References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-10-1585-2010

Water-soluble SOA from Alkene ozonolysis: composition and droplet activation kinetics inferences from analysis of CCN activity

Asa-Awuku

¹ ⁵ Nenes

¹ ² Gao

³ ⁶ Flagan

R. C.

³ ⁴ Seinfeld

J. H.

³ ⁴

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

Department of Environmental Science and Engineering, California Institute of Technology, Pasadena, CA, USA

Department of Chemical Engineering, California Institute of Technology, Pasadena, CA, USA

now at: Department of Chemical and Environmental Engineering, University of California-Riverside, CA, USA

now at: Division of Math, Science, and Technology, Nova Southeastern University, Fort Lauderdale, FL, USA

15 02 2010

10 4 1585 1597

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.

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The full text article is available as a PDF file from http://www.atmos-chem-phys.net/10/1585/2010/acp-10-1585-2010.pdf

Cloud formation characteristics of the water-soluble organic fraction (WSOC) of secondary organic aerosol (SOA) formed from the ozonolysis of alkene hydrocarbons (terpinolene, 1-methlycycloheptene and cycloheptene) are studied. Based on size-resolved measurements of CCN activity (of the pure and salted WSOC samples) we estimate the average molar volume and surface tension depression associated with the WSOC using Köhler Theory Analysis (KTA). Consistent with known speciation, the results suggest that the WSOC are composed of low molecular weight species, with an effective molar mass below 200 g mol<sup>−1</sup>. The water-soluble carbon is also surface-active, depressing surface tension 10–15% from that of pure water (at CCN-relevant concentrations). The inherent hygroscopicity parameter, κ, of the WSOC ranges between 0.17 and 0.25; if surface tension depression and molar volume effects are considered in κ, a remarkably constant "apparent" hygroscopicity ~0.3 emerges for all samples considered. This implies that the volume fraction of soluble material in the parent aerosol is the key composition parameter required for prediction of the SOA hygroscopicity, as shifts in molar volume across samples are compensated by changes in surface tension. Finally, using "threshold droplet growth analysis", the water-soluble organics in all samples considered do not affect CCN activation kinetics.

References 1

Alfarra, M. R., Paulsen, D., Gysel, M., Garforth, A. A., Dommen, J., Prevot, A. S. H., Worsnop, D. R., Baltensperger, U., and Coe, H.: A mass spectrometric study of secondary organic aerosols formed from the photooxidation of anthropogenic and biogenic precursors in a reaction chamber, Atmos. Chem. Phys., 6, 5279–5293, 2006.

Andreae, M. O. and Crutzen, P. J.: Atmospheric aerosols: Biogeochemical sources and role in atmospheric chemistry, Science, 276, 1052–1058, 1997.

Asa-Awuku, A., Nenes, A., Sullivan, A., Hennigan, C. J., and Weber, R. J.: Investigation of molar volume and surfactant characteristics of water-soluble organic compounds in biomass burning aerosol, Atmos. Chem. Phys., 8, 799–812, 2008.

Asa-Awuku, A., Engelhart, G. J., Lee, B. H., Pandis, S. N., and Nenes, A.: Relating CCN activity, volatility, and droplet growth kinetics of $\beta $-caryophyllene secondary organic aerosol, Atmos. Chem. Phys., 9, 795–812, 2009

Aschmann, S. M., Atkinson, R., and Arey, J.: Products of reaction of OH radicals with alpha-pinene, J. Geophys. Res.-A., 107, 4191, doi:10.1029/2001JD001098, 2002.

Baltensperger, U., Kalberer, M., Dommen, J., Paulsen, D., Alfarra, M. R., Coe, H., Fisseha, R., Gascho, A., Gysel, M., Nyeki, S., Sax, M., Steinbacher, M., Prevot, A. S. H., Sjoren, S., Weingartner, E., and Zenobi, R.: Secondary organic aerosols from anthropogenic and biogenic precursors, Faraday Discussions, 130, 265–278, 2005.

