References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-12-8711-2012

The formation of SOA and chemical tracer compounds from the photooxidation of naphthalene and its methyl analogs in the presence and absence of nitrogen oxides

Kleindienst

T. E.

¹ Jaoui

² Lewandowski

¹ Offenberg

J. H.

¹ Docherty

K. S.

National Exposure Research Laboratory, U.S. Environmental Protection Agency, Research Triangle Park, North Carolina 27711, USA

Alion Science and Technology, P.O. Box 12313, Research Triangle Park, North Carolina 27709, USA

27 09 2012

12 18 8711 8726

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Laboratory smog chamber experiments have been carried out to investigate secondary organic aerosol (SOA) formation from the photooxidation of naphthalene and its methyl analogs, 1- and 2-methylnaphthalene (1-MN and 2-MN, respectively). Laboratory smog chamber irradiations were conducted in a flow mode to ensure adequate collection of the aerosol at reasonably low reactant concentrations and in the presence and absence of nitrogen oxides. Phthalic acid and methyl analogs were identified following BSTFA derivatization of the aerosol extract. These compounds were examined to determine whether they could serve as reasonable molecular tracers to estimate the contributions of these precursors to ambient PM2.5. Measurements were also made to determine aerosol parameters from secondary organic aerosol from naphthalene, 1-MN, and 2-MN. A mass fraction approach was used to establish factors which could be applied to phthalic acid concentrations in ambient aerosols, assuming a negligible contribution from primary sources. Phthalic anhydride uptake (and hydrolysis) was tested and found to represent a moderate filter artifact in filter measurements with and without in-line denuders. This study provided the opportunity to examine differences using authentic standards for phthalic acid compared to surrogate standards. While the mass fraction based on a surrogate compounds was somewhat lower, the differences are largely unimportant. For naphthalene, mass fractions of 0.0199 (recommended for ambient samples) and 0.0206 were determined in the presence and absence of nitrogen oxides, respectively, based on phthalic acid standards. The mass fractions determined from the laboratory data were applied to ambient samples where phthalic acid was found and expressed "as naphthalene" since phthalic acid was found to be produced in the particle phase from other methylnaphthalenes. The mass fraction values were applied to samples taken during the 2005 SOAR Study in Riverside, CA and 2010 CalNex Study in Pasadena. In both studies an undetermined isomer of methylphthalic acid was detected in addition to phthalic acid. Laboratory experiment retention times and mass spectra suggest that the major precursor for this compound is 2-MN. For the CalNex Study, SOC values for the 2-ring precursor PAHs (as naphthalene) were found to range from below the detection limit to 20 ngC m−3 which with the laboratory mass fraction data suggests an upper limit of approximately 1 μg m−3 for SOA due to 2-ring PAHs. Temporal data over the course of the one-month CalNex study suggest that primary sources of phthalic acid were probably negligible during this study period. However, the values must still be considered upper limits given a potential hydrolysis reaction or uptake of phthalic anhydride (subsequently hydrolyzed) onto the collection media.

References 1

Biermann, H. W., Mac Leod, H, Atkinson, R., Winer, A. M., and Pitts Jr., J. N.: Kinetics of the gas-phase reactions of the OH radical-initiated reactions of naphthalene and the C$_1$- and C2-alkylnaphthalenes, Environ. Sci. Technol., 41, 2803–2810, 2007.

Birch, M. E. and Cary, R. A.: Elemental carbon-based method for monitoring occupational exposures to particulate diesel exhaust, Aerosol Sci. Technol., 25, 221–241, 1996.

California Air Resources Board: Ambient Concentrations of Polycyclic Aromatic Hydrocarbons (PAHs) at Selected Locations in California, Research Note No. 89-1, 1989.

Chan, A. W. H., Kautzman, K. E., Chhabra, P. S., Surratt, J. D., Chan, M. N., Crounse, J. D., Kürten, A., Wennberg, P. O., Flagan, R. C., and Seinfeld, J. H.: Secondary organic aerosol formation from photooxidation of naphthalene and alkylnaphthalenes: implications for oxidation of intermediate volatility organic compounds (IVOCs), Atmos. Chem. Phys., 9, 3049–3060, http://dx.doi.org/10.5194/acp-9-3049-2009doi:10.5194/acp-9-3049-2009, 2009.

