Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 10 12 2010 10.5194/acp-10-5515-2010 http://www.atmos-chem-phys.net/10/5515/2010/ http://www.atmos-chem-phys.net/10/5515/2010/acp-10-5515-2010.html http://www.atmos-chem-phys.net/10/5515/2010/acp-10-5515-2010.pdf 5515 5533 2010-06-22 Optimal estimation of the surface fluxes of methyl chloride using a 3-D global chemical transport model X. Xiao xue.xiao@rice.edu R. G. Prinn P. J. Fraser P. G. Simmonds R. F. Weiss S. O'Doherty B. R. Miller P. K. Salameh C. M. Harth P. B. Krummel L. W. Porter J. Mühle B. R. Greally D. Cunnold R. Wang S. A. Montzka J. W. Elkins G. S. Dutton T. M. Thompson J. H. Butler B. D. Hall S. Reimann M. K. Vollmer F. Stordal C. Lunder M. Maione J. Arduini Y. Yokouchi Department of Earth, Atmospheric, and Planetary Sciences, MIT, Cambridge, MA 02139, USA Center for Australian Weather and Climate Research, CSIRO Marine and Atmospheric Research, Aspendale, Victoria, 3195, Australia School of Chemistry, University of Bristol, Bristol, UK Scripps Institution of Oceanography, University of California, San Diego, La Jolla, CA 92093, USA Center for Australian Weather and Climate Research, Bureau of Meteorology, Melbourne, Victoria, 3000, Australia Georgia Institute of Technology, Atlanta, GA, USA ESRL, NOAA, Boulder, CO, USA Swiss Federal Institute for Materials Science and Technology, Laboratory for Air Pollution/Environmental Technology, Duebendorf, Switzerland Norwegian Institute for Air Research, Kjeller, Norway University of Urbino, Urbino, Le Marche, 61029, Italy National Institute for Environmental Studies, Tsukuba, Ibaraki, Japan now at: Civil & Environmental Engineering, Rice University, Houston, TX 77005, USA deceased Methyl chloride (CH₃Cl) is a chlorine-containing trace gas in the atmosphere contributing significantly to stratospheric ozone depletion. Large uncertainties in estimates of its source and sink magnitudes and temporal and spatial variations currently exist. GEIA inventories and other bottom-up emission estimates are used to construct a priori maps of the surface fluxes of CH₃Cl. The Model of Atmospheric Transport and Chemistry (MATCH), driven by NCEP interannually varying meteorological data, is then used to simulate CH₃Cl mole fractions and quantify the time series of sensitivities of the mole fractions at each measurement site to the surface fluxes of various regional and global sources and sinks. We then implement the Kalman filter (with the unit pulse response method) to estimate the surface fluxes on regional/global scales with monthly resolution from January 2000 to December 2004. High frequency observations from the AGAGE, SOGE, NIES, and NOAA/ESRL HATS in situ networks and low frequency observations from the NOAA/ESRL HATS flask network are used to constrain the source and sink magnitudes. The inversion results indicate global total emissions around 4100 ± 470 Gg yr⁻¹ with very large emissions of 2200 ± 390 Gg yr⁻¹ from tropical plants, which turn out to be the largest single source in the CH₃Cl budget. Relative to their a priori annual estimates, the inversion increases global annual fungal and tropical emissions, and reduces the global oceanic source. The inversion implies greater seasonal and interannual oscillations of