Separation and measurement of thorium, plutonium, americium, uranium and strontium in environmental matrices

A technique for the isolation of thorium (Th), plutonium (Pu), americium (Am), uranium (U) and strontium (Sr) isotopes from various environmental matrices has been adapted from a previously published method specific to water samples (Maxwell, 2006). Separation and isolation of the various elemental fractions from a single sub-sample is possible, thereby eliminating the need for multiple analyses.The technique involves sample dissolution, concentration via calcium phosphate co-precipitation, rapid column extraction using TEVA™, TRU™ and Sr-Spec™ resin cartridges, alpha spectrometry for Th, Pu, U and Am and Cerenkov counting for Sr.Various standard reference materials were analysed and chemical yields are in the range of 70-80% for Th, Am, U and Sr and 50-60% for Pu. Sample sizes of up to 10 L for water, 5 g for dry soil and sediment and 10 g for dry vegetation and seaweed can be processed using this technique.     

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.     

Spatial distribution of uranium and thorium in the surface soil around proposed uranium mining site at Lambapur and its vertical profile in the Nagarjuna Sagar Dam

The understanding and evaluation of the possible interactions of various naturally occurring radionuclides in the world's third largest man-made dam, Nagarjuna Sagar located in Andhra Pradesh, India and built on river Krishna assumed significance with the finding of uranium deposits in locations near the dam. For the present work, surface soil samples from the mineralized area of Lambapur, Mallapuram, Peddagattu and sediment core samples from the Nagarjuna Sagar dam were analyzed for naturally occurring radionuclides namely uranium and thorium using gamma spectrometric technique. Also toxic elements lead and chromium were analysed by the Energy Dispersive X-ray Fluorescence Spectrometer (EDXRF) technique. Surface soil samples show a variation from 25 to 291 Bq/kg (2.02–23.5 mg/kg) for ²³⁸U and 32–311 Bq/kg (7.9–76.9 mg/kg) for ²³²Th. U/Th concentration ratio in surface soil samples ranged from 0.19 to 0.31 and was found comparable with the nation wise average of 0.26. The study of sediment core samples reflected higher U/Th concentration ratio of 0.30–0.33 in the bottom section of the core as compared to 0.22–0.25 in the upper section. The concentration ratio in the upper section of the core was similar to the ratio 0.23 found in the western Deccan Basalt region through which the river originates. A higher concentration of lead and chromium was observed in the upper section of the core compared to bottom section indicating the impact of river input on the geochemical character of dam sediment.     

Arbuscular mycorrhiza reduces phytoextraction of uranium, thorium and other elements from phosphate rock

Uptake of metals from uranium-rich phosphate rock was studied in Medicago truncatula plants grown in symbiosis with the arbuscular mycorrhizal fungus Glomus intraradices or in the absence of mycorrhizas. Shoot concentrations of uranium and thorium were lower in mycorrhizal than in non-mycorrhizal plants and root-to-shoot ratio of most metals was increased by mycorrhizas. This protective role of mycorrhizas was observed even at very high supplies of phosphate rock. In contrast, phosphorus uptake was similar at all levels of phosphate rock, suggesting that the P was unavailable to the plant-fungus uptake systems. The results support the role of arbuscular mycorrhiza as being an important component in phytostabilization of uranium. This is the first study to report on mycorrhizal effect and the uptake and root-to-shoot transfer of thorium from phosphate rock.     

Critical compilation and review of plant/soil concentration ratios for uranium,thorium and lead

The transfer of natural radionuclides of the U decay series through the biosphere is important, especially for assessment of the impacts of mining and milling of U ores. The pathway from soil through plants to humans can contribute significantly to the overall dose received from these radionuclides. Element-specific concentration ratios (CRs) used to model the impact of radionuclides have been reported for U, Th and Pb but have not received the research or critical review accorded other radionuclides associated with the nuclear industry. This paper compiles and analyses many of the available data on CRs for U, Th and Pb and recommends values appropriate for environmental assessments. A brief overview of the statistical properties of CR values and the complex soil/plant processes encompassed by this ratio is also given, as well as an overview of some of the physical, chemical and biological factors likely to influence CR values.Our analysis showed that CR values decreased significantly as the corresponding soil concentrations increased. Although the variability was substantial, with ranges of 1000- to 30 000-fold, CR values did differ significantly among some soil and plant types. The overall geometric means were 0·0045, 0·0036 and 0·052 for U, Th and Pb, respectively.     

