A series of mesoporous iron-based spinel materials were synthesized to degrade polychlorinated biphenyls (PCBs), with CB-209 being used as a model compound. The materials were characterized by X-ray powder diffraction (XRD), pore structure analysis, and X-ray photoelectron spectroscopy (XPS). A comparison of the dechlorination efficiencies (DEs) of the materials revealed that NiFe2O4 had the highest DE, followed by Fe3O4. Newly produced polychlorinated biphenyls, chlorinated benzenes, hydroxyl species and organic acids were detected by gas chromatography-mass spectrometry, high performance liquid chromatography-mass spectrometry and ion chromatograph. Identification of the intermediate products indicates that three degradation pathways, hydrodechlorination, the breakage of C-C bridge bond and oxidative reaction, accompanied by one combination reaction, are competitively occurring over the iron-based spinels. The relative amounts of produced three NoCB isomers were illustrated by the C-CI BDEs of CB-209 at meta-, para- and ortho-positions, and their energy gap between HOMO and LUMO. The consumption of the reactive oxygen species caused by the transformation of Fe3O4 into Fe2O3 in the Fe3O4 reaction system, and the existence of the highly reactive O-2(-center dot) species in the NiFe2O4 reaction system, could provide a reason why the oxidation reaction was more favored over NiFe2O4 than Fe3O4. (C) 2013 Elsevier B.V. All rights reserved.