Atmospheric Chemistry and Physics Discussions
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10.5194/acpd-10-7675-2010
http://www.atmos-chem-phys-discuss.net/10/7675/2010/
http://www.atmos-chem-phys-discuss.net/10/7675/2010/acpd-10-7675-2010.html
http://www.atmos-chem-phys-discuss.net/10/7675/2010/acpd-10-7675-2010.pdf
7675
7697
2010-03-24
Rapid growth of HFC-227ea (1,1,1,2,3,3,3-Heptafluoropropane) in the atmosphere
J. C. Laube
j.laube@uea.ac.uk
P. Martinerie
E. Witrant
T. Blunier
J. Schwander
C. A. M. Brenninkmeijer
T. J. Schuck
M. Bolder
T. Röckmann
C. van der Veen
H. Bönisch
A. Engel
G. P. Mills
M. J. Newland
D. E. Oram
C. E. Reeves
W. T. Sturges
School of Environmental Sciences, University of East Anglia, Norwich, UK
Laboratoire de Glaciologie et Géophysique de l'Environnement (LGGE), CNRS, Université Joseph Fourier-Grenoble, Grenoble, France
Grenoble Image Parole Signal Automatique (GIPSA-lab), Université Joseph Fourier/CNRS, Grenoble, France
Centre for Ice and Climate, University of Copenhagen, Copenhagen, Denmark
Physics Institute, University of Berne, Bern, Switzerland
Max Planck Institute for Chemistry, Air Chemistry Division, Mainz, Germany
Institute for Marine and Atmospheric Research, Utrecht University, Utrecht, The Netherlands
Institute for Atmosphere and Environment, University of Frankfurt, Frankfurt, Germany
We report the first measurements of 1,1,1,2,3,3,3-heptafluoropropane
(HFC-227ea), a substitute for ozone depleting compounds, in remote regions
of the atmosphere and present evidence for its rapid growth. Observed mixing
ratios ranged from below 0.01 ppt in deep firn air to 0.59 ppt in the
northern mid-latitudinal upper troposphere. Firn air samples collected in
Greenland were used to reconstruct a history of atmospheric abundance.
Year-on-year increases were deduced, with acceleration in the growth rate
from 0.026 ppt per year in 2000 to 0.057 ppt per year in 2007. Upper
tropospheric air samples provide evidence for a continuing growth until late
2009. Furthermore we calculated a stratospheric lifetime of 370 years from
measurements of air samples collected on board high altitude aircraft and
balloons. Emission estimates were determined from the reconstructed
atmospheric trend and suggest that current "bottom-up" estimates of global
emissions for 2005 are too high by more than a factor of three.
Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Rossi, M. J., Troe, J., and Wallington, T. J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume IV – gas phase reactions of organic halogen species, Atmos. Chem. Phys., 8, 4141–4496, 2008.
Bräunlich, M., Aballain, O., Marik, T., Jöckel, P., Brenninkmeijer, C. A. M., Chappellaz, J., Barnola, J.-M., Mulvaney, R., and Sturges, W. T.: Changes in the global atmospheric methane budget over the last decades inferred from $^13$C and D isotopic analysis of Antarctic firn air, J. Geophys. Res., 106(D17), 20465–20481, 2001.
Brenninkmeijer, C. A. M., Crutzen, P., Boumard, F., Dauer, T., Dix, B., Ebinghaus, R., Filippi, D., Fischer, H., Franke, H., Frie?, U., Heintzenberg, J., Helleis, F., Hermann, M., Kock, H. H., Koeppel, C., Lelieveld, J., Leuenberger, M., Martinsson, B. G., Miemczyk, S., Moret, H. P., Nguyen, H. N., Nyfeler, P., Oram, D., O'Sullivan, D., Penkett, S., Platt, U., Pupek, M., Ramonet, M., Randa, B., Reichelt, M., Rhee, T. S., Rohwer, J., Rosenfeld, K., Scharffe, D., Schlager, H., Schumann, U., Slemr, F., Sprung, D., Stock, P., Thaler, R., Valentino, F., van Velthoven, P., Waibel, A., Wandel, A., Waschitschek, K., Wiedensohler, A., Xueref-Remy, I., Zahn, A., Zech, U., and Ziereis, H.: Civil Aircraft for the regular investigation of the atmosphere based on an instrumented container: The new CARIBIC system, Atmos. Chem. Phys., 7, 4953–4976, 2007.
Butler, J. H., Battle, M., Bender, M. L., Montzka, S. A., Clarke, A. D., Saltzman, E. S., Sucher, C. M., Severinghaus, J. P., and Elkins, J. W.: A record of atmospheric halocarbons during the twentieth century from polar firn air, Nature, 399, 749-755, 1999.
Chen, N. H. and Othmer, D. F.: New generalized equation for gas diffusion coefficient, J. Chem. Engin. Data, 7, 37–41, 1962.
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, 2007.
Deger, H.: FCKW: Anwendungen, Probleme und Wege zu deren Lösung, Nachr. Chem. Tech. Lab., 40, 1124–1132, 1992.
