Decoding oxygenation hisotory of the Earth via isotopologue analysis of sulfate

• Project/Area Number: 21H04513
• Research Category: Grant-in-Aid for Scientific Research (A)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Medium-sized Section 17:Earth and planetary science and related fields
• 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): 中川 麻悠子 東京工業大学, 地球生命研究所, 特任助教 (20647664)
• Project Period (FY): 2021-04-05 – 2025-03-31
• Project Status: Granted (Fiscal Year 2024)
• Budget Amount: ¥41,470,000 (Direct Cost: ¥31,900,000、Indirect Cost: ¥9,570,000); Fiscal Year 2024: ¥10,010,000 (Direct Cost: ¥7,700,000、Indirect Cost: ¥2,310,000); Fiscal Year 2023: ¥11,570,000 (Direct Cost: ¥8,900,000、Indirect Cost: ¥2,670,000); Fiscal Year 2022: ¥11,570,000 (Direct Cost: ¥8,900,000、Indirect Cost: ¥2,670,000); Fiscal Year 2021: ¥8,320,000 (Direct Cost: ¥6,400,000、Indirect Cost: ¥1,920,000)
• Keywords: 元素循環 / 酸素 / 硫黄 / 二重置換同位体分子

Outline of Research at the Start

大気酸素濃度の上昇は地球大気海洋における元素循環を本質的に変化させ、生物圏の有様を決定づけたと考えられている。しかしながら、それぞれの時代ごとに、酸素の生物地球化学循環を定量的に解読するための地質記録は限られている。本研究では、硫酸(SO4)の酸素・硫黄同位体を同時に計測し、かつ34S-18O二重置換度同位体分子種という全く新しいトレーサーを加えることで、硫酸塩が記録する多様な情報を引き出す。最終的に、大陸の酸化的風化、微生物硫酸還元、および熱水活動の３つの硫酸フラックスが、いつどれだけ変動したかを定量的に推定し、地球酸化史の実態を解明する。

Outline of Annual Research Achievements

硫酸同位体分子計測の精度低下を引き起こす要因を調査した結果、SiF4およびCClF4の二種が妨害分子として計測に影響を与えていることが特定された。これらの妨害分子は真空ライン内部の汚染が原因となってフッ化の際に微量ながら形成されるものであるため、フッ化真空ラインのバルブ等部品交換を順次行った。また、二種の妨害分子が影響を与える場合には、d18OとD34S18O値の間にそれぞれ特有の相関をもつ偏差を与えることから、計測値の補正法を考案すると同時に、多段階GC精製によってそれらの影響を排除できることが明らかになった。これらの分析法についてはTechnical Noteとして公表予定であり、その原稿を投稿した。
一方、これまでに行った予察的硫酸同位体分析の結果、原生代中期の硫酸塩が高い二重置換度を示し、これが報告されている硫酸D17O値の低下と同期することが明らかになった。この経年変化の要因は今後明らかにされるが、高い二重置換度はいくつかの河川水硫酸の特徴と類似するため、大陸の酸化的風化による河川水硫酸フラックスの変動と関係しているとする作業仮説を得た。これら成果の一部については2022年5月末に開催されたInternational Isotopomer Symosiumにおいて発表した。

Current Status of Research Progress

2: Research has progressed on the whole more than it was originally planned.

Reason

前年度に分析前処理装置の劣化が判明し、そのため研究計画に遅延が生じたが、その要因の特定がなされたため、改善の方向に進んでいる。また、当初計画ではリース契約であった高質量分解能質量分析計を購入することで分析法の改善が柔軟に行うことができるようになった。

Strategy for Future Research Activity

硫酸同位体分子計測の精度低下を引き起こす要因については多段階GC精製によって改善が可能だが、その行程には多くの時間を要する。多数の試料を計測してスループットを向上させる目的で、引き続き分析法の改善を行う。また、硫酸二重置換度の変動についてその要因が特定されつつあるため、仮説の実証に特化した実証実験の計画をさらに具体化し、実行する。

