Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 9 5 2009 10.5194/acp-9-1551-2009 http://www.atmos-chem-phys.net/9/1551/2009/ http://www.atmos-chem-phys.net/9/1551/2009/acp-9-1551-2009.html http://www.atmos-chem-phys.net/9/1551/2009/acp-9-1551-2009.pdf 1551 1577 2009-03-03 Temperature dependence of yields of secondary organic aerosols from the ozonolysis of α-pinene and limonene H. Saathoff K.-H. Naumann O. Möhler Å. M. Jonsson M. Hallquist A. Kiendler-Scharr Th. F. Mentel R. Tillmann U. Schurath Institute for Meteorology and Climate Research, Forschungszentrum Karlsruhe, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany Department of Chemistry, Atmospheric Science, University of Gothenburg, 412 96 Göteborg, Sweden Institute of Chemistry and Dynamics of the Geosphere 2, Forschungszentrum Jülich, 52425 Jülich, Germany Secondary organic aerosol (SOA) formation has been investigated as a function of temperature and humidity for the ozone-initiated reaction of the two monoterpenes α-pinene (243–313 K) and limonene (253–313 K) using the 84.5 m3 aerosol chamber AIDA. This paper gives an overview of the measurements done and presents parameters specifically useful for aerosol yield calculations. The ozonolysis reaction, selected oxidation products and subsequent aerosol formation were followed using several analytical techniques for both gas and condensed phase characterisation. The effective densities of the SOA were determined by comparing mass and volume size distributions to (1.25±0.10) g cm−3 for α-pinene and (1.3±0.2) g cm−3 for limonene. The detailed aerosol dynamics code COSIMA-SOA proved to be essential for a comprehensive evaluation of the experimental results and for providing parameterisations directly applicable within atmospheric models. The COSIMA-assisted analysis succeeded to reproduce the observed time evolutions of SOA total mass, number and size distributions by adjusting the following properties of two oxidation product proxies: individual yield parameters (αi), partitioning coefficients (Ki), vapour pressures (pi) and effective accommodation coefficients (γi). For these properties temperature dependences were derived and parameterised. Vapour pressures and partitioning coefficients followed classical Clausius – Clapeyron temperature dependences. From this relationship enthalpies of vaporisation were derived for the two more and less volatile product proxies of α-pinene: (59±8) kJ mol−1 and (24±9) kJ mol−1, and limonene: (55±14) kJ mol−1 and (25±12) kJ mol−1. The more volatile proxy components had a notably low enthalpy of vaporisation while the less volatile proxy components gave enthalpies of vaporisation comparable with those of typical products from α-pinene oxidation, e.g. pinonaldehyde and pinonic acid. Alfarra, M. R., Paulsen, D., Gysel, M., Garforth, A. A., Dommen, J., Prévôt, 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. Atkinson, R., Winer, A. M., and Pitts Jr., J. N.: Rate constants for the gas-phase reactions of O3 with the natural hydrocarbons isoprene and $\alpha $-pinene and $\beta $-pinene, Atmos. Environ., 16, 1017–1020, 1982. Atkinson, R.: Gas-phase tropospheric chemistry of volatile organic compounds .1. Alkanes and alkenes, J. Phys. Chem. Ref. Data, 26, 215–290, 1997. Bahreini, R., Keywood, M. D., Ng, N. L., Varutbangkul, V., Gao, S., Flagan, R. C., Seinfeld, J. H., Worsnop, D. R., and 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. Berndt, T., Böge, O., and Stratmann, F.: Gas-phase ozonolysis of $\alpha $-pinene: gaseous products and particle formation, Atmos. Environ., 37, 3933–3945, 2003. Bilde, M. and Pandis, S. N.: Evaporation rates and vapor pressures of individual aerosol species formed in