Mechanism and dynamic study of reactive red X-3B dye degradation by ultrasonic-assisted ozone oxidation process

The effectiveness of ozone combined with ultrasound techniques in degrading reactive red X-3B is evaluated. A comparison among ozone (O₃), ultrasonic (US), ozone/ultrasonic (O₃/US) for degradation of reactive red X-3B has been performed. Results show that O₃/US system was the most effective and the optimally synergetic factor reaches to 1.42 in O₃/US system. The cavitation of ultrasound plays an important role during the degradation process. It is found that 99.2% of dye is degraded within 6 min of reaction at the initial concentration of 100 mg·L⁻¹, pH of 6.52, ozone flux of 40 L·h⁻¹ and ultrasonic intensity of 200 W·L⁻¹. Ozonation reactions in conjunction with sonolysis indicate that the decomposition followed pseudo-first-order reaction kinetics but the degradation efficiencies are affected by operating conditions, particularly initial pH and ultrasonic intensity. A kinetic model is established based on the reaction corresponding to operational parameters. In addition, the main reaction intermediates, such as p-benzoquinone, catechol, hydroquinone, phthalic anhydride and phthalic acid, are separated and identified using GC/MS and a possible degradation pathway is proposed during the O₃/US process.     

Degradation of diclofenac during sonolysis, ozonation and their simultaneous application

Diclofenac is a widely used anti-inflammatory non-steroidal drug that escapes conventional urban wastewater treatment trains because of its resistance to biodegradation. Therefore it is frequently found in treated effluents, lakes and rivers. It has been reported that diclofenac can exhibit adverse effects on aquatic organisms. Advanced oxidation processes like ozonation (O₃) and sonolysis (US) can be employed for the removal of such recalcitrant compounds from water matrices. This study included the investigation of the efficiency of O₃ and US and also of their combined application (US + O₃) for the degradation and potential mineralization of diclofenac in a water matrix. Under the conditions applied, all three systems proved to be effective in inducing diclofenac oxidation, leading to 22% of mineralization for O₃ and 36% for US after 40 min of treatment. The synergy observed in the combined schemes, mainly due to the effects of US in enhancing the O₃ decomposition, led to higher mineralization (about 40%) for 40 min treatment, and to a significantly higher mineralization level for shorter treatment duration.     

Analysis of ultrasonic pre-treatment for the ozonation of humic acids

This paper presents an intensification study of an ozonation process through an ultrasonic pre-treatment for the elimination of humic substances in water and thus, improve the quality of water treatment systems for human consumption. Humic acids were used as representative of natural organic matter in real waters which present low biodegradability and a high potential for trihalomethane formation. Ultrasonic frequency (98 kHz, 300 kHz and 1 MHz), power (10–40 W) and sonicated volume (150–400 mL) was varied to assess the efficiency of the ultrasonic pre-treatment in the subsequent ozonation process. A direct link between hydroxyl radical (HO) formation and fluorescence reduction was observed during sonication pre-treatment, peaking at 300 kHz and maximum power density. Ultrasound, however, did not reduce total organic carbon (TOC). Injected ozone (O₃) dose and reaction time were also evaluated during the ozonation treatment. With 300 kHz and 40 W ultrasonic pre-treatment and the subsequent ozonation step (7.4 mg O₃/L_gas), TOC was reduced from 21 mg/L to 13.5 mg/L (36% reduction). HO attack seems to be the main degradation mechanism during ozonation. A strong reduction in colour (85%) and SUVA₂₅₄ (70%) was also measured. Moreover, changes in the chemical structure of the macromolecule were observed that led to the formation of oxidation by-products of lower molecular weight.     

