In this investigation, microwave irradiation assisted by ZnCl2 was used to transform pineapple crown (PN) waste into mesoporous activated carbon (PNAC). Complementary techniques were employed to examine the physicochemical characteristics of PNAC, including BET, FTIR, SEM-EDX, XRD, and pH at the point-of-zero-charge (pHpzc). PNAC is mesoporous adsorbent with a surface area of 1070 m2/g. The statistical optimization for the adsorption process of two model cationic dyes (methylene blue: MB and, crystal violet: CV) was conducted using the response surface methodology-Box-Behnken design (RSM-BBD). The parameters include solution pH (4-10), contact time (2-12) min, and PNAC dosage (0.02-0.1 g/100 mL). The Freundlich and Langmuir models adequately described the dye adsorption isotherm results for the MB and CV systems, whereas the pseudo-second order kinetic model accounted for the time dependent adsorption results. The maximum adsorption capacity (qmax) for PNAC with the two tested dyes are listed: 263.9 mg/g for CV and 274.8 mg/g for MB. The unique adsorption mechanism of MB and CV dyes by PNAC implicates multiple contributions to the adsorption process such as pore filling, electrostatic forces, H-bonding, and π-π interactions. This study illustrates the possibility of transforming PN into activated carbon (PNAC) with the potential to remove two cationic dyes from aqueous media.
In this pioneering study, electrostatic spraying (ES) technology with high voltages is proposed to reduce the size of hydrogel microbeads further, aiming to enhance the adsorption rate of cationic methylene blue (MB) dye. The increased voltages, ranging from 0.0 to 13.0 kV, further decreased the size of electrostatically sprayed hydrogel microbeads crosslinked by hydrogen bonds between sodium alginate (SA) and carboxymethyl chitosan (CMCS) in hydrochloric acid. The size of SA/CMCS hydrogel microbeads was successfully reduced from 2000 ± 121 μm (SC-2000) to 400 ± 15 μm (SC-400). Notably, SC-400 exhibits the highest maximum adsorption capacity (qm) and rate constant (k2) at 840.3 mg/g and 0.0598 g/mg/min, respectively, at pH 9.0 and a temperature of 25 °C in the absence of ionic compounds, which is three times higher than that of SC-2000, due to their high specific surface area and pore volume. Through a series of adsorption studies and characterization analyses, SA/CMCS hydrogel microbeads displayed heterogeneous adsorption behaviors towards MB dye through electrostatic interactions between the deprotonated carboxylic groups and cationic MB molecules, where MB adsorption efficiency could be significantly influenced by pH and ionic strength. These findings suggest that ES technology is effective in synthesizing smaller SA/CMCS hydrogel microbeads with enhanced MB removal rates and stable adsorption capacities and their applications could be further explored for removing other organic dyes and toxic metals in subsequent research studies.
Herein, a mesoporous magnetic chitosan-salicylaldehyde/calcium oxide nanoparticle (CS-SL/CaO/Fe3O4) biocomposite adsorbent that was prepared via freeze-drying. The CS-SL/CaO/Fe3O4 was utilized for the adsorption of ramazol brilliant blue (RBB) dye from aqueous solution. The physicochemical properties of the CS-SL/CaO/Fe3O4 were evaluated using diverse characterization techniques, including BET, XRD, FTIR, FESEM-EDX, CHNS, and pHpzc. The three main factors for adsorption included the following A: CS-SL/CaO/Fe3O4 dosage (0.02-0.1 g/100 mL), B: pH (4-10), and C: Time (60-540 min). These factors were improved using statistical methods, specifically the Box-Behnken design (BBD). The optimal conditions for achieving maximum RBB removal (62.5 %) are listed: CS-SL/CaO/Fe3O4 dosage of 0.1 g/100 mL, a solution pH of 7, and a contact time of 540 min. The adsorption kinetics and equilibrium isotherms were well described by the pseudo first order (PFO) kinetic and Langmuir isotherm models, respectively. Thus, the CS-SL/CaO/Fe3O4 material has a maximum adsorption capacity (qmax) of 63.3 mg/g for RBB at 25 °C. The adsorption mechanism of RBB onto the CS-SL/CaO/Fe3O4 surface was attributed to electrostatic forces, n-π stacking, H-bonding, and Pi-Pi interactions. Thus, CS-SL/CaO/Fe3O4 represents a recoverable magnetic adsorbent with potential for capture of organic dyes from wastewater.