the natural sources and sink of CH₃Cl compared to the a priori. The inversion also reflects the strong effects of the 2002/2003 globally widespread heat waves and droughts on global emissions from tropical plants, biomass burning and salt marshes, and on the soil sink. % vor jede Referenz Ayres, M. P. and Lombardero, M. J.: Assessing the consequences of global change for forest disturbance from herbivores and pathogens, Sci. Total Environ., 262, 263–286, 2000. Balzter, H., Gerard, F. F., George, C. T., Rowland, C. S., Jupp, T. E., McCallum, I., Shvidenko, A., Nilsson, S., Sukhinin, A., Onuchin, A., and Schmullius, C.: Impact of the Arctic oscillation pattern on interannual forest fire variability in Central Siberia, Geophys. Res. Lett., 32, L14709, doi:10.1029/2005GL022526, 2005. Blake, N. J., Blake, D. R., Sive, B. C., Chen, T.-Y., Rowland, F. S., Collins Jr., J. E., Sachse, G. W., and Anderson, B. E.: Biomass burning emissions and vertical distribution of atmospheric methyl halides and other reduced carbon gases in the South Atlantic region, J. Geophys. Res., 101, D19, 24151-24164, 1996. Butler, J. H., Battle, M., Bender, M., Montzka, S. A., Clarke, A. D., Saltzman, E. S., Sucher, C., Severinghaus, J., and Elkins, J. W.: A twentieth century record of atmospheric halocarbons in polar firn air, Nature, 399, 749–755, 1999. Chen, Y.-H. and Prinn, R. G.: Atmospheric modeling of high- and low-frequency methane observations: Importance of interannually varying transport, J. Geophys. Res., 110, D10303, doi:10.1029/2004JD005542, 2005. Chen, Y.-H. and Prinn, R. G.: Estimation of atmospheric methane emissions between 1996 and 2001 using a three-dimensional global chemical transport model, J. Geophys. Res., 111, D10307, doi:10.1029/2005JD006058, 2006. Ciais, P., Reichstein, M., Viovy, N., Granier, A., Ogée, J., Allard, V., Aubinet, M., Buchmann, N., Bernhofer, C., Carrara, A., Chevallier, F., Noblet, N. D., Friend, A. D., Friedlingstein, P., Grünwald, T., Heinesch, B., Keronen, P., Knohl, A., Krinner, G., Loustau, D., Manca, G., Matteucci, G., Miglietta, F., Ourcival, J. M., Papale, D., Pilegaard, K., Rambal, S., Seufert, G., Soussana, J. F., Sanz, M. J., Schulze, E. D., Vesala, T., and Valentini, R.: Europe-wide reduction in primary productivity caused by the heat and drought in 2003, Nature, 437, 529–533, 2005. Clerbaux, C. and Cunnold, D. M.: Chapter 1 in: Scientific Assessment of Ozone Depletion: 2006, Global Ozone Research and Monitoring Project Report No. 50, Geneva, Nairobi; Washington, DC, Brussells: NOAA, NASA, UNEP, WMO, EC., 1.1–1.63, 2006. Cleveland, C. C., Holland, E. A., and Neff, J. C.: Temperature regulation of soil respiration in an alpine tundra ecosystem, paper presented at the Front Range Branch Annual Meeting, Am. Geophys. Union, Golden, Colo., 8–10 February, 1993. Cox, M. L., Sturrock, G. A., Fraser, P. J., Siems, S. T., Krummel, P. B., and O'Doherty, S.: Regional sources of methyl chloride, chloroform and dichloromethane identified from AGAGE observations at Cape Grim, Tasmania, 1998–2000, J. Atmos. Chem., 45, 79–99, 2003. Cox, M. L., Fraser, P. J., Sturrock, G. A., Siems, S. T., and Porter, L. W.: Terrestrial sources and sinks of halomethanes near Cape Grim, Tasmania, Atmos. Environ., 38(23), 3839–3852, 