Bedrock platinum-group element mineralization of zonal clinopyroxenite–dunite massifs of the Middle Urals

Features of the chemical composition of platinum-group mineral assemblages from chromitites of the zonal Svetly Bor, Veresovy Bor, and Nizhny Tagil clinopyroxenite–dunite massifs of the Middle Urals are compared for the first time.     

A review of sulfur to selenium ratios in magmatic nickel–copper and platinum-group element deposits

Deviations in the sulfur to selenium ratios (S/Se) from mantle values in magmatic Ni–Cu–Platinum Group Elements (PGE) sulfide deposits have been widely used to constrain the ore forming processes. Basically, S/Se ratios greater than mantle values are interpreted to be the result of contamination of the mantle derived magma by S-rich sedimentary rocks, whereas S/Se ratios lower than mantle values are thought to be the result of S loss during post-crystallization. However, there are many other processes involved in producing a deposit and it is possible that these may be also important in controlling S/Se ratios. In order to investigate the relative importance of these processes, we have compiled a data base of S, Se, δ³⁴S and metal values from Ni–Cu–PGE sulfide deposits. This compilation shows that processes affecting S/Se ratios can be divided into two main classes: the magmatic processes and the late- to post-magmatic processes.

• 1)Magmatic processes include the well-known addition of S from sedimentary rocks, variations in the sulfide to silicate liquid ratio (R-factor), depletion of the silicate magma in Se by early segregation of the sulfide liquid, and the moderate incompatibility of Se into the first sulfide minerals to crystallize from a sulfide liquid, the monosulfide-solid-solution (MSS). This incompatibility results in a change in S/Se ratio between the Fe-rich and Cu-rich zones of magmatic sulfide ores. The fractionation of Se during crystallization of sulfide liquids has not previously been appreciated.
• 2)Late- to post-magmatic processes include: hydrothermal alteration, high-grade metamorphism, serpentinization and supergene weathering. Some metamorphosed Cu-deposits have low S/Se ratios suggesting S-loss by breakdown of sulfide minerals during a high-grade metamorphic event. However, the effectiveness of this process remains unclear and alternative models exist. The preferential remobilization of S relative to Se during hydrothermal alteration, serpentinization and supergene weathering leads to a moderate decrease of S/Se ratios values and can mask the initial S/Se ratio.

     

Distribution of platinum-group elements and Os isotopes in chromite ores from Mayarí-Baracoa Ophiolitic Belt (eastern Cuba)

The Mayarí-Baracoa ophiolitic belt in eastern Cuba hosts abundant chromite deposits of historical economic importance. Among these deposits, the chemistry of chromite ore is very variable, ranging from high Al (Cr#=0.43–0.55) to high Cr (Cr#=0.60–0.83) compositions. Platinum-group element (PGE) contents are also variable (from 33 ppb to 1.88 ppm) and correlate positively with the Cr# of the ore. Bulk PGE abundances correlate negatively with the Pd/Ir ratio showing that chromite concentrates mainly Os, Ir and Ru which gives rise to the characteristic negatively sloped, chrondrite-normalized PGE patterns in many chromitites. This is consistent with the mineralogy of PGEs, which is dominated by members of the laurite–erlichmanite solid solution series (RuS₂–OsS₂), with minor amounts of irarsite (IrAsS), Os–Ir alloys, Ru–Os–Ir–Fe–Ni alloys, Ni–Rh–As, and sulfides of Ir, Os, Rh, Cu, Ni, and/or Pd. Measured ¹⁸⁷Os/¹⁸⁸Os ratios (from 0.1304 to 0.1230) are among the lower values reported for podiform chromitites. The ¹⁸⁷Os/¹⁸⁸Os ratios decrease with increasing whole-rock PGE contents and Cr# of chromite. Furthermore, γOs values of all but one of the chromitite samples are negative indicating a subchondiritc mantle source. γOs decrease with increasing bulk Os content and decreasing ¹⁸⁷Re/¹⁸⁸Os ratios. These mineralogical and geochemical features are interpreted in terms of chromite crystallization from melts varying in composition from back-arc basalts (Al-rich chromite) to boninites (Cr-rich chromite) in a suprasubduction zone setting. Chromite crystallization occurs as a consequence of magma mixing and assimilation of preexisting gabbro sills at the mantle–crust transition zone. Cr#, PGE abundances, and bulk Os isotopic composition of chromitites are determined by the combined effects of mantle source heterogeneity, the degree of partial melting, the extent of melt-rock interactions, and the local sulfur fugacity. Small-scale (μm to cm) chemical and isotopic heterogeneities in the platinum-group minerals are controlled by the mechanism(s) of chromite crystallization in a heterogeneous environment created by the turbulent regime generated by successive inputs of different batches of melt.     

