Determination of hexavalent chromium reduction using cr stable isotopes: Isotopic fractionation factors for permeable reactive barrier materials

Cr stable isotope measurements can provide improved estimates of the extent of Cr(VI) reduction to less toxic Cr(III). The relationship between observed ⁵³Cr/⁵²Cr ratio shifts and the extent of reduction can be calibrated by determining the isotopic fractionation factor for relevant reactions. Permeable reactive barriers (PRB) made of Fe⁰ and in situ redox manipulation (ISRM) zones effectively remediate Cr-contaminated aquifers. Here, we determine the isotopic fractionations for dominant reductants in reactive barriers and reduced sediments obtained from an ISRM zone at the US DOE's Hanford site. In all cases, significant isotopic fractionation was observed; fractionation (expressed as ε) was -3.91‰ for Fe(II)-doped goethite, -2.11‰ for FeS, -2.65‰ for green rust, -2.67‰ for FeCO₃, and -3.18‰ for ISRM zone sediments. These results provide a better calibration of the relationship between Cr isotope ratios and the extent of Cr(VI) reduction and aid in interpretation of Cr isotope data from systems with reactive barriers.