Heavy metal analysis around Iskenderun Bay in Turkey

The heavy metal analysis around Iskenderun Bay in Turkey was carried out using mosses, soils, mussels, and sediments. This region is one of the most industrial areas of Turkey, including iron–steel plants, beverage, liquefied petroleum gas (LPG) plants, and oil transfer docks. Energy dispersive X‐ray fluorescence spectrometry (Epsilon 5, PANalytical, Almelo, The Netherlands) was used to analyze all samples. V, Cr, Mn, Fe, Ni, Cu, Zn, As, and Pb elements were observed in all samples studied. Although Ce was detected in some mosses and soils, Sn was detected only in some moss samples. Pb concentrations in the moss samples are higher than the soil, the mussel, and the sediment samples. This can be attributed to the mosses that absorb heavy metals such as Pb easily from the air. As the aim of this study was to analyze heavy metals, the evaluation of these elements with their potential hazards for ecology and humans is briefly discussed. Copyright © 2010 John Wiley & Sons, Ltd.     

Application of high‐energy polarized energy‐dispersive x‐ray fluorescence spectrometry to the determination of trace levels of As,Hg, and Pb in certifiable color additives

Advances in x‐ray fluorescence (XRF) using high‐energy polarized energy‐dispersive (ED)XRF spectrometry (PEDXRF) were applied to the determination of trace As, Hg, and Pb in various color additives subject to batch certification by the U.S. Food and Drug Administration (FDA). The objectives of this study were to simplify sample preparation for quantitative determination of these elements and, if possible, to achieve improved sensitivity and detection limits compared to techniques currently used for certification. PEDXRF was compared with wavelength‐dispersive x‐ray fluorescence spectrometry (WDXRF) and inductively coupled plasma – mass spectrometry (ICP‐MS) for the analysis of trace levels of As, Hg, and Pb in certifiable color additives. For these light matrices, PEDXRF provided better signal‐to‐noise and allowed quantitation in smaller amounts of color additive relative to WDXRF and equal or better precision to ICP‐MS. Determination of these trace elements in a variety of color additives was possible relative to calibrations generated from one color additive using specimens prepared simply by pouring the color additive powder into an XRF sample cup. Published 2016. This article is a U.S. Government work and is in the public domain in the USA     

A critical analysis of the application of EDXRF spectrometry on complex stratigraphies

In this work, the potentialities and limits of the investigation by portable energy‐dispersive X‐ray fluorescence (XRF) of complex polychrome stratigraphies are discussed. Data are affected by the mutual influence effects of the chemical elements that characterize mineral pigments, by the sequence and the thickness of the paint layers in the stratigraphies and by the size of pigment grains. Sequences of pictorial layers, which produce the typical stratigraphy of cold‐painted terracotta and wooden sculptures, have been prepared and then analysed by means of two portable X‐ray spectrometers: Innov X Systems Alpha 4000 (Tantalum X‐ray tube, 40 kV and 7 µA) and Assing Lithos 3000 (Molybdenum X‐ray tube, 25 kV and 300 µA). For each layer of pigment, the XRF spectrum was acquired and the areas of K and L peaks of characterizing elements were calculated. Moreover, the thickness of the layers was determined using XRF data following an algorithm already shown and the values have been compared with those measured on polished cross sections observed by optical microscope in reflected light. Copyright © 2011 John Wiley & Sons, Ltd.     

Deconvolution of distinct lithology chemistry through oversampling with the Mars Science Laboratory Alpha Particle X‐Ray Spectrometer

The Alpha Particle X‐Ray Spectrometer (APXS) determines the chemical composition of Martian rocks and soils on‐board both active National Aeronautics and Space Administration (NASA) rovers using X‐ray emission spectroscopy through complementary particle‐induced X‐ray emission (PIXE) and X‐ray fluorescence (XRF) excitation methods. A single APXS spectrum represents the sum of the signals from within the instrument's field of view (FOV). In the past, features smaller than the FOV have been investigated through repeated measurements with stepwise lateral offsets. These lateral offsets allow for empirically extracting, through elemental correlations, distinct compositions of different features. Here, we present a novel analytical method for deconvolving the endmember chemistry of visually distinct components through oversampling and the integrated analysis of the elemental data and supporting images. We discuss specifically the method's application to three targets investigated by the Mars Science Laboratory rover Curiosity during its traverse, as well as the added information that can be gained from this method in the future. Copyright © 2016 John Wiley & Sons, Ltd.     

