摘要
本研究建立了一种固相萃取结合高效液相色谱-三重四极杆质谱法分析饮用水处理厂水样中7种香豆素类化合物的方法。样品前处理过程采用HLB小柱进行固相萃取,然后采用超纯水(含025%甲酸)淋洗,最后经甲醇(含025%甲酸)洗脱。萃取液用Phenomenex Luna C18柱(100 mm×20 mm,3μm)分离后,以甲醇-01%甲酸水溶液为流动相进行梯度洗脱,在电喷雾多反应监测模式下检测。以饮用水原水和出厂水为基质考察方法的基质效应、精密度和准确度。7种香豆素类化合物在各自的线性范围内呈现良好的线性关系,相关系数(r)均大于099,方法检出限(MDL)为067~112 ng/L。不同加标水平(20、50、100 ng/L)下7种香豆素类化合物回收率为614%~915%,相对标准偏差(RSD,n=6)均≤112%。利用该方法分析了饮用水处理厂不同处理阶段的水样,其中7-羟基香豆素、6,7-二羟基香豆素、香豆素的检出率为100%,含量为021~279 ng/L。6-羟基-4-甲基香豆素在原水、混凝后水样、炭滤后水样中均未检出,只在砂滤后水样和出厂水中被检出,而且出厂水中的含量(469 ng/L)高于砂滤后水样(179 ng/L)。8-氯-7-羟基香豆素只在出厂水中被检出(028 ng/L)。本方法分析时间短,精密度和准确度良好,在监测实际水样中香豆素的含量及评估饮用水处理过程对于水样中香豆素类化合物去除方面可发挥积极作用。
Chlorinated coumarins,which are as cytotoxic as highly toxic halobenzoquinones toward CHO-K1 cells,have recently been identified as disinfection byproducts in drinking water disinfection processes.Therefore,detecting coumarins in water samples collected at various stages from drinking water treatment plants helps assess the formation of chlorinated coumarins in drinking water.Hence,a simple,rapid,accurate,and sensitive method for quantifying coumarins in water samples is required.In this study,a method was developed based on solid-phase extraction coupled with high performance liquid chromatography-triple-quadrupole mass spectrometry for analyzing seven coumarins in water samples from drinking water treatment plants,including 6,7-dihydroxycoumarin,7-hydroxycoumarin,6-hydroxy-4-methylcoumarin,8-chloro-7-hydroxycoumarin,coumarin,7-chloro-6-hydroxy-4-methylcoumarin,and 3,8-dichloro-7-hydroxycoumarin.Sample pretreatment involved solid-phase extraction using HLB columns,followed by elution with water and methanol,each containing 0.25%formic acid.The extracted solution was separated via gradient elution using a Phenomenex Luna C18 column(100 mm×2.0 mm,3 mm)with 0.1%formic acid aqueous solution and methanol as the mobile phases,with analytes detected by triple-quadrupole mass spectrometry equipped with electrospray ionization source in multiple reaction monitoring mode.The matrix effect,precision,and accuracy of the developed method were investigated using raw and treated water as matrices.Matrix effects of 0.84-1.12 were recorded for the detection of 6,7-dihydroxycoumarin,7-hydroxycoumarin,6-hydroxy-4-methylcoumarin,and coumarin in raw water,while values of 0.67-0.70 were recorded for 8-chloro-7-hydroxycoumarin,7-chloro-6-hydroxy-4-methylcoumarin,and 3,8-dichloro-7-hydroxycoumarin in finished water.The three chlorinated coumarins exhibited matrix effects above 0.80 after the finished water matrix had been diluted four times.These results suggest that only simple solid-phase extraction or sample dilution is required to accurately determine the seven coumarins in drinking water from treatment plants.In addition,these coumarins exhibited good linear relationships at their respective mass concentrations.The precision and accuracy of the method were evaluated using raw and treated water as matrices.The seven coumarins exhibited good linearities by triple-quadrupole mass spectrometry in a certain range,with correlation coefficients(r)greater than 0.99 and method detection limits(MDLs)of 0.67-1.12 ng/L.The seven coumarins exhibited recoveries of 61.4%-91.5%at three spiked levels(20,50,100 ng/L)with relative standard deviations(RSDs,n=6)≤11.2%.The developed method can be used to analyze water samples from various treatment stages of a drinking-water treatment plant.7-Hydroxycoumarin,6,7-dihydroxycoumarin,and coumarin were detected at levels of 0.21-27.9 ng/L in 100%of the samples,while 6-hydroxy-4-methylcoumarin was not detected in raw water,post-coagulated water,and post-carbon-filtered water,but was found in sand-filtered water and finished water,with higher levels recorded for the latter(4.69 ng/L)than the former(1.79 ng/L).8-Chloro-7-hydroxycoumarin was only detected in treated water(0.07 ng/L).This method is highly precise and accurate,provides results in short analysis times,and can be used to effectively monitor coumarins in real water samples and assess their removal during drinking-water treatment.
作者
矫文美
杨晶铭
徐策
高福康
沈璐瑶
元宇博
郭志芬
黄光
JIAO Wenmei;YANG Jingming;XU Ce;GAO Fukang;SHEN Luyao;YUAN Yubo;GUO Zhifen;HUANG Guang(School of Life Sciences and Chemical Engineering,Jiangsu Second Normal University,Nanjing 211200,China;School of Stomatology,Nanjing Medical University,Nanjing 210029,China;School of Public Health,Nanjing Medical University,Nanjing 211166,China;Key Laboratory of Modern Toxicology,Ministry of Education,School of Public Health,Nanjing Medical University,Nanjing 211166,China)
出处
《色谱》
CAS
北大核心
2025年第1期78-86,共9页
Chinese Journal of Chromatography
基金
江苏第二师范学院教学改革项目研究课题(JSSNUJXGG2023QN04,JSSNUJXGG2023YB11)
江苏第二师范学院2024年《分析化学》和《仪器分析》课程思政示范课程项目
江苏第二师范学院“学校高层次人才科研启动基金”
南京医科大学高层次人才启动基金(NMUR2020003).
关键词
固相萃取
高效液相色谱-串联质谱法
饮用水
香豆素
消毒副产物
solid-phase extraction(SPE)
high performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS)
drinking water
coumarins
disinfection byproducts
作者简介
通讯联系人:黄光.Tel:(025)86868401,E-mail:guanghuang@njmu.edu.cn.
