X-ray Fluorescence Microspectroscopy Research Articles

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

Soybean seeds treated with zinc evaluated by X-ray micro-fluorescence spectroscopy

Zinc (Zn) is a micronutrient considered essential to plants which can be supplied through seed treatment. The treatment of soybean [Glycine max (L.) Merr.] seeds with Zn, however, is still not well known as regards the uptake and mobilization dynamics of the nutrient during the germination process. This study aimed to evaluate the uptake and distribution dynamics of Zn applied to soybean seeds at two levels of vigor during germination using X-ray micro-fluorescence spectroscopy (µ-XRF). Zinc treatments corresponded to 0, 2, 4 and 8 g of Zn per kg of seeds. High and low vigor seeds that had been treated were located appropriately so as to promote germination. Zn intensity measurements with µ-XRF were taken in different parts (“regions”) of the seeds (seed coat, cotyledon, and embryonic axis) after 8, 16 and 24 h of imbibition and seedlings (primary root, hypocotyl, plumule, cotyledon, and seed coat) after 48, 72 and 96 h of germination. High vigor seeds showed higher Zn intensity in the embryonic axis in the first 16 h, while low vigor seeds showed higher intensity after 24 h. After 48, 72 and 96 h of germination low vigor seedlings showed higher Zn intensity than high vigor seedlings in the primary root. It was concluded that µ-XRF is an efficient technique for identifying variances in the dynamics of Zn uptake and mobilization during the germination of soybean seeds with different vigor levels.

The Technology Transfer from Europe to China in the 17th-18th Centuries: Non-Invasive On-Site XRF and Raman Analyses of Chinese Qing Dynasty Enameled Masterpieces Made Using European Ingredients/Recipes.

Two masterpieces of the Qing Dynasty (1644–1912 CE), one in gilded brass (incense burner) decorated with cloisonné enamels stylistically attributed to the end of the Kangxi Emperor’s reign, the other in gold (ewer offered by Napoleon III to the Empress as a birthday present), decorated with both cloisonné and painted enamels bearing the mark of the Qianlong Emperor, were non-invasively studied by optical microscopy, Raman microspectroscopy and X-ray microfluorescence spectroscopy (point measurements and mapping) implemented on-site with mobile instruments. The elemental compositions of the metal substrates and enamels are compared. XRF point measurements and mappings support the identification of the coloring phases and elements obtained by Raman microspectroscopy. Attention was paid to the white (opacifier), blue, yellow, green, and red areas. The demonstration of arsenic-based phases (e.g., lead arsenate apatite) in the blue areas of the ewer, free of manganese, proves the use of cobalt imported from Europe. The high level of potassium confirms the use of smalt as the cobalt source. On the other hand, the significant manganese level indicates the use of Asian cobalt ores for the enamels of the incense burner. The very limited use of the lead pyrochlore pigment (European Naples yellow recipes) in the yellow and soft green cloisonné enamels of the Kangxi incense burner, as well as the use of traditional Chinese recipes for other colors (white, turquoise, dark green, red), reinforces the pioneering character of this object in technical terms at the 17th–18th century turn. The low level of lead in the cloisonné enamels of the incense burner may also be related to the use of European recipes. On the contrary, the Qianlong ewer displays all the enameling techniques imported from Europe to obtain a painted decoration of exceptional quality with the use of complex lead pyrochlore pigments, with or without addition of zinc, as well as cassiterite opacifier.

Effectiveness of a toothpaste and a serum containing calcium silicate on protecting the enamel after interproximal reduction against demineralization

To evaluate the effectiveness of a calcium silicate/phosphate fluoridated tooth paste and a serum compared with a toothpaste containing hydroxyapatite on protecting the enamel after interproximal reduction against demineralization. 3 sets of eleven incisors were created. The teeth underwent interproximal enamel reduction (IER) of 0.5 mm. Each set was allocated to one of three groups: (1) Brushing without toothpaste (control group); (2) Vitis toothpaste + Remin Pro; (3) Regenerate toothpaste + Regenerate Serum. The agents were applied three times a day and specimens subjected to demineralization cycles for 30 days. The weight percentages of calcium (Ca) and phosphorous (P) were quantified by X-ray microfluorescence spectroscopy. Surface microhardness measurements and electron scanning microscopy (SEM) observations were made. Ca data and the Ca/P ratio were significantly higher in Group 3 than the other groups (p < 0.017), while P was significantly lower in Group 3 (p < 0.017). No significant differences were found between Groups 1 and 2 (p > 0.017). Group 3 showed significantly higher microhardness values (p < 0.05) than Group 1. No significant differences were found for other comparisons between groups (p < 0.05). SEM images showed less demineralization in Group 3. The application of a calcium silicate/phosphate fluoridated tooth paste (Regenerate advance) and a dual serum (Regenerate advance enamel serum) protect the enamel with interproximal reduction against demineralization. Therefore, this treatment could be used to prevent the dissolution of hydroxyapatite after IER.

