Headspace solid-phase microextraction gas chromatography tandem mass spectrometry for the determination of brominated flame retardants in environmental solid samples

A headspace solid-phase microextraction gas chromatography coupled with tandem mass spectrometry (HSSPME-GC-MS-MS) methodology for determination of brominated flame retardants in sediment and soil samples is presented. To the best of our knowledge, this is the first time that SPME has been applied to analyze polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs) in environmental solid samples. Analyses were performed using 0.5-g solid samples moisturized with 2 mL water, employing a polydimethylsiloxane (PDMS) fiber coating, exposed to the headspace at 100 °C for 60 min. Several types of environmental solid samples were included in this study and the extraction efficiency was related to the organic matter content of the sample. Calibration was performed using real samples, and the method showed good linearity over a wide concentration range, precision, and afforded quantitative recoveries. The obtained detection limits were in the sub-ng g⁻¹ for all the target analytes in both samples. The proposed procedure was applied to several marine and river sediments and soils, some of which were found to contain PBDEs at concentrations in the ng g⁻¹ level; BDE-47, BDE-100, and BDE-99 were the major congeners detected. The proposed method constitutes a rapid and low-cost alternative for the analysis of the target brominated flame retardants in environmental solid samples, since the clean-up steps, fractionation, and preconcentration of extracts inherent to the classical multi-step solvent extraction procedures are avoided.