Favorable Sorption Research Articles

Green synthesis of graphene oxide and magnetite nanoparticles and their arsenic removal efficiency from arsenic contaminated soil

Graphene-based nanomaterials have been proved to be robust sorbents for efficient removal of environmental contaminants including arsenic (As). Biobased graphene oxide (bGO-P) derived from sugarcane bagasse via pyrolysis, GO-C via chemical exfoliation, and magnetite nanoparticles (FeNPs) via green approach using Azadirachta indica leaf extract were synthesized and characterized by Ultraviolet-Visible Spectrophotometer (UV-vis.), Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), mean particle size and Scanning electron microscopy (SEM) along with Energy dispersive spectroscopy (EDX) analysis. Compared to cellulose and hemicellulose, the lignin fraction was less in the precursor material. The GOC, bGO-P and FeNPs displayed maximum absorption at 230, 236, and 374 nm, respectively. FTIR spectrum showed different functional groups (C-OH, C-O-C, COOH and O-H) modifying the surfaces of synthesized materials. Graphene based nanomaterials showed clustered dense flakes of GO-C and thin transparent flakes of bGO-P. Elemental composition by EDX analysis of GO-C (71.26% C and 27.36% O), bGO-P (74.54% C and 24.61% O) and FeNPs (55.61% Fe, 4.1% C and 35.72% O) confirmed the presence of carbon, oxygen, and iron in synthesized nanomaterials. Sorption study was conducted with soil amended with different doses of synthesized nanomaterials (10, 50 and 250 mg) and exposed to 100, 300 and 500 ppm of As. Arsenic concentrations were estimated by colorimetry and atomic absorption spectroscopy (AAS). GO-C, bGO-P, and FeNPs showed substantial As removal efficiency i.e., 81 to 99.3%, 65 to 98.8% and 73.1–89.9%, respectively. Green synthesis of bGO-P and magnetite nanoparticles removed substantial amounts of As compared to GO-C and can be effectively deployed for As removal or immobilization. Higher and medium sorbent doses (250 and 50 mg) exhibited greater As removal and data was best fitted for Freundlich isotherm evidencing favorable sorption. Nevertheless, at low sorbent doses, data was best fitted for both models. Newly synthesized nanomaterials emerged as promising materials for As removal strategy for soil nano-remediation and can be effectively deployed in As contaminated soils.

Chitosan-based foam composites for hexavalent chromium remediation: Effect of microcellulose and crosslinking agent content

Potentially toxic metal ions, such as hexavalent chromium (Cr6+), present in water concern the population's health due to their persistence, bioaccumulation potential, and high toxicity. Highly porous materials based on polysaccharides are promising technologies for metal removal due to their high surface area, biodegradability, and low toxicity. This study evaluated the effect of concentrations of microcellulose (0.5, 1, and 1.5 %) and glutaraldehyde (1, 2, and 3 %) in the adsorption capacity and mechanical properties of chitosan foams. The developed foams exhibited a three-dimensional structure with interconnected pores. Compared to foams without microcellulose, adding 1.5 % microcellulose increased up to 180 % in maximum stress supported by the foams and up to 135 % in Young's modulus. However, Cr6+ sorption capacity decreased with increasing microcellulose and crosslinking agent content due to the occupation of amino groups. Still, the foams exhibited a highly favorable sorption behavior, and the Sips isotherm model provided the best fit to the experimental data. The maximum sorption capacity reached approximately 1.4 mmol·g−1 at pH 4.0 and 25 °C. The foam structural integrity, enhanced mechanical properties, and efficient sorption capacity make them viable alternatives for environmentally friendly and cost-effective treatment of water contaminated with Cr6+ ions.

