Sonochemical degradation of PAH in aqueous solution. Part I: monocomponent PAH solution

The sonolysis of selected monocomponent PAH aqueous solution is studied at 20 and 506 kHz in the microg l(-1) range. The highest activity observed at 506 kHz, compared to 20 kHz, is tentatively explained by examination of the physical characteristics of bubbles (size and life-time) as well as by the calculation of the number of bubble at both frequency (5 x 10(3)bubbles l(-1) at 20 kHz and 4.5 x 10(9)bubbles l(-1) at 506 kHz). It is demonstrated that the main mechanism of sonodegradation is the pyrolysis of PAHs in the heart of the cavitation bubbles, and that a possible PAH oxidation by means of HO degrees appears as a minor way, since gaseous byproducts such as CO, CO2, C2H2 and CH4 have been detected. Correlations have been found by examination of kinetic variations in terms of the physical-chemical properties of PAHs. The rate constants of PAH degradation increase when the water solubility, the vapour pressure and the Henry's law constant increase.     

Sonolysis of aqueous 4-nitrophenol at low and high pH

The sonolysis of 4-nitrophenol in argon-saturated aqueous solution has been studied at 321 kHz. In order to evaluate separately the effect of OH radicals that are formed in the cavitational bubble and part of which react in the aqueous phase with this substrate, radiolytic studies in N2O-saturated solutions were carried out for comparison. A detailed product study of the sonolysis of 4-nitrophenol solutions shows that at pH 10, where 4-nitrophenol is deprotonated (pKa = 7.1), its sonolytic degradation is fully accounted for by OH-radical-induced reactions in the aqueous phase. At this pH, the sonolytic yield of H2O2 resulting from OH radical recombination in the solution, measured as a function of the 4-nitrophenol concentration, is reduced in line with the scavenging capacity of the 4-nitrophenolate. In contrast, at pH 4 the formation of H2O2 is already fully suppressed when the solution is 7 x 10(-4) mol dm-3 in 4-nitrophenol, and oxidative-pyrolytic degradation predominates, as exemplified by the large yields of CO and CO2 which are accompanied by a large H2 yield. The basis of this difference in behavior is a hydrophobic enrichment of 4-nitrophenol (which is undissociated at pH 4) at the interface of the cavitational bubble by a factor of about 80. The pH dependence of the yields of the pyrolytic products reflects the hydrolytic equilibrium concentration of 4-nitrophenol. The paper also demonstrates that the complexity of this sonochemical system precludes its use a gauge to determine the temperature in the interior of the cavitational bubble.     

Extreme conditions during multibubble cavitation: Sonoluminescence as a spectroscopic probe

We review recent work on the use of sonoluminescence (SL) to probe spectroscopically the conditions created during cavitation, both in clouds of collapsing bubbles (multibubble sonoluminescence, (MBSL)) and in single bubble events. The effective MBSL temperature can be controlled by the vapor pressure of the liquid or the thermal conductivity of the dissolved gas over a range from ～1600 to ～9000K. The effective pressure during MBSL is ～300bar, based on atomic line shifts. Given nanosecond emission times, this means that cooling rates are >10(12)K/s. In sulfuric and phosphoric acid, the low volatility and high solubility of any sonolysis products make bubble collapse more efficient and evidence for an optically opaque plasma core is found.     

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.     

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.     

OH-radical formation by ultrasound in aqueous solution--Part II: Terephthalate and Fricke dosimetry and the influence of various conditions on the sonolytic yield

Terephthalate and Fricke dosimetry have been carried out to determine the sonolytic energy yields of the OH free radical and of its recombination product H2O2 in aqueous solutions under various operating conditions (nature of operating gas, power, frequency, temperature). For example, in the sonolysis of Ar-saturated terephthalate solutions at room temperature, a frequency of 321 kHz, and a power of 170 W kg-1, the total yield [G(.OH) + 2 G(H2O2)], equals 16 x 10(-10) mol J-1. This represents the total of .OH that reach the liquid phase from gas phase of the cavitating bubble. The higher the solute concentration, the lower the H2O2 production as more of the OH free radicals are scavenged, in competition with their recombination. Fricke dosimetry, in the absence and presence of Cu2+ ions, shows that the yield of H atom reaching the liquid phase is much lower, with G(H.) of the order of 3 x 10(-10) mol J-1. These sonolytic yields are smaller in solutions that are at the point of gas saturation, and increase to an optimum as the initial sonication-induced degassing and effervescence subsides. The probing of the sonic field has shown that the rate of sonolytic free-radical formation may vary across the sonicated volume depending on frequency and power input.     

