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1.
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   

2.
The influence of humic acid (HA) on Ni(ii) sorption to Ca-montmorillonite was examined by using a combination of batch sorption experiments and extended X-ray absorption fine structure (EXAFS) spectroscopy technique. The sorption of Ni(ii) on HA-montmorillonite hybrids is strongly dependent on pH and temperature. At low pH, the sorption of Ni(ii) is mainly dominated by Ni-HA-montmorillonite and outer-sphere surface complexation. The EXAFS results indicate that the first coordination shell of Ni(ii) consists of ~6 O atoms at the interatomic distances of ~2.04 ? in an octahedral structure. At high pH, binary Ni-montmorillonite surface complexation is the dominant sorption mechanism. EXAFS analysis indicates the formation of mononuclear complexes located at the edges of Ca-montmorillonite platelets at pH 7.5, while a Ni-Al layered double hydroxide (LDH) phase at the Ca-montmorillonite surface formed with pH 8.5. At pH 10.0, the dissolved HA-Ni(ii) complexation inhibits the precipitation of Ni hydroxide, and Ni-Al LDH phase forms. The rise of temperature increases the sorption capacity of Ni(ii), and promotes Ni-Al LDH phase formation and the growth of crystallites. The results are important to evaluate the physicochemical behavior of Ni(ii) in the natural environment.  相似文献   

3.
MX-80 bentonite was detected using acid-based titration, XRD and FTIR in detail. The sorption behavior of 63Ni(Ⅱ) from aqueous solution to MX-80 bentonite was investigated as a function of solid content, ionic strength and pH by using batch technique. The experimental data of 63Ni(Ⅱ) sorption on MX-80 bentonite was obtained using the diffuse layer model (DLM) with the aid of FITEQL 3.1 program. The results indicated that the sorption of 63Ni(Ⅱ) on MX-80 bentonite was mainly dominated by surface complexation...  相似文献   

4.
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   

5.
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   

6.
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   

7.
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   

8.
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.  相似文献   

9.
The effects of pH, ionic strength, competing ions and initial metal concentrations on the uptake behavior and mechanism of radioactive Ni(II) onto MnO2 was investigated using a combination of classical macroscopic methods and the extended X-ray absorption fine structure (EXAFS) spectroscopy technique. The results indicated that the uptake of Ni(II) on MnO2 is obviously dependent on pH but independent of ionic strength, which suggested that the uptake of Ni(II) onto MnO2 is attributed to an inner-sphere surface complex rather than an outer-sphere surface complex. EXAFS analysis shows that the hydrated Ni(II) is adsorbed through six-fold coordination with an average Ni–O interatomic distance of 2.04 ± 0.01 ?. It can be inferred from the EXAFS analysis that the inner-sphere surface complex of Ni(II) onto MnO2 is involved in both edge-sharing and corner-sharing linkages. Both the macroscopic uptake data and the molecular level evidence of Ni(II) surface speciation at the MnO2-water interfaces should be factored into better prediction of the bioavailability and mobility of Ni(II) in soil and water environment.  相似文献   

10.
The sorption of 63Ni(II) from aqueous solution using ZSM-5 zeolite was investigated by batch technique under ambient conditions. ZSM-5 zeolite was characterized by point of zero net proton charge (PZNPC) titration. The sorption was investigated as a function of shaking time, pH, ionic strength, foreign ions, humic acid (HA), fulvic acid (FA) and temperature. The results indicate that the sorption of 63Ni(II) on ZSM-5 zeolite is strongly dependent on pH. The sorption is dependent on ionic strength at low pH, but independent of ionic strength at high pH values. The presence of HA/FA enhances 63Ni(II) sorption at low pH values, whereas reduces 63Ni(II) sorption at high pH values. The sorption isotherms are simulated by Langmuir model very well. The thermodynamic parameters (i.e., ∆H 0, ∆S 0 and ∆G 0) for the sorption of 63Ni(II) are determined from the temperature dependent sorption isotherms at 293.15, 313.15 and 333.15 K, respectively, and the results indicate that the sorption process of 63Ni(II) on ZSM-5 zeolite is spontaneous and endothermic.  相似文献   

11.
Uranium(VI) was sorbed to freshly ground and leached albite in batch and flow-through systems in the pH range 5.0-6.4. The uranium(VI) surface complexes were studied by extended X-ray absorption fine structure (EXAFS) spectroscopy and time-resolved laser-induced fluorescence spectroscopy (TRLFS). The EXAFS analysis of uranium(VI) sorbed on albite at pH 5.8 and 5 x 10(-6) M U(VI) showed one silicon atom at a USi distance of 3.09 A, which is indicative of the formation of an inner-sphere, mononuclear, bidentate uranium(VI) surface complex, Si(O)2UO2, on the silicate tetrahedra of albite. Two additional uranium(VI) sorption complexes were detected by TRLFS at higher initial aqueous U(VI) concentrations. However, the structure of these surface complexes could not be derived from EXAFS, since the measured EXAFS spectra represent the average of two surface complex structures. In order to simulate U(VI) sorption onto weathered feldspar surfaces, albite was leached with 0.01 M HClO4, resulting in surface material similar to amorphous silica gel. EXAFS showed that the equatorial oxygen shell of uranium(VI) sorbed on this material at pH 5.0 and 5.8 was split in two distances of 2.23 and 2.44 A. This indicates the formation of an inner-sphere surface complex.  相似文献   

