Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 8 4 2008 10.5194/acpd-8-15343-2008 http://www.atmos-chem-phys-discuss.net/8/15343/2008/ http://www.atmos-chem-phys-discuss.net/8/15343/2008/acpd-8-15343-2008.html http://www.atmos-chem-phys-discuss.net/8/15343/2008/acpd-8-15343-2008.pdf 15343 15373 2008-08-13 Loading-dependent elemental composition of &alpha;-pinene SOA particles J. E. Shilling Q. Chen S. M. King T. Rosenoern J. H. Kroll D. R. Worsnop P. F. DeCarlo A. C. Aiken D. Sueper J. L. Jimenez S. T. Martin scot_martin@harvard.edu School of Engineering and Applied Sciences, Harvard University, Cambridge, MA 02138, USA Aerodyne Research, Inc., Billerica, MA 08121, USA Department of Atmospheric and Oceanic Sciences University of Colorado, Boulder, CO 80309, USA Cooperative Institute for Research in the Environmental Sciences (CIRES), University of Colorado, Boulder, CO 80309, USA Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309, USA Department of Earth and Planetary Sciences, Harvard University, Cambridge, MA 02138, USA now at: Paul Scherrer Institut, Laboratory of Atmospheric Chemistry, Villigen-PSI, 5232, Switzerland The chemical composition of secondary organic aerosol (SOA) particles, formed by the dark ozonolysis of α-pinene, was characterized by a high-resolution time-of-flight aerosol mass spectrometer. The experiments were conducted using a continuous-flow chamber, allowing the particle mass loading and chemical composition to be maintained for several days. The organic portion of the particle mass loading was varied from 0.5 to &gt;140 μg/m³ by adjusting the concentration of reacted &alpha;-pinene from 0.9 to 91.1 ppbv. The mass spectra of the organic material changed with loading. For loadings below 5 μg/m³ the unit-mass-resolution <i>m/z</i> 44 signal intensity exceeded that of <i>m/z</i> 43, suggesting more oxygenated organic material at lower loadings. Composition measurements displayed a greater dependence for lower loadings (0.5 to 15 μg/m³) compared to higher loadings (15 to &gt;140 μg/m³). The high-resolution mass spectra showed that from &gt;140 to 0.5 μg/m³ the mass percentage of fragments containing carbon and oxygen (C_xH_yO_z⁺) monotonically increased from 48% to 54%. Correspondingly, the mass percentage of fragments representing C_xH_y⁺ decreased from 52% to 46%, and the atomic oxygen-to-carbon ratio increased from 0.29 to 0.45. The atomic ratios were accurately parameterized by a four-product basis set of decadal volatility (viz. 0.1, 1.0, 10, 100 μg/m^&minus;3) employing products with the empirical formulas C₁H_1.32O_0.48, C₁H_1.36O_0.39, C₁H_1.57O_0.24, and C₁H_1.76O_0.14. These findings suggest considerable caution is warranted in the extrapolation of laboratory results that were obtained under conditions of relatively high loading (i.e., &gt;15 μg/m³) to modeling applications relevant to the atmosphere, for which loadings of 0.1 to 20 μg/m³ are typical. For the lowest loadings, the particle mass spectra resembled observations reported in the literature for some atmospheric particles. Aiken, A. C., DeCarlo, P. F., and Jimenez, J. L.: Elemental analysis of organic species with electron ionization high-resolution mass spectrometry, Anal. Chem., 79, 8350–8358, 2007. Aiken, A. C., DeCarlo, P. F., Kroll, J. H., Worsnop, D. R., Huffman, J. A., Docherty, K., Ulbrich, I. M., Mohr, C., Kimmel, J. R., Sueper, D., Zhang, Q., Sun, Y., Trimborn, A., Northway, M., Ziemann, P. J., Canagaratna, M. R., Alfarra, R., Prevot, A. S. H., Dommen, J., Duplissy, J., Metzger, A., Baltensperger, U., and Jimenez, J. L.: O/C and OM/OC ratios of primary, secondary, and ambient organic aerosols with high resolution time-of-flight aerosol mass spectrometry, Environ. Sci. Technol., 42, 4478–4485, 2008. 