Total Reflection X-ray Fluorescence Measurements Research Articles

A highly sensitive method for uranium quantification in water samples at ultra-trace level by total reflection X-ray fluorescence, after its direct pre-concentration on the surface of amidoxime functionalized quartz sample supports

In this work we have developed a Total reflection X-Ray Fluorescence (TXRF) based methodology for the determination of uranium in natural water samples at ultra-trace concentration level. The methodology involves functionalization of quartz sample supports used for TXRF measurements with (3-Amidoxy) triethoxysilane, which has very high uranium uptake efficiency. (3-Amidoxy) triethoxysilane has been synthesized from (3-Cyanopropyl) triethoxysilane (CPTS). This amidoxime functionalized sample supports, simply needed to be dipped in the uranium solution for 3 h after which, it can be directly taken for TXRF measurements. The developed methodology is very fast, simple with less sample preparation steps involved. The present work utilizes Rayleigh scattered peak to construct the calibration curve for the quantification purpose. The developed methodology has improved accuracy as well as precision for the quantification of uranium at such low concentrations level. The detection limit and accuracy obtained are 0.013 ng/mL (13 ppt) and 1.9%, respectively which are the lowest using any X-Ray Fluorescence based method, to the best of our knowledge. The method was successfully applied for the U determination in natural water samples like ground water, river water and sea water.

Nondestructive discrimination of red silk single fibers using total reflection X-ray fluorescence spectrometry and synchrotron radiation X-ray fluorescence spectrometry.

In a strangulation case, when a necktie is used as a murder weapon, the dyed silk single fiber becomes an important evidence sample to solve the crime. Dyed silk single fibers contain elements, such as Cr and Co, which are obtained from dyeing using metal mordants. Currently, there are no nondestructive and sufficiently sensitive elementary analytical methods for the forensic analysis of single fibers. Therefore, in this study, eight commercially available red silk samples were collected and used for total reflection X-ray fluorescence (TXRF) and synchrotron radiation X-ray fluorescence (SR-XRF) spectrometry. Benchtop TXRF detected both S in the silk protein and Cl and Ca, which are elements absorbed from the environment by silkworms, but also Cr, which is a dyeing derivative for metal mordants. The presence of Cr and Zn, in addition to the Zn/Cr signal intensity ratios, was reported to be particularly useful identifiers. In SR-XRF, the presence of Cr, Co, Zn, and Br and the Zn/Cr signal intensity ratios were reported to be useful discriminating indicators. In this study, the nondestructive discrimination capabilities of TXRF and SR-XRF measurements for the samples were found to be 85.7% and 100%, respectively. Therefore, we propose a combination of TXRF and SR-XRF as a new nondestructive single fiber identification method for forensic science. Moreover, if partial destruction of a single fiber is allowed, the observation of the cross section and micro-Fourier-transform infrared spectroscopy measurements is useful for identifying red silk fibers.

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.

Quantification of Element Mass Concentrations in Ambient Aerosols by Combination of Cascade Impactor Sampling and Mobile Total Reflection X-ray Fluorescence Spectroscopy

Quantitative chemical analysis of airborne particulate matter (PM) is vital for the understanding of health effects in indoor and outdoor environments, as well as for enforcing EU air quality regulations. Typically, airborne particles are sampled over long time periods on filters, followed by lab-based analysis, e.g., with inductively coupled plasma mass spectrometry (ICP-MS). During the EURAMET EMPIR AEROMET project, cascade impactor aerosol sampling is combined for the first time with on-site total reflection X-ray fluorescence (TXRF) spectroscopy to develop a tool for quantifying particle element compositions within short time intervals and even on-site. This makes variations of aerosol chemistry observable with time resolution only a few hours and with good size resolution in the PM10 range. The study investigates the proof of principles of this methodological approach. Acrylic discs and silicon wafers are shown to be suitable impactor carriers with sufficiently smooth and clean surfaces, and a non-destructive elemental mass concentration measurement with a lower limit of detection around 10 pg/m3 could be achieved. We demonstrate the traceability of field TXRF measurements to a radiometrically calibrated TXRF reference, and the results from both analytical methods correspond satisfactorily.

