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1.
In this paper,the macroscopic interaction method and high resolution EXAFS technique with a bent crystal analyzer were combined to study Eu(Ⅲ)interaction mechanism and microstructure withγ-MnOOH as a function of pH.The results indicated that Eu(Ⅲ)interaction withγ-MnOOH was apparently dependent on pH but independent of ionic strength,suggesting the formation of inner-sphere surface complexation for Eu(Ⅲ)ontoγ-MnOOH.Results of EXAFS analysis indicated that Eu was surrounded by~9.0 O atoms in first coordination shell at REu–O≈2.40,and second shell of Mn atoms at REu–Mn≈3.60 was observed for the three adsorption samples.These findings suggested formation of a bidentate surface complex with Eu(Ⅲ)bonding by edge sharing to MnO6-octahedron on γ-MnOOH surface.Both the macroscopic interaction data and the molecular level evidence of Eu(Ⅲ)microstructure at the γ-MnOOH-water interface should be factored into better understanding the fate and mobility of Eu(Ⅲ)and related radionuclides in the natural soil and water environment.  相似文献   

2.
The fate and transport of toxic metal ions and radionuclides in the environment is generally controlled by sorption reactions. The removal of 60Co(II) from wastewaters by MnO2 was studied as a function of various environmental parameters such as shaking time, pH, ionic strength, foreign ions, and humic substances under ambient conditions. The results indicated that the sorption of 60Co(II) on MnO2 was strongly dependent on pH and ionic strength. At low pH, the sorption of 60Co(II) was dominated by outer-sphere surface complexation and ion exchange with Na+/H+ on MnO2 surfaces, whereas inner-sphere surface complexation was the main sorption mechanism at high pH. The presence of HA/FA enhances 60Co(II) sorption at low pH values, whereas reduces 60Co(II) sorption at high pH values. The Langmuir and Freundlich models were used to simulate the sorption isotherms of 60Co(II) at three different temperatures of 298.15, 318.15 and 338.15 K. The thermodynamic parameters (ΔH 0, ΔS 0 and ΔG 0) calculated from the temperature dependent sorption isotherms indicated that the sorption process of 60Co(II) on MnO2 was endothermic and spontaneous.  相似文献   

3.
The sorption of Cd(II) from aqueous solution on MnO2 was investigated under ambient conditions. Experiments were carried out as a function of contact time, solid content, pH, ionic strength, foreign ions, fulvic acid and temperature. The results indicated that the sorption of Cd(II) was strongly dependent on pH and ionic strength. At low pH, the sorption of Cd(II) was dominated by outer-sphere surface complexation and ion exchange with Na+/H+ on MnO2 surfaces, whereas inner-sphere surface complexation was the main sorption mechanism at high pH. The Langmuir, Freundlich and Dubinin–Radushkevich models were used to simulate the sorption isotherms at three different temperatures. The thermodynamic data (ΔG 0, ΔS 0, ΔH 0) calculated from the temperature dependent sorption isotherms suggested that the sorption of Cd(II) on MnO2 was an spontaneous and endothermic process.  相似文献   

4.
In this work, adsorption of Ni(II) from aqueous solution onto hematite under various solution chemistry and temperature was investigated. The results indicated that the pseudo-second-order rate equation fitted the kinetic adsorption well. The adsorption of Ni(II) onto hematite was strongly dependent on pH and ionic strength. At low pH, the adsorption was dominated by outer-sphere surface complexation or ion exchange, whereas inner-sphere surface complexation was the main adsorption mechanism at high pH. A positive effect of FA on Ni(II) adsorption was found at pH < 8.0, whereas a negative effect was observed at pH > 8.0. The Langmuir, Freundlich, and D–R models were applied to simulate the adsorption isotherms at three different temperatures of 293.15, 313.15 and 333.15 K. The thermodynamic parameters were calculated from the temperature dependent adsorption, and the results indicated that the adsorption was endothermic and spontaneous.  相似文献   

