Ore Geology Reviews 40 (2011) 1–26

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Ore Geology Reviews

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / o r e g e o r ev

Review

Magmatic to hydrothermal metal fluxes in convergent and collided margins

Jeremy P. Richards ⁎
Dept. of 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: Metals such as Cu, Mo, Au, Sn, and W in porphyry and related epithermal mineral deposits are derived
Received 1 December 2010 predominantly from the associated magmas, via magmatic–hydrothermal fluids exsolved upon emplacement into
Received in revised form 18 May 2011 the mid- to upper crust. Four main sources exist for magmas, and therefore metals, in convergent and collided plate
Accepted 19 May 2011
margins: the subducting oceanic plate basaltic crust, subducted seafloor sediments, the asthenospheric mantle
Available online 27 May 2011
wedge between the subducting and overriding plates, and the upper plate lithosphere. This paper firstly examines
Keywords:
the source of normal arc magmas, and concludes that they are predominantly derived from partial melting of the
Porphyry deposit metasomatized mantle wedge, with possible minor contributions from subducted sediments. Although some
Epithermal deposit metals may be transferred from the subducting slab via dehydration fluids, the bulk of the metals in the resultant
Subduction magmas are probably derived from the asthenospheric mantle. The most important contributions from the slab
Post-subduction from a metallogenic perspective are H2O, S, and Cl, as well as oxidants. Partial melting of the subducted oceanic crust
Magmatic–hydrothermal fluid and/or sediments may occur under some restricted conditions, but is unlikely to be a widespread process (in
Ore formation Phanerozoic arcs), and does not significantly differ metallogenically from slab-dehydration processes.
Primary, mantle-derived arc magmas are basaltic, but differ from mid-ocean ridge basalt in having higher water
contents (~10× higher), oxidation states (~2 log fO2 units higher), and concentrations of incompatible elements
and other volatiles (e.g., S and Cl). Concentrations of chalcophile and siderophile metals in these partial melts
depend critically on the presence and abundance of residual sulfide phases in the mantle source. At relatively
high abundances of sulfides thought to be typical of active arcs where fS2 and fO2 are high (magma/sulfide
ratio = 102–105), sparse, highly siderophile elements such as Au and PGE will be retained in the source, but
magmas may be relatively undepleted in abundant, moderately chalcophile elements such as Cu (and perhaps
Mo). Such magmas have the potential to form porphyry Cu ± Mo deposits upon emplacement in the upper crust.
Gold-rich porphyry deposits would only form where residual sulfide abundance was very low (magma/sulfide
ratio N 105), perhaps due to unusually high mantle wedge oxidation states.
In contrast, some porphyry Mo and all porphyry Sn–W deposits are associated with felsic granitoids, derived
primarily from melting of continental crust during intra-plate rifting events. Nevertheless, mantle-derived
magmas may have a role to play as a heat source for anatexis and possibly as a source of volatiles and metals.
In post-subduction tectonic settings Tulloch and Kimbrough, 2003, such as subduction reversal or migration, arc
collision, continent–continent collision, and post-collisional rifting, a subducting slab source no longer exists,
and magmas are predominantly derived from partial melting of the upper plate lithosphere. This lithosphere will
have undergone significant modification during the previous subduction cycle, most importantly with the
introduction of large volumes of hydrous, mafic (amphibolitic) cumulates residual from lower crustal
differentiation of arc basalts. Small amounts of chalcophile and siderophile element-rich sulfides may also be left
in these cumulates. Partial melting of these subduction-modified sources due to post-subduction thermal
readjustments or asthenospheric melt invasion will generate small volumes of calc-alkaline to mildly alkaline
magmas, which may redissolve residual sulfides. Such magmas have the potential to form Au-rich as well as
normal Cu± Mo porphyry and epithermal Au systems, depending on the amounts of sulfide present in the lower
crustal source. Alkalic-type epithermal Au deposits are an extreme end-member of this range of post-subduction
deposits, formed from subduction-modified mantle sources in extensional or transtensional environments.
Ore formation in porphyry and related epithermal environments is critically dependent on the partitioning of
metals from the magma into an exsolving magmatic–hydrothermal fluid phase. This process occurs most
efficiently at depths greater than ~6 km, within large mid- to upper crustal batholithic complexes fed by arc or
post-subduction magmas. Under such conditions, metals will partition efficiently into a single-phase,
supercritical aqueous fluid (~2–13 wt.% NaCl equivalent), which may exist as a separate volatile plume or as
bubbles entrained in buoyant magma. Focusing of upward flow of bubbly magma and/or fluid into the apical
regions of the batholithic complex forms cupolas, which represent high mass- and heat-flux channelways

⁎ Tel.: + 1 780 492 3430; fax: + 1 780 492 2030.

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

0169-1368/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.oregeorev.2011.05.006
2 J.P. Richards / Ore Geology Reviews 40 (2011) 1–26

towards the surface. Cupolas may be self-organizing to the extent that once formed, further magma and fluid
flow will be enhanced along the weakened and heated axes. Cupolas may form initially as breccia pipes by
volatile phase (rather than magma) reaming-out of extensional structures in the brittle cover rocks, to be
followed immediately by magma injection to form cylindrical plugs or dikes.
Cupola zones may extend to surface, where magmas and fluids vent as volcanic products and fumaroles. Between
the surface and the underlying magma chamber, a very steep thermal gradient exists (700°–800 °C over b 5 km),
which is the primary cause of vertical focusing of ore mineral deposition. The bulk of metals (Cu ± Mo± Au) that
forms porphyry ore bodies are precipitated over a narrow temperature interval between ~425° and 320 °C, where
isotherms in the cupola zone rise to within ~2 km of the surface. Over this temperature range, four important
physical and physicochemical factors act to maximize ore mineral deposition: (1) silicate rocks transition from
ductile to brittle behavior, thereby greatly enhancing fracture permeability and enabling a threefold pressure
drop; (2) silica shows retrograde solubility, thereby further enhancing permeability and porosity for ore
deposition; (3) Cu solubility dramatically decreases; and (4) SO2 dissolved in the magmatic–hydrothermal fluid
phase disproportionates to H2S and H2SO4, leading to sulfide and sulfate mineral deposition and the onset of
increasingly acidic alteration.
The bulk of the metal flux into the porphyry environment may be carried by moderately saline supercritical
fluids or vapors, with a volumetrically lesser amount by saline liquid condensates. However, these vapors rapidly
become dilute at lower temperatures and pressures, such that they lose their capacity to transport metals as
chloride complexes. They retain significant concentrations of sulfur species, however, and bisulfide complexing
of Cu and Au may enable their continued transport into the epithermal regime. In the high-sulfidation
epithermal environment, intense acidic (advanced-argillic) alteration is caused by the flux of highly acidic
magmatic volatiles (H2SO4, HCl) in this vapor phase. Ore formation, however, is paragenetically late, and may be
located in these extremely altered and leached cap rocks largely because of their high permeability and porosity,
rather than there being any direct genetic connection. Ore-forming fluids, where observed, are low- to
moderate-salinity liquids, and are thought to represent later-stage magmatic–hydrothermal fluids that have
ascended along shallower (cooler) geothermal gradients that either do not, or barely, intersect the liquid–vapor
solvus. Such fluids “contract” from the original supercritical fluid or vapor to the liquid phase. Brief intersection
of the liquid–vapor solvus may be important in shedding excess chloride and chloride-complexed metals (such
as Fe), so that bisulfide-complexed metals remain in solution. Such a restrictive pressure–temperature path is
likely to occur only transiently during the evolution of a magmatic–hydrothermal system, which may explain the
rarity of high-sulfidation Cu–Au ore deposits, despite the ubiquitous occurrence of advanced-argillic alteration in
the lithocaps above porphyry-type systems.
© 2011 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2. Magma generation in convergent and collided margins: geochemical characteristics and partitioning of metals . . . . . . . . . . . . . . . . . . 3
2.1. Slab dehydration and asthenospheric melting in subduction zones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1.1. Behavior of metals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.2. Sediment dehydration and/or melting in subduction zones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.2.1. Behavior of metals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.3. Oceanic slab melting in subduction zones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.3.1. Behavior of metals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.4. Supra-subduction zone lithospheric melting: the MASH process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.4.1. Behavior of metals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.4.2. Sources of Mo . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.5. Lithospheric melting during post-subduction events . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.5.1. Behavior of metals in subduction-modified sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.6. Crustal melting during post-collisional stress relaxation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.6.1. Sources of metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3. Behavior of metals during magma fractionation and fluid exsolution in the upper crust . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.1. Partitioning of metals from magma into exsolving hydrothermal fluid. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
4. Magmatic–hydrothermal ore formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4.1. Porphyry Cu ore formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4.2. Epithermal Cu–Au ore formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.2.1. High-sulfidation epithermal Cu–Au deposits. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.2.2. Low-sulfidation epithermal Au deposits (including alkalic-type deposits) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
5. Summary and conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
5.1. Sources of magmas and metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
5.2. Porphyry and epithermal ore formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
 J.P. Richards / Ore Geology Reviews 40 (2011) 1–26
1. Introduction
The question of the source of various elements in convergent and
collided margin magmas has challenged geologists for decades. Igneous
petrologists seek to understand the petrogenesis of such magmas
through geochemical and isotopic tracing, whereas economic geologists
are generally more interested in the source of potentially valuable
elements such as Cu, Mo, Sn, W, Au, and platinum group elements (PGE),
which may ultimately be found in intrusion-related hydrothermal
deposits.
Igneous petrologists are broadly in agreement that arc magmas are
primarily derived from hydrous melting of the asthenospheric mantle
wedge above subducting plates, but melts from the subducted oceanic
crust (including sediments) and the upper plate lithosphere may also
be involved to varying degrees.
Economic geologists are also broadly in agreement that ore-forming
elements are partitioned from such magmas into an exsolving volatile
phase upon emplacement in the upper crust, and may then be
precipitated from these fluids during cooling, fluid mixing, and wallrock
reaction processes in porphyry-type and related epithermal mineral
deposits. However, these process theories do not address where the
metals originally came from, nor why porphyry deposits vary so widely
in their metal contents (from Au-rich, through Cu± Mo ± Au, to Mo-
only deposits, with Sn–W deposits forming a distinct variant).
In addition to subduction-related calc-alkaline magmas, a diverse
suite of calc-alkaline to alkaline magmas is generated in post-
subduction and collisional tectonic settings, and these magmatic
systems may also generate porphyry and epithermal ore deposits.
Such systems raise an additional set of petrogenetic and metallogenic
questions.
It is the intent of this paper to merge these different geological
perspectives on magmagenesis and metallogeny in order to discuss
primary metal fluxes in convergent and collisional margins in terms of
igneous petrogenetic and magmatic–hydrothermal processes. The
ultimate metal inventory and metal ratios in any given porphyry or
related deposit is secondarily controlled by late-stage magmatic and
shallow crustal processes. These processes are examined, closing with a
review of fluid and metal sources and behavior in related epithermal
environments.
2. Magma generation in convergent and collided margins:
geochemical characteristics and partitioning of metals
Most magmas erupted through or emplaced within the Earth's crust
are not primary magmas (in the sense of being chemically unmodified
since extraction from their source), and most are not even primitive (in
the sense of being relatively unevolved; Hildreth and Moorbath, 1988;
Leeman, 1983; Neuendorf et al., 2005; Smith et al., 2010; Thirlwall et al.,
1996). Except for magmas produced and erupted in extensional tectonic
regimes (where rapid ascent to the surface is facilitated by normal
faulting), most deeply-derived magmas undergo some degree of
fractionation and crustal contamination during their passage towards
the surface. It is therefore challenging to isolate geochemical and
isotopic characteristics of magma source regions from the effects of later
processes (Davidson, 1996). Magmas erupted through mature conti-
nental crust are the most difficult to fingerprint uniquely in terms of
source characteristics because wallrock assimilation and fractional
crystallization (AFC; DePaolo, 1981) are ubiquitous and commonly
extensive processes that will significantly modify bulk rock geochemical
and isotopic compositions; and yet, these are also the magmas that are
most commonly associated with porphyry- and epithermal-type
mineral deposits. The difficulty in constraining source characteristics
in such magmas is perhaps responsible for the plethora of theories that
have been proposed for the origin of ore-forming magmas in convergent
margin settings, ranging from the melting of subducting oceanic crust
and/or seafloor sediments, through melting of subduction metasoma-
3
tized asthenospheric or lithospheric mantle, to melting of underplated
or primitive lower crustal rocks, and even melting of evolved crustal
rocks in the case of some felsic porphyry Mo and Sn–W magmas.
Therefore, rather than start by trying to identify a unique source
for the typical intermediate-to-felsic calc-alkaline magmas that are
associated with ore deposits in mature convergent margins, I begin
this review by focusing on the much better constrained primitive
island arc environment, where the effects of fractionation and crustal
contamination, particularly by continentally derived materials, are
minimized, and processes in mantle source regions can be more
clearly defined.
2.1. Slab dehydration and asthenospheric melting in subduction zones
There is a general consensus that, with the exception of young
oceanic lithosphere (b25 m.y.-old; Defant and Drummond, 1990) or
plate edges (Yogodzinski et al., 2001), basaltic oceanic crust undergoes
low-temperature, high pressure metamorphism upon subduction,
which releases fluids through a series of prograde dehydration reactions
to form anhydrous eclogite (Fig. 1). Water and other volatile
components and solutes (including S and Cl) were originally incorpo-
rated into oceanic crustal and upper mantle rocks during oxidizing
seafloor alteration, generating hydrous minerals such as serpentine, talc,
amphibole, micas, chlorite, zoisite, chloritoid, and lawsonite. Various
experimental studies have shown that these minerals undergo
dehydration reactions over a depth range extending to ~100 km,
corresponding to the blueschist–eclogite transition in crustal rocks;
serpentine (antigorite) and the 10 Å equivalent of chlorite may extend
this range to 200 km (e.g., Dvir et al., 2011; Forneris and Holloway, 2003;
Fumagalli and Poli, 2005; Poli and Schmidt, 2002; Schmidt and Poli,
1998; Ulmer and Trommsdorff, 1995). Below these depths, the
anhydrous eclogitic crust is essentially infusible, and the dense slab
continues its descent into the mantle without melting. See reviews of
this subject by Richards (2003, 2005, and references therein).
Numerous studies have explored the character of the fluids that are
released from the dehydrating slab, because they are thought to account
for the unique geochemical character of subduction-related magmas
during later partial melting in the metasomatized asthenospheric
mantle wedge (located between the downgoing slab and the upper
plate). Slab-derived fluids are thought to be water-rich at these depths,
and to carry significant amounts of other volatile components such as Cl
and S. For example, salinities in the range of 4–10 wt.% NaCl have been
inferred from primitive basalt or melt inclusion studies (de Hoog et al.,
2001; Kent et al., 2002; Portnyagin et al., 2007; Wallace, 2005;
Wysoczanski et al., 2006), and salinities of 0.4–2 wt.% NaCl equivalent
were measured in fluid inclusions from high-pressure rocks thought to
represent subducted oceanic mantle (Scambelluri et al., 2004). At higher
pressures (~6 GPa) and greater depths (~175 km) there may no longer
be a physical distinction between solute-rich aqueous liquids and
hydrous silicate melts, and the fluid may be supercritical in nature (e.g.,
Kessel et al., 2005a,b), but the role of such deeply released fluids in
subduction zone magmatism is unclear (see discussion in Richards and
Kerrich, 2007).
In addition to volatiles, water-soluble large ion lithophile elements
(LILE: K, Rb, Cs, Ca, Sr, and Ba, and U), and B, Pb, As, and Sb (Breeding et al.,
2004; Hattori et al., 2005; Hattori and Guillot, 2003; Kogiso et al., 1997;
Manning, 2004; Tatsumi et al., 1986) are thought to be mobilized into the
forearc mantle wedge by dehydration fluids, which may then be
convected by corner-flow into the sub-arc melting zone (Fig. 1). These
fluid–mobile components are also characteristically enriched in arc
magmas (e.g., typical ranges of: 1–3 wt.% H2O, 500–2000 ppm Cl, 900–
2500 ppm S; Davidson, 1996; Gill, 1981; Noll et al., 1996; Sobolev and
Chaussidon, 1996; Wallace, 2005; Portnyagin et al., 2007), which is taken
as evidence of aqueous fluid metasomatism of the mantle wedge magma
source. Silica may also be significantly mobilized in these slab fluids
(Aerts et al., 2010; Manning, 2004), as well as Tl and Cu (Noll et al., 1996;
4 J.P. Richards / Ore Geology Reviews 40 (2011) 1–26

