Effect of complexing anions on sorption of U(VI), <Superscript>90</Superscript>Sr,and <Superscript>90</Superscript>Y from aqueous solutions on layered double hydroxides of Mg,Al, and Nd

Sorption of ⁹⁰Sr and ⁹⁰Y from aqueous solutions on Mg-Al and Mg-Nd layered double hydroxides (LDHs) in various forms was studied. The distribution coefficients K _d of U(VI) and ⁹⁰Sr on LDH-Mg-Al-EDTA are 100–120 ml g⁻¹ in 15 min of contact of the solid and liquid phases at V/m = 50 ml g⁻¹. At the same time, under similar conditions, U(VI) and ⁹⁰Sr are not sorbed from aqueous solutions on LDH-Mg-Al-C₂O₄. The sorption of U(VI) from aqueous solutions containing H₂EDTA²⁻, C₂O₄²⁻, and CO₃²⁻ on LDH-Mg-Nd-CO₃ and LDH-Mg-Al-CO₃ strongly depends on the concentration of the complexing anions in the solution. In particular, for 10⁻³ M aqueous UO₂²⁺ solutions, with an increase in [C₂O₄²⁻] from 10⁻³ to 5 × 10⁻² M, K _d of U(VI) decreases from >5 × 10³ to 70 ml g⁻¹ for LDH-Mg-Al-CO₃ and from 170 to ∼0 ml g⁻¹ for LDH-Mg-Nd-CO₃. In the presence of 10⁻³ to 5 × 10⁻² M CO₃²⁻ in aqueous solution, U(VI) is not noticeably sorbed on LDH-Mg-Nd-CO₃ (K _d does not exceed 16 ml g⁻¹ at V/m = 50 ml g⁻¹), and on LDH-Mg-Al-CO₃ the sorption sharply decreases (K _d decreases from >5 × 10³ to ∼0 ml g⁻¹ at V/m = 50 ml g⁻¹). The presence of complexing anions in the solution does not appreciably affect the ⁹⁰Sr sorption, but noticeably affects the 90Y sorption. With an increase in their concentration, K _d of ⁹⁰Y appreciably decreases. The effect exerted by Sr²⁺ ions on the sorption of microamounts of U(VI) and by UO₂²⁺ ions on the sorption of microamounts of ⁹⁰Sr and ⁹⁰Y from aqueous solutions on LDH-Mg-Nd-CO₃ was also examined.     

Sorption properties of silicate materials based on Ca<Subscript>2</Subscript>SiO<Subscript>4</Subscript>

Sorption studies showed that a silicate material formed in the course of metallurgical slag reprocessing, containing dicalcium silicate as the major component, exhibits high affinity (logK _d [ml g⁻¹] > 4) for U(VI), Pu(IV), REE(III), and Th(IV) cations and for simple anions and appreciable affinity (logK _d [ml g⁻¹] > 2) for Cs(I) and Sr(II) cations in their sorption from river water. The sorbent can be of practical interest for separation, preconcentration, neutralization, and recovery of harmful chemical elements and radioactive substances from aqueous solutions, followed by their cementation (solidification) and safe disposal.     

Leaching of<Superscript>60</Superscript>Co and<Superscript>137</Superscript>Cs from spent ion exchange resins in cement-bentonite clay matrix

The leaching rate of⁶⁰Co and¹³⁷Cs from the spent cation exchange resins in cement-bentonite matrix has been studied. The solidification matrix was a standard Portland cement mixed with 290–350 (kg/m³) spent cation exchange resins, with or without 2–5% of bentonite clay. The leaching rates from the cementbentonite matrix for⁶⁰Co : (4,2–7,0) × 10⁻⁵ (cm/d) and¹³⁷Cs : (3,2–6,6) × 10⁻⁴ (cm/d), after 125 days were measured. From the leaching data the apparent diffusivity of cobalt and cesium in cement-bentonite clay matrix with a waste load of 290–350 (kg/m³) spent cation exchange resins, was measured for⁶⁰Co : (1,1−4,0) × 10⁻⁶ (cm²/d) and¹³⁷Cs : (0,5–2,6) x× 10⁻⁴ (cm²/d), after 125 days. The results presented in this paper are part of the results obtained in a 20-year mortar and concrete testing project which will influence the design of radio-active waste management for a future Serbian radioactive waste disposal centre.     

