Miner Deposita
DOI 10.1007/s00126-012-0413-8
ARTICLE
Platinum-group element distribution in base-metal sulfides
of the Merensky Reef from the eastern and western Bushveld
Complex, South Africa
Inga Osbahr & Reiner Klemd & Thomas Oberthr &
Helene Brtz & Robert Schouwstra
Received: 27 June 2011 / Accepted: 12 March 2012
# Springer-Verlag 2012
Abstract Base-metal sulfides in magmatic Ni-Cu-PGE
deposits are important carriers of platinum-group elements
(PGE). The distribution and concentrations of PGE in pent-
landite, pyrrhotite, chalcopyrite, and pyrite were determined
in samples from the mineralized portion of four Merensky
Reef intersections from the eastern and western Bushveld
Complex. Electron microprobe analysis was used for major
elements, and in situ laser ablation inductively-coupled
plasma mass spectrometry (LA-ICP-MS) for trace elements
(PGE, Ag, and Au). Whole rock trace element analyses were
performed on representative samples to obtain mineralogical
balances. In Merensky Reef samples from the western
Editorial handling: C. Li
Electronic supplementary material The online version of this article
(doi:10.1007/s00126-012-0413-8) contains supplementary material,
which is available to authorized users.
I. Osbahr (*) : R. Klemd : H. Brtz
GeoZentrum Nordbayern, University of Erlangen-Nrnberg,
Schlossgarten 5a,
91054 Erlangen, Germany
e-mail: osbahr@geol.uni-erlangen.de
R. Klemd
e-mail: klemd@geol.uni-erlangen.de
H. Brtz
e-mail: braetz@geol.uni-erlangen.de
T. Oberthr
Federal Institute for Geosciences and Natural Resources (BGR),
Stilleweg 2,
30655 Hannover, Germany
e-mail: thomas.oberthuer@bgr.de
R. Schouwstra
Anglo American Research,
8 Schonland Street, Theta,
Johannesburg( PO Box 106( Crown Mines 2025, South Africa
e-mail: robert.schouwstra@angloamerican.com
Bushveld, both Pt and Pd are mainly concentrated in the
upper chromitite stringer and its immediate vicinity. Sam-
ples from the eastern Bushveld reveal more complex distri-
bution patterns. In situ LA-ICP-MS analyses of PGE in
sulfides reveal that pentlandite carries distinctly elevated
PGE contents, whereas pyrrhotite and chalcopyrite only
contain very low PGE concentrations. Pentlandite is the
principal host of Pd and Rh in the ores. Palladium and Rh
concentrations in pentlandite reach up to 700 and 130 ppm,
respectively, in the samples from the eastern Bushveld, and
up to 1,750 ppm Pd and up to 1,000 ppm Rh in samples
from the western Bushveld. Only traces of Pt are present in
the base-metal sulfides (BMS). Pyrrhotite contains signifi-
cant though generally low amounts of Ru, Os, and Ir, but
hardly any Pd or Rh. Chalcopyrite contains most of the Ag
but carries only extremely low PGE concentrations. Mass
balance calculations performed on the Merensky Reef sam-
ples reveal that in general, pentlandite in the feldspathic
pyroxenite and the pegmatoidal feldspathic pyroxenite hosts
up to 100 % of the Pd and Rh and smaller amounts (10
40 %) of the Os, Ir, and Ru. Chalcopyrite and pyrrhotite
usually contain less than 10 % of the whole rock PGE. The
remaining PGE concentrations, and especially most of the Pt
(up to 100 %), are present in the form of discrete platinum-
group minerals such as cooperite/braggite, sperrylite, mon-
cheite, and isoferroplatinum. Distribution patterns of
whole rock Cu, Ni, and S versus whole rock Pd and Pt
show commonly distinct offsets. The general sequence of
offset patterns of PGE and BMS maxima, in the order
from bottom to top, is Pd in pentlanditePd in whole
rock (Cu, Ni, and S). The relationship is not that
straightforward in general; some of the reef sequences
studied only partially show similar trends or are more
complex. In general, however, the highest Pd concentra-
tions in pentlandite appear to be related to the earliest,

volumetrically rather small sulfide liquids at the base of the
Merensky Reef sequence. A possible explanation for the
offset patterns may be Rayleigh fractionation.
Keywords Merensky Reef . Bushveld Complex . South
Africa . Platinum-group elements . Base-metal sulfides .
Trace element distribution patterns . LA-ICP-MS
Introduction
The Bushveld Complex in South Africa, the largest known
layered intrusion on Earth, contains the worlds most impor-
tant platinum-group elements (PGE) reserves (e.g., Vermaak
1995; Cawthorn 1999; Hulbert and von Gruenewaldt 1982;
Misra 2000; von Gruenewaldt 1977, 1979; Willemse 1969).
The Bushveld Complex formed at 2.05 Ga in an intraplate
setting and covers an area of ca. 65,000 km2 (Walraven et al.
1990; Eales and Cawthorn 1996; Cawthorn et al. 2006). The
Complex has been subdivided into the Rustenburg Layered
Suite (RLS), the Lebowa Granite Suite, the Rashoop Grano-
phyre Suite and the Rooiberg Group (e.g., Hatton and
Schweitzer 1995; SACS 1980). The Bushveld Complex
intruded the sediments of the Transvaal Supergroup. A large
part of the Complex is covered by younger sedimentary
rocks (e.g., Cheney and Twist 1991). The Critical Zone of
the RLS hosts the PGE mineralization which occurs in three
layers, namely the Merensky Reef, the UG-2 chromitite, and
the Platreef. Detailed descriptions of the UG-2 were given
by Cawthorn (1999) and of the Platreef by Holwell and
McDonald (2006, 2007). The Merensky Reef horizon, the
object of this study, occurs in the uppermost part of the
Critical Zone and is exposed over some hundred kilometers
in the eastern and western limbs of the Bushveld Complex.
Variations in the bounding lithologies, grade, and thickness
do occur; however, the highest PGE grades tend to be found
within two thin chromitite layers, with lower grade between
them (Cawthorn 1999). Furthermore, the Merensky Reef is
characterized by elevated sulfide contents (up to ca. 3 %)
and widths between 4 cm and 4 m (commonly around 1 m).
Mining widths are usually about 80 cm. The average grade
of the Merensky reef is typically 57 g/t PGE. There are
several processes that may be responsible for the origin of
the PGE mineralization. For example, Kinloch (1982),
Campbell et al. (1983), and Naldrett (1989a) suggested that
the PGE precipitated from magma and accumulated on the
top of a crystal pile, whereas Vermaak and Hendriks (1976),
Boudreau (1992), and Boudreau and Meurer (1999)
preferred an upward infiltration process in which the
PGE have been precipitated and transported from the
footwall by ascending, volatile-rich fluids. Although the
exact process responsible for the PGE mineralization remains
under debate, the close spatial and possibly genetic relationship
Miner Deposita
between PGE mineralization and the base-metal sulfides
(BMS) is obvious.
BMS in orthomagmatic Ni-Cu-PGE deposits often carry
significant amounts of PGE. Several studies were undertaken
previously to elucidate the distribution of the PGE between
various sulfides such as pentlandite, pyrrhotite, chalcopyrite
and pyrite (e.g., Dare et al. 2010; Godel et al. 2007; Godel and
Barnes 2008; Holwell and McDonald 2010; Oberthr et al.
1997, 2003). The distribution of PGE in BMS mainly results
from sulfide liquid fractionation as revealed by experimental
investigations (e.g., Barnes and Picard 1993; Barnes et al.
1997, 2001; Li et al. 1996; Mungall et al. 2005; Naldrett
2004; Peregoedova et al. 2004). The experimental studies
indicated that subsequent to the separation of a Fe-Ni-Cu
sulfide liquid from a mafic magma, a monosulfide solid solu-
tion (mss) and a Cu-rich liquid form at ca. 1,000C (e.g.,
Kullerud et al. 1969; Naldrett 1989b). Os, Ir, Ru, and Rh, as
suggested by experimentally determined partition coefficients,
preferentially partition into the Fe-rich mss, whereas Cu, Pt,
Pd, Ag, and Au become enriched in the Cu-rich fractionated
liquid. In addition, the partition coefficients strongly depend
on the Fe/S ratio of a magmatic sulfide liquid (Barnes et al.
2001). According to Li et al. (1996), the partition coefficients
of all metals increase between mss and liquid with increasing
S content, both in the sulfide liquid and in the mss. The
Cu-rich liquid then crystallizes as intermediate solid solu-
tion (iss) at ca. 900C. At temperatures below 600C, the
iss breaks down to chalcopyrite and cubanite, and the mss
to pyrrhotite and pentlandite. As a result, pyrrhotite and
pentlandite should be enriched in Os, Ir, Ru, and Rh and
chalcopyrite in Pd, Pt, Ag, and Au, if no discrete platinum-
group minerals (PGM) crystallize or no subsolid re-
equilibration takes place on further cooling. However, in
previous studies on different Ni-Cu-PGE deposits (Barnes
et al. 2006; Dare et al. 2010; Godel et al. 2007), especially
distinct enrichments of Pd and Pt in chalcopyrite were not
observed. Consequently, postmagmatic processes are
thought to play an important role in the redistribution of
PGE in magmatic sulfide ores (see Dare et al. 2010) for
discussion and references therein). For instance, Barnes et
al. (2006) and Dare et al. (2010) suggested that the enrich-
ment of Pd in pentlandite is due to diffusion during its
exsolution from the mss. A small quantity of Pd may
originate from Pd in the original mss structure whereas
most of Pd was derived from the nearby iss by diffusion
(Dare et al. 2010).
The present study concentrates on the PGE distribution in
the Merensky Reef at two locations each of the eastern and
western Bushveld Complex. Selected samples from four
drill cores, covering the entire section of the mineralized
part of the Merensky Reef, were analyzed for major and
trace elements. In addition, the composition of the mineral
phases such as silicates, chromite, and sulfides was
Miner Deposita
determined using electron microprobe and in situ laser ab-
lation inductively-coupled plasma mass spectrometry (LA-
ICP-MS). The main objective of this study is to document
the small-scale distribution of the PGE in the ores (hosted in
sulfides and/or as discrete PGM) in order to improve our
understanding of the genetic processes which formed the
mineralization of the Merensky Reef.
Sample description
Stratigraphy
The samples investigated originate from four pristine drill
cores, SD124 and SD134 from the farm Styldrift in the
western Bushveld, and drill cores US200 and US186 from
the farm Umkoanesstad in the eastern Bushveld (Fig. 1).
The samples stem from the economically mineralized part of
the reef. The mining width generally encompasses material
from 30 cm above the top chromitite stringer down to ca.
1.5 m below the top chromitite. The cores were drilled by
Anglo American Platinum in 2008.
Fig. 1 a Simplified geological map of the Bushveld Complex, South
Africa, with the locations of the drill cores SD124 and SD134
(western limb, Styldrift farm; SD) and US200 and US186 (eastern
limb, Umkoanesstad farm, Lebowa Mine; US), modified after Cawthorn
et al. (2002). The map also shows the localities of previous whole-rock
PGE studies at Rustenburg (Godel et al. 2007; Ballhaus and Sylvester
The normal Merensky Reef sequence as described in
the literature for example by Wagner (1929) and Vermeulen
(2010) consists of a pegmatoidal (feldspathic) pyroxenite
which is occasionally interlayered with a pegmatoidal feld-
spathic harzburgite at its base. One, occasionally two, chro-
mitite layers, 12 cm thick, characterize the upper and lower
limits of the main economic mineralization. The reef undu-
lates into the footwall which commonly consists of an
approximately 5 m thick poikilitic anorthosite layer, or
occasionally of gabbronorite. The 1.53.5 m thick hanging
wall of the Merensky Reef consists of feldspathic pyroxenite
(the Merensky Pyroxenite) or norite (Fig. 2; e.g., Wagner
1929; Vermeulen 2010). The Merensky Reef shows many
variations in host rock lithologies and distribution of the
mineralization, and was for example further divided in a 4
20 cm wide thin reef facies, a 2040 cm wide medium reef
facies, and a 12 m wide thick reef facies in the Rustenburg
area of the western Bushveld (e.g., Wilson et al. 1999).
Normal sections of the Merensky Reef in the western
and eastern Bushveld are shown in Fig. 2.
All investigated drill cores show normal Merensky
Reef profiles as displayed in Fig. 2. Drill core SD124
2000), Styldrift (Naldrett et al. 2009), and Winnaarshoek (Mitchell and
Scoon 2007) as well as of LA-ICP-MS studies on PGE in base-metal
sulfides at Rustenburg (Godel et al. 2007; Ballhaus and Sylvester
2000). b Simplified stratigraphy of the Bushveld Complex (after
Eales and Cawthorn 1996)

