Henry Moll

Interaction of uranium(VI) with lipopolysaccharide

Bacteria have a great influence on the migration behaviour of heavy metals in the environment. Lipopolysaccharides form the main part of the outer membrane of Gram-negative bacteria. We investigated the interaction of the uranyl cation (UO2(2+)) with lipopolysaccharide (LPS) from Pseudomonas aeruginosa by using potentiometric titration and time-resolved laser-induced fluorescence spectroscopy (TRLFS) over a wide pH and concentration range. Generally, LPS consists of a high density of different functionalities for metal binding such as carboxyl, phosphoryl, amino and hydroxyl groups. The dissociation constants and corresponding site densities of these functional groups were determined using potentiometric titration. The combination of both methods, potentiometry and TRLFS, show that at an excess of LPS uranyl phosphoryl coordination dominates, whereas at a slight deficit on LPS compared to uranyl, carboxyl groups also become important for uranyl coordination. The stability constants of one uranyl carboxyl complex and three different uranyl phosphoryl complexes and the luminescence properties of the phosphoryl complexes are reported.

The hydrolysis of dioxouranium(VI) investigated using EXAFS and 17O-NMR

The structure of dioxouranium(VI) as a function of pH at different (CH3)4N-OH concentrations has been investigated with the aid of U LIII-edge EXAFS. Polynuclear hydroxo species were identified by an U-U interaction at 3.808 Å at pH = 4.1. The precipitate formed at pH = 7 has a schoepite like structure. In solution at high pH [0.5 M (CH3)4N-OH], the EXAFS data are consistent with the formation of a monomeric four coordinated uranium(VI) hydroxide complex UO2(OH)42- of octahedral geometry. The first shell contains two O atoms with a U=O distance of 1.830 Å, and four O atoms were identified at a U-O distance of 2.265 Å. In strong alkaline solutions [>1 M (CH3)4N)-OH], 17O-NMR spectra indicate the presence of two species, presumably UO2(OH)42- and UO2(OH)53-, the latter in low concentration, which are in rapid equilibrium with one another at 268 K in aqueous solution.

Solution coordination chemistry of uranium in the binary UO22+-SO42- and the ternary UO22+-SO42--OH- system

The structure and reaction dynamics in the systems UO22+-SO42- and UO22+-SO42--OH- were investigated using EXAFS and 17O-NMR spectroscopy. Uranium LIII edge EXAFS indicated a bidentate coordination mode of sulfate to uranyl. In solution, this is characterized by an U-S distance of 3.11 Å. Approximately 5 oxygen atoms were observed in the equatorial plane at 2.39-2.43 Å. The kinetics in the binary uranyl sulfate system can be described by four dominant exchange reactions: (1) UO22+ + SO42- ⇔ UO2SO4 (k1), (2) U*O22+ + UO2SO4 ⇔ U*O2SO4 + UO22+ (k2), (3) UO22+ + UO2(SO4)22- ⇔ 2 UO2SO4 (k3), and (4) UO2SO4 + SO42- ⇔ UO2(SO4)22- (k4). These reactions have rate constants indicating that the exchange is not of the simple Eigen-Wilkins type. Ternary uranyl sulfate hydroxide species were characterized by their 17O chemical shift and by potentiometry. There are no separate signals for the possible isomers of the ternary species indicating that they are in fast exchange with each other.

The relationship of monodentate and bidentate coordinated uranium(VI) sulfate in aqueous solution

Abstract The coordination of U(VI) sulfate complexes has been investigated by uranium LIII-edge EXAFS and HEXS measurements with the aim to distinguish monodentate and bidentate coordinated sulfate in aqueous solution. UV-vis absorption spectroscopy has been used to differentiate the species and to determine the species distribution as a function of the [SO42−]/[UO22+] ratio. A monodentate coordination prevails in solutions with [SO42−]/[UO22+] ratio of 1, where UO2SO4 is the dominant species. Besides the dominating monodentate sulfate a small amount of bidentate sulfate could be observed, indicating that two isomers may exist for UO2SO4. With increasing [SO42−]/[UO22+] ratio the UO2(SO4)22− species becomes the main species. The uranium atom of this species is coordinated by two bidentate sulfate groups.

Complexation of uranium(VI) with aromatic acids in aqueous solution : a comparison of hydroxamic acids and benzoic acid

The complex formation of uranium(VI) with salicylhydroxamic,benzohydroxamic, and benzoic acid in 0.1 M NaClO4 was studied by UV-vis spectroscopy at pH 3 and 4. Uranium(VI) species of the type MpLqHr were identified from the UV-vis spectra in all three systems. An increase in the absorption combined with a blue shift of the absorption maxima in comparison to the bands of the free uranyl ion of 22.5 ± 2 nm was observed in the uranium (VI)-salicylhydroxamic acid-system. Besides indications for a 1:2 complex, the formation of a 1:1 complex with a stability constant of log β111 = 17.12 ± 0.10 could be demonstrated by its individual absorption spectrum and molar absorption coefficient. Also in the uranium(VI)-benzohydroxamic acid-system a blue shift of the absorption maxima in comparison to the bands of the free uranyl ion of 27 ± 1.4 nm indicate the complex formation. The stability constants are log β110 = 7.96 ± 0.05 for UO2[C6H4CONHO]+ and log β120 = 15.25 ± 0.11 for UO2[C6H4CONHO]2. In contrast to the hydroxamic acids, benzoic acid shows a red shift of the absorption maxima of 2.5 ± 2 nm. Only the 1:1 complex UO2[C6H4COO]+ with a stability constant of log β110 = 3.37 ± 0.14 is existent. An estimate is made in order to discuss the dependencies observed in the absorption spectra in relation to possible coordination modes of uranium(VI). The strength of the complex formation between uranyl and the three aromatic acids is discussed.

