Synchrotron X-ray Fluorescence Research Articles

U and Th zonation in apatite observed by synchrotron X-ray fluorescence tomography and implications for the (U–Th) ∕ He system

Abstract. Synchrotron X-ray fluorescence microtomography can non-destructively image the three-dimensional distribution of several trace elements in whole apatite crystals at the resolution of 1 µm3. This allows for precise determination of the physical geometry of a crystal and the quantification of the relative abundance of the radioactive parent nuclides uranium and thorium with high fidelity. We use these data to develop a more precise alpha ejection correction for (U–Th) / He thermochronology and high-resolution models of apatite crystals that are the foundation for a new generation of three-dimensional diffusion modeling. The application of synchrotron radiation to non-destructive imaging of minerals used for geochronology sheds light on causes of long-standing unresolved problems in the field that are rooted in previously unmeasurable parent nuclide zonation, especially the pervasive overdispersion of single-crystal ages.

Heterometallic Molecular and Ionic Isomers.

Numerous descriptions of structural isomerism in metal complexes do not list any molecular vs ionic isomers. At the same time, one of the most striking examples of structural isomerism in organic chemistry is molecular urea, which has the same atomic composition as the chemically distinct ionic ammonium cyanate. This iconic organic couple now meets its inorganic heterometallic counterpart. We introduce a new class of structural isomers, molecular vs ionic, that can be consummated in complex and coordinatively unsaturated polynuclear/heterometallic compounds. We report inorganic molecular and ionic isomers of the composition [NaCrFe (acac)3(hfac)3] (acac = acetylacetonate; hfac = hexafluoroacetylacetonate). Heterometallic molecular [CrIII(acac)3-Na-FeII(hfac)3] (1m) and ionic {[CrIII(acac)3-Na-CrIII(acac)3]+[FeII(hfac)3-Na-FeII(hfac)3]-} (1i) isomers have been isolated in pure form and characterized. While both ions are heterobimetallic trinuclear entities, the neutral counterpart is a heterotrimetallic trinuclear molecule. The two isomers exhibit distinctly different characteristics in terms of solubility, volatility, mass spectrometry ionization, and thermal behavior. Unambiguous assignment of the positions and oxidation/spin states of the Periodic Table neighbors, Fe and Cr, in both isomers have been made by a combination of characterization techniques that include synchrotron X-ray resonant diffraction, synchrotron X-ray fluorescence spectroscopy, Mössbauer spectroscopy, and DART mass spectrometry. The transformation between the two isomers that does take place in solutions of noncoordinating solvents has also been tested.

Reconstructing infant mortality in Iberian Iron Age populations from tooth histology

The Neonatal Line (NNL) of the tooth serves as a unique identifier, allowing us to distinguish whether a child survived birth. This line is essential for assessing the age at death of infants from skeletal remains found in archaeological contexts. Our primary objective is to accurately determine the age of infant intramural inhumations from the Iberian Iron Age (8th-1st centuries BC) by analyzing histological sections of tooth germs. Due to their fragility and high susceptibility to taphonomic factors, these samples are challenging to handle. By accurately assessing their age, we aim to classify individuals into various stages of infant mortality, which will help reconstruct infant mortality patterns in these populations.We analyze unerupted and still-forming crown deciduous teeth from 45 infant burials. By calculating Crown Formation Time (CFT) and identifying the NNL, we determine both gestational and chronological ages. We further validate the reliability of NNL identification through Synchrotron X-ray Fluorescence (SXRF) elemental analysis (Ca, Zn, Cu) on two contemporary and two archaeological samples.Our histological study reveals the chronological age of 38 infants from Iberian settlements, ranging from the 30th week of gestation to the 2nd postnatal month. The age distribution shows an attritional mortality pattern, with nearly half experiencing perinatal mortality, including preterm births. These findings support the hypothesis that mortality was primarily attributed to natural causes. Our research enhances the understanding of infant life history events in prehistory by combining histological analysis of tooth NNL and CFT, highlighting the technique's potential and limitations.

