ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-10-11261-2010 Global modeling of organic aerosol: the importance of reactive nitrogen (NO<sub>x</sub> and NO<sub>3</sub>) Pye H. O. T. 1 3 Chan A. W. H. 1 4 Barkley M. P. 2 5 Seinfeld J. H. 1 Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California, USA School of GeoSciences, University of Edinburgh, Edinburgh, Scotland, UK now at: Atmospheric Modeling and Analysis Division, National Exposure Research Laboratory, US Environmental Protection Agency, Research Triangle Park, North Carolina, USA now at: Department of Environmental Science, Policy and Management, University of California, Berkeley, California, USA now at: EOS Group, Department of Physics and Astronomy, University of Leicester, UK 30 11 2010 10 22 11261 11276 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/10/11261/2010/acp-10-11261-2010.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/10/11261/2010/acp-10-11261-2010.pdf

Reactive nitrogen compounds, specifically NO<sub>x</sub> and NO<sub>3</sub>, likely influence global organic aerosol levels. To assess these interactions, GEOS-Chem, a chemical transport model, is updated to include improved biogenic emissions (following MEGAN v2.1/2.04), a new organic aerosol tracer lumping scheme, aerosol from nitrate radical (NO<sub>3</sub>) oxidation of isoprene, and NO<sub>x</sub>-dependent monoterpene and sesquiterpene aerosol yields. As a result of significant nighttime terpene emissions, fast reaction of monoterpenes with the nitrate radical, and relatively high aerosol yields from NO<sub>3</sub> oxidation, biogenic hydrocarbon-NO<sub>3</sub> reactions are expected to be a major contributor to surface level aerosol concentrations in anthropogenically influenced areas such as the United States. By including aerosol from nitrate radical oxidation in GEOS-Chem, terpene (monoterpene + sesquiterpene) aerosol approximately doubles and isoprene aerosol is enhanced by 30 to 40% in the Southeast United States. In terms of the global budget of organic aerosol, however, aerosol from nitrate radical oxidation is somewhat minor (slightly more than 3 Tg/yr) due to the relatively high volatility of organic-NO<sub>3</sub> oxidation products in the yield parameterization. Globally, 69 to 88 Tg/yr of organic aerosol is predicted to be produced annually, of which 14–15 Tg/yr is from oxidation of monoterpenes and sesquiterpenes and 8–9 Tg/yr from isoprene.

 References Aldener, M., Brown, S S., Stark, H., Williams, E J., Lerner, B M., Kuster, W C., Goldan, P D., Quinn, P K., Bates, T S., Fehsenfeld, F C., and Ravishankara, A R.: Reactivity and loss mechanisms of NO<sub>3</sub> and N<sub>2</sub>O$_5$ in a polluted marine environment: Results from in situ measurements during New England Air Quality Study 2002, J. Geophys. Res., 111, D23S73, \doi10.1029/2006JD007252, 2006. Archibald, A. T., Jenkin, M. E., and Shallcross, D. E.: An isoprene mechanism intercomparison, Atmos. Environ. 