Graftable SCoMPIs enable the labeling and X-ray fluorescence imaging of proteins.

Bio-imaging techniques alternative to fluorescence microscopy are gaining increasing interest as complementary tools to visualize and analyze biological systems. Among them, X-ray fluorescence microspectroscopy provides information on the local content and distribution of heavy elements (Z ≥ 14) in cells or biological samples. In this context, similar tools to those developed for fluorescence microscopy are desired, including chemical probes or tags. In this work, we study rhenium complexes as a convenient and sensitive probe for X-ray fluorescence microspectroscopy. We demonstrate their ability to label and sense exogenously incubated or endogenous proteins inside cells.

In situ observation of dynamic electrodeposition processes by soft x-ray fluorescence microspectroscopy and keyhole coherent diffractive imaging

This paper describes two novel in situ microspectroscopic approaches to the dynamic study of electrodeposition processes: x-ray fluorescence (XRF) mapping with submicrometric space resolution and keyhole coherent diffractive imaging (kCDI) with nanometric lateral resolution. As a case study, we consider the pulse-plating of nanocomposites with polypyrrole matrix and MnxCoyOz dispersoids, a prospective cathode material for zinc-air batteries. This study is centred on the detailed measurement of the elemental distributions developing in two representative subsequent growth steps, based on the combination of in situ identical-location XRF microspectroscopy—accompanied by soft-x ray absorption microscopy—and kCDI. XRF discloses space and time distributions of the two electrodeposited metals and kCDI on the one hand allows nanometric resolution and on the other hand provides complementary absorption as well as phase contrast modes. The joint information derived from these two microspectroscopies allows measurement of otherwise inaccessible observables that are a prerequisite for electrodeposition modelling and control accounting for dynamic localization processes.

Synchrotron X-ray microscopy reveals early calcium and iron interaction with crocidolite fibers in the lung of exposed mice.

Human exposure to asbestos can cause a wide variety of lung diseases that are still a current major health concern, even if asbestos has been banned in many countries. It has been shown in many studies that asbestos fibers, ingested by alveolar macrophages, disrupt lung iron homeostasis by sequestering iron. Calcium can also be deposited on the fibers. The pathways along which iron and above all calcium interact with fibers are still unknown. Our aim was that of investigating if the iron accumulation induced by the inhaled asbestos fibers also involves calcium ions accumulation. Lung sections of asbestos-exposed mice were analyzed using an extremely sensitive procedure available at the synchrotron facilities, that provides morphological and chemical information based on X-ray fluorescence microspectroscopy (μ-XRF). In this study we show that (1) where conventional histochemical procedures revealed only weak deposits of iron and calcium, μ-XRF analysis is able to detect significant deposits of both iron and calcium on the inhaled asbestos fibers; (2) the extent of the deposition of these ions is proportionally directly related and (3) iron and calcium deposition on inhaled asbestos fibers is concomitant with the appearance of inflammatory and hyperplastic reactions.

Application of confocal X-ray fluorescence micro-spectroscopy to the investigation of paint layers

A confocal micro X-ray fluorescence (MXRF) spectrometer based on polycapillary X-ray optics was used for the identification of paint layers. The performance of the confocal MXRF was studied. Multilayered paint fragments of a car were analyzed nondestructively to demonstrate that this confocal MXRF instrument could be used in the discrimination of the various layers in multilayer paint systems.

Assessment and forensic application of laser-induced breakdown spectroscopy (LIBS) for the discrimination of Australian window glass

A commercially available laser-induced breakdown spectroscopy (LIBS) instrument was evaluated for the determination of elemental composition of twenty Australian window glass samples, consisting of 14 laminated samples and 6 non-laminated samples (or not otherwise specified) collected from broken windows at crime scenes. In this study, the LIBS figures of merit were assessed in terms of accuracy, limits of detection and precision using three standard reference materials (NIST 610, 612, and 1831). The discrimination potential of LIBS was compared to that obtained using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), X-ray microfluorescence spectroscopy (μXRF) and scanning electron microscopy energy dispersive X-ray spectrometry (SEM-EDX) for the analysis of architectural window glass samples collected from crime scenes in the Canberra region, Australia. Pairwise comparisons were performed using a three-sigma rule, two-way ANOVA and Tukey’s HSD test at 95% confidence limit in order to investigate the discrimination power for window glass analysis. The results show that the elemental analysis of glass by LIBS provides a discrimination power greater than 97% (>98% when combined with refractive index data), which was comparable to the discrimination powers obtained by LA-ICP-MS and μXRF. These results indicate that LIBS is a feasible alternative to the more expensive LA-ICP-MS and μXRF options for the routine forensic analysis of window glass samples.

