ACP Atmospheric Chemistry and Physics ACP Atmos. Chem. Phys. 1680-7324 Copernicus Publications Göttingen, Germany 10.5194/acp-9-5281-2009 Multi-species inversion of CH<sub>4</sub>, CO and H<sub>2</sub> emissions from surface measurements Pison I. 1 Bousquet P. 1 Chevallier F. 1 Szopa S. 1 Hauglustaine D. 1 Laboratoire des Sciences du Climat et de l'Environnement, UMR1572, CEA-CNRS-UVSQ, IPSL, Gif-sur-Yvette, France 29 07 2009 9 14 5281 5297 Copyright: © 2009 I. Pison et al. 2009 This work is licensed under the Creative Commons Attribution 3.0 Unported License. To view a copy of this licence, visit https://creativecommons.org/licenses/by/3.0/ This article is available from https://acp.copernicus.org/articles/9/5281/2009/acp-9-5281-2009.html The full text article is available as a PDF file from https://acp.copernicus.org/articles/9/5281/2009/acp-9-5281-2009.pdf

In order to study the spatial and temporal variations of the emissions of greenhouse gases and of their precursors, we developed a data assimilation system and applied it to infer emissions of CH<sub>4</sub>, CO and H<sub>2</sub> for one year. It is based on an atmospheric chemical transport model and on a simplified scheme for the oxidation chain of hydrocarbons, including methane, formaldehyde, carbon monoxide and molecular hydrogen together with methyl chloroform. The methodology is exposed and a first attempt at evaluating the inverted fluxes is made. Inversions of the emission fluxes of CO, CH<sub>4</sub> and H<sub>2</sub> and concentrations of HCHO and OH were performed for the year 2004, using surface concentration measurements of CO, CH<sub>4</sub>, H<sub>2</sub> and CH<sub>3</sub>CCl<sub>3</sub> as constraints. Independent data from ship and aircraft measurements and satellite retrievals are used to evaluate the results. The total emitted mass of CO is 30% higher after the inversion, due to increased fluxes by up to 35% in the Northern Hemisphere. The spatial distribution of emissions of CH<sub>4</sub> is modified by a decrease of fluxes in boreal areas up to 60%. The comparison between mono- and multi-species inversions shows that the results are close at a global scale but may significantly differ at a regional scale because of the interactions between the various tracers during the inversion.

 References Bergamaschi, P., Frankenberg, F., Meirink, J F., Krol, M., Dentener, F., Wagner, T., Platt, U., Kaplan, J O., Körner, S., Heimann, M., Dlugokencky, E J., and Goede, A.: Satellite chartography of atmospheric methane from SCIAMACHY on board ENVISAT: 2. Evaluation based on inverse model simulations, J. Geophys. Res., 112, \doi10.1029/2006JD007268, 2007. Boucher, O., Moulin, C., Belviso, S., Aumont, O., Bopp, L., Cosme, E., von Kuhlmann, R., Lawrence, M G., Pham, M., Reddy, M S., Sciare, J., and Venkataraman, C.: DMS atmospheric concentrations and sulphate aerosol indirect radiative forcing: a sensitivity study to the DMS source representation and oxidation, Atmos. Chem. Phys., 3, 49–65, 2003. Bousquet, P., Peylin, P., Ciais, P., Le~Quere, C., Friedlingstein, P., and Tans, P.: Regional changes in carbon dioxide fluxes of land and ocean since 1980., Science, 290, 1342–1345, 2000. Bousquet, P., Hauglustaine, D., Peylin, P., Carouge, C., and Ciais, P.: Two decades of OH variability as inferred by an inversion of atmospheric transport and chemistry of methyl chloroform, Atmos. Chem. Phys., 5, 2635–2656, 2005. Bousquet, P., Ciais, P., Miller, J B., Dlugokencky, E J., Hauglustaine, D A., Prigent, C., Van~der