Association of 90xSr, 137Cs, 239,240Pu, 241Am,and 244Cm with Soil Absorbing Complex in Soils Typical of the Vicinity of the Chernobyl NPP

Association of the main long-lived radionuclides ¹³⁷Cs, ⁹⁰Sr, ^239,240Pu, ²⁴¹Am, and ²⁴⁴Cm with various components of the soil absorbing complexes from soil samples collected along the western, northwestern, and northern tracks of radioactive fallout in the vicinity of the Chernobyl NPP was studied by the sequential leaching. In the samples of the sandy soil collected in the floodplain of the Pripyat river along the northwestern radioactive track, more than 85% of ⁹⁰Sr, 55% of ^239,240Pu, and 75% of ²⁴¹Am and ²⁴⁴Cm are associated with various components of the soil absorbing complex and are potentially mobile species. In the soil samples collected along the narrow western track, 80-85% of ¹³⁷Cs, ⁹⁰Sr, ^239,240Pu, ²⁴¹Am, and ²⁴⁴Cm are incorporated in hot particles. The degree of ¹³⁷Cs, ⁹⁰Sr, ^239,240Pu, ²⁴¹Am, and ²⁴⁴Cm association with different components of the soil absorbing complex is a function of the radionuclide type and physicochemical features of soil.     

Distribution of <Superscript>137</Superscript>Cs, <Superscript>90</Superscript>Sr, <Superscript>239 + 240</Superscript>Pu, <Superscript>241</Superscript>Am,and <Superscript>244</Superscript>Cm among Components of Organic Matter of Soils in Near Exclusion Zone of the Chernobyl NPP

Distribution of Chernobyl-derived ¹³⁷Cs, ⁹⁰Sr, ^{239 + 240}Pu, ²⁴¹Am, and ²⁴⁴Cm among organic fractions of soddy-podzolic, sandy, soddy-meadow, and peat soils collected from the Chernobyl Exclusion Zone along the North-Western radioactive fallout track was determined. Regardless of the soil type, 80–85% of ¹³⁷Cs is tightly fixed on the mineral fraction of the soil. Depending on the soil type, 50–70% of ⁹⁰Sr and 15– 45% of ²⁴¹Am are associated with fulvic acid fractions. ²⁴¹Am and ²⁴⁴Cu are similarly distributed among the organic acid fractions. In all the soil types studied, ^{239 + 240}Pu is associated essentially with humic acid fractions. Natural ^{230, 232}Th and technogenic ^{239 + 240}Pu are similarly distributed among the organic fractions.__________Translated from Radiokhimiya, Vol. 47, No. 1, 2005, pp. 91–96.Original Russian Text Copyright © 2005 by Odintsov, Pazukhin, Sazhenyuk.     

Coprecipitation of microamounts of radionuclides on chitosans of various molecular weights in solutions

Coprecipitation of ²³³U, ²³⁹Pu, ²⁴¹Am, ¹⁵²Eu, ⁹⁰Sr, ⁹⁰Y, and ⁶⁰Co on chitosans of various molecular weights (MW) was studied. Low-molecular-weight chitosan (LMWC) with MW of 5 kDa (5 × 10³ g mol⁻¹) proved to be a more effective coprecipitant than high-molecular-weight chitosan (HMWC) with MW of 700 kDa (7 × 10⁵ g mol⁻¹). With HMWC, the degree of coprecipitation (α) was 80% for ¹⁵²Eu and ⁹⁰Y, 99% for ²³³U and ²⁴¹Am, and 85% for ²³⁹Pu. For ⁶⁰Co, α monotonically increased with an increase in the chitosan concentration in solution and reached 40% at [HMWC] = 5 g l⁻¹. For ⁹⁰Sr, α did not exceed 3% in the entire examined range of chitosan concentrations. With LMWC, the α values for An, ¹⁵²Eu, and ⁹⁰Y differed insignificantly (92–99%). For ⁶⁰Co and ⁹⁰Sr, α increased to 40% in the range of chitosan concentrations from 0 to 1 g l⁻¹. The presence of inorganic salts in solution considerably decreases α of UO₂²⁺ with chitosans but does not noticeably affect the behavior of Am, Pu, and Eu. The effect of salts on the efficiency of ²³³UO^2/2+ coprecipitation on HMWC decreases in the order Na₂SO₄ > NaCl > Na₂CO₃ > NaNO₃ > Na₃PO₄. Based on the results obtained, a procedure suitable for expedition conditions was developed for preconcentration of Pu from seawater on chitosan, with simultaneous separation of Pu from U, for radioecological monitoring of natural waters. The specific activity of Pu in samples of near-bottom seawater of gulfs of the Novaya Zemlya archipelago was (150–170) ± 20 mBq m⁻³. The results are well consistent with the published data.     

