ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-10-4403-2010 Observed and simulated global distribution and budget of atmospheric C<sub>2</sub>-C<sub>5</sub> alkanes Pozzer A. 1 2 Pollmann J. 2 Taraborrelli D. 2 Jöckel P. 2 5 Helmig D. 3 Tans P. 4 Hueber J. 3 Lelieveld J. 1 2 The Cyprus Institute, Energy, Environment and Water Research Center, P.O. Box 27456, 1645 Nicosia, Cyprus Air Chemistry Department, Max-Planck Institute of Chemistry, P.O. Box 3060, 55020 Mainz, Germany Institute of Arctic and Alpine Research (INSTAAR), University of Colorado, UCB 450, CO 80309, USA NOAA/ESRL, 325 Broadway, Boulder, CO 80303, USA now at: DLR, Institut fuer Physik der Atmosphaere, Oberpfaffenhofen, 82234 Wessling, Germany 12 05 2010 10 9 4403 4422 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/10/4403/2010/acp-10-4403-2010.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/10/4403/2010/acp-10-4403-2010.pdf

The primary sources and atmospheric chemistry of C<sub>2</sub>-C<sub>5</sub> alkanes were incorporated into the atmospheric chemistry general circulation model EMAC. Model output is compared with new observations from the NOAA/ESRL GMD Cooperative Air Sampling Network. Based on the global coverage of the data, two different anthropogenic emission datasets for C<sub>4</sub>-C<sub>5</sub> alkanes, widely used in the modelling community, are evaluated. We show that the model reproduces the main atmospheric features of the C<sub>2</sub>-C<sub>5</sub> alkanes (e.g., seasonality). While the simulated values for ethane and propane are within a 20% range of the measurements, larger deviations are found for the other tracers. According to the analysis, an oceanic source of butanes and pentanes larger than the current estimates would be necessary to match the observations at some coastal stations. Finally the effect of C<sub>2</sub>-C<sub>5</sub> alkanes on the concentration of acetone and acetaldehyde are assessed. Their chemical sources are largely controlled by the reaction with OH, while the reactions with NO<sub>3</sub> and Cl contribute only to a little extent. The total amount of acetone produced by propane, <i>i</i>-butane and <i>i</i>-pentane oxidation is 11.2 Tg/yr, 4.3 Tg/yr, and 5.8 Tg/yr, respectively. Moreover, 18.1, 3.1, 3.4, 1.4 and 4.8 Tg/yr of acetaldehyde are formed by the oxidation of ethane, propane, <i>n</i>-butane, <i>n</i>-pentane and <i>i</i>-pentane, respectively.

 References Andreae, M O. and Merlet, P.: Emission of trace gases and aerosols from biomass burning, Global Biogeochem. Cy., 15, 955–966, 2001. Arnold, S R., Chipperfield, M P., and Blitz, M.: A three-dimensional model study of the effect of new temperature-dependent quantum yields for acetone photolysis, Geophys. Res. Lett., 110, D22305, doi:10.1029/2005JD005998, 2005. Atkinson, R.: Atmospheric chemistry of VOCs and NO<sub>x</sub>, Atmos. Environ., 34, 2063–2101, 2000. Bey, I., Jacob, D J., Yantosca, R M., Logan, J A., Field, B D., Fiore, A M., Li, Q., Liu, H Y., Mickley, L J., and Schultz, M G.: Global modeling of tropospheric chemistry with assimilated meteorology: Model description and evaluation, J. Geophys. Res., 106, 23073–23095, 2001. Blake, D. and Rowland, S.: Urban leakage of liquefied petroleum gas and its impact on Mexico City air quality, Science, 269, 953–956, 1995. Blake Jr., D R., T S., T.