Solubility data of recalcitrant contaminants in cosolvents is essential to determine their potential applications in enhanced soil remediation. The solubilities of phenanthrene, anthracene, fluoranthene and benzo[a]pyrene in ethyl lactate/water and ethanol/water mixtures were measured using equilibrium techniques. The cosolvency powers derived from solubility data were then applied to the model developed from the solvophobic approach to predict the capability of ethyl lactate and ethanol in enhancing the desorption of contaminants from soils. Both ethyl lactate and ethanol cosolvents were shown to be able to enhance the solubilisation of the tested four polycyclic aromatic hydrocarbons by > 4 orders of magnitude above the levels obtained with water alone. However, ethyl lactate demonstrated a greater capacity to enhance PAH solubility than ethanol. The cosolvency powers of ethyl lactate/water system obtained from the end-to-end slope (sigma) and the end-to-half slope (sigma0.5) of the solubilisation curve were 1.0-1.5 and 2.0-2.9 higher than ethanol/water system respectively. In line with this, ethyl lactate/water was demonstrated to enhance the desorption of contaminants from soil by 20%-37% and 18%-61% higher compared to ethanol/water system in low organic content and high organic content soils respectively, with a 2:1 (V/W) ratio of solution:soil and with cosolvent fraction as low as 0.4. With the exception of benzo[a]pyrene, the experimental desorption results agreed fairly with the predicted values, under an applied solution:soil ratio that was enough to hold the capacity of released contaminants.
Acetaminophen (Ace) is a trace pollutant widely found in sewage treatment plant (STP) wastewater. We test the feasibility of coconut shell waste, a low cost adsorbent from coconut industry, for removing Ace from synthetic solution in a fixed-bed column adsorption. To enhance its performance, the surface of granular activated carbon (GAC) was pre-treated with NaOH, HNO3, ozone, and/or chitosan respectively. The results show that the chemical modification of the GAC's surface with various chemicals has enhanced its Ace removal during the column operations. Among the modified adsorbents, the ozone-treated GAC stands out for the highest Ace adsorption capacity (38.2 mg/g) under the following conditions: 40 mg/L of Ace concentration, 2 mL/min of flow rate, 45 cm of bed depth. Both the Thomas and the Yoon-Nelson models are applicable to simulate the experimental results of the column operations with their adsorption capacities: ozone-treated GAC (20.88 mg/g) > chitosan-coated GAC (16.67 mg/g) > HNO3-treated GAC (11.09 mg/g) > NaOH-treated GAC (7.57 mg/g) > as-received GAC (2.84 mg/g). This suggests that the ozone-treated GAC is promising and suitable for Ace removal in a fixed-bed reactor.
White tea contains the highest flavonoids compared to other teas. While there have been numerous studies on the components of different tea varieties, research explicitly focusing on the flavonoid content of white tea remains scarce, making the need for a good flavonoid purification process for white tea even more important. This study compared the adsorption and desorption performance of five types of macroporous resins: D101, HP20, HPD500, DM301, and AB-8. Among the tested resins, AB-8 was selected based on its best adsorption and desorption performance to investigate the static adsorption kinetics and dynamic adsorption-desorption purification of white tea flavonoids. The optimal purification process was determined: adsorption temperature 25 °C, crude tea flavonoid extract pH 3, ethanol concentration 80 %, sample loading flow rate and eluent flow rate 1.5 BV/min, and eluent dosage 40 BV. The results indicated that the adsorption process followed pseudo-second-order kinetics. Under the above purification conditions, the purity of the total flavonoids in the purified white tea flavonoid increased from approximately 17.69 to 46.23 %, achieving a 2.61-fold improvement, indicating good purification results. The purified white tea flavonoid can be further used for nutraceutical and pharmaceutical applications.
Metallic transition metal dichalcogenides (TMDs)1-8 are good catalysts for the hydrogen evolution reaction (HER). The overpotential and Tafel slope values of metallic phases and edges9 of two-dimensional (2D) TMDs approach those of Pt. However, the overall current density of 2D TMD catalysts remains orders of magnitude lower (~10-100 mA cm-2) than industrial Pt and Ir electrolysers (>1,000 mA cm-2)10,11. Here, we report the synthesis of the metallic 2H phase of niobium disulfide with additional niobium (2H Nb1+xS2, where x is ~0.35)12 as a HER catalyst with current densities of >5,000 mA cm-2 at ~420 mV versus a reversible hydrogen electrode. We find the exchange current density at 0 V for 2H Nb1.35S2 to be ~0.8 mA cm-2, corresponding to a turnover frequency of ~0.2 s-1. We demonstrate an electrolyser based on a 2H Nb1+xS2 cathode that can generate current densities of 1,000 mA cm-2. Our theoretical results reveal that 2H Nb1+xS2 with Nb-terminated surface has free energy for hydrogen adsorption that is close to thermoneutral, facilitating HER. Therefore, 2H Nb1+xS2 could be a viable catalyst for practical electrolysers.
