Degradation of phenol using a combination of ultrasonic and UV irradiations at pilot scale operation

In the present work, combination of ultraviolet (UV) irradiations (using 8 W UV tube) with ultrasonic (US) irradiations (rated power 1 kW and frequency of 25 kHz) has been investigated for the degradation of phenol at pilot scale of operation. Different modes of operation viz. UV alone, US alone, UV/US, UV/TiO₂ (photocatalysis), UV/H₂O₂, UV/NaCl, UV/US/TiO₂ (sonophotocatalysis) and H₂O₂ assisted sonophotocatalysis have been investigated with an objective of maximizing the extent of phenol degradation. Effect of presence of hydrogen peroxide and sodium chloride at a concentration of 10 g/l and TiO₂ over a range of 0.5–2.5 g/l has been investigated. It has been observed that 2.0 g/l of TiO₂ is the optimum concentration, beyond which a decrease in the extent of degradation is observed. Maximum extent of degradation of phenol was 37.75% for H₂O₂ assisted photosonocatalysis at pH of 2. The present work is first of its kind to report the use of combined ultrasonic and UV irradiations at pilot scale operation and obtained results should induce some degree of certainty in proposed industrial applications of sonochemical reactors for wastewater treatment.     

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.     

Degradation of imidacloprid containing wastewaters using ultrasound based treatment strategies

The present work deals with application of sonochemical reactors for the treatment of imidacloprid containing wastewaters either individually or in combination with other advanced oxidation processes. Experiments have been performed using two different configurations of sonochemical reactors viz. ultrasonic horn (20 kHz frequency and rated power of 240 W) and ultrasonic bath equipped with radially vibrating horn (25 kHz frequency and 1 kW rated power). The work also investigates the effect of addition of process intensifying agents such as H₂O₂ and CuO, which can enhance the production of free radicals in the system. The combination studies with advanced oxidation process involve the advanced Fenton process and combination of ultrasound with UV based oxidation. The extent of degradation obtained using combination of US and H₂O₂ at optimum loading of H₂O₂ was found to be 92.7% whereas 96.5% degradation of imidacloprid was achieved using the combination of US and advanced Fenton process. The process involving the combination of US, UV and H₂O₂ was found to be the best treatment approach where complete degradation of imidacloprid was obtained with 79% TOC removal. It has been established that the use of cavitation in combination with different oxidation processes can be effectively used for the treatment of imidacloprid containing wastewater.     

Degradation of reactive orange 4 dye using hydrodynamic cavitation based hybrid techniques

In the present work, degradation of reactive orange 4 dye (RO4) has been investigated using hydrodynamic cavitation (HC) and in combination with other AOP’s. In the hybrid techniques, combination of hydrodynamic cavitation and other oxidizing agents such as H₂O₂ and ozone have been used to get the enhanced degradation efficiency through HC device. The hydrodynamic cavitation was first optimized in terms of different operating parameters such as operating inlet pressure, cavitation number and pH of the operating medium to get the maximum degradation of RO4. Following the optimization of HC parameters, the degradation of RO4 was carried out using the combination of HC with H₂O₂ and ozone. It has been found that the efficiency of the HC can be improved significantly by combining it with H₂O₂ and ozone. The mineralization rate of RO4 increases considerably with 14.67% mineralization taking place using HC alone increases to 31.90% by combining it with H₂O₂ and further increases to 76.25% through the combination of HC and ozone. The synergetic coefficient of greater than one for the hybrid processes of HC + H₂O₂ and HC + Ozone has suggested that the combination of HC with other oxidizing agents is better than the individual processes for the degradation of dye effluent containing RO4. The combination of HC with ozone proves to be the most energy efficient method for the degradation of RO4 as compared to HC alone and the hybrid process of HC and H₂O₂.     

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.     

