Synchrotron-based Scanning Transmission X-ray Microscopy Research Articles

(Invited) Leveraging Imaging Techniques to Accelerate the Advancement of Polymer Electrolyte Membrane Water Electrolyzers

Polymer electrolyte membrane water electrolyzers (PEMWEs) are critically needed to meaningfully incorporate clean renewable energy into our energy, transportation, and manufacturing sectors, for without this energy conversion mechanism, the intermittency of renewable energy will always pose a prohibitive cost barrier to practical use. However, in addition to overcoming the intermittency issue of renewable energy, energy storage also has the power to transform current energy infrastructure, particularly when plagued by older systems that lack modularity and flexibility. For example, electricity grids are often constrained to move electricity in and out of a jurisdiction with careful predictions based on past use and future needs. This comes at a cost when electricity must be sold at a loss to prevent a catastrophic surplus of electricity in the grid. While the potential for PEMWEs is tremendous, we must reduce their capital and operating costs in order to reach widespread adoption. In recent years, important work in the field has contributed to advancing PEMWEs in a variety of areas from new materials to flow field design; however, experimental validation, particularly spatially resolved, is necessary to take a fully informed approach to tailoring these materials and architectures.In this talk, I will discuss how we use X-ray and neutron imaging, both ex situ and operando, to provide high spatial and temporal resolution experimental performance and materials characterization for PEMWEs to inform our design process for new materials fabrication, new architectures, and operating parameters. We obtained nano-scale, 3D imaging of PEMWE catalyst layers to inform the stochastic simulations used to uncover the influence of pore size and ionomer distributions on electrical and ionic conductivities. We also used operando X-ray imaging to elucidate the influence of catalyst layer and porous transport layer interfacial conditions on liquid and gas transport behaviour. By applying neutron imaging, we elucidated the impact of temperature on the distribution heterogeneity of liquid water reactant at the catalyst layer. I will also discuss how we are using soft X-rays to perform synchrotron-based scanning transmission X-ray microscopy with absorption spectroscopy to uncover heterogeneity across performance and material characteristics for the PEMWE. Through these highly resolved techniques (in terms of time and space), we aim to advance our predictive models for designing next generation materials, interfaces, and flow configurations for high performance water electrolyzers.

Nitrogen-Rich Organic Matter Formation and Stabilization in Iron Ore Tailings: A Submicrometer Investigation.

Organic matter (OM) formation and stabilization are critical processes in the eco-engineered pedogenesis of Fe ore tailings, but the underlying mechanisms are unclear. The present 12 month microcosm study has adopted nanoscale secondary ion mass spectrometry (NanoSIMS) and synchrotron-based scanning transmission X-ray microscopy (STXM) techniques to investigate OM formation, molecular signature, and stabilization in tailings at micro- and nanometer scales. In this system, microbial processing of exogenous isotopically labeled OM demonstrated that 13C labeled glucose and 13C/15N labeled plant biomass were decomposed, regenerated, and associated with Fe-rich minerals in a heterogeneous pattern in tailings. Particularly, when tailings were amended with plant biomass, the 15N-rich microbially derived OM was generated and bound to minerals to form an internal organo-mineral association, facilitating further OM stabilization. The organo-mineral associations were primarily underpinned by interactions of carboxyl, amide, aromatic, and/or aliphatic groups with weathered mineral products derived from biotite-like minerals in fresh tailings (i.e., with Fe2+ and Fe3+) or with Fe3+ oxyhydroxides in aged tailings. The study revealed microbial OM generation and subsequent organo-mineral association in Fe ore tailings at the submicrometer scale during early stages of eco-engineered pedogenesis, providing a basis for the development of microbial based technologies toward tailings' ecological rehabilitation.

