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

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

Lead is a toxic trace element that shows a highly specific accumulation in the transition zone between calcified and non-calcified articular cartilage, the so-called ‘tidemark’. Excellent agreement has been found between XANES spectra of synthetic Pb-doped carbonated hydroxyapatite and spectra obtained in the tidemark region and trabecular bone of normal human samples, confirming that in both tissues Pb is incorporated into the hydroxyapatite crystal structure of bone. During this study the µ-XANES set-up at the SUL-X beamline at ANKA was tested and has proven to be well suited for speciation of lead in human mineralized tissue samples

Atomic spectrometry update. X-ray fluorescence spectrometry

This annual review of X-ray fluorescence covers developments over the period 2006–2007 in instrumentation and detectors, matrix correction and spectrum analysis procedures, X-ray optics and micro-fluorescence, synchrotron XRF, TXRF, portable XRF and on-line applications as assessed from the published literature. The review also covers a survey of applications, including sample preparation, geological, environmental, archaeological, forensic, biological, clinical, thin films, chemical state and speciation studies. Interest continues in micro-analytical instrumentation with synchrotron-based systems benefiting from the availability of more intense beams and efficient focusing optics. Many authors have strengthened the influence of their work with data presented as elemental maps and, where appropriate, factor analysis continues to feature. In common with other analytical techniques, this review demonstrates the emerging field of metallomics to assist in the understanding of how metals and metalloids interact within cells and tissues. Progress continues to support legislation with further analytical methods and reference materials available for environmental and industrial applications. Improvements in detector resolution and excitation optics have helped to strengthen interest in EDXRF systems to meet the demands from society for a reduction in pollutants in ambient air. The writing team would welcome feedback from readers of this review and invite you to complete the Atomic Spectroscopy Updates questionnaire on www.asureviews.org

Atomic spectrometry update–X-ray fluorescence spectrometry

This comprehensive review covers the latest published activities using XRF techniques. X-ray analytical equipment continues to be integrated with X-ray emission/diffraction/absorption techniques with the growing use of synchrotron radiation (SR) sources reflected in the literature. This integration trend was also prevalent in the development of small-scale laboratory equipment. X-ray detectors have advanced with pixellated systems, micro-calorimeter types and the now established silicon drift detectors being readily used by many authors. Matrix correction and calibration procedures have developed to accommodate instrumental developments related to micro-beam and bulk analysis. SR-based micro-techniques for two and three dimensional imaging were reported in research activities in applications for clinical, biological, environmental and cultural heritage studies as well as investigations of extraterrestrial material. Sample preparation developments continue, especially for TXRF. The extension of TXRF to measure the angle dependence fluorescence signal (GI-XRF, XSW) showed increased interest with several groups applying the technique to depth profiling and thin layer analysis of nano-particles. More applications were reported this year for the reversed technique (GE-XRF) combining micro-beam analysis with surface sensitivity. Geochemical mapping of the moon is reported after space flight measurements used the Sun as a radiation source. The literature reflects increasing quantitative analysis using portable XRF with a welcomed growth in acceptance by the Food and Drug authorities and other applied users. This year's Update offers dietary delights for those who enjoy crab meat and an insight into the eating habits of elephants. Advice for gardeners contemplating a green roof is reported along with analysis of the wood treatments used in the manufacture of Stradivari and Guarneri violins. XRF has also played its part in the development of self-cleaning fabrics

2016 Atomic Spectrometry Update – a review of advances in X-ray fluorescence spectrometry and its applications

This review describes advances in the XRF group of techniques published approximately between April 2015 and March 2016. Fundamental contributions in the instrumentation sections include the development of synchrotron radiation sources, semiconductor design technology and evaluating the quality of in situ hand-held XRF results. A bench top TXRF spectrometer for the measurement of the elements from carbon to uranium is described that offers achievable detection limits that range from ng g−1 to μg g−1. The applications sections aim to give a representative overview of the range of applications that use XRF techniques with an emphasis on papers that describe technical or application innovation. Sample size investigated ranged from the planet Mercury down to nano-gram quantities of cement secreted by settlement stage barnacle larvae. The archaeological and cultural heritage section this year includes an authentic report on the use of cannabis as a filler in ancient lime plaster and heartening news that the construction of an underground parking garage in the centre of Zurich (Switzerland) unearthed the remains of seven Neolithic settlements from the 4th and 3rd millennium BC. The X-ray excitation of iron present in ancient iron-gall inks was presented as a step toward the non-invasive reading of fragile and/or unopenable documents. Feedback from readers of this review is most welcome and the review coordinator may be contacted using the email address provided

Synchrotron radiation induced TXRF- a critical review

The use of synchrotron radiation (SR) as an excitation source for total reflection X-ray fluorescence analysis (TXRF) offers several advantages over X-ray tube excitation. Detection limits in the fg range can be achieved with efficient excitation for low Z as well as high Z elements due to the features of synchrotron radiation and in particular the high brilliance in a wide spectral range and the linear polarization in the orbital plane. SR-TXRF is especially interesting for samples where only small sample masses are available. Lowest detection limits are typically achieved using multilayer monochromators since they exhibit a bandwidth of about 0.01 DE/E. Monochromators with smaller bandwidth like perfect crystals, reduce the intensity, but allow X-ray absorption spectroscopy (XAS) measurements in fluorescence mode for speciation and chemical characterisation at trace levels. SR-TXRF is performed at various synchrotron radiation facilities. An historical overview is presented and recent setups and applications as well as some critical aspects are reviewed