ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-6-2273-2006 Interactive chemistry in the Laboratoire de Météorologie Dynamique general circulation model: model description and impact analysis of biogenic hydrocarbons on tropospheric chemistry Folberth G. A. 1 3 Hauglustaine D. A. 1 Lathière J. 1 Brocheton F. 2 Laboratoire des Sciences du Climat et de l'Environnement (LSCE), Gif-sur-Yvette, France Centre National de Recherches Météorologiques (CNRM), Météo France, Toulouse, France now at: School of Earth and Ocean Science (SEOS), University of Victoria, Victoria, Canada 21 06 2006 6 8 2273 2319 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/6/2273/2006/acp-6-2273-2006.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/6/2273/2006/acp-6-2273-2006.pdf

We present a description and evaluation of LMDz-INCA, a global three-dimensional chemistry-climate model, pertaining to its recently developed NMHC version. In this substantially extended version of the model a comprehensive representation of the photochemistry of non-methane hydrocarbons (NMHC) and volatile organic compounds (VOC) from biogenic, anthropogenic, and biomass-burning sources has been included. The tropospheric annual mean methane (9.2 years) and methylchloroform (5.5 years) chemical lifetimes are well within the range of previous modelling studies and are in excellent agreement with estimates established by means of global observations. The model provides a reasonable simulation of the horizontal and vertical distribution and seasonal cycle of CO and key non-methane VOC, such as acetone, methanol, and formaldehyde as compared to observational data from several ground stations and aircraft campaigns. LMDz-INCA in the NMHC version reproduces tropospheric ozone concentrations fairly well throughout most of the troposphere. The model is applied in several sensitivity studies of the biosphere-atmosphere photochemical feedback. The impact of surface emissions of isoprene, acetone, and methanol is studied. These experiments show a substantial impact of isoprene on tropospheric ozone and carbon monoxide concentrations revealing an increase in surface O<sub>3</sub> and CO levels of up to 30 ppbv and 60 ppbv, respectively. Isoprene also appears to significantly impact the global OH distribution resulting in a decrease of the global mean tropospheric OH concentration by approximately 0.7&times;10<sup>5</sup> molecules cm<sup>-3</sup> or roughly 8% and an increase in the global mean tropospheric methane lifetime by approximately seven months. A global mean ozone net radiative forcing due to the isoprene induced increase in the tropospheric ozone burden of 0.09 W m<sup>-2</sup> is found. The key role of isoprene photooxidation in the global tropospheric redistribution of NO<sub>x</sub> is demonstrated. LMDz-INCA calculates an increase of PAN surface mixing ratios ranging from 75 to 750 pptv and 10 to 250 pptv during northern hemispheric summer and winter, respectively. Acetone and methanol are found to play a significant role in the upper troposphere/lower stratosphere (UT/LS) budget of peroxy radicals. Calculations with LMDz-INCA show an increase in HO<sub>x</sub> concentrations region of 8 to 15% and 10 to 15% due to methanol and acetone biogenic surface emissions, respectively. The model has been used to estimate the global tropospheric CO budget. A global CO source of 3019 Tg CO yr<sup>-1</sup> is estimated. This source divides into a primary source of 1533 Tg CO yr<sup>-1</sup> and secondary source of 1489 Tg CO yr<sup>-1</sup> deriving from VOC photooxidation. Global VOC-to-CO conversion efficiencies of 90% for methane and between 20 and 45% for individual VOC are calculated by LMDz-INCA.

 References Altshuller, A P.: PANs in the atmosphere, \em J. Air & Waste Manage. Assoc.\/, \em 43\/, 1221-1230, 1993. Andreae, M.: Climatic effects of changing atmospheric aerosol levels, in: \em Future Cliamtes of the World\/, edited by: Henderson-Sellers, A., Vol 16 of \em World Survey of Climatology\/, pp 341-392, Elsvier, Amsterdam, 1995. Andreae, M. and Crutzen, P.: Atmospheric aerosols: biogeochemical sources and role in atmospheric chemistry, \em Science\/, \em 276\/, 1052-1058, 1997. Andreae, M O. and Merlet, P.: Emission of trace gases and aerosols from biomass burning, \em Global Biogeochem. Cycles\/, \em 15\/, 955-966, 2001. Apel, E C., Riemer, D D., Hills, A., Baugh, W., Orlando, J., Faloona, I., Tan, D., Brune, W., Lamb, B., Westberg, H., Carroll, M A., Thornberry, T., and Geron, C D.: Measurement and interpretation of isoprene fluxes and isoprene, methacrolein, and methyl vinyl ketone mixing ratios at the prophet site during the 1998 intensive, \em J. Geophys. Res.