Microscale chemical imaging to characterize and quantify corrosion processes at the metal-electrolyte interface.

We introduce an experimental setup to chemically image corrosion processes at metal-electrolyte interfaces under stagnant, confined conditions-relevant in a wide range of situations. The setup is based on a glass capillary, in which precipitation of corrosion products in the interfacial aqueous phase can be monitored over time with optical microscopy, and chemically and structurally characterized with microscopic synchrotron-based techniques (X-ray fluorescence, X-ray diffraction, and X-ray absorption spectroscopy). Moreover, quantification of precipitates through X-ray transmission measurements provides in-situ corrosion rates.

Diffusion in Porous Rock Is Anomalous.

Molecular diffusion of chemical species in subsurface environments─rock formations, soil sediments, marine, river, and lake sediments─plays a critical role in a variety of dynamic processes, many of which affect water chemistry. We investigate and demonstrate the occurrence of anomalous (non-Fickian) diffusion behavior, distinct from classically assumed Fickian diffusion. We measured molecular diffusion through a series of five chalk and dolomite rock samples over a period of about two months.

Impact of gadolinium-based MRI contrast agent and local anesthetics co-administration on chondrogenic gadolinium uptake and cytotoxicity.

The gadolinium-based contrast agent DOTA-Gd is clinically used in combination with local anesthetics for direct magnetic resonance arthrography. It remains unclear whether gadolinium uptake into cartilage is influenced by co-administration of bupivacaine or ropivacaine and whether DOTA-Gd alters their chondrotoxicity. Gadolinium quantification of chondrogenic spheroids revealed enhanced gadolinium uptake after simultaneous exposure to local anesthetics.

Tailoring p-Type Behavior in ZnO Quantum Dots through Enhanced Sol-Gel Synthesis: Mechanistic Insights into Zinc Vacancies.

The synthesis and control of properties of p-type ZnO is crucial for a variety of optoelectronic and spintronic applications; however, it remains challenging due to the control of intrinsic midgap (defect) states. In this study, we demonstrate a synthetic route to yield colloidal ZnO quantum dots (QD) via an enhanced sol-gel process that effectively eliminates the residual intermediate reaction molecules, which would otherwise weaken the excitonic emission. This process supports the creation of ZnO with p-type properties or compensation of inherited n-type defects, primarily due to zinc vacancies under oxygen-rich conditions.

Plutonium mobility and reactivity in a heterogeneous clay rock barrier accented by synchrotron-based microscopic chemical imaging.

The long-term safe disposal of radioactive waste corresponds to a challenging responsibility of present societies. Within deep geological waste disposal concepts, host rocks correspond to the ultimate safety barrier towards the environment. To assess the performance of such barriers over extended time scales, mechanistic information on the interaction between the radiotoxic, long-lived radionuclides like plutonium and the host rock is essential.

a proterozoic cyanobacterial microfossil and implications for cyanobacteria evolution.

Deciphering the fossil record of cyanobacteria is crucial to understand their role in the chemical and biological evolution of the early Earth. They profoundly modified the redox conditions of early ecosystems more than 2.4 Ga ago, the age of the Great Oxidation Event (GOE), and provided the ancestor of the chloroplast by endosymbiosis, leading the diversification of photosynthetic eukaryotes.

Cobalt and Chromium Ions Impair Macrophage Response to Infection.

Cobalt-chromium-molybdenum (CoCrMo) alloys are routinely used in arthroplasty. CoCrMo wear particles and ions derived from arthroplasty implants lead to macrophage-driven adverse local tissue reactions, which have been linked to an increased risk of periprosthetic joint infection after revision arthroplasty. While metal-induced cytotoxicity is well characterized in human macrophages, direct effects on their functionality have remained elusive.

Synchrotron-Based X-ray Fluorescence Imaging Elucidates Uranium Toxicokinetics in .

A combination of synchrotron-based elemental analysis and acute toxicity tests was used to investigate the biodistribution and adverse effects in exposed to uranium nanoparticle (UNP, 3-5 nm) suspensions or to uranium reference (U) solutions. Speciation analysis revealed similar size distributions between exposures, and toxicity tests showed comparable acute effects (UNP LC: 402 μg L [336-484], U LC: 268 μg L [229-315]). However, the uranium body burden was 3- to 5-fold greater in UNP-exposed daphnids, and analysis of survival as a function of body burden revealed a ∼5-fold higher specific toxicity from the U exposure.