Intensified depolymerization of aqueous polyacrylamide solution using combined processes based on hydrodynamic cavitation,ozone, ultraviolet light and hydrogen peroxide

The present work deals with intensification of depolymerization of polyacrylamide (PAM) solution using hydrodynamic cavitation (HC) reactors based on a combination with hydrogen peroxide (H₂O₂), ozone (O₃) and ultraviolet (UV) irradiation. Effect of inlet pressure in hydrodynamic cavitation reactor and power dissipation in the case of UV irradiation on the extent of viscosity reduction has been investigated. The combined approaches such as HC + UV, HC + O₃, HC + H₂O₂, UV + H₂O₂ and UV + O₃ have been subsequently investigated and found to be more efficient as compared to individual approaches. For the approach based on HC + UV + H₂O₂, the extent of viscosity reduction under the optimized conditions of HC (3 bar inlet pressure) + UV (8 W power) + H₂O₂ (0.2% loading) was 97.27% in 180 min whereas individual operations of HC (3 bar inlet pressure) and UV (8 W power) resulted in about 35.38% and 40.83% intrinsic viscosity reduction in 180 min respectively. In the case of HC (3 bar inlet pressure) + UV (8 W power) + ozone (400 mg/h flow rate) approach, the extent of viscosity reduction was 89.06% whereas individual processes of only ozone (400 mg/h flow rate), ozone (400 mg/h flow rate) + HC (3 bar inlet pressure) and ozone (400 mg/h flow rate) + UV (8 W power) resulted in lower extent of viscosity reduction as 50.34%, 60.65% and 75.31% respectively. The chemical structure of the treated PAM by all approaches was also characterized using FTIR (Fourier transform infrared) spectra and it was established that no significant chemical structure changes were obtained during the treatment. Overall, it can be said that the combination of HC + UV + H₂O₂ is an efficient approach for the depolymerization of PAM solution.     

Ultrasonic synthesis and photocatalytic characterization of H3PW12O40/TiO2 (anatase)

A novel H₃PW₁₂O₄₀/TiO₂ (anatase) composite photocatalyst was prepared by a high-intensity ultrasonic method using a lower temperature (80 °C) and was characterized by XRD and FT-IR. Its photocatalytic activity, using solar light, was evaluated through the degradation of organic dye methylene blue (MB) in aqueous. When MB solution (50 mg/l, 200 ml) containing H₃PW₁₂O₄₀/TiO₂ (anatase) (0.4 g) was degraded by solar irradiation after 90 min, the removal of concentration and TOC of MB reached 95% and 73%, respectively. The photocatalyst activity of H₃PW₁₂O₄₀/TiO₂ (anatase) was much higher than TiO₂ which was prepared in the same way. H₃PW₁₂O₄₀/TiO₂ remained efficient after five repeated experiments.     

Sonocatalytic and sonophotocatalytic degradation of rhodamine 6G containing wastewaters

The present work deals with degradation of aqueous solution of Rhodamine 6G (Rh 6G) using sonocatalytic and sonophotocatalytic treatment schemes based on the use of cupric oxide (CuO) and titanium dioxide (TiO₂) as the solid catalysts. Experiments have been carried out at the operating capacity of 2 L and constant initial pH of 12.5. The effect of catalyst loading on the sonochemical degradation has been investigated by varying the loading over the range of 1.5–4.5 g/L. It has been observed that the maximum degradation of 52.2% was obtained at an optimum concentration of CuO as 1.5 g/L whereas for TiO₂ maximum degradation was observed as 51.2% at a loading of 4 g/L over similar treatment period. Studies with presence of radical scavengers such as methanol (CH₃OH) and n-butanol (C₄H₉OH) indicated lower extents of degradation confirming the dominance of radical mechanism. The combined approach of ultrasound, solid catalyst and scavengers has also been investigated at optimum loadings to simulate real conditions. The optimal solid loading was used for studies involving oxidation using UV irradiations where 26.4% and 28.9% of degradation was achieved at optimal loading of CuO and TiO_2, respectively. Studies using combination of UV and US irradiations have also been carried out using the optimal concentration of the catalysts. It has been observed that maximum degradation of 63.3% is achieved using combined US and UV with TiO₂ (4 g/L) as the photocatalyst. Overall it can be said that the combined processes give higher extent of degradation as compared to the individual processes based on US or UV irradiations.     

