Sorption behaviour of nanocrystalline MOR type zeolite for Th(IV) and Eu(III) removal from aqueous waste by batch treatment

The nanocrystalline mordenite (MOR) type zeolite materials with initial chemical composition Na(2)O:Al(2)O(3):10SiO(2):48H(2)O have been synthesized under hydrothermal conditions. MOR1 and MOR2 are spherically shaped nanocrystals, whereas MOR3 and MOR4 have rod-like morphology. This paper reports the sorption characteristics of MOR analogues for Th(IV) and Eu(III) removal from aqueous nuclear waste. Sorption of Th(IV) and Eu(III) on MOR1, MOR2, MOR3 and MOR4 in a single component system with varying initial metal ion concentration, solution pH, contact times, sorbent dose and temperatures has also been investigated. Further, the Langmuir and Freundlich sorption models have been applied to describe equilibrium isotherms at different temperatures. The adsorption capacity increases largely with increasing solution pH and temperature of the system. Specific surface area and pore volume have been investigated by Brunauer-Emmett-Teller (BET) method. The N(2) adsorption isotherm presents a type IV isotherm with narrow hysteresis loop which indicates the presence of mesopores related to inter-particle voids. Thermodynamic results indicate that the sorption follows an endothermic physisorption process. It has been found that these exchangers have good sorption capacity and out of which MOR4 has highest sorption capacity. Thus, nanocrystalline MOR4 is proved to be good sorbent for both Th(IV) and Eu(III).     

Sorption studies of europium on cerium phosphate using Box-Behnken design

Amorphous cerium phosphate was prepared and characterized. Three-level Box-Behnken design (BBD) was employed to analyze the effect of process variables such as initial pH (2–6), contact time (60–180 min), and sorbent amount (0.05–0.15 g) on the sorption capacity of europium. Analysis of variance (ANOVA) revealed that the main effect of initial pH and sorbent amount has a substantial impact on the sorption of Eu(III). Probability F-value (F = 3 × 10^-3) and correlation coefficient (R2 = 0.97) point out that the model is in good accordance with experimental data. The maximum sorption capacity of Eu(III) was found to be 42.14 mg g^-1 at initial pH 6, contact time of 180 min, and a sorbent amount of 0.05 g. Sorption isotherm data was well explained by the Langmuir model and monolayer Eu(III) sorption capacity was obtained as 30.40 mg g^-1. Kinetic data were well described by the pseudo-second-order model. Thermodynamic data suggested that the process is endothermic and spontaneous.     

Sorption of Eu(III) onto Gaomiaozi bentonite by batch technique as a function of pH, ionic strength, and humic acid

The bentonite from Gaomiaozi county (Inner Mongolia, China) (denoted as GMZ bentonite) was characterized by X-ray powder diffraction and Fourier transform infrared spectroscopy. The effect of pH, contact time, ionic strength, humic acid (HA) and Eu(III) concentrations on Eu(III) sorption to the GMZ bentonite was studied by batch technique under ambient conditions. The sorption of Eu(III) on GMZ bentonite was strongly dependent on pH and independent of ionic strength. The sorption of Eu(III) on GMZ bentonite was mainly dominated by surface complexation rather than by ion exchange. The presence of HA enhanced Eu(III) sorption at low pH values, but decreased Eu(III) sorption at high pH values. The enhanced sorption of Eu(III) on GMZ bentonite at low pH was attributed to the strong complexation of Eu(III) with surface adsorbed HA on GMZ bentonite and the reduced sorption of Eu(III) at high pH was attributed to the formation of soluble HA–Eu complexes in aqueous solution. The strong sorption of Eu(III) on GMZ bentonite suggested that the GMZ bentonite could be used as the backfill material in nuclear waste disposal.     

Evaluation of Se(IV) removal from aqueous solution by GMZ Na-bentonite: batch experiment and modeling studies

Bentonite has been studied extensively because of its strong sorption and complexation ability. In this work, the sorption of Se(IV) on purified GMZ bentonite was investigated under ambient temperature as functions of contact time, pH, Se(IV) concentration and co-existing ion Eu(III) using batch techniques. Sorption kinetics of Se(IV) was successfully described by the pseudo-second-order rate equation. The sorption amount of Se(IV) was strongly dependent on the solution pH, and a positive effect was observed on Se(IV) and Eu(III) co-sorption when these two elements existed in the same system under high surface coverage of sorbent. Double layer model was set up and used to quantitatively interpret the sorption experimental data collected in binary and ternary sorption systems. From the experimental results, one can conclude that GMZ bentonite may have good potentialities for immobilizing selenium in nuclear wastes.     