Fig. 2 Sketches showing the distribution of rock units and mineraliza-
tion in the normal Merensky Reef of the western Bushveld (Rustenburg
area) after Vermaak and Hendriks (1976) and in the eastern Bushveld
(Lebowa mine) after Schwellnus et al. (1976), modified after Naldrett
(1989a, b)
(western Bushveld) consists of a ca. 2.5-m thick pegmatoidal
feldspathic pyroxenite with small lenses of harzburgite in the
lower part. Drill core SD124 has one 5-mm thick lower
chromitite stringer and two 5- and 10-mm thick upper chro-
mitite stringers. The footwall consists of a poikilitic anortho-
site while the hanging wall consists of feldspathic pyroxenite.
The mineralization is tightly confined to the area of and
around the upper chromitite stringers (Fig. 3).
Drill core SD134 (western Bushveld) shows mineraliza-
tion mainly confined to a ca. 50-cm thick pegmatoidal
feldspathic pyroxenite which is bound by a 5-mm thick
lower chromitite stringer and two 5- and 10-mm wide upper
chromitite stringers. The footwall consists of poikilitic an-
orthosite and the hanging wall of feldspathic pyroxenite
followed by gabbronorite (Fig. 3).
Drill core US200 (eastern Bushveld) consists of a 50-
cm pegmatoidal feldspathic pyroxenite, overlain by a 7-
mm thick chromitite stringer (termed lower chromitite in
Fig. 4) and a 75-cm thick feldspathic pyroxenite fol-
lowed by norite. A sulfide stringer occurs 25 cm above
the chromitite stringer. The footwall consists of gabbro-
norite which also contains some PGE-poor sulfide
stringers. The mineralization is distributed around the
chromitite and the sulfide stringers in the pyroxenite
(Fig. 4).
Drill core US186 (eastern Bushveld) shows a 75-cm
thick pegmatoidal feldspathic pyroxenite overlain by an
at least 75-cm thick feldspathic pyroxenite. The transi-
tion between both units is characterized by a 7-mm thick
lower chromitite stringer. A 1-cm thick upper chromitite
stringer occurs about 50 cm above the lower chromitite
stringer. The footwall consists of feldspathic pyroxenite.
Miner Deposita
The mineralization is distributed around the chromitite
stringers (Fig. 4).
Petrography
Pyroxenite
Two types of pyroxenite occur in the sequence of the Merensky
Reef, the normal feldspathic pyroxenite (Fig. 5a) and the
pegmatoidal feldspathic pyroxenite (Fig. 5b). The units are
characterized by orthopyroxene contents of 7291 vol.% and
up to 10 vol.% of clinopyroxene. Both units are mineralog-
ically similar and only differ in the sizes of the orthopyrox-
ene grains which vary between 2 and 4 mm in diameter in
the feldspathic pyroxenite and up to several centimeters in
length in the pegmatoidal feldspathic pyroxenite. Clinopyr-
oxene usually occurs as inclusion in orthopyroxene and only
rarely as a matrix mineral. The other main component in
these units is xenomorphic plagioclase which has a similar
grain size as the pyroxene and normally occurs as an
interstitial mineral. In all investigated drill cores, the feld-
spathic pyroxenite and the pegmatoidal feldspathic pyroxe-
nite units contain most of the BMS, which reach up to
5 modal %. Disseminated chromite grains and accessory
phlogopite with grain sizes up to 1 and 3 mm, respectively,
are frequently present.
Norite and gabbronorite
The associated norite and gabbronorite comprise 6067 vol.%
orthopyroxene and up to 35 vol.% plagioclase with similar
grain sizes as those in the feldspathic pyroxenite. Minor
components in all investigated units are phlogopite, dissemi-
nated sulfides and chromite as well as rare rutile and olivine.
Pyroxene-bearing anorthosite
The pyroxene-bearing anorthosite (Fig. 5c) is characterized
by a plagioclase content of 80100 vol.% and up to
20 vol.% of mainly orthopyroxene. Plagioclase and pyrox-
ene reach up to 3 mm in size.
Harzburgite
Harzburgite lenses occur in the pegmatoidal feldspathic
pyroxenite of drill core SD124. The harzburgite is charac-
terized by up to 65 vol.% pyroxene contents, up to 20 vol.%
of olivine, and up to 10 vol.% of plagioclase. Olivine and
plagioclase show average grain sizes of ca. 5 mm whereas
the pyroxenes reach up to 1.5 cm in diameter. The olivine
grains are at least partly replaced by serpentine minerals
(Fig. 5d). Disseminated sulfides, chromite and phlogopite
are also present.
Miner Deposita
Fig. 3 ab Stratigraphic variation of Pd, Rh and Ru contents in pent-
landite (left) and whole rock Pt, Pd, Cu, Ni, and S contents (right) in drill
cores SD124 and SD134 (western Bushveld). The highest contents of Pd,
Rh, and Ru in pentlandite are associated with the upper chromitite stringer
Chromite
Chromite either occurs in the form of thin stringers at the top
and bottom of the Merensky Reef, or is disseminated through-
out most of the units. The chromitite stringers consist of up to
95 vol.% chromite (Fig. 5e, f). The grain sizes of the idiomor-
phic to hypidiomorphic chromite usually range between 100
and 200 m but may reach up to 750 m in diameter. The
and the underlying pegmatoidal feldspathic pyroxenite. The highest Pt
and Pd concentrations (whole rock) occur at the upper chromitite stringer
in both drill cores. Note the distinct covariance of Pd, Pt, and Cu (sulfide)
as displayed by their similar distribution patterns
chromite grains are embedded in a matrix of plagioclase with
minor pyroxene and phlogopite. Inclusions of magnetite, sul-
fides, and/or rutile are occasionally found in the chromites.
Analytical methods
Major elements were determined using a JEOL JX8 electron
microprobe at the GeoZentrum of the University of Erlangen,

Fig. 4 ab Stratigraphic variation of Pd, Rh and Ru contents in
pentlandite (left) and whole rock Pt, Pd, Cu, and Ni contents (right)
in drill cores US200 and US186 (eastern Bushveld). In drill core
US200, the highest contents of Pd, Rh, and Ru in pentlandite were
detected in the pegmatoidal feldspathic pyroxenite. Ellipses show the
three different US200 lithologies, namely the lower chromitite stringer,
which operates with a 20 kV acceleration voltage, a current of
20 nA and a focused beam with a counting time for peak and
background of 20 and 10 s, respectively. In situ trace element
analysis of sulfides was conducted by LA-ICP-MS on 43
polished thin sections from the four drill cores (13 thin sections
from drill core SD124, 11 thin sections from drill core SD134,
nine thin sections from drill core US200, and ten thin sections
from US184). Pentlandite, pyrrhotite and chalcopyrite as well
Miner Deposita
the sulfide-rich feldspathic pyroxenite, and the pegmatoidal pyroxe-
nite, investigated for PGM by Rudashevsky (2011). In drill core
US186, the highest Pd contents in pentlandite occur in the pegmatoidal
feldspathic pyroxenite below the lower chromitite stringer, whereas Rh
and Ru show maximum values further up, coinciding with the lower
and upper chromitite stringer
as minor pyrite were analyzed with the main focus on PGE, Au
and Ag concentrations.
The concentrations of the PGE (99Ru, 101Ru, 103Rh,
105
Pd, 108Pd, 189Os, 193Ir, 195Pt) as well as 197Au, 107Ag,
185
Re, 59Co, 60Ni, 61Ni, 63Cu in BMS were determined
using the LA-ICP-MS at the University of Erlangen. The
LA-ICP-MS system consists of a laser ablation unit
(UP193FX, Eximer, New Wave Research), coupled with a
Miner Deposita

