Sphalerite is the main source of In – a ‘critical’ metal widely used in high-tech electronics. In this mineral the concentration of In is commonly correlated directly with Cu content. Here we use X-ray absorption spectroscopy of synthetic compounds and natural crystals in order to investigate the substitution mechanisms in sphalerites where In is present, together with the group 11 metals. All the admixtures (Au, Cu, In) are distributed homogeneously within the sphalerite matrix, but their structural and chemical states are different. In all the samples investigated In³⁺replaces Zn in the structure of sphalerite. The In ligand distance increases by 0.12 Å and 0.09–0.10 Å for the 1st and 2nd coordination shells, respectively, in comparison with pure sphalerite. The In–S distance in the 3rd coordination shell is close to the one of pure sphalerite. Gold in synthetic sphalerites is coordinated with sulfur (N_S= 2.4–2.5,R_Au–S= 2.35 ± 0.01 Å). Our data suggest that at high Au concentrations (0.03–0.5 wt.%) the Au₂S clusters predominate, with a small admixture of the Au⁺solid solution with an Au–S distance of 2.5 Å. Therefore, the homogeneous character of a trace-element distribution, which is commonly observed in natural sulfides, does not confirm formation of a solid solution. In contrast to Au, the presence of Cu⁺with In exists only in the solid-solution state, where it is tetrahedrally coordinated with S atoms at a distance of 2.30 ± 0.03 Å. The distant coordination shells of Cu are disordered. These results demonstrate that the group 11 metals (Cu, Ag and Au) can exist in sphalerite in the metastable solid-solution state. The solid solution forms at high temperature via the charge compensation scheme 2Zn²⁺↔Me⁺+Me³⁺. The final state of the trace elements at ambient temperature is governed by the difference in ionic radii with the main component (Zn), and concentration of admixtures.

A significant part of the primary gold reserves in the world is contained in sulphide ores, many types of which are refractory in gold processing. The deposits of refractory sulphide ores will be the main potential source of gold production in the future. The refractory gold and silver in sulphide ores can be associated with micro- and nano-sized inclusions of Au and Ag minerals as well as isomorphous, adsorbed and other species of noble metals (NM) not thoroughly investigated. For gold and gold-bearing deposits of the Urals, distribution and forms of NM were studied in base metal sulphides by laser ablation-inductively coupled plasma mass spectrometry and by neutron activation analysis. Composition of arsenopyrite and As-pyrite, proper Au and Ag minerals were identified using electron probe microanalysis. The ratio of various forms of invisible gold—which includes nanoparticles and chemically bound gold—in sulphides is discussed. Observations were also performed on about 120 synthetic crystals of NM-doped sphalerite and greenockite. In VMS ores with increasing metamorphism, C_Au and C_Ag in the major sulphides (sphalerite, chalcopyrite, pyrite) generally decrease. A portion of invisible gold also decreases —from ~65–85% to ~35–60% of the total Au. As a result of recrystallisation of ores, the invisible gold is enlarged and passes into the visible state as native gold, Au-Ag tellurides and sulphides. In the gold deposits of the Urals, the portion of invisible gold is usually <30% of the bulk Au.