Uranium oxides occur in a variety of phases that differ in their crystal structure and uranium oxidation states. Electron energy loss spectroscopy (EELS) is one of the few techniques that has sufficient spatial resolution and sensitivity to electronic structure to distinguish among phases at the nanoscale. However, beam-sensitive materials, such as uranium oxides, are subject to spectral modification due to interactions with the electron beam. Therefore, theory support is essential to reliably exclude the impact of beam damage and generate true reference data sets. Here, we use a comparison of theoretical and experimental spectra to probe the impact of beam damage on the O K-edge and U N-edge (N 6,7 and N 4,5) EELS spectra of various single-valent and mixed-valence uranium oxide bulk phases. Using a low-dose experimental setup, we show that the K-edge theoretical spectra are in excellent agreement with experiment for both peak positions and relative intensities of respective peaks. In contrast, U N-edge features are less distinguishing due to the partially localized nature of the U 5f orbitals and overlapping multiplet and spin-orbit coupling effects. This work demonstrates that O K-edge EELS is sufficiently diagnostic to distinguish a wide range of uranium oxides and that the experimental approach used here minimizes beam damage and allows valence state discrimination across the U(IV), U(V), and U(VI) series. When combined with imaging modes available in electron microscopy, this work enables a detailed investigation and characterization of uranium redox transformations at the nanoscale.

Iron (oxyhydr)oxides are capable of structurally incorporating and releasing trace elements through Fe2+-induced recrystallization. However, estimation of the extent of recrystallization varies among studies using isotopic tracers and those examining the release of occluded trace elements. To provide further insight into the dynamics of Fe2+-catalyzed iron (oxyhydr)oxide recrystallization, and to accurately interpret the isotopic and elemental compositions of iron (oxyhydr)oxides in the rock record, we probed the coupled dynamics of goethite isotopic exchange and trace element cycling during Fe2+-induced recrystallization. Herein, 57Fe labeled Fe2+ was reacted with U(V)-incorporated goethite, and the resulting isotopic and elemental interactions were systematically characterized and modeled. Partial release of incorporated U (3.9%) was observed, which suggested limited recrystallization while Fe isotope measurements suggested nearly complete isotopic mixing after 30 days. A box model incorporating partial and gradual back-reaction estimated an overall goethite recrystallization extent of ∼32.8%, narrowing the gap to the observed U release (3.9%) as compared to the traditional fast back-reaction-only model (88%). This study highlights the role of Fe2+-driven recrystallization in controlling trace metal cycling and provides insights into the stability and reactivity of U-incorporated goethite in reducing environments. The findings refine our understanding of iron (oxyhydr)oxide recrystallization processes and their implications for trace element mobility in natural systems.

Meaningful interpretation of U isotope measurements relies on unraveling the impact of reduction mechanisms on the isotopic fractionation. Here, the isotope fractionation of hexavalent U [U(VI)] was investigated during its reductive mineralization by magnetite to intermediate pentavalent U [U(V)] and ultimately tetravalent U [U(IV)]. As the reaction proceeded, the remaining aqueous phase U [containing U(VI) and U(V)] systematically carried light isotopes, whereas in the bicarbonate-extracted solution [containing U(VI) and U(V)], the δ238U values varied, especially when C/C0 approached 0. This variation was interpreted as reflecting the variable relative contribution of unreduced U(VI) (δ238U < 0‰) and bicarbonate-extractable U(V) (δ238U > 0‰). The solid remaining after bicarbonate extraction included unextractable U(V) and U(IV), for which the δ238U values consistently followed the same trend that started at 0.3-0.5‰ and decreased to ∼0‰. The impact of PIPES buffer on isotopic fractionation was attributed to the variable abundance of U(V) in the aqueous phase. A few extremely heavy bicarbonate-extracted δ238U values were due to mass-dependent fractionation resulting from several hypothesized mechanisms. The results suggest the preferential accumulation of the heavy isotope in the reduced species and the significant influence of U(V) on the overall isotopic fractionation, providing insight into the U isotope fractionation behavior during its abiotic reduction process.

