Activation of persulfate by a layered double oxide supported sulfidated nano zero-valent iron for efficient degradation of 2,2′,4,4′-tetrabromodiphenyl ether in soil

Abstract

The nano zero-valent iron (nZVI) activated persulfate (PS) is recognized as a promising approach to degrade 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47), which is ubiquitous in the soil at electronic waste sites. However, all the reported studies were performed in liquids, gaps in the real behaviour and microbial contribution to the degradation of BDE-47 in soil media need to be urgently filled. The removal efficiency of BDE-47 is low using traditional nZVI as activator because of its aggregation and corrosion. Herein, we designed a novel layered double oxide supported sulfidated nano zero-valent iron (S-nZVI@LDO) composite and explored the performance of S-nZVI@LDO/PS to remediate BDE-47 contaminated soil. The results showed that S-nZVI@LDO has excellent stability and superior reduction capability. It could couple PS to achieve a rapid and efficient degradation of BDE-47, and the removal efficiency reached 92.31 % (5 mg/kg) within 6 h, which was much higher than that of n-ZVI/PS (53.38 %) or S-nZVI/PS (75.69 %). The kinetic constant of BDE-47 degradation by S-nZVI@LDO/PS was 23.6 and 3.7 times higher than that by single S-nZVI@LDO and nZVI/PS, respectively. It is attributable to the efficient production of SO₄^•-, •OH, O₂^•-, and ¹O₂ in the system, in which SO₄^•- and •OH dominated. The bioinformatic analysis demonstrate that soil remediation by S-nZVI@LDO/PS significantly enriched aromatic compounds-degrading bacteria and increased the abundance of hydrocarbon degradation functions. Microbial degradation may play important roles in the BDE-47 degradation and soil quality recovery. The identification of degradation pathways suggests that BDE-47 was degraded to very low-toxic products based on GHS toxicity prediction through a series process of debromination, hydroxylation, cleavage central oxygen, and ring opening, or even completely mineralized. The findings may provide significant implications for the in-situ clean-up of brominated flame retardants in contaminated soil using S-nZVI@LDO/PS Fenton-like system.