Atmospheric Chemistry and Physics
www.atmos-chem-phys.net
1680-7316
1680-7324
7
16
2007
10.5194/acp-7-4187-2007
http://www.atmos-chem-phys.net/7/4187/2007/
http://www.atmos-chem-phys.net/7/4187/2007/acp-7-4187-2007.html
http://www.atmos-chem-phys.net/7/4187/2007/acp-7-4187-2007.pdf
4187
4201
2007-08-16
Heterogeneous oxidation of saturated organic aerosols by hydroxyl radicals: uptake kinetics, condensed-phase products, and particle size change
I. J. George
A. Vlasenko
J. G. Slowik
K. Broekhuizen
J. P. D. Abbatt
jabbatt@chem.utoronto.ca
Department of Chemistry and Southern Ontario Centre for Atmospheric Aerosol Research, University of Toronto, 80 St. George Street, Toronto M5S 3H6, Ontario, Canada
Department of Chemistry, Colgate University, 13 Oak Dr., Hamilton, NY 13346, USA
The kinetics and reaction mechanism for the heterogeneous oxidation of
saturated organic aerosols by gas-phase OH radicals were investigated under
NO<sub>x</sub>-free conditions. The reaction of 150 nm diameter Bis(2-ethylhexyl)
sebacate (BES) particles with OH was studied as a proxy for chemical aging
of atmospheric aerosols containing saturated organic matter. An aerosol
reactor flow tube combined with an Aerodyne time-of-flight aerosol mass
spectrometer (ToF-AMS) and scanning mobility particle sizer (SMPS) was used
to study this system. Hydroxyl radicals were produced by 254 nm photolysis
of O<sub>3</sub> in the presence of water vapour. The kinetics of the
heterogeneous oxidation of the BES particles was studied by monitoring the
loss of a mass fragment of BES with the ToF-AMS as a function of OH
exposure. We measured an initial OH uptake coefficient of γ<sub>0</sub>=1.3 (±0.4), confirming that this reaction is highly efficient. The
density of BES particles increased by up to 20% of the original BES
particle density at the highest OH exposure studied, consistent with the
particle becoming more oxidized. Electrospray ionization mass spectrometry
analysis showed that the major particle-phase reaction products are
multifunctional carbonyls and alcohols with higher molecular weights than
the starting material. Volatilization of oxidation products accounted for a
maximum of 17% decrease of the particle volume at the highest OH exposure
studied. Tropospheric organic aerosols will become more oxidized from
heterogeneous photochemical oxidation, which may affect not only their
physical and chemical properties, but also their hygroscopicity and cloud
nucleation activity.
Alfarra, M. R.: Insights into Atmospheric Organic Aerosols Using an Aerosol Mass Spectrometer, Ph.D. Dissertation thesis, University of Manchester, Manchester, 2004.
Atkinson, R.: Gas-phase tropospheric chemistry of organic compounds, J. Phys. Chem. Ref. Data Monograph, 2, 1–216, 1994.
Atkinson, R.: Gas-phase tropospheric chemistry of volatile organic compounds. 1. Alkanes and alkenes, J. Phys. Chem. Ref. Data, 26, 215–290, 1997.
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., Sjögren, S., Weingartner, E., and Zenobib, R.: Secondary organic aerosols from anthropogenic and biogenic precursors, Faraday Discuss., 130, 265–278, 2005.
Bertram, A. K., Ivanov, A. V., Hunter, M., Molina, L. T., and Molina, M. J.: The reaction probability of OH on organic surfaces of tropospheric interest, J. Phys. Chem. A, 105, 9415–9421, 2001.
Braun, W, Herron, J. T., and Kahaner, D. K.: Acuchem – A computer-program for modeling complex chemical-reaction systems, Int. J. Chem. Kinet., 20, 51–62, 1988.
Cooper, P. L. and Abbatt, J. P. D.: Heterogeneous interactions of OH and HO<sub>2</sub> radicals with surfaces characteristic of atmospheric particulate matter, J. Phys. Chem., 100, 2249–2254, 1996.
de Gouw, J. A., Middlebrook, A. M., Warneke, C., Goldan, P. D., Kuster, W. C., Roberts, J. M., Fehsenfeld, F. C., Worsnop, D. R., Canagaratna, M. R., Pszenny, A. A. P., Keene, W. C., Marchewka, M., Bertman, S. B., and Bates, T. S.: Budget of organic carbon in a polluted atmosphere: Results from the New England Air Quality Study in 2002, J. Geophys. Res.-Atmos., 110, D16305, doi:10.1029/2004JD005623, 2005.
DeCarlo, P., Slowik, J. G., Worsnop, D. R., Davidovits, P., and Jimenez, J. L.: Particle morphology and density characterization by combined mobility and aerodynamic diameter measurements. Part 1: Theory, Aerosol Sci. Technol., 38, 1185–1205, 2004.