Fig. 5 Photomicrograpghs of
thin sections. a Feldspathic
pyroxenite. Note inclusions of
clinopyroxene (Cpx) and
plagioclase (Pl) in
orthopyroxene (Opx). Slide
SD124-14_1. b Pegmatoidal
feldspathic pyroxenite showing
orthopyroxene, clinopyroxene
and interstitial plagioclase
(SD124-15). c Pyroxene-
bearing anorthosite consisting
of plagioclase with interstitial
orthopyroxene and phlogopite
(SD124-30). d Harzburgite;
olivine (Ol) partly replaced by
serpentine minerals (SD124-
29). e Upper chromitite stringer
at the transition between the
feldspathic pyroxenite and the
pegmatoidal feldspathic
pyroxenite (SD124-14_2). f
Contact between pegmatoidal
feldspathic pyroxenite and
chromitite layer (US200-9)

quadrupole ICP-MS (Agilent 7500i). For external calibra-
tion the following standard reference materials (SRM) were
used: Po724 B2 SRM (synthetic pyrrhotite, Memorial Uni-
versity Newfoundland) for Pd, Rh, Pt, Ru, Os, Ir and Au;
MASS-1 polymetal sulfide (USGS) for Co, Ag, and Cu and
(Fe, Ni)1xS (Wohlgemuth-Ueberwasser et al. 2007) for Ni,
Re, and S. Reproducibility for SRM is <9 % and the accu-
racy, tested by ablating the PGE SRM FeNiS standard, is
<15 %. The standard measurements of all sessions are given
in Electronic Supplementary Material (ESM) 1.
LA-ICP-MS measurements were conducted using a spot
size of 50 m in diameter, a laser frequency of 15 Hz and
0.32 GW/cm2, and a fluence of 1.62 J/cm2. For smaller
grains, a 35 m spot was used. The carrier gas consists of
a mixture of 0.65 l/min helium and 1.06 l/min argon. Ac-
quisition time was 20 s for the background and 20 s for the
mineral analysis. Signal quantification was carried out by
GLITTER (van Achterbergh et al. 2000) using sulfur as an
internal standard as determined by means of the electron
microprobe.
Various interferences caused by the carrier and plasma
gas Ar lead to falsified results for Ru, Rh, and Pd, if not
corrected. 99Ru is interfered by 63Cu36Ar and 59Co40Ar,
101
Ru by 63Cu38Ar, 65Cu36Ar and 61Ni40Ar, 103Rh by
63
Cu40Ar, 65Cu38Ar and 67Zn36Ar, 105Pd by 65Cu40Ar and
108
Pd by 68Zn40Ar. 108Pd is additionally interfered by 108Cd.
Due to the extremely low relative isotope abundance of
36
Ar (0.337 %) and 38Ar (0.063 %), their effect on 99Ru,
101
Ru, and 103Rh is negligible. Only a few counts per second
for Zn were recorded for the sulfides in this study, thus
excluding a significant influence. However, a remarkable
impact occurs for CuAr on 103Rh and 105Pd when analyzing
chalcopyrite. The argide-unaffected 108Pd for chalcopyrite
can be used, which nonetheless requires a correction for the
elemental interference from 108Cd. A PGE-free hydrother-
mal chalcopyrite from Messina (South Africa) was analyzed
to check the 63Cu40Ar and the 65Cu40Ar production; the
results vary from 4 to 5 ppm for 103Rh and 68 ppm for
105
Pd. The corrected values for Pd and Rh in chalcopyrite
are given in ESM 2ad.
Since the interference of 61Ni40Ar lead to an overestima-
tion of 101Ru in pentlandite, 99Ru was used instead to obtain
the correct concentration. Numerous measurements on pent-
landite yield 0.5 ppm as the lowest concentration for Ru,
indicating that this value solely originates from the Ni-
argide. This concentration always lies within the 1 error
 Miner Deposita

margin for every analysis. For Co-rich minerals, the inter-
ference 99Ru by 59Co40Ar has to be corrected. However, as the
pentlandites in this study contain a maximum of 0.5 wt% Co,
no correction is needed.
The PGM distributions and their compositions were exem-
plarily investigated on some composite samples from drill core
US200 using electric pulse disaggregation (EPD) and hydro-
separation (HS) to obtain concentrates of which polished sec-
tions were prepared. The sections were studied using a
scanning electron microprobe (Camscan-4DV, Link AN-
10000). This work was conducted by CNT-Mineral Consulting
Inc. in St. Petersburg (Rudashevsky 2011). The above combi-
nation of methods delivers detailed information on grain sizes,
mineral associations, and recovery of precious metals (PGM,
Ag, and Au). For more information, see Cabri et al. (2008).
Representative samples, covering the entire section of the
mineralized part of the Merensky Reef, were taken from the
four drill cores (SD124, SD134, US200, and US186) for
bulk rock chemical analyses. Each sample with a length of
1625 cm of halved 3.5 cm diameter drill cores were pul-
verized and analyzed for Pd, Pt, and Rh using the Ni-sulfide
fire assay method. Cu, Ni, and Cr were analyzed by XRF and
S by Leco CNS. These analyses were conducted by Anglo
Americans Technical Solutions-Research (Johannesburg,
South Africa). Additional sulfur and PGE analyses were con-
ducted on smaller samples (7 cm in length) by Actlabs
(Ontario, Canada) in case of 20 cm long core samples which
had PGE contents below the detection limit.
Results
Whole-rock chemistry
The Merensky Reef is called top loaded if the maximum
PGE concentration is found within the upper chromitite
layer and its immediate vicinity (in the following referred
to as upper chromitite layer) or bottom loaded if it
occurs within the lower chromitite stringer and its immedi-
ate vicinity (in the following, referred to as lower chromi-
tite stringer). The whole rock Pd, Pt, and Rh concentrations
are listed in Table 1.
The Pt and Pd whole-rock distribution throughout the
four drill cores generally imply top loaded mineralization
in drill cores SD124 and SD134 (western Bushveld) as well
as in US200 (eastern Bushveld; Figs. 3 and 4). In drill core

Table 1 Whole-rock data of Pt, Pd and Rh, depth, lithotype, modal content of sulfides and calculated proportions of pentlandite, pyrrhotite, and
chalcopyrite

Sample From To Pt (ppm) Pd (ppm) Rh (ppm) Lithotype Modal content Pentlandite Pyrrhotite Chalcopyrite
Sulfide Calculated proportion

SD124
14 666.25 666.50 0.87 0.31 0.10 Feld. Px 1 38.75 34.34 26.91
15 666.50 666.74 5.69 1.96 0.37 Feld. Px 2 34.25 40.89 24.87
16 666.74 667.00 10.34 3.63 0.85 Upper chr. 0.5 38.39 40.78 20.83
17 667.00 667.26 2.97 1.62 0.22 Peg. Px 1.3 44.25 32.20 23.55
18 667.26 667.52 0.74 0.52 0.05 Peg. Px 0.75 41.54 5.05 53.41
19 667.52 667.78 2.70 0.89 0.13 Peg. Px 1.5 38.52 38.52 22.96
20 667.78 668.04 1.19 0.67 0.06 Peg. Px 0.5 37.59 34.57 27.84
21 668.04 668.30 0.26 0.21 <0.01 Peg. Px 0.5 43.65 32.44 23.91
22 668.30 668.56 0.59 0.41 0.04 Peg. Px 0.75 55.32 21.14 23.53
SD134
14 611.86 612.13 0.07 0.42 0.14 Feld. Px 1.5 58.76 18.51 22.73
15 612.13 612.40 1.87 1.34 0.45 Feld. Px 1.5 51.16 27.54 21.29
16 612.40 612.66 2.85 2.07 0.53 Feld. Px 2 40.74 41.46 17.81
17 612.66 612.96 8.10 5.42 0.80 U-chr./Peg. Px 3 42.55 38.71 18.74
18 612.96 613.25 9.69 2.19 0.34 Peg. Px/L-chr. 6 39.09 31.94 28.98
US200
US200-7A 918.30 918.36 3.49 5.16 0.21 Feld. Px. 4 56.63 29.36 14.01
US200-8 918.45 918.52 4.13 2.29 0.18 Sulf. Stringer 7.5 53.49 25.00 21.51
US200-9 918.72 918.78 1.74 0.21 0.06 Lower Chr. 1.5 26.97 43.35 29.67
US200-10_1 918.80 918.86 0.07 0.02 <0.2 ppb Peg. Px. 1.5 3.02 61.67 35.30
US200-11 919.05 919.11 0.26 0.39 0.01 Gabbronorite 0 18.14 55.04 26.82
US200-12 919.30 919.37 6.21 2.16 0.23 Gabbronorite 2.5 59.37 31.30 9.32
Miner Deposita
US186, platinum shows two peaks around the lower and
upper chromitite stringers whereas Pd is somewhat uniform-
ly distributed (Fig. 4).
In our samples, Pt and Pd throughout the drill cores
reveal maximum contents of 10 and 6 ppm in the western
Bushveld, and 5 and <2 ppm in the eastern Bushveld,
respectively. The contents of Pt always exceed those of Pd
in the vicinity of the chromitite stringers in all drill cores. Pt
and Pd exhibit similar trends in the area between the lower
and upper chromitite stringer.
Figures 3 and 4 show the bulk chemical distribution
patterns of Pd, Pt, Cu, Ni, and S in order to shed light on
possible relationships between the distributions of the PGE
and the sulfides. In the drill cores of the western Bushveld,
the trends of S, Ni, and Cu closely follow those of Pd and Pt.
However, Pd and Pt distribution patterns are distinctly dis-
placed compared to those of Cu and Ni in the drill cores
from the eastern Bushveld but only slightly displaced in the
drill cores from the western Bushveld (Figs. 3 and 4). The
concentration peaks of Pd and Pt always occur in or in the
immediate vicinity of the chromitite stringers, indicating a
certain link of Pd and Pt with chromitite (Figs. 3 and 4).
The whole rock PGE distribution in the drill cores SD134
and SD124 corroborate former studies which describe sim-
ilar distributions throughout the Merensky Reef in samples
Fig. 6 Whole rock data of the samples of the four drill cores studied.
Note that only samples with >0.1 ppm Pt (mineralized) are shown. a
Plot of Cu versus PPGE (Pt+Pd+Rh); note the distinct covariance.
from the Styldrift farm (drill cores SD22-3 and SD46) in the
western Bushveld (Fig. 1a; e.g., Naldrett et al. 2009). Fur-
thermore, the PGE distribution patterns throughout the Mer-
ensky Reef in the drill cores of the present study from the
eastern Bushveld, with maximum PGE+Au concentration
of 6 and 9 ppm at the lower and upper chromitite stringer,
respectively, are similar to typical Merensky Reef profiles
as reported by Mitchell and Scoon (2007)their channel
AF, Winnaarshoek. Notably, the PGE+Au concentrations in
the Merensky Reef profiles at Winnaarshoek are slightly
higher (6 and 12 ppm) at the lower and upper chromitite
stringer, respectively (Mitchell and Scoon 2007).
As indicated by the bulk rock distribution patterns, ele-
ment plots show positive covariances between whole rock
PPGE (Pt+Pd+Rh) and Cu (Fig. 6a), and also Ni (Fig. 6b)
in the samples from both the eastern and western Bushveld.
A distinct covariance is displayed by whole-rock PPGE and
S (Fig. 6c), whereas whole-rock PPGE and Cr (Fig. 6d)
show a poor interrelationship. Correlation coefficients for
each binary plot are listed in ESM 3.
The drill core samples from the western Bushveld reveal
whole rock Pt/Pd ratios between 0.2 and 16. The samples of
drill core SD124 show a Pt/Pd ratio of 16 in the vicinity of
the lower chromitite stringer, while the remaining parts of
the drill core have maximum Pt/Pd ratios of 5. The entire
b Plot of Ni versus PPGE. c Plot of whole rock PPGE versus S. d Plot
of PPGE versus Cr2O3

