Heterogeneous photocatalytic degradation of acid dyes in aqueous TiO2 suspensions: Kinetics and toxicity

This work assesses the photocatalytic (TiO2/UV) degradation of a simulated acid dye bath (Yellow 3, Red 51, Blue 74, and auxiliary chemicals). Color and phytotoxicity removal were monitored by spectrophotometry and lettuce (Lactuca sativa) seeds as the test organism, respectively. Mineralization was determined by DOC analyses. Photocatalytic, photolytic, and adsorption experiments were performed, showing that adsorption was negligible. After 240 minutes of irradiation, it was achieved 96% and 78% of color removal with photocatalysis and photolysis, respectively. 37% of mineralization occurred with photocatalysis only. The dye bath was rendered completely non-toxic after 60 minutes of photocatalytic treatment; the same result was only achieved with photolysis after 90 minutes. A kinetic model composed of two first-order in series reactions was used. The first photocatalytic decolorization rate constant was k(1) = 0.062 min(-1) and the second k(2) = 0.0043 min(-1), approximately two times greater than the photolytic ones.

Synthesis, characterization and biological analysis of the complex [VO(Hdhp)(2)] (H(2)dhp=2,3-dihydroxypyridine)

A new vanadium (IV) complex with the monoanion of 2,3-dihydroxypyridine (H(2)dhp), or 3-hydroxy-2(1H)-pyridone, was synthesized, characterized by physicochemical techniques and tested biologically. The EPR data for the [VO(Hdhp)(2)] complex in DMF are: g(x) = 1.9768, g(y) = 1.9768 and g(z) = 1.9390; A values (10(-4) cm(-1)): A(x), 59.4; A(y//), 59.4; A(z), 171.0. The vV=O band in the IR spectrum of the complex is at 986 cm(-1). The complex is paramagnetic, with mu(eff) = 1.65 BM (d(1), spin-only) at 25 degrees C. The irreversible oxidation process [V(V)/V(IV)] of the [VO(Hdhp)(2)] complex, as revealed in a cyclic voltammogram, occurs at 876 mV. The calculated molecular structure of [VO(Hdhp)(2)] shows the vanadium(IV) center in a distorted square pyramidal environment, with the oxo ligand in the apical position and the oxygen donor atoms of the Hdhp ligands in the basal positions. The ability of [VO(Hdhp)(2)] to mimic insulin, and its toxicity to hepato-biliary functions, were investigated in streptozotocin-induced diabetic rats and it was concluded that the length of treatment and the amount of [VO(Hdhp)(2)] administered were effective in reducing experimental diabetes.

Electrochemical Behavior of Verapamil at Graphite-Polyurethane Composite Electrodes: Determination of Release Profiles in Pharmaceutical Samples

A solid graphite-polyurethane composite electrode has been used to determine release profiles of verapamil, a calcium-channel blocker. The electro-oxidation process was characterized by cyclic voltammetry and electrochemical impedance spectroscopy and showed no adsorption of analyte or oxidation products, unlike at other carbon-based electrodes. Quantification gave linear ranges up to 40molL-1 with cyclic voltammetry and detection limits of 0.7molL-1 by differential pulse and square-wave voltammetry. Commercial product samples were successfully analyzed with results equal to those from spectrophotometry. Because no electrode surface renewal is needed, this electrode material has many advantages.

Influência do sistema anteoxidante da catalase no ciclo do glioxilato durante o estabelecimento pós-germinativo de cártamo (Carthamus tinctorius L.) e de girassol (Helianthus annuus L.)

