S.Afr.J .Geol.

, 1995,98(2), 157-167 157

The fractionation of platinum-group elements in magmatic systems,

with the suggestion of a novel causal mechanism

M. Tredoux
Department of Geological Sciences, University of Cape Town, Rondebosch, 7700 Republic of South Africa.

N.M. Lindsay and G. Davies

Schonland Centre, University of the Witwatersrand, Johannesburg, 2050 Republic of South Africa.

I. McDonald
Department of Geology, University of Manchester, Manchester, Ml 3 9PL, United Kingdom.

Accepted 31 Janury 1995

Compatible behaviour has been considered as a major influence on the behaviour of the platinum-group elements (PGE) in
magmatic systems. The authors believe that current models tend to over-emphasize the crystal-chemical compatibilities of
the PGE, and that the PGE cannot be modelled as partitioning into sulphides or chromite in the conventional chemical
sense. Investigation of data from igneous rocks and ores from the Kaapvaal craton lead the authors to propose a model
which relies on the well-documented siderophile nature of the PGE: the PGE might occur in magmas as metallic clusters of
50-100 atoms, rather than as cations or any molecular species. Such clusters could be stabilized by an outside 'envelope' of
ligands (e.g. S. As, Sb, Te) and this might lead to their incorporation into a sulphide melt or chromite (if available);
however, the association between the PGE clusters and the sulphide would be a mechanical rather than chemical one.

Versoenbare gedrag word as 'n groot invloed op die gedrag van die platinumgroep elemente (PGE) in magmatiese stelsels
beskou. Die outeurs is van mening dat huidige modelle neig om die kristal-chemiese versoenbaarhede van die PGE oor te
beklemtoon, en dat die PGE nie as insluitsels in sulfiedes of chromiet in die gebruiklike chemiese sin gemodelleer kan word
nie. Navorsing van die verspreiding van PGE in stollingsgesteentes en ertse van die Kaapvaalkraton het tot die voorstelling
van 'n model, wat berus op die goed gedokumenteerde siderofiele aard van die PGE, gelei: die PGE mag as metaliese trosse
van 50-100 atome, eerder as katione of enige molekulere spesie, voorkom. Sulke trosse kan deur 'n uiterlike omhulsel van
ligande (bv. S, As, Sb, Te) gestabiliseer word en dit mag tot hulle inkorporering in 'n sulfiedsmelting of chromiet (indien
beskikbaar) lei; die assosiasie tussen die PGE trosse en die sulfied sou egter meganies eerder as chemies wees.

