Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 9 1 2009 10.5194/acpd-9-3041-2009 http://www.atmos-chem-phys-discuss.net/9/3041/2009/ http://www.atmos-chem-phys-discuss.net/9/3041/2009/acpd-9-3041-2009.html http://www.atmos-chem-phys-discuss.net/9/3041/2009/acpd-9-3041-2009.pdf 3041 3094 2009-01-29 Photochemical production of aerosols from real plant emissions Th. F. Mentel t.mentel@fz-juelich.de J. Wildt A. Kiendler-Scharr E. Kleist R. Tillmann M. Dal Maso R. Fisseha Th. Hohaus H. Spahn R. Uerlings R. Wegener P. T. Griffiths E. Dinar Y. Rudich A. Wahner Institute for Chemistry and Dynamics of the Geosphere, Institute 2: Troposphere, Research Centre Jülich, 52425 Jülich, Germany Institute for Chemistry and Dynamics of the Geosphere, Institute 3: Phytosphere, Research Centre Jülich, 52425 Jülich, Germany Centre for Atmospheric Science, Department of Chemistry, Lensfield Road, University of Cambridge, Cambridge, CB2 1EW, UK Department of Environmental Sciences, Weizmann Institute, Rehovot 76100, Israel By emission of volatile organic compounds (VOC) which on oxidation form secondary organic aerosols (SOA) the vegetation is coupled to atmosphere and climate. New particle formation from tree emissions was investigated in a new setup: a plant chamber coupled to a reaction chamber for oxidizing the plant emissions and for forming SOA. The boreal tree species birch, pine, and spruce were studied and α-pinene was used as reference compound. Under the experimental conditions OH radicals were essential for inducing new particle formation, although O₃ (≤80 ppb) was always present and a part of the monoterpenes and the sesquiterpenes reacted already with ozone before OH was generated. Formation rates of 3 nm particles were linearly related to the carbon mixing ratios of the VOC, as were the maximum observed volume and the condensational growth rates. The threshold of new particle formation was lower for the tree emissions than for α-pinene. It was lowest for birch with the largest fraction of oxygenated VOC (OVOC) suggesting that OVOC may play a pivotal role in new particle formation. Incremental mass yields were ≈5% for pine, spruce and α-pinene, and ≈10% for birch. α-Pinene was a good model compound to describe the yield and the growth of SOA particles from coniferous emissions. The mass fractional yields agreed well with observations for boreal forests. Despite our somewhat enhanced VOC and OH concentrations our results may thus be up-scaled to eco-system level. Using the mass fractional yields observed for the tree emissions and weighting them with the abundance of the respective trees in boreal forests we calculate SOA mass concentrations which agree within 6% with field observations. For a future VOC increase of 50% we predict a particle mass increase due to SOA of 19% assuming today's mass contribution of pre-existing aerosol. Allan, J. D., Alfarra, M. R., Bower, K. N., Coe, H., Jayne, J. T., Worsnop, D. R., Aalto, P. P., Kulmala, M., Hyötyläinen, T., Cavalli, F., and Laaksonen, A.: Size and composition measurements of background aerosol and new particle growth in a Finnish forest during QUEST 2 using an Aerodyne Aerosol Mass Spectrometer, Atmos. Chem. Phys., 6, 315–327, 2006. Atkinson, R. and Arey, J.: Gas-phase tropospheric chemistry of biogenic volatile organic compounds: A