The use of a portable X-ray fluorescence spectrometer for measuring nickel in plants: sample preparation and validation.

X-ray fluorescence is a fast, cost-effective, and eco-friendly method for elemental analyses. Portable X-ray fluorescence spectrometers (pXRF) have proven instrumental in detecting metals across diverse matrices, including plants. However, sample preparation and measurement procedures need to be standardized for each instrument. This study examined sample preparation methods and predictive capabilities for nickel (Ni) concentrations in various plants using pXRF, employing empirical calibration based on inductively coupled plasma optical emission spectroscopy (ICP-OES) Ni data. The evaluation involved 300 plant samples of 14 species with variable of Ni accumulation. Various dwell times (30, 60, 90, 120, 300 s) and sample masses (0.5, 1.0, 1.5, 2.0 g) were tested. Calibration models were developed through empirical and correction factor approaches. The results showed that the use of 1.0 g of sample (0.14 g cm-2) and a dwell time of 60 s for the study conditions were appropriate for detection by pXRF. Ni concentrations determined by ICP-OES were highly correlated (R2 = 0.94) with those measured by the pXRF instrument. Therefore, pXRF can provide reliable detection of Ni in plant samples, avoiding the digestion of samples and reducing the decision-making time in environmental management.

High-Spatial-Resolution Benchtop X-ray Fluorescence Imaging through Bragg-Diffraction-Based Focusing with Bent Mosaic Graphite Crystals: A Simulation Study.

X-ray fluorescence imaging (XFI) can localize diagnostic or theranostic entities utilizing nanoparticle (NP)-based probes at high resolution in vivo, in vitro, and ex vivo. However, small-animal benchtop XFI systems demonstrating high spatial resolution (variable from sub-millimeter to millimeter range) in vivo are still limited to lighter elements (i.e., atomic number Z≤45). This study investigates the feasibility of focusing hard X-rays from solid-target tubes using ellipsoidal lens systems composed of mosaic graphite crystals with the aim of enabling high-resolution in vivo XFI applications with mid-Z (42≤Z≤64) elements. Monte Carlo simulations are performed to characterize the proposed focusing-optics concept and provide quantitative predictions of the XFI sensitivity, in silico tumor-bearing mice models loaded with palladium (Pd) and barium (Ba) NPs. Based on simulation results, the minimum detectable total mass of PdNPs per scan position is expected to be on the order of a few hundred nanograms under in vivo conform conditions. PdNP masses as low as 150 ng to 50 ng could be detectable with a resolution of 600 µm when imaging abdominal tumor lesions across a range of low-dose (0.8 µGy) to high-dose (8 µGy) exposure scenarios. The proposed focusing-optics concept presents a potential step toward realizing XFI with conventional X-ray tubes for high-resolution applications involving interesting NP formulations.

Multivariate analysis applied to X-ray fluorescence to assess soil contamination pathways: case studies of mass magnetic susceptibility in soils near abandoned coal and W/Sn mines.

Determining the origin and pathways of contaminants in the natural environment is key to informing any mitigation process. The mass magnetic susceptibility of soils allows a rapid method to measure the concentration of magnetic minerals, derived from anthropogenic activities such as mining or industrial processes, i.e., smelting metals (technogenic origin), or from the local bedrock (of geogenic origin). This is especially effective when combined with rapid geochemical analyses of soils. The use of multivariate analysis (MVA) elucidates complex multiple-component relationships between soil geochemistry and magnetic susceptibility. In the case of soil mining sites, X-ray fluorescence (XRF) spectroscopic data of soils contaminated by mine waste shows statistically significant relationships between magnetic susceptibility and some base metal species (e.g., Fe, Pb, Zn, etc.). Here, we show how qualitative and quantitative MVA methodologies can be used to assess soil contamination pathways using mass magnetic susceptibility and XRF spectra of soils near abandoned coal and W/Sn mines (NW Portugal). Principal component analysis (PCA) showed how the first two primary components (PC-1 + PC-2) explained 94% of the sample variability, grouped them according to their geochemistry and magnetic susceptibility in to geogenic and technogenic groups. Regression analyses showed a strong positive correlation (R2 > 0.95) between soil geochemistry and magnetic properties at the local scale. These parameters provided an insight into the multi-element variables that control magnetic susceptibility and indicated the possibility of efficient assessment of potentially contaminated sites through mass-specific soil magnetism.

