Microbeam Synchrotron Radiation X-ray Fluorescence Research Articles

Nondestructive characterization of diseased Chinese chive leaves using X-ray intensity ratios with microbeam synchrotron radiation X-ray fluorescence spectrometry.

The Chinese chive (Allium tuberosum) is a core crop grown in Kochi Prefecture, Japan. However, withering symptoms occur during greenhouse growing, which have a negative impact on crop management Chinese chive leaves with physiological disorders (PD) or necrotic streak disease (ND) present with withering as typical blight symptoms. Excess or deficiency of elements may cause such withering in Chinese chive leaves with PD. Therefore, visualizing the elemental distribution in plant bodies may help clarify the cause of this withering. In this study, using synchrotron radiation X-ray fluorescence (SR-XRF) imaging, we examined the elemental distribution conditions in healthy Chinese chive leaves without withering, those that withered due to PD, and those that withered due to ND. Segmentation analysis of inductively coupled plasma-optical emission spectroscopy (ICP-OES) was performed on the SR-XRF imaged Chinese chive leaves and the data from the two analytical methods were compared. SR-XRF imaging provided more detailed data on elemental distribution compared with segmentation analysis using ICP-OES. Based on the SR-XRF imaging results, the X-ray intensity ratios for Ca/K, Fe/Mn, and Zn/Cu were calculated. These findings support that the Ca/K, Fe/Mn, and Zn/Cu X-ray intensity ratios can be used in the early detection of withered leaves and to predict the factors causing withering.

Nondestructive Mineral Imaging of Chinese Chive Leaves Withered by Physiological Damage Using Microbeam Synchrotron Radiation X-Ray Fluorescence Analysis.

A significant problem encountered in Chinese chives (Allium tuberosum) grown in greenhouses is the reduction in the yield and quality due to symptoms of withered leaf tips. Withered leaf tips of three Chinese chive cultivars were nondestructively analyzed by microbeam synchrotron radiation X-ray fluorescence (μ-SR-XRF) imaging. Dead, wilting, and healthy parts of the leaves exhibited significant variations in the mineral composition. The Ca/K X-ray intensity ratios were significantly increased with the degree of withering.

Nondestructive Differentiation of Polyester Single White Fibers Using Synchrotron Radiation Microbeam X-ray Fluorescence Spectrometry with Vertical Focusing.

In this study, the nondestructive differentiation of individual white polyester clothing fibers was accomplished via synchrotron radiation microbeam X-ray fluorescence (SR-μ-XRF) analysis. SR-μ-XRF with vertical focusing is a useful nondestructive method for the analysis of a single polyester clothing fiber. Kirkpatrick-Baez (KB) mirror was used to vertically focus 20 keV X-rays for the analysis of 22 individual white polyester fibers taken from clothing commonly sold in Japan. SR-μ-XRF with a vertical focused 2 μm (V) × 300 μm (H) beam was approximately 12.8 times more sensitive than SR-XRF with an unfocused 300 μm (V) × 300 μm (H) beam for the detection of elements in single fibers. The minimum detection limits (MDLs) of the SR-μ-XRF method were 8.15 ppm for Cl and 0.06 ppm for Br. In addition to Ti in TiO2 delustering agents, Zr and Nb impurities in the delustering agents were detected in individual fibers. Sb from a polymerization catalyst and Co from a transesterification catalyst were also detected in individual fibers. Comparing the Ti Kβ /Sb Lα,β and Zr Kα /Nb Kα X-ray intensity ratios was a useful way to distinguish individual clothing fibers, and 98% of the fibers were differentiated when additional trace elements were used as discrimination indicators.

Impact of microscopic In fluctuations on the optical properties of InxGa1-xN blue light-emitting diodes assessed by low-energy X-ray fluorescence mapping using synchrotron radiation

Among the III-nitride semiconductors, InxGa1-xN is a key material for visible optical devices such as light-emitting diodes (LEDs), laser diodes, and solar cells. Light emission is achieved via electron-hole recombination within the InxGa1-xN layer. When InxGa1-xN-based blue LEDs were first commercialized, the high probability of electron-hole radiative recombination despite the presence of numerous threading dislocations was a mystery. Extensive studies have proposed that carrier localization in nanoscopic potential fluctuations due, for example, to the immiscibility between InN and GaN or random alloy fluctuations is a key mechanism for the high emission efficiency. In actual LED devices, not only nanoscopic potential fluctuations but also microscopic ones exist within the InxGa1-xN quantum well light-emitting layers. Herein we map the synchrotron radiation microbeam X-ray fluorescence of InxGa1-xN blue LEDs at a sub-micron level. To acquire weak signals of In, Ar, which is in the air and has a fluorescent X-ray energy similar to that of In, is evacuated from the sample chamber by He purge. As a result, we successfully visualize the spatial In distribution of InxGa1-xN layer nondestructively and present good agreement with optical properties. Additionally, we demonstrate that unlike nanoscopic fluctuations, microscopic In compositional fluctuations do not necessarily have positive effects on device performance. Appropriately controlling both nanoscopic and microscopic fluctuations at the same time is necessary to achieve supreme device performance.

