Carbon from jatropha seed hull (JC) was prepared to study the adsorption of cadmium ions (Cd(2+)) from aqueous solutions under various experimental conditions. Batch equilibrium methods have been used to study the influences of the initial metal ion concentration (0.5-50 ppm), dosage (0.2-1 g), contact time (0-300 min), pH (2-7), and temperature (26-60 °C) on adsorption behavior. It has been found that the amount of cadmium adsorbed increases with the initial metal ion concentration, temperature, pH, contact time, and amount of adsorbent. A kinetic study proved that the mechanism of Cd(2+) adsorption on JC followed a three steps process, confirmed by an intraparticle diffusion model: rapid adsorption of metal ions, a transition phase, and nearly flat plateau section. The experimental results also showed that the Cd(2+) adsorption process followed pseudo-second-order kinetics. The Langmuir and Freundlich adsorption isotherm models were used to describe the experimental data, with the former exhibiting a better correlation coefficient than the latter (R² = 0.999). The monolayer adsorption capacity of JC has been compared with the capacities of the other reported agriculturally-based adsorbents. It has been clearly demonstrated that this agricultural waste generated by the biofuel industry can be considered a potential low-cost adsorbent for the removal of Cd(2+) from industrial effluents.
In this study, AB113 dye was successfully sequestered using a novel adsorbent made of mixed fish scales (MFS). The influence of adsorbent dosage, initial pH, temperature, initial concentration and contact time on the adsorption performance was investigated. The surface chemistry and morphology of the adsorbent were examined by FTIR, TGA and SEM. Amides, phosphate and carbonate groups were evidently responsible for the high affinity of MFS towards the dye. The adsorption equilibrium and kinetic were well described by Langmuir and pseudo-second-order models, respectively. The maximum adsorption capacities of MFS were 145.3-157.3mg/g at 30-50°C. The adsorption of AB113 dye onto the adsorbent was exothermic and spontaneous as reflected by the negative enthalpy and Gibbs energy changes. The results support MFS asa potential adsorbent for AB113 dye removal.
In this study, chitosan/poly (ethylene oxide) nanofibres were fabricated at different chitosan:PEO weight ratio by electrospinning process. The effects of chitosan/PEO composition onto adsorption capability for Cu(II), Zn(II) and Pb(II) ions were studied. Formation of beadless fibres were achieved at 60:40 chitosan:PEO ratio. Average fiber diameter, maximum tensile strength and the specific surface area of the beadless fibres were found to be 115±31nm, 1.58MPa and 218m2/g, respectively. Chitosan/PEO composition that produced beadless fibres tend to possess higher hydrophilicity and maximum specific surface area. These characteristics lead the beadless fibres to the maximum adsorption capability. Adsorption equilibrium data were analysed by Langmuir and Freundlich isotherm. Freundlich isotherm showed the better fit with the experimental data and proved the existence of the monolayer adsorption conditions. The maximum adsorption capacity of the beadless fibres for Cu(II), Zn(II) and Pb(II) ions were found to be 120, 117 and 108mgg-1, respectively.
Pharmaceutical pollutants substantially affect the environment; thus, their treatments have been the focus of many studies. In this article, the fixed-bed adsorption of pharmaceuticals on various adsorbents was reviewed. The experimental breakthrough curves of these pollutants under various flow rates, inlet concentrations, and bed heights were examined. Fixed-bed data in terms of saturation uptakes, breakthrough time, and the length of the mass transfer zone were included. The three most popular breakthrough models, namely, Adams-Bohart, Thomas, and Yoon-Nelson, were also reviewed for the correlation of breakthrough curve data along with the evaluation of model parameters. Compared with the Adams-Bohart model, the Thomas and Yoon-Nelson more effectively predicted the breakthrough data for the studied pollutants.
The current status of silver nanoparticles (AgNPs) in the water environment in Malaysia was examined and reported. For inspection, two rivers and two sewage treatment plants (STPs) were selected. Two activated carbons derived from oil palm (ACfOPS) and coconut (ACfCS) shells were proposed as the adsorbent to remove AgNPs. It was found that the concentrations of AgNPs in the rivers and STPs are in the ranges of 0.13 to 10.16 mg L-1 and 0.13 to 20.02 mg L-1, respectively, with the highest concentration measured in July. ACfOPS and ACfCS removed up to 99.6 and 99.9% of AgNPs, respectively, from the water. The interaction mechanism between AgNPs and the activated carbon surface employed in this work was mainly the electrostatic force interaction via binding Ag+ with O- presented in the activated carbon to form AgO. Fifteen kinetic models were compared statistically to describe the removal of AgNPs. It was found that the experimental adsorption data can be best described using the mixed 1,2-order model. Therefore, this model has the potential to be a candidate for a general model to describe AgNPs adsorption using numerous materials, its validation of which has been confirmed with other material data from previous works.