Intensity correction of WD‐XRF spectra from 2θ to energy

Generally, the energy‐dispersive X‐ray fluorescence spectra are plotted as an equi‐energy interval with the constant energy resolution. On the other hand, the wavelength‐dispersive X‐ray fluorescence spectra are usually measured with an equi‐angle interval supposed the constant angular resolution. When the wavelength axis of wavelength‐dispersive X‐ray fluorescence spectra is converted into energy, the intensity should be also corrected. This intensity correction is important even for a narrow scan range such as Pb Lα and Lβ peaks. The intensity ordering is Lβ > Lα for 2θ plot, but it becomes Lα > Lβ for energy plot. The detailed conversion equations for abscissa and ordinate axes are presented. Copyright © 2012 John Wiley & Sons, Ltd.     

3D elemental distribution images in biological samples by XRFµCT

An X‐ray transmission microtomography (CT) system combined with an X‐ray fluorescence microtomography (XRFµCT) system was implemented in the Brazilian Synchrotron Light Laboratory (LNLS), Campinas, Brazil. The aim of this work was to determine the elemental distribution in biological samples (breast, prostate and lung samples) in order to verify the concentration of some elements correlated with characteristics and pathology of each tissue observed by the transmission CT. The experiments were performed at the X‐ray fluorescence beamline (D09B‐XRF) of the Brazilian Synchrotron Light Laboratory, Campinas, Brazil. A quasi‐monochromatic beam produced by a multilayer monochromator was used as an incident beam. The sample was placed on a high‐precision goniometer and translation stages that allow rotating as well as translating it perpendicularly to the beam. The fluorescence photons were collected with an energy dispersive HPGe detector placed at 90° to the incident beam, while transmitted photons were detected with a fast Na(Tl) scintillation counter placed behind the sample on the beam path. The CT images were reconstructed using a filtered‐back projection algorithm and the XRFµCT images were reconstructed using a filtered‐back projection algorithm with absorption corrections. The 3D images were reconstructed using the 3D‐DOCTOR software. Results from the 3D visualization showed that the distribution of iron, copper and zinc is different and heterogeneous from the analyzed samples. Copyright © 2011 John Wiley & Sons, Ltd.     

A device for X‐Ray elemental mapping using annular radioisotope source

An energy‐dispersive system is described for elemental mapping by X‐ray fluorescence spectrometry. The present study describes the design of an X‐ray fluorescence spectrometer and presents its performance in elemental mapping applications. The spectrometer is based on a new ring‐shaped collimator with a pinhole in the center of it and a ring‐shaped Am‐241 isotope mounted in the collimator as a source for excitation of X‐ray fluorescence. The photons were detected by high‐resolution Si (Li) detector coupled to a multi‐channel analyser and cooled by liquid nitrogen. In this study, we used two samples; one of them was made from pure elemental powders, and the second one was a piece of a stone and three types of maps were plotted. In the maps type one, the areas of the elements were shown with a single color. These maps only show the location of the elements in the sample. In the maps type two, the area of each element was shown with different colors because of the count (intensity) related to the area. In the third type of the maps for each element, depending on the elements' position on the sample, the counts were plotted in three dimensions. The areas with higher intensity have greater height, and areas with lower intensity have lower altitude. These two last types of maps provide information about the homogeneity or heterogeneity of the elemental distribution in the samples. The spectrometer can perform non‐destructive analyses of samples and objects in the air. Copyright © 2017 John Wiley & Sons, Ltd.     

Determination of gold and silver in dross using EDXRF technique

Gold and silver in dross were determined by energy‐dispersive X‐ray fluorescence technique. Sample was prepared by pressed pellet method using microcrystalline cellulose powder as binder, and a method of standard additions was used for quantification. L_β X‐ray of gold (11.4 keV) and K_β X‐ray of silver (24.9 keV) were used for analysis. The measured concentrations of gold and silver were 132 ± 8 and 1181 ± 84 mg kg^?1, respectively. The results were validated by instrumental neutron activation analysis technique. The t‐test indicated that there was no significant difference between results obtained by the two techniques. Energy‐dispersive X‐ray fluorescence is a simple, precise and accurate technique for the determination of gold and silver in dross. Copyright © 2014 John Wiley & Sons, Ltd.     

Analysis of the Hoard of Beçin using X‐ray‐based techniques

Four hundred and sixteen silver coins stemming from the Ottoman Empire (16th and 17th centuries) were analyzed to confirm the fineness of the coinage as well as to study the provenance of the alloy used for the coins. As most of the coins showed the typical green patina on their surfaces due to corrosion processes that have led to the depletion of copper in the near surface domains of the silver coins in comparison to their core composition, small samples had to be taken, embedded in synthetic resin, and cross sectioned to investigate the true‐heart metal composition. μ‐synchrotron micro X‐ray fluorescence analysis and μ‐proton‐induced X‐ray emission were applied to determine the silver contents as well as the minor and trace elements. The type of the alloy was investigated as well as if coins minted in different locations demonstrated homogeneous traits concerning the predominant impurities (Au and Bi), which could suggest a common ore. Finally, energy‐dispersive microanalysis in a scanning electron microscope was applied to study the homogeneity/heterogeneity of the coins and the presence of surface enrichments and to explain differences between the μ‐synchrotron micro X‐ray fluorescence analysis and μ‐proton‐induced X‐ray emission measurements concerning the main component. In general, the silver content of the analyzed specimen varies between 90 and 95%. These outcomes have not supported the historical interpretations, which predict that during the period studied, a debasement of approximately 44% of the silver content of the coins should have occurred. Copyright © 2012 John Wiley & Sons, Ltd.     

