References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-8-4117-2008

Secondary organic aerosol (SOA) formation from reaction of isoprene with nitrate radicals (NO3)

N. L.

¹ Kwan

A. J.

² Surratt

J. D.

¹ Chan

A. W. H.

¹ Chhabra

P. S.

¹ Sorooshian

¹ Pye

H. O. T.

¹ Crounse

J. D.

¹ Wennberg

P. O.

² ³ Flagan

R. C.

¹ ² Seinfeld

J. H.

¹ ²

Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USA

Division of Engineering and Applied Science, California Institute of Technology, Pasadena, CA 91125, USA

Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA 91125, USA

01 08 2008

8 14 4117 4140

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/8/4117/2008/acp-8-4117-2008.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/8/4117/2008/acp-8-4117-2008.pdf

Secondary organic aerosol (SOA) formation from the reaction of isoprene with nitrate radicals (NO3) is investigated in the Caltech indoor chambers. Experiments are performed in the dark and under dry conditions (RH&lt10%) using N2O5 as a source of NO3 radicals. For an initial isoprene concentration of 18.4 to 101.6 ppb, the SOA yield (defined as the ratio of the mass of organic aerosol formed to the mass of parent hydrocarbon reacted) ranges from 4.3% to 23.8%. By examining the time evolutions of gas-phase intermediate products and aerosol volume in real time, we are able to constrain the chemistry that leads to the formation of low-volatility products. Although the formation of ROOR from the reaction of two peroxy radicals (RO2) has generally been considered as a minor channel, based on the gas-phase and aerosol-phase data it appears that RO2+RO2 reaction (self reaction or cross-reaction) in the gas phase yielding ROOR products is a dominant SOA formation pathway. A wide array of organic nitrates and peroxides are identified in the aerosol formed and mechanisms for SOA formation are proposed. Using a uniform SOA yield of 10% (corresponding to Mo≅10 μg m−3), it is estimated that ~2 to 3 Tg yr−1 of SOA results from isoprene+NO3. The extent to which the results from this study can be applied to conditions in the atmosphere depends on the fate of peroxy radicals in the nighttime troposphere.

References 1

Alfarra, M. R., Paulsen, D., Gysel, M., Garforth, A. A., Dommen, J., Prevot, 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.

Bahreini, R., Keywood, M. D., Ng, N. L., Varutbangkul, V., Gao, S., Flagan, R. C., and Seinfeld, J. H. Measurements of secondary organic aerosol (SOA) from oxidation of cycloalkenes, terpenes, and m-xylene using an Aerodyne aerosol mass spectrometer. Environ. Sci. Technol., 39, 5674–5688, 2005.

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 Böge, O.: Gas-Phase reaction of NO3 radicals with isoprene: A kinetic and mechanistic study, Inter. J. Chem. Kinet., 29, 755–765, 1997.

Bey, I., Aumont, B., and Toupance, G.: A modeling study of the nighttime radical chemistry in the lower continental troposphere. 1. Development of a detailed chemical mechanism including nighttime chemistry, J. Geophys. Res., 106(D9), 9959–9990, 2001a. Bey, I., Aumont, B., and Toupance, G.: A modeling study of the nighttime radical chemistry in the lower continental troposphere. 2. Origin and evolution of HO$_x$, J. Geophys. Res., 106(D9), 9991–10001, 2001b.

Bey, I., Jacob, D. J., Yantosca, R. M., Logan, J. A., Field, B. D., Fiore, A. M., Li, Q. B., Liu, H. G. Y., Mickley, L. J., and Schultz, M. G.: Global modeling of tropospheric chemistry with assimilated meteorology: Model description and evaluation, J. Geophys. Res., 106(D19), 23 073–23 095, 2001c.

Biggs, P., Canosa-Mas, C. E., Fracheboud, J. M., Shallcross, D. E., and Wayne, R. P.: Investigation into the kinetics and mechanisms of the reaction of NO3 with CH3 and CH3O at 298K between 0.6 Torr and 8.5 Torr – is there a chain decomposition mechanism in operation, J. Chem. Soc., Faraday Trans., 90, 1197–1204, 1994.

