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.     

Adsorption of Eu(III) on titanate nanotubes studied by a combination of batch and EXAFS technique

The effects of pH,contact time and natural organic ligands on radionuclide Eu(Ⅲ) adsorption and mechanism on titanate nanotubes(TNTs) are studied by a combination of batch and extended X-ray absorption fine structure(EXAFS) techniques.Macroscopic measurements show that the adsorption is ionic strength dependent at pH < 6.0,but ionic strength independent at pH > 6.0.The presence of humic acid(HA) /fulvic acid(FA) increases Eu(Ⅲ) adsorption on TNTs at low pH,but reduces Eu(Ⅲ) adsorption at high pH.The results of EXAFS analysis indicate that Eu(Ⅲ) adsorption on TNTs is dominated by outer-sphere surface complexation at pH < 6.0,whereas by inner-sphere surface complexation at pH > 6.0.At pH < 6.0,Eu(Ⅲ) consists of ～ 9 O atoms at REu?O ≈ 2.40  in the first coordination sphere,and a decrease in NEu-O with increasing pH indicates the introduction of more asymmetry in the first sphere of adsorbed Eu(Ⅲ).At long contact time or high pH values,the Eu(Ⅲ) consists of ～2 Eu at REu-Eu ≈ 3.60  and ～ 1 Ti at REu-Ti ≈ 4.40 ,indicating the formation of inner-sphere surface complexation,surface precipitation or surface polymers.Surface adsorbed HA/FA on TNTs modifies the species of adsorbed Eu(Ⅲ) as well as the local atomic structures of adsorbed Eu(Ⅲ) on HA/FA-TNT hybrids.Adsorbed Eu(Ⅲ) on HA/FA-TNT hybrids forms both ligand-bridging ternary surface complexes(Eu-HA/FA-TNTs) as well as surface complexes in which Eu(Ⅲ) remains directly bound to TNT surface hydroxyl groups(i.e.,binary Eu-TNTs or Eu-bridging ternary surface complexes(HA/FA-Eu-TNTs)).The findings in this work are important to describe Eu(Ⅲ) interaction with nanomaterials at molecular level and will help to improve the understanding of Eu(Ⅲ) physicochemical behavior in the natural environment.     

静态法和EXAFS技术研究Eu(III)在钛酸纳米管上的吸附行为和微观机制

结合静态实验和X射线吸收精细结构谱学(EXAFS)技术研究了pH、时间、有机配体等环境因素对放射性核素Eu(III)在钛酸纳米管上的吸附行为和微观机制的影响.宏观实验结果表明:Eu(III)在钛酸纳米管上的吸附在pH<6.0条件下受离子强度影响,而在pH>6.0条件下不受离子强度影响;腐殖酸HA/FA在低pH条件下可以促进Eu(III)在钛酸纳米管上的吸附,而在高pH条件下抑制Eu(III)在钛酸纳米管上的吸附.EXAFS微观分析结果表明:在pH<6.0条件下,吸附属于外层吸附机理;在pH>6.0条件下,吸附属于内层吸附机理.pH<6.0时,中心原子Eu周围只有Eu-O一个配位层,其平均键长为2.40,配位数在9左右;随着pH逐渐升高,第一配位层的配位数下降,表明吸附Eu原子配位的对称性下降.当吸附时间延长或pH升高,吸附原子Eu周围出现了Eu-Eu和Eu-Ti第二配位层,其平均键长分别为3.60和4.40,配位数分别在2或1左右,表明形成了内层吸附产物或表面沉淀或表面多聚体.腐殖酸HA/FA的存在,可以改变Eu(III)在钛酸纳米管表面的吸附形态和微观原子结构,Eu(III)不仅可以与钛酸纳米管的表面羟基直接键合形成二元表面复合物(Eu-TNTs),还可以通过HA/FA的桥连作用形成三元表面复合物(HA/FA-Eu-TNTs).这些研究结果对于评估放射性核素Eu(III)与纳米材料在分子水平上的作用机理及分析Eu(III)在环境中的物理化学行为具有重要的意义.     

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.     

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.     

Adsorption of Eu(III) from aqueous solution using mesoporous molecular sieve

The adsorption behavior of Eu(III) from aqueous solution to mesoporous molecular sieves (Al-MCM-41) is investigated as a function of contact time, solid content, ionic strength, pH, foreign ions and temperature by using batch technique. The experimental results show that Eu(III) adsorption is strongly dependent on pH values, but independent of ionic strength and foreign cations under our experimental conditions. The kinetic process is described by a pseudo-second-order rate model very well. The adsorption isotherms are simulated by Langmuir model very well. The thermodynamic parameters (∆G°, ∆S°, ∆H°) are calculated from the temperature dependent adsorption isotherms at 293, 313 and 333 K, respectively, and the results suggest that the adsorption of Eu(III) on Al-MCM-41 is a spontaneous and endothermic process. Desorption studies indicate that the adsorbed Eu(III) is very difficult to be desorbed from the solid surface. Al-MCM-41 is a suitable material for the preconcentration and solidification of Eu(III) from large volumes of aqueous solutions.     

