The study investigated the impact factors of metal removal and their role in enhancing anaerobic fermentation of waste activated sludge (WAS), aiming to identify key mechanisms. By optimizing the sludge concentration, it found that a sludge suspension solid range of 10–30 g/L significantly improved the efficiency of anaerobic fermentation, and yielded SCOD of 93.8–177.1 mg/g volatile suspension solid after 8 h, respectively, which was 3.67–4.77 times higher than the control. Correspondingly, the production of short-chain fatty acids (SCFAs) was significantly enhanced. At the optimal sludge suspension solid of 10–30 g/L, the SCFAs were 1.28–1.51 times higher than that of the control. Furthermore, the study evaluated the performance of different metal removal reagents and discovered that microporous COOH reagent outperformed gel SO3H and macroporous SO3H reagent. The macroporous COOH reagent achieved 1.54 and 1.22 times higher SCOD values and significantly enhanced the production of SCFAs, demonstrating its superiority in metal removal and fermentation enhancement. Moreover, the research revealed that sludge concentration and metal removal agent types influenced the activities of key enzymes involved in anaerobic fermentation. Additionally, the macroporous COOH reagent showed the most efficient ability to remove metal ions, contributing to increased nutrient recovery in terms of nitrogen (NH4+-N) and total phosphorus (TP) release during the acidification process. In summary, the enhancing mechanism of metal removal-assistant anaerobic fermentation was discussed from the sludge floc concentration, the skeleton structure and the ion exchange group type. The identified mechanism significantly improves fermentation efficiency and facilitate the organic recovery, representing an innovative approach for wide application in WAS management and resource recovery.
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