The efficiency of the extraction and removal of pollutants from food and the environment has been an important issue in analytical science. By incorporating inorganic species into an organic matrix, a new material known as an organic-inorganic hybrid material is formed. As it possesses high selectivity, permeability, and mechanical and chemical stabilities, organic-inorganic hybrid materials constitute an emerging research field and have become popular to serve as sorbents in various separaton science methods. Here, we review recent significant advances in analytical solid-phase extraction employing organic-inorganic composite/nanocomposite sorbents for the extraction of organic and inorganic pollutants from various types of food and environmental matrices. The physicochemical characteristics, extraction properties, and analytical performances of sorbents are discussed; including morphology and surface characteristics, types of functional groups, interaction mechanism, selectivity and sensitivity, accuracy, and regeneration abilities. Organic-inorganic hybrid sorbents combined with extraction techniques are highly promising for sample preparation of various food and environmental matrixes with analytes at trace levels.
In this work, palm shell waste powder activated carbon coated by magnesium silicate (PPAC-MS) were synthesized by the impregnation of magnesium silicate (MgSiO3) using economical material (silicon dioxide powder) via mild hydrothermal approach for the first time. As an effective adsorbent, PPAC-MS simultaneously removes BPA and Pb(II) in single and binary mode. Surprisingly, PPAC-MS exhibited a homogeneous thin plate mesh-like structure, as well as meso- and macropores with a high surface area of 772.1m2g-1. Due to its specific morphological characteristics, PPAC-MS had adsorption capacities of Pb(II) as high as 419.9mgg-1 and 408.8mgg-1 in single mode and binary mode based on Freudliuch isotherm model while those for BPA by PPAC-MS were 168.4mgg-1 and 254.7mgg-1 for single mode and binary modes corresponding to Langmuir isotherm model. Experiment results also indicated that the synergistic removal of BPA occurred because the precipitation process of Pb(II) leads to the co-precipitation of BPA with Pb(OH)2 compound. PPAC-MS showed a good reusability for 5 regeneration cycles using Mg(II) solution followed by thermal treatment. Overall, PPAC-MS has a high potential in the treatment process for wastewater containing both toxic heavy metals and emerging pollutants due to its high sorption capacities and reusability.
This study focused on the residue detection of the herbicides triclopyr and glufosinate ammonium in the runoff losses from the Tasik Chini oil palm plantation area and the Tasik Chini Lake under natural rainfall conditions in the Malaysian tropical environment. Triclopyr and glufosinate ammonium are post-emergence herbicides. Both herbicides were foliar-sprayed on 0.5 ha of oil palm plantation plots, which were individualized by an uneven slope of 10-15%. Samples were collected at 1, 3, 7, 15, 30, 45, 60, 90, and 120 days after treatment. The concentrations of both herbicides quickly diminished from those in the analyzed sample by the time of collection. The highest residue levels found in the field surface leachate were 0.031 (single dosage, triclopyr), 0.041 (single dosage, glufosinate ammonium), 0.017 (double dosage, triclopyr), and 0.037 μg/kg (double dosage, glufosinate ammonium). The chromatographic peaks were observed at "0" day treatment (2 h after herbicide application). From the applied active ingredients, the triclopyr and glufosinate losses were 0.025 and 0.055%, respectively. The experimental results showed that both herbicides are less potent than other herbicides in polluting water systems because of their short persistence and strong adsorption onto soil clay particles.
