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Chloramines as an important photochemical source of chlorine atoms in the urban atmosphere

Proceedings of the National Academy of Sciences - PNAS, 2023-07, Vol.120 (30), p.e2220889120-e2220889120 [Peer Reviewed Journal]

Copyright National Academy of Sciences Jul 25, 2023 ;Copyright © 2023 the Author(s). Published by PNAS. 2023 ;ISSN: 0027-8424 ;EISSN: 1091-6490 ;DOI: 10.1073/pnas.2220889120 ;PMID: 37459517

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  • Title:
    Chloramines as an important photochemical source of chlorine atoms in the urban atmosphere
  • Author: Wang, Chen ; Liggio, John ; Wentzell, Jeremy J B ; Jorga, Spiro ; Folkerson, Andrew ; Abbatt, Jonathan P D
  • Subjects: Atmosphere ; Boundary layers ; Central business districts ; Chlorine ; Mixing ratio ; Monochloramine ; Night ; Nitrogen oxides ; Organic compounds ; Ozone ; Particulate matter ; Photochemicals ; Photochemistry ; Photolysis ; Physical Sciences ; Summer ; Sunrise ; Urban areas ; Urban atmosphere ; Winter
  • Is Part Of: Proceedings of the National Academy of Sciences - PNAS, 2023-07, Vol.120 (30), p.e2220889120-e2220889120
  • Description: Monochloramine, dichloramine and trichloramine (NH Cl, NHCl , NCl ) are measured in the ambient atmosphere, in downtown Toronto in summer (median 39, 15 and 2.8 ppt) and winter (median 11, 7.3 and 0.7 ppt). NCl and NHCl were also measured in summer (median 1.3 and 14 ppt) from a suburban Toronto location. Measurements at two locations demonstrate prevalence of chloramines in an urban atmosphere. At both sites, NCl exhibits a strong diel pattern with maximum values during the night, and photolytic loss with sunrise. At the downtown site, a strong positive correlation between NH Cl and NHCl in the summer night indicates a common source, with daily average peak mixing ratios approaching 500 and 250 ppt, respectively. As a previously unidentified source of chlorine (Cl) atoms, we demonstrate that NCl photolysis contributes 49 to 82% of the total local summertime Cl production rate at different times during the day with an average noontime peak of 3.8 × 10 atoms/cm /s, with smaller contributions from ClNO and Cl . Photolysis of NH Cl and NHCl may augment this Cl production rate. Our measurements also demonstrate a daytime enhancement of chloroacetone in both the summer and winter, demonstrating the importance of Cl photochemistry. The results suggest that chloramines are an important source of Cl atoms in urban areas, with potential impacts on the abundance of organic compounds, ozone, nitrogen oxides, and particulate matter. Future studies should explore the vertical gradients of chloramines and their contribution to Cl production throughout the boundary layer.
  • Publisher: United States: National Academy of Sciences
  • Language: English
  • Identifier: ISSN: 0027-8424
    EISSN: 1091-6490
    DOI: 10.1073/pnas.2220889120
    PMID: 37459517
  • Source: GFMER Free Medical Journals
    PubMed Central
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