ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-10-10305-2010 History of atmospheric SF<sub>6</sub> from 1973 to 2008 Rigby M. 1 Mühle J. 2 Miller B. R. 3 Prinn R. G. 1 Krummel P. B. 4 Steele L. P. 4 Fraser P. J. 4 Salameh P. K. 2 Harth C. M. 2 Weiss R. F. 2 Greally B. R. 5 O'Doherty S. 5 Simmonds P. G. 5 Vollmer M. K. 6 Reimann S. 6 Kim J. 7 Kim K.-R. 7 8 Wang H. J. 9 Olivier J. G. J. 10 Dlugokencky E. J. 11 Dutton G. S. 11 Hall B. D. 11 Elkins J. W. 11 Center for Global Change Science, Massachusetts Institute of Technology, Cambridge, MA, 02139, USA Scripps Institution of Oceanography, University of California at San Diego, La Jolla, CA, USA Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO, USA Centre for Australian Weather and Climate Research, CSIRO Marine and Atmospheric Research, Aspendale, Victoria, Australia School of Chemistry, University of Bristol, Bristol, UK Empa, Swiss Federal Laboratories for Materials Testing and Research, Switzerland School of Earth and Environmental Sciences, Seoul National University, South Korea Research Institute of Oceanography, Seoul National University, South Korea School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, GA, USA Netherlands Environmental Assessment Agency (PBL), Bilthoven, The Netherlands Earth System Research Laboratory, NOAA, Boulder, CO, USA 04 11 2010 10 21 10305 10320 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/10/10305/2010/acp-10-10305-2010.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/10/10305/2010/acp-10-10305-2010.pdf

We present atmospheric sulfur hexafluoride (SF<sub>6</sub>) mole fractions and emissions estimates from the 1970s to 2008. Measurements were made of archived air samples starting from 1973 in the Northern Hemisphere and from 1978 in the Southern Hemisphere, using the Advanced Global Atmospheric Gases Experiment (AGAGE) gas chromatographic-mass spectrometric (GC-MS) systems. These measurements were combined with modern high-frequency GC-MS and GC-electron capture detection (ECD) data from AGAGE monitoring sites, to produce a unique 35-year atmospheric record of this potent greenhouse gas. Atmospheric mole fractions were found to have increased by more than an order of magnitude between 1973 and 2008. The 2008 growth rate was the highest recorded, at 0.29 ± 0.02 pmolmol<sup>&minus;1</sup> yr<sup>&minus;1</sup>. A three-dimensional chemical transport model and a minimum variance Bayesian inverse method was used to estimate annual emission rates using the measurements, with a priori estimates from the Emissions Database for Global Atmospheric Research (EDGAR, version 4). Consistent with the mole fraction growth rate maximum, global emissions during 2008 were also the highest in the 1973–2008 period, reaching 7.4 ± 0.6 Gg yr<sup>&minus;1</sup> (1-σ uncertainties) and surpassing the previous maximum in 1995. The 2008 values follow an increase in emissions of 48 ± 20% since 2001. A second global inversion which also incorporated National Oceanic and Atmospheric Administration (NOAA) flask measurements and in situ monitoring site data agreed well with the emissions derived using AGAGE measurements alone. By estimating continent-scale emissions using all available AGAGE and NOAA surface measurements covering the period 2004–2008, with no pollution filtering, we find that it is likely that much of the global emissions rise during this five-year period originated primarily from Asian developing countries that do not report detailed, annual emissions to the United Nations Framework Convention on Climate Change (UNFCCC). We also find it likely that SF<sub>6</sub> emissions reported to the UNFCCC were underestimated between at least 2004 and 2005.

