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Total reflection X-ray fluorescence analysis (TXRF) was used to determine chromium, selenium and bromine concentrations in blood serum samples of 50 patients with parenteral nutrition treatment. The concentrations were measured two times, namely in the first day (I measurement) of the treatment and the seventh day (II measurement) after the chromium and selenium supplementation. For comparison purposes also serum samples of 50 patients without nutritional disorders, admitted to a planned surgical procedure to remove the gall bladder (cholecystectomy), were analyzed and treated as the control group. Descriptive statistics of measured concentrations of Cr, Se and Br both for the studied and control groups was determined. In order to check the effectiveness of Cr and Se supplementation, the results of the first and seventh day measurements for studied group were statistically compared with each other, with literature reference values and with the results of the control group (two-group comparison). These comparisons indicate the effectiveness of selenium supplementation in the applied treatment procedure. In the case of Cr and Br concentrations no statistically significant differences were observed. We conclude that monitoring of the concentration of the important trace elements in human serum should be standard procedure in parenteral nutrition treatment. In this monitoring the TXRF technique can be successfully used., Competing Interests: The authors have declared that no competing interests exist.

Confocal micro-beam X-ray fluorescence analysis (confocal micro-XRF) is a non-destructive analytical tool for investigation of sample composition that enables acquiring three-dimensionally resolved information. This work describes a calibration procedure of a laboratory confocal micro-XRF setup, which leads to determination of its characteristic parameters. The calibration is performed using a tabletop confocal micro-XRF spectrometer designed recently at the Czech Technical University in Prague. The calibration procedure performed within this work comprises the essential steps of the setup characterization: excitation spectrum calculation, experimental determination of energy-dependent confocal volume size and integral sensitivity and calculation of the spectrometer sensitivity function. The results of the setup calibration will be used for development of a procedure enabling quantitative evaluation of the measured depth profiles., (© The Author(s) 2019. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.)

This paper describes the implementation of a novel and robust threshold energy calibration method for photon counting detectors using polychromatic X-ray tubes. Methods often used for such energy calibration may require re-orientation of the detector or introduce calibration errors that are flux and acquisition time-dependent. Our newly proposed "differential intensity ratios" (DIR) method offers a practical and robust alternative to existing methods. We demonstrate this robustness against photon flux used in calibration, spectral errors such as pulse pile-up as well as the detector's inherent spectral resolution limits. The demonstrated significant insensitivity of the proposed DIR signature to detector spectral distortions and energy resolution is a key finding. The proposed DIR calibration method is demonstrated using Medipix3RX detectors with a CdTe sensor under varying flux conditions. A per pixel calibration using the DIR method has also been implemented to demonstrate an improvement over the global energy resolution of the PCD.

Talc may lodge in human tissues through various routes, and has been associated with the development of ovarian carcinoma in case control epidemiologic studies. Talc is detected in tissues with scanning electron microscopy and energy dispersive X-ray analysis (SEM/EDS), with expected magnesium (Mg) and silicon (Si) peaks. The theoretical atomic weight % Mg/Si ratio for talc is 0.649, and for diagnostic purposes, a range of ± 5% (~0.617 to 0.681) is often used as a standard. Our goal was to establish empirically the quantitative range for talc identification by SEM/EDS using two source materials: a Johnson's Baby Powder TM (cosmetic-grade) consumer sample, and talc from Sigma-Aldrich (particle-grade material intended for scientific use). We examined 401 Mg-Si particles with SEM/EDS across the two samples, using two different SEM microscopes. Overall, we found a mean Mg/Si atomic weight % ratio of 0.645, with minimal differences between study subsets. The standard deviation was 0.025; (± 1σ = 0.620-0.670). The currently used ± 5% diagnostic range (Mg/Si 0.617-0.681) is thus reasonably close to this study's ± 1σ range, and well within a ± 2 σ confidence interval span (Mg/Si 0.595-0.695). The ± 5% range is thus an appropriately conservative standard whose continued use seems justified.

The aim of this research is to develop a fast analytical method for multielemental analysis of the tobacco plant Virginia tobacco (cultivated in Poland) and tobacco products (cigarettes, cigars, cigarillos, snuff and two kinds of properly crafted tobacco such as a shisha and cigarette tobacco) distributed in Polish markets by means of a low-power benchtop total reflection X-ray fluorescence (TXRF) system. For this purpose, a set of certified tobacco materials and real samples was employed. In leaves and stalks of V. tobacco and tobacco products, a concentration of 18 elements (P, S, Cl, K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Br, Rb, Sr and Pb) was determined. Analyzing elemental composition of tobacco plants, one can see that concentrations of S, Ca, Ti, Mn, Zn, Sr and Pb are higher in leaves, whereas the concentrations of P, Cl, K, Fe Cu and Br are higher in stalks; the levels of Cr, Ni, As and Rb are comparable in both these parts of the tobacco plant. All of the parameters affecting sample preparation and TXRF measurements conditions were carefully evaluated. The accuracy and precision of the TXRF measurements were verified using an internal standardization approach for quantification.

