Synchrotron-based Micro Research Articles

Formation of zinc carbonate phases on dissolving calcite, aragonite, and vaterite in acidic aqueous solutions

Calcium carbonate (CaCO3) minerals serve as a major sink to retain metal ions through mineral-water interfacial reactions in which the capacity and long-term stability of contaminant uptake are influenced by coupled dissolution and precipitation reactions of both primary and secondary carbonate minerals (i.e., mineral replacement). Notably, recent studies of calcite reactivity in acidic solutions containing high levels of metal ions demonstrated complex behavior under conditions of sustained disequilibrium. We explored the reactivity of three CaCO3 polymorphs (calcite, aragonite, and vaterite) with acidic Zn2+-containing aqueous solutions using a suite of imaging techniques including optical and scanning electron microscopies, synchrotron-based micro X-ray fluorescence, and transmission X-ray microscopy. Zn uptake by calcite occurred through a two-step process: the formation of a thin layer of the zinc precipitate on the substrate surface followed by the growth of fibrous and radiating hydrozincite particles from the layer. In contrast, Zn uptake by aragonite occurred by mineral replacement where the secondary Zn carbonate phase preserved the external morphology of the original crystal (i.e., a pseudomorph). The replacement of vaterite by hydrozincite occurred within the confined space beneath the porous shell of vaterite, signifying that the primary mechanism driving Zn carbonate precipitation was chemical exchange through the pores. When multiple CaCO3 polymorphs coexisted, the replacement of aragonite and vaterite occurred preferentially over that of calcite. These results demonstrate the distinct morphological and mineralogical controls over the reactivities of calcium carbonate minerals with Zn2+ under acidic conditions.

Impact of coconut-fiber biochar on lead translocation, accumulation, and detoxification mechanisms in a soil–rice system under elevated lead stress

Biochar, an environmentally friendly material, was found to passivate lead (Pb) in contaminated soil effectively. This study utilized spectroscopic investigations and partial least squares path modeling (PLS-PM) analysis to examine the impact of coconut-fiber biochar (CFB) on the translocation, accumulation, and detoxification mechanisms of Pb in soil-rice systems. The results demonstrated a significant decrease (p < 0.05) in bioavailable Pb concentration in paddy soils with CFB amendment, as well as reduced Pb concentrations in rice roots, shoots, and brown rice. Synchrotron-based micro X-ray fluorescence analyses revealed that CFB application inhibited the migration of Pb to the rhizospheric soil region, leading to reduced Pb uptake by rice roots. Additionally, the CFB treatment decreased Pb concentrations in the cellular protoplasm of both roots and shoots, and enhanced the activity of antioxidant enzymes in rice plants, improving their Pb stress tolerance. PLS-PM analyses quantified the effects of CFB on the accumulation and detoxification pathways of Pb in the soil–rice system. Understanding how biochar influences the immobilization and detoxification of Pb in soil–rice systems could provide valuable insights for strategically using biochar to address hazardous elements in complex agricultural settings.

Synchrotron XRF and Histological Analyses Identify Damage to Digestive Tract of Uranium NP-Exposed Daphnia magna.

Micro- and nanoscopic X-ray techniques were used to investigate the relationship between uranium (U) tissue distributions and adverse effects to the digestive tract of aquatic model organism Daphnia magna following uranium nanoparticle (UNP) exposure. X-ray absorption computed tomography measurements of intact daphnids exposed to sublethal concentrations of UNPs or a U reference solution (URef) showed adverse morphological changes to the midgut and the hepatic ceca. Histological analyses of exposed organisms revealed a high proportion of abnormal and irregularly shaped intestinal epithelial cells. Disruption of the hepatic ceca and midgut epithelial tissues implied digestive functions and intestinal barriers were compromised. Synchrotron-based micro X-ray fluorescence (XRF) elemental mapping identified U co-localized with morphological changes, with substantial accumulation of U in the lumen as well as in the epithelial tissues. Utilizing high-resolution nano-XRF, 400-1000 nm sized U particulates could be identified throughout the midgut and within hepatic ceca cells, coinciding with tissue damages. The results highlight disruption of intestinal function as an important mode of action of acute U toxicity in D. magna and that midgut epithelial cells as well as the hepatic ceca are key target organs.

