The mineralogy and mineral associations of platinum-group elements and precious metals in the Aurora Cu-Ni-Au-PGE deposit, Northern Limb, Bushveld Complex

Aurora is a platinum-group element (PGE) prospect hosted in the Northern Limb of the Bushveld Complex, South Africa. It is one of only three deposits discovered in the Northern Limb so far to be hosted in the melanocratic-leucocratic gabbroic cumulates of the Main Zone of the Rustenberg Layered Suite (Aurora, Moorddrift and Waterberg T Zone deposits), rather than in predominantly ultramafic rocks (e.g. Platreef). The host cumulates at Aurora have been divided into three principal units and they intrude the dolomites of the lower Transvaal Supergroup. Base metal sulphide (BMS) mineralisation with PGE is present in the leucogabbronorites and gabbronorites of Unit 2, and in coarse grained gabbronorite veins which intrude the peridotites of Unit 1. These veins contain up to 50% interstitial pyrrhotite-pentlandite-chalcopyrite ± pyrite. Unit 2 contains 1–3% pentlandite-pyrrhotite-chalcopyrite assemblages, and 1–5% chalcopyrite ± pyrite/pyrrhotite associated with hydrothermal alteration. The PGE content of Aurora however is predominantly controlled by the presence of platinum-group minerals (PGM), not BMS. LA-ICP-MS analysis of sulphides shows the BMS in Aurora have lower PGE concentrations than other Bushveld magmatic sulphides, with pentlandite carrying much lower concentrations of Pd (average 23 ppm) than the Platreef or the Merensky Reef. SEM-EDS analysis of 26 sections characterised 995 platinum-group minerals (PGM) and precious metal-bearing minerals (PMM), with a total area of 27850 μm2 and an average size of 28.2 μm2. Of the PGM and PMM identified in Aurora 85% (by area) are Pd-Te-Bi minerals, with 6% Pd-Te minerals, 4% electrum and 3% Ag-Te minerals, along with minor Pd-Bi, Pd-As, Pt-Te-Bi, Pt-As and Pt-S minerals that collectively comprise 2% of total area. Only 25% of the PGM and PMM in Aurora are BMS hosted, with the rest hosted in silicates. Of the total PGM and PMM area 22% are hosted in alteration-silicates (quartz, chlorite or actinolite) in an alteration halo around sulphides. Unusually, 52% of the PGM and PMM are spatially removed from BMS, instead hosted in alteration silicates and within cracks in primary silicates away from any BMS. This indicates a multi-stage ore genesis model, with hydrothermal remobilisation of PGE important for ore formation. The style and host rocks for mineralisation in the Aurora deposit are fundamentally different from other deposits in the Northern Limb of the Bushveld hosted in ultramafic rocks, such as the Platreef, GNPA member deposits and the F zone of the Waterberg deposit, all of which contain a greater diversity of PGM and BMS with higher precious metal contents. The mineralisation most similar to Aurora is the T Zone of the Waterberg deposit, located to the north of Aurora, which been suggested to be an along-strike equivalent of the Aurora Main Zone mineralisation. However, despite strong similarities in PGM mineralogy and S isotope signatures there are significant differences in BMS mineralisation and host lithology meaning it is unlikely they are directly linked stratigraphically. At present it seems more likely that Aurora and the Waterberg T Zone reflect similar fluid-influenced processes operating in different parts of the Main Zone, perhaps at different times and in different structural basins, rather than a continuous mineralised zone along strike

