ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-9-2089-2009 Vertical advection and nocturnal deposition of ozone over a boreal pine forest Rannik Ü. 1 Mammarella I. 1 Keronen P. 1 Vesala T. 1 2 Department of Physical Sciences, P.O. Box 64, 00014 University of Helsinki, Helsinki, Finland Department of Forest Ecology, P.O. Box 27, 00014 University of Helsinki, Helsinki, Finland 23 03 2009 9 6 2089 2095 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/9/2089/2009/acp-9-2089-2009.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/9/2089/2009/acp-9-2089-2009.pdf

Night-time ozone deposition for a Scots pine forest in Southern Finland was studied at the SMEAR II measurement station by evaluating the turbulent eddy covariance (EC), storage change and vertical advection fluxes. Similarly to night-time carbon dioxide flux, the eddy-covariance flux of ozone was decreasing with turbulence intensity (friction velocity), and storage change of the compound did not compensate the reduction (well-known night-time measurement problem). Accounting for vertical advection resulted in invariance of ozone deposition rate on turbulence intensity. This was also demonstrated for carbon dioxide, verified by independent measurements of NEE by chamber systems. The result highlights the importance of advection when considering the exchange measurements of any scalar. Analysis of aerodynamic and laminar boundary layer resistances by the model approach indicated that the surface resistance and/or chemical sink strength was limiting ozone deposition. The possible aerial ozone sink by known fast chemical reactions with sesquiterpenes and NO explain only a minor fraction of ozone sink. Thus the deposition is controlled either by stomatal uptake or surface reactions or both of them, the mechanisms not affected by turbulence intensity. Therefore invariance of deposition flux on turbulence intensity is expected also from resistance and chemical sink analysis.

 References Altimir, N., Kolari, P., Tuovinen, J.-P., Vesala, T., Bäck, J., Suni, T., Kulmala, M.., and Hari., P.: Foliage surface ozone deposition: a role for surface moisture?, Biogesciences, 3, 209–228, 2006. Atkinson, R.: Gas-phase tropospheric chemistry of volatile organic compounds: 1. alkanes and alkenes, J. Phys. Chem. Ref., 26, 215–290, 1997. Aubinet, M., Berbigier, P., Bernhofer, Ch., Cescatti, A., Feigenwinter, C., Granier, A., Grünwald, Th., Havrankova, K., heinesch, B., Longdoz, B., Marcolla, B., Montagnani, L., and Sedlak, P.: Comparing CO<sub>2</sub> storage and advection conditions at night at different CARBOEUROFLUX sites, Bound.-Lay. Meteorol., 116, 63–94, 2005. Aubinet, M., Grelle, A., Ibrom, A., Rannik, Ü., Moncrieff, J., Foken T., Kowalski, A. S., Martin, P. H., Berbigier, P., Bernhofer, Ch., Clement, R., Elbers, J., Granier, A., Grünwald, T., Morgenstern, K., Pilegaard, K., Rebmann, C., Snijders, W., Valentini, R., and Vesala, T.: Estimates of the annual net carbon and water exchange of European forests: the EUROFLUX methodology, Adv. Ecol. Res., 30, 113–175, 2000. Bonn, B., Rannik, Ü., Hakola, H., Bäck, J., Nikinmaa, E., Niinemets, Ü., Noe, S. M., Vesala, T., Hari, P., and Kulmala, M.: Sesquiterpenes at a boreal forest site: Emission and ambient concentration, Geophys. Res. Abstr., 10, EGU2008-A-06339, 2008. Goldstein, A. H., McKay, M., Kurpius, M. R., Schade, G. W., Lee, A., Holzinger, R., and Rasmussen, R. A.: Forest thinning confirms ozone deposition to forest canopy is dominated by reaction with biogenic VOCs, Geophys. Res. Lett., 31, L22106, doi:10.1029/2004GL021259, 2004. Gu, L., Falge, E., Boden, T., Baldocchi, D., Black, T. A., Saleska, R. S., Suni, T., Verma, S. B., Vesala, T., Wofsy, S. C., and Xu, L.: Objective threshold determination for night-time eddy flux filtering, Agr. Forest Meteorol., 128, 179–197, 2005. Hakola, H., Tarvainen, V., Bäck, J., Ranta, H., Bonn, B., Rinne, J., and Kulmala, M.: Seasonal variation of mono- and sesquitepene emission rates of Scots pine, Biogeosciences, 3, 93–101, 2006. Hari, P. and Kulmala, M.: Station for measuring ecosystem-atmosphere relations (SMEAR II), Boreal Environ. Res., 10, 315–322, 2005. Holzinger, R., Lee, A., Paw, K. T., and Goldstein, U. A. H.: Observations of oxidation products above a forest imply biogenic emissions of very reactive compounds, Atmos. Chem. Phys., 5, 67–75, 2005. Holzinger, R., Lee, A. , McKay, M., and Goldstein, A. H.: Seasonal variability of monoterpene emission