Mechanisms of arsenite oxidation and arsenate adsorption by a poorly crystalline manganese oxide in the presence of low molecular weight organic acids

¹ State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Beijing 100083, P.R. China
² School of Water Resources and Environment, China University of Geosciences (Beijing), Beijing 100083, P.R. China

^* Corresponding author: hmguo@cugb.edu.cn.

Abstract

Manganese oxides are considered as one of the effective oxides capable of oxidizing arsenite and reduce the toxicity of arsenic. Since low molecular weight organic acids (LMWOAs) commonly found in nature can act as reducing and chelating agents for manganese oxides, it is particularly important to investigate how these organic acids with different numbers of carboxyl groups like citrate and EDTA affect oxidation and adsorption of arsenic by manganese oxides. In this study, low As(V) adsorption on manganese oxide is slightly enhanced by citrate and EDTA, which results from the increase in active sites via reduction of manganese oxide by LMWOAs. However, citrate and EDTA have different effects on the oxidation of As(III). Mn^III/II citrate autocatalytic cycle as a manganese-based redox system decreases As(III) oxidation rate, but EDTA does not yield autocatalysis, which slightly increases the oxidation rate of As(III). Reduction of manganese oxide by EDTA and chelation between Mn(II) and EDTA lead to exposure of more active sites. Our research highlights the different effects of low molecular weight organic acids on the reactions between arsenic and manganese oxide.