Sono-photo-degradation of carbamazepine in a thin falling film reactor: Operation costs in pilot plant

The photo-Fenton degradation of carbamazepine (CBZ) assisted with ultrasound radiation (US/UV/H₂O₂/Fe) was tested in a lab thin film reactor allowing high TOC removals (89% in 35 min). The synergism between the UV process and the sonolytic one was quantified as 55.2%.To test the applicability of this reactor for industrial purposes, the sono-photo-degradation of CBZ was also tested in a thin film pilot plant reactor and compared with a 28 L UV-C conventional pilot plant and with a solar Collector Parabolic Compound (CPC). At a pilot plant scale, a US/UV/H₂O₂/Fe process reaching 60% of mineralization would cost 2.1 and 3.8 €/m³ for the conventional and thin film plant respectively. The use of ultrasound (US) produces an extra generation of hydroxyl radicals, thus increasing the mineralization rate.In the solar process, electric consumption accounts for a maximum of 33% of total costs. Thus, for a TOC removal of 80%, the cost of this treatment is about 1.36 €/m³. However, the efficiency of the solar installation decreases in cloudy days and cannot be used during night, so that a limited flow rate can be treated.     

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).     

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.     

Mechanistic investigations in sono-hybrid (ultrasound/Fe2+/UVC) techniques of persulfate activation for degradation of Azorubine

Persulfate-based oxidation of recalcitrant pollutants has been investigated as an alternative to OH radical based advanced oxidation processes due to distinct merits such as greater stability and non-selective persistent reactivity of ${\text{SO}}_4^{\text{<mglyph src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/rad"></mglyph>}-}$ oxidant species. The present study has attempted to highlight mechanistic features of persulfate-based decolorization of textile dye (Azorubine) using sono-hybrid techniques of activation. Three activation techniques, viz. sonolysis, Fe²⁺ ions and UVC light and combinations thereof, have been examined. UVC is revealed to be the most efficient decolorization technique. The mechanism of sonolysis (i.e. thermal activation of persulfate in the bubble-bulk interfacial region) is revealed to be almost independent of the mechanism of UVC. Fe²⁺ activation is revealed to have an adverse interaction with UVC due to scavenging of sulfate radicals by Fe²⁺ ions. The best hybrid activation technique for persulfate-based degradation and mineralization of Azorubine is UVC + ultrasound. Due to independent mechanisms, degradation and mineralization of the dye obtained with simultaneous application of UVC and ultrasound is nearly equal to the sum of degradation and mineralization obtained using individual techniques.     

Degradation of orange-G by advanced oxidation processes

The degradation and mineralization of orange-G (OG) in aqueous solutions by means of ultrasound irradiation at a frequency of 213 kHz and its combination with a heterogeneous photocatalyst (TiO₂) were investigated. The effects of various operational parameters such as, the concentration of the dye and solution pH on the degradation efficiency were studied. The degradation of the dye followed first-order like kinetics under the conditions examined. The sonolytic degradation of OG was relatively higher at pH 5.8 than that at pH 12. However, an alkaline pH was favoured for the photocatalytic degradation of OG using TiO₂. Total organic carbon (TOC) measurements were also carried out in order to evaluate the mineralization efficiency of OG using sonolysis, photocatalysis and sonophotocatalysis. The hybrid technique of sonophotocatalytic degradation was compared with the individual techniques of photocatalysis and sonolysis. A simple additive effect was observed during the sonophotocatalytic oxidation of OG using TiO₂ indicating that the combined treatment offers no synergistic enhancement. TOC results also support the additive effect in the dual treatment process.     

Synthesis and photoluminescence properties of YVO4:Eu3+, Al3+ phosphor

The Y_0.95?xAl_xVO₄:5%Eu³⁺ (0≤x≤0.1) phosphors were successfully synthesized by solid state reaction at 900 °C for 6 h, and their luminescence properties were investigated under UV and VUV excitation. Monitoring at 619 nm, a strong broad absorption was enhanced by co-doping of Al³⁺ into the YVO₄:Eu³⁺ lattices at 256 nm under UV excitation. The VUV excitation spectra also showed the enhanced excitation bands at about 156 and 200 nm. Under 254 or 147 nm excitation, it was found that Y_0.95?xAl_xVO₄:Eu³⁺(0≤x≤0.1) phosphors showed strong red emission at about 619 nm corresponding to the electric dipole ⁵D₀^–7F₂ transition of Eu³⁺. The improvement of luminescence intensity of YVO₄:Eu³⁺ was also observed after partial substituting Y³⁺ by Al³⁺ and the optimal luminescence intensity appeared with incorporation of 2.5 mol% Al³⁺.     

