Total Reflection X-ray Fluorescence Analysis Research Articles

Written in ink: Elemental signatures in octopus ink successfully trace geographical origin

In recent years, validation of seafood authenticity and provenance has attracted the attention of authorities and consumers. Increasing levels of food fraud has raised awareness regarding seafood traceability, especially in highly valuable and highly consumed seafood products, such as the common octopus (Octopus vulgaris). Seafood traceability studies based on trace element fingerprinting generally focus on muscle tissues or carbonate structures whilst the ink fluid has been overlooked. Untargeted multi-element Total Reflection X-ray Fluorescence (TXRF) analysis of O. vulgaris ink successfully discriminated four collection areas [91.2 % and 84.1 % using Variable Importance in Projection Partial Least-Squares Discriminant Analysis (VIP-PLS-DA) and Linear Discriminant Analysis (LDA), respectively] along the mainland Portuguese coast (ca. 900 km coast in the Northeast Atlantic). Arsenic, Pb, Na, Sr and Rb were highlighted as elements with higher contributions for sample discrimination between the four considered capture areas. Regarding food safety, it is important to note that some ink samples Cu, Mn and Pb concentrations exceeded human consumption recommended values. Thus, the results show that untargeted TXRF spectroscopy analysis of O. vulgaris ink is a reliable tool for disentangling the geographical origin of the octopus, as well as to inform about the food safety of octopus ink.

Elemental fingerprinting of thornback ray (Raja clavata) muscle tissue as a tracer for provenance and food safety assessment

The verification of food authenticity and provenance is a complex task and has raised public concern in recent years due to multiple episodes of food fraud and potential risks to consumers. In this sense, the evaluation of multi-elemental signatures is increasingly applied to confirm and validate the site of origin of animal products. Yet, we lack understanding of its efficacy for mobile organisms such as fish. Using multi-element Total Reflection X-ray Fluorescence (TXRF) analysis of muscle of thornback ray Raja clavata we successfully identified the fishing area of individuals collected in four areas along the Portuguese Atlantic coast (Atlantic Iberian waters, Northeast Atlantic). Overall, As, Fe, Sn, V and Zn presented higher contributions to discrimination (especially Fe and Rb for neighbouring collection areas), whilst the higher concentration elements (Na, K, P, S, Ca, Cl, Br and Sr) had similar concentrations among locations. Rays captured in the two areas with higher urbanization/industrialization presented higher concentration of elements associated with anthropogenic activities (such as As, Zn, Sn and V). In terms of food safety, only 0.9% and 2.8% of the individuals surpassed the recommended thresholds values for human consumption for Hg and Cd respectively. A canonical analysis of principal components resulted in classification accuracy of thornback ray to collection site of 56.7–84.2% (depending on site), with an overall accuracy of 65.1% over c. 500 km of coast in the Northeast Atlantic.

High-accuracy determination of trace elements by total reflection X-ray fluorescence spectrometry using freeze-dried specimens.

Total reflection X-ray fluorescence (TXRF) analysis is conducted to determine trace elements in a sample solution, which is dropped onto a substrate and dried. Therefore, the form of the residue affects the quantitative results. The absorption of X-ray fluorescence (XRF) follows the Lambert-Beer law; the absorption effect of XRF in a thick residue (dotted-type residue) is stronger than that in a thin residue (film-type residue). The absorption effect is particularly remarkable during the determination of low-Z elements in a high-elemental concentration solution. In this study, we propose a new film-like-residue preparation process based on the freeze-drying method to obtain accurate TXRF results. The sample solution is dropped onto the substrate and inserted into a chamber. The chamber is cooled using liquid nitrogen; resultantly, an aliquot of the sample is frozen. The chamber is depressurized using a vacuum pump, and the freeze-dried residue is prepared by maintaining the chamber at room temperature. To evaluate the efficiency of the freeze-drying-based method for sample preparation for TXRF analysis, we prepare a multi-element solution containing high-elemental concentration components. For the residue prepared using the freeze-drying method, the relative standard deviations of the quantitative values and the minimum detection limits are improved because the absorption effect is weakened. The sample preparation process based on the freeze-drying method facilitates accurate TXRF analysis of high-elemental concentration solutions and can be applied for the analysis of trace elements in different types of solutions such as environmental water and wastewater.