Adsorption of Eu(III) on iron oxide/multiwalled carbon nanotube magnetic composites

Iron oxide/multiwalled carbon nanotube magnetic composites (denoted as magnetic composites) were synthesized and characterized in detail. The magnetic composites can be separated from aqueous solution easily by using magnetic separation method. The application of magnetic composites in the removal of Eu(III) from large volumes of aqueous solutions was studied. The results indicated that the sorption of Eu(III) on the magnetic composites was strongly dependent on pH values and weakly dependent on ionic strength. The sorption of Eu(III) on the magnetic composites was mainly dominated by inner-sphere surface complexation. The linear sorption isotherms of Eu(III) suggested that Eu(III) sorption on the magnetic composites was far from saturation. The large sorption capacity and the easy magnetic separation method indicate that the magnetic composites may be a promising suitable material in nuclear waste management in future.     

Removal of U(VI) from aqueous solutions by using MWCNTs and chitosan modified MWCNTs

In this paper, the multiwalled carbon nanotubes (MWCNTs) were modified with chitosan (CS) by using low temperature plasma grafting technique (denoted as MWCNT-CS). The prepared MWCNTs and MWCNT-CS were characterized by SEM, TEM, FTIR and Raman spectroscopy in detail and the results suggested that CS molecules were successfully grafted on the surfaces of MWCNTs. The materials were applied as adsorbents in the removal of U(VI) ions from large volumes of aqueous solutions as a function of environmental conditions. The removal of U(VI) from aqueous solution to MWCNTs and MWCNT-CS increased with increasing pH values at pH < 7, and then decreased with increasing pH values at pH > 7. The sorption of U(VI) on MWCNTs and MWCNT-CS was strongly dependent on pH and independent of ionic strength. The sorption of U(VI) on MWCNTs and MWCNT-CS was dominated by inner-sphere surface complexation rather than by ion exchange or outer-sphere surface complexation. The surface grafted chitosan molecules can enhances U(VI) sorption on MWCNTs obviously, which was also evidenced from the XPS spectroscopy analysis. The results of high sorption capacity of U(VI) on MWCNT-CS suggest that the MWCNT-CS nanomaterial is a suitable candidate in the preconcentration of U(VI) ions from large volumes of aqueous solutions.     

Effect of pH and ionic strength on U(IV) sorption to oxidized multiwalled carbon nanotubes

Multiwalled carbon nanotubes (MWCNTs) have attracted multidisciplinary study because of their unique physicochemical properties. Herein, the sorption of U(VI) from aqueous solution to oxidized MWCNTs was investigated as a function of contact time, pH and ionic strength. The results indicate that U(VI) sorption on oxidized MWCNTs is strongly dependent on pH and ionic strength. The sorption of U(VI) is mainly dominated by surface complexation and cation exchange. The sorption of U(VI) on oxidized MWCNTs is quickly to achieve the sorption equilibrium. The sorption capacity calculated from sorption isotherms suggests that oxidized MWCNTs are suitable material in the preconcentration and solidification of U(VI) from large volumes of aqueous solutions.     

Surface complexation modeling of Sr(II) and Eu(III) adsorption onto oxidized multiwall carbon nanotubes

Acid-base titrations of oxidized multiwall carbon nanotubes (MWCNTs), Sr(II) and Eu(III) adsorptions onto oxidized MWCNTs were conducted to investigate the surface charge characteristics of oxidized MWCNTs and the surface complexation interactions between Sr(II)/Eu(III) and oxidized MWCNTs. The results suggested that Sr(II) and Eu(III) adsorptions onto oxidized MWCNTs increased with increasing pH, and decreased with increasing ionic strength, and the affinity of oxidized MWCNTs for Eu(III) was much higher than that for Sr(II). The diffuse layer model (DLM) fitted the experimental data of Sr(II) and Eu(III) adsorptions well with the aid of FITEQL 3.2.     

