
et al., 2006; Lee and Bachmann, 2014; Mišković and Francis, 2006;
Romick et al., 1992; Smith et al., 2010). This is also where the calc-
alkaline (low-Fe) geochemical character is imprinted on arc magmatic
suites, caused by early crystallization of Fe-rich minerals (Grove et al.,
2003; Hamada and Fujii, 2008; Hildreth and Moorbath, 1988;
Pichavant and Macdonald, 2007; Romick et al., 1992; Stamper et al.,
2014b). Evidence from experimental petrology and deep arc crustal sec-
tions confirm that olivine, pyroxene, amphibole, and magnetite are
early crystallizing phases from hydrous arc basalts, with plagioclase
appearing relatively late on the cotectic (Blatter and Carmichael,
1998b; Larocque and Canil, 2010; Moore and Carmichael, 1998;
Müntener and Ulmer, 2006; Müntener et al., 2001; Nandedkar et al.,
2014; Tollan et al., 2012). This crystallization sequence not only results
in early Fe-depletion relative to alkalis, but can also generate high Sr/Y
and HREE-depleted compositions (high La/Yb, low Yb and Y concentra-
tions) that resemble adakites (Castillo et al., 1999; Klepeis et al., 2003;
Macpherson et al., 2006; Richards and Kerrich, 2007; Takahashi et al.,
2005; Tiepolo and Tribuzio, 2008; Tulloch and Kimbrough, 2003). Frac-
tionation of mafic and largely anhydrous minerals also enriches the
melt in incompatible elements and water (Rohrlach and Loucks, 2005)
and Plank et al. (2013) have noted that erupted arc magmas have glob-
ally uniform and elevated water contents of ~4 wt.% H2O.
Fractionation of Fe-bearing minerals can also affect the Fe3+/Fe2+
ratio of the melt. Most mafic silicates preferentially incorporate Fe2+
rather than Fe3 +, so their crystallization might be expected to
increase the ferric content of the melt. But crystallization of magnetite
(FeIII2FeIIO4) would have the opposite effect for magmas with Fe3 +/
Fe2+ ratios less than 2:
II III III II
Fe OðmeltÞ þ Fe 2 O3ðmeltÞ ¼ Fe 2 Fe O4ðmagnetiteÞ ð2Þ
In a relatively oxidized melt, where most of the Fe is present as Fe3+
(dissolved as Fe2O3), the Fe3+/Fe2+ ratio and fO2 will increase in the re-
maining melt with magnetite crystallization:
6 Fe
III
¼ 4 Fe
III II
þ O2ðmeltÞ ð3Þ
2 O3ðmeltÞ 2 Fe O4ðmagnetiteÞ
whereas oxidation state will decrease in relatively reduced melts where
most of the Fe is present as Fe2+ (dissolved as FeO):
II III II
6 Fe OðmeltÞ þ O2ðmeltÞ ¼ 2 Fe 2 Fe O4ðmagnetiteÞ ð4Þ
The boundary Fe3+/Fe2+ value for pure magnetite fractionation is
equivalent to log(Fe2O3/FeO) = 0.26, which is well above the average
for arc magmas (–0.21 ± 0.38; Figs. 2 and 3). Thus, typical arc magmas
might be expected to become more reduced with magnetite crystalliza-
tion. The onset of magnetite fractionation in relatively evolved magmas
(≥60 wt.% SiO2) has been termed the “magnetite crisis” by Jenner et al.
(2010) because of its effect on the Fe3+/Fe2+ ratio, and therefore oxida-
tion state, of the remaining magma. Reduction by this process is argued
to cause reduction of soluble and abundant sulfate to less soluble sul-
fide, leading to saturation of the magma in sulfide melt and/or minerals,
and consequent depletion of the magma in metals. However, while arc
magmas do show an overall weakly decreasing trend of Cu concentra-
tions with differentiation (Fig. 4), Fe3+/Fe2+ ratios and ΔFMQ values
generally increase (as shown in Fig. 3, and observed in individual mag-
matic suites: e.g., Richards et al., 2006, 2013). This, suggests that either
the magnetite effect is not significant, or that other processes are coun-
tering it (e.g., Fe2+-rich silicate mineral fractionation), or both.
