The Mobilization of Actinides by Microbial Ligands Taking into Consideration the Final Storage of Nuclear Waste - Interactions of Selected Actinides U(VI), Cm(III), and Np(V) with Pyoverdins Secreted by Pseudomonas fluorescens and Related Model Compounds (Final Report BMBF Project No.: 02E9985)

The groundwater bacterium Pseudomonas fluorescens (CCUG 32456) isolated at a depth of 70 m in the Äspö Hard Rock Laboratory secretes a pyoverdin-mixture with four main components (two pyoverdins and two ferribactins). The dominant influence of the pyoverdins of this mixture could be demonstrated by an absorption spectroscopy study. The comparison of the stability constants of U(VI), Cm(III), and Np(V) species with ligands simulating the functional groups of the pyoverdins results in the following order of complex strength: pyoverdins (PYO) > trihydroxamate (DFO) > catecholates (NAP, 6­HQ) > simple hydroxamates (SHA, BHA). The pyoverdin chromophore functionality shows a large affinity to bind actinides. As a result, pyoverdins are also able to complex and to mobilize elements other than Fe(III) at a considerably high efficiency. It is known that EDTA may form the strongest actinide complexes among the various organic components in nuclear wastes. The stability constants of 1:1 species formed between Cm(III) and U(VI) and pyoverdins are by a factor of 1.05 and 1.3, respectively, larger compared to the corresponding EDTA stability constants. The Np(V)-PYO stability constant is even by a factor of 1.83 greater than the EDTA stability constant. The identified Np(V)-PYO species belong to the strongest Np(V) species with organic material reported so far. All identified species influence the actinide speciation within the biologically relevant pH range. The metal binding properties of microbes are mainly determined by functional groups of their cell wall (LPS: Gram-negative bacteria and PG: Gram-positive bacteria). On the basis of the determined stability constants raw estimates are possible, if actinides prefer to interact with the microbial cell wall components or with the secreted pyoverdin bioligands. By taking pH 5 as an example, U(VI)-PYO interactions are slightly stronger than those observed with LPS and PG. For Cm(III) we found a much stronger affinity to aqueous pyoverdin species than to functional groups of the cell wall compartments. A similar behavior was observed for Np(V). This shows the importance of indirect interaction processes between actinides and bioligands secreted by resident microbes

Biosorption and Biomineralization of U(VI) by the Marine Bacterium Idiomarina loihiensis MAH1: Effect of Background Electrolyte and pH

The main goal of this study is to compare the effects of pH, uranium concentration, and background electrolyte (seawater and NaClO4 solution) on the speciation of uranium(VI) associated with the marine bacterium Idiomarina loihiensis MAH1. This was done at the molecular level using a multidisciplinary approach combining X-ray Absorption Spectroscopy (XAS), Time-Resolved Laser-Induced Fluorescence Spectroscopy (TRLFS), and High Resolution Transmission Electron Microscopy (HRTEM). We showed that the U(VI)/bacterium interaction mechanism is highly dependent upon pH but also the nature of the used background electrolyte played a role. At neutral conditions and a U concentration ranging from 5·10−4 to 10−5 M (environmentally relevant concentrations), XAS analysis revealed that uranyl phosphate mineral phases, structurally resembling meta-autunite [Ca(UO2)2(PO4)2 2–6H2O] are precipitated at the cell surfaces of the strain MAH1. The formation of this mineral phase is independent of the background solution but U(VI) luminescence lifetime analyses demonstrated that the U(VI) speciation in seawater samples is more intricate, i.e., different complexes were formed under natural conditions. At acidic conditions, pH 2, 3 and 4.3 ([U] = 5·10−4 M, background electrolyte = 0.1 M NaClO4), the removal of U from solution was due to biosorption to Extracellular Polysaccharides (EPS) and cell wall components as evident from TEM analysis. The LIII-edge XAS and TRLFS studies showed that the biosorption process observed is dependent of pH. The bacterial cell forms a complex with U through organic phosphate groups at pH 2 and via phosphate and carboxyl groups at pH 3 and 4.3, respectively. The differences in the complexes formed between uranium and bacteria on seawater compared to NaClO4 solution demonstrates that the actinide/microbe interactions are influenced by the three studied factors, i.e., the pH, the uranium concentration and the chemical composition of the solution.This work was funded by the grants CGL2009-09760 and CGL2012-36505 (Ministerio de Ciencia e Innovación), and RNM 3943 (Junta de Andalucía), Spain