Determination of the content of radioactive elements in irradiated beryllium

The elemental composition of the material of beryllium blocks of SM reactor reflector in the initial state was determined by inductively coupled plasma atom emission spectrometry (ICP AES). The α-, β-, and Γ-active components of the radiation from Be irradiated to a neutron fluence of 6 × 10²² cm⁻² (E > 0.1 MeV) were determined. Radiochemical analysis revealed the presence in the irradiated Be of ⁶⁰Co, ⁵⁴Mn, ¹³⁷Cs, ¹³⁴Cs, and ⁹⁰Sr. The following α-emitters were revealed: ^238–241Pu, ²⁴¹Am,²⁴³Am, and ²⁴⁴Cm.     

Effect of Contact Time of Liquid Radioactive Waste with Bed Rock of Underground Repository on Migration Behavior of 90Sr, 137Cs, 239Pu,and 241Am

Behavior of radionuclides caused by interaction of acidic waste with sandy bedrock in deep underground repositories is studied, including sorption-desorption of ⁹⁰Sr, ¹³⁷Cs, ²³⁹Pu, and ²⁴¹Am. The amount of mobile forms of radionuclides decreases with increasing contact time with bedrock, thus decreasing the migration rate of the radionuclides in the collector bed.     

Stability of Pu(VI) and Pu(V) in aqueous formate solutions

The behavior of Pu(VI), Pu(V), and Pu(IV) in K(Li,Na)HCO₂ and HCOOH + Li(Na)HCO₂ solutions was studied by spectrophotometry. Changes in the spectra of a Pu(VI) solution, observed on adding alkali metal formates, suggest formation of Pu(VI) formate complexes. Changes in the absorption spectra of Pu(V), observed with an increase in the concentration of LiHCO₂ or NaHCO₂, suggest the appearance of Pu(V) formate complexes. The absorption spectra of Pu(IV) indicate that, in a wide range of formate concentrations, the composition of the Pu(IV) formate complexes under the examined conditions is constant. The Pu(VI) content in formate solutions decreases at a rate exceeding the rate of the Pu(VI) disappearance in 0.5–2 M HClO₄ under the action of the ²³⁹Pu α-radiation. The tendency of Pu(V) to reduction and disproportionation in formate solutions depends in a complex fashion on the formate ion concentration and kind of the alkali metal. The kinetics of the Pu(V) consumption in HCOOH + Li(Na)HCO₂ solutions was studied. The reaction starts with the formation of a Pu(V) formate complex, which interacts with Pu(V) aqua ions and Pu(V) formate complex to form dimers, with their subsequent protonation and transformation into Pu(VI) and Pu(IV).     

Sorption of Cs,Sr, and Y radionuclides on mixed layered double hydroxides of Mg,Al, and Nd from the aqueous phase

Sorption of ¹³⁷Cs, ⁹⁰Sr, and ⁹⁰Y radionuclides from aqueous solutions on the solid phase of layered double hydroxides (LDHs) of Mg, Al, and Nd was studied. Sorption of ¹³⁷Cs from 10⁻⁵ M aqueous CsNO₃ solutions on the LDH-Mg-Al-Nd solid phase is extremely weak. At the same time, ⁹⁰Sr and ⁹⁰Y are efficiently sorbed on the LDH-Mg-Al-Nd solid phase from 10⁻⁵ M aqueous Sr(NO₃)₂ solutions. After 5-min contact of the solid and liquid phases, K _d of ⁹⁰Sr and ⁹⁰Y exceeds 10³ ml g⁻¹. With an increase in the Nd content in LDHs of mixed composition, their sorption properties toward ⁹⁰Sr and ⁹⁰Y are enhanced.     

