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This paper reviews a database of about 1500 published and 1000 unpublished microprobe analyses of platinum-group minerals (PGM) from chromite deposits associated with ophiolites and Alaskan-type complexes of the Urals. Composition, texture, and paragenesis of unaltered PGM enclosed in fresh chromitite of the ophiolites indicate that the PGM formed by a sequence of crystallization events before, during, and probably after primary chromite precipitation. The most important controlling factors are sulfur fugacity and temperature. Laurite and Os–Ir–Ru alloys are pristine liquidus phases crystallized at high temperature and low sulfur fugacity: they were trapped in the chromite as solid particles. Oxygen thermobarometry supports that several chromitites underwent compositional equilibration down to 700 °C involving increase of the Fe3/Fe2 ratio. These chromitites contain a great number of PGM including—besides laurite and alloys—erlichmanite, Ir–Ni–sulfides, and Ir–Ru sulfarsenides formed by increasing sulfur fugacity. Correlation with chromite composition suggests that the latest stage of PGM crystallization might have occurred in the subsolidus. If platinum-group elements (PGE) were still present in solid chromite as dispersed atomic clusters, they could easily convert into discrete PGM inclusions splitting off the chromite during its re-crystallization under slow cooling-rate. The presence of primary PGM inclusions in fresh chromitite of the Alaskan-type complexes is restricted to ore bodies crystallized in equilibrium with the host dunite. The predominance of Pt–Fe alloys over sulfides is a strong indication for low sulfur fugacity, thereby early crystallization of laurite is observed only in one deposit. In most cases, Pt–Fe alloys crystallized and were trapped in chromite between 1300 and 1050 °C. On-cooling equilibration to ~900 °C may produce lamellar unmixing of different Pt–Fe phases and osmium. Precipitation of the Pt–Fe alloys locally is followed by an increase of sulfur fugacity leading to crystallize erlichmanite and Ir–Rh–Ni–Cu sulfides, occurring as epitaxic overgrowth on the alloy. There is evidence that the system moved quickly into the stabilization field of Pt–Fe alloys by an increase of the oxygen fugacity marked by an increase of the magnetite component in the chromite. In summary, the data support that most of the primary PGM inclusions in the chromitites of the Urals formed in situ, as part of the chromite precipitation event. However, in certain ophiolitic chromitites undergoing annealing conditions, there is evidence for subsolidus crystallization of discrete PGM from PGE atomic-clusters occurring in the chromite. This mechanism of formation does not require a true solid solution of PGE in the chromite structure.

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 187 Os/ 188 Os (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 187 Os/ 188 Os 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.

Arsenotučekite, Ni18Sb3AsS16, is a new mineral discovered in the abandoned chromium mine of Tsangli, located in the eastern portion of the Othrys ophiolite complex, central Greece. Tsangli is one of the largest chromite deposit at which chromite was mined since 1870. The Tsangli chromitite occurs as lenticular and irregular bodies. The studied chromitites are hosted in a strongly serpentinized mantle peridotite. Arsenotučekite forms anhedral to subhedral grains that vary in size between 5 μm up to 100 μm, and occurs as single phase grains or is associated with pentlandite, breithauptite, gersdorffite and chlorite. It is brittle and has a metallic luster. In plane-polarized light, it is creamy-yellow, the bireflectance is barely perceptible and the pleochroism is weak. In crossed polarized reflected light, the anisotropic rotation tints vary from pale blue to brown. Internal reflections were not observed. Reflectance values of arsenotučekite in air (Ro, Re′ in %) are: 41.8–46.4 at 470 nm, 47.2–50.6 at 546 nm, 49.4–52.3 at 589 nm, and 51.3–53.2 at 650 nm. The empirical formula of arsenotučekite, based on 38 atoms per formula unit, and according to the structural results, is (Ni16.19Co1.01Fe0.83)Σ18.03Sb3(As0.67Sb0.32)Σ0.99S15.98. The mass density is 6.477 g·cm−3. The simplified chemical formula is (Ni,Co,Fe)18Sb3(As,Sb)S16. The mineral is tetragonal and belongs to space group I4/mmm, with a = 9.7856(3) Å, c = 10.7582(6) Å, V = 1030.2(6) Å3 and Z = 2. The structure is layered (stacking along the c-axis) and is dominated by three different Ni-coordination polyhedral, one octahedral and two cubic. The arsenotučekite structure can be considered as a superstructure of tučekite resulting from the ordering of Sb and As. The name of the new mineral species indicates the As-dominant of tučekite. Arsenotučekite occurs as rims partly replacing pentlandite and irregularly developed grains. Furthermore, it is locally associated with chlorite. These observations suggest that it was likely precipitated at relatively low temperatures during: 1) the late hydrothermal stages of the ore-forming process by reaction of Sb- and As-bearing solutions with magmatic sulfides such as pentlandite, or 2) during the serpentinization of the host peridotite. The mineral and its name have been approved by the Commission of New Minerals, Nomenclature, and Classification of the International Mineralogical Association (number 2019–135).

