Removal enhancement of persistent basic fuchsin dye from wastewater using an eco-friendly, cost-effective Fenton process with sodium percarbonate and waste iron catalyst.

In this comprehensive investigation, we evaluate the efficacy of the Fenton process in degrading basic fuchsin (BF), a resistant dye. Our primary focus is on the utilization of readily available, environmentally benign, and cost-effective reagents for the degradation process. Furthermore, we delve into various operational parameters, including the quantity of sodium percarbonate (SPC), pH levels, and the dimensions of waste iron bars, to optimize the treatment efficiency. In the course of our research, we employed an initial SPC concentration of 0.5 mM, a pH level of 3, a waste iron bar measuring 3.5 cm in length and 0.4 cm in diameter, and a processing time of 10 min. Our findings reveal the successful elimination of the BF dye, even when subjected to treatment with diverse salts and surfactants under elevated temperatures and acidic conditions (pH below 3). This underscores the robustness of the Fenton process in purifying wastewater contaminated with dye compounds. The outcomes of our study not only demonstrate the efficiency of the Fenton process but highlight its adaptability to address dye contamination challenges across various industries. Critically, this research pioneers the application of waste iron bars as a source of iron in the Fenton reaction, introducing a novel, sustainable approach that enhances the environmental and economic viability of the process. This innovative use of recycled materials as catalysts represents a significant advancement in sustainable chemical engineering practices.

Review on the impacts of external pressure on sonochemistry.

The impact of hydrostatic pressure, commonly known as ambient or external pressure, on the phenomenon of sonochemistry and/or sonoluminescence has been extensively investigated through a multitude of experimental and computational studies, all of which have emphasized the crucial role played by this particular parameter. Numerous previous studies have successfully demonstrated the existence of an optimal static pressure for the occurrence of sonoluminescence and multi-bubble or single-bubble sonochemistry. However, despite these findings, a universally accepted value for this critical pressure has not yet been established. In addition, it has been found that the cavitation effect is completely inhibited when the static pressure is either too high or too low. This comprehensive review aims to delve into the primary experimental results and elucidate their significance in relation to hydrostatic pressure. We will then conduct an analysis of numerical calculations, focusing specifically on the influence of external pressure on single bubble sonochemistry. By delving into these calculations, we will be able to gain a deeper understanding of the experimental results and effectively interpret their implications.

Sonochemistry dosimetries in seawater.

Due to the complex physical and chemical interactions taking place in the sonicated medium, various methods have been proposed in the literature for a better understanding of the sonochemical system. In the present paper, the performance of calorimetry, iodometry, Fricke, 4-nitrophenol, H2O2, and ascorbic acid dosimetry techniques have been evaluated over the electric power range from 20 to 80 W (f = 300 kHz). These methods have been analyzed for distilled and seawater in light of the literature findings. It has been found that the lowest temperatures and calorimetric energies were obtained for seawater in comparison to distilled water. However, the discrepancy between both mediums disappears with the increase in the electric power up to 80 W. Compared to the calorimetry results, a similar trend was obtained for the KI dosimetry, where the discrepancy between both solutions (seawater and distilled water) increased with the reduction in the electric power down to 20 W. In contrast, over the whole range of the electric power (20-80 W), the H2O2 dosimetry was drastically influenced by the salt composition of seawater, where, I3- formation was clearly reduced in comparison to the case of the distilled water. On the other hand, a fluctuated behavior was observed for the Fricke and 4-nitrophenol dosimetry methods, especially at the low electric powers (20 and 40 W). It has been found that dosimetry techniques based on ascorbic acid or potassium iodide are the best means for accurate quantification of the sonochemical activity in the irradiated liquid. As a result, it has been concluded, in terms of the dosimetry process's performance, that the dosimetry methods are in the following order: Ascorbic acid ≈ KI > Fricke > 4-nitrophenol > H2O2.

Phase Change Material (PCM)-based thermal storage system for managing the sonochemical reactor heat: Thermodynamic analysis of the liquid height impact.

