Photo-Fenton and TiO2 Photocatalytic Inactivation of Model Microorganisms under UV-A; Comparative Efficacy and Optimization.

Photocatalytic inactivation of pathogens in aqueous waste is gaining increasing attention. Several homogeneous and heterogeneous photocatalytic protocols exist using the Fenton's reagent and TiO2, respectively. A comprehensive study of homogeneous and heterogeneous photocatalysis on a range of microorganisms will significantly establish the most efficient method. Here, we report a comparative study of TiO2- and Fe+3-based photocatalytic inactivation under UV-A of diverse microorganisms, including Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) bacteria, bacterial spores (Bacillus stearothermophilus spores) and viruses (MS2). We also present data on the optimization of TiO2 photocatalysis, including optimal catalyst concentration and H2O2 supplementation. Our results indicate that both photo-Fenton and TiO2 could be successfully applied for the management of microbial loads in liquids. Efficient microorganism inactivation is achieved with homogeneous photocatalysis (7 mg/L Fe+3, 100 mg/L H2O2, UV-A) in a shorter processing time compared to heterogeneous photocatalysis (0.5 g/L TiO2, UV-A), whereas similar or shorter processing is required when heterogenous photocatalysis is performed using microorganism-specific optimized TiO2 concentrations and H2O2 supplementation (100 mg/L); higher H2O2 concentrations further enhance the heterogenous photocatalytic inactivation efficiency. Our study provides a template protocol for the design and further application for large-scale photocatalytic approaches to inactivate pathogens in liquid biomedical waste.

New perspectives for Advanced Oxidation Processes.

Advanced Oxidation Processes (AOPs) are called to fill the gap between the treatability attained by conventional physico-chemical and biological treatments and the day-to-day more exigent limits fixed by environmental regulations. They are particularly important for the removal of anthropogenic pollutants and for this reason, they have been widely investigated in the last decades and even applied in the treatment of many industrial wastewater flows. However, despite the great development reached, AOPs cannot be considered mature yet and there are many new fields worthy of research. Some of them are going to be briefly introduced in this paper, including hybrid processes, heterogeneous semiconductor photocatalysis, sulphate-radical oxidation and electrochemical advanced oxidation for water/wastewater treatment. Moreover, the use of photoelectrochemical processes for energy production is discussed. The work ends with some perspectives that can be of interest for the ongoing and future research.

Evaluation of an alternative method for wastewater treatment containing pesticides using solar photocatalytic oxidation and constructed wetlands.

The present study proposes an integrated system based on the synergetic action of solar photocatalytic oxidation with surface flow constructed wetlands for the purification of wastewater contaminated with pesticides. Experiments were conducted at pilot scale using simulated wastewater containing the herbicide clopyralid. Three photocatalytic methods under solar light were investigated: the photo-Fenton and the ferrioxalate reagent as well as the combination of photo-Fenton with TiO2 P25, which all led to similar mineralization rates. The subsequent treatment in constructed wetlands resulted in further decrease of DOC and inorganic ions concentrations, especially of NO3-. Clopyralid was absent in the outlet of the wetlands, while the concentration of the detected intermediates was remarkably low. These findings are in good agreement with the results of phytotoxicity of the wastewater, after treatment with the ferrioxalate/wetlands process, which was significantly reduced. Thus, this integrated system based on solar photocatalysis and constructed wetlands has the potential to effectively detoxify wastewater containing pesticides, producing a purified effluent which could be exploited for reuse applications.

Greywater as a sustainable water source: A photocatalytic treatment technology under artificial and solar illumination.

Greywater considers being a highly reclaimable water source particularly important for water-stressed nations. In this work, heterogeneous photocatalysis using artificial and solar illumination has been applied for the mineralization of simulated light greywater (effluents from dishwashers and kitchen sinks were excluded from the study). The effects on the process' efficiency of TiO2 P25 catalyst's concentration, initial concentration of H2O2 and Fe3+, pH of the solution, as well as the type of radiation, were evaluated in a bench-scale Pyrex reactor and a pilot-scale slurry fountain photoreactor. The treatment efficiency has been followed through the evolution of the organic matter content expresses as dissolved organic carbon (DOC). Best results were obtained with the photo-Fenton-assisted TiO2 photocatalytic process with 72% DOC removal after 210 min of bench scale treatment, while under the same photocatalytic conditions in the pilot reactor the DOC removal reached almost 64%. Moreover, the decrease in toxicity, phytotoxicity and biodegradability of the simulated wastewater has been observed after solar-induced photocatalytic treatment.