Research Products

• [Int'l Joint Research] 西オーストラリア大学/ゲッチンゲン大学(オーストラリア)
• [Int'l Joint Research] 西オーストラリア大学(オーストラリア)
• [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 Issue: 1 Pages: 5790-5790
  • 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): Yusuke Kubota, Fumihiro Matsuura, Kenji Shimizu, Akira Ishikawa, Yuichiro Ueno
  • Journal Title: Earth and Plenetary Science Letters Volume: 598 Pages: 117826-117826
  • DOI: 10.1016/j.epsl.2022.117826
  • Peer Reviewed / Open Access / 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., and Takai K.
  • Journal Title: Precambrian Research Volume: 373 Pages: 106628-106628
  • DOI: 10.1016/j.precamres.2022.106628
  • Peer Reviewed / Open Access / 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 / Open Access / 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 Motoko、Takahashi Yoshio、Uematsu Katsuyuki、Takeichi Yasuo、Ueno Yuichiro、Takai Ken
  • Journal Title: GEOCHEMICAL JOURNAL Volume: 56 Issue: 4 Pages: 129-133
  • DOI: 10.2343/geochemj.GJ22010
  • ISSN: 0016-7002, 1880-5973
  • Peer Reviewed / Open Access / 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: 121064-121064
  • DOI: 10.1016/j.chemgeo.2022.121064
  • Peer Reviewed / Open Access / Int'l Joint Research
• [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 Issue: 7 Pages: 1417-1417
  • DOI: 10.3390/microorganisms10071417
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Tracing sulfur sources in the crust via SIMS measurement of sulfur isotopes in apatite (2021)
  • Author(s): Hammerli Johannes、Greber Nicolas D.、Martin Laure、Bouvier Anne-Sophie、Kemp Anthony I.S.、Fiorentini Marco L.、Spangenberg Jorge E.、Ueno Yuichiro、Schaltegger Urs
  • Journal Title: Chemical Geology Volume: in press Pages: 120242-120242
  • DOI: 10.1016/j.chemgeo.2021.120242
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Spatial distribution and speciation of sulfur in Ediacaran limestones with μ-XRF imaging and XANES spectroscopy: Implications for diagenetic mobilization of sulfur species (2021)
  • Author(s): Matsu'ura Fumihiro、Nakada Ryoichi、Usui Tomohiro、Sawaki Yusuke、Ueno Yuichiro、Kajitani Iori、Saitoh Masafumi
  • Journal Title: Geochimica et Cosmochimica Acta Volume: 306 Pages: 20-43
  • DOI: 10.1016/j.gca.2021.05.010
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Multiple sulfur isotope chemostratigraphy across the Permian Triassic boundary at Chaotian, China: Implications for a shoaling model of toxic deep‐waters (2021)
  • Author(s): Saitoh Masafumi、Ueno Yuichiro、Isozaki Yukio、Yoshida Naohiro
  • Journal Title: Island Arc Volume: 30 Issue: 1
  • DOI: 10.1111/iar.12398
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Standardization for 13C‐13C clumped isotope analysis by fluorination method (2021)
  • Author(s): Taguchi Koudai、Gilbert Alexis、Ueno Yuichiro
  • Journal Title: Rapid Communications in Mass Spectrometry Volume: in press Issue: 13
  • DOI: 10.1002/rcm.9109
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Determinism of microbial community assembly by drastic environmental change (2021)
  • Author(s): Nishida Akifumi、Nakagawa Mayuko、Yamamura Masayuki
  • Journal Title: PLOS ONE Volume: 16 Issue: 12 Pages: e0260591-e0260591
  • DOI: 10.1371/journal.pone.0260591
  • Peer Reviewed / Open Access
• [Journal Article] High 3He/4He in central Panama reveals a distal connection to the Galapagos plume (2021)
  • Author(s): Bekaert D. V., Nakagawa M., et al.
  • Journal Title: Proceedings of the National Academy of Sciences Volume: 118 Issue: 47
  • DOI: 10.1073/pnas.2110997118
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Doubly substituted isotopologues of methane hydrate (13CH3D and 12CH2D2): Implications for methane clumped isotope effects, source apportionments and global hydrate reservoirs (2021)
  • Author(s): Zhang Naizhong、Snyder Glen T.、Lin Mang、Nakagawa Mayuko、Gilbert Alexis、Yoshida Naohiro、Matsumoto Ryo、Sekine Yasuhito
  • Journal Title: Geochimica et Cosmochimica Acta Volume: 315 Pages: 127-151
  • DOI: 10.1016/j.gca.2021.08.027
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Effect of tectonic processes on biosphere-geosphere feedbacks across a convergent margin (2021)
