A combination of ultrasound and a bio-catalyst: removal of 2-chlorophenol from aqueous solution

Phenolic compounds have become a cause for worldwide concern due to their persistence, toxicity and health risks. This paper reports a three-step approach to remove 2-chlorophenol from dilute aqueous solution and compares each technique. The first step utilizes Horse Radish Peroxidase (HRP) in presence of hydrogen peroxide to oxidize this organic pollutant (enzyme treatment). For a more efficient removal of 2-chlorophenol, it is necessary to add the enzyme solution gradually to the contents of the reactor instead of rapid addition. The second step, involving ultrasonic waves eliminated 2-chlorophenol through hydroxyl radical generated by the cavitation process (sono-degradation). In the third step, a combination of ultrasonic waves and enzyme was used (sono-enzyme degradation). It should be mentioned that, the enzyme can be active in the presence of ultrasonic waves under the proper sonication. The degradation has been studied at different temperatures, intensities of irradiation, and concentrations of enzyme. The rate of degradation exhibited pseudo-first order behavior and the combination method was more effective than sonolysis and enzyme treatment individually.     

Sono-catalytic degradation and fast mineralization of p-chlorophenol: La0.7Sr0.3MnO3 as a nano-magnetic green catalyst

La_0.7Sr_0.3MnO₃ (LSMO) nanoparticles with a perovskite structure were prepared by a combination of ultrasound and co-precipitation method. The synthesized catalyst was characterized by X-ray diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy. The catalytic performance of the catalyst was evaluated for the degradation of 4-chlorophenol in the presence and in the absence of ultrasound. The degradation has been studied at different temperatures, pH, catalyst dosage, and initial concentration of 4-chlorophenol. The results have shown that the degradation efficiency was higher in the presence of ultrasound than its absence under the mild conditions. More than 88% decrease in the concentration and 85% decrease in the TOC for 4-chlorophenol could be achieved in a short time of sonication with respect to the conventional method. This behavior could be attributed to the cavitation process which followed by a high mass transfer on the catalyst with high surface area. These conditions led to facilitate the removal of pollutant from aqueous solution. The results also indicated that the catalyst without recalcination can be used successfully up to five consecutive cycles without any significant loss in activity in the presence and in the absence of ultrasound. In addition, the most important is the magnetic property of the nanoparticles which separated easily from aqueous solution by an external magnetic field.     

Visible light induced sonophotocatalytic degradation of Reactive Red dye 198 using dye sensitized TiO2

In this paper we are reporting the accelerated sonophotocatalytic degradation of Reactive Red (RR) 198 dye under visible light using dye sensitized TiO(2) activated by ultrasound. The effect of sonolysis, photocatalysis and sonophotocatalysis under visible light has been examined to study the influence on the degradation rates by varying the initial substrate concentration, pH and catalyst loading to ascertain the synergistic effect on the degradation techniques. Ultrasonic activation at 47kHz contributes through cavitation leading to the splitting of H(2)O(2) produced by both photocatalysis and sonolysis. This results in the formation of oxidative species, such as singlet oxygen ((1)O(2)) and superoxide (O2-*) radicals in the presence of oxygen. Sonication increases the amount of reactive radical species, inducing faster oxidation of the substrate and degradation of intermediates and also the deaggregation of the photocatalyst which are responsible for the observed synergy. Further, the photocatalytic activity of RR 198 dye sensitized TiO(2) is demonstrated by the degradation of phenol under visible light and ultrasound. A comparative study using TiO(2), Hombikat UV 100 and ZnO was also carried out.     

Removal of organic matter and ammonia nitrogen from landfill leachate by ultrasound

Experiments on the removal of organic matters and ammonia nitrogen from landfill leachate by ultrasound irradiation were carried out. The effects of COD reduction and ammonia removal of power input, initial concentration, initial pH and aeration were studied. It was found that the sonolysis of organic matters proceeds via reaction with ()OH radicals; a thermal reaction also occurs with a small contribution. The rise of COD at some intervals could be explained by the complexity of organic pollutant sonolysis in landfill leachate. Ultrasonic irradiation was shown to be an effective method for the removal of ammonia nitrogen from landfill leachate. After 180 min ultrasound irradiation, up to 96% ammonia nitrogen removal efficiency can be obtained. It was found that the mechanism of ammonia nitrogen removal by ultrasound irradiation is largely that the free ammonia molecules in leachate enter into the cavitation bubbles and transform into nitrogen molecules and hydrogen molecules via pyrolysis under instant high temperature and high pressure in the cavitation bubbles.     

