Direct probing of acylperoxy radicals during ozonolysis of α-pinene: constraints on radical chemistry and production of highly oxygenated organic molecules
Acylperoxy radicals (RO.sub.2) are key intermediates in the atmospheric oxidation of organic compounds and different from the general alkyl RO.sub.2 radicals in reactivity. However, direct probing of the molecular identities and chemistry of acyl RO.sub.2 remains quite limited. Here, we report a com...
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description | Acylperoxy radicals (RO.sub.2) are key intermediates in the atmospheric oxidation of organic compounds and different from the general alkyl RO.sub.2 radicals in reactivity. However, direct probing of the molecular identities and chemistry of acyl RO.sub.2 remains quite limited. Here, we report a combined experimental and kinetic modeling study of the composition and formation mechanisms of acyl RO.sub.2, as well as their contributions to the formation of highly oxygenated organic molecules (HOMs) during ozonolysis of α-pinene. We find that acyl RO.sub.2 radicals account for 67 %, 94 %, and 32 % of the highly oxygenated C.sub.7, C.sub.8, and C.sub.9 RO.sub.2, respectively, but only a few percent of C.sub.10 RO.sub.2 . The formation pathway of acyl RO.sub.2 species depends on their oxygenation level. The highly oxygenated acyl RO.sub.2 (oxygen atom number â¥6) are mainly formed by the intramolecular aldehydic H shift (i.e., autoxidation) of RO.sub.2, while the less oxygenated acyl RO.sub.2 (oxygen atom number |
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However, direct probing of the molecular identities and chemistry of acyl RO.sub.2 remains quite limited. Here, we report a combined experimental and kinetic modeling study of the composition and formation mechanisms of acyl RO.sub.2, as well as their contributions to the formation of highly oxygenated organic molecules (HOMs) during ozonolysis of α-pinene. We find that acyl RO.sub.2 radicals account for 67 %, 94 %, and 32 % of the highly oxygenated C.sub.7, C.sub.8, and C.sub.9 RO.sub.2, respectively, but only a few percent of C.sub.10 RO.sub.2 . The formation pathway of acyl RO.sub.2 species depends on their oxygenation level. The highly oxygenated acyl RO.sub.2 (oxygen atom number â¥6) are mainly formed by the intramolecular aldehydic H shift (i.e., autoxidation) of RO.sub.2, while the less oxygenated acyl RO.sub.2 (oxygen atom number <6) are basically derived from the C-C bond cleavage of alkoxy (RO) radicals containing an α-ketone group or the intramolecular H shift of RO containing an aldehyde group. The acyl-RO.sub.2 -involved reactions explain 50 %-90 % of C.sub.7 and C.sub.8 closed-shell HOMs and 14 % of C.sub.10 HOMs, respectively. For C.sub.9 HOMs, this contribution can be up to 30 %-60 %. In addition, acyl RO.sub.2 contribute to 50 %-95 % of C.sub.14 -C.sub.18 HOM dimer formation. Because of the generally fast reaction kinetics of acyl RO.sub.2, the acyl RO.sub.2 + alkyl RO.sub.2 reactions seem to outcompete the alkyl RO.sub.2 + alkyl RO.sub.2 pathways, thereby affecting the fate of alkyl RO.sub.2 and HOM formation. Our study sheds lights on the detailed formation pathways of the monoterpene-derived acyl RO.sub.2 and their contributions to HOM formation, which will help to understand the oxidation chemistry of monoterpenes and sources of low-volatility organic compounds capable of driving particle formation and growth in the atmosphere.