JOURNAL GEOLOGICAL SOCIETY OF INDIA

Vol.77, April 2011, pp.295-302

Platinum Group Element (PGE) Geochemistry to understand the

Chemical Evolution of the Earth’s Mantle

SISIR K. MONDAL
Department of Geological Sciences, Jadavpur University, 188 Raja S.C. Mullick Road, Kolkata - 700 032, India
Department of Earth and Planetary Sciences, American Museum of Natural History,
Central Park West@79th Street, New York City, NY-10024, USA
Email: sisir.mondal@gmail.com

Abstract: Platinum group elements (PGE: Os, Ir, Ru, Rh, Pt, Pd) are important geochemical and cosmochemical tracers.
Depending on physical and chemical behaviour the PGEs are divided into two subgroups: IPGE (Ir, Os, Ru) and PPGE
(Pd, Pt, Rh). Platinum group elements show strong siderophile and chalcophile affinity. Base metal sulfides control the
PGE budget of the Earth’s mantle. Mantle xenoliths contain two types of sulfide populations: (1) enclosed within
silicate minerals, and (2) interstitial to the silicate minerals. In terms of PGE characters the included variety shows IPGE
enriched patterns – similar to the melt-depleted mantle harzburgite, whereas the interstitial variety shows PPGE enriched
patterns – resembling the fractionated PGE patterns of the basalt. These PGE characters of the mantle sulfides have been
interpreted to be representative of multi-stages melting process of the mantle that helped to shape the chemical evolution
of the Earth.

Keywords: Mantle xenoliths, Base metal sulfides, Platinum group element (PGE), Os isotope, Mantle heterogeneity

INTRODUCTION chemical evolution of the Earth’s mantle. The PGEs can be

Platinum group elements (PGE: Pt, Pd, Rh, Ir, Ru and
Os) are similar to one another in some respects but their
behavior differs markedly from their congeners in Group
8b of the periodic table, the transition metals Fe, Ni and Co
(Westland, 1981). The PGEs together with Au constitute a
coherent group of siderophile and chalcophile elements
having a strong repulsion to form oxygenated compound -
the so-called ‘noble’ character. Within the range of oxygen
and sulfur fugacities prevalent in the crust and upper mantle,
the PGEs commonly exhibit chalcophile behaviour (Naldrett
and Duke, 1980). The PGEs are much important as they
have distinctive geochemical behaviour that helps to
reconstruct some evolutionary aspects of the Earth. In
addition, they have a great economical relevance and
represent an important target in ore exploration. In this article
I present a short review on geochemical aspects of the
platinum group elements. In addition, the subject of the
mantle heterogeneity has been discussed with respect to the
PGE and Os isotopic compositions of the mantle.
PLATINUM GROUP ELEMENTS: GENERAL ASPECTS
Geochemistry of the PGEs helps to understand the
subdivided in two groups with contrasting characters:
(a) Ir-PGE, containing Os, Ir and Ru; and (b) Pd-PGE
containing Pd, Pt and Rh (Barnes et al. 1985). The members
of the former group are more siderophile and refractory,
whereas the latter are more chalcophile and volatile.
Table 1 summarizes some physical, geochemical and
mineralogical characteristics of the PGEs. It is evident from
the table that the ‘refractory’ PGEs (Os, Ir and Ru) have
very high fusion temperature, and the ‘fusible’ PGEs (Rh,
Pt and Pd) have lower fusion temperature. Buchanan (1988)
described the PGEs as (a) light triad: Ru, Rh and Pd, and
the (b) heavy triad: Os, Ir and Pt. The light elements have
only half the density of the platinum triad; Os, Ir and Pt
have extraordinary high densities (Table 1).
Mineralogically, the PGEs form about 150 mineral
species, including native metals, alloys, arsenides, tellurides,
selenides, antimonides and oxides, and they also enter into
solid solution in various base metal sulfides (e.g., Cabri,
1981; 2002). Platinum group elements are most commonly
found in sulfides of mafic-ultramafic rocks (e.g., Maier,
2005; Mondal and Zhou, 2010). Two types of deposit are
distinguished: primary deposits in rock, and secondary
deposits in alluvium. Alluvial deposits include modern

