New insights into persulfate decomposition by soil minerals: radical and non-radical pathways

Persulfate (PS)-based in situ chemical oxidation (ISCO) has been widely used for pollutant remediation in soil and groundwater. However, the underlying mechanism of interactions between mineral and PS was not fully explored. In this study, several soil model minerals including goethite, hematite, magnetite, pyrolusite, kaolin, montmorillonite, and nontronite were selected to investigate their potential effects on PS decomposition and free radical evolution. It was found the decomposition efficiency of PS by these minerals varied significantly, and both the radical and non-radical decomposition processes were included. Pyrolusite has the highest reactivity for PS decomposition. However, PS decomposition is prone to form SO₄^2- through non-radical pathway, and thus, the amounts of free radicals (e.g., ^•OH and SO₄^•-) produced are relatively limited. However, PS mainly decomposed to produce free radicals in the presence of goethite and hematite. In the presence of magnetite, kaolin, montmorillonite, and nontronite, PS both decomposed to produce SO₄^2- and free radicals. Furthermore, the radical process exhibited the high degradation performance for model pollutant such as phenol with relatively high utilization efficiency of PS, while non-radical decomposition has limited contribution to phenol degradation with extremely low utilization efficiency of PS. This study deepened the understanding of interactions between PS and minerals during the PS-based ISCO in soil remediation.