Amending polycyclic aromatic hydrocarbon (PAH)-contaminated soils with biochar may be cheaper and environmentally friendly than other forms of organic materials. This has led to numerous studies on the use of biochar to either bind or stimulate the microbial degradation of organic compounds in soils. However, very little or no attention have been paid to the fact that biochars can give simultaneous impact on PAH fate processes, such as volatilization, sorption and biodegradation. In this review, we raised and considered the following questions: How does biochar affect microbes and microbial activities in the soil? What are the effects of adding biochar on sorption of PAHs? What are the effects of adding biochar on degradation of PAHs? What are the factors that we can manipulate in the laboratory to enhance the capability of biochars to degrade PAHs? A triphasic concept of how biochar can give simultaneous impact on PAH fate processes in soils was proposed, which involves rapid PAH sorption into biochar, subsequent desorption and modification of soil physicochemical properties by biochar, which in turn stimulates microbial degradation of the desorbed PAHs. It is anticipated that biochar can give simultaneous impact on PAH fate processes in soils.
The occurrence and fate of antibiotic compounds in water can adversely affect human and animal health; hence, the removal of such substrates from soil and water is indispensable. Herein, we described the synthesis method of mesoporous carbon (MPC) via the pyrolysis route from a coordination polymer Fe-based MIL-53 (or MIL-53, shortly). The MPC structure was analyzed by several physical techniques such as SEM, TEM, BET, FT-IR, VSM, and XRD. The response surface methodology (RSM) was applied to find out the effects of initial concentration, MPC dosage, and pH on the removal efficiency of trimethoprim (TMP) and sulfamethoxazole (SMX) antibiotics in water. Under the optimized conditions, the removal efficiencies of TMP and SMX were found to be 87% and 99%, respectively. Moreover, the adsorption kinetic and isotherm studies showed that chemisorption and the monolayer adsorption controlled the adsorption process. The leaching test and recyclability studies indicated that the MPC structure was stable and can be reused for at least four times without any considerable change in the removal efficiency. Plausible adsorption mechanisms were also addressed in this study. Because of high maximum adsorption capacity (85.5 mg/g and 131.6 mg/g for TMP and SMX, respectively) and efficient reusability, MPC is recommended to be a potential adsorbent for TMP and SMX from water media.
Several parts of the world have been facing the problem of nitrite and nitrate contamination in ground and surface water. The acute toxicity of nitrite has been shown to be 10-fold higher than that of nitrate. In the present study, aminated silica carbon nanotube (ASCNT) was synthesised and tested for nitrite removal. The synergistic effects rendered by both amine and silica in ASCNT have significantly improved the nitrite removal efficiency. The IEP increased from 2.91 for pristine carbon nanotube (CNT) to 8.15 for ASCNT, and the surface area also increased from 178.86 to 548.21 m2 g-1. These properties have promoted ASCNT a novel adsorbent to remove nitrite. At optimum conditions of 700 ppm of nitrite concentration at pH 7 and 5 h of contact with 15 mg of adsorbent, the ASCNT achieved the maximal loading capacity of 396 mg/g (85% nitrite removal). The removal data of nitrite onto ASCNT fitted the Langmuir isotherm model better than the Freundlich isotherm model with the highest regression value of 0.98415, and also, the nonlinear analysis of kinetics data showed that the removal of nitrite followed pseudo-second-order kinetic. The positive values of both ΔS° and ΔH° suggested an endothermic reaction and an increase in randomness at the solid-liquid interface. The negative ΔG° values indicated a spontaneous adsorption process. The ASCNT was characterised using FESEM-EDX and FTIR, and the results obtained confirmed the removal of nitrite. Based on the findings, ASCNT can be considered as a novel and promising candidate for the removal of nitrite ions from wastewater.
