THE GEOCHEMICAL NATURE OF THE MERENSKY REEF:

EVIDENCE FOR LATE-STAGE REACTIONS AND CONTROLS

ON THE PLATINUM-GROUP ELEMENT MINERALISATION

C A LEE
DIVISIONAL CONSULTING GEOLOGIST
GROUP GEOLOGICAL SERVICES
JOHANNESBURG CONSOLIDATED INVESTMENT COMPANY, LIMITED

and

R T BROWN
ASSISTANT CHIEF GEOLOGIST
RUSTENBURG SECTION
RUSTENBURG PLATINUM MINES LIMITED

1994

JCI Geologists Technical Meeting, 9, p45-67

 ABSTRACT

Merensky reef drilled ahead of development and subsequently mapped in the stopes has
been analysed in detail for a range of elements. Silicate mineral chemistry was determined
on one intersection.

The major rock types are defined by the geochemistry, notwithstanding the petrographic and
textural variability. Footwall and hanging wall norite and leuconorite have contrasting
chemistry. Feldspathic pyroxenite and pegmatoidal feldspathic pyroxenite are, to a large
extent geochemically indistinguishable except for where the platinum-group elements are
concerned. On a smaller scale, geochemical changes in abundance patterns define
gradations independent of rock-type.

Platinum-group elements sequences are enriched in a variety of volatile, late-stage related

elements. Mineral chemistry and whole-rock elements ratios indicate extensive sub-solidus
redistribution of sulphide and element exchange between mineral phases within the
feldspathic and pegmatoidal feldspathic pyroxenites. Primary magmatic processes appear to
be preserved in the plagioclase-rich rocks.

1. INTRODUCTION

Geochemical studies have been conducted on four closely sampled, normal Merensky reef
sections from Frank Shaft, Rustenburg Platinum Mines – Rustenburg Section (fig.1). Frank
Shaft is ideally situated in that the Merensky reef is relatively undisturbed and, the transition
from the texturally variable thicker Merensky reef facies in the west to the thinner facies in the
east is exposed (Brown, 1991).

This paper reports on some aspects of the larger study, the subject of further reports.

The project was undertaken to obtain basic geochemical data for the Merensky reef, which is
presently not available, and which would assist in modeling the origin of the PGE enrichment
in the Merensky reef. The data can also be used as a ‘base-line’ from which to determine
geochemical changes that may occur in potholed Merensky reef. Furthermore, the data will
also assist in evaluating models published from time to time.

Normal Merensky (MR) is defined as the economic base-metal sulphide (BMS) and platinum-
group element (PGE) enriched, texturally variable, plagioclase-bearing (feldspathic)
orthopyroxenite or olivine orthopyroxenite layer, which is situated at the base of the Merensky
Unit. There is considerable variation in layer thickness, texture, and to a lesser extent, style,
grade and location of BMS and PGE mineralisation. Texturally it is either pegmatoidal,
partially pegmatoidal, or less commonly, medium-grained and, has one or more thin
chromitite layers associated with it (commonly two, but up to four). This is overlain by the
medium, to locally coarse-grained, commonly poikilitic, feldspathic orthopyroxenite of the
Merensky pyroxenite (MP), which in contrast, maintains relatively constant layer thickness.

The reef sequence paraconformably overlies the uppermost norite-leuconorite of the Boulder
Subunit, and may be directly underlain by a conformable anorthosite layer of highly variable
thickness (Brown, 1991). Typical Merensky reef sections are depicted in Figure 2.

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 2. GEOCHEMISTRY OF THE MERENSKY SUCCESSION

2.1 Methodology

High precision, low level X-ray Fluorescence (XRF), Neutron Activation Analysis (NAA) and
standard fire assay whole-rock and mineral-separate geochemical analyses were performed
on four closely, continuously sampled Merensky successions. The sample were analysed for
a range of major elements, trace elements, PGE and Au. The term Merensky succession
refers specifically, for the purposes of this study, to the sample drill sections, viz :-

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R24A: a 2.82m 32 sample section consisting of;
Hanging wall 1.25m (12)
Merensky reef 0.33m (7)
Footwall 1.24m (13)

R24A: a 3.365m 30 sample section consisting of;

Hanging wall 1.49m (12)
Merensky reef 0.28m (5)
Footwall 1.595m (13)

R26A; a 5.13m 35 sample section consisting of;

Hanging wall 2.45m (15)
Merensky reef 0.15m (3)
Footwall 2.53m (17)

R27A: a 7.07m 52 sample section consisting of;

Hanging wall 2.55m (15)
Merensky reef 1.92m (21)
Footwall 2.60m (16)

(The numbers in parentheses indicate individual numbers of samples).