12.
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   

13.
用批式法研究了Co(Ⅱ)和Ni(Ⅱ)在北山花岗岩(BS03, 600 m)上的吸附. Co(Ⅱ)和Ni(Ⅱ)在北山花岗岩上的吸附分配比(Kd)均随pH值、离子强度和吸附质浓度的变化而变化; 在低pH值范围, Co(Ⅱ)和Ni(Ⅱ)的Kd 值随离子强度的增大显著减小, 而在高pH值范围,离子强度对Kd的影响较小; Co(Ⅱ)和Ni(Ⅱ)在北山花岗岩上的吸附作用可以分别用1个离子交换反应和2个内层表面配位反应进行定量描述. 建立了表面配位反应平衡常数(K)与过渡金属二价离子水解常数(OHK)之间的线性自由能关系(LFER),据此对Pb(Ⅱ)和Cu(Ⅱ)在花岗岩上的吸附进行了预测,并与实验结果进行了对比,获得了较好的一致性.  相似文献   

14.
The mechanism of Co uptake from aqueous solution onto hectorite (a magnesian smectite) and its impact on the stability of this clay mineral were investigated as a function of Co concentration (TotCo = 20 to 200 μM, 0.3 M NaNO(3)) and ionic strength (0.3 and 0.01 M NaNO(3), TotCo = 100 μM) by combining kinetics measurements and Co K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. The morphology of the sorbent phase was characterized by atomic force microscopy (AFM) and consists of lath-type particles bounded by large basal planes and layer edges. At low ionic strength (0.01 M NaNO(3)), important Co uptake occurred within the first 5 min of reaction, consistent with Co adsorption on exchange sites of hectorite basal planes. Thereafter, the sorption rate dramatically decreased. In contrast, at high ionic strength (0.3 M NaNO(3)), Co uptake rate was much slower within the first 5 min and afterward higher than at 0.01 M NaNO(3), consistent with Co adsorption on specific surface sites located on the edges of hectorite. Time-dependent isotherms for Co uptake at high ionic strength indicated the existence of several sorption mechanisms having distinct equilibration times. The dissolution of hectorite was monitored before and after Co addition. A congruent dissolution regime was observed prior to Co addition. Just after Co addition, an excess release of Mg relatively to congruent dissolution rates occurred at both high and low ionic strengths. At high ionic strength, this excess release nearly equaled the amount of sorbed Co. The dissolution rate of hectorite then decreased at longer Co sorption times. EXAFS spectra of hectorite reacted with Co at high and low ionic strengths and for reaction times longer than 6 h, exhibited similar features, suggesting that the local structural environments of Co atoms are similar. Spectral simulations revealed the occurrence of approximately 2 Mg and approximately 2 Si neighboring cations at interatomic distances characteristic of edge-sharing linkages between Co and Mg octahedra and corner-sharing linkages between Co octahedra and Si tetrahedra, respectively. This local structure is characteristic of inner sphere mononuclear surface complexes at layer edges of hectorite platelets. The occurrence of these complexes even at low ionic strength apparently conflicts with kinetics results, as exchangeable divalent cations are known to form outer sphere surface complexes. To clarify this issue, the amount of Co adsorbed on exchange sites was calculated from the solute Co concentration, assuming that cation exchange was always at equilibrium. These calculations showed that sorbed Co was transferred within 48 h from exchange sites to edge sorption sites. Copyright 1999 Academic Press.  相似文献   

15.
Zn(II) sorption onto Al and Si oxides was studied as a function of pH (5.1-7.52), sorption density, and ionic strength. This study was carried out to determine the role of the various reaction conditions and sorbent phases in Zn complexation at oxide surfaces. Extended X-ray absorption fine structure (EXAFS) spectroscopy was used to probe the Zn atomic environment at the metal oxide/aqueous interface. For both amorphous silica and high-surface-area gibbsite, Zn sorption kinetics were rapid and reached completion within 24 h. In contrast, Zn sorption on low-surface-area-gibbsite was much slower, taking nearly 800 h for a sorption plateau to be reached. In the case of silica, EXAFS revealed that Zn was in octahedral coordination with first-shell oxygen atoms up to a surface loading of approximately 1 micro molm(-2), changing to tetrahedral coordination as surface loading and pH increased. For the high-surface-area gibbsite system, the Znz.sbnd;O first-shell distance was intermediate between values for tetrahedral and octahedral coordination over all loading levels. Zn formed inner-sphere adsorption complexes on both silica and high-surface-area gibbsite over all reaction conditions. For Zn sorption on low-surface-area gibbsite, formation of Znz.sbnd;Al layered double hydroxide (LDH) occurred and was the cause for the observed slow Zn sorption kinetics. The highest pH sample (7.51) in the Zn-amorphous silica system resulted in the formation of an amorphous Zn(OH)(2) precipitate with tetrahedral coordination between Zn and O. Aging the reaction samples did not alter the Zn complex in any of the systems. The results of this study indicate the variability of Zn complexation at surfaces prevalent in soil and aquatic systems and the importance of combining macroscopic observations with methods capable of determining metal complex formation mechanisms.  相似文献   

