Aqueous and solid phase photocatalytic degradation of perfluorooctane sulfonate by carbon- and Fe-modified bismuth oxychloride.

In this study, we prepared and tested a carbon-modified, Fe-loaded bismuth oxychloride (Fe-BiOCl/CS) photocatalyst for photocatalytic degradation of perfluorooctane sulfonate (PFOS). Structural analyses revealed a (110) facet-dominated sheet-type BiOCl crystal structure with uniformly distributed Fe and confirmed carbon modification of the photocatalyst. The presence of d-glucose facilitated the growth control of BiOCl particles and enhanced the adsorption of PFOS via added hydrophobic interaction. Adsorption kinetic and equilibrium tests showed rapid uptake rates of PFOS and high adsorption capacity with a Langmuir Qmax of 1.51 mg/g. When used for directly treating PFOS in solution, Fe-BiOCl/CS was able to mineralize or defluorinate 83% of PFOS (C0 = 100 µgL-1) under UV (254 nm, intensity = 21 mW cm-2) in 4 h; and when tested in a two-step mode, i.e., batch adsorption and subsequent photodegradation, Fe-BiOCl/CS mineralized 65.34% of PFOS that was pre-concentrated in the solid phase under otherwise identical conditions; while the total degradation percentages of PFOS were 83.48% and 80.50%, respectively, for the two experimental modes. The photoactivated electrons and/or hydrated electrons and superoxide radicals primarily initiated the desulfonation of PFOS followed by decarboxylation and defluorination, through a stepwise chain-subsiding mechanism. The elevated photocatalytic activity can be attributed to the effective separation of e-/h+ pairs facilitated by the (110) interlayer electrostatic field, Fe doping, and the presence of oxygen vacancies. This work reveals the potential of carbon-modified and Fe-co-catalyzed BiOCl for concentrating and degrading PFOS and possibly other persistent organic pollutants.

A 'Concentrate-&-Destroy' technology for enhanced removal and destruction of per- and polyfluoroalkyl substances in municipal landfill leachate.

Per- and polyfluoroalkyl substances (PFAS) are ubiquitous in landfill leachate due to their widespread applications in various industrial and consumer products. Yet, there has been no cost-effective technology available for treating PFAS in leachate because of the intrinsic persistency of PFAS and the high matrix strength of landfill leachate. We tested a two-step 'Concentrate-&-Destroy' technology for treating over 14 PFAS from a model landfill leachate through bench- and pilot-scale experiments. The technology was based on an adsorptive photocatalyst (Fe/TNTs@AC), which was able to selectively adsorb PFAS despite the strong matrix effect of the leachate. Moreover, the pre-concentrated PFAS on Fe/TNTs@AC were effectively degraded under UV, which also regenerates the material. The presence of 0.5 M H2O2 during the photocatalytic degradation enhanced the solid-phase destruction of the PFAS. Fresh Fe/TNTs@AC at a dosage of 10 g/L removed >95% of 13 PFAS from the leachate, 86% after first regeneration, and 74% when reused three times. Fe/TNTs@AC was less effective for PFBA and PFPeA partially due to the transformation of precursors and/or longer-chain homologues into these short-chain PFAS. Pilot-scale tests preliminarily confirmed the bench-scale results. Despite the strong interference from additional suspended solids, Fe/TNTs@AC removed >92% of 18 PFAS in 8 h under the field conditions, and when the PFAS-laden solids were subjected to the UV-H2O2 system, ~84% of 16 PFAS in the solid phase were degraded. The 'Concentrate-&-Destroy' strategy appears promising for more cost-effective removal and degradation of PFAS in landfill leachate or PFAS-laden high-strength wastewaters.