Campholenic aldehyde ozonolysis: a mechanism leading to specific biogenic secondary organic aerosol constituents
In the present study, campholenic aldehyde ozonolysis was performed to investigate pathways leading to specific biogenic secondary organic aerosol (SOA) marker compounds. Campholenic aldehyde, a known α-pinene oxidation product, is suggested to be a key intermediate in the formation of terpenylic ac...
| Main Authors: | , , , , , |
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| Format: | Article |
| Language: | English |
| Published: |
Copernicus Publications
2014-01-01
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| Series: | Atmospheric Chemistry and Physics |
| Online Access: | http://www.atmos-chem-phys.net/14/719/2014/acp-14-719-2014.pdf |
| _version_ | 1818179010967896064 |
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| author | A. Kahnt Y. Iinuma A. Mutzel O. Böge M. Claeys H. Herrmann |
| author_facet | A. Kahnt Y. Iinuma A. Mutzel O. Böge M. Claeys H. Herrmann |
| author_sort | A. Kahnt |
| collection | DOAJ |
| description | In the present study, campholenic aldehyde ozonolysis was performed to
investigate pathways leading to specific biogenic secondary organic aerosol
(SOA) marker compounds. Campholenic aldehyde, a known α-pinene
oxidation product, is suggested to be a key intermediate in the formation of
terpenylic acid upon α-pinene ozonolysis. It was reacted with ozone
in the presence and absence of an OH radical scavenger, leading to SOA
formation with a yield of 0.75 and 0.8, respectively. The resulting
oxidation products in the gas and particle phases were investigated
employing a denuder/filter sampling combination. Gas-phase oxidation
products bearing a carbonyl group, which were collected by the denuder, were
derivatised by 2,4-dinitrophenylhydrazine (DNPH) followed by liquid
chromatography/negative ion electrospray ionisation time-of-flight mass
spectrometry analysis and were compared to the gas-phase compounds detected
by online proton-transfer-reaction mass spectrometry. Particle-phase
products were also analysed, directly or after DNPH derivatisation, to
derive information about specific compounds leading to SOA formation. Among
the detected compounds, the aldehydic precursor of terpenylic acid was
identified and its presence was confirmed in ambient aerosol samples from
the DNPH derivatisation, accurate mass data,
and additional mass spectrometry (MS<sup>2</sup> and MS<sup>3</sup>
fragmentation studies). Furthermore, the present investigation sheds light on
a reaction pathway leading to the formation of terpenylic acid, involving
α-pinene, α-pinene oxide, campholenic aldehyde, and
terpenylic aldehyde. Additionally, the formation of diaterpenylic acid
acetate could be connected to campholenic aldehyde oxidation. The present
study also provides insights into the source of other highly functionalised
oxidation products (e.g. <i>m</i> / <i>z</i> 201, C<sub>9</sub>H<sub>14</sub>O<sub>5</sub> and <i>m</i> / <i>z</i> 215,
C<sub>10</sub>H<sub>16</sub>O<sub>5</sub>), which have been observed in ambient aerosol
samples and smog chamber-generated monoterpene SOA. The <i>m</i> / <i>z</i> 201 and 215
compounds were tentatively identified as a C<sub>9</sub>- and
C<sub>10</sub>-carbonyl-dicarboxylic acid, respectively, based on reaction
mechanisms of campholenic aldehyde and ozone, as well as detailed interpretation of
mass spectral data, in conjunction with the formation of corresponding
DNPH derivatives. |
| first_indexed | 2024-12-11T20:57:05Z |
| format | Article |
| id | doaj.art-435ab1835b714a84bd610ba2f4a31fbf |
| institution | Directory Open Access Journal |
| issn | 1680-7316 1680-7324 |
| language | English |
| last_indexed | 2024-12-11T20:57:05Z |
| publishDate | 2014-01-01 |
| publisher | Copernicus Publications |
| record_format | Article |
| series | Atmospheric Chemistry and Physics |
