Miniaturized selective pressurized liquid extraction of polychlorinated biphenyls and polybrominated diphenyl ethers from feedstuffs

A new miniaturized pressurized liquid extraction (PLE) with in-cell purification method has been developed for the simultaneous extraction of endogenous prioritary and toxic polychlorinated biphenyls (PCBs) and environmentally relevant tri- to deca-brominated diphenyl ether (PBDE) congeners from different feed matrices. Parameters affecting the efficiency of the selective PLE process, such as sorbent:matrix ratio, volume and nature of the extraction solvent, PLE working mode, extraction time and temperature, and amount of co-sorbents, were optimized. n-Hexane and n-hexane:dichloromethane (1:1, v/v) were used as extraction solvents. 8-mL of organic solvents and 3.5 g of sorbents sufficed for complete sample treatment. Only 0.25 g of feed sample were required for accurate determination of the endogenous PCBs studied using gas chromatography with a micro-electron capture detector (GC-μECD) during method development, and for PBDE analysis using either GC-μECD or gas chromatography with negative chemical ionization-quadrupole mass spectrometry (GC–NCI-qMS). Gas chromatography coupled to ion trap detection working in tandem mode, GC-ITD (MS/MS), was used for final PCB confirmation. Additional purification of the sample extracts was not required. The performance of the complete PLE-based method was evaluated at two spiking levels, 0.4 and 4 ng/g wet weight. Recoveries in the range 60–120% were obtained for PCBs, while those of PBDEs ranged from 86% to 114% for most of the target analytes. The relative standard deviations were in general lower than 20%. The optimized procedure was applied to the determination of the investigated PCBs and PBDEs in a variety of feed samples.