Journal Article Uranium reduction by magnetite – mechanism of UO2 formation monitored by STEM, SAED and EELS Get access Thomas LaGrange, Thomas LaGrange Laboratory for Ultrafast Microscopy and Electron Scattering, École polytechnique fédérale de Lausanne, CH-1015 Lausanne, Switzerland corresponding author thomas.lagrange@epfl.ch Search for other works by this author on: Oxford Academic Google Scholar Zezhen Pan, Zezhen Pan Environmental Microbiology Laboratory, École polytechnique fédérale de Lausanne, CH-1015 Lausanne, Switzerland Search for other works by this author on: Oxford Academic Google Scholar Barbora Bártová, Barbora Bártová Environmental Microbiology Laboratory, École polytechnique fédérale de Lausanne, CH-1015 Lausanne, Switzerland Search for other works by this author on: Oxford Academic Google Scholar Sergei M Butorin, Sergei M Butorin Molecular and Condensed Matter Physics, Department of Physics and Astronomy, Uppsala University, Box 516, SE-751 20 Uppsala, Sweden Search for other works by this author on: Oxford Academic Google Scholar Neil C Hyatt, Neil C Hyatt University of Sheffield, S10 2TN, UK Search for other works by this author on: Oxford Academic Google Scholar Martin C Stennett, Martin C Stennett University of Sheffield, S10 2TN, UK Search for other works by this author on: Oxford Academic Google Scholar Kristina O Kvashnina, Kristina O Kvashnina The Rossendorf Beamline at ESRF – The European Synchrotron, CS40220, 38043 Grenoble Cedex 9, FranceHelmholtz Zentrum Dresden-Rossendorf (HZDR), Institute of Resource Ecology, PO Box 510119, 01314 Dresden, Germany Search for other works by this author on: Oxford Academic Google Scholar Rizlan Bernier-Latmani Rizlan Bernier-Latmani Environmental Microbiology Laboratory, École polytechnique fédérale de Lausanne, CH-1015 Lausanne, Switzerland Search for other works by this author on: Oxford Academic Google Scholar Microscopy and Microanalysis, Volume 28, Issue S1, 1 August 2022, Pages 2444–2446, https://doi.org/10.1017/S1431927622009370 Published: 01 August 2022

Chromium of anthropogenic origin contaminates the environment worldwide. The toxicity of chromium, a group I human carcinogen, is greatest when it is in a hexavalent oxidation state, Cr(VI). Cr(VI) is actively transported into the cell, triggering oxidative damage intracellularly. Due to the abundance of unspecific intracellular reductants, any microbial species is capable of bio-transformation of toxic Cr(VI) to innocuous Cr(III), however, this process is often lethal. Only some bacterial species are capable of sustaining the vegetative growth in the presence of a high concentration of Cr(VI) and thus operate as self-sustainable bioremediation agents. One of the successful microbial Cr(VI) detoxification strategies is the activation of chromate efflux pumps. This work describes transplantation of the chromate efflux pump from the potentially pathogenic but highly Cr resistant Bacillus pseudomycoides environmental strain into non-pathogenic but only transiently Cr tolerant Bacillus subtilis strain. In our study, we compared the two Bacillus spp. strains harboring evolutionarily diverged chromate efflux proteins. We have found that individual cells of the Cr-resistant B. pseudomycoides environmental strain accumulate less Cr than the cells of B. subtilis strain. Further, we found that survival of the B. subtilis strain during the Cr stress can be increased by the introduction of the chromate transporter from the Cr resistant environmental strain into its genome. Additionally, the expression of B. pseudomycoides chromate transporter ChrA in B. subtilis seems to be activated by the presence of chromate, hinting at versatility of Cr-efflux proteins. This study outlines the future direction for increasing the Cr-tolerance of non-pathogenic species and safe bioremediation using soil bacteria.

