Although minor in abundance in Earth’s crust (U, 2–4 ppm; Th, 10–15 ppm) and in seawater (U, 0.003 ppm; Th, 0.0007 ppm), light actinides (Th, Pa, U, Np, Pu, Am, and Cm) are important environmental contaminants associated with anthropogenic activities such as the mining and milling of uranium ores, generation of nuclear energy, and storage of legacy waste resulting from the manufacturing and testing of nuclear weapons. In this review, we discuss the abundance, production, and environmental sources of naturally occurring and some man-made light actinides. As is the case with other environmental contaminants, the solubility, transport properties, bioavailability, and toxicity of actinides are dependent on their speciation (composition, oxidation state, molecular-level structure, and nature of the phase in which the contaminant element or molecule occurs). We review the aqueous speciation of U, Np, and Pu as a function of pH and Eh, their interaction with common inorganic and organic ligands in natural waters...

Environmental speciation of actinides.

Bacillus sphaericus JG-A12 is a natural isolate recovered from a uranium mining waste pile near the town of Johanngeorgenstadt in Saxony, Germany. The cells of this strain are enveloped by a highly ordered crystalline proteinaceous surface layer (S-layer) possessing an ability to bind uranium and other heavy metals. Purified and recrystallized S-layer proteins were shown to be phosphorylated by phosphoprotein-specific staining, inductive coupled plasma mass spectrometry analysis, and a colorimetric method. We used extended X-ray absorption fine-structure (EXAFS) spectroscopy to determine the structural parameters of the uranium complexes formed by purified and recrystallized S-layer sheets of B. sphaericus JG-A12. In addition, we investigated the complexation of uranium by the vegetative bacterial cells. The EXAFS analysis demonstrated that in all samples studied, the U(VI) is coordinated to carboxyl groups in a bidentate fashion with an average distance between the U atom and the C atom of 2.88 ± 0.02 A and to phosphate groups in a monodentate fashion with an average distance between the U atom and the P atom of 3.62 ± 0.02 A. Transmission electron microscopy showed that the uranium accumulated by the cells of this strain is located in dense deposits at the cell surface.

Complexation of Uranium by Cells and S-Layer Sheets of Bacillus sphaericus JG-A12

The availability of synchrotron radiation (SR) to the scientific community has literally revolutionized the way X-ray science is done in many disciplines, including low temperature geochemistry and environmental science. The key reason is that SR provides continuum vacuum ultraviolet (VUV) and X-ray radiation five to ten orders of magnitude brighter than that from standard sealed or rotating anode X-ray tubes (Winick 1987; Altarelli et al. 1998). Although SR was first observed indirectly by John Blewitt in 1945 (Blewitt 1946) and directly by Floyd Haber in 1946 at the General Electric 100-MeV Betatron in Schenectady, NY (see Elder et al. 1947; Baldwin 1975), it took 10 to 15 years before the first systematic applications of SR, which involved spectroscopic studies of the VUV absorption of selected elements (Tomboulian and Hartman 1956) using the 300-MeV synchrotron at Cornell University and of rare gases (Madden and Codling 1963) using the National Bureau of Standards SURF I synchrotron. As of September 2002, there are about 75 storage ring-based SR sources in operation, in construction, funded, or in advanced planning in 23 countries, with 10 fully dedicated SR storage ring facilities in the U.S.. A listing of these sources can be obtained at the following web site: http://www-ssrl.slac.stanford.edu/sr_sources.html .

The first SR experiments relevant to low temperature geochemistry and environmental science, although not performed on earth or environmental materials, were X-ray absorption fine structure (XAFS) spectroscopy measurements on amorphous and crystalline germanium oxide conducted on the SPEAR storage ring at the Stanford Synchrotron Radiation Project in 1971 by Dale Sayers, Farrel Lytle, and Edward Stern (Sayers et al. 1971). Prior to the availability of SR in the hard X-ray energy range (> 5 keV), XAFS spectroscopy measurements were impractical because of the high X-ray flux required and the need for a continuously tunable …

An Overview of Synchrotron Radiation Applications to Low Temperature Geochemistry and Environmental Science

