固相萃取/超高效液相色谱-质谱法筛查及检测养鱼河水中抗生素

建立了固相萃取/超高效液相色谱-串联三重四极杆质谱(UPLC-MS/MS)快速检测养鱼河水中4类(喹诺酮类、氯霉素类、四环素类以及磺胺类)15种抗生素的分析方法。取500 m L水样过滤,用盐酸调至p H4.0,加入0.5 g乙二胺四乙酸二钠(Na2EDTA)混匀后,再用HLB固相萃取柱对水样进行富集。利用超高效液相色谱-串联四极杆飞行时间质谱(UPLC-Q-TOF MS)结合基于UNIFI软件的常用抗生素数据库对养鱼河水中可能存在的抗生素进行快速筛查,筛查结果主要为喹诺酮类、氯霉素类、四环素类、磺胺类4类15种抗生素。为了提高检测结果的准确性,使用UPLC-MS/MS采用分时段多反应监测离子模式(MRM)分析样品中的抗生素,并用外标法定量。15种抗生素的空白基质加标回收率为61.0%~98.4%,相对标准偏差(n=3)为4.6%~14.0%,其线性关系良好,相关系数r≥0.990,检出限为0.01~0.3 ng/L。该方法灵敏度较高,重复性好,可用于对北京养鱼河水中抗生素的检测。

Screening and Detection of Antibiotics in Fish Pond Water by Ultra Performance Liquid Chromatography-Mass Spectrometry with Solid Phase Extraction

A method was established for the rapid detection of 15 kinds of antibiotics(quinolones,chloramphenicol,tetracycline and sulfonamides) in river water near fish farms by ultra performance liquid chromatography-tandem triple quadrupole mass spectrometry(UPLC-MS/MS) with solid-phase extraction.After filtration,a 500 mL of water sample was adjusted to pH 4.0 with hydrochloric acid,then added 0.5 g ethylenediaminetetraacetic acid disodium(Na2EDTA) to removal the interference of variousmetal ions,and finally enriched with an HLB solid-phase extraction column.The sample was detected by ultra performance liquid chromatography couple with quadrupole time-of-flight mass spectrometry(UPLC-Q-TOF MS),and screened for the antibiotics with antibiotic library.The corfirmation and quantitation of antibiotics in the sample were performed by UPLC-MS/MS in multi-period multi-reaction monitoring ion mode(MRM) with external standard method.The spiked recoveries for 15 antibiotics in blank matrix were in the range of 61.0%-98.4% with the relative standard deviations(n=3) of 4.6%-14.0%.The calibration curves of 15 antibiotics showed good linearity with the correlation coefficients not less than 0.990.The method detection limits(MDLs) ranged from 0.01 ng/L to 0.3 ng/L.With high sensitivity and good repeatability,this method could be applied in the detection of antibiotics in fish pond water in Beijing.