Mechanism of decolorization and degradation of CI Direct Red 23 by ozonation combined with sonolysis

The decolorization and degradation of CI Direct Red 23, which is suspected to be carcinogenic, were investigated using ozonation combined with sonolysis. The results showed that the combination of ozonation and sonolysis was a highly effective way to remove color from waste water. The operational parameters, namely concentration of the dye, pH, ozone dose and ultrasonic density, were investigated during the process. The decolorization of the dye followed pseudo-first-order kinetics. Increasing the initial concentration of Direct Red 23 led to a decreasing rate constant. The optimum pH for the reaction was 8.0, and both lower and higher pH decreased the removal rate. The effect of the ozone dose on the dye decolorization was much greater than that of the sonolysis density. Intermediates such as naphthalene-2-sulfonic acid, 1-naphthol, urea and acetamide were detected by gas chromatography coupled with mass spectrometry in the absence of pH buffer, while nitrate and sulfate ions and formic, acetic and oxalic acids were detected by ion chromatography. A tentative degradation pathway was proposed without any further quantitative analyses. During the degradation, all nitrogen atoms and phenyl groups of Direct Red 23 were degraded into urea, nitrate ion, nitrogen and formic, acetic and oxalic acids, etc.     

Electro-oxidation of the dye azure B: kinetics,mechanism, and by-products

In this work, the electrochemical degradation of the dye azure B in aqueous solutions was studied by electrochemical advanced oxidation processes (EAOPs), electro-Fenton, and anodic oxidation processes, using Pt/carbon-felt and boron-doped diamond (BDD)/carbon-felt cells with H₂O₂ electrogeneration. The higher oxidation power of the electro-Fenton (EF) process using BDD anode was demonstrated. The oxidative degradation of azure B by the electrochemically generated hydroxyl radicals (^?OH) follows a pseudo-first-order kinetics. The apparent rate constants of the oxidation of azure B by ^?OH were measured according to pseudo-first-order kinetic model. The absolute rate constant of azure B hydroxylation reaction was determined by competition kinetics method and found to be 1.19?×?10⁹ M^?1 s^?1. It was found that the electrochemical degradation of the dye leads to the formation of aromatic by-products which are then oxidized to aliphatic carboxylic acids before their almost mineralization to CO₂ and inorganic ions (sulfate, nitrate, and ammonium). The evolution of the TOC removal and time course of short-chain carboxylic acids during treatment were also investigated.     

Biological decolourisation of simulated azo dye in aqueous phase by algae Spirogyra species

Biological decolourisation of two azo dye effluents (direct and reactive dye) were investigated using a commonly available green algae Spirogyra sp. in viable form. Batch studies revealed the potential of algal species in removing the dye colour and dye removal was dependant on initial algal inoculum, concentration and application class of the dye. Maximum dye uptake was noticed on the third day for both the dyes. Higher dye uptake was observed in the case of direct red 28 compared to reactive red 2. Dye colour removal by the algal species may be attributed to biosorption of the dye molecules onto the surface of algal cell and subsequent diffusion and participation in metabolism (bioconversion). The remaining dye molecules could be further removed from the aqueous phase by adsorption and/or chelation reaction of the exopolymers released by the algae (biocoagulation). The results of the present study reveal the potential nature of algae in treating azo dyes which in turn can be extended to oxidation pond system of wastewater treatment.     

Fe(3+)- and Cu(2+)-reduction by phenol derivatives associated with Azure B degradation in Fenton-like reactions

Several phenol derivatives were evaluated regarding their capacities for Fe(3+) and Cu(2+) reduction. Selected compounds were assayed in Fenton-like reactions to degrade Azure B. 3,4-Dihydroxyphenylacetic, 2,5-dihydroxyterephtalic, gallic, chromotropic and 3-hydroxyanthranilic acids were the most efficient reducers of both metallic ions. The reaction system composed of 3-hydroxyanthranilic acid/Fe(3+)/H(2)O(2) was able to degrade Azure B at higher levels than the conventional Fenton reaction (87% and 75% of decolorization after 20min reaction, respectively). Gallic and syringic acids, catechol and vanillin induced Azure B degradations at lower levels as compared with conventional Fenton reaction. Azure B was not degraded in the presence of 10% (v/v) methanol or ethanol, which are OH radical scavengers, confirming the participation of this radical in the degradation reactions. Iron-containing reactions consumed substantially more H(2)O(2) than reactions containing copper. In iron-containing reactions, even the systems that caused a limited degradation of the dye consumed high concentrations of H(2)O(2). On the other hand, the reactions containing Fe(3+), H(2)O(2) and 3-hydroxyanthranilic acid or 3,4-dihydroxyphenylacetic acid were the most efficient on degradation of Azure B and also presented the highest H(2)O(2) consumption. These results indicate that H(2)O(2) consumption occurs even when the dye is not extensively degraded, suggesting that part of the generated OH radicals reacts with the own phenol derivative instead of Azure B.     

