Cr stable isotope fractionation and reaction kinetics in aqueous milieu

Mass-dependent stable Cr isotope variations show great potential to monitor the natural attenuation of anthropogenic chromate pollution as well as to investigate changes in environmental conditions in the present and the past. However, accurate interpretation of mass-dependent Cr isotope variations requires profound knowledge of the Cr isotope fractionation behaviour during redox transitions and the isotope exchange kinetics of the reactions involved. Here, we present a comprehensive dataset of stable Cr isotope fractionation and reaction kinetics during Cr(III) oxidation, Cr(VI) reduction and isotopic exchange between soluble Cr(III) and Cr(VI) in aqueous milieu. All experiments were carried out with both oxidation states (i.e. Cr(III) and Cr(VI)) in solution, using H2O2 as oxidising as well as reducing agent. The pH conditions were varied to investigate the influence of the different Cr(III) and Cr(VI) species on the Cr isotope fractionation and on the reaction mechanisms during the enforced redox transitions. All Cr stable isotope measurements were performed by high-resolution MC-ICP-MS [1]. The reduction of Cr(VI) to Cr(III) with H2O2 under strongly acidic conditions shows an equilibrium isotope fractionation of Δ(53,52Cr)Cr(III)-Cr(VI) of -3.54 ± 0.35 ‰. This value is within uncertainty equal to that of -3.4 ± 0.1 ‰ reported by Ellis et al. [2], who used natural sediment and magnetite as reducing agents at pH 6 to 7. At pH = 7 our reduction experiments show a unidirectional, kinetic isotope fractionation Δ(53,52Cr)Cr(III)-Cr(VI) of approximately -5 ‰ for reduction rates of up to 80 %, but a strong deviation from this Rayleigh-type process for higher reduction rates. However, at a pH value of 7 H2O2 supports the temporary formation and decomposition of Cr(V)-peroxo complexes that might explain this fractionation behaviour and deviation from a single Rayleigh type trend. The oxidation experiments of Cr(III) to Cr(VI) were carried out in alkaline media using H2O2 as reducing agent. The observed, small Cr isotope fractionation can not be explained by one, unidirectional oxidation process. The high energy needed to oxidise Cr(III) to Cr(VI), potential Cr(III) oligomerisation and the formation of Cr(IV) and/or Cr(V) intermediates make the oxidation of Cr(III) to Cr(VI) a very complex fractionation mechanism. Our best-fit modelling points to an overall isotope fractionation Δ(53,52Cr)Cr(VI)-Cr(III) of +0.15 ‰ during the different oxidation steps, which is overprinted by a much larger isotope fractionation Δ(53,52Cr)Cr(III)-Cr(VI) of -3.4 ‰ during the back reduction of approximately 15 % of the chromium. No isotope exchange between soluble Cr(VI) and Cr(III) species at pH values of 5.5 and 7 was revealed by our experiments over a timescale of 120 hours. This observation is in good agreement with the lack of isotope exchange between oxygen bound in dissolved chromate CrO42- and that of the surrounding water [3]. [1] Schoenberg, R. et al. (2008) Chemical Geology, 249, 294ff. [2] Ellis, A. et al. (2002) Science, 295, 2060ff. [3] Bullen, T. et al. (2009) Geochim. Cosmochim. Acta, 73 (13), Suppl. 1, A173