Do transient hydrological processes explain the variability of strontium-90 activity in groundwater downstream of a radioactive trench near Chernobyl?

The Chernobyl Pilot Site (CPS) was created in 2000 in order to study radionuclide migration processes to the geosphere from radioactive material of the Red forest buried in a trench. In this article, the data collected in the CPS up to 2015 are analyzed to identify the links between hydrological conditions and release of strontium-90 (90Sr) from the trench. Then, a flow-and-transport model is used for simulating distribution of 90Sr both in the unsaturated and saturated zones downstream of the trench. The results show that the 90Sr activity in groundwater is strongly transient in time, due to the high inter-annual variability of both the recharge rate and the groundwater level (some particularly wet winters resulted in saturation of the bottom part of the trench). In addition, the parameters that govern the sorption of 90Sr in trench material appear to vary significantly in space (the retardation factor ranges from 10 to 50 depending on the location). This spatiotemporal variability could hide some critical processes, e.g., related to a long-term trend, and needs to be characterized through an appropriate sampling frequency.

Influence of microorganisms on uranium release from mining-impacted lake sediments under various oxygenation conditions.

Microbial processes can be involved in the remobilization of uranium (U) from reduced sediments under O2 reoxidation events such as water table fluctuations. Such reactions could be typically encountered after U-bearing sediment dredging operations. Solid U(IV) species may thus reoxidize into U(VI) that can be released in pore waters in the form of aqueous complexes with organic and inorganic ligands. Non-uraninite U(IV) species may be especially sensitive to reoxidation and remobilization processes. Nevertheless, little is known regarding the effect of microbially mediated processes on the behaviour of U under these conditions.

Deciphering sources of U contamination using isotope ratio signatures in the Loire River sediments: Exploring the relevance of 233U/236U and stable Pb isotope ratios.

A broad range of contaminants has been recorded in sediments of the Loire River over the last century. Among a variety of anthropogenic activities of this nuclearized watershed, extraction of uranium and associated activities during more than 50 years as well as operation of several nuclear power plants led to industrial discharges, which could persist for decades in sedimentary archives of the Loire River. Highlighting and identifying the origin of radionuclides that transited during the last decades and were recorded in the sediments is challenging due to i) the low concentrations which are often close or below the detection limits of routine environmental surveys and ii) the mixing of different sources. The determination of the sources of anthropogenic radioactivity was performed using multi-isotopic fingerprints (236U/238U, 206Pb/207Pb and 208Pb/207Pb) and the newly developed 233U/236U tracer. For the first time 233U/236U data in a well-dated river sediment core in the French river Loire are reported here. Results highlight potential sources of contamination among which a clear signature of anthropogenic inputs related to two accidents of a former NUGG NPP that occurred in 1969 and 1980. The 233U and 236U isotopes were measured by recent high performance analytical methods due to their ultra-trace levels in the samples and show a negligible radiological impact on health and on the environment. The determination of mining activities by the use of stable Pb isotopes is still challenging probably owing to the limited dissemination of the Pb-bearing material marked by the U-ore signature downstream to the former U mines.

Combined U-Pb isotopic signatures of U mill tailings from France and Gabon: A new potential tracer to assess their fingerprint on the environment.

Uranium milling activities have produced high volumes of long-lived radioactive processed wastes stored worldwide in near surface environment. The aim of this study is to highlight relevant tracers that can be used for environmental impact assessment studies involving U mill tailings. A multi-tracer study involving elemental content, 238U decay products disequilibria and stable Pb isotopes was performed in different types of U mill tailings (alkaline, acid, neutralized acid) collected from five Tailings Management Facilities in France (Le Bosc, L'Ecarpière, Le Bernardan, and Bellezane) and Gabon (Mounana). Our results showed that U and Pb concentrations range between 30 and 594 ppm and 66-805 ppm, respectively. These tailings have a strong disequilibrium of (234U/238U) and (230Th/238U) activity ratios (1.27-1.87 and 6-65, respectively), as well as higher 206Pb/207Pb (1.86-7.15) and lower 208Pb/207Pb (0.22-2.39) compared to geochemical background ((234U/238U) and (230Th/238U) equal to unity; 206Pb/207Pb = 1.20; 208Pb/207Pb = 2.47). In situ analyzes (SEM, SIMS) showed that Pb-bearing phases with high 206Pb/207Pb are related to remaining U-rich phases, S-rich phases and potentially clay minerals or oxyhydroxides. We suggest that the combination of the 206Pb/207Pb with the (234U/238U) ratio is a relevant tool for the fingerprinting of the impact of U milling activities on the environment.

