Nighttime reactions of a series of unsaturated alcohols with NO_(3)•:Kinetics,products and mechanisms study  

作　　者：Yanyong Xu Shengrui Tong Weiran Li Meifang Chen Lin Hu Hailiang Zhang Sufan Wang Maofa Ge 

机构地区：[1]State Key Laboratory for Structural Chemistry of Unstable and Stable Species,Chinese Academy of Sciences Research/Education Center for Excellence in Molecular Sciences,Institute of Chemistry Chinese Academy of Sciences,Beijing 100190,China [2]University of Chinese Academy of Sciences,Beijing 100049,China [3]College of Chemistry and Material Science,Anhui Normal University,Wuhu 241000,China [4]College of Ecology and Environment,Xinjiang University,Urumqi 830017,China

出　　处：《Journal of Environmental Sciences》2025年第5期331-346,共16页环境科学学报(英文版)

基　　金：supported by the National Key Research and Development Program of China(No.2020YFA0607800);the National Natural Science Foundation of China(Nos.42022039 and 42130606);Beijing National Laboratory for Molecular Sciences(No.BNLMS-CXXM-202011),the Youth Innovation Promotion Association of Chinese Academy of Sciences(No.Y2021013).

摘　　要：Unsaturated alcohols are a class of Biogenic volatile organic compounds(BVOCs)emitted in large quantities by plants when damaged or under adverse environmental conditions,and studies on their atmospheric degradation at night are still lacking.We used chamber experiments to study the gas-phase reactions of three unsaturated alcohols,E-2-penten-1-ol,Z-2-hexen-1-ol and Z-3-hepten-1-ol,with NO_(3)radicals(NO_(3)•)during the night.The rate constants of these reactions were(11.7±1.76)×10^(−13),(8.55±1.33)×10^(−13)and(6.08±0.47)×10^(−13)cm^(3)/(molecule·s)at 298K and 760 Torr,respectively.In contrast,the reaction rate of similar substances with ozone was about 10^(−18)cm^(3)/(molecule·s),which indicates that the reaction with NO_(3)•is themain oxidation pathway for unsaturated alcohols at night.Small molecule aldehydes and ketones were the main gas-phase organic products of the reaction of three aldehydes and ketones with NO_(3)•,and the total small molecule aldehydes and ketones yields can reach between 45%-60%.They mainly originate from the breakage of alkoxy radicals,and different breakage sites determine different product distributions.In addition,the SOA yields of the three unsaturated alcohols with NO_(3)•were 7.1%±1.0%,12.5%±1.9%and 30.0%±4.5%,respectively,whichweremuch higher than those of similarly structured substances with O_(3)or OH radicals(•OH).The results of high-resolution mass spectrometry shows that the main components of Secondary organic aerosol(SOA)of the three unsaturated alcohols are dimeric compounds containing several nitrate groups,which are formed through the polymerization of oxyalkyl radicals.

关 键 词：Unsaturated alcohols Reaction rate Aldehyde and ketone products Secondary organic aerosol components Reaction mechanism 

分 类 号：X51[环境科学与工程—环境工程]