Waste biomass from hypersaline potash mining byproducts: Detection and visualization of Cu(II) and Cr(VI) on Croceicoccus sp. FTI14 biosorbent

Microorganisms in hypersaline potash mining byproducts and their potential environmental applications have not been extensively reported. This study reports the diverse waste-impacted microbial communities (archaea and bacteria) adapted to extreme salinity (>10–25%). Of these, halotolerant Croceicoccus sp. FTI14 was investigated as a biosorbent for removing dissolved Cu(II) and Cr(VI) from synthetic Cu(II) and Cr(VI)-contaminated DI, groundwater and saline groundwater (0.55 M ionic strength). FTI14 biomass was oven-dried, finely ground, and investigated in batch biosorption experiments. At initial metal concentrations of 40 mg/L, FTI14 removed 40 ± 0.7% (16.3 ± 0.5 mg/g) and 19 ± 0.1% (7.8 ± 0.1 mg/g) of the Cu(II) from deionized water and saline groundwater, respectively, while only 22.9 ± 0.7% (9.6 ± 0.2 mg/g) and 2.1 ± 0.6% (1.0 ± 0.3 mg/g) Cr(VI) removal was achieved. Cu(II) uptake (mg/g) exceeded Cr(VI) uptake by a factor of 1.7–7.8. Langmuir and Freundlich models were applied on FTI14 biosorption isotherm data. The Freundlich model showed a better fit for both Cu(II) and Cr(VI), as indicated by the AIC values compared with evidence ratios. Synchrotron-based scanning transmission X-ray microscopy (STXM) visualizations of the biosorbent showed a mixture of whole cells and indistinct biomass and a spatial association between metals and biomass. Metal exposure alters the amide functional groups peak in Fourier transform Infra-red (FTIR) spectra, suggesting its role in sorption process. Thus, this study indicates culturable halotolerant microorganisms from hypersaline potash mining byproducts and its potential as biosorbent applications for metal removal from impacted groundwater.

Energy material analysis via in-situ/operando scanning transmission x-ray microscopy: A review

The development of advanced energy systems is essential for replacing fossil fuel-based societies, and progress in the fundamental understanding of solid-state energy materials has revolutionized this field. In particular, investigating the inhomogeneity of reactions in energy systems requires analysis at the level of individual particles, which are the smallest units in the system. Synchrotron-based scanning transmission X-ray microscopy (STXM) is a valuable tool for exploring reaction and degradation mechanisms, and providing nanoscale site-specific information on chemical and structural changes within single particles. In-situ/operando STXM is particularly useful for observing reactions under well-controlled conditions in real time, thus providing insights into local phenomena obscured by the ensemble effect. This review highlights the research achievements of in-situ/operando STXM in the field of energy materials and provides perspectives for advanced X-ray imaging techniques that can further enhance STXM capabilities.

Janus organic semiconductor nanoparticles prepared by simple nanoprecipitation

Nanoparticles (NPs) of donor–acceptor organic semiconductors are produced by a one-step nanoprecipitation with Janus morphology. Electron donor P3HT was blended with electron acceptor PC61BM in tetrahydrofuran and then precipitated in water, first with surfactant and second without surfactant. Cryogenic transmission electron microscopy reveals an internal Janus structure at high magnification, for NPs which have, in the past, been reported to have a molecularly intermixed morphology. Synchrotron-based scanning transmission X-ray microscopy confirmed the segregation of the organic semiconductors and photoluminescence experiments showed an efficient electron transfer from P3HT to PC61BM. Organic field effect transistors were fabricated with these Janus NPs and showed that the positive charges can be efficiently transported through thin films. This behavior proves that the NPs possess an electron-accepting face (the PC61BM face) able to transport electrons and a hole-accepting face (the P3HT face) for the conduction of holes. Finally, the deposition of silver via the photoreduction of a silver salt (AgNO3(aq)) was demonstrated, as a proof of concept. These experiments show the potential of the Janus NPs for photovoltaics but also photocatalytic reactions in which reduction and oxidation reactions can occur at opposite sides of the nanoreactor (the individual Janus NPs).

Nanoscale chemical mapping of exometabolites at fungal-mineral interfaces.

