Atmospheric Chemistry and Physics Discussions
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10.5194/acpd-8-9263-2008
http://www.atmos-chem-phys-discuss.net/8/9263/2008/
http://www.atmos-chem-phys-discuss.net/8/9263/2008/acpd-8-9263-2008.html
http://www.atmos-chem-phys-discuss.net/8/9263/2008/acpd-8-9263-2008.pdf
9263
9321
2008-05-22
Do atmospheric aerosols form glasses?
B. Zobrist
C. Marcolli
D. A. Pedernera
T. Koop
thomas.koop@uni-bielefeld.de
Department of Chemistry, Bielefeld University, Bielefeld, Germany
Institute for Atmospheric and Climate Science, ETH Zurich, Zurich, Switzerland
A new process is presented by which water-soluble organics might influence ice nucleation, ice
growth, chemical reactions and water uptake of aerosols in the upper troposphere: the formation of
glassy aerosol particles. Glasses are disordered amorphous (non-crystalline) solids that form when
a liquid is cooled without crystallization until the viscosity increases exponentially and
molecular diffusion practically ceases. The glass transition temperatures, <i>T</i><sub>g</sub>,
homogeneous ice nucleation temperatures, <i>T</i><sub>hom</sub>, and ice melting temperatures,
<i>T</i><sub>m</sub>, of various aqueous inorganic, organic and multi-component solutions are investigated
with a differential scanning calorimeter. The investigated solutes are: various polyols, glucose,
raffinose, levoglucosan, an aromatic compound, sulfuric acid, ammonium bisulphate and mixtures of
dicarboxylic acids (M5), of dicarboxylic acids and ammonium sulphate (M5AS), of two polyols, of
glucose and ammonium nitrate, and of raffinose and M5AS. The results indicate that aqueous
solutions of the investigated inorganic solutes show <i>T</i><sub>g</sub>-values that are too low to be of
atmospheric importance. In contrast, aqueous organic and multi-component solutions readily form
glasses at low but atmospherically relevant temperatures (≤230 K). To apply the
laboratory data to the atmospheric situation, the measured phase transition temperatures were
transformed from a concentration to a water activity scale by extrapolating water activities
determined between 252 K and 313 K to lower temperatures. The obtained state diagrams
reveal that the higher the molar mass of the aqueous organic or multi-component solutes, the higher
<i>T</i><sub>g</sub> of their respective solutions at a given water activity. To a lesser extent,
<i>T</i><sub>g</sub> also depends on the hydrophilicity of the organic solutes. Therefore, aerosol
particles containing larger and more hydrophobic organic molecules
(≳150 g mol<sup>-1</sup>) are more likely to form glasses at intermediate to high relative
humidities in the upper troposphere. Our results suggest that the water uptake of aerosols,
heterogeneous chemical reactions in aerosol particles, as well as ice nucleation and ice crystal
growth can be significantly impeded or even completely inhibited in organic-enriched aerosols at
upper tropospheric temperatures with implications for cirrus cloud formation and upper tropospheric
relative humidity.
Ablett, S., Izzard, M J., and Lillford, P. J.: Differential Scanning Calorimetric study of frozen Sucrose and Glycerol solutions, J. Chem. Soc. Faraday\ Trans., 88, 789–794, 1992.
Albrecht, B A.: Aerosols, Cloud microphysics and Fractional Cloudiness, Science, 245, 1227–1230, 1989.
Angell, C A.: Formation of Glasses from Liquids and Biopolymers, Science, 267, 1924–1935, 1995.
Angell, C A.: Liquid fragility and the glass transition in water and aqueous solutions, Chem. Rev., 102, 2627–2649, 2002.
Angell, C A.: Insights into phases of liquid water from study of its unusual glass-forming properties, Science, 319, 582–587, 2008.
Angell, C A., Sare, E J., Donnella, J., and MacFarlane, D R.: Homogeneous Nucleation and Glass Transition Temperatures in Solutions of Li Salts in \chemD_2O and \chemH_2O. Doubly Unstable Glass Regions, J. Phys. Chem., 85, 1461–1464, 1981.
Atkins, P W.: Physikalische Chemie, p. 188–189, VCH, Weinheim, 1996.