The principal global sources of platinum-group elements (Os, Ir, Ru, Rh, Pt, Pd), collectively referred to as PGEs, are magmatic Ni-Cu sulfide deposits associated with large, layered intrusions, such as the Bushveld Complex. Recent exploration efforts have identified rock types with elevated PGE concentrations, although their potential remains uncertain. This comprehensive review synthesizes the current knowledge regarding potential sources from both natural magmatic and anthropogenic activities, as well as the environmental risks associated with the Pt, Pd, and Rh sub-group, or PPGEs. The order of Pd > Pt > Rh content in emitted particulates has been documented in dust and soil along roadsides, whereas in Fe-Ni laterite, Pt tends to accumulate residually at the top of profiles due to the higher mobility of Pd compared to Pt and Rh. The greater mobility and transfer of Pd are evidenced by higher bioaccumulation factors for Pd in plants and crops, with a higher Pd content observed in roots than in shoots. The effects of chronic occupational exposure to Pt compounds, such as allergic reactions affecting the skin and respiratory system of workers, are well-documented. Although no established permissible limits for Pt, Pd, and Rh in soil, water, or plants exist within major regulatory frameworks, the increasing applications of PPGEs and the use of Pd in catalytic converters (due to its lower cost) underscore the need for further studies on the recycling of spent catalytic converters, health impacts, ecotoxicological assessments, and the application of current technological advances to mitigate exhaust emissions.

This contribution provides a petrographic and Raman investigation of fluid inclusions found in chromitites collected in the ophiolites of Santa Elena (Costa Rica), Bracco (Italy), Otrhys and Vourinos (Greece), and Troodos (Cyprus). Most of the analyzed chromites are classified as high-Cr, with the exception of those from Bracco and some of the Othrys complexes that are high-Al. Although the investigation of fluid inclusions in chromitites is very challenging due to the poor transparency of the host chromite, the studied samples contain numerous fluid inclusions. The fluid inclusions look to be more abundant in the high-Cr chromitites, related to a subduction zone environment, compared to the high-Al chromitites generated in a mid-ocean ridge. This is in agreement with the petrogenetic model for the formation of podiform chromitites that implies the presence of a metasomatic event caused by hydrous fluids that reacted pervasively with variable depleted mantle tectonites, especially in the subduction zone setting. The fluid inclusions, between 1 and 15 µm in size, show negative crystal or irregular angular shapes. They occur when enclosed in chromite crystals that have not been affected by low-temperature processes. The fluid inclusions consist of liquid (L), vapour(V~30–50 area%) and L + V (V~40–60 area% rarely 10–80 area%). The fluid inclusions may contain only vapour and a vapour and a solid phase, too. The Raman spectra reveal the presence of CH4 in certain fluid inclusions. Considering the high number of fluid inclusions that potentially contain CH4, we suggest that the fluid inclusions in the chromite crystals and their leaching can be a possible source in order to explain the high amount of CH4 detected in some podiform chromitites, previously attributed to the Sabatier reaction. The mode of the occurrences of the studied CH4 bearing fluid inclusions, i.e., entrapped in unaltered chromite crystals formed at a magmatic temperature, suggest their abiotic origin from mantle-derived fluids, rather than those related to the low-temperature serpentinization processes. The investigation of fluid inclusions, although it is difficult and challenging or even impossible when the chromite is too opaque, can be applicable to other chromitites worldwide to verify the presence of H2O, CH4 or other gases. This information will greatly improve our understanding of the nature of the fluid phases during the formation of podiform chromitites.

