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Microbial U(VI) reduction influences the uranium mobility in contaminated subsurface environments and can affect the disposal of high-level radioactive waste by transform-ing the water-soluble U(VI) to less mobile U(IV). The reduction of U(VI) by the sulfate-reducing bacterium Desulfosporosinus hippei DSM 8344T, a close phylogenetic relative to naturally occurring microorganism present in clay rock and bentonite, was investigat-ed. D. hippei DSM 8344T showed a relatively fast removal of uranium from the superna-tants in artificial Opalinus Clay pore water. Combined speciation calculations and lumi-nescence spectroscopic investigations showed the dependence of U(VI) reduction on the initial U(VI) species. Scanning transmission electron microscopy coupled with ener-gy-dispersive X-ray spectroscopy showed uranium-containing aggregates on the cell surface and the formation of membrane vesicles. By combining different spectroscopic techniques, including UV/Vis spectroscopy, as well as uranium M4-edge X-ray absorp-tion near-edge structure (XANES) recorded in high-energy-resolution fluorescence-detection (HERFD) mode and extended X-ray absorption fine structure (EXAFS) analy-sis, the partial reduction of U(VI) could be verified, whereby the formed U(IV) product has an unknown structure. Furthermore, the U M4 HERFD-XANES showed the presence of U(V) during the process, suggesting a single-electron transfer mechanism for the microbial U(VI) reduction by sulfate reducers. These findings offer new insights into the U(VI) reduction by sulfate-reducing bacteria and contribute to a comprehensive safety concept for a repository for high-level radioactive waste.

The aim of this study is to synthesize PuO2 nanoparticles (NPs) at low pH values and characterize the materials using laboratory and synchrotron-based methods. Properties of the PuO2 NPs formed under acidic conditions (pH 1-4) are explored here at the atomic scale. High-resolution transmission electron microscopy (HRTEM) is applied to characterize the crystallinity, morphology and size of the particles. It is found that 2 nm crystalline NPs are formed with a PuO2 crystal structure. High energy resolution fluorescence detected (HERFD) X-ray absorption spectroscopy at the Pu M-4 edge has been used to identify the Pu oxidation states and recorded data are analysed using the theory based on the Anderson impurity model (AIM). The experimental data obtained on NPs show that the Pu(iv) oxidation state dominates in all NPs formed at pH 1-4. However, the suspension at pH 1 demonstrates the presence of Pu(iii) and Pu(vi) in addition to the Pu(iv), which is associated with redox dissolution of PuO2 NPs under acidic conditions. We discuss in detail the mechanism that affects the PuO2 NPs synthesis under acidic conditions and compare it with one in neutral and alkaline conditions. Hence, the results shown here, together with the first Pu M-4 HERFD data on PuF3 and PuF4 compounds, are significant for the colloid facilitated transport governing the migration of plutonium in a subsurface environment.

Clay rock represents a suitable host rock for the long-term storage of high-level radioactive waste with bentonite as backfill material. In the event of a worst-case scenario, water can enter the repository. It is possible that naturally occurring microorganisms can interact with the radionuclides and thereby change the chemical speciation or induce redox reactions. Among different sulfate-reducing bacteria, Desulfosporosinus species represent important members of the microbial communities in both clay rock and bentonite.[1,2] Desulfosporosinus hippei DSM 8344T is a close phylogenetic relative to an isolated bacterium from bentonite.[3] Therefore, this strain was selected to get a more profound insight into the uranium(VI) interactions with naturally occurring microorganisms from deep geological layers. Time-dependent experiments in artificial Opalinus Clay pore water[4] (100 µM uranium(VI), pH 5,5) showed a high removal of uranium from the supernatants within a short time range. UV/Vis studies of the dissolved cell pellets provided clear proof of a partial reduction of uranium(VI) to uranium(IV) in the samples, although bands of uranium(VI) were still observable. These findings propose a combined association-reduction process as an explanation for the ongoing interaction mechanism. Uranium aggregates formed on the cell surface were visible in TEM images. Furthermore, cells released membrane vesicles as a possible defense mechanism against cell encrustation. In addition, HERFD-XANES measurements confirmed the reduction of uranium(VI). But with these measurements also the presence of uranium(V) in the cell pellets could be demonstrated. This provides first evidence of the involvement of uranium(V) in uranium(VI) reduction by sulfate-reducing microorganisms. With the help of EXAFS measurements, different cell-related uranium species were detected. This study helps to better understand the complexity of redox processes in the environment and contribute to a safety concept for a nuclear repository in clay rock. Moreover, new insights into the uranium(VI) reduction mechanisms of sulfate-reducing bacteria were presented. References: [1] Bagnoud et al. (2016) Nat. Commun 7, 1–10. [2] Matschiavelli et al. (2019) Environ. Sci. Technol. 53, 10514–10524. [3] Vatsurina et al. (2008) Int. J. Syst. Evol. Microbiol. 58, 1228–1232. [4] Wersin et al. (2011) Appl. Geochemistry 26, 931–953.

