New insights into the effect of EDTA on pyrite oxidation and N2O emission during pyrite autotrophic denitrification

Pyrite autotrophic denitrification (PAD) is crucial for removing nitrate in groundwater and advanced wastewater treatment. While disulfide is typically seen as the electron donor, the role of iron in pyrite oxidation is often ignored. In this study, Ethylene Diamine Tetraacetic Acid (EDTA) had been proven to have the potential to facilitate pyrite oxidation by promoting the solubility of iron in solution, thereby enhancing the kinetics of pyrite autotrophic denitrification. Firstly, EDTA could improve PAD performance, i.e. the nitrate removal rate at EDTA addition of 5 mM was 0.69 mg N/L•h and twice that of the control. However, high concentrations of EDTA inhibited the activity of the nitrous oxide reductase, resulting in the maximum accumulation of N2O reaching 13.26 mg N/L with an EDTA concentration of 15 mM. Furthermore, the X-ray Photoelectron Spectroscopy (XPS) result indicated that the EDTA addition promoted the production of bioavailable sulfur, with the concentration of S0 at 15 mM EDTA being more than twice higher than that of the control. Transmission electron microscopy (TEM) analysis indicated that EDTA could relieve the damage of iron encrustation on cell activity because it was difficult for EDTA-chelated ferrous iron to penetrate the cell membrane. Microbial community analyses showed an increase abundance of iron oxidizing bacteria, suggesting that EDTA addition promoted the bioavailability of iron for Fe(II) autotrophic denitrification. Overall, this study will provide insights into the understanding of oxidation mechanism of PAD process and the practical application for efficient nitrogen removal and N2O mitigation.