Decoding CO world in early Earth and Mars

2022 Fiscal Year Annual Research Report

• Project Area: CO world
• Project/Area Number: 22H05151
• Research Institution: Tokyo Institute of Technology
• Principal Investigator: 上野 雄一郎 東京工業大学, 理学院, 教授 (90422542)
• Co-Investigator(Kenkyū-buntansha): 山田 桂太 東京工業大学, 物質理工学院, 准教授 (70323780) ; ジルベルト アレキシー 東京工業大学, 理学院, 准教授 (20726955) ; 青木 翔平 東京大学, 大学院新領域創成科学研究科, 講師 (60773629)
• Project Period (FY): 2022-06-16 – 2027-03-31
• Keywords: 同位体分子 / 初期地球 / 火星探査 / バイオマーカー

Outline of Annual Research Achievements

高質量分解能安定同位体比質量分析計のバージョンアップを行い、炭化水素類の13C-13C, 13C-2H同位体分子種に加え,存在度の低い2H-2H同位体分子計測を可能とした。　特に本年度はエタンおよびエタノールの13C-13C二重置換同位体分子種の存在度について、これまでの観測に加えて実験的研究を加え、それを解析した結果、無機的にC1化合物から合成した炭化水素ガスはその重合の際に13C-13C結合が形成されにくいことが原因となり、生物起源の炭化水素（エタン)と二重置換度が明瞭に異なることが明らかになった（Taguchi et al., 2022 Nature Communications)。
また、生物班と共同で白馬八方地域およびマリアナ前弧域深海探査を行い、蛇紋岩熱水・湧水の炭化水素および有機酸等を採取し、またこれら試料から微量な有機酸を抽出した。
一方、理論班との共同研究により、大気光化学モデルに同位体分別を導入した理論モデルを構築し、現在の火星大気COが極度に13Cに枯渇することを理論的に予測すると同時に、それが観測可能であることを示した　(Yoshida, Aoki, Ueno et al., 2023)。この成果はさらに、分担者の青木が主導する火星大気の分光観測（Aoki, Ueno et al. 査読中)と、代表者の上野が行った室内実験(Ueno, Kurokawa, Usui et al., 査読中)と調和的である。
さらに、化学班と共同して行っているCO大気の光化学実験によると、CO大気からはN2OおよびNH3からアミノ酸が合成されるだけでなく、イミダゾール等、核酸塩基に類似する複素環式化合物も合成されることが明らかになった。こうした結果は想定外のものであったが、惑星のCO環境下で生命代謝につながる化学系を構築・実証する上で重要である。

Current Status of Research Progress

1: Research has progressed more than it was originally planned.

Reason

13C-13C二重置換度による炭化水素の起源判別法(Taguchi, Gilbert, Ueno et al., 2022 Nature Communications)は新規の生物指標（バイオマーカー）を構築する上で大きな成果と言える。また、火星大気COの研究が進展し、これまで認識されてこなかったCOの炭素同位体異常について、理論・実験・観測の３方向からそのメカニズムが検証されつつある。これは、過去の惑星大気においてCOから有機物が形成されるプロセスを明らかにするうえで、その基盤が強固となった点で意義が大きい。
さらに、CO大気から実験的に複素環式化合物が合成されることを明らかになった。この結果は想定を上回るものであり、惑星のCO環境下で生命代謝につながる化学系を構築・実証する上で大きな進展である。

Strategy for Future Research Activity

環境物質の起源推定法をより強固にしていくため、これまでに確立した同位体分子計測技術を応用し、適用可能な分子種を順次拡張する。そのため、高質量分解能質量分析計を順次アップグレードする計画である。
生物班との共同研究において今後は特に採取した蛇紋岩水系の試料分析に注力すると同時に、培養実験も展開する。
理論班との共同研究においては、引き続き大気モデル・生態系モデルに同位体分別を導入する分別係数の決定を実験的に行い、観測と比較する。
化学班との共同研究においては、今後は模擬大気UV実験をC-NルートおよびC-Sルートへと展開することで、惑星CO環境において生命代謝につながる化学系を構築・実証していく。そのため、特にアミノ酸を効率よく生成する自己触媒的な化学系の構築に狙いを定める