A High-Sensitivity Benchtop X-Ray Fluorescence Emission Tomography (XFET) System With a Full-Ring of X-Ray Imaging-Spectrometers and a Compound-Eye Collimation Aperture.

The advent of metal-based drugs and metal nanoparticles as therapeutic agents in anti-tumor treatment has motivated the advancement of X-ray fluorescence computed tomography (XFCT) techniques. An XFCT imaging modality can detect, quantify, and image the biodistribution of metal elements using the X-ray fluorescence signal emitted upon X-ray irradiation. However, the majority of XFCT imaging systems and instrumentation developed so far rely on a single or a small number of detectors. This work introduces the first full-ring benchtop X-ray fluorescence emission tomography (XFET) system equipped with 24 solid-state detectors arranged in a hexagonal geometry and a 96-pinhole compound-eye collimator. We experimentally demonstrate the system's sensitivity and its capability of multi-element detection and quantification by performing imaging studies on an animal-sized phantom. In our preliminary studies, the phantom was irradiated with a pencil beam of X-rays produced using a low-powered polychromatic X-ray source (90kVp and 60W max power). This investigation shows a significant enhancement in the detection limit of gadolinium to as low as 0.1 mg/mL concentration. The results also illustrate the unique capabilities of the XFET system to simultaneously determine the spatial distribution and accurately quantify the concentrations of multiple metal elements.

Investigation of the accuracy of a portable109Cd XRF system for the measurement of iron in skin.

We have previously reported the design of a portable109Cd x-ray fluorescence (XRF) system to measure iron levels in the skin of patients with either iron overload disease, such as thalassemia, or iron deficiency disease, such as anemia. In phantom studies, the system was found to have a detection limit of 1.35µg Fe per g of tissue for a dose of 1.1 mSv. However, the system must provide accurate as well as precise measurements of iron levels in the skin in order to be suitable for human studies. The accuracy of the system has been explored using several methods. First, the iron concentrations of ten pigskin samples were assessed using both the portable XRF system and ICP-MS, and the results were compared. Overall, it was found that XRF and ICP-MS reported average values for iron in skin that were comparable to within uncertainties. The mean difference between the two methodologies was not significant, 2.5 ± 4.6µg Fe per g. On this basis, the system could be considered accurate. However, ICP-MS measurements reported a wider range of values than XRF, with two individual samples having ICP-MS results that were significantly elevated (p < 0.05) compared to XRF. SynchrotronµXRF maps of iron levels in pigskin were acquired on the BioXAS beam line of the Canadian Light Source. TheµXRF maps indicated two important features in the distribution of iron in pigskin. First, there were small areas of high iron concentration in the pigskin samples, that were predominantly located in the dermis and hypodermis at depths greater than 0.5 mm. Monte Carlo modelling using the EGS 5 code determined that if these iron 'hot spots' were located towards the back of the skin at depths greater than 0.5 mm, they would not be observed by XRF, but would be measured by ICP-MS. These results support a hypothesis that iron levels in the two samples that reported significantly elevated ICP-MS results compared to XRF may have had small blood vessels at the back of the skin. Second, the synchrotronµXRF maps also showed a narrow (approximately 100µm thick) layer of elevated iron at the surface of the skin. Monte Carlo models determined that, as expected, the XRF system was most sensitive to these skin layers. However, the simulations found that the XRF system, when calibrated against homogenous water-based phantoms, was found to accurately measure average iron levels in the skin of normal pigs despite the greater sensitivity to the surface layer. The Monte Carlo results further indicated that with highly elevated skin surface iron levels, the XRF system would not provide a good estimate of average skin iron levels. The XRF estimate could, with correction factors, provide a good estimate of the iron levels in the surface layers of skin. There is limited data on iron distribution in skin, especially under conditions of disease. If iron levels are elevated at the skin surface by diseases including thalassemia and hemochromatosis, this XRF device may prove to be an accurate clinical tool. However, further data are required on skin iron distributions in healthy and iron overload disease before this system can be verified to provide accurate measurements.