Reaction of the N-heterocylic carbene ligand $^{i}$PrIm (L$^{1}$) and lithium bis(trimethylsilyl)amide (TMSA) as a base with UCl$_{4}$ resulted in U(IV) and U(V) complexes. Uranium's +V oxidation state in (HL$^{1}$)$_{2}$[U(V)(TMSI)Cl$_{5}$] (TMSI=trimethylsilylimido) (2) was confirmed by HERFD-XANES measurements. Solid state characterization by SC-XRD and geometry optimisation of [U(IV)(L$^{1}$)$_{2}$(TMSA)Cl$_{3}$] (1) indicated a silylamido ligand mediated inverse trans influence (ITI). The ITI was examined regarding different metal oxidation states and was compared to transition metal analogues by theoretical calculations.

The aim of this study is to synthesize PuO

This chapter focuses on the basic principles of X-ray fluorescence (XRF) and micro-XRF imaging applicable to cultural heritage research, presenting basic figures of merit and application examples based on the use of advanced laboratory and synchrotron radiation sources. Related methods of analysis making use of absorption edge phenomena by X-ray absorption spectroscopy, including X-ray absorption near-edge structure and extended X-ray absorption fine structure spectroscopy will also be discussed.

Nature Communications 12(1), 4429 (2021). doi:10.1038/s41467-021-24557-z, The key to fabricating complex, hierarchical materials is the control of chemical reactions at various length scales. To this end, the classical model of nucleation and growth fails to provide sufficient information. Here, we illustrate how modern X-ray spectroscopic and scattering in situ studies bridge the molecular- and macro- length scales for assemblies of polyhedrally shaped CoO nanocrystals. Utilizing high energy-resolution fluorescence-detected X-ray absorption spectroscopy, we directly access the molecular level of the nanomaterial synthesis. We reveal that initially Co(acac)$_3$ rapidly reduces to square-planar Co(acac)$_2$ and coordinates to two solvent molecules. Combining atomic pair distribution functions and small-angle X-ray scattering we observe that, unlike a classical nucleation and growth mechanism, nuclei as small as 2 nm assemble into superstructures of 20 nm. The individual nanoparticles and assemblies continue growing at a similar pace. The final spherical assemblies are smaller than 100 nm, while the nanoparticles reach a size of 6 nm and adopt various polyhedral, edgy shapes. Our work thus provides a comprehensive perspective on the emergence of nano-assemblies in solution., Published by Nature Publishing Group UK, [London]

