Theoretical study on the atmospheric transformation mechanism of pirimiphos-methyl initiated by O-3
文献类型：期刊论文
| 作者 | Yang, Bo; Wang, Youfeng; Shu, Jinian; Zhang, Peng; Sun, Wanqi; Li, Nana; Zhang, Yani |
| 刊名 | CHEMOSPHERE
 |
| 出版日期 | 2015-11 |
| 卷号 | 138期号:1页码:966-972 |
| 关键词 | Pirimiphos-methyl Reaction mechanism O-3 Pesticides DFT Atmospheric transformation |
| 英文摘要 | Pirimiphos-methyl (PMM) is a widely used organophosphorus pesticide that can be released into the atmosphere in gas and condensed phases. It possesses a P=S bond and an N,N-dialkyl group adjacent to pyrimidine, which are common functional groups for pesticides. Currently, the reaction mechanisms of O-3 with these functional groups are poorly understood. In this study, the mechanisms and possible degradation products for O-3-initiated atmospheric oxidation of PMM were investigated using the Density Functional Theory (DFT) method. The results show that H abstraction from the alpha carbon of the N,N-diethyl group and its subsequent reactions (hydroxylation, N-dealkylation, and carbonylation reactions), as well as the transformation of the P=S bond to the P=O oxone form, are the most favorable reaction pathways for PMM and O-3. The Gibbs free energy (Delta G) indicates that the subsequent reactions tend to take place more spontaneously once the initial reaction occurs. In addition, theoretical calculations indicate that water can serve as an effective catalyst in the N-dealkylation reaction process. Water-assisted reactions lead to the activation energy decreasing by 20.2 kcal mol(-1) compared with direct reactions, and thus may represent a dominant reaction pathway for the N-dealkylation process in the atmosphere. These theoretical results provide new insights into O-3-initiated degradation of PMM and its analogues. (C) 2014 Elsevier Ltd. All rights reserved. |
| 研究领域[WOS] | Environmental Sciences |
| WOS记录号 | WOS:000361772800127 |
| 公开日期 | 2016-03-08 |
| 源URL | [http://ir.rcees.ac.cn/handle/311016/32459]  |
| 专题 | 生态环境研究中心_大气环境科学实验室 |
| 推荐引用方式 GB/T 7714 | Yang, Bo,Wang, Youfeng,Shu, Jinian,et al. Theoretical study on the atmospheric transformation mechanism of pirimiphos-methyl initiated by O-3[J]. CHEMOSPHERE,2015,138(1):966-972. |
| APA | Yang, Bo.,Wang, Youfeng.,Shu, Jinian.,Zhang, Peng.,Sun, Wanqi.,...&Zhang, Yani.(2015).Theoretical study on the atmospheric transformation mechanism of pirimiphos-methyl initiated by O-3.CHEMOSPHERE,138(1),966-972. |
| MLA | Yang, Bo,et al."Theoretical study on the atmospheric transformation mechanism of pirimiphos-methyl initiated by O-3".CHEMOSPHERE 138.1(2015):966-972. |
入库方式： OAI收割
来源：生态环境研究中心
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