Elucidation of reaction mechanisms at gas-liquid interfaces in the atmosphere

• Project/Area Number: 19H01154
• Research Category: Grant-in-Aid for Scientific Research (A)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Medium-sized Section 63:Environmental analyses and evaluation and related fields
• Research Institution: University of Tsukuba (2022-2023); National Institute for Environmental Studies (2019-2021)
• Principal Investigator: Enami Shinichi 筑波大学, 数理物質系, 教授 (00589385)
• Project Period (FY): 2019-04-01 – 2023-03-31
• Project Status: Completed (Fiscal Year 2023)
• Budget Amount: ¥46,410,000 (Direct Cost: ¥35,700,000、Indirect Cost: ¥10,710,000); Fiscal Year 2022: ¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000); Fiscal Year 2021: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000); Fiscal Year 2020: ¥6,370,000 (Direct Cost: ¥4,900,000、Indirect Cost: ¥1,470,000); Fiscal Year 2019: ¥31,590,000 (Direct Cost: ¥24,300,000、Indirect Cost: ¥7,290,000)
• Keywords: エアロゾル / 界面 / ラジラジカル / 不均一反応 / マルチフェーズ反応 / 環境 / 気候変動 / 大気汚染 / 液相 / ラジカル / 界面反応 / 大気化学 / 質量分析 / フェントン反応 / エイジング / オゾニド / バルク / 物理化学 / レボグルコサン / テルペン / 反応 / 毒性 / 表面 / フェントン / オゾン / PM2.5 / 温暖化 / 健康影響

Outline of Research at the Start

本提案研究では、気液界面反応測定手法に加えて、瞬時に起こる液相反応をその場測定できる新規手法を開発し、気液界面反応vs液相反応を直接比較できる実験システムを構築する。それにより、気液界面で起こる反応の特殊性の起源の解明を目指す。本提案研究が完成すると、大気における界面反応とバルク反応をどのように定量的に区別して扱えばよいかが明らかになり、大気モデルへの取り込みなど、多くの成果が見込まれる。

Outline of Final Research Achievements

Atmospherically important reactions at the air-water interface were investigated by interface-sensitive spray ionization mass spectrometry. Furthermore, the dual-microjets mass spectrometry was developed for direct comparison between the interface vs bulk reaction mechanisms. The important knowledge on the origin of the interface-specific mechanisms was obtained. These results will be highly valuable for future atmospheric modeling.

Academic Significance and Societal Importance of the Research Achievements

気候変動と大気汚染の問題は人類が解決すべき重大な環境問題である。これらの問題と密接に関連する大気中に浮遊する雲粒とエアロゾルの気液界面と液相で起こる化学反応機構の分子レベルでの理解は極めて重要である。本研究によって、気液界面で起こる反応の特殊性の起源の一部が初めて明らかになった。また、大気における界面反応とバルク反応をどのように定量的に区別して扱えばよいかが明らかになった。今後、大気モデルへの取り込みなど、多くの成果が見込まれるため、重要である。

