©2005 Society of Economic Geologists, Inc.

Economic Geology 100th Anniversary Volume

pp- 25-37

Magmatic Processes in the Development of Porphyry-Type Ore Systems

PHILIP A. CANDELAt AND PHILIP M. PICCOLI
Laboratory for Mineral Deposits Research, Department of Geology, University of Maryland, College Park, Maryland 20742

Abstract
The close spatial and temporal association between intermediate to felsic igneous intrusions and large ton-
nage, low-grade porphyry-type mineral deposits in arc environments is consistent with the hypothesis that mag-
mas were the dominant source of the ore metals. In this paper, we review some aspects of the origin and em-
placement of porphyry ore-related magmas, the controls on the magmatic concentration of ore metals, water,
chlorine, sulfur, and related elements, and the factors that affect the partitioning of metals in magmatic-hy-
drothermal systems.
The intermediate to felsic igneous rocks associated with ore are the end product of magmatic evolution that
begins with the generation of mantle-derived arc magmas. High-alumina basalt is generated by the complex in-
teraction of fluids released from subducting slabs oe the overlying mantle wedge. Fluids released early from
the slab may be higher in chlorine, as well as in related volatile and fluid-soluble elements. Fugacities of oxy-
gen and sulfurous gases in arc magma systems may be controlled in part by sulfate-oxide-sulfide assemblages
in the subducting plate. Water, chlorine, and sulfur may be sourced partially from seawater by way of sub-
ducted oceanic lithosphere. Ore metals in arc magmas probably have diverse origins, including the mantle
wedge, the lower continental crust, and the subducted lithosphere.
Dilational tectonic features may accommodate some high-level plutons, as well as their associated cupolas
and apophyses. The large-scale through-going fractures that host these local zones of dilation can extend to
lower crustal depths and thereby facilitate the movement of magma from depth. The structures that represent
zones of crustal weakness below the magma chamber and that promote magma ascent also provide regions of
weakness above the chamber and promote the formation of cupolas, apophyses, and zones of high vein den-
sity. During the growth of plutonic complexes, active magma chambers may be smaller than the developing
plutonic complex at any given time. Significant devolatilization may occur upon magma rise, with ore zones lo-
cated above the root-feeder zone of the chamber.
Volatile-melt-crystal interactions are important at all structural levels in the crust, and may be quite impor-
tant in controlling not only the water, sulfur, and chlorine concentrations but also the metal concentrations in
the epizonal magmas that generate porphyry ore deposits. Generally, the formation of magmatic-hydrothermal
deposits of chalcophile metals is favored by magmatic characteristics such as high Cl/H2O ratio, and early
volatile exsolution relative to crystallization progress. The oxidation state of the magma is probably important
in producing variations in ore-metal ratios in magmatic-hydrothermal ore deposits.

Introduction timing of crystallization, magma ascent, magmatic volatile-

PorpHyry and related deposits of copper, tungsten, tin, phase exsolution, magma-chamber geometry, local hydrologi-
molybdenum, gold, and silver are associated spatially and cal and rock mechanical properties, and the depth of magma
temporally with granitic (s.].) rocks (Seedorff et al., 2005). emplacement (see Cerny et al., 2005, for more discussion).
These igneous rocks are, generally, low- to high-K, metalumi- Some relatively shallow granitic bodies (i.e., those emplaced
nous to peraluminous arc magmas, and range from diorite to at depths of ca. 8 km or less) represent hie crystallized re-
true granite in composition. These associations lead to the hy- mains of magmas that were related to subvolcanic, ore-gener-
pothesis that intermediate to felsic magmas may be the ative, hydrothermal systems. Further, these shallow plutons
source for much or all of the ore material in granite-related can have associated volcanic rocks. Studies of the chemical
deposits. Indeed, many studies have shown that the chemical, and isotopic composition, texture, and field relations of these
isotopic, and thermodynamic characteristics of these “granite- igneous rocks can elucidate the processes that converge to
related” ores are consistent with this hypothesis and that or- generate porphyry, skarn, epithermal and related high-tem-
thomagmatic-hydrothermal processes have played a central perature veins, and massive sulfide deposits (Franklin et al.,
role in ore genesis. Therefore, it is reasonable to propose that 2005; Meinert et al., 2005; Seedorff et al., 2005; Simmons et
the genesis of magmatic-hydrothermal ore deposits, such as al., 2005).
the porphyry class of ores, is a by-product of the irreversible Over 65 percent of all copper mined comes from deposits
transfer of heat, by magma flow, from Earth’s interior toward associated with igneous rocks (i.e., porphyry, skarn, replace-
its surface. ment, and massive sulfide deposits), with just over half com-
Many factors affect magmatic-hydrothermal ore genesis, ing from porphyry-type ores (Singer, 1995). Singer also calcu-
including magma composition, magmatic oxidation and sulfi- lated that ~20 percent of mined gold comes from
dation state (for a discussion of the sulfidation state of por- igneous-related systems, and about one-third of igneous-re-
phyry and related ores, see Einaudi et al., 2003), the relative lated gold comes from epithermal deposits. Molybdenum is
more strongly associated with igneous rocks than is copper,
with over 99 percent of the world’s molybdenum coming from
! Corresponding author: e-mail, [email protected] porphyry-type deposits (Kirkham and Sinclair, 1996).

