In this paper, Fe3O4 nanoparticles (Fe3O4 NPs) grafted carboxyl groups of multiwalled carbon nanotubes with cationic polyelectrolyte poly (dimethyldiallylammonium chloride) (PDDA) (MWCNTs-COO−/PDDA@Fe3O4), are successfully synthesized and used for the extraction of six kinds of major toxic polychorinated biphenyls (PCBs) from a large volume of water solution. The hydrophilicity of the PDDA cage can enhance the dispersibility of sorbents in water samples, and the superparamagnetism of the Fe3O4 NPs facilitate magnetic separation which directly led to the simplification of the extraction procedure. With the magnetic solid-phase extraction (MSPE) technique based on the MWCNTs-COO−/PDDA@Fe3O4 sorbents, it requires only 30 min to extract trace levels of PCBs from 500 mL water samples. When the eluate condensed to 1.0 mL, concentration factors for PCBs became over 500. The spiked recoveries of several real water samples for PCBs were in the range of 73.3–98.9% with relative standard deviations varying from 3.8% to 9.4%, reflecting good accuracy of the method. Therefore, preconcentration of trace level of PCBs by using this MWCNTs-COO−/PDDA@Fe3O4 sorbent, which are stable for multiple reuses, from water solution can be performed.
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