Biosorption of uranium by immobilized cells of Rhodotorula glutinis

Biosorption of uranium ions from diluted solution (≤40 mg L^?1) onto immobilized cells of Rhodotorula glutinis was investigated in a batch system. Equilibrium, kinetic and thermodynamic studies were conducted by considering the effect of initial uranium concentration, contact time and temperature. Non-linear forms of Langmuir, Freundlich and Sips isotherm models were used to fit the equilibrium data, Sips model was designated as the best one. Kinetic data were simulated by non-linear pseudo-first-order, pseudo-second-order and intra-particle diffusion equations. Pseudo-first-order kinetic equation described the experimental data better than pseudo-second-order equation and intra-particle diffusion equation can fit the kinetic data with two independent curves. Thermodynamic parameters, including ?H ⁰, ?G ⁰ and ?S ⁰, were evaluated, the sorption process was determined to be spontaneous and endothermic. Uranium sorption from pure uranium solutions and uranium pit wastewater by immobilized biomass and blank beads, as well as the regeneration results indicated that immobilized R. glutinis can be use to recovery uranium from uranium pit wastewater.     

Preparation of sol–gel materials doped with ionic liquid and extractant for cerium(III) extraction

Silica materials (ILDEHPASGs) consisting of ionic liquids and di-(2-ethylhexyl)phosphoric acid (DEHPA) for Ce(III) extraction was prepared by a sol–gel method using the hydrophobic ionic liquid 1-octyl-3-methylimidazolium hexafluorophosphate ([C₈mim]PF₆) as porogen and solvent medium. The ILDEHPASGs were characterized by scanning electron microscopy, Brunauer–Emmett–Teller surface area, Fourier transform infrared, and thermogravimetric analyses. The results indicated the doping of DEHPA and [C₈mim]PF₆ in ILDEHPASG-3 would evidently affect the formation of porous structure of sol–gel materials. ILDEHPASG-3 also possessed more channels and macropores than the blank sorbent; the surface area and pore volume of ILDEHPASG-3 were 409 m² g^?1 and 0.444 cm³ g^?1, respectively. [C₈mim]PF₆ and DEHPA were only physically confined or entrapped in the growing covalent silica network rather than chemically bound to the inorganic matrix. The majority of [C₈mim]PF₆ and DEHPA were stably immobilized in the gel. Then, the effects of contact time and pH were determined. The results showed the sorption of Ce(III) strongly depended on the contact time and pH, and ILDEHPASGs had high sorption ability for Ce(III). The results were analyzed by both Langmuir and Freundlich adsorption isotherm models, and the latter was found to give a better fit.     

Synthesis of core–shell structured Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@carboxymethyl cellulose magnetic composite for highly efficient removal of Eu(III)

In this work, a carboxymethyl cellulose (CMC)-modified Fe₃O₄ (denoted as Fe₃O₄@CMC) composite was synthesized via a simple co-precipitation approach. Fourier transform infrared spectroscopy, zeta potential and thermogravimetric analysis results indicated that CMC was successfully coated on the Fe₃O₄ surfaces with a weight percent of ~30 % (w/w). The prepared Fe₃O₄@CMC composite was stable in acidic solution and could be easily collected with the aid of an external magnet. A batch technique was adopted to check the ability of the Fe₃O₄@CMC composite to remove Eu(III) as a function of various environmental parameters such as contact time, solution pH, ionic strength, solid content and temperature. The sorption kinetics process achieved equilibrium within a contact time of 7 h. The sorption isotherms were well simulated by the Langmuir model, and the maximum sorption capacity at 293 K was calculated to be 2.78 × 10^?4 mol/g, being higher than the series of adsorbent materials reported to date. The ionic strength-independent sorption behaviors, desorption experiments by using ammonium acetate and disodium ethylenediamine tetraacetate as well as the spectroscopic characterization suggested that Eu(III) was sequestrated on the hydroxyl and carboxyl sites of Fe₃O₄@CMC via inner-sphere complexation. Overall, the Fe₃O₄@CMC composite could be utilized as a cost-effective adsorbent for the removal of trivalent lanthanide/actinides (e.g., ^152+154Eu, ²⁴¹Am and ²⁴⁴Cm) from radioactive wastewater.     

