Small concentrations, big results: µM addition of photoactive iron oxides with PMS, PDS, or H2O2, leads to enhanced removal of viruses at near-neutral pH.

The photo-Fenton process is effective for pathogen removal, and its low-cost versions can be applied in resource-poor contexts. Herein, a photo-Fenton-like system was proposed using low concentrations of iron oxides (hematite and magnetite) and persulfates (peroxymonosulfate - PMS, and peroxydisulfate - PDS), which exhibited excellent inactivation performance towards MS2 bacteriophages. In the presence of bacteria, MS2 inactivation was inhibited in H2O2 and PDS systems but promoted in PMS-involved systems. The inactivation efficacy of all the proposed systems for mixed bacteria and viruses was greater than that of the sole bacteria, showing potential practical applications. The inactivation performance of humic acid-incorporated iron oxides mediating photo-Fenton-like processes was also studied; except for the PMS-involved system, the inactivation efficacy of the H2O2- and PDS-involved systems was inhibited, but the PDS-involved system was still acceptable (< 2 h). Reactive species exploration experiments indicated that ·OH was the main radical in the H2O2 and PDS systems, whereas 1O2 played a key role in the PMS-involved system. In summary, hematite- and magnetite-mediated persulfate-assisted photo-Fenton-like systems at low concentrations can be used as alternatives to the photo-Fenton process for virus inactivation in sunny areas, providing more possibilities for point-of-use drinking water treatment in developing countries.

From rust to robust disinfectants: How do iron oxides and inorganic oxidants synergize with UVA light towards bacterial inactivation?

Pathogens in drinking water remain a challenge for human health, photo-Fenton process is a promising technique for pathogen inactivation, herein, two common iron oxides, hematite and magnetite mediate persulfate (peroxymonosulfate-PMS - and peroxydisulfate-PDS) involved photo-Fenton-like processes were constructed for E. coli inactivation, and the inactivation performance was investigated and compared with the photo-Fenton process under a low intensity UVA irradiation. Results indicated that with a low dose of iron oxides (1 mg/L) and inorganic peroxides (10 mg/L), PMS-involved photo-Fenton-like process is the best substitute for the photo-Fenton one over pH range of 5-8. In addition, humic acid (HA, one of the important components of natural organic matter) incorporated iron oxide-mediated photo-Fenton-like processes for bacteria inactivation was also studied, and facilitating effect was found in UVA/hematite/PMS and UVA/magnetite/PDS systems. Reactive oxygen species (ROS) exploration experiments revealed that ·OH was the predominant radical in H2O2- and PDS-containing systems, whereas 1O2 was one of the principal reactive species in the PMS systems. In addition to the semiconductor photocatalysis of iron oxides and UVA-activated oxidants, iron-complexes (iron-oxidant complexes and iron-bacteria complexes) mediated ligand-to-metal charge transfer (LMCT) processes also made contribution to bacterial inactivation. Overall, this study demonstrates that it is feasible to replace H2O2 with PMS in a photo-Fenton-like process for water disinfection using a low dose of reagents, mediated by cheap catalysts, such as hematite and magnetite, it is also hoped to provide some insights to practical water treatment.

Attenuation of toxicity and occurrence of degradation products of the fungicide tebuconazole after combined vacuum UV and UVC treatment of drinking water.

Antifungal azoles are the most frequently used fungicides worldwide and occur as active ingredients in many antifungal pharmaceuticals, biocides, and pesticides. Azole fungicides are frequent environmental contaminants and can affect the quality of surface waters, groundwater, and drinking water. This study examined the potential of combined vacuum UV (185 nm) and UVC (254 nm) irradiation (VUV/UVC) of the azole fungicide tebuconazole and the transformation product 1,2,4-trizole on degradation and changes in ecotoxicity. In vivo ecotoxicity was examined before and after UV treatment using bioassays with test organisms from different trophic levels to integrate changes in biological effect of the parent compound and the degradation products. The test battery included the luminescent bacterium Aliivibrio fischeri, the Gram-positive bacterium Bacillus subtilis, the fungus Fusarium graminearum, the green microalga Raphidocelis subcapitata, and the crustacean Daphnia magna. The combined VUV/UVC treatment of tebuconazole in drinking water efficiently degraded the parent compound at the µg/L-mg/L level and resulted in transformation products with lower toxicity than the parent compound. A direct positive correlation was observed between the applied UV dose (fluence, J/cm2), the disappearance of tebuconazole, and the decrease in ecotoxicity. The combined VUV/UVC process does not require addition of supplementary oxidants or catalysts and our study suggests that VUV/UVC-mediated photolysis of azole fungicides in water can decrease the overall toxicity and represent a potentially environmentally friendly treatment method.

