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Transition from high- to low-NOx control of night-time oxidation in the southeastern US

Nature Geoscience volume 10, pages 490–495 (2017)Cite this article

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Abstract

The influence of nitrogen oxides (NOx) on daytime atmospheric oxidation cycles is well known, with clearly defined high- and low-NOx regimes. During the day, oxidation reactions—which contribute to the formation of secondary pollutants such as ozone—are proportional to NOx at low levels, and inversely proportional to NOx at high levels. Night-time oxidation of volatile organic compounds also influences secondary pollutants but lacks a similar clear definition of high- and low-NOx regimes, even though such regimes exist. Decreases in anthropogenic NOx emissions in the US and Europe coincided with increases in Asia over the last 10 to 20 years, and have altered both daytime and nocturnal oxidation cycles. Here we present measurements of chemical species in the lower atmosphere from day- and night-time research flights over the southeast US in 1999 and 2013, supplemented by atmospheric chemistry simulations. We find that night-time oxidation of biogenic volatile organic compounds (BVOC) is NOx-limited when the ratio of NOx to BVOC is below approximately 0.5, and becomes independent of NOx at higher ratios. The night-time ratio of NOx to BVOC in 2013 averaged 0.6 aloft. We suggest that night-time oxidation in the southeast US is in transition between NOx-dominated and ozone-dominated.

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Figure 1: Schematic of night-time BVOC oxidation.
Figure 2: Flight data from the SENEX night flights.
Figure 3: NOx/BVOC control of nocturnal BVOC oxidation.
Figure 4: Comparison of observed 1999 and 2013 southeast US composition.

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Acknowledgements

F.N.K. and J.K. acknowledge the US EPA Science to Achieve Results (STAR) program grant 83540601. This research has not been subjected to any EPA review and therefore does not necessarily reflect the views of the agency, and no official endorsement should be inferred. J.K. also acknowledges support from NASA Headquarters under the NASA Earth and Space Science Fellowship Program—grant NNX14AK97H. J.L.F. gratefully acknowledges funding from the NOAA Climate Program Office’s AC4 program (Grant No. NA13OAR4310070).

Author information

Author notes

  1. M. G. Graus

    Present address: Institute of Atmospheric and Cryospheric Sciences, University of Innsbruck, A-6020, Austria

  2. J. Kaiser

    Present address: Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, Massachusetts, 02138, USA

  3. F. N. Keutsch

    Present address: Paulson School of Engineering and Applied Sciences and Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts, 02138, USA

  4. I. B. Pollack & A. R. Ravishankara

    Present address: Departments of Chemistry and Atmospheric Science, Colorado State University, Fort Collins, Colorado, 80523, USA

Authors and Affiliations

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

    P. M. Edwards, K. C. Aikin, W. P. Dube, J. B. Gilman, J. A. de Gouw, M. G. Graus, J. Holloway, G. Hübler, B. M. Lerner, J. A. Neuman, D. D. Parrish, J. Peischl, I. B. Pollack, P. R. Veres & C. Warneke

  2. Chemical Sciences Division, NOAA Earth System Research Laboratory, Boulder, Colorado, 80305, USA

    P. M. Edwards, K. C. Aikin, W. P. Dube, J. B. Gilman, J. A. de Gouw, M. G. Graus, J. Holloway, G. Hübler, B. M. Lerner, J. A. Neuman, D. D. Parrish, J. Peischl, I. B. Pollack, A. R. Ravishankara, J. M. Roberts, T. B. Ryerson, M. Trainer, P. R. Veres, C. Warneke & S. S. Brown

  3. Department of Chemistry, Wolfson Atmospheric Chemistry Laboratories, University of York, York, YO10 5DD, UK

    P. M. Edwards

  4. Department of Chemistry, Reed College, Portland, Oregon, 97202, USA

    J. L. Fry

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

    J. A. de Gouw & S. S. Brown

  6. NASA Goddard Space Flight Center, Greenbelt, Maryland, 20771, USA

    T. F. Hanisco & G. M. Wolfe

  7. University of Wisconsin-Madison, Madison, Wisconsin, 53706, USA

    J. Kaiser & F. N. Keutsch

  8. Joint Center for Earth Systems Technology, University of Maryland Baltimore County, Baltimore, Maryland, 21250, USA

    G. M. Wolfe

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Contributions

The analysis presented in this paper was performed by P.M.E. and S.S.B. Model simulations were performed by P.M.E. All other co-authors were instrumental in the collection of the data used in this analysis. The manuscript was written by P.M.E. and S.S.B. All authors discussed the results and commented on the manuscript.

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Correspondence to S. S. Brown.

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Edwards, P., Aikin, K., Dube, W. et al. Transition from high- to low-NOx control of night-time oxidation in the southeastern US. Nature Geosci 10, 490–495 (2017). https://doi.org/10.1038/ngeo2976

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