EDGAR Project Team: European Commission, Joint Research Centre (JRC)/Netherlands Environmental Assessment Agency (PBL). Emission Database for Global Atmospheric Research (EDGAR), release version 4.0. http://edgar.jrc.ec.europa.eu, 2009.
Emmen, H. H., Hoogendijk, E. M., Klopping-Ketelaars, W. A., et al.: Human safety and pharmacokinetics of the CFC alternative propellants HFC 134a (1,1,1,2-tetrafluoroethane) and HFC 227 (1,1,1,2,3,3,3-heptafluoropropane) following whole-body exposure. Regul Toxicol. Pharmacol., 32, 22–35, 2000.
Engel A., Strunk, M., Müller, M., Haase, H.-P., Poss, C., Levin, I., and Schmidt, U.: Temporal development of total chlorine in the high-latitude stratosphere based on reference distributions of mean age derived from CO<sub>2</sub> and SF$_6$, J. Geophys. Res., 107(D12), 4136, doi:10.1029/2001JD000584, 2002.
Fabre, A., Barnola, J.-M., Arnaud, L., and Chappellaz, J.: Determination of gas diffusivity in polar firn: comparison between experimental measurements and inverse modeling, Geophys. Res. Lett., 27, 557–560, 2000.
Fraser, P. J., Oram, D. E., Reeves, C. E., Penkett, S. A., and Mc-Culloch, A.: Southern Hemispheric halon trends (1978–1998) and global halon emissions, J. Geophys. Res., 104(D13), 15985–15999, 1999.
Fuller, E. N., Schettler, P. D., and Giddings, J. C.: A new method for prediction of binary gas-phase diffusion coefficients, Ind. Eng. Chem., 58, 19–27, doi:10.1021//ie50677a007, 1966.
Geller, L. S., Elkins, J. W., Lobert, J. M., Clarke, A. D., Hurst, D. F. Butler, J. H., and Myers, R. C.: Tropospheric SF$_6$: Observed latitudinal distribution and trends, derived emissions and interhemispheric exchange time, Geophys. Res. Lett., 24, 675–678, 1997.
Hough, A. M.: The development of a two-dimensional global tropospheric model, 1, The model transport, Atmos. Environ., 23, 1235–1261, 1989.
Hynes, R. G., Mackie J. C., and Masri, A. R.: Inhibition of Premixed Hydrogen-Air Flames by 2-H Heptafluoropropane, Combust. Flame, 113, 554, 1998.
de Jager, D., Manning, M., Kuijpers, L., et al.: IPCC/TEAP Special Report on Safeguarding the Ozone Layer and the Global Climate System: Issues related to Hydrofluorocarbons and Perfluorocarbons, Cambridge University Press, Cambridge, 2005.
Kaiser, J., Engel, A., Borchers, R., and Röckmann, T.: Probing stratospheric transport and chemistry with new balloon and aircraft observations of the meridional and vertical N<sub>2</sub>O isotope distribution, Atmos. Chem. Phys., 6, 3535–3556, 2006.
Karecki, S., Pruette, L., Reif, R., Sparks, T., Beu, L., and Vartanian, V.: Use of novel hydrofluorocarbon and iodofluorocarbon chemistries for a high aspect ratio via etch in a high density plasma etch tool, J. Electrochem. Soc., 145(12), 4305–4312, 1998.
Laube, J. C., Engel, A., Bönisch, H., Möbius, T., Worton, D. R., Sturges, W. T., Grunow, K., and Schmidt, U.: Contribution of very short-lived organic substances to stratospheric chlorine and bromine in the tropics – a case study, Atmos. Chem. Phys., 8, 7325–7334, 2008.
Laube, J. C., Engel, A., Bönisch, H., Möbius, T., Sturges, W. T., Braß, M., and Röckmann, T.: Fractional release factors of long-lived halogenated organic compounds in the tropical stratosphere, Atmos. Chem. Phys., 10, 1093–1103, 2010.
MacFarling Meure, C., Etheridge, D., Trudinger, C., Steele, P., Langenfelds, R., van Ommen, T., Smith, A., and Elkins, J.: Law Dome CO<sub>2</sub>, CH<sub>4</sub> and N<sub>2</sub>O ice core records extended to 2000 years BP, Geophys. Res. Lett., 33, L14810, doi:10.1029/2006GL026152, 2006.
Martinerie, P., Nourtier-Mazauric, E., Barnola, J.-M., Sturges, W. T., Worton, D. R., Atlas, E., Gohar, L. K., Shine, K. P., and Brasseur, G. P.: Long-lived halocarbon trends and budgets from atmospheric chemistry modelling constrained with measurements in polar firn, Atmos. Chem. Phys., 9, 3911–3934, 2009.
Massman, W. J., A review of the molecular diffusivities of H<sub>2</sub>O, CO<sub>2</sub>, CH<sub>4</sub>, CO, O<sub>3</sub>, SO<sub>2</sub>, NH<sub>3</sub>, N<sub>2</sub>O, NO, and NO<sub>2</sub> in air, O<sub>2</sub> and N<sub>2</sub> near STP, Atmos. Environ., 32, 1111–1127, 1998.