25
26 CANDELA AND PICCOLI

Porphyry deposits are the archetype of granite (s.1.)-related spot tholeiites such as Kilauea, United States (Johnson et al.,
deposits. They exhibit a strong spatial and temporal relation- 1994). Associated lavas can include the full range of the basalt-
ship between shallow, porphyritic or variably-textured inter- andesite-dacite-rhyolite compositional range. Questions arise
mediate to felsic igneous rocks, and usually steep-walled, as to the extent to which the more felsic components of the
crudely cylindrical to bell-shaped sulfide-rich orebodies (See- suite owe their origin to fractionation and/or contamination of
dorff et al., 2005). The high-level igneous stocks associated high-alumina basalt by, for example, assimilation-fractional
with porphyry and related deposits typically form the roof crystallization processes (DePaolo, 1981). Partial melting of a
zones of shallow plutons where vertically elongated, high-as- mixture of lower crust and previously crystallized basalt may
pect ratio cupolas (Sutherland-Brown, 1976) are the locus of yield granulite + dacitic magma, with the dacite fractionating
upward surges of magma and associated magmatic volatiles. or being contaminated by more primitive magmas to yield the
Porphyry copper ore occurs as disseminations or stockwork full range of arc magmas (Hildreth and Moorbath, 1988).
veins yielding grades of copper on the order of 0.4 to 1 wt Richards (2003) provides a detailed discussion of the
percent, with subordinate molybdenum and gold. Porphyry processes involved in arc magma genesis with specific refer-
molybdenum deposits have grades of a few tenths of a per- ence to the origin of porphyry-type deposits.
cent MoSzs, and porphyry gold deposits contain on the order Most models for the generation of arc basalts suggest that a
of 1 ppm gold. Characteristic alteration styles represent the mobile, high-temperature aqueous phase (>50 wt % water) is
combined effects of cooling of the aqueous ore-forming released from the subducting plate over a range of appropri-
phase and the mixing of magmatic and meteoric waters ate pressures and temperatures (Wyllie, 1979; Grove et al.,
(Hedenquist and Richards, 1998). 2002; see Fig. 1). According to this paradigm, the fluids or
In this paper, we describe some of the characteristics of fluid mixtures rise into the overlying asthenosphere by virtue
porphyry ore systems that yield critical information on the of their buoyancy, and react with and metasomatize the man-
formation and development of magmatic-hydrothermal ore tle, acting as a flux to cause melting of the wedge, thus gen-
deposits; we will not focus on issues that have been described erating a volcanic arc as its surface expression. The volcanic
elsewhere in the literature, and this volume, such as detailed arc forms on the surface between 90 and 150 km above the
descriptions of ore zones, alteration, or the mineralogy or pet- devolatilizing slab. The width of volcanic arcs is typically <100
rography of the associated igneous rocks. Rather, we focus the km (d’Ars et al., 1995). According to Grove et al. (2002), the
article around a series of relevant issues that arise naturally major elements in a slab-derived fluid are HzO (~55-68 wt
from the first-order observations of these deposits, including %), NagO (~25-33 wt %), and K2O (~5-13 wt %). Further-
the following: their occurrence in arc environments; their as- more, Grove et al. (2002) suggest that this composition may
sociation with shallow, generally porphyritic, oxidized, inter- represent a mixture of fluids (a higher density “melt’-like
mediate-to-felsic intrusions; the importance of cupolas and fluid and a lower density aqueous fluid) or a supercritical
related structures; the sulfur-rich nature of the ore; the dom- equivalent derived by dehydration of the descending and
inant role of fracturing in magma emplacement and ore lo- heating slab. Given the salinities suggested by Kent et al.
calization; the saline nature of the ore-forming fluids; and the (2002), this slab-derived fluid possesses Cl/H2O ratios on the
distinctive suite of elements commonly found in the deposits. same order as the salinity of seawater (1/50). Melting of the
asthenospheric mantle wedge probably involves the interac-
Subduction: Stoking the Magmatic Hearth tion of slab-derived fluid, depleted mantle, and possibly melt
Many hydrothermal ore deposits are associated closely with from subducted sediments (McDade et al., 2003). These
volcano-plutonic complexes in present-day convergent plate components combine to produce a modified wedge peridotite
margins or their older equivalents. Given the close relation- that can melt to yield mafic are magma. In summary, complex,
ship between magmatism and subduction in arc systems, we alkali- and chloride-bearing fluids with a significant silicate
examine the varying roles that subduction may play in ore component are released over a rather wide interval from the
genesis. Subduction is a flux of serpentinized mantle, altered subducting plate, acting as a flux to cause melting of the man-
basalt and gabbro, ocean water, and sediment into the man- tle wedge, and yielding arc basalt.
tle. A portion of this mantle-directed flux, in the form of
buoyant, slab-derived fluid, is released into the overlying Whence the Ore Substance?
mantle wedge where hydrous arc magmas are subsequently Ore substance is used here in a broad sense to mean ore
formed. metals, ligands, and other components that either constitute
Here we will explore selected issues related to magmas and the target ore-metal anomaly or are ultimately responsible for
subduction, in order to elucidate how subduction affects ore delivering these constituents via an aqueous solution to the
genesis. Previous reviews on this subject include Sillitoe mineralized volume of rock. The magmatic inventory of ore
(1972, 1987) and Richards (2003). As a first step, we discuss metals and ligands may have widely diverse origins. Because
the generation of are magmas. High-alumina basalt, charac- the inventory of any given element in any igneous rock mass
terized by AlsO3 concentrations greater than 16 wt percent, is might come, in part, from the asthenospheric or lithospheric
the preferred parent of are magma systems (e.g., Berndt et mantle, the lower or upper crust, or a subducted plate, ore
al., 2005). Basaltic magmas begin crystallizing Fe-Ti oxides substances can also be expected to originate from a mixed
early at high water contents and high oxygen fugacities parentage. A wide variety of isotopic and trace- and major-
(Berndt et al., 2005). Arc magmas contain up to 6 wt percent element data suggest that both the slab and the mantle wedge
HO, compared to generally <0.4 wt percent H2O for mid- contribute materially to primary arc magmas, and therefore
ocean-ridge basalts (MORB) and <1.0 wt percent H20 for hot ore metals can be expected to come from both sources (Noll
 MAGMATIC PROCESSES IN THE DEVELOPMENT OF PORPHYRY-TYPE ORE SYSTEMS bo~l

A)

| Young, warm
lithosphere

Streamlines of
Asthenosphere mantle flow

serpentine + brucite

B)

| Old, cold
lithosphere

serpentine + brucite
Streamlines of
Asthenosphere mantle flow

metasediments
+ metabasalt
+ metaperidotite

Fic. 1. Possible scenarios for the subduction of young, warm lithosphere (A), and old, cold lithosphere (B) (after Leeman
et al., 1994). Volatiles are released over a range of temperatures. Cooler fluids result in serpentinization of the mantle wedge.
The magmatic front lies 124 + 38 km above the inclined seismic zone, and this relationship does not vary systematically with
any subduction variable, such as convergent rate, or age of lithosphere being subducted (Stem, 2002). See text for details.

et al., 1996; McInnes et al., 1999). Furthermore, the lower ocean crust. A significant proportion of sheared and perme-
crust can also be an important reservoir for the constituents able ultramafic rocks is also present (Stern, 2002). During al-
of arc magmas, especially in continental settings (Hildreth teration, water, chlorine, sulfur, and boron from seawater are
and Moorbath, 1988; Barra et al., 2002). Ore substance can added (in addition to sodium and potassium at the expense of
come from any of these sources, and it is probably best to magnesium and calcium) to the oceanic crust (Noll et al.,
think of the ore metal inventory of magma as derived from 1996). Copper, lead, zinc, manganese, cobalt, arsenic, anti-
some mixture of these deeper reservoirs. mony, thallium, selenium, tellurium, cadmium, gold, silver,
The slab reservoir comprises the subducting oceanic lithos- mercury, and bismuth are among the ore elements of interest
phere. Hydrothermal alteration on the sea floor before sub- that are probably redistributed by hydrothermal processes,
duction alters the composition of oceanic crust, changing its with many of these elements ultimately residing in sulfides in
oxidation state, and adding sulfur and other elements. Philip- the upper levels of the altered oceanic crust. This complex
pot et al. (1998) suggested that sea-floor alteration by ocean package of altered ocean lithosphere forms the raw material
water is water-dominated at the shallow levels in the oceanic for the reactions that later occur in subduction zones.
crust that comprise relatively permeable basalt and sheeted
dikes, and is rock-dominated at deeper structural levels that Chlorine
comprise gabbro. Kerrick and Connolly (2001) also point out Chlorine is stored in the oceanic crust in silicates, apatite,
that alteration is most intense in the upper kilometer of the chlorides, and as pore and inclusion fluids. Although fluid
28 CANDELA AND PICCOLI

