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

• Published in: Water research (Oxford) 2025-01, Vol.268 (Pt B), p.122698, Article 122698
• Main Authors: Zhang, Mengyue, Liu, Yuan, Hu, Shujie, Wu, Di, Zheng, Lei, Liu, Hong, Dong, Jun
• Format: Article
• Language: English
• Subjects: Benzene - chemistry; Bifunctional oxidation; Catalysis; Environmental Restoration and Remediation - methods; Groundwater; Groundwater - chemistry; In-situ activation; In-situ chemical oxidation; Manganese Compounds; Non-aqueous phase liquid; Oxidation-Reduction; Oxides; Peroxides - chemistry; Phase transfer catalysis; Trichloroethylene - chemistry; Water Pollutants, Chemical - chemistry
• ISSN: 0043-1354; 1879-2448; 1879-2448
• DOI: 10.1016/j.watres.2024.122698

•PTC-dual oxidation promoted benzene removal by 78 % compared to sole-oxidant systems.•MnO4−transfer ratio was positively related to NAPL solubility and hydrophilicity.•Colloidal MnO2 formed from KMnO4 reduction was the most effective activator of PMS.•SO4•−, O2•- and 1O2 were first observed in NAPL phase in the double-oxidant system.•Adding oxidants in sequence achieved trichloroethene and benzene removal over 75 %. 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. [Display omitted]