Valproate reverts zinc and potassium imbalance in schizophrenia-derived reprogrammed cells

Schizophrenia has been considered a devastating clinical syndrome rather than a single disease. Nevertheless, the mechanisms behind the onset of schizophrenia have been only partially elucidated. Several studies propose that levels of trace elements are abnormal in schizophrenia; however, conflicting data generated from different biological sources prevent conclusions being drawn. In this work, we used synchrotron radiation X-ray microfluorescence spectroscopy to compare trace element levels in neural progenitor cells (NPCs) derived from two clones of induced pluripotent stem cell lines of a clozapine-resistant schizophrenic patient and two controls. Our data reveal the presence of elevated levels of potassium and zinc in schizophrenic NPCs. Neural cells treated with valproate, an adjunctive medication for schizophrenia, brought potassium and zinc content back to control levels. These results expand the understanding of atomic element imbalance related to schizophrenia and may provide novel insights for the screening of drugs to treat mental disorders.

Mechanisms of metal-phosphates formation in the rhizosphere soils of pea and tomato: environmental and sanitary consequences

Purpose At the global scale, soil contamination with persistent metals such as lead (Pb), zinc (Zn), and copper (Cu) induces a serious threat of entering the human food chain. In the recent past, different natural and synthetic compounds have been used to immobilizemetals in soil environments. However, the mechanisms involved in amendment-induced immobilization of metals in soil remained unclear. The objective of the present work was therefore to determine the mechanisms involved in metal-phosphates formation in the rhizospheric soils of pea and tomato currently cultivated in kitchen gardens. Materials and methods Pea and tomato were cultivated on a soil polluted by past industrial activities with Pb and Zn under two kinds of phosphate (P) amendments: (1) solid hydroxyapatite and (2) KH2PO4. The nature and quantities of metal-P formed in the rhizospheric soils were studied by using the selective chemical extractions and employing the combination of X-ray fluorescence micro-spectroscopy, scanning electron microscopy, and electron microprobe methods. Moreover, the influence of soil pH and organic acids excreted by plant roots on metal-P complexes formation was studied. Results and discussion Our results demonstrated that P amendments have no effect on metal-P complex formation in the absence of plants. But, in the presence of plants, P amendments cause Pb and Zn immobilization by forming metal-P complexes. Higher amounts of metal-P were formed in the pea rhizosphere compared to the tomato rhizosphere and in the case of soluble P compared to the solid amendment. The increase in soil-metal contact time enhanced metal-P formation. Conclusions The different forms of metal-P formed for the different plants under two kinds of P amendments indicate that several mechanisms are involved in metal immobilization. Metal-P complex formation in the contaminated soil depends on the type of P amendment added, duration of soil-plant contact, type of plant species, and excretion of organic acids by the plant roots in the rhizosphere.

Do ‘passive’ medical titanium surfaces deteriorate in service in the absence of wear?

Globally, more than 1000 tonnes of titanium (Ti) is implanted into patients in the form of biomedical devices on an annual basis. Ti is perceived to be 'biocompatible' owing to the presence of a robust passive oxide film (approx. 4 nm thick) at the metal surface. However, surface deterioration can lead to the release of Ti ions, and particles can arise as the result of wear and/or corrosion processes. This surface deterioration can result in peri-implant inflammation, leading to the premature loss of the implanted device or the requirement for surgical revision. Soft tissues surrounding commercially pure cranial anchorage devices (bone-anchored hearing aid) were investigated using synchrotron X-ray micro-fluorescence spectroscopy and X-ray absorption near edge structure. Here, we present the first experimental evidence that minimal load-bearing Ti implants, which are not subjected to macroscopic wear processes, can release Ti debris into the surrounding soft tissue. As such debris has been shown to be pro-inflammatory, we propose that such distributions of Ti are likely to effect to the service life of the device.

