Oxidation states of uranium in depleted uranium particles from Kuwait

The oxidation states of uranium in depleted uranium (DU) particles were determined by synchrotron radiation based mu-XANES, applied to individual particles isolated from selected samples collected at different sites in Kuwait. Based on scanning electron microscopy with X-ray microanalysis prior to mu-XANES, DU particles ranging from submicrons to several hundred micrometers were observed. The median particle size depended on sources and sampling sites; small-sized particles (median 13 microm) were identified in swipes taken from the inside of DU penetrators holes in tanks and in sandy soil collected below DU penetrators, while larger particles (median 44 microm) were associated with fire in a DU ammunition storage facility. Furthermore, the (236)U/(235)U ratios obtained from accelerator mass spectrometry demonstrated that uranium in the DU particles originated from reprocessed fuel (about 10(-2) in DU from the ammunition facility, about 10(-3) for DU in swipes). Compared to well-defined standards, all investigated DU particles were oxidized. Uranium particles collected from swipes were characterized as UO(2), U(3)O(8) or a mixture of these oxidized forms, similar to that observed in DU affected areas in Kosovo. Uranium particles formed during fire in the DU ammunition facility were, however, present as oxidation state +5 and +6, with XANES spectra similar to solid uranyl standards. Environmental or health impact assessments for areas affected by DU munitions should therefore take into account the presence of respiratory UO(2), U(3)O(8) and even UO(3) particles, their corresponding weathering rates and the subsequent mobilisation of U from oxidized DU particles.     

Bioaccumulation and biological effects in the earthworm Eisenia fetida exposed to natural and depleted uranium

The accumulations of both natural (U) and depleted (DU) uranium in the earthworms (Eisenia fetida) were studied to evaluate corresponding biological effects. Concentrations of metals in the experimental soil ranged from 1.86 to 600 mg kg⁻¹. Five biological endpoints: mortality, animals’ weight increasing, lysosomal membrane stability by measuring the neutral red retention time (the NRRT), histological changes and genetic effects (Comet assay) were used to evaluate biological effects in the earthworms after 7 and 28 days of exposure. No effects have been observed in terms of mortality or weight reduction. Cytotoxic and genetic effects were identified at quite low U concentrations. For some of these endpoints, in particular for genetic effects, the dose (U concentration)-effect relationships have been found to be non-linear. The results have also shown a statistically significant higher level of impact on the earthworms exposed to natural U compared to depleted U.     

Production of radioactive particles for use in environmental studies

This paper presents an aerosol generation technique developed to produce dry aerosol particles of various sizes from aqueous solutions of salt. The technique was tested with sodium chloride, lithium carbonate and uranyl acetate at various aqueous concentrations which produced particles in the size range of 0.13-1.37 microm Mass Median Diameter (MMD). The generated aerosols were acceptably monodisperse with a geometric standard deviation of 1.4-2. Both MMD and Mass Median Aerodynamic Diameter (MMAD) increased significantly (p<0.001) with increased concentration of the salt in solution. The technique can also be used to generate aerosols of different chemical species. The results obtained indicate that the system is convenient for use with various aerosol-forming materials, with a stable particle size distribution being maintained for a long period of steady operation. The technique was successfully applied in wind tunnel studies to simulate the release of submicron radioactive particles and their interception by crops, grass and tree canopies. The relevance and application of the technique in other areas of environmental assessment studies is discussed.     

Oxidation states of uranium in DU particles from Kosovo

The oxidation states of uranium contained in depleted uranium (DU) particles were determined by synchrotron radiation based micro-XANES, applied to individual particles in soil samples collected at Ceja Mountain, Kosovo. Based on scanning electron microscopy (SEM) with XRMA prior to micro-XANES, DU particles ranging from submicrons to about 30 microm (average size: 2 microm or less) were identified. Compared to well-defined standards, all investigated DU particles were oxidized. About 50% of the DU particles were characterized as UO2, the remaining DU particles present were U3O8 or a mixture of oxidized forms (ca. 2/3 UO2, 1/3 U3O8). Since the particle weathering rate is expected to be higher for U3O8 than for UO2, the presence of respiratory U3O8 and UO2 particles, their corresponding weathering rates and subsequent remobilisation of U from DU particles should be included in the environmental or health impact assessments.     

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.     

