养猪废水和污泥中11种兽用抗生素的同时分析技术及其在生物降解过程的应用

优化了固相萃取与高效液相色谱串联质谱联用的分析条件,使之适用于检测长三角地区养猪废水和污泥中常见的11种兽用抗生素(包括4种四环素类、2种磺胺类、3种喹诺酮类和2种大环内酯类).该分析方法对养猪废水的平均加标回收率(n=3)为73.0%~105.2%,相对标准偏差为3.1%~10.2%;对污泥的平均加标回收率(n=3)为57.4%~104.6%,相对标准偏差为1.9%~10.9%.研究膜生物反应器中抗生素的浓度变化,发现废水中抗生素以四环素类和磺胺类为主,而污泥中以四环素类为主.反应器对废水中四环素类抗生素的去除率为85.2%,其中最主要的去除途径是生物分解(51.9%),其次是污泥吸附(33.2%);而磺胺类抗生素去除率为95.8%,几乎全部是依靠生物分解,污泥吸附很少.摇瓶实验结果显示,污泥中积累的抗生素未对活性污泥的有机物降解活性和硝化活性产生明显影响.

Method for Simultaneous Determination of 11 Veterinary Antibiotics in Piggery Wastewater and Sludge and Its Application in Biological Treatment

In order to determine eleven commonly used veterinary antibiotics (including four tetracyclines, two sulfonamides, three quinolones and two macrolides) in piggery wastewater and activated sludge in the Yangtze River Delta region, the conditions of solid phase extraction and high performance liquid chromatography-tandem mass spectrometry were optimized.The recovery rate and relative standard deviations of the method were confirmed as 73%-105.2%, 3.1%-10.2% for piggery wastewater (n=3) and 57.4%-104.6%, 1.9%-10.9% (n=3) respectively for the activated sludge.Removal of antibiotics was then studied in a membrane bioreactor.The results showed that antibiotics of both tetracycline and sulfonamide species took a large portion in the wastewater, while tetracycline species were the dominant in the sludge.Tetracycline species in the wastewater were removed by 85.2%, mainly through biodegradation (51.9%) and secondly by sludge adsorption (33.2%).By comparison, sulfonamide species was removed by 95.8%, almost all through biodegradation while little by sludge adsorption.Flask tests suggested that the accumulated antibiotics in the sludge give no significant influence on the microbial removal of organics and ammonium.