Degradation of azo dye Acid black 1 using low concentration iron of Fenton process facilitated by ultrasonic irradiation

A combination of ultrasonic and low concentration iron (<3 mgL(-1)) of Fenton process (US/Fenton) has been used to treat wastewater containing Acid black 1 (AB1). The results show that the oxidation power of low concentration iron of Fenton could be significantly enhanced by ultrasonic irradiation. The degradation of AB1 in aqueous solution by US/Fenton can receive better results compared with either Fenton oxidation or ultrasonic alone. Many operational parameters, such as ultrasonic power density, the pH value, the Fe(2+) dosage, the H(2)O(2) dosage, AB1 concentration and the temperature, affecting the degradation efficiency were investigated. Also, the effects of various inorganic anions (such as Cl(-), NO(3)(-), CO(3)(2-), etc.) on the oxidation efficiency of US/Fenton were studied. Under the given test conditions, 98.83% degradation efficiency was achieved after 30 min reaction by US/Fenton. The effect of various inorganic anions was in the following decreasing order: SO(3)(2-)>CH(3)COO(-)>Cl(-)>CO(3)(2-)>HCO(3)(-)>SO(4)(2-)>NO(3)(-). The results show that the US/Fenton can be an effective technology for the treatment of organic dyes in wastewater.     

Degradation of Acid Orange 7 in aqueous solution by zero-valent aluminum under ultrasonic irradiation

Degradation of azo dye Acid Orange 7 (AO7) by zero-valent aluminum (ZVAl) in combination with ultrasonic irradiation was investigated. The preliminary studies of optimal degradation methodology were conducted with sole ultrasonic, sole ZVAl/air system, ultrasonication + ZVAl/air system (US-ZVAl). In ZVAl/air system, the degradation of AO7 could almost not be observed within 30 min. The degradation of AO7 by ZVAl/air system was obviously enhanced under ultrasound irradiation, and the enhancement is mainly attributed to that the production of hydroxyl radicals in ultrasound-ZVAl process was much higher than that in sole ultrasonic or in sole ZVAl/air system. The variables considered for the effect of degradation were the power of ultrasound, the initial concentration of AO7, as well as the initial pH value and the dosage of zero-valent aluminum. The results showed that the decolorization rate increased with the increase of power density and the dosage of ZVAl, but decreased with the increase of initial pH value and initial concentration of AO7. More than 96% of AO7 removal was achieved within 30 min under optimum operational conditions (AO7: 20 mg/L, ZVAl: 2 g/L, pH: 2.5, ultrasound: 20 kHz, 300 W). This study demonstrates that ultrasound-ZVAl process can effectively decolorize the azo dye AO7 in wastewater.     

Enhanced ultrasound-assisted degradation of methyl orange and metronidazole by rectorite-supported nanoscale zero-valent iron

In this study, the rectorite-supported nanoscale zero-valent iron (nZVI/R) was synthesized through a reduction method. X-ray diffraction analysis showed the existence of the nZVI in the nZVI/R composite and X-ray photoelectron spectroscopy analysis indicated that the nZVI particles were partly oxidized into iron oxide. Scanning electron microscopy analysis revealed that the nZVI particles were highly dispersed on the surface of the rectorite. The specific surface area of the nZVI/R composite is 21.43 m²/g, which was higher than that of rectorite (4.30 m²/g) and nZVI (17.97 m²/g). In the presence of ultrasound (US), the degradation of methyl orange and metronidazole by the nZVI/R composite was over 93% and 97% within 20 min, respectively, which is much higher than that by the rectorite and the nZVI. The degradation ratio of methyl orange and metronidazole by the nZVI/R composite under US was 1.7 and 1.8 times as high as that by the nZVI/R composite without US, respectively. The mechanism of the enhanced degradation of methyl orange and metronidazole under US irradiation was studied. These results indicate that the US/nZVI/R process has great potential application value for treatment of dye wastewater and medicine wastewater.     