factors for a Ponderosa pine plantation in California, Atmos. Chem. Phys., 6, 1267–1274, 2006. Keronen, P., Reissell, A., Rannik, Ü., Pohja, T., Siivola, E., Hiltunen, V., Hari, P., Kulmala, M., and Vesala, T.: Ozone flux measurements over a Scots pine forest using eddy covariance method: performance evaluation and comparison with flux-profile method, Boreal Environ. Res., 8, 425–443, 2003. Lamaud, E., Carrara, A., Brunet, Y., Lopez, A., and Druilhet, A.: Ozone fluxes above and within a pine forest canopy in dry and wet conditions, Atmos. Environ., 36, 77–88, 2002. Lee, X.: On micrometeorological observations of surface-air exchange over tall vegetation, Agr. Forest Meteorol., 91, 39–49, 1998. Loescher, H. W., Law, B. E., Mahrt, L., Hollinger, D. Y., Campbell, J., and Wofsy, S. C.: Uncertainties in, and interpretation of, carbon flux estimates using the eddy covariance technique, J. Geophys Res., 111(D21), doi:10.1029/2005JD006932, 2006. Mammarella, I., Kolari, P., Rinne, J., Keronen, P., Pumpanen, J., and Vesala, T.: Determining the contribution of vertical advection to the net ecosystem exchange at Hyytiälä forest, Finland, Tellus B, 59B, 900–909, 2007. Marcolla, B., Cescatti, A., Montagnani, L., Manca, G., Kerschbaumer, G., and Minerbi, S.: Importance of advection in the atmospheric CO<sub>2</sub> exchanges of an alpine forest, Agr. Forest Meteorol., 130, 193–206, 2005. Michael, J. V., Allen Jr., J. E., and Brobst, W. D.: Temperature dependence of the nitric oxide + ozone reaction rate from 195 to 369 K, J. Phys. Chem., 85 (26), 4109–4117, 1981. Mikkelsen, T. N., Ro-Poulsen, H., Hovmand, M. F., Jensen, N. O., Pilegaard, K., and Egeløv, A. H.: Five-year measurements of ozone fluxes to a Danish Norway spruce canopy, Atmos. Environ., 38, 2361–2371, 2004. Paw U, K. T., Baldocchi, D. D., Meyers, T. P., and Wilson, K. B.: Correction of eddy-covariance measurements incorporating both advective effects and density fluxes, Bound.-Lay. Meteorol., 97, 487–511, 2000. Pilegaard, K., Skiba, U., Ambus, P., Beier, C., Brüggemann, N. , Butterbach-Bahl, K., Dick, J., Dorsey, J., Duyzer, J., Gallagher, M., Gasche, R., Horvath, L., Kitzler, B., Leip, A., Pihlatie, M. K., Rosenkranz, P., Seufert, G., Vesala, T., Westrate, H., and Zechmeister-Boltenstern, S.: Factors controlling regional differences in forest soil emission of nitrogen oxides (NO and N<sub>2</sub>O), Biogeosciences, 3, 651–661, 2006. Rannik, Ü., Aalto, P., Keronen, P., Vesala, T., and Kulmala, M.: Interpretation of aerosol particle fluxes over a pine forest: Dry deposition and random errors, J. Geophys Res., 108(D17), 4544, doi:10.1029/2003JD003542, 2003a. Rannik, Ü., Keronen, P., Hari, P., and Vesala, T.: Estimation of forest-atmosphere CO<sub>2</sub> exchange by direct and profile techniques, Agr. Forest Meteorol., 126, 141–155, 2004. Rannik, Ü., Markkanen, T., Raittila, J., Hari, P., and Vesala, T.: Turbulence statistics inside and over forest: influence on footprint prediction, Bound.-Lay. Meteorol., 109(2), 163–189, 2003b. Slinn, W. G. N: Predictions of particle deposition to vegetative canopies, Atmos. Environ., 16, 1785–1794, 1982. Staebler, R. M. and Fitzjarrald, D. R.: Observing subcanopy CO<sub>2</sub> advection, Agr. Forest Meteorol., 122, 139–156, 2004. Shu, Y. and Atkinson, R.: Rate constants for the gas-phase reactions of O<sub>3</sub> with a series of Terpenes and OH radical formation from the O<sub>3</sub> reactions with Sesquiterpenes at 296&plusmn;2 K, Int. J. Chem. Kinet., 26(12), 1193–1205, 2004. Sun, J. and Massman, W.: Ozone transport during the California Ozone Deposition Experiment, J. Geophys Res., 104(D10), 11939–11948, 1999. Vesala, T., Haataja, J, Aalto, P., Altimir, N., Buzorius, G., Garam, E., Hämeri, K., Ilvesniemi, H., Jokinen, V., Keronen, P., Lahti, T., Markkanen, T., Mäkelä, J. M., Nikinmaa, E., Palmroth, S., Palva, L., Pohja, T., Pumpanen, J., Rannik, Ü., Siivola, E., Ylitalo, H., Hari, P., and Kulmala, M.: Long-term field measurements of atmosphere-surface interactions in boreal forest combining forest ecology, micrometeorology, aerosol physics and atmospheric chemistry, Trends in Heat, Mass and Momentum Transfer, 4, 17–35, 1998. Vickers D. and Mahrt L.: Contrasting mean vertical motion from tilt correction methods and mass continuity, Agr. Forest. Meteorol., 138, 93–103, 2006. Wilczak, J. M., Oncley, S. P., and Stage S. A.: Sonic anemometer tilt correction algorithms, Bound.-Lay. Meteorol., 99, 127–150, 2001.