Minimum detection time (MDT) for elemental EDXRF images

When obtaining a chemical element image through energy dispersive X‐ray fluorescence (EDXRF) scanning of a specific sample, it is important to determine the minimum detection time (MDT) required per dot (pixel) and per element in order to identify the minority and the trace elements present in the sample. Starting from the statistical criteria of limit of detection, quantitative estimations can be made regarding the concentration of elements present in the samples, determining the MDT which fits to the limit of detection previously established. Given that with this technique it is possible to implement in vivo applications, in this work, a process was developed for the MDT that is capable of generating the minimum radiation exposure in imaging EDXRF. For this proposal, the MDT is determined for metals, such as Fe, Cu, and Pb, given their great biomedical interest, in a series of equivalent bone and soft tissue phantom samples. Consequently, a criteria for global scanning time per dot was established, hence providing an elemental XRF image according to the As Low As Reasonably Achievable principles, i.e. as low an exposure as reasonably possible for each sample type studied by this sort of devices, in order to obtain appropriate information for each field of application. Copyright © 2015 John Wiley & Sons, Ltd.     

Comparison of elemental content on modern and ancient papers by EDXRF

We report on the use of elemental composition, determined by energy dispersive X-ray fluorescence (EDXRF), to identify different types of paper. The concentrations of S, Cl, K, Ca, Ti, Mn, Fe, Co, Cu, Zn, As, Br, Rb, Sr, Ba and Pb were determined in papers from 1555, 1575, 1724, 1748, 1779, 1782, 1787, 1806, 1861, 1919, 1941 and 2005. A preliminary analysis was made with the use of a dendrogram. The Euclidian distances evidenced a big fluctuation in the elemental composition on most recent papers. The dendrogram also allowed us to catalogue the analysed samples into ten types of paper. Calcium, Cu, Fe, Zn and Sr were the only elements found in all paper samples. However the content of each element was different in every paper type. Calcium is the predominant element in all paper types. Applying Spearman coefficients correlations to these papers for Ca, Cu, Fe, Zn and Sr, we found moderate negative correlations between Ca-Cu. Positive correlations were also found between Fe-Cu, though not very strong. High levels of the toxic elements, Co, Ni, As and Pb were present in papers from 1779 and 1787. From this work it becomes clear that the number of elements in modern papers is lower than in older ones. PACS 39.30.+W; 78.70.En; 89.90.+n     

Use of EDXRF elemental fingerprinting for discrimination of botanical and geographical origin of Slovenian bee pollen

Bee pollen contains proteins, amino acids, carbohydrates, fats, fatty acids, vitamins, polyphenols, and mineral nutrients that make it useful as a good nutritional supplement in the human diet. It has the richest elemental composition among bee products which is not uniform and consequently varies greatly depending on botanical and geographical origin. In polyfloral and selected monofloral bee pollen samples: sweet chestnut, maple, dandelion, rapeseed, flowering ash, buckwheat, common ivy, and plantain, the concentrations of P, S, Cl, K, Ca, Mn, Fe, Zn, Br, Rb, and Sr were determined. A non-destructive energy dispersive X-ray fluorescence spectrometry was used for elemental fingerprinting. The most abundant elements in Slovenian bee pollen are K, P, S, Ca, and Cl followed by Fe, Mn, Zn, Rb, Br, and Sr. Several statistically significant differences in the content of analysed elements were found between studied groups according to the botanical and geographical origin which can be related to soil and plant elemental composition and plant metabolism. The obtained data extend our previous chemical profiling of Slovenian bee pollen and contribute to a more precise evaluation of some essential mineral nutrients in bee pollen to cover recommended dietary allowances in human nutrition. Additionally, this work contributes to a better understanding of mineral nutrient requirements in honey bee nutrition and of the environmental and agricultural impact of this product.     