review, Atmos. Environ., 37, S197–S219, 2003. Atkinson, R. and Aschmann, S. M.: OH radical production from the gas-phase reactions of O₃ with a series of alkenes under atmospheric conditions, Environ. Sci. Technol., 27, 1357–1363, 1993. Bahreini, R., Keywood, M. D., Ng, N. L., Varutbangkul, V., Gao, S., Flagan, R. C., Seinfeld, J. H., Worsnop, D. R., and Jimenez, J. L.: Measurements of secondary organic aerosol from oxidation of cycloalkenes, terpenes, and m-xylene using an Aerodyne aerosol mass spectrometer, Environ. Sci. Technol., 39, 5674–5688, 2005. Barth, M., McFadden, J. P., Sun, J., Wiedinmyer, C., Chuang, P., Collins, D., Griffin, R., Hannigan, M., Karl, T., Kim, S.-W., Lasher-Trapp, S., Levis, S., Litvak, M., Mahowald, N., Moore, K. S. N., Nemitz, E., Nenes, A., Potosnak, M., Raymond, T. M., Smith, J., Still, C., and Stroud, C.: Coupling between land ecosystems and the atmospheric hydrologic cycle through biogenic aerosol pathways, B. Am. Meteorol. Soc., 1738–1742, 2005. Bilde, M., Svenningsson, B., Monster, J., and Rosenorn, T.: Even-odd alternation of evaporation rates and vapor pressures of C₃-C$_9$ dicarboxylic acid aerosols, Environ. Sci. Technol., 37, 1371–1378, 2003. Bonn, B. and Moorgat, G. K.: New particle formation during α- and β-pinene oxidation by O₃, OH and NO₃, and the influence of water vapour: particle size distribution studies, Atmos. Chem. Phys., 2, 183–196, 2002. Bonn, B. and Moortgat, G. K.: Sesquiterpene ozonolysis: Origin of atmospheric new particle formation from biogenic hydrocarbons, Geophys. Res. Lett., 30, 1585, doi:10.1029/2003GL017000, 2003. Boy, M., Kulmala, M., Ruuskanen, T. M., Pihlatie, M., Reissell, A., Aalto, P. P., Keronen, P., Dal Maso, M., Hellen, H., Hakola, H., Jansson, R., Hanke, M., and Arnold, F.: Sulphuric acid closure and contribution to nucleation mode particle growth, Atmos. Chem. Phys., 5, 863–878, 2005. Calogirou, A., Larsen, B. R., and Kotzias, D.: Gas-phase terpene oxidation products: A review, Atmos. Environ., 33, 1423–1439, 1999. Carrasco, N., Doussin, J. F., O'Connor, M., Wenger, J. C., Picquet-Varrault, B., Durand-Jolibois, R., and Carlier, P.: Simulation chamber studies of the atmospheric oxidation of 2-methyl-3-buten-2-ol: Reaction with hydroxyl radicals and ozone under a variety of conditions, J. Atmos. Chem., 56, 33–55, 2007. Ciccioli, P., Brancaleoni, E., Frattoni, M., Cecinato, A., and Brachetti, A.: Ubiquitous occurrence of semivolatile carbonyl-compounds in tropospheric samples and their possible sources, Atmos. Environ., 27, 1891–1901, 1993. 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. Croft, K. P. C., Juttner, F., and Slusarenko, A. J.: Volatile products of the lipoxygenase pathway evolved from phaseolus-vulgaris (l) leaves inoculated with pseudomonas-syringae pv-phaseolicola, Plant Physiol., 101, 13–24, 1993. Dal Maso, M., Kulmala, M., Lehtinen, K. E. J., Makela, J. M., Aalto, P., and O'Dowd, C. D.: Condensation and coagulation sinks and formation of nucleation mode particles in coastal and boreal forest boundary layers, J. Geophys. Res., 107, 8097, doi:10.1029/2001JD001053, 2002. 