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, 7747–7789, 2006. 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., and Worsnop, D. R.: Technical note: Extraction of chemically resolved mass spectra from Aerodyne aerosol mass spectrometer data, J. Aerosol Sci., 35, 909–922, 2004. 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.: Measurement 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. 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., Sjogren, S., Weingartner, E., and Zenobi, R.: Secondary organic aerosols from anthropogenic and biogenic precursors, Faraday Discuss., 130, 265–278, 2005. Bilde, M. and Pandis, S. N.: Evaporation rates and vapor pressures of individual aerosol species formed in the atmospheric oxidation of alpha- and beta-pinene, Environ. Sci. Technol., 35, 3344–3349, 2001. Bowman, F. M. and Karamalegos, A. M.: Estimated effects of composition on secondary organic aerosol mass concentrations, Environ. Sci. Technol., 36, 2701–2707, 2002. Canagaratna, M. R., Jayne, J. T., Jimenez, J. L., Allan, J. D., Alfarra, M. R., Zhang, Q., Onasch, T. B., Drewnick, F., Coe, H., Middlebrook, A., Delia, A., Williams, L. R., Trimborn, A. M., Northway, M. J., DeCarlo, P. F., Kolb, C. E., Davidovits, P., and Worsnop, D. R.: Chemical and microphysical characterization of ambient aerosol with the Aerodyne aerosol mass spectrometer, Mass. Spectrom. Rev., 26, 185–222, 2007. Chung, S. H. and Seinfeld, J. H.: Global distribution and climate forcing of carbonaceous aerosols, J. Geophys. Res., 107, 4407, 2002. DeCarlo, P., Slowik, J., Worsnop, D., Davidovits, P., and Jimenez, J.: Particle morphology and density characterization by combined mobility and aerodynamic diameter measurements, Part 1: Theory, Aerosol Sci. Technol., 38, 1185–1205, 2004. DeCarlo, P. F., Kimmel, J. R., Trimborn, A., Jayne, J. T., Aiken, A. C., Gonin, M., Fuhrer, K., Horvath, T., Docherty, K. S., Worsnop, D. R., and Jimenez, J. L.: A field-deployable high-resolution time-of-flight aerosol mass spectrometer, Anal. Chem., 78, 8281–8289, 2006. Docherty, K. S., Wu, W., Lim, Y. B., and Ziemann, P. J.: Contributions of organic peroxides to secondary aerosol formed from reaction of monoterpenes with O₃, Environ. Sci. Technol., 39, 4049–4059, 2005. Donahue, N. M., Robinson, A. L., Stanier, C. O., and Pandis, S. N.: The coupled partitioning, dilution, and chemical aging of semivolatile organics, Environ. Sci. Technol., 40, 2635–2643, 2006. Duplissy, J., Gysel, M., Alfarra, M. R., Dommen, J., Metzger, A., Prevot, A. S. H., Weingartner, E., Laaksonen, A., Raatikainen, T., Good, N., Turner, S. F., McFiggans, G., and Baltensperger, U.: The cloud forming potential of secondary organic aerosol under near atmospheric conditions, Geophys. Res. Lett., 35, L03818, doi:10.1029/2007GL031075, 2008. 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, 10 147–10 164, 2004. Hallquist, M., Wangberg, I., and Ljungstrom, E.: Atmospheric fate of carbonyl oxidation products originating from $\alpha $-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. 