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296 SISIR K. MONDAL
Table 1. Some physical, geochemical and mineralogical characteristics of the PGEs (Source: Cabri, 1981;
2002; Buchanan, 1988)
Element Atomic Atomic
number weight
Ruthenium (Ru) 44 101
Rhodium (Rh) 45 102
Palladium (Pd) 46 107
Osmium (Os) 76 190
Iridium (Ir) 77 193
Platinum (Pt) 78 195
placers, which commonly show an association with
ultramafic/mafic complexes such as ‘Alaskan-’ or ‘Alpine-
type’ intrusions and paleoplacers. The Witwatersrand is the
only known example of the ‘paleoplacer’ that is sufficiently
rich in the platinum group elements to permit recovery
(Macdonald, 1987). The orthomagmatic class contains all
those deposits that form solely within the magmatic
environment (Naldrett, 2004; Mondal, 2008; Mungall and
Naldrett, 2008 for review).
Almost all production of the platinum group metals
comes from South Africa (supplies in 2009: Pt = 4.53 million
ounces, Pd = 2.37 million ounces and Rh = 0.663 million
ounces) - mostly from the Bushveld Complex, and Russia –
where most production comes from Norilšk in Siberia, from
where PGEs are extracted with Cu and Ni (supplies in 2009:
Pt = 0.785 million ounces, Pd = 2.675 million ounces and
Rh = 0.07 million ounces; Data source: ‘Platinum, 2010’).
The platinum group elements have many industrial uses,
which are essentially based on their very high fusion
temperature, the absence of chemical reactivity and
exceptional catalytic properties. The main end-uses of
PGE lie in electronics: Pt-Rh thermocouples are extensively
used in the measurement of high temperature in furnace; Pd
has widespread use in telephone exchange still operating
on electro-mechanical switching; the car industry
(manufacturing catalytic exhausts), jewelry (the main use
of Pt), dentistry (Pd), chemical (Pt and Rh for making glass
fibers) and the petroleum industry (Pt).
PLATINUM GROUP ELEMENTS AS
GEOCHEMICAL TRACER
Geochemistry of the platinum group elements provides
unique clues to the early origins of our planet (e.g., Carlson
Melting Density Main platinum
T °C group minerals
2334 12.4 Laurite (RuS2)
1966 12.4 Hollingworthite (RhAsS)
1552 12.0 Kotulskite (PdTe),
Braggite (Pt,Pd)S,
Merenskyite (PdTe2)
2700 22.7 Erlichmanite (OsS2)
2454 22.6 Irarsite (IrAsS)
1769 21.5 Cooperite (PtS),
Braggite (Pt,Pd)S,
Sperrylite (PtAs2),
Moncheite (PtTe2)
et al. 2008). The platinum group elements are particularly
useful as tracers of the impacting extra-planetary materials
in the strongly PGE-depleted crust of the Earth and other
planets (e.g., Palme, 2008). The distribution of PGEs within
the Earth is a subject of intense debate (Crocket, 2002;
Lorand et al. 2008). Platinum group elements have a strong
siderophile affinity (Chou, 1978). Laboratory experiments
provide the evidence that the PGEs have more than 105 times
greater preference for liquid metals than for the silicate
magmas (e.g., Righter, 2003). Therefore, during core-mantle
differentiation, the PGEs should have preferentially
partitioned into the core-forming metal, leaving the mantle
depleted in these elements relative to their original
abundances. However, the measured or estimated PGE
contents of planetary mantles are much higher than predicted
by these partition coefficients. Calculation shows that if the
Earth’s mantle was in equilibrium with its core, the mantle
would contain three orders of magnitude less of the PGE
than is observed, supporting a late addition of PGE
components (Drake and Righter, 2002).
The most common explanation put forward to account
for this disparity is that the last 1% of the Earth’s accretion
occurred after the iron-rich core had separated from the
mantle. According to this model the Earth’s mantle
underwent whole-sale bulk depletion in PGE during core
formation (at about 4.55 Gyr ago), followed by progressive
re-enrichment with PGE in response to addition of cosmic
material from the Hadean to Early Archean (4.5-3.8 Gyr
ago) through heavy meteorite bombardment - the so-called
‘late veneer’ (Chou, 1978). Another viable mechanism is
based on different crystallo-chemical properties of the
elements at high pressure and temperature. It has been
suggested that the distribution coefficients of the siderophile
elements (especially Pt, Pd and Au) between metal and
JOUR.GEOL.SOC.INDIA, VOL.77, APRIL 2011
 PGE GEOCHEMISTRY TO UNDERSTAND THE CHEMICAL EVOLUTION OF THE EARTH’S MANTLE 297