Polyethersulphone (PES) membranes blended with silicon dioxide (SiO2) nanoparticles were prepared via a dry-jet wet spinning technique for the removal of bisphenol A (BPA) by adsorption mechanism. The morphology of SiO2 nanoparticles was analysed using a transmission electron microscopy and particle size distribution was also analysed. The prepared membranes were characterized by several techniques including field emission scanning electron microscopy, Fourier transform infrared spectroscopy and water contact angle. The adsorption mechanism of membrane towards BPA was evaluated by batch experiments and kinetic model. The influence of natural organic matter (NOM) in feed water on membrane BPA removal was also studied by filtration experiments. Results showed that BPA adsorption capacity as high as 53 µg/g could be achieved by the PES membrane incorporated with 2 wt% SiO2 in which the adsorption mechanism was in accordance with the pseudo-second-order kinetic model. The intraparticles diffusion model suggested that the rate limiting factor of membrane adsorption mechanism is governed by the diffusion of BPA into the membrane pores. The presence of 10 ppm NOM has reported to negatively reduce BPA removal by 24%, as it tended to compete with BPA for membrane adsorption. This work has demonstrated that PES-SiO2 membrane has the potential to eliminate trace amount of BPA from water source containing NOM.
This paper presents the findings of a study on adsorption of dichlorodiphenythreechloroethen (DDT) and polychlorinated biphenyls (PCBs) on three nanomaterials including Multi walled Carbon Nanotube (MWNT), nano-clay and nano-alumina. DDT and PCBs are of significant concern due their high toxicity and long environmental half-lives. Experiments were conducted using batch adsorption procedures at different DDT and PCBs concentrations, from 10 to 60 mg/L. The amounts of MWNT, nano-clay and Nano-alumina used were 0.25%, 0.50%, 0.75%, 1%, 2% and 10%. The adsorption of PCBs solution onto the MWNT, nano-clay and nano-alumina was characterized by an initial rapid adsorption which eventually became constant within 22, 20, and 17 hours, respectively. The adsorption of DDT solution onto the MWNT, nano-clay and nano-alumina was also characterized by an initial rapid adsorption which gradually became constant within 22, 22 and 16 hours, respectively. Results of this study indicated that MWNT was a better adsorbent material compared to nano-clay and nano-alumina for both contaminants in this study. While at 10% of MWNT 88.9% and 77% of DDT and PCB were removed by MWNT, respectively. The effect of pH and temperature were also investigated.
The nanobiocatalyst (NBC) is an emerging innovation that synergistically integrates advanced nanotechnology with biotechnology and promises exciting advantages for improving enzyme activity, stability, capability and engineering performances in bioprocessing applications. NBCs are fabricated by immobilizing enzymes with functional nanomaterials as enzyme carriers or containers. In this paper, we review the recent developments of novel nanocarriers/nanocontainers with advanced hierarchical porous structures for retaining enzymes, such as nanofibres (NFs), mesoporous nanocarriers and nanocages. Strategies for immobilizing enzymes onto nanocarriers made from polymers, silicas, carbons and metals by physical adsorption, covalent binding, cross-linking or specific ligand spacers are discussed. The resulting NBCs are critically evaluated in terms of their bioprocessing performances. Excellent performances are demonstrated through enhanced NBC catalytic activity and stability due to conformational changes upon immobilization and localized nanoenvironments, and NBC reutilization by assembling magnetic nanoparticles into NBCs to defray the high operational costs associated with enzyme production and nanocarrier synthesis. We also highlight several challenges associated with the NBC-driven bioprocess applications, including the maturation of large-scale nanocarrier synthesis, design and development of bioreactors to accommodate NBCs, and long-term operations of NBCs. We suggest these challenges are to be addressed through joint collaboration of chemists, engineers and material scientists. Finally, we have demonstrated the great potential of NBCs in manufacturing bioprocesses in the near future through successful laboratory trials of NBCs in carbohydrate hydrolysis, biofuel production and biotransformation.