Geochemistry and mineralogy of platinum-group elements(PGE) in chromites from CentralnoyeⅠ,Polar Urals,Russia

The Polar Urals region of northern Russia is well known for large chromium(Cr)-bearing massifs with major chromite orebodies,including the Centralnoye I deposit in the Ray-Iz ultramafic massif of the Ural ophiolite belt.New data on platinum(Pt)-group elements(PGE).geochemistry and mineralogy of the host dunite shows that the deposit has anomalous iridium(Ir) values.These values indicate the predominance of ruthenium-osmium-iridium(Ru-Os-Ir)-bearing phases among the platinum-group mineral (PGM) assemblage...     

First report of platinum-group minerals from a hornblende gabbro dyke in the vicinity of the Southeast Extension Zone of the Voisey’s Bay Ni-Cu-Co deposit, Labrador

Summary This study reports the first documented occurrence of platinum group-minerals (PGM) in the vicinity of the Voisey’s Bay magmatic sulfide ore deposit. The PGM are present in a sulfide poor, hornblende gabbro dyke in the Southeast Extension Zone of the massive sulfide Ovoid deposit. The dyke has somewhat elevated concentrations of platinum-group elements (PGE) and gold (up to 1.95 g/t Pt, 1.41 g/t Pd, and 6.59 g/t Au), as well as Cu, Pb, Ag, Sn, Te, Bi and Sb. The PGM formed by magmatic processes and were little disturbed by subsequent infiltration of an externally-supplied hydrothermal fluid. To date, no similar PGM occurrences have been discovered in the Ovoid deposit itself. Whole rock REE patterns indicate that the dyke is geochemically related to the main conduit troctolites, which carry the bulk of the massive sulfide mineralization at Voisey’s Bay. The PGE mineralization is Pt- and Pd-rich, where the Pt and Pd occur predominantly as discrete PGM with minor Pd in solid solution in galena (average=1.8 ppm) and pentlandite (average=2 ppm). The discrete PGM are predominantly hosted by disseminated base-metal sulfides (bornite, chalcopyrite, and galena) (56 vol%) and are associated with other precious metal minerals (13 vol%) with only ∼3 vol% of the PGM hosted by silicate minerals. In whole rock samples, the PPGE (Pt, Pd, and Rh) correlate with abundances of chalcopyrite, bornite, galena, and other precious metal minerals (PMM), whereas the IPGE (Ir, Ru, and Rh) correlate with pyrrhotite and pentlandite. There are no correlations of the PGE with chlorine. Lead isotope compositions of galena associated with the PGE mineralization in the Southeast Extension Zone are broadly similar to those for galena in the Ovoid. The lead isotope compositions are much different from those in the Voisey’s Bay Syenite, which is a potential external hydrothermal fluid source. The observed Cu-rich, Pb-rich sulfide compositions and associated Pt-Pd-Au-Ag-Sn-Te-Bi-Sb assemblage in the dyke can be produced magmatically as late ISS differentiates (e.g., Prichard et al., 2004). Melting temperatures of the PGM are also consistent with a magmatic origin. Following crystallization of PGM from magmatic sulfide, an external REE-enriched hydrothermal fluid was introduced to the system, producing secondary amphibole and locally remobilizing the Pb and Sn from the sulfides hosting the PGM. Author’s address: M. A. E. Huminicki, Department of Earth Sciences, Memorial University of Newfoundland, St. John’s, NL, Canada A1B 3X5     

A laser ablation ICP-MS study of platinum-group and chalcophile elements in base metal sulfide minerals of the Jinchuan Ni–Cu sulfide deposit,NW China

