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Mixotrophic bacteria provide a desirable alternative to the use of classical heterotrophic or chemolithoautotrophic bacteria in environmental technology, particularly under limiting nutrients conditions. Their bi-modal ability of adapting to inorganic or organic carbon feed and sulfur, nitrogen, or even heavy metal stress conditions are attractive features to achieve efficient bacterial activity and favorable operation conditions for the environmental detoxification or remediation of contaminated waste and wastewater. This review provides an overview on the state of the art and summarizes the metabolic traits of the most promising and emerging non-model mixotrophic bacteria for the environmental detoxification of contaminated wastewater and waste containing excess amounts of limiting nutrients. Although mixotrophic bacteria usually function with low organic carbon sources, the unusual capabilities of mixotrophic electroactive exoelectrogens and electrotrophs in bioelectrochemical systems and in microbial electrosynthesis for accelerating simultaneous metabolism of inorganic or organic C and N, S or heavy metals are reviewed. The identification of the mixotrophic properties of electroactive bacteria and their capability to drive mono- or bidirectional electron transfer processes are highly exciting and promising aspects. These aspects provide an appealing potential for unearthing new mixotrophic exoelectrogens and electrotrophs, and thus inspire the next generation of microbial electrochemical technology and mixotrophic bacterial metabolic engineering. KEY POINTS: ⢠Mixotrophic bacteria efficiently and simultaneously remove C and N, S or heavy metals. ⢠Exoelectrogens and electrotrophs accelerate metabolism of C and N, S or heavy metals. ⢠New mixotrophic exoelectrogens and electrotrophs should be discovered and exploited.
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Metales Pesados , Aguas Residuales , Bacterias/genética , Procesos Heterotróficos , NitrógenoRESUMEN
Advanced oxidation processes via semiconductor photocatalysis for water treatment have been the subject of extensive research over the past three decades, producing many scientific reports focused on elucidating mechanisms and enhancing kinetics for the treatment of contaminants in water. Many of these reports imply that the ultimate goal of the research is to apply photocatalysis in municipal water treatment operations. However, this ignores immense technology transfer problems, perpetuating a widening gap between academic advocation and industrial application. In this Feature, we undertake a critical examination of the trajectory of photocatalytic water treatment research, assessing the viability of proposed applications and identifying those with the most promising future. Several strategies are proposed for scientists and engineers who aim to support research efforts to bring industrially relevant photocatalytic water treatment processes to fruition. Although the reassessed potential may not live up to initial academic hype, an unfavorable assessment in some areas does not preclude the transfer of photocatalysis for water treatment to other niche applications as the technology retains substantive and unique benefits.
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Contaminantes Químicos del Agua , Purificación del Agua , Catálisis , Oxidación-Reducción , AguaRESUMEN
It has long been established that UVC light is a very effective method for inactivating pathogens in a fluid, yet the application of UVC irradiation to modern biotechnological processes is limited by the intrinsic short penetration distance of UVC light in optically dense protein solutions. This experimental and numerical study establishes that irradiating a fluid flowing continuously in a microfluidic capillary system, in which the diameter of the capillary is tuned to the depth of penetration of UVC light, uniquely treats the whole volume of the fluid to UVC light, resulting in fast and effective inactivation of pathogens, with particular focus to virus particles. This was demonstrated by inactivating human herpes simplex virus type-1 (HSV-1, a large enveloped virus) on a dense 10% fetal calf serum solution in a range of fluoropolymer capillary systems, including a 0.75 mm and 1.50 mm internal diameter capillaries and a high-throughput MicroCapillary Film with mean hydraulic diameter of 206 µm. Up to 99.96% of HSV-1 virus particles were effectively inactivated with a mean exposure time of up to 10 s, with undetectable collateral damage to solution proteins. The kinetics of virus inactivation matched well the results from a new mathematical model that considers the parabolic flow profile in the capillaries, and showed the methodology is fully predictable and scalable and avoids both the side effect of UVC light to proteins and the dilution of the fluid in current tubular UVC inactivation systems. This is expected to speed up the industrial adoption of non-invasive UVC virus inactivation in clinical biotechnology and biomanufacturing of therapeutic molecules. Biotechnol. Bioeng. 2016;113: 1481-1492. © 2015 Wiley Periodicals, Inc.
