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.

Anthropogenic legacy of potassium-40 in French large rivers reconstructed from sediment cores.

Environmental imprint of inorganic fertilizer uses was assessed over the last hundred years at the downstream part of large French rivers (Loire, Moselle, Rhine, Rhone, Meuse and Seine rivers) based on Potassium-40 (40K) activity concentration data sets acquired from soil monitoring (1980-2022) and from sediment coes collected from 2020 to 2022 to reconstruct the temporal trajectories of 40K activity concentrations since the beginning of the last century. Cultivated soils were significantly enriched in 40K compared to non-cultivated ones in the 1980s and 1990s when they turned back to the contents of non-cultivated soils during the following decades. In riverine sediments, all the rivers displayed close 40K temporal trajectories with peaking 40K contents in fine grain size sediments in the 1980s. Maximum 40K enrichment factors from this period were related to the proportion of agricultural areas in the river catchment. In the Loire and Moselle rivers, some high 40K contents were associated with sandy sedimentary strata deposited by flood events before the end of the 1950s due to the presence of potassium enriched minerals. The comparison of 40K activity concentration in sediments with potassic fertilizer delivery in France highlighted very similar temporal trajectories giving evidence that the uses of potassic fertilizers imprint the riverine sediments of most French large rivers. Finally, the environmental resilience face to this anthropic pressure was fast as 40K levels decreased immediately after the decreases of the delivery in most of cases.

Temporal trajectories of artificial radiocaesium 137Cs in French rivers over the nuclear era reconstructed from sediment cores.

137Cs is a long-lived man-made radionuclide introduced in the environment worldwide at the early beginning of the nuclear Era during atmospheric nuclear testing's followed by the civil use of nuclear energy. Atmospheric fallout deposition of this major artificial radionuclide was reconstructed at the scale of French large river basins since 1945, and trajectories in French nuclearized rivers were established using sediment coring. Our results show that 137Cs contents in sediments of the studied rivers display a large spatial and temporal variability in response to the various anthropogenic pressures exerted on their catchment. The Loire, Rhone, and Rhine rivers were the most affected by atmospheric fallout from the global deposition from nuclear tests. Rhine and Rhone also received significant fallout from the Chernobyl accident in 1986 and recorded significant 137Cs concentrations in their sediments over the 1970-1985 period due to the regulatory releases from the nuclear industries. The Meuse River was notably impacted in the early 1970s by industrial releases. In contrast, the Seine River display the lowest 137Cs concentrations regardless of the period. All the rivers responded similarly over time to atmospheric fallout on their catchment, underlying a rather homogeneous resilience capacity of these river systems to this source of contamination.

Elevated uranium concentration and low activity ratio (234U/238U) in the Œuf river as the result of groundwater-surface water interaction (Essonne river valley, South of Paris Basin, France).

Uranium (U) is a naturally occurring radioactive heavy metal widely distributed on Earth. Noticeable elevated U concentration and low activity ratio (AR) were occasionally detected in headwater stream of the Essonne river (Seine Basin, France), the namely Œuf river. This paper aims at providing new insight on geogenic U features in headwater streams and examines the role of river-groundwater interaction. The Œuf river was sampled four times in 2020 to investigate the influence of heterogeneous geology and hydrological seasonality. The dissolved fraction of water samples was analyzed for a variety of chemical parameters (anion, major, minor and trace element concentrations, isotopes 234U and 238U). The Œuf river was shown to exhibit elevated U concentration up to 19.3 µg L-1 (exceeding by 100-fold the value of 0.19 µg L-1 known for riverine average) and low AR down to 0.41 (almost the third of the value expected in surface water, i.e., 1.17). The Œuf river got enriched in U when receiving groundwater from Beauce Limestone Aquifer System. High U concentration (above 15 µg L-1) was found in association with low AR (below 0.5) in the stream water when flowing in the outcrop zone of one BLAS unit. Taking advantage of changes in the stream flow conditions and the geochemical contrast between surface and ground waters, mixing volumes were calculated. This study first examined the potential of using U isotopes in combination with selenium as hydrogeochemical tracers of the river-groundwater continuum. In HWS, the aquifer discharge was shown to supply 12 to 59 % of the river water. This study demonstrates the key role played by the river-groundwater interaction on river water chemistry in small streams draining catchment with various geology setting. It also supports the use of combining redox sensitive trace elements to track the river-groundwater continuum.

U isotopes distribution in the Lower Rhone River and its implication on radionuclides disequilibrium within the decay series.

