超高效液相色谱-串联质谱法测定地表水中的48种药物残留

Determination of 48 drug residues in surface water by ultra-performance liquid chromatography tandem mass spectrometry

目的建立全自动固相萃取-超高效液相色谱-串联三重四极杆质谱法(UPLC-MS/MS)高通量检测地表水中的48种药物残留。方法样品经GF/C玻璃纤维滤纸过滤后,取500 ml清液,加入EDTA-Na_(4)消除金属离子的干扰,盐酸调节pH值至2.5,经BRP固相萃取小柱在100 ml/min的流速下上样富集,5%甲醇水溶液淋洗除杂,甲醇洗脱,洗脱液氮吹至近干,1.00 ml 10%甲醇水溶液溶解残留物,以0.1%甲酸水溶液和0.1%甲酸乙腈溶液为流动相,经CORTECS UPLC C_(18)色谱柱(150 mm×3.0 mm,1.6μm)梯度分离,三重四极杆质谱仪在正离子模式下多反应监测(MRM),内标法定量。结果当固相萃取上样流速达到100 ml/min时,仍可获得满意的回收率,大幅提升了工作效率。48种化合物在0.50 ng/ml~10.00 ng/ml内线性关系良好(r>0.995),方法的定量限为0.1 ng/L~1.0 ng/L,加标回收率在63.4%~140.0%,相对标准偏差在1.26%~18.40%。采用所建方法对10份地表水进行检测,共检测到13种目标物,浓度在0.4 ng/L~8.0 ng/L。结论本方法简单、快速,适用于环境水体中多种类药物残留的同时、快速检测。

Objective This paper aims to establish a high-throughput method for the determination of 48 drug residues in surface water by automatic solid phase extraction combined with ultra-performance liquid chromatography tandem triple mass spectrometry(UPLC-MS/MS).Methods After filtered with GF/C glass fiber filter,EDTA-Na_(4) was added to 500 ml supernatant sample to eliminate interfering metal ions,and then its pH was adjusted to 2.5 with hydrochloric acid solution.The solution was loaded at a flow rate of 100 ml/min on a BRP solid phase extraction column for concentration,5%methanol aque⁃ous was used for purified,and methanol was used for elution,nitrogen was used to blow the samples nearly dry.The residues were dissolved with 1.00 ml 10%methanol aqueous,0.1%formic acid aqueous solution and 0.1%formic acid acetonitrile solution were used as flowing phase,and a CORTECS UPLC C_(18) column(150 mm×3.0 mm,1.6μm)was used for gradient separation.The determination was performed by a triple quadrupole mass spectrometer in positive ion mode with multiple reac⁃tion monitoring(MRM).Results The efficiency of sample preparation was largely improved by optimizing the loading rate of solid phase extraction to 100 ml/min without reducing recovery.The linear correlation coefficients(r)of 48 drugs within 0.50 ng/L-10.00 ng/L were all greater than 0.995,with the quantification limits of 0.1 ng/L-1.0 ng/L.The recoveries were in the range of 63.4%-140.0%,with the relative standard deviations(RSDs)of 1.26%-18.40%.Ten samples were analyzed by the established method,and 13 drug residues were detected,with the concentration of 0.4 ng/L-8.0 ng/L.Conclusion The established method is simple,rapid,and suitable for the simultaneous determination of multi-drug residues in surface water.