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Técnicas Analíticas Microfluídicas/métodos , Fotólisis , Virión/efectos de la radiación , Inactivación de Virus/efectos de la radiación , Herpesvirus Humano 1/efectos de la radiación , Técnicas Analíticas Microfluídicas/instrumentación , Modelos BiológicosRESUMEN
Endocrine disruptors in water are contaminants of emerging concern due to the potential risks they pose to the environment and to the aquatic ecosystems. In this study, a solar photocatalytic treatment process in a pilot-scale compound parabolic collector (CPC) was used to remove commercial estradiol formulations (17-ß estradiol and nomegestrol acetate) from water. Photolysis alone degraded up to 50% of estradiol and removed 11% of the total organic carbon (TOC). In contrast, solar photocatalysis degraded up to 57% of estrogens and the TOC removal was 31%, with 0.6 g/L of catalyst load (TiO2 Aeroxide P-25) and 213.6 ppm of TOC as initial concentration of the commercial estradiols formulation. The adsorption of estrogens over the catalyst was insignificant and was modeled by the Langmuir isotherm. The TOC removal via photocatalysis in the photoreactor was modeled considering the reactor fluid-dynamics, the radiation field, the estrogens mass balance, and a modified Langmuir-Hinshelwood rate law, that was expressed in terms of the rate of photon adsorption. The optimum removal of the estrogens and TOC was achieved at a catalyst concentration of 0.4 g/L in 29 mm diameter tubular CPC reactors which approached the optimum catalyst concentration and optical thickness determined from the modeling of the absorption of solar radiation in the CPC, by the six-flux absorption-scattering model (SFM).
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Anticonceptivos Orales/química , Estradiol/química , Megestrol/análogos & derivados , Procesos Fotoquímicos , Energía Solar , Agua/química , Catálisis , Megestrol/químicaRESUMEN
Palm oil mill effluent (POME) is regarded as deleterious to the environment, primarily owing to the substantial volume of waste it produces during palm oil extraction. In terms of contaminant composition, POME surpasses the pollutant content typically found in standard municipal sewage, therefore releasing it without treatment into water bodies would do irreparable damage to the environment. Main palm oil mills are normally located in the proximity of natural rivers in order to take advantage of the cheap and abundant water source. The same rivers are also used as a water source for many villages situated along the river banks. As such, it is imperative to degrade POME before its disposal into the water bodies for obvious reasons. The treatment methods used so far include the biological processes such as open ponding/land application, which consist of aerobic as well as anaerobic ponds, physicochemical treatment including membrane technology, adsorption and coagulation are successful for the mitigation of contaminants. As the above methods require large working area and it takes more time for contaminant degradation, and in consideration of the strict environmental policies as well as palm oil being the most sort of vegetable oil in several countries, numerous researchers have concentrated on the emerging technologies such as advanced oxidation processes (AOPs) to remediate POME. Methods such as the photocatalysis, Fenton process, sonocatalysis, sonophotocatalysis, ozonation have attained special importance for the degradation of POME because of their efficiency in complete mineralization of organic pollutants in situ. This review outlines the AOP technologies currently available for the mineralization of POME with importance given to sonophotocatalysis and ozonation as these treatment process removes the need to transfer the pollutant while possibly degrading the organic matter sufficiently to be used in other industry like fertilizer manufacturing.
