The current novel work presents the optimization of factors affecting defluoridation by Al doped ZnO nanoparticles using response surface methodology (RSM). Al doped ZnO nanoparticles were synthesized by the sol-gel method and validated by FTIR, XRD, TEM/EDS, TGA, BET, and particle size analysis. Moreover, a central composite design (CCD) was developed for the experimental study to know the interaction between Al doped ZnO adsorbent dosage, initial concentration of fluoride, and contact time on fluoride removal efficiency (response) and optimization of the process. Analysis of variance (ANOVA) was achieved to discover the importance of the individual and the effect of variables on the response. The model predicted that the response significantly correlated with the experimental response (R2 = 0.97). Among the factors, the effect of adsorbent dose and contact time was considered to have more influence on the response than the concentration. The optimized process parameters by RSM presented the adsorbent dosage: 0.005 g, initial concentration of fluoride: 1.5 g/L, and contact time: 5 min, respectively. Kinetic, isotherm, and thermodynamic studies were also investigated. The co-existing ions were also studied. These results demonstrated that Al doped ZnO could be a promising adsorbent for effective defluoridation for water.
This paper reviews the phase structures and oxidation kinetics of complex Ti-Al alloys at oxidation temperatures in the range of 600-1000 °C. The mass gain and parabolic rate constants of the alloys under isothermal exposure at 100 h (or equivalent to cyclic exposure for 300 cycles) is compared. Of the alloying elements investigated, Si appeared to be the most effective in improving the oxidation resistance of Ti-Al alloys at high temperatures. The effect of alloying elements on the mechanical properties of Ti-Al alloys is also discussed. Significant improvement of the mechanical properties of Ti-Al alloys by element additions has been observed through the formation of new phases, grain refinement, and solid solution strengthening.
The removal of methyl orange (MO) dye has been studied using TiO2/chitosan-montmorillonite (TiO2/Cs-MT) bilayer photocatalyst which also functions as an adsorbent. The dye removal experiments were conducted in the dark and under UV-Vis light irradiation via adsorption and photocatalysis-adsorption processes, respectively. The adsorption modelings were employed on the dark experimental data and compared with the immobilized and suspended Cs-Mt counterparts. It was found that the bilayer photocatalyst closely followed the adsorption properties of immobilized Cs-Mt which obeyed the pseudo-second-order kinetic and film diffusion models. Fluorescent analysis revealed that the charge separation was enhanced in the presence of Cs-Mt as a sub-layer of TiO2. Under light irradiation, the photocatalytic activity of TiO2/Cs-MT corresponded to its adsorption counterpart trend and was optimized at pH 6.5 and 20 mg L-1 of MO dye solution. High removal efficiency and synergism of MO by TiO2/Cs-MT over TiO2 single layer were observed throughout the 10 cycles of application due to contribution of adsorption of Cs-Mt sub-layer and photocatalysis by TiO2 top layer.
The purpose of this study was to simultaneously predict the drug release and skin permeation of Piroxicam (PX) topical films based on Chitosan (CTS), Xanthan gum (XG) and its Carboxymethyl derivatives (CMXs) as matrix systems. These films were prepared by the solvent casting method, using Tween 80 (T80) as a permeation enhancer. All of the prepared films were assessed for their physicochemical parameters, their in vitro drug release and ex vivo skin permeation studies. Moreover, deep learning models and machine learning models were applied to predict the drug release and permeation rates. The results indicated that all of the films exhibited good consistency and physicochemical properties. Furthermore, it was noticed that when T80 was used in the optimal formulation (F8) based on CTS-CMX3, a satisfactory drug release pattern was found where 99.97% of PX was released and an amount of 1.18 mg/cm2 was permeated after 48 h. Moreover, Generative Adversarial Network (GAN) efficiently enhanced the performance of deep learning models and DNN was chosen as the best predictive approach with MSE values equal to 0.00098 and 0.00182 for the drug release and permeation kinetics, respectively. DNN precisely predicted PX dissolution profiles with f2 values equal to 99.99 for all the formulations.
