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.     

The sonochemical decolourisation of textile azo dye Orange II: Effects of Fenton type reagents and UV light

The removal of Orange II (O-II) from aqueous solution under irradiation at 850 kHz has been studied. The effects of both homogeneous (with FeSO₄/H₂O₂)_, and heterogeneous (Fe containing ZSM-5 zeolite/H₂O₂) Fenton type reagents are reported together with the effect of UV irradiation in combination with ultrasound both alone and with homogeneous Fenton-type reagent.Degrees of decolourisation of 6.5% and 28.9% were observed using UV radiation and ultrasound, respectively, whereas under the simultaneous irradiation of ultrasound and UV light, the decolourisation degree reached 47.8%, indicating a synergetic effect of ultrasound and UV light. The decolourisation was increased with the addition of Fenton’s reagent with an optimal Fenton molar reagent ratio, Fe²⁺:H₂O₂ of 1:50. In the combined process of ultrasound and UV light with the homogeneous Fenton system 80.8% decolourisation could be achieved after 2 h indicating that UV improves this type of Orange II degradation. The degree of decolourisation obtained using the heterogeneous sono-Fenton system (Fe containing ZSM-5 zeolite catalysts + H₂O₂ + ultrasound) were consistently lower than the traditional homogeneous ultrasound Fenton system. This can be attributed to the greater difficulty of the reaction between Fe ions and hydrogen peroxide.In all cases the Orange II ultrasonic decolourisation was found to follow first order kinetics.     

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.     

Performance and energetic analysis of hydrodynamic cavitation and potential integration with existing advanced oxidation processes: A case study for real life greywater treatment

The current work is a “first of a kind” report on the feasibility and efficacy of hydrodynamic cavitation integrated Advanced Oxidation Processes (AOP’s) towards treatment of a real life greywater stream in form of kitchen wastewater. The work has been carried out in a sequential manner starting with geometry optimization of orifice plate (cavitating device) followed by studying the effects of inlet pressure, pH, effluent dilution ratio on degradation of TOC and COD. Under optimized conditions of pH 3, 4 bar pressure, TOC and COD reduction of 18.23 and 25% were obtained using HC for a period of 120 min. To improve the performance of HC, further studies were carried out by integrating H₂O₂ and O₃ with HC. Using 5 g/h optimum dosage of H₂O₂, 87.5% reduction in COD was obtained beyond which it started decreasing. Moreover, integrating O₃ (57.5% reduction in COD) increased the treatment cost. However, a hybrid process (HC + H₂O₂ + O₃) yielded 76.26 and 98.25% reductions in TOC and COD within 60 min. The energetics of all the processes and the treatment costs were studied in detail and it was concluded that combined process of HC + H₂O₂ + O₃ surpassed by far the performances of HC + H₂O₂ and HC + O₃.     

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.     

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.     

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.     

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 a cationic dye (Rhodamine 6G) using hydrodynamic cavitation coupled with other oxidative agents: Reaction mechanism and pathway

In the present study, decolorization and mineralization of a cationic dye, Rhodamine 6G (Rh6G), has been carried out using hydrodynamic cavitation (HC). Two cavitating devices such as slit and circular venturi were used to generate cavitation in HC reactor. The process parameters such as initial dye concentration, solution pH, operating inlet pressure, and cavitation number were investigated in detail to evaluate their effects on the decolorization efficiency of Rh6G. Decolorization of Rh6G was marginally higher in the case of slit venturi as compared to circular venturi. The kinetic study showed that decolorization and mineralization of the dye fitted first-order kinetics. The loadings of H₂O₂ and ozone have been optimized to intensify the decolorization and mineralization efficiency of Rh6G using HC. Nearly 54% decolorization of Rh6G was obtained using a combination of HC and H₂O₂ at a dye to H₂O₂ molar ratio of 1:30. The combination of HC with ozone resulted in 100% decolorization in almost 5–10 min of processing time depending upon the initial dye concentration. To quantify the extent of mineralization, total organic carbon (TOC) analysis was also performed using various processes and almost 84% TOC removal was obtained using HC coupled with 3 g/h of ozone. The degradation by-products formed during the complete degradation process were qualitatively identified by liquid chromatography-mass spectrometry (LC-MS) and a detailed degradation pathway has been proposed.     

