Hexavalent chromium, a byproduct of many industrial processes, is toxic and produces mobile aqueous oxyanions, whereas Cr(III) is relatively immobile in the environment and, moreover, essential in human glucidic metabolism. For this reason, Fe(II)-Fe(III) layered double hydroxysalt green rusts, recently identified as a mineral in hydromorphic soils, were evaluated as potential Fe(II)-bearing phases for hexavalent chromium reduction. Both considered synthetic varieties, the hydroxysulfate GR(SO 4 2-) and the hydroxychloride GR(Cl -), proved to be very reactive; their interaction with potassium chromate solutions leads to the rapid and complete reduction of Cr(VI) into Cr(III). The Cr(III)bearing solid phase, studied by X-ray diffraction, Mo ¨ssbauer, X-ray photoelectron, and Raman spectroscopies, was determined to be a poorly ordered Cr(III)-Fe(III) oxyhydroxide, similar to the "2 the line ferrihydrite". The comparison between the experimental redox potential and pH values for a theoretical equilibrium diagram bearing Cr and Fe phases indicated that the solubility of this solid solution, which may govern the behavior of chromium in the environment, is of the same order as that of pure Cr(OH) 3 .

This work describes the chemical mechanisms governing transport and reduction of hexavalent chromium in soils of a contaminated industrial waste landfill. Groundwater and soil analyses indicate that the main source of chromium is a slag heap essentially consisting of mill tailings. In the groundwater, downstream migration of Cr(IV) is limited thanks to a redox mechanism involving chromate ions and ferrous ions or Fe(II)-bearing minerals. High Fe2+ concentrations in the groundwater are a result of pyrite residues from old activities at the site. Analyses of soil samples reveal that chromium is preferentially located in the soil profile at the fluctuation of the groundwater level. Grain size fractionation of four soil samples was performed, and fraction analyses show that chromium is preferentially accumulated in the clay fraction (<2 microm) and more specifically associated with montmorillonite particles. This work is a demonstration of the reduction of Cr(VI) by Fe(II) studied previously in the laboratory (Buerge, I. J.; Hug, S. J. Environ. Sci. Technol. 1997, 31, 1426-1432; Fendorf, S. E.; Li, G. Environ. Sci. Technol. 1996, 30, 1614-1617; Sedlak, D. L.; Chan, P. G. Geochim. Cosmochim. Acta 1997, 11, 2185-2192) in a field setting. Cr(VI) migration into the groundwater is stopped vertically by the very thick green clay unit and horizontally by the presence of Fe(II) acting as a chemical barrier. The specific site conditions safely prevent any extension of the Cr pollution.