Reduction of antimony by nanoparticulate Fe3O4 and FeS

Antimony finds a wide range of industrial applications, e.g. in flame retardants, brake pads and as a lead-alloy in storage batteries and ammunition and is widely distributed in the environment. Sb may occur in several oxidations states (-III, 0, III, V). Under oxic conditions, Sb0 oxidizes prevalently to SbV, forming the anionic species Sb(OH)6- which is strongly sorbed by Fe oxides[1]. In contrast, SbIII forms an uncharged complex Sb(OH)3(aq), which is more mobile. Under anoxic conditions, SbV and SbIII may be reduced by FeII-bearing minerals. Magnetite (FeIIFeIII2O4) and mackinawite (FeS) have been shown to reduce e.g. Se[2], As[3], and Pu[4]). We therefore investigated the reaction of SbIII and SbV with these two minerals at <1ppm O2 (v/v) using Sb-K XAS.
When SbIII was reacted with magnetite at pH 4.7 to 7.6 during 1 h to 67 d, the oxidation state was stable and only one Sb species was identified by EXAFS. SbIII is coordinated with 4 to 5 iron atoms at a distance of 3.6 Å. FEFF Monte Carlo simulations revealed formation of a highly ordered surface complex on the {111} faces of magnetite. The trigonal pyramidal SbO3 units occupy positions of FeIII tetrahedra, that would be ideally coordinated to six Fe06 octahedra via corner-sharing. The experimental Fe coordination numbers below six suggest that Sb occupies positions near edges of the {111} faces. When SbV was reacted with magnetite, reduction to SbIII increased linearly between pH 4.5 and 6.5, with little influence of reaction time. The SbIII produced by the surface reaction formed the same surface complex as after direct addition of SbIII.
In the presence of mackinawite, SbV was completely reduced to SbIII within 30 d and in the pH range 4.3 - 8.4. The local structure shows SbIII surrounded by three sulfur atoms at a distance of 2.5 Å as in Sb2S3. The lack of more distant atomic shells suggests a highly dissordered structure. Again the resulting surface complex is the same as after direct addition of SbIII. Cryo-XPS measurements of shock-frozen samples show that the S 2p spectra remain unchanged before and after SbV reduction, while a FeIII-shoulder emerged in the Fe 2p spectra after reduction, indicating that SbV was reduced by FeII and not by S. In no case, reduction to an oxidation state below III was observed.

[1] Scheinost et al., Geochim. Cosmochim. Acta 70 (2006) 3299-3312. [2] Scheinost & Charlet, Environ. Sci. Technol. (2008) online. [3] Gallegos et al., Environ. Sci. Technol. 41 (2007) 7781-7786. [4] Powell et al., Environ. Sci. Technol. 38 (2004) 6016-6024.