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Ultrasonic systems must be able to produce an acoustic field with the highest possible energy concentration in sonochemical reactors to accomplish maximum efficacy in the sonolytic degradation of water contaminants. In the present study, the impact of cylindrical and conical stainless-steel reflectors placed on the liquid surface on the sonochemical oxidation activity of ultrasonication reactors was investigated. The amount of effective acoustic power transferred to the ultrasonicated medium without and with reflectors was measured by calorimetric characterization of the sono-reactors at diverse ultrasonication frequencies in the interval of 300-800 kHz and different electrical powers in the range of 40-120 W. Iodide dosimetry without and with reflectors at diverse ultrasonication conditions (300-800 kHz and 40-120 W) and various aqueous solution volumes in the range of 300-500 mL was used to assess the sonochemical oxidation activity, i.e., the generation of oxidative species (mainly hydroxyl radicals). Sonochemiluminescence (SCL) imaging was used to study the active acoustic cavitation bubbles distribution in the sono-reactors without and with reflectors. Significant impacts of the position and shape of the reflectors on the active acoustic cavitation bubble distribution and the sonochemical oxidation activity were observed due to remarkable modifications of the ultrasonic field by directing and focusing of the ultrasonic waves. A significant augmentation in the triiodide formation rate was obtained in the presence of the conical reflector, especially at 630 kHz and 120 W (60.5% improvement), while iodide oxidation was quenched in the presence of the cylindrical reflector at all ultrasonication frequencies and powers. The SCL images show a noteworthy modification in the ultrasonic field and the acoustic cavitation bubble population when reflectors were used. The sonochemical oxidation activity was improved by the conical reflector when placed in the Fresnel zone (near field region)., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Author(s). Published by Elsevier B.V. All rights reserved.)

There is a lack of literature on peroxynitrite formation due to sonolysis of aerated water. In this work, the impact of sonication parameters, frequency and power, on ultrasonic peroxynitrite production in aerated alkaline water was investigated. Peroxynitrite formation was clearly established with undeniable evidence at all the tested frequencies in the range of 516-1140 kHz with a typical G-value (energy-specific yield) of 0.777 × 10 -10 , 0.627 × 10 -10 , 0.425 × 10 -10 and 0.194 × 10 -10 mol/J at 516, 558, 860 and 1140 kHz, respectively. The ultrasonication frequency has a direct impact on the sonochemical peroxynitrite production. Increasing the ultrasonication frequency in the interval 321-1140 kHz reduces peroxynitrite formation. The most practical sonochemistry dosimetries, including hydrogen peroxide production, triiodide dosimetry, Fricke dosimetry, and 4-nitrocatechol formation, were compared with the sonochemical efficiency of the reactors used to produce peroxynitrite. The G-value, energy specific yield, for the tested dosimetries was higher than that for peroxynitrite formation, regardless of frequency. For all chemical dosimetries investigated, the same trend of frequency dependence was found as for peroxynitrite generation. The influence of ultrasonication power on peroxynitrite formation by sonication at diverse frequencies in the interval 585-1140 kHz was studied. No peroxynitrite was formed at lower acoustic power levels, regardless of frequency. As the frequency increases, more power is required for peroxynitrite formation. The production of peroxynitrite increased as the acoustic power increased, despite the frequency of ultrasonic waves. Ultrasonic power is a key factor in the production of peroxynitrite by sonolysis. Since peroxynitrite is uniformly distributed in the bulk solution, peroxynitrite-sensitive solutes can be transformed both in the bulk of the solution and in the surfacial region (shell) of the cavitation bubble. The formation of peroxynitrite should be taken into account in sonochemistry, especially at higher pH values. Ultrasonic peroxynitrite formation in alkaline solution (pH 12) can be considered as a kind of chemical dosimetry in sonochemistry., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Author(s). Published by Elsevier B.V. All rights reserved.)