226Ra and 137Cs determination by inductively coupled plasma mass spectrometry: state of the art and perspectives including sample pretreatment and separation steps.

Achieving precise and accurate quantification of radium (226Ra) and cesium (137Cs) by inductively coupled plasma mass spectrometry (ICP-MS) is of particular interest in the field of radiological monitoring and more widely in environmental and biological sciences. However, the accuracy and sensitivity of the quantification depend on the analytical strategy implemented. Eliminating interferences during the sample handling step and/or during the analysis step is critical since presence of matrix elements can lead to spectral and non-spectral interferences in ICP-MS. Consequently, before the ICP-MS analysis, multiple sample preparation approaches have been applied to purify and/or pre-concentrate environmental and biological samples containing radium and cesium through years, such as (co)-precipitation, solid phase extraction (SPE) or dispersive SPE (dSPE). Separation steps using liquid chromatography and capillary electrophoresis can also be useful in complement with the abovementioned sample preparation techniques. The most attractive sample handling technique remains SPE but efficiency of the extraction procedures is currently limited by sorbent specificity. Indeed, with the recent advances in ICP-MS instrumentation, it becomes indispensable to eliminate residual interferences and improve sensitivity. It is in this direction that it will be possible to meet analytical challenges, e.g. analyzing radium and cesium at concentrations below the pg L-1 range in complex matrices of small volumes, as they are found for instance in pore waters or in biological samples. Development of new innovative sorbents based for example on hybrid and nanostructured materials has been reported with the aim of enhancing sorbent specificity and/or capacity. In the present review, the performances of the different analytical approaches are discussed, followed by an overview of applications.

Dissolved iodide in marine waters determined with Diffusive Gradients in Thin-films technique.

For the first time, Diffusive Gradient in Thin-films (DGT) focuses on the inorganic iodine species iodate (IO3-) and iodide (I-). A silver-doped Cl resin (AgdCl), which is known to selectively accumulate I-, was used to make a binding gel. Laboratory investigations were designed to verify the suitability of the AgdCl-DGT method to measure the total I- concentration in environmental waters. Total recovery of I- was obtained using an elution solution containing 100 mmol L-1 KCN. DGT validation experiments in 10 mmol L-1 NaCl showed linear accumulation of I- over time, contrary to IO3-, thus confirming the selectivity of AgdCl-binding gel. The AgdCl-DGT measurement of total I- concentration was independent of pH (4.5-8.8) and was not impacted by the presence of bicarbonate (1-5 mmol L-1). Finally, the performance of AgdCl-DGT samplers were tested in two continental waters and a synthetic seawater. The AgdCl-DGT samplers measured 27-33% of the total I- concentration in the two continental waters up to 24 h of deployment time, whereas the AgdCl-DGT response retrieved the total I- concentration in seawater up to 72 h (106 ± 7%). The difference in DGT response was attributed to the low ionic strength of the two continental waters, limiting the application of AgdCl-DGT method to media with higher ionic strength.

Climate-driven fluxes of organic-bound uranium to an alpine lake over the Holocene.