Mineral‐associated organic matter is an integral part of soil carbon pool. Biological processes contribute to the formation of such organo‐mineral complexes when soil microbes, and in particular soil fungi, deposit a suite of extracellular metabolic compounds and their necromass on the mineral surfaces. While studied in bulk, micro‐ to nanoscale fungal–mineral interactions remain elusive. Of particular interest are the mutual effects at the interface between the fungal exometabolites and proximal mineral particles. In this work, we have grown saprotrophic and symbiotic fungi in contact with two soil minerals with contrasting properties: quartz and goethite, on top of X‐ray transparent silicon nitride membrane windows and analyzed fungal hyphae by synchrotron‐based scanning transmission X‐ray microscopy in combination with near edge X‐ray fine structure spectroscopy at C(K) and Fe(L) absorption edges. In the resultant chemical maps, we were able to visualize and differentiate organic compounds constituting the fungal cells, their extracellular metabolites, and the exometabolites adsorbing on the minerals. We found that the composition of the exometabolites differed between the fungal functional guilds, particularly, in their sugar to protein ratio and potassium concentration. In samples with quartz and goethite, we observed adsorption of the exometabolic compounds on the mineral surfaces with variations in their chemical composition around the particles. Although we did not observe clear alteration in the exometabolite chemistry upon mineral encounters, we show that fungal–mineral interaction result in reduction of Fe(III) in goethite. This process has been demonstrated for bulk systems, but, to our knowledge, this is the first observation on a single hypha scale offering insight into its underlying biological mechanisms. This demonstrates the link between processes initiated at the single‐cell level to macroscale phenomena. Thus, spatially resolved chemical characterization of the microbial–mineral interfaces is crucial for an increased understanding of overall carbon cycling in soil.

Hygroscopicity and Ice Nucleation Properties of Dust/Salt Mixtures Originating from the Source of East Asian Dust Storms

Dust storms are common meteorological events that occur frequently in the late spring and early summer in arid and semi-arid areas. The resulting lofted dust and salt mixtures can impact atmospheric chemistry and climate systems through the many pathways represented by aerosol-cloud-climate interactions. In this study, dust/salt samples were collected from important sources of the East Asian dust storm, including the Badain Jaran Desert, the Tengger Desert and the Ulan Buh Desert in northwestern China. Ion chromatography (IC) measurements were performed to determine the concentrations of cations and anions. The ionic concentrations, pH and dissolvable fractions of sand samples show a positive correlation, indicating that the dissolved content is rich in alkaline ions. A positive matrix factorization (PMF) receptor model was employed to analyze the IC results, and from the PMF solutions non-obvious connections to local geography emerge. The results of hygroscopic experiments of sand samples which were measured by a vapor sorption analyzer indicate that the hygroscopicity may be related to the soluble content of samples, and the observed hygroscopic behavior can be well described by a thermodynamic model. The morphology of individual particles was chemically mapped by the synchrotron-based scanning transmission X-ray microscopy, and needle-shaped CaCO3 particles were observed to adhere to more irregular high K-containing particles. Moreover, a continuous flow diffusion chamber was used to investigate the ice nucleation abilities of typical salts, with both homogeneous freezing and deposition nucleation being observed. The results indicate that the salts primarily act as cloud condensation nuclei but can also act as ice nucleating particles at low temperatures.

Ni, Co, and Mn L3-edge X-ray absorption micro-spectroscopic study on LixNi0.88Co0.08Mn0.04O2 primary particles upon annealing from room temperature to 800 °C

LixNi0.88Co0.08Mn0.04O2 primary particles for lithium ion battery (LIB) applications were annealed in situ from room temperature (RT) to 200, 400, 600, and 800 °C. At each of these temperatures, space-resolved Ni L3-, Co L3-, and Mn L3-edge X-ray absorption spectra of the particles were acquired with 30 nm focused X-rays by using synchrotron-based scanning transmission X-ray microscopy (STXM). This study aimed to investigate the changes induced by the annealing temperature in the local oxidation number, phase, and microscale shape within the particles. At RT, the average oxidation numbers of the Ni, Co, and Mn ions were +3, +3, and +4, respectively. At 200 °C, the average oxidation numbers of the Co and Mn ions were basically the same as those at RT, and those of the Ni ions were between +2 and +3. At 400 °C, the average oxidation numbers of the Ni and Co ions decreased to +2, whereas that of the Mn ions was +4. The average oxidation number of the Ni ions was noticeably lower for smaller particles and on the edges of the particles. At 600 °C, the Ni and Co ions were mostly in the metallic state, the Mn ions were reduced to an oxidation number of +2, and the distribution of Mn ions differed from that of the Ni and Co ions. At 800 °C, the Ni and Co ions were mostly in the metallic state, and the oxidation number of the Mn ions was predominantly +2. At this temperature, strong changes in density distributions of the Mn, Ni, and Co ions occurred.