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. Denman, K. L., Brasseur, G., Chidthaisong, A., Ciais, P., Cox, P. M., Dickinson, R. E., Hauglustaine, D., Heinze, C., Holland, E., Jacob, D., Lohmann, U., Ramachandran, S., da Silva Dias, P. L., Wofsy, S. C., and Zhang, X.: Couplings between changes in the climate system and biogeochemistry, in: Climate change 2007: The physical science basis. Contribution of 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, New York, USA, 2007. 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, 2006. Folkers, A.: Sauerstoffhaltige flüchtige organische Verbindungen in der Troposphäre: Entwicklung und Anwendung einer gaschromatographischen Nachweismethode, Universität zu Köln, Köln, Germany, 2002. Folkers, A., Hüve, K., Ammann, C., Dindorf, T., Kesselmeier, J., Kleist, E., Kuhn, U., Uerlings, R., and Wildt, J.: Methanol emissions from deciduous tree species: dependence on temperature and light intensity, Plant Biology, 10, 65–75, 2008. Fu, T. M., Jacob, D. J., Wittrock, F., Burrows, J. P., Vrekoussis, M., and Henze, D. K.: Global budgets of atmospheric glyoxal and methylglyoxal, and implications for formation of secondary organic aerosols, J. Geophys. Res., 113, D15303, doi:10.1029/2007JD009505, 2008. Haapanala, S., Rinne, J., Hakola, H., Hellén, H., Laakso, L., Lihavainen, H., Janson, R., O'Dowd, C., and Kulmala, M.: Boundary layer concentrations and landscape scale emissions of volatile organic compounds in early spring, Atmos. Chem. Phys., 7, 1869–1878, 2007. Hakola, H., Tarvainen, V., Laurila, T., Hiltunen, V., Hellen, H., and Keronen, P.: Seasonal variation of voc concentrations above a boreal coniferous forest, Atmos. Environ., 37, 1623–1634, 2003. 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. Healy, R. M., Wenger, J. C., Metzger, A., Duplissy, J., Kalberer, M., and Dommen, J.: Gas/particle partitioning of carbonyls in the photooxidation of isoprene and 1,3,5-trimethylbenzene, Atmos. Chem. Phys., 8, 3215–3230, 2008. Heiden, A. C., Hoffmann, T., Kahl, J., Kley, D., Klockow, D., Langebartels, C., Mehlhorn, H., Sandermann, H., Schraudner, M., Schuh, G., and Wildt, J.: Emission of volatile organic compounds from ozone-exposed plants, Ecol. Appl., 9, 1160–1167, 1999. Heiden, A. C., Kobel, K., Langebartels, C., Schuh-Thomas, G., and Wildt, J.: Emissions of oxygenated volatile organic compounds from plants – Part I: Emissions from lipoxygenase activity, J. Atmos. Chem., 45, 143–172, 2003. Hüve, K., Christ, M. M., Kleist, E., Uerlings, R., Niinemets, U., Walter, A., and Wildt, J.: Simultaneous growth and emission measurements demonstrate an interactive control of methanol release by leaf expansion and stomata, J. Exp Bot., 58, 1783–1793, 2007. 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. Joutsensaari, J., Loivamäki, M., Vuorinen, T., Miettinen, P., Nerg, A.-M., Holopainen, J. K., and Laaksonen, A.: Nanoparticle formation by ozonolysis of inducible plant volatiles, Atmos. Chem. Phys., 5, 1489–1495, 2005. Kerminen, V. M., Lihavainen, H., Komppula, M., Viisanen, Y., and Kulmala, M.: Direct observational evidence linking atmospheric aerosol formation and cloud droplet activation, Geophys. Res. Lett., 32, L14803, doi:10.1029/2005GL023130, 2005. Korhonen, H., Lehtinen, K. E. J., Pirjola, L., Napari, I., Vehkamaki, H., Noppel, M., and Kulmala, M.: Simulation of atmospheric nucleation mode: A comparison of nucleation models and size distribution representations, J. Geophys. Res., 108, 4471, doi:10.1029/2002JD003305, 2003. Kostenidou, E., Pathak, R. K., and Pandis, S. N.: An algorithm for the calculation of secondary organic aerosol density combining ams and smps data, Aerosol. Sci. Tech., 41, 1002–1010, 2007. 