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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-3-1063-2003</article-id>
<title-group>
<article-title>Laboratory study on heterogeneous decomposition of methyl chloroform on various standard aluminosilica clay minerals as a potential tropospheric sink</article-title>
</title-group>
<contrib-group><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Kutsuna</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>Chen</surname>
<given-names>L.</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>Ohno</surname>
<given-names>K.</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>Negishi</surname>
<given-names>N.</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>Takeuchi</surname>
<given-names>K.</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>Ibusuki</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>Tokuhashi</surname>
<given-names>K.</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>Sekiya</surname>
<given-names>A.</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
</contrib-group><aff id="aff1">
<label>1</label>
<addr-line>National Institute of Advanced Industrial Science and Technology (AIST), 16-1 Onogawa, Tsukuba, Ibaraki 305-8569, Japan</addr-line>
</aff>
<pub-date pub-type="epub">
<day>21</day>
<month>07</month>
<year>2003</year>
</pub-date>
<volume>3</volume>
<issue>4</issue>
<fpage>1063</fpage>
<lpage>1082</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/3/1063/2003/acp-3-1063-2003.html">This article is available from http://www.atmos-chem-phys.net/3/1063/2003/acp-3-1063-2003.html</self-uri>
<self-uri xlink:href="http://www.atmos-chem-phys.net/3/1063/2003/acp-3-1063-2003.pdf">The full text article is available as a PDF file from http://www.atmos-chem-phys.net/3/1063/2003/acp-3-1063-2003.pdf</self-uri>
<abstract>
<p>Methyl chloroform (1,1,1-trichloroethane,
      CH&lt;sub&gt;3&lt;/sub&gt;CCl&lt;sub&gt;3&lt;/sub&gt;) was found to decompose heterogeneously on seven types of standard clay minerals (23 materials) in dry air
      at 313 K in the laboratory. All reactions proceeded through the elimination of
      HCl; CH&lt;sub&gt;3&lt;/sub&gt;CCl&lt;sub&gt;3&lt;/sub&gt;
      was converted quantitatively to CH&lt;sub&gt;2&lt;/sub&gt;=CCl&lt;sub&gt;2&lt;/sub&gt;. The activities
      of the clay minerals were compared via their pseudo-first-order reaction rate constants
      (&lt;i&gt;k&lt;/i&gt;&lt;sub&gt;1&lt;/sub&gt;). A positive correlation was observed between the &lt;i&gt;k&lt;/i&gt;&lt;sub&gt;1&lt;/sub&gt;
      value and the specific surface area (&lt;i&gt;S&lt;/i&gt;) of clay minerals, where the
      &lt;i&gt;S&lt;/i&gt; value was determined by means of the general Brunauer-Emmett-Teller (BET) equation. The
      &lt;i&gt;k&lt;/i&gt;&lt;sub&gt;1&lt;/sub&gt; value was anti-correlated with the value of &lt;i&gt;n&lt;/i&gt;, which was a parameter of the general BET equation and related to the
      average pore size of the clay minerals, and correlated with the water content that can
      be removed easily from the clay minerals. The reaction required no special pretreatment
      of clay minerals, such as heating at high temperatures; hence, the reaction can be
      expected to occur in the environment. Photoillumination by wavelengths present in the
      troposphere did not accelerate the decomposition of CH&lt;sub&gt;3&lt;/sub&gt;CCl&lt;sub&gt;3&lt;/sub&gt;, but it induced
      heterogeneous photodecomposition of CH&lt;sub&gt;2&lt;/sub&gt;=CCl&lt;sub&gt;2&lt;/sub&gt;. The temperature dependence
      of &lt;i&gt;k&lt;/i&gt;&lt;sub&gt;1&lt;/sub&gt;, the adsorption equilibrium coefficient of CH&lt;sub&gt;3&lt;/sub&gt;CCl&lt;sub&gt;3&lt;/sub&gt;
      and CH&lt;sub&gt;2&lt;/sub&gt;=CCl&lt;sub&gt;2&lt;/sub&gt;, and the surface reaction rate constant of
      CH&lt;sub&gt;3&lt;/sub&gt;CCl&lt;sub&gt;3&lt;/sub&gt; were determined for an illite sample. The &lt;i&gt;k&lt;/i&gt;&lt;sub&gt;1&lt;/sub&gt;
      value increased with increasing temperature. The amount of CH&lt;sub&gt;3&lt;/sub&gt;CCl&lt;sub&gt;3&lt;/sub&gt; adsorbed
      on the illite during the reaction was proportional to the partial pressure of
      CH&lt;sub&gt;3&lt;/sub&gt;CCl&lt;sub&gt;3&lt;/sub&gt;. The reaction was sensitive to relative humidity and the
      &lt;i&gt;k&lt;/i&gt;&lt;sub&gt;1&lt;/sub&gt; value decreased with increasing relative humidity. However, the reaction was found to proceed at a relative humidity of
      22% at 313 K, although the &lt;i&gt;k&lt;/i&gt;&lt;sub&gt;1&lt;/sub&gt; value was about one-twentieth of the value in non-humidified air. The conditions
      required for the reaction may be present in major desert regions of the world. A simple estimation
      indicates that the possible heterogeneous decomposition of CH&lt;sub&gt;3&lt;/sub&gt;CCl&lt;sub&gt;3&lt;/sub&gt; on the ground surface in arid regions
      is worth taking into consideration when inferring the tropospheric lifetime of
      CH&lt;sub&gt;3&lt;/sub&gt;CCl&lt;sub&gt;3&lt;/sub&gt; and global OH concentration from the global budget concentration of
      CH&lt;sub&gt;3&lt;/sub&gt;CCl&lt;sub&gt;3&lt;/sub&gt;.</p>
</abstract>
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