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.
Wei Sheng Yan Jiu. 2021 Sep;50(5):805-813. doi: 10.19813/j.cnki.weishengyanjiu.2021.05.017.
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.
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.
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.
The developed method was simple, rapid, no sample preparation except filtration and low reagent cosumption, which could meet the need of drinking water monitoring and achieve comprehensive screening of HCAs in drinking water. In addition, full MS/dd-MS~2 data acquisition mode could provide retrospective analysis of existing data by adding the emerging or interesting HCAs into the screening compound database.
建立一种结合传统定量检测与半靶向分析，利用离子色谱（IC）和四极杆-轨道阱（Q-Orbitrap）高分辨率质谱（HRMS）测定饮用水中常见和新出现的卤代羧酸（HCAs）的方法。
详细研究了IC-HRMS方法中色谱柱类型、流动相组成、柱后添加乙腈的流速、柱温及进样体积对其的影响，以及HRMS条件。饮用水样品经过滤后直接注入IC-HRMS进行分析。采用800 mmol/L甲胺-水作为流动相进行梯度洗脱，在AS21阴离子交换色谱柱（2 mm×250 mm）上进行色谱分离，并在柱后添加乙腈。采用电喷雾电离负离子模式在HRMS上进行检测。通过全质谱/dd-质谱²模式实现了8种卤乙酸（HAAs）的定量分析和19种HCAs的半靶向筛查。
IC-HRMS对8种HAAs中的每一种均获得了良好的线性（r＞0.996）。方法检出限（MDLs）和方法定量限（MQLs）分别在0.50 - 2.5 μg/L和1.7 - 8.3 μg/L范围内。日内和日间相对标准偏差（RSDs）分别在1.50% - 11.0%和4.58% - 10.9%范围内。回收率在61.3% - 117%（n = 6）范围内。该方法应用于分析39个饮用水样品，检测并定量了二氯乙酸和三氯乙酸，浓度范围为1.35至48.0 μg/L。此外，采用半靶向筛查方法初步鉴定出5种HCAs（二氟乙酸、三氟乙酸、溴氯乙酸、一氯丙酸和二氯丙酸）。
所建立的方法简单、快速，除过滤外无需样品前处理且试剂消耗低，能够满足饮用水监测需求，实现对饮用水中HCAs的全面筛查。此外，全质谱/dd-质谱²数据采集模式可通过将新出现的或感兴趣的HCAs添加到筛查化合物数据库中，对现有数据进行回顾性分析。
