Sonochemical degradation of azo dyes in aqueous solution: a new heterogeneous kinetics model taking into account the local concentration of OH radicals and azo dyes

The sonochemical decolorization and decomposition of azo dyes, such as C. I. Reactive Red 22 and methyl orange, were performed from the viewpoints of wastewater treatment and to determine the reaction kinetics. A low concentration of the azo dye solution was irradiated with a 200 kHz and 1.25 W/cm2 ultrasound in a homogeneous aqueous solution. The azo dye solutions were readily decolorized by the irradiation. The sonochemical decolorization was also depressed by the addition of the t-butyl alcohol radical scavenger. These results indicated that azo dye molecules were mainly decomposed by OH radicals formed from the water sonolysis. In this paper, we propose a new kinetics model taking into account the heterogeneous reaction kinetics similar to a Langmuir-Hinshelwood mechanism or an Eley-Rideal mechanism. The proposed kinetics model is based on the local reaction site at the interface region of the cavitation bubbles, where azo dye molecules are quickly decomposed because an extremely high concentration of OH radicals exists in this region. To confirm the proposed kinetics model, the effects of the initial concentration of azo dyes, irradiated atmosphere and pH on the decomposition rates were investigated. The obtained results were in good agreement with the proposed kinetics model.     

Individual and combined effects of ultrasound, ozone and UV irradiation: a case study with textile dyes

Comparative degradation of azo dyes by 520 kHz ultrasonic irradiation and its combinations with ozone and/or ultraviolet light (UV) was investigated using a probe dye C.I. Acid Orange 7. Operation parameters such as ultrasonic power density, ozone flow, UV intensity, and type and injection mode of the bubbling gas were optimized based on the rate of absorption decay in the visible and UV bands as estimated by regression analysis of absorption-time data. At equivalent initial dye concentrations and contact times, individual effects of UV irradiation, ultrasound and ozone were "no effect", "bleaching", and "bleaching/organic carbon degradation", respectively. UV irradiation, however, was found to induce a catalytic effect when applied in combination with either ultrasound or ozone schemes; and the overall degradation process was most rapid under simultaneous operation of the three in the presence of a continuous flow of a gas mixture made of argon and oxygen. The synergy observed in combined schemes was attributed to enhanced ozone diffusion by mechanical effects of ultrasound, and the photolysis of ultrasound-generated H(2)O(2) to produce hydroxyl radicals.     

Synergetic decolorization of azo dyes using ultrasounds,photocatalysis and photo-fenton reaction

In the present work, ultrasound irradiation, photocatalysis with TiO₂, Fenton/Photo-Fenton reaction, and the combination of those techniques were investigated for the decolorization of industrial dyes in order to study their synergy. Three azo dyes were selected from the weaving industry. Their degradation was examined via UV illumination, Fenton and Photo-Fenton reaction as well as ultrasound irradiation at low (20 kHz) and high frequencies (860 kHz). In these experiments, we investigated the simultaneous action of the ultrasound and UV irradiation by varying parameters like the duration of photocatalysis and ultrasound irradiation frequency. At the same time, US power, temperature, amount of TiO₂ photocatalyst and amount of Fenton reagent remained constant. Due to their diverse structure, each azo dye showed different degradation levels using different combinations of the above-mentioned Advanced Oxidation Processes (AOPs). The Photo-Fenton reagent is more effective with US 20 kHz and US 860 kHz for the azo dyes originated from the weaving industry at pH = 3 as compared to pH = 6.8. The combination of the Photo-Fenton reaction with 860 kHz ultrasound irradiation for the same dye gave an 80% conversion at the same time. Experiments have shown a high activity during the first two hours. After that threshold, the reaction rate is decreased. FT-IR and TOC measurements prove the decolorization due to the destruction of the chromophore groups but not complete mineralization of the dyes.     

