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.
The removal of four parabens, methyl-, ethyl-, propyl-, and benzyl-paraben, by β-cyclodextrin (β-CD) polymer from aqueous solution was studied. Different β-CD polymers were prepared by using two cross-linkers, i.e., hexamethylene diisocyanate (HMDI) and toluene-2,6-diisocyanate (TDI), with various molar ratios of cross-linker. β-CD-HMDI polymer with molar ratio of 1:7 and β-CD-TDI polymer with ratio 1:4 gave the highest adsorption of parabens among the β-CD-HMDI and β-CD-TDI series, and were subsequently used for further studies. The adsorption capacity of β-CD-HMDI is 0.0305, 0.0376, 0.1854 and 0.3026 mmol/g for methyl-, ethyl-, propyl-, and benzyl-paraben, respectively. β-CD-TDI have higher adsorption capacities compared with β-CD-HMDI, the adsorption capacity are 0.1019, 0.1286, 0.2551, and 0.3699 mmol/g methyl-, ethyl-, propyl-, and benzyl-paraben respectively. The parameters studied were adsorption capacity, water retention, and reusability. Role of both cross-linker in adsorption, hydrophobicity of polymers, and adsorption capacity of different parabens were compared and discussed. All experiments were conducted in batch adsorption technique. These polymers were applied to real samples and showed positive results.
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.
Industrial and urban modernization processes generate significant amounts of heavy metal wastewater, which brings great harm to human production and health. The biotechnology developed in recent years has gained increasing attention in the field of wastewater treatment due to its repeatable regeneration and lack of secondary pollutants. Pseudomonas, being among the several bacterial biosorbents, possesses notable benefits in the removal of heavy metals. These advantages encompass its extensive adsorption capacity, broad adaptability, capacity for biotransformation, potential for genetic engineering transformation, cost-effectiveness, and environmentally sustainable nature. The process of bacterial adsorption is a complex phenomenon involving several physical and chemical processes, including adsorption, ion exchange, and surface and contact phenomena. A comprehensive investigation of parameters is necessary in order to develop a mathematical model that effectively measures metal ion recovery and process performance. The aim of this study was to explore the latest advancements in high-tolerance Pseudomonas isolated from natural environments and evaluate its potential as a biological adsorbent. The study investigated the adsorption process of this bacterium, examining key factors such as strain type, contact time, initial metal concentration, and pH that influenced its effectiveness. By utilizing dynamic mathematical models, the research summarized the biosorption process, including adsorption kinetics, equilibrium, and thermodynamics. The findings indicated that Pseudomonas can effectively purify water contaminated with heavy metals and future research will aim to enhance its adsorption performance and expand its application scope for broader environmental purification purposes.
Hybrid material of surgical mask activated carbon (SMAC) and Fe2O3 (SMAC-Fe2O3) composite was prepared by simple co-precipitation method and used as potential material for the remediation of 2,4-dicholrophenol (2,4-DCP). The XRD patterns exhibited the presence of SMAC and Fe2O3, FTIR spectrum showed the FeO-carbon stretching at the wavenumber from 400 to 550 cm-1. UV-Vis DRS results showed the band gap was 1.97 eV and 2.05 eV for SMAC-Fe2O3 and Fe2O3, respectively. The SEM images revealed that the Fe2O3 doped onto the fiber morphology of SMAC. The outcomes of the BET examination exhibited a surface area of 195 m2/g and a pore volume of 0.2062 cm3/g for the SMAC/Fe2O3 composite. The batch mode study shows the maximum adsorption and photocatalytic degradation efficacies which were 97% and 78%, respectively. The experimental data was studied with both linear and nonlinear adsorption isotherm and kinetics models. The nonlinear Langmuir isotherm and pseudo-second-order kinetics (PSOK) models have well fit compared with other models. The Langmuir maximum adsorption capacity (qmax) was found 161.60 mg/g. Thermodynamic analysis shows that the 2,4-DCP adsorption onto SMAC-Fe2O3 was a spontaneous and exothermic process. The PSOK assumes that the adsorption process was chemisorption. The photocatalytic degradation rate constant of 2,4-DCP was calculated using pseudo-first-order kinetics (PFOK) and the rate constant for SMAC-Fe2O3 and Fe2O3 were 0.859 × 10-2 min-1 and 0.616 × 10-2 min-1, correspondingly. In addition, the obtained composite exhibited good reusability after a few cycles. These results confirmed that SMAC-Fe2O3 composite is an effective adsorbent and photocatalyst for removing 2,4-DCP pollutants.
