References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-10-7057-2010

Influence of relative humidity and temperature on the production of pinonaldehyde and OH radicals from the ozonolysis of α-pinene

Tillmann

¹ Hallquist

² Jonsson

Å. M.

² ⁵ Kiendler-Scharr

¹ Saathoff

³ Iinuma

⁴ Mentel

Th. F.

Institut für Chemie und Dynamik der Geosphäre 2, Forschungszentrum Jülich, 52425 Jülich, Germany

Department of Chemistry, Atmospheric Science, University of Gothenburg, 412 96 Gothenburg, Sweden

Institute for Meteorology and Climate Research, Forschungszentrum Karlsruhe, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany

Leibnitz Institute for Tropospheric Research, Permoserstr. 15, 04318 Leipzig, Germany

present address: IVL Swedish Environmental Research Institute Ltd, Aschebergsgatan 44, 411 33 Gothenburg, Sweden

03 08 2010

10 15 7057 7072

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The ozonolysis of α-pinene has been investigated under dry and humid conditions in the temperature range of 243–303 K. The results provided new insight into the role of water and temperature in the degradation mechanism of α-pinene and in the formation of secondary organic aerosols (SOA). The SOA yields were higher at humid conditions than at dry conditions. The water induced gain was largest for the lowest temperatures investigated (243 and 253 K). The increase in the SOA yields was dominated by water (and temperature) effects on the organic product distribution, whilst physical uptake of water was negligible. This will be demonstrated for the example of pinonaldehyde (PA) which was formed as a major product in the humid experiments with total molar yields of 0.30±0.06 at 303 K and 0.15±0.03 at 243 K. In the dry experiments the molar yields of PA were only 0.07±0.02 at 303 K and 0.02±0.02 at 253 K. The observed partitioning of PA as a function of the SOA mass present at 303 K limited the effective vapour pressure of pure PA pPA0 to the range of 0.01–0.001 Pa, 3–4 orders of magnitude lower than literature values. The corresponding mass partitioning coefficient was determined to KPA=0.005±0.004 m3 μg−1 and the total mass yield αPAtotal=0.37±0.08. At 303 K PA preferably stayed in the gas-phase, whereas at 253 K and 243 K it exclusively partitioned into the particulate phase. PA could thus account at least for half of the water induced gain in SOA mass at 253 K. The corresponding effect was negligible at 303 K because the PA preferably remained in the gas-phase. The yield of OH radicals, which were produced in the ozonolysis, was indirectly determined by means of the yield of cyclohexanone formed in the reaction of OH radicals with cyclohexane. OH yields of the α-pinene ozonolysis were determined to 0.67±0.17 for humid and 0.54±0.13 for dry conditions at 303 K, indicating a water dependent path of OH radical formation. For 253 and 243 K OH yields could be estimated to 0.5 with no significant difference between the dry and humid experiments. This is the first clear indication for OH radical formation by α-pinene ozonolysis at such low temperatures.

References 1

% vor jede Referenz 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 Worsnop, 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, doi:10.1016/j.jaerosci.2004.02.007, 2004.

Alvarado, A., Tuazon, E. C., Aschmann, S. M., Atkinson, R., and Arey, J.: Products of the gas-phase reactions of O(3P) atoms and O3 with $\alpha $-pinene and 1,2-dimethyl-1-cyclohexene, J. Geophys. Res.-Atmos., 103, 25541–25551, 1998.

Anglada, J. M., Aplincourt, P., Bofill, J. M., and Cremer, D.: Atmospheric Formation of OH Radicals and H2O2 from Alkene Ozonolysis under Humid Conditions, Chemphyschem, 3, 215–221, 2002.

Aschmann, S. M., Arey, J., and Atkinson, R.: OH radical formation from the gas-phase reactions of O3 with a series of terpenes, Atmos. Environ., 36, 4347–4355, 2002.

