Academy of Forensic Science, Shanghai Key Laboratory of Forensic Medicine, Shanghai Forensic Service Platform, Guangfu West Road #1347, Shanghai 200063, China; Department of Forensic Medicine, Huazhong University of Science and Technology, Hangkong Road #13, Wuhan, Hubei 430030, China.
Department of Forensic Medicine, Huazhong University of Science and Technology, Hangkong Road #13, Wuhan, Hubei 430030, China; Shenzhen Huazhong University of Science and Technology Research Institute, Yuexing Third Road #9, Nanshan District, Shenzhen, Guangdong 518000, China.
J Chromatogr A. 2022 Jan 4;1661:462684. doi: 10.1016/j.chroma.2021.462684. Epub 2021 Nov 15.
To concentrate trace level of analytes in complex wastewater, sample preparation is necessary prior to instrumental analysis. In this work, an enrichment bag-based liquid-phase microextraction (EB-LPME) system was therefore proposed for the first time to isolate and enrich the illicit drugs (amphetamine, methamphetamine, 3,4-methylenedioxymethamphetamine (MDMA), ketamine, codeine and fentanyl) from wastewater. Under the optimum EB-LPME conditions, the recoveries of the model illicit drugs were 40-93% with enrichment factors up to 93. The optimized EB-LPME was compared to hollow fiber-LPME (HF-LPME) in terms of the thickness of the supported liquid membrane (SLM), the effective SLM area, extraction recovery and mass transfer flux. Compared with HF-LPME, EB-LPME possesses larger effective SLM area, and provided higher extraction recovery. In addition, EB-LPME provided larger mass transfer flux than HF-LPME, which was mainly due to the differences in SLM thickness. Therefore, SLM thickness was identified as the main mass transfer flux-determining factor experimentally. The matrix effect of EB-LPME was evaluated using liquid chromatography-tandem mass spectrometry (LC-MS/MS), and excellent sample clean-up was confirmed. Subsequently, EB-LPME-LC-MS/MS was validated with satisfactory results, and the detection of limit of the proposed method was in the range of 0.3-8.7 ng/L. Finally, with standard addition method, EB-LPME-LC-MS/MS was successfully applied for the determination of the model drugs in a local hospital wastewater from Wuhan, China. This study clearly showed that EB-LPME displayed great potential as an efficient sample preparation method for isolation and enrichment of the drugs/pollutants from complex environmental samples for wastewater-based epidemiology in the near future.
为了浓缩复杂废水中痕量分析物，在仪器分析之前需要进行样品制备。在这项工作中，首次提出了基于富集袋的液相微萃取（EB-LPME）系统，用于从废水中分离和富集非法药物（安非他命、甲基苯丙胺、3,4-亚甲基二氧甲基苯丙胺（MDMA）、氯胺酮、可待因和芬太尼）。在最佳的 EB-LPME 条件下，模型非法药物的回收率为 40-93%，富集因子高达 93。将优化后的 EB-LPME 与中空纤维-LPME（HF-LPME）进行了比较，比较了支撑液膜（SLM）的厚度、有效 SLM 面积、萃取回收率和传质通量。与 HF-LPME 相比，EB-LPME 具有更大的有效 SLM 面积，并提供了更高的萃取回收率。此外，EB-LPME 提供的传质通量大于 HF-LPME，这主要是由于 SLM 厚度的差异。因此，实验中确定 SLM 厚度是主要的传质通量决定因素。使用液相色谱-串联质谱法（LC-MS/MS）评估了 EB-LPME 的基质效应，并证实了良好的样品净化效果。随后，对 EB-LPME-LC-MS/MS 进行了验证，结果令人满意，该方法的检测限范围为 0.3-8.7 ng/L。最后，采用标准加入法，成功应用 EB-LPME-LC-MS/MS 测定了中国武汉某医院废水模型药物。这项研究清楚地表明，EB-LPME 作为一种从复杂环境样品中分离和富集药物/污染物的有效样品制备方法，在不久的将来有望用于基于废水的流行病学研究。