Suspension assisted analysis of sulfur in petroleum coke by total-reflection X-ray fluorescence

The influence of the particle size distribution of a petroleum coke sample compared to its sulfur content was investigated. For this matrix, an optimization procedure of the Suspension Assisted Analysis (SAA) by Total-reflection X-Ray Fluorescence (TXRF) quantitative method was developed. SAA-TXRF sulfur recoveries were evaluated for three particle size distributions of the same coke sample. The sulfur recovery increased when the particle size distribution was smaller. The observed behaviour was correlated and validated with CHNS elemental analysis and microwave-assisted digestion TXRF measurements. The results indicate that the sulfur signal is strongly influenced by the particle size distribution and the deposition morphology of the petroleum coke material. This effect could be explained by the presence of a strong absorption effect for the sulfur signal in combination with the distortion of the X-ray Standing Waves (XSW) field observed between the analyte, S, and the elements Ti and Co, which were used as an internal standard. The variation in sulfur observed was up to 45.5% lower than the higher recovery obtained by CHNS. This investigation suggests that for an adequate application of the SAA-TXRF method in petroleum coke or similar matrices, careful optimization of the final particle dispersion of the ground coke is crucial and necessary. In this case, the use of a high- power ultrasound probe was the key.

Application of TXRF in monitoring trace metals in particulate matter and cloud water

Abstract. Trace metals in ambient particulate matter and cloud are considered key elements of atmospheric processes as they affect air quality, environmental ecosystems, and cloud formation. However, they are often available at trace concentrations in these media such that their analysis requires high-precision and sensitive techniques. In this study, different analytical methods were applied to quantify trace metals in particulate matter (PM) samples collected on quartz and polycarbonate filters as well as cloud water, using the Total reflection X-Ray Fluorescence (TXRF) technique. These methods considered the measurement of filter samples directly without and with chemical pretreatment. Direct measurements involved the analysis of PM samples collected on polycarbonate filters and cloud water samples after they are brought onto TXRF carrier substrates. The chemical treatment method involved the assessment of different acid digestion procedures on PM sampled on quartz filters. The solutions applied were reverse aqua regia, nitric acid, and a combination of nitric acid and hydrogen peroxide. The effect of cold-plasma treatment of samples on polycarbonate filters before TXRF measurements was also investigated. Digestion with the reverse aqua regia solution provided lower blanks and higher recovery in comparison to other tested procedures. The detection limits of the elements ranged from 0.3 to 44 ng cm−2. Ca, K, Zn, and Fe showed the highest detection limits of 44, 35, 6, and 1 ng cm−2, while As and Se had the lowest of 0.3 and 0.8 ng cm−2, respectively. The method showed higher recovery for most trace metals when applied to commercially available reference materials and field samples. TXRF measurements showed good agreement with results obtained from ion chromatography measurements for elements such as Ca and K. Cold-plasma treatment did not significantly lead to an increase in the detected concentration, and the results were element specific. Baking of the quartz filters prior to sampling showed a reduction of more than 20 % of the filter blanks for elements such as V, Sr, Mn, Zn, and Sb. The methods were applied successfully on ambient particulate matter and cloud water samples collected from the Atlas Mohammed V station in Morocco and the Cape Verde Atmospheric Observatory. The obtained concentrations were within the range reported using different techniques from similar remote and background regions elsewhere, especially for elements of anthropogenic origins such as V, Pb, and Zn with concentrations of up to 10, 19, and 28 ng m−3, respectively. Enrichment factor analysis indicated that crustal matter dominated the abundance of most of the elements, while anthropogenic activities also contributed to the abundance of elements such as Sb, Se, and Pb. The results confirm that TXRF is a useful complementary sensitive technique for trace metal analysis of particulate matter in the microgram range as well as in cloud water droplets.