Extremely defect graphene oxide (dGO) is proposed as an advanced sorbent for treatment of radioactive waste and contaminated natural waters. dGO prepared using a modified Hummers oxidation procedure, starting from reduced graphene oxide (rGO) as a precursor, shows significantly higher sorption of U(VI), Am(III), and Eu(III) than standard graphene oxides (GOs). Earlier studies revealed the mechanism of radionuclide sorption related to defects in GO sheets. Therefore, explosive thermal exfoliation of graphite oxide was used to prepare rGO with a large number of defects and holes. Defects and holes are additionally introduced by Hummers oxidation of rGO, thus providing an extremely defect-rich material. Analysis of characterization by XPS, TGA, and FTIR shows that dGO oxygen functionalization is predominantly related to defects, such as flake edges and edge atoms of holes, whereas standard GO exhibits oxygen functional groups mostly on the planar surface. The high abundance of defects in dGO results in a 15-fold increase in sorption capacity of U(VI) compared to that in standard Hummers GO. The improved sorption capacity of dGO is related to abundant carboxylic group attached hole edge atoms of GO flakes as revealed by synchrotron-based extended X-ray absorption fine structure (EXAFS) and high-energy resolution fluorescence detected X-ray absorption near edge structure (HERFD-XANES) spectroscopy.

The chemical properties of actinide materials are often predefined and described based on the data available for isostructural species. This is the case for potassium plutonyl (

The nanoscience field often produces results more mystifying than any other discipline. It has been argued that changes in the plutonium dioxide (PuO

Herein, a multi-technique study was performed to reveal the elemental speciation and microphase composition in altered granitic rock collected from the Krunkelbach Valley uranium (U) deposit area near an abandoned U mine, Black Forest, Southern Germany., RSC Advances (2020)

The chemical properties of actinide materials are often predefined and described based on the data available for isostructural species. This is the case for potassium plutonyl (PuVI) carbonate, K4PuVIO2(CO3)3(cr), a complex relevant for nuclear technology and the environment, of which the crystallographic and thermodynamic properties of which are still lacking. We report here the synthesis and characterization of PuVI achieved by single-crystal X-ray diffraction analysis and high-energy-resolution fluorescence-detected X-ray absorption near-edge structure at the Pu M4-edge coupled with electronic structure calculations. The crystallographic properties of PuVI are compared with isostructural uranium (U) and neptunium (Np) compounds. Actinyl (AnVI) axial bond lengths, [O-AnVI-O]2+, are correlated between solid, K4AnVIO2(CO3)3(cr), and aqueous, [AnVIO2(CO3)3]4-(aq) species for the UVI-NpVI-PuVI series. The spectroscopic data are compared to KPuVO2CO3(cr) and PuIVO2(cr) to tackle the trend in the electronic structure of PuVI regarding the oxidation state changes and local structural modifications around the Pu atom, Comment: Inorganic Chemistry (2020)

Understanding the complex chemistry of functional nanomaterials is of fundamental importance. Controlled synthesis and characterization at the atomic level is essential to gain deeper insight into the unique chemical reactivity exhibited by many nanomaterials. Cerium oxide nanoparticles have many industrial and commercial applications,resulting from very strong catalytic, pro-and anti-oxidant activity. However, the identity of the active species and the chemical mechanisms imparted by nanoceria remain elusive, impeding the further development of new applications. Here, we explore the behavior of cerium oxide nanoparticles of different sizes at different temperatures and trace the electronic structure changes by state-of-the-art soft and hard X-ray experiments combined with computational methods. We confirm the absence of the Ce(III) oxidation state at the surface of CeO2nanoparticles, even for particles as small as 2 nm. Synchrotron X-ray absorption experiments at Ce L3and M5edges, combined with X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and small angle X-ray scattering (SAXS) and theoretical calculations demonstrate that in addition to the nanoceria charge stability, the formation of hydroxyl groups at the surface profoundly affects the chemical performance of these nanomaterials, Comment: T. Plakhova et al, Nanoscale (2019)

International audience; Friedreich's ataxia (FRDA) is a neurodegenerative disease characterized by an increase in intracytoplasmic iron concentration. Here the nanoscale iron distribution within single fibroblasts from FRDA patients was investigated using synchrotron-radiation-based nanoscopic X-ray fluorescence and X-ray in-line holography at the ID16A nano-imaging beamline of the ESRF. This unique probe was deployed to uncover the iron cellular two-dimensional architecture of freeze-dried FRDA fibroblasts. An unsurpassed absolute detection capability of 180 iron atoms within a 30 nm  50 nm nanoscopic X-ray beam footprint was obtained using state-of-the-art X-ray focusing optics and a large-solid-angle detection system. Various micrometre-sized iron-rich organelles could be revealed for the first time, tentatively identified as endoplasmic reticulum, mitochondria and lysosomes. Also a multitude of nanoscopic iron hot-spots were observed in the cytosol, interpreted as chaperoned iron within the fibroblast's labile iron pool. These observations enable new hypotheses on the storage and trafficking of iron in the cell and ultimately to a better understanding of iron-storage diseases such as Friedreich's ataxia.

