Heino Nitsche

Uranyl(VI) carbonate complex formation: Validation of the Ca2UO2(CO3)3(aq.) species

We recently discovered a neutral dicalcium uranyl tricarbonate complex, Ca2UO2(CO3)3(aq.), in uranium mining related waters [1]. We are now reporting a further validation of the stoichiometry and the formation constant of this complex using two analytical approaches with time-resolved laser-induced fluorescence spectroscopy (TRLFS) species detection: i) titration of a non-fluorescent uranyl tricarbonate complex solution with calcium ions, and quantitative determination of the produced fluorescent calcium complex via TRLFS; and ii) variation of the calcium concentration in the complex by competitive calcium complexation with EDTA4-. Slope analysis of the log (fluorescence intensity) versus log[Ca2+] with both methods have shown that two calcium ions are bound to form the complex Ca2UO2(CO3)3(aq.). The formation constants determined from the two independent methods are: i) logβ°213=30.45±0.35 and ii) logβ°213=30.77±0.25. A bathochrome shift of 0.35 nm between the UO2(CO3)34- complex and the Ca2UO2(CO3)3(aq.) complex is observed in the laser-induced photoacoustic spectrum (LIPAS), giving additional evidence for the formation of the calcium uranyl carbonate complex. EXAFS spectra at the LII and LIII-edges of uranium in uranyl carbonate solutions with and without calcium do not differ significantly. A somewhat better fit to the EXAFS of the Ca2UO2(CO3)3(aq.) complex is obtained by including the U-Ca shell. From the similarities between the EXAFS of the Ca2UO2(CO3)3(aq.) species in solution and the natural mineral liebigite, we conclude that the calcium atoms are likely to be in the same positions both in the solution complex and in the solid. This complex influences considerably the speciation of uranium in the pH region from 6 to 10 in calcium-rich uranium-mining-related waters.

Chemical investigation of hassium (element 108).

The periodic table provides a classification of the chemical properties of the elements. But for the heaviest elements, the transactinides, this role of the periodic table reaches its limits because increasingly strong relativistic effects on the valence electron shells can induce deviations from known trends in chemical properties. In the case of the first two transactinides, elements 104 and 105, relativistic effects do indeed influence their chemical properties, whereas elements 106 and 107 both behave as expected from their position within the periodic table. Here we report the chemical separation and characterization of only seven detected atoms of element 108 (hassium, Hs), which were generated as isotopes 269Hs (refs 8, 9) and 270Hs (ref. 10) in the fusion reaction between 26Mg and 248Cm. The hassium atoms are immediately oxidized to a highly volatile oxide, presumably HsO4, for which we determine an enthalpy of adsorption on our detector surface that is comparable to the adsorption enthalpy determined under identical conditions for the osmium oxide OsO4. These results provide evidence that the chemical properties of hassium and its lighter homologue osmium are similar, thus confirming that hassium exhibits properties as expected from its position in group 8 of the periodic table.

ROBL – a CRG beamline for radiochemistry and materials research at the ESRF

The paper describes the Rossendorf beamline (ROBL) built by the Forschungszentrum Rossendorf at the ESRF. ROBL comprises two different and independently operating experimental stations: a radiochemistry laboratory for X-ray absorption spectroscopy of non-sealed radioactive samples and a general purpose materials research station for X-ray diffraction and reflectometry mainly of thin films and interfaces modified by ion beam techniques.

Sorption behavior of U(VI) on phyllite: experiments and modeling.