Three AXT size boreholes (core diameter = 32.51mm) were drilled within centimeters of one
another at each of the five sites, i.e. R23, R24, R25, R26 and R27 (labeled A, B & C
respectively). The sites were selected with variable reef thickness in mind and located as
remotely as possible from any magmatic, metasomatic or structural disturbance (Fig.3). They
were drilled from just beneath the footwall marker up to the Bastard pyroxenite (Fig.4), ahead
of advancing longwall faces, which allowed later detailed study of the intersection sites. Of
the three intersections at each site, one was used for geochemical analysis (A), another for
thin and polished sections (B), and one retained for any further work (C). R23 is also a thick
reef intersection and has been retained as a spare intersection in its entirely. This technique
has ensured that unusual reef facies have not been chosen, and the whole reef environment
and setting has been documented prior to the geochemical study.

Detailed whole-rock and mineral major and trace chemistry was completed on intersection
R27A (Fig. 5) by XRF. A thick Merensky reef was selected for this purpose as geochemical
behaviour, which may be masked to some extent in the thinner reef facies, or, sampling
intervals would have to have been unrealistically small. Intersections R24A, R25A and R26A
were analysed for trace elements. In addition, R27A and R25A were analysed for PGE and
Au, by NAA and fire assay respectively.

2.2 General

Although many trends are evident, major and trace element profiles fundamentally serve to
distinguish the combined MR/MP pyroxenite package from the underlying and overlying and
overlying norites. The Merensky reef and overlying Merensky pyroxenite are distinguishable
from one another on the basis of texture, and late-stage modification as a whole.

With very few exceptions, the pyroxenite package as a whole broadly displays either sharply
enriched, or depleted, pronounced sawtooth profiles relative to the adjacent norites.
However, noticeable smoothing of the profiles does occur at the top and bottom of the MR/MP
package, i.e. from immediately above the upper chromitite layer of the Merensky reef,
throughout the Merensky pyroxenite, and the lower ± 0.4m of the Merensky reef (in the case
of R27A). The MR/MP package may thus be subdivided into three domains.

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2.3 Detailed Geochemistry

2.3.1 Whole Rock Geochemistry

Major Elements: Average whole rock major element analyses of the R27A thick reef
Merensky succession and presented in Table 1.

With the exception of K2O and P2O5, the major elements reflect the modal mineralogy, the
major controls being exercised by the plagioclase, pyroxene and chromite. NiO may also be
singled out as not being completely controlled by the major mineral modes, as it not only
occurs in pyroxene, but is also a major constituent of accessory BMS. This relationship will
be discussed later.

All the major element profiles show either strong enrichment or strong depletion within the
MR/MP package relative to the footwall and hanging wall norites. In addition, throughout all
the profiles to a greater or lesser extent, consistent variation exists in that;

1. profiles are less variable within the footwall and hanging wall norites relative to the
pyroxenite layers;

2. the change in element abundance from the footwall norite into the Merensky reef is
accompanied by smooth profiles, which extent 0.3m to 0.5m into the Merensky reef;

3. the upper ± 1.5m of the Merensky reef is characterised by highly variable sawtooth
element profiles;

4. the overlying Merensky pyroxenite is characterized firstly by element abundances,

and secondly, by smoother element profiles than the upper part of the Merensky reef.

The Fe shows a sharp enrichment at the base of the Merensky reef from the underlying
leuconorite, and thereafter a gradual enrichment up through the Merensky reef and Merensky
pyroxenite, with a corresponding decrease in the magnesium number, Mg#, (the Mg/Mg + Fe
ratio (Fig.6). This is indicative of silicate fractionation in a closed system. The rapid, but more
gentle decrease in total Fe from the Merensky pyroxenite into the overlying norite is
consistent with the gradational contact between these layers.

