Carbonate radical ion as a key driver of rapid atmospheric sulfate formation

Abstract Carbonate radical anion ( $${{\rm{CO}}}_{{3}^{.-}}$$ CO 3 . − ) is generally considered as a marginal intermediate that rarely regulates atmospheric-relevant reactions of significance. Unexpectedly, in this work, employing a suit of the in-field measurements, lab-based validations, improved...

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Main Authors: Yangyang Liu, Xiao Li, Qiuyue Ge, Xiaozhong Fang, Tao Wang, Wenbo You, Wei Wang, Lifang Xie, Kejian Li, Kedong Gong, Le Yang, Runbo Wang, Jilun Wang, Licheng Wang, Minglu Ma, Tingting Huang, Hongbo Fu, Jianmin Chen, Xinyi Dong, Liwu Zhang
Format: Article
Language:English
Published: Nature Portfolio 2025-02-01
Series:npj Climate and Atmospheric Science
Online Access:https://doi.org/10.1038/s41612-025-00905-4
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author Yangyang Liu
Xiao Li
Qiuyue Ge
Xiaozhong Fang
Tao Wang
Wenbo You
Wei Wang
Lifang Xie
Kejian Li
Kedong Gong
Le Yang
Runbo Wang
Jilun Wang
Licheng Wang
Minglu Ma
Tingting Huang
Hongbo Fu
Jianmin Chen
Xinyi Dong
Liwu Zhang
author_facet Yangyang Liu
Xiao Li
Qiuyue Ge
Xiaozhong Fang
Tao Wang
Wenbo You
Wei Wang
Lifang Xie
Kejian Li
Kedong Gong
Le Yang
Runbo Wang
Jilun Wang
Licheng Wang
Minglu Ma
Tingting Huang
Hongbo Fu
Jianmin Chen
Xinyi Dong
Liwu Zhang
author_sort Yangyang Liu
collection DOAJ
description Abstract Carbonate radical anion ( $${{\rm{CO}}}_{{3}^{.-}}$$ CO 3 . − ) is generally considered as a marginal intermediate that rarely regulates atmospheric-relevant reactions of significance. Unexpectedly, in this work, employing a suit of the in-field measurements, lab-based validations, improved kinetic numerical calculations, and chemical transport modeling, we demonstrate that $${{\rm{CO}}}_{{3}^{.-}}$$ CO 3 . − gives a significantly overlooked contribution (~54.4%) to overall secondary sulfate formation during dust storm-relevant episodes and ~236.3% increase of SO2 uptake over mineral dust pathway during haze-relevant periods. GEOS-Chem modeling results further emphasize the important position of this radical ion in dust-driven SO2 oxidation chemistry. Our finding leaves this active intermediate no longer a marginal oxidant currently prevailing in the framework of the atmospheric science community. More importantly, after considering this rapid dust-driven sulfate formation channel mediated by carbonate radicals during pollution episodes, this study provides a clear indication that high priority should be given to reducing alkaline soil dust emissions to achieve benefits for air quality.
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institution DOAJ
issn 2397-3722
language English
publishDate 2025-02-01
publisher Nature Portfolio
record_format Article
series npj Climate and Atmospheric Science
spelling doaj-art-3958e14b629a4f648963ebe3d46f14ee2025-08-20T02:48:11ZengNature Portfolionpj Climate and Atmospheric Science2397-37222025-02-018111210.1038/s41612-025-00905-4Carbonate radical ion as a key driver of rapid atmospheric sulfate formationYangyang Liu0Xiao Li1Qiuyue Ge2Xiaozhong Fang3Tao Wang4Wenbo You5Wei Wang6Lifang Xie7Kejian Li8Kedong Gong9Le Yang10Runbo Wang11Jilun Wang12Licheng Wang13Minglu Ma14Tingting Huang15Hongbo Fu16Jianmin Chen17Xinyi Dong18Liwu Zhang19Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science and Engineering, Fudan UniversitySchool of Atmospheric Sciences, Nanjing UniversityShanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science and Engineering, Fudan UniversityShanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science and Engineering, Fudan UniversityShanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science and Engineering, Fudan UniversityShanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science and Engineering, Fudan UniversityShanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science and Engineering, Fudan UniversityShanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science and Engineering, Fudan UniversityShanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science and Engineering, Fudan UniversityShanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science and Engineering, Fudan UniversityShanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science and Engineering, Fudan UniversityShanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science and Engineering, Fudan UniversityShanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science and Engineering, Fudan UniversityShanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science and Engineering, Fudan UniversityShanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science and Engineering, Fudan UniversityShanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science and Engineering, Fudan UniversityShanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science and Engineering, Fudan UniversityShanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science and Engineering, Fudan UniversitySchool of Atmospheric Sciences, Nanjing UniversityShanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science and Engineering, Fudan UniversityAbstract Carbonate radical anion ( $${{\rm{CO}}}_{{3}^{.-}}$$ CO 3 . − ) is generally considered as a marginal intermediate that rarely regulates atmospheric-relevant reactions of significance. Unexpectedly, in this work, employing a suit of the in-field measurements, lab-based validations, improved kinetic numerical calculations, and chemical transport modeling, we demonstrate that $${{\rm{CO}}}_{{3}^{.-}}$$ CO 3 . − gives a significantly overlooked contribution (~54.4%) to overall secondary sulfate formation during dust storm-relevant episodes and ~236.3% increase of SO2 uptake over mineral dust pathway during haze-relevant periods. GEOS-Chem modeling results further emphasize the important position of this radical ion in dust-driven SO2 oxidation chemistry. Our finding leaves this active intermediate no longer a marginal oxidant currently prevailing in the framework of the atmospheric science community. More importantly, after considering this rapid dust-driven sulfate formation channel mediated by carbonate radicals during pollution episodes, this study provides a clear indication that high priority should be given to reducing alkaline soil dust emissions to achieve benefits for air quality.https://doi.org/10.1038/s41612-025-00905-4
spellingShingle Yangyang Liu
Xiao Li
Qiuyue Ge
Xiaozhong Fang
Tao Wang
Wenbo You
Wei Wang
Lifang Xie
Kejian Li
Kedong Gong
Le Yang
Runbo Wang
Jilun Wang
Licheng Wang
Minglu Ma
Tingting Huang
Hongbo Fu
Jianmin Chen
Xinyi Dong
Liwu Zhang
Carbonate radical ion as a key driver of rapid atmospheric sulfate formation
npj Climate and Atmospheric Science
title Carbonate radical ion as a key driver of rapid atmospheric sulfate formation
title_full Carbonate radical ion as a key driver of rapid atmospheric sulfate formation
title_fullStr Carbonate radical ion as a key driver of rapid atmospheric sulfate formation
title_full_unstemmed Carbonate radical ion as a key driver of rapid atmospheric sulfate formation
title_short Carbonate radical ion as a key driver of rapid atmospheric sulfate formation
title_sort carbonate radical ion as a key driver of rapid atmospheric sulfate formation
url https://doi.org/10.1038/s41612-025-00905-4
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