Removal kinetics and mechanisms of tetrabromobisphenol A (TBBPA) by HA-n-FeS colloids in the absence and presence of oxygen

Abstract

The colloid of ferrous sulfide modified by humic acid (HA-n-FeS) shows good reduction and immobilization efficiency for variable-valence heavy metals in wastewater. The removal efficiency of HA-n-FeS for halogenated organic pollutants, however, remains unclear, especially in the absence and presence of oxygen. This study addressed this issue by exploring the effect and mechanism of dissolved oxygen on the degradation of tetrabromobisphenol A (TBBPA) by the HA-n-FeS colloid in water. The results showed that the removal efficiency of different concentrations of TBBPA (5,10, and 20 μm) by the HA-n-FeS colloid was 33.16%, 20.48%, and 22.37% in the absence of oxygen, respectively. When TBBPA reacted with the HA-n-FeS colloid, the concentration of Fe(II) and S(-II) remained stable. The adsorption of HA-n-FeS was the main mechanism of removing TBBPA in the absence of oxygen. In the presence of oxygen, the removal efficiency of TBBPA by the HA-n-FeS colloid was 82.37%, 56.80%, and 43.78% (for the above-mentioned TBBPA concentrations), respectively. In addition, the removal capacity of TBBPA by HA-n-FeS was 39.63, 52.21, and 89.75 mg/g, respectively. The concentration of Fe(II) and S(-II) decreased rapidly in time. Among them, the HA-n-FeS colloid removed part of the TBBPA through chemical adsorption. The main way of chemical adsorption was pore adsorption and functional group (olefin CC, phenolic hydroxyl group O–H, alcohol group C–O) combination. Besides, the HA-n-FeS colloid degraded part of the TBBPA into BPA through reduction, in which 17.72% of TBBPA was removed by the reduction of HA-n-FeS colloid. Fe(II) was the main contributor to the reductive degradation of TBBPA. Furthermore, active species (1O2 and •O2−) played a minor role in the removal of TBBPA by the HA-n-FeS colloids with oxygen, where 13% of TBBPA was removed by 1O2 and •O2−. Therefore, in practical applications, the aeration method can be used to significantly improve the removal efficiency of TBBPA by HA-n-FeS colloids in water.