The present study synthesized nano-magnetite (Fe3O4) from milled steel chips using the high energy ball milling (HEBM) method, characterized it, and then utilized it as a sorbent to remediate boron concentration at various pH (4-9), dosages (0.1-0.5 g), contact times (20-240 min), and initial concentrations (10-100 mg/L). The nano-sorbents were characterized based on SEM structure, elemental composition (EDX), surface area analysis (BET), crystallinity (XRD), and functional group analysis (FTIR). The highest adsorption capacity of 8.44 mg/g with removal efficiency of 84% was attained at pH 8, 0.5 g dosage, contact time of 180 min, and 50 mg/L initial concentration. The experimental data fit best with the pseudo-second-order kinetic model with R2 of 0.998, while the Freundlich adsorption isotherm describes the adsorption process with an R2 value of 0.9464. A regeneration efficiency of 47% was attained even after five cycles of reusability studies. This efficiency implies that the nano-magnetite has the potential for sustainable industrial application.
Low temperature thermal pre-treatment is a low-cost method to break down the structure of extracellular polymeric substances in waste activated sludge (WAS) while improving the sludge biodegradability. However, previous models on low temperature thermal pre-treatment did not adequately elucidate the behaviour of sludge hydrolysis process for the duration ranging from 5 to 9 h. Therefore, this work had developed an inclusive functional model to describe the kinetics of sludge hydrolysis for a wide range of treatment conditions (30 °C-90 °C within 0 and 16 h). As compared with treatment duration, the treatment temperature played a greater impact in solubilizing WAS. Accordingly, the 90 °C treatment had consistently produced WAS with the highest degree of solubility. Nonetheless, the mediocre discrepancies between 90 °C and 75 °C may challenge the practicality of increasing the treatment temperatures beyond 75 °C. The effects of treatment duration on soluble chemical oxygen demand, soluble carbohydrate and soluble protein were only significant during the first 4 h, except for humic substances release that continued to increase with treatment duration. Finally, a good fit with R2 > 0.95 was achieved using an inclusive multivariate non-linear model, substantiating the functionality to predict the kinetics of sludge hydrolysis at arbitrary treatment conditions.
Many advanced technologies have shown encouraging results in removing antibiotics from domestic wastewater. However, as activated sludge treatment is the most common sewage treatment system employed worldwide, improving its effect on antibiotic removal would be more desirable. Understanding the removal mechanisms, kinetics and factors that affect antibiotic removal in the activated sludge process is important as it would allow us to improve the treatment performance. Although these have been discussed in various literature covering different types of antibiotics and wastewater, a specific review on antibiotics and domestic wastewater is clearly missing. This review paper collates, discusses and analyses the removal of antibiotics from sewage in the activated sludge process along with the removal mechanisms and kinetics. The antibiotics are categorised into six classes: β-lactam, dihydrofolate reductase inhibitor, fluoroquinolone, macrolide, sulfonamides and tetracycline. Furthermore, the factors affecting the system performance with regard to antibiotic removal are examined.
Empty fruit bunches (EFBs), a waste material from the palm oil industry, were subjected to pyrolysis and gasification. A high content of volatiles (>82%) increased the reactivity of EFBs, and more than 90% decomposed at 700°C; however, a high content of moisture (>50%) and oxygen (>45%) resulted in a low calorific value. Thermogravimetric analysis demonstrated that the higher the heating rate and the smaller the particle size, the higher the peak and final reaction temperatures. The least squares estimation for a first-order reaction model was used to study the degradation kinetics. The values of activation energy increased from 61.14 to 73.76 and from 40.06 to 47.99kJ/mol when the EFB particle size increased from 0.3 to 1.0mm for holocellulose and lignin degradation stages, respectively. The fuel characteristics of EFB are comparable to those of other biomasses and EFB can be considered a good candidate for gasification.
The intrinsic growth, substrate uptake, and product formation biokinetic parameters were obtained for the anaerobic bacterium, Clostridium ljungdahlii, grown on synthesis gas in various pressurized batch bioreactors. A dual-substrate growth kinetic model using Luong for CO and Monod for H2 was used to describe the growth kinetics of the bacterium on these substrates. The maximum specific growth rate (μ(max) = 0.195 h(-1)) and Monod constants for CO (K s,CO = 0.855 atm) and H2 (K(s,H2) = 0.412 atm) were obtained. This model also accommodated the CO inhibitory effects on cell growth at high CO partial pressures, where no growth was apparent at high dissolved CO tensions (P(CO)(∗) > 0.743 atm). The Volterra model, Andrews, and modified Gompertz were, respectively, adopted to describe the cell growth, substrate uptake rate, and product formation. The maximum specific CO uptake rate (q(max) = 34.364 mmol/g cell/h), CO inhibition constant (K(I) = 0.601 atm), and maximum rate of ethanol (R(max) = 0.172 mmol/L/h at P(CO) = 0.598 atm) and acetate (R(max) = 0.096 mmol/L/h at P(CO) = 0.539 atm) production were determined from the applied models.