Fuel particles in the Chernobyl cooling pond: current state and prediction for remediation options

During the coming years, a management and remediation strategy for the Chernobyl cooling pond (CP) will be implemented. Remediation options include a controlled reduction in surface water level of the cooling pond and stabilisation of exposed sediments. In terrestrial soils, fuel particles deposited during the Chernobyl accident have now almost completely disintegrated. However, in the CP sediments the majority of ⁹⁰Sr activity is still in the form of fuel particles. Due to the low dissolved oxygen concentration and high pH, dissolution of fuel particles in the CP sediments is significantly slower than in soils. After the planned cessation of water pumping from the Pripyat River to the Pond, significant areas of sediments will be drained and exposed to the air. This will significantly enhance the dissolution rate and, correspondingly, the mobility and bioavailability of radionuclides will increase with time. The rate of acidification of exposed bottom sediments was predicted on the basis of acidification of similar soils after liming. Using empirical equations relating the fuel particle dissolution rate to soil and sediment pH allowed prediction of fuel particle dissolution and ⁹⁰Sr mobilisation for different remediation scenarios. It is shown that in exposed sediments, fuel particles will be almost completely dissolved in 15–25 years, while in parts of the cooling pond which remain flooded, fuel particle dissolution will take about a century.     

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.     

Distribution of PBDEs in air particles from an electronic waste recycling site compared with Guangzhou and Hong Kong, South China

Air samples of total suspended particles (TSP, particles less than 30-60 microm), and particles with aerodynamic diameter smaller than 2.5 microm (PM(2.5)) were collected simultaneously at Guiyu (an electronic waste recycling site), three urban sites in Hong Kong and two urban sites in Guangzhou, South China from 16 August to 17 September 2004. Twenty-two PBDE congeners (BDE-3, -7, -15, -17, -28, -49, -71, -47, -66, -77, -100, -119, -99, -85, -126, -154, -153, -138, -156, -184, -183, -191) in TSP and PM(2.5) were measured. The results showed that the overall average concentrations of TSP and PM(2.5) collected at Guiyu were 124 and 62.1 microg m(-3), respectively. The monthly concentrations of the sum of 22 BDE congeners contained in TSP and PM(2.5) at Guiyu were 21.5 and 16.6 ng m(-3), with 74.5 and 84.3%, contributed by nine congeners (BDE-28, -47, -66, -100, -99, -154, -153, -183 and -191 respectively). This pattern was similar to Tsuen Wan site of Hong Kong. Two urban sites of Guangzhou had the same congener pattern, but were different from Yuen Long and Hok Tsui sites of Hong Kong. The results also showed that the amount of mono to penta brominated congeners, which are more toxic, accounted for 79.4-95.6% of Sigma(22)PBDEs from all sites. All congeners tested in Guiyu were up to 58-691 times higher than the other urban sites and more than 100 times higher than other studies reported elsewhere. The higher concentration in the air was due to heating or opening burning of electronic waste since PBDEs are formed when plastics containing brominated flame retardants are heated.     

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.     

Improved performance of a biomaterial-based cation exchanger for the adsorption of uranium(VI) from water and nuclear industry wastewater

The amine-modified polyhydroxyethylmethacrylate (poly(HEMA))-grafted biomaterial (tamarind fruit shell, TFS) carrying carboxyl functional groups at the chain end (PGTFS-COOH) was prepared and used as an adsorbent for the removal of uranium(VI) from water and nuclear industry wastewater. FTIR spectral analysis revealed that U(VI) ions and PGTFS-COOH formed a chelate complex. The adsorption process was relatively fast, requiring only 120 min to attain equilibrium. The adsorption kinetic data were best described by the pseudo-second-order equation. The equilibrium adsorption data were correlated with the Sips isotherm model. The maximum U(VI) ions uptake with PGTFS-COOH was estimated to be 100.79 mg/g. The complete removal of 10 mg/L U(VI) from simulated nuclear industry wastewater was achieved by 3.5 g/L PGTFS-COOH. The reusability of the adsorbent was demonstrated over 4 cycles using NaCl (1.0 M) + HCl (0.5 M) solution mixture to de-extract the U(VI). The results show that the PGTFS-COOH tested is very promising for the recovery of U(VI) from water and wastewater.     

An approach to comparative assessments of potential health risks from exposure to radionuclides and hazardous chemicals

The need to compare potential health risks to the public associated with different activities that can result in releases of hazardous substances to the environment is becoming increasingly important in decision-making. In making such comparisons, it is desirable to use equivalent indicators of potential health risks for radionuclides, chemical carcinogens, and noncarcinogenic hazardous chemicals. Current approaches to risk assessment that were developed for purposes of protecting human health do not provide equivalent indicators of potential risks from exposure to radionuclides and hazardous chemicals. Comparisons of environmental concentrations or calculated exposures or risks with standards for protection of public health also do not provide equivalent indicators of potential risks. We propose a simple approach to comparative risk assessments in which calculated exposures to any hazardous substances are expressed relative to no-observed-effect levels (NOELs) or, preferably, lower confidence limits of benchmark doses (BMDLs) in humans. This approach provides an equivalent, science-based indicator of the relative risks posed by different exposures to any hazardous substances.