The Drosophila melanogaster gut microbiota provisions thiamine to its host

The microbiota of Drosophila melanogaster has a substantial impact on host physiology and nutrition. Some effects may involve vitamin provisioning, but the relationships between microbe-derived vitamins, diet, and host health remain to be established systematically. We explored the contribution of microbiota in supplying sufficient dietary thiamine (vitamin B1) to support D. melanogaster at different stages of its life cycle. Using chemically defined diets with different levels of available thiamine, we found that the interaction of thiamine concentration and microbiota did not affect the longevity of adult D. melanogaster Likewise, this interplay did not have an impact on egg production. However, we determined that thiamine availability has a large impact on offspring development, as axenic offspring were unable to develop on a thiamine-free diet. Offspring survived on the diet only when the microbiota was present or added back, demonstrating that the microbiota was able to provide enough thiamine to support host development. Through gnotobiotic studies, we determined that Acetobacter pomorum, a common member of the microbiota, was able to rescue development of larvae raised on the no-thiamine diet. Further, it was the only microbiota member that produced measurable amounts of thiamine when grown on the thiamine-free fly medium. Its close relative Acetobacter pasteurianus also rescued larvae; however, a thiamine auxotrophic mutant strain was unable to support larval growth and development. The results demonstrate that the D. melanogaster microbiota functions to provision thiamine to its host in a low-thiamine environment. Importance: There has been a long-standing assumption that the microbiota of animals provides their hosts with essential B vitamins; however, there is not a wealth of empirical evidence supporting this idea, especially for vitamin B1 (thiamine). To determine whether this assumption is true, we used Drosophila melanogaster and chemically defined diets with different thiamine concentrations as a model. We found that the microbiota does provide thiamine to its host, enough to allow the development of flies on a thiamine-free diet. The power of the Drosophila-microbiota system allowed us to determine that one microbiota member in particular, Acetobacter pomorum, is responsible for the thiamine provisioning. Thereby, our study verifies this long-standing hypothesis. Finally, the methods used in this work are applicable for interrogating the underpinnings of other aspects of the tripartite interaction between diet, host, and microbiota

Platinum-group minerals in the Skouries Cu-Au (Pd, Pt, Te) porphyry deposit

The Skouries deposit is a platinum-group element (PGE) enriched Cu-Au porphyry system located in the Chalkidiki peninsula, Greece, with associated Ag, Bi and Te enrichment. The deposit is hosted by multiple porphyritic monzonite and syenite intrusions, which originated from a magma chamber at depth. An initial quartz monzonite porphyritic intrusion contains a quartz–magnetite ± chalcopyrite–pyrite vein stockwork with intense potassic alteration. The quartz monzonite intrusion is cross cut by a set of syenite and mafic porphyry dykes and quartz–chalcopyrite–bornite ± magnetite veins which host the majority of the Cu and Au mineralisation. Late stage quartz–pyrite veins, with associated phyllic alteration crosscut all previous vein generations. Electron microprobe and scanning electron microscopy shows that the PGE are hosted by platinum-group minerals (PGM) in the quartz-chalcopyrite–bornite ± magnetite veins and within potassic alteration assemblages. The PGE mineralisation in Skouries is therefore part of the main high temperature hypogene mineralisation event. Platinum-group minerals at Skouries include: sopcheite [Ag4Pd3Te4], merenskyite [(Pd,Pt)(Te,Bi)2] and kotulskite [Pd(Te,Bi)], with rare telargpalite [(Pd,Ag)3Te], isomertieite [Pd11Sb2As2], naldrettite [Pd2Sb], testibiopalladite [PdTe(Sb,Te)] and sobolevskite [PdBi]. The most common platinum-group mineral is sopcheite. The PGM in Skouries are small, 52 µm2 on average, and occur as spherical grains on the boundaries between sulphides and silicates, and as inclusions within hydrothermal quartz and sulphides. These observations support a “semi-metal collector model” whereby an immiscible Bi-Te melt acts as a collector for PGE and other precious metals in high temperature hydrothermal fluids. This mechanism would allow the formation of PGM in porphyries without Pt and Pd fluid saturation

Rhenium enrichment in the Muratdere Cu-Mo (Au-Re) porphyry deposit, Turkey: evidence from stable isotope analyses (δ34S, δ18O, δD) and laser ablation-inductively coupled plasma-mass spectrometry analysis of sulfides

