Groundwater As Removal by As(III), Fe(II), and Mn(II) Co-Oxidation: Contrasting As Removal Pathways with O2, NaOCl, and KMnO4

Effective arsenic (As) removal from groundwater is a pressing need in view of increasingly stringent As drinking water limits in some US states and European countries. In this study, we compared the addition of weak (O₂), intermediate (NaOCl), and strong (KMnO₄) groundwater oxidants on the fate of As during As(III), Fe(II), and Mn(II) co-oxidation. Experiments were performed with 50 μg/L As(III), 5 mg/L Fe(II), and 0.5 mg/L Mn(II) in solutions containing relevant groundwater ions, with the reaction products characterized by As K-edge X-ray absorption spectroscopy (XAS). Adding O₂ by aeration was the least effective method, unable to decrease As to below 10 μg/L, which was attributed to inefficient As(III) oxidation. Dosing NaOCl (55 μM) consistently removed As to <10 μg/L (and often <5 μg/L). The As K-edge XAS data of the NaOCl samples indicated complete As(III) oxidation and As(V) sorption to coprecipitated hydrous ferric oxide (HFO) in the binuclear, bridging (²C) complex. The most effective As removal was observed with KMnO₄ (40 μM), which completely oxidized As(III) and yielded residual As concentrations that were less than (by as much as 50%) or equal to the NaOCl experiments. Furthermore, the average As-metal bond length of the KMnO₄ solids (R_As-Fe/Mn = 3.24 ± 0.02 Å) was systematically shorter than the NaOCl solids (R_As-Fe/Mn = 3.29 ± 0.02 Å), consistent with As(V) sorption to both MnO₂ and HFO. These findings can be used to optimize groundwater As treatment to meet relevant drinking water guidelines, while considering the As uptake mode and characteristics of the particle suspension (i.e., colloidal stability and filterability).