Mechanistic insights into δ-MnO2/biochar-activated persulfate-treated wastewater containing antibiotics and heavy metals: Nonradical pathway and pivotal role of Cu(Ⅱ) at low temperature.

Herein, we present a high efficiency system based on biochar loaded with layered manganese dioxide to remove tetracycline and heavy metals from livestock wastewater. Under the optimal conditions, the degradation efficiencies of TC in the δ-MnO2/BC/PS system were 85.5% at 25 °C and 38.5% at 5 °C. Radical quenching experiments revealed that radical reactions in the δ-MnO2/BC/PS system were weak under 15 °C. Adsorption degradation experiments showed that the system maintained good adsorption performance at 5 °C. Galvanic cell experiments and cyclic voltammetry showed that the δ-MnO2/BC material had good electrochemical activity and high stability in response to temperature, indicating that TC was degraded by a nonradical pathway that was not limited by temperature, such as electron transfer. Copper ion was important coadsorbent and coactivator of the reaction system. Furthermore, FTIR, XPS, and X-ray diffraction (XRD) analyses showed that Cu(II) in the system was involved in changing the manganese valence state in the δ-MnO2/BC material and increasing the -OH content of BC. Comparison of the different products generated during metabolic testing revealed that the reaction pathway of the system at low temperature (5 °C) differed from that at normal temperature (25 °C). The δ-MnO2/BC material demonstrated good removal ability for antibiotics and heavy metals at normal and low temperatures in actual biogas slurry. The study provides insight for improving the efficiency of environmentally friendly treatments of aquaculture wastewater in cold regions, which is of great significance for resource utilization.