Prediction of micropollutant degradation kinetic constant by ultrasonic using machine learning.

A prediction model based on XGBoost is proposed for ultrasonic degradation of micropollutants' kinetic constants. After parameter optimization through iteration, the model achieves Evaluation metrics with R2 and SMAPE reaching 0.99 and 2.06%, respectively. The impact of design parameters on predicting kinetic constants for ultrasound degradation of trace pollutants was assessed using Shapley additive explanations (SHAP). Results indicate that power density and frequency significantly impact the predictive performance. The database was sorted based on power density and frequency values. Subsequently, 800 raw data were split into small databases of 200 each. After confirming that reducing the database size doesn't affect prediction accuracy, ultrasound degradation experiments were conducted for five pollutants, yielding experimental data. A small database with experimental conditions within the numerical range was selected. Data meeting both feature conditions were filtered, resulting in an optimized 60-data group. After incorporating experimental data, a model was trained for prediction. Degradation kinetic constants for experiments (kE) were compared with predicted constants (for 800 data-based model: kP-800 and for 60 data-based model: kP-60). Results showed ibuprofen, bisphenol A, carbamazepine, and 17ß-Estradiol performed better on the 60-data group (kP-60/kE: 1.00, 0.99, 1.00, 1.00), while caffeine suited the model trained on the 800-data group (kP-800/kE: 1.02).

UV/persulfate processes for the removal of total organic carbon from coagulation-treated industrial wastewaters.

Sulfate radical-based oxidation processes were investigated to understand the relationship between persulfate (PS) consumption and total organic carbon (TOC) removal from industrial wastewater under various PS concentrations. First, the degradation and mineralization of Bisphenol A (BPA) (initial concentration: 11 mg/L) were investigated in ultraviolet (UV)/PS systems. Complete degradation was achieved within 30 min of UV irradiation, and 41%-72% TOC removal was achieved at PS concentrations of 200 and 400 mg/L. The consumed concentration of S2O82- and generated concentration of SO42- increased gradually to similar levels. The ratio of the PS consumption to TOC removal based on the mass concentration (mg/L) was 14.5 and 23.2 at 180 min for 200 and 400 mg/L of S2O82-, respectively. Three types of coagulation-treated industrial wastewater from metal-processing, food-processing, and adhesive-producing plants were obtained, and TOC removal was analyzed using the same UV/PS systems (initial TOC concentration: 100 mg/L). The TOC removal rates ranged from 16.9% to 94.4% after 180 min of UV irradiation at PS concentrations of 1,000, 2,000, 4,000, and 8,000 mg S2O82-/L. Despite the higher TOC removal at higher PS concentrations, the PS activation efficiency decreased significantly as the PS concentration increased. Only approximately 30%-40% activation efficiency was achieved at a PS concentration of 8,000 mg/L. In this study, the ratio of PS consumption to TOC removal ranged from 20.6 to 43.9.

Effects of alcohols and dissolved gases on sonochemical generation of hydrogen in a 300 kHz sonoreactor.

The sonochemical generation of hydrogen (H2) was investigated using various water/alcohol solutions under argon (Ar) 100 % in a 300 kHz sonoreactor. Five types of alcohols-methanol, ethanol, isopropanol, n-propanol, and n-butanol-were used at various concentrations (0 - 100 % v/v). The H2 generation rate in water was 0.31 µmol/min in the absence of alcohols. The H2 generation rate increased, peaked, and then decreased as the alcohol concentration increased. The concentrations used for the peak H2 generation were 5 %, 1 %, 0.5 %, 0.5 %, and 0.1 % for methanol, ethanol, isopropanol, n-propanol, and n-butanol, respectively. The highest generation rate (5.46 µmol/min) was obtained for methanol 5 % among all conditions in this study, and no H2 was detected for 100 % alcohol concentrations. The reason for the enhancement of the sonochemical H2 generation by the addition of alcohols might be due to strong scavenging effect of alcohols for sonochemically generated oxidizing radicals and vigorous reactions of alcohol molecules and their derivatives with H radicals. No significant correlations were found between the H2 generation rates and physicochemical properties of the alcohols in any of the data in this study. As alcohol concentration increased, the calorimetric power decreased. This indicates that the calorimetric power does not represent the degree of sonochemical reactions in the water/alcohol mixtures. The effect of oxygen (O2) content in the dissolved gases on the generation of H2O2 (representing sonochemical oxidation activity) and H2 (representing sonochemical reduction activity) was investigated using Ar/O2 mixtures for water, methanol 5 % and n-propanol 0.5 %. In water, the highest H2O2 generation was obtained for Ar/O2 (50:50), which is similar to previous research results. However, the H2O2 generation increased as the O2 content increased. In addition, H2 generation decreased as the O2 content increased under all liquid conditions (water, methanol, and n-propanol).

