Synchrotron-Based X-ray Fluorescence Imaging Elucidates Uranium Toxicokinetics in Daphnia magna.

A combination of synchrotron-based elemental analysis and acute toxicity tests was used to investigate the biodistribution and adverse effects in Daphnia magna exposed to uranium nanoparticle (UNP, 3-5 nm) suspensions or to uranium reference (Uref) solutions. Speciation analysis revealed similar size distributions between exposures, and toxicity tests showed comparable acute effects (UNP LC50: 402 µg L-1 [336-484], Uref LC50: 268 µg L-1 [229-315]). However, the uranium body burden was 3- to 5-fold greater in UNP-exposed daphnids, and analysis of survival as a function of body burden revealed a ∼5-fold higher specific toxicity from the Uref exposure. High-resolution X-ray fluorescence elemental maps of intact, whole daphnids from sublethal, acute exposures of both treatments revealed high uranium accumulation onto the gills (epipodites) as well as within the hepatic ceca and the intestinal lumen. Uranium uptake into the hemolymph circulatory system was inferred from signals observed in organs such as the heart and the maxillary gland. The substantial uptake in the maxillary gland and the associated nephridium suggests that these organs play a role in uranium removal from the hemolymph and subsequent excretion. Uranium was also observed associated with the embryos and the remnants of the chorion, suggesting uptake in the offspring. The identification of target organs and tissues is of major importance to the understanding of uranium and UNP toxicity and exposure characterization that should ultimately contribute to reducing uncertainties in related environmental impact and risk assessments.

Limited access to oxygen reduces the release of harmful trace elements from submerged alum shale debris.

Construction and mining activities in acid-producing alum shale regions often produce large volumes of crushed rock. Disposal under groundwater level (e.g., a bog) may minimize oxygen access. In this study, the effect of varying oxygen access on the leaching potential of alum shale was investigated by submerging tunnel construction rock debris in synthetic rainwater under atmospheric (AOC) and low oxygen conditions (LOC) for 52 weeks. The sulphate increase and nitrate decrease in the leachates suggested that pyrite (FeS2) in the alum shale was oxidized, but carbonates originating from calcite dissolution provided sufficient buffering capacity (leachate pH ~7.7 over 52 weeks), resulting in neutral rock drainage. Less available oxygen led to significantly lower production of sulphate and acid from pyrite oxidation, reducing the release of harmful elements. Under LOC, the leaching of Mo, Co, Ni, Zn and Cd was 2-4 times lower than under AOC and the lower buffering requirement diminished the release of Ca as well as divalent cations (Mg, Sr, Mn) likely present as impurities in calcite. Contrastingly, limited pyrite oxidation led to less oversaturation with respect to BaSO4 and lower release of Fe in the LOC leachates. Thus, co-precipitation of 226Ra was inhibited and scavenging of leached V, As and Sb by newly formed Fe(OH)3 was not as dominant as in the AOC systems. Leaching of U was ~20 % higher under LOC likely due to enhanced complexation by dissolved carbonate. In general, element leaching rates were slower under low O2 levels. Characterization of water collected at the disposal site after ~1.2 years of discarding tunnel materials showed that the weathering of debris submerged in the open, water-filled pond occurred similarly to leaching under low oxygen conditions. Overall, these results highlight the importance of minimal oxygen access or anaerobic conditions when acid-producing rock waste is stored under water.

Synchrotron XRF and Histological Analyses Identify Damage to Digestive Tract of Uranium NP-Exposed Daphnia magna.