Aqueous batteries as grid scale energy storage solutions

Energy storage technologies are required to make full use of renewable energy sources, and electrochemical cells offer a great deal flexibility in the design of energy systems. For large scale electrochemical storage to be viable, the materials employed and device production methods need to be low cost, devices should be long lasting and safety during operation is of utmost importance. Energy and power densities are of lesser concern. For these reasons, battery chemistries that make use of aqueous electrolytes are favorable candidates where large quantities of energy need to be stored. Herein we describe several different aqueous based battery chemistries and identify some of the research challenges currently hindering their wider adoption. Lead acid batteries represent a mature technology that currently dominates the battery market, however there remain challenges that may prevent their future use at the large scale. Nickel–iron batteries have received a resurgence of interest of late and are known for their long cycle lives and robust nature however improvements in efficiency are needed in order to make them competitive. Other technologies that use aqueous electrolytes and have the potential to be useful in future large-scale applications are briefly introduced. Recent investigations in to the design of nickel–iron cells are reported with it being shown that electrolyte decomposition can be virtually eliminated by employing relatively large concentrations of iron sulfide in the electrode mixture, however this is at the expense of capacity and cycle life

The Mobilization of Actinides by Microbial Ligands Taking into Consideration the Final Storage of Nuclear Waste - Interactions of Selected Actinides U(VI), Cm(III), and Np(V) with Pyoverdins Secreted by Pseudomonas fluorescens and Related Model Compounds (Final Report BMBF Project No.: 02E9985)

The groundwater bacterium Pseudomonas fluorescens (CCUG 32456) isolated at a depth of 70 m in the Äspö Hard Rock Laboratory secretes a pyoverdin-mixture with four main components (two pyoverdins and two ferribactins). The dominant influence of the pyoverdins of this mixture could be demonstrated by an absorption spectroscopy study. The comparison of the stability constants of U(VI), Cm(III), and Np(V) species with ligands simulating the functional groups of the pyoverdins results in the following order of complex strength: pyoverdins (PYO) > trihydroxamate (DFO) > catecholates (NAP, 6­HQ) > simple hydroxamates (SHA, BHA). The pyoverdin chromophore functionality shows a large affinity to bind actinides. As a result, pyoverdins are also able to complex and to mobilize elements other than Fe(III) at a considerably high efficiency. It is known that EDTA may form the strongest actinide complexes among the various organic components in nuclear wastes. The stability constants of 1:1 species formed between Cm(III) and U(VI) and pyoverdins are by a factor of 1.05 and 1.3, respectively, larger compared to the corresponding EDTA stability constants. The Np(V)-PYO stability constant is even by a factor of 1.83 greater than the EDTA stability constant. The identified Np(V)-PYO species belong to the strongest Np(V) species with organic material reported so far. All identified species influence the actinide speciation within the biologically relevant pH range. The metal binding properties of microbes are mainly determined by functional groups of their cell wall (LPS: Gram-negative bacteria and PG: Gram-positive bacteria). On the basis of the determined stability constants raw estimates are possible, if actinides prefer to interact with the microbial cell wall components or with the secreted pyoverdin bioligands. By taking pH 5 as an example, U(VI)-PYO interactions are slightly stronger than those observed with LPS and PG. For Cm(III) we found a much stronger affinity to aqueous pyoverdin species than to functional groups of the cell wall compartments. A similar behavior was observed for Np(V). This shows the importance of indirect interaction processes between actinides and bioligands secreted by resident microbes

Measurement, model prediction and uncertainty quantification of plasma clearance of cerium citrate in humans.

Double tracer studies in healthy human volunteers with stable isotopes of cerium citrate were performed with the aim of investigating the gastro-intestinal absorption of cerium (Ce), its plasma clearance and urinary excretion. In the present work, results of the clearance of Ce in blood plasma are shown after simultaneous intravenous and oral administration of a Ce tracer. Inductively coupled plasma mass spectrometry was used to determine the tracer concentrations in plasma. The results show that about 80% of the injected Ce citrate cleared from the plasma within the 5 mins post-administration. The data obtained are compared to a revised biokinetic model of Ce, which was initially developed by the International Commission on Radiological Protection (ICRP). The measured plasma clearance of Ce citrate was mostly consistent with that predicted by the ICRP biokinetic model. Furthermore, in an effort to quantify the uncertainty of the model prediction, the laboratory animal data on which the ICRP biokinetic Ce model is based, was analyzed. The measured plasma clearance and its uncertainty was also compared to the plasma clearance uncertainty predicted by the model. It was found that the measured plasma clearance during the first 15 min after administration is in a good agreement with the modelled plasma clearance. In general, the measured clearance falls inside the 95% confidence interval predicted by the biokinetic model

The Mobilization of Actinides by Microbial Ligands Taking into Consideration the Final Storage of Nuclear Waste - Interactions of Selected Actinides U(VI), Cm(III), and Np(V) with Pyoverdins Secreted by Pseudomonas fluorescens and Related Model Compounds (Final Report BMBF Project No.: 02E9985)