A novel porous coordination polymer adsorbent (BTCA-P-Cu-CP) based on a piperazine(P) as a ligand and 1,2,4,5-benzenetetracarboxylic acid (BTCA) as a linker was synthesized and magnetized to form magnetic porous coordination polymer (BTCA-P-Cu-MCP). Fourier transform infrared (FTIR), X-ray diffraction (XRD), vibrating sample magnetometer (VSM), field emission scanning electron microscope(FESEM), energy-dispersive X-ray spectroscopy(EDS), CHN, and Brunauer-Emmett-Teller(BET) analysis were used to characterize the synthesized adsorbent. BTCA-P-Cu-MCP was used for removal and preconcentration of Pb(II) ions from environmental water samples prior to flame atomic absorption spectrometry(FAAS) analysis. The maximum adsorption capacity of BTCA-P-Cu-MCP was 582 mg g-1. Adsorption isotherm, kinetic, and thermodynamic parameters were investigated for Pb(II) ions adsorption. Magnetic solid phase extraction (MSPE) method was used for preconcentration of Pb(II) ions and the parameters influencing the preconcentration process have been examined. The linearity range of proposed method was 0.1-100 μg L-1 with a preconcentration factor of 100. The limits of detection and limits of quantification for lead were 0.03 μg L-1 and 0.11 μg L-1, respectively. The intra-day (n = 7) and inter-day (n = 3) relative standard deviations (RSDs) were 1.54 and 3.43% respectively. The recoveries from 94.75 ± 4 to 100.93 ± 1.9% were obtained for rapid extraction of trace levels of Pb(II) ions in different water samples. The results showed that the BTCA-P-Cu-MCP was steady and effective adsorbent for the decontamination and preconcentration of lead ions from the aqueous environment.
The pollution of water resources due to the disposal of industrial wastes that have organic material like phenol is causing worldwide concern because of their toxicity towards aquatic life, human beings and the environment. Phenol causes nervous system damage, renal kidney disease, mental retardation, cancer and anaemia. In this study, magnetic palm kernel biochar is used for removal of phenol from wastewater. The effect of parameters such as pH, agitation speed, contact time and magnetic biochar dosage are validated using design of experiments. The statistical analysis reveals that the optimum conditions for the highest removal (93.39%) of phenol are obtained at pH of 8, magnetic biochar dosage of 0.6 g, agitation speed at 180 rpm and time of 60 min with the initial concentration of 10 mg/L. The maximum adsorption capacities of phenol were found to be 10.84 mg/g and Langmuir and Freundlich isotherm models match the experimental data very well and adsorption kinetic obeys a pseudo-second order. Hence, magnetic palm kernel can be a potential candidate for phenol removal from wastewater.
A relationship is proposed for the interfacial partitioning of protein in poly(ethylene glycol) (PEG)-phosphate aqueous two-phase system (ATPS). The relationship relates the natural logarithm of interfacial partition coefficient, ln G to the PEG concentration difference between the top and bottom phases, Δ[PEG], with the equation ln G=AΔ[PEG]+B. Results showed that this relationship provides good fits to the partition of bovine serum albumin (BSA) in ATPS which is comprised of phosphate and PEG of four different molecular weight 1450g/mol, 2000g/mol, 3350g/mol and 4000g/mol, with the tie-line length (TLL) in the range of 44-60% (w/w) at pH 7.0. The decrease of A values with the increase of PEG molecular weight indicates that the correlation between ln G and Δ[PEG] decreases with the increase in PEG molecular weight and the presence of protein-polymer hydrophobic interaction. When temperature was increased, a non-linear relationship of ln G inversely proportional to temperature was observed. The amount of proteins adsorbed at the interface increased proportionally with the amount of BSA loaded whereas the partition coefficient, K remained relatively constant. The relationship proposed could be applied to elucidate interfacial partitioning behaviour of other biomolecules in polymer-salt ATPS.
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.
