Abstract
A laboratory study was carried out to investigate the secondary organic aerosol products from photooxidation of the aromatic hydrocarbon toluene. The laboratory experiments consisted of irradiating toluene/propylene/NOx/air mixtures in a smog chamber operated inthe dynamic mode and collecting submicron secondary organic aerosol samples through a sampling train that consisted of an XAD denuder and a ZefluorTM filter. Oxidation products in the filter extracts were treated using O-(2,3,4,5,6,-pentafluorobenzyl)-hydroxylamine (PFBHA) to derivatize carbonyl groups followed by treatment with N,O-Bis(trimethylsilyl)-acetamide (BSTFA) to derivatize OH groups. The derivatized products were detected with a positive chemical ionization (CI) gas chromatography ion trap mass spectroscopy (GC-ITMS) system. The results of the GC-ITMS analyses were consistent with the previous studies that demonstrated the formation of multi-functional oxygenates. Denuder results showed that many of these same compounds were present in the gas, as well as, the particle phase. Moreover, evidence was found for a series of multifunctional acids produced as higher order oxidation products of the toluene/NOx system. Products having nearly the same mass spectrumwere also found in the ambient environment using identical analytical techniques. These products having multiple acid and alcoholic-OH moieties have substantially lower volatility than previously reported SOA products of the toluene photooxidation and might serve as an indicator for aromatic oxidation in the ambient atmosphere.
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Bierbach, A., Barnes, I., Becker, K. H., and Wiesen, E., 1994: Atmospheric chemistry of unsaturated carbonyls: Butenedial, 4-oxo-2-pentenal, 3-hexene-2,5-dione, maleic anhydride, 3H-furan-2-one, and 5-methyl-3H-furan-2-one, Environ. Sci. Technol. 28, 715-729.
Calvert, J. G., Atkinson, R., Becker, K. H., Kamens, R. M., Seinfeld, J. H., Wallington, T. J., and Yarwood, G., 2002: The Mechanism of Atmospheric Oxidation of Aromatic Hydrocarbons, Oxford University Press, Inc. New York, NY.
Edney, E. O., Driscoll, D. J., Speer, R. E., Weathers, W. S., Kleindienst, T. E., Li, W., and Smith, D. F., 2000: Impact of aerosol liquid water on secondary aerosol yields of irradiated toluene/propylene/NOx /(NH4 ) 2SO4/air mixtures, Atmos. Environ. 34, 3907-3919.
Edney, E. O., Driscoll, D. J., Weathers, W. S., Kleindienst, T. E., Conver, T. S., McIver, C. D., and Li, W., 2001: Formation of polyketones in irradiated toluene/propylene/NOx /air mixtures, Aero. Sci. Technol. 35, 998-1008.
Edney, E. O, Kleindienst, T. E., Conver, T. S. McIver, C. D., Corse, E.W., and Weathers, W. S., 2003: Polar organic oxygenates in PM2.5 at a southeastern site in the United States, Atmos. Environ. 37, 3947-3965.
Forstner, H. J. L., Flagan, R. C., and Seinfeld, J. H., 1997: Secondary organic aerosol from the photooxidation of aromatic hydrocarbons: Molecular composition, Environ. Sci. Technol. 31, 1345-1358.
Gundel, L. A., Lee, V. C., Mahanama, K. R. R., Stevens, R. K., and Daisey, J. M., 1995: Direct determination of the phase distribution of semi-volatile polycyclic aromatic hydrocarbons using annular denuders, Atmos. Environ. 29, 1719-1733.
Holes, A., Eusebi, A., Grosjean, D., and Allen, D. T., 1997: FTIR analysis of aerosol formed in the photooxidation of 1,3,5-trimethylbenzene, Aerosol Sci. Technol. 26, 516-526.
Izumi, K. and Fukuyama, T., 1990: Photochemical aerosol formation from aromatic hydrocarbons in the presence of NOx, Atmos. Environ. 24A, 1433-1490.
Jang, M. and Kamens, R. M., 2001: Characterization of secondary aerosol from the photooxidation of toluene in the presence of NOx and 1-propene, Environ. Sci. Technol. 35, 3626-3639.
Kleindienst, T. E., Smith, D. F., Li, W., Edney, E. O., Driscoll, D. J., Speer, R. E., and Weathers, W. S., 1999, Secondary organic aerosol formation from the oxidation of aromatic hydrocarbons in the presence of dry submicron ammonium sulfate aerosol, Atmos. Environ. 33, 3669-3681.
Kleindienst, T. E., Corse, E. W., Li. W., McIver, C. D., Conver, T. S., Edney, E. O., Driscoll, D. J., Speer, R. E., Weathers, W. S., and Tejada, S. B., 2002: Secondary organic aerosol formation from the irradiation of simulated automobile exhaust, J. Air Waste Manage. Assoc. 52, 259-272.
Kleindienst, T. E., McIver, C. D., Corse, E. W., Edney, E. O., and Speer, R. E., 2003: Organic compounds measured in PM2.5 during NEOPS. Presented at the 83rd American Meteorological Society Annual Meeting. Long Beach, CA, February 9-13, 2003. Paper 6.5.
Odum, J. R., Hoffmann, T., Bowman, F., Collins, D., Flagan, R. C., and Seinfeld, J. H., 1996: Gas/particle partitioning and secondary organic aerosol yields, Environ. Sci. Technol. 30, 2580-2585.
Odum, J. R., Jungkamp, T. P. W., Griffin, R. J., Forstner, H. J. L., Flagan, R. C., and Seinfeld, J. H., 1997: Aromatics, reformulated gasoline, and atmospheric organic aerosol formation, Environ. Sci. Technol. 31, 1890-1897.
Smith, D. F., McIver, C. D., and Kleindienst, T. E., 1998: Primary product distribution from the reaction of hydroxyl radicals with toluene at ppb NOx mixing ratios, J. Atmos. Chem. 30, 209-228.
Smith, D. F., Kleindienst, T. E., and McIver, C. D., 1999: Primary product distributions from the reaction of OH with m?, p?xylene, and 1,2,4-and 1,3,5-trimethylbenzene, J. Atmos. Chem. 34, 339-364.
Tobias, H. J. and Ziemann, P. J., 2000: Thermal desorption mass spectrometric analysis of organic aerosol formed from the reactions of 1-tetradecene and ozone in the presence of alcohols and carboxylic acids, Environ. Sci. Technol. 34, 2105-2115.
Wang, S.-C., Paulson, S. E., Grosjean, D., Flagan, R. C., and Seinfeld, J. H., 1992: Aerosol formation and growth in atmospheric organic/NOx systems-I. Outdoor smog chamber studies of C7-and C8-hydrocarbons, Atmos. Environ. 26A, 403-420.
Yu, J., Flagan, R. C., Seinfeld, J. H., 1998: Identification of products containing -COOH, -OH and C=O in atmospheric oxidation of hydrocarbons, Environ. Sci. Technol. 32, 2357-2370.
Yu, J., Jeffries, H. E., and Sexton, K. G., 1997: Atmospheric photooxidation of alkylbenzenes I. Carbonyl product analyses, Atmos. Environ. 31, 2261-2280.
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Kleindienst, T.E., Conver, T.S., McIver, C.D. et al. Determination of Secondary Organic Aerosol Products from the Photooxidation of Toluene and their Implications in Ambient PM2.5 . Journal of Atmospheric Chemistry 47, 79–100 (2004). https://doi.org/10.1023/B:JOCH.0000012305.94498.28
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DOI: https://doi.org/10.1023/B:JOCH.0000012305.94498.28