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"abstract": "Clay minerals and methanogens are ubiquitous and co-exist in anoxic environments, yet it is unclear whether methanogens are able to reduce structural Fe(III) in clay minerals. In this study, the ability of methanogen\u00a0Methanosarcina barkeri\u00a0to reduce structural Fe(III) in iron-rich smectite (nontronite NAu-2) and the relationship between iron reduction and methanogenesis were investigated. Bioreduction experiments were conducted in growth medium using three types of substrate: H2/CO2, methanol, and acetate. Time course methane production and hydrogen consumption were measured by gas chromatography.\u00a0M. barkeri\u00a0was able to reduce structural Fe(III) in NAu-2 with H2/CO2\u00a0and methanol as substrate, but not with acetate. The extent of bioreduction, as measured by the 1,10-phenanthroline method, was 7\u201313% with H2/CO2\u00a0as substrate, depending on nontronite concentration (5\u201310\u00a0g/L). The extent was higher when methanol was used as a substrate, reaching 25\u201333%. Methanogenesis was inhibited by Fe(III) reduction in the H2/CO2\u00a0culture, but enhanced when methanol was used. High charge smectite and biogenic silica formed as a result of bioreduction. Our results suggest that methanogens may play an important role in biogeochemical cycling of iron in clay minerals and may have important implications for the global methane budget.",
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