Multivariate calibrations for the SR‐TXRF determination of trace concentrations of lead and arsenic in the presence of bromine

A synchrotron radiation source and total reflection x‐ray fluorescence (SR‐TXRF) spectrometry were used for the determination of lead and arsenic in aqueous samples. To overcome the serious spectral interference between the two species and the overlap of another interfering element (bromine), a partial least‐squares regression (PLSR) method was used. The calibration models PLSR2 and PLSR1 were based on the x‐ray fluorescence emission signals (9.550–13.663 keV) for a set of 26 different mixtures containing the elements of interest, lead and arsenic, as well as bromine. The results obtained by PLSR1 and PLSR2 were compared with those obtained by the conventional univariate methodology. In the latter case, the areas of the secondary emission lines (Lβ for lead and Kβ for arsenic) were used to elaborate the analytical curves. The capacity of all optimized models was verified using five synthetic samples (external validation). Subsequently the best model was used to determine lead and arsenic recovery capacities when these metals are retained on two ion‐exchange resins (Dowex 50‐X8 and Dowex 1‐X8). The best multivariate model (PLSR1) allowed the determination of lead and arsenic with root mean square errors of prediction (RMSEPs) of 0.03 and 0.24 mg l^?1, respectively. The reduction of this parameter, with respect to the values obtained by conventional univariate methodology (0.26–0.03 mg l^?1 for lead and 0.30–0.24 mg l^?1 for arsenic), indicates that the proposed multivariate methodology really overcomes the problems associated with spectral interferences and minimizes the influence of an interfering agent (bromine). Copyright © 2005 John Wiley & Sons, Ltd.     

Investigation of heavy metal distributions along 15 m soil profiles using EDXRF,XRD, SEM‐EDX,and ICP‐MS techniques

The research of soil contamination by heavy metal is an important field due to its environmental and health implications. The goal was to study the elemental mobility as a function of depth. For this reason, the distribution of heavy metals (V, Cr, Co, Ni, Cu, Zn, As, Sn, and Pb) was investigated along soil profiles up to a depth of 15 m at 9 sampling sites in the Nilufer industrial district (Bursa, Turkey). Elemental analyses were done with the Epsilon 5 energy dispersive X‐ray fluorescence and inductively coupled plasma mass spectrometry equipment. Particle analysis was performed with a JEOL scanning electron microscope equipped with a Si(Li) X‐ray detector. The crystallographic compositions of oxide compounds in soil samples were identified by a Rigaku X‐ray diffraction instrument. Different parameters such as the soil's chemical (mineralogical structure, pH, and electrical conductivity) and physical properties (the number of blows, the stiffness index, the liquidity index, the plasticity index, and the water content) were analyzed. To assess the mobility of the heavy metals, diffusion (D) and convection coefficients (?) were calculated with the finite difference method. Convection was determined to dominate the studied region. In addition, the mobility coefficient was determined for each metal. High mobilities were determined for Zn and V, moderate mobilities for Cr, Ni, Cu, and As, and low mobilities were determined for Co and Pb. The results revealed that elements had reached depths of up to 15 m, causing irreversible soil contamination that may lead to environmental health issues.     

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.     

Inclusions and metal composition of ancient copper‐based artefacts: a diachronic view by micro‐EDXRF and SEM‐EDS

A diachronic view of the metallurgy in the Portuguese territory during the first three millennia after its appearance in the Iberian Peninsula is presented based on the current state of the art. Results of micro‐energy dispersive X‐ray fluorescence (micro‐EDXRF) analyses made on metal artefacts to determine their composition and scanning electron microscopy with energy dispersive analysis (SEM‐EDS) analyses to study microstructural features as inclusions are shown to illustrate trends and specificities of each chronological period. Generally, in early periods, namely during the Copper Age and first stages of the Bronze Age, unalloyed copper and arsenical copper were at use, and only by the Late Bronze Age (LBA) did tin bronze substitute almost completely the previous role of copper. In the Early Iron Age, during the Orientalising period, a general decrease in the average tin content in bronzes seems to happen. Regarding the inclusions observed in the metal matrix, these seem to suffer a diversification with the appearance of tin bronzes. By the Copper Age, only Cu? O and Cu? As? O inclusions are observed, while by the LBA Cu? S inclusions become regular, besides others less frequent, as Sn? O, Cu? S? Fe and Pb globules. Overall, with the present analytical study, the complementary character of micro‐EDXRF and SEM‐EDS in the study of ancient metals is demonstrated, providing a first general overview of the ancient metallurgy at the Portuguese territory which is of key importance to specific investigations of the future. Copyright © 2011 John Wiley & Sons, Ltd.     

