超高效液相色谱-串联质谱法同时测定制药废水中10种抗生素

Simultaneous determination of ten antibiotics in pharmaceutical wastewater using ultra-high performance liquid chromatography-tandem mass spectrometry

建立了一种同时测定制药废水中3类10种抗生素的超高效液相色谱-串联质谱分析方法。水样用固相萃取柱富集净化，通过比较在不同的固相萃取柱和洗脱液等条件下水样中目标物的回收率，优化了前处理方法。采用Agilent C18色谱柱（75 mm×2.1 mm，2.7μm），以0.2％（v／v）甲酸水溶液和乙腈为梯度洗脱的流动相，在电喷雾-多反应监测模式下进行定性定量分析。实验结果表明：在0.1～1000μg／L 范围内，6种氨基糖苷类抗生素、螺旋霉素及3种氟喹诺酮类抗生素的峰面积与质量浓度的线性关系良好（ r2＞0.995），方法检出限为0.07～4.37 ng／L，定量限为0.22～14.55 ng／L；目标抗生素的加标水平为0.002～40μg／L 时，平均回收率为50.4％～114.1％，相对标准偏差均不高于9.89％（ n＝3）。基于上述方法，对江苏省某制药厂废水中相关物质进行检测，在各废水处理单元中检出3种目标抗生素，质量浓度范围为0.46～1033.60μg／L。该方法准确可靠、灵敏度高，适用于制药厂废水中氨基糖苷类抗生素、螺旋霉素和氟喹诺酮类抗生素的检测。

A simultaneous analytical method was established for ten selected antibiotics from three categories in pharmaceutical wastewater with ultra-high performance liquid chromatogra-phy-tandem mass spectrometry （ UPLC-MS/MS ）. The water samples were enriched and cleaned-up by solid phase extraction cartridges. The types of solid phase extraction cartridges and eluents were optimized by comparing the recoveries of the analytes in water samples under different conditions. The target compounds were separated on an Agilent C18 column（75 mm× 2. 1 mm,2. 7 μm）with the mobile phases of acetonitrile and 0. 2%（ v/v）formic acid aqueous solution,and then determined by electrospray ionization mass spectrometry（ ESI-MS）. The results showed that the calibration curves were linear in the range of 0. 1-1 000 μg/L（ r 2〉0. 995）. The limits of detection（ LODs,S/N≥3）and the limits of quantification（ LOQs,S/N≥10）of the ten compounds were 0. 07-4. 37 ng/L and 0. 22-14. 55 ng/L,respectively. The recov-ery experiments were performed with samples spiked in the range of 0. 002-40 μg/L. The recoveries of the target compounds were in the range of 50. 4%-114. 1%（ RSDs≤9. 89%,n=3）. Based on this analytical method,the raw and treated sewage samples from a pharmaceutical manufacturer wastewater treatment plant in Jiangsu Province were analyzed. Three compounds were detected in the samples from different sewage treatment units in the range of 0. 46-1 033. 60 μg/L. It shows that the method is accurate,reliable,highly sensitive and can be used＆nbsp;to analyze the water samples of pharmaceutical wastewater treatment plant containing amin-oglycosides,spiramycin and fluoroquinolones antibiotics.