Wastewaters from textile industries may contain a variety of dyes that have to be removed before their discharge into waterways. Rice hull, an agricultural by-product, was modified using ethylenediamine to introduce active sites on its surface to enable it to function as a sorbent for both basic and reactive dyes. The sorption characteristics of Basic Blue 3 (BB3) and Reactive Orange 16 (RO16) by ethylenediamine modified rice hull (MRH) were studied under various experimental conditions. Sorption was pH and concentration dependent. Simultaneous removal of BB3 and RO16 occurred at pH greater than 4. The kinetics of dye sorption fitted a pseudo-second order rate expression. Increase in agitation rate had no effect on the sorption of BB3 but increased uptake of RO16 on MRH. Decreasing particle size increased the uptake of dyes in binary dye solutions. Equilibrium data could be fitted into both the Langmuir and Freundlich isotherms. Maximum sorption capacities calculated from the Langmuir model are 14.68 and 60.24 mg/g for BB3 and RO16, respectively in binary dye solutions. This corresponds to an enhancement of 4.5 and 2.4 fold, respectively, compared to single dye solutions. MRH therefore has the potential of being used as an efficient sorbent for the removal of both dyes in textile wastewaters.
This research aims to convert pomegranate peel (PP) into microporous activated carbon (PPAC) using a microwave assisted K2CO3 activation method. The optimum activation conditions were carried out with a 1:2 PP/K2CO3 impregnation ratio, radiation power 800 W, and 15 min irradiation time. The statistical Box-Behnken design (BBD) was employed as an effective tool for optimizing the factors that influence the adsorption performance and removal of methylene blue (MB) dye. The output data of BBD with a desirability function indicate a 94.8% removal of 100 mg/L MB at the following experimental conditions: PPAC dose of 0.08 g, solution pH of 7.45, process temperature of 32.1 °C, and a time of 30 min. The pseudo-second order (PSO) kinetic model accounted for the contact time for the adsorption of MB. At equilibrium conditions, the Freundlich adsorption isotherm describes the adsorption results, where the maximum adsorption capacity of PPAC for MB dye was 291.5 mg g-1. This study supports the utilization of biomass waste from pomegranate peels and conversion into renewable and sustainable adsorbent materials. As well, this work contributes to the management of waste biomass and water pollutant sequestration.
Adsorption efficiency of a duo-material blend featuring the fabrication of modified chitosan adsorbents (powder (C-emimAc), bead (CB-emimAc) and sponge (CS-emimAc)) for the removal of Cd(II) from aqueous solution was investigated. The chitosan@activated carbon (Ch/AC) blend was developed in a green ionic solvent, 1-ethyl-3-methyl imidazolium acetate (EmimAc) and its characteristics was examined using FTIR, SEM, EDX, BET and TGA. The possible mechanism of interaction between the composites and Cd(II) was also predicted using the density functional theory (DFT) analysis. The interactions of various blend forms (C-emimAc, CB-emimAc and CS-emimAc) with Cd(II) gave better adsorption at pH 6. The composites also present excellent chemical stability in both acidic and basic conditions. The monolayer adsorption capacities obtained (under the condition 20 mg/L [Cd], adsorbent dosage 5 mg, contact time 1 h) for the CB-emimAc (84.75 mg/g) > C-emimAc (72.99 mg/g) > CS-emimAc (55.25 mg/g), as this was supported by their order of increasing BET surface area (CB-emimAc (120.1 m2/g) > C-emimAc (67.4 m2/g) > CS-emimAc (35.3 m2/g)). The feasible adsorption interactions between Cd(II) and Ch/AC occurs through the O-H and N-H groups of the composites, as supported by DFT analysis in which an electrostatic interactions was predicted as the dominant force. The interaction energy (-1309.35 eV) calculated via DFT shows that the Ch/AC with amino (-NH) and hydroxyl (-OH) groups are more effective with four significant electrostatic interactions with the Cd(II) ion. The various form of Ch/AC composites developed in EmimAc possess good adsorption capacity and stability for the adsorption Cd(II).