Research Products

• [Int'l Joint Research] コペンハーゲン大学(デンマーク)
  • Country Name: DENMARK
  • Counterpart Institution: コペンハーゲン大学
• [Int'l Joint Research] 西オーストラリア大学(オーストラリア)
  • Country Name: AUSTRALIA
  • Counterpart Institution: 西オーストラリア大学
• [Int'l Joint Research] ヘルムホルツ-センター ポツダム(ドイツ)
  • Country Name: GERMANY
  • Counterpart Institution: ヘルムホルツ-センター ポツダム
• [Int'l Joint Research] Belgian Institute for Space Aeronomy(ベルギー)
  • Country Name: BELGIUM
  • Counterpart Institution: Belgian Institute for Space Aeronomy
• [Journal Article] The noble gas and nitrogen relationship between Ryugu and carbonaceous chondrites (2023)
  • Author(s): Broadley M. W., K. Yamada, et al.
  • Journal Title: Geochimica et Cosmochimica Acta Volume: 345 Pages: 62-74
  • DOI: 10.1016/j.gca.2023.01.020
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Martian Ozone Observed by TGO/NOMAD‐UVIS Solar Occultation: An Inter‐Comparison of Three Retrieval Methods (2023)
  • Author(s): A. Piccialli, A. C. Vandaele, Y. Willame, A. Maattanen, L. Trompet, J. T. Erwin, F. Daerden, L. Neary, S. Aoki, S. Viscardy, I. R. Thomas, C. Depiesse, B. Ristic, J. P. Mason, M. R. Patel, M. J. Wolff, A. S. J. Khayat, G. Bellucci, J.‐J. Lopez‐Moreno
  • Journal Title: Earth and Space Science Volume: 10 (2) Pages: e2022EA002429
  • DOI: 10.1029/2022ea002429
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Carbon dioxide retrievals from NOMAD‐SO on ESA’s ExoMars Trace Gas Orbiter and temperature profiles retrievals with the hydrostatic equilibrium equation. II. Temperature variabilities in the mesosphere at Mars terminator. (2023)
  • Author(s): L. Trompet, A.C. Vandaele, I. Thomas, S. Aoki, F. Daerden, J. Erwin, Z. Flimon, A. Mahieux, L. Neary, S. Robert, G. Villanueva, G. Liuzzi, Lopez Valverde, A. Brines, G. Bellucci, J. J. Lopez‐Moreno, M. R. Patel
  • Journal Title: Journal of Geophysical Research: Planets Volume: 128, 3 Pages: e2022JE007279
  • DOI: 10.1029/2022je007279
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Carbon dioxide retrievals from NOMAD‐SO on ESA’s ExoMars Trace Gas Orbiter and temperature profiles retrievals with the hydrostatic equilibrium equation. I. Description of the method (2023)
  • Author(s): L. Trompet, A.C. Vandaele, I. Thomas, S. Aoki, F. Daerden, J. Erwin, Z. Flimon, A. Mahieux, L. Neary, S. Robert, G. Villanueva, G. Liuzzi, Lopez‐Valverde, A. Brines, G. Bellucci, J. J. Lopez‐Moreno, M. R. Patel
  • Journal Title: Journal of Geophysical Research: Planets Volume: 128, 3 Pages: e2022JE007277
  • DOI: 10.1029/2022je007277
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Retrieval of Martian atmospheric CO vertical profiles from NOMAD observations during the 1st year of TGO operations (2023)
  • Author(s): Ashimananda Modak, Shohei Aoki, et al.
  • Journal Title: Journal of Geophysical Research: Planets Volume: 128, 3 Pages: e2022JE007282
  • DOI: 10.1029/2022je007282
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Strong depletion of 13C in CO induced by photolysis of CO2 in the Martian atmosphere calculated by a photochemical model (2022)
  • Author(s): Yoshida, T., Aoki, S., Ueno, Y., Terada, N., Nakamura, Y., Shiobara, K., Yoshida, N., Nakagawa, H., Sakai, S., Koyama, S.,
  • Journal Title: Planetary Science Journal Volume: 4 Pages: -
  • DOI: 10.3847/PSJ/acc030
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Low 13C-13C abundances in abiotic ethane (2022)
  • Author(s): Taguchi, K., Gilbert, A., Sherwood Lollar, B., Giunta, T., Boreham, C.J., Liu, Q., Horita, J., Ueno, Y.,
  • Journal Title: Nature Communications Volume: 13 Pages: -
  • DOI: 10.1038/s41467-022-33538-9
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Sulfur in Archean komatiite implies early subduction of oceanic lithosphere (2022)