The paper presents concentrations of the platinum-group and chalcophile elements in the base metal sulfides (BMS) from the Jinchuan Ni–Cu sulfide deposit determined by laser ablation-inductively coupled plasma-mass spectrometry. Mass balance calculations reveal that pentlandite hosts a large proportion of Co, Ni and Pd (> 65%), and that pentlandite and pyrrhotite accommodate significant proportions of Re, Os, Ru, Rh, and Ag (~ 35–90%), whereas chalcopyrite contains a small amount of Ag (~ 10%) but negligible platinum-group elements. Iridium and Pt are not concentrated in the BMS and mostly occur in As-rich platinum-group minerals. The enrichments of Co, Ni, Re, Os, Ru, and Rh in pentlandite and pyrrhotite, and Cu in chalcopyrite are consistent with the fractionation of sulfide liquid and exsolution of pentlandite and pyrrhotite from the mono-sulfide solid solution (MSS). The Ir-bearing minerals exsolved from the MSS, depleting pentlandite and pyrrhotite in Ir, whereas sperrylite exsolved from the residual sulfide liquid on cooling. Diffusion of Pd from residual sulfide liquid into pentlandite during its exsolution from the MSS and crystallization of Pt-bearing minerals in the residual sulfide liquid resulted in the enrichment of Pd in pentlandite and decoupling between Pd and Pt in the Jinchuan net-textured and massive ores.     

Re–Os isotope and platinum-group element geochemistry of the Pobei Ni–Cu sulfide-bearing mafic–ultramafic complex in the northeastern part of the Tarim Craton

A number of mafic–ultramafic intrusions that host Ni–Cu sulfide mineralization occur in the northeastern Tarim Craton and the eastern Tianshan Orogenic Belt (NW China). The sulfide-mineralized Pobei mafic–ultramafic complex is located in the northeastern part of the Tarim Craton. The complex is composed of gabbro and olivine gabbro, cut by dunite, wehrlite, and melatroctolite of the Poyi and Poshi intrusions. Disseminated Ni–Cu sulfide mineralization is present towards the base of the ultramafic bodies. The sulfide mineralization is typically low grade (<0.5 wt.% Ni and <2 wt.% S) with low platinum-group element (PGE) concentrations (<24.5 ppb Pt and <69 ppb Pd); the abundance of Cu in 100 % sulfide is 1–8 wt.%, and Ni abundance in 100 % sulfide is typically >4 wt.%. Samples from the Pobei complex have εNd (at 280 Ma) values up to +8.1, consistent with the derivation of the magma from an asthenospheric mantle source. Fo 89.5 mol.% olivine from the ultramafic bodies is consistent with a primitive parental magma. Sulfide-bearing dunite and wehrlite have high Cu/Pd ratios ranging from 24,000 to 218,000, indicating a magma that evolved under conditions of sulfide saturation. The grades of Ni, Cu, and PGE in 100 % sulfide show a strong positive correlation. A model for these variations is proposed where the mantle source of the Pobei magma retained ~0.033 wt.% sulfide during the production of a PGE-depleted parental magma. The parental magma migrated from the mantle to the crust and underwent further S saturation to generate the observed mineralization along with its high Cu/Pd ratio at an R-factor varying from 100 to 1,200. The mineralization at Poshi and Poyi has very high γOs (at 280 Ma) values (+30 to +292) that are negatively correlated with the abundance of Os in 100 % sulfide (5.81–271 ppb) and positively correlated with the Re/Os ratios; this indicates that sulfide saturation was triggered by the assimilation of crustal sulfide with both high γOs and Re/Os ratios. When compared to other Permian mafic–ultramafic intrusions with sulfide mineralization in the East Tianshan, the Poyi and Poshi ultramafic bodies were formed from more primitive magmas, and this helps to explain why the sulfide mineralization has high Ni tenor.     

