ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-12-1189-2012 Deposition nucleation on mineral dust particles: a case against classical nucleation theory with the assumption of a single contact angle Wheeler M. J. 1 Bertram A. K. 1 Department of Chemistry, University of British Columbia, Vancouver, BC V6T 1Z1, Canada 30 01 2012 12 2 1189 1201 This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This article is available from http://www.atmos-chem-phys.net/12/1189/2012/acp-12-1189-2012.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/12/1189/2012/acp-12-1189-2012.pdf

Deposition nucleation on two mineral species, kaolinite and illite, was studied using a flow cell coupled to an optical microscope. The results show that the <i>S</i><sub>ice</sub> conditions when ice first nucleated, defined as the onset <i>S</i><sub>ice</sub> (<i>S</i><sub>ice,onset</sub>), is a strong function of the surface area available for nucleation, varying from 100% to 125% at temperatures between 242 and 239 K. The surface area dependent data could not be described accurately using classical nucleation theory and the assumption of a single contact angle (defined here as the single-α model). These results suggest that caution should be applied when using contact angles determined from <i>S</i><sub>ice,onset</sub> data and the single-α model. In contrast to the single-α model, the active site model, the deterministic model, and a model with a distribution of contact angles fit the data within experimental uncertainties. Parameters from the fits to the data are presented.

 References Ansmann, A., Tesche, M., Althausen, D., Müller, D., Seifert, P., Freudenthaler, V., Hesse, B., Wiegner, M., Pisani, G., Knippertz, P., and Dubovik, O.: Influence of Saharan dust on cloud glaciation in southern Morocco during the Saharan mineral dust experiment, J. Geophys. Res., 113, D04210, http://dx.doi.org/10.1029/2007JD008785doi:10.1029/2007JD008785, 2008. Archuleta, C M., DeMott, P J., and Kreidenweis, S M.: Ice nucleation by surrogates for atmospheric mineral dust and mineral dust/sulfate particles at cirrus temperatures, Atmos. Chem. Phys., 5, 2617–2634, http://dx.doi.org/10.5194/acp-5-2617-2005doi:10.5194/acp-5-2617-2005, 2005. Bailey, M. and Hallett, J.: Nucleation effects on the habit of vapour grown ice crystals from −18 to −42°C, Q. J. Roy. Meteorol. Soc., 128, 1461–1483, 2002. Baker, M B. and Peter, T.: Small-scale cloud processes and climate, Nature, 451, 299–300, http://dx.doi.org/10.1038/nature06594doi:10.1038/nature06594, 2008. Barahona, D., Rodriguez, J., and Nenes, A.: Sensitivity of the global distribution of cirrus ice crystal concentration to heterogeneous freezing, J. Geophys. Res., 115, D23213, http://dx.doi.org/10.1029/2010JD014273doi:10.1029/2010JD014273, 2010. Cantrell, W. and Heymsfield, A.: Production of ice in tropospheric clouds – A review, B. Am. Meteorol. Soc., 86, 795–807, http://dx.doi.org/10.1175/BAMS-86-6-795doi:10.1175/BAMS-86-6-795, 2005. Chen, J P., Hazra, A., and Levin, Z.: Parameterizing ice nucleation rates using contact angle and activation energy derived from laboratory data, Atmos. Chem. Phys., 8, 7431–7449, http://dx.doi.org/10.5194/acp-8-7431-2008doi:10.5194/acp-8-7431-2008, 