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Hydroxyl radical buffered by isoprene oxidation over tropical forests

Nature Geoscience volume 5, pages 190–193 (2012)Cite this article

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An Erratum to this article was published on 28 February 2012

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Abstract

The hydroxyl radical is a key oxidant in the Earth’s atmosphere. This short-lived highly reactive molecule plays an important role in the degradation of volatile organic compounds, leading to the production of ozone and the formation and growth of aerosol particles1,2,3. In this way, hydroxyl radicals influence air quality and regional climate. Measurements over tropical forests suggest that hydroxyl radicals are recycled following reaction with the volatile organic compound isoprene4,5, but the chemistry underpinning this observation is uncertain. Here, we propose a detailed chemical mechanism for the oxidation of isoprene by hydroxyl radicals. The photo-oxidation of unsaturated hydroperoxy-aldehydes—a product of isoprene oxidation—is a central part of the mechanism; their photolysis initiates a hydroxyl radical production cascade that is limited by the reaction of hydroperoxy-aldehydes with the hydroxyl radical itself. We incorporate this mechanism into a global atmospheric chemistry model and find that measurements of hydroxyl radical concentrations over a pristine region of the Amazon, and in moderately polluted conditions, are captured well. On the basis of this agreement, we suggest that isoprene oxidation can buffer hydroxyl radical concentrations, by serving as both a sink and source for these radicals.

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Figure 1: OH concentrations in the isoprene-rich forest boundary layer.
Figure 2: OH buffering mechanism.
Figure 3: OH-recycling in isoprene oxidation.
Figure 4: Annual average surface OH concentrations and OH-recycling efficiency in VOC oxidation.

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Change history

  • 28 February 2012

    This Letter was published online and in print with the author M. G. Lawrence being incorrectly affiliated to the Cyprus Institute. This has been corrected in the PDF and HTML versions of this Letter.

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Acknowledgements

We thank the GABRIEL team for collecting and providing the dataset. We thank M. Martinez, H. Harder and J. Williams for helpful discussions.

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Author notes

  1. M. G. Lawrence

    Present address: Present address: The Institute for Advanced Sustainability Studies, 14467 Potsdam, Germany,

Authors and Affiliations

  1. Max Planck Institute for Chemistry, 55128 Mainz, Germany

    D. Taraborrelli, M. G. Lawrence, J. N. Crowley, T. J. Dillon, S. Gromov, C. B. M. Groß, L. Vereecken & J. Lelieveld

  2. Cyprus Institute, PO Box 27456, Nicosia, Cyprus

    J. Lelieveld

  3. King Saud University, PO Box 2454, Riyadh, Saudi Arabia

    J. Lelieveld

Authors
  1. D. Taraborrelli
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  2. M. G. Lawrence
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  4. T. J. Dillon
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  6. C. B. M. Groß
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  7. L. Vereecken
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  8. J. Lelieveld
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Contributions

D.T. developed the oxidation mechanisms and performed the simulations. L.V. performed theoretical calculations and analysed the available experimental data on 1,6-H-shifts. C.B.M.G., T.J.D. and J.N.C. performed experiments on isoprene-derived RO2. S.G. and D.T. calculated the OH budget of the mechanism, global OH and the methane lifetime. D.T., M.G.L., J.L. and L.V. wrote the manuscript.

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Correspondence to D. Taraborrelli.

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The authors declare no competing financial interests.

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Taraborrelli, D., Lawrence, M., Crowley, J. et al. Hydroxyl radical buffered by isoprene oxidation over tropical forests. Nature Geosci 5, 190–193 (2012). https://doi.org/10.1038/ngeo1405

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