Development of a certified reference material (CRM) for seven trace elements (Al, Ca, Fe, K, Mg, Na and Ti) in high purity quartz

Certified reference material (CRM) for trace elements in quartz matrix is required to assess the performance of analytical methods in regards to their validation, calibration and for comparability of measurements between laboratories. Due to unavailability of matrix matched CRMs in our country, National Centre for Compositional Characterization of Materials (NCCCM) of Bhabha Atomic Research Centre (BARC), Hyderabad and Council of Scientific and Industrial Research CSIR-National Physical Laboratory (NPL), New Delhi have initiated a program for the production of a CRM for the certification of critical trace elements in high purity quartz. Preparation and certification of Indian Reference Material (BND 4101.01), quartz powder with certified mass fractions of seven trace impurities was carried out jointly between NCCCM and NPL; two national laboratories of Government of India. Sampling constant (Ks) were established before carrying out the homogeneity test within and between bottles. The homogeneity test was carried out by NCCCM. The certified values were assigned after Inter Laboratory Comparison Exercise (ILCE) between reputed National Laboratories in India as per ISO-Guide 34 & 35. Analytical techniques like Inductively coupled plasma atomic emission spectrometry (ICP-AES), Flame atomic absorption spectrometry (FAAS) and Total reflection x-ray fluorescence analysis (TXRF) have been used for the characterization of property values.

Predicting neurological recovery after traumatic spinal cord injury by time-resolved analysis of monocyte subsets.

Monocytes and lymphocytes elicit crucial activities for the regenerative processes after various types of injury. The survival of neurons exposed to mechanical and oxidative stress after traumatic spinal cord injury depends on a multitude of factors. In this study, we sought to evaluate a correlation between remission after traumatic spinal cord injury and the dynamics of monocyte subsets in respect to the lymphocytes' responsive potential, cytokine expression, patterns of trace element concentration and clinical covariates. We examined prospectively 18 (three female, 15 male) patients after traumatic spinal cord injury. Blood samples were drawn at admission and 4 h, 9 h, 12 h, 1 and 3 days as well as 1 and 2 weeks and 1, 2 and 3 months after the trauma. Analysis of cytokines (CCL2, IL-10, enolase 2, CXCL12, TGF-β1, TGF-β2) was performed using a multiplex cytokine panel. Plasma trace element concentrations of selenium, copper and zinc were determined by total reflection X-ray fluorescence analysis; neopterin, selenoprotein P (SELENOP) and ceruloplasmin (CP) by enzyme-linked immunosorbent assay; and selenium binding protein 1 (SELENBP1) by luminometric immunoassay. The responsive potential of lymphocytes was assessed using transformation tests. The monocyte subsets (classical, intermediate, and non-classical) and expression of CD14, CD16, CXCR4 and intracellular IL-10 were identified using a multi-colour flow cytometry analysis. The dynamics of the cluster of intermediate CD14-/CD16+/IL10+/CXCR4int monocytes differed significantly between patients with an absence of neurological remission (G0) from those with an improvement (G1) by 1 or 2 American Spinal Injury Association Impairment Scale (AIS) steps (Kruskal-Wallis Test, P = 0.010, G0 < G1, AIS+: 1 < G1, AIS+: 2) in the first 24 h. These dynamics were associated inversely with an increase in enolase and SELENBP1 14 days after the injury. In the elastic net regularized model, we identified an association between the increase of a subpopulation of intermediate CD14-/CD16+/IL10+/CXCR4int monocytes and exacerbated immune response within 24 h after the injury. These findings were reflected in the consistently elevated response to mitogen stimulation of the lymphocytes of patients with significant neurological remission. Early elevated concentrations of CD14-/CD16+/IL10+/CXCR4int monocytes were related to higher odds of CNS regeneration and enhanced neurological remission. The cluster dynamics of CD14-/CD16+/IL10+/CXCR4int monocytes in the early-acute phase after the injury revealed a maximum of prognostic information regarding neurological remission (mean parameter estimate: 0.207; selection count: 818/1000 repetitions). We conclude that early dynamics in monocyte subsets allow a good prediction of recovery from traumatic spinal cord injury.

