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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>
<abbrev-journal-title abbrev-type="nlm-ta">Atmos. Chem. Phys.</abbrev-journal-title>
</journal-title-group>
<issn pub-type="epub">1680-7324</issn>
<publisher><publisher-name>Copernicus Publications</publisher-name>
<publisher-loc>Göttingen, Germany</publisher-loc>
</publisher>
</journal-meta>
<article-meta>
<article-id pub-id-type="doi">10.5194/acp-14-1299-2014</article-id>
<title-group>
<article-title>Radical chemistry at night: comparisons between observed and modelled HO&lt;sub&gt;x&lt;/sub&gt;, NO&lt;sub&gt;3&lt;/sub&gt; and N&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;5&lt;/sub&gt; during the RONOCO project</article-title>
</title-group>
<contrib-group><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Stone</surname>
<given-names>D.</given-names>
<ext-link>https://orcid.org/0000-0001-5610-0463</ext-link>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Evans</surname>
<given-names>M. J.</given-names>
<ext-link>https://orcid.org/0000-0003-4775-032X</ext-link>
</name>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
<xref ref-type="aff" rid="aff3">
<sup>3</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Walker</surname>
<given-names>H.</given-names>
<ext-link>https://orcid.org/0000-0001-5144-1605</ext-link>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Ingham</surname>
<given-names>T.</given-names>
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<sup>1</sup>
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<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Vaughan</surname>
<given-names>S.</given-names>
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<sup>1</sup>
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<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Ouyang</surname>
<given-names>B.</given-names>
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<xref ref-type="aff" rid="aff5">
<sup>5</sup>
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<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Kennedy</surname>
<given-names>O. J.</given-names>
</name>
<xref ref-type="aff" rid="aff5">
<sup>5</sup>
</xref>
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<given-names>M. W.</given-names>
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<xref ref-type="aff" rid="aff5">
<sup>5</sup>
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<given-names>R. L.</given-names>
</name>
<xref ref-type="aff" rid="aff5">
<sup>5</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Hopkins</surname>
<given-names>J.</given-names>
</name>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
<xref ref-type="aff" rid="aff3">
<sup>3</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Punjabi</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>Lidster</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>Hamilton</surname>
<given-names>J. F.</given-names>
</name>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
<xref ref-type="aff" rid="aff3">
<sup>3</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Lee</surname>
<given-names>J. D.</given-names>
<ext-link>https://orcid.org/0000-0001-5397-2872</ext-link>
</name>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
<xref ref-type="aff" rid="aff3">
<sup>3</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Lewis</surname>
<given-names>A. C.</given-names>
</name>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
<xref ref-type="aff" rid="aff3">
<sup>3</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Carpenter</surname>
<given-names>L. J.</given-names>
</name>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
<xref ref-type="aff" rid="aff3">
<sup>3</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Forster</surname>
<given-names>G.</given-names>
</name>
<xref ref-type="aff" rid="aff6">
<sup>6</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Oram</surname>
<given-names>D. E.</given-names>
</name>
<xref ref-type="aff" rid="aff6">
<sup>6</sup>
</xref>
<xref ref-type="aff" rid="aff7">
<sup>7</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Reeves</surname>
<given-names>C. E.</given-names>
<ext-link>https://orcid.org/0000-0003-4071-1926</ext-link>
</name>
<xref ref-type="aff" rid="aff6">
<sup>6</sup>
</xref>
<xref ref-type="aff" rid="aff7">
<sup>7</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Bauguitte</surname>
<given-names>S.</given-names>
</name>
<xref ref-type="aff" rid="aff8">
<sup>8</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Morgan</surname>
<given-names>W.</given-names>
</name>
<xref ref-type="aff" rid="aff9">
<sup>9</sup>
</xref>
<xref ref-type="aff" rid="aff10">
<sup>10</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="aff9">
<sup>9</sup>
</xref>
<xref ref-type="aff" rid="aff10">