Microbeam X-ray fluorescence (XRF) spectroscopy is applied, next to an art-historical analysis, to determine the time and place of origin of Chinese blue-and-white porcelain. In the performed experiments, two groups of kraak porcelain samples (A and B) have been analyzed with XRF spectroscopy to obtain quantitative data, (trace) elemental distributions and fingerprints within different regions of interest. The outcome was processed with Principal Component Analysis (PCA), and with the obtained results it was possible to conclude that the two groups show similar elemental fingerprints and were manufactured in the same time period with a comparable use of raw materials. Additionally, X-ray absorption spectroscopy (XAS) measurements have been performed on the pigment layer, confirming the use of Cobalt Blue as an underglaze pigment.

Understanding the complex chemistry of functional nanomaterials is of fundamental importance. Controlled synthesis and characterization at the atomic level is essential to gain deeper insight into the unique chemical reactivity exhibited by many nanomaterials. Cerium oxide nanoparticles have many industrial and commercial applications, resulting from very strong catalytic, pro- and anti-oxidant activity. However, the identity of the active species and the chemical mechanisms imparted by nanoceria remain elusive, impeding the further development of new applications. Here, we explore the behavior of cerium oxide nanoparticles of different sizes at different temperatures and trace the electronic structure changes by state-of-the-art soft and hard X-ray experiments combined with computational methods. We confirm the absence of the Ce(iii) oxidation state at the surface of CeO2 nanoparticles, even for particles as small as 2 nm. Synchrotron X-ray absorption experiments at Ce L3 and M5 edges, combined with X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and small angle X-ray scattering (SAXS) and theoretical calculations demonstrate that in addition to the nanoceria charge stability, the formation of hydroxyl groups at the surface profoundly affects the chemical performance of these nanomaterials.

It is crucial to understand the structural origins of macroscopic properties in silicate glasses for their high-tech applications. An example of such an application is chemically strengthened boroaluminosilicate glasses that are exposed to an ion exchange process during which alkali ions (e.g. Na+) are replaced by larger (e.g. K+) ions. Despite the empirically thorough understanding of this exchange process, much less is known about the fundamental physics of the process. Since Fe atoms are a suitable probe for monitoring chemical stress-induced changes in the local structure in the chemically strengthened glasses, a set of chemically strengthened boroaluminosilicate glasses containing 1 mol% Fe2O3 are here studied using depth-resolved confocal X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy. Information on the Fe oxidation state, coordination number, and bond distance as a function of the sample depth and glass composition is obtained. These new insights on chemical stress-induced changes will aid in the further development and improvement of such damage-resistant glasses.

Polycapillary optics, consisting of bundles of narrow hollow glass channels, are regularly used in the field of (micro-)X-ray fluorescence (XRF) spectroscopy to focus X-rays down to a microscopic spot while increasing the flux density of the beam on the sample. Polycapillaries guide X-ray photons through multiple total reflection events, similar to how light is guided within optic fibers. Although the use of polycapillaries in XRF spectroscopy allows for fairly straightforward qualitative elemental analysis, fundamental parameter (FP) based quantification remains difficult due to the energy dependent photon transmission efficiency, focal size, acceptance, etc. of these optics. In order to predict the polycapillary and input beam parameter dependent beam forming properties, a multithreaded Monte Carlo based polycapillary X-ray ray tracing code is presented. Apart from supporting photon ray tracing in ‘ideal’ straight, conical and ellipsoidal shaped polycapillary optics, it also allows for the simulation of photon propagation through arbitrarily shaped optics to account for small deviations from the ideal shape, as is often the case in real world examples. The current code allows for the simulation of so-called ‘leak events’, where the probability of a photon traveling through a capillary wall is taken into account, and also includes support for photon beam polarization effects. The simulated results show good agreement with experimental results obtained at the BM26A beamline of the European Synchrotron Radiation Facility (ESRF, Grenoble, France). The (poly)capillary X-ray ray tracing simulation code, called ‘polycap’, developed in the C language and with bindings for Python, is released under the GPLv3 license. The code is expected to assist in the quantification of (poly)capillary based X-ray fluorescence spectroscopy and may yield additional insight into the manufacturing and development of polycapillary optics.