 References Busenberg, E. and L. N. Plummer, Dating Young Groundwater with Sulfur Hexafluoride: Natural and Anthropogenic Sources of Sulfur Hexafluoride, Water Resour. Res., 36(10), 3011–3030, doi:10.1029/2000WR900151, 2000. 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.-Atmos., 111, D10307, doi:10.1029/2005JD006058, http://www.agu.org/pubs/crossref/2006/2005JD006058.shtml, 2006. Cheng, C.: \chemSF_6 Production, Future Demand and Cooperation in China. Presented at the 4th International Conference on \chemSF_6 and the Environment, San Antonio, USA, 28–30 November 2006, 2006. Deeds, D A., Vollmer, M K., Kulongoski, J T., Miller, B R., Mühle, J., Harth, C M., Izbicki, J A., Hilton, D R., and Weiss, R F.: Evidence for crustal degassing of \chemSF_6 and \chemSF_6 in Mojave Desert groundwaters, Geochim. Cosmochim. Ac. , 72, 999–1013, doi:10.1016/j.gca.2007.11.027, 2008. Denning, A. S., Holzer, M., Gurney, K. R., Heimann, M., Law, R.M., Rayner, P.J., Fung, I.Y., Fan, S., Taguchi, S., Friedlingstein, P., Balkanski, Y., Taylor, J., Maiss, M., and Levin, I. 1999. Three-dimensional transport and concentration of \chemSF_6 : A model intercomparison study (TransCom-2), Tellus, 51B, 266–297, 1999. Dlugokencky, E., Steele, L. P., Lang, P., and Masarie, K.: The growth rate and distribution of atmospheric methane, J. Geophys. Res., 99, 17021–17043, 1994. Efron, B.: 1977 Rietz Lecture – Bootstrap Methods – Another look at the jackknife, Ann. Stat., 7, 1–26, 1979. Elkins, J. W. and Dutton, G. S.: Nitrous oxide and sulfur hexafluoride, [in State of the Climate in 2008], B. Am. Meteor. Soc., 90(8), S1–S196, 2009 Emmons, L. K., Walters, S., Hess, P. G., Lamarque, J.-F., Pfister, G. G., Fillmore, D., Granier, C., Guenther, A., Kinnison, D., Laepple, T., Orlando, J., Tie, X., Tyndall, G., Wiedinmyer, C., Baughcum, S. L., and Kloster, S.: Description and evaluation of the Model for Ozone and Related chemical Tracers, version 4 (MOZART-4), Geosci. Model Dev., 3, 43–67, doi:10.5194/gmd-3-43-2010, 2010. ESIA (European Semiconductor Industry Association): Intermediate Status Report of the Progress towards the Reduction of Perfluorocompound (PFC) Emissions from European Semiconductor Manufacturing. ECCE-ESIA, Brussels Belgium, 2007. Forster, P., Ramaswamy, V. , Artaxo, P., Berntsen, T. , Betts, R., Fahey, D.W., Haywood, J. , Lean, J., Lowe, D.C., Myhre, G., Nganga, J., Prinn, R., Raga, G., Schulz, M. and Van Dorland, R.: Changes in Atmospheric Constituents and in Radiative Forcing, in: Climate Change 2007: The Physical Science Basis. Contribution of Working Group 1 to the Fourth Assessment Report of the IPCC, edited by: Solomon, S., Qin, D., Manning, M., Chen, Z., Marquis, M., Averyt, K.B., Tignor, M. and Miller, H.L., Cambridge University Press, 2007. Fraser, P J., Porter, L W., Baly, S B., Krummel, P B., Dunse, B L., Steele, L P., Derek, N., Langenfelds, R L., Levin, I., Oram, D E., Elkins, J W., Vollmer, M K., and Weiss, R F.: Sulfur hexafluoride at Cape Grim: long term trends and regional emissions, in: Baseline Atmospheric Program Australia 2001–2002, edited by: Cainey, J M., Derek, N., and Krummel, P B., Bureau of Meteorology and CSIRO Atmospheric Research, 18–23, 