Sequencing batch reactor (SBR) is one of the various methods of biological treatments used for treating wastewater and landfill leachate. This study investigated the treatment of landfill leachate and domestic wastewater by adding a new adsorbent (powdered ZELIAC; PZ) to the SBR technique. ZELIAC consists of zeolite, activated carbon, lime stone, rice husk ash, and Portland cement. The response surface methodology and central composite design were used to elucidate the nature of the response surface in the experimental design and describe the optimum conditions of the independent variables, including aeration rate (L/min), contact time (h), and ratio of leachate to wastewater mixture (%; v/v), as well as their responses (dependent variables). Appropriate conditions of operating variables were also optimized to predict the best value of responses. To perform an adequate analysis of the aerobic process, four dependent parameters, namely, chemical oxygen demand (COD), color, ammonia-nitrogen (NH3-N), and phenols, were measured as responses. The results indicated that the PZ-SBR showed higher performance in removing certain pollutants compared with SBR. Given the optimal conditions of aeration rate (1.74 L/min), leachate to wastewater ratio (20%), and contact time (10.31 h) for the PZ-SBR, the removal efficiencies for color, NH3-N, COD, and phenols were 84.11%, 99.01%, 72.84%, and 61.32%, respectively.
Polypyrrole multi-walled carbon nanotube composite layers were used to modify the gold layer to measure heavy metal ions using the surface plasmon resonance technique. The new sensor was fabricated to detect trace amounts of mercury (Hg), lead (Pb), and iron (Fe) ions. In the present research, the sensitivity of a polypyrrole multi-walled carbon nanotube composite layer and a polypyrrole layer were compared. The application of polypyrrole multi-walled carbon nanotubes enhanced the sensitivity and accuracy of the sensor for detecting ions in an aqueous solution due to the binding of mercury, lead, and iron ions to the sensing layer. The Hg ion bonded to the sensing layer more strongly than did the Pb and Fe ions. The limitation of the sensor was calculated to be about 0.1 ppm, which produced an angle shift in the region of 0.3° to 0.6°.
Cyclodextrin-ionic liquid polymer (βCD-BIMOTs-TDI) was firstly synthesized using functionalized β-Cyclodextrin (CD) with 1-benzylimidazole (BIM) to form monofunctionalized CD (βCD-BIMOTs) and was further polymerized using toluene diisocyanate (TDI) linker to form insoluble βCD-BIMOTs-TDI. SEM characterization result shows that βCD-BIMOTs-TDI exhibits macropore size while the BET result shows low surface area (1.254 m(2)g(-1)). The unique properties of the ILs allow us to produce materials with different morphologies. The adsorption isotherm and kinetics of 2,4-dichlorophenol (2,4-DCP) onto βCD-BIMOTs-TDI is studied. Freundlich isotherm and pseudo-second order kinetics are found to be the best to represent the data for 2,4-DCP adsorption on the βCD-BIMOTs-TDI. The presence of macropores decreases the mass transfer resistance and increases the adsorption process by reducing the diffusion distance. The change in entropy (ΔS°) and heat of adsorption (ΔH°) for 2,4-DCP on βCD-BIMOTs-TDI were estimated as -55.99 J/Kmol and -18.10 J/mol, respectively. The negative value of Gibbs free energy (ΔG°) indicates that the adsorption process is thermodynamically feasible, spontaneous and chemically controlled. Finally, the interactions between the cavity of βCD-BIMOTs and 2,4-DCP are investigated and the results shows that the inclusion of the complex formation and π-π interaction are the main processes involved in the adsorption process.