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.     

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.     

Effect of pH on the sorption of uranium in soils

This work was undertaken to study the influence of soil type and chemical composition on uranium sorption ratios (SR in 1 kg-1) in order to reduce the uncertainty associated with this parameter in risk assessment models. Thirteen soil samples were collected from three different locations in France under different geological conditions. Clay content varied from 7.0 to 50.0%, pH ranged from 5.5 to 8.8 and organic matter content from 1.0 to 4.6%. Soils were incubated at room temperature in polyethylene packets for 28 days in the presence of 1 mg U kg-1 soil. Sorption ratio values varied from 0.9 to 3198 for all soils with no significant effect of soil texture or of organic matter. However, soil pH was highly linearly correlated with (log SR) as a probable consequence of the existence of different uranium complexes as a function of soil pH. The sorption behaviour differences between UO2(2+) and UO2(2+)-carbonate complexes are so great that any other effect of soil properties on U sorption is hidden. Thus, soil pH should be the focus variable for reduction of the uncertainty associated with the soil Kd value used in environmental risk assessments, even for reducing the uncertainty in site-specific Kd values.     

Reconstruction of atmospheric concentrations and deposition of uranium and decay products released from the former uranium mill at Uravan, Colorado

Radionuclide concentrations in air from uranium milling emissions were estimated for the town of Uravan, Colorado, USA and the surrounding area for a 49-yr period of mill operations beginning in 1936 and ending in 1984. Milling processes with the potential to emit radionuclides to the air included crushing and grinding of ores; conveyance of ore; ore roasting, drying, and packaging of the product (U(3)O(8)); and fugitive dust releases from ore piles, tailings' piles, and roads. The town of Uravan is located in a narrow canyon formed by the San Miguel River in western Colorado. Atmospheric transport modeling required a complex terrain model. Because historical meteorological data necessary for a complex terrain model were lacking, meteorological instruments were installed, and relevant data were collected for 1 yr. Monthly average dispersion and deposition factors were calculated using the complex terrain model, CALPUFF. Radionuclide concentrations in air and deposition on ground were calculated by multiplying the estimated source-specific release rate by the dispersion or deposition factor. Time-dependent resuspension was also included in the model. Predicted concentrations in air and soil were compared to measurements from continuous air samplers from 1979 to 1986 and to soil profile sampling performed in 2006. The geometric mean predicted-to-observed ratio for annual average air concentrations was 1.25 with a geometric standard deviation of 1.8. Predicted-to-observed ratios for uranium concentrations in undisturbed soil ranged from 0.67 to 1.22. Average air concentrations from 1936 to 1984 in housing blocks ranged from about 2.5 to 6 mBq m(-3) for (238)U and 1.5 to 3.5 mBq m(-3) for (230)Th, (226)Ra, and (210)Pb.     

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.     

Determination of uranium and radon in potable water samples

In this work, potable water samples collected from boreholes of the Migdonia valley, located NE of the city of Thessaloniki, were analyzed for the determination of uranium (238U) and radon (222Rn) concentrations. The objective of the present work is to examine if there is any correlation between radon and uranium concentrations in the water samples. For the determination of traces of uranium in water samples, an analytical technique was developed based on the selective adsorption of uranium on the chelating resin, SRAFION NMRR, and the in situ determination of the retained uranium by instrumental neutron activation analysis (INAA). By the described procedure, it was possible to determine uranium amounts in the range of microg/l. For measuring radon in water, a liquid scintillation counting system, using the Packard protocol was employed. The measured 222Rn activity concentrations are from background level up to 160 Bq l (-1).     

Radium-226 concentrations in faeces of snowshoe hares,Lepus americanus,established near uranium mine tailings

Samples of snowshoe hare faeces were collected near revegetated and chemically stabilized uranium mine tailings and at a control site. Washing the faecal pellets in water with concurrent ultrasonic agitation was ineffective in removing all traces of external contamination. Internal ²²⁶Ra levels in the faeces from the mine wastes were higher than controls. ²²⁶Ra levels in faeces are considered too low to constitute an important avenue for dispersing the radionuclide from the waste site.     