Sorption and desorption of Eu(III) on alumina

Summary Effects of ionic strength and of fulvic acid on the sorption of Eu(III) on alumina were investigated by using a batch technique. The experiments were carried out at T=25±1 °C, pH 4-6 and in the presence of 1M NaCl. The results indicate that sorption isotherms of Eu(III) are linear at low pH values. The sorption-desorption of Eu(III) on alumina at pH 4.4 is reversible, but a sorption-desorption hysteresis is found at pH 5.0. Fulvic acid has an obvious positive effect on the sorption of Eu(III) on alumina at low pH values. The migration of Eu(III) in alumina was studied by using column experiments and ^152+154Eu(III) radiotracer at pH 3.8. For column experiments, Eu(III) sorbed on alumina can be desorbed completely from the solid surface at low pH values. The findings are relevant to the evaluation of lanthanide and actinide ions in the environment.     

Sorption of Eu(III) on GMZ bentonite in the absence/presence of humic acid studied by batch and XAFS techniques

Bentonite has been extensively studied because of its strong sorption ability and low permeability. In this work, the Na-bentonite from Gaomiaozi County (China) has been characterized by XRD, FTIR and acid-base titration. The sorption of Eu(III) on Na-bentonite in the absence/presence of humic acid (HA) was studied at T = 25 ± 2 °C and in 0.01 mol/L NaClO₄ solution. The effects of pH, HA, contact time and initial Eu(III) concentrations were also investigated. The results indicate that the sorption of Eu(III) on Na-bentonite was dependent on pH values. The presence of HA had little effect on Eu(III) sorption at low pH values, but decreased Eu(III) sorption at high pH values. X-ray absorption fine structure spectroscopy (XAFS) was applied to characterize the local structural environment of the adsorbed Eu(III) on bare Na-bentonite and HA-bentonite hybrids. The results indicate that Eu(III) was bound to O atoms at a distance of about 2.39 Å at pH 4.15. The results are crucial for the evaluation of the sorption and migration of other trivalent lanthanides and actinides in bentonite as backfill materials.     

Effects of pH,ionic strength,temperature, and humic acid on Eu(III) sorption onto iron oxides

Effects of pH, Eu(III) concentration, ionic strength, temperature and humic acid (HA) on Eu(III) sorption to iron oxides were investigated in detail. The sorption of Eu(III) to iron oxides was significantly dependent on pH and weakly dependent on ionic strength, and higher temperature was gainful to Eu(III) sorption. In the presence of HA, Eu(III) sorption was enhanced significantly at low pH; whilst obvious negative effect was observed in higher pH range. Below 12 mg/L HA, HA could obviously enhanced Eu(III) sorption to iron oxides, nevertheless Eu(III) sorption decreased steeply with increasing HA while HA exceeded 12 mg/L. The results were helpful for understanding radionuclides behaviors in natural environment.     

Kinetics of radioeuropium sorption on Gorleben sand from aqueous solutions and ground water

Kinetics of Eu sorption on sandy sediment from Gorleben, Germany, containing humic substances, was studied by radiotracer method in batch experiments at very low europium concentration (3.4^.10^-8 mol/l), with the aim to find kinetic parameters suitable for modeling Eu migration in bed of the sediment and to elucidate the mechanism of the sorption. Experiments were evaluated using a new simplified method taking into account simultaneous sorption/desorption of Eu on the walls of sorption vessel. Five kinetic functions were tested, of which that describing diffusion in inert surface layer of sorbent proved most suitable. The effects of pH (3.0-8.8) by addition of Aldrich humic acid (10 mg/l), addition of hydrogencarbonates (5^.10^-3 mol/l) and preequilibration of the sediment with solution or of Eu with solution were examined. From the results it has been concluded that the kinetics and mechanism of the sorption strongly depend on pH. At pH 4.8 Eu is sorbed mainly as humate complex from the solution of humic acid. The addition of humic acid accelerates the sorption. Carbonate complexes of Eu are the probable forms sorbed at pH 8.8. The presence of humic substances in the slightly alkaline solutions suppresses the rate of the sorption due to slow dissociation of Eu-humate complexes.     

