Andrew H. Hallward-Driemeier, Jonathan R. Hall, Katie A. Spence, Benjamin P. Telicki, Amelia F. Schaeffer, Jose C. Avila, Isabel S. Albores and Anthony J. Carrasquillo*,
{"title":"二次有机气溶胶的形成和单官能团 C10 物种的羟基氧化化学反应","authors":"Andrew H. Hallward-Driemeier, Jonathan R. Hall, Katie A. Spence, Benjamin P. Telicki, Amelia F. Schaeffer, Jose C. Avila, Isabel S. Albores and Anthony J. Carrasquillo*, ","doi":"10.1021/acsearthspacechem.3c00180","DOIUrl":null,"url":null,"abstract":"<p >The formation of secondary organic aerosol (SOA), even from a simple hydrocarbon, is a complex, heterogeneous, multigenerational process involving hundreds of radical intermediate isomers and reaction pathways. Here, we compared the SOA generated from the reaction of the OH radical with five precursor species that differed in the identity of their primary functional group: <i>n</i>-decane, cyclodecane, 2-decanol, 2-decylnitrate, and 2-decanone. We compared results from smog chamber experiments and an explicit oxidation/gas-particle partitioning model of first-generation oxidation chemistry (Framework for 0-Dimensional Atmospheric Modeling–Washington Aerosol Module, F0AM-WAM) under two NO<sub><i>x</i></sub> regimes: lower NO<sub><i>x</i></sub> where RO<sub>2</sub> + HO<sub>2</sub> dominates and higher NO<sub><i>x</i></sub> where RO<sub>2</sub> + NO dominates. Our results show that while functional group identity impacted the vapor pressures of the precursor species, this alone was unable to explain trends in experimental yields. Functional groups also directed the site of initiation with the OH radical and the propagation and termination reactions that follow, with the most significant differences noted for 2-decanol. SOA production was greater in the lower NO<sub><i>x</i></sub> experiments for <i>n</i>-decane, 2-decanol, 2-decylnitrate, and 2-decanone due to production of the low volatility hydroperoxides and oxidized hydroxycarbonyls. Cyclodecane, however, produced more aerosol in higher NO<sub><i>x</i></sub> experiments, potentially due to the enhanced formation of low volatility acetals or dimers in the presence of greater concentrations of nitric acid. Finally, we predicted that as much as 67% of the first-generation products may undergo subsequent oxidation to later-generation species. While model results from first-generation chemistry alone are unable to predict experimentally observed yields and chemistry, this work provides a foundation for the incorporation of additional (e.g., later-generation or heterogeneous oxidation chemistry, condensed-phase reactions, etc.) processes.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9000,"publicationDate":"2024-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsearthspacechem.3c00180","citationCount":"0","resultStr":"{\"title\":\"Secondary Organic Aerosol Formation and Chemistry from the OH-Initiated Oxidation of Monofunctional C10 Species\",\"authors\":\"Andrew H. Hallward-Driemeier, Jonathan R. Hall, Katie A. Spence, Benjamin P. Telicki, Amelia F. Schaeffer, Jose C. Avila, Isabel S. Albores and Anthony J. Carrasquillo*, \",\"doi\":\"10.1021/acsearthspacechem.3c00180\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >The formation of secondary organic aerosol (SOA), even from a simple hydrocarbon, is a complex, heterogeneous, multigenerational process involving hundreds of radical intermediate isomers and reaction pathways. Here, we compared the SOA generated from the reaction of the OH radical with five precursor species that differed in the identity of their primary functional group: <i>n</i>-decane, cyclodecane, 2-decanol, 2-decylnitrate, and 2-decanone. We compared results from smog chamber experiments and an explicit oxidation/gas-particle partitioning model of first-generation oxidation chemistry (Framework for 0-Dimensional Atmospheric Modeling–Washington Aerosol Module, F0AM-WAM) under two NO<sub><i>x</i></sub> regimes: lower NO<sub><i>x</i></sub> where RO<sub>2</sub> + HO<sub>2</sub> dominates and higher NO<sub><i>x</i></sub> where RO<sub>2</sub> + NO dominates. Our results show that while functional group identity impacted the vapor pressures of the precursor species, this alone was unable to explain trends in experimental yields. Functional groups also directed the site of initiation with the OH radical and the propagation and termination reactions that follow, with