Validation Including Uncertainty Estimation of a GC–MS/MS Method for Determination of Selected Halogenated Priority Substances in Fish Using Rapid and Efficient Lipid Removing Sample Preparation

Slávka Nagyová,Peter Tölgyessy

doi:10.3390/foods8030101

Abstract

A rapid method is proposed for the determination of selected H2SO4 stable organic compounds—eight organochlorines (OCs; hexachloro-1,3-butadiene, pentachlorobenzene, hexachlorobenzene, hexachlorocyclohexane—HCH—isomers, heptachlor) and six polybrominated diphenyl ethers (PBDEs; BDE-28, 47, 99, 100, 153, 154)—in fish samples. In the method, a modified QuEChERS (quick, easy, cheap, effective, rugged and safe) sample preparation using pH-tuned dispersive liquid–liquid microextraction (DLLME) and H2SO4 digestion fish extract clean-up is followed by gas chromatography–triple quadrupole tandem mass spectrometry (GC–QqQ-MS/MS) analysis. The method was validated in terms of linearity, limits of the method, recovery, accuracy, analysis of standard reference material (NIST SRM 1946), and estimation of combined uncertainty of the measurement (top-down approach). For validation, chub composite samples were used, and subsequently, the method was successfully applied to analysis of real samples of eight fish species. Finally, the method passed the analytical Eco-Scale evaluation as “an acceptable green analysis method”, and showed its advantages (simplicity, rapidity, low cost, high extract clean-up efficiency, good sensitivity) when compared to other reported QuEChERS based methods.

Highlights

Anthropogenic halogenated organic compounds synthesized as pesticides, solvents or fire retardants have been found to pose a serious threat to aquatic environments, wildlife and humans due to their toxic, persistent and bioaccumulative properties [1]
The QuEChERS extracts from the chub homogenate sample with lipid content of 5.2% and water content of 74.6% spiked with test analytes at concentration level of 5 ng/mL and treated by dispersive liquid–liquid microextraction (DLLME)
matrix effect (ME) presented in the studies employing modified QuEChERS methods with dispersive solid-phase extraction (dSPE) clean-up were for selected OC pesticides incomparably higher

Summary

Introduction

Anthropogenic halogenated organic compounds synthesized as pesticides, solvents or fire retardants have been found to pose a serious threat to aquatic environments, wildlife and humans due to their toxic, persistent and bioaccumulative properties [1]. Because of these harmful effects and impacts, the production and use of large number of organochlorine (OC) pesticides and certain brominated flame retardants was banned or severely restricted in the European Union (EU), and other parts of the world [2], but their presence and release in the environment can be expected over the decades. For the determination of PBDEs in fish and other seafood, the EU Commission recommends

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