Direct determination of mineral nutrients in soybean leaves under vivo conditions by portable X-ray fluorescence spectroscopy

A portable energy dispersive X-ray fluorescence (XRF) spectrometer furnished with an Rh X-ray tube was evaluated for the determination of macronutrients and micronutrients in soybean leaves (Glycine max L.). XRF instrumental parameters were optimized in a univariate way, and emission intensities were measured for 60 s and under vacuum for macronutrients, and during 180 s, under air, and 305 μm Al/25.4 μm Ti filter, for micronutrients. Fresh and dried leaves were irradiated, and it was possible to identify P, K, Ca, S, Mn, Fe, Cu, and Zn Kα emission lines. For comparative purpose, the samples were also microwave assisted, digested and analyzed by inductively coupled plasma optical emission spectrometry. In general, linear correlations between K, Ca, Mn, Fe, Cu, and Zn concentrations in the tested samples and the corresponding portable XRF (pXRF) intensities were obtained. The linear correlation coefficients (R²) ranged from 0.42 to 0.86. In addition, the detection limits were suitable for plant nutrient diagnosis. It is demonstrated that pXRF is a simple and powerful tool for analysis of plant materials.     

Characterization of Indian Ayurvedic herbal medicines for their metal concentrations using WD‐XRF spectrometry

This article describes the details of metal concentrations evaluated using wavelength dispersive X‐ray fluorescence (WD‐XRF) spectrometry. A total of 22 elements, Na, Mg, Al, Si, P, S, K, Ti, Ca, Cr, Mn, Fe, Ni, Cu, Zn, As, Cd, Hg, Pb, Ba, Au, and Sn from 16 Ayurvedic medicines were characterized. The method was validated by analyzing the six certified reference materials of soil standards [NIST SRM‐2710, CRM 027‐050 (US‐EPA certified), PS‐1, TILL‐1 and TILL‐4 (Canadian certified reference material, CCRMP) and JSO‐1 (Japanese certified reference material)]. The elemental concentrations in all the standards are found to be within ± 10% of the reported values. Crystalline phases in the individual drug samples were explained by powder X‐ray diffraction (XRD) technique. Qualitative phase identification was done using the ICDD database. Copyright © 2010 John Wiley & Sons, Ltd.     

Determination of Mg and Ti in Ziegler–Natta catalysts by x‐ray fluorescence spectrometry

The metal content in Ziegler–Natta catalysts based on Ti and Mg derivatives could not be determined directly by x‐ray fluorescence (XRF) spectrometry owing to the instability of the catalyst. The samples were then calcined and the resultant Mg and Ti oxides were characterized by x‐ray diffraction (XRD). A series of synthetic standards were prepared with high‐purity MgO and TiO₂, since there were no available certified standards for the catalysts. Samples and standards were compressed with high‐purity H₃BO₃ flux. This protocol was shown to be reproducible, having a correlation coefficient of 0.9999. The metal contents determined by XRF were in accordance with those obtained by a complexometric titration (Mg) and a UV–visible spectrophotometric method (Ti). Copyright © 2004 John Wiley & Sons, Ltd.     

Applicability of MiniPal 4 compact EDXRF spectrometer for soil and sediment analysis

Optimum measurement parameters for analysis of soil and sediment samples with the compact MiniPal 4 (MP4)EDXRF spectrometer (PANalytical, Almelo, The Netherlands) were presented. The following elements were considered: K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As and Pb. Since the elements from low Z to medium Z region were covered, three measurement conditions (sequences) were defined. The following parameters were selected for measurement of the elements K, Ti, and V: voltage = 12 kV; current = 750 µA; filter material: Al_thin. Cr, Mn and Fe were measured at 20 kV; 300 µA with Al filter while for measurements of Ni, Cu, Zn, As, Pb, Rb, and Sr an Ag filter was selected and tube voltage and current were 30 kV and 300 µA. Each sequence was measured for 200 s and measurements were done in the air. MP4 spectrometer was characterized with acceptable precision, long‐term stability and satisfactory minimum detection limit for the analyses of soil and sediment materials. For the elements K, Mn, Fe, and Ti the precision of the analysis was better than 0.5% and for all the other elements better than 5%. Detection limits for sediment samples were 20 ppm for K, 6.1 ppm for Ti, 5.2 for Mn, 4 ppm for Fe, 4.2 ppm for As and less than 2 ppm for all the other elements. These values were significantly lower compared to typical concentrations of the same elements found in unpolluted soil and sediments. Copyright © 2008 John Wiley & Sons, Ltd.     