44, 5356–5364, doi:10.1016/J.ATMOSENV.2009.09.016, 2010. Atkinson, R. and Arey, J.: Atmospheric degration of volatile organic compounds, Chem. Rev., 103, 4605–4638, \doi10.1021/CR0206420, 2003. Bian, F. and Bowman, F M.: Theoretical method for lumping multicomponent secondary organic aerosol mixtures, Environ. Sci. Technol., 36, 2491–2497, \doi10.1021/Es015600s, 2002. Brown, S. S., deGouw, J. A., Warneke, C., Ryerson, T. B., Dubé, W. P., Atlas, E., Weber, R. J., Peltier, R. E., Neuman, J. A., Roberts, J. M., Swanson, A., Flocke, F., McKeen, S. A., Brioude, J., Sommariva, R., Trainer, M., Fehsenfeld, F. C., and Ravishankara, A. R.: Nocturnal isoprene oxidation over the Northeast United States in summer and its impact on reactive nitrogen partitioning and secondary organic aerosol, Atmos. Chem. Phys., 9, 3027–3042, doi:10.5194/acp-9-3027-2009, 2009. Butler, T. M., Taraborrelli, D., Brühl, C., Fischer, H., Harder, H., Martinez, M., Williams, J., Lawrence, M. G., and Lelieveld, J.: Improved simulation of isoprene oxidation chemistry with the ECHAM5/MESSy chemistry-climate model: lessons from the GABRIEL airborne field campaign, Atmos. Chem. Phys., 8, 4529–4546, doi:10.5194/acp-8-4529-2008, 2008. Capouet, M., Mueller, J F., Ceulemans, K., Compernolle, S., Vereecken, L., and Peeters, J.: Modeling aerosol formation in alpha-pinene photo-oxidation experiments, J. Geophys. Res., 113, D02308, \doi10.1029/2007JD008995, 2008. 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, doi:10.5194/acp-9-4987-2009, 2009. Carlton, A G., Pinder, R W., Bhave, P V., and Pouliot, G A.: To what extent can biogenic SOA be controlled?, Environ. Sci. Technol., 44, 3376–3380, \doi10.1021/Es903506b, 2010. 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, doi:10.5194/acp-9-3049-2009, 2009. Chan, A. W. H., Chan, M. N., Surratt, J. D., Chhabra, P. S., Loza, C. L., Crounse, J. D., Yee, L. D., Flagan, R. C., Wennberg, P. O., and Seinfeld, J. H.: Role of aldehyde chemistry and NO<sub>x</sub> concentrations in secondary organic aerosol formation, Atmos. Chem. Phys., 10, 7169–7188, doi:10.5194/acp-10-7169-2010, 2010. Chung, S H. and Seinfeld, J H.: Global distribution and climate forcing of carbonaceous aerosols, J. Geophys. Res., 107, 4407, \doi10.1029/2001JD001397, 2002. 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, \doi10.1029/2004JD005623, 2005. Donahue, N M., Robinson, A L., Stanier, C O., and Pandis, S N.: Coupled partitioning, dilution, and chemical aging of semivolatile organics, Environ. Sci. Technol., 40, 2635–2643, \doi10.1021/ES052297c, 2006. Eddingsaas, N C., VanderVelde, D G., and Wennberg, P O.: Kinetics and products of the acid-catalyzed ring-opening of atmospherically relevant butyl epoxy alcohols, J. Phys. Chem. A, 114, 8106–8113, \doi10.1021/jp103907c, 2010. Farina, S C., Adams, P J., and Pandis, S N.: Modeling global secondary organic aerosol formation and processing with the volatility basis set: Implications for anthropogenic secondary organic aerosol, J. Geophys. Res., 115, D09202, \doi10.1029/2009jd013046, 2010. Fry, J. L., Kiendler-Scharr, A., Rollins, A. W., Wooldridge, P. J., Brown, S. S., Fuchs, H., Dubé, W., Mensah, A., dal Maso, M., Tillmann, R., Dorn, H.-P., Brauers, T., and Cohen, R. C.: Organic nitrate and secondary organic aerosol yield from NO<sub>3</sub> oxidation of ß-pinene evaluated using a gas-phase kinetics/aerosol partitioning model, Atmos. Chem. Phys., 9, 1431–1449, doi:10.5194/acp-9-1431-2009, 2009. Goldstein, A H. and Galbally, I E.: Known and unexplored organic constituents in the earth's atmosphere, Environ. Sci. Technol., 41, 1514–1521, \doi10.1021/ES072476p, 2007. Grieshop, A. P., Logue, J. M., Donahue, N. M., and Robinson, A. L.: Laboratory investigation of photochemical oxidation of organic aerosol from wood fires 1: measurement and simulation of organic aerosol evolution, Atmos. Chem. Phys., 9, 1263–1277, doi:10.5194/acp-9-1263-2009, 2009. 