Introduction
The major platinum-group element (PGE) ores of the world
span a wide range of geological settings but most frequently
the PGE are associated, at least to some extent, with Ni-Cu
sulphides. This fact has led very naturally to the development
of geochemical models in which the PGE are treated as
chalcophile elements (e.g. Naldrett et al., 1979; Campbell et
al., 1983; Von Gruenewaldt et al., 1986).
Such models contain a tacit, usually unexpressed, assump-
tion that the PGE are chemically compatible with sulphide
melt at magmatic temperatures, i.e. that, if an immiscible sul-
phide melt should separate from a silicate magma, the PGE
would have very large positive bulk partition coefficients
(Dsu1phictc1,rnca1e) in favour of the sulphide. Thus, the fate of the
PGE (and, by implication, enhanced probability of the forma-
tion of an economically viable PGE ore horizon) within any
particular magmatic system is assumed to be controlled by the
same parameters as those which control the formation of
immiscible sulphide melt. These models have proved to be
successful enough to allow the first-order modelling of the
behaviour of Pt and Pd (see e.g. Wilson et al., 1989). How-
ever, they are much less successful when applied to the
behaviour of the other PGE (e.g. Wilson & Tredoux, 1990;
Peach et al., 1990).
Sulphide-rich layers are not the only ones in magmatic sys-
tems which can show an enrichment in PGE. Olivine-rich
ultramafic rocks, although never as enriched as sulphides, do
generally have higher PGE concentrations than associated
less mafic rocks (Davies & Tredoux, 1985; Lee & Tredoux,
1986), and chromite layers are usually enriched in PGE rela-
tive to surrounding silicates (Lee & Tredoux, 1986; De Wit &
Tredoux, 1988; Naldrett & Von Gruenewaldt, 1989 and refer-
ences therein), especially in Os, Ir, Ru, and Rh (e.g.
Agiorgitis & Wolf, 1978; Page & Talkington, 1984). In some
of these cases too, the enrichment has been ascribed to high
bulk partition coefficients in favour of olivine and/or chromite
(Doliv1ne1,11ica,e and Dchrnm1tc1,mca,e respectively). In recent experi-
mental studies, Capobianco and co-workers (1994) interpret
their data on PGE partitioning in spinels as having definite
indications that 'large crystal-chemical compatibility' control
the behaviour of Rh and Ru.
Some workers (e.g. Hiemstra, 1979; Tredoux et al., 1991;
Fleet & Stone, 1992) have suggested that the chalcophile
behaviour of the PGE in magmatic systems has, in fact, been
over-emphasized, and that the well-documented (e.g. in mete-
orites) siderophile tendency of the PGE might well dominate
even in the presence of sulphide. This idea has been reflected
in a tendency to refer to 'effective' or 'virtual' D,u1phidcJsH1ca,e
when discussing PGE enrichment in sulphide ores (Wilson &
Tredoux, 1990; Barnes, 1993). Similar doubts about the valid-
ity of interpreting the enrichments in chromite and olivine in
terms of partitioning behaviour, senso stricto, have also been
expressed (e.g. Davies & Tredoux, 1985; Barnes & Naldrett,
1987).
In this article the authors endeavour to develop an alterna-
tive model for the behaviour of the PGE in a magma, which is
less reliant on the assumption that PGE enrichment, be it in
sulphides, chromitites, or olivine-rich rocks, are primarily
driven by any crystal-chemical compatibility, although it does
acknowledge a physical association. It is felt that such a
158
model might lead to a better understanding of some of the
inconsistencies within the current paradigms.
Fractionation trends of the PGE
It is very well documented that there is a fractionation of the
POE, relative to the presumed chondritic mantle, during
igneous processes (for reviews see Crocket, 1981; Barnes et
al., 1985; Naldrett & Von Gruenewaldt, 1989): basalts have
much higher Pt(or Pd)/Ir than the komatiites, and high-
temperature cumulates have low (Pt, Pd)/Ir when compared
with the associated melt rocks. When the chondrite
normalized concentrations of all six PGE are plotted in order
of decreasing melting point, as suggested by Naldrett (1981),
smooth trends are obtained. For most igneous rocks,
regardless of whether there is sulphide present or not, these
POE patterns have positive slopes. The gradients are variable,
as would be suggested by the variation in (Pt,Pd)/Ir: basalts
have steep slopes, komatiites and cumulates have flatter ones.
The exception to this general trend of positive slopes are
some chromitites from ophiolite sequences, which have
slopes with a negative gradient (Page & Talkington, 1984; De
Wit & Tredoux, 1988).
Interpretations of the observed fractionation trends are
strongly influenced by the model preferred by the author(s)
for the igneous processes involved. For example, some
authors feel that POE fractionation took place within the
magma chamber (Capobianco & Drake, 1990) whilst others
prefer processes at the site of melting as the source of the
fractionation, with little alteration within the magma chamber
itself (Lee & Tredoux, 1986). In the case of the podiform
chromitite layers with negative trends it is relevant to the
interpretation whether they are seen as cumulates (Coleman,
1977; Leblanc & Ceuleneer, 1992) or restites (Nicolas &
Prinzhofer, 1983; De Wit & Tredoux, 1988).
Currently favoured models ascribe the fractionation of the
POE to either
1. differences in Dsuiphidc/siiicate between the various POE (i.e.
D1' < DPd). A complication to this proposal is contained in
data from the Great Dyke (Wilson & Tredoux, 1990) and
Munni-Munni off-set ores (Barnes, 1993 ), which show
that Ir is much more strongly concentrated than Pd in the
earliest sulphide that separates from a magmatic system.
This would seem to indicate that D'' > DPd; or
2. Differences in compatibility with mantle phases and/or
early cumulates (with Ir being more compatible than Pd).
Both of these models are reflected in the proposal of Barnes
et al. (1985), who divided the POE into two groups which
they termed the IPGE (Os, Ir, and Ru) and the PPGE (Pt, Pd,
and Rh). In the next sections some data, both experimental
and empirical, will be examined to assess the success of these
models in predicting and/or explaining the observed trends.
Experimenta·I evidence
Investigation of metal-sulphide-silicate systems
Most of the experimental work in this category has been
concerned with metallic systems, and as such informs on
Dlll<llll/silicate (e.g. Jones & Drake, 1986; Amosse et al., 1990;
1993; Borisov et al., 1994) and Dlll<illfsulphidc (Fleet & Stone,
1991), rather than on D~sihca,e·
S.Afr.Tydskr.Geol., 1995,98(2)
All the workers in this field agree that the D!!!illlfsilicatc values
are extremely high (105-108), thus confirming the strong
siderophile tendency of the POE. The general trend seems to
be that the Dmc,al/silicate of the different POE are all of the same
order of magnitude, but that D 1' increases much more rapidly
with increasing f 02 than does DP•, an observation which has
been implied to cause the precipitation of the IPGE with early
cumulates (Amosse et al., 1990). Increase of JS 2 seems to
lead to a different fractionation trend, in which the light POE
(Pd, Rh, and Ru) seems to favour the sulphide phases,
whereas the heavy POE (Pt, Ir, and Os) remain strongly parti-
tioned into the metal (Fleet & Stone, 1991).
Some estimates of bulk Dsu]phide/srn,a,e for the POE, calculated
for co-existing sulphides and silicates in some POE-contain-
ing horizons, are listed in Table la. The absolute values of
these calculated Ds for any one of the POE show variability
over several orders of magnitude in different deposits (see