STXM-XANES and computational investigations of adsorption of per- and polyfluoroalkyl substances on modified clay

The study investigated molecular mechanisms of per- and polyfluoroalkyl substances (PFAS) on a surfactant modified clay (SMC), which rivals or exceeds the performance of granular activated carbon in removing long-chain PFAS from contaminated water. The adsorption isotherms of four anionic and one neutral PFAS from 1 × 10–9 to 1 × 10–5 mol/L were measured to be piecewise, accompanied by the expansion of the SMC interlayer. Based on the spatial distribution of perfluorocarboxylic acid (PFOA) on SMC at the submicron scale, achieved by synchrotron-based scanning transmission X-ray microscopy (STXM) coupled with X-ray absorption near-edge structure spectroscopy (XANES), PFOA molecules were confirmed to enter the interlayer space of SMC and could form charge-charge interaction with the intercalants (quaternary ammonia cations). Revealed by the all-atom molecular dynamics (MD) simulation and density functional theory-based quantum calculations, the interactions between the positively charged surfactant and representative PFAS include charge-charge, charge-dipole, and dipole-dipole interactions. The adsorption mechanisms vary from one PFAS structure to another in terms of adsorption energy and spatial arrangement. Those interactions overcome the interaction between PFAS and water, allowing PFAS to be retained in the SMC's interlayer space. The study provides fundamental insights into how PFAS interact with clay-based materials, supporting the use of the materials for PFAS treatment and remediation.

Soft X-ray Ptychography Chemical Imaging of Degradation in a Composite Surface-Reconstructed Li-Rich Cathode.

The capability in spatially resolving the interactions between components in lithium (Li)-ion battery cathodes, especially correlating chemistry and electronic structure, is challenging but critical for a better understanding of complex degradation mechanisms for rational developments. X-ray spectro-ptychography and conventional synchrotron-based scanning transmission X-ray microscopy image stacks are the most powerful probes for studying the distribution and chemical state of cations in degraded Li-rich cathodes. Herein, we propose a chemical approach with a spatial resolution of around 5.6 nm to imaging degradation heterogeneities and interplay among components in degraded Li-rich cathodes. Through the chemical imaging reconstruction of the degraded Li-rich cathodes, fluorine (F) ions incorporated into the lattice during charging/discharging processes are proved and strongly correlate with the manganese (Mn) dissolution and oxygen loss within the secondary particles and impact the electronic structure. Otherwise, the electrode-electrolyte interphase component, scattered LiF particles (100-500 nm) along with the MnF2 layer, is also visualized between the primary particles inside the secondary particles of the degraded cathodes. The results provide direct visual evidence for the Li-rich cathode degradation mechanisms and demonstrate that the low-energy ptychography technique offers a superior approach for high-resolution battery material characterization.

Quantification of the carbon bonding state in amorphous carbon materials: A comparison between EELS and NEXAFS measurements

The quantitative determination of the carbon hybridization is critical for establishing processing-structure-properties relationships for carbon-based materials, including amorphous carbon coatings. While several techniques have been employed to characterize the amount of sp2 and sp3 carbon in these materials, direct comparisons between analytical results are limited. Here, we compare near edge X-ray absorption fine structure (NEXAFS) spectra of a silicon- and oxygen-containing hydrogenated amorphous carbon (a-C:H:Si:O) coating acquired in synchrotron-based scanning transmission X-ray microscopy (STXM) mode with electron energy loss spectra (EELS) obtained from the same a-C:H:Si:O lamella. While the fractions of sp2 carbon computed from STXM and EELS spectra are in close agreement, the comparison of NEXAFS spectra acquired in STXM mode with NEXAFS spectra collected in partial electron yield mode on a flat a-C:H:Si:O surface indicated that the destructive preparation of thin lamellae for STXM analyses induces variations in the structure of a-C:H:Si:O, namely the breakage of carbon-silicon and carbon-hydrogen bonds, a change in ordering of sp2-bonded carbon, and an increase in the sp2 carbon fraction. These findings can help scientists in the careful interpretation of spectroscopic results obtained from the analysis of samples made of metastable materials after the destructive preparation of specimens for analytical purposes.