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, 1999a. Griffin, R J., Cocker, D R., Seinfeld, J H., and Dabdub, D.: Estimate of global atmospheric organic aerosol from oxidation of biogenic hydrocarbons, Geophys. Res. Lett., 26, 2721–2724, 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. Guenther, A., Karl, T., Harley, P., Wiedinmyer, C., Palmer, P. I., and Geron, C.: Estimates of global terrestrial isoprene emissions using MEGAN (Model of Emissions of Gases and Aerosols from Nature), Atmos. Chem. Phys., 6, 3181–3210, doi:10.5194/acp-6-3181-2006, 2006. 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., 32, L18809, \doi10.1029/2005GL023831, 2005. Heald, C L., Henze, D K., Horowitz, L W., Feddema, J., Lamarque, J F., Guenther, A., Hess, P G., Vitt, F., Seinfeld, J H., Goldstein, A H., and Fung, I.: Predicted change in global secondary organic aerosol concentrations in response to future climate, emissions, and land use change, J. Geophys. Res., 113, D05211, \doi10.1029/2007JD009092, 2008. Hennigan, C. J., Bergin, M. H., Russell, A. G., Nenes, A., and Weber, R. J.: Gas/particle partitioning of water-soluble organic aerosol in Atlanta, Atmos. Chem. Phys., 9, 3613–3628, doi:10.5194/acp-9-3613-2009, 2009. Henze, D K. and Seinfeld, J H.: Global secondary organic aerosol from isoprene oxidation, Geophys. Res. Lett., 33, L09812, \doi10.1029/2006GL025976, 2006. Henze, D. K., Seinfeld, J. H., Ng, N. L., Kroll, J. H., Fu, T.-M., Jacob, D. J., and Heald, C. L.: Global modeling of secondary organic aerosol formation from aromatic hydrocarbons: high- vs. low-yield pathways, Atmos. Chem. Phys., 8, 2405–2420, doi:10.5194/acp-8-2405-2008, 2008. 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. Kroll, J H., Ng, N L., Murphy, S M., Flagan, R C., and Seinfeld, J H.: Secondary organic aerosol formation from isoprene photooxidation under high-NO<sub>x</sub> conditions, Geophys. Res. Lett., 32, L18808, \doi10.1029/2005gl023637, 2005. Kroll, J H., Ng, N L., Murphy, S M., Flagan, R C., and Seinfeld, J H.: Secondary organic aerosol formation from isoprene photooxidation, Environ. Sci. Technol., 40, 1869–1877, \doi10.1021/Es0524301, 2006. Lane, T E., Donahue, N M., and Pandis, S N.: Effect of NO<sub>x</sub> on secondary organic aerosol concentrations, Environ. Sci. Technol., 42, 6022–6027, \doi10.1021/Es703225a, 2008a. Lane, T E., Donahue, N M., and Pandis, S N.: Simulating secondary organic aerosol formation using the volatility basis-set approach in a chemical transport model, Atmos. Environ., 42, 7439–7451, \doi10.1016/J.ATMOSENV.2008.06.026, 2008b. Lelieveld, J., Butler, T M., Crowley, J N., Dillon, T J., Fischer, H., Ganzeveld, L., Harder, H., Lawrence, M G., Martinez, M., Taraborrelli, D., and Williams, J.: Atmospheric oxidation capacity sustained by a tropical forest, Nature, 452, 737–740, \doi10.1038/NATURE06870, 2008. Liao, H., Henze, D K., Seinfeld, J H., Wu, S L., and Mickley, L J.: Biogenic secondary organic aerosol over the United States: Comparison of climatological simulations with observations, J. Geophys. Res., 