Mechanistic study of the formation of ring-retaining and ring-opening products from the oxidation of aromatic compounds under urban atmospheric conditions
Aromatic hydrocarbons make up a large fraction of anthropogenic volatile organic compounds and contribute significantly to the production of tropospheric ozone and secondary organic aerosol (SOA). Four toluene and four 1,2,4-trimethylbenzene (1,2,4-TMB) photooxidation experiments were performed in a...
| Main Authors: | , , , , , , , , , , , , , |
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| Other Authors: | |
| Format: | Article |
| Language: | English |
| Published: |
Copernicus GmbH
2020
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| Online Access: | https://hdl.handle.net/1721.1/125755 |
| _version_ | 1826197408508280832 |
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| author | Zaytsev, Alexander Koss, Abigail R. Breitenlechner, Martin Krechmer, Jordan E. Nihill, Kevin J. Lim, Christopher Yung-Ta Rowe, James Clifford. Cox, Joshua L. Moss, Joshua Alexandre Roscioli, Joseph R. Canagaratna, Manjula R. Worsnop, Douglas R. Kroll, Jesse Keutsch, Frank N. |
| author2 | Massachusetts Institute of Technology. Department of Civil and Environmental Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Civil and Environmental Engineering Zaytsev, Alexander Koss, Abigail R. Breitenlechner, Martin Krechmer, Jordan E. Nihill, Kevin J. Lim, Christopher Yung-Ta Rowe, James Clifford. Cox, Joshua L. Moss, Joshua Alexandre Roscioli, Joseph R. Canagaratna, Manjula R. Worsnop, Douglas R. Kroll, Jesse Keutsch, Frank N. |
| author_sort | Zaytsev, Alexander |
| collection | MIT |
| description | Aromatic hydrocarbons make up a large fraction of anthropogenic volatile organic compounds and contribute significantly to the production of tropospheric ozone and secondary organic aerosol (SOA). Four toluene and four 1,2,4-trimethylbenzene (1,2,4-TMB) photooxidation experiments were performed in an environmental chamber under relevant polluted conditions (NOx ~ 10 ppb). An extensive suite of instrumentation including two proton-transferreaction mass spectrometers (PTR-MS) and two chemical ionisation mass spectrometers (NHC 4 CIMS and I- CIMS) allowed for quantification of reactive carbon in multiple generations of hydroxyl radical (OH)-initiated oxidation. Oxidation of both species produces ring-retaining products such as cresols, benzaldehydes, and bicyclic intermediate compounds, as well as ring-scission products such as epoxides and dicarbonyls. We show that the oxidation of bicyclic intermediate products leads to the formation of compounds with high oxygen content (an O V C ratio of up to 1.1). These compounds, previously identified as highly oxygenated molecules (HOMs), are produced by more than one pathway with differing numbers of reaction steps with OH, including both auto-oxidation and phenolic pathways. We report the elemental composition of these compounds formed under relevant urban high-NO conditions. We show that ringretaining products for these two precursors are more diverse and abundant than predicted by current mechanisms. We present the speciated elemental composition of SOA for both precursors and confirm that highly oxygenated products make up a significant fraction of SOA. Ring-scission products are also detected in both the gas and particle phases, and their yields and speciation generally agree with the kinetic model prediction. |
| first_indexed | 2024-09-23T10:47:15Z |
| format | Article |
| id | mit-1721.1/125755 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T10:47:15Z |
| publishDate | 2020 |
| publisher | Copernicus GmbH |
| record_format | dspace |