This paper aims to provide a review of the analytical extraction techniques for polycyclic aromatic hydrocarbons (PAHs) in soils. The extraction technologies described here include Soxhlet extraction, ultrasonic and mechanical agitation, accelerated solvent extraction, supercritical and subcritical fluid extraction, microwave-assisted extraction, solid phase extraction and microextraction, thermal desorption and flash pyrolysis, as well as fluidised-bed extraction. The influencing factors in the extraction of PAHs from soil such as temperature, type of solvent, soil moisture, and other soil characteristics are also discussed. The paper concludes with a review of the models used to describe the kinetics of PAH desorption from soils during solvent extraction.
The release of chlorophenoxyherbicides agrochemicals, namely 2-chloro- (2CPA), 4-chloro and 2,4,5-trichloro (TCPA) phenoxyacetates from their nanohybrids into various aqueous solutions; carbonate, sulfate and chloride was found to be controlled by pseudo-second order rate expression. The percentage saturated released was found to be anionic-dependent, in the order of carbonate>sulfate>chloride for the release media and 2CPA>4CPA>TCPA for the anionic guests. This study demonstrates that the release of the phenoxyherbicides agrochemicals from the nanohybrid compounds can be tuned by choosing the right combination of exchangeable anions both the incoming and the outgoing anions.
Using natural deep eutectic solvents (NADESs) as a green reagent is a step toward producing environmentally friendly and sustainable technology. This study screened three natural DESs developed using quaternary ammonium salt and organic acid to analyse their capability to extract nickel ions from contaminated mangrove soil, which are ChCl: Acetic Acid (ChCl-AceA), ChCl: Levulinic Acid (ChCl-LevA), and ChCl: Ethylene Glycol(ChCl-Eg) at molar ratio 1:2. The impact of various operating parameters such as washing agent concentration, pH solution, and contact time on the NADES performance in the dissolution of Ni ions batch experiments were performed. The optimal soil washing conditions for metal removal were 30% and 15% concentration, a 1:5 soil-liquid ratio, and pH 2 of ChCl-LevA and ChCl-AceA, respectively. A single removal washing may remove 70.8% and 70.0% Ni ions from the contaminated soil. The dissolution kinetic of Ni ions extraction onto NADES was explained using the linear kinetic pseudo and intraparticle mass transfer diffusion models. The kinetic validation demonstrates a good fit between the experimental and pseudo-second-order Lagergren data. The model's maximum Ni dissolution capacity, Qe are 51.56 mg g-1 and 52.00 mg g-1 of ChCl-LevA and ChCl-AceA, respectively. The synthesised natural-based DES has the potential to be a cost-effective, efficient, green alternative extractant to conventional solvent extraction of heavy metals.
In developing countries like India, an economically viable and ecologically approachable strategy is required to safeguard the drinking water. Excessive fluoride intake through drinking water can lead to dental fluorosis, skeletal fluorosis, or both. The present study has been under with an objective to investigate the feasibility of using cellulose derived from coconut fiber as an adsorbent under varying pH conditions for fluoride elimination from water. The assessment of equilibrium concentration of metal ions using adsorption isotherms is an integral part of the study. This present finding indicates the considerable effect of variation of adsorbent dosages on the fluoride removal efficiency under constant temperature conditions of 25 ± 2 °C with a contact period of 24 h. It is pertinent to mention that maximum adsorption of 88% has been observed with a pH value of 6 with 6 h time duration with fluoride dosage of 50 mg/L. The equilibrium concentration dwindled to 0.4 mg/L at fluoride concentration of 20 mg/L. The Langmuir model designates the adsorption capacity value of 2.15 mg/L with initial fluoride concentration of 0.21 mg/g with R2 value of 0.660. Similarly, the adsorption capacity using Freundlich isotherms is found to be 0.58 L/g and 0.59 L/g with fluoride concentration of 1.84 mg/L and 2.15 mg/L respectively. The results from the present study confirm that coconut fiber possesses appropriate sorption capabilities of fluoride ion but is a pH dependent phenomenon. The outcomes of the study indicate the possible use of cellulose extracted from waste coconut fiber as a low-cost fluoride adsorbent. The present study can be well implemented on real scale systems as it will be beneficial economically as well as environmentally.
