ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-11-893-2011 Modeling secondary organic aerosol formation from isoprene oxidation under dry and humid conditions Couvidat F. 1 Seigneur C. 1 CEREA, Joint Laboratory Ècole des Ponts ParisTech/EDF R&D, Université Paris-Est, 77455 Marne la Vallée, France 31 01 2011 11 2 893 909 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/11/893/2011/acp-11-893-2011.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/11/893/2011/acp-11-893-2011.pdf

A new model for the formation of secondary organic aerosol (SOA) from isoprene was developed. This model uses surrogate molecular species (hydroxy-hydroperoxides, tetrols, methylglyceric acid, organic nitrates) to represent SOA formation. The development of this model used available experimental data on yields and molecular composition of SOA from isoprene and methacrolein oxidation. This model reproduces the amount of particles measured in smog chambers under both low-NO<sub>x</sub> and high-NO<sub>x</sub> conditions. Under low-NO<sub>x</sub> conditions, the model reproduces the transitional formation of hydroxy-hydroperoxides particles, which are photolyzed and lead to SOA mass decrease after reaching a maximum. Under high-NO<sub>x</sub> conditions, particles are assumed to be formed mostly from the photo-oxidation of a PAN-type molecule derived from methacrolein (MPAN). This model successfully reproduces the complex NO<sub>x</sub>-dependence of isoprene oxidation and suggests a possible yield increase under some high-NO<sub>x</sub> conditions. Experimental data correspond to dry conditions (RH < 10%). However, particles formed from isoprene are expected to be highly hydrophilic, and isoprene oxidation products would likely partition between an aqueous phase and the gas phase at high humidity in the atmosphere. The model was extended to take into account the hydrophilic properties of SOA, which are relevant under atmospheric conditions, and investigate the effect of particulate liquid water on SOA formation. An important increase in SOA mass was estimated for humid conditions due to the hydrophilic properties. Experiments under high relative humidity conditions should be conducted to confirm the results of this study, which have implications for SOA modeling.

 References Altieri, K., Seitzinger, S., Carlton, A., Turpin, B., Klein, G., and Marshall, A.: Oligomers formed through in-cloud methylglyoxal reactions: chemical composition, properties, and mechanisms investigated by ultra-high resolution FT-ICR Mass Spectrometry, Atmos. Environ., 42, 1476–1490, \doi10.1016/j.atmosenv.2007.11.015, 2008. Barley, M H. and McFiggans, G.: The critical assessment of vapour pressure estimation methods for use in modelling the formation of atmospheric organic aerosol, Atmos. Chem. Phys., 10, 749–767, \doi10.5194/acp-10-749-2010, 2010. Carlton, A G., Wiedinmyer, C., and Kroll, J H.: A review of Secondary Organic Aerosol (SOA) formation from isoprene, Atmos. Chem. Phys., 9, 4987–5005, \doi10.5194/acp-9-4987-2009, 2009. Carter, W., Cocker~III, D., Fitz, D., Malkina, I., Bumiller, K., Sauer, C., Pisano, J., 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, \doi10.1016/j.atmosenv.2005.08.040, 2005. Chan, A., Chan, M., Surratt, J., Chhabra, P., Loza, C., Crounsoe, J., Yee, L., Flagan, R., Wennberg, P., and Seinfeld, J.: Role of aldehyde chemistry and NOx concentrations in secondary organic aerosol formation, Atmos. Chem. Phys. Discuss., 10, 10219–10269, \doi10.5194/acpd-10-10219-2010, 2010. Claeys, M., Graham, B., Vas, G., Wang, W., Vermeylen, R., Pashynska, V., Cafmeyer, J., Guyon, P., Andreae, M., Araxo, P., and Maenhaut, W.: Formation of secondary organic aerosols through photooxidation of isoprene, Science, 303, 1173–1176, \doi10.1126/science.1092805, 2004. Cocker~III, D., Flagan, R., and Seinfeld, J.: State-of-the-art chamber facility for studying atmospheric aerosol chemistry, Environ. Sci. Technol., 35, 2594–2601, \doi10.1021/es0019169, 2001. Comernolle, S., Ceulemans, K., and Müller, J.