In this paper, effective energy of pulsed X-Ray emitted from a Mather-type plasma focus device in stored energy of 2.5 kJ with six different anode's insert materials was measured using radiographic method with attenuation filters. Since intensity and energy of X-ray beam were considerably changed with changing the insert material, the method was improved by using different filters simultaneously in all the experiments and selection of the best filter in each experiment according to the appropriate criteria. Effective energy of pulsed X-ray beam was measured 16, 28, 50, 51, 34 and 44 keV when aluminum, copper, zinc, tin, tungsten and lead were used as insert materials, and aluminum, copper, silver, silver, copper and lead were used as filters, respectively., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

There is a strong need in the medical device industry to decrease failure rates of biomedical devices by reducing the incidence of defect structures and contaminants during the production process. The detection and identification of defect structures and contaminants is crucial for many industrial applications. The present study exploits reference-free X-ray fluorescence (XRF) analysis as an analytical tool for the traceable characterization of surface contaminants of medical devices, in particular N,N'-ethylene-bis (stearamide), an ubiquitous compound used in many industrial applications as a release agent or friction reduction additive. Reference-free XRF analysis as primary method has been proven to be capable of underpinning all other applied methods since it yields the absolute mass deposition of the selected N,N'-ethylene-bis (stearamide) contaminant whilst X-ray absorption fine structure analysis determines the chemical species. Ambient vibrational spectroscopy and mass spectroscopy methodologies such as Fourier transform infrared, Raman, and secondary ion mass spectroscopy have been used in this systematic procedure providing an extensive range of complementary analyses. The calibration procedure described in this paper was developed using specially designed and fabricated model systems varying in thickness and substrate material. Furthermore, typical real medical devices such as both a polyethylene hip liner and a silver-coated wound dressing have been contaminated and investigated by these diverse methods, enabling testing of this developed procedure. These well-characterized samples may be used as calibration standards for bench top instrumentation from the perspective of providing traceable analysis of biomaterials and surface treatments. These findings demonstrate the potential importance and usefulness of combining complementary methods for a better understanding of the relevant organic materials., (Copyright © 2017 Elsevier B.V. All rights reserved.)

A method of direct analysis for quantification of 15 inorganic elements (P, S, Cl, K, Ca, Mn, Fe, Ni, Cu, Zn, Br, As, Rb, Sr and Pb) in beers by Total Reflection X-Ray Fluorescence (TXRF) was developed. The experimental conditions were optimized. Direct analysis was compared with the acid digestion procedure to evaluate the effect matrix and the results were satisfactory. The evaluation of the accuracy and precision was realized by analysis of two certified reference materials of natural and waste water. For the majority of the elements, good agreement was achieved between the certified value and the value measured in the CRM´s. Low detection limits were obtained and it was adequate to determine trace elements in beers and to quality control Pb and As, whose maximum limits are 200 and 100µgL -1 , respectively. The relative standard deviation (RSD%) ranged from 2.4% to 10%. The method was applied to 30 beer samples collected in several regions of Brazil. The concentration ranges (mgL -1 ) for the studied analytes were: P: (37.40-140.85); S (10.32-50.73); Cl (82.74-281.7); K (183.8-418.5); Ca (9.82-96.0); Mn (0.06-1.42); Fe (0.07-1.57); Ni (< LLD-1.13); Cu (< LLD-0.32); Zn (0.02-1.98); As (< LLD-0.10); Br (0.01-2.04); Rb (< LLD-0.52); Sr (< LLD-0.41) and Pb (< LLD-0.18). Some beer samples showed As and Pb concentrations above the levels established by Brazilian legislation. The developed method is simple, fast, consumes low amounts of reagents and allows the determination of a large number of analytes simultaneously. TXRF proved to be attractive and useful for routine analysis., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Compton scatter-modulated fluorescence and multivariate chemometric (artificial neural network (ANN) and principal component regression (PCR)) calibration strategy was explored for direct rapid trace biometals (Mn, Fe, Cu, Zn, Se) analysis in "complex" matrices (model soft tissues). This involved spectral feature selection (multiple fluorescence signatures) normalized to or in conjunction with Compton scatter. ANN model resulted in more accurate trace biometal determination (R 2 >0.9) compared to PCR. Hybrid nested (ANN and PCR) approach led to optimized accurate biometals' concentrations in Oyster tissue (≤ ± 10%)., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Assessment of chromium content in human nail or nail clippings could serve as an effective biomarker of chromium status. The feasibility of a new portable x-ray fluorescence (XRF) approach to chromium measurement was investigated through analysis of nail and nail clipping phantoms. Five measurements of 180s (real time) duration were first performed on six whole nail phantoms having chromium concentrations of 0, 2, 5, 10, 15, and 20µg/g. Using nail clippers, these phantoms were then converted to nail clippings, and assembled into different mass groups of 20, 40, 60, 80, and 100mg for additional measurements. The amplitude of the chromium Kα characteristic x-ray energy peak was examined as a function of phantom concentration for all measurement conditions to create a series of calibration lines. The minimum detection limit (MDL) for chromium was also calculated for each case. The chromium MDL determined from the whole nail intact phantoms was 0.88±0.03µg/g. For the clipping phantoms, the MDL ranged from 1.2 to 3.3µg/g, depending on the mass group analyzed. For the 40mg clipping group, the MDL was 1.2±0.1µg/g, and higher mass collections did not improve upon this result. This MDL is comparable to chromium concentration levels seen in various studies involving human nail clippings. Further improvements to the portable XRF technique would be required to detect chromium levels expected from the lower end of a typical population., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The energy information acquired using spectral X-ray detectors allows noninvasive identification and characterization of chemical components of a material. To achieve this, it is important that the energy response of the detector is calibrated. The established techniques for energy calibration are not practical for routine use in pre-clinical or clinical research environment. This is due to the requirements of using monochromatic radiation sources such as synchrotron, radio-isotopes, and prohibitively long time needed to set up the equipment and make measurements. To address these limitations, we have developed an automated technique for calibrating the energy response of the pixels in a spectral X-ray detector that runs with minimal user intervention. This technique uses the X-ray tube voltage (kVp) as a reference energy, which is stepped through an energy range of interest. This technique locates the energy threshold where a pixel transitions from not-counting (off) to counting (on). Similarly, we have developed a technique for calibrating the energy response of individual pixels using X-ray fluorescence generated by metallic targets directly irradiated with polychromatic X-rays, and additionally γ-rays from (241)Am. This technique was used to measure the energy response of individual pixels in CdTe-Medipix3RX by characterizing noise performance, threshold dispersion, gain variation and spectral resolution. The comparison of these two techniques shows the energy difference of 1 keV at 59.5 keV which is less than the spectral resolution of the detector (full-width at half-maximum of 8 keV at 59.5 keV). Both techniques can be used as quality control tools in a pre-clinical multi-energy CT scanner using spectral X-ray detectors.