Herein, a natural material including chitosan (CTS) and algae (food-grade algae, FGA) was exploited to attain a bio-adsorbent (CTS/FGA) for enhanced methyl violet 2B dye removal. A study of the FGA loading into CTS matrix showed that the best mixing ratio between CTS and FGA to be used for the MV 2B removal was 50 %:50 % (CTS/FGA; 50:50 w/w). The present study employed the Box-Behnken design (RSM-BBD) to investigate the impact of three processing factors, namely CTS/FGA-(50:50) dose (0.02-0.1 g/100 mL), pH of solution (4-10), and contact time (5-15 min) on the decolorization rate of MV 2B dye. The results obtained from the equilibrium and kinetic experiments indicate that the adsorption of MV 2B dye on CTS/FGA-(50:50) follows the Langmuir and pseudo-second-order models, respectively. The CTS/FGA exhibits an adsorption capacity of 179.8 mg/g. The characterization of CTS/FGA-(50:50) involves the proposed mechanism of MV 2B adsorption, which primarily encompasses various interactions such as electrostatic forces, n-π stacking, and H-bonding. The present study demonstrates that CTS/FGA-(50:50) synthesized material exhibits a distinctive structure and excellent adsorption properties, thereby providing a viable option for the elimination of toxic cationic dyes from polluted water.
Analyzing metabolic pathways in systems biology requires accurate kinetic parameters that represent the simulated in vivo processes. Simulation of the fermentation pathway in the Saccharomyces cerevisiae kinetic model help saves much time in the optimization process. Fitting the simulated model into the experimental data is categorized under the parameter estimation problem. Parameter estimation is conducted to obtain the optimal values for parameters related to the fermentation process. This step is essential because insufficient identification of model parameters can cause erroneous conclusions. The kinetic parameters cannot be measured directly. Therefore, they must be estimated from the experimental data either in vitro or in vivo. Parameter estimation is a challenging task in the biological process due to the complexity and nonlinearity of the model. Therefore, we propose the Artificial Bee Colony algorithm (ABC) to estimate the parameters in the fermentation pathway of S. cerevisiae to obtain more accurate values. A metabolite with a total of six parameters is involved in this article. The experimental results show that ABC outperforms other estimation algorithms and gives more accurate kinetic parameter values for the simulated model. Most of the estimated kinetic parameter values obtained from the proposed algorithm are the closest to the experimental data.
Tyrosinase is a key enzyme in enzymatic browning, causing quality losses in food through the oxidation process. Thus, the discovery of an effective and natural tyrosinase inhibitor via green technology is of great interest to the global food market due to food security and climate change issues. In this study, Syzygium aqueum (S. aqueum) leaves, which are known to be rich in phenolic compounds (PC), were chosen as a natural source of tyrosinase inhibitor, and the effect of the sustainable, supercritical fluid extraction (SFE) process was evaluated. Response surface methodology-assisted supercritical fluid extraction (RSM-assisted SFE) was utilized to optimize the PCs extracted from S. aqueum. The highest amount of PC was obtained at the optimum conditions (55 °C, 3350 psi, and 70 min). The IC50 (661.815 μg/mL) of the optimized extract was evaluated, and its antioxidant activity (96.8 %) was determined. Gas chromatography-mass spectrometry (GC-MS) results reveal that 2',6'-dihydroxy-4'-methoxychalcone (2,6-D4MC) (82.65 %) was the major PC in S. aqueum. Chemometric analysis indicated that 2,6-D4MC has similar chemical properties to the tyrosinase inhibitor control (kaempferol). The toxicity and physiochemical properties of the novel 2,6-D4MC from S. aqueum revealed that the 2,6-D4MC is safer than kaempferol as predicted via absorption, distribution, metabolism, and excretion (ADME) evaluation. Enzyme kinetic analysis shows that the type of inhibition of the optimized extract is non-competitive inhibition with Km = 1.55 mM and Vmax = 0.017 μM/s. High-performance liquid chromatography (HPLC) analysis shows the effectiveness of S. aqueum as a tyrosinase inhibitor. The mechanistic insight of the tyrosinase inhibition using 2,6-D4MC was successfully calculated using density functional theory (DFT) and molecular docking approaches. The findings could have a significant impact on food security development by devising a sustainable and effective tyrosinase inhibitor from waste by-products that is aligned with the United Nation's SDG 2, zero hunger.