Volcanic arc
Sea level 0 km
Sediment
Oceanic crust Oceanic crust
Chlorite + Mantle
Oceanic mantle

serpentine lithosphere
lithosphere

Talc 600°C
Chlorite
Am
p
De hib 1000
hy ole Man °C
dr tle c
lith atio orne
r flo
os n o w
ph f o Zo Partial melting
Asthenosphere er ce is 100 km
e a ite 140
60 ni Metasomatized 0°C
0° c C
C C td asthenosphere
hl
10 o
00 + rite
°C se –1
rp 0Å
en p

10
tin ha E

00
e se c 14

°C
lo 00
gi
te °C
Se
rp
en
tin
e

200 km

Fig. 1. Structure and processes beneath an oceanic island arc (sources: Tatsumi and Eggins, 1995; Schmidt and Poli, 1998; Winter, 2001; Poli and Schmidt, 2002; Fumagalli and Poli,
2005). Primary hydrous basaltic arc magmas are derived from partial melting of the metasomatized asthenospheric mantle wedge. Mineral zones shown in the subducting plate
indicate lower limits of stability of hydrous phases in the basaltic oceanic crust and peridotitic mantle lithosphere. Abbreviation: Ctd = chloritoid.

Stolper and Newman, 1994). The normally relatively incompatible high
field strength elements (HFSE) Ti, Nb, and Ta are not significantly fluid
soluble under subduction zone conditions, and are retained in minerals
such as rutile either in the slab or the mantle wedge (Audétat and
Keppler, 2005; Brenan et al., 1994; Green and Adam, 2003). Arc magmas
derived from these sources therefore show characteristic negative
anomalies for these three elements on mantle-normalized spider
diagrams, but display enrichments in most other incompatible elements
(Foley et al., 2000; Gill, 1981; Klemme et al., 2005; Ryerson and Watson,
1987; Schmidt et al., 2004; Schmidt et al., 2009).
Hydrous metasomatism of the mid-ocean-ridge basalt (MORB)-
depleted asthenospheric mantle wedge causes partial melting by
lowering the solidus of peridotite (Arculus, 1994; Kushiro et al., 1968;
Stolper and Newman, 1994). This occurs either through direct infiltration
metasomatism by slab-derived fluids percolating into the hot inner zone
of the mantle wedge (Bourdon et al., 2003; Grove et al., 2006; Kelley et al.,
2010; Peacock, 1993), or by convective corner-flow mixing of metaso-
matized peridotite into these hotter central regions (Fig. 1; Schmidt and
Poli, 1998; Tatsumi, 1986; Wysoczanski et al., 2006).
Partial melting of hydrated peridotite under these conditions in
the mantle wedge generates high-Mg basalts (Greene et al., 2006;
Pichavant et al., 2002; Smith et al., 2010). Such arc basalts are
distinguished from MORB by higher contents of incompatible
elements (as noted above) and water (up to 6 wt.% H2O; Cervantes
and Wallace, 2003; Grove et al., 2003; Pichavant et al., 2002; Sobolev
and Chaussidon, 1996). Critically, Hamada and Fujii (2008) and
Zimmer et al. (2010) report that a water content of 2 wt.% separates
“dry” tholeiitic (olivine + plagioclase/orthopyroxene) from “wet”
calc-alkaline (clinopyroxene + magnetite) magmatic fractionation
trends.
Arc basalts are also characterized by distinctly higher oxidation
states than MORB (up to 2 log units above the fayalite–magnetite–
quartz buffer: ΔFMQ + 2; Ballhaus, 1993; Brandon and Draper, 1996;
Parkinson and Arculus, 1999; Rowe et al., 2009). The relatively high
oxidation state of arc magmas is a critical factor in their subsequent
metallogeny, and originates from oxidative seafloor alteration of the
oceanic plate (Staudigel et al., 1996), transmitted into the mantle wedge
by the metasomatic fluid flux (Brandon and Draper, 1996; Kelley and
Cottrell, 2009; Malaspina et al., 2009).
2.1.1. Behavior of metals
Most base and precious metals would be expected to have at least
moderate solubilities in the hot, relatively oxidized, saline aqueous
fluids exsolved from the downgoing slab. In particular, as noted in
Section 2.1, Pb, As, and Sb are strongly mobilized by such fluids, possibly
along with Tl and Cu (Noll et al., 1996). The behavior of highly
siderophile elements (HSE) such as Au and PGE is less well known under
these conditions, but studies of metasomatized mantle xenoliths from
island arc lavas suggest that Au, Re, and the Pd-group elements
(including Pt) are mobilized into the mantle wedge during subduction
metasomatism (Dale et al., 2009; Kepezhinskas et al., 2002; McInnes et
al., 1999; Sun et al., 2004a; Widom et al., 2003).
The volumetric extent and efficiency of mobilization of metals into
the mantle wedge by this process are unknown, but fluid metasomatism
clearly represents one viable mechanism for metal transfer into arc
magma sources.
The behavior of chalcophile and siderophile metals during subse-
quent partial melting of the metasomatized mantle wedge depends
critically on oxidation state (fO2) and sulfur fugacity (fS2), because these
parameters control the stability and abundance of sulfide phases. Gold
and PGE partition strongly into sulfide phases relative to silicate melts,
but Cu to a somewhat lesser degree (Campbell and Naldrett, 1979;
Peach et al., 1990), so if sulfides are abundant in the magma source
region, partial melts will be depleted in Au and PGE relative to Cu
(Fig. 2). Under the high fO2 and fS2 conditions of the supra-subduction
zone mantle wedge, the bulk of the sulfur flux will likely consist of SO2 or
 J.P. Richards / Ore Geology Reviews 40 (2011) 1–26 5

sulfate, dissolved first in slab fluids and then magma (Carroll and Nevertheless, Aizawa et al. (1999); Dreyer et al. (2010); and Duggen
Rutherford, 1985; Jenner et al., 2010; Jugo et al., 2005a). However, et al. (2007) have suggested that dehydration is the principal process
because of the equilibria between various sulfur species, at high fS2 some affecting sediments down to depths of ~100 km (i.e., to below the
condensed sulfide phases will likely also be present (McInnes et al., volcanic arc), with melting only occurring significantly at greater
2001). Consequently, Richards (2009) suggested that normal arc depths when temperatures exceed ~800 °C (possibly reflected in the
magmas will be minimally depleted in Cu (due to its higher abundance geochemistry of some back-arc magmas).
and moderate chalcophile nature) relative to sparse, highly siderophile Sediment contributions to the source of arc magmas have been the
elements such as Au and PGE, which will be strongly retained in residual subject of numerous studies, with the least ambiguous evidence
sulfide phases in the source region (e.g., Hamlyn et al., 1985; Mitchell coming from island arcs (e.g., MacDonald et al., 2000; Thirlwall et al.,
and Keays, 1981; Peach et al., 1990). This may explain the Cu-rich nature 1996; Wysoczanski et al., 2006). In continental arcs, it can be difficult
of typical arc-related porphyry deposits (relative to Au and PGE; to distinguish between chemical and isotopic signatures from
Richards, 2005). In contrast, Au-rich porphyry deposits may require subducted continent-derived sediment versus crustal contamination
atypical subduction-related or collisional tectonic settings and petro- during magma ascent (e.g., Hildreth and Moorbath, 1988; Kemp et al.,
genetic processes, which act to destabilize residual sulfide phases and 2007): both sources will contribute incompatible elements and
render Au incompatible (e.g., Jégo et al., 2010; Richards, 1995, 2009; crustal isotopic values to primary mantle-derived arc magmas
Sillitoe, 2000; Solomon, 1990; Wyborn and Sun, 1994; see Section 2.5). (Breeding et al., 2004).
The low abundances of PGE in many arc-related ore deposits suggest a Trace elements commonly used as indicators of sediment contribu-
further separation of these elements from Au and Cu, perhaps through tions to arc magmas are Ba, B, Be, Th, and Pb (Dreyer et al., 2010; Johnson
the formation of residual platinoid alloy phases (e.g., Barnes et al., 1985; and Plank, 1999), and Ba/La and Th/La ratios can be used as a measure of
Borisov and Palme, 1997; Kepezhinskas et al., 2002; Peach et al., 1990) sediment versus mantle source components (Plank, 2005; Walker et al.,
or Cr-spinels (into which Ir-group PGE strongly partition; Hattori et al., 2001). In particular, the cosmogenic radioisotope 10Be can be used as a
2010; Righter et al., 2004). tracer of recent (b10 Ma) introduction of sediments into arc magma
sources (Dreyer et al., 2010; Morris et al., 1990). However, although a
2.2. Sediment dehydration and/or melting in subduction zones clear sediment-derived isotopic signature can be observed in many
island arc systems, the volumetric contribution of sediments to island
Seafloor sediments on the surface of the downgoing slab are arc magmas seems to be relatively minor (Hawkesworth et al., 1994;
another potential source of metasomatic contributions to the mantle Kilian and Behrmann, 2003; Poli and Schmidt, 2002; Stern et al., 2006).
wedge. Much of this sedimentary material will be scraped off at the One additional element that may be added to the mantle wedge
trench to form an accretionary prism, but varying amounts may also from subducted sediments is sulfur, as suggested by the positive δ 34S
be subducted, depending on the degree of coupling between the compositions of arc magmas (de Hoog et al., 2001), which are similar
upper and lower plates, and also the sediment input load (Fig. 1). Such to those of seafloor sediments (Alt et al., 1993). Analyses of glass
sediments will be water-rich and pelitic in bulk composition, and thus inclusions in olivine from primitive arc magmas reveal concentrations
are more likely to undergo partial melting under subduction zone of up to 2900 ppm S (de Hoog et al., 2001), and Jugo et al. (2005b)
conditions than basaltic oceanic crust (Hermann and Spandler, 2008). measured experimental concentrations of up to 1.5 wt.% S in oxidized
arc basalts. These high sulfur contents have great significance for the
behavior of chalcophile and siderophile metals (see Sections 2.1.1,
2.5.1, and 3).

