Effect of Metal Ions on Oxidation of Micropollutants by Ferrate(VI): Enhancing Role of Fe^IV Species

Abstract

This paper investigated the oxidation of recalcitrant micropollutants [i.e., atenolol (ATL), flumequine, aspartame, and diatrizoic acid] by combining ferrate(VI) (Fe^VIO₄^2-, Fe^VI) with a series of metal ions [i.e., Fe(III), Ca(II), Al(III), Sc(III), Co(II), and Ni(II)]. An addition of Fe(III) to Fe^VI enhanced the oxidation of micropollutants compared solely to Fe^VI. The enhanced oxidation of studied micropollutants increased with increasing [Fe(III)]/[Fe^VI] to 2.0. The complete conversion of phenyl methyl sulfoxide (PMSO), as a probe agent, to phenyl methyl sulfone (PMSO₂) by the Fe^VI-Fe(III) system suggested that the highly reactive intermediate Fe^IV/Fe^V species causes the increased oxidation of all four micropollutants. A kinetic modeling of the oxidation of ATL demonstrated that the major species causing the increase in ATL removal was Fe^IV, which had an estimated rate constant as (6.3 ± 0.2) × 10⁴ M^-1 s^-1, much higher than that of Fe^VI [(5.0 ± 0.4) × 10^-1 M^-1 s^-1]. Mechanisms of the formed oxidation products of ATL by Fe^IV, which included aromatic and/or benzylic oxidation, are delineated. The presence of natural organic matter significantly inhibited the removal of four pollutants by the Fe^VI-Fe(III) system. The enhanced effect of the Fe^VI-Fe(III) system was also seen in the oxidation of the micropollutants in river water and lake water.