We describe assemblages of platinum-group minerals (PGM) and associated PGE–Au phases found in alluvium along the River Bolshoy Khailyk, in the western Sayans, Russia. The river drains the Aktovrakskiy ophiolitic complex, part of the Kurtushibinskiy belt, as does the Zolotaya River ~15 km away, the site of other placer deposits. Three groups of alloy minerals are described: (1) Os–Ir–Ru compositions, which predominate, (2) Pt–Fe compositions of a Pt₃Fe stoichiometry, and (3) Pt–Au–Cu alloys, which likely crystallized in the sequence from Au–(Cu)-bearing platinum, Pt(Au,Cu), Pt(Cu,Au), and PtAuCu₂, to PtAu₄Cu₅. The general trends of crystallization of PGM appear to be: [Os–Ir–Ru alloys] → Pt₃Fe-type alloy (with inclusions of Ru-dominant alloy formed by exsolution or via replacement of the host Pt–Fe phase) → Pt–Au–Cu alloys. We infer that Rh and Co mutually substitute for Fe, not Ni, and are incorporated into the pentlandite structure via a coupled mechanism of substitution: [Rh³⁺ + Co³⁺ + □ → 3Fe²⁺]. Many of the Os–Ir–Ru and Pt–Fe grains have porous, fractured or altered rims that contain secondary PGE sulfide, arsenide, sulfarsenide, sulfoantimonide, gold, Pt–Ir–Ni-rich alloys, and rarer phases like Cu-rich bowieite and a Se-rich sulfarsenide of Pt. The accompanying pyroxene, chromian spinel and serpentine are highly magnesian, consistent with a primitive ultramafic source-rock. Whereas the alloy phases indicate a highly reducing environment, late assemblages indicate an oxygenated local environment leading to Fe-bearing Ru–Os oxide (zoned) and seleniferous accessory phases.

Dunite–harzburgite–olivine-bearing orthopyroxenite successions in the subvolcanic Chapesvara-I and Chapesvara-II intrusions in the Serpentinite Belt, western Kola Peninsula, are notably magnesian. The mean Mg# value (whole-rock) is 86.6, and the olivine is Fo₈₄₋₈₉. The upper contact facies (UCF) displays a lower Mg# (81.6). It consists of grains of Fo₉₂ and abundant chromian spinel, implying rapid crystallization of an almost unfractionated melt. On average, the whole-rock Al₂O₃/TiO₂ value is 22.45, close to 22.9 (UCF) and to the primitive mantle, ~22. The rise of primitive ultramafic magma presumably occurred in a special tectonic setting at the boundary of the Paleoproterozoic Lapland Granulite Terrane and the Belomorian Composite Terrane of Archean age. The Chapesvara suite resembles examples of the Al-undepleted komatiites in the Barberton Belt, South Africa, with magmas of up to 30–35% MgO. The UCF rock yields an anomalously low molar MgO/SiO₂ value, close to that of dunitic rocks located at the center of the Chapesvara-II body. This rock is the most primitive, as indicated by the maximum Fo content of olivine, the lowest value of (Gd/Yb)_N, 0.52, and the lowest abundances of middle to heavy rare-earth elements (REE) in the chondrite-normalized spectrum. The crystallization of the Chapesvara-II sill-like intrusion likely proceeded in two stages, which are evident from the olivine compositions varying from the maximum Fo₉₂ (UCF) to Fo_≤89.5 (the central dunite zone). At Stage 1, the UCF rock (Fo₉₂) crystallized first, close to the upper contact. The area of crystallization then shifted to a central portion of the Chapesvara-II body, in which the dunitic zone (Fo_89.5) formed in situ (Stage 2). The compositional variations in chromian spinel are consistent with this suggestion. Two crystallization trends were recognized. The type-1 trend displays a relative maximum or minimum close to the center, and then diverges into two linear subtrends directed upward and downward. This pattern is manifested in the variations of Mg# in olivine and chromian spinel, the whole-rock contents of Al and Ca, and in levels of incompatible elements: Ti, V, Zr, Y, and Hf. The type-2 trend decreases or increases uniformly from top to bottom. Variations in amount of Ni in olivine, the Fe³⁺# index in chromian spinel, and in values of Mg# (rocks), follow a type-2 trend. Variations in total amounts of REE, Nb, and Th, which gradually increase downward, are also related to a type-2 trend. Thus, a contrasting development and possible interference of the two types of evolutionary trends were observed in the crystallization history of the Chapesvara-II sill-like body. A double-front crystallization, hitherto unreported, involved two fronts moving upward and downward, respectively. The upward subtrend appeared to be of subordinate importance, whereas the extent of fractional crystallization of the downward front was much greater. Crystallization proceeded from the top to the bottom, presumably because of the preferential loss of heat at the roof. Variations in the Fe³⁺# index indicate that the level of fO₂ also increased downward with progressive crystallization. Convection cells were presumably the key mechanism of accumulation of the crystallizing olivine grains to form the central dunite zone close to the center of the sill-like intrusion. The observed characteristics of the Chapesvara complex indicate the existence of a primitive-mantle source and imply a highly magnesian composition of intruding magma not only for Chapesvara, but also for the Pados-Tundra layered complex and associated suites of the Serpentinite Belt in the Kola Peninsula.

