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Due to recalcitrance of some pharmaceutically active compounds (PhACs), conventional wastewater treatment is not able to remove them effectively. Therefore, their occurrence in surface water and potential environmental impact has raised serious global concern. Biological transformation of these contaminants using white-rot fungi (WRF) and their oxidoreductase enzymes has been proposed as a low cost and environmentally friendly solution for water treatment. The removal performance of PhACs by a fungal culture is dependent on several factors, such as fungal species, the secreted enzymes, molecular structure of target compounds, culture medium composition, etc. In recent 20 years, numerous researchers tried to elucidate the removal mechanisms and the effects of important operational parameters such as temperature and pH on the enzymatic treatment of PhACs. This review summarizes and analyzes the studies performed on PhACs removal from spiked pure water and real wastewaters using oxidoreductase enzymes and the data related to degradation efficiencies of the most studied compounds. The review also offers an insight into enzymes immobilization, fungal reactors, mediators, degradation mechanisms and transformation products (TPs) of PhACs. In brief, higher hydrophobicity and having electron-donating groups, such as amine and hydroxyl in molecular structure leads to more effective degradation of PhACs by fungal cultures. For recalcitrant compounds, using redox mediators, such as syringaldehyde increases the degradation efficiency, however they may cause toxicity in the effluent and deactivate the enzyme. Immobilization of enzymes on supports can enhance the performance of enzyme in terms of reusability and stability. However, the immobilization strategy should be carefully selected to reduce the cost and enable regeneration. Still, further studies are needed to elucidate the mechanisms involved in enzymatic degradation and the toxicity levels of TPs and also to optimize the whole treatment strategy to have economical and technical competitiveness.

Biocatalytic treatment with oxidoreductase enzymes, especially laccases are an environmentally benign method for biodegradation of pharmaceutical compounds, such as carbamazepine to less harmful compounds. However, enzymes are required to be immobilized on supports to be reusable and maintain their activity. Functionalization of support prior to immobilization of enzyme is highly important because of biomolecule-support interface on enzyme activity and stability. In this work, the effect of oxidation of nanobiochar, a carbonaceous material produced by biomass pyrolysis, using HCl, HSO, HNO and their mixtures on immobilization of laccase has been studied. Scanning electron microscopy indicated that the structure of nanobiochars remained intact after oxidation and Fourier transform infrared spectroscopy confirmed the formation of carboxylic groups because of acid treatment. Titration measurements showed that the sample treated with HSO/HNO (50:50, v/v) had the highest number of carboxylic groups (4.7mmol/g) and consequently the highest efficiency for laccase immobilization. Additionally, it was observed that the storage, pH and thermal stability of immobilized laccase on functionalized nanobiochar was improved compared to free laccase showing its potential for continuous applications. The reusability tests towards oxidation of 2, 2'-azino-bis (3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) showed that the immobilized laccase preserved 70% of the initial activity after 3cycles. Finally, using immobilized laccase for degradation of carbamazepine exhibited 83% and 86% removal in spiked water and secondary effluent, respectively.

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Enzymatic degradation with ligninolytic enzyme e.g. laccase is a potential green solution for removal of pharmaceutical compounds that are released into the environment through wastewater effluent. However, the deficiencies of using the enzyme in its free forms, such as reusability and stability should be addressed before industrial applications. In this study, laccase was immobilized onto tailor-made Polyacrylonitrile-biochar composite nanofibrous membrane through covalent bonding and the parameters of immobilization were optimized. The obtained biocatalyst was utilized for removal of chlortetracycline (CTC), carbamazepine (CBZ) and diclofenac (DCF) at an environmentally-relevant concentration in batch mode. These pharmaceutical compounds represented three main categories of pharmaceutical compounds i.e. antibiotics, antidepressant, and anti-inflammatory. The results showed that the immobilized laccase has improved storage, temperature and pH stability compared to free laccase. Also, it maintained more than 17 % of its initial activity after 10 cycles of ABTS oxidation which indicated improved reusability of the enzyme. Using immobilized laccase for degradation of three pharmaceutical compounds in batch experiments exhibited 72.7%, 63.3% and 48.6% degradation efficiency for DCF, CTC, and CBZ, respectively after 8 hours of reaction. The decreasing trend of adsorption extent during reaction time for all compounds confirmed the regenerative effect of laccase on adsorption sites of biochar.

The continuous release of antibiotic compounds through wastewater effluent into environment has raised concerns about their potential problems for different organisms. Enzymatic degradation with laccase is a green option for removal of pharmaceutical compounds from aqueous media. In this study, laccase was immobilized onto homemade Polyacrylonitrile-biochar composite nanofibrous membrane and the obtained biocatalyst was employed for removal of chlortetracycline, a widely used antibiotic, from aqueous media in continuous mode. The results showed that the immobilized laccase has improved storage, temperature and pH stability compared to free laccase. Also, it retained more than 50% of its initial activity after 7cycles of ABTS oxidation which indicated improved enzyme reusability. Finally, while using immobilized laccase for degradation of chlortetracycline in continuous mode exhibited 58.3%, 40.7% and 22.6% chlortetracycline removal efficiency at flux rates of 1, 2 and 3mL/h∙cm.

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