Stable Isotope Fractionation during Chromium(III) Oxidation by δ-MnO2

Hexavalent chromium is a highly mobile anthropogenic pollutant, and reduction of Cr(VI) to the less-soluble Cr(III) is the most important natural process involved in contamination attenuation. Earlier work has shown a preferential reduction of lighter Cr stable isotopes attributed to a kinetically-controlled mechanism, and isotope ratio measurements may be used as indicators of Cr(VI) reduction [1]. Recent work has detected no significant isotope exchange between dissolved Cr(III) and Cr(VI) over a period of days to weeks, and has suggested that complex bidirectional reactions control fractionation during Cr(III) oxidation by H2O2 [2]. Previous studies on oxidation by pyrolusite (β-MnO2) have reported δ53/52Cr up to approximately +1.1‰ in the Cr(VI) product [3]. However, laboratory investigations of fractionation during Cr(III) oxidation by birnessite (δ-MnO2) have been inconclusive, and oxidation mechanisms remain unclear [4]. In order to fully exploit stable isotope fractionation during redox reactions of Cr in groundwater as an indicator of Cr attenuation, the effect of Cr(III) oxidation on isotope ratios must be better understood. We will report the latest measurements of isotope fractionation during oxidation on birnessite under varying pH and MnO2 and Cr(III) concentrations. Our preliminary findings (at initial Cr(III) and δ-MnO2 concentrations of 10 mg/L and 100 mg/L, respectively) show the Cr(VI) product shifted by -0.5‰ to +0.0‰ relative to the reactant at pH ≈ 4.5. The reaction is incomplete and plateaus within 60 min. Unlike that observed with pyrolusite, fractionation during Cr oxidation on birnessite is much smaller or absent. These initial results suggest that kinetic effects are either very small or are negated by back reaction or equilibration in the multi-step oxidation mechanism. Alternatively, in our experiments, a step involving little isotope fractionation may be rate-limiting; thus, the final magnitude of isotope fractionation during oxidation on birnessite could vary if the rate-limiting step changes. Additional experiments at different conditions will aid in the elucidation of fractionating mechanisms during Cr(III) oxidation. [1] Ellis, A. S.; Johnson, T. M.; Bullen, T. D. (2002) Science, 295(5562), 2060 [2] Zink, S.; Schoenberg, R.; Staubwasser, M. (2010) Geochim. Cosmochim. Acta, in press [3] Ellis, A. S.; Johnson, T. M.; Villalobos-Aragon, A.; Bullen, T. D. (2008) Eos Trans. AGU, 89(53), Fall Meet. Suppl., Abstract H53F-08 [4] Bain, D. J.; Bullen, T. D. (2005) Geochim. Cosmochim. Acta, 69(10), Suppl. 1, A212