ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-12-3653-2012 Emissions halted of the potent greenhouse gas SF<sub>5</sub>CF<sub>3</sub> Sturges W. T. 1 Oram D. E. 1 2 Laube J. C. 1 Reeves C. E. 1 Newland M. J. 1 Hogan C. 1 Martinerie P. 3 Witrant E. 4 Brenninkmeijer C. A. M. 5 Schuck T. J. 5 Fraser P. J. 6 The School of Environmental Sciences, University of East Anglia, Norwich NR4 7TJ, UK National Centre for Atmospheric Science, School of Environmental Sciences, Univ. of East Anglia, Norwich NR4 7TJ, UK UJF &ndash; Grenoble 1/CNRS, Laboratoire de Glaciologie et Géophysique de l'Environnement (LGGE) UMR5183, Grenoble, 38041, France Grenoble Image Parole Signal Automatique (GIPSA-lab), Université Joseph Fourier/CNRS, BP 46, 38 402 Saint Martin d'Hères, France Max Planck Institute for Chemistry, Air Chemistry Division, Mainz, Germany Centre for Australian Weather and Climate Research, Commonwealth Scientific and Industrial Research Organisation, Aspendale, Victoria 3195, Australia 19 04 2012 12 8 3653 3658 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/12/3653/2012/acp-12-3653-2012.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/12/3653/2012/acp-12-3653-2012.pdf

Long term measurements in background air (Cape Grim, Tasmania) and firn air (NEEM, Greenland) of the potent long-lived greenhouse gas SF<sub>5</sub>CF<sub>3</sub> show that emissions declined after the late 1990s, having grown since the 1950s, and became indistinguishable from zero after 2003. The timing of this decline suggests that emissions of this gas may have been related to the production of certain fluorochemicals; production of which have been recently phased out. An earlier observation of closely correlated atmospheric abundances of SF<sub>5</sub>CF<sub>3</sub> and SF<sub>6</sub> are shown here to have likely been purely coincidental, as their respective trends diverged after 2002. Due to its long lifetime (ca. 900 yr), atmospheric concentrations of SF<sub>5</sub>CF<sub>3</sub> have not declined, and it is now well mixed between hemispheres, as is also shown here from interhemispheric aircraft measurements. Total cumulative emissions of SF<sub>5</sub>CF<sub>3</sub> amount to around 5 kT.

 References Brenninkmeijer, C. A. M., Crutzen, P., Boumard, F., Dauer, T., Dix, B., Ebinghaus, R., Filippi, D., Fischer, H., Franke, H., Frieß, U., Heintzenberg, J., Helleis, F., Hermann, M., Kock, H. H., Koeppel, C., Lelieveld, J., Leuenberger, M., Martinsson, B. G., Miemczyk, S., Moret, H. P., Nguyen, H. N., Nyfeler, P., Oram, D., O'Sullivan, D., Penkett, S., Platt, U., Pupek, M., Ramonet, M., Randa, B., Reichelt, M., Rhee, T. S., Rohwer, J., Rosenfeld, K., Scharffe, D., Schlager, H., Schumann, U., Slemr, F., Sprung, D., Stock, P., Thaler, R., Valentino, F., van Velthoven, P., Waibel, A., Wandel, A., Waschitschek, K., Wiedensohler, A., Xueref-Remy, I., Zahn, A., Zech, U., and Ziereis, H.: Civil Aircraft for the regular investigation of the atmosphere based on an instrumented container: The new CARIBIC system, Atmos. Chem. Phys., 7, 4953–4976, http://dx.doi.org/10.5194/acp-7-4953-2007doi:10.5194/acp-7-4953-2007, 2007. Buizert, C., Martinerie, P., Petrenko, V. V., Severinghaus, J. P., Trudinger, C. M., Witrant, E., Rosen, J. L., Orsi, A. J., Rubino, M., Etheridge, D. M., Steele, L. P., Hogan, C., Laube, J. C., Sturges, W. T., Levchenko, V. A., Smith, A. M., Levin, I., Conway, T. J., Dlugokencky, E. J., Lang, P. M., Kawamura, K., Jenk, T. M., White, J. W. C., Sowers, T., Schwander, J., and Blunier, T.: Gas transport in firn: multiple-tracer characterisation and model intercomparison for NEEM, Northern Greenland, Atmos. Chem. Phys. Discuss., 11, 15975–16021, http://dx.doi.org/10.5194/acpd-11-15975-2011doi:10.5194/acpd-11-15975-2011, 2011. Busenberg, E. and Plummer, L. N.: Dating groundwater with trifluoromethyl sulfurpentafluoride (SF$_5$CF$_3)$, sulfur hexafluoride (SF$_6)$, CF<sub>3</sub>Cl (CFC-13), and CF<sub>2</sub>Cl<sub>2</sub> (CFC-12), Water Resour. Res., 44, W02431, http://dx.doi.org/10.1029/2007WR006150doi:10.1029/2007WR006150, 2008. Fabre, A., Barnola, J.