Coprecipitation of <Superscript>137</Superscript>Cs, <Superscript>90</Superscript>Sr,and <Superscript>90</Superscript>Y from aqueous and organic solutions with triethylenediamine complexes of <Emphasis Type="Italic">d</Emphasis>-element nitrates

Coprecipitation of ¹³⁷Cs, ⁹⁰Sr, and ⁹⁰Y with low-soluble complexes of nitrates of d elements (Cu²⁺, Ni²⁺, Zn²⁺) with triethylenediamine [(CH₂-CH₂)₃N₂] from aqueous and aqueous-organic solutions was studied. ¹³⁷Cs and ⁹⁰Sr do not noticeably coprecipitate with precipitates of complexes of Cu²⁺, Ni²⁺, and Zn²⁺ with (CH₂-CH₂)₃N₂ in water; in the process, the radionuclide recovery into the precipitate phase does not exceed 10%. At the same time, the degree of recovery of ⁹⁰Y reaches 65% depending on the experimental conditions. In C₂H₅OH and CH₃CN containing 9 and 5% H₂O, respectively, ¹³⁷Cs, ⁹⁰Sr, and ⁹⁰Y coprecipitate with the complexes to a greater extent, with the degree of recovery varying from 30 to 97% at the molar ratio M²⁺: (CH₂-CH₂)₃N₂ = 1 : 1.     

Sorption of <Superscript>137</Superscript>Cs from seawater onto resorcinol–formaldehyde resin

Sorption of ¹³⁷Cs from seawater onto a selective cation exchanger based on resorcinol–formaldehyde resin was studied. The maximal distribution coefficient of ¹³⁷Cs at the ratio S: L = 1: 1000 is (4.1–4.5) × 10³ cm³ g^–1. The sorption-selective characteristics of the resin are negatively affected by alkaline earth meal ions. In the dynamic regime, the operation life of the resorcinol–formaldehyde resin exceeds 700 bed volumes with more than 95% efficiency of cesium sorption. More than 95% of ¹³⁷Cs is eluted with a 1–3 M HNO₃ solution. The eluate volume does not exceed 10 bed volumes.     

Behavior of Microamounts of <Superscript>22</Superscript>Na, <Superscript>85</Superscript>Sr, <Superscript>137</Superscript>Cs,and <Superscript>152</Superscript>Eu in Sorption and Coprecipitation on Mixed Potassium Neodymium Ferrocyanide from Solutions

Sorption of ⁸⁵Sr, ¹³⁷Cs, ²²Na, and ¹⁵²Eu on solid mixed potassium neodymium ferrocyanide KNd[Fe(CN)₆]·4H₂O from neutral, acidic, and alkaline media and also coprecipitation of these radionuclides with KNd[Fe(CN)₆]·4H₂O in its formation from a homogeneous solution were studied. It was found that ⁸⁵Sr and ²²Na do not noticeably coprecipitate with solid KNd[Fe(CN)₆]·4H₂O and are not sorbed by this substance. In aqueous medium, depending on the cesium concentration in solution, from 80 to 98% of ¹³⁷Cs coprecipitates with solid KNd[Fe(CN)₆]·4H₂O. In this case, the distribution coefficient K_d depends on both the cesium concentration in solution and solution pH. Within 30 min of contact of the solid and liquid phases, the degree of recovery of ¹³⁷Cs from aqueous solution with KNd[Fe(CN)₆]·4H₂O is approximately 95.0% of the initial amount. ¹⁵²Eu coprecipitates with solid KNd[Fe(CN)₆]·4H₂O during its formation from a homogeneous solution to 98–99.9%. The degree of recovery of ¹⁵²Eu from aqueous solution with KNd[Fe(CN)₆]·4H₂O precipitate within 60 min of contact of the solid and liquid phases is 70.3% of the initial amount.     

Determination of the Parameters of Selective <Superscript>137</Superscript>Cs Sorption onto Natural and Ferrocyanide-Modified Glauconite and Clinoptilolite

The effect exerted by surface modification of natural aluminosilicates, glauconite and clinoptilolite, with ferrocyanides on the parameters of selective ¹³⁷Cs sorption was studied. The modification leads to an increase in the specific sorption and in the radiocesium interception potential in the presence of potassium, RIP(K). RIP(K) of the modified sorbents NPF-Gl and NPF-Cl was 6.1 × 10⁵ and 5.0 × 10⁶ mmol kg^–1, and the specific sorption capacity, 138 ± 14 and 136 ± 12 mg g^–1, respectively. The regular trends in variation of the ¹³⁷Cs distribution coefficients in sorption onto the natural and modified sorbents at K⁺ and Са²⁺ concentrations ranging from 10^–4 to 2.0 M were found. The modified sorbents exhibit high specificity to ¹³⁷Cs in a wide range of Ca and K concentrations in the solutions.     