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Contaminantes Ambientales , Ozono , Aceite de Palma , Residuos Industriales/análisis , Eliminación de Residuos Líquidos , Aceites de Plantas/química , AguaRESUMEN
The literature on photocatalytic oxidation of water pollutants often reports reaction kinetic constants, which cannot be unraveled from photoreactor type and experimental conditions. This study addresses this challenging aspect by presenting a general and simple methodology for the evaluation of fundamental "intrinsic" reaction kinetic constants of photocatalytic degradation of water contaminants, which are independent of photoreactor type, catalyst concentration, irradiance levels, and hydrodynamics. The degradation of the model contaminant, oxalic acid (OA) on titanium dioxide (TiO2) aqueous suspensions, was monitored in two annular photoreactors (PR1 and PR2). The photoreactors with significantly different geometries were operated under different hydrodynamic regimes (turbulent batch mode and laminar flow-through recirculation mode), optical thicknesses, catalyst and OA concentrations, and photon irradiances. The local volumetric rate of photon absorption (LVRPA) was evaluated by the six-flux radiation absorption-scattering model (SFM). The SFM was further combined with a comprehensive kinetic model for the adsorption and photodecomposition of OA on TiO2 to determine local reaction rates and, after integration over the reactor volume, the intrinsic reaction kinetic constants. The model could determine the oxidation of OA in both PR1 and PR2 under a wide range of experimental conditions. This study demonstrates a more meaningful way for determining reaction kinetic constants of photocatalytic degradation of water contaminants.
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Absorción de Radiación , Hidrodinámica , Luz , Fotólisis , Fotones , Contaminantes Químicos del Agua/efectos de la radiación , Contaminación del Agua/análisis , Catálisis/efectos de la radiación , Cinética , Modelos Teóricos , Ácido Oxálico/química , Oxidación-Reducción/efectos de la radiación , Radiación , Dispersión de Radiación , Titanio/químicaRESUMEN
The debate on whether photocatalysis can reach full maturity at commercial level as an effective and economical process for treatment and purification of water and wastewater has recently intensified. Despite a bloom of scientific investigations in the last 30 years, particularly with regards to innovative photocatalytic materials, photocatalysis has so far seen a few industrial applications. Regardless of the points of view, it has been realized that research on reactor design and modeling are now equally urgent to match the extensive research carried out on innovative photocatalytic materials. In reality, the development of photocatalytic reactors has advanced steadily in terms of modeling and reactor design over the last two decades, though this topic has captured a smaller specialized audience. In this critical review, we introduce the latest developments on photocatalytic reactors for water treatment from an engineering perspective. The focus is on the modeling and design of photocatalytic reactors for water treatment at pilot- or at greater scale. Photocatalytic reactors utilizing both natural sunlight and UV irradiation sources are comprehensively discussed. The most promising photoreactor designs and models are examined giving key design guidelines. Other engineering considerations, such as operation, cost analysis, patents, and several industrial applications of photocatalytic reactors for water treatment are also presented. The dissemination of key photocatalytic reactor design principles among the scientific community and the water industry is currently one of the greatest obstacles in translating PWT research into widespread real-world application.
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Purificación del Agua , Catálisis , Luz Solar , Rayos Ultravioleta , Aguas ResidualesRESUMEN
Photocatalytic degradation of waste material in aqueous solutions and simultaneous production of hydrogen was studied with the double purpose of environmental remediation and renewable energy production. Both powdered and immobilized Pt/CdS/TiO(2) photocatalysts were used to oxidize model inorganic (S(2-)/SO(3)(2-)) and organic (ethanol) sacrificial agents/pollutants in water. Powdered Pt/CdS/TiO(2) photocatalysts of variable CdS content (0-100%) were synthesized by precipitation of CdS nanoparticles on TiO(2) (Degussa P25) followed by deposition of Pt (0.5 wt %) and were characterized with BET, XRD, and DRS. Immobilized photocatalysts were deposited either on plain glass slides or on transparent conductive fluorine-doped SnO(2) electrodes. The results show that it is possible to produce hydrogen efficiently (20% quantum efficiency at 470 nm) by using simulated solar light and by photocatalytically consuming either inorganic or organic substances. CdS-rich photocatalysts are more efficient for the photodegradation of inorganics, while TiO(2)-rich materials are more effective for the photodegradation of organic substances.
