Dispersive solid-phase extraction as a simplified clean-up technique for biological sample extracts. Determination of polybrominated diphenyl ethers by gas chromatography–tandem mass spectrometry

Dispersive solid-phase extraction (DSPE) is proposed for the first time as a simplified, fast and low cost clean-up technique of biological sample extracts for polybrominated diphenyl ethers (PBDEs) determination. The combination of a traditional extraction technique, such as ultrasound-assisted leaching (USAL) with DSPE was successfully applied for sample preparation prior to gas chromatography–tandem mass spectrometry (GC–MS/MS) analysis. The analytes were first extracted from 1 g homogenized sample in n-hexane:dichloromethane (8:2) by applying USAL technique and further cleaned-up using DSPE with 0.20 g C18-silica as sorbent material. Different solvent mixtures, sorbent type and amount, and lipid digestion procedures were evaluated in terms of clean-up and extraction efficiency. Under optimum conditions, the method detection limits (MDLs) for PBDEs, calculated as three times the signal-to-noise ratio (S/N) were within the range 9–44 pg g−1 wet weight. The calibration graphs were linear within the concentration range of 53–500,000 pg g−1, 66–500,000 pg g−1, 89–500,000 pg g−1 and 151–500,000 pg g−1 for BDE-47, BDE-100, BDE-99 and BDE-153, respectively; and the coefficient of determination (r2) exceeded 0.9992 for all analytes. The proposed methodology was compared with a reference solid-phase extraction technique. The applicability of the methodology for the screening of PBDEs has been demonstrated by analyzing spiked and real samples of biological nature (fish, egg and chicken) with different lipid content as well as reference material (WELL-WMF-01). Recovery values ranged between 75% and 114% and the measured concentrations in certified material showed a reasonable agreement with the certified ones. BDE-47, BDE-100 and BDE-99 were quantified in three of the seven analyzed samples and the concentrations ranged between 91 and 140 pg g−1. In addition, this work is the first description of PBDEs detected in fish of Argentinean environment.