2004. Cunnold, D. M., Prinn, R. G., Rasmussen, R. A., Simmonds, P. G., Alyea, F. N., Cardelino, C. A., Crawford, A. J., Fraser, P. J., and Rosen, R. D.: The Atmospheric Lifetime Experiment 3. Lifetime methodology and application to three years of CFCl₃ Data, J. Geophys. Res., 88(C13), 8379–8400, 1983. Graedel, T. E. and Keene, W. C.: The tropospheric budget of reactive chlorine, Global Biogeochem. Cy., 9, 47–77, 1995. Graedel, T. E. and Keene, W. C.: The budget and cycle of Earth's natural chlorine, Pure Appl. Chem., 68, 1687–1689, 1996. Graedel, T. E. and Keene, W. C.: Preface, J. Geophys. Res., 104(D7), 8331–8332, 1999. Guenther, A., C. Hewitt, 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(D5), 8873–8892, 1995. Hamilton, J. T. G., McRoberts, W. C., Keppler, F., Kalin, R. M., and Harper, D. B.: Chloride methylation by plant pectin: An efficient environmentally significant process, Science, 301, 206–209, 2003. Hao, W. M. and Liu, M.-H.: Spatial and temporal distribution of tropical biomass burning, Global Biogeochem. Cy., 8(4), 495–503, 1994. Hartley, D. E. and Prinn, R. G.: On the feasibility of determining surface emissions of trace gases using an inverse method in a three-dimensional chemical transport model, J. Geophys. Res., 98, 5183–5198, 1993. Holland, E. A., Townsend, A. R., and Vitousek, P. M.: Variability in temperature regulation of CO₂ fluxes and N mineralization from five Hawaiian soils: Implications for a changing climate, Global Change Biol., 1, 115–123, 1995. Jöckel, P.: Cosmogenic $^14$CO as tracer for atmospheric chemistry and transport, Rpertus Carola University of Heidelberg, Heidelberg, 2000. Keene, W. C., Khalil, M. A. K., Erickson III, D. J., McCulloch, A., Graedel, T. E., Lobert, J. M., Aucott, M. L., Gong, S. L., Harper, D. B., Kleiman, G., Midgley, P., Moore, R. M., Seuzaret, C., Sturges, W. T., Benkovitz, C. M., Koropalov, V., Barrie, L. A., and Li, Y. F.: Composite global emissions of reactive chlorine from anthropogenic and natural sources: Reactive Chlorine Emissions Inventory, J. Geophys. Res., 104(D7), 8429–8440, 1999. Keppler, F., Harper, D. B., Röckmann, T., Moore, R. M., and Hamilton, J. T. G.: New insight into the atmospheric chloromethane budget gained using stable carbon isotope ratios, Atmos. Chem. Phys., 5, 2403–2411, doi:10.5194/acp-5-2403-2005, 2005. Khalil, M. A. K.: Reactive chlorine compounds in the atmosphere, in: Reactive Halogen Compounds in the Atmosphere, edited by: Fabian, P. and Singh, O. N., Springer-Verlag, Berlin, Heidelburg New York, 45–79, 1999. Khalil, M. A. K. and Rasmussen, R. A.: Atmospheric methyl chloride, Atmos. Environ., 33, 1305–1321, 1999. Khalil, M. A. K., Moore, R. M., Harper, D. B., Lobert, J. M., Erickson, D. J., Koropalov, V., Sturges, W. T., and Keene, W. C.: Natural emissions of chlorine-containing gases: Reactive Chlorine Emission Inventory, J. Geophys. Res., 104(D7), 8333–8346, 1999. Knorr, W., Gobron, N., Scholze, M., Kaminski, T., Schnur, R., and Pinty, B.: Impact of terrestrial biosphere carbon exchanges on the anomalous CO₂ increase in 2002–2003, Geophys. Res. Lett., 34, L09703, doi:10.1029/2006GL029019, 2007. Kobak, K. I., Turchinovich, I. Y., Kondrasheva, N. Y., Schulze, E. D., Schulze, W., Koch, H., and Vygodskaya, N. N.: