The effects of liquid height/volume,initial concentration of reactant and acoustic power on sonochemical oxidation

Even though much knowledge on acoustic cavitation and its application has been accumulated over the past decades, further research is still required to develop industrial uses of acoustic cavitation. It is because the available information is mainly based on small-scale sonoreactors and the design and optimization of sonoreactors for large-scale applications have not been widely studied. In this study, the effects of liquid height/volume, initial concentration of the reactant and input acoustic power on sonochemical oxidation reactions including iodide ion oxidation, As(III) oxidation, and hydrogen peroxide generation were investigated using a 291 kHz sonoreactor with various liquid height/volumes (50, 100, 200, 300, 500, and 1000 mL) and input powers (23, 40, and 82 W). As the liquid height/volume and the input power changed, the power density varied from 23 to 1640 W/L and the maximum cavitation yields of triiodide ion for 23, 40, and 82 W were observed at 0.05, 0.1, and 0.2/0.3 L, respectively. It was found that low power was more effective for the small volume and the large volume required high power level and the moderate power density, approximately 400 W/L, was suggested for the sonochemical oxidation of iodide ion in the 291 kHz sonoreactor in this study. Similar results were observed in the generation of hydrogen peroxide and the sonochemical oxidation of As(III) to As(V). It was also revealed that KI dosimetry could be applicable for the estimation of the sonochemical reactions of non-volatile compounds such as As(III).     

Sonochemical reactions with mesoporous alumina

Herein, we report the sonochemical reactions with MSU-X mesoporous alumina (m-Al₂O₃) in aqueous solutions. Sonication (f = 20 kHz, I = 30 W cm^?2, W_aq = 0.67 W mL^?1, T = 36–38 °C, Ar) causes significant acceleration of m-Al₂O₃ dissolution in the pH range of 4–11. Moreover, power ultrasound has a dramatic effect on the textural properties and phase composition of m-Al₂O₃. Short-time sonication at pH = 4 leads to the formation of nanorods and nanofibers of boehmite, AlO(OH). Prolonged ultrasonic treatment causes high aspect morphology transformation to aggregated nanosheets in weakly acid solutions or plated nanocrystals in alkaline solutions. Sonochemical products in alkaline medium are composed principally from boehmite and small amounts of bayerite, Al(OH)₃. Silent hydrolysis of m-Al₂O₃ yields boehmite at pH = 4 and bayerite at pH = 11. The effect of ultrasound on the textural properties of mesoporous alumina as well as on the transformation of nanosized bayerite to boehmite can be consistently attributed to the transient strong heating of the liquid shell surrounding the cavitation bubble which caused the chemical processes similar to those occurred during hydrothermal treatment.     

Correlation between iodide dosimetry and terephthalic acid dosimetry to evaluate the reactive radical production due to the acoustic cavitation activity

Acoustic cavitation plays an important role in sonochemical processes and the rate of sonochemical reaction is influenced by sonication parameters. There are several methods to evaluate cavitation activity such as chemical dosimetry. In this study, to comparison between iodide dosimetry and terephthalic acid dosimetry, efficacy of sonication parameters in reactive radical production has been considered by iodide and terephthalic acid dosimetries. For this purpose, efficacy of different exposure parameters on cavitations production by 1 MHz ultrasound has been studied. The absorbance of KI dosimeter was measured by spectrophotometer and the fluorescence of terephthalic acid dosimeter was measured using spectrofluorometer after sonication. The result of experiments related to sonication time and intensity showed that with increasing time of sonication or intensity, the absorbance is increased. It has been shown that the absorbance for continuous mode is remarkably higher than for pulsing mode (p-value < 0.05). Also results show that with increasing the duty cycles of pulsed field, the inertial cavitation activity is increased. With compensation of sonication time or intensity in different duty cycles, no significant absorbance difference were observed unless 20% duty cycle. A significant correlation between the absorbance and fluorescence intensities (count) at different intensity (R = 0.971), different sonication time (R = 0.999) and different duty cycle (R = 0.967) were observed (p-value < 0.05). It is concluded that the sonication parameters having important influences on reactive radical production. These results suggest that there is a correlation between iodide dosimetry and terephthalic acid dosimetry to examine the acoustic cavitation activity in ultrasound field.     