In-situ surface chemical and structural self-reconstruction strategy enables high performance of Li-rich cathode

The critical challenges hindering the commercialization of Li-rich cathodes are their rapid-decaying capacity and voltage during cycling, originating from the degradation of lattice structure and interface side reaction between electrode and electrolyte. Surface engineering is considered to be an effective strategy to mitigate these disadvantages. Herein, an in-situ self-reconstruction strategy is proposed and developed to simultaneously optimize surface chemical composition and local structure of Li-rich cathodes. Specifically, the multifunction protective layer consisting of cation disorder phase and LiTMPO 4 -like (TM: Ni, Co, Mn) phase is produced by a simple PH 3 gas treatment. LiTMPO 4 featuring the ability against high potential is responsible for preventing interface side reaction and further reduce the dissolution of Mn. Both LiTMPO 4 -like phase and surface cation disorder phase contribute to stabilizing surface oxygen structure and limiting surface O 2 release. Compared to the pristine one, better integrity of chemical phases and higher oxidation state of TM cations after long-term cycling are confirmed in the modified sample by synchrotron-based scanning transmission X-ray microscopy, highlighting the key roles of the multifunction protective layer in stabilizing the capacity and voltage during cycling. This surface self-reconstruction strategy provides a new path for guiding the interface design of high energy density cathodes. In-situ surface self-reconstruction of Li-rich cathodes enables the formation of multifunction protective layer composed of cation disorder phase and LiTMPO 4 (TM: Ni, Co, Mn)-like phase, ensuring the structural continuity of surface modification layer to bulk. • In-situ surface self-reconstruction enables formation of multifunction layer, ensures structural integrality and continuity. • Protective layer featuring the ability against high voltage, stabilizing surface oxygen structure and limiting O 2 release. • Modified cathode achieve a significant improvement in capacity and voltage, leading to twofold improvement of energy density. • Better integrity of chemical phases and higher oxidation state of cations after cycling are confirmed in the modified sample.

Intracellular amorphous Ca-carbonate and magnetite biomineralization by a magnetotactic bacterium affiliated to the Alphaproteobacteria.

Bacteria synthesize a wide range of intracellular submicrometer-sized inorganic precipitates of diverse chemical compositions and structures, called biominerals. Their occurrences, functions and ultrastructures are not yet fully described despite great advances in our knowledge of microbial diversity. Here, we report bacteria inhabiting the sediments and water column of the permanently stratified ferruginous Lake Pavin, that have the peculiarity to biomineralize both intracellular magnetic particles and calcium carbonate granules. Based on an ultrastructural characterization using transmission electron microscopy (TEM) and synchrotron-based scanning transmission X-ray microscopy (STXM), we showed that the calcium carbonate granules are amorphous and contained within membrane-delimited vesicles. Single-cell sorting, correlative fluorescent in situ hybridization (FISH), scanning electron microscopy (SEM) and molecular typing of populations inhabiting sediments affiliated these bacteria to a new genus of the Alphaproteobacteria. The partially assembled genome sequence of a representative isolate revealed an atypical structure of the magnetosome gene cluster while geochemical analyses indicate that calcium carbonate production is an active process that costs energy to the cell to maintain an environment suitable for their formation. This discovery further expands the diversity of organisms capable of intracellular Ca-carbonate biomineralization. If the role of such biomineralization is still unclear, cell behaviour suggests that it may participate to cell motility in aquatic habitats as magnetite biomineralization does.

Application of FIB-SEM Techniques for the Advanced Characterization of Earth and Planetary Materials.