Intensification of degradation of methomyl (carbamate group pesticide) by using the combination of ultrasonic cavitation and process intensifying additives

In the present work, the degradation of methomyl has been carried out by using the ultrasound cavitation (US) and its combination with H₂O₂, Fenton and photo-Fenton process. The study of effect of operating pH and ultrasound power density has indicated that maximum extent of degradation of 28.57% could be obtained at the optimal pH of 2.5 and power density of 0.155 W/mL. Application of US in combination with H₂O₂, Fenton and photo-Fenton process has further accelerated the rate of degradation of methomyl with complete degradation of methomyl in 27 min, 18 min and 9 min respectively. Mineralization study has proved that a combination of US and photo-Fenton process is the most effective process with maximum extent of mineralization of 78.8%. Comparison of energy efficiency and cost effectiveness of various processes has indicated that the electrical cost of 79892.34 Rs./m³ for ultrasonic degradation of methomyl has drastically reduced to 2277.00 Rs./m³, 1518.00 Rs./m³ and 807.58 Rs./m³ by using US in combination with H₂O₂, Fenton and photo-Fenton process respectively. The cost analysis has also indicated that the combination of US and photo-Fenton process is the most energy efficient and cost effective process.     

Degradation of imidacloprid using combined advanced oxidation processes based on hydrodynamic cavitation

The harmful effects of wastewaters containing pesticides or insecticides on human and aquatic life impart the need of effectively treating the wastewater streams containing these contaminants. In the present work, hydrodynamic cavitation reactors have been applied for the degradation of imidacloprid with process intensification studies based on different additives and combination with other similar processes. Effect of different operating parameters viz. concentration (20–60 ppm), pressure (1–8 bar), temperature (34 °C, 39 °C and 42 °C) and initial pH (2.5–8.3) has been investigated initially using orifice plate as cavitating device. It has been observed that 23.85% degradation of imidacloprid is obtained at optimized set of operating parameters. The efficacy of different process intensifying approaches based on the use of hydrogen peroxide (20–80 ppm), Fenton’s reagent (H₂O₂:FeSO₄ ratio as 1:1, 1:2, 2:1, 2:2, 4:1 and 4:2), advanced Fenton process (H₂O₂:Iron Powder ratio as 1:1, 2:1 and 4:1) and combination of Na₂S₂O₈ and FeSO₄ (FeSO₄:Na₂S₂O₈ ratio as 1:1, 1:2, 1:3 and 1:4) on the extent of degradation has been investigated. It was observed that near complete degradation of imidacloprid was achieved in all the cases at optimized values of process intensifying parameters. The time required for complete degradation of imidacloprid for approach based on hydrogen peroxide was 120 min where as for the Fenton and advance Fenton process, the required time was only 60 min. To check the effectiveness of hydrodynamic cavitation with different cavitating devices, few experiments were also performed with the help of slit venturi as a cavitating device at already optimized values of parameters. The present work has conclusively established that combined processes based on hydrodynamic cavitation can be effectively used for complete degradation of imidacloprid.     

Degradation of diclofenac sodium using combined processes based on hydrodynamic cavitation and heterogeneous photocatalysis

Diclofenac sodium, a widely detected pharmaceutical drug in wastewater samples, has been selected as a model pollutant for degradation using novel combined approach of hydrodynamic cavitation and heterogeneous photocatalysis. A slit venturi has been used as cavitating device in the hydrodynamic cavitation reactor. The effect of various operating parameters such as inlet fluid pressure (2–4 bar) and initial pH of the solution (4–7.5) on the extent of degradation have been studied. The maximum extent of degradation of diclofenac sodium was obtained at inlet fluid pressure of 3 bar and initial pH as 4 using hydrodynamic cavitation alone. The loadings of TiO₂ and H₂O₂ have been optimised to maximise the extent of degradation of diclofenac sodium. Kinetic study revealed that the degradation of diclofenac sodium fitted first order kinetics over the selected range of operating protocols. It has been observed that combination of hydrodynamic cavitation with UV, UV/TiO₂ and UV/TiO₂/H₂O₂ results in enhanced extents of degradation as compared to the individual schemes. The maximum extent of degradation as 95% with 76% reduction in TOC has been observed using hydrodynamic cavitation in conjunction with UV/TiO₂/H₂O₂ under the optimised operating conditions. The diclofenac sodium degradation byproducts have been identified using LC/MS analysis.     