Ultrathin natural biotite crystals as a dielectric layer for van der Waals heterostructure applications

Biotite, an iron-rich mineral belonging to the trioctahedral mica group, is a naturally abundant layered material (LM) exhibiting attractive electronic properties for application in nanodevices. Biotite stands out as a non-degradable LM under ambient conditions, featuring high-quality basal cleavage-a significant advantage for van der Waals heterostructure (vdWH) applications. In this work, we present the micro-mechanical exfoliation of biotite down to monolayers (1Ls), yielding ultrathin flakes with large areas and atomically flat surfaces. To identify and characterize the mineral, we conducted a multi-elemental analysis of biotite using energy-dispersive spectroscopy mapping. Additionally, synchrotron x-ray fluorescence and infrared nano-spectroscopy were employed to probe its iron content and vibrational signature in few-layer form, respectively, with sensitivity to the layer number. We have also observed good morphological and structural stability in time (up to 12 months) and no important changes in their physical properties after thermal annealing processes in ultrathin biotite flakes. Conductive atomic force microscopy evaluated its electrical capacity, revealing an electrical breakdown strength of approximately 1 V nm-1. Finally, we explore the use of biotite as a substrate and encapsulating LM in vdWH applications. We have performed optical and magneto-optical measurements at low temperatures. We find that ultrathin biotite flakes work as a good substrate for 1L-MoSe2, comparable to hexagonal boron nitride flakes, but it induces a small change of the 1L-MoSe2g-factor values, most likely due to natural impurities on its crystal structure. Furthermore, our results show that biotite flakes are useful systems to protect sensitive LMs such as black phosphorus from degradation for up to 60 days in ambient air. Our study introduces biotite as a promising, cost-effective LM for the advancement of future ultrathin nanotechnologies.

Influence of Reinforcing nano-Al<sub>2</sub>O<sub>3</sub> Particles on Microstructure and Hardness Properties of HVOF Sprayed 80Ni20Cr Coatings

80Ni20Cr coatings produced by high-velocity oxygen fuel (HVOF) thermal spray technique are novel and widely used to improve the corrosion and wear resistance of metal and steel components in many applications, especially in coal-fired power plants. The present study investigated the effects of nano-Al2O3 at 0.5 wt.% on the microstructure of HVOF-sprayed 80Ni20Cr coating deposited on AISI 304L steels corresponding to its coating hardness. The coating was successfully sprayed with a thickness of 150 – 180 µm. The microstructure and phase formed by the coating were analyzed by a field emission electron microscope (FE-SEM) and an X-ray diffractometer (XRD). Synchrotron X-ray fluorescence spectroscopy (SRXRF) was used to confirm the Cr solid solution in the Ni-based coating. The presence of the nano-Al2O3 phase in the 80Ni20Cr coating was characterized by electron backscattered diffraction (EBSD). The nano-Al2O3 particles were homogenously distributed in the coating layers. The incorporation of nano-Al2O3 into 80Ni20Cr enhanced coating characteristics by decreasing surface roughness by 23% and increasing coating hardness by around 4%.

Nanoscale elemental and morphological imaging of nitrogen-fixing cyanobacteria.