2008. Chernoff, D I. and Bertram, A K.: Effects of sulfate coatings on the ice nucleation properties of a biological ice nucleus and several types of minerals, J. Geophys. Res., 115, D20205, http://dx.doi.org/10.1029/2010JD014254doi:10.1029/2010JD014254, 2010. Claquin, T., Schulz, M., and Balkanski, Y J.: Modeling the mineralogy of atmospheric dust sources, J. Geophys. Res., 104, 22243–22256, 1999. Connolly, P J., Mohler, O., Field, P R., Saathoff, H., Burgess, R., Choularton, T., and Gallagher, M.: Studies of heterogeneous freezing by three different desert dust samples, Atmos. Chem. Phys., 9, 2805–2824, http://dx.doi.org/10.5194/acp-9-2805-2009doi:10.5194/acp-9-2805-2009, 2009. Croteau, T., Bertram, A K., and Patey, G N.: Adsorption and structure of water on kaolinite surfaces: possible insight into ice nucleation from grand canonical monte carlo calculations, J. Phys. Chem. A, 112, 10708–10712, http://dx.doi.org/10.1021/jp805615qdoi:10.1021/jp805615q, 2008. Croteau, T., Bertram, A K., and Patey, G N.: Observations of high-density ferroelectric ordered water in kaolinite trenches using monte carlo simulations, J. Phys. Chem. A, 114, 8396–8405, http://dx.doi.org/10.1021/jp104643pdoi:10.1021/jp104643p, 2010. Cziczo, D J., DeMott, P J., Brooks, S D., Prenni, A J., Thomson, D S., Baumgardner, D., Wilson, J C., Kreidenweis, S M., and Murphy, D M.: Observations of organic species and atmospheric ice formation, Geophys. Res. Lett., 31, L12116, http://dx.doi.org/10.1029/2004GL019822doi:10.1029/2004GL019822, 2004. DeMott, P J.: Laboratory Studies of Cirrus Cloud Processes, in: Cirrus, edited by: Lynch, D K., Sassen, K., Starr, D O., and Stephens, G., 102–136, Oxford University Press, New York, USA, 2002. DeMott, P J., Cziczo, D J., Prenni, A J., Murphy, D M., Kreidenweis, S M., Thomson, D S., Borys, R., and Rogers, D C.: Measurements of the concentration and composition of nuclei for cirrus formation, P. Natl. Acad. Sci. USA, 100, 14655–14660, http://dx.doi.org/10.1073/pnas.2532677100doi:10.1073/pnas.2532677100, 2003. Dymarska, M., Murray, B J., Sun, L M., Eastwood, M L., Knopf, D A., and Bertram, A K.: Deposition ice nucleation on soot at temperatures relevant for the lower troposphere, J. Geophys. Res., 111, D04204, http://dx.doi.org/10.1029/2005JD006627doi:10.1029/2005JD006627, 2006. Eastwood, M L., Cremel, S., Gehrke, C., Girard, E., and Bertram, A K.: Ice nucleation on mineral dust particles: Onset conditions, nucleation rates and contact angles, J. Geophys. Res., 113, D22203, http://dx.doi.org/10.1029/2008JD010639doi:10.1029/2008JD010639, 2008. Eastwood, M L., Cremel, S., Wheeler, M., Murray, B J., Girard, E., and Bertram, A K.: Effects of sulfuric acid and ammonium sulfate coatings on the ice nucleation properties of kaolinite particles, Geophys. Res. Lett., 36, L02811, http://dx.doi.org/10.1029/2008GL035997doi:10.1029/2008GL035997, 2009. Fletcher, N H.: Size Effect in Heterogeneous Nucleation, J. Chem. Phys., 29, 572–576, 1958. Fletcher, N H.: Entropy Effect in Ice Crystal Nucleation, J. Chem. Phys., 30, 1476–1482, 1959. Fletcher, N H.: Active Sites and Ice Crystal Nucleation, J. Atmos. Sci., 26, 1266–1271, 1969. Fornea, A P., Brooks, S