Porphyry Cu Porphyry Cu-Au 2.2.1. Behavior of metals

potential arc potential
6 magmas magmas Lead, which is significantly enriched in the continental crust (and
10
d in crustally-derived sediments) relative to the mantle, is the only metal for
che ide
105 e nri l sulf
Au idua which a clear sedimentary source can be inferred in some island arc
res
104 magmas, because it can be readily identified by its radiogenic isotopic
de composition compared with depleted mantle sources. However, in
103 ulfi
in s Cu maximized in
Cu
lfid
e magma (R ≥ 10 3) continental arcs, distinguishing a subducted sediment source of
102 ns
u
i 50 ppm Cu radiogenic Pb from crustal contamination during magma ascent is
Cu (ppm)

Au
Au (ppb)

10
ag
m a
5 ppb Au very difficult (e.g., Barreiro, 1984; Chiaradia et al., 2004; Kontak et al.,
m
1 Cu
in
gma Au maximized in 1990). This has led to diverging opinions: for example, Aitcheson et al.
ma magma (R ≥ 106)
ed
in (1995); Hildreth and Moorbath (1988); James (1982); Kay et al. (1999);
0.1 plet
de Sulfide/silicate melt partition and Tilton et al. (1981) concluded that the bulk of the radiogenic Pb in
10–2 Au coefficients:
a
D(Cu) = 103 central Andean magmas comes from upper plate crustal sources,
gm D(Au) = 105
10–3 ma whereas Macfarlane (1999); McNutt et al. (1979); Mukasa et al.
n Metal concentrations in
ui
10–4
A magma in absence of sulfide: (1990); and Sillitoe and Hart (1984) preferred a subducted sediment
Cu = 50 ppm
Au = 5 ppb source for Pb in some Andean igneous rocks and ore deposits.
10–5
Inferring a seafloor sediment source for other metallic components
1 10 102 103 104 105 106 107 108
R = (mass of silicate melt)/(mass of sulfide) in arc magmas (and related ore deposits) is much more speculative,
and generally involves the subduction of metal-rich manganese
nodules or even massive sulfide deposits. The latter, however, likely
Fig. 2. Concentrations of Cu and Au in silicate magma and coexisting sulfide liquid as a
oxidize and disperse geologically rapidly after formation on the
function of R = [mass of silicate melt]/[mass of sulfide melt] (Campbell and Naldrett,
1979; diagram modified from Richards, 2005, 2009). At R-factors below ~ 102, magmas seafloor (e.g., Edwards, 2004; Herzig et al., 1991) unless quickly
will be depleted in both Cu and Au. At R-factors between ~ 102–105, magmas will be buried by lava; they might thus only be expected to be subducted with
depleted in Au but essentially undepleted in Cu (porphyry Cu-potential magmas). At R- very young oceanic crust. Few studies have specifically invoked a
factors N105, magmas will be undepleted in Au and Cu (porphyry Cu–Au–potential subducted sediment source for ore metals other than a component of
magmas). A corollary of this diagram is that arc magmatism will leave small amounts of
relatively Au-rich sulfide in the mantle source or lithosphere during fractionation,
Pb, and the majority of authors have concluded that such a source is
which can be remelted during post-subduction tectonomagmatic processes, to form either unnecessary or unproven (e.g., Burnham, 1981; Chiaradia et al.,
small-volume, alkaline, porphyry Au-potential magmas. 2004; de Hoog et al., 2001; Fontboté et al., 1990).
6 J.P. Richards / Ore Geology Reviews 40 (2011) 1–26
2.3. Oceanic slab melting in subduction zones
The question of whether the downgoing oceanic slab, or more
specifically the basaltic oceanic crust, melts during subduction has
prompted lively debate recently, not only in the petrology literature
(e.g., Conrey, 2002; Defant and Kepezhinskas, 2001, 2002; Garrison and
Davidson, 2003), but also amongst economic geologists because of the
suggestion that “slab melts” might in some way be uniquely fertile for later
porphyry ore formation (e.g., Mungall, 2002; Oyarzun et al., 2001, 2002;
Sajona and Maury, 1998; Thiéblemont et al., 1997; for contrary opinions,
see: Rabbia et al., 2002; Richards, 2002; Richards and Kerrich, 2007).
The idea that the hydrated basaltic ocean crust might melt during
subduction was an early assumption of the plate tectonic revolution,
because it seemed conveniently to explain the relatively felsic
composition of arc magmas (as opposed to basalts formed by melting
of peridotitic mantle). The theory was given credence by the
experiments of Rapp et al. (1991) and Rapp and Watson (1995), who
showed that melting of amphibolite under upper mantle conditions
(1025 °C and 0.8–1.6 GPa) could generate an intermediate composition
tonalite–trondhjemite melt, not dissimilar to an arc andesite. Defant and
Drummond (1990) termed the products of subducted slab melting
“adakites”, after a single anomalous lava flow on Adak Island in the
Aleutians described by Kay (1978). Because garnet should be present in
the eclogitic source of these magmas, Defant and Drummond (1990)
argued that such melts could be distinguished by anomalously low
concentrations of heavy rare earth elements (HREE) and Y (which are
compatible with garnet) relative to light rare earth elements (LREE), and
high concentrations of Sr (because of the absence of plagioclase at such
depths). Thus, slab melts, or adakites, could be distinguished on Sr/Y
versus Y, or La/Yb versus Yb diagrams from normal arc magmas formed
in the absence of garnet.
However, despite the theoretical possibility of melting subducted
oceanic crust, most thermal models of subduction zones indicate that
temperatures in the slab do not normally reach melting conditions
(N800 °C) prior to dehydration and eclogitization (Fig. 1), which would
render the slab infusible (e.g., Davies and Stevenson, 1992; Peacock,
1996; Poli and Schmidt, 2002). Thus, Defant and Drummond (1990)
proposed that slab melting might be restricted to the subduction of
young (≤25 m.y. old) and therefore still hot oceanic crust, and Peacock
et al. (1994) were even more restrictive (b5 m.y. old). Other relatively
uncommon scenarios that might result in slab melting include shallow
or stalled subduction (whereby the slab has more time to heat up at
shallow depths; Gutscher et al., 2000; Peacock et al., 1994), ridge
subduction (Guivel et al., 2003; Kay et al., 1993), or edge-melting of
detached slabs or slab windows (Haschke and Ben-Avraham, 2005;
Thorkelson and Breitsprecher, 2005; Yogodzinski et al., 2001).
A further complication is added by the fact that most adakites
described in the petrology literature are not in fact primary slab melts,
but are substantially evolved, having reacted or hybridized with the
asthenosphere during ascent (and likely also the upper plate
lithosphere). This modification to the adakite slab-melting model is
required to explain the high contents of MgO, Ni, and Cr present in
some adakites relative to expected levels for hydrated basalt partial
melts (Defant and Kepezhinskas, 2001; Drummond et al., 1996;
Martin, 1999; Martin et al., 2005; Yogodzinski et al., 1995).
Direct evidence for slab melting is lacking, but supra-subduction zone
xenoliths from the Tabar-Lihir-Tanga-Feni (Papua New Guinea), Philip-
pine, and Patagonian arcs preserve hydrous, silica-rich glass inclusions
that are thought to represent migrating slab melts (respectively: Kilian
and Stern, 2002; McInnes and Cameron, 1994; Schiano et al., 1995). The
glass inclusions characterized by Schiano et al. (1995) were calc-alkaline
in composition, with high incompatible element and low Ti, Nb, and Y
contents, high LREE/HREE ratios, and homogenization temperatures of
~920 °C. They thus compositionally resemble melts that would be
predicted to form from slab melting, and appear to provide evidence that
this process occurs at least locally where conditions permit.
The chemical difference between slab dehydration and slab
melting would seem to be rather small, given that both media
would be enriched in volatiles, incompatible elements, and silica.
Indeed, as noted in Section 2.1, there may well be a continuum
between silica-rich aqueous fluids and aqueous silicate melts at
greater depths in subduction zones (Kawamoto, 2006; Kessel et al.,
2005a,b; Manning, 2004; Portnyagin et al., 2007). This likely explains
why the debate between slab melting and dehydration is somewhat
intractable, and mostly hinges on subtle trace element characteristics.
2.3.1. Behavior of metals
Slab melts are predicted to be volatile-rich (including H2O, S, and
Cl) and oxidized, and thus, like hydrous slab fluids, would be expected
to be able to transport base and precious metals at least to some
degree. However, analyses of such metals (except iron) are not
reported in most melt inclusion studies (e.g., Kilian and Stern, 2002;
McInnes and Cameron, 1994; Schiano et al., 1995), so there are no
direct constraints on the capacity of such melts to transfer chalcophile
and siderophile metals from the slab to the mantle wedge.
In a study of metasomatized mantle xenoliths from a submarine
volcano near Lihir Island, Papua New Guinea, McInnes et al. (1999)
concluded that enrichments in Cu, Au, and PGE were caused by slab fluid
metasomatism, rather than melts. In contrast, Kepezhinskas et al. (2002)
measured the concentrations of Au and PGEs in mantle xenoliths from
the Kamchatka arc, and suggested that a fluid-transported component
could be distinguished from a slab melt component by co-enrichments in
PGE and high field strength elements (HFSE) in the latter, because of the
low capacity of aqueous fluids to carry HFSE. Intriguingly, they noted no
such correlation between HFSE-enrichments and Au, and concluded that,
whereas PGE might be transported into the mantle wedge by both fluids
and melts, Au was likely only carried by hydrous fluids.
Two theoretical studies have proposed that slab melts should be
unusually effective as metal-transporting and ore-forming agents.
Oyarzun et al. (2001) argued that slab melts should be unusually
oxidized and rich in H2O and SO2 (relative to normal arc magmas
derived by asthenospheric partial melting), although no evidence was
given for this assertion. Such magmas, they argued, should be
particularly suitable for the formation of magmatic–hydrothermal
porphyry copper deposits upon emplacement in the upper crust.
Mungall (2002) presented a theoretical model for oxidation of the
mantle wedge by Fe 3+-rich slab melts to the point of complete sulfide
destruction, thereby rendering chalcophile and siderophile elements
incompatible in mantle phases, and free to partition into silicate
melts. He argued that ferric iron is a much stronger oxidant than slab-
derived water, and that slab melts should be rich in Fe 3+ generated by
oxidative seafloor alteration. Thus, slab melts might be uniquely
favorable for the subsequent generation of metal-rich, and particu-
larly Au-rich, magmas derived from the mantle wedge.
Mungall's (2002) model may have applicability for less common Au-
rich porphyry deposits formed in atypical subduction zone settings that
might cause slab melting, but does not seem well suited to explain
regular arc porphyry Cu deposits. In either case, metals are envisaged to
be sourced from the mantle wedge, not the slab. In contrast, Oyarzun et
al.'s (2001) model does not address the source of metals, and is at root
based on the assumption that slab melts are uniquely more H2O- and
SO2-rich, and more oxidized than normal arc magmas, leading to
specific ore depositional processes rather than source processes. It is not
clear that these assumptions are justified, and some have argued that
slab melts might in fact be relatively reducing because of the additional
presence of organic-rich sediment melts (Wang et al., 2007a).
2.4. Supra-subduction zone lithospheric melting: the MASH process
Hydrous basaltic magmas generated in the mantle wedge will have
temperatures in excess of 1000 °C (Eggins, 1993; Grove et al., 2006;
MacDonald et al., 2000), and perhaps as high as 1350 °C (Schmidt and
 J.P. Richards / Ore Geology Reviews 40 (2011) 1–26 7

Poli, 1998; Tatsumi, 2003). Because their densities will be lower than
the mantle but not the crust (Herzberg et al., 1983), they will tend to
rise from their asthenospheric source region and penetrate the mantle
lithosphere, but pool at the crust/mantle density barrier (“level of
neutral buoyancy”: Fig. 3; Fyfe, 1992; Hildreth, 1981). Here, if the flux
of magma and heat is maintained and supplemented by the latent
heat of crystallization as the magma begins to crystallize, high
temperatures can be brought to bear on lower crustal rocks that will
cause partial melting (Annen et al., 2006; Bergantz and Dawes, 1994;
Huppert and Sparks, 1988; Klepeis et al., 2003; Petford and Gallagher,
2001; Rushmer, 1993). Hildreth and Moorbath (1988) suggested that
it is the interaction between this hot, hydrous basalt flux from the
subduction zone and felsic crustal partial melts that gives rise to the
uniform composition of andesites in continental volcanic arcs, by a
process they dubbed melting–assimilation–storage–homogenization
(MASH). In a refinement of this model, Annen et al. (2006) referred to
the region of magma–crust interaction as a “hot zone” (Fig. 3).
Because garnet is a product of such lower crustal fractionation and
partial melting processes (Alonso-Perez et al., 2009; Berger et al.,
2009; Dufek and Bergantz, 2005; Garrido et al., 2006; Hansen et al.,
2002; Klepeis et al., 2003; Rushmer, 1993; Wolf and Wyllie, 1994),
derivative calc-alkaline magmas may display trace element compo-
sitions that resemble adakites (see Section 2.3) but which are
unrelated to slab melting (Klepeis et al., 2003; Macpherson et al.,
2006; Richards and Kerrich, 2007; Tulloch and Kimbrough, 2003).
Such common processes, affecting batches of magma crystallizing and
fractionating at different crustal depths (e.g., Annen et al., 2006) are
entirely consistent with petrological observations in arc volcanic
systems where “adakite-like” (i.e., high-Sr/Y) andesitic lavas may be
interlayered with “normal” andesites in a single volcano, and do not
require a fundamental change in magma source 100 km below the
volcano (e.g., Feeley and Davidson, 1994; Grunder et al., 2008;
Richards et al., 2006a).
Once these hybrid magmas reach basaltic andesitic to andesitic
compositions, their densities are low enough to allow them to rise
through the lower continental crust (Herzberg et al., 1983), but they
tend to stall again at a second density barrier in the middle to upper
crust below light supracrustal rocks. This is the level (5–10 km) at which
large arc batholiths will form if the flux of magma is sustained, and is
also the level at which evolved felsic melts and volatiles are accumulated
(Fig. 3; see Richards, 2003, and references therein). These volatiles drive
buoyant, bubbly, evolved magma upwards into the cover rocks to form
subvolcanic stocks and dikes, or explosive volcanic eruptions if they
reach surface. The volatiles may also separate from the magma flux to
form a separate fluid plume, which ultimately vents at the surface
(fumaroles) but may also form porphyry- and epithermal-type deposits
in the hypabyssal and near-surface environment (see discussion of
these processes in Sections 3 and 4).

