Atmospheric Chemistry and Physics
www.atmos-chem-phys.net
1680-7316
1680-7324
7
14
2007
10.5194/acp-7-3811-2007
http://www.atmos-chem-phys.net/7/3811/2007/
http://www.atmos-chem-phys.net/7/3811/2007/acp-7-3811-2007.html
http://www.atmos-chem-phys.net/7/3811/2007/acp-7-3811-2007.pdf
3811
3821
2007-07-24
Ozonolysis of α-pinene: parameterization of secondary organic aerosol mass fraction
R. K. Pathak
A. A. Presto
T. E. Lane
C. O. Stanier
N. M. Donahue
S. N. Pandis
spyros@andrew.cmu.edu
Department of Chemical Engineering, Carnegie Mellon University, Pittsburgh, USA
Chemical & Biochemical Engineering and IIHR Hydroscience and Engineering Department, Univ. of Iowa, Iowa City, USA
Department of Chemical Engineering, University of Patras, Patra, Greece
Existing parameterizations tend to underpredict the α-pinene aerosol
mass fraction (AMF) or yield by a factor of 2–5 at low organic aerosol
concentrations (<5 µg m<sup>−3</sup>). A wide range of smog chamber results
obtained at various conditions (low/high NO<sub>x</sub>, presence/absence of UV
radiation, dry/humid conditions, and temperatures ranging from 15–40°C)
collected by various research teams during the last decade are used to
derive new parameterizations of the SOA formation from α-pinene
ozonolysis. Parameterizations are developed by fitting experimental data to
a basis set of saturation concentrations (from 10<sup>−2</sup> to 10<sup>4</sup> µg m<sup>−3</sup>)
using an absorptive equilibrium partitioning model. Separate
parameterizations for α-pinene SOA mass fractions are developed for:
1) Low NO<sub>x</sub>, dark, and dry conditions, 2) Low NO<sub>x</sub>, UV, and dry conditions, 3)
Low NO<sub>x</sub>, dark, and high RH conditions, 4) High NO<sub>x</sub>, dark, and dry
conditions, 5) High NO<sub>x</sub>, UV, and dry conditions. According to the proposed
parameterizations the α-pinene SOA mass fractions in an atmosphere
with 5 µg m<sup>−3</sup> of organic aerosol range from 0.032 to 0.1 for
reacted α-pinene concentrations in the 1 ppt to 5 ppb range.
Andreae, M. O. and Crutzen, P. J.: Atmospheric aerosols: biogeochemical sources and role in atmospheric chemistry, Science, 276, 1052–1058, 1997.
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, 2001.
Czoschke, N. M. and Jang, M.: Acidity effects on the formation of a-pinene SOA in the presence of inorganic seed, Atmos. Environ, 40, 4370–4380, 2006.
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.
Donahue, N. M., Robinson, A. L., Stanier, C. O., Pandis, S. N.: Coupled partitioning, dilution, and chemical aging of semivolatile organics, Environ. Sci. Technol., 40, 2635–2643, 2006.
Fick, J., Pommer, L., Nilsson, C., and Andersson, B.: Effect of OH radicals, relative humidity, and time on the composition of the products formed in the ozonolysis of alpha-pinene, Atmos. Environ., 37, 4087–4096, 2003.
Gao, S., Ng, N. L., Keywood, M., Varutbankgkul, 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, 2004.
Griffin, R. J., Cocker, D. R., and Seinfeld, J. H.: Estimate of global atmospheric organic aerosol from oxidation of biogenic hydrocarbons, Geophys. Res. Lett., 26, 2721–2724, 1999a.
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., 104, 3555–3567, 1999b.
Guenther A., Hewitt, C. N., Erickson, D., Fall, R., Geron, C., Graedel, T., Harley, P., Klinger, L., Lerdau, M., Mckay, W.A., Pierce, T., Scholes, B., Steinbrecher, R., Tallamraju, R., Taylor, J., and Zimmerman, P.: A global-model of natural volatile organic-compound emissions, J. Geophys. Res., 100, 8873–8892, 1995.
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 is missing from current models, Geophys. Res. Lett., 32, L18809, doi:10.1029/2005GL023831, 2005.
Hoffmann, T., Odum, J. R., Bowman, F. A., Collins, D., Klockow, D., Flagan, R. C., and Seinfeld, J. H.: Formation of organic aerosol from the oxidation of biogenic hydrocarbons, J. Atmos. Chem., 26, 189–222, 1997.
Hoppel, W, Fitzgerald, J., and Frick, G.: Particle formation and growth from ozonolysis of alpha-pinene, J. Geophys. Res., 106, 27 603–27 618, 2001.
Iinuma Y., Boge, O., Gnauk, T., and Hermann, H.: Aerosol-chamber study of the $\alpha $-pinene/O<sub>3</sub> reaction: influence of particle acidity on aerosol yields and products, Atmos. Environ., 38, 761–773, 2004.
