The Use of Natural Zeolites for Radioactive Waste Treatment: Studies on Leaching from Zeolite/Cement Composites

Samples of the natural zeolites chabazite, clinoptilolite and a clinoptilolite-rich tuff, were loaded with the isotope ¹³⁷Cs. Composites of these labeled materials were made with cement and blast furnace slag. Standard leaching experiments were carried out with synthetic sea, ground and "pond" waters, as well as distilled water. Rates of leaching were calculated and compared to similar systems.     

Simultaneous determination of uranium and plutonium isotopes in soils by means of single alpha-spectrometry

A simple, rapid and reliable method was developed for the simultaneous determination of uranium and plutonium isotopes by alpha-spectrometry using a single source. A new uranium tracer²³⁰U was applied as well as the²³⁶Pu tracer to determine overall yields of uranium and plutonium isotopes throughout the entire procedure employed. The analytical procedure consists of sample leaching with 8N HNO₃ solution, purification by solvent extraction, simultaneous electrodeposition of U and Pu, and subsequent alpha-spectrometry with a silicon detector. In the solvent extraction using TOA/xylene from 8N HNO₃ solution, the preferential extractability of Pu rather than U permits to purify simultaneously the trace amounts of Pu and the macro amounts of U, as in the case of ordinary soil samples, resulting in favourable peak heights for both isotopes. From a single alpha-spectrum, the determinations of²³⁸U,²³⁴U (and their ratio of²³⁴U/²³⁸U),^239+240Pu, and²³⁸Pu contents were conveniently carried out after correcting the overall yields obtained from²³⁰U and²³⁶Pu activities in the same spectrum. This analytical method was satisfactorily applied to the determination of U and Pu isotope contents in some soils.     

Radium-226 in uranium mill tailings

A study of the physical state of²²⁶Ra in uranium mill tailings was undertaken by Chemex Laboratories Ltd. under contract to NUTP. A test portion of a leached uranium ore was collected just prior to neutralization with lime and subjected to repetitive batch water leaching. The leachates were analyzed for barium, lead,²²⁶Ra, iron and sulphate. The experimental results suggest that²²⁶Ra is co-precipitated with lead sulphate during uranium leaching of the ore with sulphuric acid. The attainment of equilibrium conditions in the pore water of the leached ore then allows a re-proportioning of²²⁶Ra between solid lead and barium sulphates resulting in a depletion of²²⁶Ra in the outer layers of the crystals of solid lead sulphate and an enrichment in²²⁶Ra in the outer layers of solid barium sulphate.     

Plutonium isotopes and 137Cs in Dolon settlement near the Semipalatinsk Nuclear Test Site: About 50 years after the first nuclear weapon testing

Recent controversies concerning the radiation doses for populations living in the village of Dolon due to the nuclear explosions carried out at the Semipalatinsk Nuclear Test Site (SNTS) have encouraged us to evaluate in more detail the levels and distributions of residual long-lived radionuclides¹³⁷Cs and Pu isotopes (²³⁸Pu,^239,240Pu) in soils within the village. Soil core samples up to a depth of about 30 cm and/or 100 cm were collected at 25 sites and subjected to analysis of ¹³⁷Cs and Pu isotopes. The inventories of ¹³⁷Cs and ^239,240Pu were found to be in the wide range of 790-10,310 and 530-14,320 Bq/m², respectively. Sequential leaching of Pu from the soil showed that more than ca. 80% of the ^239,240Pu was not leached by hot digestion with conc. HNO³ + H₂O₂, indicating the presence of Pu associated with fused silicates. Further, the presence of hot-particles from the Pu contaminants by a-track radiography technique using CR-39 polycarbonate was confirmed in the soil, even at present, after about 50 years from the first nuclear weapon testing. This revised version was published online in July 2006 with corrections to the Cover Date.     

