Central Laboratory, Beijing Center for Disease Control and Prevention, Beijing 100013, China.
J Chromatogr A. 2009 Nov 20;1216(47):8312-8. doi: 10.1016/j.chroma.2009.08.038. Epub 2009 Aug 21.
A multi-residue method for the analysis of 76 pharmaceutical agents of nine classes of drugs (tetracyclines, macrolides, fluoroquinolones, beta-agonists, beta-blockers, diuretics, sedatives, sulfonamides and chloramphenicol) in slaughterhouse wastewater and a receiving river is presented. After simultaneous extraction with an Oasis HLB solid-phase extraction (SPE) cartridge and further purification using an amino SPE cartridge, analytes were detected by liquid chromatography-electrospray ionization-tandem mass spectrometry in positive or negative ion mode. Standard addition was used for quantification to overcome unavoidable matrix effects during ESI-MS analysis. Recoveries for most analytes based on matrix-matched calibration in different test matrices were >60%. The method quantification limits of 76 pharmaceuticals were in the range 0.2-30 ng/L. Nineteen compounds of 76 drugs were found in raw and treated slaughterhouse wastewater from four main slaughterhouses in Beijing. Sulfanamides (sulfanilamide, sulfameter), fluoroquenones (ofloxacin, pefloxacin, norfloxacin, ciprofloxacin, enrofloxacin), tetracyclines (tetracycline, oxytetracycline) and macrolides (kitasamycin, tylosin, erythromycin) were most frequently detected, with the highest levels up to approximately 3 microg/L in slaughterhouse wastewater and approximately 1 microg/L in treated wastewater. Illicit drugs for animal feeding such as clenbuterol and diazepam were commonly detected in slaughterhouse wastewater. These analytes were also observed in a river receiving slaughterhouse wastewater, with a highest level of up to 0.2 microg/L.
本文建立了一种固相萃取-液相色谱-串联质谱同时测定屠宰废水中 9 类 76 种药物(四环素类、大环内酯类、氟喹诺酮类、β-激动剂、β-阻断剂、利尿剂、镇静剂、磺胺类和氯霉素)残留的分析方法。样品经 OasisHLB 固相萃取柱和氨基固相萃取柱净化后,采用液相色谱-电喷雾串联质谱在正、负离子模式下进行检测,标准加入法定量以克服电喷雾离子源分析时基质效应的影响。在不同基质中,以基质匹配标准曲线进行定量,大多数药物的回收率>60%。该方法的 76 种药物的检出限为 0.2-30ng/L。在北京市 4 家主要屠宰场的未经处理和处理后的屠宰废水中共检出 19 种药物,磺胺类(磺胺甲噁唑、磺胺间甲氧嘧啶)、氟喹诺酮类(氧氟沙星、培氟沙星、诺氟沙星、环丙沙星、恩诺沙星)、四环素类(四环素、土霉素)和大环内酯类(吉他霉素、泰乐菌素、红霉素)是主要残留药物,浓度高达 3μg/L(未经处理的废水)和 1μg/L(处理后的废水)。非法用于动物养殖的药物如克伦特罗和地西泮也在屠宰废水中普遍检出,在受屠宰废水污染的河流中也有检出,最高浓度达 0.2μg/L。