Motivation of reactive oxidation species in peracetic acid by adding nanoscale zero-valent iron to synergic removal of spiramycin under ultraviolet irradiation: Mechanism and N-nitrosodimethylamine formation potential assessment

In this study, nanoscale zero-valent iron (nZVI) was added to motivate the functions of all the reactive oxidation species in peracetic acid (PAA) mixture under ultraviolet (UV) irradiation, and to enhance the removal of spiramycin, which is a typical precursor of N-nitrosodimethylamine (NDMA). Spiramycin (<= 10 mg/L) could be completely removed within 20 min under the conditions of an initial pH of 4.0, a nZVI dose of 0.02 g/L and a PAA dose of 3.0 mg/L; additionally, 95.8% and 78.8% of PAA and H2O2 were consumed during the process. Electron paramagnetic resonance analysis and quenching experiments confirmed that 52.4% and 44.8% of spiramycin removal was contributed by hydroxyl radical (center dot OH) and carbon-centered radicals (R-C center dot), respectively; and Fe2+ released from nZVI played a critical role in radicals generation. Four degradation pathways of spiramycin were proposed and verified by the density of functional theory analysis. 65.2% of the NDMA formation potential (FP) was reduced after the reaction, and its residual was mainly contributed by the undegraded intermediate of dimethylamine. The results of multiple characterizations and continuous degradation experiments indicated that nZVI was stable in the system as the removal of spiramycin was hardly influenced even if reused three times. The nZVI/UV/PAA process is a promising advanced oxidation technology not only for the removal of refractory NDMA precursors (such as spiramycin) but also for significantly lowering the NDMA FP.