Decolorizing of azo dye Reactive red 24 aqueous solution using exfoliated graphite and H2O2 under ultrasound irradiation

At its natural pH (6.95), the decolorization of Reactive red 24 in ultrasound, ultrasound/H₂O₂, exfoliated graphite, ultrasound/exfoliated graphite, exfoliated graphite/H₂O₂ and ultrasound/exfoliated graphite/H₂O₂ systems were compared. An enhancement was observed for the decolorization in ultrasound/exfoliated graphite/H₂O₂ system. The effect of solution pH, H₂O₂ and exfoliated graphite dosages, and temperature on the decolorization of Reactive red 24 was investigated. The sonochemical treatment in combination with exfoliated graphite/H₂O₂ showed a synergistic effect for the decolorization of Reactive red 24. The results indicated that under proper conditions, there was a possibility to remove Reactive red 24 very efficient from aqueous solution.

The decolorization of other azo dyes (Reactive red 2, Methyl orange, Acid red 1, Acid red 73, Acid red 249, Acid orange 7, Acid blue 113, Acid brown 75, Acid green 20, Acid yellow 42, Acid mordant brown 33, Acid mordant yellow 10 and Direct green 1) was also investigated, at their natural pH.     

Interaction between flavin mononucleotide-containing azoreductase and azo dyes

ABSTRACT

Azoreductase, a flavin mononucleotide-containing oxidoreductase from Escherichia coli, can catalyze the reduction of azo dyes to form aromatic amine compounds. Few spectroscopic studies have explored the binding mode of azo dyes or the role of the arginine at site 59 in Azoreductase. In this article, protein engineering strategy has been used to construct one mutant in which the arginine residue at site 59 was mutated to glycine. Fluorescence spectroscopic data showed that the addition of Methyl Red and Methyl Orange resulted in the fluorescence quenching of the cofactor flavin mononucleotide bound to Azoreductase. The association constant was fitted using the standard binding equation instead of the Stern-Volmer equation. The results showed that the mutation from the arginine to glycine at site 59 weakened the association constant from 2.21?×?10⁵?L.mol^?1 to 4.55?×?10⁴?L.mol^?1 at 25°C. A similar phenomenon was also observed when Methyl Orange was used as a substrate. In each case, the association constant tended to decrease as the temperature increased from 25°C to 37°C. Thermodynamic parameter analysis revealed that the interaction type changed from a van der Waals interaction (between Azoreductase and the dyes) to a hydrogen bonding interaction (between the mutant and the dyes). Moleculcar docking was also performed in this work to provide some support for the binding mode and binding stability between Azoreductase/mutant and azo dyes.     

Rapid decolorization of azo dyes in aqueous solution by an ultrasound-assisted electrocatalytic oxidation process

In this study, we developed a novel ultrasound-assisted electrocatalytic oxidation (US–EO) process to decolorize azo dyes in aqueous solution. Rhodamine B was decolorized completely within several minutes in this developed US–EO system. Oxidation parameters such as applied potentials, power of the ultrasound, initial pH of the solution, and initial concentration of RhB were systematically studied and optimized. An obvious synergistic effect was found in decolorization of RhB by the US–EO process when comparing with either ultrasound (US) process or electrocatalytic oxidation (EO) one. Additionally, the decolorization of other azo dyes, such as methylene blue, reactive brilliant red X-3B, and methyl orange, were also effective in the US–EO system. The results indicated that US–EO system was effective for the decolorization of azo dyes, suggesting its great potential in dyeing wastewater treatment.     

Degradation of aryl-azo-naphthol dyes by ultrasound, ozone and their combination: effect of alpha-substituents

Lab-scale degradation of azo dyes with ultrasound (300 kHz), ozone and both was investigated using an aryl-azo-naphthol dye-C.I. Acid Orange 8. It was found that in all schemes color decay was faster than UV absorbance, and the rates followed pseudo-first-order kinetics except for the decay of UV-254 band by ozone. Sonication alone was sufficient for decolorization, but not for UV absorption abatement or mineralization. Ozonation was more effective than ultrasound in bleaching, but not as much for the mineralization of the dye. Combined operation of ultrasound and ozone improved the rate of bleaching and UV absorption decay and remarkably enhanced the mineralization of the dye. This was attributed to increased mass transfer of ozone in solution and its decomposition in the gas phase to yield hydroxyl radicals and other oxidative species. The effect of alpha-methyl substituent at the aryl carbon of the dye was found to decelerate the rate of degradation as a result of weakened intramolecular hydrogen bonding.     

