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High levels of nitryl chloride in the polluted subtropical marine boundary layer

Nature Geoscience volume 1, pages 324–328 (2008)Cite this article

Abstract

The cycling of halogen compounds in the lower atmosphere is poorly understood. It is known that halogens such as chlorine, bromine and iodine are converted from halides, which are relatively inert, to reactive radicals. These reactive radicals can affect ozone production and destruction, aerosol formation and the lifetimes of important trace gases such as methane, mercury and naturally occurring sulphur compounds. However, the processes by which halides are converted to reactive halogens are uncertain. Here, we report atmospheric measurements of nitryl chloride, an active halogen, along the southeast coastline of the United States and near Houston, Texas. We show that the main source of nitryl chloride is the night-time reaction of dinitrogen pentoxide with chloride-containing aerosol. The levels observed are much greater than earlier estimates based on numerical models and are sufficiently large to affect oxidant photochemistry in areas where nitrogen oxides and aerosol chloride sources coexist, such as urban areas and ship engine exhaust plumes.

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Figure 1: Maps of the study area.
Figure 2: Measurements of ClNO2 and N2O5 on two different nights.
Figure 3: Production of Cl atoms from ClNO2 photolysis.

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Acknowledgements

We thank the officers and crew of the NOAA R/V R. H. Brown for their assistance and professionalism. We thank S. Herndon and M. Zahniser for the use of their formaldehyde data. We thank J. Thornton for helpful discussions. We thank D. Tanner, G. Huey, A. Neuman, J. Nowak, W. P. Dubé and S. Ciciora for help with instrumentation. The EDGAR 3.2 NOx emissions data were obtained from the website http://www.mnp.nl/edgar/. This work was supported by the NOAA Climate Forcing and Air Quality Programs.

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Author notes

  1. Hans D. Osthoff

    Present address: Present address: Department of Chemistry, University of Calgary, Calgary, Alberta T2N 1N4, Canada,

Authors and Affiliations

  1. National Oceanic and Atmospheric Administration (NOAA) Earth System Research Laboratory, CSD, 325 Broadway, Boulder, Colorado 80305, USA

    Hans D. Osthoff, James M. Roberts, A. R. Ravishankara, Eric J. Williams, Brian M. Lerner, Roberto Sommariva, Harald Stark, James B. Burkholder, Ranajit K. Talukdar, James Meagher, Fred C. Fehsenfeld & Steven S. Brown

  2. Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, Colorado 80309, USA

    Hans D. Osthoff, Eric J. Williams, Brian M. Lerner, Roberto Sommariva, Harald Stark, Ranajit K. Talukdar & Fred C. Fehsenfeld

  3. Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309, USA

    A. R. Ravishankara

  4. National Oceanic and Atmospheric Administration (NOAA) Pacific Marine Environment Laboratory, 7600 Sand Point Way, Seattle, Washington 98115, USA

    Timothy S. Bates, Derek Coffman & Patricia K. Quinn

  5. Climate Change Research Center, Institute for the Study of Earth Oceans and Space, University of New Hampshire, Durham, New Hampshire 03824, USA

    Jack E. Dibb

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Correspondence to Hans D. Osthoff or James M. Roberts.

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Osthoff, H., Roberts, J., Ravishankara, A. et al. High levels of nitryl chloride in the polluted subtropical marine boundary layer. Nature Geosci 1, 324–328 (2008). https://doi.org/10.1038/ngeo177

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