Uranium (U) isotopic signatures and concentration in sediments are widely used as paleo-redox proxies, as the behavior of U is often controlled by bottom water oxygenation. Here, we investigated the processes controlling U accumulation in the sediments of Lake Nègre (Mediterranean Alps, South-East France) over the past 9200 years. Exceptionally high natural U concentrations (350-1250 µg·g-1) allowed the measurement of U along with other elements by high-resolution X-Ray Fluorescence core-scanning. Weathering and erosion proxies (Ti content, Zr/Al and K/Ti ratios) indicate that sedimentary inputs were controlled by Holocene climatic variations. After a period of low erosion during the Holocene Climatic Optimum, a major regime shift was recorded at 4.2 kyr BP when terrigenous fluxes consistently increased until present with high sensitivity to centennial-scale climatic events. Sedimentary organic matter (OM) inputs were dominated by terrigenous OM from the catchment soils until 2.4 kyr BP, as attested by carbon to nitrogen (C/N) and bromine to organic carbon (Br/TOC) ratios. From 2.4 kyr BP to present, lake primary production and soils equally contributed to sedimentary OM. Uranium fluxes to the sediments were well correlated to terrigenous OM fluxes from 7 kyr BP to present, showing that U supply to the lake was controlled by U scavenging in the soils of the watershed followed by transport of U bound to detrital organic particles. Higher U/OM ratios before 7 kyr BP likely reflect the development of the upstream wetland. The fluctuations of U sedimentary inputs appear to be independent of bottom water oxygenation, as estimated from constant Fe/Mn ratios and δ238U isotopic signatures, and rather controlled by the production, erosion and sedimentation of terrigenous OM. This finding confirms that the use of U (and potentially other metals with high affinity to OM) concentrations alone should be used with caution for paleo-redox reconstructions.

Diagenetic formation of uranium-silica polymers in lake sediments over 3,300 years.

The long-term fate of uranium-contaminated sediments, especially downstream former mining areas, is a widespread environmental challenge. Essential for their management is the proper understanding of uranium (U) immobilization mechanisms in reducing environments. In particular, the long-term behavior of noncrystalline U(IV) species and their possible evolution to more stable phases in subsurface conditions is poorly documented, which limits our ability to predict U long-term geochemical reactivity. Here, we report direct evidence for the evolution of U speciation over 3,300 y in naturally highly U-enriched sediments (350-760 µg ⋅ g-1 U) from Lake Nègre (Mercantour Massif, Mediterranean Alps, France) by combining U isotopic data (δ238U and (234U/238U)) with U L3 -edge X-ray absorption fine structure spectroscopy. Constant isotopic ratios over the entire sediment core indicate stable U sources and accumulation modes, allowing for determination of the impact of aging on U speciation. We demonstrate that, after sediment deposition, mononuclear U(IV) species associated with organic matter transformed into authigenic polymeric U(IV)-silica species that might have partially converted to a nanocrystalline coffinite (UIVSiO4·nH2O)-like phase. This diagenetic transformation occurred in less than 700 y and is consistent with the high silica availability of sediments in which diatoms are abundant. It also yields consistency with laboratory studies that proposed the formation of colloidal polynuclear U(IV)-silica species, as precursors for coffinite formation. However, the incomplete transformation observed here only slightly reduces the potential lability of U, which could have important implications to evaluate the long-term management of U-contaminated sediments and, by extension, of U-bearing wastes in silica-rich subsurface environments.

Estimation of fukushima radio-cesium deposits by airborne surveys: Sensitivity to the flight-line spacing.

After Fukushima Daiichi Nuclear Power Plant (FDNPP) accident, airborne gamma-ray detection was used for regional mapping of soil contamination. For such surveys, the flight-line spacing is an important factor controlling the quality of contamination maps. In this study, cesium-137 (137Cs) ground activity is interpolated and mapped using ordinary kriging method; thereafter the error of interpolation is evaluated as a function of flight-line spacing. The analyses were conducted in six 20 km × 20 km test sites with distance of less than 80 km from the FDNPP. In each site, the ordinary kriging estimators were applied to different selections of flight-lines of decreasing density, then punctual and classification errors were calculated. It is demonstrated that these variables are highly correlated (r2 > 0.78): increasing the flight-line spacing for 1 km increases the errors from 3% to 9%, depending on the site location. Therefore, flight-line spacing could be designed as a function of acceptable error, determined in the monitoring objectives.

