Removal of Cr(VI) from aqueous solutions by the culm of bamboo grass treated with concentrated sulfuric acid

We prepared a carbonaceous sorbent for Cr(VI) from the culm of Sasa kurilensis by dehydration with concentrated H₂SO₄. The removal of Cr(VI) by the sorbent was highly solution pH dependent and mainly governed by physicochemical sorption. The equilibrium data fit well in the Langmuir isotherm model and indicate the endothermic nature of the Cr(VI) sorption. The desorption experiments suggest that the Cr(VI) sorption is generally irreversible, owing to strong interaction of HCrO₄⁻ with the active sites of the sorbent.     

Modeling of adsorption isotherms and kinetics of uranium sorption by magnetic ion imprinted polymers

Application of magnetic U(VI) ion imprinted polymers (IIPs) coated on magnetic nanoparticles was investigated for pre-concentration and determination of U(VI) ions in aqueous solutions. The scanning electron micrographs revealed the microporosity of the adsorbent. Uranium leaching was successful as the energy-dispersive X-ray spectra showed. The Brunauer–Emmett–Teller (BET) surface area improved by more than 13-fold (83.1 and 6.2 m² g^?1 for the leached and unleached magnetic IIP, respectively). U(VI) uptake was optimized using batch experiments with parameters affecting the uptake performance, such as initial uranium concentration, pH, contact time, and adsorbent dose investigated. Pseudo-second-order kinetics and the Langmuir isotherm model best fitted the experimental data. The maximum adsorption capacity of uranium onto the activated magnetic IIP reached 5.4 mg g^?1. The selectivity order was determined to be U(VI) > Ni(II) > Th(IV).     

Redox potential and uranium sorption onto sediments: kinetic and thermodynamic characteristics

ABSTRACT

The effects of the flooding and initial Eh of sediments on the sorption of uranium onto the sediments were analysed by flooding and static experiments. The changes in uranium species with Eh and kinetic and thermodynamic characteristics of the uranium sorption onto the sediments were investigated. The flooding experiment indicates that the initial Eh of the sediment gradually decreased with the increase in flooding time. Based on the redox potential in the flooding experiment, simulation results obtained using the geochemical simulation software PHREEQC show that the concentration of U (VI) decreased. In contrast, the concentrations of U (III), U (IV), and U (V) gradually increased. The pseudo-second-order kinetic model well fitted the experimental data, which shows that the sorption was mainly chemical sorption. The thermodynamic parameters suggest that the entropy and enthalpy under the used conditions were positive and that ΔG^θ was negative. A thermodynamic analysis shows that the sorption was endothermic and spontaneous. These results are useful for the understanding of the sorption mechanism and migration of uranium onto the sediment under different initial sediment redox potentials and provide a good theoretical foundation for radioactive pollution remediation.     

Preparation of magnetic nanocomposite beads and optimizing the conditions for effective removal of U(VI) from aqueous solutions

Magnetic ion-imprinted polymers (IIPs) were prepared by precipitate polymerization and leached with HCl to remove uranium. Their ability to remove hexavalent uranium from wastewater effluents was studied. Batch adsorption studies to determine the optimum conditions of U(VI) removal were conducted at different levels of sample pH, sorbent amount, agitation time, and initial uranium concentration. It was observed that, under optimum conditions (i.e. pH 4, adsorbent amount of 50 mg, 45 min agitation time, and initial U(VI) concentration of 2 mg L^?1), the maximum removal of U(VI) cations was >98% and 80% for the magnetic IIP and the corresponding magnetic non-imprinted polymers (NIP), respectively. Langmuir and Freundlich isotherms were used to describe the adsorption of U(VI) onto magnetic IIP and NIP. The adsorption capacity of U(VI) was determined to be 1.06 and 0.85 mg g^?1 for the two isotherms, respectively. The order of selectivity was found to be U(VI) > Fe(III) > Pb(II). For six cycles of regeneration and reuse, the magnetic polymers maintained their stabilities with only a 4% loss in the extraction efficiency. The average extraction efficiencies of the magnetic polymers for the spiked acid mine drainage and sewage wastewater effluents were 71% and 58% for the magnetic IIP and NIP, respectively. From powder X-ray diffraction analysis, application of the Scherrer equation yielded magnetic nanoparticles of an average mean diameter of 11.9 nm. Thermo-gravimetric analysis revealed that the HCl-leached magnetic polymers had a magnetite residual weight of 5%.     