Na2O, CaO and AI2O3 are depleted within the Merensky reef and Merensky pyroxenite
relative to the adjacent norite, being the major cationic species of plagioclase. Both Na2O
and AI2O3 show an upward depletion through the MP/MR succession, while CaO, enhanced
by the calcium number, Ca# *the Ca/Ca+Na) ratio) profile, interestingly enough, shows an
upward Ca enrichment (Fig.6). This is the reverse of what would be expected from a
fractionation trend. Plagioclase occurs as an intercumulus mineral within the MR and MP
pyroxenites. It is possible therefore that, either;

1. the lack of a fractionation trend is the result of porosity being maintained at a

relatively high level (this however would appear to be in contradiction with the
pyroxene fractionation trend), or

2. the Ca enrichment may be the result of the increased abundance of clinopyroxene up

through the pyroxenites, e.g. augite oikocrysts within the MP, or

3. the Ca-enrichment is the result of late-stage modification or reaction, which has

overprinted the original intercumulus process, with the plagioclase now intermediate
in composition between cumulus and intercumulus composition. A number of
authors, e.g. Lee (1983) and Cawthorn & McCarthy (1985), have pointed out that
intercumulus plagioclase is subject to late-stage equilibration and therefore cannot be
used as a fractionation monitor.

K2O and P2O5 show an erratic enrichment within the MR/MP pyroxenite package, but as such
do not accurately define the sequence apart from the adjacent norites. These elements are

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primarily sensitive to late-stage phases such as phlogopite and apatite. In addition, these
elements do not distinguish between the Merensky reef and Merensky pyroxenite as well as
do the other major elements.

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The pyroxenite interval is marginally enriched in Ti (Fig. 7). Of interest however, is the
deviation trend where the enrichment starts within the footwall leuconorite and continues up
through the Merensky reef basal contact, maintaining a smooth profile 0.8m up into the reef.
Of note too is the fact that the uppermost chromitite layer is highly enriched in Ti (and also
Fe), while the underlying chromitite layer shows no greater enrichment than the enclosing
pyroxenite.

Trace Elements: Average whole-rock trace element analyses are listed in Table 1. The
majority of the trace element profiles, to differing extents, identify the MR/MP pyroxenite
package. They also, to differing extents and in many cases not as clearly as the major
elements, identify the three pyroxenite domains.

Through the Critical Zone cumulate sequence Ni abundance exceeds Cu (Fig. 8). This same
pattern is observed in the four Merensky successions in this study. The variance is small
within the footwall and hanging wall norites, whereas in the MR/MP package variance is high.
Sporadic samples within the reef sequence have higher Cu/Ni ratios, and in two cases, Cu
exceeds Ni. The Cu and Ni profiles for R27 and the three other Merensky reef sequences
show the variation within the reef package. This pattern is a fundamental contrast to
sequences such as the Munni Munni (Barnes & Tredoux, 1990). Munni Munni is Cu-
dominant and there is a 3 to 4-fold increase in Cu abundance within its profiles, offset from
the PGE peaks. In the case of the Great Dyke there is little variation in the Cu/Ni ratio, but
abundances do increase as an offset above the PGE peaks (Wilson & Tredoux, 1990), as in
Munni Munni. Within the Merensky sequences there is an erratic and minor increase in the
Cu/Ni ratio, the greatest variation being in the pyroxenite package, as a whole. Within the
cumulate sequence up to and beyond the pyroxenite the Cu/Ni ratio is also erratic, but shows
a slight increase. There is a drop in the ratio just above the Merensky pyroxenite, to a level
coincident with a virtual straight line, gradually increasing trend, extrapolated from the footwall
leuconorite.

The high variance within the MR/MP pyroxenite correlates with the modal mineralogy. The
sawtooth appearance of the profiles is similar to the patterns observed in element zoning in
crystals (Halden & Hawthorne, 1993). The zoning patterns have been interpreted in terms of
fractal geometry. This approach may be potentially useful in order to interpret more
accurately the sharp variation patterns obtained within the MR/MP package and in the subject
of a separate study.

Sr can be used a measure of modal variation as Sr partitions strongly into plagioclase. The
Cu/Ni ratio is influenced by the abundance of orthopyroxene and the composition of the base
metal sulphides. Some higher Cu/Cu+Ni ratios correlate with higher plagioclase (i.e. lower
silicate Ni), but in the sulphide-dominant part of the sequences this control is minimal, and is
overwhelmed by the BMS composition and abundance.

Cu, Ni and S follow very similar profiles with sympathetic peaks. There is a distinct offset of
the Zr peaks when compared with Cu, Ni and S profiles, indicating late-stage decoupling of
sulphides and incompatibles. This could have been the result of an intercumulus space
problem, with intercumulus plagioclase, BMS, late-stage accessories and trapped fluid all
competing for the same space.