Brooks, S. D., DeMott, P. J., and Kreidenweis, S. M.: Water uptake by particles containing humic materials and mixtures of humic materials with ammonium sulfate, Atmos. Environ., 38(13), 1859–1868, 2004.

Bougiatioti, A., Fountoukis, C., Kalivitis, N., Pandis, S. N., Nenes, A. and Mihalopoulos, N.: Cloud condensation nuclei measurements in the eastern Mediterranean marine boundary layer: CCN closure and droplet growth kinetics, Atmos. Chem. Phys., 9, 7053–7066, 2009.

Cachier, H., Liousse, C., Buatmenard, P., and Gaudichet, A.: Particulate Content Of Savanna Fire Emissions, J. Atmos. Chem.., 22, 123–148, 1995.

Carrico, C. M., Petters, M. D., Kreidenweis, S. M., Collett, J. L., Engling, G., and Malm, W. C.: Aerosol hygroscopicity and cloud droplet activation of extracts of filters from biomass burning experiments, J. Geophys. Res.-Atmos., 113, D08206, doi:10.1029/2007JD009274, 2008.

Claeys, M., Wang, W., Ion, A. C., Kourtchev, I., Gelencser, A., and Maenhaut, W.: Formation of secondary organic aerosols from isoprene and its gas-phase oxidation products through reaction with hydrogen peroxide, Atmos. Environ., 38, 4093–4098, 2004.

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.-A., 108, 4685, doi:10.1029/2003JD003566, 2003.

Dinar, E., Taraniuk, I., Graber, E. R., Anttila, T., Mentel, T. F., and Rudich, Y.: Hygroscopic growth of atmospheric and model humic-like substances, J. Geophys. Res.-A., 112, D05211, doi:10.1029/2006JD007442, 2007.

Dinar, E., Taraniuk, I., Graber, E. R., Katsman, S., Moise, T., Anttila, T., Mentel, T. F., and Rudich, Y.: Cloud Condensation Nuclei properties of model and atmospheric HULIS, Atmos. Chem. Phys., 6, 2465–2481, 2006.

Dommen, J., Metzger, A., Duplissy, J., Kalberer, M., Alfarra, M. R., Gascho, A., Weingartner, E., Prevot, A. S. H., Verheggen, B., and Baltensperger, U.: Laboratory observation of oligomers in the aerosol from isoprene/NO<sub>x</sub> photooxidation, Geophys. Res. Lett., 33, L13805, doi:10.1029/2006GL026523, 2006.

Engelhart, G. J., Asa-Awuku, A., Nenes, A., and Pandis, S. N.: CCN activity and droplet growth kinetics of fresh and aged monoterpene secondary organic aerosol, Atmos. Chem. Phys., 8, 3937–3949, 2008

Fitzgerald, J. W., Hoppel, W. A., and Gelbard, F.: A one-dimensional sectional model to simulate multicomponent aerosol dynamics in the marine boundary layer – 1. Model description, J. Geophys. Res.-A., 103, 16085–16102, 1998.

Forstner, H. J. L., Flagan, R. C., and Seinfeld, J. H.: Secondary organic aerosol from the photooxidation of aromatic hydrocarbons: Molecular composition, Environ. Sci. Technol., 31, 1345–1358, 1997.

Gao, S., Keywood, M., Ng, N. L., Surratt, J., Varutbangkul, V., Bahreini, R., Flagan, R. C., and Seinfeld, J. H.: Low-molecular-weight and oligomeric components in secondary organic aerosol from the ozonolysis of cycloalkenes and alpha-pinene, J. Phys. Chem. A, 108, 10147–10164, 2004a.

