制药废水中头孢类抗生素残留检测方法及环境风险评估

基于固相萃取-超高效液相色谱-两级串联质谱(SPE-UPLC/MS/MS)技术,建立了制药废水中头孢克洛、头孢曲松、头孢氨苄、头孢噻肟、头孢唑啉、头孢呋辛、头孢西丁、头孢噻吩和头孢拉定共9种头孢类抗生素的测试方法,定量限为27.5~131.8ng/L,目标物回收率为72.8%~102.2%;利用该技术,检测某采用两级生物氧化工艺的制药废水处理厂各级单元出水,共检测出头孢曲松、头孢唑啉、头孢噻肟和头孢呋辛4种头孢类抗生素,其在进水中平均浓度分别为7.6,12.9,5.6,91.6μg/L,在一级氧化出水中平均浓度分别为4.2,5.2,2.2,37.4μg/L,在二级氧化出水中平均浓度分别为2.0,2.7,0.6,24.4μg/L;风险商值法评估制药废水出水中残留的头孢曲松、头孢唑啉、头孢噻肟和头孢呋辛的环境风险均为高风险等级.

Residue analysis method and environmental risk assessment of cephalosporin antibiotics in pharmaceutical wastewater

Based on solid phase extraction (SPE) and ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), a testing method for 9 cephalosporin antibiotics, i.e., cefaclor, ceftriaxone, cephalexin, cefotaxime, cefazolin, cefuroxime, cefoxitin, cefalotin and cefradine, in pharmaceutical wastewater was established. The limit of quantitation was from 27.5 to 131.8ng/L, and the recovery efficiencies for different analytes ranged from 72.8% to 102.2%. With this method, cephalosporin antibiotics in the effluent of each processing unit of a pharmaceutical wastewater treatment plant (P-WWTP), which adopted two-stage biological oxidation processes, were tested. Ceftriaxone, cefazolin, cefotaxime and cefuroxime were found in the pharmaceutical wastewater. Their average concentrations in influents were 7.6, 12.9, 5.6 and 91.6μg/L, in effluents of first-stage oxidation unit were 4.2, 5.2, 2.2 and 37.4μg/L, and in effluents of second-stage oxidation unit were 2.0, 2.7, 0.6 and 24.4μg/L, respectively. Risk quotient method was utilized to evaluate the environmental risks of these four antibiotics in the effluents, and all the results were high risk levels.