Campbell et al., 1983). There are also large variations of rela-
tive Din different magmatic systems (e.g. D"1/D 1'for UG-2 is
-1, but for MORB it is -0.2), and even for different layers in
the same system (e.g. DP1/DPd for UG-2 is -0.4, but for the
Merensky Reef it is -1). Stone et al. (1990) point out that
such estimations of bulk D values are 'inherently suspect'
because they assume that the POE values in the sulphide ores
represent those in a sulphide melt that separated from the sur-
rounding silicates under equilibrium conditions; this remains
an untestable, but unlikely, assumption.
Experimental Dsuirhide/silica,c data are very sparse in the litera-
ture, because the practical obstacles, some of which are listed
by Fleet et al. (1991), are prodigious. Some available values
are listed in Table 1b. The experimental values for D,u,rhidc/srnca1c
are much more equivocal than those for D!!!illlfsilica,c, but the
data in Table 1b would, broadly, support most of the calcu-
lated values in Table la. The major exceptions are Lac des
Iles, the D1'/DPd of which falls very far outside the range of the
experimental data, and the extremely high values postulated
for the UG-2 layer of the Bushveld Complex (Campbell et
al., 1983). In general it appears that the Dlill!Illlidl:/silicatc for all the
POE are of the same order of magnitude in any particular sys-
tem, although the data of Stone et al. (1990) report D"' to be
10 times less than DPd and D1'; this would support the observa-
tions of Peach et al. (1990) based on the analysis of coexist-
ing sulphides and glass in MORB. There is also some
evidence that DPd>D1', which would support the observations
of Great Dyke and Munni-Munni off-set ores mentioned ear-
lier.
The data reported by Fleet et al. (1991) are interesting in
that they indicate that the D,uinrudc/silica,, of the PGE might be
dependant on their concentrations in the magma: the lower
the POE concentrations, the lower the D~@ca,c· This has
been challenged by Bezman et al. (1993) and Fleet et al.
(1993), but it should be noted that both of these latter groups
investigated compositions at the extremes of the range
reported by Fleet et al. (1991 ), and as such their data do not
reflect on the trend reported in the earlier work.
Bezman et al. (1993) and Ballhaus et al. (1994) both inves-
tigated the effects of C-0-H-S fluids on the partitioning
behaviour of the PGE. The two sets of data are somewhat
contradictory, but unfortunately not directly comparable:
Bezman et al. (] 993), on the basis of bulk analyses, report an
S.Afr.J.Geol., 1995,98(2)
Table 1a Values of apparent bulk Dsulphide/silicate for Pd, Pt, and Ir, calculated on the
grounds of the observed differences in concentration between massive sulphides and
their silicate hosts
UG-2 UG-2 Merensky Talnakh
Pd 310 000 6 375
Pt 490 000 120 000 6 450
Ir 460 000
Refs 2 2
References: (I) Campbell et al., 1983; (2) Campbell & Barnes 1984; and (3) Peach et al., 1990.
Table 1b Dsulphide/silicate for Pd, Pt, and Ir from
experimental work
Low PGE
Pd 88 000 2 000
Pt 9 100 2 000
Ir 130 000 3 000
Refs 4 5
References: (4) Stone et al., 1990; (5) Fleet et al., 1991; (6) Bezmen
et al., 1994
elevation of two orders of magnitude in DlilJ.lrlllilk/smcaic for Pd and
Ir in the presence of the fluid phase, while Ballhaus et al.
(1994), who analysed Pt in individual fluid inclusions, find
that the Pt concentrations in the fluid inclusions are extremely
inhomogeneous, and appear to reflect solubility only under
very restricted conditions (Ballhaus etal., 1994).
Peach et al. (1990) stated that as a sulfide model cannot
account adequately for the Ir abundances, they needed to pos-
tulate that 'a phase(s) other than sulfide influences Ir fraction-
ation'. Similar sentiments are expressed by the majority of
workers, for the PGE as a group: the experimental data is
never completely able to reproduce the fractionation trends
seen in nature. This difficulty is most noticeable for Os, Ir,
Ru, and Rh (Fleet et al., 1993 ). It is tempting to use the data
from the low concentration runs of Fleet et al. (1991), which
lead to Dsu1rhi<letsmcate of -103, as an indication that the calculated
D,u1rhi<letsilica1e in the literature tends to be overestimated, espe-
cially for Os, Ir, and Ru, but the authors caution against this
extrapolation on the basis that the experimental systems lack
the complexity of real silicate melts.
This caution is undoubtedly applicable to all the experi-
mental work reported here. The PGE are commonly added to
the charges as metals, and the run temperatures are always
much lower than the melting points of the PGE. Thus the
PGE must enter the melts, be it silicate, sulphide, or metal, in
some speciated form. There is virtually no data with which to
model such processes. It is interesting to note that all the
experiments mentioned above have PGE-rich alloys in the run
products. Although this is reported generally, only Ballhaus et
al. (1994) made use of this observation in their interpretation.
This point will be taken up again in a later section. It will suf-
fice to note here that the trends reported in Table 1 (DP<l>DP•
and DP<l>D 11 ) are not unique to sulphide-silicate systems, but
are also consistent with the results of metal-silicate
partitioning mentioned at the start of this section. It is thus
possible that many of the experiments that set out to investi-
gate Dsu1rhi<lc1,;u,a,, might suffer from underlying influences of
159
Pipe Lac des Iles MORB
1500 12 120 000 >23 400
978 11 >2400
160 -14 250
2 2 3
High PGE
20 000 55 000
20 000
30 000 310 000
5 6
as suggested by Ballhaus et al. (1994) and Tredoux
Dme,au,mca,e,
et al. (1991).
Investigation of oxide-silicate systems
Most recent investigation in this direction has been done by
Capobianco and co-workers ( 1990, 1994) and focuses on Ru,
Rh, and Pd. The main thrust of their work is to elucidate the
fractionation of the IPGE from the PPGE, especially in some
chromite-rich lithologies (as discussed earlier). Their data
indicate that both Ru and Rh have positive D,rinel/me1t of the
order of 102-103, while Pd appears to be incompatible with
chromite. On the strength of this data, the IPGE enrichment in
chromite is modelled as a result of processes within the
magma chamber. Capobianco et al. (1994) disagree with
Amosse et al. (1990), who postulate that Ir is passivated in
silicate melts by 0 2 , mainly on the basis that the stabilization
that this would require is 'implausibly large'. Further to this
discrepancy, it should be noted that there is growing evidence
that the experiments of Amosse et al. (1990) probably did not
reach equilibrium (C. Ballhaus, pers. comm., 1994) and as
such cannot be used to deduce relative compatibilities of the
PGE with the phases involved.
This does not mean, however, that the model of Capobianco
and co-workers is the only means with which to explain the
data: their results can as easily be interpreted to reflect the
physical collection of unreacted (high temperature) Ru and
Rh phases in spine!, rather than true structural incorporation.
As is the case in the sulphide-metal-silicate experiments,
metallic particles are common run products in the experi-
ments of the silicate-oxide systems and a fraction of these
might represent the alloys originally added to the charges.
Capobianco et al. (1994) concede that it is possible that sub-
microscopic metallic clusters might be involved in the
observed reactions, and that this would undermine the inter-
pretation of their data in terms of simple crystal-chemical
behaviour.
160 S.Afr.Tydskr.Geol., 1995,98(2)

