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All of the rocks from the Ultramafic series of the Stillwater Complex are enriched in PGE relative to most mafic magmas. Furthermore, the chromite layers are particularly enriched in IPGE (Os, Ir, and Ru) and Rh. This enrichment appears to be a common characteristic of ultramafic rocks from many types of settings, layered intrusions, ophiolites, and zoned complexes. We have carried out a petrological, mineralogical, and geochemical study to assess how the enrichment occurred in the case of the Stillwater Complex and applied our results to the chromite layers of the Bushveld and Great Dyke complexes. The minerals that now host the PGE are laurite and fine-grained intergrowths of pentlandite, millerite, and chalcopyrite. The laurite occurs as inclusions in chromite, and mass balance calculations indicate that it hosts most of the Os, Ir, and Ru. The sulfide minerals occur both as inclusions in chromite and as interstitial grains. The sulfides host much of the Pd and Rh. The IPGE and Rh correlate with Cr but not with S or Se, indicating that these elements were not collected by a sulfide liquid. Palladium, Cu, and Se correlate with each other, but not with S. The low S/Se (<1500) of the whole rock and magnetite rims around the sulfides indicate some S has been lost from the rocks. We conclude that to account for all observations, the IPGE and Rh were originally collected by chromite, and subsequently, small quantities of base metal sulfide liquid was added to the chromite layers from the overlying magma. The IPGE and Rh in the chromite diffused from the chromite into the base metal sulfides and converted some of the sulfides to laurite.

Rh-rich and Ir-poor erlichmanite-laurite OsS2-RuS2 solid solutions have been discovered at placers in Haraigawa, Misato-machi, Kumamoto, Japan. Microprobe analysis was performed to identify solid solutions containing few sub-components other than Rh. Approximately 10 at.% Rh was found to be present in the solid-solution samples. Structural refinement was performed using four natural samples: Os0.32Ru0.61Rh0.07S2, Os0.49Ru0.43Rh0.08S2, Os0.58Ru0.33Rh0.08S2 and Os0.81Ru0.09Rh0.10S2. The unit-cell parameters for the solid solutions containing Rh from Haraigawa varied from 5.61826(6) to 5.63142(8) Å. The (Os, Ru, Rh)-S distances in the Os1-x-yRuxRhyS2 system were almost constant with a small variation of 0.001 Å. Conversely, the S-S distances varied significantly, with variations approaching 0.1 Å. Rh substitution of Os rather than Ru had a larger impact on the crystal structure. The atomic displacement ellipsoid of both cations and anions was almost spherical, and no elongation along the M-S and S-S bond directions was observed. The bulk Debye temperatures were estimated from the Debye-Waller factor for the sulfide site. The bulk Debye temperatures of pure OsS2 and RuS2 were 688 K and 661 K, respectively, which suggests that the melting point of erlichmanite is higher than that of laurite. The high Debye temperature of OsS2 is inconsistent with the crystallisation of laurite prior to erlichmanite from the primitive magma, which suggests that fS2, rather than temperature, is the main cause of the known crystallisation order. The presence of several percent Rh has a significant effect on the thermal stability of OsS2 and lowers the melting point of the erlichmanite solid solution compared to that of the laurite solid solution.

— Thermodynamic properties of polycrystalline powders of ruthenium dichalcogenides have been studied using calorimetric isobaric heat capacity measurements in a wide temperature range. The adiabatic and differential scanning calorimetry data for ruthenium disulfide and ruthenium diselenide have been used to determine standard thermodynamic functions (heat capacity, entropy, enthalpy increment, and reduced Gibbs energy) of these compounds in the range 10–965 K. At 298.15 K, the functions of RuS 2 are as follows: = 60.82 ± 0.12 J/(K mol), S ° = 56.05 ± 0.11 J/(K mol), Н °(298.15 K) − Н °(0) = 9.75 ± 0.02 kJ/mol, and Ф° = 23.34 ± 0.05 J/(K mol). For RuSe 2 , we have obtained = 69.96 ± 0.14 J/(K mol), S ° = 80.62 ± 0.16 J/(K mol), Н °(298.15 K) − Н °(0) = 13.05 ± 0.03 kJ/mol, and Ф° = 36.85 ± 0.08 J/(K mol). The data obtained above 298 K have been used to determine empirical coefficients of the Maier–Kelley and Khodakovsky equations. The absolute entropies obtained in this study for the ruthenium dichalcogenides, in combination with literature data, have made it possible to evaluate the Gibbs energy of formation of RuS 2 (cr) and RuSe 2 (cr) at 298.15 K.