Reactor production and purification of <Superscript>153</Superscript>Sm radioisotope via <Superscript>nat</Superscript>Sm target irradiation

Neutron irradiation of a natural Sm target is performed to produce ¹⁵³Sm. Ion-exchange chromatography is used to separate ¹⁵³Sm from Eu radionuclides produced in the process. To prepare a target, Sm₂O₃ powder is dissolved in 0.2 ml of HNO₃ in a quartz vial. Samarium is deposited onto the vial walls by passing nitrogen gas at 120°C. The prepared samarium target is encapsulated in aluminum foil and irradiated in a 5-MW reactor in 5 × 10¹³ n cm⁻² s⁻¹ flux. The irradiated target is dissolved in 1 M HCl, and the produced radioisotopes are determined with an HPGe nuclear detector. Finally ¹⁵³Sm is separated from Eu radionuclides with ¹⁵³Sm recovery yield of more than 66% and purity better than 99.8%.     

Sorption of CH<Subscript>3</Subscript><Superscript>131</Superscript>I from water vapor-air medium on porous inorganic sorbents containing triethylenediamine and <Emphasis Type="Italic">d</Emphasis> element nitrates

Sorption of CH₃ ¹³¹I from a water vapor-air medium on porous inorganic sorbents based on silica gel of KSKG grade and containing triethylenediamine (CH₂-CH₂)₃N₂ and d element nitrates was studied. The sorbents prepared by impregnation with (CH₂-CH₂)₃N₂ and Zn, Ni, and Cu nitrates from aqueous solution recover CH₃ ¹³¹I from a water vapor-air flow poorly (degree of recovery <10%). Calcination of the sorbents at temperatures exceeding 250°C does not noticeably affect their sorption power. Heating of the complex Ag(NO₃)(OH)·(CH₂-CH₂)₃N₂H to 160°C causes its exothermic decomposition with a large heat release and formation of metallic silver. Thermal decomposition of the complex of Cu²⁺ with (CH₂-CH₂)₃N₂, synthesized from an aqueous solution at the molar ratio Cu(NO₃)₂: (CH₂-CH₂)₃N₂ = 1: 2, occurs similarly.     

Recovery of <Superscript>137</Superscript>Cs and <Superscript>90</Superscript>Sr from wastewater by sorption on finely dispersed minerals under static conditions

The natural minerals clinoptilolite and tripoli were used for sorption treatment of liquid radioactive waste (LRW) to remove ¹³⁷Cs and ⁹⁰Sr. The efficiency of sorption recovery of these radionuclides with finely dispersed mineral sorbents under static conditions was studied in relation to the sorption time, pH, size of mineral granules, sorbent amount, salt content and chemical composition of solutions, and number of successive sorption steps. The distribution coefficient of radionuclides between the sorbent and aqueous phase and the sorption capacity of sorbents for radionuclides were determined. It was found that treatment of real salt-containing LRW from the Leipunskii Institute of Energy Physics, State Scientific Center of the Russian Federation, with the natural sorbents decreased their activity by 2–3 orders of magnitude owing to recovery of ¹³⁷Cs and ⁹⁰Sr.     

Adsorption of <Superscript>99<Emphasis Type="Italic">m</Emphasis></Superscript>Tc on aluminum oxide

Adsorption of ^99m Tc under static and dynamic conditions on aluminum oxides subjected to various acid treatments at pH from 7.29 to 1.26 (until the reaction of the oxide with the acid fully ceased) was studied. In batch experiments, the maximal adsorption of ^99m T_c, more than 30% of the radionuclide activity, is attained with the oxide that absorbed 2 × 10⁻⁴ mol g⁻¹ acid. The “rate” of linear migration of ^99m T_c in a chromatographic column in the course of elution with a 0.9% NaCl solution under the conditions of limiting saturation of the oxide with the acid is 0.49–0.52 cm ml⁻¹. It is concluded that the observed deceleration of the ^99m T_c elution from the generator column is due to its “braking” by active sites of the oxide. Upon reduction of ^99m T_c with bivalent tin, its adsorption increases to 93.53%. The results obtained are of interest for the development of procedures for depositing ^99m T_c onto the surface of nanosized colloidal particles of aluminum oxide for their subsequent use in medical diagnostics.     

