Miner Deposita (2003) 38: 344–355

DOI 10.1007/s00126-002-0338-8

A RT I C L E

Thomas Oberthür Æ Thorolf W. Weiser Æ Lothar Gast

Geochemistry and mineralogy of platinum-group elements

at Hartley Platinum Mine, Zimbabwe

Part 2: Supergene redistribution in the oxidized Main Sulfide Zone of the Great Dyke,
and alluvial platinum-group minerals

Received: 27 February 2001 / Accepted: 1 November 2002 / Published online: 23 January 2003

Springer-Verlag 2003

Abstract The behaviour of platinum-group elements

(PGE) in the exogenic cycle was examined in profiles of
oxidized Main Sulfide Zone (MSZ) ores, in which the
general metal distribution patterns of the pristine MSZ
are grossly preserved. However, at similar Pt grades,
significant proportions of Pd have been lost from the
system. This indicates that Pd is more mobile than Pt
and is dispersed in the supergene environment. Sperry-
lite and cooperite/braggite are stable in the oxidized
MSZ. In contrast, the (Pt,Pd)-bismuthotellurides, com-
mon in pristine MSZ ores, have disintegrated, and ill-
defined (Pt,Pd)-oxides or (Pt,Pd)-hydroxides have
formed. The assemblage of detrital PGM present in the
Makwiro River close to the Hartley Platinum Mine in-
dicates further mineralogical changes. Sperrylite largely
remains stable whereas most cooperite/braggite grains
have been partly altered or completely destroyed. Grains
of Pt-Fe alloy are ubiquitous in the alluvial sediments.
Most likely, these grains are neo-formations that formed
either from pre-existing, unstable PGM or via a solution
stage under low-temperature conditions.
Keywords PGM Æ Oxidized Main Sulfide Zone Æ
Placers Æ Great Dyke Æ Hartley Platinum Mine Æ
Zimbabwe
Editorial handling: O. Thalhammer
T. Oberthür (&) Æ L. Gast
Federal Institute for Geosciences
and Natural Resources (BGR),
Stilleweg 2, 30655 Hannover, Germany
E-mail: thomas.oberthuer@bgr.de
T.W. Weiser
Rischkamp 63, 30659 Hannover, Germany
K. Kojonen
Geological Survey of Finland,
Betonimiehenkuja 4, 02150 Espoo, Finland
Introduction
In the Great Dyke of Zimbabwe, economic concentra-
tions of platinum-group elements (PGE) are restricted to
sulfide disseminations of the Main Sulfide Zone (MSZ),
which is found in pyroxenitic host rocks some meters
below the transition between the lower Ultramafic and
the upper Mafic Sequence of the Great Dyke. Pristine,
sulfide-bearing MSZ ores mined underground are the
major focus of mining and were described in Part 1 of
this study (Oberthür et al. 2003). Near-surface oxidized
MSZ ores have a large economic potential with an es-
timated resource of 400 Mt of ore (Prendergast 1988);
however, all previous attempts to extract the PGE from
this ore type proved uneconomic due to low PGE
recoveries achieved by conventional metallurgical
methods.
Thermodynamic data and field studies have demon-
strated that the PGE are variably mobile in the supergene
environment (e.g. Wagner 1929; Fuchs and Rose 1974;
Bowles 1986, 1995; Cook et al. 1992; Wood et al. 1992;
Evans et al. 1994; Augé et al. 1995; Cabri et al. 1996; Hey
1999; Oberthür et al. 1999, 2000; Evans and Spratt 2000).
However, PGE mobilities, the processes of PGE redis-
tribution, and PGM disintegration versus neoformation
in the supergene environment are much debated and cases
of both dispersion and concentration have been proposed
by the above authors.
The present study is based on samples from exposures
of oxidized ores of the MSZ created in the course of
mining at Hartley Platinum Mine. The present study
focuses on the redistribution of the PGE and PGM in
the supergene environment. Direct relationships between
primary and secondary PGE/PGM mineralization are
established through the investigation of samples from
pristine MSZ ores (see Part 1, Oberthür et al. 2003) and
from weathered MSZ surface exposures as well as de-
trital PGM from recent alluvial sediments in a river close
to the Hartley Platinum Mine.
 345

Geological setting

The Great Dyke layered intrusion is of linear shape and

trends over 550 km NNE at a maximum width of about
11 km, and cuts Archean granites and greenstone belts
of the Zimbabwe craton (Worst 1960). Stratigraphically,
the layered series of the Great Dyke is divided into a
lower Ultramafic Sequence of dunites, harzburgites,
olivine bronzitites and pyroxenites, with narrow layers
of chromitite at the base of cyclic units, and an upper
Mafic Sequence mainly consisting of a variety of pla-
gioclase-rich rocks (norites, gabbronorites, olivine
gabbros). Economic concentrations of PGE, Ni, and Cu
in the form of disseminations of mainly intercumulus
sulfides are found in the Main Sulfide Zone (MSZ)
hosted in pyroxenites, some meters below the transition
from the Ultramafic to the Mafic Sequence (Prendergast
and Wilson 1989).
Production of PGE from the MSZ commenced at the
Hartley Platinum Mine in the Darwendale Subchamber
in 1996. At the Hartley Platinum Mine, the MSZ out-
crop is on the western flank of the Great Dyke and
trends in a NNE direction (Fig. 1). The MSZ dips about
18E and pristine sulfide MSZ ores were mined from
100 m below surface downwards. As from late 1997,
oxidized MSZ ores were excavated in a number of open
pits following the outcrop of the MSZ (Fig. 2). How-
ever, mining of oxidized MSZ ores was terminated early
in 1999 due to insufficient, low recoveries, followed by
the suspension of underground mining later that year.
The mine is currently under care and maintenance.

