In this study, the potential for carbonaceous nanomaterials to be used as adsorbents for the mixed matrix membrane (MMM) microextraction and preconcentration of organic pollutants was demonstrated. For this method, multiwall carbon nanotubes (MWCNT) and single layer graphene (SLG) nanoparticles were individually incorporated through dispersion in a cellulose triacetate (CTA) polymer matrix to form a MWCNT-MMM and SLG-MMM, respectively. The prepared membranes were evaluated for the extraction of selected polycyclic aromatic hydrocarbons (PAHs) present in sewage pond water samples. The extraction was performed by dipping a small piece of membrane (7 mm × 7 mm) in a stirred 7.5 mL sample solution to initiate the analyte adsorption. This step was followed by an analyte desorption into 60 μL of methanol prior to high performance liquid chromatography (HPLC) analysis. When the optimum SLG-MMM microextraction technique was applied to spiked sewage pond water samples, the detection limit of the method for the PAHs were in the range of 0.02-0.09 ng/mL, with relative standard deviations of between 1.4% and 7.8%. Enrichment factors of 54-100 were achieved with relative recoveries of 99%-101%. A comparison was also made between the proposed approach and standard solid phase extraction using polymeric bonded octadecyl (C18) cartridges.
This study describes the synthesis, characterization and application of a new chrysin-based silica core-shell magnetic nanoparticles (Fe3O4@SiO2-N-chrysin) as an adsorbent for the preconcentration of Cu(II) from aqueous environment. The morphology, thermal stability and magnetic property of Fe3O4@SiO2-N-chrysin were analyzed using FTIR, FESEM, TEM, XRD, thermal analysis and VSM. The extraction efficiency of Fe3O4@SiO2-N-chrysin was analyzed using the batch wise method with flame atomic absorption spectrometry. Parameters such as the pH, the sample volume, the adsorption-desorption time, the concentration of the desorption solvent, the desorption volume, the interference effects and the regeneration of the adsorbent were optimized. It was determined that Cu(II) adsorption is highly pH-dependent, and a high recovery (98%) was achieved at a pH 6. The limit of detection (S/N=3), the limit of quantification (S/N=10), the preconcentration factor and the relative standard deviation for Cu(II) extraction were 0.3 ng mL(-1), 1 ng mL(-1), 100 and 1.9% (concentration=30 ng mL(-1), n=7), respectively. Excellent relative recoveries of 97-104% (%RSD<3.12) were achieved from samples from a spiked river, a lake and tap water. The MSPE method was also validated using certified reference materials SLRS-5 with good recovery (92.53%).
Nanobiocatalysis is a new frontier of emerging nanosized material support in enzyme immobilization application. This paper is about a comprehensive review on cellulose nanofibers (CNF), including their structure, surface modification, chemical coupling for enzyme immobilization, and potential applications. The CNF surface consists of mainly -OH functional group that can be directly interacted weakly with enzyme, and its binding can be improved by surface modification and interaction of chemical coupling that forms a strong and stable covalent immobilization of enzyme. The knowledge of covalent interaction for enzyme immobilization is important to provide more efficient interaction between CNF support and enzyme molecule. Enzyme immobilization onto CNF is having potential for improving enzymatic performance and production yield, as well as contributing toward green technology and sustainable sources.
Oil spills generally cause worldwide concern due to their detrimental effects on the environment and the economy. An assortment of commercial systems has been developed to control these spills, including the use of agricultural wastes as sorbents. This work deals with raw and modified mangrove barks (Rhizophora apiculata), an industrial lignocellulosic waste, as a low cost adsorbent for oil-product-spill cleanup in the aquatic environment. Mangrove bark was modified using fatty acids (oleic acid and palmitic acid) to improve its adsorption capacity. The oil sorption capacity of the modified bark was studied and compared with that of the raw bark. Kinetic tests were conducted with a series of contact times. The influence of particle size, oil dosage, pH and temperature on oil sorption capacity was investigated. The results showed that oleic acid treated bark has a higher sorption capacity (2,860.00 ± 2.00 mg/g) than untreated bark for Tapis crude oil. A correlation between surface functional groups, morphology and surface area of the adsorbent was studied by Fourier transform infrared spectrum, field emission scanning electron microscopy images and Brunauer-Emmett-Teller analysis. Isotherm study was conducted using the Langmuir and Freundlich isotherm models. The result showed that adsorption of crude oil on treated mangrove bark could be best described by the Langmuir model.