Table 2 List of samples and data used in Figure 2. PGE data in ppb, and MgO in per
cent. Very approximate sample locations can be deduced from Figure 1, by bearing in
mind the following: the Pongolo volcanics occur near the southeastern edge of the
Kaapvaal craton; the Ventersdo'rp lavas occur within the Witwatersrand Basin to the
south of the Bushveld Complex; the Losberg Complex is situated between the southern
tips of the two lobes of the Bushveld Complex; the Hekpoort and Dullstoom lavas occur
in the floor rocks of the eastern and western lobes of the Bushveld Complex,
respectively. Exact sample positions can be obtained from the authors
Sample Description Ir Pt Pd MgO
SARM-7 Merensky Reef equivalent (Bushveld) 63 3735 1530 20.1
WITS-I Spinifex textured komatiite (Barberton) 1.4 10 7 28.5
PBT-4 Komatiite (Barberton) 0.8 7 6 27.5
PP0-1 Chilled basalt (Pongola) 0.01 8.2
PVN-1 Chilled Mg-rich basalt (Ventersdorp) 0.9 8 IO 16.4
PLS-1 Chilled basalt (Losberg) 0.1 17 15 8.6
PLS-2 Chilled basalt (Losberg) 0.1 16 15 8.9
PWH-1 Tholeiite (Hekpoort) 0.02 6 7 5.3
PWH-2 Tholeiite (Hekpoort) 0.03 7 7 5.6
PEH-1 Tholeiite (Hekpoort) 0.01 7 8 5.1
PEH-2 Tholeiite (Hekpoort) 0.04 IO II 5.1
PED-I Tholeiite (Dullstroom) 0.03 6 2.7
PED-2 Tholeiite (Dullstroom) 0.02 5 2.7
PED-3 Tholeiite (Dullstroom) 0.02 11 3.7
PWP-1 Basalt (pre-Bushveld) 0.1 7 6 7.8
PWP-2 Basalt (pre-Bushveld) 0.09 14 15 5.9
PEP-2 Basalt (pre-Bushveld) 0.2 13 8 16.1
PWM-5 Basalt (Bushveld margin) 0.4 8 7.7
BICMGBAS Mg-rich basalt (Bushveld) 0.4 17 12 12.1
(ave of 9 samples)
BICTHOL Tholeiite (Bushveld) 0.09 II 6 6.7
(ave of 5 samples)
BI CULT Olivine cumulate sills 2.1 22 IO 33.4
(ave of 3 samples)
SID-2 Coarse-grained dunite (Barberton) 6.9 21 <10 37
PBT-3 Peridotite (Barberton) 2.8 IO 4 30.1

