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Formation of mixed-phase particles during the freezing of polar stratospheric ice clouds

Nature Chemistry volume 2, pages 197–201 (2010)Cite this article

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Abstract

Polar stratospheric clouds (PSCs) are extremely efficient at catalysing the transformation of photostable chlorine reservoirs into photolabile species, which are actively involved in springtime ozone-depletion events. Why PSCs are such efficient catalysts, however, is not well understood. Here, we investigate the freezing behaviour of ternary HNO3–H2SO4–H2O droplets of micrometric size, which form type II PSC ice particles. We show that on freezing, a phase separation into pure ice and a residual solution coating occurs; this coating does not freeze but transforms into glass below ∼150 K. We find that the coating, which is thicker around young ice crystals, can still be approximately 30 nm around older ice crystals of diameter about 10 µm. These results affect our understanding of PSC microphysics and chemistry and suggest that chlorine-activation reactions are better studied on supercooled HNO3–H2SO4–H2O solutions rather than on a pure ice surface.

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Figure 1: DSC thermograms obtained from three samples of emulsified 23 wt% HNO3 and 3 wt% H2SO4.
Figure 2: The transition temperatures for the cooling and warming of bulk25 and emulsified HNO3–H2SO4–H2O.
Figure 3: Liquid coating around ice crystals.
Figure 4: Thickness of the ice crystal coating.

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Acknowledgements

We thank E. Bertel, S.C. Wofsy and M.B. McElroy for discussions. A.B. thanks the Physical and Chemical Departments of the University of Helsinki for providing facilities to perform the experiments. We are grateful for financial support from the European Research Council (Starting Grant SULIWA) and the Austrian Science Fund (START award Y391).

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Authors and Affiliations

  1. Institute of Physical Chemistry, University of Innsbruck, Innrain 52a, Innsbruck, A-6020, Austria

    Anatoli Bogdan & Thomas Loerting

  2. Department of Chemistry, Laboratory of Polymer Chemistry, University of Helsinki, PO Box 55, Helsinki, FIN-00014, Finland

    Anatoli Bogdan & Heikki Tenhu

  3. Department of Physical Sciences, University of Helsinki, PO Box 64, Helsinki, FI-00014, Finland

    Anatoli Bogdan

  4. Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, 92093-0356, California, USA

    Mario J. Molina

  5. Institute of General, Inorganic & Theoretical Chemistry, University of Innsbruck, Innrain 52a, Innsbruck, A-6020, Austria

    Erwin Mayer

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  1. Anatoli Bogdan
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Contributions

A.B. designed the study, performed measurements and calculations, collected and analysed data, and wrote the manuscript. M.J.M. designed the study, analysed data, and wrote and corrected the manuscript. H.T., E.M. and T.L. analysed data, and wrote and corrected the manuscript. All authors discussed the results and commented on the manuscript.

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Correspondence to Anatoli Bogdan or Thomas Loerting.

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The authors declare no competing financial interests.

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Bogdan, A., Molina, M., Tenhu, H. et al. Formation of mixed-phase particles during the freezing of polar stratospheric ice clouds. Nature Chem 2, 197–201 (2010). https://doi.org/10.1038/nchem.540

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