Chronology of Pu isotopes and 236U in an Arctic ice core.

In the present work, state of the art isotopic fingerprinting techniques are applied to an Arctic ice core in order to quantify deposition of U and Pu, and to identify possible tropospheric transport of debris from former Soviet Union test sites Semipalatinsk (Central Asia) and Novaya Zemlya (Arctic Ocean). An ice core chronology of (236)U, (239)Pu, and (240)Pu concentrations, and atom ratios, measured by accelerator mass spectrometry in a 28.6m deep ice core from the Austfonna glacier at Nordaustlandet, Svalbard is presented. The ice core chronology corresponds to the period 1949 to 1999. The main sources of Pu and (236)U contamination in the Arctic were the atmospheric nuclear detonations in the period 1945 to 1980, as global fallout, and tropospheric fallout from the former Soviet Union test sites Novaya Zemlya and Semipalatinsk. Activity concentrations of (239+240)Pu ranged from 0.008 to 0.254 mBq cm(-2) and (236)U from 0.0039 to 0.053 µBq cm(-2). Concentrations varied in concordance with (137)Cs concentrations in the same ice core. In contrast to previous published results, the concentrations of Pu and (236)U were found to be higher at depths corresponding to the pre-moratorium period (1949 to 1959) than to the post-moratorium period (1961 and 1962). The (240)Pu/(239)Pu ratio ranged from 0.15 to 0.19, and (236)U/(239)Pu ranged from 0.18 to 1.4. The Pu atom ratios ranged within the limits of global fallout in the most intensive period of nuclear atmospheric testing (1952 to 1962). To the best knowledge of the authors the present work is the first publication on biogeochemical cycles with respect to (236)U concentrations and (236)U/(239)Pu atom ratios in the Arctic and in ice cores.

Micro-analytical characterisation of radioactive heterogeneities in samples from Central Asian TENORM sites.

The present work focuses on the use of micro-analytical techniques to demonstrate the heterogeneous distribution of radionuclides and metals in soils collected at Former Soviet Union mining sites in Central Asia. Based on digital autoradiography, radionuclides were heterogeneously distributed in soil samples collected at the abandoned uranium mining sites Kurday, Kazakhstan, Kadji Sai, Kyrgyzstan and Taboshar, Tajikistan. Using electron microscopy interfaced with X-ray microanalysis submicron - mm-sized radioactive particles and rock fragments with U, As, Se and toxic metals on the surfaces were identified in Kurday and Kadji Sai samples. Employing scanning and tomographic (3D) synchrotron radiation based micro-X-ray fluorescence (µ-SRXRF) and synchrotron radiation based micro-X-ray diffraction (µ-SRXRD) allowed us to observe the inner structure of the particles without physical sectioning. The distribution of elements in virtual crosssections demonstrated that U and a series of toxic elements were rather heterogeneously distributed also within individual radioactive TENORM particles. Compared to archived data, U in Kadji Sai particles was present as uraninite (U4O9+y or UO2+x) or Na-zippeite ((Na4(UO2)6[(OH)10(SO4)3]·4H2O), i.e. U minerals with very low solubility. The results suggested that TENORM particles can carry substantial amount of radioactivity, which can be subject to re-suspension, atmospheric transport and water transport. Thus, the potential radioecological and radioanalytical impact of radioactive particles at NORM and TENORM sites worldwide should be taken into account. The present work also demonstrates that radioecological studies should benefit from the use of advanced methods such as synchrotron radiation based techniques.

Environmental impact assessment of radionuclide and metal contamination at the former U site at Kadji Sai, Kyrgyzstan.

During 1949-1967, a U mine, a coal-fired thermal power plant and a processing plant for the extraction of U from the produced ash were operated at the Kadji Sai U mining site in Tonsk district, Issyk-Kul County, Kyrgyzstan. The Kadji Sai U legacy site represents a source of contamination of the local environment by naturally occurring radionuclides and associated trace elements. To assess the environmental impact of radionuclides and trace metals at the site, field expeditions were performed in 2007 and 2008 by the Joint collaboration between Norway, Kazakhstan, Kyrgyzstan, Tajikistan (JNKKT) project and the NATO SfP RESCA project. In addition to in situ gamma and Rn dose rate measurements, sampling included at site fractionation of water and sampling of water, fish, sediment, soils and vegetation. The concentrations of radionuclides and trace metals in water from Issyk-Kul Lake were in general low, but surprisingly high for As. Uptake of U and As was also observed in fish from the lake with maximum bioconcentration factors for liver of 1.6 and 75, respectively. The concentrations of U in water within the Kadji Sai area varied from 0.01 to 0.05 mg/L, except for downstream from the mining area where U reached a factor of 10 higher, 0.2 mg/L. Uranium concentrations in the drinking water of Kadji Sai village were about the level recommended by the WHO for drinking water. The (234)U/(238)U activity ratio reflected equilibrium conditions in the mining pond, but far from equilibrium outside this area (reaching 2.3 for an artesian well). Uranium, As and Ni were mainly present as low molecular mass (LMM, less than 10 kDa) species in all samples, indicating that these elemental species are mobile and potentially bioavailable. The soils from the mining sites were enriched in U, As and trace metals. Hot spots with elevated radioactivity levels were easily detected in Kadji Sai and radioactive particles were observed. The presence of particles carrying significant amount of radioactivity and toxic trace elements may represent a hazard during strong wind events (wind erosion). Based on sequential extractions, most of the elements were strongly associated with mineral matter, except for U and As having a relatively high remobilization potential. Low Kd was obtained for U (3.5 × 10(2) L/kg d.w.), intermediate Kds (~3 × 10(3) L/kg d.w.) were obtained for (226)Ra, As and Ni, while a high Kd (2.2 × 10(5) L/kg d.w.) were obtained for Pb. The accumulation of metals in fish gills reflected the LMM species in the Issyk-Kul water, and did not show any bioaccumulation. The muscle Hg concentrations in all fish species were low and did not represent any health risk even for groups at risk. Total gamma and Rn dose rate to man amounted to about 12 mSv/y, while the highest calculated dose rate for non-human species based on the ERICA Assessment Tool were obtained in terrestrial plants (164 µGy/h) due to the Ra exposure. The results obtained showed that radiation doses to resident public at all of the investigated sites in the Kadji Sai area were in general relatively low. Low radiological risk and no detrimental health impact on resident public can be expected at these sites. However, exposure to Rn and Tn in the living environment can be further reduced by implementing simple countermeasures such as ventilation of dwelling cellars. More focus in the Kadji Sai area should probably be put on trace elements, especially the As uptake in fish in Lake Issyk-Kul.

