通过式固相萃取-液相色谱-四极杆/静电场轨道阱高分辨质谱快速筛查鱼肉中全氟化合物及其前体物质

Rapid Screening and Confirmation of Perfluorinated Compounds and Their Precursors in Fish Muscle by Solid Phase Extraction Purification and Liquid Chromatography Coupled with Quadrupole/Exactive Orbitrap Mass Spectrometry

采用通过式固相萃取技术去除样品基质中脂肪和磷脂等杂质干扰,利用液相色谱-四极杆/静电场轨道阱高分辨质谱(LC-Q Exactive Orbitrap MS)的同时定性定量功能,建立了鱼肉中18种全氟化合物(Perfluorinated compounds,PFCs)及其21种前体物质的同时分析方法。样品经90%乙腈溶液提取,Oasis PRi ME HLB通过式固相萃取柱净化,C_(18)色谱柱分离,同时在液相色谱系统混合器和进样器之间串联一根延迟色谱柱,去除液相色谱系统的背景干扰;质谱数据采集使用Q Exactive高分辨质谱的Full MS/dd-MS^2监测模式,以Full MS一级质谱全扫描提取母离子精确质量数所得的色谱峰面积进行定量,以保留时间和dd-MS^2数据依赖子离子扫描所得的二级子离子质谱图进行定性确证。39种目标物的精确质量数偏差不大于3×10^(-6),浓度与母离子峰面积的线性关系良好,相关系数≥0.99,检出限为0.02~0.50μg/kg。基质加标回收率在61.7%~122%之间,相对标准偏差(RSD)为6.9%~18.8%。本方法实现了18种PFCs及其21种前体物质的同时确证和测定,拓展了生物基质中全氟化合物的检测种类,而且前处理方法更为简化、部分化合物的灵敏度比文献报道方法提高约一个数量级,为全氟化合物前体物质的生物转化研究提供了高效的技术基础。

A method was developed for the rapid screening and confirmation of 18 perfluorinated compounds（ PFCs） and 21 precursors in fish muscle by solid phase extraction and liquid chromatography coupled with quadrupole / exactive orbitrap mass spectrometry（ LC-Q Exactive Orbitrap MS）. In this method,the sample was firstly extracted with acetonitrile-water（ 90∶ 10,V / V）,cleaned-up by solid-phase extraction using Oasis PRi ME HLB column. Then,39 target compounds were separated on a BEH C_（18）（ 2.1 mm×100 mm,1.7 μm）column,and the background interference caused by LC system was eliminated by a short C_（18） HPLC column located between the mixer and the auto sampler. In the process of quantification and qualification,a full MS /dd-MS^2 experiment was adopted in mass spectrometry acquisition,accompanied with the full scan MS date for quantification,as well as the date dependent MS^2 product ion spectra for qualification. The mass accuracy error was less than 3×10^-6,and the calibration curves were linear well with correlation coefficient over 0.99. The limits of detection ranged from 0. 02 to 0. 50 μg / kg. The average spiked recoveries for 39 target compounds were between 61. 7% and 122. 0%,with relative standard derivations（ RSDs） from 6. 9% to 18.8%. The developed method was successfully applied to the simultaneous determination of 18 PFCs and 21 precursors in fish muscle with satisfactory results.