Removal of bisphenol A and methylene blue through persulfate activation by calcinated α-MnO2 nanorods: effect of ultrasonic assistance and toxicity assessment.

Abstract

This work investigates the efficacy of α-MnO2 nanorods for persulfate-mediated degradation of bisphenol A (BPA) and methylene blue (MB), in silent and ultrasonic-assisted systems. The conversion of α-MnO2 nanoparticle flakes to nanorods occurs upon calcination at a temperature of 400°C for 3h under the ramping conditions. The comparative characterization of nanomaterials pre- and post-calcination reveals better physical, chemical, and thermal properties of α-MnO2 nanorods. The impact of various operational parameters such as pH, dosage of nanorods, persulfate dose, selected contaminant concentration, ultrasound frequency and power, scavengers, and landfill leachate medium on the degradation of pollutants is also assessed. The ultrasonic assistance yields higher removal for both BPA and MB than the silent system. This may be attributed to the generation of more radicals as ultrasound activates persulfate. This can be due to acoustic cavitation, which leads to better solute dissociation and excited state. The results obtained through scavenger tests reveal that both OH• and SO4•- can contribute to degradation, but the role of SO4•- is found dominant. Significant removal of BPA and MB ((BPA)silent, 87.12%; (MB)silent, 96.54%; (BPA)ultrasonic, 88.75%; (MB)ultrasonic, 93.86%)) is observed in landfill leachate medium. The degradation pathway for pollutants is also proposed. The toxicity of pollutants and their degradation intermediates are evaluated using Ecological Structure Activity Relationships (ECOSAR) program. The results indicate reduced toxicity of BPA intermediates, while most MB degradation intermediates show higher toxicity. Therefore, it can be affirmed that removing pollutants does not ensure a completely non-toxic process. However, the study proposes a comprehensive toxicity evaluation and eliminating toxic intermediates for completely harmless wastewater treatment.