Biomonitoring of environmental pollution by thorium and uranium in selected regions of the Republic of Kazakhstan

Two former uranium mines and a uranium reprocessing factory in the city of Aktau, Kazakhstan, may represent a risk of contaminating the surrounding areas by uranium and its daughter elements. One of the possible fingerprinting tools for studying the environmental contamination is using plant samples, collected in the surroundings of this city in 2007 and 2008. The distribution pattern of environmental pollution by uranium and thorium was evaluated by determining the thorium and uranium concentrations in plant samples (Artemisia austriaca) from the city of Aktau and comparing these results with those obtained for the same species of plants from an unpolluted area (town of Kurchatov). The determination of the uranium and thorium concentrations in different parts of A. austriaca plants collected from the analyzed areas demonstrated that the main contamination of the flora in areas surrounding the city of Aktau was due to dust transported by the wind from the uranium mines. The results obtained demonstrate that all the areas surrounding Aktau have a higher pollution level due to thorium and uranium than the control area (Kurchatov). A few “hot points” with high concentrations of uranium and thorium were found near the uranium reprocessing factory and the uranium mines.     

Determination of total content and isotopic compositions of plutonium and uranium in environmental samples for safeguards purposes by ICP-QMS

The aim of this work was to determine the concentrations and isotopic compositions of plutonium and uranium in environmental samples for safeguards purposes. An analytical method was developed with a plutonium and uranium separation procedure based on extraction chromatography (using 2 mL TEVA and UTEVA columns) and detection with a quadrupole ICP-MS applying an ultra-sonic nebulizer coupled with a membrane desolvation system. Starting from blank swipes, the background equivalent concentration (BEC) was 8 fg for ²³⁹Pu and 1 ng ²³⁸U. The method was successfully applied to certified reference materials as well as to round robin samples obtained in the framework of the inter-laboratory exercise program, promoted by the Brazilian–Argentine Agency for Accounting and Control of Nuclear Materials (ABACC), together with the US Department of Energy (USDOE). After the introduction of an additional ion-exchange separation step, the methodology was applied to the IAEA-384 sediment reference sample with precise and accurate total plutonium and uranium, ²⁴⁰Pu/²³⁹Pu, ²⁴¹Pu/²³⁹Pu, ²³⁴U/²³⁸U and ²³⁵U/²³⁸U atomic ratio results.     

Uptake of uranium and thorium by native and cultivated plants

Large part of available literature on biogeochemistry of uranium and thorium refers to the studies performed either in highly contaminated areas or in nutrient solutions that have been artificially ‘spiked’ with radionuclides. Effects of background levels of natural radioactivity on soil-grown plants have not been studied to the same extent. In this paper, we summarised results of greenhouse and field experiments performed by the author from 2000 to 2006. We examined some of the factors affecting transfer of U and Th from soil to plants, differences in uptake of these radionuclides by different plants, relationships between U and Th in soil and in plants, and temporal variations of U and Th in different plant species. Concentrations of radionuclides (critical point for experimental studies on biogeochemistry of U and Th - rare trace elements in non-contaminated regions) and essential plant nutrients and trace elements were determined by instrumental neutron activation analysis.     

Depositional behaviors of plutonium and thorium isotopes at Tsukuba and Mt. Haruna in Japan indicate the sources of atmospheric dust

Monthly plutonium and thorium depositions at Tsukuba (28 m asl) and Mt. Haruna (1370 m asl) were measured during 2006 and 2007 (Jan 2006-Dec 2007 at Tsukuba, Nov 2006-Dec 2007 at Mt. Haruna). The monthly ^239,240Pu depositions ranged from 0.044 to 2.67 mBq m⁻² at Tsukuba and from 0.05 to 0.9 mBq m⁻² at Mt. Haruna during the measurement periods. Monthly ^239,240Pu deposition did not differ markedly between the two sites except in April 2007. Seasonal pattern of monthly ^239,240Pu depositions at both sites showed high in spring and low in summer, and typical of seasonal variations in northeastern Asia. Thorium deposition at Tsukuba was higher than that at Mt. Haruna except in May and June 2007. ²³⁰Th/²³²Th activity ratios were used to partition deposition samples into locally and remotely derived fractions. The results revealed that a major proportion of total ^239,240Pu and Th deposits are derived from remote sources, especially in spring.     

