超高效液相色谱-串联质谱法同时检测淡水鱼中23种全氟及多氟烷基化合物

Simultaneous determination of 23 kinds of perfluorinated and polyfluoroalkyl subtances in freshwater fishes by ultra performance liquid chromatography-tandem mass spectrometry

中文关键词:  超高效液相色谱-三重四极杆质谱  全氟及多氟烷基化合物  淡水鱼  固相萃取

英文关键词:ultra performance liquid chromatography-tandem mass spectrometry  perfluorinated and polyfluoroalkyl substances  freshwater fish  solid phase extraction

中文摘要:

      目的 建立一种有机溶剂提取、固相萃取柱净化、超高效液相色谱?串联质谱法(ultra performance liquid chromatography-tandem mass spectrometry, UPLC-MS/MS)同时测定淡水鱼中全氟烷基羧酸、全氟烷基磺酸及多氟调聚磺酸3类23种全氟及多氟烷基化合物(perfluorinated and polyfluoroalkyl substances, PFASs)的分析方法。方法 优化了色谱分离条件、质谱检测参数, 并考察了提取溶剂及固相萃取柱填料对样品加标回收率和净化效果的影响, 确定了最佳样品前处理及仪器条件。淡水鱼样品经2%甲酸/乙腈提取后, 采用去磷脂PPR Pro小柱净化, 以5 mmol/L甲酸铵水溶液和甲醇为流动相, 通过C18反相色谱柱分离目标物; 质谱采用电喷雾离子源负离子模式(electrospray ionization, ESI-), 以多反应监测模式(multiple reaction monitoring, MRM)检测, 稳定同位素内标法定量。结果 23种PFASs目标物在0.5100.0 ng/mL质量浓度范围内线性关系良好(r2>0.980), 检出限为0.030~0.170 μg/kg, 定量限为0.100~0.567 μg/kg, 方法回收率为72.9%~111.0%, 相对标准偏差为3.0%~17.5% (n=9)。结论 该方法操作简便, 灵敏度高, 抗干扰性强, 精密度好, 适用于淡水鱼中23种全氟烷基羧酸、全氟烷基磺酸及多氟调聚磺酸的快速检测分析。

英文摘要:

      Objective To develope a method based on organic solvent extraction and solid phase extraction purification combined with ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) for the simultaneous determination of 23 kinds of perfluorinated and polyfluoroalkyl substances (PFASs), including perfuluorocarboxylic acids, perfluoroalkyl sulfonic acids, and fluorotelomer sulfonic acids, in freshwater fishes. Methods The chromatographic conditions and mass spectrometry parameters were optimized, and the effects of extraction solvent and solid phase extraction column fillers on sample recovery and purification were investigated. The optimal sample pretreatment and instrument conditions were determined. Freshwater fish samples were directly extracted with 2% formic acid and purified using a lipid removal PPR Pro column. With 5 mmol/L ammonium formate aqueous solution and methanol as mobile phase, the target substances were separated by C18 chromatographic column. The mass spectrum was detected by electrospray ion source (ESI-), multi reaction monitoring (MRM) and stable isotope internal standard method. Results The 23 kinds of target PFASs had a good linear relationship within 0.5–100.0 ng/mL mass concentration range (r2>0.980), with the limits of detection was 0.030–0.146 μg/kg and the limits of quantification were 0.100–0.567 μg/kg. The spiked recoveries of serum sample were 72.9%–111.0%, with relative standard deviations of 3.0%–17.5% (n=9). Conclusion The method has the advantages of simple operation, high sensitivity, strong anti-interference and good precision, and is suitable for the rapid detection and analysis of 23 kinds of perfluoroalkyl carboxylic acids, perfluoroalkyl sulfonic acid and polyfluorotelomeric sulfonic acid in freshwater fish.