Volcanic arc

Hydrothermal Epithermal deposits

alteration Porphyry deposits
Sea level
0 km
Mid- to upper crustal
batholithic complex

Feeder dikes
Continental crust

Lower crustal
MASH or “hot zone”
600°C
50 km

1000
°C
Subcontinental
De mantle lithosphere
hy Man
dr tle c
at orne
in r flow
g
oc
O ea Partial melting
lith macea ni
c
140
0°C
os nt nic cr Metasomatized
ph le us
60

10

er t asthenosphere
00

e
0°C

14 Asthenosphere
°C

00
°C 100 km

Fig. 3. Schematic section through a continental arc, showing the development of a MASH or “hot zone” at the base of the crust where basaltic arc magmas pool at their level of neutral
buoyancy, differentiate, and interact with crustal rocks and melts. Evolved, less dense, andesitic magmas rise into the mid-to-upper crust where they pool at their new level of neutral
buoyancy to form batholithic complexes. Along with volcanic structures, porphyry and epithermal deposits may form at shallower levels above these batholithic complexes where
exsolved magmatic fluids ascend, cool, and interact with near-surface upper crustal rocks. Modified from Richards (2003, 2005); sources: Hildreth and Moorbath (1988), Winter (2001),
Annen et al. (2006), and Sillitoe (2010).
8 J.P. Richards / Ore Geology Reviews 40 (2011) 1–26
2.4.1. Behavior of metals
Some of the clearest evidence for the involvement of crustal rocks in
continental arc magmas comes from Pb isotopic data (e.g., Wörner et al.,
1992), although as noted in Section 2.2, there may be ambiguity
between lower crustal melting and the melting of subducted continent-
derived sediments. Lead and uranium are much more abundant in the
bulk continental crust (11 ppm Pb, 1.3 ppm U; Rudnick and Gao, 2003)
or lower continental crust (4 ppm Pb, 0.2 ppm U; Rudnick and Gao,
2003) than the primitive mantle (b0.2 ppm Pb, b0.02 ppm U; Taylor
and McLennan, 1985; Sun and McDonough, 1989), MORB (0.3 ppm Pb,
0.05 ppm U; Sun and McDonough, 1989), or typical low-K mafic arc
andesites (b1.8 ppm Pb, b0.2 ppm U; Gill, 1981), so it only requires
small amounts of contamination by radiogenic crustal lead to
significantly modify a magma's Pb isotopic composition. Thus, it is not
clear that a particularly large amount of Pb in arc magmas is sourced
from crustal rocks versus the subduction zone, and Macfarlane et al.
(1990) have argued that the crustal contribution is minimal in Central
Andean magmas and ores. Moreover, porphyry-type systems are
typically not Pb-rich, except in late-stage skarns and distal veins
where some of the Pb may have been derived from local host rocks (e.g.,
Mukasa et al., 1990).
Most researchers have assumed that, because of the higher
concentrations of Cu in primitive andesites (145 ppm; Gill, 1981)
compared with the bulk continental crust (27 ppm; Rudnick and Gao,
2003), the bulk of Cu in porphyry-type deposits is mantle-derived. A
similar assumption is made for Au, although the primitive mantle and
continental crust actually have comparable concentrations (1–3 ppb
Au; Rudnick and Gao, 2003; Taylor and McLennan, 1985). Moreover,
porphyry Cu–(Au) deposits are found in association with mantle-
derived arc magmas worldwide, regardless of crustal type (oceanic or
continental) or thickness (Kesler, 1973), so a crustal heritage for these
metals does not appear to be critical. Nevertheless, a lower crustal
source, perhaps hybridized with mantle-derived magmas, has been
proposed by Bouse et al. (1999) for both magmas and metals in the
Laramide porphyry systems of Arizona. Moreover, Titley (1987, 2001)
has specifically suggested that Au and Ag are crustally derived in a
range of ore deposits including porphyries in southwestern USA,
because the ratios of these elements correlate closely with two
distinct basement domains in this region. Given that Au is not
especially enriched in the mantle (see above), and that Ag is in fact
more abundant in the crust than the mantle (80 ppb in the bulk
continental crust, versus b19 ppb in the primitive mantle; Taylor and
McLennan, 1985), a crustal source for at least some proportion of
these minor metals, and especially Ag, in arc magma-related systems
may be reasonable. However, it seems unlikely that this argument can
be extended to copper, except perhaps on the margins.
2.4.2. Sources of Mo
Molybdenum occurs in varying amounts in porphyry-type deposits,
ranging from trace levels (b0.01 wt.% Mo) in porphyry Cu–(Mo) deposits,
where it may not even be recovered as a byproduct, to being the main ore
component (up to 0.3 wt.% Mo) in porphyry Mo deposits (Seedorff et al.,
2005; Westra and Keith, 1981). At the Mo-rich end of the spectrum, there
are two clearly different tectonomagmatic associations, only one of which
is directly related to subduction: calc-alkaline porphyry Mo deposits are
generally relatively low grade (0.1–0.02 wt.% Mo; Carten et al., 1993),
whereas intra-cratonic rift-related deposits associated with high-silica,
fluorine-rich, peraluminous granitoids are relatively high grade (0.1–
0.3 wt.% Mo; e.g., “Climax-type” deposits; Carten et al., 1993; Kirkham and
Sinclair, 1996; Sinclair, 2007; Stein, 1988; White et al., 1981).
Kesler (1973) noted a general association (with exceptions) of
porphyry Cu–Au deposits in island arcs, and porphyry Cu–Mo deposits
in continental arcs, and it is clear that the peraluminous felsic rocks
associated with rift-related Climax-type porphyry Mo deposits are
primarily of continental crustal origin (Farmer and DePaolo, 1984;
Stein, 1988). This has led to one view that Mo might be predominantly
derived from continental crustal sources (Farmer and DePaolo, 1984;
Stein, 1988; Klemm et al., 2008; White et al., 1981). On the other hand,
minor amounts of Mo do occur in some island arc-related porphyry
deposits where no continental crustal sources are inferred (Westra and
Keith, 1981), so a mantle (subduction zone) source for at least some Mo
cannot be excluded. Moreover, Blevin and Chappell (1992) and Blevin
et al. (1996) have demonstrated a continuum from Cu–Au deposits
associated with unevolved, mafic I-type granitoids to W–Mo deposits
associated with cogenetic, evolved granites in eastern Australia,
suggesting a common, magmatic source for all of these elements.
A complication is introduced in the Climax-type deposits, because
although the immediate source of the Mo-bearing fluids is felsic
magma of clear crustal origin, many deposits also show a close genetic
association with mafic alkaline magmas, which may have introduced
volatiles, S, and possibly Mo into the evolved felsic magma chamber
(Audétat, 2010; Carten et al., 1993; Keith et al., 1986, 1998). Keith et
al. (1997), Hattori and Keith (2001), and Maughan et al. (2002) have
also suggested that injections of mafic alkaline magmas into the
evolving Bingham Canyon magmatic system may have given rise to
the unusually large size and high grades of this porphyry Cu–Mo–Au
deposit. Along the same lines, Pettke et al. (2010) have proposed that
the unusual Cu–Mo–Au endowment of the southwestern USA (e.g.,
the giant Bingham, Butte, Climax, Henderson, and Questa porphyry
Cu–Mo–Au and porphyry–Mo deposits) reflects Cenozoic remobiliza-
tion of Proterozoic subduction-metasomatized subcontinental mantle
lithosphere (see Section 2.5).
Thus, at this time there is no consensus regarding the crustal
versus mantle origin of molybdenum in porphyry deposits, although it
is clear that the highest grade porphyry Mo deposits are formed in
intra-plate continental settings, and if a mantle source is important in
these cases, it is not directly related to subduction activity but rather
to rifting or reactivation of previously subduction-enriched litho-
spheric sources.
2.5. Lithospheric melting during post-subduction events
A number of mineral deposits with broad similarities to those
formed by subduction-related processes are also found in post-
subduction tectonic settings, such as subduction reversal or migration,
arc collision, continent–continent collision, and post-collisional rifting.
They include porphyry Sn–W, Mo, Cu–Mo, and Cu–Au deposits and
epithermal Au deposits, and in many cases are only known not to be
directly related to subduction because of precise geochronology and
plate tectonic reconstructions that place their formation after subduc-
tion has demonstrably ceased. Associated magmas are typically calc-
alkaline, but tend towards somewhat more alkaline compositions
compared with normal arc magmas (Richards, 2009).
In complex accretionary arcs, it can be very difficult to ascribe any
given pluton (and any associated mineral deposits) to a particular
subduction or collisional event, because subduction commonly con-
tinues after collision, albeit normally with a shift in the locus of
magmatism. However, in continent–continent collision zones or where
arc collision terminates subduction, there can be greater certainty about
the timing of cessation of subduction magmatism. Consequently, it is in
collisional orogens such as the Neo-Tethyan belt of southeastern Europe
and southern Asia that some of the clearest examples of post-subduction
magmatism and mineralization are found. These include, from east to
west, the Miocene Gangdese porphyry Cu–Mo belt in the Tibetan orogen
(Hou et al., 2006, 2009; Yang et al., 2009), the Miocene Kerman porphyry
Cu–Mo belt in southeastern Iran (Shafiei et al., 2009), the Miocene Sari
Gunay epithermal Au deposit in northwestern Iran (Richards et al.,
2006b), the Eocene Çöpler epithermal Au deposit in southeastern Turkey
(Keskin et al., 2008; Kuscu et al., 2010), the Pliocene Kisladag porphyry
Au deposit in western Turkey, the Miocene Skouries porphyry Cu–Au–
PGE deposit in Greece (Economou-Eliopoulos and Eliopoulos, 2000), and
 J.P. Richards / Ore Geology Reviews 40 (2011) 1–26
the Roşia Montană epithermal Au deposit in Romania (Manske et al.,
2006; Neubauer et al., 2005).
Similarly, in the southwest Pacific ocean, accurate plate tectonic
reconstructions permit the identification of a number of post-
subduction porphyry and epithermal deposits, such as the Grasberg
porphyry Cu–Au deposit in Papua, Indonesia (Cloos et al., 2005;
Paterson and Cloos, 2005), the Ok Tedi porphyry Cu–Au deposit (van
Dongen et al., 2010) and the Porgera alkalic-type epithermal Au deposit
in mainland Papua New Guinea (Richards et al., 1990; Richards and
Kerrich, 1993), the Lihir alkalic-type epithermal Au deposit on Lihir
Island, Papua New Guinea (Carman, 2003; Kennedy et al., 1990), and the
Emperor alkalic-type epithermal Au deposit in Fiji (Gill and Whelan,
1989; Setterfield et al., 1992). (For reviews of alkalic-type epithermal
deposits, see Jensen and Barton, 2000 and Richards, 1995).
Because subduction has ceased in these regions, a fresh supply of
fluids, volatiles, and other slab-derived components to the mantle
wedge no longer exists. Nevertheless, the broad geochemical similarity
of many of these magmas to normal arc magmas, including their
hydrous and generally oxidized nature, suggests some link to
subduction metasomatism. Consequently, many researchers have
implicated upper-plate lithospheric sources, modified by earlier
subduction-related fluids and/or hydrous melts (e.g., Clemens et al.,
2009; Cloos et al., 2005; Guo et al., 2007; Harris et al., 1986; Johnson
et al., 1978; Pearce et al., 1990; Pettke et al., 2010; Richards, 2009).
Previously subduction-modified asthenosphere is unlikely to be a viable
source except for a short period after subduction has ceased (e.g.,
Richards et al., 1990; Solomon, 1990), because such material will be
quickly dispersed by mantle convection.
The key to all of these models is subduction-derived water, which is
most likely stored in amphibolitic cumulates, residual from the earlier
arc magma flux and located in the deep crust or mantle lithosphere (e.g.,
Claeson and Meurer, 2004; Davidson et al., 2007; DeBari and Coleman,
1989; Jagoutz et al., 2009; Larocque and Canil, 2010; Müntener and
Ulmer, 2006; Tiepolo and Tribuzio, 2008). Water lowers the solidus of
silicate assemblages, and will lead to the formation of hydrous partial
melts during pro-grade metamorphism or mafic melt invasion (Beard
and Lofgren, 1991; Rushmer, 1991; Wolf and Wyllie, 1994).
Thermal rebound in thickened orogenic crust, delamination of
sub-continental mantle lithosphere, or post-collisional rifting (with
ingress of asthenospheric melts into the lower crust in the last two
cases) can all cause small-volume partial melting of arc-metasoma-
tized lithosphere and/or hydrous lower crustal cumulates (Fig. 4;
Brown, 2010; Clemens et al., 2009; Harris et al., 1986; Richards, 2009).
Such melts, being derived from subduction-modified sources, will
share many of the characteristic geochemical features of arc magmas,
including their relatively high water contents and oxidation states,
and potentially metal contents (see Section 2.5.1). The smaller volume
of partial melting to be expected in such tectonic settings will give
these magmas a somewhat more alkaline composition than arc
magmas (e.g., Clemens et al., 2009), and will also mean that large
batholithic complexes are unlikely to be formed, consistent with the
generally smaller and more isolated occurrence of such post-
subduction magmatic systems (compared with arc-related Cordille-
ran batholiths, or collisional S-type batholiths; Pitcher, 1997).
Because these post-subduction magmas are derived from amphibo-
litic sources in which garnet (±titanite) is likely also present, and
because their hydrous nature will suppress plagioclase fractionation
(similar to other hydrous arc magmas), they may be characterized by
elevated Sr/Y and La/Yb ratios; that is, they may display adakite-like
trace element characteristics.
2.5.1. Behavior of metals in subduction-modified sources
As discussed in Section 2.1, arc magmas are characterized by high
fO2 and fS2 relative to normal melts from MORB-depleted astheno-
sphere. Consequently, such magmas may be sulfide-saturated (at
oxidation states up to ΔFMQ + 2.3; Jugo, 2009) despite sulfur being
9
predominantly present in the melt as sulfate or SO2 (Carroll and
Rutherford, 1985). Xenoliths from supra-subduction zone mantle
(McInnes et al., 1999) and samples of mafic cumulates from lower
crustal arc roots (Fig. 5; Canil et al., 2010; Greene et al., 2006; Jagoutz
et al., 2007) reveal the common presence of small amounts of sulfide,
typically trapped as inclusions in silicate phases (suggesting a primary
magmatic rather than secondary hydrothermal origin).
Hamlyn et al. (1985), Richards (1995, 2009), Solomon (1990), and
Wyborn and Sun (1994) have explored the role of residual sulfide
phases on the metal content of fractionating magmas, and also of
partial melts formed during later, post-subduction melting events.
The high partition coefficients for chalcophile and highly siderophile
elements (HSE) between sulfide phases and silicate melt mean that
such metals should be strongly partitioned into any coexisting sulfide
phases (Campbell and Naldrett, 1979; Peach et al., 1990). As shown in
Fig. 2, at high abundances of sulfide relative to silicate melt (low R-
factor; Campbell and Naldrett, 1979), the melts will be depleted in all
of these chalcophile and siderophile elements. In contrast, at
intermediate abundances of sulfide (intermediate R-factor), only
originally sparse HSE will show significant depletions. This led
Richards (2005, 2009) to propose that small amounts of sulfide left
behind as residual phases from fractionation of arc magmas in the
deep lithosphere (or asthenosphere) will not significantly deplete
those magmas in relatively abundant chalcophile elements such as Cu
and Mo, but might significantly deplete them in highly siderophile
elements such as Au. This would give rise to magmas with relatively
high Cu/Au ratios (which might form Cu-rich porphyry deposits), but
would leave a residue of potentially HSE-rich sulfides in the mantle
and/or lower crustal amphibolitic cumulate arc roots.
As noted in Section 2.5, subduction-modified asthenospheric sources
will be rapidly convected away when subduction ceases, and so could
only contribute to immediately post-subduction magmatism. In
contrast, deep crustal amphibolites are preserved in the lithosphere,
and will be susceptible to partial melting at any later time due to thermal
rebound or reheating by invading asthenospheric melts. Under lower fS2
post-subduction conditions (a flux of S from the subduction zone is no
longer present), any residual sulfide phases would likely dissolve into
the S-undersaturated silicate melt, carrying their metal loads with them
(e.g., Ackerman et al., 2009). Richards (2009) proposed that this might
explain the occurrence of Au-rich porphyry and related epithermal
systems in some post-subduction settings, such as the alkalic-type
epithermal Au deposits of the SW Pacific, and various post-collisional Au
deposits in the Balkans–Turkey–Iran Neotethyan belt. Pettke et al.
(2010) have proposed a similar model for giant porphyry Cu–Mo–Au
deposits in the southwestern USA.
This model can also explain the occurrence of Au–poor porphyry
Cu–(Mo) deposits in post-subduction settings, such as those in Tibet
and Iran (Hou et al., 2009; Shafiei et al., 2009; Wang et al., 2007b), the
only difference being that in this case larger proportions of sulfide
may have fractionated out from the original arc magmas in the deep
crust. Such sulfides would have retained significant amounts of the
subduction flux of Cu and Mo, but HSE would be diluted to low
concentrations by the greater volume of sulfide (low R-factor; Fig. 2).
Second-stage melts from such cumulate sources would therefore be
Cu–(Mo)-rich, but not necessarily Au-rich.
A control on these two scenarios (abundant Cu-rich residual sulfide
versus sparse but HSE-rich residual sulfide, or low versus high R-factor)
might be the average oxidation state and sulfur fugacity of the generative
subduction system. In more oxidized or S-poor systems, smaller volumes
of HSE-rich sulfide would exsolve from the silicate melt (high R-factor;
Campbell and Naldrett, 1979), whereas in less oxidized or S-rich systems,
larger volumes of Cu-rich but HSE-poor sulfide would exsolve (low R-
factor; Fig. 2). In particular, the proportion of sulfides exsolving from arc
magmas may be very sensitive to small changes in their oxidation state,
because of the rapid change from sulfide to sulfate dominance in
magmatic systems between ΔFMQ +1 and +2 (Jugo et al., 2010). The
10 J.P. Richards / Ore Geology Reviews 40 (2011) 1–26

