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<article xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink" article-type="research-article" dtd-version="3.0" xml:lang="en">
<front>
<journal-meta>
<journal-id journal-id-type="publisher">ACPD</journal-id>
<journal-title-group>
<journal-title>Atmospheric Chemistry and Physics Discussions</journal-title>
<abbrev-journal-title abbrev-type="publisher">ACPD</abbrev-journal-title>
</journal-title-group>
<issn pub-type="epub">1680-7375</issn>
<publisher><publisher-name>Copernicus GmbH</publisher-name>
<publisher-loc>Göttingen, Germany</publisher-loc>
</publisher>
</journal-meta>
<article-meta>
<article-id pub-id-type="doi">10.5194/acpd-6-4273-2006</article-id>
<title-group>
<article-title>Probing stratospheric transport and chemistry with new balloon and aircraft observations of the meridional and vertical N&lt;sub&gt;2&lt;/sub&gt;O isotope distribution</article-title>
</title-group>
<contrib-group><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Kaiser</surname>
<given-names>J.</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<xref ref-type="aff" rid="aff4">
<sup>4</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Engel</surname>
<given-names>A.</given-names>
</name>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Borchers</surname>
<given-names>R.</given-names>
</name>
<xref ref-type="aff" rid="aff3">
<sup>3</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Röckmann</surname>
<given-names>T.</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<xref ref-type="aff" rid="aff5">
<sup>5</sup>
</xref>
</contrib>
</contrib-group><aff id="aff1">
<label>1</label>
<addr-line>Atmospheric Physics Division, Max Planck Institute for Nuclear Physics, Heidelberg, Germany</addr-line>
</aff>
<aff id="aff2">
<label>2</label>
<addr-line>Institute for Atmosphere and Environment, J. W. Goethe University, Frankfurt, Germany</addr-line>
</aff>
<aff id="aff3">
<label>3</label>
<addr-line>Planets and Comets Department, Max Planck Institute for Solar System Research, Katlenburg-Lindau, Germany</addr-line>
</aff>
<aff id="aff4">
<label>4</label>
<addr-line>now at: School of Environmental Sciences, University of East Anglia, Norwich, UK</addr-line>
</aff>
<aff id="aff5">
<label>5</label>
<addr-line>now at: Institute for Marine and Atmospheric Research Utrecht, Utrecht University, The Netherlands</addr-line>
</aff>
<pub-date pub-type="epub">
<day>29</day>
<month>05</month>
<year>2006</year>
</pub-date>
<volume>6</volume>
<issue>3</issue>
<fpage>4273</fpage>
<lpage>4324</lpage>
<permissions>
<license xlink:type="simple">
<license-p>This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.</license-p>
</license>
</permissions>
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<self-uri xlink:href="http://www.atmos-chem-phys-discuss.net/6/4273/2006/acpd-6-4273-2006.pdf">The full text article is available as a PDF file from http://www.atmos-chem-phys-discuss.net/6/4273/2006/acpd-6-4273-2006.pdf</self-uri>
<abstract>
<p>A comprehensive set of stratospheric balloon and aircraft samples was
analyzed for the position-dependent isotopic composition of nitrous oxide
(N&lt;sub&gt;2&lt;/sub&gt;O). Results for a total of 220 samples from between 1987 and 2003
are presented, nearly tripling the number of mass-spectrometric N&lt;sub&gt;2&lt;/sub&gt;O
isotope measurements in the stratosphere published to date. Cryogenic
balloon samples were obtained at polar (Kiruna/Sweden, 68&amp;deg; N),
mid-latitude (southern France, 44&amp;deg; N) and tropical sites
(Hyderabad/India, 18&amp;deg; 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 &lt;sup&gt;18&lt;/sup&gt;O/&lt;sup&gt;16&lt;/sup&gt;O and
position-dependent &lt;sup&gt;15&lt;/sup&gt;N/&lt;sup&gt;14&lt;/sup&gt;N isotope ratios with very high precision
(standard deviation about 0.15 per mil for &lt;sup&gt;18&lt;/sup&gt;O/&lt;sup&gt;16&lt;/sup&gt;O and average
&lt;sup&gt;15&lt;/sup&gt;N/&lt;sup&gt;14&lt;/sup&gt;N ratios, about 0.5 per mil for &lt;sup&gt;15&lt;/sup&gt;NNO/&lt;sup&gt;14&lt;/sup&gt;NNO and
N&lt;sup&gt;15&lt;/sup&gt;NO/N&lt;sup&gt;14&lt;/sup&gt;NO ratios). For mixing ratios above 200 nmol mol&lt;sup&gt;&amp;minus;1&lt;/sup&gt;,
relative isotope enrichments (&amp;delta; 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&lt;sup&gt;&amp;minus;1&lt;/sup&gt; 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.
&lt;br&gt;&lt;br&gt;
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 N&lt;sub&gt;2&lt;/sub&gt;O photochemistry and transport. Deviations
from this behavior occur where polar vortex air mixes with nearly
N&lt;sub&gt;2&lt;/sub&gt;O-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&lt;sup&gt;&amp;minus;1&lt;/sup&gt; 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 &lt;sup&gt;18&lt;/sup&gt;O/&lt;sup&gt;16&lt;/sup&gt;O and average &lt;sup&gt;15&lt;/sup&gt;N/&lt;sup&gt;14&lt;/sup&gt;N isotope ratios or
between the position-dependent &lt;sup&gt;15&lt;/sup&gt;N/&lt;sup&gt;14&lt;/sup&gt;N isotope ratios show that
photo-oxidation makes a large contribution to the total N&lt;sub&gt;2&lt;/sub&gt;O sink in the
lower stratosphere (up to 100%). Towards higher altitudes, the
temperature dependence of these isotope correlations becomes visible in the
stratospheric observations.</p>
</abstract>
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