Screening and characterization of novel biosorbent for the removal of Cadmium from contaminated water

Presence of trace metal pollutants in the aquatic system is a worldwide foremost concern. The present investigation was an attempt to find out the novel biosorbent for the removal of Cadmium(CdII) from contaminated water. The leaf of Sesbania bispinosa was screened out as a potential Cd(II) removing biosorbent from thirty different natural biomasses by physico-chemical and sorption process characterizations. Biosorption capacity of S. bispinosa was determined by batch mode biosorption method with the functions of solution pH, contact time, biosorbent dose and initial Cd(II) concentration. Obtained results were analyzed for isotherm and kinetic study. The S. bispinosa biosorbent exhibited the biosorption equilibrium of Cd(II) uptake in 30 min. At pH 4, biosorbent dose of 1 g/L was sufficient for maximum Cd(II) uptake. Scanning Electron Microscopy (SEM) images and Fourier Transform Infrared Spectroscopy (FTIR) spectra confirmed the favourable sorption surface characteristics. The data also demonstrated that Freundlich isotherm (R2=0.998) is the better fitted model compared to Langmuir model and the maximum sorption capacity was found to be 33.33 mg/g. Suitabilty of pseudo second order reaction pathway was observed during the kinetic study. Most especially, The selected biosorbent is ascertained effective in removing multimetals [Cd(II) - 67.51 %, Cr(VI) – 40.36 %, Pb(II) – 100 % and Cu(II) – 59.01 %] from a quaternary aqueous solution of Cd(II), Cr(VI), Pb(II) and Cu(II) mixture and spent biosorbent can be easily regenerated by applying 0.1 M HCl solution as a desorbing agent. It, therefore, could be concluded that leaves of S.bispinosa might be a low-cost and environmentally sound novel biosorbent for the treatment of Cd(II) contaminated water.

Effects of Selected Properties of Semi-Arid Soil of Dutse, Jigawa State on Adsorption of Pb and Cd Ions

This study determined the effects of some selected physical and chemical properties of semi-arid soil on heavy metal sorption. Soil samples were collected randomly from Federal University Dutse within Nigeria's Sudan Savannah agroecological zone. Nitrate salts were used to prepare three different concentrations (10, 20, 30 mg/kg) of CdCl2 and PbCl2. The equilibrium sorption of the study soil was determined. The equilibrium sorption data were fitted into Langmuir and Freundlich isotherms. Langmuir and Freundlich isotherm model's r2 values (1) were at par. The boundary energy b (1 mg-1) from the Langmuir isotherm model was determined to be -110.0 and 47 for Pb and Cd, respectively. Freundlich isotherm sorption intensity (n) of 1.92 and 1.67 indicated a favorable sorption, revealing physical adsorption rather than chemical adsorption. Correlation analysis established the relationship between the heavy metal sorption capacity and soil properties. The R values of 0.92 and 0.72 showed a positive relationship between Pb and Cd adsorption with soil silt content. Positive relationships (R) were obtained from the organic matter (0.68), Total Nitrogen (0.99 and 0.60), as well as particle size on adsorption of both metals. Adsorption of heavy metals was positively affected by the physical and chemical properties of the semi-arid soil.

Removal of per- and polyfluoroalkyl substances by activated hydrochar derived from food waste: Sorption performance and desorption hysteresis

