This work systematically examined the capability of ferrate (Fe(VI)) for ammonia oxidation, revealing for the first time that bromide ions (Br- ) played an important role in promoting the removal of ammonia in Fe(VI) system. In the presence of 10.0 mM Br- , the removal efficiency of ammonia was nearly 3.4 times that of the control, and 1.0 mM ammonia was almost completely removed after two rounds addition of 1.0 mM Fe(VI) in 60 min. PMSO probe test, electron paramagnetic resonance spectra and radical quenching experiments were employed to interpret the underlying promotion mechanism of Br- , and it was proposed that the formation of active bromine (HOBr/OBr- ) played a dominant role in the enhanced oxidative removal of ammonia by Fe(VI). Further kinetic model simulations revealed that HOBr/OBr- and Fe(VI) were the two major reactive species in Fe(VI)/Br- system, accounting for 66.7% and 33.0% of ammonia removal, respectively. As the target contaminant, ammonia could quickly consume the generated HOBr/OBr- , thereby suppressing the formation of brominated disinfection byproducts. Finally, NO3- was identified as the dominant transformation product of ammonia, and density functional theory (DFT) calculations revealed that six reaction stages were involved in ammonia oxidation with the first step as the rate-limiting step. This work would enable the full use of coexisting bromides for effective removal of ammonia from natural waters or wastewaters by in situ Fe(VI) oxidation method.

Enhanced removal of ammonia in Fe(VI)/Br- oxidation system: Kinetics, transformation, mechanism, and theoretical calculations

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