This work explores the effect of persulfate (PS) on the sonochemical degradation of organic pollutants taking naphthol blue black (NBB), an anionic diazo dye, as a substrate model. The sonolytic experiments were conducted in the absence and presence of PS under various experimental conditions including acoustic power (10-80W), frequency (20 and 585kHz) and saturating gas (argon, air and nitrogen). Experimental results showed that PS decomposition into sulfate radical (SO 4 - ) takes place by sonolysis and increasing PS concentration up to 1g/L would result in an increase in the NBB degradation rate. It was found that the PS-enhanced effect was strongly operating parameters dependent. The positive effect of PS decreased with increasing power and the best enhancing effect was obtained for the lowest acoustic power. Correspondingly, the PS-enhanced effect was more remarkable at low frequency (20kHz) than that observed at high frequency ultrasound (585kHz). Nitrogen saturating gas gave the best enhanced effect of PS than argon and air atmospheres. Theoretical (computer simulation of bubble collapse) and experimental measurements of the yields of free radical generation under the different experimental conditions have been made for interpreting the obtained effects of PS on the sonochemical degradation of the dye pollutant. The experimental findings were attributed to the fact that radical-radical recombination reactions occur at faster rate than the radical-organic reaction when the concentration of free radicals is too high (at higher sonochemical conditions)., (Copyright © 2016 Elsevier B.V. All rights reserved.)

In this study, we attempt for the first time to couple sonication and photo-Fenton for bacterial inactivation of secondary treated effluent. Synthetic wastewater was subjected to sequential high-frequency/low power sonication, followed by mild photo-Fenton treatment, under a solar simulator. It was followed by the assessment of the contribution of each component of the process (Fenton, US, hv) towards the removal rate and the long-term survival; sunlight greatly improved the treatment efficiency, with the coupled process being the only one to yield total inactivation within the 4-h period of treatment. The short-term beneficial disinfecting action of US and its detrimental effect on bacterial survival in long term, as well as the impact of light addition were also revealed. Finally, an investigation on the operational parameters of the process was performed, to investigate possible improvement and/or limitations of the coupled treatment; 3 levels of each parameter involved (hydraulic, environmental, US and Fenton) were tested. Only H2O2 increased improved the process significantly, but the action mode of the joint process indicated potential cost-effective solutions towards the implementation of this method., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Nano-sized starch particles (NSP) were prepared from starch granules using a purely physical method of high-intensity ultrasonication. Particle size distribution, Field Effect Scanning Electron Microscopy (FE-SEM), Raman spectroscopy, and Wide-Angle X-ray Diffraction (WAXD) were used to characterize the morphology and crystal structure of the ensuing nanoparticles. The results revealed that ultrasound treatment of the starch suspension in water and at low temperature for 75 min results in the formation of starch nanoparticles between 30 and 100 nm in size. An attempt to explain the generation of starch nanoparticles was made on the basis of WAXD, Raman analysis and FE-SEM observation. Compared to acid hydrolysis, which is the most commonly adopted process, the present approach has the advantage of being quite rapid, presenting a higher yield and not requiring any chemical treatment., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Low-frequency ultrasound (LFUS) irradiation induces morphological, optical and surface changes in the commercial nano-TiO(2)-based photocatalyst, Evonik-Degussa P-25. Low-temperature electron spin resonance (ESR) measurements performed on this material provided the first experimental evidence for the formation of oxygen vacancies (V(o)), which were also found responsible for the visible-light absorption. The V(o) surface defects might result from high-speed inter-particle collisions and shock waves generated by LFUS sonication impacting the TiO(2) particles. This is in contrast to a number of well-established technologies, where the formation of oxygen vacancies on the TiO(2) surface often requires harsh technological conditions and complicated procedures, such as annealing at high temperatures, radio-frequency-induced plasma or ion sputtering. Thus, this study reports for the first time the preparation of visible-light responsive TiO(2)-based photocatalysts by using a simple LFUS-based approach to induce oxygen vacancies at the nano-TiO(2) surface. These findings might open new avenues for synthesis of novel nano-TiO(2)-based photocatalysts capable of destroying water or airborne pollutants and microorganisms under visible light illumination., (Copyright © 2011 Elsevier B.V. All rights reserved.)

The Molybdate-catalyzed bromination of various aromatic compounds in the presence of KBr/H(2)O(2) in an aqueous/chloroform biphasic system occurred under ultrasonic irradiation, whereas the reaction did not take place under conventional mechanical stirring (1400 rpm). The sonochemical activation was found to be of secondary effect, attributed to lowering pH by sonolysis of CHCl(3)-H(2)O solvents mixture., (Copyright © 2010 Elsevier B.V. All rights reserved.)

