Effect of pH, ionic strength, foreign ions and humic substances on Th(IV) sorption to GMZ bentonite studied by batch experiments

Bentonite has been studied extensively because of its strong sorption and complexation ability. Herein, GMZ bentonite from Gaomiaozi county (Inner Mongolia, China) was investigated as the candidate of backfill material for the removal of Th(IV) ions from aqueous solutions. The results indicate that the sorption of Th(IV) is strongly dependent on pH and ionic strength at pH < 5, and independent of ionic strength at pH > 5. Outer-sphere surface complexation or ion-exchange are the main mechanism of Th(IV) sorption on GMZ bentonite at low pH values, whereas the sorption of Th(IV) at pH > 5 is mainly dominated by inner-sphere surface complexation or surface precipitation. Soil fulvic acid (FA) and humic acid (HA) have a positive influence on the sorption of Th(IV) on bentonite at pH < 5. The different addition sequences of HA and Th(IV) to GMZ bentonite suspensions have no obvious effect on Th(IV) sorption to HA-bentonite hybrids. The high sorption capacity of Th(IV) on GMZ bentonite suggests that the GMZ bentonite can remove Th(IV) ions from large volumes of aqueous solutions in real work.     

Sorption of Th(IV) from aqueous solution to GMZ bentonite: effect of pH, ionic strength, fulvic acid and electrolyte ions

Bentonite has been studied extensively because of its strong sorption and complexation ability. In this study, GMZ bentonite (China) was studied as a potential sorbent for the removal of Th(IV) from aqueous solutions. The results indicate that the sorption of Th(IV) is strongly dependent on pH and ionic strength at pH <5, and is independent of ionic strength at pH >5. Outer-sphere surface complexation or ion exchange in inter-layer sites of the montmorillonite fraction of the GMZ bentonite may be the main sorption mechanism of Th(IV) onto GMZ bentonite at low pH values, whereas the sorption of Th(IV) at pH >5 is mainly dominated by inner-sphere surface complexation or surface precipitation. The presence of soil fulvic acid has a positive influence on the sorption of Th(IV) on GMZ bentonite at pH <5. The competition between Th(IV) with aqueous or surface adsorbed cation ions (e.g., herein Li⁺, Na⁺ and K⁺) and surface functional groups of GMZ bentonite is important for Th(IV) sorption on GMZ bentonite. The results of high sorption of Th(IV) suggest that the GMZ bentonite is a suitable backfill material in nuclear waste management.     

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.     

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.     

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.     

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.     

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 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.     

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.     

Investigation of Co(II) sorption on GMZ bentonite from aqueous solutions by batch experiments

In this study, a local bentonite from Gaomiaozi county (Inner Mongolia, China) was converted to Na-bentonite and was characterized by FTIR and XRD to determine its chemical constituents and micro-structure. The removal of cobalt from aqueous solutions by Na-bentonite was investigated as a function of contact time, pH, ionic strength, foreign ions and temperature by batch technique under ambient conditions. The results indicated that the sorption of Co(II) was strongly dependent on pH. At low pH, the sorption of Co(II) was dominated by outer-sphere surface complexation or ion exchange whereas inner-sphere surface complexation was the main sorption mechanism at high pH. The Langmuir, Freundlich, and D-R models were used to simulate the sorption isotherms of Co(II) at the temperatures of 293.15, 313.15 and 333.15 K, respectively. The thermodynamic parameters (∆G°, ∆S°, ∆H°) of Co(II) sorption on GMZ bentonite calculated from the temperature-dependent sorption isotherms indicated that the sorption of Co(II) on GMZ bentonite was an exothermic and spontaneous process. The Na-bentonite is a suitable material for the preconcentration and solidification of Co(II) from aqueous solutions.     

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.     