Adsorption kinetics of 4-chlorophenol onto granular activated carbon in the presence of high frequency ultrasound

This work describes the results of investigations carried out to examine the adsorption kinetics of 4-chlorophenol (4-CP) from aqueous solution containing tert-butyl alcohol (10%, v/v) onto granular activated carbon (GAC) in the presence of ultrasound of different high frequencies (516, 800 and 1660 kHz) and acoustic powers (15.2, 21.5, 31.1 and 38.3 W). The main objective of this study is to describe the mechanism of ultrasound-assisted adsorption rather than the enhancement of adsorption capacity. Sonochemical degradation of 4-CP was studied in the absence and presence of tert-butyl alcohol. The sonolysis of 4-CP is effectively inhibited by the addition of tert-butyl alcohol (10%, v/v) and very little 4-CP degradation occurs, indicating that little or no pyrolysis of the compound occurs. Without addition of tert-butyl alcohol, after 300 min and at 1660 kHz, the removal of 4-CP in the presence of ultrasound for an acoustic power of 38.3 W was nearly total (99%), but in the conventional method only 60% was eliminated. In this case, the removal of 4-CP by GAC in the ultrasound-assisted technique is due to both adsorption and ultrasonic degradation, but the removal by simple stirring is only due to adsorption, which makes a direct comparison unacceptable. In order to distinguish sonochemical degradation and adsorption of 4-CP onto GAC and to make an exact and practical comparison of the adsorption in the absence and presence of ultrasound, kinetic adsorption experiments were conducted using aqueous solution containing 10% (v/v) tert-butyl alcohol. The obtained results show that both adsorption rate and adsorbed amount were significantly enhanced and improved in the presence of ultrasound for all the studied frequencies and powers. The enhancement of adsorption is favored by increasing ultrasonic power. Adsorption kinetic data were modeled using the liquid-film mass transfer equation and intraparticle diffusion model. The values of the intraparticle diffusion coefficient obtained in the presence of ultrasound are greater than that obtained in the absence of ultrasound. In the initial period of adsorption, where external mass transfer is assumed to predominate, liquid-film mass transfer coefficients significantly increased by the assistance of ultrasound. These results indicate that ultrasound enhances the mass transport in the pores as well as across the boundary layer. This effect increased with increasing ultrasonic power for the three studied frequencies. The average order for the studied ultrasonic waves according to the initial adsorption rate, the intraparticle diffusion coefficient and the liquid-film mass transfer coefficient is 516 kHz>800 kHz>1660 kHz.     

Sonophotocatalytic degradation of congo red and methyl orange in the presence of TiO2 as a catalyst

A comparative study between the photocatalytic and sonophotocatalytic oxidation process of congo red was carried out using titanium dioxide as a catalyst. The effect of a number of parameters, such as the initial concentration of dye, the presence of oxygen and ultrasound, the TiO(2) crystalline structure and the amount of TiO(2), was studied using an inexpensive reactor. In the second part of this document, the oxidation and reduction processes of methyl orange was studied using the same reactor, but by changing the chemical environment in order to drive either the oxidation or the reduction reaction. The results showed, for all the cases studied, a sinergistic effect between sonolysis and photocatalysis when an ultrasonic bath of 80W was used as a source of ultrasound. On the other hand, the electrochemical experiments showed that the current densities for the oxidation process of the azodyes were higher when a conducting glass electrode covered with a thin film of TiO(2) was used as a working electrode instead of a platinum electrode, showing that the TiO(2) electrode is not passivated by the oxidation reaction.     

Ultrasonic degradation of 2:4:6 trichlorophenol in presence of TiO2 catalyst.

The degradation of trichlorophenol has been studied at different intensities of irradiation using ultrasonic horn by changing the power input to the system. Effect of presence of catalyst TiO2 and concentration of catalyst on the degradation rates has also been investigated. The rates of degradation are found to be higher at higher intensities in the absence of catalyst but reverse trend is observed in the presence of catalyst. Adsorption and desorption characteristics of trichlorophenol on TiO2 catalyst have been examined. The catalyst enhances the rates of degradation but it also adsorbs some amount of TCP during the degradation process protecting it from ultrasonic degradation. Thus it is essential to consider the adsorption and desorption kinetics to get proper estimates of the degradation rates when the rates of degradation of TCP are calculated by analyzing the residual concentration of the compound in the liquid. The degradation of the pollutant seems to take place in the liquid only and that too only after desorption of the same from the solid particles. Solid particles seem to play a physical role in the overall degradation scheme, providing additional surface cavitation.     