-Atmos.\/, 107(D3), 4034, doi:10.1029/2000JD000225, 2002. Atkinson, R., Baulch, D., Cox, R., Hampson, R., Kerr, J., Rossi, M., and Troe, J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Supplement v, \em J. Physi. Chem. Ref. Data\/, \em 26\/, 1125-1568, 1997. Balkanski, Y., Jacob, D., Gardner, G., Graustein, W., and Turekian, K.: Transport and residence times of tropospheric aerosols inferred from a global three-dimensional simulation of $^210$Pb, \em J. Geophys. Res.\/, \em 98\/, 20 573-20 586, 1993. Barrie, L A., Bottenheim, J W., Schnell, R C., Crutzen, P J., and Rasmussen, R A.: Ozone destruction and photochemical-reactions at polar sunrise in the lower arctic atmosphere, \em Nature\/, \em 334\/, 138-141, 1988. Bauer, S E., Balkanski, Y., Schulz, M., Hauglustaine, D A., and Dentener, F.: Global modeling of heterogeneous chemistry on mineral aerosol surfaces: Influence on tropospheric ozone chemistry and comparison to observations, \em J. Geophys. Res.-Atmos.\/, 109, D02304, doi:10.1029/2003JD003868, 2004. Baulch, D., Cobos, C., Cox, R A., Esser, C., Frank, P., Just, T., Kerr, J., Pilling, M., Troe, J., Walker, R., and Warnatz, J.: Evaluated kinetic data for combustion modelling, \em J. Phys. Chem. Ref. Data\/, \em 21\/, 411-429, 1992. Bergamaschi, P., Hein, R., Heimann, M., and Crutzen, P J.: Inverse modeling of the global CO cycle 1. inversion of CO mixing ratios, \em J. Geophys. Res.-Atmos.\/, \em 105\/, 1909-1927, 2000. Bernard, S M., Samet, J M., Grambsch, A., Ebi, K L., and Romieu, I.: The potential impacts of climate variability and change on air pollution-related health effects in the united states, \em Environ. Health Perspect.\/, \em 109\/, 199-209, 2001. Berntsen, T K., Isaksen, I. S A., Myhre, G., Fuglestvedt, J S., Stordal, F., Larsen, T A., Freckleton, R S., and Shine, K P.: Effects of anthropogenic emissions on tropospheric ozone and its radiative forcing, \em J. Geophys. Res.-Atmos.\/, \em 102\/, 28 101-28 126, 1997. Bey, I., Jacob, D J., Yantosca, R M., Logan, J A., Field, B D., Fiore, A M., Li, Q B., Liu, H. G Y., Mickley, L J., and Schultz, M G.: Global modeling of tropospheric chemistry with assimilated meteorology: Model description and evaluation, \em J. Geophys. Res.-Atmos.\/, \em 106\/, 23 073-23 095, 2001. Bonsang, B. and Boissard, C.: Global distribution of reactive hydrocarbons in the atmosphere, in: \em Reactive Hydrocarbons in the Atmosphere\/, pp 209-265, Academic Press, 1999. Bonsang, B., Polle, C., and Lembert, G.: Evidence for marine production of isoprene, \em Geophys. Res. Lett.\/, \em 19\/, 1129-1132, 1992. Boucher, O., Pham, M., and Venkataraman, C.: Simulation of the atmospheric sulfur cycle in the laboratoire de météorologie dynamique general circulation model. Model description, model evaluation, and global and european budgets, Note scientifique de l'IPSL n 23, 2002. Bouwman, A F. and Taylor, J A.: Testing high-resolution nitrous oxide emission estimates against observations using an atmospheric transport model, \em Global Biogeochem. Cycles\/, \em 10\/, 307-318, 1996. Bradley, J N., Edwards, A D., and Gilbert, J R.: Gas-phase reactions of singlet oxygen atoms with methane, \em Journal of the Chemical Society a -Inorganic Physical Theoretical\/, p 326pp., 1971. Brasseur, G. and Chatfield, R.: The fate of biogenic trace gases in the atmosphere, in: \em Trace Gas Emissions from Plants\/, edited by: Sharkey, T., Holland, E., and Mooney, H., pp 1-27, Academic Press, 1991. Brasseur, G. and Solomon, S.: \em Aeronomy of the Middle Atmosphere: Chemistry and Physics of the Stratosphere and Mesosphere\/, Atmospheric Science Library, D. Reidel Pub. Co., 2nd edn., 1987. Brasseur, G., Orlando, J., and Tyndall, G.: \em Atmospheric Chemistry and Global Change\/, Oxford Univ. Press, New York, 1999. Brasseur, G P., Hauglustaine, D A., Walters, S., Rasch, P J., Muller, J F., Granier, C., and Tie, X X.: Mozart, a global chemical transport model for ozone and related chemical tracers 1. model description, \em J. Geophys. Res.-Atmos.\/, \em 103\/, 28 265-28 289, 1998. Brocheton, F.: \em Représentation des émissions anthropogiques dans les models globaux de chimie-transport: sensibilité à la représentation spatiale des émissions et au degré de raffinement du schéma chimique\/, Ph.D., Université Paris 12 - Val de Marne, 1999. Burden, R. and Faires, J.: \em Numerical Analysis\/, PWS, Boston, Mass., 1985. Chang, J., Brost, R., Isaksen, I., Madronich, S., Middleton, P., Stockwell, W., and Walcek, C.: A three-dimensional Eulerian acid deposition model: Physical concepts and formulation, \em J. Geophys. Res.