超高效液相色谱-串联三重四极杆质谱法检测血清中12种全氟化合物

目的 建立血清中12种全氟化合物的超高效液相色谱-串联三重四极杆质谱分析方法。方法 血清样品经乙腈沉淀蛋白质，2.0% 甲酸水溶液酸化后，经Oasis WAX 固相萃取柱净化，2.0% 氨化甲醇洗脱，氮吹至干后复溶于甲醇- 2 mmol/L乙酸铵溶液（40∶60, v/v）。采用Waters BEH C18色谱柱（2.1 mm×50 mm，1.7 μm）分离，2 mmol/L乙酸铵溶液-甲醇为流动相，梯度洗脱，流速为0.3 ml/min。采用电喷雾负离子模式电离、多反应监测模式分段检测。结果 血清中12种全氟化合物在0.050 ~ 50 μg/L范围内有良好的线性关系，相关系数大于0.999；检出限、定量限分别为0.008 ~ 0.020 μg/L、0.026 ~ 0.066 μg/L；低中高三个水平的血清加标回收率为76.0% ~ 110.2%，相对标准偏差为0.4% ~ 7.3%；基质效应在72.0% ~ 117.6%之间。方法应用于20份人血清样本检测，PFOA、PFNA、PFHxS、PFHpS、PFOS均被检出，PFDA检出率为90.0%，中位数分别为:1.43、0.16、0.30、0.07、0.74和0.07 μg/L。结论 建立的方法快速简便、准确，适用于血清中12种全氟化合物的分析，为评估人群全氟化合物暴露情况提供技术支撑。

Determination of 12 perfluoroalkyl substances in human serum by ultra high performance liquid chromatography-tandem triple quadrupole mass spectrometry

Objective To establish an ultra-high performance liquid chromatography-tandem triple quadrupole mass spectrometry (UPLC-MS/MS) for the analysis of 12 perfluoroalkyl substances (PFAS) in serum samples. Methods After the protein precipitation with acetonitrile in serum sample, the sample solution was acidized with 2.0% formic acid solution and then purified with Oasis WAX solid phase extraction (SPE) column, finally the target compounds were eluted with ammoniated methanol. The eluted solution was dried-up under a gentle stream of nitrogen and redissolved in methanol-2 mmol/L ammonium acetate solution (40:60, v/v). Waters BEH C18 (2.1 mm×50 mm, 1.7 μm) column was used for separation, methanol and 2 mmol/L ammonium acetate solution were used as mobile phase with gradient elution at a flow rate of 0.3 ml/min. PFAS were detected by tandem triple quadrupole mass spectrometer using multiple reaction monitoring (MRM) in the negative electrospray ionization (ESI) mode. Results The method detection limits and quantification limits were 0.008 to 0.020 μg/L and 0.026 to 0.066 μg/L, respectively. The spiked recoveries at three different levels were 76.0% to 110.2% with relative standard deviations of 0.4% to 7.3%. The matrix effects were in the range of 72.0% to 117.6%. The proposed method was used to detect 12 PFAS in 20 human serum samples, and the results showed that PFOA, PFNA, PFHxS, PFHpS, PFOS were detected, with the detected frequency of 90.0% for PFDA. The median concentrations were 1.43 μg/L, 0.16 μg/L, 0.30 μg/L, 0.07 μg/L, 0.74 μg/L, 0.07 μg/L, respectively. Conclusion The established method is rapid, simple, accurate, and suitable for the analysis of 12 PFAS in serum samples, which could provide technical support for the assessment of human exposure to PFAS.