In this work, sunflower (Helianthus annuus L.) seed hull (SSH), an agricultural waste, was evaluated for its ability to remove methyl violet (MV) from aqueous solutions. Sorption isotherm of MV onto the SSH was determined at 30 degrees C with the initial concentrations of MV in the range of 25-300 mg/L. The equilibrium data were analyzed using the Langmuir, Freundlich and Temkin isotherm models. The equilibrium process was described well by the Freundlich isotherm model. The maximum SSH sorption capacity was found to be 92.59 mg/L at 30 degrees C. The kinetic data were studied in terms of the pseudo-first-order, pseudo-second-order and intraparticle diffusion kinetic models. The pseudo-second-order model best described the sorption process. A single-stage batch-adsorber design of the adsorption of MV onto SSH was studied based on the Freundlich isotherm equation. The results indicated that sunflower seed hull was an attractive candidate for removing methyl violet from aqueous solution.
The remediation of wastewater requires treatment technologies which are robust, efficient, simple to operate and affordable such as adsorption. Lately, three-dimensional (3D) graphene based materials have attracted significant attention as effective adsorbents for wastewater treatment. The intrinsic properties of 3D graphene structure such as large surface area and interconnected porous structure can facilitate the transport of pollutants into the 3D network and provide abundant active sites for trapping the pollutants. For the synthesis of 3D graphene structure, ice-templating is commonly practiced due to its facile steps, cost effectiveness and high scalability potential. This review covers the ice-templating fabrication technique for 3D graphene based materials and their application as adsorbents in eliminating dyes and heavy metals from aqueous media. The assembly mechanisms of the ice-templating fsynthesis are comprehensively discussed. Further discussion on the fundamental principles, critical process parameters and characteristics of ice-templated 3D graphene structures is also included. A thorough review on the mechanisms for batch adsorption of dyes and heavy metals is presented based on the structures and properties of the 3D graphene materials. The review further evaluates the dynamic adsorption in packed columns and the regeneration of 3D graphene based materials.
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.
Fenton oxidation, an advanced oxidation process, is an efficient method for the treatment of recalcitrant wastewaters. Unfortunately, it utilizes H2O2 and iron-based homogeneous catalysts, which lead to the formation of high volumes of sludge and secondary pollutants. To overcome these problems, an alternate option is the usage of heterogeneous catalyst. In this study, a heterogeneous catalyst was developed to provide an alternative solution for homogeneous Fenton oxidation. Iron Zeolite Socony Mobile-5 (Fe-ZSM-5) was synthesized using a new two-step process. Next, the catalyst was characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, fourier transform infrared spectroscopy, and Brunauer-Emmett-Teller analysis and tested against a model wastewater containing the azo dye Acid Blue 113. Results showed that the loading of iron particles reduced the surface area of the catalyst from 293.59 to 243.93 m2/g; meanwhile, the average particle size of the loaded material was 12.29 nm. Furthermore, efficiency of the developed catalyst was evaluated by performing heterogeneous Fenton oxidation. Taguchi method was coupled with principal component analysis in order to assess and optimize mineralization efficiency. Experimental results showed that under optimized conditions, over 99.7% degradation and 77% mineralization was obtained, with a 90% reduction in the consumption of the developed catalyst. Furthermore, the developed catalyst was stable and reusable, with less than 2% leaching observed under optimized conditions. Thus, the present study proved that newly developed catalyst has enhanced the oxidation process and reduced the chemicals consumption.
Fish scale (FS) loaded TiO2 composites were investigated as photocatalysts in degradation of Methyl Orange under solar light irradiation. Composites were prepared through sol-gel method by varying mass ratio of TiO2/FS at 90:10, 70:30 and 50:50, respectively. The catalysts prepared in this study were characterized by using XRD, SEM, FT-IR and nitrogen sorption. The effects of solar irradiation, mass ratio of TiO2/FS composites, irradiation time and catalyst loadings were studied. Synergistic effect was found in TiO2/FS of 90:10 composite which performed higher photocatalytic degradation than synthesized TiO2 under solar light irradiation. However, further increasing fish scale content in the composites reduced the photocatalytic activity drastically. Under solar light irradiation, all the catalysts in this study exhibited photocatalytic activity, except TiO2/FS of 50:50 composite that only acted as a weak biosorbent without performing any photocatalytic property. Photocatalytic degradation increased with increasing catalyst loading and irradiation time but decreased with increased of initial dye concentration.