Research Products

• [Int'l Joint Research] Caltech(米国)
• [Int'l Joint Research] UC Riverside(米国)
• [Int'l Joint Research] Caltech(米国)
• [Journal Article] Impurity contribution to ultraviolet absorption of saturated fatty acids (2023)
  • Author(s): Saito Shota、Numadate Naoki、Teraoka Hidemasa、Enami Shinichi、Kobayashi Hirokazu、Hama Tetsuya
  • Journal Title: Science Advances Volume: 9 Issue: 38
  • DOI: 10.1126/sciadv.adj6438
  • Peer Reviewed / Open Access
• [Journal Article] Mechanism of Fenton Oxidation of Levoglucosan in Water (2023)
  • Author(s): Enami Shinichi、Morino Yu、Sato Kei
  • Journal Title: The Journal of Physical Chemistry A Volume: 127 Issue: 13 Pages: 2975-2985
  • DOI: 10.1021/acs.jpca.3c00512
  • Peer Reviewed
• [Journal Article] 大気マルチフェーズ化学：気液界面と液中で起こるオゾン反応 (2023)
  • Author(s): 江波進一
  • Journal Title: 大気環境学会誌 Volume: 58
  • Peer Reviewed
• [Journal Article] Direct Observation and Quantitative Measurement of OH Radical Desorption During the Ultraviolet Photolysis of Liquid Nonanoic Acid (2022)
  • Author(s): Naoki Numadate, Shota Saito, Yuki Nojima, Taka-aki Ishibashi, Shinichi Enami, and Tetsuya Hama
  • Journal Title: The Journal of Physical Chemistry Letters Volume: 13 Issue: 35 Pages: 8290-8297
  • DOI: 10.1021/acs.jpclett.2c02199
  • Peer Reviewed
• [Journal Article] Stability of Terpenoid-Derived Secondary Ozonides in Aqueous Organic Media (2022)
  • Author(s): Junting Qiu, Michiya Fujita, Kenichi Tonokura, and Shinichi Enami
  • Journal Title: The Journal of Physical Chemistry A Volume: 126 Issue: 32 Pages: 5386-5397
  • DOI: 10.1021/acs.jpca.2c04077
  • Peer Reviewed / Open Access
• [Journal Article] Proton-Catalyzed Decomposition of Multifunctionalized Organic Hydroperoxides Derived from the Reactions of Criegee Intermediates with Ethylene Glycol in Aqueous Organic Media (2022)
  • Author(s): Enami Shinichi
  • Journal Title: ACS Earth and Space Chemistry Volume: 6 Issue: 7 Pages: 1937-1947
  • DOI: 10.1021/acsearthspacechem.2c00142
  • Peer Reviewed
• [Journal Article] Decomposition of multifunctionalized α-alkoxyalkyl-hydroperoxides derived from the reactions of Criegee intermediates with diols in liquid phases (2022)
  • Author(s): Endo Yasuyuki、Sakamoto Yosuke、Kajii Yoshizumi、Enami Shinichi
  • Journal Title: Physical Chemistry Chemical Physics Volume: 24 Issue: 19 Pages: 11562-11572
  • DOI: 10.1039/d2cp00915c
  • Peer Reviewed
• [Journal Article] 未来の大気化学のための室内実験 (2022)
  • Author(s): 江波進一、石塚紳之助、羽馬哲也、猪俣敏
  • Journal Title: 大気化学研究 Volume: 47
  • Peer Reviewed
• [Journal Article] Decomposition mechanism of α-alkoxyalkyl-hydroperoxides in the liquid phase: temperature dependent kinetics and theoretical calculations (2022)
  • Author(s): Hu Mingxi、Chen Kunpeng、Qiu Junting、Lin Ying-Hsuan、Tonokura Kenichi、Enami Shinichi
  • Journal Title: Environmental Science: Atmospheres Volume: 2 Issue: 2 Pages: 241-251
  • DOI: 10.1039/d1ea00076d
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] テルペン由来クリーギー中間体の気液界面反応 (2022)
  • Author(s): 江波進一
  • Journal Title: エアロゾル研究 Volume: 37 Pages: 12-20
  • Peer Reviewed
• [Journal Article] Fates of Organic Hydroperoxides in Atmospheric Condensed Phases (2021)
  • Author(s): Enami Shinichi
  • Journal Title: The Journal of Physical Chemistry A Volume: 125 Issue: 21 Pages: 4513-4523
  • DOI: 10.1021/acs.jpca.1c01513
  • Peer Reviewed / Open Access
• [Journal Article] Hydronium Ion Acidity Above and Below the Interface of Aqueous Microdroplets (2021)
  • Author(s): Colussi Agustin J.、Enami Shinichi、Ishizuka Shinnosuke
  • Journal Title: ACS Earth and Space Chemistry Volume: 5 Issue: 9 Pages: 2341-2346
  • DOI: 10.1021/acsearthspacechem.1c00067
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Effects of Metal Ions on Aqueous-Phase Decomposition of α-Hydroxyalkyl-Hydroperoxides Derived from Terpene Alcohols (2021)
  • Author(s): Hu Mingxi、Tonokura Kenichi、Morino Yu、Sato Kei、Enami Shinichi
  • Journal Title: Environmental Science & Technology Volume: 55 Pages: 12893-12901
  • DOI: 10.1021/acs.est.1c04635
  • Peer Reviewed / Open Access
• [Journal Article] 空気－水の界面で起こる化学反応 (2021)
  • Author(s): 江波進一
  • Journal Title: ぶんせき Volume: 8 Pages: 380-386
  • NAID: 40022674772
  • Peer Reviewed
• [Journal Article] Stability of Monoterpene-Derived α-Hydroxyalkyl-Hydroperoxides in Aqueous Organic Media: Relevance to the Fate of Hydroperoxides in Aerosol Particle Phases (2020)