A novel plug-and-play setup based on polycapillary X-ray optics enables three-dimensional (3D) confocal X-ray fluorescence (XRF) and X-ray absorption spectroscopy down to 8 × 8 × 11 μm3 (17 keV) at the European Synchrotron Radiation Facility Collaborative Research Group Dutch–Belgian Beamline, BM26A. A complete description and analytical characterization is presented, together with two recently performed experimental cases. In Deep Earth diamond Sao Luiz-Frankfurt am Main 16, an olivine-rich inclusion was mapped with full 3D XRF elemental imaging. The preliminary tests on Iron Gall ink contained in an historical document, a letter from the court of King Philip II of Spain, reveal both the delicate nature of Iron Gall ink and the lack of Fe–Ni chemical bonding.

Technological developments such as atmospheric plasma jets for industry can be adapted for the conservation of cultural heritage. This application might offer a potential method for the removal or transformation of the corrosion on historical photographs. We focus on daguerreotypes and present an in-depth study of the induced changes by a multi-analytical approach using optical microscopy, scanning electron microscopy, different types of transmission electron microscopy and X-ray absorption fine structure. The H2-He afterglow removes S from an Ag2S or Cu2S layer which results in a nano-layer of metallic Ag or Cu on top of the deteriorated microstructure. In case the corrosion layer is composed of Cu-Ag-S compounds, our proposed setup can be used to partially remove the corrosion. These alterations of the corrosion results in an improvement in the readability of the photographic image.

X-ray absorption near-edge structure (XANES) spectroscopy is a well-known nondestructive technique that allows for chemical state and local structure determination. Spatially resolved oxidation state imaging is possible performing full-field transmission mode XANES experiments, providing chemical state information on the illuminated sample area, but these experiments are limited to thin, concentrated samples. Here we present the use of a unique energy dispersive (ED) pnCCD detector, the SLcam, for full-field fluorescence mode XANES experiments, thereby significantly relaxing the constraints on sample thickness. Using this new detection methodology, spatially resolved chemical state information on millimeter-sized sample areas can be obtained with microscopic resolution in moderate measuring times (less than 15 h), obtaining a XANES profile for each of nearly 70,000 points in a single measurement without the need of scanning the sample through the beam. Besides a description of the use of this detector for micro-XANES applications, we also present the proof of concept for fluorescence mode micro-XANES using a Fe(0)/Fe2O3 model sample and a Nitisol soil sample, which was measured to obtain iron chemical state distribution information.

The capabilities and limitations of nanosecond laser ablation ICP-mass spectrometry for bulk and spatially resolved (elemental mapping) analysis of iron meteorites were assessed. The quantitative data obtained were compared to those obtained i. via multi-element solution ICP-MS (after digestion) relying on external calibration and, ii. high-accuracy determination of selected platinum group elements using solution ICP-MS after target element isolation using anion exchange chromatography and deploying isotope dilution. Results generated by the different methods described show good agreement. Significant matrix effects were observed to affect the results of the ns-LA-ICP-MS analysis of iron meteorites, making quantification via a matrix-matched standard a prerequisite. Careless use of intensity distribution maps without proper correction for laser-solid coupling efficiency can lead to incorrect interpretation of the element maps. ns-LA-ICP-MS was shown to be suitable for fast and quasi-nondestructive analysis of iron meteorites, not only homogeneous ataxites and hexahedrites, but also more heterogeneous ones, when considering ablated areas of a sufficient size. In the context of elemental mapping using LA-ICP-MS, Pearson's product–moment correlation analysis was demonstrated to be a powerful tool that can provide valuable information on the fractionation of the elements in the parent bodies of meteorites.

