Textile wastewater contains methylene blue (MB), a major coloring agent in textile industry. Activated carbon (AC) is the most widely used adsorbent in removing dyes from industrial wastewater. However, high production cost of AC is the major obstacle for its wide application in dye wastewater treatment. In this study, a sustainable approach in synthesizing graphenic adsorbent from palm oil mill effluent (POME), a potential carbonaceous source, has been explored. This new development in adsorption technique is considered as green synthesis as it does not require any binder during the synthesis process, and at the same time, it helps to solve the bottleneck of palm oil industry as POME is the main cause contributed to Malaysia's water pollution problem. The synthesized GSC was characterized through XRD, FESEM, and EDX. The adsorption performance of the synthesized GSC was evaluated by adsorption of MB. The effect of initial concentration of synthetic MB solution (1-20 mg/L) and weight of GSC (5-20 g) were investigated. A remarkable change in color of synthetic MB solution from blue to crystal clear was observed at the end of adsorption study. High efficiency of the synthesized GSC for dye-contaminated wastewater treatment is concluded.
This study was conducted to investigate the potential application of oil palm empty fruit branches (OPEFB) as adsorbents to remove organic methylmercurry, MeHg(II), and inorganic Hg(II) from aqueous solution. The OPEFB was functionalized with amine containing ligand namely 3-ureidopropyltriethoxysilane (UPTES) aiming for better adsorption performance towards both mercury ions. The adsorption was found to be dependent on initial pH, initial concentraton, temperatures, and contact time. The maximum adsorption capacities (Qm.exp) of Hg(II) adsorption onto OPEFB and UPTES-OPEFB were 0.226 and 0.773 mmol/g, respectively. The Qm.exp of MeHg(II) onto OPEFB, however, was higher than UPTES-OPEFB. The adsorption kinetic data obeyed the Elovich model and the adsorption was controlled by the film-diffusion step. The calculated thermodynamic parameters indicate an endothermic adsorption process. Adsorption data analysis indicates that the adsorption mechanism may include ion-exchange, complexation, and physisorption interactions. The potential applications of adsorbents were demonstrated using oilfield produced water and natural gas condensate. The UPTES-OPEFB offered higher selectivity towards both mercury ions than OPEFB. The regenerability studies indicated that the adsorbent could be reused for multiple cycles.
The effects of dry biomass density in cryogel beads, shaking speed and initial concentration ratio of phenol to 4-chlorophenol (4-CP) on the bioregeneration efficiencies of binary phenol and 4-CP-loaded granular activated carbon (GAC) for phenol and 4-CP, respectively, were investigated under the simultaneous adsorption and biodegradation approach. The results revealed higher bioregeneration efficiencies of binary-loaded GAC for phenol and 4-CP at higher dry biomass density but moderate shaking speed. The optimum dry biomass density in cryogel beads and shaking speed for use in bioregeneration were found to be 0.01 g/mL and 250 rpm, respectively. With respect to the initial phenol to 4-CP concentration ratio, the bioregeneration efficiencies were lower under increasing phenol and 4-CP initial concentrations, respectively, with the effect being more conspicuous under increasing 4-CP concentration. Higher bioregeneration efficiencies were achieved with the use of immobilized rather than suspended biomasses.
Biochar is a stabilized, carbon-rich by-product derived from pyrolysis of biomass. Recently, biochar has received extensive attentions because of its multi-functionality for agricultural and environmental applications. Biochar can contribute to sequestration of atmosphere carbon, improvement of soils quality, and mitigation of environmental contaminations. The capability of biochar for specific application is determined by its properties which are predominantly controlled by source material and pyrolysis route variables. The biochar sorption potential is a function of its surface area, pores volume, ash contents, and functional groups. The impacts of each production factors on these characteristics of biochar need to be well-understood to design efficient biochars for pesticides removal. The effects of biomass type on biochar sorptive properties are determined by relative amounts of its lingo-cellulosic compounds, minerals content, particles size, and structure. The highest treatment temperature is the most effective pyrolysis factor in the determination of biochar sorption behavior. The expansion of micro-porosity and surface area and also increase of biochar organic carbon content and hydrophobicity mostly happen by pyrolysis peak temperature rise. These changes make biochar suitable for immobilization of organic contaminants. Heating rate, gas pressure, and reaction retention time after the pyrolysis temperatures are sequentially important pyrolysis variables effective on biochar sorptive properties. This review compiles the available knowledge about the impacts of production variables on biochars sorptive properties and discusses the aging process as the main factor in post-pyrolysis alterations of biochars sorption capacity. The drawbacks of biochar application in the environment are summarized as well in the last section.