Ultrasonic-assisted ozone degradation of organic pollutants in industrial sulfuric acid

In this work, a combination of ozone (O₃) and ultrasound (US) has been firstly used to decolorize black concentrated sulfuric acid with high organic content. The effect of different reaction factors on the transparency, extent of decolorization, H₂SO₄ mass fraction, and organic pollutants removal is studied. In addition, the systematic interaction between ultrasound and ozone on the decolorization process is reviewed through comparative experiments of O₃, US and US/O₃. A sulfuric acid product that meets the requirements for first-class products in national standards, with an extent of decolorization of 74.07%, transparency of 70 mm, and a mass fraction of 98.04%, is obtained under the optimized conditions. Under the same conditions, it has been established that the treatment time can be saved by 25% using the US/O₃ process compared to using O₃. Further, the production of oxidative free radicals (•OH) in a concentrated sulfuric acid system is enhanced using the US/O₃ process compared with O₃. In addition, the degree of effectiveness of different oxidizing components on the decolorization process is revealed by adding different free radical shielding agents when the US/O₃ process is used.     

Treatment of complex sulfur-containing solutions in ammonia desulfurization ammonium sulfate production by ultrasonic-assisted ozone technology

In this work, the cause of abnormal color in ammonium sulfate products formed by flue gas desulfurization is revealed by investigating the conversion relationship between different sulfur-containing ions and their behavior in a sulfuric acid medium. Both thiosulfate (S₂O₃²⁻) and sulfite (SO₃²⁻ ＆ HSO₃⁻) impurities affect the quality of ammonium sulfate. The S₂O₃²⁻ is the main reason for the yellowing of the product due to the formation of sulfur impurities in concentrated sulfuric acid. To address the yellowing of ammonium sulfate products, a unified technology (US/O₃), using ozone (O₃) and ultrasonic waves (US) simultaneously, is exploited to remove both thiosulfate and sulfite impurities from the mother liquor. The effect of different reaction parameters on the degree of removal of thiosulfate and sulfite is investigated. The synergistic effect of ultrasound and ozone on ion oxidation is further explored and demonstrated by the comparative experiments with O₃ and US/O₃. Under the optimized conditions, the thiosulfate and sulfite concentration in the solution is 2.07 and 5.93 g/L, respectively, and the degree of removal is 91.39 and 90.83%, respectively. The product obtained after evaporation and crystallization is pure white and meets the national standard requirements for ammonium sulfate products. Under the same conditions, the US/O₃ process has apparent advantages, such as saving reaction time compared with the O₃ process alone. Introducing an ultrasonically intensified field improves the generation of oxidation radicals ·OH, ¹O₂, and ·O₂^– in the solution. Furthermore, the effectiveness of different oxidation components in the decolorization process is studied by adding other radical shielding agents using the US/O₃ process supplemented with EPR analysis. The order of the different oxidation components is O₃(86.04%) > ¹O₂(6.53%) > •OH(4.45%) > •O₂^–(2.97%) for the oxidation of thiosulfate, and it is O₃(86.28%) > •OH(7.49%) > ¹O₂(4.99%) > •O₂^–(1.25%) for the oxidation of sulfite.     

Intensification of depolymerization of polyacrylic acid solution using different approaches based on ultrasound and solar irradiation with intensification studies

Depolymerization of polyacrylic acid (PAA) as sodium salt has been investigated using ultrasonic and solar irradiations with process intensification studies based on combination with hydrogen peroxide (H₂O₂) and ozone (O₃). Effect of solar intensity, ozone flow and ultrasonic power dissipation on the extent of viscosity reduction has been investigated for individual treatment approaches. The combined approaches such as US + solar, solar + O₃, solar + H₂O₂, US + H₂O₂ and US + O₃ have been subsequently investigated under optimum conditions and established to be more efficient as compared to individual approaches. Approach based on US (60 W) + solar + H₂O₂ (0.01%) resulted in the maximum extent of viscosity reduction as 98.97% in 35 min whereas operation of solar + H₂O₂ (0.01%), US (60 W), H₂O₂ (0.3%) and solar irradiation resulted in about 98.08%, 90.13%, 8.91% and 90.77% intrinsic viscosity reduction in 60 min respectively. Approach of US (60 W) + solar + ozone (400 mg/h flow rate) resulted in extent of viscosity reduction as 99.47% in 35 min whereas only ozone (400 mg/h flow rate), ozone (400 mg/h flow rate) + US (60 W) and ozone (400 mg/h flow rate) + solar resulted in 69.04%, 98.97% and 98.51% reduction in 60 min, 55 min and 55 min respectively. The chemical identity of the treated polymer using combined approaches was also characterized using FTIR (Fourier transform infrared) spectra and it was established that no significant structural changes were obtained during the treatment. Overall, it can be said that the combination technique based on US and solar irradiations in the presence of hydrogen peroxide is the best approach for the depolymerization of PAA solution.     

