ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-9-5447-2009 Day-time concentrations of biogenic volatile organic compounds in a boreal forest canopy and their relation to environmental and biological factors Lappalainen H. K. 1 2 Sevanto S. 2 Bäck J. 3 Ruuskanen T. M. 2 Kolari P. 3 Taipale R. 2 Rinne J. 2 Kulmala M. 2 Hari P. 3 Finnish Meteorological Institute, P. O. Box 503, 00101 Helsinki, Finland Department of Physics, P. O. Box 64, 00014 University of Helsinki, Finland Department of Forest Ecology, P. O. Box 27, 00014 University of Helsinki, Finland 03 08 2009 9 15 5447 5459 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/9/5447/2009/acp-9-5447-2009.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/9/5447/2009/acp-9-5447-2009.pdf

Atmospheric concentrations of methanol, acetaldehyde, acetone, isoprene and monoterpenes were measured using PTR-MS (proton transfer reaction mass spectrometry) in a boreal forest site in Hyytiälä, Finland (61°51' N, 24°17' E). The concentration measurements were made in the upper canopy of a Scots pine forest during 6 June, 2006–31 August, 2007. Meteorological variables such as temperature and photosynthetically active radiation were measured simultaneously. We also detected biologically sensitive turnover points such as the onsets of photosynthetic activity, onset of growing season, bud burst and stem growth during the annual cycle and compared them to changes in BVOC (biogenic volatile organic compound) concentrations. A typical seasonal pattern of winter minimum and summer maximum was found for all studied compounds except acetaldehyde. Spring time methanol and acetone concentrations increased together with photosynthetic capacity. The day-time daily median BVOC concentrations correlated best with air temperature. The intercorrelations between compounds and the analysis of meteorological conditions indicated that the measured concentrations presented well the local source. During an exceptional summer drought period the concentrations were neither connected with photosynthesis nor transpiration, but they were regulated by some other, yet unknown factors.

 References Asensio, D., Penuelas, J., Llusia, J. J., Ogaya, R., and Filella, I.: Interannual and interseasonal soil CO<sub>2</sub> efflux and VOC exchange rates in a Mediterranean holm oak forest in response to experimental drought, Soil Biol. Biochemi., 3, 2471-2484, 2007. Atkinson, R. and Arey, J.: Gas-phase tropospheric chemistry of biogenic volatile organic compounds: a review, Atmos. Environ., 37, 197–219, 2003. Bäck, J., Hari, P., Hakola, H., Juurola, E., and Kulmala, M.: Dynamics of monoterpene emissions in Pinus sylvestris during early spring, Boreal Env. Res., 10, 409–424, 2005. Copolovici, L. and Niinemets, U.:Temperature dependencies of Henry's law constants and octanol/water partition coefficients for key plant volatile monoterpenoids, Chemosphere, 61, 1390–1400, 2005. Duursma, R. A., Kolari, P., Perämäki, M., Nikinmaa, E., Hari, P., Delzon, S., Loustau, D., Ilvesniemi, H., Pumpanen, J., and Mäkelä, A.: Predicting the decline in daily maximum transpiration rate of two pine stands during drought based on constant minimum leaf water potential and plant hydraulic conductance, Tree Physiol., 28, 265–276, 2008. Fall, R.: Abundant Oxygenates in the Atmosphere: A Biochemical perspective, Chem. Rev., 103, 4941–4951, 2003. Fischbach, R. J., Staudt, M., Zimmer, I., Rambal, S., and Schnitzler, J.-P.: Seasonal pattern of monoterpene synthase activities in leaves of the evergreen tree (\textitQuercus ilex), Physiol. Plantarum, 114, 354–360, 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 Biol., 10, 65–75 2008. Galbally, I. E. and Kirstine, W.: The production of methanol by flowering plants and the global cycle of methanol, J. Atmos. Chem., 43, 195–229, 2002. Ghirardo, A., Koch, K., Schnitzler, J.