the atmospheric oxidation of α- and β-pinene, Environ. Sci. Technol., 35, 3344–3349, 2001. Bilde, M., Svenningsson, B., Monster, J., and Rosenorn, T.: Even-odd alternation of evaporation rates and vapor pressures of C3-C9 dicarboxylic acid aerosols, Environ. Sci. Technol., 37, 1371–1378, 2003. Bonn, B., Schuster, G., and Moortgat, G. K.: Influence of water vapor on the process of new particle formation during monoterpene ozonolysis, J. Phys. Chem. A, 106, 2869–2881, 2002. Bowman, F. M., Odum, J. R., Seinfeld, J. H., and Pandis, S. N.: Mathematical model for gas-particle partitioning of secondary organic aerosols, Atmos. Environ., 31, 3921–3931, 1997. Bunz, H. and Dlugi, R.: Numerical Studies on the Behavior of Aerosols in Smog Chambers, J. Aerosol Sci, 22, 441–465, 1991. Cahill, T. M., Seaman, V. Y., Charles, M. J., Holzinger, R., and Goldstein, A. H.: Secondary organic aerosols formed from oxidation of biogenic volatile organic compounds in the Sierra Nevada Mountains of California, J. Geophys. Res.-Atmos., 111, D16312, doi:16310.11029/12006JD007178, 2006. Cai, X. Y. and Griffin, R. J.: Theoretical modeling of the size-dependent influence of surface tension on the absorptive partitioning of semi-volatile organic compounds, J. Atmos. Chem., 50, 139–158, 2005. Calogirou, A., Larsen, B. R., and Kotzias, D.: Gas-phase terpene oxidation products: a review, Atmos. Environ., 33, 1423–1439, 1999. Capouet, M. and Müller, J.-F.: A group contribution method for estimating the vapour pressures of α-pinene oxidation products, Atmos. Chem. Phys., 6, 1455–1467, 2006. Chattopadhyay, S. and Ziemann, P. J.: Vapor pressures of substituted and unsubstituted monocarboxylic and dicarboxylic acids measured using an improved thermal desorption particle beam mass spectrometry method, Aerosol Sci. Technol., 39, 1085–1100, 2005. Cocker, D. R., Clegg, S. L., Flagan, R. C., and Seinfeld, J. H.: The effect of water on gas-particle partitioning of secondary organic aerosol. Part I: $\alpha $-pinene/ozone system, Atmos. Environ., 35, 6049–6072, 2001. Dahneke, B.: Simple Kinetic Theory of Brownian Diffusion in Vapors and Aerosols, Theory of Dispersed Multiphase Flow, edited by: Meyer, R. E., Academic Press, New York, 97–133 pp., 1983. DeCarlo, P. F., 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. Docherty, K. S., Wu, W., Lim, Y. B., and Ziemann, P. J.: Contributions of organic peroxides to secondary aerosol formed from reactions of monoterpenes with O3, Environ. Sci. Technol., 39, 4049–4059, 2005. Fredenslund, A., Gmehling, J., and Rasmussen, P.: Vapor-Liquid Equilibria Using UNIFAC: A Group-Contribution Method, Elsevier Scientific Publishing, New York, 380 pp., 1977. 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, 2004. Glasius, M., Lahaniati, M., Calogirou, A., Di Bella, D., Jensen, N. R., Hjorth, J., Kotzias, D., and Larsen, B. R.: Carboxylic acids in secondary aerosols from oxidation of cyclic monoterpenes by ozone, Environ. Sci. Technol., 34, 1001–1010, 2000. Griffin, R. J., Cocker, D. R., Flagan, R. C., and Seinfeld, J. H.: Organic aerosol formation from the oxidation of biogenic hydrocarbons, J. Geophys. Res.-Atmos., 104, 3555–3567, 1999a. Griffin, R. J., Cocker, D. R., Seinfeld, J. H., and Dabdub, D.: Estimate of global atmospheric organic aerosol from oxidation of biogenic hydrocarbons, Geophys. Res. Lett., 26, 2721–2724, 1999b. Griffin, R. J., Dabdub, D., and Seinfeld, J. H.: Development and initial evaluation of a dynamic species-resolved model for gas phase chemistry and size-resolved gas/particle partitioning associated with secondary organic aerosol formation, J. Geophys. Res.-Atmos., 110, D05304, doi:05310.01029/02004JD005219, 2005. 