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.     

A miniature X‐ray tube approach to measuring lead in bone using L‐XRF

Using a miniature X‐ray tube and silicon PiN diode detector, an approach to measuring lead (Pb) in bone phantoms was tested. The X‐ray tube was used to excite L‐line X‐ray fluorescence (L‐XRF) of lead in bone phantoms. The bone phantoms were made from plaster of Paris and dosed with varying quantities of lead. Phantoms were made in two sets with different shapes to model different bone surfaces. One set of bone phantoms was circular in cross‐section (2.5‐cm diameter), the other square in cross‐section (2.2 cm × 2.2 cm). Using an irradiation time of 180 s (real time), five trials were run for each bone phantom. Analysis was performed for both Lα and Lβ lead X‐rays. Based on these calibration trials, (3σ₀/slope) minimum detection limits of 7.4 ± 0.3 µg Pb g^?1 (circular cross‐section) and 8.6 ± 0.6 µg Pb g^?1 (square cross‐section) were determined for the bare bone phantoms. To simulate a more realistic in vivo scenario with soft tissue overlying bone, further trials were performed with a resin material placed between the experimental system and the bone phantom. For the square cross‐section bone phantoms, a layer of resin with a thickness of 1.2 mm was used, and a minimum detection limit of 17 ± 3 µg Pb g^?1 determined. For the circular cross‐section phantoms, a layer of resin with an average thickness of 2.7 mm was used. From these, a more realistic minimum detection limit for in vivo applications (43 ± 7 µg Pb g^?1) was determined. Copyright © 2011 John Wiley & Sons, Ltd.     

Monte Carlo simulation code for confocal 3D micro‐beam X‐ray fluorescence analysis of stratified materials

Stratified materials are of great importance for many branches of modern industry, e.g. electronics or optics and for biomedical applications. Examination of chemical composition of individual layers and determination of their thickness helps to get information on their properties and function. A confocal 3D micro X‐ray fluorescence (3D µXRF) spectroscopy is an analytical method giving the possibility to investigate 3D distribution of chemical elements in a sample with spatial resolution in the micrometer regime in a non‐destructive way. Thin foils of Ti, Cu and Au, a bulk sample of Cu and a three‐layered sandwich sample, made of two thin Fe/Ni alloy foils, separated by polypropylene, were used as test samples. A Monte Carlo (MC) simulation code for the determination of elemental concentrations and thickness of individual layers in stratified materials with the use of confocal 3D µXRF spectroscopy was developed. The X‐ray intensity profiles versus the depth below surface, obtained from 3D µXRF experiments, MC simulation and an analytical approach were compared. Correlation coefficients between experimental versus simulated, and experimental versus analytical model X‐ray profiles were calculated. The correlation coefficients were comparable for both methods and exceeded 99%. The experimental X‐ray intensity profiles were deconvoluted with iterative MC simulation and by using analytical expression. The MC method produced slightly more accurate elemental concentrations and thickness of successive layers as compared to the results of the analytical approach. This MC code is a robust tool for simulation of scanning confocal 3D µXRF experiments on stratified materials and for quantitative interpretation of experimental results. Copyright © 2011 John Wiley & Sons, Ltd.     

Feasibility for chemometric energy dispersive X‐ray fluorescence and scattering (EDXRFS) spectroscopy method for rapid soil quality assessment

Soil quality assessment (SQA) is important for modulating agricultural productivity and thus requires simple and rapid analysis of soil (macro & micro) nutrients (here called soil quality indicators – SQIs). We report proof of concept of a chemometrics‐assisted energy dispersive X‐ray fluorescence and scattering (EDXRFS) spectroscopy technique for direct rapid analysis of SQIs. The EDXRFS method exploits, in addition to fluorescence, the X‐ray scatter peaks obtained non‐invasively from soils to develop a calibration strategy for quantitative analysis of SQIs in model clay soils doped with micronutrients (Fe, Cu, and Zn) and macronutrients (NO₃^?, SO₄^2?, and H₂PO₄^?). The soil samples and certified reference materials IAEA Soil‐7 and IAEA Soil‐1 (used to build spectral library for soil classification) were irradiated at various live times (to simulate different signal‐to‐noise ratios of analyte signals and analysis speed) in a teflon holder and were analyzed using a ¹⁰⁹Cd‐excited XRF spectrometer. Principal components analysis was used for spectral data compression and pattern recognition (including for those SQI spectral signatures without any visibly discernible characteristic X‐ray lines), whereas partial least squares regression and artificial neural networks were used to build a calibration and quantitative analysis strategy. The method furnishes soil micronutrient and macronutrient information simultaneously and rapidly (t = 200 s). To the best of the authors' knowledge, this is the first time that an XRF method has demonstrated spectroanalytical potential for quantitative macronutrients analysis in soils applicable to routine SQA. Coupling EDXRFS with multivariate chemometrics enables rapid and reliable assessment of chemical SQIs. Copyright © 2011 John Wiley & Sons, Ltd.     

