Probing stratospheric transport and chemistry with new balloon and aircraft observations of the meridional and vertical N2O isotope distribution

• Published in: Atmospheric Chemistry and Physics
• Main Authors: Kaiser, Jan, Engel, Andreas, Borchers, Reinhard, Röckmann, Thomas
• Format: Article in Journal/Newspaper
• Language: English
• Published: 2006
• Subjects: ddc:550; Kiruna; North Pole
• Online Access: http://publikationen.ub.uni-frankfurt.de/frontdoor/index/index/docId/1670; https://nbn-resolving.org/urn:nbn:de:hebis:30-37462; https://doi.org/10.5194/acp-6-3535-2006; http://publikationen.ub.uni-frankfurt.de/files/1670/acp-6-3535-2006.pdf

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. 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 (3-D) models for further data interpretation. In general, the magnitude of the apparent fractionation constants (i.e., apparent isotope effects) increases continuously with altitude and decreases from the equator to the North Pole. Only the latter observation can be understood qualitatively by the interplay between the time-scales of N2O photochemistry and transport in a Rayleigh fractionation framework. Deviations from Rayleigh fractionation behavior also occur where polar vortex air mixes with nearly N2O-free upper stratospheric/mesospheric air (e.g., during the boreal winters 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 two-end-member mixing, but could be explained by continuous weak mixing between ...