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Compuestos de Cadmio/química , Hidrógeno/química , Platino (Metal)/química , Sulfuros/química , Luz Solar , Titanio/química , Contaminantes del Agua/química , Catálisis , Electrodos , Difracción de Rayos XRESUMEN
The photodegradation process of methylisothiazolinone (MIT), benzisothiazolinone (BIT), and isoxazole (ISOX) in ultrapure water and synthetic wastewater by means of UV254 photolysis and by UV254/H2O2 advanced oxidation process were investigated in a microcapillary photoreactor designed for ultrafast photochemical transformation of microcontaminants. For the first time, we estimated key photo-kinetic parameters, i.e. quantum yields (35.4â¯mmol·ein-1 for MIT, and 13.5 and 55.8â¯mmol·ein-1 for BIT at pHâ¯=â¯4-6 and 8, respectively) and rate constants of the reaction of photo-generated OH radicals with MIT and BIT (2.09·109 and 5.9·109â¯Lâ¯mol-1·s-1 for MIT and BIT). The rate constants of the reaction of photo-generated OH radicals with ISOX in MilliQ water was also estimated (2.15·109â¯Lâ¯mol-1·s-1) and it was in good agreement with literature indications obtained in different aqueous matrices. The models were extended and validated to the case of simultaneous degradation of mixtures of these compounds and using synthetic wastewater as an aqueous matrix. High resolution-accurate mass spectrometry analysis enabled identification of the main intermediates (BIT200, B200, saccharin, BIT166) and enabled proposal of a novel degradation pathway for BIT under UV254/H2O2 treatment. This study demonstrates an ultrafast method to determine key photo-kinetic parameters of contaminants of emerging concern in water and wastewater, which are needed for design and validation of photochemical water treatment processes of municipal and industrial wastewaters.
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Contaminantes Químicos del Agua , Purificación del Agua , Peróxido de Hidrógeno , Isoxazoles , Oxidación-Reducción , Fotólisis , Rayos UltravioletaRESUMEN
The self-cleaning and super hydrophilic properties of pristine TiO2 and of TiO2 doped with Er3+ or Y3+ transparent thin films deposited onto glass substrates were investigated. The thin films prepared by multiple dipping and drying cycles of the glass substrate into the pristine TiO2 sol and Er3+ or Y3+-doped TiO2 sol were characterized by X-ray diffraction, UV-vis spectrophotometry, and atomic force microscopy (AFM). The self-cleaning photocatalytic activity of the thin films towards the removal of oleic acid deposited on the surface under UVA irradiation was evaluated. A remarkable enhancement was observed in the hydrophilic nature of the TiO2 thin films under irradiation. The optical properties and wettability of TiO2 were not affected by Er3+ or Y3+ doping. However, the photocatalytic degradation of oleic acid under UVA irradiation improved up to 1.83 or 1.95 fold as the Er3+ or Y3+ content increased, respectively, due to the enhanced separation of the photogenerated carriers and reduced crystallite size. AFM analysis showed that the surface roughness increased by increasing the Er3+ or Y3+ content due to the formation of large aggregates. This in turn contributes to the increase of the active surface area enhancing the photodegradation process. This study demonstrates that TiO2 doped with low amounts of Er3+ or Y3+ down to 0.5 mol% can produce transparent, super-hydrophilic, thin film surfaces with remarkable self-cleaning properties.
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The degradation of organic substances present in winery wastewater was studied in a pilot-scale, bubble column ozonation reactor. A steady reduction of chemical oxygen demand (COD) was observed under the action of ozone at the natural pH of the wastewater (pH 4). At alkaline and neutral pH the degradation rate was accelerated by the formation of radical species from the decomposition of ozone. Furthermore, the reaction of hydrogen peroxide (formed from natural organic matter in the wastewater) and ozone enhances the oxidation capacity of the ozonation process. The monitoring of pH, redox potential (ORP), UV absorbance (254 nm), polyphenol content and ozone consumption was correlated with the oxidation of the organic species in the water. The ozonation of winery wastewater in the bubble column was analysed in terms of a mole balance coupled with ozonation kinetics modeled by the two-film theory of mass transfer and chemical reaction. It was determined that the ozonation reaction can develop both in and across different kinetic regimes: fast, moderate and slow, depending on the experimental conditions. The dynamic change of the rate coefficient estimated by the model was correlated with changes in the water composition and oxidant species.