Adsorption is one of the most efficient methods for remediating industrial recalcitrant wastewater due to its simple design and low investment cost. However, the conventional adsorbents used in adsorption have several limitations, including high cost, low removal rates, secondary waste generation, and low regeneration ability. Hence, the focus of the research has shifted to developing alternative low-cost green adsorbents from renewable resources such as biomass. In this regard, the recent progress in the modification of biomass-derived adsorbents, which are rich in cellulosic content, through a variety of techniques, including chemical, physical, and thermal processes, has been critically reviewed in this paper. In addition, the practical applications of raw and modified biomass-based adsorbents for the treatment of industrial wastewater are discussed extensively. In a nutshell, the adsorption mechanism, particularly for real wastewater, and the effects of various modifications on biomass-based adsorbents have yet to be thoroughly studied, despite the extensive research efforts devoted to their innovation. Therefore, this review provides insight into future research needed in wastewater treatment utilizing biomass-based adsorbents, as well as the possibility of commercializing biomass-based adsorbents into viable products.
Excessive use of tetracycline (TC) is alarming owing to its increased detection in water systems. In this study, a photocatalyst was developed to degrade TC using a Ce-N-co-doped AC/TiO2 photocatalyst, denoted as Ce/N-AC/TiO2, prepared using the sol-gel method assisted by microwave radiation, speeding up the synthesis process. Ce/N-AC/TiO2 achieved maximum TC degradation of 93.1% under UV light with optimum sorption system conditions of an initial concentration of 10 mg L-1, pH 7, and 30 ℃, under 120 min. Scavenger experiments revealed that holes and superoxide radicals were the active species influencing the photodegradation process. The TC degradation was appropriately fitted with Langmuir isotherms and a pseudo-second-order (PSO) kinetic model. The change in enthalpy (ΔH) (2.43 kJ mol-1), entropy (ΔS) (0.024 kJ mol-1), and Gibbs free energy (ΔG) (- 4.941 to - 5.802 kJ mol-1) suggested that the adsorption process was spontaneous, favourable, and endothermic. Electrostatic interaction, hydrogen bonding, pore-filling, cationic-π, n-π, and π-π interaction were among the interactions involved between TC and Ce/N-AC/TiO2. Furthermore, Ce/N-AC/TiO2 stability was confirmed through 80% removal efficiency even after the fifth reuse cycle. Notably, this work provides new insight into the production of efficient, reusable, and enhanced photocatalysts using a rapid and cost-effective microwave-assisted synthesis process for pollutant remediation.
As the world faces the brink of climatological disaster, it is crucial to utilize all available resources to facilitate environmental remediation, especially by accommodating waste streams. Lignocellulosic waste residues can be transformed into mesoporous biochar structures with substantial pore capacity. While biochars are considered a method of carbon dioxide removal (CDR), they are in fact an environmental double-edged sword that can be used to extract metal ions from water bodies. Biochars possess high chemical affinities through chemisorption pathways that are tuneable to specific pH conditions. This work demonstrates how biochars can be enhanced to maximise their surface area and porosity for the removal of Cu (II) in solution. It was found that bagasse derived mesoporous biochars operate preferentially at high pH (basic conditions), with the 1.18 mKOH/mSCB material reaching 97.85% Cu (II) removal in 5 min. This result is in stark contrast with the majority of biochar adsorbents that are only effective at low pH (acidic conditions). As a result, the biochars produced in this work can be directly applied to ancestral landfill sites and carbonate-rich mine waters which are highly basic by nature, preventing further metal infiltration and reverse sullied water supplies. Furthermore, to assess the value in the use of biochars produced and applied in this way, a techno-economic assessment was carried out to determine the true cost of biochar synthesis, with possible routes for revenue post-Cu being removed from the biochar.
The long-term presence of pharmaceutical pollution in water bodies has raised public awareness. Nanocellulose is often used in adsorption to remove pollutants from wastewater since it is an abundant, green and sustainable material. This paper offers an extensive overview of the recent works reporting the potential of nanocellulose-based adsorbents to treat pharmaceutical wastewater. This study distinguishes itself by not only summarizing recent research findings but also critically integrating discussions on the improvements in nanocellulose production and sorts of alterations based on the type of pharmaceutical contaminants. Commonly, charged, or hydrophobic characteristics are introduced onto nanocellulose surfaces to accelerate and enhance the removal of pharmaceutical compounds. Although adsorbents based on nanocellulose have considerable potential, several significant challenges impede their practical application, particularly concerning cost and scalability. Large-scale synthesis of nanocellulose is technically challenging and expensive, which prevents its widespread use in wastewater treatment plants. Continued innovation in this area could lead to breakthroughs in the practical application of nanocellulose as a superior adsorbent. The prospects of utilization of nanocellulose are explained, providing a sustainable way to address the existing restriction and maximize the application of the modified nanocellulose in the field of pharmaceutical pollutants removal.
