Fast degradation of atrazine by nZVI-Cu 0 /PMS: Re-evaluation and quantification of reactive species, generation pathways, and application feasibility.

Additive metal to zero-valent iron (ZVI) could enhance the reduction ability and the additive Cu ⁰ was incorporated to ZVI to accelerate PMS activation with atrazine (ATZ) as target compound. The efficiencies of ATZ degradation and PMS decomposition climbed up firstly and then declined as Cu ⁰ loading increased from 0.01 to 1.00 wt% with the maximums at 0.10 wt%. SO ₄ ^•- , HO ^• , Fe(IV), O ₂ ^•- and ¹ O ₂ were generated by nZVI-Cu ⁰ /PMS based on the results of electron paramagnetic resonance (EPR) and simultaneous degradation of nitrobenzene, ATZ, and methyl phenyl sulfoxide (PMSO). The rate constant of Fe(IV) and ATZ was estimated as 7 × 10 ⁴ M ^-1 ∙s ^-1 via the variation of methyl phenyl sulfone (PMSO ₂ )formation at different ATZ concentrations. However, Fe(IV) contributed negligibly to ATZ degradation due to the strong scavenging of Fe(IV) by PMS. SO ₄ ^•- and HO ^• were the reactive species responsible for ATZ degradation and the yield ratio of SO ₄ ^•- and HO ^• was about 8.70 at initial stage. Preliminary thermodynamic calculation on the possible activation ways revealed that the dominant production of SO ₄ ^•- might originate from the atomic H reduction of PMS in the surface layer of nZVI-Cu ⁰ . Ten products of ATZ degradation were identified by HPLC/ESI/QTOF and the possible degradation pathways were analyzed combined with theoretical calculation on ATZ structure. The decrease of temperature or increase of solution pH led to the decline of ATZ degradation, as well as the individual addition of common ions (HCO ₃ ^- , Cl ^- , SO ₄ ^2- , NH ₄ ⁺ , NO ₃ ^- and F ^- ) and natural organic matters (NOM). In real water, ATZ was still efficiently degraded with the decontamination efficiency decreasing in the sequence of tap water > surface water > simulated wastewater > groundwater. For the treatment of ATZ-polluted continuous flow, nZVI-Cu ⁰ in double-layer layout had a higher capacity than the single-layer mode. Meanwhile, the leaching TFe and TCu were limited. The results indicate nZVI-Cu ⁰ /PMS is applicable and the multiple-layer layout of nZVI-Cu ⁰ is suggested for ATZ-polluted ground water and soil remediation.
Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
(Copyright © 2023 Elsevier Ltd. All rights reserved.)