Chitosan based adsorbents have received a lot of attention for adsorption of dyes. Various modifications of this polysaccharide have been investigated to improve the adsorption properties as well as mechanical and physical characteristics of chitosan. This review paper discusses major research topics related to chitosan and its derivatives for application in the removal of dyes from water. Modification of chitosan changes the original properties of this material so that it can be more suitable for adsorption of different types of dye. Many chitosan derivatives have been obtained through chemical and physical modifications of raw chitosan that include cross-linking, grafting and impregnation of the chitosan backbone. Better understanding of these varieties and their affinity toward different types of dye can help future research to be properly oriented to address knowledge gaps in this area. This review provides better opportunity for researchers to better explore the potential of chitosan-derived adsorbents for removal of a great variety of dyes.
Agro-waste from the bark of Metroxylon sagu (sago) was studied as a low cost and effective oil sorbent in dry and aqueous environments. Sorption study was conducted using untreated sago bark (SB) and esterified sago bark (ESB) in used engine oil. Characterization study showed that esterification has successfully improved the hydrophobicity, buoyancy, surface roughness and oil sorption capacity of ESB. Sorption study revealed that water uptake of SB is higher (30 min static: 2.46 g/g, dynamic: 2.67 g/g) compared with ESB (30 min static: 0.18 g/g, dynamic: 0.14 g/g). ESB, however, showed higher oil sorption capacity in aqueous environment (30 min static: 2.30 g/g, dynamic: 2.14) compared with SB (30 min static: 0 g/g, dynamic: 0 g/g). ESB has shown great poTENTial as effective oil sorbent in aqueous environment due to its high oil sorption capacity, low water uptake and high buoyancy.
To enhance the potential of activated carbon (AC), iron incorporation into the AC surface was examined in the present investigations. Iron doped activated carbon (FeAC) material was synthesized and characterized by using surface area analysis, energy dispersive X-ray (EDX), temperature programmed reduction (TPR) and temperature programmed desorption (TPD). The surface area of FeAC (543 m(2)/g) was found to be lower than AC (1043 m(2)/g) as a result of the pores widening due to diffusion of iron particles into the porous AC. Iron uploading on AC surface was confirmed through EDX analysis, showing up to 13.75 wt.% iron on FeAC surface. TPR and TPD profiles revealed the presence of more active sites on FeAC surface. FeAC have shown up to 98% methylene blue (MB) removal from the aqueous media. Thermodynamic parameters indicated the spontaneous and exothermic nature of the sorption processes.
Carbon nanotubes-mesostructured silica nanoparticles (CNT-MSN) composites were prepared by a simple one step method with various loading of CNT. Their surface properties were characterized by XRD, N2 physisorption, TEM and FTIR, while the adsorption performance of the CNT-MSN composites were evaluated on the adsorption of methylene blue (MB) while varying the pH, adsorbent dosage, initial MB concentration, and temperature. The CNTs were found to improve the physicochemical properties of the MSN and led to an enhanced adsorptivity for MB. N2 physisorption measurements revealed the development of a bimodal pore structure that increased the pore size, pore volume and surface area. Accordingly, 0.05 g L(-1) CNT-MSN was able to adsorb 524 mg g(-1) (qm) of 60 mg L(-1) MB at pH 8 and 303 K. The equilibrium data were evaluated using the Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich isotherm models, with the Langmuir model affording the best fit to the adsorption data. The adsorption kinetics were best described by the pseudo-first order model. These results indicate the potential of CNT-MSN composites as effective new adsorbents for dye adsorption.
