Cyanotoxins, microcystins and cylindrospermopsin, are potent toxins produced by cyanobacteria in potable water supplies. This study investigated the removal of cyanotoxins from aqueous media by magnetophoretic nanoparticle of polypyrrole adsorbent. The adsorption process was pH dependent with maximum adsorption occurring at pH 7 for microcystin-LA, LR, and YR and at pH 9 for microcystin-RR and cylindrospermopsin (CYN). Kinetic studies and adsorption isotherms reflected better fit for pseudo-second-order rate and Langmuir isotherm model, respectively. Thermodynamic calculations showed that the cyanotoxin adsorption process is endothermic and spontaneous in nature. The regenerated adsorbent can be successfully reused without appreciable loss of its original capacity.
The utilization of natural zeolite (NZ) as an adsorbent for NH4+ removal was investigated. Three types of NZ (i.e., NZ01, NZ02, and NZ03) were characterized, and their NH4+ adsorption process in aqueous solution was evaluated. The effect of pH towards NH4+ adsorption showed that the NZ01 has the highest NH4+ adsorption capacity compared with other natural zeolites used. The application of NZ01 for a simultaneous removal of NH4+ and turbidity in synthetic NH4+-kaolin suspension by adsorptive coagulation process for treating drinking water was studied. The addition of NZ01 into the system increased the NH4+ removal efficiency (ηNH4+) from 11.64% without NZ01 to 41.86% with the addition of 0.2 g L-1 of NZ01. The turbidity removal (ηT), however, was insignificantly affected since the ηT was already higher than 98.0% over all studied parameter's ranges. The thermodynamic and kinetic data analyses suggested that the removal of NH4+ obeyed the Temkin isotherm model and pseudo-second-order kinetic model, respectively. Generally, the turbidity removal was due to the flocculation of destabilized solid particles by alum in the suspension system. The ηNH4+ in surface water was 29.31%, which is lower compared with the removal in the synthetic NH4+-kaolin suspension, but a high ηT (98.65%) was observed. It was found that the addition of the NZ01 could enhance the removal of NH4+ as well as other pollutants in the surface water.
Due to the rapid growth in the heavy metal-based industries, their effluent and local dumping have created significant environmental issues. In the past, typically, removal of heavy metals was handled by reverse osmosis and ion exchange techniques, but these methods have many disadvantages. Therefore, extensive work into the development of improved techniques has increased, especially for heavy metal removal. Many countries are currently researching new materials and techniques based on nanotechnology for various applications that involve extracting heavy metals from different water sources such as wastewater, groundwater, drinking water and surface water. Nanotechnology provides the possibility of enhancing existing techniques to tackle problems more efficiently. The development in nanotechnology has led to the discovery of many new materials such as magnetic nanoparticles. These nanoparticles demonstrate excellent properties such as surface-volume ratio, higher surface area, low toxicity and easy separation. Besides, magnetic nanoparticles can be easily and efficiently recovered after adsorption compared with other typical adsorbents. This review mainly emphasises on the efficiency of heavy metal removal using magnetic nanoadsorbent from aqueous solution. In addition, an in-depth analysis of the synthesis, characterisation and modification approaches of magnetic nanoparticles is systematically presented. Furthermore, future opportunities and challenges of using magnetic particles as an adsorbent for the removal of heavy metals are also discussed.