Distribution of electrical energy consumption for the efficient degradation control of THMs mixture in sonophotolytic process

Sonophotolytic degradation of THMs mixture with different electrical energy ratio was carried out for efficient design of process. The total consumed electrical energy was fixed around 50 W, and five different energy conditions were applied. The maximum degradation rate showed in conditions of US:UV = 1:3 and US:UV = 0:4. This is because the photolytic degradation of bromate compounds is dominant degradation mechanism for THMs removal. However, the fastest degradation of total organic carbon was observed in a condition of US:UV = 1:3. Because hydrogen peroxide generated by sonication was effectively dissociated to hydroxyl radicals by ultraviolet, the concentration of hydroxyl radical was maintained high. This mechanism provided additional degradation of organics. This result was supported by comparison between the concentration of hydrogen peroxide sole and combined process. Consequently, the optimal energy ratio was US:UV = 1:3 for degradation of THMs in sonophotolytic process.     

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.     

Low frequency ultrasound (42 kHz) assisted degradation of Acid Blue 113 in the presence of visible light driven rare earth nanoclusters loaded TiO2 nanophotocatalysts

An attempt has been made to render the visible light driven photocatalytic activity to the TiO₂ nanocatalysts by loading 1 wt% of rare earth (RE) nanoclusters (Gd³⁺, Nd³⁺ and Y³⁺) using a low frequency (42 kHz) producing commercial sonicator. The STEM-HAADF analysis confirms that the RE nanoclusters were residing at the surface of the TiO₂. Transmission electron microscopic (TEM) and X-ray diffraction (XRD) analyses confirm that the loading of RE nanoclusters cannot make any significant changes in the crystal structure of TiO₂. However, the optical properties of the resulted nanocatalysts were significantly modified and the nanocatalysts were employed to study the sonocatalytic, photocatalytic and sonophotocatalytic decolorization as well as mineralization of Acid Blue 113 (AB113). Among the experimented nanocatalysts maximum degradation of AB113 was achieved in the presence Y³⁺-TiO₂ nanocatalysts. The decolorization of AB113 in the presence and absence of Y³⁺ loaded TiO₂ ensues the following order sonolysis < photocatalysis < sonocatalysis < sonophotocatalysis. The sonophotocatalytic decolorization of AB113 shows 1.4-fold (synergy index) enhanced rate when compared with the two corresponding individual advanced oxidation processes. The sonophotocatalytic mineralization shows that 65% of total organic carbon (TOC) can be removed from AB113 after the 5 h of continuous irradiation however the mineralization cannot be able to show the synergetic effect.     

Sonocatalytic rapid degradation of Congo red dye from aqueous solution using magnetic Fe0/polyaniline nanofibers

Nano-sized magnetic Fe⁰/polyaniline (Fe⁰/PANI) nanofibers were used as an effective material for sonocatalytic degradation of organic anionic Congo red (CR) dye. Fe⁰/PANI_, was synthesized via reductive deposition of nano-Fe⁰ onto the PANI nanofibers at room temperature. Prepared catalyst was characterized using HR-TEM, FE-SEM, XRD, FTIR instruments. The efficacy of catalyst in removing CR was assessed colorimetrically using UV–visible spectroscopy under different experimental conditions such as % of Fe⁰ loading into the composite material, solution pH, initial concentration of dye, catalyst dosage, temperature and ultrasonic power. The optimum conditions for sonocatalytic degradation of CR were obtained at catalyst concentrations = 500 mg.L⁻¹, concentration of CR = 200 ppm, solution pH = neutral (7.0), temperature = 30 °C, % of Fe⁰ loading = 30% and 500 W ultrasonic power. The experimental results showed that ultrasonic process could remove 98% of Congo red within 30 min with higher Q_max value (Q_max = 446.4 at 25 °C). The rate of degradation of CR dye was much faster in this ultrasonic technique rather than conventional adsorption process. The degradation efficiency declined with the addition of common inorganic salts (NaCl, Na₂CO₃, Na₂SO₄ and Na₃PO₄). The rate of degradation suppressed more with increasing salt concentration. Kinetic and isotherm studies indicated that the degradation of CR provides pseudo-second order rate kinetic and Langmuir isotherm model compared to all other models tested. The excellent high degradation capacity of Fe⁰/PANI under ultrasonic irradiation can be explained on the basis of the formation of active hydroxyl radicals (OH) and subsequently a series of free radical reactions.     

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.     