The above arguments assume fractionation of pure magnetite. How-
ever, magnetite does not appear suddenly on the cotectic during mag-
matic differentiation (i.e., as a “crisis”), but rather appears as a late-
crystallizing end-member of the spinel solid-solution series, starting
with Cr-spinel in primitive basaltic magmas, followed by Ti-magnetite
in andesites, and magnetite in dacites (e.g., Macdonald et al., 2000;
Müntener and Ulmer, 2006; Müntener et al., 2001; Nandedkar et al.,
2014; Pichavant and Macdonald, 2007; Richards et al., 2006; Spandler
 J.P. Richards / Lithos 233 (2015) 27–45
et al., 2003; Tollan et al., 2012; Zimmer et al., 2010). Cr- and Ti-rich spi-
nels have lower Fe3+/Fe2+ ratios than magnetite (due to substitution of
Ti4+ and Cr3+ for Fe3+; Stamper et al., 2014b; Waychunas, 1991), and
their crystallization would therefore tend to cause an increase of the
Fe3+/Fe2+ ratio in moderately oxidized primitive to intermediate com-
position magmas (i.e., oxidation) rather than a decrease. For example, in
a volcanic suite from the Neogene Antofalla volcano in Argentina, spi-
nels ranged from chromite in basaltic andesites, through Ti-rich magne-
tite in andesites, to Ti-poor magnetite in dacites, with log(Fe2O3/FeO)
ratios increasing from −0.40 in chromite (significantly lower than the
median ratio of − 0.22 in arc magmas) to 0.19 in Ti-poor magnetite.
Magmatic oxidation states (calculated from magnetite-ilmenite pairs)
correspondingly increased from ΔFMQ = ~ 1–1.5 to ~ 2–2.5 over this
compositional range (Richards et al., 2006). Thus, early crystallization
of abundant Fe3+-poor spinel corresponds with an increase in oxidation
state of the magma, a process that continues despite fractionation of
(much smaller amounts of) Fe3 +-rich magnetite from more evolved
melts. Suffice to say, the interplay between these various redox buffers
and fractionating mineral compositions is complex and poorly under-
stood at this time, but the bulk empirical data suggest that progressive,
mild oxidation with fractionation of arc magmas is more common than
reduction.
The process most widely recognized as having an oxidative effect on
magmas as they rise towards the surface is devolatilization, especially of
reduced or weakly oxidized gaseous species such as H2, H2S, and SIVO2
(Burgisser and Scaillet, 2007; Candela, 1986; Gaillard et al., 2001;
Holloway, 2004; Mathez, 1984; Zimmer et al., 2010). Of these species,
SO2 is likely to be the most abundant in arc magmas, and SO2 is
known to be a major component of volcanic emissions worldwide
(Sharma et al., 2004; Wallace, 2001, 2005).
As for Fe, in a relatively oxidized melt in which most of the S is dis-
solved as SVIO24 − (i.e., where the average valence of S in the melt is
N+4; ΔFMQ ≥~+1; Beermann et al., 2011; Jugo et al., 2005a), fO2 will
increase with SIVO2 degassing:
VI IV
MS O4ðmeltÞ ¼ MOðmeltÞ þ S O2ðvaporÞ þ 0:5 O2ðmeltÞ
(where M is an element such as Ca or Fe; Baker and Rutherford, 1996),
whereas fO2 will decrease in a more reduced melt (i.e., where the aver-
age valence of S in the melt is b+4; ΔFMQ ≤ ~ +1):
–II IV
MS ðmeltÞ þ 1:5 O2ðmeltÞ ¼ MOðmeltÞ þ S O2ðvaporÞ
Thus, typical S-rich, moderately oxidized arc magmas are likely to
undergo late stage oxidation as a result of SO2 degassing and coupled
magnetite crystallization:
II VI III II
3 Fe OðmeltÞ þ 3 MS O4ðmeltÞ ¼ Fe 2 Fe O4ðmagnetiteÞ þ 3 MOðmeltÞ
IV
þ 3 S O2ðvaporÞ þ O2ðmeltÞ
An additional late-stage oxidative process that has been proposed by
Bell and Simon (2011) is the exsolution of saline fluids, in which Fe2+ is
more soluble than Fe3+, again having the effect of increasing the Fe3+/
Fe2+ ratio in the residual magma.