A solid phase extraction (SPE) method has been developed using a newly synthesized titanium (IV) butoxide-cyanopropyltriethoxysilane (Ti-CNPrTEOS) sorbent for polar selective extraction of aromatic amines in river water sample. The effect of different parameters on the extraction recovery was studied using the SPE method. The applicability of the sorbents for the extraction of polar aromatic amines by the SPE was extensively studied and evaluated as a function of pH, conditioning solvent, sample loading volume, elution solvent and elution solvent volume. The optimum experimental conditions were sample at pH 7, dichloromethane as conditioning solvent, 10 mL sample loading volume and 5 mL of acetonitrile as the eluting solvent. Under the optimum conditions, the limit of detection (LOD) and limit of quantification (LOQ) for solid phase extraction using Ti-CNPrTEOS SPE sorbent (0.01-0.2; 0.03-0.61 µg L(-1)) were lower compared with those achieved using Si-CN SPE sorbent (0.25-1.50; 1.96-3.59 µg L(-1)) and C18 SPE sorbent (0.37-0.98; 1.87-2.87 µg L(-1)) with higher selectivity towards the extraction of polar aromatic amines. The optimized procedure was successfully applied for the solid phase extraction method of selected aromatic amines in river water, waste water and tap water samples prior to the gas chromatography-flame ionization detector separation.
β-Cyclodextrin-ionic liquid polymer (CD-ILP) was first synthesized by functionalized β-cyclodextrin (CD) with 1-benzylimidazole (BIM) to form monofunctionalized CD (βCD-BIMOTs) and was further polymerized using a toluene diisocyanate (TDI) linker to form insoluble CD-ILP (βCD-BIMOTs-TDI). The βCD-BIMOTs-TDI polymer was characterized using various tools and the results obtained were compared with those derived from the native β-cyclodextrin polymer (βCD-TDI). The SEM result shows that the presence of ionic liquid (IL) increases the pore size, while the thermo gravimetric analysis (TGA) result shows that the presence of IL increases the stability of the polymer. Meanwhile, Brunauer-Emmett-Teller (BET) results show that βCD-BIMOTs-TDI polymer has 1.254 m(2)/g surface areas and the Barret-Joyner-Halenda (BJH) pore size distribution result reveals that the polymer exhibits macropores with a pore size of 77.66 nm. Preliminary sorption experiments were carried out and the βCD-BIMOTs-TDI polymer shows enhanced sorption capacity and high removal towards phenols and As(V).
Palm Oil Mill Effluent (POME) treatment has always been a topic of research in Malaysia. This effluent that is extremely rich in organic content needs to be properly treated to minimize environmental hazards before it is released into watercourses. The main aim of this work is to evaluate the potential of applying natural, chemically and thermally modified banana peel as sorbent for the treatment of biologically treated POME. Characteristics of these sorbents were analyzed with BET surface area and SEM. Batch adsorption studies were carried out to remove color, total suspended solids (TSS), chemical oxygen demand (COD), tannin and lignin, and biological oxygen demand (BOD) onto natural banana peel (NBP), methylated banana peel (MBP), and banana peel activated carbon (BPAC) respectively. The variables of pH, adsorbent dosage, and contact time were investigated in this study. Maximum percentage removal of color, TSS, COD, BOD, and tannin and lignin (95.96%, 100%, 100%, 97.41%, and 76.74% respectively) on BPAC were obtained at optimized pH of 2, contact time of 30 h and adsorbent dosage of 30 g/100 ml. The isotherm data were well described by the Redlich-Peterson isotherm model with correlation coefficient of more than 0.99. Kinetic of adsorption was examined by Langergren pseudo first order, pseudo second order, and second order. The pseudo second order was identified to be the governing mechanism with high correlation coefficient of more than 0.99.
This study evaluates the sugarcane bagasse derived activated carbon (SBAC) prepared by microwave heating for the adsorptive removal of ammonical nitrogen and orthophosphate from the semi-aerobic landfill leachate. The physical and chemical properties of SBAC were examined by pore structural analysis, scanning electron microscopy, Fourier transform infrared spectroscopy and elemental analysis. The effects of adsorbent dosage, contact time and solution pH on the adsorption performance were investigated in a batch mode study at 30°C. Equilibrium data were favorably described by the Langmuir isotherm model, with a maximum monolayer adsorption capacity for ammonical nitrogen and orthophosphate of 138.46 and 12.81 mg/g, respectively, while the adsorption kinetic was best fitted to the pseudo-second-order kinetic model. The results illustrated the potential of sugarcane bagasse derived activated carbon for the adsorptive treatment of semi-aerobic landfill leachate.