Investigation on the sonocatalytic degradation of acid red B in the presence of nanometer TiO2 catalysts and comparison of catalytic activities of anatase and rutile TiO2 powders

Here, the nanometer anatase and rutile titanium dioxide (TiO(2)) powders were introduced to act as the sonocatalysts during the ultrasonic degradation of azo dye-acid red B which was chosen as model compound. The ultrasound of low power was used as an irradiation source to induce TiO(2) particles performing catalytic activity. It was found that the processes of sonocatalytic degradation were different between nanometer anatase TiO(2) and nanometer rutile TiO(2). For nanometer anatase TiO(2) catalyst, the acid red B was mainly oxidated by the holes on the surface of nanometer anatase TiO(2) particles, so that the decolorization and degradation happened at the same time. For the nanometer rutile TiO(2) catalyst, the acid red B was mainly oxidated by the *OH radicals from the ultrasonic cavitation, so that the decolorization of azo bond takes place primarily, and then the degradation of naphthyl ring does. The intermediates of acid red B in the presence of nanometer anatase and rutile TiO(2) powders have been monitored by UV-vis spectra and high performance liquid chromatography (HPLC), respectively. All experiments indicated that the degradation effect of acid red B in the presence of nanometer anatase TiO(2) powder was obviously better than that in the presence of nanometer rutile TiO(2) powder. Hence, the method of sonocatalytic degradation for organic pollutants in the presence of nanometer anatase TiO(2) powder is expected to be promising as an advisable choice for the treatment of organic wastewaters in future.     

Exploring the effects of pulsed ultrasound at 205 and 616 kHz on the sonochemical degradation of octylbenzene sulfonate

Compared to continuous wave (CW) ultrasound, pulsed wave (PW) ultrasound has been shown to result in enhanced sonochemical degradation of octylbenzene sulfonate (OBS). However, pulsed ultrasound was investigated under limited pulsing conditions. In this study, pulse-enhanced degradation of OBS was investigated over a broad range of pulsing conditions and at two ultrasonic frequencies (616 and 205 kHz). The rate of OBS degradation was compared to the rate of formation of 2-hydroxyterephthalic acid (HTA) following sonolysis of aqueous terephthalic acid (TA) solutions. This study shows that sonication mode and ultrasound frequency affect both OBS degradation and HTA formation rates, but not necessarily in the same way. Unlike TA, OBS, being a surface active solute, alters the cavitation bubble field by adsorbing to the gas/solution interface of cavitation bubbles. Enhanced OBS degradation rates during pulsing are attributed to this adsorption process. However, negative or smaller pulse enhancements compared to enhanced HTA formation rates are attributed to a decrease in the high-energy stable bubble population and a corresponding increase in the transient bubble population. Therefore, sonochemical activity as determined from TA sonolysis cannot be used as a measure of the effect of pulsing on the rate of degradation of surfactants in water. Over relatively long sonolysis times, a decrease in the rate of OBS degradation was observed under CW, but not under PW conditions. We propose that the generation and accumulation of surface active and volatile byproducts on the surface and inside of cavitation bubbles, respectively, during CW sonolysis is a contributing factor to this effect. This result suggests that there are practical applications to the use of pulsed ultrasound as a method to degrade surface active contaminants in water.     

Sonophotocatalytic decomposition of water using TiO(2) photocatalyst

Sonophotocatalytic reaction is a photocatalytic reaction with ultrasonic irradiation or the simultaneous irradiation of ultrasound and light with a photocatalyst. The possibility of the effect of hybrid of sonochemical and photocatalytic reactions was examined. Liquid water was hardly decomposed to H(2) and O(2) by photocatalysis or sonolysis, independently. In order to decompose water, powdered TiO(2) photocatalyst suspended in distilled water should be simultaneously irradiated by light and ultrasound. This sonophotocatalytic reaction was effective on the decomposition of water to H(2) and O(2).     

