多溴联苯醚在硫酸根自由基高级氧化体系中的降解机制与溴元素转移规律研究

具有高风险的多溴联苯醚（PBDEs）在环境中的控制是目前研究关注的焦点，新型的硫酸根自由基高级氧化方法（SR-AOPs）能够对卤代有机污染物高效脱卤降解为PBDEs的有效控制提供了新思路。本课题研究PBDEs在SR-AOPs中的降解机制与溴元素转移规律，选取典型PBDEs同系物为研究对象，考察PBDEs在不同SR-AOPs中的降解效能及水中背景物质对其降解的影响，研究PBDEs与硫酸根自由基的反应动力学，并建立溴原子数目/位置与反应速率的构效关系；通过降解产物分析来推测PBDEs降解途径，探究硫酸根自由基对PBDEs的攻击位点与降解机制；通过监测有机溴/无机溴的变化与溴代副产物的生成情况，揭示PBDEs降解过程中溴元素的转移机制。课题研究成果将为PBDEs的有效控制提供理论依据，同时也将完善SR-AOPs降解卤代有机物时卤素的转移规律。

The removal technologies of polybrominated diphenyl ethers (PBDEs) with high risk have received a great attention, and sulfate radicals based advanced oxidation processes (SR-AOPs) which could effectively degrade halogenated organic contaminants via dehalogenation provide a novel method for PBDEs control. This project investigates PBDEs degradation and bromine transformation in SR-AOPs. Typical PBDE congeners are selected to: (i) investigate the degradation efficiency of PBDEs in SR-AOPs and the effects of water matrix on them; (ii) study the kinetics of the reactions between PBDEs with sulfate radicals and build the structure-activity relationship of rate constant and amount/position of bromine atoms; (iii) assess the degradation pathways of PBDEs and further expound the attack sites in PBDEs by sulfate radicals; (iv) measure the changes of brominated organic carbon/inorganic bromine species and detect the production of brominated-byproducts to clarify the transformation of bromine species during PBDEs degradation. These results could provide theoretical basis for PBDEs control and further understanding of bromine transformation during SR-AOPs oxidation.