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Magmatic-hydrothermal processes within an evolving Earth: Iron oxide-

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Magmatic-hydrothermal processes within an evolving Earth:
Iron oxide-copper-gold and porphyry Cu ± Mo ± Au deposits
Jeremy P. Richards1* and A. Hamid Mumin2*
1
Department of Earth and Atmospheric Sciences, University of Alberta, Edmonton, Alberta T6G 2E3, Canada
2
Department of Geology, Brandon University, 270 18th Street, Brandon, Manitoba R7A 6A9, Canada

ABSTRACT surrounded and partially overprinted by broad

Iron oxide-copper-gold (IOCG) deposits formed by magmatic-hydrothermal fluids (MH- zones of lower-temperature (<350 °C) more
IOCG) share many similarities with, but have important differences from, porphyry Cu acidic alteration (sericite-pyrite, clay) generated
± Mo ± Au (porphyry) deposits: MH-IOCG deposits predominantly occur in Precambrian by disproportionation of dissolved SO2 to form
rocks, are Fe oxide rich, and have volumetrically extensive high-temperature alteration zones, H2S and H2SO4.
whereas porphyry deposits occur almost exclusively in Phanerozoic rocks, are Fe sulfide rich, Porphyry deposits also form temporally and
and have narrower high-temperature alteration zones. We propose that these deposit types spatially separated from active arcs in post-sub-
are linked by common subduction-modified magmatic sources, but that secular changes in duction settings, from partial melting of previ-
oceanic sulfate content and geothermal gradients at the end of the Precambrian caused a ously subduction-modified lithosphere (Solo-
transition from the predominance of S-poor arc magmas and associated S-poor MH-IOCG mon, 1990; Hou et al., 2009; Richards, 2009;
systems, to S-rich arc magmas and associated S-rich porphyry deposits in the Phanerozoic. Shafiei et al., 2009; Pettke et al., 2010), a process
Phanerozoic MH-IOCG and rare Precambrian porphyry deposits are explained by local or also recently proposed for MH-IOCG deposits
periodic fluctuations in oceanic oxidation state and sulfate content, or remobilization of previ- (Groves et al., 2010). Porphyry systems formed
ously subduction-modified lithosphere in post-subduction tectonic settings. in such settings range to more alkaline compo-
sitions and may be Au rich, leading to alkaline
INTRODUCTION of chalcopyrite, bornite, molybdenite, pyrite, porphyry Cu-Au and alkalic-type epithermal
Porphyry Cu ± Mo ± Au (porphyry) and iron and magnetite, and are formed from magmatic- Au deposits (Richards, 2009). Such deposits are
oxide-copper-gold deposits of magmatic-hydro- hydrothermal fluids exsolved from relatively typically relatively S poor and Fe oxide rich, and
thermal origin (MH-IOCG; sensu Groves et al., oxidized (fayalite-magnetite-quartz buffer show the closest overlap with MH-IOCG depos-
2010) contain some of the largest concentrations [ΔFMQ] = +1 to +2), S-rich, calc-alkaline to its in terms of tectonic setting, magma composi-
of Cu, Au, U, Fe, and other metals on Earth, mildly alkaline, arc-related magmas. Mineral- tion, and ore and alteration geochemistry.
and are targets of choice for mineral explora- ization is mainly associated with central zones of Porphyry deposits occur most commonly in
tion. These deposit types have many similarities high-temperature (≥350 °C) potassic alteration Cenozoic and Mesozoic rocks, are less abun-
but also some important differences, and their (biotite–K-feldspar–amphibole–magnetite), dant in the Paleozoic, and are very rare in the
genetic relationships, if any, have been debated
extensively (Barton and Johnson, 2000; Wil-
liams et al., 2005; Pollard, 2006; Groves et al., Magmatic-hydrothermal Volcanic edifice may
Porphyry
or may not be present
2010; Mumin et al., 2010). Key differences are IOCG Breccia pipe
that MH-IOCG deposits are S poor and are com- or vent Advanced argillic
Intermediate-low sulfidation
mon in Precambrian rocks, whereas porphyry High-sulfidation
deposits are S rich and predominate in the Pha- Intermediate-sulfidation
nerozoic. We suggest below that a continuum Sinter, breccia or vein
Vein Au, Ag (As,Hg,Cu,Zn,Pb)
exists in processes and time between porphyry Cu,Ag,U,Co
Ni,Au,Bi Pyrite Clay-Chl Py Hem
and MH-IOCG deposits formed in orogenic and Propylitic
Clay-Chl
post-orogenic settings, primarily reflecting the Supracrustal Py,Hem
Sericite
recycling of volatiles into the lithosphere via sequence Vein Cu,Pb,Zn,Ag,Au
Pyrite
Propylitic Hem