D., Dooley, J B., and Saha, A.: Heterogeneous freezing of ice on atmospheric aerosols containing ash, soot, and soil, J. Geophys. Res., 114, D13201, http://dx.doi.org/10.1029/2009JD011958doi:10.1029/2009JD011958, 2009. Gorbunov, B Z. and Kakutkina, N A.: Ice Crystal Formation on Aerosol Particles with a Non-Uniform Surface, J. Aerosol Sci., 13, 21–28, 1982. Han, J H., Hung, H M., and Martin, S T.: Size effect of hematite and corundum inclusions on the efflorescence relative humidities of aqueous ammonium nitrate particles, J. Geophys. Res., 107, D104086, http://dx.doi.org/10.1029/2001JD001054doi:10.1029/2001JD001054, 2002. Hegg, D A. and Baker, M B.: Nucleation in the atmosphere, Rep. Prog. Phys., 72, 056801, http://dx.doi.org/10.1088/0034-4885/72/5/056801doi:10.1088/0034-4885/72/5/056801, 2009. Heintzenberg, J., Okada, K., and Ström, J.: On the composition of non-volatile material in upper tropospheric aerosols and cirrus crystals, Atmos. Res., 41, 81–88, 1996. Hoose, C., Lohmann, U., Erdin, R., and Tegen, I.: The global influence of dust mineralogical composition on heterogeneous ice nucleation in mixed-phase clouds, Environ. Res. Lett., 3, 025003, http://dx.doi.org/10.1088/1748-9326/3/2/025003doi:10.1088/1748-9326/3/2/025003, 2008. Hoose, C., Kristjánsson, J E., and Burrows, S M.: How important is biological ice nucleation in clouds on a global scale?, Environ. Res. Lett., 5, 024009, http://dx.doi.org/10.1088/1748-9326/5/2/024009doi:10.1088/1748-9326/5/2/024009, 2010a. Hoose, C., Kristjánsson, J E., Chen, J.-P., and Hazra, A.: A classical-theory-based parameterization of heterogeneous ice nucleation by mineral dust, soot, and biological particles in a global climate model, J. Atmos. Sci., 67, 2483–2503, http://dx.doi.org/10.1175/2010JAS3425.1doi:10.1175/2010JAS3425.1, 2010b. Houghton, J T., Ding, Y., Griggs, D J., Noguer, M., van~der Linden, P J., Dai, X., Maskell, K., and Johnson, C. A E.: IPCC, 2001: Climate Change 2001: The Scientific Basis. Contribution of Working Group I to the Third Assessment Report of the Intergovernmental Panel on Climate Change, Cambridge University Press, Cambridge, UK, and New York, USA, 2001. Hu, X L. and Michaelides, A.: Ice formation on kaolinite: Lattice match or amphoterism?, Surf. Sci., 601, 5378–5381, http://dx.doi.org/10.1016/j.susc.2007.09.012doi:10.1016/j.susc.2007.09.012, 2007. Hung, H M., Malinowski, A., and Martin, S T.: Kinetics of heterogeneous ice nucleation on the surfaces of mineral dust cores inserted into aqueous ammonium sulfate particles, J. Phys. Chem. A, 107, 1296–1306, http://dx.doi.org/10.1021/jp021593ydoi:10.1021/jp021593y, 2003. Jensen, E J. and Toon, O B.: The potential impact of soot particles from aircraft exhaust on cirrus clouds, Geophys. Res. Lett., 24, 249–252, 1997. Jensen, E J., Toon, O B., Pueschel, R F., Goodman, J., Sachse, G W., Anderson, B E., Chan, K R., Baumgardner, D., and Miake-Lye, R C.: Ice crystal nucleation and growth in contrails forming at low ambient temperatures, Geophys. Res. Lett., 25, 1371–1374, 1998. Kanji, Z A. and Abbatt, J. P D.: Ice nucleation onto Arizona test dust at cirrus temperatures: effect of temperature and aerosol size on onset relative humidity, J. Phys. Chem. A, 114, 