The present study investigated the sustainable approach for wastewater treatment using waste algal blooms. The current study investigated the removal of toxic metals namely chromium (Cr), nickel (Ni), and zinc (Zn) from aqueous solutions in batch and column studies using biochar produced by the marine algae Ulva reticulata. SEM/EDX, FTIR, and XRD were used to examine the adsorbents' properties and stability. The removal efficiency of toxic metals in batch operations was investigated by varying the parameters, which included pH, biochar dose, initial metal ion concentration, and contact time. Similarly, in the column study, the removal efficiency of heavy metal ions was investigated by varying bed height, flow rate, and initial metal ion concentration. Response Surface Methodology (Central Composite Design (CCD)) was used to confirm the linearity between the observed and estimated values of the adsorption quantity. The packed bed column demonstrated successful removal rates of 90.38% for Cr, 91.23% for Ni, and 89.92% for Zn heavy metals from aqueous solutions, under a controlled environment. The breakthrough analysis also shows that the Thomas and Adams-Bohart models best fit the regression values, allowing prior breakthroughs in the packed bed column to be predicted. Desorption studies were conducted to understand sorption and elution during different regeneration cycles. Adding 0.3 N sulfuric acid over 40 min resulted in the highest desorption rate of the column and adsorbent used for all three metal ions.
During commercial production of liquid egg yolk (LEY), phospholipase A2 (PLA2) is used to improve its emulsification capacity and thermal stability. The enzymatic treatment may occur at elevated temperatures such as 50 °C, potentially allowing foodborne pathogens, such as Bacillus cereus, to grow. Little knowledge is available concerning growth of B. cereus in LEY during PLA2 treatment. Therefore, the objective of this study was to investigate the growth kinetics of B. cereus during PLA2 treatment using pathogenic B. cytotoxicus NVH391-98, the most thermotolerant member in the B. cereus group, as a surrogate. Inoculated LEY samples were placed in precision programmable incubators to observe the growth of B. cytotoxicus NVH391-98 under multiple isothermal and dynamic temperature conditions between 20 and 53 °C. The bacterial growth was described using the differential Baranyi model coupled with two different secondary models. The kinetic parameters were determined using one-step dynamic inverse analysis of multiple growth curves. The least square method was used in combination with the 4th order Runge-Kutta method to solve the differential Baranyi model using multiple growth curves to determine the cardinal kinetic parameters. The results showed that B. cytotoxicus NVH391-98 can grow prolifically at 50 °C. The estimated minimum, optimum and maximum temperatures were 16.7 or 18.5, 47.8 or 48.1, and 52.1 or 52.4 °C, respectively, depending on the secondary models, with an optimum growth rate of 2.1 log colony-forming-unit (CFU)/g per hour. The dynamic model is validated using isothermal curves with reasonable accuracy. B. cytotoxicus died off slowly at 15 °C. At 55 °C, thermal inactivation was observed, with a D value of approximately 2.7 h. Holding at 55 °C or below 15 °C can effectively prevent the growth of B. cytotoxicus in egg yolk.
Herein, the polymer nanomatrix of chitosan/SiO2 (CHI/n-SiO2) was enriched with a π-π electron donor-acceptor system using diaromatic rings of benzil (BEZ) assisted via a hydrothermal process to obtain an effective adsorbent of chitosan-benzil/SiO2 (CHI-BEZ/n-SiO2). The polymer nanomatrix (CHI/n-SiO2) and the resulting adsorbent (CHI-BEZ/n-SiO2) were applied to remove the anionic acid red 88 (AR88) dye from aqueous media in a comparative mode. Box-Behnken design (BBD) was adopted to optimize AR88 adsorption onto CHI/n-SiO2 and CHI-BEZ/n-SiO2 with respect to variables that influence AR88 adsorption (adsorbent dose: 0.02-0.1 g/100 mL; pH: 4-10; and time: 10-90). The adsorption studies at equilibrium were conducted with a variety of initial AR88 dye concentrations (20-200 mg/L). The adsorption isotherm results reveal that the AR88 adsorption by CHI/n-SiO2 and CHI-BEZ/n-SiO2 are described by the Langmuir model. The kinetic adsorption profiles of AR88 with CHI/n-SiO2 and CHI-BEZ/n-SiO2 reveal that the pseudo-first-order model provides the best fit results. Interestingly, CHI-BEZ/n-SiO2 has a high adsorption capacity (261.2 mg/g), which exceeds the adsorption capacity of CHI/n-SiO2 (215.1 mg/g) that relates to the surface effects of SiO2 and the functionalization of chitosan with BEZ. These findings show that CHI-BEZ/n-SiO2 represents a highly efficient adsorbent for the removal of harmful pollutants from water, which outperforming the CHI/n-SiO2 system.