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, 2008. Kuhn, U., Andreae, M. O., Ammann, C., Araújo, A. C., Brancaleoni, E., Ciccioli, P., Dindorf, T., Frattoni, M., Gatti, L. V., Ganzeveld, L., Kruijt, B., Lelieveld, J., Lloyd, J., Meixner, F. X., Nobre, A. D., Pöschl, U., Spirig, C., Stefani, P., Thielmann, A., Valentini, R., and Kesselmeier, J.: Isoprene and monoterpene fluxes from Central Amazonian rainforest inferred from tower-based and airborne measurements, and implications on the atmospheric chemistry and the local carbon budget, Atmos. Chem. Phys., 7, 2855–2879, 2007. Kulmala, M.: How particles nucleate and grow, Science, 302, 1000–1001, 2003. Kulmala, M., Dal Maso, M., Makela, J. M., Pirjola, L., Vakeva, M., Aalto, P., Miikkulainen, P., Hameri, K., and O'Dowd, C. D.: On the formation, growth and composition of nucleation mode particles, Tellus B, 53, 479–490, 2001. Kulmala, M., Vehkamaki, H., Petajda, T., Dal Maso, M., Lauri, A., Kerminen, V. M., Birmili, W., and McMurry, P. H.: Formation and growth rates of ultrafine atmospheric particles: A review of observations, J. Aerosol Sci., 35, 143–176, 2004. Laaksonen, A., Kulmala, M., O'Dowd, C. D., Joutsensaari, J., Vaattovaara, P., Mikkonen, S., Lehtinen, K. E. J., Sogacheva, L., Dal Maso, M., Aalto, P., Petäjä, T., Sogachev, A., Yoon, Y. J., Lihavainen, H., Nilsson, D., Facchini, M. C., Cavalli, F., Fuzzi, S., Hoffmann, T., Arnold, F., Hanke, M., Sellegri, K., Umann, B., Junkermann, W., Coe, H., Allan, J. D., Alfarra, M. R., Worsnop, D. R., Riekkola, M. -L., Hyötyläinen, T., and Viisanen, Y.: The role of VOC oxidation products in continental new particle formation, Atmos. Chem. Phys., 8, 2657–2665, 2008. Lathiere, J., Hauglustaine, D. A., De Noblet-Ducoudre, N., Krinner, G., and Folberth, G. A.: Past and future changes in biogenic volatile organic compound emissions simulated with a global dynamic vegetation model, Geophys. Res. Lett., 32, L20818, doi:10.1029/2005GL024164, 2005. Lindfors, V. and Laurila, T.: Biogenic volatile organic compound (VOC) emissions from forests in Finland, Boreal Environ. Res., 5, 95–113, 2000. Lyubovtseva, Y. S., Sogacheva, L., Dal Maso, M., Bonn, B., Keronen, P., and Kulmala, M.: Seasonal variations of trace gases, meteorological parameters, and formation of aerosols in boreal forest, Boreal Environ. Res., 10, 493–510, 2005. McFiggans, G., Coe, H., Burgess, R., Allan, J., Cubison, M., Alfarra, M. R., Saunders, R., Saiz-Lopez, A., Plane, J. M. C., Wevill, D., Carpenter, L., Rickard, A. R., and Monks, P. S.: Direct evidence for coastal iodine particles from Laminaria macroalgae – linkage to emissions of molecular iodine, Atmos. Chem. Phys., 4, 701–713, 2004. 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. 