inclusions in eclogites can be quite saline, indicating that granodiorite of ~400 ppm, and ~50 ppm in the Johnson Gran-
chlorine can be carried to great depths in subduction zones ite Porphyry. The inferred initial chlorine concentration of
(Kent et al., 2002), one might hypothesize that early fluids re- the magmas correlates inversely with initial whole-rock
leased from the down-going slab are enriched in chlorine rel- 5$r/Sr. This result is consistent with the hypothesis that
ative to later subduction-derived fluids. To examine this pos- chlorine was added to the crust via arc magmas, ultimately
sibility, Walker et al. (2003) analyzed olivine-hosted melt from a subcrustal fluid component derived from a subducted
inclusions in voleanic rocks from across the width of the Cen- slab. This study is consistent with the hypothesis that chlo-
tral American volcanic arc. We have calculated Cl/H2O ratios rine, an important complexing agent for many metals includ-
from their data, and plotted the results versus distance be- ing copper and gold, may attain higher concentrations in
hind the volcanic front (Fig. 2). These data suggest that the magmas that have higher ratios of subcrustal versus continen- _
Cl/HsO ratio decreases with distance behind the volcanic tal crustal components.
front, from 0.1 within 20 km of the front to 0.025 at 80 km be- Taken together, these studies suggest that chlorine is con-
hind the front. Kent et al. (2002) demonstrated that the tributed significantly from subcontinental sources, and that
Cl/H20 ratio can be relatively high in primitive back-arc basin the Cl/H20 ratio is a complex function of seawater composi-
basalts that are erupted proximal to the arc front, with the tion, sea-floor alteration, and dewatering of the subducting
ratio decreasing rapidly with increasing distance from the are oceanic lithosphere, as well as interactions that occur in the
front. For basalts of the Lau basin, Scotia Sea, and Mariana lower crust.
Trough, Kent et al. (2002) reported Cl/H2O mass ratios that
vary from 0.12 less than 200 km from the arc front, to values Pathfinder elements
near 0.01 at locations in excess of 400 km from the arc front. Elements such as boron, lead, arsenic, and antimony, as
These values span the range of Cl/HsO ratios commonly re- well as strontium, the large ion lithophiles, and other ele-
ported for arc magmas (Candela and Piccoli, 1995). Kent et ments, appear to be mobilized efficiently from the slab. Vol-
al. (2002) also concluded that the slab fluid component has a canic arc basalts are enriched in boron, and their B/Zr ratios
higher Cl/H20 ratio than that expected from simple melting are generally 10 to 100 times higher than in intraplate basalts
of MORB-like mantle sources. Sisson and Bronto (1998) re- (Leeman and Carr, 1995), which can be attributed to addition
port Cl/H20 as high as 0.3 in undegassed frontal arc basalts of boron to arc magma source regions by slab-derived fluids.
from Galunggung, Indonesia, supporting the notion that chlo- In an analysis of representative transitional tholeiitic to cale-
rine is distilled early from the subducting slab. alkaline lavas from seven different arcs, including rocks rang-
Piccoli and Candela (1994) estimated model liquidus chlo- ing from subalkalic basalts to dacites, Noll et al. (1996) pre-
rine concentrations for the idealized magma for each unit of sented data consistent with the efficient mobilization of lead,
the zoned Tuolumne Intrusive Suite of the Sierra Nevada arsenic, antimony, and possibly thallium into are magma
batholith, United States. The granitic rocks of this suite range source regions by hydrothermal transport from the slab,
from the granodiorite-diorite of Kuna Crest (~59 wt % SiOz) based on the similarity of their behavior to boron. Conversely,
to the Johnson Granite (s.s.) Porphyry (~74 wt % SiOz) (Bate- tin, molybdenum, and tungsten show little such co-enrich-
man et al., 1983). The more melanocratic units, which also ment. As evidence that slab-derived fluid mobility, rather
have lower bulk-rock SiOz concentrations, have higher model than crystal fractionation or a related process, is responsible
initial chlorine concentrations, with values in the Kuna Crest for the zonation of the volatile elements they observed, Noll
et al. (1996) pointed out that arsenic, antimony, lead, and
0.18
boron concentrations decrease dramatically relative to the
light rare earth elements (LREE) with distance from the vol-
0.16 4 canic front toward the back-arc basin in Japan and the
0.14 4 Kuriles, mirroring the behavior of chlorine. They explained
the decrease in these elements across the arc by the decreas-
0.12 4 ing fluid flux as the slab progressively dewaters with depth,
0.10 4 converting to eclogite, and creating compositional gradients
in the mantle wedge related to early distillation of more fluid-
0.08 4
compatible components such as arsenic and antimony, which
(wt.%)
CI/H200.06 | ° then reside in the wedge (for a discussion, see Hattori and
0.04 + ~
Guillot, 2003). Because bismuth tends to follow antimony, at
least in near-surface hydrothermal settings, bismuth may also
0.02 | ¢ follow this trend. Hattori et al. (2002) summarized studies
0.00 suggesting that the relative preferential removal of the
0 20 40 60 80 chalcogen elements from the mantle follows the sequence, S
> Se > Te. Hattori et al. concluded that partial melting can re-
Distance Behind the Volcanic Front (in km) sult in the fractionation of sulfur, selenium, and tellurium in
the mantle and in progressively derived arc magmas. These
Fic. 2. Plot of Cl/H2O (wt % basis) in melt inclusions across the Central
American subduction zone in Guatemala. Data are from table 1 of Walker et
considerations have implications for the modification of ele-
al. (2003). Values are averages of the melt inclusion populations analyzed at mental ratios in ore magmas as a function of the amount of
each distance behind the volcanic front (measured orthogonal to the front). slab devolatilization that occurs prior to fluxing of melting in
The error bar represents the lo standard deviation of the mean. the hotter parts of the mantle. Clearly, devolatilization occurs
 MAGMATIC PROCESSES IN THE DEVELOPMENT OF PORPHYRY-TYPE ORE SYSTEMS 29

