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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">ACP</journal-id>
<journal-title-group>
<journal-title>Atmospheric Chemistry and Physics</journal-title>
<abbrev-journal-title abbrev-type="publisher">ACP</abbrev-journal-title>
</journal-title-group>
<issn pub-type="epub">1680-7324</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/acp-3-2015-2003</article-id>
<title-group>
<article-title>Heavy hydrogen in the stratosphere</article-title>
</title-group>
<contrib-group><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>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Rhee</surname>
<given-names>T. S.</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>Engel</surname>
<given-names>A.</given-names>
</name>
<xref ref-type="aff" rid="aff3">
<sup>3</sup>
</xref>
</contrib>
</contrib-group><aff id="aff1">
<label>1</label>
<addr-line>Max-Planck-Institut für Kernphysik, Bereich Atmosphärenphysik, Saupfercheckweg 1, 69117 Heidelberg, Germany</addr-line>
</aff>
<aff id="aff2">
<label>2</label>
<addr-line>Max-Planck-Institut für Chemie, Chemie der Atmosphäre, Becherweg 27, 55122 Mainz, Germany</addr-line>
</aff>
<aff id="aff3">
<label>3</label>
<addr-line>Institut für Meteorologie und Geophysik, Universität Frankfurt, Georg Voigt Str. 14, 60325 Frankfurt, Germany</addr-line>
</aff>
<pub-date pub-type="epub">
<day>19</day>
<month>11</month>
<year>2003</year>
</pub-date>
<volume>3</volume>
<issue>6</issue>
<fpage>2015</fpage>
<lpage>2023</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>
<self-uri xlink:href="http://www.atmos-chem-phys.net/3/2015/2003/acp-3-2015-2003.html">This article is available from http://www.atmos-chem-phys.net/3/2015/2003/acp-3-2015-2003.html</self-uri>
<self-uri xlink:href="http://www.atmos-chem-phys.net/3/2015/2003/acp-3-2015-2003.pdf">The full text article is available as a PDF file from http://www.atmos-chem-phys.net/3/2015/2003/acp-3-2015-2003.pdf</self-uri>
<abstract>
<p>We report measurements of the deuterium content of molecular hydrogen
      (H&lt;sub&gt;2&lt;/sub&gt;) obtained from a suite of air samples that were collected during a stratospheric balloon flight between 12 and
      33 km at 40º N in October 2002. Strong deuterium enrichments of up to 400
      permil versus Vienna Standard Mean Ocean Water (VSMOW) are observed, while the
      H&lt;sub&gt;2&lt;/sub&gt; mixing ratio remains virtually constant. Thus, as hydrogen is processed through the
      H&lt;sub&gt;2&lt;/sub&gt; reservoir in the stratosphere, deuterium is accumulated in H&lt;sub&gt;2&lt;/sub&gt;
      . Using box model calculations we investigated the effects of H&lt;sub&gt;2&lt;/sub&gt; sources and sinks on the stratospheric enrichments. Results show that considerable isotope
      enrichments in the production of H&lt;sub&gt;2&lt;/sub&gt;&amp;nbsp; from CH&lt;sub&gt;4&lt;/sub&gt; must take place, i.e., deuterium is transferred
      preferentially to H&lt;sub&gt;2&lt;/sub&gt; during the CH&lt;sub&gt;4&lt;/sub&gt; oxidation sequence. This supports recent conclusions from
      tropospheric H&lt;sub&gt;2&lt;/sub&gt; isotope measurements which show that H&lt;sub&gt;2&lt;/sub&gt; produced photochemically from
      CH&lt;sub&gt;4&lt;/sub&gt; and non-methane hydrocarbons must be enriched in deuterium to balance the
      tropospheric hydrogen isotope budget. In the absence of further data on isotope fractionations
      in the individual reaction steps of the CH&lt;sub&gt;4&lt;/sub&gt; oxidation sequence, this effect cannot be
      investigated further at present. Our measurements imply that molecular hydrogen has to be
      taken into account when the hydrogen isotope budget in the stratosphere is investigated.</p>
</abstract>
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