An effective hydrothermally prepared chitosan-benzaldehyde/SiO2 adsorbent (CTA-BZA/SiO2) employed functionalization of a CTA biopolymer with SiO2 nanoparticles and BZA. CTA-BZA/SiO2 is an adsorbent that was utilized for the adsorption of an acidic dye (acid red 88, AR88) from synthetic wastewater. The fundamental adsorption variables (A: CTA-BZA/SiO2 dosage (0.02-0.1 g); B: pH (4-10); and C: duration (10-60)) were optimized via the Box-Behnken design (BBD). The Langmuir and Freundlich isotherms (coefficients of determination R2 = 0.99) agreed well with empirical data of AR88 adsorption by CTA-BZA/SiO2. The pseudo-first-order model showed reasonable agreement with the kinetic data of AR88 adsorption by CTA-BZA/SiO2. The maximal AR88 adsorption capacity (qmax) for CTA-BZA/SiO2 was identified to be 252.4 mg/g. The electrostatic attractions between both the positively charged CTA-BZA/SiO2 adsorbent and the AR88 anions, plus the n-π, π-π, and H-bond interactions contribute to the favourable adsorption process. This study reveals that CTA-BZA/SiO2 has the capacity to be a suitable adsorbent for the removal of a wider range of organic dyes from industrial effluents.
This work aimed to develop a modified chitosan adsorbent with enhanced adsorption selectivity for Au(III) over Cu(II) from acidic chloride solutions using low-cost and green raw materials. Various adsorbents, i.e., chitosan powder, chitosan microbeads, chitosan/palm kernel fatty acid distillate (PKFAD) microcomposites, magnetite nanoparticles, and chitosan/PKFAD/magnetite nanocomposites (CPMNs), were first evaluated for their ability to adsorb Au(III) and Cu(II) from single- and binary-metal solutions across different pH levels, followed by parametric analysis of Au(III) and Cu(II) adsorption from binary- and multi-metal solutions onto CPMNs, Au(III) desorption from Au(III)-loaded CPMNs, and reusability of CPMNs. Finally, Au(III)-loaded CPMNs were characterized with SEM-EDX, XRD, FTIR, and XPS to confirm the proposed adsorption mechanisms. Among all the adsorbents studied, CPMNs exhibited outstanding performance in adsorbing Au(III) from an equimolar binary Au(III)-Cu(II) solution, achieving the highest equilibrium adsorption capacity of 0.479 mmol/g (94.4 mg/g) without reaching saturation. Under optimal adsorption conditions of pH 3, 1 g/L CPMN dosage, and 90 min contact time, CPMNs adsorbed 96 % of Au(III) with a selectivity over Cu(II) exceeding 99 %. CPMNs demonstrated excellent reusability, maintaining over 80 % adsorption and desorption efficiencies for 5 cycles. The proposed adsorption mechanisms of CPMNs for Au(III) encompass electrostatic attraction, hydrogen bonding, solvation, and reduction.