Sorption of americium from low-level liquid wastes by nanocrystalline MnO2

Nanocrystalline MnO₂, synthesized by alcoholic hydrolysis of KMnO₄, has been studied as a sorbent for removal of americium from low level liquid waste solutions. The synthesized MnO₂ was found to have BET surface area of 230 m² g^?1. Am(III) was found to be sorbed by MnO₂ quantitatively within 15 min at pH 5. The sorption was found to be more than 90 % at as low a pH as 1.2 and reached to near 100 % at all pH values above pH 3.0 There was no effect of ionic strength (0.01–1.0 M NaCl, CaCl₂) on the sorption suggesting the sorption following inner sphere complexation mechanism at all the pH values. Adsorption isotherm studies were carried out using Eu(III) as a chemical analogue of Am(III). These studies showed the isotherm data to follow Langmuir adsorption isotherm.     

Effect of humic acid, pH and ionic strength on the sorption of Eu(III) on red earth and its solid component

Sorption and desorption of radioeuropium on red earth and its solid components to remove organic matter was studied at pH 5.3±0.1 and 4.5±0.1, and in 0.01M and 0.001M NaClO₄ solutions, respectively. Eu(III) sorption showed strong pH and humic acid concentration dependency, and NaClO₄ concentration independency. The sorption increased with increasing pH and amount of HA adsorbed on red earth. The sorption of Eu(III) on red earth was mainly dominated by surface complexation. Humic acid and high pH had a great tendency to immobilize the movement of Eu(III) in red earth. Sorption-desorption hysteresis of Eu(III) on red earth indicated that the sorption was irreversible.     

Sorption of noble-metal ions on silica with chemically bonded nitrogen-containing ligands

A study has been made of the sorption of Ir(IV), Rh(III), Pt(IV), Ru(IV), Os(VIII), Pd(II) and Au(III) from aqueous solutions by silica chemically modified with nitrogen-containing organic ligands, as a function of hydrochloric acid concentration, time of contact, concentration of the element and the ionic strength. Sorption of noble-metal ions at pH > 1 on a sorbent containing monoamine groups seems to be due to a complexation mechanism, and to an anion-exchange mechanism at pH < 1. With aminopropyl-silica 1000-fold concentration of Ir(IV) and Rh(III) from their 10(-8)-10(-7)M solutions was achieved and these metals were subsequently determined on the sorbent surface by X-ray fluorescence. Detection limits were 10-20 ng/ml. There was no interference from 1000-fold quantities of non-ferrous metal ions and Fe(III). With the sorbent containing bonded diethylenetriamine groups, 1000-fold concentration of Au(III) was achieved, and it was then determined on the sorbent surface by an atomic-emission method. Conditions for desorption of Au(III) with pyridine and potassium thiocyanate were developed.     

Uptake properties of Eu(III) on Na-attapulgite as a function of pH, ionic strength and temperature

Herein, the sorption properties of Eu(III) on Na-attapulgite were performed by using batch sorption experiments under different experimental conditions, such as contact time, pH, ionic strength, humic acid and temperatures. The results indicated that the sorption of Eu(III) on Na-attapulgite was strongly dependent on pH and temperature. At low pH values, the sorption of Eu(III) was influenced by ionic strength, whereas the sorption was not affected by ionic strength at high pH values. The sorption of Eu(III) was mainly dominated by ion exchange or outer-sphere surface complexation at low pH values, and by inner-sphere surface complexation or surface precipitation at high pH values. The sorption of Eu(III) onto Na-attapulgite increased with increasing temperature. The Langmuir and Freundlich models were applied to simulate the sorption isotherms, and the results indicated that the Langmuir model simulated the sorption isotherms better than the Freundlich model. The thermodynamic parameters (∆G ^o, ∆S ^o, ∆H ^o) were calculated from the temperature dependent sorption isotherms at 293, 313 and 333 K, respectively, and the results indicated that the uptake of Eu(III) on Na-attapulgite was an endothermic and spontaneous process. The results of high Eu(III) sorption capacity on Na-attapulgite suggest that the attapulgite is a suitable material for the preconcentration and immobilization of Eu(III) ions from large volumes of aqueous solutions.     

Sorption of Th(IV) ions onto TiO2: Effects of contact time, ionic strength, thorium concentration and phosphate

Summary The sorption of Th(IV) onto TiO₂ was studied by the batch technique as a function of pH and ionic strength at moderate concentration (10^-4-10^-5 mol/l) and in the presence and absence of phosphate. It was found that the sorption rate of Th(IV) was relatively slow, the sorption percent was abruptly increased from pH 2 to 4, and the sorption was decreased with increasing ionic strength as a whole. In the concentration range of Th(IV) from trace concentration to 1.4 ^. 10^-4 mol/l and in the absence of phosphate, the sorption isotherms were roughly fitted the Freundlich equation at different ionic strengths and approximately constant pH. These sorption characteristics of Th(IV) onto TiO₂ were compared with those of uranyl on the same sorbent. In addition, the positive effect of phosphate on the sorption of Th(IV) onto TiO₂ was demonstrated obviously and can be attributed to strong surface binding of phosphate, and the subsequent formation of ternary surface complexes of Th(IV). The difference between the sorption characteristics of Th(IV) ions and uranyl ions onto TiO₂ is discussed.     

