Arsenate uptake and arsenite simultaneous sorption and oxidation by Fe–Mn binary oxides: Influence of Mn/Fe ratio, pH, Ca2+, and humic acid

Abstract

Arsenate retention, arsenite sorption and oxidation on the surfaces of Fe–Mn binary oxides may play an important role in the mobilization and transformation of arsenic, due to the common occurrence of these oxides in the environment. However, no sufficient information on the sorption behaviors of arsenic on Fe–Mn binary oxides is available. This study investigated the influences of Mn/Fe molar ratio, solution pH, coexisting calcium ions, and humic acids have on arsenic sorption by Fe–Mn binary oxides. To create Fe–Mn binary oxides, simultaneous oxidation and co-precipitation methods were employed. The Fe–Mn binary oxides exhibited a porous crystalline structure similar to 2-line ferrihydrite at Mn/Fe ratios 1:3 and below, whereas exhibited similar structures to δ-MnO2 at higher ratios. The As(V) sorption maximum was observed at a Mn/Fe ratio of 1:6, but As(III) uptake maximum was at Mn/Fe ratio 1:3. However, As(III) adsorption capacity was much higher than that of As(V) at each Mn/Fe ratio. As(V) sorption was found to decrease with increasing pH, while As(III) sorption edge was different, depending on the content of MnO2 in the binary oxides. The presence of Ca2+ enhanced the As(V) uptake under alkaline pH, but did not significantly influence the As(III) sorption by 1:9 Fe–Mn binary oxide; whereas the presence of humic acid slightly reduced both As(V) and As(III) uptake. These results indicate that As(III) is more easily immobilized than As(V) in the environment, where Fe–Mn binary oxides are available as sorbents and they represent attractive adsorbents for both As(V) and As(III) removal from water and groundwater.