Journal of Atmospheric Chemistry

, Volume 57, Issue 3, pp 215–237 | Cite as

Size dependent partitioning of organic material: evidence for the formation of organic coatings on aqueous aerosols

  • T. Anttila
  • A. Kiendler-Scharr
  • Th. F. Mentel
  • R. Tillmann
Article

Abstract

Organic aerosol formation resulting from the ozonolysis of α-pinene, myrcene and sabinene was investigated in a large aerosol chamber in the presence of aqueous seed aerosols. The chemical composition of the particles was monitored by an aerosol mass spectrometer (Aerodyne Research Inc.) as a function of time and the particle size. Smaller particles were found to contain more organics relative to sulfate than the larger ones. In contrast, the water to sulfate mass ratio was not dependent on the particle size. These experimental findings indicate the formation of organic layers on the particles. With the aid of an aerosol dynamic model we demonstrate that the observations are consistent with the formation of multilayered organic films having thicknesses of approximately 10 nm. The results also suggest that the films were formed through condensation of low-volatile oxidation products that did not take up water considerably. Even though dissolution of oxidation products into the particle aqueous phase cannot be conclusively ruled out, the most plausible interpretation of the results is that the monoterpene ozonolysis lead to the formation of organic coatings on aqueous aerosols. Such films are likely to form in regions with monoterpene emissions.

Keywords

Aerosol dynamic modeling Aerosol mass spectrometer Organic films Secondary organic aerosol 

Notes

Acknowledgments

We acknowledge the fruitful discussions with Dr. Yinon Rudich. We also acknowledge the comments of both referees which helped us to improve the manuscript substantially. This work is part of the CASOMIO project and is supported by the EC (contract number EVK2-CT-2001-00124). One of the authors (T.A.) gratefully acknowledges financial support from the Helsingin Sanomat Centennial Foundation.