The temperature dependence of the density, dynamic viscosity and ionic conductivity of several deep eutectic solvents (DESs) containing ammonium-based salts and hydrogen bond donvnors (polyol type) are investigated. The temperature-dependent electrolyte viscosity as a function of molar conductivity is correlated by means of Walden's rule. The oxidation of ferrocene (Fc/Fc+) and reduction of cobaltocenium (Cc+/Cc) at different temperatures are studied by cyclic voltammetry and potential-step chronoamperometry in DESs. For most DESs, chronoamperometric transients are demonstrated to fit an Arrhenius-type relation to give activation energies for the diffusion of redox couples at different temperatures. The temperature dependence of the measured conductivities of DES1 and DES2 are better correlated with the Vogel-Tamman-Fulcher equation. The kinetics of the Fc/Fc+ and Cc+/Cc electrochemical systems have been investigated over a temperature range from 298 to 338 K. The heterogeneous electron transfer rate constant is then calculated at different temperatures by means of a logarithmic analysis. The glycerol-based DES (DES5) appears suitable for further testing in electrochemical energy storage devices.
The treatment of high-strength organic brewery wastewater with added acetaminophen (AAP) by an anaerobic digester was investigated. An anaerobic packed-bed reactor (APBR) was operated as a continuous process with an organic loading rate of 1.5-g COD per litre per day and a hydraulic retention time of three days. The results of steady-state analysis showed that the greatest APBR performances for removing COD and TOC were as high as 98 and 93%, respectively, even though the anaerobic digestibility after adding the different AAP concentrations of 5, 10 and 15 mg L(-1) into brewery wastewater can affect the efficiency of organic matter removal. The average CH4 production decreased from 81 to 72% is counterbalanced by the increased CO2 production from 11 to 20% before and after the injection of AAP, respectively. The empirical kinetic models for substrate utilisation and CH4 production were used to predict that, under unfavourable conditions, the performance of the APBR treatment process is able to remove COD with an efficiency of only 6.8%.
The combustion characteristics of Karanj fruit hulls char (KFH-char) was investigated with thermogravimetry analysis (TGA). The TGA outlined the char combustion thermographs at a different heating rate and isoconversional methods expressed the combustion kinetics. The Kissinger-Akahira-Sunose (KAS) and Flynn-Wall-Ozawa (FWO) methods authenticated the char average activation energy at 62.13 and 68.53kJ/mol respectively, enough to derive the char to burnout. However, the Coats-Redfern method verified the char combustion via complex multi-step mechanism; the second stage mechanism has 135kJ/mol average activation energy. The TGA thermographs and kinetic parameters revealed the adequacy of the KFH-char as fuel substrate than its precursor, Karanj fruit hulls (KFH).
The use of agricultural by-products such as Moringa oleifera plants is one effort to support the reduction of environmental pollution. Activated carbon produces from agricultural wastes is relatively less expensive and can replace traditional methods such as renewable as well as nonrenewable materials such as petroleum residue and coal. In this study, the removal of bisphenol A from aqueous media was studied using activated carbon produced from M. oleifera pods and peels. A batch adsorption study was carried out by varying the parameters of the adsorption process. A maximum removal percentage of 95.46% was achieved at optimum conditions of 2.5 g L-1 adsorbent dose, pH 7, 60 min contact time and 20 mg L-1 initial concentration of BPA. The BET surface areas of MOP, MOP-AC and MOP-ACZ were found to be 12.60, 4.10 and 45.96 m2/g, respectively. The experimental data were analyzed by Langmuir, Freundlich and Temkin adsorption isotherm models. Equilibrium data fitted well with the Langmuir isotherm with a maximum monolayer adsorption capacity of 20.14 mg g-1. The rates of adsorption were found to conform to the pseudo-second-order kinetics with a good correlation. The results indicate that the M. oleifera activated carbon could be employed as a low-cost alternative to commercial activated carbon in the removal of BPA from water.