静态法和X射线吸收精细结构光谱技术研究腐殖酸对Eu(III)在高庙子膨润土上的吸附影响

膨润土由于其高吸附性和低渗透性而受到广泛的研究. 在本文中, 利用XRD、FTIR和酸碱滴定对我国内蒙古高庙子膨润土进行了详细的表征和分析. 用静态法研究在温度为25± 2 ℃和0.01 mol/L NaClO4溶液中, pH值、腐殖酸、接触时间和Eu(III)初始浓度对Eu(III)在钠基膨润土上的吸附影响. 研究结果表明Eu(III)的吸附受pH值影响明显. 在低pH值条件下, 腐殖酸对Eu(III)的吸附影响微弱, 而在高pH值条件下腐殖酸降低Eu(III)的吸附. X射线吸收精细结构光谱(XAFS)技术对吸附在膨润土上的Eu(III)局域微观结构研究结果表明, 在pH为4.15条件下, Eu在膨润土上与其周围的氧原子间的距离大约为2.39 Å. 本文中的研究结果对于评估其他三价镧系和锕系元素在作为填充材料的膨润土上的吸附和迁移具有重要的意义.     

Eu(III) adsorption on rutile: Batch experiments and modeling

Eu(III) adsorption on rutile was investigated as a function of contact time, pH, ionic strength and Eu(III) concentration by using a batch experimental method. The effects of carbonate, sulfate, and phosphate were also studied. It was found that the kinetics of Eu(III) adsorption on rutile could be described by a pseudo-second-order model. The adsorption of Eu(III) on rutile is strongly pH-dependent, but relatively insensitive to ionic strength. A double layer model (DLM) with two inner-sphere Eu(III) surface complexes was applied to quantitatively interpret the adsorption of Eu(III) on rutile. There were no apparent effects of carbonate and sulfate on Eu(III) adsorption, whereas the presence of phosphate promoted Eu(III) adsorption on rutile. The surface complexes of Eu(III) on rutile were evidenced by X-ray photoelectron spectroscopy (XPS).     

Effect of pH, ionic strength, foreign ions and temperatures on the sorption of Eu(III) on attapulgite-iron oxide magnetic composites

In this paper, the attapulgite-iron oxide magnetic composites were synthesized by coprecipitation method and were characterized by SEM, XRD and FTIR in detail. The characterization results indicated that the iron oxide was successfully formed on the surface of attapulgite. The prepared attapulgite-iron oxide magnetic composites were applied as adsorbents to remove Eu(III) from aqueous solutions by using batch sorption experiments under different experimental conditions. The sorption properties of Eu(III) on bare attapulgite were also performed as comparison. The results indicated that the sorption of Eu(III) on attapulgite-iron oxide magnetic composites was strongly dependent on pH and temperature. The attapulgite-iron oxide magnetic composites can be separated from aqueous solutions using magnetic separation method in large scale. At low pH values, the sorption of Eu(III) was influenced by ionic strength and pH obviously, while the sorption of Eu(III) was not affected by ionic strength at high pH values. The sorption of Eu(III) was dominated by ion exchange or outer-sphere surface complexation at low pH values, and mainly by inner-sphere surface complexation at high pH values. The thermodynamic parameters (i.e., ?G ^°, ?S ^°, ?H ^°) calculated from the temperature dependent sorption isotherms indicated that the sorption of Eu(III) on attapulgite-iron oxide magnetic composites was an endothermic and spontaneous process. Although the sorption capacities of Eu(III) on attapulgite-iron oxide magnetic composites were a little lower than those of Eu(III) on bare attapulgite, the magnetic separation in large scale is suitable for the application of the magnetic composites in the preconcentration of Eu(III) from large volumes of aqueous solutions in possible real applications.     

