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Reduction of structural Fe(III) in nontronite by methanogen Methanosarcina barkeri
Authors:Deng Liu  Michael E Bishop  Abinash Agrawal  Dennis D Eberl
Institution:a Key Laboratory of Biogeology and Environmental Geology of Ministry of Education, China University of Geosciences, Wuhan 430074, China
b Geomicrobiology Laboratory, State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Beijing 100083, China
c Department of Geology, Miami University, Oxford, OH 45056, USA
d Department of Earth and Environmental Sciences, Wright State University, Dayton, OH 45435, USA
e United States Geological Survey, Boulder, CO 80303, USA
f State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan 430074, China
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 Methanosarcina barkeri to 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. M. barkeri was able to reduce structural Fe(III) in NAu-2 with H2/CO2 and methanol as substrate, but not with acetate. The extent of bioreduction, as measured by the 1,10-phenanthroline method, was 7-13% with H2/CO2 as substrate, depending on nontronite concentration (5-10 g/L). The extent was higher when methanol was used as a substrate, reaching 25-33%. Methanogenesis was inhibited by Fe(III) reduction in the H2/CO2 culture, 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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