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Photosensitized reduction of nitrogen dioxide on humic acid as a source of nitrous acid

Nature volume 440, pages 195–198 (2006)Cite this article

Abstract

Nitrous acid is a significant photochemical precursor of the hydroxyl radical1,2,3,4,5,6,7,8,9,10,11,12,13, the key oxidant in the degradation of most air pollutants in the troposphere. The sources of nitrous acid in the troposphere, however, are still poorly understood. Recent atmospheric measurements7,10,11,12,13,14,15,16,17 revealed a strongly enhanced formation of nitrous acid during daytime via unknown mechanisms. Here we expose humic acid films to nitrogen dioxide in an irradiated tubular gas flow reactor and find that reduction of nitrogen dioxide on light-activated humic acids is an important source of gaseous nitrous acid. Our findings indicate that soil and other surfaces containing humic acid exhibit an organic surface photochemistry that produces reductive surface species, which react selectively with nitrogen dioxide. The observed rate of nitrous acid formation could explain the recently observed high daytime concentrations of nitrous acid in the boundary layer, the photolysis of which accounts for up to 60 per cent of the integrated hydroxyl radical source strengths3,6,7,8,9,10,11,12,13. We suggest that this photo-induced nitrous acid production on humic acid could have a potentially significant impact on the chemistry of the lowermost troposphere.

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Figure 1: Conversion of NO 2 → HONO on 1 mg layers of humic acids initiated by visible light (400–700 nm).
Figure 2: Conversion of NO 2 → HONO on irradiated soil in presence of 17 p.p.b. NO 2 and 30% relative humidity.

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Acknowledgements

We thank Y. Abd El Aal, S. Canonica, M. Birrer, J. Dommen, A. Prêvot, L. Urech and I. Alxneit for discussions or technical support. K.S. thanks the Swiss National Science Foundation for support. C.G. acknowledges the grant by Primequal2 for the project SHONO and the CNRS.

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Authors and Affiliations

  1. Paul Scherrer Institut, Laboratory of Radio- and Environmental Chemistry, Villigen, CH-5232, Switzerland

    Konrad Stemmler, Markus Ammann & Chantal Donders

  2. Bergische Universität Wuppertal, Physikalische Chemie/FB C, Wuppertal, D-42097, Germany

    Jörg Kleffmann

  3. Department of Chemistry and Biochemistry, University of Bern, Bern, CH-3012, Switzerland

    Chantal Donders

  4. Laboratoire d'Application de la Chimie à l'Environnement (UCBL-CNRS), Villeurbanne, F-69622, France

    Christian George

Authors
  1. Konrad Stemmler
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  2. Markus Ammann
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  3. Chantal Donders
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  4. Jörg Kleffmann
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  5. Christian George
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Correspondence to Konrad Stemmler.

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Reprints and permissions information is available at npg.nature.com/reprintsandpermissions. The authors declare no competing financial interests.

Supplementary information

Supplementary Figure 1

This figure compares the photoreactivity of humic acids of different origin towards NO2. Shown are data for humic acids originating from peat, soil, or lignite-coal, which are all reactive towards NO2 and a reference experiment on uncoated glass surface under the same experimental conditions which shows no measurable reactivity. (PDF 38 kb)

Supplementary Figure 2

This figure shows the spectral irradiances of the three light sources used in the present study and compares them with the solar spectral irradiance at the earth surface. (PDF 54 kb)

Supplementary Figure 3

This figure compares the photo-formation of gaseous H2O2 and HONO on an Aldrich Humic Acid surface under UV-A irradiation. While only minor amounts of H2O2 are formed, a substantial amount of HONO is produced on this surface. (PDF 47 kb)

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Stemmler, K., Ammann, M., Donders, C. et al. Photosensitized reduction of nitrogen dioxide on humic acid as a source of nitrous acid. Nature 440, 195–198 (2006). https://doi.org/10.1038/nature04603

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