Devolatilization of arc magmas begins at deep levels in the crust
with exsolution of a CO2-rich gas phase, into which some SO2 likely par-
titions (Blundy et al., 2010; Holloway, 1976; Kamenetsky et al., 2001;
King and Holloway, 2002; Lowenstern, 2001; Newman et al., 2000;
Roberge et al., 2009; Wallace, 2005). But SO2 loss increases dramatically
upon water saturation at shallower levels in the crust (5–10 km;
Burnham, 1979; Wallace, 2001, 2005), and is almost quantitative upon
eruption at surface (whole-rock S contents of erupted arc magmas are
much lower than estimated magmatic values; Alt et al., 1993; Carroll
and Rutherford, 1985). Consequently, magmas reaching the upper
crust can be expected to undergo significant oxidation due to SO2 loss,
37
which on average appears to outweigh the reductive effect of magnetite
crystallization.
The data in Fig. 3 suggest that most arc magmas are moderately ox-
idized, but can become strongly oxidized (and in some cases reduced;
Kelley and Cottrell, 2012), during differentiation. Both processes will
have major effects on the solubility of metals in the magma because of
their effects on magmatic sulfur content and speciation (Jugo et al.,
2005b; Métrich and Clocchiatti, 1996). As discussed above, reduction
will result in voluminous sulfide saturation and loss of potential to
form later magmatic hydrothermal ore deposits; this may explain the
dearth of porphyry deposits in, for example, Japan, where the lower
crust contains graphitic lithologies (Sato, 2012; Tomkins et al., 2012).
On the other hand, increasing oxidation state is likely to make sulfide
melt and mineral saturation less likely, whereas sulfate saturation and
anhydrite crystallization may occur (e.g., Audétat et al., 2004; Baker
and Rutherford, 1996; Carroll and Rutherford, 1985, 1987; Chambefort
et al., 2008; Imai et al., 1993; Luhr et al., 1984; Parat et al., 2002;
Streck and Dilles, 1998). Botcharnikov et al. (2011, 2013) have shown
that, up to ΔFMQ ≈ +1, gold solubility increases in S-bearing basalts–
andesites, but drops off sharply at higher oxygen fugacities as sulfide,
with which Au combines to dissolve in the melt, breaks down to sulfate.
In contrast, Zajacz et al. (2012) and Sun et al. (2014) have respectively
shown that Cu and Mo solubilities increase steadily with increasing
fO2, because these metals are dissolved predominantly as oxide species
(CuO0.5 and MoO3) rather than as sulfides. Consequently, given that arc
magmas globally have oxidation states in the range ΔFMQ = + 0.5 to
+2 (as reviewed above), they appear to be ideally suited to the trans-
portation of Cu, Mo, Au, as well as other minor metals. In the case of
gold, however, highly oxidized magmas (ΔFMQ N N+1) may have lim-
ited potential for Au transport and ore formation.
