Date of Award
Doctor of Philosophy
Wastewater reclamation and reuse have been increasingly practiced as sustainable strategies to meet water demands, particularly in regions threatened by water shortages. However, one of the biggest challenges for reusing wastewater effluents (WEs) as irrigation water is to remove emerging organic contaminants such as persistent and potentially bioaccumulated per- and polyfluoroalkyl substances (PFAS), whose presence may result in adverse impacts on crops, soils, aqueous ecosystems, and human health. Photocatalysis is an effective and promising technique to remediate PFAS in aqueous media. This dissertation aims to: i) Develop a novel, environmental-friendly, and low-cost treatment process for PFAS removal and degradation for water reuse; ii) Optimize the experimental conditions and investigate the removal mechanisms of PFAS with different structures in this novel process; iii) Scale up this treatment process and apply it to treatment of WEs in a point-of-use (POU) system. First, ultraviolet (UV) C /nanoscale zero-valent iron (nZVI, Fe0 nanoparticles (NPs)) system is used for the first time to induce PFAS photocatalytic removal from aqueous solution. Oxidative and/or reductive degradation of three representative PFAS - perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluorooctane sulfonate (PFOS) was achieved using Fe0 NPs under UVC light both with and without presence of oxygen. However, no PFAS removal was observed either under visible light and in the dark, and much lower PFAS degradation was achieved under UVA light. Higher degradation and defluorination efficiencies were obtained for longer chain PFNA compared to PFOA, and higher degradation and defluorination of PFAS were achieved without presence of O2 compared to with O2. The degradation of PFOA and PFOS followed first order reaction kinetics with the highest efficiencies achieved of 97.6, >99.9, and 98.5% without presence of O2 for PFOA, PFNA, and PFOS, respectively. The degradation efficiencies increased with the increase of nZVI concentrations in the range of 1-100 mg/L. The degradation efficiency of PFOA using bare Fe0 NPs was higher than that using 1% PVP-coated Fe0 NPs in the initial 6 h. Second, the removal mechanism of PFAS in UVC/Fe0 NPs system was obtained by testing the concentrations of iron ions (Fe2+/Fe3+), intermediate products, and reactive oxygen species (ROS, e.g., ·O2- and ·OH) generated, and conducting ROS quenching experiments. The proposed degradation pathway of PFCAs (PFNA and PFOA) was initiated from PFOA/PFNA oxidation by transferring an electron of the carboxylate terminal group of PFOA/PFNA to the Fe(III)-carboxylate complex, then followed by decarboxylation−hydroxylation−elimination−hydrolysis (DHEH) pathway and the accompanying CO2 and F− release. The generated shorter chain PFCAs also underwent degradation with time in the system. This proposed degradation pathway was confirmed by the formation of shorter chain PFCAs, e.g. PFHpA, PFHxA, PFPeA, and PFBA, F- ions, and rapid consumption of Fe3+. For PFOS, besides H/F exchange pathway and chain-shortening (DHEH pathway) to form short chain PFAS during PFCA degradation, desulfonation to form PFOA followed by PFOA degradation also happened. These pathways were suggested by the formation of intermediates — trace amount of shorter chain PFCAs, 6:2 FTS, PFHpS, and F- ions. ·O2- and ·OH were not involved in PFOA degradation in the UVC/Fe0 NPs system with presence of O2, while they may be involved in PFOS degradation, e.g., desulfonation to form PFOA, which were suggested by the results of quenching experiments. And introducing H2O2 into the UVC/Fe0 NPs system resulted in lower PFOA degradation efficiency and defluorination efficiency, which also indicated that ·OH may not be involved in PFOA degradation. Hydrated electrons e-aq that can be involved in desulfonation, defluorination, and C-C bond scission processes were likely quenched by the presence of oxygen to reduce the degradation and defluorination efficiencies; plus, presence of Fe0 NPs may promote the generation of hydrated electrons. Last, UVC/Fe0 NPs system was used to degrade PFAS from WEs in both bench scale and in a scale up POU system. The degradation efficiencies of PFAS in WEs from both wastewater treatment plants (WWTP) were lower than that in deionized water, likely reflecting the complex compositions in the environmental media. Optimal degradation efficiencies of 90±1%, 88±1%, and 46±2% were obtained for PFNA, PFOS, and PFOA, respectively, each starting from 0.5 µg/L using bare Fe0 at pH 3.0 after 2 h. PFAS removal and bacterial inactivation were achieved simultaneously in the POU system using Fe0 NPs without and with rGO support under UVC irradiation in WEs, although the PFAS levels were still above the regulation levels for discard. These pilot tests provided more data and experiences for the real applications of UVC/Fe0 NP system to PFAS contaminated wastewater or other water matrix treatment. Overall, this research demonstrated a cost-effective and environment-friendly method — UVC/Fe0 NPs method for PFAS (i.e., PFOA, PFNA, and PFOS) degradation from WEs for water reuse both with and without presence of oxygen. The possible degradation mechanisms of PFAS with different structures were obtained by testing the concentrations of iron ions, intermediate products, and reactive oxygen species (ROS) involved in the reactions. The developed technology can be potentially applied to treat other environmental media (e.g., groundwater, landfill leachate) that are contaminated by PFAS from previous anthropogenic activities.
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