Two sulphide populations are evident. Zr is a measure of trapped material in a cumulate. If S

and Zr are trapped simultaneously, then there will be a Zr-S correlation. If S displaces
trapped material through migration of S-melt, then a S-Zr correlation will be non-existent.
Both relationships exist for the profiles examined. This is summarized in the logZr-logS plot
shown in Figure 9. A Straight line Zr-S trend would indicate the presence of trapped primary
sulphide. Each data set shows a pattern, but consistently indicating that the footwall
leuconorites have a Zr-S correlation. A negative correlation is shown in R25A, whereas a
positive correlation in R26A is noted for the Merensky reef pyroxenite. Important is the
observation that each sequence appears to have its own geochemical character. Within
these though the footwall leuconorites have positive trends; there are insufficient data points
for the norites within one intersection to detect an in-sequence trend. As a group there is a

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positive Zr-S, with a slight S-enrichment over the leuconorites. Notwithstanding a possible Zr-
correlation in two of the sequences, as a group of 150 data points depicted in Figure. 9, the
MR pegmatoid and MP pyroxenite are higher in Zr and S, and there is no inter-relationship to
suggest co-entrapment. The overall scatter indicates post-cumulus migration.

In general Y, Zr and Nb increase in abundance and define the pyroxene cumulate sequence.
Elevated REE contents are documented for the Atok Merensky reef (Mathez, 1994)
pyroxenes, far in extent to that anticipated from partition modeling as cumulates. The high
La, F and Nb concentrations accord with this observation, and indicate significant
metasomatism within the reef sequence.

Correlation coefficients (Table 2) for trace element pairs have been calculated for the whole
R27A sequence (rock types WNXCMRL), the hanging wall norite (WN), the Merensky
pyroxenite (X), the Merensky reef (CMR), and the footwall leuconorite (L). Briefly, specific
attention may be drawn to the following correlations:-

1. S-Zr: As already suggested these two elements correlate poorly, particularly within
the Merensky reef (0.15), with a high of 0.53 in the footwall leuconorite. The average
for the whole sequence is 0.27.

2. S-Zn: These elements behave unusually in that within the hanging wall and footwall
norites they correlate highly (0.89-0.99), but within the pyroxenites the correlation is
low (non-existent in the Merensky pyroxenite). This is probably a function of the
increased pyroxene Zn content within the pyroxenites.

The S, Ni, Cu and Co intercorrelations are high throughout the different

lithologies, in the vicinity of 0.9 +, with the highest values, being in the
Merensky pyroxenite.

3. MINERAL GEOCHEMISTRY

3.1 Orthopyroxene

Average analyses for orthopyroxene mineral separate major element are shown in Table 3.
Orthopyroxene Mg# decreases, stepwise, from the footwall leuconorite, through the
pyroxenite, to the hanging wall norite. The compositional variation is small within these three
subdivisions, but significantly different between the three. The three-way grouping is
emphasized by the plot of pyroxene AI2O3 and TiO2 against Mg# (Fig. 10a,b). Leuconorite
orthopyroxene has the highest Mg#, and an inverse relationship with AI2O3. Pyroxenite
orthopyroxene has a just perceptible positive trend between AI2O3 and Mg#: this group of
pyroxenes has the greatest range in AI2O3. The hanging wall norites have the lowest Mg#
and a positive AI2O3 – Mg# trend; these orthopyroxenes have lower AI2O3 than the footwall
leuconorite orthopyroxene. Inverse relationships between AI2O3 and TiO2 exist in the
pyroxenites and the norites, whereas in the footwall leuconorite no relationship exists. Similar
relationships exist in Critical Zone pyroxenites studied by Eales et al. (1993), who discuss the
control of plagioclase on pyroxene chemistry. Ni in orthopyroxene is highest in the
pyroxenites, where a negative relationship exists with the Mg# (Fig. 11a); in hanging wall
norite there is a positive trend, and likewise, a less well defined positive trend in the
leuconorite. Ni is enhanced in the leuconorite group as an extension of the pyroxenite trend.
In the pyroxenites there is a positive correlation between orthopyroxene Ni and Whole-rock Ni
(Fig. 11b). This is indicative of Ni exchange or re-equilibration between base-metal sulphide
and orthopyroxene in this part of the sequence. High incompatible element abundance also
occur in this part of the sequence.