The quest for a good life, urbanization, and industrialization have led to the widespread distribution of endocrine-disrupting chemicals (EDCs) in water bodies through anthropogenic activities. This poses an imminent threat to both human and environmental health. In recent years, the utilization of advance materials for the removal of EDCs from wastewater has attracted a lot of attention. Metal-oxide nanocatalysts have emerged as promising candidates due to their high surface area, reactivity, and tunable properties, as well as enhanced surface properties such as mesoporous structures and hierarchical morphologies that allow for increased adsorption capacity, improved photocatalytic activity, and enhanced selectivity towards specific EDCs. As a result, they have shown extraordinary efficacy in removing a wide range of EDCs from aqueous solutions, including pharmaceuticals, agrochemicals, personal care items, and industrial chemicals. This study give insight into the unique physicochemical characteristics of metal-oxide nanocatalysts to effectively and efficiently remove harmful EDCs from wastewater. It also discussed the advances in the synthesis, and properties of metal-oxide nanocatalysts, and insight into understanding the fundamental mechanisms underlying the adsorption and degradation of EDCs on metal-oxide nanocatalysts using advanced characterization techniques such as spectroscopic analysis and electron microscopy. The findings of the study present metal-oxide nanocatalysts as a good candidate for the spontaneous sequestration of EDCs from wastewater is an intriguing approach to mitigating water pollution and safeguarding public health and the environment.
This study highlights the biosorption capacity for Cd (II), Cu (II) and Pb (II) by a locally isolated Pseudomonas aeruginosa DR7. At initial concentrations of 150 mg L-1 and 240 min of contact time, P. aeruginosa DR7 showed a 62.56 mg/g removal capacity for Cd (II) at an optimum pH of 6.0, 72.49 mg/g for Cu (II) at an optimum pH of 6.0, and 94.2 mg/g for Pb (II) at an optimum pH of 7.0. The experimental data of Cd (II), Cu (II), and Pb (II) adsorbed by the pseudo-second-order kinetic model correlates well with P. aeruginosa DR7, with R2 all above 0.99, showing that the fitting effect was satisfactory. The isothermal adsorption processes of Cd (II) (0.980) and Cu (II) (0.986) were more consistent with the Freundlich model, whereas Pb (II) was more consistent with the Langmuir model (0.978). FTIR analysis suggested the involvement of hydroxyl, carbonyl, carboxyl, and amine groups present in the inner regions of P. aeruginosa cells during the biosorption process. SEM-EDS analysis revealed that after contact with metals, there were slight changes in the surface appearance of the cells, which confirmed the deposition of metals on the bacterial surface. There was also the possibility of the metals being translocated into the bacterial inner regions by the appearance of electron-dense particles, as observed using TEM. As a conclusion, the removal of metals from solutions using P. aeruginosa DR7 was a plausible alternative as a safe, cheap, and easily used biosorbent.
Microwave heating was used in the regeneration of methylene blue-loaded activated carbons produced from fibers (PFAC), empty fruit bunches (EFBAC) and shell (PSAC) of oil palm. The dye-loaded carbons were treated in a modified conventional microwave oven operated at 2450 MHz and irradiation time of 2, 3 and 5 min. The virgin properties of the origin and regenerated activated carbons were characterized by pore structural analysis and nitrogen adsorption isotherm. The surface chemistry was examined by zeta potential measurement and determination of surface acidity/basicity, while the adsorptive property was quantified using methylene blue (MB). Microwave irradiation preserved the pore structure, original active sites and adsorption capacity of the regenerated activated carbons. The carbon yield and the monolayer adsorption capacities for MB were maintained at 68.35-82.84% and 154.65-195.22 mg/g, even after five adsorption-regeneration cycles. The findings revealed the potential of microwave heating for regeneration of spent activated carbons.