Insights into sorption species of Eu(III) on γ-Al2O3 and bentonite under different pH: Studies at macro- and micro-scales

The sorption species of Eu(III) on γ-Al₂O₃ and bentonite was investigated by batch, surface complexation model (SCM), and X-ray absorption spectroscopy (XAS). The results showed that sorption edges of Eu(III) on γ-Al₂O₃ and bentonite were as expected shifted forward high pH with the increasing in Eu(III) concentration, and sorption of Eu(III) was strongly dependent on pH. In γ-Al₂O₃ system, sorption of Eu(III) was decreased above pH 8.5 at low concentration of Eu(III) because of water soluble carbonate species of Eu(III), however the decline did not appear at high concentration of Eu(III) possibly due to a offset effect of surface precipitation. Actually, the sorption species of Eu(III) on bentonite mainly referred to at least four kinds of species including ion exchange (>X₃Eu⁰) at low pH, inner-sphere complexes (>AlOEu²⁺ and >SiOEu²⁺) at neutral condition, and hydrolysis species (>SiOEu(OH) ₂ ⁰ ) at alkaline condition. Linear combination fitting (LCF) in k space testified that hydrolysis of Eu(OH)₃(s) and oxide of Eu₂O₃ species were major for Eu(III) sorption on γ-Al₂O₃, whereas Eu³⁺(aq) and hydrolysis species comprised sorption species on bentonite. Extended X-ray absorption fine structure (EXAFS) analysis further confirmed the prediction from SCM and LCF. In addition, the typical shells of Eu–Al in R range of 3.0–3.4 Å and Eu–Si at ~4.0 Å were found in radial structure functions, which was possibly identified to edge-shared bidentate of Eu(III) on Al₂O₃ and bentonite.     

Solubility of Eu<Subscript>2</Subscript>(SeO<Subscript>3</Subscript>)<Subscript>3</Subscript> and sorption of Eu(III) onto TiO<Subscript>2</Subscript> in the presence of Se(IV)

Metal ions sorption can be significantly affected by the presence of other sorbates, especially of complexing ligands. In this study, the effect of Se(IV) on Eu(III) sorption onto TiO₂ at different pH and Eu(III) concentration was investigated. Se(IV) was found to enhance Eu(III) sorption as a function of Se(IV) concentration. Constant capacitance model was successfully used to interpret the sorption experimental data. The solubility product of Eu₂(SeO₃)₃ at ambient temperature was investigated to highlight the sorption mechanism of ternary sorption system. The pK _sp value of Eu₂(SeO₃)₃ was found to be 31.51 ± 0.95.     

Eu(Ⅲ)在蒙脱石上的吸附及碳酸根和磷酸根对其吸附的影响

锕系核素在处置库围岩和缓冲回填材料中的吸附和迁移参数是处置库安全评价的重要数据模块之一，而Eu(Ⅲ)由于其与三价锕系元素An(Ⅲ)相似的离子半径和化学性质常被用于模拟三价锕系元素的化学行为。本文通过批式吸附实验研究了固液比、接触时间、离子强度、pH、碳酸根及磷酸根等对Eu(Ⅲ)在蒙脱石上吸附的影响，重点关注了吸附机理和表面种态。研究结果表明，低pH时Eu(Ⅲ)在蒙脱石上的吸附方式为外层配位吸附，近中性时为内层配位吸附，高pH时则以表面沉淀的方式被吸附。离子强度的增大对Eu(Ⅲ)在低pH时的吸附产生抑制作用。低pH时碳酸根对Eu(Ⅲ)吸附的影响不明显，但在高pH时其会改变Eu(Ⅲ)的表面吸附种态。尽管磷酸根本身的吸附非常弱，但磷酸根会显著增强Eu(Ⅲ)的吸附。X射线光电子能谱结果和磷酸根吸附实验说明Eu(Ⅲ)在蒙脱石表面上形成了EuPO₄沉淀。本工作研究了蒙脱石/Eu(Ⅲ)二元体系和蒙脱石/Eu(Ⅲ)/阴离子三元体系的吸附行为，并用光谱技术探究了其吸附种态，为理解三价锕系核素在蒙脱石上的吸附行为提供了重要参考。     

Sorption and desorption characteristics of Eu(III) on red earth

The batch method and the column method were simultaneously employed to study the sorption and desorption of Eu(III) on red earth as a function of pH (4.6–6), the presence of a well-characterized fulvic acid (FA) and the iron oxides content of red earth. The results from both methods were consistent qualitatively. The Eu(III) sorption showed significant dependences on pH and FA, the sorption was increased with increasing pH and by addition of FA to the solutions, while the iron oxides content of the red earth had a negative contribution to the sorption of Eu(III). Additionally, the sorption-desorption hysteresis of Eu(III) on red earth occurred at a pH range of 4.6–6. Therefore, the humic substance and high pH have a great tendency to immobilize Eu(III) on red earth.