Ozonation of Cationic Red X-GRL in aqueous solution: degradation and mechanism

Ozonation of the azo dye Cationic Red X-GRL was investigated in a bubble column reactor at varying operating parameters such as oxygen flow rate, temperature, initial Cationic Red X-GRL concentration, and pH. The conversion of dye increased with the increasing of pH and oxygen flow rate. As the reaction rate constant and the volumetric mass transfer coefficient increase while the ozone equilibrium concentration decreases with the temperature, there is a minimum conversion of dye at 25 degrees C. The increasing of initial dye concentration leads to a decreasing conversion of dye while the ozonation rate increases. The formation of intermediates and the variation of pH, TOC, and nitrate ion during ozonation were investigated by the use of some analytical instruments such as GC/MS, GC, and IC. The intermediates of weak organic acids lower the pH value of the solution. The probable degradation mechanism of the Cationic Red X-GRL in aqueous solution was deliberated with the aid of Molecular Orbital calculations. The N(12)-C(13) site in Cationic Red X-GRL, instead of the N(6)-N(7) site, is found to be the principal site for ozone cycloaddition in the degradation processes. During the degradation process, among the six nitrogen atoms of Cationic Red X-GRL, one is transferred into a nitrate ion, one is converted into an amine compound, and the remaining four are transformed into two molecules of nitrogen.     

Two stage biological treatment of a diazo reactive textile dye and the fate of the dye metabolites

A two stage anaerobic/aerobic bacterial process was used to decolorize and partially mineralize a reactive vinyl sulfone diazo dye C.I. Reactive Black 5 (RB5) in a synthetic wastewater. Since the anchor group of reactive dyes reacts during the dyeing process, the effect the degree of hydrolysis of the vinyl sulfone dye had on decolorization, mineralization and toxicity in each stage was investigated. An overall color removal of approximately 65% was found for both the fully and partially hydrolyzed dye. Partial mineralization of the fully hydrolyzed RB5 was achieved in the two stage rotating disc reactors. While the anchor group metabolite p-aminobenzene-2-hydroxyethylsulfonic acid (p-ABHES) was mineralized, an oxidized form of the center metabolite (1,2-ketimino-7-amino-8-hydroxynaphthalene-3,6-disulfonic acid) remained in the aerobic stage effluent, causing the effluent to be colored although no RB5 was present. Partially hydrolyzed dye in the influent with vinyl forms of the anchor group caused cessation of biogas production and a reduction in decolorization efficiency in the anaerobic stage. No evidence for mineralization of the partially hydrolyzed dye or its metabolites was found. A method for evaluating dye mineralization using lumped parameters is presented.     

Removal of Yellow ME 7 GL from industrial effluent using electrochemical and adsorption techniques

Attempts have been made to remove toxic dye Yellow ME7GL using electrochemical and adsorption techniques. Both techniques are capable of reducing toxicity and producing clean water for reuse. The electrochemical removal is carried out at platinum electrode and cyclic voltammograms of the dye solutions have been recorded at different pH, concentrations, scan rates, etc. The adsorption of the dye has been carried out over activated charcoal and wheat husk and verified by Langmuir and Freundlich adsorption isotherms. The decolouration of the dye was also examined by monitoring the Chemical Oxygen Demand (COD) of the untreated and treated dye solutions.     