Multiscale imaging on Saxifraga paniculata provides new insights into yttrium uptake by plants

Yttrium (Y) has gained importance in high tech applications and, together with the other rare earth elements (REEs), is also considered to be an emerging environmental pollutant. The alpine plant Saxifraga paniculata was previously shown to display high metal tolerance and an intriguing REE accumulation potential. In this study, we analysed soil grown commercial and wild specimens of Saxifraga paniculata to assess Y accumulation and shed light on the uptake pathway. Laser ablation inductively coupled plasma mass spectrometry and synchrotron-based micro X-ray fluorescence spectroscopy was used to localise Y within the plant tissues and identify colocalized elements. Y was distributed similarly in commercial and wild specimens. Within the roots, Y was mostly located in the epidermis region. Translocation was low, but wild individuals accumulated significantly more Y than commercial ones. In plants of both origins, we observed consistent colocalization of Al, Fe, Y and Ce in all plant parts except for the hydathodes. This indicates a shared pathway during translocation and could explained by the formation of a stable organic complex with citrate, for example. Our study provides important insights into the uptake pathway of Y in S. paniculata, which can be generalised to other plants.

Membrane fouling remediation and modeling in phosphorous removal using electromagnetic field (EMF)-assisted nanofiltration (NF): In situ synchrotron imaging, experimental and statistical studies

Phosphorous loading in the natural waters is a current issue that is caused by the discharge of industrial water, agriculture run off, and municipal releases. Membrane technology is an emerging method to target the removal of phosphorous from wastewater and has several advantages over the traditional methods. However, the main challenge of membrane technology is membrane fouling. The main goal of this study was to optimize nanofiltration process of phosphates using electromagnetic field (EMF) as an eco-friendly membrane fouling remediation technique. To obtain this, several test runs were performed on a commercial membrane Dow NF270 for nanofiltration of synthesized water with various concentrations of phosphate. The application of EMF altered the particle size of phosphate that resulted in a significant decrease in membrane fouling while obtaining maximum flux. In situ synchrotron-based micro–Computed Tomography imaging (SR-μCT) available at the Canadian Light Source (CLS) was conducted to assess membrane fouling with and without EMF influence across layer by layer across membrane thickness. Synchrotron X-ray analysis revealed the decrease in internal membrane pores fouling, caused by increase of phosphate particles size when using EMF. In addition, SEM images of membrane showed reduced fouling. The influence of flowrate, pressure, pH, and phosphate concentration was observed on permeate volume, permeate flux, and membrane fouling. It was determined that flowrate, transmembrane pressure, and pH had were directly proportional to the permeate volume, while the phosphate concentration was indirectly proportional. Mathematical models were developed to obtain the optimized operating conditions and to determine which factor influenced water flux and membrane fouling the most. The transmembrane pressure was the most significant factor for water permeate flux, while the combination of the influence of pH and feed flowrate had also a positive effect. On the other hand, the feed concentration was the most significant for membrane fouling, according to mathematical model. The optimized conditions with the highest desirability had the concentration of phosphate at 0.368 mg/L, pressure at 97.8 psi, 6.98 pH, and flowrate of 5.13 L/min. Under these conditions, maximum flux of 7.43 mL/cm2/min and minimum fouling of 0.046 mg/cm2 was achieved.