Previous work

Geochemical and mineralogical characteristics of the

pristine MSZ reported in Oberthür et al. (2003) will be
used for comparison. Weathered, oxidized MSZ ores
were investigated by Wagner (1929), who reported
sperrylite and cooperite in ores from the Old Wedza mine
(close to Mimosa mine; see Fig. 1). Evans et al. (1994),
Oberthür et al. (1999, 2000), and Evans and Spratt (2000)
studied oxidized MSZ ores and found Pt grades similar
to those of the pristine MSZ; however, they agree that a
large proportion of the primary PGE-carriers including
PGM has been destroyed and that their PGE contents
are now distributed either in iron-hydroxides, or smec-
tites, or as discrete ‘‘PGE-oxides or -hydroxides’’.
Gordon (1923) prospected for gold and ‘‘platinum’’
in rivers along the Great Dyke close to Shurugwi (Sel-
ukwe Subchamber) and found some anomalous Pt
contents by fire assay in the concentrates. A first re-
connaissance study on alluvial PGM originating from
the Great Dyke using modern mineralogical techniques
was conducted by Oberthür et al. (1998) who reported
rare grains of sperrylite, Pt-Fe alloy, Os-Ir-Ru alloy,
atheneite, and isomertieite in heavy mineral concentrates
from various rivers flowing along the Great Dyke.
Fig. 1 Generalized geology of the Great Dyke, and locations of
platinum mines and prospects
Samples and methods
Surface and underground locations of the samples studied are
shown in Fig. 2. Two vertical profiles across the oxidized MSZ,
1.0 m (pit 130; HOP-10x) and 1.8 m (pit 5; HOP-20x) long, were
sampled about 5 and 15 m below surface in the open pits. In ad-
dition, 1-m-wide composite samples (HOP-30x) across the oxidized
MSZ were taken in two open pits (panels 102 and 120) at depths of
3, 8, 12, 16, 20, 25, and 30 m below surface. The whole rock
samples were analyzed for major and trace elements by XRF
(BGR), and PGE contents were determined by INAA after Ni-
sulfide extraction (Actlabs, Canada). In addition, heavy mineral
concentrates were prepared from the samples of oxidized MSZ
(HOP-10x: 1-kg samples; HOP-20x: 4.8-kg samples; composite
samples HOP-30x: 1.4 kg each).
At two localities along the Makwiro River, about 200 kg of
gravel and sand was sieved and panned to produce heavy mineral
concentrates. These were further treated at the BGR laboratories to
produce a final concentrate of the heaviest heavy minerals, which
346

Fig. 2 Part of the Hartley

Platinum Mine concession area
showing geographical features,
underground workings as at
June 1999, surface outcrop of
the MSZ, localities of MSZ
surface samples, and sample
points of the stream sediments

were studied under a binocular. Grains of interest were hand-

picked and transferred to an SEM sample holder. The surface Results
morphology of the grains and their chemistry were studied using an
SEM with an attached EDS system. Finally, polished sections of Oxidized MSZ: petrographic and geochemical aspects
the detrital PGM grains were prepared. Polished and thin sections
were made from the rock and concentrate samples. The sections
were investigated by reflected light microscopy and SEM/EDS. The oxide ores in the open pits form competent layers,
Mineral analyses were performed using a Cameca Camebax elec- light to dark brownish in color (Fig. 3), and locally show
tron microprobe at the analytical conditions described in Oberthür some greenish or bluish staining caused by secondary
et al. (2003).
 347

Fig. 3 Panoramic view of open pit workings of the MSZ at Hartley
Platinum Mine, panel 102, view south, February 1999. MSZ
horizon dips about 18E and is conspicuous due to its dark-brown
weathering. Overlying websterite and gabbronorites in the hanging
of the MSZ and to left side of photo have whitish weathering colors
communication) or in the course of extensive explo-
ration drilling in the Ngezi project area (H. Wilhelmij,
personal communication).