Polarographic investigation of the tautomeric transformations of β-formylacrylic acid and of the hydrolysis of its ethyl pseudoester. I

A polarographic method was used to study the cis (HA_c), trans (HA_t), and lactol (L) forms of formylacrylic acid (FAA) and its ethyl pseudoester (E) and their interconversions. It is shown that the slow step in the process E?L?HA_c?A_c ^? is hydrolysis of E. The pH of the solution has a substantial effect on the state of the equilibrium in all of the steps because of the shift in the equilibrium HA_c?A_c ^?. The equilibrium constants of all of the steps and the rate constant of the hydrolysis of E as a function of the pH of the solution were found. The most stable of the three forms of FAA is HA_t. The cis form exists only in solutions. The polarographic reduction of HA_c and HA_t at the ethylene bond proceeds at more positive potentials than the reduction of maleic and fumaric acids. In contrast to HA_c, HA_t does not form a polarographic dissociation curve; this is explained by the closeness of the potentials for the reduction of HA_t and A_t ^?.     

Monitoring 60Co activity for the characterization of the sorption process of Co2+ ions in municipal activated sludge

In large volumes produced activated sludges from wastewater treatment plants (WWTPs) with low concentrations of heavy metals can be utilized as agricultural fertilizers and soil conditioners. Increased contents of toxic xenobiotics are limiting factors that affect the utilization of these heterogeneous wastes. The main aim of our paper was to show the utilization of dried activated sludge (DAS) from municipal WWTP as potential Co²⁺ ions sorbent i.e. for non-agricultural purposes. The radio indicator method by radionuclide ⁶⁰Co and γ-spectrometry for characterization DAS sorption properties was used. DAS soluble and solid fractions were characterized by biochemical, ETAAS and CEC analysis. The sorption of Co²⁺ ions by DAS was rapid process and equilibrium was reached within 2 h. Sorption capacity of DAS (Q) increased with the initial concentration of CoCl₂ in the range from 100 to 4,000 μmol l^?1, reaching 20 and 160 μmol g^?1. Obtained Q values were depent on pH value from 2.0 to 8.0. The maximum sorption capacity (Q _max) of DAS at pH 6 calculated from mathematical model of Langmuir adsorption isotherm was 175 ± 9 μmol g^?1. FT-IR analyses showed the crucial role of carboxyl functional groups of DAS surfaces on cobalt uptake. For confirmation ion-exchange mechanism in sorption process of Co²⁺ ions by DAS scanning electron microscopy and EDX analysis were used.     

Sorption separation of Eu and As from single-component systems by Fe-modified biochar: kinetic and equilibrium study

The utilization of carbonaceous materials in separation processes of radionuclides, heavy metals and metalloids represents a burning issue in environmental and waste management. The main objective of this study was to characterize the effect of chemical modification of corncob-derived biochar by Fe-impregnations on sorption efficiency of Eu and As as a model compounds of cationic lanthanides and anionic metalloids. The biochar sample produced in slow pyrolysis process at 500 °C before (BC) and after (IBC) impregnation process was characterized by elemental, FTIR, SEM-EDX analysis to confirm the effectiveness of Fe-impregnation process. The basic physico-chemical properties showed differences in surface area and pH values of BC- and IBC-derived sorbents. Sorption processes of Eu and As by BC and IBC were characterized as a time- and initial concentration of sorbate-dependent processes. The sorption equilibrium was reached for both sorbates in 24 h of contact time. Batch equilibrium experiments revealed the increased maximum sorption capacities (Q _max) of IBC for As about more than 20 times (Q _max BC 0.11 and Q _max IBC 2.26 mg g^?1). Our study confirmed negligible effect of Fe-impregnation on sorption capacity of biochar for Eu (Q _max BC 0.89 and Q _max IBC 0.98 mg g^?1). The iron-impregnation of biochar-derived sorbents can be utilized as a valuable treatment method to produce stable and more effective sorption materials for various xenobiotics separation from liquid wastes and aqueous solutions.     