Sonolysis and ozonation as pretreatment for anaerobic digestion of solid organic waste

This study aims to compare the efficiency of sonolysis and ozonation in improving anaerobic biodegradability of source sorted organic fraction of municipal solid waste, for the enhancing of biogas production and energy recovery as well. The methane yield of solid organic material anaerobic digestion is significantly affected by substrate availability, which can be favoured by pretreatments. In this investigation, both sonolysis and ozonation effects on substrate solubilisation and anaerobic biodegradability were evaluated under different treatment conditions. Results show that both pretreatments can significantly improve the solubilisation of organic solid waste. However, during ozonation experiments, no correlation was observed between increased solubilisation and biogas production: the application of higher ozone doses led to the formation of by-products less biodegradable than untreated substrate. This evidence makes the ultrasound process more efficient than ozonation and addresses further studies for sonolysis optimisation as pretreatment for solid waste anaerobic digestion.     

Enhancement of biogas production from individually or co-digested green algae Cheatomorpha linum using ultrasound and ozonation treated biochar

This paper proposes the use of modified biochar, derived from Sawdust (SD) biomass using sonication (SSDB) and Ozonation (OSDB) processes, as an additive for biogas production from green algae Cheatomorpha linum (C. linum) either individually or co-digested with natural diet for rotifer culture (S. parkel). Brunauer-Emmett-Teller (BET), Fourier-Transform Infrared (FTIR), thermal-gravimetric (TGA), and X-ray diffraction (XRD) analyses were used to characterize the generated biochar. Ultrasound (US) specific energy, dose, intensity and dissolved ozone (O₃) concentration were also calculated. FTIR analyses proved the capability of US and ozonation treatment of biochar to enhance the biogas production process. The kinetic model proposed fits successfully with the data of the experimental work and the modified Gompertz models that had the maximum R² value of 0.993 for 150 mg/L of OSDB. The results of this work confirmed the significant impact of US and ozonation processes on the use of biochar as an additive in biogas production. The highest biogas outputs 1059 mL/g VS and 1054 mL/g VS) were achieved when 50 mg of SSDB and 150 mg of OSDB were added to C. linum co-digested with S. parkle.     

Medium-high frequency ultrasound and ozone based advanced oxidation for amoxicillin removal in water

In this study, treatment of an antibiotic compound amoxicillin by medium-high frequency ultrasonic irradiation and/or ozonation has been studied. Ultrasonic irradiation process was carried out in a batch reactor for aqueous amoxicillin solutions at three different frequencies (575, 861 and 1141 kHz). The applied ultrasonic power was 75 W and the diffused power was calculated as 14.6 W/L. The highest removal was achieved at 575 kHz ultrasonic frequency (>99%) with the highest pseudo first order reaction rate constant 0.04 min⁻¹ at pH 10 but the mineralization achieved was around 10%. Presence of alkalinity and humic acid species had negative effect on the removal efficiency (50% decrease). To improve the poor outcomes, ozonation had been applied with or without ultrasound. Ozone removed the amoxicillin at a rate 50 times faster than ultrasound. Moreover, due to the synergistic effect, coupling of ozone and ultrasound gave rise to rate constant of 2.5 min⁻¹ (625 times higher than ultrasound). In the processes where ozone was used, humic acid did not show any significant effect because the rate constant was so high that ozone has easily overcome the scavenging effects of natural water constituents. Furthermore, the intermediate compounds, after the incomplete oxidation mechanisms, has been analyzed to reveal the possible degradation pathways of amoxicillin through ultrasonic irradiation and ozonation applications. The outcomes of the intermediate compounds experiments and the toxicity was investigated to give a clear explanation about the safety of the resulting solution. The relevance of all the results concluded that hybrid advanced oxidation system was the best option for amoxicillin removal.     