Imaging metals in Caenorhabditis elegans.

Systemic trafficking and storage of essential metal ions play fundamental roles in living organisms by serving as essential cofactors in various cellular processes. Thereby metal quantification and localization are critical steps in understanding metal homeostasis, and how their dyshomeostasis might contribute to disease etiology and the ensuing pathologies. Furthermore, the amount and distribution of metals in organisms can provide insight into their underlying mechanisms of toxicity and toxicokinetics. While in vivo studies on metal imaging in mammalian experimental animals are complex, time- and resource-consuming, the nematode Caenorhabditis elegans (C. elegans) provides a suitable comparative and complementary model system. Expressing homologous genes to those inherent to mammals, including those that regulate metal homeostasis and transport, C. elegans has become a powerful tool to study metal homeostasis and toxicity. A number of recent technical advances have been made in the development and application of analytical methods to visualize metal ions in C. elegans. Here, we briefly summarize key findings and challenges of the three main techniques and their application to the nematode, namely sensing fluorophores, microbeam synchrotron radiation X-ray fluorescence as well as laser ablation (LA) coupled to inductively coupled plasma-mass spectrometry (ICP-MS).

Microdistribution of lead in human teeth using microbeam synchrotron radiation X-ray fluorescence (μ-SRXRF).

Lead (Pb) exposure is known to be associated with adverse effects on human health, especially during the prenatal period and early childhood. The Pb content in teeth has been suggested as a useful biomarker for the evaluation of cumulative Pb exposure. This study was designed to employ the microbeam synchrotron radiation X-ray fluorescence technique to determine the microdistribution of Pb within the tooth to evaluate the reliability of the technique and the effectiveness of tooth Pb as a biomarker of Pb exposure. The results showed that in the incisor sample, Pb primarily deposited in secondary dentine region close to the pulp and secondarily at enamel exterior. In addition, Pb colocalised with Zn, indicating a positive correlation between Pb and Zn. By contrast,in the two molar samples, Pb accumulated principally in the pulp, and secondarily in the enamel. At the same time, Pb in these two molar samples colocalised with Ca instead of Zn as was observed in the incisor sample. Several batches of line scans further confirmed the conclusions. The feasibility of using microbeam synchrotron radiation X-ray fluorescence to determine the microdistribution of Pb in teeth and of using the tooth Pb, especially in dentine, as a biomarker was discussed.

Preliminary investigation of trace element in Pterygium using Synchrotron radiation micro-beam X-ray fluorescence analysis (-XRF)

We have assessed the relative content and distribution of Iron and Zinc elements using microbeam synchrotron radiation X-ray fluorescence technique. One such technique is X-ray fluorescence (XRF), which has been used previously to map trace elements distribution in Physical samples. In this article a compromise is suggested in issue Pterygium samples. In this study, a prospective randomized clinical trial was conducted. Serial frozen sections of pterygium tissues and conjunctival tissues of 40 μm thickness were collected from 8 patients £¨10 eyes£©undergoing pterygium excision combine with limbal stem cell transplantation. A synchrotron-based XRF microprobe was used to map the distribution of Fe and Zn in whole frozen pterygium sections. The frozen sections were tested by synchrotron radiation X-ray fluorescence technique. These experiments were performed at BL15U in Shanghai, China. Then, the results have palyed that Iron and Zinc were present in both pterygium tissues and normal conjunctiva tissues (relevance ratio 100%). The contents of Iron and Zinc in normal conjunctiva tissues were significantly lower than in pterygium tissues (P < 0.05). The microelements were mostly clusteredin the pterygium tissues, while sparsely distributed in the normal conjunctiva tissue. Finally, we found that XRF imaging will be useful for mapping elemental distribution in Pterygium tissues. 40 μm frozen section on 6 μm mylar film is good for the test on BL15U. The contents of Iron and Zinc in pterygium tissue were significantly higher than in the control tissues. The results seem to be valuable in that Iron and Zinc may play a role in the development process of Pterygium.