Nitrogen-fixing cyanobacteria bind atmospheric nitrogen and carbon dioxide using sunlight. This experimental study focused on a laboratory-based model system, Anabaena sp., in nitrogen-depleted culture. When combined nitrogen is scarce, the filamentous prokaryotes reconcile photosynthesis and nitrogen fixation by cellular differentiation into heterocysts. To better understand the influence of micronutrients on cellular function, 2D and 3D synchrotron X-ray fluorescence mappings were acquired from whole biological cells in their frozen-hydrated state at the Bionanoprobe, Advanced Photon Source. To study elemental homeostasis within these chain-like organisms, biologically relevant elements were mapped using X-ray fluorescence spectroscopy and energy-dispersive X-ray microanalysis. Higher levels of cytosolic K+, Ca2+, and Fe2+ were measured in the heterocyst than in adjacent vegetative cells, supporting the notion of elevated micronutrient demand. P-rich clusters, identified as polyphosphate bodies involved in nutrient storage, metal detoxification, and osmotic regulation, were consistently co-localized with K+ and occasionally sequestered Mg2+, Ca2+, Fe2+, and Mn2+ ions. Machine-learning-based k-mean clustering revealed that P/K clusters were associated with either Fe or Ca, with Fe and Ca clusters also occurring individually. In accordance with XRF nanotomography, distinct P/K-containing clusters close to the cellular envelope were surrounded by larger Ca-rich clusters. The transition metal Fe, which is a part of nitrogenase enzyme, was detected as irregularly shaped clusters. The elemental composition and cellular morphology of diazotrophic Anabaena sp. was visualized by multimodal imaging using atomic force microscopy, scanning electron microscopy, and fluorescence microscopy. This paper discusses the first experimental results obtained with a combined in-line optical and X-ray fluorescence microscope at the Bionanoprobe.

Proteomic Insights into Trichome Responses to Elevated Elemental Stress in Cation Exchanger (CAX) Mutants.

Research on elemental distribution in plants is crucial for understanding nutrient uptake, environmental adaptation, and optimizing agricultural practices for sustainable food production. Plant trichomes, with their self-contained structures and easy accessibility, offer a robust model system for investigating elemental repartitioning. Transport proteins, such as the four functional cation exchangers (CAXs) in Arabidopsis, are low-affinity, high-capacity transporters primarily located on the vacuole. Mutants in these transporters have been partially characterized, with one of the phenotypes of the CAX1 mutant being altered tolerance to low-oxygen conditions. A simple visual screen demonstrated trichome density and morphology in cax1 and quadruple CAX (cax1-4: qKO) mutants remained unaltered. Here we used SXRF (Synchrotron X-Ray Fluorescence) to show that trichomes in CAX-deficient lines accumulated high levels of chlorine, potassium, calcium, and manganese. Proteomic analysis on isolated Arabidopsis trichomes. showed changes in protein abundance in response to changes in element accumulation. The CAX mutants showed an increased abundance of plasma membrane ATPase and vacuolar H-pumping proteins, and proteins associated with water movement and endocytosis, while also showing changes in proteins associated with the regulation of plasmodesmata. These findings advance our understanding of the integration of CAX transport with elemental homeostasis within trichomes and shed light on how plants modulate protein abundance under conditions of altered elemental levels.

Iron distribution and speciation in a 3D-printed hybrid food using synchrotron X-ray fluorescence and X-ray absorption spectroscopies

The bioavailability of iron from a food depends on its concentration and chemical form but also on dietary factors and nutrient interactions, which are affected by storage conditions and time. Here we investigated the time-course profile of iron in a hybrid 3D-printed food composed of alternating layers of liver and lentils after 0, 5, 7, 14 and 21 days of storage at 4 °C under oxygen or nitrogen packaging. Synchrotron X-ray fluorescence highlighted major variations in iron distribution in both the animal and plant parts of the food as a function of storage conditions. FeP and FeS positive spatial correlations pointed to iron-associated compounds. X-ray absorption near-edge structure spectroscopy showed spectral signatures specific to the animal and plant mixtures, and then highlighted interactions between animal and plant parts during food storage, with a change in iron forms in the plant part.

Habitat-specific allocations of elements in Atriplex lentiformis seeds indicate adaptation to metal toxicity.