over a range of depths (see fig. 4 of Hattori and Guillot, on isotopes of minerals in the Bagdad porphyry Cu-Mo de-
2003), and beneath mantle of various temperatures. If a sig- posit, United States. Barra et al. (2002) examined the iso-
nificant amount of devolatilization occurs from a hot plate be- topic composition of rhenium and osmium in sulfide miner-
neath cold mantle, the more volatile elements, including ar- als using osmium as a tracer for the source of ore metals in
senic and antimony, may be added to cooler mantle by the ore system. Molybdenite, chalcopyrite, and pyrite from
Rayleigh distillation from the slab, and may not be directly in- potassically altered quartz monzonite and porphyritic quartz
volved in magma generation (Leeman, 2001). The extent to monzonite were analyzed. Their results suggest that a sig-
which sediments participate in devolatilization at the depths nificant portion of the metals and magmas have a crustal
appropriate for arc magma generation may also be a major source, as has been suggested for other copper deposits and
factor in determining the volatile element inventory of an arc districts in Arizona. These two studies suggest that metals
magma system (Rupke et al., 2002). Arsenic concentrations and other elements in porphyry deposits may have diverse
can command penalties in ore concentrates from porphyry origins, with crustal sources perhaps important in the
copper deposits. Are porphyry copper deposits related to smaller deposits. However, it should be noted that it is diffi-
magmas formed from early slab fluid release higher in arsenic cult to infer confidently the origin of ore metals based on
than deposits related to magmas that formed from later slab- the behavior of isotopes of another element.
derived fluids? Tin, molybdenum, and tungsten behave more like titanium,
Of course, other variables can come into play. Boron can be niobium, and tantalum in their arc systematics, suggesting
stored in the lower crust or the mantle wedge as tourmaline, they are associated with dominantly crust derived igneous
and may be mobilized during later events. Also, boron can be rocks. The ratio of these lithophile elements to the more
mobilized by the melting of sediments in the crust, unrelated volatile chlorine, boron, arsenic, antimony and bismuth, etc.,
to position in the arc. Bismuth and sulfur may be stored in the and by extension, to the chloride-complexed metals such as
lower crust or the mantle wedge, whereas chlorine may have copper, may be determined in part by the relative importance
a much lower residence time in the lower crust. Elements of subduction fluids in the generation of the host magmas.
stored in the mantle wedge may be taken to greater depths, However, higher slab contributions to ore-generative magmas
being released later to feed magmatism that is realized land- may be indicated by higher concentrations of boron, arsenic,
ward toward the cratonic margins (Thompson et al., 1999). bismuth, and antimony in granites and their associated ores.
Indeed, Hattori and Guillot (2003) suggest that the break- If chlorine correlates with these elements, then we might also
down of serpentinites, which can act as a sink for water and expect higher concentrations of Cl-complexed metals such as
fluid-soluble elements released from the underlying slab in copper. Generally, however, metals and source regions are
the mantle wedge, can lead to arc magmatism at volcanic probably not limiting factors in the development of porphyry-
fronts. The downward movement of the serpentinite layer by type ores.
mantle flow transports these fluid-soluble elements to
deeper, hotter levels in the mantle. Sulfur (and magma oxidation state)
Sulfur in naturally occurring silicate melts can exist as both
Metals reduced (sulfide) and oxidized (sulfate) species. Carroll and
Isotopic and melt inclusion studies suggest that ore met- Rutherford (1988) showed that the sulfate/sulfide ratio in sil-
als in porphyry copper systems are sourced from a number icate melts generally increases with increasing temperature,
of different reservoirs. Based on melt inclusion data from pressure, and oxygen fugacity. Sulfur concentrations are
voleanic rocks from Galunggung volcano, Indonesia, de lower in melts in lower fo, systems saturated with sulfides
Hoog et al. (2001) suggested that arc magmas are slightly (e.g., pyrrhotite at fo, values less than two orders of magni-
enriched in copper relative to MORB, perhaps due to the tude above the quartz-fayalite-magnetite buffer, referred to
enrichment of the subarec mantle by slab-derived copper. as <QFM + 2), compared to higher fo, systems where sulfate
They also inferred that the primary Galunggung melts:con- minerals are stable (Jugo et al., 2005). Further, the volatile-
tained on the order of 290 ppm Ni, 60 ppm Co, 190 ppm magma partitioning of sulfur will be enhanced at higher oxy-
Cu, and 3 ppm Pb. Lead could have been added by the slab- gen fugacity for pyrrhotite-saturated magma (Candela and
derived fluids, whereas cobalt and nickel concentrations Blevin, 1995a). De Hoog et al. (2001) studied mafic melt in-
were largely controlled by the pre-subduction mantle. How- clusions (with sulfur contents in the range 350-2,900 ppm)
ever, it is not at all clear that these processes are significant hosted in olivine in high-Mg basalts of the Galunggung vol-
in affecting ore genesis in arcs. Isotopic data from E] Te- cano, Java, Indonesia. The authors showed that the sulfur iso-
niente, located in the central Chilean Andes and the world’s tope compositions are consistent with a slab-derived origin,
largest porphyry copper deposit, tell a different story. There, and proposed that the mantle beneath Galunggung is signifi-
mineralization occurs with magmatic-hydrothermal biotite, cantly enriched in sulfur relative to the MORB source man-
anhydrite, and tourmaline breccias hosted in Miocene mafic tle. de Hoog et al. suggested that large-scale transfer of sulfur
intrusive rocks. Skewes et al. (2002) presented lead and os- into the mantle wedge occurred during slab dehydration, and
mium isotopic data and suggested copper was derived from that the sulfur isotopic data are consistent with a slab-derived
mantle-derived magmas such as tholeiitic and calc-alkaline origin. In addition, Sasaki and Ishihara (1979) suggested that
basalts and basaltic andesites. According to their model, the enrichment of isotopically heavy sulfur in hydrous magmas in
development of ore at El Teniente involved volatile-rich are settings is common, and also concluded that seawater-de-
mantle-derived mafic magmas mixing within an open-sys- rived sulfur was added to the arc magma system via the sub-
tem magma chamber. A different story is suggested based ducted oceanic lithosphere.
 CANDELA AND PICCOLI