  • Author(s): Qiu Junting、Liang Zhancong、Tonokura Kenichi、Colussi Agustin J.、Enami Shinichi
  • Journal Title: Environmental Science & Technology Volume: 54 Issue: 7 Pages: 3890-3899
  • DOI: 10.1021/acs.est.9b07497
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Effects of pH on Interfacial Ozonolysis of α-Terpineol (2019)
  • Author(s): Qiu Junting、Ishizuka Shinnosuke、Tonokura Kenichi、Sato Kei、Inomata Satoshi、Enami Shinichi
  • Journal Title: The Journal of Physical Chemistry A Volume: 123 Issue: 32 Pages: 7148-7155
  • DOI: 10.1021/acs.jpca.9b05434
  • Peer Reviewed / Open Access
• [Journal Article] Acid-Catalyzed Oligomerization at the Air-Water Interface Modified by Competitive Adsorption of Surfactants (2019)
  • Author(s): Ishizuka Shinnosuke、Hama Tetsuya、Enami Shinichi
  • Journal Title: The Journal of Physical Chemistry C Volume: 123 Issue: 35 Pages: 21662-21669
  • DOI: 10.1021/acs.jpcc.9b07380
  • Peer Reviewed / Open Access
• [Journal Article] Comment on “The chemical reactions in electrosprays of water do not always correspond to those at the pristine air-water interface” by A. Gallo Jr, A. S. F. Farinha, M. Dinis, A.-H. Emwas, A. Santana, R. J. Nielsen, W. A. Goddard III and H. Mishra, Chem. Sci., 2019, 10, 2566 (2019)
  • Author(s): Colussi Agustin J.、Enami Shinichi
  • Journal Title: Chemical Science Volume: 10 Issue: 35 Pages: 8253-8255
  • DOI: 10.1039/c9sc00991d
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Water Dramatically Accelerates the Decomposition of α-Hydroxyalkyl-Hydroperoxides in Aerosol Particles (2019)
  • Author(s): Qiu Junting、Ishizuka Shinnosuke、Tonokura Kenichi、Colussi Agustin J.、Enami Shinichi
  • Journal Title: The Journal of Physical Chemistry Letters Volume: 10 Issue: 19 Pages: 5748-5755
  • DOI: 10.1021/acs.jpclett.9b01953
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Interfacial Water Mediates Oligomerization Pathways of Monoterpene Carbocations (2019)
  • Author(s): Ishizuka Shinnosuke、Matsugi Akira、Hama Tetsuya、Enami Shinichi
  • Journal Title: The Journal of Physical Chemistry Letters Volume: 11 Issue: 1 Pages: 67-74
  • DOI: 10.1021/acs.jpclett.9b03110
  • Peer Reviewed / Open Access
• [Presentation] 大気Å不均一科学の創成 (2024)
  • Author(s): 江波進一
  • Organizer: JSTさきがけ発展研究会
  • Invited
• [Presentation] 大気マルチフェーズ化学：気液界面と液中で起こるオゾン反応 (2022)
  • Author(s): 江波進一
  • Organizer: 第63回大気環境学会年会
  • Invited
• [Presentation] 微小不均一性は液相反応にどのような影響を与えるか？ (2022)
  • Author(s): 江波進一
  • Organizer: 第16回分子科学討論会
• [Presentation] テルペン由来オゾニドはエアロゾル中で分解するか？ (2022)
  • Author(s): 江波進一, 邱鈞霆, 藤田道也, 戸野倉賢一
  • Organizer: 第27回大気化学討論会
• [Presentation] 雲粒中で起こる化学反応の研究 (2022)
  • Author(s): 江波進一
  • Organizer: SATテクノロジー・ショーケース2023
• [Presentation] Fates of terpenoid-derived hydroperoxides in atmospheric condensed phases (2021)
  • Author(s): Enami Shinichi
  • Organizer: 6th International Workshop on Heterogeneous Kinetics Related to Atmospheric Aerosols
  • Int'l Joint Research / Invited
• [Presentation] 未来の大気化学のための室内実験 (2021)
  • Author(s): 江波進一, 石塚紳之助，羽馬哲也，猪俣敏
  • Organizer: 第26回大気化学討論会
  • Invited
• [Presentation] 空気―水の境界相で起こるラジカル反応のメカニズム (2020)
  • Author(s): 江波進一
  • Organizer: レーザー学会学術講演会第40回年次大会
  • Invited
• [Presentation] Fates of terpene alpha-hydroxyalkyl-hydroperoxides in aqueous aerosol (2019)
  • Author(s): Shinichi Enami
  • Organizer: 5th International Workshop on Heterogeneous Kinetics Related to Atmospheric Aerosols
  • Int'l Joint Research / Invited
• [Presentation] Interface-specific reaction pathways of monoterpene carbocations (2019)
  • Author(s): S. Ishizuka, A. Matsugi, T. Hama, S. Enami
  • Organizer: 35th Symposium on Chemical Kinetics and Dynamics
  • Int'l Joint Research
• [Presentation] エアロゾル中のテルペン由来過酸化物の分解メカニズム (2019)
  • Author(s): 江波進一, 邱鈞霆, 戸野倉賢一
  • Organizer: 第24回大気化学討論会
• [Presentation] Microhydration Mediates Cationic Polymerization at the Air-Water Interface (2019)
  • Author(s): S. Ishizuka, A. Matsugi, T. Hama, S. Enami
  • Organizer: 第68回高分子討論会
• [Presentation] 大気圏マルチフェーズ化学 (2019)
  • Author(s): 江波進一
  • Organizer: 京都大学生存圏研究所大気圏セミナー
  • Invited
• [Presentation] Surfactant effects on acid-catalyzed reactions at aqueous aerosol surfaces (2019)
  • Author(s): S. Ishizuka, T. Hama, S. Enami
  • Organizer: 日本地球惑星科学連合2019年大会