Proper remediation of aquatic environments contaminated by toxic organic dyes has become a research focus globally for environmental and chemical engineers. This study evaluates the adsorption potential of a polymer-based adsorbent, thiourea-modified poly(acrylonitrile-co-acrylic acid) (T-PAA) adsorbent, for the simultaneous uptake of malachite green (MG) and methylene blue (MB) dye ions from binary system in a continuous flow adsorption column. The influence of inlet dye concentrations, pH, flow rate, and adsorbent bed depth on adsorption process were investigated, and the breakthrough curves obtained experimentally. Results revealed that the sorption capacity of the T-PAA for MG and MB increase at high pH, concentration and bed-depth. Thomas, Bohart-Adams, and Yoon-Nelson models constants were calculated to describe MG and MB adsorption. It was found that the three dynamic models perfectly simulate the adsorption rate and behavior of cationic dyes entrapment. Finally, T-PAA adsorbent demonstrated good cyclic stability. It can be regenerated seven times (or cycles) with no significant loss in adsorption potential. Overall, the excellent sorption capacity and multiple usage make T-PAA polymer an attractive adsorbent materials for treatment of multicomponent dye bearing effluent in a fixed-bed column system.
The response of trilayer graphene nanoribbon (TGN)-based ion-sensitive field-effect transistor (ISFET) to different pH solutions and adsorption effect on the sensing parameters are analytically studied in this research. The authors propose a TGN-based sensor to electrochemically detect pH. To this end, absorption effect on the sensing area in the form of carrier concentration, carrier velocity, and conductance variations are investigated. Also, the caused electrical response on TGN as a detection element is analytically proposed, in which significant current decrease of the sensor is observed after exposure to high pH values. In order to verify the accuracy of the model, it is compared with recent reports on pH sensors. The TGN-based pH sensor exposes higher current compared to that of carbon nanotube (CNT) counterpart for analogous ambient conditions. While, the comparative results demonstrate that the conductance of proposed model is lower than that of monolayer graphene-counterpart for equivalent pH values. The results confirm that the conductance of the sensor is decreased and Vg-min is obviously right-shifted by increasing value of pH. The authors demonstrate that although there is not the experimental evidence reported in the part of literature for TGN sensor, but the model can assist in comprehending experiments involving nanoscale pH sensors.
In the present work, a single-step purification of recombinant nucleocapsid protein (NP) of the Newcastle disease virus (NDV) directly from unclarified feedstock using an expanded bed adsorption chromatography (EBAC) was developed. Streamline 25 column (ID = 25 mm) was used as a contactor and Streamline chelating adsorbent immobilized with Ni2+ ion was used as affinity adsorbent. The dynamic binding capacity of Ni2+ -loaded Streamline chelating adsorbent for the NP protein in unclarified feedstock was found to be 2.94 mg ml(-1) adsorbent at a superficial velocity of 200 cm h(-1). The direct purification of NP protein from unclarified feedstock using expanded bed adsorption has resulted in a 31% adsorption and 9.6% recovery of NP protein. The purity of the NP protein recovered was about 70% and the volume of processing fluid was reduced by a factor of 10. The results of the present study show that the IMA-EBAC developed could be used to combine the clarification, concentration and initial purification steps into a single-step operation.
The urgent need to address the severe environmental risk posed by chromium-contaminated industrial wastewater necessitates the development of eco-friendly cleanup methodologies. Utilizing the Ficus benghalensis plant extracts, the present study aims to develop green zinc oxide nanoparticles for the removal of Cr metal ions from wastewater. The leaves of Ficus benghalensis, often known as the banyan tree, were used to extract a solution for synthesizing ZnO NPs. These nanoparticles were developed with the goal of efficiently eliminating chromium (Cr) from industrial effluents. Batch studies were carried out to assess the efficiency of these synthesized ZnO NPs in treating leather industrial effluent, with aiming for optimal chromium removal. This involved measuring the nanoparticles' capacity to adsorb Cr ions from wastewater samples by comparing chromium levels before and after treatment. Removal efficiency for Cr was estimated through the batches such as optimization of pH, contact time, initial Cr concentration and sorbent dose of ZnO NPs were of the batches. These synthesized ZnO NPs were found to be successful in lowering chromium levels in wastewater to meet permissible limit. The nanoparticles exhibited their highest absorption capacity, reaching 94 % (46 mg/g) at pH 4, with a contact time of 7 hours with the optimum sorbent dose of 0.6 g/L. Hence, the excellent adsorption capabilities of these nanoparticles, together with their environmentally benign manufacturing technique, provide a long-term and efficient solution for chromium-contaminated wastewater treatment. Its novel nature has the potential to significantly improve the safety and cleanliness of water ecosystems, protecting the both i.e. human health and the environment.