.u our view, the high oxygen fugacity of the oceanic lithos- from a basaltic magma into juxtaposed felsic magma is possi-
phere is transmitted to the mantle wedge by the hydrogen ble, but complex lower crustal interactions are probably in-
and sulfur species in the slab-derived fluids. The higher oxy- volved in the mixing of chlorine into felsic magmas from sub-
gen fugacity of the subducted crust relative to pristine MORB crustal sources. Sulfur is more easily stored in the lower crust
(oxygen fugacity ~ QFM) results from the prior interaction of than is chlorine, and is thus more likely to be added to the
oceanic lithosphere with seawater. As the down-going slab re- subare lithosphere and possibly brought up to more shallow
leases fluid in a subduction zone, the ratios of SOs/H2S and levels in gas bubbles contained within the magma (Varekamp
H2O/Hz will reflect the range of oxygen fugacities present in et al., 1984: Lowenstern, 2001).
the dehydrating slab. These slab-derived fluids will interact
with, and will almost certainly oxidize the overlying mantle Questions Regarding the Special Role of
wedge, with the fluid becoming reduced in the process. De- Mafic Magmas in the Upper Crust
tails of these interactions determine the ultimate range of ox- The role of upper crustal mafic magmas in magmatic hy-
idation states of arc magmas. The subducting oceanic lithos- drothermal ore genesis has been debated in the recent litera-
phere will not have a unique oxygen fugacity at any given ture (e.g., Hattori and Keith, 2001). Certainly, mafic magmas
temperature and pressure, since the slab is a mosaic of rock in arc environments are mantle derived, and can contribute
types and compositions generated, in part, from variable de- heat and matter to magmatic-hydrothermal ore systems. Fur-
grees of alteration. The proportion of subducted basalt and thermore, mafic magmas represent the primitive arc magma,
peridotite altered at higher sea water/rock ratios (and there- and are clearly important in generating more felsic arc mag-
fore producing more oxidized alteration products) will deter- mas associated with porphyry-type deposits. If it is agreed
mine the aggregate oxygen fugacity of the fluid(s) released that these mafic magmas are in part the source of elevated
from the slab. chlorine and sulfur in more evolved magmas, then the only
If the evolving, slab-derived fluids derived from different question is where and when are mantle-derived mafic mag-
regions within the devolatilizing slab do mix and react upon mas involved in the parentage of ore-generative arc magmas.
dehydration, and approach some equilibrium within altered Exactly how mafic, mantle-derived components mix with
oceanic crust at any given temperature and pressure, equilib- crust-derived components to form hybrid magmas that crys-
rium may be approximated by assemblages such as quartz + tallize to yield upper crustal plutons is far from clear. Hildreth
hedenbergitic pyroxene + anhydrite + magnetite + pyrrhotite, and Moorbath (1988) proposed in their MASH (melting, as-
which can buffer the fugacities of oxygen and sulfur at any similation, storage, and homogenization) hypothesis that pro-
given pressure, temperature, and pyroxene composition. gressive gabbroic diking in the deep crust, overlapping in
Ludden et al. (1999) have shown that even the oldest oceanic space and time, is in part responsible for the variable compo-
crust contains intervals of minimally altered basalt, so the sitions that we commonly refer to as “mixed magmas”: The
ratio of oxidized to reduced rocks is likely to be related to fac- production of zoned intrusions, as well as the progression of
tors such as the gross fracture permeability of ocean floor that magmas in volcano-plutonic systems, may be controlled by
is subsequently subducted. The oxygen fugacity of the upper the deep crustal diking of mantle-derived gabbroic magma
mantle varies by several orders of magnitude (de Hoog et al., into lower crustal mafic to intermediate rocks. Richards
2004), and the titration of slab-derived fluid into the mantle (2003) expressed similar ideas in his recent review of the ori-
wedge probably increases both the oxygen and sulfur fugaci- gin of porphyry-related arc magmas.
ties of the subare mantle. Blatter and Carmichael (1998) Klepeis et al. (2003) studied exposures of early Mesozoic
showed that some oxidized, subarc mantle peridotites can arc crust in western New Zealand to elucidate magma gener-
have oxygen fugacities as high as QFM + 2.4. Jugo et al. ation and transport processes. The rocks include migmatites,
(2005) suggest that sulfides will not be stable in these more granulite-facies mineral assemblages, and layered mafic-in-
highly oxidized subare mantle regions; therefore, chalcophile termediate intrusions that formed in the lower and middle
metals such as gold and copper may not be retained in the crust of the arc at paleodepths of 25 to 50 km during the Early
crystalline residue in the arc magma source, yielding melts Cretaceous. Klepeis et al. (2003) suggested that the lower
with higher concentrations of chalcophile ore metals. crust had accumulated at least a 10-km thickness of mafic-in-
In summary, water, sulfur, carbon, and chlorine are impor- termediate magma. The first phases were dominantly gab-
tant constituents of the slab-derived fluid. Other elements, broic whereas later phases were dominantly diorite (now the
especially the pathfinder elements boron, bismuth, arsenic, Western Fiordland Orthogneiss). These magmas have been
and antimony, as well as some ore metals, also appear to be interpreted to have added sufficient heat to the lower crust to
contributed to the site of melt generation by fluids derived partially melt the vertically stratified mafic-intermediate host
from subducted oceanic lithosphere. Because of its interac- gneisses, themselves the product of similar but earlier events.
tion with ocean water, the oxygen fugacity of the slab will be Compositions of the earlier melts were granitic due to biotite
elevated compared to the initial oxidation state of pristine dehydration melting (for a discussion of the timing of biotite
MORB. However, as has been stated before (e.g., Candela dehydration melting, see Bingen and Stein, 2003), but be-
and Blevin, 1995a; Richards, 2003), discussions of the came granodioritic to tonalitic with increasing temperature as
“source” of ore metals are fraught with difficulty. Copper, the main reaction shifted to the fluid-absent melting of horn-
gold, and other ore metals can all be supplied by the sub- blende + clinozoisite. Clearly, the mixing of rocks of diverse
ducting plate, by the mantle wedge, or by the lower crust. Ore origins by diking of mantle-derived magma for long periods
metals may be stored in lower crustal mafic rocks, to be could yield fertile source rocks for the extraction of “hybrid”
tapped during later orogenic events. Chlorine partitioning melts (Hildreth and Moorbath, 1988).
 MAGMATIC PROCESSES IN THE DEVELOPMENT OF PORPHYRY-TYPE ORE SYSTEMS 3]

Forging the Magmatic Hearth: rapid oblique convergence and shallow eastward subduction
The Localization of Upper Crustal Magmatism of oceanic lithosphere under the North American plate. In
the Tertiary of North America, the Laramide was quite pro-
Broadly, M- (mantle source) and I-type (lower crust-upper ductive in generating porphyry, skarn, and associated hy-
mantle igneous source) magmas are associated with conti- drothermal deposits.
nental margins, and are characteristic of arc systems. How- At Escondida, Chile, pluton emplacement was localized
ever, the distribution of magmatism in ares is complex and is within a broad zone formed by the intersection between the
controlled by many factors. Plutonism and volcanism in are West Fissure zone and a regionally extensive northwest-trend-
terranes are episodic, and appear to be related to periods of ing structural corridor (the Archibarca lineament; Richards et
crustal deformation (Barton et al., 1988; Richards, 2003). al., 2001). These authors suggested that this structural geom-
Furthermore, in his study of granitic rocks in the western etry was conducive to the formation of transtensional pull-
United States, Glazner (1991) suggested that the obliquity of apart structures during relaxation or reversal of dextral shear
subduction affects the ratio of plutonism to volcanism at any on the West Fissure zone. The dilational structures focused
given time. Obliquity can generate strike-slip motion that, to- both the ascent and the emplacement of magma in the upper
gether with existing faults that are oriented at high angles to crust and maximized the potential for formation of magmatic-
the subduction zone, can result in local zones of extension in hydrothermal ore deposits. These histories exemplify the role
compressional settings. The resultant dilational features can played by local, dilational structures in otherwise compressive
accommodate shallow-level plutons, cupolas, and apophyses. settings, and by preexisting structures in localizing the mag-
The large-scale through-going fractures that host these local matism that focuses high-temperature magmatic hydrother-
zones of dilation can extend to lower crustal depths and mal mineralization.
thereby facilitate the ascent of deep magma. These studies suggest that some of the magmatism in
Many studies have demonstrated the importance of these Earth’s upper crust, as well as associated ores, is associated
structures in creating space for ore-generative magmas. For with large, through-going fracture systems that are controlled
example, according to Hill et al. (2002), from which the fol- by cumulative tectonic history. However, some authors (e.g.,
lowing account is taken, the Grasberg porphyry copper-gold Paterson and Schmidt, 1999) have noted that many granitic
deposit, Irian Jaya, is localized in the hanging wall of a large- plutons have no apparent relationship to specific structures.
scale (~10 km) basement-involved thrust fault. The New In part, this may be a matter of perspective. The small
Guinea margin of the Indo-Australian plate underwent rifting apophyses and cupolas, commonly localized by fracture sys-
oblique to the structural fabric in the crust, which resulted in tems and associated with magmatic hydrothermal ores de-
extensional faulting in the Jurassic. Extension was followed in posits, may occur in the roof zone of a large*r underlying plu-
the Oligocene by the collision of the Philippine-Caroline arc ton. When exposed at a somewhat deeper level, these larger,
with New Guinea. Toward the end of the middle Miocene, horizontally oriented, tabular- or funnel-shaped igneous bod-
compression was initiated in New Guinea. Few magmas were ies may show no clear evidence of structural control. Indeed,
emplaced except in areas oflocal dilation. As deformation mi- root zones and cupolas may be controlled by local, vertically
grated to the south, it reactivated preexisting extensional oriented dilational structures that form by a variety of mech-
faults. Local dilation occurred at the intersection of these anisms, including extension associated with dilational jogs in
faults with north-northeast-trending fracture zones, allowing compressional settings, whereas the larger flat-lying magma
emplacement of ore-generative magmas from the mantle or chambers couldgrow laterally by chamber-floor depression
lower crust. and roof lifting (Tosdal and Richards, 2001).
Basement-involved faults have also been postulated to exist
in the Ok Tedi district and at Porgera. The Porgera gold de- The Chamber Hearth: Magma Chambers and
posit is spatially associated with the regional-scale Porgera the Localization of Associated Mineralization
transfer structure (Corbett and Leach, 1998), which is a Magmatic-hydrothermal ores, as well as their associated ig-
through-going, arc-normal wrench fault that spans most of neous rocks, are the result of time-integrated processes (See-
Papua New Guinea. Hill et al. (2002) suggested that transfer dorff et al., 2005). Upper crustal magma chambers are open
structures may localize mineralization by providing magma systems, gaining magma from below, and losing magma to
and/or ore fluid conduits for magma-ore fluid ascent, partic- diking and volcanism. Ponding of the increasingly viscous
ularly at intersections with oblique structures. magma may be aided by tectonic factors. Magmas may be
In central British Columbia, Late Cretaceous to Eocene emplaced either in concentric fashion or adjacent to previous
granitic plutons and associated porphyry copper deposits intrusions (Vigneresse and Bouchez, 1997; Seedorff et al.,
occur in a broad northeast-trending belt. Babine Lake, Canada, 2005). Whether a magma-hydrothermal system is produced
is a porphyry copper district near the northeast terminus of as a result of a single pulse or multiple pulses of magma, and
the belt, and mineralization is associated with high-level whether the multiple pulses of magma produce a single plu-
biotite-feldspar porphyry. The andesites of the Newman vol- ton or multiple intrusive phases will be a complex function of
canic rocks are the extrusive equivalents of these intrusions. the rate of magma generation, upper crustal strain rate, and
In the Babine district, localization of magmatic and hydro- the time-integrated physical properties of the magma (Han-
thermal activity as well as porphyry copper ores was con- son and Glazner, 1985). Plutons are the product of crystal-
trolled by zones of extension (pull-apart basins) between dex- lization within a magma chamber over time, but plutons
tral strike-slip faults (MacIntyre and Villeneuve, 2000). These should not be equated with frozen magma chambers. The
authors point out that Laramide magmatism is attributed to volume of magma at any time is almost certainly less than the
3) CANDELA AND PICCOLI

