Optimization study on sample pretreatment of spent fuel storage rack

In order to evaluate radionuclide inventories as an essential item for the permanent disposal of spent fuel storage racks, chemical conditions for a sample pretreatment of a spent fuel storage rack were studied. Especially, the surface microstructure and the radionuclide distributions for the spent fuel storage rack were investigated by using a SEM–EDX and γ-spectrometer for minimizing the matrix effect which could affect a chemical separation process of some β-emitting radionuclides. The samples were pretreated with a mixed solution of 5 M HCl and 2 M HNO₃ by an ultrasonic surface leaching method. Some radionuclides in the raw racks showed the radioactivity of 10²–10³ Bq for about 10 g of sample weight. From the sample pretreatment, it was confirmed that almost all radionuclides in the rack were completely extracted from the rack when the dissolved thickness of the rack became a maximum 15 μm by the ultrasonic surface leaching method. The established pretreatment method was applied for all spent fuel storage rack generated from Korean NPPs to determine the scaling factor. The radioactivities of ⁶⁰Co and ¹³⁷Cs radionuclides in the pretreated solutions were in the range of 4.9E−1~1.5E+2 and 1.2E−1~9.0E+0 Bq/g, respectively.     

Sequential separation of <Superscript>99</Superscript>Tc, <Superscript>94</Superscript>Nb, <Superscript>55</Superscript>Fe, <Superscript>90</Superscript>Sr and <Superscript>59/63</Superscript>Ni from radioactive wastes

A sequential separation procedure has been developed for the determination of ⁹⁹Tc, ⁹⁴Nb, ⁵⁵Fe, ⁹⁰Sr and ^59/63Ni in various radioactive wastes generated from nuclear power plants. Ion exchange and extraction chromatography were adopted for individual separation of the radionuclides. Precipitation was supplementarily utilized for both purification of the individual radionuclides and preparation of the radionuclide sources for use in a radioactivity measurement. The chromatographic separation behavior of the radionuclides both from the sample matrix metals and from one another was investigated using stable metals, Re (as a surrogate of ⁹⁹Tc), Nb, Fe, Sr and Ni. The validity of the procedure for reliability and applicability was evaluated by measuring the recovery of the metal carriers added to synthetic radioactive waste solutions. The recoveries by the chromatographic separation were in the range of 84.8 to 102.2% with 2s of less than 8.6%, the recoveries by the precipitation being in the range of 84.3 to 97.3% with 2s of less than 10.9%.     

Laboratory standard for radionuclides in nuclear waste

A laboratory standard for the determination of long-lived radionuclides in nuclear waste has been prepared using concrete as matrix. It will be used to check sample preparation procedures, chemical separations and methods for the determination of nuclides, e.g., nuclear counting techniques or mass spectrometry. The material chosen was a fine-grained ready-to-use cement mixture, to which the following radionuclides were added:⁶⁰Co and¹³⁷Cs as -ray-emitting nuclides,⁹⁹Tc,⁹⁰Sr and⁵⁵Fe as radionuclides emitting pure -radiation or low-energy electrons, and²³³U,²³⁷Np,²³⁸Pu and²⁴¹Am as -emitters. Care was taken to attain a homogeneous distribution of the nuclides in the standard material. Pieces of about 1 g were formed as suitable and representative samples. Repeated analyses were carried out with the standard to check its homogeneity. The analytical procedures are described in brief. The pieces of the standard material have the same content of nuclides within ±5% at a 95% level of confidence.     

Evaluation of the 153Sm-EDTMP radiochemical purity using three chromatographic methods

The knowledge of radioactive and stable elements partitioning to natural sediment systems is essential for modelling their environmental fate. A sequential extraction method consisting of six operationally-defined fractions has been developed for determining the geochemical partitioning of natural (U, Th, ⁴⁰K) and antropogenic (Pu, ²⁴¹Am, ¹³⁷Cs) radionuclides in a 10 cm deep sediment sample collected in the Tyrrhenian sea (Gaeta Gulf, Italy) in front of the Garigliano Nuclear Power Plant. ¹³⁷Cs and ⁴⁰K were measured by gamma-spectrometry. Extraction chromatography with Microthene-TOPO (U, Th), Microthene-TNOA (Pu) and Microthene-HDEHP (Am) was used for the chemical separation of the alpha-emitters: after electrodeposition alpha-spectrometry was carried out. Some stable elements (Fe, Mn, Al, Ca, Pb, Ba, Ti, Sr, Cu, Ni) were also determined in the different fractions to get more information about the chemical association of the radionuclides.     