Mercury and selenium distribution in human brain tissue using synchrotron micro-X-ray fluorescence.

Mercury is a well-recognized environmental contaminant and neurotoxin, having been associated with a number of deleterious neurological conditions including neurodegenerative diseases, such as Alzheimer's disease. To investigate how mercury and other metals behave in the brain, we used synchrotron micro-X-ray fluorescence to map the distribution pattern and quantify concentrations of metals in human brain. Brain tissue was provided by the Rush Alzheimer's Disease Center and samples originated from individuals diagnosed with Alzheimer's disease and without cognitive impairment. Data were collected at the 2-ID-E beamline at the Advanced Photon Source at Argonne National Laboratory with an incident beam energy of 13 keV. Course scans were performed at low resolution to determine gross tissue features, after which smaller regions were selected to image at higher resolution. The findings revealed (1) the existence of mercury particles in the brain samples of two subjects; (2) co-localization and linear correlation of mercury and selenium in all particles; (3) co-localization of these particles with zinc structures; and (4) association with sulfur in some of these particles. These results suggest that selenium and sulfur may play protective roles against mercury in the brain, potentially binding with the metal to reduce the induced toxicity, although at different affinities. Our findings call for further studies to investigate the relationship between mercury, selenium, and sulfur, as well as the potential implications in Alzheimer's disease and related dementias.

Predicting cadmium fractions in agricultural soils using proximal sensing techniques.

Cadmium (Cd) accumulation in agricultural systems has caused global environmental and health concerns. Application of phosphate fertiliser to sustain plant production unintentionally accumulated Cd in agricultural soils over time. Rapid and cost-effective Cd monitoring in these soils will help to inform Cd management practices. Compared to total Cd analysis, examining chemical fractions by sequential extraction methods can provide information on the origin, availability, and mobility of soil Cd, and to assess the potential plant Cd uptake. A total of 87 air-dried topsoil (0-15 cm) samples from pastoral farms with a history of long-term application of phosphate fertiliser were analysed using wet chemistry methods for total Cd and Cd forms in exchangeable, acid soluble, metal oxides bound, organic matter bound, and residual fractions. The data acquired using three proximal sensing techniques, visible-near-infrared (vis-NIR), mid-infrared (MIR), and portable X-ray fluorescence (pXRF) spectroscopy were used as input for partial least squares regression to develop models predicting total Cd and Cd fractions. The average total Cd concentration was 0.58 mg Cd/kg soil. For total Cd, cross-validation (cv) results of models using individual vis-NIR, MIR, and pXRF data performed with normalised root mean squared error (nRMSEcv) of 26%, 30%, and 31% and concordance correlation coefficient (CCCcv) of 0.85, 0.77, and 0.75, respectively. For exchangeable Cd, model using MIR data performed with nRMSEcv of 40% and CCCcv of 0.57. For acid soluble and organic matter bound Cd, models using vis-NIR data performed with nRMSEcv of 11% and 33% and CCCcv of 0.97 and 0.84, respectively. Reflectance spectroscopy techniques could potentially be applied as complementary tools to estimate total Cd and plant available and potentially available Cd fractions for effective implementation of Cd monitoring programmes.