Baynard, T., Garland, R M., Ravishankara, A R., Tolbert, M A., and Lovejoy, E R.: Key factors influencing the relative humidity dependence of aerosol light scattering, Geophys. Res. Lett., 33, L06813, doi:10.1029/2005GL024898, 2006.
Blond, G., Simatos, D., CattĂ©, M., Dussap, C G., and Gros, J B.: Modeling of the water-sucrose state diagram below 0°C, Carbohydr. Res., 298, 139–145, 1997.
Carrico, C M., Kus, P., Rood, M J., Quinn, P K., and Bates, T S.: Mixtures of pollution, dust, sea salt, and volcanic aerosol during ACE-Asia: Radiative properties as a function of relative humidity, J. Geophys.\ Res., 108(D23), 8650, doi:10.1029/2003JD3405, 2003.
Clegg, S L., Brimblecombe, P., and Wexler, A S.: Thermodynamic model of the system H$^+$-NH$_4^+$-SO$_4^2-$-NO$_3^-$-H<sub>2</sub>O at tropospheric temperatures, J. Phys. Chem. A, 102, 2137–2154, 1998.
Colberg, C. A., Luo, B. P., Wernli, H., Koop, T., and Peter, T.: A novel model to predict the physical state of atmospheric \chemH_2SO_4/NH_3/H_2O aerosol particles, Atmos. Chem. Phys., 3, 909––924, 2003.
Craig, D. Q M., Royall, P G., Kett, V L., and Hopton, M L.: The relevance of the amorphous state to pharmaceutical dosage forms: glassy drugs and freeze dried systems, Int. J. Pharm., 179, 179–207, 1999.
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:10.1029/2004GL019 822, 2004.
Debenedetti, P G.: Metastable liquids, p. 235–239, Princeton University Press, Princeton NJ, 1996.
Debenedetti, P G. and Stillinger, F H.: Supercooled liquids and the glass transition, Nature, 410, 259–267, 2001.
Decesari, S., Fuzzi, S., Facchini, M C., Mircea, M., Emblico, L., Cavalli, F., Maenhaut, W., Chi, X., Schkolnik, G., Falkovich, A., Rudich, Y., Claeys, M., Pashynska, V., Vas, G., Kourtchev, I., Vermeylen, R., Hoffer, A., Andreae, M O., Tagliavini, E., Moretti, F., and Artaxo, P.: Characterization of the organic composition of aerosols from RondĂ´nia, Brazil, during the LBA-SMOCC 2002 experiment and its representation through model compounds, Atmos.\ Chem. Phys., 6, 375–402, 2006.
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, Proc. Natl.\ Acad. Sci., 100, 14 655–14 660, 2003.
Denkenberger, K A., Moffet, R C., Holecek, J C., Rebotier, T P., and Prather, K. A.: Real-Time, Single-Particle Measurements of Oligomers in Aged Ambient Aerosol Particles, Environ. Sci. Technol., 41, 5439–5446, 2007.
Ediger, M D., Angell, C A., and Nagel, S R.: Supercooled Liquids and Glasses, J. Phys. Chem., 100, 13 200–13 212, 1996.
Ervens, B., Feingold, G., Frost, G J., and Kreidenweis, S M.: A modeling study of aqueous production of dicarboxylic acids: 1. Chemical pathways and speciated organic mass production, J. Geophys. Res., 109, D15205, doi:10.1029/2003JD004387, 2004.
Fisseha, R., Dommen, J., Gaeggeler, K., Weingartner, E., Samburova, V., Kalberer, M., and Baltensperger, U.: Online gas and aerosol measurement of water soluble carboxylic acids in Zurich, J. Geophys. Res., 111, D12316, doi:10.1029/2005JD006782, 2006.
Folmer, J. C W. and Franzen, S.: Study of Polymer Glasses by Modulated Differential Scanning Calorimetry in the Undergraduate Physical Chemistry Laboratory, J. Chem. Educ., 80, 813–818, 2003.
Fredenslund, A., Jones, R L., and Prausnitz, J M.: Group-contribution estimation of activity-coefficients in nonideal liquid-mixtures, AICHE J., 21, 1086–1099, 1975.
Gable, C M., Betz, H F., and Maron, S H.: Phase equilibria of the system sulfur trioxide-water, J. Am. Chem. Soc., 72, 1445–1448, 1950.
