Recent advances on the application of UV-LED technology for microbial inactivation: Progress and mechanism.

Conventional technologies for the inactivation of microorganisms in food products have their limitations, especially changes in quality attributes that have led to quality deterioration, low consumer acceptance, impact on the environment, and potential health hazards (carcinogens). Ultraviolet (UV) light is an emerging promising nonthermal technology employed for microbial inactivation in water, liquid, and solid food products to curtail the limitations above. This review provides an insight into UV light-emitting diodes (UV-LEDs)' potential as an alternative to the traditional UV lamps for microbial inactivation in liquid and solid media. Also, the mechanisms of inactivation of lone and combined UVA-, UVB-, and UVC-LEDs were discussed. The strategies utilized to improve the efficacy between the UV-LED treatments at various wavelengths were summarized. Combining different UV-LEDs treatments at different wavelengths have a synergistic effect and suppression of microbial cell reactivation. The UV-LED-based advanced oxidation processes (AOPs) also have high germicidal action against numerous microorganisms and are efficient for the degradation of micropollutants. Among the UV-LEDs discussed, UVC-LED has the most antimicrobial effect with the most efficient micropollutants decomposition with regards to UV-LED-based AOPs. This review has provided vital information for future application, development, and customization of UV-LED systems that can meet the food and water safety requirements and energy efficiency.

Ultrasonic Destruction of Acid Orange 7: Effect of Humic Acid, Surfactants and Complex Matrices.

The ultrasonic degradation at 600 kHz of an azo dye, acid orange 7 (AO7), in the presence of various dissolved natural organic matters (humic acid and surfactants) and in environmentally relevant matrices (natural water and seawater) was investigated. Additionally, the dependence of AO7 degradation on several operating parameters was clarified. The obtained results showed that ultrasound completely destroyed AO7 in 90 min of treatment but only 10% of TOC was removed after a long irradiation time. Investigations using the radical scavengers tert-butyl alcohol and KI revealed that AO7 degradation proceeds through radical reactions occurring at the bubble-liquid interface. AO7 conversion was strongly affected by the operating conditions. While the degradation of the dye was not affected by the presence of humic acid, it was impacted negatively by the presence of surfactants. Replacing deionized water by natural water and seawater as real environmental matrices did not affect the degradation of the dye.

Degradation and mineralization of Bisphenol A (BPA) in aqueous solution using advanced oxidation processes: UV/H2O2 and UV/S2O8(2-) oxidation systems.

This work reports on the removal and mineralization of an endocrine disrupting chemical, Bisphenol A (BPA) at a concentration of 0.22 mM in aqueous solution using inorganic oxidants (hydrogen peroxide, H2O2 and sodium persulfate, Na2S2O8;S2O8(2-)) under UV irradiation at a wavelength of 254 nm and 40 W power (Io = 1.26 × 10(-6) E s(-1)) at its natural pH and a temperature of 29 ± 3 °C. With an optimum persulfate concentration of 1.26 mM, the UV/S2O8(2-) process resulted in ∼95% BPA removal after 240 min of irradiation. The optimum BPA removal was found to be ∼85% with a H2O2 concentration of 11.76 mM. At higher concentrations, either of the oxidants showed an adverse effect because of the quenching of the hydroxyl or sulfate radicals in the BPA solution. The sulfate-based oxidation process could be used over a wider initial pH range of 3-12, but the hydroxyl radical-based oxidation of BPA should be carried out in the acidic pH range only. The water matrix components (bicarbonate, chloride and humic acid) showed higher scavenging effect in hydroxyl radical-based oxidation than that in the sulfate radical-based oxidation of BPA. UV/S2O8(2-) oxidation system utilized less energy (307 kWh/m(3)) EE/O in comparison to UV/H2O2 system (509 kWh/m(3)) under optimum operating conditions. The cost of UV irradiation far outweighed the cost of the oxidants in the process. However, the total cost of treatment of persulfate-based system was much lower than that of H2O2-based oxidation system.

Photodegradation of amoxicillin in aqueous solution under simulated irradiation: influencing factors and mechanisms.

