Natural radioactivity in bioassay by alpha-spectrometry measurements

Personnel of nuclear facilities are checked regularly for internal contamination by bioassay measurements. Although these persons are generally not involved in any incident, natural radioactivity from U, Th and Ra can be found in their urine or faeces. Uranium total activity in urine has been found with a range of 0.051 to 3.0 mBq/24 h and in faeces from 14.5 to 380 mBq/d. ²³⁴U/²³⁸U ratio for urine is 1.48 but this ratio varies from 0.47 to 19. By comparison, the ²³⁴U/²³⁸U ratio found in urine from workers in volved with natural uranium or 4.5% enriched uranium is 1.0 and around 4.0 respectively. ²³⁰Th, ²²⁸Th and sometimes ²³²Th have also been detected. The total thorium activity varies from 0.137 to 5.6 mBq/24 h in urine and from 9 to 183 mBq/d in faeces. ²²⁸Th has generally been found in excess of ²³²Th. All these measurements were performed by alpha-spectrometry. The few ²²⁶Ra results have been measured using the Lucas or emanation method.     

Performance of alpha spectrometry in the analysis of uranium isotopes in environmental and nuclear materials

The accuracy of alpha spectrometry in the determination of uranium isotopes at various concentrations levels and with various isotope ratios was tested in a round robin international intercomparison exercise. Results of isotope activity/mass and isotope mass ratios obtained by alpha spectrometry were accurate in a wide range of uranium masses and in isotopic ratios typical of depleted, natural, and low enriched uranium samples. Determinations by alpha spectrometry compared very satisfactorily in accuracy with those by mass spectrometry. For example, determination of U isotopes in natural uranium by alpha spectrometry agreed with mass spectrometry determinations at within ±1%. However, the ²³⁶U isotope, particularly if present in activities much lower than ²³⁵U, might not be determined accurately due to overlap in the alpha particle energies of these two uranium isotopes.     

Uranium isotopes as a tracer of groundwater transport studies

The activity concentrations of ²³⁴U and ²³⁸U in thermal groundwater, deep well water and river water samples from Central Poland were determined. Concentration of ²³⁴U and ²³⁸U in the examined waters varied from <0.013 (LLD) to 16.8 mBq/dm³ and from <0.013 (LLD) to 45.5 mBq/dm³ respectively. The highest uranium activity concentrations were measured in the thermal groundwater from Mszczonow and Cieplice, while the lowest were observed in thermal ground water from Uniejow and Poddebice. In thermal groundwater from Skierniewice, uranium activity concentrations were below lower limit of detection (0.013 mBq/dm³). The ²³⁴U/²³⁸U activity ratio varied from 0.37 (Cieplice) to 1.30 (Poddebice well water).     

Determination of uranium isotopes in environmental samples

The determination of isotopes of uranium by alpha spectrometry in different environmental components (sediments, soil, water, plants and phosphogypsum) is presented and discussed in this paper. The alpha spectrometry is a very convenient and good technique for activity concentration of natural uranium isotopes (²³⁴U, ²³⁵U, ²³⁸U) in environmental samples and provides the most accurate determination of isotopic activity ratios between ²³⁴U and ²³⁸U. The analysis were provided information about possible sources of high concentrations of uranium in the examined sites determined by anthropogenic sources. The calculation of values ²³⁴U/²³⁸U in all analyzed samples was applied to identifying natural or anthropogenic uranium origin. Activity concentration of uranium isotopes in analyzed environmental samples shows that measurement of uranium levels is of great importance for environmental and safety assessment especially in contaminated areas (phosphogypsum waste heap).     

Recovery and pre-concentration of americium (III) from dilute acid solutions using an emulsion liquid membrane containing di-2-ethylhexyl phosphoric acid (D2EHPA) as extractant

Radiochemical results of U isotopes (²³⁴U, ²³⁵U and ²³⁸U) and their activity ratios are reported for well waters as local sources of drinking waters collected from the ten settlements around the Semipalatinsk Nuclear Test Site (SNTS), Kazakhstan. The results show that ²³⁸U varies widely from 3.6 to 356 mBq/L (0.3–28.7 μg/L), with a factor of about 100. The ²³⁸U concentrations in some water samples from Dolon, Tailan, Sarzhal and Karaul settlements are comparable to or higher than the World Health Organization’s restrictive proposed guideline of 15 μg (U)/L. The ²³⁴U/²³⁸U activity ratios in the measured water samples are higher than 1, and vary between 1.1 and 7.9, being mostly from 1.5 to 3. The measured ²³⁵U/²³⁸U activity ratios are around 0.046, indicating that U in these well waters is of natural origin. It is probable that the elevated concentration of ²³⁸U found in some settlements around the SNTS is not due to the close-in fallout from nuclear explosions at the SNTS, but rather to the intensive weathering of rocks including U there. The calculated effective doses to adults resulting from consumption of the investigated waters are in the range 1.0–18.7 μSv/y. Those doses are lower than WHO and IAEA reference value (100 μSv/y) for drinking water.     