Enhanced sorption of perfluorooctane sulfonate and Cr(VI) on organo montmorillonite: influence of solution pH and uptake mechanism

An effective sorbent to remove the perfluorooctane sulfonate (PFOS) and hexavalent chromium (Cr(VI)) simultaneously from simulating plating wastewater was prepared in this study. The removal of Cr was pH-dependent. However, PFOS removal on organo-montmorillonites (Mts) was not sensitive to pH changes. The presence of micelles and hemi-micelles resulted in an enhanced PFOS sorption capacity which reached 1,000 mg/g on the hexadecyltrimethylammonium bromide (HDTMAB) modified montmorillonite. The cationic surfactants on organo-Mts were largely responsible to the hydrophobic partition. For Cr(VI), the stable coordination compounds between amido, sulfhydryl groups and HCrO₄ ^? were beneficial to its sorption on AET–Mt and AET–HDTMAB–Mt (AET, 2-aminoethanethiol hydrochloride). The result indicated that the AET–HDTMAB–Mt was highly effective for removing both PFOS and Cr(VI) simultaneously, and their sorption capacities reached 890 and 14 mg/g respectively.     

Entrapment of Humic Acid in a Sol-Gel Matrix—A New Tool for Sorption Studies

Humic substances are natural complexed mixtures of organic compounds originated from the decomposition of plant and animal residues. These compounds are ubiquitous in soils, sediments, surface waters and groundwaters. They contain both hydrophobic and hydrophilic moieties, able to interact with hydrophobic organic contaminants and with heavy metals. These sorption interactions play a crucial role in contaminants fate and transport and their understanding and quantification are essential for modeling and predictions. However, sorption analyses frequently suffer from experimental problems. A novel idea presented in this study is to use sol-gel as an inert matrix to immobilize (entrap) specific, well defined, humic molecules which then be used in sorption studies. We developed a successful procedure for the immobilization of humic acid (HA) in a sol-gel matrix. After gelation and drying, the doped gel was crushed and washed several times, yielding a very stable product. It was then used in a series of batch experiments, studying the sorption of several polycyclic aromatic hydrocarbons (PAHs) with Aldrich HA. The sorption coefficients (K _oc) obtained with the immobilized HA were highly correlated with the values expected based on the hydrophobicity of the contaminants. We concluded that the entrapped HA retained its original properties and that it was accessible to the external contaminants through the pore network.     

Comparison of ordered mesoporous materials sorption properties towards amino acids

The adsorption of amino acids such as l-phenylalanine and l-histidine was carried out on a series of mesoporous carbons obtained with the use ordered silicas KIT-6, SBA-16, SBA-15 as templates and furfuryl alcohol as carbon precursor. Small angle XRD analysis confirmed the ordered mesoporous structures of all materials obtained. They were also characterised by well-developed surface areas and high pore volumes. Adsorption behaviour of amino acids on ordered mesoporous carbons was investigated in potassium phosphate buffer solutions with adjustable l-phenylalanine and l-histidine concentration, ion strength, and pH. The highest sorption capacity towards the amino acids were observed at pH close to the isoelectric point of l-phenylalanine (pI = 5.48) and l-histidine (pI = 7.59). Electrostatic, hydrophobic and steric interactions had very strong effect on the adsorption of amino acids on mesoporous carbons. The amount of l-phenylalanine and l-histidine adsorbed decreased in the following sequence: C_KIT-6 > C_SBA-16 > C_SBA-15 that was strongly related to their structure, surface areas and average pore diameters.     