112, D06201, \doi10.1029/2006JD007813, 2007. Lim, Y B. and Ziemann, P J.: Products and mechanism of secondary organic aerosol formation from reactions of n-alkanes with OH radicals in the presence of NO<sub>x</sub>, Environ. Sci. Technol., 39, 9229–9236, \doi10.1021/Es051447g, 2005. Marley, N. A., Gaffney, J. S., Tackett, M., Sturchio, N. C., Heraty, L., Martinez, N., Hardy, K. D., Marchany-Rivera, A., Guilderson, T., MacMillan, A., and Steelman, K.: The impact of biogenic carbon sources on aerosol absorption in Mexico City, Atmos. Chem. Phys., 9, 1537–1549, doi:10.5194/acp-9-1537-2009, 2009. 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, doi:10.5194/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, doi:10.5194/acp-7-3909-2007, 2007b. Ng, N. L., Kwan, A. J., Surratt, J. D., Chan, A. W. H., Chhabra, P. S., Sorooshian, A., Pye, H. O. T., Crounse, J. D., Wennberg, P. O., Flagan, R. C., and Seinfeld, J. H.: Secondary organic aerosol (SOA) formation from reaction of isoprene with nitrate radicals (NO<sub>3</sub>), Atmos. Chem. Phys., 8, 4117–4140, doi:10.5194/acp-8-4117-2008, 2008. 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.: Organic particulate material levels in the atmosphere: Conditions favoring sensitivity to varying relative humidity and temperature, P. Natl. Acad. Sci. USA, 107, 6682–6686, \doi10.1073/Pnas.1001043107, 2010. Park, R J., Jacob, D J., Chin, M., and Martin, R V.: Sources of carbonaceous aerosols over the United States and implications for natural visibility, J. Geophys. Res., 108, 4355, \doi10.1029/2002JD003190, 2003. Park, R J., Jacob, D J., Kumar, N., and Yantosca, R M.: Regional visibility statistics in the United States: Natural and transboundary pollution influences, and implications for the Regional Haze Rule, Atmos. Environ., 40, 5405–5423, \doi10.1016/J.ATMOSENV.2006.04.059, 2006. Pathak, R. K., Presto, A. A., Lane, T. E., Stanier, C. O., Donahue, N. M., and Pandis, S. N.: Ozonolysis of α-pinene: parameterization of secondary organic aerosol mass fraction, Atmos. Chem. Phys., 7, 3811–3821, doi:10.5194/acp-7-3811-2007, 2007. Perring, A. E., Wisthaler, A., Graus, M., Wooldridge, P. J., Lockwood, A. L., Mielke, L. H., Shepson, P. B., Hansel, A., and Cohen, R. C.: A product study of the isoprene+NO<sub>3</sub> reaction, Atmos. Chem. Phys., 9, 4945–4956, doi:10.5194/acp-9-4945-2009, 2009. Presto, A A., Hartz, K. E H., 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, \doi10.1021/Es050400s, 2005. Pye, H. O. T. and Seinfeld, J. H.: A global perspective on aerosol from low-volatility organic compounds, Atmos. Chem. Phys., 10, 4377–4401, doi:10.5194/acp-10-4377-2010, 2010. 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, \doi10.1126/SCIENCE.1133061, 2007. Rollins, A. W., Kiendler-Scharr, A., Fry, J. L., Brauers, T., Brown, S. S., Dorn, H.-P., Dubé, W. P., Fuchs, H., Mensah, A., Mentel, T. F., Rohrer, F., Tillmann, R., Wegener, R., Wooldridge, P. J., and Cohen, R. C.: Isoprene oxidation by nitrate radical: alkyl nitrate and secondary organic aerosol yields, Atmos. Chem. Phys., 9, 6685–6703, doi:10.5194/acp-9-6685-2009, 2009. Sakulyanontvittaya, T., Duhl, T., Wiedinmyer, C., Helmig, D., Matsunaga, S., Potosnak, M., Milford, J., and Guenther, A.: Monoterpene and sesquiterpene emission estimates for the United States, Environ. Sci. Technol., 42, 1623–1629, \doi10.1021/Es702274e, 2008. Schauer, J J., Kleeman, M J., Cass, G R., and Simoneit, B. R T.: Measurement of emissions from air pollution sources. 