INTERACTIONS BETWEEN METAL OXIDES AND/OR NATURAL ORGANIC MATTER AND THEIR INFLUENCE ON THE OXIDATIVE REACTIVITY OF MANGANESE DIOXIDE

Abstract

Mn oxides have high redox potentials and are known to be very reactive, rendering many contaminants susceptible to degradation via oxidation. Although Mn oxides typically occur as mixtures with other metal oxides (e.g., Fe, Al, and Si oxides) and natural organic matter (NOM) in soils and aquatic environments, most studies to date have studied the reactivity of Mn oxides as a single oxide system. This study, for the first time, examined the effect of representative metal oxides (Al2O3, SiO2, TiO2, and Fe oxides) and NOM or NOM-model compounds (Aldrich humic acid (AHA), Leonardite humic acid (LHA), pyromellitic acid (PA) and alginate) on the oxidative reactivity of MnO2, as quantified by the oxidation kinetics of triclosan (a widely used phenolic antibacterial agent) as a probe compound. The study also examined the effect of soluble metal ions released from the oxide surfaces on MnO2 reactivity. In binary oxide mixtures, Al2O3 decreased the reactivity of MnO2 as a result of both heteroaggregation and complexation of soluble Al ions with MnO2. At pH 5, the surface charge of MnO2 is negative while that of Al2O3 is positive resulting in intensive heteroaggregation between the two oxides. Up to 3.15 mM of soluble Al ions were detected in the supernatant of 10 g/L of Al2O3 at pH 5.0 whereas the soluble Al concentration was 0.76 mM in the mixed Al2O3 + MnO2 system at the same pH. The lower amount of soluble Al in the latter system is the result of Al ion adsorption by MnO2. The experiments with the addition of 0.001 to 0.1 mM Al3+ to MnO2 suspension indicated the triclosan oxidation rate constant decreased from 0.24 to 0.03 h-1 due to surface complexation. Fe oxides which are also negatively charged at pH 5 inhibited the reactivity of MnO2 through heteroaggregation. The concentration of soluble Fe(III) ions ( 4 mg-TOC/L or [alginate/PA] > 10 mg/L, a lower extent of heteroaggregation was also observed due to the negatively charged surfaces for all oxides. Similar effects on aggregation and MnO2 reactivity as discussed above were observed for ternary MnO2‒Al2O3‒NOM systems. HAs, particularly at high concentrations (2.0 to 12.5 mg-C/L), alleviated the effect of soluble Al ions on MnO2 reactivity as a result of the formation of soluble Al-HA complexes. Alginate and PA, however, did not form soluble complexes with Al ions so they did not affect the effect of Al ions on MnO2 reactivity. Despite the above observations, the amount of Al ions dissolved in MnO2+Al2O3+NOM mixtures was too low, as a result of NOMs adsorption on the surface to passivate oxide dissolution, to have a major impact on MnO2 reactivity. In conclusion, this study provided, for the first time, a systematical understanding of the redox activity of MnO2 in complex model systems. With this new knowledge, the gap between single oxide systems and complex environmental systems is much narrower so that it is possible to have a more accurate prediction of the fate of contaminants in the environment.