Laboratory-Based Bacterial Weathering of the Merensky Reef and Its Impact on Platinum Group Mineral Migration

Weathering of the Merensky reef was enhanced under laboratory conditions by Fe- and S-oxidizing bacteria: Acidithiobacillus ferrooxidans, Acidithiobacillus thiooxidans, and Leptospirillum ferrooxidans. These bacteria preferentially colonized pyrrhotite and pyrite, versus pentlandite and chalcopyrite (all of which were common within the rock substrate), promoting weathering. Weathering of base metal sulfides resulted in the precipitation of Fe oxides, Fe phosphate, and elemental sulfur as secondary minerals. Fe pyroxene weathered readily under acidic conditions and resulted in mineral dissolution, while other silicates (orthopyroxene and plagio-clase) precipitated Fe phosphate spherules or coatings on their surface. The deterioration of the platinum group metal (PGM) matrix (base metal sulfides and silicates) and the occurrence of a platinum grain associated with platinum nanoparticles observed in the biotic thin sections demonstrate that biogeochemical acid weathering is an important step in the active release of intact PGM grains. A platinum grain embedded in secondary Fe oxides/phosphate that had settled by gravity within the weathering solution demonstrates that secondary minerals that formed during weathering of PGM-hosting minerals also represent targets in PGM exploration by trapping and potentially slowing PGM migration. Dispersion halos surrounding or occurring downstream from PGM occurrences will likely produce two physical target classes—i.e., grains and colloids—under surficial weathering conditions.

PGE distribution in Merensky wide-reef facies of the Bushveld Complex, South Africa: Evidence for localized hydromagmatic control

ABSTRACT The wide-reef facies of the Merensky Reef in the eastern part of the western lobe of the Bushveld Complex was sampled in order to better resolve otherwise spatially constrained variation in highly siderophile elements across this geological unit. The platinum group element mineralogy and whole-rock highly siderophile element concentrations were measured across two vertical sections in close proximity. In one section, the Merensky Reef unit was bound by top and bottom platinum group elements-enriched horizons (reefs) with a well-developed pegmatoidal phase in the top third of the intrareef pyroxenite, but with neither a top nor a bottom chromitite present. The other drill core section featured a thin (<1 cm thick) chromitite layer associated with the highest platinum group element concentrations of any rock in this study as the bottom reef, but with a chromitite-absent top reef, and very poor development of the pegmatoid. Primitive mantle-normalized profiles of the main lithological units show relatively flat, primitive mantle-like highly siderophile element abundances (Cr, V, Co, Ni, platinum group elements, Au and Cu) in the Merensky pyroxenite, with modest depletion in Ir-affiliated platinum group elements. The platinum group element-rich top and bottom reefs, and the pegmatoidal upper pyroxenites, display characteristic enrichment in the Pt-affiliated platinum group elements and undepleted Ir-affiliated platinum group elements. The leuconoritic hanging wall and footwall rocks show comparable highly siderophile element profiles, distinguished from one another by relative depletion in the Pt-affiliated platinum group elements of the footwall samples. The vertical variation in highly siderophile element abundances through both sections is characterized by low platinum group element abundances through the lower reef pyroxenite, with platinum group element, Au, and Cu ± Ni concentrations increasing through the upper pegmatoidal pyroxenite, and main enrichment peaks at the top and bottom reefs. Significant localized (centimeter-scale) zones of chalcophile metal depletion are present immediately above the top reef and below the bottom reef. In addition, a wider zone of Pt-affiliated platinum group elements (with Pd more depleted than Pt)-depletion was identified within the pegmatoidal pyroxenite around one meter below the top reef. The platinum group element mineralogy of the bottom reef consists mainly of platinum group element sulfides, with minor arsenides and antimonides. In contrast, the platinum group element mineralogy of the top reef, and the small amount of data from the intrareef pyroxenite, mainly consist of Pt-affiliated platinum group elements-Bi-tellurides. The Pt-sulfides are mainly equant, relatively coarse crystals (many grains between 50 to 100 μm2 area), contrasting with the Pt-affiliated platinum group elements-Sb-As and -Bi-Te minerals that tend be high aspect-ratio grains, occurring in veinlets or as rims on earlier-forming platinum group element phases. These Te-As-Bi-Sb compounds are closely associated with chlorite, actinolite, quartz, and chalcopyrite, consistent with secondary deposition at lower temperatures and association with aqueous fluids. A model is proposed involving the emplacement of the Merensky unit as a magma pulse into at least semi-crystallized host rock, followed by aqueous fluid saturation and local migration, combined with concentration of late magmatic fluids around the top and bottom contacts of the magma pulse. Late remobilization of Pt-affiliated platinum group elements from the zones immediately (centimeter-scale) above the top reef, and from the underlying meter or two of pyroxenite, and from the centimeters underlying the bottom reef, have added additional platinum group elements to the reefs as late platinum group elements-Te-As-Bi-Sb minerals, independent of whether or not chromite is present in the reef initially.

