Surface typochemistry of hydrothermal pyrite: Electron spectroscopic and scanning probe microscopic data. II. Natural pyrite

Pyrite crystals from gold deposits of various genetic types (mesothermal and epithermal) were examined by techniques of x-ray photoelectron and Auger electron microscopy and by scanning probe microscopy. The results confirm a conclusion made in earlier hydrothermal experiments that nonautonomous phases (NP) of variable composition occur on the surface of pyrite crystals. These phases are localized within a layer of submicrometer (nanometer) thickness (up to similar to 0.5 mu m) within which the typochemistry of pyrite surface is pronounced. The development of sulfate on the surface of pyrite crystals from epithermal Au-Ag deposits is a typochemical feature of the origin of their ore mineralization at low temperatures and shallow depths. Supergene conditions are characterized by the presence of an oxi-hydroxide or oxide film of FeIII, which morphologically differs from the layer of a pyrite-like NP. The composition and properties of the NPs are different for pyrite from mesothermal and epithermal deposits: they are close to those of a pyrrhotite-like NP discovered on synthetic hydrothermal pyrite and contain an additional sulfite anion for pyrite from the former type of deposits and are close to sulfide-disulfide ensembles with trivalent Fe for pyrite from the latter type of deposits. Trace elements, including precious metals, can be accommodated in such a phase via the stabilization of clusters with Fe(3+) and SO(4) (2-) in its structure. The instability of the crystallization process in epithermal environments may bring about the development of double-level nanostructure because of the structural transformation of vicinal surfaces into a set of ordered domains and the synthesis of nonautonomous precursor phases. Such systems can be stabilized via the excess dissolution of admixtures or the transition of the surface layer into another phase state.