Pushing Limits of ICP-MS/MS for the Determination of Ultralow 236U/238U Isotope Ratios.

Determination of uranium isotope ratios is of great expedience for assessing its origin in environmental samples. In particular, the 236U/238U isotope ratio provides a powerful tool to discriminate between the different sources of uranium (uranium ore, geochemical background, and uranium from anthropogenic activities). However, in the environment, this ratio is typically below 10-8. This low abundance of 236U and the presence in large excess of major isotopes (mainly 238U and 235U) complicates the accurate detection of 236U signal by mass spectrometry and thus highly sensitive analytical instruments providing high abundance sensitivity are required. This work pushes the limits of triple quadrupole-based ICP-MS technology for accurate detection of 236U/238U isotope ratios down to 10-10, which is so far mainly achievable by AMS. Coupled with an efficient desolvating module, N2O was used as the reaction gas in the collision reaction cell of the ICP-MS/MS. This configuration allows a significant decrease of the uranium polyatomic interferences (235UH+ ions) and an accurate determination of low 236U/238U isotope ratios. This new methodology was successfully validated through measurements of certified reference material from 10-7 to 10-9 and then through comparisons with AMS measurement results for ratios down to 10-10. This is the first time that 236U/238U isotope ratios as low as 10-10 were determined by ICP-MS/MS. The possibility of measuring low 236U/238U isotope ratios can offer a large variety of geochemical applications in particular for the determination of uranium sources in the environment.

New Insights into Pb Isotope Fingerprinting of U-Mine Material Dissemination in the Environment: Pb Isotopes as a Memory Dissemination Tracer.

Stable Pb isotope ratios were measured and compared to U distributions in three soil cores located in a wetland highly impacted by water discharge of a former U-mine. Pb isotope ratios showed notable alignments in binary mixing plots, demonstrating the dissemination of radioactive-enriched material from the U-mine. Thanks to these alignments and to the measurement of the 204Pb isotope, a precise characterization of the Pb isotope composition of the U-ore was performed without the use of U-ore samples. The well-defined end-members with the help of a reevaluated isotope mixing model allowed the accurate determination of the radiogenic Pb percentages in the cores that were overall found to be >50%. Noncorrelated distributions of radiogenic 206Pb and U are observed in several of the wetland soil samples. They reveal postdepositional U redistribution explained by major U speciation changes due to redox cycling in the wetland. On the contrary, the radiogenic 206Pb showed no or little postdepositional mobility and thus can be considered to be a memory tracer of the dissemination of U-rich radioactive material: even after an important U loss, the radiogenic 206Pb is able to reveal past contamination by U-rich materials.

Experimental redox transformations of uranium phosphate minerals and mononuclear species in a contaminated wetland.

Reducing conditions and high organic carbon content make wetlands favorable to uranium (U) sequestration. However, such environments are subjected to water-table fluctuations that could impact the redox behavior of U and its mobility. Our previous study on U speciation in a contaminated wetland has suggested a major role of water-table redox fluctuations in the redistribution of U from U(IV)-phosphate minerals to organic U(VI) and U(IV) mononuclear species. Here, we investigate the mechanisms of these putative processes by mimicking drying or flooding periods via laboratory incubations of wetland samples. LCF-XANES and EXAFS analyses show the total oxidation/reduction of U(IV)/U(VI)-mononuclear species after 20 days of oxic/anoxic incubation, whereas U-phosphate minerals are partly oxidized/reduced. SEM-EDXS combined with µ-XRF and µ-XANES analyses suggest that autunite Ca(UO2)2(PO4)2⋅11H2O is reduced into lermontovite U(PO4)(OH)⋅H2O, whereas oxidized ningyoite CaU(PO4)2⋅2H2O is locally dissolved. The release of U from this latter process is observed to be limited by U(VI) adsorption to the soil matrix and further re-reduction into mononuclear U(IV) upon anoxic cycling. Analysis of incubation waters show, however, that dissolved organic carbon enhances U solubilization even under anoxic conditions. This study brings important information that help to assess the long-term stability of U in seasonally saturated organic-rich contaminated environments.