-P., and Rinne, J.: 13CO<sub>2</sub> feeding experiment of four common European boreal tree species: 13C incorporation into monoterpenes. 4th International Conference on Proton Transfer Reaction Mass Spectrometry and its applications – Contributions, 16–21, 2009, Obergurgl, Austria, Conference Series, Innsbruck University Press, 219–220, 2009. Goldstein, A. H. and Schade, G. W.: Quantifying biogenic and anthropogenic contributions to acetone mixing ratios in a rural environment, Atmos. Environ., 34, 4997–5006, 2000. Graus, M., Schnitzler, J.-P., Hansel, A., Cojocariu, C., Rennenberg, H., Wisthaler, A., and Kreuzwieser, J.: Transient Release of Oxygenated Volatile Organic Compounds during Light-Dark Transitions in Grey Poplar leaves, Plant Physiol., 135, 1967–1975, 2004. Gray, D. W., Goldstein, A. H., and Lerdau, M.:Thermal history regulates methylbutenol basal emission rate in \textitPinus ponderosa, Plant Cell Environ., 29, 1298–1308, 2006. Grote, R. and Niinements, U.: Modeling volatile isoprenoid emissions - a story with split ends, Plant Biol. (Stuttg.), 10, 8–28, 2008. Guenther, A.: Seasonal and spatial variations in natural volatile organic compound emissions, Ecol. Appl., 7, 34–45, 1997. Guenther, A. B., Monson, R. K., and Fall, R.: Isoprene and monoterpene emission rate variability: Observations with Eucalytus and emission rate algorithm development, J. Geophys. Res., 96, 10799–10808, 1991. 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 compounds emissions, J. Geophys. Res., 100, 8873–8892, 1995. Hakola, H., Hellen, H., and Laurila, T.: Ten years of light hydrocarbons (C-2-C-6) concentration measurements in background air in Finland, Atmos. Environ., 40, 3621–3630, 2006. Hakola, H., Laurila, T., Lindfors, V., Hellén, H., Gaman, A., and Rinne, J.: Variation of the VOC emission rates of birch species during the growing season, Boreal Env. Res., 6, 237–249, 2001. Hakola, H., Laurila, T., Rinne, J., and Puhto, K.; The ambient concentrations of biogenic hydrocarbons at a northern European, boreal site, Atmos. Environ., 34, 4971–4982, 2000. Hari, P. and Kulmala, M.: Station for measuring ecosystem-atmosphere relations (SMEAR II), Boreal Env. Res., 10, 315–322, 2005. Hari, P. and Kulmala L. (Eds.): Boreal forest and climate change, Advances in global change research, 34, Springer, 2008. Ilvesniemi, H., Levula, J., Ojansuu, R., Kolari, P., Kulmala, L., Pumpanen, J., Launiainen, S., Vesala, T., and Nikinmaa, E.: Long-term measurements of the carbon balance of a boreal Scots pine dominated forest ecosystem, Boreal Env. Res., 14, 731–753, 2009. Janson, R.: Monoterpene concentrations in and above a forest of scots pine, J. Atmos. Chem., 14, 385–394, 1992. Janson, R., De Serves, C., and Romero, R.: Emission of isoprene and carbonyl compounds from a boreal forest and wetland in Sweden, Agr. Forest Meteorol., 98–99, 671–681, 1999. Janson, R. and de Serves, C.: Acetone and monoterpene emissions from boreal forest i n northern Europe, Atmos. Environ., 35, 4629–4637, 2001. Karl, T., Guenther, A., Spirig, C., Hansel, A., and Fall, R.: Seasonal variation of biogenic VOC emissions above a mixed hardwood forest in northern Michigan, Geophys. Res. Lett., 30, 2186, doi:10.1029/2003GL018432, 2003. Karl, T., Harley, P., Guenther, A., Rasmussen, R., Baker, B., Jardine, K., and Nemitz, E.: The bi-directional exchange of oxygenated VOCs between a loblolly pine (\textitPinus taeda) plantation and the atmosphere, Atmos. Chem. Phys., 5, 3015–3031, 2005. Kolari, P., Lappalainen, H. K., Hänninen, H., and Hari, P.: Relationship