Brown, S. S., Ryerson, T. B., Wollny, A. G., Brock, C. A., Peltier, R., Sullivan, A. P., Weber, R. J., Dube, W. P., Trainer, M., Meagher, J. F., Fehsenfeld, F. C., and Ravishankara, A. R.: Variability in nocturnal nitrogen oxide processing and its role in regional air quality, Science, 311, 5757, 67–70, 2006.

Canosa-Mas, C. E., Flugge, M. L., King, M. D., and Wayne, R. P.: An experimental study of the gas-phase reaction of the NO3 radical with $\alpha \rm s\beta \rm t$unsaturated carbonyl compounds, Phys. Chem. Chem. Phys., 7. 643–650, 2005.

Canosa-Mas, C. E., King, M. D., Lopez, R., Percival, C. J., Wayne, R. P., Shallcross, D. E., Pyle, J. A., and Daele, V.: Is the reaction CH3C(O)O2 and NO3 important in the night-time troposphere? J. Chem. Soc., Faraday Trans., 92, 2211–2222, 1996.

Carslaw, N., Carpenter, L. J., Plane, J. M. C., Allan, B. J., Burgess, R. A., Clemitshaw, K. C., Coe, H., and Penkett, S. A.: Simultaneous measurements of nitrate and peroxy radicals in the marine boundary layer, J. Geophys. Res., 102, 18 917–18 933. 1997.

Carter, W. P. L. and Atkinson, R.: Development and evaluation of a detailed mechanism for the atmospheric reactions of isoprene and NOx, Int. J. Chem. Kinet., 28, 497–530, 1996.

Claeys, M., Graham, B., Vas, G., Wang, W., Vermeylen, R., Pashynska, V., Cafmeyer, J., Guyon, P., Andreae, M. O., Artaxo, P., and Maenhaut, W.: Formation of secondary organic aerosols through photooxidation of isoprene, Science, 303, 1173–1176, 2004.

Cocker III, D. R., Flagan, R. C., and Seinfeld, J. H.: State-of-the-art chamber facility for studying atmospheric aerosol chemistry, Environ. Sci. Technol., 35, 2594–2601. 2001.

Crounse, J. D., McKinney, K. A., Kwan, A. J., and Wennberg, P. O.: Measurements of gas-phase hydroperoxides by chemical ionization mass spectrometry, Anal. Chem., 78, 6726–6732, 2006.

Curren, K., Gillespie, T., Steyn, D., Dann, T., and Wang, D.: Biogenic isoprene in the Lower Fraser Valley, British Columbia, J. Geophys. Res., 103, D19, 25467-25477, 1998.

Daele, V., Laverdet, G., Lebras, G., and Poulet, G.: Kinetics of the reactions of CH3O+NO, CH3O+NO3, and CH3O2+NO3, J. Phys. Chem., 99, 1470–1477, 1995.

Davidson, J. A., Viggiano, A. A., Howard, C. J., Fehsenfeld, F. C., Albritton, D. L., and Ferguson, E. E.: Rate constants for the reaction of O$_2^+$, NO$_2^+$, NO$^+$, H3O$^+$, CO$_3^-$, NO$_2^-$, and halide ions with N2O$_5$ at 300 K, J. Chem. Phys., 68, 2085–2087, 1978.

Dibble, T. S.: Isomerization of OH-isoprene adducts and hydroxyalkoxy isoprene radicals, J. Phys. Chem., 106(28), 6643–6650, 2002.

Dibbe T. S.: Failures and limitations of quantum chemistry for two key problems in the atmospheric chemistry of peroxy radicals, Atmos. Environ., in press, 2008.

Docherty, K., Wu, W., Lim, Y., and Ziemann, P.: Contributions of Organic Peroxides to Secondary Aerosol Formed from Reactions of Monoterpenes with O3, Environ. Sci. Technol., 39, 4049–4059, 2005.

Dommen, J., Metzger, A., Duplissy, J., Kalberer, M., Alfarra, M. R., Gascho, A., Weingartner, E., Prevot, A. S. H., Verheggen, B., and Baltensperger, U.: Laboratory observation of oligomers in the aerosol from isoprene/NO$_x$ photooxidation, Geophys. Res. Lett., 33, L13805, doi:10.1029/2006GL026523, 2006.

