title: Surface complexation and oxidation of Sn(II) by nanomagnetite.
abstract: The long-lived fission product 126Sn is of substantial interest in the context of nuclear waste disposal in deep underground repositories. However, the prevalent redox state, the aqueous speciation as well as the reactions at the mineral-water interface under the expected anoxic and reducing conditions are a matter of debate. We therefore investigated the reaction of Sn(II) with a relevant redox-reactive mineral, magnetite (Fe(II)Fe(III)2O4) at <2 ppmv O2, and monitored Sn uptake as a function of pH and time. Tin redox state and local structure were investigated by Sn–K X-ray absorption spectroscopy (XAS). We observed a rapid uptake (<30 min) and oxidation of Sn(II) to Sn(IV) by magnetite. The local structure determined by XAS showed two Sn–Fe distances of about 3.15 and 3.60 Å in line with edge and corner sharing arrangements between octahedrally coordinated Sn(IV) and the magnetite surface, indicative of formation of tetradentate inner-sphere complexes between pH 3 and 9. Based on the EXAFS-derived surface structure, we could successfully model the sorption data with two different complexes, (Magn_sO)4Sn(IV)(OH)2–2 (logK(2,0)(–2) −14.97 ± 0.35) prevailing from pH 2 to 9, and (Magn_sO)4Sn(IV)(OH)2Fe (logK(2,1)(0) −17.72 ± 0.50), which forms at pH > 9 by coadsorption of Fe(II), thereby increasing sorption at this high pH.
authors.affiliation: Institute of Resource Ecology, Helmholtz Center Dresden Rossendorf , D-01314, Germany.
authors.forename: Siriwan
authors.initials: S
authors.lastname: Dulnee
authors.forename: Dipanjan
authors.initials: D
authors.lastname: Banerjee
authors.forename: Broder J
authors.initials: BJ
authors.lastname: Merkel
authors.forename: Andreas C
authors.initials: AC
authors.lastname: Scheinost
mesh_terms: D000327:Adsorption; D004777:Environment; D052203:Ferrosoferric Oxide / Q000737:chemistry*; D008958:Models, Molecular; D053758:Nanoparticles / Q000737:chemistry*; D010084:Oxidation-Reduction; D012996:Solutions; D013499:Surface Properties; D014001:Tin / Q000737:chemistry*; D014867:Water / Q000737:chemistry; D056928:X-Ray Absorption Spectroscopy
chemical_list: D012996:Solutions; D014867:Water; D014001:Tin; D052203:Ferrosoferric Oxide