References

  1. Alfarra, M.R., Coe, H., Allan, J.D., Bower, K.N., Boudries, H., Canagaratna, M.R., Jimenez, J.L., Jayne, J.T., Garforth, A.A., Li, S.-M., Worsnop, D.R.: Characterization of urban and ruralorganic particulate in the Lower Fraser Valley using two Aerodyne Aerosol Mass Spectrometers. Atmos. Environ. 38, 5745–5758 (2004)CrossRefGoogle Scholar
  2. Allan, J.D., Coe, H., Bower, K.N., Alfarra, M.R., Delia, A.E., Jimenez, J.L., Middlebrook, A.M., Drewnick, F., Onasch, T.B., Canagaratna, M.R., Jayne, J.T., Worsnop, D.R.: Technical note: Extraction of chemically resolved mass spectra from Aerodyne aerosol mass spectrometer data. J. Aerosol Sci. 35, 909–922 (2004)CrossRefGoogle Scholar
  3. Anttila, T., Kiendler-Scharr, A., Tillmann, R., Mentel, Th.F.: On the reactive uptake of gaseous compounds by organic-coated aqueous aerosols: theoretical analysis and application to the heterogeneous hydrolysis of N2O5. J. Phys. Chem., A 110, 10435–10443 (2006)CrossRefGoogle Scholar
  4. Aschmann, S.M., Arey, J., Atkinson, R.: OH radical formation from the gas-phase reactions of O3 with a series of terpenes. Atmos. Environ. 36, 4347–4355 (2002)CrossRefGoogle Scholar
  5. Atkinson, R., Arey, J.: Gas-phase tropospheric chemistry of biogenic volatile organic compounds: a review. Atmos. Environ. 37, Supplement no. 2, S197–S219 (2003)CrossRefGoogle Scholar
  6. Atkinson, R., Hasegawa, D., Aschmann, S.M.: Rate constants for the gas-phase reactions of O3 with a series of monoterpenes and related compounds at 296±2 K. Int. J. Chem. Kinet. 22, 871–887 (1990)CrossRefGoogle Scholar
  7. Bahreini, R., Keywood, M.D., Ng, N.L., Varutbangkul, V., Gao, S., Flagan, R.C., Seinfeld, J.H., Worsnop, D.R., Jimenez J.L.: Measurements of secondary organic aerosol from oxidation of cycloalkenes, terpenes, and m-xylene using an aerodyne aerosol mass spectrometer. Environ. Sci. Technol. 39, 5674–5688 (2005)CrossRefGoogle Scholar
  8. Barnes, G.T.: The effects of monolayers on the evaporation of liquids. Adv. Colloid Interface Sci. 25, 89–200 (1986)CrossRefGoogle Scholar
  9. Barrow, R.J.: Statistics: A Guide to the use of Statistical Methods in the Physical Sciences. Wiley, Chichester, England (1989)Google Scholar
  10. Bonn, B., Schuster, G., Moortgat, G.K.: Influence of water vapour on the process of new particle formation during monoterpene ozonolysis. J. Phys. Chem., A 106, 2869–2881 (2002)CrossRefGoogle Scholar
  11. Bowman, F.M., Odum, J.R., Seinfeld, J.H.: Mathematical model for gas/particle partitioning of secondary organic aerosols. Atmos. Environ. 31, 3921–3931 (1997)CrossRefGoogle Scholar
  12. Broekhuizen, K.E., Thornberry, T., Kumar, P.P., Abbatt, J.P.D.: Formation of cloud condensation nuclei by oxidative processing: Unsaturated fatty acids. J. Geophys. Res. 109, doi: 10.1029/2004JD005298 (2004)
  13. Chuang, P.Y.: Measurement of the timescale of hygroscopic growth for atmospheric aerosols. J. Geophys. Res. 108, 4282, doi: 10.1029/2002JD002757 (2003)CrossRefGoogle Scholar
  14. Clegg, S.L., Seinfeld, J.H., Brimblecombe, P.: Thermodynamic modelling of aqueous aerosols containing electrolytes and dissolved organic compounds. J. Aerosol Sci. 32, 713–738 (2001)CrossRefGoogle Scholar
  15. Clegg, S.L., Seinfeld, J.H., Edney, E.O.: Thermodynamic modelling of aqueous aerosols containing electrolytes and dissolved organic compounds. II. An extended Zdanovskii–Stokes–Robinson approach. J. Aerosol Sci. 34, 667–690 (2003)CrossRefGoogle Scholar
  16. Cocker III, D.R., Clegg, S.L., Flagan, R.C., Seinfeld, J.H.: The effect of water on gas-particle partitioning of secondary organic aerosol. Part I: α-pinene/ozone system. Atmos. Environ. 35, 6049–6072 (2001)CrossRefGoogle Scholar
  17. Daumer, B., Niessner, R., Klockow, D.: Laboratory studies of the influence of thin organic films on the neutralization reaction of H2SO4 aerosol with ammonia. J. Aerosol Sci. 23, 315–325 (1992)CrossRefGoogle Scholar