The purpose of this research is to synthesize environmentally friendly nanosorbents for the novel adsorption of diesel range organics (DRO) from contaminated water. Central composite design (CCD) analysis of response surface methodology (RSM) was employed in a model fitting of the variables predicting the adsorption efficiency of Moringa oleifera-functionalized zerovalent iron particles (ZINPs) for the removal of DRO. The effects of the reaction parameters on the response were screened using 24 factorial designs to determine the statistically significant independent variables. A quadratic model predicting the DRO adsorption efficiency of ZINPs with an F value of 276.84 (p value
This work aimed to develop a modified chitosan adsorbent with enhanced adsorption selectivity for Au(III) over Cu(II) from acidic chloride solutions using low-cost and green raw materials. Various adsorbents, i.e., chitosan powder, chitosan microbeads, chitosan/palm kernel fatty acid distillate (PKFAD) microcomposites, magnetite nanoparticles, and chitosan/PKFAD/magnetite nanocomposites (CPMNs), were first evaluated for their ability to adsorb Au(III) and Cu(II) from single- and binary-metal solutions across different pH levels, followed by parametric analysis of Au(III) and Cu(II) adsorption from binary- and multi-metal solutions onto CPMNs, Au(III) desorption from Au(III)-loaded CPMNs, and reusability of CPMNs. Finally, Au(III)-loaded CPMNs were characterized with SEM-EDX, XRD, FTIR, and XPS to confirm the proposed adsorption mechanisms. Among all the adsorbents studied, CPMNs exhibited outstanding performance in adsorbing Au(III) from an equimolar binary Au(III)-Cu(II) solution, achieving the highest equilibrium adsorption capacity of 0.479 mmol/g (94.4 mg/g) without reaching saturation. Under optimal adsorption conditions of pH 3, 1 g/L CPMN dosage, and 90 min contact time, CPMNs adsorbed 96 % of Au(III) with a selectivity over Cu(II) exceeding 99 %. CPMNs demonstrated excellent reusability, maintaining over 80 % adsorption and desorption efficiencies for 5 cycles. The proposed adsorption mechanisms of CPMNs for Au(III) encompass electrostatic attraction, hydrogen bonding, solvation, and reduction.
Herein, the polymer nanomatrix of chitosan/SiO2 (CHI/n-SiO2) was enriched with a π-π electron donor-acceptor system using diaromatic rings of benzil (BEZ) assisted via a hydrothermal process to obtain an effective adsorbent of chitosan-benzil/SiO2 (CHI-BEZ/n-SiO2). The polymer nanomatrix (CHI/n-SiO2) and the resulting adsorbent (CHI-BEZ/n-SiO2) were applied to remove the anionic acid red 88 (AR88) dye from aqueous media in a comparative mode. Box-Behnken design (BBD) was adopted to optimize AR88 adsorption onto CHI/n-SiO2 and CHI-BEZ/n-SiO2 with respect to variables that influence AR88 adsorption (adsorbent dose: 0.02-0.1 g/100 mL; pH: 4-10; and time: 10-90). The adsorption studies at equilibrium were conducted with a variety of initial AR88 dye concentrations (20-200 mg/L). The adsorption isotherm results reveal that the AR88 adsorption by CHI/n-SiO2 and CHI-BEZ/n-SiO2 are described by the Langmuir model. The kinetic adsorption profiles of AR88 with CHI/n-SiO2 and CHI-BEZ/n-SiO2 reveal that the pseudo-first-order model provides the best fit results. Interestingly, CHI-BEZ/n-SiO2 has a high adsorption capacity (261.2 mg/g), which exceeds the adsorption capacity of CHI/n-SiO2 (215.1 mg/g) that relates to the surface effects of SiO2 and the functionalization of chitosan with BEZ. These findings show that CHI-BEZ/n-SiO2 represents a highly efficient adsorbent for the removal of harmful pollutants from water, which outperforming the CHI/n-SiO2 system.
A low-cost fruit waste namely watermelon peel (WMP) was utilized as a promising precursor for the preparation of mesoporous activated carbon (WMP-AC) via microwave assisted-K2CO3 activation. The WMP-AC was applied as an adsorbent for methylene blue dye (MB) removal. Several types of characterizations, such as specific surface area (BET), Scanning Electron Microscopy with Energy Dispersive X-ray Spectroscopy (SEM-EDX), Elemental Analysis (CHNS/O), and Fourier Transform Infrared Spectroscopy (FTIR) were used to identify the physicochemical properties of WMP-AC. Furthermore, Box-Behnken design (BBD) was applied to optimize the influence of the adsorption operational variables (contact time, adsorbent dose, working temperature, and solution pH) on MB dye adsorption. Thus, based on significant interactions, the optimum BBD output shows the best removal of 50 mg·L-1 MB (92%) was recorded at an adsorbent dose of 0.056 g, contact time of 4.4 min, working temperature of 39 °C, and solution pH 8.4. The Langmuir uptake capacity of WMP-AC was found to be 312.8 mg·g-1, with the best fitness to the pseudo-second-order kinetics model and an endothermic adsorption process. The adsorption mechanisms of MB by WMP-AC can be assigned to the hydrogen bonding, electrostatic attraction, and π-π stacking. The findings of this study indicate that WMP is a promising precursor for producing porous activated carbon for MB dye removal.
