References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-7-5343-2007

Modeling secondary organic aerosol formation through cloud processing of organic compounds

Chen

¹ Griffin

R. J.

¹ ² Grini

³ Tulet

⁴

Institute for the Study of Earth, Oceans, and Space, University of New Hampshire, Durham, NH, USA

Department of Earth Sciences, University of New Hampshire, Durham, NH, USA

Department of Geoscience, University of Oslo, Pb 1022 Blindern, 0315, Oslo, Norway

CNRM/GMEI Météo France, Toulouse, France

17 10 2007

7 20 5343 5355

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/7/5343/2007/acp-7-5343-2007.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/7/5343/2007/acp-7-5343-2007.pdf

Interest in the potential formation of secondary organic aerosol (SOA) through reactions of organic compounds in condensed aqueous phases is growing. In this study, the potential formation of SOA from irreversible aqueous-phase reactions of organic species in clouds was investigated. A new proposed aqueous-phase chemistry mechanism (AqChem) is coupled with the existing gas-phase Caltech Atmospheric Chemistry Mechanism (CACM) and the Model to Predict the Multiphase Partitioning of Organics (MPMPO) that simulate SOA formation. AqChem treats irreversible organic reactions that lead mainly to the formation of carboxylic acids, which are usually less volatile than the corresponding aldehydic compounds. Zero-dimensional model simulations were performed for tropospheric conditions with clouds present for three consecutive hours per day. Zero-dimensional model simulations show that 48-h average SOA formation is increased by 27% for a rural scenario with strong monoterpene emissions and 7% for an urban scenario with strong emissions of aromatic compounds, respectively, when irreversible organic reactions in clouds are considered. AqChem was also incorporated into the Community Multiscale Air Quality Model (CMAQ) version 4.4 with CACM/MPMPO and applied to a previously studied photochemical episode (3–4 August 2004) focusing on the eastern United States. The CMAQ study indicates that the maximum contribution of SOA formation from irreversible reactions of organics in clouds is 0.28 μg m−3 for 24-h average concentrations and 0.60 μg m−3 for one-hour average concentrations at certain locations. On average, domain-wide surface SOA predictions for the episode are increased by 9% when irreversible, in-cloud processing of organics is considered. Because aldehydes of carbon number greater than four are assumed to convert fully to the corresponding carboxylic acids upon reaction with OH in cloud droplets and this assumption may overestimate carboxylic acid formation from this reaction route, the present study provides an upper bound estimate of SOA formation via this pathway.

References 1

Altieri, K. E., Carlton, A. G., Lim, H. J., Turpin, B. J., and Seitzinger, S. P.: Evidence for oligomer formation in clouds: Reactions of isoprene oxidation products, Environ. Sci. Technol., 40, 4956–4960, 2006.

Aumont, B., Madronich, S., Bey, I., and Tyndall, G. S.: Contribution of secondary VOC to the composition of aqueous atmospheric particles; a modeling approach, J. Atmos. Chem., 35, 59–75, 2000.

Blando, J. D., Porcja, R. J., Li, T. H., Bowman, D., Lioy, P. J., and Turpin, B. J.: Secondary formation and the Smoky Mountain organic aerosol: An examination of aerosol polarity and functional group composition during SEAVS, Environ. Sci. Technol., 32, 604–613, 1998.

Blando, J. D. and Turpin, B. J.: Secondary organic aerosol formation in cloud and fog droplets: a literature evaluation of plausibility, Atmos. Environ., 34, 1623–1632, 2000.

Byun, D. W. and Ching, J. K. S.: Science algorithms of the EPA Models-3 Community Multiscale Air Quality (CMAQ) modeling system, Report EPA/600/R-99/030, Office of Research and Development, United States Environmental Protection Agency, Washington, DC, 1999.

Carlton, A. G., Turpin, B. J., Lim, H. J., Altieri, K. E., and Seitzinger, S.: Link between isoprene and secondary organic aerosol (SOA): Pyruvic acid oxidation yields low volatility organic acids in clouds, Geophys. Res. Lett., 33, L06822, doi:10.1029/2005GL025374, 2006.

Charlson, R. J., Schwartz, S. E., Hales, J. M., Cess, R. D., Coakley Jr., J. A., Hansen, J. E., and Hofmann D. J.: Climate forcing by anthropogenic aerosols, Science, 255, 423–430, 1992.

Chen, J. and Griffin, R. J.: Modeling secondary organic aerosol formation from oxidation of $\alpha $-pinene, $\beta $-pinene, and d-limonene, Atmos. Environ., 39, 7731–7744, 2005.