Biosorptive behavior of some dead biomasses in the removal of Sr(85+89) from aqueous solutions

The knowledge of radioactive and stable elements partitioning to natural sediment systems is essential for modelling their environmental fate. A sequential extraction method consisting of six operationally-defined fractions has been developed for determining the geochemical partitioning of natural (U, Th, ⁴⁰K) and antropogenic (Pu, ²⁴¹Am, ¹³⁷Cs) radionuclides in a 10 cm deep sediment sample collected in the Tyrrhenian sea (Gaeta Gulf, Italy) in front of the Garigliano Nuclear Power Plant. ¹³⁷Cs and ⁴⁰K were measured by gamma-spectrometry. Extraction chromatography with Microthene-TOPO (U, Th), Microthene-TNOA (Pu) and Microthene-HDEHP (Am) was used for the chemical separation of the alpha-emitters: after electrodeposition alpha-spectrometry was carried out. Some stable elements (Fe, Mn, Al, Ca, Pb, Ba, Ti, Sr, Cu, Ni) were also determined in the different fractions to get more information about the chemical association of the radionuclides.     

Geochemical partitioning of actinides, 137Cs and 40K in a Tyrrhenian sea sediment sample: Comparison to stable elements

The knowledge of radioactive and stable elements partitioning to natural sediment systems is essential for modelling their environmental fate. A sequential extraction method consisting of six operationally-defined fractions has been developed for determining the geochemical partitioning of natural (U, Th, ⁴⁰K) and antropogenic (Pu, ²⁴¹Am, ¹³⁷Cs) radionuclides in a 10 cm deep sediment sample collected in the Tyrrhenian sea (Gaeta Gulf, Italy) in front of the Garigliano Nuclear Power Plant. ¹³⁷Cs and ⁴⁰K were measured by gamma-spectrometry. Extraction chromatography with Microthene-TOPO (U, Th), Microthene-TNOA (Pu) and Microthene-HDEHP (Am) was used for the chemical separation of the alpha-emitters: after electrodeposition alpha-spectrometry was carried out. Some stable elements (Fe, Mn, Al, Ca, Pb, Ba, Ti, Sr, Cu, Ni) were also determined in the different fractions to get more information about the chemical association of the radionuclides.     

Analysis of Naturally Occurring Radioisotopes in Peat moss Greenhouse Soils and Agriculture Mud in Egypt

In this work, the activity concentrations (radioactivity) and distributions of natural radionuclides in peat moss samples were investigated. The measurements were performed using HP-Ge detector and XRD technique. The samples represent six types of soils. The concentrations of radionuclides of ²³⁸U, ²²⁶Ra, ²³²Th and ⁴⁰K are ranged from 17.14 to 130.83, 13.19 to 26.09, 5.33 to 25.2 and 143.26 to 600.31 Bq · kg^–1 (dry weight), respectively, for the different samples. This work also highlights that no correlation has been observed between radionuclides present in the samples, which in turn reflects the random method behind the preparation of the samples. The obtained results from the XRD analysis were in good agreement with radiometry measurements. The safety of peat moss uses was limited for certain agricultural crops due to the presence of high percent of sulphur in some types of soil. The radon concentration calculated using the empirical formula is more accurate than those obtained from the manual measurements and significant values were expected to emanate from the samples under investigation.     

Ion chromatography inductively coupled plasma mass spectrometry (IC-ICP-MS) and radiometric techniques for the determination of actinides in aqueous leachate solutions from uranium oxide

The choice of the analytical method for the determination of actinide isotopes in leachate solutions has to be made considering several parameters: detection limit for each isotope, sample preparation procedure in terms of duration and complexity, counting time and interferences. A leachate solution obtained by keeping a pellet of UO₂ doped with ²³⁸Pu in contact with distilled water was investigated for the content of U and Pu isotopes by radiometric methods (α-, γ-spectrometry and liquid scintillation counting). The results of the radiometric methods were compared with those obtained from the analysis performed by inductively coupled plasma mass spectrometry on-line to a system for chromatographic separation (IC-ICP-MS). The comparison confirmed that IC-ICP-MS is a powerful method for the detection of long-lived radionuclides. The radiometric methods have a detection limit two orders of magnitude lower than IC-ICP-MS in the case of short-lived radioisotopes mostly due to the low background in the detector. On the other hand, the sample preparation and the analysis duration are more time-consuming compared to IC-ICP-MS; moreover, not all isotopes can be determined by using only one radiometric technique.     