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.     

Quantitative determination of mineral phase effects observed in APXS analyses of geochemical reference materials

Calibration of the Curiosity Rover's alpha particle X‐ray spectrometer (APXS) was accomplished using geochemical reference materials and a fundamental parameters treatment of the X‐ray fluorescence and particle‐induced X‐ray emission (PIXE) excitation processes. For most major and minor elements the influence of different rock types was not significant. For the three light elements, Na, Mg, and Al, which are excited almost entirely by PIXE, systematic differences among felsic and mafic rocks were observed. A qualitative explanation is found in the very shallow interrogation depth (a few microns), which suggests that the X‐rays of these elements must emerge from a single mineral rather than an assumed average over the various minerals present. A quantitative explanation was sought by determining the mineralogy of several reference materials and computing their expected PIXE X‐ray yields with an adaptation of the yield prediction sub‐routine GUYLS in the Guelph PIXE software package GUPIX. The complexity of assigning the certified overall element mass fractions to specific minerals limited this exercise to cases with only a few minerals present. Good agreement was found between the X‐ray yields determined in the calibration exercise and those predicted in this new approach. It is expected that automation of the computational approach may enable examination of mineralogically more complex reference materials. This might also offer a means of coupling results from the X‐ray diffraction and APXS instruments on Mars. Copyright © 2014 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.     

The influence of polarization and filtration of beams on the ED spectrometers sensitivity

The topic under discussion is the influence of X‐ray polarization and filtration, as well as the influence of detectors count rate on sensitivity and detection limits (DLs) in spectrometers with energy dispersion (EDS). Parameters calculation technique for searching optimal analysis conditions has been developed. Typical DLs of elements with medium and high atomic numbers on various spectrometers are given (on wave dispersive spectrometers (WDS), energy dispersive spectrometers (EDS) without polarization and energy‐dispersive polarized‐beam X‐ray spectrometers (EDPXRS). Apparently, EDS variants are preferred for determining elements with Z > 62–65, and EDPXRS spectrometers with concave targets and increased aperture are preferred for determining elements with medium atomic numbers.     

Quantitative analysis of sulphides and sulphates by WD‐XRF: Capability and constraints

In the course of geochemical characterisations, total sulphur analyses are common practice although a differentiated quantification of sulphur species could provide valuable additional information, particularly when samples from unclear or changing redox environments are investigated. Unfortunately, a likewise simple distinct determination of just sulphide and sulphate already requires considerable efforts as sample dissolution or extra equipment. Two comparatively convenient strategies based on extended routine wavelength dispersive X‐ray fluorescence spectrometry measurements were adapted and optimised for a reliable quantitative sulphur speciation whereupon the matrix influence can be neglected. About 100 synthetic samples with different concentration ratios of sulphides and sulphates have been prepared and analysed using a WD‐XRF spectrometer. The first approach to differentiate between oxidation states and their quantification takes advantage of the Kα_1,2 doublet shift. Sulphide lines are located at 2309 eV, sulphate lines at 2310 eV, and mixtures can be quantified by a regression curve of fluorescence energy versus sulphide amount. Secondly, the amount of sulphide can be calculated by a regression curve based on the quotient Kβ′/Kβ of the sulphur peak heights or areas. In contrast to sulphides, sulphates show sulphur Kβ′ satellite peaks, and the intensity of S Kβ′ increases with the increasing sulphate content. However, the applicability of this second method is limited by the lower detection limit of sulphide (10 g kg^?1 sulphide in the sample) and interferences with lead (Pb Mβ line). Both approaches are validated by an independent method, Electrothermal Vaporisation Inductively Coupled Plasma Optical Emission Spectrometry, and already employed in investigations of ore‐containing mining dumps in Saxony/Germany. Copyright © 2016 John Wiley & Sons, Ltd.     