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
The applications of polysulfides derived from natural plant oil and sulfur via the inverse vulcanization in the removal of heavy metals from aqueous solutions suffered from their low porosity and scarce surface functionality because of their hydrophobic surfaces and bulk characteristics. In this study, polysulfides from sulfur and palm oil (PSPs) with significantly enhanced porosity (13.7-24.1 m2/g) and surface oxygen-containing functional groups (6.9-8.6 wt.%) were synthesized with the optimization of process conditions including reaction time, temperature, and mass ratios of sulfur/palm oil/NaCl/sodium citrate. PSPs were applied as sorbents to remove heavy metals present in aqueous solutions. The integration of porosity and oxygen modification allowed a fast kinetic (4.0 h) and enhanced maximum sorption capacities for Pb(II) (218.5 mg/g), Cu(II) (74.8 mg/g), and Cr(III) (68.4 mg/g) at pH 5.0 and T 298 K comparing with polysulfides made without NaCl/sodium citrate. The sorption behaviors of Pb(II), Cu(II), and Cr(III) on PSPs were highly dependent on the solution pH values and ionic strength. The sorption presented excellent anti-interference capability for the coexisting cations and anions. The sorption processes were endothermic and spontaneous. This work would guide the preparation of porous polysulfides with surface modification as efficient sorbents to remediate heavy metals from aqueous solutions.
Sugar molasses from agricultural waste could be a sustainable carbon source for the synthesis of graphene adsorbent introduced in this work. The sugar molasses was successfully converted to graphene-like material and subsequently coated on the sand as graphene sand composite (GSC), as proven by XRD, XPS, Raman spectroscopy, and SEM with EDX mapping analyses. The adsorption performance of GSC was evaluated against the removal of Tetracycline (TC) and methylene blue (MB) pollutants from an aqueous solution in a fixed bed column continuous-flow adsorption setup. The effect of different process conditions: bed height (4-12 cm), influent flow rate (3-7 mL/min), and contaminants' concentration (50-150 ppm) was investigated. The results revealed that column performance was improved by increasing the bed depth and lowering the flow rate and concentration of the pollutants. The best removal efficiency was obtained when the bed height was 12 cm, the influent flow rate of 3 mL/min, and the pollutants' initial concentration was 50 mg/L. Thomas, Adams-Bohart, and Yoon-Nelson models were attempted to fit the breakthrough curves. Regeneration of the GSC indicated the decline of breakthrough time from 240-280 to 180 min, reflecting the decrease in adsorptive sites due to the incomplete regeneration process. Overall, sugar molasses was shown to be a low-cost precursor for synthesizing valuable graphene material in the form of GSC, which can reduce the problem for industrial waste management of sugar molasses, and the GSC could be used as an adsorbent for environmental application.
The adsorption of ammonium from water was studied on an activated carbon obtained using raw oil palm shell and activated with acetic acid. The performance of this adsorbent was tested at different operating conditions including the solution pH, adsorbent dosage, and initial ammonium concentration. Kinetic and equilibrium studies were carried out, and their results were analyzed with different models. For the adsorption kinetics, the pseudo-first order equation was the best model to correlate this system. Calculated adsorption rate constants ranged from 0.071 to 0.074 g/mg min. The ammonium removal was 70-80% at pH 6-8, and it was significantly affected by electrostatic interaction forces. Ammonium removal (%) increased with the adsorbent dosage, and neutral pH condition favored the adsorption of this pollutant. The best ammonium adsorption conditions were identified with a response surface methodology model where the maximum removal was 91.49% with 2.27 g/L of adsorbent at pH 8.11 for an initial ammonium concentration of 36.90 mg/L. The application of a physical monolayer model developed by statistical physics theory indicated that the removal mechanism of ammonium was multi-ionic and involved physical interactions with adsorption energy of 29 kJ/mol. This activated carbon treated with acetic acid is promising to depollute aqueous solutions containing ammonium.
