Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 7 11 2007 10.5194/acp-7-2893-2007 http://www.atmos-chem-phys.net/7/2893/2007/ http://www.atmos-chem-phys.net/7/2893/2007/acp-7-2893-2007.html http://www.atmos-chem-phys.net/7/2893/2007/acp-7-2893-2007.pdf 2893 2916 2007-06-11 Ambient sesquiterpene concentration and its link to air ion measurements B. Bonn boris.bonn@helsinki.fi A. Hirsikko H. Hakola T. Kurtén L. Laakso M. Boy M. Dal Maso J. M. Mäkelä M. Kulmala Department of Physical Sciences, University of Helsinki, Helsinki, Finland Finnish Meteorological Institute, Helsinki, Finland National Center of Atmospheric Research, Boulder, CO, USA Tampere University of Technology, Institute of Physics, Tampere, Finland now at: Estonian University of Life Sciences, Department of Plant Physiology, Tartu, Estonia Ambient air ion size distributions have been measured continuously at the Finnish boreal forest site in Hyytiälä since spring 2003. In general, these measurements show a maximum of air ions below 1.0 nm in diameter. But this physical characterization does not provide any information about the ion's chemical composition, which is one key question regarding the explanation of nucleation events observed. In this study we propose a link of the observed maximum of negative air ions between 0.56 and 0.75 nm to the so-called stabilised Criegee biradical, formed in the reaction of biogenic sesquiterpenes with ozone and predominantly destroyed by its reaction with ambient water vapour. Calculations of the electron and proton affinities of 120 kJ mol^−1 (1.24 eV) and of 960 kJ mol^−1 support this link. Other possible candidates such as sulphuric acid derived clusters are unable to explain the observations made. By using this approach, we are able to calculate the ambient concentration of sesquiterpenes at the air ion instrument inlet with a high time resolution on the daily and seasonal scale. The estimated concentration is found to reveal the same seasonal pattern as emission measurements conducted at shoot level. As expected for biogenic VOCs, the concentration is obtained highest during summer (maximum values of about 100 pptv) and smallest during winter (minimum less than 1 pptv). Because of the sesquiterpenes high reactivity and its low ambient concentrations, this approach can be a first step in understanding their emission and their impact on atmospheric chemistry in more detail. The findings presented are highly relevant for emission budgets too, since boreal forests are extended over large areas of the globe. Atkins, P. and de Paula, J.: Atkins' physical chemistry, 7th edit., Oxford Univ. Press., Oxford, 2002. 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 II – reactions of organic species, Atmos. Chem. Phys., 6, 3625–4055, 2006. Becke, A. D.: Density-functional thermochemistry. III. The role of exact exchange, J. Chem. Phys., 98, 5648–5652, 1993. Boy, M., Kulmala, M., Ruuskanen, T M., Pihlahtie, 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. Bäck, J., Hari, P., Hakola, H., Juurola, E., and Kulmala, M.: Dynbamics of monoterpene emissions in Pinus sylvestris during early spring, Boreal Environ. Res., 10, 409–424, 2005. CRC Handbook: CRC Handbook of chemistry and physics, edited by: Linde, D R., CRC press, Boca Raton, 1998. Criegee, R.: Mechanismus der Ozonolyse. Angew. Chem., 87, 765–771, 1975. Dal Maso, M., Kulmala, M., Riipinen, I., Wagner, R., Hussein, T., Aalto, P P., and Lehtinen, K E J.: Formation and growth of fresh atmospheric aerosols: eight years of aerosol size distribution data from SMEAR II, Hyytiälä, Finland, Boreal Environ. Res., 10, 323–336, 2005. Davidson, J A., Fehsenfeld, F C., and Howard, J C.: The heats of formation of \chemNO_3^- and \chemNO_3^- association complexes with \chemHNO_3 and HBr, Int. J. Chem. Kinet., 9, 17–29, 1977. Eisele, F L. and Tanner, D J.: Identification of ons in continental air. J. Geophys. Res., 95(D12), 20 539–20 550, 1990. Eisele, F L., Lovejoy, E R., Kosciuch, E., Moore, K F., Mauldin III, R L., Smith, J N., McMurry, P H., and Iida, K.: Negative atmospheric ions and their potential role in ion-induced nucleation, J. Geophys. Res., 111, D04305, doi:10.1029/2005JD006568, 