Oilseeds are a high-value natural resource, due to its use as a substitute for petroleum. However, the storage time can reduce seed viability and oil quality. Therefore, scientific efforts have been made to provide a increment of storage time, germination rates and plant establishment of high-value oilseeds. The seedling establishment depends of the plant pass over the functional transition stage, characterized by a metabolic change from heterotrophic condition to autotrophic one. The storage oil mobilization is performed by β-oxidation process and the glyoxylate cycle. Also, the functional transition involves acclimation to photosynthetic condition, which generally includes the participation of antioxidant system and the reactive oxygen species, the latter are produced in various reactions of primary and secondary metabolism. In the present study, Catalase was inhibited during the functional transition of sunflower and safflower, after were performed many analyzes to elucidate the effects caused on the SOD and APX antioxidant systems. Also, were checked the changes in expression pattern of the glyoxylate cycle enzymes markers, ICL and MLS. It was observed that after CAT inhibition, the SOD and APX antioxidant systems allow the seedling establishment. Besides, was verified that both oilseeds can be accelerate the reverse mobilization and the photosynthetic establishment when Catalase activity has dramatically decreased

Estudo e desenvolvimento de um capacitor eletrolítico de nióbio

It seeks to find an alternative to the current tantalum electrolytic capacitors in the market due to its high cost. Niobium is a potential substitute, since both belong to the same group of the periodic table and because of this have many similar physical and chemical properties. Niobium has several technologically important applications, and Brazil has the largest reserves, around 96%. There are including niobium in reserves of tantalite and columbite in Rio Grande do Norte. These electrolytic capacitors have high capacitance specifies, ie they can store high energy in small volumes compared to other types of capacitors. This is the main attraction of this type of capacitor because is growing demand in the production of capacitors with capacitance specifies increasingly high, this because of the miniaturization of various devices such as GPS devices, televisions, computers, phones and many others. The production route of the capacitor was made by powder metallurgy. The initial niobium powder supplied by EEL-USP was first characterized by XRD, SEM, XRF and laser particle size, to then be sieved into three particle size, 200, 400 e 635mesh. The powders were then compacted and sintered at 1350, 1450 and 1550°C using two sintering time 30 and 60min. Sintering is one of the most important parts of the process as it affects properties as porosity and surface cleaning of the samples, which greatly affected the quality of the capacitor. The sintered samples then underwent a process of anodic oxidation, which created a thin film of niobium pentóxido over the whole porous surface of the sample, this film is the dielectric capacitor. The oxidation process variables influence the performance of the film and therefore the capacitor. The samples were characterized by electrical measurements of capacitance, loss factor, ESR, relative density, porosity and surface area. After the characterizations was made an annealing in air ate 260ºC for 60min. After this treatment were made again the electrical measurements. The particle size of powders and sintering affected the porosity and in turn the specific area of the samples. The larger de area of the capacitor, greater is the capacitance. The powder showed the highest capacitance was with the smallest particle size. Higher temperatures and times of sintering caused samples with smaller surface area, but on the other hand the cleaning surface impurities was higher for this cases. So a balance must be made between the gain that is achieved with the cleaning of impurities and the loss with the decreased in specific area. The best results were obtained for the temperature of 1450ºC/60min. The influence of annealing on the loss factor and ESR did not follow a well-defined pattern, because their values increased in some cases and decreased in others. The most interesting results due to heat treatment were with respect to capacitance, which showed an increase for all samples after treatment

Degradação fotoquímica de hidrocarbonetos da gasolina em efluentes aquosos

Photo-oxidation processes of toxic organic compounds have been widely studied. This work seeks the application of the photo-Fenton process for the degradation of hydrocarbons in water. The gasoline found in the refinery, without additives and alcohol, was used as the model pollutant. The effects of the concentration of the following substances have been properly evaluated: hydrogen peroxide (100-200 mM), iron ions (0.5-1 mM) and sodium chloride (200 2000 ppm). The experiments were accomplished in reactor with UV lamp and in a falling film solar reactor. The photo-oxidation process was monitored by measurements of the absorption spectra, total organic carbon (TOC) and chemical oxygen demand (COD). Experimental results demonstrated that the photo-Fenton process is feasible for the treatment of wastewaters containing aliphatic hydrocarbons, inclusive in the presence of salts. These conditions are similar to the water produced by the petroleum fields, generated in the extraction and production of petroleum. A neural network model of process correlated well the observed data for the photooxidation process of hydrocarbons

Estudo da oxidação do metabissulfito de sódio contido no efluente da carcinicultura

