Sonochemical degradation of chlorophenols in water

Sonochemical degradation of dilute aqueous solutions of 2-, 3- and 4-chlorophenol and pentachlorophenol has been investigated under air or argon atmosphere. The degradation follows first-order kinetics in the initial state with rates in the range 4.5-6.6 microM min-1 under air and 6.0-7.2 microM min-1 under argon at a concentration of 100 microM of chlorophenols. The rate of OH radical formation from water is 19.8 microM min-1 under argon and 14.7 microM min-1 under air in the same sonolysis conditions. The sonolysis of chlorophenols is effectively inhibited, but not completely, by the addition of t-BuOH, which is known to be an efficient OH radical scavenger in aqueous sonolysis. This suggests that the main degradation of chlorophenols proceeds via reaction with OH radicals; a thermal reaction also occurs, although its contribution is small. The addition of appropriate amounts of Fe(II) ions accelerates the degradation. This is probably due to the regeneration of OH radicals from hydrogen peroxide, which would be formed from recombination of OH radicals and which may contribute a little to the degradation. The ability to inhibit bacterial multiplication of pentachlorophenol decreases with ultrasonic irradiation.     

Sonochemical degradation of triclosan in water and wastewater

The sonochemical degradation of 5 μg l⁻¹ triclosan, a priority micro-pollutant, in various environmental samples (seawater, urban runoff and influent domestic wastewater) as well as in model solutions (pure and saline water) was investigated. Experiments were conducted with a horn-type sonicator operating at 80 kHz frequency and a nominal applied power of 135 W, while solid-phase microextraction coupled with gas chromatography–electron capture detector (SPME/GC–ECD) was employed to monitor triclosan degradation. The latter followed pseudo-first order kinetics with the rate constant being (min⁻¹): 0.2284 for seawater > 0.1051 for 3.5% NaCl in deionised water > 0.0597 for centrifuged urban runoff  0.0523 for untreated urban runoff > 0.0272 for deionised water > 0.0063 for wastewater influent. SPME/GC–ECD and SPME coupled with gas chromatography–mass spectrometry (SPME/GC–MS) were also used to check for the formation of chlorinated and other toxic by-products; at the conditions in question, the presence of such compounds was not confirmed.     

Sonochemical activation-assisted biosynthesis of Au/Fe3O4 nanoparticles and sonocatalytic degradation of methyl orange

In this research, a sonochemical activation-assisted biosynthesis of Au/Fe₃O₄ nanoparticles is proposed. The proposed synthesis methodology incorporates the use of Piper auritum (an endemic plant) as reducing agent and in a complementary way, an ultrasonication process to promote the synthesis of the plasmonic/magnetic nanoparticles (Au/Fe₃O₄). The synergic effect of the green and sonochemical synthesis favors the well-dispersion of precursor salts and the subsequent growth of the Au/Fe₃O₄ nanoparticles.The hybrid green/sonochemical process generates an economical, ecological and simplified alternative to synthesizing Au/Fe₃O₄ nanoparticles whit enhanced catalytic activity, pronounced magnetic properties. The morphological, chemical and structural characterization was carried out by high- resolution Scanning electron microscopy (HR-SEM), Energy Dispersive X-Ray Spectroscopy (EDS) and X-Ray diffraction (XRD), respectively. Ultraviolet–visible (UV–vis) and X-ray photoelectron (XPS) spectroscopy confirm the Au/Fe₃O₄ nanoparticles obtention. The magnetic properties were evaluated by a vibrating sample magnetometer (VSM). Superparamagnetic behavior, of the Au/ Fe₃O₄ nanoparticles was observed (M_s = 51 emu/g and H_c = 30 Oe at 300 K). Finally, the catalytic activity was evaluated by sonocatalytic degradation of methyl orange (MO). In this stage, it was possible to achieve a removal percentage of 91.2% at 15 min of the sonocatalytic process (160 W/42 kHz). The initial concentration of the MO was 20 mg L⁻¹, and the Fe3O4-Au dosage was 0.075 gL⁻¹. The MO degradation process was described mathematically by four kinetic adsorption models: Pseudo-first order model, Pseudo-second order model, Elovich and intraparticle diffusion model.     