The large rivers are main pathways for the delivery of suspended sediments into coastal environments, affecting the biogeochemical fluxes and the ecosystem functioning. The radionuclides from 238U and 232Th-series can be used to understand the dynamic processes affecting both catchment soil erosion and sediment delivery to oceans. Based on annual water discharge the Rhone River represents the largest river of the Mediterranean Sea. The Rhone valley also represents the largest concentration in nuclear power plants in Europe. A radioactive disequilibrium between particulate 226Ra(p) and 238U(p) was observed in the suspended sediment discharged by the Lower Rhone River (Eyrolle et al. 2012), and a fraction of particulate 234Th was shown to derive from dissolved 238U(d) (Zebracki et al. 2013). This extensive study has investigated the dissolved U isotopes distribution in the Lower Rhone River and its implication on particulate radionuclides disequilibrium within the decay series. The suspended sediment and filtered river waters were collected at low and high water discharges. During the 4-months of the study, two flood events generated by the Rhone southern tributaries were monitored. In river waters, the total U(d) concentration and U isotopes distribution were obtained through Q-ICP-MS measurements. The Lower Rhone River has displayed non-conservative U-behavior, and the variations in U(d) concentration between southern tributaries were related to the differences in bedrock lithology. The artificially occurring 236U was detected in the Rhone River at low water discharges, and was attributed to the liquid releases from nuclear industries located along the river. The (235U/238U)(d) activity ratio (=AR) in river waters was representative of the 235U natural abundance on Earth. The (226Ra/238U)(p) AR in suspended sediment has indicated a radioactive disequilibrium (average 1.3 ± 0.1). The excess of 234Th in suspended sediment =(234Thxs(p)) was apparent solely at low water discharges. The activity of 234Thxs(p) was calculated through gamma measurements and ranged from unquantifiable to 56 ± 14 Bq kg-1. The possibility of using 234Th as a tracer for the suspended sediment dynamics in large Mediterranean river was then discussed.

Tracing the origin of suspended sediment in a large Mediterranean river by combining continuous river monitoring and measurement of artificial and natural radionuclides.

Delivery of suspended sediment from large rivers to marine environments has important environmental impacts on coastal zones. In France, the Rhone River (catchment area of 98,000 km(2)) is by far the main supplier of sediment to the Mediterranean Sea and its annual solid discharge is largely controlled by flood events. This study investigates the relevance of alternative and original fingerprinting techniques based on the relative abundances of a series of radionuclides measured routinely at the Rhone River outlet to quantify the relative contribution of sediment supplied by the main tributaries during floods. Floods were classified according to the relative contribution of the main subcatchments (i.e., Oceanic, Cevenol, extensive Mediterranean and generalised). Between 2000 and 2012, 221 samples of suspended sediment were collected at the outlet and were shown to be representative of all flood types that occurred during the last decade. Three geogenic radionuclides (i.e., (238)U, (232)Th and (40)K) were used as fingerprints in a multivariate mixing model in order to estimate the relative contribution of the main subcatchment sources-characterised by different lithologies-in sediment samples collected at the outlet. Results showed that total sediment supply originating from Pre-Alpine, Upstream, and Cevenol sources amounted to 10, 7 and 2.10(6)tons, respectively. These results highlight the role of Pre-Alpine tributaries as the main sediment supplier (53%) to the Rhone River during floods. Other fingerprinting approaches based on artificial radionuclide activity ratios (i.e., (137)Cs/(239+240)Pu and (238)Pu/(239+240)Pu) were tested and provided a way to quantify sediment remobilisation or the relative contributions of the southern tributaries. In the future, fingerprinting methods based on natural radionuclides should be further applied to catchments with heterogeneous lithologies. Methods based on artificial radionuclides should be further applied to catchments characterised by heterogeneous post-Chernobyl (137)Cs deposition or by specific releases of radioactive effluents.

Tritium and 14C background levels in pristine aquatic systems and their potential sources of variability.

Tritium and (14)C are currently the two main radionuclides discharged by nuclear industry. Tritium integrates into and closely follows the water cycle and, as shown recently the carbon cycle, as does (14)C (Eyrolle-Boyer et al., 2014a, b). As a result, these two elements persist in both terrestrial and aquatic environments according to the recycling rates of organic matter. Although on average the organically bound tritium (OBT) activity of sediments in pristine rivers does not significantly differ today (2007-2012) from the mean tritiated water (HTO) content on record for rainwater (2.4 ± 0.6 Bq/L and 1.6 ± 0.4 Bq/L, respectively), regional differences are expected depending on the biomass inventories affected by atmospheric global fallout from nuclear testing and the recycling rate of organic matter within watersheds. The results obtained between 2007 and 2012 for (14)C show that the levels varied between 94.5 ± 1.5 and 234 ± 2.7 Bq/kg of C for the sediments in French rivers and across a slightly higher range of 199 ± 1.3 to 238 ± 3.1 Bq/kg of C for fish. This variation is most probably due to preferential uptake of some organic carbon compounds by fish restraining (14)C dilution with refractory organic carbon and/or with old carbonates both depleted in (14)C. Overall, most of these ranges of values are below the mean baseline value for the terrestrial environment (232.0 ± 1.8 Bq/kg of C in 2012, Roussel-Debet, 2014a) in relation to dilution by the carbonates and/or fossil organic carbon present in aquatic systems. This emphasises yet again the value of establishing regional baseline value ranges for these two radionuclides in order to account for palaeoclimatic and lithological variations. Besides, our results obtained from sedimentary archive investigation have confirmed the delayed contamination of aquatic sediments by tritium from the past nuclear tests atmospheric fallout, as recently demonstrated from data chronicles (Eyrolle-Boyer et al., 2014a,b). Thus Sedimentary archives can be successfully used to reconstruct past (14)C and OBT levels. Additionally, sediment repositories potentially represent significant storages of OBT that may account for in case of further remobilisation. We finally show that floods can significantly affect the OBT and (14)C levels within suspended particles or sediments depending on the origin of particles reinforcing the need to acquire baseline value range at a regional scale.