Self-sustaining vegetation in metal-contaminated areas is essential for rebuilding ecological resilience and community stability in degraded lands. Metal-tolerant plants originating from contaminated post-mining areas may hold the key to successful plant establishment and growth. Yet, little is known about the impact of metal toxicity on reproductive strategies, metal accumulation, and allocation patterns at the seed stage. Our research focused on the metal tolerant Atriplex lentiformis. Specifically, we examined the effects of toxic metal(loid) concentration in soils on variability in its reproductive strategies, including germination patterns, elemental uptake, and allocation within the seeds. We employed advanced imaging techniques like synchrotron X-ray fluorescence microscopy (2D scans and 3D tomograms) combined with inductively coupled plasma mass spectrometry to reveal significant differences in metal(loid) concentration and distribution within the seed structures of A. lentiformis from contrasting habitats. Exclusive Zn hotspots of high concentrations were found in the seeds of the metallicolous accession, primarily in the sensitive tissues of shoot apical meristems and root zones of the seed embryos. Our findings offer novel insights into phenotypic variability and metal tolerance and accumulation in plants from extreme environments. This knowledge can be applied to enhance plant survival and performance in land restoration efforts.

Operando Tracking the Dissolution and Deposition Dynamics in Aqueous Zn-MnO2 Batteries

Aqueous Zn–MnO2 batteries have received extensive attention for next-generation large-scale energy storage because of their low cost and outstanding safety. Despite efforts to achieve better performances, the charge-storage chemistry of MnO2 cathodes remains controversial. Zn-ion insertion, Zn-ion/proton co-insertion, proton insertion, and electro-dissolution have been proposed as the mechanism of the MnO2 cathodes. More specifically, the pathway of Mn dissolution is debatable: while intercalation chemistry leads to dissolution caused by the Jahn–Teller effect of Mn(III), electro-dissolution relies on a conversion from Mn(IV) to Mn(II). Furthermore, it is recently considered that Mn dissolution/redeposition efficiency is crucial to the reversibility of MnO2 cathodes, depending on pre-added Mn in the electrolyte. The role of trace Mn additive is also confusing. Last but not least, Mn dissolution and deposition is conjectured to be linked to the dissolution/redeposition of Zn‐based species-that is, Zn4SO4·(OH)6·xH2O (ZSH). To understand these key scientific questions that enlighten the further design of materials and electrolytes, it is imperative to develop operando measurements of the MnO2 cathodes. In our study, we utilized synchrotron X-ray fluorescence microscopy with high spatial resolution to probe the evolution of Zn and Mn species during electrochemical cycling. We can quantify the relationship between Zn and Mn concentrations from the electrode level to the single-particle level. We conclude that during the first discharge, MnO2 delivers the capacity by electro-dissolution, accompanied by the rapid precipitation of ZSH due to change of pH. ZSH surrounds the MnO2, which has high reversibility with the pre-added Mn additive in electrolytes. Our work provides in-depth insights into the complex Zn/Mn deposition and deposition near the electrode surface which will guide the further development of aqueous Zn-MnO2 batteries.

Influence of fracturing fluids on shale matrix permeability and micro-mechanical properties after chemical interactions

Geochemical interactions between shale and hydraulic fracture fluids (HFFs), principally mineral dissolution and precipitation, can result in alteration of matrix permeability and tendency of proppant embedment, ultimately impacting hydrocarbon migration through the shale formation. This study aimed to quantify changes of core permeability and micromechanical properties after shale-HFF chemical interactions. Extent of chemical alteration of the solid phase was characterized by synchrotron X-ray fluorescence mapping, micro-computed tomography, and scanning electron microscopy. Post-reaction brine was evaluated for elemental concentrations. Both low-carbonate and high-carbonate shale exhibited carbonate dissolution, an iron oxidation zone, and barite precipitates partially infilling secondary porosity. These reactions were more obvious in the high-carbonate shale but extended further into the low-carbonate shale. Pulse-decay permeability measurements generally revealed increase in permeability after reactions, whereas hardness and modulus reduction were observed only in reaction zones of high carbonate shale. Inevitable heterogeneity of natural shale samples resulted in large deviations in hydromechanical measurements both on the core scale and on the microscale.

Native Cryo-Correlative Light and Synchrotron X-ray Fluorescence Imaging of Proteins and Essential Metals in Subcellular Neuronal Compartments

Native Cryo-Correlative Light and Synchrotron X-ray Fluorescence Imaging of Proteins and Essential Metals in Subcellular Neuronal Compartments

Characterisation of Fe Distribution in the Liquid-Solid Boundary of Al-Zn-Mg-Si Alloy Using Synchrotron X-ray Fluorescence Microscopy.