-F.: Influence of non-ideality on condensation to aerosol, Atmos. Chem. Phys., 9, 1325–1338, \doi10.5194/acp-9-1325-2009, 2009. Edney, E., Kleindienst, T., Jaoui, M., Lewabdowski, M., Offenberg, J., Wang, W., and Claeys, M.: Formation of 2-methyltetrols and 2-methylglyceric acid in secondary organic aerosol from laboratory irradiated isoprene/\textscNO$_\mathrmX$/SO<sub>2</sub>/air mixtures and their detection in ambient \textscPM2.5 samples collected in the eastern United States, Atmos. Environ., 39, 5281–5289, \doi10.1016/j.atmosenv.2005.05.031, 2005. EPRI: Organic Aerosol Partition Module Documentation, Tech. rep., 1999. Ervens, B., Carlton, A., Turpin, B., Altieri, K., Kreidenweis, S., and Feingold, G.: Secondary organic aerosol yields from cloud-processing of isoprene oxidation products, Geophys. Res. Lett., 35, L02816, \doi10.1029/2007GL031828, 2008. Fredenslund, A., Jones, R., and Prausnitz, J.: Group-contribution estimation of activity-coefficients in nonideal liquid-mixtures, AIChE J., 21, 1086–1099, 1975. Gao, S., Ng, N L., Keywood, M., 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, \doi10.1021/es049125k, 2004. Goliff, W. and Stockwell, W.: The Regional Atmospheric Chemistry Mechanism, version 2, an update, International Conference on Atmospheric Chemical Mechanisms, University of California, Davis, CA, USA, available at: http://airquality.ucdavis.edu/pages/events/2008/acm/Goliff.pdf (last access: August~2010), 2008. Guenther, A., Karl, T., Harley, P., Wiedinmyer, C., Palmer, P., and Geron, C.: Estimates of global terrestrial isoprene emissions using \textscMEGAN (\textscModel of \textscEmissions of \textscGases and \textscAerosols from \textscNature), Atmos. Chem. Phys., 6, 3181–3210, \doi10.5194/acp-6-3181-2006, 2006. Hilal, S., Ayyampalayam, S., and Carreira, L.: Air-liquid partition coefficient for a diverse set of organic compounds: Henry's law constant in water and hexadecane, Environ. Sci. Technol., 42, 9231–9236, \doi10.1021/es8005783, 2008. Jang, M., Czoschke, N M., Lee, S., and Kamens, R.: Heterogeneous atmospheric aerosol production by acid-catalysed particle-phase reactions, Science, 298, 814–817, \doi10.1126/science.1075798, 2002. Jang, M., Czoschke, N M., and Northcross, A L.: Semiempirical model for organic aerosol growth by acid-catalyzed heterogeneous reactions of organic carbonyls, Environ. Sci. Technol., 39, 164–174, \doi10.1021/es048977h, 2005. Kamens, R., Gery, M., Jeffries, H., Jacksons, M., and Cole, E.: Ozone-isoprene reactions: product formation and aerosol potential, Int. J. Chem. Kinet., 14, 955–975, 1982. Kanakidou, M., Seinfeld, J., Pandis, S., Barnes, I., Dentener, F., Facchini, M., Van~Dingenen, R., Ervens, B., Nenes, A., Nielsen, C., Swietlicki, E., Putaud, J., Balkanski, Y., Fuzzi, S., Horth, J., Moortgat, G., Winterhalter, R., Myhre, C., Tsigaridis, K., Vignati, E., Stephanou, E., and Wilson, J.: Organic aerosol and global climate modelling: a review, Atmos. Chem. Phys., 5, 1053–1123, \doi10.5194/acp-5-1053-2005, 2005. Kim, Y., Sartelet, K., and Seigneur, C.: Comparison of two gas-phase chemical kinetic mechanisms of ozone formation over Europe, J. Atmos. Chem., 62, 89–119, \doi10.1007/s10874-009-9142-5, 2009. Kleindienst, T., Lewandowski, M., Offenberg, J., Jaoui, M., and Edney, E.: Ozone-isoprene reactions: Re-examination of the formation of secondary organic aerosol, Geophys. Res. Lett., 34, L01805, \doi10.1029/2006GL027485, 2007. Kleindienst, T., Lewandowski, M., Offenberg, J., Jaoui, M., and Edney, E.: The formation of secondary organic aerosols from the isoprene + \textscOH reaction in the absence of \textscNO$_\mathrmX$, Atmos. Chem. Phys., 9, 6541–6558, \doi10.5194/acp-9-6541-2009, 2009. Kroll, J., Ng, N., Murphy, S., Flagan, R., and Seinfeld, J.: Secondary organic aerosol formation from isoprene photooxidation, Environ. Sci. Technol., 40, 1869–1877, \doi10.1021/es0524301, 2006. Kroll, J H. and Seinfeld, J H.: Chemistry of secondary organic aerosol: Formation and evolution of low-volatility organics in the atmosphere, Atmos. Environ., 42, 3593–3624, \doi10.1016/j.atmosenv.2008.01.003, 2008. Liggio, J., Li, S.