Effect of dissolved gases on sonochemical oxidation in a 20 kHz probe system: Continuous monitoring of dissolved oxygen concentration and sonochemical oxidation activity.

Dissolved gases have a substantial influence on acoustic cavitation and sonochemical oxidation reactions. Little research on the changes in dissolved gases and the resultant changes in sonochemical oxidation has been reported, and most studies have focused only on the initial dissolved gas conditions. In this study, the dissolved oxygen (DO) concentration was measured continuously during ultrasonic irradiation using an optical sensor in different gas modes (saturation/open, saturation/closed, and sparging/closed modes). Simultaneously, the resulting changes in sonochemical oxidation were quantified using KI dosimetry. In the saturation/open mode using five gas conditions of Ar and O2, the DO concentration decreased rapidly when O2 was present because of active gas exchange with the atmosphere, and the DO concentration increased when 100% Ar was used. As a result, the order of the zero-order reaction constant for the first 10 min (k0-10) decreased in the order Ar:O2 (75:25) > 100% Ar ≈ Ar:O2 (50:50) > Ar:O2 (25:75) > 100% O2, whereas that during the last 10 min (k20-30) when the DO concentration was relatively stable, decreased in the order 100% Ar > Ar:O2 (75:25) > Ar:O2 (50:50) ≈ Ar:O2 (20:75) > 100% O2. In the saturation/closed mode, the DO concentration decreased to approximately 70-80% of the initial level because of ultrasonic degassing, and there was no influence of gases other than Ar and O2. Consequently, k0-10 and k20-30 decreased in the order Ar:O2 (75:25) > Ar:O2 (50:50) > Ar:O2 (25:75) > 100% Ar > 100% O2. In the sparging/closed mode, the DO concentration was maintained at approximately 90% of the initial level because of the more active gas adsorption induced by gas sparging, and the values of k0-10 and k20-30 were almost the same as those in the saturation/closed mode. In the saturation/open and sparging/closed modes, the Ar:O2 (75:25) condition was most favorable for enhancing sonochemical oxidation. However, a comparison of k0-10 and k20-30 indicated that there would be an optimal dissolved gas condition that was different from the initial gas condition. In addition, the mass-transfer and ultrasonic-degassing coefficients were calculated using changes in the DO concentration in the three modes.

Effects of gas saturation and sparging on sonochemical oxidation activity in open and closed systems, part II: NO2-/NO3- generation and a brief critical review.

The sonochemical generation of NO2- and NO3- is considered to be one of the reasons for the low sonochemical oxidation activity in the presence of N2 in the liquid phase. In this study, the generation characteristics of NO2- and NO3- were investigated using the same 28 kHz sonoreactor and the 12 gas conditions used in Part I of this study. Three gas modes, saturation/closed, saturation/open, and sparging/closed, were applied. N2:Ar (25:75), N2:Ar (50:50), and O2:N2 (25:75) in the saturation/closed mode generated the three highest values of NO2- and NO3-. Ar and O2 were vital for generating relatively large concentrations of NO2- and NO3-. The absorption of N2 from the air resulted in high generation of NO2- and NO3- for Ar 100 % and Ar/O2 mixtures under the saturation/open mode. In addition, gas sparging enhanced the generation of NO2- and NO3- for N2:Ar (25:75), O2:N2 (25:75), and N2 significantly because of the change in the sonochemically active zone and the increase in the mixing intensity in the liquid phase, as discussed in Part I. The ratio of NO3- to NO2- was calculated using their final concentrations, and a ratio higher than 1 was obtained for the condition of Ar 100 %, Ar/O2 mixtures, and O2 100 %, wherein a relatively high oxidation activity was detected. From a summary of the results and findings of previous studies, it was revealed that the observations of NO2- + NO3- could be more appropriate for investigating the NO2- and NO3- generation characteristics. In addition, H2O2/NO2-/NO3- related activity rather than H2O2 activity was suggested to quantify the OH radical activity more appropriately in the presence of N2.