Preliminary study on trace elements distribution and electron density variation in canine mammary tissues using a synchrotron-based micro X-ray fluorescence system

Mammary neoplasms are the most common in female dogs, with high malignancy rates. Despite sharing many similarities with human breast tissues, the prevalence of this type of cancer in dogs are nearly three times higher. Taking that into account, this study aims to present preliminary results about chemical and structural changes occurring in samples of canine breast tumors. For this, we analyzed seven samples including normal, benign and malignant tissues, using micro X-ray fluorescence (μ-XRF) and Compton scattering technique. Our goal was to respectively map the spatial distribution of Fe, Cu and Zn and to determine the electron densities in selected regions of the samples. Results showed that Cu and Zn distributions were spatially correlated in normal tissues, with lower intensities in adipose regions and higher in the fibrous ones. Regarding benign neoplasms, both samples exhibited an increase in Cu intensity over the tumor area, however in different proportions. For the malignant ones, the presence of Fe was observed mostly in the tumor-adjacent regions. The electron density values obtained allowed to differentiate tissue structures, with generally higher density in tumorous regions and lower in adipose tissues.

Carbonation of fresco mural paintings with a dolomitic mortar

An innovative approach involving a collection of experiments to mimic and assess the different conditions (at selected time-pH-[Mg2+]-humidity) existing during the carbonation process in dolomitic mortars is proposed with a combination of micro-analytical imaging techniques, namely: optical and electron microscopy, micro-Fourier-Transform Infrared spectroscopy, Raman spectroscopy and synchrotron-based micro X-ray diffraction. The carbonation process was studied from short time scale to long time scale and from simple aqueous saturated solutions to fresco mock-up samples. These techniques allowed identifying both crystallized and amorphous components and revealing their in-depth distribution in multi-layered systems. The presence of Mg2+ influences the microstructure and composition of dolomitic mortars, resulting in the presence of aragonite concurrent to calcite. In later stages, i.e. once Ca2+ has transformed into carbonate, brucite can lead to the formation of magnesium carbonates and hydroxycarbonates. The results contribute explaining the lability of old dolomitic mortars observed in historical fresco paintings.

Tooth whitening, oxidation or reduction? Study of physicochemical alterations in bovine enamel using Synchrotron based Micro-FTIR

ObjectivesTooth whitening demand formulations have not evolved significantly over years being hydrogen peroxide (HP) or carbamide peroxide (CP) the main active agents used. These oxidizing compounds need high concentrations and long application times to achieve the desired whitening results, leading to painful secondary effects. A novel treatment based on a reducing agent, sodium metabisulphite (MBS) encapsulated in liposomes, demonstrated significant whitening results in just 3 minutes. The aim is to provide information about the chemical interactions of the encapsulated MBS with the enamel structure compared with CP’s and to study their penetration in the hydroxyapatite (HAP). MethodsChemical imaging is performed by synchrotron-based micro Fourier transformed infrared spectroscopy (SR-µFTIR). Continuous Stiffness Measurements (CSM) were used to determine the depth reached by the treatments in order to delimitate the area of study. ResultsPrincipal component analysis (PCA) showed that the main differences between treatments were found in the intensity of the ν3 PO3-4 peak related with tooth demineralization produced by the acidic nature of MBS; these changes were observed in deeper regions of the enamel when MBS was encapsulated. SignificanceThe obtained results indicated that CP and MBS promote different changes in the HAP mineral, and that liposomes favour the diffusion of MBS into the enamel. It is the first time that synchrotron light is used to map chemically the bovine incisor’s enamel, and to determine the effect of a whitening treatment in terms of chemical HAP modifications, and the extent in deep of these effects.

Three-dimensional deformation dynamics of porous titanium under uniaxial compression

In situ, synchrotron-based micro computerized tomography is used to investigate three-dimensional (3D) deformation dynamics of open-cell porous titanium under uniaxial compression. The 3D pore structures are captured, segmented, and transformed into separated pores (spheres) connected by throats (bars) according to the pore network model (PNM). Pore and throat size distributions are quantified via the PNM, while pore shape and orientation distributions, via gyration tensor analysis. After yield, the mean values of equivalent diameter, sphericity and aspect ratios of the pores decrease as deformation progresses, indicating increased pore anisotropy. However, the number and equivalent diameter of the throats decrease even at the elastic stage, and the average diameter decreases approximately linearly with increasing bulk strain. The collapse of individual pores is tracked, and the pores with their longest axes aligned perpendicular to the loading direction are prone to compaction compared to those aligned parallel to the loading direction, because of different stress concentrations. Microstructure-based finite element (FE) analysis reproduces the overall deformation characteristics observed in the experiments. The deformation mechanisms and FE model may be useful for guiding material assessment and design related to porous Ti.

