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The role of long-lived reactive oxygen intermediates in the reaction of ozone with aerosol particles

Nature Chemistry volume 3, pages 291–295 (2011)Cite this article

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Abstract

The heterogeneous reactions of O3 with aerosol particles are of central importance to air quality. They are studied extensively, but the molecular mechanisms and kinetics remain unresolved. Based on new experimental data and calculations, we show that long-lived reactive oxygen intermediates (ROIs) are formed. The chemical lifetime of these intermediates exceeds 100 seconds, which is much longer than the surface residence time of molecular O3 (~10−9 s). The ROIs explain and resolve apparent discrepancies between earlier quantum mechanical calculations and kinetic experiments. They play a key role in the chemical transformation and adverse health effects of toxic and allergenic air-particulate matter, such as soot, polycyclic aromatic hydrocarbons and proteins. ROIs may also be involved in the decomposition of O3 on mineral dust and in the formation and growth of secondary organic aerosols. Moreover, ROIs may contribute to the coupling of atmospheric and biospheric multiphase processes.

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Figure 1: Illustration of the atmospheric and physiological sources, coupling and effects of ROS.
Figure 2: Lennard-Jones potential energy diagram for the adsorption of molecular and dissociated O3.
Figure 3: Experimental and model results for heterogeneous ozonolysis of the PAH BaP on soot aerosol particles.
Figure 4: Energy profile for the reaction of O3 with the PAH BaP on soot.
Figure 5: Uptake coefficients of NO2 by protein particles.
Figure 6: Uptake coefficients of NO2 by O3-pretreated protein particles.

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Acknowledgements

This work was funded by the Max Planck Society, the Swiss National Science Foundation (Grant 130175) and the European Integrated Project on Aerosol, Cloud, Climate and Air Quality Interactions (036833-2 EUCAARI). We thank M. Birrer, T. Bartels-Rausch and M. Kerbrat for support, and the staff of the Paul Scherrer Institute accelerator facilities for providing the stable proton beams used to produce 13N with the PROTRAC facility. M.S. is supported by the Max Planck Graduate Center, Johannes Gutenberg University Mainz, the University of Tokyo, and the Ministry of Education, Culture, Sports, Science and Technology, Japan.

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Authors and Affiliations

  1. Department of Biogeochemistry, Max Planck Institute for Chemistry, PO Box 3060, Mainz, 55128, Germany

    Manabu Shiraiwa, Hong Yang, Yingyi Zhang & Ulrich Pöschl

  2. Paul Scherrer Institut, Laboratory of Radiochemistry and Environmental Chemistry, Villigen, CH-5232, Switzerland

    Yulia Sosedova, Aurélie Rouvière & Markus Ammann

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

    Yulia Sosedova

  4. Department of Chemistry, University of Toronto, 80 St George Street, Toronto, M5S 3H6, Ontario, Canada

    Jonathan P. D. Abbatt

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Contributions

U.P., M.A. and M.S. designed the research. M.S., Y.S., A.R. and M.A. performed tracer experiments and M.S. analysed the data. H.Y. and Y.Z. contributed to the protein studies. M.S. and U.P. conducted the kinetic modelling. M.S., U.P., M.A. and J.A. discussed the results. M.S., U.P. and M.A. co-wrote the paper.

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Correspondence to Ulrich Pöschl.

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Shiraiwa, M., Sosedova, Y., Rouvière, A. et al. The role of long-lived reactive oxygen intermediates in the reaction of ozone with aerosol particles. Nature Chem 3, 291–295 (2011). https://doi.org/10.1038/nchem.988

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