Gordon, M. and Taylor, J S.: Ideal copolymers and the 2nd-order transitions of synthetic rubbers 1. Non-crystalline copolymers, J. Appl. Chem., 2, 493–500, 1952.
Graham, B., Mayol-Bracero, O L., Guyon, P., Roberts, G C., Decesari, S., Facchini, M C., Artaxo, P., Maenhaut, W., Köll, P., and Andreae, M O.: Water-soluble organic compounds in biomass burning aerosols over Amazonia 1 Characterization by NMR and GC-MS, J. Geophys. Res., 107(D20), 8047, doi:10.1029/2001JD000336, 2002.
Hancock, B C. and Zografi, G.: Characteristics and Significance of the Amorphous State in Pharmaceutical Systems, J. Pharm. Sci., 86, 1–12, 1997.
Hansen, J E., Sato, M., Lacis, A., Ruedy, R., Tegen, I., and Matthews, E.: Climate forcings in the Industrial Era, Proc. Natl. Acad. Sci., 95, 12 753–12 758, 1998.
Haywood, J. and Boucher, O.: Estimates of the direct and indirect radiative forcing due to tropospheric aerosols: A review, Rev. Geophys., 38, 513––543, 2000.
He, X., Fowler, A., and Toner, M.: Water activity and mobility in solutions of glycerol and small molecular weight sugars: Implication for cryo- and lyopreservation, J. Appl. Phys., 100, 074702-1-11, doi:10.1063/1.2336304, 2006.
IPCC(2007), Solomon, S., Qin, D., Manning, M., Chen, Z., Marquis, M., Averyt, K B., Tignor, M., and Miller, H L.: Climate Change 2007: The Physical Science Basis. Contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change, Cambridge University Press, Cambridge, United Kingdom and New York, NY, USA, 2007.
Jensen, E. J., Smith, J. B., Pfister, L., Pittman, J. V., Weinstock, E. M., Sayres, D. S., Herman, R. L., Troy, R. F., Rosenlof, K., Thompson, T. L., Fridlind, A. M., Hudson, P. K., Cziczo, D. J., Heymsfield, A. J., Schmitt, C., and Wilson, J. C.: Ice supersaturations exceeding 100% at the cold tropical tropopause: implications for cirrus formation and dehydration, Atmos. Chem. Phys., 5, 851–862, 2005.
Johari, G P., Hallbrucker, A., and Mayer, E.: The glass-liquid transition of hyperquenched water, Nature, 330, 552–553, 1987.
Kalberer, M., Paulsen, D., Sax, M., Steinbacher, M., Dommen, J., Prevot, A. S H., Fisseha, R., Weingartner, E., Frankevich, V., Zenobi, R., and Baltensperger, U.: Identification of Polymers as Major Components of Atmospheric Organic Aerosols, Science, 303, 1659–1662, 2004.
Kanakidou, M., Seinfeld, J. H., Pandis, S. N., Barnes, I., Dentener, F. J., Facchini, M. C., Van~Dingenen, R., Ervens, B., Nenes, A., Nielsen, C. J., Swietlicki, E., Putaud, J. P., Balkanski, Y., Fuzzi, S., Horth, J., Moortgat, G. K., Winterhalter, R., Myhre, C. E. L., Tsigaridis, K., Vignati, E., Stephanou, E. G., and Wilson, J.: Organic aerosol and global climate modelling: a review, Atmos. Chem. Phys., 5, 1053–1123, 2005.
Kanno, H. and Itoi, H.: Glass formation study of sulphuric acid (in Japanese), Ryusan to Kogyo, 37, 181–187, 1984.
Kärcher, B. and Koop, T.: The role of organic aerosols in homogeneous ice formation, Atmos. Chem. Phys., 5, 703–714, 2005.
Katkov, I I. and Levine, F.: Prediction of the glass transition temperature of water solutions: comparison of different models, Cryobiology, 49, 62–82, 2004.
Kawamura, K. and Ikushima, K.: Seasonal changes in the distribution of dicarboxylic acids in the urban atmosphere, Environ. Sci. Technol., 27, 2227–2235, 1993.
Kawamura, K., SemĂ©rĂ©, R., Imai, Y., Fujii, Y., and Hayashi, M.: Water soluble dicarboxylic acids and related compounds in Antarctic aerosols, J.\ Geophys. Res., 101(D13), 18 721–18 728, 1996a.