Werf, G R., Peylin, P., Brunke, E G., Carouge, C., Langenfelds, R L., Lathiere, J., Papa, F., Ramonet, M., Schmidt, M., Steele, L P., Tyler, S C., and White, J.: Contribution of anthropogenic and natural sources to atmospheric methane variability, Nature, 443, 439–443, \doi10.1038/nature05132, 2006. Butler, T M., Rayner, P J., Simmonds, I., and Lawrence, M G.: Simultaneous mass balance inverse modeling of methane and carbon monoxide, J. Geophys. Res., 110, D21310, \doi10.1029/2005JD006071, 2005. Carmichael, G., Tang, Y., Kurata, G., Uno, I., Streets, D., Thongboonchoo, N., Woo, J., Guttikunda, S., White, A., Wang, T., et~al.: Evaluating regional emission estimates using the TRACE-P observations, J. Geophys. Res., 108(D21), 8823, https://doi.org/10.1029/2002JD003117 Carouge, C., Bousquet, P., Peylin, P., Rayner, P., and Ciais, P.: What can we learn from European continuous atmospheric CO<sub>2</sub> measurements to quantify regional fluxes, Part 1: Potential of the network, Atmos. Chem. Phys. Discuss., 8, 18591–18620, 2008a. Carouge, C., Peylin, P., Rayner, P J., Bousquet, P., Chevallier, F., and Ciais, P.: What can we learn from European continuous atmospheric CO<sub>2</sub> measurements to quantify regional fluxes, Part 2: Sensitivity of flux accuracy to inverse setup, Atmos. Chem. Phys. Discuss., 8, 18621–18649, 2008b. Chevallier, F., Fisher, M., Peylin, P., Serrar, S., Bousquet, P., Bréon, F.-M., Chédin, A., and Ciais, P.: Inferring CO<sub>2</sub> sources and sinks from satellite observations: method and application to TOVS data, J. Geophys. Res., 110, L23801, \doi10.1029/2005JD006390, 2005. Chevallier, F., Bréon, F.-M., and Rayner, P.: The contribution of the Orbiting Carbon Observatory to the estimation of CO<sub>2</sub> sources and sinks: Theoretical study in a variational data assimilation framework, J. Geophys. Res., 112, D09307, \doi10.1029/2006JD007375, 2007. Chevallier, F., Fortems, A., Bousquet, P., Pison, I., Szopa, S., Devaux, M., and Hauglustaine, D.: African CO emissions between years 2000 and 2006 as estimated from MOPITT observations, Biogeosciences, 6, 103–111, 2009. Conway, T J., Tans, P P., Waterman, L S., Thoning, K W., Kitzis, D R., Masarie, K A., and Zhang, N.: Evidence for interannual variability of the carbon cycle from the National Oceanic and Atmospheric Administration/Climate Monitoring and Diagnostic Laboratory Global Air Sampling Network, J. Geophys. Res., 99, 22831–22855, 1994. Cunnold, D., Steele, L., Fraser, P., Simmonds, P., Prinn, R., Weiss, R., Porter, L., O'Doherty, S., Langenfelds, R., Krummel, P., et~al.: In situ measurements of atmospheric methane at GAGE/AGAGE sites during 1985–2000 and resulting source inferences, J. Geophys. Res., 107, 4225, 2002. Deeter, M., Emmons, L., Francis, G., Edwards, D., Gille, J., Warner, J., Khattatov, B., Ziskin, D., Lamarque, J.-F., Ho, S.-P., Yudin, V., Attié, J.-L., Packman, D., Chen, J., Mao, D., and Drummond, J.: Operational carbon monoxide retrieval algorithm and selected results for the MOPITT instrument, J. Geophys. Res., 108(D14), 4399, \doi10.1029/2002JD003186, 2003. Deeter, M., Emmons, L., Edwards, D., Gille, J., and Drummond, J.: Vertical resolution and information content of CO profiles retrieved by MOPITT, Geophys. Res. Lett., 31, L15112, https://doi.org/10.1029/2004GL020235, 2004. Dlugokencky, E., Steele, L., Lang, P., and Masarie, K.: The growth rate and distribution of atmospheric methane, J. Geophys. Res., 99, 