This paper investigated the effects of selected common chemical species in natural waters (HCO3(-), NO3(-) and humic acids (HA)) on the photodegradation of amoxicillin (AMO) under simulated irradiation using a 300 W xenon lamp. Quenching experiments were carried out to explore the mechanisms of AMO photodegradation. The results indicated that AMO photodegradation followed pseudo-first-order kinetics. Increasing AMO concentration from 100 to 1,000 µg L(-1) led to the decrease in the photodegradation rate constant from 0.2411 to 0.1912 min(-1). The presence of NO3(-) and HA obviously inhibited the photodegradation rate of AMO because they can compete for photons with AMO. Bicarbonate, as a hydroxyl radical (·OH) scavenger, also adversely affected AMO photodegradation. Quenching experiments in pure water suggested that AMO could undergo self-sensitized photooxidation via ·OH and singlet oxygen ((1)O2), accounting for AMO removal of 34.86 and 8.26%, respectively. In HA solutions, the indirect photodegradation of AMO was mostly attributed to the produced ·OH (22.37%), (1)O2 (24.12%) and (3)HA* (20.80%), whereas the contribution of direct photodegradation was to some extent decreased.

Removal of COD and colour in real pharmaceutical wastewater by photoelectrocatalytic oxidation method.

In this study, TiO2/Ni photo-anode and multi-walled carbon nano-tubes (MWCNTs) air cathode were prepared by the dip-coating method, and the photoelectrocatalytic degradation of real pharmaceutical wastewater was investigated in the self-made reactor. The combination of the TiO2/Ni electrode and MWCNTs air cathode was adopted to treat the pharmaceutical wastewater by the process of photoelectrocatalysis. Various operational parameters to achieve optimum efficiency of this photoelectrocatalytic degradation system are presented, such as applied bias voltage, NaCl concentration, pH and different degradation methods. Under the optimal conditions, the removal of chemical oxygen demand (COD) and colour are 93.5% and 78.5% respectively. The possible roles of the anode-cathode on the reactions and the probable mechanisms of effect were also discussed. The photoelectrocatalytic technology can be used for the long-term treatment of real pharmaceutical wastewater.

Degradations of model compounds representing some phenolics in olive mill wastewater via electro-Fenton and photoelectro-Fenton treatments.

The electrochemical oxidation of vanillic acid, o-coumaric acid and protocatechuic acid, three representative toxic phenolics in olive mill wastewater, was studied using carbon felt cathode in the electro-Fenton system. Results obtained, in the presence or absence of UV support, were compared throughout the degradation processes up to mineralization. It was demonstrated that all three phenolic compounds reacted completely with hydroxyl radicals and degraded efficiently. It was shown in the photoelectro-Fenton process that the degradation and mineralization efficiency of the phenolic compounds were enhanced by the effect of UV light, especially at the later stages of the degradation processes.

[Detoxification of textile industry effluents by photocatalytic treatment]. / Détoxication des effluents d'industrie de textile par photocatalyse.

In Morocco the textile industry, representing 31% of all Moroccan industries, is accompanied by high water consumption and important wastewater discharges rejected without any treatment. The focus of this study was to characterize the effluent from the textile industry, to test separately the effect of UV light and TiO2 catalyst and to determine the optimum conditions (pH, concentration and reaction time) in photocatalytic treatment to reduce chemical oxygen demand (COD) and colour. The biodegradability of the effluent was also studied using a toxicity test before and after treatment. After 90 min of reaction time at pH 4 and with 1.5 g F' of TiO2 catalyst, the photocatalytic treatment reached a global removal rate of 53% for COD and 89% for discoloration of the effluent. The relation BOD5/COD increased from around 0 to 0.3. The effluent became accessible to a biological treatment. The toxicity was studied by the Daphnia magna test over 24 hours. The results have shown the important toxicity of these effluents, which are rich in organic matter and other chemical compounds. After treatment by photocatalytic oxidation, the CI50 24 increased from 3.8% to 22.8%. This reduction of toxicity is related to the reduction of COD (53%) and colour (89%). Photocatalytic treatment has been shown to have an environmental benefit and, in combination with a secondary biological treatment, can be important for a significant reduction in the pollution of textile effluents.

Photochemical reaction of tricresyl phosphate (TCP) in aqueous solution: Influencing factors and photolysis products.

Organophosphate triesters (OPEs) have caused great concern as a class of emerging environmental contaminants due to their widespread use and their toxicity to organisms. However, the phototransformation behavior of OPE is still not fully understood, which is important for understanding their environmental fate. In the present study, the photodegradation of tricresyl phosphate (TCP), one of the most widely detected OPEs in aqueous environments, was investigated including the direct photolysis and in the presence of several natural water factors, NO2-, Fe3+ and humic acid. The degradation process followed the pseudo-first-order kinetics, with rate constant increasing slightly with increasing initial TCP concentration. The presence of NO2- and Fe3+ was observed to promote the photochemical loss of TCP, while humic acid played a negative role on TCP transformation. Electron spin resonance (EPR) analysis showed that carbon-centered radical was produced in the photolysis process of TCP, and hydroxyl radical contributed to the promotion of rate constant for Fe3+ and NO2-. Four photolysis products were tentatively identified by HPLC-LTQ-Orbitrap MS analysis, and the possible degradation pathways of TCP were proposed. These findings provide a meaningful reference for the fate and transformation of OPEs in natural water.