In this work, two low-cost wastes, bivalve shell (BS) and Zea mays L. husk leaf (ZHL), were investigated to adsorb malachite green (MG) from aqueous solutions. The ZHL was treated with calcined BS to give the BS-ZHL, and its ability to adsorb MG was compared with untreated ZHL, calcined BS and Ca(OH)(2)-treated ZHL under several different conditions: pH (2-8), adsorbent dosage (0.25-2.5 g L(-1)), contact time (10-30 min), initial MG concentration (10-200 mg L(-1)) and temperature (303-323 K). The equilibrium studies indicated that the experimental data were in agreement with the Langmuir isotherm model. The use of 2.5 g L(-1) BS-ZHL resulted in the nearly complete removal of 200 mg L(-1) of MG with a maximum adsorption capacity of 81.5 mg g(-1) after 30 min of contact time at pH 6 and 323 K. The results indicated that the BS-ZHL can be used to effectively remove MG from aqueous media.
A novel sol-gel hybrid methyltrimethoxysilane-tetraethoxysilane (MTMOS-TEOS) was produced and applied as sorbent for solid phase extraction (SPE). Five selected organophosphorus pesticides (OPPs) were employed as model compounds to evaluate the extraction performance of the synthesized sol-gel organic-inorganic hybrid MTMOS-TEOS. Analysis was performed using gas chromatography-mass spectrometry. Several important SPE parameters were optimized. Under the optimum extraction conditions, the method using the sol-gel organic-inorganic hybrid MTMOS-TEOS as SPE sorbent showed good linearity in the range of 0.001-1 μg L(-1), good repeatability (RSD 2.1-3.1%, n=5), low limits of detection at S/N=3 (0.5-0.9 pg mL(-1)) and limit of quantification (1-3 pg mL(-1), S/N=10). The performance of the MTMOS-TEOS SPE was compared to commercial C18 Supelclean SPE since C18 SPE is widely used for OPPs. The MTMOS-TEOS SPE method LOD was 500-600 × lower than the LOD of commercial C18 SPE. The LOD achieved with the sol-gel organic-inorganic hybrid MTMOS-TEOS SPE sorbent allowed the detection of these OPPs in drinking water well below the level set by European Union (EU) at 0.1 μg L(-1) of each pesticides. The developed MTMOS-TEOS SPE method was successfully applied to real sample analysis of the selected OPPs from several water samples and its application extended to the analysis of several fruits samples. Excellent recoveries and RSDs of the OPPs were obtained from the various water samples (recoveries: 97-111%, RSDs 0.4-2.8%, n=3) and fruit samples (recoveries: 96-111%), RSDs 1-4%, n=5) using the sol-gel organic-inorganic hybrid MTMOS-TEOS SPE sorbent. Recoveries and RSDs of OPPs from river water samples and fruit samples using C18 Supelclean SPE sorbent were 91-97%, RSD 0.9-2.6, n=3 and 86-96%, RSD 3-8%, n=5, respectively). The novel sol-gel hybrid MTMOS-TEOS SPE sorbent demonstrate the potential as an alternative inexpensive extraction sorbent for OPPs with higher sensitivity for the OPPs.
The potential use of non-viable biomass of a Gram negative bacterium i.e. Acinetobacter haemolyticus to remove Cr(III) species from aqueous environment was investigated. Highest Cr(III) removal of 198.80 mg g(-1) was obtained at pH 5, biomass dosage of 15 mg cell dry weight, initial Cr(III) of 100 mg L(-1) and 30 min of contact time. The Langmuir and Freundlich models fit the experimental data (R(2)>0.95) while the kinetic data was best described using the pseudo second-order kinetic model (R(2)>0.99). Cr(III) was successfully recovered from the bacterial biomass using either 1M of CH(3)COOH, HNO(3) or H(2)SO(4) with 90% recovery. TEM and FTIR suggested the involvement of amine, carboxyl, hydroxyl and phosphate groups during the biosorption of Cr(III) onto the cell surface of A. haemolyticus. A. haemolyticus was also capable to remove 79.87 mg g(-1) Cr(III) (around 22.75%) from raw leather tanning wastewater. This study demonstrates the potential of using A. haemolyticus as biosorbent to remove Cr(III) from both synthetic and industrial wastewater.