Trace element analysis of fly ash samples by EDXRF technique

Trace element analysis of some fly ash samples and soil samples have been carried out by Energy Dispersive X-Ray Fluorescence technique. Fourteen elements namely K, Ca, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Se, Rb, Sr and Pb have been quantified in the fly ash samples by this technique. It was found that there is no huge concentration difference between the fly ash and soil samples as a result of which fly ash can be used as soil manure without any adverse impact on the plants.      

Patterns of inter‐elemental effects in EDXRF and a new correction method

A new method is suggested for improving the accuracy of energy‐dispersive x‐ray fluorescence analysis (EDXRF) and its implementation is described. This method is a result of studying changes in coefficients of the inter‐elemental effect, A = f(Z). We created a data bank for elements from K to Br, which accounts for the effect of three lighter and five heavier neighboring elements upon the sought element. This study offers a physical explanation of sharp bends in coefficient curves. We suggest principles for optimizing the analytical region parameters so as to reduce the effect of neighboring elements. Finally, we describe the principles of building a data bank A = f(Z, R) to account for the effect of energy resolution (R) change. Application of the suggested method to the exploration of oceanic nodules reduced the cobalt detection threshold by 50–75% (C_lim?0.95 = 0.032%) and decreased the standard deviation of spectrum analysis, thus enhancing confidence in EDXRF as an effective tool for research on complex objects. The approach suggested in this study can be used with newer energy‐dispersive analyzers, including TXRF models. Copyright © 2003 John Wiley & Sons, Ltd.     

Extending the quantitative analytical capabilities of the EDXRF technique for plant‐based samples

The energy‐dispersive x‐ray fluorescence (EDXRF) technique has limitations in the quantitative analysis of light elements (low‐Z analytes with Z < 10), for many reasons. This work, however, circumvents the problem through an a priori determination of low‐Z analytes, representative of plant‐based samples. The main purpose of this work was to characterize the major elements in the dark matrix of some plant‐based samples (including biomonitors) using Rutherford backscattering spectrometry (RBS), and the results provided as a generalized input for EDXRF analysis. The derived stoichiometry and mass ratio for the moss, lichen, and cotton cellulose samples analyzed were found to be similar and close to C₇H₁₀O₅, with an average matrix of C = 49.8%, H = 4.0% and O = 45.8%. Quantitative analysis of plant‐based reference material IAEA‐336 (lichen) was subsequently carried out. Use of the a priori determined dark matrix elements (from one‐time RBS spectrometry) extended the scope of applicability of the EDXRF quantitative methods used, and improved accuracy in the elemental analysis of plant‐based samples. The results obtained were in good agreement with the reference values. Copyright © 2004 John Wiley & Sons, Ltd.     

Elemental concentration analysis in some plant samples by EDXRF at Trabzon

The elemental analysis of some plant samples have been carried out in Trabzon region (Turkey) using energy-dispersive X-ray fluorescence (EDXRF) spectrometry. We have analyzed plant samples for nine stations using 1.85 GBq ⁵⁵Fe radioactive sources. We have found that potassium and calcium within 0.3-1.4% and 0.3-2.8% were present in concentration in plants for every station, respectively. The concentration of Cl and Ti generally changed according to the plant species and the sampling station.     

Identification of elemental composition of PM2.5 collected in Makkah,Saudi Arabia,using EDXRF

Makkah city, Saudi Arabia, represents the most attractive place for religious tourism for Muslims all over the world. More than 15 million visitors come to the city per year, especially during Hajj (pilgrimage) and Ramadan seasons. Due to the lack of air quality assessment data for Makkah, measurement of different pollutants in Makkah is of great interest. In the present work, airborne particulate matter with aerodynamic diameter equal to or less than 2.5 µm (PM_2.5) has been collected from two different sites in the city, namely the Grand mosque and Al‐Shraie, from December 2012 to January 2014 covering the different seasons of the year. The average mass concentrations at the sites are comparable, 48 ± 28 µg/m³ and 53 ± 27 µg/m³ for the Grand mosque and Al‐Shraie sites, respectively. For quantitative elemental analysis, energy dispersive X‐ray fluorescence (EDXRF) spectrometry was used. Twenty elements (Si, S, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Se, Br, Rb, Sr and Pb) were quantified in the PM_2.5 samples. Fortunately, the obtained results of Pb and S are below the maximum allowance level of European commission for air quality. However, the average concentration of Ni in both sites is close to the maximum allowance level 20 ng/m³ and the Ni concentration reaches 25 ng/m³ at Grand mosque site during August 2013. Based on the Positive Matrix Factorization (PMF) analysis, four source factors were found, some signalling mixed sources, showing the main influence from mineral dust, anthropogenic/industrial sources and a marine source. Copyright © 2017 John Wiley & Sons, Ltd.     