\/, \em 92\/, 14 681-14 700, 1987. Collins, W J., Derwent, R G., Johnson, C E., and Stevenson, D S.: The oxidation of organic compounds in the troposphere and their global warming potentials, \em Climatic Change\/, \em 52\/, 453-479, 2002. Constable, J. V H., Guenther, A B., Schimel, D S., and Monson, R K.: Modelling changes in voc emission in response to climate change in the continental united states, \em Global Change Biology\/, \em 5\/, 791-806, 1999. Corbett, J J., Fischbeck, P S., and Pandis, S N., Global nitrogen and sulfur inventories for oceangoing ships, \em J. Geophys. Res.-Atmos.\/, \em 104\/, 3457-3470, 1999. Crutzen, P.: The role of NO and NO$_2$ in the chemistry of the troposphere and stratosphere, \em Ann. Rev. Earth Planet. Sci.\/, \em 7\/, 443-472, 1979. Crutzen, P.: Ozone in the troposphere, in: \em Composition, Chemistry, and Climate of the Atmosphere\/, edited by: Singh, H., pp 349-393, Van Nostrand Reinold, New York, 1995. Crutzen, P. and Zimmermann, P.: The changing photochemistry of the troposphere, \em Tellus\/, \em 43\/, 136-151, 1991. De~Fries, R. and Townshend, J.: NDVI-derived land classification at global scales, \em Int. J. Remote Sens.\/, \em 15\/, 3567-3586, 1994. de~Rosnay, P. and Polcher, J.: Modelling root water uptake in acomplex land surface scheme coupled to a gcm, \em Hydrol. Earth Syst. Sci.\/, \em 2\/, 239-256, 1998. DeMore, W., Sander, S., Golden, D., Hampson, R., Kurylo, M., Howard, C., Ravishankara, A., Kolb, C., and Molina, M.: Chemical kinetics and photochemical data for use in stratospheric modeling, evaluation number 12, 1997. Dlugokencky, E. J., Masarie, K. A., Lang, P. M., and Tans, P. P.: Continuing decline in the growth rate of the atmospheric methane burden, \em Nature\/, \em 393\/, 447-450, 1998. Doskey, P. and Gao, W.: Vertical mixing and chemistry of isoprene in the atmospheric boundary layer: Aircraft-based measurements and numerical modeling, \em J. Geophys. Res.\/, \em 104\/, 21 263-21 274, 1999. Ducoudré-De~Noblet, N., Laval, K., and Perrier, A.: Sechiba, a new set of parametrizations of the hydrologic exchanges at the land/atmosphere interface within the lmd atmospheric general circulation model, \em J. Climate\/, \em 2\/, 248-273, 1993. Dufresne, J L., Friedlingstein, P., Berthelot, M., Bopp, L., Ciais, P., Fairhead, L., Le~Treut, H., and Monfray, P.: On the magnitude of positive feedback between future climate change and the carbon cycle, \em Geophys. Res. Lett.\/, 29, 10, 1405, doi:10.1029/2001GL013777, 2002. Emmons, L K., Hauglustaine, D A., Muller, J F., Carroll, M A., Brasseur, G P., Brunner, D., Staehelin, J., Thouret, V., and Marenco, A.: Data composites of airborne observations of tropospheric ozone and its precursors, \em J. Geophys. Res.-Atmos.\/, \em 105\/, 20 497-20 538, 2000. Erickson, D J. and Taylor, J A.: 3-d tropospheric co modeling - the possible influence of the ocean, \em Geophys. Res. Lett.\/, \em 19\/, 1955-1958, 1992. Fehsenfeld, F., Calvert, J., Fall, R., Goldan, P., Guenther, A., Hewitt, C., Lamb, B., Liu, S., Trainer, M., Westberg, H., and Zimmerman, P.: Emissions of volatile organic compounds from vegetation and the implications for atmospheric chemistry, \em Global Biogeochem. Cycles\/, \em 6\/, 389-430, 1992. Finlaysonpitts, B J. and Pitts, J N.: Atmospheric chemistry of tropospheric ozone formation - scientific and regulatory implications, \em J. Air & Waste Manage. Assoc.\/, \em 43\/, 1091-1100, 1993. Fishman, J.: The global consequences of increasing tropospheric ozone concentrations, \em Chemosphere\/, \em 22\/, 685-695, 1991. Folberth, G., Hauglustaine, D A., Ciais, P., and Lathiere, J.: On the role of atmospheric chemistry in the global CO$_2$ budget, \em Geophys. Res. Lett.\/, \em 32\/, L08801, doi:10.1029/2004GL021812, 2005. Friedlingstein, P., Bopp, L., Ciais, P., Dufresne, J L., Fairhead, L., Le~Treut, H., Monfray, P., and Orr, J.: Positive feedback between future climate change and the carbon cycle, \em Geophys. Res. Lett.\/, \em 28\/, 1543-1546, 2001. Fung, I., John, J., Lerner, J., Matthews, E., Prather, M., Steele, L., and Fraser, P., Three-dimensional model synthesis of the global methane cycle, \em J. Geophys. Res.-Atmos.\/, \em 96\/, 13 033-13 066, 1991. Galbally, I E. and Kirstine, W.: The production of methanol by flowering plants and the global cycle of methanol, \em J. Atmos. Chem.