Two Ni-laterite profiles from the Loma Caribe peridotite (Dominican Republic) have been investigated for their platinum group element (PGE) geochemistry and mineralogy. One profile (Loma Peguera) is characterized by PGE-enriched (up to 3.5 ppm total PGE) chromitite bodies incorporated within the saprolite, whereas the second profile is chromitite-free (Loma Caribe). Total PGE contents of both profiles slightly increase from parent rocks (36 and 30 ppb, respectively) to saprolite (∼50 ppb) and reach highest levels within the limonite zone (640 and 264 ppb, respectively). Chondrite-normalized PGE patterns of saprolite and limonite reveal rather flat shapes with positive peaks of Ru and Pd. Three types of platinum group minerals (PGM) were found by using an innovative hydroseparation technique: (i) primary PGM inclusions in fresh Cr-spinel (laurite and bowieite), (ii) secondary PGM (e.g., Ru-Fe-Os-Ir compounds) from weathering of preexisting PGM (e.g., serpentinization and/or laterization), and (iii) PGM precipitated after PGE mobilization within the laterite (neoformation). Our results provide evidence that (i) PGM occurrence and PGE enrichment in the laterite profiles is independent of chromitite incorporation; (ii) PGE enrichment is residual on the profile scale; and (iii) PGE are mobile on a local scale leading to in situ growth of PGM within limonite, probably by bioreduction and/or electrochemical metal accretion.

The six platinum group elements (PGE) are among the rarest elements in the upper continental crust of the earth. Higher values of PGE have been detected in the upper mantle and in chondrite meteorites. The PGE are siderophile and chalcophile elements and are divided into the following: (1) the Ir subgroup (IPGE) = Os, Ir, and Ru and (2) the Pd subgroup (PPGE) = Rh, Pt, and Pd. The IPGE are more refractory and less chalcophile than the PPGE. High concentrations of PGE led, in rare cases, to the formation of mineral deposits. The PGE are carried in discrete phases, the platinum group minerals (PGM), and are included as trace elements into the structure of base metal sulphides (BM), such as pentlandite, chalcopyrite, pyrite, and pyrrhotite. Similarly to PGE, the PGM are also divided into two main groups, i.e., IPGM composed of Os, Ir, and Ru and PPGM containing Rh, Pt, and Pd. The PGM occur both in mafic and ultramafic rocks and are mainly hosted in stratiform reefs, sulphide-rich lenses, and placer deposits. Presently, there are only 169 valid PGM that represent about 2.7% of all 6176 minerals discovered so far. However, 496 PGM are listed among the valid species that have not yet been officially accepted, while a further 641 are considered as invalid or discredited species. The main reason for the incomplete characterization of PGM resides in their mode of occurrence, i.e., as grains in composite aggregates of a few microns in size, which makes it difficult to determine their crystallography. Among the PGM officially accepted by the IMA, only 13 (8%) were discovered before 1958, the year when the IMA was established. The highest number of PGM was discovered between 1970 and 1979, and 99 PGM have been accepted from 1980 until now. Of the 169 PGM accepted by the IMA, 44% are named in honour of a person, typically a scientist or geologist, and 31% are named after their discovery localities. The nomenclature of 25% of the PGM is based on their chemical composition and/or their physical properties. PGM have been discovered in 25 countries throughout the world, with 64 from Russia, 17 from Canada and South Africa (each), 15 from China, 12 from the USA, 8 from Brazil, 6 from Japan, 5 from Congo, 3 from Finland and Germany (each), 2 from the Dominican Republic, Greenland, Malaysia, and Papua New Guinea each, and only 1 from Argentine, Australia, Bulgaria, Colombia, Czech Republic, England, Ethiopia, Guyana, Mexico, Serbia, and Tanzania each. Most PGM phases contain Pd (82 phases, 48% of all accepted PGM), followed, in decreasing order of abundances, by those of Pt 35 phases (21%), Rh 23 phases (14%), Ir 18 phases (11%), Ru 7 phases (4%), and Os 4 phases (2%). The six PGE forming the PGM are bonded to other elements such as Fe, Ni, Cu, S, As, Te, Bi, Sb, Se, Sn, Hg, Ag, Zn, Si, Pb, Ge, In, Mo, and O. Thirty-two percent of the 169 valid PGM crystallize in the cubic system, 17% are orthorhombic, 16% hexagonal, 14% tetragonal, 11% trigonal, 3% monoclinic, and only 1% triclinic. Some PGM are members of a solid-solution series, which may be complete or contain a miscibility gap, providing information concerning the chemical and physical environment in which the mineral was formed. The refractory IPGM precipitate principally in primitive, high-temperature, mantle-hosted rocks such as podiform and layered chromitites. Being more chalcophile, PPGE are preferentially collected and concentrated in an immiscible sulphide liquid, and, under appropriate conditions, the PPGM can precipitate in a thermal range of about 900–300 °C in the presence of fluids and a progressive increase of oxygen fugacity (fO2). Thus, a great number of Pt and Pd minerals have been described in Ni-Cu sulphide deposits. Two main genetic models have been proposed for the formation of PGM nuggets: (1) Detrital PGM represent magmatic grains that were mechanically liberated from their primary source by weathering and erosion with or without minor alteration processes, and (2) PGM reprecipitated in the supergene environment through a complex process that comprises solubility, the leaching of PGE from the primary PGM, and variation in Eh-pH and microbial activity. These two models do not exclude each other, and alluvial deposits may contain contributions from both processes.

