title: U(VI) sorption and reduction by Fe(II) sorbed on montmorillonite.
abstract: The influence of surface-bound Fe(II) on uranium oxidation state and speciation was studied as a function of time (6 min-72 h) and pH (6.1-8.5) in a U(VI)-Fe(II)-montmorillonite (Ca-montmorillonite, MONT) system under CO(2)-free, anoxic (O(2) <1 ppmv) conditions. The results show a rapid removal of U(VI) from the aqueous solution within 1 h under all pH conditions. U L(III)-edge X-ray absorption near-edge structure spectroscopy shows that 96% of the total sorbed U(VI) is reduced at pH 8.5. However, the extent of reduction significantly decreases at lower pH values as specifically sorbed Fe(II) concentration decreases. The reduction kinetics followed by X-ray photoelectron spectroscopy during 24 h at pH 7.5 demonstrates the presence of partially reduced surface species containing U(VI) and U(IV). Thermodynamically predicted mixed valence solids like U(3)O(8)/beta-U(3)O(7)/U(4)O(9) do not precipitate as verified by transmission electron microscopy and extended X-ray absorption fine-structure spectroscopy. This is also supported by the bicarbonate extraction results. The measured redox potentials of Fe(II)/Fe(III)-MONT suspensions are controlled by the Fe(II)/hydrous ferric oxide [HFO(s)] couple at pH 6.2 and by the Fe(II)/lepidocrocite [gamma-FeOOH(s)] couple at pH 7.5. The key finding of our study is the formation of a sorbed molecular form of U(IV) in abiotic reduction of U(VI) by sorbed Fe(II) at the surface of montmorillonite.
authors.affiliation: LGIT-OSUG, University of Grenoble-I, Grenoble, France. chakrabortysudipta@hotmail.com
authors.forename: Sudipta
authors.initials: S
authors.lastname: Chakraborty
authors.forename: Fabienne
authors.initials: F
authors.lastname: Favre
authors.forename: Dipanjan
authors.initials: D
authors.lastname: Banerjee
authors.forename: Andreas C
authors.initials: AC
authors.lastname: Scheinost
authors.forename: Martine
authors.initials: M
authors.lastname: Mullet
authors.forename: Jean-Jacques
authors.initials: JJ
authors.lastname: Ehrhardt
authors.forename: Jocelyne
authors.initials: J
authors.lastname: Brendle
authors.forename: Loïc
authors.initials: L
authors.lastname: Vidal
authors.forename: Laurent
authors.initials: L
authors.lastname: Charlet
mesh_terms: D000327:Adsorption; D001546:Bentonite / Q000737:chemistry*; D005296:Ferrous Compounds / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D010084:Oxidation-Reduction; D013816:Thermodynamics; D014501:Uranium / Q000737:chemistry*
chemical_list: D005296:Ferrous Compounds; D001546:Bentonite; D014501:Uranium