Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 9 5 2009 10.5194/acpd-9-20949-2009 http://www.atmos-chem-phys-discuss.net/9/20949/2009/ http://www.atmos-chem-phys-discuss.net/9/20949/2009/acpd-9-20949-2009.html http://www.atmos-chem-phys-discuss.net/9/20949/2009/acpd-9-20949-2009.pdf 20949 20977 2009-10-05 Depositional ice nucleation on solid ammonium sulfate and glutaric acid particles K. J. Baustian M. E. Wise M. A. Tolbert margaret.tolbert@colorado.edu Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO, USA Department of Atmospheric and Oceanic Science, University of Colorado, Boulder, CO, USA Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO, USA Heterogeneous ice nucleation on solid ammonium sulfate and solid amorphous glutaric acid particles was studied using optical microscopy and Raman spectroscopy. Optical microscopy was used to detect selective nucleation events as water vapor was slowly introduced into an environmental sample cell. Particles that nucleated ice were dried via sublimation and examined in detail using Raman spectroscopy. Depositional ice nucleation occurred preferentially on just a few ammonium sulfate and glutaric acid particles in each sample. For freezing temperatures between 214 K and 235 K average ice saturation ratios of <i>S</i>=1.10&plusmn;0.07 for solid ammonium sulfate and <i>S</i>=1.39&plusmn;0.16 for solid amorphous glutaric acid particles were determined. Experiments with externally mixed particles further show that ammonium sulfate is a more potent ice nucleus that glutaric acid. Our results suggest that heterogeneous nucleation on ammonium sulfate may be an important pathway for atmospheric ice nucleation and cirrus cloud formation when solid aerosol particles are available for ice formation. This pathway for ice formation may be particularly significant near the tropopause region where sulfates are abundant and other species known to be good ice nuclei are depleted. Abbatt,~J P D., Benz,~S., Cziczo,~D J., Kanji,~Z., Lohmann,~U., and Möhler,~O.: Solid ammonium sulfate aerosols as ice nuclei: A~pathway for cirrus cloud formation, Science, 313, 1770–1773, 2006. 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, 2005. Buajarern,~J., Mitchem~L., and Reid,~J P.: Charactering the formation of organic layers on the surface of inorganic aerosols by raman spectroscopy, J. Phys. Chem. A, 111, 11852–11859, 2007. Buck,~A L.: New equations for computing vapor pressure and enhancement factor, J Appl. Meteorol., 20, 1527–1532, 1981. Cantrell,~W. and Heymsfield,~A.: Production of ice in tropospheric clouds: a~review, B. Am. Meteor. Soc., 6, 795–807, 2005. Chan,~M N., Lee,~A K Y., and Chan,~C K.: Responses of ammonium sulfate particles coated with glutaric acid to cyclic changes in relative humidity: hygroscopicity and raman characterization, Environ. Sci. Technol., 40, 6983–6989, 2006. 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, doi:10.1029/2004GL019822, 2004. 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 Am. Sci. USA, 100(25), 14655–14660, 2003a. DeMott,~P J., Sassen,~K., Poellot,~M R., Baumgardner,~D., Rogers,~D C., Brooks,~S D., Prenni,~A J., and Kreidenweis,~S M.: African dust aerosols as atmospheric ice nuclei, Geophys. Res. Lett., 30(14), 1732, doi:10.1029/2003GL017410, 2003b. DeMott,~P J., Rogers,~D C., Kreidenweis,~S M., Chen,~Y., Twohy,~C H., Baumgardner,~D., Heymsfield,~A J., and Chan,~K R.: The role of heterogeneous freezing nucleation in upper tropospheric clouds: Inferences from SUCCESS, Geophys. Res. Lett., 25, 1387–1390, 1998. 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, doi:10.1029/2008GL035997, 2009. Froyd,~K D., Murphy,~D M., Sanford,~T J., Thomson,~D S., Wilson,~J C., Pfister,~L., and Lait,~L.: Aerosol composition of the tropical upper troposphere, Atmos. Chem. Phys., 9, 4363–4385, 2009. Gettelman,~A., Randel,~W J., Wu,~F., and Massie,~S T.: Transport of water vapor in the tropical tropopause layer, Geophys. Res. Lett., 29(9), 1–4, 2002. Hung,~H., Malinowski,~A., and Martin,~S T.: Ice nucleation kinetics of aerosols containing aqueous and solid ammonium sulfate particles, J Phys. Chem. A, 106, 293–306, 2002. IPCC, 2007: Climate Change 2007: The Physical Science Basis. Contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change, edited by: