Speciation of radionuclides - analytical challenges within environmental impact and risk assessments

The mobility, biological uptake and accumulation of radionuclides are essentially dependent on the physico-chemical form of the nuclides. As a major fraction of refractory radionuclides released during historical nuclear events is associated with particles, a key analytical challenge within environmental impact and risk assessments is to characterise radioactive particles with respect to properties influencing particle weathering, remobilisation and the subsequent ecosystem transfer of associated radionuclides. Preanalysis techniques are needed to fractionate, identify and localize individual particles in contaminated samples. To obtain information on particle characteristics such as particle size distributions, structures, elemental and radionuclide particle composition as well as oxidation state of matrix elements, solid-state speciation techniques are needed. Electron microscopy as well as X-ray microscopic techniques utilising synchrotron X-ray radiation have proved most useful in providing such information. The present paper summarises the present status on advanced techniques and presents historical sources that have contributed to radioactive particle contamination.     

Fractionation of radionuclide species in the environment

Naturally occurring and artificially produced radionuclides in the environment may be present in different physico-chemical forms (i.e., radionuclide species) varying in size (nominal molecular mass), charge properties and valence, oxidation state, structure and morphology, density, degree of complexation, etc. Low molecular mass (LMM) species are believed to be mobile and potentially bioavailable, while high molecular mass (HMM) species such as colloids, polymers, pseudocolloids and particles are considered inert. Due to time-dependent transformation processes such as mobilisation of radionuclide species from solid phases or interactions of mobile and reactive radionuclide species with components in soils and sediments, the original distribution of radionuclides deposited in ecosystems will change over time. To assess the environmental impact from radionuclide contamination, information on radionuclide species deposited, interactions within affected ecosystems and the time-dependent distribution of radionuclide species influencing mobility and biological uptake is essential. The development of speciation techniques to characterize radionuclide species in waters, soils and sediments should therefore be essential for improving the prediction power of impact and risk assessment models. The present paper reviews available fractionation techniques which can be utilised for radionuclide speciation purposes.     

Probabilistic biokinetic modelling of radiocaesium uptake in Arctic seal species: verification of modelled data with empirical observations

The necessity to provide information about radionuclide concentrations in Arctic marine species has been heightened in recent years due to a number of accidents in Arctic regions involving nuclear vessels and the presence of a large number of potential radioactive contamination sources. The provision for such information is largely dependent on the use of radionuclide uptake and transfer models. The uptake of radionuclides in Arctic seal species in this study has been modelled using a probabilistic biokinetic approach. In this paper, model results are compared with empirical data from relevant samples taken within the Arctic region. Results indicate that the model performs well when estimating concentrations of (137)Cs in two seal species for both median values and reproduction of the distribution of data values, but not as well for a third seal species. Likely factors affecting the results are the probability density functions used for the input parameters.     

Challenges in radioecology

Today, radioecology covers a broad scientific field; from the source to long term environmental impact from ionizing radiation. To summarize key challenges within radioecology, the present paper focuses upon knowledge gaps related to processes, mechanisms and variables contributing most to the overall uncertainties in environmental impact assessments. A series of sources related to the nuclear weapon cycle and the civil nuclear cycle has contributed, is still contributing or can potentially contribute to release of radionuclides to the environment in the future. The speciation of most radionuclides depends on the source and release conditions, and will influence ecosystem transport, biological uptake, doses and effects in flora and fauna. Radionuclides may also co-occur in contaminant mixtures (e.g., metals, organics), which potentially could lead to synergisms or antagonisms. Thus, challenges associated with the links between the source or release term – radionuclide speciation – ecosystem transfer – exposure – response relationships are highlighted.     

Sources of anthropogenic radionuclides in the environment: a review

Studies of radionuclides in the environment have entered a new era with the renaissance of nuclear energy and associated fuel reprocessing, geological disposal of high-level nuclear wastes, and concerns about national security with respect to nuclear non-proliferation. This work presents an overview on sources of anthropogenic radionuclides in the environment, as well as a brief discussion of salient geochemical behavior of important radionuclides. We first discuss the following major anthropogenic sources and current developments that have lead, or could potentially contribute, to the radionuclide contamination of the environment: (1) nuclear weapons program; (2) nuclear weapons testing; (3) nuclear power plants; (4) uranium mining and milling; (5) commercial fuel reprocessing; (6) geological repository of high-level nuclear wastes that include radionuclides might be released in the future, and (7) nuclear accidents. Then, we briefly summarize the inventory of radionuclides ⁹⁹Tc and ¹²⁹I, as well as geochemical behavior for radionuclides ⁹⁹Tc, ¹²⁹I, and ²³⁷Np, because of their complex geochemical behavior, long half-lives, and presumably high mobility in the environment; biogeochemical cycling and environment risk assessment must take into account speciation of these redox-sensitive radionuclides.     