Accurate energy calibration is critical for the application of energy-resolved photon-counting detectors in spectral imaging. The aim of this study is to investigate the feasibility of energy response calibration and characterization of a photon-counting detector using x-ray fluorescence. A comprehensive Monte Carlo simulation study was performed using Geant4 Application for Tomographic Emission (GATE) to investigate the optimal technique for x-ray fluorescence calibration. Simulations were conducted using a 100 kVp tungsten-anode spectra with 2.7 mm Al filter for a single pixel cadmium telluride (CdTe) detector with 3 × 3 mm(2) in detection area. The angular dependence of x-ray fluorescence and scatter background was investigated by varying the detection angle from 20° to 170° with respect to the beam direction. The effects of the detector material, shape, and size on the recorded x-ray fluorescence were investigated. The fluorescent material size effect was considered with and without the container for the fluorescent material. In order to provide validation for the simulation result, the angular dependence of x-ray fluorescence from five fluorescent materials was experimentally measured using a spectrometer. Finally, eleven of the fluorescent materials were used for energy calibration of a CZT-based photon-counting detector. The optimal detection angle was determined to be approximately at 120° with respect to the beam direction, which showed the highest fluorescence to scatter ratio (FSR) with a weak dependence on the fluorescent material size. The feasibility of x-ray fluorescence for energy calibration of photon-counting detectors in the diagnostic x-ray energy range was verified by successfully calibrating the energy response of a CZT-based photon-counting detector. The results of this study can be used as a guideline to implement the x-ray fluorescence calibration method for photon-counting detectors in a typical imaging laboratory.

Extensive evidence of the adverse impacts of polychlorinated biphenyls (PCBs) to wildlife, domestic animals, and humans has now been documented for over 40 years. Despite the ban on production and new use of PCBs in the United States in 1979, a number of fish consumption advisories remain in effect, and there remains considerable uncertainty regarding ongoing environmental sources and management alternatives. Using a blind sampling approach, 25 caulk samples were collected from the exterior of ten buildings in the San Francisco Bay Area and analyzed for PCBs using congener-specific gas chromatography-mass spectrometry (GC-MS) and chlorine using portable X-ray fluorescence (XRF). PCBs were detected in 88% of the caulk samples collected from the study area buildings, with 40% exceeding 50 ppm. Detectable PCB concentrations ranged from 1 to 220,000 ppm. These data are consistent with previous studies in other cities that have identified relatively high concentrations of PCBs in concrete and masonry buildings built between 1950 and 1980. Portable XRF was not a good predictor of the PCB content in caulk and the results indicate that portable XRF analysis may only be useful for identifying caulk that contains low concentrations of Cl (≤ 10,000 ppm) and by extension low or no PCBs. A geographic information system-based approach was used to estimate that 10,500 kg of PCBs remain in interior and exterior caulk in buildings located in the study area, which equates to an average of 4.7 kg PCBs per building. The presence of high concentrations in the exterior caulk of currently standing buildings suggests that building caulk may be an ongoing source of PCBs to the San Francisco Bay Area environment. Further studies to expand the currently small international dataset on PCBs in caulking materials in buildings of countries that produced or imported PCBs appear justified in the context of both human health and possible ongoing environmental release., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Imaging and analyzing gunshot residue (GSR) particles using the scanning electron microscope equipped with an energy dispersive X-ray spectrometer (SEM-EDS) is a standard technique that can provide important forensic evidence, but the discrimination power of this technique is limited due to low sensitivity to trace elements and difficulties in obtaining quantitative results from small particles. A new, faster method using a scanning proton microbeam and Particle Induced X-ray Emission (μ-PIXE), together with Elastic Backscattering Spectrometry (EBS) is presented for the non-destructive, quantitative analysis of the elemental composition of single GSR particles. In this study, the GSR particles were all Pb, Ba, Sb. The precision of the method is assessed. The grouping behaviour of different makes of ammunition is determined using multivariate analysis. The protocol correctly groups the cartridges studied here, with a confidence >99%, irrespective of the firearm or population of particles selected.