Vulnerability and adaptation of the larch forest in eastern Siberia to climate change, Water Air Soil Pollut., 92, 119–127, 1996. Krummel, P. B.: the AGAGE team and respective participating laboratory investigators: Inter-comparison of AGAGE trace gases with other laboratories: ftp://gaspublic:gaspublic@ftp.dar.csiro.au/agage/, last access: 27 January 2009. Lawrence, M. G., Crutzen, P. J., Rasch, P. J., Eaton, B. E., and Mahowald, N. M.: A model for studies of tropospheric photochemistry: Description, global distributions, and evaluation, J. Geophys. Res., 104(D21), 26245–26277, 1999. Lee-Taylor, J. M., Doney, S. C., Brasseur, G. P., and Müller, J.-F.: A global three-dimensional atmosphere-ocean model of methyl bromide distributions, J. Geophys. Res., 103(D13), 16039–16057, 1998. Lee-Taylor, J. M., Brasseur, G. P., and Yokouchi, Y.: A preliminary three-dimensional global model study of atmospheric methyl chloride distributions, J. Geophys. Res., 106(D24), 34221–34233, 2001. Lobert, J. M., Keene, W. C., Logan, J. A., and Yevich, R.: Global chlorine emissions from biomass burning: Reactive Chlorine Emissions Inventory, J. Geophys. Res., 104(D7), 8373–8389, 1999. Lucas, D. D. and Prinn, R. G.: Sensitivities of gas-phase dimethylsulfide oxidation products to the assumed mechanisms in a chemical transport model, J. Geophys. Res., 110, D21312, doi:10.1029/2004JD005386, 2005. Lyon, B: The strength of El Niño and the spatial extent of tropical drought, Geophys. Res. Lett., 31, L21204, doi:10.1029/2004GL020901, 2004. Mahowald, N. M.: Development of a 3-dimensional chemical transport model based on observed winds and use in inverse modeling of the source of CCl₃F, PhD thesis, MIT, Cambridge, 1996. Mahowald, N. M., Rasch, P. J., Eaton, B. E., Whittlestone, S., and Prinn, R. G.: Transport of $^222$radon to the remote troposphere using the Model of Atmospheric Transport and Chemistry and assimilated winds from ECMWF and the National Center for Environmental Prediction/NCAR, J. Geophys. Res., 102(D23), 28139–28151, 1997a. Mahowald, N. M., Prinn, R. G., and Rasch, P. J.: Deducing CCl₃F emissions using an inverse method and chemical transport models with assimilated winds, J. Geophys. Res., 102(D23), 28153–28168, 1997b. McCulloch, A., Aucott, M. L., Benkovitz, C. M., Graedel, T. E., Kleiman, G., Midgley, P. M., and Li, Y. F.: Global emissions of hydrogen chloride and chloromethane from coal combustion, incineration and industrial activities: Reactive Chlorine Emissions Inventory, J. Geophys. Res., 104(D7), 8391–8403, 1999. McGuire, A. D., Sitch, S., Clein, J. S., Dargaville, R., Esser, G., Foley, J., Heimann, M., Joos, F., Kaplan, J., Kicklighter, D. W., Meier, R. A., Melillo, J. M., Moore III, B., Prentice, I. C., Ramankutty, N., Reichenau, T., Schloss, A., Tian, H., Williams, L. J., and Wittenberg, U.: Carbon balance of the terrestrial biosphere in the twentieth century: analyses of CO₂, climate and land use effects with four process-based ecosystem models, Global Biogeochem. Cy., 15(1), 183–206, 2001. Montzka, S. A., Butler, J. H., Elkins, J. W., Thompson, T. M., Clarke, A. D., and Lock, L. T.: Present and future trends in the atmospheric burden of ozone-depleting halogens, Nature, 398, 690–694, 