Soil contamination by emerging pollutants tetrabromobisphenol A (TBBPA) and microplastics has become a global environmental issue in recent years. However, little is known about the effect of microplastics on degradation of TBBPA in soil, especially aged microplastics. In this study, the effect of aged polystyrene (PS) microplastics on the degradation of TBBPA in soil and the mechanisms were investigated. The results suggested that the aged microplastics exhibited a stronger inhibitory effect on the degradation of TBBPA in soil than the pristine microplastics, and the degradation efficiency of TBBPA decreased by 21.57% at the aged microplastic content of 1%. This might be related to the higher TBBPA adsorption capacity of aged microplastics compared to pristine microplastics. Aged microplastics strongly altered TBBPA-contaminated soil properties, reduced oxidoreductase activity and affected microbial community composition. The decrease in soil oxidoreductase activity and relative abundance of functional microorganisms (e.g., Bacillus, Pseudarthrobacter and Sphingomonas) caused by aged microplastics interfered with metabolic pathways of TBBPA. This study indicated the importance the risk assessment and soil remediation for TBBPA-contaminated soil with aged microplastics.
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 contemporary wastewater treatment industry, advanced oxidation techniques, membrane filtration, ion exchange, and reverse osmosis are used to treat chemically loaded wastewater. All these methods required highly toxic oxidizing chemicals, high capital investment in membrane/filter materials, and the installation of sophisticated equipment. Wastewater treatment through an adsorption process using biomass-based adsorbent is economical, user-friendly, and sustainable. Neem tree waste has been explored as an adsorbent for wastewater treatment. The chemical components in the neem biomass include carbohydrates, fat, fiber, cellulose, hemicellulose, and lignin, which support the functionalization of neem biomass. Moreover, adsorbent preparation from renewable resources is not only cost-effective and environmentally friendly but also helps in waste management for sustainable growth. Contemporary researchers explored the pre- and post-surface-modified neem biomass adsorbents in scavenging the pollutants from contaminated water. This review extensively explores the activation process of neem biomass, physical and chemical methods of surface modification mechanism, and the factors affecting surface modification. The pollutant removal through pre and post-surface-modified neem biomass adsorbents was also summarized. Furthermore, it also provides a comprehensive summary of the factors that affect the adsorption performance of the neem biomass-derived adsorbents against dyes, metal ions, and other emerging pollutants. Understanding the surface-modification mechanisms and the adsorption efficiency factor of adsorbents will help in harnessing their potential for more efficiently combatting environmental pollution and making strides toward a greener and more sustainable future.
A composite of chitosan biopolymer with microalgae and commercial carbon-doped titanium dioxide (kronos) was modified by grafting an aromatic aldehyde (salicylaldehyde) in a hydrothermal process for the removal of brilliant green (BG) dye. The resulting Schiff's base Chitosan-Microalgae-TiO2 kronos/Salicylaldehyde (CsMaTk/S) material was characterised using various analytical methods (conclusive of physical properties using BET surface analysis method, elemental analysis, FTIR, SEM-EDX, XRD, XPS and point of zero charge). Box Behnken Design was utilised for the optimisation of the three input variables, i.e., adsorbent dose, pH of the media and contact time. The optimum conditions appointed by the optimisation process were further affirmed by the desirability test and employed in the equilibrium studies in batch mode and the results exhibited a better fit towards the pseudo-second-order kinetic model as well as Freundlich and Langmuir isotherm models, with a maximum adsorption capacity of 957.0 mg/g. Furthermore, the reusability study displayed the adsorptive performance of CsMaTk/S remains effective throughout five adsorption cycles. The possible interactions between the dye molecules and the surface of the adsorbent were derived based on the analyses performed and the electrostatic attractions, H-bonding, Yoshida-H bonding, π-π and n-π interactions are concluded to be the responsible forces in this adsorption process.