Strategies to improve biological oxidation of real wastewater using cavitation based pre-treatment approaches

The present work demonstrates the effective application of pretreatment based on cavitation to improve biological oxidation of real municipal and industrial wastewater. The optimum pretreatment conditions based on ultrasonic cavitation for treatment of municipal wastewater were observed as power dissipation of 90 W, a duty cycle of 70% and H₂O₂ dosage of 0.2 g/L resulting in about 24.9% COD reduction. The use of modified sludge and ultrasonic pretreatment for biological oxidation resulted in significant reduction in treatment time (36 h) than the treatment time (60 h) required for biological oxidation using untreated sludge as inoculum. Also, significantly enhanced biodegradability index (BI) from 0.33 to 0.6 was achieved using pretreatment for biological oxidation process. For the treatment of real industrial wastewater, different pretreatment approaches based on hydrodynamic cavitation (HC) in combination with H₂O₂, ozone or Fenton were investigated. The pretreatment using best approach of HC + Fenton resulted in 44.2% of COD reduction in total whereas only 28.1% of COD reduction was achieved for the untreated effluent being applied in the biological oxidation. Overall, the present work demonstrated the effectiveness of the pretreatment based on cavitation for the improved treatment of municipal and industrial wastewaters.     

Effect of intensifying additives on the degradation of thiamethoxam using ultrasound cavitation

The present study has investigated the degradation of thiamethoxam using ultrasound cavitation (US) operated at a frequency of 20 kHz and its combination with intensifying additives viz. hydrogen peroxide, Fenton and photo-Fenton reagent. At the outset, the performance of US (20 kHz) has been maximised by the optimization of process parameters. Highest rate of degradation of thiamethoxam was observed at the optimum ultrasonic power density of 0.22 W/mL, thiamethoxam concentration of 10 ppm and the pH of 2. The established optimum values of operating parameters were used further in case of combined treatment approaches. The effect of concentration of H₂O₂ on the rate of degradation of thiamethoxam in the case of US + H₂O₂ process has confirmed the existence of optimum concentration of H₂O₂ with the ratio of thiamethoxam: H₂O₂ as 1:10. US + Fenton process indicated the optimal molar ratio of FeSO₄·7H₂O:H₂O₂ as 1:15. The combined processes of US + H₂O_2, US + Fenton and US + photo-Fenton have resulted in the extent of degradation of 20.47 ± 0.61%, 34.41 ± 1.03% and 85.17 ± 2.56% respectively after 45 min. of operation. These combined processes lead to the synergistic index of 2.04 ± 0.06, 2.26 ± 0.07 and 2.42 ± 0.07 in case of US + H₂O₂, US + Fenton and US + photo-Fenton processes respectively over only US/stirring treatment with the additive. Additionally, the extent of mineralization and the energy efficiency of individual and combined processes have been compared. US + photo-Fenton process has been found to be the best strategy for effective degradation of thiamethoxam with a significant intensification benefit. The by-products formed during the ultrasonic degradation of thiamethoxam have been identified by using LC-MS/MS analysis.     

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 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.     

Sonochemical synthesis of Ce-TiO2 nanocatalyst and subsequent application for treatment of real textile industry effluent

Treatment of real textile industry effluent using photocatalysis, sonocatalysis, sonophotocatalysis and H₂O₂ assisted sonophotocatalysis have been studied based on the use of Ce-TiO₂ nanocatalyst synthesized using sonochemical co-precipitation method. Characterization studies of the obtained catalyst revealed crystallite size as 1.44 nm with particles having spherical morphology. A shift of the absorption edge to the visible light range was also observed in UV–Vis diffuse reflectance spectra (UV-DRS) analysis. The effects of different operational parameters viz catalyst dose (0.5 g/L-2 g/L), temperature (30 °C-55 °C) and pH (3–12) on the COD reduction were studied. The reduction in the COD was higher at lower pH and the optimum temperature established was 45 °C. It was also elucidated that the required catalyst dose was lesser in combined sonophotocatalysis when compared with individual photocatalysis and sonocatalysis. Combination of processes and addition of oxidants increased the COD reduction with the sonophotocatalytic oxidation combined with H₂O₂ treatment showing the best results for COD reduction (84.75%). The highest reduction in COD for photocatalysis was only 45.09% and for sonocatalysis, it was marginally higher at 58.62%. The highest reduction in COD achieved by sonophotocatalysis was 64.41%. Toxicity tests coupled with Liquid Chromatography Mass Spectrometry (LC-MS) analysis revealed that there were no additional toxic intermediates added to the system during the treatment. Kinetic study allowed establishing that generalized kinetic model fits the experimental results well. Overall, the combined advanced oxidation processes showed better results than the individual processes with higher COD reduction and lower requirement of the catalyst.     

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.     

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.     

Synergetic effects of ultrasound and sodium alginate coating on mass transfer and qualities of osmotic dehydrated pumpkin

This research studied the effects of combined ultrasound and 3% sodium alginate (SA) coating pretreatment (US + Coat) on mass transfer kinetics, quality aspects, and cell structure of osmotic dehydrated (OD) pumpkin. The results of the pretreatment were compared with the results of control (non-pretreated osmotic dehydration) and other three pretreatment methods, which were 1) ultrasound in distilled water for 10 min (USC), 2) ultrasound in 70% (w/w) sucrose solution (US) for 10, 20 and 30 min, and 3) coating with 1%, 2%, 3% (w/w) SA. The coating pretreatments with SA resulted in a higher water loss (WL) but lower water activity and solid gain (SG) than other treatments. US pretreatments resulted in the highest effective diffusion coefficients of water (D_w) and solid (D_s) but the cell structure of the product was deformed. The 3% SA coating treatment had the highest WL/SG (5.28) but with the longest OD time (12 h). Using the US + Coat pretreatment gave satisfactory high WL/SG (5.18), D_w (1.09 × 10⁻¹⁰ m²s⁻¹) and D_s (5.15 × 10⁻¹¹ m²s⁻¹), reduced the OD time to 9 h, and preserved the cell structure of the product. This research suggests that US + Coat pretreatment can be an effective processing step in the production of OD pumpkin.     