5.
结合静态实验和X射线吸收精细结构光谱(EXAFS)技术研究了接触时问、离子强度、初始浓度以及共存电解质离子等水化学条件对放射性核:63^Ni(Ⅱ)在丝光沸石上的吸附行为和微观机制的影响.宏观实验结果表明:放射性核素。63^Ni(Ⅱ)在丝光沸石上的吸附在pH〈7的范围内受离子强度影响,而在pH〉7的范围内不受离子强度影响.放射性核素63^Ni(Ⅱ)在丝光沸石上的吸附率随着固体浓度的增加而升高,而对应的吸附量却随着固体浓度的增加而降低.溶液中共存的电解质离子对63^Ni(Ⅱ)在丝光沸石上的吸附有一定的促进或抑制作用,具体的影响趋势和程度由共存离子的性质、共存离子与63^Ni(Ⅱ)的络合能力以及与丝光沸石表面的亲和力大小共同决定.EXAFS微观结构分析结果表明:在pH6.5的溶液中,63^Ni(Ⅱ)与丝光沸石结构框架中的Na^+/Ca。’等阳离子进行离子交换,形成六水合的外层络合物,不同离子强度下63^Ni(Ⅱ)的微观形态没有明显区别.郇Ni(II)在丝光沸石上的吸附随时间的变化呈现两种不同的作用机制:在溶液pH7.2的条件下,吸附初始的快速反应阶段中63^Ni(Ⅱ)的吸附主要以通过形成内层络合物的形式进行;随着接触时间的增长63^Ni(Ⅱ)在丝光沸石上的吸附机理转变为镍页硅酸盐共沉淀或者氢氧化镍沉淀的形成.初始63^Ni(Ⅱ)浓度为100mg/L的EXAFS图谱分析结果表明表面多聚体的形成是此条件下63^Ni(Ⅱ)在丝光沸石上的主要吸附机理.放射性核素63^Ni(Ⅱ)在丝光沸石/水界面的吸附行为和形态分布对于准确预测其在环境介质中的迁移转化和生物有效性等物理化学行为具有重要的意义.  相似文献   

6.
Sorption of radionickel on attapulgite is studied as a function of contact time, ionic strength, pH and temperature. The results indicate that the sorption of Ni(II) on attapulgite is strongly ionic strength-dependent at pH <8, and independent of ionic strength at pH >8. Outer-sphere surface complexation or ion exchange contributes to Ni(II) sorption on attapulgite at pH <8, whereas the sorption of Ni(II) is mainly dominated by inner-sphere surface complexation at pH >8. The sorption of Ni(II) on attapulgite increases with increasing temperature, and the thermodynamic parameters (??H 0, ??G 0 and ??S 0) calculated from the temperature dependent sorption isotherms suggest that the sorption of Ni(II) on attapulgite is a spontaneous and endothermic process. The high sorption capacity of attapulgite suggests that attapulgite is a suitable material for the preconcentration and solidification of radionickel from large volumes of aqueous solutions.  相似文献   

7.

The removal of U(VI) by biochar fibers from aqueous solutions has been investigated prior and after MnO2 surface-deposition. The removal efficiency has been studied as a function of pH, U(VI) concentration, ionic strength, temperature and contact time. The fibers morphology and surface complexes were analyzed by SEM–EDX and FTIR, respectively. Evaluation of the experimental data indicates that the composite presents extraordinary adsorption capacity (qmax = 3.8 mmol g−1, 904 mg g−1), which is attributed to the formation of inner-sphere surface complexes, and that the adsorption reaction is a relatively fast, endothermic and entropy-driven process.

  相似文献   

8.
Ni(II) sorption onto iron oxides and in particular hydrous ferric oxide (HFO) is among the important processes impacting its distribution, mobility, and bioavailability in environment. To develop mechanistic models for Ni, extended X-ray absorption fine structure (EXAFS) analysis has been conducted on Ni(II) sorbed to HFO. Coprecipitation revealed the formation of the metastable alpha-Ni(OH)(2) at a Ni(II) loading of 3.5 x 10(-3) molg(-1). On the other hand, Ni(II) formed inner-sphere mononuclear bidentate complexes along edges of FeO(6) octahedra when sorbed to HFO surfaces with Ni-O distances of 2.05-2.07 A and Ni-Fe distances of 3.07-3.11 A. This surface complex was observed by EXAFS study over 2.8 x 10(-3) to 10(-1) ionic strength, pH from 6 to 7, a Ni(II) loading of 8 x 10(-4) to 8.1 x 10(-3) molg(-1) HFO, and reaction times from 4 hours to 8 months. The short- and long-range structure analyses suggest that the presence of Ni(II) inhibited transformation of the amorphous iron oxide into a more crystalline form. However, Ni(2+) was not observed to substitute for Fe(3+) in the oxide structure. This study systematically addresses Ni(II) adsorption mechanisms to amorphous iron oxide. The experimentally defined surface complexes can be used to constrain surface complexation modeling for improved prediction of metal distribution at the iron oxide/aqueous interface.  相似文献   