Rapid Freezing and Cryo-SEM-EDS Imaging of Foraminifera (Unicellular Eukaryotes) Using a Conductive Viscous Cryogenic Glue.

Spatial distribution of water-soluble molecules and ions in living organisms is still challenging to assess. Energy-dispersive X-ray spectroscopy (EDS) via cryogenic scanning electron microscopy (cryo-SEM) is one of the promising methods to study them without loss of dissolved contents. High-resolution cryo-SEM-EDS has challenges in sample preparation, including cross-section exposure and sample drift/charging due to insulative surrounding water. The former becomes problematic for large and inseparable organisms, such as benthic foraminifera, a unicellular eukaryote playing significant roles in marine ecosystems, which often exceed the size limit for the most reliable high-pressure freezing. Here we show graphite oxide dispersed in sucrose solution as a good glue to freeze, expose cross-section by cryo-ultramicrotome, and analyze elemental distribution owing to the glue's high viscosity, adhesion force, and electron conductivity. To demonstrate the effectiveness and applicability of the glue for cryo-SEM-EDS, deep-sea foraminifer Uvigerina akitaensis was sampled during a cruise and plunge frozen directly on the research vessel, where the liquid nitrogen supply is limited. The microstructures were preserved as faithfully in cryo-SEM images as those with the conventional resin-substituted transmission electron micrograph. We found elements colocalized within the cytoplasm originating from water-soluble compounds that can be lost with conventional dehydrative fixation.

The feasibility of K XRF bone lead measurements in mice assessed using 3D-printed phantoms.

This article describes the development of a system forin vivomeasurements of lead body burden in mice using109Cd K x-ray fluorescence (XRF). This K XRF system could facilitate early-stage studies on interventions that ameliorate or reverse organ tissue damage from lead poisoning by reducing animal numbers through a cross-sectional study approach. A novel mouse phantom was developed based on a mouse atlas and 3D-printed using PLA plastic with plaster of Paris 'bone' inserts. PLA plastic was found to be a good surrogate for soft tissue in XRF measurements and the phantoms were found to be good models of mice. As expected, lead detection limits varied with mouse size, mouse orientation, and mouse position with respect to the source and detector. The work suggests that detection limits of 10 to 20µg Pb per g bone mineral may be possible for a 2 to 3 hour XRF measurement in a single animal, an adequate limit for some pre-clinical studies. The109Cd K XRF mouse measurement system was also modeled using the Monte Carlo code MCNP. The combination of experiment and modeling found that contrary to expectation, accurate measurements of lead levels in mice required calibration using mouse-specific calibration standards due to the coherent scatter peak normalization failing when small animals are measured. MCNP modeling determined that this was because the coherent scatter signal from soft tissue, which until now has been assumed negligible, becomes significant when compared to the coherent scatter signal in bone in small animals. This may have implications for some human measurements. This work suggests that109Cd K x-ray fluorescence measurements of lead body burden are precise enough to make the system feasible for small animals if appropriately calibrated. Further work to validate the technology's measurement accuracy and performancein vivowill be required.

Prospecting for rare earth element (hyper)accumulators in the Paris Herbarium using X-ray fluorescence spectroscopy reveals new distributional and taxon discoveries.