section of this drill core reveals a slightly increasing Pt/Pd
ratio from the lower to the upper portion of the reef. Drill
core SD134 has the highest Pt/Pd ratio of 5 in the vicinity of
the lower chromitite stringer. The remaining parts of the drill
core exhibit Pt-Pd ratios of 3. Increasing Pt/Pd ratios occur
from the footwall to the hanging wall of the Merensky Reef.
In the eastern Bushveld, the samples from both drill cores
reveal tendencies of increasing Pt/Pd ratios from the lower
to the upper portion of the reef. Drill core US200 shows a
Pt/Pd ratio of 3 in the range of the upper chromitite stringer
which otherwise ranges between 0.6 and 2. Drill core
US186 has Pt/Pd ratios between 3 and 5.5 in the immediate
vicinity of the chromitite stringers. The footwall of the reef
has a Pt/Pd ratio <1 and the hanging wall of ca. 1.5.
Base-metal sulfides
Disseminated sulfides occur throughout the Merensky Reef
and the immediate wall-rocks showing larger grain sizes and
modal contents in the pegmatoidal feldspathic pyroxenite.
The BMS usually comprise coarse-grained irregular granu-
lar aggregates consisting of chalcopyrite, pentlandite, pyr-
rhotite, and minor pyrite (Fig. 7a). Occasionally, pentlandite
occurs as exsolution flames in pyrrhotite (Fig. 7b) or in
coarse-grained granular aggregates intimately intergrown
with pyrrhotite only (Fig. 7c). Cubanite and PGM are ac-
cessory minerals (Fig. 7d). The modal content of the sulfides
varies from 1 to 5 vol.% in the norite, gabbronorite, and
feldspathic pyroxenite and reaches almost 8 vol.% in the
sulfide-rich layers of the feldspathic pyroxenite of drill core
US200. The sulfide assemblage is made up of ca. 45 modal %
pentlandite, 25 % chalcopyrite, and 30 % pyrrhotite
(Table 1); however, the highest concentration of chalcopy-
rite occurs ca. 5 and 15 cm below the chromitite stringers in
the medium and the wide reefs, respectively. On the expense
of pyrrhotite, the modal amount of pyrite increases from the
bottom to the top in drill core US200. The grain sizes of the
sulfides and sulfide aggregates vary from a few micrometers
in the feldspathic pyroxenite to around 1 cm in the pegma-
toidal feldspathic pyroxenite. Notably, the majority of the
BMS occur in the pegmatoidal and feldspathic pyroxenite
units, whereas the norite and gabbronorite units are almost
barren of BMS.
PGE in pentlanditestratigraphic variation
In order to determine the trace element chemistry of the
BMS, 484 analyses were conducted. The average PGE con-
tents in pentlandite, chalcopyrite, pyrrhotite, and pyrite are
listed in ESM 2ad. In case of the detection of micro-
inclusions of PGM, individual analyses were removed from
the average values. Examples for time-resolved spectra of
laser analyses with and without a PGE-rich inclusion in
Miner Deposita
BMS are given in Fig. 8. Individual as well as multiple
grains of the various sulfides from the same polished thin
sections show very similar PGE contents, with only small
standard deviations (see ESM 2ad).
Variations of the PGE contents in BMS with stratigraphy
exist in all four drill cores. In drill core SD124, Pd
(1,800 ppm), Rh (1,400 ppm), Ru (60 ppm), and Ir (95 ppm)
in pentlandite show a top-loaded mineralization. However, the
area of the pegmatoidal feldspathic pyroxenite, located be-
tween the upper and lower chromitite stringer, also shows
elevated contents of up to 250 ppm Pd, 100 ppm Rh,
45 ppm Ru, 8 ppm Os, and 12 ppm Pt in pentlandite. The
lower chromitite stringer and its surroundings were not ana-
lyzed due to the absence of sulfides (Fig. 3).
Drill core SD134 shows a top-loaded mineralization for
Pd (500 ppm), a more irregular distribution of Rh (ca.
80 ppm in the lower and upper chromitite stringer, respec-
tively) and a bottom-loaded mineralization for Ru (50 ppm)
in pentlandite. Os, Ir, and Pt reach less than 11 ppm in the
pegmatoidal feldspathic pyroxenite. The concentrations of
Rh and Ru decrease whereas that of Pd steadily increases
from the lower to the upper chromitite stringer in the peg-
matoidal feldspathic pyroxenite (Fig. 3).
In drill core US200, Pd (700 ppm), Rh (55 ppm), Ru
(65 ppm), Os (11 ppm), Ir (14 ppm), and Pt (9 ppm) in
pentlandite show maximum concentrations in the immediate
vicinity of the pegmatoidal feldspathic pyroxenite below the
chromitite stringer. A further concentration peak is noted for
Rh (30 ppm) in the chromitite stringer. Furthermore, Pd and
Ru show additional concentration peaks (Pd0200 ppm and
Rh015 ppm) at the sulfide stringer ca. 25 cm above the
lower chromitite stringer. Note that pentlandite of the sulfide
mineralization within the gabbronorite carries very low PGE
contents only (Fig. 4).
The maximum Pd concentration (620 ppm) in pentlandite
from drill core US186 is located in the pegmatoidal feld-
spathic pyroxenite below the lower chromitite stringer. Rh
in pentlandite has its maximum concentration at the upper
chromitite stringer (130 ppm) and a further concentration
peak at the lower chromitite stringer (60 ppm). Ru shows a
maximum concentration at the lower chromitite stringer
(25 ppm) and at the upper chromitite stringer (15 ppm).
Os and Ir reach maximum concentrations of 14 and
9 ppm, respectively, in the pegmatoidal feldspathic pyroxe-
nite. A further Os and Ir concentration peak occurs in the
lower chromitite stringer with 6 ppm for both elements. Pt
maxima are 5 ppm in both the pegmatoidal feldspathic
pyroxenite and the chromitite stringers (Fig. 4).
PGE in pyrrhotite, chalcopyrite, and pyrite
Pyrrhotite generally carries much lower PGE concentrations
than pentlandite. The concentrations of Pd in pyrrhotite
Miner Deposita
Fig. 7 Photomicrographs and SEM images of polished sections. a
Mineral aggregate of pentlandite (pn, creamwhite), pyrrhotite (po,
brownish), chalcopyrite (ccp, yellowgreenish), and pyrite (py, white).
Reflected light photomicrograph in air (SD124-13). b Exsolution
flames of pentlandite (containing 75 ppm Pd) in pyrrhotite; the Pd
concentration in pyrrhotite is below the detection limit. SEM image
(US186-11). c Coarse-grained mineral aggregates of pentlandite
(creamwhite) and pyrrhotite (grayish) without chalcopyrite. Reflected
from the four drill cores are generally below 2 ppm, with a
maximum value of 71 ppm in pyrrhotite from drill core
SD134. Rh ranges from 3 to 29 ppm and Ru from 2 to
34 ppm. Os and Ir show a similar range from 1 to 8 and 4 to
light photomicrograph, in air (US186-6). d Aggregate of pentlandite
(creamwhite), chalcopyrite (yellowgreenish), pyrrhotite (grayish),
and PGM (bluegray). Reflected light photomicrograph in air
(SD134-15_1). e Coarse-grained aggregate of pentlandite (600 ppm
Pd), chalcopyrite (1 ppm Pd), and pyrrhotite (Pd below detection
limit). SEM image (US186-11). f Coarse-grained aggregate of pent-
landite (108 ppm Pd, creamwhite), pyrite (<0.004 ppm Pd, dark
gray), and pyrrhotite (light gray). SEM image (US186-5)
11 ppm, respectively. However, Ir in pyrrhotite from drill
core SD124 has higher concentrations up to 66 ppm. Similar
to the values in pentlandite, Pt concentrations range between
2 and 28 ppm.