Comparison of characterization methods in high frequency sonochemical reactors of differing configurations

The aim of this study was to compare different characterization methods in order to evaluate the sonochemical efficiency of a cavitational reactor. The selected characterization methods were calorimetry and dosimetry based on potassium iodide oxidation or nitrite and nitrate ion formation. The effects of experimental parameters on physical and chemical effects of ultrasound were quantified with two transducers at a frequency of 366 kHz. The studied factors comprised temperature (16–28 °C), acoustic power (6–38 W), power density (4–61 W L^?1) and reactor configuration (D_{reactor 1} = 65 mm, D_{reactor 2} = 102 mm). Spectrophotometry was compared to ionic chromatography as a method to quantify nitrite and nitrate ions. Spectrometry was shown to be as representative as ionic chromatography. The reaction system based on the formation of both nitrite and nitrate ions was demonstrated to be as reliable as a potassium iodide dosimeter. The representativity of calorimetry was limited since part of acoustic energy was assumed to be used in the chemical reactions observed by dosimetry. Similar sonochemical efficiencies resulted from an increase of sonified surface (D_{reactor 1} = 65 mm vs. D_{reactor 2} = 102 mm) coupled to a 2-time decrease in power density at a constant emitting surface. The effect of emitting-to-sonified surface area ratio on the acoustic field was apparently limited by the height of the liquid.     

Ultrasound-induced inactivation of gram-negative and gram-positive bacteria in secondary treated municipal wastewater

The effect of 24 kHz, high energy ultrasound in the presence and absence of titanium dioxide particles on the destruction of different bacteria groups was studied. Applying a total of 1500 W/L for 60 min (this corresponds to 5400 kJ/L specific nominal energy), the mean destruction of gram-negative bacteria such as total coliforms, faecal coliforms and Pseudomonas spp. was 99.5%, 99.2% and 99.7%, respectively. More recalcitrant to sonolytic inactivation were the gram-positive bacteria Clostridium perfringens and faecal streptococci with a mean removal of 66% and 84%, respectively. The presence of 5 g/L TiO₂ generally enhanced the destruction of gram-negative bacteria, yielding three to five logs reduction. On the other hand, the relatively weak sonochemical inactivation of gram-positive bacteria was only slightly affected by the presence of solid particles. Inactivation was found to follow first-order kinetics regarding bacteria population and was not affected significantly by the wastewater quality. Ultrasound irradiation at 4000 kJ/L specific nominal energy and in the presence of 5 g/L TiO₂ achieved less than 10³ CFU/100 mL total coliforms, thus meeting USEPA quality standards for wastewater reuse.     

Investigation of acoustic and geometric effects on the sonoreactor performance

In this work, three design configurations of a sonoreactor are considered under various operating conditions, and the acoustic characteristics during water sonication are investigated while using an immersed-type ultrasonic flat transducer probe in a sonoreactor model. Numerical models are also developed to simulate the sonication process, and they are successfully validated and compared with available data in the literature. Several sets of numerical investigations are conducted using the finite-element method and solved by the computational acoustics module in the COMSOL Multiphysics. The effects of the acoustical and geometrical parameters are investigated, analyzed, and reported, including the ultrasonic frequency, acoustic intensity, and scaling-up the reactor. The present study includes a parametric investigation examining the change of the ultrasonic frequency, intensity, and probe immersion depth on the performance. The results of the parametric study show that the highest cavitation energy corresponds to the maximum magnitude of negative pressure that takes place in the range of 60–80 kHz. The cavitation energy analyses are conducted under the conditions of 20 kHz of frequency and at 36 W input power. It is found that the cavitation energy of 15.87 W could produce 2.98 × 10⁻¹⁰ mol/J of sonochemical efficiency. In addition, the effect of altering the transducer probe depth changes the acoustic pressure field insignificantly. Furthermore, a recommendation is made to improve the sonochemical efficiency by introducing more considerable ultrasound input power while operating the sonoreactor at an ultrasonic frequency lower than 60 kHz. The results presented in this paper provide a comprehensive assessment of different sonoreactors and the feasibility of scaling-up their production rate.     