Co-precipitation of plutonium(IV) and americium(III) from nitric acid–oxalic acid solutions with bismuth oxalate

This study presents analytical methods for the determination of gross beta, ⁹⁰Sr, ²²⁶Ra and Pu isotopes using samples in the IAEA-TEL-2015-04 ALMERA Proficiency Test exercise. Samples for gross beta were prepared by evaporation and then analyzed using a gas proportional counter. ⁹⁰Sr in the liquid sample was concentrated as SrCO₃ precipitates and purified by Sr resin. Pu isotopes and ⁹⁰Sr in the soil sample were extracted from the sample by mineral acid leaching and separated using TEVA and Sr resin, respectively. Pu isotopes were determined by alpha spectrometry and ⁹⁰Sr were determined with a liquid scintillation counter. Radium in the soil sample was extracted by LiBO₂ fusion, and the radon-emanation method using LSC was applied for the determination of ²²⁶Ra.     

Thorium series disequilibrium and geochemical processes in estuarine sediments of Mandovi river

The measurements of natural radioactivity due to thorium isotopes have been carried out in estuarine sediments of Mandovi river (Goa). The geochemical behaviour of these sediments has been studied by leaching the samples with 5 % ethylenediaminetetraacetic acid at pH 3.0 in order to investigate the processes occurring on the surface of the sediment particles and the distribution of natural thorium in estuarine sediments. The²²⁸Th/²³²Th activity ratios have been found to be in the range of 2.00 to 2.12. This anomaly between²³²Th and²²⁸Th has been attributed to the preferential leaching of²²⁸Ra by water flowing over these sediments. The activities of²²⁸Ra on the surface labile layers of the sediments have also been determined. The²³⁰Th/²³²Th activity ratios have been found to be in the range of 0.94 to 1.04. These ratios are mainly dependent on the precipitation action of²³⁰Th on adjacent sediments.     

An improved method for the determination of uranium isotopes in environmental samples by alpha-spectrometry

In order to improve the selectivity of the uranium isotopes determination in environmental samples, further studies have been carried out, including (1) interference of ²¹⁰Po with uranium isotope determination, (2) distribution coefficients of polonium between 5% TOPO in toluene and aqueous hydrochloric and nitric acids, (3) decontamination factor of uranium from polonium of the recommended procedure, and (4) leaching effect comparison of two different leaching procedures in a lichen sample. Based on the new findings, a more accurate extraction chromatographic/ a-spectroscopy method has been developed. For the method's validation, four kinds of reference materials supplied by the IAEA have been tested. It is observed that nearly all the ²³⁸U, ²³⁴U and ²³⁵U concentrations obtained are in good agreement with the recommended or information values, showing that the method can give reliable results. A comparison with existing uranium determination methods has also been made. It is concluded that due to involving preconcentration and chemical separation, the extraction chromatographic/a-spectroscopy method is a more selective, very sensitive and accurate, and low cost method. This revised version was published online in July 2006 with corrections to the Cover Date.     

Separation du cesium et du baryum des terres rares dans la source d’ions d’un separateur electromagnetique d’isotopes

In a previous work we studied the separation of cesium from a lanthanum target bombarded by protons in the thermoionic ion source of an electromagnetic isotope separator. After irradiation the principal elements found in the targets were Cs, Ba, Ce and La. We have extended this method to the separation of cesium and barium from metallic lanthanum targets and from lanthanum oxides. It is based on the thermoionization efficiency and on the behaviour of the element studied in the heated cavity, which depends on its volatility if it is under metallic form, and on its reduction and on the volatility of resulting compounds if it is under compound form. In the metallic system we obtained on the collector successively cesium and barium with respective overall yields of about 5% and 0.2%. In the oxide system, we obtained cesium as Cs⁺ ions and simultaneously barium as BaO⁺ ions which are separated from Ba⁺ by 16 masses avoiding the interference with cesium isotopes. The overall yield of the barium separation is about 0.2%. A discussion on the value of barium ionization potential is given.      