-Y-Chen, Whipple, W., and Rowland, F S.: Effects of biomassburning on summertime nonmethane hydrocarbon concentrationsin the Canadian wetlands, J. Geophys. Res., 99, 1699–1719, 1993. Blake, N., R., B D., Sive, B., Ketzenstein, A S., Meinardi, S., Wingenter, O., Atlas, E L., Flocke, F., Ridley, B A., and Sherwood, F.: The seasonalevolution of NMHCs and light alkyl nitrates at mniddle to high northern latitudes during TOPSE, J. Geophys. Res., 108, 8359, doi:10.1129/2001JD001467, 2003. Blitz, M., Heard, D., Pilling, M., Arnold, S R., and Chipperfield, M P.: Pressure and temperature-dependent quantum yields for the photodissocuation od acetone between 279 and 327.5 nm, Geophys. Res. Lett., 31, L06111, doi:10.1029/2003GL018793, 2004. Bozzano, R., Siccardi, A., Schiano, M. E., Borghini, M., and Castellari, S.: Comparison of ECMWF surface meteorology and buoy observations in the Ligurian Sea, Ann. Geophys., 22, 317–330, doi:10.5194/angeo-22-317-2004, 2004. Broadgate, W J., Liss, P S., and Penkett, S A.: Seasonal emissions of isoprene and other reactive hydrocarbon gases from the ocean, Geophys. Res. Lett., 24, 2675–2678, 1997. Brühl, C., Pöschl, U., Crutzen, P J., and Steil, B.: Acetone and PAN in the upper troposphere: impact on ozone production from aircraft emissions, Atmos. Environ., 34, 3931–3938, 2000. Brunner, D., Staehelin, J., Rogers, H. L., Köhler, M. O., Pyle, J. A., Hauglustaine, D., Jourdain, L., Berntsen, T. K., Gauss, M., Isaksen, I. S. A., Meijer, E., van Velthoven, P., Pitari, G., Mancini, E., Grewe, G., and Sausen, R.: An evaluation of the performance of chemistry transport models by comparison with research aircraft observations. Part 1: Concepts and overall model performance, Atmos. Chem. Phys., 3, 1609–1631, doi:10.5194/acp-3-1609-2003, 2003. Cardelino, C A. and Chameides, W L.: Natural hydrocarbons, urbanization, and urban ozone, J. Geophys. Res., 95, 13971–13979, 1990. Daescu, D., Sandu, A., and Carmichael, G.: Direct and Adjoint Sensitivity Analysis of Chemical Kinetic Systems with KPP: II – Validation and Numerical Experiments, Atmos. Environ., 37, 5097–5114, 2003. Damian, V., Sandu, A., Damian, M., Potra, F., and Carmichael, G.: The Kinetic PreProcessor KPP – A Software Environment for Solving Chemical Kinetics, Computers and Chemical Engineering, 26, 2002. Emmons, L K., Hauglustaine, D A., Müller, 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, J. Geophys. Res., 105, 20497–20538, 2000. Etiope, G. and Ciccioli, P.: Earth's Degassing: A Missing Ethane and Propane Source, Science, 323, p 478, 2009. Folberth, G. A., Hauglustaine, D. A., Lathière, J., and Brocheton, F.: Interactive chemistry in the Laboratoire de Météorologie Dynamique general circulation model: model description and impact analysis of biogenic hydrocarbons on tropospheric chemistry, Atmos. Chem. Phys., 6, 2273–2319, doi:10.5194/acp-6-2273-2006, 2006. Folkins, I. and Chatfield, R.: Impact of acetone on ozone production and OH in the upper troposphere at high NOx, J. Geophys. Res., 105, 11585–11599, 2000. Friedrich, R. and Obermeier, A.: Anthropogenic emissions of volatile organic compounds, Academic, San Diego, California, 2–38, 1999. Gautrois, M., Brauers, T., Koppmann, R., Rohrer, F., Stein, O., and Rudolph, J.: Seasonal variability and trends of