Multibubble sonoluminescence as a tool to study the mechanism of formic acid sonolysis

Sonoluminescence spectra collected from 0.1 to 3.0 M aqueous solutions of formic acid sparged with argon show the OH(A²Σ⁺−X²Π_i) and C₂(d³Π_g → a³Π_u) emission bands and a broad continuum typical for multibubble sonoluminescence. The overall intensity of sonoluminescence and the sonochemical yield of HCOOH degradation vary in opposite directions: the sonoluminescence is quenched while the sonochemical yield increases with HCOOH concentration. By contrast, the concentration of formic acid has a relatively small effect on the intensity of C₂ Swan band. It is concluded that C₂ emission originates from CO produced by HCOOH degradation rather than from direct sonochemical degradation of HCOOH. The intensity of C₂ band is much stronger at high ultrasonic frequency compared to 20 kHz ultrasound which is in line with higher yields of CO at high frequency. Another product of HCOOH sonolysis, carbon dioxide, strongly quenches sonoluminescence, most probably via collisional non-radiative mechanism.     

Dual frequency cavitation event sensor with iodide dosimeter

The inertial cavitation activity depends on the sonication parameters. The purpose of this work is development of dual frequency inertial cavitation meter for therapeutic applications of ultrasound waves. In this study, the chemical effects of sonication parameters in dual frequency sonication (40 kHz and 1 MHz) were investigated in the progressive wave mode using iodide dosimetry. For this purpose, efficacy of different exposure parameters such as intensity, sonication duration, sonication mode, duty factor and net ultrasound energy on the inertial cavitation activity have been studied. To quantify cavitational effects, the KI dosimeter solution was sonicated and its absorbance at a wavelength of 350 nm was measured. The absorbance values in continuous sonication mode was significantly higher than the absorbance corresponding to the pulsed mode having duty factors of 20–80% (p < 0.05). Among different combination modes (1 MHz_100% + 40 kHz_100%, 1 MHz_100% + 40 kHz_80%, 1 MHz_80% + 40 kHz_100%, 1 MHz_80% + 40 kHz_80%), the continuous mode for dual frequency sonication is more effective than other combinations (p < 0.05). The absorbance for this combined dual frequency mode was about 1.8 times higher than that obtained from the algebraic summation of single frequency sonications. It is believed that the optimization of dual frequency sonication parameters at low-level intensity (<3 W/cm²) by optically assisted cavitation event sensor can be useful for ultrasonic treatments.     

Effect of ultrasound frequency on antioxidant activity,total phenolic and anthocyanin content of red raspberry puree

Ultrasound in the 20–1000 kHz range show unique propagation characteristics in fluid media and possess energy that can break down fruit matrices to facilitate the extraction of valuable bioactive compounds. Red raspberries carry significant amounts of specific antioxidants, including ellagitannins and anthocyanins that are important for human health. The objective of this study was to investigate the effects of ultrasound frequencies associated with cavitation (20 kHz) and microstreaming (490 and 986 kHz) on total antioxidant activity (AOA), total phenolics content (TPC), and total monomeric anthocyanin content (ACY) of red raspberry puree prepared from crushed berries. The pureed fruit was subjected to high-intensity (20 kHz) and higher frequency-low intensity (490 and 986 kHz) ultrasound for 30 min. The temperature of treated purees increased to a maximum of 56 °C with 986 kHz. Sonication at 20 and 490 kHz significantly (p < 0.05) affected the AOA, ACY, and TPC of red raspberry puree, while 986 kHz had no significant effect on ACY and AOA (p < 0.05). In all cases, ultrasound treatment had significant and positive effect on at least one of the measured parameters up to 30 min. Sonication beyond 10 min (and up to 30 min) using 20 kHz either produced no change or caused a drop in AOA and ACY. However, for 986 and 20 kHz, TPC, increased by 10% and 9.5%, respectively after 30 min (p < 0.05) compared to the control. At 20 kHz, AOA and ACY increased by 17.3% and 12.6% after 10 min. It was demonstrated that 20 kHz ultrasound treatment, when limited to 10 min, was the most effective for extraction of bioactive compounds in red raspberry compared to 490 and 986 kHz although the effect could be similar at the higher frequencies if different amplitudes are used.     