Determination of essential elements (Mn, Fe, Cu and Zn) in herbal teas by TXRF, FAAS and ICP‐OES

The aim of this study was the comparison of the results obtained in the determination of the content of essential elements such as Mn, Fe, Cu and Zn in vegetation samples using different analytical approaches, including suspension preparation and total reflection X‐ray fluorescence (TXRF) analysis as well as most commonly used spectroscopic methods in the field of vegetal analysis such as acid digestion in combination with atomic emission (AES) and atomic absorption spectrometry (AAS). In the case of TXRF analysis, two instruments equipped with different X‐ray tubes anodes (W and Mo) were used to better evaluate the potential of TXRF for vegetal samples analysis. Analytical figures of merit for the considered methods were determined by the analysis of plant reference materials. The one‐way analysis of variance (ANOVA) applied to the analysed and certified values showed that the results were not statistically different at the significance level of p‐values &lt;0.05. Therefore, suspension preparation and TXRF analysis proved to be a sustainable and fast analytical alternative to the most commonly used ones involving a previous digestion of the sample and inductively coupled plasma optical emission spectrometry (ICP‐OES) or flame atomic absorption spectrometry (FAAS) analysis. Finally, the different analytical approaches were applied to the determination of Mn, Fe, Cu and Zn in a set of herbal teas used for medical purposes.

Studies of Element Concentration in the Lymphocytes, Erythrocytes, and Plasma of Healthy Human Donors Using Total Reflection X-ray Fluorescence.

In this article, the total reflection X-ray fluorescence (TXRF) analysis was used for determination of element concentrations in three isolated peripheral blood components: lymphocytes, erythrocytes, and plasma, collected from 36 healthy donors (15 men and 21 women) from eastern Poland. The studied blood components were isolated from whole peripheral blood using Histopaque-1077 density gradient centrifugation. In the lymphocytes, the following elements were measured: P, S, Cl, K, Ca, Fe, Zn, Br, Sr, and Pb. In the erythrocytes: P, S, Cl, K, Cr, Mn, Fe, Cu, Zn, Se, Br, Rb, and Pb, while in the plasma samples: P, S, Cl, K, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Br, Se, Sr, and Pb. The descriptive statistics parameters of concentration such as: mean value, standard deviation, median, first and third quartiles, 10th and 90th percentiles were calculated for all samples of the studied blood components, as well as separately for male and female groups. The measured element concentrations and calculated parameters can be used as the reference values. Element concentration distributions for male and female groups were statistically compared using the non-parametric Mann-Whitney test and statistical significance differences (α = 0.05) were found for: P (in lymphocytes), Se and Rb (in erythrocytes), and V (in plasma). The multigroup statistical comparison of element concentration distribution for different blood components was also done (Mann-Whitney and Kruskal-Wallis tests). The statistical tests show that the concentration levels are usually different, except in the following cases: Zn, Fe (lymphocytes and plasma, Fe only for female group), Cr (erythrocytes and plasma). The obtained concentration ranges were compared with literature-based data available for element concentration in lymphocytes, erythrocytes, and plasma. In this work, the application of the TXRF method allowed additionally for the simultaneous determination of the concentrations of such elements as: P, S, Cl, Br, Sr and Pb in lymphocytes, S, Cl and Br in erythrocytes, and P, S, Cl, K, Ti, Br and Pb in plasma. From an analytical point of view, the article describes in detail the measurement procedure including the isolation of blood components and samples preparation for TXRF measurements, and later the detection limit of the method is discussed.

Total reflection X-ray fluorescence analysis of high purity quartz: A bottom-up approach of uncertainty evaluation

High purity quartz was analyzed using Total Reflection X-Ray Fluorescence (TXRF) spectrometry, during our participation in proficiency testing programme. The sample was digested in HF-HNO3 medium and the silica matrix was removed as silicon tetra fluoride by evaporation and repeated treatments with HNO3. Trace metallic impurities viz. K, Ca, Ti and Fe were quantified via the internal standard (using Ga) method in TXRF spectrometry. The z-score, zeta score and quality control sample analysis revealed the accuracy of the present determinations for all the analytes. Combined uncertainty for the measurement was evaluated through the bottom-up approach. Relative sensitivity of the TXRF spectrometer for the analyte with respect to the internal standard was found to hold the highest share of uncertainty. Detection limits for both the process blank and sample solutions were compared. Detection limits in the sample solutions were 1.86, 0.95, 0.94 and 0.30 mg kg−1 for K, Ca, Ti and Fe respectively. These studies brought out the importance of appropriate concentration of standard solutions for calibration and sensitivity measurements of the spectrometer, in addition to the quality of reference standard solution, for ensuring accuracy of the results.

