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Geochemistry and the Origin of Life: From Extraterrestrial Processes, Chemical Evolution on Earth, Fossilized Life’s Records, to Natures of the Extant Life
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Serpentinization: Connecting Geochemistry, Ancient Metabolism and Industrial Hydrogenation

Institute of Molecular Evolution, University of Düsseldorf, 40225 Düsseldorf, Germany
Division of Archaea Biology and Ecogenomics, Department of Ecogenomics and Systems Biology, University of Vienna, Althanstrasse 14 UZA I, 1090 Vienna, Austria
Department of Earth Sciences, Palaeobiology, Uppsala University, Geocentrum, Villavägen 16, SE-752 36 Uppsala, Sweden
School of the Earth, Ocean, and Environment, University of South Carolina, 701 Sumter St. EWS 401, Columbia, SC 29208, USA
Department of Earth Sciences, Durham University, South Road, DH1 3LE Durham, UK
Institute for Physical Chemistry, University of Düsseldorf, 40225 Düsseldorf, Germany
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany
Laboratory for Atmospheric and Space Physics, University of Colorado, Boulder, CO 80309, USA
Department of Geological Sciences, Stockholm University, SE-106 91 Stockholm, Sweden
Authors to whom correspondence should be addressed.
Received: 27 August 2018 / Revised: 18 September 2018 / Accepted: 20 September 2018 / Published: 22 September 2018
(This article belongs to the Special Issue Geochemistry and the Origin of Life)
Rock–water–carbon interactions germane to serpentinization in hydrothermal vents have occurred for over 4 billion years, ever since there was liquid water on Earth. Serpentinization converts iron(II) containing minerals and water to magnetite (Fe3O4) plus H2. The hydrogen can generate native metals such as awaruite (Ni3Fe), a common serpentinization product. Awaruite catalyzes the synthesis of methane from H2 and CO2 under hydrothermal conditions. Native iron and nickel catalyze the synthesis of formate, methanol, acetate, and pyruvate—intermediates of the acetyl-CoA pathway, the most ancient pathway of CO2 fixation. Carbon monoxide dehydrogenase (CODH) is central to the pathway and employs Ni0 in its catalytic mechanism. CODH has been conserved during 4 billion years of evolution as a relic of the natural CO2-reducing catalyst at the onset of biochemistry. The carbide-containing active site of nitrogenase—the only enzyme on Earth that reduces N2—is probably also a relic, a biological reconstruction of the naturally occurring inorganic catalyst that generated primordial organic nitrogen. Serpentinization generates Fe3O4 and H2, the catalyst and reductant for industrial CO2 hydrogenation and for N2 reduction via the Haber–Bosch process. In both industrial processes, an Fe3O4 catalyst is matured via H2-dependent reduction to generate Fe5C2 and Fe2N respectively. Whether serpentinization entails similar catalyst maturation is not known. We suggest that at the onset of life, essential reactions leading to reduced carbon and reduced nitrogen occurred with catalysts that were synthesized during the serpentinization process, connecting the chemistry of life and Earth to industrial chemistry in unexpected ways. View Full-Text
Keywords: rock–water–carbon interactions; origin of life; carbides; iron sulfur; early metabolism rock–water–carbon interactions; origin of life; carbides; iron sulfur; early metabolism
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Preiner, M.; Xavier, J.C.; Sousa, F.L.; Zimorski, V.; Neubeck, A.; Lang, S.Q.; Greenwell, H.C.; Kleinermanns, K.; Tüysüz, H.; McCollom, T.M.; Holm, N.G.; Martin, W.F. Serpentinization: Connecting Geochemistry, Ancient Metabolism and Industrial Hydrogenation. Life 2018, 8, 41.

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