Edney, E. O., Kleindienst, T. E., Jaoui, M., Lewandowski, M., Offenberg, J. H., Wang, W., and Claeys, M.: Formation of 2-methyl tetrols and 2-methylglyceric acid in secondary organic aerosol from laboratory irradiated isoprene/NOx/SO2/air mixtures and their detection in ambient PM$_2.5$ samples collected in the eastern United States, Atmos. Environ., 39, 5281–5289, 2005.

Fan, J. and Zhang, R.: Atmospheric oxidation mechanism of isoprene, Environ. Chem., 1, 140–149, doi:10.1071/EN04045, 2004.

Fuentes, J. D., Wang, D., Rowling, 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.

Gao, S., Keywood, M. D., Ng, N. L., Surratt, J. D., Varutbangkul, V., Bahreini, R., Flagan, R. C., and Seinfeld, J. H.: Low molecular weight and oligomeric components in secondary organic aerosol from the ozonolysis of cycloalkenes and $\alpha $-pinene, J. Phys. Chem. A, 108, 10 147–10 164, 2004a.

Gao, S., Ng, N. L., Keywood, M. D., 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, 2004b.

Gao, S., Surratt, J. D., Knipping, E. M., Edgerton, E. S., Shahgholi, M., and Seinfeld, J. H.: Characterization of polar organic components in fine aerosols in the southeastern United States: Identity, origin, and evolution, J. Geophys. Res., 111, D14314, doi:10.1029/2005JD006601, 2006.

Ghigo, G., Maranzana, A., and Tonachini, G.: Combustion and atmospheric oxidation o hydrocarbons: Theoretical study of the methyl peroxyl self-reaction, J. Chem. Phys., 118, 23, 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., Matsunaga, A., and Ziemann, P.: Products and mechanism of secondary organic aerosol formation from reactions of linear alkenes with NO3 radicals, J. Phys. Chem., 109, 4312–4324, 2005.

Gómez-González, Y., Surratt, J. D., Cuyckens, F., Szmigielski, R., Vermeylen, R., Jaoui, M., Lewandowski, M., Offenberg, J. H., Kleindienst, T. E., Edney, E. O., Blockhuys, F., Van Alsenoy, C., Maenhaut, W. and Claeys, M.: Characterization of organosulfates from the photooxidation of isoprene and unsaturated fatty acids in ambient aerosol using liquid chromatography/(–) electrospray ionization mass spectrometry, J. Mass Spectrom., 43(3), 371–382, doi:10.1002/jms.1329, 2007.

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(D5), 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.

Heintz, F., Platt, U., Flentje, H., and Dubois, R.: Long-term observation of nitrate radicals at the tor station, Kap Arkona (Rugen), J. Geophys. Res., 101(D17), 22 891–22 910, 1996.

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, 2008. %

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. %Discuss., 7, 14 569–14 601, 2007.

Horowitz, L. W., Fiore, A. M., Milly, G. P., Cohen, R. C., Perring, A., Wooldridge, P. J., Hess, P.G., Emmons, L. K., and Lamarque, J.: Observational constraints on the chemistry of isoprene nitrates over the eastern United States, J. Geophys. Res., 112, D12S08, doi:10.1029/2006JD007747, 2007.

Iinuma, Y., Müller, C., Berndt, T., Böge, O., Claeys, M., and Herrmann, H.: Evidence for the existence of organosulfates from $\beta $-pinene ozonolysis in ambient secondary organic aerosol, Environ. Sci. Technol., 41, 6678–6683, 2007b.

Iinuma, Y., Müller, C., Böge, O., Gnauk, T., and Herrmann, H.: The formation of organic sulfate esters in the limonene ozonolysis secondary organic aerosol (SOA) under acidic conditions, Atmos. Environ., 41, 5571–5583, 2007a.

Jay, K. and Stieglitz, L.: The gas phase addition of NOx to olefins, Chemosphere, 19, 1939–1950, 1989.