16.
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   

17.
Sequestration of Ni(II) on diatomite as a function of reaction time, pH, ionic strength, foreign ions and temperature were investigated by batch sorption technique. The results indicated that the sorption of Ni(II) on diatomite was quickly in the first contact time of 2 h and then slowly with increasing contact time. The interaction of Ni(II) with diatomite was strongly pH- and ionic strength-dependent at low pH values (i.e., which was dominated by ion exchange or outer-sphere surface complexation), while the pH-dependent and ionic strength-independent sorption at high pH suggested that inner-sphere or multinuclear surface complexation was the main sorption mechanism. With increasing temperature, the sorption of Ni(II) on diatomite increased and the experimental data were well fitted by Langmuir model. The sorption samples at pH 6.8 and 10.0 were also characterized by XPS spectroscopy, and the results suggested that Si atoms also participated in Ni(II) sorption on diatomite. The results are important to evaluate the physicochemical behavior of Ni(II) and other similar radionuclides and heavy metal ions in the environment.  相似文献   

18.
In this work, Na-montmorillonite was used as a novel adsorbent for the sorption of Ni(II) from aqueous solutions. The sorption and desorption of Ni(II) on Na-montmorillonite was investigated as the function of pH, ionic strength, Ni(II) concentrations and temperature. The results indicated that the sorption of Ni(II) on Na-montmorillonite was strongly dependent on pH, ionic strength and temperature. The sorption of Ni(II) increases slowly from 22.1 to 51.4% at pH range 2–6.5, abruptly at pH 6.5–9, and at last maintains high level with increasing pH at pH > 9 in 0.1 mol/L NaNO3 solutions. The Ni(II) kinetic sorption on Na-montmorillonite was fitted by the pseudo-second-order model better than by the pseudo-first-order model and the experimental data implies that Ni(II) sorption on montmorillonite were mainly controlled by the film diffusion mechanism. The Langmuir, Freundlich and D–R models were used to simulate the sorption data at three different temperatures (298.15, 318.15 and 338.15 K) and the results indicated that Langmuir model simulates the experimental data better than Freundlich and D–R models. The sorption–desorption isotherm of Ni(II) on montmorillonite suggested that the sorption is irreversible. The irreversible sorption of Ni(II) on montmorillonite indicates that montmorillonite can be used to pre-concentration and solidification of Ni(II) from large volumes of solution and to storage Ni(II) ions stably.  相似文献   

19.
The graphene oxides(GOs) have attracted multidisciplinary study because of their special physicochemical properties. The high surface area and large amounts of oxygen-containing functional groups make GOs suitable materials for the efficient elimination of heavy metal ions from aqueous solutions. Herein the sorption of Ni(II) on GOs was studied using batch experiments, and the results showed that the sorption of Ni(II) is strongly dependent on p H and ionic strength at pH8, and independent of ionic strength at pH8. The sorption of Ni(II) is mainly dominated by outer-sphere surface complexation and ion exchange at low p H, and by inner-sphere surface complexation at high p H. The interaction of Ni(II) with GOs was also investigated by theoretical density functional theory(DFT) calculations, and the results show that the sorption of Ni(II) on GOs is mainly attributed to the –COH and –COC groups and the DFT calculations show that Ni(II) forms stable GO_Ni_triplet structure with the binding energy of -39.44 kcal/mol, which is in good agreement with the batch sorption experimental results. The results are important for the application of GOs as adsorbents in the efficient removal of Ni(II) from wastewater in environmental pollution cleanup.  相似文献   

20.
In this paper, the sorption of Co(II) from aqueous solution to Ca-montmorillonite was studied under ambient conditions by using batch technique. The effects of contact time, solid content, pH, ionic strength and temperature on the sorption of Co(II) to Ca-montmorillonite was also investigated. The results indicated that the sorption of Co(II) was strongly dependent on pH values. The sorption was dependent on ionic strength at low pH values, but independent of ionic strength at high pH values. Outer-sphere surface complexes were formed on the surface of Ca-montmorillonite at low pH values, whereas inner-sphere surface complexes were formed at high pH values. The Langmuir, Freundlich and Dubinin–Radushkevich (D–R) models were used to simulate the sorption isotherms of Co(II) at three different temperatures. The thermodynamic parameters (ΔH 0, ΔS 0 and ΔG 0) were calculated from the temperature dependent sorption isotherms, and the results indicated that the sorption reaction of Co(II) to Ca-montmorillonite was an endothermic and spontaneous process. The high sorption capacity of Co(II) on Ca-montmorillonite suggests that the Ca-montmorillonite is a suitable material for the preconcentration and solidification of radiocobalt from aqueous solutions.  相似文献   

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