Adsorption and surface oxidation of Fe(II) on metal (hydr)oxides.

T. Hiemstra, W.H. van Riemsdijk

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Abstract

The Fe(II) adsorption by non-ferric and ferric (hydr)oxides has been analyzed with surface complexation modeling. The CD model has been used to derive the interfacial distribution of charge. The fitted CD coefficients have been linked to the mechanism of adsorption. The Fe(II) adsorption is discussed for TiO2, ¿-AlOOH (boehmite), ¿-FeOOH (lepidocrocite), ¿-FeOOH (goethite) and HFO (ferrihydrite) in relation to the surface structure and surface sites. One type of surface complex is formed at TiO2 and ¿-AlOOH, i.e. a surface-coordinated Fe2+ ion. At the TiO2 (Degussa) surface, the Fe2+ ion is probably bound as a quattro-dentate surface complex. The CD value of Fe2+ adsorbed to ¿-AlOOH points to the formation of a tridentate complex, which might be a double edge surface complex. The adsorption of Fe(II) to ferric (hydr)oxides differs. The charge distribution points to the transfer of electron charge from the adsorbed Fe(II) to the solid and the subsequent hydrolysis of the ligands that coordinate to the adsorbed ion, formerly present as Fe(II). Analysis shows that the hydrolysis corresponds to the hydrolysis of adsorbed Al(III) for ¿-FeOOH and ¿-FeOOH. In both cases, an adsorbed M(III) is found in agreement with structural considerations. For lepidocrocite, the experimental data point to a process with a complete surface oxidation while for goethite and also HFO, data can be explained assuming a combination of Fe(II) adsorption with and without electron transfer. Surface oxidation (electron transfer), leading to adsorbed Fe(III)(OH)2, is favored at high pH (pH > 7.5) promoting the deprotonation of two FeIII-OH2 ligands. For goethite, the interaction of Fe(II) with As(III) and vice versa has been modeled too. To explain Fe(II)¿As(III) dual-sorbate systems, formation of a ternary type of surface complex is included, which is supposed to be a monodentate As(III) surface complex that interacts with an Fe(II) ion, resulting in a binuclear bidentate As(III) surface complex.
Original languageEnglish
Pages (from-to)5913-5933
JournalGeochimica et Cosmochimica Acta
Volume71
Issue number24
DOIs
Publication statusPublished - 2007

Keywords

  • oxide-water interface
  • lepidocrocite gamma-feooh
  • ray-absorption-spectroscopy
  • aqueous-solution interface
  • intrinsic proton affinity
  • solid-solution interface
  • electrical double-layer
  • charge-distribution
  • ferrous iron
  • ion adsorption

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