References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-7-3909-2007

Secondary organic aerosol formation from m-xylene, toluene, and benzene

N. L.

¹ Kroll

J. H.

¹ ² Chan

A. W. H.

¹ Chhabra

P. S.

¹ Flagan

R. C.

¹ Seinfeld

J. H.

Departments of Chemical Engineering and Environmental Science and Engineering, California Institute of Technology, Pasadena, CA 91125, USA

now at: Aerodyne Research, Inc. 45 Manning Road, Billerica, MA 01821, USA

24 07 2007

7 14 3909 3922

This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

This article is available from http://www.atmos-chem-phys.net/7/3909/2007/acp-7-3909-2007.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/7/3909/2007/acp-7-3909-2007.pdf

Secondary organic aerosol (SOA) formation from the photooxidation of m-xylene, toluene, and benzene is investigated in the Caltech environmental chambers. Experiments are performed under two limiting NOx conditions; under high-NOx conditions the peroxy radicals (RO2) react only with NO, while under low-NOx conditions they react only with HO2. For all three aromatics studied (m-xylene, toluene, and benzene), the SOA yields (defined as the ratio of the mass of organic aerosol formed to the mass of parent hydrocarbon reacted) under low-NOx conditions substantially exceed those under high-NOx conditions, suggesting the importance of peroxy radical chemistry in SOA formation. Under low-NOx conditions, the SOA yields for m-xylene, toluene, and benzene are constant (36%, 30%, and 37%, respectively), indicating that the SOA formed is effectively nonvolatile under the range of Mo(>10 μg m−3) studied. Under high-NOx conditions, aerosol growth occurs essentially immediately, even when NO concentration is high. The SOA yield curves exhibit behavior similar to that observed by Odum et al. (1996, 1997a, b), although the values are somewhat higher than in the earlier study. The yields measured under high-NOx conditions are higher than previous measurements, suggesting a "rate effect" in SOA formation, in which SOA yields are higher when the oxidation rate is faster. Experiments carried out in the presence of acidic seed aerosol reveal no change of SOA yields from the aromatics as compared with those using neutral seed aerosol.

References 1

Andino, J. M., Smith, J. N., Flagan, R. C., Goddard III, W. A., and Seinfeld, J. H.: Mechanism of atmospheric photooxidation of aromatics: A theoretical study, J. Phys. Chem., 100, 10 967–10 980, 1996.

Atkinson, R., Aschmann, S. M., Arey, J., and Carter, W. P. L.: Formation of ring-retaining products from the OH radical-initiated reactions of benzene and toluene, Int. J. Chem. Kinet., 21, 801–827, 1989.

Atkinson, R. and Aschmann, S. M.: Products of the gas-phase reactions of aromatic hydrocarbons: effect of NO2 concentration, Int. J. Chem. Kinet., 26, 929–944, 1994.

Bahreini, R., Keywood, M. D., Ng, N. L., Varutbangkul, V., Gao, S., Flagan, R. C., and Seinfeld, J. H.: Measurements of secondary organic aerosol (SOA) from oxidation of cycloalkenes, terpenes, and m-xylene using an Aerodyne aerosol mass spectrometer, Environ. Sci. Technol., 39, 5674–5688, 2005.

Calvert, J. G., Atkinson, R., Becker, K. H., Kamens, R. M., Seinfeld, J. H., Wallington, T. J., and Yarwoord, G.: The Mechanisms of Atmospheric Oxidation of Aromatic Hydrocarbons, Oxford University Press, New York, 556pp., 2002.

Chan, A. W. H., Kroll, J. H., Ng, N. L., and Seinfeld, J. H.: Kinetic modeling of secondary organic aerosol formation: effects of particle- and gas-phase reactions of semivolatile products, Atmos. Chem. Phys. Discuss., 7, 7051–7085, 2007.

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.

Cocker III, D. R., Flagan, R. C., and Seinfeld, J. H.: State-of-the-art chamber facility for studying atmospheric aerosol chemistry, Environ. Sci. Technol., 35, 2594–2601. 2001.

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., 110, D16305, doi:10.1029/2004JD005623, 2005.

Edney, E. O., Kleindienst, T. E., Jaoui, M., Lewandowski, M., Offenberg, J. H., Wang, W., and Claeys, M.: Formation of 2-methyl tetrols and 2-methylglyceric acid in secondary organic aerosol from laboratory irradiated isoprene/NOx/SO2/air mixtures and their detection in ambient PM$_2.5$ samples collected in the eastern United States, Atmos. Environ., 39, 5281–5289, 2005.