Uranium isotopic signatures can be harnessed to monitor the reductive remediation of subsurface contamination or to reconstruct paleo-redox environments. However, the mechanistic underpinnings of the isotope fractionation associated with U reduction remain poorly understood. Here, we present a coprecipitation study, in which hexavalent U (U(VI)) was reduced during the synthesis of magnetite and pentavalent U (U(V)) was the dominant species. The measured δ238U values for unreduced U(VI) (∼-1.0‰), incorporated U (96 ± 2% U(V), ∼-0.1‰), and extracted surface U (mostly U(IV), ∼0.3‰) suggested the preferential accumulation of the heavy isotope in reduced species. Upon exposure of the U-magnetite coprecipitate to air, U(V) was partially reoxidized to U(VI) with no significant change in the δ238U value. In contrast, anoxic amendment of a heavy isotope-doped U(VI) solution resulted in an increase in the δ238U of the incorporated U species over time, suggesting an exchange between incorporated and surface/aqueous U. Overall, the results support the presence of persistent U(V) with a light isotope signature and suggest that the mineral dynamics of iron oxides may allow overprinting of the isotopic signature of incorporated U species. This work furthers the understanding of the isotope fractionation of U associated with iron oxides in both modern and paleo-environments.

Metal-reducing microorganisms such as Shewanella oneidensis MR-1 reduce highly soluble species of hexavalent uranyl (U(VI)) to less mobile tetravalent uranium (U(IV)) compounds. The biologically mediated immobilization of U(VI) is being considered for the remediation of U contamination. However, the mechanistic underpinnings of biological U(VI) reduction remain unresolved. It has become clear that a first electron transfer occurs to form pentavalent (U(V)) intermediates, but it has not been definitively established whether a second one-electron transfer can occur or if disproportionation of U(V) is required. Here, we utilize the unusual properties of dpaea2– ((dpaeaH2=bis(pyridyl-6-methyl-2-carboxylate)-ethylamine)), a ligand forming a stable soluble aqueous complex with U(V), and investigate the reduction of U(VI)–dpaea and U(V)–dpaea by S. oneidensis MR-1. We establish U speciation through time by separating U(VI) from U(IV) by ion exchange chromatography and characterize the reaction end-products using U M4-edge high resolution X-ray absorption near-edge structure (HR-XANES) spectroscopy. We document the reduction of solid phase U(VI)–dpaea to aqueous U(V)–dpaea but, most importantly, demonstrate that of U(V)–dpaea to U(IV). This work establishes the potential for biological reduction of U(V) bound to a stabilizing ligand. Thus, further work is warranted to investigate the possible persistence of U(V)–organic complexes followed by their bioreduction in environmental systems.

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 sediment. 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 natural sediment mimicking the environmental conditions during bioremediation. Bioreduced sediment retrieved from the columns and harboring NCU(IV) was 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 sediment, bioreduced U(IV) species remain vulnerable to oxidation and remobilization in the aqueous phase even after a 12-month aging period.

Uranium (U) is a ubiquitous element in the Earth’s crust at ~2 ppm. In anoxic environments, soluble hexavalent uranium (U(VI)) is reduced and immobilized. The underlying reduction mechanism is unknown but likely of critical importance to explain the geochemical behavior of U. Here, we tackle the mechanism of reduction of U(VI) by the mixed-valence iron oxide, magnetite. Through high-end spectroscopic and microscopic tools, we demonstrate that the reduction proceeds first through surface-associated U(VI) to form pentavalent U, U(V). U(V) persists on the surface of magnetite and is further reduced to tetravalent UO 2 as nanocrystals (~1–2 nm) with random orientations inside nanowires. Through nanoparticle re-orientation and coalescence, the nanowires collapse into ordered UO 2 nanoclusters. This work provides evidence for a transient U nanowire structure that may have implications for uranium isotope fractionation as well as for the molecular-scale understanding of nuclear waste temporal evolution and the reductive remediation of uranium contamination.

