Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 8 16 2008 10.5194/acp-8-4529-2008 http://www.atmos-chem-phys.net/8/4529/2008/ http://www.atmos-chem-phys.net/8/4529/2008/acp-8-4529-2008.html http://www.atmos-chem-phys.net/8/4529/2008/acp-8-4529-2008.pdf 4529 4546 2008-08-05 Improved simulation of isoprene oxidation chemistry with the ECHAM5/MESSy chemistry-climate model: lessons from the GABRIEL airborne field campaign T. M. Butler tmb@mpch-mainz.mpg.de D. Taraborrelli C. Brühl H. Fischer H. Harder M. Martinez J. Williams M. G. Lawrence J. Lelieveld Max Planck Institute for Chemistry, Mainz, Germany The GABRIEL airborne field measurement campaign, conducted over the Guyanas in October 2005, produced measurements of hydroxyl radical (OH) concentration which are significantly higher than can be simulated using current generation models of atmospheric chemistry. Based on the hypothesis that this "missing OH" is due to an as-yet undiscovered mechanism for recycling OH during the oxidation chain of isoprene, we determine that an OH recycling of about 40–50% (compared with 5–10% in current generation isoprene oxidation mechanisms) is necessary in order for our modelled OH to approach the lower error bounds of the OH observed during GABRIEL. Such a large amount of OH in our model leads to unrealistically low mixing ratios of isoprene. In order for our modelled isoprene mixing ratios to match those observed during the campaign, we also require that the effective rate constant for the reaction of isoprene with OH be reduced by about 50% compared with the lower bound of the range recommended by IUPAC. We show that a reasonable explanation for this lower effective rate constant could be the segregation of isoprene and OH in the mixed layer. Our modelling results are consistent with a global, annual isoprene source of about 500 Tg(C) yr^−1, allowing experimentally derived and established isoprene flux rates to be reconciled with global models. Agee, E. and Gluhovsky, A.: LES model sensitivities to domains, grids, and large-eddy timescales, J. Atmos. Sci., 56, 599–604, 1999. Anfossi, D., Rizza, U., Mangia, C., Degrazia, G A., and Marques, E P.: Estimation of the ratio between the Lagrangian and Eulerian time scales in an atmospheric boundary layer generated by large eddy simulation, Atmos. Environ., 40, 326–337, 2006. 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, J. Geophys. Res., 107, 4034, doi:10.1029/2000JD000225, 2002. Avissar, R. and Schmidt, T.: An evaluation of the scale at which ground-surface heat flux patchiness affects the convective boundary layer using large-eddy simulations, J. Atmos. Sci., 55, 2666–2689, 1998. Bartenbach, S., Williams, J., Plass-Dulmer, C., Berresheim, H., and Lelieveld, J.: In-situ measurement of reactive hydrocarbons at Hohenpeissenberg with comprehensive two-dimensional gas chromatography (GC x GC-FID): use in estimating HO and NO₃, Atmos. Chem. Phys., 7, 1–14, 2007. Campuzano-Jost, P., Williams, M B., D'Ottone, L., and Hynes, A J.: Kinetics and mechanism of the reaction of the hydroxyl radical with h(8)-isoprene and d(8)-isoprene: Isoprene absorption cross sections, rate coefficients, and the mechanism of hydroperoxyl radical production, J. Phys. Chem. A, 108, 1537–1551, 2004. Carslaw, N., Creasy, D J., Harrison, D., Heard, D E., Hunter, M C., Jacobs, P J., Jenkin, M E., Lee, J D., Lewis, A C., Pilling, M J., Saunders, S M., and Seakins, P W.: OH and HO₂ radical chemistry in a forested region of north-western Greece, Atmos. Environ., 35, 4725–4737, 2001. Ciccioli, P., Brancaleoni, E., Frattoni, M., Palo, V D., Valentini, R., Tirone, G., Seufert, G., Bertin, N., Hansen, U., Csiky, O., Lenz, R., and Sharma, M.: Emission of reactive terpene compounds from orange orchards and their removal by within-canopy processes, J. Geophys. Res., 104, 8077–8094, 1999. Denman, K., Brasseur, G., Chidthaisong, A., Ciais, P., Cox, P., Dickinson, R., Hauglustaine, D., Heinze, C., Holland, E., Jacob, D., Lohmann, U., Ramachandran, S., da~Silva~Dias, P., Wofsy, S., and