Carbonaceous materials, derived from waste biomass, have proven to be a viable and appealing alternative for removing emerging micro-pollutants, such as per- and polyfluoroalkyl substances (PFAS). To assess the feasibility and efficacy of using material derived from food waste to alleviate PFAS pollution, this study prepared activated hydrochar (AHC) for sorbing ten PFAS, including five perfluoroalkyl carboxylic acids (PFCA; C4–C8), three perfluoroalkyl sulfonic acids (PFSA; C4, C6, C8), and two emerging PFAS, namely hexafluoropropylene oxide dimer acid (commercial name GenX, an alternative to perfluorooctanoic acid (PFOA)) and 6:2 fluorotelomer sulfonic acid (6:2 FTS). The results demonstrated that AHC possessed a relatively high specific surface area (207 m2/g) and hydrophobic surface properties. At environmentally relevant concentrations (40 μg/L), the sorption partition coefficients (log Kd) of PFAS on AHC ranged from 2.33 to 6.49 L/kg. Notably, GenX exhibited a lower log Kd value (2.33 L/kg) than PFOA (3.88 L/kg). The AHC showed favorable sorption performance for all tested PFAS, with log Kd values surpassing other reported sorbents (e.g., 0.83 for GenX on pyrochar, and 2.83 for PFOA on commercial biochar). Additionally, desorption hysteresis was observed for all PFAS, except for PFOA, and was particularly pronounced in PFBA, GenX, and 6:2 FTS at high initial concentrations, with Hysteresis Index (HI) values varying from 0.31 to 1.45, 0.68 to 1.88, and 0.51 to 1.85, respectively. Given its robust sorption capacity and desorption hysteresis toward PFAS, AHC is expected to be a favorable candidate for remediating PFAS-contaminated water. This study underscores, for the first time, the potential of food waste-derived hydrochar as an efficient sorbent for alleviating PFAS contamination, and further study is needed to investigate the sorption and desorption behaviors of PFAS on AHC at various environmental conditions.

Variability of Radionuclide Sorption Efficiency on Muscovite Cleavage Planes

AbstractIn deep geological repositories for nuclear waste, the surrounding rock formation serves as an important barrier against radionuclide migration. Multiple potential host rocks contain phyllosilicates, which have shown high efficiency in radionuclide sorption. Recent experimental studies report a heterogeneous distribution of adsorbed radionuclides on nanotopographic mineral surfaces. In this study, the energetic differences of surface sorption sites available at nanotopographic structures such as steps, pits, and terraces are investigated. Eleven important surface sites are selected and the energies of ad‐ and desorption reactions are obtained from density functional theory calculations. The adsorption energies are then used for the parameterization of a kinetic Monte Carlo model simulating the distribution of adsorbed europium on a typical nanotopographic muscovite surface. On muscovite, silicon step sites are favorable for europium sorption and lead to an increased adsorption in regions with high step concentrations. Under identical chemical conditions, sorption on typical nanotopographic surfaces is increased by a factor of three compared to atomically flat surfaces. Desorption occurs preferentially at terrace sites, leading to an overall 2.5 times increased retention at nanotopographic structures. This study provides a mechanistic explanation for heterogeneous sorption on nanotopographic mineral surfaces due to the availability of energetically favorable sorption sites.

Isotherms and Kinetics Study for Adsorption of Nitrogen from Air using Zeolite Li-LSX to Produce Medical Oxygen

This research investigates the adsorption isotherm and adsorption kinetics of nitrogen from air using packed bed of Li-LSX zeolite to get medical oxygen. Experiments were carried out to estimate the produced oxygen purity under different operating conditions: input pressure of 0.5 – 2.5 bar, feed flow rate of air of 2 – 10 L.min-1 and packing height of 9-16 cm. The adsorption isotherm was studied at the best conditions of input pressure of 2.5 bar, the height of packing 16 cm, and flow rate 6 Lmin-1 at ambient temperature, at these conditions the highest purity of oxygen by this system 73.15 vol % of outlet gas was produced. Langmuir isotherm was the best models representing the experimental data., and the model parameters were the maximum monolayer coverage (qm) 200 mg. g-1 and Kl 0.00234 L.mg -1. Also, from the Freundlich isotherm model, the sorption intensity (n) indicated favorable sorption of 1.435. The average free energy estimated from the DRK isotherm model was 0.02 KJ.mol-1, which proved the adsorption process to follow physical nature. The results got from experiments showed a coincidence to the pseudo-first-order kinetic model.