Low frequency sonocatalytic degradation of Azo dye in water using Fe-doped zeolite Y catalyst

Sonocatalytic degradation of acid red B (ARB) dye was investigated using Fe doped zeolite Y catalysts with the assistance of low frequency (20 kHz) ultrasonic irradiation. Low concentration of Fe ions from different precursors was loaded onto the zeolite using wet impregnation method. Catalytic degradation of ARB dye was found to be accelerated by the reaction between Fe (II) and Fe (III) ions and hydrogen peroxide (H₂O₂) generated in situ by the ultrasound-mediated dissociation of water molecules. Fe (II)/Y exhibited higher degradation efficiency at the beginning of the reaction but achieved almost similar degradation at the end of the process. The increase of pH significantly decreased the degradation efficiency of ARB dye and strongly affected the leaching and catalyst stability. The highest efficiency was achieved at an initial pH of 3 with nearly 100% degradation in less than 60 min. Both catalysts showed no significant changes in terms of their mean particle sizes before and after reaction. Finally, Fe (III)/Y showed better performance evaluated based on leaching of Fe and also catalyst reusability. Only minor physical changes occurred during the degradation process for four consecutive runs of reaction.     

Eu-doped ZnO nanoparticles: Sonochemical synthesis,characterization, and sonocatalytic application

Undoped and europium (III)-doped ZnO nanoparticles were prepared by a sonochemical method. The prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS) analysis. The crystalline sizes of undoped and 3% Eu-doped ZnO were found to be 16.04 and 8.22 nm, respectively. The particle size of Eu-doped ZnO nanoparticles was much smaller than that of pure ZnO. The synthesized nanocatalysts were used for the sonocatalytic degradation of Acid Red 17. Among the Eu-doped ZnO catalysts, 3% Eu-doped ZnO nanoparticles showed the highest sonocatalytic activity. The effects of various parameters such as catalyst loading, initial dye concentration, pH, ultrasonic power, the effect of oxidizing agents, and the presence of anions were investigated. The produced intermediates of the sonocatalytic process were monitored by GC–Mass (GC–MS) spectrometry.     

Titanium-based MAX-phase with sonocatalytic activity for degradation of oxytetracycline antibiotic

In light of growing environmental concerns over emerging contaminants in aquatic environments, antibiotics in particular, have prompted the development of a new generation of effective sonocatalytic systems. In this study, a new type of nano-laminated material, Ti₂SnC MAX phase, is prepared, characterized, and evaluated for the sonocatalytic degradation of oxytetracycline (OTC) antibiotic. A variety of identification analyses, including X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectrometry, Brunauer-Emmett-Teller, and diffuse reflectance spectroscopy, were conducted to determine the physicochemical properties of the synthesized catalyst. By optimizing the operating factors, total degradation of OTC occurs within 120 min with 1 g L^-1 catalyst, 10 mg L^-1 OTC, at natural pH of 7.1 and 150 W ultrasonic power. The scavenger studies conclude that the singlet oxygen and superoxide ions are the most active species during the sonocatalytic reaction. Based on the obtained data and GC–MS analysis, a possible sonocatalytic mechanism for the OTC degradation in the presence of Ti₂SnC is proposed. The catalyst reusability within eight consecutive runs reveals the proper stability of Ti₂SnC MAX phase. The results indicate the prospect for MAX phase-based materials to be developed as efficient sonocatalysts in the treatment of antibiotics, suggesting a bright future for the field.     

Sonochemical degradation of cyclic nitroxides in aqueous solution

The sonochemical degradation of eight five- and six-membered nitroxides has been studied by EPR spectroscopy after exposure to ultrasound at a frequency of 354 kHz in argon-saturated aqueous solution. Concentration vs. time profiles do not follow a simple rate law. Octanol/water partition functions have been determined for all eight nitroxides, and an excellent linear correlation has been found between initial decomposition rates and hydrophobicity (log K(octanol/water)). Variation of initial rate with concentration was investigated for one compound (TEMPONE) and is largely consistent with an equilibrium distribution of substrate between bulk solution and the gas/liquid interface.     

Characterization and relative sonocatalytic efficiencies of a new MWCNT and CdS modified TiO2 catalysts and their application in the sonocatalytic degradation of rhodamine B

TiO₂ nanoparticles modified with MWCNTs and CdS were synthesized by the sol–gel method followed by solvothermal treatment at low temperature. The chemical composition and surface structure of the CdS/CNT–TiO₂ composites were investigated by X-ray diffraction, specific surface area measurements, energy-dispersive X-ray spectroscopy, transmission electron microscopy, and scanning electron microscopy. Then a series of sonocatalytic degradation experiments were carried out under ultrasonic irradiation in the presence of CNT/TiO₂ and the CdS/CNT–TiO₂ composites. It was found that RhB was quickly and effectively degraded under different ultrasonic conditions. As expected, the nanosized CdS/CNT–TiO₂ photocatalyst showed enhanced activity compared with the non CdS treated CNT/TiO₂ material in the sonocatalytic degradation of RhB. The sonocatalyst CCTb with 34.68% contents of Ti heat treated at 500 °C for 1 h showed the highest sonocatalytic activity. The synergistic effect of the greater surface area and catalytic activities of the composite catalysts was examined in terms of their strong adsorption ability and interphase interaction by comparing the effects of different amounts of MWCNTs and CdS in the catalysts and their roles. The mechanism of sonocatalytic degradation over the CdS/CNT modified TiO₂ composites under different ultrasonic conditions was also discussed.     