Advanced microanalytical techniques such as high-resolution transmission electron microscopy (HRTEM), atom probe tomography (APT), and synchrotron-based scanning transmission X-ray microscopy (STXM) enable one to characterize the structure and chemical and isotopic compositions of natural materials down towards the atomic scale. Dual focused ion beam-scanning electron microscopy (FIB-SEM) is a powerful tool for site-specific sample preparation and subsequent analysis by TEM, APT, and STXM to the highest energy and spatial resolutions. FIB-SEM also works as a stand-alone technique for three-dimensional (3D) tomography. In this review, we will outline the principles and challenges when using FIB-SEM for the advanced characterization of natural materials in the Earth and Planetary Sciences. More specifically, we aim to highlight the state-of-the-art applications of FIB-SEM using examples including (a) traditional FIB ultrathin sample preparation of small particles in the study of space weathering of lunar soil grains, (b) migration of Pb isotopes in zircons by FIB-based APT, (c) coordinated synchrotron-based STXM characterization of extraterrestrial organic material in carbonaceous chondrite, and finally (d) FIB-based 3D tomography of oil shale pores by slice and view methods. Dual beam FIB-SEM is a powerful analytical platform, the scope of which, for technological development and adaptation, is vast and exciting in the field of Earth and Planetary Sciences. For example, dual beam FIB-SEM will be a vital technique for the characterization of fine-grained asteroid and lunar samples returned to the Earth in the near future.

Molecular Mechanisms of Chromium(III) Immobilization by Organo-Ferrihydrite Co-precipitates: The Significant Roles of Ferrihydrite and Carboxyl.

The interaction mechanisms of heavy metals with organo-Fe hydroxides co-precipitates (OFC) remain unclear due to the structural complexity of the OFC. In this study, batch experiments were conducted to investigate the immobilization mechanisms of Cr(III) by the OFC, which was prepared by co-precipitating Fe3+ with rice/rape straw-derived dissolved organic carbon, through sorption and co-precipitation using synchrotron-based X-ray absorption near-edge structure (XANES) spectroscopy and scanning transmission X-ray microscopy (STXM). At an Fe/C molar ratio ≥ 0.3, both the sorption and co-precipitation immobilized the majority of Cr(III), but the co-precipitation desorbed less Cr(III) than the sorption regardless of DOC loadings and sources. In contrast, Cr(III) immobilization was significantly reduced at an Fe/C molar ratio of 0.1 for both reactions. Linear combination fitting of Cr K-edge XANES spectra revealed the predominance of ferrihydrite-bound Cr(III), but enhanced organic Cr(III) occurred with increased organic carbon (OC) loading for both the sorption and co-precipitation. STXM coupled with multi-edge XANES analysis confirmed the primary association of Cr(III) with ferrihydrite and directly probed carboxyl as the binding site for Cr(III) retention on the OC constituents of the OFC. These results provided new molecular-level insights into the Cr(III) retention mechanisms on the OFC, particularly for the interactions of Cr(III) and OC constituents of the OFC, which could benefit the management of Cr-contaminated soils with straw returning.

Ultrahigh Density of Gas Molecules Confined in Surface Nanobubbles in Ambient Water

To understand the unexpected and puzzling long-term stability of nanoscale gas bubbles, it is crucial to probe their nature and intrinsic properties. We report herein synchrotron-based scanning transmission X-ray microscopy (STXM) evidence of highly condensed oxygen gas molecules trapped as surface nanobubbles. Remarkably, the analysis of absorption spectra of a single nanobubble revealed that the oxygen density inside was 1-2 orders of magnitude higher than that in atmospheric pressure, and these bubbles were found in a highly saturated liquid environment with the estimated oxygen concentration to be hundreds of times higher than the known oxygen solubility in equilibrium. Molecular dynamics simulations were performed to investigate the stability of surface nanobubbles on a heterogeneous substrate in gas-oversaturated water. These results indicated that gas molecules within confinement such as the nanobubbles could maintain a dense state instead of the ideal gas state, as long as their surrounding liquid is supersaturated. Our findings should help explain the surprisingly long lifetime of the nanobubbles and shed light on nanoscale gas aggregation behaviors.