This work deals with the ultrasonic degradation (800 kHz) of crystal violet (CV) under different experimental conditions. The effects of saturating gas (argon, carbon dioxide and air), CV concentration (2.45-1225 μmol L(-1)), pH (3-9) and power (20-80 W) were evaluated. The best performances were obtained at 80 W with argon as a saturating gas. The pH had no significant effect. The influence of several water matrices containing anions (chloride, sulphate and bicarbonate) and cations (Fe(2+)) on the sonolytic degradation of CV was also investigated. Significant differences were not observed with the presence of chloride and sulphate. However, at relatively low pollutant concentration (2.45 μmol L(-1)) bicarbonate showed a particular effect: a high bicarbonate concentration (350 mmol L(-1)) produced a detrimental effect, while a low bicarbonate concentration (3 mmol L(-1)) increased the efficiency of the process. The presence of Fe(2+) (1 mmol L(-1)) also increased the CV (49 μmol L(-1)) degradation by 32% after 180 min. Analyses of intermediates by GC-MS led to the identification of several sonochemical by-products: N,N-dimethylaminobenzene, 4-(N,N-dimethylamino)-4'-(N',N'-dimethylamino)benzophenone, and N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane. The presence of these aromatic structures showed that the main ultrasonic CV degradation pathway is linked to the reaction with *OH radicals. At the end of the treatment, these early products were converted into biodegradable organic by-products which could be easily treated in a subsequent biological treatment., (Copyright © 2010 Elsevier B.V. All rights reserved.)

Sonochemical degradation of phenol (Ph), 4-isopropylphenol (4-IPP) and Rhodamine B (RhB) in aqueous solutions was investigated for a large range of initial concentrations in order to analyze the reaction kinetics. The initial rates of substrate degradation and H(2)O(2) formation as a function of initial concentrations were determined. The obtained results show that the degradation rate increases with increasing initial substrate concentration up to a plateau and that the sonolytic destruction occurs mainly through reactions with hydroxyl radicals in the interfacial region of cavitation bubbles. The rate of H(2)O(2) formation decreases with increasing substrate concentration and reaches a minimum, followed by almost constant production rate for higher substrate concentrations. Sonolytic degradation data were analyzed by the models of Okitsu et al. [K. Okitsu, K. Iwasaki, Y. Yobiko, H. Bandow, R. Nishimura, Y. Maeda, Sonochemical degradation of azo dyes in aqueous solution: a new heterogeneous kinetics model taking into account the local concentration OH radicals and azo dyes, Ultrason. Sonochem. 12 (2005) 255-262.] and Seprone et al. [N. Serpone, R. Terzian, H. Hidaka, E. Pelizzetti, Ultrasonic induced dehalogenation and oxidation of 2-, 3-, and 4-chlorophenol in air-equilibrated aqueous media. Similarities with irradiated semiconductor particulates, J. Phys. Chem. 98 (1994) 2634-2640.] developed on the basis of a Langmuir-type mechanism. The five linearized forms of the Okitsu et al.'s equation as well as the non-linear curve fitting analysis method were discussed. Results show that it is not appropriate to use the coefficient of determination of the linear regression method for comparing the best-fitting. Among the five linear expressions of the Okitsu et al.'s kinetic model, form-2 expression very well represent the degradation data for Ph and 4-IPP. Non-linear curve fitting analysis method was found to be the more appropriate method to determine the model parameters. An excellent representation of the experimental results of sonolytic destruction of RhB was obtained using the Serpone et al.'s model. The Serpone et al.'s model gives a worse fit for the sonolytic degradation data of Ph and 4-IPP. These results indicate that Ph and 4-IPP undergo degradation predominantly at the bubble/solution interface, whereas RhB undergoes degradation at both bubble/solution interface and in the bulk solution., ((c) 2010 Elsevier B.V. All rights reserved.)