The adsorption of tributyltin (TBT), onto three mesoporous silica adsorbents functionalized with calix[4]arene, p-tert-butylcalix[4]arene and p-sulfonatocalix[4]arene (MCM-TDI-C4, MCM-TDI-PC4 and MCM-TDI-C4S, respectively) has been compared. Batch adsorption experiments were carried out and the effect of contact time, initial TBT concentration, pH and temperature were studied. The Koble-Corrigan isotherm was the most suitable for data fitting. Based on a Langmuir isotherm model, the maximum adsorption capacities were 12.1212, 16.4204 and 7.5757 mg/g for MCM-TDI-C4, MCM-TDI-PC4 and MCM-TDI-C4S, respectively. The larger uptake and stronger affinity of MCM-TDI-PC4 than MCM-TDI-C4 and MCM-TDI-C4S probably results from van der Waals interactions and the pore size distribution of MCM-TDI-PC4. Gibbs free energies for the three adsorption processes of TBT presented a negative value, reflecting that TBT/surface interactions are thermodynamic favorable and spontaneous. The interaction processes were accompanied by an increase of entropy value for MCM-TDI-C4 and MCM-TDI-C4S (43.7192 and 120.7609 J/mol K, respectively) and a decrease for MCM-TDI-PC4 (-37.4704 J/mol K). It is obviously observed that MCM-TDI-PC4 spontaneously adsorbs TBT driven mainly by enthalpy change, while MCM-TDI-C4 and MCM-TDI-C4S do so driven mainly by entropy changes.
Carbon Nanotubes (CNTs) are generally nano-scale tubes comprising a network of carbon atoms in a cylindrical setting that compared with silicon counterparts present outstanding characteristics such as high mechanical strength, high sensing capability and large surface-to-volume ratio. These characteristics, in addition to the fact that CNTs experience changes in their electrical conductance when exposed to different gases, make them appropriate candidates for use in sensing/measuring applications such as gas detection devices. In this research, a model for a Field Effect Transistor (FET)-based structure has been developed as a platform for a gas detection sensor in which the CNT conductance change resulting from the chemical reaction between NH3 and CNT has been employed to model the sensing mechanism with proposed sensing parameters. The research implements the same FET-based structure as in the work of Peng et al. on nanotube-based NH3 gas detection. With respect to this conductance change, the I-V characteristic of the CNT is investigated. Finally, a comparative study shows satisfactory agreement between the proposed model and the experimental data from the mentioned research.
The toxicity of organophosphate insecticides for nontarget organism has been the subject of extensive research for sustainable agriculture. Pakistan has banned the use of methyl/ethyl parathions, but they are still illegally used. The present study is an attempt to estimate the residual concentration and to suggest remedial solution of adsorption by different types of soils collected and characterized for physicochemical parameters. Sorption of pesticides in soil or other porous media is an important process regulating pesticide transport and degradation. The percentage removal of methyl parathion and ethyl parathion was determined through UV-Visible spectrophotometer at 276 nm and 277 nm, respectively. The results indicate that agricultural soil as compared to barren soil is more efficient adsorbent for both insecticides, at optimum batch condition of pH 7. The equilibrium between adsorbate and adsorbent was attained in 12 hours. Methyl parathion is removed more efficiently (by seven orders of magnitude) than ethyl parathion. It may be attributed to more available binding sites and less steric hindrance of methyl parathion. Adsorption kinetics indicates that a good correlation exists between distribution coefficient (Kd) and soil organic carbon. A general increase in Kd is noted with increase in induced concentration due to the formation of bound or aged residue.