Production and radiochemical separation of no-carrier-added <Superscript>88</Superscript>Y by liquid-liquid extraction

A method was suggested for the cyclotron production of ⁸⁸Y with liquid-liquid extraction. The sedimented ^natSrCO₃ target was irradiated with 18-MeV protons at current of 20 μA for 10 h. The ⁸⁸Y yields of about 1.326 MBq μA⁻¹ h⁻¹ were experimentally obtained. Solvent extraction of no-carrier-added ⁸⁸Y from irradiated strontium carbonate target in the hydrochloric acid solution was studied using di(2-ethylhexyl) hydrogen phosphate (HDEHP). The optimum separation was achieved in the system n-hexane/10% HDEHP-0.1 M HCl. Yttrium radionuclides were recovered from the HDEHP phase by stripping with 60 ml of 9 M HC1. Also, excitation functions of the proton, deuteron, and α-particle induced reactions of ⁸⁹Y, ⁸⁸Sr, ^natSr, and natRb were determined using computer codes and compared to the existing data.     

Coprecipitation of Trace Amounts of <Superscript>137</Superscript>Cs and <Superscript>85</Superscript>Sr with [Na(18-Crown-6]BPh<Subscript>4</Subscript> from Neutral and Alkaline Solutions

Coprecipitation of ¹³⁷Cs and ⁸⁵Sr with [Na(18-crown-6]BPh₄ solid phase from aqueous, aqueous-ethanolic, and alkaline solutions is studied. ¹³⁷Cs and ⁸⁵Sr cocrystallize with [Na(18-crown-6]BPh₄ from aqueous and aqueous-ethanolic solutions. The cocrystallization coefficients D of ¹³⁷Cs and ⁸⁵Sr from aqueous solutions are 2.6±0.5 and 3.3±0.3, respectively. For aqueous-ethanolic solutions, the corresponding values are 4.4±0.5 and 3.4±0.4. In the alkaline solutions (0.1 and 1 M NaOH), 54–74% of ¹³⁷Cs and 37–51% of ⁸⁵Sr pass into the [Na(18-crown-6]BPh₄ solid phase, depending on the crown ether concentration in the system.__________Translated from Radiokhimiya, Vol. 47, No. 3, 2005, pp. 257–260.Original Russian Text Copyright © 2005 by Kulyukhin, Konovalova, Rumer, Kamenskaya, Mikheev.     

A study of ferrocyanide sorbents on hydrated titanium dioxide support using physicochemical methods

The paper describes how the conditions of preparing ferrocyanides on hydrated titanium dioxide support affect the surface texture of the resulting materials, their elemental and phase composition, and their ability to sorb cesium. The sorbents prepared under the optimal conditions exhibited increases specificity to Cs (K _d = 10^5.6±1.0 ml g⁻¹) and high capacity (no less than 270 mg g⁻¹).     

Behavior of 131I and 137Cs in the oil-water and oil-gas phase systems

The behavior of ¹³¹I and ¹³⁷Cs in various chemical forms in the oil-water and oil-gas phase systems and the sorption of these radionuclides from radioactive transformer oil onto various inorganic and organic sorbents was studied. The degree of the ¹³⁷Cs extraction depends neither on the time of contact of the oil with aqueous solutions nor on the ¹³⁷CsI concentration in the solution. Under all the experimental conditions, the degree of extraction of ¹³⁷Cs did not exceed 5%. The degree of ¹³¹I extraction from water by the oil depends on the chemical form of the radionuclide: ¹³¹I^?, ³¹IO ₃ ^? , or ¹³¹I₂. The maximal extraction (～70%) is observed for K¹³¹IO₃, and the minimal (～25%), for ¹³¹I₂. Granulated nanocomposites containing particles of carbon or NaX zeolite and Fizkhimin sorbents based on coarsely porous silica gel and containing Ag and Ni in 1: 4 ratio allow efficient removal of ¹³⁷Cs and ¹³¹I from spent transformer oil of GK grade.     

