Diverse studies were performed in order to investigate the behavior of the platinum-group minerals (PGM) in the weathering cycle in the Bushveld Complex of South Africa and the Great Dyke of Zimbabwe. Samples were obtained underground, from core, in surface outcrops, and from alluvial sediments in rivers draining the intrusions. The investigations applied conventional mineralogical methods (reflected light microscopy) complemented by modern techniques (scanning electron microscopy (SEM), mineral liberation analysis (MLA), electron-probe microanalysis (EPMA), and LA-ICPMS analysis). This review aims at combining the findings to a coherent model also with respect to the debate regarding allogenic versus authigenic origin of placer PGM. In the pristine sulfide ores, the PGE are present as discrete PGM, dominantly PGE-bismuthotellurides, -sulfides, -arsenides, -sulfarsenides, and -alloys, and substantial though variable proportions of Pd and Rh are hosted in pentlandite. Pt–Fe alloys, sperrylite, and most PGE-sulfides survive the weathering of the ores, whereas the base metal sulfides and the (Pt,Pd)-bismuthotellurides are destroyed, and ill-defined (Pt,Pd)-oxides or -hydroxides develop. In addition, elevated contents of Pt and Pd are located in Fe/Mn/Co-oxides/hydroxides and smectites. In the placers, the PGE-sulfides experience further modification, whereas sperrylite largely remains a stable phase, and grains of Pt–Fe alloys and native Pt increase in relative proportion. In the Bushveld/Great Dyke case, the main impact of weathering on the PGM assemblages is destruction of the unstable PGM and PGE-carriers of the pristine ores and of the intermediate products of the oxidized ores. Dissolution and redistribution of PGE is taking place, however, the newly-formed products are thin films, nano-sized particles, small crystallites, or rarely µm-sized grains primarily on substrates of precursor detrital/allogenic PGM grains, and they are of subordinate significance. In the Bushveld/Great Dyke scenario, and in all probability universally, authigenic growth and formation of discrete, larger PGM crystals or nuggets in the supergene environment plays no substantial role, and any proof of PGM “neoformation” in a grand style is missing. The final PGM suite which survived the weathering process en route from sulfide ores via oxidized ores into placers results from the continuous elimination of unstable PGM and the dispersion of soluble PGE. Therefore, the alluvial PGM assemblage represents a PGM rest spectrum of residual, detrital grains.

Base-metal sulphides (BMS) are important host minerals for platinum-group elements (PGE) in orthomagmatic Ni-Cu-PGE deposits. The PGE distribution and concentration in the BMS provide important genetic, exploration and mineral processing information. Therefore, detailed mineralogical work and an in situ laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) analysis of trace elements were conducted on the BMS of mineralised samples from the Overysel and Sandsloot localities of the Mogalakwena Platinum Mine. These localities access the Platreef of the northern Bushveld Complex. Platinum-group element enrichment trends in the BMS are similar in the Overysel and Sandsloot samples, although the overall PGE concentrations in the Overysel BMS are lower than those in the Sandsloot BMS. A general decoupling of the PGE from the BMS due to fluid activity, as advocated by other authors for the Sandsloot reef lithologies, was not observed in the samples studied. A major portion of the PGE mineralisation is associated with BMS as is indicated by the ‘moderate’ (Overysel r = +0.62) to ‘very good’ (Sandsloot r = +0.79) PPGE-S bulk-rock correlation, whereas an excellent PPGE-Ni correlation (especially at Overysel) indicates that pentlandite is a major PGE- carrier. These results are corroborated by the trace element contents of the BMS and by mass balance calculations. For instance, the LA-ICP-MS BMS study revealed average concentrations of 65 to 165 ppm Pd and 0.17 to 13 ppm Rh at Overysel, and 156 to 412 ppm Pd and 18 to 57 ppm Rh at Sandsloot in pentlandite of both the mineralized pyroxenites. In contrast, chalcopyrite and pyrrhotite are almost devoid of PGE. Platinum and the IPGE (Ir, Os, Ru) are very low in the BMS and, therefore, are thought to be hosted in discrete PGM grains. This conclusion is supported by the mass balance calculations for Pt and by the actual presence of PGM grains in both sample suites. The presence of discrete PGM grains explains the calculated gap between the whole-rock PPGE concentrations and the PPGE concentration in the mineral phases as revealed by the mass balance calculations. The PPGE concentrations in the BMS and the complementary mass balance calculations are in general agreement with those of the Merensky Reef and the UG-2, in both of which large proportions of the whole-rock Pd and Rh are hosted by pentlandite, whereas Pt and the IPGE mainly occur in discrete PGM rather than being hosted by BMS. However, comparison of our results with those of the Merensky Reef and the UG-2 indicates that the average maximum Pd and Rh concentrations in pentlandite are distinctly lower in the Platreef.