Al-Zn-Mg-Si alloy coatings have been developed to inhibit the corrosion of cold-rolled steel sheets by offering galvanic and barrier protection to the substrate steel. It is known that Fe deposited from the steel strip modifies the microstructure of the alloy. We cast samples of Al-Zn-Mg-Si coating alloys containing 0.4 wt% Fe and directionally solidified them using a Bridgman furnace to quantify the effect of this Fe addition between 600 °C and 240 °C. By applying a temperature gradient, growth is encouraged, and by then quenching the sample in coolant, the microstructure may be frozen. These samples were analysed using scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) to determine the morphological effects of the Fe distribution across the experimental temperature range. However, due to the sub 1 wt% concentration of Fe, synchrotron X-ray fluorescence microscopy (XFM) was applied to quantitatively confirm the Fe distribution. Directionally solidified samples were scanned at 7.05 keV and 18.5 keV using X-ray fluorescence at the Australian Synchrotron using the Maia array detector. It was found that a mass nucleation event of the Fe-based τ6 phase occurred at 495 °C following the nucleation of the primary α-Al phase as a result of a peritectic reaction with remaining liquid.

In vivo imaging of nickel-rich laticifers: A breakthrough in metal hyperaccumulation

The discovery of the nickel-rich latex of the New Caledonian endemic tree Pycnandra acuminata introduced the term ‘hyperaccumulator’ and gave rise to a new field of research. This then instigated a global quest for these unusual hyperaccumulator plants, even while the underlying mechanisms of nickel acquisition, transport, and internal elemental distribution remained unknown for this original laticifer-bearing hyperaccumulator plant. Here we reveal for the first time the distribution of nickel-filled laticifers in the different plant organs of P. acuminata. The pressurised nickel laticifers were imaged multimodally with a combination of synchrotron X-ray fluorescence (XRF) microscopy, microtomography (XRF-μCT) and synchrotron X-ray phase contrast imaging microtomography (PCI-μCT). These advanced synchrotron methodologies allowed for complimentary non-invasive reconstructions of an in-situ model of the laticiferous system in this species. The data shows the distribution of the nickel-rich laticifers within whole plant tissues from roots to apical tip, thus suggesting nickel trafficking in the laticifer network. The extraordinary concentration of nickel within P. acuminata laticifers functions as an effective natural tracer for XRF-μCT and PCI-μCT to probe the structure and organization of these cells, thereby permitting insights into the development and physiological functioning of this unique duct system.

Microbial Mobilization and Reprecipitation of Transition Metals in Waste Rock from an Abandoned Pyrite Mine: Implications for Metal Recovery