Micro‐EDXRF study of Chalcolithic copper‐based artefacts from Southern Portugal

A collection of 39 metallic artefacts recovered in archaeological sites of Southern Portugal was studied by micro‐EDXRF to identify their compositions and the use of metal among ancient communities. Artefacts presented different typologies such as tools (e.g. awls, chisels and a saw) and weapons (e.g. daggers and arrowheads) mostly belonging to 2500–2000 BC. The results show copper with variable amounts of As and very low content of other impurities, such as Fe, Pb or Sb. Moreover, nearly half of the collection is composed by arsenical copper alloys, and an association was found between arsenic content and typology because the weapons group (mostly daggers) present higher values than tools (mostly awls). These results suggest some criteria in the selection of arsenic‐rich copper ores or smelting products. Finally, the compositions were compared to those of other collections from neighbouring regions and different chronology to determine metallurgical parallels. Copyright © 2015 John Wiley & Sons, Ltd.     

Characterization of x‐rays emerging from between reflector and sample carrier in reflector‐assisted TXRF analysis

The possible application of an Si reflector, which is placed just above the sample carrier in total reflection x‐ray fluorescence (TXRF) analysis, was investigated. The x‐rays that were emitted from an Mo tube and passed between the Si reflector and the Si sample carrier were analyzed with an Si drift detector. In our experimental setup, the angle between the reflector and the sample carrier can be changed by adjusting the inclination of the reflector. The intensity of the x‐rays that emerged from between the two Si surfaces drastically changed depending on the reflector angle. At a proper reflector angle, this intensity showed a maximum and, in addition, the Compton peak in the x‐ray spectrum was suppressed. When this x‐ray beam was used for excitation of TXRF signals, the highest intensity of x‐ray fluorescence emitted from the sample was detected, indicating that these experimental conditions are useful for the enhancement of TXRF intensities. Copyright © 2004 John Wiley & Sons, Ltd.     

Composition,components and sources of fine aerosol fractions using multielemental EDXRF analysis

The extensive characterization of the elemental composition of some important components and of major sources of particulate matter PM10 and PM2.5, sampled in parallel three times per week in Milan, for the whole year 2001 is described. More than 250 PM samples were analysed and major, minor and trace element concentrations were obtained by EDXRF. A strong seasonal modulation of particulate matter and element concentrations and an important contribution to PM from secondary compounds originating from gaseous precursors were observed. The main sources and their contribution were obtained by the application of absolute principal factor analysis to the large data set of elemental concentration. Copyright © 2004 John Wiley & Sons, Ltd.     

Unraveling the electronic structure of transition metal dimers using resonant four‐wave mixing

The potential of two‐color resonant and degenerate four‐wave mixing spectroscopy for investigations of the complex spectra of transition metal dimers is explored. Two‐color resonant and degenerate four‐wave mixing spectroscopy scans of the well‐known A‐X and B‐X transitions in Cu₂ are reported and compared with previous experimental data obtained from standard single‐resonance techniques. The selectivity of the method is shown to enable the measurement of isotopologue pure spectra without the need for isotopically enriched metal targets. Specific subsets of the rovibronic structure are separated in a congested spectral region of overlapping transitions. The sensitivity of the method compares satisfactorily with linear spectroscopic methods such as laser‐induced fluorescence and cavity ring‐down. A new laser vaporization source for the production of transition metal dimers and clusters has been constructed. The new design aims for a high number density and maximum possible shot‐to‐shot stability. The possibilities of further applications of non‐linear four‐wave mixing spectroscopy to Cu₂ and other transition metal dimers are discussed. Copyright © 2015 John Wiley & Sons, Ltd.     

Micro‐EDXRF investigation of Chalcolithic gold ornaments from Portuguese Estremadura

Chalcolithic gold artefacts assigned to the Bell Beaker Culture in Portuguese Estremadura were analysed by micro‐energy dispersive X‐ray fluorescence spectrometry. These high‐status jewels comprise beads of tubular, spiral and double‐conical type, a spiral ring and a wire fragment. The collection is mainly composed of gold with 8.7–16.3 wt% Ag and <0.04 wt% Cu. Additionally, there is a typologically uncommon double‐conical bead showing a lower Ag content (6.7 wt%). The relative intensity of the Ag‐Kα and Ag‐Lα X‐rays from artefacts established the existence of a surface layer depleted in silver, while the reasonable effective penetration depth of the Ag‐Kα (about 25–30 μm) provided suitable results for such high fineness gold alloys. A uniform Au–Ag composition at the joint indicates that the double‐conical bead was made by joining two sheets without solder. Overall, the collection shows a composition that is similar to known Chalcolithic gold in Portuguese Estremadura but different from coeval gold in Southwestern Iberian Peninsula. The distinct compositional pattern of Chalcolithic gold in Portuguese Estremadura seems to be inconsistent with the natural variability of silver content in alluvial deposits of gold in Iberian Peninsula, thus suggesting a continuous use of particular sources and limited exchange of nuggets and jewels with the neighbouring region. Copyright © 2017 John Wiley & Sons, Ltd.     

