6533b827fe1ef96bd128726c

RESEARCH PRODUCT

New perspectives on diastereoselective determination of hexabromocyclododecane traces in fish by ultra high performance liquid chromatography-high resolution orbitrap mass spectrometry.

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a b s t r a c t 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 includ- ing destructive removal of matrix components with sulphuric acid and acid-impregnated silica gel, and Florisil adsorption column chromatography. Ultra high performance liquid chromatography (UPLC) cou- pled 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 analy- sis 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 1.3-3.0 pg on column for three HBCD diastereoisomers corresponding to the method LOQ of 0.005-0.012 ng g −1 wet weight (w.w.) The presence of HBCD diastereoisomers was confirmed in all the analyzed Baltic salmon samples in the concentration range of 0.39-3.82 ng g−1 w.w. with an average of 1.59 ng g −1 w.w. for total HBCD. The diastereomer pattern typical for aquatic biota was observed with strong predominance of -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.