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, 2007a. Pathak, R. K., Stanier, C. O., Donahue, N. M., and Pandis, S. N.: Ozonolysis of α-pinene at atmospherically relevant concentrations: Temperature dependence of aerosol mass fractions (yields), J. Geophys. Res., 112, D03201, doi:10.1029/2006JD007436, 2007b. Paulson, S. E., Chung, M., Sen, A. D., and Orzechowska, G.: Measurement of OH radical formation from the reaction of ozone with several biogenic alkenes, J. Geophys. Res., 103, 25533–25539, 1998. Paulson, S. E., Flagan, R. C., and Seinfeld, J. H.: Atmospheric photooxidation of isoprene, 2. The ozone-isoprene reaction, Int. J. Chem. Kinet., 24, 103–125, 1992. Pinto, D. M., Tiiva, P., Miettinen, P., Joutsensaari, J., Kokkola, H., Nerg, A. M., Laaksonen, A., and Holopainen, J. K.: The effects of increasing atmospheric ozone on biogenic monoterpene profiles and the formation of secondary aerosols, Atmos. Environ., 41, 4877–4887, 2007. 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. 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 a-pinene and limonene, Atmos. Chem. Phys. Discuss., 8, 15595–15664, 2008. Schimang, R., Folkers, A., Kleffmann, J., Kleist, E., Miebach, M., and Wildt, J.: Uptake of gaseous nitrous acid (HONO) by several plant species, Atmos. Environ., 40, 1324–1335, 2006. Schuh, G., Heiden, A. C., Hoffmann, T., Kahl, J., Rockel, P., Rudolph, J., and Wildt, J.: Emissions of volatile organic compounds from sunflower and beech: Dependence on temperature and light intensity, J. Atmos. Chem., 27, 291–318, 1997. Seco, R., Penuelas, J., and Filella, I.: Short-chain oxygenated VOCs: Emission and uptake by plants and atmospheric sources, sinks, and concentrations, Atmos. Environ., 41, 2477–2499, 2007. Spirig, C., Neftel, A., Ammann, C., Dommen, J., Grabmer, W., Thielmann, A., Schaub, A., Beauchamp, J., Wisthaler, A., and Hansel, A.: Eddy covariance flux measurements of biogenic VOCs during ECHO 2003 using proton transfer reaction mass spectrometry, Atmos. Chem. Phys., 5, 465–481, 2005. Tarvainen, V., Hakola, H., Rinne, J., Hellen, H., and Haapanala, S.: Towards a comprehensive emission inventory of terpenoids from boreal ecosystems, Tellus B, 59, 526–534, 2007. Tillmann, R., Hallquist, M., Iinuma, Y., Jonsson, A. M., Kiendler-Scharr, A., Saathoff, H., and Mentel, T. F.: Water and temperature dependence of pinonaldehyde and OH yields from ozonolyis of a-pinene, in preparation, 2009. Tsigaridis, K. and Kanakidou, M.: Secondary organic aerosol importance in the future atmosphere, Atmos. Environ., 41, 4682–4692, 2007. Tunved, P., Hansson, H. C., Kerminen, V. M., Strom, J., Dal Maso, M., Lihavainen, H., Viisanen, Y., Aalto, P. P., Komppula, M., and Kulmala, M.: High natural aerosol loading over boreal forests, Science, 312, 261–263, 2006. Tunved, P., Stroem, J., Kulmala, M., Kerminen, V.-M., Dal Maso, M., Svenningson, B., Lunder, C., and Hansson, H.-C.: The natural aerosol over northern europe and its relation to anthropogenic emissions – implications of important climate feedbacks, Tellus B, 60, 473–484, 2008. VanReken, T. M., Greenberg, J. P., Harley, P. C., Guenther, A. B., and Smith, J. N.: Direct measurement of particle formation and growth from the oxidation of biogenic emissions, Atmos. Chem. Phys., 6, 4403–4413, 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. Went, F. W.: Blue hazes in the atmosphere, Nature, 187, 641–643, 1960. Wildt, J., Kley, D., Rockel, A., Rockel, P., and Segschneider, H. J.: Emission of NO from several higher plant species, J. Geophys. Res., 102, 5919–5927, 1997. Wildt, J., Kobel, K., Schuh-Thomas, G., and Heiden, A. C.: Emissions of oxygenated volatile organic compounds from plants – part ii: Emissions of saturated aldehydes, J. Atmos. Chem., 45, 173–196, 2003.