2004. Geller, L., Elkins, J. W., Lobert, J., Clarke, A., Hurst, D. F., Butler, J., and Myers, R.: Tropospheric \chemSF_6: Observed latitudinal distribution and trends, derived emissions and interhemispheric exchange time, Geophys. Res. Lett., 24, 675–678, 1997. Gloor, M., Dlugokencky, E., Brenninkmeijer, C., Horowitz, L., Hurst, D F., Dutton, G., Crevoisier, C., Machida, T., and Tans, P.: Three-dimensional \chemSF_6 data and tropospheric transport simulations: Signals, modeling accuracy, and implications for inverse modeling, J. Geophys. Res.-Atmos., 112, D15112, doi:10.1029/2006JD007973, http://www.agu.org/pubs/crossref/2007/2006JD007973.shtml, 2007. Hall, B. D., Dutton, G. S., and Elkins, J. W., The NOAA nitrous oxide standard scale for atmospheric observations, J. Geophys. Res., 112, D09305, doi:10.1029/2006JD007954, 2007. Hall, T. and Waugh, D.: Tracer transport in the tropical stratosphere due to vertical diffusion and horizontal mixing, Geophys. Res. Lett., 24, 1383–1386, 1997. Hurst, D. F., Lin,J. C., Romashkin, P. A., Daube, B. C., Gerbig, C. , Matross, D. M., Wofsy, S. C., Hall, B. D., and Elkins, J. W., Continuing global significance of emissions of Montreal Protocol – restricted halocarbons in the United States and Canada, J. Geophys. Res., 111, D15302, doi:10.1029/2005JD006785, 2006. IPCC (Intergovernmental Panel on Climate Change): 2006 Guidelines for National Greenhouse Gas Inventories, edited by: Eggleston, S., Buendia, L., Miwa, K., Ngara, T., and Tanabe, K., IPCC-TSU NGGIP, IGES, Japan, 2006. JRC/PBL (Joint Research Centre of the European Commission/Netherlands Environmental Assessment Agency), Emission Database for Global Atmospheric Research (EDGAR), release version 4.0, http://edgar.jrc.ec.europa.eu, 2009. Kalnay, E., Kanamitsu, M., Kistler, R., Collins, W., Deaven, D., Gandin, L., Iredell, M., Saha, S., White, G., Woollen, J., Zhu, Y., Chelliah, M., Ebisuzaki, W., Higgins, W., Janowiak, J., Mo, K., Ropelewski, C., Wang, J., Leetmaa, A., Reynolds, R., Jenne, R., and Joseph, D.: The NCEP/NCAR 40-year reanalysis project, B. Am. Meteorol. Soc., 77, 437–471, 1996. Knopman, D. and Smythe, K.: 2004–2006 \chemSF_6 data summary. Project Memorandum PM-2327-NEMA, 25 June 2007. With data table 1961–2006, 2007. Langenfelds, R L., Fraser, P J., Francey, R J., Steele, L P., Porter, L W., and Allison, C E.: The Cape Grim air archive: The first seventeen years, 1978–1995, in: Baseline Atmospheric Program (Australia) 1994–95, edited by: Francey, R J., Dick, A L., and Derek, N., 53–70, 1996. 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, doi:10.5194/acp-10-2655-2010, 2010. Maiss, M. and Levin, I.: Global Increase Of \chemSF_6 Observed In The Atmosphere, Geophys. Res. Lett., 21, 569–572, 1994. Maiss, M., Steele, L., Francey, R., Fraser, P., Langenfelds, R., Trivett, N., and Levin, I.: Sulfur hexafluoride - A powerful new atmospheric tracer, Atmos. Environ., 30(10–11), 1621–1629, 1996. Maiss, M. and Brenninkmeijer, C.M.: Atmospheric \chemSF_6: Trends, Sources, and Prospects, Environ. Sci. Technol., 32, 3077–3086, 1998. Miller, B R., Weiss, R F., Salameh, P K., Tanhua, T., Greally, B R., Mühle, J., and Simmonds, P G.: Medusa: A sample preconcentration and GC/MS detector system for in situ measurements of atmospheric