935–941, http://dx.doi.org/10.1021/jp908661mdoi:10.1021/jp908661m, 2010. Kanji, Z A., Florea, O., and Abbatt, J. P D.: Ice formation via deposition nucleation on mineral dust and organics: dependence of onset relative humidity on total particulate surface area, Environ. Res. Lett., 3, 025004, http://dx.doi.org/10.1088/1748-9326/3/2/025004doi:10.1088/1748-9326/3/2/025004, 2008. Kärcher, B.: Aircraft-generated aerosols and visible contrails, Geophys. Res. Lett., 23, 1933–1936, 1996. Kärcher, B.: Physicochemistry of aircraft-generated liquid aerosols, soot, and ice particles – 1. Model description, J. Geophys. Res., 103, 17111–17128, 1998. Kärcher, B., Busen, R., Petzold, A., Schröder, F P., Schumann, U., and Jensen, E J.: Physicochemistry of aircraft-generated liquid aerosols, soot, and ice particles – 2. Comparison with observations and sensitivity studies, J. Geophys. Res., 103, 17129–17147, 1998. Khvorostyanov, V I. and Curry, J A.: A new theory of heterogeneous ice nucleation for application in cloud and climate models, Geophys. Res. Lett., 27, 4081–4084, 2000. Khvorostyanov, V I. and Curry, J A.: The theory of ice nucleation by heterogeneous freezing of deliquescent mixed CCN. Part I: Critical radius, energy, and nucleation rate, J. Atmos. Sci., 61, 2676–2691, 2004. Khvorostyanov, V I. and Curry, J A.: The theory of ice nucleation by heterogeneous freezing of deliquescent mixed CCN. Part II: Parcel model simulation, J. Atmos. Sci., 62, 261–285, 2005. Khvorostyanov, V I. and Curry, J A.: Critical humidities of homogeneous and heterogeneous ice nucleation: Inferences from extended classical nucleation theory, J. Geophys. Res., 114, D04207, http://dx.doi.org/10.1029/2008JD011197doi:10.1029/2008JD011197, 2009. Klein, H., Nickovic, S., Haunold, W., Bundke, U., Nillius, B., Ebert, M., Weinbruch, S., Schuetz, L., Levin, Z., Barrie, L A., and Bingemer, H.: Saharan dust and ice nuclei over central Europe, Atmos. Chem. Phys., 10, 10211–10221, http://dx.doi.org/10.5194/acp-10-10211-2010doi:10.5194/acp-10-10211-2010, 2010. Koehler, K A., Kreidenweis, S M., DeMott, P J., Petters, M D., Prenni, A J., and Mohler, O.: Laboratory investigations of the impact of mineral dust aerosol on cold cloud formation, Atmos. Chem. Phys., 10, 11955–11968, http://dx.doi.org/10.5194/acp-10-11955-2010doi:10.5194/acp-10-11955-2010, 2010. Kulkarni, G. and Dobbie, S.: Ice nucleation properties of mineral dust particles: determination of onset RH$_i$, IN active fraction, nucleation time-lag, and the effect of active sites on contact angles, Atmos. Chem. Phys., 10, 95–105, http://dx.doi.org/10.5194/acp-10-95-2010doi:10.5194/acp-10-95-2010, 2010. Li, R. and Min, Q.-L.: Impacts of mineral dust on the vertical structure of precipitation, J. Geophys. Res., 115, D09203, http://dx.doi.org/10.1029/2009JD011925doi:10.1029/2009JD011925, 2010. Lide, D R., ed.: CRC Handbook of Chemistry and Physics, CRC Press LLC, Boca Raton, USA, 82 edn., 2001. Lüönd, F., Stetzer, O., Welti, A., and Lohmann, U.: Experimental study on the ice nucleation ability of size-selected kaolinite particles in the immersion mode, J. Geophys. Res., 115, D14201, http://dx.doi.org/10.1029/2009JD012959doi:10.1029/2009JD012959, 