A 5-km-thick reservoir with >380,000 km3 of magma within the ancient Earth's crust

Several recent studies have argued that large, long-lived and molten magma chambers1–10 may not occur in the shallow Earth’s crust11–23. Here we present, however, field-based observations from the Bushveld Complex24 that provide evidence to the contrary. In the eastern part of the complex, the magmatic layering was found to continuously drape across a ~4-km-high sloping step in the chamber floor. Such deposition of magmatic layering implies that the resident melt column was thicker than the stepped relief of the chamber floor. Prolonged internal differentiation within such a thick magma column is further supported by evolutionary trends in crystallization sequence and mineral compositions through the sequence. The resident melt column in the Bushveld chamber during this period is estimated to be >5-km-high in thickness and >380,000 km3 in volume. This amount of magma is three orders of magnitude larger than any known super-eruptions in the Earth’s history25 and is only comparable to the extrusive volumes of some of Earth’s large igneous provinces26. This suggests that super-large, entirely molten and long-lived magma chambers, at least occasionally, occur in the geological history of our planet. Therefore, the classical view of magma chambers as ‘big magma tanks’1–10 remains a viable research concept for some of Earth’s magmatic provinces.

Oberthürite, Rh3(Ni,Fe)32S32 and torryweiserite, Rh5Ni10S16, two new platinum-group minerals from the Marathon deposit, Coldwell Complex, Ontario, Canada: Descriptions, crystal-chemical considerations, and comments on the geochemistry of rhodium

ABSTRACT Oberthürite, Rh3(Ni,Fe)32S32, and torryweiserite, Rh5Ni10S16, are two new platinum-group minerals discovered in a heavy-mineral concentrate from the Marathon deposit, Coldwell Complex, Ontario, Canada. Oberthürite is cubic, space group , with a 10.066(5) Å, V 1019.9(1) Å3, Z = 1. The six strongest lines of the X-ray powder-diffraction pattern [d in Å (I)(hkl)] are: 3.06(100)(311), 2.929(18)(222), 1.9518(39)(115,333), 1.7921(74)(440), 1.3184(15)(137,355) and 1.0312(30)(448). Associated minerals include: vysotskite, Au-Ag alloy, isoferroplatinum, Ge-bearing keithconnite, majakite, coldwellite, ferhodsite-series minerals (cuprorhodsite–ferhodsite), kotulskite, and mertieite-II, and the base-metal sulfides, chalcopyrite, bornite, millerite, and Rh-bearing pentlandite. Grains of oberthürite are up to 100 × 100 μm and the mineral commonly develops in larger composites with coldwellite, isoferroplatinum, zvyagintsevite, Rh-bearing pentlandite, and torryweiserite. The mineral is creamy brown compared to coldwellite and bornite, white when compared to torryweiserite, and gray when compared chalcopyrite and millerite. No streak or microhardness could be measured. The mineral shows no discernible pleochroism, bireflectance, or anisotropy. The reflectance values (%) in air for the standard COM wavelengths are: 36.2 (470 nm), 39.1 (546 nm), 40.5 (589 nm), and 42.3 (650 nm). The calculated density is 5.195 g/cm3, determined using the empirical formula and the unit-cell parameter from the refined crystal structure. The average result (n = 11) using energy-dispersive spectrometry is: Rh 10.22, Ni 38.83, Fe 16.54, Co 4.12, Cu 0.23 S 32.36, total 100.30 wt.%, which corresponds to (Rh2Ni0.67Fe0.33)Σ3.00(Ni19.30Fe9.09Co2.22Rh1.16Cu0.12)∑31.89S32.11, based on 67 apfu and crystallochemical considerations, or ideally, Rh3Ni32S32. The name is for Dr. Thomas Oberthür, a well-known researcher on alluvial platinum-group minerals, notably those found in deposits related to the Great Dyke (Zimbabwe) and the Bushveld complex (Republic of South Africa). Torryweiserite is rhombohedral, space group , with a 7.060(1), c 34.271(7) Å, V 1479.3(1), Z = 3. The six strongest lines of the X-ray powder-diffraction pattern [d in Å (I)(hkl)] are: 3.080(33)(021), 3.029(58)(116,0110), 1.9329(30)(036,1115,1210), 1.7797(100)(220,0216), 1.2512(49)(0416), and 1.0226(35)(060,2416,0232). Associated minerals are the same as for oberthürite. The mineral is slightly bluish compared to oberthürite, gray when compared to chalcopyrite, zvyagintsevite, and keithconnite, and pale creamy brown when compared to bornite and coldwellite. No streak or microhardness could be measured. The mineral shows no discernible pleochroism, bireflectance, or anisotropy. The reflectance values (%) in air for the standard COM wavelengths are: 34.7 (470 nm), 34.4 (546 nm), 33.8 (589 nm), and 33.8 (650 nm). The calculated density is 5.555 g/cm3, determined using the empirical formula and the unit-cell parameters from the refined crystal structure. The average result (n = 10) using wavelength-dispersive spectrometry is: Rh 28.02, Pt 2.56, Ir 1.98, Ru 0.10, Os 0.10, Ni 17.09, Fe 9.76, Cu 7.38, Co 1.77 S 30.97, total 99.73 wt.%, which corresponds to (Rh4.50Pt0.22Ir0.17Ni0.08Ru0.02Os0.01)∑5.00(Ni4.73Fe2.89Cu1.92Co0.50)Σ10.04S15.96, based on 31 apfu and crystallochemical considerations, or ideally Rh5Ni10S16. The name is for Dr. Thorolf (‘Torry') W. Weiser, a well-known researcher on platinum-group minerals, notably those found in deposits related to the Great Dyke (Zimbabwe) and the Bushveld complex (Republic of South Africa). Both minerals have crystal structures similar to those of pentlandite and related minerals: oberthürite has two metal sites that are split relative to that in pentlandite, and torryweiserite has a layered structure, comparable, but distinct, to that developed along [111] in pentlandite. Oberthürite and torryweiserite are thought to develop at ∼ 500 °C under conditions of moderate fS2, through ordering of Rh-Ni-S nanoparticles in precursor Rh-bearing pentlandite during cooling. The paragenetic sequence of the associated Rh-bearing minerals is: Rh-bearing pentlandite → oberthürite → torryweiserite → ferhodsite-series minerals, reflecting a relative increase in Rh concentration with time. The final step, involving the formation of rhodsite-series minerals, was driven via by the oxidation of Fe2+ → Fe3+ and subsequent preferential removal of Fe3+, similar to the process involved in the conversion of pentlandite to violarite. Summary comments are made on the occurrence and distribution of Rh, minerals known to have Rh-dominant chemistries, the potential existence of both Rh3+ and Rh2+, and the crystallochemical factors influencing accommodation of Rh in minerals.