Preliminary results on the effect of power ultrasound on nitrogen oxide and dioxide atmosphere in nitric acid solutions.

The effect of ultrasound (20 kHz, 3 W cm-2) on the kinetics of HNO2 and H2O2 formation was investigated in a 1 M HNO3 medium for NO2-Ar and NO-Ar gas mixtures in various volume fractions (f(NO2) < 1.7 vol% and f(NO) < 1.1 vol%, respectively). The H2O2 formation rate measured in 1 M HNO3 in the presence of N2H5NO3 was observed to be much lower than that of HNO2 without N2H5NO3, and was relatively independent of the NO2 or NO gas volume fractions in the argon atmosphere. The HNO2 formation rate increased under ultrasound, and was higher with NO than with NO2. The induction period observed without ultrasound disappeared when ultrasound was applied. The first step in the sonochemical mechanism of HNO2 formation in the presence of NO2 involves thermal decomposition of NO2 into NO within the cavitation bubble. In the second step of HNO2 formation, NO reacts either with HNO3 in the cavitation bubble, or with NO2 in the cavitation bubble or at the bubble/solution interface.     

Mechanism of W(CO)6 sonolysis in diphenylmethane

The present work analyses the mechanism of W₂C/C nanocomposite formation during sonolysis of W(CO)₆ in diphenylmethane (DPhM) solutions. Carbon supported WC_x nanoparticles attract much interest as an alternative fuel cell electrocatalysts. Sonolysis of neat DPhM under the effect of 20 kHz power ultrasound in argon at 80 °C yields a sonopolymer as a solid product and acetylene, hydrogen, methane, diacetylene and benzene as gaseous products. Diacetylene is formed due to the secondary sonochemical dimerisation of acetylene obtained at the primary stage of DPhM sonolysis. FTIR and μ-Raman studies show that the sonopolymer consists of a mixture of some polymeric partially oxidized aromatic species, and disordered carbon. Sonolysis of W(CO)₆ in diphenylmethane solutions follows the first order kinetics. This process yields monodispersed 2-3 nm X-ray amorphous WC_x nanoparticles embedded in amorphous sonopolymer. The annealing of air sensitive as-prepared solids in an inert atmosphere at 600 °C causes formation of stable W₂C/C nanocomposite with W₂C average particle size in the range of 4-7 nm and hexagonal carbon fine particles with the average size of 30-40 nm. Kinetic study revealed that tungsten carbide is formed inside the cavitation bubble due to the reaction of tungsten nanoparticles originated from primary sonolysis of W(CO)₆ with acetylene produced as a result of diphenylmethane sonochemical degradation.     

Sonochemical polymerization of diphenylmethane

Sonolysis of diphenylmethane (DPhM) has been studied under the effect of 20 kHz ultrasound (absorbed acoustic power 0.45 W/ml, surface area of sonotrode 1 cm(2), volume of sonicated solution 100 ml) under argon at 60 degrees C. The solid product of the sonolysis was characterized by elemental analysis, FTIR, 13C MAS NMR, TGA/DSC, XRD and TEM techniques. It was found that the sonolysis of DPhM causes formation of the polymer with the composition similar to crosslinked polystyrene. Assumed mechanism of DPhM sonolysis consists of DPhM molecules dissociation inside the cavitating bubble. Secondary radical scavenging and radical recombination processes yields the sonopolymer in the liquid phase. The breakdown of the aromatic ring during DPhM sonolysis confirms that a very high temperature established in the cavitating bubble.     