In this study freely suspended and Ca-alginate immobilized C. vulgaris cells were used for the biosorption of Fe(II), Mn(II), and Zn(II) ions, from the aqueous solution. Experimental data showed that biosorption capacity of algal cells was strongly dependent on the operational condition such as pH, initial metal ions concentration, dosages, contact time and temperature. The maximum biosorption of Fe(II) 43.43, Mn(II) 40.98 and Zn(II) 37.43 mg/g was achieved with Ca-alginate immobilized algal cells at optimum pH of 6.0, algal cells dosage 0.6 g/L, and contact time of 450 min at room temperature. The biosorption efficiency of freely suspended and immobilized C. vulgaris cells for heavy metals removal from the industrial wastewater was validated. Modeling of biosorption kinetics showed good agreements with pseudo-second-order. Langmuir and D-R isotherm models exhibited the best fit of experimental data. The thermodynamic parameters (ΔG°, ΔH°, and ΔS°) revealed that the biosorption of considered metal ions was feasible, spontaneous and exothermic at 25-45°C. The SEM showed porous morphology which greatly helps in the biosorption of heavy metals. The Fourier transform infrared spectrophotometer (FTIR) and X-rays Photon Spectroscopy (XPS) data spectra indicated that the functional groups predominately involved in the biosorption were C-N, -OH, COO-, -CH, C=C, C=S and -C-. These results shows that immobilized algal cells in alginate beads could potentially enhance the biosorption of considered metal ions than freely suspended cells. Furthermore, the biosorbent has significantly removed heavy metals from industrial wastewater at the optimized condition.
This study is based on the removal of methylene blue (MB) from aqueous solution by cost effective and biodegradable adsorbent carboxymethyl starch grafted polyvinyl pyrolidone (Car-St-g-PVP). The Car-St-g-PVP was synthesized by grafting vinyl pyrolidone onto carboxymethyl starch by free radical polymerization reaction. The structure and different properties of Car-St-g-PVP were determined by 1H NMR, FT-IR, XRD, TGA and SEM. A series of batch experiments were conducted for the removal of MB, The adsorption affecting factors such as temperature, contact time, initial concentration of MB dye, dose of Car-St-g-PVP and pH were studied in detail. The other parameters like the thermodynamic study, kinetics and isothermal models were fitted to the experimental data. The results showed that pseudo 2nd order kinetics and Langmuir's adsorption isotherms were best fitted to experimental data with regression coefficient R2 viz. 0.99 and 0.97. The kinetic study showed that the adsorption mechanism favored chemisorption. The Gibbs free energy (ΔG°) for the adsorption process was found to be -7.31 kJ/mol, -8.23 kJ/mol, -9.00 kJ/mol and -10.10 kJ/mol at 25 °C, 35 °C, 45 °C and 55 °C respectively. The negative values of ΔG° suggested the spontaneous nature of the adsorption process. Similarly, the positive values of entropy (ΔS°) and enthalpy (ΔH°) 91.27 J/k.mol and 19.90 kJ/mol showed the increasing randomness and endothermic nature of the adsorption process. The value of separation factor (RL) was found to be less than one (RL
Due to increasing antibiotic pollution in the water environment, green and efficient adsorbents are urgently needed to solve this problem. Here we prepare magnetic bamboo-based activated carbon (MDBAC) through delignification and carbonization using ZnCl2 as activator, resulting in production of an activated carbon with large specific surface area (1388.83 m2 g-1). The influencing factors, such as solution pH, initial sulfadiazine (SD) concentration, temperature, and contact time, were assessed in batch adsorption experiments. The Langmuir isotherm model demonstrated that MDBAC adsorption capacity on SD was 645.08 mg g-1 at its maximum, being higher than majority of previously reported adsorbents. In SD adsorption, the kinetic adsorption process closely followed the pseudo-second kinetic model, and the thermodynamic adsorption process was discovered to be exothermic and spontaneous in nature. The MDBAC exhibited excellent physicochemical stability, facile magnetic recovery and acceptable recyclability properties. Moreover, the synergistic interactions between MDBAC and SD mainly involved electrostatic forces, hydrogen bonding, π-π stacking, and chelation. Within the benefits of low cost, ease of production and excellent adsorption performance, the MDBAC biosorbent shows promising utilization in removing antibiotic contaminants from wastewater.
