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.     

Removal of uranium (VI) from aqueous solution by adsorption of hematite

Hematite, a type of inorganic-sorptive medium, was used for the removal of U (VI) from aqueous solutions. Variables of the batch experiments including solution pH, contact time, initial concentration, temperature, calcium and magnesium ions were studied. The results indicated that the adsorption capacities are strongly affected by the solution pH, contact time and initial concentration. A higher pH favors higher U (VI) removal. The adsorption was also affected by temperature and calcium and magnesium ions, but the effect is very weak. The maximum adsorption capacity (q_m) only increased from 3.36 mg g⁻¹ to 3.54 mg g⁻¹ when the temperature was increased from 293 K to 318 K. A two-stage kinetic behavior was observed in the adsorption of uranium (VI): very rapid initial adsorption in a few minutes, followed by a long period of slower uptake. It was found that an increase in temperature resulted in a higher uranium (VI) loading per unit weight of the sorbent. The adsorption of uranium by hematite had good efficiency, and the equilibrium time of adsorbing uranium (VI) was about 6 h. The isothermal data were fitted with both Langmuir and Freundlich equations, but the data fitted the former better than the latter. The pseudo-first-order kinetic model, pseudo-second-order kinetic model and intraparticle diffusion model were used to describe the kinetic data, but the pseudo-second-order kinetic model was the best. The thermodynamic parameter ΔG⁰ were calculated, the negative ΔG⁰ values of uranium (VI) at different temperatures confirmed the adsorption processes were spontaneous.     

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.     

Biosorption of uranium (VI) by immobilized Aspergillus fumigatus beads

Biosorption of uranium (VI) ions by immobilized Aspergillus fumigatus beads was investigated in a batch system. The influences of solution pH, biosorbent dose, U (VI) concentration, and contact time on U (VI) biosorption were studied. The results indicated that the adsorption capacity was strongly affected by the solution pH, the biosorbent dose and initial U (VI) concentration. Optimum biosorption was observed at pH 5.0, biosrobent dose (w/v) 2.5%, initial U (VI) concentration 60 mg L⁻¹. Biosorption equilibrium was established in 120 min. The adsorption process conformed to the Freunlich and Temkin isothermal adsorption models. The dynamic adsorption model conformed to pseudo-second order model.     

Differences in U root-to-shoot translocation between plant species explained by U distribution in roots

Accumulation and distribution of uranium in roots and shoots of four plants species differing in their cation exchange capacity of roots (CECR) was investigated. After exposure in hydroponics for seven days to 100 μmol U L⁻¹, distribution of uranium in roots was investigated through chemical extraction of roots. Higher U concentrations were measured in roots of dicots which showed a higher CECR than monocot species. Chemical extractions indicated that uranium is mostly located in the apoplasm of roots of monocots but that it is predominantly located in the symplasm of roots of dicots. Translocation of U to shoot was not significantly affected by the CECR or distribution of U between symplasm and apoplasm. Distribution of uranium in roots was investigated through chemical extraction of roots for all species. Additionally, longitudinal and radial distribution of U in roots of maize and Indian mustard, respectively showing the lowest and the highest translocation, was studied following X-ray fluorescence (XRF) analysis of specific root sections. Chemical analysis and XRF analysis of roots of maize and Indian mustard clearly indicated a higher longitudinal and radial transport of uranium in roots of Indian mustard than in roots of maize, where uranium mostly accumulated in root tips. These results showed that even if CECR could partly explain U accumulation in roots, other mechanisms like radial and longitudinal transport are implied in the translocation of U to the shoot.     

Removal of uranium(VI) from aqueous solutions and nuclear industry effluents using humic acid-immobilized zirconium-pillared clay

Removal of uranium [U(VI)] from aqueous solutions with humic acid-immobilized zirconium-pillared clay (HA-Zr-PILC) was investigated using a batch adsorption technique. The adsorbent was characterized using XRD, FTIR, SEM, TG/DTG, surface area analyzer and potentiometric titration. The effects of pH, contact time, initial concentration, adsorbent dose, and adsorption isotherm on the removal process were evaluated. A maximum removal of 97.6 ± 2.1 and 94.7 ± 3.3% was observed for an initial concentration of 50 and 100 mg L⁻¹, respectively at pH 6.0 and an adsorbent dose of 2.0 g L⁻¹. Equilibrium was achieved in approximately 180 min. The mechanism for the removal of U(VI) ions by HA-Zr-PILC was based on an ion exchange reaction. The experimental kinetic and isotherm data were analyzed using a second-order kinetic equation and Langmuir isotherm model, respectively. The monolayer adsorption capacity for U(VI) removal was found to be 132.68 ± 5.04 mg g⁻¹. An increase of temperature of the medium caused an increase in metal adsorption. Complete removal (≅100%) of U(VI) from 1.0 L of a simulated nuclear industry effluent sample containing 10.0 mg U(VI) ions was possible with 1.5 g of HA-Zr-PILC. The adsorbent was suitable for repeated use (over 4 cycles) without any noticeable loss of capacity.     

