离线和在线固相萃取-液相色谱-质谱法测定污水中5种芬太尼类物质及其代谢物

Determination of 5 Fentanyl Analogues and Metabolites in Wastewater by Liquid Chromatography-Tandem Mass Spectrometry Using Off-line and On-line Solid-Phase Extraction

近年来芬太尼类物质的滥用在世界范围内呈显著上升趋势,本研究应用离线和在线固相萃取结合液相色谱-质谱联用技术,建立了污水中芬太尼、乙酰芬太尼及其3种主要代谢物的检测方法。样品前处理分别考察了基于PRiME MCX阳离子交换柱的离线固相萃取以及基于HLB Direct Connect HP反相柱的在线固相萃取,结果显示,前者对于复杂污水基质中目标物的提取效果优于后者,但后者操作简便更适于大批量样品检测。液相色谱-质谱联用检测均使用C18色谱柱,0.1%甲酸水和0.1%甲酸乙腈线性梯度洗脱,正离子化多反应监测模式进行定量分析。经同位素内标校正,两种固相萃取模式下5种目标物在0.5~200 ng·L-1范围内线性关系良好(r>0.995),定量结果误差小于10%,日内和日间精密度相对标准偏差(RSD)均小于6%,说明方法高效可靠。本方法适用于污水中5种芬太尼类物质及其代谢物的定量检测,为利用污水流行病学原理监测该类物质的滥用提供了新的手段。

Recently,a significant rise in the popularity and abuse of fentanyl analogues was observed worldwide.In this study,both off-line and on-line solid-phase extraction(SPE)combined with liquid chromatography-tandem mass spectrometry(LC-MS/MS)were developed for the detection of fentanyl,acetyl fentanyl and their three main metabolites in wastewater.For LC-MS/MS analysis,chromatographic separation was performed on C18 column with mobile phase consisting of 0.1%formic acid aqueous solution and 0.1%formic acid acetonitrile solution by linear gradient elution.Target analytes were then detected by positive electrospray ionization(ESI+)mode and multiple reaction monitoring mode(MRM)for quantitative analysis.Two wastewater sample preparation methods,i.e.,off-line solid-phase extraction based on a mixed cation exchange column(PRiME MCX)and on-line solid-phase extraction based on a reversed-phase column(HLB Direct Connect HP)were studied.The former one showed higher recoveries of target analytes from complex wastewater matrices,while the latter one was more suitable for batch analysis for its convenient operation.When calibrated by isotope internal standards,both methods obtained a linear range of 0.5-200 ng/L for all target analytes with linear regression coefficient(r)higher than 0.995,while the relative errors(REs)were below 10%,and the intra-day and inter-day precision RSDs were less than 6%,indicating that the methods were efficient and reliable.This strategy is applicable to the quantitative analysis of the fentanyl analogues in real wastewater samples,providing a new means of monitoring and assessing the trends of fentanyl analogues abuse via wastewater-based epidemiology.