Effects of weathering on in situ portable X‐ray fluorescence analyses of geological outcrops: dolerite and rhyolite outcrops from the Preseli Mountains,South Wales

Laboratory experiments were undertaken to investigate the effect of weathering on dolerite and rhyolite samples from the Preseli Mountains, South Wales, an area of archaeological significance for the provenancing of archaeological artefacts. Portable XRF (PXRF) analysis was used to construct a depth profile of elemental concentrations through the weathering layer of suitable rock samples. These measurements were made by sequentially grinding away successive layers, each time measuring the newly exposed surface by PXRF. The elements studied included K, Ca, Ti, Mn, Fe, Ba, Nb, Pb, Sr, Y and Zr. In dolerite samples, Ca, Fe and Y were generally depleted in heavily weathered surface layers, whereas K and Pb were enhanced, the latter element significantly so, probably as a result of anthropogenic activities (emissions from leaded automobile fuel). Element behaviour in rhyolites was less consistent. A correction factor was derived for each element based on the ratio of the weathered surface concentration to the corresponding steady‐state (fresh rock) concentration beneath the altered layer. This correction factor was evaluated as a possible means of compensating for elemental discrepancies when measuring weathered surfaces. Improved data were obtained for a significant number of elements, but further work is required to evaluate this procedure fully. Copyright © 2005 John Wiley & Sons, Ltd.     

X‐ray spectrometry applied for characterization of bricks of Brazilian historical sites

This paper presents the results of X‐ray fluorescence (XRF) analysis of bricks sampled from historical places in Pernambuco, a state in the northeastern region of Brazil. In this study, twenty bricks found in historical sites were analyzed. Two bricks made in the 17th century, presumably used as ballast in ships coming from Holland, five locally manufactured bricks: one from 18th century, three from 19th century, and one from 20th century, and thirteen bricks collected from a recent Archeological investigation of Alto da Sé, in the town of Olinda. Qualitative determination of the chemical elements present in the samples was undertaken using a self‐assembled portable XRF system based on a compact X‐ray tube and a thermoelectrically cooled Si‐PIN photodiode system, both commercially available. X‐ray diffraction analysis was also carried out to assess the crystalline mineral phases present in the bricks. The results showed that quartz (SiO₂) is the major mineral content in all bricks. Although less expressive in the XRD patterns, mineral phases of illite, kaolinite, anorthite, and rutile are also identified. The trace element distribution patterns of the bricks, determined by the XRF technique, is dominated by Fe and, in decreasing order, by K, Ti, Ca, Mn, Zr, Rb, Sr, Cr, and Y with slight differences among them. Analyses of the chemical compositional features of the bricks, evaluated by principal component analysis of the XRF datasets, allowed the samples to be grouped into five clusters with similar chemical composition. These cluster groups were able to identify both age and manufacturing sites. Dutch bricks prepared with different geological clays compositions were defined.     

Spectroscopic investigations on kidney stones using Fourier transform infrared and X‐ray fluorescence spectrometry