Sulfur determination on stone monuments with a transportable EDXRF system

An important part of the world's cultural heritage is represented by stone monuments. A very dangerous weathering process that deteriorates stone monuments and is caused by human activity is air pollution. One of the worst pollutants for stone monuments is associated with sulfur compounds, especially with gypsum. Gypsum is a rather soluble compound that may be washed away by rain. It leaves the surface of the stone clean but eroded and open to new corrosive processes. With transportable energy dispersive x‐ray fluorescence (EDXRF) instruments it is possible to conduct in situ investigations, mappings, registrations and evaluations of the stone‐degradation phenomena related to sulfate formation on stone and stone‐like materials by quantifying sulfur concentrations directly associated with the presence of gypsum. The EDXRF instrument used in this project is a commercial system comprising a miniaturized low‐power, air‐cooled tungsten x‐ray tube and a silicon drift detector (SDD) Peltier‐cooled detector. The EDXRF instrument was calibrated using a series of standard samples specifically developed for this project with a sulfur content ranging from 0.5 to 15%. Correlating the sulfur peak counts with sulfur concentrations, a straight calibration line (R² = 0.9985) was obtained. Several high voltage levels of the x‐ray tube were tried to define the best operating conditions. The silicon escape peak of calcium had to be accounted for owing to its interference with the sulfur peak. In this paper we shall discuss the working method adopted and the results achieved following the examination of a number of stone monuments such as the “Fanciulla di Anzio” and other ancient Roman statues housed in the Roman National Museum, and the Sarcophagus of Pope Boniface VIII sculpted by Arnolfo di Cambio and situated in the Crypt of the Vatican Basilica. Copyright © 2007 John Wiley & Sons, Ltd.     

An EDXRF method for determination of uranium and thorium in AHWR fuel after dissolution

A fast energy dispersive x‐ray fluorescence (EDXRF) method requiring only microgram amounts of analytes, i.e. uranium (U) and thorium (Th), in their mixtures in solution form is described. Calibration solutions and samples covering the fuel composition range (0–5% of U in U + Th) of advanced heavy water reactor (AHWR) were prepared by mixing uranium and thorium solutions. A known fixed amount of internal standard yttrium (Y) was added to these solutions. EDXRF spectra of calibration solutions and samples were measured by taking 20 µl aliquots on 30 mm diameter filter papers, after drying, using a Rh target tube operated at 40 kV and 500 µA. Calibration plots were made by plotting U/Y, U/Th and Th/Y amount ratios against the respective intensity ratios of Th Lα, U Lα and Y Kα. In the first set, U was determined using Y as an internal standard, and for Th determination, U, thus determined, was used as an internal standard since the amounts of Th and Y were kept constant in the calibration solutions and samples. In the second set, both U and Th were varied and determined using Y as internal standard. The results of U and Th determinations showed a precision of about 3% (1s) and the results deviated from the expected values by <3% in most of the cases. This approach has an advantage that it requires only microgram amounts of sample, thus mitigating radiation hazards associated with radioactive samples as well as the amount of radioactive analytical waste generated is quite less. Copyright © 2009 John Wiley & Sons, Ltd.     