Abstract The Pyrite Mines in Sulphide, Ontario are a collection of historic mine workings representing one of more than 6000 abandoned mines in Ontario. Historic mines are receiving renewed interest as potential sources of critical minerals for use in low carbon technologies. This study characterizes waste rock from the Pyrite Mines in the context of metal distribution, microbial activity, bioleaching, and acid mine drainage (AMD) bioremediation for the recovery of metals. Acidophilic Fe-oxidizing bacteria cultured from the waste rock produced schwertmannite [Fe8O8(OH)8−2x(SO4)x·nH2O] and ammoniojarosite [NH4Fe3(SO4)2(OH)6] with similar morphologies to those often observed in acidic sulfidic mine settings. Fe- and S-oxidizing bacteria found naturally in the waste rock were used in waste rock bioleaching column experiments that demonstrated AMD formation and metal mobilization. The columns produced acidic leachates (pH = 1.75) containing dissolved constituents, including sulfur (1577 mg/L), iron (547.7 mg/L), nickel (12.6 mg/L), manganese (7.3 mg/L), copper (2.3 mg/L), zinc (2.0 mg/L), chromium (1.5 mg/L), and titanium (0.7 mg/L). The proportion of metals successfully leached from the waste rock was variable, with leaching efficiencies calculated for nickel (31%), manganese (10.5%), iron (1.5%), chromium (1.4%), and titanium (0.02%). The leachates produced by the bioleaching columns were amended in subsequent bioremediation columns using sulfate reducing bacteria cultured from the mine site. Remediation efficiencies for elements of interest were calculated as cobalt (100%), chromium (100%), copper (100%), iron (90%), titanium (68%), nickel (52%), manganese (52%), and sulfur (43%). Mapping elemental distributions in thin sections from one of the bioleaching columns using synchrotron X-ray fluorescence microscopy revealed the heterogeneity of the waste rock. Iron was observed in both euhedral mineral grains, likely pyrite, and in secondary cements coating grains in the waste rock. Nickel, manganese, and chromium were primarily co-located with the iron. Titanium was primarily co-located with calcium in titanite (CaTiSiO5), making it challenging to target with bioleaching. This study demonstrates the heterogeneous nature of metal distribution in waste rock from this historic mine site. It indicates that successful metal recovery from legacy mine waste will require such materials to be treated as anthropogenic mineral deposits that require “exploration” and characterization much like naturally occurring ore deposits.

Uranium mineralization in the Thrace Basin, NW Türkiye: Evidence from radiation-induced defects in detrital quartz and synchrotron XRF/XANES analysis

The Paleogene-Neogene Thrace Basin in northwestern Türkiye has long been known to host economic gas and oil resources and has recently been reported to potentially host sandstone-type uranium deposits in the Oligocene Süloğlu Formation. The latter discovery raises questions about the source and deposition mechanism of uranium mineralization in the basin. This contribution reports on the results of a detailed electron paramagnetic resonance (EPR) spectroscopic study of detrital quartz from four sandstone and one mudstone samples in the Süloğlu Formation and documents the distribution and speciation of uranium using combined microbeam synchrotron X-ray fluorescence maps (μsXRF) and microbeam X-ray near edge structure spectroscopy (μsXANES). The EPR spectra of quartz separates are characterized by the presence of diagnostic radiation-induced defects (i.e., silicon-vacancy hole centers H′3, H′4, and H′7 with gmax = 2.049, 2.034, and 2.018, respectively, and the oxygen-vacancy electron center E′1), formed by the bombardment of alpha particles emitted from uranium, thorium, and their unstable progenies. Moreover, notable decreases in the intensity of silicon-vacancy hole centers in the EPR spectra of quartz separates after partial dissolution with hydrofluoric acid, provide compelling evidence for the circulation of uranium-bearing fluids in the Thrace Basin. The μsXRF and μsXANES data reveal the occurrences of mixed U6+ and U4+ species in hematite partially replacing pyrite aggregates but dominantly U4+ in disseminated pyrite and illite in sandstones of the Süloğlu Formation. These results provide new insights into uranium transport, reduction, and deposition mechanisms, with important implications for better understanding sandstone-type uranium deposits in general and further exploration in the Thrace Basin.

Impact of Pyrite Textures Prevalence on Flotation Performance in Mount Isa Copper Orebodies

ABSTRACT Pyrite, the most abundant sulfide mineral in base-metal deposits, presents significant challenges in mineral processing due to its deleterious effects when not properly managed. Its undesirable association with valuable minerals leads to low-quality concentrates, hindering smelting processes. Pyrite’s distinct textures and variable elemental compositions affect its floatability, with complex textures challenging to depress. Moreover, since multiple textures can be present within an orebody, their relative proportion in the ore could affect the overall flotation performance. Therefore, understanding the types of pyrite present, their abundance, and how they affect the flotation behavior of the ore is critical for an efficient depression and possible reclamation of pyrite. At the Mount Isa copper deposit, framboidal or ‘carbonaceous’ pyrite has been an ongoing challenge to the copper concentration operation, reducing the flotation circuit’s efficiency. Previous work by Yenial-Arslan et al. showed that high pyrite recoveries could be strongly linked to the prevalence of fine-grained pyrite. However, samples belonging to the coarse pyrite domain exhibited low natural floatability. This study further investigates the effect of the prevalence of pyrite textures on the flotation performance of copper orebodies at the Mount Isa deposit. The prevalence of pyrite textures was quantified and statistically linked to the natural floatability of pyrite, proving that fine-grained and framboidal pyrite greatly influence pyrite’s overall recovery. Furthermore, various mineral characterization techniques, such as synchrotron X-ray fluorescence microscopy (XFM) analysis, were used to explore how the natural floatability of pyrite was affected.

