近日，广东工业大学环境健康与污染控制研究院、环境科学与工程学院余应新教授团队题为《Mixed bromine/chlorine transformation products of tetrabromobisphenol A: Potential specific molecular markers in e-waste dismantling areas》的研究性论文在Journal of Hazardous Materials (JHM，https://doi.org/10.1016/j.jhazmat.2021.127126)杂志上发表。论文第一作者为博士研究生葛翔和讲师马盛韬，通讯作者为余应新教授。该论文报道了贵屿镇(广东省汕头市)电子垃圾拆解区域表层土壤中的四溴双酚A(TBBPA)，双酚A(BPA)，以及TBBPA的脱溴产物(Br_xBPA, x = 1–3)和混合溴/氯转化产物(Cl_yBr_xBPAs, x = 1–3; y = 1–2)，详细分析了污染物的浓度分布、来源以及可能的转化路径。通过对比另一电子垃圾拆解区域(广东省清远市)和阻燃剂生产基地(山东省寿光市)的污染特征，讨论了Cl_yBr_xBPAs作为电子垃圾拆解活动的特异性分子标志物的可能性。本研究为更深入地了解这些转化产物的排放特征和现代电子垃圾拆解行业的环境足迹提供了新的见解。

 

电子垃圾拆解活动会排放出大量的有机阻燃剂，且在不同电子垃圾拆解场地检测出了相同的污染物，尽管它们所处理电子垃圾种类和回收工艺有所差别。贵屿镇于2015年建立了循环经济园区，主要从事电路板的回收和处理。清远市在此之前也建立了一些园区，供私人企业来回收电线电缆以及废旧塑料。有趣的是，电路板中含有大量的TBBPA，而电线电缆保护套中几乎没有，这可能会导致两个场地的主要污染物有所差别。TBBPA，BPA，Br_xBPAs和Cl_yBr_xBPAs在贵屿镇的表层土壤中被广泛检出，长期从事电子垃圾拆解活动的园区内污染程度较高，均值浓度分别为1.08 × 10⁴，2.35 × 10⁴，7.24 × 10³和237 ng/g dw。因清远市(物理粉碎电线电缆、塑料)和贵屿镇(高温热解电路板)在所处理的电子垃圾种类及工艺上有别，Cl_yBr_xBPAs在清远市的检出和浓度更低；而阻燃剂生产基地寿光市没有Cl_yBr_xBPAs检出。源解析结果表示，Cl_yBr_xBPAs可能由TBBPA和BPA先经脱溴和加溴，再经“溴-氯”转化反应生成。园区内的Cl_yBr_xBPAs可能来自于电子垃圾拆解过程；周边地区的既可能来自于园区内的迁移，也可能来自于TBBPA和BPA在存在氯源的条件下的自行孵化。浓度分布显示Cl_yBr_xBPAs更集中于园区内高温工艺段附近，意味着Cl_yBr_xBPAs的生成可能和高温有关。然而在清远市园区内物理粉碎回收电线电缆和塑料的过程中，产生的高温具有不稳定性，无法判断高温是否为Cl_yBr_xBPAs生成的必要条件。然而，母体化合物TBBPA和BPA，以及氯源的同时存在是Cl_yBr_xBPAs生成的必要前提。因此，即使Cl_yBr_xBPAs可以作为电子垃圾拆解活动可能的分子标志物，但也存在一定的局限性，它可以产生于任何具备上述条件的工业活动中。

论文DOI：https://doi.org/10.1016/j.jhazmat.2021.127126

 

图文摘要：

 

 

英文摘要：

Mixed bromine/chlorine transformation products (Cl_yBr_xBPAs) of tetrabromobisphenol A (TBBPA) were recently identified for the first time in an electronic waste (e-waste) dismantling site. To determine whether these compounds can be used as specific molecular markers of e-waste dismantling activities, the environmental occurrences and distributions of TBBPA and its transformation products including debromination products (Br_xBPAs) and Cl_yBr_xBPAs were analyzed in soil samples from three sites in China: Guiyu (an e-waste site), Qingyuan (a former e-waste site now mainly used for old wire and cable recycling), and Shouguang (a flame retardant production base). Levels of the target analytes in Guiyu were significantly higher than in Qingyuan and Shouguang. Br_xBPAs and Cl_yBr_xBPAs were widely detected in Guiyu at concentrations between 1 and 4 orders of magnitude lower than their parent compound TBBPA. The highest concentration was found in an e-waste dismantling park, with lower concentrations in surrounding area. The levels of Cl_yBr_xBPAs in Qingyuan were much lower, indicating that the Cl_yBr_xBPAs may come from the processing of wires and cables, but not rule out the incubation on their own in soils. None of Cl_yBr_xBPAs were detected in Shouguang. Cl_yBr_xBPAs may thus be useful as specific molecular markers for determining the intensity of e-waste dismantling activities.

项目资助：本研究得到国家自然科学基金(41991311, 41977303, 41703092, 41731279)，粤港澳污染物暴露与健康联合实验室(2020B1212030008)和广东工业大学百人计划的支持。