Advanced oxidation of Reactive Blue 181 solution: A comparison between Fenton and Sono-Fenton Process

In this work, the decolorization of C.I. Reactive Blue 181 (RB181), an anthraquinone dye, by Ultrasound and Fe²⁺ H₂O₂ processes was investigated. The effects of operating parameters, such as Fe²⁺ dosage, H₂O₂ dosage, pH value, reaction time and temperature were examined. Process optimisation [pH, ferrous ion (Fe²⁺), hydrogen peroxide (H₂O₂), and reaction time], kinetic studies and their comparison were carried out for both of the processes. The Sono-Fenton process was performed by indirect sonication in an ultrasonic water bath, which was operated at a fixed 35-kHz frequency. The optimum conditions were determined as [Fe²⁺] = 30 mg/L, [H₂O₂] = 50 mg/L and pH = 3 for the Fenton process and [Fe²⁺] = 10 mg/L, [H₂O₂] = 40 mg/L and pH = 3 for the Sono-Fenton process. The colour removals were 88% and 93.5% by the Fenton and Sono-Fenton processes, respectively. The highest decolorization was achieved by the Sono-Fenton process because of the production of some oxidising agents as a result of sonication. The paper also discussed kinetic parameters. The decolorization kinetic of RB181 followed pseudo-second-order reaction (Fenton study) and Behnajady kinetics (Sono-Fenton study).     

Critical factors in sonochemical degradation of fumaric acid

The effects of critical factors such as Henry’s Law constant, atmospheric OH rate constant, initial concentration, H₂O₂, FeSO₄ and tert-butanol on the sonochemical degradation of fumaric acid have been investigated. The pseudo first-order rate constant for the sonochemical degradation of 1 mM fumaric acid is much lower than those for chloroform and phenol degradation, and is related to solute concentration at the bubble/water interface and reactivity towards hydroxyl radicals. Furthermore, fumaric acid is preferentially oxidized at the lower initial concentration. It is unreactive to H₂O₂ under agitation at room temperature. However, the degradation rate of fumaric acid increases with the addition of H₂O₂ under sonication. 0.1 mM of fumaric acid suppresses H₂O₂ formation thanks to water sonolysis, while degradation behavior is also dramatically affected by the addition of an oxidative catalyst (FeSO₄) or radical scavenger (tert-butanol), indicating that the degradation of fumaric acid is caused by hydroxyl radicals generated during the collapse of high-energy cavities.     

Optimization of a heterogeneous catalytic hydrodynamic cavitation reactor performance in decolorization of Rhodamine B: Application of scrap iron sheets

A low pressure pilot scale hydrodynamic cavitation (HC) reactor with 30 L volume, using fixed scrap iron sheets, as the heterogeneous catalyst, with no external source of H₂O₂ was devised to investigate the effects of operating parameters of the HC reactor performance. In situ generation of Fenton reagents suggested an induced advanced Fenton process (IAFP) to explain the enhancing effect of the used catalyst in the HC process. The reactor optimization was done based upon the extent of decolorization (ED) of aqueous solution of Rhodamine B (RhB). To have a perfect study on the pertinent parameters of the heterogeneous catalyzed HC reactor, the following cases as, the effects of scrap iron sheets, inlet pressure (2.4–5.8 bar), the distance between orifice plates and catalyst sheets (submerged and inline located orifice plates), back-pressure (2–6 bar), orifice plates type (4 various orifice plates), pH (2–10) and initial RhB concentration (2–14 mg L^?1) have been investigated. The results showed that the highest cavitational yield can be obtained at pH 3 and initial dye concentration of 10 mg L^?1. Also, an increase in the inlet pressure would lead to an increase in the ED. In addition, it was found that using the deeper holes (thicker orifice plates) would lead to lower ED, and holes with larger diameter would lead to the higher ED in the same cross-sectional area, but in the same holes’ diameters, higher cross-sectional area leads to the lower ED. The submerged operation mode showed a greater cavitational effects rather than the inline mode. Also, for the inline mode, the optimum value of 3 bar was obtained for the back-pressure condition in the system. Moreover, according to the analysis of changes in the UV–Vis spectra of RhB, both degradation of RhB chromophore structure and N-deethylation were occurred during the catalyzed HC process.     

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.     

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.     

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.     

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.     

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.     

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.     

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).     

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.