I18-Microfocus Spectroscopy
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Abstract: The results obtained in this thesis demonstrate that NCLX plays a relevant role in the pathophysiology of ischemic stroke, particularly during the reperfusion phase, by modulating ROS production, lipid peroxidation, and iron metabolism. In the murine model, NCLX inhibition effectively reduced infarct volume and cerebral iron overload, although its effects did not extend to other critical aspects of functional recovery, such as oedema, neurodegeneration or glial inflammation. These findings indicate that ferroptosis represents one of the multiple pathological mechanisms involved in ischemic stroke and highlight the relevance of the mitochondrial exchanger NCLX as a key factor at the intersection of mitochondrial metabolism, oxidative stress, and iron homeostasis.
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Mar 2026
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I18-Microfocus Spectroscopy
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Sara
Callegaro
,
Don R.
Baker
,
Kalotina
Geraki
,
Angelo
De Min
,
Leone
Melluso
,
Andrea
Marzoli
,
Manfredo
Capriolo
,
Frances M.
Deegan
,
Francesco
Caraffini
,
Jean
Bédard
,
Joshua H. F. L.
Davies
,
Andrea
Boscaini
,
Paul R.
Renne
Open Access
Abstract: Large Igneous Province (LIP) volcanism is a major driver of past global change via degassing of large volumes of climate-altering and poisonous gases (such as H₂O, CO₂, CH₄, SO2). These volatile species can produce contrasting effects on the atmosphere, from long-term global warming to short-lived volcanic winters. We know from historical cases (e.g., the 1783–84 Laki fires, the 1991 Pinatubo eruption) that sulfur-rich eruptions can produce global cooling with societal consequences. In deep time, repeated volcanic winters occurring during LIP emplacement, superimposed on long-term warming, could have stressed ecosystems and contributed to mass extinction, but their short duration makes them difficult to detect in the stratigraphic record (Callegaro et al., 2020; 2023; Kent et al., 2024). Sedimentary proxies of short-term cooling such as glendonite crystallization are being explored, but their signals remain ambiguous (Vickers et al., 2020). We propose a complementary, “within-magma” approach for tracing sulfur-rich magmatic pulses capable of generating volcanic winters. Using synchrotron X-ray microfluorescence, we measure sulfur concentrations in clinopyroxene from LIP magmas, and calculate equilibrium melt concentrations with established partition coefficients. Since clinopyroxene is an early and almost ubiquitous phase in LIPs magmas, this method allows the detection of variations in sulfur budgets throughout the stratigraphy of a lava pile, identifying intervals of sulfur-rich lavas as potential drivers of volcanic winters. We discuss future developments of the method, and results obtained for magmas of the Deccan Traps (Western Ghats lava pile, India), and Franklin large igneous province.
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Mar 2026
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I14-Hard X-ray Nanoprobe
I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[39618, 39938, 302085, 31588, 5116, 36811]
Open Access
Abstract: Correlative microscopy linking synchrotron X-ray fluorescence (SXRF) with optical imaging is valuable for contextualizing chemical element distributions in biology. The spatial correlation necessary to achieve this presents fundamental challenges and can be a significant constraint on accuracy and data interpretation. We present a technical solution based on a finder grid concept, optimized for SXRF correlative studies of metals in biological tissues, with scope for wider adaptation and application. A hierarchically patterned fiducial system was directly etched onto spectroscopically clean quartz substrates via femtosecond laser ablation. This design enables improved correlation among SXRF, optical imaging, and histological staining over a greater range of length scales than conventional registration methods such as the use of tissue architecture from serial sections and the use of electron-microscopy-resolution finder grids and applied fiduciary markers that can introduce XRF-signal-dominating levels of elements such as copper, nickel, gold, and titanium. We present two quartz finder grid formats: a microgrid and a nanogrid design. We demonstrate their utility for rapid ROI relocalization and same-section correlative workflows using human brain tissue. The etched quartz finder grid approach facilitates rapid and reproducible ROI relocalization and alignment across instruments, particularly where integral fiducial markers are sparse or ambiguous.
