Rapid Production of Highly Oxidized Molecules in Isoprene Aerosol via Peroxy and Alkoxy Radical Isomerization Pathways in Low and High NO(x) Environments: Combined Laboratory, Computational and Field Studies
| Autor: | Krzysztof J. Rudzinski, Mohammed Jaoui, Rafal Szmigielski, Ivan R. Piletic, Theran P. Riedel, Tadeusz E. Kleindienst, Michael Lewandowski |
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| Jazyk: | angličtina |
| Rok vydání: | 2021 |
| Předmět: |
Aerosols
Chemical ionization Environmental Engineering Ozone Autoxidation Radical Photochemistry Pollution Article chemistry.chemical_compound Hemiterpenes chemistry Isomerism Alcohols Alkoxy group Butadienes Environmental Chemistry Laboratories Waste Management and Disposal Isomerization Isoprene NOx |
| Zdroj: | Sci Total Environ |
| Popis: | Recently, we identified seven novel hydroxy-carboxylic acids resulting from gas-phase reactions of isoprene in the presence of nitrogen oxides (NO(x)), ozone (O(3)), and/or hydroxyl radicals (OH). In the present study, we provide evidence that hydroxy-carboxylic acids, namely methyltartaric acids (MTA) are: (1) reliable isoprene tracers, (2) likely produced via rapid peroxy radical hydrogen atom (H) shift reactions (autoxidation mechanism) and analogous alkoxy radical H shifts in low and high NO(x) environments respectively and (3) representative of aged ambient aerosol in the low NO(x) regime. Firstly, MTA are reliable tracers of isoprene aerosol because they have been identified in numerous chamber experiments involving isoprene conducted under a wide range of conditions and are absent in the oxidation of mono- and sesquiterpenes. They are also present in numerous samples of ambient aerosol collected during the past 20 years at several locations in the U.S. and Europe. Furthermore, MTA concentrations measured during a year-long field study in Research Triangle Park (RTP), NC in 2003 show a seasonal trend consistent with isoprene emissions and photochemical activity. Secondly, an analysis of chemical ionization mass spectrometer (CIMS) data of several chamber experiments in low and high NO(x) environments show that highly oxidized molecules (HOMs) derived from isoprene that lead to MTAs may be produced rapidly and considered as early generation isoprene oxidation products in the gas phase. Density functional theory calculations show that rapid intramolecular H shifts involving peroxy and alkoxy radicals possess low barriers for methyl-hydroxy-butenals (MHBs) that may represent precursors for MTA. From these results, a viable rapid H shift mechanism is proposed to occur that produces isoprene derived HOMs like MTA. Finally, an analysis of the mechanism shows that autoxidation-like pathways in low and high NO(x) may produce HOMs in a few OH oxidation steps like commonly detected methyl tetrol (MT) isoprene tracers. The ratio of MTA/MT in isoprene aerosol is also shown to be significantly greater in field versus chamber samples indicating the importance of such pathways in the atmosphere even for smaller hydrocarbons like isoprene. |
| Databáze: | OpenAIRE |
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