Adsorption behavior of cesium on montmorillonite-type clay in the presence of potassium ions

The adsorption behavior of Cs ions on a montmorillonite-type clay was investigated in the presence of potassium ions, using a radiotracer technique. The initial concentration of K⁺ added to the CsCl was between 10^-4 and 10^-1 mol/l. The addition of K⁺ to the CsCl solution at different concentrations (10^-6-10^-2 mol/l) reduced the amount of Cs⁺ adsorbed on clay. The maximum ratio of Cs⁺ exchanged, calculated from a linearized form of Langmuir plot was in agreement with the ion exchange isotherms of Cs-K ions. Sorption energy evaluated from the graph of corrected selectivity coefficients vs. equivalent fraction of Cs in the solid phase was compared to the energy values obtained from Dubinin-Radushkevich (D-R) isotherms. Freundlich isotherm parameters were used to characterize a site distribution function, which provides information about the affinity ratio of the adsorption sites of Cs⁺ and K⁺ ions. The ion exchange isotherm of Cs-K systems exhibited a Langmuir type curve for all K⁺ concentrations.     

A new ecomaterial zirconyl molybdopyrophosphate for the removal of 137Cs and 90Sr from HLLW

A new ecomaterial, zirconyl molybdopyrophosphate (ZMPP), was prepared by a coprecipitation method. The removal of Cs⁺ and Sr²⁺ ions from simulated strong acid HLLW using the ion exchange process on ZMPP had been investigated. It showed that there are more than 90% Cs⁺ and Sr²⁺ removed from the simulated HLLW on ZMPP despite the presence of other metal ions, such as Na⁺, Al³⁺, Fe³⁺, etc. in excess. Then ZMPP may likely be a selective ion exchanger for the removal of ¹³⁷Cs and ⁹⁰Sr directly from strong acid HLLW.     

Affinity and removal of radionuclides mixture from low-level liquid waste by synthetic ferrierites

The affinity and removal efficiency of ¹³⁷Cs⁺, ¹³³Ba²⁺, ⁸⁵Sr²⁺ and ²⁴¹Am³⁺ mixture from aqueous solutions using two synthetic ferrierites HSZ 700KOA and 700KOD commercially used as a catalyst in oil industry were investigated. The uptake of metal ions as a function of different parameters has been studied using batch equilibrium technique. Kinetic curves showed that the equilibrium was mostly reached within 45 min for Cs⁺ and Ba²⁺ and revealed to be longer for Sr²⁺ and Am³⁺. Using Freundlich and Langmuir adsorption isotherms, the results showed that the affinity and adsorption capacity of 700KOA and 700KOD follow the order: Cs⁺ > Ba²⁺ > Sr²⁺ > Am³⁺ with higher values for first material. Both adsorbents exhibited significant high capacity for Cs⁺ relative to other cations giving q _max 1.97 and 1.78 mmol g⁻¹ for 700KOA and 700KOD, respectively. All metals uptake found to be concentration dependant and independent of the pH over 2 to 10 range except Am³⁺; this reveals that the adsorption mechanism is controlled mainly by pure ion exchange reaction for Cs⁺, Ba²⁺, Sr²⁺ and by surface complexation mechanism for Am³⁺. These simple nontoxic materials are recommended to be used for radioactive waste treatment especially fission product ¹³⁷Cs and activation product ¹³³Ba.     

Separation of strontium and yttrium in nitric acid solutions using zirconium titanium phosphate and Dowex exchangers

Sulfonated ion irradiated (H⁺ and He²⁺) PEEK films were synthesized with a range of cross-linking density and a variety of sulfonation degrees. Batch adsorption experiments were carried out at an initial pH of 6.0 ± 0.2, initial concentrations of Pb²⁺ and ¹³⁷Cs ions of 10.0 mg L⁻¹ and 5500 Bq L⁻¹, respectively. The maximum adsorption capacity was 60 mg g⁻¹ for Pb²⁺, and the distribution coefficient reached 6200 cm³ g⁻¹ for ¹³⁷Cs. The results indicated that sulfonation could be used to recycle low cross-linked PEEK and prepare efficient adsorbents to remove toxic Pb²⁺ and ¹³⁷Cs from polluted aqueous solutions.