the most significant differences noted for 2-decanol. SOA production was greater in the lower NO<sub><i>x</i></sub> experiments for <i>n</i>-decane, 2-decanol, 2-decylnitrate, and 2-decanone due to production of the low volatility hydroperoxides and oxidized hydroxycarbonyls. Cyclodecane, however, produced more aerosol in higher NO<sub><i>x</i></sub> experiments, potentially due to the enhanced formation of low volatility acetals or dimers in the presence of greater concentrations of nitric acid. Finally, we predicted that as much as 67% of the first-generation products may undergo subsequent oxidation to later-generation species. While model results from first-generation chemistry alone are unable to predict experimentally observed yields and chemistry, this work provides a foundation for the incorporation of additional (e.g., later-generation or heterogeneous oxidation chemistry, condensed-phase reactions, etc.) processes.</p>\",\"PeriodicalId\":15,\"journal\":{\"name\":\"ACS Earth and Space Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.9000,\"publicationDate\":\"2024-04-23\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.acs.org/doi/epdf/10.1021/acsearthspacechem.3c00180\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Earth and Space Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acsearthspacechem.3c00180\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Earth and Space Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acsearthspacechem.3c00180","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Secondary Organic Aerosol Formation and Chemistry from the OH-Initiated Oxidation of Monofunctional C10 Species
The formation of secondary organic aerosol (SOA), even from a simple hydrocarbon, is a complex, heterogeneous, multigenerational process involving hundreds of radical intermediate isomers and reaction pathways. Here, we compared the SOA generated from the reaction of the OH radical with five precursor species that differed in the identity of their primary functional group: n-decane, cyclodecane, 2-decanol, 2-decylnitrate, and 2-decanone. We compared results from smog chamber experiments and an explicit oxidation/gas-particle partitioning model of first-generation oxidation chemistry (Framework for 0-Dimensional Atmospheric Modeling–Washington Aerosol Module, F0AM-WAM) under two NOx regimes: lower NOx where RO2 + HO2 dominates and higher NOx where RO2 + NO dominates. Our results show that while functional group identity impacted the vapor pressures of the precursor species, this alone was unable to explain trends in experimental yields. Functional groups also directed the site of initiation with the OH radical and the propagation and termination reactions that follow, with the most significant differences noted for 2-decanol. SOA production was greater in the lower NOx experiments for n-decane, 2-decanol, 2-decylnitrate, and 2-decanone due to production of the low volatility hydroperoxides and oxidized hydroxycarbonyls. Cyclodecane, however, produced more aerosol in higher NOx experiments, potentially due to the enhanced formation of low volatility acetals or dimers in the presence of greater concentrations of nitric acid. Finally, we predicted that as much as 67% of the first-generation products may undergo subsequent oxidation to later-generation species. While model results from first-generation chemistry alone are unable to predict experimentally observed yields and chemistry, this work provides a foundation for the incorporation of additional (e.g., later-generation or heterogeneous oxidation chemistry, condensed-phase reactions, etc.) processes.
期刊介绍:
The scope of ACS Earth and Space Chemistry includes the application of analytical, experimental and theoretical chemistry to investigate research questions relevant to the Earth and Space. The journal encompasses the highly interdisciplinary nature of research in this area, while emphasizing chemistry and chemical research tools as the unifying theme. The journal publishes broadly in the domains of high- and low-temperature geochemistry, atmospheric chemistry, marine chemistry, planetary chemistry, astrochemistry, and analytical geochemistry. ACS Earth and Space Chemistry publishes Articles, Letters, Reviews, and Features to provide flexible formats to readily communicate all aspects of research in these fields.