Antagonism between transition metal pro-oxidants in polyethylene films

The oxidation of linear low density polyethylene (LLDPE) films containing the combination of pro-oxidants titanium (IV) dioxide (TiO2) with either cobalt (II) stearate (CoSt) or iron (II) stearate (FeSt) have been evaluated under accelerated photo- and thermo-oxidative conditions as well as on outdoor weathering. LLDPE containing only surface-compatibilised nano-TiO2 rapidly photo-whitens and embrittles at a low apparent extent of oxidation (as measured by carbonyl index) due to formation of microscopic voids of ∼150 nm. When CoSt was also included in the film, antagonism occurred shown by embrittlement times longer by ∼90%, higher carbonyl index and absence of film whitening. In contrast, films containing TiO2/FeSt whitened during photo-oxidation and exhibited lower antagonism with only 44% longer times to embrittlement and lower carbonyl index. Antagonism between pro-oxidants was not observed under dark thermo-oxidative conditions. X-ray Fluorescence Microspectroscopy elemental maps revealed that the TiO2 nanoparticles were spatially correlated with iron and cobalt metal ions allowing scavenging of electrons and holes through cycling of the redox states of the metal without producing radical species to initiate polymer oxidation. It is suggested that the antagonism differences between TiO2/CoSt and TiO2/FeSt pro-oxidants is related to the respective reduction potentials of Co3+/2+ and Fe3+/2+ and their effect on the UV conduction and valence band edges of the TiO2 particle. In these ways the photochemistry of TiO2 is suppressed and the photo-oxidative lifetime is governed by the chemistry of the transition metal pro-oxidant.

Chemical element imaging for speleothem geochemistry: Application to a uranium-bearing corallite with aragonite diagenesis to opal (Eastern Siberia, Russia)

Two complementary image-based microanalysis methods, digital autoradiography of radioactive elements and X-ray fluorescence microspectroscopy (micro-XRF), were used to study the geochemistry of a speleothem from Eastern Siberia. Our objective was to show the interest of these micro-chemical methods to investigate the distribution of U and some other elements as Ca, Sr, and Si in speleothems. The sample studied was a corallite concretion that formed slowly by the precipitation of minerals from moisture that had condensed underground. Polished sections of the sample revealed alternating laminas of gray calcite and white aragonite. The concretion, which is older than 400Kyr (U/Th-TIMS), showed no signs of detrital contamination (230Th/232Th>10,000). Digital autoradiography and XRF analyses indicated exceptionally high uranium contents, ranging from 3–10 to more than 1300μg∙g−1 in different areas of the sample. Element maps for calcium (Ca), uranium (U), strontium (Sr) and silicon (Si) showed inverse correlations between Ca and U and between Ca and Si, but there is a strong correlation between Si and U. Under the optical microscope, the low Ca appears as corrosion voids, which were found to contain uranium-enriched amorphous silica replacing areas of aragonite and, in some cases, calcite. This postgenetic amorphous and uraniferous silica is composed of two kinds of opal: opal A formed by large microspheres of 30–40μm in diameter and a gray opal CT with irregular lepispheres. This late opal, dated around 385–412Kyr, is probably due to a special volcanic event formed by uraniferous glass ashes easily soluble by meteoric waters, as suggested by the presence of volcanic suite in the fine fraction of the opal. Opal precipitated after speleothem crystallization by evaporation or cryogenic supersaturation. The study of this exceptional concretion shows the value of direct chemical imaging methods, as they easily revealed the presence and distribution of U in the concretion, and allowed an unusual case of opal diagenesis in a carbonate speleothem to be described. Given the value of speleothems as geo-chronometers and recorders of environmental changes at different time scales, from season to isotopic stage, this methodology opens new perspectives in understanding the geochemical system and consequently the validity of radiometric datings, U/Th and U/Pb, especially in speleothem samples.

Environmental impact of sunscreen nanomaterials: Ecotoxicity and genotoxicity of altered TiO2 nanocomposites on Vicia faba

Mineral sunscreen nanocomposites, based on a nano-TiO2 core, coated with aluminium hydroxide and dimethicone films, were submitted to an artificial ageing process. The resulting Altered TiO2 Nanocomposites (ATN) were then tested in the liquid phase on the plant model Vicia faba, which was exposed 48 h to three nominal concentrations: 5, 25 and 50 mg ATN/L. Plant growth, photosystem II maximum quantum yield, genotoxicity (micronucleus test) and phytochelatins levels showed no change compared to controls. Oxidative stress biomarkers remained unchanged in shoots while in roots, glutathione reductase activity decreased at 50 mg ATN/L and ascorbate peroxidase activity decreased for 5 and 25 mg ATN/L. Nevertheless, despite the weak response of biological endpoints, ICP-MS measurements revealed high Ti and Al concentrations in roots, and X-ray fluorescence micro-spectroscopy revealed titanium internalization in superficial root tissues. Eventual long-term effects on plants may occur.

