Wang Weimin, Guo Changsheng, Chen Like, Qiu Ziwen, Yin Xingxing, Xu Jian
State Key Laboratory of Environmental Criteria and Risk Assessment, State Environmental Protection Key Laboratory of Ecological Effect and Risk Assessment of Chemicals, Chinese Research Academy of Environmental Sciences, Beijing, 100012, China; College of Water Sciences, Beijing Normal University, Beijing, 100875, China.
State Key Laboratory of Environmental Criteria and Risk Assessment, State Environmental Protection Key Laboratory of Ecological Effect and Risk Assessment of Chemicals, Chinese Research Academy of Environmental Sciences, Beijing, 100012, China.
Environ Pollut. 2021 Mar 15;273:116424. doi: 10.1016/j.envpol.2021.116424. Epub 2021 Jan 8.
An enantioselective method for quantifying amphetamine-type chiral illicit drugs (CIDs) in wastewater and surface water was developed, validated, and applied to samples from a wastewater treatment plant (WWTP) and its effluent-receiving river in Beijing, China. Water samples were subjected to solid-phase extraction (SPE) and then quantified via liquid chromatography-tandem mass spectrometry. The enantioseparation of CIDs was performed with a CHIRALPAK CBH column. Chromatographic parameters, including mobile phase composition and flow rates, were tested to identify the satisfactory enantiomeric resolution. The SPE method was optimized by evaluating variables, including SPE cartridge types, extraction solvents, and solvent volumes. The Oasis HLB sorbent showed good performance with recoveries exceeding 60% and matrix effects ranging from -19.6% to 26.6% for most target enantiomers, except for norephedrine (NE), in three different aquatic matrixes. The established method was superior to previously reported methods and had a low limit of detection, low limit of quantification, and short runtime (<45 min). The repeatability and reproducibility of the method reached 19.1% and 17.8%, respectively. The method was successfully utilized to monitor the daily variations in CIDs in the influent, effluent, and effluent-receiving river of a WWTP in Beijing over 1 week. The common occurrence of 1 R,2 S-(-)-ephedrine (1 R,2 S-(-)-EPH), 1 S,2 S-(+)-pseudoephedrine (1 S,2 S-(+)-PEPH), R-(-)-methamphetamine (METH), and S-(+)-METH in wastewater samples was observed. Ephedrines (1 R,2 S-(-)-EPH and 1 S,2 S-(+)-PEPH) were the most abundant CIDs in the influent, effluent, upstream, and downstream samples with concentrations of 725.8 ± 181.2 ng/L, 22.9 ± 4.9 ng/L, 12.96 ± 0.79 ng/L, and 11.6 ± 6.7 ng/L, respectively. METH was detectable in most water samples and was present in excess in S-enantiomer form in the influent and in R-enantiomer form in the effluent and surface water. R-(-)-MDMA was detected at a concentration of up to 2.4 ng/L in the influent. The metabolites norketamine (NK), amphetamine(AMP), MDA, and NE were not detected in water samples given the low concentration of their parent drugs.
开发并验证了一种对废水和地表水中苯丙胺类手性非法药物（CIDs）进行定量分析的对映体选择性方法，并将其应用于中国北京某污水处理厂（WWTP）及其受纳河流的水样分析。水样经过固相萃取（SPE），然后通过液相色谱-串联质谱法进行定量分析。使用CHIRALPAK CBH色谱柱实现了CIDs的对映体分离。测试了包括流动相组成和流速在内的色谱参数，以确定令人满意的对映体分离度。通过评估SPE柱类型、萃取溶剂和溶剂量等变量对SPE方法进行了优化。在三种不同的水生基质中，除去甲麻黄碱（NE）外，Oasis HLB吸附剂表现出良好的性能，大多数目标对映体的回收率超过60%，基质效应在-19.6%至26.6%之间。所建立的方法优于先前报道的方法，具有低检测限、低定量限和短运行时间（<45分钟）。该方法的重复性和再现性分别达到19.1%和17.8%。该方法成功用于监测北京某污水处理厂进水、出水和受纳河流中CIDs在1周内的每日变化情况。观察到废水样品中常见1R,2S-(-)-麻黄碱（1R,2S-(-)-EPH）、1S,2S-(+)-伪麻黄碱（1S,2S-(+)-PEPH）、R-(-)-甲基苯丙胺（METH）和S-(+)-METH。麻黄碱类（1R,2S-(-)-EPH和1S,2S-(+)-PEPH）是进水、出水、上游和下游样品中含量最高的CIDs，浓度分别为725.8±181.2 ng/L、22.9±4.9 ng/L、12.96±0.79 ng/L和11.6±6.7 ng/L。大多数水样中均可检测到METH，进水样中以S-对映体形式过量存在，而出水和地表水样中以R-对映体形式存在。进水样中检测到R-(-)-摇头丸（MDMA）的浓度高达2.4 ng/L。由于母体药物浓度较低，水样中未检测到代谢产物去甲氯胺酮（NK）、苯丙胺（AMP）、MDA和NE。
