固相萃取-超高效液相色谱-电喷雾串联质谱法同时测定地表水中9种微囊藻毒素

Simultaneous determination of nine microcystins in surface water by solid phase extraction and ultra performance liquid chromatography-electrospray ionization tandem mass spectrometry

建立了固相萃取-超高效液相色谱-电喷雾串联三重四极杆质谱(SPE-UPLC-ESI-MS/MS)联用技术分析水中9种微囊藻毒素的方法。样品经SPE提取和净化后,以Waters ACQUITY UPLCTM BEH C18色谱柱为分离柱,以含0.1%甲酸乙腈和含0.1%甲酸水作为流动相进行梯度洗脱,电喷雾离子源电离、正离子多反应监测模式质谱进行定性和定量分析。9种微囊藻毒素在0.1～50μg/L或0.5～100μg/L质量浓度范围内线性良好,相关系数为0.999 0～0.999 8,方法的检出限(以3倍信噪比计)为0.1～0.5 ng/L;高、中、低3个添加水平的回收率为75.8%～109%,相对标准偏差为0.49%～10.0%。结果表明,该方法灵敏、准确,检测范围广,分析速度快。应用该方法检测了杭州市两处水库水样中的微囊藻毒素,分别检出了3种和8种微囊藻毒素。

A method has been developed for the simultaneous determination of nine microcystins （MCs） in surface water by solid phase extraction-ultra performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry （SPE-UPLC-ESI-MS/MS）. The samples were enriched and purified by an HLB solid phase extraction column. The separa- tion was performed on an ACQUITY UPLCTM system with a BEH C18 column with the gradient elution of acidified acetonitrile and water （both containing 0. 1% （v/v） formic acid）. The nine MCs were determined in the modes of electrospray positive ionization （ ESI ＋ ） and multiple reaction monitoring （MRM）. Good linearities were observed in the ranges of 0. 1 -50μg/L for MC-RR and 0.5 - 100 μg/L for the others with correlation coefficients over 0. 999 0 and the lim- its of detection for the nine MCs were in the range of 0. 1 - 0.5 ng/L. The recoveries were in the range of 75.8% - 109% in the three spiked levels of 1. 0, 10 and 50μg/L with the relative standard deviations of 0.49% - 10.0%. The method is characterized by high sensitivity and precision, extensive analytical range and quick analytical rate. This method was used in the analysis of water samples from two reservoirs situated in Hangzhou, and the 3 and 8 microcystins were detected individually.