Peroxydisulfate-assisted sonocatalytic degradation of metribuzin by La-doped ZnFe layered double hydroxide

Metribuzin is an herbicide that easily contaminates ground and surface water. Herein, La-doped ZnFe layered double hydroxide (LDH) was synthesized for the first time and used for the degradation of metribuzin via ultrasonic (US) assisted peroxydisulfate (PDS) activation. The synthesized LDH had a lamellar structure, an average thickness of 26 nm, and showed mesoporous characteristics, including specific surface area 110.93 m² g⁻¹, pore volume 0.27 cm³ g⁻¹, and pore diameter 9.67 nm. The degradation efficiency of the US/La-doped ZnFe LDH/PDS process (79.1 %) was much greater than those of the sole processes, and the synergy factor was calculated as 3.73. The impact of the reactive species on the sonocatalytic process was evaluated using different scavengers. After four consecutive cycles, 10.8 % loss occurred in the sonocatalytic activity of the La-doped LDH. Moreover, the efficiency of the US/La-doped LDH/PDS process was studied with respect to the degradation of metribuzin in a wastewater matrix. According to GC–MS analysis, six by-products were detected during the degradation of metribuzin. Our results indicate that the US/La-doped ZnFe LDH/PDS process has great potential for efficient degradation of metribuzin-contaminated water and wastewater.     

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.     

Sonochemical formation of nitrate and nitrite in water

The formation of nitrite and nitrate ions in water under irradiation with 900 kHz ultrasound was studied as a function of time, temperature and gas (oxygen/nitrogen) composition. The rate decreases as temperature increases, and is below the detection limit when there is no O2 gas present. The absolute rate of formation of NOx- ions obtained (about 30 x 10(-9) mol min-1 W-1) agrees well with previous similar studies. The differences in the NO2-/NO3- ratio found between various studies can be satisfactorily explained though a mechanism where HNO2 and HNO3 are formed in the gas phase of the imploding cavity, and then dissolve in the water and dissociate to ions. The NO2- species is initially substantially favoured, as considerably more NO is formed than NO2. Thermodynamic calculations indicate that at the 'hot spot' temperature of about 5000 K believed to be present, there would very large amounts of NO and OH radicals present, and at such high temperatures, thermodynamics would be a good approximation of the situation, since the rates of reactions would be very rapid. The reaction needs O2 in order to proceed to a significant degree; no NOx- was detected in the absence of oxygen gas.     

Sonochemical degradation of martius yellow dye in aqueous solution

The sonolytic degradation of the textile dye martius yellow, also known as either naphthol yellow or acid orange 24, was studied at various initial concentrations in water. The degradation of the dye followed first-order kinetics under the conditions examined. Based on gas chromatographic results and sonoluminescence measurements of sonicated aqueous solutions of the dye, it is concluded that pyrolysis does not play a significant role in its degradation. The chromatographic identification of hydroxy added species indicates that an OH radical induced reaction is the main degradation pathway of the dye. Considering the non-volatility and surface activity of the dye, the degradation of the dye most probably takes place at the bubble/solution interface. The quantitative and qualitative formation of the degradation intermediates and final products were monitored using HPLC and ESMS. The analytical results suggest that the sonolytic degradation of the dye proceeds via hydroxylation of the aryl ring and also by C-N bond cleavage of the chromophoric ring, either through OH radical attack or through another unidentified process. The identification of various intermediates and end products also imply that the degradation of martius yellow proceeds through multiple reaction pathways. Total organic carbon (TOC) analyses of the dye solutions at various times following sonication revealed that sonolysis was effective in the initial degradation of the parent dye but very slow in achieving mineralization. The slow rate of mineralization is likely to be due to the inability of many of the intermediate products such as, the carboxylic acids, to accumulate at the bubble (air/water) interface and undergo decomposition due to their high water solubility (low surface activity).     