Direct non-destructive total reflection X-ray fluorescence elemental determinations in zirconium alloy samples.

The development of a direct non-destructive synchrotron-radiation-based total reflection X-ray fluorescence (TXRF) analytical methodology for elemental determinations in zirconium alloy samples is reported for the first time. Discs, of diameter 30 mm and about 1.6 mm thickness, of the zirconium alloys Zr-2.5%Nb and Zircalloy-4 were cut from plates of these alloys and mirror polished. These specimens were presented for TXRF measurements directly after polishing and cleaning. The TXRF measurements were made at the XRF beamline at Elettra synchrotron light source, Trieste, Italy, at two different excitation energies, 1.9 keV and 14 keV, for the determinations of low- and high-Z elements, respectively. The developed analytical methodology involves two complementary quantification schemes, i.e. using either the fundamental parameter method or relative sensitivity based method, allowing quantification of fifteen minor and trace elements with respect to Zr with very good precision and accuracy. In order to countercheck the TXRF analytical results, some samples were analyzed using the DC arc carrier distillation atomic emission spectrometry technique also, which shows an excellent agreement with the results of the TXRF-based methodology developed in this work. The present work resulted in a non-destructive TXRF elemental characterization methodology of metal and alloy samples avoiding the cumbersome dissolution and matrix separation which arenormally required in other techniques and traditional methods of TXRF determination. In addition, the production of analytical waste could also be avoided to a large extent. Although the work was carried out for specific applications in the nuclear industry, it is equally suitable for other such samples in different industrial applications.

A comparison of different nanoscopic silver species with respect to their capacity to bind mercury from the gas-phase using total reflection X-ray fluorescence

Mercury compounds like mercury chloride (HgCl2) were often used to protect cultural heritage specimens, e.g., herbaria and paintings from damage. Over time, Hg0 is formed by bacterial activity and released into the air.Here we present our study on the performance of different nanoscopic Ag species to collect airborne Hg, which is subsequently analyzed by total reflection X-ray fluorescence (TXRF). We studied silver nanoparticles (AgNPs) of different size, i.e., 10 nm and 100 nm AgNPs(Citrate) and particles with presumably weaker stabilizers, i.e., 10 nm AgNPs(borohydride(BH4−)) as well as species from light-exposed (LE) pure aqueous (LE-AgNO3(H2O)) and ammoniacal silver nitrate solutions (LE-AgNO3(NH3)). Hg capture was highest for the LE-AgNO3(NH3) species with a ratio of Hg/Ag of 0.78 in the amalgam. The performance to capture Hg decreased from LE-AgNO3(NH3) to AgNPs(Citrate) in the following order LE-AgNO3(NH3) > LE-AgNO3(H2O) > 10 nm AgNPs(BH4−) > 10 nm AgNPs(Citrate) > 100 nm AgNPs(Citrate), the latter collected airborne Hg with a ratio of Hg/Ag of 0.0006. The relative standard deviation of the TXRF measurements of Hg collected from a saturated atmosphere (n = 3 and n = 5) was lowest with 9% for LE-AgNO3(H2O) and highest for the AgNPs(Citrate) with 38%. The AgNPs(BH4−) and AgNPs(Citrate) species were also used to study Hg capture from the gas-phase in concentrations between 0.0012 mg/m3 and 0.024 mg/m3 (European Union regulated threshold: 0.02 mg/m3; saturated Hg atmosphere: 13.6 mg/m3 at 20 °C). Detection limits were found to be 0.018 μg/m3 for AgNPs(BH4−) and AgNPs(Citrate).

