超高效液相色谱串联质谱法测定水产养殖水体中49种兽药的残留量

Determination of 49 veterinary drug residues in aquaculture water by ultra-performance liquid chromatography-tandem mass spectrometry

建立了超高效液相色谱串联质谱测定水产养殖水体中硝基呋喃类、磺胺类、氟喹诺酮类、大环内酯类等11类、49种药物的分析方法。样品分别采用固相萃取法和冷冻干燥法浓缩后,经Kinetex C18色谱柱分离,乙腈和0.1%甲酸水作为流动相梯度洗脱,正负离子同时扫描,多时段-多反应监测模式下测定,外标法定量。各种药物在相应的浓度范围内线性关系良好,相关系数大于0.998。冷冻干燥法各种药物的方法检出限为5~30 ng/L,加标回收率为63.1%~120%,相对标准偏差<15.2%。固相萃取法各种药物的方法检出限为1~5 ng/L,除孔雀石绿类外,加标回收率为67.1%~119%,相对标准偏差<13.6%。方法灵敏度高、重现性好,适用于测定水产养殖场池塘水样中残留的多种类药物。

An accurate, sensitive and reliable ultra performance liquid chromatography -tandem mass spectrometry method was developed for the simultaneous determination of 49 veterinary drugs in water samples. The samples were enriched by solid phase extraction and lyophilization, respectively. Chromatography separation was performed on a Ki- netex ClS column under gradient elution condition utilizing acetonitrile and 0.1% formic acid as mobile phases. The compounds were quantitated with external standard method in the multiple -period multiple reaction monitoring （MRM） mode using both positive and negative eleetrospray ionization. The good linearity was achieved in the corre- sponding concentration range of each analyte and the coefficient of correlation （r） was greater than 0. 998. The limits of detection （LOD） were in the range of 5 - 30 ng/L, and the recoveries of analytes in spiked samples were between 63.1% and 120% with relative standard deviations （RSD） less than 15.2% by lyophilization. The LODs were in the range of 1 -5 ng/L, and the recoveries of analytes （except for triphenylmethane dyes） in spiked samples were be- tween 67.1% and 119% with RSDs less than 13.6% by solid phase extraction. The proposed method can be applied to the determination of 49 veterinary drugs in real water samples.