2006. Ferguson, E E. and Arnold, F.: Ion chemistry of the stratosphere, Accounts Chem. Res., 14, 327–334, 1981. Foresman, J. B. and Frisch, \AE.: Exploring Chemistry with Electronic Structure Methods, 2nd edition, Gaussian, Inc., Wallingford CT, U.S., 1996. Friedlander, S K.: Smoke, dust and haze, 2nd edit., Oxford Univ. Press., Oxford, 2000. Frisch, M J., Trucks, G W., Schlegel, H B., Scuseria, G E., Robb, M A., Cheeseman, J R., Montgomery, Jr., J A., Vreven, T., Kudin, K N., Burant, J C., Millam, J M., Iyengar, S S., Tomasi, J., Barone, V., Mennucci, B., Cossi, M., Scalmani, G., Rega, N., Petersson, G A., Nakatsuji, H., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Klene, M., Li, X., Knox, J E., Hratchian, H P., Cross, J B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R E., Yazyev, O., Austin, A J., Cammi, R., Pomelli, C., Ochterski, J W., Ayala, P Y., Morokuma, K., Voth, G A., Salvador, P., Dannenberg, J J., Zakrzewski, V G., Dapprich, S., Daniels, A D., Strain, M C., Farkas, O., Malick, D K., Rabuck, A D., Raghavachari, K., Foresman, J B., Ortiz, J V., Cui, Q., Baboul, A G., Clifford, S., Cioslowski, J., Stefanov, B B., Liu, G., Liashenko, A., Piskorz, P., Komaromi, I., Martin, R L., Fox, D J., Keith, T., Al-Laham, M A., Peng, C Y., Nanayakkara, A., Challacombe, M., Gill, P M W., Johnson, B., Chen, W., Wong, M W., Gonzalez, C., and Pople, J A.: Gaussian 03, Revision C.02, Gaussian, Inc., Wallingford CT, 2004. Fuchs, N A. and Sutugin, A G.: High dispersed aerosols: in: Topics in current aerosol research, edited by: Hidy, G M. and Brock, J R., vol. 2, Pergamon Press, Oxford, 1971. Goldstein, A H., McKay, M., Kurpius, M R., Schade, G W., Lee, A., Holzinger, R., and Rasmussen, R.: Forest thinning experiment confirms ozone deposition to forest canopy is dominated by reaction with biogenic VOCs, Geophys. Res. Lett., 31, L22106, doi:10.1029/2004GL021259, 2004. Geiger, H., Barnes, I., Becker, K.-H., Bohn. B., Brauers, T., Donner, B., Dorn, H.-P., Elend, M., Freitas Dinis, C M., Grossmann, D., Hass, H., Hein, H., Hoffmann, A., Hoppe, L., Hülsemann, F., Kley, D., Klotz, B., Libuda, H G., Maurer, T., Mihelcic, D., Moortgat, G K., Olariu, R., Neeb, P., Poppe, D., Ruppert, L., Sauer., C G., Shestakov, O., Somnitz, H., Stockwell, W R., Thüner, L P., Wahner, A., Wiesen, P., Zabel, F., Zellner, R., and Zetzsch, C.: Chemical mechanism development, J. Atmos. Chem., 42, 323–357, 2002. Groß mann, D.: Die Gasphasenozonolyse von Alkenen in Gegenwart von Wasserdampf als Quelle für Wasserstoffperoxid und organische Peroxide in der Atmosphäre, Ph.D. thesis, University Mainz, Mainz, 1999. 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. Hakola, H., Tarvainen, V., Laurila, T., Hiltunen, V., Hellén, H., and Keronen, P.: Seasonal variation of VOC concentrations above a boreal coniferous forest, Atmos. Environ., 37, 1623–1637, 2003. Hari, P. and Kulmala, M.: Station for measuring ecosystem-atmosphere relations, Boreal Environ. Res., 10, 315–322, 2005. Hakola, H., Tarvainen, V., Bäck, J., Ranta, H., Bonn, B., Rinne, J., and Kulmala, M.: Seasonal variation of mono- and sesquiterpene emission rates of Scots pine, Biogeosciences, 2, 93–101, 2006. Hellén, H., Hakola, H., Reissell, A., and Ruuskanen, T M.: Carbonyl compounds in boreal coniferous forest air in Hyytiälä, Southern Finland, Atmos. Chem. Phys., 4, 1771–1780, 2004. Hirsikko, A., Laakso, L., H\~orrak, U., Aalto, P P., Kerminen, V.-M., and Kulmala, M.: Annual and size dependent variation of growth rates and ion concentrations in boreal forest, Boreal Environ. Res., 10, 357–369, 2005. Hoppel, W. A. and Frick, G. M.: Ion-aerosol attachment coefficients and the steady-state charge distribution on aerosols in a bipolar ion environment, Aerosol Sci. Technol., 5, 1–21, 1986. Isra\"el, H.: Atmospheric electricity, vol. I, Israel program for Sci. Transl. & NSF, Jerusalem, 1970. Jensen, F.: Introduction to Computational Chemistry, 2nd edition, John Wiley & Sons, Ltd, West Sussex, UK, 2007. Kauppila, T J., Kuuranne, T., Meurer, E C., Eberlin, M N., Kotiaho, T., and Kostiainen, R.: Atmospheric pressure photoionization mass spectrometry. Ionization mechanism and the effect of solvent on the ionization of naphtalenes, Anal. Chem., 74, 5470–5479, 2002. Kilpatrick, W D.: An experimental mass-mobility relation for ions in the air at atmospheric pressure, Proc. Annu. Conf. Massspectrosc., 19, 320–325, 1971. Kulmala, M., Pirjola, L., and Mäkelä, J M.: Stable sulphate clusters as a source of new atmospheric particles, Nature, 404, 66–69, 2000. Kulmala, M., Hämeri, K., Aalto, P P., Mäkelä, J M., Pirjola, L., Douglas Nilsson, E., Buzorius, G., Rannik, Ü., Dal Maso, M., Seidl, W., Hoffmann, T., Janson, R., Hansson, H.