     

A method for the replacement of 137Cs with 40K as a non-hazardous radioactive tracer for open-source decommissioning research applications

The potential of ⁴⁰K as a radioactive tracer analogue of ¹³⁷Cs in ion exchange experiments is reported. Solutions of varying concentrations of potassium chloride (KCl) have been monitored radiometrically in a sodium iodide well-counter to determine the activity-concentration relationship. Ion exchange reactions using an exemplar ion exchange resin, KCl and non-radioactive caesium chloride (CsCl) solutions have been studied radiometrically. The adsorbed amounts of potassium and caesium are observed, inferred from displaced K⁺ ions, to be consistent with the total exchange capacity of the resin. Adsorption isotherm models have been applied to the experimental data, with the Freundlich isotherm observed to fit the data with the highest degree of consistency. The reported results indicate that decontamination techniques involving hazardous isotopes of anthropogenic origin such as ¹³⁷Cs can be developed, evaluated and optimised by substituting a chemically and physically similar non-hazardous radioactive isotope, in this case ⁴⁰K. This represents a means by which innovative decontamination techniques and regimes might be identified without the need to use ¹³⁷Cs and thus avoids additional generation of radioactive wastes.     

A Novel Vanadosilicate with Hexadeca‐Coordinated Cs+ Ions as a Highly Effective Cs+ Remover

The effective removal of ¹³⁷Cs⁺ ions from contaminated groundwater and seawater and from radioactive nuclear waste solutions is crucial for public health and for the continuous operation of nuclear power plants. Various ¹³⁷Cs⁺ removers have been developed, but more effective ¹³⁷Cs⁺ removers are still needed. A novel microporous vanadosilicate with mixed‐valence vanadium (V⁴⁺ and V⁵⁺) ions is now reported, which shows an excellent ability for Cs⁺ capture and immobilization from groundwater, seawater, and nuclear waste solutions. This material is superior to other known materials in terms of selectivity, capacity, and kinetics, and at very low Cs⁺ concentrations, it was found to be the most effective material for the removal of radioactive Cs⁺ ions under the test conditions. This novel vanadosilicate also contains hexadeca‐coordinated Cs⁺ ions, which corresponds to the highest coordination number ever described.     

Batch and continuous fixed-bed column adsorption of Cs+ and Sr2+ onto montmorillonite–iron oxide composite: Comparative and competitive study

A montmorillonite–iron oxide composite (MIOC) was prepared to assess its effectiveness in the removal of Cs⁺ and Sr²⁺ from aqueous solution. A comparative and competitive adsorption study was conducted in single and binary systems. Used materials have been characterized by X-ray diffraction (XRD) and Infrared spectroscopy. Adsorption of Cs⁺ and Sr²⁺ as a function of contact time and pH was investigated, adsorption data of single metal solutions were well fitted to the Freundlich–Langmuir isotherm models. Equilibrium isotherms for the binary removal of Cs⁺ and Sr²⁺ by MIOC have been analyzed by using non modified and extended Langmuir models with a satisfactory R ² values. Neutral solution pH was found to be favorable for both single and binary systems. The adsorption model analysis revealed that MIOC was more selective for Sr than Cs. The maximum adsorption capacities for individual Cs⁺ and Sr²⁺ solutions were 52.6 and 55.5 mg g^?1, respectively. While the maximum uptakes in the binary system were 41.6 and 47.6 mg g^?1 for Cs⁺ and Sr²⁺, respectively. Column adsorption experiments were carried out at room temperature under the effect of various operating parameters such as bed depth, initial cation concentration and flow rate, Breakthrough curves were well fitted to the Thomas model. Desorption experiments were also conducted to assess the possibility for the reuse of adsorbent and the recovery of cations.     

Structural characterization of ammonium molybdophosphate with different amount of cesium adsorption

Powdered crystal AMP was synthesized by precipitation method and different Cs-loading AMP samples were prepared in this work. They were studied by modern methods of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA) to gain a better understanding of the ion exchange mechanism of ammonium molybdophosphate (AMP). The XRD patterns combined with the FT-IR analysis indicate that the Keggin structure is retained after Cs adsorption, while the changes of certain characteristic diffraction peaks show crystal lattice distortion caused by the mismatching sizes of Cs⁺ and [NH₄]⁺. The TGA showed that the weight percent of H₂O and [NH₄]⁺ decreases as the amount of Cs adsorbed onto AMP increases, which corresponds with the theory of isomorphous exchange.     

