B18-Core EXAFS
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Diamond Proposal Number(s):
[17243, 13559]
Abstract: As the dominant radionuclide by mass in many radioactive wastes, the control of uranium mobility in contaminated environments is of high concern. U speciation can be governed by microbial interactions, whereby metal-reducing bacteria are able to reduce soluble U(VI) to insoluble U(IV), providing a method for removal of U from contaminated groundwater. Although microbial U(VI) reduction is widely reported, the mechanism(s) for the transformation of U(VI) to poorly soluble U(IV) phases are poorly understood. By combining a suite of analyses, including luminescence, U M4-edge HERFD-XANES and U L3-edge XANES/EXAFS we show that the microbial reduction of U(VI) by the model Fe(III)-reducing bacterium, Shewanella oneidensis MR1, proceeds via a single electron transfer to form a pentavalent U(V) intermediate which disproportionates to form U(VI) and U(IV). Furthermore, we have identified significant U(V) present in post reduction solid phases, implying that U(V) may be stabilised for up to 120.5 hours.
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Jan 2020
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B18-Core EXAFS
I20-Scanning-X-ray spectroscopy (XAS/XES)
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Luke T.
Townsend
,
Samuel
Shaw
,
Naomi E. R.
Ofili
,
Nikolas
Kaltsoyannis
,
Alex S.
Walton
,
J. Frederick W.
Mosselmans
,
Thomas S.
Neil
,
Jonathan R.
Lloyd
,
Sarah
Heath
,
Rosemary
Hibberd
,
Katherine
Morris
Diamond Proposal Number(s):
[13559, 17376, 17243]
Open Access
Abstract: Uranium is a risk-driving radionuclide in both radioactive waste disposal and contaminated land scenarios. In these environments, a range of biogeochemical processes can occur, including sulfate reduction, which can induce sulfidation of iron (oxyhydr)oxide mineral phases. During sulfidation, labile U(VI) is known to reduce to relatively immobile U(IV); however, the detailed mechanisms of the changes in U speciation during these biogeochemical reactions are poorly constrained. Here, we performed highly controlled sulfidation experiments at pH 7 and pH 9.5 on U(VI) adsorbed to ferrihydrite and investigated the system using geochemical analyses, X-ray absorption spectroscopy (XAS), and computational modeling. Analysis of the XAS data indicated the formation of a novel, transient U(VI)–persulfide complex as an intermediate species during the sulfidation reaction, concomitant with the transient release of uranium to the solution. Extended X-ray absorption fine structure (EXAFS) modeling showed that a persulfide ligand was coordinated in the equatorial plane of the uranyl moiety, and formation of this species was supported by computational modeling. The final speciation of U was nanoparticulate U(IV) uraninite, and this phase was evident at 2 days at pH 7 and 1 year at pH 9.5. Our identification of a new, labile U(VI)-persulfide species under environmentally relevant conditions may have implications for U mobility in sulfidic environments pertinent to radioactive waste disposal and contaminated land scenarios.
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Dec 2019
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I20-Scanning-X-ray spectroscopy (XAS/XES)
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Diamond Proposal Number(s):
[17472]
Abstract: Reductive immobilization of uranium has been explored as a remediation strategy for the U-contaminated subsurface. Via the in-situ biostimulation of microbial processes, hexavalent U is reduced to less soluble tetravalent species which are immobilized within the sediments. Although the mineral uraninite (UO2) was initially considered the dominant product of biological reduction, non-crystalline U(IV) species (NCU(IV)) are found to be abundant in the environment, despite their greater susceptibility to oxidation and remobilization. However, it has been recently proposed that, through aging, NCU(IV) might transform into UO2, which would potentially enhance the stability of the reduced U pool. In this study, we performed column experiments to produce NCU(IV) species in a natural sediment mimicking the environmental conditions during bioremediation. Bioreduced sediments retrieved from the columns and harboring NCU(IV), were incubated in static microcosms under anoxic conditions, to allow the systematic monitoring of U coordination by X-ray absorption spectroscopy (XAS) over 12 months. XAS revealed that, under the investigated conditions, the speciation of U(IV) does not change over time. Thus, because NCU(IV) is the dominant species in the sediments, bioreduced U(IV) species remain vulnerable to oxidation and remobilization in the aqueous phase even after a 12-month aging period.
