微波辅助离子液体分散液-液微萃取DART-Orbitrap质谱法测定环境水中的溴代阻燃剂

doi:10.7503/cjcu20180026

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (9): 1934.doi: 10.7503/cjcu20180026

微波辅助离子液体分散液-液微萃取DART-Orbitrap质谱法测定环境水中的溴代阻燃剂

苏蕊¹(), 汪亿晗¹, 陈长宝¹, 孙秀丽¹, 刘淑莹^1,², 杨洪梅¹()

1.长春中医药大学吉林省人参科学研究院, 长春 130117
2.中国科学院长春应用化学研究所, 长春 130022

收稿日期:2018-01-09 出版日期:2018-09-07 发布日期:2018-06-04
作者简介:
联系人简介: 苏蕊, 女, 博士, 副研究员, 主要从事复杂基质的质谱分析研究. E-mail: sranalchem@163.com; 杨洪梅, 女, 博士, 副研究员, 博士生导师, 主要从事质谱分析研究. E-mail: yanghm@sina.cn
基金资助:
吉林省科技厅重点科技攻关项目(批准号: 20160204027YY, 201603080YY, 201603003YY, 20170307028YY)资助.

Determination of Brominated Flame Retardants in Environmental Water by Microwave-assisted Ionic Liquid/ionic Liquid Dispersive Liquid-liquid Microextraction Coupled with DART-Orbitrap Mass Spectrometry^†

SU Rui^1,^*(), WANG Yihan¹, CHEN Changbao¹, SUN Xiuli¹, LIU Shuying^1,², YANG Hongmei^1,^*()

1. Jilin Ginseng Academy, Changchun University of Chinese Medicine, Changchun 130117, China
2. Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China

Received:2018-01-09 Online:2018-09-07 Published:2018-06-04
Contact: SU Rui,YANG Hongmei E-mail:sranalchem@163.com;yanghm@sina.cn
Supported by:
? Supported by the Project of Science and Technology Department of Jilin Province, China(Nos. 20160204027YY, 201603080YY, 20170307028YY, 201603003YY).

摘要/Abstract

摘要：

采用微波辅助离子液体分散液-液微萃取(MA-IL/IL-DLLME)的方法提取了环境水样品中的溴代阻燃剂(BFRs), 以[C₆MIM][PF₆]为萃取剂, [C₄MIM][BF₄]为分散剂, 辅以微波照射, 在短时间内获得较高提取效率, 并结合DART串联高分辨静电场轨道阱质谱仪(DART-Orbitrap MS)对环境水中的BFRs进行测定, 建立了一种快速、灵敏、简便且准确测定环境水中BFRs的方法. 通过对BFRs萃取条件及DART离子源参数进行优化, 获得了最优实验条件. 为进一步明确BRFs在DART-MS中的气相离子反应特征, 讨论了5种BFRs的特征离子信息, 确定了目标离子, 明确了发生机理. 实验结果表明, 采用MA-IL/IL-DLLME萃取水样中的BFRs能够有效提高方法的灵敏度, 结合DART离子源的耐盐效应, 可将离子液体应用于质谱测定的同时, 解决DART离子源灵敏度低的难题. 在最优实验条件下, 对环境水样进行分析, 方法的回收率为80.7%~107%, RSD≤10.2%, 检出限为0.212~1.82 μg/L.

关键词: 微波辅助离子液体分散液-液微萃取, DART串联高分辨静电场轨道阱质谱仪, 溴代阻燃剂, 快速检测, 环境水

Abstract:

A new method termed microwave-assisted ionic liquid/ionic liquid dispersive liquid-liquid microextraction coupled with DART-Orbitrap mass spectrometry(MA-IL/IL-DLLME) was developed for the determination of selected five brominated flame retardants(BFRs) in environmental water. Instead of using hazardous organic solvents, two kinds of ionic liquids(ILs), hydrophobic IL([C₆MIM][PF₆]) and hydrophilic IL([C₄MIM][BF₄]), were used as extraction solvent and dispersion agent, respectively, in this method. In the extraction procedure, BFRs were extracted entirely into the [C₆MIM][PF₆] from environmental water samples with the help of [C₄MIM][BF₄]. After extraction, IL phase containing analytes was analyzed by direct analysis in real time-mass spectrometry(DART-MS). Several experimental parameters that might affect the extraction efficiency were investigated and optimized. Under the optimized experimental conditions, low limits of detection(LODs, 0.212—1.82 μg/L) were obtained. The present method also provides good recoveries(80.7%—107%) and acceptable precision(RSDs<10.2%). In addition, the negative ionization characteristics of 5 different BFRs were investigated using DART-Orbitrap MS. The experimental results demonstrated that the developed method contains the advantages including easy-to-use, high speed and high sensitivity for the analysis of BFRs in environmental water samples, showing potential application in the environmental science and environment pollution protection.

