Abstract

Secondary organic aerosol contributes to the atmospheric particle burden with implications for air quality and climate. Biogenic volatile organic compounds such as terpenoids emitted from plants are important secondary organic aerosol precursors with isoprene dominating the emissions of biogenic volatile organic compounds globally. However, the particle mass from isoprene oxidation is generally modest compared to that of other terpenoids. Here we show that isoprene, carbon monoxide and methane can each suppress the instantaneous mass and the overall mass yield derived from monoterpenes in mixtures of atmospheric vapours. We find that isoprene ‘scavenges’ hydroxyl radicals, preventing their reaction with monoterpenes, and the resulting isoprene peroxy radicals scavenge highly oxygenated monoterpene products. These effects reduce the yield of low-volatility products that would otherwise form secondary organic aerosol. Global model calculations indicate that oxidant and product scavenging can operate effectively in the real atmosphere. Thus highly reactive compounds (such as isoprene) that produce a modest amount of aerosol are not necessarily net producers of secondary organic particle mass and their oxidation in mixtures of atmospheric vapours can suppress both particle number and mass of secondary organic aerosol. We suggest that formation mechanisms of secondary organic aerosol in the atmosphere need to be considered more realistically, accounting for mechanistic interactions between the products of oxidizing precursor molecules (as is recognized to be necessary when modelling ozone production).

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All data used are shown as figures or tables in the manuscript or in Supplementary Information. Raw data are available from the corresponding author on reasonable request.

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References

  1. 1.

    Hallquist, M. et al. The formation, properties and impact of secondary organic aerosol: current and emerging issues. Atmos. Chem. Phys. 9, 5155–5236 (2009).

  2. 2.

    Jimenez, J. L. et al. Evolution of organic aerosols in the atmosphere. Science 326, 1525–1529 (2009).

  3. 3.

    Goldstein, A. H. & Galbally, I. E. Known and unexplored organic constituents in the Earth’s atmosphere. Environ. Sci. Technol. 41, 1514–1521 (2007).

  4. 4.

    Spracklen, D. V. et al. Aerosol mass spectrometer constraint on the global secondary organic aerosol budget. Atmos. Chem. Phys. 11, 12109–12136 (2011).

  5. 5.

    Kanakidou, M. et al. Organic aerosol and global climate modelling: a review. Atmos. Chem. Phys. 5, 1053–1123 (2005).

  6. 6.

    Guenther, A. et al. Estimates of global terrestrial isoprene emissions using MEGAN (Model of Emissions of Gases and Aerosols from Nature). Atmos. Chem. Phys. 6, 3181–3210 (2006).

  7. 7.

    Guenther, A. et al. The Model of Emissions of Gases and Aerosols from Nature version 2.1 (MEGAN2.1): an extended and updated framework for modeling biogenic emissions. Geosci. Model Dev. 5, 1471–1492 (2012).

  8. 8.

    Carlton, A. G., Wiedinmyer, C. & Kroll, J. H. A review of secondary organic aerosol (SOA) formation from isoprene. Atmos. Chem. Phys. 9, 4987–5005 (2009).

  9. 9.

    Clark, C. H. et al. Temperature effects on secondary organic aerosol (SOA) from the dark ozonolysis and photo-oxidation of isoprene. Environ. Sci. Technol. 50, 5564–5571 (2016).

  10. 10.

    Liu, J. et al. Efficient isoprene secondary organic aerosol formation from a non-IEPOX pathway. Environ. Sci. Technol. 50, 9872–9880 (2016).

  11. 11.

    Edney, E. O. et al. Formation of 2-methyl tetrols and 2-methylglyceric acid in secondary organic aerosol from laboratory irradiated isoprene/NOx/SO2/air mixtures and their detection in ambient PM2.5 samples collected in the eastern United States. Atmos. Environ. 39, 5281–5289 (2005).

  12. 12.