-C., Viisanen, Y., Laaksonen, A., and O'Dowd, C D.: Overview of the international project on biogenic aerosol formation in the boreal forest (BIOFOR), Tellus, 53B, 324–343, 2001. Laakso, L., Mäkelä, J M., Pirjola, L., and Kulmala, M.: Model studies on ion-induced nucleation in the atmosphere, J. Geophys. Res., 107(D20), 4427, doi:10.1029/2002JD002140, 2002. Lee, C., Yang, W., and Parr, R G.: Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density, Phys. Rev. B, 37, 785–789, 1988. Loreto, F., Mannozzi, M., Maris, C., Nascetti, P., Ferranti, F., and Pasqualini, S.: Ozone quenching properties of isoprene and its antioxidant role in leaves, Plant Physiol., 126, 993–1000, 2001. Perkins, M D. and Eisele, F L.: First mass spectrometric measurements of atmospheric ions at ground level, J. Geophys. Res., 89(D6), 9649–9657, 1984. Pirjola, L., Kulmala, M., Wilck, M., Bischoff, A., Stratmann, F., and Otto, E.: Formation of sulphuric acid aerosols and cloud condensation nuclei: An expression for significant nucleation and model comparison, J. Aerosol Sci., 30, 1079–1094, 1999. Seinfeld, J H. and Pandis, S N.: Atmospheric chemistry and physics, Wiley Interscience Pub., New York, 1998. Shu, Y. and Atkinson, R.: Rate constants for the gas-phase reactions of \chemO_3 with a series of terpenes and OH radical formation from the \chemO_3 reactions with sesquiterpenes at 296\unit\pm2 K, Int. J. Chem. Kin., 26, 1193–1205, 1994. Shu, Y. and Atkinson, R.: Atmospheric lifetimes and fates of a series of sesquiterpenes, J. Geophys. Res., 100(D4), 7275–7281, 1995. Tammet, H.: Size and mobility of nanometer particles, clusters and ions, J. Aerosol Sci., 26, 459–475, 1995. Tammet, H.: Reduction of air ion mobility to standard conditions, J. Geophys. Res., 103(D12), 13 933–13 937, 1998. Tammet, H.: Balanced Scanning Mobility Analyzer, in: Proc. 16th International Conference on Nucleation & Atmospheric Aerosols, Kyoto, 2004. Tammet, H.: Simulation tool for atmospheric aerosol nucleation bursts, J. Aerosol Sci., 36, 173–196, 2005. Tammet, H.: Continuous scanning of the mobility and size distribution of charged clusters and nanometer particles in atmospheric air and the Balanced Scanning Mobility Analyzer BSMA, Atmos. Res., 82, 523–535, 2006. Tammet, H., H\~orrak, U., Laakso, L., and Kulmala, M.: Factors of air ion balance in a coniferous forest according to measurements in Hyytiälä, Finland, Atmos. Chem. Phys., 6, 3377–3390, 2006. Tarvainen, V., Hakola, H., Hellén, H., Bäck, J., Hari, P., and Kulmala, M.: Temperature and light dependence of the VOC emissions of Scots pine, Atmos. Chem. Phys., 5, 989–998, 2005. Vana, M., Kulmala, M., Dal Maso, M., H\~orrak, U., and Tamm, E.: Comparative study of nucleation mode aerosol particles and intermediate air ions formation events at three site, J. Geophys. Res., 109, D17201, doi:10.1029/2003JD004413, 2004. Viggiano, A A., Perry, R A., Albritton, D L.,Ferguson, E E., and Fehsenfeld, F C.: The role of \chemH_2SO_4 in stratospheric negative-ion chemistry, J. Geophys. Res., 85(NC8), 4551–4555, 1980. von Niessen, W., Schirmer, J., and Cederbaum, L. S.: Computational methods for the one-particle Green's function, Comput. Phys. Rep., 1, 57–125, 1984. Vuorinen, T., Nerg, A.-M., Vapaavuori, E., and Holopainen, J K.: Emission of volatile organic compounds from two silver birch (\it Betula pendula Roth) clones grown under ambient and elevated \chemCO_2 and different \chemO_3 concentrations, Atmos. Environ., 39, 1185–1197, 2005. Went, F W.: Blue hazes in the atmosphere, Nature, 187, 641–643, 1960. Zakrzewski, V. G. and Ortiz, J. V.: Semidirect algorithms for third-order electron propagator calculations, Int. J. Quantum Chem., 53, 583–590, 1995.