\/, \em 43\/, 195-229, 2002. Ganzeveld, L. and Lelieveld, J.: Dry Deposition Parameterization in a Chemistry General-Circulation Model and Its Influence On the Distribution of Reactive Trace Gases, \em J. Geophys. Res.-Atmos.\/, \em 100(D10)\/, 20 999-21 012, 1995. Ganzeveld, L. and Lelieveld, J., and Roelofs, G. J.: A dry deposition parameterization for sulfur oxides in a chemistry and general circulation model, \em J. Geophys. Res.-Atmos. \/, \em 103(D5) \/, 5679-5694, 1998. Gardner, R et~al., ANCAT/EC2 global aircraft emission inventories for 1991/92 and 2015: Report by the ECAC/ANCAT and EC Working Group, Tech. rep., Def. Eval. and Res. Agency, Farnborough, UK, 1998. Giorgi, F. and Chameides, W.: The rainout parameterization in a photochemical model, \em J. Geophys. Res.\/, \em 90\/, 7872-7880, 1985. Graedel, T.: Terpenoids in the atmosphere, \em Rev. Geophys. Space Phys.\/, \em 17\/, 937-947, 1979. Granier, C., Petron, G., Muller, J., and Brasseur, G.: The impact of natural and anthropogenic hydrocarbons on the tropospheric budget of carbon monoxide, \em Atmos. Environ.\/, \em 34\/, 5255-5270, 2000. Greenberg, R. and Heicklen, J.: The reaction of O($^1$D) with CH$_4$, \em Int. J. Chem. Kinet.\/, \em 4\/, 471, 1972. Guenther, A., Hewitt, C., Erickson, D., Fall, R., Geron, C., Graedel, T., Harley, P., Klinger, L., Lerdau, M., McKay, W., Pierce, T., Scholes, B., Steinbrecher, R., Tallamraju, R., Taylor, J., and Zimmerman, P.: A global model of natural volatile organic compound emissions, \em J. Geophys. Res.\/, \em 100\/, 8873-8892, 1995. Guenther, A., Archer, S., Greenberg, J., Harley, P., Helmig, D., Klinger, L., Vierling, L., Wildermuth, M., Zimmerman, P., and Zitzer, S.: Biogenic hydrocarbon emissions and landcover/climate change in a subtropical savanna, \em Phys. Chem. Earth Part B-Hydrol. Oceans Atmos.\/, \em 24\/, 659-667, 1999. Guenther, A., Geron, C., Pierce, T., Lamb, B., Harley, P., and Fall, R.: Natural emissions of non-methane volatile organic compounds; carbon monoxide, and oxides of nitrogen from north america, \em Atmos. Environ.\/, \em 34\/, 2205-2230, 2000. Hall, I., Wayne, R P., Cox, R A., Jenkin, M., and Hayman, G.: Kinetics of the reaction of NO$_3$ with HO$_2$, \em J. Phys. Chem.\/, 92(17), 5049-5054, 1988. Hao, W. and Liu, M.: Spatial and temporal distribution of tropical biomass burning, \em Global Biogeochem. Cycles\/, \em 8\/, 495-503, 1994. Harzallah, A. and Sadourny, R.: Internal versus sst-forced atmospheric variability as simulated by an atmospheric general-circulation model, \em J. Climate\/, \em 8\/, 474-495, 1995. Hauglustaine, D A. and Brasseur, G P.: Evolution of tropospheric ozone under anthropogenic activities and associated radiative forcing of climate, \em J. Geophys. Res.-Atmos.\/, \em 106\/, 32 337-32 360, 2001. Hauglustaine, D A., Granier, C., Brasseur, G P., and Megie, G.: The importance of atmospheric chemistry in the calculation of radiative forcing on the climate system, \em J. Geophys. Res.-Atmos.\/, \em 99\/, 1173-1186, 1994. Hauglustaine, D A., Brasseur, G P., Walters, S., Rasch, P J., Muller, J F., Emmons, L K., and Carroll, C A.: Mozart, a global chemical transport model for ozone and related chemical tracers 2. model results and evaluation, \em J. Geophys. Res.-Atmos.\/, \em 103\/, 28 291-28 335, 1998. Hauglustaine, D A., Hourdin, F., Jourdain, L., Filiberti, M A., Walters, S., Lamarque, J F., and Holland, E A.: Interactive chemistry in the laboratoire de meteorologie dynamique general circulation model: Description and background tropospheric chemistry evaluation, \em J. Geophys. Res.-Atmos.\/, \em 109\/, D04314, doi:10.1029/2003JD003 957, 2004. Hauglustaine, D A., Lathière, J., Szopa, S., and Folberth, G A.: Future tropospheric ozone simulated with a climate-chemistry-biosphere model, \em Geophys. Res. Lett.\/, \em 32, L24807, doi:10.1029/2005GL024031, 2005. Heikes, B G., Chang, W N., Pilson, M. E Q., Swift, E., Singh, H B., Guenther, A., Jacob, D J., Field, B D., Fall, R., Riemer, D., and Brand, L.: Atmospheric methanol budget and ocean implication, \em Global Biogeochem. Cycles\/, 16(4), 1133, doi:10.1029/2002GB001895, 2002. Highwood, E J., Shine, K P., Hurley, M D., and Wallington, T J.: Estimation of direct radiative forcing due to non-methane hydrocarbons, \em Atmos. Environ.\/, \em 33\/, 759-767, 1999. Horowitz, L W., Walters, S., Mauzerall, D L., Emmons, L K., Rasch, P J., Granier, C., Tie, X X., Lamarque, J F., Schultz, M G., Tyndall, G S., Orlando, J J., and Brasseur, G P.: A global simulation of tropospheric ozone and related tracers: Description and evaluation of MOZART, version 2, \em J. Geophys. Res.