  18. Decesari, S., Facchini, M.C., Mircea, M., Cavalli, F., Fuzzi, S.: Solubility properties of surfactants in atmospheric aerosol and cloud /fog water samples. J. Geophys. Res., 108, 4685, doi: 10.1029/2003JD003566 (2003)CrossRefGoogle Scholar
  19. Docherty, K.S., Ziemann, P.J.: Effects of Stabilized Criegee Intermediate and OH Radical Scavengers on Aerosol Formation from Reactions of α-Pinene with O3. Aerosol Sci. Tech. 37, 877–891 (2003)CrossRefGoogle Scholar
  20. Ellison, G., Tuck, A., Vaida, V.: Atmospheric processing of organic aerosols. J. Geophys. Res. 104, 11633–11641 (1999)CrossRefGoogle Scholar
  21. Falkovich, A., Schkolnik, G., Ganor, E., Rudich, Y.: Adsorption of organic compounds pertinent to urban environments onto mineral dust particles. J. Geophys. Res. 109, doi: 2003JD02208 (2004)
  22. Feingold, G., Chuang, P.Y.: Analysis of the infuence of film forming compounds on droplet growth: Implications for cloud microphysical processes and climate. J. Atmos. Sci. 59, 2006–2018 (2002)CrossRefGoogle Scholar
  23. Fillo, J.D., Koehler, C.A., Nguyen, T.P., De Haan, D.O., Gilbery, B.A., Flinn, K.P.: Simulating secondary organic aerosol activation by condensation of multiple organics on seed particles. Environ. Sci. Technol. 37, 4672–4677 (2003)CrossRefGoogle Scholar
  24. Folkers, M.: Bestimmung der Reaktionswahrscheinlichkeit von N2O5 an troposphärisch relevanten Aerosolen, Dissertation, University of Cologne, Cologne, Germany (2002)Google Scholar
  25. Folkers, M., Mentel, T.F., Wahner, A.: Influence of an organic coating on the reactivity of aqueous aerosols probed by the heterogeneous hydrolysis of N2O5. Geophys. Res. Lett. 30, doi: 10.1029/2003GL017168 (2003)
  26. Fuchs, N.A., Sutugin, A.G.: Highly Dispersed Aerosols. Newton, MA, Butterworth-Heinemann (1970)Google Scholar
  27. Fuentes, J.D., Lerdau, M., Atkinson, R., Baldocchi, D., Bottenheim, J.W., Ciccioli, P., Lamb, B., Geron, C., Gu, L., Guenther, A., Sharkey, T.D., Stockwell, W.: Biogenic hydrocarbons in the atmospheric boundary layer: A review. Bull. Am. Meteorol. Soc. 81, 1537–1575 (2000)CrossRefGoogle Scholar
  28. Garland, R. Wise, M.E., Beaver, M.R., DeWitt, H.L., Alken, A.C., Jimenez, J.L., Tolbert, M.A.: Impact of palmitic acid coating on the water uptake and loss of ammonium sulfate particles. Atmos. Chem. Phys. Discuss. 5, 2047–2074 (2005)Google Scholar
  29. Gill, P.S., Graedel, T.E., Weschler, C.J.: Organic films on atmospheric aerosol particles, fog droplets, cloud droplets, raindrops, and snowflakes. Rev. Geophys. 21, 903–920 (1983)Google Scholar
  30. Gilman, J.B., Eliason, T.L., Fast, A., Vaida, V.: Selectivity and stability of organic films at the air-aqueous interface. J. Coll. Int. Sci. 280, 234–243 (2004)CrossRefGoogle Scholar
  31. Griffin, R.J., Cocker III, D.R., Flagan, R.C., and Seinfeld, J.H.: Organic aerosol formation from the oxidation of biogenic hydrocarbons. J. Geophys. Res. 104, 3555–3567 (1999)CrossRefGoogle Scholar
  32. 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., Zimmermann, P.: A global model of natural volatile organic emissions. J. Geophys. Res., 100, 8873–8892 (1995)CrossRefGoogle Scholar
  33. Held, A., Nowak, A., Birmili, W., Wiedensohler, A., Forkel, R., and Klemm, O.: Observations of particle formation and growth in a mountainous forest region in central Europe. J. Geophys. Res. 109, doi: 10.1029/2004JD005346 (2004)
  34. Hoppel, W., Fitzgerald, J., Frick, G., Caffrey, P.F., Pasternack, L., Hegg, D., Gao, S., Leaitch, R., Shantz, N., Cantrell, C., Albrechcinski, T., Ambrusko, J.W., Sullivan, W.: Particle formation and growth from ozonolysis of α-pinene. J. Geophys. Res. 106, 27 603–27 618 (2001)Google Scholar
  35. Iinuma Y., Böge, O., Gnauk, T., Herrmann, H.: Aerosol-chamber study of the α-pinene/O3 reaction: Influence of particle acidity on aerosol yields and products. Atmos. Environ. 38, 761–773 (2004)CrossRefGoogle Scholar
  36. Jayne, J., Leard, D., Zhang, X., Davidovits, P., Smith, K., Kolb, C., Worsnop, D.: Development of an aerosol mass spectrometer for size and composition analysis of submicron particles. Aerosol. Sci. Technol. 33, 49–70 (2000)CrossRefGoogle Scholar