Calix[4]arene/polyurethane (C4PU) has been synthesized and characterized as an alternative adsorbent for the adsorption of methylene blue (MB) and malachite green (MG) dyes from the aqueous solution. C4PU was synthesized by reacting p-tert-butyl calix[4]arene with hexamethylene diisocyanate (HMDI) as the cross-linking agent. Different polymer ratios were synthesized, and C4PU-4 shows better adsorption than other ratios. The polymer was characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), Brunauer-Emmett-Teller (BET) analysis, and point of zero charges (pHPZC). The isotherms and kinetics of the adsorption of MB and MG were studied under a range of experimental conditions, including pH, adsorbent dosage, initial dye concentration, and contact time. The adsorption was determined by the adsorption percentage of MB and MG dyes from the solution. The Langmuir isotherm model best describes the adsorption process for both dyes, and it follows a pseudo-second-order kinetic model, with the maximum adsorption capacity (qmax) of MB and MG, respectively, was found to be 1.991 mg·g-1 and 2.240 mg·g-1.
This research aims to convert pomegranate peel (PP) into microporous activated carbon (PPAC) using a microwave assisted K2CO3 activation method. The optimum activation conditions were carried out with a 1:2 PP/K2CO3 impregnation ratio, radiation power 800 W, and 15 min irradiation time. The statistical Box-Behnken design (BBD) was employed as an effective tool for optimizing the factors that influence the adsorption performance and removal of methylene blue (MB) dye. The output data of BBD with a desirability function indicate a 94.8% removal of 100 mg/L MB at the following experimental conditions: PPAC dose of 0.08 g, solution pH of 7.45, process temperature of 32.1 °C, and a time of 30 min. The pseudo-second order (PSO) kinetic model accounted for the contact time for the adsorption of MB. At equilibrium conditions, the Freundlich adsorption isotherm describes the adsorption results, where the maximum adsorption capacity of PPAC for MB dye was 291.5 mg g-1. This study supports the utilization of biomass waste from pomegranate peels and conversion into renewable and sustainable adsorbent materials. As well, this work contributes to the management of waste biomass and water pollutant sequestration.
Perfluoroalkyl carboxylic acids (PFCAs) are sub-class of perfluoroalkyl substances commonly detected in water matrices. They are persistent in the environment, hence highly toxic to living organisms. Their occurrence at trace amount, complex nature and prone to matrix interference make their extraction and detection a challenge. This study consolidates current advancements in solid-phase extraction (SPE) techniques for the trace-level analysis of PFCAs from water matrices. The advantages of the methods in terms of ease of applications, low-cost, robustness, low solvents consumption, high pre-concentration factors, better extraction efficiency, good selectivity and recovery of the analytes have been emphasized. The article also demonstrated effectiveness of some porous materials for the adsorptive removal of the PFCAs from the water matrices. Mechanisms of the SPE/adsorption techniques have been discussed. The success and limitations of the processes have been elucidated.
