固相萃取-超高效液相色谱-串联质谱法测定污水中83种药物和生物标志物  

Determination of 83 kinds of Pharmaceuticals and Biomarkers in Wastewater via Solid Phase Extraction Coupled with Ultra-performance Liquid Chromatography-Tandem Mass Spectrometry

作　　者：张瑞玲 刘昕 赵时真 张干[2] 郭鹏然 ZHANG Rui-Ling;LIU Xin;ZHAO Shi-Zhen;ZHANG Gan;GUO Peng-Ran(Guangdong Provincial Key Laboratory of Chemical Measurement and Emergency Test Technology,Institute of Analysis,Guangdong Academy of Sciences(China National Analytical Center Guangzhou),Guangzhou 510070,China;State Key Laboratory of Organic Geochemistry,Guangzhou Institute of Geochemistry,Chinese Academy of Sciences,Guangzhou 510640,China;Anti-Drug Technology Center of Guangdong Province and National Anti-Drug Laboratory Guangdong Regional Center,Guangzhou 510230,China)

机构地区：[1]广东省科学院测试分析研究所(中国广州分析测试中心),广东省化学测量与应急检测技术重点实验室,广州510070 [2]中国科学院广州地球化学研究所,有机地球化学国家重点实验室,广州510640 [3]广东省毒品实验技术中心(国家毒品实验室广东分中心),广州510230

出　　处：《分析化学》2024年第8期1192-1199,共8页Chinese Journal of Analytical Chemistry

基　　金：广东省科学院发展专项资金(No.2023GDASZH-2023010103);“一带一路”国际科学组织联盟项目(No.ANSO-CR-KP-2021-05);中国科学院青年创新促进会项目(No.2022359);广东省基础与应用基础研究基金项目(No.2023B1515020067)。

摘　　要：污水流行病学(WBE)可用于快速评估人群健康状况,但目前鲜有能同时检测污水中多种药物及生物标志物的分析方法。本研究建立了一种固相萃取-超高效液相色谱-串联质谱(SPE-UPLC-MS/MS)方法用于分析污水处理厂进水中83种药物和生物标志物。将含目标物的200 mL水样等分为两份,分别在pH 6.7和pH 2.0的条件下采用HLB柱富集和净化,再分别采用6 mL甲醇和6 mL含2%甲酸的甲醇洗脱,氮吹、浓缩后复溶至0.5 mL,经0.22μm尼龙过滤器过滤,采用UPLC-MS/MS法在电喷雾离子源多反应监测模式下测定,内标法定量分析。83种目标物在0.1~500 ng/mL浓度范围内线性关系良好(r>0.996),日内和日间精密度为1.2%~16.5%;纯净水和污水处理厂进水中目标物的回收率分别为51.6%~166.6%和56.4%~150.1%,相对标准偏差(RSD)分别为0.2%~31.9%和0.3%~20.9%,方法检出限为0.02~7.72 ng/L。应用本方法测定广州市某污水处理厂实际进水样品中的典型药物和生物标志物,共检出50种药物和4种生物标志物,药物中对乙酰氨基酚和红霉素浓度最高,分别为1.6~3.4μg/L和0.6~1.1μg/L;生物标志物中咖啡因浓度最高,为33.3~43.9μg/L。本方法灵敏度高、稳定性好,适用于污水处理厂进水中药物和生物标志物的准确定量分析,可为开展污水流行病学研究提供分析方法支撑。Wastewater-based epidemiology(WBE)can effectively assess population health status,but it is lack of analytical methods which can simultaneously analyze a number of pharmaceuticals and biomarkers in wastewater.In this work,a method including sample pretreatment and instrumental detection for quantifying 83 kinds of pharmaceuticals and biomarkers in the influent of wastewater treatment plants(WWTPs)was established by sing solid phase extraction-ultra performance liquid chromatography-tandem mass spectrometry(SPE-UPLC-MS/MS).The water sample(200 mL)with 83 kinds of target compounds was divided into two aliquots,which were then enriched and purified using HLB columns at pH=6.7 and pH=2 respectively,followed by elution with 6 mL of methanol and 6 mL of methanol containing 2%(V/V)formic acid,respectively,and then dried by nitrogen blown,concentrated,and finally redissolved to 0.5 mL,filtered through a nylon filter(0.22μm).The target compounds in the samples were determined using UPLC-MS/MS in electrospray ionization under both positive and negative ion multiple reaction monitoring modes,with quantification using the internal standard method.The method exhibited good linearity(r>0.996)for the 83 kinds of target compounds in the concentration range of 0.1–500 ng/mL,and intra-day and inter-day precisions were 1.2%–16.5%.The recoveries of target substances in pure water and influent samples from a WWTP were 51.6%–166.6%and 56.4%–150.1%,respectively,with relative standard deviations of 0.2%–31.9%and 0.3%–20.9%,respectively.The method detection limits of target compounds were 0.02–7.72 ng/L.This method was applied to determine pharmaceuticals and biomarkers in the influent samples of a WWTP in Guangzhou,and 54 kinds of pharmaceuticals and 4 kinds of biomarkers were detected.The concentrations of acetaminophen and erythromycin were the highest among the pharmaceuticals,1.6–3.4μg/L and 0.6–1.1μg/L,respectively.The concentration of caffeine was the highest among the biomarkers,i.e.,33.3–43.9μg/L.This met

关 键 词：药物 生物标志物 污水 超高效液相色谱-串联质谱法 固相萃取 

分 类 号：O657.63[理学—分析化学] X832[理学—化学]