The Muratdere Cu-Mo (Au) porphyry deposit in western Turkey contains elevated levels of rhenium and is hosted within granodioritic intrusions into an ophiolitic mélange sequence in the Anatolian belt. The deposit contains several stages of mineralization: early microfracture-hosted molybdenite and chalcopyrite, followed by a quartz-pyrite-chalcopyrite vein set associated with Cu-Au grade, a quartz-chalcopyrite-pyrite-molybdenite vein set associated with Cu-Mo-Re grade, and a later polymetallic quartz-barite-sphalerite-galena-pyrite vein set. The rhenium in Muratdere is hosted within two generations of molybdenite: early microfracture-hosted molybdenite and later vein-hosted molybdenite. In situ laser ablation-inductively coupled plasma-mass spectrometry analysis of sulfides shows that the later molybdenite has significantly higher concentrations of Re (average 1,124 ppm, σ = 730 ppm, n = 43) than the early microfracture-hosted molybdenite (average 566 ppm, σ = 423 ppm, n = 28). Pyrite crystals associated with the Re-rich molybdenite have higher Co and As concentrations than those in other vein sets, with Au associated with As. The microfracture-hosted sulfides have δ34S values between −2.2‰ and +4.6‰, consistent with a magmatic source. The vein-hosted sulfides associated with the high-Re molybdenite have a δ34S signature of 5.6‰ to 8.8‰, similar to values found in peridotite lenses in the Anatolian belt. The later enrichment in Re and δ34S-enriched S may be sourced from the surrounding ophiolitic country rock or may be the result of changing redox conditions during deposit formation

Trace element systematics and ore-forming processes in mafic VMS deposits: Evidence from the Troodos ophiolite, Cyprus

The volcanogenic massive sulfide (VMS) deposits in the Troodos ophiolite (Cyprus) are ancient analogues for modern day seafloor massive sulfide mineralisation formed in a supra-subduction zone environment. In this study we present the first detailed in situ study of trace elements in sulfides from twenty VMS deposits hosted in the Troodos ophiolite to better understand factors that influence the distribution, enrichment and incorporation of trace elements in different sulfide minerals. On a mineral scale, trace elements exhibit systematic variations between pyrite, chalcopyrite and sphalerite. Pyrite preferentially incorporates As, Sb, Au and Te, whilst chalcopyrite is enriched in Co and Se. Sphalerite is trace element poor with the exception of Ag and Cd. Selenium averages 278 ppm (n = 150) in chalcopyrite but only 42 ppm (n = 1322) in pyrite. Bismuth and Te in pyrite show a weak positive correlation (R2 = 0.35) in some VMS deposits possibly linked with the occurrence of Bi-telluride inclusions. Trace element concentrations also vary between colloform and euhedral pyrite, with an enrichment of Au, As, Sb, Cu and Zn in colloform compared to euhedral pyrite. Time resolved laser ablation profiles reveal that the trace element distribution on a mineral scale is not uniform and varies with crystallographic effects, fluctuating physicochemical fluid conditions such as temperature, pH, fS2, fO2 and ligand availability during sulfide precipitation. Incorporation mechanisms in sulfides differ between elements in pyrite, Ag, As, Se and Pb are hosted in solid solution or as nanoscale inclusions, whilst Au, Sb and Te may form micro-scale inclusions. On a regional scale (20 km) the distribution of trace elements exhibits systematic variations between three major structural domains; namely the Solea, Mitsero and Larnaca grabens. The VMS deposits of the magmatic-tectonic Solea graben are enriched in Se, Co, Te, Au and Cu relative to Mitsero, which is a purely extensional feature. Therefore, we hypothesise that a variable magmatic volatile influx related to a) ‘magma’ volume, b) migration of the magmatic-hydrothermal crack front and associated brine liberation or c) a variation in protolith metal concentration are responsible for regional scale variations in VMS geochemistry. This is suggested to be intrinsically linked to the spreading architecture of Troodos

Mineral-scale variation in the trace metal and sulfur isotope composition of pyrite: implications for metal and sulfur sources in mafic VMS deposits

The link between metal enrichment and the addition of a magmatic volatile phase in volcanogenic massive sulfide deposits and actively forming seafloor massive sulfide deposits remains poorly characterized. This is especially true when considering how metal, sulfur and fluid flux change with time. In this study, we combine in situ sulfur isotope (δ34S; n = 31) measurements with trace metal chemistry of pyrite (n = 143) from the Mala VMS deposit, Troodos, Cyprus. The aim of our study is to assess the links between volatile influx and metal enrichment and establish how, or indeed if, this is preserved at the scale of individual mineral grains. We classify pyrite based on texture into colloform, granular, disseminated and massive varieties. The trace metal content of different pyrite textures is highly variable and relates to fluid temperature and secondary reworking that are influenced by the location of the sample within the mound. The sulfur isotope composition of pyrite at Mala ranges from − 17.1 to 7.5‰ (n = 31), with a range of − 10.9 to 2.5‰ within a single pyrite crystal. This variation is attributed to changes in the relative proportion of sulfur sourced from (i) SO2 disproportionation, (ii) thermochemical sulfate reduction, (iii) the leaching of igneous sulfur/sulfide and (iv) bacterial sulfate reduction. Our data shows that there is no correlation between δ34S values and the concentration of volatile elements (Te, Se) and Au in pyrite at Mala indicating that remobilization of trace metals occurred within the mound