The present study intended to develop efficient hydrogel spheres in treating simulated wastewater contaminated with p-chlorophenol. Herein, copper-modified nanocellulose was grafted onto alginate to produce eco-friendly hydrogel spheres to utilize as a viable biosorbent. Fabricated spheres were characterized through scanning electron microscopy, thermogravimetry, surface area measurement, point of zero charge and zeta potential analyses. The adsorption of p-chlorophenol was optimized by altering various experimental conditions. Pseudo second order kinetics and Langmuir adsorption isotherm best described the adsorption of p-chlorophenol onto copper-modified cellulose nanocrystal-based spheres. The maximum adsorption capacity was 66.67 mg g-1 with a reusability up to five regeneration cycles. The thermodynamic study directed that p-chlorophenol adsorption was exothermic, spontaneous, and reversible within the analyzed temperature range. Weber-Morris model revealed that intraparticle diffusion was not the singular rate-controlling step in the adsorption process. Hence, copper-modified nanocellulose spheres could be employed as a sustainable and effective biosorbent for p-chlorophenol adsorption from wastewater.
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.
The natural zeolite has been modified with sulphate and phosphate. The adsorption of thorium from the aqueous solutions by using the natural and modified zeolites has been investigated via a batch method. The adsorbent samples were characterized by X-ray Diffraction (XRD), N2 adsorption-desorption (BET), Fourier transform infrared (FTIR), field emission scanning electron microscopy (FESEM), and energy dispersive X-ray spectroscopy (EDX). Modification of natural zeolite with sulphate and phosphate was found to increase its adsorption capacity of thorium but reduced its specific surface area (SBET). The adsorption experiments were expressed by Langmuir, Freundlich and Dubinin-Radushkevitch (D-R) isotherm models and the results of adsorption demonstrated that the adsorption of thorium onto the natural and modified zeolites correlated better with the Langmuir isotherm model than with the Freundlich isotherm model. The maximum adsorption capacity (Qo) was determined using the Langmuir isotherm model at 25 °C and was found to be 17.27, 13.83, and 10.21 mg/g for phosphate-modified zeolite, sulfate-modified zeolite, and natural zeolite, respectively. The findings of this study indicate that phosphate-modified zeolite can be utilized as an effective and low-cost adsorbent material for the removal of thorium from aqueous solutions.
In this study, adsorption behavior of anthill-eggshell composite (AEC) for the removal of hexavalent chromium (Cr6+) from aqueous solution was investigated. The raw AEC sample was thermally treated at 864 °C for 4 h and characterized using Brunauer-Emmett-Teller (BET), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), and X-ray fluorescence (XRF) techniques. The effects of adsorption process variables including initial Cr6+ concentration, contact time, and adsorbent dosage on the Cr6+ removal efficiency were investigated using central composite design (CCD) of response surface methodology (RSM). Equilibrium adsorption isotherm and kinetic were also studied. From the analysis of variance (ANOVA), the three variables proved to be significant and the optimum conditions for Cr6+ adsorption were obtained to be 150 mg/L initial Cr6+ concentration, 45.04-min contact time, and 0.5 g adsorbent dosage, which resulted in 86.21% of Cr6+ adsorbed. Equilibrium isotherm study showed that Freundlich model fitted well to the experimental data. The pseudo-second-order kinetic model appeared to better describe the experimental data. The study showed that mixed anthill-eggshell is a promising adsorbent for removing Cr6+ from aqueous solution.
This work describes the development of supported zeolite-Y membranes, prepared using the hydrothermal method, for the removal of nickel from an aqueous solution. Alumina hollow fibers prepared using the phase inversion and sintering technique were used as an inert support. The supported zeolite-Y membranes were characterized using the field emission scanning electron microscope (FESEM), X-ray diffraction (XRD), and the water permeation and rejection test. The performance of the supported zeolite-Y membranes for heavy metal removal using batch adsorption and filtration test was studied using the atomic absorption spectroscopy (AAS). The adsorption study shows that the removal of nickel was pH-dependent but affected by the presence of α-alumina. The seeded zeolite-Y membrane gave the highest adsorption capacity which was 126.2 mg g-1. This enabled the membrane to remove 63% of nickel ions from the aqueous solution within 180 min of contact time. The adsorption mechanism of nickel onto the zeolite-Y membrane was best fitted to the Freundlich isotherm. The kinetic study concluded that the adsorption was best fitted to pseudo-second-order model with higher correlation coefficient (R2 = 0.9996). The filtration study proved that the zeolite-Y membrane enabled to reduce the concentration of heavy metal at parts per billion level.