Gao, S., Ng, N. L., Keywood, M., Varutbangkul, V., Bahreini, R., Nenes, A., He, J. W., Yoo, K. Y., Beauchamp, J. L., Hodyss, R. P., Flagan, R. C., and Seinfeld, J. H.: Particle phase acidity and oligomer formation in secondary organic aerosol, Environ. Sci. Technol., 38, 6582–6589, 2004b.

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.

Guenther, A., Hewitt, C. N., Erickson, D., Fall, R., Geron, C., Graedel, T., Harley, P., Klinger, L., Lerdau, M., McKay, W. A., Pierce, T., Scholes, B., Steinbrecher, R., Tallamraju, R., Taylor, J., and Zimmerman, P.: A Global-Model of Natural Volatile Organic-Compound Emissions, J. Geophys. Res.-A., 100, 8873–8892, 1995.

Gysel, M., Weingartner, E., Nyeki, S., Paulsen, D., Baltensperger, U., Galambos, I. and Kiss, G.: Hygroscopic properties of water-soluble matter and humic-like organics in atmospheric fine aerosol, Atmos. Chem. Phys., 4, 35–50, 2004

Hamilton, J. F., Lewis, A. C., Reynolds, J. C., Carpenter, L. J., and Lubben, A.: Investigating the composition of organic aerosol resulting from cyclohexene ozonolysis: low molecular weight and heterogeneous reaction products, Atmos. Chem. Phys., 6, 4973–4984, 2006.

Henning, S., Rosenorn, T., D'Anna, B., Gola, A. A., Svenningsson, B., and Bilde, M.: Cloud droplet activation and surface tension of mixtures of slightly soluble organics and inorganic salt, Atmos. Chem. Phys., 5, 575–582, 2005.

Huff-Hartz, K. E., Rosenorn, T., Ferchak, S. R., Raymond, T. M., Bilde, M., Donahue, N. M., and Pandis, S. N.: Cloud condensation nuclei activation of monoterpene and sesquiterpene secondary organic aerosol, J. Geophys. Res.-A., 110, D14208, doi:10.1029/2004JD005754, 2005.

Jurányi, Z., Gysel, M., Duplissy, J., Weingartner, E., Tritscher, T., Dommen, J., Henning, S., Ziese, M., Kiselev, A., Stratmann, F., George, I. and Baltensperger, U.: Influence of gas-to-particle partitioning on the hygroscopic and droplet activation behaviour of $\alpha $-pinene secondary organic aerosol, Phys. Chem. Chem. Phys., 11, 8091–8097, doi:10.1039/b904162a, 2009.

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.

Kalberer, M., Sax, M., and Samburova, V.: Molecular size evolution of oligomers in organic aerosols collected in urban atmospheres and generated in a smog chamber, Environ. Sci. Technol., 40, 5917–5922, 2006.

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.

Keywood, M. D., Varutbangkul, V., Bahreini, R., Flagan, R. C., and Seinfeld, J. H.: Secondary organic aerosol formation from the ozonolysis of cycloalkenes and related compounds, Environ.. Sci. Technol., 38, 4157–4164, 2004.

King, S. M., Rosenoern, T., Shilling, J. E., Chen, Q., and Martin, S. T.: Increased cloud activation potential of secondary organic aerosol for atmospheric mass loadings, Atmos. Chem. Phys., 9, 2959–2971, 2009.

King, S. M., Rosenoern, T., Shilling, J. E., Chen, Q., and Martin, S. T.: Cloud condensation nucleus activity of secondary organic aerosol particles mixed with sulfate, Geophys. Res. Lett., 34(24), L24806, doi:10.1029/2007GL030390, 2007.

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.

Köhler, H.: The nucleus in and the growth of hygroscopic droplets, Transactions of the Faraday Society, 43, 1152–1161, 1936.

Kroll, J. H., Ng, N. L., Murphy, S. M., Flagan, R. C., and Seinfeld, J. H.: Secondary organic aerosol formation from isoprene photooxidation, Environ. Sci. Technol., 40, 1869–1877, 2006.