Comparative study of the degradation of real textile effluents by photocatalytic reactions involving UV/TiO2/H2O2 and UV/Fe2+/H2O2 systems.

This work investigated the treatability of real textile effluents using several systems involving advanced oxidation processes (AOPs) such as UV/H2O2, UV/TiO2, UV/TiO2/H2O2, and UV/Fe2+/H2O2. The efficiency of each technique was evaluated according to the reduction levels observed in the UV absorbance of the effluents, COD, and organic nitrogen reduction, as well as mineralization as indicated by the formation of ammonium, nitrate, and sulfate ions. The results indicate the association of TiO2 and H2O2 as the most efficient treatment for removing organic pollutants from textile effluents. In spite of their efficiency, Fenton reactions based treatment proved to be slower and exhibited more complicated kinetics than the ones using TiO2, which are pseudo-first-order reactions. Decolorization was fast and effective in all the experiments despite the fact that only H2O2 was used.

Enhanced photocatalytic degradation of pollutants in petroleum refinery wastewater under mild conditions.

A circulating photocatalytic reactor was used for removing aliphatic and aromatic organic pollutants in refinery wastewater. The TiO(2) added wastewater samples, while saturating with air, were irradiated with an immersed mercury UV lamp (400 W, 200-550 nm). Optimal catalyst concentration, fluid pH and temperature were obtained at amounts of near 100 mgL(-1), 3 and 318K, respectively. A maximum reduction in chemical oxygen demand of more than 90% was achieved after about 4h irradiation and hence, 73% after about only 90 min; significant pollutant removal was also achievable in the other conditions. The identification of the organic pollutants, provided by means of a GC/MS and a GC analysis systems, equipped with headspace injection technique, showed that the major compounds were different fractions of petroleum aliphatic hydrocarbons (up to C(10)) and the well-known aromatic compounds such as benzene, toluene and ethylbenzene. The results showed a high efficiency degradation of all of these pollutants.

Direct and indirect photolysis of seven micropollutants in secondary effluent from a wastewater lagoon.

The photodegradation of seven micropollutants commonly found in municipal wastewater, namely caffeine, carbamazepine, diuron, simazine, sulfamethoxazole, triclosan and 2,4-D, was investigated in pure water and secondary effluent to understand the direct and indirect photolysis of these compounds under natural sunlight irradiation. Sulfamethoxazole and triclosan were readily photodegraded with half-lives of 5.8 and 1.8 h, respectively, whilst the others were relatively resistant towards sunlight irradiation. Enhanced degradation was observed in secondary effluent compared with in the pure water matrix for all compounds, except for triclosan. It was confirmed that hydroxyl radicals played an important role in the photodegradation of the micropollutants while singlet oxygen may also play a role. The contribution of hydroxyl radical to the overall degradation of the five compounds that were resistant to direct sunlight accounted for 32%-70%. The impact of humic acid and nitrate, two known photosensitisers and wastewater components, on the photodegradation of the seven micropollutants in pure water was investigated under simulated solar radiation. The presence of nitrate promoted the photochemical loss of all seven micropollutants, however, humic acid caused promotion or inhibition, depending on the characteristics of the micropollutant. Humic acid enhanced the photolytic degradation of caffeine, sulfamethoxazole and diuron, while it hindered the photodegradation of the other four compounds by absorbing the available irradiation energy and/or reforming the parent compound. Furthermore, it was shown that there was only a small increase (up to 15%) in photodegradation of the compounds at 25 °C compared with that at 10 °C in the simulated system.

Can visible light impact litter decomposition under pollution of ZnO nanoparticles?

ZnO nanoparticles is one of the most used materials in a wide range including antibacterial coating, electronic device, and personal care products. With the development of nanotechnology, ecotoxicology of ZnO nanoparticles has been received increasing attention. To assess the phototoxicity of ZnO nanoparticles in aquatic ecosystem, microcosm experiments were conducted on Populus nigra L. leaf litter decomposition under combined effect of ZnO nanoparticles and visible light radiation. Litter decomposition rate, pH value, extracellular enzyme activity, as well as the relative contributions of fungal community to litter decomposition were studied. Results showed that long-term exposure to ZnO nanoparticles and visible light led to a significant decrease in litter decomposition rate (0.26 m-1 vs 0.45 m-1), and visible light would increase the inhibitory effect (0.24 m-1), which caused significant decrease in pH value of litter cultures, fungal sporulation rate, as well as most extracellular enzyme activities. The phototoxicity of ZnO nanoparticles also showed impacts on fungal community composition, especially on the genus of Varicosporium, whose abundance was significantly and positively related to decomposition rate. In conclusion, our study provides the evidence for negatively effects of ZnO NPs photocatalysis on ecological process of litter decomposition and highlights the contribution of visible light radiation to nanoparticles toxicity in freshwater ecosystems.

