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<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-6-6255-2006</article-id>
<title-group>
<article-title>Pronounced signature of arctic surface ozone depletion events after polar sunrise on &amp;Delta;&lt;sup&gt;17&lt;/sup&gt;O in atmospheric nitrate</article-title>
</title-group>
<contrib-group><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Morin</surname>
<given-names>S.</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>Savarino</surname>
<given-names>J.</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>Bekki</surname>
<given-names>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>Gong</surname>
<given-names>S.</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>Bottenheim</surname>
<given-names>J. W.</given-names>
</name>
<xref ref-type="aff" rid="aff3">
<sup>3</sup>
</xref>
</contrib>
</contrib-group><aff id="aff1">
<label>1</label>
<addr-line>Laboratoire de Glaciologie et de G&amp;eacute;ophysique de l’Environnement, Grenoble, France</addr-line>
</aff>
<aff id="aff2">
<label>2</label>
<addr-line>Service d’A&amp;eacute;ronomie, Institut Pierre Simon Laplace, Paris, France</addr-line>
</aff>
<aff id="aff3">
<label>3</label>
<addr-line>Environment Canada, Toronto, Ontario, Canada</addr-line>
</aff>
<pub-date pub-type="epub">
<day>12</day>
<month>07</month>
<year>2006</year>
</pub-date>
<volume>6</volume>
<issue>4</issue>
<fpage>6255</fpage>
<lpage>6297</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-discuss.net/6/6255/2006/acpd-6-6255-2006.html">This article is available from http://www.atmos-chem-phys-discuss.net/6/6255/2006/acpd-6-6255-2006.html</self-uri>
<self-uri xlink:href="http://www.atmos-chem-phys-discuss.net/6/6255/2006/acpd-6-6255-2006.pdf">The full text article is available as a PDF file from http://www.atmos-chem-phys-discuss.net/6/6255/2006/acpd-6-6255-2006.pdf</self-uri>
<abstract>
<p>We report in this paper the first measurements of the isotopic anomaly of
oxygen in Arctic atmospheric inorganic nitrate. Data and samples were
collected at Alert, Nunavut, Canada (82&amp;deg;30&apos; N, 62&amp;deg;19&apos; W) in
spring 2004. Focusing on the polar sunrise period, characterized by the
occurrence of severe boundary layer ozone depletion events (ODEs), our data
show a significant correlation between the evolution of atmospheric ozone
(O&lt;sub&gt;3&lt;/sub&gt;) mixing ratios and &amp;Delta;&lt;sup&gt;17&lt;/sup&gt;O in nitrate
&amp;Delta;&lt;sup&gt;17&lt;/sup&gt;O(NO&lt;sup&gt;&amp;minus;&lt;/sup&gt;&lt;sub&gt;3&lt;/sub&gt;)). This relationship can be expressed as:
&amp;Delta;&lt;sup&gt;17&lt;/sup&gt;O(NO&lt;sup&gt;&amp;minus;&lt;/sup&gt;&lt;sub&gt;3&lt;/sub&gt;)/&amp;permil;=0.15 O&lt;sub&gt;3&lt;/sub&gt;/
(nmol&amp;nbsp;mol&lt;sup&gt;&amp;minus;1&lt;/sup&gt;) + 28.6, with R&lt;sup&gt;2&lt;/sup&gt;=0.70&amp;nbsp;(n=12), for &amp;Delta;&lt;sup&gt;17&lt;/sup&gt;O(NO&lt;sup&gt;&amp;minus;&lt;/sup&gt;&lt;sub&gt;3&lt;/sub&gt;) ranging between 29 and 34. To
quantitatively interpret this relationship, we derive from mechanisms at play
in the arctic boundary layer isotopic mass-balance equations, which depend on
the concentrations of reactive species and their isotopic characteristics.
Changes in the relative importance of O&lt;sub&gt;3&lt;/sub&gt;, RO&lt;sub&gt;2&lt;/sub&gt; and BrO
in the oxidation of NO&lt;sub&gt;x&lt;/sub&gt; during ODEs, and the large isotopic anomalies
that O&lt;sub&gt;3&lt;/sub&gt; and BrO carry, are the driving force for the high
variability in the measured &amp;Delta;&lt;sup&gt;17&lt;/sup&gt;O(NO&lt;sup&gt;&amp;minus;&lt;/sup&gt;&lt;sub&gt;3&lt;/sub&gt;). BrONO&lt;sub&gt;2&lt;/sub&gt;
hydrolysis is found to be the major source of nitrate in the arctic boundary
layer, in agreement with recent modeling studies. In addition, the isotopic
fingerprint of the activity of ozone in a relatively stable compound appears
somewhat promising in the perspective of using the isotopic composition of
nitrate embedded in polar ice-cores as a paleo-indicator of the atmospheric
ozone level that may yield an indirect proxy for the oxidative power of past
atmospheres.</p>
</abstract>
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