Decolorization of azo dye Orange G by aluminum powder enhanced by ultrasonic irradiation

In this work, the decolorization of azo dye Orange G (OG) in aqueous solution by aluminum powder enhanced by ultrasonic irradiation (AlP-UI) was investigated. The effects of various operating operational parameters such as the initial pH, initial OG concentration, AlP dosage, ultrasound power and added hydrogen peroxide (H₂O₂) concentration were studied. The results showed that the decolorization rate was enhanced when the aqueous OG was irradiated simultaneously by ultrasound in the AlP-acid systems. The decolorization rate decreased with the increase of both initial pH values of 2.0–4.0 and OG initial concentrations of 10–80 mg/L, increased with the ultrasound power enhancing from 500 to 900 W. An optimum value was reached at 2.0 g/L of the AlP dosage in the range of 0.5–2.5 g/L. The decolorization rate enhanced significantly by the addition of hydrogen peroxide in the range of 10–100 mM to AlP-UI system reached an optimum value of 0.1491 min⁻¹. The decolorization of OG appears to involve primarily oxidative steps, the cleavage of NN bond, which were verificated by the intermediate products of OG under the optimal tested degradation system, aniline and 1-amino-2-naphthol-6,8-disulfonate detected by the LC–MS.     

Sonocatalytic removal of naproxen by synthesized zinc oxide nanoparticles on montmorillonite

ZnO/MMT nanocomposite as sonocatalyst was prepared by immobilizing synthesized ZnO on the montmorillonite surface. The characteristics of as-prepared nanocomposite were studied by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM) and X-ray diffraction (XRD) techniques. The synthesized samples were used as a catalyst for sonocatalytic degradation of naproxen. ZnO/MMT catalyst in the presence of ultrasound irradiation was more effective compared to pure ZnO nanoparticles and MMT particles in the sonocatalysis of naproxen. The effect of different operational parameters on the sonocatalytic degradation of naproxen including initial drug concentration, sonocatalyst dosage, solution pH, ultrasonic power and the presence of organic and inorganic scavengers were evaluated. It was found that the presence of the scavengers suppressed the sonocatalytic degradation efficiency. The reusability of the nanocomposite was examined in several consecutive runs, and the degradation efficiency decreased only 2% after 5 repeated runs. The main intermediates of naproxen degradation were determined by gas chromatography–mass spectrometry (GC–Mass).     

Sonolytic and sonophotolytic degradation of Carbamazepine: Kinetic and mechanisms

An in-depth investigation on the ultrasonic decomposition of Carbamazepine (CBZ), one of the most regularly identified drugs in the environment, was conducted. The effects of diverse variables were evaluated, such as frequency, power, solution pH, initial CBZ concentration and varied inorganic anions. Reaction order was determined on the basis of analyzing reaction kinetics of CBZ degradation. The sonophotolysis and photolysis of CBZ was also examined in this contribution. The influence of water composition on the sonolytic and sonophotolytic elimination of CBZ was analyzed. Additionally, 21 intermediates were identified during sonolytic degradation of CBZ based on LC/ESI-MS/MS analysis, among which two escaped from the detection in previous studies. Possible decay pathways were proposed accordingly. The epoxidation, cleavage of double bond, hydration, hydroxylation, ring contraction and intramolecular cyclization were believed to be involved in sonochemical degradation of CBZ.     

Enhanced degradation of 2,4-dichlorophenol by ultrasound in a new Fenton like system (Fe/EDTA) at ambient circumstance

This study investigated the effect of ultrasound (US) enhancement on the degradation of 2,4-DCP in a new Fenton like system. An obviously synergistic effect was observed after introduction of US into the Fe/EDTA system. Good correspondences with pseudo-first-order kinetic were found in each reaction system. It was demonstrated that the degradation rate constant (k_obs) of DCP in US/Fe/EDTA was 7 and 32 times higher than those in Fe/EDTA and US system alone. Simultaneously, lower first-order k_obs was also obtained in the investigation of decomposition of EDTA. At 60 min reaction time, Removals of 81% TOC, complete DCP and 89% EDTA were achieved. Low molecular weight organic acids are identified as the main products, which contribute to the solution self-buffer at about pH 6.5 along with the reaction. In addition, the effect of initials condition, i.e., iron addition, EDTA dosage, DCP concentration and US input power as well as reaction temperature were studied and reaction activation energy (E_a) was also calculated.     