Effects of magmatic volatile influx in mafic VMS hydrothermal systems: Evidence from the Troodos ophiolite, Cyprus

The Troodos ophiolite, Cyprus is the principal on- land analogue for mafic-hosted volcanogenic massive sulfide (VMS) deposits. This study, for the first time, presents sulfur isotope (δ34S) data on a regional scale from VMS deposits and other mineralised zones across the Troodos ophiolite. In combination δ34S, Se/S ratios and trace element chemistry (e.g., Se, Cu and Au) of different hydrothermal sulfides are used to assess variations in magmatic volatile influx and the source of metals and sulfur in ancient hydrothermal systems. Sulfur isotope analyses (n = 180) across 19 mineral deposits indicate a variable source of sulfur in the Troodos VMS hydrothermal system, this in turn allows a variable source of metals to be inferred. Pyrite δ34S range from −5.5‰ to +13.2‰ with an average of +4.6‰ (n = 160) for all deposits investigated. These δ34S variations cannot only be explained by variable proportions of thermochemical seawater sulfate reduction (δ34S +18 to +19‰) and leaching of primary magmatic sulfur from igneous rocks (δ34S 0-1‰). Consequently, two processes are proposed, explaining the trace metal and δ34S variation across the Troodos ore-forming systems including, i) a variable source of metals in the sheeted dyke complex and ii) the addition of a magmatic volatile-rich phase to the VMS hydrothermal systems. Two distinct lava units exist in the Troodos stratigraphy, namely the upper and lower pillow lavas (UPL and LPL). The more primitive UPL are enriched in Au, Se and Cu relative to As, Sb and Zn that are concentrated in the LPL. Some VMS deposits pre-date the formation of the UPL (e.g., Agrokipia A) suggesting Se, Cu and Au depleted source rocks. Hence, the stratigraphic position of VMS deposits and the ratio of UPL:LPL affinity elements (e.g., As + Zn + Sb vs. Cu + Se + Au) imply a systematic relationship between trace element distribution and stratigraphic depth; this relates to the relative proportion of UPL and LPL affinity lavas within the metal source region. δ34S values <0‰ recorded in some VMS deposits that are less than the Troodos magmatic mean of 0- 1‰ may be related to anhydrite buffering during fluid ascent, microbial sulfate reduction or the direct contribution of magmatically derived sulfur, to the hydrothermal system from an underlying magma chamber via volatile exsolution. We propose that negative δ34S values combined with Se/S 106 ratios >500 in pyrite suggest the contribution of a magmatic volatile component (e.g., Apliki and Skouriotissa). We demonstrate that the source of metals and sulfur in the Troodos VMS hydrothermal system is affected by regional scale processes related to i) variable source lithologies and, ii) the contribution of a magmatic volatile phase to some Troodos VMS hydrothermal systems

The mineralogy and mineral associations of platinum-group elements and precious metals in the Aurora Cu-Ni-Au-PGE deposit, Northern Limb, Bushveld Complex