Highly effective removal of 22Na, 134Cs and 60Co from aqueous solutions by titanosilicate: a radiotracer study

Sorption of Na(I), Cs(I) and Co(II) radionuclides from aqueous solutions by titanosilicate have been investigated. The time dependent studies for metal ions showed relatively rapid sorption kinetics between 5 and 30 min to reach equilibrium. A batch adsorption model based on assumption of the pseudo-second-order mechanism was applied to predict the sorption rate, while the equilibrium capacity was calculated at different temperatures. The adsorption of different radionuclides onto titanosilicate was found to be favored at high ions concentrations and low temperature for Na⁺ and Co²⁺ while at high temperature for Cs⁺. Activation energy of adsorption was computed to be 2.35, 24.11 and 5.74 kJ/mol for adsorption of Na(I), Cs(I) and Co(II), respectively. The results revealed that the adsorption of Cs⁺ is the highest relative to Na⁺ and Co²⁺ at different conditions which may be attributed to its low hydration energy. Further, the equilibrium isotherm for the interested ions was analyzed and it was found to obey Frundlich equation.     

Synthesis and characterization of Nb–Ge doped titanosilicate nanoparticles and study of their selectivity for absorption of 137Cs and 90Sr

In this research, for the first time Nb and Ge were doped into titanosilicate nanoparticles up to 25% simultaneously. Crystalline phases and morphology of the synthesized samples were studied by X-ray diffraction (XRD) method and scanning electron microscope (SEM), respectively. Elemental analysis of the samples was performed using X-ray fluorescence (XRF) and Energy dispersive X-ray (EDX) techniques. Surface area of the samples was measured by BET method. Ion exchange potential of the synthesized samples for Sr²⁺ and Cs⁺ and effective parameters such as concentration, temperature, time, and pH were investigated. In addition,¹³⁷Cs and ⁹⁰Sr radio nuclides absorption in the best appropriate sample was examined. The selectivity of the samples for absorption of ¹³⁷Cs and ⁹⁰Sr was studied by gamma spectroscopy, liquid scintillation spectrometry, and atomic absorption spectroscopy methods. The obtained results showed that the prepared samples had good potential for absorption of ¹³⁷Cs and ⁹⁰Sr from the model solution. The sample containing equal amount of niobium and germanium, removed completely the ¹³⁷Cs within the waste water of Tehran nuclear reactor and ⁹⁰Sr in the desired solution.     

Heats of adsorption of water on vermiculite having large singly-charged cations in the exchange complex

The isotherms and differential heats of adsorption of water vapor on K-, NH₄-, Rb-, and Cs-vermiculites have been studied by means of a Calvet microcalorimeter having a microweighing adsorption attachment. The results are interpreted taking into account that the large cations K₊, NH₄ ⁺, Rb⁺, and especially Cs⁺, may not replace the initial exchange complexes (Na⁺ or Mg²⁺) of the mineral completely, so that besides hydration of the principal exchange cations the reaction of water molecules being adsorbed with the residual Na⁺ or Mg⁺ cations also takes place. The presence of a certain number of the initial cations (Na⁺ or Mg²⁺) in the Cs form of vermiculite is confirmed by the results of studying the ion exchange equilibria on the Na and natural (Mg) forms of the mineral involving the participation of the Cs₊ ions. The nature of the variation in the dependence of the differential heats of adsorption with an increase in the amount of adsorbed substance indicates the segregation (isolation) of the principal (K⁺, NH₄ ⁺, Rb⁺, Cs⁺) and the residual (Na⁺, Mg²⁺) exchange cation in the structure of the mineral.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 22, No. 1, pp. 91–96, January–February, 1986.     

Effect of Cs+ ions on the electrochemical nanogravimetric response of platinum electrode in acid media

Platinum electrodes have been investigated in sulfuric acid solutions in the presence and absence of Cs⁺ ions by electrochemical quartz crystal nanobalance (EQCN). An unusual potential dependence of the quartz crystal frequency response has been observed in the presence of Cs⁺ ions. The frequency decrease is more pronounced in the region of the underpotential deposition of hydrogen, and the frequency decrease in the double layer region diminishes as the concentration ratio of Cs⁺ and H⁺ ions increases. After immersion in Cs₂SO₄ solutions the frequency change was higher than that expected taking into account the density and viscosity. The effects observed can be explained by the specific adsorption of Cs⁺ ions on the Pt surface, which competes with the hydrogen adsorption. At more positive potentials than the potential of zero charge (pzc) a desorption of the Cs⁺ ions starts. In this potential region both Cs⁺ and HSO₄^? ions are adsorbed at the platinum surface. In the double layer region the mass change caused by the desorption of Cs⁺ ions and the starting adsorption of sulfate ions compensates each other.     