Mixed dye consists of six commercial dyes and textile effluents from cotton dyeing process were treated by electrochemical-assisted photodegradation under halogen lamp illumination. Two types of effluents were collected which are samples before and after undergone pre-treatment at the factory wastewater treatment plant. The photodegradation process was studied by evaluating the changes in concentration employing UV-vis spectrophotometer (UV-vis) and total organic carbon (TOC) analysis. The photoelectrochemical degradation of mixed dye was found to follow the Langmuir Hinshelwood pseudo-first order kinetic while pseudo-second order kinetic model for effluents by using TOC analyses. The chemical oxygen demand (COD) and biochemical oxygen demand (BOD) values of mixed dye and raw effluents were reported. Photoelectrochemical characteristic of pollutants was studied using the cyclic voltammetry technique. Raw effluent was found to exhibit stronger reduction behaviour at cathodic bias potential but slightly less photoresponse at anodic bias than mixed dye.
Electrochemical-assisted photodegradation of methyl orange has been investigated using TiO2 thin films. The films were prepared by sol-gel dip-coating method. Several operational parameters to achieve optimum efficiency of this electrochemical-assisted photodegradation system have been tested. Photoelectrochemical degradation was studied using different light sources and light intensity. The light sources chosen ranged from ultraviolet to visible light. The effect of agitation of the solution at different speeds has also been studied. Slight improvement of photodegradation rate was observed by applying higher agitation speed. Investigation on the electrode after repeated usages show the electrode can be reused up to 20 times with percentage of deficiency less than 15%. The study on the effect of solution temperature indicated that the activation energy of the methyl orange degradation is 18.63 kJ mol(-1).
Azo dyes are the most varied class of synthetic chemicals with non-degradable characteristics. They are complex compounds made up of many different parts. It was primarily utilized for various application procedures in the dyeing industry. Therefore, it's crucial to develop an economical and environmentally friendly approach to treating azo dyes. Our present investigation is an integrated approach to the electrooxidation (EO) process of azo dyes using RuO2-IrO2-TiO2 (anode) and titanium mesh (cathode) electrodes, followed by the biodegradation process (BD) of the treated EO dyes. Chemical oxygen demand (COD) removal efficiency as follows MB (55%) ≥ MR (45%) ≥ TB (38%) ≥ CR (37%) correspondingly. The fragment generated during the degradation process which was identified with high-resolution mass spectrometry (HRMS) and its degradation mechanism pathway was proposed as demethylation reaction and N-N and C-N/C-S cleavage reaction occurs during EO. In biodegradation studies by Aeromonas hydrophila AR1, the EO treated dyes were completely mineralized aerobically which was evident by the COD removal efficiency as MB (98%) ≥ MR (92.9%) ≥ TB (88%) ≥ CR (87%) respectively. The EO process of dyes produced intermediate components with lower molecular weights, which was effectively utilized by the Aeromonas hydrophila AR1 and resulted in higher degradation efficiency 98%. We reported the significance of the enhanced approach of electrochemical oxidation with biodegradation studies in the effective removal of the pollutants in dye industrial effluent contaminated water environment.