Sonochemical effect on size reduction of CaCO3 nanoparticles derived from waste eggshells

A novel combination of mechanochemical and sonochemical techniques was developed to produce high-surface-area, bio-based calcium carbonate (CaCO₃) nanoparticles from eggshells. Size reduction of eggshell achieved via mechanochemical and followed by sonochemical method. First, eggshells were cleaned and ground, then ball milled in wet condition using polypropylene glycol for ten hours to produce fine particles. The ball milled eggshell particles were then irradiated with a high intensity ultrasonic horn (Ti-horn, 20 kHz, and 100 W/cm²) in the presence of N,N-dimethylformamide (DMF); decahydronaphthalene (Decalin); or tetrahydrofuran (THF). The ultrasonic irradiation times varied from 1 to 5 h. Transmission electron microscopic (TEM) studies showed that the resultant particle shapes and sizes were different from each solvent. The sonochemical effect of DMF is more pronounced and the particles were irregular platelets of ～10 nm. The BET surface area (43.687 m²/g) of these nanoparticles is much higher than that of other nanoparticles derived from eggshells.     

Synergism between ultrasonic pretreatment and white rot fungal enzymes on biodegradation of wheat chaff

Lignocellulosic biomass samples (wheat chaff) were pretreated by ultrasound (US) (40 kHz/0.5 W cm⁻²/10 min and 400 kHz/0.5 W cm⁻²/10 min applied sequentially) prior to digestion by enzyme extracts obtained from fermentation of the biomass with white rot fungi (Phanerochaete chrysosporium or Trametes sp.). The accessibility of the cellulosic components in wheat chaff was increased, as demonstrated by the increased concentration of sugars produced by exposure to the ultrasound treatment prior to enzyme addition. Pretreatment with ultrasound increased the concentration of lignin degradation products (guaiacol and syringol) obtained from wheat chaff after enzyme addition. In vitro digestibility of wheat chaff was also enhanced by the ultrasonics pretreatment in combination with treatment with enzyme extracts. Degradation was enhanced with the use of a mixture of the enzyme extracts compared to that for a single enzyme extract.     

Lysis of Chlamydomonas reinhardtii by high-intensity focused ultrasound as a function of exposure time

Efficient lysis of microalgae for lipid extraction is an important concern when processing biofuels. Historically, ultrasound frequencies in the range of 10–40 kHz have been utilized for this task. However, greater efficiencies might be achievable if higher frequencies could be used. In our study, we evaluated the potential of using 1.1 MHz ultrasound to lyse microalgae for biofuel production while using Chlamydomonas reinhardtii as a model organism. The ultrasound was generated using a spherically focused transducer with a focal length of 6.34 cm and an active diameter of 6.36 cm driven by 20 cycle sine-wave tone bursts at a pulse repetition frequency of 2 kHz (3.6% duty cycle). The time-average acoustic power output was 26.2 W while the spatial-peak-pulse-average intensity (I_SPPA) for each tone burst was 41 kW/cm². The peak compressional and rarefactional pressures at the focus were 102 and 17 MPa, respectively. The exposure time was varied for the different cases in the experiments from 5 s to 9 min and cell lysis was assessed by quantifying the percentage of protein and chlorophyll release into the supernate as well as the lipid extractability. Free radical generation and lipid oxidation for the different ultrasound exposures were also determined. We found that there was a statistically significant increase in lipid extractability for all of the exposures compared to the control. The longer exposures also completely fragmented the cells releasing almost all of the protein and chlorophyll into the supernate. The cavitation activity did not significantly increase lipid oxidation while there was a minor trend of increased free radical production with increased ultrasound exposure.     

A phenomenological investigation into the opposing effects of fluid flow on sonochemical activity at different frequency and power settings. 2. Fluid circulation at high frequencies

Sonochemical activity is dependent on flow patterns within the reactor and either no affect or a decrease in activity was observed at 376, 995, and 1179 kHz from overhead stirring. The interaction of fluid flow with ultrasound was further investigated in this study with circulatory flow. The effect of fluid circulation on radical production was investigated at two circulation speeds, with and without surface stabilisation. The sonochemical activity was determined by the yield of hydrogen peroxide, measured by iodide dosimetry. The sonochemically active region was pictured using sonochemiluminescence imaging and the flow fields were visualised with dyed flow videos. At 376 and 995 kHz, an increase in sonochemical activity was observed with the slower flow rate; however at 1179 kHz, the sonochemical activity was either not affected or decreased. The observed changes in sonochemical activity were attributed to an increase in asymmetry of the bubble collapse brought about by fluid motion.     

