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: Institute of Science Tokyo
• 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

当初使用していた硫酸塩標準試料が世界的に枯渇したため、今年度はまず新たに海水硫酸標準試料の作成を行った。前年度までに、地表における硫化鉄の酸化的風化過程が高い二重置換度をもち、他の硫酸リザバーと区別可能であるとの仮説を得ていた。本年度はこれを実証し、メカニズムを明らかにするため、風化実験を行い、その硫黄同位体、酸素同位体、二重置換度の同時計測を主に行った。また共同研究者からも同種の実験試料を入手し計測した。その結果、硫酸の酸素は（１）水、(2)大気中酸素の二者に由来するが、その割合はいくつかのパラメーター（酸化鉄の有無等）によって異なることが判明した。この条件の違いにより、酸化的風化過程においても二重置換度は常に高い値をとるとは限らないことが分かった。一方、これまで計測した河川硫酸試料はほぼ高い二重置換度を示しており、その要因を明らかにすることが重要である。一方、原生代の硫黄循環について、これまでに硫酸塩試料は限られていたが、頁岩中硫化鉄の四主硫黄同位体計測をmm空間スケールの局所分析で行うことにより、還元前の硫酸硫黄同位体組成を復元可能であることが示された。これら成果については日本地球化学会等において発表した。

Current Status of Research Progress

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

Reason

今年度は標準試料の作成など、当初想定していない手間がかかったが、酸化的風化過程が特異的な二重置換度を持つことが示唆されたため、鍵となるプロセスの解明に集中する方向性が具体的になった。また、当初想定していなかった手法で過去の海水硫酸硫黄同位体組成を復元できる見通しがついた。

Strategy for Future Research Activity

硫酸同位体分子計測のスループット向上はまだ達成されておらず、これをCoF3フッ化法を用いて達成する計画である。また、硫酸二重置換度の変動要因について、引き続き風化実験を行うとともに、本年度は硫酸還元菌の培養実験について本格的に取り組む。

Research Products

• [Int'l Joint Research] 西オーストラリア大学(オーストラリア)
• [Int'l Joint Research] ゲッチンゲン大学(ドイツ)
• [Int'l Joint Research] USGS(米国)
• [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] Deep Subseafloor Biogeochemical Processes and Microbial Populations Potentially Associated with the 2011 Tohoku-oki Earthquake at the Japan Trench Accretionary Wedge (IODP Expedition 343) (2023)
  • Author(s): Kawagucci Shinsuke、Sakai Sanae、Tasumi Eiji、Hirai Miho、Takaki Yoshihiro、Nunoura Takuro、Saitoh Masafumi、Ueno Yuichiro、Yoshida Naohiro、Shibuya Takazo、Clifford Sample James、Okumura Tomoyo、Takai Ken
  • Journal Title: Microbes and Environments Volume: 38 Issue: 2 Pages: n/a
  • DOI: 10.1264/jsme2.ME22108
  • ISSN: 1342-6311, 1347-4405
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Nitrogen Isotope Record From a Mid‐oceanic Paleo‐Atoll Limestone to Constrain the Redox State of the Panthalassa Ocean in the Capitanian (Late Guadalupian, Permian) (2023)
  • Author(s): Saitoh Masafumi、Nishizawa Manabu、Ozaki Kazumi、Ikeda Masayuki、Ueno Yuichiro、Takai Ken、Isozaki Yukio
  • Journal Title: Paleoceanography and Paleoclimatology Volume: 38 Issue: 6
  • DOI: 10.1029/2022pa004573
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Large sulfur isotope fractionation during abiotic consumption of hydrogen sulfide after cessation of bacterial growth in batch culture experiments of sulfate reducing bacteria (2023)
  • Author(s): Matsu'ura Fumihiro、Makita Hiroko、Takai Ken、Nakagawa Mayuko、Ueno Yuichiro
  • Journal Title: Earth and Planetary Science Letters Volume: 624 Pages: 118446-118446
  • DOI: 10.1016/j.epsl.2023.118446
  • 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 Issue: 1 Pages: 5790-5790
  • DOI: 10.1038/s41467-022-33538-9
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• [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
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• [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] Redox change in Paleoproterozoic estimated from multiple sulfur isotope analysis of Francevillian successions in Gabon (2023)
  • Author(s): 栗原在, 佐藤友彦, 澤木佑介, Moussavou Mathieu, 上野雄一郎
  • Organizer: JpGU 2023
• [Presentation] 硫酸同位体分子が語る酸化的風化、微生物硫酸還 元および熱水循環 (2023)
  • Author(s): 上野 雄一郎, Jakub Surma
  • Organizer: 2023年度 日本地球化学会 第70回年会
• [Presentation] Wavelength dependent fractionation of carbon isotopes and its implication for carbon cycle on early Mars (2023)
  • Author(s): Yuichiro Ueno and Matthew Stanley Johnson
  • Organizer: AGU Annual Meeting 2023
  • Int'l Joint Research / Invited
• [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
• [Book] 最新 地学事典 (2023)
  • Author(s): 上野雄一郎 ほか
  • Total Pages: 2046
  • Publisher: 平凡社
  • ISBN: 9784582115086
• [Remarks] 動画で見る東工大研究2023 ～4分で知る！未来を創る最先端研究～
  • URL: https://www.titech.ac.jp/news/2023/066994