The present work was aimed at evaluating the multi-metals column adsorption of lead(II), cadmium(II) and manganese(II) ions onto natural bentonite. The bentonite clay adsorbent was characterized for physical and chemical properties using X-ray diffraction, X-ray fluorescence, Brunauer-Emmett-Teller surface area and cation exchange capacity. The column performance was evaluated using adsorbent bed height of 5.0 cm, with varying influent concentrations (10 mg/L and 50 mg/L) and flow rates (1.4 mL/min and 2.4 mL/min). The result shows that the breakthrough time for all metal ions ranged from 50 to 480 minutes. The maximum adsorption capacity was obtained at initial concentration of 10 mg/L and flow rate of 1.4 mL/min, with 2.22 mg/g of lead(II), 1.71 mg/g of cadmium(II) and 0.37 mg/g of manganese(II). The order of metal ions removal by natural bentonite is lead(II) > cadmium(II) > manganese(II). The sorption performance and the dynamic behaviour of the column were predicted using Adams-Bohart, Thomas, and Yoon-Nelson models. The linear regression analysis demonstrated that the Thomas and Yoon-Nelson models fitted well with the column adsorption data for all metal ions. The natural bentonite was effective for the treatment of wastewater laden with multi-metals, and the process parameters obtained from this work can be used at the industrial scale.
Chitosan ionic liquid beads were prepared from chitosan and 1-butyl-3-methylimidazolium based ionic liquids to remove Malachite Green (MG) from aqueous solutions. Batch adsorption experiments were carried out as a function of initial pH, adsorbent dosage, agitation time and initial MG concentration. The optimum conditions were obtained at pH 4.0, 0.008g of adsorbent dosage and 20min of agitation time were utilized in the kinetic and isotherm studies. Three kinetic models were applied to analyze the kinetic data and pseudo-second order was found to be the best fitted model with R2>0.999. In order to determine the adsorption capacity, the sorption data were analyzed using the linear form of Langmuir, Freundlich and Temkin equations. The isotherm was best fitted by Langmuir isotherm model. The maximum adsorption capacity (qmax) obtained from Langmuir isotherm for two chitosan beads 1-butyl-3-methylimidazolium acetate A and 1-butyl-3-methylimidazolium B are 8.07mgg-1 and 0.24mgg-1 respectively.
The main challenge in the lead removal simulation is the behaviour of non-linearity relationships between the process parameters. The conventional modelling technique usually deals with this problem by a linear method. The substitute modelling technique is an artificial neural network (ANN) system, and it is selected to reflect the non-linearity in the interaction among the variables in the function. Herein, synthesized deep eutectic solvents were used as a functionalized agent with carbon nanotubes as adsorbents of Pb2+. Different parameters were used in the adsorption study including pH (2.7 to 7), adsorbent dosage (5 to 20 mg), contact time (3 to 900 min) and Pb2+ initial concentration (3 to 60 mg/l). The number of experimental trials to feed and train the system was 158 runs conveyed in laboratory scale. Two ANN types were designed in this work, the feed-forward back-propagation and layer recurrent; both methods are compared based on their predictive proficiency in terms of the mean square error (MSE), root mean square error, relative root mean square error, mean absolute percentage error and determination coefficient (R2) based on the testing dataset. The ANN model of lead removal was subjected to accuracy determination and the results showed R2 of 0.9956 with MSE of 1.66 × 10-4. The maximum relative error is 14.93% for the feed-forward back-propagation neural network model.
A chitosan/polyvinyl alcohol (PVA)/zeolite composite was fabricated in this study. The composite was analyzed through field emission scanning electron microscopy, Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), thermogravimetric analysis, and weight loss test. FTIR and XRD results revealed a strong interaction among chitosan, PVA, and zeolite. Weight loss test results indicated that the composite was stable in acidic and basic media. Congo red was removed through flocculation, and the removal rate was 94% at an initial concentration of 100mg/L for a dose of 1g/L. The removal rate of methyl orange was controlled by adsorption at an initial concentration of less than 100mg/L. Flocculation occurred at high concentrations. The removal rate was also 94% at an initial concentration of 500mg/L for a dose of 5g/L. The adsorption behavior of the composite for the removal of methyl orange and Cr(VI) was described by using a pseudo-second-order kinetic model. The adsorption capacity of the composite for Cr(VI) was 450mg/g. Therefore, the synthesized composite exhibited versatility during the removal of dyes and heavy metals.
