A detailed assessment of studies of oxidising redox fronts around fractures at depth in otherwise “reducing” environments suggests that the usual explanation, in terms of past disturbances that have resulted in deep penetration of oxidising water, are incompatible with hydrogeological and/or geochemical observations. An alternative hypothesis, microbial catalysis of kinetically slow or hindered reactions involving oxyanions such as sulphate or carbonate, appears potentially more credible. Although still not always taken into account by the geochemical community, the role of microbial metabolism in low temperature geochemistry is supported by the rapidly expanding database on subsurface microbial populations. These populations are demonstrated to be viable and, therefore, could potentially be active at levels close to or below current detection limits in deep geological systems. Indeed, inspection of information available from several analogue studies or repository site characterisation programmes suggests that such activity may explain some of the geochemical anomalies encountered. This paper examines the current (indirect) evidence for microbial redox catalysis in relevant subsurface rock matrix environments and considers the implications that this would have for the development of site understanding — and in particular the identification of factors that may distinguish between different locations during site selection. Further, it examines the wider implications of more extensive roles of microbes in repository systems on the overall post-closure safety case and the need for further focused analogue studies to develop answers to these open questions.

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