Using a portable total reflection X‐ray fluorescence system for a multielement analysis of Swiss mice brains with experimental Alzheimer's disease induced by β‐amyloid oligomers

Alzheimer's disease (AD) is a progressive and irreversible disorder whose pathological features include β‐amyloid (Aβ) plaques and neuronal and synaptic loss. Metals such as iron, copper, and zinc are increased in the brains of patients with AD. Those metals can interact with Aβ, resulting in the promotion of Aβ deposition and formation of plaque. However, no study analyzing the effects of single injection of Aβ soluble oligomers (AβOs) in the elements' homeostasis in mice was developed. Total reflection X‐ray fluorescence (TXRF) is a multielement analytical technique that can be utilized to identify and quantify trace elements present in a sample at very low concentrations. In this study, in order to evaluate the concentration of metals in brain regions of Swiss mice, three groups of female mice and three of male mice were studied: control, AD10, and AD100. The AD groups received an AβOs intracerebroventricular injection so as to induce experimental AD. Afterwards, a craniotomy was performed, and six brain compartments were dissected and evaluated. TXRF measurements were performed using a portable TXRF system that uses an X‐ray tube with a molybdenum anode and a detector Si‐PIN. It is proved to determine the following elements' concentrations: phosphorus, sulfur, potassium, iron, copper, zinc, and rubidium. Results showed differences in the elemental concentration in some brain regions between AD groups. These alterations suggest that AβOs act quickly, even before the amyloid plaques' formation, explaining cognitive deficits independently of amyloid plaques. This study helped to understand that this modification on elemental concentration can be influenced by AβOs.

Development of Methods to Evaluate Several Levels of Uranium Concentrations in Drainage Water Using Total Reflection X-Ray Fluorescence Technique.

As a country's law stipulates the effluent standard uranium concentration in drainage water, the uranium concentration must be determined when drainage water is released from a uranium handling facility, such as the Fukushima Daiichi nuclear power plant. The maximum allowable limit for uranium release at each facility is defined taking into consideration the situation of the facility, such as 1/10 to 1/100 of this effluent standard value. Currently, the uranium concentration of drainage water is commonly determined by α-particle spectrometry, in which several liters of drainage water must be evaporated, requiring about half of a day followed by 2–3 h of measurements, due to the low specific radioactivity of uranium. This work proposes a new methodology for the rapid and simple measurement of several levels of uranium in drainage water by a total reflection X-ray fluorescence (TXRF) analysis. Using a portable device for TXRF measurements was found to enable measurements with 1/10 the sensitivity of the effluent standard value by 10 times condensation of the uranium-containing sample solution; a benchtop device is useful to measure uranium concentrations <1/100 of the effluent standard value. Therefore, the selective usage of methods by a portable and benchtop devices allows for screening and precise evaluation of uranium concentrations in drainage water.

Pattern of Altered Plasma Elemental Phosphorus, Calcium, Zinc, and Iron in Alzheimer\u2019s Disease

Metal/mineral dyshomeostasis has been implicated in the development of Alzheimer’s disease (AD). The aim of the study was to investigate the difference in absolute and percentage levels of plasma phosphorus, calcium, iron, zinc, copper, selenium in cognitively normal (CN) and AD subjects. Total reflection X-ray fluorescence (TXRF) spectroscopy was used to detect plasma metals/minerals in CN and AD subjects (n = 44 per group). TXRF detected significantly increased plasma levels of phosphorus (p = 1.33 × 10−12) and calcium (p = 0.025) in AD compared to CN subjects, with higher phosphorus/calcium (p = 2.55 × 10−14) ratio in the former. Percentage concentrations calculated for phosphorus, calcium, iron, zinc, copper, selenium by dividing the concentration of each element by the total concentration of these elements and multiplying by 100%, demonstrated phosphorus was higher in AD compared to CN subjects, while calcium, iron, zinc, copper and selenium were lower in AD subjects, with area under the curves as high as 0.937 (p = 6 × 10−5) computed from receiver operating curves. With exclusion of high levels of phosphorus and calcium from percentage calculations, iron levels remained low in AD whereas zinc was higher in AD, and copper and selenium levels were similar. We demonstrate altered distribution of elements in the plasma of AD subjects with high interdependencies between elemental levels and propose the potential of TXRF measurements for disease monitoring.