The lopolithic Pados-Tundra layered complex, the largest member of the Serpentinite belt–Tulppio belt (SB–TB) megastructure in the Fennoscandian Shield, is characterized by (1) highly magnesian compositions of comagmatic dunite–harzburgite–orthopyroxenite, with primitive levels of high-field-strength elements; (2) maximum values of Mg# in olivine (Ol, 93.3) and chromian spinel (Chr, 57.0) in the Dunite block (DB), which exceed those in Ol (91.7) and Chr (42.5) in the sills at Chapesvara, and (3) the presence of major contact-style chromite–IPGE-enriched zones hosted by the DB. A single batch of primitive, Al-undepleted komatiitic magma crystallized normally as dunite close to the outer contact, then toward the center. A similar magma gave rise to Chapesvara and other suites of the SB–TB megastructure. Crystallization proceeded from the early Ol + Chr cumulates to the later Ol–Opx and Opx cumulates with accessory Chr in the Orthopyroxenite zone. The accumulation of Chr resulted from efficient cooling along boundaries of the Dunite block. The inferred front of crystallization advanced along a path traced by vectors of Ol and Chr compositions. Grains and aggregates of Chr were mainly deposited early after the massive crystallization of olivine. Chromium, Al, Zn and H₂O, all incompatible in Ol, accumulated to produce podiform segregations or veins of chromitites. This occurred episodically along the moving front of crystallization. Crystallization occurred rapidly owing to heat loss at the contact and to a shallow level of emplacement. The Chr layers are not continuous but rather heterogeneously distributed pods or veins of Chr–Ol–clinochlore segregations. Isolated portions of melt enriched in H₂O and ore constituents accumulated during crystallization of Ol. Levels of fO₂ in the melt and, consequently, the content of ferric iron in Chr, increased progressively, as in other intrusions of the SB–TB megastructure. The komatiitic magma vesiculated intensely, which led to a progressive loss of H₂ and buildup in fO₂. In turn, this led to the appearance of anomalous Chr–Ilm parageneses. Diffuse rims of Chr grains, abundant in the DB, contain elevated levels of Fe³⁺ and enrichments in Ni and Mn. In contrast, Zn is preferentially partitioned into the core, leading to a decoupling of Zn from Mn, also known at Chapesvara. The sulfide species display a pronounced Ni-(Co) enrichment in assemblages of cobaltiferous pentlandite, millerite (and heazlewoodite at Khanlauta), deposited at ≤630 °C. The oxidizing conditions have promoted the formation of sulfoselenide phases of Ru in the chromitites. The attainment of high degrees of oxidation during crystallization of a primitive parental komatiitic magma accounts for the key characteristics of Pados-Tundra and related suites of the SB–TB megastructure.

Compositional variations of major and minor elements were examined in Pt–Fe alloys from various geological settings and types of deposits, both lode and placer occurrences. They included representatives of layered intrusions, Alaskan-Uralian-(Aldan)-type and alkaline gabbroic complexes, ophiolitic chromitites, and numerous placers from Canada, USA, Russia, and other localities worldwide. Pt–Fe alloy grains in detrital occurrences are notably larger in size, and these are considered to be the result of a special conditions during crystallization such as temperature, pressure, geochemistry or time. In addition, the number of available statistical observations is much greater for the placer occurrences, since they represent the end-product of, in some cases, the weathering of many millions of tonnes of sparsely mineralized bedrock. Typically, platinum-group elements (PGE) present in admixtures (Ir, Rh, and Pd) and minor Cu, Ni are incorporated into a compositional series (Pt, PGE)_2–3(Fe, Cu, Ni) in the lode occurrences. Relative Cu enrichment in alloys poor in Pt implies crystallization from relatively fractionated melts at a lower temperature. In contrast to the lode deposits, the distribution of Ir, Rh, and Pd is fairly chaotic in placer Pt–Fe grains. There is no relationship between levels of Ir, Rh, and Pd with the ratio Σ(Pt + PGE):(Fe + Cu + Ni). The compositional series (Pt, PGE)_2–3(Fe, Cu, Ni) is not as common in the placer occurrences; nevertheless, minor Cu and Ni show their maximums in members of this series in the placer grains. Global-scale datasets yield a bimodal pattern of distribution in the Pt–Fe diagram, which is likely a reflection of the miscibility gap between the ordered Pt₃Fe structure (isoferroplatinum) and the disordered structure of native or ferroan platinum. In the plot Pt versus Fe, there is a linear boundary due to ideal Pt ↔ Fe substitution. Two solid solution series are based on the Ir-for-Pt and Pd-for-Pt substitutions. The incorporation of Ir is not restricted to Pt₃Fe–Ir₃Fe substitution (isoferroplatinum and chengdeite, plus their disordered modifications). Besides, Ir⁰ appears to replace Pt⁰ in the disordered variants of (Pt–Ir)–Fe alloys. There is a good potential for the discovery of a new species with a Pd-dominant composition, (Pd, Pt)₃Fe, most likely in association with the alkaline mafic-ultramafic or gabbroic complexes, or the mafic units of layered intrusions. The “field of complicated substitutions” is recognized as a likely reflection of the crystallochemical differences of Pd and Ir, extending along the Ir-Pd axis of the Ir–Pd–Rh diagram. The inferred solid solution extends approximately along the line Ir–(Pd:Rh = 2:3). Minor Pd presumably enters the solid solution via a coupled substitution in combination with the Rh. An Ir-enrichment trend in Pt–Fe alloys typically occurs in the Alaskan-type complexes. The large size of the Pt–Fe nuggets associated with some of these complexes is considered to be related to an ultramafic-mafic pegmatite facies, whereas significant Pd-enrichment is characteristic of gabbroic source-rocks (e.g., Coldwell Complex), resulting in a markedly different trend for the Pt versus Fe (wt.%). However, based on our examination of a large dataset of Pt–Fe alloys from numerous origins, we conclude that they exhibit compositional overlaps that are too large to be useful as reliable index-minerals.

