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      Chemical evolution of primordial salts and organic sulfur molecules in the asteroid 162173 Ryugu

      research-article
      1 , , 1 , 2 , 1 , 3 , 1 , 4 , 5 , 4 , 6 , 7 , 7 , 8 , 9 , 1 , 10 , 7 , 7 , 1 , 11 , 11 , 12 , 13 , 14 , 15 , 2 , 16 , 17 , 17 , 17 , 17 , 17 , 17 , 17 , 17 , 17 , 17 , 17 , 17 , 18 , 17 , 10 , 17 , 17 , 19 , Hayabusa2-initial-analysis SOM team
      Nature Communications
      Nature Publishing Group UK
      Asteroids, comets and Kuiper belt, Meteoritics

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          Abstract

          Samples from the carbonaceous asteroid (162173) Ryugu provide information on the chemical evolution of organic molecules in the early solar system. Here we show the element partitioning of the major component ions by sequential extractions of salts, carbonates, and phyllosilicate-bearing fractions to reveal primordial brine composition of the primitive asteroid. Sodium is the dominant electrolyte of the salt fraction extract. Anions and NH 4 + are more abundant in the salt fraction than in the carbonate and phyllosilicate fractions, with molar concentrations in the order SO 4 2− > Cl − > S 2O 3 2− > NO 3 − > NH 4 +. The salt fraction extracts contain anionic soluble sulfur-bearing species such as S n -polythionic acids ( n < 6), C n -alkylsulfonates, alkylthiosulfonates, hydroxyalkylsulfonates, and hydroxyalkylthiosulfonates ( n < 7). The sulfur-bearing soluble compounds may have driven the molecular evolution of prebiotic organic material transforming simple organic molecules into hydrophilic, amphiphilic, and refractory S allotropes.

          Abstract

          The asteroid Ryugu samples are by far the freshest extraterrestrial carbonaceous material. The authors report soluble ions and organic sulfur molecules linked with primordial brine and prebiotic organic evolution of the primitive asteroid.

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          Most cited references48

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          High molecular diversity of extraterrestrial organic matter in Murchison meteorite revealed 40 years after its fall.

          Numerous descriptions of organic molecules present in the Murchison meteorite have improved our understanding of the early interstellar chemistry that operated at or just before the birth of our solar system. However, all molecular analyses were so far targeted toward selected classes of compounds with a particular emphasis on biologically active components in the context of prebiotic chemistry. Here we demonstrate that a nontargeted ultrahigh-resolution molecular analysis of the solvent-accessible organic fraction of Murchison extracted under mild conditions allows one to extend its indigenous chemical diversity to tens of thousands of different molecular compositions and likely millions of diverse structures. This molecular complexity, which provides hints on heteroatoms chronological assembly, suggests that the extraterrestrial chemodiversity is high compared to terrestrial relevant biological- and biogeochemical-driven chemical space.
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            On the chemical evolution of the carbonaceous chondrites

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              Organosulfate formation in biogenic secondary organic aerosol.

              Organosulfates of isoprene, alpha-pinene, and beta-pinene have recently been identified in both laboratory-generated and ambient secondary organic aerosol (SOA). In this study, the mechanism and ubiquity of organosulfate formation in biogenic SOA is investigated by a comprehensive series of laboratory photooxidation (i.e., OH-initiated oxidation) and nighttime oxidation (i.e., NO3-initiated oxidation under dark conditions) experiments using nine monoterpenes (alpha-pinene, beta-pinene, d-limonene, l-limonene, alpha-terpinene, gamma-terpinene, terpinolene, Delta(3)-carene, and beta-phellandrene) and three monoterpenes (alpha-pinene, d-limonene, and l-limonene), respectively. Organosulfates were characterized using liquid chromatographic techniques coupled to electrospray ionization combined with both linear ion trap and high-resolution time-of-flight mass spectrometry. Organosulfates are formed only when monoterpenes are oxidized in the presence of acidified sulfate seed aerosol, a result consistent with prior work. Archived laboratory-generated isoprene SOA and ambient filter samples collected from the southeastern U.S. were reexamined for organosulfates. By comparing the tandem mass spectrometric and accurate mass measurements collected for both the laboratory-generated and ambient aerosol, previously uncharacterized ambient organic aerosol components are found to be organosulfates of isoprene, alpha-pinene, beta-pinene, and limonene-like monoterpenes (e.g., myrcene), demonstrating the ubiquity of organosulfate formation in ambient SOA. Several of the organosulfates of isoprene and of the monoterpenes characterized in this study are ambient tracer compounds for the occurrence of biogenic SOA formation under acidic conditions. Furthermore, the nighttime oxidation experiments conducted under highly acidic conditions reveal a viable mechanism for the formation of previously identified nitrooxy organosulfates found in ambient nighttime aerosol samples. We estimate that the organosulfate contribution to the total organic mass fraction of ambient aerosol collected from K-puszta, Hungary, a field site with a similar organosulfate composition as that found in the present study for the southeastern U.S., can be as high as 30%.
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                Author and article information