Sorption of Cd(II) onto carbon-based materials—a comparative study

The sorption behaviour of Cd(II) on three carbon-based materials including activated carbon (AC), carbon nanotubes (CNTs) and carbon-encapsulated magnetic nanoparticles (CEMNPs) which were prepared under similar conditions by nitric acid treatment were investigated. Generally, sorption of cadmium on these materials increased with the increase of pH. For AC and CNTs very similar results were obtained, while CEMNPs exhibits much higher affinity for Cd(II) despite of almost the same surface acidity. Thus, cadmium retention on tested sorbents was more dependent on the concentration of specific active sites than the total surface area available. The equilibrium sorption data were better fitted to Langmuir isotherm. The theoretical saturation capacity of the monolayer derived from this model at pH 8.0 for AC, CNTs and CEMNPs are 9.91 mg g^?1, 20.37 mg g^?1 and 91.0 mg g^?1, respectively. The kinetic of Cd(II) sorption is fitted for pseudo-second order equation and could be described as a combination of film diffusion and intra-particle diffusion, whereby the last one dominates. The experimental parameters for preconcentration of cadmium on a microcolumn packed with CEMNPs prior to its determination by flame atomic absorption spectrometry have been investigated. Cadmium can be quantitatively retained at pH 8 from sample volumes up to 150 mL and then eluted completely with 3 mL of 0.5 mol L^?1 HNO₃.     

Potential Hydrothermal-Humification of Vegetable Wastes by Steam Explosion and Structural Characteristics of Humified Fractions

In this work, steam explosion (SE) was exploited as a potential hydrothermal-humification process of vegetable wastes to deconstruct their structure and accelerate their decomposition to prepare humified substances. Results indicated that the SE process led to the removal of hemicellulose, re-condensation of lignin, degradation of the cellulosic amorphous region, and the enhancement of thermal stability of broccoli wastes, which provided transformable substrates and a thermal-acidic reaction environment for humification. After SE treatment, total humic substances (HS), humic acids (HA_s), and fulvic acids (FA_s) contents of broccoli samples accounted for up to 198.3 g/kg, 42.3 g/kg, and 166.6 g/kg, and their purification were also facilitated. With the increment of SE severity, structural characteristics of HA_s presented the loss of aliphatic compounds, carbohydrates, and carboxylic acids and the enrichment of aromatic structures and N-containing groups. Lignin substructures were proved to be the predominant aromatic structures and gluconoxylans were the main carbohydrates associated with lignin in HA_s, both of their signals were enhanced by SE. Above results suggested that SE could promote the decomposition of easily biodegradable matters and further polycondensation, aromatization, and nitrogen-fixation reactions during humification, which were conducive to the formation of HA_s.     

Study of the gadolinium sorption on the C100 ion-exchange resin for the development of the antineutrino detector targets

Adsorption of the gadolinium from H₂O and HCl solutions on the ion-exchange resin C100 is investigated. The experiments were carried out by varying the acidity of the liquid phase, the amount of sorbent, and the temperature. The maximal sorption of the ions Gd³⁺ is observed from the solution 0–0.2 M HCl under optimal conditions, the sorption reaches more than 99.5%. Sorption of Gd³⁺ on C100 from H₂O solution occurs most intensively during the first 3 min then for 30 min the system smoothly comes to equilibrium. The maximal sorption capacity of the resin C100 amounted to 1.2 ± 0.1 mmol g^?1. The thermodynamic parameters of sorption: ΔG = ? 24.20 kJ mol^?1, ΔS = ? 90.27 J mol^?1 K^?1, ?H = ? 50.93 kJ mol^?1 were evaluated. It is shown that the sorption of gadolinium on the ion-exchange resin C100 is described by models of kinetically pseudo-first and pseudo-second order. It is established that the Gd³⁺ sorption on the C100 resin is reversible second order chemical reaction.     

Biosorption of uranyl ions from aqueous solution by Saccharomyces cerevisiae cells immobilized on clinoptilolite

This study deals with the uptake of uranyl ions from aqueous solution using bio-modified natural clinoptilolite. The biosorption experiments were carried out in a batch system. Cell immobilization process and sorption of uranyl ions were confirmed by scanning electron microscopy and inductively coupled plasma-optical emission spectroscopy techniques, respectively. The adsorption equilibrium was reached in 4 h, the optimum pH was 4.5 and the temperature had no significant effect on the uranyl biosorption. The experimental data were well fitted with Langmuir isotherm and pseudo-second-order kinetic models. The maximum sorption capacity of cell immobilized clinoptilolite was 0.148 mmol ( \( {\text{UO}}_{2}^{2 + } \) ) g^?1 dry sorbent.     