Lance, S., Medina, J., Smith, J. N., and Nenes, A.: Mapping the operation of the DMT Continuous Flow CCN counter, Aerosol Sci. Tech., 40, 242–254, 2006.

Lance, S., Nenes, A., Mazzoleni, C., Dubey, M., Gates, H., Varutbangkul, V., Rissman, T. A., Murphy, S. M., Sorooshian, A., Brechtel, F., Flagan, R. C., Seinfeld, J. H., Feingold, G., and Jonsson, H.: CCN Activity, Closure and Droplet Growth Kinetics of Houston Aerosol During the Gulf of Mexico Atmospheric Composition and Climate Study (GoMACCS), J. Geoph. Res., 114, D00F15, doi:10.1029/2008JD011699, 2009

Langmuir, I.: The constitution and fundamental properties of solids and liquids. II. Liquids, J. Am. Chem. Soc., 39, 1848–1906, 1917.

Li, Z. D., Williams, A. L., and Rood, M. J.: Influence of soluble surfactant properties on the activation of aerosol particles containing inorganic solute, J. Atmos. Sci., 55, 1859–1866, 1998.

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.

Moore, R. H., Ingall, E. D., Sorooshian, A., and Nenes, A.: Molar mass, surface tension, and droplet growth kinetics of marine organics from measurements of CCN activity, Geophys. Res. Lett., 35, L07801, doi:10.1029/2008GL033350, 2008.

Murphy, S. M., Agrawal, H., Sorooshian, A., Padró, L. T., Gates, H., Hersey, S., Welch, W. A., Jung, H., Miller, J. W., Cocker III, D. R., Nenes, A., Jonsson, H. H., Flagan, R. C., and Seinfeld, J. H.: Comprehensive simultaneous shipboard and airborne characterization of exhaust from a modern container ship at sea, Environ. Sci. Technol., 43(13), 4626–4640, doi:10.1021/es802413j, 2009.

Nenes, A., Moore, R. H, and Medina, J.: Scanning Mobility CCN Analysis – A method for fast measurements of size resolved CCN activity and growth kinetics, Aerosol Sci. Technol., in review, 2010.

Padró, L. T., Asa-Awuku, A., Morisson, R., and Nenes, A.: Inferring Thermodynamic Properties from CCN Activation Experiments: Single-component and Binary Aerosols, Atmos. Chem. Phys., 7, 5263–5274, 2007.

Padró, L. T., Tkacik, D., Lathem, T., Hennigan, C. J., Sullivan, A. P., Weber, R. J., Huey, L. G., and Nenes, A., Investigation of CCN relevant properties and droplet growth kinetics of water-soluble aerosol fraction in Mexico City, J. Geophys. Res., in press, 2010.

Petters, M. D. and Kreidenweis, S. M.: A single parameter representation of hygroscopic growth and cloud condensation nucleus activity, Atmos. Chem. Phys., 7, 1961–1971, 2007.

Petters, M. D., Wex, H., Carrico, C. M., Hallbauer, E., Massling, A., McMeeking, G. R., Poulain, L., Wu, Z., Kreidenweis, S. M., and Stratmann, F.: Towards closing the gap between hygroscopic growth and activation for secondary organic aerosol – Part 2: Theoretical approaches, Atmos. Chem. Phys., 9, 3999–4009, 2009.

Petters, M. D., Kreidenweis, S. M., Prenni, A. J., Sullivan, R. C., Carrico, C. M., Koehler, K. A., and P. J. Ziemann, Role of molecular size in cloud droplet activation, Geoph. Res. Lett., 36, L22801, doi:10.1029/2009GL040131, 2009

Prenni, A. J., Petters, M. D., Kreidenweis, S. M., DeMott, P. J., and Ziemann, P. J.: Cloud droplet activation of secondary organic aerosol, J. Geophys. Res., 112, D10223, doi:10.1029/2006JD007963, 2007

Rissler, J., Vestin, A., Swietlicki, E., Fisch, G., Zhou, J., Artaxo, P., and Andreae, M. O.: Size distribution and hygroscopic properties of aerosol particles from dry-season biomass burning in Amazonia, Atmos. Chem. Phys., 6, 471–491, 2006.

