A laccase named LAC-4 was purified from Ganoderma lucidum
. Firstly, the enzymatic properties of purified LAC-4 laccase, and the degradation of three chlorophenol pollutants 2,6-dichlorophenol (2,6-DCP), 2,3,6-trichlorophenol (2,3,6-TCP) and 3-chlorophenol (3-CP) by LAC-4 were systematically studied. LAC-4 had a strong ability for 2,6-DCP and 2,3,6-TCP degradation. The degradation ability of LAC-4 to 3-CP was significantly lower than that of 2,6-DCP and 2,3,6-TCP. LAC-4 also had a good degradation effect on the chlorophenol mixture (2,6-DCP + 2,3,6-TCP). The results of kinetics of degradation of chlorophenols by LAC-4 suggested that the affinity of LAC-4 for 2,6-DCP was higher than 2,3,6-TCP. The catalytic efficiency and the catalytic rate of LAC-4 on 2,6-DCP were also significantly higher than 2,3,6-TCP. During degradation of 2,6-DCP and 2,3,6-TCP, LAC-4 had a strong tolerance for high concentrations of different metal salts (such as MnSO4
) and organic solvents (such as ethylene glycol and glycerol). Next, detoxification of chlorophenols by LAC-4 was also systematically explored. LAC-4 treatment had a strong detoxification ability and a good detoxification effect on the phytotoxicity of individual chlorophenols (2,6-DCP, 2,3,6-TCP) and chlorophenol mixtures (2,6-DCP + 2,3,6-TCP). The phytotoxicities of 2,6-DCP, 2,3,6-TCP and chlorophenol mixtures (2,6-DCP + 2,3,6-TCP) treated with LAC-4 were considerably reduced or eliminated. Finally, we focused on the degradation mechanisms and pathways of 2,6-DCP and 2,3,6-TCP degradation by LAC-4. The putative transformation pathway of 2,6-DCP and 2,3,6-TCP catalyzed by laccase was revealed for the first time. The free radicals formed by LAC-4 oxidation of 2,6-DCP and 2,3,6-TCP produced dimers through polymerization. LAC-4 catalyzed the polymerization of 2,6-DCP and 2,3,6-TCP, forming dimer products. LAC-4 catalyzed 2,6-DCP into two main products: 2,6-dichloro-4-(2,6-dichlorophenoxy) phenol and 3,3′,5,5′-tetrachloro-4,4′-dihydroxybiphenyl. LAC-4 catalyzed 2,3,6-TCP into two main products: 2,3,6-trichloro-4-(2,3,6-trichlorophenoxy) phenol and 2,2′,3,3′,5,5′-hexachloro-[1,1′-biphenyl]-4,4′-diol.