Ultrasound (US), Ultraviolet light (UV) and combination (US + UV) assisted semiconductor catalysed degradation of organic pollutants in water: Oscillation in the concentration of hydrogen peroxide formed in situ

Application of Advanced Oxidation Processes (AOP) such as sono, photo and sonophoto catalysis in the purification of polluted water under ambient conditions involve the formation and participation of Reactive Oxygen Species (ROS) like OH, HO₂, O₂⁻, H₂O₂ etc. Among these, H₂O₂ is the most stable and is also a precursor for the reactive free radicals. Current investigations on the ZnO mediated sono, photo and sonophoto catalytic degradation of phenol pollutant in water reveal that H₂O₂ formed in situ cannot be quantitatively correlated with the degradation of the pollutant. The concentration of H₂O₂ formed does not increase corresponding to phenol degradation and reaches a plateau or varies in a wave-like fashion (oscillation) with well defined crests and troughs, indicating concurrent formation and decomposition. The concentration at which decomposition overtakes formation or formation overtakes decomposition is sensitive to the reaction conditions. Direct photolysis of H₂O₂ in the absence of catalyst or the presence of pre-equilibrated (with the adsorption of H₂O₂) catalyst in the absence of light does not lead to the oscillation. The phenomenon is more pronounced in sonocatalysis, the intensity of oscillation being in the order sonocatalysis > photocatalysis ⩾ sonophotocatalysis while the degradation of phenol follows the order sonophotocatalysis > photocatalysis > sonocatalysis > sonolysis > photolysis. In the case of sonocatalysis, the oscillation continues for some more time after discontinuing the US irradiation indicating that the reactive free radicals as well as the trapped electrons and holes which interact with H₂O₂ have longer life time (memory effect).     

Effect of process intensifying parameters on the hydrodynamic cavitation based degradation of commercial pesticide (methomyl) in the aqueous solution

Methomyl, a carbamate pesticide, is classified as a pesticide of category-1 toxicity and hence shows harmful effects on both human and aquatic life. In the present work, the degradation of methomyl has been studied by using hydrodynamic cavitation reactor (HC) and its combination with intensifying agents such as H₂O₂, fenton reagent and ozone (hybrid processes). Initially, the optimization of operating parameters such pH and inlet pressure to the cavitating device (circular venturi) has been carried out for maximizing the efficacy of hydrodynamic cavitation. Further degradation study of methomyl by the application of hybrid processes was carried out at an optimal pH of 2.5 and the optimal inlet pressure of 5 bar. Significant synergetic effect has been observed in case of all the hybrid processes studied. Synergetic coefficient of 5.8, 13.41 and 47.6 has been obtained by combining hydrodynamic cavitation with H₂O₂, fenton process and ozone respectively. Efficacy of individual and hybrid processes has also been obtained in terms of energy efficiency and extent of mineralization. HC + Ozone process has proved to be the most effective process having highest synergetic coefficient, energy efficiency and the extent of mineralization. The study has also encompassed the identification of intermediate by-products generated during the degradation and has proposed the probable degradation pathway. It has been conclusively established that hydrodynamic cavitation in the presence of intensifying agents can effectively be used for complete degradation of methomyl.     

Degradation of 2,4-dinitrophenol using a combination of hydrodynamic cavitation,chemical and advanced oxidation processes

In the present work, degradation of 2,4-dinitrophenol (DNP), a persistent organic contaminant with high toxicity and very low biodegradability has been investigated using combination of hydrodynamic cavitation (HC) and chemical/advanced oxidation. The cavitating conditions have been generated using orifice plate as a cavitating device. Initially, the optimization of basic operating parameters have been done by performing experiments over varying inlet pressure (over the range of 3–6 bar), temperature (30 °C, 35 °C and 40 °C) and solution pH (over the range of 3–11). Subsequently, combined treatment strategies have been investigated for process intensification of the degradation process. The effect of HC combined with chemical oxidation processes such as hydrogen peroxide (HC/H₂O₂), ferrous activated persulfate (HC/Na₂S₂O₈/FeSO₄) and HC coupled with advanced oxidation processes such as conventional Fenton (HC/FeSO₄/H₂O₂), advanced Fenton (HC/Fe/H₂O₂) and Fenton-like process (HC/CuO/H₂O₂) on the extent of degradation of DNP have also been investigated at optimized conditions of pH 4, temperature of 35 °C and inlet pressure of 4 bar. Kinetic study revealed that degradation of DNP fitted first order kinetics for all the approaches under investigation. Complete degradation with maximum rate of DNP degradation has been observed for the combined HC/Fenton process. The energy consumption analysis for hydrodynamic cavitation based process has been done on the basis of cavitational yield. Degradation intermediates have also been identified and quantified in the current work. The synergistic index calculated for all the combined processes indicates HC/Fenton process is more feasible than the combination of HC with other Fenton like processes.     