Uranium and thorium in soils,mineral sands,water and food samples in a tin mining area in Nigeria with elevated activity

The activity concentrations of uranium and thorium have been determined in soils and mineral sands from the Nigerian tin mining area of Bisichi, located in the Jos Plateau, and from two control areas in Nigeria (Jos City and Akure) using high-purity germanium detectors (HPGe). High resolution sector field inductively coupled plasma mass spectroscopy (HR-SF-ICP-MS) was used to determine uranium and thorium in liquids and foodstuffs consumed locally in the mining area. The activities of uranium and thorium measured in the soils and mineral sands from Bisichi ranged from 8.7 kBq kg⁻¹ to 51 kBq kg⁻¹ for ²³⁸U and from 16.8 kBq kg⁻¹ to 98 kBq kg⁻¹ for ²³²Th, respectively. These values were significantly higher than those in the control areas of Jos City and Akure and than the reference values reported in the literature. They even exceeded the concentrations reported for areas of high natural radioactive background. Radionuclide concentrations in samples of the local foodstuffs and in water samples collected in Bisichi were found to be higher than UNSCEAR reference values. The results reveal the pollution potential of the mining activities on the surrounding areas.     

Fractionation of plutonium in environmental and bio-shielding concrete samples using dynamic sequential extraction

Fractionation of plutonium isotopes (²³⁸Pu, ^239,240Pu) in environmental samples (i.e. soil and sediment) and bio-shielding concrete from decommissioning of nuclear reactor were carried out by dynamic sequential extraction using an on-line sequential injection (SI) system combined with a specially designed extraction column. Plutonium in the fractions from the sequential extraction was separated by ion exchange chromatography and measured using alpha spectrometry. The analytical results show a higher mobility of plutonium in bio-shielding concrete, which means attention should be paid to the treatment and disposal of nuclear waste from decommissioning.     

Evaluation of the readsorption of plutonium and americium in dynamic fractionations of environmental solid samples

A dynamic extraction system exploiting sequential injection (SI) for sequential extractions incorporating a specially designed extraction column is developed to fractionate radionuclides in environmental solid samples such as soils and sediments. The extraction column can contain up to 5 g of a soil sample, and under optimal operational conditions it does not give rise to creation of back pressure. Attention has been placed on studies of the readsorption problems during sequential extraction using a modified Standards, Measurements and Testing (SM&T) scheme with four-step sequential extractions. The degree of readsorption in dynamic and conventional batch extraction systems is compared and evaluated by using a double-spiking technique. A high degree of readsorption of plutonium and americium (>75%) was observed in both systems, and they also exhibited similar distribution patterns of the two radionuclides. However, the dynamic system is fully automated, eliminates manual separations, significantly reduces the operational time required, and offers detailed kinetic information.     

Americium,plutonium and uranium contamination and speciation in well waters,streams and atomic lakes in the Sarzhal region of the Semipalatinsk Nuclear Test Site,Kazakhstan