Synthesis and Characterization of Stable Cu-Pt Nanoparticles under Reductive and Oxidative Conditions.

We report a synthesis method for highly monodisperse Cu-Pt alloy nanoparticles. Small and large Cu-Pt particles with a Cu/Pt ratio of 1:1 can be obtained through colloidal synthesis at 300 °C. The fresh particles have a Pt-rich surface and a Cu-rich core and can be converted into an intermetallic phase after annealing at 800 °C under H.

Synchrotron XRF and Histological Analyses Identify Damage to Digestive Tract of Uranium NP-Exposed .

Micro- and nanoscopic X-ray techniques were used to investigate the relationship between uranium (U) tissue distributions and adverse effects to the digestive tract of aquatic model organism following uranium nanoparticle (UNP) exposure. X-ray absorption computed tomography measurements of intact daphnids exposed to sublethal concentrations of UNPs or a U reference solution (U) showed adverse morphological changes to the midgut and the hepatic ceca. Histological analyses of exposed organisms revealed a high proportion of abnormal and irregularly shaped intestinal epithelial cells.

Vadose-zone alteration of metaschoepite and ceramic UO in Savannah River Site field lysimeters.

Uranium dioxide (UO) and metaschoepite (UO•nHO) particles have been identified as contaminants at nuclear sites. Understanding their behavior and impact is crucial for safe management of radioactively contaminated land and to fully understand U biogeochemistry. The Savannah River Site (SRS) (South Carolina, USA), is one such contaminated site, following historical releases of U-containing wastes to the vadose zone.

First evidence of nanoparticle uptake through leaves and roots in beech (Fagus sylvatica L.) and pine (Pinus sylvestris L.).

Trees have been used for phytoremediation and as biomonitors of air pollution. However, the mechanisms by which trees mitigate nanoparticle pollution in the environment are still unclear. We investigated whether two important tree species, European beech (Fagus sylvatica L.

Intracellular bound chlorophyll residues identify 1 Gyr-old fossils as eukaryotic algae.

The acquisition of photosynthesis is a fundamental step in the evolution of eukaryotes. However, few phototrophic organisms are unambiguously recognized in the Precambrian record. The in situ detection of metabolic byproducts in individual microfossils is the key for the direct identification of their metabolisms.

Chemical state mapping of simulant Chernobyl lava-like fuel containing material using micro-focused synchrotron X-ray spectroscopy.

Uranium speciation and redox behaviour is of critical importance in the nuclear fuel cycle. X-ray absorption near-edge spectroscopy (XANES) is commonly used to probe the oxidation state and speciation of uranium, and other elements, at the macroscopic and microscopic scale, within nuclear materials. Two-dimensional (2D) speciation maps, derived from microfocus X-ray fluorescence and XANES data, provide essential information on the spatial variation and gradients of the oxidation state of redox active elements such as uranium.

Arabidopsis thaliana Zn2+-efflux ATPases HMA2 and HMA4 are required for resistance to the necrotrophic fungus Plectosphaerella cucumerina BMM.

Zinc is an essential nutrient at low concentrations, but toxic at slightly higher ones. It has been proposed that hyperaccumulator plants may use the excess zinc to fend off pathogens and herbivores. However, there is little evidence of a similar response in other plants.

Direct evidence for eoarchean iron metabolism?

Metasedimentary rocks from Isua, West Greenland (> 3,700 million years old) contain carbonaceous compounds, compatible with a biogenic origin (Hassenkam, Andersson, Dalby, Mackenzie, & Rosing, 2017; Ohtomo, Kakegawa, Ishida, Nagase, & Rosing, 2014; Rosing, 1999). The metamorphic mineral assemblage with garnet and quartz intergrowths contains layers of carbonaceous inclusions contiguous with carbon-rich sedimentary beds in the host rock. Previous studies (Hassenkam et al.

Spatio-Chemical Heterogeneity of Defect-Engineered Metal-Organic Framework Crystals Revealed by Full-Field Tomographic X-ray Absorption Spectroscopy.

The introduction of structural defects in metal-organic frameworks (MOFs), often achieved through the fractional use of defective linkers, is emerging as a means to refine the properties of existing MOFs. These linkers, missing coordination fragments, create unsaturated framework nodes that may alter the properties of the MOF. A property-targeted utilization of this approach demands an understanding of the structure of the defect-engineered MOF.

