A sustainable nano-hybrid system of laccase@M-MWCNTs for multifunctional PAHs and PhACs removal from water, wastewater, and lake water

Abstract

This study examined the use of modified multiwall carbon nanotubes (M-MWCNTs) with immobilized laccase (L@M-MWCNTs) for removing ciprofloxacin (Cip), carbamazepine (Cbz), diclofenac (Dcf), benzo[a]pyrene (Bap), and anthracene (Ant) from different water samples. The synthesized materials were characterized using an array of advanced analytical techniques. The physical immobilization of laccase onto M-MWCNTs was confirmed through Scanning electron microscope (SEM)-dispersive X-ray spectroscopy (EDS) analysis and Brunner-Emmet-Teller (BET) surface area measurements. The specific surface area of M-MWCNTs decreased by 65% upon laccase immobilization. There was also an increase in nitrogen content seen by EDS analysis asserting successful immobilization. The results of Boehm titration and Fourier transform infrared (FTIR) exhibited an increase in acidic functional groups after laccase immobilization. L@M-MWCNTs storage for two months maintained 77.8%, 61.6%, and 57.6% of its initial activity for 4 °C, 25 °C, and 35 °C, respectively. In contrast, the free laccase exhibited 55.3%, 37.5%, and 23.5% of its initial activity at 4 °C, 25 °C, and 35 °C, respectively. MWCNTs improved storability and widened the working temperature range of laccase. The optimum removal conditions of studied pollutants were pH 5, 25 °C, and 1.6 g/L of M-MWCNTs. These parameters led to >90% removal of the targeted pollutants for four treatment cycles of both synthetic water and spiked lake water. L@M-MWCNTs demonstrated consistent removal of >90% for up to five cycles even with spiked wastewater. The adsorption was endothermic and followed Langmuir isotherm. Oxidation, dehydrogenation, hydroxylation, and ring cleavage seem to be the dominant degradation mechanisms.