Due to increasing antibiotic pollution in the water environment, green and efficient adsorbents are urgently needed to solve this problem. Here we prepare magnetic bamboo-based activated carbon (MDBAC) through delignification and carbonization using ZnCl2 as activator, resulting in production of an activated carbon with large specific surface area (1388.83 m2 g-1). The influencing factors, such as solution pH, initial sulfadiazine (SD) concentration, temperature, and contact time, were assessed in batch adsorption experiments. The Langmuir isotherm model demonstrated that MDBAC adsorption capacity on SD was 645.08 mg g-1 at its maximum, being higher than majority of previously reported adsorbents. In SD adsorption, the kinetic adsorption process closely followed the pseudo-second kinetic model, and the thermodynamic adsorption process was discovered to be exothermic and spontaneous in nature. The MDBAC exhibited excellent physicochemical stability, facile magnetic recovery and acceptable recyclability properties. Moreover, the synergistic interactions between MDBAC and SD mainly involved electrostatic forces, hydrogen bonding, π-π stacking, and chelation. Within the benefits of low cost, ease of production and excellent adsorption performance, the MDBAC biosorbent shows promising utilization in removing antibiotic contaminants from wastewater.
The potential use of non-viable biomass of a Gram negative bacterium i.e. Acinetobacter haemolyticus to remove Cr(III) species from aqueous environment was investigated. Highest Cr(III) removal of 198.80 mg g(-1) was obtained at pH 5, biomass dosage of 15 mg cell dry weight, initial Cr(III) of 100 mg L(-1) and 30 min of contact time. The Langmuir and Freundlich models fit the experimental data (R(2)>0.95) while the kinetic data was best described using the pseudo second-order kinetic model (R(2)>0.99). Cr(III) was successfully recovered from the bacterial biomass using either 1M of CH(3)COOH, HNO(3) or H(2)SO(4) with 90% recovery. TEM and FTIR suggested the involvement of amine, carboxyl, hydroxyl and phosphate groups during the biosorption of Cr(III) onto the cell surface of A. haemolyticus. A. haemolyticus was also capable to remove 79.87 mg g(-1) Cr(III) (around 22.75%) from raw leather tanning wastewater. This study demonstrates the potential of using A. haemolyticus as biosorbent to remove Cr(III) from both synthetic and industrial wastewater.
In low concentration, fluoride is considered a necessary compound for human health. Exposure to high concentrations of fluoride is the reason for a serious disease called fluorosis. Fluorosis is categorized as Skeletal and Dental fluorosis. Several Asian countries, such as India, face contamination of water resources with fluoride. In this study, a comprehensive overview on fluoride contamination in Asian water resources has been presented. Since water contamination with fluoride in India is higher than other Asian countries, a separate section was dedicated to review published articles on fluoride contamination in this country. The status of health effects in Asian countries was another topic that was reviewed in this study. The effects of fluoride on human organs/systems such as urinary, renal, endocrine, gastrointestinal, cardiovascular, brain, and reproductive systems were another topic that was reviewed in this study. Different methods to remove fluoride from water such as reverse osmosis, electrocoagulation, nanofiltration, adsorption, ion-exchange and precipitation/coagulation were introduced in this study. Although several studies have been carried out on contamination of water resources with fluoride, the situation of water contamination with fluoride and newly developed technology to remove fluoride from water in Asian countries has not been reviewed. Therefore, this review is focused on these issues: 1) The status of fluoride contamination in Asian countries, 2) health effects of fluoride contamination in drinking water in Asia, and 3) the existing current technologies for defluoridation in Asia.