Kidney stone is the most painful and prevalent urological disorder of the urinary system throughout the world. Thus, analysis of kidney stones is an integral part in the evaluation of patents having stone disease. Spectroscopic investigations of stones provide an idea about the pathogenesis of stones for its better cure and treatment. Hence, the present work targets multispectroscopic investigations on kidney stones using Fourier transform infrared (FTIR) and wave dispersive X‐ray fluorescence (WD‐XRF) spectroscopy which are the most useful analytical methods for the purpose of bio‐medical diagnostics. In the present study, FTIR spectral method is used to investigate the chemical composition and classification of kidney stones. The multicomponents of kidney stones such as calcium oxalate, hydroxyl apatite, phosphates, carbonates, and struvite were investigated and studied. Qualitative and quantitative determination of major and trace elements present in the kidney stones was performed employing WD‐XRF spectroscopy. The wide range of elements determined in the kidney stones were calcium (Ca), magnesium (Mg), phosphorous (P), sodium (Na), potassium (K), chlorine (Cl), sulfur (S), silicon (Si), iodine (I), titanium (Ti), iron (Fe), ruthenium (Ru), zinc (Zn), aluminum (Al), strontium (Sr), nickel (Ni), copper (Cu), and bromine (Br). For the first time, ruthenium was detected in kidney stone samples employing WD‐XRF in very low concentration. Our results revealed that the presence and relative concentrations of trace elements in different kinds of stones are different and depend on the stone types. From the experiments carried out on kidney stones for trace elemental detection, it was found that WD‐XRF is a robust analytical tool that can be useful for the diagnosis of urological disorders. We have also compared our findings with the results reported using XRF technique. The results obtained in the present paper show interesting prospects for FTIR and WD‐XRF spectrometry in nephrolithiasis. Copyright © 2017 John Wiley & Sons, Ltd.     

Time‐resolved x‐ray fluorescence for monitoring the intake of mineral nutrients in living plants

We have applied a time‐resolved means of measurement for studying living plants. The intake of mineral nutrients in a living plant such as stevia has been observed by this measuring instrument. A solution containing K, Ca, Mn, Fe, Cu, and Zn compounds was used as the mineral nutrient solution. The concentrations of the standard solutions were specifically chosen to obtain optimal intensities of the x‐ray peaks. The time dependence of the x‐ray fluorescence (XRF) intensity showed specific intake processes depending on the type of element. In addition, the experimental results suggest differences in the translocation of each element in the stevia stem. We conclude that time‐resolved XRF is a powerful technique for studying living plants. Copyright © 2007 John Wiley & Sons, Ltd.     

In vivo time‐resolved X‐ray fluorescence mapping measurements of Egeria densa immersed in Cr(VI) aqueous solution

In vivo time‐resolved Cr and Ca X‐ray fluorescence (XRF) mapping measurements were performed in a laboratory over a period of 69 days on a living common aquatic plant Egeria densa that was immersed in 5 mM K₂CrO₄ aqueous solution. The time and spatial resolution for each time‐resolved XRF map were ~1.6 days and 1 × 1 mm², respectively. The obtained XRF maps exhibited characteristic localized Cr and Ca areas where the XRF signals were especially strong (‘hot spots’), and this indicated the necessity of preliminary millimeter‐resolution surveying in XRF microscopy. Ca hot spots were detected prior to Cr(VI) immersion and nearly disappeared after immersion in deionized water for 2 weeks and the Cr(VI) solution for 1 week. After these immersions, a Cr hot spot was formed at approximately the same location of the missing Ca hot spot, which suggests that the original Ca‐accumulated regions were substituted for the isolation of Cr species when they were introduced. The sizes and intensity distributions of the Cr hot spots were sensitive to the Cr(VI) exposure approximately 1 week prior to each XRF measurement. This sensitivity suggests potential applications of E. densa as a Cr(VI) biomonitor in aquatic environments. Copyright © 2014 John Wiley & Sons, Ltd.     

The use of combined trace element XRF and EDXRD data as a histopathology tool using a multivariate analysis approach in characterizing breast tissue

The concentrations of K, Fe, Cu and Zn were measured in 77 breast tissue samples (38 classified as normal and 39 classified as diseased) using x‐ray fluorescence (XRF) techniques. The coherent scattering profiles were also measured using energy‐dispersive x‐ray diffraction (EDXRD), from which the proportions of adipose and fibrous tissue in the samples were estimated. The data from 30 normal samples and 30 diseased samples were used as a training set to construct two calibration models, one using a partial least‐squares (PLS) regression and one using a principal component analysis (PCA) for a soft independent modelling of class analogy (SIMCA) technique. The data from the remaining samples, eight normal and nine diseased, were presented to each model and predictions were made of the tissue characteristics. Three data groups were tested, XRF, EDXRD and a combination of both. The XRF data alone proved to be most unreliable indicator of disease state with both types of analysis. The EDXRD data were an improvement, but with both methods of modelling the ability to predict the tissue type most accurately was by using a combination of the data. Copyright © 2004 John Wiley & Sons, Ltd.     