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Nov 2019
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B18-Core EXAFS
I14-Hard X-ray Nanoprobe
I18-Microfocus Spectroscopy
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William R.
Bower
,
Katherine
Morris
,
Francis R.
Livens
,
J. Frederick W.
Mosselmans
,
Connaugh M.
Fallon
,
Adam J.
Fuller
,
Louise S.
Natrajan
,
Christopher
Boothman
,
Jonathan R.
Lloyd
,
Satoshi
Utsunomiya
,
Daniel
Grolimund
,
Dario
Ferreira Sanchez
,
Tom
Jilbert
,
Julia E.
Parker
,
Thomas S.
Neill
,
Gareth T. W.
Law
Diamond Proposal Number(s):
[15085, 17270, 13559, 18053]
Abstract: Metaschoepite is commonly found in U contaminated environments and metaschoepite-bearing wastes may be managed via shallow or deep disposal. Understanding metaschoepite dissolution and tracking the fate of any liberated U is thus important. Here, discrete horizons of metaschoepite (UO3●nH2O) particles were emplaced in flowing sediment/groundwater columns representative of the UK Sellafield site. The column systems either remained oxic or became anoxic due to electron donor additions, and the columns were sacrificed after 6- and 12-months for analysis. Solution chemistry, extractions, and bulk and micro-/nano-focus X-ray spectroscopies were used to track changes in U distribution and behavior. In the oxic columns, U migration was extensive, with UO22+ identified in effluents after 6-months of reaction using fluorescence spectroscopy. Unusually, in the electron-donor amended columns, during microbially-mediated sulfate reduction, significant amounts of UO2-like colloids (>60% of the added U) were found in the effluents using TEM. XAS analysis of the U remaining associated with the reduced sediments confirmed the presence of trace U(VI), non-crystalline U(IV), and biogenic UO2, with UO2 becoming more dominant with time. This study highlights the potential for U(IV) colloid production from U(VI) solids under reducing conditions and the complexity of U biogeochemistry in dynamic systems.
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Jul 2019
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I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[15046]
Abstract: Results are presented from the analysis of aqueous and solid-phase V speciation within samples collected from the Hazeltine Creek catchment affected by the August 2014 Mount Polley mine tailings dam failure, Canada. Electron microprobe and XANES analysis found that V is present as V3+ substituted into magnetite, and V3+ and V4+ substituted into titanite, both of which occur in the spilled Mount Polley tailings. Secondary Fe oxyhydroxides forming in inflow waters and on creek beds have V K-edge XANES spectra exhibiting E½ positions and pre-edge features consistent with the presence of V5+ species, suggesting sorption of this species on these secondary phases. PHREEQC modelling suggests that the stream waters mostly contain V5+, and the inflow and pore waters contain a mixture of V3+ and V5+. These data, and stream, inflow and pore water chemical data, suggest that dissolution of V(III)-bearing magnetite, V(III,IV)-bearing titanite, V(V)-bearing Fe(-Al-Si-Mn) oxhydroxides, V-bearing Al(OH)3 and/or -clay minerals may have occurred. In the circumneutral pH environment of Hazeltine Creek elevated V concentrations are likely naturally attenuated by formation of V(V)-bearing secondary Fe oxyhydroxide, Al(OH)3 or clay mineral colloids, suggesting that the V is not bioavailable. A conceptual model is presented describing the origin and fate of V in Hazeltine Creek that is applicable to other river systems.