A Comparative Study of Sulfur Isotope Variations within the Flatreef and Merensky Reef of the Bushveld Complex, South Africa

ABSTRACT The Flatreef, a down-dip, sub-horizontal extension of the Platreef, which underlies the Turfspruit and Macalacaskop farms, represents the future of platinum mining in South Africa. The stratigraphic connection between the Platreef, located at the base of the northern limb of the Bushveld Complex, and the Merensky Reef in the western and eastern limbs of the complex, was disputed for many years due to the heterogeneous nature of the Platreef along strike. However, the discovery of the Flatreef led to a new perspective on the Platreef as the former allowed for the study of a magmatic stratigraphy less affected by footwall interaction. Here, we report whole-rock S isotope (δ34S) compositions across the stratigraphic units of the Flatreef and its footwall and hanging wall as intersected by boreholes UMT-276 and UMT-393, as well as stratigraphic units of the Merensky Reef at Two Rivers Platinum mine in the eastern limb. The units of the Flatreef containing platinum group element mineralization, namely the Main Reef and Upper Reef, have δ34S values that overlap with the range recorded for the Merensky Reef in the western and eastern limbs. In UMT-393, Main Reef δ34S values range between 0.2 and 1.5‰ (with the exception of three outliers, 9.7‰, 11.1‰, and 7.9‰), and 0.52‰ and 11.2‰ for two Upper Reef samples. However, in UMT-276, Main Reef δ34S values range between –0.96 and 2.24‰ and 3.19‰ was recorded for an Upper Reef sample. The S isotope compositions recorded for the Merensky Reef pyroxenite at Two Rivers Platinum mine are relatively higher with δ34S values ranging between 1.24 and 4.83‰. The top unit of the Flatreef, which is a transition zone below the Main Zone, as well as the Footwall Cyclic Unit have heavier S isotope compositions with δ34S values ranging between 6 and 17‰ for the former and 0.7 and 18.6‰ for the latter. At Two Rivers Platinum mine, the hanging-wall anorthosite has a δ34S value of 2.9‰ in contrast to the 5.7‰ measured for the footwall anorthosite and 3.27‰ for the footwall feldspathic pyroxenite. The consistent near-mantle S isotope signature and accompanying metal enrichment in the Main Reef of the Flatreef may be explained by extensive interaction of sulfide minerals in a Lower Zone conduit/pre-Platreef staging chamber with large volumes of uncontaminated magma. The δ34S values of the Merensky Reef at Two Rivers Platinum mine are slightly higher compared to that of the Main Reef at Turfspruit and Macalacaskop possibly due to interaction with underlying carbonate rocks.

Supergene mobilization and redistribution of platinum-group elements in the Merensky Reef, eastern Bushveld Complex, South Africa

ABSTRACT Near-surface supergene ores of the Merensky Reef in the Bushveld Complex, South Africa, contain economic grades of platinum-group elements, however, these are currently uneconomic due to low recovery rates. This is the first study that investigates the variation in platinum-group elements in pristine and supergene samples of the Merensky Reef from five drill cores from the eastern Bushveld. The samples from the Richmond and Twickenham farms show different degrees of weathering. The whole-rock platinum-group element distribution was studied by inductively coupled plasma-mass spectrometry and the platinum-group minerals were investigated by reflected-light microscopy, scanning electron microscopy, and electron microprobe analysis. In pristine (“fresh”) Merensky Reef samples, platinum-group elements occur mainly as discrete platinum-group minerals, such as platinum-group element-sulfides (cooperite–braggite) and laurite as well as subordinate platinum-group element-bismuthotellurides and platinum-group element-arsenides, and also in solid solution in sulfides (especially Pd in pentlandite). During weathering, Pd and S were removed, resulting in a platinum-group mineral mineralogy in the supergene Merensky Reef that mainly consists of relict platinum-group minerals, Pt-Fe alloys, and Pt-oxides/hydroxides. Additional proportions of platinum-group elements are hosted by Fe-hydroxides and secondary hydrosilicates (e.g., serpentine group minerals and chlorite). In supergene ores, only low recovery rates (ca. 40%) are achieved due to the polymodal and complex platinum-group element distribution. To achieve higher recovery rates for the platinum-group elements, hydrometallurgical or pyrometallurgical processing of the bulk ore would be required, which is not economically viable with existing technology.