In the present study, and taking into account the microanalytical capability of total reflection X-ray spectrometry (TXRF), we explored the possibilities of hollow fibre liquid-phase microextraction (HF-LPME) and dispersive liquid-liquid microextraction (DLLME) combined with TXRF for the determination of low amounts of inorganic Sb species in waters. For each of the LPME configurations aforementioned, experimental parameters affecting Sb extraction but specially the proper sample preparation process (deposition volume on the reflective carrier and drying mode) and measurement conditions for subsequent TXRF analysis have been carefully evaluated. The best analytical strategy for the determination of Sb(III) and Sb(V) in the low μg L(-1) range was found to be the application of the DLLME mode before TXRF analysis. The developed methodology was successfully applied to the determination of inorganic Sb speciation in different types of spiked water samples., (Copyright © 2013 Elsevier B.V. All rights reserved.)

In manganese-enhanced magnetic resonance imaging (MEMRI), the paramagnetic divalent ion of manganese (Mn(2+)) is injected into animals to generate tissue contrast, typically at much higher exposures than have been previously used in studies of Mn toxicity. Here we investigate the effect of these injections on the homeostasis of the transition metals iron and copper in mice to see if there are disruptions which should be considered in MEMRI studies. Manganese shares transport proteins with other transition metals including iron and copper, so it is possible that changes in manganese levels in tissue following injections of the metal may affect other metal levels too. This in turn may affect MRI contrast or the investigation of disease processes in the animal models being imaged. In this study, we measured manganese, iron, and copper concentrations in the blood, kidney, liver and in brain regions in mice treated with four injections of 30 mg/kg MnCl(2) 4H(2)O (dry chemical weight/body weight)-a common dose used in MEMRI. In addition to the expected increases in manganese in tissues, we noted a statistically significant reduction in copper in the kidney and liver. Also, we noted a statistically significant decrease in concentration of iron in the thalamus of the brain. These findings suggest that the high doses of manganese injected in MEMRI studies can disrupt the homeostasis of other transition metals in mice.

Total reflection X-ray spectrometry is an instrumental technique based on X-ray fluorescence, which offers detection limits low enough to quantify trace element concentrations with negligible interference from matrix components. The technique is well established in material sciences and now reaches out to extended applications in life sciences and pharmaceutical quality control. In our study we focused on possible applications for the quantification of gold and platinum containing active ingredients in trace concentrations (ppb range) in a matrix of biological origin (cell suspensions). General aspects of sample preparation as well as selected important method performance parameters (precision, recovery rates) were investigated. Overall, TXRF represents an useful option to quantify metals in ppb concentrations with acceptable precision and recovery., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Palladium (Pd) is extensively used in pharmaceutical small molecule drug substance processes, however it must be removed prior to release of the active pharmaceutical ingredient (API). Evaluation of four TXRF instruments and configurations were compared to ICP-MS instrumentation for trace metal analysis, most importantly for Pd. Standards and six pharmaceutical drug substances, triprolidine HCl, diphenhydramine HCl, chlorpheniramine maleate, pseudoephedrine HCl, ephedrine sulfate, and scopolamine HBr, were analyzed to determine linearity, sensitivity, accuracy, and precision for Pd plus Cr, Fe, Cu, Rh, and Pt versus interferences, particularly from Cl, S, and Ar, on the various X-ray fluorescence lines. Irrespective of instrument platform, in general X-ray sources capable of accessing Pd-K lines were found to be most effective in determination of Pd in APIs., (Copyright © 2012 Elsevier B.V. All rights reserved.)

In-vivo measurement of bone lead by means of K-X-ray fluorescence (KXRF) is the preferred biological marker of chronic exposure to lead. Unfortunately, considerable measurement error associated with KXRF estimations can introduce bias in estimates of the effect of bone lead when this variable is included as the exposure in a regression model. Estimates of uncertainty reported by the KXRF instrument reflect the variance of the measurement error and, although they can be used to correct the measurement error bias, they are seldom used in epidemiological statistical analyzes. Errors-in-variables regression (EIV) allows for correction of bias caused by measurement error in predictor variables, based on the knowledge of the reliability of such variables. The authors propose a way to obtain reliability coefficients for bone lead measurements from uncertainty data reported by the KXRF instrument and compare, by the use of Monte Carlo simulations, results obtained using EIV regression models vs. those obtained by the standard procedures. Results of the simulations show that Ordinary Least Square (OLS) regression models provide severely biased estimates of effect, and that EIV provides nearly unbiased estimates. Although EIV effect estimates are more imprecise, their mean squared error is much smaller than that of OLS estimates. In conclusion, EIV is a better alternative than OLS to estimate the effect of bone lead when measured by KXRF., (Copyright © 2010 Elsevier Inc. All rights reserved.)

