I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[34311]
Abstract: Rice is a staple food for over half the world's population. This study uniquely investigates the spatial distribution of key micronutrients (Cu, Mn, Fe, Zn) in cooked brown, white, and parboiled rice using Synchrotron Micro-X-ray Fluorescence (sXRF) for the first time. Complementary analysis with Inductively Coupled Plasma Mass Spectrometry (ICP-MS) validates bulk elemental concentrations. Results from this dual-approach study reveal significantly higher micronutrient concentrations in brown rice compared to white or parboiled rice, with nutrients predominantly localised in the peripheral layers and minimal presence in the endosperm. Notably, sXRF imaging identified nutrient-rich pockets within the grain periphery, offering new perspectives on nutrient distribution beyond peripheral accumulation. Additional insights include the impact of rice section thickness (50 and 150 μm) and beam dwell times (0.5 and 30s) on sXRF sensitivity and resolution, highlighting trade-offs in detection capabilities, advancing our understanding of micronutrient localisation in cooked rice.
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Dec 2025
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I14-Hard X-ray Nanoprobe
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Gaewyn
Ellison
,
Rhiannon E.
Boseley
,
Meg
Willans
,
Sarah
Williams
,
Evelyn S.
Innes
,
Paige
Barnard
,
Julia
Koehn
,
Somayra S. A.
Mamsa
,
Paul
Quinn
,
Daryl L.
Howard
,
Simon A.
James
,
Mark J.
Hackett
Diamond Proposal Number(s):
[34101]
Open Access
Abstract: Understanding the role of metal ions in normal and abnormal cell function continues to emerge as a critical research area in the biological and biochemical sciences. This is especially true in the context of brain health and neurodegenerative diseases, as the brain is especially enriched in metal ions. A range of microscopy and bioanalytical techniques are available to assist in characterizing and observing changes to the brain metallome. As is the case in many other scientific fields, the integration of multiple analytical methods often yields a more complete chemical picture and deeper biological understanding. Herein, we present a case study applying 4 different analytical methods to provide spatially resolved characterization of chemical and biochemical parameters relating to the iron (Fe) metallome within a specific brain region, cornu ammonis sector 1 (CA1) of the hippocampus. The CA1 hippocampal sector was chosen for investigation due to its known endogenous enrichment in Fe and its selective vulnerability to neurodegeneration. The 4 analytical techniques applied were X-ray fluorescence microscopy (to quantify Fe distribution); X-ray absorption near-edge structure (XANES) spectroscopy to reveal information on Fe oxidation state and coordination environment; immuno-fluorescence to reveal relative abundance of Fe storage proteins (heavy chain ferritin and mitochondrial ferritin); and spatial transcriptomics to reveal gene expression pathways relevant to Fe homeostasis. Collectively, the results highlight that although pyramidal neurons in lateral and medial regions of the hippocampal CA1 sector are morphologically similar, key differences in the Fe metallome are evident. The observed differences within the hippocampal CA1 sector potentially indicate a higher oxidative environment and higher metabolic turnover in medial CA1 neurons relative to lateral CA1 neurons, which may account for the heightened vulnerability to neurodegeneration that is observed in the medial CA1 sector.
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Oct 2025
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I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[35162]
Open Access
Abstract: Enamel erosion alters the structural integrity of the tooth surface, which can be measured using indentation techniques. However, traditional single-load indentation methods assume homogeneity within the eroded enamel, overlooking potential stratification within the subsurface lesion. This study investigates the presence of mechanical and porosity gradients within the enamel following simulated dietary acid exposure and examines how lesion depth and structure change with continued erosion. We applied varying-load micro-indentation to human enamel subjected to citric acid challenge, revealing a distinct stratification of mechanical properties. A soft superficial layer (~1- to 2-µm thick) exhibited significantly reduced hardness and was easily removed by ultrasonication, indicating its fragility. Beneath this layer, mechanical properties stabilized despite prolonged acid exposure (~3 min), suggesting a saturation point in lesion development. Profilometric analysis confirmed that although material loss increased with erosion time, the depth of the altered subsurface zone remained constant. To explore the porosity distribution, we used a novel gold nanoparticle labeling technique coupled with synchrotron-based X-ray fluorescence imaging. Nanoparticles (~20 nm) penetrated to depths of 15 to 20 µm, aligning closely with mechanical gradients inferred from indentation measurements. These findings indicate that subsurface enamel exhibits not only mechanical stratification but also corresponding variations in porosity. Our results demonstrate the limitations of single-load indentation in characterizing erosion-affected enamel and highlight the utility of multiload approaches in detecting structural heterogeneity. The correlation between mechanical softening and increased porosity suggests that the enamel subsurfaces are differentially affected. These findings raise important implications for therapeutic intervention: should remineralization strategies shift from bulk mineral delivery to layer-specific, functionally informed repair?