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Mar 2019
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B18-Core EXAFS
I15-Extreme Conditions
I22-Small angle scattering & Diffraction
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Diamond Proposal Number(s):
[12704, 13559, 15276, 15966]
Abstract: Uranium is typically the most abundant radionuclide by mass in radioactive wastes and is a significant component of effluent streams at nuclear facilities. Actinide (IV) (An(IV)) colloids formed via various pathways, including corrosion of spent nuclear fuel, have the potential to greatly enhance the mobility of poorly soluble An(IV) forms, including uranium. This is particularly important in conditions relevant to decommissioning of nuclear facilities and the geological disposal of radioactive waste. Previous studies have suggested that silicate could stabilise U(IV) colloids. Here the formation, composition and structure of U(IV)-silicate colloids under the alkaline conditions relevant to spent nuclear fuel storage and disposal were investigated using a range of state of the art techniques. The colloids are formed across a range of pH conditions (9-10.5) and silicate concentrations (2-4 mM) and have a primary particle size 1-10 nm, also forming suspended aggregates < 220 nm. X-ray absorption spectroscopy, ultrafiltration and scanning transmission electron microscopy confirm the particles are U(IV)-silicates. Additional evidence from X-ray diffraction and pair distribution function data suggests the primary particles are composed of a UO2-rich core and a U-silicate shell. U(IV)-silicate colloids formation correlates with the formation of U(OH)3(H3SiO4)32- complexes in solution indicating they are likely particle precursors. Finally, these colloids form under a range of condition relevant to nuclear fuel storage and geological disposal of radioactive waste and represent a potential pathway for U mobility in these systems.
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Jul 2018
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I20-Scanning-X-ray spectroscopy (XAS/XES)
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Diamond Proposal Number(s):
[9157]
Abstract: A molecular level understanding of the thermodynamics and kinetics of the chemical bonding between mercury, Hg(II), and natural organic matter (NOM) associated thiol functional groups (NOM-RSH) is required if bioavailability and transformation processes of Hg in the environment are to be fully understood. This study provides the thermodynamic stability of the Hg(NOM-RS)2 structure using a robust method in which cysteine (Cys) served as a competing ligand to NOM (Suwanee River 2R101N sample) associated RSH groups. The concentration of the latter was quantified to be 7.5 ± 0.4 µmol g−1 NOM by Hg LIII-edge EXAFS spectroscopy. The Hg(Cys)2 molecule concentration in chemical equilibrium with the Hg(II)-NOM complexes was directly determined by HPLC-ICPMS and losses of free Cys due to secondary reactions with NOM was accounted for in experiments using 1H NMR spectroscopy and 13C isotope labeled Cys. The log K ± SD for the formation of the Hg(NOM-RS)2 molecular structure, Hg2+ + 2NOM-RS− = Hg(NOM-RS)2, and for the Hg(Cys)(NOM-RS) mixed complex, Hg2+ + Cys− + NOM-RS− = Hg(Cys)(NOM-RS), were determined to be 40.0 ± 0.2 and 38.5 ± 0.2, respectively, at pH 3.0. The magnitude of these constants was further confirmed by 1H NMR spectroscopy and the Hg(NOM-RS)2 structure was verified by Hg LIII-edge EXAFS spectroscopy. An important finding is that the thermodynamic stabilities of the complexes Hg(NOM-RS)2, Hg(Cys)(NOM-RS) and Hg(Cys)2 are very similar in magnitude at pH values < 7, when all thiol groups are protonated. Together with data on 15 low molecular mass (LMM) thiols, as determined by the same method (Liem-Ngyuen et al., 2017),1 the constants for Hg(NOM-RS)2 and Hg(Cys)(NOM-RS) represent an inherently consistent thermodynamic data set which we recommend is used in studies where the chemical speciation of Hg(II) is determined in presence of NOM and LMM thiols.
