Cr stable isotopes as indicators of Cr(VI) reduction in groundwater: A detailed time-series study of a point-source plume

Chromium stable isotope ratios show promise as indicators of Cr(VI) reduction in groundwater, but no published study has yet demonstrated that expected relationships between ⁵³Cr/⁵²Cr and Cr(VI) concentration, position, and time occur in an actual groundwater plume. We present an extensive data set from a point-source plume in Berkeley, CA; data extend over 5 years and 14 locations covering the entire plume. We interpret the data using a Rayleigh distillation model with an effective fractionation factor that incorporates an intrinsic fractionation factor determined from incubations of site sediments and accounts for reservoir effects in the restricted subsurface zones where Cr(VI) reduction is thought to occur. The groundwater ⁵³Cr/⁵²Cr and Cr(VI) concentration data are consistent with a scenario where the system has reached a steady state: Cr(VI) reduction continues, the extent of reduction at any point is constant over time, reduction proceeds to completion at the downgradient edge of the plume, and the plume is no longer advancing. The overall consistency of the results with a reasonable model for the site supports the use of Cr isotope-based estimates of reduction, but we discuss current uncertainties and limitations of the approach as well.