Uranium isotopes in groundwater from the “Jeffara coastal aquifer” (southeastern Tunisia)

The distributions of ²³⁸U and ²³⁴U in groundwater from the “Jeffara aquifer” were studied by using alpha spectrometric methods. The concentration ranges of ²³⁸U and ²³⁴U/²³⁸U activity ratios were 1.34 ± 0.17 to 3.43 ± 0.38 ppb, and 1.43 ± 0.23 to 1.82 ± 0.27 respectively. Variations in concentrations can be related not only to lithostratigraphic formations but also to different origins of groundwater. U content of Jeffara are found very similar to those of Continental Intercalaire aquifer in both El Hamma and Chenchou regions, indicating that the Continental Intercalaire is the dominant source of the groundwater.     

The combined effect of uranium and gamma radiation on biological responses and oxidative stress induced in Arabidopsis thaliana

Uranium never occurs as a single pollutant in the environment, but always in combination with other stressors such as ionizing radiation. As effects induced by multiple contaminants can differ markedly from the effects induced by the individual stressors, this multiple pollution context should not be neglected. In this study, effects on growth, nutrient uptake and oxidative stress induced by the single stressors uranium and gamma radiation are compared with the effects induced by the combination of both stressors. By doing this, we aim to better understand the effects induced by the combined stressors but also to get more insight in stressor-specific response mechanisms. Eighteen-day-old Arabidopsis thaliana seedlings were exposed for 3 days to 10 μM uranium and 3.5 Gy gamma radiation. Gamma radiation interfered with uranium uptake, resulting in decreased uranium concentrations in the roots, but with higher transport to the leaves. This resulted in a better root growth but increased leaf lipid peroxidation. For the other endpoints studied, effects under combined exposure were mostly determined by uranium presence and only limited influenced by gamma presence. Furthermore, an important role is suggested for CAT1/2/3 gene expression under uranium and mixed stressor conditions in the leaves.     

On the influence of faulting on small-scale soil-gas radon variability: a case study in the Iberian Uranium Province

In order to evaluate the influence of faulting on the variability of geogenic radon at detailed scale (1:2000), data on gamma ray fluxes, U and Th concentrations in rocks, radon in soil-gas and radon in groundwater were collected in three target areas on the Oliveira do Hospital region (Central Portugal). This region stands on the Iberian Uranium Province, and is dominantly composed of Hercynian granites and metasedimentary rocks of pre-Ordovician age, crosscut by faults with dominant strike N35°E, N55°E and N75°E. Radiometric anomalies are frequent, associated with faults of the referred systems and metasedimentary enclaves; the analytical data confirms that these anomalies are produced by local high uranium contents in rocks and fault-filling materials (n = 34, range 13-724 ppm), while other radiogenic elements are relatively constant (e.g. Th 4-30 ppm). Radon concentration in soil can be extremely high, up to 12,850 kBq m⁻³ (n = 215), with a large proportion of results above 100 kBq m⁻³. Unsurprisingly, groundwater also shows high radon concentrations, with observed values in the range 150-4850 Bq.L⁻¹ (n = 17). From the results it is concluded that metasedimentary enclaves, as well as faults, can accumulate uranium from circulating fluids, and as a consequence, strongly locally enhance geogenic radon potential. Due to this fact, for the purpose of land use planning in such uranium-enriched regions, very detailed geological mapping is needed to precisely recognize radon high risk areas. A correlation between radon concentration in soil or in groundwater and gamma ray fluxes was established pointing to the possible use of these fluxes as a first step in assessing geogenic radon potential, at least to geological setting similar to the study area.     

A study of radionuclides, metals and stable lead isotope ratios in sediments and soils in the vicinity of natural U-mineralisation areas in the Northern Territory

Australian guidelines recommend that tailings materials from uranium (U) mining and milling be contained without any detrimental impact on the environment for at least 1000 years. Natural analogue sites are being investigated to determine if they can provide data on the rates of natural erosion processes which occur over these timescales, for input into predictive geomorphic computer models. This paper presents radionuclide, metal and stable lead (Pb) isotope data from sediment cores and surface soils in the vicinity of two mineralised areas in the Alligator Rivers Region.Surface scrapes from the natural Anomaly #2, south of the Ranger mineral lease, exhibit radiogenic ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁷Pb ratios, and elevated U and metal concentrations typical for a near surface U anomaly. In contrast, samples taken from the Koongarra mineral lease (KML) show radionuclide activity and metal concentrations similar to natural areas elsewhere in the Alligator Rivers Region and Pb isotope ratios are closer to present day average crustal ratios (PDAC), as the orebodies at KML are covered by surficial sand. A sediment core collected from Anbangbang Billabong, downstream of KML, exhibits small variations in Pb isotope ratios that indicate that approximately 1% of the upper sediments in the sediment core may be derived from material originating from the U anomaly at Koongarra.