Computational and Experimental Simulations of Cr(VI) Remediation via In Situ Reduction in an Alluvial Aquifer at Hinkley, California

Abstract:

The accumulation of hexavalent chromium (Cr(VI)) in groundwater due to natural and human-induced processes poses a significant health threat as Cr(VI) is both a carcinogen and mutagen. Anthropogenic Cr(VI) contamination has compromised drinking water in the alluvial aquifer underlying the town of Hinkley, CA and extensive in-situ remediation (ISR) is underway to mitigate the threat to residents. ISR capitalizes on the redox sensitivity of chromium by using ethanol to reduce soluble, toxic, Cr(VI) to insoluble and non-hazardous Cr(III). However, the sequence of reduction reactions that occurs within the aquifer is not well understood. Therefore, we use computer-modeled and experimental redox titrations to examine how pH, oxygen supply, mineral surface chemistry, agitation, and microbial activity impact the reduction of Cr(VI) by ethanol. We further use experimental titrations to confirm the validity of our modeled results. Aqueous and gaseous phases are monitored throughout the experiment to track changes in pH, dissolved oxygen, CO₂, Mn(II), Fe(II), and SO₄^2-. Aqueous Fe(II) is a dominant control on Cr(VI) reduction; thus the cycling of Fe in the system must be considered. Our modeled results show that reductive dissolution of manganese oxides and Fe(III) (oxy)hydroxides increases pH, making sulfate reduction thermodynamically favorable. Simultaneous Fe(III) and sulfate reduction allows precipitation of iron sulfide minerals, limiting the available Fe(II) to reduce Cr(VI). Computational model results indicate that elevated organic buffer (HEPES, MOPS, EPPS) concentrations are required to maintain pH values below 8.8 where simultaneous reduction of Fe(III) and SO₄^2- during ethanol oxidation becomes thermodynamically favorable. Microbial activity within the aquifer may also play a significant role in the transfer of electrons from ethanol to the terminal electron acceptors.