As an alternative to a water-based cooling system for a sonoreactor, the present work presents for the first time the use of a phase change material for the management and storage of the dissipated heat within the sonicated water. The performance of the PCM is analyzed as a function of liquid height (LH = 5.1, 10.2, 15.3, and 20.4 cm) at a frequency of 300 kHz and two electric powers (PE = 20 and 60 W). The effective powers dissipated in the irradiated water were determined by the calorimetric technique. A computational fluid dynamics (CFD) model (implemented in ANSYS Fluent® software), was used for the analysis of the combined system (sonoreactor + PCM-thermal unit) at different operating conditions (liquid height and electric power). By analyzing the different outputs (variation of temperature, velocity, enthalpy, liquid fraction of PCM) of the used CFD model, more clarifications are provided about the behaviour of the combined system (sonoreactor + PCM-thermal unit) as function of the liquid height (5.1-20.4 cm) and electric power (20 and 60 W). In terms of temperature, velocity, enthalpy and liquid fraction of the PCM, promising results were obtained in spite of the low thermal conductivity of the employed PCM. The best performance of the combined system (sonoreactor and thermal unit) was obtained at the liquid height of 15.3 cm (corresponding to a water volume of 300 mL) with a similar behaviour (evolution of temperature, velocity, enthalpy, and liquid fraction of the PCM) at both electric powers (i.e., 20 and 60 W) with an intensified response at the PE = 60 W.

The impact of methanol mass transport on its conversion for the production of hydrogen and oxygenated reactive species in sono-irradiated aqueous solution.

This study aims principally to assess numerically the impact of methanol mass transport (i.e., evaporation/condensation across the acoustic bubble wall) on the thermodynamics and chemical effects (methanol conversion, hydrogen and oxygenated reactive species production) of acoustic cavitation in sono-irradiated aqueous solution. This effect was revealed at various ultrasound frequencies (from 213 to 1000 kHz) and acoustic intensities (1 and 2 W/cm2) over a range of methanol concentrations (from 0 to 100%, v/v). It was found that the impact of methanol concentration on the expansion and compression ratios, bubble temperature, CH3OH conversion and the molar productions inside the bubble is frequency dependent (either with or without consideration of methanol mass transport), where this effect is more pronounced when the ultrasound frequency is decreased. Alternatively, the decrease in acoustic intensity decreases clearly the effect of methanol mass transport on the bubble sono-activity. When methanol mass transfer is eliminated, the decrease of the bubble temperature, CH3OH conversion and the molar yield of the bubble with the rise of methanol concentration was found to be more amortized as the wave frequency is reduced from 1 MHz to 213 kHz, compared to the case when the mass transport of methanol is taken into account. Our findings indicate clearly the importance of incorporating the evaporation and condensation mechanisms of methanol throughout the numerical simulations of a single bubble dynamics and chemical activity.

Critical Analysis of Hydrogen Production by Aqueous Methanol Sonolysis.

Recently, several experimental and theoretical studies have demonstrated the feasibility of enhancing the sonochemical production of hydrogen via methanol pyrolysis within acoustic cavitation bubbles (i.e. sonolysis of aqueous methanol solution). This review includes both the experimental and theoretical achievements in the field of hydrogen production by methanol sonolysis. Additionally, the limits of the process's applicability and plausible solutions are highlighted. The impact of different parameters influencing the process performance is discussed. Finally, the effects of methanol concentration on the size distribution of active cavitation bubbles are analyzed.

Estimation of the number density of active cavitation bubbles in a sono-irradiated aqueous solution using a thermodynamic approach.

An alternative semi-empirical technique is developed to determine the number density of active cavitation bubbles (N) formed in sonicated solutions. This was achieved by relating the acoustic power supplied to the solution (i.e., determined experimentally) to the released heat by a single bubble. The energy dissipation via heat exchange is obtained by an advanced cavitation model accounting for the liquid compressibility and viscosity, the non-equilibrium condensation/evaporation of water vapor, and heat conduction across the bubble wall and heats of chemical reactions resulting within the bubble at the collapse. A good concordance was observed between our results and those found in the literature. It was found that the number of active bubbles increased proportionally with a rise in ultrasound frequency. Additionally, the increase of acoustic intensity increases the number of active bubbles, whatever the sonicated solution's volume. On the other hand, it was observed that the rise of the irradiated solution volume causes the number of active bubbles to be reduced even when the acoustic power is increased. A decrease in acoustic energy accelerates this negative impact.