Jayne, J. T., Leard, D. C., Zhang, X., Davidovits, P., Smith, K. A., Kolb, C. E., and Worsnop, D. W.: Development of an Aerosol Mass Spectrometer for size and composition analysis of submicron particles, Aerosol Sci. Technol., 33, 49–70, 2000.

Kan, C. S., Calvert, J. G., and Shaw, J. H.: Reactive channels of the CH3O2-CH3O2 reaction, J. Phys. Chem., 84, 3411–3417, 1980.

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.

Keywood, M. D., Varutbangkul, V., Bahreini, R., Flagan, R. C., and Seinfeld, J. H.: Secondary organic aerosol formation from the ozonolysis of cycloalkenes and related compounds, Environ. Sci. Technol., 38, 4157–4164, 2004.

Kirchner, F. and Stockwell, W. R.: Effect of peroxy radical reactions on the predicted concentrations of ozone, nitrogenous compounds, and radicals, J. Geophys. Res., 101(D15), 21 007–21 022, 1996.

Knopf, D. A., Mak, J., Gross, S., and Bertram, A. K.: Does atmospheric processing of saturated hydrocarbon surfaces by NO3 lead to volatilization?, Geophys. Res. Lett., 33, L17816, doi:10.1029/2006GL026884, 2006.

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-NOx conditions, J. Geophys. Res., 32, L18808, doi:10.1029/2005GL023637, 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, 2006.

Kwok, E. S. C., Aschmann, S. M., Arey, J., and Atkinson, R.: Product formation from the reaction of the NO3 radical with isoprene and rate constants for the reactions of methacrolein and methyl vinyl ketone with the NO3 radical, Inter. J. Chem. Kinet. 28, 925–934, 1996.

Liggio, J. and Li, S. M.: Organosulfate formation during the uptake of pinonaldehyde on acidic sulfate aerosols, Geophys. Res. Lett., 33, L13808, doi:10.1029/2006GL026079, 2006.

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, 2005.

Lightfoot, P. D., Cox, R..A., Crowley, J. N., Destriau, M. Hayman, G. D., Jenkin, M. E., Moortgat G. K., and Zabel, F.: Organic peroxy radicals – kinetics, spectroscopy and tropospheric chemistry, Atmos. Environ., 26, 1805–1961, 1992.

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.

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 NOx level on secondary organic aerosol (SOA) formation from the photooxidation of terpenes, Atmos. Chem. Phys., 7, 5159–5174, 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, 2007b.

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.

Niki, H, Maker, P. D., Savage, C. M., and Breitenbach L.P.: Fourier Transform Infrared studies of the self-reaction of CH3O$_2 $ radicals, J. Phys. Chem., 85, 877–881, 1981.

Niki, H, Maker, P. D., Savage, C. M., and Breitenbach L.P.: Fourier Transform Infrared studies of the self-reaction of C2H$_5$O$_2 $ radicals, J. Phys. Chem., 86, 3825–3829, 1982.

Noda, J., Nyman, G., and Langer S.: Kinetics of the gas-phase reaction of some unsaturated alcohols with the nitrate radical, J. Phys. Chem., 106, 945–951, 2002.

Odum, J. R., Hoffmann, T., Bowman, F., Collins, D., R. C. Flagan, R. C., and Seinfeld, J. H.: Gas/particle partitioning and secondary organic aerosol yields, Environ. Sci. Technol., 30, 2580–2585, 1996.

Odum, J. R., Jungkamp, T. P. W., Griffin, R. J., Flagan, R. C., and Seinfeld, J. H.: The atmospheric aerosol-forming potential of whole gasoline vapor, Science, 276, 96–99, 1997a.

Odum, J. R., Jungkamp, T. P. W., Griffin, R. J., Forstner, H. J. L., Flagan, R. C., and Seinfeld, J. H.: Aromatics, reformulated gasoline and atmospheric organic aerosol formation, Environ. Sci. Technol., 31, 1890–1897, 1997b.

