Sequestration and reoxidation of chromium in experimental microcosms

Groundwater containing hexavalent chromium, Cr(VI), downgradient from the Pacific Gas and Electric Company (PG&E) Hinkley compressor station in the Mojave Desert, 80 miles northeast of Los Angeles, California, is undergoing bioremediation using added ethanol as a reductant in a volume of the aquifer defined as the in situ reactive zone (IRZ). This treatment reduces Cr(VI) to trivalent chromium, Cr(III), which is rapidly sequestered by sorption to aquifer particle surfaces and by co-precipitation within iron (Fe) or manganese (Mn) bearing minerals forming in place as reduction proceeds. Successful mitigation of the Cr(VI) plume is projected to require 10–95 years, at which time bioremediation with ethanol will likely cease. This projection assumes that Cr(VI) removal is permanent and that no Cr(III) will oxidize back to Cr(VI) in the event of changing hydrologic conditions that may cause oxygen-rich water to re-enter the IRZ. Laboratory microcosm experiments were done to explore the process of reductive sequestration of Cr(VI) to Cr(III) and the potential for reoxidation of Cr(III) to Cr(VI).

In reductive sequestration experiments, batch microcosms were prepared with aquifer materials collected from sites upgradient of the Cr(VI) regulatory plume. Control microcosms were prepared using Fe- and Mn-coated quartz sand. Unfiltered Mojave River groundwater containing an added tracer of isotopically labeled chromium-50 were reacted with microcosm materials for up to 2 years; during this time, bio-reduction was stimulated by repeated additions of diluted ethanol to maintain reduced conditions within appropriate ranges, avoiding sulfate reducing or methanogenic conditions as much as possible while mimicking field conditions. Analysis of chromium-50, Fe, and Mn obtained by sequential extraction from microcosms harvested (incubation terminated and microcosm contents analyzed) at various times showed that some aqueous chromium (Cr) was sorbed to particle surfaces within hours; reduction to Cr(III) and incorporation into amorphous and crystalline solid phases occurred during the next few months. Amorphous Cr-containing fractions included Fe and Mn hydroxides and organic matter. Ultimately, most of the chromium-50 tracer was present in the less reactive crystalline phase. However, Fe and Mn were broadly distributed at later stages of reduction, and both were spatially co-located with Cr on a micrometer (μm) scale. Solid-phase data collected using scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS) and X-ray absorption spectroscopy (XAS) indicated that some Cr(III) was associated with mixed valence Fe oxides like magnetite and Fe-Mn oxides like jacobsite. Additionally, Cr(III) was observed within several μm of Fe and Mn embedded in clays and in mineral coatings.

To evaluate the potential for reoxidation of Cr(III) to Cr(VI), additional batch microcosms of aquifer materials and mixtures of Fe- and Mn-coated sand were first reduced for more than 1 year and subsequently oxidized for almost 2 years. Hexavalent chromium was formed and was available for release to the aqueous phase during oxidation of all materials; however, the timing and amount of Cr(VI) formed and released varied among substrates. Artificial substrates containing more Mn produced more Cr(VI). Site material characteristic of recent Mojave River deposits contained within the IRZ produced the least Cr(VI) during oxidation, while site materials composed of older Mojave River aquifer material (containing more Mn) produced more Cr(VI). Site material collected from within the IRZ contained more Cr but produced an intermediate amount of Cr(VI) following oxidation. The combined results of microcosm chemistry and solid-phase analyses showed that the nature and locus of Cr(III) sequestration influenced its vulnerability to reoxidation to Cr(VI). It was concluded that co-location of Cr with Mn at later stages of reduction influenced the susceptibility of Cr(III) to reoxidation in microcosms.

Reoxidation of Cr(III) to Cr(VI) was observed in experiments with previously reduced material after just 14 days exposure to oxygen. As much as 10 percent of added Cr was oxidized to Cr(VI) in microcosms prepared using recent Mojave River aquifer material, and as much as 20 percent of added Cr was oxidized to Cr(VI) in microcosms prepared using older Mojave River aquifer material. Less Cr(VI) (less than 3 percent of Cr added before reduction) was released to the aqueous phase, and this release occurred following longer oxygen exposure. Site managers may need to plan for long-term monitoring and the possibility of active maintenance of anoxic conditions within the IRZ to ensure permanent sequestration of Cr after bioremediation with ethanol ceases.