Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 7 2 2007 10.5194/acpd-7-3589-2007 http://www.atmos-chem-phys-discuss.net/7/3589/2007/ http://www.atmos-chem-phys-discuss.net/7/3589/2007/acpd-7-3589-2007.html http://www.atmos-chem-phys-discuss.net/7/3589/2007/acpd-7-3589-2007.pdf 3589 3627 2007-03-12 Investigation of molar volume and surfactant characteristics of water-soluble organic compounds in biomass burning aerosol A. Asa-Awuku A. Nenes nenes@eas.gatech.edu A. P. Sullivan C. J. Hennigan R. J. Weber School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, GA, USA School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, GA, USA now at: Department of Atmospheric Sciences, Colorado State University, Fort Collins, CO, USA In this study, we characterize the CCN activity of the water-soluble organics in biomass burning aerosol. The aerosol after collection upon filters is dissolved in water using sonication. Hydrophobic and hydrophilic components are fractionated from a portion of the original sample using solid phase extraction, and subsequently desalted. The surface tension and CCN activity of these different samples are measured with a KSV CAM 200 goniometer and a DMT Streamwise Thermal Gradient CCN Counter, respectively. The measurements show that the strongest surfactants are isolated in the hydrophobic fraction, while the hydrophilics exhibit negligible surface tension depression. The presence of salts (primarily (NH₄)₂SO₄) in the hydrophobic fraction substantially enhances surface tension depression; their synergistic effects considerably enhance CCN activity, exceeding that of pure (NH₄)₂SO₄. For our analysis, average thermodynamic properties (i.e., molar volume) are determined for samples using our newly developed Köhler Theory Analysis (KTA) method. We have found that, the molar mass of the hydrophilic and hydrophobic aerosol components is estimated to be 87±26 g mol^−1 and 780±231 g mol^−1, respectively. KTA also suggests that the relative proportion (in moles) of hydrophobic to hydrophilic compounds in the original sample to be 1:3. For the first time, KTA is applied to an aerosol with this level of complexity and displays its potential for providing physically-based constraints for GCM parameterizations of the aerosol indirect effect. Andreae, M. O. and Crutzen, P. J.: Atmospheric aerosols: Biogeochemical sources and role in atmospheric chemistry, Science, 276, 1052–1058, 1997. Baumann, K., Ift, F., Zhao, J. Z., and Chameides, W. L.: Discrete measurements of reactive gases and fine particle mass and composition during the 1999 Atlanta Supersite Experiment, J. Geophys. Res., 108, 8416, doi:10.1029/2001JD001210, 2003. Cachier, H., Liousse, C., Buatmenard, P., and Gaudichet, A.: Particulate Content of Savanna Fire Emissions, J. Atmos. Chem., 22, 123–148, 1995. Cruz, C. N. and Pandis, S. N.: Deliquescence and hygroscopic growth of mixed inorganic-organic atmospheric aerosol, Environ. Sci. Technol., 34, 4313–4319, 2000. Decesari, S., Facchini, M. C., Fuzzi, S., and Tagliavini, E.: Characterization of water-soluble organic compounds in atmospheric aerosol: A new approach, J. Geophys. Res., 105, 1481–1489, 2000. Decesari, S., Facchini, M. C., Mircea, M., Cavalli, F., and Fuzzi, S.: Solubility properties of surfactants in atmospheric aerosol and cloud/fog water samples, J. Geophys. Res., 108, 4685, doi:10.1029/2003JD003566, 2003. Duarte, R. and Duarte, A. C.: Application of non-ionic solid sorbents (XAD resins) for the isolation and fractionation of water-soluble organic compounds from atmospheric aerosols, J. Atmos. Chem., 51, 79–93, 2005. Facchini, M. C., Decesari, S., Mircea, M., Fuzzi, S., and Loglio, G.: Surface tension of atmospheric wet aerosol and cloud/fog droplets in relation to their organic carbon content and chemical composition, Atmos. Environ., 34, 4853–4857, 2000. Facchini, M. C., Fuzzi, S., Zappoli, S., Andracchio, A., Gelencser, A., Kiss, G., Krivacsy, Z., Meszaros, E., Hansson, H. C., Alsberg, T., and