Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Letter
  • Published:

Nitric acid photolysis on forest canopy surface as a source for tropospheric nitrous acid

Nature Geoscience volume 4, pages 440–443 (2011)Cite this article

Subjects

Abstract

Photolysis of nitrous acid generates hydroxyl radicals—a key atmospheric oxidant—in the lower atmosphere. Significant concentrations of nitrous acid have been reported in the rural atmospheric boundary layer during the day, where photolysis of nitrous acid accounts for up to 42% of sunlight-induced radical production1,2,3,4,5,6,7. The observed concentrations of nitrous acid are thought to be sustained by heterogeneous reactions involving precursors such as nitrogen oxides1,2,3,8,9,10,11,12 and nitric acid5,6,8,13. Here, we present direct measurements of nitrous acid flux over a rural forest canopy in Michigan, together with surface nitrate loading at the top of the canopy. We report a significant upward flux of nitrous acid during the day, with a peak around noontime. Daytime nitrous acid flux was positively correlated with the product of leaf surface nitrate loading and the rate constant of nitrate photolysis. We suggest that the photolysis of nitric acid on forest canopies is a significant daytime source of nitrous acid to the lower atmosphere in rural environments, and could serve as an important pathway for the remobilization of deposited nitric acid.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Diurnal variations of UV intensity, HONO mixing ratio, and HONO flux.
Figure 2: Relationship between HONO flux and surface HNO3 photolysis potential, Js_HNO3×Lnitrate.
Figure 3: Observed and predicted daytime nitrate loading at the top of the forest canopy.

Similar content being viewed by others

References

  1. Acker, K. et al. Strong daytime production of OH from HNO2 at a rural mountain site. Geophys. Res. Lett. 33, L02809 (2006).

    Article  Google Scholar 

  2. Kleffmann, J. et al. Daytime formation of nitrous acid: A major source of OH radicals in a forest. Geophys. Res. Lett. 32, L05818 (2005).

    Article  Google Scholar 

  3. Kleffmann, J. Daytime sources of nitrous acid (HONO) in the atmospheric boundary layer. ChemPhysChem 8, 1137–1144 (2007).

    Article  Google Scholar 

  4. Ren, X. et al. OH, HO2, and OH reactivity during the PMTACS-NY Whiteface Mountain 2002 campaign: Observations and model comparison. J. Geophys. Res. 111, D10S03 (2006).

    Article  Google Scholar 

  5. Zhou, X. et al. Summertime nitrous acid chemistry in the atmospheric boundary layer at a rural site in New York State. J. Geophys. Res. 107, 4590 (2002).

    Google Scholar 

  6. Zhou, X., Huang, G., Civerolo, K., Roychowdhury, U. & Demerjian, K. L. Summertime observations of HONO, HCHO, and O3 at the summit of Whiteface Mountain, New York. J. Geophys. Res. 112, D08311 (2007).

    Google Scholar 

  7. Ren, X. et al. Measurement of atmospheric nitrous acid at Blodgett Forest during BEARPEX2007. Atmos. Chem. Phys. Discuss. 10, 7383–7419 (2010).

    Article  Google Scholar 

  8. He, Y., Zhou, X., Hou, J., Gao, H. & Bertman, S. B. Importance of dew in controlling the air-surface exchange of HONO in rural forested environments. Geophys. Res. Lett. 33, L02813 (2006).

    Google Scholar 

  9. Kleffmann, J. et al. Measured and simulated vertical profiles of nitrous acid—Part I: Field measurements. Atmos. Environ. 37, 2949–2955 (2003).

    Article  Google Scholar 

  10. Vogel, B., Vogel, H., Kleffmann, J. & Kurtenbach, R. Measured and simulated vertical profiles of nitrous acid, Part II—model simulations and indications for a photolytic source. Atmos. Environ. 37, 2957–2966 (2003).

    Article  Google Scholar 

  11. George, C., Strekowski, R. S., Kleffmann, J., Stemmler, K. & Ammann, M. Photoenhanced uptake of gaseous NO2 on solid-organic compounds: A photochemical source of HONO? Farad. Discussions 130, 195–210 (2005).

    Article  Google Scholar 

  12. Stemmler, K., Ammann, M., Donders, C., Kleffmann, J. & George, C. Photosensitized reduction of nitrogen dioxide on humic acid as a source of nitrous acid. Nature 440, 195–198 (2006).

    Article  Google Scholar 

  13. Zhou, X. et al. Nitric acid photolysis on surfaces in low-NOx environments: Significant atmospheric implications. Geophys. Res. Lett. 30, 2217 (2003).

    Google Scholar 

  14. Carroll, M. A., Bertman, S. B. & Shepson, P. B. Overview of the program for research on oxidants: Photochemistry, emissions, and transport (PROPHET) summer 1998 measurements intensive. J. Geophys. Res. 106, 24275–24288 (2001).

    Article  Google Scholar 

  15. Zhang, N. et al. Aircraft measurement of HONO vertical profiles over a forested region. Geophys. Res. Lett. 36, L15820 (2009).

    Google Scholar 

  16. Hogg, A. Stomatal and Non-Stomatal Fluxes of Ozone, NOx and NOy to a Northern Mixed Hardwood Forest. Doctoral Thesis, Univ. Michigan (2007).

  17. Hill, K. A., Shepson, P. B., Galbavy, E. S. & Anastasio, C. Measurement of wet deposition of inorganic and organic nitrogen in a forest environment. J. Geophys. Res. 110, G02010 (2005).

