An important mechanism for ice cloud formation in the Earth's atmosphere is homogeneous nucleation of ice in aqueous droplets, and this process is generally assumed to produce hexagonal ice1,2. However, there are some reports that the metastable crystalline phase of ice, cubic ice, may form in the Earth's atmosphere3,4,5. Here we present laboratory experiments demonstrating that cubic ice forms when micrometre-sized droplets of pure water and aqueous solutions freeze homogeneously at cooling rates approaching those found in the atmosphere. We find that the formation of cubic ice is dominant when droplets freeze at temperatures below 190 K, which is in the temperature range relevant for polar stratospheric clouds and clouds in the tropical tropopause region. These results, together with heat transfer calculations, suggest that cubic ice will form in the Earth's atmosphere. If there were a significant fraction of cubic ice in some cold clouds this could increase their water vapour pressure, and modify their microphysics and ice particle size distributions5. Under specific conditions this may lead to enhanced dehydration of the tropopause region5.
This is a preview of subscription content, access via your institution
Subscribe to Journal
Get full journal access for 1 year
only $3.90 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Get time limited or full article access on ReadCube.
All prices are NET prices.
Young, K. C. Microphysical Processes in Clouds (Oxford Univ. Press, New York, 1993)
Pruppacher, H. R. & Klett, J. D. Microphysics of Clouds and Precipitation (Kluwer, Dordrecht, 1997)
Whalley, E. Scheiner's halo: evidence for ice Ic in the atmosphere. Science 211, 389–390 (1981)
Riikonen, M. et al. Halo observations provide evidence of airborne cubic ice in the Earth's atmosphere. Appl. Opt. 39, 6080–6085 (2000)
Murphy, D. M. Dehydration in cold clouds is enhanced by a transition from cubic to hexagonal ice. Geophys. Res. Lett. 30, doi:10.1029/2003GL018566 (2003)
Peter, T. Microphysics and heterogeneous chemistry of polar stratospheric clouds. Annu. Rev. Phys. Chem. 48, 785–822 (1997)
Baker, M. B. Cloud microphysics and climate. Science 276, 1072–1078 (1997)
DeMott, P. J. in Cirrus (eds Lynch, D. K., Sassen, K., Starr, D. C. & Stephens, G.) 102–135 (Oxford Univ. Press, New York, 2002)
Kohl, I., Mayer, E. & Hallbrucker, A. The glassy water-cubic ice system: a comparative study by X-ray diffraction and differential scanning calorimetry. Phys. Chem. Chem. Phys. 2, 1579–1586 (2000)
Mayer, E. & Hallbrucker, A. Cubic ice from liquid water. Nature 325, 601–602 (1987)
Huang, J. F. & Bartell, L. S. Kinetics of homogeneous nucleation in the freezing of large water clusters. J. Phys. Chem. 99, 3924–3931 (1995)
Lepault, J., Bigot, D., Studer, D. & Erk, I. Freezing of aqueous specimens: an X-ray diffraction study. J. Microsc. 187, 158–166 (1997)
Dowell, L. G., Moline, S. W. & Rinfret, A. P. A low-temperature X-ray diffraction study of ice structure formed in aqueous gelatin gels. Biochim. Biophys. Acta 59, 158–167 (1962)
Dowell, L. G. & Rinfret, A. P. Low-temperature forms of ice as studied by X-ray diffraction. Nature 188, 1144–1148 (1960)
Jenniskens, P. & Blake, D. F. Structural transitions in amorphous water ice and astrophysical implications. Science 265, 753–756 (1994)
Steytler, D. C., Dore, J. C. & Wright, C. J. Neutron diffraction study of cubic ice nucleation in a porous silica network. J. Phys. Chem. 87, 2458–2459 (1983)
Takahashi, T. On the role of cubic structure in ice nucleation. J. Cryst. Growth 59, 441–449 (1982)
Kiefte, H., Clouter, M. J. & Whalley, E. Cubic ice, snowflakes, and rare-gas solids: surface energy, entropy, and the stability of small crystals. J. Chem. Phys. 81, 1419–1420 (1984)
Svishchev, I. M. & Kusalik, P. G. Crystallization of liquid water in a molecular dynamics simulation. Phys. Rev. Lett. 73, 975–978 (1994)
Yamada, M., Mossa, S., Stanley, H. E. & Sciortino, F. Interplay between time-temperature transformation and the liquid-liquid phase transition in water. Phys. Rev. Lett. 88, 195701 (2002)
McClune, W. F. Powder Diffraction File-2 (The International Centre for Diffraction Data, Newtown Square, 2002)
Kuhs, W. F., Bliss, D. V. & Finney, J. L. High-resolution neutron powder diffraction study of ice-Ic. J. Phys. Colloq. 48, 631–636 (1987)
Eidelman, N., Azoury, R. & Sarig, S. Reversal of trends in impurity effects on crystallization parameters. J. Cryst. Growth 74, 1–9 (1986)
Murray, B. J. & Plane, J. M. C. The uptake of atomic oxygen on ice films: Implications for noctilucent clouds. Phys. Chem. Chem. Phys. 5, 4129–4138 (2003)
Ostwald, W. Studien über die Bildung und Umwandlung fester Körper. Z. Phys. Chem. 22, 289–330 (1897)
Gao, R. S. et al. Evidence that nitric acid increases relative humidity in low-temperature cirrus clouds. Science 303, 516–520 (2004)
Chang, H. Y. A., Koop, T., Molina, L. T. & Molina, M. J. Phase transitions in emulsified HNO3/H2O and HNO3/H2SO4/H2O solutions. J. Phys. Chem. A 103, 2673–2679 (1999)
Koop, T., Kapilashrami, A., Molina, L. T. & Molina, M. J. Phase transitions of sea-salt/water mixtures at low temperatures: Implications for ozone chemistry in the polar marine boundary layer. J. Geophys. Res. 105, 26393–26402 (2000)
Bertram, A. K., Koop, T., Molina, L. T. & Molina, M. J. Ice formation in (NH4)2SO4-H2O particles. J. Phys. Chem. A 104, 584–588 (2000)
Koop, T., Luo, B. P., Tsias, A. & Peter, T. Water activity as the determinant for homogeneous ice nucleation in aqueous solutions. Nature 406, 611–614 (2000)
We thank D. M. Murphy for several helpful discussions on cubic ice, G. N. Patey for discussions on theoretical calculations, and A. Lam and B. Patrick for their assistance with X-ray diffraction measurements and interpretation. We are also grateful to M. Raudsepp for discussions on crystallography. This research was supported by the Canadian Foundation for Climate and Atmospheric Sciences, the Natural Sciences and Engineering Research Council of Canada, and the Canadian Foundation for Innovation.
The authors declare that they have no competing financial interests.
About this article
Cite this article
Murray, B., Knopf, D. & Bertram, A. The formation of cubic ice under conditions relevant to Earth's atmosphere. Nature 434, 202–205 (2005). https://doi.org/10.1038/nature03403
This article is cited by
Influence of Mechanical Loads on the State of Water in the Hydrophobic Environment of Methyl Silica Particles
Theoretical and Experimental Chemistry (2022)
Nature Communications (2021)
Nature Materials (2020)
Nature Communications (2019)
Journal of Visualization (2018)