Activated carbons are regularly used the treatment of dye wastewater. They can be produced from various organics materials having high level of carbon content. In this study, a novel Pinang frond activated carbon (PFAC) was produced at various CO₂ flow rates in the range of 150-600 mL/min at activation temperature of 800°C for 3 hours. The optimum PFAC sample is found on CO₂ flow rate of 300 mL/min which gives the highest BET surface area and pore volume of 958 m²/g and 0.5469 mL/g, respectively. This sample shows well-developed pore structure with high fixed carbon content of 79.74%. The removal of methylene blue (MB) by 95.8% for initial MB concentration of 50 mg/L and 72.6% for 500 mg/L is achieved via this sample. The PFAC is thus identified to be a suitable adsorbent for removing MB from aqueous solution.
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.
As Malaysia is one of the world's largest producer of palm oil, large amounts of palm oil mill effluent (POME) is generated. It was found that negatively charged components are accountable for POME color. An attempt was made to remove residual contaminants after conventional treatment using anion base resin. Adsorption experiments were carried out in fixed bed column. Various models such as the Thomas, the Yoon-Nelson, the Wolborska and BDST model were used to fit the experimental data. It was found that only the BDST model was fitted well at the initial breakthrough time. A wavelet neural network model (WNN) was developed to model the breakthrough curves in fixed bed column for multicomponent system. The results showed that the WNN model described breakthrough curves better than the commonly used models. The effects of pH, flow rate and bed depth on column performance were investigated. It was found that the highest uptake capacity was obtained at pH 3. The exhaustion time appeared to increase with increase in bed length and decrease in flow rate.
The present work was conducted to investigate the effect of purification and conjugation processes on functional properties of durian seed gum (DSG) used for stabilization of water in oil in water (W/O/W) emulsion. Whey protein isolate (WPI) was conjugated to durian seed gum through the covalent linkage. In order to prepare WPI-DSG conjugate, covalent linkage of whey protein isolate to durian seed gum was obtained by Maillard reaction induced by heating at 60 °C and 80% (±1%) relative humidity. SDS-polyacrylamide gel electrophoresis was used to test the formation of the covalent linkage between whey protein isolate and durian seed gum after conjugation process. In this study, W/O/W stabilized by WPI-conjugated DSG A showed the highest interface activity and lowest creaming layer among all prepared emulsions. This indicated that the partial conjugation of WPI to DSG significantly improved its functional characteristics in W/O/W emulsion. The addition of WPI-conjugated DSG to W/O/W emulsion increased the viscosity more than non-conjugated durian seed gum (or control). This might be due to possible increment of the molecular weight after linking the protein fraction to the structure of durian seed gum through the conjugation process.
Poly(ethyl hydrazide)-grafted oil palm empty fruit bunch fibre (peh-g-opefb) was successfully prepared by heating poly(methyl acrylate)-grafted opefb (pma-g-opefb) at 60 °C for 4 h with a solution of hydrazine hydrate (15% v/v) in ethanol. The Fourier transform infrared spectrum of the product shows a secondary amine peak at 3267 cm⁻¹, with amide carbonyl peaks at 1729 cm⁻¹ and 1643 cm⁻¹. The chelating ability of peh-g-opefb was tested with copper ion in aqueous solution. A batch adsorption study revealed that maximum adsorption of copper ion was achieved at pH 5. An isotherm study showed the adsorption follows a Langmuir model, with a maximum adsorption capacity of 43.48 mg g-1 at 25 °C. A kinetic study showed that the adsorption of copper ion rapidly reaches equilibrium and follows a pseudo-second-order kinetic model, with a constant rate of 7.02 × 10⁻⁴ g mg⁻¹ min⁻¹ at 25 °C. The Gibbs free energy, ∆G⁰, value is negative, indicating a spontaneous sorption process. Entropy, ∆S⁰, gives a positive value, indicating that the system is becoming increasingly disordered after the adsorption of copper ion. A positive enthalpy value, ∆H⁰, shows that the endothermic process takes place during the adsorption and is more favourable at high temperatures.