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:10.1029/2005GL023831, 2005. Jang, M. and Kamens, R. M.: Newly characterized products and composition of secondary aerosols from the reaction of $\alpha $-pinene with ozone, Atmos. Environ., 33, 459–474, 1999. Jayne, J. T., Leard, D. C., Zhang, X., Davidovits, P., Smith, K. A., Kolb, C. E., and Worsnop, D. R.: Development of an aerosol mass spectrometer for size and composition analysis of submicron particles, Aerosol Sci. Technol., 33, 70, 2000. Jenkin, M.: Modeling the formation and composition of secondary organic aerosol from $\alpha $- and $\beta $-pinene with O₃, Atmos. Chem. Phys., 2004, 1741–1754, 2004. Jimenez, J. L., Shi, Q., Kolb, C. E., Worsnop, D. R., Yourshaw, I., Seinfeld, J. H., Flagan, R. C., Zhang, X., Smith, K. A., Morris, J. W., and Davidovits, P.: Ambient aerosol sampling using the aerodyne aerosol mass spectrometer, J. Geophys. Res., 108, 8425, 2003. Johnson, D., Utembe, S. R., Jenkin, M. E., Derwent, R. G., Hayman, G. D., Alfarra, M. R., Coe, H., and McFiggans, G.: Simulating regional scale secondary organic aerosol formation during the Torch 2003 campaign in the southern UK, Atmos. Chem. Phys., 6, 403–418, 2006. 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. Katrib, Y., Martin, S. T., Rudich, Y., Davidovits, P., Jayne, J. T., and Worsnop, D. R.: Density changes of aerosol particles as a result of chemical reaction, Atmos. Chem. Phys., 5, 275–291, 2005. King, S. M., Rosenorn, T., Chen., Q., Shilling, J. E., and Martin, S. T.: CCN activity of mixed sulfate/SOA aerosols, Geophys. Res. Lett., 34, L24806, 10.1029/2007GL030390, 2007. Kleindienst, T. E., Smith, D. F., Li, W., Edney, E. O., Driscoll, D. J., Speer, R. E., and Weathers, W. S.: Secondary organic aerosol formation from the oxidation of aromatic hydrocarbons in the presence of dry submicron ammonium sulfate aerosol, Atmos. Environ., 33, 3669–3681, 1999. 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. and Seinfeld, J. H.: Chemistry of secondary organic aerosol: Formation and evolution of low-volatility organics in the atmosphere, Atmos. Environ., 42, 3593–3624, 2008. Lanz, V. A., Alfarra, M. R., Baltensperger, U., Buchmann, B., Hueglin, C., and Prevot, A. S. H.: Source apportionment of submicron organic aerosols at an urban site by factor analytical modeling of aerosol mass spectra, Atmos. Chem. Phys., 7, 1503–1522, 2007. Lanz, V. A., Alfarra, M. R., Baltensperger, U., Buchmann, B., Hueglin, C., Szidat, S., Wehrli, M. N., Wacker, L., Weimer, S., Caseiro, A., Puxbaum, H., and Prevot, A. S. H.: Source attribution of submicron organic aerosols during wintertime inversions by advance factor analysis of aerosol mass spectra, Environ. Sci. Technol., 42, 214–220, 2008. Marcolli, C., Canagaratna, M. R., Worsnop, D. R., Bahreini, R., deGouw, J. A., Warneke, C., Goldan, P. D., Kuster, W. C., Wiliams, E. J., Lerner, B. M., Roberts, J. M., Meagher, J. F., Fehsenfeld, F. C., Marchewka, M. L., Bertman, S. B., and Middlebrook, A. M.: Cluster analysis of the organic peaks in bulk mass spectra obtained during the 2002 New England Air Quality study with an Aerodyne aerosol mass spectrometer, Atmos. Chem. Phys., 6, 5649-5666, 2006. Pankow, J. F.: An absorption-model of gas-particle partitioning of organic-compounds in the atmosphere, Atmos. Environ., 28, 185–188, 1994a. Pankow, J. F.: An absorption-model of the gas aerosol partitioning involved in the formation of secondary organic aerosol, Atmos. Environ., 28, 189–193, 1994b. Pankow, J. F. and Asher, W. E.: Simpol.1: A simple group contribution method for predicting vapor pressures and enthalpies of vaporization of multifunctional organic compounds, Atmos. Chem. Phys., 8, 2773–2796, 2008. 