</description><identifier>ISSN: 1680-7316</identifier><language>eng</language><publisher>Copernicus GmbH</publisher><ispartof>Atmospheric chemistry and physics, 2023-10, Vol.23 (19), p.12691</ispartof><rights>COPYRIGHT 2023 Copernicus GmbH</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784</link.rule.ids></links><search><creatorcontrib>Zang, Han</creatorcontrib><creatorcontrib>Huang, Dandan</creatorcontrib><creatorcontrib>Zhong, Jiali</creatorcontrib><creatorcontrib>Li, Ziyue</creatorcontrib><creatorcontrib>Li, Chenxi</creatorcontrib><creatorcontrib>Xiao, Huayun</creatorcontrib><creatorcontrib>Zhao, Yue</creatorcontrib><title>Direct probing of acylperoxy radicals during ozonolysis of α-pinene: constraints on radical chemistry and production of highly oxygenated organic molecules</title><title>Atmospheric chemistry and physics</title><description>Acylperoxy radicals (RO.sub.2) are key intermediates in the atmospheric oxidation of organic compounds and different from the general alkyl RO.sub.2 radicals in reactivity. However, direct probing of the molecular identities and chemistry of acyl RO.sub.2 remains quite limited. Here, we report a combined experimental and kinetic modeling study of the composition and formation mechanisms of acyl RO.sub.2, as well as their contributions to the formation of highly oxygenated organic molecules (HOMs) during ozonolysis of α-pinene. We find that acyl RO.sub.2 radicals account for 67 %, 94 %, and 32 % of the highly oxygenated C.sub.7, C.sub.8, and C.sub.9 RO.sub.2, respectively, but only a few percent of C.sub.10 RO.sub.2 . The formation pathway of acyl RO.sub.2 species depends on their oxygenation level. The highly oxygenated acyl RO.sub.2 (oxygen atom number â¥6) are mainly formed by the intramolecular aldehydic H shift (i.e., autoxidation) of RO.sub.2, while the less oxygenated acyl RO.sub.2 (oxygen atom number <6) are basically derived from the C-C bond cleavage of alkoxy (RO) radicals containing an α-ketone group or the intramolecular H shift of RO containing an aldehyde group. The acyl-RO.sub.2 -involved reactions explain 50 %-90 % of C.sub.7 and C.sub.8 closed-shell HOMs and 14 % of C.sub.10 HOMs, respectively. For C.sub.9 HOMs, this contribution can be up to 30 %-60 %. In addition, acyl RO.sub.2 contribute to 50 %-95 % of C.sub.14 -C.sub.18 HOM dimer formation. Because of the generally fast reaction kinetics of acyl RO.sub.2, the acyl RO.sub.2 + alkyl RO.sub.2 reactions seem to outcompete the alkyl RO.sub.2 + alkyl RO.sub.2 pathways, thereby affecting the fate of alkyl RO.sub.2 and HOM formation. Our study sheds lights on the detailed formation pathways of the monoterpene-derived acyl RO.sub.2 and their contributions to HOM formation, which will help to understand the oxidation chemistry of monoterpenes and sources of low-volatility organic compounds capable of driving particle formation and growth in the atmosphere.</description><issn>1680-7316</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2023</creationdate><recordtype>article</recordtype><recordid>eNptkMtKAzEUhmehYK2-Q8CVi5FkOpeMu1JvhYLgZV3Sk5NpZJqUyQx0fAgfwXfwFfTFPPUCFuQsAuf__vz5sxcNRC55XIxEfhAdhvDEeZJxkQ6i1wvbILRs3fiFdRXzhino6zU2ftOzRmkLqg5Md82X-uydr_tgwxb8eHl_i9fWocNzBt6FtlHWtaS5XyeDJa4sCT1TTm9TdAetJYD8S1st655RUIVOtaiZbyrlLLCVrxG6GsNRtG8oH49_zmH0eHX5MLmJZ7fX08l4FleCizIuJBQqyTKJqMscRIJgVKKNKhMgIF1IkSWl0kVpjISMZwLyNAFp0lQUnMvRMDr5vrdSNc6tM566AL0c5uMil9moGOUlUWf_UDSaStIHoLG03zGc7hiIaXHTVqoLYT69v_vLfgLyhYcf</recordid><startdate>20231011</startdate><enddate>20231011</enddate><creator>Zang, Han</creator><creator>Huang, Dandan</creator><creator>Zhong, Jiali</creator><creator>Li, Ziyue</creator><creator>Li, Chenxi</creator><creator>Xiao, Huayun</creator><creator>Zhao, Yue</creator><general>Copernicus GmbH</general><scope>ISR</scope></search><sort><creationdate>20231011</creationdate><title>Direct probing of acylperoxy radicals during ozonolysis of α-pinene: constraints on radical chemistry and production of highly oxygenated organic