短链全氟烷酸替代物在城市污水深度处理工艺中的分布和排放
Occurrence and Discharge of Short-Chain Perfluoroalkyl Acids (PFAAs) Substitutes during Advanced Treatment Process in Municipal Wastewater Treatment Plants
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摘要: 随着全氟辛烷羧酸（PFOA）和全氟辛烷磺酸（PFOS）等长链全氟烷酸（PFAAs）逐渐被禁用，全氟丁烷羧酸（PFBA）、全氟己烷羧酸（PFHxA）、全氟丁烷磺酸（PFBS）和全氟己烷磺酸（PFHxS）等短链PFAAs已作为PFOA和PFOS的替代物被生产和使用。城市污水处理厂是PFAAs等微量有害污染物的源和汇，前期研究发现短链PFAAs在城市污水进水和二级生物处理系统出水中广泛存在，目前，污水厂开始普遍采用三级深度处理工艺，然而深度处理工艺中PFAAs的污染特征还不清楚。调查了中国7个城市11座城市污水处理厂深度处理工艺短链PFAAs替代物的分布及排放量。研究发现，在深度处理进、出水中PFOA、PFOS及短链的PFBA和PFHxA检出率均为100%；进水和出水中4种短链PFAAs的总浓度分别为3.53~155.97 ng·L-1和4.44~192.48 ng·L-1；PFBA、PFHxS和PFBS是进水中浓度最高的短链PFAAs，出水中主要为PFBA和PFHxS。转盘过滤、基于紫外、基于氯和臭氧的深度处理技术均无法有效去除短链替代物，甚至臭氧等还存在负去除现象，表明可能存在前体物的转化。调查的污水厂中4种短链PFAAs日排放总量范围为0.27~39.31 g·d-1，万吨水排放总量范围为40~800 mg。本研究将为城市污水深度处理技术综合评估和水环境微量有害污染物的管理提供科学基础。Abstract: Along with the prohibition and restriction for the use of perfluorooctanoic acid (PFOA) and perfluorooctyl sulfonate (PFOS), which belong to the long chain perfluoroalkyl acids (PFAAs), the short-chain PFAAs (e.g., perfluorobutanoic acid (PFBA), perfluorohexanoic acid (PFHxA), perfluorobutyl sulfonate (PFBS), and perfluorohexyl sulfonate (PFHxS)) have been produced and used as the substitutes for PFOA and PFOS. Municipal wastewater treatment plants (WWTPs) are considered as an important source of micropollutants, such as PFAAs, in environment. Previous studies have indicated that the prevalence of short-chain PFAAs in the influents and secondary effluents from municipal WWTPs. However, information of the pollution characteristics of the short-chain PFAAs during advanced treatment processes was still limited. In this study, the occurrence and discharge of short-chain PFAAs substitutes during the advanced treatment processes in 11 municipal WWTPs located in seven cities were investigated. The results show that PFOA, PFOS, PFBA, and PFHxA were detected in all samples. The total concentrations of the four short-chain substitutes were 3.53~155.97 ng·L-1 and 4.44~192.48 ng·L-1 in influents and effluents from the advanced treatment processes, respectively. PFBA, PFHxS and PFBS presented in the influents with the highest concentration, whilst PFBA and PFHxS were the predominant types in the effluents. The four kinds of advanced treatment processes (rotary disc-filter, UV, Cl2 and O3) could not remove short-chain substitutes and the concentrations of short-chain substitutes were even increased after O3 treatment process. The total daily discharge mass of short-chain PFAAs from the investigated WWTPs were 0.27~39.31 g·d-1, and the total discharge mass per ten thousand tons of water was 40~800 mg. This study provides a scientific basis for the comprehensive assessment of advanced treatment technologies in WWTPs and the management of micropollutants in water environment.
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