Aurora is a platinum-group element (PGE) prospect hosted in the Northern Limb of the Bushveld Complex, South Africa. It is one of only three deposits discovered in the Northern Limb so far to be hosted in the melanocratic-leucocratic gabbroic cumulates of the Main Zone of the Rustenberg Layered Suite (Aurora, Moorddrift and Waterberg T Zone deposits), rather than in predominantly ultramafic rocks (e.g. Platreef). The host cumulates at Aurora have been divided into three principal units and they intrude the dolomites of the lower Transvaal Supergroup. Base metal sulphide (BMS) mineralisation with PGE is present in the leucogabbronorites and gabbronorites of Unit 2, and in coarse grained gabbronorite veins which intrude the peridotites of Unit 1. These veins contain up to 50% interstitial pyrrhotite-pentlandite-chalcopyrite ± pyrite. Unit 2 contains 1-3% pentlandite-pyrrhotite-chalcopyrite assemblages, and 1-5% chalcopyrite ± pyrite/pyrrhotite associated with hydrothermal alteration. The PGE content of Aurora however is predominantly controlled by the presence of platinum-group minerals (PGM), not BMS. LA-ICP-MS analysis of sulphides shows the BMS in Aurora have lower PGE concentrations than other Bushveld magmatic sulphides, with pentlandite carrying much lower concentrations of Pd (average 23 ppm) than the Platreef or the Merensky Reef. SEM-EDS analysis of 26 sections characterised 995 platinum-group minerals (PGM) and precious metal-bearing minerals (PMM), with a total area of 27850 μm 2 and an average size of 28.2 μm 2 . Of the PGM and PMM identified in Aurora 85% (by area) are Pd-Te-Bi minerals, with 6% Pd-Te minerals, 4% electrum and 3% Ag-Te minerals, along with minor Pd-Bi, Pd-As, Pt-Te-Bi, Pt-As and Pt-S minerals that collectively comprise 2% of total area. Only 25% of the PGM and PMM in Aurora are BMS hosted, with the rest hosted in silicates. Of the total PGM and PMM area 22% are hosted in alteration-silicates (quartz, chlorite or actinolite) in an alteration halo around sulphides. Unusually, 52% of the PGM and PMM are spatially removed from BMS, instead hosted in alteration silicates and within cracks in primary silicates away from any BMS. This indicates a multi-stage ore genesis model, with hydrothermal remobilisation of PGE important for ore formation. The style and host rocks for mineralisation in the Aurora deposit are fundamentally different from other deposits in the Northern Limb of the Bushveld hosted in ultramafic rocks, such as the Platreef, GNPA member deposits and the F zone of the Waterberg deposit, all of which contain a greater diversity of PGM and BMS with higher precious metal contents. The mineralisation most similar to Aurora is the T Zone of the Waterberg deposit, located to the north of Aurora, which been suggested to be an along-strike equivalent of the Aurora Main Zone mineralisation. However, despite strong similarities in PGM mineralogy and S isotope signatures there are significant differences in BMS mineralisation and host lithology meaning it is unlikely they are directly linked stratigraphically. At present it seems more likely that Aurora and the Waterberg T Zone reflect similar fluid-influenced processes operating in different parts of the Main Zone, perhaps at different times and in different structural basins, rather than a continuous mineralised zone along strike

Extreme enrichment of selenium in the Apliki Cyprus-type VMS deposit, Troodos, Cyprus

The Troodos ophiolite Cyprus hosts the type locality for Cyprus-type, mafic volcanogenic massive sulfide (VMS) deposits. Regional soil geochemical data for Troodos are highly variable with the Solea graben, one of three regional graben structures on Cyprus, showing enrichment in Te and Se. Of the three VMS sampled within the Solea graben, Apliki exhibits the most significant enrichment in Se. Samples from the South Apliki Breccia Zone; a zone of hematite-rich breccia containing euhedral pyrite and chalcopyrite, contain up to 4953 and 3956 ppm Se in pyrite and chalcopyrite, respectively. Four paragenetic stages are identified at Apliki and different generations of pyrite are distinguishable using trace-element chemistry analysed via laser ablation inductively coupled plasma mass spectrometry. Results indicate stage I pyrite formed under reduced conditions at high temperatures >280°C and contains 182 ppm (n = 22 σ = 253) Se. Late stage III pyrite which is euhedral and overprints chalcopyrite and hematite is enriched in Se (averaging 1862 ppm; n = 23 σ = 1394). Sulfide dissolution and hematite formation displaced large amounts of Se as hematite cannot accommodate high concentrations of Se in its crystal structure. The mechanisms proposed to explain the pronounced change in redox are twofold. Fault movement leading to localized seawater ingress coupled with a decreasing magmatic flux that generated locally oxidizing conditions and promoted sulfide dissolution. A Se/S ratio of 9280 indicates a probable magmatic component for late stage III pyrite, which is suggested as a mechanism explaining the transition from oxidizing back to reduced conditions. This study highlights the significance of changes in redox which promote sulfide dissolution, mobilization and enrichment of Se