Selective pressurized liquid extraction of three classes of halogenated contaminants in fish

Abstract

Pressurized liquid extraction (PLE) combined with in-cell clean-up of co-extracts, so-called selective-PLE (S-PLE), is a fast and accepted method for the analysis of halogenated organic contaminants in fish. However, many of the existing methods were optimized for use with single classes of contaminants. The main objective of this research was to develop an S-PLE method that elutes a minimal amount of fats while simultaneously extracting halogenated pesticides, polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) from fat-rich fish. The optimized method uses n-hexane:dichloromethane (75:25, v/v) as the extraction solvent, a 0.0078 fat to fat-retainer ratio (FFR) with Florisil as the fat retainer, three individual 5-min extractions with flush volumes of 150% and a selection of labeled surrogate standards (isotope dilution). This method resulted in a mean recovery of 77% for all target analytes in spiked samples and an average relative standard deviation of 6.3%. The method was validated with a certified reference material; the mean measured analyte concentrations agreed with the reference values except in the case of individual endosulfan isomers. It is likely that interconversion from the beta- to alpha-endosulfan isomer had occurred in the CRM, resulting in low measured concentrations for beta-endosulfan and high measured concentrations for alpha-endosulfan when compared with the reference values. Finally, the method was tested on three fish species with varying fat content. Different contaminant patterns were observed in the various species.