  • Author(s): Kubota, Y., Matsu’ura, F., Shimizu, K., Ishikawa, A., Ueno, Y.,
  • Journal Title: Earth and Planetary Science Letters Volume: 598 Pages: -
  • DOI: 10.1016/j.epsl.2022.117826
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Spatial distribution of organic functional groups in Ediacaran acritarchs from the Doushantuo Formation in South China as revealed by micro-FTIR spectroscopy (2022)
  • Author(s): Igisu, M., Ueno, Y., Komiya, T., Awramik, S.M., Ikemoto, Y., Takai, K.,
  • Journal Title: Precambrian Research Volume: 373 Pages: -
  • DOI: 10.1016/j.precamres.2022.106628
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Sulfur isotope systematics of granitoids from the Yilgarn Craton shed new light on the fluid reservoirs of Neoarchean orogenic gold deposits (2022)
  • Author(s): Caruso, S., Fiorentini, M.L., Champion, D.C., Lu, Y., Ueno, Y., Smithies, R.H.,
  • Journal Title: Precambrian Research Volume: 326 Pages: 199-213
  • DOI: 10.1016/j.gca.2022.03.023
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] STXM-XANES analyses of carbonaceous matter in seafloor hydrothermal deposits from the ~3.5 Ga Dresser Formation in the North Pole area, Western Australia (2022)
  • Author(s): Igisu, M., Takahashi, Y., Uematsu, K., Takeichi, Y., Ueno, Y., Takai, K.,
  • Journal Title: Geochemical Journal Volume: 56 Pages: 129-133
  • DOI: 10.2343/geochemj.GJ22010
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Sulfur mass-independent fractionation during SO2 photolysis in low-temperature/pressure atmospheres (2022)
  • Author(s): Endo, Y., Sekine, Y., Ueno, Y.,
  • Journal Title: Chemical Geology Volume: 609 Pages: -
  • DOI: 10.1016/j.chemgeo.2022.121064
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Photochemical synthesis of ammonia and amino acids from nitrous oxide (2022)
  • Author(s): Zang, X., Ueno, Y., Kitadai, N.,
  • Journal Title: Astrobiology Volume: 22 Pages: 387-398
  • DOI: 10.1089/ast.2021.0064
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Re-evaluation of the 13C isotope fractionation associated with lipids biosynthesis by position-specific isotope analysis of plant fatty acids (2022)
  • Author(s): Julien M., Zhao Y., Ma R., Zhou Y.P., Nakagawa M., Yamada K., Yoshida N., Remaud G.S., Gilbert A.
  • Journal Title: Organic Geochemistry Volume: 174 Pages: -
  • DOI: 10.1016/j.orggeochem.2022.104516
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] First asteroid gas sample delivered by the Hayabusa2 mission: A treasure box from Ryugu (2022)
  • Author(s): Okazaki R. Yamada. K, et al.
  • Journal Title: Science Advances Volume: 8 Pages: 2375-2548
  • DOI: 10.1126/sciadv.abo7239
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] The GAs Extraction and Analyses system (GAEA) for immediate extraction and measurements of volatiles in the Hayabusa2 sample container (2022)
  • Author(s): Miura Y.N., Okazaki R., Takano Y., Sakamoto K., Tachibana S., Yamada K., Sakai s., Sawada H.
  • Journal Title: Earth, Planets and Space Volume: 74 Pages: -
  • DOI: 10.1186/s40623-022-01638-x
  • Peer Reviewed / Open Access
• [Journal Article] Source analysis of dissolved methane in Chukchi Sea and Bering Strait during summer-autumn of 2012 and 2013 (2022)
  • Author(s): Kudo K., Toyoda S., Yamada K., Yoshida N. Sasano D., Kosugi N., Muata A., Uchida H., Nishino S.
  • Journal Title: Marine Chemistry Volume: 243 Pages: -
  • DOI: 10.1016/j.marchem.2022.104119
  • Peer Reviewed
• [Journal Article] Hydrocarbon Cycling in the Tokamachi Mud Volcano (Japan): Insights from Isotopologue and Metataxonomic Analyses (2022)
  • Author(s): A. Gilbert, Mayuko Nakagawa, Koudai Taguchi, Naizhong Zhang, Akifumi Nishida, Naohiro Yoshida
  • Journal Title: Microorganisms Volume: 7 Pages: 1417
  • DOI: 10.3390/microorganisms10071417