volume of the existing pluton, and there are still outstand- The magmatic system may be saturated with one volatile
ing questions concerning how upper crustal magma cham- phase, or two volatile phases (i.e., vapor and brine). Models of
bers grow, and how chamber evolution is related to the gen- magmatic volatile phase exsolution from the melt are cen-
erally episodic nature of magmatic hydrothermal ore tered on the percolation of the volatile phase or phases
formation. Consequently, the geometry of volatile egress in through pore space in shallow intrusions, and convection of
relation to the present-day geometry of a given pluton may bubble-laden foam. Candela (1991) and Candela and Blevin
not be clear. (1995b) suggested that plumes of bubble-laden magma
The ascending magma in a developing and growing cham- and/or volatile phase permeability through interconnected
ber may undergo volatile exsolution and crystallization that volumes of the magmatic volatile phase act to transport
yields variably ctextured porphyritic stocks (Candela and volatiles toward the top of a chamber. As an alternative to the
Blevin, 1995b). The structures that represent zones of crustal model of Candela (1991), Shinohara et al. (1995) suggested
weakness below the magma chamber and that promote that bubble-rich magma undergoes open-system degassing at
magma ascent can also provide regions of weakness above the shallow depths by convective transport of bubble-rich magma
chamber and promote the formation of cupolas or other to upper regions where it loses volatiles, then sinks back into
apophyses. As a result, these structures can lead to the devel- the chamber.
opment of high densities of hydrothermal veins (Seedorff et Melt inclusions from the Bishop Tuff exhibit a range of
al., 2005). H2O and COs: concentrations in the glass that correlate with
As a magma chamber grows by any process, new magma trace-element concentration gradients, as well as calculated
input at the bottom of the chamber may rise through the ex- Fe-Ti oxide temperatures, inferred to reflect depth in the
isting magma if a significant bubble fraction is present. The magma column (Wallace et al., 1999; Anderson et al., 2000).
probability of a high bubble fraction in the melt entering the These data suggest the formation of a stagnant evolved cap of
chamber is favored by low total (lithostatic) pressures in the differentiated magma in the upper reaches of the magma
chamber (i.e., proximity to the surface), high volatile concen- body. Some plumes might rise into the upper level of the
trations, high ratios of (COzg + SOz)/H20, and crystallization chamber, but the cap is clearly not well mixed, as one might
of the input magma. Magma may reach a growing, upper level expect if vigorous convection occurred (T. Sisson, pers. com-
magma chamber already saturated with respect to an H20- mun, 2005).
COz-H2S-SOsz volatile phase (Lowenstern, 2001). In this case, We suggest that buoyant, volatile phase-saturated and bub-
the entering magma may devolatilize over the root zone (e.g., ble-bearing magma may ascend into a magma chamber, then
Roy and Clowes, 2000) of a growing chamber. With decreas- subsequently rise to the top of the chamber where it can de-
ing pressure and increasing crystallization progress in the host volatilize. As the chamber grows, the partially devolatilized
magma, the exsolving volatile phase may become progres- magma may move laterally, and more volatile-charged magma
sively richer in water as less soluble carbonic and sulfurous may be brought into the chamber from below. Alternatively,
components are preferentially removed in the earlier fluids periods of crystallization and devolatilization in a stratified
(Lowenstern, 2001). magma, accompanied by permeable flow of the magmatic
Candela and Blevin (1995a) pointed out that plutons with volatile phase and formation of a highly crystalline mush, may
any composition can occur without associated mineralization be punctuated periodically by the incremental addition of
or alteration, suggesting that physical magmatic parameters magma during tectonic dilation. This process may continue
are impcrtant in determining whether or not the end stages over a protracted period of time. This model obviates the
of magma evolution will include the generation of associated need to propose that large volumes of magmatic volatiles be
hydrothermal mineral deposits. There have been few models scavenged from a large magma chamber and focused into a
of magmatic volatile phase egress from magmatic systems. By small apical region. The cupola would sit over the root zone
magmatic volatile phase, we mean the water and/or salt-rich of the chamber, with the root and the cupola-apophyses oc-
phases in, or issuing from, the magma, and that may variably cupying the same structural weakness (Fig. 3). This model
be defined as vapor, brine, or supercritical gas. We define would produce a horizontally elongated pluton, with distal
these phases in the following way. A supercritical gas (a gas is portions of the pluton forming largely from the partly de-
a state of matter that fills its container, and therefore all su- gassed magma. This model is consistent with the structures,
percritical fluids are gases) is such that changes in composi- determined by geophysical methods, for the Guichon Creek
tion alone will yield neither condensation (formation of a batholith, Canada (Roy and Clowes, 2000).
high-salinity brine) nor vaporization (formation of a low-salin-
ity vapor). In other words, there is no dew point or bubble Granite textures in the porphyry ore environment
point at the temperature and pressure of interest. Here, we Many of the igneous rocks associated with magmatic hy-
define vapor as a low-density gas that can be brought to its drothermal ores are porphyritic in character. However, the
dew point by changes in composition alone, at the tempera- study of granitic textures, especially of those rocks associated
ture and pressure of interest, and we define brine as a salt- with ores, is problematic. A comparison of the textures found
rich aqueous liquid that can be brought to its bubble point by in pristine felsic volcanic rocks and in typical granitic-gran-
changes in composition alone, at the temperature and pres- odioritic rocks of closely similar composition reveals some
sure of interest. However, the reader should note that, be- similarities, yet some important differences as well. Early
cause we are attempting to categorize elements of a contin- formed, calcium-rich minerals in volcanic and plutonic rocks
uum, definitions of phases near critical points are commonly tend to exhibit shared textural elements. Zoning and euhe-
less than satisfying. dral crystal morphology in plagioclase and titanite are good
 MAGMATIC PROCESSES IN THE DEVELOPMENT OF PORPHYRY-TYPE ORE SYSTEMS 33