Degradation of Acid Blue 25 in aqueous media using 1700 kHz ultrasonic irradiation: ultrasound/Fe(II) and ultrasound/H2O2 combinations

In this work, the sonolytic degradation of an anthraquinonic dye, C.I. Acid Blue 25 (AB25), in aqueous phase using high frequency ultrasound waves (1700 kHz) for an acoustic power of 14 W was investigated. The sonochemical efficiency of the reactor was evaluated by potassium iodide dosimeter, Fricke reaction and hydrogen peroxide production yield. The three investigated methods clearly show the production of oxidizing species during sonication and well reflect the sonochemical effects of high frequency ultrasonic irradiation. The effect of operational conditions such as the initial AB25 concentration, solution temperature and pH on the degradation of AB25 was studied. Additionally, the influence of addition of salts on the degradation of dye was examined. The rate of AB25 degradation was dependent on initial dye concentration, pH and temperature. Addition of salts increased the degradation of dye. Experiments conducted using distilled and natural waters demonstrated that the degradation was more efficient in the natural water compared to distilled water. To increase the efficiency of AB25 degradation, experiments combining ultrasound with Fe(II) or H₂O₂ were conducted. Fe(II) induced the dissociation of ultrasonically produced hydrogen peroxide, leading to additional OH radicals which enhance the degradation of dye. The combination of ultrasound with hydrogen peroxide looks to be a promising option to increase the generation of free radicals. The concentration of hydrogen peroxide plays a crucial role in deciding the extent of enhancement obtained for the combined process. The results of the present work indicate that ultrasound/H₂O₂ and ultrasound/Fe(II) processes are efficient for the degradation of AB25 in aqueous solutions by high frequency ultrasonic irradiation.     

Degradation of C.I. Direct Black 168 from aqueous solution by fly ash/H2O2 combining ultrasound

Degradation of C.I. Direct Black 168 from aqueous solution using Fenton-like reactions combining ultrasound was investigated. In the presence of H₂O₂, the effect of the heterogeneous catalysts, such as fly ash, kaolinite or diatomaceous earth on the degradation of Direct Black 168 was observed under ultrasound. The fly ash was the most efficient catalyst. It is apparent that ultrasound can prompt the reaction to take place and give in higher degradation. In the combination of ultrasound and fly ash/H₂O₂, the effect of different system variables namely concentration of the dye, dosage of fly ash, concentration of H₂O₂, pH of solution and the addition of NaCl were studied. 99.0% removal ratio was achieved at initial concentration 100 mg/L, pH 3.0, and dosage of fly ash 2.0 g/L, as well as 2.94 mM H₂O₂. NaCl exhibited only a minor effect on the dye removal.     

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

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

Degradation of C.I. Acid Orange 7 by the advanced Fenton process in combination with ultrasonic irradiation

The combination of ultrasound and the advanced Fenton process (AFP, zero-valent iron and hydrogen peroxide) for the degradation of C.I. Acid Orange 7 was studied. The effect of hydrogen peroxide concentration, initial pH, ultrasonic power density, dissolved gas, and iron powder addition on the decolorization of C.I. Acid Orange 7 was investigated. A modified pseudo-first order kinetic model was used to simulate the experimental results. The results showed that the decolorization rate increased with the increase of hydrogen peroxide concentration and power density, but decreased with the increase of initial pH value. There existed an optimal iron powder addition when decolorization rate was concerned. The decolorization efficiency also increased with the increase of hydrogen peroxide concentration, but decreased with the increase of initial pH value. It varied little at different power densities or iron powder additions at the fixed hydrogen peroxide concentration. The presence of dissolved gas would enhance color removal, and the enhancement was more significant when dissolved oxygen was present. More hydrogen peroxide dosage and reaction duration are required to achieve a relatively high COD removal than those employed to simply break the chromophore group.     

Removal of carbamazepine from aqueous solution using sono-activated persulfate process

This study investigated systematically the removal of carbamazepine (CBZ) in solution using the combination of ultrasound and persulfate anions to identify the factors affecting the kinetics of the process. The effects of reaction time, initial persulfate anion concentration, initial CBZ concentration, ultrasonic power input, solution pH and temperature on CBZ removal efficiency were examined. The sulfate radical oxidation of CBZ in the presence of ultrasonic irradiation showed a significant synergistic effect on CBZ removal. It is found that up to 89.4% CBZ removal efficiency was achieved after 120 min reaction. The removal process of CBZ in solution could be described using pseudo-first-order kinetics. In this system, sulfate radicals (SO₄⁻) were considered to be the mainly oxidant to remove CBZ while ultrasound power input could affect CBZ removal efficiency significantly. Changing solution pH influenced the CBZ removal efficiency and the best performance would be achieved at pH 5.0.     