Uranium (U) speciation was investigated in anoxically preserved porewater samples of a natural mountain wetland in Gola di Lago, Ticino, Switzerland. U porewater concentrations ranged from less than 1 μg/L to tens of μg/L, challenging the available analytical approaches for U speciation in natural samples. Asymmetrical flow field-flow fractionation coupled with inductively coupled plasma mass spectrometry allowed the characterization of colloid populations and the determination of the size distribution of U species in the porewater. Most of the U was associated with three fractions: <0.3 kDa, likely including dissolved U and very small U colloids; a 1-3 kDa fraction containing humic-like organic compounds, dispersed Fe, and, to a small extent, Fe nanoparticles; and a third fraction (5-50 nm), containing a higher amount of Fe and a lower amount of organic matter and U relative to the 1-3 kDa fraction. The proportion of U associated with the 1-3 kDa colloids varied spatially and seasonally. Using anion exchange resins, we also found that a significant proportion of U occurs in its reduced form, U(IV). Tetravalent U was interpreted as occurring within the colloidal pool of U. This study suggests that U(IV) can occur as small (1-3 kDa), organic-rich, and thus potentially mobile colloidal species in naturally reducing wetland environments.

Arsenic contamination in groundwater is pervasive throughout deltaic regions of Southeast Asia and threatens the health of millions. The speciation of As in sediments overlying contaminated aquifers is poorly constrained. Here, we investigate the chemical and mineralogical compositions of sediment cores collected from the Mekong Delta in Vietnam, elucidate the speciation of iron and arsenic, and relate them to the sediment depositional environment. Gradual dissolution of ferric (oxyhydr)oxides with depth is observed down to 7 m, corresponding to the establishment of reducing conditions. Within the reduced sediment, layers originating from marine, coastal or alluvial depositional environments are identified and their age is consistent with a late Holocene transgression in the Mekong Delta. In the organic matter- and sulfur-rich layers, arsenic is present in association with organic matter through thiol-bonding and in the form of arsenian pyrite. The highest arsenic concentration (34-69 ppm) is found in the peat layer at 16 m and suggests the accumulation of arsenic due to the formation of thiol-bound trivalent arsenic (40-55%) and arsenian pyrite (15-30%) in a paleo-mangrove depositional environment (∼8079 yr BP). Where sulfur is limited, siderite is identified, and oxygen- and thiol-bound trivalent arsenic are the predominant forms. It is also worth noting that pentavalent arsenic coordinated to oxygen is ubiquitous in the sediment profile, even in reduced sediment layers. But the identity of the oxygen-bound arsenic species remains unknown. This work shows direct evidence of thiol-bound trivalent arsenic in the Mekong Delta sediments and provides insight to refine the current model of the origin, deposition, and release of arsenic in the alluvial aquifers of the Mekong Delta.

Hundreds of tons of depleted uranium (DU) ammunition were used in previous armed conflicts in Iraq, Bosnia and Herzegovina, and Serbia/Kosovo. The majority (>90%) of DU penetrators miss their target and, if left in the environment, corrode in these postconflict zones. Thus, the best way to understand the fate of bulk DU material in the environment is to characterize the corrosion products of intact DU penetrators under field conditions for extended periods of time. However, such studies are scarce. To fill this knowledge gap, we characterized corrosion products formed from two intact DU penetrators that remained in soils in Bosnia and Herzegovina for over seven years. We used a combination of X-ray powder diffraction, electron microscopy, and X-ray absorption spectroscopy. The results show that metaschoepite (UO3(H2O)2) was a main component of the two DU corrosion products. Moreover, studtite ((UO2)O2(H2O)2·2(H2O)) and becquerelite (Ca(UO2)6O4(OH)6·8(H2O)) were also identified in the corrosion products. Their formation through transformation of metaschoepite was a result of the geochemical conditions under which the penetrators corroded. Moreover, we propose that the transformation of metaschoepite to becquerelite or studtite in the DU corrosion products would decrease the potential for mobilization of U from corroded DU penetrators exposed to similar environments in postconflict areas.

