Effects of incorporating Mn into goethite on adsorption of dissolved organic matter and potentially toxic elements in soil: Isotherms, kinetics, and mechanisms

Goethite is ubiquitous in the environment and plays key role in preserving dissolved organic matter (DOM) and deactivating potentially toxic elements (PTEs) by adsorbing DOM and PTEs. Various non-Fe metals are usually incorporated into natural goethite, substituting Fe in the goethite structure, which dramatically influence the physico-chemical properties and adsorption behavior of the goethite. In the present study, adsorption of DOM and Pb(II) on Mn-substituted goethite samples was investigated. The results displayed that the specific surface area (SSA) of mineral samples increased by 67.6% as the incorporation of Mn for Fe, from 25.71 m2 g-1 for pure goethite to 43.09 m2 g-1for Mn-goethite. Besides, the Mn substitution caused more hydroxyl groups and relatively fewer positive charges on mineral surface, and Mn in the Mn-goethite samples was predominantly present as Mn(III). The amount of DOM adsorbed to per unit mass of goethite was increased as Mn content increased, which was attributed to Mn incorporation increasing the SSA of mineral samples. However, the SSA-normalized absorption capacity for goethite to DOM was decreased by Mn because Mn substitution decreased the number of positive charges of mineral samples, which weakened the electrostatic attraction between DOM and the minerals. The amount of Pb(II) adsorbed to per unit mass of goethite was increased by Mn substitution, and the amount of Pb(II) adsorbed to per unit SSA of goethite increased as the amount of Mn substitution increased, indicating that the increased capacity for adsorbing Pb was not only caused by the SSA increasing but also by there were more surface hydroxyl groups on the Mn-goethite than pure goethite and Pb(II) preferentially adsorbed to Mn sites on the Mn-goethite. The present study results showed that Mn-goethite could be used to sequester DOM and remediate soil contaminated with PTEs because Mn-goethite has a high adsorption capacity and is environmentally benign.