Kawamura, K., Kasukabe, H., and Barrie, L A.: Source and reaction pathways of dicarboxylic acids, ketoacids and dicarbonyls in arctic aerosols: One year of observations, Atmos. Env., 30, 1709–1722, 1996b.
KerÄŤ, J. and SrÄŤiÄŤ, S.: Thermal analysis of glassy pharmaceuticals, Thermochimica Acta, 248, 81–95, 1995.
Kilmartin, P A., Reid, D S., and Samson, I.: The measurement of the glass transition temperature of sucrose and maltose solutions with added NaCl, J.\ Sci. Food Agric., 80, 2196–2202, 2000.
Kiss, G., Tombácz, E., Varga, B., Alsberg, T., and Persson, L.: Estimation of the average molecular weight of humic-like substances isolated from fine atmospheric aerosol, Atmos. Env., 37, 3783––3794, 2003.
Kohl, I., Bachmann, L., Hallbrucker, A., Mayer, E., and Loerting, T.: Liquid-like relaxation in hyperquenched water at $\leq$140 K, Phys. Chem.\ Chem. Phys., 7, 3210–3220, 2005.
Koleske, J V. and Lundberg, R D.: Lactone Polymers. I. Glass Transition Temperature of Poly-epsilon-caprolactone by Means of Compatible Polymer Mixtures, J. Polym. Sci. A, 7, 795–807, 1969.
Koop, T.: The water activity of aqueous solutions in equilibrium with ice, Bull. Chem. Soc. Jpn., 75, 2587–2588, 2002.
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.
Krivácsy, Z., GelencsĂ©r, A., Kiss, G., MĂ©száros, E., Molnár, A., Hoffer, A., MĂ©száros, T., Sárvári, Z., Temesi, D., Varga, B., Baltensperger, U., Nyeki, S., and Weingartner, E.: Study on the Chemical Character of Water Soluble Organic Compounds in Fine Atmospheric Aerosol at the Jungfraujoch, J. Atmos. Chem., 39, 235–259, 2001.
Krivácsy, Z., Kiss, G., Ceburnis, D., Jennings, G., Maenhaut, W., Salma, I., and Shooter, D.: Study of water-soluble atmospheric humic matter in urban and marine environments, Atmos. Res., 87, 1–12, 2008.
Langer, R. and Vacanti, J P.: Tissue Engineering, Science, 260, 920–926, 1993.
Lawson, R. P., Pilson, B., Baker, B., Mo, Q., Jensen, E., Pfister, L., and Bui, P.: Aircraft measurements of microphysical properties of subvisible cirrus in the tropical tropopause layer, Atmos. Chem. Phys., 8, 1609–1620, 2008.
Lerici, C R., Piva, M., and Rosa, M D.: Water activity and freezing point depression of aqueous solutions and liquid foods, J. Food Sci., 48, 1667–1669, 1983.
Levine, H. and Slade, L.: A polymer physico-chemical approach to the study of commercial Starch Hydrolysis Products (SHPs), Carbohydr. Polym., 6, 213– 44, 1986.
Lohmann, U. and Feichter, J.: Global indirect aerosol effects: a review, Atmos. Chem. Phys., 5, 715–737, 2005.
Luyet, B. and Rasmussen, D.: Study by differential thermal analysis of the temperatures of instability of rapidly cooled solutions of glycerol, ethylene glycol, sucrose and glucose, Biodynamica, 10, 167–191, 1968.
Maltini, E., Anese, M., and Shtylla, I.: State diagrams of some organic acid-water systems of interest in food, Cryoletters, 18, 263–268, 1997.
Marcolli, C., Luo, B P., and Peter, T.: Mixing of the organic aerosol fractions: Liquids as the thermodynamically stable phases, J. Phys. Chem.\ A, 108, 2216–2224, 2004.
Martin, S T.: Phase transitions of aqueous atmospheric particles, Chem. Rev., 100, 3403––3453, 2000.
Middlebrook, A M., Murphy, D M., and Thomson, D S.: Observations of organic material in individual marine particles at Cape Grim during the First Aerosol Characterization Experiment (ACE 1), J. Geophys. Res., 103, 16 475–16 483, 1998.
Miyata, K. and Kanno, H.: Supercooling behavior of aqueous solutions of alcohols and saccharides, J. Mol. Liquids, 119, 189–193, 2005.