Paulot, F., Crounse, J. D., Kjaergaard, H. G., Kroll, J. H., Seinfeld, J. H., and Wennberg, P. O.: Isoprene photooxidation mechanism: resonance channels and implications for the production of nitrates and acids, accepted, Atmos. Chem. Phys. Discuss., 2008.

Paulson, S. E. and Seinfeld, J. H.: Development and evaluation of a photooxidation mechanism for isoprene, J. Geophys. Res., 97(D18), 20 703–20 715, 1992.

Penkett, S. A., Burgess, R. A., Coe, H., Coll, I., Hov, Ø., Lindskog, A., Schmidbauer, N., Solberg, S., Roemer, M., Thijsse, T., Beck, J., and Reeves C. E.: Evidence for large average concentrations of the nitrate radical (NO$_3)$ in Western Europe from the HANSA hydrocarbon database, Atmos. Environ., 41, 3465–3478, 2007.

Platt, U. and Janssen, C.: Observation and role of the free radicals NO3, ClO, BrO and IO in the troposphere, Faraday Discuss., 100, 175–198, 1995.

Platt, U., Perner, D., Schroder, J., Kessler, C., and Toennissen, A.: The diurnal variation of NO3, J. Geophys. Res., 86, 11 965–11 970, 1981.

Rudich, Y., Donahue, N. M., and Mentel, T. F.: Aging of organic aerosol: Bridging the gap between laboratory and field studies, Annu. Rev. Phys. Chem., 58, 321–352, 2007.

Sharkey, T. D., Singsaas, E. L., Vanderveer, P. J., and Geron, C.: Field measurements of isoprene emission from trees in response to temperature and light, Tree Physiol., 16, 649–654, 1996.

Skov, H., Benter, Th., Schindler, R. N., Hjorth, J., and Restelli, G.: Epoxide formation in the reactions of the nitrate radical with 2,3-dimethyl-2-butene, cis- and trans-2-butene and isoprene, Atmos. Environ., 28, 1583–1592, 1994.

Skov, H., Hjorth, J., Lohse, C., Jensen, N. R. and Restelli, G.: Products and mechanisms of the reactions of the nitrate radical (NO$_3)$ with isoprene, 1,3-butadiene and 2,3-dimethyl-1,3-butadiene in air, Atmos. Environ., 26A(15), 2771–2783, 1992.

Smith, N., Plane, J. M. C., Nien, C. F., and Solomon, P. A.: Nighttime radical chemistry in the San-Joaquin Valley, Atmos. Environ., 29, 2887–2897, 1995.

Sorooshian, A., Brechtel F. J., Ma, Y. L., Weber R. J., Corless, A., Flagan, R. C., and Seinfeld, J. H.: Modeling and characterization of a particle-into-liquid sampler (PILS), Aerosol Sci. Technol., 40, 396–409, 2006.

Starn, T. K., Shepson, P. B., Bertman, S. B., Riemer, D. D., Zika, R. G. and Olszyna, K.: Nighttime isoprene chemistry at an urban-impacted forest site, J. Geophys. Res., 103(D17), 22 437–22 447, 1998.

Steinbacher, M., Dommen, J. Ordonez, C., Reimann, S., Gruebler, F. C., Staehelin, J., Andreani-Aksoyoglu, S., and Prevot, A. S. H.: Volatile organic compounds in the Po Bason. Part B: Biogenic VOCs, J. Atmos. Chem., 51, 293–315, 2005.

Stroud, C. A., Roberts, J. M., Williams E. J., Hereid, D., Angevine, W. M., Fehsenfeld, F. C., Wisthaler, A., Hansel, A., Martinez-Harder, M., Harder, H., Brune, W. H., Hoenninger, G., Stutz, J., and White, A. B.: Nighttime isoprene trends at an urban forested site during the 1999 Southern Oxidant Study, J. Geophys. Res., 107(D16), 4291, doi:10.1029/2001JD000959, 2002.

Su, T. and Chesnavich, W. J.: Parametrization of the ion–polar molecule collision rate constant by trajectory calculations, The Journal of Chemical Physics, 76, 5183, 1982.

Suh, I., Lei, W., and Zhang, R.: Experimental and theoretical studies of isoprene reaction with NO3, J. Phys. Chem., 105, 6471–6478, 2001.

