Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 9 3 2009 10.5194/acp-9-771-2009 http://www.atmos-chem-phys.net/9/771/2009/ http://www.atmos-chem-phys.net/9/771/2009/acp-9-771-2009.html http://www.atmos-chem-phys.net/9/771/2009/acp-9-771-2009.pdf 771 782 2009-02-02 Loading-dependent elemental composition of α-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), Univ. 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: Pacific Northwest National Laboratory, Atmospheric Sciences and Global Change Division, Richland, WA 99352, 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 >140 μg/m³ by adjusting the concentration of reacted α-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 (CO₂⁺) signal intensity exceeded that of <i>m/z</i> 43 (predominantly C₂H₃O⁺), suggesting more oxygenated organic material at lower loadings. The composition varied more for lower loadings (0.5 to 15 μg/m³) compared to higher loadings (15 to >140 μg/m³). The high-resolution mass spectra showed that from >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/m³) employing products having empirical formulas of 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., >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. % vor jede Referenz 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. % vor jede Referenz Aiken, A. C., DeCarlo, P. F., Kroll, J. H., Worsnop, D. R., Huffman, J. A., Cocherty, 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. % vor jede Referenz 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. % vor jede Referenz 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. % vor jede Referenz 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. % vor jede Referenz 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. % vor jede Referenz 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. % vor jede Referenz Bowman, F. M. and Karamalegos, A. M.: Estimated effects of composition on secondary organic aerosol mass concentrations, Environ. Sci. Technol., 36, 2701–2707, 2002. % vor jede Referenz 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. % vor jede Referenz Chung, S. H. and Seinfeld, J. H.: Global distribution and climate forcing of carbonaceous aerosols, J. Geophys. Res., 107, 4407, doi:10.1029/2001JD001397, 2002. % vor jede Referenz 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. Tech., 38, 1185–1205, 2004. % vor jede Referenz 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. % vor jede Referenz 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. % vor jede Referenz 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. % vor jede Referenz 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. % vor jede Referenz 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, 2004. % vor jede Referenz Grieshop, A. P., Donahue, N. M., and Robinson, A. L.: Is the gas-particle partitioning in alpha-pinene secondary organic aerosol reversible?, Geophys. Res. Lett., 34, L14810, doi:10.1029/2007GL029987, 2007. % vor jede Referenz Hallquist, M., Wangberg, I., and Ljungstrom, 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. % vor jede Referenz 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. % vor jede Referenz Jang, M. and Kamens, R. M.: Newly characterized products and composition of secondary aerosols from the reaction of α-pinene with ozone, Atmos. Environ., 33, 459–474, 1999. % vor jede Referenz 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. Tech., 33, 49–70, 2000. % vor jede Referenz 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. % vor jede Referenz 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, 10.1029/2001JD001213, 2003. % vor jede Referenz 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. % vor jede Referenz 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. % vor jede Referenz 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. % vor jede Referenz 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, doi:10.1029/2007GL030390, 2007. % vor jede Referenz 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. % vor jede Referenz 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. Tech., 41, 1002–1010, 2007. % vor jede Referenz Lanz, V. A., Alfarra, M. R., Baltensperger, U., Buchmann, B., Hueglin, C., and Prévôt, A. S. H.: Source apportionment of submicron organic aerosols at an urban site by factor analytical modelling of aerosol mass spectra, Atmos. Chem. Phys., 7, 1503–1522, 2007. % vor jede Referenz 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. % vor jede Referenz Marcolli, C., Canagaratna, M. R., Worsnop, D. R., Bahreini, R., de Gouw, J. A., Warneke, C., Goldan, P. D., Kuster, W. C., Williams, E. J., Lerner, B. M., Roberts, J. M., Meagher, J. F., Fehsenfeld, F. C., Marchewka, M., 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. % vor jede Referenz Pang, Y., Turpin, B. J., and Gundel, L. A.: On the importance of organic oxygen for understanding organic aerosol particles, Aerosol Sci. Tech., 40, 128–133, 2006. % vor jede Referenz Pankow, J. F.: An absorption-model of gas-particle partitioning of organic-compounds in the atmosphere, Atmos. Environ., 28, 185–188, 1994a. % vor jede Referenz 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. % vor jede Referenz 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. % vor jede Referenz 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. % vor jede Referenz 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. % vor jede Referenz 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. Tech., 37, 728–734, 2003. % vor jede Referenz Seinfeld, J. H. and Pankow, J. F.: Organic atmospheric particulate material, Annu. Rev. Phys. Chem., 54, 121–140, 2003. % vor jede Referenz 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. % vor jede Referenz 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 α-pinene, Geophys. Res. Lett., 37, L20803, doi:10.1029/2007GL030720, 2007. % vor jede Referenz Takegawa, N., Miyakawa, T., Kawamura, K., and Kondo, Y.: Contribution of selected dicarboxylic and ω-oxycarboxylic acids in ambient aerosol to the m/z 44 signal of an Aerodyne aerosol mass spectrometer, Aerosol Sci. Tech., 41, 418–437, 2007. % vor jede Referenz 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, doi:10.1029/2006GL025815, 2006. % vor jede Referenz 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. % vor jede Referenz Turpin, B. J. and Lim, H.-J.: Species contributions to PM2.5 mass concentrations: Revisiting common assumptions for estimating organic mass, Aerosol Sci. Tech., 35, 602–610, 2001. % vor jede Referenz 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. % vor jede Referenz 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. % vor jede Referenz White, W. H. and Roberts, P. T.: On the nature and origins of visibility reducing species in the Los Angeles basin, Atmos. Environ., 11, 803–812, 1977. % vor jede Referenz Yu, J., Cocker III, D. R. , Griffin, R. J, Flagan, R. C., and Seinfeld, J. H.: Gas-phase ozone oxidation of monterpenes: Gaseous and particulate products, J. Atmos. Chem., 34, 207–258, 1999. % vor jede Referenz 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, 11053–11063, 2006. % vor jede Referenz 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. % vor jede Referenz 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. % vor jede Referenz 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. % vor jede Referenz 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.