Enhancement of heat transfer in forced convection by using dual low-high frequency ultrasound

Combined sonication with dual-frequency ultrasound has been investigated to enhance heat transfer in forced convection. The test section used for this study consists of a channel with, on one hand, heating blocks normal to the water flow, equipped with thermocouples, and, on the other hand, two ultrasonic emitters. One is facing the heating blocks, thus the ultrasonic field is perpendicular, and the second ultrasonic field is collinear to the water flow. Two types of ultrasonic waves were used: low-frequency ultrasound (25 kHz) to generate mainly acoustic cavitation and high-frequency ultrasound (2 MHz) well-known to induce Eckart’s acoustic streaming. A thermal approach was conducted to investigate heat transfer enhancement in the presence of ultrasound. This approach was completed with PIV measurements to assess the hydrodynamic behavior modifications under ultrasound. Sonochemiluminescence experiments were performed to account for the presence and the location of acoustic cavitation within the water flow. The results have shown a synergetic effect using combined low-and-high-frequency sonication. Enhancement of heat transfer is related to greater induced turbulence within the water flow by comparison with single-frequency sonication. However, the ultrasonically-induced turbulence is not homogeneously distributed within the water flow and the synergy effect on heat transfer enhancement depends mainly on the generation of turbulence along the heating wall. For the optimal configuration of dual-frequency sonication used in this work, a local heat transfer enhancement factor up to 366% was observed and Turbulent Kinetic Energy was enhanced by up to 84% when compared to silent regime.     

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.     

Intensification of sonophotocatalytic degradation of p-nitrophenol at pilot scale capacity

Sonophotocatalysis involves the use of a combination of ultrasonic irradiation, ultraviolet radiation and a semiconductor photocatalyst, which enhances the rates of chemical reactions by the formation of enhanced amounts of free radicals. In the present work, the sonophotocatalytic degradation of p-nitrophenol has been investigated using low frequency ultrasound waves (25 kHz) with an acoustic power of 1 kW and UV tube of 11 W power rating at an operating volume of 7 L. The efficacy of combination of sonochemistry and photocatalysis has been initially compared with the individual operation of sonolysis and photocatalytic oxidation. The effect of operational conditions such as the initial p-nitrophenol concentration, pH and catalyst concentration on the extent of degradation has been investigated using sonophotocatalysis. The initial concentration of the pollutant was varied in the range 10 to 100 ppm whereas pH in the range of 2.5-11 and catalyst loading in the range of 0.5-4 g/l. Intensification studies have been carried out using hydrogen peroxide and Fenton chemistry. In all the systems investigated, maximum extent of degradation (94.6%) was observed for 10 ppm of p-nitrophenol initial concentration (w/v) using combination of sonophotocatalysis and optimum quantity of H(2)O(2). Use of Fenton chemistry also plays an effective role in enhancing the extent of degradation though the concentration of additive needs to be carefully adjusted in order to get maximum beneficial effects.     

A combination of ultrasound and oxidative enzyme: sono-biodegradation of substituted phenols

Sonolysis, enzyme treatment, and a combination of the two processes were tested for the degradation of substituted phenols (phenol, p-chlorophenol, p-bromophenol, p-iodophenol, p-methoxyphenol, p-cresol and p-nitrophenol) in aqueous medium. These organic pollutants are divided into three groups according to their degradation behaviour. In group (I), p-nitrophenol, horseradish peroxidase (HRP) in presence of hydrogen peroxide had a negligible effect on its decomposition. The combined method showed the same effect as sonolysis. Therefore, it is convenient to degrade p-nitrophenol by ultrasonic waves alone. In group (II), p-methoxyphenol and p-cresol, the combined method was approximately the same as enzyme treatment. It means that, the ultrasound had a negligible effect and the enzyme treatment alone was more favourable. Phenol and its halogenated compounds (choloro, bromo and iodo) were placed in group (III) and showed different behaviour than the two mentioned cases. The combined method was more efficient than the sonolysis and enzyme treatment individually. It should be noted that the effect of enzyme on this group (III) was in the medium level in compare of the two other groups (I and II) which the enzyme had a lower and higher effects respectively.     

Study of the sonophotocatalytic degradation of basic blue 9 industrial textile dye over slurry titanium dioxide and influencing factors

The sonophotocatalytic degradation of basic blue 9 industrial textile dye has been studied in the presence of ultrasound (20 kHz) over a TiO(2) slurry employing an UV lamp (15 W, 352 nm). It was observed that the color removal efficiency was influenced by the pH of the solution, initial dye concentration and TiO(2) amount. It was found that the dye degradation followed apparent first order kinetics. The rate constant increased by decreasing dye concentration and was affected by the pH of the solution with the highest degradation obtained at pH 7. The first order rate constants obtained with sonophotocatalysis were twofold and tenfold than those obtained under photocatalysis and sonolysis, respectively. The chemical oxygen demand was abated over 80%.     

