Isotopic Abundances in the Atmosphere and Sources

  • C. M. Stevens
Part of the NATO ASI Series book series (volume 13)


The ultimate goal of isotopic studies of atmospheric CH4 is to contribute to the understanding of the atmospheric CH4 cycle by determining the relative fluxes from various categories of sources and the causes of the increasing concentration (Stevens and Engelkemeir, 1988; Quay et al.,1988; Wahlen et al., 1989). Because the large number of generic anthropogenic source types makes it impossible to determine their relative strengths based on carbon-13 data alone, Stevens and Engelkemeir (1988) and Craig et al. (1988) used the isotopic data to calculate the flux of the source with the greatest uncertainty, namely biomass burning, making use of the estimated fluxes for the other sources from emission inventories. This method determined the flux and isotopic composition of the natural sources from the concentration and isotopic composition of CH4 in old polar ice cores assuming the same lifetime as now. The lifetime was mostly determined by the fluxes based on the emissions inventories. This approach does not use the lifetime as a constraint nor contribute to the knowledge of the major sources, which have significant uncertainties in the estimates based on emissions inventories. A better approach is to start with the constraint of the lifetime value based on the methyl chloroform cycle (see Mayer et al., 1982; Khalil and Rasmussen, 1983; Prinn et al., 1987; Cicerone and Oremland, 1988). Then it is possible to calculate the fluxes of the two most isotopically different sources, providing an estimate based on emissions inventories for one of the anthropogenic sources is used as a constraint. A source is chosen that introduces the least error, namely landfills, which is one of the smallest and has an isotopic composition closest to the average.