Synergistic degradation of methyl orange in an ultrasound intensified photocatalytic reactor

An original ultrasound (US) directly intensified photocatalytic reactor was designed to degrade azo dye pollutant methyl orange (MeO) using Degussa TiO(2) as the photocatalyst. The sonolytic, photocatalytic and sonophotocatalytic degradation of MeO in the new reactor and the synergistic effect between sonolysis and photocatalysis were investigated. Effects of operation parameters i.e., US power, TiO(2) dosage, liquid circulation velocity and air flow rate on degradation efficiency were investigated and optimized. The results showed that all parameters have optimal values for the sonophotocatalytic degradation of MeO, and the optimum conditions for the new process are US power 600 W, TiO(2) dosage 3g/L, liquid circulation velocity 4.05×10(-2) m/s and air flow rate 0.2 L/min. Under the optimum conditions, 91.52% MeO had been degraded within 1h, and the combination of sonolysis and TiO(2) photocatalysis exhibited an obvious synergetic effect.     

Effects of ultrasound on the enzymatic degradation of pectin

Ultrasound-assisted enzymatic maceration (UAEM) has gained considerable interest in the fruit juice industry, owing to its potential to increase juice yield and content of polyphenols while simultaneously saving time and energy. In this study, the effects of UAEM (ultrasonic probe, 20 kHz, 21 W*cm⁻² and 33 W*cm⁻²) on pectin degradation in a continuous circulation system were investigated over 60 and 90 min. Main pectinolytic enzymes activities of (polygalacturonase, pectin lyase and pectin methylesterase) of a commercial enzyme preparation were examined for individual synergistic effects with US. Pectin hydrolysis by UAEM differed significantly compared to treatment with ultrasound or enzymes alone regarding the profile of degradation products compared to treatment with ultrasound or enzymes alone. Ultrasound fragmented pectin to less branched oligomers of medium molecular weight (Mp approx. 150 kDa), which were further degraded by pectinolytic activities. The low molecular weight fraction (<30 kDa), which is known to be beneficial for juice-quality by adding nutritional value and stabilizing polyphenols, was enriched in small oligomers of homogalacturonan-derived, rhamnogalacturonan I-derived, and rhamnogalacturonan II-derived residues. Synergistic effects of ultrasound application enhanced the effective activities of polygalacturonase and pectin lyase and even prolonged their performance over 90 min, whereas the effective activity of pectin methylesterase was not affected. Final marker concentrations determined by each enzyme assay revealed a considerable higher total process output after UAEM treatment at reduced temperature (30 °C) comparable to the output after conventional batch maceration at 50 °C. The obtained results demonstrate the high potential of UAEM to produce high-quality juice by controlling pectin degradation while reducing process temperature and equally highlight the matrix and enzyme specific effects of a simultaneous US treatment.     

Theoretical mechanistic studies on the degradation of alizarin yellow R initiated by hydroxyl radical