Complexation of uranium(VI) with aromatic acids in aqueous solution: a combined computational and experimental study.

The complexes of uranium(VI) with salicylhydroxamate, benzohydroxamate, and benzoate have been investigated in a combined computational and experimental study using density functional theory methods and extended X-ray absorption fine structure spectroscopy, respectively. The calculated molecular structures, relative stabilities, as well as excitation spectra from time-dependent density functional theory calculations are in good agreement with experimental data. Furthermore, these calculations allow the identification of the coordinating atoms in the uranium(VI)-salicylhydroxamate complex, i.e. salicylhydroxamate binds to the uranyl ion via the hydroxamic acid oxygen atoms and not via the phenolic oxygen and the nitrogen atom. Carefully addressing solvation effects has been found to be necessary to bring in line computational and experimental structures, as well as excitation spectra.

Complex formation of curium(III) with amino acids of different functionalities: L-threonine and O -phospho-L-threonine

The speciation of curium(III) with L-threonine and O-phospho-L-threonine was determined by time-resolved laser-induced fluorescence spectroscopy (TRLFS) at trace Cm(III) concentrations (3 × 10−7 M). Curium species of the type MpHqLr were identified in the L-threonine- and O-phospho-L-threonine system. These complexes are characterized by their individual luminescence spectra and luminescence lifetimes. The following formation constants were determined (a) for L-threonine: log β101 = 6.72 ± 0.07, log β102 = 10.22 ± 0.09, and log β1–22 =−(7.22 ± 0.19) at ionic strength I = 0.5 M and (b) for O-phospho-L-threonine: log β121 = 18.03 ± 0.13 and log β111 = 14.17 ± 0.09 at ionic strength I = 0.154 M. Possible structures of the identified curium species are discussed on the basis of the luminescence lifetime measurements and the magnitude of the formation constants.

The interaction of Desulfovibrio äspöensis DSM 10631T with plutonium

Microbes are widely distributed in nature and they can strongly influence the migration of actinides in the environment. This investigation describes the interaction of plutonium in mixed oxidation states (Pu(VI) and Pu(IV)-polymers) with cells of the sulfate-reducing bacterial (SRB) strain Desulfovibrio äspöensis DSM 10631T, which frequently occurs in the deep granitic rock aquifers at the Äspö Hard Rock Laboratory (Äspö HRL), Sweden. In this study, accumulation experiments were performed in order to obtain information about the amount of Pu bound by the bacteria in dependence on the contact time and the initial plutonium concentration. We used solvent extractions, UV-Vis absorption spectroscopy and X-ray absorption near edge structure (XANES) spectroscopy to determine the speciation of Pu oxidation states. Extended X-ray absorption fine structure (EXAFS) spectroscopy was used to study the coordination of the Pu bound by the bacteria. In the first step, the Pu(VI) and Pu(IV)-polymers are bound to the biomass. Solvent extractions showed that 97% of the initially present Pu(VI) is reduced to Pu(V) due to the activity of the cells within the first 24 h of contact time. Most of the formed Pu(V) dissolves from the cell envelope back to the aqueous solution due to the weak complexing properties of this plutonium oxidation state. Indications were found for a penetration of Pu species inside the bacterial cells.

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.

Combined computational and experimental study of uranyl(VI) 1:2 complexation by aromatic acids.

The bis(salicylhydroxamato) and bis(benzohydroxamato) complexes of UO(2)(2+) in aqueous solution have been investigated in a combined experimental and computational effort using extended X-ray absorption fine structure and UV-vis spectroscopy and density functional theory (DFT) techniques, respectively. The experimentally unknown bis(benzoate) complex of UO(2)(2+) was investigated computationally for comparison. Experimental data indicate 5-fold UO(2)(2+) coordination with mean equatorial U-O distances of 2.42 and 2.40 A for the salicyl- and benzohydroxamate systems, respectively. DFT calculations on microsolvated model systems [UO(2)L(2)OH(2)] indicate UO(2)(2+) eta(2)-chelation via the hydroxamate oxygen atoms in excellent agreement with experimental data; calculated complex stabilities support that UO(2)(2+) prefers hydroxamate over carboxylate coordination. The 414 nm absorption band of UO(2)(2+) in aqueous solution is blue-shifted to 390 and 386 nm upon complexation by salicyl- and benzohydroxamate, respectively. Calculated time-dependent DFT excitation energies of [UO(2)L(2)OH(2)], however, occasionally fail to reproduce accurately experimental UV-vis spectra, which are dominated by UO(2)(2+) <-- L(-) charge-transfer contributions. We additionally show that the U(VI) large-core pseudopotential approximation recently developed by some of the authors can routinely be applied for electronic structure calculations not involving uranium 5f occupations significantly different from U(VI).