ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-10-10421-2010 Atmospheric three-dimensional inverse modeling of regional industrial emissions and global oceanic uptake of carbon tetrachloride Xiao X. 1 8 Prinn R. G. 1 Fraser P. J. 2 Weiss R. F. 3 Simmonds P. G. 4 O'Doherty S. 4 Miller B. R. 5 Salameh P. K. 3 Harth C. M. 3 Krummel P. B. 2 Golombek A. 1 Porter L. W. 6 9 Butler J. H. 5 Elkins J. W. 5 Dutton G. S. 5 Hall B. D. 5 Steele L. P. 2 Wang R. H. J. 7 Cunnold D. M. 7 9 Department of Earth, Atmospheric, and Planetary Sciences, MIT, Cambridge, MA 02139, USA Centre for Australian Weather and Climate Research, CSIRO Marine and Atmospheric Research, Aspendale, Victoria 3195, Australia Scripps Institution of Oceanography, University of California, San Diego, La Jolla, CA 92093, USA School of Chemistry, University of Bristol, Bristol, UK ESRL, National Oceanic and Atmospheric Administration (NOAA), Boulder, CO 80305, USA Centre for Australian Weather and Climate Research, Australian Government Bureau of Meteorology, Melbourne, Victoria 3000, Australia School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, GA 30332, USA now at: Civil and Environmental Engineering, Rice University, Houston, TX 77005, USA deceased 08 11 2010 10 21 10421 10434 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/10/10421/2010/acp-10-10421-2010.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/10/10421/2010/acp-10-10421-2010.pdf

Carbon tetrachloride (CCl<sub>4</sub>) has substantial stratospheric ozone depletion potential and its consumption is controlled under the Montreal Protocol and its amendments. We implement a Kalman filter using atmospheric CCl<sub>4</sub> measurements and a 3-dimensional chemical transport model to estimate the interannual regional industrial emissions and seasonal global oceanic uptake of CCl<sub>4</sub> for the period of 1996–2004. The Model of Atmospheric Transport and Chemistry (MATCH), driven by offline National Center for Environmental Prediction (NCEP) reanalysis meteorological fields, is used to simulate CCl<sub>4</sub> mole fractions and calculate their sensitivities to regional sources and sinks using a finite difference approach. High frequency observations from the Advanced Global Atmospheric Gases Experiment (AGAGE) and the Earth System Research Laboratory (ESRL) of the National Oceanic and Atmospheric Administration (NOAA) and low frequency flask observations are together used to constrain the source and sink magnitudes, estimated as factors that multiply the a priori fluxes. Although industry data imply that the global industrial emissions were substantially declining with large interannual variations, the optimized results show only small interannual variations and a small decreasing trend. The global surface CCl<sub>4</sub> mole fractions were declining in this period because the CCl<sub>4</sub> oceanic and stratospheric sinks exceeded the industrial emissions. Compared to the a priori values, the inversion results indicate substantial increases in industrial emissions originating from the South Asian/Indian and Southeast Asian regions, and significant decreases in emissions from the European and North American regions.

 References Allen, N. D. C., Bernath, P. F., Boone, C. D., Chipperfield, M. P., Fu, D., Manney, G. L., Oram, D. E., Toon, G. C., and Weisenstein, D. K.: Global carbon tetrachloride distributions obtained from the Atmospheric Chemistry Experiment (ACE), Atmos. Chem. Phys., 9, 7449–7459, doi:10.5194/acp-9-7449-2009, 2009. Butler, J. H., Battle, M., Bender, M. L., Montzka, S. A., Clarke, A. D., Saltzman, E. S., Sucher, C. M., Severinghaus, J. P., and Elkins, J. W.: A record of atmospheric halocarbons during the twentieth century from polar firn air, Nature, 399, 749–755, 1999. 