9.
The interaction between radionuclides and solid/water interfaces is important to understand the physicochemical processes of radionuclides in the natural environment.Herein,the interaction of 60Co(Ⅱ) with TiO 2 in aqueous solution as a function of pH and ionic strength was studied by using batch technique combined with surface complexation model and density functional theory(DFT) calculations.The batch experimental results showed that the adsorption of 60Co(Ⅱ) was dependent on pH and independent of ionic strength,indicating the formation of inner-sphere surface complexes on TiO 2 surfaces.The results of surface complexation models and DFT calculations indicated that the surface species of 60Co(Ⅱ) adsorbed on TiO 2 followed the trend:B structure(i.e.,60Co(Ⅱ) was linked to one bridge oxygen site) was the dominant surface species at low pH,and TT structure(i.e.,60Co(Ⅱ) was linked to two terminal oxygen sites) became the important surface complex at neutral and alkaline pH values.These results demonstrated that a multi-technique approach could lead to definitive information on the structures of adsorbed 60Co(Ⅱ) at the molecular level at the TiO 2 /water interfaces,as well as realistic models to rationalize and accurately evaluate the macroscopic manifestations of radionuclide adsorption phenomena.  相似文献   

10.
A novel hierarchically structured γ-MnO2 has been synthesized using a simple chemical reaction between MnSO4 and KMnO4 in aqueous solution without using any templates, surfactants, catalysts, calcination and hydrothermal processes. As an example of potential applications, hierarchically structured γ-MnO2 was used as adsorbent in radionuclide 63Ni(II) treatment, and showed an excellent ability. The effects of pH, ionic strength, temperature, humic acid (HA) and fulvic acid (FA) on the sorption of radionuclide 63Ni(II) to hierarchically structured γ-MnO2 have been investigated by using batch techniques. The results indicated that the sorption of 63Ni(II) on γ-MnO2 is obviously dependent on pH values but independent of ionic strength. The presence of HA/FA strongly enhances the sorption of 63Ni(II) on γ-MnO2 at low pH values, whereas reduces 63Ni(II) sorption at high pH values. The sorption of 63Ni(II) on γ-MnO2 is attributed to inner-sphere surface complexation rather than outer-sphere surface complexation or ion exchange. The thermodynamic parameters (ΔH 0, ΔS 0, ΔG 0) are also calculated from the temperature dependent sorption isotherms, and the results suggest that the sorption of 63Ni(II) on γ-MnO2 is a spontaneous and endothermic process.  相似文献   

11.
In this work, sorption of Ni(II) from aqueous solution to goethite as a function of various water quality parameters and temperature was investigated. The results indicated that the pseudo-second-order rate equation fitted the kinetic sorption well. The sorption of Ni(II) to goethite was strongly dependent on pH and ionic strength. A positive effect of HA/FA on Ni(II) sorption was found at pH < 8.0, whereas a negative effect was observed at pH > 8.0. The Langmuir, Freundlich, and D-R models were applied to simulate the sorption isotherms at three different temperatures of 293.15 K, 313.15 K and 333.15 K. The thermodynamic parameters (ΔH 0, ΔS 0 and ΔG 0) were calculated from the temperature dependent sorption, and the results indicated that the sorption was endothermic and spontaneous. At low pH, the sorption of Ni(II) was dominated by outer-sphere surface complexation or ion exchange with Na+/H+ on goethite surfaces, whereas inner-sphere surface complexation was the main sorption mechanism at high pH.  相似文献   

12.
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.  相似文献   

13.
The sorption speciation of Ni(II) on Ca-montmorillonite was evaluated using a combination of batch experiments, extended X-ray absorption fine structure (EXAFS) spectroscopy and modeling. The pH and temperature at the aqueous-montmorillonite interface affects both the extent of Ni(II) sorption as well as the local atomic structure of the adsorbed Ni(II) ions. At 0.001 mol L(-1) Ca(NO(3))(2) and low pH, the study reveals that the majority of Ni(II) is adsorbed in the interlayers of Ca-montmorillonite coordinated by six water molecules in an octahedron as an outer-sphere complex. At higher pH, inner-sphere surface complexes are formed. The Ni-Si/Al distances (R(Ni-Al) = 3.00 ?, R(Ni-Si1) = 3.10 ? and R(Ni-Si2) = 3.26 ?) determined by EXAFS confirm the formation of mononuclear complexes located at the edges of Ca-montmorillonite platelets at pH 7.5 and 8.5. At pH 10.0, the Ni-Ni/Si distances (R(Ni-Ni) = 3.07 ? and R(Ni-Si) = 3.26 ?) indicates the formation of Ni-phyllosilicate precipitates. A rise in temperature promotes inner-sphere complexation, which in turn leads to an increase in Ni(II) sorption on Ca-montmorillonite. Sorption edges are fitted excellently by surface complexation model (SCM) with the aid of surface species determined from EXAFS spectroscopy.  相似文献   