Biosorption of lanthanum from aqueous solutions using magnetic alginate beads

Magnetic alginate beads are potential biosorbent for sorption of lanthanum(III) from an aqueous medium. Batch experiments were carried out to study the equilibrium, kinetics, and thermodynamics of lanthanum sorption. The effects of initial solution pH, initial lanthanum concentration, and temperature on lanthanum sorption were investigated. The optimum pH value was defined to be 4. Kinetic and isotherm experiments were carried out at the optimum pH. It was enough to reach the adsorption equilibrium at 4 hours, and the maximum uptake capacity was (1.8 mmol g^?1) at 25°C. Uptake kinetics and sorption isotherms were obtained and modeled using conventional and simple equations: best results were respectively obtained with the pseudo-second-order rate equation and the Langmuir equation. The La(III) loaded magnetic alginate beads were regenerated using 0.1 M CaCl₂ without activity loss.     

Application of modified multiwall carbon nanotubes as a sorbent for zirconium (IV) adsorption from aqueous solution

Modified multiwall carbon nanotubes (MWCNTs) by nitric acid solution were used to investigate the adsorption behavior of zirconium from aqueous solution. Pristine and oxidized MWCNTs were characterized using nitrogen adsorption/desorption isotherm, Boehm’s titration method, thermogravimetry analysis, transmission electron microscopy and Fourier transform infrared spectroscopy. The results showed that the surface properties of MWCNTs such as specific surface area, total pore volume, functional groups and the total number of acidic and basic sites were improved after oxidation. These improvements are responsible for their hydrophobic properties and consequently an easy dispersion in water and suitable active sites for more adsorption of zirconium. The adsorption of Zr(IV) as a function of initial concentration of zirconium, contact time, MWCNTs dosage, HCl and HNO₃ concentration and also ionic strength was investigated using a batch technique under ambient conditions. The experimental results indicated that sorption of Zr(IV) was strongly influenced by zirconium concentrations, oxidized MWCNTs content and acid pH values. The calculated correlation coefficient of the linear regressions values showed that Langmuir model fits the adsorption equilibrium data better than the Freundlich model. Kinetic data of sorption indicated that equilibrium was achieved within 60 min and the adsorption process can be described by the pseudo second-order reaction rate model. Based on the experimental results, surface complexation is the major mechanism for adsorption of Zr(IV) onto MWCNTs. Also, Study on the desorption process of zirconium showed that the complete recovery can be obtained using nitric or hydrochloric acids of 4 M.     

Adsorption characteristics of tributyltin on municipal solid waste compost

The sorption behaviour of tributyltin (TBT) from reconstituted seawater onto municipal solid waste (MSW) compost was investigated to give first insights into the equilibrium and kinetic behaviour of this process. The rate of adsorption, the influence of pH, and the adsorbate hydrophobicity on the partitioning process were investigated. Adsorption kinetics indicated an initial fast rate of adsorption of TBT followed by a slower rate. The similarity of Freundlich sorption and desorption coefficients for TBT showed that the sorption process is also reversible, similar to that for the adsorption of TBT onto marine sediments. It was found that the adsorption capacity for TBT onto compost was highest at pH 6.7, and for other organotins it increased with increasing adsorbate hydrophobicity, following the trend tripropyltin < TBT < tripentyltin. The use of washed MSW compost as a sorbent for the purification of TBT‐contaminated wash waters as generated in large quantities during hull cleaning in dry docks is suggested as a mitigatory measure against pollution of the marine environment by TBT. Calculations suggest that modest amounts of compost will likely be required to treat the contaminated wastewaters generated from the Malta dry docks if a multiple batch system is adopted. Copyright © 2005 John Wiley & Sons, Ltd.     