The feasibility of biomass-based activated carbons has received a huge attention due to their excellent characteristics such as inexpensiveness, good adsorption behaviour and potential to reduce a strong dependency towards non-renewable precursors. Therefore, in this research work, eco-friendly activated carbon from palm kernel shell that has been produced from one-stage physical activation by using the Box-Behnken design of Response Surface Methodology is highlighted. The effect of three input parameters-temperature, dwell time and gas flow rate-towards product yield and carbon dioxide (CO2) uptake at room temperature and atmospheric pressure are studied. Model accuracy has been evaluated through the ANOVA analysis and lack-of-fit test. Accordingly, the optimum condition in synthesising the activated carbon with adequate CO2 adsorption capacity of 2.13 mmol/g and product yield of 25.15 wt% is found at a temperature of 850 °C, holding time of 60 min and CO2 flow rate of 450 cm3/min. The synthesised activated carbon has been characterised by diverse analytical instruments including thermogravimetric analyser, scanning electron microscope, as well as N2 adsorption-desorption isotherm. The characterisation analysis indicates that the synthesised activated carbon has higher textural characteristics and porosity, together with better thermal stability and carbon content as compared to pristine palm kernel shell. Activated carbon production via one-step activation approach is economical since its carbon yield is within the industrial target, whereas CO2 uptake is comparable to the synthesised activated carbon from conventional dual-stage activation, commercial activated carbon and other published data from literature.
This study has applied the concept of the hybrid PAC-UF process in the treatment of the final effluent of the palm oil industry for reuse as feedwater for low-pressure boilers. In a bench-scale set-up, a low-cost empty fruit bunch-based powdered activated carbon (PAC) was employed for upstream adsorption of biotreated palm oil mill effluent (BPOME) with the process conditions: 60 g/L dose of PAC, 68 min of mixing time and 200 rpm of mixing speed, to reduce the feedwater strength, alleviate probable fouling of the membranes and thus improve the process flux (productivity). Three polyethersulfone ultrafiltration membranes of molecular weight cut-off (MWCO) of 1, 5 and 10 kDa were investigated in a cross-flow filtration mode, and under constant transmembrane pressures of 40, 80, and 120 kPa. The permeate qualities of the hybrid processes were evaluated, and it was found that the integrated process with the 1 kDa MWCO UF membrane yielded the best water quality that falls within the US EPA reuse standard for boiler-feed and cooling water. It was also observed that the permeate quality is fit for extended reuse as process water in the cement, petroleum and coal industries. In addition, the hybrid system's operation consumed 37.13 Wh m(-3) of energy at the highest applied pressure of 120 kPa, which is far lesser than the typical energy requirement range (0.8-1.0 kWh m(-3)) for such wastewater reclamation.
For the synthesis of a highly active TiO2-chitosan nanocomposite, pH plays a crucial role towards controlling its morphology, size, crystallinity, thermal stability, and surface adsorption properties. The presence of chitosan (CS) biopolymer facilitates greater sustainability to the photoexcited electrons and holes on the catalysts' surface. The variation of synthesis pH from 2 to 5 resulted in different physico-chemical and photocatalytic properties, whereby a pH of 3 resulted in TiO2-chitosan nanocomposite with the highest photocatalytic degradation (above 99 %) of methylene orange (MO) dye. This was attributed to the efficient surface absorption properties, high crystallinity, and the presence of reactive surfaces of -NH2 and -OH groups, which enhances the adsorption-photodegradation effect. The larger surface oxygen vacancies coupled with reduced electron-hole recombination further enhanced the photocatalytic activity. It is undeniable that the pH during synthesis is critical towards the development of the properties of the TiO2-chitosan nanocomposite for the enhancement of photocatalytic activity.
Substantial discharge of hazardous substances, especially dyes and heavy metal ions to the environment, has become a global concern due to many industries neglecting the environmental protocols in waste management. A massive discharge of contaminantsfrom different anthropogenic activities, can pose alarming threats to living species and adverse effect to the ecosystem stability. In the process of treating the polluted water, various methods and materials are used. Hybrid nanocomposites have attained numerous interest due to the combination of remarkable features of the organic and inorganic elements in a single material. In this regards, carbon and polymer based nanocomposites have gained particular interest because of their tremendous magnetic properties and stability. These nanocomposites can be fabricated using several approaches that include filling, template, hydrothermal, pulsed-laser irradiation, electro-spinning, detonation induced reaction, pyrolysis, ball milling, melt-blending, and many more. Moreover, carbon-based and polymer-based magnetic nanocomposites have been utilized for an extensive number of applications such as removal of heavy metal and dye adsorbents, magnetic resonance imaging, and drug delivery. This review emphasized mainly on the production of magnetic carbon and polymer nanocomposites employing various approaches and their applications in water and wastewater treatment. Furthermore, the future opportunities and challenges in applying magnetic nanocomposites for heavy metal ion and dye removal from water and wastewater treatment plant.