-M., and McLaren, R.: Heterogeneous Reactions of Glyoxal on Particulate Matter: Identification of Acetals and Sulfate Esters, Environ. Sci. Technol., 39, 1532–1541, \doi10.1021/es048375y, 2005. Meylan, W. and Howard, P.: Bond contribution method for estimating Henry's law constants, Environ. Toxicol. Chem, 10, 1283–1293, \doi10.1002/etc.5620101007, 1991. Meylan, W. and Howard, P.: SRC's EPI suite, v3.20, Tech. rep., Syracuse Research Corporation, 2000. Ng, N L., Chhabra, P S., Chan, A. W H., Surratt, J D., Kroll, J H., Kwan, A J., McCabe, D C., Wennberg, P O., Sorooshian, A., Murphy, S M., Dalleska, N F., Flagan, R C., and Seinfeld, J H.: Effect of NO<sub>x</sub> level on secondary organic aerosol (SOA) formation from the photooxidation of terpenes, Atmos. Chem. Phys., 7, 5159–5174, \doi10.5194/acp-7-5159-2007, 2007a. Ng, N L., Kroll, J H., Chan, A. W H., Chhabra, P S., Flagan, R C., and Seinfeld, J H.: Secondary organic aerosol formation from m-xylene, toluene, and benzene, Atmos. Chem. Phys., 7, 3909–3922, \doi10.5194/acp-7-3909-2007, 2007b. Ng, N., Kwan, A., Surratt, J., Chan, A., Chhabra, P., Sorooshian, A., Pye, H., Crounse, J., Wennberg, P., Flagan, R., and Seinfeld, J.: Secondary organic aerosol (\textscSOA) formation from reaction of isoprene with nitrate radicals (\textscNO<sub>3</sub>), Atmos. Chem. Phys., 8, 4117–4140, \doi10.5194/acp-8-4117-2008, 2008. Nguyen, T., Bateman, A., Bones, D., Nizkorodov, S., Laskin, J., and Laskin, A.: High-resolution mass spectrometry analysis of secondary organic aerosol generated by ozonolysis of isoprene, Atmos. Environ., 44, 1032–1042, \doi10.1016/j.atmosenv.2009.12.019, 2010. Odum, J., Hoffman, T., Bowman, F., Collins, D., Flagan, R., and Seinfeld, J.: Gas/particle partitioning and secondary organic aerosol yields, Environ. Sci. Technol., 30, 2580–2585, \doi10.1021/es950943+, 1996. Pandis, S., Paulson, S., Seinfeld, J., and Flagan, R.: Aerosol formation in the photooxidation of isoprene and β-pinene, Atmos. Environ., 25, 997–1008, \doi10.1021/es0524301, 1991. Pankow, J.: An absorption model of gas/particle partitioning of organic compounds in the atmosphere, Atmos. Environ., 28A, 185–188, 1994a. Pankow, J.: An absorption model of the gas/aerosol partitioning involved in the formation of secondary organic aerosol, Atmos. Environ., 28A, 189–193, 1994b. Pankow, J. and Asher, W.: \textscSIMPOL.1: a simple group contribution method for predicting vapor pressures and enthalpies of vaporization of multifunctional organic compounds, Atmos. Chem. Phys., 8, 2773–2796, \doi10.5194/acp-8-2773-2008, 2008. Pöschl, U., Von~Kuhlmann, R., Poisson, N., and Crutzen, P.: Development and intercomparison of condensed isoprene oxidation mechanisms for global atmospheric modeling, J. Atmos. Chem., 37, 29–52, \doi10.1023/A:1006391009798, 2000. Pun, B.: Development and initial application of the sesquiversion of \textscMADRID, J. Geophys. Res., 113, D12212, \doi10.1029/2008JD009888, 2008. Pun, B. and Seigneur, C.: Investigative modeling of new pathways for secondary organic aerosol formation, Atmos. Chem. Phys., 7, 2199–2216, \doi10.5194/acp-7-2199-2007, 2007. Pun, B., Griffin, R., Seigneur, C., and Seinfeld, J.: Secondary organic aerosol 2. Thermodynamic model for gas/particle partitioning of molecular constituents, J. Geophys. Res., 107, 4333, \doi10.1029/2001JD000542, 2002. Pun, B., Wu, S.