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A large atomic chlorine source inferred from mid-continental reactive nitrogen chemistry

Nature volume 464, pages 271–274 (2010)Cite this article

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Abstract

Halogen atoms and oxides are highly reactive and can profoundly affect atmospheric composition. Chlorine atoms can decrease the lifetimes of gaseous elemental mercury1 and hydrocarbons such as the greenhouse gas methane2. Chlorine atoms also influence cycles that catalytically destroy or produce tropospheric ozone3, a greenhouse gas potentially toxic to plant and animal life. Conversion of inorganic chloride into gaseous chlorine atom precursors within the troposphere is generally considered a coastal or marine air phenomenon4. Here we report mid-continental observations of the chlorine atom precursor nitryl chloride at a distance of 1,400 km from the nearest coastline. We observe persistent and significant nitryl chloride production relative to the consumption of its nitrogen oxide precursors. Comparison of these findings to model predictions based on aerosol and precipitation composition data from long-term monitoring networks suggests nitryl chloride production in the contiguous USA alone is at a level similar to previous global estimates for coastal and marine regions5. We also suggest that a significant fraction of tropospheric chlorine atoms6 may arise directly from anthropogenic pollutants.

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Figure 1: Schematic of chlorine activation by night-time NO x chemistry.
Figure 2: Time series of key quantities observed in Boulder, Colorado, from 11 to 25 February 2009.
Figure 3: Observed and modelled relationships of ClNO 2 and particulate chloride.
Figure 4: Annual average components of over the US.

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Acknowledgements

Funding for the ClNO2 observations and analysis was provided by NSF grants ATM-0633897 and ATM-0846183 to J.A.T. Boulder field measurements were supported in part by the NOAA Atmospheric Chemistry and Climate Program. J.P.K. thanks the Camille and Henry Dreyfus Foundation for a postdoctoral fellowship in environmental chemistry. N.L.W. thanks the National Research Council for a postdoctoral fellowship.

Author Contributions This was largely a collaborative effort. All authors contributed to the collection of observations during the 2009 intensive campaign described here. J.P.K., W.P.D., J.A.T. and S.S.B conceived of the need and initial designs for the measurement campaign; J.A.T. performed much of the final analysis and modelling; T.P.R. performed the predictions of continental-scale ClNO2 production; and J.A.T. wrote the paper with significant input from all co-authors, especially S.S.B.

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Author notes

  1. James P. Kercher

    Present address: Present address: Department of Chemistry, Hiram College, Hiram, Ohio 44234, USA.,

Authors and Affiliations

  1. Department of Atmospheric Sciences,,

    Joel A. Thornton, James P. Kercher, Theran P. Riedel, Glenn M. Wolfe & Becky Alexander

  2. Department of Chemistry, University of Washington, Seattle, Washington 98195, USA,

    Theran P. Riedel & Glenn M. Wolfe

  3. Earth Systems Research Laboratory, National Oceanic and Atmospheric Administration, Boulder, Colorado 80305, USA ,

    Nicholas L. Wagner, Julie Cozic, John S. Holloway, William P. Dubé, Ann M. Middlebrook & Steven S. Brown

  4. Cooperative Institute for Research in Environmental Studies, Boulder, Colorado 80309, USA ,

    Julie Cozic, John S. Holloway & William P. Dubé

  5. Pacific Marine Environmental Laboratory, National Oceanic and Atmospheric Administration, Seattle, Washington 98115, USA ,

    Patricia K. Quinn

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Correspondence to Joel A. Thornton.

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This file contains Supplementary Methods and Discussion, Supplementary Notes and References, Supplementary Figures 1-10 with Legends, and Supplementary Table 1. (PDF 1691 kb)

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Thornton, J., Kercher, J., Riedel, T. et al. A large atomic chlorine source inferred from mid-continental reactive nitrogen chemistry. Nature 464, 271–274 (2010). https://doi.org/10.1038/nature08905

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