Lithological and hydrochemical controls on distribution and speciation of uranium in groundwaters of hard-rock granitic aquifers of Madurai District,Tamil Nadu (India)

Uranium is a radioactive element normally present in hexavalent form as U(VI) in solution and elevated levels in drinking water cause health hazards. Representative groundwater samples were collected from different litho-units in this region and were analyzed for total U and major and minor ions. Results indicate that the highest U concentration (113 µg l^?1) was found in granitic terrains of this region and about 10 % of the samples exceed the permissible limit for drinking water. Among different species of U in aqueous media, carbonate complexes [UO₂(CO₃) ₂ ^2? ] are found to be dominant. Groundwater with higher U has higher pCO₂ values, indicating weathering by bicarbonate ions resulting in preferential mobilization of U in groundwater. The major minerals uraninite and coffinite were found to be supersaturated and are likely to control the distribution of U in the study area. Nature of U in groundwater, the effects of lithology on hydrochemistry and factors controlling its distribution in hard rock aquifers of Madurai district are highlighted in this paper.     

Selective binding of uranyl cation by a novel calmodulin peptide

A 33-amino acid peptide corresponding to the helix-loop-helix motif of the calcium binding site I of the protein calmodulin from Paramecium Tetraurelia has been synthesized its binding properties with heavy metal ions have been studied. Herein, we demonstrate that two mutations of two aspartic acid residues in the peptide sequence gave access to a new peptide, which was selective for the uranyl ion UO₂ ²⁺. This new peptide can be useful for the development of selective uranyl biosensors to monitor the presence of uranium in contaminated environments.     

Biosorption of Cu(II) and Zn(II) onto a lignocellulosic substrate extracted from wheat bran

We studied the removal of copper and zinc ions from aqueous solutions using a lignocellulosic substrate obtained by an acido-basic treatment of wheat bran. The sorption capacity of this material was investigated through batch and column experiments. Batch experimental results showed that the retention capacity of the lignocellulosic substrate was 0.20×10^–3 mol g^–1 at pH 4.5 for copper(II) and 0.24×10^–3 mol g^–1 at pH 6.5 for zinc(II). Column experiments showed a reduced sorption capacity for both ions compared to batch experiments. Batch and column data were analysed using the Langmuir equation in order to determine the affinity constant and the binding capacity of the sorbent and to compare both retention processes.     

Decrease of Pb bioavailability in solis by addition of phosphate ions

Bioavailability of Pb in contaminated soils can be highly decreased by conversion of labile Pb species into pyromorphite Pb₅(PO₄)₃Cl, induced by amendment with a phosphate source. However, PO₄ ³⁻ can be specifically adsorbed on goethite α-Fe(OH)₃ present in soils. We demonstrate that despite the stability of phosphate ions adsorbed on goethite surface, the reaction between goethite-adsorbed phosphates and aqueous lead in the presence of Cl⁻ results in crystallization of pyromorphite. Two morphological forms of pyromorphite formed on goethite were observed: 1) incrustations, indicating direct reaction of Pb and Cl ions with PO₄ ³⁻ adsorbed on goethite surface, and 2) aggregates of pyromorphite crystals indicating that the reaction with PO₄ ³⁻ ions took place in the volume of the solution. This suggests that precipitation of pyromorphite is faster than desorption of phosphates and that aqueous Pb may serve as a sink for phosphate ions by shifting the equilibrium and inducing PO₄ ³⁻ desorption.     

Preconcentration of tin in environmental and biological samples by ion exchange using modified Amberlite XAD-2

Utilization of Amberlite XAD-2 surface modified by covalent immobilization of brilliant green through an azo spacer for adsorptive enrichment of Sn(II) from environmental and biological samples was highlighted. The resulting resin was characterized by Fourier transform infrared spectroscopy, elemental analysis, thermogravimetric analysis, and scanning electron microscopy. The resin retained Sn(II) ions at an optimum pH of 9.5 with a sorption capacity of 40 mg g^?1. The modified sorbent could be reused for 10 cycles without significant changes in sorption capacity. The recovery of Sn(II) was 98% when eluted with 0.1 mol L^?1 ethylenediaminetetraacetic acid. Scatchard analysis revealed that binding sites in the modified resin were homogeneous. The equilibrium adsorption data were analyzed using the Langmuir, Freundlich, Temkin, and Redlich–Peterson isotherm models. The method was applied with satisfactory results for determination of Sn(II) ions in human plasma and sea water.     