Zebuhr, Y.: Partitioning of the organic aerosol component between fog droplets and interstitial air, J. Geophys. Res., 104, 26 821–26 832, 1999a. Facchini, M. C., Mircea, M., Fuzzi, S., and Charlson, R. J.: Cloud albedo enhancement by surface-active organic solutes in growing droplets, Nature, 401, 257–259, 1999b. Falkovich, A. H., Graber, E. R., Schkolnik, G., Rudich, Y., Maenhaut, W., and Artaxo, P.: Low molecular weight organic acids in aerosol particles from Rondonia, Brazil, during the biomass-burning, transition and wet periods, Atmos. Chem. Phys., 5, 781–797, 2005. Feingold, G. and Chuang, P. Y.: Analysis of the Influence of Film-Forming Compounds on droplet Growth: Implications for Cloud Microphysical Processes and Climate, J. Atmos. Science., 59, 2006–2018, 2002. Graber, E. R. and Rudich, Y.: Atmospheric HULIS: How humic-like are they? A comprehensive and critical review, Atmos. Chem. Phys., 6, 729–753, 2006. Graham, B., Mayol-Bracero, O. L., Guyon, P., Roberts, G. C., Decesari, S., Facchini, M. C., Artaxo, P., Maenhaut, W., Koll, 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, 8047, doi:10.1029/2001JD000336, 2002. Havers, N., Burba, P., Lambert, J., and Klockow, D.: Spectroscopic characterization of humic-like substances in airborne particulate matter, J. Atmos. Chem., 29, 45–54, 1998. Holmberg, K.: 1946-Surfactants and polymers in aqueous solution., John Wiley & Sons, Chichester, West Sussex, England, Hoboken, NJ, 2003. Hunter, R. J.: Foundations of colloid science, Oxford University Press, Oxford, New York, 2001. Climate Change 2001: The Scientific Basis – Contribution of Working Group I to the Third Assessment Report of the Intergovernmental Panel on Climate Change, edited by: Houghton, J. T., Ding, Y., Griggs, D. J., Noguer, M., van der Linden, P. J., and Xiaosu, D., Cambridge University Press, 2001. 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. Kiss, G., Tombacz, E., and Hansson, H. C.: Surface tension effects of humic-like substances in the aqueous extract of tropospheric fine aerosol, J. Atmos. Chem., 50, 279–294, 2005. Kiss, G., Varga, B., Galambos, I., and Ganszky, I.: Characterization of water-soluble organic matter isolated from atmospheric fine aerosol, J. Geophys. Res., 107, 8339, doi:10.1029/2001JD000603, 2002. Kiss, G., Varga, B., Gelencser, A., Krivacsy, Z., Molnar, A., Alsberg, T., Persson, L., Hansson, H. C., and Facchini, M. C.: Characterisation of polar organic compounds in fog water, Atmos. Environ., 35, 2193–2200, 2001. Köhler, H.: The nucleus in and the growth of hygroscopic droplets, Transactions of the Faraday Society, 43, 1152–1161, 1936. Krivacsy, Z., Gelencser, A., Kiss, G., Meszaros, E., Molnar, A., Hoffer, A., Meszaros, T., Sarvari, 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. Krivacsy, Z., Kiss, G., Varga, B., Galambos, I., Sarvari, Z., Gelencser, A., Molnar, A., Fuzzi, S., Facchini, M. C., Zappoli, S., Andracchio, A., Alsberg, T., Hansson, H. C., and Persson, L.: Study of humic-like substances in fog and interstitial aerosol by size-exclusion chromatography and capillary electrophoresis, Atmos. Environ., 34, 4273–4281, 2000. Lance, S., Medina, J., Smith, J. N., and Nenes, A.: Mapping the operation of the DMT Continuous Flow CCN counter, Aerosol Sci. Technol., 40, 242–254, 2006. Lance, S., Nenes, A., and Rissman, T. A.: Chemical and dynamical effects on cloud droplet number: Implications for estimates of the aerosol indirect effect, J. Geophys. Res., 109, D22208, doi:10.1029/2004JD004596, 2004. Langmuir, I.: The constitution and fundamental properties of solids and liquids. II. Liquids, J. Am. Chem. Soc., 39, 1848–1906, 1917. Limbeck, A., Kulmala, M., and Puxbaum, H.: Secondary organic aerosol formation in the atmosphere via heterogeneous reaction of gaseous isoprene on acidic particles, Geophys. Res. Lett., 30, 1996, doi:10.1029/2003GL017738, 