A comprehensive study of apatite grains in Ryugu rock fragments

AbstractApatite is present as an accessory phase in many meteorites and is often formed as a secondary product of aqueous alteration. Its propensity to incorporate rare earth elements (REE) results in apatite usually being the main REE‐bearing phase in hydrously altered meteorites. Asteroid Ryugu is thought to have experienced pervasive aqueous alteration and material collected from the surface of Ryugu is expected to provide insight into asteroidal aqueous alteration processes without influence by terrestrial weathering. Morphologies and mineral associations of apatite grains from five rock fragments collected from the asteroid Ryugu by the Hayabusa2 spacecraft were examined and their REE concentrations were measured by synchrotron X‐ray fluorescence (SXRF) spectroscopy. The main minerals associated with apatite are dolomite, magnetite, and pyrrhotite. Grain boundary corrosion of the interfaces between apatite assemblages and the surrounding matrix suggest that paragenetic formation on the asteroid was followed by a later episode of hydrous alteration. Light REE (LREE) concentration levels recorded at 20–150 times those of bulk CI levels together with a steady increase from LREE toward enrichment of medium REE (MREE, up to Er) at 50–400 times bulk CI levels may suggest postgenetic removal of LREE from Ryugu apatite grains by late‐stage circulation of a hydrothermal fluid.

The Fate of Vanadium-Bearing Iron Oxyhydroxides in Marine Sediments: Integrating Gel-Based In Situ Mineral Probes with Synchrotron X-ray Fluorescence Microspectroscopy

The Fate of Vanadium-Bearing Iron Oxyhydroxides in Marine Sediments: Integrating Gel-Based In Situ Mineral Probes with Synchrotron X-ray Fluorescence Microspectroscopy

Tooth acellular extrinsic fibre cementum incremental lines in humans are formed by parallel branched Sharpey’s fibres and not by its mineral phase

In humans, the growth pattern of the acellular extrinsic fibre cementum (AEFC) has been useful to estimate the age-at-death. However, the structural organization behind such a pattern remains poorly understood. In this study tooth cementum from seven individuals from a Mexican modern skeletal series were analyzed with the aim of unveiling the AEFC collagenous and mineral structure using multimodal imaging approaches. The organization of collagen fibres was first determined using: light microscopy, transmission electron microscopy (TEM), electron tomography, and plasma FIB scanning electron microscopy (PFIB-SEM) tomography. The mineral properties were then investigated using: synchrotron small-angle X-ray scattering (SAXS) for T-parameter (correlation length between mineral particles); synchrotron X-ray diffraction (XRD) for L-parameter (mineral crystalline domain size estimation), alignment parameter (crystals preferred orientation) and lattice parameters a and c; as well as synchrotron X-ray fluorescence for spatial distribution of calcium, phosphorus and zinc. Results show that Sharpey’s fibres branched out fibres that cover and uncover other collagen bundles forming aligned arched structures that are joined by these same fibres but in a parallel fashion. The parallel fibres are not set as a continuum on the same plane and when they are superimposed project the AEFC incremental lines due to the collagen birefringence. The orientation of the apatite crystallites is subject to the arrangement of the collagen fibres, and the obtained parameter values along with the elemental distribution maps, revealed this mineral tissue as relatively homogeneous. Therefore, no intrinsic characteristics of the mineral phase could be associated with the alternating AEFC incremental pattern.