UPLC-MS/MS法同时测定地表水中6种双酚类化合物残留

Simultaneous Determination of Six Bisphenol Residues in Surface Water by UPLC-MS/MS

为了准确地检测双酚类化合物在地表水中的残留水平,建立了固相萃取-超高效液相色谱-电喷雾串联质谱(SPE-UPLC-ESI-MS/MS)法分析水中包括双酚A在内的6种双酚类化合物残留。样品经HLB固相萃取柱富集和净化后,采用Waters Acquity UPLC BEH T3色谱柱,以2mmol/L乙酸铵-甲醇溶液和2mmol/L乙酸铵-水溶液作为流动相进行梯度洗脱,电喷雾离子源电离,负离子多反应监测模式进行定性和定量分析。结果表明:6种双酚类化合物在0.10~50.0μg/L或0.50~100μg/L浓度范围内的线性关系良好,相关系数在0.997~0.999之间,方法的检出限为0.05~0.31ng/L;高、中、低三个添加水平的回收率为74.8%~122%,相对标准偏差在3.33%~12.4%之间。采用该方法对杭州市部分河流和水库的地表水样品进行分析,共检出5种污染物。该方法灵敏、准确、检测范围广、分析速度快,适用于实际水样中6种双酚类化合物的同时测定。

A method of solid phase extraction-ultra performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry （SPE-UPI.C-ESI-MS/ MS） was developed for the determination of six bisphenol residues in surface water, including bisphenol A, bisphenol AF, bisphenol C, bisphenol F, bisphenol S, and tetrabromobisphenol A. The water samples were concentrated and purified through HLB solid phase extraction cartridges. UPLC separation was performed on a Waters Acquity UPLC BEH T3 column （1.7 μm×2.1 mm× 100 mm） utilizing a gradient elution program of methanol （containing 2 mmol/L ammonium acetate） and water （containing 2 mmol/L ammonium acetate） as the mobile phases at a flow rate of 0. 2 mL/min. The MS/MS detection was performed under negative electrospray ionization （ESI^-） in multiple reaction monitoring （MRM）mode. The results showed that good linearity was observed in the range of 0. 10-50.0μg/L or 0. 50-100 μg/L with the correlation coefficients from 0. 997 to 0. 999, the limits of detection （LODs） for the six bisphenols were in the range of 0.05-0.31 ng/L. The recoveries ranged from 74.8% to 122% at three spiking levels, and the relative standard deviations （n= 6） were between 3.33% and 12.4%. The developed method was applied to analysis of the investigated compounds in surface water samples, which were collected from rivers and reservoirs in Hangzhou, and 5 pollutants were found. This method has high sensitivity and precision, extensive analytical range and quick analytical rate, which is suitable for analysis of the six investigated pollutants in surface water.