Data from the Kaapvaal craton
To gain some further information about processes which
affect the evolution of the PGE during partial melting and
fractional crystallization, 30 fine-grained basalts (assumed to
represent the original magmas) from the Kaapvaal craton in
South Africa, were analysed for Ir, Ru, Rh, Pt, and Pd. Also
included, for the purpose of comparison, were various
cumulate rocks from the Bushveld Complex and coarse-
grained dunites from the Barberton region. These data, with
brief descriptions of the samples, are listed in Table 2.
Approximate regional positions can be deduced in Figure 1,
and more information about the exact localities can be
obtained from the authors.
When the PGE data are plotted against MgO (as an indica-
tion of the degree of partial melting at the time of magma
extraction), as shown in Figure 2, some interesting trends are
observed. Pd seems to enter the melt quite readily at the
degrees of melting attained by tholeiitic magmas. Pt is
slightly less readily mobilized into the melt than Pd, but Ir
will only do so in appreciable quantities during very high
temperature events such as the extraction of komatiites. The
data from this study is supported by data on volcanic rocks
from Australia (Keays, 1982) and Russia (Briigmann et al.,
1993), also plotted on Figure 2. Although not presented in
Figure 2, the data for Rh follow trends very similar to that of
Pt, while the Ru data follow Ir. It would therefore appear that
the degree of partial melting (and by implication, the temper-
ature) at which magmatic processes happen, might exercise a
primary control over the behaviour of the PGE. A similar con-
clusion was reached by Fryer & Greenough, (1992) who com-
pared the behaviour of Ir and Pd in ocean island basalt,
MORB, and komatiites.
Chondrite-normalized plots of the Kaapvaal PGE, a sub-set
of which is shown in Figure 3, show the expected trends: all
the samples have patterns that are positively sloped. The
slopes of the lower temperature tholeiites and basalts are con-
S.Afr.J.Geol., 1995,98(2) 161