In this study, a magnetic chitosan grafted-benzaldehyde (CS-BD/Fe3O4) was hydrothermally prepared using benzaldehyde as a grafting agent to produce a promising adsorbent for the removal of acid red 88 (AR88) dye. The CS-BD/Fe3O4 was characterized by infrared spectroscopy, surface area analysis, scanning electron microscopy-energy dispersive X-ray, vibrating sample magnetometry, powder X-ray diffraction, CHN elemental analysis, and point of zero charge (pHPZC). The Box-Behnken design (BBD) was adopted to study the role of variables that influence AR88 dye adsorption (A: CS-BD/Fe3O4 dose (0.02-0.1 g), B: pH (4-10), and time C: (10-90 min)). The ANOVA results of the BBD model indicated that the F-value for the AR88 removal was 22.19 %, with the corresponding p-value of 0.0002. The adsorption profiles at equilibrium and dynamic conditions reveal that the Temkin model and the pseudo-first-order kinetics model provide an adequate description of the isotherm results, where the maximum adsorption capacity (qmax) with the AR88 dye was 154.1 mg/g. Several mechanisms, including electrostatic attraction, n-π interaction, π-π interaction, and hydrogen bonding, regulate the adsorption of AR88 dyes onto the CS-BD/Fe3O4 surface. As a result, this research indicates that CS-BD/Fe3O4 can be utilized as an effective and promising bio-adsorbent for azo dye removal from contaminated wastewater.
Adsorption efficiency of a duo-material blend featuring the fabrication of modified chitosan adsorbents (powder (C-emimAc), bead (CB-emimAc) and sponge (CS-emimAc)) for the removal of Cd(II) from aqueous solution was investigated. The chitosan@activated carbon (Ch/AC) blend was developed in a green ionic solvent, 1-ethyl-3-methyl imidazolium acetate (EmimAc) and its characteristics was examined using FTIR, SEM, EDX, BET and TGA. The possible mechanism of interaction between the composites and Cd(II) was also predicted using the density functional theory (DFT) analysis. The interactions of various blend forms (C-emimAc, CB-emimAc and CS-emimAc) with Cd(II) gave better adsorption at pH 6. The composites also present excellent chemical stability in both acidic and basic conditions. The monolayer adsorption capacities obtained (under the condition 20 mg/L [Cd], adsorbent dosage 5 mg, contact time 1 h) for the CB-emimAc (84.75 mg/g) > C-emimAc (72.99 mg/g) > CS-emimAc (55.25 mg/g), as this was supported by their order of increasing BET surface area (CB-emimAc (120.1 m2/g) > C-emimAc (67.4 m2/g) > CS-emimAc (35.3 m2/g)). The feasible adsorption interactions between Cd(II) and Ch/AC occurs through the O-H and N-H groups of the composites, as supported by DFT analysis in which an electrostatic interactions was predicted as the dominant force. The interaction energy (-1309.35 eV) calculated via DFT shows that the Ch/AC with amino (-NH) and hydroxyl (-OH) groups are more effective with four significant electrostatic interactions with the Cd(II) ion. The various form of Ch/AC composites developed in EmimAc possess good adsorption capacity and stability for the adsorption Cd(II).
Several water and wastewater technologies have been implored for the removal of dyes during wastewater treatments; however; different types have been reportedly found in surface and groundwater systems. Hence, there is a need to investigate other water treatment technologies for the complete remediation of dyes in aquatic environments. In this study, novel chitosan-based polymer inclusion membranes (PIMs) were synthesized for the removal of malachite green dye (MG) which is a recalcitrant of great concern in water. Two types of PIMs were synthesized in this study, the first PIM (PIMs-A) was composed of chitosan, bis-(2-ethylhexyl) phosphate (B2EHP), and dioctyl phthalate (DOP). While, the second PIMs (PIMs-B) were composed of chitosan, Aliquat 336, and DOP. The physico-thermal stability of the PIMs was investigated using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA), both PIMs demonstrated good stability with a weak intermolecular force of attraction amongst the various components of the membranes. The effects of the initial concentration of MG, pH of the MG solution, stripping solution, and time were investigated. At optimum conditions, both membranes (PIM-A and B) recorded the highest efficiencies of 96 % and 98 % at pH 4 and initial contaminants concentration of 50 mg/L, respectively. Finally, both PIMs were used for the removal of MG in different environmental samples (river water, seawater, and tap water) with an average removal efficiency of 90 %. Thus, the investigated PIMs can be considered a potential suitable technique for the removal of dyes and other contaminants from aquatic matrices.