Routine x‐ray fluorescence analysis of powder materials using the ‘VERBA‐XRF’ mode

A new version of the ‘VERBA‐XRF’ mode was developed for the determination of the contents of principal elements with atomic numbers Z > 10 and SUM9, that is, the sum of the contents of complementary elements with Z < 9 in powder materials without alloying with borax. An original set of equations provides determination of the SUM9. Analysis was made on 120 samples: dust from electric filters, clay, clinker, gypsum, bauxite, slag, candle‐end, shale, schlamm and chalk. The results obtained in the determination of the elements Fe, Ti, Ca, K, S, Si, Al and Mg have relative standard errors of 1–2%. The availability of the value of the SUM9 provided the possibility of determining chemical compositions in samples. The content of mineral white in natural gypsum was calculated. Copyright © 2004 John Wiley & Sons, Ltd.     

ED‐XRF set‐up for size‐segregated aerosol samples analysis

The knowledge of size‐segregated elemental concentrations in atmospheric particulate matter (PM) gives a useful contribution to the complete chemical characterisation; this information can be obtained by sampling with multi‐stage cascade impactors. In this work, samples were collected using a low‐pressure 12‐stage Small Deposit Impactor and a 13‐stage rotating Micro Orifice Uniform Deposit Impactor^?. Both impactors collect the aerosol in an inhomogeneous geometry, which needs a special set‐up for X‐ray analysis. This work aims at setting up an energy dispersive X‐ray fluorescence (ED‐XRF) spectrometer to analyse quantitatively size‐segregated samples obtained by these impactors. The analysis of cascade impactor samples by ED‐XRF is not customary; therefore, as additional consistency test some samples were analysed also by particle‐induced X‐ray emission (PIXE), which is more frequently applied to size‐segregated samples characterised by small PM quantities. A very good agreement between ED‐XRF and PIXE results was obtained for all the detected elements in samples collected with both impactors. The good inter‐comparability proves that our methodology is reliable for analysing size‐segregated samples by ED‐XRF technique. The advantage of this approach is that ED‐XRF is cheaper, easier to use, and more widespread than PIXE, thus promoting an intensive use of multi‐stage impactors. Copyright © 2011 John Wiley & Sons, Ltd.     

Focus on sulfur count rates along marine sediment cores acquired by XRF Core Scanner

The aim of this study is to investigate the information provided by sulfur count rates obtained by X‐ray fluorescence core scanner (XRF‐CS) along sedimentary records. The analysis of two marine sediment cores from the Niger Delta margin shows that XRF‐CS sulfur count rates obtained at the surface of split core sections with XRF‐CS correlate with both direct quantitative pyrite concentrations, as inferred from X‐ray powder diffraction (XRD) and sulfur determination by wavelength dispersive X‐ray fluorescence (WD‐XRF) spectrometry, and total dissolved sulfide (TDS) contents in the sediment pore water. These findings demonstrate the potential of XRF‐CS for providing continuous profiles of pyrite distribution along split sections of sediment cores. The potential of XRF‐CS to detect TDS pore water enrichments in marine sediment records, even a long time after sediment recovery, will be further discussed. Copyright © 2016 The Authors. X‐Ray Spectrometry Published by John Wiley & Sons Ltd.     

Levels and sources of heavy metal contamination in road dust in selected major highways of Accra,Ghana

Environmental studies have revealed significant contributions of vehicular exhaust emissions to high pollution levels in urban dwellings. The levels and sources of heavy metal contaminations of some major roads in Accra have been investigated in this work. Street dust samples collected from four major roads in Accra (Mallam Junction‐Weija road, John Teye‐Pokuase road, Tema Motorway and Tetteh Quarshie Interchange in Accra) were analysed for their elemental concentrations using energy‐dispersive X‐ray fluorescence. Twenty elements were identified: K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, As, Se, Br, Rb, Sr, Y, Zr and Pb. Significant concentration levels were obtained for K, Ca, Ti, V, Cr, Mn, Fe, Cu, Zn, Br, Rb, Sr, Y, Zr and Pb in all the samples and were used for the source identification. Enrichment factors and principal component analysis were used to verify the anthropogenic contribution to road dust. Results obtained for the enrichment factors showed moderate enrichment for V, Cr and Cu, while Zn, Br, Zr and Pb were significantly enriched. Principal component analysis identified four sources and their contributions to the elemental contents in the road dust. Natural crust, brake wear, tyre wear and vehicle exhaust emission were the four sources identified. The contribution of vehicular non‐exhaust emissions to heavy metal contamination in the road dust was found to be greater than that of exhaust emissions. Copyright © 2012 John Wiley & Sons, Ltd.     