  • Author(s): Fullerton Katherine M.、Nakagawa Mayuko、Giovannelli Donato、Lloyd Karen G. et al.
  • Journal Title: Nature Geoscience Volume: 14 Issue: 5 Pages: 301-306
  • DOI: 10.1038/s41561-021-00725-0
  • Peer Reviewed / 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] 火星からの手紙 (2022)
  • Author(s): 上野 雄一郎
  • Organizer: ISAS Astrobiology Symposium
  • Int'l Joint Research / Invited
• [Presentation] Sulfur mass-independent fractionation patterns during SO2 photolysis under low temperature and low pressure atmosphere: implication for Archean atmospheric composition (2021)
  • Author(s): Yoshiaki Endo, Yasuhito Sekine, Yuichiro Ueno
  • Organizer: JpGU2021
• [Presentation] The micro-scale speciation analyses of sulfur in the Ediacaran limestones: Implications for diagenetic mobilization of sulfur species (2021)
  • Author(s): Fumihiro Matsuura, Ryoichi Nakada, Yusuke Sawaki, Yuichiro Ueno, Masafumi Saitoh, Kajitani Iori, Tomohiro Usui
  • Organizer: JpGU2021
• [Presentation] Geochemical drivers of microbial mediated iron reduction/oxidation in Proterozoic analogue environments (2021)
  • Author(s): Fatima Li-Hau, Mayuko Nakagawa, Lewis M. Ward, Takeshi Kakegawa, Yuichiro Ueno, Shawn McGlynn
  • Organizer: JpGU2021
• [Presentation] Application of fluorination method to isotopologue biogeochemistry (2021)
  • Author(s): Yuichiro Ueno, Koudai Taguchi, Toshiki Katsuta, Mayuko Nakagawa, Naohiro Yoshida, Alexis Gilbert
  • Organizer: Goldschmidt Conference
  • Int'l Joint Research
• [Presentation] Low 13C-13C clumping on abiotic hydrocarbons (2021)
  • Author(s): Koudai Taguchi, Alexis Gilbert, Yuichiro Ueno
  • Organizer: Goldschmidt Conference
  • Int'l Joint Research
• [Presentation] Δ34S18O systematics of modern sulfate (2021)
  • Author(s): Toshiki Katsuta, Yuichiro Ueno, Mayuko Nakagawa, Riho Aoki, Naohiro Yoshida
  • Organizer: Goldschmidt Conference
  • Int'l Joint Research
• [Presentation] Speciation and quantification of sulfur distributed in the Ediacaran limestones: Implications for diagenetic mobilization of sulfur species (2021)
  • Author(s): Fumihiro Matsuura, Ryoichi Nakada, Yusuke Sawaki, Yuichiro Ueno, Masafumi Saitoh, Kajitani Iori, Tomohiro Usui
  • Organizer: Goldschmidt Conference
  • Int'l Joint Research
• [Presentation] Missing negative Δ33S reservoir in mantle inferred from 2.7 Ga komatiite (2021)
  • Author(s): Shun Nakano, Akira Ishikawa, Yuichiro Ueno, Tetsuya Yokoyama
  • Organizer: Goldschmidt Conference
  • Int'l Joint Research
• [Presentation] Highly siderophile elements behavior in the Paleoarchean Camel Creek komatiites from East Pilbara Terrane, Western Australia (2021)
  • Author(s): Yusuke Kubota, Fumihiro Matsu'ura, Kenji Shimizu, Akira Ishikawa, Yuichiro Ueno
  • Organizer: Goldschmidt Conference
  • Int'l Joint Research
• [Presentation] Ancient Organic Material and Improving Detection Confidence Using Stable Isotopes (2021)
  • Author(s): Yuichiro Ueno
  • Organizer: NAS Committee on Astrobiology and Planetary Sciences 2021 Fall Meeting
  • Int'l Joint Research
• [Presentation] Atmospheric CO in prebiotic Earth-like planet (2021)
  • Author(s): Yuichiro Ueno
  • Organizer: AGU Fall Meeting
  • Int'l Joint Research / Invited
• [Presentation] Δ34S18O systematics of modern sulfate (2021)
  • Author(s): Toshiki Katsuta, Yuichiro Ueno, Mayuko Nakagawa, Riho Aoki, Naohiro Yoshida
  • Organizer: GOLDSCHMIDT
  • Int'l Joint Research
• [Presentation] The role of ferrous saponite in the formation of sulfur-bearing organic matter on early Earth and early Mars (2021)
  • Author(s): Natsumi Noda, Yasuhito Sekine, Yoshio Takahashi, Hiroshi Sakuma, Takahiro Kawai, Mayuko Nakagawa, Norio Kitadai, Kristin Johnson-Finn, Shawn E McGlynn
  • Organizer: GOLDSCHMIDT
  • Int'l Joint Research
• [Presentation] Volatile characteristics of Central American geothermal fluids (2021)
  • Author(s): Peter H Barry, David V Bekaert, Maarten de Moor, Jabrane Labidi, Esteban Gazel, Mayuko Nakagawa, Donato Giovannelli, Matt Schrenk, Karen Lloyd
  • Organizer: GOLDSCHMIDT
  • Int'l Joint Research