Characterization of Manganese Oxide Modified Activated Carbon for Remediation of Redox-Sensitive Contaminants

Abstract

Manganese oxide modified activated carbon (MOMAC) was synthesized as a novel in situ sediment and soil amendment for treatment of redox-sensitive contaminants, such as mercury (Hg), through buffering of reduction–oxidation (redox) potential and sorption. This study characterized MOMAC synthesis products at three different Mn concentrations on activated carbon (AC) surfaces and compared them with homogeneously precipitated Mn oxide (MnOx) and unmodified AC for properties influencing redox buffering and sorption capacity. Bulk spectroscopic analyses (XAS and XPS), XRD, and electron microscopy showed that homogeneous MnOx matched the local structure of vernadite (δ-Mn(IV)O₂), while MOMAC formed aggregates on the AC surface composed mostly of vernadite with fractions of manganite (γ-Mn(III)OOH) (17–46%) and sorbed Mn(II) (11–21%). Higher bulk surface area and lower Mn average oxidation state were associated with MOMAC and are attributed to the reduction of Mn(IV) by Mn(II) adsorbed on AC or diffused into AC pores. Cation exchange reactions of Na⁺ and Ca²⁺ also contributed to Mn oxidation state changes by driving disproportionation of Mn(III) to Mn(II) and Mn(IV). In batch slurry experiments with and without Hg-contaminated sediment from Oak Ridge National Laboratory (TN, U.S.A.), addition of MOMAC and MnOx resulted in higher solution redox potential and lower pH compared to AC and no-amendment controls. MnOx poised solution redox at higher potential than MOMAC, but MOMAC was more effective at sorbing Hg released by the oxidation of sediment HgS(s), Hg⁰, and/or organic-associated Hg. By combining redox buffering with sorption, MOMAC is a promising in situ amendment that may efficiently target redox-sensitive contaminants in aquatic sediments.