Spores of a number of clostridial species, and their resistance to thermal treatment is a major concern for the food industry. Spore resistance to wet heat is related to the level of spore hydration, which is inversely correlated with the content of calcium and dipicolinic acid (DPA) in the spore core. It is widely believed that the accumulation of DPA and calcium in the spore core is a fundamental component of the sporulation process for all endospore forming species. We have noticed heterogeneity in the heat resistance capacity and overall DPA/calcium content among the spores of several species belonging to Clostridium sensu stricto group: two C. acetobutylicum strains (DSM 792 and 1731), two C. beijerinckii strains (DSM 791 and NCIMB 8052), and a C. collagenovorans strain (DSM 3089). A C. beijerinckii strain (DSM 791) and a C. acetobutylicum strain (DSM 792) display low Ca and DPA levels. In addition, these two species, with the lowest average Ca/DPA content amongst the strains considered, also exhibit minimal heat resistance. There appears to be no correlation between the Ca/DPA content and the phylogenetic distribution of the C. acetobutylicum and C. beijerinckii species based either on the 16S rRNA or the spoVA gene. This finding suggests that a subset of Clostridium sensu stricto species produce spores with low resistance to wet heat. Additionally, analysis of individual spores using STEM-EDS and STXM revealed that DPA and calcium levels can also vary amongst individual spores in a single spore population.

MgB2 wire is a promising superconductor for the superconducting links for the high-luminosity upgrade of the large Hadron collider at CERN. The mechanical properties of MgB2 must be fully quantified for the cable design, and in this study, we evaluate the Young's modulus of MgB2 filaments in wires with a practical level of critical current. The Young's moduli of MgB2 filaments by two different processes, in situ and ex situ, were compared. Two different evaluation methods were applied to an in situ MgB2 wire, a single-fiber tensile test and a tensile test after removing Monel. In addition, the Young's modulus of the few-micron-thick Nb-Ni reaction layer in an ex situ processed wire was evaluated using a nanoindentation testing technique to improve the accuracy of analysis based on the rule of mixtures. The Young's moduli of the in situ and ex situ MgB2 wires were in the range of 76-97 GPa and no distinct difference depending on the fabrication process was found.

The thin films techniques applied to Superconducting RF (SRF) have a long history at CERN. A large panel of cavities has been coated from LEP, to LHC. For the current and future projects (HIE-ISOLDE, HL-LHC, FCC) there is a need offurther higher RF-performances with focus on minimizing residual resistance Rres and maximizing quality factor Q0 of the cavities. This paper will present CERN’s developments on thin films to achieve these goals through the following main axes of research: The first one concerns the application of different coating techniques for Nb (DC-bias diode sputtering, magnetron sputtering and HiPIMS). Another approach is the investigation of alternative materials like Nb3Sn. These lines of development will be supported by a material science approach to characterize and evaluate the layer properties by means of FIB-SEM, TEM, XPS, XRD, etc. In addition a numerical tool for plasma simulation will be exploited to develop adapted coating systems and optimize the coating process, from plasma generation to thin film growth.

In the framework of high luminosity upgrade of Large Hadron Collider at CERN, superconducting links are being developed. MgB 2 wire is a candidate conductor for use in high-current cables. Mechanical properties of this material are of key importance for the definition of the cable design and operating conditions. In this study, we evaluated the Young's modulus of MgB 2 filaments extracted from ex situ processed composite wires. The wires were produced in unit lengths of about 1 km and used in high-current cables. Single fiber tensile test was carried out on filaments composed of MgB 2 , Nb barrier, and Nb-Ni reaction layer. From the unloading modulus of filament specimens measured with different gauge lengths, the Young's modulus of composite filaments extracted from two different strands was determined to be 114 and 122 GPa at room temperature, respectively. By using the rule-of-mixture, the Young's modulus of MgB 2 was estimated to be lower than that reported for highly dense MgB 2 bulks. The reason for such difference is discussed from the viewpoint of void fraction.