terns than basalts, komatiite-hosted ores have flatter patterns

than basalt-hosted ones.
NAMIBIA These observations place constraints on models that look to
differences in D, and processes within the magma chamber, to
explain the observed trends: for this to hold true, all mantle
derived melts would have to have flat, chondritic POE pat-
terns. It is believed that, though there might be some fraction-
SOUTH AFRICA

• Cape Town
• •
illlll!II Bushveld Igneous Complex
[2J Kaapvaal Craton
• Barberton Greenstone Belt .c
Q.
Q. 10
• • • •
0

Figure 1 A schematic map of southern Africa, indicating the

'C
Q. •• • 0
0
•
approximate outline of the Kaapvaal craton. The locations of the two •• •
most important regions mentioned in Table 2, namely, the -3.5 Ga
Barberton greenstone belt and the -2 Ga Bushveld Complex, are
also shown.
0 +----,----.---,--.-----..-,---r---~
0 10 20 30
sistently steeper than those of the komatiites, which are the MgO %
products of much higher temperature melting events. When
comparing the trends of high-temperature cumulate rocks and
restites with associated volcanic rocks (e.g. the olivine-rich
sills of the Bushveld with the tholeiites and basalts; and the 30 - - - - - - - - - - - - - - - - - - - ,
coarse-grained dunites in Barberton with the komatiites) the
cumulates and restites always display a relative enrichment in
the PGE with the highest melting points, namely, Os, Ir, and
20 -
Ru.
.c
Q.
Barnes et al. (1985) had interpreted these trends as result- Q.

ing from differences in the solubility of the PGE in silicates,

but Fleet & Stone ( 1991) found that the PGE solubilities are
not proportional to melting point. It has been mooted by
Tredoux et al. (1986) that the smooth trends that result when
the PGE are plotted in order of decreasing melting point
might not be coincidence. Our interpretation of the PGE
trends in Figure 3, and the PGE versus MgO plots in Figure 2, 0
is that PGE behaviour might be correlated to melt tempera-
ture. This has led us to sub-divide the PGE into two groups,
namely, high-temperature (HTPGE: Ir and Ru) and low-tem-
perature (LTPGE: Pt, Pd, and Rh). These groups are equiva- 3 -r--------------------,
lent to the IPGE and PPGE of Barnes et al. (1985), except
that there is practical significance to the temperature division 0
on the x-axis of the chondrite normalized plots, as an active
mechanism which influences the fractionation of the POE. 2 -
Another interesting observation contained in this data .c
appears to show that only minimal fractionation happens
Q.
Q. 0
0
•
within the magma chamber, that is, that an ore has a very sim-
ilar PGE trend to its associated magma - see Figure 4a for a
comparison of basalts and tholeiites of the Bushveld Com-
• •
plex, and their associated Merensky and U0-2 Reef ores; data • •
from the J-M Reef of the Stillwater Complex is also plotted,
although no direct data about its associated magma is availa-
ble, and it is consistent with the Bushveld data. There are no
0
0
·- ----· I

10
.6
I

POE ores associated with the komatiites in Barberton, but a
similar trend to that of the Bushveld data is seen when the
POE data from komatiite-associated ores in Australia and
Canada are compared with the komatiite data from Barberton
(see Figure 4b), that is, as komatiites have flatter POE pat-
20 30
MgO %
Figure 2 Plots of Pd, Pt, and Ir versus MgO. The solid diamonds
represent the data from Table 2, the open circles are komatiite data
from Australia (Keays, 1982) and the open triangles are basalts from
the Siberian traps (Briigmann et al., 1993).
162 S.Afr.Tydskr.Geol.,1995,98(2)

10 - 1

II)
w
Cl
a.
10-2 .,
'Cl

..
II)
N
w
Cl
a.
.,
'Cl

.!:!
-
E
0
,::

ai ';-
0
~ 10-3
0
,::
...'
0

10 -4

Os Ir Ru Rh Pt Pd

10 -.-------------,

(b)

Os Ir Ru Rh Pt Pd

Figure 3 Chondrite normalized plots of the PGE in magmas and

cumulates/restites. The x-axis shows the PGE in order of decreasing
melting point, as suggested by Naldrett (1981 ). The chondrite values
used are given in Tredoux et al. (1989). The symbols are: solid II)
w
circles = MgO-rich basalts of the Bushveld Complex; solid triangles Cl
a.
= tholeiites of the Bushveld Complex, solid squares = olivine-rich
sills of the Bushveld Complex, open triangels = a komatiite from the .,
'Cl .1

Barberton region (Davies & Tredoux, 1985), and open squares = a ..