                Contributors
                yoshimurat@jamstec.go.jp
                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group UK (London )
                2041-1723
                18 September 2023
                18 September 2023
                2023
                : 14
                : 5284
                Affiliations
                [1 ]GRID grid.410588.0, ISNI 0000 0001 2191 0132, Biogeochemistry Research Center (BGC), Japan Agency for Marine-Earth Science and Technology (JAMSTEC), ; Natsushima 2-15, Yokosuka, Kanagawa 237-0061 Japan
                [2 ]GRID grid.177174.3, ISNI 0000 0001 2242 4849, Department of Earth and Planetary Sciences, , Kyushu University, ; 744 Motooka, Nishi-ku, Fukuoka, 819-0395 Japan
                [3 ]GRID grid.466781.a, ISNI 0000 0001 2222 3430, Geological Survey of Japan (GSJ), National Institute of Advanced Industrial Science and Technology (AIST), ; 1-1-1 Higashi, Tsukuba, Ibaraki 305-8567 Japan
                [4 ]GRID grid.4567.0, ISNI 0000 0004 0483 2525, Helmholtz Zentrum München, Analytical BioGeoChemistry, Ingolstaedter Landstrasse 1, ; 85764 Neuherberg, Germany
                [5 ]GRID grid.6936.a, ISNI 0000000123222966, Technische Universität München, Analytische Lebensmittel Chemie, Maximus-von-Forum 2, ; 85354 Freising, Germany
                [6 ]GRID grid.39158.36, ISNI 0000 0001 2173 7691, Institute of Low Temperature Science (ILTS), , Hokkaido University, ; N19W8 Kita-ku, Sapporo, 060-0189 Japan
                [7 ]GRID grid.133275.1, ISNI 0000 0004 0637 6666, Solar System Exploration Division, NASA Goddard Space Flight Center, ; Greenbelt, MD 20771 USA
                [8 ]HORIBA Advanced Techno, Co., Ltd., Kisshoin, Minami-ku, Kyoto, 601-8510 Japan
                [9 ]HORIBA Techno Service Co., Ltd. Kisshoin, Minami-ku, Kyoto 601-8510 Japan
                [10 ]GRID grid.27476.30, ISNI 0000 0001 0943 978X, Department of Earth and Planetary Sciences, , Nagoya University, ; Nagoya, 464-8601 Japan
                [11 ]GRID grid.459494.1, Thermo Fisher Scientific Inc., 3-9 Moriyacho, Kanagawa-ku, ; Yokohama-shi, Kanagawa 221-0022 Japan
                [12 ]GRID grid.32197.3e, ISNI 0000 0001 2179 2105, Department of Earth and Planetary Sciences, , Tokyo Institute of Technology, Ookayama, ; Meguro, Tokyo 152-8551 Japan
                [13 ]GRID grid.39158.36, ISNI 0000 0001 2173 7691, Creative Research Institution (CRIS), Hokkaido University, ; Sapporo, Hokkaido 001-0021 Japan
                [14 ]GRID grid.69566.3a, ISNI 0000 0001 2248 6943, Department of Earth Science, , Tohoku University, ; Sendai, 980-8678 Japan
                [15 ]GRID grid.258799.8, ISNI 0000 0004 0372 2033, Department of Earth and Planetary Sciences, , Kyoto University, ; Kyoto, 606-8502 Japan
                [16 ]GRID grid.257022.0, ISNI 0000 0000 8711 3200, Earth and Planetary Systems Science Program, Hiroshima University, ; Higashi Hiroshima, 739-8526 Japan
                [17 ]GRID grid.450279.d, ISNI 0000 0000 9989 8906, Institute of Space and Astro-nautical Science, Japan Aerospace Exploration Agency (ISAS/JAXA), ; Sagamihara, Kanagawa 229-8510 Japan
                [18 ]GRID grid.419709.2, ISNI 0000 0004 0371 3508, Kanagawa Institute of Technology, ; Atsugi, 243-0292 Japan
                [19 ]GRID grid.26999.3d, ISNI 0000 0001 2151 536X, UTokyo Organization for Planetary and Space Science (UTOPS), University of Tokyo, ; Bunkyo-ku, Tokyo 113-0033 Japan
                [20 ]GRID grid.177174.3, ISNI 0000 0001 2242 4849, Graduate School of Pharmaceutical Sciences, , Kyushu University, ; Fukuoka, 812-8582 Japan
                [21 ]GRID grid.27476.30, ISNI 0000 0001 0943 978X, Graduate School of Bioagricultural Sciences, , Nagoya University, ; Nagoya, 464-8601 Japan
                [22 ]GRID grid.133275.1, ISNI 0000 0004 0637 6666, Center for Research and Exploration in Space Science and Technology, NASA Goddard Space Flight Center, ; Greenbelt, MD 20771 USA
                [23 ]GRID grid.39936.36, ISNI 0000 0001 2174 6686, Department of Physics, , The Catholic University of America, ; Washington, DC 20064 USA
                [24 ]GRID grid.20861.3d, ISNI 0000000107068890, Division of Geological and Planetary Sciences, California Institute of Technology, ; Pasadena, CA 91125 USA
                [25 ]GRID grid.463924.e, ISNI 0000 0004 0452 4645, Université Aix-Marseille, CNRS, Laboratoire de Physique des Interactions Ioniques et Moléculaires, ; Marseille, 13397 France
