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The three-mode distribution of trace-element (TE) concentrations is observed in accordance with three main forms of TE occurrence in mineral: structural, surficial, and phase (native TE phases). Minerals of hydrothermally synthesized pyrite–pyrrhotite–magnetite–greenockite assemblage in the presence of Au and Mn are studied. Discrimination of modes is made, using the method of statistical sample of analytical data for single crystals (SSADSC), which is based on the postulate that individual crystals can contain predominantly one of possible forms. This is supported by study of Cd modes of occurrence by element thermorelease atomic-absorption spectrometry. X-ray photoelectron spectroscopy and atomic-force microscopy were used to examine the surficial TE forms. It has been confirmed that the dependence of the TE content on the crystal size in the sample is mainly due to surficial nonautonomous phases absorbing TEs. The effect of correspondence of chemical-component forms on the surfaces of coexisting minerals is also corroborated. This phenomenon is not related to the mutual contamination of phases but is due to the induction of the corresponding states of chemical forms in coexisting nonautonomous phases. It is possible to obtain true coefficients of interface distribution, characterizing structural TE impurities. These coefficients differ strongly from apparent distribution coefficients calculated from the bulk contents of impurities, except for Mn in pyrrhotite and magnetite, where its structural mode is predominant. The results obtained show that TEs can be used as quantitative geochemical indicators, which help to obtain correct information about the parameters of mineral formation and TE contents in the fluid phase.

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The dual distribution coefficients (D) that are related to structurally and superficially bound trace element (TE) in pyrite (Py) and pyrrhotite (Po) associations, crystallized hydrothermally at 400 °C and 1 kbar pressure, were determined. Three independent methods were used to estimate the structural and surficial TE contents (Cstr and Csur) and the corresponding D Py/Po values (Dstr and Dsur), which were found, on average, to be 12.4, 0.8, 0.9, and 0.06 (Dstr) and 2.6, 0.7, 2.0, and 0.07 (Dsur) for Ag, Pd, Cd, and Mn, respectively. The coincidence of a dual D for several elements was a result of coupled changes in Csur and Cstr. The selectivity (S) of the surficial nonautonomous phases (NAPs) that were responsible for TE accumulation (which is the ratio of TE concentrations in surficial and structural modes) was determined. It was shown that the interpretation of TE uptake by surficial phases was adequate and that this phenomenon is common in nature, independently of the system where it occurs—i.e., in experimental autoclaves or in hydrothermal ore deposits. Studies of NAPs selectivity can help in evaluating the total element compatibility in minerals and the maximum possible contents of structurally bound admixtures of the element (solubility) in minerals under given conditions. A significant surficial impurity accumulation effect is most important and well-pronounced for incompatible micro-elements with concentrations of less than ~0.1 wt%. The surficial mode may be a source of Pd and other platinum group elements and more abundant and easily refined than the structurally bound mode.

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