Contamination of the Bushveld Complex (South Africa) magmas by basinal brines: Stable isotopes in phlogopite from the UG2 chromitite

There is abundant evidence for significant H2O in evolved melts from the platinum-rich UG2 chromitite and the Merensky Reef of the Bushveld Complex (South Africa), but there is no consensus about the source of H2O. We report triple-oxygen and hydrogen isotope ratios of interstitial, late-magmatic phlogopite from three localities of the UG2 layer. The phlogopite yielded δD values of –43‰ to –23‰, which is >30‰ higher than previously known from Bushveld rocks and far above the mantle values of ~–75‰. The phlogopite triple-oxygen isotope ratios are the first to be reported for Bushveld rocks, with values of Δ′17O0.5305 (17O excess relative to the reference line 0.5305) from –0.069‰ to –0.044‰ (δ18O 5.2‰–6.2‰). The oxygen data support existing models of as much as 30%–40% contamination of mantlederived magmas in the lower to middle crust. However, the high δ values require a second step of contamination, which we attribute to brines from the marine sediments in the Transvaal Basin at the emplacement level.

Testing Trace-Element Distribution and the Zr-Based Thermometry of Accessory Rutile from Chromitite

Trace element distribution and Zr-in-rutile temperature have been investigated in accessory rutile from stratiform (UG2, Merensky Reef, Jacurici), podiform (Loma Peguera), and metamorphic chromitites in cratonic shields (Cedrolina, Nuasahi). Rutile from chromitite has typical finger-print of Cr-V-Nb-W-Zr, whose relative abundance distinguishes magmatic from metamorphic chromitite. In magmatic deposits, rutile precipitates as an intercumulus phase, or forms by exsolution from chromite, between 870 °C and 540 °C. The Cr-V in rutile reflects the composition of chromite, both Nb and Zr are moderately enriched, and W is depleted, except for in Jacurici, where moderate W excess was a result of crustal contamination of the mafic magma. In metamorphic deposits, rutile forms by removal of Ti-Cr-V from chromite during metamorphism between 650 °C and 400 °C, consistent with greenschist-amphibolite facies, and displays variable Cr-Nb, low V-Zr, and anomalous enrichment in W caused by reaction with felsic fluids emanating from granitoid intrusions. All deposits, except Cedrolina, contain Rutile+PGM composite grains (<10 µm) locked in chromite, possibly representing relics of orthomagmatic assemblages. The high Cr-V content and the distinctive W-Nb-Zr signature that typifies accessory rutile in chromitite provide a new pathfinder to trace the provenance of detrital rutile in placer deposits.

An overview of global layered intrusions, with a special focus on the Bushveld Complex, South Africa

Layered intrusions host some of the world’s most important ore deposits, yet their global distribution, age, and petrogenesis remain poorly known. Here we provide an update on our current understanding and highlight some key outstanding research questions, notably on the potential importance of reactive flow. We present some preliminary data on water contents of Bushveld orthopyroxenes from which we calculated the water contents of the magma. The analysed Bushveld rocks, including the Merensky Reef, crystallised from relatively water-poor magma, similar to many other continental basalts.

Assessing the extent of local crust assimilation within the Flatreef, northern limb of the Bushveld Igneous Complex, using sulfur isotopes and trace element geochemistry

The proximity to metasedimentary footwall rocks relative to platinum group element (PGE) mineralized intrusive rocks in the northern limb of the Bushveld Igneous Complex (BIC) has resulted in complex local contamination in the intrusions. To assess the extent of incorporation of non-magmatic material and its effects on PGE mineralization, major element, trace element, and S isotopic data were collected from drill core UMT094 on the Turfspruit farm, where core logging has shown that the mineralized Platreef, forming the Flatreef deposit, is located stratigraphically well above local sedimentary footwall rocks. The S isotopic data combined with whole rock geochemistry data (including CaO/Al2O3, (V/Ti)PM, (Ni/Cr)PM, S/Se, loss on ignition) were used to assess incorporation of a range of local footwall material. The δ34S data show a steady decrease from the footwall assimilation zone (δ34S typically + 8 to + 9‰, maximum 12‰) to near constant δ34S values (δ34S < + 4‰) below the main PGE reef. Similar values have been documented for the Merensky Reef in the eastern and western limbs of the BIC (δ34S ~ 0 to + 3.5‰). Other geochemical parameters, such as S/Se and CaO/Al2O3, also match the ranges documented for the Merensky Reef elsewhere in the BIC. In addition, parameters such as whole rock V/Ti, normalized to primitive mantle (V/Ti)PM, are shown to be useful indicators of contamination and the type of contaminant with 1 < (V/Ti)PM < 2 for uncontaminated magmatic units; [V/Ti]pm > 2 for shale assimilation; and [V/Ti]pm < 1 for carbonate assimilation. The results suggest that the main PGE mineralization in the Flatreef deposit formed without significant in situ contamination and that the primary mechanism of PGE mineralization in the Platreef at Turfspruit was no different than the mechanism that generated the Merensky Reef in the eastern and western limbs of the BIC.