Comparison of techniques for detecting metal contamination in silicon wafers

In this work we present the results of experiments aimed at comparing the performances of various techniques for the detection of metal contamination in the silicon technology. Techniques for the measurement of surface contamination such as Total Reflection X-Ray Fluorescence (TXRF) and Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) are compared with techniques for the measurement of contamination in the silicon volume, specifically the Deep Level Transient Spectroscopy and techniques for the measurement of carrier lifetime. Carrier lifetime measurements were obtained by photocurrent measurements and by Surface Photovoltage measurements.In a first experiment, Synchrotron-Radiation TXRF (SR-TXRF) was used as the reference technique to assess the sensitivity of a commercial TXRF instrument and of carrier lifetime measurements to detect iron contamination in wafers cleaned by ordinary cleaning processes.Samples intentionally contaminated by spinning with various elements were used for another experiment comparing TXRF and ToF-SIMS measurements of surface contamination.Then, a few case studies are discussed, specifically tungsten contamination by sputtering in ion-implanted samples and palladium contamination due to contact with a contaminated chuck.In all these experiments, advantages and disadvantages of the different techniques are discussed. The results of this study clearly show that it is not possible to define a unique recipe that can be applied in all cases. The maximum tolerated contaminant concentration per unit area depends on the contaminant diffusivity, and is much lower for slow diffusers. The contaminant diffusivity and solid solubility in silicon determine the in-depth distribution of the contaminant, and hence the most effective approach.

Determination of uranium in immersion liquid of demolition waste using total reflection X-ray fluorescence analysis

In this study, we proposed a novel methodology based on total reflection X-ray fluorescence (TXRF) analysis for rapid evaluation of uranium radioactivity concentration in water samples, which will be found in the decommissioning field of Fukushima Daiichi Nuclear Power Plant containing various impurities. Sample solutions were prepared by mixing a multi-element standard solution containing uranium and thorium with an immersion liquid of the demolition debris in order to examine the effect of components of the demolition debris. An indium standard solution was added to the samples as an internal standard. Since the Rb Kα peak overlapped with the U Lα and Th Lα peaks, Gaussian fitting was performed to determine the net intensity of the U Lα peak. Moreover, due to the largely different contents of uranium and rubidium, reducing the number of fitting parameter made the Gaussian fitting easier. To determine the widths of the peaks, long-time TXRF measurement of the standard solutions for each element was performed. In the Gaussian fitting, only the peak intensities were considered as fitting parameters because the peak widths and peak energies could be fixed. The relative intensity of the U Lα peak was calculated as the net intensity of the U Lα peak normalized by that of the In Kα peak. The relative intensity was directly proportional to the uranium concentration. The estimated minimum detection limit of uranium with a measurement time of 15 min was significantly lower than the effluent standard value for uranium concentration in drainage water as defined by the Japanese Water Pollution Prevention Law, 20 mBq/cm3. All in all, we believe that this method will be useful in determining the uranium concentration in drainage water in the decommissioning field of Fukushima Daiichi Nuclear Power Plant.

Evaluation of total-reflection X-ray fluorescence measurements for the prospective determination of uranium in the decommissioning of the Fukushima Daiichi Nuclear Power Plant reactor

