目的: 建立一种磁性固相萃取-超高效液相色谱-串联质谱（MSPE-UHPLC-MS/MS）快速检测污水中14个芬太尼类毒品的方法。方法: 污水样品经新型混合模式弱阳离子交换磁性固相萃取材料Fe3O4@poly（ST/DVB/MA-COOH）净化和浓缩后,采用Waters Acquity UPLC HSS T3（150 mm×2.1 mm,1.8 μm）色谱柱进行分离,以0.1%甲酸-水溶液（A）和0.1%甲酸-乙腈溶液（B）为流动相,梯度洗脱,柱温40 ℃,流速0.3 mL · min-1,进样量2.5 µL,随后进入质谱电喷雾离子源,在多反应检测模式下进行检测。结果: 14个芬太尼类毒品质量浓度在0.04~4 ng · L-1范围内线性关系良好（r≥0.998 4）,检出限（LOD）为0.013 ng · L-1,定量限（LOQ）为0.04 ng · L-1。14个分析物在低、中、高3种加标浓度下方法的回收率为85.4%~114.7%,日内精密度（n=6）为2.0%~6.4%,日间精密度（n=3）为0.4%~2.4%。在5份实际污水样品中检测出芬太尼,浓度范围为0.21~0.46 ng · L-1。结论: 本方法具有前处理时间短,操作简单,溶剂用量少,灵敏度高和重现性好等优点,适用于污水样品中芬太尼类毒品的高通量筛查和定量分析。
Objective: To establish a magnetic solid-phase extraction-ultra performance liquid chromatography-tandem mass spectrometry (MSPE-UHPLC-MS/MS) method for rapidly detecting 14 fentanyl analogs in wastewater. Methods: Wastewater samples were purified and concentrated using a novel mixed-mode weak cation exchange magnetic solid phase extraction adsorbent, Fe3O4@poly (ST/DVB/MA-COOH), followed by analysis with UHPLC-MS/MS method. Separation was performed on a Waters Acquity UPLC HSS T3 column (150 mm×2.1 mm, 1.8 μm)at 40 ℃. The mobile phase consisted of 0.1% formic acid-aqueous solution(A) and 0.1% formic acid-acetonitrile solution(B) with gradient elution. The flow rate was 0.3 mL · min-1, and an injection volume was 2.5 µL. Detection was carried out using electrospray ionization in multiple reaction monitoring mode. Results: The calibration curves for the 14 fentanyl analogs showed good linearity over the range of 0.04-4 ng · L-1 (r≥0.998 4). The limit of detection (LOD) was 0.013 ng · L-1 and the limit of quantitation (LOQ) was 0.04 ng · L-1. The recovery rates at low, medium and high spiked levels ranged from 85.4% to 114.7%. The intra-day precision(n=6) was between 2.0% and 6.4%, and the inter-day precision(n=3) was between 0.4% and 2.4%. Fentanyl was detected in five actual wastewater samples, with concentrations ranging from 0.21 to 0.46 ng · L-1. Conclusion: This method has the advantages of short pretreatment time, simple operation, low solvent consumption, high sensitivity, and good reproducibility. It is suitable for high-throughput screening and quantitative analysis of fentanyl analogs in wastewater samples.
[1] RUBIN R.Illicit fentanyl driving opioid overdose deaths[J].JAMA,2017,318(22):2174
[2] PALAMAR JJ,FITZGERALD N,CARR TH,et al.National and regional trends in fentanyl seizures in the United States,2017—2023[J].Int J Drug Policy,2025,138:104417
[3] SALGUEIRO N,ZUCCATO E,CASTIGLIONI S.Nationwide investigation on the use of new psychoactive substances in Italy through urban wastewater analysis[J].Sci Total Environ,2022,843:156982
[4] LIN W,HUANG Z,GAO S,et al.Evaluating the stability of prescription drugs in municipal wastewater and sewers based on wastewater-based epidemiology[J].Sci Total Environ,2021,754:142414
[5] 韩兴,何美欣,李堪,等.基于污水毒品监测技术的依托咪酯同系物筛查预警[J].药物分析杂志,2024,44(6):1046
HAN X,HE MX,LI K,et al.Screening and early warning of etomidate homolog based on sewage drug monitoring technology[J].Chin J Pharm Anal,2024,44(6):1046
[6] 郑吴淇,宁弘宇,陈昊,等.流动注射-串联质谱法分析污水中11种毒品[J].分析试验室,2024,43(5):705
ZHENG WQ,NING HY,CHEN H,et al.Analysis of 11 drugs in sewage by flow injection-tandem mass spectrometry[J].Chin J Anal Lab,2024,43(5):705
[7] 原帅,向平,于治国,等.污水中毒品分析方法研究进展[J].中国司法鉴定,2020(4):23
YUAN S,XIANG P,YU ZG,et al.Research progress on analytical methods of drugs in sewage[J].Chin J Forensic Sci,2020(4):23
[8] MUNOZ M,GARRIGUES S,ESTEVE FA.Micro-solid phase extraction of pharmaceuticals and illicit drugs from wastewaters using monolith-coated syringe filters[J].Microchem J,2024,200:110484
[9] 周洁丹,孟辰颖.液相色谱-串联质谱法测定生活污水中8种芬太尼类化合物[J].化学分析计量,2022,31(12):33
ZHOU JD,MENG CY.Determination of 8 fentanyl compounds in domestic sewage by LC-MS/MS[J].Chem Anal Meter,2022,31(12):33
[10] DMITRIENKO SG,APYARI VV,TOLMACHEVA VV,et al.Dispersive and magnetic solid-phase extraction of organic compounds:review of reviews[J].J Anal Chem,2024,79(2):105
[11] WU A,ZHAO X,WANG J,et al.Application of solid-phase extraction based on magnetic nanoparticle adsorbents for the analysis of selected persistent organic pollutants in environmental water:a review of recent advances[J].Crit Reviews Environ Sci Technol,2021,51(1):44
[12] 李翔,梁晓静,王立成,等.磁性固相萃取吸附剂用于富集环境和食品中残留农药的研究进展[J].分析试验室,2022,41(12):1485
LI X,LIANG XJ,WANG LC,et al.Research advances of magnetic solid phase extraction adsorbents for the enrichment of pesticide residues in environment and food[J].Chin J Anal Lab,2022,41(12):1485
[13] NING H,FAN Y,CHEN H,et al.Preparation of mixed-mode weak cation exchange magnetic solid-phase extraction sorbent and its application in the extraction of 21 illicit drugs from wastewater[J].J Hazard Mater,2024,464:133007
[14] 赵苑余,陈江,温晓静,等.高分辨质谱法快速测定芬太尼类物质及其质谱裂解规律[J].刑事技术,2022,47(2):111
ZHAO YY,CHEN J,WEN XJ,et al.Rapid determination of fentanyl and its fragmentation pattern by high resolution mass spectrometry[J].Forensic Sci Technol,2022,47(2):111
[15] BADE R,ABDELAZIZ A,NGUYEN L,et al.Determination of 21 synthetic cathinones,phenethylamines,amphetamines and opioids in influent wastewater using liquid chromatography coupled to tandem mass spectrometry[J].Talanta,2020,208:120479
[16] BOLEDA MR,GALCERAN MT,VENTURA F.Monitoring of opiates,cannabinoids and their metabolites in wastewater,surface water and finished water in Catalonia,Spain[J].Water Res,2009,43(4):1126
[17] HUERTA M,GALCERAN MT,MARTIN J,et al.Occurrence of psychoactive stimulatory drugs in wastewaters in north-eastern Spain[J].Sci Total Environ,2008,397(1-3):31