subduction, coupled with a progressive decrease

in lithospheric geotherms and increase in deep- Cu,Au Co Ag U Hematite Cu Au Mo
seawater sulfate abundance since the Archean. Magnetite
Vein
Na-Ca Au,Ag
Ser

Sericite
K-fsp

FORMATION OF PORPHYRY CU ± MO K-feldspar

± AU DEPOSITS Propylitic
1 km Albite Na-Ca Mag+Py Chl = Chlorite
The formation of porphyry deposits has been K-fsp Hem = Hematite
1 km K-fsp = Potassium feldspar
described extensively in the literature (e.g., Na Mag = Magnetite
Sillitoe, 1972, 2010; Richards, 2003, 2011; Basement rocks Na-Ca Na = Sodic alteration
Na-Ca = Sodic-calcic alteration
Seedorff et al., 2005), and only key points are Py = Pyrite
Batholith Ser = Sericite
noted here (Fig. 1; Table 1). Porphyry deposits
are large geochemical anomalies of Fe and S, Figure 1. Schematic model for magmatic-hydrothermal systems illustrating relationship be-
with lesser but economically important enrich- tween S-rich porphyry Cu ± Mo ± Au deposits (right side) and S-poor magmatic-hydrothermal
ments in Cu ± Mo ± Au. They consist of veins iron oxide-copper-gold (MH-IOCG) deposits (left side). Approximate hydrothermal mineral
and disseminations with variable proportions transitions and relative spatial footprint are shown for albite–K-feldspar, K-feldspar–sericite,
and magnetite-hematite transitions. Prograde and retrograde overprinting of alteration as-
semblages and mineralization is common. Spatial relationships for porphyry deposits after
*E-mails: Jeremy.Richards@ualberta.ca; Mumin Seedorff et al. (2005), Sillitoe (2010), and Richards (2011); for MH-IOCG, after Hitzman et al.
@BrandonU.ca. (1992), Williams et al. (2005), and Mumin et al. (2010).

