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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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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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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E01-JEM ARM 200CF
E02-JEM ARM 300CF
I18-Microfocus Spectroscopy
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N.
Topping
,
J. C.
Bridges
,
L. J.
Hicks
,
L.
Petera
,
C. S.
Allen
,
J.
Ryu
,
D. G.
Hopkinson
,
M.
Danaie
,
L.
Blase
,
F. M.
Willcocks
,
G.
Douglas
,
H. G.
Changela
,
T.
Noguchi
,
T.
Matsumoto
,
A.
Miyake
Diamond Proposal Number(s):
[30752, 31953, 32874, 35976, 29615, 31641, 35046]
Open Access
Abstract: A correlative multi-technique approach, including electron microscopy and X-ray synchrotron work, has been used to obtain both structural and compositional information of a sulfur-bearing serpentine identified in several carbonaceous chondrites (Winchcombe CM2, Aguas Zarcas CM2, Ivuna CI, and Orgueil CI), and in Ryugu samples returned by the Hayabusa2 mission. S-K edge X-ray absorption spectroscopy was used to determine the oxidation state of sulfur in the serpentine in all samples except Ryugu. The abundance of this phase varies across these samples, with the largest amount in Winchcombe; ~12 vol% of phyllosilicates are identified as sulfur-bearing serpentine characterized by ~10 wt% SO3 equivalent. HRTEM studies reveal a d001-spacing range of 0.64–0.70 nm across all sulfur-bearing serpentine sites, averaging 0.68 nm, characteristic of serpentine. Sulfur-serpentine has variable S6+/ΣStotal values and different sulfur species dependent on specimen type, with CM sulfur-bearing serpentine having values of 0.1–0.2 and S2− as the dominant valency, and CIs having values of 0.9–1.0 with S6+ as the dominant valency. We suggest sulfur is structurally incorporated into serpentine as SH− partially replacing OH−, and trapped as SO42− ions, with an approximate mineral formula of (Mg Fe2+ Fe3+ Al)2-3(Si Al)2O5(OH)5-6(HS−)1-2(SO4)2−0.1-0.7. We conclude that much of the material identified in previous studies of carbonaceous chondrites as TCI-like or PCPs could be sulfur-bearing serpentine. The relatively high abundance of sulfur-bearing serpentine suggests that incorporation of sulfur into this phase was a significant part of the S-cycle in the early Solar System.
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Nov 2025
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I18-Microfocus Spectroscopy
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Rémi
Kinet
,
Joanna
Sikora
,
Marie-Laure
Arotcarena
,
Melina
Decourt
,
Eric
Balado
,
Evelyne
Doudnikoff
,
Sylvain
Bohic
,
Marta
Vesnaver
,
Anna
Lovisotto
,
Marie-Laure
Thiolat
,
Nathalie
Dutheil
,
Claire
Mazzocco
,
Karim
Harhouri
,
Rémy
Steinschneider
,
Severine
Menoret
,
Laurent
Tesson
,
Ignacio
Anegon
,
Michele
Morari
,
Miquel
Vila
,
François
Georges
,
Erwan
Bezard
,
Pierre-Olivier
Fernagut
,
Benjamin
Dehay
Diamond Proposal Number(s):
[29838]
Open Access
Abstract: Mutations in the ATP13A2 gene were identified as the cause of Kufor-Rakeb syndrome (KRS), a juvenile-onset form of Parkinson’s disease (PD). Developing relevant and predictive models for the rare PD forms is necessary to understand the pathological mechanisms and validate therapeutic strategies. Herein, we aimed to comprehensively characterize the first transgenic Atp13a2 knockout rat model. Behavioral assessment demonstrated specific developmental deficits in animals with deletion of Atp13a2. Further analysis revealed that Atp13a2 knockout rats displayed age-dependent fine motor skills deficits and impaired locomotor habituation similar to those observed in PD patients at the early stage of motor symptoms. In contrast, no change in the nigrostriatal integrity was observed. An extended investigation on heavy metals homeostasis, autophagy-related markers, and lipofuscin accumulation showed significant changes reminiscent of KRS. Finally, we tested whether inducing pathology by viral-mediated overexpression of human α-synuclein or human tyrosinase exacerbated the onset or extent of pathological changes. This Atp13a2 KO rat model could help better understand autophagy in PD pathogenesis and open new therapeutic validation opportunities.