The sorption of U(VI) onto low-grade metamorphic rock phyllite was modeled with the diffuse double layer model (DDLM) using the primary mineralogical constituents of phyllite, i.e. quartz, chlorite, muscovite, and albite, as input components, and as additional component, the poorly ordered Fe oxide hydroxide mineral, ferrihydrite. Ferrihydrite forms during the batch sorption experiment as a weathering product of chlorite. In this process, Fe(II), leached from the chlorite, oxidizes to Fe(III), hydrolyses and precipitates as ferrihydrite. The formation of ferrihydrite during the batch sorption experiment was identified by Mössbauer spectroscopy, showing a 2.8% increase of Fe(III) in the phyllite powder. The ferrihydrite was present as Fe nanoparticles or agglomerates with diameters ranging from 6 to 25 nm, with indications for even smaller particles. These Fe colloids were detected in centrifugation experiments of a ground phyllite suspension using various centrifugal forces. The basis for the successful interpretation of the experimental sorption data of uranyl(VI) on phyllite were: (1) the determination of surface complex formation constants of uranyl with quartz, chlorite, muscovite, albite, and ferrihydrite in individual batch sorption experiments, (2) the determination of surface acidity constants of quartz, chlorite, muscovite, and albite obtained from separate acid-base titration, (3) the determination of surface site densities of quartz, chlorite, muscovite, and albite evaluated independently of each other with adsorption isotherms, and (4) the quantification of the secondary phase ferrihydrite, which formed during the batch sorption experiments with phyllite. The surface complex formation constants and the protolysis constants were optimized by using the experimentally obtained data sets and the computer code FITEQL. Surface site densities were evaluated from adsorption isotherms at pH 6.5. The uranyl(VI) sorption onto phyllite was accurately modeled with these newly determined constants and parameters of the main mineralogical constituents of phyllite and the secondary mineralization phase ferrihydrite. The modeling indicated that uranyl sorption to ferrihydrite clearly dominates uranyl sorption, showing the great importance of secondary iron phases for sorption studies.

Study of uranyl(VI) malonate complexation by time-resolved laser-induced fluorescence spectroscopy (TRLFS)

Summary The uranyl(VI) malonate complex formation was studied by time-resolved laser-induced fluorescence spectroscopy (TRLFS) at pH 4 and an ionic strength of 0.1 M NaClO4. The uranium concentration was 5 × 10−6 M at ligand concentrations from 1 × 10−5 to 1 × −2 M. The measured fluorescence lifetimes of the 1:1 and 1:2 uranyl(VI) malonate complexes are 1.24 ± 0.02 µs and 6.48 ± 0.02 µs, respectively. The fluorescence lifetime of the uranyl(VI) ion is 1.57 ± 0.06 µs in 0.1 M perchloric media. The main fluorescence bands of the malonate complexes show a bathochromic shift compared to the uranyl(VI) ion and are centered at 494 nm, 515 nm and 540 nm for the 1:1 complexes and at 496 nm, 517 nm and 542 nm for the 1:2 complex. The spectra of the individual uranyl(VI) malonate complexes were calculated using a multi exponential fluorescence decay function for each intensity value at each wavelength, covering the entire wavelength range. Stability constants were determined for the complexes UO2C3H2O4°(aq) and UO2(C3H2O4)22− from results of spectra deconvolution using a least square fit algorithm (logβ1° = 4.48 ± 0.06, logβ2° = 7.42 ± 0.06 or logK2° = 2.94 ± 0.04). The results are compared with literature values obtained by potentiometric measurements.

URANIUM(VI) SULFATE COMPLEXATION STUDIED BY TIME-RESOLVED LASER-INDUCED FLUORESCENCE SPECTROSCOPY (TRLFS)

