地表水中20种四环素类抗生素及其转化产物的同时检测方法研究和应用  

Research and application of simultaneous detection method for 20 tetracyclines and transformation products in surface water

作　　者：黄梦凡 李敏[1] 刘娟 姚巧 王超[2] 冯承莲[3] 孙福红[3] 陈瑀 常红 HUANG Mengfan;LI Min;LIU Juan;YAO Qiao;WANG Chao;FENG Chenglian;SUN Fuhong;CHEN Yu;CHANG Hong(College of Environmental Sciences&Engineering,Beijing Forestry University,Beijing,100083,China;China CDC Key Laboratory of Environment and Human Health,National Institute of Environmental Health,Chinese Center for Disease Control and Prevention,Beijing,100021,China;State Key Laboratory of Environmental Criteria and Risk Assessment,Chinese Research Academy of Environmental Sciences,Beijing,100012,China)

机构地区：[1]北京林业大学环境科学与工程学院,北京100083 [2]中国疾病预防控制中心环境与健康相关产品安全所,中国疾病预防控制中心环境与人群健康重点实验室,北京100021 [3]中国环境科学研究院,环境基质与风险评估国家重点实验室,北京100012

出　　处：《环境化学》2024年第7期2194-2205,共12页Environmental Chemistry

基　　金：国家重点研发计划项目(2022YFC3201901);国家自然科学基金(42077306)资助.

摘　　要：四环素类抗生素(TCs)由于水解和光解等作用容易生成多种转化产物、且有些转化产物具有更强的毒性效应,因此,TCs转化产物的环境存在引起的风险不容忽视.本研究建立了超高效液相色谱串联三重四极杆质谱(UPLC-MS/MS)同时检测地表水体中7种TCs及13种转化产物的分析方法,细致研究了TCs及其转化产物的质谱碎裂和液相色谱分离规律.水样添加5 g·L^(-1)Na_(2)EDTA后经Oasis HLB固相萃取柱富集净化、1%甲酸甲醇洗脱后用UPLC-MS/MS测定.流动相为甲醇和0.1%甲酸水溶液,在Waters BEH C18柱上采用梯度洗脱,实现了20种TCs及其转化产物的准确鉴定.实际水样中绝大多数目标污染物的加标回收率为60%—130%,方法检出限在24.5—927 pg·L^(-1)之间.应用此方法于永定河(北京段)27个样品,检测出6种原型TCs(平均浓度70.0—560 pg·L^(-1);检出频率3.7%—29.6%)和9种转化产物(70.0—1980 pg·L^(-1);3.7%—37%),转化产物与原型物质的检出浓度和检出频率在同一水平上、甚至稍高,应该重视与TCs同时存在的转化产物所引起的环境和健康风险.Due to the hydrolysis and photolysis of tetracycline antibiotics(TCs),they are easy to generate a variety of transformation products,and some of them even have stronger toxicities.Therefore,the risks caused by the environmental occurrences of TC transformation products could not be ignored.A method of ultra-performance liquid chromatography tandem mass spectrometry(UPLC-MS/MS)combined with solid-phase extraction(SPE)has been developed for simultaneous analysis of 7 TCs and 13 transformation products in surface water.It was studied in detail about their mass spectrometric fragmentation pattern and chromatographic separation.After adding 5 g·L^(-1) Na_(2)EDTA,the water samples were enriched through Oasis HLB cartridges,and eluted with 1%formic acid in methanol for UPLC-MS/MS detection.The detection used gradient elution process on Waters BEH C18 column with methanol and 0.1%formic acid in water as the mobile phase to achieve accurate identification of these 20 analytes.The method detection limits were 24.5—927 pg·L^(-1) and spiking recoveries of 60%—130%for most target analytes in surface sample.Application of this method for 27 water samples collected from the Yongding River in Beijing area showed that 6 TCs and 9 transformation products were detected with the average concentrations of 70.0—560 pg·L^(-1)(detection frequencies of 3.7%—29.6%)and 70.0—1980 pg·L^(-1)(3.7%—37%),respectively.The detection concentrations and detection frequencies of transformation products are close to those of TCs,thus more attention should be paid to the environmental and health risks caused by the coexisting TC transformation products.

关 键 词：新污染物 抗生素 四环素 转化产物 高效液相色谱质谱 地表水 

分 类 号：X-1[环境科学与工程] O6[理学—化学]