Sonochemistry of cytochrome c. Evidence for superoxide formation by ultrasound in argon-saturated aqueous solution

Formation of superoxide anion radicals (O₂^·−) induced by 50 kHz ultrasound in argon (Ar)-saturated aqueous solution was studied. Although EPR-spin trapping study with 5,5-dimethyl-1-pyrroline N-oxide (DMPO;100 mM) revealed the formation of DMPO-adducts of hydroxyl radicals (^·OH) and hydroperoxy radicals (HO₂^·; acid form of O2^·−) in O₂-saturated solution after sonication, no evidence of HO₂^· was found in Ar-saturated solution. When ferricytochrome c (cytochrome c) in Ar-saturated aqueous solution was sonicated, the reduced form of cytochrome c was observed and 80% of its formation was inhibited by the addition of superoxide dismutase (SOD). Sodium formate enhanced the production of the reduced form of cytochrome c. The % inhibition by SOD for the reduction increased in the order of Xe > Ar > He in accord with the higher temperatures of the cavitation bubbles. These results indicate that the O₂^·− is formed by directly by the sonolysis of water in the absence of O₂ when the temperature of cavitation bubble collapse is sufficiently high.     

Sonolysis of chlorobenzene in Fenton-type aqueous systems

The influence of ultrasounds (200 kHz frequency) on the decomposition of chlorobenzene (CB) in a water solution (around 100 ppm concentration) containing iron or palladium sulfates was investigated. The intermediates of the sonolysis were identified, thus allowing a deeper insight into the degradation mechanism. It was established that CB degradation starts by pyrolysis inside the cavitation bubbles. The initial sonolysis product is benzene, formed in a reaction occurring outside the cavitation from phenyl radicals and the hydrogen atoms sonolytically generated from the water. Polyphenols as products of the CB sonochemical degradation are reported for the first time. The palladium salt was found to be a useful and sensitive indicator for differentiating the sites and mechanisms of the product formation. An alternative mechanism for the CB sonolysis is advanced, explaining the formation of phenols, polyphenols, chlorophenols and benzene.     

超声药物释放空化动力学行为研究

以直径1 μm的脂质体为空化研究对象,从修正的Rayleigh空化方程入手,研究机械系数(MI)对300 kHz和1 MHz超声作用时空化效应的影响。脂质体的药物释放以超声作用前后脂质体中钙黄绿素的荧光强度为量度。模拟结果表明:在微泡振荡过程中,由超声波驱动产生的负向最大泡壁运动速度促使微泡半径从最大快速减小接近于零,微泡积聚到最大能量。对于300 kHz和1 MHz的激励超声,存在一个拐点(MI)值,当MI小于接近0.4时,1 MHz微泡半径变化幅度强于300 kHz;当MI>0.4时,300 kHz微泡半径变化幅度强于1 MHz。这一结果预示在此范围内,300 kHz的药物释放效果好于1 MHz。本研究为超声空化效应研究及超声药物释放应用提供了理论依据。     

Limitations of the Weissler reaction as a model reaction for measuring the efficiency of hydrodynamic cavitation

The Weissler reaction in which iodide is oxidised to a tri-iodide complex (I(3)(-)) has been widely used for measurement of the intensity of ultrasonic and hydrodynamic cavitation. It was used in this work to compare ultrasonic cavitation at 24kHz with hydrodynamic cavitation using two different devices, one a venturi and the other a sudden expansion, operated up to 8.7bar. Hydrodynamic cavitation had a maximum efficiency of about 5x10(-11) moles of I(3)(-) per joule of energy compared with the maximum of almost 8x10(-11)molJ(-1) for ultrasonic cavitation. Hydrodynamic cavitation was found to be most effective at 10 degrees C compared with 20 degrees C and 30 degrees C and at higher upstream pressures. However, it was found that in hydrodynamic conditions, even without cavitation, I(3)(-) was consumed at a rapid rate leading to an equilibrium concentration. It was concluded that the Weissler reaction was not a good model reaction for the assessment of the effectiveness of hydrodynamic cavitation.     