Stable Aqueous Solutions of Naked Titanate Nanotubes

Aqueous solutions of naked nanotubes with Ti concentration up to 10 mM are obtained by hydrothermal synthesis followed by extensive ultrasound treatment. The morphology, surface characteristics, and solution behavior of the solubilized nanotubes are investigated. The time course of the solubilization process driven by ultrasound follows a first‐order kinetic law and is mediated by the competition between Na⁺ and H⁺ for surface sites. The dynamics of interaction with small cations (i.e. the sodium ion) is studied by nuclear magnetic resonance spectroscopy and is demonstrated to be a multifaced process, since Na⁺ is in part free to exchange between the binding sites on nanotubes and the bulk and in part is confined to slowly exchanging nanotube sites. The aqueous titanate nanotube solutions are stable for months, thus opening new perspectives for the use of this material in drug delivery and in homogeneous photocatalysis.     

Selective adsorption of europium/III/ and americium/III/ in non-proliferative mycobacterial suspensions

The absorption effect of 5% w/w non-proliferative cell suspensions of Mycobacterium smegmatis on labelled solutions of Eu³⁺ ions, both alone and in admixtures with Am³⁺, Co²⁺ and Cs⁺, was studied at pH 1.0 as a function of time and cationic concentration. For 10 M concentrations of Eu, Co and Cs, selective adsorption of the trivalent lanthanide and actinide ions was practically quantitative after 90 min; no significant adsorption was observed for cobalt and cesium ions. Column adsorption measurements with the mycobacterial biomass showed that desorption of the M³⁺ ions did not occur at less than 2M HCl and remained incomplete even at higher acidities.     

Oligoether‐Strapped Calix[4]pyrrole: An Ion‐Pair Receptor Displaying Cation‐Dependent Chloride Anion Transport

A ditopic ion‐pair receptor ( 1 ), which has tunable cation‐ and anion‐binding sites, has been synthesized and characterized. Spectroscopic analyses provide support for the conclusion that receptor 1 binds fluoride and chloride anions strongly and forms stable 1:1 complexes ([ 1? F]^? and [ 1? Cl]^?) with appropriately chosen salts of these anions in acetonitrile. When the anion complexes of 1 were treated with alkali metal ions (Li⁺, Na⁺, K⁺, Cs⁺, as their perchlorate salts), ion‐dependent interactions were observed that were found to depend on both the choice of added cation and the initially complexed anion. In the case of [ 1? F]^?, no appreciable interaction with the K⁺ ion was seen. On the other hand, when this complex was treated with Li⁺ or Na⁺ ions, decomplexation of the bound fluoride anion was observed. In contrast to what was seen with Li⁺, Na⁺, K⁺, treating [ 1?F ]^? with Cs⁺ ions gave rise to a stable, host‐separated ion‐pair complex, [F ?1? Cs], which contains the Cs⁺ ion bound in the cup‐like portion of the calix[4]pyrrole. Different complexation behavior was seen in the case of the chloride complex, [ 1? Cl]^?. Here, no appreciable interaction was observed with Na⁺ or K⁺. In contrast, treating with Li⁺ produces a tight ion‐pair complex, [ 1? Li ? Cl], in which the cation is bound to the crown moiety. In analogy to what was seen for [ 1? F]^?, treatment of [ 1? Cl]^? with Cs⁺ ions gives rise to a host‐separated ion‐pair complex, [Cl ?1? Cs], in which the cation is bound to the cup of the calix[4]pyrrole. As inferred from liposomal model membrane transport studies, system 1 can act as an effective carrier for several chloride anion salts of Group 1 cations, operating through both symport (chloride+cation co‐transport) and antiport (nitrate‐for‐chloride exchange) mechanisms. This transport behavior stands in contrast to what is seen for simple octamethylcalix[4]pyrrole, which acts as an effective carrier for cesium chloride but does not operates through a nitrate‐for‐chloride anion exchange mechanism.     