1999. Montzka, S. A., Spivakovsky, C. M., Butler, J. H., Elkins, J. W., Lock, L. T., and Mondeel, D. J.: New observational constraints for atmospheric hydroxyl on global and hemispheric scales, Science, 288, 500–503, 2000. Montzka, S. A. and Fraser, P. J.: Controlled substances and other gas sources, Chapter 1 in: Scientific Assessment of Ozone Depletion: 2002, Global Ozone Research and Monitoring Project Report No. 47, Geneva, Nairobi; Washington, D.C., Brussells: WMO, UNEP, NOAA, NASA, EC., 1.1–1.83, 2003. Moore, R. M., Groszko, W., and Niven, S. J.: Ocean-atmosphere exchange of methyl chloride: Results from NW Atlantic and Pacific Ocean studies, J. Geophys. Res., 101(C12), 28529–28538, 1996. Moore, R. M., Gut, A., and Andreae, M. O.: A pilot study of methyl chloride emissions from tropical woodrot fungi, Chemosphere, 58(2), 221–225, 2005. Mulquiney, J. E. and Norton, J. P.: A new inverse method for trace gas flux estimation 1. State-space model identification and constraints, J. Geophys. Res., 103(D1), 1417–1427, 1998. Prinn, R. G.: Measurement equation for trace chemicals in fluids and solution of its inverse, in: Inverse Methods in Global Biogeochemical Cycles, edited by: Kasibhatla, P., Heimann, M., Rayner, P., et al., Geophys. Monogr. Ser., 114, 3–18, AGU, Washington, DC, 2000. Prinn, R. G., Weiss, R. F., Fraser, P. J., Simmonds, P. G., Cunnold, D. M., Alyea, F. N., O'Doherty, S., Salameh, P., Miller, B. R., Huang, J., Wang, R. H. J., Hartley, D. E., Harth, C., Steele, L. P., Sturrock, G., Midgley, P. M., and McCulloch, A.: A history of chemically and radiatively important gases in air deduced from ALE/GAGE/AGAGE, J. Geophys. Res., 105(D14), 17751–17792, 2000. Prinn, R. G., Huang, J., Weiss, R. F., Cunnold, D. M., Fraser, P. J., Simmonds, P. G., McCulloch, A., Harth, C., Salameh, P., O'Doherty, S., Wang, R. H. J., Porter, L., and Miller, B. R.: Evidence for variability of atmospheric hydroxyl radicals over the past quarter century, Geophys. Res. Lett., 32, L07809, doi:10.1029/2004GL022228, 2005. Rasch, P. J., Mahowald, N. M., and Eaton, B. E.: Representations of transport, convection, and the hydrologic cycle in chemical transport models: Implications for the modeling of short-lived and soluble species, J. Geophys. Res., 102(D23), 28127–28138, 1997. Rhew, R. C., Miller, B. R., and Weiss, R. F.: Natural methyl bromide and methyl chloride emissions from coastal salt marshes, Nature, 403, 292–295, 2000. 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 No. 15, JPL Publication 06-2, Jet Propulsion Laboratory, Pasadena, Calif, 2006. Schär, C., Vidale, P. L., Lüthi, D., Frei, C., Häberli, C., Liniger, M. A., and Appenzeller, C.: The role of increasing temperature variability in European summer heatwaves, Nature, 427, 332–336, 2004. Seinfeld, J. H. and Pandis, S. N.: Atmospheric chemistry and physics: from air pollution to climate change, A Wiley-Interscience publication, USA, 1326~pp., 1998. Shorter, J. H., Kolb, C. E., Crill, P. M., Kerwin, R. A., Talbot, R. W., Hines, M. E., and Harriss, R. C.: Rapid degradation of atmospheric methyl bromide in soils, Nature, 377, 717–719, 1995. Simmonds, P. G., Derwent, R. G., Manning, A. J., Fraser, P. J., Krummel, P. B., O'Doherty, S., Prinn, R. G., Cunnold, D. M., Miller, B. R., Wang, H. J., Ryall, D. B., Porter, L. W., Weiss, R. F., and