GEOLOGY, July 2013; v. 41; no. 7; p. 767–770 | doi:10.1130/G34275.1 | Published online 16 May 2013
GEOLOGY
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2013 Geological 2013 | of
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 TABLE 1. COMPARISON BETWEEN PORPHYRY AND MAGMATIC-HYDROTHERMAL IOCG DEPOSITS
Characteristic
Major metal association
Minor metal association
Sulfur content
Ore minerals
Ore fluid
Fluid oxidation state; acidity
Source of fluid
Source of metals
Alteration geochemistry
Width of high-temperature (>350–400 °C) alteration
Depth of formation
Geothermal gradient
Regional metamorphism
Magma association; composition; oxidation state
Tectonic setting
Kinematic setting
Age range
Note: Characteristics of post-subduction porphyry deposits shown in square brackets. IOCG—iron oxide-copper-gold; ΔFMQ—fayalite-magnetite-quartz buffer; REE—
rare earth element.
Precambrian. One explanation for this temporal
distribution is that arc-related porphyry deposits
form in environments of active uplift and ero-
sion, commonly followed by collision, and as
such they are highly susceptible to loss through
erosion (Kesler and Wilkinson, 2006). However,
it is difficult to explain the extreme rarity of
Precambrian deposits by erosion alone, and we
find no credible evidence that porphyry deposits
were in fact formed in abundance prior to the
Phanerozoic. We note that many Precambrian
supracrustal sequences are preserved around the
world, including arc successions, but indisput-
able porphyry-type deposits in these rocks are
almost nonexistent (Seedorff et al., 2005).
FORMATION OF MH-IOCG DEPOSITS
Major MH-IOCG systems are found in con-
tinental orogenic to post-orogenic settings from
the late Archean (e.g., Carajas district, Brazil)
and Proterozoic (e.g., Olympic Dam and Clon-
curry districts, Australia; Norrbotten, Sweden;
Great Bear, Canada; Williams et al., 2005;
Groves et al., 2010; Mumin et al., 2010; Skir-
row, 2010), to the Mesozoic (e.g., Candelaria–
Punta del Cobre and Manto Verde in Chile;
Raul-Condestable and Mina Justa in Peru;
Marschik and Fontboté, 2001) (Table 1).
MH-IOCG deposits also constitute large
geochemical enrichments in Fe, but mainly as
Fe oxides (± Fe silicates, Fe carbonates) with
relatively minor Fe sulfides; they contain eco-
nomically important enrichments in Cu ± Au
± U ± REE (rare earth elements) ± Co (Table 1).
They are commonly associated with relatively
oxidized but apparently S-poor, calc-alkaline
to mildly alkaline magmas. They display broad
zones of high-temperature (~600–400 °C)
768
Porphyry Cu ± Mo ± Au
[post-subduction porphyry]
Cu, Mo, Au
Ag, Sn, W
High: sulfides and sulfates [lower]
Chalcopyrite, bornite, molybdenite, magnetite;
abundant pyrite with sericite
H2O-NaCl-KCl
Oxidized (ΔFMQ = +3 to +5); neutral to acidic
Magmatic
Subducted slab and asthenosphere [subduction-
modified lithosphere]
K-(Na)-Fe-S-SiO2
1–2 km
1–5 km
Normal
Minimal to low grade
Calc-alkaline [mildly alkaline]; intermediate to felsic
[mafic to felsic]; ΔFMQ = +1 to +2
Subduction [post-subduction]
Transpression or transtension
Dominant in Phanerozoic, rare in Precambrian
Na (albite-amphibole-pyroxene), Na-Ca-Fe
(magnetite-actinolite-apatite), or K-Fe (K-feld-
spar–magnetite–biotite–amphibole) altera-
tion (Fig. 1). Unlike porphyry systems, lower-
temperature alteration zones (<400 °C; e.g.,
hematite-chlorite-sericite-carbonate) are char-
acterized by persistence of near-neutral to only
mildly acidic pH conditions, with rare highly
acidic alteration, reflecting lower abundances of
H2SO4 in the hydrothermal fluids.
Whereas fluids and metals in porphyry
deposits are derived primarily from underlying
magmatic sources (see the review in Richards,