Atkinson, R., Aschmann, S. M., Arey, J., and Shorees, B.: Formation of OH Radicals in the Gas Phase Reactions of O3 with a Series of Terpenes, J. Geophys. Res.-Atmos., 97, 6065–6073, 1992.

Atkinson, R. and Arey, J.: Gas-phase tropospheric chemistry of biogenic volatile organic compounds: a review, Atmos. Environ., 37, S197–S219, 2003.

Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Rossi, M. J., and Troe, J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume I - gas phase reactions of Ox, HOx, NOx and SOx species, Atmos. Chem. Phys., 4, 1461–1738, doi:10.5194/acp-4-1461-2004, 2004.

Baker, J., Aschmann, S. M., Arey, J., and Atkinson, R.: Reactions of Stabilized Criegee Intermediates from the Gas-Phase Reactions of O3 with Selected Alkenes, Int. J. Chem. Kinet., 34, 73–85, 2001.

Berndt, T., Böge, O., and Stratmann, F.: Gas-phase ozonolysis of $\alpha $-pinene: gaseous products and particle formation, Atmos. Environ., 37, 3933–3945, doi:10.1016/s1352-2310(03)00501-6, 2003.

Bonn, B., Schuster, G., and Moortgat, G. K.: Influence of Water Vapor on the Process of New Particle Formation during Monoterpene Ozonolysis, J. Phys. Chem. A, 106, 2869–2881, doi:10.1021/jp012713p, 2002.

Brunekreef, B. and Forsberg, B.: Epidemiological evidence of effects of coarse airborne particles on health, Eur. Respir. J., 26, 309–318, 2005.

Cahill, T. M., Seaman, V. Y., Charles, M. J., Holzinger, R., and Goldstein, A. H.: Secondary organic aerosols formed from oxidation of biogenic volatile organic compounds in the Sierra Nevada Mountains of California, J. Geophys. Res.-Atmos., 111, D16312, doi:10.1029/2006jd007178, 2006.

Calogirou, A., Larsen, B. R., and Kotzias, D.: Gas-phase terpene oxidation products: a review, Atmos. Environ., 33, 1423–1439, 1999.

Calvert, J. G., Atkinson, R., Kerr, J. A., Madronich, S., Moortgat, G. K., Wallington, T. J., and Yarwood, G.: The mechanisms of atmospheric oxidation of the alkenes Oxford Univ. Press, New York, 552~pp., 2000.

Cocker, D. R., Clegg, S. L., Flagan, R. C., and Seinfeld, J. H.: The effect of water on gas-particle partitioning of secondary organic aerosol. Part I: $\alpha $-pinene/ozone system, Atmos. Environ., 35, 6049–6072, 2001.

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

Donahue, N. M., Hartz, K. E. H., Chuong, B., Presto, A. A., Stanier, C. O., Rosenhorn, T., Robinson, A. L., and Pandis, S. N.: Critical factors determining the variation in SOA yields from terpene ozonolysis: A combined experimental and computational study, Faraday Discuss., 130, 295–309, 2005.

Gautrois, M., and Koppmann, R.: Diffusion technique for the production of gas standards for atmospheric measurements, J. Chromatogr. A, 848, 239–249, 1999.

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, 1999.

Hakola, H., Arey, J., Aschmann, S. M., and Atkinson, R.: Product formation from the gas-phase reactions of radicals and O3 with a series of monoterpenes, J. Atmos. Chem., 18, 75–102, 1994.

Hallquist, M., Wängberg, I., and Ljungström, E.: Atmospheric Fate of Carbonyl Oxidation Products Originating from $\alpha $-Pinene and $\Delta ^3$-Carene: Determination of Rate of Reaction with OH and NO3 Radicals, UV Absorption Cross Sections, and Vapor Pressures, Environ. Sci. Technol., 31, 3166–3172, 1997.