Modeling of Textile Dye Removal from Wastewater Using Innovative Oxidation Technologies (Fe(II)/Chlorine and H2O2/Periodate Processes): Artificial Neural Network-Particle Swarm Optimization Hybrid Model.

An efficient optimization technique based on a metaheuristic and an artificial neural network (ANN) algorithm has been devised. Particle swarm optimization (PSO) and ANN were used to estimate the removal of two textile dyes from wastewater (reactive green 12, RG12, and toluidine blue, TB) using two unique oxidation processes: Fe(II)/chlorine and H2O2/periodate. A previous study has revealed that operating conditions substantially influence removal efficiency. Data points were gathered for the experimental studies that developed our ANN-PSO model. The PSO was used to determine the optimum ANN parameter values. Based on the two processes tested (Fe(II)/chlorine and H2O2/periodate), the proposed hybrid model (ANN-PSO) has been demonstrated to be the most successful in terms of establishing the optimal ANN parameters and brilliantly forecasting data for RG12 and TP elimination yield with the coefficient of determination (R2) topped 0.99 for three distinct ratio data sets.

Ultrasound/chlorine sono-hybrid-advanced oxidation process: Impact of dissolved organic matter and mineral constituents.

In this work, after exploring the first report on the synergism of combining ultrasound (US: 600 kHz) and chlorine toward the degradation of Allura Red AC (ARAC) textile dye, as a contaminant model, the impact of various mineral water constituents (Cl-, SO42-, NO3-, HCO3- and NO2-) and natural organic matter, i.e., humic acid (HA), on the performance of the US/chlorine sono-hybrid process was assessed for the first time. Additionally, the process effectiveness was evaluated in a real natural mineral water (NMW) of a known composition. Firstly, it was found that the combination of ultrasound and chlorine (0.25 mM) at pH 5.5 in cylindrical standing wave ultrasonic reactor (f = 600 kHz and Pe = 120 W, equivalent to PA âˆ¼ 2.3 atm) enhanced in a drastic manner the degradation rate of ARAC; the removal rate being 320% much higher than the arithmetic sum of the two separated processes. The source of the synergistic effect was attributed to the effective implication of reactive chlorine species (RCS: Cl, ClO and Cl2-) in the degradation process. Radical probe technique using nitrobenzene (NB) as a specific quencher of the acoustically generated hydroxyl radical confirmed the dominant implication of RCS in the overall degradation rate of ARAC by US/chlorine system. Overall, the presence of humic acid and mineral anions decreased the efficiency of the sono-hybrid process; however, the inhibition degrees depend on the type and the concentration of the selected additives. The reaction of these additives with the generated RCS is presumably the reason for the finding results. The inhibiting effect of Cl-, SO42-, NO3- and NO2- was more pronounced in US/chlorine process as compared to US alone, whereas the inverse scenario was remarked for the effect of HA. These outcomes were associated to the difference in the reactivity of HA and mineral anions toward RCS and OH oxidizing species, in addition to the more selective character of RCS than hydroxyl radical. The displacement of the reaction zone with increasing the additive concentration may also be another influencing factor that favors competition reactions, which subsequently reduce the available reactive species in the reacting medium. The NMW exerted reductions of 43% and 10% in the process efficiency at pH 5.5 and 8, respectively, thereby confirming the RCS-quenching mechanism by the water matrix constituents. Hence, this work provided a precise understanding of the overall mechanism of chlorine activation by ultrasound to promote organic compounds degradation in water.

The multiple role of inorganic and organic additives in the degradation of reactive green 12 by UV/chlorine advanced oxidation process.