Various species of local wood modified with N-(3-chloro-2-hydroxypropyl)-trimethylammonium chloride showed sorption enhancement for hydrolyzed Reactive Blue 2 (HRB) compared to the untreated samples. The enthalpy of sorption of HRB on Simpoh (Dillenia suffruticosa) was found to be endothermic. Maximum sorption capacity calculated from the Langmuir isotherm was 250.0 mg/g. Under continuous flow conditions HRB could be successfully removed. Dye removal was a function of bed depth and flow rate. However, the bed depth service time model of Bohart and Adams was not applicable in the HRB-quaternized wood system. The modified wood was applied to a sample of industrial textile effluent, and it was found to be able to remove the color successfully under batch conditions.
Electrospinning technology was applied for the preparation of polyacrylonitrile (PAN) nanofiber membrane in this work. After hot pressing, alkaline hydrolysis and neutralization treatment, a weak acid cation exchange membrane (P-COOH) was prepared. By the covalent coupling reaction between the acidic membrane and aminomethane sulfonic acid (AMSA), a strong acidic nanofiber membrane (P-SO3H) was obtained. The surface morphology, chemical structure, and thermal stability of the prepared ion exchange membranes were analyzed via SEM, FTIR and TGA. Analytical results showed that the membranes were prepared successfully and thermally stable. The ion exchange membrane (IEX) was conducted with the newly designed membrane reactor, and different operating conditions affecting the adsorption efficiency of Toluidine Blue dye (TBO) were investigated by dynamic flow process. The results showed that dynamic binding capacity (DBC) of weak and strong IEX membranes for TBO dye was ~170 mg/g in a dynamic flow process. Simultaneously, the ion exchange membranes were also used for purifying lysozyme from chicken egg white (CEW). Results illustrated that the recovery yield and purification factor of lysozyme were 93.43% and 29.23 times (P-COOH); 90.72% and 36.22 times (P-SO3H), respectively. It was revealed that two type ion exchange membranes were very suitable as an adsorber for use in dye waste treatment and lysozyme purification process. P-SO3H strong ion-exchange membrane was more effective either removal of TBO dye or purification of lysozyme. The ion exchange membranes not only effectively purified lysozyme from CEW solution, but also effectively removed dye from wastewater.
In this study, the potential for carbonaceous nanomaterials to be used as adsorbents for the mixed matrix membrane (MMM) microextraction and preconcentration of organic pollutants was demonstrated. For this method, multiwall carbon nanotubes (MWCNT) and single layer graphene (SLG) nanoparticles were individually incorporated through dispersion in a cellulose triacetate (CTA) polymer matrix to form a MWCNT-MMM and SLG-MMM, respectively. The prepared membranes were evaluated for the extraction of selected polycyclic aromatic hydrocarbons (PAHs) present in sewage pond water samples. The extraction was performed by dipping a small piece of membrane (7 mm × 7 mm) in a stirred 7.5 mL sample solution to initiate the analyte adsorption. This step was followed by an analyte desorption into 60 μL of methanol prior to high performance liquid chromatography (HPLC) analysis. When the optimum SLG-MMM microextraction technique was applied to spiked sewage pond water samples, the detection limit of the method for the PAHs were in the range of 0.02-0.09 ng/mL, with relative standard deviations of between 1.4% and 7.8%. Enrichment factors of 54-100 were achieved with relative recoveries of 99%-101%. A comparison was also made between the proposed approach and standard solid phase extraction using polymeric bonded octadecyl (C18) cartridges.
This study describes the synthesis, characterization and application of a new chrysin-based silica core-shell magnetic nanoparticles (Fe3O4@SiO2-N-chrysin) as an adsorbent for the preconcentration of Cu(II) from aqueous environment. The morphology, thermal stability and magnetic property of Fe3O4@SiO2-N-chrysin were analyzed using FTIR, FESEM, TEM, XRD, thermal analysis and VSM. The extraction efficiency of Fe3O4@SiO2-N-chrysin was analyzed using the batch wise method with flame atomic absorption spectrometry. Parameters such as the pH, the sample volume, the adsorption-desorption time, the concentration of the desorption solvent, the desorption volume, the interference effects and the regeneration of the adsorbent were optimized. It was determined that Cu(II) adsorption is highly pH-dependent, and a high recovery (98%) was achieved at a pH 6. The limit of detection (S/N=3), the limit of quantification (S/N=10), the preconcentration factor and the relative standard deviation for Cu(II) extraction were 0.3 ng mL(-1), 1 ng mL(-1), 100 and 1.9% (concentration=30 ng mL(-1), n=7), respectively. Excellent relative recoveries of 97-104% (%RSD<3.12) were achieved from samples from a spiked river, a lake and tap water. The MSPE method was also validated using certified reference materials SLRS-5 with good recovery (92.53%).