Effect of pH,foreign ions and temperature on radionickel sorption onto bentonite from Inner Mongolia,China

The development of nuclear power releases large amounts of radionuclides into the natural environment. Herein, the sorption of radionuclide ⁶³Ni on bentonite from Gaomiaozi county (Inner Mongolia, China) at different experimental conditions such as pH, contact time, ionic strength, foreign cations and anions, and temperatures were investigated by using batch technique. The results indicated that the sorption of ⁶³Ni on the bentonite was quickly at first contact time and then increased slowly with increasing contact time. The sorption of ⁶³Ni was strongly dependent on ionic strength at low pH values and independent of ionic strength at high pH values. The sorption of ⁶³Ni on bentonite was mainly dominated by outer-sphere surface complexation or ion exchange at low pH values, whereas inner-sphere surface complexation was the main sorption mechanism at high pH values. The Langmuir, Freundlich, and D–R models were applied to simulate the sorption isotherms of ⁶³Ni at three different temperatures, and the thermodynamic parameters (i.e., ΔH°, ΔS° and ΔG°) calculated from the temperature-dependent sorption isotherms indicated that the sorption of ⁶³Ni on bentonite was an endothermic and spontaneous process. Experimental results indicate that the bentonite is a suitable material for the preconcentration and solidification of ⁶³Ni from large volume of solutions in radionickel pollution cleanup.     

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.     

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.     

Wireless sensing determination of uranium(IV) based on its inhibitory effect on a catalytic precipitation reaction

The adsorption of Eu(III) on multiwalled carbon nanotubes (MWCNTs) as a function of pH, ionic strength and solid contents are studied by batch technique. The results indicate that the adsorption of Eu(III) on MWCNTs is strongly dependent on pH values, dependent on ionic strength at low pH values and independent of ionic strength at high pH values. Strong surface complexation and ion exchange contribute to the adsorption of Eu(III) on MWCNTs at low pH values, whereas surface complexation and surface precipitation are the main adsorption mechanism of Eu(III) on MWCNTs. The desorption of adsorbed Eu(III) from MWCNTs by adding HCl is also studied and the recycling use of MWCNTs in the removal of Eu(III) is investigated after the desorption of Eu(III) at low pH values. The results indicate that adsorbed Eu(III) can be easily desorbed from MWCNTs at low pH values, and MWCNTs can be repeatedly used to remove Eu(III) from aqueous solutions. MWCNTs are suitable material in the preconcentration and solidification of radionuclides from large volumes of aqueous solutions in nuclear waste management.     

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.     

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.     

The sorption of Eu(III) on calcareous soil: effects of pH,ionic strength,temperature, foreign ions and humic acid

The sorption of Eu(III) on calcareous soil as a function of pH, humic acid (HA), temperature and foreign ions was investigated under ambient conditions. Eu(III) sorption on soil was strongly pH dependent in the observed pH range. The effect of ionic strength was significant at pH < 7, and not obvious at pH > 8. The type of salt cation used had no visible influence on Eu(III) uptake on soil, however at low pH values, the influence of anions was following the order: Cl⁻ ≈ NO₃ ⁻ > ClO₄ ⁻. In the presence of HA, the sorption edge obviously shifted about two pH units to the lower pH, whilst in range of pH 6–7, the sorption of Eu(III) decreased with increasing pH because a considerable amount of Eu(III) was present as humate complexes in aqueous phase, then increased again at pH > 11. The results indicated that the sorption of Eu(III) on soil mainly formed outer-sphere complexes and/or ion exchange below pH ~7; whereas inner-sphere complexes and precipitation of Eu(OH)₃(s) may play main role above pH ~8.     

Impact of environmental conditions on the removal of Ni(II) from aqueous solution to bentonite/iron oxide magnetic composites

The sorption of radionuclide ⁶³Ni(II) on bentonite/iron oxide magnetic composites was investigated by batch technique under ambient conditions. The effect of contact time, solid content, pH, coexistent electrolyte ions, fulvic acid, and temperature on Ni(II) sorption to bentonite/iron oxide magnetic composites was examined. The results demonstrated that the sorption of Ni(II) was strongly dependent on pH and ionic strength at pH <8.0, and was independent of pH and ionic strength at high pH values. The sorption of Ni(II) was dominated by outer-sphere surface complexation or ion exchange at low pH, whereas inner-sphere surface complexation was the main sorption mechanism at high pH. The experimental data were well fitted by Langmuir model. The thermodynamic parameters (∆G°, ∆S°, ∆H°) calculated from the temperature-dependent sorption isotherms indicated that the sorption of Ni(II) on bentonite/iron oxide magnetic composites was an endothermic and spontaneous processes. The results show that bentonite/iron oxide magnetic composites are promising magnetic materials for the preconcentration and separation of radionickel from aqueous solutions in environmental pollution.     

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.