Characterization of the ultrafine and fine particles formed during laser cladding with the Inconel 718 metal powder by means of X-ray spectroscopic techniques

Additive manufacturing is a rapidly growing industrial technology. Still, there is a lack of knowledge regarding the fine particle emission and new particle formation during the processes and their consequences on the performance of the operation and the operator's health as well. Therefore, we studied the properties of the emitted particles during the 3D printing process using the Inconel 718 (Ni-based) superalloy. The number and the mass concentrations were measured with a Scanning Mobility Particle Counter and Sizer. Size-fractionated samples were collected by a cascade impactor, and the elemental composition of the particles was determined by total-reflection X-ray fluorescence analysis, Scanning Electron Microscopy, Energy Dispersive Spectroscopy, and microscopic X-ray fluorescence analysis in the different size fractions. The oxidation states of the metals (Cr, Mn, Fe, Ni) in the samples were determined with the X-ray absorption near-edge structure (XANES) method. Most of the particles were found in the ultrafine region with a size below 100 nm, and the mass size distribution had the maximum at 85 nm. In the original powder, Ni was dominating with appr. 52 wt%, and the proportion of Cr was around 20 wt%, and Mn was below 1 wt%. In the released particles, the Ni content decreased to appr. 26 wt%, the Cr content increased to appr. 47 wt% and Mn increased to around 10 wt% for particles with a size between 0.07 and 10 μm. According to the XANES results, Cr, Mn and Fe were found to be oxidized significantly, whereas Ni remained in the metallic form in the total emitted aerosol containing mostly ultrafine particles. The enrichment and oxidation of metals were correlated with each other.

Comparative analysis of X-ray fluorescence methods for elemental composition determination of the archaeological ceramics from low sample quantity

Wavelength-dispersive X-ray fluorescence analysis (WDXRF) and total-reflection X-ray fluorescence (TXRF) analysis were applied to study the elemental composition of the Late Neolithic ancient ceramics collected at the Popovsky Lug burial site (Kachug, Upper Lena river, Russia). Semi-quantitative non-destructive analysis of ceramic pieces showed that measurements of the upper and lower sides of the ceramic are less informative than the measurement of its cut. Various sample preparation techniques for the low quantity of crushed ceramics such as fusion, pressing and preparation of suspensions were compared to preserve the material. Samples were prepared as 150 mg fused beads and 250 mg pressed pellets for WDXRF, and as suspensions of 20 mg sample based on the aqueous solution of the Triton X-100 surfactant for TXRF. Certified methods were used to validate the obtained contents of rock-forming oxides and inductively coupled plasma mass spectrometry was used to confirm the results of trace elements determination. Based on the carried-out studies, a combination of the wavelength-dispersive X-ray fluorescence analysis (glass) and total-reflection X-ray fluorescence analysis (suspension) methods was chosen to obtain the data on the elemental bulk composition of archaeological ceramics. The proposed combination allowed the quantitative determination of Na, Mg, Al, Si, P, K, Ca, Ti, Mn, Fe, V, Cr, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Pb, and Ba from the sample of crushed ceramics weighing only about 170 mg.

A round robin test for total reflection X-ray fluorescence analysis using preselected and well characterized samples

A TXRF round robin test using preselected micro- and nanoscaled samples has been performed and shows excellent results, demonstrating the strength and reliability of the TXRF method when decoupled from unfavorable sample preparations.

Total reflection X-ray fluorescence analysis with a glass substrate treated with a He atmospheric pressure plasma jet

A glass substrate treated with a He atmospheric pressure plasma jet gave a film-like residue from a small droplet of the red wine. This technique was effective in decreasing the matrix effect for TXRF analysis of low-Z elements.

Total reflection X-ray fluorescence analysis of aerosol particles with direct dissolution of the collection filter on a substrate

In this study, a novel method based on total reflection X-ray analysis was developed for determining the trace elements in aerosol particles.