                [26 ]GRID grid.5252.0, ISNI 0000 0004 1936 973X, Department of Chemistry and Pharmacy, , Ludwig-Maximilians-University, ; Munich, 81377 Germany
                [27 ]GRID grid.510544.1, Excellence Cluster ORIGINS, ; Garching, 85748 Germany
                [28 ]GRID grid.457026.2, Université Grenoble Alpes, Centre National de la Recherche Scientifique (CNRS), Centre National d’Etudes Spatiales, L’Institut de Planétologie et d’Astrophysique de Grenoble, ; Grenoble, 38000 France
                [29 ]GRID grid.32197.3e, ISNI 0000 0001 2179 2105, Earth-Life Science Institute (ELSI), Tokyo Institute of Technology, ; Tokyo, 152-8550 Japan
                [30 ]GRID grid.254124.4, ISNI 0000 0001 2294 246X, Planetary Exploration Research Center, Chiba Institute of Technology, ; Narashino, 275-0016 Japan
                [31 ]GRID grid.4444.0, ISNI 0000 0001 2112 9282, Université Paris-Saclay, CNRS, Institut de Chimie Physique, ; Orsay, 91405 France
                [32 ]GRID grid.418051.9, ISNI 0000 0000 8774 3245, Department of Life, Environment and Material Science, , Fukuoka Institute of Technology, ; Fukuoka, 811-0295 Japan
                [33 ]GRID grid.69566.3a, ISNI 0000 0001 2248 6943, Department of Earth Science, , Tohoku University, ; Sendai, 980-8578 Japan
                [34 ]HORIBA Techno Service Co., Ltd., Kyoto, 601-8305 Japan
                [35 ]LECO Japan Corp., Tokyo, 105-0014 Japan
                [36 ]GRID grid.26091.3c, ISNI 0000 0004 1936 9959, Institute for Advanced Biosciences (IAB), Keio University, Kakuganji, ; Tsuruoka, Yamagata 997-0052 Japan
                [37 ]Human Metabolome Technologies (HMT) Inc., Kakuganji, Tsuruoka, Yamagata 997-0052 Japan
                [38 ]GRID grid.26999.3d, ISNI 0000 0001 2151 536X, Department of Health Chemistry, Graduate School of Pharmaceutical Sciences, , The University of Tokyo, Hongo, ; Tokyo, 113-0033 Japan
                [39 ]GRID grid.69566.3a, ISNI 0000 0001 2248 6943, Department of Robotics, Graduate school of Engineering, , Tohoku University, ; Sendai, Miyagi 980-8579 Japan
                Author information
                http://orcid.org/0000-0003-0478-4239
                http://orcid.org/0000-0003-1151-144X
                http://orcid.org/0000-0001-5728-0590
                http://orcid.org/0000-0001-5249-4995
                http://orcid.org/0000-0002-3823-6444
                http://orcid.org/0000-0003-0824-2664
                http://orcid.org/0000-0002-2519-2905
                http://orcid.org/0000-0002-6852-3604
                http://orcid.org/0000-0002-3961-8997
                http://orcid.org/0000-0002-0131-1981
                http://orcid.org/0000-0002-0302-2171
                http://orcid.org/0000-0003-2247-7232
                http://orcid.org/0000-0003-0702-0533
                http://orcid.org/0000-0001-7211-2595
                http://orcid.org/0000-0002-4625-5362
                http://orcid.org/0000-0001-5138-5324
                http://orcid.org/0000-0002-7971-510X
                http://orcid.org/0000-0003-2392-1497
                http://orcid.org/0000-0001-7427-2285
                http://orcid.org/0000-0002-3717-9185
                http://orcid.org/0000-0001-6381-8107
                http://orcid.org/0000-0002-4653-293X
                http://orcid.org/0000-0003-4250-1826
                http://orcid.org/0000-0002-5820-2102
                http://orcid.org/0000-0002-4603-9440
                Article
                40871
                10.1038/s41467-023-40871-0
                10507048
                37723151
                2b6d4cef-1575-47ba-8a43-6cf10f40d461
                © Springer Nature Limited 2023

                Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.

                History
                : 23 February 2023
                : 10 August 2023
                Funding
                Funded by: FundRef https://doi.org/10.13039/501100001691, MEXT | Japan Society for the Promotion of Science (JSPS);
                Award ID: 21H01204
                Award ID: 21KK0062
                Award ID: 20H00202
                Award ID: 21H04501&21H05414
                Award Recipient :
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                © Springer Nature Limited 2023

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                asteroids, comets and kuiper belt,meteoritics
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                asteroids, comets and kuiper belt, meteoritics

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