The shrimp farming is a process of creation of shrimp that has been growing rapidly in the country, occupying a meaningful space in the Brazilian exporting. In 2003, this activity presented a volume of 60 millions of tons and 220 millions of dollars, being the main generator of employment and income of the primary sector of the northeast economy. However, it is a new activity with c.a. five years in the Rio Grande do Norte State and therefore needs investment in the technological area. Among the wastewaters of this activity, the sulphite solution is being usually applied in the process of fishing, i.e. retrieval of the shrimps from the farming. The aim of this work is to present the oxidation experimental results of the sulphite that may be and to determine what it s the most efficient method, trough laboratory experiments. The measurements were carried out in a mixing reactor inserting air and with hydrogen peroxide addition with and without UV light. The solutions were prepared synthetically with concentrations found in the wastewater of fishing and also collected in locu. The oxidation process using air was monitorated by iodometric analysis for the sulphite and the oxidation using hydrogen peroxide was evaluated with turbidimetric analysis for sulphate, by spectrophotometer. The sulphite was totally oxidized in both processes. The experimental results permit to conclude that the oxidation by hydrogen peroxide is more efficient and allowed to determine the optimum operational conditions in terms of concentration and time of treatment

Estudo da remoção de compostos orgânicos, benzeno e tolueno, em solução aquosa por processo oxidativo avançado do tipo Fenton

The oil and petrochemical industry is responsable to generate a large amount of waste and wastewater. Among some efluents, is possible find the benzene, toluene, ethilbenze and isomers of xilenes compounds, known as BTEX. These compounds are very volatily, toxic for environment and potencially cancerigenous in man. Oxidative advanced processes, OAP, are unconventional waste treatment, wich may be apply on treatment and remotion this compounds. Fenton is a type of OAPs, wich uses the Fenton s reactant, hydrogen peroxide and ferrous salt, to promove the organic degradation. While the Photo-Fenton type uses the Fenton s reactant plus UV radiation (ultraviolet). These two types of OAP, according to literature, may be apply on BTEX complex system. This project consists on the consideration of the utilization of technologies Fenton and Photo-Fenton in aqueous solution in concentration of 100 ppm of BTEX, each, on simulation of condition near of petrochemical effluents. Different reactors were used for each type of OAP. For the analyticals results of amount of remotion were used the SPME technique (solid phase microextraction) for extraction in gaseous phase of these analytes and the gas chromatography/mass espectrometry The arrangement mechanical of Photo-Fenton system has been shown big loss by volatilization of these compounds. The Fenton system has been shown capable of degradate benzene and toluene compounds, with massic percentage of remotion near the 99%.

Avaliação de diferentes processos oxidativos avançados no tratamento de resíduos de petróleo

The petroleum industry deals with problems which are difficult to solve because of their relation to environmental issues. This is because amounts of residue are generated which vary in type and danger level. The soil contamination by non aqueous liquid phase mixtures, specifically hydrocarbon petroleum has been a reason for great concern, mainly the aromatic and polycyclic aromatic, which present risk to human health due to its carcinogenic and mutagenic character. The Advanced Oxidative Processes (AOP) are efficient technologies for destruction of organic compounds of difficult degradation and, often, they are present in low concentrations. They can be considered clean technologies, because there is no formation of solid by-products or the transfer of pollutor phases. This work focuses on the study of the degradation of petroleum industrial waste, by Advanced Oxidation Processes. Treatments tackling petroleum residues, contaminated soil, and water occurring in the production of petroleum reached the following Polycyclic Aromatic Hydrocarbons (PAH) degradation levels: solid residues 100% in 96 treatment hours; water residue - 100% in 6 treatment hours; soil contamination (COT degradation) - 50.3% in 12 treatment hours. AOP were effective in dealing with petroleum residues thus revealing themselves to be a promising treatment alternative

Synthesis, characterization and biological analysis of the complex [VO(Hdhp)(2)] (H(2)dhp=2,3-dihydroxypyridine)