1994. Dlugokencky, E., Myers, R., Lang, P., Masarie, K., Crotwell, A., Thoning, K., Hall, B., Elkins, J., and Steele, L.: Conversion of NOAA atmospheric dry air CH 4 mole fractions to a gravimetrically prepared standard scale, J. Geophys. Res, 110, D18306, https://doi.org/10.1029/2005JD006035, 2005. Dubovik, O., Lapyonok, T., Kaufman, Y., Chin, M., Ginoux, P., Kahn, R., and Sinyuk, A.: Retrieving global aerosol sources from satellites using inverse modeling, Atmos. Chem. Phys., 8, 209–250, 2008. Edwards, D., Halvorson, C., and Gille, J.: Radiative transfer modeling of the EOS Terra Satellite MOPITT instrument, J.Geophys. Res., 104(D14), 16755–16775, https://doi.org/10.1029/2002JD002378, 1999. Elbern, H., Strunk, A., Schmidt, H., and Talagrand, O.: Emission rate and chemical state estimation by 4-dimensional variational inversion, Atmos. Chem. Phys., 7, 3749–3769, 2007. Emmons, L., Deeter, M., Gille, J., Edwards, D., and Attie, J.-L.: Validation of measurements of MOPITT CO retrievals with aircraft in situ profiles, J. Geophys. Res., 108, D03309, https://doi.org/10.1029/2003JD004101, 2004. Emmons, L., Pfister, G., Edwards, D., Gille, J., Sachse, G., Blake, D., Wofsy, S., Gerbig, C. ans~Matross, D., and Nedelec, P.: MOPITT validation exercises during summer 2004 field campaigns over North America, J. Geophys. Res., 112, D12S02, https://doi.org/10.1029/2006JD007833, 2007. Folberth, G., Hauglustaine, D., Ciais, P., and Lathière, J.: On the role of atmospheric chemistry in the global CO<sub>2</sub> budget, Geophys. Res. Lett., 32, L08801, \doi10.1029/2004GL021812, 2005. 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. Francey, R., Steele, L., Langenfelds, R., and Pak, B.: High Precision Long-Term Monitoring of Radiatively Active and Related Trace Gases at Surface Sites and from Aircraft in the Southern Hemisphere Atmosphere, J. Atmos. Sci., 56, 279–285, 1999. Frankenberg, C., Meirink, J., van Weele, M., Platt, U., and Wagner, T.: Assessing methane emissions from global space-borne observations, Science, 308, 1010–1014, \doi10.1126/science.1106644, 2005. Fung, I., John, J., Lerner, J., Matthews, E., Prather, M., Steele, L., and Fraser, P.: Three-dimensional model synthesis of the global methane cycle, J. Geophys. Res., 96, 13033–13065, 1991. Geels, C., Gloor, M., Ciais, P., Bousquet, P., Peylin, P., Vermeulen, A., Dargaville, R., Aalto, T., Brandt, J., Christensen, J., et~al.: Comparing atmospheric transport models for future regional inversions over Europe–Part\~ 1: mapping the atmospheric CO<sub>2</sub> signals, Atmos. Chem. Phys., 7, 3461–3479, 2007. Gilbert, J.-C. and Lemaréchal, C.: Some numerical experiments with variable-storage quasi-Newton algorithms, Math. Program., 45, 407–435, 1989. GLOBALVIEW-CH4: Cooperative Atmospheric Data Integration Project - Methane, NOAA ESRL (Boulder, Colorado), CD-ROM [Also available on Internet via anonymous FTP to ftp.cmdl.noaa.gov, Path: ccg/ch4/GLOBALVIEW], 2005. GLOBALVIEW-CO: Cooperative Atmospheric Data Integration Project - Carbon Monoxide, NOAA ESRL (Boulder, Colorado), CD-ROM [Also available on Internet via anonymous FTP to ftp.cmdl.noaa.gov, Path: ccg/co/GLOBALVIEW], 2005. Gurney, K., Law, R., Denning, A., Rayner, P., Pak, B., Baker, D., Bousquet, P., Bruhwiler, L., Chen, Y., Ciais, P., et~al.: Transcom 3 inversion intercomparison: Model mean results for the estimation of seasonal carbon sources and sinks, Global Biogeochem. Cy., 18, GB1010, https://doi.org/10.1029/2003GB002111, 