DOI: 10.1016/j.atmosenv.2014.05.063
Scopus记录号: 2-s2.0-84901479099
论文题名: Role of stabilized Criegee Intermediate in secondary organic aerosol formation from the ozonolysis of α-cedrene
作者: Yao L ; , Ma Y ; , Wang L ; , Zheng J ; , Khalizov A ; , Chen M ; , Zhou Y ; , Qi L ; , Cui F
刊名: Atmospheric Environment
ISSN: 0168-2563
EISSN: 1573-515X
出版年: 2014
卷: 94 起始页码: 448
结束页码: 457
语种: 英语
英文关键词: Criegee Intermediate
; Ozonolysis
; Reaction mechanism
; Secondary organic aerosol
; Sesquiterpene
; α-Cedrene
Scopus关键词: Atmospheric aerosols
; Decomposition
; Environmental chambers
; Experiments
; Free radicals
; Mass spectrometry
; Olefins
; Ozone
; Sulfur dioxide
; Criegee intermediates
; Ozonolysis
; Reaction mechanism
; Secondary organic aerosols
; Sesquiterpenes
; Reaction intermediates
; alcohol
; ammonium sulfate
; cyclohexane
; hydroxyl radical
; volatile organic compound
; aerosol
; chemical composition
; density
; mass spectrometry
; organic acid
; ozone
; particle size
; terpene
; alpha cedrene ozonolysis
; article
; atmospheric pressure
; chemical analysis
; controlled study
; criegee intermediate
; decomposition
; high performance liquid chromatography
; limit of detection
; mass spectrometry
; molecular weight
; ozonolysis
; photooxidation
; priority journal
; reaction analysis
; secondary organic aerosol
; signal noise ratio
Scopus学科分类: Environmental Science: Water Science and Technology
; Earth and Planetary Sciences: Earth-Surface Processes
; Environmental Science: Environmental Chemistry
英文摘要: Atmospheric ozonolysis of sesquiterpenes is an important source of secondary organic aerosols (SOA). The mechanisms by which Criegee Intermediates (CIs) react to form SOA precursors and the influence of environmental conditions, however, remain unclear. On the basis of environmental chamber experiments coupled with detailed characterization of gas-phase and particle-phase products, we present evidence that a significant fraction of CIs from ozonolysis of α-cedrene are stabilized and bimolecular reactions of these stabilized CIs (SCIs) play a key role in the formation of SOA precursors. Ozonolysis experiments were conducted in a 4.5m3 collapsible fluoropolymer chamber under various conditions in the presence of the OH radical and SCI scavengers. The size and mass of SOA particles produced during ozonolysis were measured directly and used for calculation of particle effective density and mass yield. Gaseous and particulate products were analyzed by several mass spectrometry methods. A total of 14 compounds in gas phase and 17 compounds in particle phase were tentatively identified. The major gas-phase products are secondary ozonides (SOZ) from intramolecular reactions of SCIs. Multifunctional organic acids are dominant particle-phase products. The measured density of aerosol particles is 1.04±0.03 to 1.38±0.03g/cm3, and the aerosol mass yield is (23.7±0.4)% to (46.4±6.5)%, depending on reaction conditions. The presence of acetic acid, an SCI scavenger, inhibits new particle formation, but leads to increased aerosol mass yield. In contrast, the addition of SO2 dramatically enhances new particle formation and total aerosol yield. The calculated OH formation yield decreases from (62.4±4.9)% to (9.0±1.6)% upon addition of SCI scavengers CH3COOH and SO2, indicating that a large fraction of excited CIs are collisionally stabilized and unimolecular decomposition of SCIs via the hydroperoxide channel can be suppressed by bimolecular reactions. The reaction of SCIs with SO2 leads to the formation of sulfuric acid, an important nucleation precursor. From the consumption of SO2 added as SCI scavenger, a lower-limit yield of SCIs from α-cedrene ozonolysis is estimated at ~88%. Our work underscores the key role of SCIs in SOA formation and observed composition of gas- and particle-phase products from α-cedrene ozonolysis. Bimolecular reactions of sesquiterpene CIs with atmospherically relevant species (e.g. SO2, H2O) need to be considered when assessing the atmospheric relevance of ozonolysis of sesquiterpenes. © 2014 Elsevier Ltd. Citation statistics:
资源类型: 期刊论文
标识符: http://119.78.100.158/handle/2HF3EXSE/80906
Appears in Collections: 气候变化事实与影响
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作者单位: School of Environmental Science and Engineering, Nanjing University of Information Science and Technology, Nanjing 210044, China; Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, Nanjing 210044, China; Department of Environmental Science and Engineering, Fudan University, Shanghai 200433, China; Department of Chemistry and Environmental Science, New Jersey Institute of Technology, Newark, NJ 07102, United States
Recommended Citation:
Yao L,, Ma Y,, Wang L,et al. Role of stabilized Criegee Intermediate in secondary organic aerosol formation from the ozonolysis of α-cedrene[J]. Atmospheric Environment,2014-01-01,94