Organic contaminants (OCs), such as pharmaceuticals, personal care products, flame retardants, and plasticisers, are societally ubiquitous, environmentally hazardous, and structurally diverse chemical compounds whose recalcitrance to conventional wastewater treatment necessitates the development of more effective remedial alternatives. The engineered application of ligninolytic oxidoreductase fungal enzymes, principally white-rot laccase, lignin peroxidase, and manganese peroxidase, has been identified as a particularly promising approach for OC remediation due to their strong oxidative power, broad substrate specificity, low energy consumption, environmental benignity, and cultivability from lignocellulosic waste. By applying an understanding of the mechanisms by which substrate properties influence enzyme activity, a set of semi-quantitative physicochemical criteria (redox potential, hydrophobicity, steric bulk and pKa) was formulated, against which the oxidoreductase degradation susceptibility of twenty-five representative OCs was assessed. Ionisable, compact, and electron donating group (EDG) rich pharmaceuticals and antibiotics were judged the most susceptible, whilst hydrophilic, bulky, and electron withdrawing group (EWG) rich polyhalogenated compounds were judged the least susceptible. OC susceptibility scores were in general agreement with the removal rates reported for experimental oxidoreductase treatments (R2 = 0.60). Based on this fundamental knowledge, and recent developments in enzyme immobilisation techniques, microbiological enzymic treatment strategies are proposed to formulate a new generation of biological wastewater treatment processes for the biodegradation of environmentally challenging OC compounds.
Keywords: enzymatic degradation; organic contaminant; oxidoreductase enzymes; redox potential.