Novel approaches based on ultrasound for treatment of wastewater containing potassium ferrocyanide

Industrial wastewaters containing biorefractory compounds like cyanide offer significant environmental problems attributed to the fact that the conventional methods have limited effectiveness and hence developing efficient treatment approaches is an important requirement. The present work investigates the use of novel treatment approach of ultrasound (US) combined with advanced oxidation techniques for the degradation of potassium ferrocyanide (KFC) for the first time. An ultrasonic bath equipped with longitudinal horn (1 kW rated power and 25 kHz frequency) has been used. The effect of initial pH (2–9) on the progress of degradation has been investigated initially and subsequently using the optimized pH, effect of addition of hydrogen peroxide (ratio of KFC:H₂O₂ varied over the range of 1:0.5–1:5) and TiO₂ in the presence of H₂O₂ (1:1 ratio by weight of TiO₂) as process intensifying approach has been studied. Combination of ultrasonic irradiation with ozone (O₃) (100–400 mg/h) and ultraviolet irradiation (UV) has also been investigated. Use of combination of US with H₂O_2, H₂O₂ + TiO₂ and ozone resulted in extent of KFC degradation as 54.2%, 74.82% and 82.41% respectively. Combination of US with both UV and ozone was established to be the best approach yielding 92.47% degradation. The study also focused on establishing kinetic rate constants for all the treatment approaches which revealed that all the approaches followed first order kinetic mechanism with higher rate constants for the combination approaches. Overall, it has been conclusively established that ultrasound based combined treatment schemes are very effective for the treatment of KFC containing wastewaters.     

Sonozonation (sonication/ozonation) for the degradation of organic contaminants – A review

Ozonation (OZ) is an important advanced oxidation process to purify water and wastewater. Because of the lower solubility and instability of ozone (O₃), selective oxidation and dependence on pH value, the industrial applications of OZ have been hindered by the following disadvantages: incomplete removal of pollutants, lower mineralization efficiency and the formation of toxic by-products. Meanwhile, OZ seems to have higher processing costs than other technologies. To improve the treatment efficiency and O₃ utilization, several combined processes, such as H₂O₂/O₃, UV/O₃, and Cavitation/O₃, have been explored, while the combined method of ultrasonication (US) with OZ is a promising treatment technology with a complex physicochemical mechanism. In US alone, the sonolysis of water molecules can produce more powerful unselective oxidant hydroxyl radicals (OH), and directly cause the sonochemical pyrolysis of volatile pollutants. In US/OZ, US can promote the mass transfer of O₃, and also drive the chemical conversion of O₃ to enhance the formation of OH. Various layouts of US/OZ devices and the interactive effects of US/OZ (synergism or antagonism) on the degradation of various organics are illustrated in this review. The main factors, including US frequency, pH value, and radical scavengers, significantly affect the mass transfer and decomposition of O₃, the formation of OH and H₂O₂, the degradation rates of organics and the removal efficiencies of COD and TOC (mineralization). As a result, US can significantly increase the yield of OH, thereby improving the degradation efficiency and mineralization of refractory organics. However, US also enhances the decomposition of ozone, thereby reducing the concentration of O₃ in water and impairing the efficiency of selective oxidation with O₃ molecules.     

Hybrid hydrodynamic cavitation (HC) technique for the treatment and disinfection of lake water

Water reclamation from lakes needs to be accomplished efficiently and affordably to ensure the availability of clean, disinfected water for society. Previous treatment techniques, such as coagulation, adsorption, photolysis, ultraviolet light, and ozonation, are not economically feasible on a large scale. This study investigated the effectiveness of standalone HC and hybrid HC + H₂O₂ treatment techniques for treating lake water. The effect of pH (3 to 9), inlet pressure (4 to 6 bar), and H₂O₂ loading (1 to 5 g/L) were examined. At pH = 3, inlet pressure of 5 bar and H₂O₂ loadings of 3 g/L, maximum COD and BOD removal were achieved·H₂O₂ was observed to significantly improve the performance of the HC when used as a chemical oxidant. In an optimal operating condition, a COD removal of 54.5 % and a BOD removal of 51.5 % using HC alone for 1 h is observed. HC combined with H₂O₂ removed 64 % of both COD and BOD. The hybrid HC + H₂O₂ treatment technique resulted in a nearly 100% removal of pathogens. The results of this study indicate that the HC-based technique is an effective method for removing contaminants and disinfection of the lake water.     