Sphalerite weathering and controls on Zn and Cd migration in mine waste rock: An integrated study from the molecular scale to the field scale

Degraded water quality and environmental impacts caused by weathering of sulfide-bearing mine wastes are a legacy remaining at many historical mine sites. Release and mobilization of toxic metals (e.g., Zn and Cd) in mine drainage are often associated with weathering of primary sulfide minerals and precipitation and dissolution of secondary minerals. This study aims to couple field-scale measurements of physicochemical parameters with μm- and nm-scale mineralogical characterization to investigate sphalerite weathering and controls on Zn and Cd migration in an uncovered mine waste-rock pile. Elevated concentrations of Zn and Cd, potentially harmful to the receiving environment, were detected in waste-rock pore water and seepage. A suite of analytical techniques, including scanning electron microscopy – energy dispersive X-ray spectroscopy (SEM-EDS), scanning transmission electron microscopy (STEM) with EDS, electron microprobe analysis (EMPA), and synchrotron-based micro X-ray fluorescence (μ-XRF) mapping and micro X-ray absorption near edge structure (μ-XANES) spectroscopy were utilized in a high-resolution investigation of elemental- and secondary-mineral associations with sphalerite grains. EMPA and μ-XRF elemental maps and STEM investigations show depletion of Zn, Fe, S, and Cd, local enrichment of Cu, and distinct dissolution pits at the margins of sphalerite grains. Using μ-XANES, the speciation of solid phases containing Zn, Cu, Fe, and S indicates the dominance of primary sphalerite with microscopic inclusions of chalcopyrite, along with sparse occurrence of secondary Cu-bearing sulfides formed during weathering. These results suggest sphalerite oxidation leads to congruent dissolution without formation of distinct secondary-mineral coatings. Sphalerite weathering significantly contributes to elevated aqueous concentrations of Zn and Cd. Field-scale observations and mineralogical investigations indicate common occurrence of Fe-oxyhydroxides in the waste-rock pile. Seepage chemistry and surface complexation modeling results suggest that pH-dependent variations in reactions on the surfaces of the Fe-oxyhydroxides control aqueous concentrations of Zn and Cd, and the Zn/Cd ratio in the seepage. This work highlights the importance of understanding the mechanisms of sulfide-mineral oxidation and subsequent surface precipitation and adsorption, such that appropriate remediation action can be implemented to limit mobilization of metals to sensitive ecosystems.

Synchrotron-based micro computed tomography investigation of the implant-abutment fatigue-induced microgap changes

ObjectiveThis study evaluates the effect of dynamic-loading on the microgap of the IAC when different supratructure heights are applied. Materials and methods: Forty-eight dental implants (24 each of butt-joint (H) and internal-conical connections (C)) were tested in this study. Each group was further divided into three groups (n = 8) according to the applied suprastructure height (H1, C1: 10 mm, H2, C2: 14 mm and H3, C3: 18 mm). All specimens were subjected to cyclic loading in a chewing-simulator with a load of 98 N for 5 × 106 chewing cycles. The microgap at the IAC was inspected before and after loading, using synchrotron-based micro computed tomography (SRμCT) and light microscopy (LM). Results: SRμCT revealed an internal microgap range between 0.26 μm and 0.5 μm in the group C, whereas the group H exhibited a microgap range between 0.26 μm and 0.47 μm prior to loading. After chewing simulation, a smaller microgap size in all groups was detected ranging from 0.11 μm to 0.26 μm (group C: 0.11μm–0.26 μm; group H: 0.21μm–0.25 μm). The LM investigation showed mean microgap values at the outer IAC junction before loading from 5.8 μm to 11.3 μm and from 3.9 μm to 7.2 μm after loading. All specimens exhibited a vertical intrusion displacement of the abutment. Conclusion: Regardless of the crown height, the microgap between the abutment and implant systematically decreased after loading in both butt-joint and internal-conical connections.