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.-Atmos., 100, 8873–8892, 1995. Hallquist, M., Wängberg, I., and Ljungström, E.: Atmospheric fate of carbonyl oxidation products originating from α-pinene and $\Delta ^3$-carene: Determination of rate of reaction with OH and NO3 radicals, UV absorption cross sections, and vapor pressures, Environ. Sci. Technol., 31, 3166–3172, 1997. Hamilton, J. F., Lewis, A. C., Carey, T. J., and Wenger, J. C.: Characterization of polar compounds and oligomers in secondary organic aerosol using liquid chromatography coupled to mass spectrometry, Anal. Chem., 80, 474–480, 2008. Heald, C. L., Jacob, D. J., Park, R. J., Russell, L. M., Huebert, B. J., Seinfeld, J. H., Liao, H., and Weber, R. J.: A large organic aerosol source in the free troposphere missing from current models, Geophys. Res. Lett., 32, L18809, doi:18810.11029/12005GL023831, 2005. Hoffmann, T., Odum, J. R., Bowman, F., Collins, D., Klockow, D., Flagan, R. C., and Seinfeld, J. H.: Formation of organic aerosols from the oxidation of biogenic hydrocarbons, J. Atmos. Chem., 26, 189–222, 1997. Hoppel, W., Fitzgerald, J., Frick, G., Caffrey, P., Pasternack, L., Hegg, D., Gao, S., Leaitch, R., Shantz, N., Cantrell, C., Albrechcinski, T., Ambrusko, J., and Sullivan, W.: Particle formation and growth from ozonolysis of $\alpha $-pinene, J. Geophys. Res.-Atmos., 106, 27603–27618, 2001. Iinuma, Y., Böge, O., Gnauk, T., and Herrmann, H.: Aerosol-chamber study of the $\alpha $-pinene/O3 reaction: influence of particle acidity on aerosol yields and products, Atmos. Environ., 38, 761–773, 2004. Iinuma, Y., Boge, O., Miao, Y., Sierau, B., Gnauk, T., and Herrmann, H.: Laboratory studies on secondary organic aerosol formation from terpenes, Faraday Discuss., 130, 279–294, 2005. Iinuma, Y., Muller, C., Boge, O., Gnauk, T., and Herrmann, H.: The formation of organic sulfate esters in the limonene ozonolysis secondary organic aerosol (SOA) under acidic conditions, Atmos. Environ., 41, 5571–5583, 2007. Jang, M. S., Carroll, B., Chandramouli, B., and Kamens, R. M.: Particle growth by acid-catalyzed heterogeneous reactions of organic carbonyls on preexisting aerosols, Environ. Sci. Technol., 37, 3828–3837, 2003. 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. Johnson, D. and Marston, G.: The gas-phase ozonolysis of unsaturated volatile organic compounds in the troposphere, Chem. Soc. Rev., 37, 699–716, doi:10.1039/b704260b, 2008. Jonsson, Å. M., Hallquist, M., and Ljungström, E.: Impact of humidity on the ozone initiated oxidation of limonene, $\Delta ^3$-carene, and $\alpha $-pinene, Environ. Sci. Technol., 40, 188–194, 2006. Jonsson, Å. M., Hallquist, M., and Saathoff, H.: Volatility of secondary organic aerosols from the ozone initiated oxidation of $\alpha $-pinene and limonene, J. Aerosol Sci, 38, 843–852, 2007. Jonsson, Å. M., Hallquist, M., and Ljungstrom, E.: Influence of OH scavenger on the water effect on secondary organic aerosol formation from ozonolysis of limonene, $\Delta ^3$-carene, and $\alpha $-pinene, Environ. Sci. Technol., 42, 5938–5944, 2008a. Jonsson, Å. M., Hallquist, M., and Ljungstr�m, E.: The effect of temperature and water on secondary organic aerosol formation from ozonolysis of limonene, $\Delta ^3$-carene and $\alpha $-pinene, Atmos. Chem. Phys., 8, 6541–6549, 2008b. 