Journal cover Journal topic
Atmospheric Chemistry and Physics An interactive open-access journal of the European Geosciences Union
Atmos. Chem. Phys., 15, 6867-6877, 2015
© Author(s) 2015. This work is distributed under
the Creative Commons Attribution 3.0 License.
Research article
23 Jun 2015
Chlorine isotope composition in chlorofluorocarbons CFC-11, CFC-12 and CFC-113 in firn, stratospheric and tropospheric air
S. J. Allin1, J. C. Laube1, E. Witrant2, J. Kaiser1, E. McKenna1, P. Dennis1, R. Mulvaney3, E. Capron3, P. Martinerie4, T. Röckmann5, T. Blunier6, J. Schwander7, P. J. Fraser8, R. L. Langenfelds8, and W. T. Sturges1 1Centre for Ocean and Atmospheric Sciences, School of Environmental Sciences, University of East Anglia, Norwich, UK
2Grenoble Image Parole Signal Automatique, Université Joseph Fourier/CNRS, Grenoble, France
3British Antarctic Survey, Natural Environment Research Council, Cambridge, UK
4CNRS/Univ. Grenoble Alpes, 38041, Grenoble, France
5Institute for Marine and Atmospheric Research Utrecht, Utrecht University, Utrecht, the Netherlands
6Centre for Ice and Climate, University of Copenhagen, Copenhagen, Denmark
7Physics Institute, University of Bern, Bern, Switzerland
8Centre for Australian Weather and Climate Research, Oceans and Atmosphere Flagship, Commonwealth Scientific and Industrial Research Organisation, Aspendale, Australia
Abstract. The stratospheric degradation of chlorofluorocarbons (CFCs) releases chlorine, which is a major contributor to the destruction of stratospheric ozone (O3). A recent study reported strong chlorine isotope fractionation during the breakdown of the most abundant CFC (CFC-12, CCl2F2, Laube et al., 2010a), similar to effects seen in nitrous oxide (N2O). Using air archives to obtain a long-term record of chlorine isotope ratios in CFCs could help to identify and quantify their sources and sinks. We analyse the three most abundant CFCs and show that CFC-11 (CCl3F) and CFC-113 (CClF2CCl2F) exhibit significant stratospheric chlorine isotope fractionation, in common with CFC-12. The apparent isotope fractionation (ϵapp) for mid- and high-latitude stratospheric samples are respectively −2.4 (0.5) and −2.3 (0.4) ‰ for CFC-11, −12.2 (1.6) and −6.8 (0.8) ‰ for CFC-12 and −3.5 (1.5) and −3.3 (1.2) ‰ for CFC-113, where the number in parentheses is the numerical value of the standard uncertainty expressed in per mil. Assuming a constant isotope composition of emissions, we calculate the expected trends in the tropospheric isotope signature of these gases based on their stratospheric 37Cl enrichment and stratosphere–troposphere exchange. We compare these projections to the long-term δ (37Cl) trends of all three CFCs, measured on background tropospheric samples from the Cape Grim air archive (Tasmania, 1978–2010) and tropospheric firn air samples from Greenland (North Greenland Eemian Ice Drilling (NEEM) site) and Antarctica (Fletcher Promontory site). From 1970 to the present day, projected trends agree with tropospheric measurements, suggesting that within analytical uncertainties, a constant average emission isotope delta (δ) is a compatible scenario. The measurement uncertainty is too high to determine whether the average emission isotope δ has been affected by changes in CFC manufacturing processes or not. Our study increases the suite of trace gases amenable to direct isotope ratio measurements in small air volumes (approximately 200 mL), using a single-detector gas chromatography–mass spectrometry (GC–MS) system.

Citation: Allin, S. J., Laube, J. C., Witrant, E., Kaiser, J., McKenna, E., Dennis, P., Mulvaney, R., Capron, E., Martinerie, P., Röckmann, T., Blunier, T., Schwander, J., Fraser, P. J., Langenfelds, R. L., and Sturges, W. T.: Chlorine isotope composition in chlorofluorocarbons CFC-11, CFC-12 and CFC-113 in firn, stratospheric and tropospheric air, Atmos. Chem. Phys., 15, 6867-6877,, 2015.
Publications Copernicus
Short summary
Stratospheric ozone protects life on Earth from harmful UV-B radiation. Chlorofluorocarbons (CFCs) are man-made compounds which act to destroy this barrier. This paper presents (1) the first measurements of the stratospheric δ(37Cl) of CFCs -11 and -113; (2) the first quantification of long-term trends in the tropospheric δ(37Cl) of CFCs -11, -12 and -113. This study provides a better understanding of source and sink processes associated with these destructive compounds.
Stratospheric ozone protects life on Earth from harmful UV-B radiation. Chlorofluorocarbons...