Assessing the chronic effect of the bioavailable fractions of radionuclides and heavy metals on stream microbial communities: A case study at the Rophin mining site.

This study aimed to assess the potential impact of long-term chronic exposure (69 years) to naturally-occurring radionuclides (RNs) and heavy metals on microbial communities in sediment from a stream flowing through a watershed impacted by an ancient mining site (Rophin, France). Four sediment samples were collected along a radioactivity gradient (for 238U368 to 1710 Bq.Kg-1) characterized for the presence of the bioavailable fractions of radionuclides (226Ra, 210Po), and trace metal elements (Th, U, As, Pb, Cu, Zn, Fe). Results revealed that the available fraction of contaminants was significant although it varied considerably from one element to another (0 % for As and Th, 5-59 % for U). Nonetheless, microbial communities appeared significantly affected by such chronic exposure to (radio)toxicities. Several microbial functions carried by bacteria and related with carbon and nitrogen cycling have been impaired. The high values of fungal diversity and richness observed with increasing downstream contamination (H' = 4.4 and Chao1 = 863) suggest that the community had likely shifted toward a more adapted/tolerant one as evidenced, for example, by the presence of the species Thelephora sp. and Tomentella sp. The bacterial composition was also affected by the contaminants with enrichment in Myxococcales, Acidovorax or Nostocales at the most contaminated points. Changes in microbial composition and functional structure were directly related to radionuclide and heavy metal contaminations, but also to organic matter which also significantly affected, directly or indirectly, bacterial and fungal compositions. Although it was not possible to distinguish the specific effects of RNs from heavy metals on microbial communities, it is essential to continue studies considering the available fraction of elements, which is the only one able to interact with microorganisms.

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.

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.

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.

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.

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.

High (36)Cl/Cl ratios in Chernobyl groundwater.

After the explosion of the Chernobyl Nuclear Power Plant in April 1986, contaminated material was buried in shallow trenches within the exclusion zone. A (90)Sr plume was evidenced downgradient of one of these trenches, trench T22. Due to its conservative properties, (36)Cl is investigated here as a potential tracer to determine the maximal extent of the contamination plume from the trench in groundwater. (36)Cl/Cl ratios measured in groundwater, trench soil water and leaf leachates are 1-5 orders of magnitude higher than the theoretical natural (36)Cl/Cl ratio. This contamination occurred after the Chernobyl explosion and currently persists. Trench T22 acts as an obvious modern point source of (36)Cl, however other sources have to be involved to explain such contamination. (36)Cl contamination of groundwater can be explained by dilution of trench soil water by uncontaminated water (rainwater or deep groundwater). With a plume extending further than that of (90)Sr, radionuclide which is impacted by retention and decay processes, (36)Cl can be considered as a suitable tracer of contamination from the trench in groundwater provided that modern release processes of (36)Cl from trench soil are better characterized.

Sufentanil is not superior to morphine for the treatment of acute traumatic pain in an emergency setting: a randomized, double-blind, out-of-hospital trial.

STUDY OBJECTIVE: We determine the best intravenous opioid titration protocol by comparing morphine and sufentanil for adult patients with severe traumatic acute pain in an out-of-hospital setting, with a physician providing care. METHODS: In this double-blind randomized clinical trial, patients were eligible for inclusion if aged 18 years or older, with acute severe pain (defined as a numeric rating scale score ≥ 6/10) caused by trauma. They were assigned to receive either intravenous 0.15 µg/kg sufentanil, followed by 0.075 µg/kg every 3 minutes or intravenous 0.15 mg/kg morphine and then 0.075 mg/kg. The primary endpoint of the study was pain relief at 15 minutes, defined as a numeric rating scale less than or equal to 3 of 10. Secondary endpoints were time to analgesia, adverse events, and duration of analgesia during the first 6 hours. RESULTS: A total of 108 patients were included, 54 in each group. At 15 minutes, 74% of the patients in the sufentanil group had a numeric rating scale score of 3 or lower versus 70% of those in the morphine group (Δ4%; 95% confidence interval -13% to 21%). At 9 minutes, 65% of the patients in the sufentanil group experienced pain relief versus 46% of those in the morphine group (Δ18%; 95% confidence interval 0.1% to 35%). The duration of analgesia was in favor of the morphine group. Nineteen percent of patients experienced an adverse event in both groups, all mild to moderate. CONCLUSION: Intravenous morphine titration using a loading dose of morphine followed by strictly administered lower doses at regular intervals remains the criterion standard. Moreover, this study supports the idea that the doses studied should be considered for routine administration in severe pain protocols.