The use of the ΟΡΟ technique in laser induced spectroscopic instrumentation is a new and improved spectroscopic technique. Solid crystals for the tunable laser allows one to perform laser spectroscopy over a wide wavelength range without the use of a dye laser. We have demonstrated that the laser output of the ΟΡΟ-system (in our case 270 nm) is suitable for time-resolved laser-induced fluorescence measurements. The uranyl sulfate complexation was investigated for the first time by fluorescence measurements. Compared to spectrophotometric methods, lower uranyl concentrations can be investigated and therefore measurements could be made in seepage waters of uranium mine tailing piles. The measured lifetimes of the 1:1, 1:2, and 1:3 uranyl sulfate complexes are 4.3 + / 0.5 μβ, 11.0 + / 1.0 με and 18.8 + / 1.0 μβ, respectively. The main fluorescence bands of the sulfate complexes are centered at 498 nm, 515 nm and 538 nm and no significant shift of the fluorescence maxima was found between the three complexes. The complex formation constants of the first two uranyl sulfate complexes at an ionic strength of 0.2 M were measured as log βι(ο.2Μ) = 2.42 and log β2(0 2 M) 3.30, respectively. The complex formation constants for the three uranyl sulfate complexes at an ionic strength of 1 M were measured as log β1(1οΜ) = 1-88, log β2.(, 0M) = 2.9 and log β3(ι.0Μ) = 3.2, respectively. A speciation diagram was calculated from the results of the time resolved measurements.

Uranyl Precipitation by Pseudomonas aeruginosa via Controlled Polyphosphate Metabolism

ABSTRACT The polyphosphate kinase gene from Pseudomonas aeruginosa was overexpressed in its native host, resulting in the accumulation of 100 times the polyphosphate seen with control strains. Degradation of this polyphosphate was induced by carbon starvation conditions, resulting in phosphate release into the medium. The mechanism of polyphosphate degradation is not clearly understood, but it appears to be associated with glycogen degradation. Upon suspension of the cells in 1 mM uranyl nitrate, nearly all polyphosphate that had accumulated was degraded within 48 h, resulting in the removal of nearly 80% of the uranyl ion and >95% of lesser-concentrated solutions. Electron microscopy, energy-dispersive X-ray spectroscopy, and time-resolved laser-induced fluorescence spectroscopy (TRLFS) suggest that this removal was due to the precipitation of uranyl phosphate at the cell membrane. TRLFS also indicated that uranyl was initially sorbed to the cell as uranyl hydroxide and was then precipitated as uranyl phosphate as phosphate was released from the cell. Lethal doses of radiation did not halt phosphate secretion from polyphosphate-filled cells under carbon starvation conditions.

Uranium speciation in waters of different uranium mining areas

Abstract The uranium speciation in three uranium mining-related waters from Saxony/Germany was experimentally determined by laser spectroscopy. The obtained species distributions were successfully compared with modeling predictions for the different U(VI) species that were calculated with the modeling software EQ3/6 using the NEA data base 1 , 2 . Three different solution complexes characterize the uranium speciation in the investigated waters: 1. In carbonate- and calcium-containing mine water from Schlema at pH 7.1, Ca2UO2(CO3)3 (aq.); 2. In carbonate-containing and calcium-poor tailing water from Helmsdorf at pH 9.8, UO2(CO3)34−; 3. In sulfate-rich mine water from Konigstein at pH 2.6, UO2SO4 (aq.).

EXAFS investigation of uranium(VI) complexes formed at Bacillus cereus and Bacillus sphaericus surfaces

Uranium(VI) complex formation at vegetative cells and spores of Bacillus cereus and Bacillus sphaericus was studied using uranium LII-edge and LIII-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. A comparison of the measured equatorial U-O distances and other EXAFS structural parameters of uranyl species formed at the Bacillus strains with those of the uranyl structure family indicates that the uranium is predominantly bound as uranyl complexes with phosphoryl residues.

DETERMINATION OF PLUTONIUM OXIDATION STATES AT TRACE LEVELS PERTINENT TO NUCLEAR WASTE DISPOSAL

A scheme was developed for the determination of oxidation states of plutonium in environmental samples. The method involves a combination of solvent extractions and coprecipitation. It was tested on solutions with both high-level and trace-level concentrations. The scheme was used to determine Pu oxidation states in solutions from solubility experiments in groundwater from a potential nuclear waste disposal site. At steady-state conditions, Pu was found to be soluble predominantly as Pu(V) and Pu(VI).