Studies on the Great Dyke pyroxene and olivine cumulates (Wilson, 1992) have revealed a
fine scale relationship between Mg# and the incompatible elements such as P and Zr. P v
Mg# (or Zr v Mg#) plots were found to define individual cryptorhythmic units in the Dyke. A
Zr v Mg# plot (Fig. 12) for the R27A succession defines three distinct groups. The footwall

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leuconorites have low Zr and high Mg#, which lies on an extension of the negative trend
shown in the pyroxenites. The third grouping consists of the hanging wall norites, which show
evolved Mg# and low Zr, but no distinct trend. Unlike the Great Dyke no cyclicity is
detectable. This pattern is similar to that shown by the higher variability AI2O3-Zr plots, where
there is evidence of late-stage interaction between these elements.

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Minor components analysed include Cr2O3 and Zn, which have identical distribution patterns
with respect to Mg#. Three distinct lithological groupings are again evident. Lowest Cr2O3
and Zn correlate positively with Mg# in the hanging wall norites. Intermediate values correlate
occur in the pyroxenites, while the highest values show a negative correlation in the footwall
leuconorite. These relationships are a repeat of those shown for AI2O3-Mg#.

3.2 Plagioclase

Major element analyses for plagioclase mineral separates are presented in Table 4.
Compositional profiles for plagioclase separates define two lithological groupings on Ca#, Fe
and K2O contents, amongst others. Footwall and hanging wall plagioclase cumulates have
very similar compositions, whereas the pyroxene cumulates have lower, evolved Ca# and
higher K2O and Fe abundances, all with high variability. Binary plots of Rb, Sr, Na2O, CaO
and K2O show contrasted patterns. A positive relationship exists for K2O-Rb in the
pyroxenites, but not in the plagioclase cumulates, which form a tight cluster with low
abundances of these elements. CaO-Sr (Fig. 13a) defines two groups, both with positive
trends. The pyroxenites show a steep positive trend and somewhat lower abundances than
the separate plagioclase cumulates. The latter define a group with higher CaO-Sr
abundances and a positive trend. CaO-Rb (Fig. 13b) is the anticipated opposite of K2O-Rb
and there a negative relationship exists. The plagioclase cumulates from a tight cluster with
higher CaO and low Rb. The binary Na2O-CaO plot also shows the delineated lithologies.
Here there is no geochemical sympathy in the plagioclase cumulates, while a negative trend
exists in the pyroxenites. The norites of both the hanging wall and footwall occupy a single
field and the MR/MP pyroxenite package occupies a second field. This, particularly within the
pyroxenite package, suggests some late-stage re-equilibration.

The plagioclase Ca# - pyroxenite Mg# binary plot (Fig. 14) also strongly illustrates the three
separate stratigraphically and lithologically defined groups. The footwall plagioclase
cumulates fall into a tight high Mg#-Ca# group, but do not show evidence of any geochemical
relationship. The pyroxene cumulates have evolved Ca# and Mg# and show a steep positive
relationship. The hanging wall plagioclase cumulates from the third group, and show the

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most evolved Mg#, but high Ca# and a negative trend. This trend is stratigraphically related,
in contrast to the footwall cumulates and overlying pyroxenites, with the uppermost sample
Ca#-rich and Mg#-poor.

The Ca# profile shows a variable increasing trend within the hanging wall norite and pyroxene
anorthosite in R27A. This would appear to be a late-stage effect, as suggested earlier. There
is a close inter-relationship between plagioclase and pyroxene mineral chemistry (Fig.15).
This can be demonstrated in a plot if TiO2 in pyroxene and Ca# of plagioclase. This shows
two trends. In the plagioclase cumulates the positive relationship would reflect primary
liquidus conditions where the higher TiO2 and higher Ca#, the higher temperature of the
liquidus. Pyroxene and postcumulus plagioclase have a trend of decreasing TiO2 with
increasing Ca# as a result of the two phases forming at different times. Low TiO2 in pyroxene
may indicate restricted interaction of this mineral with trapped liquid at close to magmatic
temperatures, when the Ca# of plagioclase is also high. Greater interaction at lower
temperatures is indicated by high TiO2 and low Ca#. Thus in the feldspathic pyroxenites a
systematic interaction with trapped liquid can be inferred.

The relationship between the incompatible element chemistry and that of the cumulate (and
dominant intercumulus) minerals is of importance. The interaction of trapped intercumulus

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liquid and late-stage reaction and re-equilibration with cumulus orthopyroxene is known to
have compositional effects on the pyroxenes (Wilson, 1992).

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3.3 Platinum-Group Elements

PGE occur with sulphides in several environments, each with a particular geochemical
characteristic. This feature has complicated efforts to produce an overall model for PGE
concentration in the Merensky reef.