Solid state speciation and potential bioavailability of depleted uranium particles from Kosovo and Kuwait.

A combination of synchrotron radiation based X-ray microscopic techniques (mu-XRF, mu-XANES, mu-XRD) applied on single depleted uranium (DU) particles and semi-bulk leaching experiments has been employed to link the potential bioavailability of DU particles to site-specific particle characteristics. The oxidation states and crystallographic forms of U in DU particles have been determined for individual particles isolated from selected samples collected at different sites in Kosovo and Kuwait that were contaminated by DU ammunition during the 1999 Balkan conflict and the 1991 Gulf war. Furthermore, small soil or sand samples heavily contaminated with DU particles were subjected to simulated gastrointestinal fluid (0.16 M HCl) extractions. Characteristics of DU particles in Kosovo soils collected in 2000 and in Kuwait soils collected in 2002 varied significantly depending on the release scenario and to some extent on weathering conditions. Oxidized U (+6) was determined in large, fragile and bright yellow DU particles released during fire at a DU ammunition storage facility and crystalline phases such as schoepite (UO(3).2.25H(2)O), dehydrated schoepite (UO(3).0.75H(2)O) and metaschoepite (UO(3).2.0H(2)O) were identified. As expected, these DU particles were rapidly dissolved in 0.16 M HCl (84 +/- 3% extracted after 2 h) indicating a high degree of potential mobility and bioavailability. In contrast, the 2 h extraction of samples contaminated with DU particles originating either from corrosion of unspent DU penetrators or from impacted DU ammunition appeared to be much slower (20-30%) as uranium was less oxidized (+4 to +6). Crystalline phases such as UO(2), UC and metallic U or U-Ti alloy were determined in impacted DU particles from Kosovo and Kuwait, while the UO(2,34) phase, only determined in particles from Kosovo, could reflect a more corrosive environment. Although the results are based on a limited number of DU particles, they indicate that the structure and extractability of DU particles released from similar sources (metallic U penetrators) will depend on the release scenarios (fire, impact) and to some extent environmental conditions. However, most of the DU particles (73-96%) in all investigated samples were dissolved in 0.16 M HCl after one week indicating that a majority of the DU material is bioaccessible.

Characterization of U/Pu particles originating from the nuclear weapon accidents at Palomares, Spain, 1966 and Thule, Greenland, 1968.

Following the USAF B-52 bomber accidents at Palomares, Spain in 1966 and at Thule, Greenland in 1968, radioactive particles containing uranium (U) and plutonium (Pu) were dispersed into the environment. To improve long-term environmental impact assessments for the contaminated ecosystems, particles from the two sites have been isolated and characterized with respect to properties influencing particle weathering rates. Low (239)Pu/(235)U (0.62-0.78) and (240)Pu/(239)Pu (0.055-0.061) atom ratios in individual particles from both sites obtained by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) show that the particles contain highly enriched U and weapon-grade Pu. Furthermore, results from electron microscopy with Energy Dispersive X-ray analysis (EDX) and synchrotron radiation (SR) based micrometer-scale X-ray fluorescence (micro-XRF) 2D mapping demonstrated that U and Pu coexist throughout the 1-50 microm sized particles, while surface heterogeneities were observed in EDX line scans. SR-based micrometer-scale X-ray Absorption Near Edge Structure Spectroscopy (micro-XANES) showed that the particles consisted of an oxide mixture of U (predominately UO(2) with the presence of U(3)O(8)) and Pu ((III)/(IV), (IV)/(V) or (III), (IV) and (V)). Neither metallic U or Pu nor uranyl or Pu(VI) could be observed. Characteristics such as elemental distributions, morphology and oxidation states are remarkably similar for the Palomares and Thule particles, reflecting that they originate from similar source and release scenarios. Thus, these particle characteristics are more dependent on the original material from which the particles are derived (source) and the formation of particles (release scenario) than the environmental conditions to which the particles have been exposed since the late 1960s.

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.

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.

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.