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.

Several Cyprus-type volcanogenic massive sulphide (VMS) deposits occur in the Jurassic ophiolitic series of the Northern Apennines. Stratabound, stratiform and stockwork deposits were formed in the western limb of the Neotethys (Ligurian Ocean) and are observed today in basalt, gabbro and serpentinised peridotite host rocks. The studied stockwork deposit at Boccassuolo occurs in basalt and basalt breccia. Detailed petrography, fluid inclusion study, Raman spectroscopy analyses and chlorite thermometry calculations were used to determine the P, T, X conditions of the fluid circulation system. The veins contain three quartz generations, calcite, chlorite, epidote and sericite as gangue minerals and pyrite, chalcopyrite, sphalerite, pyrrhotite and galena as ore minerals. Based on the fluid inclusion study, the earlier defined three vein types (1., 2. and 3.) precipitated from the same type of evolving fluid, though at slightly different stratigraphic positions. The determined ranges of temperature (370-60°C), salinity (6.2-11.4 NaCl equiv. wt%), pressure (30-44 MPa) and methane content (average 0.28 mol/kg) suggest an evolved seawater origin for the hydrothermal fluid, modified by fluid-rock interactions and possibly by mixing of magmatic volatiles. The fluid characteristics and the mineralogical observations have proven a slightly distal position in relation to the centre of the fluid flow for all the studied locations, but more central and more distant blocks were also recognised. The temporal evolution of the system developed into a low temperature event, occurring after the main mineral stage of formation, but still within the same overall process.

The research interest for many authors has been focused on the origin, recovery, and exploration of critical metals, including platinum-group elements (PGEs), with the aim of finding new potential sources. Many giant porphyry Cu deposits are well known around the Pacific Rim, in the Balkan–Carpathian system, Himalayas, China, and Malaysia. However, only certain porphyry Cu-Au deposits are characterized by the presence of significant Pd and Pt contents (up to 20 ppm). This contribution provides new analytical data on porphyry-Cu-Au±Pd±Pt deposits from the Chalkidiki Peninsula and an overview of the existing geochemical characteristics of selected porphyry-Cu deposits worldwide in order to define significant differences between PGE-fertile and PGE-poor porphyry-Cu intrusions. The larger Mg, Cr, Ni, Co, and Re contents and smaller LILE elements (Ba and Sr) in fertile porphyry-Cu-Au-(PGE) reflect the larger contribution from the mantle to the parent magmas. In contrast, the smaller Mg, Cr, Ni, Co, and Re contents and larger Ba and Sr in PGE-poor porphyry-Cu-Mo deposits from the Chalkidiki Peninsula (Vathi, Pontokerasia, and Gerakario) and Russia–Mongolia suggest the presence of parent magmas with a more crustal contribution. Although there is an overlap in the plots of those elements, probably due to the evolution of the ore-forming system, consideration of the maximum contents of Mg, Cr, Ni, and Co is proposed. Magnetite which separated from the mineralized Skouries porphyry of Greece showed small negative Eu anomalies (Eu/Eu* ≥ 0.55), reflecting a relatively high oxidation state during the cooling of the ore-forming system. The relatively high, up to 6 ppm (Pd+Pt), and low Cr content towards the transition from the porphyry to epithermal environment, coupled with the occurrence of Pd, Te, and Se minerals (merenskyite, clausthalite), and tetrahedrite–tennantite in fertile porphyry Cu deposits (Elatsite deposit, Bulgaria), reflect a highly fractionated ore-forming system. Thus, in addition to the crustal and mantle recycling, metasomatism, high oxidation state, and abundant magmatic water, other factors required for the origin of fertile porphyry-Cu deposits are the critical degree of mantle melting to release Pt and Pd in the ore-forming fluids and the degree of fractionation, as reflected in the mineral chemistry and geochemical data.