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. Keywood, M. D., Kroll, J. H., Varutbangkul, V., Bahreini, R., Flagan, R. C., and Seinfeld, J. H.: Secondary organic aerosol formation from cyclohexene ozonolysis: Effect of OH scavenger and the role of radical chemistry, Environ. Sci. Technol., 38, 3343–3350, 2004. Khamaganov, V. G., and Hites, R. A.: Rate constants for the gas-phase reactions of ozone with isoprene, α- and $\beta $-pinene, and limonene as a function of temperature, J. Phys. Chem. A, 105, 815–822, 2001. Koch, S., Winterhalter, R., Uherek, E., Kolloff, A., Neeb, P., and Moortgat, G. K.: Formation of new particles in the gas-phase ozonolysis of monoterpenes, Atmos. Environ., 34, 4031–4042, 2000. Kostenidou, E., Pathak, R. K., and Pandis, S. N.: An Algorithm for the Calculation of Secondary Organic Aerosol Density Combining AMS and SMPS Data, Aerosol Sci. Technol., 41, 1002–1010, 2007. Kroll, J. H., Chan, A. W. H., Ng, N. L., Flagan, R. C., and Seinfeld, J. H.: Reactions of semivolatile organics and their effects on secondary organic aerosol formation, Environ. Sci. Technol., 41, 3545–3550, 2007. Leungsakul, S., Jaoui, M., and Kamens, R. M.: Kinetic mechanism for predicting secondary organic aerosol formation from the reaction of d-limonene with ozone, Environ. Sci. Technol., 39, 9583–9594, 2005. Matsunaga, S. N., Wiedinmyer, C., Guenther, A. B., Orlando, J. J., Karl, T., Toohey, D. W., Greenberg, J. P., and Kajii, Y.: Isoprene oxidation products are a significant atmospheric aerosol component, Atmos. Chem. Phys. Discuss., 5, 11143–11156, 2005. Müller, J. F.: Geographical-Distribution and Seasonal-Variation of Surface Emissions and Deposition Velocities of Atmospheric Trace Gases, J. Geophys. Res.-Atmos., 97, 3787–3804, 1992. Naumann, K. H.: COSIMA – a computer program simulating the dynamics of fractal aerosols, J. Aerosol Sci., 34, 1371–1397, 2003. Naumann, K. H.: COSIMA-SOA – a model to simulate formation and dynamics of secondary organic aerosol, J. Aerosol Sci., in preparation, 2009. Northcross, A. L. and Jang, M.: Heterogeneous SOA yield from ozonolysis of monoterpenes in the presence of inorganic acid, Atmos. Environ., 41, 1483–1493, 2007. Odum, J. R., Hoffmann, T., Bowman, F., Collins, D., Flagan, R. C., and Seinfeld, J. H.: Gas/particle partitioning and secondary organic aerosol yields, Environ. Sci. Technol., 30, 2580–2585, 1996. Offenberg, J. H., Kleindienst, T. E., Jaoui, M., Lewandowski, M., and Edney, E. O.: Thermal properties of secondary organic aerosols, Geophys. Res. Lett., 33, L03816, doi:03810.01029/02005GL024623, 2006. Pankow, J. F.: An Absorption-Model of the Gas Aerosol Partitioning Involved in the Formation of Secondary Organic Aerosol, Atmos. Environ., 28, 189–193, 1994. Pathak, R. K., Presto, A. A., Lane, T. E., Stanier, C. O., Donahue, N. M., and Pandis, S. N.: Ozonolysis of α-pinene: parameterization of secondary organic aerosol mass fraction, Atmos. Chem. Phys., 7, 3811–3821, 2007a. Pathak, R. K., Presto, A. A., Lane, T. E., Stanier, C. O., Donahue, N. M., and Pandis, S. N.: Ozonolysis of α-pinene: parameterization of secondary organic aerosol mass fraction, Atmos. Chem. Phys., 7, 3811–3821, 2007b. Plewka, A., Gnauk, T., Bru\" ggemann, E., and Herrmann, H.: Biogenic contributions to the chemical composition of airborne particles in a coniferous forest in Germany, Atmos. Environ., 40, S103–S115, 2006. Poling, B. E., Prausnitz, J. M., and Reid, R. C.: The Properties of Gases and Liquids, 4 ed., McGraw-Hill, New York, 581 pp., 1987. Presto, A. A. and Donahue, N. M.: Investigation of $\alpha $-pinene plus ozone secondary organic aerosol formation at low total aerosol mass, Environ. Sci. Technol., 40, 3536–3543, 2006. Saathoff, H., Moehler, O., Schurath, U., Kamm, S., Dippel, B., and Mihelcic, D.: The AIDA soot aerosol characterisation campaign 1999, J. Aerosol Sci, 34, 1277–1296, 2003. Seinfeld, J. H. and Pankow, J. F.: Organic atmospheric particulate material, Annu. Rev. Phys. Chem., 54, 121–140, 2003. Sheehan, P. E. and Bowman, F. M.: Estimated effects of temperature on secondary organic aerosol concentrations, Environ. Sci. Technol., 35, 2129–2135, 2001. Shilling, J. E., Chen, Q., King, S. M., Rosenoern, T., Kroll, J. H., Worsnop, D. R., McKinney, K. A., and Martin, S. T.: Particle mass yield in secondary organic aerosol formed by the dark ozonolysis of α-pinene, Atmos. Chem. Phys., 8, 2073–2088, 2008. Simpson, D., Yttri, K. E., Klimont, Z., Kupiainen, K., Caseiro, A., Gelencser, A., Pio, C., Puxbaum, H., and Legrand, M.: Modeling carbonaceous aerosol over Europe: Analysis of the CARBOSOL and EMEP EC/OC campaigns, J. Geophys. Res.