Syntheses and separating properties of triazacrown and AM18C6 bonded Merrifield peptide resins

Separation of lithium and magnesium isotopes by cation exchange elution chromatography was carried out with a synthesized 1,13,16-trioxa-4,7,10-triazacyclooctadecane (N₃O₃)-4,7,10-trimerrifield peptide resin and with a 2^′-aminomethyl-18-crown-6 (AM18C6) bonded Merrifield peptide resin. The resins have a capacity of 0.1 and 2.3 meq/g dry resin. A single stage separation factor of lithium isotopes, 1.018 was obtained by the Glueckauf theory from the elution curve and isotopic assays. The heavier isotope, ⁷Li was concentrated in the resin phase, while the lighter isotope, ⁶Li concentrated in the solution phase. On the other hand, the heavier isotopes of magnesium were concentrated in the solution phase, while the lighter isotopes were concentrated in the resin phase. The separation factors of ²⁴Mg-²⁵Mg, ²⁴Mg-²⁶Mg, and ²⁵Mg-²⁶Mg isotope pair fractionations were 1.012, 1.022, and 1.012, respectively.     

Low level detection of <Superscript>135</Superscript>Cs and <Superscript>137</Superscript>Cs in environmental samples by ICP-MS

The measurement of fission product cesium isotopes ¹³⁵Cs and ¹³⁷Cs at low femtogram (fg) 10⁻¹⁵ levels in ground water by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) is reported. To eliminate the natural barium isobaric interference on the cesium isotopes, in-line chromatographic separation of the cesium from barium was performed followed by high sensitivity ICP-MS analysis. A high efficiency desolvating nebulizer system was employed to maximize ICP-MS sensitivity ~10 cps/fg. The three sigma detection limit for ¹³⁵Cs was 2 fg/mL (0.1 μBq/mL) and for ¹³⁷Cs 0.9 fg/mL (0.0027 Bq/mL) measured from the standard with analysis time of less than 30 min/sample. Cesium detection and 135/137 isotope ratio measurement at very low femtogram levels using this method in a spiked ground water matrix is also demonstrated.     

Development of a sequential method for the determination of238U,234U,232Th,230Th,228Th,228Ra,226Ra,and210Pb. in environmental samples

A sequential analytical method for the determination of²³⁸U,²³⁴U,²³²Th,²³⁰Th,²²⁸Th,²²⁸Ra,²²⁶Ra and²¹⁰Pb in environmental samples was developed. Uranium and thorium isotopes are first chromatographically sepaaated using tri-n-octyl phosphine oxide (TOPO) supported on silica gel. The uranium isotopes are determined by alpha-spectrometry following extraction with TOPO onto a polymeric membrane. Thorium isotopes are co-precipitated with lanthanum fluoride before counting in an alpha spectrometer. Radium isotopes and²¹⁰Pb are separated by co-precipitation/precipitation with mixed barium/lead sulphate. Radium-226 is determined by gross alpha counting of the final BaSO₄ precipitate and²²⁸Ra by gross beta counting of the same source. Lead-210 is determined through beta counting of its daughter product²¹⁰Bi.     

Effect of neutralizing agent content on137Cs leaching from solidified boric acid waste products

For the preservation of environment from radioactive contamination, one of the properties necessary for solidified radioactive wastes is resistance to the release of radionuclides due to leaching by ground water after land disposal. In order to seek the optimum solidifying formulation for cement solidified boric acid concentrate from pressurized water reactor, a variety of specimens were prepared, varying the content of neutralizing agents and neutralization methods. For the leaching measurements, the ANS 16.1 Standard Leach Test was carried out for the specimens which had been mixed with small concentration of¹³⁷Cs to estimate the leachability index. According to our investigation, the optimum contents of neutralizing agents for neutralization of boric acid radioactive waste were determined in view of resistance ability to leaching. Eventually the leachability indices have turned out to be 5.807.91 depending on the formulations.     

Dosage du237Np en trances dans l'uranium et le plutonium

The²³⁷Np content of²³⁸Pu or²³⁹Pu samples were determined by the gammaspectrometry of²³⁸Np formed by thermal neutron activation. The measurements were carried out on irradiated²³⁸Pu samples directly, and after the chemical separation of²³⁹Pu samples. The²³⁷Np content of natural uranium was determined from the ratio of the alpha-activities of²³⁸Pu and²³⁹Pu isotopes formed from the decay of neptunium isotopes produced by the activation of²³⁷Np and²³⁸U isotopes, respectively.      