Quantification of sonochemical and sonophysical effects in a 20 kHz probe-type sonoreactor: Enhancing sonophysical effects in heterogeneous systems with milli-sized particles.

Even though acoustic cavitation has been widely investigated, only few researchers focused on the relationship between sonochemical and sonophysical activities and on the enhancement of sonophysical activity. In this study, sonochemical and sonophysical activities were investigated in a heterogeneous system to understand the relationship between these two activities and to suggest optimal conditions for ultrasonic desorption/extraction processes comprising milli-sized glass beads. The sonochemical activity was quantitatively analyzed using potassium iodide dosimetry in homogeneous and heterogeneous systems. Sonophysical activity was quantitatively and qualitatively analyzed using paint-coated bead desorption tests and aluminum foil erosion tests under three probe positions of "T" (1 cm below the liquid surface), "B" (1 cm above the vessel bottom), and "M" (midpoint between "T" and "B"). Three different sizes of glass beads (diameter: 0.2, 1.0, and 4.0 mm) were used in this study. The highest sonochemical activity was obtained at "B" in both homogeneous and heterogeneous systems. However, three times lower sonochemical activity was observed in the heterogeneous system than in the homogeneous system because significant attenuation and unstable reflection of ultrasound occurred in the bead layer and suspension. Higher sonophysical activity was observed, when the bead size decreased and the probe approached the bottom. However, no significant sonophysical activity was detected when the beads were attached to the bottom. Therefore, the sonophysically active region was the zone around the probe body, opposite to the ultrasound irradiation tip, and only suspended beads could undergo severe cavitational actions. This was confirmed via aluminum foil tests. Several erosion marks on the foil were observed in the area around the probe body, whereas no severe damage was observed at the bottom. Moreover, the degree of sonophysical activity did not change for various saturating gases. This might be due to the different thresholds of sonochemical and sonophysical activities.

Ultrasound-assisted soil washing processes for the remediation of heavy metals contaminated soils: The mechanism of the ultrasonic desorption.

Ultrasound-assisted soil washing processes were investigated for the removal of heavy metals (Cu, Pb, and Zn) in real contaminated soils using HCl and EDTA. The ultrasound-assisted soil washing (US/Mixing) process was compared with the conventional soil washing (Mixing) process based on the mechanical mixing. High removal efficiency (44.8% for HCl and 43.2% for EDTA) for the metals was obtained for the most extreme conditions (HCl 1.0 M or EDTA 0.1 M and L:S = 10:1) in the Mixing process. With the aide of ultrasound, higher removal efficiency (57.9% for HCl and 50.0% for EDTA) was obtained in the same extreme conditions and similar or higher removal efficiency (e.g., 54.7% for HCl 0.5 M and L:S = 10:1 and 50.5% for EDTA 0.05 M and L:S = 5:1) was achieved even in less extreme conditions (lower HCl or EDTA concentration and L:S ratio). Therefore, it was revealed that the US/Mixing was advantageous over the conventional Mixing processes in terms of metal removal efficiency, consumption of chemicals, amount of generated washing leachate, and volume/size of washing reactor. In addition, the heavy metals removal was enhanced for the smaller soil particles in the US/Mixing process. It was due to more violent movement of smaller particles in slurry phase and more violent sonophysical effects. In order to understand the mechanism of ultrasonic desorption, the desorption test was conducted using the paint-coated beads with three sizes (1, 2, and 4 mm) for the free and attached conditions. It was found that no significant desorption/removal of paint from the beads was observed without the movement of beads in the water including floatation, collision, and scrubbing. Thus, it was suggested that the simultaneous application of the ultrasound and mechanical mixing could enhance the physical movement of the particles significantly and the very high removal/desorption could be attained.

Effects of gas sparging and mechanical mixing on sonochemical oxidation activity.