New data are reported on the concentrations, isotopic composition and speciation of americium, plutonium and uranium in surface and ground waters in the Sarzhal region of the Semipalatinsk Test Site, and an adjacent area including the settlement of Sarzhal. The data relate to filtered water and suspended particulate from (a) streams originating in the Degelen Mountains, (b) the Tel′kem 1 and Tel′kem 2 atomic craters, and (c) wells on farms located within the study area and at Sarzhal. The measurements show that ²⁴¹Am, ^239,240Pu and ²³⁸U concentrations in well waters within the study area are in the range 0.04–87 mBq dm⁻³, 0.7–99 mBq dm⁻³, and 74–213 mBq dm⁻³, respectively, and for ²⁴¹Am and ^239,240Pu are elevated above the levels expected solely on the basis of global fallout. Concentrations in streams sourced in the Degelen Mountains are similar, while concentrations in the two water-filled atomic craters are somewhat higher. Suspended particulate concentrations in well waters vary considerably, though median values are very low, at 0.01 mBq dm⁻³, 0.08 mBq dm⁻³ and 0.32 mBq dm⁻³ for ²⁴¹Am, ^239,240Pu and ²³⁸U, respectively. The ²³⁵U/²³⁸U isotopic ratio in almost all well and stream waters is slightly elevated above the ‘best estimate’ value for natural uranium worldwide, suggesting that some of the uranium in these waters is of test-site provenance. Redox analysis shows that on average most of the plutonium present in the microfiltered fraction of these waters is in a chemically reduced form (mean 69%; 95% confidence interval 53–85%). In the case of the atomic craters, the proportion is even higher. As expected, all of the americium present appears to be in a reduced form. Calculations suggest that annual committed effective doses to individual adults arising from the daily ingestion of these well waters are in the range 11–42 μSv (mean 21 μSv). Presently, the ground water feeding these wells would not appear to be contaminated with radioactivity from past underground testing in the Degelen Mountains or from the Tel′kem explosions.     

Sector field inductively coupled plasma mass spectrometry, another tool for plutonium isotopes and plutonium isotope ratios determination in environmental matrices

The transfer of radio nuclides into the different compartments of the environment are widely studied and leads to the elaboration of transfer models in order to evaluate potential impact onto the environment and humans. Accurate experimental data are needed to validate these models for all types of matrices (air, water, sediments, soils, biota and food...). Among these radionuclides, 238Pu, 239Pu, 240Pu and 241Pu, are often mentioned. They have been released into the environment by nuclear weapon tests, nuclear facilities, reactors or satellite accidents. These different sources have different 240Pu/239Pu ratios and therefore this ratio is used to provide information on the source of contamination into the environment. The most conventional analytical tools used for plutonium isotope determination are liquid scintillation and alpha spectrometry, and thermal ionisation mass spectrometry (TIMS) is still considered as the primary method for determination of plutonium isotope ratios. During the last decade, mass spectrometers equipped with plasma ion sources and sector field analysers were developed and can offer now another alternative method for the accurate determination of isotope content and ratios of long-lived radionuclides in environmental samples. This paper presents and discusses the results obtained for 239Pu, 240Pu and 241Pu content and isotope ratios by sector field ICP-MS in different environmental matrices.     

Influence of plant activity and phosphates on thorium bioavailability in soils from Baotou area, Inner Mongolia

Harm of thorium to living organisms is governed by its bioavailability. Thorium bioavailability in the soil-plant system of Baotou rare earth industrial area was studied using pot experiments of wheat and single extraction methods. The effects of wheat growth stage and phosphate on thorium bioavailability were also investigated. Based on extractabilities of various extraction methods (CaCl₂, NH₄NO₃, EDTA, HOAc) and correlation analysis of thorium uptake by wheat plant and extractable thorium, a mixture of 0.02 M EDTA + 0.5 M NH₄OAc (pH 4.6) was found suitable for evaluation of thorium bioavailability in Baotou soil, which could be predicted quantitatively by multiple regression models. Because of differences of wheat root activities, thorium bioavailability in rhizosphere soil was higher than in bulk soil at tillering stage, but the reverse occurred at jointing stage. Phosphate addition induced the mineralization of soluble thorium by forming stable thorium phosphate compounds, and reduced thorium bioavailability in soil.     

