Scanning Transmission X-ray Microspectroscopy Research Articles

Micro-Nanoparticle Characterization: Establishing Underpinnings for Proper Identification and Nanotechnology-Enabled Remediation.

Microplastics (MPLs) and nanoplastics (NPLs) are smaller particles derived from larger plastic material, polymerization, or refuse. In context to environmental health, they are separated into the industrially-created "primary" category or the degradation derivative "secondary" category where the particles exhibit different physiochemical characteristics that attenuate their toxicities. However, some particle types are more well documented in terms of their fate in the environment and potential toxicological effects (secondary) versus their industrial fabrication and chemical characterization (primary). Fourier Transform Infrared Spectroscopy (FTIR/µ-FTIR), Raman/µ-Raman, Proton Nuclear Magnetic Resonance (H-NMR), Curie Point-Gas Chromatography-Mass Spectrometry (CP-gc-MS), Induced Coupled Plasma-Mass Spectrometry (ICP-MS), Nanoparticle Tracking Analysis (NTA), Field Flow Fractionation-Multiple Angle Light Scattering (FFF-MALS), Differential Scanning Calorimetry (DSC), Thermogravimetry (TGA), Differential Mobility Particle [Sizing] (DMPS), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), and Scanning Transmission X-ray Microspectroscopy (STXM) are reviewed as part of a suite of characterization methods for physiochemical ascertainment and distinguishment. In addition, Optical-Photothermal Infrared Microspectroscopy (O-PTIR), Z-Stack Confocal Microscopy, Mueller Matrix Polarimetry, and Digital Holography (DH) are touched upon as a suite of cutting-edge modes of characterization. Organizations, like the water treatment or waste management industry, and those in groups that bring awareness to this issue, which are in direct contact with the hydrosphere, can utilize these techniques in order to sense and remediate this plastic polymer pollution. The primary goal of this review paper is to highlight the extent of plastic pollution in the environment as well as introduce its effect on the biodiversity of the planet while underscoring current characterization techniques in this field of research. The secondary goal involves illustrating current and theoretical avenues in which future research needs to address and optimize MPL/NPL remediation, utilizing nanotechnology, before this sleeping giant of a problem awakens.

Location, speciation, and quantification of carbon in silica phytoliths using synchrotron scanning transmission X-ray microspectroscopy.

Phytoliths of biogenic silica play a vital role in the silicon biogeochemical cycle and occlude a fraction of organic carbon. The location, chemical speciation, and quantification of this carbon within phytoliths have remained elusive due to limited direct experimental evidence. In this work, phytoliths (bilobate morphotype) from the sugarcane stalk epidermis are sectioned with a focused ion beam to produce lamellas (≈10 × 10 μm2 size, <500 nm thickness) and probed by synchrotron scanning transmission X-ray microspectroscopy (≈100-200 nm pixel size; energies near the silicon and carbon K-absorption edges). Analysis of the spectral image stacks reveals the complementarity of the silica and carbon spatial distributions, with carbon found at the borders of the lamellas, in islands within the silica, and dispersed in extended regions that can be described as a mixed silica-carbonaceous matrix. Carbon spectra are assigned mainly to lignin-like compounds as well as to proteins. Carbon contents of 3-14 wt.% are estimated from the spectral maps of four distinct phytolith lamellas. The results provide unprecedented spatial and chemical information on the carbon in phytoliths obtained without interference from wet-chemical digestion.

Arbuscular Mycorrhizal Fungi Drive Organo-Mineral Association in Iron Ore Tailings: Unravelling Microstructure at the Submicron Scale by Synchrotron-Based FTIR and STXM-NEXAFS.

Arbuscular mycorrhizal (AM) fungi play an important role in organic matter (OM) stabilization in Fe ore tailings for eco-engineered soil formation. However, little has been understood about the AM fungi-derived organic signature and organo-mineral interactions in situ at the submicron scale. In this study, a compartmentalized cultivation system was used to investigate the role of AM fungi in OM formation and stabilization in tailings. Particularly, microspectroscopic analyses including synchrotron-based transmission Fourier transform infrared (FTIR) and scanning transmission X-ray microspectroscopy combined with near-edge X-ray absorption fine structure spectroscopy (STXM-NEXAFS) were employed to characterize the chemical signatures at the AM fungal-mineral and mineral-OM interfaces at the submicron scale. The results indicated that AM fungal mycelia developed well in the tailings and entangled mineral particles for aggregation. AM fungal colonization enhanced N-rich OM stabilization through organo-mineral association. Bulk spectroscopic analysis together with FTIR mapping revealed that fungi-derived lipids, proteins, and carbohydrates were associated with Fe/Si minerals. Furthermore, STXM-NEXAFS analysis revealed that AM fungi-derived aromatic, aliphatic, and carboxylic/amide compounds were heterogeneously distributed and trapped by Fe(II)/Fe(III)-bearing minerals originating from biotite-like minerals weathering. These findings imply that AM fungi can stimulate mineral weathering and provide organic substances to associate with minerals, contributing to OM stabilization and aggregate formation as key processes for eco-engineered soil formation in tailings.

