Impact of zero-valent iron on nitrifying granular sludge for 17α-ethinylestradiol removal and its mechanism

Aerobic granulation of nitrifying activated sludge could enhance the removal of 17α-ethinylestradiol (EE2) via abiotic nitration induced by reactive nitrogen species, cometabolism by ammonia-oxidizing bacteria and biodegradation by heterotrophic bacteria. Zero-valent iron (ZVI), a promising and low-cost material, has previously been applied to effectively enhance biological wastewater treatment. The impact and the effect mechanism of ZVI on nitrifying granular sludge (NGS) for EE2 removal was investigated in this study. The results showed that the addition of ZVI achieved better EE2 removal, though ZVI was not conducive to the accumulation of nitrite in NGS which reduced the abiotic transformation of EE2. Moreover, ZVI enriched heterotrophic denitrifying bacteria such as Arenimonas, thus changing the EE2 removal pathway and improving the degradation and mineralization of EE2. In addition, ZVI reduced the emission risk of the greenhouse gas N₂O and strengthened the stability of the granules. Metagenomic analysis further revealed that the functional genes related to EE2 mineralization, nitrite oxidation, N₂O reduction and quorum sensing in NGS were enriched with ZVI addition. This study provides meaningful guidance for ZVI application in the NGS process to achieve efficient and simultaneous removal of ammonia and emerging contaminants.