This study presents new compositional and S-Os isotope data for primary Ru-Os sulfides within a platinum-group mineral (PGM) assemblage from placer deposits associated with the Verkh-Neivinsk massif, which is part of the mantle ophiolite association of Middle Urals (Russia). The primary nature of Ru-Os sulfides represented by laurite (RuS2)–erlichmanite (OsS2) series is supported by occurrence of euhedral inclusions of high-Mg olivine (Fo92–94) that fall within the compositional range of mantle (primitive) olivine (Fo 88–93). The sulfur isotope signatures of Ru-Os sulfides reveal a range of δ34S values from 0.3 to 3.3‰, with a mean of 2.05‰ and a standard deviation of 0.86‰ (n = 18), implying that the sulfur derived from a subchondritic source. A range of sub-chondritic initial 187Os/188Os values defined for Ru-Os sulfides (0.1173–0.1278) are clearly indicative of derivation from a sub-chondritic source. Re-depletion (TRD) ages of the Verkh-Neivinsk Ru-Os sulfides are consistent with prolonged melt-extraction processes and likely multi-stage evolution of highly siderophile elements (HSE) within the upper mantle. A single radiogenic 187Os/188Os value of 0.13459 ± 0.00002 determined in the erlichmanite is indicative of a supra-chondritic source of HSE. This feature can be interpreted as evidence of a radiogenic crustal component associated with a subduction event or as an indication of an enriched mantle source. The mineralogical and Os-isotope data point to a high-temperature origin of the studied PGM and two contrasting sources for HSE in Ru-Os sulfides of the Verkh-Neivinsk massif.

Heavy mineral concentrates from rivers and river terraces near York, Freetown Peninsula, Sierra Leone have been examined for their platinum-group mineral (PGM) content. The alluvial PGM are 0.1 to 1.5 mm in size and include Cu-bearing isoferroplatinum (Pt3Fe) and disordered Pt3-xFe (x ≤ 0.38), tulameenite (Pt2FeCu), hongshiite (PtCu), cooperite-vysotskite (PtS-PdS), laurite (RuS2), erlichmanite (OsS2), Os-Ir alloy, Os-Ru alloy and native copper. Are the alluvial nuggets primary or a neoformation? Comparison of the PGM mineralogy of fresh rocks, weathered rocks and the saprolite, with the alluvial suite shows strongly contrasting features highlighted by the mineral assemblage. Cooperite in the fresh rocks is rare in the alluvium whilst Pt-Fe alloys become more abundant. Oxidized PGM are a feature only of the weathering process and disordering of the Pt-Fe alloys develops during weathering. Palladium is much less abundant in the alluvial suite than in the primary minerals whereas Cu, present as Cu-sulfides in the fresh rocks, occurs in the alluvium as a minor component of the Pt-Fe alloys and as hongshiite alteration to the Pt-Fe alloys. The size difference is striking; the primary mineralogy is micrometre-sized whereas the alluvial PGM are three orders of magnitude larger. Delicate PGM with alteration textures are seen only in the weathered rocks whilst delicate dendritic PGM are reported only from the alluvial suite. An organic coating to the alluvial PGM may be indicative of an organic or bacterial involvement. Some alluvial PGM occur in a drainage basin devoid of outcrops of PGE-bearing horizons. Together these contrasting features of the primary and placer PGM support the proposal that the Freetown nuggets developed as a result of breakdown of the primary PGM during weathering, movement of the PGE in solution, and growth of new PGM in placers with a different mineral assemblage, mineralogy and mineral chemistry.

