Association of plutonium with sediments from the Ob and Yenisey Rivers and Estuaries

The present study applied sequential extraction techniques to investigate the binding and mobility of plutonium (Pu) in sediments from the rivers and estuaries of the Ob and Yenisey. As a study site, the Ob and Yenisey are particularly interesting as both rivers have weapons-grade Pu sources in their catchment areas, including the Russian Pu production and reprocessing plants at Mayak, Tomsk-7 and Krashnoyarsk, and the Semipalantinsk nuclear weapons testing site in Kazakhstan. Plutonium activity and ²⁴⁰Pu/²³⁹Pu ratios were determined using accelerator mass spectrometry (AMS). Sequential extractions showed that between 47 and 80% of the Pu in Yenisey River sediments and 35–53% of the Pu in soils around the Techa River are mobilized with weak oxidising agents, which can indicate that Pu is bound to organic material. In contrast, Pu in Ob and Yenisey Estuarine sediments was more strongly bound, with 60–100% being found in the HNO₃-extractable fraction. This change in speciation could reflect either that Pu bound to organic material in the Techa and Yenisey River sediments becomes more fixed to the sediments with time, or that organic-bound Pu is mobilized and released to the water when the sediments encounter the more saline water of the Ob and Yenisey estuaries. In general, ²⁴⁰Pu/²³⁹Pu ratios were relatively consistent between different extraction fractions, although, in whole sediments, an increase in ratio was observed with distance from the source. This reflects the increased influence of weapon fallout from catchment runoff within the river systems, as compared to the weapons-grade sources close to the production and reprocessing plants. Knowledge of Pu speciation in the Ob and Yenisey Rivers, and the processes controlling its behaviour in estuarine systems, can improve predictions of its transfer and subsequent environmental impact to Arctic Seas.     

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

A combination of synchrotron radiation based X-ray microscopic techniques (μ-XRF, μ-XANES, μ-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 (UO₃·2.25H₂O), dehydrated schoepite (UO₃·0.75H₂O) and metaschoepite (UO₃·2.0H₂O) 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 UO₂, 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.     

Use of AMS in the marine environment

In recent years, the field of AMS has expanded into many areas of science. This paper reviews a variety of applications of AMS in the marine environment, focusing particularly on recent developments and applications. Following a brief summary of the three main isotope techniques used in environmental studies: dating, tracing and source identification, a number of applications are considered. Traditional (14)C-dating is no longer the dominant application of AMS measurements, and together with measurements of (10)Be, (26)Al and (36)Cl, much of the research is now directed towards an understanding of global climate change via studies of oceanic circulation, atmospheric processes and past climates by cosmic ray exposure dating. Profiles of long-lived cosmogenic radionuclides in sediments and ice cores, as a function of depth and, thus, age, provide key information on past solar variability, production rate changes and atmospheric transport and deposition mechanisms. Useful paleoclimatic information may be derived from these archives both because deposition is influenced by climate and because solar activity (which influences production) and solar radiance (which influences climate) are correlated. In recent years, emphasis has been put on the development and application of AMS techniques for the measurement of heavier long-lived isotopes, including (99)Tc, (129)I, (236)U and other actinide isotopes. AMS combines ultra low detection limits and the possibility to analyse isotope ratios that can be difficult with traditional instruments and has been used in a number of applications on the consequences and uses of releases from nuclear energy. Finally, the use AMS in environmental sciences is expected to expand further in the foreseeable future with long-lived cosmogenic radionuclides contributing to a large body of knowledge on processes involving atmosphere, oceans, ice sheets, biosphere, soils and sediments.     

Outdoor 220Rn, 222Rn and terrestrial gamma radiation levels: investigation study in the thorium rich Fen Complex, Norway

The present study was done in the Fen Complex, a Norwegian area rich in naturally occurring radionuclides, especially in thorium ((232)Th). Measurement of radioactivity levels was conducted at the decommissioned iron (Fe) and niobium (Nb) mining sites (TENORM) as well as at the undisturbed wooded sites (NORM), all open for free public access. The soil activity concentrations of (232)Th (3280-8395 Bq kg(-1)) were significantly higher than the world and the Norwegian average values and exceeded the Norwegian screening level (1000 Bq kg(-1)) for radioactive waste, while radium ((226)Ra) was present at slightly elevated levels (89-171 Bq kg(-1)). Terrestrial gamma dose rates were also elevated, ranging 2.6-4.4 μGy h(-1). Based on long-term surveys, the air concentrations of thoron ((220)Rn) and radon ((222)Rn) reached 1786 and 82 Bq m(-3), respectively. Seasonal variation in the outdoor gamma dose rates and Rn concentrations was confirmed. Correlation analyses showed a linear relationship between air radiation levels and the abundance of (232)Th in soil. The annual outdoor effective radiation doses for humans (occupancy 5 h day(-1)) were estimated to be in the range of 3.0-7.7 mSv, comparable or higher than the total average (summarized indoor and outdoor) exposure dose for the Norwegian population (2.9 mSv year(-1)). On the basis of all obtained results, this Norwegian area should be considered as enhanced natural radiation area (ENRA).     