Transuranium elements in liquid radioactive wastes from the Shelter

The volume activity of ⁹⁰Sr, ¹³⁷Cs, ²³⁸Pu, ^239+240Pu, ²⁴¹Am, and ²⁴⁴Cm in water taken from unorganized water accumulations on lower marks of the Shelter was determined. Separate water accumulations are characterized by their specific radionuclide activity ratios ²³⁸Pu/^239+240Pu, ²⁴¹Am/^239+240Pu, and ²⁴⁴Cm/²⁴¹Am. The activity ratios ²⁴¹Am/^239+240Pu and ²⁴⁴Cm/^239+240Pu in the water accumulations are 5–10 times higher than in the irradiated fuel of the 4th Unit of the Chernobyl NPP and in lava-like fuel-containing materials.     

Sorption of Cs,Sr, U,and Pu radionuclides on natural and modified clays

The ability of natural and modified montmorillonite clays from Belgorod oblast to sorb Cs, Sr, U, and Pu radionuclides was studied. The clays were modified by treatment with metal (Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Fe²⁺, Zn²⁺) chloride solutions or aqueous HCl. The natural and modified clays studied show high performance in sorption treatment of solutions to remove Cs radionuclides. The natural clay and the Na and Mg forms of clays show the best sorption characteristics with respect to Cs. The distribution coefficient K _d of ¹³⁷Cs in sorption on the above samples from a 0.1 M NaNO₃ solution is (1.1–1.4) × 10⁴ cm³ g⁻¹, which is 4–5 times higher compared to natural clinoptilolite. The Sr, U, and Pu radionuclides are sorbed on the examined clay samples to a considerably lesser extent. The K _d values in sorption of these radionuclides from tap water are lower by 2–3 orders of magnitude than in sorption of Cs. Addition of clay materials in the course of cementation of liquid radioactive wastes, including NPP bottom residues, allows the rate of radiocesium leaching from the hardened cement compounds to be decreased by a factor of 5–16. The most efficient sorption additive in cementation of NPP bottom residues is natural montmorillonite clay.     

Kinetics of Pu(V) disproportionation in CH<Subscript>3</Subscript>COOH-CH<Subscript>3</Subscript>COOLi aqueous solutions

The behavior of Pu(IV–VI) in CH₃COOH-CH₃COOLi solutions was studied by spectrophotometry. The Pu(VI) absorption spectrum changes essentially with an increase in the CH₃COOLi concentration. Owing to formation of Pu(VI) acetate complexes, the maximum of the main absorption band is shifted from 830.6 (in HClO₄ solution) to 845 nm, with the band intensity decreasing by a factor of approximately 8. The Pu(V) and Pu(IV) absorption spectra at low concentrations of acetate ions vary insignificantly relative to the spectra in noncomplexing media. With an increase in the acetate concentration in the system to 1–3 mM, the effect of Pu(V) complexation on its absorption spectrum becomes noticeable (the absorption intensity considerably decreases), whereas the Pu(IV) absorption spectra remain essentially unchanged. Solutions containing 1–2 mM Pu(V) and 0.2–0.5 M CH₃COOLi remain unchanged at 18–25°C for 2 days. In solutions with [CH₃COOLi] = 1–3 M, Pu(V) disproportionates with the formation of soluble Pu(VI) complexes and a suspension of Pu(IV) hydroxide. Introduction of CH₃COOH to a concentration of 0.1–1.0 M prevents the formation of a suspension of Pu(IV) hydroxide, but only up to a temperature of 45°C. The Pu(V) loss follows a second-order rate law, with the reaction products, Pu(IV) and Pu(VI), accelerating the Pu(V) consumption. The reaction rate at a constant concentration of acetate ions is proportional to [H⁺]. The reaction order with respect to Ac⁻ ions is close to 1.6. The activation energy of the Pu(V) disproportionation in the range 19–45°C is estimated at 74.5 kJ mol⁻¹. It is assumed that the disproportionation mechanism involves the formation of dimers from Pu(V) acetate complexes and aqua ions, their protonation, and decomposition with the transformation into Pu(IV) and Pu(VI).     