Chen, J., Mao, H., Talbot, R. W., and Griffin, R. J.: Application of the CACM and MPMPO modules using the CMAQ model for the eastern United States, J. Geophys. Res., 111, D23S25, doi:10.1029/2006JD007603, 2006.

Claeys, M., Wang, W., Ion, A. C., Kourtchev, I., Gelencser, A., and Maenhaut, W.: Formation of secondary organic aerosols from isoprene and its gas-phase oxidation products through reaction with hydrogen peroxide, Atmos. Environ., 38, 4093–4098, 2004.

Daescu, D., Sandu, A., and Carmichael, G. R.: Direct and adjoint sensitivity analysis of chemical kinetic systems with KPP: II Numerical validations and applications, Atmos. Environ., 37, 5097–5114, 2003.

Damian, V., Sandu, A., Damian, M., Potra, F., and Carmichael, G. R.: The kinetic preprocessor KPP – A software environment for solving chemical kinetics, Comput. Chem. Eng., 26, 1567–1579, 2002.

Decesari, S., Facchini, M. C., Fuzzi, S., and Tagliavini, E.: Characterization of water-soluble organic compounds in atmospheric aerosol: A new approach, J. Geophys. Res., 105, 1481–1489, 2000.

Dutot, A., Rude, J., and Aumont, B.: Neural network method to estimate the aqueous rate constants for the OH reactions with organic compounds, Atmos. Environ., 37, 269–276, 2003.

Ervens, B., George, C., Williams, J. E., et al.: CAPRAM 2.4 (MODAC mechanism): An extended and condensed tropospheric aqueous phase mechanism and its application, J. Geophys. Res., 108, 4426, doi:10.1029/2002JD002202, 2003.

Ervens, B., Feingold, G., Frost, G. J., and Kreidenweis, S. M.: A modeling study of aqueous production of dicarboxylic acids: 1. Chemical pathways and speciated organic mass production, J. Geophys. Res., 109, D15205, doi:10.1029/2003JD004387, 2004.

Gelencser, A. and Varga, Z.: Evaluation of the atmospheric significance of multiphase reactions in atmospheric secondary organic aerosol formation, Atmos. Chem. Phys., 5, 2823–2831, 2005.

Griffin, R. J., Cocker III, D. R., Flagan, R. C., and Seinfeld, J. H.: Organic aerosol formation from the oxidation of biogenic hydrocarbons, J. Geophys. Res., 104, 3555–3567, 1999.

Griffin, R. J., Dabdub, D., and Seinfeld, J. H.: Secondary organic aerosol, 1. Atmospheric chemical mechanism for production of molecular constituents, J. Geophys. Res., 107, 4332, doi:10.1029/2001JD000541, 2002.

Griffin, R. J., Dabdub, D., and Seinfeld, J. H.: Development and initial evaluation of a dynamic species-resolved model for gas-phase chemistry and size-resolved gas/particle partitioning associated with secondary organic aerosol formation, J. Geophys. Res., D05304, doi:10.1029/2004JD005219, 2005.

Griffin, R. J., Nguyen, K., Dabdub, D., and Seinfeld, J. H.: A coupled hydrophobic-hydrophilic model for predicting secondary organic aerosol formation, J. Atmos. Chem., 44, 171–190, 2003.

Hastings, W. P., Koehler, C. A., Bailey, E. L., and DeHaan, D. O.: Secondary organic aerosol formation by glyoxal hydration and oligomer formation: Humidity effects and equilibrium shifts during analysis, Environ. Sci. Technol., 39, 8728–8735, 2005.

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., L18809, doi:10.1029/2005GL023831, 2005.

Heald, C. L., Jacob, D. J., Turquety, S., et al.: Concentrations and sources of organic carbon aerosols in the free troposphere over North America, J. Geophys. Res., 111, D23S47, doi:1029/2006JD007705, 2006.

Herrmann, H., Tilgner, A., Barzaghi, P., Majdik, Z., Gligorovski, S., Poulain, L., and Monod, A.: Towards a more detailed description of tropospheric aqueous phase organic chemistry: CAPRAM 3.0, Atmos. Environ., 39, 4351–4363, 2005.

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.

Jones, A., Roberts, L., and Slingo, A.: A climate model study of indirect radiative forcing by anthropogenic sulphate aerosols, Nature, 370, 450–453, 1994.

Kalberer, M., Paulsen, D., Sax, M., et al.: Identification of polymers as major components of atmospheric organic aerosols, Science, 303, 1659–1662, 2004.

Kanakidou, M., Seinfeld, J. H., Pandis, S. N., et al.: Organic aerosol and global climate modeling: a review, Atmos. Chem. Phys., 5, 1053–1123, 2005.

Kawamura, K. and Ikushima, K.: Seasonal changes in the distribution of dicarboxylic acids in the urban atmosphere, Environ. Sci. Technol., 27, 2227–2235, 1993.

