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

2019 Fiscal Year Annual Research Report

• Project/Area Number: 19H01154
• Research Institution: National Institute for Environmental Studies
• Principal Investigator: 江波 進一 国立研究開発法人国立環境研究所, 環境計測研究センター, 主任研究員 (00589385)
• Project Period (FY): 2019-04-01 – 2023-03-31
• Keywords: エアロゾル / エイジング / 毒性 / 界面 / 表面 / 液相 / フェントン / オゾン

Outline of Annual Research Achievements

大気エアロゾルが関与する反応には界面反応とバルク（液中）反応が混在しており、これまでの研究ではそれぞれの寄与を定量的に評価することができなかった。また界面で起こる反応とバルク中で起こる反応の違いが何に起因しているのかという物理化学的な起源に関しても、よくわかっていない。昨年度の成果として、瞬時に起こる液相反応をその場測定できる新規手法の立ち上げと実験条件の最適化などを行った。ヨウ化物イオンとオゾンの液相反応、酸塩基反応などを用いて、10マイクロ秒以内で起こる液相反応をモニターできることを確認した。また大気中で起こる界面反応と液相反応を個別に研究し、そのメカニズムを解明した。

Current Status of Research Progress

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

Reason

順調に立ち上げ、実験条件の最適化を行うことができている。また本研究の予備成果として、以下の論文を発表した。
J. Qiu, Z. Liang, K. Tonokura, A. J. Colussi, S. Enami, Structure and stability of alpha-hydroxyalkyl-hydroperoxides in aqueous organic media - Relevance to the fate of hydroperoxides in aerosol particle phases, Environ. Sci. Technol., 2020, 54, 3890-3899.
S. Ishizuka, A. Matsugi, T. Hama, S. Enami, Interfacial water mediates oligomerization pathways of monoterpene carbocations, J. Phys. Chem. Lett., 2020, 11, 67-74.
J. Qiu, S. Ishizuka, K. Tonokura, A. J. Colussi, S. Enami, Water dramatically accelerates the decomposition of alpha-hydroxyalkyl-hydroperoxides in aerosol particles, J. Phys. Chem. Lett., 2019, 10, 5748-5755.
S. Ishizuka, T. Hama, S. Enami, Acid-catalyzed oligomerization at the air-water interface modified by competitive adsorption of surfactants, J. Phys. Chem. C, 2019, 123, 21662-21669.
J. Qiu, S. Ishizuka, K. Tonokura, K. Sato, S. Inomata, S. Enami, Effects of pH on interfacial ozonolysis of alpha-terpineol, J. Phys. Chem. A, 2019, 123, 7148-7155.

Strategy for Future Research Activity

実際の大気化学反応I- + O3やFe2+ + O3に応用し、界面vs液中反応機構の違いを研究する。

Research Products

• [Int'l Joint Research] Caltech(米国)
  • Country Name: U.S.A.
  • Counterpart Institution: Caltech
• [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 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 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 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 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 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 Pages: 67～74
  • DOI: 10.1021/acs.jpclett.9b03110
  • Peer Reviewed / Open Access
• [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