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Persulfate (PS) is widely used to degrade emerging organic contaminants in groundwater and soil systems, and various PS activation methods (e.g., energy or chemical inputs) have been considered to increase oxidation strength. This study investigates PS activation through manganese amendment in the form of potassium permanganate (KMnO₄) and manganese dioxide (MnO₂) to subsequently degrade the emerging and recalcitrant groundwater contaminant 1,4-dioxane (1,4-D). The activation of PS by MnO₂ was confirmed by radical trap and by product formation. The degradation kinetics of 1,4-D by PS was also compared with varying amendments of KMnO₄ and MnO₂. The results showed that MnO₂ activated PS, which increased the degradation rate constant of 1,4-D. KMnO₄ activation of PS was not observed even though the binary oxidant mixture did enhance the degradation of 1,4-D. These results have implications for applying in situ chemical oxidation in subsurface systems, especially for conditions wherein manganese exists naturally in groundwater or aquifer minerals to support possible PS activation.