-M., Arnaud, L., and Chappellaz, J.: Determination of gas diffusivity in polar firn: Comparison between experimental measurements and inverse modelling, Geophys. Res. Lett., 27, 557–560, http://dx.doi.org/10.1029/1999GL010780doi:10.1029/1999GL010780, 2000. Fraser, P. J., Oram, D. E., Reeves, C. E., Penkett, S. A., and Mc-Culloch, A.: Southern Hemispheric halon trends (1978–1998) and global halon emissions, J. Geophys. Res., 104, 15985–15999, 1999. Gerstell, M. F., Francisco, J. S., Yung, Y. L., Boxe, C., and Aaltonee, E. T.: Keeping Mars warm with new super greenhouse gases, P. Natl. Acad. Sci., 98, 2154–2157, http://dx.doi.org/10.1073/pnas.051511598doi:10.1073/pnas.051511598, 2001. Hough, A. M.: The development of a two-dimensional global tropospheric model, 1, the model transport, Atmos. Environ., 23, 1235–1261, 1989. Hough, A. M.: Development of a two-dimensional global tropospheric model: Model chemistry, J. Geophys. Res., 96, 7325–7362, 1991. Huang, L., Zhu, L., Pan, X., Zhang, J., Ouyang, B., and Hou, H.: One potential source of the potent greenhouse gas SF$_5$CF<sub>3</sub>: The reaction of SF$_6$ with fluorocarbon under discharge, Atmos. Environ., 39, 1641–653, http://dx.doi.org/10.1016/j.atmosenv.2004.11.013doi:10.1016/j.atmosenv.2004.11.013, 2005. Laube, J. C., Martinerie, P., Witrant, E., Blunier, T., Schwander, J., Brenninkmeijer, C. A. M., Schuck, T. J., Bolder, M., Röckmann, T., van der Veen, C., Bönisch, H., Engel, A., Mills, G. P., Newland, M. J., Oram, D. E., Reeves, C. E., and Sturges, W. T.: Accelerating growth of HFC-227ea (1,1,1,2,3,3,3-heptafluoropropane) in the atmosphere, Atmos. Chem. Phys., 10, 5903–5910, http://dx.doi.org/10.5194/acp-10-5903-2010doi:10.5194/acp-10-5903-2010, 2010. Levin, I., Naegler, T., Heinz, R., Osusko, D., Cuevas, E., Engel, A., Ilmberger, J., Langenfelds, R. L., Neininger, B., Rohden, C. v., Steele, L. P., Weller, R., Worthy, D. E., and Zimov, S. A.: The global SF6 source inferred from long-term high precision atmospheric measurements and its comparison with emission inventories, Atmos. Chem. Phys., 10, 2655–2662, http://dx.doi.org/10.5194/acp-10-2655-2010doi:10.5194/acp-10-2655-2010, 2010. Martinerie, P., Nourtier-Mazauric, E., Barnola, J.-M., Sturges, W. T., Worton, D. R., Atlas, E., Gohar, L. K., Shine, K. P., and Brasseur, G. P.: Long-lived halocarbon trends and budgets from atmospheric chemistry modelling constrained with measurements in polar firn, Atmos. Chem. Phys., 9, 3911–3934, http://dx.doi.org/10.5194/acp-9-3911-2009doi:10.5194/acp-9-3911-2009, 2009. Miller, T. M., Arnold, S. T., Viggiano, A. A., and Knighton, W. B.: Electron attachment of SF$_5$CF<sub>3</sub> (296–563 K) and calculations of the neutral and anion thermochemistry, J. Chem. Phys., 116, 6021–6027, http://dx.doi.org/10.1063/1.1457442doi:10.1063/1.1457442, 2002. Montzka, S. A., Reimann, S. (Coordinating Lead Authors), Engel, A., Krüger, K., O'Doherty, S., Sturges, W., Blake, D., Dorf, M., Fraser, P., Froidevaux, L., Jucks, K., Kreher, K., Kurylo, M., Mellouki, A., Miller, J., Nielsen, O.