Goethite-humic acid coprecipitate mediated Fenton-like degradation of sulfanilamide: The role of coprecipitated humic acid in accelerating Fe(III)/Fe(II) cycle and degradation efficiency

Abstract

While extensive studies found that dissociative and iron mineral-adsorbed humic acid (HA) could either stimulate or inhibit Fenton-like processes, little was known about the influence of iron mineral-coprecipitated HA on Fenton-like reactions. Here, goethite and HA (Gt-HA) coprecipitates having different C:Fe molar ratios (C:Fe = 0.16-0.99) were biologically prepared, and for the first time, investigated for their abilities of H₂O₂ activation and catalytic degradation of sulfanilamide. For system containing Gt-HA with the optimal C:Fe ratio of 0.30, over 91.1% of sulfanilamide (10 mg/L) was removed in 2 h, which was 46.2% higher than that of the control Gt system. Additionally, H₂O₂ decomposition, •OH production, and organic carbon removal in Gt-HA systems were all more efficient than those in Gt system. Higher carbon moieties stability and lower micropore surface area of Gt-HA decreased the competition for •OH and H₂O₂, thus helped to improve degradation efficiency. Electrochemical analysis, quenching experiments, and Fe species detection showed that the coprecipitated HA could serve as electron shuttle and complex with Fe(III) mainly via carboxyl groups at octahedral sites to improve Fe(III)/Fe(II) transformation. This study improved our understanding of Fe(III)/Fe(II) cycling in Fe‒C coprecipitates and demonstrated the potential of developing Fe‒C coprecipitates as efficient catalysts in Fenton-like processes.

Keywords: Coprecipitate; Fenton-like reaction; Humic acid; Sulfanilamide.