Recent advances in field-portable X-ray fluorescence (FP XRF) spectrometer technology have made it a potentially valuable screening tool for the industrial hygienist to estimate worker exposures to airborne metals. Although recent studies have shown that FP XRF technology may be better suited for qualitative or semiquantitative analysis of airborne lead in the workplace, these studies have not extensively addressed its ability to measure other elements. This study involved a laboratory-based evaluation of a representative model FP XRF spectrometer to measure elements commonly encountered in workplace settings that may be collected on air sample filter media, including chromium, copper, iron, manganese, nickel, lead, and zinc. The evaluation included assessments of (1) response intensity with respect to location on the probe window, (2) limits of detection for five different filter media, (3) limits of detection as a function of analysis time, and (4) bias, precision, and accuracy estimates. Teflon, polyvinyl chloride, polypropylene, and mixed cellulose ester filter media all had similarly low limits of detection for the set of elements examined. Limits of detection, bias, and precision generally improved with increasing analysis time. Bias, precision, and accuracy estimates generally improved with increasing element concentration. Accuracy estimates met the National Institute for Occupational Safety and Health criterion for nearly all the element and concentration combinations. Based on these results, FP XRF spectrometry shows potential to be useful in the assessment of worker inhalation exposures to other metals in addition to lead.

Synchrotron-based X-ray absorption near-edge structure (XANES) spectroscopy is becoming an increasingly used tool for the element speciation in complex samples. For phosphorus (P) almost all XANES measurements have been carried out at the K-edge. The small number of distinctive features at the P K-edge makes in some cases the identification of different P forms difficult or impossible. As indicated by a few previous studies, the P L(2,3)-edge spectra were richer in spectral features than those of the P K-edge. However, experimentally consistent spectra of a wide range of reference compounds have not been published so far. In this study a library of spectral features is presented for a number of mineral P, organic P and P-bearing minerals for fingerprinting identification. Furthermore, the effect of radiation damage is shown for three compounds and measures are proposed to reduce it. The spectra library provided lays a basis for the identification of individual P forms in samples of unknown composition for a variety of scientific areas.

A field-portable X-ray fluorescence analyzer, factory-calibrated for soil analysis, was used to measure bromine (Br) mass fractions in reference materials, flour, bakery products, malted barley, selected U.S. Food and Drug Administration Total Diet Study foods, and other food products. By using a calibration based on instrumental neutron activation analysis results for Br in reference materials, accurate quantitative results, confirmed by z-scores, could be obtained for mass fractions of about 2-55 mg/kg. These results confirmed accuracy of results (with larger uncertainties) obtained by applying a simple correction factor to the analyzer's output value. Results showed that very short analysis times (<2 min) would be needed to screen foods for Br content at regulatory levels for brominated and enriched brominated flour (24 mg/kg Br) and whole wheat flour and bakery products (36 mg/kg Br). Feasibility for determination of Br in malted barley at the regulatory level (75 mg/kg Br) was demonstrated, but quantitative results at that level could not be assured because no reference material with a suitable mass fraction was available. Br mass fractions for all foods tested were well below regulatory levels.

The use of least-squares regression to probe the level of lead contamination of plaster of Paris standards in the calibration of (109)Cd KXRF systems for bone lead measurement, as well as the use of iteratively reweighted least-squares (IRLS) in the case of violation of the assumptions for ordinary least-squares (OLS), is discussed here. One common violation is non-uniform residual variance, which makes the use of OLS inappropriate due to strong influence of points with large variance on the calibration line and variance of the slope and intercept. Comparison between OLS and IRLS in that case showed that IRLS estimates of the intercept are significantly smaller and more precise than OLS estimates, while a less marked increase in the calibration slope is observed when IRLS is used. Moreover, OLS underestimates bone lead concentrations at low levels of lead exposure and overestimates those concentrations at higher levels. These discrepancies are smaller in magnitude than the measurement uncertainty of conventional systems, except for high concentrations. For the newly developed cloverleaf systems, the suggested differences at bone lead concentrations below 17 ppm are comparable to the minimum detection limit, but are larger than the measurement uncertainty for bone lead concentrations above 60 ppm.

For the first time a method has been developed for the extended X-ray absorption fine structure (EXAFS) data analyses of biological samples containing multiple oxidation states of chromium. In this study, the first shell coordination and interatomic distances based on the data analysis of known standards of potassium chromate (Cr(VI)) and chromium nitrate hexahydrate (Cr(III)) were investigated. The standards examined were mixtures of the following molar ratios of Cr(VI):Cr(III), 0:1, 0.25:0.75, 0.5:0.5, 0.75:0.25, and 1:0. It was determined from the calibration data that the fitting error associated with linear combination X-ray absorption near edge structure (LC-XANES) fittings was approximately +/-10% of the total fitting. The peak height of the Cr(VI) pre-edge feature after normalization of the X-ray absorption (XAS) spectra was used to prepare a calibration curve. The EXAFS fittings of the standards were also investigated and fittings to lechuguilla biomass samples laden with different ratios of Cr(III) and Cr(VI) were performed as well. An excellent agreement between the XANES data and the data presented in the EXAFS spectra was observed. The EXFAS data also presented mean coordination numbers directly related to the ratios of the different chromium oxidation states in the sample. The chromium oxygen interactions had two different bond lengths at approximately 1.68 and 1.98 A for the Cr(VI) and Cr(III) in the sample, respectively.

Background: Experimental bone metastases are typically analyzed when the skeletal tumor burden is large enough to be detected by imaging or histology. By this time, the bone microenvironment is usually destroyed, preventing useful analysis of tumor-bone interactions., Methods: Small intraosseous tumors generated by intratibial injection of C4-2B prostate cancer cells transfected with green fluorescent protein (GFP) were assessed using in vivo and ex vivo fluorescence imaging, radiography, histology, and fluorometric analysis of bone lysates., Results: Ex vivo fluorescence imaging and fluorometric analysis were capable of detecting tiny bone tumors as early as 10 days after injection. Ex vivo fluorescence imaging allowed simple quantification of small skeletal tumor burden and was useful in measuring the effect of systemic therapy., Conclusions: Ex vivo fluorescence imaging is a sensitive and easy method to quantify small skeletal tumor burden. This technique allows investigation of tumor-bone interactions while the bone microanatomy is still intact., ((c) 2006 Wiley-Liss, Inc.)