Zhang, X.: Couplings Between Changes in the Climate System and Biogeochemistry, in: Climate Change 2007: The Physical Science Basis. Contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change, edited by Solomon, S., Qin, D., Manning, M., Chen, Z., Marquis, M., Averyt, K., M.Tignor, and Miller, H., Cambridge University Press, Cambridge, United Kingdom and New York, NY, USA, 2007. Di Carlo, P., Brune, W H., Martinez, M., Harder, H., Lesher, R., Ren, X R., Thornberry, T., Carroll, M A., Young, V., Shepson, P B., Riemer, D., Apel, E., and Campbell, C.: Missing OH reactivity in a forest: Evidence for unknown reactive biogenic VOCs, Science, 304, 722–725, 2004. Eerdekens, G., Ganzeveld, L., Vilà-Guerau de Arellano, J., Klüpfel, T., Sinha, V., Yassaa, N., Williams, J., Harder, H., Kubistin, D., Martinez, M., and Lelieveld, J.: Flux estimates of isoprene, methanol and acetone from airborne PTR-MS measurements over the tropical rainforest during the GABRIEL 2005 campaign, Atmos. Chem. Phys. Discuss, 8, 12 903–12 969, 2008. 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, 2006. Ganzeveld, L N., van Aardenne, J A., Butler, T M., Lawrence, M G., Metzger, S M., Stier, P., Zimmermann, P., and Lelieveld, J.: Technical Note: Anthropogenic and natural offline emissions and the online EMissions and dry DEPosition submodel EMDEP of the Modular Earth Submodel system (MESSy), Atmos. Chem. Phys. Discuss, 6, 5457–5483, 2006. George, L A., Hard, T M., and O'Brien, R J.: Measurement of free radicals OH and HO₂ in Los Angeles smog, J. Geophys. Res., 104, 11 643–11 655, 1999. Goldstein, A H. and Galbally, I E.: Known and unexplored organic constituents in the earth's atmosphere, Environ. Sci. Technol., 41, 1514–1521, 2007. 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., Karl, T., Harley, P., Wiedinmyer, C., Palmer, P I., and Geron, C.: Estimates of global terrestrial isoprene emissions using MEGAN (Model of Emissions of Gases and Aerosols from Nature), Atmos. Chem. Phys., 6, 3181–3210, 2006. Harrison, D., Hunter, M C., Lewis, A C., Seakins, P W., Bonsang, B., Gros, V., Kanakidou, M., Touaty, M., Kavouras, I., Mihalopoulos, N., Stephanou, E., Alves, C., Nunes, T., and Pio, C.: Ambient isoprene and monoterpene concentrations in a Greek fir (\emphAbies Borisii-regis) forest. Reconciliation with emissions measurements and effects on measured OH concentrations, Atmos. Environ., 35, 4699–4711, 2001. Heard, D E. and Pilling, M J.: Measurement of OH and HO₂ in the troposphere, Chem. Rev., 103, 5163–5196, 2003. Houweling, S., Dentener, F., and Lelieveld, J.: The impact of nonmethane hydrocarbon compounds on tropospheric photochemistry, J. Geophys. Res., 103, 10 673–10 696, 1998. 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., Aardenne, J V., 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, 2006. Karl, T., Guenther, A., Yokelson, R J., Greenberg, J., Potosnak, M., Blake, D R., and Artaxo, P.: The tropical forest and fire emissions experiment: Emission, chemistry, and transport of biogenic volatile organic compounds in the lower atmosphere over Amazonia, J. Geophys. Res., 112, D18302, doi:10.1029/2007JD008539, 2007. 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, 2006. Krol, M. and Lelieveld, J.: Can the variability in tropospheric OH be deduced from measurements of 1,1,1-trichloroethane (methyl chloroform)?, J. Geophys. Res., 108, 4125, doi:10.1029/2002JD002423, 2003. Krol, M C., Molemaker, M J., and de~Arellano, J. V G.: Effects of turbulence and heterogeneous emissions on photochemically active species in the convective boundary layer, J. Geophys. Res., 105, 6871–6884, 2000. Kubistin, D., Harder, H., Martinez, M., Rudolf, M., Sander, R., Bozem, H., Eerdekens, G., Fischer, H., Gurk, C., Klüpfel, T., Königsstedt, R., Parchatka, U., Schiller, C., Stickler, A., Taraborrelli, D., Williams, J., and Lelieveld, J.: Hydroxyl radicals in the tropical troposphere over the Suriname rain