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Technical Note: A technique to convert NO.sub.2 to NO.sub.2.sup.- with S and its application to measuring nitrate photolysis

Atmospheric chemistry and physics, 2024-04, Vol.24 (7), p.4411 [Peer Reviewed Journal]

COPYRIGHT 2024 Copernicus GmbH ;ISSN: 1680-7316 ;EISSN: 1680-7324

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  • Title:
    Technical Note: A technique to convert NO.sub.2 to NO.sub.2.sup.- with S and its application to measuring nitrate photolysis
  • Author: Lieberman, Aaron ; Picco, Julietta ; Onder, Murat ; Anastasio, Cort
  • Subjects: Measurement ; Methods ; Nitric oxide ; Nitrogen dioxide ; Photolysis ; Physical instruments
  • Is Part Of: Atmospheric chemistry and physics, 2024-04, Vol.24 (7), p.4411
  • Description: Nitrate photolysis is a potentially significant mechanism for "renoxifying" the atmosphere, i.e., converting nitrate into nitrogen oxides - nitrogen dioxide (NO.sub.2) and nitric oxide (NO) - and nitrous acid (HONO). Nitrate photolysis in the environment occurs through two channels which produce (1) NO.sub.2 and hydroxyl radical (â«OH) and (2) nitrite (NO2-) and an oxygen atom (O(.sup.3 P)). Although the aqueous quantum yields and photolysis rate constants of both channels have been established, field observations suggest that nitrate photolysis is enhanced in the environment. Laboratory studies investigating these enhancements typically only measure one of the two photo-channels, since measuring both channels generally requires separate analytical methods and instrumentation. However, measuring only one channel makes it difficult to assess whether secondary chemistry is enhancing one channel at the expense of the other or if there is an overall enhancement of nitrate photochemistry. Here, we show that the addition of S(IV), i.e., bisulfite and sulfite, can convert NO.sub.2 to NO2-, allowing for measurement of both nitrate photolysis channels with the same equipment. By varying the concentration of S(IV) and exploring method parameters, we determine the experimental conditions that quantitatively convert NO.sub.2 and accurately quantify the resulting NO2-. We then apply the method to a test case, showing how an â«OH scavenger in solution prevents the oxidation of NO2- to NO.sub.2 but does not enhance the overall photolysis efficiency of nitrate.
  • Publisher: Copernicus GmbH
  • Language: English
  • Identifier: ISSN: 1680-7316
    EISSN: 1680-7324
  • Source: Geneva Foundation Free Medical Journals at publisher websites
    AUTh Library subscriptions: ProQuest Central
    Alma/SFX Local Collection
    DOAJ Directory of Open Access Journals
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