Impact of sonolytic ozonation (O3/US) on degradation of pesticide residues in fresh vegetables and fruits: Case study of Faisalabad,Pakistan

High pesticide residues in fresh produce is a serious food safety issue. This study was aimed at assessing the pesticides residues in some important vegetables and fruits marketed in Faisalabad, Pakistan and the impact of sonolytic ozonation (O₃/US) treatment in removing these contaminants. From a short grower’s survey, five registered and mostly used pesticides (acetamiprid, carbendazim, imidacloprid, thiacloprid and thiamethoxam) were identified. A time optimization trial of O₃/US application (05, 10 and 15 min) on okra, showed that 10 min treatment significantly reduced three identified chemicals (thiamethoxam 100 %, imidacloprid and thiacloprid 97.17 %), without any adverse effect on its quality. In follow up trial, five fresh vegetables (cauliflower, chillies, cucumber, spinach and tomato) three fresh fruits (grapes, guava and peach) collected from three markets of Faisalabad, were pooled together to have uniform samples. Vegetables and fruits were treated with O₃/US for 10 and 6 min, respectively, along with control (simple tap wash) for determining the impacts on pesticides degradation. Samples were processed for extraction, clean up and analysis using HPLC-UV–Vis in isocratic mode. The data revealed the presence of five mentioned chemicals, with an accumulative mean residue of 9.006 and 1.921 µg/g in tested vegetables and fruits, respectively. After subjecting to O₃/US, the accumulative chemical residues were reduced to 3.214 µg/g (64.313 %) and 1.064 (44.6 %) in treated vegetables and fruits respectively. Irrespective of fresh produce, the mean residues of thiamethoxam, imidachloprid, acetamiprid and thiachloprid and carbendazim were reduced by 99.3 %, 52.6 %, 65.2 %, 87.3 % and 72% respectively. It was concluded that sonolytic ozonation treatment was effective in significant reduction of pesticide residues from vegetables and fruits and thus can be employed as a good food safety practice at culinary level to reduce the associated health hazardous risks.     

Ultrasonic degradation of selected dyes using Ti3C2Tx MXene as a sonocatalyst

MXene, a new family of two dimensional materials, was utilized as a sonocatalyst in an ultrasonic treatment (US) process for removal of methylene blue (MB) and acid blue 80 (AB). The physico-chemical properties of MXene were characterized using scanning electron microscopy, transmission electron microscopy, porosimetry, and a zeta potential analyzer. Degradation of dyes by US was systemically investigated under several experimental conditions including: power density of US (45, 90, 135, and 180 W L⁻¹), frequency of US (28 and 970 kHz), pH of dye solution (3.5, 7, and 10.5), solution temperature (293, 303, and 313 K), and addition of hydroxyl radical promotor (H₂O₂) and scavenger (t-BuOH) to concentrations of 25 mM. Based on the experimental results, the quantity of H₂O₂, which was used as an indicator of hydroxyl radical concentration, was an important factor in determining the degradation rate of MB and AB in this US study. Additionally, synergetic indices for removal of both dyes were higher than 1.0 in all cases, indicating the outstanding efficiency of MXene as a sonocatalyst in the US reactor for removal of both, due to an increase in both (i) the quantity of H₂O₂ in the US reactor and (ii) active sites for adsorbates from dispersion effects. A stability test on MXene in the US process was conducted using X-ray diffraction and five-cycle recycling performance tests. Based on our experimental data, MXene can be utilized as a sonocatalyst in the US process for a high removal rate for dyes (e.g., MB).     

