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Cclf3), CFC-114 (C 2Cl2f4), and CFC-115 (C2clf5

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Cclf3), CFC-114 (C 2Cl2f4), and CFC-115 (C2clf5 Atmos. Chem. Phys., 18, 979–1002, 2018 https://doi.org/10.5194/acp-18-979-2018 © Author(s) 2018. This work is distributed under the Creative Commons Attribution 4.0 License. Atmospheric histories and emissions of chlorofluorocarbons CFC-13 (CClF3), 6CFC-114 (C2Cl2F4), and CFC-115 (C2ClF5) Martin K. Vollmer1, Dickon Young2, Cathy M. Trudinger3, Jens Mühle4, Stephan Henne1, Matthew Rigby2, Sunyoung Park5, Shanlan Li5, Myriam Guillevic6, Blagoj Mitrevski3, Christina M. Harth4, Benjamin R. Miller7,8, Stefan Reimann1, Bo Yao9, L. Paul Steele3, Simon A. Wyss1, Chris R. Lunder10, Jgor Arduini11,12, Archie McCulloch2, Songhao Wu5, Tae Siek Rhee13, Ray H. J. Wang14, Peter K. Salameh4, Ove Hermansen10, Matthias Hill1, Ray L. Langenfelds3, Diane Ivy15, Simon O’Doherty2, Paul B. Krummel3, Michela Maione11,12, David M. Etheridge3, Lingxi Zhou16, Paul J. Fraser3, Ronald G. Prinn15, Ray F. Weiss4, and Peter G. Simmonds2 1Laboratory for Air Pollution and Environmental Technology, Empa, Swiss Federal Laboratories for Materials Science and Technology, Überlandstrasse 129, 8600 Dübendorf, Switzerland 2Atmospheric Chemistry Research Group, School of Chemistry, University of Bristol, Bristol, UK 3Climate Science Centre, CSIRO Oceans and Atmosphere, Aspendale, Victoria, Australia 4Scripps Institution of Oceanography, University of California at San Diego, La Jolla, California, USA 5Kyungpook Institute of Oceanography, Kyungpook National University, South Korea 6METAS, Federal Institute of Metrology, Lindenweg 50, Bern-Wabern, Switzerland 7Earth System Research Laboratory, NOAA, Boulder, Colorado, USA 8Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, Colorado, USA 9Meteorological Observation Centre (MOC), China Meteorological Administration (CMA), Beijing, China 10Norwegian Institute for Air Research, Kjeller, Norway 11Department of Pure and Applied Sciences, University of Urbino, Urbino, Italy 12Institute of Atmospheric Sciences and Climate, Italian National Research Council, Bologna, Italy 13Korea Polar Research Institute, KIOST, Incheon, South Korea 14School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, Georgia, USA 15Center for Global Change Science, Massachusetts Institute of Technology, Cambridge, Massachusetts, USA 16Chinese Academy of Meteorological Sciences (CAMS), China Meteorological Administration (CMA), Beijing, China Correspondence: Martin K. Vollmer ([email protected]) Received: 8 October 2017 – Discussion started: 10 October 2017 Revised: 6 December 2017 – Accepted: 11 December 2017 – Published: 25 January 2018 Abstract. Based on observations of the chlorofluorocar- provide the first comprehensive global analysis. This com- bons CFC-13 (chlorotrifluoromethane), 6CFC-114 (com- pound increased monotonically from its first appearance in bined measurement of both isomers of dichlorotetrafluo- the atmosphere in the late 1950s to a mean global abun- roethane), and CFC-115 (chloropentafluoroethane) in atmo- dance of 3.18 ppt (dry-air mole fraction in parts per trillion, spheric and firn samples, we reconstruct records of their tro- pmolmol−1) in 2016. Its growth rate has decreased since pospheric histories spanning nearly 8 decades. These com- the mid-1980s but has remained at a surprisingly high mean pounds were measured in polar firn air samples, in am- level of 0.02 pptyr−1 since 2000, resulting in a continuing bient air archived in canisters, and in situ at the AGAGE growth of CFC-13 in the atmosphere. 6CFC-114 increased (Advanced Global Atmospheric Gases Experiment) network from its appearance in the 1950s to a maximum of 16.6 ppt and affiliated sites. Global emissions to the atmosphere are in the early 2000s and has since slightly declined to 16.3 ppt derived from these observations using an inversion based in 2016. CFC-115 increased monotonically from its first ap- on a 12-box atmospheric transport model. For CFC-13, we pearance in the 1960s and reached a global mean mole frac- Published by Copernicus Publications on behalf of the European Geosciences Union. 980 M. K. Vollmer et al.: Minor CFCs tion of 8.49 ppt in 2016. Growth rates of all three compounds global warming potentials (GWPs), with those for CFC-13 over the past years are significantly larger than would be ex- (13 900 for GWP-100 yr and ∼ 16 000 for GWP-500 yr) only pected from zero emissions. Under the assumption of un- surpassed by very few other greenhouse gases. changing lifetimes and atmospheric transport patterns, we Removal of these CFCs from the atmosphere occurs pre- derive global emissions from our measurements, which have dominantly in the stratosphere through ultraviolet (UV) pho- remained unexpectedly high in recent years: mean yearly tolysis and reaction with excited atomic oxygen (O(1D)), and emissions for the last decade (2007–2016) of CFC-13 are to a lesser extent by Lyman-α photolysis in the mesosphere. at 0:48 ± 0:15 ktyr−1 (> 15 % of past peak emissions), of The atmospheric lifetime for CFC-13 of 640 years used