TXRF quantification of interfering heavy metals using deconvolution,cross‐correlation,and external standard calibration

We developed a general procedure that includes external standard calibration and a deconvolution of spectral signals, which determined with high accuracy the relative proportion and absolute quantification of elements that habitually overlap in total reflection X‐ray fluorescence spectroscopy. The deconvolution proposed takes advantage of the well‐known method of a cross‐correlation technique, offering improvements in identification of simultaneous signals and in the determination of the relative elemental proportions. The external standard calibration was studied determining its range of application for the elements of interest and implemented in certified standard samples producing excellent results for the quantification of the mentioned elements. In this paper, we show the quality of the results obtained for specific heavy metals of currently health and industrial interest in the range of linear response of 0.2–200 ng. Copyright © 2013 John Wiley & Sons, Ltd.     

Evaluation of error in the measurement of displacement vector components by using electronic speckle pattern interferometry

We report on the errors obtained by comparing in- and out-of-plane displacements calculated from the sensitivity matrix with all its components, and when only the component from the largest contributing of each one of the three interferometers is considered. Divergent illumination is considered in the evaluation of sensitivity vector to measure displacement vector components. This analysis is performed for a flat elastic target which is loaded in the x-direction and after in the z-direction. The technique applied is electronic speckle pattern interferometry.     

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.     

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.     

Assessment of teeth elemental content using μ‐EDXRF: effects by in‐office and at‐home bleaching products

The purpose of this in vitro study is to assess whether the elemental content of tooth enamel is altered when bleaching the teeth with bleaching gel. Because of tooth bleaching growing popularity and to match the public demands, manufacturers increased the range of bleaching products available, changing its presentation, techniques and concentration of active principles. This way, two different bleaching products were compared, one for in‐office and another for domestic use. In order to perform this evaluation, sound vestibular surfaces of anterior healthy teeth, extracted for periodontal or orthodontic reasons, were treated with the bleaching products accordingly to manufacturer instructions. Spectra were acquired using the M4 Tornado μ‐XRF setup, and quantitative calculations were performed using fundamental parameter method to determine the elemental composition of the analyzed samples before and after treatment. No significant statistical differences in the mineral content of the analyzed teeth were obtained. Copyright © 2014 John Wiley & Sons, Ltd.     

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.     

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.     

Zinc in native tissues and cultured cell lines of human prostate studied by SR‐XRF and XANES

During longlasting attempts to understand the aetiology of prostate cancer (CaP) on molecular level, attention has been paid to a unique capability of prostate epithelial cells to accumulate zinc. The latter plays role in a wide range of cellular processes such as the function of immune system, angiogenesis or apoptosis. Zinc has a significant antioxidant function, and its presence in prostate cells is strongly connected with their metabolism. This paper reports on the analysis of zinc concentration and oxidation level in the samples of human CaP tissues and cultured human prostate cell lines such as DU‐145, LNCaP and PC‐3, aided by x‐ray bioimaging. The study was performed by means of synchrotron radiation (SR) techniques. Bioimaging on cellular level, available through the SR x‐ray fluorescence (SR‐XRF) methods, applied to the samples of native prostate tissue, revealed a complexity of structures, while cell culture samples provided areas of homogeneity required for reliable analysis. SR‐XRF enabled us to establish the dependence of zinc concentration upon histological status of tissue (healthy, hyperplastic or cancerous). In‐depth studies of local chemical environment of an x‐ray absorbing zinc atom, including determination of Zn K‐edge position, were possible through the use of x‐ray absorption near edge structure (XANES) analysis. Copyright © 2009 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.     

Synchrotron‐induced EDXRF determination of uranium and thorium in mixed uranium–thorium oxide pellets

Uranium and thorium in their mixed oxides were determined by synchrotron‐induced energy dispersive X‐ray fluorescence (EDXRF) spectrometry. Mixed oxide calibration mixtures containing uranium and thorium in different relative amounts and approximately fixed amount of yttrium were prepared in the form of pellets. The EDXRF spectra of the pellets were measured at the microfocus XRF (BL‐16) beam line of Indus‐2 synchrotron radiation facility (Raja Ramanna Centre of Advanced Technology, Indore, India). Characteristic X‐ray lines U Lα, Th Lα, and Y Kα were used as analyte lines. Calibration plot for the determination of uranium was prepared by plotting amount ratios of U and Y against the intensity ratios of U Lα and Y Kα. Similarly, a calibration plot for thorium analysis was also made. The amounts of uranium and thorium in the sample mixtures prepared in similar way as the calibration mixtures were determined using the aforementioned calibration plots. The precision values obtained for uranium and thorium determinations were found to be 0.3 and 0.2% (relative standard deviation, 1σ), respectively. The EDXRF results deviated from the expected values by 1% for uranium and 0.9% for thorium determinations. These analytical features are much superior compared with laboratory‐based analysis results. Copyright © 2012 John Wiley & Sons, Ltd.