Radionuclide speciation and its relevance in environmental impact assessments

To assess the long-term environmental impact of radioactive contamination of ecosystems, information on source terms including radionuclide speciation, mobility and biological uptake is needed. A major fraction of refractory radionuclides released from nuclear sources such as nuclear weapons tests and reactor accidents is present as radioactive particles, whilst radionuclides are also present as colloids or low molecular mass species in effluents from nuclear installations. Low molecular mass species are more mobile (lower apparent K(d)) and bioavailable (higher apparent BCF) than colloids and particles. Soils and sediments act as sinks for particles and colloids. Due to particle weathering, associated radionuclides can be remobilised over time. Thus, information on particle characteristics such as composition, particle size, crystalline structures and oxidation states influencing weathering rates and subsequent mobilisation is essential. The present article summarises current knowledge on radioactive particles released from different sources, and the relevance of radionuclide speciation for mobility and biological uptake.     

Determination of technetium-99 using electrothermal vaporization inductively coupled plasma-mass spectrometry (ETV-ICP-MS) and NH4OH as chemical modifier

In recent years, developments in ICP-MS have led to improved methods for determination of long-lived radionuclides. This paper reports the use of NH(4)OH as a matrix modifier and ETV sample introduction for the determination of technetium-99 ((99)Tc) in a variety of environmental and biological samples, using Re as carrier and (99m)Tc as yield monitor in the chemical separation method. Addition of an excess of NH(4)OH led to a stable (99)Tc signal, reduced memory effect, better reproducibility and reduced detection limits. Following radiochemical separation of (99)Tc from the sample matrix, detection limits in the order of a few microBq have been achieved. ETV has also proved applicable for rapid, direct analysis of a number of environmental samples having relatively high concentrations of (99)Tc (sediment extracts and river water close to nuclear installations). However, in this case, control of matrix effects (signal reduction and enhancement) using standard additions is necessary.     

Assessment of radionuclide and metal contamination in a thorium rich area in Norway

The Fen Central Complex in southern Norway, a geologically well investigated area of magmatic carbonatite rocks, is assumed to be among the world largest natural reservoirs of thorium ((232)Th). These rocks, also rich in iron (Fe), niobium (Nb), uranium ((238)U) and rare earth elements (REE), were mined in several past centuries. Waste locations, giving rise to enhanced levels of both radionuclides and metals, are now situated in the area. Estimation of radionuclide and metal contamination of the environment and radiological risk assessment were done in this study. The average outdoor gamma dose rate measured in Fen, 2.71 μGy h(-1), was significantly higher than the world average dose rate of 0.059 μGy h(-1). The annual exposure dose from terrestrial gamma radiation, related to outdoor occupancy, was in the range 0.18-9.82 mSv. The total activity concentrations of (232)Th and (238)U in soil ranged from 69 to 6581 and from 49 to 130 Bq kg(-1), respectively. Enhanced concentrations were also identified for metals, arsenic (As), lead (Pb), chromium (Cr) and zinc (Zn), in the vicinity of former mining sites. Both radionuclide and heavy metal concentrations suggested leaching, mobilization and distribution from rocks into the soil. Correlation analysis indicated different origins for (232)Th and (238)U, but same or similar for (232)Th and metals As, Cr, Zn, nickel (Ni) and cadmium (Cd). The results from in situ size fractionation of water demonstrated radionuclides predominately present as colloids and low molecular mass (LMM) species, being potentially mobile and available for uptake in aquatic organisms of Norsj? Lake. Transfer factors, calculated for different plant species, showed the highest radionuclide accumulation in mosses and lichens. Uptake in trees was, as expected, lower. Relationship analysis of (232)Th and (238)U concentrations in moss and soil samples showed a significant positive linear correlation.