Simple approach for the determination of brominated flame retardants in environmental solid samples based on solvent extraction and solid-phase microextraction followed by gas chromatography–tandem mass spectrometry

A viable approach for the analysis of polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs) in sewage sludge samples is presented in this paper. The proposed method combines ultrasound-assisted extraction (UAE) of the solid sample and headspace solid-phase microextraction (HS–SPME) of the obtained extract, followed by gas chromatography coupled to tandem mass spectrometry (GC–MS–MS) analysis. Different parameters affecting the extraction process are evaluated and optimized. The addition of a small amount of Florisil to the sample during UAE provides a significant improvement of the chromatographic background and, at the same time, a much more efficient HS–SPME. Extensive method validation is performed using real sewage sludge samples. The proposed method exhibits good performance in terms of linearity and precision, with recoveries exceeding 92% and limits of detection in the sub ng g−1 level. Practical applicability is demonstrated through the analysis of real contaminated sewage sludge and sediment samples in which some of the target PBDEs are detected and quantified. This proposed combined methodology represents a large time-saving when compared to other classic multi-step solvent extraction methods and it constitutes a suitable approach for the analysis of the target compounds in environmental complex solid samples.