volatile organic compounds in the lower polar troposphere, J. Geophys. Res., 108, 4393, doi:10.1029/2002JD002765, 2003. Goldan, P D., Kuster, W., Fehsenfeld, F., and Montzka, S.: Hydrocarbon measurements in the southeastern United States: The Rural Oxidants in the Southern Environment (ROSE) program 1990, J. Geophys. Res., 100, 35945–35963, 1995. Goldan, P D., Parrish, D D., Kuster, W C., Trainer, M., McKeen, S., Holloway, J., Jobson, B., Sueper, D., and Fehsenfeld: Airborne measurements of isoprene,CO, and anthropogenic hydrocarbons and their implications, J. Geophys. Res., 105, 9091–9105, 2000. 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, 8873–8892, 1995. 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, Atmos. Environ., 34, 2205–2230, 2000. Gupta, M L., Cicerone, R J., Blake, D R., Rowland, F S., and Isaksen, I. S A.: Global atmospheric distributions and source strengths of light hydrocarbons and tetrachloroethene, J. Geophys. Res., 103, 28219–28235, 1998. Haas-Laursen, D. and Hartley, D.: Consistent sampling methods for comparing models to CO<sub>2</sub> flask data, J. Geophys. Res., 102, 19059–19071, 1997. Hagerman, L M., Aneja, V P., and Lonneman, W A.: Characterization of non-methane hydrocarbons in the rural southeast United States, Atmos. Environ., 23, 4017–4038, 1997. Helmig, D., Tanner, D., Honrath, R., Owen, R., and Parrish, D.: Nonmethane hydrocarbons at Pico Mountain, Azores: 1. Oxidation chemistry in the North Atlantic region, J. Geophys. Res., 113, D20S91, doi:10.1029/2007JD008930, 2008. Houweling, S., Dentener, F., and Lelieveld, J.: The impact of non-methane hydrocarbon compounds on tropospheric photochemistry, J. Geophys. Res., 103, 10673–10696, 1998. Jacob, D., Field, B., Jin, E., Bey, I., Li, Q., Logan, J., and Yantosca, R.: Atmospheric budget of acetone, J. Geophys. Res., 107, 4100, doi:10.1029/2001JD000694, 2002. Jaeglé, L., Jacob, D J., Brune, W H., and Wennberg, P O.: Chemistry of HO$_x$ radicals in the upper troposphere, Atmos. Environ., 35, 469–489, 2001. Jeuken, A., Siegmund, P., Heijboer, L., Feichter, J., and Bengtsson, L.: On the potential assimilating meteorological analyses in a global model for the purpose of model validation, J. Geophys. Res., 101, 16939–16950, 1996. Jobson, B T., Wu, Z., Niki, H., and Barrie, L A.: Seasonal trends of isoprene, alkanes, and acetylene at a remote boreal site in Canada, J. Geophys. Res., 99, 1589–1599, 1994. Jöckel, P., Sander, R., Kerkweg, A., Tost, H., and Lelieveld, J.: Technical Note: The Modular Earth Submodel System (MESSy) – a new approach towards Earth System Modeling, Atmos. Chem. Phys., 5, 433–444, doi:10.5194/acp-5-433-2005, 2005. Jöckel, P., Tost, H., Pozzer, A., Brühl, C., Buchholz, J., Ganzeveld, L., Hoor, P., Kerkweg, A., Lawrence, M. G., Sander, R., Steil, B., Stiller, G., Tanarhte, M., Taraborrelli, D., van Aardenne, J., and Lelieveld, J.: The atmospheric chemistry general circulation model ECHAM5/MESSy1: consistent simulation of ozone from the surface to the mesosphere, Atmos. Chem. Phys., 6, 5067–5104, doi:10.5194/acp-6-5067-2006, 2006. Kerkweg, A., Buchholz, J., Ganzeveld, L., Pozzer, A., Tost, H., and Jöckel, P.: Technical Note: An implementation of the dry removal processes DRY DEPosition and SEDImentation in the Modular Earth Submodel System (MESSy), Atmos. Chem. Phys., 