PNNL

Abstract

In the presence of sulfate-reducing bacteria (Desulfovibrio desulfuricans) hematite (a-Fe2O3) dissolution is affected and hydrogen sulfide, the product of sulfate reduction is released. As a consequence, ferrous ions are free to react with excess H2S to form insoluble iron sulfides. X-ray photoelectron spectra indicate binding energies consistent with the iron sulfides having a pyrrhotite structure (Fe2p3/2 708.4 eV; S2p3/2 161.5 eV). Other sulfur species identified at the surface include sulfate, sulfite and polysulfides. X-ray diffraction suggests an unidentifiable crystal structure at the hematite surface develops within 3 months, HRTEM confirms the presence of a hexagonal structure again suggesting the formation of pyrrhotite. The identification of pyrrhotite is inconsistent with previous reports in which mackinawite and greigite were products of biological sulfate reduction (Rickard 1969; Herbert et al 1998). The apparent differences in stoiciometries may be related to the availability of Fe2+(aq.) at the mineral surface through respiratory iron reduction by subsurface bacteria. The significance of pyrrhotite and polysulfide production in relation to the S- and Fe-cycles and to trace metal bioavailability is discussed.