This paper explores the degradation of a model pollutant, bisphenol A, by an advanced oxidation process that combines sonolysis, Fe(2+), and TiO(2) in a photoassisted process. Experiments were done under saturated oxygen conditions. The effect of different Fe(2+) (0.56 and 5.6 mg/L) and TiO(2) (10 and 50 mg/L) concentrations was investigated on both the elimination and mineralization of the pollutant. A pronounced synergistic effect that led to the complete and rapid elimination of dissolved organic carbon (DOC) was observed even at low catalyst loadings. In this system, almost a complete removal of DOC (93%) was observed after 4 h using 10 and 5.6 mg/L of TiO(2) and Fe(2+), respectively, whereas at the same time, only 5, 6, and 22% of DOC was removed by an individual process alone (TiO(2) photocatalysis, ultrasound, and photo-Fenton, respectively). In this system, ultrasound has the principal role of eliminating the initial substrate and providing hydrogen peroxide for the photocatalytic systems, while photo-Fenton and TiO(2) photocatalysis are mainly responsible for the transformation of the intermediates in CO(2) and H(2)O. The role of H(2)O(2) generated from the sonochemical process is also discussed., (Copyright (c) 2009 Elsevier Ltd. All rights reserved.)

The influence of bicarbonate and carbonate ions on sonolytic degradation of cationic dye, Rhodamine B (RhB), in water was investigated. As a consequence of ultrasonic cavitation that generates .OH radicals, carbonate radicals were secondary products of water sonochemistry when it contains dissolved bicarbonate or carbonate ions. The results clearly demonstrated the significant intensification of sonolytic destruction of RhB in the presence of bicarbonate and carbonate, especially at lower dye concentrations. Degradation intensification occurs because carbonate radicals sonochemically formed undergo radical-radical recombination at a lesser extent than hydroxyl radicals. The generated carbonate radicals are likely able to migrate far from the cavitation bubbles towards the solution bulk and are suitable for degradation of an organic dye such as RhB. Therefore, at low dye concentrations, carbonate radical presents a more selective reactivity towards RhB molecules than hydroxyl radical. In the presence of bicarbonate, degradation rate reached a maximum at 3 g L(-1) bicarbonate, but subsequent addition retards the destruction process. In RhB solutions containing carbonate, the oxidation rate gradually increased with increasing carbonate concentration up to 10 g L(-1) and slightly decreased afterward. Carbonate radicals sonochemically generated are suitable for total removal of COD of sonicated RhB solutions., ((c) 2009 Elsevier B.V. All rights reserved.)

The aim of this work was to study the emulsification assisted by ultrasonic probe (22.5kHz) and investigate the removal of copper(II) ions from aqueous solution using water-in-oil-in-water (W/O/W) emulsion liquid membrane process (ELM). The membrane was prepared by dissolving the extractant bis(2-ethylhexyl)phosphoric acid (D2EHPA) and the hydrophobic surfactant sorbitan monooleate (Span 80) in hexane (diluent). The internal phase consisted of an aqueous solution of sulfuric acid. Effects of operating parameters such as emulsification time, ultrasonic power, probe position, stirring speed, carrier (D2EHPA) and surfactant (Span 80) concentrations volume ratios of organic phase to internal striping phase and of external aqueous phase to membrane (W/O) phase, internal phase concentration and choice of diluent on the membrane stability were studied. With ultrasound, the W/O emulsion lifetime were much higher than those reported previously by mechanical agitation. The effect of carrier and Cu(II) initial concentration on the extraction kinetics was also investigated. Nearly all of the Cu(II) ions present in the continuous phase was extracted within a few minutes. Additionally, the influence of H(2)SO(4) concentration on the stripping efficiency was examined.

Sonochemical elimination of organic pollutants can take place through two degradation pathways. Molecules with relatively large Henry's law constants will be incinerated inside the cavitation bubble, while nonvolatile molecules with low Henry's law constants will be oxidised by the OH(*) ejected from the bubble of cavitation. Taking bisphenol-A as a model pollutant, this study points out an alternate degradation route, mediated by bicarbonate ions, which is significant for the elimination of micro-pollutants at concentrations present in natural waters. In this process, OH(*) radicals react with bicarbonate ions to produce the carbonate radical, which, unlike the OH(*) radical, can migrate towards the bulk of the solution and therefore induce the degradation of the micro-pollutants present in the bulk solution. As a consequence, initial degradation rate is increased by a factor 3.2 at low concentration of bisphenol-A (0.022 micromol l(-1)) in presence of bicarbonate in water.