trace halocarbons, hydrocarbons, and sulfur compounds, Anal. Chem., 80, 1536–1545, doi:10.1021/ac702084k, http://pubs.acs.org/doi/abs/10.1021/ac702084k, 2008. Niemeyer, L. and Chu, F.: \chemSF_6 and the Atmosphere, IEEE. T. Electr. Insul., 27(1), 184–187, 1992. Nike: Corporate Responsibility Report, FY04, 2005. Patra, P. K., Takigawa, M., Dutton, G. S., Uhse, K., Ishijima, K., Lintner, B. R., Miyazaki, K., and Elkins, J. W.: Transport mechanisms for synoptic, seasonal and interannual SF6 variations and "age" of air in troposphere, Atmos. Chem. Phys., 9, 1209–1225, doi:10.5194/acp-9-1209-2009, 2009. Peters, W., Krol, M., Dlugokencky, E., Dentener, F., Bergamaschi, P., Dutton, G., von Velthoven, P., Miller, J., Bruhwiler, L., and Tans, P.: Toward regional-scale modeling using the two-way nested global model TM5: Characterization of transport using \chemSF_6, J. Geophys. Res.-Atmos., 109, D19314, doi:10.1029/2004JD005020, 2004. Prinn, R.: 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., Mahowald, N., Prinn, R. G., and Hartley, D. E., American Geophysical Union, Washington DC, 2000. Prinn, R., Weiss, R., Fraser, P., Simmonds, P., Cunnold, D., Alyea, F., O'Doherty, S., Salameh, P., Miller, B., Huang, J., Wang, R., Hartley, D., Harth, C., Steele, L., Sturrock, G., Midgley, P., 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, doi:10.1029/2000JD900141, 2000. Ravishankara, A., Solomon, S., Turnipseed, A., and Warren, R.: Atmospheric Lifetimes of Long-Lived Halogenated Species, Science, 259, 194–199, 1993. Rinsland, C., Brown, L., and Farmer, C.: Infrared Spectroscopic Detection of Sulfur-Hexafluoride (\chemSF_6) in the Lower Stratosphere and Upper Troposphere, J. Geophys. Res.-Atmos., 95, 5577–5585, 1990. SPS (Science and Policy Services): Sales of sulphur hexafluoride (\chemSF_6) by end-use applications, Annual sales for 1961 through 1996, Sales projections for 1997 through 2000, Washington, March, 1997. Santella, N., Ho, D T., Schlosser, P., and Stute, M.: Widespread elevated atmospheric \chemSF_6 mixing ratios in the Northeastern United States: Implications for groundwater dating, J. Hydrol., 349, 139–146, doi:10.1016/j.jhydrol.2007.10.031, 2008. Smythe, K. D: Trends in \chemSF_6 Sales and End-Use Applications: 1961-2003. Presented at the 3rd International Conference on \chemSF_6 and the Environment, Scottsdale, USA, 1–3 December 2004, with data table 1961–2003, 2004. SIA (Semiconductor Industry Association): Total Semiconductor World Market Sales and Shares for 1982–2005, San Jose, 2006. UNFCCC (United Nations Framework on Climate Change): Data (1990–2007) from CRF data files submitted by Annex I countries to the UN Framework Convention on Climate Change as part of their 2009 National Inventory Report submission, Bonn, Switzerland, 2010. Vollmer, M K. and Weiss, R F.: Simultaneous determination of sulfur hexafluoride and three chlorofluorocarbons in water and air, Mar. Chem., 78, 137–148, 2002. Vollmer, M K., Zhou, L X., Greally, B R., Henne, S., Yao, B., Reimann, S., Stordal, F., Cunnold, D M., Zhang, X C., Maione, M., Zhang, F., Huang, J., and Simmonds, P G.: Emissions of ozone-depleting halocarbons from China, Geophys. Res. Lett., 36, L15823, doi:10.1029/2009GL038659, 2009.