泳池水中新型芳香族卤代消毒副产物的检测鉴定、生成机制、转化特征、毒性效应及控制原理研究

Aromatic halogenated disinfection byproducts (DBPs) are a new category of DBPs with relatively high toxicity and thus have drawn increasing concern. However, in most of previous studies, aromatic halogenated DBPs were investigated in drinking water or wastewater effluents, and few studies reported the systematic investigation of aromatic halogenated DBPs in swimming pool water. Thus, the objectives of this project are to systematically detect and identify aromatic halogenated DBPs in swimming pool water, to explore the formation and transformation of aromatic halogenated DBPs in swimming pool water, to evaluate the toxicity of aromatic halogenated DBPs in swimming pool water and to establish the proper control strategies for aromatic halogenated DBPs in swimming pool water. Firstly, the targeted and non-targeted detection and identification of aromatic halogenated DBPs in swimming pool water will be conducted, and then the concentrations of the identified aromatic halogenated DBPs are to be measured in swimming pool water. The concentrations of these aromatic halogenated DBPs in swimming pool water will be compared with those in the incoming tap water to figure out the occurrence and source of aromatic halogenated DBPs in swimming pool water. Secondly, the formation and transformation of aromatic halogenated DBPs in swimming pool water will be investigated, including the precursors, pathways, kinetics and factors. Thirdly, the cytotoxicity of the identified aromatic halogenated DBPs in swimming pool water will be evaluated, and the human health risk assessment is to be conducted for these aromatic halogenated DBPs in swimming pool water. Finally, the control strategies of aromatic halogenated DBPs in swimming pool water will be established based on the principle of “precursor removal + optimization of disinfection mode + DBP removal + optimization of water circulation”.

芳香族卤代消毒副产物（DBPs）是近年来新发现的一类高毒性DBPs，前人对此类DBPs的研究主要集中在饮用水和污水中，而对泳池水中的芳香族卤代DBPs缺乏系统性研究。本项目拟针对泳池水中新型芳香族卤代DBPs的检测鉴定、生成机制与转化特征、毒性效应及控制原理展开系统性研究。首先建立靶向与非靶向分析相结合的泳池水中芳香族卤代DBPs的全面定性分析方法，再通过进一步的准确定量解析泳池水中芳香族卤代DBPs的浓度水平，并基于泳池水与其填充自来水的对比阐明泳池水中此类DBPs的赋存特征及来源；全面解析泳池水中芳香族卤代DBPs的生成机制和转化特征；系统分析泳池水中芳香族卤代DBPs的毒性效应，并基于浓度水平和毒性效应数据对泳池水中芳香族卤代DBPs所造成的人体健康风险进行评估；构建基于“前驱物削减+消毒方式优化+DBPs去除+泳池水循环体系优化”的泳池水中芳香族卤代DBPs的控制新技术原理。

游泳是一种常见的休闲健身方式，泳池水的水质安全备受关注。消毒副产物（DBPs）是泳池水中一类重要的污染物，其对人体健康的影响不容忽视，而芳香族卤代DBPs是近年来新发现的一类高毒性DBPs。本研究针对泳池水中新型芳香族卤代DBPs的检测鉴定、生成机制与转化特征、毒性效应及控制原理展开了系统性研究。首先建立了基于固相萃取前处理和高效液相色谱-电喷雾离子化-三重四级杆质谱（HPLC-ESI-tqMS）检测的芳香族卤代DBPs的定性定量分析方法，并采用该方法对南京市7个大型室内公共游泳池的泳池水及其填充自来水水样进行了分析，在泳池水中检出6类共50种芳香族卤代DBPs，其中41种为首次检出，其平均浓度大小顺序为：卤代苯醌>卤代苯酚>卤代羟基苯甲酸>卤代羟基苯甲醛>卤代苯胺>卤代硝基苯酚；在此基础上选取了特征性的芳香族卤代DBPs种类，系统探究了泳池水中典型前驱物氯化生成芳香族卤代DBPs的机制，包括生成路径、生成动力学和影响因素，发现人为引入的有机质是泳池水中芳香族卤代DBPs的重要前驱物，另外全面解析了泳池水中芳香族卤代DBPs在氯化/氯胺化消毒中的转化特征，包括转化产物、转化路径、转化动力学和影响因素，发现芳香族卤代DBPs在氯化/氯胺化消毒中转化生成脂肪族卤代DBPs，且卤代苯醌是重要的中间产物；采用人体肝癌细胞系统评估了泳池水中芳香族卤代DBPs的细胞毒性，并对泳池水中芳香族卤代DBPs的细胞毒性贡献进行了计算，发现泳池水中不同种类芳香族卤代DBPs的细胞毒性贡献大小顺序为卤代苯醌>卤代苯酚>卤代硝基苯酚>卤代羟基苯甲酸>卤代羟基苯甲醛>卤代苯胺；最后探究了人为引入的有机质对泳池水中新型芳香族卤代DBPs生成的影响，不同消毒方式对新型芳香族卤代DBPs生成的影响，以及活性炭吸附对新型芳香族卤代DBPs的去除效果，提出了基于“前驱物削减+消毒方式优化+DBPs去除”的泳池水中新型芳香族卤代DBPs的初步控制建议。本研究重点阐明了泳池水中芳香族卤代DBPs的赋存特征、生成机制与转化特征、毒性效应及其控制技术，为游泳池水质安全保障提供了重要的理论依据。