X-Ray Absorption Spectroscopies AFS) are employed in order to gather a thorough insight on the uptake mechanism of Cr(VI) by Fe3O4 nanoparticles under water treatment conditions. The XANES measurements identify that the reducing potential of Fe3O4 activates the precipitation of Cr(VI) in the form of insoluble and non-toxic Cr(III). However, electron donation from Fe(II) is responsible for its gradual consumption, resulting in the presence of a surface maghemite layer and the formation of structural vacancies. EXAFS analysis reveal that adsorption of Cr(III)-oxyanions occurs on sorption sites provided by the vacancies in the maghemite layer, where Cr(III) is involved in a bidentate binuclear (2E) geometry with Fe-octahedra while it also forms monodentate (V-1) complexes with the Fe(III)O-4 tetrahedra. The surface maghemitization along with the reduced Cr(III) adsorption into the vacancies, tracks the degree of Cr-reduction, since this surface structural modifications hinder Cr(VI) access to the Fe(II) ions of the magnetite nanoparticles. Thus, high surface coverage leads to the passivation of the reduction ability since physisorbed Cr(VI) is also detected through the formation of outer sphere complexes. (C) 2015 Elsevier B.V. All rights reserved.