Biodegradation and biosorption of acid anthraquinone dye

The acid anthraquinone dye Tectilon Blue (TB4R) is a major coloured component from the aqueous effluent of a carpet printing plant in Northern Ireland. The aerobic biodegradation of TB4R has been investigated experimentally in batch systems, using three strains of bacteria, namely, Bacillus gordonae (NCIMB 12553), Bacillus benzeovorans (NCIMB 12555) and Pseudomonas putida (NCIMB 9776). All three strains successfully decolourised the dye, and results were correlated using Michaelis-Menten kinetic theory. A recalculation of the reaction rate constants, to account for biosorption, gave an accurate simulation of the colour removal over a 24-h period. Up to 19% of the decolorisation was found to be caused by biosorption of the dye onto the biomass, with the majority of the decolorisation caused by utilisation of the dye by the bacteria. The reaction rate was found to be intermediate between zero and first order at dye concentrations of 200-1000 mg/l.     

直接红染料的臭氧脱色与中间产物研究

以直接红B模拟染料废水为研究对象,考察了臭氧化过程中染料溶液的吸光度和TOC的变化,同时利用离子色谱仪和GC/MS对染料的降解过程进行了分析,最后用发光细菌法检测了染料溶液急性毒性的变化。结果表明,臭氧对染料的降解符合一级反应动力学,20 min时对染料的脱色率达到99.2%;反应40 min后TOC减少32.55%,染料分子有97.8%的S被氧化为SO^2-₄,偶氮键被臭氧化为N₂,分子中的仲胺基小部分转化成游离NH⁺₄和NO^-₃;在臭氧化过程前期新生成的醛类和酰胺类物质使溶液急性毒性迅速上升,25 min后溶液毒性开始逐渐下降。     

Solar light induced and TiO2 assisted degradation of textile dye reactive blue 4

Aqueous solutions of reactive blue 4 textile dye are totally mineralised when irradiated with TiO2 photocatalyst. A solution containing 4 x 10(-4) M dye was completely degraded in 24 h irradiation time. The intensity of the solar light was measured using Lux meter. The results showed that the dye molecules were completely degraded to CO2, SO4(2-), NO3-, NH4+ and H2O under solar irradiation. The addition of hydrogen peroxide and potassium persulphate influenced the photodegradation efficiency. The rapidity of photodegradation of dye intermediates were observed in the presence of hydrogen peroxide than in its absence. The auxiliary chemicals such as sodium carbonate and sodium chloride substantially affected the photodegradation efficiency. High performance liquid chromatography and chemical oxygen demand were used to study the mineralisation and degradation of the dye respectively. It is concluded that solar light induced degradation of textile dye in wastewater is a viable technique for wastewater treatment.     

生物技术在印染和染料废水处理中的应用

本文从微生物降解染料的机理、生物处理工艺两个不同角度，介绍了生物技术在国内外印染和染料废水处理的应用情况，并指出了处理这种含染料废水的研究方向。     

活性黑KN-B染料模拟废水电化学脱色

为进一步明确活性染料在可溶性阳极电化学体系中的脱色机理,以铝为牺牲阳极,不锈钢为阴极,在恒电流操作模式下,针对活性黑KN-B模拟废水,考察了电流密度、初始pH值、电解质种类及浓度、温度、染料浓度因素对染料脱色过程的影响。结果表明：(1)电流密度、电解液初始pH值、氯化钠电解质浓度、温度、染料浓度对染料溶液脱色效率影响显著,在一定实验条件下,染料溶液脱色率可达到88%;(2) 在不同pH的范围内,活性黑KN-B表现的脱色机理不同,pH 4～9为混凝与阴极还原脱色共同作用;pH＜4和＞9则表现为阴极还原脱色为主; (3) 氯化钠的加入在增强染料脱色的同时,也有助于芳环类物质的后续混凝去除。     

Adsorption kinetics of methyl violet onto perlite

This study examines adsorption kinetics and activation parameters of methyl violet on perlite. The effect of process parameters like contact time, concentration of dye, temperature and pH on the extent of methyl violet adsorption from solution has been investigated. Results of the kinetic studies show that the adsorption reaction is first order with respect to dye solution concentration with activation energy of 13.2 kJ mol(-1). This low activation energy value indicates that the adsorption reaction is diffusion controlled. The activation parameters using Arrhenius and Eyring equations have been calculated. Adsorption increases with increase of variables such as contact time, initial dye concentration, temperature and pH.     