Semiconductor metal oxide with TiO2 nanoparticles removes hazardous compounds from environmental samples. TiO2 nanoparticles have shown potential as an efficient photocatalyst by being employed as a nano-catalyst for the breakdown of organic contaminants in wastewater samples. To separate substances from contaminated samples, combined UV and visible light irradiation has been used. Sol-gel synthesis was used to produce a copper chromite-titanium nanocomposite, which was then evaluated using analytical methods, such as XRD, BET, DRS-UV, and FT-IR. Using visible light, the photocatalytic activity of a nanocomposite made of CuCr2O4 and TiO2 was investigated for its role in the breakdown of malachite green. The effects of several parameters, including pH change, anions presence, contact time, catalyst amount, concentration variation, and the kinetics of photocatalytic degradation were investigated. The magnitude of transition energy calculated using UV-DRS spectra was found to be 3.1 eV for CuCr2O4-TiO2 nanocomposite. Maximum degradation was observed at pH 7.0. The surface area and pore volume of the co-doped samples of Cr2O4 - TiO2 obtained from BET were found to be 6.1213 m2/g and 0.045063 cm3/g respectively. The average particle size of the catalyst of the nano-catalysts calculated from XRD was found to be 8 nm for TiO2 and 66 nm for TiO2-CuCrO4. The peaks obtained in FTIR between the range of 900-500 cm-1 were due to the presence of an aromatic compound. The binding mechanism of a dye molecule to the surface of CuCr2O4-TiO2 nanocomposite was analysed using quantum chemical calculations with the self-consistent reaction field technique employing integral equation formalism for the polarized continuum method and the UFF atomic radii set.
Bioregeneration of mono-amine modified silica gel (MAMS) adsorbent loaded with Acid Orange 7 (AO7), Acid Yellow 9 (AY9) and Acid Red 14 (AR14), respectively, was investigated under two different operational conditions, namely absence/presence of sucrose/bacto-peptone as the co-substrate and different biomass acclimation concentrations. The results revealed that the AY9- and AR14-loaded MAMS adsorbents could almost be completely bioregenerated but only in the presence of co-substrate whereas the bioregeneration of AO7-loaded MAMS could achieve up to 71% in the absence of the co-substrate. These differences could be related to the structural properties of the investigated azo dyes. In addition, the results showed that the bioregeneration duration of AO7-loaded MAMS could be progressively shortened by using biomass acclimated to increasingly higher AO7 concentration. However, the bioregeneration efficiencies were found to be relatively unchanged under different biomass acclimation concentrations.
Dye-ligand affinity chromatography in a stirred fluidized bed has been developed for the rapid recovery of malate dehydrogenase (MDH) from highly turbid baker's yeast cell homogenate in a single step. The most suitable dye, namely Reactive Orange 4, in its optimal immobilized concentration of 8.78 mg/mL was immobilized onto high-density STREAMLINE matrix. To further examine optimal adsorption and elution conditions, the enzyme recovery operation was carried out using unclarified cell homogenates in stirred fluidized bed system. Aiming to develop a non-specific eluent, namely NaCl, to effectively elute the MDH adsorbed, direct recovery of MDH from highly turbid cell homogenate (50% w/v) in a stirred fluidized bed adsorption system was performed. The proposed system successfully achieved a recovery yield of 73.6% and a purification factor of 73.5 in a single step by using 0.6 M NaCl as an eluent at a high liquid velocity of 200 cm/h.
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.
Dyeing wastewater was known to have strong color and refractory organic pollutants. In this study irradiation alone was used for dyes wastewater treatment. This paper studies the effect of the concentrations of pollutants to its removal at various dosages using electron beam technology. Irradiation was effective in removing the highly colored and refractory organic compounds. The color removal for initial concentrations of 255 CU, 520 CU, 990 CU and 1900 CU treated using irradiation at 0.5 kGy were 61%, 48%, 28% and 16%, respectively. However, at the dose of 108 kGy and higher, the color removal between 87% and 96% were recorded with no apparent trend. COD removal also reported similar trend but at relatively lower removal percentage. The COD removal at 0.5 kGy for initial COD concentrations of 57 mg/l and 515 mg/l were 10% and 0%, respectively. At irradiation dose of 108 kGy, the removal for initial COD concentrations of 57 mg/l and 515 mg/l were 37% and 13%, respectively. This showed that concentrations of pollutants and dose of irradiation applied to remove color and COD were dependent to each other.