Claeys, M., Szmigielski, R., Kourtchev, I., Van der Veken, P., Vermeylen, R., Maenhaut, W., Jaoui, M., Kleindienst, T. E., Lewandowski, M., Offenberg, J. H., and Edney, E. O.: Hydroxydicarboxylic acids: Markers for secondary organic aerosol from the photooxidation of $\alpha $-pinene, Environ. Sci. Technol., 41, 6828–6834, 2007.

deGouw, 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.

deGouw, J. A., Brock, C. A., Atlas, E. L., Bates, T. S., Fehsenfeld, F. C., Goldan, P. D., Holloway, J. S., Kuster, W. C., Lerner, B. M., Matthew, B. M., Middlebrook, A. M., Onasch, T. B., Peltier, R. E., Quinn, P. K., Senff, C. J., Stohl, A., Sullivan, A. P., Trainer, M., Warneke, C., Weber, R. J., and Williams, E. J.: Sources of particulate matter in the northeastern United States in summer: 1. Direct emissions and secondary formation of organic matter in urban plumes, J. Geophys. Res., 113, D08301, http://dx.doi.org/10.1029/2007JD009243doi:10.1029/2007JD009243, 2008.

Docherty, K. S., Stone, E. A., Ulbrich, I. M., DeCarlo, P. F., Snyder, D. C., Schauer, J. J., Peltier, R. E., Weber, R. J., Murphy, S. M., Seinfeld, J. H., Grover, B. D., Eatough, D. J., and Jimenez, J. L.: Apportionment of Primary and secondary organic aerosols in Southern California during the 2005 Study of Organic Aerosols in Riverside (SOAR-1), Environ. Sci. Technol., 42, 7655–7662, 2008.

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/NO$_\textx$/SO2/air mixtures and their detection in ambient PM$_2.5$ samples collected in the eastern U.S., Atmos. Environ., 39, 5281–5289, 2005.

Fine, P. M., Chakrabarti, B., Krudysz, M., Schauer, J. J., and Sioutas, C.: Diurnal variations of individual organic compound constituents of ultrafine and accumulation mode particulate matter in the Los Angeles basin, Environ. Sci. Technol., 38, 1296–1304, 2004.

Fraser, M. P., Cass, G. R., and Simoneit, B. R. T.: Air quality model evaluation data for organics. 6. C3-C$_24$ organic acids, Environ. Sci. Technol., 37, 446–453, 2003.

Gundel, L. A., Lee, V. C., Mahanama, K. R. R., Stevens, R. K., and Daisey, J. M.: Direct determination of the phase distribution of semi-volatile polycyclic aromatic hydrocarbons using annular denuders, Atmos. Environ., 29, 1719–1733, 1995.

Hallquist, M., Wenger, J. C., Baltensperger, U., Rudich, Y., Simpson, D., Claeys, M., Dommen, J., Donahue, N. M., George, C., Goldstein, A. H., Hamilton, J. F., Herrmann, H., Hoffmann, T., Iinuma, Y., Jang, M., Jenkin, M. E., Jimenez, J. L., Kiendler-Scharr, A., Maenhaut, W., McFiggans, G., Mentel, Th. F., Monod, A., Prévôt, A. S. H., Seinfeld, J. H., Surratt, J. D., Szmigielski, R., and Wildt, J.: The formation, properties and impact of secondary organic aerosol: current and emerging issues, Atmos. Chem. Phys., 9, 5155–5236, http://dx.doi.org/10.5194/acp-9-5155-2009doi:10.5194/acp-9-5155-2009, 2009.

Heald, C. L., Jacobs, 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, Geophy. Res. Lett., 32, L18809, http://dx.doi.org/10.1029/2005GL023831doi:10.1029/2005GL023831, 2005.

Hu, D., Bian, Q., Li, T. W. Y., Lau, A. K. H., and Yu, J. Z., Contributions of isoprene, monoterpenes, $\beta $-caryophyllene, and toluene to secondary organic aerosols in Hong Kong during the Summer of 2006, J. Geophys. Res., 113, D22206, http://dx.doi.org/10.1029/2008JD010437doi:10.1029/2008JD010437, 2008.

Jaoui, M., Kleindienst, T. E., Lewandowski, and Edney, E. O.: Identification and quantification of aerosol polar oxygenated compounds bearing carboxylic or hydroxyl groups. 1. Method development, Anal. Chem., 76, 4765–4778, 2004.