-Atmos.\/, 108(D24), 4784, doi:10.1029/2002JD002853, 2003. Hourdin, F. and Armengaud, A.: The use of finite-volume methods for atmospheric advection of trace species-1. test of various formulations in a general circulation model, \em Mon. Wea. Rev.\/, 127(5), 822-837, 1999. Houweling, S., Dentener, F., and Lelieveld, J.: The impact of nonmethane hydrocarbon compounds on tropospheric photochemistry, \em J. Geophys. Res.\/, \em 103\/, 10 673-10 696, 1998. Jacob, D J.: Heterogeneous chemistry and tropospheric ozone, \em Atmos. Environ.\/, \em 34\/, 2131-2159, 2000. Jacob, D J., Field, B D., Jin, E M., Bey, I., Li, Q B., Logan, J A., Yantosca, R M., and Singh, H B.: Atmospheric budget of acetone, \em J. Geophys. Res.-Atmos.\/, 107(D10), 4100, doi:10.1029/2001JD000694, 2002. Jaeglé, L., Jacob, D J., Brune, W H., and Wennberg, P O.: Chemistry of hox radicals in the upper troposphere, \em Atmos. Environ.\/, \em 35\/, 469-489, 2001. Jenkin, M. and Cox, R A.: Kinetics of the gas-phase reaction of oh with nitrous acid, \em Chem. Phys. Lett.\/, 137(6), 548-552, 1987. Jourdain, L. and Hauglustaine, D.: The global distribution of lightning nox simulated on-line in a general circulation model, \em Phys. Chem. Earth Part B-Hydrol. Oceans Atmos.\/, \em 26\/, 585-591, 2001. Kanakidou, M., Tsigaridis, K., Dentener, F., and Crutzen, P.: Human-activity-enhanced formation of organic aerosols by biogenic hydrocarbon oxidation, \em J. Geophys. Res.\/, \em 105\/, 9243-9254, 2000. Kasibhatla, P.: NO$_\mathrmy$ from sub-sonic aircraft emissions: A global, three-dimensional model study, \em Geophys. Res. Lett.\/, \em 20\/, 1707-1710, 1993. Kellomaki, S., Rouvinen, I., Peltola, H., Strandman, H., and Steinbrecher, R.: Impact of global warming on the tree species composition of boreal forests in finland and effects on emissions of isoprenoids, \em Global Change Biology\/, \em 7\/, 531-544, 2001. Kirstine, W., Galbally, I., Ye, Y R., and Hooper, M.: Emissions of volatile organic compounds (primarily oxygenated species) from pasture, \em J. Geophys. Res.-Atmos.\/, \em 103\/, 10 605-10 619, 1998. Komhyr, W., Oltmans, S., Franchois, P., Evans, W., and Matthews, W., The latitudinal distribution of ozone to 35km altitude from ecc ozonesonde observations, 1985-1987, in: \em Ozone in the atmosphere\/, edited by: Bojkov, R. and Fabian, P., A. Deepak, Hampton, VA, 1989. Krinner, G., Viovy, N., De~Noblet-Ducoudré, N., Ogee, J., Polcher, J., Friedlingstein, P., Ciais, P., Sitch, A., and Prentice, I., A dynamical global vegetation model for studies of the coupled atmosphere-biosphere system, \em Global Biogeochem. Cycles\/, \em 19\/, GB1015, 2005. Kroeze, C., Mosier, A., and Bouwman, L.: Closing the global n2o budget: a retrospective analysis 1500-1994, \em Global Biogeochem. Cycles\/, \em 13\/, 1-8, 1999. Kukui, A., Jungkamp, T., and Schindler, R., Aldehyde formation in the reaction of methoxy radicals with NO$_3$, \em Ber. Bunsenges. Phys. Chem.\/, \em 99\/, 1565-1567, 1995. Lacis, A A., Wuebbles, D J., and Logan, J A.: Radiative forcing of climate by changes in the vertical-distribution of ozone, \em J. Geophys. Res.-Atmos.\/, \em 95\/, 9971-9981, 1990. Lathière, J., Hauglustaine, D A., Friend, A., De~Noblet-Ducoudré, N., Viovy, N., and Folberth, G.: Impact of climate variability and land use changes on global biogenic volatile organic compound emissions, \em Atmos. Chem. Phys. Discuss.\/, 5, 10 613-10 656, 2005. Lathière, J., Hauglustaine, D A., De~Noblet-Ducoudré, N., Krinner, N., and Folberth, G. A.: Past and future changes in biogenic volatile organic compound emissions simulated with a global dynamic vegetation model, \em Geophys. Res. Lett.\/, \em 32, doi:10.1029/2005GL024164, 2005a. Lawrence, M., Crutzen, P., Rasch, P., Eaton, B., and Mahowald, N.: A model for studies of tropospheric photochemistry: Description, global distributions, and evaluation, \em J. Geophys. Res.\/, \em 104\/, 26 245-26 277, 1999. Lawrence, M G., Jockel, P., and von Kuhlmann, R.: What does the global mean oh concentration tell us?, \em Atmos. Chemi. Phys.\/, \em 1\/, 37-49, 2001. Le~Treut, H., Li, Z X., and Forichon, M.: Sensitivity of the lmd general-circulation model to greenhouse forcing associated with 2 different cloud-water parameterizations, \em J. Climate\/, \em 7\/, 1827-1841, 1994. Lelieveld, J. and Dentener, F.: What controls tropospheric ozone, \em J. Geophys. Res.