Matrix solid-phase dispersion combined with gas chromatography–mass spectrometry for the determination of fifteen halogenated flame retardants in mollusks

This study presents the development and validation of a new analytical method for the simultaneous determination of fifteen analytes classified as halogenated flame retardants (HFRs) – nine brominated diphenyl ethers (BDEs) and six novel HFRs – in different kinds of mollusks using matrix solid-phase dispersion (MSPD) followed by gas chromatography coupled to negative chemical ionization-mass spectrometry (GC–NCI-MS). The proposed method is the first one developed for such a broad range of HFRs in aquatic biota, featuring several advantages, including low solvent and sample intake, simplicity of operation, reduced cost and integration of extraction and clean-up into a single step. Under optimal conditions, 0.5 g of freeze-dried sample, 0.5 g of a primary-secondary amine (PSA) as solid support, a sorbent combination of 1.75 g of florisil (deactivated with 5% Milli-Q water), 1.75 g of acidified silica (10% (w/w) H2SO4) and 0.5 g of silica, and 10 mL dichloromethane as elution solvent were used. Standard addition over the extract was required however for the correct quantification due to matrix effects in the GC system, particularly for novel HFRs, that could not be compensated with the internal standards. The method afforded LODs in the range of 0.003–0.07 ng g−1 dry weight (0.0006–0.014 ng g−1 on a wet weight basis, assuming an 80% sample water content), except for decabromodiphenyl ethane (DBDPE) (0.6 ng g−1 dry weight, 0.12 ng g−1 wet weight). The accuracy of the method was evaluated with three different types of spiked mollusk species using surrogate standards and standard addition over the extract for quantification and the recoveries were in the 70–120% range, except for bis(2-ethylhexyl)-3,4,5,6-tetrabromo-phthalate (DEHTBP) in clam (Ruditapes philippinarum) samples (46% recovery). Moreover, the method was successfully validated with standard reference materials (SRMs) of salmon and mussel tissues for BDEs. Finally, the method was applied to the determination of HFRs in different kind of freeze-dried mollusks: mussel (Mytilus galloprovincialis), cockle (Cerastoderma edule) and clam (R. philippinarum). Raft cultured mussels showed the highest concentrations of HFRs (up to 0.8 ng g−1 wet weight of BDE-209).