14.
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.  相似文献   

15.
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.  相似文献   

16.
The sorption behavior and microscopic sequestration mechanisms of radionuclide 63Ni(II) on mordenite as a function of aging time,ionic strength,initial 63Ni(Ⅱ) concentrations,solid content and coexistent electrolyte ions were investigated by the com-bination of batch and EXAFS techniques.Macroscopic experiment results show that the sorption of 63Ni(Ⅱ) is dependent on ionic strength at pH<7,and independent of ionic strength at pH>7.The sorption percentage of 63Ni(Ⅱ) on mordenite increases with increasing solid content,while the sorption capacity decreases as solid content increases.The presence of different elec-trolyte ions can enhance or inhibit the sorption of Ni(II) on mordenite in various degrees.EXAFS analysis results of the sam-ples under three different ionic strengths suggest that the retained 63Ni(Ⅱ) in these samples exists in an octahedral environment with six water ligands.In the initial period of rapid uptake,the sorption of 63Ni(Ⅱ) is dominated by the formation of in-ner-sphere surface complexes.As aging time increases,63Ni(Ⅱ) sequestration behavior tends to be mainly controlled by the formation of Ni phyllosilicate co-precipitates and/or Ni(OH)2(s) precipitates.Results for the second shell fit of the sample pre-pared at an initial 63Ni(Ⅱ) concentration of 100 mg/L indicate the possible formation of Ni polynuclear surface complexes.Both the macroscopic sorption data and the molecular level evidence of 63Ni(Ⅱ) surface speciation at the mordenite/water in-terfaces should be factored into better predictions of the mobility and bioavailability of 63Ni(Ⅱ) in environment mediums.  相似文献   

17.
A kinetic study of the oxidation of [Co(H2L)(H2O)2]2+ (H2L = N,N-bis (salicylaldehyde-1,2-diaminoethane) Schiff base) by periodate in aqueous solution was performed over pH (2.3–3.4) range, (0.1–0.5) mol dm−3 ionic strength and temperatures 20–35 °C for a range of periodate and complex concentrations. The reaction rate showed a first-order dependence on both reactants and increased with pH over the range studied. The effects of Cu(II) and Fe(II) on the reaction rate were investigated over the (1.0–9.0) × 10−5 mol dm−3 range. The reaction was inhibited as the concentration of Cu(II) increased, and it was independent on Fe(II) concentrations over the ranges studied. An inner-sphere mechanism is proposed for the oxidation pathways of both the protonated and deprotonated CoII complex species.  相似文献   

18.
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.  相似文献   

19.
A novel adsorbent, TiO2/eggshell composite, was synthesized by sol–gel method, and characterized by XRD and FTIR. The removal of 60Co(II) from aqueous solution by TiO2/eggshell was studied as a function of contact time, pH, ionic strength, foreign ions, humic substances and temperature. The results indicated that the sorption of 60Co(II) on TiO2/eggshell was strongly dependent on pH and ionic strength. The Langmuir, Freundlich and D-R models were applied to simulate the sorption of 60Co(II) at temperatures of 303.15, 323.15 and 343.15 K. The thermodynamic parameters (ΔH 0, ΔS 0, ΔG 0) calculated from the temperature dependent sorption isotherms indicated that the sorption process of 60Co(II) on TiO2/eggshell was endothermic and spontaneous. At low pH, the sorption of 60Co(II) was dominated by outer-sphere surface complexation or ion exchange, whereas inner-sphere surface complexation was the main sorption mechanism at high pH. TiO2/eggshell composites have good potentialities for cost-effective disposal of 60Co(II) bearing wastewaters.  相似文献   

20.
The adsorption efficiency of Opuntia ficus indica fibres regarding the removal of hexavalent uranium [U(VI)] from aqueous solutions has been investigated prior and after the chemical treatment (e.g. phosphorylation and MnO2-coating) of the biomass. The separation/removal efficiency has been studied as a function of pH, uranium concentration, adsorbent mass, ionic strength, temperature and contact time. Evaluation of the experimental data shows that biosorption is strongly pH-depended and that the MnO2-coated product presents the highest adsorption capacity followed by the phosphorylated and non-treated material. Experiments with varying ionic strength/salinity don’t show any significant effect on the adsorption efficiency, indicating the formation of inner-sphere surface complexes. The adsorption reactions are in all cases exothermic and relatively fast, particularly regarding the adsorption on the MnO2-coated product. The results of the present study indicate that adsorption of uranium from waters is very effective by cactus fibres and particularly the modified treated fibres. The increased adsorption efficiency of the cactus fibres is attributed to their primary and secondary fibrillar structure, which result in a relative relative high specific surface available for sorption.  相似文献   

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