Protein adsorption onto membrane surfaces is important in fields related to separation science and biomedical research. This study explored the molecular interactions between protein, bovine serum albumin (BSA), and nitrocellulose films (NC) using electrokinetic phenomena and the effects of these interactions on the streaming potential measurements for different membrane pore morphologies and pH conditions. The data were used to calculate the streaming ratios of membranes-to-proteins and to compare these values to the electrostatic or hydrophobic attachment of the protein molecules onto the NC membranes. The results showed that different pH and membrane pore morphologies contributes to different protein adsorption mechanisms. The protein adsorption was significantly reduced under conditions where the membrane and protein have like-charges due to electrostatic repulsion. At the isoelectric point (IEP) of the protein, the repulsion between the BSA and the NC membrane was at the lowest; thus, the BSA could be easily attached onto the membrane/solution interface. In this case, the protein was considered to be in a compact layer without intermolecular protein repulsions.
The adsorption of methyl orange dye from aqueous solution onto penta-bismuth hepta-oxide nitrate, Bi(5)O(7)NO(3), synthesized by precipitation method, was studied in a batch adsorption system. The effects of operation parameters such as adsorbent dose, initial dye concentration, pH and temperature were investigated. The adsorption equilibrium and mechanism of adsorption was evaluated by Langmuir and Freundlich isotherm and different kinetic models, respectively. The results indicate that adsorption is highly dependent on all operation parameters. At optimum conditions, the adsorption capacity was found to be 18.9 mg/g. The adsorption data fits well with the Langmuir isotherm model indicating monolayer coverage of adsorbate molecules on the surface of Bi(5)O(7)NO(3). The kinetic studies show that the adsorption process is a second-order kinetic reaction. Although intra-particle diffusion limits the rate of adsorption, the multi-linearity plot of intra-particle model shows the importance of both film and intra-particle diffusion as the rate-limiting steps of the dye removal. Thermodynamic parameters show that the adsorption process is endothermic, spontaneous and favourable at high temperature.
Adsorption capacity of an agricultural waste, palm-tree fruit stones (date stones), for phenolic compounds such as phenol (Ph) and p-nitro phenol (PNPh) at different temperatures was investigated. The characteristics of such waste biomass were determined and found to have a surface area and iodine number of 495.71 m2/g and 475.88 mg/g, respectively. The effects of pH (2-12), adsorbent dose (0.6-0.8 g/L) and contact time (0-150 min) on the adsorptive removal process were studied. Maximum removal percentages of 89.95% and 92.11% were achieved for Ph and PNPh, respectively. Experimental equilibrium data for adsorption of both components were analyzed by the Langmuir, Freundlich and Tempkin isotherm models. The results show that the best fit was achieved with the Langmuir isotherm equation with maximum adsorption capacities of 132.37 and 161.44 mg/g for Ph and PNPh, respectively. The kinetic data were fitted to pseudo-first order, pseudo-second order and intraparticle diffusion models, and was found to follow closely the pseudo-second order model for both components. The calculated thermodynamic parameters, namely ΔG, ΔH, and ΔS showed that adsorption of Ph and PNPh was spontaneous and endothermic under examined conditions.
Wood sawdust was converted into a high-quality activated carbon (WSAC) via microwave-induced K(2)CO(3) activation. The operational variables including chemical impregnation ratio, microwave power and irradiation time on the carbon yield and adsorption capability were identified. The surface physical characteristics of WSAC were examined by pore structural analysis, scanning electron microscopy and nitrogen adsorption isotherms. The adsorptive behavior of WSAC was quantified using methylene blue as model dye compound. The best conditions resulted in activated carbon with a monolayer adsorption capacity of 423.17 mg/g and carbon yield of 80.75%. The BET surface area, Langmuir surface area and total pore volume were corresponded to 1496.05 m(2)/g, 2245.53 m(2)/g and 0.864 cm(3)/g, respectively. The findings support the potential to prepare high surface area and mesoporous activated carbon from wood sawdust by microwave assisted chemical activation.