A palygorskite-iron oxide nanocomposite (Pal-IO) was synthesized in situ by embedding magnetite into the palygorskite structure through co-precipitation method. The physico-chemical characteristics of Pal-IO and their pristine components were examined through various spectroscopic and micro-analytical techniques. Batch adsorption experiments were conducted to evaluate the performance of Pal-IO in removing Pb(II) from aqueous solution. The surface morphology, magnetic recyclability and adsorption efficiency of regenerated Pal-IO using desorbing agents HCl (Pal-IO-HCl) and ethylenediaminetetraacetic acid disodium salt (EDTA-Na2) (Pal-IO-EDTA) were compared. The nanocomposite showed a superparamagnetic property (magnetic susceptibility: 20.2 emu g-1) with higher specific surface area (99.8 m2 g-1) than the pristine palygorskite (49.4 m2 g-1) and iron oxide (72.6 m2 g-1). Pal-IO showed a maximum Pb(II) adsorption capacity of 26.6 mg g-1 (experimental condition: 5 g L-1 adsorbent loading, 150 agitations min-1, initial Pb(II) concentration from 20 to 500 mg L-1, at 25 °C) with easy separation of the spent adsorbent. The adsorption data best fitted to the Langmuir isotherm model (R2 = 0.9995) and pseudo-second order kinetic model (R2 = 0.9945). Pb(II) desorption using EDTA as the complexing agent produced no disaggregation of Pal-IO crystal bundles, and was able to preserve the composite's magnetic recyclability. Pal-IO-EDTA exhibited almost 64% removal capacity after three cycles of regeneration and preserved the nanocomposite's structural integrity and magnetic properties (15.6 emu g-1). The nanocomposite holds advantages as a sustainable material (easily separable and recyclable) for potential application in purifying heavy metal contaminated wastewaters.
A novel hydrous iron-nickel-manganese (HINM) trimetal oxide was successfully fabricated using oxidation and coprecipitation method for metalloid arsenite removal. The atomic ratio of Fe:Ni:Mn for this adsorbent is 3:2:1. HINM adsorbent was identified as an amorphous nanosized adsorbent with particle size ranged from 30 nm to 60 nm meanwhile the total active surface area and pore diameter of HINM area of 195.78 m2/g and 2.43 nm, respectively. Experimental data of arsenite adsorption is best fitted into pseudo-second order and Freundlich isotherm model. The maximum adsorption capacity of arsenite onto HINM was 81.9 mg/g. Thermodynamic study showed that the adsorption of arsenite was a spontaneous and endothermic reaction with enthalpy change of 14.04 kJ/mol and Gibbs energy of -12 to -14 kJ/mol. Zeta potential, thermal gravimetric (TGA) and Fourier transform infrared (FTIR) analysis were applied to elucidate the mechanism of arsenite adsorption by HINM. Mechanism of arsenite adsorption by HINM involved both chemisorption and physisorption based on the electrostatic attraction between arsenite ions and surface charge of HINM. It also involved the hydroxyl substitution by arsenite ions through the formation of inner-sphere complex. Reusability of HINM trimetal oxide was up to 89% after three cycles of testing implied that HINM trimetal oxide is a promising and practical adsorbent for arsenite.
Hepatitis B virus-like particles expressed in Escherichia coli were purified using anion exchange adsorbents grafted with polymer poly(oligo(ethylene glycol) methacrylate) in flow-through chromatography mode. The virus-like particles were selectively excluded, while the relatively smaller sized host cell proteins were absorbed. The exclusion of virus-like particles was governed by the accessibility of binding sites (the size of adsorbents and the charge of grafted dextran chains) as well as the architecture (branch-chain length) of the grafted polymer. The branch-chain length of grafted polymer was altered by changing the type of monomers used. The larger adsorbent (90 μm) had an approximately twofold increase in the flow-through recovery, as compared to the smaller adsorbent (30 μm). Generally, polymer-grafted adsorbents improved the exclusion of the virus-like particles. Overall, the middle branch-chain length polymer grafted on larger adsorbent showed optimal performance at 92% flow-through recovery with a purification factor of 1.53. A comparative study between the adsorbent with dextran grafts and the polymer-grafted adsorbent showed that a better exclusion of virus-like particles was achieved with the absorbent grafted with inert polymer. The grafted polymer was also shown to reduce strong interaction between binding sites and virus-like particles, which preserved the particles' structure.
