Elimination of tetracyclines in seawater by laccase-mediator system

Long-term exposure of antibiotics at low level leads to the accumulation of antibiotics in environmental media and organisms, inducing the formation of antibiotic resistance genes. Seawater is an important sink for many contaminants. Here, laccase from Aspergillus sp. and mediators that follow different oxidation mechanisms were combined to degrade tetracyclines (TCs) at environmentally relevant levels (ng·L-1-μg·L-1) in coastal seawater. The high salinity and alkaline of seawater changed the enzymatic structure of laccase, resulting in a reduced affinity of laccase to the substrate in seawater (Km of 0.0556 mmol·L-1) than that in buffer (Km of 0.0181 mmol·L-1). Although the stability and activity of the laccase decreased in seawater, laccase at a concentration of 200 U·L-1 with a laccase/syringaldehyde (SA) ratio of 1 U: 1 μmol could completely degrade TCs in seawater at initial concentrations of less than 2 μg·L-1 in 2 h. Molecular docking simulation showed that the interaction between TCs and laccase mainly includes hydrogen bond interaction and hydrophobic interaction. TCs were degraded into small molecular products through a series of reactions: demethylation, deamination, deamidation, dehydration, hydroxylation, oxidation, and ring-opening. Prediction of the toxicity of intermediates showed that the majority of TCs can be degraded into low-toxic or non-toxic, small-molecule products within 1 h, indicating that the degradation process of TCs by a laccase-SA system has good ecological safety. The successful removal of TCs by the laccase-SA system demonstrates its potential for the elimination of pollutants in marine environment.