Montzka, S. A., Butler, J. H., Elkins, J. W., Thompson, T. M., Clarke, A. D. and Lock, L. T.: Present and future trends in the atmospheric burden of ozone-depleting halogens, Nature, 398, 690–694, 1999.
Naik, V., Jain, A. K., Patten, K. O., and Wuebbles, D. J.: Consistent sets of atmospheric lifetimes and radiative forcings on climate for CFC replacements: HCFCs and HFCs, J. Geophys. Res., 105, 6903–6914, 2000.
Oram, D. E., Sturges, W. T., Penkett, S. A., McCulloch, A., and Fraser, P. J.: Growth of fluoroform (CHF<sub>3</sub>, HFC-23) in the background atmosphere, Geophys. Res. Lett., 25, 35–38, 1998.
Park, J.-Y., Lim, J. S., Lee B. G., and Lee, Y. W.: Phase equilibria of CFC alternative refrigerant mixtures: 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea)+difluoromethane (HFC-32), +1,1,1,2-tetrafluoroethane (HFC-134a), and +1,1-difluoroethane (HFC-152a), Int. J. Thermophys., 22, 901–917, 2001.
Prinn, R. G., Huang, J., Weiss, R. F., Cunnold, D. M., Fraser, P. J., Simmonds, P. G., McCulloch, A., Harth, C., Salameh, P., O'Doherty, S., Wang, R. H. J., Porter, L., and Miller, B. R.: Evidence for substantial variations of atmospheric hydroxyl radicals in the past two decades, Science, 292(5523), 1882–1888, 2001.
Prinn, R. G., Weiss, R. F., Fraser, P. J., Simmonds, P. G., Cunnold, D. M., Alyea, F. N., O'Doherty, S., Salameh, P., Miller, B. R., Huang, J., Wang, R. H. J., Hartley, D. E., Harth, C., Steele, L. P., Sturrock, G., Midgley, P. M., and McCulloch, A.: A History of Chemically and Radiatively Important Gases in Air deduced from ALE/GAGE/AGAGE, J. Geophys. Res., 105, 17751–17792, 2000.
Plumb, R. A. and Ko, M. K. W.: Interrelationships between mixing ratios of long-lived stratospheric constituents, J. Geophys. Res., 97, 10145–10156, 1992.
Reeves, C. E., Sturges, W. T., Sturrock, G. A., Preston, K., Oram, D. E., Schwander, J., Mulvaney, R., Barnola, J.-M., and Chappellaz, J.: Trends of halon gases in polar firn air: implications for their emission distributions, Atmos. Chem. Phys., 5, 2055–2064, 2005.
Rommelaere V., Arnaud, L., and Bamola, J. M.: Reconstructing recent atmospheric, trace gas concentrations from polar firn and bubbly ice data by inverse methods, J. Geophys. Res. 102(D25), 30069–30083, 1997.
Schwander, J., Barnola, J.-M., Andrie, C., Leuenberger, M., Ludin, A., Raynaud, D., and Stauffer, B.: The age of the air in the firn and ice at Summit, Greenland, J. Geophys. Res., 98, 2831–2838, 1993.
Stemmler, K., Folini, D., Ubl, S., Vollmer, M. K., Reimann, S., O'Doherty, S., Greally, B. R., Simmonds, P. G., and Manning, A. J.: European emissions of HFC-365mfc, a chlorine free substitute for the foam blowing agents HCFC-141b and CFC-11, Environ. Sci. Technol., 41, 1145–1151, 2007.
Sturrock, G. A., Etheridge, D. M., Trudinger, C. M., Fraser, P. J., and Smith, A. M.: Atmospheric histories of halocarbons from analysis of Antarctic firn air: Major Montreal Protocol species, J. Geophys. Res., 107, 4765, doi:10.1029/2002JD002548, 2002.
Volk, C.M., Elkins, J. W., Fahey, D. W., Sutton, G. S., Gilligan, J. M., Loewenstein, M., Podolske, J. R., Chan, K. R., and Gunson, M. R.: Evaluation of source gas lifetimes from stratospheric observations, J. Geophys. Res., 102(D21), 25543–25564, 1997.
Vollmer, M. K., Reimann, S., Folini, D., Porter, L. W., and Steele, L. P.: First appearance and rapid growth of anthropogenic HFC-245fa (CHF2CH2CF3) in the atmosphere, Geophys. Res. Lett., 33, L20806, doi:10.1029/2006GL026763, 2006.
Yquel, J.-P.: Aerosol device for dispensing a composition with relatively high viscosity, US Patent 5467902, 1995.
Zellner, R., Bednarek, G., Hoffmann, A., Kohlmann, J. P., Mörs, V., and Saathoff, H.: Rate and Mechanism of the Atmospheric Degradation of 2H-Heptafluoropropane (HFC-227), Ber. Bunsenges. Phys. Chem., 98, 141–146, 1994.