Occurrence and behaviour of radionuclides in the Moselle River—Part III: Dispersion of radionuclides along the river course

Knowledge about propagation of radionuclides from nuclear power plants (NPPs) along the course of a river is of great interest in radioecological assessments. By use of a model previously applied in the cases of the Rhine and Weser Rivers, the distribution of various radionuclides released into the Moselle from the NPP Cattenom at normal operation is described with ⁵⁸Co, ⁶⁰Co and ^110mAg as tracers. A comparison of field measurements with calculated values revealed that the radionuclide concentrations in suspended matter and nuclide loads calculated from emission rates agreed with the measured data by a factor of less than two on average.Radionuclide concentrations and loads along the river course decrease mainly due to deposition of particulate radioactive matter in high-sedimentation areas and due to dilution with uncontaminated material from tributaries and other sources. The rate constants of both processes were evaluated, and the mean range of suspended radioactive particles in the Moselle was estimated. Moreover, this study showed anew that suspended matter has to be considered as the main carrier by which the radionuclides from NPPs may be transported over long distances.     

Assessing field-scale migration of radionuclides at the Nevada Test Site: "mobile" species

Many long-lived radionuclides are present in groundwater at the Nevada Test Site (NTS) as a result of 828 underground nuclear weapons tests conducted between 1951 and 1992. In conjunction with a comprehensive geochemical review of radionuclides ((3)H, (14)C, (36)Cl, (99)Tc and (129)I) that are presumably mobile in the subsurface, we synthesized a body of radionuclide activity data measured from groundwater samples collected at 18 monitoring wells, to qualitatively assess their migration at the NTS over distances of hundreds of meters and over timescales of decades. Tritium and (36)Cl showed little evidence of retardation, while the transport of (14)C may have been retarded by its isotopic exchange with carbonate minerals in the aquifer. Observed local reducing conditions (either natural or test-induced) will impact the mobility of certain redox-sensitive radionuclides (especially (99)Tc) that were otherwise soluble and readily transported under oxidizing conditions. Conversely, strongly oxidizing conditions may impact the mobility of (129)I which is mobile under reducing conditions. The effect of iodine speciation on its transport deserves further attention. Indication of delayed transport of some "mobile" radionuclides (especially (99)Tc) in the groundwater at the NTS suggested the importance of redox conditions of the natural system in controlling the fate and transport of radionuclides, which has implications in the enhanced performance of the potential Yucca Mountain repository, located adjacent to the NTS, to store high-level nuclear wastes as well as management of radionuclide contamination in legacy nuclear operations facilities.     

Radioactive impact in sediments from an estuarine system affected by industrial wastes releases

A big fertilizer industrial complex and a vast extension of phosphogypsum piles (12 km2), sited in the estuary formed by the Odiel and Tinto river mouths (southwest of Spain), are producing an unambiguous radioactive impact in their surrounding aquatic environment through radionuclides from the U-series. The levels and distribution of radionuclides in sediments from this estuarine system have been determined. The analyses of radionuclide concentrations and activity ratios have provided us with an interesting information to evaluate the extension, degree and routes of the radioactive impact, as well as for the knowledge of the different pathways followed for the radioactive contamination to disturb this natural system. The obtained results indicate that the main pathway of radioactive contamination of the estuary is through the dissolution in its waters of the radionuclides released by the industrial activities and their later fixation on the particulate materials. Tidal activity also plays an important role in the transport and homogenization along the estuary of the radioactivity released from the fertilizer plants.     

Transfer of radioactivity to fruit: significant radionuclides and speciation

One of the roles of the BIOMASS Theme 3 Fruit Working Group was to identify significant radionuclides to support its work programme. This paper provides a short review of radionuclide emissions to atmosphere together with comments on their relative dosimetric impacts to identify those radionuclides most relevant to the Fruit Working Group. Speciation of the identified radionuclides is also discussed to identify the most likely chemical forms to which fruits might be exposed. It is noted that no information currently exists on radionuclide speciation in regard to the uptake and retention of radionuclides in fruit crops.     