A risk assessment study of heavy metals in ambient air by WD‐XRF spectrometry using aerosol‐generated filter standards

A risk assessment study of the air quality in the surrounding of roads covered with slags coming from the non‐ferrous metal industry was performed. A monitoring campaign was carried out at three locations in Flanders by collecting the PM10 fraction and the total suspended particulates (TSP) of the airborne dust particles, entrapping heavy metals, on membrane filters. The heavy metal concentration on the dust filters was determined by wavelength‐dispersive x‐ray fluorescence (WD‐XRF) spectrometry. The XRF calibration curves were set up with filter standards prepared in the laboratory using an aerosol‐generated loading system. The acquired WD‐XRF results were confirmed by inductively coupled plasma atomic emission spectrometric (ICP‐AES) measurements after acid digestion on a selected number of filters. Electron probe microanalysis (EPMA) confirmed that aerosol‐loaded filter standards and dust filters with a concentration level of the analyzed element below 3300 ng cm^?2 were homogeneously distributed. Dust filters with higher concentrations, and especially filters loaded with the TSP fraction, reflected an inhomogeneous distribution of the analyzed element on the filter. The WD‐XRF analytical results acquired in the monitoring campaign revealed that the concentration of Pb on the dust filters never exceeded the immission standard (yearly average) of 2000 ng m^?3. It can be stated that the impact on human health is limited and can still be reduced by covering the polluted roads with a layer of asphalt. Further evaluation of soil and water samples from the nearby surroundings reveals that the heavy metal content in the slags makes an important contribution to environmental pollution, especially the contamination of groundwater. Copyright © 2003 John Wiley & Sons, Ltd.     

A comparative study on the total reflection X‐ray fluorescence determination of low Z elements using X‐ray tube and synchrotron radiation as excitation sources

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

Comparison between XRF and EPMA applied to study the ionic exchange in zeolites

Zeolites are crystalline aluminosilicates consisting of SiO₄ and AlO₄ tetrahedral as primary units. One peculiar characteristic of zeolites is the ion exchange capacity defined as the capacity to locate specific cations in the framework of zeolites; it depends on the chemical composition and varies with the structure of the zeolite and with the cation nature. This work studies the exchange of the Na⁺ monovalent cation of 5A and 13X synthetic zeolites by the Ca²⁺ bivalent cation present in a CaCl₂ solution. X‐ray fluorescence (XRF) and electron probe microanalysis (EPMA) techniques were used to determine the cation exchange capacity (CEC). The efficiencies of the two X‐ray detectors were compared and the minimum detection limits of the zeolite elements were calculated. Although both techniques differ in the sample excitation mode, the results obtained were compatible. The results showed that the CEC was higher for the 5A zeolite, in agreement with its lower SiO₂/Al₂O₃ ratio and its greater BET area. It was also found that the amount of Na⁺ ions exchanged by Ca²⁺ ions was in complete agreement with the corresponding molar balance. The determination of the CEC using X‐ray spectroscopy techniques can be considered a novelty as XRF and EPMA techniques permit to analyze the sample directly. Copyright © 2009 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.     

Preparation of arsenic‐containing white rice grains as calibration standards for X‐ray fluorescence analysis of total arsenic in cereals

A preparation method of arsenic‐containing white rice grains as calibration standards was developed for the X‐ray fluorescence (XRF) analysis of arsenic in rice grains. Calibration standards were prepared by adding 10 g of white rice grains (from Japan) to 100 ml methanol‐containing dimethylarsinic acid corresponding to 2–100 µg arsenic. The mixture was heated, dried at 150 °C, cooled to room temperature, and then stored in a silica gel desiccator. A total of 5.0 g of each calibration standard was packed into a polyethylene cup (32 mm internal diameter and 23 mm height) covered with a 6‐µm‐thick polypropylene film and then analyzed by wavelength‐dispersive XRF spectrometry. The calibration curve for arsenic obtained from the white rice grains containing arsenic showed good linearity over a concentration range of 0.21–5.00 mg kg^?1 arsenic. The limit of detection of arsenic was 0.080 mg kg^?1. To check the reliability of the XRF method, the concentrations of arsenic in six samples of grain cereals and two samples of flour were compared with those obtained by atomic absorption spectrometry after acid decomposition. The values obtained by both analytical methods showed good agreement. Copyright © 2016 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.     