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. Clerbaux, C., Cunnold, D. M., Anderson, J., Engel, A., Fraser, P. J., Mahieu, E., Manning, A., Miller, J., Montzka, S. A., Nassar, R., Prinn, R. G., Reimann, S., Rinsland, C. P., Simmonds, P. G., Verdonik, D., Weiss, R. F., Wuebbles, D., Yokouchi, Y.: Chapter 1 Long-lived compounds, in: Scientific Assessment of Ozone Depletion: 2006, Global Ozone Research and Monitoring Project – Report No. 50., World Meteorological Organization, Geneva, Switzerland, 2007. Cunnold, D. M., Weiss, R. F., Prinn, R. G., Hartley, D. E., Simmonds, P. G., Fraser, P. J., Miller, B. R., Alyea, F. N., and Porter, L.: GAGE/AGAGE measurements indicating reductions in global emissions of CCl<sub>3</sub>F and CCl<sub>2</sub>F<sub>2</sub> in 1992–1994, J. Geophys. Res., 102(D1), 1259–1269, 1997. Golombek, A. and Prinn, R. G.: A global three-dimensional model of the circulation and chemistry of CFCl<sub>3</sub>, CF<sub>2</sub>Cl<sub>2</sub>, CH<sub>3</sub>CCl<sub>3</sub>, CCl<sub>4</sub>, and N<sub>2</sub>O, J. Geophys. Res., 91(D3), 3985–4001, 1986. Golombek, A. and Prinn, R. G.: Global three-dimensional model calculations of the budgets and present-day atmospheric lifetimes of CF<sub>2</sub>ClCFCl<sub>2</sub> (CFC-113) and CHClF<sub>2</sub> (CFC-22), Geophys. Res. Lett., 16(10), 1153–1156, 1989. Golombek, A. and Prinn, R. G.: A global three-dimensional model of the stratospheric sulfuric acid layer, J. Atmos. Chem., 16, 179–199, 1993. Happell, J. D. and Roche, M. P.: Soils: a global sink of atmospheric carbon tetrachloride, Geophys. Res. Lett., 30(\refeq2), 1088, doi:10.1029/2002GL015957, 2003. Jöckel, P., Brenninkmeijer, C. A. M., Lawrence, M. G., Jeuken, A. B. M., and van Velthoven, P. F. J.: Evaluation of stratosphere-troposphere exchange and the hydroxyl radical distribution in three-dimensional global atmospheric models using observations of cosmogenic $^14$CO, J. Geophys. Res., 107(D20), 4446, doi:10.1029/2001JD001324, 2002. Kindler, T. P., Chameides, W. L., Wine, P. H., Cunnold, D. M., Alyea, F. N., and Franklin, J. A.: The fate of atmospheric phosgene and the stratospheric chlorine loadings of its parent compounds: CCl<sub>4</sub>, C<sub>2</sub>Cl<sub>4</sub>, C<sub>2</sub>HCl<sub>3</sub>, CH<sub>3</sub>CCl<sub>3</sub>, and CHCl<sub>3</sub>, J. Geophys. Res., 100(D1), 1235–1251, 1995. Krummel, P. B.: the AGAGE team and respective participating laboratory investigators: Intercomparison of AGAGE trace gases with other laboratories, unpublished report presented at the 37$^\rm th$ meeting of AGAGE scientists, Grindelwald, Switzerland, June 2008, 19~pp., 2008. Mahowald, N. M.: Development of a 3-dimensional chemical transport model based on observed winds and use in inverse modeling of the source of CCl<sub>3</sub>F, 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 CCl<sub>3</sub>F emissions using an inverse method and chemical transport models with assimilated winds, J. Geophys. Res., 102(D23), 28153–28168, 1997b. Montzka, S. A., Butler, J. H., Meyers, R. C., Thompson, T. M., Swanson, T. H., Clarke, A. D., Locke, L. T., and Elkins, J. W.: Decline in the tropospheric abundance of halogen from halocarbons: Implications for stratospheric ozone depletion, Science, 272, 1318–1322, 1996. Montzka, S. A., Butler, J. H., Elkins, J. W., Thompson, T. M., Clarke, A. D., and Locke, L. T.: Present and future trends in the atmospheric burden of ozone-depleting halogens, Nature, 398, 690–694, 1999. Montzka, S. A., Fraser, P. J., Butler, J. H., Connell, P. S., Cunnold, D. M., Daniel, J. S., Derwent, R. G., Lal, S., McCulloch, A., Oram, D. E., Reeves, C. E., Sanhueza, E., Steele, L. P., Velders, G. J. M., Weiss, R. F., and Zander, R. J.: Chapter 1 Controlled substances and other source gases, in: Scientific Assessment of Ozone Depletion: 2002, Global Ozone Research and Monitoring Project – Report No. 47., World Meteorological Organization, Geneva, Switzerland, 2003. Palmer, P. I., Jacob, D. J., Mickley, L. J., Blake, D. R., Sachse, G. W., Fuelberg, H. E., and Kiley, C. M.: Eastern Asian emissions of anthropogenic halocarbons deduced from aircraft concentration data, J. Geophys. Res., 108(D24), 