between temperature and the seasonal course of photosynthesis in Scots pine at northern timberline and in southern boreal zone, Tellus B, 59, 542–552, 2007. Kourtchev, I., Ruuskanen, T. M., Keronen, P., Sogcheva, L., Maso, D. M., Chi, X., Vermeyerl, R., Kulmala, M., Maenhaut, W., and Claeys, M.: Determination of isoprene and α-/β-pinene oxidation products in boreal forest aerosols from Hyytiälä, Finland: diurnal variations and possible links with particle formation events, Plant Biol., 10, 138–149, 2008. Kreuzwieser, J., Harren, F. J. M., Laarhoven, L. J. J., Boamfa, I., te Lintel-Hekkert, S., Scheerer, U., Hüglin, C., and Rennenberg, H.: Acetaldehyde emission by the leaves of trees – correlation with physiological and environmental parameters, Physiol. Plantarum, 113, 41–49, 2001. Kreuzwieser, J., Papadopoulou, E., and Rennenberg, H.: Interaction of flooding with carbon metabolism of forest trees, Plant Biol., 6, 299–306, 2004. Kulmala, M., Riipinen, I., Sipilä, M., Manninen, H. E., Petäjä, T., Junninen, H., Dal Maso, M., Mordas, G., Mirme, A., Vana, M., Hirsikko, A., Laakso, L., Harrison, R. M., Hanson, I., Leung, C., Lehtinen, K., and Kerminen, V.-M.: Toward Direct Measurement of Atmospheric Nucleation, Science, 318, 89–92, 2007. Kulmala, M., Suni, T., Lehtinen, K. E. J., Dal Maso, M., Boy, M., Reissell, A., Rannik, Ãœ., Aalto, P., Keronen, P., Hakola, H., Bäck, J., Hoffmann, T., Vesala, T., and Hari, P.: A new feedback mechanism linking forests, aerosols, and climate, Atmos. Chem. Phys., 4, 557–562, 2004. Lappalainen, H. and Heikinheimo, M.: Relations between climate and plant phenology. Part 1. survey of plant phenological observations in Finland from 1896 to 1965, Meteorological publications, No. 20, 34~pp., 1992. Leff, J. W. and Fierer, N.: Volatile organic compound (VOC) emissions from soil and litter samples, Soil Biol. Biochem., 40, 1629–1636, 2008. Legreida, G., Löövb, J. B., Staehelinb, J., Hueglina, C., Hilla, M., Buchmanna, B., Prevotc, A. S. H., and Reimanna, S.: Oxygenated volatile organic compounds (OVOCs) at an urban background site in Zürich (Europe): Seasonal variation and source allocation, Atmos. Environ., 41, 8409–8423, 2007. Lindinger, W., Hansel, A., and Jordan, A.: On-line monitoring of volatile organic compopunds 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. Linkosalo, T., Lappalainen, H. K, and Hari, P.: Comparision of phenological models of leaf bud burts and flowering of borela trees using independent observation data, Tree Physiol., 28, 1873–1882, 2008. Linkosalo,T. and Lechowicz, M.: Twilight far-red treatment advances leaf bud burst of silver birch (\textitBetula pendula), Tree Physiol., 26, 1249–1256, 2006. Lindfors, V. and Laurila, T.: Biogenic volatile organic compound (VOC) emissions from forests in Finland, Boreal Env. Res., 5, 95–113, 2000. Monson, R., Lerdau, M., Sharkey, T., and Schimel, D.: Biological aspects of construction organic compound emission inventories, Atmos. Environ., 29, 2989–3002, 1995. Mäkelä, A., Hari, P., Berninger, F., Hänninen, H., and Nikinmaa, E.: Acclimation of photosynthetic capacity in Scots pine to the annual cycle temperature, Tree Physiol., 24, 369–378, 2004. Mäkelä, A., Kolari, P., Karimäki, J., Nikinmaa, E., Perämäki, M., and Hari, P.: Modelling five years of weather-driven variation of GPP in a boreal forest, Agr. Forest Meterol., 139, 382–398, 2006. Niinemets, U. and Reichstein, M.: Controls on the emission of plant volatiles through stomata: Differential sensitivity of emission rates to stomatal closure explained, J. Geophys. Res., 108(D7), 4208, doi:10.1029/2002JD002620, 2003. Niinemets, U., Tenhunen, J. D., Harley, P. C., and Steinbrecher, R.: A model of isoprene