Application of Conventional and Microbeam Synchrotron Radiation X-Ray Fluorescence and Absorption for the Characterization of Human Nails

The synchrotron radiation based spectroscopies X-ray fluorescence and X-ray absorption fine structure are used to detect illness-related changes in the elemental distribution and bonding environment of metals in human nails. The effective atomic number of a collection of nails is determined using two methods, the X-ray transmittance and the scattering method, and is found equal to 7.5 +/- 0.5. X-ray fluorescence maps of the elemental distributions, recorded with a lateral resolution of 5 microm, reveal that S, Ca and Zn are distributed homogeneously while Fe tends to cluster. In the Fe-rich clusters, which have a diameter in the range 15-30 microm, the Fe concentration is 10 times higher than in the matrix. The Zn K edge X-ray Absorption Fine Structure spectra reveal that Zn, in the nails from healthy donors and patients suffering from lung diseases, is four-fold coordinated with N and S and the Zn-N and Zn-S distances are equal to 2.03 A and 2.25 A, respectively. Finally the signature of various bonds in the C-, O- and N- K near edge X-ray absorption fine structure spectra is discussed.

Toxicological study of injuries of rat’s hippocampus after lead poisoning by synchrotron microradiography and elemental mapping

The hippocampus, a major component of the brain, is one of the target nervous organs in lead poisoning. In this work, a rat’s hippocampal injury caused by lead was studied. The lead concentrations in blood, bone and hippocampus collected from rats subject to lead poisoning were quantified by Inductively Coupled Plasma Mass Spectrometry while morphological information and elemental distributions in the hippocampus were obtained with synchrotron radiation X-ray phase contrast imaging and synchrotron radiation micro-beam X-ray fluorescence, respectively. For comparison, identical characterization of the specimens from the rats in the control group was done in parallel. Results show that the ratios between the lead content in the treated group and that in the control group of the hippocampus, bone, and blood are about 2.66, 236, and 39.6, respectively. Analysis also revealed that some health elements such as S, K, Cl and P increase in the regions with high lead content in the treated hippocampus. Morphological differences between the normal and lead-exposed hippocampus specimens in some local areas were observed. Explicitly, the structure of the lead-exposed hippocampus was tortuous and irregular, and the density of the neurons in the Dentate Gyrus was significantly lower than that from the control group. The study shows that the synchrotron radiation methods are very powerful for investigating structural injury caused by heavy metals in the nervous system.

Correlation of concentrations of selected trace elements with Gleason grade of prostate tissues

The causes of prostate cancer are still obscure but some evidence indicates that there is a close connection between several trace elements and processes which may lead to malignant cells. In our study the microbeam synchrotron radiation X-ray fluorescence emission (micro-SRIXE) technique was applied for quantitative analysis of selected elements. For the first time, we correlate the concentrations of Mn, Fe, Cu, and Zn with the clinical stage of the prostate cancer at the time of operation (described by Gleason grade). Serial sections of prostate tissues were collected from patients undergoing radical prostatectomy. One section, stained with hematoxylin and eosin, was prepared for histopathological analysis; a second, adjacent unstained section was used in micro-SRIXE experiments. All experiments were performed at beamline L at HASYLAB, DESY, Germany. Our results seem to be valuable in light of the determination of the changes in the concentrations of trace elements as a potential diagnostic marker and their etiological involvement in the different stages of prostate diseases.

Ecotoxicological assessment of lanthanum with Caenorhabditis elegans in liquid medium

With their widespread applications in industry, agriculture and many other fields, more and more rare earth elements (REEs) are getting into the environment, especially the aquatic systems. Therefore, understanding the aquatic ecotoxicity of REEs has become more and more important. In the present work, Caenorhabditis elegans (C. elegans) was used as a test organism and life-cycle endpoints were chosen along with elemental assay to evaluate the aquatic toxicity of lanthanum (La), a representative of REEs. The results show La³+ had significant adverse effects on the growth and reproduction of worms above a concentration of 10 μmol L⁻¹. The elemental mapping by microbeam synchrotron radiation X-ray fluorescence (μ-SRXRF) illustrated how La treatment disturbed the metals distribution in the whole body of a single tiny nematode at lower levels. Our results suggested that the high-level REEs in some polluted water bodies would lead to an aquatic ecological crisis. The assessment we performed in the present work could be developed as a standardized test design for aquatic toxicological research.