| spelling | doaj.art-435ab1835b714a84bd610ba2f4a31fbf2022-12-22T00:51:05ZengCopernicus PublicationsAtmospheric Chemistry and Physics1680-73161680-73242014-01-0114271973610.5194/acp-14-719-2014Campholenic aldehyde ozonolysis: a mechanism leading to specific biogenic secondary organic aerosol constituentsA. Kahnt0Y. Iinuma1A. Mutzel2O. Böge3M. Claeys4H. Herrmann5Leibniz-Institut für Troposphärenforschung (TROPOS), Permoserstr. 15, Leipzig, 04318, GermanyLeibniz-Institut für Troposphärenforschung (TROPOS), Permoserstr. 15, Leipzig, 04318, GermanyLeibniz-Institut für Troposphärenforschung (TROPOS), Permoserstr. 15, Leipzig, 04318, GermanyLeibniz-Institut für Troposphärenforschung (TROPOS), Permoserstr. 15, Leipzig, 04318, GermanyDepartment of Pharmaceutical Sciences, University of Antwerp (Campus Drie Eiken), 2610 Antwerp, BelgiumLeibniz-Institut für Troposphärenforschung (TROPOS), Permoserstr. 15, Leipzig, 04318, GermanyIn the present study, campholenic aldehyde ozonolysis was performed to investigate pathways leading to specific biogenic secondary organic aerosol (SOA) marker compounds. Campholenic aldehyde, a known α-pinene oxidation product, is suggested to be a key intermediate in the formation of terpenylic acid upon α-pinene ozonolysis. It was reacted with ozone in the presence and absence of an OH radical scavenger, leading to SOA formation with a yield of 0.75 and 0.8, respectively. The resulting oxidation products in the gas and particle phases were investigated employing a denuder/filter sampling combination. Gas-phase oxidation products bearing a carbonyl group, which were collected by the denuder, were derivatised by 2,4-dinitrophenylhydrazine (DNPH) followed by liquid chromatography/negative ion electrospray ionisation time-of-flight mass spectrometry analysis and were compared to the gas-phase compounds detected by online proton-transfer-reaction mass spectrometry. Particle-phase products were also analysed, directly or after DNPH derivatisation, to derive information about specific compounds leading to SOA formation. Among the detected compounds, the aldehydic precursor of terpenylic acid was identified and its presence was confirmed in ambient aerosol samples from the DNPH derivatisation, accurate mass data, and additional mass spectrometry (MS<sup>2</sup> and MS<sup>3</sup> fragmentation studies). Furthermore, the present investigation sheds light on a reaction pathway leading to the formation of terpenylic acid, involving α-pinene, α-pinene oxide, campholenic aldehyde, and terpenylic aldehyde. Additionally, the formation of diaterpenylic acid acetate could be connected to campholenic aldehyde oxidation. The present study also provides insights into the source of other highly functionalised oxidation products (e.g. <i>m</i> / <i>z</i> 201, C<sub>9</sub>H<sub>14</sub>O<sub>5</sub> and <i>m</i> / <i>z</i> 215, C<sub>10</sub>H<sub>16</sub>O<sub>5</sub>), which have been observed in ambient aerosol samples and smog chamber-generated monoterpene SOA. The <i>m</i> / <i>z</i> 201 and 215 compounds were tentatively identified as a C<sub>9</sub>- and C<sub>10</sub>-carbonyl-dicarboxylic acid, respectively, based on reaction mechanisms of campholenic aldehyde and ozone, as well as detailed interpretation of mass spectral data, in conjunction with the formation of corresponding DNPH derivatives.http://www.atmos-chem-phys.net/14/719/2014/acp-14-719-2014.pdf |
| spellingShingle | A. Kahnt Y. Iinuma A. Mutzel O. Böge M. Claeys H. Herrmann Campholenic aldehyde ozonolysis: a mechanism leading to specific biogenic secondary organic aerosol constituents Atmospheric Chemistry and Physics |
| title | Campholenic aldehyde ozonolysis: a mechanism leading to specific biogenic secondary organic aerosol constituents |
| title_full | Campholenic aldehyde ozonolysis: a mechanism leading to specific biogenic secondary organic aerosol constituents |
| title_fullStr | Campholenic aldehyde ozonolysis: a mechanism leading to specific biogenic secondary organic aerosol constituents |
| title_full_unstemmed | Campholenic aldehyde ozonolysis: a mechanism leading to specific biogenic secondary organic aerosol constituents |
| title_short | Campholenic aldehyde ozonolysis: a mechanism leading to specific biogenic secondary organic aerosol constituents |
| title_sort | campholenic aldehyde ozonolysis a mechanism leading to specific biogenic secondary organic aerosol constituents |
| url | http://www.atmos-chem-phys.net/14/719/2014/acp-14-719-2014.pdf |
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