Determination of traces of uranium and thorium in (Ba, Sr) TiO3 ferroelectrics by inductively coupled plasma mass spectrometry

 Traces of uranium and thorium in barium(II), strontium(II) titanate ((Ba, Sr)TiO₃) ferroelectric materials were determined by inductively coupled plasma mass spectrometry (ICP-MS). Samples were completely dissolved by a mixture of 1.4% H₂O₂ and 1.0 mol⋅l^-1 HNO₃. For a complete separation of the analytes from the matrix elements, a two step separation technique involving leaching and anion-exchange was applied. By the leaching step with HNO₃ more than 90% of the matrix can be removed whereas the analytes completely remained in the solution. The anion-exchange step was carried out on a BIO⋅RAD AG1-X8 column with a mixture of 1.0 mol⋅l^-1 HF and 0.5 mol⋅l^-1 HNO₃ as eluent. The content of uranium and thorium was subsequently measured by ICP-MS. The detection limits (D.L.) obtained were 0.043 ng g^-1 and 0.035 ng g^-1 for U and Th, respectively. The reproducibility was satisfactory with a relative standard deviation of less than 3% (at the 1 ng g^-1 level, n=5). The matrix concentrations in the final solution were reduced to the sub-μg ml^-1 level which is in the range of the detection limits of USN-ICP-AES (ultrasonic nebulization-ICP-atomic emission spectroscopy). The method was successfully applied to the determination of uranium and thorium in three synthetic (Ba, Sr)TiO₃ samples spiked with the analytes at levels of 1, 5 and 10 ng g^-1 and three (Ba, Sr)TiO₃ ferroelectric samples containing sub-ng g^-1 levels of the analytes. Received: 26 February 1996/Revised: 28 May 1996/Accepted: 5 June 1996     

Determination of traces of uranium and thorium in (Ba, Sr) TiO3 ferroelectrics by inductively coupled plasma mass spectrometry

 Traces of uranium and thorium in barium(II), strontium(II) titanate ((Ba, Sr)TiO₃) ferroelectric materials were determined by inductively coupled plasma mass spectrometry (ICP-MS). Samples were completely dissolved by a mixture of 1.4% H₂O₂ and 1.0 mol⋅l^-1 HNO₃. For a complete separation of the analytes from the matrix elements, a two step separation technique involving leaching and anion-exchange was applied. By the leaching step with HNO₃ more than 90% of the matrix can be removed whereas the analytes completely remained in the solution. The anion-exchange step was carried out on a BIO⋅RAD AG1-X8 column with a mixture of 1.0 mol⋅l^-1 HF and 0.5 mol⋅l^-1 HNO₃ as eluent. The content of uranium and thorium was subsequently measured by ICP-MS. The detection limits (D.L.) obtained were 0.043 ng g^-1 and 0.035 ng g^-1 for U and Th, respectively. The reproducibility was satisfactory with a relative standard deviation of less than 3% (at the 1 ng g^-1 level, n=5). The matrix concentrations in the final solution were reduced to the sub-μg ml^-1 level which is in the range of the detection limits of USN-ICP-AES (ultrasonic nebulization-ICP-atomic emission spectroscopy). The method was successfully applied to the determination of uranium and thorium in three synthetic (Ba, Sr)TiO₃ samples spiked with the analytes at levels of 1, 5 and 10 ng g^-1 and three (Ba, Sr)TiO₃ ferroelectric samples containing sub-ng g^-1 levels of the analytes. Received: 26 February 1996/Revised: 28 May 1996/Accepted: 5 June 1996     

Thermal and structure analysis of FeSO4·H2O-BaO2 mixtures

Investigations on the thermal decomposition of FeSO₄·H₂O-BaO₂ mixtures were carried out under isothermal conditions by using simultaneously solid electrolyte cell (EMF-method). Evoked interactions producing oxygen in the temperature range 553-673 K were established by means of a solid electrolyte oxygen analyzer. Based on Mössbauer spectroscopy data and X-ray analysis it was proved that these reactions were associated with the release of oxygen from barium peroxide, oxidation of ferrosulphate-monohydrate to FeOHSO₄, and formation of barium ferrites such as BaFe₂O₄ and BaFe₁₂O₁₉.     