5. The magmatic to hydrothermal transition
Water solubility in silicate melts increases with pressure (Baker and
Alletti, 2012; Burnham, 1979). Typical andesitic arc magmas contain
ð5Þ ~4 wt.% upon ascent into the upper crust (Plank et al., 2013), and can
be expected to saturate in H2O as pressure falls to 1–2 kb, or upon rising
to depths of ~3–6 km (Burnham, 1979). This process is sometimes re-
ferred to as “first boiling” (due to decompression upon ascent), whereas
“second boiling” is caused by post-emplacement crystallization and
concentration of water in the residual melt (Candela, 1989). Likely
these two processes overlap, but it is clear that the bulk of dissolved
ð6Þ
magmatic water exsolves during second boiling at relatively shallow
levels in the crust, whereas CO2, which has much lower solubility in sil-
icate melts, begins to degas much earlier and at depth (i.e., during first
boiling; Holloway, 1976; King and Holloway, 2002). It is this shallow-
level volatile exsolution that is critical to the formation of magmatic-
hydrothermal ore deposits, by partitioning metals from the melt into
an initially high temperature, saline, S-rich hydrothermal fluid phase,
ð7Þ in which metals are solvated as chloride, sulfide, or bisulfide complexes
(Candela and Holland, 1984; Candela and Piccoli, 1995; Frank et al.,
2011; Hedenquist and Lowenstern, 1994; Heinrich et al., 1999;
Migdisov et al., 2014; Pokrovski et al., 2008; Seo et al., 2009; Simon
et al., 2005, 2006; Webster, 2004; Williams et al., 1995; Zajacz and
Halter, 2009). The efficiency of this partitioning process is controlled
by several factors, governed primarily by the availability of metals in
the melt, the volume of hydrothermal fluid exsolved relative to the vol-
ume of melt, and the efficiency with which that fluid physically mixes
with the melt as bubbles prior to separation as a discrete volatile
plume (Cline and Bodnar, 1991; Cloos, 2001; Henley and McNabb,
1978; Shinohara and Hedenquist, 1997).
In their seminal study, Cline and Bodnar (1991) showed that the
depth of emplacement of the source magma body critically affects the
availability of metals and the salinity of the exsolved fluid. Deeply
emplaced magmas (~2 kb) exsolve a relatively saline fluid after ~ 60%
crystallization, which can efficiently scavenge chloride-soluble metals
38 J.P. Richards / Lithos 233 (2015) 27–45
such as Cu from the residual magma (see also Candela, 1992; Chiaradia
et al., 2012; Cline, 1995; Huber et al., 2012). In contrast, shallowly
emplaced magmas (0.5–1 kb) initially exsolve low salinity vapors that
are inefficient in dissolving chloride-soluble metals. Salinity of the
exsolved fluid increases at late stages of crystallization (≥90%), but by
this point most of the metal content of the magma has been locked up
at background concentrations in crystals. Gold, on the other hand,
may be solubilized early by dilute fluids because it is thought to be dis-
solved as bisulfide species rather than as chlorides; this may explain the
observation that Cu-poor porphyry Au deposits are characteristically
emplaced at shallow depths (Muntean and Einaudi, 2000; Murakami
et al., 2010; Sillitoe, 2000; Vila and Sillitoe, 1991).
Several authors have suggested that late-stage sulfide saturation
prior to volatile exsolution in the upper crust might be an important
preconcentration step, by first partitioning chalcophile and siderophile
metals into a sulfide melt or crystalline phase. These sulfides would
then be susceptible to oxidation and/or redissolution by exsolving aque-
ous fluids, and transfer of the contained metals to the fluid (Halter et al.,
2002, 2005; Jugo et al., 1999; Keith et al., 1997; Larocque et al., 2000;
Nadeau et al., 2010, 2013; Spooner, 1993; Stavast et al., 2006;
Wilkinson, 2013). While the presence of sparse sulfide inclusions in
phenocrysts in plutonic rocks associated with porphyry deposits is not
uncommon (op. cit., and Borrok et al., 1999), it is not clear how impor-
tant this process is to enhancing the efficiency of magma-to-fluid trans-
fer of metals, or whether this two-step process is more efficient than a
one-step process of partitioning metals directly from the melt into an
exsolving volatile phase (Audétat and Pettke, 2006; Candela and
Holland, 1984; Candela and Piccoli, 1995; Cline and Bodnar, 1991).