Cu- and Ni-minerals. The orthopyroxenes of the py- Oxidized MSZ: ore mineralogy
roxenites show only incipient alteration, but the inter-
stitial network is filled by iron-hydroxides and brownish The samples are characterized by an interstitial network
smectites. All samples of this study, taken down to 30 m filled by iron-hydroxides and brownish smectites, and
below surface, are pervasively oxidized with regard to rare relict sulfides, mainly pyrrhotite, surrounded by
the sulfides. Relict sulfides, transected and surrounded rims of iron-hydroxides. Pentlandite, the major carrier
by iron-hydroxides, are rare. of Pd in the pristine MSZ ores, is generally destroyed,
Geochemical profiles of oxidized MSZ resemble although relict shapes of this mineral, now replaced by
those of pristine MSZ sequences with respect to their iron-hydroxides, are discernable. Microprobe analyses
general shapes and Pt grades. However, the element show that a large proportion of the Ni and Cu is hosted
distributions show a wider dispersion, in part proba-
bly also due to the larger sample widths of 20 cm.
In profile, HOP-20x (Fig. 4), the decoupling of
Pd fi Pt fi Au, is well discernable, but the peaks of Ni
and Cu are not as pronounced as in profiles of pris-
tine MSZ (c.f. Oberthür et al. 2003; Fig. 3). Notably,
a variable proportion of the Pd is "missing" relative to
Pt when compared with the pristine MSZ ores.
Whereas average Pt/Pd ratios of 1.30 characterize
pristine sulfide MSZ (Brown 1998a), the two profiles
of oxidized MSZ investigated have Pt/Pd ratios of
2.05 and 2.26, respectively, and the average Pt/Pd
ratio of the composite samples is 2.41. Similar profiles
from Ngezi, Unki, and Mimosa have Pt/Pd ratios
ranging from 2 to 3.5 (Oberthür 2002, unpublished
data). The increased Pt/Pd ratios corroborate the
findings of, for example, Wagner (1929), Fuchs and
Rose (1974), and Evans et al. (1994) that Pd is more
mobile than Pt and is dispersed in the supergene en-
vironment. It is recalled in this context (see Part 1)
that most of the Pd is hosted in pentlandite (Weiser
et al. 1998; Oberthür et al. 2000), whereas Pt is
dominantly present in the form of discrete PGM in
the pristine MSZ. Moreover, worth mentioning is that
cementation zones or enrichment horizons in the oxi- Fig. 4 Profile HOP-20x (9 samples, each 20 cm wide) across
dized MSZ ores were not observed during open pit oxidized MSZ showing the distribution patterns of Cu and Ni (in
mining at Hartley Platinum Mine (R. Brown, personal ppm), Pt, Pd, and Au (in ppb)
348

in smectites and not in the iron oxides/hydroxides. Ore
microscopic studies reveal that discrete PGM are ex-
tremely rare in polished sections (Fig. 5a). Therefore,
heavy mineral concentrates were prepared from the ox-
ide MSZ samples. Altogether 807 discrete PGM and 613
gold grains were extracted from the concentrates.
Sperrylite grains are most common (58%), followed by
cooperite/braggite (35%) and Pt-Fe alloy grains (3.6%).
Relict (Pt,Pd)-bismuthotellurides (3.3%) were found in a
few samples only. These PGM proportions (by number)
differ considerably from those found in the pristine MSZ
ores (see Oberthür et al. 2003), which are dominated by
Pt-rich (55%) and Pd-rich bismuthotellurides (16%),
followed by sperrylite (11%), cooperite/braggite (11%),
hollingworthite/platarsite/irarsite [RhAsS/PtAsS/IrAsS]
(2%), and some rarer PGM.

Fig. 5 Photomicrographs,
scanning electron microscope
(SEM), and backscatter
electron images (BEI) of PGM
in oxidized MSZ. a Idiomorphic
sperrylite (light gray) with
roundish inclusion of pyrrhotite
and chalcopyrite (dark gray) in
situ in weathered MSZ ore
consisting of iron-hydroxides
(medium gray) and smectites
(dark gray). BEI, sample
HOP-05, ps 5663a. b Sperrylite
grain from heavy mineral
concentrate. SEM image,
sample HOP-102, grain 2350.
c Porous grain of Pt-Fe alloy
surrounded by a mixture of
secondary oxides/hydroxides
and silicates. BEI, concentrate
sample HOP-206a, ps 5910a.
d Braggite group grain showing
internal inhomogeneity of Pt-
rich (lighter) and Pd-rich
(darker) areas. Polished section,
BEI, sample HOP-103, ps
5657c. e Grain of michenerite
(white, center) in disintegration.
Alteration rim (gray) of
probable (Pt,Pd)-oxide/
hydroxide phases shows Pd, Cu,
and Fe as major elements.
Polished section, BEI, sample
HOP-206a, ps 5910a.
f Colloform, banded grain of
PGE-oxide/hydroxide phase
with shrinkage cracks. Polished
section, BEI, sample NGZ 1C
from Adit A, Ngezi concession,
ps 5711b
 349