Degradation of the biorecalcitrant pharmaceutical micropollutant ibuprofen (IBP) was carried out by means of several advanced oxidation hybrid configurations. TiO(2) photocatalysis, photo-Fenton and sonolysis - all of them under solar simulated illumination - were tested in the hybrid systems: sonophoto-Fenton (FS), sonophotocatalysis (TS) and TiO(2)/Fe(2+)/sonolysis (TFS). In the case of the sonophoto-Fenton process, the IBP degradation (95%) and mineralization (60%) were attained with photo-Fenton (FH). The presence of ultrasonic irradiation slightly improves the iron catalytic activity. On the other hand, total removal of IBP and elimination of more than 50% of dissolved organic carbon (DOC) were observed by photocatalysis with TiO(2) in the presence of ultrasound irradiation (TS). In contrast only 26% of mineralization was observed by photocatalysis with H(2)O(2) (TH) in the absence of ultrasound irradiation. Additional results showed that, in the TFS system, 92% of DOC removal and complete degradation of IBP were obtained within 240 min of treatment. The advanced oxidation hybrid systems seems to be a promising alternative for full elimination/mineralization for the recalcitrant micro-contaminant IBP.

This work presents the application of experimental design for the ultrasonic degradation of alachlor which is pesticide classified as priority substance by the European Commission within the scope of the Water Framework Directive. The effect of electrical power (20-80W), pH (3-10) and substrate concentration (10-50mgL(-1)) was evaluated. For a confidential level of 90%, pH showed a low effect on the initial degradation rate of alachlor; whereas electrical power, pollutant concentration and the interaction of these two parameters were significant. A reduced model taking into account the significant variables and interactions between variables has shown a good correlation with the experimental results. Additional experiments conducted in natural and deionised water indicated that the alachlor degradation by ultrasound is practically unaffected by the presence of potential *OH radical scavengers: bicarbonate, sulphate, chloride and oxalic acid. In both cases, alachlor was readily eliminated ( approximately 75min). However, after 4h of treatment only 20% of the initial TOC was removed, showing that alachlor by-products are recalcitrant to the ultrasonic action. Biodegradability test (BOD5/COD) carried out during the course of the treatment indicated that the ultrasonic system noticeably increases the biodegradability of the initial solution.

The application of ultrasound (US) waves for remediation of wastewater is an area of increasing interest and promising results. The aim of this paper is to evaluate the influence of several parameters of the US process on the degradation of ibuprofen (IBP), a widely used non-steroidal anti-inflammatory recalcitrant drug found in water. Applied US power, dissolved gas, pH and initial concentration of IBP were the parameters investigated under sonication (300 kHz). Ultrasound increased the degradation of IBP from 30 to 98% in 30 min. Initial rate of IBP degradation was evaluated in the range of 1.35 and 6.1 micromolL(-1)min(-1) for initial concentrations of 2 to 21 mgL(-1) or 9.7 micromolL(-1) to 101 micromolL(-1), respectively. Under air and oxygen the degradation rate of IBP was 4 micromolL(-1)min(-1) being higher than that when argon was used. The most favorable degradation pH was acidic media. Complete removal of IBP was achieved but some dissolved organic carbon (DOC) remained in solution showing that long-lived intermediates were recalcitrant to the US irradiation. However, chemical and biological oxygen demands (COD and BOD(5)) indicated that the process oxidize the ibuprofen compound to biodegradable substances removable in a subsequent biological step.