The degradation of azo dyes has attracted many research efforts not only due to the resulting environmental problems but also because the azo compounds with various substituents may show different degradation mechanism. It has been computationally found here, for the first time, that the HO? initiated cleavages of C–N and N–N bonds of alizarin yellow R with carboxyl group are kinetically competitive. In view of the formation of HO? adducts, the C–N and N–N bond cleavages of the hydrazone tautomer of alizarin yellow R are also kinetically competitive, but the former is more thermodynamically favorable. This result is different from that previously reported for the hydrozone tautomers of Acid Orange 7 and Acid Orange 8 containing hydroxyl and azo groups in neighboring positions, which are favorable to follow C–N bond cleavage mechanism both kinetically and thermodynamically. The decarboxylation occurs via an attack of HO? to the benzene ring carbon connecting to the carboxyl group rather than a direct attack of HO? to the carboxyl carbon atom. The anion form has higher reactivity than the neutral form in all of the reactions investigated. In addition, a water molecule as a proton relay reagent could significantly reduce the energy barrier for the N–N bond cleavage of alizarin yellow R. Copyright © 2014 John Wiley & Sons, Ltd.     

输入电功率在大范围内变动时声致发光与电功率之间的关系

采用频率为１．１ＭＨｚ，声辐射面积为３ｃｍ＾２换能器，在输入电功率０－１２０Ｗ范围内研究了被空气自然饱和纯水中声致发光强度和输入电功率在大范围内变化时的关系，结果表明，声致发光在输入电功率为７０－９０Ｗ之间，不再随输入电功率的增加而增加，呈现出饱和现象，在饱和值的出现前，发光强度随输入电功率的增加呈不规则的阶状增加，在饱和值结束后，随输入电功率的增加，发光强度迅速减小，本文对实验结果进行了些定性的     

UV-spectral changes for some azo compounds in the presence of different solvents

The electronic absorption spectra of four azo dyes with different substituents (such as Cl, I, OH) are determined at room temperature in twenty-one solvents with different polarities. The electronic transitions of azo dyes are interpreted. Linear solvation energy relationships have been investigated for solvatochromic behaviors and solute-solvent interactions of azo dyes. Linear solvation energy relationships were performed by multiple linear regression analysis using dielectric function, refractive index function and Kamlet-Taft parameters. We have observed that the hydrogen bonding acceptor ability and the induction-dispersive forces of solvent molecules have caused the bathochromic shift in absorption maxima of azo dyes.     

Ultrasound assisted enzymatic degumming of crude soybean oil

The present work deals with ultrasound assisted enzymatic degumming (UAED) of crude soybean oil quantifying the extent of degumming (EOD), cavitational yield and synergistic index (f) for the combination approaches. The effect of different operating parameters such as enzyme loading, pH, presence of water, temperature and ultrasonic power on the EOD has been investigated. Ultrasound combined with enzyme at loading of 2.0 ml/L resulted in EOD as 92.2% under ambient conditions. Addition of water (5%) in combination with ultrasound and enzyme at 2.0 ml/L loading and pH of 5 resulted in maximum EOD (98.4%) in 120 min of treatment. The extent of phospholipid separation was also observed to be dependent on the power dissipation and maximum phospholipids separation was obtained at 100 W. Scale-up studies were performed at 500 ml and 1 L operating volume under optimized conditions of 2.0 ml/L as the enzyme loading, pH of 5, 5% water addition and ultrasonic power of 100 W where 93.63% and 91.15% phospholipid separation respectively was obtained. The effects of ultrasonic treatment were also quantified in terms of the acid value reduction and oxidative stability for the processed oil. It was demonstrated that suitable reduction in acid value (final value less than 1) and oxidative stability (TOTOX less than 4) is effectively obtained using UAED. Overall the approach of UAED was established to show much higher efficacy for soybean oil processing as compared to only ultrasound or only enzymatic treatment.     

Decomposition of an azo dye in aqueous solution by combination of ultrasound and visible light

The degradation of Acid Orange 7 in aqueous solution has been investigated under the irradiation of ultrasound and visible light respectively and simultaneously. We have observed that the maximum removal percentage K increases from 4% to 35% when the ultrasonic frequency f and power P change from f=20 KHz and P=3 W to f=1 MHz and P=40 W. On the other hand, the K-value is approximately 3% under the irradiation of visible light at 632 nm and 100 mW/mm(2). Under the simultaneous irradiation of ultrasound (1 MHz, 40 W) and visible light (632 nm, 100 mW/mm(2)), the K-value reaches to approximately 65%, indicating a synergistic effect of ultrasound and visible light irradiations. A simple model based on the band gap theory and cavitation theory is proposed to explain the synergistic phenomenon.     

