ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH GΓΆttingen, Germany 10.5194/acp-10-3847-2010 Temperature effect on physical and chemical properties of secondary organic aerosol from <i>m</i>-xylene photooxidation Qi L. 1 Nakao S. 1 Tang P. 1 Cocker III D. R. 1 Department of Chemical and Environmental Engineering, Bourns College of Engineering, University of California, Riverside, CA 92521, USA and College of Engineering, Center for Environmental Research and Technology (CE-CERT), 1084 Columbia Avenue, Riverside 26 04 2010 10 8 3847 3854 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/10/3847/2010/acp-10-3847-2010.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/10/3847/2010/acp-10-3847-2010.pdf

The chemical and physical differences of secondary organic aerosol (SOA) formed at select isothermal temperatures (278 K, 300 K, and 313 K) are explored with respect to density, particle volatility, particle hygroscopicity, and elemental chemical composition. A transition point in SOA density, volatility, hygroscopicity and elemental composition is observed near 290–292 K as SOA within an environmental chamber is heated from 278 K to 313 K, indicating the presence of a thermally labile compound. No such transition points are observed for SOA produced at 313 K or 300 K and subsequently cooled to 278 K. The SOA formed at the lowest temperatures (278 K) is more than double the SOA formed at 313 K. SOA formed at 278 K is less hydrophilic and oxygenated while more volatile and dense than SOA formed at 300 K or 313 K. The properties of SOA formed at 300 K and 313 K when reduced to 278 K did not match the properties of SOA initially formed at 278 K. This study demonstrates that it is insufficient to utilize the enthalpy of vaporization when predicting SOA temperature dependence.

 References 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(21), 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., Onasch, T. B., 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., Prιvτt, 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. Berndt, T., BΓΆge, O., and Stratmann, F.: Gas-phase ozonolysis of $\alpha $-pinene: gaseous products and particle formation, Atmos. Environ. 37, 3933–3945, 2003. Brechtel F. J. and Kreidenweis S. M.: Predicting particle critical supersaturation from hygroscopic growth measurements in the humidified TDMA. part I: Theory and sensitivity studies, J. Atmos. Sci., 57, 1854–1871, 2000. Carter, W. P. L., Cocker, D. R., Fitz, D. R., Malkina, I. L., Bumiller, K., Sauer, C. G., Pisano, J. T., Bufalino, C., and Song, C.: A new environmental chamber for evaluation of gas-phase chemical mechanisms and secondary aerosol formation, Atmos. Environ., 39, 7768–7788, 2005. Cocker, D. R., Clegg, S. L., Flagan, R. C., and Seinfeld, J. H.: The effect of water on gas-particle partitioning of secondary organic aerosol. Part I: $\alpha $-pinene/ozone system, Atmos. Environ. 35, 6049–6072, 2001a. Cocker, D. R., Flagan, R. C., and Seinfeld, J. H.: State-of-the-art facility for studying atmospheric aerosol chemistry, Environ. Sci. Technol., 35, 2594–2601, 2001b. Cocker, D. R., Mader, B. T., Kalberer, M., Flagan, R. C., and Seinfeld, J. H.: The effect of water on gas-particle partitioning of secondary organic aerosol: II. m-xylene and 1,3,5-trimethylbenzene photooxidation systems, Atmos. Environ., 35, 6073–6085, 2001c. Davidson, C. I., Phalen, R. F., and Solomon, P. A.: Airborne Particulate Matter and Human Health: A Review, Aerosol Sci. Technol., 39, 737–749, 2005. DeCarlo, P. F., Kimmel, J. R., Trimborn, A., Northway, M. J., Jayne, J. T., Aiken, A. C., Gonin, M., Fuhrer, K., Horvath, T., Docherty, K., Worsnop, D. R., and Jimenez, J. L.: Field-Deployable, High-Resolution, Time-of-Flight Aerosol Mass Spectrometer, Anal. Chem., 78, 8281–8289, 2006. Ehara, K., Hagwood, C., and Coakley, K. J.: Novel method to classify aerosol particles according to their mass-to-charge ratio-aerosol particle mass analyzer, J. Aerosol Sci., 27(2), 217–234, 1996. Eldering, A. and Cass, G. R.: Source-oriented model for air pollutant effects on visibility, J. Geophys. Res.