Fractal breakage of porous carbonate sand particles: Microstructures and mechanisms

In situ, three-dimensional (3D) characterizations of particle breakage in porous carbonate sands are presented, for the first time, with synchrotron-based micro computed tomography. Evolution of grain-scale characteristics are identified and quantified via elaborate image processing and topology analyses. The sequential 3D images reveal distinctly different fracture mechanisms for carbonate sands from silica sands. The angular shape of carbonate sand particles facilitates bending fracture, and particles with a lower sphericity and a higher porosity are more prone to break. 3D crack networks extracted from fractured particles imply considerable cleavage along initial pores. The fractal dimension of crack networks increases with external loading due to crack branching via cleavage. The resultant fragment size distribution also appears fractal and the fractal feature is valid down to the breakage limit of calcium carbonate. Crack propagation along the initial pores reduces the energy barrier for particle breakage and thus fracture strength of particles.

A novel calcium-based magnetic biochar is effective in stabilization of arsenic and cadmium co-contamination in aerobic soils

This study developed a novel calcium-based magnetic biochar by pyrolysing rice straw mixed with calcium carbonate and iron oxide for stabilization of contamination of multiple metals. A 160-day incubation study was conducted to investigate its performance in stabilization of cadmium and arsenic co-contamination in soil. Both biochar and Ca-MBC treatments increased soil pH, decreased the bioavailability of cadmium. Ca-MBC decreased but biochar enhanced the bioavailability of arsenic. The BCR (European Community Bureau of Reference) sequential extraction confirmed Ca-MBC facilitated the transformation of the unstable fraction of arsenic to stable fractions. The stabilization mechanisms were explored through synchrotron-based micro X-ray fluorescence and X-ray absorption near edge structure. The results show that Ca-MBC remediated the dual contamination of arsenic and cadmium through (1) elevated pH and cation exchange capacity (for Cd); (2) the formation of bi-dentate chelate and ternary surface complexes on the surface of iron oxide; (3) enhanced adsorption ability of porous biochar. In addition, Ca-MBC increased the abundance and diversity of bacterial community, and modified the relative abundances of bacterial taxa, leading to a shift of the composition. These new insights provide valuable information for stabilization of co-contamination of arsenic and cadmium in soil using the potential material Ca-MBC.

Speciation and location of arsenic and antimony in rice samples around antimony mining area

Arsenic (As) and antimony (Sb) are considered as priority environmental pollutants and their accumulation in crop plants particularly in rice has posed a great health risk. This study endeavored to investigate As and Sb contents in paired soil-rice samples obtained from Xikuangshan, the world largest active Sb mining region, situated in China, and to investigate As speciation and location in rice grains. The soil and rice samples were analyzed by coupling the wet chemistry, laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS), synchrotron-based micro X-ray fluorescence mapping (μ-XRF) and micro X-ray absorption near-edge structure (μ-XANES) spectroscopy. The results of field survey indicated that the paddy soil in the region was co-polluted by Sb (5.91–322.35 mg kg−1) and As (0.01–57.21 mg kg−1). Despite the higher Sb concentration in the soil, rice accumulated more As than Sb indicating the higher phytoavailability of As. Dimethylarsinic acid (DMA) was the predominant species (>60% on average) in the rice grains while the percentage of inorganic As species was 19%–63%. The μ-XRF mapping of the grain section revealed that the most of As was distributed and concentrated in rice husk, bran and embryo. Sb was distributed similarly to As but was not in the endosperm of rice grain based on LA-ICP-MS. The present results deepened our understanding of the As/Sb co-pollution and their association with the agricultural-product safety in the vicinity of Sb mining area.