The effect of corrosion inhibition of low carbon steel in water based medium containing lignin was investigated via weight loss method. The evolution of surface morphology has been carried out for 7 to 42 days via optical microscopy (OM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX) and X-ray photoelectron microscopy (XPS). Immersion of metal specimen without lignin shows that significant increase in the surface roughness. The longer the immersion time, the more the oxide crust formed. The surface degradation of metal specimen was well protected by immersion in lignin solution. A protective layer containing of lignin was formed on the surface of metal specimens after 7 and 21 days immersion. The corrosion inhibition gives about 13 and 53% inhibition for both 7 and 21 days immersion, respectively. The protective layers were spalling and separated from the metal surface after 42 days immersion in lignin solution possibly due to the increase in corrosion attack after long time immersion according to the increase in dissolved oxygen and may also due to the thermal mismatch between oxide and substrate. The adsorption of protective layer containing lignin was temporary adsorbed on the surface.
The methyl ester sulfonates represent a promising group of anionic surfactants which have the potential for improved performance and biocompatibility in a range of applications. Their solution properties, in particular their tolerance to hard water, suggests that surface ordering may occur in the presence of multi-valent counterion. Understanding their adsorption properties in a range of different circumstances is key to the exploitation of their potential. Neutron reflectivity and surface tension have been used to characterise the adsorption at the air-aqueous solution interface of the anionic surfactant sodium tetradecanoic 2-sulfo 1-methyl ester, C14MES, in the absence of electrolyte and in the presence of mono, di, and tri-valent counterions, Na+, Ca2+, and Al3+. In particular the emphasis has been on exploring the tendency to form layered structures at the interface. In the absence of electrolyte and in the presence of NaCl and CaCl2 and AlCl3 at low concentrations monolayer adsorption is observed, and the addition of electrolyte results in enhanced adsorption. In the presence of NaCl and CaCl2 only monolayer adsorption is observed. However at higher AlCl3 concentrations surface multilayer formation is observed, in which the number of bilayers at the surface depends upon the surfactant and AlCl3 concentrations.
In this study, biochars derived from waste fiberboard biomass were applied in tetracycline (TC) removal in aqueous solution. Biochar samples were prepared by slow pyrolysis at 300, 500, and 800°C, and were characterized by ultimate analysis, Fourier transform infrared (FTIR), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller (BET), etc. The effects of ionic strength (0-1.0 mol/L of NaCl), initial TC concentration (2.5-60 ppm), biochar dosage (1.5-2.5 g/L), and initial pH (2-10) were systemically determined. The results present that biochar prepared at 800°C (BC800) generally possesses the highest aromatization degree and surface area with abundant pyridinic N (N-6) and accordingly shows a better removal efficiency (68.6%) than the other two biochar samples. Adsorption isotherm data were better fitted by the Freundlich model (R2 is 0.94) than the Langmuir model (R2 is 0.85). Thermodynamic study showed that the adsorption process is endothermic and mainly physical in nature with the values of ΔH0 being 48.0 kJ/mol, ΔS0 being 157.1 J/mol/K, and ΔG0 varying from 1.02 to -2.14 kJ/mol. The graphite-like structure in biochar enables the π-π interactions with a ring structure in the TC molecule, which, together with the N-6 acting as electron donor, is the main driving force of the adsorption process.
To develop a green and facile adsorbent for removing indoor polluted formaldehyde (HCHO) gas, the biomass porous nanofibrous membranes (BPNMs) derived from microcrystalline cellulose/chitosan were fabricated by electrospinning. The enhanced chemical adsorption sites with diverse oxygen (O) and nitrogen (N)-containing functional groups were introduced on the surface of BPNMs by non-thermal plasma modification under carbon dioxide (CO2) and nitrogen (N2) atmospheres. The average nanofiber diameters of nanofibrous membranes and their nanomechanical elastic modulus and hardness values decreased from 341 nm to 175-317 nm and from 2.00 GPa and 0.25 GPa to 1.70 GPa and 0.21 GPa, respectively, after plasma activation. The plasma-activated nanofibers showed superior hydrophilicity (WCA = 0°) and higher crystallinity than that of the control. The optimal HCHO adsorption capacity (134.16 mg g-1) of BPNMs was achieved under a N2 atmosphere at a plasma power of 30 W and for 3 min, which was 62.42 % higher compared with the control. Pyrrolic N, pyridinic N, CO and O-C=O were the most significant O and N-containing functional groups for the improved chemical adsorption of the BPNMs. The adsorption mechanism involved a synergistic combination of physical and chemical adsorption. This study provides a novel strategy that combines clean plasma activation with electrospinning to efficiently remove gaseous HCHO.