Synergistic degradation of methyl orange in an ultrasound intensified photocatalytic reactor

An original ultrasound (US) directly intensified photocatalytic reactor was designed to degrade azo dye pollutant methyl orange (MeO) using Degussa TiO(2) as the photocatalyst. The sonolytic, photocatalytic and sonophotocatalytic degradation of MeO in the new reactor and the synergistic effect between sonolysis and photocatalysis were investigated. Effects of operation parameters i.e., US power, TiO(2) dosage, liquid circulation velocity and air flow rate on degradation efficiency were investigated and optimized. The results showed that all parameters have optimal values for the sonophotocatalytic degradation of MeO, and the optimum conditions for the new process are US power 600 W, TiO(2) dosage 3g/L, liquid circulation velocity 4.05×10(-2) m/s and air flow rate 0.2 L/min. Under the optimum conditions, 91.52% MeO had been degraded within 1h, and the combination of sonolysis and TiO(2) photocatalysis exhibited an obvious synergetic effect.     

Sonolytic degradation of endocrine disrupting chemical 4-cumylphenol in water

The sonolytic degradation of endocrine disrupting compound 4-cumylphenol (4-CyP) in aqueous solution was investigated. The influence of operating parameters for sonication process such as 4-CyP initial concentration, frequency, power, pH, temperature and saturating gas was examined. The extent of degradation was inversely proportional to the initial substrate concentration. The rate of 4-CyP degradation was frequency dependent. The degradation rate increased proportionally with increasing ultrasonic power from 20 to 100 W and temperature in the range of 20-50°C. The most favorable degradation pH was acidic media. Destruction in the presence of saturating gas follows the order: argon>air>nitrogen. The 4-CyP degradation was inhibited in the presence of nitrogen gas owing to the free radical scavenging effect in vapor phase within the bubbles of cavitation. The ultrasonic degradation of 4-CyP was clearly promoted in the presence of bromide anions and the promoting effect on degradation increased with increasing bromide concentration. At low 4-CyP concentration (0.05 mg L(-1)), bicarbonate ion drastically enhanced the rate of 4-CyP degradation. Experiments conducted using pure and natural water demonstrated that the sonolytic treatment was more efficient in the natural water compared to pure water.     

Intensification of sonophotocatalytic degradation of p-nitrophenol at pilot scale capacity

Sonophotocatalysis involves the use of a combination of ultrasonic irradiation, ultraviolet radiation and a semiconductor photocatalyst, which enhances the rates of chemical reactions by the formation of enhanced amounts of free radicals. In the present work, the sonophotocatalytic degradation of p-nitrophenol has been investigated using low frequency ultrasound waves (25 kHz) with an acoustic power of 1 kW and UV tube of 11 W power rating at an operating volume of 7 L. The efficacy of combination of sonochemistry and photocatalysis has been initially compared with the individual operation of sonolysis and photocatalytic oxidation. The effect of operational conditions such as the initial p-nitrophenol concentration, pH and catalyst concentration on the extent of degradation has been investigated using sonophotocatalysis. The initial concentration of the pollutant was varied in the range 10 to 100 ppm whereas pH in the range of 2.5-11 and catalyst loading in the range of 0.5-4 g/l. Intensification studies have been carried out using hydrogen peroxide and Fenton chemistry. In all the systems investigated, maximum extent of degradation (94.6%) was observed for 10 ppm of p-nitrophenol initial concentration (w/v) using combination of sonophotocatalysis and optimum quantity of H(2)O(2). Use of Fenton chemistry also plays an effective role in enhancing the extent of degradation though the concentration of additive needs to be carefully adjusted in order to get maximum beneficial effects.     

The kinetics and mechanism of ultrasonic degradation of p-nitrophenol in aqueous solution with CCl4 enhancement

The ultrasonic degradation of p-nitrophenol (p-NP) in aqueous solution with CCl₄ enhancement was studied. The effects of operating parameters such as CCl₄ dosage, ultrasonic power, media temperature, the initial concentration of p-NP and initial pH value of the aqueous solution on the degradation of p-NP were investigated, and the enhancement mechanism of CCl₄ for p-NP sonolysis was also discussed. The results showed that the sonochemical degradation of p-NP was obviously enhanced by adding CCl₄. It attributed to the increase OH radicals concentration in the presence of CCl₄ as a hydrogen atom scavenger, and the formation of some oxidizing agents such as free chlorine and chlorine-containing radicals. The degradation of p-NP follows a pseudo-first-order kinetics. The degradation rate of p-NP increased with decreasing the temperature, the initial pH value of the solution and decreasing the initial concentration of p-NP. It was also found that p-NP can be mineralized in this process.     