Study of uranium isotopic composition in groundwater and deviation from secular equilibrium condition

Uranium concentration in groundwater reflect both redox conditions and uranium content in host rock. In the present study an attempt has been made to study the uranium concentration and activity ratios of uranium isotopes to present the geochemical conditions of the groundwater in Malwa region of Punjab state, India and the reason for high uranium levels and variation of activity ratios from secular equilibrium conditions. Uranium concentration in groundwater samples was found to be in the range of 13.9 ± 1.2 to 172.8 ± 12.3 μg/l with an average value of 72.9 μg/l which is higher than the national and international guideline values. On the basis of uranium concentration, the groundwater of the study region may be classified as oxidized aquifer on normal uranium content strata (20 %) or oxidized aquifer on enhanced uranium content strata (80 %). The ²³⁸U, ²³⁵U and ²³⁴U isotopic concentration in groundwater samples was found to be in the range of 89.2–1534.5, 4.4–68.5, and 76.4–1386.2 mBq/l, respectively. Activity ratios of ²³⁴U/²³⁸U varies from 0.94 to 1.85 with a mean value of 1.11 which is close to unity that shows secular equilibrium condition. High value of ²³⁴U isotope than ²³⁸U may be due to alpha recoil phenomenon. The plot of AR of ²³⁴U/²³⁸U against the total uranium content in log scale reveals that the groundwaters of the study region either belongs to stable accumulation or normal oxidized aquifer.     

Effect of humic acid,pH and ionic strength on the sorption of Eu(III) on red earth and its solid component

A highly sensitive separation procedure has been developed to investigate uranium and thorium activities and their isotopic ratios in environmental water samples in Tokushima, Japan. Uranium and thorium isotopes in environmental water samples were simultaneously isolated from interfering elements with extraction chromatography using an Eichrom UTEVA™ resin column. After the chemical separation, activities of U and Th isotopes coprecipitated with samarium fluoride (SmF₃) were measured by α-spectrometry. It has been confirmed that uranium isotopes are isolated successfully from thorium decay chains by analyzing a test aqueous solution as a simulation of an environmental water sample. The separation procedure has been first applicable to the determination of U and Th activities and their isotopic ratios in a drinking well water named “Kurashimizu” in Tokushima City, Japan. The specific activities of ²³⁸U and ²³²Th in “Kurashimizu” were deduced to be within the upper limits of <0.31 and <0.19 mBq/l, respectively.     

Radioanalytical investigations of uranium concentrations in natural spring, mineral, spa and drinking waters in Hungary

Within this work, the activity concentrations of uranium isotopes (²³⁴U, ²³⁵U, and ²³⁸U) were analyzed in some of the popular and regularly consumed Hungarian mineral-, spring-, therapeutic waters and tap waters. Samples were selected randomly and were taken from different regions of Hungary (Balaton Upland, Bükk Mountain, Somogy Hills, Mez?föld, and Lake Hévíz). Concentration (mBq L^?1) of ²³⁴U, ²³⁵U, and ²³⁸U in the waters varied from 1.1 to 685.2, from <0.3 to 7.9, and from 0.8 to 231.6 respectively. In general, the highest uranium concentrations were measured in spring waters, while the lowest were found in tap waters. In most cases radioactive disequilibrium was observed between uranium isotopes (²³⁴U and ²³⁸U). The activity ratio between ²³⁴U and ²³⁸U varies from 0.57 to 4.97. The calculated doses for the analyzed samples of spring water are in the range 0.07–32.39 μSv year^?1 with an average 4.32 μSv year^?1. This is well below the 100 μSv year^?1 reference level of the committed effective dose recommended by WHO and the EU Council. The other naturally occurring alpha emitting radionuclides (²²⁶Ra and ²¹⁰Po) will be analyzed later to complete the dose assessment. This study provides preliminary information for consumers and authorities about their internal radiological exposure risk due to annual intake of uranium isotopes via water consumption.     