in 6CFC-114 at 1:90 ± 0:84 ktyr−1 (∼ 10 % of peak emis- the present study is based on a study by Ravishankara et al. sions), and of CFC-115 at 0:80±0:50 ktyr−1 (> 5 % of peak (1993) and is dominated (80 %) by the removal through reac- emissions). Mean yearly emissions of CFC-115 for 2015– tion with O(1D); see Table1. The lifetimes for CFC-114 and 2016 are 1:14 ± 0:50 ktyr−1 and have doubled compared to CFC-115 have recently been revised as part of the SPARC the 2007–2010 minimum. We find CFC-13 emissions from (Stratosphere–troposphere Processes And their Role in Cli- aluminum smelters but if extrapolated to global emissions, mate) lifetimes assessment (SPARC, 2013). In that study they cannot account for the lingering global emissions deter- the lifetime of CFC-114 was reported as 189 years (153– mined from the atmospheric observations. We find impurities 247 years) with 72 % of the loss from UV photolysis and 1 of CFC-115 in the refrigerant HFC-125 (CHF2CF3) but if ex- 28 % from reaction with O( D) (Burkholder and Mellouki, trapolated to global emissions, they can neither account for 2013). However, our closer inspection of the literature from the lingering global CFC-115 emissions determined from the laboratory studies, used to derive UV absorption spectra and atmospheric observations nor for their recent increases. We O(1D) reaction rates (Sander et al., 2011), suggests that no also conduct regional inversions for the years 2012–2016 for consideration was given in these older studies with regard the northeastern Asian area using observations from the Ko- to potential impurities of CFC-114a in CFC-114. Such im- rean AGAGE site at Gosan and find significant emissions for purities are likely present (Supplement, Laube et al., 2016), 6CFC-114 and CFC-115, suggesting that a large fraction of in which case they could have biased the CFC-114 UV ab- their global emissions currently occur in northeastern Asia sorption spectra, leading to an underestimate of its lifetime, and more specifically on the Chinese mainland. as its absorption is significantly weaker compared to that of CFC-114a in the critical photolysis wavelength region (Davis et al., 2016; J. B. Burkholder, personal communica- tion, November 2017). O(1D) kinetics for the two isomers are 1 Introduction similar and hence would not have affected lifetime estimates as much if such impurities were present (Baasandorj et al., Chlorofluorocarbons (CFCs) are very stable man-made com- 2011, 2013; Davis et al., 2016). For CFC-115 the lifetime has pounds known to destroy stratospheric ozone. For this reason been significantly reduced from 1700 years in earlier stud- they were regulated for phase-out under the Montreal Proto- ies (Ravishankara et al., 1993) to 540 years (404–813 years) col on Substances that Deplete the Ozone Layer and its sub- (SPARC, 2013) mainly due to significantly revised O(1D) ki- sequent amendments. The ban has been effective since the netics (Baasandorj et al., 2013). This revised lifetime gives end of 1995 for developed countries and the end of 2010 37 % of the loss derived from UV photolysis and 63 % from for developing countries. The ban is put on production for reaction with O(1D) and a minor contribution from Lyman-α emissive use and does not cover production for feedstock photolysis (Burkholder and Mellouki, 2013). or recycling of used CFCs for recharging of old equipment, CFC-13 and its R-503 blend with 40 % by mass of the latter being applied particularly in the refrigeration sec- HFC-23 (CHF3) have been used as special-application tor. While the dominant CFCs in the atmosphere are CFC- low-temperature refrigerants (IPCC/TEAP, 2005; Calm and 12 (CCl2F2), CFC-11 (CCl3F), and CFC-113 (C2Cl3F3), Hourahan, 2011) but small enhancements in CFC-13 were this article reports on CFC-13 (chlorotrifluoromethane, also found in the emissions from aluminum plants (Harnisch, CClF3), 6CFC-114, here defined as the combined iso- 1997; Penkett et al., 1981). CFC-13 could also be present mer 1,2-dichlorotetrafluoroethane (CClF2CClF2, CFC-114, as an impurity in CFC-12 (CCl2F2) due to over-fluorination CAS 76-14-2) and 1,1-dichlorotetrafluoroethane (CCl2FCF3, during production. CFC-114a, CAS 374-07-2), and CFC-115 (chloropentaflu- Reports on atmospheric CFC-13 in peer-reviewed arti- oroethane, C2ClF5). The compounds were mainly used in cles are rare. Early measurements were reported on by Ras- specialized refrigeration; hence, their abundances in the at- mussen and Khalil (1980), Penkett et al. (1981), and Fabian mosphere are considerably smaller than those of the three et al.(1981), who measured a first atmospheric vertical pro- major CFCs. However, their atmospheric lifetimes are sig- file of this compound. CFC-13 measurements were made by nificantly longer (see Table1 for climate metrics). Ozone de- Oram(1999) in the samples of the Southern Hemisphere pletion potentials (ODPs) for the three compounds are high Cape Grim Air Archive (CGAA) covering 1978–1995. He and their radiative efficiencies are high, thereby yielding high found increasing mole fractions from 1.2 pptv (therein re- Atmos.
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