The elemental composition of Stradivari's musical instruments: new results through non‐invasive EDXRF analysis

During recent decades, many researchers have tried to understand the main influences on the extraordinary sound and beauty of the masterpieces made by the ancient violin makers. This is still a challenge for many others today. Mainly because of a lack of written historical documents, the rediscovery of some of the ancient violin‐making processes was made possible thanks to scientific analyses performed on their materials by means of diagnostic techniques. However, understanding which substances were adopted is a very hard task, because the analyses are influenced by many factors: for example, alterations, wear, retouches, and the heterogeneity of materials. This paper presents some new EDXRF results collected on eight‐stringed musical instruments made by Antonio Stradivari between 1669 and 1734 (“Clisbee” 1669, “Hellier” 1679, “Ford‐Rougemont” 1703, “Joachim‐Ma” 1714, “Russian Federation” viola 1715, “Cremonese” 1715, “Vesuvius” 1727, and “Scotland” 1734) and now preserved at the Museo del Violino in Cremona. A brief comparison with a modern violin made by Simone Ferdinando Sacconi (“Hellier copy” 1941), one of the most eminent violin makers of the 20th century and one of the greatest experts on Stradivari's work, is also provided. This represents the first comparative analysis of a wide number of ancient musical instruments made by the same violin maker over an extended period. A non‐destructive and non‐invasive approach was followed to (a) understand the elemental composition differences between the best conserved and most worn‐out surfaces; (b) check if there are elemental similarities among the finishing materials of violins made in different years by the same violin maker; (c) give new suggestions about the materials used. To distinguish the best conserved areas from the worn‐out ones, a preliminary investigation by UV‐induced fluorescence photography was performed. In addition, stereomicroscopic observations and Fourier transform infrared spectroscopy (FTIR) analyses were performed on selected areas to validate the hypotheses. The results, in some cases comparable with previous research on Stradivari instruments, have increased the pool of information about materials and treatments adopted in the Stradivari workshop.     

Figure of merit for spectrometers for EDXRF

How should one select the best detector for a particular measurement in energy dispersive X‐ray fluorescence (EDXRF)? How should one select the optimum system configuration, i.e. the best shaping time and beam current? Manufacturers provide a variety of specifications, such as energy resolution and maximum count rate, but these are indirectly related to the end use of an EDXRF instrument, the measurement and detection limit of the measured elemental concentrations. We suggest in this paper using the time required to achieve a given statistical uncertainty as a figure of merit. We derive scaling rules for this figure of merit based on conventional specifications, including energy resolution, peaking time, maximum count rate, detector area, and intrinsic efficiency. These scaling rules also include the peak to background ratio of a photopeak and the number of overlapping peaks. We then show how this figure of merit can be used to select the optimum detector and spectrometer configuration for specific applications and compare the results to data obtained with typical systems. Copyright © 2012 John Wiley & Sons, Ltd.     

Radioisotope‐induced EDXRF investigation of elemental uptake in cauliflower grown at MSW‐contaminated site

A ¹⁰⁹Cd radioisotope‐induced energy dispersive X‐ray fluorescence (EDXRF) study has been performed on samples of cauliflower consisting of the flower, the leaves and the associated root soil. The cauliflowers are collected from farms near the main dumping site of municipal solid waste (MSW) in the city of Kolkata, India, and also from uncontaminated farms about 50 km away from the city. The systematic investigation is primarily aimed at achieving two correlated objectives. Firstly, a unified calibration approach is undertaken for the study tool viz., EDXRF spectrometer, through the use of same instrumental scattering constants for quantification in widely differing matrices like soil and plant. Quality control was done by quantitative reproduction of National Institute of Standards and Technology–Standard Reference Materials (NIST–SRMs). Subsequently, the second objective is to comparatively study elemental uptake in the cauliflower samples from contaminated and uncontaminated farms using the same calibration. This study suggests that the elemental concentrations in the root soils and leaves of the samples vary from farm to farm, whereby the concentrations of Cu, Zn and Pb in root soils of MSW‐contaminated farms are higher by almost an order of magnitude compared to uncontaminated farms. But the most notable feature of this study is the strikingly similar elemental concentrations in the edible flower part of all samples irrespective of the soil type. Plots of the ratio of concentrations of elements in leaf to soil and in flower to leaf, observed from the present EDXRF study suggests that a preferential uptake of elements takes place at different stages. Copyright © 2010 John Wiley & Sons, Ltd.     