Determination and preconcentration of natural and radio-cesium from aqueous solution

This work reports a modified atomic emission spectrometric (AES) method to determine cesium(I), based on the measurement of emission intensity at 455.5 nm with a limit of quantitation (LOQ) of 5.5 mg/l and a linear range up to 100 mg/l. In order to increase the sensitivity and lower the detection limits, potential sorbents were investigated for preconcentrating Cs from natural waters. Among the various ion-exchange materials synthesized, potassium hexanitrocobaltate (PHNCo) yielded the highest capacity for ¹³⁷Cs tagged Cs⁺ solutions as measured by gamma-spectrometry with a HPGe detector, showing the potential of a cesium preconcentration sorbent. As an alternative to AES determination, the PHNCo sorbent may be used for Cs⁺ collection from radiocesium tagged solutions and the retained activity in the dry solid exchanger be determined by gamma-spectrometry. This revised version was published online in August 2006 with corrections to the Cover Date.     

Effect of halides and alkali cations on the Zn(Hg)/Zn(II) electrode reactions

The title subject has been studied by galvanostatic single-pulse, chronopotentiometric and equilibrium measurements on the Zn(Hg)/Zn(II) electrode in x M KI+(1?x) M KCl (x from 0 to 1), 1 M KBr and 1 M MeCl (Me=Li, Na, K and Cs) solutions of pH 3 at 25°C. Quantitative information about the effect of specifically adsorbed halides on the rates of the Zn(II)/Zn(I) and the Zn(I)/Zn(Hg) steps is obtained separately (for the latter step mainly at potentials near ?1.0 V(SCE)), and the latter step seems to be more influenced than the former by the adsorption. An attempt is made to correlate the adsorption effect on the rate of the Zn(II)/Zn(I) step to double-layer parameters according to recent models for such effects. The extra current observed at potentials where the halides are adsorbed, seems to vary with the surface activity of the specifically adsorbed ion. The lack of any observed kinetic effect of Cs⁺, which is specifically adsorbed at these potentials, is possibly due to the Cs⁺ specific adsorption enhancing the Cl^? specific adsorption and vice versa, so that the decelerating and accelerating effects by these ions may cancel each other.     

Comparison of two methods for ginsenosides quantitation

The present study provides a comparison of two liquid chromatography–tandem mass spectrometry methods for ginsenosides analysis. The two methods have the same liquid chromatography separation procedure, and both use tandem mass spectrometry detection. However, one method uses multiple reaction monitoring transitions commonly recommended in the literature starting with [M + Na]⁺ as the molecular ions and with detection of specific fragment ions from the molecules M, while the other is an original method using [M + Cs]⁺ as molecular ions and Cs⁺ as fragment ion. The method using [M + Cs]⁺ as molecular ion has a very high sensitivity allowing the measurement of concentrations in the injecting solutions as low as 4 ng/ml with peaks at this concentration showing signal to noise ratio of 20 or higher. The procedures were utilized for the measurement of eight ginsenosides (Rb1, Rb2, Rc, Rd, Re, Rf (S), Rg1, and Rg2), although the method using [M + Cs]⁺ has the potential for measuring other ginsenosides. As an application, the ginsenosides were measured in several types of ginseng root, several dietary supplements containing ginseng extracts, four energy drinks, and a sample of ashwagandha.     

Stepwise Reduction of Azapentabenzocorannulene

Mono‐ and dianions of 2‐tert‐butyl‐3a²‐azapentabenzo[bc,ef,hi,kl,no]corannulene ( 1 a ) were synthesized by chemical reduction with sodium and cesium metals, and crystallized as the corresponding salts in the presence of 18‐crown‐6 ether. X‐ray diffraction analysis of the sodium salt, [{Na⁺(18‐crown‐6)(THF)₂}₃{Na⁺(18‐crown‐6)(THF)}( 1 a ^2?)₂], revealed the presence of a naked dianion. In contrast, controlled reaction of 1 a with Cs allowed the isolation of singly and doubly reduced forms of 1 a , both forming π‐complexes with cesium ions in the solid state. In [{Cs⁺(18‐crown‐6)}( 1 a ^?)]?THF, asymmetric binding of the Cs⁺ ion to the concave surface of 1 a ^? is observed, whereas in [{Cs⁺(18‐crown‐6)}₂( 1 a ^2?)], two Cs⁺ ions bind to both the concave and convex surfaces of the dianion. The present study provides the first successful isolation and characterization of the reduced products of heteroatom‐containing buckybowl molecules.