Fig. 6 suggests that quite large volumes of sulfide (N~ 1%) would need
to unmix or crystallize from the magma before a significant proportion
of the dissolved Cu could be extracted. With the possible exception of
some dikes associated with the Bingham porphyry, Utah (which contain
up to 0.1 modal % sulfide globules; Keith et al., 1997), such high sulfide
concentrations have not been observed in porphyry-related intrusive
rocks. It could be argued that the sulfides have been redissolved prior
to final crystallization, and that the evidence has therefore been lost
(e.g., Larocque et al., 2000), but one might still expect to see abundant
sulfide inclusions trapped in and protected by phenocrysts if this pro-
cess was important, whereas these inclusions are in fact sparse. Instead,
the relatively high and increasing oxidation state of evolved arc magmas
reaching the upper crust (ΔFMQ = +1 to +2) suggests that the bulk of
S in these magmas is present as sulfate (Carroll and Rutherford, 1985;
Chambefort et al., 2008), with sparse sulfides being stable only because
of high total sulfur fugacity (and therefore also high fH2S).
Hydrothermal fluids exsolved from these magmas will have similar-
ly high oxidation states, approximately corresponding to the sulfur gas
(SO2–H2S) buffer curve (~ ΔFMQ = + 2; Fig. 7; Einaudi et al., 2003;
Hedenquist and Richards, 1998; Ohmoto, 1986; Ohmoto and Rye,
1979). With cooling below ~ 450 °C, the SO2–H2S buffer curve crosses
the magnetite–hematite buffer (Fig. 7), as reflected in the commonly
observed late-stage oxidation of early hydrothermal magnetite (associ-
ated with chalcopyrite in potassic alteration) to hematite + pyrite
(Einaudi et al., 2003; Sun et al., 2013). A key reaction from the point of
view of ore deposition from these magmatic-hydrothermal fluids is
the disproportionation of SO2 (the predominant sulfur species in high-
temperature fluids) to H2S and H2SO4, which occurs progressively as
the fluid cools below ~ 400 °C (Holland, 1965; Kusakabe et al., 2000;
Whitney, 1988):
IV –II VI
4 S O2ðaqÞ þ 4 H2 O ¼ H2 S ðaqÞ þ 3 H2 S O4ðaqÞ ð8Þ
This reaction, for the first time in the evolution of typical arc mag-
matic to hydrothermal systems, generates high activities of dissolved
sulfide, which cause the early precipitation of Cu- and Mo-bearing sul-
fide minerals (chalcopyrite, bornite, and molybdenite, along with
1/T x 103
1.5 1.0
–5
–10 I-type
Magmas
Porphyry
log fO
2 Cu-Au Deposits
–15
MORB
S-type
Magmas
–20
Porphyry
Sn-W Deposits
–25
400 500 600 700 800 900 1000 1100
T (°C)
Fig. 7. Temperature vs. log fO2 diagram, showing the ranges of conditions characteristic of
porphyry Cu-Au deposits, I-type calc-alkaline magmas, S-type magmas, and mid-ocean-
ridge basalts (MORB). The main mineral and volatile fO2 buffer curves are also shown.