In the present study, iminodiacetic acid (IDA)-modified kenaf fiber, K-IDA formed by the chemical modification of plant kenaf biomass was tested for its efficacy as a sorbent material towards the purification of waste water. The K-IDA fiber was first characterized by the instrumental techniques like Fourier transform infrared (FTIR) analysis, elemental analysis (CHNSO), and scanning electron microscopy (SEM). On testing for the biosorption, we found that the K-IDA has an increment in the adsorption of Cu2+ ions as compared against the untreated fiber. The Cu2+ ions adsorption onto K-IDA fits very well with the Langmuir model and the adsorption maximum achieved to be 91.74mg/g. Further, the adsorption kinetics observed to be pseudo second-order kinetics model and the Cu2+ ions adsorption is a spontaneous endothermic process. The desorption study indicates a highest percentage of Cu2+ of 97.59% from K-IDA under 1M HCl solution against H2SO4 (72.59%) and HNO3 (68.66%). The reusability study indicates that the efficiency did not change much until the 4th cycle and also providing enough evidence for the engagement of our biodegradable K-IDA fiber towards the removal of Cu2+ ions in real-time waste water samples obtained from the electroplating and wood treatment industries.
A critical challenge in producing an antibody-based assay with the highest reproducibility and sensitivity is the strategy to immobilize antibodies to solid phase. To date, numerous methods of antibody immobilization were reported but each was subjected to its advantages and limitations. The current study proposes a new potential antibody binding protein, the human neonatal fragment crystallizable (Fc) receptor. This protein has shown its high affinity to the Fc of antibody either in vivo or in vitro. Human neonatal Fc receptor is a heterodimer constructed by p51 α-heavy chain and β2-microglobulin light chain; however, the binding sites toward the antibody are located in the p51 α-heavy chain. Hence, vector cloning and recombinant protein expression were carried out to express the p51 α-heavy chain of the human neonatal Fc receptor (hFcRn-α). The recombinant protein expressed, hFcRn-α, was adopted to pin rabbit IgG against hepatitis B virus surface antigen to a solid phase. A sandwich enzyme-linked immunosorbent assay was further developed to evaluate the efficiency of hFcRn-α-directed immobilization in antigen detection. The result was compared with the conventional physical adsorption method. The findings demonstrated that human neonatal Fc receptor was efficient in pinning antibodies and generating higher signals compared with the physical adsorption of antibody.
Dead calcareous skeletons (CSs) as low-cost adsorbents were studied to remove lead ions (Pb (II)) in an aqueous solution. Factors influencing the efficiency of CSs were evaluated by adsorbent size, contact time, initial concentration, dosage concentration and pH. The optimum CS size for removal of Pb (II) was 710 μm at an equilibrium time of 720 min. The best dosage of CS was 10 g/L for a 99% removal efficiency without pH adjustment. Pb (II) ions were effectively removed in the initial pH of the metal solution. CS was able to remove a high concentration (100 mg/L) of Pb (II) at a removal efficiency of 99.92% and at an adsorption capacity of 13.06 mg/g. Our results demonstrated the potential of CS as a metal adsorbent in the aqueous phase with a high-removal efficiency and distinct physical characteristics.
In this work, mesoporous-activated carbon (CSAC) was prepared from chitosan flakes (CS) via single-step sodium hydroxide activation for the adsorption of methylene blue (MB). CSAC was prepared using different impregnation ratios of NaOH:CS (1:1, 2:1, 3:1, and 4:1) at 800°C for 90min. The adsorption performance of CSAC was evaluated for MB at different adsorption variables, such MB initial concentrations (25-400mg/L), solution pH (3-11), and temperature (30-50°C). The adsorption isotherm data of CSAC-MB were well fitted to Langmuir model with a maximum adsorption capacity 143.53mg/g at 50°C. Best representation of kinetic data was obtained by the pseudo-second order model. CSAC exhibited excellent adsorption uptake for MB and can potentially be used for other cationic dyes.