Superior sorption capacity and one-step reduction of Au(III) by a novel chitosan-based electrospun fiber mat: A cheap and simple technique

In this study, electrospinning technique was used to synthesize a novel cost-effective fiber mat chitosan-glutaraldehyde-thiourea (CS-Glu-Th) with superior maximum sorption capacity, sorption rate, and selectivity. The sorption results showed that CS-Glu-Th performed perfectly at both low and high concentrations of Au(III), with the maximum sorption capacity above 2.28 × 106 mg/kg at high concentrations and a recovery efficiency of 98.44% at low concentrations; sorption equilibrium was reached in about 5 h. Sorption of Au(III) on CS-Glu-Th was driven by a combination of both electrostatic attraction and coordination interaction with C–N, CN, and CS groups. Importantly, 94.55% of the sorbed Au(III) was directly reduced to elemental gold by the electron donor C-N group. Additionally, CS-Glu-Th showed favorable sorption selectivity for Au(III); its recovery efficiency reached 97.30% under the interference of co-existing elements (i.e., Cu(II), Ni(II), Pb(II), Zn(II), and Pt(IV)) at a same concentration of 2 mg/L. A cost-benefit analysis showed that if one synthesizes 1 kg of CS-Glu-Th, a profit of 33044.7 RMB can be achieved by recovering Au(III) from an industrial application scenario, equivalent to a profit rate of 22.0%. Our findings highlight that the finally-synthesized fiber mat CS-Glu-Th is a promising material to recover gold from the aqueous phase with excellent performance.

Ion exchange resin – Bipolar membrane electrodialysis hybrid process for reverse osmosis permeate remineralization: Cation exchange resins equilibria and kinetics

Reverse osmosis (RO) membrane technology is widely used for producing high-quality drinking water. Yet RO permeate is by itself acidic (pH = 5.5 to 6.0), unbuffered and has low mineral content, therefore post treatment i.e., remineralization is mostly required. An ion exchange resin – bipolar membrane electrodialysis hybrid process was developed for sustainable RO permeate remineralization. Fundamental phenomena in the recovery of calcium and magnesium by ion exchange to remineralize reverse osmosis permeate were investigated. Sorption equilibrium and mass transfer kinetics were investigated for weakly acidic (Amberlite IRC747, Amberlite IRC748, Lewatit S8227) and strongly acidic (DOWEX Marathon MSC) cation exchange resins. Most suitable resin for the remineralization process should have high selectivity for calcium and magnesium and low selectivity for monovalent ions to avoid adding undesired ions to the remineralised water downstream as well as relatively fast mass transfer kinetics. The isotherms were correlated with the stoichiometric ion exchange isotherm and the Langmuir-Freundlich (Sips) isotherm. All resins showed high selectivity for ions with higher valence, but weakly acidic cation exchange (WAC) resins showed significantly lower selectivity towards monovalent ions than the strongly acidic cation exchange resin. The influence of each resin functional group, charge density and degree of protonation was shown to have a major effect on the resin selectivity. Amberlite IRC748 had the lowest selectivity (KNH4+/Na+ = 0.77 ± 0.19) and removal (46%) for ammonium in a single-component system. The mass transfer rate was found to be controlled by intraparticle diffusion rather than film diffusion. Amberlite IRC748 is recommended for use in a remineralization process where divalent ions are present because of its favourable sorption and higher mass transfer kinetics (Ks = 8.65 ± 0.58 × 10−12, 7.95 ± 0.38 × 10−12 m2/s for calcium and magnesium, respectively).

Microplastics and organics - A comparative study of sorption of triclosan and malachite green onto polyethylene.

This study aims to elucidate interaction of organics with microplastics in a comparative manner via the use of two model compounds (i.e., triclosan (TCS) and malachite green (MG)) having different physicochemical properties, onto polyethylene (PE). TCS, is hydrophobic with low solubility, while MG is hydrophilic with high aqueous solubility. Kinetic studies indicate faster sorption (teq = 24 h) and equilibrium studies show much higher capacity (qe = 6,921 μg/g) for TCS, when compared to those of MG (teq = 5 d, qe = 221 μg/g). While pseudo-kinetic model fits sorption of both organics to PE, equilibrium isotherms as well as the results on effect of particle size and pH indicate dissimilar sorption mechanisms. Considering pHPZC = 2, observation of favourable sorption of TCS in acidic regions and sorption being unaffected by particle size was explained by TCS sorption to be dominated by hydrophobic interactions in amorph regions of PE. Higher removal of MG was observed at lower surface charge of PE, and a clear favourable impact of surface area on MG sorptive capacity pointed to the presence of non-specific van der Waals type interactions on the surface of PE. Mechanistic evaluations presented here contribute to our understanding of interaction of MPs with organics in aquatic ecosystems.