2011), the origin of IOCG fluids has been widely
debated, ranging from metamorphic and crustal
sources to magmatic hydrothermal fluids. Here,
we restrict our discussion to magma-driven sys-
tems involving primary magmatic fluids, albeit
with variable crustal contributions (Barton and
Johnson, 2000; Pollard, 2006; Groves et al.,
2010; Skirrow, 2010).
MH-IOCG systems form primarily during
extensional or transtensional deformation peri-
ods, in tectonic settings ranging from back-arc or
distal arc (e.g., Olympic Dam; Skirrow, 2010) to
intra-arc (e.g., Candelaria–Punta del Cobre, Mar-
cona; Marschik and Fontboté, 2001; Chen et al.,
2010), and to post-collision extensional settings
(e.g., Great Bear; Mumin et al., 2013). These
geotectonic environments are shared by arc-
related and post-subduction porphyry deposits.
GENERATION OF FERTILE MAGMAS
IN ARC AND POST-SUBDUCTION
ENVIRONMENTS
A key factor in the generation of magmatic
hydrothermal porphyry and IOCG deposits is the
recycling of H2O into the mantle via subduction
Magmatic-hydrothermal IOCG
Fe, Cu, Au
U, REE, Co, Ag
Low: minor sulfides
Magnetite, hematite, chalcopyrite, bornite, chalcocite
H2O-CO2-NaCl-KCl
Likely ΔFMQ = +3 to >+5; neutral to mildly acidic,
rarely acidic
Magmatic ± crustal fluids
Subduction-modified lithosphere and fluxing from host
rocks
Na-K-Fe-P-Ca-CO2-SiO2
1 to ≥7 km
Surface to ~10 km
Elevated
Low to high grade
Calc-alkaline to mildly alkaline; mafic to felsic;
uncertain, but likely ΔFMQ = 0 to +2
Distal, back-arc, or post-subduction
Extension to transtension
Dominant in Precambrian, important in Mesozoic
of seafloor-altered oceanic lithosphere. Dehy-
dration of the subducting slab releases aqueous
fluids that metasomatize the overlying astheno-
spheric mantle wedge and cause partial melting
to form hydrous basaltic magmas. Fractionation
and interaction of these magmas with the upper
plate lithosphere generates evolved, hydrous,
relatively oxidized (ΔFMQ = +1 to +2), calc-
alkaline magmas. Upon emplacement at shal-
low crustal depths, volatiles are released due to
cooling, and these fluids may go on to form mag-
matic-hydrothermal ore deposits (Hedenquist
and Lowenstern, 1994; Richards, 2003).
Richards (2009, 2011) proposed that mag-
matic-hydrothermal ore deposits can also form
temporally and/or spatially distal to active sub-
duction zones by remelting of lower crustal
amphibolitic cumulates and/or metasomatized
mantle lithosphere residual from precursor arc
magmatism. A significant amount of the chalco-
phile (e.g., Cu) and highly siderophile element
(e.g., Au and platinum group elements [PGE])
content of the arc magma flux may be left as
residual sulfides in these deep lithospheric
cumulate or metasomatized zones. Second-stage
partial melting of these amphibolitic rocks may
occur at any later time due to tectonic processes
that increase temperature or reduce pressure,
such as crustal thickening or lithospheric mantle
delamination during arc or continent collision,
post-collisional extension, or back-arc rifting.
Lacking a fresh supply of subduction-sourced
sulfur, derivative partial melts will be relatively
S poor, and will dissolve a significant propor-
tion of any residual Cu ± Au–rich sulfides; such
magmas may go on to form relatively S-poor
magmatic-hydrothermal Cu ± Au deposits
(Richards, 2009). Porphyry and MH-IOCG
www.gsapubs.org | July 2013 | GEOLOGY
 Figure 2. Global changes
deposits have now been recognized from all of affecting magmatic-hy- 28 A
Present-day sulfate concentration
these post-subduction tectonic settings (Pollard, drothermal ore deposits
2006; Hou et al., 2009; Richards, 2009; Groves from Archean to present. 24 300