Classification of hot particles from the Chernobyl accident and nuclear weapons detonations by non-destructive methods.

Both after the Chernobyl accident and nuclear weapon detonations, agglomerates of radioactive material, so-called hot particles, were released or formed which show a behaviour in the environment quite different from the activity released in gaseous or aerosol form. The differences in their characteristic properties, in the radionuclide composition and the uranium and actinide contents are described in detail for these particles. While nuclear bomb hot particles (both from fission and fusion bombs) incorporate well detectable trace amounts of 60Co and 152Eu, these radionuclides are absent in Chernobyl hot particles. In contrast, Chernobyl hot particles contain 125Sb and 144Ce which are absent in atomic bomb HPs. Obvious differences are also observable between fusion and fission bombs' hot particles (significant differences in 152Eu/l55Eu, 154Eu/155Eu and 238Pu/239Pu ratios) which facilitate the identification of HPs of unknown provensence. The ratio of 239Pu/240Pu in Chernobyl hot particles could be determined by a non-destructive method at 1:1.5. A non-destructive method to determine the content of non-radioactive elements by Kalpha-emission measurements was developed by which inactive Zr, Nb, Fe and Ni could be verified in the particles.     

Transport and fate of radionuclides in aquatic environments--the use of ecosystem modelling for exposure assessments of nuclear facilities

In safety assessments of nuclear facilities, a wide range of radioactive isotopes and their potential hazard to a large assortment of organisms and ecosystem types over long time scales need to be considered. Models used for these purposes have typically employed approaches based on generic reference organisms, stylised environments and transfer functions for biological uptake exclusively based on bioconcentration factors (BCFs). These models are of non-mechanistic nature and involve no understanding of uptake and transport processes in the environment, which is a severe limitation when assessing real ecosystems. In this paper, ecosystem models are suggested as a method to include site-specific data and to facilitate the modelling of dynamic systems. An aquatic ecosystem model for the environmental transport of radionuclides is presented and discussed. With this model, driven and constrained by site-specific carbon dynamics and three radionuclide specific mechanisms: (i) radionuclide uptake by plants, (ii) excretion by animals, and (iii) adsorption to organic surfaces, it was possible to estimate the radionuclide concentrations in all components of the modelled ecosystem with only two radionuclide specific input parameters (BCF for plants and Kd). The importance of radionuclide specific mechanisms for the exposure to organisms was examined, and probabilistic and sensitivity analyses to assess the uncertainties related to ecosystem input parameters were performed. Verification of the model suggests that this model produces analogous results to empirically derived data for more than 20 different radionuclides.     

Suspended particle adhesion on aquatic plant surfaces: implications for 137Cs and 133Cs uptake rates and water-to-plant concentration ratios

Suspended particle adhesion on aquatic biota can significantly increase the apparent concentration of radionuclides above their endogenous value, leading to an overestimation of the uptake rate and concentration ratios. This study is an attempt to assess quantitatively the importance of suspended particle adhesion on periphyton samples (biological material coating submerged surfaces). The concentrations of 137Cs and stable Cs (133Cs) in periphyton, suspended particles and filtered water were measured to determine the net water-to-periphyton concentration ratios for 137Cs and stable Cs. The net amount of 133Cs (or 137Cs) taken up by periphyton was calculated by subtracting from the total amount of 133Cs (or 137Cs) on the collected material (periphyton + inorganic particles), the 133Cs (or 137Cs) due to the inorganic particles adhering to periphyton. The mass of suspended particles adhering to the periphyton surface was calculated using scandium as an indicator of the mineral fraction of the suspended particles. The relationship between the concentration ratios for 137Cs and stable Cs and suspended particle adhesion on periphyton external surfaces is discussed.     

