Global S&T Development Trend Analysis Platform of Resources and Environment
DOI | 10.5194/acp-18-15105-2018 |
The oxidation regime and SOA composition in limonene ozonolysis: roles of different double bonds, radicals, and water | |
Gong, Yiwei; Chen, Zhongming; Li, Huan | |
2018-10-19 | |
发表期刊 | ATMOSPHERIC CHEMISTRY AND PHYSICS
![]() |
ISSN | 1680-7316 |
EISSN | 1680-7324 |
出版年 | 2018 |
卷号 | 18期号:20页码:15105-15123 |
文章类型 | Article |
语种 | 英语 |
国家 | Peoples R China |
英文摘要 | Volatile organic compounds play an important role in air quality and climate change, largely because they contribute to the formation of oxidizing compounds and secondary organic aerosol (SOA). In this study, a series of products, including peroxides and carbonyl compounds in both gaseous and particulate phases, were simultaneously detected to investigate the oxidation regime and SOA composition in limonene ozonolysis. The roles of different double bonds (DBs), radicals, and water were also examined In our first investigation, we focused on representative oxidizing compounds produced in limonene ozonolysis, including stabilized Criegee intermediates (SCIs), OH radicals, and peroxides. The dependence of H2O2 and hydroxymethyl hydroperoxide (HMHP) formation on RH demonstrates that the reaction with water is an important reaction pathway for limonene SCIs, and the lower limit SCI yields of endocyclic and exocyclic DBs were estimated to be similar to 0.24 and similar to 0.43, respectively. The OH yield was determined by adding sufficient amounts of an OH scavenger, and the OH yields of endocyclic and exocyclic DBs were similar to 0.65 and similar to 0.24, respectively. These results indicate that in limonene ozonolysis the endocyclic DB is inclined to generate OH radicals through the hydroperoxide channel, while the exocyclic DB has a higher fraction of forming SCIs. Additionally, other gas-phase and particle-phase peroxides were also studied in this work. The formation of performic acid (PFA) and peracetic acid (PAA) was promoted significantly by increasing RH and the degree of oxidation, and the discrepancy between the experimental and model results suggested some missing formation pathways. Considerable generation of H202 from SOA in the aqueous phase was observed, especially at a high [O-3] / [limonene] ratio, which was mainly attributed to the hydration and decomposition of unstable peroxides in SOA such as peroxycarboxylic acids and peroxyhemiacetals. Different DBs and OH scavengers had a large impact on the particulate peroxides, and their stability indicated that the types of peroxides in SOA changed under different conditions. As for the contribution of peroxides to SOA, the results demonstrated that the mass fraction of particulate peroxides in limonene SOA was less than 0.2 at a low [O-3] / [limonene] ratio, while the mass fraction was 0.40.6 at a high [O-3] / [limonene] ratio. The partitioning behavior of peroxides showed that multi-generation oxidation helped produce more low-volatility peroxides, which partially explained the higher SOA yield. The partitioning behavior of carbonyls was also examined and the experimental partitioning coefficients (K-r) were found to be typically several orders of magnitude higher than the theoretical values. This study provided new insights into the oxidation regime and SOA composition in limonene ozonolysis, and limonene showed its specificity in many aspects when both endocyclic and exocyclic DBs were ozonated. We suggest that the atmospheric implications of terpenes containing more than one DB and the SOA composition, especially particulate peroxides, need further study. |
领域 | 地球科学 |
收录类别 | SCI-E |
WOS记录号 | WOS:000447779800006 |
WOS关键词 | SECONDARY ORGANIC AEROSOL ; GAS-PHASE OZONOLYSIS ; STABILIZED CRIEGEE INTERMEDIATE ; CONFORMER-DEPENDENT REACTIVITY ; ATMOSPHERIC HYDROGEN-PEROXIDE ; OZONE-ALKENE REACTION ; BETA-PINENE ; OH RADICALS ; RELATIVE-HUMIDITY ; CARBONYL OXIDES |
WOS类目 | Environmental Sciences ; Meteorology & Atmospheric Sciences |
WOS研究方向 | Environmental Sciences & Ecology ; Meteorology & Atmospheric Sciences |
引用统计 | |
文献类型 | 期刊论文 |
条目标识符 | http://119.78.100.173/C666/handle/2XK7JSWQ/19499 |
专题 | 地球科学 |
作者单位 | Peking Univ, Coll Environm Sci & Engn, State Key Lab Environm Simulat & Pollut Control, Beijing 100871, Peoples R China |
推荐引用方式 GB/T 7714 | Gong, Yiwei,Chen, Zhongming,Li, Huan. The oxidation regime and SOA composition in limonene ozonolysis: roles of different double bonds, radicals, and water[J]. ATMOSPHERIC CHEMISTRY AND PHYSICS,2018,18(20):15105-15123. |
APA | Gong, Yiwei,Chen, Zhongming,&Li, Huan.(2018).The oxidation regime and SOA composition in limonene ozonolysis: roles of different double bonds, radicals, and water.ATMOSPHERIC CHEMISTRY AND PHYSICS,18(20),15105-15123. |
MLA | Gong, Yiwei,et al."The oxidation regime and SOA composition in limonene ozonolysis: roles of different double bonds, radicals, and water".ATMOSPHERIC CHEMISTRY AND PHYSICS 18.20(2018):15105-15123. |
条目包含的文件 | 条目无相关文件。 |
除非特别说明,本系统中所有内容都受版权保护,并保留所有权利。
修改评论