Acoustic noise spectra under hydrothermal conditions

Acoustic noise spectra were studied for the first time in overheated water using sonohydrothermal reactor operating at 20 kHz ultrasound in the temperature range from 25 to 200 °C at the autogenic pressure of 1–14 bar. The obtained results highlighted a dominating role of stable cavitation during ultrasonic treatment of hot water. Heating of sonicated water results in the formation of large number of nonlinearly oscillating bubbles synchronous with the driving frequency. At 200 °C, the acoustic spectra also display strong subharmonic and multiple ultraharmonic bands. Moreover, cavitation bubbles formed at 200 °C exhibit chaotic and random motions. It has been shown that the addition of TiO₂ nanoparticles to hydrothermal water heated at 200 °C allows to eliminate subharmonic/ultraharmonic bands and stochastic oscillations as well. This effect was assigned to Pickering-like bubble stabilization due to the particle accumulation at the bubble surface.     

Comparative study of sonochemical reactors with different geometry using thermal and chemical probes

Laboratory scale 20 kHz sonochemical reactors with different geometries have been tested using thermal probes, the kinetics of H(2)O(2) formation, and the kinetics of diphenylmethane (DPhM) sonochemical darkening. Results revealed that the overall sonochemical reaction rates in H(2)O and DPhM are driven by the total absorbed acoustic energy and roughly independent the geometry of the studied reactors. However, the sonochemical efficiency, defined as eta=VG/S, where G is a sonochemical yield of H(2)O(2), V is a volume of sonicated liquid, and S is a surface of the sonotrode, was proved to increase with the decrease of S. This phenomenon was explained by growing of the maximum cavitating bubble size with ultrasonic intensity and its independence towards the specific absorbed acoustic power. For the cleaning bath reactor the kinetics of the sonochemical reactions in H(2)O and DPhM depends strongly on the reaction vessel materials: the reaction rates decreased with the increase of the materials elasticity. Kinetic study of H(2)SO(4) sonolysis using a sonoreactor without direct contact with titanium sonotrode showed that sulphate anion is an effective scavenger of OH() radicals formed during water sonolysis.     

Estimation of chemical and physical effects of cavitation by analysis of cavitating single bubble dynamics

Cavitation events create extreme conditions in a localized ‘bubble collapse’ region, leading to the formation of hydroxyl radicals, shockwaves and microscopic high-speed jets, which are useful for many chemical and physical transformation processes. Single bubble dynamics equations have been used previously to investigate the chemical and physical effects of cavitation. In the present study, the state of the art of the single bubble dynamics equations was reviewed and certain noteworthy modifications were implemented. Simulations reaffirmed previously reported collapse temperatures of the order ~5,000 K and collapse pressures well over ~1,000 bar under varying operating conditions. The chemical effects were assessed in terms of the hydroxyl radical generation rate (OHG), calculated by applying the minimization of the Gibb’s Free Energy method using simulated collapse conditions. OHG values as high as 1x10¹² OH molecules per collapse event were found under certain operating conditions. A new equation was proposed to assess the physical effects, in terms of the impact pressure of the water jet - termed as the jet hammer pressure (JHP), formed due to the asymmetrical collapse of a bubble near a wall. The predicted JHP were found to be within a range of ~100 to 1000 bar under varying operating conditions. Important issues such as the onset of cavitation and chaotic solutions, for a cavitating single bubble dynamics were discussed. The Blake threshold pressure was found to be a sufficient criterion to capture the onset of cavitation. The impact of key operating parameters on the chemical and physical effects of cavitation were investigated exhaustively through simulations, over the parameter ranges relevant to acoustic and hydrodynamic cavitation processes. Presented methodology and results will be useful for optimisation and further investigations of a broad range of acoustic and hydrodynamic cavitation-based applications.     