2004. Gurney, K., Law, R., Denning, A., Rayner, P., Baker, D., Bousquet, P., Bruhwiler, L., Chen, Y., Ciais, P., Fan, S., Fung, I., Gloor, M., Heimann, M., Higuchi, K., John, J., Maki, T., Maksyutov, S., Masarie, K., Peylin, P., Prather, M., Pak, B., Randerson, J., Sarmiento, J., Taguchi, S., Takahashi, T., and Yuen, C.: Towards robust regional estimates of CO<sub>2</sub> sources and sinks using atmospheric transport models, Nature, 415, 626–630, 2002. Hauglustaine, D. and Ehhalt, D.: A three-dimensional model of molecular hydrogen in the troposphere, J. Geophys. Res., 107(D17), 4330, \doi10.1029/2001JD001156, 2002. Hauglustaine, D., Hourdin, F., Jourdain, L., Filiberti, M., Walters, S., Lamarque, J., and Holland, E.: Interactive chemistry in the Laboratoire de Météorologie Dynamique general circulation model: Description and background tropospheric chemistry evaluation, J. Geophys. Res., 109, D04314, \doi10.1029/2003JD003957, 2004. Heald, C., Jacob, D., Jones, D., Palmer, P., Logan, J., Streets, D., Sachse, G., Gille, J., Hoffman, R., and Nehrkorn, T.: Comparative inverse analysis of satellite (MOPITT) and aircraft (TRACE-P) observations to estimate Asian sources of carbon monoxide, J. Geophys. Res, 109, D23306, https://doi.org/10.1029/2004JD005185, 2004. Hourdin, F. and Armengaud, A.: The use of finite-volume methods for atmospheric advection of trace species. Part I: Test of various formulations in a general circulation model, Mon. Weather Rev., 127, 822–837, 1999. IPCC: Climate change 2007 – Synthesis Report, Cambridge University Press, 996 pp.,2007. Krol, M., Lelieveld, J., Oram, D., Sturrock, G., Penkett, S., Brenninkmeijer, C., Gros, V., Williams, J., and Scheeren, H.: Continuing emissions of methyl chloroform from Europe, Nature, 421, 131–135, \doi10.1038/nature01311, 2003. Lowe, D., Brenninkmeijer, C., Tyler, S., and Dlugkencky, E.: Determination of the Isotopic Composition of Atmospheric Methane and its Application in the Antarctic, J. Geophys. Res., 96, 15455–15467, 1991. Matsueda, H., Sawa, Y., Wada, A., Inoue, H Y., Suda, K., Hirano, Y., Tsuboi, K., and Nishioka, S.: Methane standard gases for atmospheric measurements at the MRI and JMA and intercomparison experiments, Pap. Meteor. Geophys., 54, 91–109, 2004. Meirink, J F., Bergamaschi, P., and Krol, M C.: Four-dimensional variational data assimilation for inverse modelling of atmospheric methane emissions: method and comparison with synthesis inversion, Atmos. Chem. Phys., 8, 6341–6353, 2008. Montzka, S., Spivakovsky, C., Butler, J., Elkins, J., Lock, L., and Mondeel, D.: New Observational Constraints for Atmospheric Hydroxyl on Global and Hemispheric Scales, Science, 288, 500, 2000. Novelli, P., Steele, P., and Tans, P.: Mixing ratios of carbon monoxide in the troposphere, J. Geophys. Res., 97(D18), 20731–20750, 1992. Novelli, P., Lang, P., Masarie, K., Hurst, D., Myers, R., and Elkins, J.: Molecular hydrogen in the troposphere- Global distribution and budget, J. Geophys. Res., 104(D23), 30427–30444,1999. Ohara, T., Akimoto, H., Kurokawa, J., Horii, N., Yamaji, K., Yan, X., and Hayasaka, T.: An Asian emission inventory of anthropogenic emission sources for the period 1980–2020, Atmos. Chem. Phys., 7, 4419–4444, 2007. Olivier, J. G J. and Berdowski, J. J M.: The Climate System, chap. Global emissions sources and sinks, A. A. Balkema/Swets & Zeitlinger, J. Berdowski, R. Guichert, B. Heij, 33–37, 2001. Palmer, P., Jacob, D., Jones, D., Heald, C., Yantosca, R., Logan, J., Sachse, G., and Streets, D.: Inverting for emissions of carbon monoxide from Asia using aircraft