Heterogeneous formation of nitryl chloride and its role as a nocturnal NOx reservoir species during CalNex‐LA 2010

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dc.contributor.authorMielke, L. H.
dc.contributor.authorStutz, J.
dc.contributor.authorTsai, C.
dc.contributor.authorHurlock, S. C.
dc.contributor.authorRoberts, J. M.
dc.contributor.authorVeres, P. R.
dc.contributor.authorFroyd, K. D.
dc.contributor.authorHayes, P. L.
dc.contributor.authorCubison, M. J.
dc.contributor.authorJimenez, J. L.
dc.contributor.authorWashenfelder, R. A.
dc.contributor.authorYoung, C. J.
dc.contributor.authorGilman, J. B.
dc.contributor.authorGouw, J. A.
dc.contributor.authorFlynn, J. H.
dc.contributor.authorGrossberg, N.
dc.contributor.authorLefer, B. L.
dc.contributor.authorLiu, J.
dc.contributor.authorWeber, R. J.
dc.contributor.authorOsthoff, H. D.
dc.date.accessioned2021-06-29T02:58:19Z
dc.date.available2021-06-29T02:58:19Z
dc.date.issued2013-08-29
dc.description.abstractThe nocturnal conversion of dinitrogen pentoxide (N2O5) to nitryl chloride (ClNO2) on chloride-containing aerosol can be a regionally important NOx (= NO + NO2) recycling and halogen activation pathway that affects oxidant photochemistry the following day. Here we present a comprehensive measurement data set acquired at Pasadena, California, during the CalNex-LA campaign 2010 that included measurements of odd nitrogen and its major components (NOy = NOx + NO3 + 2N2O5 + ClNO2 + HNO3 + HONO + peroxyacyl, alkyl, and aerosol nitrates) and aerosol size distribution and composition. Nitryl chloride was present during every night of the study (median mixing ratio at sunrise 800 pptv) and was usually a more significant nocturnal NOx and odd oxygen (Ox = O3 + NO2 + 3N2O5 + ClNO2) reservoir species than N2O5 (whose concentrations were calculated from its equilibrium with NO2 and NO3). At sunrise, ClNO2 accounted for 21% of NOz (=NOy − NOx), 4% of NOy, and 2.5% of Ox, respectively (median values). Kinetic parameters for the N2O5 to ClNO2 conversion were estimated by relating ClNO2 concentrations to their time-integrated heterogeneous production from N2O5 and were highly variable between nights. Production of ClNO2 required conversion of N2O5 on submicron aerosol with average yield (φ) and N2O5 reactive uptake probability (γ) of γφ = 0.008 (maximum 0.04), scaled with submicron aerosol chloride content, and was suppressed by aerosol organic matter and liquid water content. Not all of the observed variability of ClNO2 production efficiency could be rationalized using current literature parameterizations.en_US
dc.identifier.citationMielke, L. H., Stutz, J., Tsai, C., Hurlock, S. C., Roberts, J. M., Veres, P. R., … Osthoff, H. D. (2013). Heterogeneous formation of nitryl chloride and its role as a nocturnal NO x reservoir species during CalNex‐LA 2010. Journal of Geophysical Research: Atmospheres, 118(18). doi:10.1002/jgrd.50783en_US
dc.identifier.doihttp://dx.doi.org/10.1002/jgrd.50783en_US
dc.identifier.urihttp://hdl.handle.net/1880/113559
dc.language.isoengen_US
dc.publisherAmerican Geophysical Unionen_US
dc.publisher.departmentChemistryen_US
dc.publisher.facultyScienceen_US
dc.publisher.hasversionpublishedVersionen_US
dc.publisher.institutionUniversity of Calgaryen_US
dc.publisher.policyhttps://www.agu.org/Publish-with-AGU/Publish/Author-Resources/Policies/Permission-policyen_US
dc.rights©2013. American Geophysical Union. All Rights Reserved.en_US
dc.titleHeterogeneous formation of nitryl chloride and its role as a nocturnal NOx reservoir species during CalNex‐LA 2010en_US
dc.typejournal articleen_US
ucalgary.item.requestcopytrueen_US
ucalgary.scholar.levelFacultyen_US
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