Podiform chromitites, a part of Nidar ophiolite complex from the Indus Suture Zone (ISZ), southeast Ladakh, host significant platinum-group elements (PGE) and platinum-group of minerals. These high Cr chromitites are found to be enveloped within the dunite rocks in the form of massive, semi-massive and stringers and as disseminated grains in all the ultramafic rocks. The PGE mineralization in these chromitites exhibits wide ranges (1487–4431 ppb). The Nidar ophiolite chromitites are rich in laurites (RuS 2 ) and IPGE phases. The predominance of laurite phases in these chromitite samples is a distinctive feature of PGE mineralization, indicating their formation with interaction in an S-saturated tholeiitic magma and depleted harzburgites. The predominance of IPGE sulfides specifies a high sulfur fugacity in the melt. The higher content of PGE in the high Cr chromitites of Nidar ophiolite is not only a function of the degree of partial melting, but is related to the interaction between melt and harzburgite during the formation of chromitites. Research highlights A new set of PGE geochemistry of Nidar ophiolite chromitite is presented Laurite and millerite are common PGM and BMM in the chromitites The higher content of PGE is indicative of high degree of partial melting The PGE mineralization in these chromitites is due to the high sulfur fugacity

Inclusions of platinum-group minerals (PGM) within alluvial isoferroplatinum nuggets from the Freetown Peninsula, Sierra Leone, are aligned with their shape determined by the structure of their host. The edges of the majority of the inclusions lie at 0°, 45° or 90° to external crystal edges of the nugget which shows that the inclusions are not randomly oriented earlier minerals incorporated within their host. The inclusions are later infills, probably formed at the surface of the nugget during growth and subsequently enclosed by the growing nugget. PGM on the present surface of the nugget represent the last stage of this partnership. A single nugget containing abundant inclusions is described here but similar features are observed in other nuggets from the same area. The inclusions contain laurite (RuS2), irarsite-hollingworthite (IrAsS-RhAsS), Pd-Te-Bi-Sb phases, Ir-alloy, Os-alloy, Pd-bearing Au, an Rh-Te phase, Pd-Au alloy and Pd-Pt-Cu alloy. PGM found on the nugget surface include laurite, irarsite and cuprorhodsite (CuRh2S4). The Pd-Te-Bi-Sb phases may include Sb-rich keithconnite (Pd20S7) and compositions close to the kotulskite-sobolevskite solid-solution series (PdTe-BiTe). Textural evidence suggests that formation of the nuggets began with the isoferroplatinum host and the voids were filled starting intergrowths of laurite and irarsite-hollingworthite with both laurite and irarsite-hollingworthite often showing compositional zonation and each of them replacing the other. Filling of the voids probably continued with Pd-Cu-bearing gold, Sb-rich keithconnite (Pd,Pt)20.06(Te,Sb,Bi)6.94, keithconnite, telluropalladinite Pd9(Te,Bi)4, RhTe and finally Ir-alloy and then Os-alloy. The nuggets are thought to be neoform growths in the organic- and bacterial-rich soils of the tropical rain forest cover of the Freetown intrusion. The mineralogical assemblage in the layered gabbros of the intrusion has been previously shown to differ from the alluvial assemblage in the rivers and these inclusions, not seen in Pt3Fe in the unaltered rocks, add a further item to the catalogue of differences.

We report the first results of a combined focused ion beam and high-resolution transmission electron microscopy (FIB/HRTEM) investigation of zoned laurite (RuS2)-erlichmanite (OS2) in mantle-hosted chromitites. These platinum-group minerals form isolated inclusions (<50 µm across) within larger crystals of unaltered chromite form the Ojén ultramafic massif (southern Spain). High-magnification electron microscopy (HMEM), high angle-annular dark field (HAADF) and precession electron diffraction (PED) data revealed that microscale normal zoning in laurite consisting of Os-poor core and Os-rich rims observed by conventional micro-analytical techniques like field emission scanning electron microscope and electron microprobe analysis (FE-SEM and EPMA) exist at the nanoscale approach in single laurite crystals. At the nanoscale, Os poor cores consist of relatively homogenous pure laurite (RuS2) lacking defects in the crystal lattice, whereas the Os-richer rim consists of homogenous laurite matrix hosting fringes (10–20 nm thickness) of almost pure erlichmanite (OsS2). Core-to-rim microscale zoning in laurite reflects a nonequilibrium during laurite crystal growth, which hampered the intra-crystalline diffusion of Os. The origin of zoning in laurite is related to the formation of the chromitites in the Earth’s upper mantle but fast cooling of the chromite-laurite magmatic system associated to fast exhumation of the rocks would prevent the effective dissolution of Os in the laurite even at high temperatures (~1200 °C), allowing the formation/preservation of nanoscale domains of erlichmanite in laurite. Our observation highlights for the first time the importance of nanoscale studies for a better understanding of the genesis of platinum-group minerals in magmatic ore-forming systems.

