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Presents a study on the initial oxidation of pyrite surfaces in air using X-ray and ultraviolet photoelectron spectroscopy (XPS and UPS) and scanning tunneling microscopy. Comparison of valence-bond photoemission spectra for cleaned pyrite; Pyrite valence-band electronic structure; UPS valence-band spectra; XPS valence-band spectra.

The ability of mackinawite, an iron(II) monosulphide, to reduce Cr(VI) was studied at pH values of 5 and 7, Cr(VI) solution concentrations ranging from 10-4 to 6 × 10-3M and fixed ionic strength. Mackinawite suspensions (0.6gL-1 and 1.2gL-1) and Cr(VI) solutions were reacted for 4.5h in a nitrogen atmosphere. The oxidation of mackinawite was determined by analysing both solutions and solid phases after Cr(VI) reaction. The solid phases were characterised by using complementary electrokinetic measurements and X-ray Photoelectron Spectroscopy and by Transmission Electron Microscopy. Solutions were analysed using colorimetric methods for Fe(II) and Cr(VI) and capillary electrophoresis for sulphur speciation. Mackinawite was found to be a very effective reductant of Cr(VI) under the conditions of the experiments. The removal capacity was determined to be around 130mg Cr(VI)/g FeS at pH 7 and 240mg Cr(VI)/g FeS at pH 5. The presence of an iron(III) and chromium(III) (oxyhydr)oxide layer covering the mackinawite crystals was evidenced with a constant Cr to Fe ratio of 1.4 ± 0.2. The extent of the metal (oxyhydr)oxide layer increases with the initial Cr(VI) concentration, thus probably limiting the Cr(VI) reduction at high initial Cr(VI) concentrations. [Copyright &y& Elsevier]