DeMore, W. B., Sander, S. P., Golden, D. M., Hampson, R. F., Kurylo, M. J., Howard, C. J., Ravishankara, A. R., Kolb, C. E., and Molina, M. J.: Chemical kinetics and photochemical data for use in stratospheric modelling, Evaluation No. 12, JPL Publication 97-4, 1997.
Docherty, K. S. and Ziemann, P. J.: Reaction of oleic acid particles with NO<sub>3</sub> radicals: Products, mechanism, and implications for radical-initiated organic aerosol oxidation, J. Phys. Chem. A, 110, 3567–3577, 2006.
Drewnick, F., Hings, S. S., DeCarlo, P., Jayne, J. T., Gonin, M., Fuhrer, K., Weimer, S., Jimenez, J. L., Demerjian, K. L., Borrmann, S., and Worsnop, D. R.: A new time-of-flight aerosol mass spectrometer (TOF-AMS) - Instrument description and first field deployment, Aerosol Sci. Technol., 39, 637–658, 2005.
Eliason, T. L., Gilman, J. B., and Vaida, V.: Oxidation of organic films relevant to atmospheric aerosols, Atmos. Environ., 38, 1367–1378, 2004.
Finlayson-Pitts, B. J. and Pitts, J. N.: Chemistry of the Upper and Lower Atmosphere: Theory, Experiments, and Applications, Academic Press, 2000.
Fuchs, N. A. and Sutugin, A. G.: Highly Dispersed Aerosols, Ann Arbor Science Publishers, 1970.
Hearn, J. D. and Smith, G. D.: Kinetics and product studies for ozonolysis reactions of organic particles using aerosol CIMS, J. Phys. Chem. A, 108, 10 019–10 029, 2004.
Hearn, J. D. and Smith, G. D.: Measuring rates of reaction in supercooled organic particles with implications for atmospheric aerosol, Phys. Chem. Chem. Phys., 7, 2549–2551, 2005.
Hearn, J. D. and Smith G. D.: A mixed-phase relative rates technique for measuring aerosol reaction kinetics, Geophys. Res. Lett., 33, L17805, doi:10.1029/2006GL026963, 2006.
Hearn, J. D., Renbaum, L. H., Wang, Xi, and Smith, G. D.: Kinetics and products from reaction of Cl radicals with dioctyl sebacate (DOS) particles in O<sub>2</sub>: a model for radical-initiated oxidation of organic aerosols, Phys. Chem. Chem. Phys., 2007, doi:10.1039/b707523e.
Ivanov, A. V., Trakhtenberg, S., Bertram, A. K., Gershenzon, Y. M., and Molina, M. J.: OH, HO<sub>2</sub>, and ozone gaseous diffusion coefficients, J. Phys. Chem. A, 111, 1632–1637, 2007.
Jacobson, M. C., Hansson, H. C, Noone, K. J., and Charlson, R. J.: Organic atmospheric aerosols: Review and state of the science, Rev. Geophys., 38, 267–294, 2000.
Jang, M., Czoschke, N. M., Lee, S., and Kamens, R. M.: Heterogeneous atmospheric aerosol production by acid-catalyzed particle-phase reactions, Science, 298, 814–817, 2002.
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., Dingenen, R. V., 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.
Katrib, Y., Martin, S. T., Hung, H. M., Rudich, Y., Zhang, H. Z., Slowik, J. G., Davidovits, P., Jayne, J. T., and Worsnop, D. R.: Products and mechanisms of ozone reactions with oleic acid for aerosol particles having core-shell morphologies, J. Phys. Chem. A, 108, 6686–6695, 2004.
Katrib, Y., Biskos, G., Buseck, P. R., Davidovits, P., Jayne, J. T., Mochida, M., Wise, M. E., Worsnop, D. R., and Martin, S. T.: Ozonolysis of mixed oleic-acid/stearic-acid particles: Reaction kinetics and chemical morphology, J. Phys. Chem. A, 109, 10 910–10 919, 2005.
Knopf, D. A., Anthony, L. M., and Bertram, A. K.: Reactive uptake of O<sub>3</sub> by multicomponent and multiphase mixtures containing oleic acid, J. Phys. Chem. A, 109, 5579–5589, 2005.
Knopf, D. A., Mak, J., Gross, S., and Bertram, A. K.: Does atmospheric processing of saturated hydrocarbon surfaces by NO<sub>3</sub> lead to volatilization?, Geophys. Res. Lett., 33, L17816, doi:10.1029/2006GL026884, 2006.
Kwan, A. J., Crounse, J. D., Clarke, A. D., Shinozuka, Y., Anderson, B. E., Crawford, J. H., Avery, M. A., McNaughton, C. S., Brune, W. H., Singh, H. B., and Wennberg, P. O.: On the flux of oxygenated volatile organic compounds from organic aerosol oxidation, Geophys. Res. Lett., 33, L15815, doi:10.1029/2006GL026144, 2006.