Removal and recovery of uranium(VI) by adsorption onto a lignocellulosic-based polymeric adsorbent containing amidoxime chelating functional group

A new adsorbent (ABS) with amidoxime functional group was prepared through graft polymerization of acrylonitrile onto banana stem (BS) using ceric ammonium nitrate (CAN)/HNO₃ initiator system, followed by treatment with hydroxylamine hydrochloride in alkaline solution. Infrared spectroscopy, surface area analyzer, thermogravimetry, and potentiometric titration were used for the characterization of the adsorbent. Effective removal of U(VI) ions was demonstrated at the pH range 4.0–6.0. The mechanism for the removal of U(VI) ions by ABS was based on complexation adsorption model. Equilibrium was achieved in approximately 3 h. The experimental kinetic data were analyzed using first-order, second-order, and Elovich kinetic models, and are well fitted with second-order kinetics. The temperature dependence indicates an exothermic process. U(VI) adsorption was found to decrease with increase of ionic strength. The Freundlich isotherm model fitted the experimental equilibrium data well. The adsorption efficiency was tested using synthetic nuclear industry effluents. The maximum adsorption capacity for U(VI) removal was found to be 80 mg g^-1 at 20°C. Adsorbed U(VI) ions were desorbed effectively, about 99% by 0.2 M HCl. Repeated adsorption/desorption cycles show the feasibility of the ABS for the removal of U(VI) ions from water and nuclear industry effluents.     

Removal of cadmium(II), lead(II), and chromium(VI) ions from aqueous solution using clay

Removal of cadmium(II), lead(II), and chromium(VI) from aqueous solution using clay, a naturally occurring low-cost adsorbent, under various conditions, such as contact time, initial concentration, temperature, and pH has been investigated. The sorption of these metals follows both Langmuir and Freundlich adsorption isotherms. The magnitude of Langmuir and Freundlich constants at 30°C for cadmium, lead, and chromium indicate good adsorption capacity. The kinetic rate constants (K _ad) indicate that the adsorption follows first order. The thermodynamic parameters: free energy change (ΔG ^o), enthalpy change (ΔH ^o), and entropy change (ΔS ^o) show that adsorption is an endothermic process and that adsorption is favored at high temperature. The results reveal that clay is a good adsorbent for the removal of these metals from wastewater.     

Quantitative analysis and sorption of cadmium in environmental samples with a functionalized synthetic polymer

Quantitative analysis of cadmium in environmental samples was achieved with a polymeric sorbent synthesized by copolymerization of N,N-dimethylacrylamide and allyl glycidyl ether/iminodiacetic acid as chelating monomers with N,N′-methylenebisacrylamide as cross-linker. The polymer was characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, elemental analysis, and scanning electron microscopy. The sorption capacity of the functionalized sorbent was 70 mg g^?1. The equilibrium sorption data of Cd(II) on polymeric sorbent were analyzed using Langmuir, Freundlich, Temkin, and Redlich–Peterson models. Based on equilibrium adsorption data, the constants at pH 4.2 and 20 °C were determined for the first three as 0.33 (L mg^?1), 17.5 (mg g^?1) (L mg^?1)^1/n, and 12.9 (J mol^?1). Recovery of 94% of the metal ion was obtained with 0.5 mol L^?1 nitric acid as an eluting agent.     

A contribution to the study of phosphate sorption by three Greek fly ashes

Three fly ashes from Greece, produced from lignite burning, proved efficient in removing phosphate from solution. Maximum amounts of phosphate removed ranged from 0.064 to 0.099 mmol PO³ ₄ ^– per g of material. Fly ashes that contained higher amounts of calcite and anhydrite seemed to be better sinks for phosphate. From the various adsorption isotherm equations tested, the Langmuir equation described phosphate sorption satisfactorily. Although, the exact mechanism of phosphate sorption could not be revealed, it is believed that it involved an adsorption and/or precipitation process.     

