Model simulation and mechanism of Fe(0/II/III) cycle activated persulfate degradation of methylparaben based on hydroxylamine enhanced nano-zero-valent iron.

ABSTRACT

The mechanism of Fe2+-activated peroxodisulfate (PDS) by hydroxylamine (HA) has been investigated, however, nano zero-valent iron-activated persulfate (nZVI/PDS) has a more optimal effect and needs further investigation. This study investigated the addition of HA to nZVI/PDS to improve Fe2+ regeneration and accelerate methylparaben (MP) degradation by Fe (0/II/III) cycle. After 60 min of reaction, the HA-enhanced nZVI/PDS (HA/nZVI/PDS) system afforded a 21% increase in MP degradation, reaching 93.26% (1 mM HA, 1 mM nZVI, and 2 mM PDS). nZVI/PDS system was a second-order reaction, but after adding HA, the reaction was more suitable for the first-order reaction. The addition of HA effectively promoted the reduction of Fe3+ to Fe2+ to improve the effect and reaction rate of PDS degradation of MP (k increased from 0.0127 min-1 to 0.0198 min-1) and broadened the reaction pH range. The results of various characterizations of nZVI before and after the reaction revealed that nZVI changed from a spherical structure to a bundle structure and was slightly oxidized. Changes in the Fe2+ and Fe3+ concentrations as well as in the pH of the reaction systems were monitored and the possible reactions of the HA/nZVI/PDS system were derived for the first time (knZVI/PDS<3.7 × 106 M-1 s-1, kFe3+/NH2O· >4.2 min-1). 12 potential compounds were investigated and MP breakdown pathways were speculated; hydroxylation was determined to be the most important pathway of degradation. And the HA/nZVI/PDS system had universal applicability.