References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-7-295-2007

Evidence for a CO increase in the SH during the 20th century based on firn air samples from Berkner Island, Antarctica

Assonov

S. S.

¹ Brenninkmeijer

C. A. M.

¹ Jöckel

¹ Mulvaney

² Bernard

³ Chappellaz

Max Planck Institute for Chemistry, PO 3060, 55020 Mainz, Germany

British Antarctic Survey, High Cross, Madingley Road, Cambridge CB3 0ET, UK

Laboratoire de Glaciologie et Géophysique de l'Environnement, 54 rue Molière, Domaine Universitaire, BP 96, 38402 St. Martin d'Hères Cedex, France

19 01 2007

7 2 295 308

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Trends of carbon monoxide (CO) for the past 100 years are reported as derived from Antarctic firn drilling expeditions. Only one of 3 campaigns provided high quality results. The trend was reconstructed using a firn air model in the forward mode to constrain age distributions and assuming the CO increase to be proportional to its major source, namely CH4. The results suggest that CO has increased by ~38%, from 38±7 to 52.5±1.5 ppbv over a period of roughly 100 years. The concentrations are on the volumetric scale which corresponds to ~1.08 of the scale used by NOAA/CMDL. The estimated CO increase is somewhat larger than what is estimated from the CO budget estimations and the CH4 growth alone. The most likely explanation might be an increase in biomass burning emissions. Using CH3Cl as another proxy produces a very similar reconstruction.

References 1

Albert, M. R., Effects of snow and firn ventilation on sublimation rates. Ann. Glaciol., 35, 52–56, 2002.

Andreae, M. O. and Merlet, P., Emission of trace gases and aerosols from biomass burning, Global Biogeochem. Cyc. 15, 955–966, 2001.

Assonov, S. S., Brenninkmeijer, C. A. M., and Jöckel, P.: The $^18$O isotope exchange rate between firn air CO2 and the firn matrix at three Antarctic sites, J. Geophys. Res.-Atmos., 110, D18310 doi:10.1029/2005JD005769, 2005.

Aydin, M., Saltzman, E. S., De Bruyn, W. J., Montzka, S. A. B., Butler, J. H., and Battle, M.: Atmospheric variability of methyl chloride during the last 300 years from an Antarctic ice core and firn air, Geophys. Res. Lett., 21, L02109, doi:10.1029/2003GL018750, 2004.

Bergamaschi, P., Hein, R., Heimann, M., and Crutzen, P. J.: Inverse modeling of the global CO cycle 1, Inversion of CO mixing ratios, J. Geophys. Res.-Atmos., 105, 1909–1927, 2000.

Bräunlich, M., Aballain, O., Marik, Th., et al.: 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.-Atmos., 106, 20 465–20 481, 2001.

Brenninkmeijer, C. A. M.: Measurement of the abundance of $^14$CO in the atmosphere and the $^13$C/$^12$C and $^18$O/$^16$O ratio of atmospheric CO with applications in New-Zealand and Antarctica, J. Geophys. Res.-Atmos., 98, 10 595–10 614, 1993.

Brenninkmeijer, C. A. M., Manning, M. R., Lowe, D. C., Wallace, G., Sparks, R. J., and Volz-Thomas, A.: Interhemispheric \mboxasymmetry in OH abundance inferred from measurements of atmospheric $^14$CO, Nature, 356, 50–52, 1992.

Brenninkmeijer, C. A. M., Koeppel, C., Röckmann, T., Scharffe, D. S., Bräunlich, M., and Gros, V.: Absolute measurement of the abundance of atmospheric carbon monoxide. J. Geophys. Res.-Atmos., 106, 10 003–10 010, 2001.

Brunke, E. G., Scheel, H. E., and Seiler, W.: Trends of Tropospheric CO, N2O and CH4 as observed at Cape Point, South-Africa, Atmos. Environ. Part A - Gen., 24, 585–595, 1990.

Butler, J. H., Battle, M., Bender, M. L., et al.: A record of atmospheric halocarbons during the twentieth century from polar firn air, Nature, 399, 749–755, 1999.