Some PGE deposits are compared below as an example of inter-complex variability.

The metal content of the Great Dyke, Munni Munni and Finland deposits is variable and grade
varies little with width over the mineralized sequence. In the Merensky reef however, the
metal content is constant and grade varies with reef thickness. This is a fundamental contrast
between the Merensky reef and other PGE mineralized sequences, one which has to be
incorporated into interpretations, which to date has not been done.

Many mafic layered rocks, in particular those which host economic PGE occurrences, are
PGE-bearing throughout. The PGE occur at very low levels and exhibit a lithologically
controlled pattern to the abundances. Studies in the Bushveld Complex show chromite >
feldspathic pyroxenite > norite > anorthosite to be the decreasing order of PGE abundance in
‘non-mineralised’ rocks (Lee, 1989).

In the mineralize complexes, the PGE-sulphide enriched rocks have no footwall indicator in
the geochemistry to suggest or predict the overlying PGE-carrier. The Great Dyke has <1
ppm Pt and Pd (with Pt/Pd < 1) in the footwall, and then an abrupt 2 to 6-fold increase in both
elements and a change in the Pt/Pd ratio to > 1. Abundances decrease rapidly into the
hanging wall (Wilson & Tredoux, 1990). The Munni Munni Complex in Pd-dominant. Here,
geochemical profiles show a gradual increase in Pd relative to Pt below the mineralized zone
and a rapid decrease in both elements above the sequence.

Both the Great Dyke and the Munni Munni complexes have hanging wall offset Cu-Ni peaks,
decoupled from the underlying precious metal peaks. These differ from the Merensky reef
and Platreef PGE-BMS patterns. The silicate cumulates, which enclose the UG2, and other
PGE-elevated chromitites, are also at background abundances in the immediate vicinity of the
chromitite.

In most cases the Pt/Pd ratio maintains the overall Pt-dominant or Pd-dominant character of
an intrusion, i.e. of the silicate host rocks and, provided they are not extreme adcumulates,
will have a PGE metal ratios with the same characteristics as the mineralized sequence. An
exception is the Great Dyke where there is a change from Pd-dominance in the cumulates to
a Pt-dominance in the mineralized layers.

The ‘adcumulate’ or ‘sintering’ effect on PGE needs emphasis. In a PGE study of the MG and
LG chromitites, a correlation between high modal chromite and depleted PGE has been
documented (Lee & Parry, 1988). Anorthosite and leuconorite in the Rustenburg layered
sequence are generally PGE-depleted compared to the feldspathic pyroxenites. These rocks
tend to exhibit lithology-specific Pt/Pd ratios, with pyroxenite < 1 and plagioclase cumulates >
1. Thus there is some evidence of lithological and textural influence on the element
abundances and ratios. This feature is demonstrated by the generally higher noble metal
contents in chromitite, or rock with accessory chromite (Lee, 1989).

The geochemical patterns for PGE and related chalcophile elements differ according to
overall abundance. The geochemical inter-relationships are best displayed in mineralized
sequences. In rocks with trace amounts of these elements, inter-relationships are poor to
non-existent. Furthermore, each mineralized sequence has particular and unique
geochemical patterns, and metal contents, which have to be accounted for in analysis of PGE
geochemistry.

Contrasted PGE patterns in various Bushveld rocks are part of the interpretive approach in
understanding PGE mineralisation. Geochemical inter-relationships in the PGE are a function
of overall abundance. At lower levels PGM have a greater influence on the inter-relationship
compared to rocks where BMS exist with PGM.

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Table 1 lists the PGE and Au analytical data for boreholes R27A. As is typical of Merensky
reef abundances are Pt > Pd > Ru > Rh > Au < > Ir > Os.

With the exception of Pd, all the PGE follow similar stratigraphic profiles, with the highest
values being associated with the chromitite layers. In each case the higher of the two Cr
peaks coincides with the lower chromitite layer. The profiles in general show variable PGE
enrichments within the upper ± 1.5m of the Merensky reef; these decrease above the
uppermost chromitite layer and at ± 0.4m above the reef basal contact. The profiles are
broadly comparable with the S, Cu and Ni profiles, with some localized decoupling. Pd
follows an almost reverse profile, with its highest values towards the bottom of the reef, with
an irregular upward increasing trend. Notably the highest peaks are not associated with the
chromitite layers. Au follows a trend similar to Pd, but unlike the PGE it shows relatively
elevated values within the Merensky pyroxenite, and a higher value in the upper chromitite
layer, rather than the lower one.