Spatial properties of soil analyses and airborne measurements for reconnaissance of soil contamination by 137Cs after Fukushima nuclear accident in 2011.

Following Fukushima nuclear disaster, several data gathering campaigns surveyed the radionuclide propagation in the environment. However, the acquired datasets do not have the same sampling dimension. For example, the airborne measurements are some sort of averaging over a circular field of view, beneath the sensor; while the soil analyses are much more punctual. The objective of this work is to compare the soil samples and an airborne survey to investigate whether these two datasets reflect the same spatial patterns or not. This is prerequisite for combining the multiresolution data to create and update the contamination map in a post-accidental situation. The analyses were performed on square tiles of 20 km side to study large- and small-dimension variations in 137Cs deposition. The former was modelled by fitting a plane (called trend) to the georeferenced data points; and the latter was modelled by computing the difference (called residual) between the trend and the initial data. Dip direction and dip angle of trends as well as minimum spatial correlation distance and anisotropy of residuals were computed for both the soil and airborne datasets and compared. Dip directions are compatible in 73% of the tiles and dip angles are generally close. Anisotropy directions are compatible in 49% of the tiles and minimum spatial correlation distances are significantly more marked for the airborne dataset. The soil samples and airborne measurements are therefore more in agreement in large-dimension (trend) rather than in small-dimension (residual) variations. More generally, both the datasets allow highlighting the main contamination plumes distinguishable because of high concentration values. The airborne dataset yet appears to be more powerful to quantify spatial correlations, which could be linked to the contamination mechanisms.

An evidence of chemically and physically mediated migration of 238U and its daughter isotopes in the vicinity of a former uranium mine.

The present study reports the evidence of a radioactive contamination in a wetland located downstream from a former French U mine in Brittany. This situation is demonstrated according to the measurements of gamma dose rates and activity ratios of 238U and 232Th-decay series nuclides, which give the justification regarding the accumulation of significant amounts of 238U, 230Th and 226Ra in this wetland. The dose rate map highlights an increase of radiation level along the former mine water pathway compared to the background value, with a maximum value of 1500 nSv.h-1 reached in the wetland. Activities of 238U, 230Th and 226Ra and 232Th/238U ratios measured in surface wetland soils are significantly higher than the geochemical background. 230Th/238U ratios less than unity suggest a preferential accumulation of U in the wetland, compared to its daughter isotopes. Moreover, the loss of 226Ra compared to 230Th raises its higher mobility compared to its parent isotope. In far-field sediments, 226Ra/238U ratio of 1.76 implies a different geochemical behavior of U, which could be explained by the occurrence of mobile U species. The results suggest that contamination of wetland soils and far-field sediments could result from discharges of underground mine waters.

Redox Fluctuations and Organic Complexation Govern Uranium Redistribution from U(IV)-Phosphate Minerals in a Mining-Polluted Wetland Soil, Brittany, France.

Wetlands have been proposed to naturally attenuate U transfers in the environment via U complexation by organic matter and potential U reduction. However, U mobility may depend on the identity of particulate/dissolved uranium source materials and their redox sensitivity. Here, we examined the fate of uranium in a highly contaminated wetland (up to 4500 mg·kg-1 U) impacted by former mine water discharges. Bulk U LIII-EXAFS and (micro-)XANES combined with SEM-EDXS analyses of undisturbed soil cores show a sharp U redox boundary at the water table, together with a major U redistribution from U(IV)-minerals to U(VI)-organic matter complexes. Above the water table, U is fully oxidized into mono- and bidentate U(VI)-carboxyl and monodentate U(VI)-phosphoryl complexes. Minute amounts of U(VI)-phosphate minerals are also observed. Below the water table, U is fully reduced and is partitioned between U(IV)-phosphate minerals (i.e., ningyoite and a lermontovite-like phase), and bidentate U(IV)-phosphoryl and monodentate U(IV)-carboxyl complexes. Such a U redistribution from U-minerals inherited from mine water discharge deposits could result from redox cycling nearby the water table fluctuation zone. Oxidative dissolution of U(IV)-phosphate minerals could have led to U(VI)-organic matter complexation, followed by subsequent reduction into U(IV)-organic complexes. However, uranium(IV) minerals could have been preserved in permanently waterlogged soil.