Lambe, A. T., Zhang, J., Sage, A. M., and Donahue, N. M.: Controlled OH radical production via ozone-alkene reactions for use in aerosol aging studies, Environ. Sci. Technol., 41, 2357–2363, 2007.
Massman, W. J.: A review of the molecular diffusivities of H<sub>2</sub>O, CO<sub>2</sub>, CH<sub>4</sub>, CO, O<sub>3</sub>, SO<sub>2</sub>, NH<sub>3</sub>, N<sub>2</sub>O, NO, and NO<sub>2</sub> in air, O<sub>2</sub> and N<sub>2</sub> near STP, Atmos. Environ., 32, 1111–1127, 1998.
McFiggans, G., Alfarra, M. R., Allan, J., Bower, K., Coe, H., Cubison, M., Topping, D., Williams, P., Decesari, S., Facchini, C., and Fuzzi, S.: Simplification of the representation of the organic component of atmospheric particulates, Faraday Discuss., 130, 341–362, doi:10.1039/b419435, 2005.
Moise, T. and Rudich, Y.: Uptake of Cl and Br by organic surfaces - a perspective on organic aerosols processing by tropospheric oxidants, Geophys. Res. Lett., 28(21), 4083–4086, 2001.
Moise, T. and Rudich, Y.: Reactive uptake of ozone by aerosol-associated unsaturated fatty acids: Kinetics, mechanisms and products, J. Phys. Chem. A, 106, 6469–6476, 2002.
Moise, T., Talukdar, R. K., Frost, G. J., Fox, R. W., and Rudich, Y.: Reactive uptake of NO<sub>3</sub> by liquid and frozen organics, J. Geophys. Res., 107(D2), 4014, doi:10.1029/2001JD000334, 2002.
Molina, M. J., Ivanov, A. V., Trakhtenberg, S., and Molina, L. T.: Atmospheric evolution of organic aerosol, Geophys. Res. Lett., 31, L22104, doi:10.1029/2004GL020910, 2004.
Morris, J. W., Davidovits, P., Jayne, J. T., Jimenez, J. L., Shi, Q., Kolb, C. E., Worsnop, D. R., Barney, W. S., and Cass, G.: Kinetics of submicron oleic acid aerosols with ozone: A novel aerosol mass spectrometric technique, Geophys. Res. Lett., 29(9), 1357, doi:10.1029/2002GL014692, 2002.
Picquet-Varrault, B., Doussin, J.-F., Durand-Jolibois, R., and Carlier, P.: FTIR spectroscopic study of the OH-induced oxidation of isopropyl, isobutyl, and \textittert-butyl acetates, J. Phys. Chem. A, 106, 2895–2902, 2002.
Ramanathan, V., Crutzen, P. J., Kiehl, J. T., and Rosenfeld, D.: Aerosols, climate, and the hydrological cycle, Science, 294, 2119–2124, 2001.
Robinson, A. L., Donahue, N. M., and Rogge, W. F.: Photochemical oxidation and changes in molecular composition of organic aerosol in the regional context, J. Geophys. Res., 111, D03302, doi:10.1029/2005JD006265, 2006.
Russell, G. A.: Deuterium-isotope effects in the autooxidation of aralkyl hydrocarbons: Mechanism of the interaction of peroxy radicals, J. Am. Chem. Soc., 79, 3871–3877, 1957.
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 and Physics: From Air Pollution to Climate Change, Wiley-Interscience, 1998.
Takegawa, N., Miyakawa, T., Kondo, Y., Blake, D. R., Kanaya, Y., Koike, M., Fukuda, M., Komazaki, Y., Miyazaki, Y., Shimono, A., and Takeuchi, T.: Evolution of submicron organic aerosol in polluted air exported from Tokyo, Geophys. Res. Lett., 33, L15814, doi:10.1029/2006GL025815, 2006.
Thornberry, T. D. and Abbatt, J. P. D.: Heterogeneous reaction of ozone with liquid unsaturated fatty acids: Detailed kinetics and gas-phase product studies, Phys. Chem. Chem. Phys., 6, 84–93, 2004.
Worsnop, D. R., Morris, J. W., Shi, Q., Davidovits, P., and Kolb, C. E.: A chemical kinetic model for reactive transformations of aerosol particles, Geophys. Res. Lett., 29(20), 1357, doi:10.1029/2002GL015542, 2002.
Zhang, Q., Worsnop, D. R., Canagaratna, M. R., and Jimenez, J. L.: Hydrocarbon-like and oxygenated organic aerosols in Pittsburgh: Insights into sources and processes of organic aerosols, Atmos. Chem. Phys., 5, 3289–3311, 2005.
Ziemann, P. J.: Aerosol products, mechanisms, and kinetics of heterogeneous reactions of ozone with oleic acid in pure and mixed particles, Faraday Discuss., 130, 469–490, 2005.