X-ray Fluorescence Techniques for Element Abundance Analysis in Wine.

The elemental composition has been extensively used to characterize wine and to find correlations with environmental and winemaking factors. Although X-ray fluorescence (XRF) techniques offer many advantages, they have been rarely used for wine analysis. Here, we show the comparison of wine elemental composition results obtained by total reflection X-ray fluorescence (TXRF) and energy dispersive X-ray fluorescence (EDXRF) for elements K, Ca, Mn, Fe, Cu, Zn, Br, Rb, and Sr. The results obtained by TXRF and EDXRF have been additionally verified by inductively coupled plasma-mass spectrometry. The important analytical features of XRF techniques in wine science have been described, the preservation of volatile elements (e.g., Br) being one of their main advantages. In addition, we have shown that XRF techniques offer an optimal analytical approach for building large data sets containing highly reliable and reproducible results of elemental abundances in wines, corresponding soils, and grape juice. Such data sets are especially important for the geographic authentication of wine. This has been shown for 37 Austrian and Croatian wines collected together with respective soils from selected wine regions. The element abundances in soil reflect in a large portion in grape juice and finished wine suggesting that the contribution of the soil, that is, the plant uptake capacity expressed as c i(wine)/c i(soil) concentration factors, can be a highly discriminating factor for wine fingerprinting. This indeed has been proved in the present study in comparison to discrimination based only on wine element abundances. We have identified Fe, Zn, Br, Rb, and Sr as the best discriminator elements for the geographical authentication of wine. The study opens a new perspective in extending the application of XRF techniques as a cost-effective analytical tool for creating large databases of soil, grape juice, and wine element abundances for the evaluation of soil characteristics and other environmental parameters on wine composition.

Measurement of the

We present a measurement of the low-energy (0-60 keV) γ-ray spectrum produced in the α decay of ^{233}U using a dedicated cryogenic magnetic microcalorimeter. The energy resolution of ∼10 eV, together with exceptional gain linearity, allows us to determine the energy of the low-lying isomeric state in ^{229}Th using four complementary evaluation schemes. The most precise scheme determines the ^{229}Th isomer energy to be 8.10(17) eV, corresponding to 153.1(32) nm, superseding in precision previous values based on γ spectroscopy, and agreeing with a recent measurement based on internal conversion electrons. We also measure branching ratios of the relevant excited states to be b_{29}=9.3(6)% and b_{42}<0.7%.

Total reflection X-ray fluorescence analysis of elemental composition of herbal infusions and teas.

BACKGROUND: The elemental composition of herbal infusions and teas has not been sufficiently investigated. It could potentially be used for defining fingerprints for individual herbal / tea infusions, differentiation of botanical families, detecting the influence of packaging, and other purposes. The objective of this study was to determine the elemental composition, including the trace element content, of various herbal infusions and teas by means of total reflection X-ray fluorescence analysis (TXRF), with a chemometrics approach using principal component analysis (PCA). RESULTS: This study determined the elemental composition of various herbal infusions and teas, including trace elements, using total reflection X-ray fluorescence (TXRF). The methodology for the sample preparation was established, including the multiple-steepings procedure for the two tea samples (Oolong and Pu-erh). Data from 29 samples were collected. We hypothesized that the elemental content of infusions could reflect certain features, such as the influence of processing and the type of tea. CONCLUSION: A chemometric approach (PCA) was applied, and differences between teas and herbal infusions were found. This was further corroborated by explicit differentiation of one botanical family, Theaceae. The influence of packaging (tea bags) on herbal material was identified. The three types of tea (Camellia sinensis) appeared to be separated with PCA, and elemental concentrations in Pu-erh changed with multiple steepings.

Detection and imaging of gadolinium accumulation in human bone tissue by micro- and submicro-XRF.