Fig. 8 Time-resolved spectra, laser ablation ICP-MS analysis of pyr-
rhotite. a Spectrum of inclusion-free pyrrhotite. b Spectrum indicating
the presence of a Ru-Rh-Os-rich inclusion
Chalcopyrite hardly contains any PGE (generally below
11 ppm), but has significant contents of silver, between 30 and
40 ppm Ag in drill core US186. Pentlandite has up to 9 ppm,
pyrrhotite and pyrite between 1 and 2 ppm Ag. The Ag
concentration of 20 ppm is lower in chalcopyrite from drill
core US200. The BMS from the western Bushveld drill cores
SD124 and SD134 show maximum contents of 12 ppm Ag.
Pyrite mostly has PGE concentrations below the detection
limit. Only pyrite from the drill cores SD124 and US186
revealed significant concentrations of Ru (1223 ppm), Rh
(829 ppm), and Pt (526 ppm).
A comparison of mantle-normalized PGE spectra in pent-
landite, pyrrhotite and chalcopyrite is shown in Fig. 9. Pent-
landite is strongly enriched in Pd and Rh compared to the
Ir-PGE (IPGE; Os, Ir, and Ru) in all units of the four drill
cores. In the chromitite stringers and in the pegmatoidal
feldspathic pyroxenite, pentlandite carries distinctly elevated
PGE contents compared to pentlandite in the feldspathic
pyroxenite (Fig. 9ad). In contrast, pyrrhotite and chalcopyrite
show more variable PGE patterns at much lower PGE con-
tents (Figs. 9eh and il). In all units of the four drill cores,
gold in BMS mostly lies below the detection limit of 20 ppb.
The interrelationships between the different PGE in pent-
landite is described as follows: With respect to their
Miner Deposita
coherence during magmatic processes, the PGE are subdi-
vided into the PPGE-group (Pt, Pd, and Rh) and the IPGE
group (Os, Ir, and Ru; e.g., Barnes et al. 1985; Mungall
2005). Therefore, a positive chemical coherence is to be
expected within the subgroups of PPGE and IPGE. Howev-
er, the present study indicates a positive correlation between
Pd and Rh of the PPGE group only (Fig. 10a), not with Pt
(Fig. 10b). Furthermore, there is no covariance of Pt with Rh
and with the IPGE in pentlandite (Fig. 10c). In contrast, in
pentlandite from all four drill cores, the elements of the
IPGE group reveal excellent positive correlations between
Os, Ir, and Ru (Fig. 10d). Correlation coefficients of each
binary plot are listed in ESM 4.
Platinum-group minerals
PGM in drill core US200 from the eastern Bushveld were
exemplarily investigated using EPD and HS with subsequent
SEM analyses. Samples for PGM analyses were taken from
three different lithologies, namely the lower chromitite string-
er, the sulfide-rich feldspathic pyroxenite, and the pegmatoidal
pyroxenite (Fig. 4).
Most PGM were individual grains (70 %) or intergrown
with pentlandite or chalcopyrite (2025 %). The remaining
PGM (5 %) were associated with silicate minerals (Table 2).
Inclusions of PGM in silicates or chromite grains were not
detected (Rudashevsky 2011).
The PGM assemblage of the samples from core US200 is
dominated by Pt-rich minerals, namely cooperite/braggite
[(Pt, Pd, Ni)S], moncheite [Pt(Te, Bi)2], rare laurite (RuS2),
isoferroplatinum (Pt3Fe), gold and minor sperrylite (PtAs2).
In addition, rustenburgite (Pt3Sn) and an unnamed phase
with the composition (PtSnS) were identified. Most of the
PGM were detected in the chromitite stringer (94 PGM plus
four gold grains) and in the sulfide stringer above (40 PGM
plus 10 gold grains), whereas only four PGM grains were
found in the pegmatoidal feldspathic pyroxenite unit (Table 2
and Fig. 11). The PGM (n094) in the vicinity of the chromitite
stringer are dominated by cooperite (50 %) and mon-
cheite (23 %) followed by the unnamed PtSnS mineral
(11 %), rustenburgite (7 %), sperrylite (4 %), braggite
(2 %), native gold (four grains), isoferroplatinum and
niggliite (one grain each). In the sulfide stringer (n PGM+
gold050), cooperite (58 %) dominates followed by native
gold (20 %), moncheite (18 %), and one grain each of
braggite and the unnamed PtSnS. The five grains from
the pegmatoidal feldspathic pyroxenite are isoferroplati-
num and moncheite (two grains each) and native gold.
The precious metal grains are mostly irregular in shape
with an average grain size of between 30 and 40 m in
diameter (Rudashevsky 2011).
Cooperite compositions are similar in the chromite- and
sulfide stringer samples with average Pt and S contents of
Miner Deposita
Fig. 9 Mantle-normalized patterns of PGE contents in pentlandite,
pyrrhotite, and chalcopyrite in the four drill cores of the western
(SD124, SD134) and the eastern (US200, US186) Bushveld. Pentland-
ite (ad) has enhanced Pd and Rh values compared to the IPGE in all
units. Pentlandite in chromitite stringers and in the pegmatoidal
84.5 and 14.35 wt%, respectively. Ni contents are usually
below 1 wt%.
Braggite shows a more variable composition with 71.7
57.1 wt% Pt, 1015.6 wt% Pd, and 2.56.7 wt % Ni in the
chromitite stringer area and in the sulfide stringer area,
respectively.
Moncheite has a similar composition in the chromitite
and sulfide-rich areas (Pt040.4 wt%, Te042.7 wt% and Bi0
16.6 wt%) but reveals somewhat higher Te contents (47.7 wt%)
feldspathic pyroxenite is always more enriched in PGE than those in
the unit of the feldspathic pyroxenite (ad). Pyrrhotite (eh) and
chalcopyrite (il) show more variable PGE patterns compared to those
in pentlandite, at much lower PGE levels
and lower Bi contents (10.7 wt%) in the samples of the pegma-
toidal feldspathic pyroxenite.
Rustenburgite was only detected in the chomitite area and
shows a composition of 66.6 wt% Pt, 15 wt% Pd, and
19 wt% Sn.
Isoferroplatinum has a very consistent composition of
90.4 wt% Pt and 8.9 wt% Fe. The Unnamed PtSnS was
only found in the sulfide-rich area.
Native gold contains between 15.8 and 21.8 wt% silver.

Fig. 10 PGE contents in pentlandite (n0281) in samples of the eastern
and western Bushveld (for correlation matrices and coefficients see
ESM 4). a Distinct positive correlation of Pd versus Rh. b Indistinct
Altogether, 26 PGM grains were identified in the pol-
ished sections of the samples from the western Bushveld
(SD124, SD 134). The PGM assemblage comprises cooper-
ite, braggite, laurite, sperrylite, moncheite, isoferroplatinum,
and hollingworthite.
It should be noted that dominantly Pt-rich PGM are
present in the ores, which supports that a bimodal
distribution of the various PGE, i.e., Pd and Rh occur-
ring mainly in sulfides (see Fig. 9) and Pt in the form
of discrete PGM.
Summary and discussion
The whole rock chemical distribution patterns of Pt and Pd in
the Merensky Reef sequences show distinct mineralization
sequences with usually one well-defined peak of Pt and Pd
in the western Bushveld or two peaks in the eastern Bushveld.
The LA-ICP-MS analyses of PGE in BMS reveal
distinct and elevated PGE contents, mainly of Pd and
Rh, in pentlandite. Pyrrhotite and chalcopyrite contain
very low PGE contents. In general, these results are in
agreement with earlier, mainly single PGE analyses in
BMS of the Merensky Reef (e.g., Ballhaus and Sylvester
Miner Deposita
positive correlation of Pt versus Pd. c Indistinct positive correlation of
Pt vs. Ir. d Positive correlation of Ir versus Os
2000; Godel et al. 2007). Pentlandite is the principal host of
Pd and Rh in the Merensky Reef, and both elements appear to
be homogenously distributed in the crystal lattice of individual
pentlandite grains, with up to 700 ppm Pd and 130 ppm Rh in
the samples from the eastern Bushveld and up to 1,750 ppm
Pd and 1,000 ppm Rh in the western Bushveld. Pd contents in
pyrrhotite mostly are below the detection limit of 65 ppb
whereas Rh reaches a maximum of 25 ppm. Pentlandite
further may contain Ru (up to 60 ppm), Os (up to 17 ppm),
and Ir (up to 14 ppm), whereas pyrrhotite may contain up to
ca. 30 ppm of Ru, Os, and Ir, respectively. Concentration
peaks of Pd, Rh, and Ru in pentlandite closely coincide with
the upper chromitite stringer in the western Bushveld, whereas
in the eastern Bushveld the peaks of Pd, Rh, and Ru in
pentlandite are located in the pegmatoidal feldspathic pyrox-
enite below the lower chromitite stringer. The maximum Pd
concentration (700 ppm) measured in pentlandite in drill core
SD134 is similar to that (600 ppm) from Rustenburg pub-
lished by Godel et al. (2007), but the concentration of Pd in
pentlandite in drill core SD124 is distinctly higher
(1,400 ppm). The concentrations of the other PGE in pent-
landite are in fair agreement with data reported by Godel et al.
(2007) from the Rustenburg area. Furthermore, chalcopyrite
contains most of the Ag.
Miner Deposita

Table 2 PGM and their associ-

ations, core US200, eastern Number L Lp Pn Ccp Po Py Silicate
Bushveld (Rudashevsky 2011)
Lower chromitite stringer
Cooperite 47 29 8 4 4
Moncheite 22 7 10 1 9 2
Braggite 2 1 1 1
Isoferroplatinum 1 1
Rustenburgite 7 1 17 8
Niggliite 1
Sperrylite 4 4 4
unnamed mineral (PtSnS) 10 10 3
Au 4 3 1 1
Total 98 38 53 6 30 0 0 3
Sulfide-rich feldspathic pyroxenite
Cooperite 29 20 1 2 3 4 1
Moncheite 9 2 1 3 1 3 1
Braggite 1 1
unnamed mineral (PtSnS) 1 1
Au 10 4 2 2 4 1
Total 50 26 4 5 11 5 4 2
L Liberated (free) precious Pegmatoidal pyroxenite
metal, Lp more than one Moncheite 2 1 1
precious metal completely
liberated (free), Pn in contact Isoferroplatinum 2 1 1
with pentlandite, Ccp (Au,Ag) 1 1
chalcopyrite, Po pyrrhotite, Total 5 3 0 0 0 1 0 1
Py pyrite, silicates

Comparing the concentration peaks of Pd and Pt (1) in
whole rock and (2) in pentlandite reveals distinct offset pat-
terns, mainly for Pd, in the eastern Bushveld. The concentra-
tion peak of Pd in pentlandite shows a displacement of ca.
50 cm (US200) and ca. 1 m (US186) relative to the maximum
concentration of Pd in whole rock. In drill core US200, this
phenomenon is also observed for Rh, Ru, and Pt.
The covariance of whole rock Pd, Pt, and Rh concen-
trations is positive and significant between all PPGE. In
pentlandite, a distinct positive correlation exists only be-
tween Pd and Rh, a finding which may be related to the
coherent behavior of these elements in a sulfide liquid prior
to mss or iss formation, and a different behavior of the
individual PGE during partitioning into the BMS.
The similar distribution patterns of whole rock PPGE vs.
Cu, Ni, and S (Figs. 3 and 4) are a consequence of the fact
that Pd is mainly hosted in pentlandite, and of the intimate
association of Pt with PGM (mainly sulfides and tellurides).
This is further confirmed by the excellent positive covari-
ance of whole-rock PPGE with Cu, Ni, and S in the eastern
and western Bushveld (Fig. 6ac).
Furthermore, a general sequence of offset patterns of
PGE and BMS maxima, in the order from bottom to top, Pd
in pentlanditePd in whole rock(Cu, Ni, S) can be ob-
served in cores SD124 and US200. The sequences of cores SD
134 and US186 are more complex in detail, but partially show
similar trends.
Mass balance
Trace element analyses of representative samples from drill
cores SD124 (six samples), SD134 (nine samples), and drill
core US200 (six half-core samples: US200-7a, US200-8,
US200-9, US200-10_1, US200-11, US200-12) were used
to conduct mass balance calculations to shed some light on
the distribution of the PGE, especially Pd, between the
different BMS (Tables 3, 4 and 5). In order to calculate the
weight proportions of PGE in BMS, the following formula,
which requires whole-rock chemical data, the weight frac-
tion of the BMS and the concentration of the element in the
BMS was used (Godel et al. 2007):


Psul i Fsul Csul i =Cwr i  100
with Fsul as the weight fraction of the BMS, Csul as the
concentration of the element i in the BMS, and Cwr as the
concentration of the element i in the whole rock.
The weight fraction of the BMS was calculated for pent-
landite: (Fpn 0Niwr/Nipn), chalcopyrite (FCcp 0Cuwr/CuCcp),
Miner Deposita
 Miner Deposita

