Uranium Speciation in a Chalky Soil.

In this article, the speciation and behavior of anthropogenic metallic uranium deposited on natural soil are approached by combining EXAFS (extended X-ray absorption fine structure) and TRLFS (time-resolved laser-induced fluorescence spectroscopy). First, uranium (uranyl) speciation was determined along the vertical profile of the soil and bedrock by linear combination fitting of the EXAFS spectra. It shows that uranium migration is strongly limited by the sorption reaction onto soil and rock constituents, mainly mineral carbonates and organic matter. Second, uranium sorption isotherms were established for calcite, chalk, and chalky soil materials along with EXAFS and TRLFS analysis. The presence of at least two adsorption complexes of uranyl onto carbonate materials (calcite) could be inferred from TRLFS. The first uranyl tricarbonate complex has a liebigite-type structure and is dominant for low loads on the carbonate surface (<10 mgU/kg(rock)). The second uranyl complex is incorporated into the calcite for intermediate (∼10 to 100 mgU/kg(rock)) to high (high: >100 mgU/kg(rock)) loads. Finally, the presence of a uranium-humic substance complex in subsurface soil materials was underlined in the EXAFS analysis by the occurrence of both monodentate and bidentate carboxylate (or/and carbonate) functions and confirmed by sorption isotherms in the presence of humic acid. This observation is of particular interest since humic substances may be mobilized from soil, potentially enhancing uranium migration under colloidal form.

Centrifugal ultrafiltration preconcentration for studying the colloidal phase of a uranium-containing soil suspension.

The objective of this work was to explore centrifugal ultrafiltration (UF) to separate and / or preconcentrate natural colloidal particles for their characterization. A soil suspension obtained by batch leaching was used as a laboratory reference sample. It was preconcentrated with concentration factors (CF) varying from 10 to 450. The dimensional analysis of the colloidal phase was carried out by Asymmetric Flow Field-Flow Fractionation (AF4)-multidetection. The colloidal masses were estimated by mass balance of the initial suspension, its concentrates and filtrates. The size-dependent distribution (expressed in gyration radius) and total colloidal mass (especially recovery), as well as chemical composition and concentration (including species partitioning between dissolved and colloidal phases) were determined to assess the effects of UF preconcentration on colloidal particles. The gyration radius of the colloidal particles recovered in these concentrated suspensions ranged from about 20 nm to over 150 nm. Neither de-agglomeration nor agglomeration was observed. However, only (64 ± 4) % (CF = 10) of the colloidal particles initially in the soil suspension were found in the recovered concentrated suspensions, and this percentage decreased as CF increased. The filter membrane trapped all other particles, mainly the larger ones. Whatever the CF, the centrifugal UF did not appear to change the dissolved-colloidal partitioning of certain species (Al, organic carbon); whereas it led to an enrichment of the colloidal phase for others (Fe, U). The enrichment rate was specific to each species (15% for Fe; 100% for U). By fitting the observed trends (i.e. conservation, depletion or enrichment of the colloidal phase in the concentrate) as a function of CF, the colloidal concentrations (total and species) were assessed without bias. This methodology offers a new perspective for determining physicochemical speciation in natural waters, with a methodology applicable for environmental survey or site remediation studies.

Colloidal mobilization from soil and transport of uranium in (sub)-surface waters.

An analytical methodology was developed to characterize the colloidal distribution of trace elements of interest in environmental waters sampled in a same site and enables the different colloidal distributions from waters to be compared. The purpose was to provide consistent information related to the origin and nature of colloids responsible for the transport of trace element(s). The work was motivated by the observed enhanced mobility of uranium in soil. The colloidal size continuum was investigated by a multi-technique approach involving asymmetric flow field-flow fractionation (AF4) coupled with ultraviolet spectroscopy (UV), multi angle light scattering (MALS), and atomic mass spectrometry (ICPMS). To take into consideration the size and shape variability specific to each sample, the size distributions were established from the gyration radii measured from MALS, also considering the size information from standard nanospheres fractionated by AF4. A new parameter called "shape index" was proposed. It expresses the difference in hydrodynamic behavior between analytes and spherical particles taken as reference. Under AF4 diffusion conditions, it can be considered as an evaluator of the deviation from the sphericity of the fractionated analytes. AF4-UV-MALS-ICPMS enabled the dimensional and chemical characteristics of the colloidal size continuum to be obtained. As a "proof of concept", the developed methodology was applied at a field scale, in a reference study site. In order to have a "dynamic understanding", the investigation was based on the joint characterization of colloids from surface waters and soil leachates from static and dynamic processes. In the water samples of the study site, the continuum of gyration radius ranged from a few nanometers up to 200 nm. Colloids containing iron, aluminum, and organic carbon were involved in the uranium transport in the soil column and surface waters. The colloidal uranium concentration in the surface water increased from the upstream location (approximately 13 ng (U) L-1) to the downstream location (approximately 60 ng (U) L-1).