Interaction between aqueous uranium (VI) and sulfide minerals: Spectroscopic evidence for sorption and reduction

作者：Paul Wersin, Michael F. Hochella, Per Inge Persson, George D. Redden, James O. Leckie, D. E. Harris · 发表于：Geochimica et Cosmochimica Acta · 年份：1994 · DOI：10.1016/0016-7037(94)90117-1 · 被引用次数：303 · 研究领域：Radioactive element chemistry and processing、Geochemistry and Geologic Mapping、Metal Extraction and Bioleaching

The interaction of aqueous U(VI) with galena and pyrite surfaces under anoxic conditions has been studied by solution analysis and by spectroscopic methods. The solution data indicate that uranyl uptake is strongly dependent on pH; maximum uptake (>98%) occurs above a pH range of between 4.8 and 5.5, depending on experimental conditions. Increasing the sorbate/sorbent ratio results in a relative decrease in uptake of uranyl and in slower sorption kinetics. Auger electron spectroscopy (AES) analysis indicates an inhomogeneous distribution of sorbed uranium at the surface. In the case of galena, formation of small precipitates (~40 nm wide needles) of a uranium oxide compound are found. Pyrite shows a patchy distribution of uranium, mainly associated with oxidized surface species of sulfur and iron. X-ray photoelectron spectroscopy (XPS) yields insight into possible redox processes indicating, for both sulfides, the concomitant formation of polysulfides and a uranium oxide compound with a mixed oxidation state at a U(VI)/U(IV) ratio of ~2. Furthermore, in the case of pyrite, at pH above 6 increased oxidation of sulfur and iron and higher relative amounts of unreduced surface-uranyl are observed. Fourier Transformed Infrared (FTIR) analysis of surface-bound uranyl shows a significant shift of the asymmetric stretching frequency to lower wavenumbers which is consistent with the formation of a U3O8-type compound and thus, independently, confirms the partial reduction of uranyl at ...