Biological activation of hydrous ferric oxide for reduction of hexavalent chromium in the presence of different anions

Shewanella alga BrY, a dissimilatory iron reducing bacterium (DIRB), transformed inert ferric oxides that are common in sediments, aquifer material and passivated permeable reactive iron barriers (PRBs), producing dissolved and sorbed Fe(II) capable of rapidly reducing and immobilizing Cr(VI). The effect of groundwater chemistry on the formation and reactivity of such microbial-produced, abiotic reductants was investigated. Batch reactors with high carbonate concentration (10 mM) were the most reactive, removing 66.0% ± 2.8 of Cr (VI) (76 mg/l) from liquid phase within 5 min. Treatments with high concentrations of sulfate (5.2 mM), chloride (10 mM), phosphate (1 mM) or silica (0.75 mM) were less reactive (about 40% removal). Loss of reactivity was observed possibly due to oxidation of Fe(II) (sorbed and dissolved) by Cr(VI). Normalization of Cr(VI) removal to the mass of biogenic solid present showed the following molar Cr/Fe ratios in solid phase: 0.185 ± 0.041 (carbonate), 0.146 ± 0.013 (sulfate), 0.092 ± 0.010 (silica), 0.075 ± 0.012 (phosphate) and 0.062 ± 0.012 (chloride). Overall, these results show that bacterial transformation of inert ferric oxides can contribute to the (abiotic) natural attenuation of Cr(VI) in and around PRBs, and that groundwater chemistry is an important determinant of biogenic solids reactivity.