Box-Behnken model of response surface methodology was used to study the effect of adsorption process parameters for Rhodamine B (RhB) removal from aqueous solution through optimized large surface area date stone activated carbon. The set experiments with three input parameters such as time (10-600min), adsorbent dosage (0.5-10g/L) and temperature (25-50°C) were considered for statistical significance. The adequate relation was found between the input variables and response (removal percentage of RhB) and Fisher values (F- values) along with P-values suggesting the significance of various term coefficients. At an optimum adsorbent dose of 0.53g/L, time 593min and temperature 46.20°C, the adsorption capacity of 210mg/g was attained with maximum desirability. The negative values of Gibb(')s free energy (ΔG) predicted spontaneity and feasibility of adsorption; whereas, positive Enthalpy change (ΔH) confirmed endothermic adsorption of RhB onto optimized large surface area date stone activated carbons (OLSADS-AC). The adsorption data were found to be the best fit on the Langmuir model supporting monolayer type of adsorption of RhB with maximum monolayer layer adsorption capacity of 196.08mg/g.
To develop a novel granular adsorbent to remove arsenic and antimony from water, calcined Mg/Al-layered double-hydroxide (CLDH)-incorporated polyethersulfone (PES) granular adsorbents (PES-LDH) were prepared using a core-shell method having 25% PES in an N,N-dimethylformamide solution. The PES-LDH displayed a spherical hollow shape having a rough surface and the average particle size of 1-2 mm. On the PES-LDH surface, nanosized CLDH (100-150 nm) was successfully immobilized by consolidation between PES and CLDH. The adsorption of Sb(V) by PES-LDH was found to be more favorable than for As(V), with the maximum adsorption capacity of As(V) and Sb(V) being 7.44 and 22.8 mg/g, respectively. The regeneration results indicated that a 0.5 M NaOH and 5 M NaCl mixed solution achieved an 80% regeneration efficiency in As(V) adsorption and desorption. However, the regeneration efficiency of Sb(V) gradually decreased due to its strong binding affinity, even though the PES-LDH showed much higher Sb(V) adsorption efficiency than As(V). This study suggested that PES-LDH could be a promising granular adsorbent for the remediation of As(V) and Sb(V) contained in wastewater.
Palm oil mill wastes (palm kernel shell (PKS)) were used to prepare activated carbons, which were tested in the removal of colorants from water. The adsorbents were prepared by 1-h impregnation of PKS with ZnCl2 as the activating agent (PKS:ZnCl2 mass ratios of 1:1 and 2:1), followed by carbonization in autogenous atmosphere at 500 and 550 °C during 1 h. The characterization of the activated carbons included textural properties (porosity), surface chemistry (functional groups), and surface morphology. The dye removal performance of the different activated carbons was investigated by means of the uptake of methylene blue (MB) in solutions with various initial concentrations (25-400 mg/L of MB) at 30 °C, using a 0.05-g carbon/50-mL solution relationship. The sample prepared with 1:1 PKS:ZnCl2 and carbonized at 550 °C showed the highest MB adsorption capacity (maximum uptake at the equilibrium, q max = 225.3 mg MB / g adsorbent), resulting from its elevated specific surface area (BET, 1058 m2/g) and microporosity (micropore surface area, 721 m2/g). The kinetic experiments showed that removals over 90% of the equilibrium adsorptions were achieved after 4-h contact time in all the cases. The study showed that palm oil mill waste biomass could be used in the preparation of adsorbents efficient in the removal of colorants in wastewaters.