-Atmos., 101, 19343–19369, 1996. Griffin, R. J., Cocker, D. R., Flagan, R. C., and Seinfeld, J. H.: Organic aerosol formation from the oxidation of biogenic hydrocarbons, J. Geophys. Res.-Atmos., 104, 3555–3567, 1999. Hildebrandt, L., Donahue, N. M., and Pandis, S. N.: High formation of secondary organic aerosol from the photo-oxidation of toluene, Atmos. Chem. Phys., 9, 2973–2986, 2009. Hoffmann, T., Odum, J. R., Bowman, F., Collins, D., Klockow, D., Flagan, R. C., and Seinfeld, J. H.: Formation of organic aerosols from the oxidation of biogenic hydrocarbons, J. Atmos. Chem., 26, 189–222, 1997. Intergovernmental Panel on Climate Change (IPCC) Fourth Assessment Report: Climate Change 2007. Jimenez, J. L., Jayne, J. T., Shi, Q., Kolb, C. E., Worsnop, D. R., Yourshaw, I., Seinfeld, J. H., Flagan, R. C., Zhang, X., Smith, K. A., Morris, J., and Davidovits, P.: Ambient Aerosol Sampling with an Aerosol Mass Spectrometer, J. Geophys. Res.-Atmos., 108(D7), 8425, doi:10.1029/2001JD001213, 2003. Kalberer, M., Paulsen, D., Sax, M., Steinbacher, M., Dommen, J., PrΓ©vΓ΄t, 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. Malloy, Q. G. J., Nakao, S., Qi, L., Austin, R., Stothers, C., Hagino, H., and Cocker, D. R.: Real-Time Aerosol Density Determination Utilizing a Modified Scanning Mobility Particle SizerAerosol Particle Mass Analyzer System, Aerosol Sci. Technol., 43, 673–678, 2009. 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. 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. Pathak, R. K., Presto, A. A., Lane, T. E., Stanier, C. O., Donahue, N. M., and Pandis, S. N.: Ozonolysis of Ξ±-pinene: parameterization of secondary organic aerosol mass fraction, Atmos. Chem. Phys., 7, 3811–3821, 2007. Pathak, R. K., Stanier, C. O., Donahue, N. M., and Pandis, S. N.: Ozonolysis of $\alpha $-pinene at atmospherically relevant concentrations: temperature dependence of aerosol mass fractions (yields), J. Geophys. Res.-Atmos., 112, D03201, doi:10.1029/2006JD007436, 2007. Philippin, S., Wiedensohler, A., and Stratmann, F.: Measurements of non-volatile fractions of pollution aerosols with an eight-tube volatility tandem differential mobility analyzer (VTDMA-8), J. Aerosol Sci., 35, 185–203, 2004. Pope, C. A. and Dockery, D. W.: Health effects of fine particulate air pollution: lines that connect, J. Air Waste Manage. Assoc., 56, 709–742, 2006. Qi, L., Nakao, S., Malloy, Q., Warren, B., and Cocker, D. R.: Can secondary organic aerosol formed in an atmospheric simulation chamber continuously age?, Atmos. Environ., under review, 2009. 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 Ξ±-pinene, Atmos. Chem. Phys., 8, 2073–2088, 2008. Stanier, C. O., Pathak, R. K., and Pandis, S. N.: Measurements of the volatility of aerosols from alpha-pinene ozonolysis, Environ. Sci. Technol., 41, 2756–2763, 2007. Takekawa, H., Minoura, H., and Yamazaki, S.: Temperature dependence of secondary organic aerosol formation by photo-oxidation of hydrocarbons, Atmos. Environ., 37, 3413–3424, 2003. Turpin, B. J. and Huntzicker, J. J.: Identification of secondary organic aerosol episodes and quantitation of primary and secondary organic aerosol concentrations during SCAQS, Atmos. Environ., 23, 3527–3544, 1995. Warren, B., Austin, R. L., and Cocker, D. R.: Temperature dependence of secondary organic aerosol, Atmos. Environ., 43, 3548–3555, 2009a. Warren, B., Song, C., and Cocker, D. R.: Light intensity and light source influence on secondary organic aerosol formation for the m-xylene/NOx photooxidation system, Environ. Sci. Technol., 42, 5461–5466, 2009b. 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., De-Carlo, 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 Northern Hemisphere midlatitudes, Geophys. Res. Lett., 34, L13801, doi:10.1029/2007GL029979, 2007.