Acta Chim. Sinica ›› 2016, Vol. 74 ›› Issue (7): 557-564.DOI: 10.6023/A16040178 Previous Articles     Next Articles

Accounts

卤代芳烃在环境友好高级氧化过程中产生内源性化学发光的分子机制及应用研究

朱本占, 邵波, 毛莉, 高慧颖   

  1. 中国科学院生态环境研究中心 环境化学与生态毒理学国家重点实验室 北京 100085
  • 收稿日期:2016-04-11 出版日期:2016-07-15 发布日期:2016-07-19
  • 通讯作者: 朱本占 E-mail:bzhu@rcees.ac.cn
  • 基金资助:

    项目受中国科学院战略性先导科技专项(B类)(XDB01020300)、国家自然科学基金(21577149,21477139,21237005,21321004)和环境化学与生态毒理学国家重点实验室开放基金(KF2012-09)资助.

Intrinsic Chemiluminescence Production during Environmentally-friendly Advanced Oxidation of Halogenated Aromatics and Its Applications

Zhu Benzhan, Shao Bo, Mao Li, Gao Huiying   

  1. State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China
  • Received:2016-04-11 Online:2016-07-15 Published:2016-07-19
  • Supported by:

    Project supported by the Strategic Priority Research Program of CAS (Grant No. XDB01020300), National Natural Science Foundation of China (Nos. 21577149, 21477139, 21237005 and 21321004), and Open Foundation from State Key Laboratory of Environmental Chemistry and Ecotoxicology (No. KF2012-09).

Haloaromatics (XAr) have been widely used as pesticides, personal care agents, pharmaceuticals and flame retardants, which are now ubiquitously present in our environment. The carcinogenicity coupled with their ubiquitous occurrence have raised public concerns on the potential risks to both human health and the ecosystem posed by XAr. Advanced oxidation processes (AOPs) have been increasingly employed as an "environmentally-friendly" technology for remediating such highly toxic and recalcitrant XAr. During these AOPs systems, the most reactive radical intermediate formed at near-ambient temperature and pressure is the hydroxyl radical (·OH). Recently, we found that an intrinsic chemiluminescence can be generated during the advanced oxidation of the priority pollutant pentachlorophenol and all other XAr. Furtherly, by the complementary application of electron spin resonance (ESR) with 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as the spin-trapping agent, fluorescence method with terephthalic acid (TPA) as the ·OH probe, chemiluminescence analysis in the presence of classic ·OH scavengers and several typical ·OH-generating systems, the chemiluminescence was confirmed to be directly dependent on the production of the extremely reactive ·OH. Further studies showed that halogenated quinoid intermediates were produced during the degradation of XAr by ·OH-generating system, which could produce weak chemiluminescence that was greatly enhanced by addition of extra ·OH. We proposed that this unusual chemiluminescence generation was due to hydroxyl radical-dependent production of halogenated quinoid intermediates and electronically excited carbonyl species. In addition, the time course of chemiluminescence emission correlated well with the degradation of XAr: when the degradation level of XAr reached the maximum, no further chemiluminescence emission could be observed. Based on these findings, we developed a rapid, sensitive, simple, and effective chemiluminescence method to not only measure trace amount of XAr, but also monitor their real-time degradation kinetics. These new findings may have broad chemical, pharmaceutical, toxicological and environmental implications for future studies on remediation of these halogenated persistent organic pollutants by AOPs.

Key words: chemiluminescence, halogenated aromatics, hydroxyl radicals, advanced oxidation processes, Fenton and Fenton-like reactions