In vitro Lead (Pb(2+)) binding capacity of two probiotic bacteria strains, namely Bifidobacterium longumBB79 and Lactobacillus pentosusITA23, was assessed following incubation with the intestinal contents (IC) of laying hens. Results of this study demonstrated that IC treatment significantly enhanced (P<0.01) Pb(2+) binding capacity of both bacterial strains. Fourier transform infrared analysis indicated that several functional groups (O-H or N-H, C-H, C˭O, C-O, and C-O-C) on the bacteria cell wall involved in metal ion binding were altered after IC incubation, and new groups appeared between the 3700cm(-1) and 4000cm(-1)bands. Transmission electron microscopy demonstrated that after incubation with IC, unidentified IC components created new binding sites on the bacterial cell surface. These particles also changed the mechanism of Pb(2+) binding of the two strains from intracellular accumulation to extracellular adsorption.
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.
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.
Improving the stability of cuprous oxide (Cu2 O) is imperative to its practical applications in artificial photosynthesis. In this work, Cu2 O nanowires are encapsulated by metal-organic frameworks (MOFs) of Cu3 (BTC)2 (BTC=1,3,5-benzene tricarboxylate) using a surfactant-free method. Such MOFs not only suppress the water vapor-induced corrosion of Cu2 O but also facilitate charge separation and CO2 uptake, thus resulting in a nanocomposite representing 1.9 times improved activity and stability for selective photocatalytic CO2 reduction into CH4 under mild reaction conditions. Furthermore, direct transfer of photogenerated electrons from the conduction band of Cu2 O to the LUMO level of non-excited Cu3 (BTC)2 has been evidenced by time-resolved photoluminescence. This work proposes an effective strategy for CO2 conversion by a synergy of charge separation and CO2 adsorption, leading to the enhanced photocatalytic reaction when MOFs are integrated with metal oxide photocatalyst.
Presence of copper within water bodies deteriorates human health and degrades natural environment. This heavy metal in water is treated using a promising biochar derived from rambutan (Nephelium lappaceum) peel through slow pyrolysis. This research compares the efficacies of artificial neural network (ANN), adaptive neuro-fuzzy inference system (ANFIS), and multiple linear regression (MLR) models and evaluates their capability in estimating the adsorption efficiency of biochar for the removal of Cu (II) ions based on 480 experimental sets obtained in a laboratory batch study. The effects of operational parameters such as contact time, operating temperature, biochar dosage, and initial Cu (II) ion concentration on removing Cu (II) ions were investigated. Eleven different training algorithms in ANN and 8 different membership functions in ANFIS were compared statistically and evaluated in terms of estimation errors, which are root mean squared error (RMSE), mean absolute error (MAE), and accuracy. The effects of number of hidden neuron in ANN model and fuzzy set combination in ANFIS were studied. In this study, ANFIS model with Gaussian membership function and fuzzy set combination of [4 5 2 3] was found to be the best method, with accuracy of 90.24% and 87.06% for training and testing dataset, respectively. Contribution of this study is that ANN, ANFIS, and MLR modeling techniques were used for the first time to study the adsorption of Cu (II) ions from aqueous solutions using rambutan peel biochar.
The effects of microwave irradiation on the drug release property of pectinate beads loaded internally with chitosan (chitosan-pectinate beads) were investigated against the pectinate beads and beads coacervated with chitosan externally (pectinate-chitosonium beads). These beads were prepared by an extrusion method using sodium diclofenac as the model water-soluble drug. The beads were subjected to microwave irradiation at 80 W for 5, 10, 21 and 40 min. The profiles of drug dissolution, drug content, drug-polymer interaction and polymer-polymer interaction were determined by drug dissolution testing, drug content assay, drug adsorption study, differential scanning calorimetry (DSC) and Fourier transform infra-red spectroscopy (FTIR) techniques. Treatment of pectinate beads by microwave did not lead to a decrease, but an increase in the extent of drug released at 4h of dissolution owing to reduced pectin-pectin interaction via the CO moiety of polymer. In addition, the extent of drug released from the pectinate beads could not be reduced merely through the coacervation of pectinate matrix with chitosan. The reduction in the extent of drug released from the pectinate-chitosonium beads required the treatment of these beads by microwave, following an increase in drug-polymer and polymer-polymer interaction in the matrix. The extent of drug released from the pectinate beads was reduced through incorporating chitosan directly into the interior of pectinate matrix, owing to drug-chitosan adsorption. Nonetheless, the treatment of chitosan-pectinate matrix by microwave brought about an increase in the extent of drug released unlike those of pectinate-chitosonium beads. Apparently, the loading of chitosan into the interior of pectinate matrix could effectively retard the drug release without subjecting the beads to the treatment of microwave. The microwave was merely essential to reduce the release of drug from pectinate beads when the chitosan was introduced to the pectinate matrix by means of coacervation. Under the influences of microwave, the drug release property of beads made of pectin and chitosan was mainly modulated via the CH, OH and NH moieties of polymers and drug, with CH functional group purported to retard while OH and NH moieties purported to enhance the drug released from the matrix.