Homogeneous photocatalytic oxidation of UV filter para-aminobenzoic acid in aqueous solutions.

The presence of personal care product (PCP) residues in the aquatic environment is an emerging issue due to their uncontrolled release through graywater; for this reason, efforts are being made to develop methods to inactivate or eliminate this class of substances in the environment. In this work, homogeneous photocatalysis has been applied for the degradation of UV filter para-aminobenzoic acid (PABA), which exists in several types of PCPs, in order to identify the optimum degradation conditions. The oxidation of PABA by photo-Fenton and oxalate-induced photo-Fenton (ferrioxalate) processes was investigated, and the effect of various operating variables has been assessed, i.e., Fe3+ (0.0035-0.014 g L-1), H2O2 (0.025-0.2 g L-1), T (280-323 K), and type of radiation (UV-A, visible). Furthermore, experiments under optimal conditions have been performed in order to evaluate the transformation pathways and phytotoxicity of the treated PABA solution.

Homogenous photocatalytic decontamination of prion infected stainless steel and titanium surfaces.

Prions are notorious for their extraordinary resistance to traditional methods of decontamination, rendering their transmission a public health risk. Iatrogenic Creutzfeldt-Jakob disease (iCJD) via contaminated surgical instruments and medical devices has been verified both experimentally and clinically. Standard methods for prion inactivation by sodium hydroxide or sodium hypochlorite have failed, in some cases, to fully remove prion infectivity, while they are often impractical for routine applications. Prion accumulation in peripheral tissues and indications of human-to-human bloodborne prion transmission, highlight the need for novel, efficient, yet user-friendly methods of prion inactivation. Here we show both in vitro and in vivo that homogenous photocatalytic oxidation, mediated by the photo-Fenton reagent, has the potential to inactivate the pathological prion isoform adsorbed on metal substrates. Photocatalytic oxidation with 224 µg mL(-1) Fe (3+), 500 µg mL(-1) h(-1) H 2O 2, UV-A for 480 min lead to 100% survival in golden Syrian hamsters after intracranial implantation of stainless steel wires infected with the 263K prion strain. Interestingly, photocatalytic treatment of 263K infected titanium wires, under the same experimental conditions, prolonged the survival interval significantly, but failed to eliminate infectivity, a result that we correlate with the increased adsorption of PrP(Sc) on titanium, in comparison to stainless steel. Our findings strongly indicate that our, user--and environmentally--friendly protocol can be safely applied to the decontamination of prion infected stainless steel surfaces.

Electrochemical enhancement of solar photocatalysis: degradation of endocrine disruptor bisphenol-A on Ti/TiO2 films.

The photoelectrocatalytic oxidation over immobilized Ti/TiO(2) films in the presence of simulated solar light was investigated for the degradation of bisphenol-A (BPA) in water. The catalyst, consisting of 75:25 anatase:rutile, was prepared by a sol-gel method and characterized by cyclic voltammetry, X-ray diffraction and scanning electron microscopy. Experiments were conducted to assess the effect of applied current (0.02-0.32 mA/cm(2)), TiO(2) loading (1.3-9.2 mg), BPA concentration (120-820 µg/L), initial solution pH (1 and 7.5) and the aqueous matrix (pure water and treated effluent) on BPA photoelectrocatalytic degradation which was monitored by high performance liquid chromatography equipped with a fluorescence detector. The reaction was favored at anodic currents up to 0.04 mA/cm(2) and lower substrate concentrations, but it was hindered by the presence of residual organic matter and radical scavengers (e.g. bicarbonates) in treated effluents. Moreover, a pseudo-first order kinetic model could fit the experimental data well with the apparent reaction constant taking values between 2.9 and 32.4 10(-3)/min. The degradation of BPA by pure photocatalysis or electrochemical oxidation alone was also studied leading to partial substrate removal. In all cases, the contribution of applied potential to photocatalytic degradation was synergistic with the photocatalytic efficiency increasing between 24% and 97% possibly due to a more efficient separation and utilization of the photogenerated charge carriers. The effect of photoelectrocatalysis on the ecotoxic and estrogenic properties of BPA was also evaluated measuring the bioluminescence inhibition of Vibrio fischeri and performing the yeast estrogen screening assay, respectively.

