Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 9 4 2009 10.5194/acp-9-1431-2009 http://www.atmos-chem-phys.net/9/1431/2009/ http://www.atmos-chem-phys.net/9/1431/2009/acp-9-1431-2009.html http://www.atmos-chem-phys.net/9/1431/2009/acp-9-1431-2009.pdf 1431 1449 2009-02-23 Organic nitrate and secondary organic aerosol yield from NO₃ oxidation of β-pinene evaluated using a gas-phase kinetics/aerosol partitioning model J. L. Fry A. Kiendler-Scharr A. W. Rollins P. J. Wooldridge S. S. Brown H. Fuchs W. Dubé A. Mensah M. dal Maso R. Tillmann H.-P. Dorn T. Brauers R. C. Cohen rccohen@berkeley.edu Department of Chemistry, University of California, Berkeley, CA, USA ICG-2: Troposphäre, Forschungszentrum Jülich, 52425 Jülich, Germany Chemical Sciences Division, NOAA Earth System Research Laboratory, Boulder, CO, USA The yields of organic nitrates and of secondary organic aerosol (SOA) particle formation were measured for the reaction NO₃+β-pinene under dry and humid conditions in the atmosphere simulation chamber SAPHIR at Research Center Jülich. These experiments were conducted at low concentrations of NO₃ (NO₃+N₂O₅<10 ppb) and β-pinene (peak~15 ppb), with no seed aerosol. SOA formation was observed to be prompt and substantial (~50% mass yield under both dry conditions and at 60% RH), and highly correlated with organic nitrate formation. The observed gas/aerosol partitioning of organic nitrates can be simulated using an absorptive partitioning model to derive an estimated vapor pressure of the condensing nitrate species of <i>p</i>_vap~5&times;10^&minus;6 Torr (6.67&times;10^&minus;4 Pa), which constrains speculation about the oxidation mechanism and chemical identity of the organic nitrate. Once formed the SOA in this system continues to evolve, resulting in measurable aerosol volume decrease with time. The observations of high aerosol yield from NO_x-dependent oxidation of monoterpenes provide an example of a significant <i>anthropogenic</i> source of SOA from <i>biogenic</i> hydrocarbon precursors. Estimates of the NO₃+β-pinene SOA source strength for California and the globe indicate that NO₃ reactions with monoterpenes are likely an important source (0.5–8% of the global total) of organic aerosol on regional and global scales. SAPHIR homepage: http://www.fz-juelich.de/icg/icg-2/saphir/, last access: 18~February~2009. 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 NO₃ and N₂O$_5$ in a polluted marine environment: Results from in situ measurements during New England Air Quality Study 2002, J. Geophys. Res.-Atmos., 111, D23S73, doi:10.1029/2006JD007252, 2006. Alfaro-Moreno, E., Nawrot, T. S., Nemmar, A., and Nemery, B.: Particulate matter in the environment: pulmonary and cardiovascular effects, Curr. Opin. Pulm. Med., 13, 98–106, 2007. Alfarra, M. R., Paulsen, D., Gysel, M., Garforth, A. A., Dommen, J., Prévôt, 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. Allan, J. D., Delia, A. E., Coe, H., Bower, K. N., Alfarra, M. R., Jimenez, J. L., Middlebrook, A. M., Drewnick, F., Onasch, T. B., Canagaratna, M. R., Jayne, J. T., and Worsnopf, D. R.: A generalised method for the extraction of chemically resolved mass spectra from aerodyne aerosol mass spectrometer data, J. Aerosol Sci., 35, 909–-922, 2004. Apel, E. C., Brauers, T., Koppmann, R., Bandowe, B., Bossmeyer, J., Holzke, C., Tillmann, R., Wahner, A., Wegener, R., Brunner, A., Jocher, M., Ruuskanen, C., Spirig, C., Steigner, R., Steinbrecher, R., Gomez Alvarez, E., Mueller, K., Burrows, J. P., Schade, G., Solomon, S. J., Ladstaetter-Weissenmayer, A., Simmonds, P., Young, D., Hopkins, J. R., Lewis, A. C., Legreid, G., Reimann, S., Hansel, A., Wisthaler, A., Blake, R. S., Ellis, A. M., Monks, P. S., and Wyche, K. P.: Intercomparison of oxygenated volatile organic compound (OVOC) measurements at the SAPHIR atmosphere simulation chamber, J. Geophys. Res.