Low-energy X-ray fluorescence microscopy opening new opportunities for bio-related research

Biological systems are unique matter with very complex morphology and highly heterogeneous chemical composition dominated by light elements. Discriminating qualitatively at the sub-micrometer level the lateral distribution of constituent elements, and correlating it to the sub-cellular biological structure, continues to be a challenge. The low-energy X-ray fluorescence microspectroscopy, recently implemented in TwinMic scanning transmission mode, has opened up new opportunities for mapping the distribution of the light elements, complemented by morphology information provided by simultaneous acquisition of absorption and phase contrast images. The important new information that can be obtained in bio-related research domains is demonstrated by two pilot experiments with specimens of interest for marine biology and food science. They demonstrate the potential to yield important insights into the structural and compositional enrichment, distribution and correlation of essential trace elements in the lorica of Tintinnopsis radix, and the lateral distribution of trace nutrients in the seeds of wheat Triticum aestivum.

Electron Microprobe and Synchrotron X-ray Fluorescence Mapping of the Heterogeneous Distribution of Copper in High-Copper Vineyard Soils

The response of microorganisms to metal contamination of soils varies significantly from one investigation to another. One explanation is that metals are heterogeneously distributed at spatial scales relevant to microbes and that microoorganisms are able to avoid zones of intense contamination. This article aims to assess the microscale distribution of Cu in a vineyard soil. The spatial distribution of Cu was measured at two resolutions (0.3 mm and 20 microm) in thin sections of the surface 4 cm of undisturbed soil by electron microprobe and synchrotron X-ray microfluo-rescence spectroscopy. Bulk physicochemical analyses of Cu, pH, organic matter, texture, and mineralogy were performed. The results indicate that the Cu distribution is strongly heterogeneous at both scales of observation. Entire regions of the thin sections are virtually devoid of Cu, whereas highly localized "hotspots" have Cu signal intensities thousands of times higher than background. The distribution of Rb, or Al and Si, indicators of clay minerals, or Fe (iron (hydr)oxides), show that Cu is not preferentially associated with these mineral phases. Instead, Cu hotspots are associated with particulate organic matter. These observations suggest modification of current sampling protocols, and design of ecotoxicological experiments involving microorganisms, for contaminated soils.

Quantitative trace element analysis of individual fly ash particles by means of X-ray microfluorescence.

A new quantification procedure was developed for the evaluation of X-ray microfluorescence (XRF) data sets obtained from individual particles, based on iterative Monte Carlo (MC) simulation. Combined with the high sensitivity of synchrotron radiation-induced XRF spectroscopy, the method was used to obtain quantitative information down to trace-level concentrations from micrometer-sized particulate matter. The detailed XRF simulation model was validated by comparison of calculated and experimental XRF spectra obtained for glass microsphere standards, resulting in uncertainties in the range of 3-10% for the calculated elemental sensitivities. The simulation model was applied for the quantitative analysis of X-ray tube and synchrotron radiation-induced scanning micro-XRF spectra of individual coal and wood fly ash particles originating from different Hungarian power plants. By measuring the same particles by both methods the major, minor, and trace element compositions of the particles were determined. The uncertainty of the MC based quantitative analysis scheme is estimated to be in the range of 5-30%.

X-ray probe microanalyses and scanning x-ray microscopies

The analytical techniques based on excitation of inner-shell electrons by an incident X-ray photon beam suffer generally from their poor degree of lateral localization. Nevertheless it is possible to perform the microanalysis of a sample in the forms of a thin film by: (i) X-ray photoelectron spectroscopy (XPS or ESCA) and X-ray-induced Auger electron spectroscopy (XAES) for surface analysis; (ii) X-ray absorption spectroscopy (XAS) and X-ray microfluorescence spectroscopy (XMS) for bulk analysis. The corresponding images can also be obtained in the scanning mode: scanning X-ray photoelectron microscopy (SXPM), scanning X-ray-induced Auger electron microscopy (SXAEM) and scanning X-ray microradiography (SXM). The experimental arrangement and the results obtained are described here, together with further improvements and comparisons with other technical solutions.