2010. Marcolli, C., Gedamke, S., Peter, T., and Zobrist, B.: Efficiency of immersion mode ice nucleation on surrogates of mineral dust, Atmos. Chem. Phys., 7, 5081–5091, http://dx.doi.org/10.5194/acp-7-5081-2007doi:10.5194/acp-7-5081-2007, 2007. Martin, S T., Han, J H., and Hung, H M.: The size effect of hematite and corundum inclusions on the efflorescence relative humidities of aqueous ammonium sulfate particles, Geophys. Res. Lett., 28, 2601–2604, 2001. Min, Q L., Li, R., Lin, B., Joseph, E., Wang, S., Hu, Y., Morris, V., and Chang, F.: Evidence of mineral dust altering cloud microphysics and precipitation, Atmos. Chem. Phys., 9, 3223–3231, http://dx.doi.org/10.5194/acp-9-3223-2009doi:10.5194/acp-9-3223-2009, 2009. Möhler, O., Benz, S., Saathoff, H., Schnaiter, M., Wagner, R., Schneider, J., Walter, S., Ebert, V., and Wagner, S.: The effect of organic coating on the heterogeneous ice nucleation efficiency of mineral dust aerosols, Environ. Res. Lett., 3, 025007, http://dx.doi.org/10.1088/1748-9326/3/2/025007doi:10.1088/1748-9326/3/2/025007, 2008a. Möhler, O., Schneider, J., Walter, S., Heymsfield, A J., Schmitt, D., and Ulanowski, Z J.: How coating layers influence the deposition mode ice nucleation on mineral particles, in: 15th Int. Conf. Clouds and Precipitation, Int. Comm. on Clouds and Precip., Cancun, Mexico, 2008b. Morrison, H., Curry, J A., and Khvorostyanov, V I.: A new double-moment microphysics parameterization for application in cloud and climate models. Part I: Description, J. Atmos. Sci., 62, 1665–1677, 2005. Murray, B J. and Bertram, A K.: Formation and stability of cubic ice in water droplets, Phys. Chem. Chem. Phys., 8, 186–192, http://dx.doi.org/10.1039/b513480cdoi:10.1039/b513480c, 2006. Murray, B J., Knopf, D A., and Bertram, A K.: The formation of cubic ice under conditions relevant to Earth's atmosphere, Nature, 434, 202–205, http://dx.doi.org/10.1038/nature03403doi:10.1038/nature03403, 2005. Murray, B J., Broadley, S L., Wilson, T W., Atkinson, J D., and Wills, R H.: Heterogeneous freezing of water droplets containing kaolinite particles, Atmos. Chem. Phys., 11, 4191–4207, http://dx.doi.org/10.5194/acp-11-4191-2011doi:10.5194/acp-11-4191-2011, 2011. Niedermeier, D., Hartmann, S., Shaw, R A., Covert, D., Mentel, T F., Schneider, J., Poulain, L., Reitz, P., Spindler, C., Clauss, T., Kiselev, A., Hallbauer, E., Wex, H., Mildenberger, K., and Stratmann, F.: Heterogeneous freezing of droplets with immersed mineral dust particles - measurements and parameterization, Atmos. Chem. Phys., 10, 3601–3614, http://dx.doi.org/10.5194/acp-10-3601-2010doi:10.5194/acp-10-3601-2010, 2010. Niedermeier, D., Shaw, R A., Hartmann, S., Wex, H., Clauss, T., Voigtländer, J., and Stratmann, F.: Heterogeneous ice nucleation: exploring the transition from stochastic to singular freezing behavior, Atmospheric Chemistry and Physics, 11, 8767–8775, http://dx.doi.org/10.5194/acp-11-8767-2011doi:10.5194/acp-11-8767-2011, 2011. Parsons, M T., Mak, J., Lipetz, S R., and Bertram, A K.: Deliquescence of malonic, succinic, glutaric, and adipic acid particles, J. Geophys. Res., 109, D06212, http://dx.doi.org/10.1029/2003JD004075doi:10.1029/2003JD004075, 2004. Prenni, A J., Petters, M D., Kreidenweis, S