emission based on energetic requirements for isoprene synthesis and leaf photosynthetic properties for \textitLiquidambar and \textitQuercus, Plant Cell Environ., 22, 1319–1335, 1999. Öquist, G. and Huner, N.: Photosynthesis of overwintering evergreen plants, Annual Review of Plant Biology, 54, 329–355, 2003. Owen, S. M. and Penuelas, J.: Opportunistic emissions of volatile isoprenoids, TRENDS in Plant Science, 10, 420–426, 2005. Penuelas, J. and Llusia, J.: Plant VOC emissions: making use of the unavoidable, TRENDS in Ecology and Evolution, 19, 402–404, 2004. Penuelas, J. and Munne-Bosch, S.: Isoprenoids: an evolutionary pool for photoprotection, TRENDS in Plant Science, 10, 166–169, 2005. Rinne, J., Ruuskanen, T. M., Reissell, A., Taipale, R., Hakola, H., and Kulmala, M.: On-line PTR-MS measurements of atmospheric concentrations of volatile organic compounds in a European boreal forest ecosystem, Boreal Env. Res., 10, 425–436, 2005. Rinne, J., Taipale, R., Markkanen, T., Ruuskanen, T. M., Hellén, H., Kajos, M. K., Vesala, T., and Kulmala, M.: Hydrocarbon fluxes above a Scots pine forest canopy: measurements and modeling, Atmos. Chem. Phys., 7, 3361–3372, 2007. Ruuskanen, T. M., Taipale, R., Rinne, J., Kajos, M. K., Hakola, H., and Kulmala, M.: Quantitative long-term measurements of VOC concentrations by PTR-MS: annual cycle at a boreal forest site, Atmos. Chem. Phys. Discuss., 9, 81–134, 2009. Sarvas, R.: Investigations on the annual cycle of development of forest trees. Active period, Communicationes Instituti Forestalis Fenniae, 76, 1–110, 1972. Schade, G. W. and Goldstein, A. H.: Fluxes of oxygenated volatile organic compounds from a ponderosa pine plantation, J. Geophys. Res.-Atmos., 106, 3111–3123, 2001. Schade, G. W. and Goldstein, A. H.: Seasonal measurements of acetone and methanol: Abundances and implications for atmospheric budgets, Global Biogeochem. Cy., 20, GB1011, doi:10.1029/2005GB002566, 2006. Sevanto, S., Hölttä, T., Markkanen, T., Perämäki, M., Nikinmaa, E., and Vesala, T.: Relationships between diurnal xylem diameter variation and environmental factors in Scots pine, Boreal Env. Res., 10, 447–458, 2005. Shao, M., Czapiewski, K. V., Heiden, A. C., Kobel, K., Komenda, M., Koppman, R., and Wildt, J.: Volatile organic compound emissions from Scots pine: Mechanisms and description by algorithms, J. Geophys. Res., 106, 20483–20491, 2001. Taipale, R., Ruuskanen, T. M., Rinne, J., Kajos, M. K., Hakola, H., Pohja, T., and Kulmala, M.: Technical Note: Quantitative long-term measurements of VOC concentrations by PTR-MS – measurement, calibration, and volume mixing ratio calculation methods, Atmos. Chem. Phys., 8, 6681–6698, 2008. 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. Tingey, D., Manning, M., Grothaus, L., and Burns W. F.: Influence of light and temperature on monoterpene emission rates from Slash pine, Plant. Physiol. 65, 797–801, 1980. Tunved, P., Korhonen, H., Strom, J., Hansson, H. C., Lehtinen, K. E. J., and Kulmala, M.: Is nucleation capable of explaining observed aerosol integral number increase during southerly transport over Scandinavia?, Tellus B, 58, 129–140, 2006. Vesala, T., Haataja, J., Aalto, P., et al.: Long-term field measurements of atmosphere-surface interactions in boreal forest ecology, micrometeorology, aerosol physics and atmospheric chemistry, Trends in Heat, Mass and Momentum Transfer, 4, 17–35, 1998. Warneke, C., Karl, T., Judmaier, H., Hansel, A., Jordan, A., Lindinger, W., and Crutzen, P. J.: Acetone, methanol and other partially oxidized volatile organic emissions from dead plant matter by abiological processes: significance for atmospheric HO<sub>x</sub> chemistry, Global Biogeochem. Cy., 13, 9–15, 1999.