  37. Jenkin, M.E.: Modelling the formation and composition of secondary organic aerosol from α- and β-pinene ozonolysis using MCM v3. Atmos. Chem. Phys. 4, 1741–1757 (2004)Google Scholar
  38. 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., Wilson, J.: Organic aerosol and global climate modelling: A review. Atmos. Chem. Phys. 5, 1053–1123 (2005)CrossRefGoogle Scholar
  39. Kesselmeier, J., Staudt, M.: Biogenic volatile organic compounds (VOC): An overview on emission. physiology and ecology. J. Atmos. Chem. 33, 23–88 (1999)CrossRefGoogle Scholar
  40. Kulmala, M., Vehkamäki, H., Petäja, T., Dal Maso, M., Lauri, A., Kerminen, V.-M., Birmili, W., McMurry, P.H.: Formation and growth rates of ultrafine atmospheric particles: a review of observations. J. Aerosol. Sci. 35, 143–176 (2004a)CrossRefGoogle Scholar
  41. Kulmala, M., Kerminen, V.-M., Anttila, T., Laaksonen, A., O’Dowd, C.D.: Organic aerosol formation via sulphate cluster activation. J. Geophys. Res. 109, D04205, doi: 10.1029/2003JD003961 (2004b)CrossRefGoogle Scholar
  42. Leck, C., Bigg, E.K.: Source and evolution of the marine aerosol – A new perspective. Geophys. Res. Lett., 32, doi: 10.1029/2005GL023651 (2005)
  43. Lindinger, W., Hansel, A., Jordan, A.: On-line monitoring of volatile organic compounds at ppt levels by means of proton-transfer-reaction mass spectrometry (PTR-MS) medical applications, food control and environmental research. Int. J. Mass Spectrom. Ion Process. 173, 191–241 (1998)CrossRefGoogle Scholar
  44. McFiggans, G., Artaxo, P., Baltensperger, U., Coe, H., Facchini, M.C., Feingold, G., Fuzzi, S., Gysel, M., Laaksonen, A., Lohmann, U., Mentel, T.F., Murphy, D.M., O’Dowd, C.D., Snider, J.R., Weingartner, E.: The effect of physical and chemical aerosol properties on warm cloud droplet activation. Atmos. Chem. Phys. 6, 2593–2649 (2006)Google Scholar
  45. McNeill, V.F., Patterson, J., Wolfe, G.M., Thornton, J.A.: The effect of varying levels of surfactant on the reactive uptake of N2O5 to aqueous aerosol. Atmos. Chem. Phys. 6, 1635–1644 (2006)Google Scholar
  46. Medina, J., Nenes, A.: Effects of film-forming compounds on the growth of giant cloud condensation nuclei: Implications for cloud microphysics and the aerosol indirect effect. J. Geophys. Res., 109, D20207, doi: 10.1029/2004JD004666 (2004)
  47. Mentel, T.F., Bleilebens, D., Wahner A.: A study of nighttime nitrogen oxide oxidation in a large reaction chamber – The fate of NO2 N2O5, HNO3, and O3 at different humidities. Atmos. Environ. 30, 4007–4020 (1996)CrossRefGoogle Scholar
  48. Mircea, M., Facchini, M.C., Decesari, S., Fuzzi, S., Charlson, R.J.: The influence of the organic aerosol component on CCN supersaturation spectra for different aerosol types. Tellus B 54, 74–81 (2002)CrossRefGoogle Scholar
  49. Mochida, M., Kitamori, Y., Kawamura, K., Nojiri, Y., Suzuki, K.: Fatty acids in the marine atmosphere: Factors governing their concentrations and evaluation of organic films on sea-salt particles. J. Geophys. Res. 107, doi: 10.1029/2001JD4325 (2002)
  50. Moroi, Y., Rusdi, M., and Kubo, I.: Differences in surface properties between insoluble monolayer and adsorbed film from kinetics of water evaporation and BAM image. J. Phys. Chem., B 108, 6351–6358 (2004)CrossRefGoogle Scholar
  51. O’Dowd, C.D., Facchini, M.C., Ceburnis, F.D., Mircea, M., Decesari, S., Yoon, Y.J., Putaud, J.-P.: Biogenically driven organic contribution to marine aerosol, Nature 431, 676–680 (2004)CrossRefGoogle Scholar
  52. Odum, J.R., Hofmann, T., Bowman, F., Collins, D., Flagan, R.C., Seinfeld, J.H.: Gas/particle partitioning and organic aerosol yields. Environ. Sci. Technol. 30, 2580–2585 (1996)CrossRefGoogle Scholar
  53. Pankow, J.F.: Review and comparative analysis of the theories on partitioning between the gas and aerosol particulate phases in the atmosphere. Atmos. Environ. 21, 2275–2283 (1987)CrossRefGoogle Scholar