Sonochemical preparation of SbS1−xSexI nanowires

A sonochemical method for direct preparation of nanowires of SbS_1?xSe_xI solid solution has been established. The SbS_1?xSe_xI gel was synthesized using elemental Sb, S, Se and I in the presence of ethanol under ultrasonic irradiation (35 kHz, 2 W/cm²) at 50 °C for 2 h. The product was characterized by using techniques such as powder X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, energy dispersive X-ray analysis, selected area electron diffraction, and optical diffuse reflection spectroscopy. The SEM and HRTEM investigations exhibit that the as-prepared samples are made up of large quantity nanowires with lateral dimensions of about 10–50 nm and lengths reaching up to several micrometers and single-crystalline in nature. The increase of molar composition of Se affects linear decrease of the indirect forbidden optical energy gap as well as the distance between (121) planes of the SbS_1?xSe_xI nanowires.     

Ce0.8Sm0.2O1.9 synthesis for solid oxide fuel cell electrolyte by ultrasound assisted co-precipitation method

In this study, the synthesis of Ce_0.8Sm_0.2O_1.9 (SDC) solid electrolyte by the ultrasound assisted co-precipitation method was accomplished to explore the effects of ultrasound power, ultrasound pulse ratio and probe type upon the ionic conductivity of SDC as well as the lattice parameter, the microstructure and the density. Fine powders of uniform crystallite sizes (average 11.70 ± 0.62 nm) were obtained, needing lower sintering temperature. The SDC powders were successfully sintered to a relative density of over 95% at 1200 °C (5 °C min^?1) for 6 h. The micrograph of SDC pellets showed non-agglomerated and well-developed grains with average size of about 200 nm. X-ray diffraction analysis showed that the lattice parameter increased with increasing acoustic intensity and reached a maximum for the 14.94 W cm^?2. Further, a linear relationship was detected between the lattice parameter and the ionic conductivity, inspiring a dopant like effect of US on the electrolyte properties. The highest ionic conductivity as σ_800°C = 3.07 × 10^?2 S cm^?1 with an activation energy E_a = 0.871 kJ mol^?1 was obtained with pulsed ultrasound for an acoustic intensity of 14.94 W cm^?2, using 19 mm probe and 8:2 pulse ratio.     

Inactivation of Enterobacter aerogenes in reconstituted skim milk by high- and low-frequency ultrasound

The inactivation of Enterobacter aerogenes in skim milk using low-frequency (20 kHz) and high-frequency (850 kHz) ultrasonication was investigated. It was found that low-frequency acoustic cavitation resulted in lethal damage to E. aerogenes. The bacteria were more sensitive to ultrasound in water than in reconstituted skim milk having different protein concentrations. However, high-frequency ultrasound was not able to inactivate E. aerogenes in milk even when powers as high as 50 W for 60 min were used. This study also showed that high-frequency ultrasonication had no influence on the viscosity and particle size of skim milk, whereas low-frequency ultrasonication resulted in the decrease in viscosity and particle size of milk. The decrease in particle size is believed to be due to the breakup of the fat globules, and possibly to the cleavage of the κ-casein present at the surface of the casein micelles. Whey proteins were also found to be slightly affected by low-frequency ultrasound, with the amounts of α-lactalbumin and β-lactoglobulin slightly decreasing.     

Dielectric relaxation of CsHSeO4 above room temperature

Dielectric measurements of CsHSeO₄ show a distinct relaxation at low frequencies at several isotherms (T < 363 K). For example, the relaxation frequency is around 4 kHz at 323 K and increases to higher frequencies (~ 100 kHz) as the temperature increases. The relaxation has an activation energy of 0.8 eV, which is in close agreement with that associated with transport of charge carriers. We suggest that the observed dielectric relaxation could be produced by the H⁺ jump and SeO₄^? 2 reorientation that cause distortion and change the local lattice polarizability, inducing dipoles like HSeO₄^?.     