Fig. 4. Post-subduction tectonic environments conducive to the formation of porphyry and epithermal deposits by remobilization of previously subduction-modified lithosphere
(modified from Richards, 2009). (a) Porphyry Cu ± Mo deposits formed in normal arc settings; a continental arc is shown, but similar processes can occur in mature island arcs. (b–d)
During post-subduction tectonic processes, previously subduction-modified sub-continental lithospheric mantle (SCLM) or lower crustal hydrous cumulate zones residual from
previous arc magmatism (black layer) may undergo small-volume partial melting. Such magmas may remobilize Au as well as Cu ± Mo left behind in residual sulfide phases by arc
magmatism, leading to the potential formation of porphyry Cu ± Au ± Mo and alkalic-type epithermal Au deposits. Magmas may be characterized by high Sr/Y and La/Yb ratios due
to the presence of hornblende (± garnet, titanite) in the amphibolitic lower crustal source rocks. See text for discussion.

oxidation state of the mantle wedge will depend on the character of the
flux from the subducting slab (e.g., a higher proportion of subducted
organic-rich sediment would lead to lower oxidation states; Wang et al.,
2007a); this property is therefore likely to have a characteristic average
value along any given arc at any particular period of time.
Variations in oxidation state over typical ranges for arc magmas
(ΔFMQ= 0 to +2; Ballhaus, 1993; Brandon and Draper, 1996; Blatter
and Carmichael, 1998; Malaspina et al., 2009; Parkinson and Arculus,
1999; Rowe et al., 2009) will not greatly affect the potential to form syn-
subduction porphyry Cu–(Mo) deposits, but might control the Cu/HSE
ratio in later magmas formed by post-subduction melting of these
sulfide-bearing residues. Specifically, Au-rich (low Cu/Au) post-subduc-
tion porphyries might form in settings where previous arc magmatism
was relatively oxidized (sparse but HSE-rich sulfide residue), whereas
Au-poor (high Cu/Au) post-subduction porphyries might form where
previous arc magmatism was relatively reduced (more abundant Cu-rich
sulfide residue). Such a mechanism might also explain why coeval belts
of porphyry deposits tend to have characteristic Cu/Au ratios.
Finally, partial melting of predominantly reduced, sulfide-rich crustal
rocks in orogenic settings may lead to chalcophile and siderophile
element-depleted, but potentially lithophile element-rich S-type
magmas (see Section 2.6).
2.6. Crustal melting during post-collisional stress relaxation
Collisional orogens commonly undergo crustal thickening followed
by extensional or transpressional collapse. Bimodal magmatism is
characteristic of such tectonic settings, resulting from partial melting of
pelitic protoliths in the deep crust triggered by the heat from upwelling
asthenospheric melts (Hildreth, 1981). Peraluminous S-type granites
(Chappell and White, 1974) are subsequently emplaced as large
batholith complexes in the mid- to upper orogenic crust (e.g., the
Hercynian peraluminous granites of Europe; Barbarin, 1996; Clemens,
2003; Darbyshire and Shepherd, 1994; Harris et al., 1986; Wyllie et al.,
1976). These granites tend to be enriched in lithophile rather than
chalcophile elements, reflecting their crustal origins, and may generate
magmatic–hydrothermal deposits containing Sn, W, U, Mo, REE, Li, Be, B,
and F.
2.6.1. Sources of metals
Tin and especially tungsten commonly accompany molybdenum in
porphyry deposits as trace metals and byproducts, but they also form a
class of porphyries on their own, associated with S-type granites in
continental orogens (Hart et al., 2005; Ishihara, 1981; Ishihara and
Murakami, 2006; Kerrich and Beckinsale, 1988; Kirkham and Sinclair,
1996; Lehmann, 1982). The Hercynian tin granites of Europe, and the
Bolivian and SE Asian tin belts are examples of such deposits, with
mineralization occurring in skarns and greisens around the granite
intrusions, and to a lesser extent as internal stockworks and
disseminations (e.g., Černý et al., 2005; Meinert et al., 2005). As with
the source magmas, metals in these deposits appear to be predomi-
nantly of crustal origin (Hedenquist and Lowenstern, 1994). For
example, in a recent assessment of the source of Sn in the Cornubian
batholith of SW England, Williamson et al. (2010) concluded that all of
 J.P. Richards / Ore Geology Reviews 40 (2011) 1–26
(a)
Chalcopyrite
(b)
Pyrite
Chalcopyrite
Pyrrhotite
Fig. 5. Reflected light photomicrographs of sulfide inclusions in amphibole-rich lower
crustal arc cumulates from: (a) the Talkeetna arc, Alaska; (b) the Bonanza arc,
Vancouver Island, Canada (samples courtesy A. Greene and D. Canil, respectively).
the Sn could have been extracted from the crustally-derived granites.
Uranium is also significantly enriched in crustal rocks versus the mantle
(0.91 ppm versus ~0.02 ppm, respectively; Taylor and McLennan,
1985), and so is unlikely to have a mantle source in such deposits.
However, Dietrich et al. (1999) have suggested a possible role for
mantle-derived magmas in triggering volatile (and metal) release from
evolved, felsic magmas in the Bolivian tin belt, and Walshe et al. (2011)
have identified a mantle Nd isotopic signature in tin granites from
eastern Australia.
In contrast, in the case of W skarns associated with Mo mineraliza-
tion in calc-alkaline I-type magmas, a shared mantle origin with Mo
might be indicated (e.g., Newberry and Swanson, 1986), consistent with
the similar siderophile tendencies of these two elements, and their
position in the periodic table (group VIB).
3. Behavior of metals during magma fractionation and fluid
exsolution in the upper crust
Key to the formation of magmatic–hydrothermal deposits of
chalcophile and siderophile elements in the upper crust is the lack of
significant saturation with and loss of sulfide phases prior to aqueous
volatile exsolution from a cooling magma (Candela, 1989b, 1992;
Candela and Holland, 1986; Candela and Piccoli, 2005; Richards, 1995;
Richards and Kerrich, 1993; Spooner, 1993). As discussed in Sections
2.1.1 and 2.5.1, chalcophile and siderophile elements partition
11
strongly into sulfide phases exsolving or crystallizing from silicate
melts. Thus, if extensive fractionation and removal of magmatic
sulfide phases were to occur, the remaining silicate melt would be
strongly depleted in these elements (Jugo et al., 1999; Lynton et al.,
1993). This is in essence the model for formation of orthomagmatic
sulfide deposits from relatively reduced mafic magmas (e.g., Naldrett,
1989), and perhaps explains the deficiency of chalcophile elements
such as Cu and Au in more reduced, evolved, Sn–W-bearing S-type
magmas (Blevin and Chappell, 1992; Hedenquist and Lowenstern,
1994).
In more oxidized subduction-related or post-subduction magmas,
although sulfide saturation likely occurs at some point during their
evolution (as indicated by the common presence of sparse sulfide
inclusions in phenocrysts in arc volcanic rocks as well as lower crustal
arc cumulates; e.g., Burnham, 1979; Halter et al., 2002; Hattori, 1997;
Keith et al., 1997; Stavast et al., 2006; Fig. 5), it may not occur to the
extent that sulfides physically separate from the magma, or at least
not in large amounts. Instead, small sulfide droplets or crystals may be
entrained in magma ascending buoyantly through the crust (e.g.,
Bockrath et al., 2004; Tomkins and Mavrogenes, 2003) or as inclusions
in silicate phenocrysts, and will not be substantially lost to the overall
magma flux. Indeed, several authors have argued that pre-concen-
tration of ore metals in magmatic sulfide phases may be an important
step in porphyry metallogenesis (e.g., Jenner et al., 2010). In these
models, sulfide phases subsequently break down due to changes in
oxidation state and sulfur fugacity in response to volatile exsolution
and magnetite crystallization upon emplacement in the upper crust,
thereby rendering metals available for redissolution in the volatile
phase (e.g., Cygan and Candela, 1995; Halter et al., 2002, 2005; Jugo et
al., 1999; Keith et al., 1997; Stavast et al., 2006). Other authors have
argued that this process, while it may occur, is not critical to metal
behavior in magmatic–hydrothermal systems, and that direct parti-
tioning from the silicate melt to the hydrothermal fluid phase is the
dominant mechanism (e.g., Audétat and Pettke, 2006; Lynton et al.,
1993; Simon et al., 2008; Sun et al., 2004b). As noted in Section 2.5.1,
Richards (2009) suggested that separation of small amounts of sulfide
from arc magmas at depth in lower crustal MASH cumulate zones may
provide a source of metals (especially HSE) for later post-subduction
magmas, but that this process may not substantially affect the Cu
content of the original arc magmas.
Regardless of the exact role of magmatic sulfides, the ultimate
relationship is that of partitioning of metals between silicate melts and
exsolving hydrothermal fluids, with sulfides as a possible intermediary
step. Our current understanding of these partitioning processes is now
quite advanced following several decades of hydrothermal experiments
(e.g., Candela and Piccoli, 1995) and more recently the advance of
quantitative single fluid and melt inclusion analysis (e.g., Heinrich et al.,
2003a,b), which has enabled direct measurement of metal contents in
ore-forming fluids and melts. In the following sections, I review some of
the key factors in metal solvation and transport in magmatic–
hydrothermal fluids.
3.1. Partitioning of metals from magma into exsolving hydrothermal
fluid
Subduction-related magmas commonly contain at least 4 wt.% H2O
during crustal ascent, as evidenced by the presence of hornblende and
biotite phenocrysts in many andesitic volcanic rocks and arc plutons
(Burnham, 1979; Naney, 1983; Rutherford and Devine, 1988). In
response to the decreasing solubility of water in silicate melts as
pressure decreases, such hydrous magmas inevitably exsolve an
aqueous volatile phase upon emplacement at shallow crustal levels or
on eruption (Burnham, 1979, 1997; Eichelberger, 1995). This process
has in the past rather confusingly been called first and second boiling
(although neither process is technically “boiling”), the first event
occurring during ascent and depressurization of the magma, and the
12 J.P. Richards / Ore Geology Reviews 40 (2011) 1–26

second occurring after emplacement as crystallization progressively (a)

increases the concentration of volatiles in the residual melt (Candela, Deep
V-L isotherm (vapour)
supercritical
1989a). In reality, volatile exsolution is probably a more-or-less 2000 magmatic V-L isotherm (liquid)
1 fluid exsolution Critical / boiling curve
continuous process during arc magma ascent and cooling, starting at (10 wt.% NaCl) H2 O critical point
depth with the exsolution of relatively insoluble CO2 (Blundy et al., Halite saturation
2010; Holloway, 1976; Lowenstern, 2001; Wallace, 2005). However, Salinity isopleth
Supercritical Supercritical fluid
the bulk of the magmatic water content likely exsolves relatively 1500 fluid intersects Liquid path
rapidly as the magma approaches its solvus, at depths of ~ 5–10 km, 2-phase surface

P (bars)
Vapour path

depending on magma composition and water content (Burnham, Coexisting vapour+liquid

1979). V+L Liquid phase

progressively
The composition of this exsolved magmatic volatile phase is 1000 separates from

ite
al
dominantly aqueous, containing sulfur species (predominantly SO2 in vapour

H
L+
oxidized systems, but also some reduced S species), CO2, NaCl, KCl, HCl, Shallow
magmatic fluid
and metal chlorides. The exact composition depends on many variables, exsolution 2
including the depth of exsolution and the magma composition 500

0
ry

Cl 10
(especially the initial magmatic Cl/H2O ratio and alkali content; Candela, hy

Na 0 80
rp

ite
1989c; Candela and Piccoli, 2005; Cline and Bodnar, 1991; Webster, Po

al

t.% 6
+H
1992), but typical estimates for a single-phase supercritical fluid 0

W 40
0
90
exsolved at depths below the H2O–NaCl solvus are ~2–13 wt.% NaCl

0
80

0
70

20
0
0
60

50
equivalent (average 5 wt.% NaCl equivalent) with minor CO2 (Audétat

0
40
T (°C)

0
30

0
20

0
0
and Pettke, 2003; Audétat et al., 2008; Burnham, 1979; Candela, 1989c;