Natural radioactivity levels in mineral,therapeutic and spring waters in Tunisia

Radioactivity measurements were carried out in 26 groundwater samples from Tunisia. Activity concentrations of uranium were studied by radiochemical separation procedures followed by alpha spectrometry and that for radium isotopes by gamma-ray spectrometry.The results show that, the concentrations in water samples range from 1.2 to 69 mBq/L.1, 1.3 to 153.4 mBq/L, 2.0 to 1630.0 mBq/L and 2.0 to 1032.0 mBq/L for ²³⁸U, ²³⁴U, ²²⁶Ra and ²²⁸Ra, respectively. The U and Ra activity concentrations are low and similar to those published for other regions in the world. The natural radioactivity levels in the investigated samples are generally increased from mineral waters through therapeutic to the spring waters.The results show that a correlation between total dissolved solids (TDS) values and the ²²⁶Ra concentrations was found to be high indicating that ²⁶⁶Ra has a high affinity towards the majority of mineral elements dissolved in these waters. High correlation coefficients were also observed between ²²⁶Ra content and chloride ions for Cl^?–Na⁺ water types. This can be explained by the fact that radium forms a complex with chloride and in this form is more soluble.The isotopic ratio of ²³⁴U/²³⁸U and ²²⁶Ra/²³⁴U varies in the range from 0.8 to 2.6 and 0.6 to 360.8, respectively, in all investigated waters, which means that there is no radioactive equilibrium between the two members of the ²³⁸U series. The fractionation of isotopes of a given element may occur because of preferential leaching of one, or by the direct action of recoil during radioactive decay.The annual effective doses due to ingestion of the mineral waters have been estimated to be well below the 0.1 mSv/y reference dose level.     

Uranium series disequilibrium in the coastal surface sediments and sea water of the Arabian Sea

Nearshore surface sediments from various locations of the West Coast of India were leached by saturated ammonium carbonate solution for the extraction of uranium isotopes. The reagent chosen was found to have high efficiency for leaching uranium isotopes without attacking the mineral core of the sediment particle. The activity ratios of²³⁴U/²³⁸U are in the range of 1.11 to 1.14 and the activity ratios of²³⁵U/²³⁵U are in the range of 0.045 to 0.047. The respective activity ratios in leachates, and residues after removal of surface organic matter from the sediment particles by treatment with hydrogen peroxide and 0.05M HCl, revealed disequilibrium between²³⁸U and²³⁴U only in the surface organic matter. The activity ratios of²³⁴U/²³⁸U and²³⁵U/²³⁸U have also been determined in some seawater samples from the Arabian Sea.     

Vertical distribution of uranium concentrations and 235U/238U atom ratios in the coastal water off Aomori, Japan: A survey prior to the operation of a nuclear fuel reprocessing facility

Summary From the viewpoint of environmental radioactivity monitoring, the determination of uranium and its isotope ratio is important for identifying and assessing the environmental impact of any unexpected release from nuclear facilities. In this work, a survey was conducted to determine ²³⁸U concentrations and ²³⁵U/²³⁸U atom ratios in coastal waters off Rokkasho Village, Aomori, Japan, where several uranium-related nuclear facilities have been operating since 1992, and a newly constructed nuclear fuel reprocessing plant is scheduled to be commissioned in 2006. Seawater samples were analyzed directly after a 10-fold dilution using isotope dilution sector-field ICP-MS. Based on the results, we concluded that there is no observable uranium contamination in the investigated sites. In addition, for the first time, a correlation between uranium concentration and salinity was established in coastal waters using the SF-ICP-MS technique.     

Determination of U isotope ratios in sediments using ICP-QMS after sample cleanup with anion-exchange and extraction chromatography

The determination of uranium is important for environmental radioactivity monitoring, which investigates the releases of uranium from nuclear facilities and of naturally occurring radioactive materials by the coal, oil, natural gas, mineral, ore refining and phosphate fertilizer industries, and it is also important for studies on the biogeochemical behavior of uranium in the environment. In this paper, we describe a quadrupole ICP-MS (ICP-QMS)-based analytical procedure for the accurate determination of U isotope ratios (²³⁵U/²³⁸U atom ratio and ²³⁴U/²³⁸U activity ratio) in sediment samples. A two-stage sample cleanup using anion-exchange and TEVA extraction chromatography was employed in order to obtain accurate and precise ²³⁴U/²³⁸U activity ratios. The factors that affect the accuracy and precision of U isotope ratio analysis, such as detector dead time, abundance sensitivity, dwell time and mass bias were carefully evaluated and corrected. With natural U, a precision lower than 0.5% R.S.D. for ²³⁵U/²³⁸U atom ratio and lower than 2.0% R.S.D. for ²³⁴U/²³⁸U activity ratio was obtained with less than 90 ng uranium. The developed analytical method was validated using an ocean sediment reference material and applied to an investigation into the uranium isotopic compositions in a sediment core in a brackish lake in the vicinity of U-related nuclear facilities in Japan.     