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Water vapor vertical distribution on Mars during perihelion season of MY 34 and MY 35 with ExoMars‐TGO/NOMAD observations (2022)
  • Author(s): A. Brines, M. A. Lopez‐Valverde, A. Stolzenbach, A. Modak, B. Funke, F. G. Galindo, S. Aoki, G. L. Villanueva, G. Liuzzi, I. R. Thomas, J. T. Erwin, U. Grabowski, F. Forget, J. J. Lopez‐Moreno, J. Rodriguez‐Gomez, F. Daerden, L. Trompet, B. Ristic, M. R. Patel, G. Bellucci, A. C. Vandaele
  • Journal Title: Journal of Geophysical Research: Planets Volume: 128, 3 Pages: e2022JE007273
  • DOI: 10.1029/2022je007273
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Martian atmospheric temperature and density profiles during the 1st year of NOMAD/TGO solar occultation measurements (2022)
  • Author(s): Miguel‐Angel Lopez Valverde, Shohei Aoki, et al.
  • Journal Title: Journal of Geophysical Research: Planets Volume: 128, 2 Pages: e2022JE007278
  • DOI: 10.1029/2022je007278
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Global variations in water vapour and saturation state throughout the Mars Year 34 dusty season (2022)
  • Author(s): J. A. Holmes, S. R. Lewis, M. R. Patel, J. Alday, S. Aoki, G. Liuzzi, G. L. Villanueva, M. M. J. Crismani, A. A. Fedorova, K. S. Olsen, D. M. Kass, A. C. Vandaele, O. Korablev
  • Journal Title: Journal of Geophysical Research: Planets Volume: 127, 10 Pages: e2022JE007203
  • DOI: 10.1029/2022je007203
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Global vertical distribution of water vapor on Mars: Results from 3.5 years of ExoMars‐TGO/NOMAD science operations (2022)
  • Author(s): S. Aoki, A. C. Vandaele, F. Daerden, G. L. Villanueva, G. Liuzzi, R. T. Clancy, M. A. Lopez‐Valverde, A. Brines, I. R. Thomas, L. Trompet, J. T. Erwin, L. Neary, S. Robert, A. Piccialli, J. A. Holmes, M. R. Patel, N. Yoshida, J. Whiteway, M. D. Smith, B. Ristic, G. Bellucci, J. J. Lopez‐Moreno, A. A. Fedorova
  • Journal Title: Journal of Geophysical Research: Planets Volume: 127, 9 Pages: e2022JE007231
  • DOI: 10.1029/2022je007231
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Planet‐Wide Ozone Destruction in the Middle Atmosphere on Mars During Global Dust Storm (2022)
  • Author(s): F. Daerden, S. Aoki, et al.
  • Journal Title: Geophysical Research Letters Volume: 49 (11) Pages: e2022GL098821
  • DOI: 10.1029/2022gl098821
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] The deuterium isotopic ratio of water released from the Martian caps as measured with TGO/NOMAD (2022)
  • Author(s): Geronimo L. Villanueva, Shohei Aoki, et al.
  • Journal Title: Geophysical Research Letters Volume: 49 (12) Pages: e2022GL098161
  • DOI: 10.1029/2022gl098161
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Variations in Vertical CO/CO 2 Profiles in the Martian Mesosphere and Lower Thermosphere Measured by the ExoMars TGO/NOMAD: Implications of Variations in Eddy Diffusion Coefficient (2022)
  • Author(s): Nao Yoshida, Shohei Aoki, et al.
  • Journal Title: Geophysical Research Letters Volume: 49 (10) Pages: e2022GL098485
  • DOI: 10.1029/2022GL098485
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Density and temperature of the upper mesosphere and lower thermosphere of Mars retrieved from the OI 557.7 nm dayglow measured by TGO/NOMAD (2022)
  • Author(s): S. Aoki, L. Gkouvelis, J.‐C. Gerard, L. Soret, B. Hubert, M. A. Lopez‐Valverde, F. Gonzalez‐Galindo, H. Sagawa, I. R. Thomas, B. Ristic, Y. Willame, C. Depiesse, J. Mason, M. R. Patel, G. Bellucci, J.‐J. Lopez‐Moreno, F. Daerden, A. C. Vandaele
  • Journal Title: Journal of Geophysical Research: Planets Volume: 127, 6 Pages: e2022JE007206
  • DOI: 10.1029/2022JE007206
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] The Mars oxygen visible dayglow: A MARTIAN YEAR OF NOMAD/UVIS OBSERVATIONS (2022)