On the Sorption Mode of U(IV) at Calcium Silicate Hydrate: A Comparison of Adsorption, Absorption in the Interlayer, and Incorporation by Means of Density Functional Calculations

Calcium silicate hydrate (C-S-H) is the main product of cement hydration and has also been shown to be the main sorbing phase of actinide ions interacting with cement. U(IV) has been chosen as an exemplary actinide ion to study actinide sorption at C-S-H as U is the main element in highly active radioactive waste and because reducing conditions are foreseen in a deep geological repository for such waste. U(IV) surface adsorption, absorption in the interlayer, and incorporation into the calcium oxide layer of C-S-H has been modeled quantum mechanically, applying a density functional approach. For each sorption mode various sites have been considered and a combined dynamic equilibration and optimization approach has been applied to generate a set of representative stable sorption complexes. At the surface and in the interlayer similar U(IV) hydroxo complexes stabilized by Ca2+ ions have been determined as sorbates. Surface adsorption tends to be preferred over absorption in the interlayer for the same type of sites. Incorporation of U(IV) in the CaO layer yields the most favorable sorption site. This result is supported by good qualitative agreement of structures with EXAFS results for other actinides in the oxidation state IV, leading to a new interpretation of the experimental results.

Quantifying the coupled monovalent and divalent ions sorption in dense ion-exchange membranes

As a universal phenomenon in solution-membrane systems, the coupled competitive monovalent and divalent ions sorption significantly impacts the transport process in ion-exchange membranes. Often, the quantitative and qualitative relationships between them are unclear. Here, we present a lattice-based molecular model to capture the interplay effect of ion-pairing and electrostatic interaction on the competitive partitioning process. In particular, we utilize statistical mechanics to formulate how the monovalent and divalent counterions competitively pair with the fixed charge group in the membranes. To this end, the model can quantify (a) the counterions sorption and (b) the coion repulsion within the membranes, which, collectively, allow us to quantify the ion partitioning and the pairing site saturation. To showcase the capability of our model, we compare our results with published experiment data, where we achieve a relatively good agreement between them. We demonstrate that the competitive ion partitioning depends highly upon (i) the entropy change generated by the counterions pairing with the fixed charge group, (ii) the binding energy, and (iii) the osmotic pressure, and (iv) the electrostatic interaction. These different factors can explain the favorable sorption of divalent counterions in the cation-exchange membranes but monovalent counterions in the anion ones, as previously reported. Altogether, our theoretical approach provides an insight into the fundamental understanding of coupled competitive monovalent and divalent ions sorption within the dense ion-exchange membranes, further enhancing the knowledge of the competitive ion partitioning process.

Recovery of critical metals from leach solution of electronic waste using magnetite electrospun carbon nanofibres composite.