| spelling | mit-1721.1/1257552022-09-30T23:02:47Z Mechanistic study of the formation of ring-retaining and ring-opening products from the oxidation of aromatic compounds under urban atmospheric conditions Zaytsev, Alexander Koss, Abigail R. Breitenlechner, Martin Krechmer, Jordan E. Nihill, Kevin J. Lim, Christopher Yung-Ta Rowe, James Clifford. Cox, Joshua L. Moss, Joshua Alexandre Roscioli, Joseph R. Canagaratna, Manjula R. Worsnop, Douglas R. Kroll, Jesse Keutsch, Frank N. Massachusetts Institute of Technology. Department of Civil and Environmental Engineering Aromatic hydrocarbons make up a large fraction of anthropogenic volatile organic compounds and contribute significantly to the production of tropospheric ozone and secondary organic aerosol (SOA). Four toluene and four 1,2,4-trimethylbenzene (1,2,4-TMB) photooxidation experiments were performed in an environmental chamber under relevant polluted conditions (NOx ~ 10 ppb). An extensive suite of instrumentation including two proton-transferreaction mass spectrometers (PTR-MS) and two chemical ionisation mass spectrometers (NHC 4 CIMS and I- CIMS) allowed for quantification of reactive carbon in multiple generations of hydroxyl radical (OH)-initiated oxidation. Oxidation of both species produces ring-retaining products such as cresols, benzaldehydes, and bicyclic intermediate compounds, as well as ring-scission products such as epoxides and dicarbonyls. We show that the oxidation of bicyclic intermediate products leads to the formation of compounds with high oxygen content (an O V C ratio of up to 1.1). These compounds, previously identified as highly oxygenated molecules (HOMs), are produced by more than one pathway with differing numbers of reaction steps with OH, including both auto-oxidation and phenolic pathways. We report the elemental composition of these compounds formed under relevant urban high-NO conditions. We show that ringretaining products for these two precursors are more diverse and abundant than predicted by current mechanisms. We present the speciated elemental composition of SOA for both precursors and confirm that highly oxygenated products make up a significant fraction of SOA. Ring-scission products are also detected in both the gas and particle phases, and their yields and speciation generally agree with the kinetic model prediction. NSF award (AGS-1638672) Core Center grant (grant no. P30-ES002109) from the National Institute of Environmental Health Sciences, National Institutes of Health National Science Foundation (grant no. AGS-1638672) National Institute of Environmental Health Sciences (grant no. P30-ES002109) Austrian Science Fund (grant no. J-3900) 2020-06-09T21:28:19Z 2020-06-09T21:28:19Z 2019-12 2019-11 2020-05-28T17:18:54Z Article http://purl.org/eprint/type/JournalArticle 1680-7316 1680-7324 https://hdl.handle.net/1721.1/125755 Zaytsev, Alexander, et al. "Mechanistic study of the formation of ring-retaining and ring-opening products from the oxidation of aromatic compounds under urban atmospheric conditions." Atmospheric Chemistry and Physics, 19, 23 (December 2019): 1511-15129. © 2019 Author(s). en http://dx.doi.org/10.5194/ACP-19-15117-2019 Atmospheric Chemistry and Physics Creative Commons Attribution 4.0 International license https://creativecommons.org/licenses/by/4.0/ application/pdf Copernicus GmbH Copernicus Publications |
| spellingShingle | Zaytsev, Alexander Koss, Abigail R. Breitenlechner, Martin Krechmer, Jordan E. Nihill, Kevin J. Lim, Christopher Yung-Ta Rowe, James Clifford. Cox, Joshua L. Moss, Joshua Alexandre Roscioli, Joseph R. Canagaratna, Manjula R. Worsnop, Douglas R. Kroll, Jesse Keutsch, Frank N. Mechanistic study of the formation of ring-retaining and ring-opening products from the oxidation of aromatic compounds under urban atmospheric conditions |
| title | Mechanistic study of the formation of ring-retaining and ring-opening products from the oxidation of aromatic compounds under urban atmospheric conditions |
| title_full | Mechanistic study of the formation of ring-retaining and ring-opening products from the oxidation of aromatic compounds under urban atmospheric conditions |
| title_fullStr | Mechanistic study of the formation of ring-retaining and ring-opening products from the oxidation of aromatic compounds under urban atmospheric conditions |
| title_full_unstemmed | Mechanistic study of the formation of ring-retaining and ring-opening products from the oxidation of aromatic compounds under urban atmospheric conditions |
| title_short | Mechanistic study of the formation of ring-retaining and ring-opening products from the oxidation of aromatic compounds under urban atmospheric conditions |
| title_sort | mechanistic study of the formation of ring retaining and ring opening products from the oxidation of aromatic compounds under urban atmospheric conditions |
| url | https://hdl.handle.net/1721.1/125755 |
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