Bisphenol A (BPA), a chemical compound largely used in the plastics industry, can end up in aquatic systems, which it disturbs by its endocrine disrupting effect (EDE). This study investigated the BPA degradation upon ultrasonic action under different experimental conditions. The effect of saturating gas (oxygen, argon and air), BPA concentration (0.15-460 micromol L(-1)), ultrasonic frequency (300-800 kHz) and power (20-80 W) were evaluated. For a 118 micromol L(-1)-BPA solution, with the best performance obtained at 300 kHz, 80 W, with oxygen as saturating gas. In these conditions, BPA can be readily eliminated by the ultrasound process (approximately 90 min). However, even after long ultrasound irradiation times (9 h), more than 50% of chemical oxygen demand (COD) and 80% of total organic carbon (TOC) remained in the solution. Analyses of intermediates using HPLC-MS investigation identified several products: monohydroxylated bisphenol A, 4-isopropenylphenol, quinone of monohydroxylated bisphenol A, dihydroxylated bisphenol A, quinone of dihydroxylated bisphenol A, monohydroxylated-4-isopropenylphenol and 4-hydroxyacetophenone. The presence of these hydroxylated aromatic structures showed that the main ultrasonic BPA degradation pathway is related to the reaction of BPA with the *OH radical. After 2h, these early products were converted into biodegradable aliphatic acids.

Bisphenol A (BPA), a xenobiotic that exhibits endocrine disrupting action can be found in surface water. Its complete elimination can be obtained by advanced oxidation processes, notably upon the application of ultrasonic waves. In order to evaluate the feature of ultrasound relevance and the involvement of the hydroxyl radical in the BPA sonochemical degradation, ultrasound action was compared to Fenton's reaction in the cases of deionised acidic water (pH 3) and natural water (pH 7.6, main ions concentration: Ca(2+)=486mgL(-1), Na(+)=9.1mgL(-1), Cl(-)=10mg L(-1), SO(4)(2-)=1187mgL(-1), HCO(3)(-)=402mgL(-1)). Ultrasound was performed at 300kHz and 80W. Fenton's process was operated using ferrous sulphate (100micromolL(-1)) and continuous H(2)O(2) addition at the rate as it is produced when sonication is applied in water in absence of substrate. Experiments carried out in deionised water show that both processes exhibit identical BPA elimination rate and identical primary intermediates. Main chemical pathways involve reactions with OH radical. Chemical oxygen demand (COD) and total organic carbon (TOC) analyses show that the Fenton's process is slightly more efficient than ultrasonic treatment for the removal of BPA by-products in the case of deionised water. Experiments conducted in natural water evidenced the inhibition of the Fenton process while the ultrasound action was not hampered.

Acoustic cavitation, induced by ultrasound, can be used to eliminate organic pollutants from water. This type of ultrasonic treatment of polluted water can be grouped with those generally referred to as advanced oxidative processes since it involves hydroxyl radicals. In this case these highly active species are generated from the dissociation of water and oxygen dissociation caused by cavitation bubble collapse. The cavitation induced degradation rates of organic compounds in water are mainly linked to their vapor pressure and solubility and here we will further explore these links by examining the degradation of a mixture of two materials with different physical properties, chlorobenzene and 4-chlorophenol. The results obtained when a dilute solution of a mixture of these compounds saturated with argon is subjected to sonication at 300 kHz, parallels previous observations achieved in an aerated aqueous medium at 500 kHz. The two compounds exhibit sequential degradation with the more volatile chlorobenzene entering the cavitation bubble and being destroyed first. The 4-chlorophenol degradation occurs subsequently only when the chlorobenzene has been completely destroyed. The two compounds exhibit different behavior when sonicated in water saturated with oxygen. Under these conditions the two compounds are degraded simultaneously, a remarkable result for which two explanations can be proposed, both of which are based on the formation of additional OH radical species: The ability to produce conditions for the simultaneous elimination of two organic compounds by the use of oxygen is of great importance in the developing field of ultrasonic water treatment.

Bisphenol A (BPA), an organic compound largely used in the plastic industry as a monomer for production of epoxy resins and polycarbonate, is an emerging contaminant that is released in the environmentfrom bottles and packaging. BPA degradation (118 micromol L(-1)) under sonochemical conditions was investigated in this study, using a 300 kHz frequency, with a 80 W electrical power. Under these conditions, BPA was eliminated by the ultrasound process (-90 min). However, even after long ultrasound irradiation periods (10 h), more than 50% of chemical oxygen demand (COD) and 80% of total organic carbon (TOC) remained in the solution, indicating that most BPA intermediates are recalcitrant toward ultrasonic action. Accumulation of hydrogen peroxide from *OH and *OOH radical recombination was also observed. To increase the efficiency of BPA treatment, experiments combined ultrasound with Fe2+ (100 micromol L(-1)) and/or UV radiation (254 nm): Ultrasound/UV; Ultrasound/Fe2+; Ultrasound/UV/ Fe2+. Both UV and Fe2+ induced hydrogen peroxide dissociation, leading to additional *OH radicals and complete COD and TOC removal. Thus difficulties in obtaining mineralization of micropollutants like BPA through ultrasonic action alone, can be overcome by the Ultrasound/UV/ Fe2+ combination. Moreover, this technique was found to be the most cost-effective one. So, the integrated ultrasound-UV-iron(ll) process was shown to be of interest for the treatment of wastewaters contaminated with BPA.