    Surratt, J. D. et al. Reactive intermediates revealed in secondary organic aerosol formation from isoprene. Proc. Natl Acad. Sci. USA 107, 6640–6645 (2010).

  13. 13.

    Claeys, M. et al. Formation of secondary organic aerosols from isoprene and its gas-phase oxidation products through reaction with hydrogen peroxide. Atmos. Environ. 38, 4093–4098 (2004).

  14. 14.

    Robinson, N. H. et al. Evidence for a significant proportion of secondary organic aerosol from isoprene above a maritime tropical forest. Atmos. Chem. Phys. 11, 1039–1050 (2011).

  15. 15.

    Xu, L. et al. Effects of anthropogenic emissions on aerosol formation from isoprene and monoterpenes in the southeastern United States. Proc. Natl Acad. Sci. USA 112, 37–42 (2015).

  16. 16.

    Lee, A. et al. Gas-phase products and secondary aerosol yields from the ozonolysis of ten different terpenes. J. Geophys. Res. 111, D07302 (2006).

  17. 17.

    Lee, A. et al. Gas-phase products and secondary aerosol yields from the photooxidation of 16 different terpenes. J. Geophys. Res. 111, D17305 (2006).

  18. 18.

    Ng, N. L. et al. Effect of NOx level on secondary organic aerosol (SOA) formation from the photooxidation of terpenes. Atmos. Chem. Phys. 7, 5159–5174 (2007).

  19. 19.

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

  20. 20.

    Kanawade, V. P. et al. Isoprene suppression of new particle formation in a mixed deciduous forest. Atmos. Chem. Phys. 11, 6013–6027 (2011).

  21. 21.

    Lee, S. H. et al. Isoprene suppression of new particle formation: Potential mechanisms and implications. J. Geophys. Res. Atmos. 121, 14621–14635 (2016).

  22. 22.

    Ehn, M. et al. A large source of low-volatility secondary organic aerosol. Nature 506, 476–479 (2014).

  23. 23.

    Jenkin, M. E., Derwent, R. G. & Wallington, T. J. Photochemical ozone creation potentials for volatile organic compounds: rationalization and estimation. Atmos. Environ. 163, 128–137 (2017).

  24. 24.

    Odum, J. R. et al. Gas/particle partitioning and secondary organic aerosol yields. Environ. Sci. Technol. 30, 2580–2585 (1996).

  25. 25.

    Hoffmann, T. et al. Formation of organic aerosols from the oxidation of biogenic hydrocarbons. J. Atmos. Chem. 26, 189–222 (1997).

  26. 26.

    Seinfeld, J. H. & Pankow, J. F. Organic atmospheric particulate material. Annu. Rev. Phys. Chem. 54, 121–140 (2003).

  27. 27.

    Matsunaga, A. & Ziemann, P. J. Gas-wall partitioning of organic compounds in a Teflon film chamber and potential effects on reaction product and aerosol yield measurements. Aerosol Sci. Technol. 44, 881–892 (2010).

  28. 28.

    Zhang, X. et al. Influence of vapor wall loss in laboratory chambers on yields of secondary organic aerosol. Proc. Natl Acad. Sci. USA 111, 5802–5807 (2014).

  29. 29.

    Zhang, X. et al. Vapor wall deposition in Teflon chambers. Atmos. Chem. Phys. 15, 4197–4214 (2015).

  30. 30.

    Krechmer, J. E., Pagonis, D., Ziemann, P. J. & Jimenez, J. L. Quantification of gas-wall partitioning in Teflon environmental chambers using rapid bursts of low-volatility oxidized species generated in situ. Environ. Sci. Technol. 50, 5757–5765 (2016).

  31. 31.

    Sarrafzadeh, M. et al. Impact of NOx and OH on secondary organic aerosol formation from β-pinene photooxidation. Atmos. Chem. Phys. 16, 11237–11248 (2016).

  32. 32.