forest: Comparison of measurements with the box model MECCA, Atmos. Chem. Phys. Discuss., accepted, 2008. Kuhn, U., Andreae, M O., Ammann, C., Araújo, A C., Brancaleoni, E., Ciccioli, P., Dindorf, T., Frattoni, M., Gatti, L V., Ganzeveld, L., Kruijt, B., Lelieveld, J., Lloyd, J., Meixner, F X., Nobre, A D., Pöschl, U., Spirig, C., Stefani, P., Thielmann, A., Valentini, R., and Kesselmeier, J.: Isoprene and monoterpene fluxes from Central Amazonian rainforest inferred from tower-based and airborne measurements, and implications on the atmospheric chemistry and the local carbon budget, Atmos. Chem. Phys., 7, 2855–2879, 2007. Kurpius, M R. and Goldstein, A H.: Gas-phase chemistry dominates O₃ loss to a forest, implying a source of aerosols and hydroxyl radicals to the atmosphere, Geophys. Res. Lett., 30, 1371, doi:10.1029/2002GL016785, 2003. Lawrence, M G., Rasch, P J., von Kuhlmann, R., Williams, J., Fischer, H., de~Reus, M., Lelieveld, J., Crutzen, P J., Schultz, M., Stier, P., Huntrieser, H., Heland, J., Stohl, A., Forster, C., Elbern, H., Jakobs, H., and Dickerson, R R.: Global chemical weather forecasts for field campaign planning: predictions and observations of large-scale features during MINOS, CONTRACE, and INDOEX, Atmos. Chem. Phys., 3, 267–289, 2003. Lelieveld, J., Dentener, F J., Peters, W., and Krol, M C.: On the role of hydroxyl radicals in the self-cleansing capacity of the troposphere, Atmos. Chem. Phys., 4, 2337–2344, 2004. Lelieveld, J., Butler, T M., Crowley, J N., Dillon, T J., Fischer, H., Ganzeveld, L., Harder, H., Lawrence, M G., Martinez, M., Taraborrelli, D., and Williams, J.: Atmospheric oxidation capacity sustained by a tropical forest, Nature, 452, 737–740, 2008. Martinez, M., Harder, H., Kubistin, D., Rudolf, M., Bozem, H., Fischer, H., Gurk, C., Königsstedt, R., Klüpfel, T., Parchatka, U., Schiller, C., Stickler, A., Williams, J., and Lelieveld, J.: Hydroxyl radicals in the tropical troposphere over the Suriname rain forest: Airborne measurements Atmos. Chem. Phys. Discuss., accepted, 2008. Pöschl, U., von Kuhlmann, R., Poisson, N., and Crutzen, P J.: Development and intercomparison of condensed isoprene oxidation mechanisms for global atmospheric modeling, J. Atmos. Chem., 37, 29–52, 2000. 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, 2007. Prinn, R G., Huang, J., Weiss, R F., Cunnold, D M., Fraser, P J., Simmonds, P G., McCulloch, A., Harth, C., Reimann, S., Salameh, P., O'Doherty, S., Wang, R. H J., Porter, L W., Miller, B R., and Krummel, P B.: Evidence for variability of atmospheric hydroxyl radicals over the past quarter century, Geophys. Res. Lett., 32, L07809, doi:10.1029/2004GL022228, 2005. Ren, X., Brune, W H., Oliger, A., Metcalf, A R., Simpas, J B., Shirley, T., Schwab, J J., Bai, C., Roychowdhury, U., Li, Y., Cai, C., Demerjian, K L., He, Y., Zhou, X., Gao, H., and Hou, J.: OH, HO₂, and OH reactivity during the PMTACS-NY Whiteface Mountain 2002 campaign: Observations and model comparison, J. Geophys. Res., 111, D10S03, doi:10.1029/2005JD006126, 2006. Roeckner, E., Bäuml, G., Bonaventura, L., Brokopf, R., Esch, M., Giorgetta, M., Hagemann, S., Kirchner, I., Kornbluch, L., Manzini, E., Rhodin, A., Schlese, U., Schulzweida, U., and Tompkins, A.: The atmospheric general circulation model ECHAM5: part 1, model description, Tech. Rep. 349, Max Planck Institut für Meteorologie, Hamburg, 2003. Sander, R., Kerkweg, A., Jöckel, P., and Lelieveld, J.: Technical note: The new comprehensive atmospheric chemistry module MECCA, Atmos. Chem. Phys., 5, 445–450, 2005. Sander, S P., Friedl, R R., Golden, D M., Kurylo, M J., Moortgat, G K., Keller-Rudek, H., Wine, P H., Ravishankara, A R., Kolb, C E., Molina, M J., Finlayson-Pitts, B J., Huie, R E., and Orkin, V L.: Chemical kinetics and photochemical data for use in atmospheric studies, Evaluation Number 15, JPL Publication 06-2, Jet Propulsion Laboratory, Pasadena, 2006. 