2003. Mayol-Bracero, O. L., Guyon, P., Graham, B., Roberts, G., Andreae, M. O., Decesari, S., Facchini, M. C., Fuzzi, S., and Artaxo, P.: Water-soluble organic compounds in biomass burning aerosols over Amazonia - 2. Apportionment of the chemical composition and importance of the polyacidic fraction, J. Geophys. Res., 107, 8091, doi:10.1029/2001JD000522, 2002. Nenes, A., Charlson, R. J., Facchini, M. C., Kulmala, M., Laaksonen, A., and Seinfeld, J. H.: Can chemical effects on cloud droplet number rival the first indirect effect?, Geophys. Res. Lett., 29, 1848, doi:10.1029/2002GL015295, 2002. Nenes, A., Pandis, S. N., and Pilinis, C.: ISORROPIA: A new thermodynamic equilibrium model for multiphase multicomponent inorganic aerosols, Aquatic Geochemistry, 4, 123–152, 1998. Perry, R. H., Green, D. W., and Maloney, J. O.: Perry's Chemical Engineers' Handbook., McGraw-Hill, New York, 1997. Raymond, T. R. and Pandis, S. N.: Cloud activation of single-component organic aerosol particles, J. Geophys. Res., 107, 4787, doi:10.1029/2002JD002159, 2002. Roberts, G. C. and Nenes, A.: A continuous-flow streamwise thermal-gradient CCN chamber for atmospheric measurements, Aerosol Sci. Technol., 39, 206–221, 2005. Sannigrahi, P., Sullivan, A. P., Weber, R. J., and Ingall, E. D.: Characterization of water-soluble organic carbon in urban atmospheric aerosols using solid-state C-13 NMR spectroscopy, Environ. Sci. Technol., 40, 666–672, 2006. Seinfeld, J. H. and Pandis, S. N.: Atmospheric Chemistry & Physics: From Air Pollution to Climate Change, John Wiley & Sons, 1998. Shulman, M. L., Jacobson, M. C., Carlson, R. J., Synovec, R. E., and Young, T. E.: Dissolution behavior and surface tension effects of organic compounds in nucleating cloud droplets, Geophys. Res. Lett., 23, 277–280, 1996. Sullivan, A. P., Peltier, R. E., Brock, C. A., de Gouw, J. A., Holloway, J. S., Warneke, C., Wollny, A. G., and Weber, R. J.: Airborne measurements of carbonaceous aerosol soluble in water over northeastern United States: Method development and an investigation into water-soluble organic carbon sources, J. Geophys. Res., 111, D23S46, doi:10.1029/2006JD007072, 2006. Sullivan, A. P. and Weber, R. J.: Chemical characterization of the ambient organic aerosol soluble in water: 1. Isolation of hydrophobic and hydrophilic fractions with a XAD-8 resin, J. Geophys. Res., 111, D05314, doi:10.1029/2005JD006485, 2006a. Sullivan, A. P. and Weber, R. J.: Chemical characterization of the ambient organic aerosol soluble in water: 2. Isolation of acid, neutral, and basic fractions by modified size-exclusion chromatography, J. Geophys. Res., 111, D05315, doi:10.1029/2005JD006486, 2006b. Sullivan, A. P., Weber, R. J., Clements, A. L., Turner, J. R., Bae, M. S., and Schauer, J. J.: A method for on-line measurement of water-soluble organic carbon in ambient aerosol particles: Results from an urban site, Geophys. Res. Lett., 31, L13105, doi:10.1029/2004GL019681, 2004. Turpin, B. J. and Lim, H. J.: Species contributions to PM2.5 mass concentrations: Revisiting common assumptions for estimating organic mass, Aerosol Sci. Tech., 35, 602–610, 2001. Yamasoe, M. A., Artaxo, P., Miguel, A. H., and Allen, A. G.: Chemical composition of aerosol particles from direct emissions of vegetation fires in the Amazon Basin: water-soluble species and trace elements, Atmos. Environ., 34, 1641–1653, 2000. Yaws, C. L.: Chemical properties handbook : physical, thermodynamic, environmental, transport, safety, and health related properties for organic and inorganic chemicals, edited by: Yaws, C. L.., pp. vii, 779 p.: ill.; 729 cm., McGraw-Hill, New York, 1999. Zappoli, S., Andracchio, A., Fuzzi, S., Facchini, M. C., Gelencser, A., Kiss, G., Krivacsy, Z., Molnar, A., Meszaros, E., Hansson, H. C., Rosman, K., and Zebuhr, Y.: Inorganic, organic and macromolecular components of fine aerosol in different areas of Europe in relation to their water solubility, Atmos. Environ., 33, 2733–2743, 1999.