Effect of Mn²⁺ on the phosphorus removal and bioflocculation under anoxic condition

Manganese ion (Mn²⁺) generated from metallurgical, steel making and chemical industries enters sewage treatment plants and affects the sludge activity and flocculation. The effect of Mn²⁺ on the removal of chemical oxygen demand (COD) and total phosphorus (TP) and sludge activity were investigated in anoxic zone of an anaerobic/anoxic/oxic (A²O) process. The compositions and structures of extracellular polymeric substances (EPS) were characterized using three-dimensional excitation emission matrix fluorescence spectroscopy (3D-EEM), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) to reveal the relationship among Mn²⁺, EPS and sludge flocculation. The results showed that low concentration of Mn²⁺ (<5 mg/L) improved removal efficiencies of COD and TP and increased the activity of alkaline phosphatase, acid phosphatase and dehydrogenase. Meanwhile, the addition of Mn²⁺ increased total EPS, sludge contact angle, Zeta potential and sludge particle size, and thus enhanced sludge flocculation. However, high concentration of Mn²⁺ (>10 mg/L) hindered microbial flocculation and reduced removal efficiencies of the pollutants. When Mn²⁺was 5 mg/L, removal efficiencies of COD and TP reached 65% and 90%, respectively. Sludge flocculation was the best and SVI was 70.56 mL/g. The changes of Mn²⁺ concentration caused deviation of groups' compositions in LB-EPS and TB-EPS, where the main components were always protein (PN) and polysaccharide (PS). The addition of Mn²⁺ resulted in the degradation of humic acids. However, it did not give rise to significant morphology changes of EPS.