Incipient chemical weathering at bedrock fracture interfaces in a tropical critical zone system, Puerto Rico

Abstract The processes that control chemical weathering of bedrock in the deep critical zone at a mm-scale are still poorly understood, but may produce 100 s of meters of regolith and substantial fluxes of silicate weathering products and thus may be important for modeling long-term, global CO2. Weathering controls are also difficult to ascertain, as laboratory determined dissolution rates tend to be 2–5 orders of magnitude faster than field determined dissolution rates. This study aims to establish (i) the incipient processes that control the chemical weathering of the Bisley bedrock and (ii) why weathering rates calculated for the watershed may differ from laboratory rates (iii) why rates may differ across different scales of measurement. We analyzed mineralogy, elemental chemistry, and porosity in thin sections of rock obtained from drilled boreholes using Scanning Electron Microscopy (SEM) with energy dispersive spectrometry, electron probe microanalysis, and synchrotron-based Micro X-ray Fluorescence (µXRF) and X-ray Absorption Near Edge Structure (XANES). Weathering ages were determined from U-series isotope analysis. Mineral specific dissolution rates were calculated from solid-state mineralogical gradients and weathering ages. Mineralogical and elemental transects across thin sections and SEM images indicate that trace pyrite is the first mineral to dissolve. Micro-XRF mapping at 2 µm resolution revealed sulfate in pore space adjacent to dissolving pyrite, indicating that the incipient reaction is oxidative. The oxidative dissolution of pyrite produces a low pH microenvironment that aids the dissolution of pyroxene and chlorite. The rate-limiting step of weathering advance, and therefore the creation of the critical zone in the Bisley watershed, is pyrite oxidation, despite the low abundance (∼0.5 vol%) of pyrite in the parent rock. The naturally determined dissolution rates presented here either approach, converge with, or in some cases exceed, rates from the literature that have been experimentally determined. The U-series weathering age data on the mm-scale integrates the weathering advance rate over the ∼4.2 ± 0.3 kyrs that the weathering rind took to form. The weathering advance rate calculated at a watershed scale (from stream chemistry data) represents a contemporary weathering advance rate, which compares well with that calculated for the weathering rind, suggesting that the Bisley watershed has been weathering at steady-state for the last ∼4 kyrs.

Time-resolved X-ray fluorescence analysis of element distribution and concentration in living plants: An example using manganese toxicity in cowpea leaves

The distribution and concentration of nutrients and contaminants affect almost every metabolic process in plants but analytical limitations have hindered the determination of microscopic changes over time within living plant tissues. We developed a novel method using synchrotron-based micro X-ray fluorescence (μ-XRF) that, for the first time, allows quantification of the spatial and temporal changes of multiple elements in the same area of living leaves. The utility of this approach was tested by examining changes over 48 h in unifoliate leaves of 7-d-old cowpea (Vigna unguiculata) plants simultaneously at 0.2 and 30 μM Mn in nutrient solution, with 30 μM Mn known to be toxic to cowpea and cause the formation of Mn-dense lesions. The fast X-ray fluorescence detector system reduced dwell on living leaf samples. This produced no evidence of tissue damage through repeated μ-XRF scanning, thereby overcoming previously noted experimental artifacts. This permitted, for the first time, visual and quantitative assessments of spatial and temporal changes in nutrient concentrations. By focusing on changes in Mn status, this study illustrated extension of two-dimensional μ-XRF scans to a three-dimensional geometry of Mn kinetics in the same area of leaves. The multi-element potential of this method was exemplified through the measurement of distributions and concentrations of K, Ca, Fe, Cu, and Zn within living plant leaves. This novel method and accompanying information on changes in Mn distribution showed the potential for microscopic, time-resolved, in vivo examination of changes in elemental distribution. We consider that this method will be of benefit for a wide range of studies, including functional characterization of molecular biology, examining changes in the distribution of nutrients, and understanding the movement and toxicity of contaminants.