Assessing field-scale migration of radionuclides at the Nevada Test Site: “mobile” species

Many long-lived radionuclides are present in groundwater at the Nevada Test Site (NTS) as a result of 828 underground nuclear weapons tests conducted between 1951 and 1992. In conjunction with a comprehensive geochemical review of radionuclides (³H, ¹⁴C, ³⁶Cl, ⁹⁹Tc and ¹²⁹I) that are presumably mobile in the subsurface, we synthesized a body of radionuclide activity data measured from groundwater samples collected at 18 monitoring wells, to qualitatively assess their migration at the NTS over distances of hundreds of meters and over timescales of decades. Tritium and ³⁶Cl showed little evidence of retardation, while the transport of ¹⁴C may have been retarded by its isotopic exchange with carbonate minerals in the aquifer. Observed local reducing conditions (either natural or test-induced) will impact the mobility of certain redox-sensitive radionuclides (especially ⁹⁹Tc) that were otherwise soluble and readily transported under oxidizing conditions. Conversely, strongly oxidizing conditions may impact the mobility of ¹²⁹I which is mobile under reducing conditions. The effect of iodine speciation on its transport deserves further attention. Indication of delayed transport of some “mobile” radionuclides (especially ⁹⁹Tc) in the groundwater at the NTS suggested the importance of redox conditions of the natural system in controlling the fate and transport of radionuclides, which has implications in the enhanced performance of the potential Yucca Mountain repository, located adjacent to the NTS, to store high-level nuclear wastes as well as management of radionuclide contamination in legacy nuclear operations facilities.     

Radioactive contamination in the marine environment adjacent to the outfall of the radioactive waste treatment plant at ATOMFLOT,northern Russia

RTP "ATOMFLOT" is a civilian nuclear icebreaker base located on the Kola Bay of northwest Russia. The objectives of this study were to determine the distributions of man-made radionuclides in the marine environment adjacent to the base, to explain the form of the distributions in sediments and to derive information concerning the fate of radionuclides discharged from ATOMFLOT. Mean activity concentrations (d.w.) for surface sediment, of 63 Bq kg(-1 137Cs, 5.8 Bq kg(-1) 90Sr and 0.45 Bq kg(-1 239,240)Pu were measured. Filtered seawater activity levels were in the range of 3--6.9 Bq m(-3) 137Cs, 2.0-11.2 Bq m(-3) 90Sr, and 16-40 m Bq m(-3), 239,240Pu. Short-lived radionuclides were present at sediment depths in excess of 10cm indicating a high degree of sediment mixing. Correlations of radionuclide activity concentrations with grain-size appear to be absent; instead, the presence of relatively contaminated sediment appears to be related to the existence of radioactive particles.     

Sorption and transport of radionuclides by tumbleweeds from two plastic-lined radioactive waste ponds

Previous research has examined the uptake of radionuclides by tumbleweeds growing in contaminated soils, but none has heretofore examined the sorption of radionuclides to tumbleweeds blowing into radioactively contaminated water. Three tumbleweed species; Russian thistle (Salsola kali), Jim Hill mustard (Sisymbrium altissimum) and summer cypress (Kochia scoparia) blow in, and out of, two plastic-lined radioactive wastewater ponds, constructed in 1993 on the US Department of Energy's Idaho National Engineering and Environmental Laboratory in southeast Idaho. This research quantified radionuclide sorption to tumbleweeds, tumbleweed movement from the ponds, and determined radionuclide transport from the ponds. Average plant/water concentration factors associated with tumbleweeds taken from the ponds ranged from 5 for 152Eu to over 9000 for 54Mn. Based on changes in tumbleweed numbers and average concentrations associated with them, 66.2 MBq were estimated to have been transported from the ponds via tumbleweeds between 18 October 1994 and 8 November 1996. This amounts to about 0.01% of the non-tritium and 0.0002% of the tritium activity released to the ponds through 8 November 1996. A power function best described the radionuclide buildup curve for tumbleweeds submerged in the ponds. Visually marked tumbleweeds traveled from the ponds in the predominant wind direction a maximum of 737 m. Management practices which may reduce the number of tumbleweeds blowing both into and out of contaminated ponds are discussed.     

Bioavailability of sediment-associated and low-molecular-mass species of radionuclides/trace metals to the mussel Mytilus edulis