3. C-1-C-29 organic compounds from fireplace combustion of wood, Environ. Sci. Technol., 35, 1716–1728, \doi10.1021/ES001331e, 2001. Schichtel, B A., Malm, W C., Bench, G., Fallon, S., McDade, C E., Chow, J C., and Watson, J G.: Fossil and contemporary fine particulate carbon fractions at 12 rural and urban sites in the United States, J. Geophys. Res., 113, D02311, \doi10.1029/2007JD008605, 2008. 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 a-pinene, Atmos. Chem. Phys., 8, 2073–2088, doi:10.5194/acp-8-2073-2008, 2008. Shrivastava, M K., Lipsky, E M., Stanier, C O., and Robinson, A L.: Modeling semivolatile organic aerosol mass emissions from combustion systems, Environ. Sci. Technol., 40, 2671–2677, \doi10.1021/ES0522231, 2006. Stanier, C O., Donahue, N., and Pandis, S N.: Parameterization of secondary organic aerosol mass fractions from smog chamber data, Atmos. Environ., 42, 2276–2299, 2008. Surratt, J D., Lewandowski, M., Offenberg, J H., Jaoui, M., Kleindienst, T E., Edney, E O., and Seinfeld, J H.: Effect of acidity on secondary organic aerosol formation from isoprene, Environ. Sci. Technol., 41, 5363–5369, \doi10.1021/Es0704176, 2007. Surratt, J D., Chan, A. W H., Eddingsaas, N C., Chan, M N., Loza, C L., Kwan, A J., Hersey, S P., Flagan, R C., Wennberg, P O., and Seinfeld, J H.: Reactive intermediates revealed in secondary organic aerosol formation from isoprene, P. Natl. Acad. Sci. USA, 107, 6640–6645, \doi10.1073/Pnas.0911114107, 2010. Szidat, S.: Radiocarbon analysis of carbonaceous aerosols: Recent developments, Chimia, 63, 157–161, \doi10.2533/CHIMIA.2009.157, 2009. Tsigaridis, K. and Kanakidou, M.: Global modelling of secondary organic aerosol in the troposphere: a sensitivity analysis, Atmos. Chem. Phys., 3, 1849–1869, doi:10.5194/acp-3-1849-2003, 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, \doi10.1029/2006GL026899, 2006. Warneke, C., de~Gouw, J A., Goldan, P D., Kuster, W C., Williams, E J., Lerner, B M., Jakoubek, R., Brown, S S., Stark, H., Aldener, M., Ravishankara, A R., Roberts, J M., Marchewka, M., Bertman, S., Sueper, D T., McKeen, S A., Meagher, J F., and Fehsenfeld, F C.: Comparison of daytime and nighttime oxidation of biogenic and anthropogenic VOCs along the New England coast in summer during New England Air Quality Study 2002, J. Geophys. Res., 109, D10309, \doi10.1029/2003jd004424, 2004. Weber, R J., Sullivan, A P., Peltier, R E., Russell, A., Yan, B., Zheng, M., de~Gouw, J., Warneke, C., Brock, C., Holloway, J S., Atlas, E L., and Edgerton, E.: A study of secondary organic aerosol formation in the anthropogenic-influenced southeastern United States, J. Geophys. Res., 112, D13302, \doi10.1029/2007JD008408, 2007. Wesely, M L.: Parameterization of surface resistances to gaseous dry deposition in regional-scale numerical-models, Atmos. Environ., 23, 1293–1304, 1989. Zhang, L M., Gong, S L., Padro, J., and Barrie, L.: A size-segregated particle dry deposition scheme for an atmospheric aerosol module, Atmos. Environ., 35, 549–560, 2001. Zhang, J Y., Hartz, K. E H., 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, 11053–11063, \doi10.1021/Jp06286f, 2006.