Novel phase transfer catalysis coupled with bifunctional oxidation for enhanced remediation of groundwater polluted with multiple NAPL: Performance and mechanisms

Abstract

Structural differences among non-aqueous phase liquids (NAPLs) result in varying oxidation rates, limiting mass transfer between NAPLs and oxidants and seriously impairing the effectiveness of remediation via traditional in-situ chemical oxidation. To tackle this challenge, a novel approach is proposed for remediating multi-NAPL-polluted groundwater that leverages phase transfer catalysis (PTC) to enhance heterogeneous mass transfer by transferring oxidants from groundwater to NAPLs. Meanwhile, “oxidation-in-situ activation” is achieved through bifunctional oxidation using permanganate and peroxymonosulfate (PP). The proposed approach is referred to PTC-PP in this study. Herein, trichloroethene (TCE) and benzene serve as a representative multi-NAPL system. Experimental results indicated that PP significantly improved degradation efficiency of benzene in multi-NAPL system by at least 60.8 % compared to single-oxidant systems, and further enhancement (17.6 %) was achieved when PP was combined with PTC compared to PP alone. Dissolved Mn(II) and MnO₂ generated by MnO₄⁻ reduction effectively activated peroxymonosulfate in PTC-PP system, with colloidal MnO₂ being the most effective activator. Consequently, SO₄^•−, O₂^•− and ¹O₂ were formed in both NAPL and aqueous phases, while ^•OH was formed in aqueous phase, playing a crucial role in benzene oxidation. In phase transfer process of PTC-PP, the proportion of MnO₄⁻ transferred to benzene exceeded that to TCE. This finding illustrated that nondirectional phase transfer of oxidants posed a challenge for simultaneous promotion of TCE and benzene degradation. However, TCE and benzene removal efficiencies were both >75.7 % by applying peroxymonosulfate after KMnO₄ addition. These findings lay the theoretical groundwork for PTC-PP application in groundwater remediation.