Cs,Pu and Am in bottom sediments and surface water of Lake Päijänne,Finland

The concentrations and vertical distribution of ^239,240Pu, ²⁴¹Am and ¹³⁷Cs in the bottom sediments and water samples of Lake Päijänne were investigated. This lake is important, since the Päijänne area received a significant deposition from the Chernobyl fallout. Furthermore Lake Päijänne is the raw water source for the Helsinki metropolitan area. In addition no previous data on the distribution of plutonium and americium in the sediment profiles of Lake Päijänne exist. Only data covering the surface layer (0–1 cm) of the sediments are previously available. In the sediments the average total activities were 45 ± 15 Bq/m² and 20 ± 7 Bq/m² for ^239,240Pu and ²⁴¹Am, respectively. The average ²⁴¹Am/^239,240Pu ratio was 0.45 ± 0.14. The ²⁴¹Am/^239,240Pu ratio is lowest in the surface layer of the sediments and increases as a function of depth. The ²³⁸Pu/^239,240Pu ratio of the sediment samples varied between 0.012 ± 0.025 and 0.162 ± 0.079, decreasing as a function of depth. The average activity in water was 4.9 ± 0.9 mBq/m³ and 4.1 ± 0.2 mBq/m³ for ^239,240Pu and ²⁴¹Am, respectively. The ²⁴¹Am/^239,240Pu ratio of water samples was 0.82 ± 0.17. ^239,240Pu originating from the Chernobyl fallout calculated from the average total activities covers approximately 1.95 ± 0.01% of the total ^239,240Pu activity in the bottom sediments. The average total ¹³⁷Cs activity of sediment profiles was 100 ± 15 kBq/m² and 19.3 ± 1.4 Bq/m³ in water samples.     

Determination of thorium, uranium and potassium elemental concentrations in surface soils in Cyprus

A comprehensive study was conducted to determine thorium, uranium and potassium elemental concentrations in surface soils throughout the accessible area of Cyprus using high-resolution gamma-ray spectrometry. A total of 115 soil samples was collected from all over the bedrock surface of the island based on the different lithological units of the study area. The soil samples were air-dried, sieved through a fine mesh, sealed in 1000-ml plastic Marinelli beakers, and measured in the laboratory in terms of their gamma radioactivity for a counting time of 18 h each. From the measured gamma-ray spectra, elemental concentrations were determined for thorium (range from 2.5 x 10(-3) to 9.8 microg g(-1)), uranium (from 8.1 x 10(-4) to 3.2 microg g(-1)) and potassium (from 1.3 x 10(-4) to 1.9%). The arithmetic mean values (A.M. +/- S.D.) calculated from all samples are: (1.2+/-1.7 microg g(-1)), (0.6+/-0.7) microg g(-1), and (0.4+/-0.3%), for thorium, uranium and potassium, respectively, which are by a factor of three-six lower than the world average values of 7.4 microg g(-1) (Th), 2.8 microg g(-1) (U) and 1.3% (K) derived from all data available worldwide. The best-fitting relation between the concentrations of Th and K versus U and also of K versus Th, is essentially of linear type with a correlation coefficient of 0.93, 0.84 and 0.90, respectively. The Th/U, K/U and K/Th ratios (slopes) extracted are equal to 2.0, 2.8 x 10(3) and 1.4 x 10(3), respectively.     

Laboratory and field studies of polonium and plutonium in marine plankton

Uptake experiments were successfully undertaken for polonium and plutonium in the marine diatom Skeletonema costatum. Experiments were complemented with a field study which yielded concentration factors for these radionuclides for plankton samples collected in the eastern Irish Sea.     

Proposal for new best estimates of the soil-to-plant transfer factor of U,Th, Ra,Pb and Po

There is increasing interest in radiological assessment of discharges of naturally occurring radionuclides into the terrestrial environment. Such assessments require parameter values for the pathways considered in predictive models. An important pathway for human exposure is via ingestion of food crops and animal products. One of the key parameters in environmental assessment is therefore the soil-to-plant transfer factor to food and fodder crops. The objective of this study was to compile data, based on an extensive literature survey, concerning soil-to-plant transfer factors for uranium, thorium, radium, lead, and polonium. Transfer factor estimates were presented for major crop groups (Cereals, Leafy vegetables, Non-leafy vegetables, Root crops, Tubers, Fruits, Herbs, Pastures/grasses, Fodder), and also for some compartments within crop groups. Transfer factors were also calculated per soil group, as defined by their texture and organic matter content (Sand, Loam, Clay and Organic), and evaluation of transfer factors' dependency on specific soil characteristics was performed following regression analysis. The derived estimates were compared with estimates currently in use.     