Characterization of Nanoplastics, Fibrils, and Microplastics Released during Washing and Abrasion of Polyester Textiles.

Nanoplastics (defined here as plastic particles smaller than 1000 nm) released during the daily use of plastic products are gaining increasing attention due to their potential effects on human and environmental health. Formation of nanoplastics has been reported so far for diverse plastic products under varying conditions of use. The washing of synthetic textiles has been identified as an important source of microplastic fibers (MPF) released to the environment. In addition, abrasion of textiles was shown to induce further fragmentation of fibers and subsequent formation of much smaller and shorter fibrils. The aim of this work was to identify whether washing and wearing of textiles also results in the formation of nanoplastics. We designed washing and abrasion experiments to investigate the morphology, number, and size of micro- and nanoplastics released from polyester textiles. Using a combination of techniques including scanning transmission X-ray microspectroscopy (STXM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and nanoparticle tracking analysis (NTA), we were able to quantify nanoplastics (average hydrodynamic diameter 173-188 nm), microplastic fibrils (diameter 3 ± 1 μm, length 20-160 μm), and MPFs (diameter 16 ± 7 μm, length up to 5 mm). The presence of polyester nanoplastics was confirmed by the near edge X-ray absorption fine spectra (NEXAFS) of the nanoparticles in the abrasion and washing samples for particles larger than 100 nm. We estimated that in the abraded samples, 1 g of fleece textile released an average of 2.1× 1011 nanoplastic particles (1.4 mg), 1.4 × 104 MPFs (1.0 mg), and 5.3 × 105 fibrils (0.5 mg) based on SEM images and NTA. In the nonabraded samples, 1 g of textile released an average of 3.3 × 1011 nanoplastic particles (2.1 mg), 2.8 × 103 MPFs (0.2 mg), and no fibrils. The present study is the first to show a significant release of polyester nanoplastics during the washing and abrasion of synthetic textiles.

Metatranscriptomic Insights Into the Response of River Biofilm Communities to Ionic and Nano-Zinc Oxide Exposures.

Manufactured Zn oxide nanoparticle (ZnO-NP) are extensively used world-wide in personal care and industrial products and are important contaminants of aquatic environments. To understand the overall impact of ZnO-NP contamination on aquatic ecosystems, investigation of their toxicity on aquatic biofilms is of particular consequence, given biofilms are known sinks for NP contaminants. In order to assess alterations in the functional activity of river microbial biofilm communities as a result of environmentally-relevant ZnO-NP exposure, biofilms were exposed to ionic zinc salt or ZnOPs that were uncoated (hydrophilic), coated with silane (hydrophobic) or stearic acid (lipophilic), at a total concentration of 188 μg l–1 Zn. ICP-MS analyses of biofilms indicated ZnO-NP concentrated in the biofilms, with hydrophilic, hydrophobic, and lipophilic treatments reaching 0.310, 0.250, and 0.220 μg Zn cm–2 of biofilm, respectively, while scanning transmission X-ray microspectroscopy (STXM) analyses of biofilms confirmed that Zn was extensively- and differentially-sorbed to biofilm material. Microbial community composition, based on taxonomic affiliation of mRNA sequences and enumeration of protozoa and micrometazoa, was not affected by these treatments, and the total transcriptional response of biofilms to all experimental exposures was not indicative of a global toxic-response, as cellular processes involved in general cell maintenance and housekeeping were abundantly transcribed. Transcripts related to major biological processes, including photosynthesis, energy metabolism, nitrogen metabolism, lipid metabolism, membrane transport, antibiotic resistance and xenobiotic degradation, were differentially expressed in Zn-exposures relative to controls. Notably, transcripts involved in nitrogen fixation and photosynthesis were decreased in abundance in response to Zn-exposure, while transcripts related to lipid degradation and motility-chemotaxis were increased, suggesting a potential role of Zn in biofilm dissolution. ZnO-NP and ionic Zn exposures elicited generally overlapping transcriptional responses, however hydrophilic and hydrophobic ZnO-NPs induced a more distinct effect than that of lipophilic ZnO-NPs, which had an effect similar to that of low ionic Zn exposure. While the physical coating of ZnO-NP may not induce specific toxicity observable at a community level, alteration of ecologically important processes of photosynthesis and nitrogen cycling are an important potential consequence of exposure to ionic Zn and Zn oxides.