Micro- and nanoscopic X-ray techniques were used to investigate the relationship between uranium (U) tissue distributions and adverse effects to the digestive tract of aquatic model organism Daphnia magna following uranium nanoparticle (UNP) exposure. X-ray absorption computed tomography measurements of intact daphnids exposed to sublethal concentrations of UNPs or a U reference solution (URef) showed adverse morphological changes to the midgut and the hepatic ceca. Histological analyses of exposed organisms revealed a high proportion of abnormal and irregularly shaped intestinal epithelial cells. Disruption of the hepatic ceca and midgut epithelial tissues implied digestive functions and intestinal barriers were compromised. Synchrotron-based micro X-ray fluorescence (XRF) elemental mapping identified U co-localized with morphological changes, with substantial accumulation of U in the lumen as well as in the epithelial tissues. Utilizing high-resolution nano-XRF, 400-1000 nm sized U particulates could be identified throughout the midgut and within hepatic ceca cells, coinciding with tissue damages. The results highlight disruption of intestinal function as an important mode of action of acute U toxicity in D. magna and that midgut epithelial cells as well as the hepatic ceca are key target organs.

Selenium Speciation Analysis Reveals Improved Antioxidant Status in Finisher Pigs Fed L-Selenomethionine, Alone or Combined with Sodium Selenite, and Vitamin E.

Conditions associated with selenium (Se) and/or vitamin E (VitE) deficiency are still being reported in high-yielding pigs fed the recommended amounts. Here, the dietary effects of Se source (sodium selenite, NaSe, 0.40 or 0.65 mg Se/kg; L-selenomethionine, SeMet, 0.19 or 0.44 mg Se/kg; a NaSe-SeMet mixture, SeMix, 0.44-0.46 mg Se/kg) and VitE concentration (27, 50-53 or 101 mg/kg) on the antioxidant status of finisher pigs were compared with those in pigs fed non-Se-supplemented diets (0.08-0.09 mg Se/kg). Compared to NaSe-enriched diets, SeMet-supplemented diets resulted in significantly (p < 0.0018) higher plasma concentrations of total Se (14-27%) and selenospecies (GPx3, SelP, SeAlb; 7-83%), significantly increased the total Se accumulation in skeletal muscles, myocardium, liver and brain (10-650%), and enhanced the VitE levels in plasma (15-74%) and tissues (8-33%) by the end of the 80-day trial, proving better Se distribution and retention in pigs fed organic Se. Injecting lipopolysaccharide (LPS) intravenously half-way into the trial provoked a pyrogenic response in the pigs followed by a rapid increase of inorganic Se after 5-12 h, a drastic drop of SeMet levels between 12 and 24 h that recovered by 48 h, and a small increase of SeCys by 24-48 h, together with a gradual rise of GPx3, SelP and SeAlb in plasma up to 48 h. These changes in Se speciation in plasma were particularly significant (0.0024 > p > 0.00007) in pigs receiving SeMet- (0.44 mg Se/kg, above EU-legislated limits) or SeMix-supplemented (SeMet and NaSe both at 0.2 mg Se/kg, within EU-legislated limits) diets, which demonstrates Se metabolism upregulation to counteract the LPS-induced oxidative stress and a strengthened antioxidant capacity in these pigs. Overall, a Se source combination (without exceeding EU-legislated limits) and sufficient VitE supplementation (≥ 50 mg/kg) improved the pigs' antioxidant status, while doubling the allowed dietary organic Se increased the Se in tissues up to sixfold without compromising the animal's health due to toxicity. This study renders valuable results for revising the current dietary SeMet limits in swine rations.

Effects of flow on uranium speciation in soils impacted by acidic waste fluids.