Objective: To determine if long-term exposure to high levels of lead in the environment is associated with decrements in cognitive ability in older Americans., Methods: We completed a cross-sectional analysis using multiple linear regression to evaluate associations of recent (in blood) and cumulative (in tibia) lead dose with cognitive function in 991 sociodemographically diverse, community-dwelling adults, aged 50 to 70 years, randomly selected from 65 contiguous neighborhoods in Baltimore, MD. Tibia lead was measured with (109)Cd induced K-shell X-ray fluorescence. Seven summary measures of cognitive function were created based on standard tests in these domains: language, processing speed, eye-hand coordination, executive functioning, verbal memory and learning, visual memory, and visuoconstruction., Results: The mean (SD) blood lead level was 3.5 (2.2) microg/dL and tibia lead level was 18.7 (11.2) microg/g. Higher tibia lead levels were consistently associated with worse cognitive function in all seven domains after adjusting for age, sex, APOE-epsilon4, and testing technician (six domains p

The DXAS Calibration computer program provides a quantitative and automated solution to the problem of calibrating spectra from dispersive XAS beamlines. Such spectra, obtained in arbitrary energy units, are calibrated with respect to the absorption features of a supplied reference spectrum, which has been obtained under similar conditions on a calibrated beamline. In addition to basic energy coordinate transformation parameters, DXAS Calibration supplies instrument corrections to compensate for mismatches in instrument response functions between the dispersive and reference beamlines.

Originally developed for time-resolved X-ray absorption spectroscopy (XAS), energy-dispersive absorption spectroscopy offers new opportunities for applications such as fluorescence detection and microbeams for scanning probe spectroscopy, thanks to recent developments in both instrumentation and optics. In this context, this paper presents a first example of chemical mapping recorded at ID24, the energy-dispersive XAS beamline at the ESRF. Attributes of this geometry for microanalysis are addressed. Finally, present and future plans are discussed and developed in the light of the evolution of the focal spot on this instrument in the past ten years.

Accurate normalization of X-ray absorption data is essential for quantitative analysis of near-edge features. A method, implemented as the program MBACK, to normalize X-ray absorption data to tabulated mass absorption coefficients is described. Comparison of conventional normalization methods with MBACK demonstrates that the new normalization method is not sensitive to the shape of the background function, thus allowing accurate comparison of data collected in transmission mode with data collected using fluorescence ion chambers or solid-state fluorescence detectors. The new method is shown to have better reliability and consistency and smaller errors than conventional normalization methods. The sensitivity of the new normalization method is illustrated by analysis of data collected during an equilibrium titration.

An international comparison for plutonium isotopic composition measurement, known as the Pu-2000 exercise, was organized by the ESARDA NDA-WG (European Safeguards Research and Development Association, Working Group on Techniques and Standards for Non-Destructive Assay). The aim of this comparison was to test X- and gamma-ray spectrometry methods over a large range of isotopic ratios. These methods are based on the complex analysis of several X- and gamma-rays in the KX region of the plutonium spectrum and also in the 120-700 keV energy range. The results obtained by the participants with their corresponding uncertainties are presented in this document and compared to the declared values. The main conclusions of the work are also given. No important bias due to an inadequate knowledge of the nuclear data for plutonium isotopes was observed.

The purposes of this study are: (1) to determine whether proficiency analytical test (PAT) materials from the American Industrial Hygiene Association can be used to provide quality data for portable X-ray fluorescence analysis (XRF) of lead in dust wipe surface samples; (2) to provide data to determine whether the on-site analysis of field dust wipe samples by XRF and the laboratory method of inductively coupled plasma emission analysis (ICP) are comparable; and (3) to determine if differences exist between different wipe materials. Several wipes meet the ASTM E1792 performance requirements of lead background level less than 5 microg per wipe, be only one layer thick, yield recovery rates of 80- 120% from spiked samples, remain damp throughout the sampling procedure, and do not contain aloe. The wipes used in this study were Pace Wipes, which are used for the PAT materials, and, for the field samples, Palintest Wipes, which were supplied by the instrument manufacturer, and Ghost Wipes, which are popular because they digest in hot, concentrated acid, so that chemical analysis is simplified. Twenty PAT wipe samples were obtained from four different proficiency test rounds. Surface wipe samples were taken at three different locations representing different industry types. All samples were analyzed using a portable XRF spectrometer and by ICP. Strong linear relationships were found for the analysis of wipe samples by ICP and by portable XRF. For the PAT samples, the results from the ICP and XRF analysis were not statistically equivalent, which indicates a bias in the ICP analysis. The bias was not excessive, since all ICP analyses fell within the acceptable range for the proficiency samples. The good correlation between the proficiency sample reference values and the XRF determinations is not surprising considering similar proficiency samples were used to calibrate the instrument response. Users of this portable XRF analyzer could enroll in the proficiency test program as part of their quality assurance program. For field samples, the relationship was strongest for Palintest wipes, and the values found for all three industries could be combined. However, the results from the ICP and XRF analysis were not statistically equivalent using the correction factor in the calculation algorithm as supplied with the instrument, and a new coefficient was derived. The mean relative error for the XRF analysis versus the ICP analysis was greater than 25%, such that the method falls within the realm of screening procedures. For Ghost Wipe samples, the precision was different for different industries, and the results could not be pooled. Differences between the two wipe materials may be related to the number of folds required for analysis.