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Residuos Industriales , Ozono , Eliminación de Residuos Líquidos/métodos , Vino , Biodegradación Ambiental , Flavonoides/análisis , Peróxido de Hidrógeno , Concentración de Iones de Hidrógeno , Cinética , Oxidantes/análisis , Oxidación-Reducción , Fenoles/análisis , Proyectos Piloto , Polifenoles , PortugalRESUMEN
The simultaneous production of acetate from bicarbonate (from CO2 sequestration) and hydrogen gas, with concomitant removal of Cd(II) heavy metal in water is demonstrated in multifunctional metallurgical microbial electrosynthesis systems (MES) incorporating Cd(II) tolerant electrochemically active bacteria (EAB) (Ochrobactrum sp. X1, Pseudomonas sp. X3, Pseudomonas delhiensis X5, and Ochrobactrum anthropi X7). Strain X5 favored the production of acetate, while X7 preferred the production of hydrogen. The rate of Cd(II) removal by all EAB (1.20-1.32 mg/L/h), and the rates of acetate production by X5 (29.4 mg/L/d) and hydrogen evolution by X7 (0.0187 m3/m3/d) increased in the presence of a circuital current. The production of acetate and hydrogen was regulated by the release of extracellular polymeric substances (EPS), which also exhibited invariable catalytic activity toward the reduction of Cd(II) to Cd(0). The intracellular activities of glutathione (GSH), catalase (CAT), superoxide dismutase (SOD) and dehydrogenase were altered by the circuital current and Cd(II) concentration, and these regulated the products distribution. Such understanding enables the targeted manipulation of the MES operational conditions that favor the production of acetate from CO2 sequestration with simultaneous hydrogen production and removal/recovery of Cd(II) from metal-contaminated and organics-barren waters.
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Acetatos/síntesis química , Bacterias/metabolismo , Reactores Biológicos , Cadmio/aislamiento & purificación , Carbono/química , Técnicas Electroquímicas/métodos , Hidrógeno/química , Bacterias/clasificación , Bacterias/enzimología , CatálisisRESUMEN
The aim of this study was to evaluate the bactericidal effect of reactive oxygen species (ROS) generated upon irradiation of photocatalytic TiO2 surface coatings using low levels of UVA and the consequent killing of Staphylococcus aureus. The role of intracellular enzymes catalase and superoxide dismutase in protecting the bacteria was investigated using mutant strains. Differences were observed in the intracellular oxidative stress response and viability of S. aureus upon exposure to UVA; these were found to be dependent on the level of irradiance and not the total UVA dose. The wild type bacteria were able to survive almost indefinitely in the absence of the coatings at low UVA irradiance (LI, 1â¯mW/cm2), whereas in the presence of TiO2 coatings, no viable bacteria were measurable after 24â¯h of exposure. At LI, the lethality of the photocatalytic effect due to the TiO2 surface coatings was correlated with high intracellular oxidative stress levels. The wild type strain was found to be more resistant to UVA at HI compared with an identical dose at LI in the presence of the TiO2 coatings. The UVA-irradiated titania operates by a "stealth" mechanism at low UVA irradiance, generating low levels of extracellular lethal ROS against which the bacteria are defenceless because the low light level fails to induce the oxidative stress defence mechanism of the bacteria. These results are encouraging for the deployment of antibacterial titania surface coatings wherever it is desirable to reduce the environmental bacterial burden under typical indoor lighting conditions.
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Titanio/química , Rayos Ultravioleta , Proteínas Bacterianas/genética , Catálisis , Vidrio/química , Microscopía Electrónica de Rastreo , Mutación , Estrés Oxidativo/efectos de la radiación , Especies Reactivas de Oxígeno/metabolismo , Staphylococcus aureus/genética , Staphylococcus aureus/efectos de la radiaciónRESUMEN
The oxidative degradation of organic pollutants present in cork-processing water at natural pH (6.45) was studied in a bubble column ozonation reactor. A steady reduction in both chemical oxygen demand (COD) and total organic carbon (TOC) was observed under the action of ozone alone and the feasibility of deep mineralisation (organic matter removal more than 90% in 120 min under the following experimental conditions: liquid volume 9L; superficial gas velocity 6.8x10(-3) m s(-1); ozone partial pressure 1.31 kPa; initial COD 328 mg L(-1); initial TOC 127 mg L(-1)) was demonstrated. The monitoring of pH, redox potential (ORP) and the mean oxidation number of carbon (MOC) was correlated with the oxidation and mineralisation of the organic species in the water. The ozonation of cork-processing water in the bubble column was analysed in terms of a mole balance coupled with ozonation kinetics modelled by the two-film theory of mass transfer and chemical reaction. Under the experimental conditions used, and in contrast with the literature, it was determined that the reaction follows a fast kinetic regime at the beginning of the oxidation process, shifting to the moderate and the slow kinetic regimes at later stages of the oxidation reaction. The dynamic change of the rate coefficient estimated by the model was correlated to changes in the water composition.
