离子色谱-轨道阱质谱法测定饮用水中卤代羧酸  

Determination of halogenated carboxylic acids in drinking water by ion chromatography-orbitrap mass spectrometry method

作　　者：骆春迎[1] 赵璇 罗新月 杨觅 高舸[2] 徐布一[3] 王焱[1] 屈卫东[4] 邹晓莉[1] Luo Chunying;Zhao Xuan;Luo Xinyue;Yang Mi;Gao Ge;Xu Buyi;Wang Yan;Qu Weidong;Zou Xiaoli(Department of Public Health Laboratory Science,West China School of Public Health/West China Fourth Hospital,Sichuan University,Chengdu 610041,China;Chengdu Center for Disease Control&Prevention,Chengdu 610047,China;Sichuan Provincial Public Security Department,Chengdu 610041,China;School of Public Health,Fudan University,Shanghai 200032,China)

机构地区：[1]四川大学华西公共卫生学院/四川大学华西第四医院卫生检验与检疫系,成都610041 [2]成都市疾病预防控制中心,成都610047 [3]四川省公安厅,成都610041 [4]复旦大学公共卫生学院,上海200032

出　　处：《卫生研究》2021年第5期805-813,共9页Journal of Hygiene Research

基　　金：四川省医学科研课题计划(No.Q18001);四川省科技厅重点项目(No.2020YFS0056)。

摘　　要：目的建立饮用水中卤代羧酸的四极杆-轨道阱高分辨质谱法联用离子色谱法定量分析和半靶向筛查方法。方法对色谱柱的种类、流动相的浓度、柱后添加乙腈的流速、柱温以及进样量进行考察,同时对质谱条件进行优化。饮用水样品过滤后直接注入离子色谱-轨道阱质谱分析。经AS21阴离子交换色谱柱(2 mm×250 mm)分离,800 mmol/L甲胺-水梯度洗脱后,与柱后添加的乙腈一起进入质谱仪,在电喷雾电离源负离子模式下进行检测,采用一级质谱全扫描和数据依赖的二级质谱扫描(full MS/dd-MS^(2))模式对8种卤代乙酸进行定量分析,对19种卤代羧酸进行半靶向筛查。结果 8种卤代乙酸在各自的线性范围内线性良好,相关系数均高于0.996,方法检出限和定量限分别为0.50~2.5μg/L和1.7~8.3μg/L,日内精密度为1.50%~11.0%,日间精密度为4.58%~10.9%,回收率为61.3%~117%(n=6)。将建立的方法用于39份饮用水样品的实际测定,定量检出二氯乙酸和三氯乙酸,浓度范围为1.35~48.0μg/L;采用半靶向筛查方法识别出了5种卤代羧酸,即二氟乙酸、三氟乙酸、一溴一氯乙酸、一氯丙酸和二氯丙酸。结论建立了卤代羧酸的四极杆-轨道阱高分辨质谱法联用高效离子色谱法的分析方法。方法简单、快捷,除过滤外未经任何前处理,试剂消耗量少,能满足饮用水监测的需求,可实现对饮用水中卤代羧酸的全面筛查。本研究采用的full MS/dd-MS^(2)模式还可通过将新兴的或感兴趣的卤代羧酸加入到数据库中,实现对已采集数据的回顾性分析。OBJECTIVE To establish a method for determination of the common and emerging halogenated carboxylic acids(HCAs) in drinking water by ion chromatography(IC) and quadrupole-orbitrap(Q-Orbitrap) high resolution mass spectrometry(HRMS) combined the traditional quantitative detection with semi-target analysis. METHODS Effects on the type of chromatographic column, the composition of mobile phase, the flow rate of acetonitrile added post column, the column temperature, and the injection volume were studied in detail for IC-HRMS method, also for HRMS conditions. Drinking water sample was directly injected into IC-HRMS for analysis after filtration. The chromatography separation was performed on an AS21 anion exchange chromatography column(2 mm×250 mm) with the gradient elution using 800 mmol/L methylamine-water as mobile phase, and acetonitrile was added after column. The detection was conducted on HRMS with the electrospray ionization negative mode. And the quantitative analysis of 8 haloacetic acids(HAAs) and semi-target screening of 19 HCAs were achieved by full MS/dd-MS^(2) mode. RESULTS Good linearity(r>0.996) was obtained for each of 8 HAAs for IC-HRMS. The method detection limits(MDLs) and method quantification limits(MQLs) were in the range of 0.50-2.5 μg/L and 1.7-8.3 μg/L, respectively. Intra-and inter-day relative standard deviations(RSDs) were in the range of 1.50%-11.0% and 4.58%-10.9%, respectively. The recoveries were in the range of 61.3%-117%(n=6). The proposed method was applied to analyze 39 drinking water samples, and dichloroacetic acid and trichloroacetic acid were detected and quantified, with concentrations ranging from 1.35 to 48.0 μg/L. Besides, five HCAs(difluoroacetic acid, trifluoroacetic acid, bromochloroacetic acid, monochloropropionic acid and dichloropropionic acid) were preliminary identified with semi-target screening method. CONCLUSION The developed method was simple, rapid, no sample preparation except filtration and low reagent cosumption, which could meet the need of drinking w

关 键 词：卤代羧酸 饮用水 消毒副产物 定量分析 半靶向筛查 离子色谱联用高分辨质谱 

分 类 号：O657.63[理学—分析化学] R115[理学—化学]