Chromium Isotopic Fractionation During Biogeochemical Cr (IV) Reduction in Hanford Sediment Column Experiments with Native Aquifer Microbial Communities

Hexavalent Chromium contamination in groundwater within the DOE complex, including the Hanford 100D and 100H sites has been a long-standing issue. It has been established that certain bacteria (including denitrifying and sulfate-reducing bacteria) harbor enzymes that catalyze Cr(VI) reduction to relatively nontoxic Cr(III). Microbial reduction of Cr(VI) also occurs indirectly by products of microbial respiration, such as sulfide and Fe(II). Chromium isotopes can be fractionated during Cr(VI) reduction and provides a potential basis for characterizing and discriminating between different microbial metabolic and geochemical pathways associated with Cr(VI) reductive immobilization. Addition of electron donor to contaminated groundwater systems to create conditions favorable for reductive metal immobilization has become a widely utilized remediation practice. We conducted a series of small-scale column experiments with homogenized material from the Hanford 100H aquifer to examine the effects of differing electron acceptors on local microbial communities. All columns have a continuous inflow of solutions with constant concentrations of Cr(VI), lactate (electron donor), and the appropriate electron acceptor (e.g. nitrate or sulfate). The Cr isotopic composition in the effluent was measured using a 50-54 double-spike technique and a Triton TIMS. Cr concentration measurements showed that the greatest Cr(VI) reduction occurred in the sulfate columns. Our preliminary Cr isotopic data show that under these conditions the delta 53Cr value increased from close to 0 to 4 per mil while the Cr concentration decreased from 260 ppb to 30 ppb in the effluent. This yields an apparent fractionation factor of 0.9979 (2.1 per mil). A decrease in Cr concentration from 260 ppb to 190 ppb in a nitrate-reducing column was accompanied by an increase of 1 per mil in delta 53Cr. Further Cr isotopic data will be presented and the effects of differing flow rates and electron acceptors will be evaluated.