The effects of air sparging (0-16 L min-1) and mechanical mixing (0-400 rpm) on enhancing the sonochemical degradation of rhodamine B (RhB) was investigated using a 28 kHz sonoreactor. The degradation of RhB followed pseudo first-order kinetics, where sparging or mixing induced a large sonochemical enhancement. The kinetic constant varied in three stages (gradually increased â†’ increased exponentially â†’ decreased slightly) as the rate of sparging or mixing increased, where the stages were similar for both processes. The highest sonochemical activity was obtained with sparging at 8 L min-1 or mixing at 200 rpm, where the standing wave field was significantly deformed by sparging and mixing, respectively. The cavitational oxidation activity was concentrated at the bottom of the sonicator when higher sparging or mixing rates were employed. Therefore, the large enhancement in the sonochemical oxidation was attributed mainly to the direct disturbance of the ultrasound transmission and the resulting change in the cavitation-active zone in this study. The effect of the position of air sparging and mixing was investigated. The indirect inhibition of the ultrasound transmission resulted in less enhancement of the sonochemical activity. Moreover, the effect of various sparging gases including air, N2, O2, Ar, CO2, and an Ar/O2 (8:2) mixture was compared, where all gases except CO2 induced an enhancement in the sonochemical activity, irrespective of the concentration of dissolved oxygen. The highest activity was obtained with the Ar/O2 (8:2) mixture. Therefore, it was revealed that the sonochemical oxidation activity could be further enhanced by applying gas sparging using the optimal gas.

Application of persulfate with hydrodynamic cavitation and ferrous in the decomposition of pentachlorophenol.

Hydrodynamic cavitation (HC) and Fe(II) are advanced oxidation processes, in which pentachlorophenol (PCP) is treated by the redox method of activating persulfate (PS). The kinetics and mechanism of the HC and Fe(II) activation of PS were examined in aqueous solution using an electron spin resonance (ESR) spin trapping technique and radical trapping with pure compounds. The optimum ratio of Fe(II)/PS was 1:2, and the hydroxyl radical (HO) and sulfate radical (SO4-) generation rate were 5.56 mM h-1 and 8.62 µM h-1, respectively. The generation rate and Rct of HO and SO4- at pH 3 and 50 °C in the Fe(II)/PS/HC system are 7584.6 µM h-1, 0.013 and 24.02 µM h-1, 3.95, respectively. The number of radicals was reduced as the pH increased, and it increased with increasing temperature. The PCP reaction rate constants was 4.39 × 10-2 min-1 at pH 3 and 50 °C. The activation energy was 10.68 kJ mol-1. In addition, the mechanism of PCP treatment in the Fe(II)/PS/HC system was a redox reaction, and the HO-/SO4- contribution was 81.1 and 18.9%, respectively. In this study, we first examined PCP oxidation through HO and SO4- quantification using only the Fe(II)/PS/HC process. Furthermore, the results provide the foundation for activation of PS by HC and Fe(II), but also provide a data basis for similar organic treatments other than PCP.

Development of modified mesoporous carbon (CMK-3) for improved adsorption of bisphenol-A.

The adsorption of bisphenol-A (BPA) on ordered mesoporous carbon (CMK-3) and modified CMK-3 (MCMK-3) for decontamination of aqueous medium was investigated. The CMK-3 and MCMK-3 materials had uniform pore sizes of 3.60 and 3.70 nm and high Brunauer-Emmett-Teller (BET) surface areas of 751 and 564 m2 g-1, respectively. The maximum adsorption capacities of CMK-3 and MCMK-3 were 178.57 (0.24 mg m-2) and 238.01 (0.42 mg m-2) mg g-1, respectively at 298 K (pH 6.4). The difference in the adsorption capacities is attributed to the specific surface area and hydrophobicity of the adsorbents. The adsorption of BPA on CMK-3 and MCMK-3 may be influenced by π-π bonding and hydrophobic and electrostatic interactions, and the excellent adsorption capacity of MCMK-3 is attributed to its unique sp2-hybridized single-atom-layer structure. The kinetics and isotherm data were described by the pseudo-second order kinetic model and the Langmuir isotherm, respectively. This difference in the adsorption kinetics of CMK-3 and MCMK-3 is caused by the increase in the pore diameter of the latter. Further, CMK-3 and MCMK-3, with an open geometry consisting of interlinked nanorods, allow for faster intraparticle diffusion. Overall, CMK-3 and MCMK-3 could be promising adsorbents for the removal of chemicals containing benzene rings from wastewater.