Gadolinium-based contrast agents (GBCAs) are frequently used in patients undergoing magnetic resonance imaging. In GBCAs gadolinium (Gd) is present in a bound chelated form. Gadolinium is a rare-earth element, which is normally not present in human body. Though the blood elimination half-life of contrast agents is about 90 minutes, recent studies demonstrated that some tissues retain gadolinium, which might further pose a health threat due to toxic effects of free gadolinium. It is known that the bone tissue can serve as a gadolinium depot, but so far only bulk measurements were performed. Here we present a summary of experiments in which for the first time we mapped gadolinium in bone biopsy from a male patient with idiopathic osteoporosis (without indication of renal impairment), who received MRI 8 months prior to biopsy. In our studies performed by means of synchrotron radiation induced micro- and submicro-X-ray fluorescence spectroscopy (SR-XRF), gadolinium was detected in human cortical bone tissue. The distribution of gadolinium displays a specific accumulation pattern. Correlation of elemental maps obtained at ANKA synchrotron with qBEI images (quantitative backscattered electron imaging) allowed assignment of Gd structures to the histological bone structures. Follow-up beamtimes at ESRF and Diamond Light Source using submicro-SR-XRF allowed resolving thin Gd structures in cortical bone, as well as correlating them with calcium and zinc.

Increased zinc accumulation in mineralized osteosarcoma tissue measured by confocal synchrotron radiation micro X-ray fluorescence analysis.

Abnormal tissue levels of certain trace elements such as zinc (Zn) were reported in various types of cancer. Little is known about the role of Zn in osteosarcoma. Using confocal synchrotron radiation micro X-ray fluorescence analysis, we characterized the spatial distribution of Zn in high-grade sclerosing osteosarcoma of nine patients (four women/five men; seven knee/one humerus/one femur) following chemotherapy and wide surgical resection. Levels were compared with adjacent normal tissue. Quantitative backscattered electron imaging as well as histological examinations was also performed. On average, the ratio of medians of Zn count rates (normalized to calcium) in mineralized tumor tissue was about six times higher than in normal tissue. There was no difference in Zn levels between tumor fraction areas with a low fraction and a high fraction of mineralized tissue, which were clearly depicted using quantitative backscattered electron imaging. Moreover, we found no correlation between the Zn values and the type of tumor regression according to the Salzer-Kuntschik grading. The underlying mechanism of Zn accumulation remains unclear. Given the emerging data on the role of trace elements in other types of cancer, our novel results warrant further studies on the role of trace elements in bone cancer. Copyright © 2016 The Authors. X-Ray Spectrometry published by John Wiley & Sons Ltd.

µXRF Elemental Mapping of Bioresorbable Magnesium-Based Implants in Bone.

This study investigated the distribution of the elemental constituents of Mg-based implants at various stages of the degradation process in surrounding bone tissue, with a focus on magnesium (Mg), as the main component of the alloy, and yttrium (Y), due to its potential adverse health effects. The measurements were performed on the implant-bearing thin sections of rat bone in a time series of implant degradation between one and 18 months. Micro X-ray fluorescence analysis (µXRF) with a special spectrometer meeting the requirements for the measurements of low-Z elements was used. It was found that the migration and accumulation behaviour of implant degradation products is element-specific. A sharp decrease in Mg was observed in the immediate vicinity of the interface and no specific accumulation or aggregation of Mg in the adjacent bone tissue was detected. By contrast, Y was found to migrate further into the bone over time and to remain in the tissue even after the complete degradation of the implant. Although the nature of Y accumulations must still be clarified, its potential health impact should be considered.

Increased strontium uptake in trabecular bone of ovariectomized calcium-deficient rats treated with strontium ranelate or strontium chloride.

Based on clinical trials showing the efficacy to reduce vertebral and non-vertebral fractures, strontium ranelate (SrR) has been approved in several countries for the treatment of postmenopausal osteoporosis. Hence, it is of special clinical interest to elucidate how the Sr uptake is influenced by dietary Ca deficiency as well as by the formula of Sr administration, SrR versus strontium chloride (SrCl(2)). Three-month-old ovariectomized rats were treated for 90 days with doses of 25 mg kg(-1) d(-1) and 150 mg kg(-1) d(-1) of SrR or SrCl(2) at low (0.1% Ca) or normal (1.19% Ca) Ca diet. Vertebral bone tissue was analysed by confocal synchrotron-radiation-induced micro X-ray fluorescence and by backscattered electron imaging. Principal component analysis and k-means clustering of the acquired elemental maps of Ca and Sr revealed that the newly formed bone exhibited the highest Sr fractions and that low Ca diet increased the Sr uptake by a factor of three to four. Furthermore, Sr uptake in bone of the SrCl(2)-treated animals was generally lower compared with SrR. The study clearly shows that inadequate nutritional calcium intake significantly increases uptake of Sr in serum as well as in trabecular bone matrix. This indicates that nutritional calcium intake as well as serum Ca levels are important regulators of any Sr treatment.

