Inhibition mechanisms of Fe2+/Fe3+ and Mn2+ on fungal laccase-enabled bisphenol a polyreaction

Bisphenol A (BPA) is regarded as an endocrine disruptor associated with negative health effects in animals and humans. Laccase from white-rot fungus can enable BPA oxidation and auto-polymerization to circumvent its biotoxicity, but the work concerning the effect mechanisms of divalent and trivalent metal ions (MIs) on BPA polyreaction have rarely been reported. Herein, Trametes versicolor laccase-started BPA conversion within 1 h followed pseudo-first order kinetics, and the rate constant ( k prcs ) and half-life were respectively 0.61 h −1 and 1.14 h. The presence of Ca 2+ , Mg 2+ , Cu 2+ , Pb 2+ , Cd 2+ , Zn 2+ and Al 3+ exhibited insignificant impact on BPA removal, whereas Fe 2+ , Fe 3+ and Mn 2+ had a strong inhibiting effect. Compared with MI-free, the k prcs values of BPA respectively lowered 34.4%, 44.3% and 98.4% in the presence of Fe 2+ , Fe 3+ and Mn 2+ . Enzymatic activity and differential absorption spectrum disclosed that the inhibitory actions were accomplished by two different mechanisms. One is Fe 2+ was preferentially oxidized into Fe 3+ that restrained laccase activity at the initial stage of reaction, and subsequently, the formed Fe 3+ complex bound with laccase T1-Cu site and thus impeded the single-electron transfer system. The other is Mn 2+ was instantly oxidized by laccase to generate Mn 3+ -citrate complex, which completely consumed the dissolved O 2 in solution and consequently terminated BPA removal. Considering environmental bioremediation, T. versicolor laccase-enabled auto-polymerization is a simple and convenient candidate to eliminate BPA in enzymatic wastewater treatment, however the effects of Fe 2+ /Fe 3+ and Mn 2+ on BPA decontamination should be cautiously assessed. • T. versicolor laccase caused BPA polyreaction through radical-based covalent coupling. • Fe 3+ complex bound with laccase T1-Cu site and hindered the electron transfer system. • Mn 3+ -citrate complex completely consumed O 2 and thus terminated BPA polyreaction. • Laccase-enabled BPA removal with MIs in water should be prudently considered.