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.

Palladosilicide, Pd₂Si, is a new mineral (IMA 2014-080) discovered in chromite-rich samples from the Kapalagulu intrusion, western Tanzania (30°03′51′′E 5°53′16′′S and 30°05′37′′E 5°54′26′′S) and from the UG-2 chromitite, Bushveld complex, South Africa. A total of 13 grains of palladosilicide, ranging in size from 0.7 to 39.1 μm (equivalent circle diameters), were found. Synthetic Pd₂Si is hexagonal, space group P62m, with a = 6.496(5), c = 3.433(4) Å, V = 125.5(1) ų, c:a = 0.529 with Z = 3. The strongest lines calculated from the powder pattern (Anderko and Schubert, 1953) are [d in Å (I) (hkl)] 2.3658 100 (111); 2.1263 37 (120); 2.1808 34 (021); 3.240 20 (110); 1.8752 19 (030); 1.7265 12 (002); 1.3403 11 (122); 1.2089 10 (231). The calculated density for three analyses varies from 9.562 to 9.753 g cm^–3. Palladosilicide is considered to be equivalent to synthetic Pd₂Si based on results from electron backscattered diffraction analyses. Reflectance data in air for the four Commission on Ore Mineralogy wavelengths are [λ nm, R₁ (%) R₂ (%)] 470 49.6 52.7; 546 51.2 53.8; 589 51.6 53.7; 650 51.7 53.3 and the mineral is bright creamy white against chromite, weakly bireflectant and displays no discernible pleochroism or twinning. It is weakly anisotropic, has weak extinction and rotation tints in shades of blue and olive green. Electron probe microanalyses of palladosilicide yield a simplified formula of Pd₂Si.

Hexaferrum, defined as anhcpFe mineral containing varying amounts of Ru, Os, or Ir (Mochalovet al.1998) was re-examined in the light of new analyses of similar alloys from the Loma Peguera and Loma Larga chromitites, in the central part of Loma Caribe peridotite, Cordillera Central of the Dominican Republic, together with a review of the phase chemistry in the Fe–Ni–Ir and Fe–Ru–Ir systems. We conclude that thehcp(Fe,Ir) mineral corresponds to the ε-phase of Raubet al.(1964) and should be differentiated from hexaferrum [(Fe,Os) and (Fe,Ru)] because it is separated by one to two miscibility gaps and therefore is not a continuous solid solution with Fe.