Atmos. Chem. Phys. Discuss., 8, 18993-19034, 2008
© Author(s) 2008. This work is distributed
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This discussion paper has been under review for the journal Atmospheric Chemistry and Physics (ACP). Please refer to the corresponding final paper in ACP.
Oxygen isotopic signature of CO2 from combustion processes
M. Schumacher1,2,3,*, R. E. M. Neubert1, H. A. J. Meijer1, H. G. Jansen1, W. A. Brand2, H. Geilmann2, and R. A. Werner3
1Centre for Isotope Research, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands
2Max-Planck-Institute for Biogeochemistry, Hans-Knoell-Straße 10, 07745 Jena, Germany
3Institute of Plant Sciences, Swiss Federal Institute of Technology Zürich, Universitätsstrasse 2, 8092 Zürich, Switzerland
*now at: Alfred Wegener Institute for Polar and Marine Research, AWIPEV Research Base, 9173 Ny-Ålesund, Svalbard, Norway

Abstract. For a comprehensive understanding of the global carbon cycle precise knowledge of all processes is necessary. Stable isotope (13C and 18O) abundances provide information for the qualification and the quantification of the diverse source and sink processes. This study focuses on the δ18O signature of CO2 from combustion processes, which are widely present both naturally (wild fires), and human induced (fossil fuel combustion, biomass burning) in the carbon cycle. All these combustion processes use atmospheric oxygen, of which the isotopic signature is assumed to be constant with time throughout the whole atmosphere. The combustion is generally presumed to take place at high temperatures, thus minimizing isotopic fractionation. Therefore it is generally supposed that the 18O signature of the produced CO2 is equal to that of the atmospheric oxygen. This study, however, reveals that the situation is much more complicated and that important fractionation effects do occur. From laboratory studies fractionation effects in the order of about 26‰ became obvious, a clear differentiation of about 7‰ was also found in car exhausts which were sampled directly under ambient atmospheric conditions.

We investigated a wide range of materials (both different raw materials and similar materials with different inherent 18O signature), sample geometries (e.g. texture and surface-volume ratios) and combustion circumstances. We found that the main factor influencing the specific isotopic signatures of the combustion-derived CO2 and of the concomitantly released oxygen-containing side products, is the case-specific rate of combustion. This points firmly into the direction of (diffusive) transport of oxygen to the reaction zone as the cause of the isotope fractionation. The original 18O signature of the material appeared to have little or no influence.

Citation: Schumacher, M., Neubert, R. E. M., Meijer, H. A. J., Jansen, H. G., Brand, W. A., Geilmann, H., and Werner, R. A.: Oxygen isotopic signature of CO2 from combustion processes, Atmos. Chem. Phys. Discuss., 8, 18993-19034, doi:10.5194/acpd-8-18993-2008, 2008.
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