Due to signal attenuation in overlying soft tissue, development of x-ray fluorescence systems to measure low atomic number elements, such as strontium, in human bone required a search for a skeletal site with thin overlying tissue. This paper reports ultrasound measurements of overlying tissue on 10 subjects, at four anatomical sites. The average tissue thickness at the finger was (2.9+/-0.7) mm. The average tissue thicknesses were (3.6+/-0.7) mm, (4.8+/-2.0) mm, and (8.4+/-1.7) mm at forehead, tibia and heel, respectively. Additionally, both parametric and nonparametric approaches to the relationship between body mass index (BMI) and tissue thickness suggest that there is a significant linear correlation between the subject's BMI and overlying tissue at the finger and heel bone. These correlations might be used as a criterion to perform XRF measurements, however a larger data set is required to address these correlations more clearly.

The present paper reports significant enhancement of the detection power for total-reflection X-ray fluorescence (TXRF). The employment of an efficient wavelength-dispersive spectrometer rather than a conventional Si(Li) detector, as well as the use of a quasi-monochromatic undulator X-ray source, completely changed the quality of X-ray florescence spectra. The energy resolution is 20 times better, which effectively contributes to reducing the low-energy tail of the scattering background and to separating neighboring X-ray florescence peaks. Another advantage is its capability with respect to high-counting-rate measurements, which ensure the detection of weak signals from trace materials. The absolute and relative detection limit for nickel are 3.1 x 10(-16) g and 3.1 ppt (pg/g) for a 0.1-microL droplet of pure water, respectively, which is nearly 50 times better than the current best data achieved by conventional energy-dispersive TXRF using a Si(Li) detector system.

The aim of this study was to apply the technique of (109)Cd-based K-shell X-ray fluorescence (XRF) bone lead measurements to swine femurs and to validate the concentrations obtained therefrom against an independent chemical measurement of bone lead: atomic absorption spectrometry (AAS). The femurs ranged in lead concentration from 1.0 to 24.5 microg of lead per gram of ashed bone, as measured by AAS. On average, XRF overestimated AAS-measured femur lead by 2.6 microg/g [95% confidence interval (CI), 1.1-4.0 microg/g], approximately 2 microg/g poorer than that observed in studies of human tibiae. Measurements of swine femur and, by extension, of nonhuman bones may require adjustment of the XRF spectrum peak extraction method.

The purpose of this study was to remeasure in vivo tibia lead levels in a lead-acid battery manufacturing workforce measured in a previous survey and believed to be unrealistically high. Tibia lead levels were measured by K-shell X-ray fluorescence (XRF) spectroscopy in a stratified random sample (n=40) of the original study group (n=381). The repeat survey showed much lower tibia lead levels (median=54.3 microg lead/g bone mineral, compared to 217.9 microg lead/g bone mineral, n=40). Tibia lead levels were significantly correlated with duration of occupational exposure, zinc protoporphyrin levels, and cumulative blood lead index, but not with current blood lead levels. Thirty-eight of the 40 subjects underwent two consecutive tibia lead measurements to assess the test-retest repeatability of the XRF tibia lead measurement technique. The intraclass correlation coefficient between repeated measurements was 0.926 (P=0.0001). Three measurement pairs differed by more than 20 microg/g. There was no fixed or proportional bias between the two sets of measurements. We conclude that the technique offers a highly repeatable measurement of tibia bone lead. However, care needs to be taken to avoid contamination when performing measurements on active lead workers., (Copyright 2000 Academic Press.)

An energy dispersive X-ray fluorescence analysis was applied for determining the spatial (two-dimensional) distribution of elemental concentrations in rat brain sections. Freeze-dried brain sections prepared from normal and ischemic rats with middle cerebral artery occlusion were scanned with a collimated X-ray beam (0.18 mm in diameter, 50-kV acceleration voltage). The fluorescent Kalpha X-rays of P, S, Cl, and K were detectable, so that the two-dimensional distribution of fluorescent X-ray intensities could be determined for these elements. Furthermore, quantitative determination was possible for P and K by using the fundamental parameter technique. However, the accurate determination of Na and Ca was difficult, because of the low energy of Kalpha X-ray of Na, and the interference of K-Kbeta with Ca-Kalpha. The change in elemental concentrations in ischemic tissue, including the decrease in K concentration and increase in Cl concentration, was demonstrated by this method as a two-dimensional contour map. Since it is possible to obtain a pictorial representation of the elemental concentration in tissue sections, this method may be useful to evaluate the ionic changes in injured brain tissue in relation to histological or autoradiographical observations.

The U.S. Environmental Protection Agency and the U.S. Department of Housing and Urban Development sponsored a field study of portable technologies for testing for lead in paint in three U.S. cities in 1993. Six chemical test kits and six X-ray fluorescence instruments, which represented the two main types of portable technologies available for residential lead testing at that time, were evaluated. Painted building components in single-family and multifamily housing units were selected to assess the performance of these products under real-world conditions. The study found that the chemical test kits were not effective in distinguishing lead-based paint, as defined by federal standards, from nonlead based paint. The X-ray fluorescence instruments were, under certain circumstances, found to be effective. The study filled an informational gap about the accuracy and precision of the portable lead-testing technologies. This article describes the design of the study and its major findings.