Butler, T. M., Rayner, P. J., Simmonds, I., and Lawrence, M. G.: Simultaneous mass balance inverse modeling of methane and carbon monoxide, Geophys. Res.-Atmos., 110, D21310, doi:10.1029/2005JD006071, 2005.

Cainey, J. M., Derek, N., and Krummel, P. B.: Baseline Atmospheric Program (Australia) 2001–2002, Melbourne, 2004.

Craig, H., Chou, C. C., Welhan, J. A., Stevens, C. M., and Engelkemeir, A.: The isotopic composition of methane in polar ice cores, Science, 242, 1535–1539, 1988.

Etheridge, D. M., Steele, L. P., Francey, R. J., and Langenfelds, R. L.: Atmospheric methane between 1000 AD and present: Evidence of anthropogenic emissions and climatic variability, J. Geophys. Res.-Atmos., 103, 15 979–15 993, 1998.

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.

Ferretti, D. F., Miller, J. B., White, J. W. C., et al.: Unexpected changes to the global methane budget over the past 2000 years, Science, 309, 1714–1717, 2005.

Haan, D. and Raynaud, D.: Ice core record of CO variations during the last two millennia: atmospheric implications and chemical interactions within the Greenland ice, Tellus Ser. B, 50, 253–262, 1998.

Haan, D., Zuo, Y., Gros, V., and Brenninkmeijer, C. A. M.: Photochemical production of carbon monoxide in snow, J. Atmos. Chem., 40, 217–230, 2001.

Hutterli, M. A., Bales, R. C., Mcconnell, J. R., and Stewart, R. W.: HCHO in Antarctic snow: Preservation in ice cores and air-snow exchange, Geophys. Res. Lett., 29, 1235, doi:10.1029/2001GL014256, 2002.

Hutterli, M. A., Mcconnell, J. R., Chen, G., Bales, R. C., Davis, D. D., and Lenschow, D. H.: Formaldehyde and hydrogen peroxide in air, snow and interstitial air at South Pole. Atmos. Environ., 38, 5439–5450, 2004.

Kaspers, K. A., van de Wal, R. S. W., de Gouw, J. A., et al.: Seasonal cycles of nonmethane hydrocarbons and methyl chloride, as derived from firn air from Dronning Maud Land, Antarctica. J. Geophys. Res.-Atmos., 109, D02307, doi:10.1029/2003JD003950, 2004.

Khalil, M. A. K. and Rasmussen, R. A.: Carbon-Monoxide in the Earths Atmosphere–Indications of a Global Increase, Nature, 332, 242–245, 1988.

Mak, J. E. and Brenninkmeijer, C. A. M.: Compressed-air sample technology for isotopic analysis of atmospheric carbon-monoxide, J. Atmos. Oceanic Technol., 11, 425–431, 1994.

Manning, M. R., Brenninkmeijer, C. A. M., and Allan, W.: Atmospheric carbon monoxide budget of the southern hemisphere: Implications of $^13$C/$^12$C measurements, J. Geophys. Res.-Atmos., 102, 10 673–10 682, 1997.

Manning, M. R., Lowe, D. C., Moss, R. C., Bodeker, G. E. and Allan, W.: Short term variations in the oxidising power of the atmosphere, Nature, 436 (7053), 1001–1004, 2005.

Mulvaney, R. Oerter, H., Peel, D. A., et al.: 1000 year ice-core records from Berkner Island, Antarctica, Ann. Glaciol., 35, 45–51, 2002.

Neumann, T. A. and Waddington, E. D.: Effects of firn ventilation on isotopic exchange, J. Glaciology, 50, 183–194, 2004.

Novelli, P. C.: CO in the atmosphere: measurement techniques and related issues, Chemosphere - Global Change Science, 1, 115–126, 1999.

Novelli, P. C., Connors, V. S., Reichle, H. G., et al.: An internally consistent set of globally distributed atmospheric carbon monoxide mixing ratios developed using results from an intercomparison of measurements, J. Geophys. Res.-Atmos., 103, 19 285–19 293, 1998a.