Quantitative imaging of element spatial distribution in the brain section of a mouse model of Alzheimer's disease using synchrotron radiation X-ray fluorescence analysis

A method for quantitative imaging of trace elements in sections of bio-tissues using synchrotron radiation microbeam X-ray fluorescence (SR-μXRF) analysis was developed. The Compton scattering in the SR-μXRF spectrum was utilized as an internal standard to compensate the differences in thickness and density of thin bio-tissue sections. The ratios of element sensitivities to Compton scattering peak obtained from two matrix-matched standard reference materials were used for the calculation of the concentrations of metals in a brain section. The concentrations of Ca, Fe, Cu and Zn in the standard reference material (GBW 08551, pig liver) determined by this method were in good agreement with the certified values. The detection limits of Ca, Fe, Cu and Zn at 2 s detection were 1.15, 0.53, 0.21, and 0.20 μg g−1, respectively. The method has been successfully applied in accurate and precise imaging of the element variations in the brain section of a transgenic mouse model of Alzheimer's disease.

Synchrotron radiation microbeam X-ray fluorescence analysis of zinc concentration in remineralized enamel in situ

Objective Remineralization is an indispensable phenomenon during the natural healing process of enamel decay. The incorporation of zinc (Zn) into enamel crystal could accelerate this remineralization. The present study was designed to investigate the concentration and distribution of Zn in remineralized enamel after gum chewing. Methods The experiment was performed at the Photon Factory. Synchrotron radiation was monochromatized and X-rays were focused into a small beam spot. The X-ray fluorescence (XRF) from the sample was detected with a silicon (Si) (lithium (Li)) detector. X-ray beam energy was tuned to detect Zn. The examined samples were small enamel fragments remineralized after chewing calcium phosphate-containing gum in situ. The incorporation of Zn atom into hydroxyapatite (OHAP), the main component of enamel, was measured using Zn K-edge extended X-ray absorption fine structure (EXAFS) with fluorescence mode at the SPring-8. Results A high concentration of Zn was detected in a superficial area 10-μm deep of the sectioned enamel after gum chewing. This concentration increased over that in the intact enamel. The atomic distance between Zn and O in the enamel was calculated using the EXAFS data. The analyzed atomic distances between Zn and O in two sections were 0.237 and 0.240 nm. Conclusion The present experiments suggest that Zn is effectively incorporated into remineralized enamel through the physiological processes of mineral deposition in the oral cavity through gum-chewing and that Zn substitution probably occurred at the calcium position in enamel hydroxyapatite.

Chemical Speciation of Arsenic-Accumulating Mineral in a Sedimentary Iron Deposit by Synchrotron Radiation Multiple X-ray Analytical Techniques

The comprehensive characterization of As(V)-bearing iron minerals from the Gunma iron deposit, which were probably formed by biomineralization, was carried out by utilizing multiple synchrotron radiation (SR)-based analytical techniques at BL37XU at SPring-8. SR microbeam X-ray fluorescence (SR-mu-XRF) imaging showed a high level of arsenic accumulation in the iron ore as dots of ca. 20 microm. Based on SEM observations and SR X-ray powder diffraction (SR-XRD) analysis, it was found that arsenic is selectively accumulated in strengite (FePO4 x 2H2O) with a concentric morphology, which may be produced by a biologically induced process. Furthermore, the X-ray absorption fine structure (XAFS) analysis showed that arsenic in strengite exists in the arsenate (AsO4(3-)) form and is coordinated by four oxygen atoms at 1.68 angstroms. The results suggest that strengite accumulates arsenic by isomorphous substitution of AsO4(3-) for PO4(3-) to form a partial solid-solution of strengite and scorodite (FeAsO4 x 2H2O). The specific correlation between the distribution of As and biominerals indicates that microorganisms seems to play an important role in the mineralization of strengite in combination with an arsenic-accumulating process.

Mapping technique for biodistribution of elements in a model organism, Caenorhabditis elegans, after exposure to copper nanoparticles with microbeam synchrotron radiation X-ray fluorescence

To investigate the toxicological effects of nanomaterials, experimental studies on the absorption and accumulation in organisms are of broad interest. In the present study, Caenorhabditis elegans (C. elegans) was used as a “model” organism to investigate the bioaccumulation and toxicological effects of engineered copper nanoparticles with a scanning technique of microbeam synchrotron radiation X-ray fluorescence (μ-SRXRF). The adult hermaphrodite is anatomically simple with 959 somatic cells and 1 mm in length. The mapping results of the whole organism indicate that the exposure to copper nanoparticles can result in an obvious elevation of Cu and K levels, and a change of bio-distribution of Cu in nematodes. Accumulation of Cu occurs in the head and at a location 1/3 of the way up the body from the tail compared to the un-exposed control. In contrast, a higher amount of Cu was detected in other portion of worm body, especially in its excretory cells and intestine when exposed to Cu2+. The results compared well with total Cu levels in nematodes, which were 4.10 ± 0.54, 12.32 ± 0.49 and 5.22 ± 0.63 μg g−1 dry weight for the PBS, Cu2+ and Cu nanoparticle groups, respectively, measured by ICP-MS. The nondestructive and multi-elemental μ-SRXRF provides an important tool for mapping the elemental distribution in the whole body of a single tiny nematode at lower levels.