-Y., Seigneur, C., Seinfeld, J., Griffin, R., and Pandis, S.: Uncertainties in Modeling Secondary Organic Aerosols: Three-Dimensional Modeling Studies in Nashville/Western Tennessee, Environ. Sci. Technol., 37, 3647–3661, \doi10.1021/es0341541, 2003. Pun, B., Seigneur, C., and Lohman, K.: Modeling secondary organic aerosol formation via multiphase partitioning with molecular data, Environ. Sci. Technol., 40, 4722–4731, \doi10.1021/es0522736, 2006. Raventos-Duran, T., Camredon, M., Valorso, R., and Aumont, B.: Structure-activity relationships to estimate the effective Henry's law coefficients of organics of atmospheric interest, Atmos. Chem. Phys. Discuss., 10, 4617–4647, \doi10.5194/acpd-10-4617-2010, 2010. Rollins, W., Kiender-Scharr, A., Fry, J., Brauers, T., Brown, S., Dorn, H.-P., Dubé, W., Fuchs, H., Mensah, A., Mentel, T., Tillmann, R., Wegener, R., Wooldridge, P., and Cohen, R.: Isoprene oxidation by nitrate radical: alkyl nitrate and secondary organic aerosol yields, Atmos. Chem. Phys., 9, 6685–6703, \doi10.5194/acp-9-6685-2009, 2009. Ruppert, L. and Becker, K.: A product study of the OH radical-initiated oxidation of isoprene: formation of C$_5$-unsaturated diols, Atmos. Environ., 34, 1529–1542, \doi10.1016/S1352-2310(99)00408-2, 2000. Surratt, J., Murphy, S., Kroll, J., Ng, N., Hildebrandt, L., Sorooshian, A., Szmigielski, R., Vermeylen, R., Maenhaut, W., Claeys, M., Flagan, R., and Seinfeld, J.: Chemical composition of secondary organic aerosol formed from the photooxidation of isoprene, J. Phys. Chem. A, 110, 9665–9690, \doi10.1021/jp061734m, 2006. Surratt, J., Chan, A., Eddingsaas, N., Chan, M., Loza, C., Kwan, A., Hersery, S., Flagan, R., Wennberg, P., and Seinfeld, J.: Reactive intermediates revealed in secondary organic aerosol formation from isoprene, Proc. Natl. Acad. Sci., 107, 6640–6645, \doi10.1073/pnas.0911114107, 2010. Suzuki, T., Ohtaguchi, K., and Koide, K.: Application of principal components analysis to calculate Henry's constant from molecular structure, Computers Chem., 16, 41–52, 1992. Verwer, J., Spee, E., Bloom, J., and Hundsdorfer, W.: A second-order rosenbrock method applied to photochemical dispersion problems, SIAM J. Sci. Comput., 20, 1456–1480, \doi10.1137/S1064827597326651, 1999. Volkamer, R., Ziemann, P J., and Molina, M J.: Secondary Organic Aerosol Formation from Acetylene (C<sub>2</sub>H<sub>2</sub>): seed effect on SOA yields due to organic photochemistry in the aerosol aqueous phase, Atmos. Chem. Phys., 9, 1907–1928, \doi10.5194/acp-9-1907-2009, 2009. Yu, S., Bhave, P., Dennis, R., and Marthur, R.: Seasonal and regional variations of primary and secondary organic aerosols over the Continental United States: Semi-empirical estimates and model evaluation, Environ. Sci. Technol., 41, 4690–4697, \doi10.1021/es061535g, 2007. Zhang, Q., Jimenez, J., Canagaratna, M., Allan, J., Coe, H., Ulbrich, I., Alfarra, M., Takami, A., Middlebrook, A., Sun, Y., Dzepina, K., Dunlea, E., Docherty, K., De-Carlo, P., Salcedo, D., Onasch, T., Jayne, J., 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., Rautiainen, J., Sun, J., Zhang, Y., and Worsnop, D.: Ubiquity and dominance of oxygenated species in organic aerosols in anthropogenically-influence Northern Hemisphere mildlatitudes, Geophys. Res. Lett., 34, \doi10.1029/2007GL029979, 2007a. Zhang, Y., Huang, J.-P., Henze, D., and Seinfeld, J.: Role of isoprene in secondary organic aerosol formation on a regional case, J. Geophys. Res., 112, D20 207, \doi10.1029/2007JD008675, 2007b. Zuend, A., Marcolli, C., Peter, T., and Seinfeld, J H.: Computation of liquid-liquid equilibria and phase stabilities: implications for RH-dependent gas/particle partitioning of organic-inorganic aerosols, Atmos. Chem. Phys., 10, 7795–7820, \doidoi:10.5194/acpd-10-12497-2010, 2010.