Evaluation of the joint effects of Cu2+, Zn2+ and Mn2+ on completely autotrophic nitrogen-removal over nitrite (CANON) process

The completely autotrophic nitrogen-removal over nitrite (CANON) process has merits in energy saving and consumption reducing, thus being considered as an attractive alternative over the common denitrification technology. In this study, the effects of three common heavy metals (Cu2+, Zn2+ and Mn2+) in wastewater to the CANON process were evaluated comprehensively. A central composite design with response surface methodology was utilized to investigate the joint effect of these three metal ions on the nitrogen removal performance of CANON process. In accordance with the determined optimal dosage in batch tests, four bioreactors were established with different amounts of heavy metal dosage in long-term operation, which determined the optimal concentrations for Cu2+, Zn2+ and Mn2+ to be 0.25, 0.81 and 1.00 mg/L, respectively. However, the optimal dosing level determined in batch tests showed no promotion during long-term experiment. This indicated that the actual concentration of heavy metals in bioreactors during long-term operation could be higher than expectation, leading to the difference between short-term tests and long-term experiment. The distribution of metal ions revealed that Mn2+ was mainly absorbed in anammox bacteria cells while Cu2+ and Zn2+ were mostly identified inside AOB cells. Moreover, the addition of heavy metals consistently showed positive effects for the relative abundance of AOB, while only a low level of dosage could promote the abundance of anammox bacteria. Furthermore, a mathematical model was established to simulate the CANON system considering the impacts of heavy metals, which was calibrated and validated using independent dataset in this study.