Fig. 11 BSE images of polished sections showing various PGM. a, c, calculated proportions for the PGE in BMS of drill core
and f are gold and PGM detected in concentrates obtained by EPD+
HS, Merensky Reef samples of core US200. a Gold (Au,Ag) with
US200 are given in Tables 3, 4 and 5.
inclusion of moncheite and adjacent chalcopyrite. b Laurite attached to The proportions of all PGE in BMS were calculated for
chalcopyrite; SD134-15. c Euhedral inclusion of isoferroplatinum (Pt, the six samples (US200-7a, US200-8, US200-9, US200-10,
Fe) in pentlandite. d Cooperite intergrown with pentlandite; US186-5. US200-11, and US200-12) of drill core US200. For the
e Sperrylite intergrown with pentlandite and pyrrhotite; SD134-15. f
Gold (Au, Ag) intergrown with the unnamed mineral (PtSnS)
samples from the western Bushveld, a calculation was only
possible for the PPGE since whole rock IPGE were not
available.
and pyrrhotite (Fpo 0Swr SCcp FCcp SPn FPn/SPo) assum- The eastern Bushveld drill core samples US200-7a,
ing that all Cu is hosted by chalcopyrite, Ni by pentlandite US200-8, and US200-12 are sulfide-rich (38 vol.% sul-
and all S by these three sulfides (Godel et al. 2007). A total fides), whereas samples US200-9, US200-10, and US200-
of 0.09 wt% Ni was subtracted from the whole-rock Ni 11 have lower sulfide contents (<1 vol.% sulfides) and
since electron microprobe data revealed a significant amount contain a chromitite stringer (US200-9). In the case of the
of Ni in pyroxene and pyrrhotite. Pyrite is regarded as three sulfide-rich samples, a high percentage of PGE is
negligible due to its low modal content. The calculated hosted by base-metal sulfides and the remaining amounts
weight fractions of the BMS are listed in Table 1. The in PGM, whereas in the presence of a chromitite stringer or
in case of relatively low sulfide contents, most of the PGE
Table 3 Calculated proportions (in percent) of the six PGE in BMS of are located in discrete PGM (Table 3; Fig. 12). The mass
drill core US200 (eastern Bushveld) using the mass balance calculation balance revealed that in the sulfide-rich samples (US200-7a,
of Godel et al. (2007)
US200-8, US200-12), pentlandite hosts between 62 and
Os Ir Ru Rh Pt Pd 100 % of the Pd, 55 to nearly 100 % of the Rh, most of
the Ru (up to 90 %), 1060 % of Os and most of the Ir
US200-7a 918.30 m (Table 3). Chalcopyrite contains up to 10 % of the Os, 25 %
Pn 55.67 10.03 90.98 53.48 0.02 62.53 of the Ir, 4 % of the Ru and 0.35 and 3 % of the Pd and Rh,
Chp 4.60 0.27 0.00 0.20 0.01 0.16 respectively. Pyrrhotite contains up to 9 % of the Os, 11 %
Po 0.84 5.39 0.00 17.71 0.00 0.00 of the Ir, and 4 % of the Ru (Table 3).
all sulfides 61.11 15.68 90.98 71.40 0.03 62.69 Less than 0.5 % of Pt is hosted by the base-metal sulfides
US200-8 918.45 m (Table 3). Therefore, it is apparent that Pt is present in the
Pn 66.55 97.74 98.27 97.92 2.58 99.89 form of discrete PGM such as cooperite, isoferroplatinum,
Chp 10.56 25.10 4.06 3.46 0.04 0.15 sperrylite or moncheite, and Au occurs as native gold. The
Po 9.91 11.76 4.79 1.62 0.01 0.00 silicates and chromite contain no detectable amounts of
all sulfides 87.02 134.60 107.12 103.01 2.63 100.05 PGE, which is in accordance with results of Ballhaus and
US200-9 918.72 m Sylvester (2000) and Godel et al. (2008).
Pn 0.05 1.51 0.18 5.38 0.03 13.19 In the sulfide-poor samples (US200-9, US200-10,
Chp 0.05 0.00 0.03 0.16 0.00 0.05 US200-11), pentlandite generally contains less Pd (13
Po 0.00 0.00 0.00 0.05 0.00 0.00 42 %) than in sulfide-rich samples. Furthermore, pentlandite
all sulfides 0.11 1.51 0.20 5.59 0.04 13.24 in the sulfide-poor samples contains less Rh (35 %), Ir
US200-10 918.80 m (1 %), Os and Ru (0.55 %; Table 3). Only exceptionally,
Pn 0.05 0.35 0.31 3.52 0.02 26.05 one sulfide-poor sample (US200-11) was found to contain up
Chp 1.75 0.00 0.00 2.28 0.01 1.07 to 90 % Rh and Ir, respectively. Chalcopyrite and pyrrhotite
Po 0.00 43.31 0.00 61.94 0.45 0.34 contain less than 0.16 % of the PGE (Table 3). The presence
all sulfides 1.80 43.66 0.31 67.74 0.48 27.46 of many discrete PGM such as cooperite and braggite mainly
US200-11 919.05 m in and in the vicinity of the chromitite stringer may explain
Pn 0.00 95.09 5.05 99.25 0.86 42.37 the lower Pd concentration in pentlandite in the sulfide-poor
Chp 0.00 2.01 0.15 2.36 0.01 0.07 samples compared to the sulfide-rich samples which contain
Po 0.00 7.07 0.81 0.13 0.00 0.00 less PGM.
all sulfides 0.00 104.17 6.01 101.73 0.87 42.45 In the sulfide-rich samples (US200-7a, US200-8, US200-
US200-12 919.30 m 12), 55100 % of Pd, Rh and Ru as well as 1168 % of Os and
Pn 10.96 38.99 7.84 53.21 1.29 99.63 Ir are hosted by the BMS. In samples US200-9, US200-10,
Chp 0.00 0.00 0.08 2.06 0.01 0.35 and US200-11, which are relatively poor in sulfides, only 0.5
Po 0.00 1.79 0.00 0.75 0.00 0.00
40 % of Pd, Rh, and Ru as well as less than 3 % of Os and Ir
all sulfides 10.96 40.77 7.92 56.02 1.30 99.98
are hosted in BMS (Table 3); the remaining PGE are hosted in
PGM such as cooperite, braggite, and moncheite.
 Miner Deposita

In the western Bushveld, pentlandite from samples in and

in the vicinity of the chromitite stringers contain between 50
and 80 % of the Pd. Pentlandite grains in the feldspathic
pyroxenite and the pegmatoidal feldspathic pyroxenite con-
tain up to 100 % of the Pd (Tables 4 and 5; Fig. 12). The
remaining Pd is hosted by discrete PGM (mostly braggite),
whereas chalcopyrite and pyrrhotite are almost devoid of PGE.
The positive covariance between the Pd content in pent-
landite and whole rock Pd in the samples of the western
Bushveld is absent in the samples from the eastern Bushveld
(Fig. 13). This corresponds with the results of the mass bal-
ance calculation and is also displayed by Figs. 3 and 4 which
show that the Pd concentration peak in pentlandite and that of
whole rock Pd largely overlap in the western Bushveld, but
are displaced from each other in the eastern Bushveld.

Table 4 Calculated proportions (in percent) of Pd, Rh, and Pt in the

BMS of drill core SD134 (western Bushveld) using the mass balance
calculation of Godel et al. (2007)

SD134

611.59 m Pd Rh Pt
Pn 0.76 0.00 0.01
Po 0.00 0.00 0.00
Chp 0.11 0.00 0.00
All sulfides 0.87 0.00 0.01
611.86 m
Pn 2.15 0.38 0.15
Po 0.09 0.27 0.55
Chp 0.04 0.11 0.00
All sulfides 2.28 0.76 0.70
612.13 m
Pn 5.71 0.34 0.02
Po 0.04 0.13 0.03
Chp 0.02 0.06 0.00
All sulfides 5.77 0.52 0.05
612.40 m
Pn 12.76 0.42 0.02
Po 0.05 0.19 0.04
Chp 0.02 0.06 0.00
All sulfides 12.82 0.67 0.05
612.66 m
Fig. 12 Results of mass balance calculations of Pd in BMS and Pd in
Pn 57.11 58.03 0.05
discrete PGM in drill cores SD124 and SD134 (western Bushveld) and
US200 (eastern Bushveld). Pentlandite in and around the chromitite Po 0.02 0.15 0.06
stringers contains between 50 and 80 % of the whole-rock Pd in Chp 0.01 0.06 0.00
samples from the western Bushveld. Pentlandite contains up to All sulfides 57.14 58.25 0.11
100 % of the Pd in the feldspathic pyroxenite and the pegmatoidal
feldspathic pyroxenite. In the samples from the eastern Bushveld 613.16 m
(US200), pentlandite incorporates only up to 10 % of the whole rock Pn 46.80 80.85 0.12
Pd in the range of the chromitite stringer. In the units of the feldspathic Po 6.29 1.19 0.13
pyroxenite and the pegmatoidal feldspathic pyroxenite, pentlandite
Chp 16.48 30.32 0.00
hosts up to 100 % of the Pd. The remaining Pd is hosted by discrete
PGM since chalcopyrite and pyrrhotite are almost devoid of PGE All sulfides 69.57 112.37 0.25
Miner Deposita

Table 5 Calculated proportions (in percent) of Pd, Rh, and Pt in the

BMS of drill core SD124 (western Bushveld) using the mass balance
calculation of Godel et al. (2007)

