The biogeochemistry and bioremediation of uranium and other priority radionuclides

The reduction kinetics of Fe(III)citrate, Fe(III)NTA, Co(III)EDTA-, U(VI)O(2) (2+), Cr(VI)O(4) (2-), and Tc(VII)O(4) (-) were studied in cultures of dissimilatory metal reducing bacteria (DMRB): Shewanella alga strain BrY, Shewanella putrefaciens strain CN32, Shewanella oneidensis strain MR-1, and Geobacter metallireducens strain GS-15. Reduction rates were metal specific with the following rate trend: Fe(III)citrate > or = Fe(III)NTA > Co(III)EDTA- >> UO(2)(2+) > CrO(4)(2-) > TcO(4)(-), except for CrO(4) (2-) when H(2) was used as electron donor. The metal reduction rates were also electron donor dependent with faster rates observed for H(2) than lactate- for all Shewanella species despite higher initial lactate (10 mM) than H2 (0.48 mM). The bioreduction of CrO(4) (2-) was anomalously slower compared to the other metals with H(2) as an electron donor relative to lactate and reduction ceased before all the CrO(4)(2-) had been reduced. Transmission electron microscopic (TEM) and energy-dispersive spectroscopic (EDS) analyses performed on selected solids at experiment termination found precipitates of reduced U and Tc in association with the outer cell membrane and in the periplasm of the bacteria. The kinetic rates of metal reduction were correlated with the precipitation of reduced metal phases and their causal relationship discussed. The experimental rate data were well described by a Monod kinetic expression with respect to the electron acceptor for all metals except CrO(4)(2-), for which the Monod model had to be modified to account for incomplete reduction. However, the Monod models became statistically over-parameterized, resulting in large uncertainties of their parameters. A first-order approximation to the Monod model also effectively described the experimental results, but the rate coefficients exhibited far less uncertainty. The more precise rate coefficients of the first-order model provided a better means than the Monod parameters, to quantitatively compare the reduction rates between metals, electron donors, and DMRB species.

/pdf/reduction-kinetics-of-fe-iii-co-iii-u-vi-cr-vi-and-tc-vii-in-bdg396d1hb.pdf

Reduction kinetics of Fe(III), Co(III), U(VI), Cr(VI), and Tc(VII) in cultures of dissimilatory metal‐reducing bacteria

Modern approaches for bioremediation of radionuclide contaminated environments are based on the ability of microorganisms to effectively catalyze changes in the oxidation states of metals that in turn influence their solubility. Although microbial metal reduction has been identified as an effective means for immobilizing highly-soluble uranium(VI) complexes in situ, the biomolecular mechanisms of U(VI) reduction are not well understood. Here, we show that c-type cytochromes of a dissimilatory metal-reducing bacterium, Shewanella oneidensis MR-1, are essential for the reduction of U(VI) and formation of extracelluar UO 2 nanoparticles. In particular, the outer membrane (OM) decaheme cytochrome MtrC (metal reduction), previously implicated in Mn(IV) and Fe(III) reduction, directly transferred electrons to U(VI). Additionally, deletions of mtrC and/or omcA significantly affected the in vivo U(VI) reduction rate relative to wild-type MR-1. Similar to the wild-type, the mutants accumulated UO 2 nanoparticles extracellularly to high densities in association with an extracellular polymeric substance (EPS). In wild-type cells, this UO 2-EPS matrix exhibited glycocalyx-like properties and contained multiple elements of the OM, polysaccharide, and heme-containing proteins. Using a novel combination of methods including synchrotron-based X-ray fluorescence microscopy and high-resolution immune-electron microscopy, we demonstrate a close association of the extracellular UO 2 nanoparticles with MtrC and OmcA (outer membrane cytochrome). This is the first study to our knowledge to directly localize the OM-associated cytochromes with EPS, which contains biogenic UO 2 nanoparticles. In the environment, such association of UO 2 nanoparticles with biopolymers may exert a strong influence on subsequent behavior including susceptibility to oxidation by O 2 or transport in soils and sediments.

/pdf/c-type-cytochrome-dependent-formation-of-u-iv-nanoparticles-43gbs44bvw.pdf

c-Type cytochrome-dependent formation of U(IV) nanoparticles by Shewanella oneidensis.

Researchers are now discovering that naturally occurring environmental nanoparticles can play a key role in important chemical characteristics and the overall quality of natural and engineered waters. The detection of nanoparticles in virtually all water domains, including the oceans, surface waters, groundwater, atmospheric water, and even treated drinking water, demonstrates a distribution near ubiquity. Moreover, aquatic nanoparticles have the ability to influence environmental and engineered water chemistry and processes in a much different way than similar materials of larger sizes. This review covers recent advances made in identifying nanoparticles within water from a variety of sources, and advances in understanding their very interesting properties and reactivity that affect the chemical characteristics and behaviour of water. In the future, this science will be important in our vital, continuing efforts in water safety, treatment, and remediation.

Aquatic environmental nanoparticles

Is trace metal release in wetland soils controlled by organic matter mobility or Fe-oxyhydroxides reduction?

https://digital.library.unt.edu/ark:/67531/metadc736199/m2/1/high_res_d/799444.pdf

Uranium Co-precipitation with Iron Oxide Minerals

https://digitalcommons.unl.edu/cgi/viewcontent.cgi?article=1249&context=usdoepub

Douglas B. Hunter

Papers

Uranium Co-precipitation with Iron Oxide Minerals

Influence of Mn oxides on the reduction of uranium(VI) by the metal-reducing bacterium Shewanella putrefaciens

Crystal chemistry of clay-Mn oxide associations in soils, fractures, and matrix of the Bandelier Tuff, Pajarito Mesa, New Mexico