The capability of laccase to oxidate a broad range of polyphenols and aromatic substrates in vitro offers a new technological option for the remediation of polycyclic aromatic hydrocarbon (PAH) pollution with high cytotoxicity. However, laccase application in the remediation of PAH-contaminated sites mainly suffers from a low oxidation rate and high cost because of the difficulty in its recovery. In this study, laccases were immobilized on magnetic Fe3O4 particles coated with chitosan (Fe3O4@SiO2-chitosan) to improve the operational stability and reusability in the treatment of PAH pollution. The enzyme fixation capacity reached 158 mg g-1, and 79.1% of free laccase activities were reserved under the optimum immobilized condition of 4% glutaraldehyde, 1.0 mg mL-1 laccase, 2 h covalent bonding time, and 6 h fixation time. The degradation efficiencies of anthracene (ANT) and benzo[a]pyrene (B(a)P) by Fe3O4@SiO2-chitosan immobilized laccase in 48 h were 81.9% and 69.2%, respectively. Furthermore, it is very easy to magnetically recover the immobilized laccase from reaction systems and reuse it in a new batch. The relative activities of immobilized laccase were over 50% for the degradation of ANT and B(a)P in three catalytic runs, reaching the goal of substantially reducing cost in practice. According to the results from quantum calculations and mass spectrum analyses, the degradation products of ANT and B(a)P by laccase were anthraquinone and B(a)P-dione, respectively. The findings from this study provide valuable insight in promoting the application of immobilized laccase technology in the remediation of PAH contamination.
Keywords: Degradation mechanisms; Fe(3)O(4)@SiO(2)-chitosan; Polycyclic aromatic hydrocarbons; Recoverable immobilized laccase; Structure of immobilized laccase.
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