Key words: Microwave-assisted ionic liquid/ionic liquid dispersive liquid-liquid microextraction, DART-Orbitrap MS, Brominated flame retardant, Rapid detection, Environmental water

中图分类号:

O654

TrendMD:

苏蕊, 汪亿晗, 陈长宝, 孙秀丽, 刘淑莹, 杨洪梅. 微波辅助离子液体分散液-液微萃取DART-Orbitrap质谱法测定环境水中的溴代阻燃剂. 高等学校化学学报, 2018, 39(9): 1934.

SU Rui,WANG Yihan,CHEN Changbao,SUN Xiuli,LIU Shuying,YANG Hongmei. Determination of Brominated Flame Retardants in Environmental Water by Microwave-assisted Ionic Liquid/ionic Liquid Dispersive Liquid-liquid Microextraction Coupled with DART-Orbitrap Mass Spectrometry^†. Chem. J. Chinese Universities, 2018, 39(9): 1934.

图/表 8

Fig.1 Structures of BFRs

Fig.2 Schematic procedure of MA-IL/IL-DLLME DART-Orbitrap MS

Fig.3 Mass spectra of 3,3',4-tribromodiphenyl ether(A, B) and tetrabromobisphenol A(C, D) obtained using helium(A, C) and argon nitrogen(B, D) as DART carrier gas

Fig.4 Ar-DART Orbitrap mass spectra of 2,2',4,4'-tetrabromodiphenyl ether(A), 2,2',4,4',6- pentabromodiphenyl ether(B) and pentabromophenyl ether(C) in negative ion mode

Fig.5 Influence of six solvents on signal intensities obtained for BFRs in negative ion modea. Methylbenzene; b. acetonitrile; c. methanol; d. acetone; e. water; f. isopropanol. Data points are mean values of three determinations.

Fig.6 Effect of type of extraction solvent on signal intensities of BFRs in negative ion mode

Fig.7 Effect of type of dispersant on signal intensities of BFRs in negative ion mode

Table 1 Analytical performance of the proposed method, and recoveries obtained for analysis of the five BFRs spiked in environmental water sample

Analyte	10^-2 Linear range/ (μg·L^-1)	Regression equation^*	Correlation coefficient	LOD/ (μg·L^-1)	Sipked sample concentration/ (μg·L^-1)	Recovery (%, n=6)	RSD(%, n=6)
Pentabromophenyl ether	0.500—1.00	y=36673c+15343	0.999	0.212	5.0	86.1	8.16
					50.0	90.4	4.74
2,2',4,4',6-Pentabromodiphenyl ether	5.00—2.50	y=17073c-4522	0.998	1.73	5.0	92.3	5.65
					50.0	0.0101	7.43
2,2',4,4'-Tetrabromodiphenyl ether	5.00—2.50	y=1938c+6688	0.997	1.82	5.0	80.7	8.51
					50.0	0.0107	9.26
3,3',4-Tribromodiphenyl ether	5.00—2.50	y=3925c+3761	0.998	1.55	5.0	90.6	10.20
					50.0	94.4	6.48
Tetrabromobisphenol A	5.00—2.50	y=17491c+8981	0.998	1.78	5.0	85.7	7.84
					50.0	91.9	8.60

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微波辅助离子液体分散液-液微萃取DART-Orbitrap质谱法测定环境水中的溴代阻燃剂

Determination of Brominated Flame Retardants in Environmental Water by Microwave-assisted Ionic Liquid/ionic Liquid Dispersive Liquid-liquid Microextraction Coupled with DART-Orbitrap Mass Spectrometry^†

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