\/, \em 105\/, 3531-3551, 2000. Levy, H.: Normal atmosphere: Large radical and formaldehyde concentrations predicted, \em Science\/, \em 173\/, 141-143, 1971. Levy~II, H., Kasibhatla, P., Moxim, W., Klonecki, A., Hirsch, A., Oltmans, S., and Chameides, W.: The global impact of human activity on tropospheric ozone, \em Geophys. Res. Lett.\/, \em 24\/, 791-794, 1997. Li, D. and Shine, K.: A 4-dimensional ozone climatology for UGAMP models, UGAMP internal report, U.K. Univ. Global Atmos. Model. Program, Swindon, 1995. Logan, A.: An analysis of ozonesonde data for the troposphere: recommendations for testing 3-D-models and development of a gridded climatology for tropospheric ozone, \em J. Geophys. Res.\/, \em 104\/, 16 115-16 149, 1999. MacDonald, R. and Fall, R.: Detection of substantial emissions of methanol from plants to the atmosphere, \em Atmos. Environ.\/, \em 27\/, 1709-1713, 1993. Madronich, S. and Flocke, S.: \em The role of solar radiation in atmospheric chemistry\/, in: Handbook of Environmental Chemistry, Springer-Verlag, Heidelberg, pp 1-26, 1998. Martinez, M., Arnold, T., and Perner, D.: The role of bromine and chlorine chemistry for arctic ozone depletion events in ny-alesund and comparison with model calculations, \em Annales Geophysicae-Atmospheres Hydrospheres and Space Sciences\/, \em 17\/, 941-956, 1999. Matsumi, Y., Tonokura, K., Inagaki, Y., and Kawasaki, M.: Isotopic branching ratios and translational energy release of H and D atoms in reactions of O($^1$D) atoms with alkanes and alkyl chlorides, \em J. Phys. Chem.\/, \em 97\/, 6816-6821, 1993. Matzkies, F. and Manthe, U.: Accurate quantum calculations of thermal rate constants employing MCTDH: H$_2$ + OH=H + H$_2$O and D$_2$ + OH=D + DOH, \em J. Phys. Chem.-A\/, \em 108\/, 4828-4836, 1998. McCabe, D C., Gierczak, T., Talukdar, R K., and Ravishankara, A R.: Kinetics of the reaction OH plus CO under atmospheric conditions, \em Geophys. Res. Lett.\/, \em 28\/, 3135-3138, 2001. Mickley, L., Murti, P., Jacob, D., Logan, J., Rind, D., and Koch, D.: Radiative forcing from tropospheric ozone calculated with a unified chemistry-climate model, \em J. Geophys. Res.\/, \em 104\/, 30 153-30 172, 1999. Miyoshi, A., Hatakeyama, S., and Washida, N., Oh radical-initiated photooxidation of isoprene - an estimate of global co production, \em J. Geophys. Res.-Atmos.\/, \em 99\/, 18 779-18 787, 1994. Moxim, W J., Levy, H., and Kasibhatla, P S.: Simulated global tropospheric pan: Its transport and impact on nox, \em J. Geophys. Res.-Atmos.\/, \em 101\/, 12 621-12 638, 1996. Muller, J F. and Brasseur, G.: Images - a 3-dimensional chemical-transport model of the global troposphere, \em J. Geophys. Res.-Atmos.\/, \em 100\/, 16 445-16 490, 1995. Nevison, C. and Weiss, R.: Global oceanic emissions of nitrous oxide, \em J.Geophys. Res.\/, \em 100\/, 15 809-15 820, 1995. Novelli, P C., Masarie, K A., Lang, P M., Hall, B D., Myers, R C., and Elkins, J W.: Reanalysis of tropospheric co trends: Effects of the 1997-1998 wildfires, \em J. Geophys. Res.-Atmos.\/, 108(D15), 4464, doi:10.1029/2002JD003031, 2003. Olivier, J. and Berdowski, J.: Global emission sources and sinks, in: \em The Climate System\/, edited by: Berdowski, J., Guicherit, R., and Heij, B., A. A. Balkema Publishers/Swets & Zeitlinger Publishers, Lisse, pp 33-78, 2001. Olivier, J., Bouwman, A., van~der Maas, C., Berdowski, J., Veldt, C., Bloos, J., Visschedijk, A., Zandveld, P., and Haverlag, J.: Description of edgar version 2.0: A set of global emission inventories of greenhouse gases and ozone-depleting substances for all anthropogenic and most natural sources on a per country basis and on a 1x1 degree grid, RIVM report 771060 002/TNO-MEP report R96/119, National Institute of Public Health and the Environment, 1996. Olivier, J., Berdowski, J., Peters, J., Bakker, J., Visschedijk, A., and Bloos, J.: Applications of edgar. including a description of edgar 3.0: reference database with trend data for 1970-1995, RIVM report 773301 001, RIVM, 2001. Oltmans, S. and Levy~II, H.: Seasonal cycle of surface ozone over the western north atlantic, \em Nature\/, \em 358\/, 392-394, 1992. Oltmans, S. and Levy~II, H.: Surface ozone measurements from a global network, \em Atmos. Environ.\/, \em 28\/, 9-24, 1994. Oltmans, S., Komhyr, W., Franchois, P., and Matthews, W.: Tropospheric ozone: Variations from surface and ecc ozonesonde observations, in: \em Ozone in the atmosphere\/, edited by: Bojkov, R. and Fabian, P., A. Deepak, Hampton, VA, 1989. Poisson, N., Kanakidou, M., and Crutzen, P J.: Impact of non-methane hydrocarbons on tropospheric chemistry and the oxidizing power of the global troposphere: 3- dimensional modelling results, \em J. Atmos. Chem.