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Detecting Intermediates and Products of Fast Heterogeneous Reactions on Liquid Surfaces via Online Mass Spectrometry

Colussi, Agustín J. and Enami, Shinichi (2019) Detecting Intermediates and Products of Fast Heterogeneous Reactions on Liquid Surfaces via Online Mass Spectrometry. Atmosphere, 10 (2). Art. No. 47. ISSN 2073-4433. doi:10.3390/atmos10020047.

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One of the research priorities in atmospheric chemistry is to advance our understanding of heterogeneous reactions and their effect on the composition of the troposphere. Chemistry on aqueous surfaces is particularly important because of their ubiquity and expanse. They range from the surfaces of oceans (360 million km2), cloud and aerosol drops (estimated at ~10 trillion km2) to the fluid lining the human lung (~150 m2). Typically, ambient air contains reactive gases that may affect human health, influence climate and participate in biogeochemical cycles. Despite their importance, atmospheric reactions between gases and solutes on aqueous surfaces are not well understood and, as a result, generally overlooked. New, surface-specific techniques are required that detect and identify the intermediates and products of such reactions as they happen on liquids. This is a tall order because genuine interfacial reactions are faster than mass diffusion into bulk liquids, and may produce novel species in low concentrations. Herein, we review evidence that validates online pneumatic ionization mass spectrometry of liquid microjets exposed to reactive gases as a technique that meets such requirements. Next, we call attention to results obtained by this approach on reactions of gas-phase ozone, nitrogen dioxide and hydroxyl radicals with various solutes on aqueous surfaces. The overarching conclusion is that the outermost layers of aqueous solutions are unique media, where most equilibria shift and reactions usually proceed along new pathways, and generally faster than in bulk water. That the rates and mechanisms of reactions at air-aqueous interfaces may be different from those in bulk water opens new conceptual frameworks and lines of research, and adds a missing dimension to atmospheric chemistry.

Item Type:Article
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URLURL TypeDescription
Colussi, Agustín J.0000-0002-3400-4101
Enami, Shinichi0000-0002-2790-7361
Additional Information:© 2019 The Author(s). This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0). Received: 8 January 2019 / Revised: 20 January 2019 / Accepted: 22 January 2019 / Published: 26 January 2019. (This article belongs to the Special Issue Physical Chemistry of the Air-Water Interface) A.J.C. acknowledges support from the National Science Foundation USA, grant AGS-1744353. SE acknowledges support from the JSPS KAKENHI, grant numbers 15H05328 and 15K12188. Author Contributions: A.J.C. and S.E. designed experiments. S.E. performed experiments. A.J.C. and S.E. analyzed results and wrote the paper. The authors declare no conflict of interest.
Funding AgencyGrant Number
Japan Society for the Promotion of Science (JSPS)15H05328
Japan Society for the Promotion of Science (JSPS)15K12188
Subject Keywords:fast gas-liquid reactions; online electrospray ionization mass spectrometry; heterogeneous atmospheric chemistry
Issue or Number:2
Record Number:CaltechAUTHORS:20190130-121937435
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Official Citation:Colussi, A.J.; Enami, S. Detecting Intermediates and Products of Fast Heterogeneous Reactions on Liquid Surfaces via Online Mass Spectrometry. Atmosphere 2019, 10, 47.
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:92530
Deposited By: George Porter
Deposited On:31 Jan 2019 00:09
Last Modified:16 Nov 2021 03:51

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