M., Heald, C L., Martin, S T., Artaxo, P., Garland, R M., Wollny, A G., and Pöschl, U.: Relative roles of biogenic emissions of Saharan dust as ice nuclei in the Amazon basin, Nat. Geosci., 2, 402–405, http://dx.doi.org/10.1038/NGEO517doi:10.1038/NGEO517, 2009. Pruppacher, H R. and Klett, J D.: Microphysics of Clouds and Precipitation, Atmospheric and oceanographic sciences library, Kluwer Academic Publishers, Dordrecht, The Netherlands, 2nd edn., 1997. Reist, P C.: Aerosol Science and Technology, McGraw-Hill, Inc., 2nd edn., 1993. Salam, A., Lohmann, U., Crenna, B., Lesins, G., Klages, P., Rogers, D., Irani, R., MacGillivray, A., and Coffin, M.: Ice nucleation studies of mineral dust particles with a new continuous flow diffusion chamber, Aerosol Sci. Tech., 40, 134–143, http://dx.doi.org/10.1080/02786820500444853doi:10.1080/02786820500444853, 2006. Sassen, K.: Indirect climate forcing over the western US from Asian dust storms, Geophys. Res. Lett., 29, 1465, http://dx.doi.org/10.1029/2001GL014051doi:10.1029/2001GL014051, 2002. Sassen, K., DeMott, P J., Prospero, J M., and Poellot, M R.: Saharan dust storms and indirect aerosol effects on clouds: CRYSTAL-FACE results, Geophys. Res. Lett., 30, 1633, http://dx.doi.org/10.1029/2003GL017371doi:10.1029/2003GL017371, 2003. Saunders, R W., Möhler, O., Schnaiter, M., Benz, S., Wagner, R., Saathoff, H., Connolly, P J., Burgess, R., Murray, B J., Gallagher, M., Wills, R., and Plane, J. M C.: An aerosol chamber investigation of the heterogeneous ice nucleating potential of refractory nanoparticles, Atmos. Chem. Phys., 10, 1227–1247, http://dx.doi.org/10.5194/acp-10-1227-2010doi:10.5194/acp-10-1227-2010, 2010. Seifert, P., Ansmann, A., Mattis, I., Wandinger, U., Tesche, M., Engelmann, R., Müller, D., Pérez, C., and Haustein, K.: Saharan dust and heterogeneous ice formation: Eleven years of cloud observations at the central European EARLINET site, J. Geophys. Res., 115, D20201, http://dx.doi.org/10.1029/2009JD013222doi:10.1029/2009JD013222, 2010. Twohy, C H. and Poellot, M R.: Chemical characteristics of ice residual nuclei in anvil cirrus clouds: evidence for homogeneous and heterogeneous ice formation, Atmos. Chem. Phys., 5, 2289–2297, http://dx.doi.org/10.5194/acp-5-2289-2005doi:10.5194/acp-5-2289-2005, 2005. Vali, G.: Nucleation Terminology, J. Aerosol Sci., 16, 575–576, 1985. Welti, A., Lüönd, F., Stetzer, O., and Lohmann, U.: Influence of particle size on the ice nucleating ability of mineral dusts, Atmos. Chem. Phys., 9, 6705–6715, http://dx.doi.org/10.5194/acp-9-6705-2009doi:10.5194/acp-9-6705-2009, 2009. Zimmermann, F., Ebert, M., Worringen, A., Schütz, L., and Weinbruch, S.: Environmental scanning electron microscopy (ESEM) as a new technique to determine the ice nucleation capability of individual atmospheric aerosol particles, Atmos. Environ., 41, 8219–8227, http://dx.doi.org/10.1016/j.atmosenv.2007.06.023doi:10.1016/j.atmosenv.2007.06.023, 2007. Zimmermann, F., Weinbruch, S., Schütz, L., Hofmann, H., Ebert, M., Kandler, K., and Worringen, A.: Ice nucleation properties of the most abundant mineral dust phases, J. Geophys. Res., 113, D23204, http://dx.doi.org/10.1029/2008JD010655doi:10.1029/2008JD010655, 2008.