Intensified sonochemical degradation of 2-Picoline in combination with advanced oxidizing agents

2-picoline is a very important pyridine derivative with significant applications though it is also poisonous and harmful having considerable adverse influence on aquatic life, environment and organisms. The need for developing effective treatment methodologies for 2-Picoline directed the current work focusing on degradation of 2-Picoline using the combination of ultrasound and advanced oxidants such as hydrogen peroxide (H₂O₂), potassium persulphate (KPS), Fenton’s reagent, and Peroxymonosulphate (PMS) along with the use of Titanium oxide (TiO₂) as catalyst. Ultrasonic bath having 8 L capacity and operating frequency of 40 ± 2 kHz has been used. The effect of parameters like power, initial pH, temperature, time and initial concentration of 2-Picoline were studied to establish best operating conditions which were further used in the combination treatment approaches of ultrasound with oxidising agents. The chemical oxygen demand (COD) reduction for the optimized approaches of ultrasound in combination with oxidizing agents was also determined. Degradation experiments were performed using oxidising agents also in absence of ultrasound to investigate the individual treatment capacity of the oxidants and also the synergetic index for the combination. Kinetic study demonstrated that second order model suited for all the treatment approaches except US/Fenton where first order model fitted better. Ultrasound in combination with Fenton reagent demonstrated a substantial synergy for the degradation of 2-Picoline compared to other treatment approaches showing highest degradation of 97.6 %, synergetic index as 5.71, cavitational yield of 1.82 × 10⁻⁵ mg/J and COD removal of 82.4 %.     

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.     

Tertiary treatment of real abattoir wastewater using combined acoustic cavitation and ozonation

This work reports the influence of ultrasound alone and combined with ozone for the treatment of real abattoir wastewater. Three different frequencies were studied (44, 300 and 1000 kHz) at an applied power of 40 W. The injected ozone dose was fixed at 71 mg/L and the treatment time varied from 1 to 60 min. Using ultrasound alone, 300 kHz was the only frequency showing a reduction in chemical oxygen demand (COD, 18% reduction) and biological oxygen demand (BOD, 50% reduction), while no diminution in microbial content was measured for any of the frequencies studied. Combining ultrasound with ozone, on the contrary, led to a significant decrease in COD (44%) and BOD (78%) removal for the three frequencies under study. A complete inactivation of total coliforms (TC) was obtained, as well as a final value of 99 CFU/mL in total viable counts (TVC, 5 log reduction). That is, the ozonation-sonication combined system was the only treatment method (compared to sonication and ozonation alone) reaching direct discharge limits, as well as meeting drinking water standards for microbial disinfection (TC and TVC).     

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.     

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.     

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.     

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.     

Superior selectivity of high-frequency ultrasound toward chorine containing-pharmaceuticals elimination in urine: A comparative study with other oxidation processes through the elucidation of the degradation pathways

This work considered the sonochemical degradation (using a bath-type reactor, at 375 kHz and 106.3 W L^-1, 250 mL of sample) of three representative halogenated pharmaceuticals (cloxacillin, diclofenac, and losartan) in urine matrices. The action route of the process was initially established. Then, the selectivity of the sonochemical system, to degrade the target pharmaceuticals in simulated fresh urine was compared with electrochemical oxidation (using a BDD anode, at 1.88 mA cm⁻²), and UVC/H₂O₂ (at 60 W of light and 500 mol L^-1 of H₂O₂). Also, the treatment of cloxacillin in an actual urine sample by ultrasound and UVC/H₂O₂ was evaluated. More than 90% of the target compounds concentration, in the simulated matrix, was removed after 60 min of sonication. However, the sono-treatment of cloxacillin in the real sample was less efficient than in the synthetic urine. The ultrasonic process achieved 43% of degradation after 90 min of treatment in the actual matrix. In the sonochemical system, hydroxyl radicals in the interfacial zone were the main degrading agents. Meanwhile, in the electrochemical process, electrogenerated HOCl was responsible for the elimination of pharmaceuticals. In turn, in UVC/H₂O₂ both direct photolysis and hydroxyl radicals degraded the target pollutants. Interestingly, the degradation by ultrasound of the pharmaceuticals in synthetic fresh urine was very close to the observed in distilled water. Indeed, the sonodegradation had a higher selectivity than the other two processes. Despite the sono-treatment of cloxacillin was affected by the actual matrix components, this contrasts with the UVC/H₂O₂, which was completely inhibited in the real urine. The sonochemical process led to 100% of antimicrobial activity (AA) elimination after 75 min sonication in the synthetic urine, and ∼ 20% of AA was diminished after 90 min of treatment in the real matrix. The AA decreasing was linked to the transformations of the penicillin nucleus on cloxacillin, the region most prone to electrophilic attacks by radicals according to a density theory functional analysis. Finally, predictions of biological activity confirmed that the sono-treatment decreased the activity associated with cloxacillin, diclofenac, and losartan, highlighting the positive environmental impact of degradation of chlorinated pharmaceuticals in urine.     

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.     

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.     

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.