Isotopic Composition Biomass Burning Carbon Isotopic Composition Natural Wetland Emission Inventory 
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  1. Bingemer, H.G., P.J. Crutzen. 1987. The production of methane from solid wastes. J. Geophys. Res., 92: 2181–2187.CrossRefGoogle Scholar
  2. Blake, D.R., F.S. Rowland. 1988. Continuing worldwide increase in tropospheric methane. Science, 239: 1129–1131.PubMedCrossRefGoogle Scholar
  3. Burke, R.A., W.M. Sackett. 1986. Stable hydrogen and carbon isotopic compositions of biogenic methane from several shallow aquatic environments. In: Organic Marine Geochemistry (M.L. Sohn, ed.,) American Chemical Society, Washington, D.C., p. 297.Google Scholar
  4. Cantrell, C.A., R.E. Shetter, A.H. McDaniel, J.G. Calvert, J.A. Davidson, D.C. Lowe, S.C. Tyler, R.J. Cicerone, J.P. Greenberg. 1990. Carbon kinetic isotope effect in the oxidation of methane by hydroxyl radicals. J. Geophys. Res., 95: 22455–22462.CrossRefGoogle Scholar
  5. Chanton, J.P., C.S. Martens. 1988. Seasonal variations in ebullitive flux and carbon isotopic composition of methane in a tidal freshwater estuary. Global Biogeochem. Cycles, 2: 289.CrossRefGoogle Scholar
  6. Chanton, J.P., G.G. Pauly, C.S. Martens, N.E. Blair. 1988. Carbon isotopic composition of methane in Florida Everglades soils and fractionation during its transport to the troposphere. Global Biogeochem. Cycles, 2: 245.CrossRefGoogle Scholar
  7. Cicerone, R.J., R.S. Oremland. 1988. Biogeochemical aspects of atmospheric methane. Global Biogeochemical Cycles, 2: 299–327.CrossRefGoogle Scholar
  8. Craig, H. 1953. The geochemistry of the stable carbon isotopes. Geochim. Cosmochim. Acta, 3: 53–92.CrossRefGoogle Scholar
  9. Craig, H., C.C. Chou. 1982. Methane: The record in polar ice cores. Geophys. Res. Lett., 9: 1212–1224.CrossRefGoogle Scholar
  10. Craig, H., C.C. Chou, C.M. Stevens, A. Engelkemeir. 1988. Isotopic composition of methane in polar ice cores. Science, 242: 1535–1539.PubMedCrossRefGoogle Scholar
  11. Crutzen, P.J., M.O. Andreae. 1990. Biomass burning in the tropics: Impact on atmospheric chemistry and biogeochemical cycles. Science, 250: 1, 669.CrossRefGoogle Scholar
  12. Crutzen, P.J., I. Aselmann, W. Seiler. 1986. Methane production by domestic animals, wild ruminants, other herbivorous fauna, and humans. Tellus, 38B: 271–284.Google Scholar
  13. Deines, P. 1980. The isotopic composition of reduced organic carbon. In: Handbook of Environmental Isotope Geochemistry, Vol. 1 (P. Fritz and J.C. Fontes, eds.), Elsevier Scientific, Chapter 9, p. 329–406.Google Scholar
  14. Friedli, H., H. Lotscher, H. Oeschger, U. Siegenthaler, B. Stauffer. 1986. Ice core record of the 13C/12C ratio of Atmospheric CO2 in the past two centuries. Nature, 324: 237.CrossRefGoogle Scholar
  15. Games, L.M., J.M. Hayes. 1976. On the mechanisms of CO2 and CH4 production in natural anaerobic environments. In: Proc. of the 2nd International Conference on Environmental Biogeochemistry, Vol. 1 ( J.O. Nriague, ed.), Butterworth, Stoneham, Mass., p 51.Google Scholar
  16. Gordon, S., W.A. Mulac. 1975. Reactions of the OH (X2II radical produced by the pulse radiolysis of water vapor. Int. J. Chem. Kinet., 7: 289.CrossRefGoogle Scholar
  17. Harriss, R.C. 1989. Historical trends in atmospheric methane concentration and the temperature sensitivity of methane outgassing from boreal and polar regions. In: Proceedings of a Joint Symposium by the Board on Atmospheric Sciences and Climate and the Committee on Global Change Commission on Physical Sciences, Mathematics and Resources. National Academic Press, Washington D.C., p. 79.Google Scholar
  18. Hitchcock, D.R., A.E. Wechsler. 1972. Biological cycling of atmospheric trace gases. Contr. Rep. NASA-CR 126663. Natl. Aeron. Space Adm., Washington D.C., p. 117.Google Scholar
  19. Holzapfel-Pschorn, A., W. Seiler. 1986. Methane during a cultivation period from an Italian rice paddy. J. Geophy. Res., 91: 1 1803.Google Scholar
  20. Hough, A., R.G. Derwent. 1990. Changes in the global concentration of tropospheric ozone due to human activities. Nature, 344:645.CrossRefGoogle Scholar
  21. Keeling, C.D., W.G. Mook, P.P. Tans. 1979. Recent trends in the 13C/12C ratio of atmospheric carbon dioxide. Nature, 277: 121.CrossRefGoogle Scholar
  22. Khalil, M.A.K., R.A. Rasmussen. 1983. Sources, sinks, and seasonal cycles of atmospheric methane. J. Geophys. Res., 88: 5131–5144.CrossRefGoogle Scholar
  23. Khalil, M.A.K., R.A. Rasmussen. 1990. Atmospheric methane: Recent global trends. Environ. Sci. Technol., 24: 549.CrossRefGoogle Scholar
  24. Khalil, M.A.K., R.A. Rasmussen. 1991. Methane emissions from rice fields in China. Environ. Sci. TechnoL, 25: 979.CrossRefGoogle Scholar
  25. Lachenbruch, A.H., B.V. Marshall. 1986. Changing climate: Geothermal evidence from permafrost in the Alaskan Arctic. Science, 234: 689.PubMedCrossRefGoogle Scholar
