A new atmospherically relevant oxidant of sulphur dioxide

Abstract

Atmospheric oxidation is a key phenomenon that connects atmospheric chemistry with globally challenging environmental issues, such as climate change1, stratospheric ozone loss2, acidification of soils and water3, and health effects of air quality4. Ozone, the hydroxyl radical and the nitrate radical are generally considered to be the dominant oxidants that initiate the removal of trace gases, including pollutants, from the atmosphere. Here we present atmospheric observations from a boreal forest region in Finland, supported by laboratory experiments and theoretical considerations, that allow us to identify another compound, probably a stabilized Criegee intermediate (a carbonyl oxide with two free-radical sites) or its derivative, which has a significant capacity to oxidize sulphur dioxide and potentially other trace gases. This compound probably enhances the reactivity of the atmosphere, particularly with regard to the production of sulphuric acid, and consequently atmospheric aerosol formation. Our findings suggest that this new atmospherically relevant oxidation route is important relative to oxidation by the hydroxyl radical, at least at moderate concentrations of that radical. We also find that the oxidation chemistry of this compound seems to be tightly linked to the presence of alkenes of biogenic origin.

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Figure 1: Data from a boreal forest site, obtained during summer 2010.
Figure 2: Plots showing that alkenes emitted by vegetation are possibly the source of oxidant X.
Figure 3: Proposed mechanism for the formation of oxidant X.
Figure 4: H2SO4 produced from X + SO2 can explain the difference between the Hyytiälä 2010 H2SO4 measurements and calculated values using only OH + SO2.

References

  1. 1

    Liao, H. et al. Effect of chemistry-aerosol-climate coupling on predictions of future climate and future levels of tropospheric ozone and aerosols. J. Geophys. Res.. 114, D10306, http://dx.doi.org/10.1029/2008JD010984 (2009)

  2. 2

    Rowland, F. S. Stratospheric ozone depletion. Phil. Trans. R. Soc. Lond. B 361, 769–790 (2006)

    CAS  Article  Google Scholar 

  3. 3

    Likens, G. E., Bormann, F. H. & Johnson, N. M. Acid rain. Environment 14, 33–40 (1974)

    Google Scholar 

  4. 4

    Fenger, J. Air pollution in the last 50 years — from local to global. Atmos. Environ. 43, 13–22 (2009)

    CAS  ADS  Article  Google Scholar 

  5. 5

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

    CAS  ADS  Article  Google Scholar 

  6. 6

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

    CAS  ADS  Article  Google Scholar 

  7. 7

    Su, H. et al. Soil nitrite as a source of atmospheric HONO and OH radicals. Science 333, 1616–1618 (2011)

    CAS  ADS  Article  Google Scholar 

  8. 8

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

    CAS  ADS  Article  Google Scholar 

  9. 9

    Lou, S. et al. Atmospheric OH reactivities in the Pearl River Delta – China in summer 2006: measurements and model results. Atmos. Chem. Phys. 10, 11243–11260 (2010)

    CAS  ADS  Article  Google Scholar 

  10. 10

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

    CAS  ADS  Article  Google Scholar 

  11. 11

    Montzka, S. A. et al. Small interannual variability of global atmospheric hydroxyl. Science 331, 67–70 (2011)

    CAS  ADS  Article  Google Scholar 

  12. 12

    Sipilä, M. et al. The role of sulfuric acid in atmospheric nucleation. Science 327, 1243–1246 (2010)

    ADS  Article  Google Scholar 

  13. 13

    Eisele, F. L. & Tanner, D. J. Ion-assisted tropospheric OH measurements. J. Geophys. Res. 96, 9295–9308 (1991)

    CAS  ADS  Article  Google Scholar 

  14. 14

    Petäjä, T. et al. Sulfuric acid and OH concentrations in a boreal forest site. Atmos. Chem. Phys. 9, 7435–7448 (2009)

    ADS  Article  Google Scholar 

  15. 15

    Hakola, H. Seasonal variation of VOC concentrations above a boreal coniferous forest. Atmos. Environ. 37, 1623–1634 (2003)

    CAS  ADS  Article  Google Scholar 

  16. 16

    Lappalainen, H. K. et al. Day-time concentrations of biogenic volatile organic compounds in a boreal forest canopy and their relation to environmental and biological factors. Atmos. Chem. Phys. 9, 5447–5459 (2009)

    CAS  ADS  Article  Google Scholar 

  17. 17

    Cocks, A. T., Fernando, R. P. & Fletcher, I. S. The gas-phase reaction of the methylperoxy radical with sulphur dioxide. Atmos. Environ. 20, 2359–2366 (1986)

    CAS  ADS  Article  Google Scholar 

  18. 18

    Xie, Z. D. Formation mechanism of condensation nuclei in nighttime atmosphere and the kinetics of the SO2-O3-NO2 system. J. Phys. Chem. 96, 1543–1547 (1992)

    CAS  Article  Google Scholar 

  19. 19

    Kurtén, T., Lane, J. R., Jørgensen, S. & Kjaergaard, H. Nitrate radical addition-elimination reactions of atmospherically relevant sulfur-containing molecules. Phys. Chem. Chem. Phys. 12, 12833–12839 (2010)