Chemically modified biochar produced from conocarpus waste increases NO<Subscript>3</Subscript> removal from aqueous solutions

Biochar has emerged as a universal sorbent for the removal of contaminants from water and soil. However, its efficiency is lower than that of commercially available sorbents. Engineering biochar by chemical modification may improve its sorption efficiency. In this study, conocarpus green waste was chemically modified with magnesium and iron oxides and then subjected to thermal pyrolysis to produce biochar. These chemically modified biochars were tested for NO₃ removal efficiency from aqueous solutions in batch sorption isothermal and kinetic experiments. The results revealed that MgO-biochar outperformed other biochars with a maximum NO₃ sorption capacity of 45.36 mmol kg^?1 predicted by the Langmuir sorption model. The kinetics data were well described by the Type 1 pseudo-second-order model, indicating chemisorption as the dominating mechanism of NO₃ sorption onto biochars. Greater efficiency of MgO-biochar was related to its high specific surface area (391.8 m² g^?1) and formation of strong ionic complexes with NO₃. At an initial pH of 2, more than 89 % NO₃ removal efficiency was observed for all of the biochars. We conclude that chemical modification can alter the surface chemistry of biochar, thereby leading to enhanced sorption capacity compared with simple biochar.     

Solid phase extraction of trace metals from environmental samples using Amberlite XAD-7 loaded with 2-hydroxy-propiophenone-4-phenyl-3-thiosemicarbazone and determination by inductively coupled plasma–atomic emission spectrometry

A method for the solid phase extraction of trace metals, namely Co, Cu, Pb, Ni and Zn, from environmental and biological samples using column Amberlite XAD-7 loaded with 2-hydroxy-propiophenone-4-phenyl-3-thiosemicarbazone (HPPPTSC) and determination by inductively coupled spectrometry (ICP–AES) has been developed. The reagent has the capacity to form chelate complexes with the metals because of three binding sites in the reagent molecule. The optimum experimental conditions for the quantitative sorption of five metals, pH, effect of flow rate, concentration of eluent, sorption capacity and the effect of diverse ions on the preconcentration of analytes have been investigated. The sorption capacity of the resin has 83, 127, 35, 88 and 85?µmol?g^?1 for Co²⁺, Cu²⁺, Pb²⁺, Ni²⁺ and Zn²⁺, respectively. The preconcentration factors for Co²⁺, Cu²⁺, Pb²⁺, Ni²⁺ and Zn²⁺ were 100, 110, 120, 140 and 150, respectively. The accuracy of the proposed procedure was evaluated by standard reference materials. The achieved results were in good agreement with certified values. The proposed method was applied for the determination of trace metals in river water and plant leaves.     

The effect of selenium on fluoride — clay interactions: Possible environmental health implications

Previous epidemiological studies have shown that dental fluorosis is endemic in the lowland, dry zone of Sri Lanka, which is considered to be an area in which excessive quantities of fluorides are present in the drinking water supplies. It has been found that kaolinitic clay forms a suitable raw material in the defluoridation of water.It is shown that there is a noticeable effect of selenium and media pH on the reactions involved in the interaction of fluoride with clay. In this study, 1 mM fluoride solutions containing SeO ₃ ^2– (selenite) concentrations of 0 mM, 0.1 mM, 0.5 mM and 1 mM were used in the reactions with kaolinitic clay. The effect of pH was monitored in the range 4 to 8. It was observed that fluoride adsorption was maximum at a pH of 5.6 without either SeO ₃ ^2– or SeO ₄ ^2– , the adsorption capacity being 15.2 mol F^– g^–1 clay. However, when the SeO ₃ ^2– concentration was increased up to 0.5 mM at this optimum pH, the adsorption capacity reduced to 12.8 mol F^– g^–1 clay. Monitoring of the effect of SeO ₄ ^2– and media pH on fluoride adsorption showed that when the SeO ₄ ^2– concentration increases from zero to 0.1 mM, there is a reduction of fluoride adsorption capacity. However, when the SeO ₄ ^2– concentration is further increased from 0.1 mM to 1.0 mM, there was an increase in the fluoride adsorption capacity, indicating a more consistent effect of SeO ₃ ^2– on fluoride-kaolinitic clay interaction than SeO ₄ ^2– .Fluoride concentrations in drinking water supplies have a marked effect on dental health and the geochemistry of selenium appears to play an important role in the geochemical mobility of fluoride ions.     

1,3,5-triazine-triethylenetetramine polymer: an efficient adsorbent for removal of Cr(VI) ions from aqueous solution

The synthesis of 1,3,5-triazine-triethylenetetramine (TATETA), its characterization by infrared spectroscopy and elemental analysis, and its application for removal of Cr(VI) ions from aqueous solution is reported. The effects of pH, contact time, initial concentration of Cr(VI), sorbent dose, and temperature on adsorption were investigated and optimized by batch adsorption experiments. Adsorption was highest at acidic conditions with an equilibration time of 25 min. The adsorption followed a Langmuir model, with an adsorption capacity of 303 mg g^?1, was second order in its kinetics, and exothermic and thus spontaneous.     