Degradation of reactive,acid and basic textile dyes in the presence of ultrasound and rare earths [Lanthanum and Praseodymium]

Degradation of five textile dyes, namely Reactive Red 141 (RR 141), Reactive Blue 21 (RB 21), Acid Red 114 (AR 114), Acid Blue 113 (AB 113) and Basic Violet 16 (BV 16) in aqueous solution has been carried out with ultrasound (US) and in combination with rare earth ions (La³⁺ and Pr³⁺). Kinetic analysis of the data showed a pseudo-first order degradation reaction for all the dyes. The rate constant (k), half life (t_1/2) and the process efficiency (φ) for various processes in degradation of dyes under different experimental conditions have been calculated. The influence of concentrations of dyes (16–40 mg/L), pH (5, 7 and 9) and rare earth ion concentration (4, 12 and 20 mg/L) on the degradation of dyes have also been studied. The degradation percentage increased with increasing rare earth amount and decreased with increasing concentration of dyes. Both horn and bath type sonicators were used at 20 kHz and 250 W for degradation. The sonochemical degradation rate of dyes in the presence of rare earths was related to the type of chromophoric groups in the dye molecule. Degradation sequence of dyes was further examined through LCMS and Raman spectroscopic techniques, which confirmed the sonochemical degradation of dyes to non-toxic end products.     

Degradation of Acid Orange 7 in aqueous solution by zero-valent aluminum under ultrasonic irradiation

Degradation of azo dye Acid Orange 7 (AO7) by zero-valent aluminum (ZVAl) in combination with ultrasonic irradiation was investigated. The preliminary studies of optimal degradation methodology were conducted with sole ultrasonic, sole ZVAl/air system, ultrasonication + ZVAl/air system (US-ZVAl). In ZVAl/air system, the degradation of AO7 could almost not be observed within 30 min. The degradation of AO7 by ZVAl/air system was obviously enhanced under ultrasound irradiation, and the enhancement is mainly attributed to that the production of hydroxyl radicals in ultrasound-ZVAl process was much higher than that in sole ultrasonic or in sole ZVAl/air system. The variables considered for the effect of degradation were the power of ultrasound, the initial concentration of AO7, as well as the initial pH value and the dosage of zero-valent aluminum. The results showed that the decolorization rate increased with the increase of power density and the dosage of ZVAl, but decreased with the increase of initial pH value and initial concentration of AO7. More than 96% of AO7 removal was achieved within 30 min under optimum operational conditions (AO7: 20 mg/L, ZVAl: 2 g/L, pH: 2.5, ultrasound: 20 kHz, 300 W). This study demonstrates that ultrasound-ZVAl process can effectively decolorize the azo dye AO7 in wastewater.     

In vitro effects of ultrasound with different energies on the conduction properties of neural tissue

The effect of ultrasound at various energy levels on the conduction properties of neural tissue is explored in this in vitro study. Excised sciatic nerves from the bullfrog were used for experiments. The nerves were stimulated by 3.5 MHz continuous wave ultrasound at 1, 2, and 3 W for 5 min. The peak-to-peak amplitude of the electrically evoked compound action potential (CAP) and the conduction velocity (CV) were measured in the nerves before and during ultrasound stimulation. The CV of the nerves increased by 5-20% for ultrasound stimulations at 1-3 W. The CAP amplitude increased by 8% during stimulation with 1 W ultrasound, and progressively decreased for 2 and 3 W ultrasound. This indicates that the effect of lower energy ultrasound increases both the CV and the CAP amplitude and that the reduction in the CAP amplitude for higher energy ultrasound is associated largely with ultrasonic thermal effects.     