A simultaneous,direct microwave/ultrasound-assisted digestion procedure for the determination of total Kjeldahl nitrogen

Simultaneous direct irradiation with microwaves and ultrasound was used to determine total Kjeldahl nitrogen. The method involves chemical digestion in two steps, mineralization with sulfuric acid and oxidation with H₂O₂. The most influential variables for the microwave/ultrasound (MW/US)-assisted digestion were optimized using tryptophan as the model substance. The optimum conditions were: H₂SO₄ volume, 10 mL; H₂O₂ volume, 5 mL; weight of sample, 0.05 g; MW power, 500 W; US power, 50 W; digestion time, 7 min (i.e., 5 min mineralization and 2 min oxidation). A modification of the classical Kjeldahl (Hach) method and an US-assisted digestion method were used for comparison. The latter was also optimized; the optimum conditions were: H₂SO₄ volume, 10 mL; H₂O₂ volume, 5 mL; sonication time with H₂SO₄, 15 min; sonication time with H₂O₂,10 min; US power, 50 W; weight of sample, 0.05 g. Five pure amino acids and two certified reference materials (NIST standard reference materials 1547 (peach leaves), and soil, NCS DC 73322) were analyzed to assess the accuracy of our new MW/US-assisted digestion method, that was successfully applied to five real samples. The significant reduction in digestion time (being 30 min and 25 min for classical Kjeldahl and US-assisted digestion methods, respectively) and consumption of reagents show that simultaneous and direct MW/US irradiation is a powerful and promising tool for low-pressure digestion of solid and liquid samples.     

Sonocatalytic degradation of organic dyes and comparison of catalytic activities of CeO2/TiO2, SnO2/TiO2 and ZrO2/TiO2 composites under ultrasonic irradiation

The CeO₂/TiO₂, SnO₂/TiO₂ and ZrO₂/TiO₂ composites were prepared by dispersing various nano-sized oxides (CeO₂, SnO₂, ZrO₂ and TiO₂) with ultrasound and mixing TiO₂ with CeO₂, SnO₂ and ZrO₂, respectively, in boiling water in a molar ratio of 4:1, followed by calcining temperature 500 °C for 60 min. Then a series of sonocatalytic degradation experiments were carried out under ultrasonic irradiation in the presence of CeO₂/TiO₂, SnO₂/TiO₂ and ZrO₂/TiO₂ composites and nano-sized TiO₂ powder. Also, the influences of heat-treatment temperature and heat-treatment time on the sonocatalytic activities of CeO₂/TiO₂, SnO₂/TiO₂ and ZrO₂/TiO₂ composites, and of irradiation time and solution acidity on the sonocatalytic degradation of Acid Red B were investigated by UV–vis spectra. It was found that the sonocatalytic degradation of Acid Red B shows significant variation in rate and ratio that decreases in order: CeO₂/TiO₂ > SnO₂/TiO₂ > TiO₂ > ZrO₂/TiO₂ > SnO₂ > CeO₂ > ZrO₂, and the corresponding ratios of Acid Red B in aqueous solution are 91.32%, 67.41%, 65.26%, 41.67%, 28.34%, 26.75% and 23.33%, respectively. And that the degradation ratio is only 16.67% under onefold ultrasonic irradiation. Because of the good degradation efficiency, this method may be an advisable choice for the treatment of non- or low-transparent wastewaters in the future.     

Enhanced OH radical generation by dual-frequency ultrasound with TiO2 nanoparticles: Its application to targeted sonodynamic therapy

The present study demonstrated the enhanced hydroxyl (OH) radical generation by combined use of dual-frequency (0.5 MHz and 1 MHz) ultrasound (US) and titanium dioxide (TiO₂) nanoparticles (NPs) as sonocatalyst. The OH radical generation became the maximum, when 0.5 MHz US was irradiated at an intensity of 0.8 W/cm² and 1 MHz US was irradiated at intensities at 0.4 W/cm² in the presence of TiO₂ NPs under the examined conditions. After incorporation of TiO₂ NPs modified with targeting protein pre-S1/S2, HepG2 cancer cells were subjected to the dual-frequency US at optimum irradiation intensities (“targeted-TiO₂/dual-US treatment”). Growth of the HepG2 cells was reduced by 46% compared with the control condition after irradiation of dual-frequency US for 60 s with TiO₂ NPs incorporation. In contrast, HepG2 cell growth was almost the same as that in the control condition when cells were irradiated with either 0.5 MHz or 1 MHz ultrasound alone without TiO₂ NP incorporation.     