Cross-linked chitosan/sepiolite composite was prepared from sepiolite clay and chitosan, and was cross-linked using epichlorohydrin. Among the various weight ratio percentage of chitosan and sepiolite clay composites, CS50SP50 was selected as the best adsorbent for both methylene blue (MB) and reactive orange 16 (RO 16). At an optimum adsorbent dosage of 0.2g/100mL, the effects of initial dye concentration (25-400mg/L) and pH (3-11) on MB and RO 16 adsorption onto CS50SP50 composite were studied. Monolayer adsorption capacities of CS50SP50 composite for MB and RO 16 were 40.986mg/g and 190.965mg/g, respectively at 30°C. Freundlich, Langmuir and Temkin isotherms applied on the adsorption data for both the dyes reveal that data fitted best for Freundlich model. For both the dyes pseudo-second-order kinetics were found to describe the adsorption process better than pseudo-first-order kinetics. The adsorption capacity of CS50SP50 composite for both the dyes was found better compared to previous studies thus making it potentially low-cost adsorbent for removal of both cationic and reactive dyes.
Fabrication of an immobilized cross-linked chitosan-epichlorohydrine thin film (CLCETF) onto glass plate for adsorption of reactive orange 16 (RO16) dye was successfully studied using the direct casting technique. Adsorption experiments were performed as a function of contact time, initial dye concentration (25mg/L to 350mg/L), and pH (3-11). The adsorption isotherm followed the Langmuir model. The adsorption capacity of CLECTF for RO16 was 356.50mg/g at 27±2°C. The kinetics closely followed the pseudo-second-order model. Results supported the potential use of an immobilized CLECTF as effective adsorbent for the treatment of reactive dye without using filtration process.
In the current study, we have synthesized an imidazolium based cross-linked polymer, namely, 1-vinyl-3-ethylimidazolium bis(trifluoromethylsulfonyl)imide (poly[veim][Tf2N]-TRIM) using trimethylolpropane trimethacrylate as cross linker, and demonstrated its efficiency for the removal of two extensively used ionic dyes—methylene blue and orange-II—from aqueous systems. The detailed characterization of the synthesized poly[veim][Tf2N]-TRIM was performed with the help of 1H NMR, TGA, FT-IR and FE-SEM analysis. The concentration of dyes in aqueous samples before and after the adsorption process was measured using an UV-vis spectrophotometer. The process parameters were optimised, and highest adsorption was obtained at a solution pH of 7.0, adsorbent dosage of 0.75 g/L, contact time of 7 h and dye concentrations of 100 mg/L and 5.0 mg/L for methylene blue and orange-II, respectively. The adsorption kinetics for orange-II and methylene blue were well described by pseudo-first-order and pseudo−second-order models, respectively. Meanwhile, the process of adsorption was best depicted by Langmuir isotherms for both the dyes. The highest monolayer adsorption capacities for methylene blue and orange-II were found to be 1212 mg/g and 126 mg/g, respectively. Overall, the synthesized cross-linked poly[veim][Tf2N]-TRIM effectively removed the selected ionic dyes from aqueous samples and provided >90% of adsorption efficiency after four cycles of adsorption. A possible adsorption mechanism between the synthesised polymeric adsorbent and proposed dyes is presented. It is further suggested that the proposed ionic liquid polymer adsorbent could effectively remove other ionic dyes and pollutants from contaminated aqueous systems.
Aim: Time-based microfluidic absorption sampling was proposed using cotton fiber-based device made in swab stick. The assay was optimized and compared with conventional pipetted drop sampling using the same device. Materials & methods: Reagents were integrated into cotton fiber device for assessing concentration of analytes by the colorimetric detection method through time-based absorption sampling microfluidic system. All assay parameters were first optimized using conventional pipette-based drop sampling. Results: The color intensity is linear in the relevant concentration range of the analytes. The LOD are 0.189 mM for glucose and 6.56 μM for nitrite, respectively. These values are better than conventional drop sampling. The fiber-containing swab itself functions as sampling, assay and calibration device. Conclusion: Microfluidic cotton fiber-based assay device was fabricated and can determine analyte concentration in artificial salivary samples, colorimetrically, by time-based absorption sampling without the need of complex equipments.