Coprecipitation of 90Sr and 90Y with Lead Phosphate

Coprecipitation of ⁹⁰Sr and ⁹⁰Y with lead phosphate as influenced by various factors was studied with the aim to find conditions for their separation. It was shown that, under certain conditions, these radionuclides can be quantitatively recovered from a solution; however, it is impossible to provide efficient separation of strontium and yttrium in one stage of precipitation of lead phosphate solely by varying pH. The studies of coprecipitation of ⁹⁰Sr and ⁹⁰Y with lead phosphate in the presence of DTPA and stable yttrium showed that the presence of this complexing agent does not hinder quantitative precipitation of strontium, while practically all yttrium remains in the solution. The optimal conditions of precipitation of lead phosphate ensuring high degree of separation (up to 97% in one precipitation stage) of ⁹⁰Sr from ⁹⁰Y were determined.     

Plutonium Contamination Level and Isotopic Composition in Soils around St. Petersburg

Plutonium isotopic composition including ²³⁸Pu, ²³⁹Pu, ²⁴⁰Pu, and ²⁴¹Pu and the Pu contamination level are determined in soils around St. Petersburg using an advanced procedure involving radiochemical separation stage followed by the -ray spectrometric and mass spectrometric determination. The Pu specific activity in surface horizons (0-25 cm) ranges from 0.2 to 0.44 Bq kg^-1. The mean ²³⁸Pu/239,240Pu activity ratio is found to be 0.033±0.007. The Pu contamination level of the surface horizon (0-25 cm) is 62±5 Bq m^-2. The ²³⁸Pu/²³⁹Pu, ²⁴⁰Pu/²³⁹Pu, and ²⁴¹Pu/²³⁹Pu isotopic ratios are (2.0±0.5)×10^-4, 0.172±0.004, and 0.003±0.002, respectively. These ratios are close to the values typical of plutonium from the global radioactive fallout due to nuclear weapons tests in the atmosphere. The effect of the Chernobyl accident and regional potential contamination sources, including the Leningrad NPP, on the Pu isotopic composition and contamination level in the soil is insignificant.     

Influence of temperature on the sorption properties of rocks from the Nizhnekansky massif

The kinetics of radionuclide sorption onto finely divided samples of rocks from the Nizhnekansky massif, taken from the level of the planned arrangement of deep radioactive waste repository, was studied, and the times in which the sorption equilibrium was attained at 20 and 90°С were determined. The distribution coefficients of actinides (²³³U, ²³⁹Pu, ²⁴¹Am) and fission products (¹³⁷Cs, ⁹⁰Sr) were determined. Increasing the temperature from 20 to 90°С intensifies the sorption of the radionuclides studied, except cesium for which the sorption slightly decreases.     

Behavior of plutonium in various oxidation states in aqueous solutions: I. Behavior of polymeric Pu(IV) and of Pu(VI) at 10<Superscript>−5</Superscript>–10<Superscript>−8</Superscript> M concentrations in solutions with pH ∼8

Pu(V) does not exist for a long time in solutions at pH ∼8 and concentrations of 10⁻⁵–10⁻⁸ M because of disproportionation to polymeric Pu(IV) and Pu(VI), which form a common polymeric structure that subsequently does not significantly change. Plutonium(III) at its concentrations from 10⁻⁵ to 10⁻⁸ M in solutions at pH ∼8 undergoes oxidation, transforming into polymeric Pu(IV). The data obtained can be useful for interpretation of the plutonium behavior under natural conditions.     

Synthesis of New Crystalline Pu(V) Compounds from Solutions: VIII. Structure and Properties of Double Pu(V) Malonates MPuO2(OOC)2CH2 · nH2O (M = Na, NH4, Cs)

Preparation conditions and properties of some double Pu(V) malonates MPuO₂L · nH₂O [L = CH₂(COO)₂; M = Na, NH₄, Cs] were determined. These compounds are isostructural to the corresponding double Np(V) malonates obtained previously. The Pu(V) malonates crystallize in the form of needles from solutions with [L²⁻] = 0.05–0.3 M containing 0.5–2 M of salts of outer-sphere cations as salting- out agents. Dry crystals are stable for no less than 3 weeks. The IR spectra of these compounds were recorded. Their thermal behavior was studied. The outer-sphere cations presumably form ionic bonds with plutonyl(V) cations, which are weakened with an increase in the cation radius. __________ Translated from Radiokhimiya, Vol. 47, No. 5, 2005, pp. 431–433. Original Russian Text Copyright ? 2005 by Krot, Bessonov, Grigor'ev, Makarenkov.     