The writing in carbonized Herculaneum scrolls, covered and preserved by the pyroclastic events of the Vesuvius in 79 AD, was recently revealed using X-ray phase-contrast tomography, without the need of unrolling the sensitive scrolls. Unfortunately, some of the text is difficult to read due to the interference of the papyrus fibers crossing the written text vertically and horizontally. Recently, lead was found as an elemental constituent in the writing, rendering the text more clearly readable when monitoring the lead X-ray fluorescence signal. Here, several hypotheses are postulated for the origin and state of lead in the papyrus writing. Multi-scale X-ray fluorescence micro-imaging, Monte Carlo quantification and X-ray absorption microspectroscopy experiments are used to provide additional information on the ink composition, in an attempt to determine the origin of the lead in the Herculaneum scrolls and validate the postulated hypotheses.

Many historical silver objects are composed of sterling silver, a silver alloy containing small amounts of copper. Besides the dramatic impact of copper on the corrosion process, the chemical composition of the corrosion layer evolves continuously. The evolution of the surface during the exposure to a Na2S solution was monitored by means of visual observation at macroscopic level, chemical analysis at microscopic level and analysis at the nanoscopic level. The corrosion process starts with the preferential oxidation of copper, forming mixtures of oxides and sulphides while voids are being created beneath the corrosion layer. Only at a later stage, the silver below the corrosion layer is consumed. This results in the formation of jalpaite and at a later stage of acanthite. The acanthite is found inside the corrosion layer at the boundaries of jalpaite grains and as individual grains between the jalpaite grains but also as a thin film on top of the corrosion layer. The corrosion process could be described as a sequence of 5 subsequent surface states with transitions between these states.

Recently, a radically new synchrotron radiation-based elemental imaging approach for the analysis of biological model organisms and single cells in their naturalin vivostate was introduced. The methodology combines optical tweezers (OT) technology for non-contact laser-based sample manipulation with synchrotron radiation confocal X-ray fluorescence (XRF) microimaging for the first time at ESRF-ID13. The optical manipulation possibilities and limitations of biological model organisms, the OT setup developments for XRF imaging and the confocal XRF-related challenges are reported. In general, the applicability of the OT-based setup is extended with the aim of introducing the OT XRF methodology in all research fields where highly sensitivein vivomulti-elemental analysis is of relevance at the (sub)micrometre spatial resolution level.

We report on a radically new elemental imaging approach for the analysis of biological model organisms and single cells in their natural, in vivo state. The methodology combines optical tweezers (OT) technology for non-contact, laser-based sample manipulation with synchrotron radiation confocal X-ray fluorescence (XRF) microimaging for the first time. The main objective of this work is to establish a new method for in vivo elemental imaging in a two-dimensional (2D) projection mode in free-standing biological microorganisms or single cells, present in their aqueous environment. Using the model organism Scrippsiella trochoidea, a first proof of principle experiment at beamline ID13 of the European Synchrotron Radiation Facility (ESRF) demonstrates the feasibility of the OT XRF methodology, which is applied to study mixture toxicity of Cu-Ni and Cu-Zn as a result of elevated exposure. We expect that the new OT XRF methodology will significantly contribute to the new trend of investigating microorganisms at the cellular level with added in vivo capability.

A general strategy for the determination of Tc oxidation state by new approach involving X-ray absorption near edge spectroscopy (XANES) at the Tc L3 edge is shown. A comprehensive series of 99Tc compounds, ranging from oxidation states I to VII, was measured and subsequently simulated within the framework of crystal-field multiplet theory. The observable trends in the absorption edge energy shift in combination with the spectral shape allow for a deeper understanding of complicated Tc coordination chemistry. This approach can be extended to numerous studies of Tc systems as this method is one of the most sensitive methods for accurate Tc oxidation state and ligand characterization., Comment: 21/10/2020: Corrected a spelling error in the author list. Added affiliations in pdf file