silicate phases can be changed under high pressure and
temperature conditions, owing to which the lower mantle
materials may contain higher amount of siderophile elements
(e.g., Cottrell and Walker, 2006; Righter et al. 2008; Brenan
and McDonough, 2009). Another idea, that the PGE-rich
liquid outer core material can be transported back into the
mantle, as trace elements in plumes, rooted at the core-mantle
boundary has also received a great deal of attention (e.g.,
Brandon and Walker, 2005).
The relative effects of these processes can be assessed
using PGE abundance patterns as well as Re-Os isotopic
systematics of the mantle materials (e.g., Shirey and
Walker, 1998). Conventional radiogenic isotope studies of
mantle differentiation traditionally involve elements (Sr, Nd,
Hf, Pb) that strongly prefer melt over residual solid (e.g.,
Faure, 1986). Therefore, mantle residues after melt
extraction are difficult to study because they have very
low concentrations of these elements. Unlike any other
element in a radioisotope system, Os is a compatible element
which stays in the residue during melting in the mantle. As
a result, most magmas, and the crust formed from such
magmas, have high Re/Os ratios compared to the mantle
rocks. The advantage of using the Os isotope system is
that this system develops large parent-daughter contrasts
among magma sources, it records prior melt depletion effects
in mantle sources, and also helps to identify the effects of
any secondary event over primary magmatic events. In
addition, the 187Re/188Os isotope system (where the decay
constant, D, for 187Re=1.666×10-11 year-1, Smoliar et al.
1996) is particularly useful for discriminating between
long-term melt-depleted reservoirs, including the sub-
continental lithospheric mantle (SCLM; Walker et al. 1989;
Pearson, 1999; Mondal et al. 2007).
Base metal sulfide minerals are common in mantle
rocks (Fig. 1), but are not widely characterized in detail for
the purpose to look and to examine the processes shaping
the chemical evolution of the Earth’s mantle. It has been
documented that sulfide minerals in mantle peridotites
control the PGE budget of mantle rocks along with their
behaviour during mantle melting. Hence, the sulfide minerals
in mantle rocks can be used to trace the petrogenetic
processes responsible for the differentiation of the Earth

EPV

ROLYLQH

EPV

MP
Fig.1. SEM image of a kimberlitic mantle xenolith (mantle peridotite) from west Greenland. Sample showing base metal sulfides as
inclusion within olivine (bms-1) and at the interstitial spaces of olivine (bms-2). SEM imaging conducted by the author at the
EPMA laboratory, University of Copenhagen. Sample courtesy Minik Rosing, Natural History Museum of Copenhagen, University
of Copenhagen.