Competitive adsorption of dye metanil yellow and RB15 in acid solutions on chemically cross-linked chitosan beads

One kind of adsorbent with a high adsorption capacity for anionic dyes was prepared using ionically and chemically cross-linked chitosan beads. A batch system was applied to study the adsorption behavior of one acid dye (MY, metanil yellow) and one reactive dye (RB15, reactive blue 15) in aqueous solutions by the cross-linked chitosan beads. The adsorption capacities was 3.56 mmol g(-1) (1334 mg g(-1)) for dye MY and 0.56 mmol g(-1) (722 mg g(-1)) for dye RB15 at pH4, 30 degrees C. The Langmuir model agreed very well with the experimental data (R(2)>0.996). The kinetics of adsorption for a single dye and the kinetics of removal of ADMI color value in mixture solutions at different initial dye concentrations were evaluated by the nonlinear first-order and second-order models. The first-order kinetic model fits well with the dynamical adsorption behavior of a single dye for lower initial dye concentrations, while the second-order kinetic model fits well for higher initial dye concentrations. The competitive adsorption favored the dye RB15 in the mixture solution (initial conc. (mM): MY=1.34; RB15=1.36); while it favored the dye MY in the mixture solution (initial conc. (mM): MY=3.00; RB15=1.34) and the adsorption kinetics for dye RB15 has the tendency to shift to a slower first order model.     

In situ photoelectrochemical/photocatalytic study of a dye discoloration in a microreactor system using TiO2 thin films

Introduction

In this work, we report in situ studies of UV photoelectrocatalytic discoloration of a dye (indigo carmine) by a TiO₂ thin film in a microreactor to demonstrate the driving force of the applied electrode potential and the dye flow rate toward dye discoloration kinetics.

Methods

TiO₂ 65-nm-thick thin films were deposited by PVD magnetron sputtering technique on a conducting glass substrate of fluorinated tin oxide. A microreactor to measure the discoloration rate, the electrode potential, and the photocurrent in situ, was developed. The dye solutions, before and after measurements in the microreactor, were analyzed by Raman spectroscopy.

Results

The annealed TiO₂ thin films had anatase structure with preferential orientation (101). The discoloration rate of the dye increased with the applied potential to TiO₂ electrode. Further, acceleration of the photocatalytic reaction was achieved by utilizing dye flow recirculation to the microreactor. In both cases the photoelectrochemical/photocatalytic discoloration kinetics of the dye follows the Langmuir?CHinshelwood model, with first-order kinetics.

Conclusions

The feasibility of dye discoloration on TiO₂ thin film electrodes, prepared by magnetron sputtering using a flow microreactor system, has been clearly demonstrated. The discoloration rate is enhanced by applying a positive potential (E _AP) and/or increasing the flow rate. The fastest discoloration and shortest irradiation time (50?min) produced 80% discoloration with an external anodic potential of 0.931?V and a flow rate of 12.2?mL?min^?1.     

Biosorption of alpacide blue from aqueous solution by lignocellulosic biomass: <Emphasis Type="Italic">Luffa cylindrica</Emphasis> fibers

The aim of the present work is to develop an effective and inexpensive pollutant-removal technology using lignocellulosic fibers: Luffa cylindrica, for the biosorption of an anionic dye: alpacide blue. The influence of some experimental parameters such as pH, temperature, initial concentration of the polluted solution, and mass of the sorbent L. cylindrica on the biosorption of alpacide blue by L. cylindrica fibers has been investigated. Optimal parameters for maximum quantity of biosorption dye were achieved after 2 h of treatment in a batch system using an initial dye concentration of 20 mg/L, a mass of 1 g of L. cylindrica fibers, and pH 2. In these conditions, the quantity of dye retained is 2 mg/g and the retention rate is 78 %. Finally, a mathematical modeling of kinetics and isotherms has been used for mathematical modeling; the model of pseudo-second order is more appropriate to describe this phenomenon of biosorption. Concerning biosorption isotherms, the Freundlich model is the most appropriate for a biosorption of alpacide blue dye by L. cylindrica fibers.     