A low-cost fruit waste namely watermelon peel (WMP) was utilized as a promising precursor for the preparation of mesoporous activated carbon (WMP-AC) via microwave assisted-K2CO3 activation. The WMP-AC was applied as an adsorbent for methylene blue dye (MB) removal. Several types of characterizations, such as specific surface area (BET), Scanning Electron Microscopy with Energy Dispersive X-ray Spectroscopy (SEM-EDX), Elemental Analysis (CHNS/O), and Fourier Transform Infrared Spectroscopy (FTIR) were used to identify the physicochemical properties of WMP-AC. Furthermore, Box-Behnken design (BBD) was applied to optimize the influence of the adsorption operational variables (contact time, adsorbent dose, working temperature, and solution pH) on MB dye adsorption. Thus, based on significant interactions, the optimum BBD output shows the best removal of 50 mg·L-1 MB (92%) was recorded at an adsorbent dose of 0.056 g, contact time of 4.4 min, working temperature of 39 °C, and solution pH 8.4. The Langmuir uptake capacity of WMP-AC was found to be 312.8 mg·g-1, with the best fitness to the pseudo-second-order kinetics model and an endothermic adsorption process. The adsorption mechanisms of MB by WMP-AC can be assigned to the hydrogen bonding, electrostatic attraction, and π-π stacking. The findings of this study indicate that WMP is a promising precursor for producing porous activated carbon for MB dye removal.
In this study, a magnetic chitosan grafted-benzaldehyde (CS-BD/Fe3O4) was hydrothermally prepared using benzaldehyde as a grafting agent to produce a promising adsorbent for the removal of acid red 88 (AR88) dye. The CS-BD/Fe3O4 was characterized by infrared spectroscopy, surface area analysis, scanning electron microscopy-energy dispersive X-ray, vibrating sample magnetometry, powder X-ray diffraction, CHN elemental analysis, and point of zero charge (pHPZC). The Box-Behnken design (BBD) was adopted to study the role of variables that influence AR88 dye adsorption (A: CS-BD/Fe3O4 dose (0.02-0.1 g), B: pH (4-10), and time C: (10-90 min)). The ANOVA results of the BBD model indicated that the F-value for the AR88 removal was 22.19 %, with the corresponding p-value of 0.0002. The adsorption profiles at equilibrium and dynamic conditions reveal that the Temkin model and the pseudo-first-order kinetics model provide an adequate description of the isotherm results, where the maximum adsorption capacity (qmax) with the AR88 dye was 154.1 mg/g. Several mechanisms, including electrostatic attraction, n-π interaction, π-π interaction, and hydrogen bonding, regulate the adsorption of AR88 dyes onto the CS-BD/Fe3O4 surface. As a result, this research indicates that CS-BD/Fe3O4 can be utilized as an effective and promising bio-adsorbent for azo dye removal from contaminated wastewater.
A composite of chitosan biopolymer with microalgae and commercial carbon-doped titanium dioxide (kronos) was modified by grafting an aromatic aldehyde (salicylaldehyde) in a hydrothermal process for the removal of brilliant green (BG) dye. The resulting Schiff's base Chitosan-Microalgae-TiO2 kronos/Salicylaldehyde (CsMaTk/S) material was characterised using various analytical methods (conclusive of physical properties using BET surface analysis method, elemental analysis, FTIR, SEM-EDX, XRD, XPS and point of zero charge). Box Behnken Design was utilised for the optimisation of the three input variables, i.e., adsorbent dose, pH of the media and contact time. The optimum conditions appointed by the optimisation process were further affirmed by the desirability test and employed in the equilibrium studies in batch mode and the results exhibited a better fit towards the pseudo-second-order kinetic model as well as Freundlich and Langmuir isotherm models, with a maximum adsorption capacity of 957.0 mg/g. Furthermore, the reusability study displayed the adsorptive performance of CsMaTk/S remains effective throughout five adsorption cycles. The possible interactions between the dye molecules and the surface of the adsorbent were derived based on the analyses performed and the electrostatic attractions, H-bonding, Yoshida-H bonding, π-π and n-π interactions are concluded to be the responsible forces in this adsorption process.
