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<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-12-7737-2012</article-id>
<title-group>
<article-title>Summertime photochemistry during CAREBeijing-2007: RO&lt;sub&gt;x&lt;/sub&gt; budgets and O&lt;sub&gt;3&lt;/sub&gt; formation</article-title>
</title-group>
<contrib-group><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Liu</surname>
<given-names>Z.</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<xref ref-type="aff" rid="aff6">
<sup>6</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Wang</surname>
<given-names>Y.</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>Gu</surname>
<given-names>D.</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>Zhao</surname>
<given-names>C.</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</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>Huey</surname>
<given-names>L. G.</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>Stickel</surname>
<given-names>R.</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>Liao</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>Shao</surname>
<given-names>M.</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>Zhu</surname>
<given-names>T.</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>Zeng</surname>
<given-names>L.</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>Amoroso</surname>
<given-names>A.</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>Costabile</surname>
<given-names>F.</given-names>
</name>
<xref ref-type="aff" rid="aff4">
<sup>4</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Chang</surname>
<given-names>C.-C.</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>Liu</surname>
<given-names>S.-C.</given-names>
</name>
<xref ref-type="aff" rid="aff5">
<sup>5</sup>
</xref>
</contrib>
</contrib-group><aff id="aff1">
<label>1</label>
<addr-line>School of Earth and Atmospheric Science, Georgia Institute of Technology, Atlanta, GA, USA</addr-line>
</aff>
<aff id="aff2">
<label>2</label>
<addr-line>College of Environmental Sciences and Engineering, Peking University, Beijing, China</addr-line>
</aff>
<aff id="aff3">
<label>3</label>
<addr-line>Institute for Atmospheric Pollution, National Research Council (CNR-IIA), Rome, Italy</addr-line>
</aff>
<aff id="aff4">
<label>4</label>
<addr-line>Institute for Atmospheric Sciences and Climate (ISAC), CNR, Rome, Italy</addr-line>
</aff>
<aff id="aff5">
<label>5</label>
<addr-line>Research Center for Environmental Changes (RCEC), Academic Sinica, Taipei, China</addr-line>
</aff>
<aff id="aff6">
<label>6</label>
<addr-line>now at: Combustion Research Facility, Sandia National Laboratories, Livermore, CA, USA</addr-line>
</aff>
<aff id="aff7">
<label>7</label>
<addr-line>now at: the Pacific Northwest National Laboratory, Richland, Washington, USA</addr-line>
</aff>
<pub-date pub-type="epub">
<day>28</day>
<month>08</month>
<year>2012</year>
</pub-date>
<volume>12</volume>
<issue>16</issue>
<fpage>7737</fpage>
<lpage>7752</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.net/12/7737/2012/acp-12-7737-2012.pdf">The full text article is available as a PDF file from http://www.atmos-chem-phys.net/12/7737/2012/acp-12-7737-2012.pdf</self-uri>
<abstract>
<p>We analyze summertime photochemistry near the surface in Beijing, China,
using a 1-D photochemical model (Regional chEmical and trAnsport Model,
REAM-1D) constrained by in situ observations, focusing on the budgets of
RO&lt;sub&gt;x&lt;/sub&gt; (OH + HO&lt;sub&gt;2&lt;/sub&gt; + RO&lt;sub&gt;2&lt;/sub&gt;) radicals and O&lt;sub&gt;3&lt;/sub&gt; formation.
While the modeling analysis focuses on near-surface photochemical budgets,
the implications for the budget of O&lt;sub&gt;3&lt;/sub&gt; in the planetary boundary layer
are also discussed. In terms of daytime average, the total RO&lt;sub&gt;x&lt;/sub&gt;
primary production rate near the surface in Beijing is 6.6 ppbv per hour
(ppbv h&lt;sup&gt;−1&lt;/sup&gt;, among the highest found in urban atmospheres. The largest
primary RO&lt;sub&gt;x&lt;/sub&gt; source in Beijing is photolysis of oxygenated volatile
organic compounds (OVOCs), which produces HO&lt;sub&gt;2&lt;/sub&gt; and RO&lt;sub&gt;2&lt;/sub&gt; at
2.5 ppbv h&lt;sup&gt;−1&lt;/sup&gt; and 1.7 ppbv h&lt;sup&gt;−1&lt;/sup&gt;, respectively. Photolysis of
excess HONO from an unknown heterogeneous source is the predominant primary
OH source at 2.2 ppbv h&lt;sup&gt;−1&lt;/sup&gt;, much larger than that of O&lt;sup&gt;1&lt;/sup&gt;D+H&lt;sub&gt;2&lt;/sub&gt;O
(0.4 ppbv h&lt;sup&gt;−1&lt;/sup&gt;). The largest RO&lt;sub&gt;x&lt;/sub&gt; sink is via OH + NO&lt;sub&gt;2&lt;/sub&gt;
reaction (1.6 ppbv h&lt;sup&gt;−1&lt;/sup&gt;), followed by formation of RO&lt;sub&gt;2&lt;/sub&gt;NO&lt;sub&gt;2&lt;/sub&gt;
(1.0 ppbv h&lt;sup&gt;−1&lt;/sup&gt;) and RONO&lt;sub&gt;2&lt;/sub&gt; (0.7 ppbv h&lt;sup&gt;−1&lt;/sup&gt;). Due to the large
aerosol surface area, aerosol uptake of HO&lt;sub&gt;2&lt;/sub&gt; appears to be another
important radical sink, although the estimate of its magnitude is highly
variable depending on the uptake coefficient value used. The daytime average
O&lt;sub&gt;3&lt;/sub&gt; production and loss rates near the surface are 32 ppbv h&lt;sup&gt;−1&lt;/sup&gt; and
6.2 ppbv h&lt;sup&gt;−1&lt;/sup&gt;, respectively. Assuming NO&lt;sub&gt;2&lt;/sub&gt; to be the source of
excess HONO, the NO&lt;sub&gt;2&lt;/sub&gt; to HONO transformation leads to considerable
O&lt;sub&gt;3&lt;/sub&gt; loss and reduction of its lifetime. Our observation-constrained
modeling analysis suggests that oxidation of VOCs (especially aromatics) and
heterogeneous reactions (e.g. HONO formation and aerosol uptake HO&lt;sub&gt;2&lt;/sub&gt;)
play potentially critical roles in the primary radical budget and O&lt;sub&gt;3&lt;/sub&gt;
formation in Beijing. One important ramification is that O&lt;sub&gt;3&lt;/sub&gt; production
is neither NO&lt;sub&gt;x&lt;/sub&gt; nor VOC limited, but in a transition regime where
reduction of either NO&lt;sub&gt;x&lt;/sub&gt; or VOCs could result in reduction of
O&lt;sub&gt;3&lt;/sub&gt; production. The transition regime implies more flexibility in the
O&lt;sub&gt;3&lt;/sub&gt; control strategies than a binary system of either NO&lt;sub&gt;x&lt;/sub&gt; or
VOC limited regime. The co-benefit of concurrent reduction of both NO&lt;sub&gt;x&lt;/sub&gt; 
and VOCs in reducing column O&lt;sub&gt;3&lt;/sub&gt; production integrated in the
planetary boundary layer is significant. Further research on the spatial
extent of the transition regime over the polluted eastern China is critically
important for controlling regional O&lt;sub&gt;3&lt;/sub&gt; pollution.</p>
</abstract>
<counts><page-count count="16"/></counts>
</article-meta>
</front>
<body/>
<back>
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