observations over the western Pacific, J. Geophys. Res., 108(D21), 8828, https://doi.org/10.1029/2003JD003397, 2003. Pétron, G., Granier, C., Khattatov, B., Yudin, V., Lamarque, J., Emmons, L., Gille, J., and Edwards, D.: Monthly CO surface sources inventory based on the 2000-2001 MOPITT satellite data, Geophys. Res. Lett., 31, L21107.1–L21107.5, \doi10.1029/2004GL020560, 2004. Peylin, P., Rayner, P J., Bousquet, P., Carouge, C., Hourdin, F., Heinrich, P., Ciais, P., and contributors, A.: Daily CO<sub>2</sub> flux estimates over Europe from continuous atmospheric measurements: 1, inverse methodology, Atmos. Chem. Phys., 5, 3173–3186, 2005. Pfister, G., Hess, P., Emmons, L., Lamarque, J.-F., Wiedinmyer, C., Edwards, D., Pétron, G., Gille, J., and Sachse, G.: Quantifying CO emissions from the 2004 Alaskan wildfires using MOPITT CO data, Geophys. Res. Lett., 32, L11809, https://doi.org/10.1029/2005GL022995, 2005. Price, H., Jaeglé, L., Rice, A., Quay, P., Novelli, P C., and Gammon, R.: Global budget of molecular hydrogen and its deuterium content: Constraints from ground station, cruise, and aircraft observations, J. Geophys. Res., 112, D22108, https://doi.org/10.1029/2006JD008152, 2007. Prinn, R., Huang, J., Weiss, R., Salameh, P., Miller, B., Fraser, P., Simmonds, P., O'Doherty, S., Cunnold, D., and Alyea, F.: 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., Huang, J., Weiss, R., Cunnold, D., Fraser, P., Simmonds, P., McCulloch, A., Harth, C., Reimann, S., Salameh, P., O'Doherty, S., Wang, R., Porter, L., Miller, B., and Krummel, P.: Evidence for variability of atmospheric hydroxyl radicals over the past quarter century, Geophys. Res. Lett., 32, L07809, https://doi.org/10.1029/2004GL022228, 2005. Rayner, P J., Enting, I G., Francey, R J., and Langenfelds, R.: Reconstructing the recent carbon cycle from atmospheric CO<sub>2</sub>,$\delta^13$C and O<sub>2</sub>/N<sub>2</sub> observations, Tellus B, 51, 213–232, 1999. Sadourny, R. and Laval, K.: New Perspectives in Climate Modeling, chap. January and July performance of the LMD general circulation model, edited by: Bergerand, A. L. and Nicolis, C., Amsterdam, The Netherlands, Elsevier press edn., 173–197, 1984. Schmidt, M., Ramonet, M., Wastine, B., Delmotte, M., Galdemard, P., Kazan, V., Messager, C., Royer, A., Valant, C., Xueref, I., and Ciais, P.: RAMCES: The French Network of Atmospheric Greenhouse Gas Monitoring, in: 13th WMO/IAEA Meeting of Experts on Carbon Dioxide Concentration and Related Tracers Measurement Techniques, Report WMO 168, 165–174, 2006. Stavrakou, T. and Müller, J.-F.: Grid-based versus big region approach for inverting CO emissions using MOPITT data, J. Geophys. Res., 34, D15304, https://doi.org/10.1029/2007GL030231, 2006. Turquety, S., Logan, J A., Jacob, D J., Hudman, R C., Leung, F Y., Heald, C L., Yantosca, R M., Wu, S., Emmons, L K., Edwards, D P., and Sachse, G W.: Inventory of boreal fire emissions for North America in 2004: Importance of peat burning and pyroconvective injection, J. Geophys. Res., 112, D12S03, \doi10.1029/2006JD007281, 2007. van~der Werf, G R., Randerson, J T., Giglio, L., Collatz, G J., Kasibhatla, P S., and Arellano, Jr., A F.: Interannual variability in global biomass burning emissions from 1997 to 2004, Atmos. Chem. Phys., 6, 3423–3441, 2006. Worthy, D., Levin, I., Trivett, N., Kuhlmann, A., Hopper, J., and Ernst, M.: Seven years of continuous methane observations at a remote boreal site in Ontario, Canada, J. Geophys. Res., 103(D13), 15995–16007, 1998.