BACKGROUND: Rare earth elements (REEs) are increasingly crucial for modern technologies. Plants could be used as a biogeochemical pathfinder and a tool to extract REEs from deposits. However, a paucity of information on suitable plants for these tasks exists. METHODS: We aimed to discover new REE-(hyper)accumulating plant species by performing an X-ray fluorescence (XRF) survey at the Herbarium of the Muséum national d'Histoire naturelle (MNHN, Paris, France). We selected specific families based on the likelihood of containing REE-hyperaccumulating species, using known taxa that accumulate REEs. A total of 4425 specimens, taken in the two main evolutionary lineages of extant vascular plants, were analysed, including the two fern families Blechnaceae (n = 561) and Gleicheniaceae (n = 1310), and the two flowering plant families Phytolaccaceae (n = 1137) and Juglandaceae (n = 1417). KEY RESULTS: Yttrium (Y) was used as a proxy for REEs for methodological reasons, and a total of 268 specimens belonging to the genera Blechnopsis (n = 149), Dicranopteris (n = 75), Gleichenella (n = 32), Phytolacca (n = 6), Carya (n = 4), Juglans (n = 1) and Sticherus (n = 1) were identified with Y concentrations ranging from the limit of detection (LOD) >49 µg g-1 up to 1424 µg g-1. Subsequently, analysis of fragments of selected specimens by inductively coupled plasma atomic emission spectroscopy (ICP-AES) revealed that this translated to up to 6423 µg total REEs g-1 in Dicranopteris linearis and up to 4278 µg total REEs g-1 in Blechnopsis orientalis which are among the highest values ever recorded for REE hyperaccumulation in plants. It also proved the validity of Y as an indicator for REEs in XRF analysis of herbarium specimens. The presence of manganese (Mn) and zinc (Zn) was also studied by XRF in the selected specimens. Mn was detected in 1440 specimens ranging from the detection limit at 116 µg g-1 up to 3807 µg g-1 whilst Zn was detected in 345 specimens ranging from the detection limit at 77 µg g-1 up to 938 µg g-1. CONCLUSIONS AND IMPLICATIONS: This study led to the discovery of REE accumulation in a range of plant species, substantially higher concentrations in species known to be REE hyperaccumulators, and records of REE hyperaccumulators outside of the well-studied populations in China.

Benchtop x-ray fluorescence to quantify elemental content in nails non-destructively.

Metals continue to impose health issues among world populations. A non-invasive alternative biomarker for assessment of metals and other elements has been explored in other studies using toenail samples. Some benefits of using toenails as biomarkers over blood samples include cost efficiency, ease of collection, and a longer biological half-life within samples. The objective of this study was to employ desktop XRF for the purpose of measuring metal concentrations in human nail samples, thus conducting a non-destructive assessment. These benefits paired with comparable accuracy in exposure detection could prove toenail samples to be a preferred biomarker for many studies. Current elemental quantification techniques in toenail samples could be improved. The standard practice for measuring metal exposure in toenails, inductively coupled plasma mass spectrometry (ICP-MS), has a counterpart in x-ray fluorescence. While maintaining similar quantification capabilities, x-ray fluorescence could provide decreased cost, preservation of samples, and ease of operation. Portable XRF machines have been tested for measuring toenail samples, but they have drastically increased detection limits in comparison to ICP-MS. New benchtop XRF systems should give comparable detection limits to ICP-MS. This study compares the benchtop XRF measurements of lead (Pb), copper (Cu), iron (Fe), and Selenium (Se) levels to that of ICP-MS measurements of toenail samples and calculates estimated detection limits for 23 other elements. We found strong correlations for the toenail lead (R2 = 0.92), copper (R2 = 0.95), selenium (R2 = 0.60), and iron (R2 = 0.77) comparison between desktop XRF and ICP-MS measurements. Median minimum detection limits over the 23 elements were found to be 0.2 µg/g using a 7.5-min measurement. Benchtop XRF provides a lower detection limit than previously studied portable XRF machines, which gives it the capability of accurately detecting almost any desired element in nail samples. Benchtop XRF provides a non-destructive alternative to ICP-MS in surveillance of nail samples.

Hazardous elements in plastic and rubber granules as infill material from sports facilities? Field Portable-XRF spectroscopy as 'white analytical technique' reveals hazardous elements in fall sports facilities in Rzeszów (Podkarpackie, Poland).