0
10
Hedenquist et al., 1998; John, 1991; Redmond et al., 2004), and up to
1.3 wt.% Cu and 0.3 wt.% Fe (Klemm et al., 2007; Rusk et al., 2004, 2008; (b)
Deep
Sawkins and Scherkenbach, 1981). These high observed metal solubil- supercritical V-L isotherm (vapour)
2000 magmatic V-L isotherm (liquid)
ities are consistent with or exceed experimental observations and fluid exsolution Critical / boiling curve
(10 wt.% NaCl)
theoretical predictions based on chloride complexing alone (e.g., H2 O critical point
Halite saturation
Candela and Holland, 1984, 1986), and suggest that other volatile
Supercritical Salinity isopleth
ligands such as sulfide species may enhance the solubility of chalcophile fluid never Supercritical fluid
elements such as Cu and Au in high temperature aqueous fluids (e.g., 1500 intersects Liquid path
V+L 3 2-phase
P (bars)

4 Vapour path
Heinrich et al., 1992; Pokrovski et al., 2005, 2008; Seo et al., 2009; Simon surface
Contraction path
et al., 2006; Zajacz et al., 2008, 2011). Supercritical Coexisting vapour+liquid

Shallowly emplaced magmas will exsolve fluids under pressure– fluid intersects
2-phase surface Liquid phase
1000 progressively
temperature (P–T) conditions that lie within the two-phase liquid–

ite
separates from

al
H
vapor field for the bulk fluid composition, resulting in immediate vapour

L+
formation of an immiscible low salinity vapor and high salinity brine
Vapour phase
(Fig. 6a). 500
departs from
2-phase surface Low to
The critical point in the H2O–NaCl system (which is commonly

0
moderate

Cl 10
salinity
used as a proxy for magmatic fluids) occurs between ~1.0 and 1.4 kb

Na 0 80
ite

liquids
al

for fluid temperatures between 600° and 800 °C (the typical al

t.% 6
+H

temperature range for fluids exsolved from intermediate to felsic

0
rm
V

W 40
e
0

ith
90

0
80

magmas) (Pitzer and Pabalan, 1986; Sourirajan and Kennedy, 1962), Ep

70

20
0
0
60

50

0
40

which is equivalent to depths of between ~ 3 and 5 km at lithostatic

30

T (°C)
0
20

0
0
10

pressures. Most porphyry deposits and their host plutons are

emplaced at depths between 1 and 6 km (Seedorff et al., 2005), so
fluids exsolving directly from magmas at these depths will typically
form immiscible liquid and vapor plumes (e.g., Henley and McNabb,
1978; Nash, 1976). However, the bulk of the fluids and metals in
porphyry deposits are likely initially sourced at deeper levels (5–
10 km, as noted above) from larger volumes of magma in mid- to
upper crustal batholithic complexes (Candela and Piccoli, 2005; Cloos,
2001; Damon, 1986; John, 1991; Richards, 2003, 2005; Shinohara and
Hedenquist, 1997), at which depths the fluids will be supercritical. As
these deep fluids rise into shallow cupola zones extending above the
main batholith, they will likely intersect the solvus on the vapor side,
and will begin to condense a dense saline brine (Ahmad and Rose,
1980; Figs. 6a and 7).
Supercritical fluids are highly mobile (e.g., Coumou et al., 2008; Dunn
and Hardee, 1981; Norton and Dutrow, 2001) and behave differently in
terms of magma–fluid partitioning compared to fluids exsolved at
shallower depths in the two-phase field. In particular, Henley and
McNabb (1978) suggested that the higher density and viscosity of saline
brine condensates might restrict their flow, leaving them as a dense
residual liquid in the deeper parts of evolving magmatic hydrothermal
systems (see also: Lewis and Lowell, 2009; White et al., 1971). The lower
density vapor or supercritical fluid would be expected to be highly
upwardly mobile, as well as larger in terms of both volume and mass than
Fig. 6. P–T–XNaCl phase diagram, modified from Driesner and Heinrich (2007), illustrating
fluid pathways for a magmatic–hydrothermal fluid exsolved with an initial bulk salinity of
10 wt.% NaCl. (a) Early, high thermal gradient fluids exsolved from deeply (path 1) and
shallowly (path 2) emplaced magmas (porphyry environment). (b) Late, low thermal
gradient fluids exsolved from deeply emplaced magma (high-sulfidation epithermal
environment). Path 3 illustrates the supercritical fluid contraction path proposed by
Hedenquist et al. (1998), whereas path 4 illustrates a slightly steeper thermal gradient
with brief intersection of the 2-phase (L–V) field, as proposed by Heinrich et al. (2004).
Note that in the two-phase field, the dense saline liquid phase progressively separates from
the vapour phase, and the two-phase pathways shown do not represent a closed system.
See text for discussion.
the brine phase (assuming an initial bulk salinity below ~20 wt.% NaCl),
and so has much greater potential as an efficient transporting medium for
ore components. However, until fairly recently, it was assumed that low
salinity vapors would not have the capacity to dissolve large quantities of
base metals as chloride complexes, and the brine phase was therefore the
favored ore-forming medium (e.g., Bodnar and Beane, 1980; Cline and
Bodnar, 1991; Eastoe, 1982; Hedenquist and Richards, 1998; Moore and
Nash, 1974; Nash, 1976; Shinohara, 1994; Williams et al., 1995).
Observations of chalcopyrite crystals trapped in some vapor-rich fluid
inclusions (e.g., Bodnar and Beane, 1980) were explained by some as
products of heterogeneous trapping (see discussion in Mavrogenes and
 J.P. Richards / Ore Geology Reviews 40 (2011) 1–26 13

Fig. 7. Schematic cross-section through a typical coupled arc batholith–cupola–volcanic system, with associated porphyry Cu ± Au and linked high sulfidation Cu–Au epithermal
deposits. Also shown are the thermal structure, fluid flow pathways and characteristics during the main stage of hydrothermal activity, and overlapping hydrothermal alteration
zones. Propylitic alteration by circulating heated groundwaters can be assumed to affect all the supracrustal rocks in the field of view, with greatest intensity (epidote, actinolite)
close to the intrusions, fading to background distally. Modified from Richards (2005); sources: Sillitoe (1973, 2010), Dilles (1987), Shinohara and Hedenquist (1997), Hedenquist et
al. (1998), and Fournier (1999).

Bodnar, 1994). The advent of quantitative analysis of single fluid
inclusions by synchrotron X-ray microprobe, proton-induced X-ray
emission spectroscopy (PIXE), and laser ablation-inductively coupled
plasma-mass spectrometry (LA-ICP-MS) revealed that, contrary to these
earlier assumptions, considerable amounts of metal, including Cu and Au,
were indeed consistently present in some vapor-rich inclusions (Audétat
et al., 2000; Harris et al., 2003; Heinrich et al., 1992, 1999; Klemm et al.,
2007; Lowenstern et al., 1991; Simon et al., 2005, 2006; Ulrich et al.,
2001), and subsequent work has shown that much of this metal content
is transported as sulfide complexes rather than as (or in addition to)
chloride complexes (Cauzid et al., 2007; Heinrich et al., 1992, 1999;
Pokrovski et al., 2005, 2008; Seo et al., 2009; Simon et al., 2006; Zajacz and
Halter, 2009; Zajacz et al., 2010).
Early resistance to these ideas was, I believe, at least in part due to
confusions of terminology: most papers dealing with this subject have
referred to metal solubility and transport in a vapor phase, suggesting to
the unwary a low density, low salinity gas, whereas for the most part the
fluids in question were either single-phase supercritical fluids, or
relatively high density vapors just below their critical points. Under such
high P–T conditions, vapors are almost as saline as the initial single-
phase fluid from which they evolved, and therefore they still contain
plenty of chloride for base metal complexing. But perhaps more
importantly, as noted above, these vapors will also contain a high
concentration of volatile sulfur species, which now appear to be
essential for the efficient solvation of chalcophile elements under high
P–T conditions. When combined with the higher mass proportion of the
vapor phase (versus brine condensate) and its high mobility, a model for
transport of the bulk of the metal flux in porphyries by relatively dense
vapors or supercritical fluids is now well established (Klemm et al.,
2007; Landtwing et al., 2010; Williams-Jones and Heinrich, 2005).
The rapid reduction in the efficiency of transport of metals as the
vapor plume rises, cools, and becomes less dense by brine condensation,
may explain precipitation of the bulk of Cu, Mo, and some Au over a
relatively narrow temperature interval between 425°–320 °C (Hemley et
al., 1992; Klemm et al., 2007; Landtwing et al., 2005). At shallower depths
and lower temperatures, the vapor phase may become too dilute to
transport significant amounts of base metals as chloride complexes, but
may continue to carry some metals such as Au, Cu, As, and Sb as sulfide
complexes (Deditius et al., 2009; Simon et al., 2006, 2007), eventually
either venting them to the surface in high-temperature fumaroles (e.g.,
Chaplygin et al., 2007; Hedenquist et al., 1994a; Symonds et al., 1987;
Tarana et al., 1995; Tessalina et al., 2008) or precipitating them in the
near-surface high-sulfidation epithermal environment (see Section 4.2.1;
Deditius et al., 2009; Hedenquist et al., 1993, 1994b; Heinrich et al., 1999,
2004; Larocque et al., 2008; Murakami et al., 2010; Pudack et al., 2009;
Williams-Jones and Heinrich, 2005).
4. Magmatic–hydrothermal ore formation
The focus of this paper is on the flux of metals in subduction-
related magmatic systems, but this would be of little practical interest
if that flux did not ultimately lead to ore formation. Thus far, we have
focused on the importance of firstly not losing significant amounts of
metal to a fractionating or residual sulfide phase, and then efficiently
partitioning those metals into a highly mobile aqueous fluid phase.
What subsequently happens to that fluid phase dictates whether
economic concentrations of metals are precipitated (grade), whereas
the scale of the magmatic and derivative hydrothermal system
controls the total amount of metals precipitated (tonnage).
4.1. Porphyry Cu ore formation
In a landmark paper, Cline and Bodnar (1991) presented a model
for the evolution of magmatic-hydrothermal systems from initial
14 J.P. Richards / Ore Geology Reviews 40 (2011) 1–26
aqueous fluid exsolution to cooling and mineral precipitation. A key
finding of this work was that, although there are many variables that
can affect the specific evolutionary path of a given system, an
economic porphyry Cu deposit can potentially be formed from quite
small volumes of typical andesitic arc magma. For example, the
authors showed that 15–90 km 3 of andesitic magma initially contain-
ing 50 ppm Cu, 2.5 wt.% H2O, and with a Cl/H2O ratio = 1, is sufficient
to generate a 250 Mt deposit with a grade of 0.75 wt.% Cu. The range of
required magma volumes reflects variables such as the depth of
magma emplacement and the compatibility of Cu with fractionating
mineral phases (larger volumes are required if Cu is compatible with
early fractionating silicate, oxide, or sulfide minerals). Details of the
model, later updated in Cline (1995), show that magmas emplaced at
moderate depths (1.0 to 2.0 kb, equivalent to depths of ~ 4–8 km)
most efficiently partition Cu into early saturating saline fluids,
whereas Cu and Cl are only released from shallowly emplaced
(0.5 kb, or ~2 km) magmas during late stages of crystallization (see
also Candela, 1989b). (Note that these depths reflect the locus of fluid
and metal exsolution from the magma under lithostatic pressure
conditions, as opposed to the depth of subsequent hydrothermal
metal deposition, which will be at shallower levels and likely under
hydrostatic pressure conditions; Fournier, 1999.) In large measure,
these differences reflect the change in properties of the magmatic–
hydrothermal fluid, which will separate initially as a moderately
saline supercritical fluid in deeper systems (Fig. 6a, path 1), but as
immiscible vapor and brine at shallower levels (Fig. 6a, path 2). Cline
(1995) concluded that optimum conditions for porphyry Cu ore
formation are obtained where magma containing ~ 4 wt.% H2O and
with a high initial Cl/H2O (typical of most arc magmas) is emplaced at
moderate crustal depths, thereby maximizing the efficiency of Cu
partitioning into an early saline fluid phase.
The results of these studies indicate that no special conditions or
magmatic metal enrichment are required to form even large porphyry
Cu deposits. Instead, the question is rather one of process efficiency:
where (what depth) and how are metalliferous fluids released and
channeled? This finding is of fundamental importance from an
exploration perspective, because it shifts the focus from seeking
anomalously metal-rich magmas (which have proven elusive; Jenner
et al., 2010) to searching for optimal ore depositional settings in
otherwise normal tectonomagmatic environments (e.g., Tosdal and
Richards, 2001).
Cloos (2001), Shinohara et al. (1995), and Shinohara and Hedenquist
(1997) considered the question of process efficiency from the
perspective of physical separation and focusing of volatile release
from the magma. Cloos (2001) suggested that the classic cupola shape
(Norton, 1982) of porphyry systems above larger batholithic magma
chambers reflects convective circulation of bubbly magma into the
shallow apical parts of these systems (at 1–3 km depth), where volatiles
physically separate from the melt and coalesce to form a discrete fluid-
filled cupola. The now-dense, volatile-depleted magma forms a
downward return flow to complete the convective cycle. In contrast,
Shinohara and Hedenquist (1997) envisaged fluids physically separat-
ing from the magma at greater depth within the underlying magma
chamber, and rising as a discrete plume up apical channelways formed
by fractures and dikes in the brittle carapace (Fig. 7).
A key aspect of both of these models is that volatile separation, and
Cu partitioning, occurs from a much larger volume of magma
(emplaced at deeper levels) than that preserved and commonly
visible within the shallow-level ore body. In Cloos's (2001) model,
volatile-rich, bubbly magma rising from the underlying batholith
convects through the cupola zone where it releases its fluids, whereas
in Shinohara and Hedenquist's (1997) model, vesiculation and
convective circulation occur in the underlying magma chamber itself,
and fluids are released as a plume into the base of the apical dike
system. Combining these models with (Cline, 1995; Cline and
Bodnar's, 1991) calculations suggests that maximum ore-forming
efficiency in porphyry systems is likely achieved where volatile
saturation occurs in large (≥ 100 km 3) mid- to upper crustal magma
chambers at depths ≥6 km, containing moderately hydrous (N4 wt.%
H2O) and Cl-rich magmas. These fluids either rise as bubbly magma or
as a separate volatile plume into the apical parts of the system
where decreasing pressure and temperature cause deposition of Cu
and Mo ± Au (Candela, 1989b; Shinohara et al., 1995).
Focusing of magma ascent and fluid flow into narrow apical
regions, or cupolas, is likely to be a function of structure in the brittle
rocks overlying the batholithic system (Tosdal and Richards, 2001,
and references therein). Shallow crustal magma emplacement will
cause extensional doming in the cover rocks, with dilational fault
zones providing high-permeability pathways for fluid and magma
ascent (Burnham, 1979). Evidence from the dike emplacement
literature suggests that such fractures may first be opened and
propagated by volatile pressure, and only later filled by more viscous
magma (Burnham, 1979; Carrigan et al., 1992; Rubin, 1995). This
raises the intriguing possibility that the cylindrical shapes of many
porphyry stocks may have arisen first as breccia pipes or diatremes
bored out by rapidly escaping volatiles, only later to be back-filled
with porphyritic magma (Fig. 8; Norton and Cathles, 1973; see also
Fig. 2 in Anderson et al., 2009, and Fig. 8 in Sillitoe, 2010, and Fig. 17 in
Vry et al., 2010).
To some extent, focusing of magma and fluid flow along narrow
conduits may be self-organizational, because once initial channel
ways have developed, they will represent high-permeability path-
ways and are likely to thermally weaken the wall rocks and promote
further fracturing and channeling.
Narrow focusing of apical fracturing and subsequent fluid flow are
likely to be critical to the formation of high grade porphyry deposits
(e.g., El Teniente, Chile; Vry et al., 2010), while multiple breccia/
intrusive events can potentially increase tonnage (provided that later
events do not destroy earlier mineralization).
Given suitable fluid flow focusing, three further factors combine to
cause maximum efficiency of metal deposition within relatively small
volumes in porphyry Cu ± Mo ± Au deposits. All three effects are
related to the steep temperature gradient in the cupola zone (Fig. 7),
and they therefore control the vertical range of ore deposition. On the
other hand, fluid focusing controls the lateral extent of mineralization.
In combination, the highest grades will occur where ore deposition is
both focused laterally and restricted vertically.
The first factor is that Cu solubility (as chloride species) decreases
dramatically as fluids cool through the temperature interval ~ 400° to
300 °C (Crerar and Barnes, 1976; Hemley et al., 1992; Klemm et al.,
2007; Landtwing et al., 2005; Xiao et al., 1998). Given the very sharp
temperature gradient implied by near-surface emplacement of
magma (Fig. 7), this temperature interval will correspond to a narrow
depth range, likely with 1 or 2 km of the surface (although it may
extend to greater depths with time as the magmatic–hydrothermal
system begins to cool). This depth range is typical for ore formation in
many porphyry systems.
The second factor is that SO2 dissolved in the magmatic–
hydrothermal fluid phase progressively disproportionates to H2S
and H2SO4 as the fluid cools below ~ 400 °C (Holland, 1965; Kusakabe
et al., 2000; Reeves et al., 2010; Sakai and Matsubaya, 1977):
4SO2 + 4H2 O ⇔ H2 S + 3H2 SO4 : ð1Þ
This reaction generates both hydrogen sulfide, which initiates
abundant precipitation of sulfide minerals (i.e., chalcopyrite, pyrite,
molybdenite), and also sulfuric acid, which causes early deposition of
large volumes of anhydrite in the potassic alteration zone, and
progressively increasing degrees of hydrolytic alteration (an initial
shift from feldspar-stable potassic alteration, to muscovite/sericite-
stable phyllic alteration). Consequently, the bulk of Cu-sulfide miner-
alization occurs at the low-temperature, late-stage end of the potassic
 J.P. Richards / Ore Geology Reviews 40 (2011) 1–26
(a)
Mixed magmatic-
hydrothermal
breccia
Porphyry
intrusion
Cuspate
intrusive
border
(c)
Limestone
wallrock
clast
Fig. 8. Photographs of porphyritic magma invading co-magmatic hydrothermal breccia pipe (a, c) and breccia vein/dike (b) from the Pachapaqui Ag–Cu–Pb–Zn deposit, Péru. The
breccia consists of fragments of porphyry magma and country rock; note scalloped, cuspate margins of the porphyry body in (a, b) and porphyry clasts in (c), indicating that the
magma was molten at the time of breccia formation and subsequent intrusion into the breccias. In (b), large vuggy spaces are partially filled with hydrothermal quartz, reflecting the
role of fluids in breccia formation. Scale in (c) is in centimeters.
alteration phase, just prior to the onset of phyllic alteration (i.e.,
corresponding to the “ore shell” of the classic Lowell and Guilbert, 1970,
porphyry Cu model).
The third factor is the increased permeability over this tempera-
ture range caused by a combination of the transition in silicate rocks
from ductile to brittle behavior at temperatures (between ~400°–
350 °C; i.e., the brittle–ductile transition; Fig. 7; Cathles, 1991;
Fournier, 1999; Landtwing et al., 2005), and a window of retrograde
silica solubility (between ~550–350 °C; Fournier, 1985). Not only do
these processes result in the formation of open-standing brittle veins
and porosity, thereby facilitating rapid upward fluid flow and
wallrock permeation (e.g., the crackle breccias, stockworks, and
disseminated mineralization textures so characteristic of porphyry Cu
deposits), but this transition also represents the boundary between
lithostatic and hydrostatic fluid pressures (a pressure differential of
~ 3×). Sudden depressurization of fluids across this boundary can be
expected to have major effects on fluid properties, including phase
separation (Fig. 6) and consequent changes in metal solubility (e.g.,
Landtwing et al., 2005, 2010; Murakami et al., 2010).
In combination, these four factors, (1) spatial focusing of fluid flow in
narrow cupolas, (2) reduction of metal solubility, (3) increased
dissolved sulfide activity, and (4) permeability increase due to transition
from ductile to brittle fracturing and retrograde silica solubility (with a
15
(b)
Porphyry
intruding
comagmatic
breccia
Porphyry
dike
Hydrothermal
quartz filling
cavity
~20 cm
Cuspate
porphyry Mixed magmatic-
clast hydrothermal
breccia
large pressure drop), serve to narrowly focus Cu-sulfide mineralization
both laterally and vertically within cupola zones above large mid- to
upper crustal batholithic complexes. The most likely reasons for
otherwise prospective porphyry systems to be unproductive will be
either a failure to focus fluid flow, or simply insufficient fluid supply
(likely due to an insufficiently large underlying magmatic system).
4.2. Epithermal Cu–Au ore formation
4.2.1. High-sulfidation epithermal Cu–Au deposits
As noted in Section 3.1, although the bulk of Cu (and Mo) appears to
be precipitated over the temperature interval 425°–320 °C, some Cu and
other metals such as Au, Sb, and As may remain in solution as sulfide
complexes, to be carried into the shallow epithermal regime. Observa-
tions from rare fluid inclusions in high-sulfidation epithermal Cu–Au
deposits suggest that the ore-forming fluid was a low- to moderate-
salinity liquid (0.2 to 4.5 wt.% NaCl equivalent; Hedenquist et al., 1994b;
Mancano and Campbell, 1995), which paragenetically post-dates
advanced argillic alteration formed by highly acidic magmatic gasses
(Arribas, 1995; Hedenquist et al., 1994b; Stoffregen, 1987). This
apparent inconsistency has been explained by Hedenquist et al.
(1998), Heinrich et al. (2004), and Heinrich (2005) in terms of
contraction of a moderate salinity supercritical magmatic fluid or
16 J.P. Richards / Ore Geology Reviews 40 (2011) 1–26

