Enhancing microbial iron reduction in hyperalkaline, chromium contaminated sediments by pH amendment

Soil collected from beneath a chromite ore processing residue (COPR) disposal site contained a diverse population of anaerobic alkaliphiles, despite receiving a continuous influx of a Cr(VI) contaminated, hyperalkaline leachate (pH 12.2). Chromium was found to have accumulated in this soil as a result of an abiotic reaction of Cr(VI) with Fe(II) present in the soil. This sediment associated Fe(II) was, therefore, acting as a natural reactive zone beneath the COPR and thereby preventing the spread of Cr(VI). In anaerobic microcosm experiments soil microorganisms were able to reduce NO3- at pH 11.2 coupled to the oxidation of electron donors derived from the original soil organic matter, but progressive anoxia did not develop to the point of Fe reduction over a period of 9 months. It is not clear, therefore, if Fe(II) can be actively replenished by microbial processes occurring within the soil at in situ conditions. Sodium bicarbonate was added to this soil to investigate whether bioreduction of Fe in hyperalkaline Cr contaminated soils could be enhanced by reducing the pH to a value optimal for many alkaliphilic bacteria. The addition of NaHCO3 produced a well buffered system with a pH of ∼9.3 and Fe reducing conditions developed within 1 month once complete denitrification had occurred. Fe(III) reduction was associated with an increase in the proportion of genetic clone libraries that were from the phylum Firmicutes, suggesting that these species are responsible for the Fe(III) reduction observed. Amendment of the pH using bicarbonate may provide a suitable strategy for stimulating the bioreduction of Fe(III) in COPR leachate contaminated soils or other environments where microbial reduction is inhibited by elevated pH.