Ore body

ly
evolatilization

Propagating
crack

Feeder dike
B) Mineralized

Oui Variably Textured and

Sometimes Miarolitic
Granite

Fic. 3. One possible scenario for the growth of amagma chamber, showing (A) devolatilization focused above the feeder
of the growing chamber. In this hypothesis, magma rises from the lower crust by fracture flow. Volatiles partially exsolve upon
ascent and accumulate near the top of the chamber by plume or bubble rise, or by flow in permeable channels (Candela,
1991). (B) Magma spreads laterally into the growing chamber, creating space for new batches of magma. (C) Successive
batches of volatile-charged magma form a composite cupola, each batch representing bubble-laden froth related to cham-
ber-recharge events.

examples. Apatite in both volcanic and plutonic rocks can than feldspar, explaining the existence of quartz eyes in mod-
have a similar range of morphologies, with some crystals erately super cooled granite dikes. This may also be a factor
equant and others acicular. On the other hand, plutonic alkali in the case of granitic rocks associated with hydrothermal ore
feldspar and magnetite both exhibit compositions that deviate deposits.
significantly from their volcanic counterparts, owing to the An important distinction must be made between isobaric
fact that these minerals reequilibrate and react with alteration devolatilization (i.e., crystallization-driven devolatilization at a
(Piccoli et al., 2000). Quartz in typical hypidiomorphic granu- static level in the crust) which can be a near-equilibrium
lar granite is anhedral and interstitial, whereas in volcanic process, and devolatilization due to depressurization, which
rocks and some hypabyssal porphyries, it is commonly phe- commonly occurs under moderately to strongly irreversible
nocrystic. In fact, many of the shallow-level porphyries asso- conditions. Most likely, the porphyritic texture of ore-related
ciated with magmatic hydrothermal ores are called “quartz plutons is due to the latter, and is therefore probably indica-
porphyries.” Usually, these rocks have phenocryst assem- tive of decompression of a partially crystallized magma, De-
blages comprising quartz, feldspars, and other minerals; the compression may occur due to an upward surge of magma
quartz phenocrysts remain prominent even after extensive al- into a cupola or dike, or may be due to the lowering of the
teration. However, locally quartz may form more rapidly than magma chamber pressure from lithostatic to a lower pressure
feldspar phenocrysts, in magmas cosaturated with both quartz by the breeching of the barrier that separates a shallow
and feldspar, due to kinetic factors. Candela (1997) and Pic- magma chamber from the hydrostatic regime that surrounds
coli et al. (2000) suggested that quartz nucleates more easily it (Fournier, 1999). The magma may be already saturated
34 CANDELA AND PICCOLI

with respect to a volatile-phase, or decompression may initi- the formation of sulfur-rich magmatic hydrothermal ores. One
ate volatile-phase saturation. In either case, the concentration would expect that sulfur would only be present in low concen-
of water and other volatiles in the melt may be lowered nearly tration in highly differentiated granites such as magmas asso-
isothermally. Supersaturation of the melt phase with respect ciated with Climax-type porphyry molybdenum deposits (Can-
to anumber of minerals can occur, with a degree of supersat- dela and Holland, 1986). Yet, even the highly fractionated
uration causing a high nucleation rate, leading to the produc- magmas that give rise to porphyry Mo deposits contain sulfur.
tion of a larger number of crystals per unit volume, and there- This suggests that the convergence of physical and chemical
fore smaller crystals. effects plays a role in the formation of such ore systems, with
Candela (1997) suggested that plumes of rising, volatile- the whole being greater than the sum of the parts.
saturated melts lead to the formation of miarolitic cavities. The basic premise of the magmatic hydrothermal model for
However, it should also be noted that most miarolitic granites the origin of porphyry-type mineral deposits involves the par-
are rather leucocratic. This association could result from sub- titioning of ore metals from a mixture of melt + crystals into
tle kinetic factors that may only be speculated on here (see exsolving and evolving magmatic volatile phase(s) (Candela
Cerny et al., 2005, for more discussion). The high concentra- and Piccoli, 1995, 1998). Crystal separation has been recog-
tion of iron and magnesium in hotter, less felsic melts (e.g., nized as a first-order process of magmatic differentiation
granodiorites) may poison the nucleation of quartz and since at least the time of Darwin (1844), and crystal fraction-
feldspar to such an extent that their integrated nucleation ation processes are likely to be a first-order control on the ore
rates are lower in the less felsic melts (Swanson and Fenn, potential of any given magmatic system. Crystal fractionation
1986). In more felsic melts, nucleation is more rapid, and is seen commonly as a force that promotes formation of in-
crystal sizes are smaller. For a granite to be miarolitic, the compatible element-rich ore deposits. Whereas fractionation
characteristic crystal size must be on the same order as the does increase the concentration of incompatible trace ele-
characteristic bubble diameter, or smaller. If the crystals are ments (with 1 > D > 0, where D is the bulk crystal/melt par-
on the same size as the bubbles, or larger, then the volatile tition coefficient for the element in question) in the remain-
phase will form an inter-granular film, the geometry of which ing melt phase, thereby increasing the (intensive) chemical
is more difficult to preserve in the rock record. potential of the ore substance, the total extensive amount of
any given metal in the melt phase decreases, and this in-
The Chemistry of Volatile Phase Exsolution evitably decreases the total tonnage available for ore forma-
Magina rising in the crust may be saturated or undersatu- tion. However, higher concentrations of metals in the melt
rated with respect to a volatile phase; saturation will occur lead to higher concentrations in a magmatic-hydrothermal
when the total confining pressure is reduced to the total ore fluid, and this can increase the probability of forming an
vapor pressure of the magma. Rising magma may reach the ore deposit, ceteris paribus.
surface and erupt; alternatively, magma ascent may be slowed A necessary step in the development of our understanding
by external structural factors or by an increase in viscosity due of fractionation is to measure the partitioning of elements be-
to crystallization or bubble production. As magma ascent tween silicate melts and volatile phases on one hand, and be-
slows, some crystallization will occur due to irreversible loss tween silicate melts and minerals on the other. Partition coef-
of heat to the cooler surroundings of a magma, and volatile ficients have been measured for the distribution of copper,
exsolution will be driven, increasingly, by crystallization rather gold, zinc, molybdenum, and other constituents between a
than by decompression. Depending upon the Cl/H2O ratio in melt and a supercritical gas, or in some cases, subcritical va-
the melt and pressure-temperature conditions, the magma pors and brines. The partitioning of copper, gold, molybde-
may saturate with respect to a supercritical gas, a vapor + num, tungsten, and other metals has also been studied be-
brine, or brine alone (see Webster et al., 1999; Webster, 2004). tween melts and various mineral phases. Many of these
Magmatic brines and vapors are thought to be critical agents partition coefficients have been collected and reported in
in ore formation because of their high fluidity and buoyancy, other reviews (e.g., Candela and Piccoli, 1995), and are not
and because of the affinity of many ore metals for volatile reproduced here. Furthermore, since many other papers
phases relative to rock-forming minerals (cf. Candela and Pic- have discussed the chemistry of magmatic devolatilization
coli, 1995). The data presented by Lowenstern (2001), for ex- (e.g., Candela and Piccoli, 1995; Ulrich et al., 1999; Frank et
ample, show that silicate melts are commonly saturated with al. 2002; Simon et al., 2005), only the chemical magmatic
respect to volatiles in the Earth’s mid- to upper crust. processes leading up to devolatilization will be covered here.
Lowenstern (1994) studied inclusions in the Pine Grove Modeling (Candela, 1989; Candela and Piccoli, 1995) has
porphyry molybdenum deposit, and found quartz-hosted suggested a number of factors may be important in magmatic
melt inclusions with up to 8 wt percent water and almost 0.1 hydrothermal ore genesis. Blevin and Chappell (1992) showed
wt percent COs. With these high volatile contents, the melts convincingly that the type of mineralization that forms in a
would be saturated at depths of nearly 16 km. It is hard to magmatic hydrothermal setting is a function of oxygen fugac-
imagine that magma with a long history of volatile exsolution ity. Decreasing magmatic oxygen fugacity increases =the parti-
or fractionation could yield such high CO: concentrations tioning of molybdenum relative to tungsten into crystalline
without late inputs of CO: from either crustal or subcrustal phases, thus decreasing the probability of Mo (relative to W)
sources. In fact, COz may be a marker for recharge of a felsic partitioning into an evolving ore fluid in reduced systems
magma chamber, or lack of significant prior loss of volatiles. (Candela and Bouton, 1990), consistent with the observations
Because the sulfurous gases behave similarly to COg during summarized by Burnham and Ohmoto (1980) and Thompson
volatile exsolution, these considerations may also be critical in et al. (1999).
 MAGMATIC PROCESSES IN THE DEVELOPMENT OF PORPHYRY-TYPE ORE SYSTEMS 35