Mineralogy and composition of the chromitites and their platinum-group minerals from Ortaca (Muğla-SW Turkey): evidence for ophiolitic chromitite genesis

Summary A large number of podiform chromitite bodies of massive, disseminated and nodular type have been located in ultramafic units, composed of depleted mantle harzburgite and dunite of the Marmaris Peridotite from Ortaca (Mula, SW Turkey). The chromite ore bodies are surrounded by dunite envelopes of variable thickness, exhibiting transitional boundaries to harzburgite host rocks. Chromitites, containing a large number of inclusions, i.e. silicates, base metal sulphides and alloys, and platinum-group minerals (PGM) have a wide range of chemical composition. The Cr# [Cr/(Cr+Al)] values of most chromitites are high (0.61–0.81) and Mg# [Mg/(Mg+Fe²⁺)] values range between 0.65 and 0.71 with TiO₂ content lower than 0.24wt.%, which may reflect the crystallization of chromites from boninitic magmas in supra-subduction setting environment.Platinum-group minerals (PGM) such as laurite, erlichmanite and Os–Ir alloys, silicates such as olivine, clinopyroxene and amphibole, and base metal sulphides (BM-S), alloys (BM-A) and arsenides (BM-As) are found as inclusions in chromite or in the serpentine matrix. Platinum-group element (PGE) concentrations of the Ortaca chromitites (OC) are low in all samples. Total PGE (Ir+Ru+Rh+Pt+Pd) ranges from 63ng/g to 266ng/g and Pd/Ir ratios range between 0.23 and 4.75. PGE content is higher and the Pd/Ir ratio lower in Cr-rich chromitites compared to Al-rich ones. There is a strong negative correlation between the Cr# and Pd/Ir ratios (r=–0.930). The PGE patterns show a negative slope from Ru to Pt and a positive slope from Pt to Pd. The low PGE content in the majority of the OC may reflect a lack of sulphur saturation during an early stage of their crystallization. The laurite compositions show a wide range of Ru–Os substitution caused by relatively low temperature and increasing f(S₂) during the chromite crystallization. The high Cr# of and hydrous silicate mineral inclusions in chromite imply that chromite crystallized in a supra-subduction setting.     

Petrology of Al- and Cr-rich ophiolitic chromitites from the Muğla,SW Turkey: implications from composition of chromite,solid inclusions of platinum-group mineral,silicate, and base-metal mineral,and Os-isotope geochemistry

Ultramafic rocks around the city of Muğla in SW Turkey are represented by mantle peridotites depleted to various degrees, ranging from cpx-rich harzburgites to depleted harzburgite and dunite. Cpx-rich harzburgites are thought to be the residua left after extraction of MORB-type basalt, from which high-Al chromitite [49.2 < Cr# = 100 × Cr/(Cr + Al) < 53.5] crystallised with a higher proportion of ¹⁸⁷Os/¹⁸⁸Os (average of 0.1361). However, depleted harzburgites are assumed to be the residua left after extraction of hydrous boninitic melt produced by second stage partial melting of already depleted mantle due to a subducting slab, from which high-Cr chromitites (64.2 < Cr# < 85.9) with lower and heterogeneous ¹⁸⁷Os/¹⁸⁸Os ratio (average of 0.1324) were crystallised as a result of melt–rock interaction in a supra-subduction environment. Dunites around the chromite deposits are considered to be the product of melt–peridotite interaction. Most of the chromitites contain high-Cr chromite and display enrichment in IPGE (Os, Ir, Ru) over PPGE (Rh, Pt, Pd), with PGE concentrations between 61 and 1,305 ppb. Consistently, laurite-erlichmanite series minerals with various Os concentrations are found to be the most abundant PGM inclusions in chromite. Os–Ir–Ru alloy, irarsite, and kashinite, as well as Pt–Fe alloy and Pt-oxide, which are not common in ophiolitic chromitites, were also detected as magmatic PGM inclusions. Pentlandite, millerite, and, rarely heazlewoodite form the magmatic inclusions of base-metal sulphide. The presence of olivine and clinopyroxene, as well as hydrous silicate inclusions such as amphibole and phlogopite, in high-Cr chromitite supports the idea that high-Cr chromitites were formed in a supra-subduction environment.     