Methodology development and optimization for direct quantification of total selenium concentration in mine water by total-reflection X-ray fluorescence spectrometry

Methodology for direct quantification of total selenium (Se) concentration in mine water by total-reflection X-ray fluorescence (TXRF) spectrometry was developed and optimized. Inductively coupled plasma – mass spectrometry (ICP-MS), as a recognized standard test method, was used as a benchmark for results verification. Preliminary measurements with aqueous multi-element standard solutions showed that Se concentration can be accurately determined down to 10 ng/g by using a single-drop of solution (10 μL) and a measurement time of 600 s. Quantification of lower Se concentration below 10 ng/g was subsequently optimized, also with aqueous multi-element standard solutions. Improvement in detection limit was accomplished by increasing amount of sample deposition as well as increasing measurement time. TXRF analysis of SRM1640a, Trace Elements in Natural Water, was also performed for accuracy check. The developed methodology was applied to analyze five raw mine water samples (MW-1, MW-2, MW-3, MW-4 and MW-5) collected from anonymous mine site locations. TXRF analysis was performed on the as-received samples directly without filtration, dilution and digestion. Samples were prepared as single-drop specimens and analyzed using a measurement time of 600 s. Se and fifteen other elements were detected in varying degree in the as-received samples. Se concentrations quantified by TXRF were 256.5 ± 22.5, 88.4 ± 1.4 and 61.3 ± 2.8 ng/g for mine water samples MW-1, MW-2 and MW-3, respectively, compared to 255.3 ± 5.6, 87.3 ± 2.6 and 59.7 ± 3.5 ng/g by ICP-MS. No clear Se-Kα peak above background was observed for samples MW-4 and MW-5. Increasing amount of sample deposition by preparing triple-drop specimens and using a longer measurement time of 1800 s, allowed a Se-Kα peak to emerge above the background for MW-4, but not MW-5. Se concentration in MW-4 quantified by TXRF was 4.9 ± 0.5 ng/g, compared to 6.7 ± 0.7 ng/g by ICP-MS, which represents an agreement within three standard deviation values between the two techniques. For sample MW-5, even after using triple-drop specimens and increasing the measurement time to 1800 s, Se concentration could not be determined because a Se-Kα peak was not detected by TXRF, compared to the Se concentration of 0.83 ± 0.1 ng/g obtained by ICP-MS. Overall, our analysis results showed that the TXRF technique can be used for direct analysis of total Se concentration in raw mine water samples down to ng/g range, providing high-quality, accurate and repeatable analysis comparable to ICP-MS while requiring much simpler sample preparation.

Study of chromium, selenium and bromine concentrations in blood serum of patients with parenteral nutrition treatment using total reflection X-ray fluorescence analysis.

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.

Characterization of archaeological ceramics from eastern Siberia by total-reflection X-ray fluorescence spectrometry and principal component analysis

The study of the composition of archaeological ceramics provides information used to assess possible transportation routes and cultural connections between ancient people living in different regions. Total-reflection X-ray fluorescence (TXRF) was applied for the analysis of ceramics as a promising method due to the rapidity, cost-efficiency, and capability to analyze a very small amount of a sample (<20 mg), which is important for the preservation of archaeological material. Two techniques of sample preparation for the TXRF analysis of ceramics have been considered. The analysis of suspensions was applied to obtain information on the bulk composition of ceramics. Acid leaching was used for the elemental analysis of the clay component of the ceramics, with the separation of non-soluble mineral phase. The proposed TXRF techniques have been successfully validated by the analysis of reference material and comparison with independent analytical methods. Reproducibility (interlaboratory precision) was evaluated for the proposed TXRF leaching method involving two different laboratories. The application of grazing incidence X-ray fluorescence (GI-XRF) showed homogeneous distribution of elements in the specimen and correspondence of the measurements to the conditions of total external reflection. TXRF method was applied to collect the first data on the composition of archaeological samples of ceramics from Popovsky Lug, eastern Siberia (Russia). The obtained data on the elemental composition were used to classify the samples by statistical methods of analysis, including the method of principal components and factor analysis. Three different compositional groups of ceramic have been separated and accepted as corresponding to archaeological interpretation.