    Eddingsaas, N. C. et al. Alpha-pinene photooxidation under controlled chemical conditions—Part 2: SOA yield and composition in low- and high-NOx environments. Atmos. Chem. Phys. 12, 7413–7427 (2012).

  33. 33.

    Zhang, X., Pandis, S. N. & Seinfeld, J. H. Diffusion-limited versus quasi-equilibrium aerosol growth. Aerosol Sci. Technol. 46, 874–885 (2012).

  34. 34.

    O’Meara, S., Topping, D. O. & McFiggans, G. The rate of equilibration of viscous aerosol particles. Atmos. Chem. Phys. 16, 5299–5313 (2016).

  35. 35.

    Surratt, J. D. et al. Effect of acidity on secondary organic aerosol formation from isoprene. Environ. Sci. Technol. 41, 5363–5369 (2007).

  36. 36.

    Gaston, C. J. et al. Reactive uptake of an isoprene-derived epoxydiol to submicron aerosol particles. Environ. Sci. Technol. 48, 11178–11186 (2014).

  37. 37.

    Riva, M. et al. Effect of organic coatings, humidity and aerosol acidity on multiphase chemistry of isoprene epoxydiols. Environ. Sci. Technol. 50, 5580–5588 (2016).

  38. 38.

    Berndt, T. et al. Accretion product formation from self- and cross-reactions of RO2 radicals in the atmosphere. Angew. Chem. Int. Ed. 57, 3820–3824 (2018).

  39. 39.

    Tröstl, J. et al. The role of low-volatility organic compounds in initial particle growth in the atmosphere. Nature 533, 527–531 (2016).

  40. 40.

    Mohr, C. et al. Ambient observations of dimers from terpene oxidation in the gas phase: implications for new particle formation and growth. Geophys. Res. Lett. 44, 2958–2966 (2017).

  41. 41.

    Yan, C. et al. Source characterization of highly oxidized multifunctional compounds in a boreal forest environment using positive matrix factorization. Atmos. Chem. Phys. 16, 12715–12731 (2016).

  42. 42.

    Wennberg, P. O. et al. Gas-phase reactions of isoprene and its major oxidation products. Chem. Rev. 118, 3337–3390 (2018).

  43. 43.

    Simpson, D. et al. The EMEP MSC-W chemical transport model—technical description. Atmos. Chem. Phys. 12, 7825–7865 (2012).

  44. 44.

    Stadtler, S. et al. Ozone impacts of gas-aerosol uptake in global chemistry-transport models. Atmos. Chem. Phys. 18, 3147–3171 (2018).

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Acknowledgements

The EMEP modelling work was funded partially by EMEP under UNECE. Computer time for EMEP model runs was supported by the Research Council of Norway through the NOTUR project EMEP (NN2890K) for the central processing unit (CPU) time, and NorStore project European Monitoring and Evaluation Programme (NS9005K) for storage of data. The research presented is a contribution to the Swedish strategic research area ‘ModElling the Regional and Global Earth system’ (MERGE). This work was supported by Formas (grant numbers 214-2010-1756 and 942-2015-1537); the Swedish Research Council (grant number 2014-5332) and the European Research Council (Starting grant number 638703, ‘COALA’). Å.M.H. acknowledges Formas (grant number 214-2013-1430) and Vinnova, Sweden’s Innovation Agency (grant number 2013-03058), including support for her research stay at Forschungszentrum Jülich. The participation of the Manchester group was facilitated by the UK Natural Environment Research Council (NERC)-funded CCN-Vol project (NE/L007827/1) and National Centre for Atmospheric Science (NCAS) funding. J.A.T. was supported by a grant from the U.S. Department of Energy Office of Science: DE-SC0018221.

Reviewer information

Nature thanks F. Yu, P. Ziemann and the other anonymous reviewer(s) for their contribution to the peer review of this work.