Plastic and rubber granules are commonly used as infill material in all-weather sports facilities, providing an ideal activity surface for millions of Europeans on a daily basis. However, concerns have been raised about the presence of hazardous elements in these granules, which can pose risks both to the environment and human health. Our study focusses on the elemental composition of rubber granules used in fall sports facilities in Rzeszów, (Podkarpackie, Poland) using field portable X-ray fluorescence (FP-XRF) as a non-destructive and 'white analytical technique'. The results show the content of Zn, Fe, Cr, Ba, Br, Ti, Cu, Cd, As, Au, Bi, Pb, Ni, Sb, and Sn in the rubber granule samples. This study highlights the need for stringent quality control measures and regulations to ensure the safety of all-weather sports facilities and protect the well-being of sportsman. When modern FP-XRF spectrometry is employed as a "white analytical technique," for the first time it becomes possible to identify the presence of hazardous elements, addressing the pressing concerns highlighted by the ECHA and enabling proactive measures to mitigate potential risks. This approach ensures the protection of the health and sustainability of sports facilities, contributing to the ongoing hot topics in the field.

Elemental analysis using portable X-ray fluorescence: Guidelines for the study of dry human bone.

OBJECTIVE: X-ray fluorescence (XRF) is a non-destructive technique that measures the elemental concentration of different materials, including human bone. Recently, it began to be applied to paleopathological studies due to the development of portable devices and their relative ease of use. However, the lack of uniform procedures hampers comparability and reproducibility. This paper aims to provide guidelines for an efficient and standardized evaluation of bone elemental composition with a portable XRF (pXRF) device. MATERIALS: This technical note is based on the application of the Thermo Scientific Niton XL3t 900 GOLDD+. METHODS: This work includes suggestions for the choice and preparation of human bone samples, both from archaeological context and documented collections, and methodological procedures in pXRF setup, such as choice of calibration, assessment of accuracy, and analysis run time. Additionally, recommendations for data validation and statistical analysis are also included. CONCLUSIONS: This technique has great potential in paleopathology since bone chemical variations may be associated with different pathological conditions, environmental contamination (e.g., lead), and/or administered treatments, such as mercury. Following an expected increase in the number of studies, it is essential to establish good practices that allow results from different researchers to be comparable. SIGNIFICANCE: X-ray fluorescence is a non-destructive technique that measures small concentrations (ppm) of elements from magnesium (12Mg) through bismuth (83Bi). LIMITATIONS: pXRF does not detect elements lighter than Mg, and its lower energy excitation penetrates less than other techniques. SUGGESTIONS FOR FURTHER RESEARCH: Other research groups should test these guidelines and comment on their usefulness and replicability.

Correcting correlation quality of portable X-ray fluorescence to better map heavy metal contamination by spatial co-kriging interpolation.

High-precision mapping based on portable X-ray fluorescence (PXRF) data is currently being studied extensively; however, owing to poor correlation with soil metal concentration, the original PXRF data directly used for co-kriging interpolation (CKI) cannot accurately map contaminated sites with heterogeneous concentrations. Therefore, this study selected a landfill-contaminated site for research, explored the best correlation mode between PXRF variants and actual heavy metal concentration, analyzed the impact of improving the correlation model on the CKI of the spatial distribution of heavy metals, and explored the most appropriate CKI mode and point density. The results showed the following: (1) After nonlinear transformation, the correlation model between PXRF and the actual concentration was significantly improved, and the correlation coefficients of five heavy metals increased from 0.214-0.232 to 0.936-0.986. (2) The introduction of corrected PXRF data significantly improves the accuracy of CKI. Compared with the original PXRF co-kriging interpolation (OP-CKI), the ME of the corrected PXRF co-kriging interpolation (CP-CKI) for Zn, Pb, and Cu decreased by 78.2 %, 45.5 %, and 65.3 %, respectively. In terms of the spatial distribution of heavy metal pollutant concentrations, CP-CKI effectively improved the influence of local anomalous high-value points on the interpolation accuracy. (3) When the sample density measured by inductively coupled plasma mass spectrometry (ICP-MS) was less than 4 boreholes/hm2, CKI accuracy decreased significantly, indicating that the sample density should not be less than a certain threshold during CKI. (4) When the sample density measured by PXRF exceeded 7 boreholes/hm2, the mean error and root mean square error of CKI continued to decrease, suggesting that the introduction of enough sample density measured by PXRF can effectively improve the accuracy of CKI.