-Atmos., in press, 2009. Apodaca, R. L., Simpson, W. R., Ball, S. M., Brauers, T., Brown, S. S., Cohen, R. C., Crowley, J., Dorn, H.-P., Dubé, W. P., Fry, J. L., Fuchs, H., Haseler, R., Heitmann, U., Kato, S., Kajii, Y., Kiendler-Scharr, A., Kleffmann, J., Labazan, I., Matsumoto, J., Nishida, S., Rollins, A. W., Tillmann, R., Wahner, A., Wegener, R., and Wooldridge, P. J.: Intercomparison of N₂O$_5$ sensors using SAPHIR reaction chamber, Atmos. Chem. Phys., in preparation, 2009. Atkinson, R.: Gas-phase tropospheric chemistry of volatile organic compounds, 1. Alkanes and alkenes, J. Phys. Chem. Ref. Data, 26, 215–290, 1997. Barnes, I., Bastian, V., Becker, K. H., and Tong, Z.: Kinetics and Products of the Reactions of NO₃ with Monoalkenes, Dialkenes, and Monoterpenes, J. Phys. Chem., 94, 2413–2419, 1990. Berndt, T. and Boge, O.: Products and mechanism of the gas-phase reaction of NO₃ radicals with a-pinene, J. Chem. Soc. Faraday T., 93, 3021–3027, 1997. Bohn, B., Rohrer, F., Brauers, T., and Wahner, A.: Actinometric measurements of NO₂ photolysis frequencies in the atmosphere simulation chamber SAPHIR, Atmos. Chem. Phys., 5, 493–503, 2005. Bonn, B. and Moorgat, G. K.: New particle formation during a- and b-pinene oxidation by O₃, OH and NO₃, and the influence of water vapour: particle size distribution studies, Atmos. Chem. Phys., 2, 183–196, 2002. Bossmeyer, J., Brauers, T., Richter, C., Rohrer, F., Wegener, R., and Wahner, A.: Simulation chamber studies on the NO₃ chemistry of atmospheric aldehydes, Geophys. Res. Lett., 33, L18810, doi:10.1029/2006GL026778, 2006. Brauers, T., Bossmeyer, J., Dorn, H.-P., Schlosser, E., Tillmann, R., Wegener, R., and Wahner, A.: Investigation of the formaldehyde differential absorption cross section at high and low spectral resolution in the simulation chamber SAPHIR, Atmos. Chem. Phys., 7, 3579–3586, 2007. Burkholder, J. B., Baynard, T., Ravishankara, A. R., and Lovejoy, E. R.: Particle nucleation following the O₃ and OH initiated oxidation of alpha-pinene and beta-pinene between 278 and 320 K, J. Geophys. Res.-Atmos., 112, D10216, doi:10.1029/2006JD007783, 2007. Calvert, J. G., Atkinson, J. A., Kerr, J. A., Madronich, S., Moortgat, G. K., Wallington, T. J., and Yarwood, G.: Mechanisms of the atmospheric oxidation of the alkenes, Oxford University Press, New York, NY, 2000. Canagaratna, M. R., Jayne, J. T., Jimenez, J. L., Allan, J. D., Alfarra, M. R., Zhang, Q., Onasch, T. B., Drewnick, F., Coe, H., Middlebrook, A., Delia, A., Williams, L. R., Trimborn, A. M., Northway, M. J., DeCarlo, P. F., Kolb, C. E., Davidovits, P., and Worsnop, D. R.: Chemical and microphysical characterization of ambient aerosols with the aerodyne aerosol mass spectrometer, Mass Spectrom. Rev., 26, 185–222, 2007. Capouet, M. and Müller, J.-F.: A group contribution method for estimating the vapour pressures of α-pinene oxidation products, Atmos. Chem. Phys., 6, 1455–1467, 2006. Capouet, M., Müller, J. F., Ceulemans, K., Compernolle, S., Vereecken, L., and Peeters, J.: Modeling aerosol formation in alpha-pinene photo-oxidation experiments, J. Geophys. Res.