JOUR.GEOL.SOC.INDIA, VOL.77, APRIL 2011

298 SISIR K. MONDAL
(Mitchell and Keays, 1981; Morgan, 1986; Guo et al. 1999;
Aulbach et al. 2009). Because at equilibrium, the
concentration of all of the PGEs is at least 10,000 times
higher in sulfide melt than in coexisting silicate melt, sulfide
is an extremely potent agent for the collection and
segregation of PGE (e.g., Fleet et al. 1999; Sattari et al.
2002; Brenan and McDonough, 2005). Major research has
been focused on immiscible sulfides in mantle derived
magmas; however, very little is known about the origin of
these mantle sulfides and studies in this direction are also
scarce.
OSMIUM ISOTOPIC CONSTRAINTS ON
MANTLE HETEROGENEITY
It has been shown that in terms of Os isotopic
compositions, the Earth’s convecting upper mantle is
chondritic (e.g., Meisel et al. 2001; Walker et al. 2002).
However, there are strong evidences for mantle
heterogeneity in terms of siderophile elements, particularly
with respect to Os isotopic signatures (Frei et al. 2006;
Bernstein et al. 2006; Ahmed et al. 2006). Peridotites that
have recently been removed from the old sub-continetal
lithospheric mantle (SCLM) are observed to have Os
isotopic compositions that are much less radiogenic than
chondritic meteorites (e.g., Walker et al. 1989; Pearson et
al. 1995). The depleted, subchondritic Os isotopic
compositions in these rocks have been attributed to long-
term Re depletion, which evidently reflects ancient melt
removal, coupled with the moderate incompatibility of
Re but compatibility of Os, during mantle melting (e.g.,
Walker and Shirey, 1998; Mondal et al. 2007 and references
therein).
Similarly less radiogenic Os compositions were found
in orogenic peridotites, which are thought to represent
Proterozoic SCLM (Reisberg and Lorand, 1995). Walker
and Stone (2001) reported significantly subchondritic Os
isotopic compositions for an Archean high-Mg volcanic
rock, the Boston Creek flow of the Abitibi greenstone belt
(Ontario, Canada), suggesting derivation from ancient
SCLM. In addition to SCLM, 187Os depleted materials have
also been identified in oceanic rocks (e.g., Harvey et al.
2006). The depleted compositions were interpreted to reflect
either derivation from long-term Re-depleted SCLM that
had been delaminated from the craton, or survival of highly
Re-depleted reservoirs for more than 1 Ga in the convecting
mantle.
The observations from the mantle xenoliths confirm
that the SCLM is geochemically distinct from the convective
mantle, and has remained stable as residue of extensive
partial melt extraction in the Archean (Boyd, 1989; Bernstein
et al. 1998; Griffin et al. 2003; Herzberg, 2004; Carlson et
al. 2005). Some peridotite xenoliths removed from the
SCLM underlying Archean portions of the cratons e.g.,
Greenland, Siberian, Kaapvaal, Wyoming and Tanzania
cratons, indicate melt depletion as much as 3.6 Ga ago (e.g.,
Mondal et al. 2007 and references therein). Osmium isotopic
studies of unaltered chromites from the Nuasahi and Sukinda
ultramafic-mafic complexes, in the Singhbhum craton of the
Indian shield, indicate the existence of a SCLM domain
beneath the Singhbhum craton that started to form in 3.7 Ga
ago by depletion of a primitive mantle (Mondal et al. 2007).
The average initial 187Os/188Os compositions of unaltered
chromites of massive chromitite layers from two igneous
complexes are subchondritic: 0.1031±0.0007 (Nuasahi) and
0.1029±0.0005 (Sukinda), with negative JOs values of
-1.78±0.65 and -2.04±0.43, respectively. The subchondritic
signatures of Os in the Singhbhum chromites are comparable
with results of age-constrained chromites from ultramafic
intrusions in the Zimbabwe craton (e.g., Nägler et al. 1997).
They indicate the sub-chondritic nature of the source mantle,
and are more compatible with subcontinental lithospheric
mantle extraction characteristics.
KNOWLEDGE GATHERED FROM THE STUDIES OF
SULFIDE MINERALS IN MANTLE XENOLITHS
Within the peridotitic mantle xenoliths, sulfide
minerals are mostly present as inclusions as well as at the
interstitial spaces of olivine, garnet, clinopyroxene and
orthopyroxene (Fig. 1). The PGE abundances and Os
isotopic characters of these sulfide minerals, have been used
as a tracer of geochemical evolution of the source mantle,
from where these xenoliths were sampled by the kimberlitic
magma or a basaltic magma. Together with petrological
information, PGE geochemical and Os isotopic data of the
sulfide minerals can help to assess the importance of
magmatic processes (e.g., mantle melting) versus primary
differentiation process responsible for the chemical character
of the mantle. In particular, one can determine whether or
not the source of the xenoliths is part of a long term Re-
depleted cratonic mantle reservoir (i.e. SCLM), the timing
of the depletion of the mantle, and what the various Os
isotopes as well as variation in PGE contents among the
included and interstitial base metal sulfides tell us about
how metals were redistributed in subsolidus environments.
When the upper mantle peridotite undergoes partial
melting, its abundances of siderophile elements are
fractionated. If plotted in order of decreasing melting
temperature, PGE abundances in magmas (e.g., basalt)
JOUR.GEOL.SOC.INDIA, VOL.77, APRIL 2011
 PGE GEOCHEMISTRY TO UNDERSTAND THE CHEMICAL EVOLUTION OF THE EARTH’S MANTLE 299

produce positively sloped patterns, while restitic mantle 

D
rocks (e.g., harzburgite) show smooth negative slopes

(Fig. 2). The mechanism of fractionation is not known in
detail, but likely involves the selective uptake of Os, Ir and 
,QFOXGHGVXOILGH