Sorption of cesium on finely dispersed composite ferrocyanide sorbents

Sorption of microamounts of cesium on finely dispersed composite ferrocyanide sorbents was studied. The sorbents were prepared by precipitation of nickel potassium ferrocyanide in the presence of various mineral supports (chalk, wollastonite, bentonite, clinoptilolite, diatomite, biosilica). The distribution coefficient (K _d) of ¹³⁷Cs on composite ferrocyanide sorbents is considerably higher than on nickel potassium ferrocyanide without support. The K _d values on the composite sorbents increase by a factor of 25–110 when separating the solid phase with a paper filter and by a factor of 4.3–8.2 when using a microfiltration membrane. Considerable increase in K _d of ¹³⁷Cs on composite sorbents is attributed to the formation of a nickel potassium ferrocyanide phase firmly fixed on the support surface and resistant to peptization. Composite ferrocyanide sorbents were tested for the ¹³⁷Cs recovery from a simulated NPP bottom residue in the pH range 8.5–12.0. On the composite sorbents, K _d of ¹³⁷Cs is 2.5–3.0 times higher than on the nickel ferrocyanide precipitate throughout the examined pH range. The composite sorbent based on biosilica and nickel potassium ferrocyanide was tested for treatment of real liquid radioactive waste with a total salt content of 22.0 g dm⁻³ to remove ¹³⁷Cs. The decontamination factor as high as 5190 was attained owing to simultaneous use of the finely dispersed composite ferrocyanide sorbent and an ultrafiltration ceramic membrane.     

Cocrystallization of microamounts of <Superscript>137</Superscript>Cs, <Superscript>90</Superscript>Sr,and <Superscript>90</Superscript>Y from aqueous solutions with the solid phase of mixed potassium neodymium ferrocyanide

Cocrystallization of microamounts of ¹³⁷Cs, ⁹⁰Sr, and ⁹⁰Y with the solid phase of mixed potassium neodymium ferrocyanide was studied in relation to the K₄[Fe(CN)₆]: Nd(NO₃)₃ ratio in aqueous solution. At the K₄[Fe(CN)₆]: Nd(NO₃)₃ ratio higher than 2, all the radionuclides studied virtually quantitatively (to 96–99%) cocrystallize with the KNd[Fe(CN)₆]·4H₂O solid matrix. The cocrystallization coefficients D calculated by the Henderson-Krechek equation exceed 10³. Leaching of ¹³⁷Cs and ¹⁵²Eu from the K(¹³⁷Cs)Nd(¹⁵²Eu)· [Fe(CN)₆]·4H₂O solid matrix with water and with aqueous solutions of HNO₃ (0.1 and 1.0 M) and KOH (4.0 M) was studied.     

A sorbent based on natural dolomite for recovery of cobalt radionuclides

Granulated sorbents for recovery of cobalt radionuclides were prepared from carbonate natural raw material (dolomite) using thermal activation. The chemical and phase composition and the main physicochemical properties of the sorbents were determined. Their ability to sorb ⁶⁰Co under dynamic conditions was evaluated. Among all the tested samples, the sorbent prepared at 900°C exhibits the best sorption and service characteristics (degree of recovery 0.8–1.0, distribution coefficient 1.7 × 10³ ml g⁻¹, total absorbed specific activity 7.7 × 10⁴ Bq g⁻¹).     

Ultrapurification of <Superscript>76</Superscript>Ge-enriched GeH<Subscript>4</Subscript> by distillation

⁷⁶Ge-enriched germane has been ultrapurified by low-temperature distillation. The nature and concentration of molecular impurities in the germane samples were determined by gas chromatography/mass spectrometry, high-resolution Fourier transform IR spectroscopy, and gas chromatography. The distillate contains no more than 10⁻⁵ mol % hydrocarbons, 10⁻⁴ mol % carbon dioxide, 10⁻³ to 10⁻¹ mol % digermane and trigermane, and <3 × 10⁻⁵ mol % other impurities. A distinctive feature of the impurity composition of the isotopically enriched germane samples is the presence of silicon tetrafluoride and sulfur hexafluoride impurities.     

Conversion of I<Subscript>2</Subscript> into ionic species on composite materials in the NPP primary coolant

The conversion of I₂ into its ionic species in aqueous solutions, including the simulated primary coolant, at 20, 40, and 60°C on the solid phase of composite materials prepared by modification of KU-2 cation exchanger containing d elements was studied. These materials are capable of converting I₂ into its ionic species to 99% both in distilled water and in a solution corresponding in its composition to the aqueous primary coolant of NPP with WWER-type reactors. Practically complete conversion of I₂ (to more than 95.0%) is attained in 15 min. AV-18 anion exchanger is capable of sorbing I₂ in the form of I₃⁻ from aqueous solution with the distribution coefficients K _d >10³ ml g⁻¹ upon 24-h contact of the solid and liquid phases at V/m = 100.