Novelli, P. C., Masarie, K. A. and Lang, P. M.: Distributions and recent changes of carbon monoxide in the lower troposphere, J. Geophys. Res.-Atmos., 103, 19 015–19 033, 1998b.

Novelli, P. C., Masarie, K. A., Lang, P. M., Hall, B. D., Myers, R. C., and Elkins, J. W.: Reanalysis of tropospheric CO trends: Effects of the 1997–1998 wildfires, J. Geophys. Res.-Atmos., 108, 4464, doi:10.1029/2002JD003031, 2003.

Perrier, S., Houdier, S., Domine, F., et al.: Formaldehyde in Arctic snow. Incorporation into ice particles and evolution in the snowpack, Atmos. Environ., 36, 2695–2705, 2002.

Röckmann, T. Brenninkmeijer, C. A. M., Saueressig, G., et al.: Mass-independent oxygen isotope fractionation in atmospheric CO as a result of the reaction CO+OH, Science, 281, 544–546, 1998.

Röckmann, T., Kaiser, J., and Brenninkmeijer, C. A. M.: The isotopic fingerprint of the pre-industrial and the anthropogenic N2O source, Atmos. Chem. Phys. 3, 315–323, 2003.

Rommelaere, V., Arnaud, L., and Barnola, J. M.: Reconstructing recent atmospheric trace gas concentrations from polar firn and bubbly ice data by inverse methods, J. Geophys. Res.-Atmos., 102, 30 069–30 083, 1997.

Schwander, J.: The transformation of snow to ice and the occlusion of gases, in The Environmental Record in Glaciers and Ice Sheets, edited by: Oeschger, H. and Langway Jr., C. C., pp. 53–67, John Wiley, New York, 1989.

Severinghaus, J. P., Grachev, A., and Battle, M: Thermal fractionation of air in polar firn by seasonal temperature gradients, Geochem. Geophys. Geosyst., 2, art. no. 2000GC000146, 2001.

Sowers, T., Bernard, S., Aballain, O., Chappellaz, J., Barnola, J.-M., and Marik, T.: Records of the $\delta ^13$C of atmospheric CH4 over the last 2 centuries as recorded in Antarctic snow and ice, Global Biogeochem. Cyc., 19, GB2002, doi:10.1029/2004GB002408, 2005.

Sturges, W. T., McIntyre, H. P., Penkett, S. A., et al.: Methyl bromide, other brominated methanes, and methyl iodide in polar firn air, J. Geophys. Res.-Atmos., 106, 1595–1606, 2001a.

Sturges, W. T., Penkett, S. A., Barnola, J. M., Chappellaz, J., Atlas, E. and Stroud, V.: A long-term record of carbonyl sulfide (COS) in two hemispheres from firn air measurements, Geophys. Res. Lett., 28, 4095–4098, 2001b.

Sumner, A. L., Shepson, P. B., Grannas, A. M., et al.: Atmospheric chemistry of formaldehyde in the Arctic troposphere at Polar Sunrise, and the influence of the snowpack. Atmos. Environ., 36, 2553–2562, 2002.

Trudinger, C. M., Etheridge, D. M., Rayner, P. J., Enting, I. G., Sturrock, G. A., and Langenfelds, R. L.: Reconstructing atmospheric histories from measurements of air composition in firn, J. Geophys. Res.-Atmos., 107, doi:10.1029/2002JD002545, 2002.

Trudinger, C. M., Etheridge, D. M., Sturrock, G. A., Fraser, P. J., Krummel, P. B., and Mcculloch, A.: Atmospheric histories of halocarbons from analysis of Antarctic firn air: Methyl bromide, methyl chloride, chloroform, and dichloromethane, J. Geophys. Res.-Atmos., 109, D22310 doi:10.1029/2004JD004932, 2004.

Volz, A., Ehhalt, D. H., and Derwent, R. G.: Seasonal and latitudinal variation of $^14$CO and tropospheric concentration of OH radicals, J. Geophys. Res.-Oceans and Atmos., 86, 5163–5171, 1981.

Weiler, K., Schwander J., Leuenberger, M., et al.: Geophys. Res. Abstracts, presentation on EGU-2005, 7, 03632, 2005.