Comparative study on the process behavior and reaction kinetics in sonocatalytic degradation of organic dyes by powder and nanotubes TiO2

Sonocatalytic degradation of various organic dyes (Congo Red, Reactive Blue 4, Methyl Orange, Rhodamine B and Methylene Blue) catalyzed by powder and nanotubes TiO₂ was studied. Both catalysts were characterized using transmission electron microscope (TEM), surface analyzer, Raman spectroscope and thermal gravimetric analyzer (TGA). Sonocatalytic activity of powder and nanotubes TiO₂ was elucidated based on the degradation of various organic dyes. The former catalyst was favorable for treatment of anionic dyes, while the latter was more beneficial for cationic dyes. Sonocatalytic activity of TiO₂ nanotubes could be up to four times as compared to TiO₂ powder under an ultrasonic power of 100 W and a frequency of 42 kHz. This was associated with the higher surface area and the electrostatic attraction between dye molecules and TiO₂ nanotubes. Fourier transform-infrared spectrometer (FT-IR) was used to identify changes that occurred on the functional group in Rhodamine B molecules and TiO₂ nanotubes after the reaction. Sonocatalytic degradation of Rhodamine B by TiO₂ nanotubes apparently followed the Langmuir-Hinshelwood adsorption kinetic model with surface reaction rate of 1.75 mg/L min. TiO₂ nanotubes were proven for their high potential to be applied in sonocatalytic degradation of organic dyes.     

Sonochemically enhanced adsorption and degradation of methyl orange with activated aluminas

Removal of Methyl orange (MO), as a model contaminants, in aqueous solution by the simultaneous application of ultrasound with the addition of porous adsorbent powders is reported. Activated alumina powders in acidic form were used as an adsorbent. Results showed that MO could be degraded by ultrasonic irradiation at 130 kHz with the first order rate constant of 8x10(-4) and 5x10(-4) sec(-1), in acidic and basic conditions, respectively, without adsorbents. Adsorption rates of MO by activated alumina mainly depended on the acidity of alumina, the pH of solution and the stirring speed. At pH=4.2 with mechanical stirring without ultrasonic radiation, acidic activated alumina (0.1 g/100 ml) removed MO at about two times more rapidly than ultrasonic irradiation. In the case of simultaneous application of ultrasound irradiation and activated alumina, MO was almost removed from the solution within 10 min, which corresponded to as a rate constant of 5x10(-3) sec(-1). This kind of synergistic enhancement of removal rate with ultrasound and adsorbents should be practically useful for the elimination of contaminants in the water treatment processes. In addition, the effects of pH and coexisting chemicals in the solution were examined for the processes. Although the adsorption process was effective in some selected conditions, ultrasonic degradation was more robust in wider range of pH and coexisting chemicals. Simultaneous application of the two processes can perform complementary.     

C.I. Reactive Black 5 decolorization by combined sonolysis and ozonation

Decolorization of the azo dye C.I. Reactive Black 5 (RB5) in solution by a combination of sonolysis and ozonation was investigated. The results showed that the optimum pH for the reaction was 11.0, and both lower and higher pH decreased the decolorization rate. Increasing the initial concentration of RB5 led to a decreasing decolorization rate. Under the experimental conditions, the decolorization rate increased with an increase in temperature. The decolorization of RB5 followed pseudo-first-order reaction kinetics. Based on the decolorization rate constants obtained at different temperatures within the range 287-338K and the Arrhenius equation, the apparent activation energy (E(a)) was calculated to be 11.2kJmol(-1). This indicated that the reaction has little dependence on temperature. The color decay was considerably faster than the decrease in total organic carbon (TOC), which was attributed to the ease of chromophore destruction. Hence the efficiency of decolorization was 84% compared with 4% of TOC removal after 5min reaction. Additionally, muconic acid, (2Z)-pent-2-enedioic acid and maleic acid were identified as main oxidation products by gas chromatography coupled with mass spectrometry (GC-MS) after 150min of reaction.