On the structure and chemistry of fossils of the earliest woody plant

AbstractPalaeontology relies on the description of fossil morphologies to understand the evolutionary history of life on Earth. Yet much remains unknown about the impact of fossilization processes, even though these may introduce biases into palaeobiological interpretations. Here, we report the characterization of fossilized remains of the earliest known woody plant Armoricaphyton chateaupannense preserved either in 2D (as flat carbonaceous films) or in 3D (as organo‐mineral structures) in early Devonian shales (c. 407 Ma) of the Armorican Massif on the northern margin of Gondwana. To document the fine‐scale structure and the chemistry of the tracheids of this ancient plant, we used propagation phase contrast synchrotron radiation X‐ray microcomputed tomography (PPC‐SRμCT), transmission electron microscopy (TEM) and synchrotron‐based scanning transmission X‐ray microscopy (STXM) coupled with X‐ray absorption near edge structure (XANES) spectroscopy. PPC‐SRμCT enables digital visualization of cell walls in unprecedented detail for the specimens preserved in 3D revealing structures similar to those observed in extant lignified cells, thereby strongly suggesting that the earliest woody plant A. chateaupannense originally contained lignin compounds. STXM‐based XANES and TEM data show that, whatever the preservation modes (3D vs 2D), the remaining organic matter has a chemical composition rather typical of pyrobitumen compounds, raising the possibility of an original source other than lignin. The pyrobitumen compounds also contains automorphic Ti‐nanominerals interpreted as a diagenetic feature. Altogether, the present study illustrates that anatomical and chemical preservations may not always be correlated.

Hybrid films of cellulose nanofibrils, chitosan and nanosilica—Structural, thermal, optical, and mechanical properties

Organic-inorganic hybrid films were fabricated from cellulose nanofibrils (CNF) and nanosilica (5–30% wt) embedded in a chitosan (Chi) biopolymer matrix using a slow evaporation method. The self-standing films exhibited high strength and modulus up to 120 ± 5 MPa and 7.5 ± 0.4 GPa, respectively, which are remarkably high values for biopolymer/chitosan hybrids. Scanning electron microscopy showed that the nanosilica is formed of larger aggregates within the lamellar CNF network structure. This observation was further confirmed using synchrotron-based scanning transmission x-ray microscopy (STXM) with the capability to determine the spatial and chemical distribution analysis of the constituents of films. It is interesting that the thermal stability of the hybrid films improved as the nanosilica content increased. Furthermore, the nanosilica effectively filled the pores in the CNF network, thus decreasing the UV transmission and the visible light transmittance of the films.

Correlative Spectromicroscopy and Tomography for Biomedical Applications Involving Electron, Ion, and Soft X-ray Microscopies

Abstract

Aqueous alteration of porous microchondrules in Semarkona: Implications for hydration, oxidation and elemental exchange processes

Porous, igneous glassy microchondrules are relatively common in Semarkona and other unequilibrated ordinary chondrites (UOC), occurring embedded within the fine-grained matrices and the chondrule rims. We have investigated the effects of aqueous alteration on two porous microchondrules and associated amorphous silicate materials in the fine-grained matrix of the Semarkona (LL3.00) ordinary chondrite. The iron valency was measured by synchrotron-based scanning transmission X-ray microscopy (STXM) and detailed compositional and mineralogical data were obtained by transmission electron microscopy (TEM). Our STXM data show that the iron in both microchondrules and the amorphous matrix materials is highly oxidized, with elevated ferric iron contents (up to Fe3+/∑Fe ratio 81%). The oxidation process appears to be the result of the interaction of aqueous fluids produced by melting of water ice that accreted into the LL chondrite parent body. The lack of secondary phases such as phyllosilicates or FeO-rich olivines in the microchondrules and the surrounding fine-grained matrix indicates that aqueous alteration was extremely limited. The distribution of major and minor elements indicates limited elemental exchange between the porous microchondrules and the adjacent fine-grained matrix, suggesting that the chemical composition of the two porous microchondrules was not extensively modified during the aqueous alteration. Therefore, these results strongly support the recent conclusions that porous and nonporous microchondrules have different precursor compositions, since their bulk compositions are different and have not been extensively modified by secondary processes.