Assessment of chemical species of lead accumulated in tidemarks of human articular cartilage by X-ray absorption near-edge structure analysis.

A highly specific accumulation of the toxic element lead was recently measured in the transition zone between non-calcified and calcified normal human articular cartilage. This transition zone, the so-called `tidemark', is considered to be an active calcification front of great clinical importance. However, little is known about the mechanisms of accumulation and the chemical form of Pb in calcified cartilage and bone. Using spatially resolved X-ray absorption near-edge structure analysis (µ-XANES) at the Pb L(3)-edge, the chemical state of Pb in the osteochondral region was investigated. The feasibility of the µ-XANES set-up at the SUL-X beamline (ANKA synchrotron light source) was tested and confirmed by comparing XANES spectra of bulk Pb-reference compounds recorded at both the XAS and the SUL-X beamline at ANKA. The µ-XANES set-up was then used to investigate the tidemark region of human bone (two patella samples and one femoral head sample). The spectra recorded at the tidemark and at the trabecular bone were found to be highly correlated with the spectra of synthetic Pb-doped carbonated hydroxyapatite, suggesting that in both of these very different tissues Pb is incorporated into the hydroxyapatite structure.

Improved micro x-ray fluorescence spectrometer for light element analysis.

Since most available micro x-ray fluorescence (micro-XRF) spectrometers operate in air, which does not allow the analysis of low-Z elements (Z or = 6). It offers improved excitation and detection conditions necessary for light element analysis. To eliminate absorption of the exciting and fluorescent radiation, the system operates under vacuum condition. Sample mapping is automated and controlled by specialized computer software developed for this spectrometer. Several different samples were measured to test and characterize the spectrometer. The spot size has been determined by scans across a 10 microm Cu wire which resulted in a full width at half maximum of 31 microm for Mo Kalpha line (17.44 keV) and 44 microm effective beam size for the Cu K edge and 71 microm effective beam size for the Cu L edge. Lower limits of detection in the picogram range for each spot (or microg/cm(2)) were obtained by measuring various thin metal foils under different conditions. Furthermore, detection limits in the parts per million range were found measuring NIST621 standard reference material. Area scans of a microscopic laser print and NaF droplet were performed to show mapping capabilities.

Direct analysis of Al2O3 powders by total reflection X-ray fluorescence spectrometry.

A direct analysis procedure for the determination of trace impurities of Ca, V, Cr, Mn, Fe, Ni, Cu, Zn and Ga in Al2O3 ceramic powders by total reflection X-ray fluorescence spectrometry (TXRF) is described. The powders were analysed in the form of slurries containing 1-10 mg mL(-1) of powder. The use of the procedure in the case of powders with differing grain size and for different slurry concentrations was investigated. Three different quantification possibilities were compared, namely the use of Al as a matrix component, the use of Fe as a trace element contained in the sample or of Co added in concentrations of 200 microg g(-1) as internal standard. The homogeneity of elemental distributions in sample layers deposited on the TXRF quartz carriers by evaporating 5 microL of the 10 mg mL(-1) slurries was studied by scanning the 4- to 5-mm-diameter spots of two samples by synchrotron radiation TXRF at Hasylab. For powders with differing graininess but mainly finer than about a few 10 microm, no systematic influence of the grain size on the accuracy of the determinations of Ca, V, Fe, Ni, Cu and Zn could be observed. The measurement precision, however, seemed to be limited by inhomogeneous distributions of the trace elements in the samples as testified by the synchrotron radiation TXRF scans. Detection limits of the developed TXRF procedure for Ca, V, Cr, Mn, Fe, Ni, Cu, Zn and Ga were found to be in the 0.3-7 microg g(-1) range and were shown to increase slightly with the grain size of the samples. Quantification using Al (matrix) as internal standard led to systematically higher values out of the accuracy required, whereas the other two approaches in all cases led to reliable results.