We describe similar assemblages of minerals found in two placers in Russia, both probably derived from an ophiolitic source. The first is located along the River Rudnaya in the western Sayan province, Krasnoyarskiy kray, and the second pertains to the Miass placer zone, Chelyabinsk oblast, in the southern Urals. The platinum-group element (PGE) mineralization in both cases is mostly (at least 80%) represented by alloy minerals in the system Ru-Os-Ir, in the order of occurrence osmium, ruthenium and iridium. The remainder consists of Pt-Fe alloys and species of PGE sulfides, arsenides, sulfarsenides, etc. The associated olivine and amphiboles are supermagnesian, and the chromian spinel has a high Cr# value. The observed enrichment in Ru, typical of an ophiolitic source, may be due to high-temperature hydrothermal equilibration and mobilization in the ophiolite, as is the enrichment in Mg and Cr. Low-temperature replacement of the alloys led to the development of laurite, sulfoarsenides and arsenides. Some placer grains in both suites reveal unusual phases of sulfo-arsenoantimonides of Ir-Rh, e.g. the unnamed species (Rh,Ir)SbS and (Cu,Ni)1+x(Ir,Rh)1-xSb, where x = 0.2, and rhodian tolovkite, (Ir,Rh)SbS. Two series of natural solid-solutions appear to occur in the tolovkite-type phases. Among the oddities in the Rudnaya suite are globules of micrometric PGE sulfides, crystallites of platinum-group minerals, amphibole, and chalcopyrite bearing skeletal micrometric monosulfide-like compounds (Cu,Pt,Rh)S and (Pd,Cu)S1-x. Pockets of fluxed evolved melt seem to have persisted well below the solidus of the host Pt3Fe-type alloy.

Laurite, ideally (Ru,Os)S2, is a common accessory mineral in podiform and stratiform chromitites and, to a lesser extent, it also occurs in placer deposits and is associated with Ni-Cu magmatic sulfides. In this paper, we report on the occurrence of zoned laurite found in the Merensky Reef of the Bushveld layered intrusion, South Africa. The zoned laurite forms relatively large crystals of up to more than 100 µm, and occurs in contact between serpentine and sulfides, such as pyrrhotite, chalcopyrite, and pentlandite, that contain small phases containing Pb and Cl. Some zoned crystals of laurite show a slight enrichment in Os in the rim, as typical of laurite that crystallized at magmatic stage, under decreasing temperature and increasing sulfur fugacity, in a thermal range of about 1300–1000 °C. However, most of the laurite from the Merensky Reef are characterized by an unusual zoning that involves local enrichment of As, Pt, Ir, and Fe. Comparison in terms of Ru-Os-Ir of the Merensky Reef zoned laurite with those found in the layered chromitites of the Bushveld and podiform chromitites reveals that they are enriched in Ir. The Merensky Reef zoned laurite also contain high amount of As (up to 9.72 wt%), Pt (up to 9.72 wt%) and Fe (up to 14.19 wt%). On the basis of its textural position, composition, and zoning, we can suggest that the zoned laurite of the Merensky Reef is “hydrothermal” in origin, having crystallized in the presence of a Cl- and As-rich hydrous solution, at temperatures much lower than those typical of the precipitation of magmatic laurite. Although, it remains to be seen whether the “hydrothermal” laurite precipitated directly from the hydrothermal fluid, or it represents the alteration product of a pre-existing laurite reacting with the hydrothermal solution.