Reductive biomining of pyrite by methanogens

Abstract

Pyrite (FeS₂) is the most abundant iron sulfide mineral in Earth's crust. Until recently, FeS₂ has been considered a sink for iron (Fe) and sulfur (S) at low temperature in the absence of oxygen or oxidative weathering, making these elements unavailable to biology. However, anaerobic methanogens can transfer electrons extracellularly to reduce FeS₂ via direct contact with the mineral. Reduction of FeS₂ occurs through a multistep process that generates aqueous sulfide (HS^-) and FeS₂-associated pyrrhotite (Fe_1-xS). Subsequent dissolution of Fe_1-xS provides Fe(II)_(aq), but not HS^-, that rapidly complexes with HS^-_(aq) generated from FeS₂ reduction to form soluble iron sulfur clusters [nFeS_(aq)]. Cells assimilate nFeS_(aq) to meet Fe/S nutritional demands by mobilizing and hyperaccumulating Fe and S from FeS₂. As such, reductive dissolution of FeS₂ by methanogens has important implications for element cycling in anoxic habitats, both today and in the geologic past.

Keywords: extracellular electron transfer; iron; mackinawite; methanogens; pyrrhotite; sulfur.