Characterization of cavitation in a flow-through exposure chamber by means of a resonant bubble detector

Ultrasonic cavitation at frequencies of 0.514, 0.866, 1.03 and 1.61 MHz in water flowing through tubes was observed by counting bubbles downstream with a resonant bubble detector (RBD) operated at 0.89 or 1.7 MHz. In a 21 mm diameter, thin-walled tube, cavitation thresholds in tap water flowing at 5.3 cm s^?1 ranged from 2.0 – 2.5 bar at 0.514 MHz to 3 – 4 bar at 1.61 MHz. When high speed injections were employed to trigger the ultrasonic cavitation with hydrodynamically-generated bubbles, the thresholds were reduced to about 2 bar and bubble production was enhanced for 1.03 and 1.61 MHz exposures. Ultrasonic radiation forces on the bubbles and bubble coalescence appeared to cause, under some conditions, a reduction in bubble counts during subthreshold exposures when bubbles were injected into the flow. The RBD method is a useful tool for detecting and semi-quantitatively observing cavitation in a flow-through exposure system.     

Sonochemical and sonocatalytic degradation of monolinuron in water

The degradation of the phenylurea monolinuron (MLN) by ultrasound irradiation alone and in the presence of TiO(2) was investigated in aqueous solution. The experiments were carried out at low and high frequency (20 and 800 kHz) in complete darkness. The degradation of MLN by ultrasounds occurred mainly by a radical pathway, as shown the inhibitory effect of adding tert-butanol and bicarbonate ions to scavenge hydroxyl radicals. However, CO(3)(-) radicals were formed with bicarbonate and reacted in turn with MLN. In this study, the degradation rate of MLN and the rate constant of H(2)O(2) formation were used to evaluate the oxidative sonochemical efficiency. It was shown that ultrasound efficiency was improved in the presence of nanoparticles of TiO(2) and SiO(2) only at 20 kHz. These particles provide nucleation sites for cavitation bubbles at their surface, leading to an increase in the number of bubbles when the liquid is irradiated by ultrasound, thereby enhancing sonochemical reaction yield. In the case of TiO(2), sonochemical efficiency was found to be greater than with SiO(2) for the same mass introduced. In addition to the increase in the number of cavitation bubbles, activated species may be formed at the TiO(2) surface that promote the formation of H(2)O(2) and the decomposition of MLN.     

Luminescence of Tb3+ and Gd3+ ions in sonolysis under the conditions of a single bubble moving in aqueous solutions of TbCl3 and GdCl3

Luminescence bands of Tb³⁺ and Gd³⁺ ions are detected during sonolysis in the regime of a moving single bubble in aqueous solutions of TbCl₃ and GdCl₃ salts with concentration 1–2 mol/L. Saturation with argon, low temperatures of solutions (?5°C), and a high concentration of salts are the factors facilitating sonoluminescence of the metal. Comparison with the characteristics of sonoluminescence of lanthanide ions studied earlier in the regimes of multibubble and single-bubble sonolysis with a stationary bubble shows that the electron excitation of metal ions in the given case is associated with translational displacements of the bubble. Our results confirm the validity of the sonochemical model of microdroplet injection, which explains the penetration of nonvolatile salts into cavitation bubbles as a result of their deformation during intense movements.     

Sonochemical reduction of carbon dioxide

Sonolysis of carbon dioxide dissolved in water was performed from a standpoint of reducing this material in atmosphere. During one hour of sonication, the amount of CO2 decreased to about half at 5 degrees C under CO2-Ar atmosphere. The decreasing rate for CO2 followed the order Ar > He > H2 > N2 and it was down with increasing temperature in the range of 5-45 degrees C. The most favorable concentration for reducing CO2 was 0.03 (mole fraction of CO2 in gas phase). This concentration in gas phase means an equal mixture of CO2 and Ar in water, because CO2 is more soluble than Ar. Since carbon dioxide dissolved in water would be partly ionized, the roles of ions on the sonolysis were also examined. Gaseous reaction products were CO, H2 and a small amount of O2. Carbon monoxide and hydrogen might be obtained from CO2 and H2O by sonolysis, respectively. Both gases are fuel and react each other to C1 compounds such as methanol, and so on. Therefore, irradiation of ultrasonic waves should be an important technique for reducing CO2.