  54. Pankow, J.F.: An absorption model of gas/particle partitioning of organic compounds in the atmosphere. Atmos. Environ. 28, 185–188 (1994)CrossRefGoogle Scholar
  55. Raatikainen, T., Laaksonen, A.: Application of several activity coefficient models to water-organic-electrolyte aerosols of atmospheric interest. Atmos. Chem. Phys. 5, 2475–2495 (2005)CrossRefGoogle Scholar
  56. Russell, L.M., Maria, S.F., Myneni, S.C.B.: Mapping organic coatings on atmospheric particles. Geophys. Res. Lett. 29, doi: 10.1029/2002GL014874 (2002)
  57. Saathoff, H., Naumann, K.-H., Schnaiter, M., Schöck, W., Möhler, O., Schurath, U., Weingartner, E., Gysel, M., Baltensperger, U.: Coating of soot and (NH4)2SO4 particles by ozonolysis products of α-pinene. J. Aerosol Sci. 34, 1297–1321 (2003)CrossRefGoogle Scholar
  58. Seidl, W.: Model for a surface film of fatty acids on rain water and aerosol particles. Atmos. Environ. 34, 4917–4932 (2000)CrossRefGoogle Scholar
  59. Seinfeld, J.H., Pandis, S.N.: Atmospheric Chemistry and Physics: From Air Pollution to Climate Change. Wiley, New York, USA (1998)Google Scholar
  60. Seinfeld, J.H., Pankow, J.F.: Organic atmospheric particulate material. Annu. Rev. Phys. Chem. 54, 121–140 (2003)CrossRefGoogle Scholar
  61. Stroud, C.A., Makar, P., Michelangeli, D.V., Mozurkewich, M., Hastie, D.R., Barbu, A., Humble, A.: Simulating organic aerosol formation during the photooxidation of toluene/NOx mixtures: Comparing the equilibrium and kinetic assumption. Environ. Sci. Technol. 38, 1471–1479 (2004)CrossRefGoogle Scholar
  62. Tabazadeh, A.: Organic aggregate formation in aerosols and its impact on the physicochemical properties of atmospheric particles. Atmos. Environ. 39, 5472–5480 (2005)CrossRefGoogle Scholar
  63. Tang, I.N., Munkelwitz, H.R.: Water activities, densities, and refractive indices of aqueous sulfates and sodium nitrate droplets of atmospheric importance. J. Geophys. Res. 99, 18 801–18 808 (1994)CrossRefGoogle Scholar
  64. Tervahattu, H., Hartonen, K., Kerminen, V.-M., Kupiainen, K., Aarnio, P., Koskentalo, T., Tuck, A.F., Vaida, V.: New evidence of an organic layer on marine aerosols. J. Geophys. Res. 107, doi: 19.1029/2000JD000282 (2002a)
  65. Tervahattu, H., Juhanoja, J., Kupiainen, K.: Identification of an organic coating on marine aerosol particles by TOF-SIMS. J. Geophys. Res. 107, doi: 10.1029/2001JD001403 (2002b)
  66. Tervahattu, H., Juhanoja, J., Vaida, V., Tuck, A.F., Niemi, J.V., Kupiainen, K., Kulmala, M., Vehkamaki, H.: Fatty acids on continental sulphate aerosol particles. J. Geophys. Res. 110, D06207 (2005)CrossRefGoogle Scholar
  67. Winterhalter, R., Dingenen, R.V., Larsen, B.R., Jensen, N.R., Hjorth, J.: LC-MS analysis of aerosol particles from the oxidation of α-pinene by ozone and OH-radicals. J. Atmos. Chem. Phys. Discuss. 3, 1–39 (2003)CrossRefGoogle Scholar
  68. Varutbangkul, V., Brechtel, F.J., Bahreini, R., Ng, N.L., Keywood, M.D., Kroll, J.H., Flagan, R.C., Seinfeld J.H., Lee, A., 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)CrossRefGoogle Scholar
  69. Virkkula, A., Van Dingenen, R., Raes, F., Hjorth, J.: Hygroscopic properties of aerosol formed by oxidation of limonene, α-pinene, and β-pinene. J. Geophys. Res. 104, 3569–3579 (1999)CrossRefGoogle Scholar
  70. Yu, J., Cocker III, D.R., Griffin, R.J., Flagan, R.C., Seinfeld, J.H.: Gas-phase ozone oxidation of monoterpenes: gaseous and particulate products. J. Atmos. Chem. 34, 207–258 (1999)CrossRefGoogle Scholar
  71. Zelenyuk, A., Imre D., Cuadra-Rodriguez, L.A.: Evaporation of water from particles in the aerodynamic lens inlet: An experimental study. Anal. Chem. 78, 6942–6947 (2006)CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, B.V. 2007

Authors and Affiliations

  • T. Anttila
    • 2
  • A. Kiendler-Scharr
    • 1
  • Th. F. Mentel
    • 1
  • R. Tillmann
    • 1
  1. 1.ICG-2: Troposphäre, Forschungszentrum JülichJülichGermany
  2. 2.Finnish Meteorological Institute, Research and Development, Climate and Global ChangeHelsinkiFinland

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