The impact of various mineral anions, diverse organic substrates and different environmental matrices on the removal of C.I. reactive green 12 (RG12), a refractory textile dye, by UV/chlorine emerging advanced oxidation process (AOP) was performed. The co-exposure of RG12 (20 mg L-1) to UV and chlorine (0.5 mM) at pH 5 produced a strong synergism on the degradation rate. Radical probe technique showed that ●OH and Cl2●- were the main source of the synergistic effect. Bromide, bicarbonate and chloride at small dosage, i.e. 1 mM, enhanced the rate of RG12 degradation, but higher concentrations of these anions quenched the degradation process. Sulphate anions did not alter the degradation rate of the dye, but nitrite quenched it at ∼ 90%. The inhibiting effect of nitrate appeared only at advanced reaction time (>1 min).On the other hand, natural organic matter (NOM) reduced effectively the degradation rate. Besides, SDS surfactant at only 1 µM accelerated the degradation efficiency by ∼12%. However, Tween 80 has shown an insignificant effect, whereas reductions of 10% and 30% were recorded by Triton X100 and Tween 20, respectively. The RG12-degradation rate was not affected in the mineral water, but it was drastically improved in seawater. Conversely, a huge drop in the RG12-degradation efficiency was obtained in the wastewater effluent. UV/chlorine process is highly viable for degrading pollutant in matrices free of NOM. However, the process losses its potential application in matrices riche of NOM.

An alternative technique for determining the number density of acoustic cavitation bubbles in sonochemical reactors.

The present paper introduces a novel semi-empirical technique for the determination of active bubbles' number in sonicated solutions. This method links the chemistry of a single bubble to that taking place over the whole sonochemical reactor (solution). The probe compound is CCl4, where its eliminated amount within a single bubble (though pyrolysis) is determined via a cavitation model which takes into account the non-equilibrium condensation/evaporation of water vapor and heat exchange across the bubble wall, reactions heats and liquid compressibility and viscosity, all along the bubble oscillation under the temporal perturbation of the ultrasonic wave. The CCl4 degradation data in aqueous solution (available in literature) are used to determine the number density through dividing the degradation yield of CCl4 to that predicted by a single bubble model (at the same experimental condition of the aqueous data). The impact of ultrasonic frequency on the number density of bubbles is shown and compared with data from the literature, where a high level of consistency is found.

Insight into the impact of excluding mass transport, heat exchange and chemical reactions heat on the sonochemical bubble yield: Bubble size-dependency.

Numerical simulations have been performed on a range of ambient bubble radii, in order to reveal the effect of mass transport, heat exchange and chemical reactions heat on the chemical bubble yield of single acoustic bubble. The results of each of these energy mechanisms were compared to the normal model in which all these processes (mass transport, thermal conduction, and reactions heat) are taken into account. This theoretical work was carried out for various frequencies (f: 200, 355, 515 and 1000 kHz) and different acoustic amplitudes (PA: 1.5, 2 and 3 atm). The effect of thermal conduction was found to be of a great importance within the bubble internal energy balance, where the higher rates of production (for all acoustic amplitudes and wave frequencies) are observed for this model (without heat exchange). Similarly, the ignorance of the chemical reactions heat (model without reactions heat) shows the weight of this process into the bubble internal energy, where the yield of the main species (OH, H, O and H2) for this model was accelerated notably compared to the complete model for the acoustic amplitudes greater than 1.5 atm (for f = 500 kHz). However, the lowest production rates were registered for the model without mass transport compared to the normal model, for the acoustic amplitudes greater than 1.5 atm (f = 500 kHz). This is observed even when the temperature inside bubble for this model is greater than those retrieved for the other models. On the other hand, it has been shown that, at the acoustic amplitude of 1.5 atm, the maximal production rates of the main species (OH, H, O and H2) for all the adopted models appear at the same optimum ambient-bubble size (R0 ~ 3, 2.5 and 2 µm for, respectively, 355, 500 and 1000 kHz). For PA = 2 and 3 atm (f = 500 kHz), the range of the maximal yield of OH radicals is observed at the range of R0 where the production of OH, O and H2 is the lowest, which corresponds to the bubble temperature at around 5500 K. The maximal production rate of H, O and H2 is shifted toward the range of ambient bubble radii corresponding to the bubble temperatures greater than 5500 K. The ambient bubble radius of the maximal response (maximal production rate) is shifted toward the smaller bubble sizes when the acoustic amplitude (wave frequency is fixed) or the ultrasound frequency (acoustic power is fixed) is increased. In addition, it is observed that the increase of wave frequency or the acoustic amplitude decrease cause the range of active bubbles to be narrowed (scenario observation for the four investigated models).