Determination of depleted uranium in environmental samples by gamma-spectroscopic techniques

The military use of depleted uranium initiated the need for an efficient and reliable method to detect and quantify DU contamination in environmental samples. This paper presents such a method, based on the gamma spectroscopic determination of 238U and 235U. The main advantage of this method is that it allows for a direct determination of the U isotope ratio, while requiring little sample preparation and being significantly less labor intensive than methods requiring radiochemical treatment. Furthermore, the fact that the sample preparation is not destructive greatly simplifies control of the quality of measurements. Low energy photons are utilized, using Ge detectors efficient in the low energy region and applying appropriate corrections for self-absorption. Uranium-235 in particular is determined directly from its 185.72 keV photons, after analyzing the 235U-226Ra multiplet. The method presented is applied to soil samples originating from two different target sites, in Southern Yugoslavia and Montenegro. The analysis results are discussed in relation to the natural radioactivity content of the soil at the sampling sites. A mapping algorithm is applied to examine the spatial variability of the DU contamination.     

Use of HPGe gamma-ray spectrometry to assess the isotopic compositiion of uranium in soils

Gamma-ray spectrometry was used to determine uranium activity and investigate the presence of depleted uranium in soil samples collected from camping sites of the Greek expeditionary force in Kosovo. Assessment of 238U concentrations was based on measurements of the 63.3 keV and 92.38 keV emissions of its first daughter nuclide, 234Th. To determine the isotopic ratio of 238U/235U, secular equilibrium along the two radioactive series was first ensured and thereby the contribution of 235U under the 186 keV peak was deduced. The uranium activity in the samples varied from 48 to 112 Bq kg(-1), whereas the activity ratio of 238U/235U averaged 23.1+/-4.3.     

Size-fractionated thorium isotopes (228Th, 230Th, 232Th) in surface waters in the Jiulong River estuary, China

Thorium isotopes (228Th, 230Th, 232Th and 234Th) are useful tracers for studying particle dynamics and trace element scavenging in marine environments. In this study, surface waters were collected along a salinity gradient from the Jiulong River estuary, China, for determination of activity concentrations of 228Th, 230Th and 232Th in different size fractions, namely, the >53 microm, 10-53 microm, 2-10 microm, 0.4-2 microm, 10 kDa-0.4 microm and the <10 kDa fractions. Our results indicated that the activity concentrations of 228Th, 230Th and 232Th in the Jiulong River estuarine waters were significantly higher than most of the previously reported values in coastal and oceanic seawaters, suggesting a higher lithogenic U and Th contribution from the Jiulong River Basin. When normalized to the particulate mass concentration, the activity concentrations of the three thorium isotopes decreased with increasing particle size, demonstrating the important role of surface areas of particles in controlling the scavenging of thorium from the water column. The partitioning of three thorium isotopes showed a common characteristic, i.e., the >53 microm fraction had the least share (0-1%), while the 10-53 microm fraction had the largest share of Th isotopes. The average value of the 230Th/232Th activity ratio (230Th/232Th)(A.R.) increased from 0.8 in the >53 microm fraction to 3.7 in the 10 kDa-0.4 microm fraction, indicating that the radiogenic Th isotopes are preferentially scavenged by the small size particles. (230Th/232Th)(A.R.) in the <10 kDa and 10 kDa-0.4 microm fractions were similar, however, suggesting a similar chemical composition and/or equilibrium partitioning between the low molecular weight and colloidal Th. It was very interesting to note that the geochemical behaviors of the three Th isotopes were different from each other. Dissolved 228Th had the highest concentration in the mid-salinity region, showing a non-conservative behavior with additional input. In contrast, dissolved 232Th showed a concave profile, indicating a net removal of 232Th during the mixing of fresh water with seawater. The behavior of Th isotopes in the <10 kDa fraction followed those in the dissolved phases. The difference in geochemical behaviors among three Th isotopes was ascribed to their different sources in the estuary.     