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Jul 2018
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B18-Core EXAFS
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Diamond Proposal Number(s):
[7367, 7593, 8070]
Open Access
Abstract: Radiotoxic uranium contamination in natural systems and nuclear waste containment can be sequestered by incorporation into naturally abundant iron (oxyhydr)oxides such as hematite (α-Fe2O3) during mineral growth. The stability and properties of the resulting uranium-doped material are impacted by the local coordination environment of incorporated uranium. While measurements of uranium coordination in hematite have been attempted using extended X-ray absorption fine structure (EXAFS) analysis, traditional shell-by-shell EXAFS fitting yields ambiguous results. We used hybrid functional ab initio molecular dynamics (AIMD) simulations for various defect configurations to generate synthetic EXAFS spectra which were combined with adsorbed uranyl spectra to fit experimental U L3-edge EXAFS for U6+-doped hematite. We discovered that the hematite crystal structure accommodates a trans-dioxo uranyl-like configuration for U6+ that substitutes for structural Fe3+, which requires two partially protonated Fe vacancies situated at opposing corner-sharing lattice sites. Surprisingly, the best match to experiment included significant proportions of vacancy configurations other than the minimum-energy configuration, pointing to the importance of incorporation mechanisms and kinetics over thermodynamics in determining the state of an impurity incorporated in a host phase under low temperature hydrothermal conditions.
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May 2018
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I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[9151]
Abstract: The effects of zinc (Zn) speciation on plant growth in Zn-contaminated soil in the presence of bacteria are unknown but are critical to our understanding of metal biodynamics in the rhizosphere where bacteria are abundant. A 6-week pot experiment investigated the effects of two plant growth promoting bacteria (PGPB), Rhizobium leguminosarum and Pseudomonas brassicacearum, on Zn accumulation and speciation in Brassica juncea grown in soil amended with 600 mg kg-1 elemental Zn as three Zn species - soluble ZnSO4 and nanoparticles of ZnO and ZnS. Measures of plant growth were higher across all Zn treatments inoculated with PGPB compared to uninoculated controls but Zn species effects were not significant. Transmission electron microscopy identified dense particles in the epidermis and intracellular spaces in roots, suggesting Zn uptake in both dissolved and particulate forms. X-ray absorption near edge structure (XANES) analysis of roots revealed differences in Zn speciation between treatments. Uninoculated plants exposed to ZnSO4 contained Zn predominantly in the form of Zn phytate (35%), and Zn polygalacturonate (30%), whereas Zn cysteine (57%) and Zn polygalacturonate (37%) dominated in roots exposed to ZnO nanoparticles. Inoculation with PGPB increased (> 50%) the proportion of Zn cysteine under all Zn treatments, suggesting Zn co-ordination with cysteine as the predominant mechanism of Zn toxicity reduction by PGPB. Using this approach we show, for the first time, that although speciation is important, the presence of rhizospheric bacteria completely overrides speciation effects such that most of the Zn in plant tissue exists as complexes other than the original form.
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Feb 2018
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B18-Core EXAFS
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Diamond Proposal Number(s):
[7593, 10163, 12767]
Abstract: Technetium is a problematic contaminant at nuclear sites and little is known about how repeated microbiologically-mediated redox cycling impacts its fate in the environment. We explore this question in sediments representative of the Sellafield Ltd. site, UK, over multiple reduction and oxidation cycles spanning ~ 1.5 years. We found the amount of Tc remobilised from the sediment into solution significantly decreased after repeated redox cycles. X-ray Absorption Spectroscopy (XAS) confirmed that sediment bound Tc was present as hydrous TcO2-like chains throughout experimentation and that Tc’s increased resistance to remobilisation (via reoxidation to soluble TcO4-) resulted from both shortening of TcO2 chains during redox cycling and association of Tc(IV) with Fe phases in the sediment. We also observed that Tc(IV) remaining in solution during bioreduction was likely associated with colloidal magnetite nanoparticles. These findings highlight crucial links between Tc and Fe biogeochemical cycles that have significant implications for Tc’s long-term environmental mobility, especially under ephemeral redox conditions.
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Nov 2017
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