Sonochemical degradation of phenol in water: a comparison of classical equipment with a new cylindrical reactor

Cavitation due to ultrasonic waves produces highly reactive oxidising species in water. As a result, it can be used to oxidise organic pollutants such as aromatic compounds in dilute aqueous solutions. Recent studies have demonstrated that reactors operating in the high frequency range (e.g. 500 kHz) are more efficient than reactors working at lower frequency (20 kHz) for the destruction of these kinds of contaminants. Our study describes the degradation of phenol with the help of a cylindrical ultrasonic apparatus that operates at 35 kHz (Sonitube-SODEVA). To date, the use of this type of reactor has not been reported. The reaction rates thus obtained were compared to those obtained at the same ultrasonic power (50 W) with more classical devices operating at 20 and 500 kHz. The general result is that in aqueous solution, the rate of phenol destruction is higher at 500 kHz than at 35 or 20 kHz. Addition of hydrogen peroxide and copper sulphate to the medium provides a different oxidative system that proceeds more efficiently at 35 kHz; the time of destruction was about one-third of the time needed at 500 kHz. It was also observed that the intermediate organic compounds are eliminated much faster at 35 kHz in comparison with the two frequencies. The observation of such different behaviour is not necessarily a pure frequency effect, but can be due to a response to other parameters such as the acoustic field and intensity.     

Sonochemical degradation for toxic halogenated organic compounds.

This paper describes the degradation of p-chlorophenol using three different ultrasonic devices. The dissipated power in the reaction matrix was measured based on calorimetric method. The study showed that hydrogen peroxide can improve the sonochemical reaction and gases dissolved in reaction matrix can affect the process to a small extent. The reaction mechanism and kinetics of degradation were also investigated.     

Fe3O4@MIL-100(Fe) modified ZnS nanoparticles with enhanced sonocatalytic degradation of tetracycline antibiotic in water

Sonocatalysis has attracted excellent research attention to eradicate hazardous pollutants from the environment effectively. This work synthesised an organic/inorganic hybrid composite catalyst by coupling Fe₃O₄@MIL-100(Fe) (FM) with ZnS nanoparticles using the solvothermal evaporation method. Remarkably, the composite material delivered significantly enhanced sonocatalytic efficiency for removing tetracycline (TC) antibiotics in the presence of H₂O₂ compared to bare ZnS nanoparticles. By adjusting different parameters such as TC concentration, catalyst dosage and H₂O₂ amount, the optimized composite (20 %Fe₃O₄@MIL-100(Fe)/ZnS) removed 78.25% antibiotic in 20 min at the cost of 1 mL of H₂O₂. These much superior activities are attributed to the efficient interface contact, effective charge transfer, accelerated transport capabilities and strong redox potential for the superior acoustic catalytic performance of FM/ZnS composite systems. Based on various characterization, free radical capture experiments and energy band structures, we proposed a mechanism for the sonocatalytic degradation of tetracycline based on S-scheme heterojunctions and Fenton like reactions. This work will provide an important reference for developing ZnS-based nanomaterials to study sonodegradation of pollutants.     

Sonochemical degradation of trimethoprim in water matrices: Effect of operating conditions,identification of transformation products and toxicity assessment

The sonochemical degradation of trimethoprim (TMP), a widely used antibiotic, in various water matrices was investigated. The effect of several parameters, such as initial TMP concentration (0.5–3 mg/L), actual power density (20–60 W/L), initial solution pH (3–10), inorganic ions, humic acid and water matrix on degradation kinetics was examined. The pseudo-first order degradation rate of TMP was found to increase with increasing power density and decreasing pH, water complexity (ultrapure water > bottled water > secondary wastewater) and initial TMP concentration.TMP degradation is accompanied by the formation of several transformation products (TPs) as evidenced by LC-QToF-MS analysis. Nine such TPs were successfully identified and their time-trend profiles during degradation were followed. An in silico toxicity evaluation was performed showing that several TPs could potentially be more toxic than the parent compound towards Daphnia magna, Pimephales promelas and Pseudokirchneriella subcapitata.     

Ultrasound-engineered synthesis of WS2@CeO2 heterostructure for sonocatalytic degradation of tylosin

The main aim of the present investigation was the intercalation of WS₂ nanosheets in the structure of ceria (CeO₂) to be used for the efficient catalytic destruction of tylosin (TYL) as a macrolide antibiotic in water. As-synthesized heterostructured catalyst was placed in a sono-reactor (40 kHz and 300 W) in order to degrade TYL through the sonocatalysis. 15 wt% WS₂/CeO₂ was chosen for performing the systematic experiments. Decreasing the concentration of TYL, along with increasing the WS₂/CeO₂ dosage led to reduced degradation efficiency. The water hardness was demonstrated to be a suppressive agent on the sonocatalysis of the target pollutant. As-generated holes, OH, and also O₂⁻ were responsible for the degradation of TYL. Increasing the ultrasound power and operating temperature enhanced the degradation efficiency. The degradation rate boosted up when the temperature was raised from 10 °C (0.0107 1/min) to 40 °C (0.0165 1/min). Moreover, the lowest activation energy (E_a) for sonocatalytic degradation was obtained as 10.81 kJ/mol. The sonocatalytic activity of WS₂/CeO₂ in the sono-reactor encountered insignificant change within five consecutive operational runs (~15% reduction). The mechanism and pathways of the sonocatalytic decomposition of TYL are also proposed.     

