Multiphase reactions of organic peroxides and nitrite as a source of atmospheric organic nitrates
Abstract Organic nitrates (ONs) are considered as important tracers of secondary organic aerosol formation and are ubiquitous in ambient aerosols. However, the mechanisms of ON formation in the atmosphere are not well understood. Here, we show that ONs can be formed via multiphase reactions of organ...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2025-07-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-60696-3 |
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| author | Yu Yang Liubin Huang Min Zhao Yan Wu Yihang Xu Qinyi Li Wenxing Wang Likun Xue |
| author_facet | Yu Yang Liubin Huang Min Zhao Yan Wu Yihang Xu Qinyi Li Wenxing Wang Likun Xue |
| author_sort | Yu Yang |
| collection | DOAJ |
| description | Abstract Organic nitrates (ONs) are considered as important tracers of secondary organic aerosol formation and are ubiquitous in ambient aerosols. However, the mechanisms of ON formation in the atmosphere are not well understood. Here, we show that ONs can be formed via multiphase reactions of organic peroxides with nitrite. Yields of ONs are measured as 12.8–14.9% at pH 3. The mechanism involves the recombination of a [RO• •NO2] caged radical pair resulting from the homolytic cleavage of alkyl peroxynitrite intermediate. ON yield decreases with the decreasing pH values, which may be ascribed to the positive dependence of its hydrolysis rate on the solution acidity. Additionally, it is found that the second-order rate constant of the reaction is closely dependent on pH and the molecular structure of organic peroxides. Extrapolation of kinetic and mechanistic results to the real atmosphere suggests that this pathway is important for ON formation in aerosols under typical atmospheric conditions, particularly in polluted urban areas. |
| format | Article |
| id | doaj-art-07d5d9228ad343c1847d9300a2b65df9 |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-07-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-07d5d9228ad343c1847d9300a2b65df92025-08-20T03:45:35ZengNature PortfolioNature Communications2041-17232025-07-011611810.1038/s41467-025-60696-3Multiphase reactions of organic peroxides and nitrite as a source of atmospheric organic nitratesYu Yang0Liubin Huang1Min Zhao2Yan Wu3Yihang Xu4Qinyi Li5Wenxing Wang6Likun Xue7Environment Research Institute, Shandong UniversityEnvironment Research Institute, Shandong UniversityEnvironment Research Institute, Shandong UniversitySchool of Environmental Science and Engineering, Shandong UniversitySchool of Environmental Science and Engineering, Shandong UniversityEnvironment Research Institute, Shandong UniversityEnvironment Research Institute, Shandong UniversityEnvironment Research Institute, Shandong UniversityAbstract Organic nitrates (ONs) are considered as important tracers of secondary organic aerosol formation and are ubiquitous in ambient aerosols. However, the mechanisms of ON formation in the atmosphere are not well understood. Here, we show that ONs can be formed via multiphase reactions of organic peroxides with nitrite. Yields of ONs are measured as 12.8–14.9% at pH 3. The mechanism involves the recombination of a [RO• •NO2] caged radical pair resulting from the homolytic cleavage of alkyl peroxynitrite intermediate. ON yield decreases with the decreasing pH values, which may be ascribed to the positive dependence of its hydrolysis rate on the solution acidity. Additionally, it is found that the second-order rate constant of the reaction is closely dependent on pH and the molecular structure of organic peroxides. Extrapolation of kinetic and mechanistic results to the real atmosphere suggests that this pathway is important for ON formation in aerosols under typical atmospheric conditions, particularly in polluted urban areas.https://doi.org/10.1038/s41467-025-60696-3 |
| spellingShingle | Yu Yang Liubin Huang Min Zhao Yan Wu Yihang Xu Qinyi Li Wenxing Wang Likun Xue Multiphase reactions of organic peroxides and nitrite as a source of atmospheric organic nitrates Nature Communications |
| title | Multiphase reactions of organic peroxides and nitrite as a source of atmospheric organic nitrates |
| title_full | Multiphase reactions of organic peroxides and nitrite as a source of atmospheric organic nitrates |
| title_fullStr | Multiphase reactions of organic peroxides and nitrite as a source of atmospheric organic nitrates |
| title_full_unstemmed | Multiphase reactions of organic peroxides and nitrite as a source of atmospheric organic nitrates |
| title_short | Multiphase reactions of organic peroxides and nitrite as a source of atmospheric organic nitrates |
| title_sort | multiphase reactions of organic peroxides and nitrite as a source of atmospheric organic nitrates |
| url | https://doi.org/10.1038/s41467-025-60696-3 |
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