A new vanadium (IV) complex with the monoanion of 2,3-dihydroxypyridine (H(2)dhp), or 3-hydroxy-2(1H)-pyridone, was synthesized, characterized by physicochemical techniques and tested biologically. The EPR data for the [VO(Hdhp)(2)] complex in DMF are: g(x) = 1.9768, g(y) = 1.9768 and g(z) = 1.9390; A values (10(-4) cm(-1)): A(x), 59.4; A(y//), 59.4; A(z), 171.0. The vV=O band in the IR spectrum of the complex is at 986 cm(-1). The complex is paramagnetic, with mu(eff) = 1.65 BM (d(1), spin-only) at 25 degrees C. The irreversible oxidation process [V(V)/V(IV)] of the [VO(Hdhp)(2)] complex, as revealed in a cyclic voltammogram, occurs at 876 mV. The calculated molecular structure of [VO(Hdhp)(2)] shows the vanadium(IV) center in a distorted square pyramidal environment, with the oxo ligand in the apical position and the oxygen donor atoms of the Hdhp ligands in the basal positions. The ability of [VO(Hdhp)(2)] to mimic insulin, and its toxicity to hepato-biliary functions, were investigated in streptozotocin-induced diabetic rats and it was concluded that the length of treatment and the amount of [VO(Hdhp)(2)] administered were effective in reducing experimental diabetes.

Tecnologia eletroquímica como tratamento alternativo de efluentes têxteis sintéticos utilizando ânodos de platina e diamante

In this work, the treatment of synthetic wastewaters containing Remazol Red BR (RRB) and Novacron Blue C-D (NB) by anodic oxidation using boron doped diamond anodes (BDD) and Novacron Yellow (YN) using BDD and Platinum (Pt) anodes was investigated. Galvanostatic electrolyses of RRB and NB synthetic wastewaters have led to the complete decolorization removal at different operating conditions (current density, pH and temperature). The influence of these parameters was investigated in order to find the best conditions for dyestuff colour removal. According to the experimental results obtained, the electrochemical oxidation process is suitable for decolorizing wastewaters containing these textile dyes, due to the electrocatalytic properties of BDD and Pt anode. Energy requirements for removing colour during galvanostatic electrolyses of RRB, NB and YN synthetic solutions depends mainly on the operating conditions; for example for RRB, it passes from 3.30 kWh m-3 at 20 mA cm-2 to 4.28 kWh m-3 at 60 mA cm-2 (pH = 1); 15.23 kWh m-3 at 20 mA cm-2 to 24.75 kWh m-3 at 60 mA cm-2 (pH = 4.5); 10.80 kWh m-3 at 20 mA cm-2 to 31.5 kWh m-3 at 60 mA cm-2 (pH = 8) (data estimated per volume of treated effluent). In order to verify the Brazilian law regulations of NB and RRB synthetic solutions after electrochemical decolourisation treatment, Hazen Units values were determined and the total colour removal was achieved; remaining into the regulations. Finally, electrical energy cost for removing colour was estimated

Avaliação da remoção de hidrocarbonetos aromáticos (BTEX) em águas utilizando materiais nanoestruturados do tipo Ti-MCM-41

Volatile Organic Compounds are pollutants coming mainly from activities that use fossil fuels. Within this class are the BTEX (benzene, toluene, ethylbenzene and xylenes) compounds that are considered hazardous. Among the various existing techniques for degradation of pollutants, there is advanced oxidation using H2O2 generating hidoxil radical ( OH). In this work, the mesoporous material of MCM-41 was synthesized by hydrothermal method and then was used as support, the impregnation of titanium by the method of synthesis with excess solvent to obtain the catalyst Ti-MCM-41. The catalyst was used in the reaction catalyzed removal of BTEX in water using H2O2 as oxidant. The materials were characterized by: XRD, TG/DTG, FTIR, nitrogen adsorption-desorption and FRX-EDX, in order to verify the method of impregnation of the mesoporous titanium support was effective. Catalytic tests were carried out in reactors of 20 mL containing BTEX (100.0 μg/L), H2O2 (2.0 M) and Ti-MCM-41 (2.0 g/L) in acid medium. The reaction occurred for 5 h at 60 °C and analysis were performed by gas chromatography with photoionization detector and static headspace sampler. The characterizations have proven the effectiveness of the synthesis method used and the incorporation of titanium lt in the support. The catalytic tests showed satisfactory results with conversion of more than 95 % for the studied compounds, where the catalyst 48% Ti-MCM-41 showed a higher removal efficiency of the compounds under study