Sorption of uranium(VI) on Na-attapulgite as a function of contact time,solid content,pH, ionic strength,temperature and humic acid

Sorption of U(VI) from aqueous solution to Na-attapulgite was investigated at different experimental chemistry conditions by using batch technique. The attapulgite sample was characterized by FTIR and XRD. Sorption of U(VI) on attapulgite was strongly dependent on pH and ionic strength. The sorption of U(VI) on attapulgite increased quickly with rising pH at pH < 6, and decreased with increasing pH at pH > 7. The presence of humic acid (HA) enhanced the sorption of U(VI) on attapulgite obviously at low pH because of the strong complexation of surface adsorbed HA with U(VI) on attapulgite surface. Sorption of U(VI) on attapulgite was mainly dominated by ion exchange and/or outer-sphere surface complexation at low pH values, whereas the sorption was attributed to the inner-sphere surface complexation or precipitation at high pH values. The sorption increased with increasing temperature and the thermodynamic parameters calculated from the temperature dependent sorption isotherms suggested that the sorption of U(VI) on attapulgite was a spontaneous and endothermic process. The results indicate that attapulgite is a very suitable material for the preconcentration of U(VI) ions from large volumes of aqueous solutions.     

Sorption of strontium ions from aqueous solutions by oxidized multiwall carbon nanotubes

Multiwall carbon nanotubes (MWCNTs) oxidized by nitric acid solution were used to investigate the adsorption behavior of strontium from aqueous solutions similar to the nuclear waste media. The physical properties of both as produced and oxidized MWCNTs were studied by Boehm’s titration method and nitrogen adsorption/desorption. The results showed that the surface properties of MWCNTs such as specific surface area, functional groups and the total number of acid sites were improved after oxidation. Furthermore, the effect of solution conditions such as initial concentration of strontium(II), pH, ionic strength, MWCNT concentration and contact time were studied at room temperature. The results of this study showed that the adsorption of strontium(II) was significantly influenced by the pH value and the solution ionic strength. According to the Langmuir model, the maximum adsorption capacities of strontium(II) onto the as produced and oxidized MWCNTs were obtained as 1.62 and 6.62 mg g^?1, respectively. The contact time to reach equilibrium was 100 min. The good adsorption of strontium(II) on oxidized MWCNTs at the lower ionic strength, the relatively high pH and the short equilibrium time indicate that the oxidized MWCNTs have great potential applications in the field of the environmental protection.     

Influence of pH,ionic strength,foreign ions and FA on adsorption of radiocobalt on goethite

This work contributed to the adsorption of radiocobalt on goethite as a function of contact time, pH, ionic strength and foreign ions in the absence and presence of fulvic acid (FA) under ambient conditions. The results indicated that adsorption of Co(II) was dependent on ionic strength and foreign ions at low pH values (pH < 7.8), and independent of ionic strength and foreign ions at high pH values (pH > 7.8). Outer-sphere surface complexation and/or ion exchange were the main mechanisms of Co(II) adsorption on goethite at low pH values, whereas inner-sphere surface complexation was the main adsorption mechanism at high pH values. The presence of FA enhanced Co(II) adsorption at low pH values, but reduced Co(II) adsorption at high pH values. The thermodynamic data (ΔH ⁰, ΔS ⁰, ΔG ⁰) were calculated from the temperature dependent adsorption isotherms, and the results suggested that adsorption process of Co(II) on goethite was spontaneous and endothermic. The results are crucial to understand the physicochemical behavior of Co(II) in the nature environment.     

Impact of environmental conditions on sorption of <Superscript>210</Superscript>Pb(II) to NKF-5 zeolite

The sorption of Pb(II) from aqueous solution using NKF-5 zeolite was investigated by batch technique under ambient conditions. The NKF-5 zeolite sample was characterized by using FTIR and X-ray powder diffraction in detail. The sorption of Pb(II) was investigated as a function of pH, ionic strength, foreign ions, and humic substances. The results indicated that the sorption of Pb(II) on NKF-5 zeolite was strongly dependent on pH. The sorption was dependent on ionic strength at low pH, but independent of ionic strength at high pH. At low pH, the sorption of Pb(II) was dominated by outer-sphere surface complexation and ion exchange with H⁺ on NKF-5 zeolite surfaces, whereas inner-sphere surface complexation was the main sorption mechanism at high pH. From the experimental results, one can conclude that NKF-5 zeolite has good potentialities for cost-effective preconcentration of Pb(II) from large volumes of aqueous solutions.     

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.     