Scarcity in mining and geo-political direction diverts attention toward critical metal recycling. Gallium (Ga), indium (In) and germanium (Ge) are among the critical metals that consume approximately 80% of world mining in the innovative production of electrical and electronic equipment. The fast obsolescing rate generates a large amount of electronic waste, which is now seen as a secondary reservoir for critical metals. These metal resources need to be dealt with with effective recycling capabilities. Based on solid-phase extraction, magnetic nano-hydrometallurgy is opening a new area of metallic contents recovery in conventional hydrometallurgy. In the present work, polyacrylonitrile (PAN) based electrospun nanofibres were synthesized and carbonized at 800°C in an inert environment. After surface oxidation, carbon nanofibres were decorated with magnetite particles through co-precipitation. The saturation magnetization value (Ms = 23.6emu/g) confirms high loading of magnetite particles. The selected critical metal ions are freely present in an aqueous solution at pH 1 to 3; thus, highest removal efficiency was observed at pH 2. Pseudo-second-order kinetics confirm the chemical/charge interaction between sorbent and sorbate ions. Maximum sorption capacity calculated through Langmuir isotherm was 226, 191 and 171mg/g for Ge(IV), Ga(III) and In(III) metal ions, respectively. The RL value (0 < RL < 1) indicates favourable sorption process. The sorbed target metal ions were collectively eluted using 1mol/L hydrochloric acid. The preconcentration factor was calculated at 1080 for Ge(IV) and In(III) while 1260 for Ga(III). The method was validated with 5µg/mL spiked multi-element standards and applied to multiple acid-leached electronic waste samples like PCBs, waste LCD panels and solar panels. Recoveries in the range of 96.2% for Ga(III), 95.6% for In(III) and 97.4% for Ge(IV) in the presence of diverse ions indicate the suitability of the proposed method for target metal ions even in a complex matrix.

Sorption Profile of Low Specific Activity 99Mo on Nanoceria-Based Sorbents for the Development of 99mTc Generators: Kinetics, Equilibrium, and Thermodynamic Studies.

99Mo/99mTc generators play a significant role in supplying 99mTc for diagnostic interventions in nuclear medicine. However, the applicability of using low specific activity (LSA) 99Mo asks for sorbents with high sorption capacity. Herein, this study aims to evaluate the sorption behavior of LSA 99Mo towards several CeO2 nano-sorbents developed in our laboratory. These nanomaterials were prepared by wet chemical precipitation (CP) and hydrothermal (HT) approaches. Then, they were characterized using XRD, BET, FE-SEM, and zeta potential measurements. Additionally, we evaluated the sorption profile of carrier-added (CA) 99Mo onto each material under different experimental parameters. These parameters include pH, initial concentration of molybdate solution, contact time, and temperature. Furthermore, the maximum sorption capacities were evaluated. The results reveal that out of the synthesized CeO2 nanoparticles (NPs) materials, the sorption capacity of HT-1 and CP-2 reach 192 ± 10 and 184 ± 12 mg Mo·g–1, respectively. For both materials, the sorption kinetics and isotherm data agree with the Elovich and Freundlich models, respectively. Moreover, the diffusion study demonstrates that the sorption processes can be described by pore diffusion (for HT-synthesis route 1) and film diffusion (for CP-synthesis route 2). Furthermore, the thermodynamic parameters indicate that the Mo sorption onto both materials is a spontaneous and endothermic process. Consequently, it appears that HT-1 and CP-2 have favorable sorption profiles and high sorption capacities for CA-99Mo. Therefore, they are potential candidates for producing a 99Mo/99mTc radionuclide generator by using LSA 99Mo.

A novel approach to sorbent-based remediation of soil impacted by organic micropollutants and heavy metals using granular biochar amendment and magnetic separation

Soil remediation by sorbent amendment is a popular method to immobilize contaminants but it is limited by the fact that the sorbent cannot be retrieved from the soil, posing as a threat to its quality, due to the gradual leaching of the sorbed contaminants. To address this challenge, this work proposes the use of granular-sized, magnetically retrievable sorbents for soil remediation. Specifically, granular biochar, that offers favorable sorption sites for both organic and inorganic contaminants, was used to treat contaminated soil samples. It is demonstrated that sorbent size plays a crucial role in its separation from the soil matrix by magnetic field. Granular magnetic biochar (gMBC) of 1–2 mm was found to be the most suitable sorbent size because it does not assimilate into the soil matrix and can be quantitatively retrieved both from wet and dry soil by means of magnetism, yielding a sorbent-free matrix. In this manner, the soil is relieved from both the hazardous contaminants and the contaminant-laden sorbent. Using gMBC, the remediation of contaminated soil from both organic micropollutants and heavy metals was optimized accomplishing remediation efficiencies from 40% to 90% for organic compounds and 30–65% for heavy metals through sorption and chemical transformation of the contaminants. The results of the study show that granular magnetic sorbents can be an effective and practical solution to the remediation of soils by facilitating their retrieval directly from the solid matrix which is not possible with micro/nanoparticle sorbents.