<sup>10</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Aruffo</surname>
<given-names>E.</given-names>
</name>
<xref ref-type="aff" rid="aff11">
<sup>11</sup>
</xref>
<xref ref-type="aff" rid="aff12">
<sup>12</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Dari-Salisburgo</surname>
<given-names>C.</given-names>
</name>
<xref ref-type="aff" rid="aff11">
<sup>11</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Giammaria</surname>
<given-names>F.</given-names>
</name>
<xref ref-type="aff" rid="aff12">
<sup>12</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Di Carlo</surname>
<given-names>P.</given-names>
<ext-link>https://orcid.org/0000-0003-4971-4509</ext-link>
</name>
<xref ref-type="aff" rid="aff11">
<sup>11</sup>
</xref>
<xref ref-type="aff" rid="aff12">
<sup>12</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Heard</surname>
<given-names>D. E.</given-names>
<ext-link>https://orcid.org/0000-0002-0357-6238</ext-link>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<xref ref-type="aff" rid="aff4">
<sup>4</sup>
</xref>
</contrib>
</contrib-group><aff id="aff1">
<label>1</label>
<addr-line>School of Chemistry, University of Leeds, Leeds, UK</addr-line>
</aff>
<aff id="aff2">
<label>2</label>
<addr-line>National Centre for Atmospheric Science, University of York, York, UK</addr-line>
</aff>
<aff id="aff3">
<label>3</label>
<addr-line>Department of Chemistry, University of York, York, UK</addr-line>
</aff>
<aff id="aff4">
<label>4</label>
<addr-line>National Centre for Atmospheric Science, University of Leeds, Leeds, UK</addr-line>
</aff>
<aff id="aff5">
<label>5</label>
<addr-line>Department of Chemistry, University of Cambridge, Cambridgeshire, UK</addr-line>
</aff>
<aff id="aff6">
<label>6</label>
<addr-line>School of Environmental Sciences, University of East Anglia, Norwich, UK</addr-line>
</aff>
<aff id="aff7">
<label>7</label>
<addr-line>National Centre for Atmospheric Science,  University of East Anglia, Norwich, UK</addr-line>
</aff>
<aff id="aff8">
<label>8</label>
<addr-line>Facility for Airborne Atmospheric Measurements, Bedfordshire, UK</addr-line>
</aff>
<aff id="aff9">
<label>9</label>
<addr-line>School of Earth Atmospheric and Environmental Science, University of Manchester, Manchester, UK</addr-line>
</aff>
<aff id="aff10">
<label>10</label>
<addr-line>National Centre for Atmospheric Science, University of Manchester, Manchester, UK</addr-line>
</aff>
<aff id="aff11">
<label>11</label>
<addr-line>Center of Excellence CETEMPS Universita&apos; degli studi di L&apos;Aquila, L&apos;Aquila, Italy</addr-line>
</aff>
<aff id="aff12">
<label>12</label>
<addr-line>Dipartimento di Fisica, Universita&apos; degli studi di L&apos;Aquila, L&apos;Aquila, Italy</addr-line>
</aff>
<pub-date pub-type="epub">
<day>05</day>
<month>02</month>
<year>2014</year>
</pub-date>
<volume>14</volume>
<issue>3</issue>
<fpage>1299</fpage>
<lpage>1321</lpage>
<permissions>
<copyright-statement>Copyright: &#x000a9; 2014 D. Stone et al.</copyright-statement>
<copyright-year>2014</copyright-year>
<license license-type="open-access">
<license-p>This work is licensed under the Creative Commons Attribution 3.0 Unported License. To view a copy of this licence, visit <ext-link ext-link-type="uri"  xlink:href="https://creativecommons.org/licenses/by/3.0/">https://creativecommons.org/licenses/by/3.0/</ext-link></license-p>
</license>
</permissions>
<self-uri xlink:href="https://acp.copernicus.org/articles/14/1299/2014/acp-14-1299-2014.html">This article is available from https://acp.copernicus.org/articles/14/1299/2014/acp-14-1299-2014.html</self-uri>
<self-uri xlink:href="https://acp.copernicus.org/articles/14/1299/2014/acp-14-1299-2014.pdf">The full text article is available as a PDF file from https://acp.copernicus.org/articles/14/1299/2014/acp-14-1299-2014.pdf</self-uri>
<abstract>
<p>The RONOCO (ROle of Nighttime chemistry in controlling the Oxidising Capacity of the
AtmOsphere) aircraft campaign during July 2010 and January 2011 made
observations of OH, HO&lt;sub&gt;2&lt;/sub&gt;, NO&lt;sub&gt;3&lt;/sub&gt;, N&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;5&lt;/sub&gt; and a number of
supporting measurements at night over the UK, and reflects the first
simultaneous airborne measurements of these species. We compare the observed
concentrations of these short-lived species with those calculated by a box
model constrained by the concentrations of the longer lived species using a
detailed chemical scheme. OH concentrations were below the limit of
detection, consistent with model predictions. The model systematically
underpredicts HO&lt;sub&gt;2&lt;/sub&gt; by ~200% and overpredicts NO&lt;sub&gt;3&lt;/sub&gt;
and N&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;5&lt;/sub&gt; by around 80  and 50%, respectively.