Fan, J. and Zhang, R.: Atmospheric oxidation mechanism of $p$-xylene: A density function theory study, J. Phys. Chem. A, 110, 7728–7737, 2006.

Forstner, H. J. L., Flagan, R. C., and Seinfeld, J. H.: Secondary organic aerosol from the photooxidation of aromatic hydrocarbons: Molecular composition, Environ. Sci. Technol., 31, 1345–1358, 1997.

Gao, S., Keywood, M. D., Ng, N. L., Surratt, J. D., Varutbangkul, V., Bahreini, R., Flagan, R. C., and Seinfeld, J. H.: Low-molecule weight and oligomeric components in secondary organic aerosol from the ozonolysis of cycloalkenes and α-pinene, J. Phys. Chem., A, 108, 10 147–10 164, 2004a.

Gao, S., Ng, N. L., Keywood, M. D., Varutbangkul, V., Bahreini, R., Nenes, A., He, J., 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, 2004b.

Hatakeyama, S., Izumi, K., Fukuyama, T., Akimoto, H., Washida, N.: Reactions of OH with α-pinene and β-pinene in air: Estimates of global CO production from the atmospheric oxidation of terpenes, J. Geophys. Res., 96(D1), 947–958, 1991.

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.

Heald, C. L., Jacob, D.J., Turquety, S., Hudman, R.C., Weber, R. J., Sullivan, A.P., Peltier, R. E., Atlas, E. L., de Gouw, J.A., Warneke, C., Holloway, J. S., Neuman, J. A., F. Flocke, M., and Seinfeld, J. H.: Concentration and sources of organic carbon aerosols in the free troposphere over North America, J. Geophys. Res., 111(D23), D23S47, doi:10.1029/2006JD007705, 2006.

Hurley, M. D., Sokolov, O., Wallington, T. J., Takekawa, H., Karasawa, M., Klotz, B., Barnes, I., and Becker, K. H.: Organic aerosol formation during the atmospheric degradation of toluene, Environ. Sci. Technol., 35, 1358–1366, 2001.

Iinuma, Y., Böge, O., Gnauk, T., and Herrmann, H.: Aerosol-chamber study of the pinene/O3 reaction: Influence of particle acidity on aerosol yields and products, Atmos. Environ., 38, 761–773, 2004.

Izumi, K. and Fukuyama, T.: Photochemical aerosol formation from aromatic hydrocarbons in the presence of NOx, Atmos. Environ., 24A, 1433–1441, 1990.

Jang, M. and Kamens, R. M.: Characterization of secondary organic aerosol from the photooxidation of toluene in the presence of NOx and 1-propene, Environ. Sci. Technol., 35, 3626–3639, 2001.

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.

Johnson, D., Jenkin, M. E., Wirtz, K., and Martín-Reviejo, M.: Simulating the formation of secondary organic aerosol from the photooxidation of toluene, Environ. Chem., 1, 150–165, 2004.

Johnson, D., Jenkin, M. E., Wirtz, K., and Martín-Reviejo, M.: Simulating the formation of secondary organic aerosol from the photooxidation of aromatic hydrocarbons, Environ. Chem., 2, 35–48, 2005.

Kalberer, M., Paulsen, S., 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.

Keywood, M. D., Varutbangkul, V., Bahreini, R., Flagan, R. C., and Seinfeld, J. H.: Secondary organic aerosol formation from the ozonolysis of cycloalkenes and related compounds, Environ. Sci. Technol., 38, 4157–4164, 2004.

Kleindienst, T. E., Conver, T. S., McIver, C. D., and Edney, E. O.: Determination of secondary organic aerosol products from the photooxidation of toluene and their implications in ambient PM$_2.5$, J. Atmos. Chem., 47, 79–100, 2004.

Koch, R., Knispel, R., Elend, M., Siese, M., and Zetzsch, C.: Consecutive reactions of aromatic-OH adducts with NO, NO2, and O2: Benzene, toluene, $m$-and $p$-xylene, hexamethylbenzene, phenol, $m$-cresol, and aniline, Atmos. Chem. Phys. Discuss., 6, 7623–7656, 2006.

Kroll, J. H., Ng, N. L., Murphy, S. M., Flagan, R. C., and Seinfeld, J. H.: Secondary organic aerosol formation from isoprene photooxidation, Environ. Sci. Technol., 40, 1869–1877, 2006.

