Enhanced dissimilatory nitrate reduction to ammonium and electron transfer mechanisms in bidirectional electron transfer biofilm constructed by iron phthalocyanine.

Bidirectional electron transfer biofilms (BETB) could efficiently reduce nitrate without accumulating nitrite, representing a promising biological electrochemical denitrification technology. This study utilized iron phthalocyanine modified carbon felt (FePc-CF) to enrich electroactive bacteria, constructing a long-term stable FePc-BETB. Its nitrate removal rate reached 91%, far exceeding the traditional nitrate-reducing biocathode (45%) and Con-BETB (46%). The dissimilatory nitrate reduction to ammonium (DNRA) dominated nitrate reduction in FePc-BETB, consuming 35% of the total electrons. Additionally, FePc-BETB effectively reduced the accumulation of NO2--N and N2O. Electrochemical analysis demonstrated FePc-BETB exhibited stronger electrochemical activity and electron transfer capability. Mediated electron transfer (MET) enhanced by increased extracellular humic acid in FePc-BETB favored the electron supplement for nitrate removal. The relative abundance of nrfA, marker of the DNRA, increased significantly. This study provided new insights into regulating denitrification and DNRA pathways and treating nitrate wastewater lacking electron donors.