Sperrylite mostly shows euhedral crystal shapes

(Fig. 5a, b). Cooperite/braggite, in contrast, are usually
present as splinters of irregular shapes with clean sur-
faces (Fig. 5c). In general, the sperrylite and cooperite/
braggite grains show no distinct features of alteration.
Under the binocular, most grains have silver-white sur-
faces; however, some grains have very thin, black surface
coatings. Internally, the braggite grains often display a
mosaic of Pt-rich and Pd-rich areas when viewed in the
BSE mode in polished sections (Fig. 5d). Grain sizes of
the PGM range from 50–400 lm for hand-picked grains.
However, sizes down to 1 lm were also observed of
PGM grains attached to or included in various gangue
minerals in polished sections of the concentrates. In
addition, some porous grains of Pt-Fe alloy were de-
tected (Fig. 5c), which probably represent replacements
of some other precursor PGM of unknown chemical
composition. Notably, Schneiderhöhn and Moritz
(1939) showed texturally similar porous grains of native
Pt from oxidized Merensky reef and proposed that these
grains represent relicts of former sperrylite or cooperite
grains.
The formation of mineralogically and chemically
ill-defined ‘‘PGE-oxides/hydroxides’’ was observed
around relict, disintegrating (Pt,Pd)-bismuthotellurides Fig. 6 Mineralogical variation of discrete PGM grains (n=number
(Fig. 5e). These alteration phases are generally porous at of PGM grains) in profile HOP-20x across oxidized MSZ (compare
various degrees. Chemically, the alteration phases are with Fig. 4) as found in heavy mineral concentrates made from
quite inhomogeneous and are characterized by the rel- samples of 4.8-kg weight each
ative loss of Bi and Te, an upgrade of Pt and/or Pd
contents (e.g. from ca. 30–35 at% Pt in moncheite to 60– pristine sulfide MSZ as shown in Fig. 9 of Oberthür et al.
70 at% Pt in the alteration rims; oxygen not analysed), (2003). Furthermore, some relict (Pt,Pd)-bismuthotellu-
and substantial gains in Fe and Cu (up to some wt%). ride grains, slightly altered along their rims or nearly
Occasionally, strongly elevated contents of Se and V (up completely disintegrated (Fig. 5e), are present in the
to some wt%) are present. In addition to the alteration center of the profile, i.e. on and above the Pt peak. Rare
rims around disintegrating (Pt,Pd)-bismuthotellurides, Pt-Fe alloy grains are commonly porous (Fig. 5c) and
individual, colloform grains of (Pt,Pd)-oxide/hydroxide were only found on and below the Pt peak in profile
phases were detected (Fig. 5f). Although up to 20 ele- HOP-20x. The concentrates of the composite samples
ments were analyzed, totals of only 80–90 wt% were (HOP-30x) mainly contained varying proportions of
achieved, indicating that these phases are oxides or sperrylite and cooperite/braggite grains only, indicating
hydroxides. Notably, Evans and Spratt (2000) also that pervasive oxidation of the MSZ penetrates down to
described various (Pt,Pd)-oxides/hydroxides from the at least 30 m below surface in the open pits at Hartley
Zinca prospect and reported similar low analytical to- Platinum Mine. Indeed, with the exception of a few relict
tals. Gold grains (40–300 lm) have shapes (filigree, grains of Pd-rich (Pt,Pd)-bismuthotellurides, the ores of
hooked, platy with crystal faces) that far more resemble oxidized MSZ only contain discrete grains of Pt-rich
gold from primary deposits rather than rounded, detrital PGM.
gold.
A distinct vertical zonation with respect to the dis-
crete PGM grains extracted and their proportions was Detrital PGM, Makwiro River
noted within the profiles. From the four samples of
profile HOP-10x, 142 PGM grains (66 sperrylite and 76 The headwaters of the Makwiro River are some 25 km
cooperite/braggite) were extracted. The ratio of sperry- NE of Selous in Archean granite-greenstone terrain.
lite to cooperite/braggite grains increases from 1:3 at the From there, the river flows in a westerly direction and
bottom to 9:1 on top of the profile. Similarly, the nine crosses the Great Dyke some 15 km north of Selous,
samples of profile HOP-20x (407 PGM grains) demon- where it changes direction towards the south, mainly
strate a steady relative increase of the ratio sperrylite to flowing on rocks of the Great Dyke on its western side,
cooperite/braggite from bottom to top, with cooperite/ close to the contact with Archean granites (see also
braggite grains being present in the lower portion of the Fig. 2). The heavy mineral concentrates from the
profile only (Fig. 6). The varying proportions of these Makwiro River are mainly made up of grains of chro-
two PGM probably reflect an original feature of the mite (>90%), magnetite, rutile, ilmenite, zircon,
350
monazite, rare pyrite, and pentlandite, as well as the
phase [Ni6FeCu], identified as a Cu-bearing awaruite by
XRD analyses. Notably, this awaruite was found to
carry up to 19.96 at% Pt (substituting for Ni).
We recovered 162 PGM and 271 gold grains from the
concentrates by panning (Table 1). The Pt grade of the
gravel was calculated to be around 15 ppb Pt by taking