-J., Orkin, V., Prinn, R., Rhew, R., Santee, M., Stohl, A., and Verdonik, D.: Scientific Assessment of Ozone Depletion: 2010, Global Ozone Research and Monitoring Project, Report No. 52, 516 pp., Chapter 1, Ozone-Depleting Substances (ODSs) and Related Chemicals, World Meteorological Organization, Geneva, Switzerland, 2011. Mühle, J., Ganesan, A. L., Miller, B. R., Salameh, P. K., Harth, C. M., Greally, B. R., Rigby, M., Porter, L. W., Steele, L. P., Trudinger, C. M., Krummel, P. B., O'Doherty, S., Fraser, P. J., Simmonds, P. G., Prinn, R. G., and Weiss, R. F.: Perfluorocarbons in the global atmosphere: tetrafluoromethane, hexafluoroethane, and octafluoropropane, Atmos. Chem. Phys., 10, 5145–5164, http://dx.doi.org/10.5194/acp-10-5145-2010doi:10.5194/acp-10-5145-2010, 2010. Oram, D. E., Reeves, C. E., Fraser, P. J., and Penkett, S. A.: Measurements of HCFC-142b and HCFC-141b in the Cape Grim air archive: 1978–1993, Geophys. Res. Lett., 22, 2741–2744, http://dx.doi.org/10.1029/95GL02849doi:10.1029/95GL02849, 1995. Oram, D. E., Mani, F. S., Laube, J. C., Newland, M. J., Reeves, C. E., Sturges, W. T., Penkett, S. A., Brenninkmeijer, C. A. M., Röckmann, T., and Fraser, P. J.: Long-term tropospheric trend of octafluorocyclobutane (c-C4F8 or PFC-318), Atmos. Chem. Phys., 12, 261–269, http://dx.doi.org/10.5194/acp-12-261-2012doi:10.5194/acp-12-261-2012, 2012. Paul, A. G., Jones, K. C., and Sweetman, A. J.: A First Global Production, Emission and Environmental Inventory for Perfluorooctane Sulfonate, Environ. Sci. Technol., 43, 386–392, http://dx.doi.org/10.1021/es802216ndoi:10.1021/es802216n, 2009. Reeves, C. E., Sturges, W. T., Sturrock, G. A., Preston, K., Oram, D. E., Schwander, J., Mulvaney, R., Barnola, J.-M., and Chappellaz, J.: Trends of halon gases in polar firn air: implications for their emission distributions, Atmos. Chem. Phys., 5, 2055–2064, http://dx.doi.org/10.5194/acp-5-2055-2005doi:10.5194/acp-5-2055-2005, 2005. Renner, R.: The long and the short of perfluorinated replacements, Environ, Sci. Technol., 40, 12–13, http://dx.doi.org/10.1021/es062612adoi:10.1021/es062612a, 2006. Rommelaere, V., Arnaud, L., and Barnola, J.: Reconstructing recent atmospheric trace gas concentrations from polar firn and bubbly ice data by inverse methods, J. Geophys. Res., 102, 30069–30083, 1997. Rosiek, J., Lasa, J., Sliwka, I., and Ró\.zański, K.: Application of GC and Modulated ECD for the Determination of SF$_5$CF<sub>3</sub> Mixing Ratios in the Atmosphere, Chem. Anal. (Warsaw), 52, 235–242, 2007. Santoro, M. A.: Clarifying the SF$_5$CF<sub>3</sub> record, Science, 290, p 935, 2000. Solovev, S., Palmentieri, A., Potekhina, N. D., and Madey, T. E.: Mechanism for Electron-Induced SF$_5$CF<sub>3</sub> Formation in Condensed Molecular Films, J. Phys. Chem. C, 111, 18271–18278, 2007. Sturges, W. T., Wallington, T. J., Hurley, M. D., Shine, K. P., Sihra, K., Engel, A., Oram, D. E., Penkett, S. A., Mulvaney, R., and Brenninkmeijer, C. A. M.: A Potent Greenhouse Gas Identified in the Atmosphere: SF$_5$CF<sub>3</sub>, Science, 289, 611–613, http://dx.doi.org/10.1126/science.289.5479.611doi:10.1126/science.289.5479.611, 2000. Weiss, R. F., Mühle, J., Salameh, P. K., and Harth, C. M.: Nitrogen trifluoride in the global atmosphere, Geophys. Res. Lett., 35, L20821, http://dx.doi.org/10.1029/2008GL035913doi:10.1029/2008GL035913, 2008. Witrant, E., Martinerie, P., Hogan, C., Laube, J. C., Kawamura, K., Capron, E., Montzka, S. A., Dlugokencky, E. J., Etheridge, D., Blunier, T., and Sturges, W. T.: A new multi-gas constrained model of trace gas non-homogeneous transport in firn: evaluation and behavior at eleven polar sites, Atmos. Chem. Phys. Discuss., 11, 23029–23080, http://dx.doi.org/10.5194/acpd-11-23029-2011doi:10.5194/acpd-11-23029-2011, 2011. Worton, D. R., Sturges, W. T., Gohar, L. K., Shine, K. P., Martinerie, P., Oram, D. E., Humphrey, S. P., Begley, P., Gunn, L., Barnola, J.-M., Schwander, J., and Mulvaney, R.: Atmospheric Trends and Radiative Forcings of CF<sub>4</sub> and C<sub>2</sub>F$_6$ Inferred from Firn Air, Environ. Sci. Technol., 41, 2184–2189, http://dx.doi.org/10.1021/es061710tdoi:10.1021/es061710t, 2007.