Sono-degradation and sono-enzyme degradation of phenols were performed on the mixtures of double compounds (phenol, p-chlorophenol; phenol, p-cresol; phenol, p-nitrophenol; and p-chlorophenol, p-cresol) in aqueous medium. Sono-degradation of phenol and its substituted compounds individually behaved approximately the same, but in the case of mixture behaved differently. Sono-degradation of substituted phenols was easier than phenol in a mixture, but there was an exception in the combination of phenol and p-nitrophenol that the degradation of phenol was faster than substituted compound. This behavior was the same in sono-enzyme degradation, but with higher degradation rate. Between these mixtures, the combination of phenol and p-cresol presented a significant different behavior in case of single and double compounds solutions. In this system, the sono-degradation of phenol in mixture was more difficult than phenol alone but, the sono-degradation of p-cresol in mixture was easier in comparison with p-cresol alone. In sono-enzyme degradation, p-cresol as a more reactive compound facilitated the remove of phenol in mixture in compare of the individual case.

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.

Multibubble sonoluminescence spectra were recorded in the 300-350 nm wavelength range in the case of H(2)O/Ar, D(2)O/Ar and H(2)O/Kr solutions (acoustic frequency: 20 kHz; spectral resolution optimized to 0.34 nm). Three groups of rotational components (R(1)/R(2), Q(1)/Q(2) and P(1)/P(2)) were identified in the OH/D A2sigma(+)-X2pi(i) (0,0) transitions via the substitution of H(2)O for D(2)O. The congestion of bands and the origin of a red shading extending up to 350 nm are broached.

The aim of this work is the evaluation of the effects of ultrasound on p-chlorophenol adsorption-desorption on granular activated carbon. Adsorption equilibrium experiments and batch kinetics studies were carried out in the presence and the absence of ultrasound at 21 kHz. Results indicate that the adsorption of p-chlorophenol determined in the presence of ultrasound is lower than the adsorption observed in the absence of ultrasound. Desorption of p-chlorophenol from activated carbon with and without the application of ultrasound was studied. The desorption rates were favoured by increased ultrasound intensity. This rise is more noticeable as temperature increases. The addition of ethanol or NaOH to the system causes an enhancement of the amount of p-chlorophenol desorbed, especially in the presence of ultrasound. A synergetic enhancement of the desorption rate was observed when ultrasonic irradiation was coupled with ethanol chemical regeneration.

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.

Ultrasonic decompositions of chlorobenzene (ClBz), 1,4-dichlorobenzene and 1-chloronaphthalene were investigated at 500 kHz in order to gain insight into the kinetics and mechanisms of the decomposition process. The disappearance of ClBz on sonication is almost simultaneously accompanied by the release of chloride ions as a result of the rapid cleavage of carbon-chlorine bonds with a concomitant release of CO, C2H2, CH4 and CO2. The intermediates resulting from attack of HO. radicals were detected but in a quite low yield (less than 2 microM). The generation of H2O2 on sonolysis is not significantly affected by the presence of aqueous ClBz while the generation of NO2- and NO3- is inhibited initially due to the presence of ClBz which diffuses into the gas-bubble interfaces and inhibits the interactions between free radicals and nitrogen. Moreover, brown carbonaceous particles are present throughout the ultrasonic irradiation process, which are consistent with soot formation under pyrolytic conditions. These important features suggest that, at the relatively high initial substrate concentrations used in this study, ultrasonic degradation of ClBz takes place predominantly both within the bubbles and within the liquid-gas interfaces of bubbles where it undergoes high-temperature combustion. Under these conditions, the oxidation of ClBz by free radical HO. outside of bubbles is a minor factor (though results of recent studies suggest that attack by HO. is more important at lower initial substrate concentrations). The sonochemical decomposition of volatiles follows pseudo-first-order reaction kinetics but the degradation rates are affected by operating conditions, particularly initial substrate concentration and ultrasonic intensity.