Hallquist, M., Wenger, J. C., Baltensperger, U., Rudich, Y., Simpson, D., Claeys, M., Dommen, J., Donahue, N. M., George, C., Goldstein, A. H., Hamilton, J. F., Herrmann, H., Hoffmann, T., Iinuma, Y., Jang, M., Jenkin, M. E., Jimenez, J. L., Kiendler-Scharr, A., Maenhaut, W., McFiggans, G., Mentel, Th. F., Monod, A., Prévôt, A. S. H., Seinfeld, J. H., Surratt, J. D., Szmigielski, R., and Wildt, J.: The formation, properties and impact of secondary organic aerosol: current and emerging issues, Atmos. Chem. Phys., 9, 5155–5236, doi:10.5194/acp-9-5155-2009, 2009.

Hasson, A. S., Ho, A. W., Kuwata, K. T., and Paulson, S. E.: Production of stabilized Criegee intermediates and peroxides in the gas phase ozonolysis of alkenes 2. Asymmetric and biogenic alkenes, J. Geophys. Res.-Atmos., 106, 34143–34153, 2001.

Hasson, A. S., Chung, M. Y., Kuwata, K. T., Converse, A. D., Krohn, D., and Paulson, S. E.: Reaction of Criegee intermediates with water vapor - An additional source of OH radicals in alkene ozonolysis?, J. Phys. Chem. A, 107, 6176–6182, 10.1021/jp0346007, 2003.

Hatakeyama, S., Izumi, K., Fukuyama, T., and Akimoto, H.: Reactions of ozone with $\alpha $-pinene and $\beta $-pinene in air: yields of gaseous and particulate products, J. Geophys. Res.-Atmos., 94, 13013–13024, 1989.

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.-Atmos., 113, D05211, doi:10.1029/2007jd009092, 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.

Hoppel, W., Fitzgerald, J., Frick, G., Caffrey, P., Pasternack, L., Hegg, D., Gao, S., Leaitch, R., Shantz, N., Cantrell, C., Albrechcinski, T., Ambrusko, J., and Sullivan, W.: Particle formation and growth from ozonolysis of $\alpha $-pinene, J. Geophys. Res.-Atmos., 106, 27603–27618, 2001.

Iinuma, Y., Böge, O., Gnauk, T., and Herrmann, H.: Aerosol-chamber study of the $\alpha $-pinene/O3 reaction: influence of particle acidity on aerosol yields and products, Atmos. Environ., 38, 761–773, 2004.

IPCC: Climate change 2007: The Physical Science Basis, University Press: Cambridge, Cambridge, 2007.

IUPAC Subcommittee for Gas Kinetic Data Evaluation, Data sheet Ox_VOC3_O3, available online at: http://www.iupac-kinetic.ch.cam.ac.uk/datasheets/pdf/Ox_VOC3_O3_alkene.pdf, (last access July 2010), 2005.

Jayne, J. T., Leard, D. C., Zhang, X. F., Davidovits, P., Smith, K. A., Kolb, C. E., and Worsnop, D. R.: Development of an Aerosol Mass Spectrometer for Size and Composition Analysis of Submicron Particles, Aerosol. Sci. Tech., 33, 49–70, 2000.

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, doi:10.5194/acp-4-1741-2004, 2004.

Jimenez, J. L., Jayne, J. T., Shi, Q., Kolb, C. E., Worsnop, D. R., Yourshaw, I., Seinfeld, J. H., Flagan, R. C., Zhang, X. F., Smith, K. A., Morris, J. W., and Davidovits, P.: Ambient aerosol sampling using the Aerodyne Aerosol Mass Spectrometer, J. Geophys. Res.-Atmos., 108, 8425, doi:10.1029/2001jd001213, 2003.

Johnson, D. and Marston, G.: The gas-phase ozonolysis of unsaturated volatile organic compounds in the troposphere, Chem. Soc. Rev., 37, 699–716, 2008.

Jonsson, Å. M., Hallquist, M., and Ljungström, E.: Impact of Humidity on the Ozone Initiated Oxidation of Limonene, $\Delta ^3$-Carene, and $\alpha $-Pinene, Environ. Sci. Technol., 40, 188–194, 2006.