Improving sono-activated persulfate oxidation using mechanical mixing in a 35-kHz ultrasonic reactor: Persulfate activation mechanism and its application

This study investigated the degradation of ibuprofen (IBP), an activated persulfate (PS), when subjected to ultrasonic (US) irradiation and mechanical mixing (M). The effects of several critical factors were evaluated, including the effect of rpm on M, PS concentration, and initial pH, and that of temperature on IBP degradation kinetics and the PS activation mechanism. The resulting IBP oxidation rate constant was significantly higher at 400 rpm. As the PS load increased, the IBP oxidation rate constant increased. The value of the IBP reaction rate increased with decreasing pH; below pH 4.9, there was no significant difference in the IBP oxidation rate constant. The IBP oxidation activation energy when using the US/M-PS system was 18.84 kJ mol⁻¹. In the US/M-PS system, PS activation was the primary effect of temperature at the interface during the explosion of cavitation bubbles. These encouraging results suggest that the US-PS/M process is a promising strategy for the treatment of IBP-based water pollutants.     

Intensification of sonochemical degradation of ammonium perfluorooctanoate by persulfate oxidant

Ammonium perfluorooctanoate (APFO) is an emerging environmental pollutant attracting significant attention due to its global distribution, high persistence, and bioaccumulation properties. The decomposition of APFO in aqueous solution with a combination of persulfate oxidant and ultrasonic irradiation was investigated. The effects of operating parameters, such as ultrasonic power, persulfate concentration, APFO concentration, and initial media pH on APFO degradation were discussed. In the absence of persulfate, 35.5% of initial APFO in 46.4 μmol/L solution under ultrasound irradiation, was decomposed rapidly after 120 min with the defluorination ratio reaching 6.73%. In contrast, when 10 mmol/L persulfate was used, 51.2% of initial APFO (46.4 μmol/L) was decomposed and the defluorination ratio reached 11.15% within 120 min reaction time. Enhancement of the decomposition of APFO can be explained by acceleration of substrate decarboxylation, induced by sulfate radical anions formed from the persulfate during ultrasonic irradiation. The SO₄^−•/APFO reactions at the bubble-water interface appear to be the primary pathway for the sonochemical degradation of the perfluorinated surfactants.     

Experimental design approach to the optimization of ultrasonic degradation of alachlor and enhancement of treated water biodegradability

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.     

Alternate pulses of ultrasound and electricity enhanced electrochemical process for p-nitrophenol degradation

A novel alternated ultrasonic and electric pulse enhanced electrochemical process was developed and used for investigating its effectiveness on the degradation of p-nitrophenol (PNP) in an aqueous solution. The impacts of pulse mode, pH, cell voltage, supporting electrolyte concentration, ultrasonic power and the initial concentration of PNP on the performance of PNP degradation were evaluated. Possible pathway of PNP degradation in this system was proposed based on the intermediates identified by GC–MS. Experimental results showed that 94.1% of PNP could be removed at 2 h in the dual-pulse ultrasound enhanced electrochemical (dual-pulse US-EC) process at mild operating conditions (i.e., pulse mode of electrochemical pulse time (T_EC) = 50 ms and ultrasonic pulse time (T_US) = 100 ms, initial pH of 3.0, cell voltage of 10 V, Na₂SO₄ concentration of 0.05 M, ultrasonic powder of 48.8 W and initial concentration of PNP of 100 mg/L), compared with 89.0%, 58.9%, 2.4% in simultaneous ultrasound enhanced electrochemical (US-EC) process, pulsed electrochemical (EC) process and pulsed ultrasound (US), respectively. Moreover, energy used in the dual-pulse US-EC process was reduced by 50.4% as compared to the US-EC process. The degradation of PNP in the pulsed EC process, US-EC process and dual-pulse process followed pseudo-first-order kinetics. Therefore, the dual-pulse US-EC process was found to be a more effective technique for the degradation of PNP and would have a promising application in wastewater treatment.