    Article  Google Scholar 

  20. 20

    Kurtén, T., Lane, J. R., Jørgensen, S. & Kjaergaard, H. A. Computational study of the oxidation of SO2 to SO3 by gas-phase organic oxidant. J. Phys. Chem. A 115, 8669–8681 (2011)

    Article  Google Scholar 

  21. 21

    Hatakeyama, S., Kobayashi, H., Lin, Z.-Y., Tagaki, H. & Akimoto, H. Mechanism for the reaction of H2COO with SO2 . J. Phys. Chem. 90, 4131–4135 (1986)

    CAS  Article  Google Scholar 

  22. 22

    Johnson, D., Lewin, A. G. & Marston, G. The effect of Criegee-intermediate scavengers on the OH yield from the reaction of ozone with 2-methylbut-2-ene. J. Phys. Chem. A 105, 2933–2935 (2001)

    CAS  Article  Google Scholar 

  23. 23

    Jiang, L., Xu, Y. & Ding, A. J. Reaction of stabilized Criegee intermediates from ozonolysis of limonene with sulfur dioxide: ab initio and DFT study. J. Phys. Chem. A 114, 12452–1246 (2010)

    CAS  Article  Google Scholar 

  24. 24

    Welz, O. et al. Direct kinetic measurements of Criegee intermediate (CH2OO) formed by reaction of CH2I with O2 . Science 335, 204–207 (2012)

    CAS  ADS  Article  Google Scholar 

  25. 25

    Cox, R. A. & Penkett, S. A. Oxidation of atmospheric SO2 by products of the ozone-olefin reaction. Nature 230, 321–322 (1971)

    CAS  ADS  Article  Google Scholar 

  26. 26

    Drozd, G. T., Kroll, J. & Donahue, N. M. 2,2-Dimethyl-2-butene (TME) ozonolysis: pressure dependence of stabilized Criegee intermediates and evidence of stabilized vinyl hydroperoxides. J. Phys. Chem. A 115, 161–166 (2011)

    CAS  Article  Google Scholar 

  27. 27

    Heald, C. L. et al. Predicted change in global secondary organic aerosol concentrations in response to future climate, emissions, and land use change. J. Geophys. Res.. 113, D05211, http://dx.doi.org/10.1029/2007JD009092 (2008)

  28. 28

    Spracklen, D. V. et al. Contribution of particle formation to global cloud condensation nuclei concentrations. Geophys. Res. Lett.. 35, L06808, http://dx.doi.org/10.1029/2007GL033038 (2008)

  29. 29

    Arneth, A., Unger, N., Kulmala, M. & Andreae, M. O. Clean the air, heat the planet? Science 326, 672–673 (2009)

    CAS  Article  Google Scholar 

  30. 30

    DeMore, W. et al. Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling. Evaluation 12. JPL Publication 97-4 (Jet Propulsion Laboratory, 1997)

  31. 31

    Tanner, D. J., Jefferson, A. & Eisele, F. L. Selected ion chemical ionization mass spectrometric measurement of OH. J. Geophys. Res. 102, 6415–6425 (1997)

    CAS  ADS  Article  Google Scholar 

  32. 32

    Mauldin, R. L., III et al. OH measurements during ACE-1: observations and model comparisons. J. Geophys. Res. 103, 16713–16729 (1998)

    CAS  ADS  Article  Google Scholar 

  33. 33

    Berndt, T. et al. Laboratory study on new particle formation from the reaction OH + SO2: influence of experimental conditions, H2O vapour, NH3 and the amine tert-butylamine on the overall process. Atmos. Chem. Phys. 10, 7101–7116 (2010)

    CAS  ADS  Article  Google Scholar 

  34. 34

    Hari, P. & Kulmala, M. Station for measuring ecosystem atmosphere relations (SMEAR II). Boreal Environ. Res. 10, 315–322 (2005)

    CAS  Google Scholar 

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Acknowledgements

We thank K. Pielok and A. Rohmer for technical assistance. This work was partially funded by the European Commission Sixth Framework programme project EUCAARI, contract no. 036833-2 (EUCAARI), the Academy of Finland (251427, 139656, Finnish centre of excellence 141135), the European Research Council (ATMNUCLE), the Kone Foundation, the Väisälä Foundation, the Maj and Tor Nessling Foundation (2010212), the Otto Malm Foundation and the US National Science Foundation.

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R.L.M., T.B. and M.S. designed the experiments, R.L.M., T.B., M.S. and S.K. performed the laboratory experiments, R.L.M., T.P. and M.S. conducted the field measurements, T.B., T.K., and P.P. performed the model and theoretical calculations, and R.L.M., T.B., M.S. and P.P. analysed the data. All authors (R.L.M., T.B., M.S., P.P., T.P., S.K., T.K., F.S., V.-M.K., and M.K.) contributed to the interpretation and to manuscript preparation.

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Correspondence to R. L. Mauldin III.

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The authors declare no competing financial interests.

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Mauldin III, R., Berndt, T., Sipilä, M. et al. A new atmospherically relevant oxidant of sulphur dioxide. Nature 488, 193–196 (2012). https://doi.org/10.1038/nature11278

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