Water bodies with the dye methylene blue pose serious environmental and health risks to humans. Therefore, the creation and investigation of affordable, potential adsorbents to remove methylene blue dye from water resources as a long-term fix is one focus of the scientific community. Food plants and other carbon-source serve as a hotspot for a wider range of application on different pollutants that impact the environment and living organisms. Here, we reviewed the use of treated and untreated biosorbents made from plant waste leaves for removing the dye methylene blue from aqueous media. After being modified, activated carbon made from various plant leaves improves adsorption performance. The range of activating chemicals, activation methods, and bio-sorbent material characterisation using FTIR analysis, Barunauer-Emmett-Teller (BET) surface area, scanning electron microscope (SEM-EDX), and SEM-EDX have all been covered in this review. It has been thoroughly described how the pH solution of the methylene blue dye compares to the pHPZC of the adsorbent surface. The presentation also includes a thorough analysis of the application of the isotherm model, kinetic model, and thermodynamic parameters. The selectivity of the adsorbent is the main focus of the adsorption kinetics and isotherm models. It has been studied how adsorption occurs, how surface area and pH affect it, and how biomass waste compares to other adsorbents. The use of biomass waste as adsorbents is both environmentally and economically advantageous, and it has been discovered to have exceptional color removal capabilities.
An effective hydrothermally prepared chitosan-benzaldehyde/SiO2 adsorbent (CTA-BZA/SiO2) employed functionalization of a CTA biopolymer with SiO2 nanoparticles and BZA. CTA-BZA/SiO2 is an adsorbent that was utilized for the adsorption of an acidic dye (acid red 88, AR88) from synthetic wastewater. The fundamental adsorption variables (A: CTA-BZA/SiO2 dosage (0.02-0.1 g); B: pH (4-10); and C: duration (10-60)) were optimized via the Box-Behnken design (BBD). The Langmuir and Freundlich isotherms (coefficients of determination R2 = 0.99) agreed well with empirical data of AR88 adsorption by CTA-BZA/SiO2. The pseudo-first-order model showed reasonable agreement with the kinetic data of AR88 adsorption by CTA-BZA/SiO2. The maximal AR88 adsorption capacity (qmax) for CTA-BZA/SiO2 was identified to be 252.4 mg/g. The electrostatic attractions between both the positively charged CTA-BZA/SiO2 adsorbent and the AR88 anions, plus the n-π, π-π, and H-bond interactions contribute to the favourable adsorption process. This study reveals that CTA-BZA/SiO2 has the capacity to be a suitable adsorbent for the removal of a wider range of organic dyes from industrial effluents.
Water contamination can be detrimental to the human health due to higher concentration of carcinogenic heavy metals such as chromium (Cr) in the wastewater. Many traditional methods are being employed in wastewater treatment plants for Cr removal to control the environmental impacts. Such methods include ion exchange, coagulation, membrane filtration, and chemical precipitation and microbial degradation. Recent advances in materials science and green chemistry have led to the development of nanomaterial that possess high specific surface areas and multiple functions, making them suitable for removing metals such as Cr from wastewater. Literature shows that the most efficient, effective, clean, and long-lasting approach for removing heavy metals from wastewater involves adsorbing heavy metals onto the surface of nanomaterial. This review assesses the removal methods of Cr from wastewater, advantages and disadvantages of using nanomaterial to remove Cr from wastewater and potential negative impacts on human health. The latest trends and developments in Cr removal strategies using nanomaterial adsorption are also explored in the present review.
Development of strategies for removing heavy metals from aquatic environments is in high demand. Cadmium is one of the most dangerous metals in the environment, even under extremely low quantities. In this study, kenaf and magnetic biochar composite were prepared for the adsorption of Cd2+. The synthesized biochar was characterized using (a vibrating-sample magnetometer VSM), Scanning electron microscopy (SEM), X-ray powder diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). The adsorption batch study was carried out to investigate the influence of pH, kinetics, isotherm, and thermodynamics on Cd2+ adsorption. The characterization results demonstrated that the biochar contained iron particles that help in improving the textural properties (i.e., surface area and pore volume), increasing the number of oxygen-containing groups, and forming inner-sphere complexes with oxygen-containing groups. The adsorption study results show that optimum adsorption was achieved under pH 5-6. An increase in initial ion concentration and solution temperature resulted in increased adsorption capacity. Surface modification of biochar using iron oxide for imposing magnetic property allowed for easy separation by external magnet and regeneration. The magnetic biochar composite also showed a higher affinity to Cd2+ than the pristine biochar. The adsorption data fit well with the pseudo-second-order and the Langmuir isotherm, with the maximum adsorption capacity of 47.90 mg/g.