Improved direct synthesis of TiO2 catalyst using sonication and its application for the desulfurization of thiophene

TiO₂ catalyst was synthesized in the presence of ultrasound (ultrasonic horn at 20 kHz frequency and 70% duty cycle) at different power (80 W to 120 W) and durations as well as surfactant concentration with an objective of establishing best conditions for achieving lowest particle size of the photocatalyst. Detailed characterization in terms of crystal phase, crystallinity, functional groups and morphology of the photocatalyst has been performed using SEM, XRD and FTIR analysis. It was demonstrated that sonication significantly reduced the particle size with high degree of sphericity and homogeneity as compared to conventionally synthesized TiO₂ with similar crystallinity in both cases. The catalytic performance was subsequently evaluated for the deep desulfurization of thiophene. Different desulfurization approaches including individual US (ultrasonic horn at 20 kHz frequency, 110 W power and 70% duty cycle) and UV irradiations, US/UV, US/UV/H₂O₂, US/UV/TiO₂ and US/UV/H₂O₂/TiO₂ were applied to evaluate the catalytic activity. The best approach was demonstrated as US/UV/H₂O₂/TiO₂ and also activity of catalyst synthesized using ultrasound was much better compared to conventionally synthesized catalyst. The studies related to different model solvents demonstrated lowest reactivity for toluene whereas n-hexane and n-octane resulted in complete desulfurization in 60 min and 50 min treatment respectively. The desulfurization followed pseudo first order reaction kinetics irrespective of the solvent used. Overall the work clearly demonstrated the efficacy of ultrasound in improving the catalyst synthesis as well as desulfurization of thiophene.     

Application of hybrid oxidative processes based on cavitation for the treatment of commercial dye industry effluents

The present work demonstrates the significant role of ultrasound (US) in intensifying the efficacy of the combination with Fenton reagent and/or ozone for the treatment of real dye industry industrial effluent procured from the local industry. Initial part of the work focused on analysing the literature based on combination approaches of US with different oxidants applied for the treatment of real and simulated effluents focusing on the dyes. The work also provides guidelines for the selection of optimal operating parameters for maximizing the intensification of the degradation. The second part of the work presents an experimental study into combined approaches of ultrasound with ozone (O₃) and Fenton’s reagent for treatment of real effluent. Under optimized conditions (100 W, 20 kHz and duty cycle of 70%), maximum COD reductions of 94.79% and 51% were observed using a combined approach of US + Fenton oxidation followed by lime treatment for the treatment of effluent-I and effluent-II respectively at H₂O₂ loading of 17.5 g/L, H₂O₂/Fe²⁺ ratio of 3, pH of 4, CaO dose of 1 g/L and an overall treatment time of 70 min. US + Fenton + O₃ followed by lime was also applied for treatment under ozone loading of 1 g/h for the treatment of effluent-I and it was found that maximum COD reduction of 95.12% was obtained within 30 min of treatment time, indicating use of ozone did not result in significant value addition in terms of COD reduction but resulted in faster treatment. HC (inlet pressure: 4 bar) + Fenton + Lime scheme was successfully replicated on a pilot-scale resulting in maximum COD reduction of 57.65% within 70 min of treatment time. Overall, it has been concluded that the hybrid oxidative processes as US + Fenton followed by lime treatment is established as the best approach ensuring effective COD reduction at the same time obtaining final colourless/reusable effluent.     

Removal of 2,4-dinitrophenol using hybrid methods based on ultrasound at an operating capacity of 7 L

Sonochemical removal of 2,4-dinitrophenol (DNP) has been investigated using ultrasonic bath, with an operating capacity of 7 L, fitted with a large transducer with longitudinal vibrations having a 1 kW rated power output and operating frequency of 25 kHz. It has been revealed from calorimetric studies that maximum power is dissipated at a capacity of 7 L. The concentration of DNP has been monitored with an objective of evaluation of the efficacy of ultrasonic reactor in combination with process intensifying approaches for the removal of DNP. The effect of operating pH and additives such as hydrogen peroxide and ferrous iron activated persulfate on the extent of removal of DNP has been investigated. It has been observed that the extent of removal is greater at lower pH (pH 2.5 and 4) than at higher pH (pH 10). The combined treatment strategies such as ultrasound (US)/Fenton, US/advanced Fenton and US/CuO/H₂O₂ have also been investigated with an objective of obtaining complete removal of DNP using hybrid treatment strategies. The extent of removal has been found to increase significantly in US/Fenton process (98.7%) as compared to that using US alone (5.8%) which demonstrates the efficacy of the combined process. First order kinetics has been fitted for all the approaches investigated in the work. Calculations of cavitational yield indicated the superiority of the reactor design as compared to the conventional ultrasonic horn type reactors. The main intermediates formed during the process of removal of DNP have been identified.     