6, 4617–4632, doi:10.5194/acp-6-4617-2006, 2006a. Kerkweg, A., Sander, R., Tost, H., and Jöckel, P.: Technical note: Implementation of prescribed (OFFLEM), calculated (ONLEM), and pseudo-emissions (TNUDGE) of chemical species in the Modular Earth Submodel System (MESSy), Atmos. Chem. Phys., 6, 3603–3609, doi:10.5194/acp-6-3603-2006, 2006b. Kerkweg, A., Jöckel, P., Pozzer, A., Tost, H., Sander, R., Schulz, M., Stier, P., Vignati, E., Wilson, J., and Lelieveld, J.: Consistent simulation of bromine chemistry from the marine boundary layer to the stratosphere – Part 1: Model description, sea salt aerosols and pH, Atmos. Chem. Phys., 8, 5899–5917, doi:10.5194/acp-8-5899-2008, 2008a. Kerkweg, A., Jöckel, P., Warwick, N., Gebhardt, S., Brenninkmeijer, C. A. M., and Lelieveld, J.: Consistent simulation of bromine chemistry from the marine boundary layer to the stratosphere – Part 2: Bromocarbons, Atmos. Chem. Phys., 8, 5919–5939, doi:10.5194/acp-8-5919-2008, 2008b. Kesselmeier, J. and Staudt, M.: Biogenic Volatile Organic Compounds (VOC): An Overview on Emission, Physiology and Ecology, J. Atmos. Chem., 33, 23–88, 1999. Lee, H B., Munger, J., Steven, C., and Goldstein, A H.: Anthropogenic emissions of nonmethane hydrocarbons in the northeastern United Sates: Measured seasonal variations from 1992–1996 and 1999–2001, J. Geophys. Res., 111, D20307, doi:10.1029/2005JD006172, 2006. Lelieveld, J., Brühl, C., Jöckel, P., Steil, B., Crutzen, P. J., Fischer, H., Giorgetta, M. A., Hoor, P., Lawrence, M. G., Sausen, R., and Tost, H.: Stratospheric dryness: model simulations and satellite observations, Atmos. Chem. Phys., 7, 1313–1332, doi:10.5194/acp-7-1313-2007, 2007. Logan, J A.: Tropospheric ozone: Seasonal behavior, trends, and anthropogenic influence, J. Geophys. Res., 90, 10463–10482, 1985. Marandino, C., De~Bruyn, W., Miller, S., Prather, M., and Saltzmann, E.: Oceanic uptake and the global atmospheric acetone budget, Geophys. Res. Lett., 32, L15806, doi:10.1029/2005GL023285, 2005. McKeen, S A., Gierczak, T., Burkholder, J B., Wennberg, P O., Hanisco, T F., Keim, E R., Gao, R.-S., Liu, S C., Ravishankara, A R., and Fahey, D W.: The photochemistry of acetone in the upper troposphere: A source of odd-hydrogen radicals, Geophys. Res. Lett., 24, 3177–3180, 1997. McLaren, R., Singleton, D L., Lai, J Y., Khouw, B., Singer, E., Wu, Z., and Niki, H.: Analysis of motor vehicle sources and their contribution to ambient hydrocarbon distributions at urban sites in Toronto during the Southern Ontario Oxidants Study, Atmos. Environ., 30, 2219–2232, 1996. Middleton, P., Stockwell, W R., and Carter, W. P L.: Aggregation and analysis of volatile organic compound emissions for regional modeling, Atmos. Environ., 24A, 1107–1133, 1990. Millet, D. B., Guenther, A., Siegel, D. A., Nelson, N. B., Singh, H. B., de Gouw, J. A., Warneke, C., Williams, J., Eerdekens, G., Sinha, V., Karl, T., Flocke, F., Apel, E., Riemer, D. D., Palmer, P. I., and Barkley, M.: Global atmospheric budget of acetaldehyde: 3-D model analysis and constraints from in-situ and satellite observations, Atmos. Chem. Phys., 10, 3405–3425, doi:10.5194/acp-10-3405-2010, 2010. Moxim, W J., Levy, H., and Kasibhatla, P S.: Simulated global tropospheric PAN: Its transport and impact on NO<sub>x</sub>, J. Geophys. Res., 101, 12621–12638, 1996. Müller, J.