Assessing the potential of portable X-ray fluorescence (XRF) as a rapid, onsite screening tool in the assessment of cadmium surface decontamination effectiveness.

Portable X-ray fluorescence has successfully been used to effectively evaluate occupational exposure to airborne and surface metal contaminants nondestructively. Traditional methods of assessing metal surface contamination involve the costly, time-consuming collection and laboratory analysis of wipe samples, making portable X-ray fluorescence an attractive alternative method for screening worksites by reducing delays in risk assessment decision-making. Existing research into this use of portable X-ray fluorescence has primarily been centered on the analysis of airborne and surface lead contamination. The extant literature is sparse on the use of portable X-ray fluorescence with other metals for surface contamination with respect to occupational exposure. The present study evaluated the use of portable X-ray fluorescence in the screening of cadmium surface contamination to determine if the effectiveness of decontamination measures can be ascertained by this technique. Wipe samples were collected and screened with portable X-ray fluorescence before being sent to the laboratory for definitive analysis to assess the correlation between portable X-ray fluorescence readings in percent mass with laboratory results in µg/ft2. Portable X-ray fluorescence readings demonstrated a strong linear correlation with laboratory results, as indicated by the R2 value of 0.993. Therefore, this technique may be further developed and deployed as a screening tool for wipe samples used for evaluating contamination and decontamination of metal-contaminated areas.

Ultrasensitive determination of selenium in food samples and its speciation in water and beverages using thiosemicarbazide-incorporated graphene and total-reflection X-ray fluorescence spectrometry.

The paper presents a new analytical procedure for the determination and speciation of trace and ultratrace selenium in water, beverages, seafood, milk, and vegetables. The developed method is based on the dispersive micro-solid phase extraction with the use of new thiosemicarbazide-incorporated graphene as a solid sorbent, in combination of the total-reflection X-ray fluorescence spectrometry (TXRF). As a result, we have created an auspicious analytical tool for fast and sensitive analysis of samples with a complex matrix. Regardless of the specimen type, the method is characterized by a very low detection limit of 1.7 pg mL-1 and high precision. The developed strategy allowed us to solve common problems associated with selenium loss during the sample preparation for the TXRF measurement and also improve its performance toward the analysis of beverages and high saline/solid samples, which may even be impossible to perform using standard sample preparation procedures for a TXRF measurement.

EDXRF and the relative presence of K, Ca, Fe and as in amyloidogenic tissues.

Trace and minor elements play crucial roles in a variety of biological processes, including amyloid fibrils formation. Mechanisms include activation or inhibition of enzymatic reactions, competition between elements and metal proteins for binding positions, also changes to the permeability of cellular membranes. These may influence carcinogenic processes, with trace and minor element concentrations in normal and amyloid tissues potentially aiding in cancer diagnosis and etiology. With the analytical capability of the spectroscopic technique X-ray fluorescence (XRF), this can be used to detect and quantify the presence of elements in amyloid characterization, two of the trace elements known to be associated with amyloid fibrils. In present work, involving samples from a total of 22 subjects, samples of normal and amyloid-containing tissues of heart, kidney, thyroid, and other tissue organs were obtained, analyzed via energy-dispersive X-ray fluorescence (EDXRF). The elemental distribution of potassium (K), calcium (Ca), arsenic (As), and iron (Fe) was examined in both normal and amyloidogenic tissues using perpetual thin slices. In amyloidogenic tissues the levels of K, Ca, and Fe were found to be less than in corresponding normal tissues. Moreover, the presence of As was only observed in amyloidogenic samples; in a few cases in which there was an absence of As, amyloid samples were found to contain Fe. Analysis of arsenic in amyloid plaques has previously been difficult, often producing contradictory results. Using the present EDXRF facility we could distinguish between amyloidogenic and normal samples, with potential correlations in respect of the presence or concentration of specific elements.