Sonocatalytic degradation of various organic dyes (Congo Red, Reactive Blue 4, Methyl Orange, Rhodamine B and Methylene Blue) catalyzed by powder and nanotubes TiO(2) was studied. Both catalysts were characterized using transmission electron microscope (TEM), surface analyzer, Raman spectroscope and thermal gravimetric analyzer (TGA). Sonocatalytic activity of powder and nanotubes TiO(2) was elucidated based on the degradation of various organic dyes. The former catalyst was favorable for treatment of anionic dyes, while the latter was more beneficial for cationic dyes. Sonocatalytic activity of TiO(2) nanotubes could be up to four times as compared to TiO(2) powder under an ultrasonic power of 100 W and a frequency of 42 kHz. This was associated with the higher surface area and the electrostatic attraction between dye molecules and TiO(2) nanotubes. Fourier transform-infrared spectrometer (FT-IR) was used to identify changes that occurred on the functional group in Rhodamine B molecules and TiO(2) nanotubes after the reaction. Sonocatalytic degradation of Rhodamine B by TiO(2) nanotubes apparently followed the Langmuir-Hinshelwood adsorption kinetic model with surface reaction rate of 1.75 mg/L min. TiO(2) nanotubes were proven for their high potential to be applied in sonocatalytic degradation of organic dyes.
The utilization of renewable and functional group enriched nano-lignin as bio-additve in fabricating composite has become the focus of attention worldwide. Herein, lignin nanoparticles in the form of hollow spheres with the diameter of the order of 138 ± 39 nm were directly prepared from agro-industrial waste (palm kernel shell) using recyclable tetrahydrofuran in an acidified aqueous system without any chemical modification steps. We then fabricated a new chitosan/nano-lignin composite material as highly efficient sorbent, as demonstrated by efficient removal (~83%) of methylene blue (MB) dye under natural pH conditions. The adsorption process obeyed pseudo-second-order kinetics and adequate fitting of the adsorption data using Langmuir model suggested a monolayer adsorption with a maximum adsorption capacity of 74.07 mg g-1. Moreover, thermodynamic study of the system revealed spontaneous and endothermic nature of the sorption process. Further studies revealed that chitosan composite with nano-lignin showed better performance in dye decontamination compared to native chitosan and chitosan/bulk lignin composite. This could essentially be attributed to synergistic effects of size particularity (nano-effect) and incorporated functionalities due to lignin nanoparticles. Recyclability study performed in four repeated adsorption/regeneration cycles revealed recyclable nature of as-prepared composite, whilst adsorption experiments using spiked real water samples indicated recoveries as high as 89%. Based on this study, as-prepared bio-nanocomposite may thus be considered as an efficient and reusable adsorptive platform for the decontamination of water supplies.
In this work, chitosan (Chi) was cross-linked with glyoxal (Gly) and deposited onto glass plate to be a superior adsorbent film for two structurally different reactive orange 16 (RO-16) and methyl orange (MO) dyes by using non-conventional adsorption system without filtration process. The characterizations indicate that the cross-linked chitosan-glyoxal (Chi-Gly) film has a low swelling index, high adherence strength on glass plate, amine group (NH2) content was 32.52%, and pHpzc of ∼6.0 indicating a negative surface charge occurs above pHpzc. The adsorption isotherm data of RO-16 and MO by Chi-Gly film were in agreement with Langmuir isotherm, with maximum adsorption capacities of 1554.3 mg/g and 1451.9 mg/g, respectively. The pseudo-first-order kinetic model best described the kinetic data. The adsorption process was spontaneous and exothermic in nature at Chi-Gly film thickness of 8.55 μm, and pH ~3. The mechanism of adsorption included mainly electrostatic attractions, dipole-dipole hydrogen bonding interactions, n-π stacking attractions, and Yoshida H-bonding. This study reveals that immobilized Chi-Gly film as a good candidate for adsorption of reactive and acid dyes as it does not require any filtration process and adsorbent recovery during and post-adsorption process.