Ultrasonic pilot-scale reactor for enzymatic bleaching of cotton fabrics

The potential of ultrasound-assisted technology has been demonstrated by several laboratory scale studies. However, their successful industrial scaling-up is still a challenge due to the limited pilot and commercial sonochemical reactors. In this work, a pilot reactor for laccase-hydrogen peroxide cotton bleaching assisted by ultrasound was scaled-up. For this purpose, an existing dyeing machine was transformed and adapted by including piezoelectric ultrasonic devices. Laboratory experiments demonstrated that both low frequency, high power (22 kHz, 2100 W) and high frequency, low power ultrasounds (850 kHz, 400 W) were required to achieve satisfactory results. Standard half (4 g/L H₂O₂ at 90 °C for 60 min) and optical (8 g/L H₂O₂ at 103 °C for 40 min) cotton bleaching processes were used as references. Two sequential stages were established for cotton bleaching: (1) laccase pretreatment assisted by high frequency ultrasound (850 kHz, 400 W) and (2) bleaching using high power ultrasound (22 kHz, 2100 W). When compared with conventional methods, combined laccase-hydrogen peroxide cotton bleaching with ultrasound energy improved the whitening effectiveness. Subsequently, less energy (temperature) and chemicals (hydrogen peroxide) were needed for cotton bleaching thus resulting in costs reduction. This technology allowed the combination of enzyme and hydrogen peroxide treatment in a continuous process. The developed pilot-scale reactor offers an enhancement of the cotton bleaching process with lower environmental impact as well as a better performance of further finishing operations.     

Sonolysis of levodopa and paracetamol in aqueous solutions

Pharmaceutical products are often present in wastewater treatment effluents, rivers, lakes and, more rarely, in groundwater. The advanced oxidation methods, like ultrasound, find a promising future in the area of wastewater treatment. The aim of this paper is to evaluate the influence of several parameters of the ultrasound process on the degradation of paracetamol, a widely used non-steroidal anti-inflammatory recalcitrant drug found in water and levodopa, the most frequently prescribed drug for the treatment of Parkinson disease. Experiments were carried out at 574, 860 and 1134 kHz of ultrasonic frequency with horn-type sonicator and actual power values of 9, 17, 22 and 32 W at 20 °C. Initial concentrations of 25, 50, 100 and 150 mg L^?1 of both products were used. Treatment efficiency was assessed following changes in pharmaceuticals concentration and chemical oxygen demand.The sonochemical degradation of both products follows a pseudo-first-order reaction kinetics. Complete removal of pharmaceuticals was achieved in some cases but some dissolved organic carbon remains in solution showing that long lived intermediates were recalcitrant to ultrasound irradiation. Pollutants conversion and COD removal were found to decrease with increasing the initial solute concentration and decreasing power. The best results were obtained with 574 kHz frequency. Investigations using 1-butanol as radical scavenger and H₂O₂ as promoter revealed that pollutants degradation proceeds principally through radical reactions, although some differences were observed between both molecules. Addition of H₂O₂ had a positive effect on degradation rate, but the optimum concentration of hydrogen peroxide depends on the pollutant.     

Ultrasound assisted the preparation of 1-butoxy-4-nitrobenzene under a new multi-site phase-transfer catalyst – Kinetic study

In the present research work deals with the preparation of 1-butoxy-4-nitrobenzene was successfully carried out by 4-nitrophenol with n-butyl bromide using aqueous potassium carbonate and catalyzed by a new multi-site phase-transfer catalyst (MPTC) viz., N¹,N⁴-diethyl-N¹,N¹,N⁴,N⁴-tetraisopropylbutane-1,4-diammonium dibromide, under ultrasonic (40 kHz, 300 W) assisted organic solvent condition. The pseudo first-order kinetic equation was applied to describe the overall reaction. Under ultrasound irradiation (40 kHz, 300 W) in a batch reactor, it shows that the overall reaction greatly enhanced with ultrasound irradiation than without ultrasound. The present study provides a method to synthesize nitro aromatic ethers by ultrasound assisted liquid–liquid multi-site phase-transfer catalysis condition.