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:

Hydroxyl radical buffered by isoprene oxidation over tropical forests

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

Subjects

An Erratum to this article was published on 28 February 2012

This article has been updated

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.

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: 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.

Similar content being viewed by others

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.

References

  1. Ganzeveld, L. & Lelieveld, J. Impact of Amazonian deforestation on atmospheric chemistry. Geophys. Res. Lett. L06105 (2004).

  2. Arneth, A. et al. Terrestrial biogeochemical feedbacks in the climate system. Nature Geosci. 3, 525–532 (2010).

    Article  Google Scholar 

  3. Pöschl, U. et al. Rainforest aerosols as biogenic nuclei of clouds and precipitation in the Amazon. Science 329, 1513–1516 (2010).

    Article  Google Scholar 

  4. Lelieveld, J. et al. Atmospheric oxidation capacity sustained by a tropical forest. Nature 452, 737–740 (2008).

    Article  Google Scholar 

  5. Butler, T. M. et al. Improved simulation of isoprene oxidation chemistry with the ECHAM5/MESSy chemistry-climate model: Lessons from the GABRIEL airborne field campaign. Atmos. Chem. Phys. 8, 4529–4546 (2008).

    Article  Google Scholar 

  6. Lawrence, M. G., Jöckel, P. & von Kuhlmann, R. What does the global mean OH concentration tell us? Atmos. Chem. Phys. 1, 37–49 (2001).

    Article  Google Scholar 

  7. Levy, H. I. Normal atmosphere: Large radical and formaldehyde concentrations predicted. Science 141–143 (1971).

    Article  Google Scholar 

  8. Guenther, A. et al. A global model of natural volatile organic compound emissions. J. Geophys. Res. 100, 8873–8892 (1995).

    Article  Google Scholar 

  9. Dillon, T. J. & Crowley, J. N. Direct detection of OH formation in the reactions of HO2 with CH3C(O)O2 and other substituted peroxy radicals. Atmos. Chem. Phys. 8, 4877–4889 (2008).

    Article  Google Scholar 

  10. Hofzumahaus, A. et al. Amplified trace gas removal in the troposphere. Science 324, 1702–1704 (2009).

    Article  Google Scholar 

  11. Kiendler-Scharr, A. et al. New particle formation in forests inhibited by isoprene emissions. Nature 461, 381–384 (2009).

    Article  Google Scholar 

  12. Kubistin, D. et al. Hydroxyl radicals in the tropical troposphere over the Suriname rain forest: Comparison of measurements with the box model MECCA. Atmos. Chem. Phys. 10, 9705–9728 (2010).

    Article  Google Scholar 

  13. Paulot, F. et al. Unexpected epoxide formation in the gas-phase photooxidation of isoprene. Science 325, 730–733 (2009).

    Article  Google Scholar 

  14. Peeters, J. & Müller, J-F. HOx radical regeneration in isoprene oxidation via peroxy radical isomerisations. II: Experimental evidence and global impact. Phys. Chem. Chem. Phys. 10, 14227–14235 (2010).

    Article  Google Scholar 

  15. Peeters, J., Nguyen, T. L. & Vereecken, L. HOx radical regeneration in the oxidation of isoprene. Phys. Chem. Chem. Phys. 11, 5935–5939 (2009).

    Article  Google Scholar 

  16. Vilà-Guerau de Arellano, J. et al. The role of boundary layer dynamics on the diurnal evolution of isoprene and the hydroxyl radical over tropical forests. J. Geophys. Res. 116, D07304 (2011).

    Article  Google Scholar 

  17. Saunders, S. M., Jenkin, M. E., Derwent, R. G. & Pilling, M. J. Protocol for the development of the master chemical mechanism, MCM v3 (part a): Tropospheric degradation of non-aromatic volatile organic compounds. Atmos. Chem. Phys. 34, 161–180 (2003).

    Article  Google Scholar 

  18. Martinez, M. et al. Hydroxyl radicals in the tropical troposphere over the Suriname rainforest: Airborne measurements. Atmos. Chem. Phys. 10, 3759–3773 (2010).

    Article  Google Scholar 

  19. Whalley, L. K. et al. The chemistry of OH and HO2 radicals in the boundary layer over the tropical Atlantic ocean. Atmos. Chem. Phys. 10, 1555–1576 (2010).

    Article  Google Scholar 

  20. Archibald, A. T., Tonokura, K., Kawasaki, M., Percival, C. J. & Shallcross, D. E. On the impact of HO2−H2O complexes in the marine boundary layer: A possible sink for HO2 . Terr. Atmos. Ocean. Sci. 22, 71–78 (2011).

    Article  Google Scholar 

  21. Fuchs, H. et al. Detection of HO2 by laser-induced fluorescence: Calibration and interferences from RO2 radicals. Atmos. Meas. Tech. 4, 1209–1225 (2011).

    Article  Google Scholar 

  22. Rohrer, F. & Berresheim, H. Strong correlation between levels of tropospheric hydroxyl radicals and solar ultraviolet radiation. Nature 442, 184–187 (2006).

    Article  Google Scholar 

  23. Di Carlo, P. Missing OH reactivity in a forest: Evidence for unknown reactive biogenic VOCs. Science 304, 722–725 (2004).

    Article  Google Scholar 

  24. Sinha, V. et al. OH reactivity measurements within a boreal forest: Evidence for unknown reactive emissions. Environ. Sci. Technol. 44, 6614–6620 (2010).

    Article  Google Scholar 

  25. Mentel, T. F. et al. Photochemical production of aerosols from real plant emissions. Atmos. Chem. Phys. 9, 4387–4406 (2009).

    Article  Google Scholar 

  26. Crounse, J. D., Paulot, F., Kjaergaard, H. G. & Wennberg, P. O. Peroxy radical isomerization in the oxidation of isoprene. Phys. Chem. Chem. Phys. 13, 13607–13613 (2011).

    Article  Google Scholar 

  27. Karl, T., Guenther, A., Turnipseed, A., Tyndall, G., Artaxo, P. & Martin, S. Rapid formation of isoprene photo-oxidation products observed in Amazonia. Atmos. Chem. Phys. 20, 7753–7767 (2009).

    Article  Google Scholar 

  28. Hewitt, C. N. et al. Overview: Oxidant and particle photochemical processes above a south-east Asian tropical rainforest (the OP3 project): Introduction, rationale, location characteristics and tools. Atmos. Chem. Phys. 10, 169–199 (2010).

    Article  Google Scholar 

  29. Sinha, V., Williams, J., Crowley, J. N. & Lelieveld, J. The comparative reactivity method—a new tool to measure total OH reactivity in ambient air. Atmos. Chem. Phys. 8, 2213–2227 (2008).

    Article  Google Scholar 

  30. Gu, L. et al. Advantages of diffuse radiation for terrestrial ecosystem productivity. J. Geophys. Res. 107, 4050 (2002).

    Google Scholar 

Download references

Acknowledgements

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

Author information

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
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. M. G. Lawrence
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. J. N. Crowley
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. T. J. Dillon
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. S. Gromov
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. C. B. M. Groß
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. L. Vereecken
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. J. Lelieveld
    View author publications

    You can also search for this author in PubMed Google Scholar

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.

Corresponding author

Correspondence to D. Taraborrelli.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

Supplementary Information (PDF 2403 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

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

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/ngeo1405

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