Determination of uranium and thorium isotopes in mineral spring waters

Concentrations levels of uranium and thorium isotopes have been analyzed in the m mineral spring waters of a high background region of Brazil: Poços de Caldas and Águas da Prata. The procedure was based on the determination of²³⁸U,²³⁴U,²³²Th,²³⁰Th and²²⁸Th by -spectrometry after separation and purification of the isotopes of interest by using anion-exchange chromatography and preparation of the samples for -measurements by electrodeposition. The concentration varied from <1.1 to 28.4 mBq.l^–1 and from <1.6 to 141 mBq.l^–1 for²³⁸U and²³⁴U, respectively. Thorium isotope measurements varied from <0.2 to 1.8 mBq.l^–1 from <0.3 to 4.9 mBq.l^–1 and from <0.8 to 19.9 mBq.l^–1 for²³²Th,²³⁰Th and²²⁸Th, respectively. Calculations of thorium and uranium isotopic activity ratios were carried out giving values ranging from 1.9 to 7.2, from 1.2 to 3.0 and from 7.7 to 15.3 for²³⁴U/²³⁸U,²³⁰Th/²³²Th and²²⁸Th/²³²Th, respectively. The effective doses due to the intake of²³⁸U and²³⁴U present in these waters are expected to reach values up to 1.4×10^–3 mSv y^–1 and 8.0×10^–3 mSv y^–1, respectively.     

Uranium determination in water samples with elevated salinity from Southern Poland by micro coprecipitation using alpha spectrometry

Due to the importance of water in human life, its quality must be strictly controlled; so simple and reliable analytical methods must be available. For this purpose a rapid procedure for the determination of uranium isotopes in natural water samples with elevated salinity was adopted. It was tested in 16 water samples from Upper and Lower Silesia Regions in Poland. Water samples had salinity in a range of 290–26,925 mg l^{− 1}.In water samples the concentrations of ²³⁴U and ²³⁸U ranged from 2.07 to 52.08 mBq l^{– 1} and from 2.18 to 43.38 mBq l^{– 1} respectively, while ²³⁵U level was below MDA (0.7 mBq l^{− 1}).The isotopic ratio of ²³⁴U/²³⁸U varies in the range from 0.949 to 3.344 in all investigated waters which means that there is usually no radioactive equilibrium between the parent nuclide ²³⁸U and its daughter product ²³⁴U.These results do not show a correlation between total dissolved solids (TDS) values and concentration of dissolved uranium isotopes.Committed effective dose for adults due to uranium intake as a result of drinking water usage was in range of 0.15–3.29 µSv y^{− 1} with an average value of 1.09 µSv y^{− 1} far below the 100 µSv y^{− 1} WHO recommendation.     

Plutonium Isotopes in Sediments from the Sudanese Coast of the Red Sea

This paper presents the activity concentrations of Pu isotopes in surface marine sediments collected from the Sudanese coast of the Red Sea. The following concentration ranges were determined: ²³⁸Pu, 4.7–28.6 mBq/kg; ^239+240Pu, 53–343 mBq/kg dry weight. The average activity ratios of ²³⁸Pu/^239+240Pu (0.075±0.045 mBqk/kg) and ^239+240Pu/¹³⁷Cs (0.026±0.025 mBq/kg) are appropriately comparable to the literature values that are characteristic of the global fallout from the atmospheric nuclear weapon tests. However, ^239+240Pu/¹³⁷Cs ratio in sediments collected from the biologically rich fringing reef is an order of magnitude higher compared to other sampling locations.     

Analysis of Ores and its Purified Constituents by γ‐Spectrometry with Calculation of Uranium Isotopic Atom,Mass, and Activity Ratios

