Halogenation of polycyclic aromatic hydrocarbons by photochemical reaction under simulated tidal flat conditions
Halogenation of polycyclic aromatic hydrocarbons by photochemical reaction under simulated tidal flat conditions
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模拟滩涂条件下多环芳烃的光化学反应卤化
DOI：
10.1080/10406638.2013.770406
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发表时间：
2013
影响因子：
2.4
通讯作者：
Shinohara R.
中科院分区：
文献类型：
--
作者：
Sankoda K.;Nomiyama K;Kuribayashi T.;Shinohara R.
选择6种多环芳烃（PAHs）（萘NA、菲PHE、蒽ANT、荧蒽FLR、芘PYR和苯并[a]芘B[a]P），在模拟潮滩条件下暴露于自然光，考察其在海岸环境中光化学生成卤代衍生物的可能性.根据PM 6哈密顿量，得到了11个分子描述符，光化学反应诱导了13种卤代衍生物的生成，其中包括7种未知产物。在所测定的6种卤代衍生物中，6-氯苯并[a]芘的生成量最高。此外，PYR表现出的行为，产生卤代衍生物显着高于其结构异构体的FLR。在确定生产量后，卤化衍生物的生产量和单个多环芳烃的分子描述符之间的相关性进行了检查。最高占据分子轨道和最低未占据分子轨道之间的能隙（EHOMO-LUMO）（其是化学稳定性的量度）显示出最强的显著性（p< 0.01），并且对结构异构体之间的产生量的差异给出了足够的解释。具有小EHOMO-LUMO的多环芳烃表现出很高的潜力，产生卤代衍生物。ANT、PYR和B[a]P在沿海环境中可能具有较高的诱导卤代衍生物的能力。进一步讨论了光化学反应对多环芳烃和卤代多环芳烃环境归趋的影响。在我们以前的实地调查中观察到的同系物配置文件似乎表明光化学反应的贡献发生的氯多环芳烃。
Selected six kinds of polycyclic aromatic hydrocarbons (PAHs) (naphthalene: NA, phenanthrene: (PHE), anthracene (ANT), fluoranthene (FLR), pyrene (PYR), and benzo[a]pyrene (B[a]P)) were exposed to natural sunlight under simulated tidal flat conditions, to check possibilities for photochemical productions of halogenated derivatives in the coastal environment. Moreover, 11 molecular descriptors were derived based on PM6 Hamiltonian for each PAH.Photochemical reaction induced productions of various 13 kinds of halogenated derivatives, which include 7 unknown products. In the determined 6 halogenated derivatives, the highest production amount was 6-chlorobenzo[a]pyrene. Moreover, PYR showed the behavior that produced halogenated derivatives significantly higher than its structural isomer of FLR. After the determination of production amounts, correlation between the production amounts of halogenated derivatives and the molecular descriptors of individual PAHs were examined. The energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital (EHOMO–LUMO), which is a measure of chemical stability, showed the strongest significance (p< 0.01) and give enough explanation for differences in the production amounts among structural isomers. PAHs that have small EHOMO–LUMOshowed high potential to produce halogenated derivatives. ANT, PYR and B[a]P would have potentially high capability to induce halogenated derivatives in the coastal environment. We further discussed the impact of photochemical reaction on environmental fate of PAHs and halogenated PAHs. Congener profiles observed in our previous field surveys seemed to suggest contributions of photochemical reaction to occurrences of Cl-PAHs.