Long-term stability of hydroxyapatite bone phantoms for the calibration ofin vivox-ray fluorescence spectrometry-based systems of bone lead and strontium quantification.

Hydroxyapatite (HAp) phantoms have been proposed as an alternative to plaster of Paris (poP) phantoms for the calibration of x-ray fluorescence-based systems for thein vivoquantification of bone lead and strontium which employ a coherent normalization procedure. The chemical composition of the material becomes critical in the calculation, or omission, of the coherent correction factor (CCF) required in this normalization procedure. This study evaluated the long-term chemical stability of HAp phantoms. Phantoms were prepared and allowed to age for a two week period and over a seven year period in ambient conditions. The chemical composition of the phantoms was then assessed by powder x-ray diffraction. Two week old phantoms were found to be composed of HAp with only a small amount of contamination from CaHPO4·2H2O. Seven year old phantoms were found to have converted nearly completely to a carbonate-bearing apatite in the form of Ca10(PO4)6(CO3)0.75(OH)0.5indicating that the HAp phantom material likely reacts with carbon dioxide in air over time forming a carbonate-bearing apatite. The influence of this chemical conversion was assessed at the level of relevant cross-sections. Calibration under the assumption that the material is HAp when in fact it is a carbonate-bearing apatite would result in not more than a 0.2%-2% bias in the total mass attenuation coefficient within the photon energy range of 0-100 keV. Differential scattering cross-section for coherent scattering was found to differ between HAp and carbonate-bearing apatite by 0.9%-2% for both a 35.5 keV and 88.0 keVγ-ray. This variation in the differential scattering cross-section for coherent scattering may introduce a ca. 2% bias in the CCF used within the coherent normalization-based calibration procedure. Using HAp phantoms as calibrators thus requires acknowledgement of this conversion in chemical form and possible introduction of uncertainty into the calibration procedure.

Laboratory comparison of field portable X-ray fluorescence spectrometer (FP-XRF) and inductively coupled plasma mass spectrometry (ICP-MS) for determination of airborne metals in stainless steel welding fume.

Welding fume is a common exposure in occupational settings. Gravimetric analysis for total particulate matter is common; however, the cost of laboratory analyses limits the availability of quantitative exposure assessment for welding fume metal constituents in occupational settings. We investigated whether a field portable X-ray fluorescence spectrometer (FP-XRF) could provide accurate estimates of personal exposures to metals common in welding fume (chromium, copper, manganese, nickel, vanadium, and zinc). The FP-XRF requires less training and is easier to deploy in many settings than traditional wet laboratory analyses. Filters were analyzed both by FP-XRF and inductively coupled plasma mass spectrometry (ICP-MS). We estimated the FP-XRF limit of detection for each metal and developed a correction factor accounting for the non-uniform deposition pattern on filter samples collected with an Institute of Medicine (IOM) inhalable particulate matter sampler. Strong linear correlation was observed for all metals (0.72

Metals quantification in e-cigarettes liquids by Total Reflection X-ray Spectrometry.

Electronic cigarettes (e-cig) have gained popularity around the world and its health risks demands more research. This study aims at characterizing e-cig liquids (e-liquids) and its constituents by Total Reflection X-ray Spectrometry (TXRF). The internal standard method was the quantification procedure employed. The spectrometer's performance was evaluated with one certified reference material and spiked samples. It was possible to quantify K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, Br, and Pb in the e-liquids. Concentrations above the limit for potable water were found in 10 out of 38 samples. Principal component analysis was useful for identifying toxic samples. TXRF is a promising technique for e-liquids evaluation due to its simplicity and performance.