The platiniferous dunite pipes are discordant orebodies in the Bushveld Complex. The Onverwacht pipe is a large body (>300 m in diameter) of magnesian dunite (Fo_80–83) that crosscuts a sequence of cumulates in the Lower Critical Zone of the Bushveld Complex. In a pipe-in-pipe configuration, the main dunite pipe at Onverwacht hosts a carrot-shaped inner pipe of Fe-rich dunite pegmatite (Fo_46–62) which comprises the platinum-bearing orebody. The latter was ca. 18 m in diameter and a mining depth of about 320 m was reached. In the present work, a variety of ore samples were studied by whole-rock geochemistry, including analyses of platinum group elements, ore microscopy, and electron probe microanalysis. Olivine of the ore zone displays considerable chemical variation (range 46–62 mol.% Fo) and may represent either a continuum, or different batches of magma, or vertical or horizontal zonation within the ore zone. Chromite is principally regarded to be a consanguineous component of the pipe magma that crystallized in situ and simultaneously with olivine. The Onverwacht mineralization is Pt-dominated (>95% of the platinum group elements) and the ore is virtually devoid of sulfides. Platinum-dominated platinum group minerals predominate, followed by Rh-, Pd-, and Ru-species. Pt-Fe alloys are most frequent, followed by Pt-Rh-Ru-arsenides and -sulfarsenides, platinum group element antimonides, and platinum group element sulfides. Our hypothesis on the genesis of the Onverwacht pipe and its mineralization is as follows: After near-consolidation of the layered series of the Critical Zone, the magnesian dunite pipe of Onverwacht was formed by upward penetration of magmas that replaced the existing cumulates initially by infiltration, followed by the development of a central channel where large volumes of magma flowed through. Fractional crystallization of olivine within the deeper magma chamber and/or during ascent of the melt resulted in the formation of a consanguineous, residual, more iron-rich melt. This melt also contained highly mobile, supercritical, water-bearing fluids and was continuously enriched in platinum group elements and other incompatible elements. In several closing pulses, the platinum group element-enriched residual melts crystallized and sealed the inner ore pipe. Crystallization of the melt resulted in the coeval formation of Fe-rich olivine, chromite, and platinum group minerals. The non-sulfide platinum group element mineralization was introduced in the form of nanoparticles and small droplets of platinum group minerals, which coagulated to form larger grains during evolution of the mineralizing system. The suspended platinum group minerals acted as collectors of other platinum group elements and incompatible elements during generation and ascent of the melt. With decreasing temperature, the platinum group mineral grains annealed and recrystallized, leading to the formation of composite platinum group mineral grains, complex intergrowths, or lamellar exsolution bodies. On further cooling, platinum group minerals overgrowing Pt-Fe alloys formed by reaction of leached elements and ligands like Sb, As, and S mobilized by supercritical magmatic/hydrothermal fluids. Redistribution of platinum group elements/platinum group minerals apparently only occurred on the scale of millimeters to centimeters. Finally, surface weathering led to the local formation of platinum group element oxides/hydroxides by oxidation of reactive precursor platinum group minerals.

The Mooihoek pipe is one of several platiniferous dunite pipes in the eastern Bushveld Complex that were discovered in 1924 and mined until 1930. It has a diameter of about 180 by 400 m and consists of magnesian dunite that crosscuts a sequence of layered leucocratic wall rocks of the lower part of the upper Critical Zone of the Bushveld Complex. The Mg-dunite pipe at Mooihoek hosts a smaller, carrot-shaped inner pipe, 13–16 m in diameter and cylindrical in shape near surface, consisting of mainly iron-rich dunite/wehrlite pegmatite, comprising the platinum-bearing orebody. Specific characteristics of the mineralization are the near absence of sulfides and Pt being the predominant platinum-group element (PGE). The present work comprises whole rock analyses, ore microscopy, scanning electron microscopy, and electron probe microanalysis. The main findings are as follows: Chondrite-normalized distribution patterns of the PGE in the Mooihoek samples demonstrate that mainly Pt is strongly enriched relative to the other PGE and Au. The shapes of the patterns are subparallel to each other and also to those of the Onverwacht pipe, indicating a similar mode of origin. Olivine of the ore zone is iron-rich and is frequently accompanied by coarse Ti-magnetite and ilmenite, whereas chromite is rare. Two major generations of platinum-group minerals (PGM) are present at Mooihoek, namely: (1) Early inclusions of mainly ferroan platinum in (magmatic) olivine, Ti-magnetite, and ilmenite, and (2) a later, more complex PGM assemblage, commonly associated with thin veinlets of magnetite, mainly found along grain boundaries of silicates and oxides. This assemblage consists of various Pt-Fe alloys and PGE-antimonides, -sulfarsenides, -arsenides, and -sulfides. Overall, and in line with the geochemical data of the mineralization, Pt-dominated PGM predominate (~70%), followed by Rh, Pd, and Ru species. Pt-Fe alloys are the most frequent PGM (∼44% by number of grains). Our hypothesis on the genesis of the Mooihoek pipe and its mineralization largely corresponds to that proposed for the Onverwacht pipe (Oberthür et al. 2021): The magnesian dunite pipe was formed by upward penetration of magmas which replaced the existing cumulates. Fractional crystallization of olivine within a deeper magma chamber and/or during ascent of the melt resulted in the formation of a consanguineous residual, more iron-rich, and PGE-enriched melt. This melt also contained highly mobile, supercritical fluids and was continuously enriched in PGE and other incompatible elements. The PGE-enriched residual melts formed and sealed the inner ore pipe. Apparently, the PGE mineralization is not related to the well-established mechanism of sulfide collection. Instead, it was introduced in the form of nanoparticles and small droplets of PGM, which coagulated to form larger grains during evolution of the mineralizing system. Concomitant supercritical magmatic to hydrothermal fluids were continuously active and caused a certain redistribution of the initial PGE inventory and possibly added further quantities of PGE from lower parts of the mineralizing system. Reactions with ligands like Sb, As, and S led to the formation of composite PGM grains and complex intergrowths in a continuous process of mineralization. The present work underlines that sulfide-poor magmas may constitute fertile potential precursors of PGE deposits and, therefore, deserve more attention in future exploration.