A self-sufficient system for removal of synthetic dye by coupling of spore-displayed triphenylmethane reductase and glucose 1-dehydrogenase

Biodegradation of triphenylmethane dyes by microorganisms is hampered by the transport barrier imposed by cell membranes. On the other hand, cell-free systems using enzyme-based biodegradation strategy are costly. Therefore, an efficient and inexpensive approach circumventing these problems is highly desirable. Here, we constructed a self-sufficient system for synthetic dye removal by coupling of spore surface-displayed triphenylmethane reductase (TMR) and glucose 1-dehydrogenase (GDH) for the first time. Display of both TMR and GDH significantly enhanced their stability under conditions of extreme pH and temperature. These engineered spores also exhibited more robust long-term stability than their purified counterparts. Furthermore, we observed that a high ratio of spore-displayed GDH is necessary for high dye degradation efficiency. These results indicate that this continuous dye removal system with cofactor regeneration offers a promising solution for dye biodegradation applications.     

Degradation and decolorization of a biodegradable-resistant polymeric dye by chelator-mediated Fenton reactions

Chelator-mediated Fenton reactions (CMFRs) were used to decolorize a biodegradable-resistant polymeric dye (Poly R-478). Screening of different iron chelators was performed on Fe(3+)-reduction activity. All chelators showed Fe(3+)-reduction activity over a wide range of pH (2-7) and each mol of catecholate chelators (3,4-dihydroxiphenilacetic acid--DOPAC and 2,3-dihydroxibenzoic acid--DHBA) reduced about 5-6 moles of Fe(3+) whereas hydroxamate chelators (acetohydroxamic acid-AHA and desferrioxamine B-DFB) reduced Fe(3+) stoichiometrically. The most effective decolorization of Poly R-478 was achieved by CMFR using catecholate chelators. In addition, a 2(4) factorial design was performed with the aim of evaluating the effects of the variables considered in this study (pH, [DOPAC], [Fe(3+)] and [H(2)O(2)]) and optimizing the dye decolorization, using response surface methodology. Statistical analysis of results showed that, in the range studied, except for Fe(3+), all variables have a significant effect on dye decolorization. A second-order model is proposed to represent the Poly R-478 decolorization. At optimum conditions, complete decolorization of the dye (degradation of the chromophoric group) and also complete chemical degradation of the dye was observed.     

Treatment of Basic Red 29 dye solution using iron-aluminum electrode pairs by electrocoagulation and electro-Fenton methods

The aim of this study is the treatment of Basic Red 29 (BR29) dye solution using hybrid iron-aluminum electrodes by electrocoagulation and electro-Fenton methods. The effect of current density, initial pH, supporting electrolyte, H₂O₂, and initial dye concentration on dye removal efficiency was investigated, and the best experimental conditions were obtained. Time-coarse variation of UV-Vis spectra and toxicity and chemical oxygen demand (COD) removal were also examined at the best experimental conditions. Both systems were found very successful for the removal of BR29 dye. The removal efficiency of >95 % for BR29 dye solution was reached easily in a short time. At the best experimental conditions, for the initial BR29 concentration of 100 mg/L, >95 % BR29 dye and 71.43 % COD removal were obtained after 20 and 40 min of electrolysis, respectively. Additionally, toxicity results for electro-Fenton treatment of 100 mg/L BR29 were also very promising. According to the results obtained, although electro-Fenton is more effective, both systems can be used successfully to treat textile wastewater including dyes.     

Photocatalytic degradation of azo dyes by nitrogen-doped TiO2 nanocatalysts

This study examined the photocatalytic degradation of three azo dyes, acid orange 7 (AO7), procion red MX-5B (MX-5B) and reactive black 5 (RB5) using a new type of nitrogen-doped TiO2 nanocrystals. These newly developed doped titania nanocatalysts demonstrated high reactivity under visible light (lambda>390 nm), allowing more efficient usage of solar light. The doped titania were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Experiments were conducted to compare the photocatalytic activities of nitrogen-doped TiO2 nanocatalysts and commercially available Degussa P25 powder using both UV illumination and solar light. It is shown that nitrogen-doped TiO2 after calcination had the highest photocatalytic activity among all three catalysts tested, with 95% of AO7 decolorized in 1 h under UV illumination. The doped TiO2 also exhibited substantial photocatalytic activity under direct sunlight irradiation, with 70% of the dye color removed in 1h and complete decolorization within 3 h. Degussa P25 did not cause detectable dye decolorization under identical experimental conditions using solar light. The decrease of total organic carbon (TOC) and evolution of inorganic sulfate (SO4(2-)) ions in dye solutions were measured to monitor the dye mineralization process.