The suitability and efficacy of three-dimensional (3D) graphene, including its derivatives, have garnered widespread attention towards the development of novel, sustainable materials with ecological amenability. This is especially relevant towards its utilization as adsorbents of wastewater contaminants, such as heavy metals, dyes, and oil, which could be majorly attributed to its noteworthy physicochemical features, particularly elevated chemical and mechanical robustness, advanced permeability, as well as large specific surface area. In this review, we emphasize on the adsorptive elimination of oil particles from contaminated water. Specifically, we assess and collate recent literature on the conceptualization and designing stages of 3D graphene-based adsorbents (3DGBAs) towards oil adsorption, including their applications in either batch or continuous modes. In addition, we analytically evaluate the adsorption mechanism, including sorption sites, physical properties, surface chemistry of 3DGBA and interactions between the adsorbent and adsorbate involving the adsorptive removal of oil, as well as numerous effects of adsorption conditions on the adsorption performance, i.e. pH, temperature, initial concentration of oil contaminants and adsorbent dosage. Furthermore, we focus on the equilibrium isotherms and kinetic studies, in order to comprehend the oil elimination procedures. Lastly, we designate encouraging avenues and recommendations for a perpetual research thrust, and outline the associated future prospects and perspectives.
A novel preparation method of magnetized palm shell waste-based powdered activated carbon (MPPAC, avg. size 112 μm) was developed. The prepared MPPAC was assessed by several physicochemical analyses, and batch tests were performed for ibuprofen (IBP) removal. Field emission scanning electron microscopy (FESEM) and N2 gas isotherms revealed that magnetite and maghemite were homogeneous and deposited mostly on the surface of PPAC without a significant clogging effect on the micropores. Isotherm results showed that 3.8% Fe (w/w) impregnated PPAC [MPPAC-Fe(3.8%)] had about 2.2-fold higher maximum sorption capacity (157.3 mg g-1) and a 2.5-fold higher sorption density (0.23 mg m-2) than pristine PPAC. Both Fourier-transform infrared spectroscopy (FTIR) and isotherm data indicated that the high sorption capacity and density of IBP by MPPAC was primarily attributable to donor-acceptor complexes with the C = O group and dispersive π-π interactions with the carbon surface. Based on kinetic and repeated adsorption tests, pore diffusion was the rate-limiting step, and MPPAC-Fe(3.8%) had about 1.9~2.8- and 9.1~15.8-fold higher rate constants than MPPAC-Fe(8.6%) and palm shell-waste granular activated carbon (PGAC, avg. size 621 μm), respectively. MPPAC showed almost eight fold greater re-adsorption capacity than PPAC due to a thermal catalytic effect of magnetite/maghemite.
Triethoxyphenylsilane (TEPS)-functionalized magnetic palm-based powdered activated carbon (MPPAC-TEPS) was prepared and characterized using various spectroscopic methods, and then tested for the removal of bisphenol A, carbamazepine, ibuprofen and clofibric acid. Magnetite film on MPPAC-TEPS was homogeneously coated on the outer surface of palm-based powdered activated carbon (PPAC) through a hydrothermal co-precipitation technique. Followed by silanization of phenyl-functionalized organosilane on MPPAC's magnetic film. As results, micro/mesopore surface area and volume increased without significant pore clogging and iron (Fe) dissolution under the acidic conditions was greatly decreased. The unique structural and chemical features of MPPAC-TEPS were found to be the main reasons for the enhanced adsorption rates and removal capacities of POPs. The presence of electrolytes and different pH values greatly affected the sorption efficiencies. The dominant sorption mechanism of POPs by MPPAC-TEPS was determined to be π-π interaction (physisorption), based on thermodynamic (ΔG°) and differential scanning calorimetry (DSC). Thermal regeneration at a low temperature (350 °C) was an effective method to desorb the retained POPs and enabled to reactivate MPPAC-TEPS with sustained sorption rates and capacities, whereas PPAC was largely exhausted. As a new type of sorbent for POPs, MPPAC-TEPS has operational advantages, such as magnetic separation and stable regeneration.