毒性引导的游泳池水中高毒性副产物识别及生成机制研究

The pollutants in swimming pool are mainly introduced from filling water (dissolved organic matters), swimmers (cosmetics, excreta), and the corresponding disinfection by-products during continuous disinfection process, which would cause potential health risk. The present research proposal focuses on both of indoor and outdoor swimming pools with typical water treatment processes, collects water samples under various running conditions and concentrates pollutants by resins, isolates into several fractions with different physicochemical properties. On one hand, measure the toxicity effects of all water fractions, and screen out the ones with high toxicity. On the other hand, separate and identify the major toxic by-products using LC/MS, GC/MS, HRMS and NMR tools; Disclose the formation characteristics of major toxic by-products during the continuous disinfection process, and trace the corresponding toxicity variation as well; Analyze the possible correlation between the occurrence of major toxic by-products and toxicity. Finally, propose the possible formation mechanisms of toxic by-products during the continuous disinfection process in swimming pools on the basis of chemical reaction principles, theoretical computation and model studies. Simultaneously, select some typical pollutants contained in filling water, released from swimmers, and key intermediates as models, perform continuous disinfection in pure water and in real swimming pool water under various experimental conditions, respectively, to validate the proposed transformation mechanisms. The results of this research proposal would throw more light on the occurrence, formation and toxicity characteristics of highly toxic disinfection by-products during continuous disinfection treatment in swimming pool, and provide scientific reference for optimizing disinfection process of swimming pools.

游泳池水中主要含有补充水源（自来水）和人源（游泳者使用的护理品、分泌/排泄物）污染物、及其在循环消毒中生成的副产物，组成复杂、危害健康。本课题拟选择典型处理工艺的室内、室外游泳池为研究对象，在毒性效应引导下，首先富集水体中主要污染物，根据理化性质差异将其分离为不同组分，通过检测各组分的毒性特征，筛选出高毒性组分。其次，借助色谱、高分辨质谱、核磁共振等技术，分离、识别高毒性组分中主要毒性副产物的分子结构；揭示其在游泳池水循环消毒处理中的演化规律，并解析与毒性变化特征间的相关性。在此基础上，结合化学反应原理和理论计算，阐释高毒性副产物在循环消毒过程中的生成机制；选择典型人源和补充水源中的前驱物、制备的关键中间体为模型化合物，验证其在游泳池水循环消毒处理中的转化机制和毒性变化特征。通过本课题的研究，旨在揭示游泳池水体中高毒性污染物的赋存形态、转化机制及毒性效应，为优化游泳池消毒工艺提供科学依据。

消毒是游泳池水处理必不可少的环节,但游泳池水组成复杂，既有原水中残留的污染物，更有游泳者带入的各种污染物，如排泄物、擦涂的护肤品、防晒剂等。这些物质可能与消毒剂反应生成副产物，威胁人体健康。本研究模拟游泳池消毒环节，借助毒性测试和仪器分析手段，研究了模拟体液和典型二苯甲酮类紫外防晒剂在氯、氯胺、紫外-氯胺等消毒处理中的毒性变化及产物生成情况，主要取得以下成果：.（1）研究游泳池中模拟体液在氯化消毒过程中的毒性变化，发现低剂量氯（小于1 mg/L）消毒后急性毒性显著升高，高剂量氯（5 mg/L）消毒后毒性降低。多个游泳池水样中检出二苯甲酮类防晒剂及其氯代产物，消毒处理后毒性显著升高。.（2）揭示了紫外防晒剂BP-4在氯胺消毒处理中的转化和毒性变化特征。在消毒体系中识别出23种主要产物，提出了BP-4在氯胺消毒处理中的转化路径，主要涉及氨基取代、氯代、氧化、水解、偶联等反应。随pH升高，BP-4去除率和转化速率增大，毒性逐渐升高。随氯胺剂量的增加，BP-4去除率和速率增加，毒性先升高后降低，5倍氯胺剂量时毒性最大。通过对产物与毒性的相关性分析，推测苯醌类产物P13和P13’为主要毒性产物。.（3）揭示了BP-4在氯胺-UV联合消毒体系中的转化行为。BP-4在紫外照射条件下难降解，但在氯胺反应体系中生成的中间体可迅速光解，共检测出10种光解产物。且UV处理后毒性迅速升高。随pH升高和氯胺剂量增加，反应体系的毒性也逐渐升高。相关性分析提示产物T2和T5可能是主要的毒性产物。氯胺-紫外联合处理体系中溴、碘离子的存在减弱了反应后溶液的毒性、及毒性上升的趋势。.（4）考察了14种二苯甲酮类化合物在氯化消毒中生成三氯甲烷的情况。发现在pH7及5倍氯剂量条件下，各目标物生成三氯甲烷的量各不相同，其中2,2′,4,4′-四羟基二苯甲酮的生成量最大（6.3 mg/L），二苯甲酮的生成量最低（0.19 mg/L），这对于研究游泳池水在消毒过程产生三氯甲烷机理方面具有重要意义。