A comprehensive numerical analysis of heat and mass transfer phenomenons during cavitation sono-process.

The present study treats the effects of mass transport, heat transfer and chemical reactions heat on the bubble dynamics by spanning a range of ambient bubble radii. The thermodynamic behavior of the acoustic bubble was shown for three wave frequencies, 355, 515 and 1000 kHz. The used acoustic amplitude ranges from 1 to 3 atm. It has been demonstrated that the ambient bubble radius, R0, of the maximal response (i.e., maximal bubble temperature and pressure, Tmax and Pmax) is shifted toward lower values if the acoustic amplitude (at fixed frequency) or the ultrasonic frequency (at fixed amplitude) are increased. The range of the ambient bubble radius narrows as the ultrasonic frequency increases. Heat exchange at the bubble interface was found to be the most important mechanism within the bubble internal energy balance for acoustic amplitudes lower than 2.5 and 3 atm for ultrasonic frequencies of 355 and 515 kHz, respectively. For acoustic amplitudes greater or equal to 2.5 and 3 atm, corresponding to 355 and 515 kHz, respectively, mass transport mechanism (i.e., evaporation and condensation of water vapor) becomes dominant compared to the other mechanisms. At 1000 kHz, the mechanism of heat transfer persists to be dominant for all the used acoustic amplitudes (from 1 to 3 atm). Practically, all the above observations were maintained for bubbles at and around the optimum bubble radius, whereas no significant impact of the three energetic mechanisms was observed for bubbles of too lower and too higher values of R0 (limits of the investigated ranges of R0).

How do dissolved gases affect the sonochemical process of hydrogen production? An overview of thermodynamic and mechanistic effects - On the "hot spot theory".

Although most of researchers agree on the elementary reactions behind the sonolytic formation of molecular hydrogen (H2) from water, namely the radical attack of H2O and H2O2 and the free radicals recombination, several recent papers ignore the intervention of the dissolved gas molecules in the kinetic pathways of free radicals, and hence may wrongly assess the effect of dissolved gases on the sonochemical production of hydrogen. One may fairly ask to which extent is it acceptable to ignore the role of the dissolved gas and its eventual decomposition inside the acoustic cavitation bubble? The present opinion paper discusses numerically the ways in which the nature of dissolved gas, i.e., N2, O2, Ar and air, may influence the kinetics of sonochemical hydrogen formation. The model evaluates the extent of direct physical effects, i.e., dynamics of bubble oscillation and collapse events if any, against indirect chemical effects, i.e., the chemical reactions of free radicals formation and consequently hydrogen emergence, it demonstrates the improvement in the sonochemical hydrogen production under argon and sheds light on several misinterpretations reported in earlier works, due to wrong assumptions mainly related to initial conditions. The paper also highlights the role of dissolved gases in the nature of created cavitation and hence the eventual bubble population phenomena that may prevent the achievement of the sonochemical activity. This is particularly demonstrated experimentally using a 20 kHz Sinaptec transducer and a Photron SA 5 high speed camera, in the case of CO2-saturated water where degassing bubbles are formed instead of transient cavitation.

Box-Wilson design modeling of photocatalytic degradation of industrial dye and wastewater in semi-pilot solar photoreactor.

This work focuses on the treatment of a dye solution, C.I. Basic Blue 41 (BB41), and industrial wastewater by UV/TiO2 photocatalytic process using aqueous catalyst suspensions of titanium dioxide (TiO2), Degussa P25. The procedures were carried out in a semi-pilot scale prototype solar photoreactor under solar radiation. Response surface methodology (RSM) based on Box-Wilson design was applied to assess individual effects of the five main independent parameters: initial dye concentration ([BB41]), TiO2 concentration ([TiO2]), flow rate (Q) initial pH and accumulated solar energy (Qvn) on the decolorization efficiency and to optimise the UV/TiO2 process. Photocatalytic mineralisation was carried out at the optimal conditions found by RSM and results were evaluated by total organic carbon (TOC) abatement for BB41 sloution and industrial wastewater. The optimal conditions found by RSM were: 0.4 g/L, 14.04 mg/L, 1,479.6 L/h, 5.52 and 80 KJ/L for TiO2 concentration, initial dye concentration, flow rate, initial pH and accumulated solar energy, respectively. Photocatalytic mineralisation results show that for accumulated visible solar energy equal to 377.714 kJ/L (after 6 hours of irradiation), under these conditions, the percentage of the initial TOC reduction is about 88% and 85.5% for industrial waste and BB41 solution, respectively.

