Matrix solid-phase dispersion of polybrominated diphenyl ethers and their hydroxylated and methoxylated analogues in lettuce, carrot and soil

• MSPD for the extraction of PBDEs, MeO-PBDEs and OH-PBDEs in lettuce, carrot and soil.
• Chromatographic separation by GC-NCI-MS.
• Different strategies for the derivatization of OH-PBDEs.
• Application of developed method for lettuce, carrot and soil.

In the present work, a novel analytical method for the simultaneous determination of ten polybrominated diphenyl ethers (PBDEs), eight methoxylated PBDEs (MeO-PBDEs) and seven hydroxylated PBDEs (OH-PBDEs) in soil, lettuce and carrot samples was developed. The procedure was based on matrix solid-phase dispersion (MSPD) followed by gas chromatography coupled to negative chemical ionization-mass spectrometry (GC–NCI-MS). Under optimum conditions, 0.5 g of sample (freeze-dried in the case of lettuce and carrot samples) was dispersed with 0.5 g of octadecyl-functionalized silica (C18) and 1.75 g of acidified silica (10% H2SO4, w/w) was used as clean-up sorbent. A two-step fractionated elution was carried out. First, PBDEs and MeO-PBDEs were eluted in 75:25% (v/v) n-hexane/dichloromethane mixture and, then, the retained OH-PBDEs were eluted in pure dichloromethane. Both extracts were analyzed by GC-NCI-MS separately, in the case of OH-PBDEs after derivatization with N-methyl-N-(trimethylsilyl) trifluoroacetamide. The developed method was validated in terms of accuracy for soil, lettuce and carrot matrices, spiked at two fortification levels (5 and 25 ng g−1). After correction with the corresponding surrogate, apparent recovery values (defined as the recovery obtained after correction with the corresponding surrogate) were in the 80–129% range. Precision (as relative standard deviation) in the 1–21% range and method detection limits (MDLs) in the 0.003 and 0.3 ng g−1 range for soil and in the 0.003–0.4 ng g−1 range (dry weight) for lettuce and carrot samples were obtained. For PBDEs the method was also validated with a standard reference material (SRM-2585) of house dust. Finally, the method was applied for the determination of target analytes in soil, lettuce and carrot.