into account both the grain sizes and the Pt contents of
the PGM recovered. The detrital PGM assemblage dis-
tinctly contrasts with that of both the pristine and the
oxidized MSZ (Table 1). Sperrylite (47%) and Pt-Fe
alloys (33%) predominate in the gravels, followed by
cooperite/braggite (15%). Other PGM comprise three
grains of potarite [Pd,Hg] and one grain of atheneite
[(Pd,Hg)3As].
Pt-Fe alloy grains are mainly equidimensional,
usually rounded, and they display smooth, convex,
polished, silver-white surfaces when viewed under a
binocular microscope (Fig. 7a). Internally, the Pt-Fe
grains are generally compact and chemically homoge-
neous (25–26 at% Fe). Intergrowths and inclusions are
rare. Sperrylite is mostly present in the form of well-
crystallized grains. Grain surfaces occasionally display
etch pits (Fig. 7b), and overgrowths of native Pt are
also common (Fig. 7c). Partial replacements of
sperrylite grains or overgrowths of pure Pt are also
obvious in polished sections (Fig. 7d). Cooperite/
braggite grains are inconspicuous in general. Some
grains, however, are distinct by features of external
corrosion and partial internal leaching along irregular
corrosion channels. A number of porous PGM grains
(Fig. 7e) essentially consist of Pt (95–99 at% Pt,
1–2 at% Pd). Potarite and atheneite form irregular,
chemically homogeneous grains. Internally, the ath-
eneite grain shows a foam pattern characterized by
darker and lighter areas due to slightly varying con-
tents of Hg (Fig. 7f). PGM grain sizes range from 65–
480 lm (mostly between 150 and 200 lm), those of the
gold grains from 50–750 lm.
Table 1 Relative proportions by number and in % of discrete PGM
grains in pristine and oxidized MSZ, Hartley Platinum Mine, and
of detrital PGM grains from the Makwiro River
PGM type Locality
Sulfide MSZ Oxide MSZ Makwiro River
n=181 n=807 n=162
(Pt,Pd)(Bi,Te)a % 71 3.3 – gether make up 22% of the discrete PGM only. There-
PtAs2 % 11 58 47
(Pt,Pd,Ni)S % 11 35 15
Pt and Pt-Fe alloys % 1 3.6 33
b
PGE-AsS % 2 0.1 –
Others % 4c xd 5e
Gold (n) 26 613 271
a
(Pt,Pd)(Bi,Te)=(Pt,Pd)-bismuthotellurides
b
PGE-AsS=PGE-sulfarsenides (see text)
c
PtSnS (5x), RuS2 (3x)
d
Unspecified (Pt,Pd)-oxides/-hydroxides
e
PdHg (5x), (Pd,Hg)3As (2x), unspecified Pd-arsenide (1x)
Summary and discussion
Oxidized MSZ
Thermodynamic data and field studies have demon-
strated that the platinum-group elements are variably
mobile in supergene environments; however, the pro-
cesses of PGE redistribution and their mobilities in the
supergene environment are much debated and cases of
both dispersion and concentration have been proposed.
Near-continuous underground and surface exposures
of the MSZ allowed us to investigate the behaviour of
the PGE and PGM in the exogenic environment in
detail.
Based on a thermodynamic approach, Mountain and
Wood (1988) suggested that Pt and Pd may be mobile in
a variety of environments. They found that the stability
field of sperrylite is much larger than that of Pt-sulfides,
even down to 25 C, which explains the common pres-
ence of sperrylite in placers. Wood and Vlassopoulos
(1990) investigated the dispersion of Pt, Pd, and Au
around PGE mineralization in Quebec, and observed
that Pt and Au seemed to be dispersed mainly in par-
ticulate form by mechanical processes, whereas Pd is
dispersed mainly in true solution and is ultimately
drained away. However, the above authors also com-
ment that experimental data on the dissolution in vari-
ous media and the transport of Pt, Pd, and Au
simulating natural processes are largely missing.
In the oxidized MSZ ores at Hartley Platinum Mine,
the sulfide aggregates have been replaced by iron hy-
droxides. Considerable amounts of Ni and Cu are pre-
sent in smectites. Pt/Pd ratios of the oxide ores are
elevated relative to their sulfide counterparts, underlin-
ing that Pd is more mobile than Pt in the supergene
environment. Pentlandite, the major carrier of Pd in the
pristine MSZ, has been destroyed in the course of oxi-
dation of the MSZ ores. The discrete PGM grains pre-
sent at Hartley Platinum Mine are Pt-phases (mainly
sperrylite and cooperite/braggite) which are regarded as
representing relict phases of the primary MSZ ores. This
is underlined by the similar frequencies and vertical
distribution patterns of these minerals in pristine and
oxidized MSZ (see Fig. 9 in Oberthür et al. 2003, and
Fig. 6 of this study). However, it must be recalled that
(Pt,Pd)-bismuthotellurides predominate (71%) in the
pristine MSZ, and sperrylite plus cooperite/braggite to-
fore, about 70% of the Pt and nearly 100% of the Pd of
the pristine MSZ are not present in a particulate form in
the oxidized MSZ. Evans et al. (1994) proposed that
Pt-Fe alloys formed from (Pt,Pd)-bismuthotellurides in
oxidized MSZ ores from the Zinca area. The present
study identified a number of porous Pt-Fe grains in
oxidized ore (Fig. 5c), which may support the view of
Evans et al. (1994). However, the small number of Pt-Fe
alloy grains identified indicates that an additional pro-
cess must have taken place and that a large proportion
 351