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Oct 2025
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I14-Hard X-ray Nanoprobe
I22-Small angle scattering & Diffraction
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Diamond Proposal Number(s):
[19466, 26220, 22709]
Open Access
Abstract: The deposition of calcium phosphate mineral within a collagen matrix plays a pivotal role in the formation of bone and teeth, yet understanding its precise mechanism and time-dependence remains a significant challenge. Conventional approaches are often constrained to ex situ studies and as a result the intrinsic dynamics governing collagen mineralization remains unclear. To address this knowledge gap, we developed a custom thermal flow cell to enable in situ characterization using Raman spectroscopy and small/wide-angle X-ray scattering for comparable sample settings. This approach allowed us to monitor the intricate process of collagen matrix mineralization from the initial infiltration of precursor phases to the formation of intermediate phosphate phases, and ultimately to the predominant growth of hydroxyapatite. Our findings reveal a striking expansion of the collagen matrix during initial infiltration, followed by compression in the early stages of mineralization, likely driven by water expulsion, which suggests the development of pre-stress similar to that observed in bone. As mineralization progressed, the matrix expanded once again, correlated with crystal growth. Post-mortem analyses confirmed the presence of intrafibrillar mineralization, with remarkable agreement to bone formation at up to 9 h of mineralization before over-mineralization occurred. Our study further identified a tessellated mineralization pattern within the collagen matrix, a feature also seen in bone, pointing to a highly regulated physico-chemical control of the mineralization dynamics. These insights deepen our understanding of the fundamental processes governing bone mineralization with broad implications for designing advanced biomaterials.
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Oct 2025
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I14-Hard X-ray Nanoprobe
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Diamond Proposal Number(s):
[34794]
Abstract: Nanoscale molecular interactions between growing crystals and charged polyelectrolytes are crucial to understand the self-assembly of hierarchical organic–inorganic superstructures. Little is known about earth alkaline sulfate biominerals. Yet, a detailed understanding of bioinspired crystallization is crucial for developing general descriptors for bottom-up syntheses of complex ceramics. This study investigates biomimetic strontium sulfate (SrSO4) crystallization in the presence of poly(α-glutamic acid) using multiscale microscopy and vibrational spectroscopy. Using scanning electron microscopy, we observed doughnut-shaped spherulites with granular surface texture. Biomolecule inclusion led to pronounced peak broadening in synchrotron X-ray powder diffraction, wide-angle X-ray scattering, and Raman spectroscopy, commensurate with nanoscale domain sizes and pronounced lattice strain. Texture-like wide-angle X-ray scattering patterns and nanosized domains in transmission electron microscopy support the notion of mesocrystalline organization. Based on Z-contrast STEM imaging, intercalated organics are organized as elongated nanoclusters. Diffracting planes radiate outward from the crystal center, indicating a centrosymmetric strain field. The three-dimensional (3D) chemistry was investigated using atom probe tomography, which revealed a helical distribution of organic inclusions. This approach exemplifies how organic–inorganic templating can guide the evolution of intricate biomorphic crystal shapes. Round strontium sulfate crystals bear technological potential in the field of optoelectronics, such as IR–vis conversion materials or curved waveguides.
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Oct 2025
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I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[22220]
Open Access
Abstract: Sulfurisation of organic matter (OM) is a prominent preservation mechanism, however iron sulfide precipitation, particularly pyrite (FeS2), can counteract this mechanism. There is a dearth of high-resolution, spatially-resolved spectroscopic (redox) information on sulfur and iron inventories within organic-rich rocks that would improve our understanding of prevailing environmental conditions during deposition. Here, state-of-the-art synchrotron-based X-ray absorption and fluorescence analyses of key organic- and sulfur-rich mudstones demonstrate the potential of these techniques to non-destructively map and produce detailed spectroscopic information. Detailed high-resolution analyses (μm- to mm-scale) reveal the presence of widespread sulfurised OM in the Blackstone Band of the Kimmeridge Clay Formation, in line with a persistence of euxinia over a long temporal span and low reactive iron input, facilitating the preservation of OM through sulfurisation. In contrast, the presence of sulfurised OM was transitional in the Monterey Formation, consistent with fluctuating water column redox conditions, and is less significant in the Whitby Mudstone Formation, likely due to the high reactive iron concentrations outcompeting sulfurised OM formation. Analyses of sulfur species using model compounds further indicate that the Whitby Formation is strongly enriched in inorganic reduced sulfur minerals, while both the Kimmeridge Clay and Monterey Formations are dominated by organic sulfur species. These synchrotron-based observations improve our understanding of environmental conditions during the time of deposition of these mudstones and thus show great promise in the study of organic-rich sediments, especially in allowing their depositional settings to be more accurately reconstructed.
