Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 8 17 2008 10.5194/acp-8-5143-2008 http://www.atmos-chem-phys.net/8/5143/2008/ http://www.atmos-chem-phys.net/8/5143/2008/acp-8-5143-2008.html http://www.atmos-chem-phys.net/8/5143/2008/acp-8-5143-2008.pdf 5143 5149 2008-09-02 First atmospheric observations of three chlorofluorocarbons J. C. Laube j.laube@iau.uni-frankfurt.de A. Engel Institute for Atmosphere and Environment, University of Frankfurt (Main), Germany We report the first atmospheric observations of the Chlorofluorocarbons (CFCs) trifluorochloroethene, 3-chloropentafluoropropene and 4,4-dichlorohexafluoro-1-butene by means of Gas Chromatography with Electron Capture and Mass Spectrometric detection (GC-ECD-MS) in air samples taken at the Taunus Observatory operated by the University of Frankfurt (Main) and the Jungfraujoch High Altitude Research Station in Switzerland. These substances belong to a class of CFCs containing a double bond and are suspected to originate from the production and thermal degradation of widely used fluoropolymers like polychlorotrifluoroethene (PCTFE). Their atmospheric lifetimes are expected to be rather short. A quantitative calibration could only be derived for trifluorochloroethene but not for the other species by now. Thus, we use a relative sensitivity method to get a first indication of the observed atmospheric abundances. Identification was possible because of an air plume containing high concentrations of these substances. We suggest that the abundances found on this occasion originated from a local source. However, we have also observed the novel CFCs in air masses representative of background conditions, though with much lower concentrations. These species and some of their degradation products are toxic and could also be relevant for stratospheric and tropospheric ozone depletion. Abusleme, J. A. and Manzoni, C.: Synthesis of thermoplastic perhalogenated (co)polymers of chlorotrifluoroethylene, European Patent, EP1067146, 2004. Birnbaum, H. A., Scheel, L. D., and Coleman, W. E.: The toxicology of the pyrolysis products of polychlorotrifluoroethylene, Am. Ind. Hyg. Assoc. J., 29, 61–65, 1968. Clayton, J. W.: Toxicology of the fluoroalkenes: review and research needs, Environ. Health Persp., 21, 255–267, 1977. Clerbaux, C., Cunnold, D. M., Anderson, J., et al.: Halogenated Long-lived Compounds, Scientific assessment of ozone depletion: 2006, Global Ozone Research and Monitoring Project, Report No 50, Chapter 1, World Meteorological Organization, Geneva, Switzerland, 2007. Cook, E. W. and Pierce, J. S.: Toxicology of fluoro-olefins, Nature, 242, 337–338, 1973. Field, J. A. and Sierra-Alvarez, R.: Biodegradability of chlorinated solvents and related chlorinated aliphatic compounds, Rev. Environ. Sci. Biotechnol., 3, 185–254, 2004. Laube, J. C. and Engel, A.: First atmospheric observations of three chlorofluorocarbons, Atmos. Chem. Phys. Discuss., 8, 6683–6695, 2008. Law, K. S., Sturges, W. T., Blake, D. R., et al.: Halogenated very short-lived substances, Scientific assessment of ozone depletion: 2006, Global Ozone Research and Monitoring Project, World Meteorological Organization, Geneva, Switzerland, Report No 50, Chapter 2, 2007. Lo, E. S. and Elizabeth, N. J.: Copolymers of dichlorohexafluorobutene, US-Patent 2914514, 1959. Long, G. R., Prentice, L. D., and Bialkowski, S. E.: Chemical reactions following the IRMPD of C₂F₃Cl, Appl. Phys. B-Photo, 34, 97–106, 1984. National Institute of Standards and Technology: Mass Spectral Search Program for the NIST/EPA/NIH Mass Spectral Library, Version 2.0 d, National Institute of Standards and Technology, Gaithersburg, MD, USA, 2005. Reimann, S., Vollmer, M. K., Folini, D., Steinbacher, M., Hill, M., Buchmann, B., Zander, R., and Mahieu, E.: Observations of Long-Lived Anthropogenic Halocarbons at the High-Alpine site of Jungfraujoch (Switzerland) for Assessment of Trends and European Sources, Sci. Total Environ., 391(2–3), 224–231, 2008. Robb, L. E. and Westfield, N. J.: Polyblends of a thermoplastic tetra-fluoroethylene polymer, US-Patent 3019206, 1962. Solomon, S.: Stratospheric ozone depletion: a review of concepts and history, Rev. Geophys., 37, 275–316, 1999. Thun, M. and Kimbrough, R. D.: Fatal chemical pneumonia from 1,1,2,3,3-pentafluoro-3-chloropropene in an unmarked gas tank, Clin. Toxicol., 18, 481–487, 1981. Utracki, L. A.: History of commercial polymer alloys and blends (from a perspective of the patent literature), Polym. Eng. Sci, 35, 2–17, 1995. Zulfiqar, S., Zulfiqar, M., Rizvi, M., Munir, A., and McNeill, I. C.: Study of the thermal degradation of polychlorotrifluoroethylene, poly(vinylidene fluoride) and copolymers of chlorotrifluoroethylene and vinylidene fluoride, Polym. Degrad. Stabil., 43, 423–430, 1994.