Removal of oil spillage from the environment is a global concern. Various methods, including the use of fibers as sorbents, have been developed for oil spill control. Oil palm empty fruit bunch (OPEFB) fiber is a plant biomass that may be acetylated by acetic anhydride using N-bromosuccinimide (NBS) as a catalyst; here, the extent of acetylation may be calculated in terms of weight percent gain (WPG). The modified fiber was used to remove Tapis and Arabian crude oils. The optimum time, temperature, and catalyst concentration were 4 h, 120 °C, and 3 %, respectively, and these parameters could achieve an 11.49 % increase in WPG. The optimized parameters improved the adsorption capacity of OPEFB fibers for crude oil removal. The acetylated OPEFB fibers were characterized by using Fourier transform infrared spectroscopy and field emission scanning electron microscopy to observe the functional groups available and morphology. Kinetic and isotherm studies were conducted using different contact times and oil/water ratios. The rate of oil sorption onto the OPEFB fibers can be adequately described by the pseudo-second-order equation. Adsorption studies revealed that adsorption of crude oil on treated OPEFB fiber could be best described by the Langmuir isotherm model.
Two superior adsorbents, namely bentonite and graphene oxide (GO), were hybridised to study the removal of copper and nickel ions from synthetic and industrial wastewater. The as-synthesised GO, bentonite/GO and bentonite were characterised by Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy and N2 adsorption-desorption analysis. The factors influencing the adsorption behaviours including contact time, initial solution pH, ionic strength, initial concentration of metal ions, temperature and adsorbent dosage were systematically investigated by batch equilibrium method. The adsorption equilibrium for copper and nickel onto bentonite was attained in 90 min while equilibrium was reached in 60 min on bentonite/GO. The adsorption of copper and nickel was pH-dependent in the range from pH 2 to pH 7 and from pH 2 to pH 8. Pseudo-first-order kinetic model excellently described the adsorption of copper and nickel onto bentonite and bentonite/GO. The equilibrium adsorption data was well described by the Langmuir isotherm model and the maximum adsorption capacity was 248.9 mg/g, 558.4 mg/g, 215.8 mg/g and 402.5 mg/g for bentonite-copper, bentonite/GO-copper, bentonite-nickel and bentonite/GO-nickel adsorption systems, respectively. The bentonite/GO composite exhibited a higher adsorption capacity of both cations from synthetic wastewater than pure bentonite owning to the synergistic effect between bentonite and GO. In all adsorption studies, copper was more efficiently removed than nickel due to its higher tendency to form bond with adsorbent surfaces. The adsorption of copper and nickel on bentonite/GO was mainly due to cation exchange, intermolecular and electrostatic interactions and physisorption dominated the adsorption processes. The practical application of bentonite/GO on adsorption of copper was investigated using real wastewater and its removal efficiency was beyond 98%. The excellent adsorption performances of composites for the copper and nickel removal from wastewater demonstrated its significant potential for pollution mitigations.
Adsorption capacity and percentage removal efficiency of Cu(II) and Ni(II) ions were studied and compared between raw kaolinite and acid-activated kaolinite. Acid-activated kaolin was prepared by refluxing raw kaolinite with concentrated sulphuric acid followed by calcination to enhance its surface properties and adsorption ability. Both raw and acid-activated kaolinite samples were characterized by Fourier transform infrared spectroscopy, energy dispersive X-ray, scanning electron micrograph and zeta potential analysis. Upon acid treatment, acid-activated kaolinite was discovered to have altered chemical composition and larger BET surface area as compared with raw kaolinite. The batch adsorption studies on aqueous solution were performed under different factors such as contact time, pH condition, adsorbent dosage, initial metal ion concentration and temperature. The optimum condition was selected for each factor including a contact time of 60 min, pH of 7.0, adsorbent dosage of 0.1 g, initial metal ion concentration of 100 mg/L and temperature of 25 °C. Then, the adsorption studies on wastewater samples were carried out at the selected optimum conditions. Acid-activated kaolinite always had better adsorption capacity and percentage removal efficiency than raw kaolinite due to the increasing amount of negative charges on the adsorbent surface and the number of metal ion binding sites upon acid treatment. The adsorption kinetic obtained was well described by the pseudo-second-order model, whereas the adsorption isotherms obtained were well described by either the Freundlich or the Langmuir adsorption model. The results showed that acid-activated kaolinite adsorbent is a better option as a favourable and feasible commercial low-cost adsorbent for wastewater treatment.