Ultrasound assisted synthesis of TiO2–WO3 heterostructures for the catalytic degradation of Tergitol (NP-9) in water

TiO₂–WO₃ heterostructures were synthesized at room temperature, ambient pressure, and short reaction time via a sonochemical approach. TEM and EDX images show that the prepared TiO₂–WO₃ heterostructures consist of globular agglomerates (∼250 nm in diameter) composed of very small (<5 nm) dense particles (WO₃) dispersed inside the globules. The observed less intense monoclinic WO₃ diffraction peak (around 2θ = 22° belonging to (0 0 1) plane) and the high intense hexagonal WO₃ diffraction peak (around 2θ = 28° belonging to (2 0 0) plane) in XRD indicate that there may be phase transition occurring due to the formation of intimate bond between TiO₂ and WO₃. In addition, the formation of such new phase was also observed from Raman spectra with a new peak at 955 cm⁻¹, which is due to the symmetric stretching of W = O terminal. The catalytic activity of TiO₂–WO₃ heterostructures was tested for the degradation of wastewater pollutant containing Tergitol (NP-9) by a process combined with ozonation and it showed two-fold degradation rate compared with ozone process alone.     

Combined treatment approaches based on ultrasound for removal of triazophos from wastewater

Pesticides have been the major contributors to the growth of agricultural productivity, but the wide spread use in the fields and discharge from the manufacturing industries have also contributed to environmental concerns. In the present work, degradation of triazophos (O,O-diethyl-O-(1-phenyl-1H-1,2,4-triazol-3-yl) phosphorothioate) as a model pollutant has been investigated using high volume continuous ultrasonic flow cell for the first time. Effect of power dissipation and initial pH on the extent of triazophos degradation using acoustic cavitation has been investigated initially. Under the optimized set of operating power dissipation and pH, effect of addition of hydrogen peroxide (ratio of C₁₂H₁₆N₃O₃PS (Triazophos):H₂O₂ over the range of 1:1–1:5), ozone (over the flow rate of 100–400 mg/h) and Fenton’s reagent (C₁₂H₁₆N₃O₃PS:FeSO₄:H₂O₂ ratio over the range of 1:1:1–1:4:4) has been investigated as possible process intensification strategy. Combined operation of US with H₂O₂ and Ozone resulted in 48.6% and 54.6% triazophos degradation respectively whereas combination of US and Fenton’s reagent resulted in maximum degradation as 92.2% and also resulted in maximum COD removal as 88.5%. The study also focused on identification of intermediate products formed during the degradation as well as establishing the kinetic rate constants and the synergistic index for different approaches. The study has established that cavitation can be effectively used for triazophos degradation with significant intensification benefits based on the use of combination approach.     

Ultrasonic assisted-Fenton-like degradation of nitrobenzene at neutral pH using nanosized oxides of Fe and Cu

Ultrasonic-assisted heterogeneous Fenton reaction was used for degradation of nitrobenzene (NB) at neutral pH conditions. Nano-sized oxides of α-Fe₂O₃ and CuO were prepared, characterized and tested in degradation of NB (10 mg L⁻¹) under sonication of 20 kHz at 25 °C. Complete degradation of NB was effected at pH 7 in presence of 10 mM H₂O₂ after 10 min of sonication in presence of α-Fe₂O₃ (1.0 g L⁻¹), (k = 0.58 min⁻¹) and after 25 min in case of CuO (k = 0.126 min⁻¹). α-Fe₂O₃ showed also effective degradation under the conditions of 0.1 g L⁻¹ oxide and 5.0 mM of H₂O₂, even though with a lower rate constant (0.346 min⁻¹). Sonication plays a major role in enhancing the production of hydroxyl radicals in presence of solid oxides. Hydroxyl radicals-degradation pathway is suggested and adopted to explain the differences noted in rate constants recorded on using different oxides.