Re–Os isotopic constraints on the source of platinum-group minerals (PGMs) from the Vestřev pyrope-rich garnet placer deposit,Bohemian Massif

Mineralogical studies of the heavy fraction from a Holocene pyrope-rich garnet placer deposit at Vestřev (Krkonoše Piedmont Basin, Bohemian Massif) have identified the presence of very rare grains of platinum group minerals (PGM). Pt–Fe alloy grains are accompanied by Os–Ir–Ru minerals (native osmium, iridium, and ruthenium) with inclusions of Pt–Fe alloy and hongshiite (PtCu). This mineral assemblage is typical for several mantle settings including ophiolites. The chemistry of the Os–Ir–Ru minerals shows an enrichment of the PGM in Ru, which is typical of ophiolites. The grain morphology of PGM and pyrope-rich garnet (mostly rounded with numerous euhedral/subhedral grains) does not exclude a common source. In-situ laser-ablation MC-ICP-MS was used to measure the Re–Os isotopic compositions of single Os-rich grains, which show heterogeneous subchondritic Os isotopic compositions (¹⁸⁷Os/¹⁸⁸Os = 0.12082–0.12505 ± 0.00003). This precludes their low-temperature origin and indicates derivation of platinum-group elements (PGEs) essentially from mantle-derived rocks without a significant contribution of crustal Os. The mantle model age (T_MA) and Re-depletion model age (T_RD) model ages range from ~ 0.4 to ~ 1.0 Ga and most likely reflect a long history of melt depletion that affected the mantle sources of PGM.     

Using platinum-group elements and Au geochemistry to constrain the genesis of podiform chromitites and associated peridotites from the Soghan mafic–ultramafic complex,Kerman, Southeastern Iran

The podiform chromite deposit of the Soghan mafic–ultramafic complex is one of the largest chromite deposits in south-east Iran (Esfandagheh area). The Soghan complex is composed mainly of dunite, harzburgite, lherzolite, pyroxenite, chromitite, wehrlite and gabbro. Olivine, orthopyroxene, and to a lesser extent clinopyroxene with highly refractory nature, are the primary silicates found in the harzburgites and dunites. The forsterite content of olivine is slightly higher in dunites (Fo₉₄) than those in harzburgites (Fo₉₂) and lherzolites (Fo₈₉). Chromian spinel mainly occurs as massive chromitite pods and as thin massive chromitite bands together with minor disseminations in dunites and harzburgites. Chromian spinels in massive chromitites show very high Cr-numbers (80–83.6), Mg-numbers (62–69) and very low TiO₂ content (averaging 0.17 wt.%) for which may reflect the crystallization of chromite from a boninitic magma. The Fe^3 +-number is very low, down to < 0.04 wt.%, in the chromian spinel of chromitites and associated peridotites of the Soghan complex.PGE contents are variable and range from 80 to 153 pbb. Chromitites have strongly fractionated chondrite-normalized PGE patterns, which are characterized by enrichments in Os, Ir and Rh relative to Pt and Pd. Moreover, the Pd/Ir value which is an indicator of PGE fractionation ranges from < 0.08 to 0.24 in chromitite of the Soghan complex. These patterns and the low PGE abundances are typical of ophiolitic chromitites and indicating a high degree of partial melting (about 20–24%) of the mantle source. Moreover, the Pd_N/Ir_N ratios in dunites are unfractionated, averaging 1.2, whereas the harzburgites and lherzolites show slightly positive slopes PGE spidergrams, together with a small positive Ru and Pd anomaly, and their Pd_N/Ir_N ratio averages 1.98 and 2.15 respectively.The mineral chemistry data and PGE geochemistry, along with the calculated parental melts in equilibrium with chromian spinel of the Soghan chromitites indicate that the Soghan complex was generated from an arc-related magma with boninitic affinity above a supra-subduction zone setting.     

