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Title: The reaction between CH 3O 2 and OH radicals: Product yields and atmospheric implications

The reaction between CH 3O 2 and OH radicals has been shown to be fast and to play an appreciable role for the removal of CH 3O 2 radials in remote environments such as the marine boundary layer. Two different experimental techniques have been used here to determine the products of this reaction. The HO 2 yield has been obtained from simultaneous time-resolved measurements of the absolute concentration of CH 3O 2, OH, and HO 2 radicals by cw-CRDS. The possible formation of a Criegee intermediate has been measured by broadband cavity enhanced UV absorption. A yield of Φ HO2 = (0.8 ± 0.2) and an upper limit for Φ Criegee = 0.05 has been determined for this reaction, suggesting a minor yield of methanol or stabilized trioxide as a product. The impact of this reaction on the composition of the remote marine boundary layer has been determined by implementing these findings into a box model utilizing the Master Chemical Mechanism v3.2, and constraining the model for conditions found at the Cape Verde Atmospheric Observatory in the remote tropical Atlantic Ocean. Inclusion of the CH 3O 2+OH reaction into the model results in up to 30% decrease in the CHmore » 3O 2 radical concentration while the HO 2 concentration increased by up to 20%. Finally, production and destruction of O 3 are also influenced by these changes, and the model indicates that taking into account the reaction between CH 3O 2 and OH leads to a 6% decrease of O 3.« less
Authors:
 [1] ;  [2] ;  [3] ;  [3] ; ORCiD logo [1] ;  [1] ; ORCiD logo [1]
  1. Univ. Lille, Lille (France)
  2. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  3. Univ. of Leeds, Leeds (United Kingdom)
Publication Date:
Report Number(s):
SAND-2017-1088J
Journal ID: ISSN 0013-936X; 650902
Grant/Contract Number:
AC04-94AL85000
Type:
Accepted Manuscript
Journal Name:
Environmental Science and Technology
Additional Journal Information:
Journal Volume: 51; Journal Issue: 4; Journal ID: ISSN 0013-936X
Publisher:
American Chemical Society (ACS)
Research Org:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org:
USDOE National Nuclear Security Administration (NNSA)
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES
OSTI Identifier:
1343626

Assaf, Emmanuel, Sheps, Leonid, Whalley, Lisa, Heard, Dwayne, Tomas, Alexandre, Schoemaecker, Coralie, and Fittschen, Christa. The reaction between CH3O2 and OH radicals: Product yields and atmospheric implications. United States: N. p., Web. doi:10.1021/acs.est.6b06265.
Assaf, Emmanuel, Sheps, Leonid, Whalley, Lisa, Heard, Dwayne, Tomas, Alexandre, Schoemaecker, Coralie, & Fittschen, Christa. The reaction between CH3O2 and OH radicals: Product yields and atmospheric implications. United States. doi:10.1021/acs.est.6b06265.
Assaf, Emmanuel, Sheps, Leonid, Whalley, Lisa, Heard, Dwayne, Tomas, Alexandre, Schoemaecker, Coralie, and Fittschen, Christa. 2017. "The reaction between CH3O2 and OH radicals: Product yields and atmospheric implications". United States. doi:10.1021/acs.est.6b06265. https://www.osti.gov/servlets/purl/1343626.
@article{osti_1343626,
title = {The reaction between CH3O2 and OH radicals: Product yields and atmospheric implications},
author = {Assaf, Emmanuel and Sheps, Leonid and Whalley, Lisa and Heard, Dwayne and Tomas, Alexandre and Schoemaecker, Coralie and Fittschen, Christa},
abstractNote = {The reaction between CH3O2 and OH radicals has been shown to be fast and to play an appreciable role for the removal of CH3O2 radials in remote environments such as the marine boundary layer. Two different experimental techniques have been used here to determine the products of this reaction. The HO2 yield has been obtained from simultaneous time-resolved measurements of the absolute concentration of CH3O2, OH, and HO2 radicals by cw-CRDS. The possible formation of a Criegee intermediate has been measured by broadband cavity enhanced UV absorption. A yield of ΦHO2 = (0.8 ± 0.2) and an upper limit for ΦCriegee = 0.05 has been determined for this reaction, suggesting a minor yield of methanol or stabilized trioxide as a product. The impact of this reaction on the composition of the remote marine boundary layer has been determined by implementing these findings into a box model utilizing the Master Chemical Mechanism v3.2, and constraining the model for conditions found at the Cape Verde Atmospheric Observatory in the remote tropical Atlantic Ocean. Inclusion of the CH3O2+OH reaction into the model results in up to 30% decrease in the CH3O2 radical concentration while the HO2 concentration increased by up to 20%. Finally, production and destruction of O3 are also influenced by these changes, and the model indicates that taking into account the reaction between CH3O2 and OH leads to a 6% decrease of O3.},
doi = {10.1021/acs.est.6b06265},
journal = {Environmental Science and Technology},
number = 4,
volume = 51,
place = {United States},
year = {2017},
month = {1}
}