ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-12-4081-2012 Distributions, long term trends and emissions of four perfluorocarbons in remote parts of the atmosphere and firn air Laube J. C. 1 Hogan C. 1 Newland M. J. 1 Mani F. S. 1 2 Fraser P. J. 3 Brenninkmeijer C. A. M. 4 Martinerie P. 5 Oram D. E. 6 Röckmann T. 7 Schwander J. 8 Witrant E. 9 Mills G. P. 1 Reeves C. E. 1 Sturges W. T. 1 School of Environmental Sciences, University of East Anglia, Norwich, UK School of Applied Sciences, Fiji National University, Suva, Fiji Centre for Australian Weather and Climate Research, Commonwealth Scientific and Industrial Research Organisation, Aspendale, Victoria 3195, Australia Max Planck Institute for Chemistry, Air Chemistry Division, Mainz, Germany UJF – Grenoble 1/CNRS, Laboratoire de Glaciologie et Géophysique de l'Environnement (LGGE) UMR5183, Grenoble, 38041, France National Centre for Atmospheric Science, School of Environmental Sciences, University of East Anglia, Norwich, UK Institute for Marine and Atmospheric Research, Utrecht University, Utrecht, The Netherlands Physics Institute, University of Berne, Bern, Switzerland UJF – Grenoble1/CNRS, Grenoble Image Parole Signal Automatique (GIPSA-lab), UMR5216, B.P. 46, 38402 St. Martin d'Hères, France 08 05 2012 12 9 4081 4090 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/12/4081/2012/acp-12-4081-2012.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/12/4081/2012/acp-12-4081-2012.pdf

We report the first data set of atmospheric abundances for the following four perfluoroalkanes: n-decafluorobutane (n-C<sub>4</sub>F<sub>10</sub>), n-dodecafluoropentane (n-C<sub>5</sub>F<sub>12</sub>), n-tetradecafluorohexane (n-C<sub>6</sub>F<sub>14</sub>) and n-hexadecafluoroheptane (n-C<sub>7</sub>F<sub>16</sub>). All four compounds could be detected and quantified in air samples from remote locations in the Southern Hemisphere (at Cape Grim, Tasmania, archived samples dating back to 1978) and the upper troposphere (a passenger aircraft flying from Germany to South Africa). Further observations originate from air samples extracted from deep firn in Greenland and allow trends of atmospheric abundances in the earlier 20th century to be inferred. All four compounds were not present in the atmosphere prior to the 1960s. n-C<sub>4</sub>F<sub>10</sub> and n-C<sub>5</sub>F<sub>12</sub> were also measured in samples collected in the stratosphere with the data indicating that they have no significant sinks in this region. Emissions were inferred from these observations and found to be comparable with emissions from the EDGAR database for n-C<sub>6</sub>F<sub>14</sub>. However, emissions of n-C<sub>4</sub>F<sub>10</sub>, n-C<sub>5</sub>F<sub>12</sub> and n-C<sub>7</sub>F<sub>16</sub> were found to differ by up to five orders of magnitude between our approach and the database. Although the abundances of the four perfluorocarbons reported here are currently small (less than 0.3 parts per trillion) they have strong Global Warming Potentials several thousand times higher than carbon dioxide (on a 100-yr time horizon) and continue to increase in the atmosphere. We estimate that the sum of their cumulative emissions reached 325 million metric tonnes CO<sub>2</sub> equivalent at the end of 2009.

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