-Atmos., 113, D02308, doi:10.1029/2007JD008995, 2008. Cottrell, L. D., Griffin, R. J., Jimenez, J. L., Zhang, Q., Ulbrich, I., Ziemba, L. D., Beckman, P. J., Sive, B. C., and Talbot, R. W.: Submicron particles at Thompson Farm during ICARTT measured using aerosol mass spectrometry, J. Geophys. Res.-Atmos., 113, D08212, doi:10.1029/2007JD009192, 2008. Cowie, J. M. G.: Polymers: Chemistry and physics of modern materials, 2nd ed., Blackie Academic & Professional, Glasgow, UK, 28 pp., 1991. Day, D. A., Wooldridge, P. J., Dillon, M. B., Thornton, J. A., and Cohen, R. C.: A thermal dissociation laser-induced fluorescence instrument for in situ detection of NO₂, peroxy nitrates, alkyl nitrates, and HNO₃, J. Geophys. Res.-Atmos., 107(D5–6), 4046, doi:10.1029/2001JD000779, 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.-Atmos., 110, D16305, doi:10.1029/2004JD005623, 2005. DeCarlo, P. F., Slowik, J. G., Worsnop, D. R., Davidovits, P., and Jimenez, J. L.: Particle morphology and density characterization by combined mobility and aerodynamic diameter measurements. Part 1: Theory, Aerosol Sci. Tech., 38, 1185–1205, 2004. Docherty, K. S. and Ziemann, P. J.: Effects of stabilized Criegee intermediate and OH radical scavengers on aerosol formation from reactions of \textit$\beta $-pinene with O₃, Aerosol Sci. Tech., 37, 877–891, 2003. Dockery, D. W. and Pope, C. A.: Acute Respiratory Effects of Particulate Air-Pollution, Annu. Rev. Publ. Health, 15, 107–132, 1994. Dorn, H. P., Apodaca, R. L., Ball, S. M., Brauers, T., Brown, S. S., Cohen, R. C., Crowley, J., Dubé, W. P., Fry, J. L., Fuchs, H., Haseler, R., Heitmann, U., Jones, R., Kato, S., Kajii, Y., Kiendler-Scharr, A., Labazan, I., Matsumoto, J., Meinen, J., Nishida, S., Platt, U., Rohrer, F., Rollins, A.W., Ruth, A. A., Schlosser, E., Schuster, G., Shillings, A., Simpson, W., Thieser, J., Tillmann, R., Varma, R., Venables, D., Wahner, A., Wegener, R., and Wooldridge, P. J.: Intercomparison of NO₃ measurement techniques at the simulation chamber SAPHIR, Atmos. Chem. Phys., in preparation, 2009. Dubé, W. P., Brown, S. S., Osthoff, H. D., Nunley, M. R., Ciciora, S. J., Paris, M. W., McLaughlin, R. J., and Ravishankara, A. R.: Aircraft instrument for simultaneous, in situ measurement of NO₃ and N₂O$_5$ via pulsed cavity ring-down spectroscopy, Rev. Sci. Instrum., 77, 034101, doi:10.1063/1.2176058, 2006. Dubowski, Y., Sumner, A. L., Menke, E. J., Gaspar, D. J., Newberg, J. T., Hoffman, R. C., Penner, R. M., Hemminger, J. C., and Finlayson-Pitts, B. J.: Interactions of gaseous nitric acid with surfaces of environmental interest, Phys. Chem. Chem. Phys., 6, 3879–3888, 2004. Farmer, D. K., Cohen, R. C., Perring, A. E., Wooldridge, P. J., Blake, D., Baker, A., Huey, L. G., Sjostedt, S., Tanner, D., Vargas, O., de Gouw, J., Warneke, C., Kuster, W., Murphy, J. G.: NO_y partitioning and the role of alkyl nitrates in air quality in the Mexico City Area, Atmos. Chem. Phys., in preparation, 2009. Forkel, R., Klemm, O., Graus, M., Rappengluck, B., Stockwell, W. R., Grabmer, W., Held, A., Hansel, A., and Steinbrecher, R.: Trace gas exchange and gas phase chemistry in a Norway spruce forest: a study with a coupled 1-dimensional canopy atmospheric chemistry emission model, Atmos. Environ., 40, 28–42, 2006. Forster, P., Ramaswamy, V., Artaxo, P., Berntsen, T., Betts, R., Fahey, D. W., Haywood, J., Lean, J., Lowe, D. C., Myhre, G., Nganga, J., Prinn, R., Raga, G., Schulz, M., and Van Dorland, R.: Changes in Atmospheric