Determination of bioavailable rhenium fraction in agricultural soils

Rhenium (Re) mobility in agricultural soils was studied in order to obtain information relevant to (99)Tc mobility in soil-to-plant systems. Since water soluble Tc and Re are highly bioavailable, extraction of Re with water was carried out in addition to a total Re determination in the soils. The geometric means of total Re for paddy field, upland field and other soils were 0.34, 0.23, and 0.28 ng g(-1), respectively, while those of water soluble Re (<0.45 microm membrane filterable) were 0.053, 0.015 and 0.008 ng g(-1), respectively. There were no differences for total Re among soil uses; however, the water soluble Re/total Re ratio was significantly higher in paddy field soils (16%) than in other soil uses (6% for upland fields and 3% for other uses). Rhenium mobility and plant availability were higher in paddy fields than in other agricultural fields, and similar phenomena would be expected for (99)Tc.     

239+240Pu, 90Sr and 137Cs inventories in surface soils of Vietnam

Fallout 239+240Pu, 238Pu, 90Sr and 137Cs inventories in surface soils were measured for 20 locations in northern Vietnam yielding the mean values (+/- standard error) of 26.5+/-3.8 Bq m(-2) for 239+240Pu, 1048+/-143 Bq m(-2) for 137Cs and 212+/-28 Bq m(-2) for 90Sr. The concentrations of 137Cs and plutonium isotopes strongly correlate with each other resulting in a stable 239+240Pu/137Cs inventory ratio of 0.025+/-0.002. Among soil parameters, organic matter and fulvic acids strongly correlate with caesium and plutonium isotopes, especially in the 0-10 cm layer. 137Cs and 239+240Pu are distributed rather similarly over the 0-10 cm and 10-20 cm layers. At locations with high contents of sand (82-93%) along the South China Sea coast, the downward percolation by rainwater results in a higher accumulation of 239+240Pu and 137Cs in the 10-20 cm layer. The mean 137Cs/ 90Sr inventory ratio is 9.3+/-2.2, and the correlation is weak between these isotopes.     

Fractionation of natural radionuclides in soils from a uranium mineralized area in the south-west of Spain

A new version of a classical method was applied to study the distribution of natural radionuclides (238U, 230Th, and 226Ra) in the soil fractions obtained by a sequential extraction procedure. The potential significance of the fractions obtained with this method was tested on two very similar soils but with very different contents of the three radionuclides, collected in the proximity of a disused uranium mine located in the Extremadura region in the south-west of Spain. The results confirmed that, if only non-residual fractions are considered, the sequential method applied shows a characteristic speciation pattern of these natural radionuclides in this soil matrix, i.e., the distribution of each of the three radionuclides was very similar for the two soil samples.     

Plant induced changes in concentrations of caesium, strontium and uranium in soil solution with reference to major ions and dissolved organic matter

For a better understanding of the soil-to-plant transfer of radionuclides, their behavior in the soil solution should be elucidated, especially at the interface between plant roots and soil particles, where conditions differ greatly from the bulk soil because of plant activity. This study determined the concentration of stable Cs and Sr, and U in the soil solution, under plant growing conditions. The leafy vegetable komatsuna (Brassica rapa L.) was cultivated for 26 days in pots, where the rhizosphere soil was separated from the non-rhizosphere soil by a nylon net screen. The concentrations of Cs and Sr in the rhizosphere soil solution decreased with time, and were controlled by K+NH(4)(+) and Ca, respectively. On the other hand, the concentration of U in the rhizosphere soil solution increased with time, and was related to the changes of DOC; however, this relationship was different between the rhizosphere and non-rhizosphere soil.     

Radiological assessment of surface water quality around proposed uranium mining site in India

The gross alpha and gross beta activities were estimated for radiological assessment of surface water quality around the proposed uranium mining site Kylleng Pyndengsohiong Mawthabah (Domiasiat), West Khasi Hills District, Meghalaya situated in a high rainfall area (12,000 mm) in India. 189 Surface water samples were collected over different seasons of the year from nine different locations covering around 100 km². Gross beta activities were found to vary from 144 to 361 mBq/L which is much below the prescribed WHO limit of 1000 mBq/L for drinking water. Gross alpha activities varied from 61 to 127 mBq/L. These values are much below the reported gross alpha values by other countries. In about 7% of the samples the alpha activities remain exceeded the WHO guideline limit of 100 mBq/L. Surface water samples collected during the summer season of the year show higher activity whereas low activity was found from samples collected during monsoon season. Results show that all water sources are acceptable as drinking water for human consumption from the radiological point of view, the higher gross alpha concentrations in a few locations remains so only for short duration during the summer season.