Fig. 7 Photomicrographs,
scanning electron microscope
(SEM), and backscatter
electron images (BEI) of
platinum-group minerals from
the Makwiro River. a Well-
rounded grain of Pt-Fe alloy.
SEM image, grain 1007. b Well-
crystallized sperrylite grain with
crystallographically orientated
etch pits. SEM image, grain
4413. c Sperrylite grain with
thin overgrowth of native
platinum. SEM image, grain
4423. d Sperrylite (gray) with
thin, discontinuous rim of
chemically pure native platinum
(white). Polished section, BEI,
ps 5981. e Porous grain of
native platinum. Polished
section, BEI, ps 5981. f Grain of
atheneite [(Pd,Hg)3As] showing
internal foam texture. Lighter
areas have slightly higher Hg
contents. Polished section, BEI,
ps 5981

of the Pt and Pd must be present in some other miner-
alogical form.
Evidence has mounted in recent years that PGE-
oxides or PGE-hydroxides exist in the oxidized zone or
in laterites of many deposits in the world (e.g. Weiser
1990; Augé and Legendre 1994; Augé et al. 1995; Jedwab
1995; Salpéteur et al. 1995; Hey 1999; Evans and Spratt
2000; Oberthür et al. 2000). These phases are incon-
spicuous in reflected light and, therefore, may have been
overlooked in previous studies.
Recent work of Evans and Spratt (2000) and Obe-
rthür et al. (2000) has identified a number of these ill-
defined PGE-oxides/hydroxides in ores of the MSZ,
where these phases occur in two major modes. Relict
(Pt,Pd)-bismuthotelluride grains have rims of low-
reflecting, porous, (Pt,Pd)-oxide/hydroxide phases which
352
occasionally show shrinkage cracks. Microprobe ana-
lyses of these grains indicate that they are oxides or
hydroxides. Their alteration largely takes the form of
removal of Te and Bi and addition of oxygen (O, OH),
accompanied by an overall upgrading of the Pt contents
of the neoformed phases relative to their precursor
minerals. In a second manner, individual, occasionally
distinctly zoned grains of (Pt,Pd)-oxide/hydroxide
phases are found interstitially to silicates and in part
intergrown with secondary phases. These grains may
represent relicts of disintegrated sulfide aggregates in-
cluding Pd-bearing pentlandite, or precipitates from
dissolved PGE which were mobilized by supergene
fluids.
A first attempt to quantify the problem of the
‘‘missing’’ Pt and Pd contents not present as distinct
minerals was made by Evans and Spratt (2000). These
authors re-investigated oxidized MSZ samples from the
Zinca area and identified cooperite/braggite and
sperrylite grains as well as various Pt-oxide/hydroxide
phases. The latter made up about 60 wt% of the Pt
phases and could therefore largely account for the
‘‘missing’’ Pt (ca. 70% at Hartley Platinum Mine),
whereas the fate of much of the Pd is still unknown.
Although the presence of Pt and Pd in the form of the
mineralogically and chemically ill-defined PGE-oxides/
hydroxides has been substantiated at Hartley Platinum
Mine, more work is needed to chemically characterize
these phases. Furthermore, the relative proportions of Pt
and Pd present as distinct PGM, hosted by (Pt,Pd)-
oxide/hydroxide phases and also by iron-hydroxides or
by smectites, still have to be evaluated.
Apparent grain sizes of the PGM, measured in pol-
ished sections, in general range from <5 to 50 lm in
diameter in the pristine MSZ (exceptionally, some lath-
shaped moncheite grains reach up to about 250 lm in
length). In marked contrast, true grain sizes (in con-
centrates) of ca. 50–400 lm are typical for the PGM
found in the oxide ores. These differences in grain sizes
can be explained by either (1) growth of the PGM in the
supergene environment, as, for example, proposed by
Bowles (1986, 1995), or (2) the different methods of in-
vestigation (polished sections of pristine MSZ versus
concentrates and sections of oxidized MSZ). The present
observations favour destruction of primary PGM rather
than PGM growth or neo-formation (a possible excep-
tion is the generation of porous Pt-Fe grains; Fig. 5c).
Many crystal surfaces of discrete PGM in the oxidized
ores show signs of etching or are blackish under the
binocular due to thin surface layers of unknown com-
position, both indicating chemical breakdown rather
than crystallization. It is recalled in this context that Ney
(1977) tabulated the probability of finding gold grains in
polished sections (20 mm in diameter) of gold ores.
Accordingly, if an ore has 10 g Au/t, and if the gold
grains have diameters of 150 lm, about 100 polished
sections have to be studied to find one grain of gold
only. In order to solve the observed discrepancy in size
distributions, one sample of pristine MSZ, weighing
about 1 kg, was treated by electric pulse disintegration
at the University of Leoben. Altogether, 75 PGM grains
larger than 50 lm were hand-picked from this sample.
The observed maximum true diameters were 480 lm for
(Pt,Pd)-bismuthotellurides (moncheite), 85 lm for
sperrylite, 195 lm for cooperite/braggite, and 300 lm
for Pt-Fe alloy grains. These data underline (1) that
coarser PGM are present in the pristine MSZ, and (2)
that the observed differences in grain sizes result from
the different methods of sampling and investigation.
Gold grains in the oxidized MSZ also are of larger
size (40–300 lm) compared to those of the pristine MSZ
(<5–30 lm). However, the shape of the gold grains,
their textural positions, and intergrowths indicate that
gold coagulates to form larger grains in the supergene
environment.
Detrital PGM
The redistribution of PGE and PGM in the exogenic
cycle was complemented by a study of detrital PGM
found in the Makwiro River. The general trends ob-
served from pristine via oxidized MSZ into the fluvial
environment are shown in Fig. 8. The PGM assemblage
found in the Makwiro River is distinctly different from
that of pristine and oxidized MSZ (Table 1, Fig. 8). In
the concentrates of the Makwiro River, (Pt,Pd)-
bismuthotellurides are absent, and cooperite/braggite
grains are scarce. Besides sperrylite, ubiquitous Pt-Fe
alloy grains are present as well as the rare Pd-Hg and
Pd-Hg-As minerals potarite and atheneite. It is proposed
that the sperrylite grains are relict phases originating
from the MSZ, thus indicating that sperrylite is a stable
phase in the supergene environment. Most of the
cooperite/braggite grains show signs of disintegration.
Obviously, a large proportion of the grains has been
destroyed in the course of prolonged oxidation (i.e. they
are "metastable" in the oxidized MSZ ores), as shown by
Fig. 8 Summary of trends of PGE mineralogy and geochemistry
from pristine MSZ via oxidized MSZ into the fluvial environment
of the Makwiro River. (Pt,Pd)(Bi,Te)*=(Pt,Pd)-bismuthotellu-
rides. (Pt,Pd,Ni)S=cooperite/braggite. Pt/Pd ratios relate to whole
rock data of pristine and oxidized MSZ, and estimate from PGM
abundance in sediments of the Makwiro River