Microbial conversion of syngas to energy-dense biofuels and valuable chemicals is a potential technology for the efficient utilization of fossils (e.g., coal) and renewable resources (e.g., lignocellulosic biomass) in an environmentally friendly manner. However, gas-liquid mass transfer and kinetic limitations are still major constraints that limit the widespread adoption and successful commercialization of the technology. This review paper provides rationales for syngas bioconversion and summarizes the reaction limited conditions along with the possible strategies to overcome these challenges. Mass transfer and economic performances of various reactor configurations are compared, and an ideal case for optimum bioreactor operation is presented. Overall, the challenges with the bioprocessing steps are highlighted, and potential solutions are suggested. Future research directions are provided and a conceptual design for a membrane-based syngas biorefinery is proposed.
The thermoluminescence (TL) glow curves and kinetics parameters of Thulium (Tm) doped silica cylindrical fibers (CF) are presented. A linear accelerator (LINAC) was used to deliver high-energy radiation of 21MeV electrons and 10MV photons. The CFs were irradiated in the dose range of 0.2-10Gy. The experimental glow curve data was reconstructed by using WinREMS. The WinGCF software was used for the kinetic parameters evaluation. The TL sensitivity of Tm-doped silica CF is about 2 times higher as compared to pure silica CF. Tm-doped silica CF seems to be more sensitive to 21MeV electrons than to 10MV photons. Surprisingly, no supralinearity was displayed and a sub-linear response of Tm-doped silica CF was observed within the analyzed dose range for both 21MeV electrons and 10MV photons. The Tm-doped silica CF glow curve consists of 5 individual glow peaks. The Ea of peak 4 and peak 5 was highly dependent on dose when irradiated with photons. We also noticed that the electron radiation (21MeV) caused a shift of glow peak by 7-13°C to the higher temperature region compared with photons radiation (10MV). Our Tm-doped fibers seem to give high TL response after 21MeV electrons, which gives around 2 times higher peak integral as compared with 10MV photon radiation. We concluded that peak 4 is the first-order kinetic peak and can be used as the main dosimetric peak of Tm-doped silica CF.
This study was conducted to evaluate the kinetic characteristics of proteolytic activity of proteases on Channa striatus protein fractions. Degree of hydrolysis (DH), amino acid composition and kinetic parameters of sarcoplasmic and myofibrillar proteins were investigated when incubated with proteinase K and thermolysin, separately. After 30 min incubation with proteases, a decrease in DH of sarcoplasmic protein was observed whereas, hydrolysis of myofibrillar protein with proteases took 2 h with an increase in DH. The major amino acids were glutamic acid (16.6%) in thermolysin- myofibrillar hydrolysate followed by aspartic acid (11.1%) in sarcoplasmic protein fraction with no enzyme treatment and lysine (10%) in thermolysin-myofibrillar hydrolysate. The apparent Michaelis constant of proteinase K was lower than thermolysin for both sarcoplasmic and myofibrillar proteins. However, rate of turnover and enzyme efficiency suggested that sarcoplasmic and myofibrillar proteins are suitable substrates for proteinase K and thermolysin hydrolytic reaction, respectively.
The values of pseudo-first-order rate constants (k(obs)) for alkaline hydrolysis of 1, obtained at 1.0 mM NaOH and within [C(m)E(n)]T (total concentration of C(m)E(n)) range of 3.0-5.0 mM for C(12)E(23) and 10-20 mM for C(18)E(20), fail to obey pseudophase micellar (PM) model. The values of the fraction of near irreversible C m E n micellar trapped 1 molecules (F(IT1)) vary in the range ~0-0.75 for C(12)E(23) and ~0-0.83 for C(18)E(20) under such conditions. The values of F(IT1) become 1.0 at ≥ 10 mM C(12)E(23) and 50 mM C(18)E(20). Kinetic analysis of the observed data at ≥ 10 mM C(12)E(23) shows near irreversible micellar entrapment of 1 molecules under such conditions.