Jonsson, Å. M., Hallquist, M., and Saathoff, H.: Volatility of secondary organic aerosols from the ozone initiated oxidation of a-pinene and limonene, J. Aerosol Sci., 38, 843–852, doi:10.1016/j.jaerosci.2007.06.008, 2007.

Jonsson, Å. M., Hallquist, M., and Ljungstr�m, E.: The effect of temperature and water on secondary organic aerosol formation from ozonolysis of limonene, $\Delta ^3$-carene and α-pinene, Atmos. Chem. Phys., 8, 6541–6549, doi:10.5194/acp-8-6541-2008, 2008a.

Jonsson, Å. M., Hallquist, M., and Ljungström, E.: Influence of OH Scavenger on the Water Effect on Secondary Organic Aerosol Formation from Ozonolysis of Limonene, $\Delta ^3$-Carene, and $\alpha $-Pinene, Environ. Sci. Technol., 42, 5938–5944, 2008b.

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, doi:10.5194/acp-5-1053-2005, 2005.

Kavouras, I. G., Mihalopoulos, N., and Stephanou, E. G.: Formation of atmospheric particles from organic acids produced by forests, Nature, 395, 683–686, 1998.

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 10.1029/2005jd006437, 2006.

Liao, H., Chen, W. T., and Seinfeld, J. H.: Role of climate change in global predictions of future tropospheric ozone and aerosols, J. Geophys. Res.-Atmos., 111, D12304, doi:10.1029/2005jd006852, 2006.

Lindinger, W., Hansel, A., and Jordan, A.: Proton-transfer-reaction mass spectrometry (PTR-MS): on-line monitoring of volatile organic compounds at pptv levels, Chem. Soc. Rev., 27, 347–354, 1998.

Ma, Y., Willcox, T. R., Russell, A. T., and Marston, G.: Pinic and pinonic acid formation in the reaction of ozone with $\alpha $-pinene, Chem. Commun., 15, 1328–1330, 2007.

Northcross, A. L. and Jang, M.: Heterogeneous SOA yield from ozonolysis of monoterpenes in the presence of inorganic acid, Atmos. Environ., 41, 1483–1493, 2007.

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.

Pathak, R. K., Stanier, C. O., Donahue, N. M., and Pandis, S. N.: Ozonolysis of $\alpha $-pinene at atmospherically relevant concentrations: Temperature dependence of aerosol mass fractions (yields), J. Geophys. Res.-Atmos., 112, D03201, doi:10.1029/2006JD007436, 2007.

Pio, C., Alves, C., and Duarte, A.: Organic components of aerosols in a forested area of central Greece, Atmos. Environ., 35, 389–401, 2001.

Plewka, A., Gnauk, T., Brüggemann, E., and Herrmann, H.: Biogenic contributions to the chemical composition of airborne particles in a coniferous forest in Germany, Atmos. Environ., 40, S103–S115, 2006.

Pöschl, U.: Atmospheric Aerosols: Composition, Transformation, Climate and Health Effects, Angew. Chem. Int. Edit., 44, 7520–7540, 10.1002/anie.200501122, 2005.

Presto, A. A. and Donahue, N. M.: Investigation of $\alpha $-Pinene + Ozone Secondary Organic Aerosol Formation at Low Total Aerosol Mass, Environ. Sci. Technol., 40, 3536–3543, doi:10.1021/es052203z, 2006.

Saathoff, H., Möhler, O., Schurath, U., Kamm, S., Dippel, B., and Mihelcic, D.: The AIDA soot aerosol characterisation campaign 1999, J. Aerosol Sci., 34, 1277–1296, 10.1016/s0021-8502(03)00363-x, 2003.

Saathoff, H., Naumann, K.-H., Möhler, O., Jonsson, Å. M., Hallquist, M., Kiendler-Scharr, A., Mentel, Th. F., Tillmann, R., and Schurath, U.: Temperature dependence of yields of secondary organic aerosols from the ozonolysis of α-pinene and limonene, Atmos. Chem. Phys., 9, 1551–1577, doi:10.5194/acp-9-1551-2009, 2009.

