One-step process for debromination and mineralization of tetrabromobisphenol a by a layered double oxide-supported sulfurized nanoscale zero-valent iron under ambient conditions

Abstract

Tetrabromobisphenol A (TBBPA), currently the most widely used brominated flame retardant, has attracted significant attention. However, traditional methods for deep debromination or mineralization of TBBPA usually include multiple steps and require external oxidants. In this study, we report a complete degradation of TBBPA through a one-step process of only adding a layered double oxide-supported sulfurized nanoscale zero-valent iron (S-nZVI@LDO) under ambient conditions. TBBPA was rapidly removed by S-nZVI@LDO with an efficiency of 95.6 % (10 mg⋅L-1) within 12 h. The kinetic rate constant (0.0035 min−1) was greater when compared with traditional reductants. The produced Br- ion occupied 76.7 % of total Br content, and the concentration of total organic carbon decreased by over 50 %, suggesting a deep debromination and mineralization of TBBPA by S-nZVI@LDO. It is caused by the substantial improvement of electron transfer, O2 adsorption, and hydrophobicity of S-nZVI@LDO facilitating synchronous reductive debromination and O2 activation to produce ·O2– and ·OH, as approved by electrochemical test, O2-TPO analysis, EPR analysis, and density functional theory calculations. The enriched structural S(−II) and enhanced Fe(III)/Fe(II) redox cycling exerted vital roles in maintaining the reduction potential of the composite. The degradation pathways analysis confirmed that debromination-mineralization mechanisms dominated the complete degradation of TBBPA. This study demonstrates the feasibility of the one-step mineralization removal of TBBPA only using S-nZVI@LDO under ambient conditions and offers insight into external oxidant-free in-situ elimination of halogenated persistent organic pollutants in a natural environment.