Volume 97, Issue 7 - Chemical Speciation

In this paper we show how molecular dynamics simulation can improve comprehension of structure and dynamics of water solvent around heavy cations. In particular, metal-water radial distribution function obtained from molecular dynamics can be used into EXAFS equation to improve the experimental signal fitting. Here we show results on structure and dynamics of Co 2+ , that is a radiocontaminant cation in its isotopic form 60 Co, and lanthanoids(III) that are the chemical analogues of actinides(III) in aqueous solution.

Protactinium occupies a key position in the actinide series between thorium and uranium. In aqueous acidic solution, it is stable at oxidation state (V), occurring either as an oxocation or as a naked ion, depending on the media. Very few structural information on the hydration sphere of Pa(V) in acidic medium is available, in particular in hydrofluoric acid. Combined EXAFS and theoretical calculations have been used in this work to characterize the protactinium coordination sphere at various HF concentrations. The correlation of the XAFS data with quantum chemical calculations provides complementary structural and electronic models from ab initio techniques. At HF concentrations from 0.5 to 0.05 M, both theoretical calculations and EXAFS data suggest that the protactinium coordination sphere is mainly composed of fluoride ions. At the lowest HF concentration, the occurrence of a monooxo bond is observed with EXAFS, in agreement with the literature. A comparison of these data with related neptunium(V) and plutonium(V) diooxocations in perchloric acid is also presented.

The surprising speciation of actinides and lanthanides in ionic liquids (ILs) is reviewed, based on both experimental and theoretical studies. The unusual nature of ILs is shown to induce unique solvation, complexation and extraction features. The effect of water is also detailed.

Solvent extraction in the conditions of tracer scale chemistry was used to study protactinium(V) complexation with sulphate, chloride, oxalate and diethylene-triamine-pentaacetate. Extraction experiments were conducted using the chelating agent thenoyltrifluoroacetone (TTA) in toluene at constant ionic strength and temperature. Information on the species involved in partition equilibria relative to protactinium(V) complexation were deduced from a systematic study of the variations of distribution coefficient of Pa(V) as function of ligands, protons and TTA concentration.

Uranium is a naturally abundant element which has been used in several industries. Internal exposure could occur via three main pathways that are ingestion, inhalation and wounds. It has been recently shown that chronic ingestion of uranium in drinking water induces an important uranium accumulation in kidney with a perturbation of iron metabolism in this organ. Whereas uranium speciation is a key parameter to elucidate the chemical reactivity and the mobility of an element, it remains poorly documented in most of environmental and biological media. A few examples of uranium complexation with biomolecules have been published recently but most of them are in vitro studies whereas in vivo experiments remain poorly investigated. In order to better understand possible competition of uranium towards metals involved in the metal-protein binding, i.e. iron, copper, calcium, a study on uranium speciation was investigated by doing an in vivo screening of target proteins likely to bind it in kidneys of exposed rats. Rats were chronically exposed via contaminated drinking water at 40 mg L -1 and killed 9 months after the beginning of exposure. Kidneys were dissected out and protein extract was prepared. Then, separation of renal proteins by isoelectric focusing gel electrophoresis (IEF) and two-dimensional gel electrophoresis (2-DE) followed by LA-ICPMS analysis were performed. IEF-LA-ICP MS showed that uranium could specifically bind few proteins in kidney whereas 2-DE-LA-ICP MS could indicate that uranium is not covalently bound to proteins in this organ. The results suggested that even at moderate concentrations of exposure, uranium can be observed chelated with some renal proteins that is very encouraging to understand the entry, storage and elimination of this element in kidneys.

This study illustrates the potential of physicochemical techniques to speciate uranium (U) and selenium (Se) in biological samples. Speciation, defined here as the study of structural environment, of both toxic elements, was characterized at several levels in biological media and directly in human cells or bacteria once the metal(loid)s were internalized. External speciation that is extracellular speciation in culture media was predicted by thermodynamic equilibrium computer modelling using the JChess software and validated by spectroscopic measurements (XANES and EXAFS). Internal speciation that is intracellular speciation in eukaryotic and prokaryotic cells was studied in vitro with a soil bacterium Cupriavidus metallidurans CH34 and ROS 17/2.8 osteoblasts, human cells responsible for bone formation. XANES, EXAFS, HPLC-ICP-MS and SDS-PAGE coupled to particle induced X-ray emission (PIXE) permitted the identification and quantification of complexes formed with organic or inorganic molecules and/or larger proteins.