    Article  Google Scholar 

  18. Horii, C. V. et al. Atmospheric reactive nitrogen concentration and flux budgets at a Northeastern U.S. forest site. Agr. Forest Meteorol. 133, 210–225 (2005).

    Article  Google Scholar 

  19. Horii, C. V. et al. Fluxes of nitrogen oxides over a temperate deciduous forest. J. Geophys. Res. 109, D08305 (2004).

    Article  Google Scholar 

  20. Masel, R. I. Principles of Adsorption and Reaction on Solid Surfaces (John Wiley, 1996).

    Google Scholar 

  21. Ramazan, K. A., Syomin, D. & Finlayson-Pitts, B. J. The photochemical production of HONO during the heterogeneous hydrolysis of NO2 . Phys. Chem. Chem. Phys. 6, 3836–3843 (2004).

    Google Scholar 

  22. Zhu, C., Xiang, B., Chu, L. T. & Zhu, L. 308 nm photolysis of nitric acid in the gas phase, on aluminum surfaces, and on ice films. J. Phys. Chem. 114, 2561–2568 (2010).

    Article  Google Scholar 

  23. Marshall, J. D. & Cadle, S. H. Evidence for trans-cuticular uptake of HNO3 vapor by foliage of Eastern white pine (Pinus strobus L.). Environ. Pollut. 60, 15–28 (1989).

    Article  Google Scholar 

  24. Hari, P. et al. Ultraviolet light and leaf emission of NOx . Nature 422, 134 (2003).

    Article  Google Scholar 

  25. Businger, J. A. & Oncley, S. P. Flux measurement with conditional sampling. J. Atmos. Ocean. Technol. 7, 349–352 (1990).

    Article  Google Scholar 

  26. Westberg, H. et al. Measurement of isoprene fluxes at the PROPHET site. J. Geophys. Res. 106, 24347–24358 (2001).

    Article  Google Scholar 

  27. Kleinman, L. et al. Peroxy radical concentration and ozone formation rate at a rural site in southeastern United States. J. Geophys. Res. 100, 7263–7273 (1995).

    Article  Google Scholar 

  28. Madronich, S. Photodissociation in the atmosphere, 1. Actinic flux and the effects of ground reflections and clouds. J. Geophys. Res. 92, 7263–7273 (1987).

    Article  Google Scholar 

  29. Thornberry, T. et al. Observation of reactive oxidized nitrogen and speciation of NOy during the PROPHET summer 1998 intensive. J. Geophys. Res. 106, 24359–24386 (2001).

    Article  Google Scholar 

  30. Seinfeld, J. H. & Pandis, S. N. Atmospheric Chemistry and Physics, From Air Pollution to Climate Change 2nd edn (John Wiley, 2006).

    Google Scholar 

Download references

Acknowledgements

We thank fellow PROPHETeers for their assistance and University of Michigan Biological Station for outstanding logistical support during the field deployments. This research was supported by National Science Foundation ATM-0632548.

Author information

Authors and Affiliations

  1. New York State Department of Health, Wadsworth Center, Albany, New York 12201, USA

    Xianliang Zhou

  2. Department of Environmental Health Sciences, State University of New York, Albany, New York 12201, USA

    Xianliang Zhou, Ning Zhang & Jian Hou

  3. Department of Biological and Environmental Engineering, Cornell University, Ithaca, New York 14850, USA

    Michaela TerAvest

  4. Department of Psychology, State University of New York, Stony Brook, New York 11794, USA

    David Tang

  5. Department of Chemistry, Western Michigan University, Kalamazoo, Michigan 49008, USA

    Steve Bertman

  6. Departments of Chemistry, and Earth and Atmospheric Sciences, Purdue University, West Lafayette, Indiana 47907, USA

    Marjan Alaghmand & Paul B. Shepson

  7. Department of Atmospheric, Oceanic and Space Science, University of Michigan, Ann Arbor, Michigan 48109, USA

    Mary Anne Carroll

  8. The School of Public and Environmental Affairs, Indiana University, Bloomington, Indiana 47405-1701, USA

    Stephen Griffith, Sebastien Dusanter & Philip S. Stevens

Authors
  1. Xianliang Zhou
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Ning Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Michaela TerAvest
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. David Tang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Jian Hou
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Steve Bertman
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Marjan Alaghmand
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Paul B. Shepson
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Mary Anne Carroll
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Stephen Griffith
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Sebastien Dusanter
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Philip S. Stevens
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

X.Z. conceived and initiated the study. X.Z, N.Z. and S.B designed the HONO measurement. N.Z., D.T. and J.H. measured HONO flux and concentration. M.T. measured surface nitrate loading. S.B. and M.A.C. measured Eppley ultraviolet. M.A. and P.B.S. measured NOx. S.G., S.D. and P.S.S. measured OH. X.Z., S.B. and M.A.C. coordinated the study. X.Z. wrote the paper. All the authors discussed the results and commented on the manuscript.

Corresponding author

Correspondence to Xianliang Zhou.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Zhou, X., Zhang, N., TerAvest, M. et al. Nitric acid photolysis on forest canopy surface as a source for tropospheric nitrous acid. Nature Geosci 4, 440–443 (2011). https://doi.org/10.1038/ngeo1164

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/ngeo1164

This article is cited by

Search

Advanced search

Quick links

Nature Briefing Microbiology

Sign up for the Nature Briefing: Microbiology newsletter — what matters in microbiology research, free to your inbox weekly.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing: Microbiology