AbstractOxidation chemistry controls both combustion processes and the atmospheric transformation of volatile emissions. In combustion engines, radical species undergo isomerization reactions that allow fast addition of O2. This chain reaction, termed autoxidation, is enabled by high engine temperatures, but has recently been also identified as an important source for highly oxygenated species in the atmosphere, forming organic aerosol. Conventional knowledge suggests that atmospheric autoxidation requires suitable structural features, like double bonds or oxygen-containing moieties, in the precursors. With neither of these functionalities, alkanes, the primary fuel type in combustion engines and an important class of urban trace gases, are thought to have minor susceptibility to extensive autoxidation. Here, utilizing state-of-the-art mass spectrometry, measuring both radicals and oxidation products, we show that alkanes undergo autoxidation much more efficiently than previously thought, both under atmospheric and combustion conditions. Even at high concentrations of NOX, which typically rapidly terminates autoxidation in urban areas, the studied C6–C10 alkanes produce considerable amounts of highly oxygenated products that can contribute to urban organic aerosol. The results of this inter-disciplinary effort provide crucial information on oxidation processes in both combustion engines and the atmosphere, with direct implications for engine efficiency and urban air quality.
Bibliographical noteKAUST Repository Item: Exported on 2021-02-23
Acknowledged KAUST grant number(s): OSR-2016-CRG5-3022
Acknowledgements: This work was supported by the National Natural Science Foundation of China (Grant 51976208), National Key Research and Development Program of China (Grant 2019YFA0405602), King Abdullah University of Science and Technology Office of Sponsored Research (Grant OSR-2016-CRG5-3022), the European Research Council (Grant 638703-COALA), the US National Science Foundation (Grant AGS1801897) and the Academy of Finland (Grants 299574, 326948, 307331, 317380, and 320094).