Arsenic is a highly toxic element that supports a surprising range of biogeochemical transformations. The biochemical basis of these microbial interactions is described, with an emphasis on energy-yielding redox biotransformations that cycle between the As5+ and As3+ oxidation states. The subsequent impact of As3+-oxidising and As5+-reducing prokaryotes on the chemistry of selected environments is also described, focusing on soda lakes with naturally high concentrations of the metalloid and on Southeast Asian aquifer sediments, where the microbial reduction of sorbed As5+ and subsequent mobilisation of As3+ into water abstracted for drinking and irrigation threaten the lives of millions.

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