As the ratio of the initial water content of the melt to the of mafic arc magmas with both lower crust rocks and more
saturation water content of the melt decreases, the efficiency felsic magmas, control the magmatic concentrations of car-
of compatible-element removal from the magma into an ex- bon dioxide, sulfur, water, and chlorine. Whether or not mag-
solving magmatic volatile phase decreases. For example, for mas are sulfide-saturated deep in the crust exerts a strong
magmas of a given initial water, copper, and molybdenum control on the amount of gold, copper, and other ore metals
concentration, the integrated Cu/(Mo+W) ratio of a (poten- and pathfinder elements that are available for partitioning
tial) ore fluid decreases with increasing depth in the crust. into exsolving magmatic volatile phase at shallower levels.
The general observation of shallow copper and deeper molyb- Whereas extensive pyrrhotite formation and sequestering of
denum and tungsten porphyry deposits supports this mag- copper due to fractionation can inhibit the development of a
matic hydrothermal theory, and this also follows from the magmatic hydrothermal copper deposit, it has less of an ef-
quantitative model (Candela, 1992). Thus, melts at deeper fect on gold owing to its lower partitioning into pyrrhotite rel-
levels can fractionate further, before volatile saturation, rela- ative to copper; however, fractionation of even small amounts
tive to melts that crystallize at a shallow level. In this model, of Cu-Fe sulfides in the magma can deplete a melt in gold. By
compatible elements are sequestered in the crystallization contrast, a high oxygen fugacity can preclude the formation of
products, relative to more incompatible elements. magmatic sulfides. Candela and Blevin (1995a) argued that
Partitioning data (Lynton et al., 1993; Jugo et al., 1999) ore formation in the magmatic hydrothermal environment is
show that copper partitions strongly into pyrrhotite from sil- probabilistic in nature, with a number of factors combining to
icate melts. Gold also can be accommodated in pyrrhotite, al- produce ore deposits, and rarely, giant ore deposits; if too few
though it partitions more strongly into magmatic Cu-Fe sul- of these factors operate, then subeconomic deposits may re-
fides (Jugo et al., 2000). A study by Simon et al. (2003) sult. We concur with Clark (1993), Tosdal and Richards
suggested a partition coefficient for gold between magnetite (2001), and others who have suggested that porphyry Cu-Mo-
and melt on the order of 4. Early volatile exsolution or con- Au deposits require the coincidence and positive interaction
ditions that minimize magnetite and/or Cu-Fe sulfide crys- of a series of individually commonplace geological processes
tallization favor the partitioning of copper and gold into such as convergent margin magmatism, and that they reflect
volatile phases relative to crystalline phases at the magmatic the dynamic interplay between magmatic, hydrothermal, and
stage. tectonic processes.
Scaillet and Evans (1999) confirm that pyrrhotite is stable
Acknowledgments
in magmas up to an oxygen fugacity ofQFM + 2, a result that
is broadly consistent with the recent results by Jugo et al. We thank Jeff Hedenquist and John Thompson for the in-
(2005). Below this oxygen fugacity, pyrrhotite can be stable, vitation to write this paper. Jake Lowenstern is thanked for his
and the tonnage of copper available to the hydrothermal sys- early contributions to the paper, and for his continuing en-
tem may be diminished if pyrrhotite is left behind, se- couragement during the writing process. Comments by Mark
questered in the crystalline residuum that may be distributed Cloos, Steve Kesler, Tom Sisson, Jeremy Richards, and Jeff
throughout the crust as the result of the protracted evolution .Hedenquist are greatly appreciated. This work was sup-
of magmas during their repeated chambering and upward ported, in part, by the National Science Foundation (EAR-
movement. Magmatic sulfides that occur in the variably tex- 0125805 and EAR-0309967). We would like to thank Callan
tured plutons proximal to the sites of ore deposition in por- Bentley for his contributions to the drafting of figures for this
phyry and related deposits may be the mere vestige of the sul- paper.
fides that have been removed from magmas during their
transcrustal evolution (Simon et al., 2003). Volatile saturation REFERENCES
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Barra, F., Ruiz, J., Ryan, M., and Titley, S., 2002, A Re-Os study of sulfide
volatile saturation critical. If a significant amount of minerals from the Bagdad porphyry Cu-Mo deposit, northern Arizona,
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