Effect of grain size on the sorption and desorption of SeO4 2− and SeO3 2− in columns of crushed granite and fracture infill from granitic water under dynamic conditions

The sorption of 2 × 10^?5 mol/dm³ Na₂SeO₄ and Na₂SeO₃ dissolved in synthetic granitic water (SGW) were investigated in columns of crushed granite and fracture infill (clay minerals) of various grain sizes. Desorption was studied using pure SGW. The goal of study was the quantification of the effect of grain size on the retardation and distribution coefficients of SeO₄ ^2? and SeO₃ ^2?, as well as on the other transport parameters (Peclet number and hydrodynamic dispersion coefficient). A model based on the erfc-function, assuming a non-linear reversible equilibrium sorption/desorption isotherm, was used for evaluation of sorption/desorption and transport parameters. The determination of selenium was performed using an ICP-MS technique. The experimental breakthrough curves were fitted using non-linear regression procedure, in the course of which the parameters mentioned were sought. Summing up, no sorption was recorded in the case of SeO₄ ^2? under these conditions. The values of retardation coefficients were practically one for all studied grain sizes. On the other hand, significant sorption was found for SeO₃ ^2?: depending on the grain size, the retardation coefficients varied between 1.6–8.7 in pure granite and 1.8–37.2 in infill materials. These values correspond to distribution coefficients of 0.2–2.5 and 0.2–12.7 cm³/g, respectively. The both parameters have similar values in a case of desorption which reflects the reversible character of sorption process. It was found that retardation and distribution coefficients and sorption capacity for SeO₃ ^2? also increase with decreasing grain size.     

Sorption of plutonium from low level liquid waste using nano MnO2

Nano-crystalline MnO₂ has been synthesized by the method of alcoholic hydrolysis of KMnO₄ and its potential as a sorbent for plutonium present in the low level liquid waste (LLW) solutions was investigated. The kinetic studies on the sorption of Pu by MnO₂ reveal the attainment of equilibrium sorption in 15 h, however 90 % of sorption could be achieved within an hour. In the studies on optimization of the solution conditions for sorption, it was observed that the sorption increases with the pH of the aqueous solution, attains the maximum value of 100 % at pH = 3 and remains constant thereafter. The sorption was found to be nearly independent of the ionic strength (0.01–1.0 M) of the aqueous solutions maintained using NaClO₄, indicating the inner sphere complexation between the Pu⁴⁺ ions and the surface sites on MnO₂. Interference studies with different fission products, viz., Cs⁺, Sr²⁺ and Nd³⁺, revealed decrease in the percentage sorption with increasing pH of the suspension indicating the competition between the metal ions. However, at the metal ion concentrations prevalent in the low level liquid waste solutions, the decrease in the Pu sorption was only marginally decreased to 90 % at pH = 3, the decrease being more in the case of Nd³⁺ than that in the case of Cs⁺. This study, therefore, shows nano-crystalline MnO₂ can be used as a sorbent for separation of Pu from LLW solutions.     

Encapsulation of silica nano-spheres with polymerized ionic liquid for selective isolation of acidic proteins

A nanocomposite is prepared by encapsulating silica nano-spheres with polymerized ionic liquid in aqueous medium without use of any organic solvents. Vinyl groups are covalently introduced on to the surface of silica nano-spheres, which are then encapsulated by copolymerization of 1-vinyl-3-ethylimidazolium bromide (monomer) and 1,4-butanediyl-3,3′-bis-l-vinylimidazolium dibromide (cross-linker) at room temperature. The derived nanocomposite, PIL@SiO₂, provides a green adsorbent for protein sorption. PIL@SiO₂ is selective toward acidic proteins, and its selectivity can be controlled via varying the amount of monomer used in the copolymerization process. At pH 6.0, use of 5 mg PIL@SiO₂ nanocomposite results in a sorption efficiency of up to 95 % for 200 mg L^?1 ovalbumin in 1 mL sample solution. Electrostatic and hydrophobic interactions between PIL@SiO₂ and protein species dominate the adsorption process. The ovalbumin adsorption behavior is consistent with the Langmuir model, giving a sorption capacity of 333.3 mg g^?1. The retained ovalbumin is recovered by elution with 0.2 % SDS solution. Circular dichroism spectra reveal virtually no change to the α-helix content of ovalbumin after elimination of SDS by use of dialysis. In summary, high-purity ovalbumin is isolated from chicken egg-white by use of the PIL@SiO₂ nanocomposite as adsorbent.