\/, \em 36\/, 157-230, 2000. Pöschl, U., von Kuhlmann, R., Poisson, N., and Crutzen, P J.: Development and intercomparison of condensed isoprene oxidation mechanisms for global atmospheric modeling, \em J. Atmos. Chem.\/, \em 37\/, 29-52, 2000. Prather, M., Ehhalt, D., Dentener, F., Derwent, R., Dlugokencky, E., E., H., Isaksen, I., Katima, J., V., K., Matson, P., Midgley, P., and Wang, M.: Atmospheric chemistry and greenhouse gases, in: \em Climate Change 2001: The Scientific Basis. Contribution of Working Group 1 to the Third Assesment Report of the Intergovernmental Panel on Climate Change\/, edited by: Houghton, J., Ding, Y., Griggs, D., Noguer, M., van~der Linden, P., Dai, X., Maskell, K., and Johnson, C., 801pp., Cambridge University Press, Cambrige, UK and New York, USA, 2001. Prinn, R.: Evidence for substential variations of atmospheric hydroxyl radicals in the past two decades, \em Science\/, \em 292\/, 1882-1888, 2001. Prinn, R., Weiss, R., Miller, B., Huang, J., Alyea, F., Cunnold, D., Fraser, P., Hartley, D., and Simmonds, P.: Atmospheric trends and lifetime of ch3ccl3 and global oh concentrations, \em Science\/, \em 269\/, 187-192, 1995. Roberts, J.: The atmospheric chemistry of organic nitrates, \em Atmos. Environ.\/, \em 24A\/, 243, 1990. Sadourny, R. and Laval, K.: January and july performance of the lmd general circulation model, in: \em New Perspectives in Climate Modeling\/, edited by: Berger, A. and Nicolis, C., pp 173-197, Elsevier, 1984. Sander, R.: Compilation of henry's law constants for inorganic and organic species of potential importance in environmental chemistry (version 3), http://www.mpch-mainz.mpg.de/~sander/res/henry.html, 1999. Sander, S., Golden, D., Hampson, R., Kurylo, M., Howard, C., Ravishankara, A., Kolb, C., and Molina, M.: Chemical kinetics and photochemical data for use in stratospheric modeling. supplement to evaluation 12: Update of key reactions, \em JPL Publ.\/, \em 00-3\/, 2000. Sander, S., Golden, D., Hampson, R., Kurylo, M., Howard, C., Ravishankara, A., Kolb, C., and Molina, M.: Chemical kinetics and photochemical data for use in stratospheric modeling, evaluation number 14, \em JPL Publ.\/, \em 02-25\/, 2002. Sanderson, M. G. and Jones, C. D. and Collins, W. J., Johnson, C. E., and Derwent, R. G.: Effect of climate change on isoprene emissions and surface ozone levels, \em Geophys. Res. Lett., \em 30(18), 1936, doi:10.1029/2003GL017642, 2003. Seinfeld, J. and Pandis, S.: \em Atmospheric Chemistry and Physics\/, John Wiley & Sons, Inc., New York, 1998. Shallcross, D. and Monks, P.: New directions: a role for isoprene in biosphere-climate-chemistry feedbacks, \em Atmos. Environ.\/, \em 34\/, 1659-1660, 2000. Sharkey, T. and Singsaas, E.: Why plants emit isoprene, \em Nature\/, \em 374\/(6525), 769-769, 1995. Singh, H., Chen, Y., Tabazadeh, A., Fukui, Y., Bey, I., Yantosca, R., Jacob, D., Arnold, F., Wohlfrom, K., Atlas, E., Flocke, F., Blake, D., Blake, N., Heikes, B., Snow, J., Talbot, R., Gregory, G., Sachse, G., Vay, S., and Kondo, Y.: Distribution and fate of selected oxygenated organic species in the troposphere and lower stratosphere over the atlantic, \em J. Geophys. Res.-Atmos.\/, \em 105\/, 3795-3805, 2000. Singh, H., Chen, Y., Staudt, A., Jacob, D., Blake, D., Heikes, B., and Snow, J.: Evidence from the pacific troposphere for large global sources of oxygenated organic compounds, \em Nature\/, \em 410\/, 1078-1081, 2001. Singh, H B., Herlth, D., Ohara, D., Zahnle, K., Bradshaw, J D., Sandholm, S T., Talbot, R., Gregory, G L., Sachse, G W., Blake, D R., and Wofsy, S C.: Summertime distribution of pan and other reactive nitrogen species in the northern high-latitude atmosphere of eastern canada, \em J. Geophys. Res.-Atmos.\/, \em 99\/, 1821-1835, 1994a. Singh, H B., Ohara, D., Herlth, D., Sachse, W., Blake, D R., Bradshaw, J D., Kanakidou, M., and Crutzen, P J.: Acetone in the atmosphere - distribution, sources, and sinks, \em J. Geophys. Res.-Atmos.\/, \em 99\/, 1805-1819, 1994b. Sitch, S., Smith, B., Prentice, I C., Arneth, A., Bondeau, A., Cramer, W., Kaplan, J O., Levis, S., Lucht, W., Sykes, M T., Thonicke, K., and Venevsky, S.: Evaluation of ecosystem dynamics, plant geography and terrestrial carbon cycling in the lpj dynamic global vegetation model, \em Global Change Biology\/, \em 9\/, 161-185, 2003. Spivakovsky, C., Yevich, R., Logan, J., Wofsy, S., and McElroy, M.: Tropospheric oh in a three-dimensional chemical tracer model: An assessment based on observations of ch3ccl3, \em J. Geophys. Res.