Correction: Synthesis and characterisation of brannerite compositions (UCe) M TiO (M = Gd, Ca) for the immobilisation of MOX residues.

[This corrects the article DOI: 10.1039/C7RA11742F.].

Correction: Multimodal X-ray microanalysis of a UFeO particle: evidence for the environmental stability of ternary U(V) oxides from depleted uranium munitions testing.

Correction for 'Multimodal X-ray microanalysis of a UFeO4 particle: evidence for the environmental stability of ternary U(v) oxides from depleted uranium munitions testing' by Daniel E. Crean et al., Environ.

Multimodal X-ray microanalysis of a UFeO: evidence for the environmental stability of ternary U(v) oxides from depleted uranium munitions testing.

An environmentally aged radioactive particle of UFeO recovered from soil contaminated with munitions depleted uranium (DU) was characterised by microbeam synchrotron X-ray analysis. Imaging of uranium speciation by spatially resolved X-ray diffraction (μ-XRD) and X-ray absorption spectroscopy (μ-XAS) was used to localise UFeO in the particle, which was coincident with a distribution of U(v). The U oxidation state was confirmed using X-ray Absorption Near Edge Structure (μ-XANES) spectroscopy as +4.

In Situ and Ex Situ Characterization of the Microstructure Formation in Ni-Cr-Si Alloys during Rapid Solidification-Toward Alloy Design for Laser Additive Manufacturing.

Laser beam-based deposition methods such as laser cladding or additive manufacturing of metals promises improved properties, performance, and reliability of the materials and therefore rely heavily on understanding the relationship between chemical composition, rapid solidification processing conditions, and resulting microstructural features. In this work, the phase formation of four Ni-Cr-Si alloys was studied as a function of cooling rate and chemical composition using a liquid droplet rapid solidification technique. Post mortem x-ray diffraction, scanning electron microscopy, and in situ synchrotron microbeam X-ray diffraction shows the present and evolution of the rapidly solidified microstructures.

X-ray absorption linear dichroism at the Ti K-edge of rutile (001) TiO single crystal.

X-ray absorption linear dichroism of rutile TiO at the Ti K-edge provides information about the electronic states involved in the pre-edge transitions. Here, linear dichroism with high energy resolution is analyzed in combination with ab initio finite difference method calculations and spherical tensor analysis. It provides an assignment of the three pre-edge peaks beyond the octahedral crystal field splitting approximation and estimates the spatial extension of the corresponding final states.

Nickel Poisoning of a Cracking Catalyst Unravelled by Single-Particle X-ray Fluorescence-Diffraction-Absorption Tomography.

Ni contamination from crude oil in the fluid catalytic cracking (FCC) process is one of the primary sources of catalyst deactivation, thereby promoting dehydrogenation-hydrogenation and speeding up coke growth. Herein, single-particle X-ray fluorescence, diffraction and absorption (μXRF-μXRD-μXAS) tomography is used in combination with confocal fluorescence microscopy (CFM) after thiophene staining to spatially resolve Ni interaction with catalyst components and study zeolite degradation, including the processes of dealumination and Brønsted acid sites distribution changes. The comparison between a Ni-lean particle, exposed to hydrotreated feedstock, and a Ni-rich one, exposed to non-hydrotreated feedstock, reveals a preferential interaction of Ni, found in co-localization with Fe, with the γ-Al O matrix, leading to the formation of spinel-type hotspots.

Toward time-resolved laser T-jump/X-ray probe spectroscopy in aqueous solutions.

Most chemical and biochemical reactions in nature and in industrial processes are driven by thermal effects that bring the reactants above the energy barrier for reaction. In aqueous solutions, this process can also be triggered by the laser driven temperature jump (T-jump) method, in which the water vibrational (stretch, bend, or combination) modes are excited by a short laser pulse, leading to a temperature increase in the irradiated volume within a few picoseconds. The combination of the laser T-jump with X-ray spectroscopic probes would add element-specificity as well as sensitivity to the structure, the oxidation state, and the spin state of the intermediates of reactions.

Metaschoepite Dissolution in Sediment Column Systems-Implications for Uranium Speciation and Transport.

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 (UO·HO) particles were emplaced in flowing sediment/groundwater columns representative of the UK Sellafield Ltd.