4753, doi:10.1029/2003JD003591, 2003. Prinn, R. G., Zander, R., Cunnold, D. M., Elkins, J. W., Engel, A., Fraser, P. J., Gunson, M. R., Ko, M. K. W., Mahieu, E., Midgley, P. M., Russell III, J. M., Volk, C. M., and Weiss, R. F.: Chapter 1 Long-lived ozone-related compounds, in: Scientific Assessment of Ozone Depletion: 1998, Global Ozone Research and Monitoring Project – Report No. 44., World Meteorological Organization, Geneva, Switzerland, 1999. Prinn, R. G.: Measurement equation for trace chemicals in fluids and solution of its inverse, in: Inverse Methods in Global Biogeochemical Cycles, Geophys. Monogr. Ser., 114, edited by: Kasibhatla, P., Heimann, M., Rayner, P., et al., AGU, Washington DC, USA, 3–18, 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 histoty of chemically and radiatively important gases in air deduced from ALE/GAGE/AGAGE, J. Geophys. Res., 105(D14), 17751–17792, 2000. 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. Simmonds, P. G., Cunnold, D. M., Weiss, R. F., Miller, B. R., Prinn, R. G., Fraser, P. J., McCulloch, A., Alyea, F. N., and O'Doherty, S.: Global trends and emission estimates of CCl<sub>4</sub> from in situ background observations from July 1978 to June 1996, J. Geophys. Res., 103(D13), 16017–16027, 1998. Solomon, S., Qin, D., Manning, M., Alley, R. B., Berntsen, T., Bindoff, N. L., Chen, Z., Chidthaisong, A., Gregory, J. M., Hegerl, G. C., Heimann, M., Hewitson, B., Hoskins, B. J., Joos, F., Jouzel, J., Kattsov, V., Lohmann, U., Matsuno, T., Molina, M., Nicholls, N., Overpeck, J., Raga, G., Ramaswamy, V., Ren, J., Rusticucci, M., Somerville, R., Stocker, T. F., Whetton, P., Wood, R. A., and Wratt, D.: Technical Summary. 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. B., Tignor, M., and Miller, H. L., Cambridge University Press, Cambridge, United Kingdom and New York, NY, USA, 2007. Stohl, A., Seibert, P., Arduini, J., Eckhardt, S., Fraser, P., Greally, B. R., Lunder, C., Maione, M., Mühle, J., O'Doherty, S., Prinn, R. G., Reimann, S., Saito, T., Schmidbauer, N., Simmonds, P. G., Vollmer, M. K., Weiss, R. F., and Yokouchi, Y.: An analytical inversion method for determining regional and global emissions of greenhouse gases: Sensitivity studies and application to halocarbons, Atmos. Chem. Phys., 9, 1597–1620, doi:10.5194/acp-9-1597-2009, 2009. United Nations Environment Programme, Montreal Protocol on Substances that Deplete the Ozone Layer, UNEP, 1987, http://www.unep.ch/ozone/mont_t.htm, last access: September 1997. United Nations Environment Programme: Production and consumption of ozone depleting substances under the Montreal Protocol: 1986–2004, Ozone secretariat, Nairobi, Kenya, http://www.unep.org/ozone/publications/Production_and_consumption2005.pdf, 2005. Volk, C. M., Elkins, J. W., Fahey, D. W., Dutton, G. S., Gilligan, J. M., Loewenstein, M., Podolske, J. R., Chan, K. R., and Gunson, M. R.: Evaluation of source gas lifetimes from stratospheric observations, J. Geophys. Res., 102(D21), 25543–25564, 1997. Xiao, X.: Optimal estimation of the surface fluxes of chloromethanes using a 3-D global atmospheric chemical transport model, Ph.D. thesis, MIT, Cambridge, http://globalchange.mit.edu/files/document/Xiao_PhD_08.pdf, 2008. Xiao, X., Prinn, R. G., Fraser, P. J., Simmonds, P. G., Weiss, R. F., O'Doherty, S., Miller, B. R., Salameh, P. K., Harth, C. M., Krummel, P. B., Porter, L. W., Mühle, J., Greally, B. R., Cunnold, D., Wang, R., Montzka, S. A., Elkins, J. W., Dutton, G. S., Thompson, T. M., Butler, J. H., Hall, B. D., Reimann, S., Vollmer, M. K., Stordal, F., Lunder, C., Maione, M., Arduini, J., and Yokouchi, Y.: Optimal estimation of the surface fluxes of methyl chloride using a 3-D global chemical transport model, Atmos. Chem. Phys., 10, 5515–5533, doi:10.5194/acp-10-5515-2010, 2010. Yvon-Lewis, S. A. and Butler, J. H.: Effect of oceanic uptake on atmospheric lifetimes of selected trace gases, J. Geophys. Res., 107(D20), 4414, doi:10.1029/2001JD001267, 2002.