Murphy, D M., Cziczo, D J., Froyd, K D., Hudson, P K., Matthew, B M., Middlebrook, A M., Peltier, R E., Sullivan, A., Thomson, D S., and Weber, R J.: Single-particle mass spectrometry of tropospheric aerosol particles, J. Geophys. Res., 111, D23S32, doi:10.1029/2006JD007340, 2006.
Narukawa, M., Kawamura, K., Okada, K., Zaizen, Y., and Makino, Y.: Aircraft measurement of dicarboxylic acids in the free tropospheric aerosol over the western to central North Pacific, Tellus, 55B, 777–786, 2003.
Novakov, T., Hegg, D A., and Hobbs, P V.: Airborne measurements of carbonaceous aerosol on the East Coast of the United States, J. Geophys.\ Res., 102(D25), 30 023–30 030, 1997.
Pegg, D E. and Karow, A. M.: The Biophysics of Organ Cryopreservation, Plenum Pres, New York, 1987.
Peter, T., Marcolli, C., Spichtinger, P., Corti, T., Baker, M. B., and Koop, T.: When dry air is too humid, Science, 314, 1399–1402, 2006.
Quinn, P K., Bates, T S., Baynard, T., Clarke, A D.,~Onasch, T B., Wang, W., Rood, M. J.,~Andrews, E., Allan, J., Carrico, C M., Coffman, D., and Worsnop, D.: Impact of particulate organic matter on the relative humidity dependence of light scattering: A simplified parameterization, Geophys. Res. Lett., 32, L22 809, doi:10.1029/2005GL024322, 2005.
Rampp, M., Buttersack, C., and LĂĽdemann, H D.: c,T-dependence of the viscosity and the self-diffusion coefficients in some aqueous carbohydrate solutions, Carbohydr. Res., 328, 561–572, 2000.
Rasmussen, D H. and MacKenzie, A P.: Effect of solute on ice-solution interfacial free energy; calculation from measured homogeneous nucleation temperatures, in: Water structure at the water polymer interface, edited by Jellinek, H. H G., pp. 126–145, Plenum Press, New York, 1972.
Rogge, W F., Mazurek, M A., Hildemann, L M., Cass, G R., and Simoneit, B R. T.: Quantification of Urban Organic Aerosols at a Molecular level: Identification, Abundance and Seasonal Variation, Atmos. Env., 27A, 1309––1330, 1993.
Roos, Y H.: Melting and glass transitions of low molecular weight carbohydrates, Carbohydr. Res., 238, 39–48, 1993.
Satoh, K. and Kanno, H.: Anomalous crystallization behavior in the glass forming composition region of the \chemH_2O-\chemHNO_3-system, Bull.\ Chem. Soc. Jpn., 55, 1645–1646, 1982.
Saxena, P. and Hildemann, L M.: Water-Soluble Organics in Atmospheric Particles: A Critical Review of the Literature and Application of Thermodynamics to Identify Candidate Compounds, J. Atmos. Chem., 24, 57––109, 1996.
Seo, J A., Kim, S J., Oh, J., Kim, H K., Hwang, Y H., and Yang, Y S.: Brillouin scattering and DSC studies of glass transition temperatures of glucose-water mixtures, J. Korean Phys. Soc., 44, 523–526, 2004.
Shalaev, E Y., Franks, F., and Echlin, P.: Crystalline and amorphous phases in the ternary system water-sucrose-sodium chloride, J. Phys. Chem., 100, 1144–1152, 1996.
Slade, L. and Levine, H.: Water and the Glass Transition - Dependence of the Glass Transition on Composition and Chemical Structure: Special Implications for Flour Functionality in Cookie Baking, J. Food Eng., 22, 143–188, 1994.
Stokes, R H. and Robinson, R A.: Interactions in aqueous nonelectrolyte solutions I. Solute-solvent equilibria, J. Phys. Chem., 70, 2126–2131, 1966.
Young, F. E.: D-Glucose-water phase diagram, J. Phys. Chem., 61, 616–619, 1957.
Zahardis, J. and Petrucci, G. A.: The oleic acid-ozone heterogeneous reaction system: products, kinetics, secondary chemistry, and atmospheric implications of a model system - a review, Atmos. Chem. Phys., 7, 1237––1274, 2007.