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Platinum-Group Elements
James E. Mungall and Anthony J. Naldrett*
1811-5209/0004-0253$2.50
INTRODUCTION
The concentration of platinum in the parts of the Earth that
are exposed on land is about 0.4 ppb (FIG. 1). To be worth
mining, Pt ores must contain amounts similar to 4 ppm, a
10,000-fold enrichment over typical crustal rock. However,
from 4 ppm, an ore must be further refined until the Pt concentration is 100,000 times higher before this precious
metal appears in the jewelers alloy we call white gold. How
can we detect ores with such low concentrations that the
metal is invisible except to the most precise geochemical
analysis, and how does the metal become 10,000 times
more abundant in some rocks than in others? No other
commonly used element requires such extreme concentration to become useful, and therefore none pose such
extraordinary challenges to petrologists and economic
geologists. The reason for the extreme depletion of the
platinum-group elements (PGE) in the silicate Earth is the
topic of the articles in this issue by Palme (2008) and
Lorand et al. (2008). In this article we examine the ways in
which that extreme depletion can be undone to the extent
that we can mine and extract the PGE for practical uses.
At equilibrium, the concentration of all of the PGE is at
least 10,000 times higher in sulfide melt than in coexisting
silicate melt, making sulfide an extremely potent agent for
the collection and segregation of PGE from magmas in
which each PGE normally occurs at concentrations less
than 15 ppb (Fleet et al. 1999; Arndt et al. 2005). The
extreme enrichment of PGE in sulfide liquid with respect to
coexisting silicate melt is a consequence of the preference
shown by the PGE for covalent bonding with sulfide ions in
sulfide melt over the more ionic character of the bonds
formed with oxygen ions in silicate melts. The processes
controlling the formation of PGE deposits are therefore
inextricably tied to the igneous geochemistry of sulfur.
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FIGURE 1
SOURCES THEREIN
formation of intraplate picritic magmas. When these magmas form, the degree of melting is high enough to completely dissolve all the sulfur in their mantle source regions
(Arndt et al. 2005; Barnes and Lightfoot 2005).
In order to form a PGE deposit, a fertile magma must become
saturated with sulfide melt at a place in the crust where the
sulfide can accumulate in a structure that will later be accessible to mining operations. Because primitive fertile magmas must be generated under sulfide-undersaturated
conditions and further, because sulfide solubility increases
with decreasing pressure, such magmas begin their residence in the crust strongly sulfide undersaturated and
hence do not readily produce an immiscible sulfide phase.
Two mechanisms can work, singly or in concert, to provoke
sulfide saturation. In the first, because sulfide does not
enter any of the common fractionating solid phases in a
cooling silicate magma, its concentration increases with
progressive cooling and crystallization until the magma
eventually reaches sulfide saturation. This might require a
large degree of crystallization, so the magma from which
sulfide eventually segregates may be as highly evolved as a
ferrobasalt. In this case, nucleation of the first immiscible
sulfide will be somewhat inhibited due to the large interfacial tension between sulfide and the highly evolved silicate
melt. Widely spaced droplets of sulfide will grow by diffusion until they are large enough to settle to the bottom of
the magma body; this process can be described as fractional, like a distillation. In a moonshine still, the first
fumes to leave contain the highest concentration of those
volatile alcohols that are most strongly partitioned into the
vapor. Similarly, during fractional removal of sulfide, the
first sulfide to fall out will contain the most strongly chalcophile elements. These are the PGE, so the first appearance
of sulfide is expected to produce thin layers containing very
small amounts of sulfide with extremely high PGE concentrations. Due to the fractional nature of this process, a chromatographic segregation of the chalcophile elements is
anticipated as a consequence of the interplay of their partiELEMENTS
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sulfide liquid begins to segregate in a previously sulfideundersaturated magma column, then a distinct sulfide-rich
layer may form in consequence.
If sulfide droplets accumulate at the base of a melt body in
sufficient quantity to form a continuous pool of sulfide
melt, they will subsequently undergo a process of magmatic
evolution largely or wholly decoupled from the evolution
of the parental silicate magma. Although sulfide melt is
superheated at magmatic conditions typical of basaltic
magmas, a sulfide melt pool will eventually cool to its liquidus temperature and begin to solidify by forming crystals
of monosulfide solid solution (mss) or magnetite, or both.
Eventually the mss and magnetite are joined on the liquidus by intermediate solid solution (iss; i.e. magmatic
cubanitechalcopyrite solid solution), and during the latest
stages of cooling, the sulfide melt may solidify to a variety
of phases including pentlandite, millerite, bornite, and a
variety of rare copper-sulfide minerals. Platinum, palladium,
and gold are rejected by all of these minerals except perhaps
pentlandite, with the result that fractionated sulfide melts
are highly enriched in these elements compared with the
sulfide that initially equilibrated with the silicate magma.
As a result, even sulfides that segregate at fairly high sulfide/silicate mass ratios and consequently are not initially
very rich in PGE may ultimately generate small volumes of
very high-grade PGE mineralization, provided that the residual melts are able to migrate away from the mssmagnetite
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Processes governing the formation of PGE deposits. Sulfides (red dots) persist in the mantle during early stages
of mantle melting and are not exhausted until much melting has
occurred. PGE deposits may form in layered intrusions when magmas
reach sulfide saturation during fractional crystallization, by transport of
PGE-rich fluids through cumulate crystal piles (uppers), or by magma
recharge and mixing events (downers). The Norilsk deposit type
occurs when fertile magma in a magma conduit encounters sulfide-rich
sediments and becomes sulfide saturated.
FIGURE 2
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FIGURE 3
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PGE MINERALIZATION
OF THE BUSHVELD COMPLEX
The Bushveld Igneous Complex contains by far the majority of PGE mined today (FIG. 3). The mechanism by which
PGE were concentrated in the Merensky Reef has given rise
to considerable debate. Hypotheses fall into two principal
groups: (1) those (christened uppers) according to which
the PGE were scavenged from the underlying cumulates by
ascending, chloride-rich, aqueous fluids that had been
released as anhydrous minerals segregated from trapped,
intercumulus magma (Boudreau and McCallum 1992); and
(2) those (christened downers) that maintain that the
PGE were scavenged from overlying magma by settling sulfides that had segregated in response to either magma mixing (Campbell et al. 1983) or pressure change (Cawthorn
2005). These hypotheses are illustrated in FIGURE 2.
Recently, Naldrett et al. (2008) pointed to marked upward
decreases in PGE tenor and Pd/Cu in sulfides, which they
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FIGURE 4
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ACKNOWLEDGMENTS
FUTURE OUTLOOK
Future prospects for the discovery of PGE ore deposits are
interesting to contemplate. Discoveries of relatively small
PGE deposits in mafic and ultramafic rocks continue to be
made every year; however, it is unlikely that another layered intrusion of the stupendous scale of the Bushveld
Complex remains to be found. We suspect that if a future
discovery of another group of deposits on a scale approach-
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