6XOILGH&,&KRQGULWH
Ru, relative to Pt and Pd, in residual olivine, Cr-spinel and

crystalline monosulfide solid solution (Righter et al. 2004;
Brenan et al. 2005; Ballhaus et al. 2006 and references  ,QWHUVWLWLDOVXOILGH

therein).
From a detailed study of the mantle xenoliths Alard et 

al. (2000) described two texturally and compositionally

 HRO066&S HRO066 L&XULFK3Q
distinct types of sulfides in mantle-derived peridotites: (1) L&XULFK3Q
L3Q
HRO066 L&XULFK3Q

rounded monosulfide solid solution enclosed in silicates, 

2V ,U 5X 5K 3W 3G
usually in depleted, S-poor samples, and (2) interstitial 
sulfides, often rich in Ni or Cu. Both types, commonly, occur
in a single sample. Figure 2 shows comparison of the
abundances of selected PGEs, measured in-situ using LA-
ICP-MS by Alard et al. (2000) in sulfide grains from the
mantle lherzolite (Fig. 2a), and the abundances in residual
harzburgite and basalt (Fig. 2b). The PGE signature of the
sulfides enclosed in olivine is almost identical to that of the
residual harzburgite. With the exception of platinum, the
PGE in the interstitial sulfides found between the grains,
display a signature similar to that of the basalt. So, the two
sulfides have the complementary patterns that are expected
for a melt and its mantle residue. From these data, Alard et
al. (2000) argue that the unusual patterns of PGE abundances
seen in mantle peridotites can be explained by ordinary
melting processes. They interpreted the silicate-enclosed
sulfides as the residues of melting processes, and the
interstitial sulfides as the crystallization products of sulfide-
bearing (metasomatic) fluids. These strong differences
between monosulfide solid solution and interstitial sulfides
agree with experimental data that suggest a strong affinity
of the IPGE (Ir, Os, Ru) for the monosulfide solid solution,
while Pt and Pd partition into the coexisting sulfide liquids
(Bockrath et al. 2004).
Using LA-ICP-MS, Pearson et al. (2002) determined
Os isotopic compositions of sulfides in kimberlitic mantle
xenoliths, and showed that sulfide inclusions in silicates
preserve significantly less radiogenic compositions than
interstitial sulfides and accordingly produce significantly
older and more realistic Re-Os age information than bulk
rock analysis. The in-situ analyses using LA-ICP-MS by
other workers (e.g., Alard et al. 2002; Griffin et al. 2004)
also showed that the two generations of sulfides are not
contemporaneous: ‘basaltic’ intergranular sulfides are 1-2
billion years younger than ‘restitic’ sulfides, suggesting that
the interstitial sulfides are likely metasomatically introduced
phases in the melt-depleted peridotites. Therefore, it seems
very likely that the abundances of PGE measured in modern
JOUR.GEOL.SOC.INDIA, VOL.77, APRIL 2011
E
KDU]EXUJLWH
KDU]EXUJLWH 025% 025%

5RFN&,&KRQGULWH
+DU]EXUJLWH

%DVDOW


2V ,U 5X 5K 3W 3G
Fig.2. Comparison of the chondrite-normalized PGE patterns of
the included (e-ol MSS) and and interstitial sulfides (i-Cu-
rich Pn; i-Pn) from the mantle lherzolite (data source: Alard
et al. 2000). The PGE patterns of the included sulfides show
similarity with the chondrite-normalized PGE patterns of
the melt depleted mantle harzburgite, whereas the PGE
patterns for the interstitial sulfides are similar to the basalt.
Mantle harzburgite xenolith (East African Rift) data from
Lorand et al. (2003); Basalt (Southern and Middle
Kolbeinsey Ridge) data from Rehkämper et al. (1999).
Chondrite data from McDonough and Sun (1995). Figure
is based on Alard et al. 2000; Rehkämper, 2000).
mantle rocks were overprinted by the magmatic processes,
especially melt removal and refertilization. Evidences from
the Os isotopic studies of peridotitic sulfide inclusions in
diamond from the SCLM even suggest metasomatic
signatures in 3.5 Ga Slave craton, and favours subduction
process can be the key to forming the earliest cratonic nuclei
(e.g., Shirey et al. 2004). In this regard, apart from
understanding the initial differentiation of the planet, it is
important to also evaluate the magmatic processes that
contributed in the evolution of the Earth’s mantle regions,
in terms of material addition and material recycling through
time.
300 SISIR K. MONDAL
Acknowledgements: I am dedicating this article to honour the
vast contributions of B. P. Radhakrishna to the Indian geology.
This review article is based on a collaborative project on the
kimberlitic mantle xenoliths from west Greenland. I am thankful
to Steve Shirey (Department of Terrestrial Magnetism, Carnegie
Institution, Washington), Stefan Bernstein (Natural History
Museum of Denmark, University of Copenhagen), Minik
Rosing (Natural History Museum of Denmark, University of
Copenhagen) and Ed Mathez (American Museum of Natural
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(Received: 21 December 2010; Revised form accepted: 28 January 2011)

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