Roberts, G. C. and Nenes, A.: A continuous-flow streamwise thermal-gradient CCN chamber for atmospheric measurements, Aerosol Sci. Tech., 39, 206–221, 2005.

Robinson, A. L., Donahue, N. M., Shrivastava, M. K., Weitkamp, E. A., Sage, A. M., Grieshop, A. P., Lane, T. E., Pierce, J. R., and Pandis, S. N.: Rethinking organic aerosols: Semivolatile emissions and photochemical aging, Science, 315, 1259–1262, 2007.

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. Environ., 27, 1309–1330, 1993.

Salma, I., Ocskay, R., Varga, I., and Maenhaut, W.: Surface tension of atmospheric humic-like substances in connection with relaxation, dilution, and solution pH, J. Geophys. Res.-A., 111, D23205, doi:10.1029/2005JD007015, 2006.

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.

Seinfeld, J. H. and Pandis, S. N.: Atmospheric Chemistry & Physics: From Air Pollution to Climate Change, John Wiley & Sons, 761–823, 1998.

Shilling, J. E., King, S. M., Mochida, M., and Martin, S. T.: Mass spectral evidence that small changes in composition caused by oxidative aging processes alter aerosol CCN properties, J. Phys. Chem. A, 111, 3358–3368, 2007.

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.

Snider, J. R. and Brenguier, J. L.: Cloud condensation nuclei and cloud droplet measurements during ACE-2, Tellus B, 52, 828–842, 2000.

Sorjamaa, R. and Laaksonen, A.: The influence of surfactant properties on critical supersaturations of cloud condensation nuclei, J. Aerosol Sci., 37, 1730–1736, 2006.

Sorjamaa, R., Svenningsson, B., Raatikainen, T., Henning, S., Bilde, M., and Laaksonen, A.: The role of surfactants in Kohler theory reconsidered, Atmos. Chem. Phys., 4, 2107–2117, 2004.

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.-A., 111, D05314, doi:10.1029/2005JD006485, 2006.

Tabazadeh, A.: Organic aggregate formation in aerosols and its impact on the physicochemical properties of atmospheric particles, Atmos. Env., 39, 5472–5480, 2005.

Turpin, B. J. and Lim, H. J.: Species contributions to PM2.5 mass concentrations: Revisiting common assumptions for estimating organic mass, Aerosol Sci. Technol., 35, 602–610, 2001.

Varutbangkul, V., Brechtel, F. J., Bahreini, R., Ng, N. L., Keywood, M. D., Kroll, J. H., Flagan, R. C., Seinfeld, J. H., Lee, A., and Goldstein, A. H.: Hygroscopicity of secondary organic aerosols formed by oxidation of cycloalkenes, monoterpenes, sesquiterpenes, and related compounds, Atmos. Chem. Phys., 6, 2367–2388, 2006.

Wex, H., Hennig, T., Salma, I., Ocskay, R., Kiselev, A., Henning, S., Massling, A., Wiedensohler, A., and Stratmann, F.: Hygroscopic growth and measured and modeled critical super-saturations of an atmospheric HULIS sample, Geophys. Res. Lett., 34, 34, L02818, doi:10.1029/2006GL028260, 2007.

Wex, H., Petters, M. D., Carrico, C. M., Hallbauer, E., Massling, A., McMeeking, G. R., Poulain, L., Wu, Z., Kreidenweis, S. M., and Stratmann, F.: Towards closing the gap between hygroscopic growth and activation for secondary organic aerosol: Part 1 – Evidence from measurements, Atmos. Chem. Phys., 9, 3987–3997, 2009.

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.