双固相萃取柱净化-超快速液相色谱-串联质谱法同时测定贝类组织中全氟羧酸及其前体物质

建立同时测定贝类中13种全氟羧酸类化合物、6种氟调聚饱和酸和3种氟调聚不饱和酸的超快速液相色谱-串联质谱分析方法。样品经90%乙腈溶液超声提取,Oasis WAX和Envi-Carb双固相萃取柱净化,Kinetex XB-C_(18)色谱柱(2.1 mm×100 mm,2.6μm)分离,多反应监测负离子模式扫描,同位素内标法定量。22种目标物在各自相应质量浓度范围内线性良好,相关系数不低于0.995,定量限为0.03~1.67 ng/g。基质加标回收率在63.05%~127.18%之间,相对标准偏差为4.70%~17.1%。本方法实现了复杂贝类基质(肌肉、肝脏、外套膜、鳃、性腺等)中PFCAs及其前体物质的同时测定,采用双柱净化方式,大大降低了杂质成分的干扰,部分化合物的灵敏度优于现有方法,适用于贝类样品中PFCAs及其前体物质的监控分析,为研究PFCAs前体物质的生物转化提供了新技术手段。

Simultaneous Determination of Perfluorinated Acids and Their Precursors in Bivalve Shellfish by Double SPE Columns Purification and Ultra Fast Liquid Chromatography-Tandem Mass Spectrometry

A method for the simultaneous identification and quantification of thirteen perfluoroalkyl carboxylic acids (PFCAs), six fluorotelomer saturated carboxylic acids (FTCAs) and three fluorotelomer unsaturated carboxylic acids (FTUCAs) in bivalve shellfish tissues was developed using ultra fast liquid chromatography-tandem mass spectrometry (UFLC-MS/MS). Samples were extracted with acetonitrile-water (90:10, V/V), and the extract was cleaned up by solid-phase extraction (SPE) using Oasis WAX SPE coupled in-line to ENVI-Carb. Then, the separation was performed on a Kinetex XB-C18 column (2.1 mm × 100 mm, 2.6 μm) with gradient elution using a mixture of 95% methanol solution containing 5 mmol/L ammonium acetate and 5% methanol solution containing 5 mmol/L ammonium acetate as the mobile phase. Mass spectrometry was carried out under the multiple reaction monitoring (MRM) mode with negative electrospray ionization and the internal standard method was employed for quantification. The calibration curves for 22 analytes were linear well with correlation coefficient over 0.995. The limits of quantification ranged from 0.03 to 1.67 ng/g. The average spiked recoveries for 22 analytes were between 63.05% and 127.18%, with relative standard deviations (RSDs) from 4.70% to 17.1%. This method was successfully applied for the simultaneous determination of 13 PFCAs and 9 potential precursors in bivalve shellfish tissue samples.