On radiocarbon and plutonium leakage to groundwater in the vicinity of a shallow-land radioactive waste repository

A shallow-land radioactive waste repository operated in boggy forest environment from 1963 to 1989. During the operation period, a considerable amount of technogenic radionuclides, in solidified state, was disposed into the vault established in the geological structure at the depth of up to 3 m. Environmental monitoring activities started after the closure of the repository in 1989. Recent investigations revealed transfer of radiocarbon and plutonium to the groundwater in the prevailing flow direction. Activity concentration of ^239,240Pu in non-filtered fraction of the groundwater from observation well no. 4 determined by alpha-spectrometry was 6.4 × 10⁻⁵ Bq l⁻¹ in 2005, and 3.2 × 10⁻⁴ Bq l⁻¹ in 2006. Further analysis of colloid-facilitated transport of plutonium is planned. Variation of ¹⁴C activity concentration in the same well was monitored in 2006. It varied from 0.2 ± 0.1 Bq l⁻¹ in October to 2.8 ± 0.6 Bq l⁻¹ in June and July. Results imply further research into radiocarbon transfer to atmosphere and selected plant species.     

Using sequential extraction techniques to assess the partitioning of plutonium and neptunium-237 from multiple sources in sediments from the Ob River (Siberia)

Sequential extraction techniques have been developed to assess partitioning of anthropogenic radionuclides (²⁴⁰Pu, ²³⁹Pu, and ²³⁷Np), originating from a variety of sources, as identified by using bulk sediment isotopic composition. Sediments were leached sequentially with a series of six chemical treatments designed to approximate different environmental processes that may occur or to selectively extract trace metals contained in different solid phases of the sediments (i.e., exchangeable, reducible, carbonate, organic, acid leachable, and refractory). Results indicate the majority of Pu and Np is similarly distributed within many of the extracted fractions, with the largest percentage (66–97%) of both elements being observed in sediments treated with buffered citrate dithionite (CDB), which targets easily reduced constituents such as Mn and Fe hydrous oxides. While these results do indicate an association of Pu and Np with redox sensitive elements, the environmental implications are unclear given that the CDB treatment is more extreme than naturally occurring conditions. Minor amounts of Np partition differently from Pu in sediments. The NH₄-acetate treatment, which is designed to liberate trace metals that are loosely adsorbed onto the surfaces of sedimentary materials such as hydrated iron oxides and humic substances, or present at exchangeable sites in clay minerals, mobilized ∼12% of the total Np while Pu levels were below detection. The H₂O₂ treatment, which is designed to liberate trace metals bound to organic matter, mobilized ∼8 and ∼1% of Np and Pu, respectively. These results indicate that a minor portion of the total Np may be affected by environmental conditions that have little or no effect on Pu. Between 7 and 24% of the Pu was observed in treatments designed to liberate Pu and Np that are tightly bound to lithogenic phases or refractory silicates. The ²⁴⁰Pu/²³⁹Pu observed in accessible and refractory fractions ranged between 0.11 and 0.18. With the exception of one sample, the ²⁴⁰Pu/²³⁹Pu isotope ratios measured in the refractory fractions are essentially identical having a mean ratio value of 0.123 ± 0.001 (1σ). The ²⁴⁰Pu/²³⁹Pu ratios provide isotopic evidence that suggests a portion of non-fallout contamination has a refractory nature. The presence of similarly low ²⁴⁰Pu/²³⁹Pu ratios in refractory fractions of sediments from the Ob and Irtysh Rivers suggests the existence of a source of refractory Pu which is consistent with refractory “hot particles” derived from surface tests at the Semipalitinsk test site.     

