The origin of native selenium microparticles during the oxidation of sideritic mudstones in the Verovice Formation (Outer Western Carpathians)

Abstract

Microparticles of native selenium were detected in weathered sideritic mudstones of the Veřovice Formation (Aptian) of the Silesian Unit (Outer Western Carpatians, NE part of the Czech Republic). This mineral forms small needle-like crystals with lengths of up to 20 μm, and is confined to fissures in sideritic mudstones covered by goethite or rarely also by hydrated Mn-oxide minerals. The oxidized sideritic mudstones show zonal structure and resemble the initial stage of the formation of the so-called rattle stones. From the superposition of phase diagrams of selenium and Fe-oxyhydroxides, Fe apparently occupies a large field in which Se(0) and FeOOH and/or Fe(OH)3 can co-exist. The reduction of selenites or selenates by pyrite or by any other phase, capable of charge transfer, is likely to have been responsible for the formation of microparticles of native selenium. The crucial factor controlling the origin of these particles is the extremely low solubility of Se(0). The source of Se is not obvious. It can be released in trace concentrations during the weathering of pyrite. Sediments of the Veřovice Formation correspond to the anoxic event OAE1b and accumulation of siderophile elements in similar sediments is very probable. A probable mechanism for the origin of Se microcrystals is gradual crystallization from solution.