Aldazines (Bis-Schiff bases) 1-24 were synthesized using aromatic aldehydes (heterocyclic and benzaldehydes) and hydrazine hydrate under reflux using conventional heating and/or via ultrasound irradiation using BiCl3 as catalyst. Ultrasonication conditions with cat. BiCl3 proved to be an effective, environmentally friendly synthetic procedure. This methodology is robust in the presence of electron donating and electron withdrawing groups affording desired products with high yields (>95%) in just a couple of minutes vs. hours using conventional heating.
Closed form solutions for unsteady free convection flows of a second grade fluid near an isothermal vertical plate oscillating in its plane using the Laplace transform technique are established. Expressions for velocity and temperature are obtained and displayed graphically for different values of Prandtl number Pr, thermal Grashof number Gr, viscoelastic parameter α, phase angle ωτ and time τ. Numerical values of skin friction τ 0 and Nusselt number Nu are shown in tables. Some well-known solutions in literature are reduced as the limiting cases of the present solutions.
A recombinant Trichoderma reesei cellulase was used for the ultrasound-mediated hydrolysis of soluble carboxymethyl cellulose (CMC) and insoluble cellulose of various particle sizes. The hydrolysis was carried out at low intensity sonication (2.4-11.8 W cm(-2) sonication power at the tip of the sonotrode) using 10, 20, and 40% duty cycles. [A duty cycle of 10%, for example, was obtained by sonicating for 1 s followed by a rest period (no sonication) of 9 s.] The reaction pH and temperature were always 4.8 and 50°C, respectively. In all cases, sonication enhanced the rate of hydrolysis relative to nonsonicated controls. The hydrolysis of CMC was characterized by Michaelis-Menten kinetics. The Michaelis-Menten parameter of the maximum reaction rate Vmax was enhanced by sonication relative to controls, but the value of the saturation constant Km was reduced. The optimal sonication conditions were found to be a 10% duty cycle and a power intensity of 11.8 W cm(-2) . Under these conditions, the maximum rate of hydrolysis of soluble CMC was nearly double relative to control. In the hydrolysis of cellulose, an increasing particle size reduced the rate of hydrolysis. At any fixed particle size, sonication at a 10% duty cycle and 11.8 W cm(-2) power intensity improved the rate of hydrolysis relative to control. Under the above mentioned optimal sonication conditions, the enzyme lost about 20% of its initial activity in 20 min. Sonication was useful in accelerating the enzyme catalyzed saccharification of cellulose.
This study was to investigate the mineralization of wastewater containing methyl orange (MO) in integrated anaerobic-aerobic biofilm reactor with coconut fiber as bio-material. Different aeration periods (3h in phase 1 and 2; 3, 6 and 15 h in phase 3; 24 h in phase 4 and 5) in aerobic chamber were studied with different MO concentration 50, 100, 200, 200 and 300 mg/L as influent from phase 1-5. The color removals estimated from the standard curve of dye versus optical density at its maximum absorption wavelength were 97%, 96%, 97%, 97%, and 96% and COD removals were 75%, 72%, 63%, 81%, and 73% in phase 1-5, respectively. The MO decolorization and COD degradation followed first-order kinetic model and second-order kinetic model, respectively. GC-MS analysis indicated the symmetrical cleavage of azo bond and the reduction in aromatic peak ensured the partial mineralization of MO.
Hydrogen production by cyanobacteria could be one of the promising energy resources in the future. However, there is very limited information regarding the kinetic modeling of hydrogen production by cyanobacteria available in the literature. To provide an in-depth understanding of the biological system involved during the process, the Haldane's noncompetitive inhibition equation has been modified to determine the specific hydrogen production rate (HPR) as a function of both dissolved CO2 concentration (CTOT) and oxygen production rate (OPR). The highest HPR of 15 [Formula: see text] was found at xCO2 of 5% vol/vol and the rate consequently decreased when the CTOT and OPR were 0.015 k mol m(-3) and 0.55 mL h(-1), respectively. The model provided a fairly good estimation of the HPR with respect to the experimental data collected.