EDXRF determination of impurities in potassium dihydrogenphosphate single crystals and raw materials

A fast and simple preconcentration procedure for recovering various cation impurities from potassium dihydrogenphosphate (KDP) single crystals and raw materials, followed by energy‐dispersive X‐ray fluorescence analysis (EDXRF), is described. The technique is based on the adsorption of metal 8‐hydroxyquinoline complexes from aqueous solutions of KDP on activated carbon, separation of the concentrate on a Nuclepore filter and subsequent determination by EDXRF. To fix activated carbon powder on a filter surface, an amount of 1‐hexadecanol is added to the KDP solution during the preconcentration procedure. The optimum conditions for the best recovery of the impurities were established. It was shown that a preconcentration factor of 100 can be achieved and the detection limit for a number of elements was down to 0.01 µg g^?1. The relative standard deviations were 6–17% for element concentrations of 0.2 µg g^?1. The method was successfully applied to the determination of Fe, Co, Cu, Ni, Zn, Mn, Ti and Bi in KDP single crystals and raw materials. Copyright © 2005 John Wiley & Sons, Ltd.     

High‐energy polarized‐beam EDXRF for trace metal analysis of vegetation samples in environmental studies

The aim of this work was to achieve improved instrumental sensitivity and detection limits for the determination of several trace elements (Cd, Pb, As, Cu, Fe and Zn) in different vegetation species collected at two mining areas in Spain (Aran Valley and Cartagena) by using new instrumentation based on high‐energy polarized‐beam energy‐dispersive x‐ray fluorescence analysis. Cd was determined by using its Kα line, while the mutual interference of As and Pb was solved by employing selective excitation conditions with targets of different materials. The use of a standardless fundamental parameter approach (IAEA QXAS) allowed the determination of other metals in the absence of suitable certified reference materials and to compensate accurately for self‐attenuation effects in the sample. The proposed methodology provides an alternative analytical tool to classical destructive analytical methods, commonly applied for the determination of these toxic elements in vegetation matrices, with accuracy and precision levels fulfilling the requirements for environmental studies. Copyright © 2006 John Wiley & Sons, Ltd.     

Transportable EDXRF analysis of environmental water samples using Amberlite IRC748 ion‐exchange preconcentration

Transportable energy‐dispersive X‐ray fluorescence spectrometers allow on‐site assessment of metal‐contaminated soils, sediments and other solids. Multi‐element analysis of liquid samples, such as surface water, groundwater, acid leach and aqueous soil extracts, would enhance on‐site environmental assessments. However, transportable spectrometers typically have detection limits for metals in waters of approximately 1–10 mg l^?1, whereas many toxic elements are regulated at concentrations of 1–100 µg l^?1. If detection limits for this technique can be lowered, then only one analytical tool, a transportable XRF spectrometer, may be sufficient for remote areas, increasing program flexibility and reducing the amount of equipment that needs to be purchased, transported and operated. This research develops an in‐field preconcentration technique using Amberlite IRC748 cation‐exchange resin, followed by XRF analysis of Fe, Ni, Cu, Zn and Pb at µg l^?1 concentrations in aqueous samples. The operational parameters tested to maximise analyte recovery included flow rate, and the mass and chemical form of the resin. The method was tested with extracts from landfill soils and surface waters from a derelict base metal mine. The method recovered Cu, Zn and Pb accurately, and Ni and Fe at concentrations satisfactory for screening purposes. Copyright © 2010 John Wiley & Sons, Ltd.     