vapor by rapid cooling during ascent such that it does not touch, or
barely touches, the two-phase solvus (Figs. 6b and 9, paths 3 and 4,
respectively). Because of the curvature of the solvus crest (critical curve)
to lower salinities at low temperatures and pressures, this moderately
saline fluid will lie on the liquid side of the solvus at shallow depths,
although it may have contracted from what was originally a vapor or
supercritical fluid phase at higher temperatures and depths.
Heinrich et al. (2004) specifically suggested that brief intersection
with the solvus at high pressures and temperatures (Figs. 6b and 9, path
4) might be an important way to shed chloride-complexed components
such as Fe from the vapor in a brine condensate, leaving bisulfide ligands
free to bond with Cu and Au in the residual vapor and transport it to
shallower (epithermal) levels. This model requires that the vapor leaves
the two-phase surface again by cooling at pressure, thereby passing over
the crest of the solvus (the critical curve; (Figs. 6b and 9, path 4); upon
subsequent ascent and depressurization, this fluid will be a liquid, as
described above. Heinrich et al. (2004) argued that the Fe-rich brine
condensation step is essential for retention of Au (and Cu) in the vapor
phase, because otherwise Fe will tend to precipitate as Cu–Fe-sulfide
minerals and strip the fluid of bisulfide ligands, thus causing Au to co-
precipitate at depth (a possible mechanism for the formation of
porphyry Cu–Au deposits). However, this condensation step must
then be followed by cooling while still at depth, in order to “lift” the
vapor phase off the two-phase surface, and allow it to contract to a liquid
(Figs. 6b and 9, path 4).
A more detailed analysis of the phase diagram shown in Fig. 6
reveals that a typical magmatic fluid of 2–13 wt.% NaCl would have to
first intersect the solvus at temperatures above ~ 400°–500 °C for this
model to work optimally, otherwise it would fall on the liquid side of
the two-phase field, and would become more saline by boiling off a
dilute vapor (Figs. 9 and 10). Assuming that this did indeed happen,
then the smaller (by mass) vapor component would have to leave the
two-phase surface again at pressure before cooling below ~400 °C,
otherwise its salinity rapidly falls to sub-weight percent levels at
lower temperatures and lower pressures (Figs. 6 and 10), which are
inconsistent with fluid inclusion evidence for low to moderately saline
liquids in high-sulfidation epithermal ore formation (Hedenquist et
al., 1994b; Mancano and Campbell, 1995). Thus, the P–T trajectory of a
fluid that satisfies Heinrich et al.'s (2004) model for high-sulfidation
epithermal Cu–Au mineralization (Figs. 6b and 9, path 4) is somewhat
unique, and may occur only rarely or fleetingly during the waning
stages of a cooling magmatic–hydrothermal system.
A more normal, or early ascent pathway for a magmatic–
hydrothermal fluid would be for it to rise more-or-less is enthalpically
or quasi-adiabatically along a steep P–T gradient (e.g., Hemley and
Hunt, 1992; Henley and Hughes, 2000; Wood and Spera, 1984), and
therefore to dive deeply into the two-phase field and separate into an
increasingly dilute vapor phase and a saline brine (Figs. 6 and 9, path
1), or even to boil dry to halite plus vapor (Figs. 6 and 9, path 2). Such
fluid pathways might be consistent with the widespread and intense

0 100 200 300 400 500 600 700 800 900 1000
Wet granite solidus

Wet granodiorite solid

V-L solvus (vapour)

8 (lith)
V-L solvus (liquid)
2000

.%
Deep
magmatic wt
7 (lith)
20

fluid
exsolution
t.%
us

w
(hydrostatic)

10
(lithostatic)
Ductile
Brittle

6 (lith)
1500 15 (hyd)
.%
5 wt 14 (hyd)
5 (lith)
13 (hyd)
Deep
Depth (km)

single- 12 (hyd)
P (bars)

phase
fluid
11 (hyd)
4 (lith)
1000 3 10 (hyd)

4 9 (hyd)
1 1 wt.%
km 8 (hyd) 3 (lith)
°C/
Early 300otherm
erm

porphyry Shallow
magmatic g e 7 (hyd)
oth

veins
(2-phase fluid
ge

fluid) exsolution 6 (hyd)

/km

2 (lith)
500
°C

2 5 (hyd)
30

4 (hyd)
3 (hyd)
Main-stage 1 (lith)
brittle
2 (hyd)
V/

porphyry
L+

veins V+Halite
Ha

1 (hyd)
li

Epithermal
te

0 0
0 100 200 300 400 500 600 700 800 900 1000
T (°C)

Fig. 9. Pressure (depth)–temperature section through the H2O–NaCl phase diagram, with vapour–liquid (V–L) solvi drawn for 1, 5, 10, and 20 wt.% NaCl (data from Driesner, 2007;
Driesner and Heinrich, 2007). Red curves indicate that the solvus phase is a vapor, blue curves that it is a liquid; the transition point corresponds to the critical point for that
composition. Also shown are the wet granite and granodiorite solidi (Burnham, 1979), and average crustal (30 °C/km) and high (300 °C/km, near active volcanism) geothermal
gradients (Barbier, 2002; Goff et al., 1992; Noorollahi et al., 2007). Depths are indicated for hydrostatic (hyd) and lithostatic (lith) pressure conditions. Typical temperature–depth
ranges for supercritical magmatic fluid exsolution, early high-temperature porphyry veins, later main-stage brittle porphyry veins, and epithermal mineralization are indicated. Four
fluid P–T paths are shown corresponding to: (1) a typical porphyry-forming fluid path; (2) a shallow high-temperature path boiling to dryness (V + Halite field); (3) the deep
contraction path of Hedenquist et al. (1998); and (4) the contraction with minor brine condensation path of Heinrich et al. (2004).
 J.P. Richards / Ore Geology Reviews 40 (2011) 1–26 17

-8 -7 -6 -5 -4 -3 -2 -1 0 10 20 30 40 50 60 70 80 90 100
1300 Single
1300
V-L solvus (liquid) phase 700°C
V-L solvus (vapour) mag-

rve
1200 matic 1200
V-H solvus (vapour) fluid

Critical cu
1100 V+L
1100
(700°C)

1000 1000

600°C
900 900

800 V 800
V+L
(600°C)
700
P (bars)

700

600 500°C 600

L+H (600°C)
L (600°C)
500 500
V+L
(500°C)

L+H (500°C)
L (500°C)

L+H (700°C)
400 400

L (700°C)
V+H (600°C)

V+H (500°C)

L+H (400°C)
300 400°C 300

L (400°C)
V+H (700°C)
Critical P V+L
200 of H2O (400°C) 200
V+H (400°C)

100 100

0 0
-8 -7 -6 -5 -4 -3 -2 -1 0/1 10 20 30 40 50 60 70 80 90 100
log (wt.% NaCl) wt.% NaCl
scale
change