Submicron Distribution and Association of Copper and Organic Carbon in A Contaminated Soil Using Scanning Transmission X-ray Microspectroscopy

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On the magnetic properties of iron nanostructures fabricated via focused electron beam induced deposition and autocatalytic growth processes

We employ Electron beam induced deposition (EBID) in combination with autocatalytic growth (AG) processes to fabricate magnetic nanostructures with controllable shapes and thicknesses. Following this route, different Fe deposits were prepared on silicon nitride membranes under ultra-high vacuum conditions and studied by scanning electron microscopy (SEM) and scanning transmission x-ray microspectroscopy (STXM). The originally deposited Fe nanostructures are composed of pure iron, especially when fabricated via autocatalytic growth processes. Quantitative near-edge x-ray absorption fine structure (NEXAFS) spectroscopy was employed to derive information on the thickness dependent composition. X-ray magnetic circular dichroism (XMCD) in STXM was used to derive the magnetic properties of the EBID prepared structures. STXM and XMCD analysis evinces the existence of a thin iron oxide layer at the deposit–vacuum interface, which is formed during exposure to ambient conditions. We were able to extract magnetic hysteresis loops for individual deposits from XMCD micrographs with varying external magnetic field. Within the investigated thickness range (2–16 nm), the magnetic coercivity, as evaluated from the width of the hysteresis loops, increases with deposit thickness and reaches a maximum value of ∼160 Oe at around 10 nm. In summary, we present a viable technique to fabricate ferromagnetic nanostructures in a controllable way and gain detailed insight into their chemical and magnetic properties.

Morphology changes of ionic liquid encapsulating polymer microcontainers upon X-ray irradiation

Microencapsulated ionic liquids represent a novel type of material with high potential for various applications in chemical synthesis, catalysis or separation processes. We present a detailed morphological analysis of this material by means of two imaging techniques, i.e., scanning transmission X-ray microspectroscopy (STXM) and transmission electron microscopy (TEM). While TEM can be utilized only in the dry state, STXM offers access to high-resolution imaging in liquid surroundings. In either case prolonged illumination leads to degradation of the stabilizing polymer. We discuss potential scenarios, e.g., formation of perforations within the polymer shell, to explain the experimental findings.

Employing microspectroscopy to track charge trapping in operating pentacene OFETs

Ultrathin pentacene films resemble benchmark and model materials for organic field-effect transistors (OFETs). We employ scanning transmission X-ray microspectroscopy (STXM) and confocal Raman microspectroscopy as highly resolving probes to obtain insight into the correlation of morphology and charge transport in pentacene OFETs. By combining the operation-induced intensity increase in Raman-active bands with micromorphology, we are able to visualize charge-induced effects, in particular charge trapping in pentacene OFETs during operation. The high sensitivity and specificity of Raman microscopy allows to distinguish between orientation and charge-induced effects and thus to locate the trapped charges at grain boundaries.

In Situ Synchrotron Radiation X‐Ray Microspectroscopy of Polymer Microcontainers

Direct, real-time analytical techniques that provide high-resolution information on the chemical composition and submicrometer structure of various polymer micro- and nanoparticles are in high demand in a range of life science disciplines. Synchrotron-based scanning transmission X-ray microspectroscopy (STXM) combines both local-spot chemical information (assessed via near-edge X-ray absorption fine structure spectroscopy) and imaging with resolution of several tens of nanometers, and thus can yield new insights into the nanoscale properties of these materials. Furthermore, this method allows in situ examination of soft-matter samples in aqueous/gaseous environments and under external stimuli, such as temperature, pressure, ultrasound, and light irradiation. This Minireview highlights some recent progress in the application of the STXM technique to study the temperature-dependent behavior of polymer core-shell microcapsules and to characterize the physicochemical properties of the supporting shells of gas-filled microbubbles in their natural hydrated state.

Microspectroscopic Analysis of the X-Ray-induced Photoreduction in Fe- and Mn-containing SMMs

Scanning transmission X-ray microspectroscopy (STXM) and L-edge near-edge X-ray absorption fine structure (NEXAFS) spectroscopy have been applied to study the valence states of metal ions in various Fe- and Mn-containing single-molecule magnet materials, in particular the ligand-stabilized metal complexes NaFe6 (so-called “ferric wheel”), Fe4 (so-called “ferric star”) and Mn7 (so-called “manganese wheel”).We compare dose-dependent L-edge absorption spectra with the results of theoretical studies of the involved metal ions to conclude on the change in oxidation state upon increasing the X-ray dose. It is found that even low-intensity irradiation induces the reduction of the weakly interacting metal ions, and that the soft X-ray-induced photoreduction is less pronounced in microcrystalline films.