the increasing ratio of sperrylite to cooperite/braggite
from pristine via oxidized MSZ to the fluvial environ-
ment. The high proportion of Pt-Fe alloy grains is
conspicuous. Possible sources of the Pt-Fe alloy grains
comprise the following: (1) they are direct descendants
from the MSZ. This is improbable as they are rare in
pristine and oxidized MSZ ores, and a prolonged con-
centration and upgrading of these grains in the fluvial
environment appears unlikely. Furthermore, Pt-Fe alloy
grains should be present in similar proportions relative
to sperrylite as in the MSZ, which is not the case (see
Table 1); (2) the Pt-Fe alloy grains originate from dis-
seminated occurrences in other rock units of the Great
Dyke, e.g. chromitites. This possibility is not supported
by the present work as no PGM were found further
upstream in the Makwiro River, and Pt-Fe alloy grains
have not been reported from chromitites of the Great
Dyke (Germann and Schmidt 1999; Oberthür 2002); and
(3) Pt-Fe alloy grains represent neo-formations that
came into existence in the course of weathering of the
MSZ ores and the concomitant supergene redistribution
of the ore elements. Observations in the oxidized MSZ
ores (porous Pt-Fe alloy grains; Fig. 5c) and of PGM in
ferralitic soils of Madagascar (Salpéteur et al. 1995) are
in support of hypothesis (3), but do not fully explain the
quantity of Pt-Fe alloys present. At the current state of
knowledge, it must be speculated that some of the Pt-Fe
alloy grains are true neo-formations that formed in the
supergene environment. Their precursor phases either
are pre-existing, unstable PGM (note Pt coatings and
partial replacements of cooperite/braggite and also of
sperrylite; Fig. 7d), or may even have formed via a so-
lution stage under low-temperature conditions. Future
microprobe work aims at the chemical characterization
of the various Pt and Pt-Fe alloy phases, and it is hoped
that some indications of the processes responsible for
their formation will be obtained from the analyses.
The rare Pd-Hg and Pd-Hg-As phases, which are not
present in the MSZ ores, are regarded as neo-formations
which probably formed from dispersed elements during
supergene processes. The generally large sizes of the
PGM (65–480 lm) and gold grains (50–750 lm) com-
pared to those from the MSZ ores are proposed to
mainly reflect sedimentological sorting processes, as
smaller grains were probably removed in suspension.
Some of the gold grains found in the concentrates may
also originate from the granite-greenstone terrains
drained by the Makwiro River.
Metallurgical implications
The recovery of PGE from pristine, sulfide MSZ was
86% for Pt and 90% for Pd at Hartley Platinum Mine
(Rule 1998). Problems encountered in flotation are
ubiquitous talc, present in larger quantities in shear zones
of different size and scale, the finely dispersed nature of
the sulfides, and the small grain sizes of the PGM. Pre-
vious tests at processing oxidized MSZ ores achieved Pt
353
recoveries of 23.4% by gravity concentration and 28%
by flotation only (Menell and Frost 1926). Prendergast
(1990) states that all early attempts at processing oxide
ores showed Pt recoveries below 50% by either method.
In contrast, flotation recoveries of about 70%, slightly
lower than those of the sulfide MSZ, were assumed when
operating the open pits and working oxidized MSZ ore at
Hartley Platinum Mine. However, total PGE recoveries
dropped to about 50% when these ores were mixed with
sulfide MSZ ores at about equal proportions, demon-
strating that PGE recoveries from the oxidized MSZ ores
were much lower than expected. As a consequence, open
pit mining was terminated early in 1999.
Metallurgical test work performed by Zimplats on
pervasively oxidized MSZ ores (from surface down to
about 10–15 m) from the Ngezi Project achieved re-
coveries of 15–30% only. These results indicate that
probably only relict sperrylite and cooperite/braggite