Influence of processing conditions on the synergism between UV irradiation and chlorine toward the degradation of refractory organic pollutants in UV/chlorine advanced oxidation system.

The synergy of applying UV/chlorine advanced oxidation process (AOP) for the degradation of organic pollutants was usually reported. However, very limited information is available on the influence of processing conditions on the resulted synergism. In this work, C.I. reactive green 12 (RG12), a refractory textile dye, has been selected as a pollutant model to examine the synergism dependence of operational conditions in UV/chlorine AOP. Initial tests conducted with 500 µM of chlorine and 20 mg L-1 of RG12 have resulted in a high synergy index (SI) of 3. Operating conditions sensitively affect the value of SI. This latter increased with increasing initial chlorine and RG12 concentrations up to certain optimums at 500 µM of chlorine and 20 mg L-1 of RG12 and decreased afterward. The best SI value, i.e. 3, was obtained at pH 5, followed by pH 7 (SI = 2.2) and then pH 9-10.5 (SI ~ 2). On the other hand, the synergistic index decreased importantly from 3 at 25 °C to only 1.2 at 55 °C. Finally, by using different radical scavengers, it was found that among various suspected oxidants, only ●OH and Cl2●- play a key role in the synergistic effect between UV and chlorine toward RG12 degradation.

Impact of seawater salinity on the sonochemical removal of emerging organic pollutants.

The results presented in this study illustrate the multiple roles of seawater salinity toward the sonochemical degradation, at variable frequencies (300-1700 kHz), of several hazardous substances, i.e. propylparaben (PPR) endocrine disruptor and several synthetic dyes: naphthol blue black (NBB), malachite green (MG), basic red 29 (BR29), acid orange 7 (AO7), Rhodamine B (RhB) and basic fuchsin (BF). Sonochemical treatment degraded all pollutants in seawater at faster rates than in deionized water. The seawater-salts through increasing the ionic strength of the solution act as a potential pusher of hydrophilic pollutants toward the reactive interfacial area of cavitation bubbles. Additionally, the salts reduce the bubble coalescence, which yields higher number of active bubbles in the irradiating media. Analysing the degradation rate of PPR and NBB with two heterogeneous models based on Langmuir kinetics mechanism indicated that the bubble interfacial area was the preferred reaction zone for the ultrasonic degradation of PPR and NBB in seawater.

Using photoactivated acetone for the degradation of Chlorazol Black in aqueous solutions: Impact of mineral and organic additives.

This study examined the effect of different mineral and organic additives on the degradation of Chlorazol Black (CB, 25.5 µM) in aqueous media by UV/acetone process. Initially, it was found that acetone (50 mM)-assisted UV irradiation accelerated the CB removal within 30 min to 98% against 34% for the sole UV, presumably due to the implication of methyl radicals in the degradation process as confirmed by O2 saturation and nitrite addition (as CH3-specific scavengers). While NaCl and Na2SO4 have no impact on the degradation kinetics of CB upon UV/acetone process, NaHCO3 and Na2CO3 slightly inhibited it and a relatively more inhibition was observed with NaNO3 and KBr. The degradation performance was somewhat decreased in natural mineral water. On the other hand, ascorbic acid, as free radicals scavenger, at low concentration (0.1 mM) completely quenched the positive effect of acetone confirming the free radical mechanism on CB degradation. Besides, the implication of OH was excluded by adding 2­propanol (up to 50 mM). Furthermore, the slight decrease in CB removal in the presence of sucrose, glucose and humic acid is a clear indication that UV/acetone process is a promising technique for removing organic dyes from environmental samples.