Polyethylene glycol functionalized with oxygenated multi-walled carbon nanotubes (O-PEG-MWCNTs) as an efficient nanomaterial for the in vitro adsorption/release of curcumin (CUR) anticancer agent. The synthesized material was morphologically characterized using scanning electron microscopy, Fourier transform infrared spectroscopy and transmission electron microscopy. In addition, the CUR adsorption process was assessed with kinetic and isotherm models fitting well with pseudo-second order and Langmuir isotherms. The results showed that the proposed O-PEG-MWCNTs has a high adsorption capacity for CUR (2.0 × 103 mg/g) based on the Langmuir model. The in vitro release of CUR from O-PEG-MWCNTs was studied in simulating human body fluids with different pHs (ABS pH 5, intestinal fluid pH 6.6 and body fluid pH 7.4). Lastly, to confirm the success compliance of the O-PEG-MWCNT nanocomposite as a drug delivery system, the parameters affecting the CUR release such as temperature and PEG content were investigated. As a result, the proposed nanocomposite could be used as an efficient carrier for CUR delivery with an enhanced prolonged release property. Graphical Abstract ᅟ.
Extensive use of organophosphorus pesticides in agriculture leads to adverse effects to the environment and human health. Sample preparation is compulsory to enrich target analytes prior to detection as they often exist at trace levels and this step is critical as it determines the concentration of pollutants present in samples. The selection of a suitable extraction method is of great importance. The analytical performance of the extraction methods is influenced by the selection of sorbents as sorbents play a vital role in the sensitivity and selectivity of an analytical method. To date, numerous sorbent materials have been developed to cater to the needs of selective and sensitive pesticides' detection. Comprehensive details pertaining to extraction methods, developed sorbents, and analytical performance are provided. This review intended to provide a general overview on different extraction techniques and sorbents that have been developed in the last 10 years for organophosphorus pesticides' determinations in food and water samples.
Herein, this work targets to employ the blended fruit wastes including rambutan (Nephelium lappaceum) peel and durian (Durio zibethinus) seed as a promising precursor to produce activated carbon (RPDSAC). The generation of RPDSAC was accomplished through a rapid and practical procedure (microwave-ZnCl2 activation). To evaluate the adsorptive capabilities of RPDSAC, its efficacy in eliminating methylene blue (MB), a simulated cationic dye, was measured. The Box-Behnken design (BBD) was utilized to optimize the crucial adsorption parameters, namely A: RPDSAC dose (0.02-01 g/100 mL), B: pH (4-10), and C: time (2-6 min). The BBD design determined that the highest level of MB removal (79.4%) was achieved with the condition dosage of RPDSAC at 0.1 g/100 mL, contact time (6 min), and pH (10). The adsorption isotherm data is consistent with the Freundlich concept, and the pseudo-second-order versions adequately describe the kinetic data. The monolayer adsorption capacity (qmax) of RPDSAC reached 120.4 mg/g at 25 °C. Various adsorption mechanisms are involved in the adsorption of MB dye onto the surface of RPDSAC, including π-π stacking, H-bonding, pore filling, and electrostatic forces. This study exhibits the potential of the RPDSAC as an adsorbent for removal of toxic cationic dye (MB) from contaminated 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.