Lead concentration in feces and urine of exposed rats by x‐ray fluorescence and electrothermal atomic absorption spectrometry

Measurements made in feces and urine of Wistar rats exposed to lead acetate (n = 20) in drinking water since the fetal period were compared with those obtained from a control group (n = 20) in order to assess the age influence on Pb excretion. The measurements were made in different collections of rats aging between 1 and 11 months. To determine the Pb content of the samples, total reflection X‐ray fluorescence (TXRF) and electrothermal atomic absorption spectrometry (ETAAS) were used for the urine samples and energy dispersive X‐ray fluorescence (EDXRF) was used for the feces. The results show high concentrations of Pb being eliminated from the organism by urine and feces in contaminated rats. Values vary from (600 ± 140) µg l^?1 to (5 460 ± 115) µg l^?1 in urine and from (4 500 ± 300) µg g^?1 to (11 400 ± 3 300) µg g^?1 in dry feces. The control rats show, in general, low lead concentrations or below detection limits. The fecal/urinary ratio was studied. It was shown to be about three to four orders of magnitude and positively correlated with time. It was verified in feces and urine that excretion decreases with the animal age and that this decrease is made by different levels of excretion. The excretions of Pb in urine and in feces are positively correlated. A good agreement was found between the results obtained with TXRF and ETAAS for urine samples. This work also stresses the suitability of these techniques in the study of Pb intoxication. Copyright © 2011 John Wiley & Sons, Ltd.     

A pigment (CuS) identified by micro‐Raman spectroscopy on a Chinese funerary lacquer ware of West Han Dynasty

A blue pigment was identified by micro‐Raman spectroscopy, X‐ray fluorescence spectroscopy (XRF), scanning electron microscopy (SEM)/energy dispersive X‐ray (EDX) and X‐ray diffraction (XRD). The test sample, a funerary lacquer tray, belongs to West Han Dynasty (206 BC–AD 8) of China and was decorated with faint blue patterns. The result from Raman spectroscopy showed that the faint blue is covellite (CuS) due to the presence of a characteristic peak at 474.5 cm⁻¹, which further was confirmed by XRF, SEM–EDX and XRD. This research indicated that CuS had been used as a blue pigment to decorate lacquer wares from the West Han Dynasty in China. Copyright © 2009 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.     

Development of a high‐resolution confocal micro‐XRF instrument equipped with a vacuum chamber

A confocal micro‐X‐ray fluorescence (micro‐XRF) instrument equipped with a vacuum chamber was newly developed. The instrument is operated under a vacuum condition to reduce the absorption of XRF in the atmosphere. Thin metal layers were developed to evaluate the confocal volume, corresponding to depth resolution. A set of thin metal layers (Al, Ti, Cr, Fe, Ni, Cu, Zr, Mo, and Au) was prepared by a magnetron sputtering technique. The depth resolutions of the new instrument were varied from 56.0 to 10.9 µm for an energy range from 1.4 to 17.4 keV, respectively. The lower limit of detection (LLD) was estimated by comparison with a glass standard reference material NIST SRM 621). The LLDs obtained by a conventional micro‐XRF were compared with the LLDs obtained by a confocal micro‐XRF instrument. The LLDs were improved in the measurement under confocal configuration because of the reduction of background intensity. Finally, layered materials related to forensic investigation were measured. The confocal micro‐XRF instrument was able to nondestructively obtain the distribution of light elements that cannot be detected by measurement in air. Copyright © 2013 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.     

The determination of elements in welding fume by X‐ray spectrometry and UniQuant

Welding is a hazardous process with an associated risk of health effects related to the fume arising from the core metal, flux components and welding surface. X‐ray fluorescence (XRF) is commonly used to determine elemental concentrations as part of occupational hygiene investigations using conventional calibrations. A method is proposed to determine elements in welding fume using XRF and a fundamental parameter software package known as UniQuant^®. This was found to remove the need for special dust standards being prepared as the calibration used was based on a series of standards supplied with UniQuant that would cover all sample types. A conventional calibration and UniQuant calibration were set up and elements found in welding fume were determined from tin to titanium. Samples obtained from the Health and Safety Laboratory Workplace Analysis Scheme for Proficiency (WASP) programme were also analysed by both methods for nickel, iron, manganese and chromium. For the normal calibration, average recovery results for the WASP samples were between 92 and 103% of the target value with relative standard deviations of 3‐7%. For the UniQuant calibration, average recovery results for the WASP samples were between 97 and 112% of the target value with relative standard deviations of 3‐10%. These results are well within analytical performance expectations for the type of welding fume matrix analysed. The method was applied to real welding fume samples collected from workplaces. Copyright © 2011 John Wiley & Sons, Ltd.     