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Residuos Industriales , Ozono/química , Eliminación de Residuos Líquidos , Algoritmos , Concentración de Iones de Hidrógeno , Cinética , Oxígeno/metabolismo , Factores de TiempoRESUMEN
Various methods to prepare and characterize TiO(2) photocatalyst loaded onto activated carbon (AC) support have been developed over the last decade. This photocatalyst has been used in a variety of investigations, i.e. from water decontamination to direct pollutant degradation in aqueous and gas phase systems using UV irradiation and lately with the assistance of ultrasonic sound waves. Chemical vapor deposition (CVD) method is one of the most promising and well-researched methods for deposition of catalysts onto supports. Given its advantage, from an engineering and fundamental aspect, CVD method also has commercial applications. A detailed search of published reports of these investigations was carried out and analyzed in this paper with focus on CVD techniques, activated carbon support and sonication.
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Contaminantes Atmosféricos/química , Contaminación del Aire/prevención & control , Carbón Orgánico/química , Colorantes/química , Titanio/química , Contaminantes Químicos del Agua/química , Purificación del Agua/métodos , Catálisis , Técnicas Químicas Combinatorias , Fotoquímica , Propiedades de SuperficieRESUMEN
Recently, layered double hydroxides (LDHs) have attracted much consideration due to their versatility and easily manipulating properties and their potential applications such as anion exchangers, support of catalysts, flame retardants, biomedical drug delivery. A novel method for the in-situ preparation in situ of LDHs, using electrocoagulation (EC) processes was developed, the EC process was performed under two different conditions, at 5 mA m-2, changing polarity of the electrodes to find out the composition that leads to LDHs generation. The final product was characterized using XRD, BET and FTIR techniques. This method presented the following advantages: (1) Simultaneously LDHs synthesis and wastewater treatment by ion removal; (2) Polarity control allows to manipulate the M2+/M3+ molar ratio, LDHs properties and its potential applications; (3) The method spent less time to carry out the synthesis and; (4) it did not need complicated solid-liquid separation processes.
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The concentration of antiretroviral drugs in wastewater treatment plants (WWTP) effluents and surface waters of many countries has increased significantly due to their widespread use for HIV treatment. In this study, the removal of stavudine and zidovudine under UV254 photolysis or UV254/H2O2 was investigated in a microcapillary film (MCF) photoreactor, using minimal water samples quantities. The UV254 quantum yield of zidovudine, (2.357⯱â¯0.0589)·10-2â¯molâ¯ein-1 (pH 4.0-8.0), was 28-fold higher that the yield of stavudine (8.34⯱â¯0.334)·10-4â¯molâ¯ein-1 (pH 6.0-8.0). The second-order rate constant kOH,iof reaction of hydroxyl radical with the antiretrovirals (UV254/H2O2 process) were determined by kinetics modeling: (9.98⯱â¯0.68)·108â¯M-1â¯s-1 (pH 4.0-8.0) for zidovudine and (2.03⯱â¯0.18)·109â¯M-1â¯s-1 (pH 6.0-8.0) for stavudine. A battery of ecotoxicological tests (i.e. inhibition growth, bioluminescence, mutagenic and genotoxic activity) using bacteria (Aliivibrio fischeri, Salmonella typhimurium), crustacean (Daphnia magna) and algae (Raphidocelis subcapitata) revealed a marked influence of the UV dose on the ecotoxicological activity. The UV254/H2O2 treatment process reduced the ecotoxicological risk associated to direct photolysis of the antiretrovirals aqueous solutions, but required significantly higher UV254 doses (≥2000 mJâ¯cm-2) in comparison to common water UV disinfection processes.