Kroll, J., 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.

Lay, T. H., Bozzelli, J. W., and Seinfeld, J. H.: Atmospheric photochemical oxidation of benzene: Benzene+OH and the benzene-OH adduct, J. Phys. Chem., 100, 6543–6554, 1996.

Martin-Revíejo, M. and Wirtz, K.: Is benzene a precursor for secondary organic aerosol? Environ. Sci. Technol., 39, 1045–1054, 2005.

Ng, N. L., Kroll, J. H., Keywood, M. D., Bahreini, R., Varutbangkul, V., Flagan, R. C., Seinfeld, J. H., Lee, A., and Goldstein, A. H.: Contribution of first- versus second-generation products to secondary organic aerosols formed in the oxidation of biogenic hydrocarbons, Environ. Sci. Technol., 40, 2283–2297, 2006.

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.

Odum, J. R., Jungkamp, T. P. W., Griffin, R. J., Flagan, R. C., and Seinfeld, J. H.: The atmospheric aerosol-forming potential of whole gasoline vapor, Science, 276, 96–99, 1997a.

Odum, J. R., Jungkamp, T. P. W., Griffin, R. J., Forstner, H. J. L., Flagan, R. C., and Seinfeld, J. H.: Aromatics, reformulated gasoline and atmospheric organic aerosol formation, Environ. Sci. Technol., 31, 1890–1897, 1997b.

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:10.1029/2005GL024623, 2006.

Presto, A. A., Huff Hartz, K. E., and Donahue, N. M.: Secondary organic aerosol production from ozonolysis: 2. Effect of NOx concentration, Environ. Sci. Technol., 39, 7046–7054, 2005.

Presto, A. A. and Donahue, N. M.: Investigation of α-pinene+ozone secondary organic aerosol formation at low total aerosol mass, Environ. Sci. Technol., 40, 3536–3543, 2006.

Seinfeld, J. H. and Pandis, S. N.: Atmospheric Chemistry and Physics: From Air Pollution to Climate Change, Wiley, New Jersey, 1203pp., 2006.

Song, C., Na, K., and Cocker III, D. R.: Impact of the hydrocarbon to NOx ratio on secondary organic aerosol formation, Environ. Sci. Technol, 39, 3143–3149, 2005.

Stroud, C. A., Makar, P. A., Michelangeli, D. V., Mozurkewich, M., Hastie, D. R., Barbu, A., and Humble, J.: Simulating organic aerosol formation during photooxidation of toluene/NOx mixtures: Comparing the equilibrium and kinetic assumption, Environ. Sci. Technol., 38, 1471–1479, 2004.

Suh, I., Zhang, R., Molina, L. T., and Molina, M. J.: Oxidation mechanism of aromatic peroxy and bicyclic radicals from OH-toluene reactions, J. Am. Chem. Soc., 125, 12 655–12 665, 2003.

Surratt, J. D., Kroll, J. H., Kleindienst, T. E., Edney, E. O., Claeys, M., Sorooshian, A., Ng, N. L., Offenberg, J. H., Lewandowski, M., Jaoui, M., Flagan, R. C., and Seinfeld, J. H.: Evidence for organosulfates in secondary organic aerosol, Environ. Sci. Technol., 41, 517–527, 2007.

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.

Tsigaridis, K. and Kanakidou, M.: Global modelling of secondary organic aerosols in the troposphere: A sensitivity study, Atmos. Chem. Phys., 3, 1849–1869, 2003.

Volkamer, R., Klotz, B., Barnes, I., Imamura, T., Wirtz, K., Washida, N., Becker, K. H., and Platt, U.: OH-initiated oxidation of benzene, Part I, phenol formation under atmospheric conditions, Phys. Chem. Chem. Phys., 4, 1589–1610, 2002.

Volkamer, R., Jimenez, J. L., San Martini, F., Dzepina, K., Zhang, Q., Salcedo, D., Molina, L. T., Worsnop, D. R., 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.

Zhang, S., Shaw, M., Seinfeld, J. H., and Flagan, R. C.: Photochemical aerosol formation from α-pinene and β-pinene, J. Geophys. Res., 97, 20 717–20 729, 1992.

Zhao, J., Zhang, R., Misawa, K., and Shibuya K.: Experimental product study of the OH-initiated oxidation of $m$-xylene, J. Photochem Photobio A., 199–207, 2005.