Photocatalytic oxidation of Cibacron Yellow LS-R.

The photocatalytic degradation of Cibacron Yellow LS-R (CIY), an azo dye, has been investigated in aqueous heterogeneous solutions containing semiconductor oxides as photocatalysts. The disappearance of the organic molecule follows approximately a pseudo-first kinetic order according to the Langmuir-Hinshelwood model. Various commercial photocatalysts are compared with respect to their decolorization efficiency, the COD, as well as the toxicity reduction. The effect of the temperature on the reaction rate is ascertained.

Sonochemical disinfection of municipal wastewater.

The application of high intensity, low frequency ultrasound for the disinfection of simulated and septic tank wastewaters is evaluated in this work. Laboratory scale experiments were conducted at 24 and 80kHz ultrasound frequency with horn-type sonicators capable of operating in continuous and pulsed irradiation modes at nominal ultrasound intensities up to 450W. For the experiments with simulated wastewaters, Escherichia coli were used as biological indicator of disinfection efficiency, while for the experiments with septic tank wastewaters, the total microbiological load was used. Complete elimination of E. coli could be achieved within 20-30min of irradiation at 24kHz and 450W with the efficiency decreasing with decreasing intensity and frequency. Moreover, continuous irradiation was more effective than intermittent treatment based on a common energy input. Irradiation of the septic tank effluent prior to biological treatment at 24kHz and 450W for 30min resulted in a three-log total microbiological load reduction, and this was nearly equal to the reduction that could be achieved during biological treatment. Bacterial cell elimination upon irradiation was irreversible as no reappearance of the microorganisms occurred after 24h.

Optimized photocatalytic degradation of Alcian Blue 8 GX in the presence of TiO2 suspensions.

The photocatalytic degradation of Alcian Blue 8 GX, a cationic copper phthalocyanine dye, has been investigated in aqueous suspensions containing the commercial catalyst TiO(2) P-25. The photodegradation of the organic molecule follows approximately a pseudo-first kinetic order, according to the Langmuir-Hinshelwood model. The effect of catalyst concentration, pH of the initial solution and the H(2)O(2) concentration upon the reaction rate was ascertained. It was shown that the photocatalytic degradation reaction can be mathematically described as a function of parameters such as pH, H(2)O(2) concentration and irradiation time, being modeled by the use of the response surface methodology. Optimized values for oxidizing agent, concentration, pH and UV exposure time for the studied system were determined.

Titanium dioxide photocatalytic inactivation of prions.

Prions are postulated to be the infectious agents of a family of transmissible, fatal, neurodegenerative disorders affecting both humans and animals. The possibility of prion transmission constitutes a public-health risk that confronts regulatory authorities everywhere. The main problem in handling prions is the fact that they are extremely resistant to standard decontamination methods. Thus, the use of harsh and expensive practices to destroy prions is inevitable. The development of applicable and efficient prion-inactivation practices is still highly important for the prevention of accidental transmission. In the search for effective and environmentally friendly methods to eliminate organic compounds and bacteria, much attention has been focused on the so-called advanced oxidation processes. These are based on the formation of hydroxyl radicals, which are known to possess a high reductive potential. This study tested the potential of titanium dioxide, an inexpensive and completely inert reagent, to inactivate prions in a heterogeneous photocatalytic process. Initial in vitro experiments were followed by a bioassay with the scrapie strain 263K in Syrian hamsters. The results obtained from this study indicate that titanium dioxide photocatalytic treatment of scrapie-infected brain homogenates reduces infectivity titres significantly.