Rapid aqueous-phase dark reaction of phenols with nitrosonium ions: Novel mechanism for atmospheric nitrosation and nitration at low pH

Cai, Baohua1; Wang, Yixiang1; Yang, Xin1,2; Li, Yanchen1; Zhai, Jinghao1,2; Zeng, Yaling1,2; Ye, Jianhuai1,2; Zhu, Lei1,2; Fu, Tzung-May1,2; Zhang, Qi3

2024-09-18

10.1093/pnasnexus/pgae385

PNAS NEXUS   影响因子和分区

2752-6542

Dark aqueous-phase reactions involving the nitrosation and nitration of aromatic organic compounds play a significant role in the production of light-absorbing organic carbon in the atmosphere. This process constitutes a crucial aspect of tropospheric chemistry and has attracted growing research interest, particularly in understanding the mechanisms governing nighttime reactions between phenols and nitrogen oxides. In this study, we present new findings concerning the rapid dark reactions between phenols containing electron-donating groups and inorganic nitrite in acidic aqueous solutions with pH levels <3.5. This reaction generates a substantial amount of nitroso- and nitro-substituted phenolic compounds, known for their light-absorbing properties and toxicity. In experiments utilizing various substituted phenols, we demonstrate that their reaction rates with nitrite depend on the electron cloud density of the benzene ring, indicative of an electrophilic substitution reaction mechanism. Control experiments and theoretical calculations indicate that the nitrosonium ion (NO+) is the reactive nitrogen species responsible for undergoing electrophilic reactions with phenolate anions, leading to the formation of nitroso-substituted phenolic compounds. These compounds then undergo partial oxidation to form nitro-substituted phenols through reactions with nitrous acid (HONO) or other oxidants like oxygen. Our findings unveil a novel mechanism for swift atmospheric nitrosation and nitration reactions that occur within acidic cloud droplets or aerosol water, providing valuable insights into the rapid nocturnal formation of nitrogen-containing organic compounds with significant implications for climate dynamics and human health.

brown carbon phenols nitrosonium ions fast aqueous-phase dark reaction

ESCI

英语

第一 ; 通讯

Shenzhen Key Laboratory of Precision Measurement and Early Warning Technology for Urban Environmental Health Risks[ZDSYS20220606100604008] ; Guangdong Provincial Observation and Research Station for Coastal Atmosphere and Climate of the Greater Bay Area[2021B1212050024] ; Shenzhen Science and Technology Program["KQTD20210811090048025","KCXFZ20230731093601003"] ; U.S. National Science Foundation[AGS-2308645]

Science & Technology - Other Topics ; Social Sciences - Other Topics

Multidisciplinary Sciences ; Social Sciences, Interdisciplinary

WOS:001320899300003

OXFORD UNIV PRESS

Web of Science

1.Southern Univ Sci & Technol, Sch Environm Sci & Engn, Shenzhen Key Lab Precis Measurement & Early Warnin, Shenzhen 518055, Guangdong, Peoples R China
2.Prov Observat & Res Stn Coastal Atmosphere & Clima, Shenzhen 518055, Peoples R China
3.Univ Calif Davis, Dept Environm Toxicol, Davis, CA 95616 USA

Cai, Baohua,Wang, Yixiang,Yang, Xin,et al. Rapid aqueous-phase dark reaction of phenols with nitrosonium ions: Novel mechanism for atmospheric nitrosation and nitration at low pH[J]. PNAS NEXUS,2024,3(9).

Cai, Baohua.,Wang, Yixiang.,Yang, Xin.,Li, Yanchen.,Zhai, Jinghao.,...&Zhang, Qi.(2024).Rapid aqueous-phase dark reaction of phenols with nitrosonium ions: Novel mechanism for atmospheric nitrosation and nitration at low pH.PNAS NEXUS,3(9).

Cai, Baohua,et al."Rapid aqueous-phase dark reaction of phenols with nitrosonium ions: Novel mechanism for atmospheric nitrosation and nitration at low pH".PNAS NEXUS 3.9(2024).