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Sep 2025
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I14-Hard X-ray Nanoprobe
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Diamond Proposal Number(s):
[34086]
Open Access
Abstract: Compared with conventional laboratory-scale X-ray techniques, synchrotron based X-rays with higher brilliance and higher coherence allow for the investigation of various material properties with high spatial resolution. The microscopic behaviours of materials can be examined using the Hard X-ray Nanoprobe beamline (I14) at Diamond Light Source, which provides a 50 nm focused beam and has been successfully employed to identify nanoscale optoelectronic features in energy-harvesting materials such as halide perovskites that exhibit local heterogeneity. We have developed X-ray beam-induced current (XBIC) measurement capability at I14 to address the growing demand for operando analysis in energy-harvesting research. Here, we demonstrate that X-ray fluorescence (XRF)/XBIC multimodal measurements are feasible at I14 and apply these newly implemented techniques to study perovskite solar cells with various additive concentrations to understand the effect of the additive on nanoscale optoelectronic performance. This expanded operando characterization capability offers the possibility of monitoring nanometre-scale compositional variations and corresponding optoelectronic features of actual solar cell configurations.
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Sep 2025
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B18-Core EXAFS
I14-Hard X-ray Nanoprobe
I18-Microfocus Spectroscopy
I19-Small Molecule Single Crystal Diffraction
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Diamond Proposal Number(s):
[33674, 35117, 35776, 40942, 37789]
Open Access
Abstract: Achieving safe and sustainable nanomaterials remains challenging—not necessarily from limited synthetic innovation but due to gaps in observing structural and chemical transformations under environmental conditions. Here, we make a call for a tri-beam operando characterization strategy, integrating synchrotron, neutron, and X-ray free-electron laser (XFEL) techniques into one synergistic experimental framework. Unlike traditional methods providing disconnected snapshots, tri-beam analysis dynamically tracks nanomaterial evolution from atomic-scale changes to structural collapse under near-real-world/quasi-realistic conditions. This holistic approach reveals previously hidden degradation pathways, transient states, and physicochemical thresholds that reshape definitions of material safety. Enhanced by robotic automation, machine learning, and findable, accessible, interoperable, and reusable (FAIR) data principles, our method directly supports Europe’s safe and sustainable by design (SSbD) initiative. We propose embedding tri-beam datasets into regulatory standards, predictive models, and AI-driven screening workflows. Ultimately, tri-beam operando characterization represents a transformative platform for designing resilient, high-performance nanomaterials that meet the environmental and societal demands of the 21st century.
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Sep 2025
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I14-Hard X-ray Nanoprobe
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Open Access
Abstract: This chapter (Nano-Imaging for Advanced X-ray Fluorescence and Absorption Spectroscopy Applications) is a contribution to the Geostandards and Geoanalytical Research Handbook of Rock and Mineral Analysis – an online textbook that is a fully revised and updated edition of A Handbook of Silicate Rock Analysis (P. J. Potts, 1987, Blackie, Glasgow).
Chapter 16 (from Section 3 of the handbook devoted to microbeam techniques) has been designed to provide a coherent progression, starting with a brief introduction of the essential fundamentals and the practical information needed to understand the experimental specifics of nano-XRF imaging. This concise yet crucial information is followed by a comprehensive presentation of current applications of nano-XRF imaging, with examples showcasing elemental measurement and XAS applications based on nano-XRF imaging. To conclude, the final section offers a brief overview of emerging perspectives that should be of particular interest to young researchers at the beginning of their careers.
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Aug 2025
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B18-Core EXAFS
I14-Hard X-ray Nanoprobe
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You Cheng
Khng
,
Gianni F.
Vettese
,
Satoshi
Utsunomiya
,
Joyce W. L.
Ang
,
Jessica M.
Walker
,
Julia
Parker
,
Thomas
Neil
,
Katherine
Morris
,
Liam
Abrahamsen-Mills
,
Mirkka
Sarparanta
,
Gareth T. W.
Law
Diamond Proposal Number(s):
[31916, 31395]
Open Access
Abstract: Uranium dioxide (UO₂) particles can be released from mines, nuclear fuel manufacturing, reactor accidents, and weapons use. They pose inhalation risks, yet their behavior in the human lung remains poorly understood. This study investigates the long-term chemical alteration and dissolution of µm-sized UO₂ particles in two model lung fluids: Simulated Lung Fluid (SLF) and Artificial Lysosomal Fluid (ALF), representing extracellular and intracellular lung environments, respectively. Particles were exposed to each fluid at 37°C for up to 180 days (SLF) and 900 days (ALF). In SLF, UO₂ showed low apparent solubility (<2% U released to solution), but solid-phase analyses revealed significant oxidation of U(IV) (~50%) and formation of autunite-like sheets on the UO2 surface. Secondary phase formation may lessen overall UO2 dissolution, promoting long-term particle retention, whilst modifying particle chemical toxicity and cell uptake. In contrast, Monte Carlo simulations indicate that the SLF-induced surface alteration would reduce (>50%) external radiation dose from the particles. In contrast, UO₂ readily dissolved in ALF (~75% uranium released to solution in 60 days, ~100% by 900 days). There was no evidence of secondary phase formation in ALF, but extensive particle matrix dissolution/disaggregation was observed by 30 days. Fragmentation of the UO2 polycrystalline matrix may lead to release of smaller UO₂ crystallites, which could translocate more readily. Overall, this work provides new mechanistic insight into the fate of inhaled UO₂ under physiologically relevant conditions, highlighting a possible need to consider particle reactivity and alteration processes in health risk assessments.
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Aug 2025
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