grains were recovered, as also suggested by the present
mineralogical study.
Evidently, the PGE contents not recovered from the
pervasively oxidized ores either are present in the form
of PGE-oxides/hydroxides, or are dispersed in iron-
hydroxides or in smectites, at still unknown relative
proportions. Characterization of the mineralogical siting
of the PGE and quantification of the proportions of
PGE-bearing phases are needed to develop new metal-
lurgical processes which will make the vast resources of
PGE-bearing oxidized ores—not only of the Great
Dyke—technologically available.
Conclusions
The present study revealed new details on the mineral-
ogical siting and distribution of the PGE in the oxidized
MSZ, and on the redistribution of the PGE and the fate
of the PGM in the exogenic environment. Major find-
ings comprise the following:
1. The redistribution of the PGE in the exogenic cycle
was studied in the oxidized MSZ ores at Hartley
Platinum Mine, which showed pervasive oxidation
down to at least 30 m below surface. In profiles of
oxidized MSZ, the general metal distribution and
zoning patterns of the pristine MSZ are grossly
preserved. However, at similar Pt grades, some Pd
has been lost from the system as shown by the
increasing Pt/Pd ratios from pristine (1.3) to oxidized
(2–2.4) MSZ. This indicates that Pd is more mobile
than Pt and was partly removed, probably in solution
(ground- and/or surface waters), in the exogenic
environment.
2. Regarding the PGE mineralogy of the oxidized MSZ,
it was found that sperrylite and cooperite/braggite
are stable minerals. Major changes from pristine to
oxidized MSZ comprise the disintegration of the
(Pt,Pd)-bismuthotellurides and the concomitant neo-
formation of chemically and mineralogically
354
ill-defined (Pt,Pd)-oxides/-hydroxides. Furthermore,
there are indications that at least some porous grains
of Pt-Fe alloy are formed in situ from unknown
precursor PGM in the oxidized ores.
3. Processing of oxidized MSZ ores using conventional
techniques resulted in unsatisfactory PGE recoveries.
Therefore, novel methods have to be developed for
this ore type. These have to be based on a better
chemical and mineralogical characterization of the
(Pt,Pd)-oxides/-hydroxides, and on a precise knowl-
edge of the proportions of PGE hosted in discrete
PGM, being present as (Pt,Pd)-oxides/-hydroxides,
or found in a dispersed form in iron-oxides/-hydrox-
ides, or in smectites.
4. The assemblage of detrital PGM in the Makwiro
River close to the mine indicates that mineralogical
changes continue in the exogenic cycle. Sperrylite is
relatively stable in this environment, whereas most
cooperite/braggite grains have been altered or com-
pletely destroyed. (Pt,Pd)-oxides/-hydroxides were
not observed, probably due to the fact that the
porous and friable grains were mechanically de-
stroyed and/or removed in suspension. Ubiquitous
Pt-Fe alloy grains make their appearance in the
alluvial sediments. Most likely, the Pt-Fe alloy grains
are neo-formations that formed either from pre-
existing, unstable PGM, or via a solution stage under
low-temperature conditions.
Acknowledgements Sincere thanks go to G.L. Holland and R.
Brown, chief geologists of BHP/Hartley Platinum Mine, as well as
P. Vanderspuy, H. Wilhelmij, and H. O’Keeffe of Zimplats, for
their continuous support of our fieldwork in Zimbabwe, editorial
suggestions, and for permission to publish this paper. K. Kap-
penschneider of Hartley Platinum Mine kindly provided digital
maps. Laboratory work was ably performed by J. Lodziak (elec-
tron microprobe), C. Wöhrl (SEM), K. Souto Otero (map draw-
ings), A. Weitze, C. Laurisch, and S. Pietrzok (image processing),
P. Schlüter and S. Schwarz (data evaluation and drawings). Critical
reviews by Johan Kruger, Wolfgang Maier, Frank Melcher, and
Oskar Thalhammer considerably improved the paper.
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