Redox chemistry of sulphate and uranium in a phosphogypsum tailings dump

The present study aims to assess the effect of redox conditions existing within the tailings dump on the stability of phosphogypsum (e.g. sulphate reduction) and uranium(VI). Phosphogypsum sampling and in-situ measurements were carried out at a coastal tailings dump in Vasiliko Cyprus, pH, E_H and solubility experiments were performed in simulated laboratory systems and thermodynamic calculations using MINTEQA2. Generally, in the open tailings dump oxidizing conditions predominate stabilizing sulphur and uranium in their hexavalent oxidation states. On the other hand, after the application of a soil/vegetative cover and in the presence of natural organic matter, anoxic conditions prevail (E_H < −70 mV) resulting in S(VI) and U(VI) reduction to S(−II) and U(IV), respectively. Although, the sulphide anion can form very insoluble compounds with heavy metal ions (e.g. Cd(II), Pb(II) etc.) and U(IV) oxide has very low solubility, partial reduction of sulphate to sulphide within gypsum may affect the stability of phosphogypsum resulting in enhanced erosion of the material by rain- and seawater and washing out of contaminants in particulate/colloidal form.     

Comparison of airborne and terrestrial gamma spectrometry measurements - evaluation of three areas in southern Sweden

The Geological Survey of Sweden (SGU) has been conducting airborne gamma spectrometry measurements of natural radioactivity in Sweden for more than 40 years. Today, the database covers about 80% of the country’s land surface. This article explores the first step of putting this data into use in radioactive source search at ground level. However, in order to be able to use the airborne background measurements at ground level, SGU data must be validated against terrestrial data. In this work, we compare the SGU data with data measured by a portable backpack system. This is done for three different areas in southern Sweden. The statistical analysis shows that a linear relationship and a positive correlation exist between the air and ground data. However, this linear relationship could be revealed only when the region possessed large enough variations in areal activity. Furthermore, the activity distributions measured show good agreement to those of SGU. We conclude that the SGU database could be used for terrestrial background assessment, given that a linear transfer function is established.     

Characterization of uranium and plutonium containing particles originating from the nuclear weapons accident in Thule, Greenland, 1968

To improve long-term radioecological impact assessment for the contaminated ecosystem of Bylot Sound, Greenland, U and Pu containing particles have been characterized with respect to particle size, elemental distribution, morphology and oxidation states. Based on scanning electron microscopy with XRMA, particles ranging from about 20 to 40 microm were isolated. XRMA and mu-XRF mapping demonstrated that U and Pu were homogeneously distributed throughout the particles, indicating that U and Pu have been fused. Furthermore, mu-XANES showed that U and Pu in the particles were present as mixed oxides. U was found to be in oxidation state IV whereas Pu apparently is a mixture of Pu(III) and Pu(IV). As previous assessments are based on PuO2 only, revisions should be made, taking Pu(III) into account.     

Internal distribution of uranium and associated genotoxic damages in the chronically exposed bivalve Corbicula fluminea

Uranium (U) internal distribution and involved effects in the bivalve Corbicula fluminea have been studied after direct chronic exposure (90 d, 10 μg.L-1). U distribution was assessed at the subcellular level (Metal Rich Granules -MRG-, pellets and cytosol fractions) in two main organs of the bivalve (gills and visceral mass). Micro-localisation was investigated by TEM-EDX analysis in the gills epithelium. DNA damage in gill and hemolymph samples was measured by the Comet assay. The 90-d exposure period led to a significant increase of U concentration in gills over time (×5) and a large U quantity in subcellular granules in gills. Finally, a significant increase (×2) in DNA damage was noted in exposed gills and haemocytes. This study shows that the accumulation levels and consequently the potential toxicity cannot be successfully predicted only on the basis of concentration in water or in tissues and subcellular fractions after chronic exposure.