Surface sensitivity in scanning transmission x-ray microspectroscopy using secondary electron detection

The successful integration of electron detection into an existing scanning transmission x-ray microspectroscope (STXM) at the Swiss Light Source is demonstrated. In conventional x-ray detection using a photomultiplier, STXM offers mainly bulk sensitivity combined with high lateral resolution. However, by implementation of a channeltron electron multiplier, the surface sensitivity can be established by the detection of secondary electrons emitted from the sample upon resonant excitation. We describe the experimental setup and discuss several relevant aspects, in particular the schemes to correct for self-absorption in the specimen due to back illumination in case of thicker films.

Water-dispersible PVA-based dry microballoons with potential for biomedical applications

This paper reports on the preparation and characterization of stable poly(vinyl alcohol) (PVA)-based dry hollow microparticles, readily convertible to gas-filled microballoons (MBs) in water suspension. The rehydrated MBs can be used as ultrasound contrast agents and for targeted drug delivery, while the dry MBs are suitable for encapsulation of biologically active gases. The MBs powder material is obtained by freeze-drying the as-prepared telechelic PVA-shelled MBs aqueous dispersion. The microstructure of the lyophilized MBs as well as of the starting and the reconstituted MBs in water suspension was examined using transmission electron microscopy (TEM), scanning electron microscopy (SEM), scanning transmission X-ray microspectroscopy (STXM) and confocal laser scanning microscopy (CLSM). STXM observations below and above the oxygen K-edge reveal that 80% of the MBs originating from the lyophilized particles are gas-filled. Moreover, local carbon K near-edge X-ray absorption fine structure spectroscopy (NEXAFS) measurements evidenced that the chemical composition of the polymeric shell is preserved during the freeze-drying process and subsequent shelf storage for at least more than one year.

Investigations of clay colloid aggregates by scanning transmission X-ray microspectroscopy of suspensions

The environmental behaviour of colloidal clay in aquatic systems is linked to the properties of their aggregates. Earlier investigations of clay colloids were performed with electron microscope techniques which caused de-hydration of the particles. Information on the structure of colloid aggregates is needed for understanding their sedimentation behaviour, as well as colloid contaminant transport properties in natural systems. Scanning transmission X-ray microspectroscopy successfully produced images of montmorillonite colloid aggregates in a pseudo-equilibrium state in 1 mM NaCl suspensions equilibrated for more than a year. These clay aggregates were revealed at photon energies below the O absorption edges of clay and water. They were spherical or ellipsoidal with diameters of the order of 100-800 nm. The aggregates are porous and gel like with lower densities than the clay mineral. These investigations are important for modelling the occurrence of clay aggregates in aqueous environments.

Soft X-ray induced modifications of PVA-based microbubbles in aqueous environment: a microspectroscopy study

We use scanning-transmission X-ray microspectroscopy (STXM) for in situ characterization of the physicochemical changes in air-filled poly(vinyl alcohol) (PVA) based microbubbles upon soft X-ray irradiation. The microbubbles were illuminated directly in aqueous suspension with 520 eV X-rays and a continuous shrinkage of the particles with an illumination time/radiation dose was observed. Utilizing the intrinsic absorption properties of the species and the high spatial resolution of the STXM, the modifications of the particles' structure were simultaneously recognized. A thorough characterization of the microbubble volume, membrane thickness and absorption coefficient was performed by quantitative fitting of the radial transmittance profiles of the targeted microbubbles. Apart from the observed volume contraction, there was no significant change in the shell thickness. The chemical changes in the membranes were clarified via C K-edge near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. It was revealed that the observed structural alterations go along with a continuous degradation of the PVA network associated with formation of carbonyl- and carboxyl-containing species as well as an increased content of unsaturated bonds.

A study of diesel PM with X-ray microspectroscopy

Carbonaceous particulate matter from diesel fuel combustion was studied with Scanning Transmission X-ray Microspectroscopy, a novel synchrotron radiation-based technique, which combines X-ray absorption spectroscopy and microscopy. Single soot particles were chemically identified with a spatial resolution of better than 100 nm. Near-edge X-ray Absorption Fine Structure spectra from the carbon K-absorption edge could be assigned to specific particle regions, making it possible to distinguish graphitic carbon in the soot particles from hydrocarbons, such as residual lubricating oil and diesel fuel and their reaction products.