Radium isotopes and <Superscript>222</Superscript>Rn in Austrian drinking waters

The activity concentrations of the Ra isotopes, ²²⁶Ra and ²²⁸Ra, as well as of ²²²Rn were measured in Austrian tap waters. Rn was extracted into a mineral oil cocktail not miscible with water and measured by liquid scintillation counting using pulse-shape analysis for α/β-separation. Ra isotopes were co-precipitated with BaSO₄ or concentrated by filtration through an element specific filter. EDTA solution was used to redissolve the precipitate as well as to release the Ra from the filter. After mixing with a cocktail, the EDTA solution was measured by liquid scintillation counting, too. From our results the effective ingestion doses for adults and 3 months old babies were calculated.     

Leaching behavior of137Cs in cement

To assess the safety of disposal of a radioactive waste-cement composite, the leaching of¹³⁷Cs from a waste composite into a surrounding fluid has been studied. Leaching tests were carried out in accordance with a method recommended by IAEA.¹ The leachability was measured as a function of bentonite clay to cement ratio. The fraction of¹³⁷-Cs leached from a specimen of Portland cement is 0.03–0.13 at a leaching time of 400 d. Results presented in this paper are examples of data obtained in a 10 y mortar and concrete testing project, which will influence the design of the engineered trench system for a future Yugoslav radioactive waste storage center.^2,3     

A new approach to determine Pm in irradiated fuel solutions

Developments carried out in the Laboratory of Isotopic, Nuclear and Elementary Analyses in order to quantify ¹⁴⁷Pm in spent nuclear fuels analyzed at the CEA within the framework of the Burn Up Credit research program for neutronic code validation are presented here. This determination is essential for safety-criticality studies.The quantity and the nature of the radionuclides in irradiated fuel solutions force us to separate the elements of interest before measuring their isotopic content by mass spectrometry. The main objective of this study is to modify the separation protocol used in our laboratory in order to recover and to measure the ¹⁴⁷Pm at the same time as the other lanthanides and actinides determined by mass spectrometry.A very complete study on synthetic solution (containing or not ¹⁴⁷Pm) was undertaken in order to determine the yield of the various stages of separation carried out before obtaining the isolated Pm fraction from the whole of the elements present in the spent fuel solutions. With the lack of natural tracer to carry out the measurement with the isotope dilution technique, the great number of isotopes in fuel, the originality of this work rests on the use of another present lanthanide in fuel to define the output of separation. The yields were measured at the conclusion of each stage of separation with two others lanthanides in order to show that one of them could be used as a tracer to correct the measurement of the ¹⁴⁷Pm with the separation yield. The total yield (at the conclusion of the two stages of separation) was measured at the same time by ICP-MS and liquid scintillation. This last determination made it possible to validate the use of the ¹⁴⁷Sm (natural) to measure the ¹⁴⁷Pm in ICP-MS since the outputs determined in liquid scintillation and ICP-MS (starting from the radioactive decrease of the source having been used to make the synthetic solution) were equivalent. It is the first time that such measurement is performed in ICP-MS.The measurement of the ¹⁴⁷Pm was finally taken on fuels UOx and MOx by using the ¹⁵³Eu like a tracer of the separation yield. The results obtained are in very good agreement with those obtained from neutronic calculation code.     

Extraction of the 131Cs from neutron irradiated barium oxide under microwave radiation

In this work, the solubility dependence of radioactive baric samples under influence of microwave radiation (MWR) has been investigated at various concentrations of HCl after irradiation of BaO target at a flux of thermal neutrons. It is established that the use of MWR for dissolution of a sparingly-soluble barium oxide will accelerate a dissolution process at almost an order of magnitude in comparison with usual heating. Each time after separation of the ¹³¹Cs from radioactive barium solution analyses on radionuclide purity of the ¹³¹Cs product solutions were carried out.