Localization, Characterization and Local Biokinetics of Tattoo Pigment Particles in Human Skin and Lymph Nodes by Means of Synchrotron-based Micro- and NanoXRF

Localization, Characterization and Local Biokinetics of Tattoo Pigment Particles in Human Skin and Lymph Nodes by Means of Synchrotron-based Micro- and NanoXRF

The nature of ancient Egyptian copper-containing carbon inks is revealed by synchrotron radiation based X-ray microscopy

For the first time it is shown that carbon black inks on ancient Egyptian papyri from different time periods and geographical regions contain copper. The inks have been investigated using synchrotron-based micro X-ray fluorescence (XRF) and micro X-ray absorption near-edge structure spectroscopy (XANES) at the European Synchrotron Radiation Facility (ESRF). The composition of the copper-containing carbon inks showed no significant differences that could be related to time periods or the geographical locations. This renders it probable that the same technology for ink production was used throughout Egypt for a period spanning at least 300 years. It is argued that the black pigment material (soot) for these inks was obtained as by-products of technical metallurgy. The copper (Cu) can be correlated with the following three main components: cuprite (Cu2O), azurite (Cu3[CO3]2[OH]2) and malachite (Cu2CO3[OH]2).

Manganese distribution and speciation help to explain the effects of silicate and phosphate on manganese toxicity in four crop species.

Soil acidity and waterlogging increase manganese (Mn) in leaf tissues to potentially toxic concentrations, an effect reportedly alleviated by increased silicon (Si) and phosphorus (P) supply. Effects of Si and P on Mn toxicity were studied in four plant species using synchrotron-based micro X-ray fluorescence (μ-XRF) and nanoscale secondary ion mass spectrometry (NanoSIMS) to determine Mn distribution in leaf tissues and using synchrotron-based X-ray absorption spectroscopy (XAS) to measure Mn speciation in leaves, stems and roots. A concentration of 30μM Mn in solution was toxic to cowpea and soybean, with 400μM Mn toxic to sunflower but not white lupin. Unexpectedly, μ-XRF analysis revealed that 1.4mMSi in solution decreased Mn toxicity symptoms through increased Mn localization in leaf tissues. NanoSIMS showed Mn and Si co-localized in the apoplast of soybean epidermal cells and basal cells of sunflower trichomes. Concomitantly, added Si decreased oxidation of Mn(II) to Mn(III) and Mn(IV). An increase from 5 to 50μMP in solution changed some Mn toxicity symptoms but had little effect on Mn distribution or speciation. We conclude that Si increases localized apoplastic sorption of Mn in cowpea, soybean and sunflower leaves thereby decreasing free Mn2+ accumulation in the apoplast or cytoplasm.

In Situ Multimodal 3D Chemical Imaging of a Hierarchically Structured Core@Shell Catalyst.

A Cu/ZnO/Al2O3@ZSM-5 core@shell catalyst active for one-step conversion of synthesis gas to dimethyl ether (DME) was imaged simultaneously and in situ using synchrotron-based micro X-ray fluorescence (μ-XRF), X-ray diffraction (μ-XRD), and scanning transmission X-ray microscopy (STXM) computed tomography (CT) with micrometer spatial resolution. An identical sample volume was imaged stepwise, first under oxidizing and reducing atmospheres (imitating calcination and activation processes), and then under model reaction conditions for DME synthesis (H2:CO:CO2 ratio of 16:8:1, up to 250 °C). The multimodal imaging methods offered insights into the active metal structure and speciation within the catalyst, and allowed imaging of both the catalyst core and zeolite shell in a single acquisition. Dispersion of nanosized Cu species was observed in the catalyst core during reduction, with formation of a metastable Cu+ phase at the core-shell interface. Under DME reaction conditions at 1 bar, the coexistence of Cu0 in the active catalyst core together with partially oxidized Cu species was unraveled. The zeolite shell and core-shell interface remained stable under all conditions, preserving the bifunctional nature of the catalyst. These observations are inaccessible using standard bulk techniques like X-ray absorption spectroscopy (XAS) and XRD, demonstrating the potential of multimodal in situ X-ray CT for characterization of hierarchically designed materials, which stand to benefit tremendously from such 3D spatially resolved measurements.