Chlorine isotope composition in chlorofluorocarbons CFC-11, CFC-12 and CFC-113 in firn, stratospheric and tropospheric air

• Published in: Atmospheric Chemistry and Physics
• Main Authors: Allin, S. J., Laube, J. C., Witrant, Emmanuel, Kaiser, J., Mckenna, E., Dennis, P., Mulvaney, R., Capron, E., Martinerie, P., Röckmann, T., Blunier, T., Schwander, J., Fraser, P. J., Langenfelds, R. L., Sturges, W. T.
• Other Authors: School of Environmental Sciences Norwich, University of East Anglia Norwich (UEA), GIPSA - Systèmes linéaires et robustesse (GIPSA-SLR), Département Automatique (GIPSA-DA), Grenoble Images Parole Signal Automatique (GIPSA-lab), Université Pierre Mendès France - Grenoble 2 (UPMF)-Université Stendhal - Grenoble 3-Université Joseph Fourier - Grenoble 1 (UJF)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Pierre Mendès France - Grenoble 2 (UPMF)-Université Stendhal - Grenoble 3-Université Joseph Fourier - Grenoble 1 (UJF)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Grenoble Images Parole Signal Automatique (GIPSA-lab), Université Pierre Mendès France - Grenoble 2 (UPMF)-Université Stendhal - Grenoble 3-Université Joseph Fourier - Grenoble 1 (UJF)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Pierre Mendès France - Grenoble 2 (UPMF)-Université Stendhal - Grenoble 3-Université Joseph Fourier - Grenoble 1 (UJF)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS), British Antarctic Survey (BAS), Natural Environment Research Council (NERC), Laboratoire de glaciologie et géophysique de l'environnement (LGGE), Observatoire des Sciences de l'Univers de Grenoble (OSUG), Université Joseph Fourier - Grenoble 1 (UJF)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut national des sciences de l'Univers (INSU - CNRS)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Savoie Mont Blanc (USMB Université de Savoie Université de Chambéry )-Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut national des sciences de l'Univers (INSU - CNRS)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Savoie Mont Blanc (USMB Université de Savoie Université de Chambéry )-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institute for Marine and Atmospheric Research Utrecht (IMAU), Utrecht University Utrecht, Centre for Ice and Climate Copenhagen, Niels Bohr Institute Copenhagen (NBI), Faculty of Science Copenhagen, University of Copenhagen = Københavns Universitet (UCPH)-University of Copenhagen = Københavns Universitet (UCPH)-Faculty of Science Copenhagen, University of Copenhagen = Københavns Universitet (UCPH)-University of Copenhagen = Københavns Universitet (UCPH), University of Bern, Centre for Australian Weather and Climate Research (CAWCR)
• Format: Article in Journal/Newspaper
• Language: English
• Published: HAL CCSD 2015
• Subjects: [PHYS.PHYS.PHYS-AO-PH]Physics [physics]/Physics [physics]/Atmospheric and Oceanic Physics [physics.ao-ph]; [INFO.INFO-AU]Computer Science [cs]/Automatic Control Engineering; Fletcher Promontory; Greenland; Grim; Antarc*; Antarctica; North Greenland
• Online Access: https://hal.science/hal-01259074; https://hal.science/hal-01259074/document; https://hal.science/hal-01259074/file/acp-15-6867-2015.pdf; https://doi.org/10.5194/acp-15-6867-2015

International audience 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 ...