Cycling between NO&lt;sub&gt;3&lt;/sub&gt; and N&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;5&lt;/sub&gt; is fast and thus we define the
NO&lt;sub&gt;3x&lt;/sub&gt; (NO&lt;sub&gt;3x&lt;/sub&gt;=NO&lt;sub&gt;3&lt;/sub&gt;+N&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;5&lt;/sub&gt;) family. Production
of NO&lt;sub&gt;3x&lt;/sub&gt; is overwhelmingly dominated by the reaction of NO&lt;sub&gt;2&lt;/sub&gt; with
O&lt;sub&gt;3&lt;/sub&gt;, whereas its loss is dominated by aerosol uptake of N&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;5&lt;/sub&gt;,
with NO&lt;sub&gt;3&lt;/sub&gt;+VOCs (volatile organic compounds) and NO&lt;sub&gt;3&lt;/sub&gt;+RO&lt;sub&gt;2&lt;/sub&gt; playing smaller roles. The production of HO&lt;sub&gt;x&lt;/sub&gt; and RO&lt;sub&gt;x&lt;/sub&gt; radicals is mainly due to the
reaction of NO&lt;sub&gt;3&lt;/sub&gt; with VOCs. The loss of these radicals occurs through a
combination of HO&lt;sub&gt;2&lt;/sub&gt;+RO&lt;sub&gt;2&lt;/sub&gt; reactions, heterogeneous processes and
production of HNO&lt;sub&gt;3&lt;/sub&gt; from OH+NO&lt;sub&gt;2&lt;/sub&gt;, with radical propagation
primarily achieved through reactions of NO&lt;sub&gt;3&lt;/sub&gt; with peroxy radicals. Thus
NO&lt;sub&gt;3&lt;/sub&gt; at night plays a similar role to both OH and NO during the day in
that it both initiates RO&lt;sub&gt;x&lt;/sub&gt; radical production and acts to propagate the
tropospheric oxidation chain. Model sensitivity to the N&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;5&lt;/sub&gt;
aerosol uptake coefficient (&amp;gamma;&lt;sub&gt;N&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;5&lt;/sub&gt;&lt;/sub&gt;) is discussed  and we find
that a value of &amp;gamma;&lt;sub&gt;N&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;5&lt;/sub&gt;&lt;/sub&gt;=0.05 improves model simulations for
NO&lt;sub&gt;3&lt;/sub&gt; and N&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;5&lt;/sub&gt;, but that these improvements are at the expense
of model success for HO&lt;sub&gt;2&lt;/sub&gt;. Improvements to model simulations for
HO&lt;sub&gt;2&lt;/sub&gt;, NO&lt;sub&gt;3&lt;/sub&gt; and N&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;5&lt;/sub&gt; can be realised simultaneously on
inclusion of additional unsaturated volatile organic compounds, however the
nature of these compounds is extremely uncertain.</p>
</abstract>
<counts><page-count count="23"/></counts>
</article-meta>
</front>
<body/>
<back>
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