XRF spectrometer calibration for copper determination in wood

Method of X‐ray fluorescence (XRF) spectrometer calibration for copper analysis in wood was elaborated. Copper salt standard solutions for XRF measurements of liquid samples were prepared, and calibration curve of copper content dependence on impulse counts was determined. Specimens of pine wood (Pinus sylvestris L.) were treated with different solutions of copper‐based preservative (alkaline copper quarternary ammonium compound type) applying model low‐pressure preservation process. After treatment, wood specimens were sliced into six pieces, and exposed surfaces were analyzed using mapping option of XRF spectrometer. Then, wood from each analyzed surface was peeled with abrasive paper and dissolved in 65% nitric (V) acid. Copper content in solutions was determined using obtained calibration curve, and calibration dependence of copper content in wood on the average impulse counts on particular surfaces was calculated. Obtained results of copper content were consistent with values calculated on the basis of differences of samples weight before and after treatment. It confirms that proposed procedure is correct, and obtained equation may be used for unknown samples examination. Copyright © 2012 John Wiley & Sons, Ltd.     

Determination of Calcium and Iron and Measurements of Ash Content in the Brown Coal

Applying the XRF technique and the low-energy X-ray backscattering method an attempt of calcium and iron determination, as well as measurement of the ash content in the brown coal was made. A ²³⁸Pu source, an argon filled propotional counter and a three channel pulse height analyser were used. A simple theoretical model is proposed and obtained results are discussed.     

The comparative analytical performance of the Beagle 2 X‐ray Spectrometer for in situ geochemical analysis on Mars

The Beagle 2 X‐ray Spectrometer (B2 XRS) instrument was part of the Beagle 2 Mars lander payload and intended to perform in situ geochemical analyses of geological materials on Mars. The analytical performance of a spare version of the B2 XRS was compared with (1) a portable X‐ray fluorescence (PXRF) spectrometer designed to perform terrestrial fieldwork and (2) a laboratory‐based wavelength‐dispersive (WD‐XRF) system used to produce high quality geochemical data. The criteria used to assess the performance were based on fitting precision, accuracy and detection limit, determined from the analysis of international geochemical reference materials. The fitting precision of the B2 XRS and PXRF was found to be in agreement with the Horwitz function (a benchmark relating the analysed concentration of an analyte to its uncertainty) over 4 orders of magnitude of concentration range from 10^?1 to 10^?5 g/g. The PXRF generally had a better fitting precision than the B2 XRS because of its better resolution. In order of improving accuracy, the spectrometers generally are ranked B2 XRS, PXRF and WD‐XRF for various major and trace elements. A limiting factor in the accuracy of the B2 XRS was the application of the algorithm used for its quantitative analysis. The detection limits for the spectrometers ranked in the same order as the accuracy as a result of improving signal‐to‐noise ratio (SNR) of elemental peaks, which is a direct consequence of improving resolution between these spectrometers. Overall, the B2 XRS was found to have a favourable analytical performance compared to the benchmark spectrometers, despite having met considerable design constraints and qualification tests as a planetary instrument. Copyright © 2009 John Wiley & Sons, Ltd.     

A multi‐technique approach for the characterization of decorative stones and non‐destructive method for the discrimination of similar rocks

In this paper, a multi‐technique approach, at different scale of observation, is used to characterize a group of decorative stones and to permit to distinguish rocks with similar aspect but coming from different areas. In particular, the samples under study are sedimentary and metamorphic rocks, widely used as building blocks of modern and historical constructions and sculptures. The petrographic and mineralogical features of such rocks were performed by optical microscopy and Raman and Fourier transform infrared absorbance spectroscopies. These techniques permitted to obtain a complete structural, textural, and mineralogical characterization. At elemental level, the investigation was carried out by X‐ray fluorescence (XRF). In particular, XRF and Raman measurements were collected using portable instrumentations, whose advantages for the in situ analysis have been pointed out. The obtained results evidenced the high discriminant capability of the portable XRF for the decorative stones especially when this method is coupled with mineralogical and petrographic information. In this context, we propose to create a database for precious ornamental stones, which could be a starting point for a non‐destructive characterization, even useful for provenance study and/or certification of origin. Copyright © 2013 John Wiley & Sons, Ltd.