Solid-phase micro-extraction has been used for identifying, quantifying and following the evolution of intermediate products of octanol degradation by two advanced oxidation treatments (AOTs), photocatalytic and ultrasound processes, inducing mainly the same active species. Headspace extraction enabled direct extraction of the organic compounds in a heterogeneous process like photocatalysis. The presence of a solid does not affect the extraction percentage of alkanes, alkenes and aldehydes while alcohols and carboxylic acids are not completely extracted if the extraction time is too short. To extract C3-C8 alkanes, alkenes and aldehydes a Carboxen/PDMS fiber and an extraction time of 25 min are used. The presence of alcohol and carboxylic acids requires the use of the presence of salt under acidic conditions, a longer extraction time and a polyacrylate fiber (PA), having a polar fiber. The in situ derivatization--pyrenyldiazomethane on a PA fiber--increases the carboxylic acid extraction containing smaller hydrocarboned chain while diazomethane derivatization is not as efficient due to its volatility. Whatever be the treatment, photocatalysis or ultrasound processes, aldehydes are the main intermediate products, which is not surprising since the same oxidation species (HO2(o), O2(o-), OH(o)) are formed. Alkanes and alkenes are also detected in both processes; however, alkane formation is more important in photocatalysis while alkenes are formed in higher amounts by ultrasound. Moreover, the presence of carboxylic acids in more important amounts by ultrasound than by photocatalysis is attributed to the presence of holes (h+) in photocatalysis which induces photo-Kolbe degradation. The sonochemical formation of small-chained dienes and alkynes is probably due to pyrolysis of hydrophobic compounds in cavitation bubbles.

The sonolysis of 4-nitrophenol (4-NP) and aniline in O2-saturated aqueous solutions was performed at 610 kHz with ultrasonic power of 25 W and aqueous temperature of 15 +/- 1 degrees C. The initial rate of degradation of both 4-NP and aniline in sonolysis of aqueous media follows pseudo-first-order reaction kinetics. Investigation of the H2O2 generation rate in phosphate buffer media (0.01 M) over the range of pH 2-9 revealed a maximum yield at pH approximately 3.2. The pH, which results in modification of the physical properties (including charge) of molecules with ionisable functional groups, plays an important role in the sonochemical degradation of chemical contaminants. For hydrophilic substrates, the neutral species more easily diffuse to and accumulate at the hydrophobic interface of liquid-gas bubbles in comparison with their corresponding ionic forms. As a consequence, the degradation rate of 4-NP under ultrasonic irradiation decreases with increasing pH. In contrast, the disappearance rate of aniline exhibits a maximum under alkaline conditions due to the high solubility of the ionic anilinium ion and the (potentially) preferential movement of the uncharged form to the interface. Additionally, the rate of reaction of the uncharged aniline molecule (which dominates at pH > 4.6) with hydroxyl radicals is reported to be about three times as fast as the rate of reaction of the cationic anilinium species.

Organic compounds in aqueous solution submitted to an ultrasonic irradiation behave differently according to their physical and chemical properties. In this work, hydrogen peroxide formation and the degradation rate of phenol and carbon tetrachloride have been studied at different frequencies: 20, 200, 500 and 800 kHz. Whatever the frequency, it is easier to decompose CCl4 than phenol by means of ultrasonic wave. It is shown that the rates of reactions involving hydroxyl radicals (hydrogen peroxide formation and phenol degradation) have a maximum value at 200 kHz. The best yield observed at 200 kHz for the phenol degradation may be the result of better HO radicals availability outside of the bubble of cavitation. The degradation rate for carbon tetrachloride which decomposes into the bubble of cavitation increases with frequency. Calculating the reaction rate for one ultrasonic period shows that the efficiency of one ultrasonic cycle decreases as frequency increases.