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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-12-10651-2012</article-id>
<title-group>
<article-title>Cyclobutyl methyl ketone as a model compound for pinonic acid to elucidate oxidation mechanisms</article-title>
</title-group>
<contrib-group><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Praplan</surname>
<given-names>A. P.</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>Barmet</surname>
<given-names>P.</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>Dommen</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>Baltensperger</surname>
<given-names>U.</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
</contrib-group><aff id="aff1">
<label>1</label>
<addr-line>Laboratory of Atmospheric Chemistry, Paul Scherrer Institute, Villigen PSI, Switzerland</addr-line>
</aff>
<pub-date pub-type="epub">
<day>24</day>
<month>04</month>
<year>2012</year>
</pub-date>
<volume>12</volume>
<issue>4</issue>
<fpage>10651</fpage>
<lpage>10678</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-discuss.net/12/10651/2012/acpd-12-10651-2012.pdf">The full text article is available as a PDF file from http://www.atmos-chem-phys-discuss.net/12/10651/2012/acpd-12-10651-2012.pdf</self-uri>
<abstract>
<p>3-Methyl-1,2,3-tricarboxylic acid (MBTCA), terpenylic acid and
      diaterpenylic acid acetate were identified in secondary
      organic aerosol (SOA) from α-pinene photooxidation or
      ozonolysis. These compounds display interesting structural
      features: MBTCA has a high oxygen to carbon ratio, terpenylic
      acid contains a lactone ring in its structure and
      diaterpenylic acid acetate possesses an ester functional
      group. The reaction mechanisms leading to these products are
      still unknown, but it was demonstrated experimentally in
      earlier studies that MBTCA is formed from pinonic acid,
      a primary ozonolysis product of α-pinene.  Because the
      direct observation of pinonic acid oxidation in a smog chamber
      would be difficult due to its relatively low volatility,
      a model compound possessing the substructure of interest was
      used instead: cyclobutyl methyl ketone (CMK). From its
      oxidation, several organic acids could be measured with ion
      chromatography (IC) coupled to a mass spectrometer
      (MS). Succinic acid, the analogous product of MBTCA is formed
      at molar yields of 2 to 5%. Butyrolactone is detected as
      butanoic acid, due to hydrolysis in the sampling
      device. A monocarboxylic acid with nominal mass 146 was
      detected in the absence of nitrogen oxides (NO&lt;sub&gt;x&lt;/sub&gt;) and
      could be the analogous product of diaterpenylic acid
      acetate. However, due to a lack of available standards, the
      exact structure of this compound remains
      unelucidated. Finally, 4-oxobutanoic acid could also be
      measured and two structures of its expected analogous compound
      from pinonic acid oxidation are proposed. Because these
      compounds are primary products of the CMK oxidation, reaction
      mechanisms capable of adding one or two carboxylic functional
      groups without formation of stable intermediate products needs
      to be formulated. Such a formation mechanism of MBTCA from
      pinonic acid was found in the literature; however, it includes
      a hydrogen atom migration to an acyloxy radical, which is
      expected to loose carbon dioxide (CO&lt;sub&gt;2&lt;/sub&gt;) very
      rapidly. A competitive reaction pathway is expected to lead to
      the formation of a monocarboxylic acid with nominal mass 144,
      instead of this acyloxy radical; however, no such
      monocarboxylic acid was measured and other reaction pathways
      still need to be explored.</p>
</abstract>
<counts><page-count count="28"/></counts>
</article-meta>
</front>
<body/>
<back>
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</back>
</article>