Redox transitions of uranium [from U(VI) to U(IV)] in low-temperature sediments govern the mobility of uranium in the environment and the accumulation of uranium in ore bodies, and inform our understanding of Earth’s geochemical history. The molecular-scale mechanistic pathways of these transitions determine the U(IV) products formed, thus influencing uranium isotope fractionation, reoxidation, and transport in sediments. Studies that improve our understanding of these pathways have the potential to substantially advance process understanding across a number of earth sciences disciplines. Detailed mechanistic information regarding uranium redox transitions in field sediments is largely nonexistent, owing to the difficulty of directly observing molecular-scale processes in the subsurface and the compositional/physical complexity of subsurface systems. Here, we present results from an in situ study of uranium redox transitions occurring in aquifer sediments under sulfate-reducing conditions. Based on molecular-scale spectroscopic, pore-scale geochemical, and macroscale aqueous evidence, we propose a biotic–abiotic transition pathway in which biomass-hosted mackinawite (FeS) is an electron source to reduce U(VI) to U(IV), which subsequently reacts with biomass to produce monomeric U(IV) species. A species resembling nanoscale uraninite is also present, implying the operation of at least two redox transition pathways. The presence of multiple pathways in low-temperature sediments unifies apparently contrasting prior observations and helps to explain sustained uranium reduction under disparate biogeochemical conditions. These findings have direct implications for our understanding of uranium bioremediation, ore formation, and global geochemical processes.

https://www.pnas.org/content/pnas/110/12/4506.full.pdf

Uranium redox transition pathways in acetate-amended sediments

We used molecular dynamics simulations to study the adsorption of aqueous uranyl species (UO22+) onto clay mineral surfaces in the presence of sodium counterions and carbonato ligands. The large system size (10 000 atoms) and long simulation times (10 ns) allowed us to investigate the thermodynamics of ion adsorption, and the atomistic detail provided clues for the observed adsorption behavior. The model system consisted of the basal surface of a low-charge Na-montmorillonite clay in contact with aqueous uranyl carbonate solutions with concentrations of 0.027 M, 0.081 M, and 0.162 M. Periodic boundary conditions were used in the simulations to better represent an aqueous solution interacting with an external clay surface. Uranyl adsorption tendency was found to decrease as the aqueous uranyl carbonate concentration was increased, while sodium adsorption remained constant. The observed behavior is explained by physical and chemical effects. As the ionic strength of the aqueous solution was increased, electrostatic factors prevented further uranyl adsorption once the surface charge had been neutralized. Additionally, the formation of aqueous uranyl carbonate complexes, including uranyl carbonato oligomers, contributed to the decreased uranyl adsorption tendency.

Molecular dynamics simulation of uranyl(VI) adsorption equilibria onto an external montmorillonite surface.

Citrate enhanced uranyl adsorption on goethite: An EXAFS analysis

Association of uranyl with the cell wall of Pseudomonas fluorescens inhibits metabolism.

This study investigated the partitioning of uranyl within a quaternary system made up of uranyl, citrate, goethite, and the bacterium Pseudomonas fluorescens. In the absence of cells, uranyl was sorbed to goethite as a complex involving surface groups and/or citrate. Measurements of the evolution of CO2 indicated that the addition of bacterial cells lead to the gradual biodegradation of citrate. Throughout the biodegradation process, uranyl remained sorbed to the insoluble fraction comprised of goethite and cells. EXAFS (Extended X-ray Absorption Fine Structure) measurements showed that bacterial cells outcompeted goethite for uranyl under the experimental conditions and caused the repartitioning of uranyl from goethite to cell matter, independently from citrate degradation. Citrate degradation caused further release of uranyl from goethite surfaces, followed by subsequent association of uranyl with cells. At long equilibration times (3 months), cell lysis and phosphate release resulted in the precipitati...

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Rizlan Bencheikh-Latmani

Papers

Citrate enhanced uranyl adsorption on goethite: An EXAFS analysis

Association of uranyl with the cell wall of Pseudomonas fluorescens inhibits metabolism.

Fate of uranyl in a quaternary system composed of uranyl, citrate, goethite, and Pseudomonas fluorescens.