A Method for Determining the Isotope Composition of U, Pu, Am, and Cm in "Hot" Particles and Spent Nuclear Fuel

A method was proposed for determining the content of ^234-238U, ^238-242Pu, ^241-243Am, and ^242-244Cm in "hot" fuel particles and spent nuclear fuel. The method is based on high-precision measurement of the -activity in the sample and calculation of the relative contributions of individual nuclides or radionuclide groups to the total activity. Partitioning of U, Pu, Am, and Cm was carried out by ion-exchange chromatography. The contents of ²³⁴U, ²³⁶U, ²³⁸U, ²³⁸Pu, ^239+240Pu, ²⁴²Pu, ²⁴¹Am, ^242mAm, ²⁴³Am, ²⁴²Cm, and ²⁴⁴Cm in "hot" particles sampled in the Chernobyl area were reported. The applicability of the method proposed to determining the radionuclide composition of spent nuclear fuel was discussed.     

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.     

New approaches to reprocessing of oxide nuclear fuel

Dissolution of UO₂, U₃O₈, and solid solutions of actinides in UO₂, including those containing Cs, Sr, and Tc, in weakly acidic (pH 0.9–1.4) aqueous solutions of Fe(III) nitrate or chloride was studied. Complete dissolution of the oxides is attained at a molar ratio of Fe(III) nitrate or chloride to uranium of 1.6 or 2.0, respectively. In the process, actinides pass into the solution in the form of U(VI), Np(V), Pu(III), and Am(III). At 60°C, actinide oxides dissolve in these media faster than at room temperature. In the solutions obtained, U(VI) and Pu(III) are stable both at room temperature and at elevated temperatures (60°C), and also at high U concentrations (up to 300 mg ml⁻¹) typical of process solutions (6–8 M HNO₃, ∼60–80°C). After the oxide fuel dissolution, U and Pu are recovered from the solution by peroxide precipitation. In so doing, the content of Fe, Tc, Cs, and Sr in the precipitate does not exceed ∼0.05 wt %. From the solution after the U and Pu separation, the fission lanthanides, Tc, Cs, and Sr can be recovered by precipitation of Fe hydroxides in the presence of ferrocyanide ions and can be immobilized in appropriate matrices suitable for long-term and environmentally safe storage.     

Estimation of the Solubility of Radioactive Aerosol Particles in Biological Liquids

The solubility of the aerosol hot particles, sampled in 1987 in the town of Pripyat, in the simulated lung fluid (SLF) (Gamble or Ringer solution) and in 0.1 M HCl was studied under static conditions. Leaching of radionuclides from the hot particles in the SLF decreases in the order ¹³⁷Cs > ⁹⁰Sr >> ^239+240Pu ²⁴¹Am, and in 0.1 M HCl, in the order ⁹⁰Sr > ²⁴¹Am >> ¹³⁷Cs > ^239+240Pu. The degree of passing into 0.1 M HCl solution for ⁹⁰Sr and ²⁴¹Am was estimated at 3.3-21 and 2.7-17%, respectively. Depending on the particle size, 0.06-2.2% of ²⁴¹Am and 0.2-1.8% of ^239+240Pu passes into the SLF within 28 days.     

Extraction-chromatographic isolation of 90Y for medical purposes

A procedure is described for isolating ⁹⁰Y from its equilibrium mixture with ⁹⁰Sr. It is based on extraction-chromatographic separation of ⁹⁰Sr and ⁹⁰Y on columns packed with a solid extractant based on di-2-ethylhexyl hydrogen phosphate. Further purification of ⁹⁰Y is made by its sorption on a column with an yttrium-specific sorbent based on octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide in TBP, and then on a cation-exchange resin. The whole process is performed in a nitric acid solution, which, in contrast to hydrochloric acid solutions, does not cause strong corrosion of stainless steel equipment, thus facilitating decontamination of the final product from inactive impurity cations.