The influence of particle size and structure on the sorption and oxidation behavior of birnessite: I. Adsorption of As(V) and oxidation of As(III)

Sorption and oxidation reactions in the environment may affect substantially the mobility of redox-sensitive toxic trace elements and compounds. Investigating the environmental factors that influence these reactions is crucial in understanding and predicting the geochemical fate of these environmental species, as well as to design appropriate engineered remediation schemes. Arsenic is a widespread contaminant of concern, especially in its oxidized forms, and Mn oxide minerals are some of the major contributors to its oxidation. The goal of this work was to investigate the influence of particle size and structural differences of environmentally-relevant Mn(IV) birnessites on the adsorption of As(V) and on the oxidation of As(III). An acid birnessite of 39 m(2)/g and a delta-MnO2 of 114 m(2)/g were used. Both birnessites sorbed a maximum Pb(II) of 0.3 Pb/Mn, indicating a significantly larger layer cationic vacancy content for acid birnessite, and a density of reactive edge sites for both of 12 sites/nm(2). As(V) forms a bidentate bridging complex on singly-coordinated surface sites at the birnessite particle edges regardless of loading, pH, birnessite type, and presence of pre-sorbed metals(II). Maximum As(V) adsorption, under repulsive electrostatic pH conditions did not yield adsorption congruency behavior between both birnessites at constant pH, presumably because the increase in internal vacancy content causes negative electrostatic repulsion towards external As(V) oxyanion binding.