In situ Re–Os isotopic analysis of platinum-group minerals from the Mayarí-Cristal ophiolitic massif (Mayarí-Baracoa Ophiolitic Belt,eastern Cuba): implications for the origin of Os-isotope heterogeneities in podiform chromitites

Chromitite pods in the Mayarí-Cristal ophiolitic massif (eastern Cuba) were formed in the Late Cretaceous when island arc tholeiites and MORB-like back-arc basin basalts reacted with residual mantle peridotites and generated chromite-rich bodies enclosed in dunite envelopes. Platinum-group minerals (PGM) in the podiform chromitites exhibit important Os-isotope heterogeneities at the kilometric, hand sample and thin section scales. ¹⁸⁷Os/¹⁸⁸Os calculated at the time of chromitite crystallization (~90 Ma) ranges between 0.1185 and 0.1295 (γOs = −7.1 to +1.6, relative to enstatite chondrite), and all but one PGM have subchondritic ¹⁸⁷Os/¹⁸⁸Os. Grains in a single hand sample have initial ¹⁸⁷Os/¹⁸⁸Os that spans from 0.1185 to 0.1274, and in one thin section it varies between 0.1185 and 0.1232 in two PGM included in chromite which are only several millimeters apart. As the Os budget of a single micrometric grain derives from a mantle region that was at least several m³ in size, the variable Os isotopic composition of PGM in the Mayarí-Cristal chromitites probably reflects the heterogeneity of their mantle sources on the 10–100 m scale. Our results show that this heterogeneity was not erased by pooling and mingling of individual melt batches during chromitite crystallization but was transferred to the ore deposits on mineral scale. The distribution of the Os model ages calculated for PGM shows four main peaks, at ~100, 500, 750 and 1,000 Ma. These variable Os model ages reflect the presence of different depleted domains in the oceanic (Pacific-related) upper mantle of the Greater Antilles paleo-subduction zone. The concordance between the age of crystallization of the Mayarí-Cristal chromitites and the most recent peak of the Os model age distribution in PGM supports that Os in several grains was derived from fertile domains of the upper mantle, whose bulk Os isotopic composition is best approximated by that of enstatite chondrites; on the other hand, most PGM are crystallized by melts that tapped highly refractory mantle sources.     

Atypical stratiform sulfide-poor platinum-group element mineralisation in the Agnew – Wiluna Belt komatiites,Wiluna, Western Australia

A new style of komatiite-associated sulfide-poor platinum-group element (PGE: Os, Ir, Ru, Rh, Pt, Pd) mineralisation has been identified at Wiluna in the strongly nickel sulfide (NiS) mineralised Agnew – Wiluna Greenstone Belt, Western Australia. The komatiite sequence at Wiluna is ～200 m thick and comprises a basal pyroxenite layer, a thick ortho-to-mesocumulate-textured peridotite core, which is overlain by rhythmically layered wehrlite, oikocrystic pyroxenite and thick upper gabbroic margins. Pegmatoid and dendritic (harrisitic) domains are common features, whereas spinifex-textured horizons and flow-top breccias are absent. The presence of anomalous PGE-enriched horizons (ΣPt – Pd = 200 – 500 ppb) in the oikocrystic pyroxenite and in the layered melagabbro and gabbronorite horizons directly overlying the wehrlite unit is due to the presence of fine-grained (1 – 10 μm) platinum-group minerals (PGMs). More than 70 PGM grains were identified, and a considerable mineralogical variability was constrained. However, only Pd – Pt-bearing phases were identified, whereas no Ir – Ru-bearing PGMs were found in any of the sections examined. Interestingly, all PGMs are not in paragenetic association with sulfides, and only sulfide-poor/free intervals contain significant PGM concentrations. The whole-rock PGE sequence largely reflects the PGM distribution. It is hypothesised that the Pd – Pt enrichment in the oikocrystic pyroxenite and melagabbros and the overall Ir – Ru depletion in the upper mafic section of the sequence are the result of extensive olivine and chromite crystallisation in the basal ultramafic section. PGE saturation was driven by extensive crystallisation of silicate and oxide phases in a sulfide-undersaturated environment. The crystallisation of clinopyroxene in the oikocrystic pyroxenite horizon may have triggered the formation of Pt – Pd-bearing alloys and arsenides, which were the first PGMs to form. Stratiform sulfide-poor PGE mineralisation at Wiluna is more similar in stratigraphic setting, style and composition to PGE-rich sulfide-poor mineralisation zones in thick differentiated intrusions, rather than to other PGE-enriched zones in komatiite-hosted systems, where PGE enrichment is directly associated with accumulations of magmatic sulfides.     