The Pt/Pd ratio expresses the relative abundances of Pt and Pd. The Pt/Pd profile follows a
variable profile through the Merensky reef and Merensky pyroxenite, but does not show any
convincing increasing or decreasing trends. This suggests that the PGE were not subjected
to fractionation, unlike the Great Dyke, where an upward decreasing trend in the Pt/Pd ratio
occurs (A.H. Wilson, pers. comm.,). The mean Pt/Pd ratio for the R27A MR/MP pyroxenite
package is 2.6, while those for the Merensky reef are 2.8 (including the chromitite layers), and
2.4 (excluding the chromitite layers). The mean Pt/Pd ratio of the chromitite layers
themselves is 6.1 (equivalent to a Pt/(Pt+Pd) ratio ± 0.86). These values all indicate a
considerable enrichment of Pt over Pd on all the Merensky reef components.

The relationship of total PGE+Au in the study section to base metals and to standard
geochemical parameters is shown in Figure 16a,b. Mineral Mg# and Ca# profiles show
several patterns of variance progressing up the sequence. Although sharp lithological
boundaries exist in places, the changes in mineral composition are gradational, and
composition variance in offset from the lithological contact. These in turn can be correlated
with whole rock data for Cu, Ni and PGE. There is thus decoupling between the mode, and
trace element content and mineralization. Also significant is the close geochemical similarity
of pyroxenite and pegmatoidal pyroxenite, notwithstanding the textural contrasts. A similar
observation has been made at Atok (Lee & Butcher, 1990), with high, but very variable
mineral composition and trace element contents. A second profile, 25A, reveals similar
patterns with respect to PGE.

Rock by rock correlation analysis for PGE and trace elements of the Bushveld Complex
reveals specific lithological control on the resulting geochemical relationship.

Correlation coefficients were calculated for PGE+Au pairs (Table 5) and PGE+Au (Table 6)
and base element pairs for the entire R27A sampled sequence, and for the mineralized
Merensky reef alone.

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Considering the PGE+Au pairs, the correlation coefficients are generally lower in the
Merensky reef alone as opposed to the entire sequence. These lower correlation coefficients
tend to support the evidence for pronounced late-stage modification to the Merensky reef. In
both cases Pd correlates poorly with the other PGE, and not at all with Os, but shows a
relatively high correlation with Au. Similarly, Au shows a poor correlation with all the PGE,
save for Pd. This suggests that Pd has decoupled from the other PGE. Other evidence in
this study has already shown that PGE fractionation did not occur in the Merensky reef. This
would then suggest that Pd decoupling was a secondary late-stage process, whereby Pd may
have gone into-solid solution. The other five PGE show high correlation coefficients in excess
of 0.9 with one another.

The PGE correlations with the base elements (Table 6) do not show any general decrease in
coefficients within the Merensky reef. With the notable exceptions of Pd and Au, all PGE
show relatively high correlations with Cr2O3, which is consistent with the high peak values
associated with the chromitite layers. The reef correlations show increases in these
coefficients and further decreases for Pd and Au. Next to Cr2O3, the PGE-Zn correlations are
also high. This is likely to be a function of the Zn content of chromite.

It would be expected that the PGE-S correlation coefficients would be high if total S control
existed over the PGE mineralisation. However, these values are relatively low, with Pd and
Au showing the highest within the reef in the order of 0.64. Pt, Rh and Ir show correlations of
approximately 0.5, while Os and Ru show very low correlations in the order of 0.3. This
evidence, along with other evidence in this study, strongly suggest that sulphide control is
only part of the mineralisation scenario, and with Pd showing the highest dependence,
probably not what might have been expected. The As-PGE correlations are similar to the S-
PGE correlations with some minor differences. For instance Pt correlates more highly with As
than it does with S; Pd and Au considerably lower; Ir and Ru slightly higher; and Os
considerably higher.

Again, the PGE-base element correlations show the differing behaviour of Pd (& Au),
suggesting a late-stage decoupling. The Os-PGE and Os-base element correlations are the
next most obvious deviations from the average
PGE behaviour in this regard.

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 4. SUMMARY AND CONCLUSIONS

Close scale (cm intervals) sampling of seemingly monotonous rock sequences has proved to
be a valuable technique in revealing fine scale geochemical processes (Wilson 1992). This
technique has been applied to the study of four Merensky reef intersections, of which profile
R27 is an example.