Modified from Burnham and Ohmoto (1980) and Hedenquist and Richards (1998). Abbre-
viations: Fay = fayalite; Hm = hematite; Mt = magnetite; Po = pyrrhotite; Py = pyrite;
Qz = quartz.
pyrite). Anhydrite is also precipitated in abundance due to the high ac-
tivities of dissolved sulfate (Gustafson and Hunt, 1975; Lowell and
Guilbert, 1970). As temperatures continue to cool and Eq. (8) progresses
further to the right, the fluids become increasingly acidic from the disso-
ciation of H2SO4 (and HCl; Hedenquist and Taran, 2013), leading to the
characteristic formation of sericite (phyllic alteration) and then clays
(argillic alteration) in originally feldspar-stable wallrocks (potassic al-
teration; Beane and Titley, 1981; Harris and Golding, 2002; Hemley
and Jones, 1964; Montoya and Hemley, 1975; Reed et al., 2013). Copper
and Mo precipitate from these fluids in response to: (1) cooling be-
tween ~ 425°–350 °C (Crerar and Barnes, 1976; Hemley et al., 1992;
Hurtig and Williams-Jones, 2014b; Klemm et al., 2007; Landtwing
et al., 2005, 2010; Redmond et al., 2004); (2) the increase in fH2S
resulting from SO2 disproportionation (Simon and Ripley, 2011); and
(3) in the case of Mo, decreasing pH (Rempel et al., 2008, 2009; Seo
et al., 2012). Gold may also precipitate with these sulfide minerals
(Simon et al., 2005), and/or may stay in solution to lower temperatures
as bisulfide or chloride complexes, potentially to be precipitated in the
geothermal/epithermal environment (Gammons and Williams-Jones,
1997; Hedenquist et al., 1993, 1998; Heinrich et al., 2004; Hurtig and
Williams-Jones, 2014a; Kouzmanov and Pokrovski, 2012; Pudack
et al., 2009; Simmons and Brown, 2007).
6. Conclusions
The purpose of this review has been to explore the roles of one inten-
sive parameter (oxidation state) and one extensive parameter (sulfur
content) in arc magma-genesis and metallogeny. These two parameters
together exercise fundamental controls on the behavior of metals
during partial melting in the mantle, differentiation in the crust, and dur-
ing volatile exsolution and cooling. The additional essential presence of
water in these magmatic-to-hydrothermal systems is taken as read
(e.g., Burnham, 1979; Candela, 1992; Richards, 2011b).
The majority of experimental and analytical observations suggest
that seafloor alteration and sedimentation since the Neoproterozoic
 J.P. Richards / Lithos 233 (2015) 27–45
Oxygenation Event introduces a flux of oxidized components into the
mantle wedge upon subduction and slab devolatilization. Chief among
these oxidants is probably sulfate, originally derived from seawater
and fixed in altered seafloor basalts or sediments. Ferric iron is less mo-
bile in hydrothermal fluids, but may cause further oxidation of sulfides
to soluble sulfates during prograde metamorphism by in situ conversion
to ferrous iron. Ferric iron may also be efficiently mobilized by partial
melts of the slab.
The process of hydration and oxidation of the mantle wedge above
the subducting and devolatilizing slab is likely to be slow and incremen-
tal, possibly requiring up to 10 m.y. to achieve a steady state condition of
1 or 2 log fO2 units above background depleted mantle values (e.g., up to
ΔFMQ ≈ +1). However, this modest increase in oxidation state is suffi-
cient to shift the balance between dissolved sulfide and sulfate compo-
nents in the melt towards more soluble sulfates, allowing the magmas
to dissolve much larger amounts of sulfur than reduced melts. The re-
quirement for a considerable amount of time before the mantle wedge
becomes “primed” to generate potentially fertile (moderately oxidized,
S-rich, hydrous) melts may explain the rarity of porphyry deposits in
primitive island arcs, and the late appearance of large porphyry deposits
within magmatic cycles in many continental arcs.
Although some metals may be carried into the mantle wedge by the
subduction zone fluids, this is not essential, because the mantle already
contains substantial background concentrations of base and precious
metals (e.g., 30 ppm Cu, 1 ppb Au, 6.2 ppb Pt in depleted mantle;
Salters and Stracke, 2004). The significance of the flux of water and ox-
idized sulfur from the slab is that it lowers the solidus of peridotite caus-
ing partial melting, and lowers the stability of condensed sulfide phases
(melts or minerals) while maintaining a high fS2. Consequently,
chalcophile and siderophile elements will behave incompatibly
(where residual sulfides are absent) or weakly compatibly (where sul-
fide abundances are low), and will tend to partition into the silicate
melt, whose sulfur load will be dominantly in the form of sulfate.