Methodology for the determination of minor and trace elements in petroleum cokes by wavelength‐dispersive X‐ray fluorescence (WD‐XRF)

This article describes a methodology for the analysis of minor and trace elements in petroleum cokes by wavelength‐dispersive X‐ray fluorescence (WD‐XRF) spectrometry. The methodology was developed in order to have a rapid and reliable control method of these elements, because they determine coke end uses. There are a number of standard methods of chemical analysis by WD‐XRF or inductively coupled plasma atomic emission spectrometry (ICP‐OES) techniques. However, the standards that use WD‐XRF measurement give detection limits (L_D) above 10 mg·kg^?1 and only analyse a few elements of interest, whereas the ICP‐OES method requires extensive sample handling and long sample preparation times, with the ensuing errors. In order to improve the method described in the standard ASTM D6376 and reach the L_D and quantification limits (L_Q) required, the different stages of the process, ranging from sample preparation to measurement conditions: analytical line, detector, crystal, tube power, use of primary beam filters, and measurement time, were optimised. The samples were prepared in the form of pressed pellets, under conditions of high cleanliness of the mills, crushers, presses, and dies, and of the laboratory itself. The following reference materials were used in measurement calibration and validation: SRM 1632c, SRM 2718, SRM 2719, SRM 2685b, AR 2771, AR 2772, SARM 18, SARM 19, and CLB‐1. In addition, a series of materials were analysed by WD‐XRF and ICP‐OES, and the results were compared. The developed methodology, which uses WD‐XRF, is rapid and accurate, and very low L_D and measurement uncertainties were obtained for the following elements: Al, Ba, Ca, Cr, Cu, Fe, Ge, K, Mg, Mn, Mo, Na, Ni, P, Pb, S, Sb, Se, Si, Sn, Sr, Ti, V, and Zn. Copyright © 2010 John Wiley & Sons, Ltd.     

X‐ray fluorescence determination of Cs,Ba, La,Ce, Nd,and Ta concentrations in rocks of various composition

The technique has been developed for the quantification of small tantalum, cesium, barium, lanthanum, cerium, and neodymium concentration in rocks with X‐ray wavelength dispersive spectrometer S8 TIGER (Bruker AXS, Germany). The optimum conditions have been chosen for registration of the analyzed elements characteristic radiation and background positions. To determine the concentrations of analyzed elements accurately, the contribution of overlapping lines to the experimental intensities of the analytical lines has been taken into account. The sample of mass about 1.2 g has been pressed into pellet by the hydraulic press. Metrological studies showed that the accuracy in the determination of the concentration of analyzed elements for the developed technique meets the requirements for methods of III accuracy class. The Ta detection limits calculated for TaL_β1‐analytical and CsL_α1‐analytical lines were 2.6 and 3.4 ppm, respectively. The detection limit of Ba, La, Ce, and Nd was (in ppm), respectively, 4.3, 2.7, 5.8, and 4.7. The metrological characteristics of the previously developed and adapted techniques were compared. Ta concentration in granite pegmatite samples has been quantified. The samples of the highest tantalum content have been investigated additionally by powder diffraction and X‐ray microprobe analysis. The X‐ray diffraction method turned out to be insensitive to the detection of mineral phase of tantalum niobates, while micro‐XRF allowed detecting its presence in tourmaline grains. Copyright © 2017 John Wiley & Sons, Ltd.     