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, 2003. Shirley, T R., Brune, W H., Ren, X., Mao, J., Lesher, R., Cardenas, B., Volkamer, R., Molina, L T., Molina, M J., Lamb, B., Velasco, E., Jobson, T., and Alexander, M.: Atmospheric oxidation in the Mexico City Metropolitan Area (MCMA) during April 2003, Atmos. Chem. Phys., 6, 2753–2765, 2006. Spivakovsky, C M., Wofsy, S C., and Prather, M J.: A numerical-method for parameterization of atmospheric chemistry – computation of tropospheric OH, J. Geophys. Res., 95, 18 433–18 439, 1990. Spivakovsky, C M., Logan, J A., Montzka, S A., Balkansky, Y J., Foreman-Fowler, M., Jones, D. B A., Horowitz, L W., Fusco, A C., Brenninkmeijer, C. A M., Prather, M J., Wofsey, S C., and McElroy, M B.: Three-dimensional climatological distribution of tropospheric \uppercaseOH: \uppercaseUpdate and evaluation, J. Geophys. Res., 105, 8931–8980, 2000. Stevenson, D S., Dentener, F J., Schultz, M G., Ellingsen, K., van Noije, T. P C., Wild, O., Zeng, G., Amann, M., Atherton, C S., Bell, N., Bergmann, D J., Bey, I., Butler, T., Cofala, J., Collins, W J., Derwent, R G., Doherty, R M., Drevet, J., Eskes, H J., Fiore, A M., Gauss, M., Hauglustaine, D A., Horowitz, L W., Isaksen, I. S A., Krol, M C., Lamarque, J F., Lawrence, M G., Montanaro, V., Müller, J F., Pitari, G., Prather, M J., Pyle, J A., Rast, S., Rodriguez, J M., Sanderson, M G., Savage, N H., Shindell, D T., Strahan, S E., Sudo, K., and Szopa, S.: Multi-model ensemble simulations of present-day and near-future tropospheric ozone, J. Geophys. Res., 111, D08301, doi:10.1029/2005JD006338, 2006. Stickler, A., Fischer, H., Bozem, H., Gurk, C., Schiller, C., Martinez-Harder, M., Kubistin, D., Harder, H., Williams, J., Eerdekens, G., Yassaa, N., Ganzeveld, L., Sander, R., and Lelieveld, J.: Chemistry, transport and dry deposition of trace gases in the boundary layer over the tropical Atlantic Ocean and the Guyanas during the GABRIEL field campaign, Atmos. Chem. Phys., 7, 3933–3956, 2007. Taraborrelli, D., Lawrence, M. G., Butler, T. M., Sander, R., and Lelieveld, J.: Mainz Isoprene Mechanism 2 (MIM2): an isoprene oxidation mechanism for regional and global atmospheric modelling, Atmos. Chem. Phys. Discuss., 8, 14033–14085, 2008. Tan, D., Faloona, I., Simpas, J B., Brune, W., Shepson, P B., Couch, T L., Summer, A L., Carroll, M A., Thornberry, T., Apel, E., Riemer, D., and Stockwell, W.: HO$_x$ budgets in a deciduous forest: Results from the PROPHET summer 1998 campaign, J. Geophys. Res., 106, 24 407–24 427, 2001. Thornton, J A., Wooldridge, P J., Cohen, R C., Martinez, M., Harder, H., Brune, W H., Williams, E J., Roberts, J M., Fehsenfeld, F C., Hall, S R., Shetter, R E., Wert, B P., and Fried, A.: Ozone production rates as a function of NO$_x$ abundances and HO$_x$ production rates in the Nashville urban plume, J. Geophys. Res., 107, 4146, doi:10.1029/2001JD000932, 2002. Tost, H., Jöckel, P., and Lelieveld, J.: Influence of different convection parameterisations in a GCM, Atmos. Chem. Phys., 6, 5475–5493, 2006a. Tost, H., Jöckel, P J., 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, 2006b. Tost, H., Jöckel, P J., and Lelieveld, J.: Lightning and convection parameterisations - uncertainties in global modelling, Atmos. Chem. Phys., 7, 4553–4568, 2007. Verver, G. H L., van Dop, H., and Holtslag, A. A M.: Turbulent mixing and the chemical breakdown of isoprene in the atmospheric boundary layer, J. Geophys. Res., 105, 3983–4002, 2000. von Kuhlmann, R., Lawrence, M G., and Crutzen, P J.: A model for studies of tropospheric ozone and nonmethane hydrocarbons: Model evaluation of ozone-related species, J. Geophys. Res., 108, 4729, doi:10.1029/2002JD003348, 2003. von Kuhlmann, R., Lawrence, M G., Pöschl, U., and Crutzen, P J.: Sensitivities in global scale modeling of isoprene, Atmos. Chem. Phys., 4, 1–17, 2004. Williams, J., Gros, V., Bonsang, B., and Kazan, V.: HO cycle in 1997 and 1998 over the southern Indian Ocean derived from CO, radon, and hydrocarbon measurements made at Amsterdam Island, J. Geophys. Res., 106, 12 719–12 725, 2001.