The present study investigated the sustainable approach for wastewater treatment using waste algal blooms. The current study investigated the removal of toxic metals namely chromium (Cr), nickel (Ni), and zinc (Zn) from aqueous solutions in batch and column studies using biochar produced by the marine algae Ulva reticulata. SEM/EDX, FTIR, and XRD were used to examine the adsorbents' properties and stability. The removal efficiency of toxic metals in batch operations was investigated by varying the parameters, which included pH, biochar dose, initial metal ion concentration, and contact time. Similarly, in the column study, the removal efficiency of heavy metal ions was investigated by varying bed height, flow rate, and initial metal ion concentration. Response Surface Methodology (Central Composite Design (CCD)) was used to confirm the linearity between the observed and estimated values of the adsorption quantity. The packed bed column demonstrated successful removal rates of 90.38% for Cr, 91.23% for Ni, and 89.92% for Zn heavy metals from aqueous solutions, under a controlled environment. The breakthrough analysis also shows that the Thomas and Adams-Bohart models best fit the regression values, allowing prior breakthroughs in the packed bed column to be predicted. Desorption studies were conducted to understand sorption and elution during different regeneration cycles. Adding 0.3 N sulfuric acid over 40 min resulted in the highest desorption rate of the column and adsorbent used for all three metal ions.
The presence of emerging water pollutants such as endocrine-disrupting compounds (EDCs), including 17-ethynylestradiol (EE2), bisphenol A (BPA), and perfluorooctanoic acid (PFOA), in contaminated water sources poses significant environmental and health challenges. This study aims to address this issue by investigating the efficiency of novel calcium-based metal-organic frameworks, known as mixed-linker calcium-based metal-organic frameworks (Ca-MIX), in adsorbing these endocrine-disrupting compounds. This study analyzed the influence of influent concentration, bed height, and flow rate on pollutant removal, with bed height emerging as a crucial factor. From the breakthrough curves, it was determined that the column maximum adsorption capacities followed the order of 17-ethynylestradiol (101.52 μg/g; 40%) > bisphenol A (99.07 μg/g; 39%) > perfluorooctanoic acid (81.28 μg/g; 32%). Three models were used to predict the adsorption process, with the Yan model outperforming the other models. This suggests the potential of mixed-linker calcium-based metal-organic frameworks for removing endocrine-disrupting compounds from water, using the Yan model as an effective predictor. Overall, this study provides valuable insights for the development of effective water treatment methods using mixed-linker calcium-based metal-organic frameworks to remove endocrine-disrupting compounds from contaminated water sources.
This study investigates the feasibility of spent tea waste extract (STWE) as a green modifying agent for the modification of chitosan adsorbent towards aspirin removal. Response surface methodology based on Box-Behnken design was employed to find the optimal synthesis parameters (chitosan dosage, spent tea waste concentration, and impregnation time) for aspirin removal. The results revealed that the optimum conditions for preparing chitotea with 84.65% aspirin removal were 2.89 g of chitosan, 18.95 mg/mL of STWE, and 20.72 h of impregnation time. The surface chemistry and characteristics of chitosan were successfully altered and improved by STWE, as evidenced by FESEM, EDX, BET, and FTIR analysis. The adsorption data were best fitted to pseudo 2nd order, followed by chemisorption mechanisms. The maximum adsorption capacity of chitotea was 157.24 mg/g, as fitted by Langmuir, which is impressive for a green adsorbent with a simple synthesis method. Thermodynamic studies demonstrated the endothermic nature of aspirin adsorption onto chitotea.