Optimized determination of polybrominated diphenyl ethers and polychlorinated biphenyls in sheep serum by solid-phase extraction–gas chromatography–mass spectrometry

Abstract

We describe a solid-phase extraction (SPE) method, followed by gas chromatography–mass spectrometry (GC–MS), for the simultaneous determination of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in sheep serum samples. The denaturation of serum proteins by formic acid, water-1-propanol and water-2-propanol were compared and optimized. Seven different solid-phase sorbents were tested and it was found that Strata-X cartridge (200mg, 6mL) gave the best recoveries (92–106%, SD<6%, n=3) for all the target analytes. The different extraction solvents (iso-hexane and dichloromethane), either alone or in combination, were used to extract these persistent organic compounds from spiked serum samples by SPE. Removal of co-extracted biogenic materials was achieved using adsorption chromatography with acid modified silica and activated silica. Iso-hexane was found to be the most appropriate solvent for clean-up providing good recoveries and clear chromatographic separation; its use is preferable to that of DCM because it is less environmentally toxic. The limits of detection (LOD) of the proposed method were 47–105pgg−1 and 16–24pgg−1 for the different PBDEs and PCBs studied, respectively. The developed method was linear over the range from 0.05 to 30ngg−1, for all PBDEs except PBDE 183 (0.10–30ngg−1), and from 0.02 to 30ngg−1 for all tested PCB congeners. The established method was successfully applied to sheep serum samples from Scotland, UK, for the determination of the target PBDEs and PCBs.