Selenite reduction by nano-crystalline green rust, magnetite, siderite and mackinawite: EXAFS identification of Se species

Selenium oxoanions are abiotically reduced on Fe(II/III) hydroxide (green rust) and Fe(0) metal surfaces to Se oxidation states of 0, -I or –II with relatively slow reaction kinetics 1, 2]. The unequivocal phase characterization by EXAFS spectroscopy, which is a key for the determination/prediction of Se solubility, was hindered by incomplete reduction, insufficient spectral data ranges and the similarity in short-range structures of the potential mineral phases. In a recent study [3], however, we were able to clearly identify the reduction product of selenite co-sorbed with Fe2+ to montmorillonite as nano-particulate, trigonal Se(0) by collecting low-noise EXAFS spectra at 15 K (Rossendorf Beamline at ESRF, Grenoble, France) and by employing advanced data analysis methods [4, 5]. Here, we present data on the reduction of selenite by green rust, magnetite, siderite and mackinawite. In the presence of green rust, selenite was completely reduced to trigonal Se(0) within one day, which was further converted to ferroselite (orthorombic FeSe2) within one month. The associated Fe(II) oxidation and magnetite formation quantified by Moessbauer spectroscopy allowed us to establish the following reaction scheme: 32 [FeII 12FeIII 5(OH)34 Cl-5 H2O](s) + 38 SeIVO3 2- ⇔ 19 [FeIISe-I 2](s) + 175 [FeIIFeIII 2O4 formed. The observed differences in reaction end products and reduction kinetics may significantly affect Se bioavailability and Se migration.
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