高效液相色谱-质谱联用法同步测定城市污水处理厂活性污泥中的多类抗生素残留

Simultaneous Determination of Several Classes of Antibiotics in the Activated Sludge of Municipal Sewage Treatment Plants by High Performance Liquid Chromatography-Mass Spectrometry

采用超声萃取、固相萃取及高效液相色谱-质谱联用技术(LC-MS),建立了活性污泥中3类共9种抗生素(包括5种磺胺类、3种四环素类及1种大环内酯类)的同时分析方法。样品经甲醇-Na2EDTA/McIlvaine缓冲液(1∶1,体积比)超声萃取,HLB固相萃取柱净化富集后,以Symmetry C18反相柱为分析柱,0.2%甲酸-乙腈为流动相梯度洗脱,采用电喷雾电离源在选择离子扫描模式下进行抗生素的定性及定量分析。方法的线性范围为0.001～1 mg/L,相关系数均大于0.99,在3个加标水平下的回收率分别为80%～108%(磺胺类)、91%～112%(四环素类)及50%～59%(大环内酯类),日内及日间相对标准偏差分别不大于7.4%和13.7%,方法检出限为1～16μg/kg。该方法被成功地应用于北京市两家污水处理厂活性污泥中的抗生素残留分析,5种目标抗生素被检出,其中磺胺类的检出量为124.9～523.3μg/kg,四环素类的检出量为166.5～2 296.4μg/kg。

A highly selective and sensitive analytical method was developed for simultaneous determination of three classes of commonly used antibiotics, including five sulfonamides, three tetracyclines and one macrolide in the activated sludge of municipal sewage treatment plants（STPs） by ultrasonic extraction, solid-phase extraction and high performance liquid chromatography - mass spectrometry （ LC - MS）. The activated sludge sample was ultrasonically extracted with a mixture of methanol and Na2EDTA/Mcllvaine buffer（ 1 ： 1 ） , then concentrated and purified with an HLB cartridge. The separation of targeted compound was performed with a Waters Symmetry C18 column using 0.2% formic acid（A） -acetonitrile（B） as mobile phase. The qualification and quantification of the selected antibiotics were carried out by MS with an electrospray ionization（ESl） under the positive ion mode. The of detection （LOD） were between 1 μg/kg and 16 μg/kg. The developed method was applied in the detection of the activated sludge samples collected from two STPs located in Beijing and five target antibiotics were detected with concentrations of 124. 9 -523.3 μg/kg for sulfanomindes and 166.5 - 2 296.4μg/kg for tetraeyclines, respectively.