Jaoui, M., Kleindienst, T. E., Lewandowski, M., Offenberg, J. H., and Edney, E. O.: Identification and quantification of aerosol polar oxygenated compounds bearing carboxylic or hydroxyl groups. 2. Organic tracer compounds from monoterpenes, Environ. Sci. Technol., 39, 5661–5673, 2005.

Jaoui, M., Lewandowski, M., Kleindienst, T. E., Offenberg, J. H., and Edney, E. O.: beta-caryophyllinic acid: An atmospheric tracer for beta-caryophyllene secondary organic aerosol, Geophys. Res. Lett., 34, L05816, http://dx.doi.org/10.1029/2006GL028827doi:10.1029/2006GL028827, 2007.

Kautzman, K. E., Surratt, J. D., Chan, M. N., Chan, A. W. H., Hersey, S. P., Chhabra, P. S., Dalleska, N. F., Wennberg, P. O., Flagan, R. C., and Seinfeld, J. H.: Chemical composition of gas- and aerosol-phase products from the photooxidation of naphthalene, J. Phys. Chem. A, 114, 913–934, 2010.

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 implication in PM$_2.5$, J. Atmos. Chem., 47, 79–100, 2004.

Kleindienst, T. E., Jaoui, M., Lewandowski, M., Offenberg, J. H., Lewis, C. W., Bhave, P. V., and Edney, E. O.: Estimates of the contributions of biogenic and anthropogenic hydrocarbons to secondary organic aerosol at a southeastern US location, Atmos. Environ., 41, 8288–8300, 2007.

Kleindienst, T. E., Lewandowski, M., Offenberg, J. H., Jaoui, M., and Edney, E. O.: The formation of secondary organic aerosol from the isoprene + OH reaction in the absence of NOx, Atmos. Chem. Phys., 9, 6541–6558, http://dx.doi.org/10.5194/acp-9-6541-2009doi:10.5194/acp-9-6541-2009, 2009.

Kleindienst, T. E., Lewandowski, M., Offenberg, J. H., Edney, E. O., Jaoui, M., Zheng, M., Ding, X., and Edgerton, E. S.: Contribution of primary and secondary sources to organic aerosol and PM2.5 at SEARCH Network Sites, J. Air Waste Manage. Assoc., 60, 1388–1399, 2010a.

Kleindienst, T. E., Lewandowski, M., Offenberg, J. H., Jaoui, M., and Docherty, K. S.: Investigations of tracers from naphthalene and its methyl analogs. Presented at the annual conference of the American Association for Aerosol Research Annual Conference, Portland, OR, 24–28 October, 2010b.

Lewandowski, M., Jaoui, M., Offenberg, J. H., Kleindienst, T. E., Edney, E. O., Sheesley, R. J., and Schauer, J. J.: Primary and secondary contribution to ambient PM in the Midwestern United States, Environ. Sci. Technol., 42, 3303–3309, 2008.

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

Nishino, N., Arey, J., and Atkinson, R.: Formation of nitro products from the gas-phase OH radical-initiated reactions of toluene, naphthalene, and biphenyl: Effect of NO2 concentration, Environ. Sci. Technol., 42, 9203–9209, 2008.

Nishino, N., Arey, J., and Atkinson, R.: Yields of glyoxal and ring-cleavage co-products from the OH radical initiated reactions of naphthalene and selected alkylnaphthalenes, Environ. Sci. Technol., 43, 8554–8560, 2009a.

Nishino, N., Arey, J., and Atkinson, R.: Formation and reactions of 2-formylcinnamaldehyde in the OH radical-initiated reaction of naphthalene, Environ. Sci. Technol. 43, 1349–1353, 2009b.

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 aerosol, Geophys. Res. Lett., 33, L03816, http://dx.doi.org/10.1029/2005GL024623doi:10.1029/2005GL024623, 2006.

Phousongphouang, P. T. and Arey, J.: Rate constants for the gas-phase reactions of a series of alkylnaphthalenes with the OH radical, Environ. Sci. Technol., 36, 1947–1952, 2002.

Pio, C., Alves, C., and Duarte, A.: Organic components of aerosols in a forested area of central Greece, Atmos. Environ., 35, 389–401, 2001.