-F. and Brasseur, G.: IMAGES: A three-dimensional chemical transport model of the global troposphere, J. Geophys. Res., 100, 16445–16490, 1995. Neeb, P.: Structure-Reactivity Based Estimation of the Rate Constants for Hydroxyl Radical Reactions with Hydrocarbons, J. Atmos. Chem., 35, 295–315, 2000. Olivier, J. G J., Bouwman, A F., van~der Maas, C. W M., Berdowski, J. J M., Veldt, C., Bloos, J. P J., Visschedijk, A. J J., Zandveld, P. Y J., and Haverlag, J L.: Description of EDGAR Version 2.0: A set of global inventories of greenhouse gases and ozone-depleting substances for all anthrophogenic and most natural sources on a per country $1^\circ \times 1^\circ$ grid, RIVM Rep. 771060002, Rijksinstituut, Bilthoven, Netherlands, 1996. Olivier, J. G J., Bloos, J. P J., Berdowski, J. J M., Visschedijk, A. J H., and Bouwman, A F.: A 1990 global emission inventory of anthropogenic sources of carbon monoxide on $1^\circ \times 1^\circ$ developed in the framework of EDGAR/GEIA, Chemosphere, 1, 1–17, 1999. Parrish, D., Stohl, A., Forster, C., Atlas, E., Blake, D., Goldan, P., Kuster, W C., and de~Gouw, J.: Effects of mixing on evoultion of hydrocarbon ratios in the troposphere, J. Geophys. Res., 112, D10S34, doi:10.1029/2006JD007583, 2007. Plass-Dülmer, C., Koppmann, R., Ratte, M., and Rudolph, J.: Light non-methane hydrocarbons in seawater, Global Biogeochem. Cy., 9, 79–100, 1995. 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, J. Atmos. Chem., 36, 157–230, 2000. Pollmann, J., Helmig, D., Hueber, J., Plass-Dülmer, C., and Tans, P.: Sampling,storage and analysis $C_2-C_7$ non-methane hydrocarbons from the US National Oceanic and Atmospheric Administration Cooperative Air Sampling Network glass flasks, J. Chromatogr. A, 1188, 75–87, 2008. Potter, C., Klooster, S., Bubenheim, D., Singh, H B., and Myneni, R.: Modeling terrestrial biogenic sources of oxygenated organic emissions, Earth Interaction, 7, 1–15, 2003. Pozzer, A., Jöckel, P., Tost, H., Sander, R., Ganzeveld, L., Kerkweg, A., and Lelieveld, J.: Simulating organic species with the global atmospheric chemistry general circulation model ECHAM5/MESSy1: a comparison of model results with observations, Atmos. Chem. Phys., 7, 2527–2550, doi:10.5194/acp-7-2527-2007, 2007. Pozzer, A., Jöckel, P., and Van Aardenne, J.: The influence of the vertical distribution of emissions on tropospheric chemistry, Atmos. Chem. Phys., 9, 9417–9432, doi:10.5194/acp-9-9417-2009, 2009. Roberts, J., Jutte, R., Fehsenfeld, F., Albriton, D., and Sievers, R.: Measurements of anthropogenic hydrocarbon concentration ratios in the rural troposphere: Discrimination between background and urban sources, Atmos. Environ., 19, 1945–1950, 1985. Roeckner, E., Brokopf, R., Esch, M., Giorgetta, M., Hagemann, S., Kornblueh, L., Manzini, E., Schlese, U., and Schulzweida, U.: Sensitivity of simulated climate to horizontal and vertical resolution in the ECHAM5 atmosphere model, J. Climate, 19, 3771–3791, 2006. Roelofs, G.