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      Organic synthesis on Mars by electrochemical reduction of CO 2

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          Abstract

          Organic synthesis on Mars occurs by the electrochemical reduction of CO 2, a reaction that is highly relevant for abiotic organic synthesis on early Earth.

          Abstract

          The sources and nature of organic carbon on Mars have been a subject of intense research. Steele et al. (2012) showed that 10 martian meteorites contain macromolecular carbon phases contained within pyroxene- and olivine-hosted melt inclusions. Here, we show that martian meteorites Tissint, Nakhla, and NWA 1950 have an inventory of organic carbon species associated with fluid-mineral reactions that are remarkably consistent with those detected by the Mars Science Laboratory (MSL) mission. We advance the hypothesis that interactions among spinel-group minerals, sulfides, and a brine enable the electrochemical reduction of aqueous CO 2 to organic molecules. Although documented here in martian samples, a similar process likely occurs wherever igneous rocks containing spinel-group minerals and/or sulfides encounter brines.

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          Most cited references67

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          Electrochemical CO2 Reduction on Metal Electrodes

          Y Hori (2008)
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            Organic molecules in the Sheepbed Mudstone, Gale Crater, Mars

            The Sample Analysis at Mars (SAM) instrument on board the Mars Science Laboratory Curiosity rover is designed to conduct inorganic and organic chemical analyses of the atmosphere and the surface regolith and rocks to help evaluate the past and present habitability potential of Mars at Gale Crater. Central to this task is the development of an inventory of any organic molecules present to elucidate processes associated with their origin, diagenesis, concentration, and long-term preservation. This will guide the future search for biosignatures. Here we report the definitive identification of chlorobenzene (150–300 parts per billion by weight (ppbw)) and C2 to C4 dichloroalkanes (up to 70 ppbw) with the SAM gas chromatograph mass spectrometer (GCMS) and detection of chlorobenzene in the direct evolved gas analysis (EGA) mode, in multiple portions of the fines from the Cumberland drill hole in the Sheepbed mudstone at Yellowknife Bay. When combined with GCMS and EGA data from multiple scooped and drilled samples, blank runs, and supporting laboratory analog studies, the elevated levels of chlorobenzene and the dichloroalkanes cannot be solely explained by instrument background sources known to be present in SAM. We conclude that these chlorinated hydrocarbons are the reaction products of Martian chlorine and organic carbon derived from Martian sources (e.g., igneous, hydrothermal, atmospheric, or biological) or exogenous sources such as meteorites, comets, or interplanetary dust particles. Key Points First in situ evidence of nonterrestrial organics in Martian surface sediments Chlorinated hydrocarbons identified in the Sheepbed mudstone by SAM Organics preserved in sample exposed to ionizing radiation and oxidative condition
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              Organic matter preserved in 3-billion-year-old mudstones at Gale crater, Mars

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                Author and article information

                Journal
                Sci Adv
                Sci Adv
                SciAdv
                advances
                Science Advances
                American Association for the Advancement of Science
                2375-2548
                October 2018
                31 October 2018
                : 4
                : 10
                : eaat5118
                Affiliations
                [1 ]Carnegie Institution for Science, Geophysical Laboratory, Washington, DC 20015, USA.
                [2 ]German Research Centre for Geosciences, GFZ, Telegrafenberg, 14473 Potsdam, Germany.
                [3 ]Department of Earth Sciences, Free University of Berlin, 12249 Berlin, Germany.
                [4 ]School of Earth and Environment, University of Leeds, Leeds LS2 9JT, UK.
                [5 ]RISE Research Institutes of Sweden, Bioscience and Materials/Chemistry, Materials and Surfaces, Box 5607, 114 86 Stockholm, Sweden.
                [6 ]NASA, Johnson Space Center, Houston, TX 77058, USA.
                [7 ]Department of Terrestrial Magnetism, Carnegie Institution of Washington, 5241 Broad Branch Rd, Washington, DC 20015, USA.
                [8 ]Earth and Environmental Sciences, Rensselaer Polytechnic Institute, 110 8th Street, Troy, NY 12180, USA.
                [9 ]NASA Goddard Space Flight Center, Greenbelt, MD 20771, USA.
                [10 ]USRA–Science and Technology Institute, 320 Sparkman Drive, Huntsville, AL 35805, USA.
                [11 ]Advanced Light Source, 1 Cyclotron Road, MS 7R0222, LBNL, Berkeley, CA 94720, USA.
                [12 ]ICRAG, Department of Geology, Trinity College Dublin, Dublin 2, Ireland.
                Author notes
                [* ]Corresponding author. Email: asteele@ 123456carnegiescience.edu
                [†]

                Deceased.

                Author information
                http://orcid.org/0000-0001-9643-2841
                http://orcid.org/0000-0001-9972-5578
                http://orcid.org/0000-0002-4975-6074
                http://orcid.org/0000-0002-7449-4774
                http://orcid.org/0000-0001-5724-3343
                http://orcid.org/0000-0001-7588-4603
                http://orcid.org/0000-0003-3089-1986
                http://orcid.org/0000-0003-1983-2774
                http://orcid.org/0000-0002-7671-2413
                http://orcid.org/0000-0002-8805-8690
                http://orcid.org/0000-0001-5978-3001
                Article
                aat5118
                10.1126/sciadv.aat5118
                6209388
                30402538
                6bf1ec9e-8ae8-4e7b-9f7d-14d85eb428f8
                Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).

                This is an open-access article distributed under the terms of the Creative Commons Attribution-NonCommercial license, which permits use, distribution, and reproduction in any medium, so long as the resultant use is not for commercial advantage and provided the original work is properly cited.

                History
                : 06 March 2018
                : 25 September 2018
                Funding
                Funded by: doi http://dx.doi.org/10.13039/100000015, U.S. Department of Energy;
                Award ID: DE-AC02-05CH11231
                Funded by: doi http://dx.doi.org/10.13039/100000104, National Aeronautics and Space Administration;
                Award ID: NNX13AJ19G
                Funded by: doi http://dx.doi.org/10.13039/100000104, National Aeronautics and Space Administration;
                Award ID: NNX14AT28G
                Funded by: doi http://dx.doi.org/10.13039/501100001859, Swedish National Space Board;
                Award ID: 121/11
                Funded by: doi http://dx.doi.org/10.13039/501100001859, Swedish National Space Board;
                Award ID: 198/15
                Funded by: doi http://dx.doi.org/10.13039/501100010956, Helmholtz-Zentrum Potsdam - Deutsches GeoForschungsZentrum GFZ;
                Award ID: RECRUITING INITIATIVE
                Funded by: doi http://dx.doi.org/10.13039/501100001862, Swedish Research Council Formas;
                Award ID: 2015-04129
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                Space Sciences
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