Seasonal variations of atmospheric210Pb and7Be concentrations at Kumamoto, Japan and their removal from the atmosphere as wet and dry depositions</p> </p>

Summary A relatively simple chemical separation procedure has been developed for the simultaneous determination of⁸⁹Sr and ⁹ 0Sractivities in water samples and on aerosol-filters of the Nuclear Power Plant (NPP) Paks origin. The procedure combines the cation-exchange chromatographic (Dowex 50 WX 8 resin) and solid phase extraction (EIChroM Sr.Spec?, DC18C6 crown ether) steps. The beta-radiation of radionuclides can be measured directly after the chemical separation by LSC. The activities of⁸⁹Sr,⁹⁰Sr and⁹⁰Y are calculated from an over determined set of equations using a method of constrained optimization technique. The equations are based on LSC measurements performed in three counting windows plus the⁹⁰Sr-⁹⁰Y decay law. The chemical yield of strontium is determined by ICP-AES. The lowest limits of detectable activity, for the measurement time of 600 minutes, are 30 mBq/sample and 18 mBq/sample for⁸⁹Sr and⁹⁰Sr, respectively.     

An ion chromatographic separation method for the sequential determination of <Superscript>90</Superscript>Sr, <Superscript>241</Superscript>Am and Pu isotopes in a urine sample

A radiobioassay method has been developed for the sequential determination of ⁹⁰Sr, ²⁴¹Am and Pu isotopes in a urine sample. Unlike the existing methods using multiple extraction chromatographic cartridges, this work demonstrates an application of an automated ion chromatographic (IC) system for the separation of these radionuclides on a single IC column. The method meets the bioassay performance criteria for relative bias and relative precision as recommended by ANSI/HPS N13.30-2011. The detection limits for the radionuclides are found to be satisfactory for medical intervention in case of an accidental exposure scenario. Sample preparation time is less than 11 h.     

Characterization of an extraction chromatographic resin for the separation and determination of 36Cl and 129I

The monitoring of long-lived radionuclides is of great importance in the context of the surveillance of nuclear facilities, during their operation as well as during their decommissioning. This is especially true for radionuclides of rather volatile elements, such as chlorine and iodine, the main interest being in ³⁶Cl and ¹²⁹I. Liquid Scintillation Counting (LSC) is a widely used measurement technique especially for the determination of ³⁶Cl that requires a thorough and selective sample preparation in order to give accurate results. Sample preparation methods frequently employed such as volatilization and/or repeated precipitation steps can be rather elaborate and time consuming. Therefore, an attempt has been made to develop an ‘easy to use’ extraction chromatographic resin that allows extraction, and subsequent separation, of chloride and iodide from pretreated environmental and decommissioning samples for their determination via LSC. First results of the characterization of the resin including D _w values of Cl^?, I^? and potential interferents, and of the method development are presented as well as the result of the analysis of a simulated real sample.     

Labelled compounds as radiopharmaceuticals for radiosynoviorthesis

Radiopharmaceuticals for radiosynoviorthesis are designed as suspension (colloidal) of particles in sterile and pyrogen free form, where radionuclide (active substance) fix on carrier which is form solid particles or gel form. Generally, radionuclide and carrier have to fulfil the request of sterility, chemical purity, non toxicity, non allergen and low cost preparation. In term of the radionuclide purity, beta-emission with sufficient energy for penetration and ablation the synovial tissue and low gamma-radiation is requested. The radionuclide gold-198 in colloidal form was used as radiopharmaceutical for radiosynoviorthesis at first. Presently, beta-emitting radionuclides, which have no or only a minimal gammaemission, are used. Between such radionuclides is possible to insert: yttrium-90, rhenium-186 and radiolanthanoides — dysprosium-165, holmium-166 and erbium-169. In this paper are presented experiences with preparation [¹⁶⁶Ho] Holmium-Macroaggregates ([¹⁶⁶Ho] holmium-MA), [¹⁶⁶Ho] holmium-Polylactic Acid Microspheres ([¹⁶⁶Ho] Ho-PLA-MS) which are potential candidate for radiosynoviorhesis.     

