Enhanced nitrogen and phosphorus removal by iron-manganese mediated autotrophic denitrification in electrochemical system and the underlying mechanisms

At present, the research on Fe/Mn autotrophic denitrification is very limited, and the underlying mechanism in electrochemical system is not clear. In this study, an electrochemical system based on Fe-Mn autotrophic denitrification was constructed for the treatment of low C/N wastewater. The underlying mechanism and electrochemical process of Fe/Mn-mediated autotrophic denitrification were elucidated. The results showed that pyrite and manganese mineral matrix had no significant effect on COD removal, but had significant effect on nitrogen removal. R1 (activated carbon matrix) had the lowest nitrogen removal rate, with an average of 66.06%. The mean removal rate of R2 (iron matrix) and R3 (manganese matrix) were 93.94% and 95.89%, respectively. The coupling of iron/manganese ammoxidation and autotrophic denitrification was the main mechanism to achieve efficient nitrogen removal. ICP and FIRT results showed that strong REDOX reactions of Fe, Mn and sulfur occurred at the anode of MFC. Direct precipitation of iron and manganese and electrochemical flocculation (FeOOH) effectively improved phosphorus removal. The phosphorus removal rates of R2 and R3 reached 93.89% and 95.85%, respectively. R3 has high electron transfer efficiency with a maximum voltage of 680 mV. Metagenomic analysis showed that 19 important transcripts associated with nitrogen metabolism pathways and 4 nitrogen metabolism pathways were detected. Enzymes encoded by nap A and nar G genes were abundant in R3 system. Reductase encoded by nrfA and nrfH genes was abundant in R2 system. Iron REDOX genes iroE, iroN, oorA, and manganese REDOX genes moxR, moxA were detected. The results of metabolic pathways and related enzymes further revealed the coupling cycle relationship between metal elements and nitrogen, phosphorus and sulfur in electrochemical systems. This study can not only provide a new method for efficient nitrogen and phosphorus removal of sewage, but also provide scientific basis for improving the geochemical cycle of metal elements and nitrogen elements.