Sonochemical degradation of ethylbenzene in aqueous solution: a product study

The degradation of ethylbenzene in aqueous solution by 520 kHz ultrasound was investigated. The products formed were analysed using solid phase microextraction (SPME), a sampling technique that allows convenient GC-MS and GC-FID analysis in the micromolar range. A broad range of monosubstituted monocyclic and dicyclic aromatic hydrocarbons was found as well as some oxygenated products. The results clearly indicate that pyrolysis is an important pathway of ethylbenzene degradation. The side chain is dehydrogenated, forming styrene, or cleaved. The radicals formed upon cleavage are subsequently added to the double bond of the styrene side chain or recombined. This mechanism explains the formation of most of the products. Formation and breakdown of the reaction products follow first-order kinetics in spite of the fact that the selectivity of the reactions depends on the initial ethylbenzene concentration considerably. Changes in the temperature and the pressure of cavitation are expected to cause this dependence.     

Sonochemical degradation of ciprofloxacin and ibuprofen in the presence of matrix organic compounds

Ciprofloxacin (CIPRO) and ibuprofen (IBU), a hydrophilic and a hydrophobic compound, respectively, were degraded by ultrasound at the frequencies of 20 and 620 kHz in aqueous solution containing matrix organic compounds. Compared to in its absence, in the presence of terephthalate (TA), a commonly used OH scavenger, CIPRO degradation was inhibited by a factor of 40–1500 depending on the frequency and initial concentration. However, the degradation rates of IBU were only reduced between 30% and 80% with TA present compared to in its absence. Similar to TA, the presence of Suwannee River Fulvic Acid (SRFA) inhibited CIPRO degradation to a greater extent than that of IBU but overall inhibition by SRFA was dramatically less than by TA. Although both TA and SRFA inhibited the degradation of CIPRO and IBU, the mechanisms of inhibition are different. TA reacts with OH in bulk solution and our evidence also indicates that it accumulates on or interacts with cavitation bubbles. On the other hand, SRFA stays in bulk solution, quenching OH and/or associating with the target compounds.     

Photocatalytic,sonocatalytic and sonophotocatalytic degradation of Rhodamine B using ZnO/CNTs composites photocatalysts

A series of ZnO nanoparticles decorated on multi-walled carbon nanotubes (ZnO/CNTs composites) was synthesized using a facile sol method. The intrinsic characteristics of as-prepared nanocomposites were studied using a variety of techniques including powder X-ray diffraction (XRD), high resolution transmission electron microscope (HR-TEM), transmission electron microscope (TEM), scanning electron microscope (SEM) with energy dispersive X-ray analysis (EDX), Brunauer Emmett Teller (BET) surface area analyzer and X-ray photoelectron spectroscopy (XPS). Optical properties studied using UV–Vis diffuse reflectance spectroscopy confirmed that the absorbance of ZnO increased in the visible-light region with the incorporation of CNTs. In this study, degradation of Rhodamine B (RhB) as a dye pollutant was investigated in the presence of pristine ZnO nanoparticles and ZnO/CNTs composites using photocatalysis and sonocatalysis systems separately and simultaneously. The adsorption was found to be an essential factor in the degradation of the dye. The linear transform of the Langmuir isotherm curve was further used to determine the characteristic parameters for ZnO and ZCC-5 samples which were: maximum absorbable dye quantity and adsorption equilibrium constant. The natural sunlight and low power ultrasound were used as an irradiation source. The experimental kinetic data followed the pseudo-first order model in photocatalytic, sonocatalytic and sonophotocatalytic processes but the rate constant of sonophotocatalysis is higher than the sum of it at photocatalysis and sonocatalysis process. The sonophotocatalysis was always faster than the respective individual processes due to the more formation of reactive radicals as well as the increase of the active surface area of ZnO/CNTs photocatalyst. Chemical oxygen demand (COD) of textile wastewater was measured at regular intervals to evaluate the mineralization of wastewater.