Constitutents and in Radiative Forcing, in: Climate Change 2007: The Physical Science Basis. Contribution fo Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change, edited by: Solomon, S., Qin, D., Manning, M., Chen, Z., Marquis, M., Averyt, K. B., Tignor, M., and Miller, H. L., Cambridge University Press, Cambridge, United Kingdom and New York, NY, USA, 2007. Fountoukis, C., Nenes, A., Sullivan, A., Weber, R., VanReken, T., Fischer, M., Matías, E., Moya, M., Farmer, D., and Cohen, R. C.: Thermodynamic characterization of Mexico City aerosol during MILAGRO 2006, Atmos. Chem. Phys. Discuss., 7, 9203–9233, 2007. Fuchs, H. Brown, S. S., Dubé, W., et al.: Intercomparison of instruments measuring NO₂ at the atmosphere simulation chamber SAPHIR, Atmos. Chem. Phys., in preparation, 2009. Fuentes, J. D., Wang, D., Bowling, D. R., Potosnak, M., Monson, R. K., Goliff, W. S., and Stockwell, W. R.: Biogenic hydrocarbon chemistry within and above a mixed deciduous forest, J. Atmos. Chem., 56, 165–185, 2007. Fuzzi, S., Andreae, M. O., Huebert, B. J., Kulmala, M., Bond, T. C., Boy, M., Doherty, S. J., Guenther, A., Kanakidou, M., Kawamura, K., Kerminen, V.-M., Lohmann, U., Russell, L. M., and Pöschl, U.: Critical assessment of the current state of scientific knowledge, terminology, and research needs concerning the role of organic aerosols in the atmosphere, climate, and global change, Atmos. Chem. Phys., 6, 2017–2038, 2006. Geyer, A., Alicke, B., Konrad, S., Schmitz, T., Stutz, J., and Platt, U.: Chemistry and oxidation capacity of the nitrate radical in the continental boundary layer near Berlin, J. Geophys. Res.-Atmos., 106, 8013–8025, 2001. Geyer, A., Alicke, B., Ackermann, R., Martinez, M., Harder, H., Brune, W., di Carlo, P., Williams, E., Jobson, T., Hall, S., Shetter, R., and Stutz, J.: Direct observations of daytime NO₃: Implications for urban boundary layer chemistry, J. Geophys. Res.-Atmos., 108(D12), 4268, doi:10.1029/2002JD002967, 2003. Goldstein, A. H. and Galbally, I. E.: Known and unexplored organic constituents in the earth's atmosphere, Environ. Sci. Technol., 41, 1514–1521, 2007. Gong, H. M., Matsunaga, A., and Ziemann, P. J.: Products and mechanism of secondary organic aerosol formation from reactions of linear alkenes with NO₃ radicals, J. Phys. Chem. A, 109, 4312–4324, 2005. Goto, D., Takemura, T., and Nakajima, T.: Importance of global aerosol modeling including secondary organic aerosol formed from monoterpene, J. Geophys. Res.-Atmos., 113, D07205, doi:10.1029/2007JD009019, 2008. 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, 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.-Atmos., 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, 2006. Hallquist, M., Wangberg, I., Ljungstrom, E., Barnes, I., and Becker, K. H.: Aerosol and product yields from NO₃ radical-initiated oxidation of selected monoterpenes, Environ. Sci. Technol., 33, 553–559, 1999. Hanke, M., Uecker, J., Reiner, T., and Arnold, F.: Atmospheric peroxy radicals: ROXMAS, a new mass-spectrometric methodology for speciated measurements of HO₂ and $§igma$RO₂ and first results, Int. J. Mass Spec., 213, 91–99, 2002. 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, doi:10.1029/2005GL023831, 2005. 