Partitioning of natural radionuclides in sediments around a former uranium mine and mill

Partitioning of natural radionuclides in sediments from streams affected by the waste piles of the former uranium mine and mill located at ?irovski vrh, Slovenia, was performed by applying a sequential extraction procedure. The sediments were collected at three sites located upstream and three sites located downstream of the waste piles. Then the four-step Community Bureau of Reference (BCR) sequential extraction protocol was applied to the samples and the natural radionuclides ²³⁸U, ²³⁰Th, ²²⁶Ra, ²¹⁰Pb and ²¹⁰Po were analysed in each extraction fraction. It was expected that the fractionation of natural radionuclides originating from the waste piles would differ from that upstream of the influence of waste piles because their chemical environment had been altered during the processes of uranium extraction. This difference could allow tracing of the radionuclides coming from the waste piles downstream of the affected watercourses. The results definitely showed that the total activity concentrations at sites downstream of the influence of the waste piles were higher than at sites upstream of the piles. However, this difference was geographically very limited and could no longer be detected already at a distance of about 5 km downstream. Unexpectedly, the fractionation of radionuclides upstream and downstream of the area of influence of the waste piles did not appear to be significantly altered. The sole differences found were for ²³⁸U and ²²⁶Ra in the second fraction (the “Fe/Mn oxides” fraction) and for ²¹⁰Po in the fourth fraction (the “residue” fraction) of the BCR sequential extraction protocol.     

Rapid determination of 226Ra in environmental samples

A new rapid method for the determination of ²²⁶Ra in environmental samples has been developed at the Savannah River Site Environmental Lab (Aiken, SC, USA) that can be used for emergency response or routine sample analyses. The need for rapid analyses in the event of a Radiological Dispersive Device or Improvised Nuclear Device event is well-known. In addition, the recent accident at Fukushima Nuclear Power Plant in March, 2011 reinforces the need to have rapid analyses for radionuclides in environmental samples in the event of a nuclear accident. ²²⁶Ra (T1/2?=?1,620?years) is one of the most toxic of the long-lived alpha-emitters present in the environment due to its long life and its tendency to concentrate in bones, which increases the internal radiation dose of individuals. The new method to determine ²²⁶Ra in environmental samples utilizes a rapid sodium hydroxide fusion method for solid samples, calcium carbonate precipitation to preconcentrate Ra, and rapid column separation steps to remove interferences. The column separation process uses cation exchange resin to remove large amounts of calcium, Sr Resin to remove barium and Ln Resin as a final purification step to remove ²²⁵Ac and potential interferences. The purified ²²⁶Ra sample test sources are prepared using barium sulfate microprecipitation in the presence of isopropanol for counting by alpha spectrometry. The method showed good chemical recoveries and effective removal of interferences. The determination of ²²⁶Ra in environmental samples can be performed in less than 16?h for vegetation, concrete, brick, soil, and air filter samples with excellent quality for emergency or routine analyses. The sample preparation work takes less than 6?h. ²²⁵Ra (T1/2?=?14.9?day) tracer is used and the ²²⁵Ra progeny ²¹⁷At is used to determine chemical yield via alpha spectrometry. The rapid fusion technique is a rugged sample digestion method that ensures that any refractory radium particles are effectively digested. The preconcentration and column separation steps can also be applied to aqueous samples with good results.     

Measuring alpha and beta activity of filter and swab samples with LSC

Analysis of alpha and beta emitters in aerosol filters and swabs of different materials by liquid scintillation counter is discussed. This method appears suitable for fast determination of activity of radionuclides due to direct alpha and beta separation, measurement in 4π geometry and without sample treatment. The selected group of radionuclides was chosen with respect to military significance, radiotoxicity, and possibility of potential misuse. ⁹⁰Sr and ²³⁹Pu were selected as model radionuclides. Three types of filters were examined, and the attention was also focused on optimizing the type and volume of LSC cocktail. The efficiencies for ²³⁹Pu and ⁹⁰Sr were 90% and 79%, respectively. This method was the most effective for the glass fiber filters measured with the MaxiLight cocktail.     

