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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-5-9731-2005</article-id>
<title-group>
<article-title>Measurements and modelling of I&lt;sub&gt;2&lt;/sub&gt;, IO, OIO, BrO and NO&lt;sub&gt;3&lt;/sub&gt; in the mid-latitude marine boundary layer</article-title>
</title-group>
<contrib-group><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Saiz-Lopez</surname>
<given-names>A.</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>Shillito</surname>
<given-names>J. 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>Coe</surname>
<given-names>H.</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>Plane</surname>
<given-names>J. M. C.</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
</contrib-group><aff id="aff1">
<label>1</label>
<addr-line>School of Environmental Sciences, University of East Anglia, Norwich, UK</addr-line>
</aff>
<aff id="aff2">
<label>2</label>
<addr-line>School of Earth, Atmospheric and Environmental Sciences, University of Manchester, Manchester, UK</addr-line>
</aff>
<pub-date pub-type="epub">
<day>10</day>
<month>10</month>
<year>2005</year>
</pub-date>
<volume>5</volume>
<issue>5</issue>
<fpage>9731</fpage>
<lpage>9767</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/5/9731/2005/acpd-5-9731-2005.html">This article is available from http://www.atmos-chem-phys-discuss.net/5/9731/2005/acpd-5-9731-2005.html</self-uri>
<self-uri xlink:href="http://www.atmos-chem-phys-discuss.net/5/9731/2005/acpd-5-9731-2005.pdf">The full text article is available as a PDF file from http://www.atmos-chem-phys-discuss.net/5/9731/2005/acpd-5-9731-2005.pdf</self-uri>
<abstract>
<p>Time series observations of molecular iodine (I&lt;sub&gt;2&lt;/sub&gt;), iodine
oxides (IO, OIO), bromine oxide (BrO), and the nitrate radical
(NO&lt;sub&gt;3&lt;/sub&gt;) in the mid-latitude coastal marine boundary layer
(MBL) are reported. Measurements were made using a new long-path
DOAS instrument during a summertime campaign at Mace Head on the
west coast of Ireland. I&lt;sub&lt;2&lt;/sub&gt; was detected using the
&lt;i&gt;B&lt;/i&gt;&lt;sup&gt;3&lt;/sup&gt;&amp;Pi;(0&lt;sup&gt;+&lt;/sup&gt;&lt;sub&gt;u&lt;/sub&gt;)&amp;minus;&lt;i&gt;X&lt;/i&gt;&lt;sup&gt;1&lt;/sup&gt;&amp;Sigma;&lt;sup&gt;x&lt;/sup&gt;&lt;sub&gt;g&lt;/sub&gt; electronic transition
between 535 and 575 nm.  The I&lt;sub&gt;2&lt;/sub&gt; mixing ratio was found to
vary from below the detection limit (~5 ppt) up to a nighttime
maximum of 93 ppt. Along with I&lt;sub&gt;2&lt;/sub&gt;, observations of IO, OIO
and NO&lt;sub&gt;3&lt;/sub&gt; were also made during the night.  Surprisingly, IO
and OIO were detected at mixing ratios up to 2.5 and 10.8 ppt,
respectively.  A model is employed to show that the reaction
between I&lt;sub&gt;2&lt;/sub&gt; and NO&lt;sub&gt;3&lt;/sub&gt; is the likely nighttime source of
these radicals.  The BrO mixing ratio varied from below the
detection limit at night (~1 ppt) to a maximum of 6 ppt in the
first hours after sunrise. A model shows that this diurnal
behaviour can be explained by halogen recyling in sea-salt aerosol
building up photolabile precursors of atomic Br during the preceding
night. In the same campaign a zenith sky DOAS was employed to
determine the column density variation of NO&lt;sub&gt;3&lt;/sub&gt; as a function
of solar zenith angle (SZA) during sunrise, from which vertical
profiles of NO&lt;sub&gt;3&lt;/sub&gt; through the troposphere were obtained.  On
several occasions a positive gradient of NO&lt;sub&gt;3&lt;/sub&gt; was observed
over the first 2 km, possibly due to dimethyl sulphide (DMS)
removing NO&lt;sub&gt;3&lt;/sub&gt; at the ocean surface.</p>
</abstract>
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