Fig. 10. Pressure–XNaCl section through the H2O–NaCl phase diagram, with vapor–liquid (V–L) solvi drawn at various temperatures (data from Driesner, 2007; Driesner and Heinrich,
2007). Red curves indicate that the solvus phase is a vapor, blue curves that it is a liquid; below the vapor–halite (V–H) solvus, vapor curves are shown in orange. Note the scale
change on the salinity axis at 1 wt.% NaCl, in order to illustrate the extremely low salinity of low-temperature vapor phases. The range of salinity for typical deeply exsolved single-
phase (supercritical) magmatic fluids (2–13 wt.% NaCl) is shown in gray. Fluids that intersect the V–L solvus above ~ 400°–500 °C will be moderate-density vapors and will condense
a small amount of dense, saline liquid; fluids that intersect the solvus below this temperature will be liquids and will boil off a dilute, low-density vapor phase.

acidic (advanced argillic) alteration commonly found at shallow levels
above porphyry systems, which is caused by acidic gasses (H2SO4,
HCl) condensing from a low-density vapor plume. As Heinrich et al.
(2004) noted, such acidic vapors do not appear to transport Au (or Cu)
effectively because bisulfide (HS –) ligands are hydrolized to H2S. This
may explain why advanced argillic alteration caps are commonly
barren (in terms of Au and Cu) and merely generate permeability that
potentially focuses later ore-forming fluid flow. Thus, mineralization
may only occur where later moderate salinity liquids have followed a
higher pressure, rather specialized cooling path, as described above
(Heinrich et al., 2004).
4.2.2. Low-sulfidation epithermal Au deposits (including alkalic-type
deposits)
Although low-sulfidation epithermal Au deposits are commonly
found in volcanic terrains, their link to magmatism is more tenuous
than high-sulfidation deposits, and there is commonly evidence for a
greater involvement of meteoric groundwater in their formation than
magmatic fluids (e.g., Faure et al., 2002; Field and Fifarek, 1985; Heald
et al., 1987). Nevertheless, alkalic-type epithermal Au deposits, which
are mineralogically similar to low-sulfidation deposits (adularia and
sericite — or roscoelite [vanadium mica] — are stable), do show a
strong temporal and genetic relationship to alkalic magmas, typically
in relatively small and isolated intrusive complexes located in back-
arc or post-subduction settings (e.g., Jensen and Barton, 2000; Kelley
et al., 1998; Müller and Groves, 1993; Mutschler et al., 1985; Richards,
1995; Thompson et al., 1985).
Fluids in these alkalic-type deposits are commonly low- to
moderate salinity (0–10 wt.% NaCl equiv.), low temperature (typically
≤250 °C) liquids, with evidence for decompressional boiling or fluid
mixing as the prime ore depositional mechanism in high grade
breccias and veins (Jensen and Barton, 2000; Richards, 1995). Stable
isotopic compositions of these fluids are generally ambiguous, and
permit interpretations of the involvement of either isotopically
exchanged meteoric waters or magmatic fluids, or both (Ahmad et
al., 1987; Carman, 2003; Richards, 1995; Richards and Kerrich, 1993;
Ronacher et al., 2004; Scherbarth and Spry, 2006; Zhang and Spry,
1994). Similar stable isotopic data from other low-sulfidation deposits
are commonly interpreted to reflect a meteoric fluid source because of
the absence of clearly coeval magmatism (as noted above). However,
the close link with magmatism in alkalic-type systems suggests that a
magmatic fluid source is more likely (e.g., Carman, 2003; Scherbarth
and Spry, 2006; Simmons and Brown, 2007), and the vapor
contraction model described in Section 4.2.1 could explain the
observed characteristics of these ore fluids (i.e., direct contraction to
a moderate salinity liquid from a high temperature magmatic fluid at
depth). Because of the association of these deposits with relatively
small intrusive complexes, and therefore a smaller crustal thermal
anomaly, a shallower fluid P–T path with cooling at depth is more
likely, consistent with a model of vapor contraction.
18 J.P. Richards / Ore Geology Reviews 40 (2011) 1–26
5. Summary and conclusions
5.1. Sources of magmas and metals
Magmatic–hydrothermal porphyry Cu ±Mo±Au, Au, Mo, and Sn–W
deposits (and related epithermal Au deposits), derive their metals from
their associated magmas. With the exception of porphyry Sn–W deposits
that are associated with crustally derived S-type granites, most
other deposits in this grouping are formed by calc-alkaline to mildly
alkaline I-type granitoids directly or indirectly related to subduction.
Sources of these magmas include subduction-metasomatized astheno-
spheric mantle wedge, basaltic oceanic crust and/or seafloor sediments,
and, in post-subduction settings, subduction-modified upper plate
lithosphere. The majority of normal arc porphyry systems are generated
from hydrous mantle wedge melts that have interacted to varying
degrees with the upper plate lithosphere during passage towards the
surface. Assimilation and fractional crystallization processes fundamen-
tally change the composition of the primary basaltic arc magmas to
intermediate calc-alkaline compositions, with fractionated trace element
patterns and evolved (crustal) isotopic signatures.
Seafloor sediments and basaltic oceanic crust only melt under
unusually hot subduction zone conditions or locally at plate edges, and
despite widespread claims of the identification of slab melts (adakites)
in the literature based on high Sr/Y and La/Yb ratios in some evolved
granitoids, this process is unlikely to be a major contributor to arc
magmatism and metallogeny. Rather, these subtle trace element ratios
can be readily explained by fractionation of hornblende ± titanite and
residual garnet, and suppression of plagioclase fractionation from
water-rich mantle wedge basaltic magmas. These trace element
characteristics are therefore an indicator of high magmatic water
content rather than being a source signature, and this likely explains the
common association of high-Sr/Y (i.e., hydrous) magmas with mag-
matic–hydrothermal ore deposits — without magmatic water, such
deposits cannot form.
Potential sources of metals in arc magmas include the oceanic crust
and sediments (via dehydration fluids or melting), the mantle wedge,
and the upper plate crust. Fluid–mobile elements such as K, Rb, Cs, Ca, Sr,
Ba, U, B, Pb, As, Sb, Tl, and possibly Cu, Au, Re, and the Pd-group
elements, along with large amounts of H2O, Cl, and S, are fluxed from the
dehydrating subducting slab into the mantle wedge, causing metaso-
matism and partial melting by lowering the peridotite solidus. Although
there is some evidence for slab-derived fluid contributions of chalco-
phile and highly siderophile elements (Cu, Au, PGE) to the mantle
wedge, it is not clear that this is a necessary metallogenic step, the upper
mantle already containing significant amounts of these elements. Likely,
a more important control on the metal content of subsequent partial
melts is the abundance and stability of residual sulfide phases in the
asthenospheric mantle source. Under the high fO2 and fS2 conditions of
arc magmatism, sulfur will be dominantly present as sulfate and sulfate,
but saturation in small amounts of sulfide phases is also likely. These
sulfide phases will tend to deplete the magma in highly siderophile
elements (Au and PGE), but will not be present in sufficient volume to
significantly deplete the magma in more abundant chalcophile elements
such as Cu and Mo. Such magmas therefore have the potential
subsequently to form porphyry Cu–Mo deposits. Thus, Cu (and perhaps
Mo) are thought to be predominantly derived from the mantle, plus or
minus contributions from the subducting slab. Gold and silver present in
minor amounts in such deposits may also be derived from subduction
sources, although there is some evidence for additional contributions
from the upper plate crust (especially for Ag, and also perhaps Mo).
Arc-like magmas and related porphyry and epithermal ore deposits
also occur in post-subduction tectonic settings, such as subduction
reversal or migration, arc collision, continent–continent collision, and
post-collisional rifting. They are distinguished from normal subduction-
related suites by slightly higher magmatic alkali (K2O and Na2O)
contents, and by the occurrence of Au-rich deposits (although normal
porphyry Cu–Mo deposits can also occur). Such magmatic–metallogenic
systems are thought to form by remelting of previously subduction-
modified upper plate lithosphere, and in particular the lower crustal
amphibolitic cumulate roots of former arc magmatic complexes.
Remelting can be triggered by crustal thickening and thermal rebound
following arc or continent collision, delamination of sub-continental
mantle lithosphere causing direct exposure of the lower crust to
asthenospheric temperatures and melts, and asthenospheric upwelling
during rifting of former arc crust. Sparse sulfide phases in these arc
cumulates, residual from fractionation of previous arc magmas, will
likely be rich in chalcophile and highly siderophile elements. During
low-volume melting under relatively low fS2 conditions (in the absence
of a flux of S from active subduction), these sulfide phases will likely
redissolve in the mildly alkaline partial melt, and may provide a source
for Au-rich (±PGE) post-subduction porphyry Cu–Au and epithermal
Au systems: examples include the Roşia Montană, Skouries, Kisladag,
Çöpler, and Sari Gunay porphyry Cu–Au and epithermal Au deposits in
the Neo-Tethyan belt of Romania, Greece, Turkey, and Iran, and the
Grasberg, Ok Tedi, Porgera, Lihir, and Emperor porphyry Cu–Au and
epithermal Au deposits in the southwest Pacific. However, gold
enrichments may not occur where more abundant sulfides were
present in the former arc complex, leading to more “normal” porphyry
Cu± Mo systems: examples include the Kerman porphyry Cu belt of
central Iran, and the Gangdese porphyry Cu belt of Tibet.
Porphyry Mo and Sn–W deposits associated with felsic magmas in
continental interiors are thought to form mainly by partial melting of
continental crust during rifting to form S-type, lithophile element-rich
granitic magmas. A role for mafic, mantle-derived magmas is suggested
by the common association with such rocks, but their role may be
predominantly as a heat source for crustal melting and a trigger for
volatile saturation and eruption, rather than as a unique source of
metals.
5.2. Porphyry and epithermal ore formation
In the porphyry and epithermal ore depositional environment, a
critical role is played by aqueous fluids exsolving from hydrous
magmas emplaced in the mid- to upper crust. The P–T–X properties of
magmatic hydrothermal fluids, approximated by the H2O–NaCl
system, combined with volatile solubility in intermediate composition
magmas, suggest that fluid saturation occurs at depths of 5–10 km in
the batholithic roots of arc magmatic systems. Volatile exsolution may
lead to the upward propagation of buoyant bubbly magma as dikes
and stocks intruded into the overlying shallow crust (with or without
subsequent eruption at surface), and/or the rapid ascent of a separate
volatile plume. Structural focusing and chanelling of these evolved
magmas and fluids creates a cupola zone characterized by high
thermal gradients and fluid flux. Metals (Cu, Mo, Au), which partition
strongly into the saline (2–13 wt.% NaCl equivalent) and S-rich
magmatic hydrothermal phase at high P and T in the underlying
batholithic magma chamber, experience rapid reduction in solubility
as these fluids ascend, depressurize, and cool, with the bulk of Cu and
Mo being precipitated over a temperature range of 425°–320 °C at 1–
6 km (commonly ≤2 km) depth.
This depth–temperature interval is critical because it also repre-
sents: (1) the upward transition from ductile to brittle behavior in the
cover rocks (~400°–350 °C), which facilitates fracturing and rapid fluid
depressurization; (2) a window of retrograde silica solubility (~550°–
350 °C), which enhances permeability and porosity for ore deposition;
and (3) the temperature range (b400 °C) over which SO2 in the fluid
phase begins to disproportionate to H2S and H2SO4, which causes
precipitation of sulfide minerals (chalcopyrite, pyrite, molybdenite, rare
bornite). This reaction also generates increasingly acidic fluids, leading
to the characteristic progression from feldspar-stable alteration assem-
blages (potassic), through muscovite/sericite-stable assemblages
 J.P. Richards / Ore Geology Reviews 40 (2011) 1–26
(phyllic), to clay- (argillic) and alunite-stable assemblages (advanced
argillic).
Depending on the depth of exsolution, the initial magmatic fluid will
either be a supercritical fluid (below ~6 km depth) or will exist as a two-
phase moderate salinity vapor and high density brine. As the plume
ascends, it will intersect its solvus (in the case of a deeply exsolved
supercritical fluid), and the vapor phase will become progressively less
saline through brine condensation. At the level of porphyry ore
formation, both the brine and vapor phase may contribute to metal
transport and deposition, although there is increasing evidence for the
importance of the vapor phase as a large-volume, highly upwardly
mobile transportation medium. However, as this vapor phase continues
to ascend, it will rapidly decrease in salinity, such that chloride-
complexed metals are unlikely to be transported by such fluids to
shallow epithermal levels. It will also increase in acidity, thereby
reducing the solubility of bisulfide-complexed metals such as Au (and
perhaps also Cu) by protonation of HS– to H2S. This acidic vapor phase is
responsible for the extreme acid leaching in advanced argillic lithocaps
above porphyry systems.
High-sulfidation epithermal Cu–Au deposits are hosted by these
highly permeable advanced argillic alteration zones, but appear to have
been formed by later, moderately saline (0.2 to 4.5 wt.% NaCl
equivalent), less acidic liquids. Two models have been proposed to
explain the origin of these paragenetically late mineralizing fluids in
terms of contraction of a single phase (supercritical) magmatic fluid,
with (Heinrich et al., 2004) or without (Hedenquist et al., 1998) brief
intersection of the solvus. Because of the topology of the P–T–XNaCl
phase diagram, such fluids contract to a liquid phase upon cooling at
pressure. Thus, these authors propose that high-sulfidation epithermal
Cu–Au deposits may be formed directly from late-stage magmatic
hydrothermal fluids.
Although low sulfidation epithermal Au deposits have not been
discussed in detail in this paper, because most such deposits are not
directly related to porphyry-type magmatic–hydrothermal systems,
the vapor contraction mechanism might have applicability to alkalic-
type epithermal gold deposits, which do show a close genetic
relationship to post-subduction alkalic magmas.
Acknowledgments
I would like to thank Nigel Cook and Timothy Horscroft for inviting
me to submit this paper. Review papers, by their nature, draw heavily on
the work of others, and I would particularly like to acknowledge the
following people who have influenced my thinking on this subject: P.
Candela, J. Cline, J. Dilles, J. Hedenquist, C. Heinrich, R. Sillitoe, and R.
Tosdal. An anonymous reviewer is thanked for helpful and constructive
comments. This work was funded by a Discovery Grant from the Natural
Sciences and Engineering Research Council of Canada.
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