Institute of Food Safety, Animal Health and Environment "BIOR", Lejupes iela 3, Riga LV-1076, Latvia; University of Latvia, Department of Chemistry, Kr. Valdemara iela 48, Riga LV-1013, Latvia.
Institute of Food Safety, Animal Health and Environment "BIOR", Lejupes iela 3, Riga LV-1076, Latvia.
J Chromatogr A. 2014 Feb 21;1330:30-9. doi: 10.1016/j.chroma.2014.01.023. Epub 2014 Jan 18.
A new analytical method is presented for diastereoisomer-specific identification and quantitation of hexabromocyclododecanes (HBCD) in fish samples. The method is based on extraction of the target analytes from samples with a mixture of organic solvents, with further three-stage clean-up including destructive removal of matrix components with sulphuric acid and acid-impregnated silica gel, and Florisil adsorption column chromatography. Ultra high performance liquid chromatography (UPLC) coupled with high resolution (HR) Orbitrap mass spectrometry featuring heated electrospray ionization (HESI-II) interface operated in negative ion mode was employed for the identification/quantitation of contaminants. The developed methodology was robustly validated in terms of recovery, repeatability, intermediate precision, linear calibration ranges, limits of detection and quantitation, and used for analysis of twenty five Baltic wild salmon (Salmo salar) samples. Under the optimized conditions, recoveries for selected analytes were within the range of 91.4-103.6%, and the repeatability and intermediate precision in terms of relative standard deviations (RSDs) were in the ranges 1.6-8.3% and 1.6-12.5%, respectively, for all three validation levels. The elaborated method achieved instrumental limits of quantification (i-LOQ) of 1.3-3.0pg on column for three HBCD diastereoisomers corresponding to the method LOQ of 0.005-0.012ngg(-1) wet weight (w.w.) The presence of HBCD diastereoisomers was confirmed in all the analyzed Baltic salmon samples in the concentration range of 0.39-3.82ngg(-1) w.w. with an average of 1.59ngg(-1) w.w. for total HBCD. The diastereomer pattern typical for aquatic biota was observed with strong predominance of α-HBCD. The newly developed methodology could be employed for a regular diastereomer-specific monitoring of HBCD content in fish samples, representing a good alternative to existing LC-MS/MS methods in terms of sensitivity and accuracy, and providing further possibilities for inclusion of other contaminants in the scope of analysis.
一种新的分析方法被提出，用于对鱼类样品中六溴环十二烷（HBCD）的对映异构体进行特异性识别和定量分析。该方法基于用有机溶剂混合物从样品中提取目标分析物，然后进行三阶段净化，包括用硫酸和酸浸渍硅胶破坏基质成分，以及 Florisil 吸附柱色谱。超高效液相色谱（UPLC）与高分辨率（HR）轨道阱质谱联用，采用加热电喷雾电离（HESI-II）接口，在负离子模式下用于污染物的鉴定/定量。所开发的方法在回收率、重复性、中间精密度、线性校准范围、检测限和定量限方面进行了稳健验证，并用于分析 25 个波罗的海野生三文鱼（Salmo salar）样品。在优化条件下，选定分析物的回收率在 91.4-103.6%范围内，重复性和中间精密度（RSD）分别在 1.6-8.3%和 1.6-12.5%范围内，适用于所有三个验证水平。该方法在仪器定量限（i-LOQ）方面达到了 3.0pg 柱上的水平，对于三种 HBCD 对映异构体，相应的方法定量限（LOQ）为 0.005-0.012ngg(-1)湿重（w.w.）。在所分析的所有波罗的海三文鱼样品中均证实存在 HBCD 对映异构体，浓度范围为 0.39-3.82ngg(-1) w.w.，平均为 1.59ngg(-1) w.w.，总 HBCD。观察到了与水生生物典型的对映异构体模式，其中α-HBCD 占主导地位。新开发的方法可用于鱼类样品中 HBCD 含量的定期对映异构体特异性监测，在灵敏度和准确性方面优于现有的 LC-MS/MS 方法，并为在分析范围内纳入其他污染物提供了进一步的可能性。