Visible-light driven degradation of ibuprofen using abundant metal-loaded BiVO4 photocatalysts.

An efficient method for the degradation of ibuprofen as an aqueous contaminant was developed under visible-light irradiation with as-prepared bismuth vanadate (BiVO4) catalysts. The metal-loaded catalysts Cu-BiVO4 and Ag-BiVO4 were synthesized using a hydrothermal process and then a wet-impregnation method. All of the materials were fully characterized by X-ray diffraction, scanning electron microscopy, UV-vis diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy and BET surface area. The results indicated that all of the prepared samples had monoclinic scheelite structures. In the metal-loaded catalysts, silver existed as a mixture of Ag and Ag2O on the surface of the catalysts. However, copper existed as Cu2O and CuO. Additionally, the band gap values of BiVO4, Ag-BiVO4, and Cu-BiVO4 were 2.38, 2.31, and 2.30eV, respectively. Compared to the BiVO4 catalyst, the metal-loaded BiVO4 catalysts showed superior photocatalytic properties for the degradation of ibuprofen.

Impact of temperature, microwave radiation and organic loading rate on methanogenic community and biogas production during fermentation of dairy wastewater.

This study analyzed dairy wastewater fermentation in convection- and microwave-heated hybrid reactors at loadings of 1 and 2 kg COD/(m3 d) and temperatures of 35 and 55 °C. The biomass was investigated at a molecular level to determine the links between the operational parameters of anaerobic digestion and methanogenic Archaea structure. The highest production of biogas with methane content of ca. 67% was noted in the mesophilic microwave-heated reactors. The production of methane-rich biogas and the overall diversity of Archaea was determined by Methanosarcinaceae presence. The temperature and the application of microwaves were the main factors explaining the variations in the methanogen community. At 35 °C, the microwave heating stimulated the growth of highly diverse methanogen assemblages, promoting Methanosarcina barkeri presence and excluding Methanosarcina harudinacea from the biomass. A temperature increase to 55 °C lowered Methanosarcinaceae abundance and induced a replacement of Methanoculleus palmolei by Methanosarcina thermophila.

Degradation of methyl orange through synergistic effect of zirconia nanotubes and ultrasonic wave.

Zirconia nanotubes with a length of 25 µm, inner diameter of 80 nm, and wall thickness of 35 nm were prepared by anodization method in mixture of formamide and glycerol (volume ratio = 1:1) containing 1 wt% NH(4)F and 1 wt% H(2)O. Experiments showed that zirconia nanotubes and ultrasonic wave had synergistic degradation effect for methyl orange and the efficiency of ultrasonic wave increased by more than 7 times. The decolorization percentage was influenced by pH value of the solution. Methyl orange was easy to be degraded in acidic solution. The decolorization percentage of methyl orange reached 97.6% when degraded for 8h in 20mg/L methyl orange solution with optimal pH value 2. The reason of synergistic degradation effect for methyl orange might be that adsorption of methyl orange onto zirconia nanotubes resulted in the easy degradation of the methyl orange through ultrasonic wave.

Reaction pathways for the photodegradation of the organophosphorus cyanophos in aqueous solutions.

Photodegradation in aqueous solutions is an important pathway for many agrochemicals such as pesticides. In the present work, the photochemical transformation of cyanophos (CYA) was investigated in aqueous solutions using UV light within the 254-313 nm range as well as solar light. The study was performed in order to have a deep insight into the mechanistic pathways for the photochemical disappearance of CYA. Upon UV irradiation of an aerated solution of CYA, the degradation quantum yield was found equal to 1.8 x 10(-2). It is independent of the excitation wavelength but varies with oxygen concentration. It increased by a factor of 2 from oxygen-saturated to oxygen-free solution. Photosensitized experiments were performed using acrylamide and hydroquinone as energy acceptor and energy donor substrates, respectively. They show that both singlet and triplet excited states were involved in the photochemical behavior of CYA. The laser flash photolysis experiments clearly showed the involvement of the triplet excited state which was efficiently quenched by molecular oxygen and acrylamide with the rate constants 1.97 x 10(9) and 2.71 x 10(9) mol(-1) L s(-1), respectively. The photoproducts structures were proposed according to the mass spectral data using the LC/MS technique. The analytical study shows that various processes such as hydrolysis, homolytic bond dissociations and Photo-Fries process occur.