—The paper focuses on compositional variations of olivine and chromian spinel in the Monchepluton and Pados-Tundra layered intrusions, which host significant chromitite mineralization. Ore-bearing dunite (with up to 25–30 vol.% Mcr) in the Sopcheozerskoe chromite deposit from the Monchepluton complex, Kola Peninsula, Russia, bears an assemblage of phases with exceptionally high magnesium contents: Fo₉₆ + augite (Mg# = 94) + magnesiochromite, Mcr (Mg# ≈ 65); Mg# = 100·Mg/(Mg + Fe²⁺ + Mn). However, olivine in the host dunite has normal maximum values of Mg# comparable to those in cumulus olivine from layered intrusions worldwide (Fo_≤91–92). The Fo₉₆ phase in the Sopcheozerskoe deposit shows the most primitive composition ever reported from any layered intrusion. Magnesiochromite occurs as unzoned homogeneous euhedral crystals unaffected by subsolidus exchange or metasomatic effects. Olivine in ore-bearing dunite (20–25 vol.% magnesian chromite) from the Pados-Tundra complex attains Fo_93, with the Mg# value notably higher than the range (Fo_85.5–90.6) in olivine from orthopyroxenite, harzburgite, and dunite within the intrusion. Olivine and chromian spinel in the two complexes behave coherently, with covarying patterns of Mg# and Ni contents in olivine at R = 0.75 (n = 160) and positive correlation between Mg# in coexisting chromian spinel and olivine grains at R = 0.8 (n = 150). This behavior indicates that the two phases attained equilibrium during crystallization. It appears unlikely that the extremely high Mg enrichment in olivine (Fo₉₆), as well as in all associated phases of the Monchepluton complex, would result from a subsolidus reaction between olivine and chromian spinel or low-temperature alteration of olivine. We suggest a more realistic explanation that the olivine (+ high-Mg augite)–chromian spinel assemblage crystallized from komatiitic magma under the conditions of progressively increasing oxygen fugacity (fO₂). The high Mg# in the Mcr-chromite-enriched system, above the maximum values common in cumulus olivine from layered intrusions (up to Fo₉₆ against Fo_≤91–92), may be caused by shortage of ferrous iron.

We report the results of a mineralogical investigation of placer samples from the upper reaches of the Sisim watershed, near Krasnoyarsk, in Eastern Sayans, Russia. The placer grains are predominantly Os–Ir–(Ru) alloys (80%) that host various inclusions (i.e., platinum-group elements (PGE)-rich monosulfide, PGE-rich pentlandite, Ni–Fe–(As)-rich laurite, etc.) and subordinate amounts of Pt–Fe alloys. Analytical data (wavelength- and energy-dispersive X-ray spectroscopy) are presented for all the alloy minerals and the suite of micrometer-sized inclusions that they contain, as well as associated grains of chromian spinel. The assemblage was likely derived from chromitite units of the Lysanskiy mafic–ultramafic complex, noted for its Ti–(V) mineralization. In the Os–Ir–(Ru) alloys, the ratio Ru/Ir is ≤1, Ir largely substitutes for Os, and compositional variations indicate the scheme [Ir + Ru] → 2Os. In contrast, in the laurite–erlichmanite series, Ir and Os are strongly and positively correlated, whereas Ir and Ru are negatively correlated; Ru and Os are inversely correlated. These compositions point to the scheme [Os²⁺ + 2Ir³⁺ + □] → 4Ru²⁺ or alternatively, to Os²⁺ + Ir²⁺ → 2Ru²⁺. We deduce a potential sequence of crystallization in the parental rock and address the effects of decreasing temperature and increasing fugacity of sulfur and arsenic on the assemblage. Inclusions of Ti-rich minerals in the alloy grains are consistent with the Lysanskiy setting; the complete spectrum of chromite–magnesiochromite compositions indicates that an important part of that complex was eroded. A localized fluid-dominated micro-environment produced the unique association of laurite with monazite-(Ce), again considered a reflection of the special attributes of the Lysanskiy complex.