Assessing silicon deposits in Zilfi province,Saudi Arabia,using XRF and XRD techniques

The aim of this project is to create a geochemical database of the Nafud Desert in Zilfi Province, which lies 260 km northwest of Riyadh, capital of Saudi Arabia, and assess its potential as a silicon mine. The area of study was surveyed during December 2012 collecting 21 geological samples from 7 places (Alsabla, Almatal, Shlwan, Alaaga, Jaway, Magra and Althuare). Elemental composition was determined using X‐ray fluorescence spectrometry, while mineral content and crystallography analysis was performed using X‐ray diffraction. Analysis results revealed that silicon was abundant in the area, in fairly homogeneous amounts. Silica was found in concentrations of around 93% per sampled mass, and silicon concentrations were around 42%, in the surface layers down to the depth of 40 cm. Other elements (Al, K, Ca, Ti, Cr, Mn, Fe, Sr, Zr and Pd ) were present in very low concentrations, except for aluminium oxide, which was present in three areas (Jaway, Magra and Althuare) at concentrations around 5%, while Alsabla samples showed higher concentrations of CaO. Thus, according to the results, the Nafud Desert is a rich source of silicon that can be exploited very cheaply because of the presence of the raw material on the surface. Copyright © 2016 John Wiley & Sons, Ltd.     

Study of the Microstructure,Crystallographic Structure and Thermal Stability of Al–Ti–Nb Alloys Produced by Selective Electron Beam Alloying

This paper aims an investigation of the microstructure and crystallographic structure as well as the thermal stability of Al–Ti–Nb formed by selective electron beam surface alloying. The fabrication of the samples has been carried out using circular sweep mode, as two velocities of the sample movement have been chosen: V₁ = 1 cm/s and V₂ = 0.5 cm/s. The studied microstructure and crystallographic structure have been investigated by X-ray diffraction (XRD) and Scanning electron microscopy (SEM) respectively. The thermal behavior of the obtained surface alloys are evaluated by the coefficient of thermal expansion (CTE) which has been evaluated by neutron diffraction measurements at high temperature. The results show that in the earlier stages of formation, the microstructure of the intermetallic phase is mainly in the form of coarse fractions, but at the following moments they dissolve, forming separated alloyed zone and base Al substrate as the alloyed zone consists of fine (Ti,Nb)Al₃ particles dispersed in the Al matrix with small amount of undissolved intermetallic fractions. Formation of preferred crystallographic orientation as a function of the speed of specimen motion has not been observed. The performed neutron diffraction measurements show that the lattice parameters of the obtained intermetallic (Ti,Nb)Al₃ are less upshifted in comparison to pure Al. It has been found that the aluminium lattice is much more unstable at high temperatures than that of the intermetallic phase. The CTE for the intermetallic phase is 8.70 ppm/K for a axis and 7.75 ppm/K for c axis respectively while considering Al it is 12.95 ppm/K.     

藏药珠西的化学成分与结构分析

采用X射线荧光(XRF)、电感耦合等离子体发射光谱(ICP-OES)和X射线衍射(XRD)对不同来源藏药珠西中的元素成分和结构组成进行测定,以期揭示其药理作用的物质基础。XRF和ICP-OES分析结果表明,藏药珠西中主要元素为Fe,S和O,及少量的Si,Na,Mg,Al,K,Ni,Ca,Ti等元素。XRD分析表明,藏药珠西中主要存在立方晶系FeS2,此外还含有少量的斜方晶系Fe+3O(OH)等。通过XRF,ICP-OES和XRD分析,获得了藏药珠西的化学成分和结构组成基本数据,为其药理作用物质基础的揭示和质量标准的制定提供了科学依据。     

Energy‐dispersive x‐ray fluorescence analysis of modern coloured glasses from Marinha Grande (Portugal)

The elemental composition (K, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Sr, Ba, Nd and Pb) of modern coloured glasses was obtained by energy‐dispersive x‐ray fluorescence (EDXRF) spectrometry. This non‐destructive technique is frequently used in the analysis of historical glass objects. Two reference glasses were also measured to assess the overall accuracy of the EDXRF method. Reference and unknown glasses were analysed without any preparation. The coloured glass samples studied belong to the Glass Museum of Marinha Grande and were chosen from two distinct collections, which were characterized by the different concentrations of some elements (K, Ti, Cr, Mn, Fe, Ba and Pb). The determined major elements allowed the identification of two raw materials used in glass manufacture, sand and lime. Multivariate statistical analysis, namely principal component extraction, simplified the identification of some of the colouring chemical elements, associating them with the different colours of the glass objects. Copyright © 2003 John Wiley & Sons, Ltd.