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Antirretrovirales , Peróxido de Hidrógeno , Estavudina , Rayos Ultravioleta , Contaminantes Químicos del Agua , Zidovudina , Aliivibrio fischeri/efectos de los fármacos , Aliivibrio fischeri/crecimiento & desarrollo , Animales , Antirretrovirales/química , Antirretrovirales/toxicidad , Daphnia/efectos de los fármacos , Daphnia/fisiología , Ecotoxicología , Peróxido de Hidrógeno/química , Peróxido de Hidrógeno/efectos de la radiación , Cinética , Salmonella typhimurium/efectos de los fármacos , Salmonella typhimurium/genética , Estavudina/química , Estavudina/toxicidad , Contaminantes Químicos del Agua/química , Contaminantes Químicos del Agua/toxicidad , Zidovudina/química , Zidovudina/toxicidadRESUMEN
A novel and simple one step hydrothermal process is used to prepare TiO(2)/WO(3) nanocomposites, in which WO(3) and TiO(2) are present in hexagonal and anatase crystalline forms, respectively, and have enhanced photocatalytic activity towards trichloroethylene degradation in the gas phase.
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The role of Fe(III) was investigated as an electron-shuttle mediator to enhance the reduction rate of the toxic heavy metal hexavalent chromium (Cr(VI)) in wastewaters, using microbial fuel cells (MFCs). The direct reduction of chromate (CrO4-) and dichromate (Cr2O72-) anions in MFCs was hampered by the electrical repulsion between the negatively charged cathode and Cr(VI) functional groups. In contrast, in the presence of Fe(III), the conversion of Cr(VI) and the cathodic coulombic efficiency in the MFCs were 65.6% and 81.7%, respectively, 1.6 times and 1.4 folds as those recorded in the absence of Fe(III). Multiple analytical approaches, including linear sweep voltammetry, Tafel plot, cyclic voltammetry, electrochemical impedance spectroscopy and kinetic calculations demonstrated that the complete reduction of Cr(VI) occurred through an indirect mechanism mediated by Fe(III). The direct reduction of Cr(VI) with cathode electrons in the presence of Fe(III) was insignificant. Fe(III) played a critical role in decreasing both the diffusional resistance of Cr(VI) species and the overpotential for Cr(VI) reduction. This study demonstrated that the reduction of Cr(VI) in MFCs was effective in the presence of Fe(III), providing an alternative and environmentally benign approach for efficient remediation of Cr(VI) contaminated sites with simultaneous production of renewable energy.
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Fuentes de Energía Bioeléctrica , Cromo/química , Electrones , Hierro/química , Algoritmos , Difusión , Electroquímica , Electrodos , Oxidación-Reducción , Aguas Residuales/análisisRESUMEN
The feasibility of simultaneous recovery of heavy metals from wastewater (e.g., acid mining and electroplating) and production of electricity is demonstrated in a novel photoelectrochemical cell (PEC). The photoanode of the cell bears a nanoparticulate titania (TiO2) film capped with the block copolymer [poly(ethylene glycol)-b-poly(propylene glycol)-b-poly(ethylene glycol)] hole scavenger, which consumed photogenerated holes, while the photogenerated electrons transferred to a copper cathode reducing dissolved metal ions and produced electricity. Dissolved silver Ag+, copper Cu2+, hexavalent chromium as dichromate Cr2O72- and lead Pb2+ ions in a mixture (0.2mM each) were removed at different rates, according to their reduction potentials. Reduced Ag+, Cu2+ and Pb2+ ions produced metal deposits on the cathode electrode which were mechanically recovered, while Cr2O72- reduced to the less toxic Cr3+ in solution. The cell produced a current density Jsc of 0.23mA/cm2, an open circuit voltage Voc of 0.63V and a maximum power density of 0.084mW/cm2. A satisfactory performance of this PEC for the treatment of lead-acid battery wastewater was observed. The cathodic reduction of heavy metals was limited by the rate of electron-hole generation at the photoanode. The PEC performance decreased by 30% after 9 consecutive runs, caused by the photoanode progressive degradation.