Removal of Eu3+, Ce3+, Sr2+, and Cs+ ions from radioactive waste solutions by modified activated carbon prepared from coconut shells

As a biomass agricultural waste material, coconut shells were used for the preparation of high-quality modified activated carbon. Chemical modification of the surface of the prepared activated carbon is done by oxidation using H₂O₂ and HNO₃, respectively. The surface area and pore volume of the coconut shells activated carbon are increased by the chemical modification, and followingly the removal of the metals is improved. The structural morphology and composition of the modified activated carbon coconut shells (MACCS) were evaluated by Fourier transform infrared (FTIR) spectra, thermogravimetric analysis–differential thermal analysis (TGA-DTA), scanning electron microscope (SEM), X-ray diffraction (XRD), surface area analysis (SAA), X-ray fluorescence (XRF), and carbon, hydrogen, nitrogen, and sulfur (CHNS) elemental analysis. The prepared MACCS has reasonably good chemical stability. The influence of solution pH, contact time, adsorbent dosage, adsorption temperature, initial metal concentrations, and interfering ions on the adsorption performance of the investigated ions onto the prepared sorbent was examined by a batch method. The selectivity sequence for sorption of Eu³⁺, Ce³⁺, Sr²⁺, and Cs⁺ ions on MACCS was found to be Eu^3+?>?Ce^3+?>?Sr^2+?>?Cs⁺. The saturation capacities of MACCS for the studied metal ions were found to be 136.84, 85.55, 69.85, and 60.00?mg?g^?1 for Eu³⁺, Ce³⁺, Sr²⁺, and Cs⁺ ions, respectively. The thermodynamic parameters, ΔH°, ΔS°, and ΔG° were also evaluated.     

Seasonal changes in inorganic nutrient concentration in the alexandria western harbour (Egypt)

Surface and bottom water samples were collected on a monthly basis from six locations in the Alexandria Western Harbour between April 2002 and March 2003. Total nitrogen, ammonia, nitrite, nitrate, total phosphorus, reactive phosphate and silicate were analysed. The average content of total nitrogen ranged from 81.1 to 65.7?µmol?l^?1 in the surface and bottom waters, respectively, while ammonia ranged from 13.77 to 15.79?µmol?l^?1 in surface and bottom waters, respectively. Also, the average concentration of nitrite was relatively higher in surface waters than in bottom waters (0.89 and 0.61?µmol?l^?1, respectively). The results of this study also indicated a considerable temporal variation in nitrate concentrations which ranged from 1.12 to 13.83?µmol?l^?1. Total phosphorus displayed an irregular pattern throughout the year, ranging from 1.9 to 11.8?µmol?l^?1 in surface waters and from 1.7 to 9.1?µmol?l^?1 in bottom waters. The results of PO₄-P analysis showed higher values in surface waters (0.28–2.75?µmol?l^?1) than in bottom waters (0.10–1.70?µmol?l^?1). The average concentration of silicates was relatively lower in the surface than in the bottom waters (8.97 and 10.1?µmol?l^?1, respectively). The analysis of variance (ANOVA) among seasons and sites revealed significant differences for ammonia, total nitrogen and phosphate, while nitrate showed no significant differences among stations. Finally, silicate did not show any significant variance among sites and seasons (ANOVA, P?>?0.05).     

A comparative study of modified and unmodified maize tassels for removal of selected trace metals in contaminated water

Powdered maize tassels were studied and found to exhibit metal sorption properties due to the availability of functional groups. The tassels have a high amount of soluble organic substances that can dissolve in aqueous media, contributing to secondary pollution during a water treatment process. A chelating agent was chemically attached on the maize tassels with a view to increase the sorption capacity, minimize leaching, and enhance the tassels’ stability. Thermogravimetric analysis confirmed that modification improved their thermal stability to withstand temperatures above 600°C as well as reduced the “secondary pollution”. The modified sorbent was employed for the sorption of lead, copper, and cadmium ions in both the model solutions and the real samples. The contact time and pH were optimized after which Langmuir and Freundlich isotherms were applied to the data. The sorption capacities for Cu²⁺, Cd²⁺, and Pb²⁺ improved from 3.4, 0.8, and 1.7?g?kg^?1, respectively, to 6.3, 2.6, and 2.6?g?kg^?1 in the same order. The sorbent was shown to remove up to 95% of the metals in less than 10 min. This study has a potential application for the remediation of polluted waters.