  26. Lassey, K.R., D.C. Lowe, C.A.M. Brenninkmeijer, A.J. Gomez. 1993. Atmospheric methane and its carbon isotopes in the southern hemisphere: Their time series and an instructive model. Chemosphere, 26 (1–4): 95–110.CrossRefGoogle Scholar
  27. Levin, I., P. Bergamaschi, H. Dörr, D. Trapp. 1993. Stable isotopic signature of methane from different sources in western Europe. Chemosphere, 26 (1–4): 161–178.CrossRefGoogle Scholar
  28. Logan, J.A. 1985. Tropospheric ozone: Seasonal behavior, trends and anthropogenic influence. J. Geophys. Res., 90: 10463.CrossRefGoogle Scholar
  29. Lowe, D.C., C.A.M. Brenninkmeijer, S.C. Tyler, E.J. Dlugokencky. 1991. Determination of the isotopic composition of atmospheric methane and its application in the antarctic. J. Geophys. Res., 96: 15455–15467.CrossRefGoogle Scholar
  30. Matthews, E., I. Fung. 1987. Methane emissions from natural wetlands: Global distribution area, and environmental characteristics of sources. Global Biogeochem. Cycles, 1: 61.CrossRefGoogle Scholar
  31. Mayer, E.W., D.R. Blake, S.C. Tyler, Y. Makide, D.C. Montague, F.S. Rowland. 1982. Methane: interhemispheric concentration gradient and atmospheric residence time. Proc,. Natl. Acad. Sci., 79: 1366–1370.CrossRefGoogle Scholar
  32. Oona, S., E.S. Deevey. 1960. Carbon 13 in lake waters and its possible bearing on paleolimnology. Am. J. Sci., 258A: 253.Google Scholar
  33. Ovsyannikov, V.M., V.S. Lebedev. 1967. Isotopic composition of carbon in gases of biogenic origin. Geochem. Int., 4: 453.Google Scholar
  34. Prinn, R., D. Cunnold, R.A. Rasmussen, P. Simmonds, F. Alyea, A. Crawford, P. Fraser, R. Rosen. 1987. Atmospheric trends in methylchioroform and the global average for the hydroxyl radical. Science, 238: 945.PubMedCrossRefGoogle Scholar
  35. Quay, P., S.L. King, J.M. Lansdown, D.O. Wilbur. 1988. Isotopic composition of methane released from wetlands: Implications for the increase in atmospheric methane. Global Biogeochem. Cycles, 2: 385.CrossRefGoogle Scholar
  36. Quay, P., S.L. King, J. Stutsman, D.O. Wilbur, L.P. Steele, I. Fung, R.H. Gammon, T.A. Brown, G.W. Farwell, P.M. Grootes, F.H. Schmidt. 1991. Carbon isotopic composition of atmospheric CH4: fossil and biomass burning source strengths. Global Biogeochem. Cycles, 5: 25.CrossRefGoogle Scholar
  37. Rice, D.D., G.E. Claypool. 1981. Generation, accumulation and resource potential of biogenic gas. Bull. Am. Assoc. Pet. Geol., 65: 5.Google Scholar
  38. Rust, F.E. 1981. Ruminant methane 5(13C/12C) values: Relationship to atmospheric methane. Science, 211: 1044–1046.PubMedCrossRefGoogle Scholar
  39. Schoell, M. 1980. The hydrogen and carbon isotopic composition of methane from natural gases of various origins. Geochem. Cosmochim. Acta, 44: 649.CrossRefGoogle Scholar
  40. Schütz, H., A. Holzapfel-Pschorn, R. Conrad, H. Rennenberg, W. Seiler. 1989. A 3-year continuous record on the influence of daytime, season, and fertilizer treatment om methane emission rates from an Italian rice paddy. J. Geophys. Res., 94: 16405.CrossRefGoogle Scholar
  41. Stevens, C. 1988. Atmospheric methane. Chem. Geol., 71: 11.CrossRefGoogle Scholar
  42. Stevens, C., A. Engelkemeir. 1988. Stable carbon isotopic composition of methane from some natural and anthropogenic sources. J. Geophys Res., 93: 725.CrossRefGoogle Scholar
  43. Stevens, C., A. Engelkemeir, R. Rasmussen. 1985. Causes of increasing methane fluxes based on carbon isotope studies. In: Special Environmental Report No. 16 (WMO-No.647); Lectures presented at the WMO Technical Conference on Observations and Measurement of Atmospheric Contaminants. World Meterol. Org., Geneva, Switzerland, p. 237.Google Scholar
  44. Tyler, S.C. 1986. Stable carbon isotope ratios in atmospheric methane and some of its sources. J. Geophys. Res., 91: 13232.CrossRefGoogle Scholar
  45. Tyler, S.C., P R Zimmerman, C. Cumberbatch, J. Greenberg, C. Westberg, J.P.E.C. Darlington. 1988. Measurements and interpretation of 813C of methane from termites, rice paddies, and wetlands in Kenya. Global Biogeochem. Cycles, 2: 341.CrossRefGoogle Scholar
  46. United Nations Statistical Yearbook. 1988.Google Scholar
  47. Wahlen, M., N. Tanaka, R. Henry, B. Deck, Zeglan, J.S. Vogel, J. Southon, A. Shemesh, R. Fairbanks, W. Broecker. 1989. Carbon-14 in methane sources and in atmospheric methane: The contribution from fossil carbon. Science, 245: 286.PubMedCrossRefGoogle Scholar
  48. Wahlen, M., N. Tanaka, B. Deck, R. Henry. 1990. 8D in CH4: Additional constraints for a global budget. EOS, 71 (43): 1249.Google Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 1993

Authors and Affiliations

  • C. M. Stevens
    • 1
  1. 1.Chemical Technology DivisionArgonne National LaboratoryArgonneUSA

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