Schwarze, P. E., Ovrevik, J., Lag, M., Refsnes, M., Nafstad, P., Hetland, R. B., and Dybing, E.: Particulate matter properties and health effects: consistency of epidemiological and toxicological studies, Hum. Exp. Toxicol., 25, 559–579, doi:10.1177/096032706072520, 2006.

Seinfeld, J. H. and Pandis, S. N.: Atmospheric chemistry and physics : from air pollution to climate change, John Wiley & Sons, Inc., New York, 1326 pp., 1998.

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.

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 α-pinene, Atmos. Chem. Phys., 8, 2073–2088, doi:10.5194/acp-8-2073-2008, 2008.

Sioutas, C., Delfino, R. J., and Singh, M.: Exposure Assessment for Atmospheric Ultrafine Particles (UFPs) and Implications in Epidemiologic Research, Environ. Health Persp., 113, 947–955, doi:10.1289/ehp.7939, 2005.

Story, P. R., Hall, T. K., Morrison, W. H., and Farine, J. C.: Thermal Decomposition of Ozonides, Tetrahedron Lett., 52, 5397–5400, 1968.

Tillmann, R., Saathoff, H., Brauers, T., Kiendler-Scharr, A., and Mentel, T. F.: Temperature dependence of the rate coefficient for the α-pinene reaction with ozone in the range between 243 K and 303 K, Phys. Chem. Chem. Phys., 11, 2323–2328, doi:10.1039/b813407c, 2009.

Varutbangkul, V., Brechtel, F. J., Bahreini, R., Ng, N. L., Keywood, M. D., Kroll, J. H., Flagan, R. C., Seinfeld, J. H., Lee, A., and Goldstein, A. H.: Hygroscopicity of secondary organic aerosols formed by oxidation of cycloalkenes, monoterpenes, sesquiterpenes, and related compounds, Atmos. Chem. Phys., 6, 2367–2388, doi:10.5194/acp-6-2367-2006, 2006.

von Hessberg, C., von Hessberg, P., P�schl, U., Bilde, M., Nielsen, O. J., and Moortgat, G. K.: Temperature and humidity dependence of secondary organic aerosol yield from the ozonolysis of β-pinene, Atmos. Chem. Phys., 9, 3583–3599, doi:10.5194/acp-9-3583-2009, 2009.

Warscheid, B. and Hoffmann, T.: On-line measurements of $\alpha $-pinene ozonolysis products using an atmospheric pressure chemical ionisation ion-trap mass spectrometer, Atmos. Environ., 35, 2927–2940, 2001.

Wayne, R.: Chemistry of Atmospheres, 2nd ed., Oxford University Press, Oxford, 1991.

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.

Went, F. W.: Blue hazes in the atmosphere, Nature, 187, 641–643, 1960.

Yokouchi, Y. and Ambe, Y.: Aerosols formed from the chemical reaction of monoterpenes and ozone, Atmos. Environ., 19, 1271–1276, 1985.

Yu, J. Z., Cocker, D. R., Griffin, R. J., Flagan, R. C., and Seinfeld, J. H.: Gas-Phase Ozone Oxidation of Monoterpenes: Gaseous and Particulate Products, J. Atmos. Chem., 34, 207–258, 1999a.

Yu, J. Z., Griffin, R. J., Cocker, D. R., Flagan, R. C., Seinfeld, J. H., and Blanchard, P.: Observation of gaseous and particulate products of monoterpene oxidation in forest atmospheres, Geophys. Res. Lett., 26, 1145–1148, 1999b.

Zhang, D. and Zhang, R.: Ozonolysis of $\alpha $-pinene and $\beta $-pinene: Kinetics and mechanism, J. Chem. Phys., 122, 114308, doi:10.1063/1.1862616, 2005.