Homogeneous sonophotolysis of food processing industry wastewater: Study of synergistic effects,mineralization and toxicity removal

The mineralization of industrial wastewater coming from food industry using an emerging homogeneous sonophotolytic oxidation process was evaluated as an alternative to or a rapid pretreatment step for conventional anaerobic digestion with the aim of considerably reducing the total treatment time. At the selected operation conditions ([H₂O₂] = 11,750 ppm, pH = 8, amplitude = 50%, pulse length (cycles) = 1), 60% of TOC is removed after 60 min and 98% after 180 min when treating an industrial effluent with 2114 ppm of total organic carbon (TOC). This process removed completely the toxicity generated during storing or due to intermediate compounds.An important synergistic effect between sonolysis and photolysis (H₂O₂/UV) was observed. Thus the sonophotolysis (ultrasound/H₂O₂/UV) technique significantly increases TOC removal when compared with each individual process.Finally, a preliminary economical analysis confirms that the sono-photolysis with H₂O₂ and pretreated water is a profitable system when compared with the same process without using ultrasound waves and with no pretreatment.     

Improved photoluminescence of BaMgAl10O17 blue phosphor prepared by spray pyrolysis

BaMgAl₁₀O₁₇:Eu²⁺ (BAM) blue phosphor particles with improved photoluminescence (PL) intensity under vacuum ultraviolet (VUV) excitation were prepared by a spray pyrolysis process. In order to improve the PL intensity, Er³⁺ and Nd³⁺ ions were used as co-doping elements. The VUV characteristics of BAM:Eu²⁺, M⁺ (M=Er, Nd) were monitored with varying the Er³⁺ and Nd³⁺ content in order to find the optimal co-doping concentration when they were prepared by spray pyrolysis. It was found that doping Er³⁺ or Nd³⁺ enhances the PL intensity of BAM:Eu²⁺ blue phosphor particles. In particular, the M³⁺ doping effect on the PL intensity was pronounced when the prepared BAM:Eu²⁺, M³⁺ particles were excited by 172 nm VUV. The maximum intensity was obtained when the M³⁺ content was 1.0 at% with respect to Ba element. The PL intensity of BAM:Eu²⁺, M⁺ (M=Er³⁺, Nd³⁺) particles was also further improved by producing them in a spherical shape, which was successfully achieved by controlling the spray solution. The optimized BAM:Eu²⁺, M⁺ particles had about 10% higher PL intensity than that of the commercial particles, which are made by a conventional solid-state reaction.     

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.     

Luminescent vacuum ultraviolet spectroscopy of Cr3+ ions in nanostructured aluminum oxide

Impurity Cr³⁺ centers in submicron and nanostructured Al₂O₃ crystals of different phase compositions at temperatures of 300 and 7.5 K were studied by a luminescent vacuum ultraviolet (VUV) spectroscopy method. Photoluminescence (PL) spectra and the energies of ²E, ⁴T₂, and ⁴T₁ excited states of Cr³⁺ ion depend on the type of crystalline samples phase. The PL excitation spectrum of R-line in α-Al₂O₃ nanoscale crystals is formed by intracenter transitions (2.5–5.5 eV region), by charge transfer band (6.9 eV) and by effective formation of impurity-bound excitons (9.0 eV region). Such impurity-bound excitons correspond to O₂p→Al₃s electron transition in surroundings of an impurity Cr³⁺ center. The efficiency of impurity-bound excitons formation decreases with the increase of the grain size above 100 nm. The size dependence is noticeably shown in PL excitation spectra in VUV region. Excitons bound to impurity centers do not appear in nanostructured δ+θ-Al₂O₃ crystals. The effect of the electron excitation multiplication is observed distinctly in nanostrucured α-Al₂O₃ at an excitation energy above 19 eV (more than 2E_g).     

Effect of nitrate ions on the efficiency of sonophotochemical phenol degradation

A sonophotochemical oxidation process has been used for the treatment of an aqueous solution of phenol. The aim of this work is to evaluate the effect of nitrate ions on hydroxyl radical production and on phenol oxidation. It has been demonstrated that ultrasound can produce NOx (nitrate and nitrite), with a production rate of 2.2 μM min⁻¹. The photolysis of nitrate can significantly improve the hydroxyl radical production. The apparent rate constant for hydroxyl radical production increased from 0.0015 min⁻¹ to 0.0073 min⁻¹ while increasing initial nitrate concentration from 0 to 0.5 mM. The concentration of hydroxyl radical was directly proportional to the initial nitrate concentration. Using US/UV process, the apparent reaction rate constant of phenol degradation in the presence of nitrate reached 0.020 min⁻¹, which was relatively lower than the value obtained (0.027 min⁻¹) in the absence of nitrate. It appeared that, nitrate ions can inhibit the sonochemical degradation of organic compounds such as phenol.     