Sonochemical water splitting in the presence of powdered metal oxides

Kinetics of hydrogen formation was explored as a new chemical dosimeter allowing probing the sonochemical activity of argon-saturated water in the presence of micro- and nano-sized metal oxide particles exhibiting catalytic properties (ThO₂, ZrO₂, and TiO₂). It was shown that the conventional sonochemical dosimeter based on H₂O₂ formation is hardly applicable in such systems due to catalytic degradation of H₂O₂ at oxide surface. The study of H₂ generation revealed that at low-frequency ultrasound (20 kHz) the sonochemical water splitting is greatly improved for all studied metal oxides. The highest efficiency is observed for relatively large micrometric particles of ThO₂ which is assigned to ultrasonically-driven particle fragmentation accompanied by mechanochemical water molecule splitting. The nanosized metal oxides do not exhibit particle size reduction under ultrasonic treatment but nevertheless yield higher quantities of H₂. The enhancement of sonochemical water splitting in this case is most probably resulting from better bubble nucleation in heterogeneous systems. At high-frequency ultrasound (362 kHz), the effect of metal oxide particles results in a combination of nucleation and ultrasound attenuation. In contrast to 20 kHz, micrometric particles slowdown the sonolysis of water at 362 kHz due to stronger attenuation of ultrasonic waves while smaller particles show a relatively weak and various directional effects.     

Degradation of 4-chloro 2-aminophenol using combined strategies based on ultrasound,photolysis and ozone

The present work investigates the degradation of 4-chloro 2-aminophenol (4C2AP), a highly toxic organic compound, using ultrasonic reactors and combination of ultrasound with photolysis and ozonation for the first time. Two types of ultrasonic reactors viz. ultrasonic horn and ultrasonic bath operating at frequency of 20 kHz and 36 kHz respectively have been used in the work. The effect of initial pH, temperature and power dissipation of the ultrasonic horn on the degradation rate has been investigated. The established optimum parameters of initial pH as 6 (natural pH of the aqueous solution) and temperature as 30 ± 2 °C were then used in the degradation studies using the combined approaches. Kinetic study revealed that degradation of 4C2AP followed first order kinetics for all the treatment approaches investigated in the present work. It has been established that US + UV + O₃ combined process was the most promising method giving maximum degradation of 4C2AP in both ultrasonic horn (complete removal) and bath (89.9%) with synergistic index as 1.98 and 1.29 respectively. The cavitational yield of ultrasonic bath was found to be eighteen times higher as compared to ultrasonic horn implying that configurations with higher overall areas of transducers would be better selection for large scale treatment. Overall, the work has clearly demonstrated that combined approaches could synergistically remove the toxic pollutant (4C2AP).     

SonoFenton degradation of an azo dye,Direct Red

The degradation of a reactive azo dye, Direct Red 81 (DR81), by Fenton process and in conjunction with sonolysis (SonoFenton) was studied. The synergistic effect of Fenton process and sonolysis enhanced the degradation of Direct Red 81 in aqueous solutions and the reaction followed the mechanism of hydroxyl radical (HO) oxidation. The influence of the initial substrate concentration, pH and catalyst loading on the rate of decolorisation were studied. The dye decolorisation followed apparent first order kinetics. The optimum conditions for decolorisation were pH = 3.0, [Fe²⁺] = 0.2 g/l, [H₂O₂] = 5.1 × 10⁻³ mol/l and ultrasonic frequency = 120 kHz, 60 W. These conditions yielded 99% decolorisation of DR81 within 75 min. The sonolytic degradation products of DR81 were identified using Electrospray Ionization-Mass Spectrometry (ESI-MS). The presence of CO₃²⁻, HCO₃⁻, Cl⁻, NO₃⁻, and SO₄²⁻ ions in the dye solution did not have a considerable effect on the decolorisation efficiency. This study demonstrates that Fenton and SonoFenton methods can effectively decolorize DR81 dye in waste water. The dye concentration used in this study is higher compared to earlier studies illustrating the effective mineralization by the SonoFenton process. The mechanism of dye degradation is also proposed.