Hybrid reactor based on hydrodynamic cavitation, ozonation, and persulfate oxidation for oxalic acid decomposition during rare-earth extraction processes.

A cost-effective method for treating oxalic acid (OA) during rare-earth extraction was developed using hydrodynamic cavitation (HC), ozone (O3), and persulfate (PS) (HC@PS@O3 process). The results showed that the optimal inlet pressure during HC was 5.10 kg cm-2 with an orifice plate diameter of 2 mm. Moreover, HC was shown to activate PS, providing an alternative activation method to base or heat as an ultrasound activation method for chemical oxidation. O3 was also shown to activate PS. For OA oxidation using the HC@PS@O3 process, the optimum pH was 3 and the reaction rate increased with increasing temperature. Further, the activation energy was 36.69 kJ mol-1. The mechanisms unveiled in this study will allow optimization of the HC@PS@O3 process as a chemical oxidation technology. The kinetic investigation and economic evaluation of the HC@PS@O3 process can be used as the basis for real wastewater treatment processes in the future.

Application of pea-like yolk-shell structured Fe3O4@TiO2 nanosheets for photocatalytic and photo-Fenton oxidation of bisphenol-A.

Uniform pea-like yolk-shell (PLYS) structured magnetic TiO2(PLYS-Fe3O4@TiO2) nanosheets have been prepared via a combined kinetics-controlled mechanical force-driven and hydrothermal etching assisted crystallization method and characterized. The resulting PLYS-Fe3O4@TiO2 nanosheets possess well defined yolk-shell structures with a large BET surface area (∼187.26 m2 g-1) and a strong magnetic susceptibility (∼17.4 emu g-1). The reaction rate constant was 24.2 × 10-2 min-1 as a result of oxidative decomposition of BPA using UV/PLYS-Fe3O4@TiO2/H2O2 system. This is 1.1 and 8.34 times faster than the BPA decomposition reaction rate constant in UV/TiO2/H2O2 and UV/Fe3O4/H2O2 systems, respectively. The synthesized catalyst also exhibited excellent recycle capability and excellent acid decomposition performance.

Enhancement of sonochemical oxidation reactions using air sparging in a 36 kHz sonoreactor.

The effect of air sparging on sonochemical oxidation reactions was investigated using a relatively large reactor equipped with a 36 kHz transducer module at the bottom. KI dosimetry and luminol techniques were used for quantitative and qualitative analysis of the reactions. The cavitation yield increased and then varied minimally as the liquid height increased from 1λ (42 mm) to 8λ (333 mm) with no air sparging. The flow rate of the air used for sparging and the position of the sparger significantly affected the extent of the sonochemical oxidation reactions. A significant enhancement in the sonochemical oxidation by air sparging was observed for higher liquid height and higher flow rate conditions at a constant input power. This enhancement is attributed to the violent mixing effect and the significant change in the sound field and cavitation-active zone in the liquid. Higher sonochemical activity was obtained when air sparging was applied closer to the transducer module at a higher flow rate. Imaging the motion of the liquid surface and sonochemiluminescence revealed that the instability of the liquid body was directly related to the sonochemical activity.

Degradation of polychlorinated dibenzo-p-dioxins and dibenzofurans in real-field soil by an integrated visible-light photocatalysis and solvent migration system with p-n heterojunction BiVO4/Bi2O3.