Processing of these largely metal-undepleted magmas in lower
crustal MASH or “hot zones” under mildly oxidized but marginally
sulfide-saturated (high fS2) conditions can be expected to leave at
least some of the metal load of the magma flux in cumulates and gab-
broic plutons, but available data do not indicate that these rocks contain
much more than background concentrations of metals such as Cu. Data
for Au and PGE are sparse, and it is possible that these highly siderophile
elements may be significantly enriched in residual sulfides, and may
represent a source of metals for later, post-subduction magmatism.
Thus, segregation of this material does not seem to significantly deplete
the remaining magma in Cu (or Mo), although Au and PGE may be lost.
Andesitic magmas rising into the upper crust still typically contain be-
tween 50–100 ppm Cu, which has been shown to be more than ade-
quate to form large porphyry Cu deposits (Cline and Bodnar, 1991).
Transferring the remaining metal load of the magma into a hydro-
thermal fluid phase that can generate porphyry Cu-Mo ± Au minerali-
zation might be either a one- or two-step process, involving either
direct partitioning of metals from the melt into the exsolving hydrother-
mal fluid, or preconcentration of metals in an immiscible or crystallizing
sulfide phase, followed by redissolution of these sulfides by hydrother-
mal fluid. The high and increasing oxidation states of evolved arc
magmas suggests that, while some condensed sulfide may indeed be
present in late-stage magmas, it will not be abundant, and is therefore
not likely to significantly affect the overall metal budget of the system.
Occam’s razor suggest that, in the absence of clear evidence to the con-
trary, the simpler one-step magma-to-fluid partitioning process can ef-
ficiently form large porphyry deposits, and the processes involved are
well established in the literature.
Sulfur content and oxidation state have one last, essential role to
play in the precipitation of sulfide ores from metalliferous magmatic-
hydrothermal fluids. The bulk of the sulfur in moderately oxidized,
high temperature hydrothermal fluids is dissolved as SO2, but this mol-
ecule begins to back-react with its solvent (H2O) as temperatures start
39
to fall below ~ 400 °C to form H2S and H2SO4. The newly formed H2S
quickly bonds with dissolved metals to precipitate as sulfide minerals
(chalcopyrite, molybdenite, pyrite), while the H2SO4 (and HCl) causes
increasingly acidic forms of wallrock alteration at lower temperatures
(b350 °C; sericite and clay).
In summary, the combination of high water and sulfur contents, and
moderate oxidation state (ΔFMQ ≈ +1) of typical arc magmas is suffi-
cient to mobilize metals such as Cu and Mo from the asthenospheric
mantle wedge above subduction zones into the upper crust, where
they can be partitioned into exsolving hydrothermal fluids and
reprecipitate upon cooling to form porphyry-type ore deposits. Condi-
tions that might cause retention of large volumes of sulfide, either in
the mantle source or during lower crustal MASH processes, will likely
reduce the potential for direct porphyry ore formation, although these
sulfides and their contained metals might be remobilized during later
(post-subduction) melting events.
Acknowledgements
This work was supported by a Discovery Grant from the Natural
Sciences and Engineering Research Council of Canada. I thank Derek
Wyman for inviting this contribution, which is dedicated to the memory
of Robert Kerrich. Rob was my post-doctoral supervisor, and instilled in
me a sense of balanced and rigorous enquiry that I hope this review
does justice to. The loss of Rob’s influence and mentorship is a great
blow to our discipline. I thank Katy Evans and David Cooke for helpful
reviews of the manuscript, and Clayton Deutsch for statistical advice.
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