Sulfide-associated mineral assemblages in the Bushveld Complex, South Africa: platinum-group element enrichment by vapor refining by chloride–carbonate fluids

The petrology of base metal sulfides and associated accessory minerals in rocks away from economically significant ore zones such as the Merensky Reef of the Bushveld Complex has previously received only scant attention, yet this information is critical in the evaluation of models for the formation of Bushveld-type platinum-group element (PGE) deposits. Trace sulfide minerals, primarily pyrite, pyrrhotite, pentlandite, and chalcopyrite are generally less than 100 microns in size, and occur as disseminated interstitial individual grains, as polyphase assemblages, and less commonly as inclusions in pyroxene, plagioclase, and olivine. Pyrite after pyrrhotite is commonly associated with low temperature greenschist alteration haloes around sulfide grains. Pyrrhotite hosted by Cr- and Ti-poor magnetite (Fe₃O₄) occurs in several samples from the Marginal to Lower Critical Zones below the platiniferous Merensky Reef. These grains occur with calcite that is in textural equilibrium with the igneous silicate minerals, occur with Cl-rich apatite, and are interpreted as resulting from high temperature sulfur loss during degassing of interstitial liquid. A quantitative model demonstrates how many of the first-order features of the Bushveld ore metal distribution could have developed by vapor refining of the crystal pile by chloride–carbonate-rich fluids during which sulfur and sulfide are continuously recycled, with sulfur moving from the interior of the crystal pile to the top during vapor degassing.     

Reply to comments by L.J. Cabri on “Changes in sulfides and platinum-group minerals with the degree of alteration in the Roby, Twilight, and High Grade Zones of the Lac des Iles Complex, Ontario, Canada”

Dr. Cabri has a number of criticisms of Djon and Barnes (2012). Some of the criticisms are valid and are the result of what we consider to be minor errors and omissions that can occur when an M.Sc. is converted to a paper. However, none of these change our conclusions, and we stand by our interpretations.     

Closed-system behaviour of the Re–Os isotope system recorded in primary and secondary platinum-group mineral assemblages: Evidence from a mantle chromitite at Harold's Grave (Shetland Ophiolite Сomplex,Scotland)

This study evaluates in detail the mineral chemistry, whole-rock and mineral separate Os-isotope compositions of distinct platinum-group mineral (PGM) assemblages in an isolated chromitite pod at Harold's Grave which occurs in mantle tectonite in the Shetland Ophiolite Complex (SOC), Scotland. This was the first ophiolite sequence worldwide that was shown to contain ppm levels of all six platinum-group elements (PGE) in podiform chromitite, including the contrasting type localities found here and at Cliff. At Harold's Grave the primary PGM assemblage is composed mainly of laurite and/or Os-rich iridium and formed early together with chromite, whereas the secondary PGM assemblage dominated by laurite, Os-rich laurite, irarsite, native osmium and Ru-bearing pentlandite is likely to reflect processes including in-situ serpentinization, alteration during emplacement and regional greenschist metamorphism. The osmium isotope data define a restricted range of ‘unradiogenic’ ¹⁸⁷Os/¹⁸⁸Os values for coexisting laurite and Os-rich alloy pairs from ‘primary’ PGM assemblage (0.12473–0.12488) and similar ‘unradiogenic’ ¹⁸⁷Os/¹⁸⁸Os values for both ‘primary’ and ‘secondary’ PGM assemblages (0.1242 ± 0.0008 and 0.1245 ± 0.0006, respectively), which closely match the bulk ¹⁸⁷Os/¹⁸⁸Os value of their host chromitite (0.1240 ± 0.0006). The unprecedented isotopic similarity between primary or secondary PGM assemblages and chromitite we report suggests that the osmium isotope budget of chromitite is largely controlled by the contained laurite and Os-rich alloy. This demonstrates that closed system behaviour of the Re–Os isotope system is possible, even during complex postmagmatic hydrothermal and/or metamorphic events. The preserved mantle Os-isotope signatures provide further support for an Enstatite Chondrite Reservoir (ECR) model for the convective upper mantle and are consistent with origin of the complex as a Caledonian ophiolite formed in a supra-subduction zone setting shortly before obduction.