-Atmos., 112, D23S14, doi:10.1029/2006JD008158, 2007. Song, C., Zaveri, R. A., Alexander, M. L., Thornton, J. A., Madronich, S., Ortega, J. V., Zelenyuk, A., Yu, X. Y., Laskin, A., and Maughan, D. A.: Effect of hydrophobic primary organic aerosols on secondary organic aerosol formation from ozonolysis of α-pinene, Geophys. Res. Lett., 34, L20803, doi:20810.21029/22007GL030720, 2007. Stanier, C. O., Pathak, R. K., and Pandis, S. N.: Measurements of the volatility of aerosols from α-piniene ozonolysis, Environ. Sci. Technol., 41, 2756–2763, 2007. Svendby, T. M., Lazaridis, M., and Torseth, K.: Temperature dependent secondary organic aerosol formation from terpenes and aromatics, J. Atmos. Chem., 59, 25–46, 2008. Takekawa, H., Minoura, H., and Yamazaki, S.: Temperature dependence of secondary organic aerosol formation by photo-oxidation of hydrocarbons, Atmos. Environ., 37, 3413–3424, 2003. Tillmann, R., Saathoff, H., Brauers, T., Kiendler-Scharr, A., and Mentel, T. F.: Rate constants for the gas phase ozonolysis of $\alpha $-pinene in the temperature range of 243–303 K, Phys. Chem. Chem. Phys., doi:10.1039/B813407C, 2008. Tillmann, R., Kiendler-Scharr, A., Mentel, T., Jonsson, Å. M., Hallquist, M., Iinuma, Y., and Saathoff, H.: Water and Temperature Dependence of Pinonaldehyde and OH yields from Ozonolyis of α-pinene, Atmos. Chem. Phys. Discuss., in preparation, 2009. Tsigaridis, K., Lathière, J., Kanakidou, M., and Hauglustaine, D. A.: Naturally driven variability in the global secondary organic aerosol over a decade, Atmos. Chem. Phys., 5, 1891–1904, 2005. Tsigaridis, K., and Kanakidou, M.: Secondary organic aerosol importance in the future atmosphere, Atmos. Environ., 41, 4682–4692, 2007. Walser, M. L., Desyaterik, Y., Laskin, J., Laskin, A., and Nizkorodov, S. A.: High-resolution mass spectrometric analysis of secondary organic aerosol produced by ozonation of limonene, Phys. Chem. Chem. Phys., 10, 1009–1022, 2008. Wentzel, M., Gorzawski, H., Naumann, K. H., Saathoff, H., and Weinbruch, S.: Transmission electron microscopical and aerosol dynamical characterization of soot aerosols, J. Aerosol Sci., 34, 1347–1370, 2003. Wirtz, K. and Martin-Reviejo, M.: Density of secondary organic aerosols, J. Aerosol Sci., 34, S223–S224, 2003. Yu, J. Z., Cocker, D. R., Griffin, R. J., Flagan, R. C., and Seinfeld, J. H.: Gas-phase ozone oxidation of monoterpenes: Gaseous and particulate products, J. Atmos. Chem., 34, 207–258, 1999a. Yu, J. Z., Griffin, R. J., Cocker, D. R., Flagan, R. C., Seinfeld, J. H., and Blanchard, P.: Observation of gaseous and particulate products of monoterpene oxidation in forest atmospheres, Geophys. Res. Lett., 26, 1145–1148, 1999b. Zhang, J. Y., Hartz, K. E. H., Pandis, S. N., and Donahue, N. M.: Secondary organic aerosol formation from limonene ozonolysis: Homogeneous and heterogeneous influences as a function of NOx, J. Phys. Chem. A, 110, 11053–11063, 2006. Zhang, Q., Alfarra, M. R., Worsnop, D. R., Allan, J. D., Coe, H., Canagaratna, M. R., and Jimenez, J. L.: Deconvolution and quantification of hydrocarbon-like and oxygenated organic aerosols based on aerosol mass spectrometry, Environ. Sci. Technol., 39, 4938–4952, 2005.