Evaluating the risk of chromium reoxidation in aquifer sediments following a reductive bioremediation treatment

Remediation of chromium contamination typically involves reducing the toxic and soluble hexavalent form, Cr(VI), to the relatively harmless and mostly immobile trivalent state, Cr(III). The objective of this study is to investigate the potential for reduced chromium precipitates to be remobilized under oxidizing conditions that are expected to be prevalent some time after the bioremediation treatment is completed. In an initial phase of the experiment, reduction under anaerobic conditions was observed for over 12 months by subjecting flow-through columns containing homogenized sediments from the Hanford 100H aquifer to different dominant electron acceptors, i.e. NO₃^-, Fe(III), or SO₄^2-, in the presence of 5 μM Cr(VI) and 5 mM lactate. Cr(VI) was depleted in the effluent solutions of the nitrate-treated columns, all of which exhibited denitrification, as well as in sulfate-amended columns in which fermentative conditions became dominant (with a minor amount of sulfate reduction). In the second phase of the study, oxygenated water with 2 mM nitrate was flowed through the denitrifying and fermentative columns for several months, without addition of Cr(VI) or lactate. The results show that the chromium that precipitated in the denitrifying columns was steadily mobilized under the oxidizing conditions, although the concentration of Cr(VI) in the effluent remained low (<0.25 μM). However, measurable Cr(VI) was not detected in the effluent from the fermentative sulfate-amended column. Reducing conditions were sustained in the fermentative column despite the continuous influx of O₂, as indicated by the decrease of nitrate and accumulation of nitrite, potentially due to the presence of sulfides precipitated during the initial reducing phase of the experiment. The results from this study suggest that the biogeochemical conditions present during the reductive treatment phase can substantially impact the long-term sustainability of the remediation effort.