Factors Controlling Natural Radionuclides Migration in Sedimentary Rock Samples,Gabal Um‐Hamd,Southwestern Sinai,Egypt

The activity concentrations of some radionuclides (²³⁸U, ²³⁴U, ²³⁰Th, ²²⁶Ra, ²³²Th, ⁴⁰K and ²³⁵U) were measured by γ‐ray spectrometry in order to study their behavior and the relation between them in Carboniferous rock samples collected from Gabal (mountain) Um‐Hamd, southwestern Sinai, Egypt. The whole samples are located in the two limbs and trough of a synclinal form structure to identify the radionuclides migration processes which have occurred in these rock samples. The average activity concentrations of ²³⁸U, ²³²Th, ²²⁶Ra, and ⁴⁰K measured in the all samples except sandy dolostone sample are higher than the worldwide average values as reported by UNSCEAR 2008. The activity ratios (²³⁴U/²³⁸U) for half of the samples are in equilibrium, while the other half samples are below unity indicates migration‐out of uranium. The hazard indices were also calculated. The variations in lithologic types and the configuration of the structural synform played its roles beside the physical and chemical properties of different radionuclides in their fractionations.     

A fast and very sensitive LSC procedure to determine Fe-55 in steel and concrete

This procedure for determining Fe-55 contributes to a safe and economically reasonable decommissioning of nuclear power plants. Co-60, Fe-55 and Ni-63 are the most abundant, long-lived radionuclides associated with contaminated piping, hardware, and concrete for several decades of years after shutdown. The analysis of Fe takes about three hours until the measurement with an anticoincidence shielded LSC Quantulus 1220 starts. The decontamination factors are ranging from greater than 10⁵ to 10⁹ for all important naturally and artificially occurring radionuclides except Sb. The chemical yield stays constant at a value of about 92% up to 0.1 g stable Fe in steel, concrete or other material. The detection limits (confidence level 95%) reach values of 8 mBq per sample or about 60 mBq/g steel and 1.5 mBq/g concrete at a counting time of 1000 minutes. Four to eight analyses are performed by one technician during eight hours.     

Determination of difficult-to-measure actinides in evaporator concentrate

Radiochemical separation of americium, neptunium and plutonium was tested on model solution of evaporator concentrate sample for isolation of each of them for alpha-spectrometry analysis. A good chemical separation of radionuclides of interest from the matrix and interfering radionuclides is required, once the relatively small difference in alpha-particle energy makes it difficult to spectrometrically separate the peaks. This paper describes use of the molecular recognition technology product AnaLig^®Pu-01 gel from IBC Advanced Technologies, Inc. to effectively and selectively pre-concentrate, separate and recover americium, neptunium and plutonium from model solution of evaporator concentrate samples from Nuclear Power Plant which belong to the most difficult matrices to analyse. The method is suitable for analysing highly contaminated samples of radioactive waste in a relatively short time. For counting the alpha activity of ²⁴¹Am, ^239,240Pu, ²³⁸Pu and ²³⁷Np ORTEC 576A alpha-spectrometer equipped with ULTRA^TM ion implanted silicon detectors (600 mm² active area) was used. The spectra were processed by using the Alpha-vision^TM 32-bit emulation software from the EG&G ORTEC company.     

Nanotome cluster bombardment to recover spatial chemistry after preparation of biological samples for SIMS imaging

A C₆₀⁺ cluster ion projectile is employed for sputter cleaning biological surfaces to reveal spatio-chemical information obscured by contamination overlayers. This protocol is used as a supplemental sample preparation method for time of flight secondary ion mass spectrometry (ToF-SIMS) imaging of frozen and freeze-dried biological materials. Following the removal of nanometers of material from the surface using sputter cleaning, a frozen-patterned cholesterol film and a freeze-dried tissue sample were analyzed using ToF-SIMS imaging. In both experiments, the chemical information was maintained after the sputter dose, due to the minimal chemical damage caused by C₆₀⁺ bombardment. The damage to the surface produced by freeze-drying the tissue sample was found to have a greater effect on the loss of cholesterol signal than the sputter-induced damage. In addition to maintaining the chemical information, sputtering is not found to alter the spatial distribution of molecules on the surface. This approach removes artifacts that might obscure the surface chemistry of the sample and are common to many biological sample preparation schemes for ToF-SIMS imaging.