Radioactive acidic liquid waste is a common byproduct of uranium (U) and plutonium (Pu) enrichment and recycling processes whose accidental and planned release has led to a significant input of U into soils and sediments across the world, including at the U.S. DOE's Hanford site (WA, USA). Because of the particularly hazardous nature of U, it is important to predict its speciation when introduced into soils and sediments by acidic waste fluids. Of fundamental importance are the coupled effects of acid-driven mineral transformation and reactive transport on U speciation. To evaluate the effect of waste-fluid residence time and co-associated dissolved phosphate concentrations on U speciation in impacted soils and sediments, uncontaminated surface materials (from the Hanford Site) were reacted with U-containing synthetic acidic waste fluids (pH 2) amended with dissolved phosphate concentrations in both batch (no flow) and flow-through column systems for 7-365 days. By comparing dissolved U behavior and solid phase speciation as a function of flow regimen, we found that the availability of proton-promoted dissolution products (such as Si) to sequester U into uranyl silicates was dependent on waste fluid-sediment contact time as uranyl silicates were not detected in short contact time flow-through systems but were detected in no-flow, long contact time, reactors. Moreover, the dominance of uranyl phosphate as neoprecipitate U scavenger (principally in the form of meta-ankoleite) in phosphate amended systems confirmed the importance of phosphate amendments for an efficient sequestration of U in the soils and sediments. Overall, our experiments suggest that the formation of uranyl silicates in soils impacted by acidic waste fluids is likely to be limited unless reaction products are allowed to accumulate in soil pores, highlighting the importance of investigating soil U speciation in flow-through, transport-driven systems as opposed to no-flow, batch systems. This study provides insights into uranium speciation and its potential changes under acidic conditions for better prediction of risks and subsequent development of efficient remediation strategies.

Phosphate controls uranium release from acidic waste-weathered Hanford sediments.

Mineral dissolution and secondary phase precipitation may control the fate of inorganic contaminants introduced to soils and sediments during liquid waste discharges. When the solutions are aggressive enough to induce transformation of native minerals, incorporated contaminants may be released during dissolution due to percolation of meteoric waters. This study evaluated the release of uranium (U) from Hanford sediments that had been previously reacted for 180 or 365 days with liquid waste solutions containing U with and without 3 mM dissolved phosphate at pH 2 and 3. Flow-through column experiments were conducted under continuous saturated flow with a simulated background porewater (BPW; pH ~7) for 22 d. Up to 5% of the total U was released from the sediments reacted under PO4-free conditions, attributable to the dissolution of becquerelite and boltwoodite formed during weathering. Contrastingly, negligible U was released from PO4-reacted sediments, where meta-ankoleite was identified as the main U-mineral phase. Linear combination fits of U LIII-edge EXAFS spectra of sediments before and after BPW leaching and thermodynamic calculations suggest that the formed becquerelite and meta-ankoleite transformed into schoepite and a phosphuranylite-type phase, respectively. These results demonstrate the stabilization of U as recalcitrant uranyl minerals formed in sediments and highlight the key role of PO4 in U release at contaminated sites.

Dissolved Carbonate and pH Control the Dissolution of Uranyl Phosphate Minerals in Flow-Through Porous Media.

Uranyl phosphate minerals represent an important secondary source of uranium release at contaminated sites. In flow-through column experiments with background porewater (BPW) of typical freshwater aquifer composition (pH 7.0, ∼0.2 mM total carbonate (TC)), dissolution of K-ankoleite (KUO2PO4·3H2O), Na-autunite (NaUO2PO4·3H2O), and Ca-autunite (Ca(UO2)2(PO4)2·6H2O) was controlled by mineral solubility at steady-state U release. Effluent concentrations indicated exchange with BPW cations, and postreaction characterization showed alteration of the initial mineral composition, changes in structure (decreased crystallinity, increased disorder, and distortion of U-P mineral sheets) and possible neoformation of phases of similar structure. Increasing the BPW pH and TC to 8.1-8.2 and 2.2-3.7 mM, respectively, resulted in mineral undersaturation and produced ca. 2 orders-of-magnitude higher U and P release without reaching steady state. Minerals incorporated less BPW cations into their structures compared to low carbonate BPW experiments but showed structural disorder and distortion. Faster dissolution rates were attributed to the formation of binary and ternary uranyl carbonate complexes that accelerate the rate-determining step of uranyl detachment from the uranyl-phosphate layered structure. Calculated dissolution rates (log Rs between -8.95 and -10.32 mol m-2 s-1), accounting for reaction and transport in porous media, were similar to dissolution rates of other classes of uranyl minerals. In undersaturated solutions, dissolution rates for uranyl phosphate, oxyhydroxide, and silicate minerals can be predicted within 1-2 orders-of-magnitude from pH ∼5-10 on the basis of pH/carbonate concentration.