Several geochemical features reported in this study indicate and confirm later sub-magmatic
reactions within the PGE-BMS mineralized sequence, associated with in-situ recrystallisation
of feldspathic pyroxenite.

1. Y, Zr, P and similar late stage, low temperature elements are concentrated in the
pyroxenite sequence.

2. Pyroxenite and pegmatoidal pyroxenite silicates have re-equilibrated with lower

temperature fluids, revealed from the mineral chemistry.

3. Reaction between Ni-bearing base-metal sulphides and orthopyroxene has enriched

the pyroxenite orthopyroxenes in Ni.

4. There is no correlation between S and Zr and this decoupling indicates late

movement within the mineralized sequence of either controlling phases. Alternatively
sulphur was introduced into the system by mechanics unknown.

5. The geochemical similarity of the pyroxenite and the pegmatoidal pyroxenite indicates
in-situ alteration.

6. The Merensky reef is apparently unique amongst PGE occurrences in that precious
metal content is constant, is diluted by silicate phases in thick reef facies, and is
highly concentrated in thin reef facies.

7. PGE and BMS phases occur in pyroxenite sequences with highest geochemical
variability, as well as being geochemically anomalous.

8. Within the pyroxenite and pegmatoidal pyroxenite, it is only the occurrence of PGE
and BMS, which defines the reef; in all other respects the pyroxenite sequence is
geochemically indistinct.

While there is now ample evidence to suggest in-situ recrystallisation of the silicate phase in
the Merensky reef, the source of the fluid and the relationship to the mineralization, if any, has
still to be deduced.

5. ACKNOWLEDGEMENTS

Thanks are extended to the Management of RPM Rustenburg Section, from where the
original data were collected and for permission to present this data.

Thanks are also due to Ray’s wife, Amy Brown, for retyping and scanning this into electronic
format in 2003.

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 6. REFERENCES

BARNES, S J (1986) The effect of trapped liquid crystallization on cumulus mineral

compositions in layered intrusions.
Contrib. Mineral. Petrol, 93, p 524-531.

BARNES, S J & KEAYS, R R (1992) Distribution of sulphides and PGE within the porphyritic
websterite zone of the Munni Munni Complex, Western Australia.

BROWN, R T (1991). The inter-relationship between the variability of the Merensky reef and
its footwall stratigraphy at Frank Shaft, Rustenburg Platinum Mines.
JCI Geologists Technical Meeting, 6, p 24-44.

CAWTHORN, R G & McCARTHY, T S (1985) Incompatible Trace Element Behaviour in the

Bushveld Complex.
Econ. Geol., 80, p 1016-1026.

EALES, H V, TEIGLER, B & MAIER, W D (1993) Cryptic variations of minor elements AI,
Cr, Ti, Mn in lower and critical zone orthopyroxenes of the Western Bushveld Complex.
Mineralogical Magazine, 57, 257-264.

HALDEN, N M & HAWTHORNE, F C (1993) The fractal geometry of oscillatory zoning in

crystals: Application to zircon.
Am. Mineral., 78, p 1113-1116.

LEE, C A (1983) Trace and Platinum-Group Element Geochemistry and the Development of
the Merensky Unit of the Western Bushveld Complex.
Mineral. Deposita, 18, p 173-190.

LEE, C A & PARRY, S J (1988) Platinum element geochemistry of the lower and middle
group chromitites of the eastern Bushveld Complex.
Econ. Geol. 83, 1127-1139.

LEE, C A (1989) Pt, Pd, Ir and Au distribution in the critical zone and part of the main zone,
Rustenburg Section, Rustenburg Platinum Mines, and their relevance in evaluating PGE
targets.
JCI Res. Unit Report No. 237/89.

LEE C A & BUTCHER, A R (1990) Cyclicity in Sr isotope profiles in the Merensky reef, Atok
Section.
Econ. Geol. 85. 877-883.

MATHEZ, E A (1994) Magmatic metasomatism and formation of the Merensky reef,

Bushveld Complex.
Nature (in press).

WILSON, A H & TREDOUX, M (1990) Lateral and vertical distribution of platinum-group

elements and petrogenetic controls on the sulphide mineralization in the P1 pyroxenite layer
of the Darwendale subchamber of the Great Dyke, Zimbabwe.
Econ. Geol. 85, 556-584.

WILSON, A H (1992) The Geology of the Great Dyke, Zimbabwe: Crystallisation, Layering
and Cumulate Formation in the Pyroxenite of Cyclic Unit 1 of the Darwendale Subchamber.
J. Petrol., 33, p 611-663.

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