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.