This work explores the feasibility of orange peel, a citrus processing biomass as an alternative precursor for preparation of activated carbon (OPAC) via microwave assisted K(2)CO(3) activation. The operational parameters, chemical impregnation ratio, microwave power and irradiation time on the carbon yield and adsorption capability were investigated. The virgin characteristics of OPAC were examined by pore structural analysis, scanning electron microscopy, Fourier transform infrared spectroscopy, nitrogen adsorption isotherm, elemental analysis, surface acidity/basicity and zeta potential measurement. The optimum conditions resulted in OPAC with a monolayer adsorption capacity of 382.75 mg/g for methylene blue and carbon yield of 80.99%. The BET surface area, Langmuir surface area and total pore volume were identified to be 1104.45 m(2)/g, 1661.04 m(2)/g and 0.615 m(3)/g, respectively. Equilibrium data were simulated using the Langmuir, Freundlich, Dubinin-Radushkevich, Redlich-Peterson, and Toth isotherms, and kinetic data were fitted to the pseudo-first-order, pseudo-second-order and Elovich kinetic models.
The presence of heavy metals in the environment results in a number of environmental problems. In this study, the potential of Rambai stem (Baccaurea motleyana) of Malaysia in removing nickel ion from aqueous solution has been evaluated. The raw material used in this study was obtained from local orchard. The collected material passed through physical preparation and treatment process. The adsorbent was thoroughly characterized by SEM, EDX and FTIR studies. The effect of initial nickel concentration, dosage of adsorbent and pH on the adsorption process were investigated. The highest adsorption capacity obtained at weak acidic conditions (pH 4-5) when dosage and initial concentrations are 0.1 and 30 ppm respectively. The percentage of removal of nickel from the solution was found to be 51%. The experimental data fitted well in Freundlich isotherms indicating the adsorption of nickel on Rambai stem (Baccaurea motleyana) followed heterogenous surface phenomena.
The potential application of Chlorella vulgaris UMACC 001 for bioremediation of textile wastewater (TW) was investigated using four batches of cultures in high rate algae ponds (HRAP) containing textile dye (Supranol Red 3BW) or TW. The biomass attained ranged from 0.17 to 2.26 mg chlorophyll a/L while colour removal ranged from 41.8% to 50.0%. There was also reduction of NH(4)-N (44.4-45.1%), PO(4)-P (33.1-33.3%) and COD (38.3-62.3%) in the TW. Supplementation of the TW with nutrients of Bold's Basal Medium (BBM) increased biomass production but did not improve colour removal or reduction of pollutants. The mechanism of colour removal by C. vulgaris is biosorption, in accordance with both the Langmuir and Freundlich models. The HRAP using C. vulgaris offers a good system for the polishing of TW before final discharge.
The potential of physic seed hull (PSH), Jantropha curcas L. as an adsorbent for the removal of Cd(2+) and Zn(2+) metal ions from aqueous solution has been investigated. It has been found that the amount of adsorption for both Cd(2+) and Zn(2+) increased with the increase in initial metal ions concentration, contact time, temperature, adsorbent dosage and the solution pH (in acidic range), but decreased with the increase in the particle size of the adsorbent. The adsorption process for both metal ions on PSH consists of three stages-a rapid initial adsorption followed by a period of slower uptake of metal ions and virtually no uptake at the final stage. The kinetics of metal ions adsorption on PSH followed a pseudo-second-order model. The adsorption equilibrium data were fitted in the three adsorption isotherms-Freundlich, Langmuir and Dubinin-Radushkevich isotherms. The data best fit in the Langmuir isotherm indication monolayer chemisorption of the metal ions. The adsorption capacity of PSH for both Zn(2+) and Cd(2+) was found to be comparable with other available adsorbents. About 36-47% of the adsorbed metal could be leached out of the loaded PSH using 0.1M HCl as the eluting medium.