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. Jay, K. and Stieglitz, L.: The Gas-Phase Addition of NOx to Olefins, Chemosphere, 19, 1939–1950, 1989. Jenkin, M. E.: Modelling the formation and composition of secondary organic aerosol from α- and β-pinene ozonolysis using MCM v3, Atmos. Chem. Phys., 4, 1741–1757, 2004. Kamens, R., Jang, M., Chien, C. J., and Leach, K.: Aerosol formation from the reaction of alpha-pinene and ozone using a gas-phase kinetics aerosol partitioning model, Environ. Sci. Technol., 33, 1430–1438, 1999. Kanakidou, M., Seinfeld, J. H., Pandis, S. N., Barnes, I., Dentener, F. J., Facchini, M. C., Van Dingenen, R., Ervens, B., Nenes, A., Nielsen, C. J., Swietlicki, E., Putaud, J. P., Balkanski, Y., Fuzzi, S., Horth, J., Moortgat, G. K., Winterhalter, R., Myhre, C. E. L., Tsigaridis, K., Vignati, E., Stephanou, E. G., and Wilson, J.: Organic aerosol and global climate modelling: a review, Atmos. Chem. Phys., 5, 1053–1123, 2005. Korhonen, H., Lehtinen, K. E. J., and Kulmala, M.: Multicomponent aerosol dynamics model UHMA: model development and validation, Atmos. Chem. Phys., 4, 757–771, 2004. Kurtenbach, R., Ackermann, R., Becker, K. H., Geyer, A., Gomes, J. A. G., Lorzer, J. C., Platt, U., and Wiesen, P.: Verification of the contribution of vehicular traffic to the total NMVOC emissions in Germany and the importance of the NO₃ chemistry in the city air, J. Atmos. Chem., 42, 395–411, 2002. 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 aerosol yields from the ozonolysis of ten different terpenes, J. Geophys. Res.-Atmos., 111, D07302, doi:10.1029/2005JD006437, 2006. Lelieveld, J. and Crutzen, P. J.: The Role of Clouds in Tropospheric Photochemistry, J. Atmos. Chem., 12, 229–267, 1991. Lindinger, W., Hansel, A., and Jordan, A.: On-line monitoring of volatile organic compounds at pptv levels by means of proton-transfer-reaction mass spectrometry (PTR-MS) – Medical applications, food control and environmental research, Int. J. Mass. Spectrom., 173, 191–241, 1998. Moise, T., Talukdar, R. K., Frost, G. J., Fox, R. W., and Rudich, Y.: Reactive uptake of NO₃ by liquid and frozen organics, J. Geophys. Res., 107(D2), 4014, doi:10.1029/2001JD000334, 2002. Moldanova, J. and Ljungstrom, E.: Modelling of particle formation from NO₃ oxidation of selected monoterpenes, J. Aerosol Sci., 31, 1317–1333, 2000. 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 (NO₃), Atmos. Chem. Phys., 8, 4117–4140, 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.: 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. Poling, B. E., Prausnitz, J. M., and O'Connell, J. P.: The properties of gases and liquids, 5th ed., McGraw-Hill, New York, 2001. Pope, C. A., Dockery, D. W., and Schwartz, J.: Review of Epidemiological Evidence of Health-Effects of Particulate Air-Pollution, Inhal. Toxicol., 7, 1–18, 1995. Pope, C. A.: Mortality effects of longer term exposures to fine particulate air pollution: Review of recent epidemiological evidence, Inhal. Toxicol., 19, 33–38, 2007. Quinn, P. K., Bates, T. S., Coffman, D., Onasch, T. B., Worsnop, D., Baynard, T., de Gouw, J. A., Goldan, P. D., Kuster, W. C., Williams, E., Roberts, J. M., Lerner, B., Stohl, A., Pettersson, A., and Lovejoy, E. R.: Impacts of sources and aging on submicrometer aerosol properties in the marine boundary layer across the Gulf of Maine, J. Geophys. Res.-Atmos., 111, D23S36, doi:10.1029/2006JD007582, 2006. Richter, K., Knoche, R., Schoenemeyer, T., Smiatek, G., and Steinbrecher, R.: Estimate of biogenic hydrocarbon emissions, Umweltwissenschaften und Schadstoff-Forschung, 10, 319–325, 1998. Rohrer, F., Bohn, B., Brauers, T., Brüning, D., Johnen, F.