\/, \em 95\/, 18 441-18 471, 1990. Spivakovsky, C M., Logan, J A., Montzka, S A., Balkanski, Y J., Foreman-Fowler, M., Jones, D. B A., Horowitz, L W., Fusco, A C., Brenninkmeijer, C. A M., Prather, M J., Wofsy, S C., and McElroy, M B.: Three-dimensional climatological distribution of tropospheric oh: Update and evaluation, \em J. Geophys. Res.-Atmos.\/, \em 105\/, 8931-8980, 2000. Sprengnether, M., Demerjian, K L., Donahue, N M., and Anderson, J G.: Product analysis of the oh oxidation of isoprene and 1,3-butadiene in the presence of no, \em J. Geophys. Res.-Atmos.\/, 107(D15), 4268, doi:10.1029/2001JD000716, 2002. Stockwell, W., Kirchner, F., Kuhn, M., and Seefeld, S.: A new mechanism for regional atmospheric chemistry modeling, \em J. Geophys. Res.\/, \em 102\/, 25 847-25 879, 1997. Tang, T. and McConnell, J C.: Autocatalytic release of bromine from arctic snow pack during polar sunrise, \em Geophys. Res. Lett.\/, \em 23\/, 2633-2636, 1996. Taylor, G E.: Risk assessment of tropospheric ozone: Human health, natural resources, and ecology, \em Human and Ecological Risk Assessment\/, \em 7\/, 1183-1193, 2001. Tiedtke, M.: A comprehensive mass flux scheme for cumulus parameterization in large-scale models, \em Mon. Wea. Rev.\/, \em 117\/, 1779-1800, 1989. Tsigaridis, K. and Kanakidou, M.: Global modelling of secondary organic aerosol in the troposphere: a sensitivity analysis, \em Atmos. Chem. Phys.\/, \em 3\/, 1849-1869, 2003. Tyndall, G., Wallington, T., and Ball, J.: FTIR product study of the reactions CH3O2 + CH$_3$O$_2$ and CH$_3$O$_2$ + O$_3$, \em J. Phys. Chem.-A\/, \em 102\/, 2547-2554, 1998. Tyndall, G S., Orlando, J J., and Calvert, J G.: Upper limit for the rate coefficient for the reaction HO$_2$ + NO$_2$ $\rightarrow$ HONO + O$_2$, \em Environ. Sci. Technol.\/, \em 29\/, 202-206, 1995. Van~der Werf, G R., Randerson, J T., Collatz, G J., and Giglio, L.: Carbon emissions from fires in tropical and subtropical ecosystems, \em Global Change Biology\/, \em 9\/, 547-562, 2003. Van~Leer, B.: Towards the ultimate conservative difference scheme. part iv: A new approach to numerical convection, \em J. Comput. Phys.\/, \em 23\/, 276-299, 1977. von Kuhlmann, R., Lawrence, M. G., Pöschl, U., and Crutzen, P. J.: Sensitivities in global scale modelling of isoprene, \em Atmos. Chem. Phys.\/, \em 4\/, 1-17, 2004. Walcek, C., Brost, R., Chang, J., and Wesely, M.: SO$_2$, sulfate and HNO$_3$ deposition velocities computed using regional landuse and meteorological data, \em Atmos. Environ.\/, \em 20\/, 949-964, 1986. Walmsley, J L. and Wesely, M L.: Modification of coded parametrizations of surface resistances to gaseous dry deposition, \em Atmos. Environ.\/, \em 30\/, 1181-1188, 1996. Wang, Y H., Jacob, D J., and Logan, J A.: Global simulation of tropospheric O$_3$-NO$_\mathrmx$-hydrocarbon chemistry 1. model formulation, \em J. Geophys. Res.-Atmos.\/, \em 103\/, 10 713-10 725, 1998a. Wang, Y H., Logan, J A., and Jacob, D J.: Global simulation of tropospheric O$_3$-NO$_\mathrmx$-hydrocarbon chemistry 2. model evaluation and global ozone budget, \em J. Geophys. Res.-Atmos.\/, \em 103\/, 10 727-10 755, 1998b. Wang, Y H., Jacob, D J., and Logan, J A.: Global simulation of tropospheric O$_3$-NO$_\mathrmx$-hydrocarbon chemistry 3. origin of tropospheric ozone and effects of nonmethane hydrocarbons, \em J. Geophys. Res.-Atmos.\/, \em 103\/, 10 757-10 767, 1998c. 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 hox chemistry, \em Global Biogeochem. Cycles\/, \em 13\/, 9-17, 1999. Wennberg, P.: Atmospheric chemistry - bromine explosion, \em Nature\/, \em 397\/, 299pp., 1999. Wesely, M.: Parameterization of surface resistances to gaseous dry deposition in regional-scale numerical models, \em Atmos. Environ.\/, \em 23\/, 1293-1304, 1989. Wesely, M L. and Hicks, B B.: A review of the current status of knowledge on dry deposition, \em Atmos. Environ.\/, \em 34\/, 2261-2282, 2000. World~Meteorological~Organisation: Scientific assessment of ozone depletion: 1998, \em Rep. 44\/, Global Ozone Obs. Syst., Geneva, Switzerland, 1998. Yienger, J. and Levy~II, H.: Empirical model of global soil-biogenic nox emissions, \em J. Geophys. Res.\/, \em 100\/, 11 447-11 464, 1995. Yu, H. and Varandas, A.: Dynamics of H(D) + O$_3$ reactions on a double many-body expansion potential-energy surface for ground state HO$_3$, \em J. Chem. Soc. - Faraday Trans.\/, \em 93\/, 2,651-2,656, 1997.