N

very coarse-grained dunite from the Stolzburg Complex, Barberton

(Tredouxetal., 1989).
-
E
0
,::

ation of the PGE within a magma chamber [e.g. the
modification of Pd/Ir if the Bushveld ores as commented on
by Naldrett & Von Gruenewaldt (1989)], these result, at best,
only in alteration of an primary trend which is 'inherited'
from the dynamics of the melting process. In terms of this
model, the negative trends of some ophiolitic chromitites is
seen as indicators that these rocks are indeed restites, as has
been suggested by De Wit & Tredoux (1988), rather than
magma chamber cumulates.
Physical state of the PGE in a magma
It would seem that the behaviour of the PGE in a silicate
magma may be strongly influenced in the first instance by the
way in which their phases in the protolith respond to the
melting event that causes the magma. Experimental data with
which to evaluate this process, namely, information about the
thermal stabilities and melting behaviour of the common PGE
minerals, are very sparse, and exist in practical terms only for
Pt, Pd, and Rh (very few) (Toma & Murphy, 1977; Cabri &
Laflamme, 1981; Westland, 1981; Berlincourt et al., 1981;
';-
0
.01
.001 +--,---,--~--,---.----,---,
Os Ir Ru Rh Pt Pd
Figure 4 Chondrite normalized plots of the PGE in magmas and
associated sulphides: (a) basalts, and (b) komatiites. The x-axis
shows the PGE in order of decreasing melting point, as suggested by
Naldrett (1981). The chondrite values used are given in Tredoux et
al. (1989). The symbols are: (a) solid circles = MgO-rich basalts of
the Bushveld Complex (Davies & Tredoux, 1985); solid triangles =
tholeiites of the Bush veld Complex (Davies & Tredoux, 1985), solid
squares= the PGE standard SARM-7 (or PT0-1, Steele et al., 1975),
solid diamonds = the UG-2 reef of the Bushveld Complex, crosses =
sulphide ore from Noril'sk-Talnakh, Russia, plus signs= the JM reef
of the Stillwater Complex, U.S.A. (Naldrett, 1981); and (b) open
diamonds = ore from the Kambalda region, Australia, and open
triangles= ore from the Langmuir deposit, Canada (Naldrett, 1981),
solid circles= WITS-I (see Table 2), solid triangles= PBT (Table 2).
S.Afr.J.Geol., 1995,98(2)
Lindsay, 1989). The experimental data presented in the
previous section is not necessarily applicable because of
uncertainty about how well the PGE metals used can
represent the actual mantle phases.
In terms of our proposed model of primary temperature
control on the behaviour of the PGE, the HTPGE mantle
phases (typically alloys) are more refractory than those of the
LTPGE (also possibly alloys), and they might not be melted at
all during magma extraction. These elements might, conse-
quently, be present in the silicate melt in the form in which
they most commonly occur in the mantle, i.e. as inter-PGE
alloys (osmiridium, ruthosmiriduim, etc.) and it may be rele-
vant to see them as micro-xenocrysts, rather like diamonds in
a kimberlite (McDonald, 1993 ).
It is well known to all PGE analysts and mineralogists that
the PGE are very heterogeneously distributed in rocks at a
microscopic level. There now is a growing body of evidence
that this is also true at a sub-microscopic level, both in metal-
lurgical systems (Lindsay, 1989; Amosse et al., 1990), and
with respect to the 'invisible' PGE in naturally occurring sys-
tems (Chryssoulis et al., 1991; Ballhaus et al., 1994). The
nature of the discrete PGE phase(s) is not known, but it is
possible that they may occur in nature as bona fide 'metal
clusters' (Schmid, 1985), as has been suggested by Tredoux
et al. ( 1991 ), Ballhaus et al. (l 994) and Capobianco et al.
(1994). If this is the case, it would be possible to model PGE
behaviour in terms of cluster chemistry.
Special properties of metal clusters
Cluster chemistry is a relatively new field of study, and is
concerned with the transition in behaviour between the
atomic (or simple molecular) state and solid state of a
metallic element (Schmid, 1985; Stace, 1988; Cohen &
Knight, 1990). Research in the field initially centred mainly
on low-temperature gaseous clusters, but, more recently, work
at higher temperatures has been tremendously active because
of indications that cluster behaviour might underlie the ill-
understood processes of catalysis. Although cluster chemistry
still is in its scientific infancy, the following trends are already
quite clear:
1. Clusters are defined as any structure of 3-1000 atoms, in
which all atoms are connected to at least two other atoms
by metal-metal bonds (Schmid, 1985). The popular way to
describe clusters is the 'jellium' model (Cohen & Knight,
1990), in which the cluster is seen as having a central core
of atoms, surrounded by a cloud of electrons. Each atom
in the cluster contributes one electron to a cloud, and the
structure as a whole is uncharged.
2. Mass spectrometric studies has shown that certain 'magic
number' structures are favoured and are exceptionally
stable (Schmid, 1985). Explanation for these magic
numbers is contained in the jellium model for clusters
(Cohen & Knight, 1990). In discussions of heavy
transition metal clusters, a size of 10-100 atoms is most
commonly assumed (Schmid, 1985; Stace, 1988).
3. The heavy transition elements form more stable clusters
than the light transition elements (Vargas & Nicholls,
1986). This is due to the much more extensive overlap of
the d-orbitals of the more massive atoms. Thus, elements
in the second series will form more stable clusters than
163
Os, To = 30452 C
3000
-- --- ---- -----------------------------------------·-----
Ru, To= 2130RC
Rh, To = 19f56GC
2000
6
~
...••...
...
:I Pd, To = 1554!!C
HIOO
•Q.
E
~
Au, To = 106411C
1000
---· --- --- -------------- ---- -----------------·
• Calculated Tm
soo
o Experimental Tm
(Au only)
lO 20
Particle Diameter (nm)
Figure 5 Plot of experimentally determined depression of the melt-
ing point of Au as a function of cluster size (Buffat & Borel, 1976).
Also plotted are theoretical curves of values for Au and the PGE,
calcula~ed using the following equation (Allen et al., 1986): Tmffo =
I - (3(e/ps - e/p1)/(1 r) where: Tm= bulk melting temperature; To=
0
particle melting temperature; es, e1 = specific surface temperature of
solid and liquid resp.; Ps, p1 = density of solid and liquid resp.; lo=
latent heat per mass unit; and r = particle radius in nm.; the close cor-
respondense between the experimental and calculated values for Au
is taken as an indication that the curves for the PGE are realistic.
those in the first series, and the third series elements
should form the most stable clusters. The PGE will be
more inclined towards cluster behaviour than the base
metals, and Os, Ir and, Pt will form more stable clusters
than Ru, Rh, and Pd.
4. The behaviour of clusters cannot be predicted by
'classical' chemical principles: various studies on such
diverse properties as ionization potentials and nearest
neighbour distance has shown that the values for clusters
of an element is intermediate between that obtained for its
individual atoms and the bulk metal (Stace, 1988). An
example of how the melting point of Au is affected by
cluster size (Buffat & Borel, 1976) is shown in Figure 5,
with equivalent calculations for the PGE. It is clear that
clusters are more reactive than bulk metals, and that the
values of many physical properties (e.g. melting point) are
depressed in clusters relative to the bulk values.
5. Clusters are stabilized by the presence of appropriate
ligands (Schmid, 1985; Pruchnik, 1990). Most of the
pioneering experimental work has been done using
complex organic reagents (see Schmid, 1985, for some
164
examples), but theoretically most of the 'soft' ligands
(such as S, As, Sb, Te, CO) should be suitable to effect
such stabilization (Lindsay, 1989; McDonald, 1993). The
ligands do not form 'formal' chemical bonds with the
cluster core, but rather arrange themselves as symmetrical
(usually nearly spherical) envelopes around the cluster in
such a way that repulsion is minimized (Schmid, 1985).