Absorption kinetics of ozone in water with ultrasonic radiation

A mathematical model was proposed to depict classical unsteady state method that was used to determine volumetric mass transfer coefficient of ozone from gaseous phase to aqueous phase during sonolysis. The rate constant of ozone self-decomposition with ultrasonic radiation, which was one of the parameters in the model, was determined with separate experiments. The results showed that self-decomposition rate constants of ozone were enhanced by ultrasound. The self-decomposition rate constant of ozone is linearly dependent on ultrasonic power, but the increase of the decomposition rate could not enhance ozone mass transfer coefficient. The volumetric mass transfer coefficients of ozone were also enhanced by ultrasonic radiation, while ultrasonic power had little effect on volumetric mass transfer coefficient of ozone. The degassing effect of ozone due to ultrasonic radiation was insignificant in the sparged system when ozone was bubbled during sonolysis.     

Sonochemical and photosonochemical degradation of 4-chlorophenol in aqueous media

The degradation of 4-chlorophenol (4-CP) in aqueous media by 516 kHz ultrasonic irradiation was investigated in order to clarify the degradation mechanism. The degradation of concentrated 4-CP solution by means of ultrasound, UV irradiation and their combined application was also studied. The obtained results indicate that *OH radical are the primary reactive species responsible for 4-CP ultrasonic degradation. Very little 4-CP degradation occurs if the sonolysis is carried out in the presence of the *OH radical scavenger tert-butyl alcohol, also indicating that little or no pyrolysis of the compound occurs. The dominant degradation mechanism is the reaction of substrate with *OH radicals at the gas bubble-liquid interface rather than high temperature direct pyrolysis in ultrasonic cavities. This mechanism can explain the lower degradation rate of the ionic form of 4-CP that is partly due to the rapid dissociation of *OH radicals in alkaline solutions. The sonochemical destruction of concentrated 4-CP aqueous solution is obtained with low rate. Coupling photolysis with ultrasound irradiation results in increased efficiency compared to the individual processes operating at common conditions. Interestingly, the photosonochemical decomposition rate constant is greater than the additive rate constants of the two processes. This may be the result of three different oxidative processes direct photochemical action, high frequency sonochemistry and reaction with ozone produced by UV irradiation of air, dissolved in liquid phase because of the geyser effect of ultrasound streaming. Additionally, the photodecomposition, at 254 nm, of hydrogen peroxide produced by ultrasound generating *OH radical can partly explain the destruction enhancement.     

声化学新发展——纳米材料的超声制备

声空化所引发的特殊的物理，化学环境为制备具有特殊性能的新型材料提供了一条重要的途径，近年来，声化学处理已成为制备纳米材料的一种十分有效的技术，文章综合介绍了超声法制备纳米材料的主要类型，其中包括超声声解法，声化学还原法，超声共沉淀法，超声微乳液法等，并着重阐述了超声的作用原理和各种方法的特点。     

激光协同聚焦超声辐照生物样品增强热效应的实验和理论研究

对中等强度聚焦超声在生物样品中产生的热效应以及激光协同超声增强热效应进行了实验和理论研究。实验上,对生物和仿生样品在超声作用和激光协同超声作用下加热情况进行测量,通过对比表明,激光协同超声作用于生物样品,引起空化效应以及温度升高更为明显。同时,理论上对聚焦超声在生物样品中衰减产生的热效应、超声空化以及激光协同超声增强空化及其产生热效应进行机理分析。通过对机理的分析表明,激光引起的光致核化使超声空化更易于产生,有效的增强空化效应,进而增强热效应。为对具体实验给出量化分析和估算,通过理论与实验结果相拟合,对超声传播引起的温度升高进行计算,并估算超声和激光协同超声产生空化微泡对加热效应的不同贡献,为空化效应在超声治疗中的贡献提供参考数据。      

Laser-enhanced thermal effects during focused ultrasound radiation on biological tissues

The thermal effects induced by a moderate intensity focused ultrasound and enhanced by combined laser pulses for bio-tissues and tissue-phantom are studied experimentally and theoretically. At first, the heating effects of bio-tissues and tissue-phantom induced by ultrasound and enhanced by laser are measured experimentally. The heating processes induced by attenuations of focused ultrasonic waves and cavitation effects of the focused ultrasound and combined laser are analyzed theoretically. By analyzing the mechanisms of these effects, it is found that the laser nucleation makes the cavitation bubble generation more easily, which can effectively enhance the ultrasonic cavitation effects, and then enhance the thermal effects of the samples. On the other hand, to evaluate quantitatively the heating processes induced by the focused ultrasound and enhanced by the pulsed laser, by fitting the theoretical calculations to the experimental results, the corresponding cavitation bubbles and rising temperatures induced by the focused ultrasound with and without laser can be estimated approximately.