Solomon,~S., Qin,~D., Manning,~M., Chen,~Z., Marquis,~M., Averyt,~K B., Tignor,~M., and Miller,~H L., Cambridge University Press, Cambridge, UK and New York, NY, USA, 996 pp., 2007. Jensen,~E J., Pfister,~L., Bui,~T V., Lawson,~P., Baker,~B., Mo,~Q., Baumgardner,~D., Weinstock,~E M., Smith,~J B., Moyer,~E J., Hanisco,~T F., Sayres,~D S., St. Clair,~J M., Alexander,~M J., Toon,~O B., and Smith,~J A.: Formation of large ($\sim $100 \unit\mum) ice crystals near the tropical tropopause, Atmos. Chem. Phys., 8, 1621–1633, 2008. Jensen,~E J., Toon,~O B., Pfister,~L., and Selkirk,~H B.: Dehydration of the upper troposphere and lower stratosphere by subvisible cirrus clouds near the tropical tropopause, Geophys. Res. Lett., 23(8), 825–828, 1996. 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, 7 pp., 025004, doi:10.1088/1748-9326/3/2/025004, 2008. Kanji,~Z A. and Abbatt,~J P D.: Laboratory studies of ice formation via deposition mode nucleation onto mineral dust and n-hexane soot samples, J. Geophys. Res., 111, D16204, doi:10.1029/2005JD006766, 2006. Kärcher,~B. and Lohmann,~U.: A~parameterization of cirrus cloud formation: Heterogeneous freezing, J Geophys. Res., 108, 4402, doi:10.1029/2002JD003220, 2003. Koop,~T., Luo,~B P., Tsias,~A., and Peter,~T.: Water activity as the determinant for homogeneous ice nucleation in aqueous solutions, Nature, 406, 611–614, 2000. Koop,~T., Ng,~H P., Molina,~L T., Molina,~M J.: A~new optical technique to study aerosol phase transitions: the nucleation of ice from \chemH_2SO_4 aerosols, J. Phys. Chem. A, 102, 8924–8931, 1998. Mangold,~A., Wagner,~R., Saathoff,~H., Schurath,~U., Giesemann,~C., Ebert, ~V., Kramer,~M., and Möhler,~O.: Experimental investigation of ice nucleation by different types of aerosols in the aerosol chamber AIDA: implications to microphysics of cirrus clouds, Meteorol Z., 14, 485–497, 2005. Martin,~S T.: Phase transitions of aqueous atmospheric particles, Chem. Rev., 100, 3403–3453, 2000. Marti,~J. and Mauersberger,~K.: A~survey and new measurements of ice vapor pressure at temperatures between 170 and 250 \unitK, Geophys. Res. Lett., 20, 363–366, 1993. 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, 8 pp., 2008. Möhler,~O., Field,~P R., Connolly,~P., Benz,~S., Saathoff,~H., Schnaiter,~M., Wagner,~R., Cotton,~R., Kramer,~M., Mangold,~A., and Heymsfield,~A J.: Efficiency of the deposition mode ice nucleation on mineral dust particles, Atmos. Chem. Phys., 6, 3007–3021, 2006. Möhler,~O., Stetzer,~O., Schaefers,~S., Linke,~C., Schnaiter,~M., Tiede, ~R., Saathoff ,~H., Kramer,~M., Mangold,~A., Budz,~P., Zink,~P., Schreiner,~J., Mauersberger,~K., Haag,~W., Karcher,~B., and Schurath,~U.: Experimental investigation of homogeneous freezing of sulphuric acid particles in the aerosol chamber AIDA, Atmos. Chem. Phys., 3, 211–223, 2003. Mund,~C. and Zellner,~R.: Freezing nucleation of levitated single sulfuric acid$/$\chemH_2O micro-droplets. A~combined Raman- and Mie spectroscopic study, J Mol. Struct., 661–662, 491–500, 2003. Onasch,~T B., Siefert,~R L., Brooks,~S D., Prenni,~A J., Murray,~B., Wilson,~M A., and Tolbert,~M A.: Infrared spectroscopic study of the deliquescence and efflorescence of ammonium sulfate aerosol as a~function of temperature, J Geophys. Res., 104(D17), 317–326, 1999. 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, doi:10.1029/2003JD004075, 2004. Pruppacher,~H R. and Klett,~J D.: Microphysics of clouds and precipitation, Kluwer Academic Publishers, Dordrecht, The Netherlands, 1997. Prenni,~A J., Wise,~M E., Brooks,~S D., and Tolbert,~M A.: Ice nucleation in sulfuric acid and ammonium sulfate particles, J Geophys. Res., 106(D3), 3037–3044, 2001a. Prenni,~A J., DeMott,~P J., Kreidenweis,~S M., Sherman,~D E., Russell, ~L M., and Ming,~Y.: The effects of low molecular weight dicarboxylic acids on cloud formation, J Phys. Chem. A, 105, 11240–11248, 2001b. Shilling,~J E., Fortin,~T J., and Tolbert,~M A.: Depositional ice nucleation on crystalline organic and inorganic solids, J Geophys. Res., 111, D12204, doi:10.1029/2005JF006664, 2006. Targino,~A C., Krejci,~R., Noone,~K J., and Glantz,~P.: Single particle analysis of ice crystal residuals observed in orographic wave clouds over Scandinavia during INTACC experiment, Atmos. Chem. Phys., 6, 1977–1990, 2006. 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, 2005.