Trivalent Actinide Uptake by Iron (Hydr)oxides

Abstract

The retention of Am(III) by coprecipitation with or adsorption onto preformed magnetite was investigated by X-ray diffraction (XRD), solution chemistry, and X-ray absorption spectroscopy (XAS). In the coprecipitation experiment, XAS data indicated the presence of seven O atoms at 2.44(1) Å, and can be explained by an Am incorporation at Fe structural sites at the magnetite surface. Next-nearest Fe were detected at distances suggesting that Am and Fe polyhedra share corners in geometries ranging from bent to close to linear Am-O-Fe bonds. After aging for two years, the coordination number and the distance to the first O shell significantly decreased, and atomic shells were detected at higher distances. These data suggest a structural reorganization and an increase in structural order around sorbed Am. Upon contact with preformed Fe₃O₄, Am(III) forms surface complexes with cosorbed Fe at the surface of magnetite, a possible consequence of the high concentration of dissolved Fe. In a separate experiment, chloride green rust (GR) was synthesized in the presence of Am(III), and subsequently converted to Fe(OH)₂(s) intermixed with magnetite. XAS data indicated that the actinide is successively located first at octahedral brucite-like sites in the GR precursor, then in Fe(OH)₂(s), an environment markedly distinct from that of Am(III) in Fe₃O₄. The findings indicate that the magnetite formation pathway dictates the magnitude of Am(III) incorporation within this solid.