SD124

666.25 m Pd Rh Pt
Pn 72.31 10.94 0.59
Po 1.79 4.75 1.21
Chp 2.18 4.25 0.02
All sulfides 76.28 19.94 1.82
666.50 m
Pn 98.14 8.96 0.06
Po 0.02 0.04 0.02 Fig. 13 Diagram showing close covariance between the Pd content in
pentlandite and whole rock Pd in the samples of the western Bushveld,
Chp 0.25 0.26 0.01 but not in the samples from the eastern Bushveld, underlining the mass
All sulfides 98.41 9.27 0.08 balance calculations. Compare also Figs. 3 and 4 which show that the
666.74 m Pd concentration peak in pentlandite and that of whole-rock Pd are
consistent in the samples from the western Bushveld, but are displaced
Pn 99.57 99.00 0.26
in the sample sequences of the eastern Bushveld
Po 0.00 0.60 0.99
Chp 0.37 0.48 0.00 The mass balance calculations are in excellent agreement
All sulfides 99.94 100.08 1.25 with our geochemical and mineralogical data and also former
667.00 m studies on PGE contents in BMS of the Bushveld Complex
Pn 74.85 99.00 0.60 and other layered intrusions (e.g., Barnes et al. 2008; Dare et
Po 0.00 0.85 0.34 al. 2010; Godel et al. 2007). For instance, Godel et al. (2007)
Chp 0.12 0.62 0.14 calculated that 50100 % of whole-rock Pd and Rh are
All sulfides 74.97 100.47 1.08 predominantly hosted by BMS, mostly pentlandite, in
667.26 m Merensky Reef samples from the western Bushveld. Fur-
Pn 53.80 99.00 0.15 thermore, Godel et al. (2007) reported that 3572 % of
Po 0.00 1.19 0.04 whole rock Os, Ir, and Ru are hosted by BMS located in
Chp 0.67 3.48 0.94 the silicate rocks but only 0.212 % of the whole-rock Os,
All sulfides 54.47 103.67 1.13 Ir, and Ru are hosted in BMS in the chromitite layers. Godel
667.52 m et al. (2007) also suggested that the Pt is hosted by PGM
Pn 51.51 23.39 0.00 rather than by BMS.
Po 0.38 0.40 0.01
Chp 0.05 4.45 0.01
All sulfides 51.93 28.24 0.01 Offset patterns
667.78 m
Pn 52.15 28.86 0.00 So-called offset patterns, i.e., distinct chemical zonations
Po 0.05 0.59 0.01 of PGE and BMS in ore sequences, were described for
Chp 0.04 0.21 0.01 some ore bodies in layered intrusions including the Bush-
All sulfides 52.24 29.67 0.03 veld (Maier and Barnes 2010), the Great Dyke (Oberthr
668.04 m 2002, 2011; Wilson et al. 1989), Munni Munni (Barnes
Pn 73.05 0.79 3.03 1993) and the Stella intrusions (Maier et al. 2003).
Po 0.11 0.00 0.72
These authors reported offset patterns between the PGE
Chp 0.92 6.62 0.02
distribution and that of the base metals (Cu, Ni, and S), as
All sulfides 74.08 7.41 3.77
well as of Pd and Pt, in whole-rock analyses. Mungall
(2002) interpreted such offsets as a reflection of progressive-
668.30 m
ly decreasing diffusion rates of the chalcophile elements into
Pn 13.76 45.12 4.17
the segregating sulfide liquid. Wilson et al. (1989) and
Po 0.03 0.52 0.14
Barnes (1993) suggested models of fractional segregation
Chp 0.05 1.93 0.49
of sulfide liquid being responsible for PGE offsets in the
All sulfides 13.83 47.58 4.80
Great Dyke and the Munni Munni intrusions. Another pos-
sible explanation for the offsets, e.g., in the Great Dyke, is
that Pt and Pd were decoupled from the other base metals by

a Rayleigh fractionation process. In this case, it was sug-
gested that the most strongly chalcophile elements preferen-
tially concentrate in the first sulfide liquid and become
rapidly depleted in the residual liquid (Wilson et al. 1989;
Oberthr 2011).
Indeed, the present study revealed a general sequence of
distinct offset patterns of PGE and BMS maxima, in the
order from bottom to top, Pd in pentlanditePd in whole
rock(Cu, Ni, S) in cores SD124 and US200. The sequen-
ces of cores SD 134 and US186 are more complex in detail,
but partially show similar trends.
For example, in drill core US200, the peaks of Ni and Cu
are ca. 25 cm above those of Pt and Pd. Furthermore, the
concentration peak of Pd in pentlandite is decoupled by 25 cm
from the concentration peaks of Pd, Ni, and Cu in whole rock.
Notably, the PGE concentration peaks in pentlandite are nei-
ther consistent with the Ni and Cu nor with the Pd and Pt
whole rock concentration peaks. The offset patterns observed
in drill core US200 closely resemble those observed in the
Main Sulfide Zone of the Great Dyke (e.g., Oberthr 2011).
Rayleigh fractionation, therefore, is a possible explanation for
the offset feature in core US200.
PGE behavior during the evolution of a Cu-Ni-Fe-liquid
The present study identified high concentrations of Pd in
pentlandite and low concentrations in chalcopyrite, a finding
that contradicts experimental and theoretical results which
show that Pd has a stronger affinity to partition into the Cu-
rich liquid (e.g., Barnes et al. 2001; Li et al. 1996; Mungall
et al. 2005; Naldrett 2004). However, our results are in fair
agreement with previous studies of PGE in BMS in natural
samples (Godel et al. 2007; Holwell and McDonald 2007).
In the present sample set from the Bushveld as well as
in samples from other layered intrusions (e.g., Dare et al.
2010), Pd is enriched in pentlandite instead of chalcopy-
rite. Dare et al. (2010) conducted studies on samples from
the Sudbury Complex and suggested that the Pd enrich-
ment in pentlandite is caused by diffusion of Pd from the
nearby Cu-rich portion (iss and/or Pd-bearing PGM) into
the pentlandite and that a small quantity of Pd is believed
to stem from the Pd that had originally partitioned into the
mss. Dare et al. (2010) further described three types of
pentlandite with the highest Pd contents in the coarse-
grained pentlandite, lower contents in pentlandite veinlets
while Pd in exsolution flames of pentlandite was below
detection. However, the Merensky Reef samples of the
present study mainly contain coarse-grained pentlandite,
intimately intergrown with chalcopyrite, pyrrhotite, and
pyrite and rare pentlandite exsolution flames in pyrrhotite.
Our study revealed high Pd concentrations (up to 650 ppm)
in the coarse-grained pentlandite that is in immediate
contact with chalcopyrite and, in addition, significant Pd
Miner Deposita
concentrations in the exsolution flames of pentlandite in pyr-
rhotite (up to 75 ppm; Figs. 7e and b). Furthermore, coarse-
grained pentlandite which is in immediate contact with matrix
silicates but not with chalcopyrite also contains significant
amounts of Pd independent of the stratigraphic level in the
Merensky Reef sequence (107 ppm in the upper chromitite
stringer or 30 ppm in the feldspathic pyroxenite below the upper
chromitite stringer; Fig. 7f). Our findings may be explained by
diffusion of Pd through the matrix silicate grains or along their
grain boundaries (Godel et al. 2006; Mungall and Su 2005), or,
in our opinion, the partitioning of large amounts of Pd into mss
may have taken place during an earlier magmatic stage.
Conclusions
1. In the studied samples of the Merensky Reef, the dis-
tinct covariance of the whole rock PGE, Cu, and Ni
indicates a strong relation of the PGE to sulfides. The
highest whole-rock PGE contents are mostly found
within and around the upper and lower chromitite
stringer and locally in sulfide stringers. Pt and Pd are
the dominant PGE in the Merensky Reef with Pt/Pd
ratios generally between 3 and 5.
2. Pentlandite is the principal host of Pd and Rh and also
contains small quantities of Ru, Os, and Ir. Pyrrhotite
may contain elevated amounts of Ru, Os, Ir, and Pt, but
is devoid of Pd or Rh. Chalcopyrite carries very low
PGE contents but hosts most of the Ag.
3. In the Merensky Reef sequence, the concentrations of
Pd and Rh in pentlandite are unevenly distributed. In the
samples from the western Bushveld, the highest Pd and
Rh contents in pentlandite are present in samples from
the upper chromitite stringer. In contrast, in the samples
from the eastern Bushveld, the highest Pd and Rh con-
centrations in pentlandite occur below the lower chro-
mitite, in the pegmatoidal feldspathic pyroxenite unit.
4. Mass balance calculations performed on the Merensky
Reef samples reveal that in general, pentlandite in the
feldspathic pyroxenite and the pegmatoidal feldspathic
pyroxenite hosts most of the Pd and Rh (up to 100 %)
and smaller amounts (1040 %) of the Os, Ir, and Ru.
Chalcopyrite and pyrrhotite usually contain less than
10 % of the whole rock PGE. The remaining PGE
concentrations, and especially most of the Pt (up to
100 %), are present in the form of discrete PGM.
5. Pt-dominant mineral species are the principal PGM;
most common are cooperite, braggite, and moncheite,
followed by rarer Pt-Fe alloys and rustenburgite.
6. The high Pd concentrations in pentlandite are thought to
be the result of large amounts of Pd partitioning into
mss at an early magmatic stage or due to diffusion from
the iss at a later stage.
Miner Deposita
7. Distribution patterns of whole rock Cu, Ni, and S versus
whole rock Pd and Pt show commonly distinct offsets.
The general sequence of offset patterns of PGE and
BMS maxima, in the order from bottom to top, is Pd in
pentlanditePd in whole rock(Cu, Ni, S). The rela-
tionship is not that straightforward in general; some of
the reef sequences studied only partially show similar
trends. Especially the resolution in the samples from the
western Bushveld may have been hampered by the
relatively thin mineralized zones.
8. In general, however, the highest Pd concentrations in pent-
landite appear to be related to the earliest, volumetrically
rather small sulfide liquids at the base of the Merensky
Reef sequence. A possible explanation for the offset
patterns may be Rayleigh fractionation.
Acknowledgments Anglo American Platinum is thanked for provid-
ing the drill cores, analytical data and logistic assistance. Especially
Jacques Roberts supported us through logistical help, continuous interest
and enthusiasm with regard to the study. Thanks to Nikolay Rudashevsky
who conducted EPD, HS, and SEM analyses on selected samples from
the eastern Bushveld and provided us with an excellent report on the
PGM assemblages. Belinda Godel and Sarah Dare provided helpful and
constructive reviews which are acknowledged with thanks.
References
Ballhaus C, Sylvester P (2000) Noble metal enrichment processes in
the Merensky Reef, Bushveld Complex. J Petrol 41:545561
Barnes SJ (1993) Partitioning of the platinum group elements and gold
between silicate and sulphide magmas in the Munni Munni Com-
plex, western Australia. Geochim Cosmochim Acta 57:12771290
Barnes SJ, Picard CP (1993) The behaviour of platinum-group ele-
ments during partial melting, crystal fractionation, sulphide seg-
regation: an example from the Cape Smith Fold Belt, northern
Quebec. Geochim Cosmochim Acta 57:7987
Barnes SJ, Naldrett AJ, Gorton MP (1985) The origin of the fractionation
of platinum-group elements in terrestrial magmas. Chem Geol
53:303323
Barnes SJ, van Achterbergh E, Makovicky M, Rose-Hansen J,
Karup-Moller S (1997) Partition coefficient for Ni, Cu, Pd, Pt, Rh
and Ir between monosulfide solid solution and sulfide liquid and the
formation of compositionally zoned Ni-Cu sulfide bodies by frac-
tional crystallization of sulfide liquid. Can J Earth Sci 34:366374
Barnes SJ, van Achterbergh E, Makovicky E, Li C (2001) Proton
microprobe results for the partioning of platinum-group elements
between monosulphide solid solution and sulphide liquid. S Afr J
Geol 104:275286
Barnes SJ, Cox RA, Zientek ML (2006) Platinum-group element, gold,
silver and base metal distribution in compositionally zoned sul-
fide droplets from the Medvezky Creek Mine, Norilsk, Russia.
Contrib Mineral Petrol 152:187200
Barnes SJ, Prichard HM, Cox RA, Fisher PC, Godel B (2008) The
location of the chalcophile and siderophile elements in platinum-
group element ore deposits (a textural, microbeam and whole-rock
geochemical study): Implication for the formation of the deposits.
Chem Geol 248:295317
Boudreau AE (1992) Volatile fluid overpressure in layered intrusions
and the formation of potholes. Aus J Earth Sci 39:277287
Boudreau AE, Meurer WP (1999) Chromatographie separation of the
platinum-group elements, gold, base-metals and sulfur during
degassing of a compacting and solidifying igneous crystal pile.
Contrib Mineral Petrol 134:174185
Cabri LJ, Rudashevsky NS, Rudashevsky VN, Oberthr T (2008)
Electric-pulse disaggregation (Epd), hydroseperation (Hs) and
their use in combination for mineral processing and advanced
characterization of ores. Proceedings 40th Annual Canadian Mineral
Processors Conference, paper 14
Campbell IH, Naldrett AJ, Barnes SJ (1983) A model for the origin of
the platinum-group sulfide horizons in the Bushveld and Still-
water Complexes. J Petrol 24:133165
Cawthorn RG (1999) The platinum and palladium resources of the
Bushveld Complex. S Afr J Sci 95:481489
Cawthorn RG, Merkle RKW, Viljoen MJ (2002) Platinum-group element
deposits in the Bushveld complex, South Africa. In: Cabri LJ (ed)
The geology, geochemistry, mineralogy and mineral benification of
platinum-group elements. Can Inst Mining Metall Petroleum Spec
54:389430
Cawthorn RG, Eales HV, Walraven F, Uken R, Watkeys MK (2006)
The Bushveld complex In: Johnson, MR, Anhaeusser, CR and
Thomas, RJ (eds). The geology of South Africa. Geological
Society of South Africa, 261281
Cheney ES, Twist D (1991) The conformable emplacement of the
Bushveld mafic rocks along a regional unconformity in the Trans-
vaal succession of South Africa. Prec Res 52:115132
Dare SAS, Barnes SJ, Prichard H (2010) The distribution of platinum
group elements (PGE) and other chalcophile elements among
sulphides from the Creighton Ni-Cu-PGE sulphide deposit,
Sudbury, Canada, and the origin of palladium in pentlandite. Miner
Deposita 45:765793
Eales HV, Cawthorn RG (1996) The Bushveld Complex. In: Cawthorn
RG (ed) Layered intrusions. Elsevier, Amsterdam, pp 181229
Godel B, Barnes SJ (2008) Platinum-group elements in sulphide minerals
and the whole rocks of the J-M Reef (Stillwater Complex): impli-
cation for the formation of the Reef. Chem Geol 248:272294
Godel B, Barnes SJ, Maier WD (2006) 3-D distribution of sulfide
minerals in the Merensky Reef (Bushveld Complex, South Africa)
and the J-M Reef (Stillwater Complex, USA) and their relation-
ship to microstructures using X-ray computed tomography. J
Petrol 47:18531872
Godel B, Barnes SJ, Maier WD (2007) Platinum-group elements in
sulphide minerals, platinum-group minerals, and whole-rocks of
the Merensky Reef (Bushveld Complex, South Africa): implica-
tions for the formation of the Reef. J Petrol 48:15691604
Hatton CJ, Schweitzer JK (1995) Evidence for synchronous extrusive
and intrusive Bushveld Complex. Can Miner 17:579594
Holwell DA, McDonald I (2006) Petrology, geochemistry and the mech-
anisms determining the distribution of platinum-group elements and
base metal mineralisation in the Platreef at Overysel, northern
Bushveld Complex, South Africa. Miner Deposita 41:575598
Holwell DA, McDonald I (2007) Distribution of platinum-group ele-
ments in the Platreef at Overysel, northern Bushveld Complex: a
combined PGM and LA-ICP-MS study. Contrib Mineral Petrol
154:171190
Holwell DA, McDonald I (2010) A review of the behaviour of platinum
group elements within natural magmatic sulphide ore systems.
Platin Met Rev 54:2636
Hulbert LJ, von Gruenewaldt G (1982) Nickel, copper and platinum
mineralisation in the lower zone of the Bushveld Complex, south
of Potgieterus. Econ Geol 77:12961306
Kinloch ED (1982) Regional trends in the platinum-group mineralogy
of the Critical Zone of the Bushveld Complex, South Africa. Econ
Geol 77:13281347
Kullerud G, Yund RA, Moh GH (1969) Phase relations in the Cu-Fe-S,
Cu-Ni-S and Fe-Ni-S systems. Econ Geol Monograph 4:323343