Author information

Author notes

    • Iida Pullinen

    Present address: Department of Applied Physics, University of Eastern Finland, Kuopio, Finland

    • Sebastian Schmitt

    Present address: TSI, Aachen, Germany

    • Cheng Wu

    Present address: Department of Environmental Science and Analytical Chemistry, Stockholm University, Stockholm, Sweden

    • Carl J. Percival

    Present address: Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, USA

Affiliations

  1. School of Earth and Environmental Sciences, University of Manchester, Manchester, UK

    • Gordon McFiggans
    • , Michael Le Breton
    • , M. Rami Alfarra
    • , Thomas J. Bannan
    • , Carl J. Percival
    • , Michael Priestley
    •  & David Topping
  2. Institut für Energie- und Klimaforschung, IEK-8, Forschungszentrum Jülich, Jülich, Germany

    • Thomas F. Mentel
    • , Jürgen Wildt
    • , Iida Pullinen
    • , Sungah Kang
    • , Sebastian Schmitt
    • , Monika Springer
    • , Ralf Tillmann
    • , Cheng Wu
    • , Defeng Zhao
    •  & Astrid Kiendler-Scharr
  3. Institut für Bio- und Geowissenschaften, IBG-2, Forschungszentrum Jülich, Jülich, Germany

    • Jürgen Wildt
    •  & Einhard Kleist
  4. Department of Atmospheric and Oceanic Sciences and Institute of Atmospheric Sciences, Fudan University, Shanghai, China

    • Defeng Zhao
  5. Atmospheric Science, Department of Chemistry and Molecular Biology, University of Gothenburg, Gothenburg, Sweden

    • Mattias Hallquist
    • , Cameron Faxon
    • , Michael Le Breton
    •  & Robert Bergström
  6. IVL Swedish Environmental Research Institute, Gothenburg, Sweden

    • Åsa M. Hallquist
  7. Department of Earth, Space and Environment, Chalmers University of Technology, Gothenburg, Sweden

    • David Simpson
    •  & Robert Bergström
  8. EMEP MSC-W, Norwegian Meteorological Institute, Oslo, Norway

    • David Simpson
  9. Swedish Meteorological and Hydrological Institute, Norrköping, Sweden

    • Robert Bergström
  10. Atmospheric Chemistry Services, Okehampton, UK

    • Michael E. Jenkin
  11. Institute for Atmospheric and Earth System Research/Physics, Faculty of Science, University of Helsinki, Helsinki, Finland

    • Mikael Ehn
  12. Department of Atmospheric Sciences, University of Washington, Seattle, WA, USA

    • Joel A. Thornton
  13. National Centre for Atmospheric Science (NCAS), University of Manchester, Manchester, UK

    • M. Rami Alfarra
    •  & David Topping
  14. I. Physikalisches Institut, Universität zu Köln, Cologne, Germany

    • Astrid Kiendler-Scharr

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Contributions

G.M., T.F.M. and J.W. edited the manuscript and Supplementary Information. G.M., T.F.M., J.W., A.K.-S., M.H., D.S. and M.E.J. conceptualized and planned the study, and conducted data interpretation. J.W., I.P., S.K., E.K., S.S., M.S., R.T., C.W., D.Z., C.F., M.L.B., Å.M.H., M.R.A., T.J.B., C.J.P., M.P. and D.T. conducted data collection and analysis. D.S., R.B. and M.E.J. contributed the global model calculations. J.A.T., M.E., Å.M.H. and M.H. provided specific inputs to the manuscript and Supplementary Information. All co-authors discussed the results and commented on the manuscript and Supplementary Information.

Competing interests

The authors declare no competing interests.

Corresponding author

Correspondence to Thomas F. Mentel.

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  1. Supplementary Information

    The supplement contains one single pdf file. The material is ordered in 9 sections, which describe in detail the experiments and the applied methods. It contains Figures (17) and Tables (5), and additional references (69). The supplement provides all additional information which informed our findings

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