Synchrotron-based X-ray fluorescence,imaging and elemental mapping from biological samples

The present study utilized the new hard X-ray microspectroscopy beamline facility, X27A, available at NSLS, BNL, USA, for elemental mapping. This facility provided the primary beam in a small spot of the order of ∼10 μm, for focussing. With this spatial resolution and high flux throughput, the synchrotron-based X-ray fluorescent intensities for Mn, Fe, Zn, Cr, Ti and Cu were measured using a liquid-nitrogen-cooled 13-element energy-dispersive high-purity germanium detector. The sample is scanned in a ‘step-and-repeat’ mode for fast elemental mapping measurements and generated elemental maps at 8, 10 and 12 keV, from a small animal shell (snail). The accumulated trace elements, from these biological samples, in small areas have been identified. Analysis of the small areas will be better suited to establish the physiology of metals in specific structures like small animal shell and the distribution of other elements.     

EDXRF and TXRF analysis of elemental size distributions and environmental mobility of airborne particles in the city of Riga,Latvia

Airborne particles were investigated in the central part of Riga during October 2000. Mass, black carbon and elemental concentrations of airborne particles were measured on Teflon filters from a dichotomous impactor, which samples fine (<2.5 µm) and coarse (2.5–10 µm) fractions of particles. In order to obtain more detailed information on the size distributions of different elements, a seven‐stage Batelle cascade impactor was used, in which quartz plates treated with silicone grease were utilized as backing for the different stages. Total reflection x‐ray fluorescence (TXRF) and energy‐dispersive x‐ray fluorescence (EDXRF) spectrometry were used for elemental analysis on the quartz plates and Teflon filters. The environmentally mobile part of the fine particle elements in the aerosol was determined by subtraction of x‐ray spectra measured before and after sequential leaching of the aerosol filters. The results of the different measurements show that naturally generated street dust and soil particles are dominant in coarse particles, whereas particles generated by human activities are dominant in the size fraction <0.5 µm. Copyright © 2004 John Wiley & Sons, Ltd.     

Nitrogen determination by SEM‐EDS and elemental analysis

This paper describes a methodology for the analysis of nitrogen by scanning electron microscope with an energy dispersive X‐ray spectrometer (SEM‐EDS). The methodology was developed to have a rapid and accurate alternative method to the elemental analysis by combustion and thermoconductivity detection that does not imply the decomposition of the sample. Two methods by SEM‐EDS were established: a quantitative method trying to construct a calibration curve with reference materials and another using the standardless method provided with the instrument software, and the results were compared with those obtained by elemental analysis using two instruments that work at different temperature. An important matrix effect was found when trying to construct a calibration curve for SEM‐EDS for any kind of material, being corrected when using the standardless method because this method corrects the matrix effect. The quantification of nitrogen by SEM‐EDS is a good alternative to elemental analysis by combustion and thermoconductivity detection in those cases where the sample has a very high decomposition temperature. Copyright © 2013 John Wiley & Sons, Ltd.     

Betterment in EDXRF analytical results for compositional characterization of mixed uranium thorium oxide samples with bead specimens compared with pressed pellet specimens

A comparative study on the energy dispersive X‐ray fluorescence analytical results of uranium determinations, in uranium and uranium–thorium mixed oxides, using specimens in the form of fused beads and pressed pellets, has been made. It was observed that in case of fusion bead specimens, the intensity of the analyte lines was approximately 1.6 times of that observed in pellet specimens under identical instrumental conditions. In case of uranium oxide samples, the analytical results with bead specimens were slightly better compared with the pellet specimens. However, in case of the uranium–thorium oxide mixtures, the average precision obtained with bead specimen was significantly better (1%, 1 s) in comparison with that achieved using pellet specimens (7%, 1 s). This difference may be due to the hardness of thorium oxide compared with uranium oxide, which affects the homogeneity of the pellet specimens prepared. In fusion bead method of sample preparation, even highly refractory material like ThO₂ forms uniform glass beads. Addition of internal standard further improves the analytical results, with reduction in the percent deviation of energy dispersive X‐ray fluorescence results from the expected values to 3% from 7% compared with that obtained using without internal standard. The fusion bead method of sample preparation will be very useful for characterization of sintered (U,Th)O₂ pellets, which are highly refractory and difficult to dissolve. Copyright © 2016 John Wiley & Sons, Ltd.