超高效液相色谱-三重四极杆质谱法测定水中11大类145种药品和个人护理品

Determination of 145 pharmaceuticals and personal care products in eleven categories in water by ultra-high performance liquid chromatography-triple quadrupole mass spectrometry

药品和个人护理品(PPCPs)在水环境中频繁检出,是一类受到国内外环保部门普遍关注的新污染物。准确掌握水环境中PPCPs存在的种类及浓度水平,获取水环境中各类PPCPs的基础污染数据,是环境管理部门进行新污染物管控的重要基础。为此,必须开发准确灵敏、方便快捷且能实现高通量筛查及定量分析的检测方法。本研究采用大体积直接进样-超高效液相色谱-三重四极杆质谱法测定水环境中11大类(抗生素、降压药、降糖药、抗病毒药、β-受体激动剂、硝基咪唑类药物、H2受体拮抗剂、精神麻醉类药物、降血脂药、非甾体抗炎药及其他类药物和杀菌剂类个人护理品)145种PPCPs。水样经0.22μm的再生纤维素滤膜过滤,加入乙二胺四乙酸二钠(Na2EDTA)并调节pH值至6.0~8.0,加入内标混匀后,采用Phenomenex Kinetex C18柱(50 mm×3 mm,2.6μm)进行色谱分离,以含5 mmol/L甲酸铵的0.1%甲酸水溶液-乙腈为正离子扫描模式下的流动相、5 mmol/L甲酸铵水溶液-乙腈为负离子扫描模式下的流动相,分别进行梯度洗脱,质谱智能化分时间段-多反应选择离子监测(Schedule-MRM)模式检测,内标法定量。145种PPCPs在一定的范围内线性良好,方法检出限为0.015~5.515 ng/L,在低、中、高3个加标水平下的回收率为80.4%~128%,相对标准偏差为0.6%~15.6%。将该方法应用于11份地表水样品和6份饮用水样品的检测,结果显示,145种PPCPs中共检出93种化合物,地表水中PPCPs总含量为276.9~2705.7 ng/L,其中抗病毒药、降糖药和精神麻醉类药品的检出率为100%且含量占比最大;饮用水中检出的PPCPs总含量为140.5~211.5 ng/L,主要检出抗生素、抗病毒药和降糖药。该方法简单快捷,可实现上百种PPCPs的同时测定,适用于环境水体中多种PPCPs残留的测定。

Pharmaceuticals and personal care products(PPCPs)are emerging contaminants frequently detected in aquatic environments at trace levels.These chemicals have diverse structures and physicochemical properties and includes pharmaceuticals like antibiotics,antihypertensive drugs,antiviral drugs,and psychotropic drugs that are widely used in large quantities worldwide.Considering the large number of pharmaceuticals currently in usage,it is crucial to establish a priority list of PPCPs that should be monitored and/or treated first.An accurate understanding of the occurrence and levels of PPCPs in aquatic environments is essential for providing objective materials for monitoring these emerging contaminants.Therefore,accurate,efficient,sensitive,and high-throughput screening techniques need to be established for determining and quantifying PPCPs.This study developed a method for the determination of 145 PPCPs(grouped into eleven categories:antibiotics,antihypertensive drugs,antidiabetic drugs,antiviral drugs,β-receptor agonists,nitroimidazoles,H 2 receptor antagonists,psychotropic drugs,hypolipidemic drugs,non-steroidal anti-inflammatory drugs,and others)in water.The method was based on large volume direct injection without sample enrichment and cleanup and used ultra-high performance liquid chromatography-triple quadrupole mass spectrometry(UHPLC-MS/MS).Water samples were collected and filtered through a 0.22-μm regenerated cellulose(RC)filter membrane.Subsequently,Na 2EDTA was added to the samples to adjust their pH to 6.0-8.0.Internal standards were mixed with the solutions,and because of the addition of Na 2EDTA,the interference of metal ions could be eliminated in the determination of compounds,especially for tetracycline and quinolone antibiotics.Among the six filter membranes tested in this study(PES,PFTE-Q,PFTE,MCE,GHP,and RC),RC filter membranes were screened for water sample filtration.The UHPLC-MS/MS parameters were optimized by comparing the results of various mobile phases,as well as by establishing the best instrumental conditions.The 145 PPCPs were separated using an Phenomenex Kinetex C18 column(50 mm×3 mm,2.6μm)via gradient elution.The mobile phases were 0.1%(v/v)formic acid aqueous solution containing 5 mmol/L ammonium formate and acetonitrile for positive ion modes,5 mmol/L aqueous solutions of ammonium formate and acetonitrile for negative ion modes.The samples were quantified using the scheduled multiple reaction monitoring(scheduled-MRM)mode with electrospray ionization in positive and negative ion modes.A standard internal calibration procedure was used to calculate contents of sample.The established method was systematically verified,and it demonstrated a good linear relationship.The average recoveries of the 145 PPCPs at the three spiked levels were in the range of 80.4%-128%with relative standard deviations(RSDs,n=6)of 0.6%-15.6%.The method detection limits(MDLs)ranged from 0.015 to 5.515 ng/L.Finally,the optimization method was applied to analyze the 145 PPCPs in 11 surface water samples and 6 drinking water samples.Overall,93(64%)out of the 145 analytes were detected.The total contents of the PPCPs in surface water samples ranged from 276.9 to 2705.7 ng/L.The detection frequencies of antidiabetic,antiviral,and psychotropic drugs were 100%.The total contents of the PPCPs in drinking water samples ranged from 140.5 to 211.5 ng/L,and antibiotics,antidiabetic drugs,and antiviral drugs comprised the largest proportion of analytes(by mass concentration)in drinking water samples.Our method exhibited high analytical speed and high sensitivity.It is thus suitable for the trace analysis and determination of the 145 PPCPs in environmental water and showed improved detection efficiency for PPCPs in water,indicating that it has a high potential for practical applications.This study can extend technical support for further pollution-level analysis of PPCPs in water and provide an objective basis for environmental management.