Sediments can act as a sink for contaminants in effluents from industrial and nuclear installations or when released from dumped waste. However, contaminated sediments may also act as a potential source of radionuclides and trace metals to the water phase due to remobilisation of metals as dissolved species and resuspension of particles. The marine mussel Mytilus edulis is a filter-feeding organism that via the gills is subjected to contaminants in dissolved form and from contaminants associated to suspended particles via the digestive system. In this paper the bioavailability of sediment-associated and seawater diluted Cs, Co, Cd and Zn radioactive tracers to the filtering bivalve M. edulis has been examined. The mussels were exposed to tracers diluted in ultrafiltered (<10 kDa) seawater (Low Molecular Mass form) or to tracers associated with sediment particles from the Stepovogo Fjord at Novaya Zemlya in short-term uptake experiments, followed by 1-month depuration experiments in flow-through tanks. A toxicokinetic model was fitted to the uptake and depuration data, and the obtained parameters were used to simulate the significance of the two uptake pathways at different suspended sediment loads and sediment-seawater distribution coefficients. The results of the model simulations, assuming steady state conditions, suggest that resuspended particles from contaminated sediments can be a highly significant pathway for mussels in the order ¹⁰⁹Cd ≌ ⁶⁵Zn < ¹³⁴Cs < ⁶⁰Co. The significance increases with higher suspended sediment load and with higher K_d. Furthermore, the experimental depuration data suggest that Cs is retained longer and Co, Cd and Zn shorter by the mussels when associated with ingested sediments, than if the metals are taken up from the low molecular mass (LMM) phase.     

Deposition of gaseous radionuclides to fruit

14C, 35S and 3H are released to the environment during the operation of gas-cooled reactors and were identified as radionuclides of interest by the BIOMASS Fruits Working Group. This paper provides a review of the deposition, uptake, allocation and loss of these radionuclides with respect to fruit and conceptual models for gaseous radionuclides. It is concluded that the mechanisms for the uptake of CO35S, HTO and 14CO2 are well understood and that their deposition velocities have been quantified. There is also a reasonable body of work on the translocation of 14C once in the crop, but much less for 35S and 3H, which are considered to follow source-sink relationships. The loss rates of the three radionuclides show large differences, with tritium lost rapidly in the form of HTO but retained longer when converted to OBT. The losses of 14C are less and those of sulphur are minimal post fixation. When fruit crops alone are considered, the quantity of information is further reduced but predictions on possible behaviour of these radionuclide species can be made from the current knowledge.     

Uranium mill tailings: nuclear waste and natural laboratory for geochemical and radioecological investigations

Uranium mill tailings (UMT) are a high volume, low specific activity radioactive waste typically disposed in surface impoundments. This review focuses on research on UMT and related earth materials during the past decade relevant to the assessment of: (1) mineral hosts of radionuclides; (2) the use of soil analogs in predicting long-term fate of radionuclides; (3) microbial and diagenetic processes that may alter radionuclide mobility in the surficial environment; (4) waste-management technologies to limit radionuclide migration; and (5) the impact of UMT on biota.     

Radioactive impact of Fukushima accident on the Iberian Peninsula: evolution and plume previous pathway

High activity concentrations of several man-made radionuclides (such as (131)I, (132)I, (132)Te, (134)Cs and (137)Cs) have been detected along the Iberian Peninsula from March 28th to April 7th 2011. The analysis of back-trajectories of air masses allowed us to demonstrate that the levels of manmade radionuclide activity concentrations in the southwest of the Iberian Peninsula come from the accident produced in the nuclear power plant of Fukushima. The pathway followed by the radioactive plume from Fukushima into Huelva (southwest of the Iberian Peninsula) was deduced through back-trajectories analysis, and this fact was also verified by the activity concentrations measured of those radionuclides reported in places crossed by this radioactive cloud. In fact, activity concentrations reported by E.P.A., and by IAEA, in several places of Japan, Pacific Ocean and United States of America are according to the expected ones from the air mass trajectory arriving at Huelva province.     

An inventory of long-lived radionuclides residual from underground nuclear testing at the Nevada test site, 1951-1992

An inventory of long-lived radionuclides produced by 828 underground nuclear tests conducted at the Nevada test site (NTS) from 1951 to 1992 includes residual tritium, fission products, actinides, and activation products. Recently, the US Department of Energy approved the declassification of the NTS radionuclide inventory by principal geographic test centers. This permits unclassified publication of radionuclide totals for the Yucca Flat, Pahute Mesa-Area 19, Pahute Mesa-Area 20, Frenchman Flat, and Rainier Mesa/Shoshone Mountain testing locations. Activities are reported as of September 23, 1992, the date of the last underground nuclear test conducted at the NTS, and September 23, 2492, after 500 years of radioactive decay. The availability of these data affords an opportunity for the analysis of the radiologic source term within the boundaries of local hydrogeologic units and provides insight to where radionuclides are sited relative to potential exposure pathways.