Degradation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in real-field soil was conducted using an integrated photocatalysis-solvent migration system of BiVO4/Bi2O3 and n-hexane. The photocatalyst BiVO4/Bi2O3 was synthesized, and its performance was found to be affected by the BiVO4 content, with 20wt% BiVO4 showing the best performance owing to its p-n heterojunction being well formed. Migration was affected by the amount of n-hexane, with 15% n-hexane giving the most effective transportation of PCDD/Fs. 37.2% of 17 PCDD/Fs was removed in 60h by the integrated photocatalysis-solvent migration system, although the reaction zone covered 8.5% of the volume of the soil. The result showed that migration via n-hexane fulfilled the aim of carrying contaminants from inside of the soil to the surface. Electron-scavenging experiments with BiVO4/Bi2O3 showed an 18.4% of performance in removal compared to no-scavenging condition, which showed that the main reactions driving BiVO4/Bi2O3 visible-light photocatalysis for aryl-chloride were found to be reduction-based. Owing to the hindering effect of Cl atoms, degradation by hydroxyl radical could proceed after initial dechlorination. This study establishes the applicability of integrated photocatalysis-solvent migration systems in real-field settings, and is the first report of a visible-light photocatalyst, BiVO4/Bi2O3, for the degradation of PCDD/Fs in soil.

A review on heterogeneous sonocatalyst for treatment of organic pollutants in aqueous phase based on catalytic mechanism.

Heterogeneous sonocatalysis, as an emerging advanced oxidation process (AOP), has shown immense potential in water treatment and been widely demonstrated to remove persistent organic compounds in the past decade. The present article aims to provide a comprehensive review on the development of a heterogeneous catalyst for enhancing the ultrasonic degradation rate of organic pollutants from a viewpoint of sonocatalytic mechanism. The rational design and fundamentals for preparing sonocatalysts are presented in the context of facilitating the heterogeneous nucleation and photo-thermal-catalytic effects as well as considering the mechanical stability and separation capacity of the heterogeneous catalyst. In addition, some new trends, ongoing challenges and possible methods to overcome these challenges are also highlighted and proposed.

Synthesis, characterization and sonocatalytic applications of nano-structured carbon based TiO2 catalysts.

In order to enhance sonocatalytic oxidation of a recalcitrant organic pollutant, rhodamine B (RhB), it is necessary to study the fundamental aspects of sonocatalysis. In this study, TiO2-incorporated nano-structured carbon (i.e., carbon nanotubes (CNTs) or graphene (GR)) composites were synthesized by coating TiO2 on CNTs or GR of different mass percentages (0.5, 1, 5, and 10 wt%) by a facile hydrothermal method. The sonocatalytic degradation rates of RhB were examined for the effect of ultrasound (US) frequency and calcination temperature by using the prepared TiO2-NSC composites. Since US frequency affected the sonoluminescence (SL) intensities, it was proposed that there exists a correlation between the surface area or band-gap of the sonocatalysts and the degradation kinetic constants of RhB. In addition, the reusability of TiO2-GR composites was also investigated. Overall, the performance of TiO2-GRs prepared by the hydrothermal method was better than that of calcined TiO2-CNTs. Among TiO2-GRs, 5% GR incorporated media (TiO2-GR-5) showed the best performance. Interestingly, the kinetic constants of sonocatalysts prepared under hydrothermal conditions had a negative linear relationship with the band-gap energy for the corresponding media. Furthermore, the strongest SL intensity and highest degradation rates of RhB for both carbonaceous composites were observed at 500 kHz. The kinetic constants of calcined media decreased linearly as the specific area of the media decreased, while the band-gap energy could not be correlated with the kinetic constants. The GR combined TiO2 composite might be a good sonocatalyst in wastewater treatment using ultrasound-based oxidation because of its high stability.

A review on sonoelectrochemical technology as an upcoming alternative for pollutant degradation.

Sonoelectrochemical process has emerged as a novel integrated technology for various applications starting from sonoelectroplating till the remediation of a wide range of contaminants. Although a promising new technology, the application of sonoelectrochemical technology for pollutant degradation are mostly on a laboratory scale, utilizing the conventional reactor configuration of the electrolytic vessel and ultrasonic horns dipped in it. This type of configuration has been believed to be responsible for its sluggish evolution with lower reproducibility, scale-up and design aspects. To achieve a major turn with an enhanced synergy, refinements in the form of optimizing the co-ordination of the governing parameters of both the technologies (e.g., power, frequency, liquid height, electrode material, electrode size, electrode gap, applied voltage, current density etc.) have been validated. Besides, in order to supplement knowledge in the already existing pool, rigorous research on the past and present status has been done. Challenges were also identified and to overcome them, critical discussions covering an overview of the progressive developments on combining the two technologies and its major applications on pollutant degradation were conducted.