Biogeochemical controls on the product of microbial U(VI) reduction

Biologically mediated immobilization of radio-nuclides in the subsurface is a promising strategy for the remediation of uranium-contaminated sites. During this process, soluble U(VI) is reduced by indigenous microorganisms to sparingly soluble U(TV). The crystalline U(IV) phase uraninite, or UO2, is the preferable end-product of bioremediation due to its relatively high stability and low solubility in comparison to biomass-associated nonuraninite U(IV) species that have been reported in laboratory and under field conditions. The goal of this study was to delineate the geochemical conditions that promote the formation of nonuraninite U(IV) versus uraninite and to decipher the mechanisms of its preferential formation. U(IV) products were prepared under varying geochemical conditions and characterized with X-ray absorption spectroscopy (XAS), scanning transmission X-ray microscopy (STXM), and various wet chemical methods. We report an increasing fraction of nonuraninite U(IV) species with decreasing initial U concentration. Additionally, the presence of several common groundwater solutes (sulfate, silicate, and phosphate) promote the formation of nonuraninite U(IV). Our experiments revealed that the presence of those solutes promotes the formation of bacterial extracellular polymeric substances (EPS) and increases bacterial viability, suggesting that the formation of nonuraninite U(IV) is due to a biological response to solute presence during U(VI) reduction. The results obtained from this laboratory-scale research provide insight into biogeochemical controls on the product(s) of uranium reduction during bioremediation of the subsurface.

Non-uraninite products of microbial U(VI) reduction

Rizlan Bernier-Latmani, Elena Cristina Dalla Vecchia, Jonathan Sharp, Elena Suvorova Buffat, Harish Veeramani, Nicholas Wigginton

A promising remediation approach to mitigate subsurface uranium contamination is the stimulation of indigenous bacteria to reduce mobile U(VI) to sparingly soluble U(IV). The product of microbial uranium reduction is often reported as the mineral uraninite. Here, we show that the end products of uranium reduction by several environmentally relevant bacteria (Gram-positive and Gram-negative) and their spores include a variety of U(IV) species other than uraninite. U(IV) products were prepared in chemically variable media and characterized using transmission electron microscopy (TEM) and X-ray absorption spectroscopy (XAS) to elucidate the factors favoring/inhibiting uraninite formation and to constrain molecular structure/composition of the non-uraninite reduction products. Molecular complexes of U(IV) were found to be bound to biomass, most likely through P-containing ligands. Minor U(IV)-orthophosphates such as ningyoite [CaU(PO4)(2)], U2O(PO4)(2), and U-2(PO4)(P3O10) were observed in addition to uraninite. Although factors controlling the predominance of these species are complex, the presence of various solutes was found to generally inhibit uraninite formation. These results suggest a new paradigm for U(IV) in the subsurface, i.e., that non-uraninite U(IV) products may be found more commonly than anticipated. These findings are relevant for bioremediation strategies and underscore the need for characterizing the stability of non-uraninite U(IV) species in natural settings.

2010

Coupled Biogeochemical Processes for the Reduction and Immobilization of Uranium

Harish Veeramani

The substantial decrease in solubility accompanying the reduction of U(VI) to U(IV), producing the sparingly soluble mineral uraninite, is viewed as a potential mechanism for the sequestration of environmental uranium contamination. In recent years, a variety of bacteria have been reported to exhibit this reductive capacity. To obtain an understanding of the microbial uranium transformation, to develop a practical approach for the acceleration of in-situ bioreduction, and to predict the long-term fate of environmental uranium, several aspects of the microbial reduction process have been experimentally explored. This dissertation outlines the research that investigates rates of microbial uranium reduction under various experimental conditions, probes the product(s) of enzymatic U(VI) reduction and elaborates the structure of one product –biogenic uraninite– demonstrating the structure- and reactivity-modifying effect of a dopant (Mn(II)) and lastly identifies the products of abiotic uranium reduction by biogenic magnetite and vivianite.

EPFL2010

Products of abiotic U(VI) reduction by biogenic magnetite and vivianite

Daniel Scott Alessi, Rizlan Bernier-Latmani, Elena Suvorova Buffat, Harish Veeramani

Reductive immobilization of uranium by the stimulation of dissimilatory metal-reducing bacteria (DMRB) has been investigated as a remediation strategy for subsurface U(VI) contamination. In those environments, DMRB may utilize a variety of electron acceptors, such as ferric iron which can lead to the formation of reactive biogenic Fe(II) phases. These biogenic phases could potentially mediate abiotic U(VI) reduction. In this work, the DMRB Shewanella putrefaciens strain CN32 was used to synthesize two biogenic Fe(II)-bearing minerals: magnetite (a mixed Fe(II)-Fe(III) oxide) and vivianite (an Fe(II)-phosphate). Analysis of abiotic redox interactions between these biogenic minerals and U(VI) showed that both biogenic minerals reduced U(VI) completely. XAS analysis indicates significant differences in speciation of the reduced uranium after reaction with the two biogenic Fe(II)-bearing minerals. While biogenic magnetite favored the formation of structurally ordered, crystalline UO2, biogenic vivianite led to the formation of a monomeric U(IV) species lacking U-U associations in the corresponding EXAFS spectrum. To investigate the role of phosphate in the formation of monomeric U(IV) such as sorbed U(IV) species complexed by mineral surfaces, versus a U(IV) mineral, uranium was reduced by biogenic magnetite that was pre-sorbed with phosphate. XAS analysis of this sample also revealed the formation of monomeric U(IV) species suggesting that the presence of phosphate hinders formation of UO2. This work shows that U(VI) reduction products formed during in situ biostimulation can be influenced by the mineralogical and geochemical composition of the surrounding environment, as well as by the interfacial solute-solid chemistry of the solid-phase reductant. (C) 2011 Elsevier Ltd. All rights reserved.

Elsevier2010