Conciliação entre modelos de mecanismos avançados de oxidação eletroquímica

Many pollutants dumped in waterways, such as dyes and pesticides, have become so ubiquitous that they represent a serious threat to human health. The electrochemical oxidation is presented as an alternative clean, efficient and economic degradation of wastewater containing organic compounds and a number of advantages of this technique is to just not make use of chemical reagents, since only electrical energy is consumed during the removal of pollutants organic. However, despite being a promising alternative, still needs some tweaking in order to obtain better efficiency in the elimination of persistent pollutants. Thus, this study sought a relationship between a recently discovered phenomenon that reflects the participation of dissolved oxygen in solution in the electrochemical oxidation process, as an anomaly, present a kinetic model that shows instantaneous current efficiency (ICE) above 100% limited by theory, manifested for some experiments with phenolic compounds with H2SO4 or HClO4 as supporting electrolyte with electrodes under anodic oxidation on boron doped diamond (BDD). Therefore it was necessary to reproduce the data ICE exposes the fault model, and thus the 2-naphthol was used as phenolic compound to be oxidised at concentrations of 9, 12 and 15 mmol L-1, and H2SO4 and HClO4 to 1 mol L-1 as a supporting electrolyte under a current density of 30 mA cm-2 in an electrochemical reactor for continuous flow disk configuration, and equipped with anodes DDB at room temperature (25 oC). Experiments were performed using N2 like as purge gas for eliminate oxygen dissolved in solution so that its influence in the system was studied. After exposure of the anomaly of the ICE model and investigation of its relationship with dissolved O2, the data could be treated, making it possible for confirmation. But not only that, the data obtained from eletranálise and spectroscopic analysis suggest the involvement of other strongly oxidizing species (O3 (ozone) and O radicals and O2 -), since the dissolved O2 can be consumed during the formation of new strong oxidizing species, not considered until now, something that needs to be investigated by more accurate methods that we may know a little more of this system. Currently the performance of the electrocatalytic process is established by a complex interaction between different parameters that can be optimized, so it is necessary to the implementation of theoretical models, which are the conceptual lens with which researchers see

Degradação eletroquímica de benzeno, tolueno e xileno via oxidação eletroquímica utilizando eletrodo Ti/Pt

This work is directed to the treatment of organic compounds present in produced water from oil using electrochemical technology. The water produced is a residue of the petroleum industry are difficult to treat , since this corresponds to 98 % effluent from the effluent generated in the exploration of oil and contains various compounds such as volatile hydrocarbons (benzene, toluene, ethylbenzene and xylene), polycyclic aromatic hydrocarbons (PAHs), phenols, carboxylic acids and inorganic compounds. There are several types of treatment methodologies that residue being studied, among which are the biological processes, advanced oxidation processes (AOPs), such as electrochemical treatments electrooxidation, electrocoagulation, electrocoagulation and eletroredution. The electrochemical method is a method of little environmental impact because instead of chemical reagents uses electron through reactions of oxide-reducing transforms toxic substances into substances with less environmental impact. Thus, this paper aims to study the electrochemical behavior and elimination of the BTX (benzene, toluene and xylene) using electrode of Ti/Pt. For the experiment an electrochemical batch system consists of a continuous source, anode Ti/Pt was used, applying three densities of current (1 mA/cm2, 2,5 mA/cm2 and 5 mA/cm2). The synthetic wastewater was prepared by a solution of benzene, toluene and xylene with a concentration of 5 ppm, to evaluate the electrochemical behavior by cyclic voltammetry and polarization curves, even before assessing the removal of these compounds in solution by electrochemical oxidation. The behavior of each of the compounds was evaluated by the use of electrochemical techniques indicate that each of the compounds when evaluated by cyclic voltammetry showed partial oxidation behavior via adsorption to the surface of the Ti/Pt electrode. The adsorption of each of the present compounds depends on the solution concentration but there is the strong adsorption of xylene. However, the removal was confirmed by UV-Vis, and analysis of total organic carbon (TOC), which showed a percentage of partial oxidation (19,8 % - 99,1 % TOC removed), confirming the electrochemical behavior already observed in voltammetry and cyclic polarization curves