Microbial reduction of Fe(III) under alkaline conditions relevant to geological disposal.

To determine whether biologically mediated Fe(III) reduction is possible under alkaline conditions in systems of relevance to geological disposal of radioactive wastes, a series of microcosm experiments was set up using hyperalkaline sediments (pH ~11.8) surrounding a legacy lime working site in Buxton, United Kingdom. The microcosms were incubated for 28 days and held at pH 10. There was clear evidence for anoxic microbial activity, with consumption of lactate (added as an electron donor) concomitant with the reduction of Fe(III) as ferrihydrite (added as the electron acceptor). The products of microbial Fe(III) reduction were black and magnetic, and a range of analyses, including X-ray diffraction, transmission electron microscopy, X-ray absorption spectroscopy, and X-ray magnetic circular dichroism confirmed the extensive formation of biomagnetite in this system. The addition of soluble exogenous and endogenous electron shuttles such as the humic analogue anthraquinone-2,6-disulfonate and riboflavin increased both the initial rate and the final extent of Fe(III) reduction in comparison to the nonamended experiments. In addition, a soluble humic acid (Aldrich) also increased both the rate and the extent of Fe(III) reduction. These results show that microbial Fe(III) reduction can occur in conditions relevant to a geological disposal facility containing cement-based wasteforms that has evolved into a high pH environment over prolonged periods of time (>100,000 years). The potential impact of such processes on the biogeochemistry of a geological disposal facility is discussed, including possible coupling to the redox conditions and solubility of key radionuclides.