Decomposition of aniline in aqueous solution by UV/TiO2 process with applying bias potential.

Application of bias potential to the photocatalytic decomposition of aniline in aqueous solution was studied under various solution pH, bias potentials and concentrations of potassium chloride. The decomposition of aniline by UV/TiO(2) process was found to be enhanced with the application of bias potential of lower voltages; however, the electrolysis of aniline became more dominant as the applying bias potential exceeding 1.0 V. Based on the experimental results and calculated synergetic factors, the application of bias potential improved the decomposition of aniline more noticeably in acidic solutions than that in alkaline solutions. Decomposition of aniline by UV/bias/TiO(2) process in alkaline solutions was increased to certain extent with the concentration of potassium chloride present in aqueous solution. Experimental results also indicated that the energy consumed by applying bias potential for aniline decomposition by UV/bias/TiO(2) process might be much lower than that consumed for increasing light intensity for photocatalysis.

Fabrication of porous TiO2 film on Ti foil by hydrothermal process and its photocatalytic efficiency and mechanisms with ethyl violet dye.

Most of commercial dyes and pigments have rather complicated polyaromatic chemical structures with prolonged lifetime surviving in the Mother Nature. However, TiO(2) has been reported as one of the best photocatalytic candidates for degrading dye pollutants. In this report, TiO(2) film/Ti foil was prepared by hydrothermal reaction in alkali solution, the porous TiO(2) film with microcrystalline structure has been obtained. The porous structure of TiO(2) film was analyzed and characterized by XRD, FE-SEM and XPS. This is the first report that demonstrates that TiO(2) film/Ti foil has an excellent commercial application potential for photocatalytic degradation of Ethyl Violet (EV). Especially, because of refluxing at 100 degrees C, the porous TiO(2) film structure remained undisturbed, and EV decomposed in the period of 20 h. In addition, porous TiO(2)-mediated EV photo degradation mechanism has been proposed, as intermediates are isolated and clearly identified by GC-MS and HPLC-PDA-ESI-MS.

Various factors affecting photodecomposition of methylene blue by iron-oxides in an oxalate solution.

The effect of various factors on the photodecomposition of methylene blue (MB) by iron oxides calcined at various temperatures in various concentrations of oxalate solutions was investigated by illuminating with UV, visible and solar radiation. Iron oxides were prepared by a gel evaporation method and calcined at 200-700 degrees C. XRD showed that the as-synthesized iron oxides were amorphous, but formed maghemite (gamma-Fe(2)O(3)) at 200-400 degrees C and hematite (alpha-Fe(2)O(3)) at > or =500 degrees C. The effect of the various iron oxides, their contents, the oxalate concentration and wavelength of the light source (UV, visible and solar) were all found to strongly influence MB photodecomposition. The optimal contents of the iron oxides increased greatly from 25 to 2000 mg/L at higher calcining temperatures. The MB photodecomposition rate at each optimal iron oxide content was related to the calcining temperature in the order 700 degrees C6, consistent with the presence of iron-oxalate complexes. A much higher concentration of hydroxyl radicals was generated in the present system compared with those from a commercial TiO(2) (ST-01), as determined by the coumarin method. Since this process does not require the addition of hydrogen peroxide and shows good efficiency even under solar light, it is an economically viable method for pre-treating and/or decolorizing wastewaters containing dyes.

Comparison of alternative treatments for 4-chlorophenol removal from aqueous solutions: use of free and immobilized soybean peroxidase and KrCl excilamp.

The removal of 4-chlorophenol (4-CP) from industrial wastewater continues to be an important environmental issue and some interesting results have been obtained using oxidoreductive enzymes such as peroxidases and UV, generated by novel excilamps. In this study enzyme (free and immobilized soybean peroxidase) and UV (produced by a KrCl excilamp) were used to treat 4-CP solutions at concentrations ranging from 50 to 500 mg L(-1). It was shown that the excilamp can facilitate higher removal efficiencies in all cases with complete 4-CP elimination taking place between 5 and 90 min. The enzyme removed approximately 80% of the 4-CP concentrations in both the free and immobilized state up to concentrations of 250 mg L(-1). At 500 mg L(-1) the immobilized system shows much higher removal efficiency due to increased enzyme stability in the presence of higher formation of by-products.