Owing to the strong earthquake and subsequent tsunami in March 2011, the Fukushima Daiichi Nuclear Power Plant was exceedingly damaged and is currently under decommissioning. Herein, we propose a methodology to evaluate the uranium concentration in the drainage water from the decommissioning field. Model sample solutions were prepared by mixing multi-element standard solutions containing uranium with an immersion liquid containing demolition debris. A very small amount (10 μL) of the sample solutions was dropped onto a quartz optical flat directory with or without a chromatography resin separation. The total-reflection X-ray fluorescence (TXRF) spectrometry measurement was performed using a portable device. These measurements showed an overlap of the Rb Kα and U Lα peaks in the TXRF spectrum of the sample solution prepared without chromatography resin separation. By contrast, no overlap was observed in the TXRF spectrum of the sample solution after the separation using a chromatography resin. When the drainage water is composed of 0.04% U-234, 5% U-235, and 94.96% U-238, the measurement times in both methods (i.e., with and without pretreatment) required to attain detection limits lower than the effluent standard value are 15 and 5 min, respectively. Additionally, the detection limits, analysis times, required sample volumes, and procedures of the two methods are compared.

A dilute-and-shoot sample preparation strategy for new and used lubricating oils for Ca, P, S and Zn determination by total reflection X-ray fluorescence

In this work, a dilute-and-shoot method was developed for Ca, P, S and Zn determination in new and used lubricating oil samples by total reflection X-ray fluorescence (TXRF). The oil samples were diluted with organic solvents followed by addition of yttrium as internal standard and the TXRF measurements were performed after solvent evaporation. The method was optimized using an interlaboratorial reference material. The experimental parameters evaluated were sample volume (50 or 100μL), measurement time (250 or 500s) and volume deposited on the quartz glass sample carrier (5 or 10μL). All of them were evaluated and optimized using xylene, kerosene and hexane. Analytical figures of merit (accuracy, precision, limit of detection and quantification) were used to evaluate the performance of the analytical method for all solvents. The recovery rates varied from 99 to 111% and the relative standard deviation remained between 1.7% and 10% (n=8). For all elements, the results obtained by applying the new method were in agreement with the certified value. After the validation step, the method was applied for Ca, P, S and Zn quantification in eight new and four used lubricating oil samples, for all solvents. The concentration of the elements in the samples varied in the ranges of 1620–3711mgL−1 for Ca, 704–1277mgL−1 for P, 2027–9147mgL−1 for S, and 898–1593mgL−1 for Zn. The association of TXRF with a dilute-and-shoot sample preparation strategy was efficient for Ca, P, S and Zn determination in lubricating oils, presenting accurate results. Additionally, the time required for analysis is short, the reagent volumes are low minimizing waste generation, and the technique does not require calibration curves.

Total reflection X-ray spectroscopy as a rapid analytical method for uranium determination in drainage water

ABSTRACTUranium concentrations in drainage water are typically determined by α-spectrometry. However, due to the low specific radioactivity of uranium, the evaporation of large volumes of drainage water, followed by several hours of measurements, is required. Thus, the development of a rapid and simple detection method for uranium in drainage water would enhance the operation efficiency of radiation control workers. We herein propose a novel methodology based on total reflection X-ray fluorescence (TXRF) for the measurement of uranium in contaminated water. TXRF is a particularly desirable method for the rapid and simple evaluation of uranium in contaminated water, as chemical pretreatment of the sample solution is not necessary, measurement times are typically several seconds, and the required sample volume is low. We herein employed sample solutions containing several different concentrations of uranyl acetate with yttrium as an internal standard. The solutions were placed onto sample holders, and were dried prior to TXRF measurements. The relative intensity, otherwise defined as the net intensity ratio of the Lα peak of uranium to the Kα peak of yttrium, was directly proportional to the uranium concentration. Using this method, a TXRF detection limit for uranium in contaminated water of 0.30 µg/g was achieved.

