超高效液相色谱-串联三重四级杆质谱法快速测定尿液中4种除草剂

Rapid determination of four herbicides in urine with ultra-high performance liquid chromatography-triple quadrupole tandem mass spectrometry

目的建立超高效液相色谱-串联三重四级杆质谱法同时快速测定尿液中二氯喹啉酸、乙草胺、丁草胺和异丙甲草胺。方法人工尿液稀释10倍后配制混合标准溶液,在色谱柱ACQUITY UPLC BEH C18(100 mm×2.1 mm,1.7μm)上以0.1%甲酸和乙腈为流动相进行梯度洗脱,采用电喷雾正离子源、多反应监测模式检测二氯喹啉酸、乙草胺、丁草胺和异丙甲草胺含量。结果4种除草剂在色谱柱ACQUITY UPLC BEH C18(100 mm×2.1 mm,1.7μm)上可有效分离。二氯喹啉酸、乙草胺和丁草胺在1~25μg/L范围内,异丙甲草胺在0.2~25μg/L范围内线性关系良好,相关系数均>0.999。二氯喹啉酸、乙草胺、丁草胺和异丙甲草胺的检出限分别为0.10、0.10和0.20和0.01μg/L。在5μg/L加标水平下尿液中二氯喹啉酸、乙草胺和丁草胺的回收率分别为107.42%、93.94%和90.27%,相对标准偏差分别为4.82%、3.84%和6.76%;在0.5μg/L加标水平下,异丙甲草胺的回收率为89.51%,相对标准偏差为8.98%。结论本方法优化了色谱和质谱条件,可实现尿液中二氯喹啉酸、乙草胺、异丙甲草胺和丁草胺的同时快速测定。

Objective To establish a ultra-high performance liquid chromatography-tandem triple quadrupole mass spectrometry method for rapid simultaneous determination of quinclorac,acetochlor,butachlor and metolachlor in urine.Methods Urine samples were diluted 10 times,prepared into the mixed standard solution,and subjected to gradient elution on the ACQUITY UPLC BEH C18 column(100 mm×2.1 mm,1.7μm)with 0.1%formic acid and acetonitrile as the mobile phase.The quinclorac,acetochlor,metolachlor and butachlor levels were determined using electrospray ionizationpositive ultra-high performance liquid chromatography-tandem triple quadrupole mass spectrometry with the multiple reaction monitoring mode.Results Four herbicides were effectively separated on the ACQUITY UPLC BEH C18 column(100 mm×2.1 mm,1.7μm),and good linear relationships were observed for quinclorac,acetochlor and butachlor at 1to 25μg/L and for metolachlor at 0.2 to 25μg/L,with all linear correlation coefficients of>0.999.The detection limts of quinclorac,acetochlor,butachlor and metolachlor were 0.10,0.10,0.20 and 0.01μg/L,respectively.The recovery rates of quinclorac,acetochlor and butachlor were 107.42%,93.94%and 90.27%from urine samples at a spiked level of 5μg/L,with relative standard deviations of 4.82%,3.84%and 6.76%,and the recovery rate of metolachlor was89.51%at a spiked level of 0.5μg/L,with a relative standard deviation of 8.98%.Conclusion The chromatography and mass spectrometry conditions are optimized in this ultra-high performance liquid chromatography-tandem mass spectrometry,which is effective for rapid simultaneous determination of quinclorac,acetochlor,metolachlor and butachlor in urine samples.