Linking heterogeneous distribution of radiocaesium in soils and pond sediments in the Fukushima Daiichi exclusion zone to mobility and potential bioavailability.

During the Fukushima Daiichi Nuclear Power Plant (FDNPP) accident in 2011 significant amounts of radiocaesium were released into the atmosphere from the reactor units 1, 2 and 3. This caused a non-uniform deposition, in composition and direction, of 134Cs and 137Cs in the near field (<30 km) from the reactors. In this work, we elucidate the influence of speciation, including radioactive particles, on mobility and potential bioavailability of radiocaesium in soils and sediments from sites located in different directions and distances from the FDNPP. Samples collected in September 2016 were characterized and subjected to sequential chemical extractions and simulated gastrointestinal fluid leaching, and the 137Cs and 134Cs activities were determined in bulk, grain-size and extracted fractions. The results show that radiocaesium was mainly irreversibly bound and in an inert form. Combined, the two forms contained >90% of the activity present in soils and ~84% in sediments. Digital autoradiography revealed that the inert fraction was predominantly associated with heterogeneities, an indication of radioactive particles. The frequency of heterogeneities was correlated with 137Cs activity concentrations, and both were in agreement with the ambient equivalent air doses measured in situ during sampling. Moreover, in situ gamma spectrometry measurements were used in the InSiCal software tool to derive 134Cs and 137Cs surface contamination. Soil activity concentrations and contamination density estimations, decay-corrected to the day of the FDNPP accident, resulted in 134Cs/137Cs ratios that match the reported release and deposition plumes from the reactor units. Overall, these results demonstrate the persistence of the particle contamination in the Fukushima near field and highlight the importance of including radioactive particles in environmental impact assessments.

Beneficial antioxidant status of piglets from sows fed selenomethionine compared with piglets from sows fed sodium selenite.

BACKGROUND: Studies in mammals proved dietary organic selenium (Se) being superior to inorganic Se regarding effects on growth performance, antioxidative status, immune response, and Se homeostasis. However, the picture of possible effects of different Se sources and - levels can be expanded. The present field study evaluated the effects on weight gain, hematological and selected biochemical variables as well as plasma concentrations of vitamin E (vitE), total Se and selenobiomolecules in piglets throughout the suckling period. METHODS: Piglets were monitored from birth to 38 days of age (d). The mother sows' diets were enriched with l-selenomethionine (SeMet-0.26 and -0.43 mg Se/kg feed) or sodium selenite (NaSe-0.40 and -0.60 mg Se/kg feed) from 1 month prior to farrowing until the end of lactation period. Piglets received pelleted feed supplemented with Se similarly to the sows' diets from one week of age. Selenite at 0.40 mg Se/kg (NaSe-0.40) represents a common Se source and -level in pig feed and served as control diet. RESULTS: From 24d, piglets in SeMet-groups had higher mean body weight (BW) compared with piglets from sows fed NaSe-0.40. Furthermore, from five-d and above, piglets from sows fed NaSe-0.60 had significantly higher BW than offspring from sows fed NaSe-0.40. Neonatal piglets in group SeMet-0.43 had significantly lower red blood cell counts (RBC), hemoglobin (Hgb) and hematocrit (Hct) concentrations compared with piglets from sows fed with NaSe-0.40. Neonatal and 5d-old piglets in group SeMet-0.26 showed higher gamma-glutamyl transferase activity than piglets in group NaSe-0.40. From five d and above, group NaSe-0.60 excelled with increased specific hematological variables culminating at age 38d with increased Hct, mean corpuscular volume (MCV), and MC hemoglobin (MCH) as well as increased activities of aspartate transaminase and lactate dehydrogenase compared with the other groups. Generally, offspring in the SeMet groups had higher total Se-concentrations in plasma than those from sows fed selenite, and showed a dose-response effect on plasma Se-concentrations. Furthermore, SeMet-fed piglets had higher plasma levels of the selenoproteins (Sel) glutathione peroxidase 3 (GPx3) and SelP as well as selenoalbumin. Plasma vitE levels were significantly negatively correlated with RBC throughout trial period. CONCLUSIONS: Maternal supplementation with SeMet during gestation influenced hematology and clinical biochemistry in neonatal piglets in a different way than in offspring from sows receiving selenite enriched diets. Growth performance was positively influenced by both dietary Se source and Se level. Higher plasma levels of GPx3 observed in piglets receiving SeMet probably improved the protection against birth or growth related oxidative stress. These might prime the piglets for demanding situations as indicated by higher weight gain in offspring from sows fed with SeMet-supplemented diets. Our results on some enzyme activities might indicate that piglets fed NaSe-0.60 had to cope with increased levels of oxidative stress compared with those originating from sows fed SeMet or lower dietary levels of selenite. We assume that combining inorganic and organic Se sources in complete feed for breeding sows might be beneficial fro reproduction and the offspring's performance.