Pun, B. K., Wu, S.-Y., Seigneur, C., Seinfeld, J. H., Griffin, R. J., and Pandis, S. N.: Uncertainties in modeling secondary organic aerosols: Three-dimensional modeling studies in Nashville/Western Tennessee, Environ. Sci. Technol., 37, 3747–3761, 2003.

Reisen, F. and Arey, J.: Atmospheric Reactions Influence Seasonal PAH and Nitro-PAH Concentrations in the Los Angeles Basin, Environ. Sci. Technol., 39, 64–73, 2005.

Robinson, A. L., Donahue, N. M., Shrivastava, M. K., Weitkamp, E. A., Sage, A. M., Grieshop, A. P., Lane, T. E., Pierce, J. R., and Pandis, S. N.: Rethinking organic aerosols: Semivolatile emissions and photochemical aging, Science, 315, 1259–1262, 2007.

Sasaki, J., Aschmann, S. M., Kwok, E. S. C., Atkinson, R., and Arey, J.: Products of the gas-phase OH and NO3 radical-initiated reactions of naphthalene, Environ. Sci. Technol., 31, 3173–3179, 1997.

Schauer, J. J., Rogge, W. F., Hildemann, L. M., Mazurek, M. A., and Cass, G. R.: Source apportionment of airborne particulate matter using organic compounds as tracers, Atmos. Environ., 30, 3837–3855, 1996.

Schauer, J. J., Kleeman, M. J., Cass, G. R., and Simoneit, B. R. T.: Measurement of emissions from air pollution sources. 2. C$_1$ through C$_30$ organic compounds from medium duty diesel trucks, Environ. Sci. Technol., 33, 1578–1587, 1999.

Schauer, J. J., Fraser, M. P., Cass, G. R., and Simoneit, B. R. T., Source reconciliation of atmospheric gas-phase and particle phase pollutants during a severe photochemical smog episode, Environ. Sci. Technol., 36, 3806–3814, 2002.

Shakya, K. M. and Griffin, R. J., Secondary organic aerosol from the photooxidation of polycyclic aromatic hydrocarbons, Environ. Sci. Technol., 44, 8134–8139, 2010.

Stone, E. A., Zhou, J., Snyder, D. C., Rutter, A. P., Mieritz, M., and Schauer, J. J.: A comparison of summertime secondary organic aerosol source contributions at contrasting urban locations, Environ. Sci. Technol., 43, 3448–3454, 2009.

Szmigielski, R., Surratt, J. D., Yadian Gomez-Gonzalez, Y., Van der Veken, P., Kourtchev, I., Vermeylen, R., Blockhuys, F., Jaoui, M., Kleindienst, T. E., Lewandowski, M., Offenberg, E. O., Seinfeld, J. H., Maenhaut, W., and Claeys, M.: 3-Methyl-1,2,3-butanetricarboxylic acid: An atmospheric tracer for terpene secondary organic aerosol, J. Geophys. Res., 34, L24811, http://dx.doi.org/10.1029/2007GL031338doi:10.1029/2007GL031338, 2007.

Volkamer, R., San Martini, F., Molina, L. T., Salcedo, D., Jimenez, J. L., and Molina, M. J.: A missing sink for gas-phase glyoxal in Mexico City: Formation of secondary organic aerosol, Geophys. Res. Lett., 34, L19807, http://dx.doi.org/10.1029/2007GL030752doi:10.1029/2007GL030752, 2007.

Wang, L., Atkinson, R., and Arey, J.: Dicarbonyl products of the OH radical-initiated reactions of naphthalene and the C$_1$- and C2-alkylnaphthalenes, Environ. Sci. Technol., 41, 2803–2810, 2007.

Washenfelder, R. A., Young, C. J., Brown, S. S., Angevine, W. M., Etlas, E. L., Blake, D. R., Bon, D. M., Cubison, M. J., de Gouw, J. A., Dusanter, S., Flynn, J., Gilman, J. B., Graus, M., Griffith, S., Grossberg, N., Hayes, P. L., Jimenez, J. L., Kuster, W. C., Lefer, B. L., Pollack, I. B., Ryerson, T. B., Stark, H., Stevens, P. S., and Trainer, M. K.: The glyoxal budget and its contribution to organic aerosol for Los Angeles, California, during CalNex 2010, J. Geophys. Res., 116, D00V02, http://dx.doi.org/10.1029/2011JD016314doi:10.1029/2011JD016314, 2011.