N-methylpyrrolidone (NMP) is widely used as an effective solvent for various lithium battery cathode materials. In this study, a microbial electrolysis cell-anaerobic baffled reactor (MEC-ABR) was developed to investigate the performance of simultaneous removal of NMP and sulfate under varying NMP concentrations. The MEC-ABR system achieved an average sulfate removal of 88.13 %, significantly higher than the ABR control (78.64 %), and removal progressively increased across stages, indicating enhanced sulfate reduction via microbial electron transfer. In the first stage (NMP 1 mmol/L) and third stage (NMP 10 mmol/L), the removal rates of NMP by the MEC-ABR were about 20 % and 88 %, respectively. The NMP removal improved over time (MEC-ABR 88.96 %, ABR 90.73 %), but MEC did not significantly enhance NMP removal, attributed to oxygen-dependent NMP degradation and electron competition with methanogens and sulfate-reducing bacteria. Fluorescence 3D excitation-emission matrix spectroscopy (EEM), sludge morphology, cyclic voltammetry, and electrochemical impedance spectroscopy (EIS) analyses confirmed that MEC promoted secretion of electron-active proteins, enhanced electron generation and transfer, and improved sludge flocculation. Microbial and functional gene analyses revealed dominant methanogens (Methanothrix) and sulfate-reducing bacteria, increased expression of electron-generation (mdh) and electron-transfer (sdhA) genes, and voltage-stimulated amo/hao expression, facilitating NMP hydrolysis and nitrification. Overall, MEC enhanced system stability and sulfate reduction, while NMP removal remained limited by oxygen-dependent degradation and microbial electron competition. These findings provide mechanistic insights into MEC-ABR operation and offer guidance for optimizing lithium battery wastewater treatment.
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