The groundwater bacterium Pseudomonas fluorescens (CCUG 32456) isolated at a depth of 70 m in the Äspö Hard Rock Laboratory secretes a pyoverdin-mixture with four main components (two pyoverdins and two ferribactins). The dominant influence of the pyoverdins of this mixture could be demonstrated by an absorption spectroscopy study. The comparison of the stability constants of U(VI), Cm(III), and Np(V) species with ligands simulating the functional groups of the pyoverdins results in the following order of complex strength: pyoverdins (PYO) > trihydroxamate (DFO) > catecholates (NAP, 6­HQ) > simple hydroxamates (SHA, BHA). The pyoverdin chromophore functionality shows a large affinity to bind actinides. As a result, pyoverdins are also able to complex and to mobilize elements other than Fe(III) at a considerably high efficiency. It is known that EDTA may form the strongest actinide complexes among the various organic components in nuclear wastes. The stability constants of 1:1 species formed between Cm(III) and U(VI) and pyoverdins are by a factor of 1.05 and 1.3, respectively, larger compared to the corresponding EDTA stability constants. The Np(V)-PYO stability constant is even by a factor of 1.83 greater than the EDTA stability constant. The identified Np(V)-PYO species belong to the strongest Np(V) species with organic material reported so far. All identified species influence the actinide speciation within the biologically relevant pH range. The metal binding properties of microbes are mainly determined by functional groups of their cell wall (LPS: Gram-negative bacteria and PG: Gram-positive bacteria). On the basis of the determined stability constants raw estimates are possible, if actinides prefer to interact with the microbial cell wall components or with the secreted pyoverdin bioligands. By taking pH 5 as an example, U(VI)-PYO interactions are slightly stronger than those observed with LPS and PG. For Cm(III) we found a much stronger affinity to aqueous pyoverdin species than to functional groups of the cell wall compartments. A similar behavior was observed for Np(V). This shows the importance of indirect interaction processes between actinides and bioligands secreted by resident microbes

Role of the hydroxo function of citric acid within the Am(III) complexation

International audienceAlpha-hydroxycarboxylic acids are important molecules that can be used as complexing agent or buffer in aqueous phase in actinide selective separation processes. They are also present in the environment as a degradation product of cellulose. Therefore the alpha these molecules are likely to influence the speciation in the fuel cycle processes as well as in the migration mechanisms. In this double context, the behavior and complexation of americium with this type of ligand was studied, taking citric acid as a representative of this family. Actinide(III)-citric acid system was already examined, but most of the studies are incomplete because the citric acid is one of the most complicated compounds of the family due to its three carboxylic acids able to be deprotonated and to coordinate the metallic cation. On one side, the thermodynamic studies provide only complexation constants and the stoichiometry [ , ] of the different complexes without any information on the coordination spheres (the number of complexing carboxylate groups, the presence or not of the hydroxo function as a coordinating group and the ligand protonation state). On the other side, the rare structural studies relate to polynuclear [ ] or polymeric species [ , , , ] unlike the complexes identified in solution in the previous thermodynamic studies. In this study, thermodynamics and structural data were assessed in solution for the same chemical conditions to finally describe the speciation of the Am(III)-citrate system. A focus was done on the role played by the hydroxyl group does it coordinate the actinide? Is it protonated? To better understand its role, the Am-citrate system was compared to the Am-tricarballylate system (analogue to citric acid without the hydroxyl group). The complexation constants have been determined and the complexes were characterized using X-ray absorption, NMR, TRLFS and capillary electrophoresis

Uranium(VI) Binding Forms in Selected Human Body Fluids: Thermodynamic Calculations versus Spectroscopic Measurements

Human exposure to uranium increasingly becomes a subject of interest in many scientific disciplines such as environmental medicine, toxicology, and radiation protection. Knowledge about uranium chemical binding forms (speciation) in human body fluids can be of great importance to understand not only its biokinetics but also its relevance in risk assessment and in designing decorporation therapy in the case of accidental overexposure. In this study, thermodynamic calculations of uranium speciation in relevant simulated and original body fluids were compared with spectroscopic data after ex-situ uranium addition. For the first time, experimental data on U­(VI) speciation in body fluids (saliva, sweat, urine) was obtained by means of cryogenic time-resolved laser-induced fluorescence spectroscopy (cryo-TRLFS) at 153 K. By using the time dependency of fluorescence decay and the band positions of the emission spectra, various uranyl complexes were demonstrated in the studied samples. The variations of the body fluids in terms of chemical composition, pH, and ionic strength resulted in different binding forms of U­(VI). The speciation of U­(VI) in saliva and in urine was affected by the presence of bioorganic ligands, whereas in sweat, the distribution depends mainly on inorganic ligands. We also elucidated the role of biological buffers, i.e., phosphate (H₂PO₄^–/HPO₄^2–) on U­(VI) distribution, and the system Ca²⁺/UO₂²⁺/PO₄^3– was discussed in detail in both saliva and urine. The theoretical speciation calculations of the main U­(VI) species in the investigated body fluids were significantly consistent with the spectroscopic data. Laser fluorescence spectroscopy showed success and reliability for direct determination of U­(VI) in such biological matrices with the possibility for further improvement