Evaluation of the concentration of chemical elements in suspended particulate matter inside a small bronze and iron foundry industry,using a streaker sampler and EDXRF

The aim of this study was to determine and evaluate the temporal profiles of the concentration of chemical elements in the suspended particulate matter present inside a small bronze and an iron foundry industry. To collect the samples, we used a streaker sampler that separates particles with aerodynamic diameters smaller than 10 µm (PM₁₀) in two fractions: fine (particles with aerodynamic diameters less than 2.5 µm; PM_2.5) and coarse (between 2.5 µm and less than 10 µm; PM_10–2.5). The collection of samples was taken every 20 min during a total time of 8 and 5 h of molding and casting of bronze and iron, respectively. The samples collected in the form of strips on a filter (fine fraction) and an impactor (coarse fraction) were analyzed by the energy dispersive X‐ray fluorescence technique. In the excitation, an X‐ray tube with Mo target and Zr filter was used, operated at 30 mA/30 kV. For detecting the characteristic of X‐rays, a semiconductor Si(Li) detector was used, coupled to a multi‐channel spectrometer, with a 300 s excitation/detection time. The results of the temporal profiles of chemical element concentrations in coarse and fine fractions were discussed and compared with the maximum levels set by the Brazilian and international environmental agencies. Copyright © 2013 John Wiley & Sons, Ltd.     

The advantages of using digital signal processing in polarized x‐ray fluorescence analysis

Improving the specificity and productivity of XRF is of great relevance for the determination of trace elements in samples of diverse origin. The advantages of using digital signal processing in energy‐dispersive polarized x‐ray fluorescence analysis are demonstrated by comparing the instrumental sensitivities achieved with those obtained by using a conventional analogue signal processing‐based spectrometer. A compact geometry secondary target arrangement was designed to increase the effective solid angles and to reduce the distances between secondary target, sample and detector, thus achieving larger x‐ray fluxes for both the excitation and detection process, resulting in improved instrumental sensitivities. The performance of both spectrometers was evaluated for two different detectors: an Si(Li) detector and a thermoelectrically cooled passivated‐implanted planar silicon detector (X‐PIPS). The uncertainties achieved and accuracy are illustrated for the analysis of a group of sediment and organic‐origin certified reference materials using two different quantitative procedures. Copyright © 2006 John Wiley & Sons, Ltd.     

Nondestructive rare earth element imaging of fish teeth from deep‐sea sediments

X‐ray fluorescence computed tomography is an emerging imaging modality that allows for the nondestructive reconstruction of the internal distribution of elements within a sample. The common use of X‐ray excitation energy (up to approximately 20 keV) has necessitated the use of l ‐shell fluorescence for heavy elements. In this study, based on high energy X‐ray at BL13W1 of the Shanghai Synchrotron Radiation Facility, we employed high‐energy excitation for tomographic imaging of the heavy metals (rare earth elements) in fish teeth from deep‐sea sediments on the micrometer scale using K‐shell X‐ray fluorescence. The virtual cross‐sectional distribution of La, Ce, Pm, Pr, Nd, and Sm were obtained, thereby providing a feasible approach for analyzing the enrichment mechanism of rare earth elements. Copyright © 2015 John Wiley & Sons, Ltd.     

EDXRF and multivariate statistical analysis of fragments from Marajoara ceramics

In this work, 102 fragments of Marajoara ceramics, belonging to the National Museum collection (Rio de Janeiro, Brazil), were analyzed using energy dispersive X‐ray fluorescence (EDXRF) and principal component analysis (PCA) in order to identify possible groups of samples that present similar behaviors or different characteristics. This information will give an important aid to a more accurate classification of these artifacts. The EDXRF measurements were carried out with a portable system developed in the Nuclear Instrumentation Laboratory consisting of an Oxford TF3005 X‐ray tube, with W anode, and an Si‐PIN XR‐100CR detector from Amptek, working at 25 kV and 100 µA, acquisition time of 600 s and a beam collimation of 2 mm. PCA applied to the X‐ray fluorescence results revealed a clear cluster separation to the samples. Copyright © 2009 John Wiley & Sons, Ltd.     

Energy dispersive X‐ray fluorescence analysis of archeological metal artifacts from the Final Bronze Age

Energy dispersive X‐ray fluorescence (EDXRF) is widely used in the study of archeological metal artifacts, heritage and art history, where the fragile nature of the objects requires the use of noninvasive techniques such as the EDXRF, which in addition, is fast and very affordable. An EDXRF analysis of copper‐based artifacts from Late Bronze Age metal hoards from Central Portugal is presented. The EDXRF measurements were carried out by using an X‐ray tube with a Mo anode and a commercial Si‐PIN detector. The data acquisition was performed by keeping small distances between the X‐ray window, the sample and the detector. Both patinated and polished areas were analyzed: the relative composition of the artifacts was inferred from the fluorescence spectra obtained. Copyright © 2012 John Wiley & Sons, Ltd.