Uranium Release from Acidic Weathered Hanford Sediments: Single-Pass Flow-Through and Column Experiments.

The reaction of acidic radioactive waste with sediments can induce mineral transformation reactions that, in turn, control contaminant fate. Here, sediment weathering by synthetic uranium-containing acid solutions was investigated using bench-scale experiments to simulate waste disposal conditions at Hanford's cribs (Hanford, WA). During acid weathering, the presence of phosphate exerted a strong influence over uranium mineralogy and a rapidly precipitated, crystalline uranium phosphate phase (meta-ankoleite [K(UO2)(PO4)·3H2O]) was identified using spectroscopic and diffraction-based techniques. In phosphate-free system, uranium oxyhydroxide minerals such as K-compreignacite [K2(UO2)6O4(OH)6·7H2O] were formed. Single-pass flow-through (SPFT) and column leaching experiments using synthetic Hanford pore water showed that uranium precipitated as meta-ankoleite during acid weathering was strongly retained in the sediments, with an average release rate of 2.67 × 10-12 mol g-1 s-1. In the absence of phosphate, uranium release was controlled by dissolution of uranium oxyhydroxide (compreignacite-type) mineral with a release rate of 1.05-2.42 × 10-10 mol g-1 s-1. The uranium mineralogy and release rates determined for both systems in this study support the development of accurate U-release models for the prediction of contaminant transport. These results suggest that phosphate minerals may be a good candidate for uranium remediation approaches at contaminated sites.

Study of uranium(VI) and radium(II) sorption at trace level on kaolinite using a multisite ion exchange model.

Uranium and the long-lived decay product radium-226 are abundantly present in mine wastes produced during uranium extraction activities. In the case of release to the surrounding environment, these radionuclides are at trace level compared to groundwater solutes, and the presence, content and properties of clay minerals in the host environment influence the extent of radionuclide sorption and, in turn, migration. Since clays are known to have the distinctive property of retaining ions, the aim of this work was to study the sorption of trace U(VI) and Ra(II) on a common phyllosilicate mineral, kaolinite, in the presence of excess K, a common groundwater cation, in order to obtain a thermodynamic database that describes the ion exchange equilibria occurring at the mineral-solution interface. Following a detailed experimental protocol using chemical and radiochemical analytical techniques, batch experiments over a wide pH range (from 2 to 11) and fixed concentration (ca. 10(-9) M), and additional adsorption isotherms at two different solution pH (6.2 and 10.4) over a concentration range (10(-10) to 10(-4) M) were carried out to measure the distribution coefficient (Kd) of U(VI) and Ra(II) sorption on kaolinite. The experimental sorption data was processed according to a general multisite sorbent/multispecies sorbate ion exchange model, which allowed deducing the charge of adsorbed species and the stoichiometry of the associated adsorption equilibria on kaolinite's surface sites. Aqueous speciation calculations predicted Ra(II) as Ra(2+) over the working pH range, and its adsorption curves and isotherms were explained using three sorption sites. Adsorption of U(VI) occurred on four sorption sites and was governed by its solution speciation, with positively charged hydroxylated (UO2(2+) and UO2(OH)(+)) and silicate (UO2(H3SiO4)(+)) species being adsorbed between pH 2 and 6, whereas its negatively charged forms (UO2(OH)3(-) and UO2(OH)4(2-)) dominated U(VI) sorption at pH > 7. Nonlinear fitting of the experimental data using the ion exchange model provided the associated equilibrium constants as corrected selectivity coefficients.