Removal of alkylphenols from polluted sites using surfactant-assisted soil washing and photocatalysis.

BACKGROUND AND PURPOSE: Surfactant-assisted soil washing and photocatalysis are well-known remediation processes of environmental concern. The application of photocatalysis to treat soil washing extracts containing 4-methylphenol, 4-ethylphenol and 4-tert-butylphenol in the presence of nonionic (C(12)E(8) and C(12)E(23)) and anionic (SDS) surfactants and some of their binary mixtures was investigated in this work by studying the pollutants degradation in the presence of TiO(2) dispersions irradiated with simulated solar light. MATERIALS AND METHODS: Clean soil samples were spiked with the investigated alkylphenols. Aqueous solutions of the chosen surfactants were placed in contact for some hours with the spiked soil samples in a rotatory mixer. The pollutants recoveries were evaluated via HPLC analysis. Photocatalytic experiments were performed in solarbox on aqueous solutions and on aqueous surfactant solutions containing the pollutants. RESULTS: The pollutants removal from the soil was proven effective using the examined surfactant solutions. The photocatalytic treatment of the wastes was faster using Brij 35, but also SDS and C(12)E(8)-SDS mixtures can be applied. After 2-5 h the complete pollutants abatement was obtained, depending on the surfactant chosen and on the amount of TiO(2) employed. On the contrary, the treatment of wastes containing C(12)E(8) was an extremely slow process. CONCLUSIONS: The photocatalytic approach can be applied to remove the examined aromatic pollutants from the washing wastes, confirming the viable coupling between this advanced oxidation method and the surfactant-based soil remediation treatments. Surfactant adsorption onto TiO(2) and micelles concentration play a dominant role.

Intermediate distributions and primary yields of phenolic products in nitrobenzene degradation by Fenton's reagent.

Nitrobenzene thermal degradation was investigated using the Fenton reagent in different experimental conditions. Reaction products were analyzed by HPLC, GC-MS, LC-MS and IC. The products obtained at different nitrobenzene conversion degrees show that degradation mainly involves successive hydroxylation steps of the aromatic ring and its subsequent opening followed by oxidation of corresponding aliphatic compounds. Our results show as primary reaction products: 4-nitrophenol, 3-nitrophenol, 2-nitrophenol, phenol and 1,3-dinitrobenzene, indicating that both hydroxylation and nitration reactions are involved. The formation of phenolic products can be explained by postulating an initial step of HO() addition to nitrobenzene ring. The mechanisms of primary reaction pathways are discussed and a detailed kinetic analysis to obtain the true primary yields of phenolic products is proposed. The relative yields observed for nitrophenol isomers do not follow the expected orientation according to deactivating characteristics of the nitro group but significantly depend on Fe(+2), Fe(+3), H(2)O(2) and O(2) concentrations. The understanding of the effect of reaction conditions on the relative product distribution benefits the application of Fenton and Fenton-like systems to waste water treatment.

Azo-dyes photocatalytic degradation in aqueous suspension of TiO2 under solar irradiation.

The photodegradation of two common and very stable azo-dyes, i.e. methyl-orange (C14H14N3SO3Na) and orange II (C16H11N2SO4Na), is reported. The photocatalytic oxidation was carried out in aqueous suspensions of polycrystalline TiO2 irradiated by sunlight. Compound parabolic collectors, installed at the "Plataforma Solar de Almería" (PSA, Spain) were used as the photoreactors and two identical reacting systems allowed to perform photoreactivity runs for the two dyes at the same time and under the same irradiation conditions. The disappearance of colour and substrates together with the abatement of total organic carbon content was monitored. The main sulfonate-containing intermediates were found to be in lower number in respect to those obtained under artificial irradiation. In particular there were no more evidence of the presence of hydroxylated transients. The dependence of dye photooxidation rate on: (i) substrate concentration; (ii) catalyst amount; and (iii) initial pH was investigated. The influence of the presence of strong oxidant species (H2O2, S2O8(2-)) and some ions (Cl-, SO4(2-)) on the process was also studied.