-J. and Lelieveld, J.: Tropospheric ozone simulation with a chemistry-general circulation model: Influence of higher hydrocarbon chemistry, J. Geophys. Res., 105, 22697–22712, 2000. Rood, R B.: Numerical advection algorithms and their role in atmospheric transport and chemistry models, Rev. Geophys., 25, 71–100, 1987. Rudolph, J.: The tropospheric distribution and budget of ethane, J. Geophys. Res., 100, 11369–11381, 1995. Saito, T., Yokouchi, Y., and Kawamura, K.: Distribution of C<sub>2</sub>–C$_6$ hydrocarbons over the western north Pacific and eastern Indian Ocean, Atmos. Environ., 34, 4373–4381, 2000. Salstein, D., Ponte, R., and Cady-Pereira, K.: Uncertainties in atmospheric surface pressure fields from global analyses, J. Geophys. Res., 113, D14107, doi:10.1029/2007JD009531, 2008. Sander, R., Kerkweg, A., Jöckel, P., and Lelieveld, J.: Technical note: The new comprehensive atmospheric chemistry module MECCA, Atmos. Chem. Phys., 5, 445–450, doi:10.5194/acp-5-445-2005, 2005. Sandu, A., Daescu, D., and Carmichael, G.: Direct and Adjoint Sensitivity Analysis of Chemical Kinetic Systems with KPP: I – Theory and Software Tools, Atmos. Environ., 37, 5083–5096, 2003. Saunders, S. M., Jenkin, M. E., Derwent, R. G., and Pilling, M. J.: Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A): tropospheric degradation of non-aromatic volatile organic compounds, Atmos. Chem. Phys., 3, 161–180, doi:10.5194/acp-3-161-2003, 2003. Seinfeld, J H. and Pandis, S.: Atmospheric Chemistry and Physics: From Air Pollution to Climate Change, Wiley-Interscience, 1997. Sharma, U K., Kajii, Y., and Akimoto, H.: Seasonal variation of C<sub>2</sub>-C$_6$ NMHCs at Happo, a remote site in Japan, Atmos. Environ., 34, 4447–4458, 2000. Singh, H., Salas, l., Chatfield, R., Czech, E., Fried, A., Walega, J., Evans, M., Field, B., Jacob, D., Blake, D., Heikes, B., Talbot, R andSachse, G., Crawford, J., Avery, M., Sandholm, S., and Fuelberg, H.: Analysis of the atmospheric distriburion, sources, and sinks of oxygenated volatile organic chemicals based in measurements over the Pacific during TRACE-P, J. Geophys. Res., 105(D3), D15S07, doi:10.1029/2003JD003883, 2004. Singh, H B. and Zimmermann, P.: Atmospheric distribution and sources of nonmethane hydrocarbons, John Wiley, New York, 1992. Singh, H B., O'Hara, D., Herlth, D., Sachse, W., Blake, D R., Bradshaw, J D., Kanakidou, M., and Crutzen, P J.: Acetone in the atmosphere: Distribution, source, and sinks, J. Geophys. Res., 99, 1805–1819, 1994. Singh, H B., Kanakidou, M., Crutzen, P J., and Jacob, D J.: High concentrations and photochemical fate of oxygenated hydrocarbons in the global troposphere, Nature, 378, 50–54, 1995. Singh, H B., Chen, Y., Staudt, A C., Jacob, D J., Blake, D R., Heikes, B G., and Snow, J.: Evidence from the Pacific troposphere for large global sources of oxygenated organic compounds, Nature, 410, 1078–1081, 2001. Singh, H B., Tabazadeh, A., Evans, M J., Field, B D., Jacob, D J., Sachse, G., Crawford, J H., Shetter, R., and Brune, W H.: Oxygenated volatile organic chemicals in the oceans: Inferences and implications based on atmospheric observations and air-sea exchange models, Geophys. Res. Lett., 30, 1862, doi:10.1029/2003GL017933, 2003. Singh, H B., Salas, L. J., Ridley, B. A., Shetter, J. D., Donahue, N. M., Fehsenfeld, F. C., Fahey, D. W., Parrish, D. D., Williams, E. J., Liu, S. C., Hübler, G., and Murphy, P. C.: Relationship between peroxyacetyl nitrate (PAN) and nitrogen oxides in the clean troposphere, Nature, 318, 347–349, 1985. 