molecules</title><author>Zang, Han ; Huang, Dandan ; Zhong, Jiali ; Li, Ziyue ; Li, Chenxi ; Xiao, Huayun ; Zhao, Yue</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-g1019-78c7a2558eed96c12ecfa2dfa92c1014b81529ad79ff8c5051c642c8f44170083</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2023</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Zang, Han</creatorcontrib><creatorcontrib>Huang, Dandan</creatorcontrib><creatorcontrib>Zhong, Jiali</creatorcontrib><creatorcontrib>Li, Ziyue</creatorcontrib><creatorcontrib>Li, Chenxi</creatorcontrib><creatorcontrib>Xiao, Huayun</creatorcontrib><creatorcontrib>Zhao, Yue</creatorcontrib><collection>Gale In Context: Science</collection><jtitle>Atmospheric chemistry and physics</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Zang, Han</au><au>Huang, Dandan</au><au>Zhong, Jiali</au><au>Li, Ziyue</au><au>Li, Chenxi</au><au>Xiao, Huayun</au><au>Zhao, Yue</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Direct probing of acylperoxy radicals during ozonolysis of α-pinene: constraints on radical chemistry and production of highly oxygenated organic molecules</atitle><jtitle>Atmospheric chemistry and physics</jtitle><date>2023-10-11</date><risdate>2023</risdate><volume>23</volume><issue>19</issue><spage>12691</spage><pages>12691-</pages><issn>1680-7316</issn><abstract>Acylperoxy radicals (RO.sub.2) are key intermediates in the atmospheric oxidation of organic compounds and different from the general alkyl RO.sub.2 radicals in reactivity. However, direct probing of the molecular identities and chemistry of acyl RO.sub.2 remains quite limited. Here, we report a combined experimental and kinetic modeling study of the composition and formation mechanisms of acyl RO.sub.2, as well as their contributions to the formation of highly oxygenated organic molecules (HOMs) during ozonolysis of α-pinene. We find that acyl RO.sub.2 radicals account for 67 %, 94 %, and 32 % of the highly oxygenated C.sub.7, C.sub.8, and C.sub.9 RO.sub.2, respectively, but only a few percent of C.sub.10 RO.sub.2 . The formation pathway of acyl RO.sub.2 species depends on their oxygenation level. The highly oxygenated acyl RO.sub.2 (oxygen atom number â¥6) are mainly formed by the intramolecular aldehydic H shift (i.e., autoxidation) of RO.sub.2, while the less oxygenated acyl RO.sub.2 (oxygen atom number <6) are basically derived from the C-C bond cleavage of alkoxy (RO) radicals containing an α-ketone group or the intramolecular H shift of RO containing an aldehyde group. The acyl-RO.sub.2 -involved reactions explain 50 %-90 % of C.sub.7 and C.sub.8 closed-shell HOMs and 14 % of C.sub.10 HOMs, respectively. For C.sub.9 HOMs, this contribution can be up to 30 %-60 %. In addition, acyl RO.sub.2 contribute to 50 %-95 % of C.sub.14 -C.sub.18 HOM dimer formation. Because of the generally fast reaction kinetics of acyl RO.sub.2, the acyl RO.sub.2 + alkyl RO.sub.2 reactions seem to outcompete the alkyl RO.sub.2 + alkyl RO.sub.2 pathways, thereby affecting the fate of alkyl RO.sub.2 and HOM formation. Our study sheds lights on the detailed formation pathways of the monoterpene-derived acyl RO.sub.2 and their contributions to HOM formation, which will help to understand the oxidation chemistry of monoterpenes and sources of low-volatility organic compounds capable of driving particle formation and growth in the atmosphere.</abstract><pub>Copernicus GmbH</pub><tpages>12691</tpages></addata></record> |
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title | Direct probing of acylperoxy radicals during ozonolysis of α-pinene: constraints on radical chemistry and production of highly oxygenated organic molecules |
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