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Nov 2025
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I18-Microfocus Spectroscopy
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Nana
Li
,
Wenge
Yang
,
Jiayi
Guan
,
Limin
Yan
,
Xiaozhi
Yan
,
Mingtao
Li
,
Xuqiang
Liu
,
Kai
Zhang
,
Feiyu
Li
,
Shu
Cai
,
Haini
Dong
,
Adama
N-Diaye
,
Junjie
Zhang
,
Yantao
Cao
,
Hanjie
Guo
,
Qingyu
Kong
,
Liling
Sun
,
Monica
Amboage
Diamond Proposal Number(s):
[36140]
Abstract: Recent discoveries of pressure-induced high-temperature superconductivity in bilayer and trilayer Ruddlesden–Popper nickelates have sparked global research interest in these unconventional superconducting systems. Understanding the crystal and electronic structures is essential to uncover the underlining mechanism of superconductivity. For trilayer La4Ni3O10−δ, structural studies have only been conducted at ambient temperature, leaving a vast P–T space unexplored. Here we report our in situ investigations using X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS), covering pressures from 0 to 51.3 GPa and temperatures from 10 to 300 K, to explore the critical P–T phase diagram of La4Ni3O10−δ. Our results show that La4Ni3O10−δ undergoes a phase transition from monoclinic (P21/a) to tetragonal (I4/mmm) under pressure and is further transformed to an orthorhombic (Bmab) phase as it enters the superconducting state upon cooling at pressures above 48 GPa. Additionally, the Ni valence state increases with the pressure and remains stable at low temperatures. The p and d orbitals of Ni and the enhanced hybridization between Ni 3d and O 2p orbitals play a significant role in the superconducting state due to the distortion of the NiO6 octahedra. Our study provides important insights into the mechanisms driving high-Tc superconductivity in nickelates and establishes a basis for further investigation into related superconducting systems.
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Nov 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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B16-Test Beamline
I16-Materials and Magnetism
I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[15884, 15926, 11645]
Open Access
Abstract: Our bone health as an adult is defined by patterns of development in early life, with perturbed growth during fetal and neonatal periods predisposing individuals to poor bone health in adulthood. Studies have identified poor maternal diet during pregnancy as a critical factor in shaping offspring bone development, with significant impacts on adult bone structure and health. However, the association between a father’s diet and the bone health of his offspring remains poorly defined. To address this knowledge gap, we fed male C57BL/6 mice either a control normal protein diet (NPD; 18% protein) or an isocaloric low protein diet (LPD; 9% protein) for a minimum of 8 weeks. Using these males, we generated offspring through artificial insemination, in combination with vasectomised male mating. Using this approach, we derived offspring from either NPD or LPD sperm but in the presence of NPD or LPD seminal plasma. Using micro-computed tomography and synchrotron X-ray diffraction, we observed significant changes in offspring femur morphology and hydroxyapatite crystallographic parameters from just 3 weeks of age in offspring derived from LPD sperm or seminal plasma. We also observed that differential femur morphology and hydroxyapatite crystallographic parameters were maintained into adulthood and into a second generation. Analysis of paternal sperm identified a down regulation of 26 osteogenic genes associated with extracellular matrix levels and maintenance, transcription and growth factors and bone ossification. These observations indicate that poor paternal diet at the time of conception affects offspring bone development and morphology in an age and generation specific manner.
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Oct 2025
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I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[39923]
Abstract: Climate change is accelerating sea-level rise (SLR), increasing the intensity and frequency of saltwater intrusion, and coastal storm flooding. Areas that are heavily contaminated with pollutants such as arsenic (As) in coastal areas may be influenced by tidal cycles. The effects of seawater intrusion and prolonged flooding will drive chemical and mineralogical changes which may threaten water quality and coastal ecosystem health. We investigated the re-mobilization of As from heavily contaminated urban sediments (13.3 g kg-1 As), over a seawater salinity gradient for 35 d combining anoxic incubation and X-ray absorption spectroscopy. We observed that As mobility is closely related to the reductive dissolution of Fe oxyhydroxides because the variation of ~1.3% of the total Fe dissolution was associated with ~9% of total As release in solution. Sulfidation boosted by salinity increased FeIII-mineral reductive dissolution, which increased As release at short term incubation (before 14 d), however at long term incubation (at 35 d), sulfidation also re-immobilized the soluble As to stable new solid phases such as Asx-Sy minerals and coprecipitation/adsorption with FeS minerals. Our results demonstrate the threat that SLR has on As release and immobilization from contaminated coastal sediments or soils due to biogeochemical redox cycling of Fe and S.
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Oct 2025
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