利用高分辨质谱靶标、非靶标策略高通量筛查黄河和海河中新型污染物（EPs）及其风险评估

In China, which has a rapidly growing economy, increasing numbers of Emerging Pollutants (EPs) are released into surface water bodies, and many of these compounds become potential threat to the environment. While the most relevant studies reported are dedicated to one or a few known EPs, often the full range of EPs are not covered and the whole picture is missing, and the studies about unknown compounds is limited. The rapid development of target, suspect and non-target screening strategies based on LC-HRMS allows high-throughput screening of EPs in the environment. Accordingly, we propose to establish a fast and efficient high-throughput screening approach of LC-HRMS to study EPs comprehensively in the Yellow River and Hai River which are the most essential water resource to North and West regions in China. Based on our previous work, in this study a LC-HRMS high-throughput screening approach that combined target, suspect and non-target strategies is proposed in order to identify known and unknown EPs, furthermore to investigate the occurrence, spatial and temporal distribution, risk assessment and priorization of main chemicals for a set of surface water samples in the Yellow River and the Hai River. The samples will be taken from different sites of the rivers in high flow and low flow periods respectively. The success of this project will be helpful to provide essential data for the regulation and policy making of the regularly monitoring, assessment and management of EPs in aquatic environment in China.

随着我国经济迅速增长，层出不穷的新型污染物（EPs）持续排入地表水，对环境构成潜在威胁。目前研究多局限于几种EPs，缺乏对水体中大量EPs 的整体认识，并且对未知EPs的报道较少。液相色谱高分辨质谱联用(LC-HRMS)和多种污染物筛查策略（靶标、可疑物和非靶标）的发展，使得高通量识别EPs成为可能。据此我们提出建立一种基于LC-HRMS的快速有效的高通量筛查方法，对我国华北、西北地区最不可替代的水资源黄河、海河中EPs进行综合研究的设想。本项目拟在前期工作的基础上，在丰水期和枯水期，采集黄河、海河不同断面的地表水样品，利用靶标、可疑物及非靶标策略对 EPs进行LC-HRMS高通量筛查，探究这类污染物在北方两大水体中的整体存在状况及时空分布特征，并结合风险评估对主要化学因子进行优选。为我国水环境保护中新型污染物的管控、相关标准和政策制定提供重要的基础数据。

种类繁多的新型污染物（EPs）持续排入地表水，对环境构成潜在威胁。然而，目前对于该类污染物在地表水中的整体存在状况和生态风险的认识很有限。据此，基于液相色谱高分辨质谱技术（LC-HRMS），我们建立了一种综合靶标、可疑物和非靶标策略的高通量筛查地表水中EPs的方法, 并对我国黄河、海河中EPs进行综合研究。主要工作如下：①基于超高效液相色谱-四极杆-飞行时间串联质谱技术及靶标、可疑物及非靶标筛查策略，建立了与LC-HRMS高通量识别EPs相匹配的样品前处理以及仪器分析方法；②完成了黄河、海河不同区域地表水样品的采集、分析并识别大量EPs，揭示了黄河和海河中EPs的整体存在状况及分布特征，共识别出106种新型污染物，包括药物37种、农药33种、工业产品21种、个人护理用品9种、食品添加剂4种和转化产物2种。海河和黄河分别检出79种、84种EPs，两河均有检出的污染物有58种。23种EPs检出率高于70%，39种检出率高于50%。其中苯并三唑、安替比林、2-羟基莠去津、二丁基莠去津和肌酸酐检出率为100%。对84种EPs定量，浓度为0.07-3538.10 ng/L。黄河、海河高检出率及高浓度的特征EPs构成不同，且EPs分布特征与空间及周边环境与排污情况相关，总体EPs累积浓度黄河高于海河，支流高于干流，中下游样品累积浓度高于上游;③对67种EPs的3种营养级模式生物物种进行生态风险评估，结合化合物浓度及在环境中的生物有效性计算风险熵，优选出黄河、海河的风险化学因子分别为21种、19种。实验结果表明，本研究建立的高分辨质谱靶标、可疑物和非靶标策略的高通量筛查方法能够在对样品无先验信息的情况下，为全面识别新型污染物提供有效的技术手段，不仅快速、准确，还能为后续生态风险评估及主要化学风险因子优选提供重要依据。