-J., Wahner, A., and Kleffmann, J.: Characterisation of the photolytic HONO-source in the atmosphere simulation chamber SAPHIR, Atmos. Chem. Phys., 5, 2189–2201, 2005. Russell, M. and Allen, D. T.: Predicting secondary organic aerosol formation rates in southeast Texas, J. Geophys. Res.-Atmos., 110, D07S17, doi:10.1029/2004JD004722, 2005. 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, 2008. Sander, S. P., Golden, D. M., Kurylo, M. J., Moortgat, G. K., Wine, P. H., Ravishankara, A. R., Kolb, C. E., Molina, M. J., Finlayson-Pitts, B. J., Huie, R. E., Orkin, V. L., Friedl, R. R., and Keller-Rudek, H.: Chemical kinetics and photochemical data for use in atmospheric studies: evaluation number 15, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, 2006. Saunders, S. M., Jenkin, M. E., Derwent, R. G., and Pilling, M. J.: Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A): tropospheric degradation of non-aromatic volatile organic compounds, Atmos. Chem. Phys., 3, 161–180, 2003. 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.-Atmos., 113, D02311, doi:10.1029/2007JD008605, 2008. Scott, K. I. and Benjamin, M. T.: Development of a biogenic volatile organic compounds emission inventory for the SCOS97-NARSTO domain, Atmos. Environ., 37, 39–49, 2003. Seinfeld, J. H. and Pankow, J. F.: Organic Atmospheric Particulate Material, Annu. Rev. Phys. Chem., 54, 121–140, doi:10.1146/annurev.physchem.54.011002.103756, 2003. Simpson, D., Guenther, A., Hewitt, C. N., and Steinbrecher, R.: Biogenic Emissions in Europe. 1. Estimates and Uncertainties, J. Geophys. Res.-Atmos., 100, 22875–22890, 1995. Spittler, M., Barnes, I., Bejan, I., Brockmann, K. J., Benter, T., and Wirtz, K.: Reactions of NO₃ radicals with limonene and alpha-pinene: Product and SOA formation, Atmos. Environ., 40, S116–S127, 2006. Thornton, J. A., Wooldridge, P. J., and Cohen, R. C.: Atmospheric NO₂: In situ laser-induced fluorescence detection at parts per trillion mixing ratios, Anal. Chem., 72, 528–539, 2000. TSI, I.: Aerosol Instrument Manager Software for SMPS Spectrometer User's Manual P/N 1930038 Revision G, October, 2007. 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., 29, 3527–3544, 1995. Verheggen, B. and Mozurkewich, M.: An inverse modeling procedure to determine particle growth and nucleation rates from measured aerosol size distributions, Atmos. Chem. Phys., 6, 2927–2942, 2006. 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. Wangberg, I., Barnes, I., and Becker, K. H.: Product and mechanistic study of the reaction of NO₃ radicals with alpha-pinene, Environ. Sci. Technol., 31, 2130–2135, 1997. 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.-Atmos., 112, D13302, doi:10.1029/2007JD008408, 2007. Wegener, R., Brauers, T., Koppmann, R., Bares, S. R., Rohrer, F., Tillmann, R., Wahner, A., Hansel, A., and Wisthaler, A.: Simulation chamber investigation of the reactions of ozone with short-chained alkenes, J. Geophys. Res.-Atmos., 112, D13301, doi:10.1029/2006JD007531, 2007. Winer, A. M., Atkinson, R., and Pitts, J. N.: Gaseous Nitrate Radical: Possible Nighttime Atmospheric Sink for Biogenic Organic Compounds, Science, 224, 156–159, 1984. Winterhalter, R., Neeb, P., Grossmann, D., Kolloff, A., Horie, O., and Moortgat, G.: Products and Mechanism of the Gas Phase Reaction of Ozone with \textit$\beta $–Pinene, J. Atmos. Chem., 35, 165–197, 2000. 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., DeCarlo, 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., Rautiainen, 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.