  • Author(s): L. Soret, J.‐C. Gerard, S. Aoki, L. Gkouvelis, I. R. Thomas, B. Ristic, B. Hubert, Y. Willame, C. Depiesse, A.C. Vandaele, M. R. Patel, J. P. Mason, F. Daerden, J.‐J. Lopez‐Moreno, G. Bellucci
  • Journal Title: Journal of Geophysical Research: Planets Volume: 127, 6 Pages: e2022JE007220
  • DOI: 10.1029/2022JE007220
  • Peer Reviewed / Int'l Joint Research
• [Presentation] Can CO world create life? Opening talk (2023)
  • Author(s): Ueno Y.
  • Organizer: CO world workshop on Chemical Roots of Metabolism
  • Int'l Joint Research
• [Presentation] 初期火星大気のCOから生成する有機物 (2023)
  • Author(s): 上野 雄一郎
  • Organizer: 第24回 惑星圏研究会 (SPS2023)
  • Int'l Joint Research / Invited
• [Presentation] Large carbon isotope fractionation implies a CO world on early Mars (2023)
  • Author(s): Ueno Y., Schmidt J., Johnson M., Ozaki K., Kurokawa H., Usui T.
  • Organizer: NOMAD SWT#23 (International conference on new insights into Mars achieved by remote-sensing observation, numerical simulation, and laboratory experiment of trace gases)
  • Int'l Joint Research
• [Presentation] UPDATE ON ISOTOPE STUDY: 13C/12C RATIO IN CO OBSERVED BY IRTF/ISHELL (FIRST ATTEMPT (2023)
  • Author(s): 青木 翔平
  • Organizer: NOMAD SWT meeting #23, Matsushima, Japan
  • Int'l Joint Research
• [Presentation] Tracing oxygen in sulfate using 34S-18O clumping (2022)
  • Author(s): Ueno Y, Surma J, Katsuta T, Ishimaru T, Nakagawa M, Crockford P.W., Bao H., Yoshida N.
  • Organizer: ISI2022
  • Int'l Joint Research
• [Presentation] The compositional dichotomy of ca. 3.3 Ga komatiites from the West Pilbara (2022)
  • Author(s): Kubota Y., Nakano S., Ishikawa A., and Ueno Y.
  • Organizer: Goldschmidt Conference
  • Int'l Joint Research
• [Presentation] Potential mechanisms to synthesize amino acids from nitrous oxide and carbon monoxide through large molecular weight precursor (2022)
  • Author(s): Zang, X., Ueno, Y.
  • Organizer: Goldschmidt Conference
  • Int'l Joint Research / Invited
• [Presentation] 還元的な初期火星大気のCOから生成する有機物の異常な13C枯渇 (2022)
  • Author(s): Ueno Y., Schmidt J., Johnson M., Zang X.
  • Organizer: 地球化学会年会
  • Int'l Joint Research
• [Presentation] Can CO world create an evolvable chemical system? (2022)
  • Author(s): Ueno Y., Ozaki K., Zang X., Smith E., Kurokawa H., Schmidt J., Johnson M.S., Kitadai N., Suzuki S.
  • Organizer: ELSI mini symposium
  • Int'l Joint Research
• [Presentation] Deciphering Hydrocarbons’ Sources and Sinks through Isotopologue measurements (2022)
  • Author(s): Alexis Gilbert
  • Organizer: GRC Organic Geochemistry
  • Int'l Joint Research / Invited
• [Presentation] Isotopologues of organic molecules: method developments and applications (2022)
  • Author(s): Alexis Gilbert
  • Organizer: ISI/Isotopes 2022
  • Int'l Joint Research / Invited
• [Presentation] Global vertical distribution of water vapor on Mars: Results from 2 Mars years of ExoMars-TGO/NOMAD science operations (2022)
  • Author(s): 青木 翔平
  • Organizer: Seventh international workshop on the Mars atmosphere: Modelling and observations, Paris,
  • Int'l Joint Research
• [Presentation] 13C/12C RATIO IN CO OBSERVED BY NOMAD SO CHANNEL ~PRELIMINARY RESULTS~ (2022)
  • Author(s): 青木 翔平
  • Organizer: NOMAD SWT meeting #22, IASB-BIRA, Brussels
  • Int'l Joint Research
• [Presentation] UPDATE ON WATER AND HCL RETRIEVALS FROM THE SO-CHANNEL (2022)
  • Author(s): 青木 翔平
  • Organizer: NOMAD SWT meeting #22, IASB-BIRA, Brussels
  • Int'l Joint Research
• [Remarks] CO環境の生命惑星化学
  • URL: https://co-world.jp
• [Remarks] 生命由来の有機分子を見分ける新手法を開発： 生物由来のエタン分子が持つ特徴的な13C-13C結合度
  • URL: https://www.titech.ac.jp/news/2022/065170
• [Remarks] Detect the Signature of Biotic Hydrocarbons
  • URL: https://www.titech.ac.jp/english/news/2022/065167