Atmos. Chem. Phys. Discuss., 6, 4273-4324, 2006
www.atmos-chem-phys-discuss.net/6/4273/2006/
doi:10.5194/acpd-6-4273-2006
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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.
Probing stratospheric transport and chemistry with new balloon and aircraft observations of the meridional and vertical N2O isotope distribution
J. Kaiser1,*, A. Engel2, R. Borchers3, and T. Röckmann1,**
1Atmospheric Physics Division, Max Planck Institute for Nuclear Physics, Heidelberg, Germany
2Institute for Atmosphere and Environment, J. W. Goethe University, Frankfurt, Germany
3Planets and Comets Department, Max Planck Institute for Solar System Research, Katlenburg-Lindau, Germany
*now at: School of Environmental Sciences, University of East Anglia, Norwich, UK
**now at: Institute for Marine and Atmospheric Research Utrecht, Utrecht University, The Netherlands

Abstract. A comprehensive set of stratospheric balloon and aircraft samples was analyzed for the position-dependent isotopic composition of nitrous oxide (N2O). Results for a total of 220 samples from between 1987 and 2003 are presented, nearly tripling the number of mass-spectrometric N2O isotope measurements in the stratosphere published to date. Cryogenic balloon samples were obtained at polar (Kiruna/Sweden, 68° N), mid-latitude (southern France, 44° N) and tropical sites (Hyderabad/India, 18° N). Aircraft samples were collected with a newly-developed whole air sampler on board of the high-altitude aircraft M55 Geophysica during the EUPLEX 2003 campaign. All samples were analyzed by laboratory mass spectrometry for their 18O/16O and position-dependent 15N/14N isotope ratios with very high precision (standard deviation about 0.15 per mil for 18O/16O and average 15N/14N ratios, about 0.5 per mil for 15NNO/14NNO and N15NO/N14NO ratios). For mixing ratios above 200 nmol mol−1, relative isotope enrichments (δ values) and mixing ratios display a compact relationship, which is nearly independent of latitude and season and which can be explained equally well by Rayleigh fractionation or mixing. However, for mixing ratios below 200 nmol mol−1 this compact relationship gives way to meridional, seasonal and interannual variations. A comparison to a previously published mid-latitude balloon profile even shows large zonal variations, justifying the use of three-dimensional models for further data interpretation.

In general, the magnitude of the apparent fractionation constants (apparent isotope effects) increases continuously with altitude and decreases from the equator to the North pole, which can be qualitatively understood by the interplay between the time-scales of N2O photochemistry and transport. Deviations from this behavior occur where polar vortex air mixes with nearly N2O-free upper stratospheric/mesospheric air (e.g., during the boreal winter of 2003 and possibly 1992). Aircraft observations in the polar vortex at mixing ratios below 200 nmol mol−1 deviate from isotope variations expected for both Rayleigh fractionation and end-member mixing, but could be explained by continuous weak mixing between intravortex and extravortex air (Plumb et al., 2000). Finally, correlations between 18O/16O and average 15N/14N isotope ratios or between the position-dependent 15N/14N isotope ratios show that photo-oxidation makes a large contribution to the total N2O sink in the lower stratosphere (up to 100%). Towards higher altitudes, the temperature dependence of these isotope correlations becomes visible in the stratospheric observations.


Citation: 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 N2O isotope distribution, Atmos. Chem. Phys. Discuss., 6, 4273-4324, doi:10.5194/acpd-6-4273-2006, 2006.
 
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