~ Paleo heat production (% present value)

et al., 2010; Skirrow, 2010), and it is here that A: Increase in seawater

Seawater sulfate concentration (mM)

we observe the closest overlap between these sulfate concentration ~ De
and decrease in heat pro- 20 crea
two broad deposit types. se in
duction relative to pres- pale
o he
ent-day values. Sulfur 16 at pr Porphyry 200
oduc
DISCUSSION concentrations from Kah tion Cu most
Despite the similarities noted above, por- et al. (2004) and Gill et al. Porphyry Cu rare
abundant
12
(2007); paleo-heat pro-
phyry and MH-IOCG deposits vary somewhat duction from Plant and
in both economic and trace-element signatures, Saunders (1996), Hand 8 IOCG Deposits 100
are distinct in their alteration footprints, and vary et al. (1999), and Araki
Initial
in abundance over geological time. We argue et al. (2005). IOCG—iron 4 biospheric ate
oxide-copper-gold. B: er sulf
below that these differences may be explained oxygen
S eawat
Atmospheric O2 levels as
by secular changes in the abundance of seawater a percentage of present 0 0
sulfate entering magmatic-hydrothermal sys- 2.5 2.0 1.5 Age Ga 1.0 0.5 0
atmospheric level (%PA;

O2 (% present atmosphere)
tems, and decreasing lithospheric geothermal blue dashed line) super- Oxic upper ocean
B 0.5
imposed on correspond-

Deep ocean O2 (mM)

gradients since the Precambrian. 100
Anoxic deep ocean with widespread 0.4
ing ocean redox condi-
tions (after Canfield, sulfidic bottom waters 0.3
10 Anoxic Oxic deep
Fe-Oxide Versus Fe-Sulfide Deposits: The 2005; Shields-Zhou and deep
? O -%PA 2
ocean
O Max2
0.2
Role of Seawater Sulfate Och, 2011). Following the 1 ocean O Min 0.1
A key difference between Fe oxide–rich MH- Neoproterozoic Oxygen- 2

