Sensitive determination of illicit drugs in wastewater using enrichment bag-based liquid-phase microextraction and liquid-chromatography tandem mass spectrometry

Abstract 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.