Li C, Makovicky E, Rose-Hansen J, Makovicky M (1996) Partioning of Ni,
Cu, Ir, Rh, Pt, Pd between mss and sulphide liquid: effects of com-
position and temperature. Geochim Cosmochim Acta 60:12311238
Maier WD, Barnes SJ (2010) The petrogenesis of platinum-group
element reefs in the upper main zone of the northern lobe of the
Bushveld Complex on the farm Moorddrift, South Africa. Econ
Geol 105:841854
Maier WD, Barnes SJ, Gartz V, Andrews G (2003) Pt-Pd reefs in
magnetites of the Stella layered intrusion, South Africa: a world
of new exploration opportunities for platinum-group elements.
Geology 31:885888
Misra KC (2000) Understanding mineral deposits. Kluwer, Netherlands
Mitchell AA, Scoon RN (2007) The Merensky Reef at Winnaarshoek,
Eastern Bushveld Complex: a primary magmatic hypothesis
based on a wide reef facies. Econ Geol 102:9711009
Mungall JE (2002) Kinetic controls on the partitioning of trace ele-
ments between silicate and sulphide liquids. J Petrol 43:749768
Mungall JE (2005) Magmatic geochemistry of the platinum-group
elements; exploration for PGE deposits. In: Mungall JE (ed)
Mineralog Assoc Canada, short course series volume 35
Mungall JE, Su S (2005) Interfacial tension between magmatic sulfide
and silicate liquids: constraints on kinetics of sulfide liquation and
sulfide migration through silicate rocks. Earth Planetary Sci Let
234:135149
Mungall JE, Andrews DRA, Cabri L, Sylvester PJ, Tubrett M
(2005) Partitioning of Cu, Ni, Au and platinum-group elements
between monosulphide solid solution and sulphide melt under con-
trolled oxygen and sulfur fugacities. Geochim Cosmochim Acta
69:43494360
Naldrett AJ (1989a) Magmatic sulfide deposits. Oxford University
Press, Oxford, p 189
Naldrett AJ (1989b) Stratiform PGE deposits in layered intrusions. Rev
Econ Geol 4:135165
Naldrett A (2004) Magmatic sulphide deposits. Geology, geochemistry
and exploration. Springer, Berlin, p 728
Naldrett AJ, Wilson A, Kinnaird J, Chunnett G (2009) PGE tenor and
metal ratios within and below the Merensky Reef, Bushveld
Complex: implications for its genesis. J Petrol 50:625659
Oberthr T (2002) Platinum-group element mineralisation of the Great
Dyke, Zimbabwe. In: Cabri LJ (ed) The geology, geochemistry,
mineralogy and mineral beneficiation of platinum-group ele-
ments, Canad Inst Min Metal Pet vol 54:483506
Oberthr T (2011) Platinum-group element mineralization of the Main
Sulfide Zone, Great Dyke, Zimbabwe. Rev Econ Geol 17:329349
Oberthr T, Cabri LJ, Weiser Th, McMahon G, Mller P (1997) Pt, Pd
and other trace elements in sulfides of the Main Sulfide Zone,
Great Dyke, Zimbabwea reconnaissance study. Canad Mineral
35:597609
Oberthr T, Weiser TW, Gast L, Kojonen K (2003) Geochemistry and
mineralogy of platinum-group elements at Hartley Mine, Zimbabwe.
Mineral Deposita 38:327343
Miner Deposita
Peregoedova A, Barnes SJ, Baker DR (2004) The formation of Pt-Ir
alloys and Cu-Pd-rich sulphide melts by partial desulfurization of
Fe-Ni-Cu sulphides: results of experiments and implications for
natural systems. Chem Geol 208:247264
Rudashevsky VN (2011) Precious metal minerals in ores from the
Merensky reef, drill core US200 D6, eastern Bushveld (US200-
7a/8, US200-9, US200-11). Internal report to BGR, 27 pp plus
appendices
SACS (South African Commitee for Stratigraphy) (1980) Stratigraphy
of South Africa. Part 1 (Kent, L.E., Comp.), Lithostratigraphy of
the Republic of South Africa, South West Africa/Namibia, and the
Republics of Bophuthatswana, Transkei and Venda. Handbook
geological survey South Africa 8, pp 690
Schwellnus JSI, Hiemstra SA, Gasparrini E (1976) The Merensky Reef at
the Atok Platinum Mine and its environs. Econ Geol 71:249260
van Achterbergh E, Ryan CG, Griffin WL (2000) GLITTER (version
3.0, on-line interactive data reduction for LA-ICPMS). Maquarie
research Ltd
Vermaak CF (1995) The platinum-group metals. A global perspective.
MINTEK, Randburg, p 247
Vermaak CF, Hendriks LP (1976) A review of the mineralogy of the
Merensky Reef, with specific reference to new data on the pre-
cious metal mineralogy. Econ Geol 71:12441269
Vermeulen GJ (2010) Merensky reef facies delineation on the farms
Boschkoppie and Styldrift in the western Bushveld complex.
BRPM geological services report, 42 pp
Von Gruenewaldt G (1977) The mineral resources of the Bushveld
Complex. Miner Sci Eng 9:8395
Von Gruenewaldt G (1979) A review of some recent concepts of the
Bushveld Complex, with particular reference to sulfide minerali-
zation. Can Miner 17:233256
Wagner PA (1929) The platinum deposits and mines of South Africa.
Oliver and Boyd, Edinburgh, pp 306316
Walraven F, Armstrong RA, Kruger FJ (1990) A chronostratigraphic
framework for the north-central Kaapvaal craton, the Bushveld
Complex and Vredefort structure. Tectonophysics 171:2348
Willemse J (1969) The geology of the Bushveld Complex the largest
repository of magmatic ore deposits in the world. Econ Geol
Monograph 4:122
Wilson AH, Naldrett AJ, Tredoux M (1989) Distribution and control of
platinum-group element and base metal mineralisation in the
Darwendale sub-chamber of the Great Dyke, Zimbabwe. Geology
17:649652
Wilson AH, Lee CA, Brown RT (1999) Geochemistry of the Merensky
Reef, Rustenburg Section, Bushveld Complex: controls on the
silicate framework and distribution of trace elements. Miner
Deposita 34:657672
Wohlgemuth-Ueberwasser CC, Ballhaus C, Berndt J, Meisel T (2007)
Synthesis of PGE sulfide standards for laser ablation inductively
coupled plasma mass spectrometry (LA-ICP-MS). Contrib Mineral
Petrol 154:607617