IOCG deposits and Fe sulfide–rich porphyry
deposits reflects a difference in magmatic sulfur
content in otherwise similar hydrous, relatively
oxidized, calc-alkaline to mildly alkaline source
magmas. Phanerozoic arc magmas and related
porphyry and high-sulfidation epithermal depos-
its are S rich, with the bulk of the sulfur being
derived from seawater via the subduction cycle
(De Hoog et al., 2001; Wallace and Edmonds,
2011). In contrast, Prouteau and Scaillet (2013)
have shown that arc magmas generated in the
Precambrian were relatively S poor, and this
correlates with the scarcity of S-rich Precam-
brian porphyry deposits.
A secular increase in the sulfur content of
arc magmas may relate to a parallel increase in
the abundance of dissolved sulfate in seawater
over time. Seawater sulfate concentrations are
estimated to have been ~0.2 mM from the late
Archean to earliest Proterozoic, with a gradual
increase to the early Phanerozoic, followed
by a rapid increase to modern day values of
~28 mM (Fig. 2; Kah et al., 2004; Gill et al.,
2007). The increase in seawater sulfate content
is directly linked to the availability of biogenic
oxygen and the onset of oxidative weathering,
which released continent-derived sulfate to the
oceans beginning at ca. 2.3 Ga (Kasting, 2001).
A dramatic spike in both seawater and seafloor
sulfate content occurred in the Phanerozoic due
to sulfide oxidation by ocean ventilation and
marine bioturbation (Canfield and Farquhar,
2009; Shields-Zhou and Och, 2011). Subduc-
tion of this oxidized material would introduce
abundant sulfate to the mantle wedge for the
first time, and generate S-rich arc magmas.
Thus, we propose that subduction-related mag-
mas would have been S poor in the Precambrian,
inhibiting the formation of S-rich porphyry-type
deposits (except in locally anomalous environ-
ments, such as subduction of shallow marine
ation Event, deep ocean 0.1 Ocean basalt and sediments
O2 levels (black short
dashed lines) varied rapidly over short time intervals (Holland, 2006), resulting in variable
sulfate additions to oceanic crust.
basins where conditions were oxidizing; Fig. 2),
but favoring the development of S-poor MH-
IOCG systems. Conversely, S-rich Phanerozoic
arc magmas favor the formation of porphyry-
type deposits, although periodic swings back to
anoxic deep-ocean conditions, particularly evi-
dent in the Mesozoic (Holland, 2006), could lead
to the intermittent formation of S-poor magmas
favorable for MH-IOCG formation.
The Role of Decreasing Geothermal
Gradients
Not all differences between MH-IOCG and
porphyry deposits can be explained on the basis
of sulfur content, including the full nature and
extent of high-temperature alteration in MH-
IOCG deposits, and their different minor-ele-
ment contents (e.g., U and REE). Given that
the source magmas and therefore initial fluid
temperatures for both deposit types are similar
(~700 °C), one explanation for these further dif-
ferences may be that ambient rock temperatures
in the upper crust were higher under steeper Pre-
cambrian geothermal gradients, due to higher
radiogenic heat output and higher primordial
heat loss (Araki et al., 2005). Some estimates
suggest that geothermal gradients were approxi-
mately twice current values at 2 Ga (Richter,
1988; Plant and Saunders, 1996), while Hand
et al. (1999) argued for highly variable paleo-
geotherms depending on the concentration of
radioactive elements (U, K, Th) in Proterozoic
rocks. They calculated that high-heat-produc-
ing granites such as those associated with the
Olympic Dam and Cloncurry mining districts
could have had geothermal gradients double the
0.0
Sulfate accumulation
Proterozoic average at the time of mineraliza-
tion (1.6 Ga).
Most MH-IOCG deposits are associated with
extensional environments, and many are close
to their source batholiths, which places them
in host rocks with significantly higher-than-
normal thermal gradients (e.g., Hitzman, 2000).
In contrast, most porphyry deposits are formed
at shallow levels (~1–5 km depth) above deeper
batholiths (~5–10 km), and thus in cooler coun-
try rocks. High ambient temperatures in the host
rocks to MH-IOCG deposits would facilitate the
formation of extensive zones of high-tempera-
ture alteration, from which a significant flux of
crustally derived lithophile elements such as Fe,
K, Ca, U, and REE could be derived.
Temporal Overlap between MH-IOCG and
Porphyry Deposits
This model does not preclude the formation
of rare porphyry deposits in the Precambrian
where magmatic sulfur contents were locally
high, for example due to subduction of oxidized
shallow-marine sediments. It also does not pre-
clude the formation of MH-IOCG deposits in
the Phanerozoic from S-poor magmas generated
from partial melting of relatively S-poor asthe-
nospheric or subduction-modified lithospheric
sources that may be linked to periods of deep
ocean anoxia, or in extensional zones with high
thermal gradients.
CONCLUSIONS
Porphyry Cu ± Mo ± Au and magmatic-
hydrothermal IOCG deposits share many attri-
butes, such as their association with calc-alkaline

GEOLOGY | July 2013 | www.gsapubs.org 769


to mildly alkaline magmas, broad geotectonic
relationships, and metal contents; and yet they
remain distinctive. The closest overlap between
these two deposit types is found in post-subduc-
tion alkalic porphyry Cu-Au deposits, which are
magnetite rich and relatively S poor. We pro-
pose that higher geothermal gradients and lower
seawater sulfate contents in the Precambrian
favored the formation of S-poor arc magmas and
MH-IOCG deposits during that period, whereas
the reverse was true in the Phanerozoic, favor-
ing S-rich porphyry formation. Exceptions exist,
however, and we explain the overlap by local
variations in geothermal gradients and source
sulfur contents.
ACKNOWLEDGMENTS
This paper is dedicated to the memory of Rob Ker-
rich, an innovative thinker and inspiring mentor. We
acknowledge the support of Discovery Grants from the
Natural Sciences and Engineering Research Council
of Canada, our industry collaborators, and discussions
with numerous colleagues that have challenged us to
try to make sense of the porphyry-IOCG conundrum.
We particularly thank Mark Barton, David Cooke, and
Adam Simon for perceptive and constructive reviews.
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Manuscript received 29 November 2012
Revised manuscript received 11 February 2013
Manuscript accepted 14 February 2013
Printed in USA
www.gsapubs.org | July 2013 | GEOLOGY