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. Saunders, S. M., Jenkin, M. E., Derwent, R. G., and Pilling, M. J.: Protocol for the development of the master chemical mechanism, MCM v3 (part a): Tropospheric degradation of non-aromatic volatile organic compounds, Atmos. Chem. Phys., 3, 161–180, 2003. Seinfeld, J. H., Kleindienst, T. E., Edney, E. O., and Cohen, J. B.: Aerosol growth in a steady-state, continuous flow chamber: Application to studies of secondary aerosol formation, Aerosol Sci. Technol., 37, 728–734, 2003. Seinfeld, J. H. and Pankow, J. F.: Organic atmospheric particulate material, Annu. Rev. Phys. Chem., 54, 121–140, 2003. Shilling, J. E., Chen, Q., Rosenoern, T., King, S. M., 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 $\alpha $-pinene Atmos. Chem. Phys., 8, 2073–2088, 2008. Song, C., Zaveri, R. A., Alexander, M. L., Thorton, 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 $\alpha $-pinene, Geophys. Res. Lett., 37, L20803, doi:10.1029/2007GL030720, 2007. Takegawa, N., Miyakawa, T., Kawamura, K., and Kondo, Y.: Contribution of selected dicarboxylic and $\omega $-oxycarboxylic acids in ambient aerosol to the m/z 44 signal of an Aerodyne aerosol mass spectrometer, Aerosol Sci. Technol., 41, 418–437, 2007. Takegawa, N., Miyakawa, T., Kondo, Y., Blake, D. R., Kanaya, Y., Koike, M., Fukada, 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, 10.1029/2006GL025815, 2006. Tolocka, M. P., Jang, M., Ginter, J. M., Cox, F. J., Kamens, R. M., and Johnston, M. V.: Formation of oligomers in secondary organic aerosol, Environ. Sci. Technol., 38, 1428–1434, 2004. Ulbrich, I. M., Canagaratna, M. R., Zhang, Q., Worsnop, D. R., and Jimenez, J. L.: Interpretation of organic components from positive matrix factorization of aerosol mass spectrometric data, Atmos. Chem. Phys. Discuss., 8, 6729–6791, 2008. Volkamer, R., Jimenez, J. L., San Martini, F., Dzepina, K., Zhang, Q., Salcedo, D., Molina, L. T., Worsnop, D. R., and Molina, M. J.: Secondary organic aerosol formation from anthropogenic air pollution: Rapid and higher than expected, Geophys. Res. Lett., 33, L17811, doi:10.1029/2006GL026899, 2006. Yu, J., III, D. R. C., 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, 1999. Zhang, J., Huf-Hartz, K. E., Pandis, S. N., and Donahue, N. M.: Secondary organic aerosol formation from limonene ozonolysis: Homogeneous and heterogeneous influences as a function of NO_x, J. Phys. Chem. A, 110, 11 053–11 063, 2006. Zhang, Q., Alfarra, M. R., Worsnop, D., Allan, J. D., Coe, H., Canagaranta, M., 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, 2005a. 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, 2005b. Zhang, Q., Canagaratna, M. R., Jayne, J. T., Worsnop, D. R., and Jimenez, J.-L.: Time- and size-resolved chemical compositions of submicron particles in Pittsburgh: Implications for aerosol sources and processes, J. Geophys. Res., 110, D070S079, doi:10.1029/2004JD004649, 2005c. Zhang, Q., Jimenez, J. L., Canagaratna, M. R., Allan, J. D., Coe, H., Ulbrich, I., Alfarra, M. R., Takami, A., Middlebrook, A. M., Sun, Y. L., Dzepina, K., Dunlea, E., Docherty, K., DeCarlo, P. F., Salcedo, D., Onasch, T., Jayne, J. T., Miyoshi, T., Shimono, A., Hatakeyama, S., Takegawa, N., Kondo, Y., Schneider, J., Drewnick, F., Borrmann, S., Weimer, S., Demerjian, K., Williams, P., Bower, K., Bahreini, R., Cottrell, L., Griffin, R. J., Rautianinen, J., Sun, J. Y., Zhang, Y. M., and Worsnop, D. R.: Ubiquity and dominance of oxygenated species in organic aerosols in anthropogenically-influenced nothern hemisphere midlatitudes, Geophys. Res. Lett., 34, L13801, doi:10.1029/2007GL029979, 2007.