Palm oil fuel ash (POFA) is an agricultural waste which was employed in this study to produce novel adsorptive ceramic hollow fibre membranes. The membranes were fabricated using phase inversion-based extrusion technique and sintered at 1150 °C. The membranes were then evaluated on their ability to adsorb cadmium (Cd(II)). These membranes were characterised using (nitrogen) N2 adsorption-desorption analysis, field emission scanning electron microscopy-energy-dispersive X-ray spectroscopy (FESEM-EDX) mapping, X-ray fluorescence (XRF), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) analyses while adsorptivity activity was examined by batch adsorption studies. The adsorption test results show that the quantity of hollow fibre used and water pH level significantly affected the adsorption performance with the 3-fibre membrane yielding 96.4% Cd(II) removal in 30 min equilibrium time at pH 7. These results are comparable to those reported by other studies, and hence demonstrate a promising alternative of low-cost hollow fibre adsorbent membrane. Graphical abstract Figure of FESEM image of the hollow fibre, proposed mechanism and the graph of percentage removal of Cd(II) using POFA.
The CO2 capture capacity and cyclic stability of calcium oxide (CaO) prepared from cockle shells (CS) were enhanced by incorporating rice husk (RH) and binder through wet-mixing method. The cyclic reaction of calcination and carbonation was demonstrated using thermal gravimetric analyzer (TGA) which the calcination was performed in a pure N2 environment at 850 °C for 20 min and carbonation at 650 °C for 30 min in 20 vol% of CO2 in N2. The analysis using x-ray fluorescence (XRF) identified silica (Si) as the major elements in the sorbents. The RH-added sorbents also contained several types of metal elements such as which was a key factor to minimize the sintering of the sorbent during the cyclic reaction and contributed to higher CO2 capture capacity. The presence of various morphologies also associated with the improvement of the synthesized sorbents performance. The highest initial CO2 capture capacity was exhibited by CS+10%RH sorbent, which was 12% higher than the RH-free sorbent (CS). However, sorbents with the higher RH loading amount such as 40 and 50 wt% were preferred to maintain high capture capacity when the sorbents were regenerated and extended to the cyclic reaction. The sorbents also demonstrated the lowest average sorption decay, which suggested the most stable sorbent for cyclic-reaction. Once regenerated, the capture capacity of the RH-added sorbent was further increased by 12% when clay was added into the sorbent. Overall, the metal elements in RH and clay were possibly the key factor that enhances the performance of CaO prepared from CS, particularly for cyclic CO2 capture. Graphical abstract Cyclic calcination and carbonation reaction.
This work presents the synthesis of the novel silica-cyanopropyl functionalized magnetic graphene oxide (MGO/SiO2-CN) hybrid nanomaterial derived by sol-gel method as a cheap efficient magnetic sorbent for the removal of extremely hazardous lead ions from aqueous media. The integration of the magnetic property, the carbon substrate, and the nitrile (-C ≡ N) containing organic grafted silica matrix promoted the adsorption capability against lead ions along with its simple synthesis recovery and low cost. The prepared nanocomposite was comprehensively characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. Adsorption of lead was found to be pH dependent because of the charged nature of both analyte and adsorbent surface. Adsorption experiments were conducted under the optimum conditions, and the obtained experimental data from atomic absorption spectroscopy were analyzed using the popular isothermal models namely Langmuir, Freundlich, and Dubinin-Radushkevich isotherms as well as kinetically studied and evaluated for adsorption standard free energy (E). The experimental results have demonstrated the enhanced adsorption capability of the proposed sorbent nanocomposite for lead ion removal with the maximum adsorption capacity of 111.11 mg/g at pH 5.0. The proposed mechanism of lead adsorption was mainly attributed to the complexation of lead positive ions with the grafted -C ≡ N bond. The synergistic effect of the combination of three components (i.e., the magnetic graphene oxide matrix, the triple bond containing organic moiety, and the inorganic porous silica framework) excelled the adsorption capability and proved to be a good candidate as adsorbent for the removal of lead ions.