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Mar 2026
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I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[36744]
Open Access
Abstract: The integration of nanoencapsulation techniques with foliar application presents a promising approach to enhance selenium (Se) biofortification in agriculture. This study examined the foliar uptake of liposome-encapsulated Se in wheat leaves (Triticum aestivum) using synchrotron-based micro-X-ray fluorescence (μ-XRF) and confocal microscopy. μ-XRF mapping showed Se accumulation at leaf edges after 24 h, suggesting initial uptake via stomata, while free Se was absorbed and transported more rapidly, highlighting the slow-release effect provided by liposomal encapsulation, longer than the analyzed time. No immediate translocation of Se to the stem was observed, suggesting that more time is required for this internal movement. Micro-X-ray absorption near-edge structure (μ-XANES) speciation analysis demonstrated that Se was metabolized into organic forms within the plant. Finally, confocal fluorescence microscopy confirmed liposome absorption through the plant surface within 24 h, corroborating the μ-XRF findings. These results are crucial for optimizing liposome formulation to maximize Se transfer to edible parts.
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Mar 2026
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I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[35970]
Open Access
Abstract: We have determined the pressure dependence of the ratio S6+/(S2-+S6+) in silicate melts by measuring the effects of pressure on the concentrations of sulfide (S2-) and sulfate (SO42-) species at known fugacities of sulfur and oxygen. For S2- we controlled f(S2) using mixtures of Ag and Ag2S with oxygen fugacity held at the CCO buffer. For S6+ we measured molten CaSO4 solubility as a function of pressure. We define sulfide capacity and sulfate capacity from the S2- and S6+ contents of the melt as (Fincham and Richardson, 1954): and .
The dependences of and on pressure were found, with P in bars and T in K, to be:
and . The negative pressure dependences are due to the differences in partial molar volumes between sulfide S2- and oxide O2– species and sulfate SO42 -and oxide O2– which we calculate to be ∼ 10.7 cm3/mol and ∼ 31.6 cm3/mol respectively. These are similar to the differences in volumes between CaS and CaO (10.96 cm3/mol) and CaSO4 and CaO (29.2 cm3/mol).
We used these and equations to calculate the pressure dependence of the “crossover” oxygen fugacity at which S2- transforms to S6+ in silicate melts of different composition. The crossover is shifted in absolute f(O2) by + 0.25 log units or, relative to FMQ, by −0.41 log units as pressure is increased from 1 bar to 1 GPa at 1400 °C. This demonstrates that the effect of pressure on sulfur oxidation state is small and may be neglected for many purposes. The pressure dependence of the S2-—S6+ crossover means that there would be some electron exchange between Fe2+ and S6+ during decompression in a closed system (S2-+8Fe3+ = S6++8Fe2+). The effect is small, but largest in melts which start at oxygen fugacities close to and above FMQ and would, for a basalt containing 1500 ppm S lead to an increase in oxygen fugacity of 0.4 to 0.5 logf(O2) units during decompression from 1.5 GPa to 1 bar.
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Mar 2026
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I18-Microfocus Spectroscopy
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Open Access
Abstract: Understanding the impact of volcanic eruptions on climate over the last two millennia is essential to place current anthropogenic climate change into a long-term context. High-resolution proxy archives are crucial for this purpose, yet their availability decreases rapidly back in time. Besides ice cores, speleothems and corals, tree rings represent a uniquely valuable archive, providing records with annual resolution of past-climate change. Volcanic eruptions are among the most impactful natural forcings on Earth’s climate, through the injection of gaseous plumes into the atmosphere that can induce warming or cooling of the planet surface. While some of these impacts are well-known and studied, there are many older volcanic events whose details are unknown or uncertain, due to the lack of direct historical evidence.
Volcanic plumes transport volatile elements (e.g., S, Fe, Zn, Cu, Hg) that can be absorbed by trees and recorded in the yearly tree-ring layers. So far, dendrochemistry has been widely applied to assess anthropogenic pollution, but our research explores its potential as a novel proxy: by identifying chemical spikes of these elements in tree rings of known age, it may be possible to correlate them with known volcanic eruptions or identify previously unrecognized volcanic events. Here we present data obtained at Diamond synchrotron on tree rings from juniper (Juniperus communis) samples from Kevo, Finland, whose dendrochronological records extend back to the early Middle Ages. These measurements revealed distinct peaks in metal elements such as Zn and Cu, which are typically enriched in volcanic plumes and can be hosted in the wood as semi-nutrients. Some concentration peaks detected in the tree rings correspond to the ages of major Icelandic eruption from the lower Middle Ages.
These preliminary results suggest that dendrochemical analyses may provide a new archive of past volcanic activity. If validated, this approach could significantly improve reconstructions of volcanic eruptions of the past and corresponding climate variability over the last two millennia.
