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Serpentinization: Connecting geochemistry, ancient metabolism and industrial hydrogenation

Preiner, Martina; Xavier, Joana C.; Sousa, Filipa L.; Zimorski, Verena; Neubeck, Anna; Lang, Susan Q.; Greenwell, Chris; Kleinermanns, Karl; Tüysüz, Harun; McCollom, Tom M.; Holm, Nils G.; Martin, William F.

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Martina Preiner

Joana C. Xavier

Filipa L. Sousa

Verena Zimorski

Anna Neubeck

Susan Q. Lang

Karl Kleinermanns

Harun Tüysüz

Tom M. McCollom

Nils G. Holm

William F. Martin


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.


Preiner, M., Xavier, J. C., Sousa, F. L., Zimorski, V., Neubeck, A., Lang, S. Q., …Martin, W. F. (2018). Serpentinization: Connecting geochemistry, ancient metabolism and industrial hydrogenation. Life, 8(4), Article 41.

Journal Article Type Article
Acceptance Date Sep 20, 2018
Online Publication Date Sep 22, 2018
Publication Date Sep 22, 2018
Deposit Date Sep 20, 2018
Publicly Available Date Sep 26, 2018
Journal Life
Publisher MDPI
Peer Reviewed Peer Reviewed
Volume 8
Issue 4
Article Number 41


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Copyright Statement
© 2018 by the authors. Licensee MDPI, Basel, Switzerland. This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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