Effect of organic complexing agents on the interactions of Cs(+), Sr(2+) and UO(2)(2+) with silica and natural sand.

Sorption processes play a key role in controlling radionuclide migration through subsurface environments and can be affected by the presence of anthropogenic organic complexing agents found at contaminated sites. The effect of these complexing agents on radionuclide-solid phase interactions is not well known. Therefore the aim of this study was to examine the processes by which EDTA, NTA and picolinate affect the sorption kinetics and equilibria of Cs(+), Sr(2+) and UO2(2+) onto natural sand. The caesium sorption rate and equilibrium were unaffected by the complexing agents. Strontium however showed greater interaction with EDTA and NTA in the presence of desorbed matrix cations than geochemical modelling predicted, with SrNTA(-) enhancing sorption and SrEDTA(2-) showing lower sorption than Sr(2+). Complexing agents reduced UO2(2+) sorption to silica and enhanced the sorption rate in the natural sand system. Elevated concentrations of picolinate reduced the sorption of Sr(2+) and increased the sorption rate of UO2(2+), demonstrating the potential importance of this complexing agent. These experiments provide a direct comparison of the sorption behaviour of Cs(+), Sr(2+) and UO2(2+)onto natural sand and an assessment of the relative effects of EDTA, NTA and picolinate on the selected elements.

Evaluation of electrospray ionisation mass spectrometry as a technique for the investigation of competitive interactions: a case study of the ternary Th-Mn-EDTA system.

RATIONALE: Electrospray ionisation mass spectrometry (ESI-MS) is a useful tool for exploring the speciation of solution-phase metal complexes; however, the quantification of ternary systems is challenging due to the differences in the electrospray response of different species. Here, the Th-Mn-EDTA system was investigated to evaluate the capability of ESI-MS for quantifying the species present. METHODS: Increasingly complex mixtures of Th(IV), Mn(II) and EDTA were analysed using manual flow injection of samples into an HPLC grade water mobile phase delivered to an ion trap mass spectrometer fitted with an ESI interface (ThermoQuest Finnigan Mat LCQ). Mass spectra were obtained in the positive and negative ion modes over a mass-to-charge (m/z) range from 50-2000. RESULTS: The instrumental response to EDTA was affected by the addition of Th(NO(3))(4) but not MnCl(2), while the response to both Th-EDTA and Mn-EDTA species was affected by addition of the other metal salt. Internal standards were also found to suppress signals to different extents. Therefore, each signal suppression was carefully quantified as the solution became more complex, and signal correction factors were used in conjunction with regular external calibration. Mixed metal signals were quantified adequately. CONCLUSIONS: This study showed the complexity of quantifying a ternary system involving different co-existing species. Nonetheless, the step-wise protocol developed provided quantitative data on the displacement of Mn from its EDTA complex by Th.

The effect of EDTA, NTA and picolinic acid on Th(IV) mobility in a ternary system with natural sand.

Organic complexing agents, such as ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA) and picolinic acid, have been widely used at nuclear sites and are therefore found as common co-contaminants in radioactive contaminated land. This study has explored the mechanisms by which these three complexing agents affect the sorption of Th(IV) to pure silica and a natural sand. EDTA, NTA and, to a lesser extent, picolinic acid decreased the sorption of Th to silica, demonstrating the formation and solubility of Th complexes. However, Th sorption to sand was kinetically controlled and complexation enhanced the rate of Th sorption. EDTA and NTA did not sorb significantly to the sand, and metal desorption indicated that the mechanism involved exchange with sand-associated metals. At equilibrium, however, Th sorption was not affected by the presence of the ligands, and modelling suggested that the interaction between Th and the surface binding sites controlled Th sorption thermodynamically.