The physical verifications, that the national and international inspectors carry out in order to perform a credibility control, often consist in the measurement of physical quantities, related to the declared nuclear material properties, by Non‐destructive Assay (NDA). Analysis of ores and its purified constituent's samples has been carried out in this work using non‐destructive gamma assay technique. The spectrometer based on HpGe detector and its electronics was calibrated using standard IAEA multi‐lines gamma sources. The efficiency calibration curve was plotted for broad gamma energies; 50–2600 keV. The gamma transition of ²³⁵U (143.7, 163.3, 185.7, and 205.3 keV) and ²³⁸U (63, 766.3, and 1001.03 keV) were used for qualitative and quantitative assay of the samples. The specific activities of the samples were calculated based on the determined efficiency, branching ratio (emission probability per disintegration), mass of sample and count rate of the characteristics gamma transitions of uranium isotopes at fixed geometrical conditions. A simplified equation was derived for calculation of ²³⁵U atom ratios. The results of calculation show natural origin of the analyzed samples; around 0.72 %. Where, the anthropogenic ²³⁶U was not detected at all in the spectra. The uranium activity ratios (²³⁵U/²³⁸U) were calculated based on the measured activity. The uranium isotopic mass and total uranium content of the investigated samples were also calculated. The results obtained are depicted, tabulated and discussed in comparison with recent published national and international works.     

Determination of iodine-129 and iodine-127 in environmental samples collected in Japan

Analytical method for the determination of¹²⁹I and¹²⁷I in environmental samples has been developed by using radiochemical neutron activation analysis. The¹²⁹I levels in the samples such as soil (0.9–41 mBq/kg), precipitation (0.002–0.11 mBq/kg), pine needles (1.2–32 mBq/kg) and seaweed (<0.1–17 mBq/kg) collected near the nuclear facilities in Tokaimura were higher than those from the other areas in Japan. The highest¹²⁹I concentration was found in surface soil (0–5 cm), and the highest¹²⁹I/¹²⁷I ratios were found in pine needles and precipitation. The¹²⁹I/¹²⁷I ratio was higher in rice paddy soil than those in wheat field soil collected around Tokaimura, while the concentration of¹²⁹I somewhat higher in wheat field soil.     

Activity disequilibrium between 234U and 238U isotopes in natural environment

The aim of this work was to calculate the values of the ²³⁴U/²³⁸U activity ratio in natural environment (water, sediments, Baltic organisms and marine birds from various regions of the southern Baltic Sea; river waters (the Vistula and the Oder River); plants and soils collected near phosphogypsum waste heap in Wi?linka (Northern Poland) and deer-like animals from Northern Poland. On the basis of the studies it was found that the most important processes of uranium geochemical migration in the southern Baltic Sea ecosystem are the sedimentation of suspended material and the vertical diffusion from the sediments into the bottom water. Considerable values of the ²³⁴U/²³⁸U are characterized for the Vistula and Oder Rivers and its tributaries. The values of the ²³⁴U/²³⁸U activity ratio in different tissues and organs of the Baltic organisms, sea birds and wild deer are varied. Such a large variation value of obtained activity ratios indicates different behavior of uranium isotopes in the tissues and organisms of sea birds and wild animals. This value shows that uranium isotopes can be disposed at a slower or faster rate. The values of the ²³⁴U/²³⁸U activity ratio in the analyzed plants, soils and mosses collected in the vicinity of phosphogypsum dumps in Wi?linka are close to one and indicate the phosphogypsum origin of the analyzed nuclides. Uranium isotopes ²³⁴U and ²³⁸U are not present in radioactive equilibrium in the aquatic environment, which indicates that their activities are not equal. The inverse relationship is observed in the terrestrial environment, where the value of the of the ²³⁴U/²³⁸U activity ratio really oscillates around unity.     

Optimization of a radioanalytical procedure for the determination of uranium isotopes in environmental samples

A radiochemical procedure is described for the fast and sensitive measurement of uranium isotopes in gaseous and liquid effluents of nuclear facilities. Equally, this procedure is suitable to measure uranium isotopes in all kinds of environmental samples. Uranium is leached from ashed sample materials with HNO₃, HF, and Al(NO₃)₃ solution and separated from matrix elements by extraction with trioctylphosphinic oxide and backextraction with NH₄F. After radiochemical cleaning by coprecipitation with LaF₃ and anion exchange, uranium isotopes are electroplated on stainless steel discs from HCl/oxalate solution. The preparation is measured by alpha-spectrometry using surface barrier detectors. The detection limit for 1000 minutes of counting time is 2 mBq per sample and nuclide, the chemical yield is in the range of 50 to 80%.     

Determination of234U/238U and235U/238U ratios from commercially available uranium compounds by α-spectrometry

The²³⁴U/²³⁸U and²³⁵U/²³⁸U ratios from uranium compounds by -spectrometry technique have been obtained. Ten commercially available uranium reagents were analyzed. The well-separated peaks corresponding to uranium isotopes are evident, providing an energy spectrum of the -particles of uranium isotopes. It was found that some commerical uranium salts were depleted in²³⁴U and²³⁵U.