The calibration and application of a facility, based on energy dispersive X-ray fluorescent analysis (EDXRF) using 109Cd as an excitation source, for in vivo and in vitro estimation of Ca, Pb, Sr and Zn in tooth enamel is described. During the in vivo measurements, the device ensures tissue protection of face and mouth cavity from radiation, and only a small part of tooth surface under study is irradiated. To calibrate the facility, the contents of Ca, Sr and Zn were analyzed simultaneously in the enamel of 50 teeth by EDXRF and instrumental neutron activation analysis (INAA). Standards prepared from powdered tooth enamel with additions of chemically pure lead compounds were used to calibrate for lead graduation. Enamel calcium is suggested as an internal standard during in vivo EDXRF of teeth. The content of enamel Sr, Zn and Pb was determined by EDXRF in 35 permanent intact teeth of teenagers and adults. It was shown that lead concentration didn't exceed 3 micrograms/g for all the teeth.

Bone lead levels (finger and tibia) were measured, both in vivo and in vitro, with an x-ray fluorescence technique. In vivo finger-bone lead levels of 105 volunteers were estimated and subsequently re-estimated after a 5-y period. In many instances, elevated levels in some of these individuals probably resulted from lead ingested during childhood (i.e., more than 60 y ago). A decline in finger-bone lead from the initial value was accompanied by a mean finger-bone lead half-life of 6.2 y (n = 25); many individual's half-life values were less than 3.0 y. Perhaps one reason for these low values is the special propensity of finger bone to resorption during the involutional period, at which time there are high levels of circulating parathormone.

A k-x-ray fluorescence (K-XRF) instrument that can measure in vivo bone lead at low levels was used on a population of 34 adults with no known history of excessive lead exposure. A questionnaire that gathered information relevant to occupational and environmental lead exposure was administered prior to the measurement. A 30-min measurement that produced an average estimated uncertainty of 6 mcg lead/g bone mineral was taken at the mid-tibial diaphysis for each subject. Eighteen subjects had bone lead levels below the measurement uncertainty. The remainder had bone lead levels ranging up to 21 mcg lead/g bone mineral. Bone lead levels were greater among older subjects. Among young adult subjects, bone lead levels greater than the measurement uncertainty were confined entirely to subjects who had grown up in housing that was estimated to have been build prior to 1955. Such a childhood environment is at high risk of fostering exposure to biologically absorbable lead through ingestion of lead paint-contaminated dust and lead pipe-contaminated water. We conclude that the K-XRF technique has the potential to distinguish between low levels of lead burden in epidemiologic studies.

A microwave acid digestion method for the preparation of biological samples for PIXE analysis is presented. The precision and accuracy of the entire PIXE analytical procedure, including the microwave digestion step, were evaluated by analyzing eight certified reference materials. For elements heavier than K, and for concentration levels from 2 micrograms/g upward, the total random error of a single analysis is in the range of 2-5%. The accuracy is better than 5%. The detection limits are down to 0.3 micrograms/g.

Emission spectrometers provide alternative, relatively inexpensive methods for detecting the concentration of respiratory gas nitrogen. Mass spectrometers are accepted as reliable monitors of end-tidal nitrogen for detection of venous air embolisms. We evaluated an inexpensive emission spectrometer for detecting changes in nitrogen levels and compared it with a mass spectrometer for detecting increased end-tidal nitrogen levels in dogs with venous air embolisms. During in vitro gas flow studies (helium; oxygen; helium/oxygen mixtures; or 70% nitrous oxide/30% oxygen with 0, 1, 2, or 3% isoflurane), air boluses (0.01 to 5.0 ml) were injected into a gas flow circuit and outlet nitrogen levels were measured by a Collins 21232 emission spectrometer. Responses were greater after each bolus when helium rather than oxygen was the major diluent gas. During in vivo studies, 5 dogs were anesthetized, ventilated, denitrogenated, and given venous air embolisms (0.1, 0.5, and 1.0 ml.kg-1) during oxygen and then during Heliox (20% oxygen:80% helium) breathing. End-tidal nitrogen increased approximately two-fold after venous air embolisms given during Heliox as compared with oxygen ventilation. In all 0.1-ml.kg-1 venous air embolisms end-tidal nitrogen increased when the emission spectrometer was used, but venous air embolisms less than 1.0 ml.kg-1 were not consistently detected by mass spectrometry. Emission spectrometry can be used to detect increased end-tidal nitrogen levels indicative of venous air embolism and may be a more sensitive detector than mass spectrometry.

A simple and rapid method for the simultaneous determination of 11 metals (As, Be, Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, and Zn) in urine by inductively coupled argon plasma-atomic emission spectrometry is presented. Acidification of the urine was the only sample preparation required. Background correction was applied to ensure accuracy. Analytical calibration was based on matrix matching using a "simulated urine" solution. Detection limits in the low mg/L range and linearity over three orders of magnitude were obtained for all 11 metals. In the Occupational Health Laboratory, this procedure has been applied for routine screening of workers for occupational exposure to toxic metals.