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, J. Geophys. Res., 105, 8931–8980, 2000. Swanson, A., Blake, N., Atlas, E., Flocke, F., Blake, D R., and Sherwood, F.: Seasonal variation of $C_2-C_4$ nonmethane hydrocarbons and $C1-C4$ alkyl nitrates at the Summit research station in Greenland, J. Geophys. Res., 108, 4065, doi:10.1129/2001JD001445, 2003. Taddei, S., Toscano, P., Gioli, B., Matese, A., Miglietta, F., Vaccari, F P., Zaldei, A., Custer, T., and Williams, J.: Carbon Dioxide and Acetone Air¿Sea Fluxes over the Southern Atlantic, Environ. Sci. Technol., 43, 5218–5222, 2009. Taylor, K.: Summarizing multiple aspects of model performance in a single diagram, J. Geophys. Res., 106, 7183–7192, 2001. Tost, H., Jöckel, P., Kerkweg, A., Sander, R., and Lelieveld, J.: Technical note: A new comprehensive SCAVenging submodel for global atmospheric chemistry modelling, Atmos. Chem. Phys., 6, 565–574, doi:10.5194/acp-6-565-2006, 2006. Tyndall, G S., Staffelbach, T A., Orlando, J J., and Calvert, J G.: Rate coefficients for the reactions of \chemOH radicals with methylglyoxal and acetaldehyde, Int. J. Chem. Kinetics, 27, 1009–1020, 1995. Tyndall, G S., Orlando, J J., Wallington, T J., Hurley, M D., Goto, M., and Kawasaki, M.: Mechanism of the reaction of OH radicals with acetone and acetaldehyde at 251 and 296 K, Phys. Chem. Chem. Phys., 4, 2189–2193, 2002. van Aardenne, J., Dentener, F., Olivier, J., Peters, J., and Ganzeveld, L.: The EDGAR 3.2 Fast Track 2000 dataset (32FT2000), online available at: http://www.mnp.nl/edgar/model/v32ft2000edgar/docv32ft2000/, 2005. van Aardenne, J A., Dentener, F J., Olivier, J. G J., Klein Goldewijk, C. G M., and Lelieveld, J.: A $1\deg \times 1\deg$ resolution data set of historical anthropogenic trace gas emissions for the period 1890–1990, Global Biogeochem. Cy., 15, 909–928, 2001. Van~der Werf, G R., Randerson, J T., Collatz, G J., Giglio, L., Kasibhatla, P S., Avelino, A., Olsen, S C., and Kasischke, E.: Continental-scale partitioning of fire emissions during the 1997–2001 El Nino/La Nina period, Science, 303, 73–76, 2004. von Kuhlmann, R., Lawrence, M G., Crutzen, P J., and Rasch, P J.: A model for studies of tropospheric ozone and nonmethane hydrocarbons: Model description and ozone results, J. Geophys. Res., 108, 4294, doi:10.1029/2002JD002893, 2003a. von Kuhlmann, R., Lawrence, M G., Crutzen, P J., and Rasch, P J.: A Model for Studies of Tropospheric Ozone and Non-Methane Hydrocarbons: Model Evaluation of Ozone Related Species, J. Geophys. Res., 108, 4729, doi:10.1029/2002JD003348, 2003b. Wang, Y., Jacob, D J., and Logan, J A.: Global simulation of tropospheric O<sub>3</sub>-NO$_x$-hydrocarbon chemistry, 1. Model formulation, J. Geophys. Res., 103, 10713–10725, 1998. Wennberg, P O., Hanisco, T F., Jaeglé, L., Jacob, D., Hintsa, E J., Lanzendorf, E J., Anderson, J G., Gao, R.-S., Keim, E R., Donnelly, S G., Negro, L. A D., Fahey, D W., McKeen, S A., Salawitch, R J., Webster, C R., May, R D., Herman, R L., Proffitt, M H., Margitan, J J., Atlas, E L., Schauffler, S M., Flocke, F., McElroy, C T., and Bui, T P.: Hydrogen radicals, nitrogen radicals, and the production of O<sub>3</sub> in the upper troposphere, Science, 279, 49–53, 1998. World Meteorological~Organization, W.: A WMO/GAW expert workshop on global long-term measurements of volatile organic compounds (VOCs), Tech. rep., WMO Rep 171, Geneva, Switzerland, 2007.