Carbonate Facilitated Mobilization of Uranium from Lacustrine Sediments under Anoxic Conditions.

Sorbed U(IV) species can be major products of U(VI) reduction in natural reducing environments as sediments and waterlogged soils. These species are considered more labile than crystalline U(IV) minerals, which could potentially influence uranium migration in natural systems subjected to redox oscillations. In this study, we examined the role of oxygen and carbonate on the remobilization of uranium from lake sediments, in which ∼70% of the 150-300 ppm U is under the form of mononuclear U(IV) sorbed species. Our results show that both drying and oxic incubation only slightly increase the amount of remobilized U after 8 days, compared to anoxic drying and anoxic incubation. In contrast, the amount of remobilized U increases with the quantity of added bicarbonate even under anoxic conditions. Moreover, U LIII-edge XANES data show that a significant amount of the solid U(IV) is mobilized in such conditions. Thermodynamic speciation calculations based on the supernatant composition indicates the predominance of aqueous UO2(CO3)34- and, to a lesser extent, CaUO2(CO3)32- complexes. These results suggest that monomeric U(IV) species could be oxidized into aqueous U(VI) carbonate complexes even under anoxic conditions via carbonate promoted oxidative dissolution, which emphasizes the need for considering such a process when modeling U dynamics in reducing environments.

Silicon isotope ratio measurements by inductively coupled plasma tandem mass spectrometry for alteration studies of nuclear waste glasses.

High-level, long-lived nuclear waste arising from spent fuel reprocessing is vitrified in silicate glasses for final disposal in deep geologic formations. In order to better understand the mechanisms driving glass dissolution, glass alteration studies, based on silicon isotope ratio monitoring of 29Si-doped aqueous solutions, were carried out in laboratories. This work explores the capabilities of the new type of quadrupole-based ICP-MS, the Agilent 8800 tandem quadrupole ICP-MS/MS, for accurate silicon isotope ratio determination for alteration studies of nuclear waste glasses. In order to avoid silicon polyatomic interferences, a new analytical method was developed using O2 as the reaction gas in the Octopole Reaction System (ORS), and silicon isotopes were measured in mass-shift mode. A careful analysis of the potential polyatomic interferences on SiO+ and SiO2+ ion species was performed, and we found that SiO+ ion species suffer from important polyatomic interferences coming from the matrix of sample and standard solutions (0.5M HNO3). For SiO2+, no interferences were detected, and thus, these ion species were chosen for silicon isotope ratio determination. A number of key settings for accurate isotope ratio analysis like, detector dead time, integration time, number of sweeps, wait time offset, memory blank and instrumental mass fractionation, were considered and optimized. Particular attention was paid to the optimization of abundance sensitivity of the quadrupole mass filter before the ORS. We showed that poor abundance sensitivity leads to a significant shift of the data away from the Exponential Mass Fractionation Law (EMFL) due to the spectral overlaps of silicon isotopes combined with different oxygen isotopes (i.e. 28Si16O18O+, 30Si16O16O+). The developed method was validated by measuring a series of reference solutions with different 29Si enrichment. Isotope ratio trueness, uncertainty and repeatability were found to be <0.2%, <0.5% and <0.6%, respectively. These performances meet the requirements of the studies of nuclear glasses alteration and open up possibilities to use this method for precise determination of silicon content in natural samples by Isotope Dilution.