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.

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.

Transgressive nature and chilled margins of the Upper Zone in the western Bushveld Complex, South Africa

ABSTRACT The Upper Zone of the Bushveld Complex has long been known to have formed from a major influx of magma into the chamber that caused large-scale erosion of the chamber floor cumulates. The most dramatic manifestations of this process are two major gap areas (Northern and Southern) in the western Bushveld Complex in which the Upper Zone appears to have eroded away the underlying cumulates down to the very base of the Complex. However, due to almost complete lack of outcrops in the gap areas, no direct field observations have ever been reported to confirm the transgressive nature of the Upper Zone. Here, we present for the first time such observations from the Kameelhoek chromite mine located at the margin of the Northern Gap. In the open pit we have documented several transgressive depressions (up to 40 m in width) in the orthopyroxenite and chromitites of the Lower Critical Zone that are filled in with magnetite gabbro of the Upper Zone. The magnetite gabbro is chilled against the sidewalls of the depressions, forming glassy and fine-grained textured rocks with plagioclase laths arranged in radial clusters. Mineralogically and chemically, the magnetite gabbro correlates with cumulates from the lowermost part of the Upper Zone at its normal position in the complex. Three major points that have emerged from this study are: (1) the Critical Zone has been eroded away by magma that was parental to the Upper Zone, (2) this eroding magma was not the one that initiated formation of the Pyroxenite Marker, but rather the evolved melt that replenished the chamber at some later stage, and (3) the melt was phenocryst-free and likely derived from a deep-seated staging chamber. Our study thus supports a recent notion that even during the formation of the Upper Zone, the Bushveld chamber had still been operating as an open system that was replenished by melts from deeper magma sources.

High grade ores of the Onverwacht platinum pipe, eastern Bushveld, South Africa

ABSTRACT 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 (Fo80–83) 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 (Fo46–62) 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.

Sintering as a key process in the textural evolution of chromitite seams in layered mafic-ultramafic intrusions

ABSTRACT Nearly monomineralic stratiform chromitite seams of variable thickness (millimeters to meters) occur in many of the world's layered mafic-ultramafic intrusions. These seams are often associated with economically significant quantities of platinum group metals, yet the petrogenesis of these societally important materials remains enigmatic. Here we evaluate processes associated with late-magmatic (postcumulus) textural maturation of chromitite seams from four layered mafic-ultramafic intrusions of different ages and sizes. From largest to smallest, these intrusions are the ∼2060 Ma Bushveld Complex (South Africa), the ∼2710 Ma Stillwater Complex (USA), the ∼1270 Ma Muskox Intrusion (Canada), and the ∼60 Ma Rum Eastern Layered Intrusion (Scotland). Three endmember chromitite textures are described, based on chromite grain size and degree of textural equilibration: (1) coarse-grained chromite crystals (>0.40 mm) that occur in the central portions of seams and exhibit high degrees of solid-state textural equilibration; (2) fine-grained chromite crystals (0.11–0.44 mm) at the margins of seams in contact with and disseminated throughout host anorthosite or pyroxenite; and (3) fine-grained chromite crystals (0.005–0.28 mm) hosted within intra-seam orthopyroxene, clinopyroxene, and olivine oikocrysts. Crystal size distribution and spatial distribution pattern analyses are consistent with coarsening occurring through processes of textural maturation, including the sintering of grains by coalescence. We propose that textural maturation initially occurred in the supra-solidus state followed by an important stage of solid-state textural maturation and that these equilibration processes played a major role in the eventual microstructural and compositional homogeneity of the chromitite seams.