A comparative study of Keane''s and Stacey''s equations of state

Chitosan acetate-ammonium nitrate (NH₄NO₃) films have been prepared by the solution-cast technique. Fourier transform infrared spectroscopy (FTIR) showed that complexation has occurred. FTIR exhibited shifts in amine and carbonyl bands from 1553 to 1520 cm⁻¹ and 1636 to 1617 cm⁻¹. A new peak was also observed at 1746 cm⁻¹. XRD shows that all complexes are amorphous. The highest conductivity at room temperature is 2.53×10⁻⁵ S cm⁻¹ for the film containing 45 wt% NH₄NO₃. The conductivity of the samples is dependent on the number of mobile ions and mobility.     

Degradation of ibuprofen by hydrodynamic cavitation: Reaction pathways and effect of operational parameters

Ibuprofen (IBP) is an anti-inflammatory drug whose residues can be found worldwide in natural water bodies resulting in harmful effects to aquatic species even at low concentrations. This paper deals with the degradation of IBP in water by hydrodynamic cavitation in a convergent–divergent nozzle. Over 60% of ibuprofen was degraded in 60 min with an electrical energy per order (E_EO) of 10.77 kWh m⁻³ at an initial concentration of 200 μg L⁻¹ and a relative inlet pressure p_in = 0.35 MPa. Five intermediates generated from different hydroxylation reactions were identified; the potential mechanisms of degradation were sketched and discussed. The reaction pathways recognized are in line with the relevant literature, both experimental and theoretical. By varying the pressure upstream the constriction, different degradation rates were observed. This effect was discussed according to a numerical simulation of the hydroxyl radical production identifying a clear correspondence between the maximum kinetic constant k_OH and the maximum calculated OH production. Furthermore, in the investigated experimental conditions, the pH parameter was found not to affect the extent of degradation; this peculiar feature agrees with a recently published kinetic insight and has been explained in the light of the intermediates of the different reaction pathways.     

Ultrasound-assisted degradation of organic dyes over magnetic CoFe2O4@ZnS core-shell nanocomposite

Magnetic CoFe₂O₄@ZnS core-shell nanocomposite was successfully synthesized via one-step hydrothermal decomposition of zinc(II) diethanoldithiocarbamate complex over CoFe₂O₄ nanoparticles at low temperature of 200 °C. The obtained nanocomposite was characterized by X-ray diffraction, Fourier-transform infrared spectroscopy, UV–Vis spectroscopy, field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, magnetic measurements, and Brunauere-Emmette-Teller. The results confirmed the formation of CoFe₂O₄@ZnS nanocomposite with the average crystallite size of 18 nm. The band gap of 3.4 eV was obtained using UV–vis absorption of CoFe₂O₄@ZnS nanocomposite, which made it a suitable candidate for sono-/photo catalytic processes. This nanocomposite was applied as a novel sonocatalyst for the degradation of organic pollutants under ultrasound irradiation. The results showed complete degradation of methylene blue (MB) (25 mg/L) within 70 min in the presence of CoFe₂O₄@ZnS nanocomposite and H₂O₂ (4 mM). The trapping experiments indicated that OH radicals are the main active species in dye degradation. In addition, sonocatalytic activity of the CoFe₂O₄@ZnS nanocomposite was higher than those of pure ZnS and CoFe₂O₄, showing that the combining ZnS with magnetic CoFe₂O₄ could be an excellent choice to improve its sonocatalytic activity. The nanocomposite could be magnetically separated and reused without any observable change in its structure and performance even after five consecutive runs.     

Synthesis and characterization of Eu2+ activated X12Al10.6Si3.4O32Cl5.4 (X=Sr,Ca) phosphors

In this article, we have reported emission characteristics of Eu²⁺ activated Sr₁₂Al_10.6Si_3.4O₃₂Cl_5.4 and Ca₁₂Al_10.6Si_3.4O₃₂Cl_5.4 phosphors, prepared by combustion synthesis. The PL excitation was monitored at two different wavelengths 254 nm (mercury excitation) and 354 nm (mercury free excitation), which shows broad-blue emission bands at 432 nm, and 438 nm for 354 nm excitation wavelength. Under mercury excitation at 254 nm it shows emission wavelengths at 470 nm, 589 nm, 592 nm, and 617 nm for the prepared Sr₁₂Al_10.6Si_3.4O₃₂Cl_5.4 and Ca₁₂Al_10.6Si_3.4O₃₂Cl_5.4 phosphors. Further it was characterized by XRD, for the investigation of phase and purity of the phosphors. Thermal degradation of the phosphors was also studied at different temperatures.