Environment Research Institute, Shandong University, Binhai Road 72, Qingdao, 266237, China.
Environ Sci Pollut Res Int. 2018 Aug;25(24):24241-24252. doi: 10.1007/s11356-018-2504-2. Epub 2018 Jun 13.
Chloroalkenes are among the important anthropogenic organic compounds emitted in the atmosphere as a result of their wide use in synthetic processes in industry. Despite their well-known adverse effects on human health and air quality, the chemistry of these chloroalkenes remains poorly explored. In this work, reactions of 4-chloro-1-butene (CBE), a representative example of chloroalkenes, with O, OH, NO, and Cl are investigated in a 100-L Teflon reaction chamber equipped with gas chromatography-flame ionization detector (GC-FID). The absolute rate method was used for the reaction with O while the relative rate method was used for reactions with OH, NO, and Cl. The following rate constants were obtained at room temperature (298 ± 2) K and atmospheric pressure: (3.96 ± 0.43) × 10, (2.63 ± 0.96) × 10, (4.48 ± 1.23) × 10, and (2.35 ± 0.90) × 10 cm molecule s, for reactions with O, OH, NO, and Cl, respectively. Atmospheric lifetimes of CBE calculated from rate constants of the different reactions obtained in this work showed that reaction with OH is the main loss process for CBE, while in coastal areas and in the marine boundary layer, the CBE loss by Cl reaction becomes important. Estimation of the value of the photochemical ozone creation potential (POCP) indicated that CBE has a large ozone formation potential. The present work underlines the need for further studies on the atmospheric chemistry of chlorinated VOCs.
氯烯烃是由于在工业合成过程中的广泛应用而作为人为有机化合物排放到大气中的重要物质之一。尽管它们对人类健康和空气质量有明显的不利影响,但这些氯烯烃的化学性质仍未得到充分研究。在这项工作中,使用配备气相色谱-火焰离子化检测器(GC-FID)的 100-L 特氟隆反应室研究了代表氯烯烃的 4-氯-1-丁烯(CBE)与 O、OH、NO 和 Cl 的反应。对于与 O 的反应,使用绝对速率法,对于与 OH、NO 和 Cl 的反应,使用相对速率法。在室温(298 ± 2)K 和大气压下获得了以下速率常数:与 O 的反应速率常数为 (3.96 ± 0.43) × 10、与 OH 的反应速率常数为 (2.63 ± 0.96) × 10、与 NO 的反应速率常数为 (4.48 ± 1.23) × 10 和与 Cl 的反应速率常数为 (2.35 ± 0.90) × 10 cm 分子 s。根据本工作中获得的不同反应的速率常数计算的 CBE 大气寿命表明,与 OH 的反应是 CBE 的主要损失过程,而在沿海地区和海洋边界层中,Cl 反应的 CBE 损失变得重要。光化学臭氧产生潜能(POCP)值的估算表明 CBE 具有很大的臭氧形成潜能。本工作强调了进一步研究氯化挥发性有机化合物大气化学的必要性。