Enhanced Atmospheric Water Harvesting with Sunlight-Activated Sorption Ratcheting.

The global challenge of clean water scarcity needs to be confronted with novel sustainable, climate neutral solutions, over the entire spectrum of possible clean water availability. Atmospheric moisture represents a major untapped resource that can be harvested by sorbents, enabling water production in dry inland regions where it is needed. While benefiting from the utilization of an important renewable energy source, solar-driven, sorbent-based atmospheric water harvesting systems are inseparably based on a single water harvesting cycle per day, which severely limits the daily water productivity and the competitiveness of this very promising technology. Here, we rationally design an atmospheric water harvesting strategy, using durable hydrogel sorbents, that operates with sorption "ratcheting"─a large sequence of rapid adsorption and subsequent desorption steps─activated by direct sunlight. Employing theoretical considerations, we tailor the ratcheting timescales to the inherent sorption properties of the hydrogels, optimally exploiting their natural harvesting capabilities, while maintaining the sustainable utility of the daily cycle. Amplified by the favorable sorption properties and ratcheting stability of the sorbent, this strategy demonstrates an impressive ∼80% increase in water harvesting yield over the daily cycle systems. The generic nature of the ratcheting concept shows great potential to advance the water harvesting capabilities of a range of related systems.

Insights into sorption speciation of uranium on phlogopite: Evidence from TRLFS and DFT calculation

Knowledge of the sorption speciation of uranium at mineral/water interface is essential to construct reliable retention and migration models. In this work, the sorption speciation of U(VI) at the phlogopite/water interface was studied at trace concentrations by combining batch sorption, time-resolved luminescence spectroscopy, and theoretical calculation. Batch experiments showed that the sorption of U(VI) on phlogopite was strongly dependent on pH but weakly affected by ionic strength, implying that the inner-sphere surface complexation was mainly responsible for U(VI) sorption on phlogopite. The diverse luminescence spectral characteristics indicated the formation of multiple inner-sphere surface species at the phlogopite/water interface, whose abundances varied as a function of pH. A portion of U(VI) precipitated as uranyl oxyhydroxides such as metaschoepite and becquerelite at high pH. Density functional theory calculation revealed that the bidentate complex at the edge of phlogopite (≡AlO-MgO-UO2(H2O)3) was the most favorable sorption configuration for U(VI) at acidic condition. The increasing temperature enhanced the sorption of U(VI) on phlogopite without altering the sorption species, and such enhancement in U(VI) sorption was withdrawn once the temperature decreased. These findings are essential for understanding the immobilization mechanism of U(VI) in mica-rich granitic terrains at a molecular scale and building a reliable retention model.

Carbon Nanotubes Hybrid Hydrogels for Environmental Remediation: Evaluation of Adsorption Efficiency under Electric Field.

The performance of Carbon Nanotubes hybrid hydrogels for environmental remediation was investigated using Methylene Blue (MB), Rhodamine B (RD), and Bengal Rose (BR) as model contaminating dyes. An acrylate hydrogel network with incorporated CNT was synthesized by photo-polymerization without any preliminary derivatization of CNT surface. Thermodynamics, isothermal and kinetic studies showed favorable sorption processes with the application of an external 12 V electric field found to be able to influence the amount of adsorbed dyes: stronger interactions with cationic MB molecules ( and of 19.72 and 33.45 mg g−1, respectively) and reduced affinity for anionic RD ( and of 28.93 and 13.06 mg g−1, respectively) and neutral BR ( and of 36.75 and 15.85 mg g−1, respectively) molecules were recorded. The influence of pH variation on dyes adsorption was finally highlighted by reusability studies, with the negligible variation of adsorption capacity after five repeated sorption cycles claiming for the suitability of the proposed systems as effective sorbent for wastewater treatment.

