Robin Steudtner

Fluorescence properties of a uranyl(V)-carbonate species [U(V)O2(CO3)3]5− at low temperature

Fluorescence properties of a uranyl(V)-carbonate species in solution are reported for the first time. The fluorescence characteristics of the stable aqueous uranyl(V)-carbonate complex [U(V)O(2)(CO(3))(3)](5-) was determined in a frozen solution (T=153K) of 0.5mM uranium and 1.5M Na(2)CO(3) at pH 11.8 by time resolved laser-induced fluorescence spectroscopy (TRLFS). Two different wavelengths of 255nm and 408nm, respectively were used to independently of each other excite the uranyl(V)-carbonate species. The resulting U(V) fluorescence emission bands were detected between 380nm and 440nm, with a maxima at 404.7nm (excitation with 255nm) and 413.3nm (excitation with 408nm), respectively. It was found that by using an excitation wavelength of 255nm the corresponding extinction coefficient was much higher and the fluorescence spectrum better structured than the ones excited at 408nm. The fluorescence lifetime of the uranyl(V)-carbonate species was determined at 153K as 120micros. TRLFS investigations at room temperature, however, showed no fluorescence signal at all.

Ternary uranium(VI) carbonato humate complex studied by cryo-TRLFS

Abstract The complex formation of U(VI) with humic acid (HA) in the presence of carbonate was studied by time-resolved laser-induced fluorescence spectroscopy at low temperature (cryo-TRLFS) at pH 8.5. In the presence of HA, a decrease of the luminescence intensity of U(VI) and no shift of the emission band maxima in comparison to the luminescence spectrum of the UO2(CO3)34− complex, the dominating U(VI) species under the applied experimental conditions in the absence of HA, was observed. The formation of a ternary U(VI) carbonato humate complex of the type UO2(CO3)2HA(II)4− starting from UO2(CO3)34− was concluded from the luminescence data. For this complex a complex stability constant of log K=2.83 ± 0.17 was determined. Slope analysis resulted in a slope of 1.12 ± 0.11, which verifies the postulated complexation reaction. The results agree very well with literature data. Speciation calculations show that the formation of the ternary U(VI) carbonato humate complex can significantly influence the U(VI) speciation under environmental conditions.

Binary and ternary uranium(VI) humate complexes studied by attenuated total reflection Fourier-transform infrared spectroscopy

The complexation of U(VI) with humic acid (HA) in aqueous solution has been investigated at an ionic strength of 0.1 M (NaCl) in the pH range between pH 2 and 10 at different carbonate concentrations by attenuated total reflection Fourier-transform infrared (ATR FT-IR) spectroscopy. For the first time, the formation of binary and ternary U(VI) humate complexes was directly verified by in situ spectroscopic measurements. The complex formation constants for the binary U(VI) humate complex (UO(2)HA(II)) and for the ternary U(VI) mono hydroxo humate complex (UO(2)(OH)HA(I)) as well as the ternary U(VI) dicarbonato humate complex (UO(2)(CO(3))(2)HA(II)(4-)) determined from the spectroscopic data amount to log β(0.1 M) = 6.70 ± 0.25, log β(0.1 M) = 15.14 ± 0.25 and log β(0.1 M) = 24.47 ± 0.70, respectively, and verify literature data.

A spectroscopic study on U(VI) biomineralization in cultivated Pseudomonas fluorescens biofilms isolated from granitic aquifers.

The interaction between the Pseudomonas fluorescens biofilm and U(VI) were studied using extended X-ray absorption fine structure spectroscopy (EXAFS), and time-resolved laser fluorescence spectroscopy (TRLFS). In EXAFS studies, the formation of a stable uranyl phosphate mineral, similar to autunite (Ca[UO2]2[PO4]2•2–6H2O) or meta-autunite (Ca[UO2]2[PO4]2•10–12H2O) was observed. This is the first time such a biomineralization process has been observed in P. fluorescens. Biomineralization occurs due to phosphate release from the cellular polyphosphate, likely as a cell’s response to the added uranium. It differs significantly from the biosorption process occurring in the planktonic cells of the same strain. TRLFS studies of the uranium-contaminated nutrient medium identified aqueous Ca2UO2(CO3)3 and UO2(CO3)34− species, which in contrast to the biomineralization in the P. fluorescens biofilm, may contribute to the transport and migration of U(VI). The obtained results reveal that biofilms of P. fluorescens may play an important role in predicting the transport behavior of uranium in the environment. They will also contribute to the improvement of remediation methods in uranium-contaminated sites.