Lim, H. J., Carlton, A. G., and Turpin, B. J.: Isoprene forms secondary organic aerosol through cloud processing: model simulations, Environ. Sci. Technol., 39, 4441–4446, 2005.

Loeffler, K. W., Koehler, C. A., Paul, N. M., and DeHaan, D. O.: Oligomer formation in evaporating aqueous glyoxal and methyl glyoxal solutions, Environ. Sci. Technol., 40, 6318–6323, 2006.

Malm, W. C.: Atmospheric haze: Its sources and effects on visibility in rural areas of the continental United States, Environ. Monit. Assess., 12, 203–225, 1989.

Mao, H., Talbot, R., Troop, D., Johnson, R., Businger, S., and Thompson, A. M.: Smart balloon observations over the North Atlantic: O3 data analysis and modeling, J. Geophys. Res., 111, D23S56, doi:10.1029/2005JD006507, 2006.

Martin, L. R. and Good, T. W.: Catalyzed oxidation of sulfur dioxide in solution: the iron-manganese synergism, Atmos. Environ., 25A, 2395–2399, 1991.

Murphy, D. M., Thomson, D. S., and Mahoney, M. J.: In situ measurements of organics, meteoritic material, mercury, and other elements in aerosols at 5 to 19 kilometers, Science, 282, 1664–1669, 1998.

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.

Pandis, S. N. and Seinfeld, J. H.: Sensitivity analysis of a chemical mechanism for aqueous-phase atmospheric chemistry, J. Geophys. Res., 94, 1105–1126, 1989.

Pankow, J. F.: An absorption model of the gas/aerosol partitioning involved in the formation of secondary organic aerosol, Atmos. Environ., 28, 189–193, 1994.

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.

Pun, B. K., Griffin, R. J., Seigneur, C., and Seinfeld, J. H.: Secondary organic aerosol: II: Thermodynamic model for gas/particle partitioning of molecular constituents, J. Geophys. Res., 107, 4333, doi:10.1029/2001JD000542, 2002.

Sandu, A., Daescu, D., and Carmichael, G. R.: Direct and adjoint sensitivity analysis of chemical kinetic systems with KPP: I – Theory and software tools, Atmos. Environ., 37, 5083–5096, 2003.

Sandu, A., Verwer, J. G., Blom, J. G., Spee, E. J., Carmichael, G. R., and Potra, F. A.: Benchmarking stiff ODE solvers for atmospheric chemistry problems II: Rosenbrock methods, Atmos. Environ., 31, 3459–3472, 1997.

Schwartz, S. E.: Mass-transport considerations pertinent to aqueous-phase reactions of gases in liquid-water clouds, in: Chemistry of Multiphase Atmospheric Systems, edited by: Jaeschke, W., Springer, New York, 1986.

Sorooshian, A., Varutbangkul, V., Brechtel, F. J., et al.: Oxalic acid in clear and cloudy atmospheres: Analysis of data from International Consortium for Atmospheric Research on Transport and Transformation 2004, J. Geophys. Res., 111, D23S45, doi:10.1029/2005JD006880, 2006.

Sorooshian, A., Lu, M. L., Brechtel, F. J., Jonsson, H., Feingold, G., Flagan, R. C., and Seinfeld, J. H.: On the source of organic acid aerosol layers above clouds, Environ. Sci. Technol., 41, 4647–4654, 2007.

Tulet, P., Grini, A., Griffin, R. J., and Petitcol, S.: ORILAM-SOA: A computationally efficient model for predicting secondary organic aerosols in 3D atmospheric models, J. Geophys. Res., D23208, doi:10.1029/2006JD007152, 2006.

Turpin, B. J., Saxena, P., and Andrews, E.: Measuring and simulating particulate organics in the atmosphere: Problems and prospects, Atmos. Environ., 34, 2983–3013, 2000.

Warneck, P.: The relative importance of various pathways for the oxidation of sulfur dioxide and nitrogen dioxide in sunlit continental fair weather clouds, Phys. Chem. Chem. Phys., 1, 5471–5483, 1999.

Warneck, P.: In-cloud chemistry opens pathway to the formation of oxalic acid in the marine atmosphere, Atmos. Environ., 37, 2423–2427, 2003.

Yao, X., Fang, M., and Chan, C. K.: Size distributions and formation of dicarboxylic acids in atmospheric particles, Atmos. Environ., 36, 2099–2107, 2002.

Zaveri, R.: Development and evaluation of a comprehensive tropospheric chemistry model for regional and global application, dissertation, Virginia Polytechnic Institute and State University, Blacksburg, Virginia, 1997.