Adsorption isotherm, kinetics, and thermodynamic studies of O,O‐diethyl‐O‐(3,5,6‐trichloropyridin‐2‐yl) phosphorothioate (chlorpyrifos) on cinnamon verum–based activated carbon

AbstractCinnamon verum was used as a low‐cost precursor to produce microporous‐activated carbons with a high surface area (894 m2/g) and large total pore volume (0.49 cm3/g). Thermogravimetric analysis scanning electron microscopy, Fourier‐transform infrared spectroscopy, Brunauer–Emmett–Teller surface area, and pore size analyzer techniques were used to characterize the new sorbent. The new porous carbon's ability to remove chlorpyrifos (CPS), an organo‐phosphorus surrogate of ware gases and the active component in most insecticides and pesticides, has been assessed by a batch adsorption procedure. Different sorption factors such as initial CPS concentrations, contact time, pH, solution temperature, and sorbent dosage have been studied. The results show that the new sorbent could remove 100% of CPS at low concentrations of 20 ppm within 20 min of contact time under a favorable sorption process. CPS adsorption was found to be exothermic, and the adsorption capacity decreases with increasing temperature. Equilibrium results were modeled using three isotherm models: Langmuir, Freundlich, and Temkin. The Langmuir isotherm model was found to be the best model to represent the CPS adsorption data. The kinetic results were fitted to pseudo–first‐order, pseudo–second‐order, and intraparticle diffusion models and thoroughly followed the pseudo–second‐order kinetic model. Thermodynamic factors such as enthalpy (ΔHo), entropy (ΔSo), and free energy (ΔGo) were assessed. The negative values of ΔHo and ΔGo indicate the exothermic and spontaneous nature of the adsorption process. The sorbent from waste cinnamon bark was economically practical and eliminates organophosphorus compounds from aqueous solutions.

Effect of superfine pulverization of powdered activated carbon on adsorption of carbamazepine in natural source waters

The purpose of this study is to investigate adsorptive removal of carbamazepine from natural source waters by superfine pulverized powdered activated carbon. Superfine pulverization is becoming an increasingly attractive approach to decrease the diffusion path of a target adsorbate molecule and improve the overall the kinetics of activated carbon adsorption. Here we report the impact of pulverization on powdered activated carbon characteristics, and carbamazepine adsorption behavior in distilled and deionized water and natural organic matter solutions. The superfine pulverization decreased the particle size of activated carbon by 50 folds and the specific surface area by 24%. In addition, the micropore volume of the activated carbon decreased from 0.23 cm3/g to 0.14 cm3/g, while mesopore and macropore volumes increased from 0.15 cm3/g and 0.11 cm3/g to 0.18 cm3/g and 0.48 cm3/g, respectively. In terms of surface chemistry, the oxygen and iron contents of the activated carbon increased notably after pulverization. Despite the decrease in surface area and increase in surface polarity, the pulverization improved the adsorption kinetics especially for short contact times i.e., < 6-h. In general, the dissolved organic carbon concentration negatively influenced the kinetic advantage of superfine pulverized activated carbon. Isotherm results indicated that the parent adsorbent has a higher adsorption capacity than superfine activated carbon in distilled and deionized water and in natural waters. This was attributed to the losses in specific surface area and favorable sorption sites inside micropores. Our literature analysis indicated that unlike the small molecular weight hydrophilic organic compounds, the pseudo-equilibrium adsorption capacity could be increased or at least not deteriorated for hydrophobic molecules (Kow > 3). Therefore, superfine pulverization of PAC can serve as a promising approach to remove micropollutants from natural source waters with a kinetic advantage.