Characterization of PM2.5 in the ambient air of Shanghai city by analyzing individual particles

PM2.5 samples were collected simultaneously at three representative areas (central city, industrial area and clean air suburban) of Shanghai city. Their morphologies and elemental compositions were determined by scanning electron microscopy coupled with energy analysis (SEM-EDX). The particles were classified into four groups based on morphology and elemental composition. Soot aggregates and spherical fly ash particles were the two dominant types and they were identified as originating from automobile exhaust, metallurgical industry and coal combustion. The size distribution of the particles showed that most had diameters in the range of 0.2–1.4 μm. Individual particles were measured by synchrotron radiation micro-beam X-ray fluorescence (micro-SXRF) and the micro-SXRF spectra were obtained. Pattern recognition techniques, which took the micro-SXRF spectrum of a single aerosol particle as its fingerprint, were used to identify the origins of the particles. Seven source types were identified. They were: metallurgical industry, vehicle exhaust, soil dust, coal combustion, diesel exhaust, oil combustion and motorcycle exhaust. Metallurgical industry, automobile exhaust, and coal combustion were recognized to be the main pollution sources of PM2.5 in the air of Shanghai city.

Intraneuronal investigations of organic components and trace elements with the use of synchrotron radiation

AbstractThree techniques based on synchrotron radiation microbeam analysis were applied to biochemical investigations of human central nervous system (CNS) tissue. Thin tissue slices representing Parkinson's disease (PD), amyotrophic lateral sclerosis (ALS) and control cases were studied. Synchrotron radiation microbeam x‐ray fluorescence (micro‐SRXRF) was applied to the analysis of the elemental distribution inside single nerve cells. Investigation of copper oxidation state was performed with the use of micro x‐ray absorption near‐edge structure spectroscopy (micro‐XANES). Moreover, the organic components of the tissues were analyzed by means of synchrotron radiation Fourier transform infrared microspectroscopy (SR‐FTIRM). Topographic differences in elemental composition were observed for the nerve cell body. Higher levels of Fe, Zn and Ca were found for the neurons of PD cases in comparison with the control group. The IR spectra measured in neurons of PD, ALS and control cases showed differences in absorption bands associated with characteristic groups of selected biological molecules. Additionally, results of SR‐FTIRM measurements indicated inhomogeneous accumulation of the main organic components in PD nerve cells, in contrast to the control cases. Copyright © 2005 John Wiley &amp; Sons, Ltd.

Implementation of X-ray fluorescence microscopy for investigation of elemental abnormalities in central nervous system tissue

The microbeam synchrotron radiation X-ray fluorescence technique (micro-SRXRF) was applied to topographic and quantitative elemental analysis of human spinal cord tissue sections. The feasibility of this technique for the determination of elemental abnormalities caused by neurodegenerative disorder, i.e. amyotrophic lateral sclerosis (ALS), was verified. The applied measurement conditions allowed detecting: P, S, Cl, K, Ca, Fe, Cu, Zn and Br in thin tissue slices. Two-dimensional maps of the elemental distribution were recorded. Quantitative differences in elemental concentration between gray matter, nerve cells and white matter were observed for all analyzed cases. For the motor neuron bodies higher accumulation of S, Cl, K, Fe, Zn and Br was noticed. The results showed significant differences of elemental accumulation between the analyzed ALS cases. Moreover, the feasibility of using tissue sections fixed and embedded in paraffin for micro-SRXRF analysis was tested. These studies were performed on the samples of rat brain.

Spatial Distribution of Metal Ions in Spruce Wood by Synchrotron Radiation Microbeam X-Ray Fluorescence Analysis

Summary The possibility of using synchrotron radiation microbeam X-ray fluorescence (μ -XRF) for the determination of the morphological distribution of inorganic elements in wood has been investigated. A number of samples were analyzed and some of the results are presented in this paper. The new application of the method showed good results and it was concluded that the technique is useful for specific in situ metal ion analysis of wood. One of its special advantages is that it is a non-destructive method, which may allow analysis of the same sample before and after a chemical treatment. This study shows the natural distribution of a selection of metal ions in wood. Some differences in the distribution and amount of certain metals could also be observed in a sample that had been subjected to treatment with an EDTA-solution.