Salameh, P. K.: AGAGE observations of methyl bromide and methyl chloride at Mace Head, Ireland, and Cape Grim, Tasmania, 1998–2001, J. Atmos. Chem., 47(3), 243–269, 2004. Simmonds, P. G., Manning, A. J., Derwent, R. G., Ciais, P., Ramonet, M., Kazan, V., and Ryall, D.: A burning question. Can recent growth rate anomalies in the greenhouse gases be attributed to large-scale biomass burning events?, Atmos. Environ., 39, 2513–2517, 2005. Singh, H. B.: Halogens in the atmospheric environment, in Composition, Chemistry and Climate of the Atmosphere, edited by: Singh, H. B., 216–250, Van Nostrand Reinhold, New York, 1995. Trudinger, C. M., Etheridge, D. M., Sturrock, G. A., Fraser, P. J., Krummel, P. B., and McCulloch, A.: Atmospheric histories of halocarbons from analysis of Antarctic firn air: Methyl bromide, methyl chloride, chloroform, and dichloromethane, J. Geophys. Res., 109, D22310, doi:10.1029/2004JD004932, 2004. Varner, R. K., Crill, P. M., and Talboat, R. W.: Wetlands: a potentially significant source of atmospheric methyl bromide and methyl chloride, Geophys. Res. Lett., 26(16), 2433–2436, 1999. 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(D9), 4294, doi:10.1029/2002JD002893, 2003. Watling, R. and Harper, D. B.: Chloromethane production by wood-rotting fungi and an estimate of the global flux to the atmosphere, Mycol. Res., 102, 769–787, 1998. Xiao, X., Prinn, R. G., Simmonds, P. G., Steele, L. P., Novelli, P. C., Huang, J., Langenfelds, R. L., O'Doherty, S., Krummel, P. B., Fraser, P. J., Porter, L. W., Weiss, R. F., Salameh, P., and Wang, R. H. J.: Optimal estimation of the soil uptake rate of molecular hydrogen from the Advanced Global Atmospheric Gases Experiment and other measurements, J. Geophys. Res., 112, D07303, doi:10.1029/2006JD007241, 2007. Xiao, X.: Optimal estimation of the surface fluxes of chloromethanes using a 3-D global atmospheric chemical transport model, PhD thesis, MIT, Cambridge, 2008. Xiao, X., Prinn, R. G., Fraser, P. J., Weiss, R. F., Simmonds, P. G., O'Doherty, S., Miller, B. R., Salameh, P. K., Harth, C. M., Krummel, P. B., Golombek, A., Porter, L. W., Elkins, J. W., Dutton, G. S., Hall, B. D., Steele, L. P., Wang, R. H. J., and Cunnold, D. M.: Atmospheric three-dimensional inverse modeling of regional industrial emissions and global oceanic uptake of carbon tetrachloride, Atmos. Chem. Phys. Discuss., 10, 12225–12260, doi:10.5194/acpd-10-12225-2010, 2010. Yokouchi, Y., Noijiri, Y., Barrie, L. A., Toom-Sauntry, D., Machida, T., Inuzuka, Y., Akimoto, H., Li, H. J., Fujinuma, Y., and Aoki, S.: A strong source of methyl chloride to the atmosphere from tropical coastal land, Nature, 403, 295–298, 2000. Yokouchi, Y., Ikeda, M., Inuzuka, Y., and Yukawa, T.: Strong emission of methyl chloride from tropical plants, Nature, 416, 163–165, 2002. Yoshida, Y., Wang, Y., Shim, C., Cunnold, D., Blake, D. R., and Dutton, G. S.: Inverse modeling of the global methyl chloride sources, J. Geophys. Res., 111, D16307, doi:10.1029/2005JD006696, 2006. Zeng, N., Qian, H., Roedenbeck, C., and Heimann, M.: Impact of 1998–2002 midlatitude drought and warming on terrestrial ecosystem and the global carbon cycle, Geophys. Res. Lett., 32, L22709, doi:10.1029/2005GL024607, 2005.