An MCM modeling study of nitryl chloride (ClNO2) impacts on oxidation, ozone production and nitrogen oxide partitioning in polluted continental outflow

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dc.contributor.authorRiedel, T. P.
dc.contributor.authorWolfe, G. M.
dc.contributor.authorDanas, K. T.
dc.contributor.authorGilman, J. B.
dc.contributor.authorKuster, W. C.
dc.contributor.authorBon, D. M.
dc.contributor.authorVlasenko, A.
dc.contributor.authorLi, S. M.
dc.contributor.authorWilliams, E. J.
dc.contributor.authorLerner, B.M.
dc.contributor.authorVeres, P. R.
dc.contributor.authorRoberts, J. M.
dc.contributor.authorHolloway, J.S.
dc.contributor.authorLefer, B.
dc.contributor.authorBrown, S. S.
dc.contributor.authorThornton, J. A.
dc.date.accessioned2020-09-16T17:31:47Z
dc.date.available2020-09-16T17:31:47Z
dc.date.issued2014-04-16
dc.description.abstractNitryl chloride (ClNO₂) is produced at night by reactions of dinitrogen pentoxide (N₂O₅) on chloride containing surfaces. ClNO₂ is photolyzed during the morning hours after sunrise to liberate highly reactive chlorine atoms (Cl·). This chemistry takes place primarily in polluted environments where the concentrations of N₂O₅ precursors (nitrogen oxide radicals and ozone) are high, though it likely occurs in remote regions at lower intensities. Recent field measurements have illustrated the potential importance of ClNO₂ as a daytime Cl· source and a nighttime NOx reservoir. However, the fate of the Cl· and the overall impact of ClNO₂ on regional photochemistry remain poorly constrained by measurements and models. To this end, we have incorporated ClNO₂ production, photolysis, and subsequent Cl· reactions into an existing master chemical mechanism (MCM version 3.2) box model framework using observational constraints from the CalNex 2010 field study. Cl· reactions with a set of alkenes and alcohols, and the simplified multiphase chemistry of N₂O₅, ClNO₂, HOCl, ClONO₂, and Cl₂, none of which are currently part of the MCM, have been added to the mechanism. The presence of ClNO₂ produces significant changes to oxidants, ozone, and nitrogen oxide partitioning, relative to model runs excluding ClNO₂ formation. From a nighttime maximum of 1.5 ppbv ClNO₂, the daytime maximum Cl· concentration reaches 1 × 10⁵ atoms cm⁻³ at 07:00 model time, reacting mostly with a large suite of volatile organic compounds (VOC) to produce 2.2 times more organic peroxy radicals in the morning than in the absence of ClNO₂. In the presence of several ppbv of nitrogen oxide radicals (NOx = NO + NO₂), these perturbations lead to similar enhancements in hydrogen oxide radicals (HOx = OH + HO₂). Neglecting contributions from HONO, the total integrated daytime radical source is 17% larger when including ClNO₂, which leads to a similar enhancement in integrated ozone production of 15%. Detectable levels (tens of pptv) of chlorine containing organic compounds are predicted to form as a result of Cl· addition to alkenes, which may be useful in identifying times of active Cl· chemistry.en_US
dc.description.sponsorshipThis work was supported by a grant from the National Science Foundation (NSF CAREER ATM-0846183 to J. A. Thornton). T. P. Riedel is grateful for an Earth System Science graduate fellowship from the National Aeronautics and Space Administration (NASA NESSF NNX10AN48H). G. M. Wolfe acknowledges support from a NOAA Climate and Global Change Postdoctoral Fellowship administered by the University Corporation for Atmospheric Research. This research was support in part by the NOAA Health of the Atmosphere Program. We also thank the crew of the R/V Atlantis and the Pasadena ground site science team for their tireless efforts and continual support throughout the CalNex study.en_US
dc.description.urihttps://acp.copernicus.org/articles/14/3789/2014/en_US
dc.format.extent12 pagesen_US
dc.genrejournal articlesen_US
dc.identifierdoi:10.13016/m2cpi6-z9tm
dc.identifier.citationRiedel, T. P., Wolfe, G. M., Danas, K. T., Gilman, J. B., Kuster, W. C., Bon, D. M., Vlasenko, A., Li, S.-M., Williams, E. J., Lerner, B. M., Veres, P. R., Roberts, J. M., Holloway, J. S., Lefer, B., Brown, S. S., and Thornton, J. A.: An MCM modeling study of nitryl chloride (ClNO2) impacts on oxidation, ozone production and nitrogen oxide partitioning in polluted continental outflow, Atmos. Chem. Phys., 14, 3789–3800, https://doi.org/10.5194/acp-14-3789-2014, 2014.en_US
dc.identifier.urihttps://doi.org/10.5194/acp-14-3789-2014
dc.identifier.urihttp://hdl.handle.net/11603/19663
dc.language.isoen_USen_US
dc.publisherCopernicusen_US
dc.relation.isAvailableAtThe University of Maryland, Baltimore County (UMBC)
dc.relation.ispartofUMBC Joint Center for Earth Systems Technology
dc.relation.ispartofUMBC Physics Department
dc.relation.ispartofUMBC Faculty Collection
dc.rightsThis item is likely protected under Title 17 of the U.S. Copyright Law. Unless on a Creative Commons license, for uses protected by Copyright Law, contact the copyright holder or the author.
dc.rightsPublic Domain Mark 1.0*
dc.rightsThis work was written as part of one of the author's official duties as an Employee of the United States Government and is therefore a work of the United States Government. In accordance with 17 U.S.C. 105, no copyright protection is available for such works under U.S. Law.
dc.rights.urihttp://creativecommons.org/publicdomain/mark/1.0/*
dc.titleAn MCM modeling study of nitryl chloride (ClNO2) impacts on oxidation, ozone production and nitrogen oxide partitioning in polluted continental outflowen_US
dc.typeTexten_US

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