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Mar 2026
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B18-Core EXAFS
I18-Microfocus Spectroscopy
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Swaroop
Chakraborty
,
Iuliia
Mikulska
,
Pankti
Dhumal
,
Nathan
Langford
,
Susan
Nehzati
,
Rhiannon
Boseley
,
Sang
Pham
,
Christian
Pfrang
,
Manpreet
Kaur
,
Eugenia
Valsami-Jones
,
Konstantin
Ignatyev
,
Dhruv
Menon
,
Superb K.
Misra
,
Iseult
Lynch
Diamond Proposal Number(s):
[33674, 35117, 35776, 40080, 40942]
Open Access
Abstract: Metal–organic frameworks (MOFs) hold immense potential for applications from separations to catalysis, yet their long-term behavior across real-world environments remains unclear. Here we introduce a hierarchical exposure framework that tracks the structural and chemical transformations in the archetypal zirconium MOF UiO-66 across sequential compartments─atmospheric gases, air, aqueous media and a biological host─and resolves how prior exposures condition or prime subsequent transformations. Using synchrotron-based spectroscopy, we find that oxidative/reactive gases leave the Zr-carboxylate nodes essentially intact, whereas exposure to environmentally relevant aqueous media initiates partial shifts in local Zr coordination and introduces oxygen into the pores─with transformation extent governed by the chemistry of the environmental matrices. Strikingly, acute exposure (24 h) to the water flea Daphnia magna drives profound framework degradation and respeciation to Zr hydroxide species. Microfocus XRF maps show that Zr is highly localized in the animal’s digestive tract, and region-specific XANES confirms uniform speciation across its tissues. Our findings establish a paradigm shifting cross-compartment transformation hierarchy in which biological processes can dominate the fate of stable MOFs even when abiotic exposures appear benign. Thus, organism-level biotransformation should be performed as a necessary part of environmental safety assessments and materials design.
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Jan 2026
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B18-Core EXAFS
I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[33674, 35117, 35776, 40942]
Open Access
Abstract: Metal–organic frameworks (MOFs) are entering water technologies on the premise that abiotic stability predicts ecological safety. We overturn this assumption by showing that UiO-66 – often regarded as chemically and structurally robust – remains intact after 7-day aging in natural borehole water yet undergoes rapid in vivo transformation in Daphnia magna. Synchrotron Microfocus X-ray absorption spectroscopy (XAS) revealed collapse of the ordered Zr–carboxylate coordination into disordered Zr–O environments within the gut; Extended X-ray Absorption Fine Structure (EXAFS) showed loss of second-shell features, and Transmission Electron Microscopy (TEM) confirmed loss of crystallinity with nanoscale aggregates appearing within 24 h of ingestion. Although acute immobilization was limited (48 h EC50 ≈ 26.5 μg mL–1), a sublethal, environmentally relevant exposure (10 μg mL–1) caused pronounced chronic effects: brood initiation was delayed by 3–5 days and cumulative reproduction decreased by ∼74% without mortality. We attribute these outcomes to gut-level transformation and associated energetic/physiological burdens, not captured by standard acute tests. These results show that abiotic stability does not necessarily imply biological inertness and highlight the need to integrate in vivo transformation pathways with chronic end points in environmental risk assessment for water-sector materials. This perspective provides a mechanistic basis to inform Safe-and-Sustainable-by-Design (SSbD) MOFs before widespread deployment in water treatment.
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Dec 2025
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I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[31815]
Open Access
Abstract: Dehydroxylate I, a product of the thermal decomposition of serpentine, has been observed in heated carbonaceous chondrite meteorites. To better understand the occurrence of dehydroxylate I on carbonaceous asteroids, we have experimentally heated the carbonaceous chondrite Murchison from 400 to 550 °C at 25°C temperature steps, during which in situ micro X-ray diffraction (µXRD) patterns were collected using synchrotron radiation. µXRD was utilized such that the dehydroxylate I’s diffraction pattern could be isolated and characterized. This was successfully achieved, with the phase being detected at 400 °C. A diffraction pattern for dehydroxylate I was isolated at 525 °C, where it displayed crystallographic similarities to the mineral carlosturanite. We propose dehydroxylate I is produced when gaps form in serpentine’s tetrahedral sheet during its breakdown, which is consistent with previous studies on serpentine decomposition. The d-spacings for dehydroxylate I described here can be used to better identify it in natural and experimentally heated terrestrial and meteoritic samples.
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Dec 2025
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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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