Synthesis and characterization of magnetic nano-material for removal of Eu3+ ions from aqueous solutions

Ferrite coated apatite magnetic nano-material was synthesized by a co-precipitation method and applied in removal of Eu(III) ions from aqueous solutions. The sample was firstly characterized using Fourier transform infrared spectroscopy, thermogravimetric analyses, deferential thermal analysis, X-ray powder diffraction, surface area by nitrogen adsorption and scanning electron microscopy. The results of physicochemical properties indicated that the synthesized magnetic nano-adsorbent had a crystalline structure and possessed a surface area amounted to 85.11 m² g^?1. Further, it was found to have high thermal resistance up to 600 °C and mean particle size of about 63 nm. The kinetic of Eu(III) sorption indicated that equilibrium state was attained within 12 h with using 5 mg as an appropriate nano-adsorbent weight. The sorption process was pH and ionic strength dependent. The maximum adsorbed amount of Eu(III) was attained at pH 2.5 with value reached to 157.14 mg g^?1. Desorption of Eu(III) from loaded samples was studied using various eluents and maximum recovery was obtained using FeCl₃ solution.     

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.     

Impact of environmental conditions on the sorption behavior of UO<Subscript>2</Subscript><Superscript>2+</Superscript> onto attapulgite studied by batch experiments

The sorption of UO₂ ²⁺ from aqueous solution on attapulgite was investigated as a function of contact time, solid content, pH, ionic strength, foreign ions, humic acid (HA), and fulvic acid (FA) under ambient conditions by using batch technique. The attapulgite sample was characterized by XRD and FTIR in detail. The results indicated that the sorption of UO₂ ²⁺ was strongly dependent on pH and ionic strength. The sorption of UO₂ ²⁺ on attapulgite increased quickly with rising pH at pH < 6.5, and decreased with increasing pH at pH > 6.5. The presence of HA or FA enhanced the sorption of UO₂ ²⁺ on attapulgite obviously at low pH because of the strong complexation of surface adsorbed HA/FA with UO₂ ²⁺ on attapulgite surface. Sorption of UO₂ ²⁺ on attapulgite was mainly dominated by ion-exchange or outer-sphere surface complexation at low pH values, but by inner-sphere surface complexation at high pH values. The results indicate that attapulgite is a very suitable adsorbent for the preconcentration and solidification of UO₂ ²⁺ from large volumes of aqueous solutions because of its negative surface charge and large surface areas.     

Sorption of 63Ni(II) to montmorillonite as a function of pH, ionic strength, foreign ions and humic substances

Different kinds of clay minerals have been studied extensively in the removal of radionuclides from large volumes of aqueous solutions because of their high sorption capacity. Herein, the Na-montmorillonite was characterized by using XRD and FTIR in detail. The sorption of ⁶³Ni(II) from aqueous solution to montmorillonite as a function of pH, ionic strength, foreign ions, humic substances and temperature was studied by batch technique. The sorption of ⁶³Ni(II) on montmorillonite achieved equilibration quickly. The sorption of ⁶³Ni(II) to montmorillonite was strongly dependent on pH, and dependent on ionic strength at low pH and independent of ionic strength at high pH values. The sorption of ⁶³Ni(II) on montmorillonite was enhanced at low pH in the presence of humic acid (HA), while a negative effect of HA on ⁶³Ni(II) sorption was found at high pH values. At low pH values, the sorption of ⁶³Ni(II) was attributed to outer-sphere surface complexation or ion exchange, whereas the sorption was dominated by inner-sphere surface complexation at high pH values. The montmorillonite sample is a suitable material in the preconcentration of radionuclides from large volumes and the material can be used as backfill material in nuclear waste repository.     

Removal of U(VI) from aqueous solutions by using attapulgite/iron oxide magnetic nanocomposites

The attapulgite/iron oxide magnetic nanocomposites were prepared by coprecipitation method and characterized by scanning electron microscopy, X-ray diffraction, vibrating sample magnetometer and Fourier transform infrared sorption spectroscopy. The results of characterization showed that iron oxides were successfully deposited on the surfaces of attapulgite. The prepared magnetic nanocomposites were applied to remove radionuclide U(VI) ions from aqueous solutions by using batch technique and magnetic separation method. The results showed that the sorption of U(VI) on attapulgite/iron oxide magnetic composites was strongly dependent on ionic strength and pH at low pH values, and was independent of ionic strength at high pH values. The interaction of U(VI) with the magnetic nanocomposites was mainly dominated by outer-sphere surface complexation or ion exchange at low pH values, and was controlled by inner-sphere surface complexation or multinuclear surface complexation at high pH values. With increasing temperature, the sorption of U(VI) on attapulgite/iron oxide magnetic composites increased and the thermodynamic parameters calculated from the temperature dependent sorption isotherms suggested that the sorption of U(VI) on the magnetic nanocomposites was a spontaneous and endothermic process. The high sorption capacity and easy magnetic separation of the attapulgite/iron oxide magnetic composites make the material as suitable sorbent in nuclear waste management.