Biotransformation and detoxification of selenite by microbial biogenesis of selenium-sulfur nanoparticles

This study combines the interaction between the toxic oxyanions selenite and selenate and the plant growth promoting bacterium Azospirillum brasilense with a comprehensive characterization of the formed selenium particles. As selenium is an essential trace element, but also toxic in high concentrations, its state of occurrence in nature is of major concern. Growth of the bacterium was affected by selenite (1-5mM) only, observable as a prolonged growth lag-phase of 3days. Subsequently, selenite reduction occurred under aerobic conditions resulting in extracellularly formed insoluble Se0 particles. Complementary studies by microscopic and spectroscopic techniques revealed the particles to be homogeneous and stable Se8-nSn structured spheres with an average size of 400nm and highly negative surface charge of -18mV in the neutral pH range. As this is the first study showing Azospirillum brasilense being able to biotransform selenite to selenium particles containing a certain amount of sulfur, even if environmental waters supplemented with selenite were used, they may significantly contribute to the biogeochemical cycling of both elements in soil as well as to their soil-plant transfer. Therefore, microbial biotransformation of selenite under certain circumstances may be used for various bio-remediation and bio-technological applications.

Speciation Studies of Metals in Trace Concentrations: The Mononuclear Uranyl(VI) Hydroxo Complexes

A direct luminescence spectroscopic experimental setup for the determination of complex stability constants of mononuclear uranyl(VI) hydrolysis species is presented. The occurrence of polynuclear species is prevented by using a low uranyl(VI) concentration of 10–8 M (2.4 ppb). Time-resolved laser-induced fluorescence spectra were recorded in the pH range from 3 to 10.5. Deconvolution with parallel factor analysis (PARAFAC) resulted in three hydrolysis complexes. A tentative assignment was based on thermodynamic calculations: UO22+, UO2(OH)+, UO2(OH)2, UO2(OH)3–. An implementation of a Newton–Raphson algorithm into PARAFAC allowed a direct extraction of complex stability constants during deconvolution yielding log(β1M,1°C)1:1 = −4.6, log(β1M,1°C)1:2 = −12.2, log(β1M,1°C)1:3 = −22.3. Extrapolation to standard conditions gave log(β0)1:1 = −3.9, log(β0)1:2 = −10.9, and log(β0)1:3 = −20.7. Luminescence characteristics (band position, lifetime) of the individual mononuclear hydroxo species were derived to serve as a reference data set for further investigations. A correlation of luminescence spectroscopic features with Raman frequencies was demonstrated for the mononuclear uranyl(VI) hydroxo complexes for the first time. Thereby a signal-to-structure correlation was achieved and the complex assignment validated.

Nanofiltration of uranium-contaminated water – focus on separation mechanisms

Nanofiltration offers new perspectives for the treatment of mine drain-age from former uranium mines, e.g. in East Germany. In this study the performance of various commercial nanofiltration membranes for a real mine water sample was determined experimentally and modelled. Experimental data is key to membrane selection and is necessary to validate modelling results. Mathematical modelling offers deeper insights into the interaction of uranium species with solid surfaces which also has the potential to extrapolate to other research fields.

Multidisciplinary characterization of U(VI) sequestration by Acidovorax facilis for bioremediation purposes

The contamination of the environment by U may affect plant life and consequently may have an impact on animal and human health. The present work describes U(VI) sequestration by Acidovorax facilis using a multidisciplinary approach combining wet chemistry, transmission electron microscopy, and spectroscopy methods (e.g. cryo-time resolved laser-induced fluorescence spectroscopy, extended X-ray absorption fine structure spectroscopy, and in-situ attenuated total reflection Fourier transform infrared spectroscopy). This bacterial strain is widely distributed in nature including U-contaminated sites. In kinetic batch experiments cells of A. facilis were contacted for 5 min to 48 h with 0.1 mM U(VI). The results show that the local coordination of U species associated with the cells depends upon time contact. U is bound mainly to phosphate groups of lipopolysaccharide (LPS) at the outer membrane within the first hour. And, that both, phosphoryl and carboxyl functionality groups of LPS and peptidoglycan of A. facilis cells may effectuate the removal of high U amounts from solution at 24-48 h of incubation. It is clearly demonstrated that A. facilis may play an important role in predicting the transport behaviour of U in the environment and that the results will contribute to the improvement of bioremediation methods of U-contaminated sites.

Impact of Haloarchaea on Speciation of Uranium—A Multispectroscopic Approach

Haloarchaea represent a predominant part of the microbial community in rock salt, which can serve as host rock for the disposal of high level radioactive waste. However, knowledge is missing about how Haloarchaea interact with radionuclides. Here, we used a combination of spectroscopic and microscopic methods to study the interactions of an extremely halophilic archaeon with uranium, one of the major radionuclides in high level radioactive waste, on a molecular level. The obtained results show that Halobacterium noricense DSM 15987T influences uranium speciation as a function of uranium concentration and incubation time. X-ray absorption spectroscopy reveals the formation of U(VI) phosphate minerals, such as meta-autunite, as the major species at a lower uranium concentration of 30 μM, while U(VI) is mostly associated with carboxylate groups of the cell wall and extracellular polymeric substances at a higher uranium concentration of 85 μM. For the first time, we identified uranium biomineralization in the presence of Halobacterium noricense DSM 15987T cells. These findings highlight the potential importance of Archaea in geochemical cycling of uranium and their role in biomineralization in hypersaline environments, offering new insights into the microbe-actinide interactions in highly saline conditions relevant to the disposal of high-level radioactive waste as well as bioremediation.