The atoms in the ligand layer are highly mobile, so that
the structure as a whole develops a solid-like core with a
liquid-like surface (Schmid, 1985). This feature would
further enhance the reactivity of the clusters.
Evidence for the existence of PGE clusters
PGE clusters are easily formed under laboratory conditions
(Schmid, 1985); compounds such as Os,z(C0h 6 and
Os 20(C0) 40 are remarkably stable (Lewis & Moss, 1993; Si.iss-
Fink, 1991 ), and stable clusters containing 55 atoms have
been synthesized with Au, Pt, and Ru (Schmid, 1985). To
date, however, there is no direct evidence for the presence of
PGE clusters in natural materials. Nevertheless it is believed
that strong indications of cluster-like behaviour can be
deduced from the following:
In the experimental systems discussed earlier, there are
many features which could be modelled as being underpinned
by cluster behaviour, for example the fractionation of the light
PGE relative to the heavy PGE observed by Fleet & Stone
(1991), and the 'very small spherules' of an Fe-PGE alloy
reported by Amosse et al. (1990) within the quenched glass
products of their runs. It is possible that these spherules repre-
COALESCENCE STABILISATION
~ COLLECTION
/.nch pafuway
Figure 6 Schematic diagram of the behaviour of PGE clusters in a magmatic system, taken from Lindsay ( 1989).
S.Afr.Tydskr.Geol., 1995,98(2)
sent PGE clusters which coalesced in the molten silicate prior
to quenching. Ballhaus et al. (1994) specifically interpret
their results for Pt in fluid inclusions in terms of clusters, and
Capobianco et al. (1994) concede that clusters may be present
in the products of their experiments.
SIMS investigation of metallurgical NiCuS mattes has
shown that all the PGE except Pd.are distributed inhomogene-
ously, and tend to occur as discrete sub-microscopic inclu-
sions within the base metal sulphides (Lindsay, 1989). These
inclusions could be the solidified equivalents of PGE clusters,
which in the molten state were surrounded and stabilized by a
ligand envelope of S (± As, Sb,Te, etc.) anions. Analysis of
the Noril'sk sulphide ores by high resolution ion beam tech-
niques (Chryssoulis et al., 1991) showed a distribution of the
PGE which is exactly analogous to that of the synthetic
mattes.
Other results of natural systems include the micro-PIXE
analyses by Hattori et al. (1992) of sulphides in peridotite
xenoliths from Japan, Alaska, and South Africa, which show
that the PGE are extremely inhomogeneous. Those authors
suggest that the PGE in the mantle are probably present as
'discrete fine metal alloys' which are sub-microscopic in size.
Peach et al. who analysed co-existing sulphide and glass in
MORB, state that
'failure of the [sulphide] model to account for the
observed Ir abundances suggests that a phase(s) other
than sulfide influences Ir fractionation' (1990: 3388).
The authors of this article believe that it is reasonable to
suggest that this phase might be metallic Ir-rich clusters.
~ o r pathway
KEY: PGE
~ Fe
C)s
O As
S.Afr.J.Geol., 1995,98(2)
Cluster based model for PGE crystallization
The authors would like to propose the following model (see
Figure 6):
1. The PGE are present in a melt initially as metallic clusters
(-50-100 atoms per cluster) and not as single atoms nor
as individual PGE molecules (e.g. PGE-S or PGE-0,).
The depression of melting point which appears to be a
function of cluster-based behaviour (see Figure 5) would
offer an explanation for the apparently high reactivity of
the PGE at magmatic temperatures, in environments
which are essentially super-cooled with respect to most
PGE phases in the mantle;
2. The clusters are stabilized by surface adsorption of chal-
cogenides (S, As, Sb, Te; Lindsay, 1989) or other 'soft'
ligands (e.g. CO) (Schmid, 1985; McDonald, 1993). The
ligands are not bonded to the clusters in the classical
sense, but are merely adsorbed on the cluster surfaces: in
such systems, the application of formal concepts such as
partitioning and distribution coefficients would not be
appropriate;
3. In S-rich environments the PGE clusters, activated ('wet-
ted') by their chalcogenide envelopes, become primed for
inclusion in the sulphide melt. The PGE clusters remain
associated with the sulphide melt until they coalesce and
precipitate out (at the appropriate temperature) to form
PGE arsenides, tellurides, alloys, and complex sulphides.
That proportion of the PGE clusters which is not removed
by this mechanism, will later precipitate with the base
metal sulphides (BMS) as sub-microscopic inclusions.
Lower temperature lattice reorganization of the BMS can
lead to the expulsion of the PGE clusters along the grain
boundaries, where they will precipitate as PGM.
4. In S-poor environments the clusters will remain sus-
pended in the silicate melt until they can coalesce to form
alloys. If such coalescence happens early enough during
the crystallization history of the magma, the resulting
PGM might provide nucleation centres for early-forming
silicates and oxides. The well-documented association of
Os and Ir with such early crystallates is entirely in keeping
with the cluster model, because the high melting points
and electron shell characteristics of these two elements
predict that they should form the most stable and abundant
clusters. PGE clusters which remain too dispersed to pre-
cipitate as PGM may concentrate into the residual fluid,
which could become enriched in PGE, especially the LT-
PGE, analogous to the observations of Ballhaus et al.,
(1994). Such LTPGE-enriched intercumulus liquid would
provide the source of the late-stage remobilized PGE en-
richments seen in the hortonolite dunite pipes in the east-
ern lobe of the Bushveld Complex (McDonald, 1993).
Conclusions
A model is presented to explain the fractionation of the PGE
which implies a strong primary temperature control, and the
presence of the PGE in the mantle and in the magmas as poly-
atomic metallic clusters. According to this model, 'the PGE
collection (by sulphides, chromites) ... is ... largely a mecha-
nical process' (Lindsay, 1989). Because the distribution of the
PGE between the phases the magmatic system does not de-
pend on partitioning behaviour per se, it becomes unneces-
165
sary to postulate excessively high apparent D values for the
PGE, as has been suggested, for example, for some sulphide
deposits. The high apparent D values of these deposits can be
modelled as a Dmeta1/,ilica,e component (in which the 'metal' is
the metallic clusters) that is overprinted by the presence of
sulphide melt. This would bring the estimates based on geo-
logical observations in closer agreement with the experimen-
tal data, as in both cases very high values would refer to
metal-silicate, and not sulphide-silicate, partitioning.
This does not mean to imply that the PGE have no chal-
cophile tendencies, but rather that the presently inferred chal-
cophility as often deduced in the literature for those systems
which lead to S-poor, extremely PGE-rich ores (such as the
Merensky, UG-2 and J-M reefs) might be misleading, and
that such systems perhaps should not be subjected to rigour-
ous applications of sulphide models. It is suggested that the
possible contribution from an underlying siderophile control
should be kept in mind at all times. This might be especially
true for the HTPGE (Os, Ir, and Ru) and perhaps even Rh, and
might explain why the behaviour of these elements cannot be
predicted on the basis of the conventional sulphide models.
Acknowledgements
MT would like to thank the Foundation for Research Founda-
tion of South Africa, and the UCT Research Grant Committee
for financial support. The bulk of this work was done while
we were all at the Schonland Research Centre of the Univer-
sity of the Witwatersrand, which is retrospectively thanked
for generous support. Petrus le Roux is thanked for help with
preparing Figure 1. The thoughtful reviews of Chris Ballhaus
and Maryse Ohnenstetter are acknowledged with gratitude.
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