A comparative study on the total reflection X-ray fluorescence determination of lowZelements using X-ray tube and synchrotron radiation as excitation sources

Detailed total reflection X-ray fluorescence (TXRF) studies for the detection and quantification of low atomic number elements were carried out by using a laboratory dual source TXRF spectrometer equipped with a vacuum chamber and at the International Atomic Energy Agency multi-purpose end-station facility, operated at the XRF beamline of Elettra Sincrotrone Trieste, Italy. Multi-elemental standard aqueous solutions of low Z elements (F, Na, Al, S, K, Sc, and Ti) with different elemental concentrations of 2, 10, 20, and 30 µg/ml were prepared and measured in both setups. The measurements at the synchrotron setup were performed in a scanning mode across the sample residue and perpendicular to the incident beam in order to account properly for a possible non-uniform deposition of certain elements. The accuracy and the detection limits obtained from the TXRF measurements in both setups were determined and comparatively evaluated and assessed. Significant improvement in the TXRF detection limits at the synchrotron beamline end-station was obtained for the elements with Z ≤ 13 (Al). Copyright © 2017 John Wiley & Sons, Ltd.

Multi-element analysis of vegetal foodstuff by means of low power total reflection X-ray fluorescence (TXRF) spectrometry

In this work, an analytical methodology in combination with a low power benchtop total reflection X-ray fluorescence (TXRF) system has been developed for multi-elemental analysis of vegetal materials. An easy and rapid sample preparation consisting in suspending 20mg of sample in de-ionized water showed to be the most suitable for this kind of samples. However, for comparison purposes, two digestion procedures were also applied.A set of fifteen certified reference materials and three real vegetal samples were employed for the quantitative determination of K, Ca, Mn, Fe, Cu, Zn, Br, Rb, Sr, Pb, As and Sn. All the parameters affecting sample preparation and TXRF measurements conditions were carefully evaluated. Accurate and precise results were obtained for mid-high Z elements (Mn-Sr) using internal standardization as quantification approach, while for light Z elements (K and Ca), due to absorption effects, an improvement of analytical results by external calibration was necessary.

Measurement uncertainty in Total Reflection X-ray Fluorescence

Total Reflection X-ray Fluorescence (TXRF) spectrometry is a multi-elemental technique using micro-volumes of sample. This work assessed the components contributing to the combined uncertainty budget associated with TXRF measurements using Cu and Fe concentrations in different spiked and natural water samples as an example. The results showed that an uncertainty estimation based solely on the count statistics of the analyte is not a realistic estimation of the overall uncertainty, since the depositional repeatability and the relative sensitivity between the analyte and the internal standard are important contributions to the uncertainty budget. The uncertainty on the instrumental repeatability and sensitivity factor could be estimated and as such, potentially relatively straightforward implemented in the TXRF instrument software. However, the depositional repeatability varied significantly from sample to sample and between elemental ratios and the controlling factors are not well understood. By a lack of theoretical prediction of the depositional repeatability, the uncertainty budget can be based on repeat measurements using different reflectors. A simple approach to estimate the uncertainty was presented. The measurement procedure implemented and the uncertainty estimation processes developed were validated from the agreement with results obtained by inductively coupled plasma — optical emission spectrometry (ICP-OES) and/or reference/calculated values.

Residual metallic contamination of transferred chemical vapor deposited graphene.

Integration of graphene with Si microelectronics is very appealing by offering a potentially broad range of new functionalities. New materials to be integrated with the Si platform must conform to stringent purity standards. Here, we investigate graphene layers grown on copper foils by chemical vapor deposition and transferred to silicon wafers by wet etching and electrochemical delamination methods with respect to residual submonolayer metallic contaminations. Regardless of the transfer method and associated cleaning scheme, time-of-flight secondary ion mass spectrometry and total reflection X-ray fluorescence measurements indicate that the graphene sheets are contaminated with residual metals (copper, iron) with a concentration exceeding 10(13) atoms/cm(2). These metal impurities appear to be partially mobile upon thermal treatment, as shown by depth profiling and reduction of the minority charge carrier diffusion length in the silicon substrate. As residual metallic impurities can significantly alter electronic and electrochemical properties of graphene and can severely impede the process of integration with silicon microelectronics, these results reveal that further progress in synthesis, handling, and cleaning of graphene is required to advance electronic and optoelectronic applications.