Iron-oxides and iron-citrate as new photocatalysts in solar inactivation of Escherichia coli in water: mechanistic aspects

This study addresses the bacterial inactivation mechanism by photo-Fenton process at near-neutral pH, focusing on iron-oxides and iron-citrate as photocatalysts for solar water disinfection and using E. coli as a bacteria model. Cell envelope damage during bacterial inactivation by photo-Fenton and TiO2 photocatalysis were investing providing evidence for lipid peroxidation and cell permeability. TiO2 photocatalysis induced significant cell membrane damage, in contrast to the photo-Fenton process, but the inactivation kinetics for both disinfection processes was similar. A higher efficiency of photo-generation of reactive oxygen species (ROS) in the presence of TiO2 photocatalyst compared with the photo-Fenton system was observed. The bactericidal effect of Fe3+/hv seems possible due to the adsorption of Fe3+ ions on the bacterial cell wall followed by photosensitization of iron-bacteria exciplexes oxidizing the cell membrane. In contrast, the effect of Fe2+/hv was associated with diffusion into the cell giving raise to intracellular dark Fenton¿s reactions. We suggest that cell envelope damage might not necessarily be a unique pathway in bacterial inactivation by photo-Fenton treatment. In particular, the enhancement of an internal (photo)-Fenton process by the synergistic action of UVA and the external Fenton's reactants appears to be an important contribution to bacterial inactivation. Bacterial inactivation by the heterogeneous photo-Fenton process was carried out via iron (hydr)oxide particles, i.e. hematite, goethite, wüstite and magnetite. We found that, the iron (hydr)oxides act as photocatalytic semiconductors and catalysts in the heterogeneous photo-Fenton process with the exception of magnetite, which needs H2O2 as electron acceptors. The Hydroxyl radical and superoxide radical were the principal ROS produced by iron (hydr)oxide particles under light in the absence or presence of H2O2. Natural organic matter (NOM) and inorganic substances did not interfere with the photocatalytic semiconducting action of hematite during bacterial inactivation, but enhanced bacterial inactivation mediated by hematite used as the photo-Fenton reagent. Our results demonstrated, for the first time, that low concentration of iron (hydr)oxides (0.6 mg/L) under sunlight, acting both as semiconductors or catalysts of the heterogeneous photo-Fenton process, may serve as a disinfection method for waterborne bacterial pathogens. Bacterial inactivation by the homogeneous photo-Fenton process was carried out using Fe¿citrate complex as a source of iron. The efficiency of the homogeneous photo-Fenton process using Fe-citrate complex strongly improved bacterial inactivation as compared with the FeSO4 and goethite as sources of iron. The bacterial inactivation rate increased in the order of goethite < FeSO4 < Fe-citrate, which agreed with the ¿OH radicals detected by ESR. Encouraging results were also obtained while applying this treatment for bacterial inactivation in natural water samples at pH 8.5. No bacterial reactivation and/or growth were observed showing that Fe-citrate-based photo-Fenton process efficiently inactivate bacteria using a low iron concentration of Fe-citrate, while avoiding precipitation of ferric hydroxides. The application of the photo-Fenton process at near-neutral pH is a promising technique for bacterial inactivation, due to its simplicity, the use of the sun, the low concentration of reagents and does not produce toxic waste.

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