Surratt, J. D., Kroll, J. H., Kleindienst, T. E., Edney, E. O., Claeys, M., Sorooshian, A., Ng, N. L., Offenberg, J. H., Lewandowski, M., Jaoui, M., Flagan, R. C., and Seinfeld, J. H.: Evidence for organosulfates in secondary organic aerosol, Environ. Sci. Technol., 41, 517–527, 2007a.

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, 2007b.

Surratt, J. D., Murphy, S. M., Kroll, J. H., Ng, N. L., Hildebrandt, L., Sorooshian, A., Szmigielski, R., Vermeylen, R., Maenhaut, W., Claeys, M., Flagan, R. C., and Seinfeld, J. H.: Chemical composition of secondary organic aerosol formed from the photooxidation of isoprene, J. Phys. Chem. A, 110, 9665–9690, 2006.

Szmigielski, R., Surratt, J. D., Vermeylen, R., Szmigielska, K., Kroll, J. H., Ng, N. L., Murphy, S. M., Sorooshian, A., Seinfeld, J. H., and Claeys, M.: Characterization of 2-methylglyceric acid oligomers in secondary organic aerosol formed from the photooxidation of isoprene using trimethylsilylation and gas chromatography/ion trap mass spectrometry, J. Mass Spectrom., 42, 101–116, 2007.

Tyndall, G. S., Cox, R. A., Granier, C., Lesclaux, R., Moortgat, G. K., Pilling, M. J., Ravishankara, A. R., and Wallington, T. J.: Atmospheric chemistry of small peroxy radicals, J. Geophys. Res., 106(D11), 12 157–12 182, 2001.

Tyndall, G. S., Wallington, T. J., and Ball, J. C.: FTIR product study of the reactions of CH3O2+CH3O2 and CH3O2+O3, J. Phys. Chem., 102, 2547–2554, 1998.

Vaughan, S. Canosa-Mas, C. E., Pfrang, C., Shallcross, D. E., Watson, L., and Wayne, R. P.: Kinetic studies of reactions of the nitrate radical (NO$_3)$ with peroxy radicals (RO$_2)$: an indirect source of OH at night? Phys. Chem. Chem. Phys., 8, 3749–3760, 2006.

von Friedeburg, C., Wagner, T., Geyer, A., Kaiser, N., Platt, U., Vogel, B. and Vogel, H.: Derivation of tropospheric NO3 profiles using off-axis differential optical absorption spectroscopy measurements during sunrise and comparison with simulations, J. Geophys. Res., 107(D13), 4168, doi:10.1029/2001JD000481, 2002.

Wallington, T. J., Dagaut, P., and Kurylo, M. J.: Ultraviolet absorption cross-sections and reaction kinetics and mechanisms for peroxy radicals in the gas phase, Chem. Rev., 92, 667–710, 1992.

Wallington, T. J., Gierczak, C. A., Ball, J. C., and Japar, S. M.: Fourier Transform Infrared studies of the self-reaction of C2H$_5$O$_2 $radicals in air at 295 K, Int. J. Chem. Kinet., 21, 1077–1089, 1989.

Werner, G., Kastler, J., Looser, R., and Ballschmiter, K.: Organic nitrates of isoprene as atmospheric trace compounds, Angew. Chem. Int. Ed., 38(11), 1634–1637, 1999.

Wu, S. L., Mickley, L. J., Jacob, D. J. Logan, J. A., Yantosca, R. M., and Rind, D.: Why are there large differences between models in global budgets of tropospheric ozone? J. Geophys. Res., 112(D5), D05302, doi:10.1029/2006JD007801, 2007.

Zhang, D. and Zhang, R.: Unimolecular decomposition of nitrooxyalkyl radicals from NO3-isoprene reaction, J. Chem. Phys., 116(22), 9721–9728, 2002.

Ziemann, P.: Evidence for low-volatility diacyl peroxides as a nucleating agent and major component of aerosol formed from reactions of O3 with cyclohexene and homologous compounds, J. Phys. Chem., 106, 4390–4402, 2002.