Jang, M. and Kamens, R. M.: A thermodynamic approach for modeling partitioning of semivolatile organic compounds on atmospheric particulate matter: Humidity effects, Environ. Sci. Technol., 32, 1237–1243, 1998.
Koo, B. Y., Ansari, A. S., and Pandis, S. N.: Integrated approaches to modeling the organic and inorganic atmospheric aerosol components, Atmos. Environ., 37, 4757–4768, 2003.
Lee, A., Goldstein, A. H., Keywood, M. D., Gao, S., Varutbangkul, V., Bahreini, R., Ng, N. L., Flagan, R. C., and Seinfeld, J. H.: Gas-phase products and secondary organic aerosol yields from the ozonolysis of ten different terpenes, J. Geophys. Res., 111, D07302, doi:10.1029/2005JD006437, 2006.
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.
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.
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.
Pankow, J. F., Seinfeld, J. H., and Asher, W. E.: Modeling the formation of secondary organic aerosol. 1. Application of theoretical principles to measurements obtained in the alpha-pinene/, beta- pinene/, sabinene/, Delta(3)-carene/, and cyclohexene/ozone systems, Environ. Sci. Technol., 35, 1164–1172, 2001.
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., 112, D03201, doi:10.1029/2006JD007436, 2007.
Presto, A. A., Huff-Hartz, K. E., and Donahue, N. M.: Secondary organic aerosol production from terpene ozonolysis: 1. Effect of UV radiation, Environ. Sci. Technol., 39, 7036–7045, 2005a.
Presto, A. A., Huff-Hartz, K. E., and Donahue, N. M.: Secondary organic aerosol production from terpene ozonolysis: 2. Effect of NO<sub>x</sub> concentration, Environ. Sci. Technol., 39, 7046–7054, 2005b.
Presto, A. A. and Donahue, N. M.: Investigation of $\alpha $-pinene + ozone secondary organic aerosol formation at low total aerosol mass, Environ. Sci. Technol., 40, 3536–3543, 2006.
Pun, B. K., Griffin, R. J., Seigneur, C., and Seinfeld, J. H.: Secondary organic aerosol – 2. Thermodynamic model for gas/particle partitioning of molecular constituents, J. Geophys. Res., 107, 4333, doi:2001D000542, 2002.
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, 3647–3661, 2003.
Saathoff, H., Linke, C., Naumann, K. H., Wagner, R., Weingartner, E., Schurath, U.: Temperature dependence of the yield of secondary organic aerosol from the ozonolysis of $\alpha $-pinene and limonene, Abstracts of European Aerosol Conference, S151–S152, 2004.
Seinfeld, J. H., Erdakos, G. B., and Asher, W. E.: Modeling the formation of secondary organic aerosol (SOA). 2. The predicted effects of relative humidity on aerosol formation in the alpha-pinene-, beta-pinene-, sabinene-, Delta(3)-Carene-, and cyclohexene-ozone systems, Environ. Sci. Technol., 35, 1806–1817, 2001.
Seinfeld, J. H. and Pankow, J. F.: Organic atmospheric particulate material, Ann. Rev. Phys. Chem., 54, 121–140, 2003.
Stanier, C. O., Pathak, R. K., and Pandis, S. N.: Measurements of the volatility of aerosols from $\alpha $-pinene ozonolysis, Environ. Sci. Tech., 41, 2756–2763, 2007.
Strader, R., Gurciullo, C., Pandis, S. N., Kumar N., and Lurmann, F. W.: Final Report STI-997510-1822, Coordinating Research Council, Alpharetta, GA, 1998, NTIS PB99-128738, 1999a.
Strader, R., Lurmann, F., and Pandis, S. N.: Evaluation of secondary organic aerosol formation in winter, Atmos. Environ., 33, 4849–4863, 1999b.
Takegawa, N., Miyakawa, T., Kondo, Y., Blake, D. R., Kanaya, Y., Koike, M., Fukuda, 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.
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.
Tsigaridis, K. and Kanakidou, M.: Global modeling of secondary organic aerosol in the troposphere: a sensitivity analysis, Atmos. Chem. Phys., 3, 1849–1869, 2003.
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.
Winterhalter, R., Van Dingenen, R., Larsen, B. R., Jensen, N. R., and Hjorth, J.: LC-MS analysis of aerosol particles from the oxidation of $\alpha $-pinene by ozone and OH-radicals, Atmos. Chem. Phys. Discuss., 3, 1–39, 2003.
Yu, J., Cocker, D. R., Griffin, R. J., Flagan, R. C., and Seinfeld J. H.: Gas-phase ozone oxidation of monoterpenes: Gaseous and particulate products, J. Atmos. Chem., 34, 207–258, 1999.
Zhang, J., Huff-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<sub>x</sub>, J. Phys. Chem. A., 110, 11 053–11 063, 2006.