Towards a calibration of laboratory setups for grazing incidence and total-reflection X-ray fluorescence analysis

Grazing-Incidence X-ray fluorescence (GIXRF) analysis, which is closely related to total-reflection XRF, is a very powerful technique for the in-depth analysis of many types of technologically relevant samples, e.g. nanoparticle depositions, shallow dopant profiles, thin layered samples or even well-ordered nanostructures. However, the GIXRF based determination of the depth-dependent information about the sample is usually based on a modeling of the experimental data. This requires profound knowledge of the geometrical parameters of the setup employed, especially the incident beam profile as well as the detector aperture parameters. Together they determine the incident angle dependent so-called effective solid angle of detection which must be known in order to model any experimental data set. In this work, we demonstrate how these instrumental parameters, which are typically not known with sufficient accuracy, can be determined using dedicated experiments with a well-known calibration sample. In addition, this paves the way for a full calibration of the setup, as also information about other parameters, e.g. the incident photon flux is gained. Here, we are using a commercially available instrument for this demonstration but the principle can also be applied for other GIXRF setups.

Features of sample preparation techniques in the total-reflection X-ray fluorescence analysis of tea leaves

Tea is a popular drink around the world and contains essential minerals and trace elements for human health. In this study, the analytical capabilities of the total-reflection X-ray fluorescence method (TXRF) were considered for the analysis of tea. Different sample preparation techniques, e.g. suspension, open vessel acid digestion, and microwave acid digestion were examined. The influence of particle size was investigated in the analysis of the suspension of tea samples. Mass-absorption coefficients for the tea matrix and the critical surface density of the specimen were calculated. The data obtained explain the presence of absorption effects in the determination of P, S, Cl, and K in suspensions. The digestion procedure is chosen as an optimal sample preparation technique for the TXRF analysis of tea. Nineteen real tea samples were analyzed using TXRF. The advantages of TXRF have been presented through the comparison of results with the wavelength-dispersive X-ray fluorescence spectrometry method.

INVESTIGATION AND OPTIMIZATION OF COMPLEXATION OF MANGANESE (II) IONS WITH DIHY-DROQUERCETIN IN AQUEOUS SOLUTIONS

The purpose of this work was to study and optimize the complexation reaction of Mn2+ ions with flavonoid dihydroquercetin (DHQ) in aqueous solutions. It was found that the interaction of DHQ (0.015–0.030 M) with manganese (II) salts at molar ratios of DHQ : Mn2+ from 1 : 1 to 1 : 3 at pH 6.9–7.9 leads to the formation of a complex compound (CC) with a stoichiometric ratio of metal : flavonoid ligand (Met : L) 1 : 1. The conditions for the complexation of Mn2+ ions with dihydroquercetin at laboratory conditions optimized for the yield of the product, are proposed. The maximum yield of the complex (95%) was achieved at the interaction of DHQ with Mn(CH3COO)2∙4H2O under conditions: pH 7.7, 70 °C, the reaction time was 15 min, the molar ratio of the initial reagents DHQ: Mn2+ was 1 : 1.5, the initial concentrations were 0.020 M DHQ and 0.030 M Mn2+. The most probable composition of the complex with the determination of the amount of bound water [MnL(OH)(H2O)2] and the structure of the complex were established using the data of thermogravimetry (TG), differential scanning calorimetry (DSC), elemental analysis and X-ray fluorescence analysis (XRF), confirmed by the data of total reflection X-ray fluorescence analysis (TXRF), and EPR spectroscopy data.

Total reflection X-ray fluorescence analysis of uranium in the presence of competing elements☆

The analysis of uranium in environmental samples, quantified using total reflection X-ray fluorescence (TXRF) analysis, would be adversely affected by the presence of rubidium and strontium in larger amounts than uranium as coexisting elements. This is because the U Lα line at 13.61 keV is close to the Rb Kα line at 13.40 keV and the Sr Kα line at 14.17 keV. Using the U Lβ1 line (instead of the U Lα line), which does not overlap with the peaks of coexisting elements, we will be able to avoid these adverse effects. Since there is no TXRF device that can perform a quantitative analysis of uranium by using the U Lβ1 line, the following modifications were made to the existing device with the intention of rapid on-site analysis. The X-ray tube of the new device has a silver anode instead of a tungsten anode, and the sensitive area of the detector was expanded. In addition, the mechanism for adjusting the position of the sample stage was changed from manual to computerized control. These changes made it possible to screen uranium in environmental samples rapidly on site without chemical separation.